Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I.
2004-01-01
The Red Dog Zn-Pb deposits are hosted in organic-rich mudstone and shale of the Mississippian Kuna Formation. A complex mineralization history is defined by four sphalerite types or stages: (1) early brown sphalerite, (2) yellow-brown sphalerite, (3) red-brown sphalerite, and (4) late tan sphalerite. Stages 2 and 3 constitute the main ore-forming event and are volumetrically the most important. Sulfides in stages 1 and 2 were deposited with barite, whereas stage 3 largely replaces barite. Distinct chemical differences exist among the different stages of sphalerite. From early brown sphalerite to later yellow-brown sphalerite and red-brown sphalerite, Fe and Co content generally increase and Mn and Tl content generally decrease. Early brown sphalerite contains no more than 1.9 wt percent Fe and 63 ppm Co, with high Mn (up to 37 ppm) and Tl (126 ppm), whereas yellow-brown sphalerite and red-brown sphalerite contain high Fe (up to 7.3 wt %) and Co (up to 382 ppm), and low Mn (<27 ppm) and Tl (<37 ppm). Late tan sphalerite has distinctly lower Fe (< 0.9 wt %) and higher Tl (up to 355 ppm), Mn (up to 177 ppm), and Ge (426 ppm), relative to earlier sphalerite. Wide ranges in concentrations of Ag, Cu, Pb, and Sb characterize all sphalerite types, particularly yellow-brown sphalerite and red-brown sphalerite, and most likely reflect submicroscopic inclusions of galena, chalcopyrite and/or tetrahedrite in the sphalerite. In situ ion microprobe sulfur isotope analyses show a progression from extremely low ??34S values for stage 1 (as low as -37.20???) to much higher values for yellow-brown sphalerite (mean of 3.3???; n = 30) and red-brown sphalerite (mean of 3.4; n = 20). Late tan sphalerite is isotopically light (-16.4 to -27.2???). The textural, chem ical, and isotopic data indicate the following paragenesis: (1) deposition of early brown sphalerite with abundant barite, minor pyrite, and trace galena immediately beneath the sea floor in unconsolidated mud; (2) deposition of yellow-brown sphalerite during subsea-floor hydrothermal recrystallization and coarsening of preexisting barite; (3) open-space deposition of barite, red-brown sphalerite and other sulfides in veins and coeval replacement of barite; and (4) postore sulfide deposition, including the formation of late tan sphalerite breccias. Stage 1 mineralization took place in a low-temperature environment where fluids rich in Ba mixed with pore water or water-column sulfate to form barite, and metals combined with H2S derived from bacterial sulfate reduction to form sulfides. Higher temperatures and salinities and relatively oxidized ore-stage fluids (stages 2 and 3) compared with stage 1 were probably important controls on the abundances and relative amounts of metals in the fluids and the resulting sulfide chemistry. Textural observations and isotopic data show that preexisting barite was reductively dissolved, providing a source of H2S for sulfide mineral formation. In stage 3, the continued flow of hydrothermal fluids caused thermal alteration of organic-rich mudstones and a build-up of methane that led to fluid overpressuring, hydrofracturing, and vein formation. Barite, red-brown sphalerite, and other sulfides were deposited in the veins, and preexisting barite was pervasively replaced by red-brown sphalerite. Hydrothermal activity ceased until Jurassic time when thrusting and large-scale fluid flow related to the Brookian orogeny remobilized and formed late tan sphalerite in tectonic breccias. ?? 2004 by Economic Geology.
Cao, Mingli; Liu, Qi
2006-09-15
Zinc sulfate is a well-known selective depressant for zinc sulfide minerals such as sphalerite during the flotation of complex Cu-Pb-Zn sulfide ores. It deactivates sphalerite flotation by substituting the activating metal ions, and depresses sphalerite flotation by forming hydrophilic coatings of zinc hydroxyl species on sphalerite surfaces. However, we recently observed that zinc sulfate could also induce coagulation of fine sphalerite particles and such coagulation significantly reduced the mechanical entrainment of the fine sphalerite. Therefore, it seems that the effectiveness of zinc sulfate as a selective sphalerite depressant is not only due to its ability to make mineral surface hydrophilic, which reduces genuine flotation, but also due to its ability to coagulate the mineral, which reduces mechanical entrainment. Zinc sulfate is a "dual function" selective flotation depressant.
Trace and minor elements in sphalerite from metamorphosed sulphide deposits
NASA Astrophysics Data System (ADS)
Lockington, Julian A.; Cook, Nigel J.; Ciobanu, Cristiana L.
2014-12-01
Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.
Pfaff, Katharina; Koenig, Alan; Wenzel, Thomas; Ridley, Ian; Hildebrandt, Ludwig H.; Leach, David L.; Markl, Gregor
2011-01-01
Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.
NASA Astrophysics Data System (ADS)
Liu, Jian; Wen, Shuming; Deng, Jiushuai; Chen, Xiumin; Feng, Qicheng
2014-08-01
The interaction among sphalerite (1 1 0) surface, copper and ethyl xanthate (EX) was simulated using the density functional theory (DFT). The results of DFT indicate that four types of stable interaction models exist among sphalerite surface, copper and EX, i.e., EX interacts with the Cu substituted for Zn, Cu adsorbed on the top site of S, Cu adsorbed on the bridge site of S and Cu(OH)2 adsorbed on the sphalerite surface. The four interaction models can result in the activation flotation of sphalerite. Density of states (DOS) analysis shows that the energy level discrepancy of the Zn 3d orbital in ZnS and the bonding S 3p orbital in EX results in the weak adsorption of EX on un-activated sphalerite surface. However, after copper activation, the Cu 3d orbital peak and bonding S 3p orbital peak are just maximally overlapped nearby the Fermi level. This study provides an insight into the nature that sphalerite responds not well to EX and also a comprehensive understanding on the possible interaction cases existing among sphalerite surface, copper and EX.
The role of mineral surface chemistry in modified dextrin adsorption.
Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A
2011-05-15
The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Bauer, Matthias E.; Seifert, Thomas; Burisch, Mathias; Krause, Joachim; Richter, Nancy; Gutzmer, Jens
2017-12-01
At the Hämmerlein skarn deposit, located in the western Erzgebirge (Germany), a major cassiterite-dominated Sn mineralization stage is spatially associated with a younger Zn-Cu-In sulfide mineralization stage. In this contribution, we provide the first detailed description of the Zn-Cu-In sulfide mineralization stage, based on field geological observations combined with detailed petrographic studies and electron probe microanalysis data. Indium-rich sulfide mineralization occurs as irregular, semi-massive lenses or as infill of short, discontinuous veinlets that crosscut the cassiterite-bearing skarn assemblage. Indium- and Cu-rich sphalerite and roquesite are found to be closely associated with In-bearing chalcopyrite. The highest In concentrations in sphalerite occur at the rims and along cracks of sphalerite grains. The distribution resembles diffusion profiles, suggesting that the In enrichment is due to an hydrothermal overprint that postdates the initial formation of both sphalerite and chalcopyrite. Textural relations illustrate that the diffusion fronts in sphalerite grains are thicker where they are in contact to anhedral masses of hematite and magnetite. Our observations suggest that In enrichment in sphalerite at the Hämmerlein skarn deposit is due to the decomposition of In-bearing chalcopyrite. The resultant release of Fe led to the formation of hematite and magnetite, whereas Cu and In were incorporated into sphalerite along grain boundaries and micro fractures. Incorporation into the sphalerite lattice took place by coupled substitution of Cu+ + In3+ ↔ 2Zn2+, suggesting that the concurrent availability of Cu and In may be an essential factor to enrich In in sphalerite in hydrothermal ore-forming environments.
Chalcopyrite disease in sphalerite: pathology and epidemiology.
Barton, P.B.; Bethke, P.M.
1987-01-01
This descriptive paper identifies three widely occurring textures designated as 'watermelon', 'dusting' and 'bimodal' that characterize the replacement of original Fe-bearing sphalerite by an aggregate of chalcopyrite and low-Fe sphalerite as an integral part of the mineralization process. Replacement probably predominates over alternative modes of origin for small chalcopyrite blebs in sphalerite from most vein and sea-floor massive sulphide deposits that formed in the 200-400oC temperature range and that have not been subsequently subjected to higher T. Sphalerite from the epithermal Ag-Pb-Zn deposit at Creede, Colorado, displays a rich variety of features ("bead chains') that are primary crystal dislocations decorated by exsolved chalcopyrite.-J.A.Z.
Vasanthakumar, B; Ravishankar, H; Subramanian, S
2013-12-01
The selective flotation of sphalerite from a sphalerite-galena mineral mixture has been achieved using cells and extracellular secretions of Bacillus megaterium after adaptation to the chosen minerals. The extracellular secretions obtained after thermolysis of bacterial cells adapted to sphalerite yield the highest flotation recovery of sphalerite with a selectivity index value of 24.5, in comparison to the other cellular and extra-cellular bio-reagents studied. The protein profile for the unadapted and mineral-adapted cells has been found to differ distinctly, attesting to variation in the yield and nature of extra-cellular polymeric substances (EPS). The changes induced in the bacterial cell wall components after adaptation to sphalerite or galena with respect to the contents of phosphate, uronic acid and acetylated sugars of B. megaterium have been quantified. The role of the dissolved metal ions from the minerals as well as that of the constituents of extracellular secretions in modulating the surface charge of the bacterial cells as well as the minerals under study has been confirmed using various enzymatic treatments of the bacterial cells. It has been demonstrated that the induction of additional molecular weight protein fractions as well as the higher amount of extracellular proteins and phosphate secreted after adaptation to sphalerite vis-à-vis galena are contributory factors for the selective separation of sphalerite from galena. Copyright © 2013 Elsevier B.V. All rights reserved.
Bawden, T.M.; Einaudi, M.T.; Bostick, B.C.; Meibom, A.; Wooden, J.; Norby, J.W.; Orobona, M.J.T.; Chamberlain, C.P.
2003-01-01
We identified submicrometer-sized framboidal sphalerite (ZnS) below the base of supergene oxidation in a Carlin-type gold deposit of Eocene age in Nevada, United States, where the framboidal sphalerite forms a blanket-like body containing >400,000 metric tons of zinc. Framboidal sphalerite <0.1 ??m in diameter, formed in the early Miocene, ranges from <0.1 to 0.35 mol% FeS; the ??34S values range from -25??? to -70???, the lowest values measured in a marine or terrestrial environment. These S isotope data demonstrate the involvement of sulfate-reducing bacteria and provide the first documentation that sphalerite can form significant supergene sulfide-enrichment blankets.
Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0
Stanton, M.R.; Gemery-Hill, P. A.; Shanks, Wayne C.; Taylor, C.D.
2008-01-01
High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).
Karakus, M.; Hagni, R.D.; Koenig, A.; Ciftc, E.
2008-01-01
Natural sphalerite associated with copper, silver, lead-zinc, tin and tungsten deposits from various world-famous mineral deposits have been studied by cathodoluminescence (CL), laser ablasion inductively coupled plasma mass spectrometry (LA-ICP-MS), electron probe microanalysis (EPMA) and electron paramagnetic resonance (EPR) to determine the relationship between trace element type and content and the CL properties of sphalerite. In general, sphalerite produces a spectrum of CL colour under electron bombardment that includes deep blue, turquoise, lime green, yellow-orange, orange-red and dull dark red depending on the type and concentration of trace quantities of activator ions. Sphalerite from most deposits shows a bright yellow-orange CL colour with ??max centred at 585 nm due to Mn2+ ion, and the intensity of CL is strongly dependent primarily on Fe2+ concentration. The blue emission band with ??max centred at 470-490 nm correlates with Ga and Ag at the Tsumeb, Horn Silver, Balmat and Kankoy mines. Colloform sphalerite from older well-known European lead-zinc deposits and late Cretaceous Kuroko-type VMS deposits of Turkey shows intense yellowish CL colour and their CL spectra are characterised by extremely broad emission bands ranging from 450 to 750 nm. These samples are characterised by low Mn (<10 ppm) and Ag (<1 ppm), and they are enriched in Tl (1-30 ppm) and Pb (80-1500 ppm). Strong green CL is produced by sphalerite from the Balmat-Edwards district. Amber, lime-green and red-orange sphalerite produced weak orange-red CL at room temperatures, with several emission bands centred at 490, 580, 630, 680, 745, with ??max at 630 nm being the strongest. These emission bands are well correlated with trace quantities of Sn, In, Cu and Mn activators. Sphalerite from the famous Ogdensburg and Franklin mines exhibited brilliant deep blue and orange CL colours and the blue CL may be related to Se. Cathodoluminescence behaviour of sphalerite serves to characterise ore types and help detect technologically important trace elements.
NASA Astrophysics Data System (ADS)
Choi, S. K.; Pak, S. J.; Kim, J.; Park, J. W.; Son, S. K.
2017-12-01
Sn-rich chimney fragments (up to 1,720 ppm) were recovered with ultramafic rocks from ocean core complex (OCC-4-1) of Central Indian Ridge, 12.4°S. The chimney fragments are featured by barite-free and Zn-rich (up to 50.1 wt.%) ores. The chimney fragments are mainly composed of sphalerite, isocubanite, pyrrhotite, chalcopyrite and marcasite with galena and electrum as minor minerals. The precipitation sequences of the minerals are categorized into three stages by mineral assemblage; early stage with low-temperature minerals, late stage with high-temperature minerals and seawater weathering stage with covellite, Fe-oxyhydroxides and amorphous silica. Early stage is characterized by sphalerite, intermittently showing colloform-texture, closely co-existed with anhedral marcasite and minor galena, whereas late stage is dominated by aggregates of isocubanite with chalcopyrite exsolution lamellae, pyrrhotite partially replaced by long prismatic marcasite and FeS enriched sphalerite (up to 42.69 FeS mole%). Electrums, main phase of gold mineralization, are mostly visible grains (< 3 um in diameter), occuring in sphalerite and isocubanite as inclusions and/or free gold in amorphous silica through the whole mineralization stages. On the basis of semi-quantified analysis, electrum grains are likely to have Au-rich composition. High Sn concentrations are typically observed in altered rim along the grain boundaries between sphalerite and isocubanite, going up to 5.5 wt.% in sphalerite. LA-ICP-MS mapping exhibits that Sn is preferentially incorporated into sphalerite relative to isocubanite, especially showing the highest values in boundaries between both minerals, but significantly lower in marcasite. Stoichiometry of Sn-enriched sphalerite rim seems to have a uniform ratio of atomic proportion of Cu to Sn as almost 2:1, implying that stannite micro-inclusions may result in Sn-enrichment. The LA-ICP-MS spectra also shows abrupt increase in Sn signal intensity, indicating Sn-bearing inclusions are distributed within sphalerite. Therefore, Sn-bearing mineral in sphalerite and isocubanite is likely to be fine particle of stannite in late stage and subsequently one of the possible ways to precipitate these particles could be reworking process of previously deposited Sn-bearing sulfides.
Cadmium contamination of agricultural soils and crops resulting from sphalerite weathering.
Robson, T C; Braungardt, C B; Rieuwerts, J; Worsfold, P
2014-01-01
The biogeochemistry and bioavailability of cadmium, released during sphalerite weathering in soils, were investigated under contrasting agricultural scenarios to assess health risks associated with sphalerite dust transport to productive soils from mining. Laboratory experiments (365 d) on temperate and sub-tropical soils amended with sphalerite (<63 μm, 0.92 wt.% Cd) showed continuous, slow dissolution (0.6-1.2% y(-1)). Wheat grown in spiked temperate soil accumulated ≈38% (29 μmol kg(-1)) of the liberated Cd, exceeding food safety limits. In contrast, rice grown in flooded sub-tropical soil accumulated far less Cd (0.60 μmol kg(-1)) due to neutral soil pH and Cd bioavailability was possibly also controlled by secondary sulfide formation. The results demonstrate long-term release of Cd to soil porewaters during sphalerite weathering. Under oxic conditions, Cd may be sufficiently bioavailable to contaminate crops destined for human consumption; however flooded rice production limits the impact of sphalerite contamination. Copyright © 2013 Elsevier Ltd. All rights reserved.
Recalibration of the sphalerite cosmobarometer: Experimental and theoretical treatment
NASA Astrophysics Data System (ADS)
Balabin, Alexey I.; Urusov, Vadim S.
1995-04-01
Temperature dependence of the composition of sphalerite in equilibrium with troilite + metallic iron has been determined experimentally from 400 to 840°C at 1 bar. The high-temperature runs (660-840°C) were conducted in evacuated silica tubes; a new version of the recrystallization in anhydrous halide flux technique was used for attaining equilibrium at 600-400°C. The zero-pressure solvus of sphalerite proved to be at higher FeS contents than was located by Barton and Toulmin (1966). Detailed calculations, based on updated thermochemical appraisal of the sphalerite (Zn,Fe)S solution, have shown the new solvus to be in apparent consistency with the high-pressure experimental data of Hutchison and Scott (1983 ). An improved calibration of the cosmobarometer is presented, based on our experimental results and those of Hutchison and Scott (1983) ; the calibration takes into account some inferences regarding thermodynamic properties of sphalerite solution and low-temperature polymorphism in FeS. Recently published metallographic cooling rates of iron meteorites (Saikumar and Goldstein, 1988) provide estimates of blocking temperatures for Fe diffusion in sphalerite, which fall in the range 205-217°C. Pressures of formation of these meteorites calculated from available sphalerite compositions range from 0 for Landes to 1.8 kbar for Toluca. The most reliable of the pressure estimates exhibit a linear relationship with wt% Ni of the meteorite.
Curtis, Susan B; Hewitt, Jeff; Macgillivray, Ross T A; Dunbar, W Scott
2009-02-01
During mineral processing, concentrates of sulfide minerals of economic interest are formed by froth flotation of fine ore particles. The method works well but recovery and selectivity can be poor for ores with complex mineralogy. There is considerable interest in methods that improve the selectivity of this process while avoiding the high costs of using flotation chemicals. Here we show the first application of phage biotechnology to the processing of economically important minerals in ore slurries. A random heptapeptide library was screened for peptide sequences that bind selectively to the minerals sphalerite (ZnS) and chalcopyrite (CuFeS2). After several rounds of enrichment, cloned phage containing the surface peptide loops KPLLMGS and QPKGPKQ bound specifically to sphalerite. Phage containing the peptide loop TPTTYKV bound to both sphalerite and chalcopyrite. By using an enzyme-linked immunosorbant assay (ELISA), the phage was characterized as strong binders compared to wild-type phage. Specificity of binding was confirmed by immunochemical visualization of phage bound to mineral particles but not to silica (a waste mineral) or pyrite. The current study focused primarily on the isolation of ZnS-specific phage that could be utilized in the separation of sphalerite from silica. At mining sites where sphalerite and chalcopyrite are not found together in natural ores, the separation of sphalerite from silica would be an appropriate enrichment step. At mining sites where sphalerite and chalcopyrite do occur together, more specific phage would be required. This bacteriophage has the potential to be used in a more selective method of mineral separation and to be the basis for advanced methods of mineral processing.
Zinc isotopes in sphalerite from base metal deposits in the Red Dog district, northern Alaska
Kelley, K.D.; Wilkinson, J.J.; Chapman, J.B.; Crowther, H.L.; Weiss, D.J.
2009-01-01
Analyses of sphalerite samples from shale-hosted massive sulfide and stratigraphically underlying vein breccia deposits in the Red Dog district in northern Alaska show a range ??66Zn values from zero to 0.60 per mil. The lowest values are observed in the vein breccia deposits, and the stratigraphically overlying (but structurally displaced) shale-hosted massive sulfide deposits show a systematic trend of increasing ??66Zn values from south to north (Main-Aqqaluk-Paalaaq-Anarraaq). The ??66Zn values are inversely correlated with sphalerite Fe/Mn ratio and also tend to be higher in low Cu sphalerite, consistent with precipitation of lower ??66Zn sphalerite closer to the principal hydrothermal fluid conduits. The most likely control on isotopic variation is Rayleigh fractionation during sulfide precipitation, with lighter zinc isotopes preferentially incorporated in the earliest sphalerite to precipitate from ore fluids at deeper levels (vein breccias) and close to the principal fluid conduits in the orebodies, followed by precipitation of sulfides with higher ??66Zn values in shallower and/or more distal parts of the flow path. There is no systematic variation among the paragenetic stages of sphalerite from a single deposit, suggesting an isotopically homogeneous zinc source and consistent transport-deposition conditions and/or dissolution-reprecipitation of earlier sphalerite without significant fractionation. Decoupled Zn and S isotope compositions are best explained by mixing of separate metal- and sulfur-bearing fluids at the depositional site. The results confirm that Zn isotopes may be a useful tracer for distinguishing between the central and distal parts of large hydrothermal systems as previously suggested and could therefore be of use in exploration. ?? 2009 by Economic Geology.
NASA Astrophysics Data System (ADS)
Tonkacheev, Dmitry; Chareev, Dmitry; Abramova, Vera; Tagirov, Boris
2016-04-01
Sphalerite and covellite are widespread minerals in the different genetic types of deposits and forms under the various conditions. The purpose of this work is to determine the possible range of concentration and chemical state of Au and PGE (Pt, Pd, Rh) in sphalerite (Zn,Fe) S and covellite (CuS). These minerals were synthesized using gas transport and salt flux techniques. The crystals of ZnS were grown using the gas transport method at 850°C and the salt flux one using NaCl/KCl, CsCl/NaCl/KCl, and LiCl/RbCl eutectic mixtures at 850, 645 and 470°C, respectively. CuS crystals were synthesized using the salt flux method in RbCl/LiCl melt at 470 and 340°C. The trace metal activity was always controlled by the presence of pure metal or its sulfide, and, therefore, the concentration of these elements in synthesized phases represent the maximum possible value for given T/f(S2) synthesis parameters. The LA-ICP-MS and/or EPMA techniques were used to determine the Au concentration in synthesized phases. The concentration of Au in sphalerite, synthesized at 850°C with admixture of Cd, Se, In, Fe, and Mn, reached 0.3wt%, whereas the sphalerite cell parameter extremely increased up to 5.4161Å relatively to 5.4060 Å for pure ZnS. It was found that the observed high Au concentration is caused by the presence of In (2091±46 ppm Au in sample with Fe and In in comparison with 14±7 for Se-bearing ZnS, 94±12 ppm for Fe-Mn-bearing sphalerite, and 96±46 for Fe-bearing sphalerite. The concentration of Au in Fe-bearing sphalerite synthesized at 645°C does not exceed 5 ppm. Therefore, increase of temperature results in the increase of Au concentration in sphalerite. The concentration of Au in another Fe-bearing-sphalerite series synthesized using gas transport method at 850°C various from 200 to 500 ppm and depends on the iron content. This fact could be related to the oxidation state or Fe in ZnS-FeS solid solution series. The concentration of Pt and Pd, Rh in sphalerite is below the detection limit of LA-ICP-MS (~30 ppb). However, these trace elements change the cathodoluminescence properties of ZnS. The concentration or gold in covellite was determined by both LA-ICP-MS and EPMA techniques and the final values clearly fit together. The maximum concentration can be observed at 450° and equal to 0.3wt%. This value changes minor due to the increasing of the temperature. In principle, adding admixtures of In, Zn, Se, Cu, Sb, Bi did not affect on the concentration of Au. However, in experiment where sulfur is excessive and a mixture of In, Zn, Se, Cu, Sb, Bi, were added the concentration of Au is equal 0.128+0.028 ppm. The gold distribution in covellite and sphalerite is always homogeneous. According to XANES data, atoms of Au in the crystal structure covellite is in triangles, formed by the atoms of Cu. In sphalerite gold is in "invisible" state too.
NASA Astrophysics Data System (ADS)
Pašava, Jan; Tornos, Fernando; Chrastný, Vladislav
2014-10-01
We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from -0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S = +6.6 and stage 2 has δ34S = -0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from -0.80 to -0.01 per mil (mostly between -0.80 and -0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250-320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S > mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn accompanied by heavy δ34S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ66Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.
Commentary on the sphalerite geobarometer
Toulmin, P.; Barton, P.B.; Wiggins, L.B.
1991-01-01
The FeS content of sphalerite in assemblages with pyrite and pyrrhotite has been widely used and widely criticized as a geobarometer. The commonly accepted form of the geobarometer is based on the composition of sphalerite being independent of temperature below about 550??C at all pressures up to at least 10 kbar, but strong thermodynamic arguments require a significant temperature dependence in this region. Most minor components have a negligible effect on the relevant equilibria, but the effect of CuS is somewhat more significant. Molar and partial molar volumes for binary (ZnS-FeS) and ternary (ZnS-FeS-CuS) sphalerite solutions are presented; the ternary data are consistent with charge transfer between Cu and Fe. -from Authors
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ambers, C.P.
1993-03-01
Sphalerite is associated with very well crystallized kaolinite (VWCK) in geodes, siderite nodules and coal cleats in the Illinois Basin and allows estimation of the temperature of formation of the VWCK using fluid inclusions. The approximate depth of kaolinite growth and the relative timing of coal fracturing can then be ascertained. Sphalerite associated with VWCK was extracted from Mississippian geodes collected near Keokuk, Iowa, and from Pennsylvanian siderite nodules and coal collected in SW Indiana. Inclusions in the sphalerite consist of VWCK; large, negative crystal, two-phase fluid inclusions; small, fracture-related, two-phase fluid inclusions; and organic inclusions. Homogenization temperatures of 89more » C [+-] 10, 115 C [+-] 15, 89 C [+-] 5 were measured for the two-phase inclusions in sphalerite from the geodes, siderite nodules and coal, respectively. Freezing temperatures of the inclusions in the geode and siderite nodule sphalerite were measured at [minus]13.5 C [+-] 0.5 and [minus]9.4 C [+-] 0.2, indicating moderate salinity. Using a geothermal gradient range of 23--36 C/km and an average surface temperature of 20 C, kaolinite and sphalerite probably grew at depths of about 1.9 to 4.1 km. In SW Indiana, VWCK occurs in vertical, non-penetrative joints in vitrinite layers. Penetrative joint sets rarely contain VWCK. At nearly all of the 28 sites studied, two sets of barren cleats occur oriented N10W to NSE and N80E to N95E. The orientation of barren, penetrative cleats shows that the maximum horizontal stress rotated CW from the earlier stress field. Rare VWCK in the late cleats suggests they also formed at depth after the thermal maxima.« less
The effect of iron and copper impurities on the wettability of sphalerite (110) surface.
Simpson, Darren J; Bredow, Thomas; Chandra, Anand P; Cavallaro, Giuseppe P; Gerson, Andrea R
2011-07-15
The effect of impurities in the zinc sulfide mineral sphalerite on surface wettability has been investigated theoretically to shed light on previously reported conflicting results on sphalerite flotation. The effect of iron and copper impurities on the sphalerite (110) surface energy and on the water adsorption energy was calculated with the semi-empirical method modified symmetrically orthogonalized intermediate neglect of differential overlap (MSINDO) using the cyclic cluster model. The effect of impurities or dopants on surface energies is small but significant. The surface energy increases with increasing surface iron concentration while the opposite effect is reported for increasing copper concentration. The effect on adsorption energies is much more pronounced with water clearly preferring to adsorb on an iron site followed by a zinc site, and copper site least favorable. The theoretical results indicate that a sphalerite (110) surface containing iron is more hydrophilic than the undoped zinc sulfide surface. In agreement with the literature, the surface containing copper (either naturally or by activation) is more hydrophobic than the undoped surface. Copyright © 2011 Wiley Periodicals, Inc.
NASA Astrophysics Data System (ADS)
Lyubimtseva, N. G.; Bortnikov, N. S.; Borisovsky, S. E.; Prokofiev, V. Yu.; Vikent'eva, O. V.
2018-03-01
The mineral assemblages, mode of occurrence, and chemical compositions of coexisting fahlore and sphalerite from the Darasun gold deposit have been described. Three generations of fahlore and three generations of sphalerite have been recognized. The FeS content in sphalerite coexisting with fahlore ranges from 0.8 to 9.4 mol %. The complete solid solution series Fe-tetrahedrite-Zn-tetrahedrite-Fe-tennantite-Zn-tennantite reflected in Sb/(Sb + As) and Fe/(Fe + Zn) ratios ranging from 0 to 0.97 and from 0.07 to 1.00, respectively, with a predominant negative relationship between these ratios has been identified for the first time at the deposit. Stepped, oscillatory, and combined stepped-oscillatory growth zonings within fahlore grains and heterogeneous aggregates of fahlore have been found. Fahlore is enriched in As with respect to Sb, and Zn-tetrahedrite is followed by Fe- and Zn-tennantite from early to late generation; Zn-tetrahedrite is followed by Fe-tennantite in zoned grains and overgrown rims; sphalerite crystallized at decreased temperature and sulfur fugacity. The evolution of the chemical composition of fahlores was caused by the evolving temperature, fluid salinity, and conditions of metal migration.
A novel property of DNA - as a bioflotation reagent in mineral processing.
Vasanthakumar, Balasubramanian; Ravishankar, Honnavar; Subramanian, Sankaran
2012-01-01
Environmental concerns regarding the use of certain chemicals in the froth flotation of minerals have led investigators to explore biological entities as potential substitutes for the reagents in vogue. Despite the fact that several microorganisms have been used for the separation of a variety of mineral systems, a detailed characterization of the biochemical molecules involved therein has not been reported so far. In this investigation, the selective flotation of sphalerite from a sphalerite-galena mineral mixture has been achieved using the cellular components of Bacillus species. The key constituent primarily responsible for the flotation of sphalerite has been identified as DNA, which functions as a bio-collector. Furthermore, using reconstitution studies, the obligatory need for the presence of non-DNA components as bio-depressants for galena has been demonstrated. A probable model involving these entities in the selective flotation of sphalerite from the mineral mixture has been discussed.
A Novel Property of DNA – As a Bioflotation Reagent in Mineral Processing
Vasanthakumar, Balasubramanian; Ravishankar, Honnavar; Subramanian, Sankaran
2012-01-01
Environmental concerns regarding the use of certain chemicals in the froth flotation of minerals have led investigators to explore biological entities as potential substitutes for the reagents in vogue. Despite the fact that several microorganisms have been used for the separation of a variety of mineral systems, a detailed characterization of the biochemical molecules involved therein has not been reported so far. In this investigation, the selective flotation of sphalerite from a sphalerite-galena mineral mixture has been achieved using the cellular components of Bacillus species. The key constituent primarily responsible for the flotation of sphalerite has been identified as DNA, which functions as a bio-collector. Furthermore, using reconstitution studies, the obligatory need for the presence of non-DNA components as bio-depressants for galena has been demonstrated. A probable model involving these entities in the selective flotation of sphalerite from the mineral mixture has been discussed. PMID:22768298
Vasanthakumar, Balasubramanian; Ravishankar, Honnavar; Subramanian, Sankaran
2014-03-01
Studies were carried out to assess the utility of the cellular and extracellular constituents of Bacillus megaterium for the flotation of sphalerite and galena minerals. Based on the flotation results on the individual minerals, it was observed that sphalerite was preferentially floated compared to galena. A maximum selectivity index (SI) value of 11.7 was achieved in the presence of the soluble fraction of the thermolysed cells, which was higher than that obtained with the intact cells (SI of 6.5) and the insoluble fraction of the thermolysed cells (SI of 9.6). The results of the various enzymatic treatment tests revealed that extracellular DNA played a vital role in the selective flotation of sphalerite. A noteworthy finding was that the single-stranded DNA (ssDNA) had a higher biocollector capacity vis-à-vis the double-stranded DNA (dsDNA), leading to better flotation efficiency. About 95 % recovery of sphalerite could be achieved from the mineral mixture by the combined addition of the ssDNA with the non-DNA components of the bacterial cells, resulting in a maximum SI of 19.1. Calcium and phosphate components of the nutrient media were found to be essential for better selectivity of separation of sphalerite. The mechanisms of microbe-mineral interaction are discussed.
NASA Astrophysics Data System (ADS)
Ambers, Clifford P.
2001-09-01
A minor, normal fault related to compaction of the grainstone shoal facies of the Salem Limestone in south-central Indiana provides an unusual opportunity to test the pressure and temperature of both faulting and associated stylolitization. Syn-deformational sphalerite occurs in voids along the fault where it intersects an organic-rich shale parting in the sand flat facies overlying the grainstone. The sphalerite contains fluid inclusions that can be used for microthermobaric measurements. Most fluid inclusions in the sphalerite are demonstrably cogenetic with the host sphalerite and of the two-phase aqueous type common in Indiana, although many contain petroleum and others contain gas. Crushing tests in kerosene indicate that the aqueous inclusions contain dissolved methane in varying amounts as high as 1000 ppm. Microthermometry shows that late sphalerite growth, late fault movement, and late stylolitization all occurred as conditions approached 108°C and 292 bars. This pressure is in accord with a normal, basinal, geothermal gradient of 32.5°C/km that would produce the observed temperature under hydrostatic conditions at a burial depth of 2.7 km using an average fluid density of 1.1 g/cm 3. These results serve as a reminder that fluid inclusions in diagenetic minerals hold important temperature and pressure information regarding burial diagenesis of Paleozoic rocks across the North American midcontinent. Detailed study of dissolved gases in fluids trapped in disseminated sphalerite that is common across the midcontinent could help resolve the enigma of sedimentary rocks with high thermal maturity exposed at the surface across the region.
The experimental refinement of the sphalerite-troilite cosmobarometer
NASA Astrophysics Data System (ADS)
Balabin, A. I.; Urusov, V. S.; Senin, V. G.; Osadchii, E. G.
1987-04-01
Discrepancies were observed by comparing the equation of Barton and Toulmin (1966) for the limiting solubility of FeS in sphalerite (which is the 'scale' in the sphalerite-troilite barometer of Barton and Toulmin) and the data on FeS solubility of Sorokin and Chichagov (1974). For this paper, some of the Barton and Toulmin experiments were repeated; in addition, the effect of Ni as an impurity in metallic Fe on the FeS solubility was investigated. A new relationship was obtained between the limiting solubility of FeS in sphalerite, the absolute temperature, and the pressure, which is slightly different from that obtained on the basis of Barton and Toulmin data and which agrees with the results of Sorokin and Chichagov. Introduction of Ni had little effect. The pressures of formation for several meteorites were estimated and compared with pressures obtained, on the basis of Barton and Toulmin data, by Hutchison and Scott (1983). The greatest discrepancies are observed for meteorites formed at very low pressures.
Chandra, A P; Gerson, A R
2009-01-30
A review of the considerable, but often contradictory, literature examining the specific surface reactions associated with copper adsorption onto the common metal sulfide minerals sphalerite, (Zn,Fe)S, and pyrite (FeS(2)), and the effect of the co-location of the two minerals is presented. Copper "activation", involving the surface adsorption of copper species from solution onto mineral surfaces to activate the surface for hydrophobic collector attachment, is an important step in the flotation and separation of minerals in an ore. Due to the complexity of metal sulfide mineral containing systems this activation process and the emergence of activation products on the mineral surfaces are not fully understood for most sulfide minerals even after decades of research. Factors such as copper concentration, activation time, pH, surface charge, extent of pre-oxidation, water and surface contaminants, pulp potential and galvanic interactions are important factors affecting copper activation of sphalerite and pyrite. A high pH, the correct reagent concentration and activation time and a short time delay between reagent additions is favourable for separation of sphalerite from pyrite. Sufficient oxidation potential is also needed (through O(2) conditioning) to maintain effective galvanic interactions between sphalerite and pyrite. This ensures pyrite is sufficiently depressed while sphalerite floats. Good water quality with low concentrations of contaminant ions, such as Pb(2+)and Fe(2+), is also needed to limit inadvertent activation and flotation of pyrite into zinc concentrates. Selectivity can further be increased and reagent use minimised by opting for inert grinding and by carefully choosing selective pyrite depressants such as sulfoxy or cyanide reagents. Studies that approximate plant conditions are essential for the development of better separation techniques and methodologies. Improved experimental approaches and surface sensitive techniques with high spatial resolution are needed to precisely verify surface structures formed after copper activation. Sphalerite and pyrite surfaces are characterised by varying amounts of steps and defects, and this heterogeneity suggests co-existence of more than one copper-sulfide structure after activation.
Mn distribution in natural sphalerites: a micronalytical and EPR study
NASA Astrophysics Data System (ADS)
di Benedetto, F.; Bernardini, G. P.; Cipriani, C.; Plant, D.; Romanelli, M.; Vaughan, D. J.
2003-04-01
Electron Paramagnetic Resonance (EPR) has been successfully applied to determine the local coordination and distribution of transition metal cations in sulphides and sulphosalts (Di Benedetto et al., 2002). Due to its enhanced sensitivity and element-specificity it is one of the best tools to monitor Mn(II) behaviour down to very low concentrations. In order to reach a fuller understanding of the spectroscopic results, a microanalytical study has also been undertaken by means of Electron Microprobe Analysis. Operating conditions were chosen to achieve the lowest possible detection limits, taking into account that Mn can replace Zn in the sphalerite lattice both as a minor and trace element, and that EPR can detect Mn(II) below the ppm range. Six natural samples from the Museo di Storia Naturale, Università di Firenze, were selected to have pure single crystals and avoid magnetically active phases associated with the sphalerite. The Mn concentration determined ranges between 30 and 14300 ppm and Mn content varies considerably within the same sample, leading to differences up to the 50% as compared to the mean value. X-ray images confirm Mn to be distributed with an unusual pattern, unrelated to the other common Zn-replacing cations, Fe and Cd, present in the samples. Powder EPR spectra reveal at least three different Mn(II) signals: two sextets, overlapping in all samples containing Mn as trace element, and a single line, present only in the more concentrated samples. While the latter have been attributed to an inhomogeneous Mn distribution, due to an enhanced Mn-Mn superexchange interaction, the difference between the two sextets, observed by means of EEPR investigations in a synthetic sphalerite (Di Benedetto et al., 2002), appears unrelated to the Mn concentration and may be attributed to small differences in the local coordination of Mn(II) ions. This, in turn, may be explained by the segregation of small amounts of Mn into polytypic domains, features which usually characterise large sphalerite crystals. This study shows the distinctive behaviour of Mn in sphalerite, both at the micron and submicron scales. These features point to sphalerites "preserving" the out-of-equilibrium conditions of their genesis. Mn(II) magnetic interactions may play an important role in the stabilisation of polytypic hexagonal domains during the growth of sphalerite crystals. Di Benedetto, F., Bernardini, G.P., Caneschi, A., Cipriani, C., Danti, C., Pardi, L. and Romanelli, M. (2002): EPR and magnetic investigations on sulfides and sulfosalts. Eur. J. Mineral., 4(6), 1053.
Xiao, Yunhua; Liu, Xueduan; Dong, Weiling; Liang, Yili; Niu, Jiaojiao; Gu, Yabing; Ma, Liyuan; Hao, Xiaodong; Zhang, Xian; Xu, Zhen; Yin, Huaqun
2017-07-01
This study used an artificial microbial community with four known moderately thermophilic acidophiles (three bacteria including Acidithiobacillus caldus S1, Sulfobacillus thermosulfidooxidans ST and Leptospirillum ferriphilum YSK, and one archaea, Ferroplasma thermophilum L1) to explore the variation of microbial community structure, composition, dynamics and function (e.g., copper extraction efficiency) in chalcopyrite bioleaching (C) systems with additions of pyrite (CP) or sphalerite (CS). The community compositions and dynamics in the solution and on the ore surface were investigated by real-time quantitative PCR (qPCR). The results showed that the addition of pyrite or sphalerite changed the microbial community composition and dynamics dramatically during the chalcopyrite bioleaching process. For example, A. caldus (above 60%) was the dominant species at the initial stage in three groups, and at the middle stage, still dominated C group (above 70%), but it was replaced by L. ferriphilum (above 60%) in CP and CS groups; at the final stage, L. ferriphilum dominated C group, while F. thermophilum dominated CP group on the ore surface. Furthermore, the additions of pyrite or sphalerite both made the increase of redox potential (ORP) and the concentrations of Fe 3+ and H + , which would affect the microbial community compositions and copper extraction efficiency. Additionally, pyrite could enhance copper extraction efficiency (e.g., improving around 13.2% on day 6) during chalcopyrite bioleaching; on the contrary, sphalerite restrained it.
Geochemical Modeling of Zinc Silicate Ore Formation from Sedimentary Hydrothermal Fluids
NASA Astrophysics Data System (ADS)
Appold, M. S.
2008-12-01
Sediment-hosted zinc deposits dominated by willemite (Zn2SiO4) instead of sphalerite (ZnS) are known from several prominent occurrences worldwide, including Vazante, Brazil, the Aroona Trend, Australia, Kabwe, Zambia, Berg Aukas, Namibia, and Abu Samar, Sudan. Although willemite-dominant zinc deposits appear to be much less common and are on average smaller than sphalerite-dominant zinc deposits, they nonetheless represent major enrichments of zinc in the Earth's crust, reaching sizes on the order of 1's to 10's of millions of tons and grades commonly between 20 and 40%. Sediment-hosted willemite- and sphalerite-dominant deposits share many similarities including their predominantly carbonate host rocks, gangue mineralogy, presumed derivation from sedimentary basinal brines, and spatial proximity. However, the conditions and processes that led to one style of mineralization versus the other have only recently begun to be investigated. The current study presents solubility, reaction path, and reactive transport modeling results that attempt to define more clearly the conditions that favor willemite ore formation in sedimentary basins, with a focus on the Vazante deposit. Solubility calculations for willemite and sphalerite as a function of temperature, pH, salinity, and oxidation potential were carried out using a simple 3 molal NaCl solution saturated with respect to quartz. The results show that (1) willemite solubility is relatively insensitive to changes in temperature and oxidation potential whereas sphalerite solubility decreases sharply with decreasing temperature and oxidation potential, (2) willemite solubility decreases more strongly than sphalerite with increasing pH, (3) willemite and sphalerite have a similar strong decrease in solubility with decreasing salinity. The results support a previously proposed genetic model for a willemite-dominant, sphalerite-subordinate ore body like Vazante in which a hot, acidic, metal-rich ore fluid mixed with a cooler, more oxidizing, dilute, and basic fluid. This scenario was investigated further with reaction path and reactive transport modeling. In these models, a more complex ore fluid was used that was assumed to have a major element composition similar to the global average for Mississippi Valley-type (MVT) deposits determined from the literature, modified by heating from 150 to 300° C, saturated with respect to dolomite and quartz, moderately acidic, and an oxidation potential near the value defined by magnetite-hematite equilibrium. The ore fluid was allowed to mix with a second, possibly meteoric fluid with about three orders of magnitude lower salinity, neutral pH, and a temperature of 50° C. The modeling results showed general agreement with the mineral assemblage observed at Vazante, and confirmed the need for a strong pH increase to induce willemite precipitation, and no more than a moderate increase in oxidation potential to allow some sphalerite to precipitate. The localization of mineralization within a shear zone was found to depend strongly on the shear zone having acted as a high permeability conduit for the ore fluid from deeper parts of the sedimentary basin.
NASA Astrophysics Data System (ADS)
Xiong, Suo-Fei; Gong, Yong-Jun; Jiang, Shao-Yong; Zhang, Xiao-Jing; Li, Qian; Zeng, Guo-Ping
2018-01-01
The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.
Assessment of the geoavailability of trace elements from selected zinc minerals
Driscoll, Rhonda L.; Hageman, Phillip L.; Benzel, William M.; Diehl, Sharon F.; Morman, Suzette; Choate, LaDonna M.; Lowers, Heather
2014-01-01
This assessment focused on five zinc-bearing minerals. The minerals were subjected to a number of analyses including quantitative X-ray diffraction, optical microscopy, leaching tests, and bioaccessibility and toxicity studies. Like a previous comprehensive assessment of five copper-bearing minerals, the purpose of this assessment was to obtain structural and chemical information and to characterize the reactivity of each mineral to various simulated environmental and biological conditions. As in the copper minerals study, analyses were conducted consistent with widely accepted methods. Unless otherwise noted, analytical methods used for this study were identical to those described in the investigation of copper-bearing minerals. Two sphalerite specimens were included in the zinc-minerals set. One sphalerite was recovered from a mine in Balmat, New York; the second came from a mine in Creede, Colorado. The location and conditions of origin are significant because, as analyses confirmed, the two sphalerite specimens are quite different. For example, data acquired from a simulated gastric fluid (SGF) study indicate that the hydrothermally formed Creede sphalerite contains orders of magnitude higher arsenic, cadmium, manganese, and lead than the much older metamorphic Balmat sphalerite. The SGF and other experimental results contained in this report suggest that crystallizing conditions such as temperature, pressure, fluidization, or alteration processes significantly affect mineral properties—properties that, in turn, influence reactivity, solubility, and toxicity. The three remaining minerals analyzed for this report—smithsonite, hemimorphite, and hydrozincite—are all secondary minerals or alteration products of zinc-ore deposits. In addition, all share physical characteristics such as tenacity, density, streak, and cleavage. Similarities end there. The chemical composition, unit-cell parameters, acid-neutralizing potential, and other observable and quantifiable properties indicate very different minerals. Only one of each of these minerals was studied. Had this assessment included multiples of these minerals, geochemical and mineralogical distinctions would have emerged, similar to the results for the two sphalerite specimens.
Microbially induced flotation and flocculation of pyrite and sphalerite.
Patra, Partha; Natarajan, K A
2004-07-15
Cells of Paenibacillus polymyxa and their metabolite products were successfully utilized to achieve selective separation of sphalerite from pyrite, through microbially induced flocculation and flotation. Adsorption studies and electrokinetic investigations were carried out to understand the changes in the surface chemistry of bacterial cells and the minerals after mutual interaction. Possible mechanisms in microbially induced flotation and flocculation are outlined.
Geochemistry of the Patricia Zn-Pb-Ag Deposit (paguanta, NE Chile)
NASA Astrophysics Data System (ADS)
Chinchilla Benavides, D.; Merinero Palomares, R.; Piña García, R.; Ortega Menor, L.; Lunar Hernández, R.
2013-12-01
The Patricia Zn-Pb-Ag ore deposit is located within the Paguanta mining project, situated at the northern end of the Andean Oligocene Porphyry Copper Belt of Chile. The sulfide mineralization occurs as W-E oriented veins hosted in volcanic rocks, mainly andesite (pyroclastic, ash and lavas), of Upper Cretaceous to Middle Tertiary age. The ore mineralogy (obtained by EMPA analyses) comprises in order of abundance, pyrite, sphalerite (5.5 - 10.89 wt % Fe, 9.8-19 % molar FeS and 0.52 wt % Cd), galena, arsenopyrite, chalcopyrite and Ag-bearing sulfosalts. The veins show a zoned and banded internal structure with pyrite at the edges and sphalerite in the center. The Ag occurs mostly as Ag-Cu-Sb sulfosalts, in order of abundance: series freibergite - argentotennantite -polybasite and stephanite. Other minor Ag phases such as argentite, pyrargirite and diaphorite were also identified. These Ag phases are typically associated with the base-metal sulfides. Freibergite occurs filling voids within sphalerite, chalcopyrite and at the contact between sphalerite and galena. Polybasite, stephanite, pyrargirite and argentite are mostly in close association with freibergite. In the case of diaphorite, it commonly occurs filling voids between galena crystals or as inclusions within galena. Some minor Ag-bearing sulfosalts are also identified between pyrite crystals. The alteration minerals are dominated by chlorite, illite and kaolinite. The gangue minerals consist of quartz and carbonates identified by XRD as kutnahorite. We obtained linear correlation statistically significant only for Ag, As Au, Cd, Cu, Pb, Sb and Zn and therefore we generated an enhanced scatter plot matrix of these elements. Bulk rock analyses (ICP/MS and XRF) of drill cores show that Ag is strongly and positively correlated with Pb and As, moderately with Cd, Sb, Au and Zn and weakly with Cu, while Au is moderately and positively correlated with Ag, As, Cd, Sb and Zn and weakly with Cu and Pb. These results are consistent with bulk rock analyses of selected and mineralized samples were similar correlations have been obtained. Ag positive correlations indicate that the formation of Ag-bearing minerals is mainly associated with galena, arsenopyrite and sphalerite occurrence. Au positive correlations indicate that this element occurs in close relationship with Ag-bearing minerals, arsenopyrite and sphalerite. The weak correlation between Cu and Ag and Au indicate that the formation of chalcopyrite is not related with the main stages of Ag-Au mineralization. The main conclusion of this study is that geochemical analyses along drill cores that cut mineralization confirm that the occurrence of Ag and Au in the Paguanta deposit is associated with the formation of galena, arsenopyrite and sphalerite. This study also confirm previous conclusions suggesting that the Patricia Pb-Zn-Ag ore deposit probably represents an example of epithermal mineralization of intermediate sulfidation state, with periods of lower sulfidation state during sphalerite deposition.
Viets, J.G.; Leach, D.L.; Lichte, F.E.; Hopkins, R.T.; Gent, C.A.; Powell, J.W.
1996-01-01
Paragenetic and minor- and trace-element studies were conducted on samples of epigenetic ore and gangue minerals collected from mines and drill core in the Silesian-Cracow (S-C) district of southern Poland. Four discrete mineral suites representing four mineralizing stages can be identified throughout the district. The earliest epigenetic minerals deposited during stage 1 consist of a late dolomite cement together with minor pyrite and marcasite. Stage 2 was the first ore-forming stage and included repetitive deposition of sphalerite and galena in a variety of morphologies. Stage 3 abruptly followed the first ore stage and deposited marcasite and pyrite with variable amounts of late sphalerite and galena. In the samples studied, minerals deposited during stage 3 are predominately marcasite-pyrite with minor sphalerite and galena in the Pomorzany and Olkusz mines, whereas, at the Trzebionka mine, stage 3 mineralization deposited mostly galena and sphalerite with little marcasite or pyrite. Stage 4 minerals include contains barite, followed by calcite, with very minor pyrite and a rare, late granular sphalerite. Compared to other major Mississippi Valley-type (MVT) districts of the world, the Silesian-Cracow district contains sphalerite with the second largest range in Ag concentrations and the largest range in Fe and Cd concentrations of any district. Unlike in other districts, very wide ranges in minor- and trace-element concentrations are also observed in paragenetically equivalent samples collected throughout the district. This wide range indicates that the minor- and trace-element content of the ore-forming environment was highly variable, both spatially and temporally, and suggests that the hydrologic system that the ore fluids traversed from their basinal source was very complex. Throughout the district, a significant increase in Tl, Ge, and As concentrations is accompanied by a lightening of sulfur isotopes between stage 2 and stage 3 minerals. This change appears to record a major district-scale hydrologic event that probably reflects the introduction of fluids with significantly different geochemistry than that of earlier ore-forming fluids.
Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)
Garnit, Hechmi; Bouhel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker
2012-01-01
The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.
Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)
NASA Astrophysics Data System (ADS)
Garnit, Hechmi; Bouhlel, Salah; Barca, Donatella; Johnson, Craig A.; Chtara, Chaker
2012-06-01
The Sekarna Zn-Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn-Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation-inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000-20,000 ppm) and galena (12-189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80-130°C. The final ice melting temperatures range from -22°C to -11°C, which correspond to salinities of 15-24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (-11.2‰ to -9.3‰) and galena (-16‰ to -12.3‰). The δ34S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.
NASA Astrophysics Data System (ADS)
Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong
2018-01-01
Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.
Sphalerite is a geochemical catalyst for carbon−hydrogen bond activation
Shipp, Jessie A.; Gould, Ian R.; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.
2014-01-01
Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth’s deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon−hydrogen bond in the dimethylcyclohexanes. PMID:25071186
Sphalerite is a geochemical catalyst for carbon-hydrogen bond activation.
Shipp, Jessie A; Gould, Ian R; Shock, Everett L; Williams, Lynda B; Hartnett, Hilairy E
2014-08-12
Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth's deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon-hydrogen bond in the dimethylcyclohexanes.
Ferromagnetism in sphalerite and wurtzite CdS nanostructures
2013-01-01
Room-temperature ferromagnetism is observed in undoped sphalerite and wurtzite CdS nanostructures which are synthesized by hydrothermal methods. Scanning electron microscopy and transmission electron microscopy results indicate that the sphalerite CdS samples show a spherical-like shape and the wurtzite CdS ones show a flower-like shape, both of which are aggregated by lots of smaller particles. The impurity of the samples has been ruled out by the results of X-ray diffraction, selected-area electron diffraction, and X-ray photoelectron spectroscopy. Magnetization measurements indicate that all the samples exhibit room-temperature ferromagnetism and the saturation magnetization decreases with the increased crystal sizes, revealing that the observed ferromagnetism is defect-related, which is also confirmed by the post-annealing processes. This finding in CdS should be the focus of future electronic and spintronic devices. PMID:23294671
NASA Astrophysics Data System (ADS)
Liu, Jian; Wang, Yu; Luo, Deqiang; Chen, Luzheng; Deng, Jiushuai
2018-05-01
The copper activation and potassium butyl xanthate (PBX) adsorption on sphalerite and marmatite surfaces were comparatively investigated using in situ local electrochemical impedance spectroscopy (LEIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and surface adsorption tests. Comparing the LEIS and surface adsorption results, it was found that the activation time is a key factor influencing the copper activation and PBX adsorption on marmatite surface, but it has a negligible influence on sphalerite. For a short activation time within 10 min, the Fe impurity in marmatite shows an adverse influence on the speed of Cu adsorption and ion exchange as well as on the subsequent PBX adsorption. For a long activation time of 30 min, the LEIS, ToF-SIMS and surface adsorption results suggested that the Fe impurity in marmatite enhances the copper adsorption, whereas such enhanced copper adsorption of marmatite cannot result in corresponding enhancing of PBX adsorption. DFT result showed that the Fe impurity in marmatite has harmful influence on the PBX interaction with the Cu-activated surface by increasing the interaction energy. ToF-SIMS result further indicated that the Cu distribution in the outermost surface of marmatite is less than that of the sphalerite, which also results in the less PBX adsorption for the marmatite.
Microcrystalline sphalerite in resin globules suspended in Lake Kivu, East Africa
Degens, E.T.; Okada, H.; Honjo, S.; Hathaway, J.C.
1972-01-01
The origin and chemical nature of micron-sized spheres found as suspended particles in Lake Kivu are examined. It can be shown that the hollow spheres, with a wall thickness of 500 A??, consist of a complex polymeric resinous material which has little functionality, except for hydroxyl groups. The spheres arise in the process of degassing of water samples at depth. Tiny gas bubbles, about 1 micron in size, act as scavengers of dissolved resinous material. The newly created resinous membrane promotes the selective coordination of zinc dissolved in the water column. In the prevailing H2S regime, formation of sphalerite crystals in induced. The size range of the crystals, 5 to 50 A??, corresponds to 1 to 10 unit cells and suggests that the resinous membrane also acts as a template in sphalerite growth processes. The sources of the zinc and dissolved gases (CO2, CH4, H2S) are hydrothermal springs seeping from the lake bottom into the basin. Water discharge is substantial; about 100 years are required to fill the lake to its present level (ca. 550 km3 water). The average Kivu water contains 2 ppm zinc. Thus, 1 million tons of zinc are contained in Lake Kivu in the form of sphalerite. ?? 1972 Springer-Verlag.
Xiao, Yunhua; Xu, YongDong; Dong, Weiling; Liang, Yili; Fan, Fenliang; Zhang, Xiaoxia; Zhang, Xian; Niu, Jiaojiao; Ma, Liyuan; She, Siyuan; He, Zhili; Liu, Xueduan; Yin, Huaqun
2015-12-01
This study used an artificial enrichment microbial consortium to examine the effects of different substrate conditions on microbial diversity, composition, and function (e.g., zinc leaching efficiency) through adding pyrite (SP group), chalcopyrite (SC group), or both (SPC group) in sphalerite bioleaching systems. 16S rRNA gene sequencing analysis showed that microbial community structures and compositions dramatically changed with additions of pyrite or chalcopyrite during the sphalerite bioleaching process. Shannon diversity index showed a significantly increase in the SP (1.460), SC (1.476), and SPC (1.341) groups compared with control (sphalerite group, 0.624) on day 30, meanwhile, zinc leaching efficiencies were enhanced by about 13.4, 2.9, and 13.2%, respectively. Also, additions of pyrite or chalcopyrite could increase electric potential (ORP) and the concentrations of Fe3+ and H+, which were the main factors shaping microbial community structures by Mantel test analysis. Linear regression analysis showed that ORP, Fe3+ concentration, and pH were significantly correlated to zinc leaching efficiency and microbial diversity. In addition, we found that leaching efficiency showed a positive and significant relationship with microbial diversity. In conclusion, our results showed that the complicated substrates could significantly enhance microbial diversity and activity of function.
Kozdon, R.; Kita, N.T.; Huberty, J.M.; Fournelle, J.H.; Johnson, C.A.; Valley, J.W.
2010-01-01
Secondary ion mass spectrometry (SIMS) measurement of sulfur isotope ratios is a potentially powerful technique for in situ studies in many areas of Earth and planetary science. Tests were performed to evaluate the accuracy and precision of sulfur isotope analysis by SIMS in a set of seven well-characterized, isotopically homogeneous natural sulfide standards. The spot-to-spot and grain-to-grain precision for δ34S is ± 0.3‰ for chalcopyrite and pyrrhotite, and ± 0.2‰ for pyrite (2SD) using a 1.6 nA primary beam that was focused to 10 µm diameter with a Gaussian-beam density distribution. Likewise, multiple δ34S measurements within single grains of sphalerite are within ± 0.3‰. However, between individual sphalerite grains, δ34S varies by up to 3.4‰ and the grain-to-grain precision is poor (± 1.7‰, n = 20). Measured values of δ34S correspond with analysis pit microstructures, ranging from smooth surfaces for grains with high δ34S values, to pronounced ripples and terraces in analysis pits from grains featuring low δ34S values. Electron backscatter diffraction (EBSD) shows that individual sphalerite grains are single crystals, whereas crystal orientation varies from grain-to-grain. The 3.4‰ variation in measured δ34S between individual grains of sphalerite is attributed to changes in instrumental bias caused by different crystal orientations with respect to the incident primary Cs+ beam. High δ34S values in sphalerite correlate to when the Cs+ beam is parallel to the set of directions , from [111] to [110], which are preferred directions for channeling and focusing in diamond-centered cubic crystals. Crystal orientation effects on instrumental bias were further detected in galena. However, as a result of the perfect cleavage along {100} crushed chips of galena are typically cube-shaped and likely to be preferentially oriented, thus crystal orientation effects on instrumental bias may be obscured. Test were made to improve the analytical precision of δ34S in sphalerite, and the best results were achieved by either reducing the depth of the analysis pits using a Köhler illuminated primary beam, or by lowering the total impact energy from 20 keV to 13 keV. The resulting grain-to-grain precision in δ34S improves from ± 1.7‰ to better than 0.6‰ (2SD) in both procedures. With careful use of appropriate analytical conditions, the accuracy of SIMS analysis for δ34S approaches ± 0.3‰ (2SD) for chalcopyrite, pyrite and pyrrhotite and ± 0.6‰ for sphalerite. Measurements of δ34S in sub-20 µm grains of pyrite and sphalerite in ∼ 3.5 Ga cherts from the Pilbara craton, Western Australia show that this analytical technique is suitable for in situ sulfur isotope thermometry with ± 50 °C accuracy in appropriate samples, however, sulfides are not isotopically equilibrated in analyzed samples.
Mineralogical variation of skarn ore from the Tellerhäuser deposit, Pöhla, Germany
NASA Astrophysics Data System (ADS)
Simons, Bethany; Andersen, Jens Christian; Rollinson, Gavyn; Armstrong, Robin; Dolgopolova, Alla; Seltmann, Reimar; Stanley, Chris; Roscher, Marco
2017-04-01
The polymetallic Zn-Fe-Sn-Cu-In skarns at Pöhla Tellerhäuser in the western Erzgebirge represent some of the largest unexploited occurrences of Sn and In in Europe. The skarns developed in schists and gneisses at the margin of the Schwarzenberg Gneiss cupola and the Eibenstock granites. The flat-lying skarn layers display extreme mineralogical variability with alternating units of pyroxene, sphalerite, magnetite, amphibole and calc-silicate skarns with hanging wall schist and feeder stockwork. The polymetallic skarn ores represent a complex challenge for mineral processing, with fine-grained, locked target minerals and partitioning of target metals into silicates (e.g. Sn in malayaite). Optical microscopy, QEMSCAN® and electron-probe microanalysis have been used to determine the mineralogical variability of the skarn types with the aim to determine the deportment of the target metals to guide mineral processing test work. The composition of the skarns is extremely variable reflecting the complex mineralogy and indicating substantial variability associated with replacement reactions through the protolith(s). Cassiterite (SnO2) is the dominant Sn-bearing mineral in all the skarn types. However, the skarns also carry malayaite (CaSnO[SiO4], up to 0.03 vol%), which locally dominates over cassiterite. Cassiterite is intergrown with Fe-amphibole, grossular garnet, fluorite and magnetite. The cassiterite is unaltered, but some grains have rare iron oxide rims and inclusions. Malayaite shows a similar association to cassiterite and is intergrown as clusters of grains with silicate gangue, particularly Fe amphibole and grossular garnet and remains unaltered with no inclusions. Zinc is exclusively hosted in sphalerite and varies from 0.02 wt.% in the hanging wall schist to 36.5 wt.% in the sphalerite skarn. The high Zn values are accompanied by high values of Cd (locally in excess of 1000 ppm) and In (up to 180 ppm). Sphalerite grains are locally up to 4 mm, subhedral with chalcopyrite disease and pyrite epitaxial growth along contacts between sphalerite and magnetite. Inclusions in sphalerite include bornite, enargite, chalcocite and arsenopyrite. Magnetite comprises up to 94 vol% (mean 32 vol%) of the magnetite skarn and displays extensive haematite alteration. Intergrown with magnetite are subordinate cassiterite and sphalerite with chalcopyrite disease and high In concentrations. The mineralogical complexity is the most significant challenge for processing of the Tellerhäuser ore. Some Sn is locked within silicates leading to an expected loss in processing. The diverse gangue mineralogy is likely to interfere with traditional gravity and magnetic separation techniques. Biohydrometallurgy may offer a particularly attractive method of recovery for Zn, Cu and In. This contribution is sponsored by the EU Horizon 2020 project "FAME" (grant 641650)
Fluid-inclusion data on samples from Creede, Colorado, in relation to mineral paragenesis
Woods, T.L.; Roedder, Edwin; Bethke, P.M.
1982-01-01
Published and unpublished data on 2575 fluid inclusions in ore and gangue minerals from the Creede, Colorado, Ag-Pb-Zn-Cu vein deposit collected in our laboratories from 1959 to 1981 have shown that the average salinity (wt. % NaCl equivalent, hereinafter termed wt.% eq.) and homogenization temperature (Th), and the ranges of these two parameters for fluid inclusions in sphalerite, quartz, fluorite, and rhodochrosite, respectively, are 8.1 (4.6 - 13.4), 239?C (195-274?C); 6.1 (1.1-10.0), 260?C (190->400?C); 10.7 (6.1-11.1), 217?C (213-229?C) and 260?C (247-268?C) (bimodal distribution of Th); and 9.9 (9.3 - 10.6), 214?C (185-249?C). Inclusions have been measured in minerals from four of the five stages of mineralization previously recognized at Creede. The few inclusions of fluids depositing rhodochrosite (A-stage, earliest in the paragenesis) yield Th and salinity values more similar to those of the low-temperature (average Th 217?C) fluids forming some of the much later fluorite (C-stage) than to any of the other fluids. Th measurements on A-stage quartz range from 192?C to 263?C and average 237?C. The early, fine-grained, B-stage sphalerites yielded Th of 214 to 241?C and salinities of 6.1 to 10.2 wt. % eq. D-stage sphalerite (late in the paragenesis) has been studied in detail (growth-zone by growth-zone) for several localities along the OH vein and reveals a generally positive correlation among Th, salinity and iron content of the host sphalerite. The deposition of D-stage sphalerite was characterized by repeated cycling through different regions of salinity/Th space, as Th and salinity generally decreased with time. Seventeen salinity-Th measurements were made on D-stage sphalerite from one locality on the Bulldog Mountain vein system, which, like the OH vein, is one of four major ore-producing vein systems at Creede. These data suggest a lower Th for a given salinity fluid from sphalerite on the Bulldog Mountain vein than on the OH vein. The very high values of Th for some quartz samples (mostly D-stage) are believed to be a result of the trapping of both gas and liquid from a boiling fluid in the upper levels of the vein system. Boiling of fluids depositing D-stage quartz is indicated by the presence of steam inclusions in quartz and the extreme variability of Th values measured on quartz. The pressure was low (< 125 kg/cm 2) throughout ore deposition. Three major growth zones in D-stage sphalerite are recognized throughout the OH vein. Deposition of the first major zone began from fluids having intermediate salinities and temperatures (7.8-9.2 wt. % eq., 240?C) but the characteristics of the fluids oscillated after that, ranging from 7.2 to 10.1 wt. % eq. and from 225?C to 270?C. Deposition of the second major, most Fe-rich zone began with the hottest, most saline fluids present during D-stage mineralization (. 270?C, 10.5-12.5 wt. % eq., 3 mole % FeS in sphalerite). The fluid then oscillated with respect to Th and salinity (213-274?C, 5.2-12.5 wt. % eq.) but showed a general decrease in both with time. Deposition of the youngest major zone began with a very Fe-poor sphalerite (0.25-0.75 mole % FeS), from the least saline, coolest fluids (5-6.5 wt. % eq., 200-212?C) and ended with a trend of increasing temperature at approximately constant salinity. The fluid-inclusion data can best be explained by a mixing model involving at least two fluids--one hot and saline, the other cool and fresher. Sudden changes in the mixing ratio, presumably from changes in the plumbing, punctuated long periods of remarkably uniform conditions of ore fluid flow and deposition. The effects of other processes such as convection and heat exchange with wall rocks must have been superimposed on this simple mixing model, however. In contrast to an earlier interpretation, several aspects of the inclusion data may be interpreted to suggest exceedingly slow ore deposition. Work in progress may resolve some of these ambiguities and refine
Mineralogy, chemical composition and structure of the MIR Mound, TAG Hydrothermal Field
NASA Astrophysics Data System (ADS)
Stepanova, T. V.; Krasnov, S. G.; Cherkashev, G. A.
The study of samples collected from the surface of the MIR mound (TAG Hydrothermal Field) by video-controlled hydraulic grab allowed identification of a number of mineralogical types. These include pyrite-chalcopyrite (Py-Cp), bornite-chalcopyrite-opaline (Bn-Cp-Op) and sphalerite-opaline (Sp-Op) sulfide chimneys, massive sulfides composed of pyrite (Py), chalcopyrite-pyrite (Cp-Py), marcasite-pyrite-opaline (Mc-Py-Op), sphalerite-pyrite-opaline (Sp-Py-Op) and sphalerite-chalcopyrite-pyrite-opaline (Sp-Cp-Py-Op), as well as siliceous and Fe-Mn oxide hydrothermal deposits. Most of the minor elements (Ag, Au, Cd, Ga, Hg, Sb and Pb) are associated with Zn-rich massive sulfides, Co Bi, Pb, and As with Ferich ones, while Cu-rich sulfides are depleted of trace metals. Cu-enriched assemblages are concentrated in the northern part, Zn-enriched in the center, and siliceous rocks in the south of the MIR mound. According to paragenetic relations, the development of the mound started with the formation of quartz (originally opaline) rocks and dendritic assemblages of melnikovite-pyrite, followed by deposition of chalcopyrite and recrystallization of primary pyrite, subsequent generation of sphalerite-rich assemblages and final deposition of opaline rocks. The late renewal of hydrothermal activity led to local formation of Cu-rich chimneys enriched in Au, Ag, Hg and Pb probably due to their remobilization from inner parts of the deposit.
Full potential calculations on the electron bandstructures of Sphalerite, Pyrite and Chalcopyrite
NASA Astrophysics Data System (ADS)
Edelbro, R.; Sandström, Å.; Paul, J.
2003-02-01
The bulk electronic structures of Sphalerite, Pyrite and Chalcopyrite have been calculated within an ab initio, full potential, density functional approach. The exchange term was approximated with the Dirac exchange functional, the Vosko-Wilk-Nusair parameterization of the Cepler-Alder free electron gas was used for correlation and linear combinations of Gaussian type orbitals were used as basis functions. The Sphalerite (zinc blende) band gap was calculated to be direct with a width of 2.23 eV. The Sphalerite valence band was 5.2 eV wide and composed of a mixture of sulfur and zinc orbitals. The band below the valence band located around -6.2 eV was mainly composed of Zn 3d orbitals. The S 3s orbitals gave rise to a band located around -12.3 eV. Pyrite was calculated to be a semiconductor with an indirect band gap of 0.51 eV, and a direct gap of 0.55 eV. The valence band was 1.25 eV wide and mainly composed of non-bonding Fe 3d orbitals. The band below the valence band was 4.9 eV wide and composed of a mixture of sulfur and iron orbitals. Due to the short inter-atomic distance between the sulfur dumbbells, the S 3s orbitals in Pyrite were split into a bonding and an anti-bonding range. Chalcopyrite was predicted to be a conductor, with no band-crossings at the Fermi level. The bands at -13.2 eV originate from the sulfur 3s orbitals and were quite similar to the sulfur 3s bands in Sphalerite, though somewhat shifted to lower energy. The top of the valence band consisted of a mixture of orbitals from all the atoms. The lower part of the same band showed metal character. Computational modeling as a tool for illuminating the flotation and leaching processes of Pyrite and Chalcopyrite, in connection with surface science experiments, is discussed.
Bethke, P.M.; Rye, R.O.
1979-01-01
The hydrogen isotopic composition of fluids responsible for formation of the near-surface silver-base metal vein deposits at Creede was measured by direct analysis of inclusion fluids in sphalerite, quartz, and rhodochrosite and was estimated from analyses of illite and chlorite. The oxygen isotopic composition was determined directly on inclusion fluids in sphalerite and was estimated from analyses of quartz, illite, rhodochrosite, siderite, and adularia. The carbon isotopic composition was estimated from analyses of rhodochrosite and siderite. The ranges in isotopic composition for water and CO2 in the fluids associated with the formation of each of the minerals is given below (number of determinations given in parentheses):Mineral delta D (sub H2) O ppm delta 18 O (sub H2) O ppm delta 13 C (sub CO2) ppmSphalerite -81 to -54 (4) -10.1 to -4.5 (4)Quartz -97 to -86 (4) -5.9 to 1.8 (18)Illite -62 to -50 (8) -1.6 to 1.2(7)Chlorite -64 to -55 (10) -2.2 to 0.8 (10)Adularia 4.2 (1)Rhodochrosite -82 to -78 (2) 4.2 to 9.4 (9) -5.7 to -4.2 (9)Siderite 4.9 to 9.9 (6) -6.9 to -2.7 (6)The delta D (sub H2) O and delta 18 O (sub H2) O values of fluids associated with the formation of sphalerite, quartz, illite/chlorite, and carbonate minerals differ substantially from one another, and these differences appear to have been maintained throughout the depositional history, regardless of the positions of the minerals in the paragenetic sequence.The data suggest that waters from three coexisting reservoirs fed the vein system alternately and episodically during vein formation, and apparently there was little mixing of the fluids from the different reservoirs. The hydrogen, oxygen, and carbon isotope data suggest that the carbonate waters were deep seated, probably dominantly magmatic, in origin. The sphalerite and illite/chlorite waters must have been dominantly meteoric in origin and substantially oxygen shifted by exchange with the volcanic country rocks. The quartz waters were also oxygen shifted meteoric waters but were some 40 per mil lower in deuterium content than the sphalerite and illite/chlorite waters.We propose that the quartz fluids entered the vein system from reservoirs beneath the mountainous areas to the north in the vicinity of the present Continental Divide, but that the sphalerite and illite/chlorite fluids entered the vein system from a topographically low area to the south along the structural moat of the Creede caldera. The difference in delta D between the two meteoric waters may reflect differences in altitude of the recharge areas for the two reservoirs or may be clue to isotopic evolution of the closed-basin lake and interstitial waters in the moat surrounding the Creede caldera.
Pecina-Treviño, E T; Ramos-Escobedo, G T; Gallegos-Acevedo, P M; López-Saucedo, F J; Orrantia-Borunda, E
2012-09-01
Surface oxidation of sulfides and copper (Cu) activation are 2 of the main processes that determine the efficiency of flotation. The present study was developed with the intention to ascertain the role of the phenomena in the biomodification of sulfides by Acidithiobacillus ferrooxidans culture (cells and growth media) and their impact in bioflotation. Surface characteristics of chalcopyrite, sphalerite, and pyrrhotite, alone and in mixtures, after interaction with A. ferrooxidans were evaluated. Chalcopyrite floatability was increased substantially by biomodification, while bacteria depressed pyrrhotite floatability, favoring separation. The results showed that elemental sulfur concentration increased because of the oxidation generated by bacterial cells, the effect is intensified by the Fe(III) left in the culture and by galvanic contact. Acidithiobacillus ferrooxidans culture affects the Cu activation of sphalerite. The implications of elemental sulfur concentration and Cu activation of sphalerite are key factors that must be considered for the future development of sulfide bioflotation processes, since the depressive effect of cells could be counteracted by elemental sulfur generation.
Bodnar, R.J.; Bethke, P.M.
1984-01-01
Measured homogenization T of fluid inclusions in fluorite and sphalerite may be higher than the true homogenization T of samples that have been previously heated in the laboratory or naturally in post-entrapment events. As T and with it internal P is increased, the resulting volume increase may become inelastic. If the volume increase exceeds the precision of T measurement, the inclusion is said to have stretched. More than 1300 measurements on fluid inclusions in fluorite and sphalerite indicate that stretching is systematically related to P-V-T-X properties of the fluid, inclusion size and shape, physical properties of the host mineral, and the confining P. Experimental methods are detailed in an appendix. The mechanism of stretching is probably plastic deformation or - not observed - microfracturing. The systematic relationship between the internal P necessary to initiate stretching and the inclusion volume provides a means of recognizing previously stretched inclusions and estimating the magnitude of post-entrapment thermal events. -G.J.N.
NASA Astrophysics Data System (ADS)
Rogulina, L. I.; Moiseenko, V. G.; Ponomarchuk, V. A.
2018-04-01
New data on the composition of the major minerals from the skarn and vein polymetallic deposits of the Dal'negorskii ore region are reported. Analysis of galena and sphalerite was carried out by the X-ray fluorescent energy-dispersive method of synchrotron radiation for the first time. It is shown that the minor elements in major minerals of different deposits are typomorphic. Among these elements are Fe, Cu, Ni, Cd, Ag, Sn, and Sb, as well as In in sphalerite and Te in galena. The high concentrations of Ag, Cu, Te, Cd, and In in the extracted minerals indicate the complex character of mineralization. The compositional patterns of ore minerals characterize the sequence of mineral formation from the skarn to vein ores, and the sequence of deposits from the mesothermal to epithermal conditions. This provides geochemical evidence for the stage model of the formation of mineralization in the Dal'negorskii ore region.
Optimization of Cu-Zn Massive Sulphide Flotation by Selective Reagents
NASA Astrophysics Data System (ADS)
Soltani, F.; Koleini, S. M. J.; Abdollahy, M.
2014-10-01
Selective floatation of base metal sulphide minerals can be achieved by using selective reagents. Sequential floatation of chalcopyrite-sphalerite from Taknar (Iran) massive sulphide ore with 3.5 % Zn and 1.26 % Cu was studied. D-optimal design of response surface methodology was used. Four mixed collector types (Aer238 + SIPX, Aero3477 + SIPX, TC1000 + SIPX and X231 + SIPX), two depressant systems (CuCN-ZnSO4 and dextrin-ZnSO4), pH and ZnSO4 dosage were considered as operational factors in the first stage of flotation. Different conditions of pH, CuSO4 dosage and SIPX dosage were studied for sphalerite flotation from first stage tailings. Aero238 + SIPX induced better selectivity for chalcopyrite against pyrite and sphalerite. Dextrin-ZnSO4 was as effective as CuCN-ZnSO4 in sphalerite-pyrite depression. Under optimum conditions, Cu recovery, Zn recovery and pyrite content in Cu concentrate were 88.99, 33.49 and 1.34 % by using Aero238 + SIPX as mixed collector, CuCN-ZnSO4 as depressant system, at ZnSO4 dosage of 200 g/t and pH 10.54. When CuCN was used at the first stage, CuSO4 consumption increased and Zn recovery decreased during the second stage. Maximum Zn recovery was 72.19 % by using 343.66 g/t of CuSO4, 22.22 g/t of SIPX and pH 9.99 at the second stage.
Cerro de Pasco and other massive sulfide deposits of central Peru
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cheney, E.S.
1985-01-01
The famous Cerro de Pasco Pb-Zn-Ag deposit historically has been considered to be hydrothermally derived from an adjacent Tertiary volcanic vent. However, texturally massive pyrite-chert and pyrite-sphalerite-galena in the deposit have the same strike and cross folds as the adjacent pre-Tertiary strata. Both the deposit and the strata are cut by one of the large Longitudinal Faults. Both dikes and pyrite-enargite veins associated with the vent cut the massive sulfides; fragments of massive pyrite occur in the vent. A few examples of laminated pyrite and chert, banded pyrite and chert, banded pyrite and sphalerite, and banded pyrite, sphalerite, and galenamore » are preserved in the massive sulfide portion of the deposit. The deposit has the composition and zoning patterns typical of shale-hosted massive sulfides. Cerro de Pasco probably in part of the pelitic Devonian Excelsior formation. The Colquijirca deposit 8 km to the south and the San Cristobal district 110 km to the south likewise have been considered to be Tertiary volcanic hydrothermal deposits. Colquijirca consists of stratigraphically controlled mantos of layered pyrite, chert and tuff in the Tertiary Calera formation. The mantos of the San Cristobal district are along the upper contact of the pyritic, Permian, Catalina felsic volcanic rocks; some ore consists of laminated pyrite and sphalerite. Tertiary plutons are conspicuously absent at San Cristobal, and the ores are brecciated by Tertiary folding.« less
Characterization of flotation color by machine vision
NASA Astrophysics Data System (ADS)
Siren, Ari
1999-09-01
Flotation is the most common industrial method by which valuable minerals are separated from waste rock after crushing and grinding the ore. For process control, flotation plants and devices are equipped with conventional and specialized sensors. However, certain variables are left to the visual observation of the operator, such as the color of the froth and the size of the bubbles in the froth. The ChaCo-Project (EU-Project 24931) was launched in November 1997. In this project a measuring station was built at the Pyhasalmi flotation plant. The system includes an RGB camera and a spectral color measuring instrument for the color inspection of the flotation. The RGB camera or visible spectral range is also measured to compare the operators' comments on the color of the froth relating to the sphalerite concentration and the process balance. Different dried mineral (sphalerite) ratios were studied with iron pyrite to find out about the minerals' typical spectral features. The correlation between sphalerite spectral reflectance and sphalerite concentration over various wavelengths are used to select the proper camera system with filters or to compare the results with the color information from the RGB camera. Various machine vision candidate techniques are discussed for this application and the preprocessed information of the dried mineral colors is used and adapted to the online measuring station. Moving froth bubbles produce total reflections, disturbing the color information. Polarization filters are used and the results are reported. Also the reflectance outside the visible light is studied and reported.
NASA Astrophysics Data System (ADS)
Todoran, R.; Todoran, D.; Anitas, E. M.; Szakács, Zs
2016-08-01
We propose reflectance measurements as a method for the evaluation of the kinetics of adsorption processes, to compute the diffusion times of the adsorption products at the thin layers formed at the sphalerite natural mineral-potassium ethyl xanthate solution interface. The method is based on the intensity measurement of the reflected monochromatic radiation obtained from the mineral-xanthate thin layer as a function of time. These determinations were made at the thin layer formed between the sphalerite or activated sphalerite natural minerals with potassium ethyl xanthate, for different solutions concentrations and pH values at constant temperature. Diffusion times of desorbed molecular species into the liquid bring important information about the global kinetics of the ions in this phase during adsorption processes at interfaces. Analysing the time dependence of this parameter one concluded on the diffusion properties of the xanthate molecule in the solution depending on its concentration and pH, knowing that at the initial time these molecules had a uniform spread. This method enabled us to determine that, in time interval of approximately 35 minutes to achieve dynamic equilibrium in the formation of the interface layer, one had three different kinetic behaviours of our systems. In the first 5-8 min one had highly adsorbent character, the state of equilibrium is followed by low adsorbent properties. Gaining information on the adsorption kinetics in the case of xanthate on mineral surface leads to the optimization of the industrial froth flotation process.
The solubility of sphalerite (ZnS) in sulfidic solutions at 25°C and 1 atm pressure
NASA Astrophysics Data System (ADS)
Daskalakis, Kostas D.; Helz, George R.
1993-10-01
The solubility of both synthetic and natural sphalerite have been measured at 25°, pH 2.2 to 9.1, and ΣS(-II) 0.1 to 0.0004 M. Inversion of wurtzite to sphalerite during equilibration precluded measuring wurtzite solubilities. To hinder colloid formation, we used well-crystallized ZnS preleached with EDTA. Run durations were several months. Clean-room analytical procedures were used. Measured solubilities are much lower than those of GüBELI and STE-MARIE (1967), whose solutions probably contained colloids. Colloidal ZnS sols are shown not to equilibrate with sphalerite even over several months. The new data are consistent with, and complementary to those of HAYASHI et al. (1990). The solubility of Zn 2+ in equilibrium with sphalerite is given by a Zn2+a 2HS-/a H2 S = 10 18.47 +- 0.01. Aqueous Zn-polysulfides appear to be unimportant under the conditions studied. In terms of anhydrous, mononuclear complexes, Zn solubility can be described by a series of complexes whose formation is represented by: ZnS( sp) + (2 y- z-2) HS- + ( z- y+1) H2SaqZnSyHz-(2 y- z-2) , Kyz. Three complexes are essential to model the results adequately: Zn( HS) -24, logK44 = -3.83 ± 0.17; ZnS( HS) -, logK21 = -4.64 ± 0.08; and ZnS( HS) -22, logK32 = -5.33 ± 0.07. Additional complexes improve the fit marginally. Others have suggested that ZnS(HS) -22 should be represented by its hydrated formula, Zn(OH)(HS) -23. The observed stability of this complex is much greater than predicted for a mixed ligand complex derived from Zn(HS) -24 and Zn(OH) -24. Based on recent calculations, less than 3/4 of the discrepancy can be accounted for by molecular orbital stabilization. A tetranuclear formula suggested by known Zn-thiolate structures and supported by EXAFS evidence of multinuclearity is a possible alternative. The solubility of Zn in anoxic marine waters is determined largely by ZnS(HS) -, which dominates in mildly alkaline solutions at low σS(-II). According to the new data, anoxic zones in Framvaren Fjord and the Black Sea are undersaturated with respect to sphalerite, except immediately below the oxic/anoxic interface. This suggests that scavenging, rather than precipitation, controls Zn.
Mercury Isotopes as Proxies to Identify Sources and Environmental Impacts of Mercury in Sphalerites
Yin, Runsheng; Feng, Xinbin; Hurley, James P.; Krabbenhoft, David P.; Lepak, Ryan F.; Hu, Ruizhong; Zhang, Qian; Li, Zhonggen; Bi, Xianwu
2016-01-01
During the past few years, evidence of mass independent fractionation (MIF) for mercury (Hg) isotopes have been reported in the Earth’s surface reservoirs, mainly assumed to be formed during photochemical processes. However, the magnitude of Hg-MIF in interior pools of the crust is largely unknown. Here, we reported significant variation in Hg-MIF signature (Δ199Hg: −0.24 ~ + 0.18‰) in sphalerites collected from 102 zinc (Zn) deposits in China, indicating that Hg-MIF can be recorded into the Earth’s crust during geological recycling of crustal material. Changing magnitudes of Hg-MIF signals were observed in Zn deposits with different formations, evidence that Hg isotopes (especially Hg-MIF) can be a useful tracer to identify sources (syngenetic and epigenetic) of Hg in mineral deposits. The average isotopic composition in studied sphalerites (δ202Hgaverage: −0.58‰; Δ199Hgaverage: +0.03‰) may be used to fingerprint Zn smelting activities, one of the largest global Hg emission sources. PMID:26728705
Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.
Matthies, R; Krahé, L; Blowes, D W
2014-07-15
Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Deng, Jiu-shuai; Mao, Ying-bo; Wen, Shu-ming; Liu, Jian; Xian, Yong-jun; Feng, Qi-cheng
2015-02-01
Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satisfactory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mechanisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions released from the ancient fluids reached 1.02 × 10-6 mol/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 × 10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.
Mineralogy and chemistry of massive sulfide deposits from the Juan de Fuca Ridge.
Koski, R.A.; Clague, D.A.; Oudin, E.
1984-01-01
Two types of massive sulphide were dredged from one of the six vent sites located in the axial valley of the southern Juan de Fuca ridge. Type A samples are angular slabs of dark grey Zn-rich sulphide with interlayers and a thin, partly-oxidized crust of Fe-sulphide. These layered sulphide aggregates appear to be fragments of a sulphide wall enclosing an active hydrothermal vent. The outer sulphide wall is composed of colloform Fe sulphide and Fe-poor sphalerite deposited under low-T conditions when sea-water and hydrothermal fluid mix above the discharge point. Inside the wall the intensifying hydrothermal sytem deposits a higher-T assemblage of granular Fe-rich sphalerite, wurtzite, pyrite and minor Cu-Fe sulphide. Type B sulphide samples are sub-rounded, spongy-textured fragments composed almost entirely of dendritic aggregates of pale Fe-poor colloform sphalerite and opaline silica. This type of sulphide is deposited in settings peripheral to sites of focused discharge and in open spaces by moderate- to low-T fluid discharging at a slow but variable rate; the fluid becomes increasingly oxidizing, resulting in late-stage deposits of hematite, baryte and sulphur.-L.di H.
Physical chemistry mechanisms of CDR system in sulphide mineral flotation
NASA Astrophysics Data System (ADS)
Pak, To-Hyon; Sun, Ti-Chang; Kou, Jue; Huang, Chol-Ryong
2012-03-01
The flotation tests, zeta potential measurements, and Fourier transform infrared spectroscopy (FTIR) analysis on galena, sphalerite, and pyrite were studied in a collecting-depressing-reactivating (CDR) system. In this system, sulphide minerals were first collected and activated by the collector, and then depressed strongly by Ca(OH)2 in a strong alkaline solution. Finally, they were reactivated by H2SO4. The flotation tests of pure minerals showed that in the Ca(OH)2 depressing process sulphide minerals had similar flotation characteristics because they had already been influenced by the collector. Hence, the flotability differences between them were reduced. However, in the H2SO4 reactivating process considerable differences in the flotability between galena and sphalerite/pyrite were produced. That is to say, galena was relatively easy to be reactivated by H2SO4, but sphalerite and pyrite were not reactivated at pH > 11. The zeta potentials of sulfide minerals measured by the Zeta Plus presented irreversible characteristics on the change of pH values. The results of the FTIR spectra analysis indicated that the collectors already adsorbed on the mineral surface were removed partially by Ca(OH)2.
Hayba, D.O.
1997-01-01
Detailed fluid inclusion studies on coarse-grained sphalerite from the OH vein, Creede, Colorado, have shown that the abrupt color changes between growth zones correspond to abrupt changes in the nature of the ore fluids. Within each growth zone, however, the composition of the fluids remained constant. The base of a distinctive orange-brown growth zone marks a sharp increase in both temperature and salinity relative to the preceding yellow-white zone. The orange-brown growth zone can be correlated along much of the vein and is believed to represent a time-stratigraphic interval. Along the vein, temperatures and salinities of fluid inclusions within this interval show a systematic decrease from about 285??C and 11.5 wt percent NaCl equiv near the base of the vein to about 250??C and 8 wt percent NaCl equiv, respectively, near the top of the vein. The iron concentration of this sphalerite growth zone shows a similar pattern, decreasing from about 2.8 to 1.2 mole percent FeS. When plotted on an enthalpy-salinity diagram, the fluid inclusion data define a spatial trend indicating the progressive mixing of deeply circulating hydrothermal brines with overlying, dilute ground waters. The hydrothermal brines entered the OH vein from below at a temperature, salinity, and density of approximately 285??C, 11.5 wt percent NaCl equiv, and 860 kg/m3, respectively, whereas the overlying ground waters appear to have been preheated to roughly 150??C and had an assumed salinity of 0 wt percent and a density of 920 kg/m3. The greater density of the heated ground water promoted mixing with the hydrothermal brine within the open fractures, causing sphalerite deposition. Although there were also episodes of boiling during vein mineralization, boiling appears unimportant for this sphalerite. Isotopic evidence and geochemical modeling studies also indicate that mixing was the depositional mechanism for sphalerite. An important aspect of the mixing hydrology of the Creede system involves an aquitard overlying the OH vein. This low permeability zone restricted the flow of ground water into the vein from above and forced the upwelling hydrothermal fluids to flow laterally along the vein. The mixing environment thus occurred along the interface between a deeply circulating hydrothermal convection cell and a topographically driven shallow ground-water system.
Atomistic simulations of activated processes in nanoparticles synthesis
NASA Astrophysics Data System (ADS)
Giberti, Federico; Galli, Giulia
Core-shell and Janus nanopartices are promising building blocks for new, highly efficient solar cells. One of the most common synthetic pathways to produce such nanostructures is the use of cation exchange reactions. Although widely used, these procedures are not completely understood. We employed classical Molecular Dynamics and Monte Carlo simulations to understand these transformation at the molecular level; in particular we investigated the conversion from CdSe (sphalerite) to PbSe (rocksalt) NPs with 2-3 nm diameter. In order to recover the equilibrium free energy surfaces we used state of the art enhanced sampling techniques, including Metadynamics. The formation of hybrid core-shell structures resulted to be an activated process, where the limiting step is the transition of a sphalerite to a rocksalt PbSe nucleus. We found that the barrier height and the stability of the two phases depend on the size of the PbSe nucleus, suggesting that the process could proceed via a two step mechanism, where a small sphalerite nucleus is formed first, and it then transforms to a rocksalt nucleus. Our results give insight into possible manipulation processes at the molecular scale, which could be used to stabilize metastable NPs and tune their physical and chemical properties. This work was supported by the DOE Grant No. DE-FG02-06ER46262.
NASA Astrophysics Data System (ADS)
Mondillo, Nicola; Arfè, Giuseppe; Herrington, Richard; Boni, Maria; Wilkinson, Clara; Mormone, Angela
2018-02-01
Supergene nonsulfide ores form from the weathering of sulfide mineralization. Given the geochemical affinity of Ge to Si4+ and Fe3+, weathering of Ge-bearing sulfides could potentially lead to Ge enrichments in silicate and Fe-oxy-hydroxide minerals, although bulk rock Ge concentrations in supergene nonsulfide deposits are rarely reported. Here, we present the results of an investigation into Ge concentrations and deportment in the Cristal supergene Zn nonsulfide prospect (Bongará, northern Peru), which formed from the weathering of a preexisting Mississippi Valley-type (MVT) sulfide deposit. Material examined in this study originates from drillcore recovered from oxidized Zn-rich bodies 15-20 m thick, containing 5-45 wt% Zn and Ge concentrations 100 ppm. Microanalysis and laser ablation-ICP-MS show that precursor sphalerite is rich in both Fe (mean Fe = 8.19 wt%) and Ge (mean Ge = 142 ppm). Using the mineral geothermometer GGIMFis—geothermometer for Ga, Ge, In, Mn, and Fe in sphalerite—proposed by Frenzel et al. (Ore Geol Rev 76:52-78, 2016), sphalerite trace element data from the Cristal prospect suggest a possible formation temperature ( T GGIMFis) of 225 ± 50 °C, anomalously high for a MVT deposit. Germanium concentrations measured in both goethite (mean values 100 to 229 ppm, max 511 ppm) and hemimorphite (mean values 39 to 137 ppm, max 258 ppm) are similar to concentrations measured in hypogene sphalerite. Additionally, the Ge concentrations recorded in bulk rock analyses of sphalerite-bearing and oxidized samples are also similar. A persistent warm-humid climate is interpreted for the region, resulting in the development of an oxidation zone favoring the formation of abundant Zn hydrosilicates and Fe hydroxides, both able to incorporate Ge in their crystal structure. In this scenario, Ge has been prevented from dispersion during the weathering of the Ge-bearing sulfide bodies and remains in the resultant nonsulfide ore.
Gallium-bearing sphalerite in a metal-sulfide nodule of the Qingzhen (EH3) chondrite
NASA Technical Reports Server (NTRS)
Rambaldi, E. R.; Rajan, R. S.; Housley, R. M.; Wang, D.
1986-01-01
The composition and possible history of the Qingshen (EH3) chondrite is presented. The chondrite contains a population of spheroidal metal-sulfide nodules, which display textural evidence of reheating and melting. Evidence of metal sulfuration is also present, suggesting replacement of metal by sulfide during melting. This process has led to the nucleation of perryite along metal-sulfide interfaces. The Ga-bearing sphalerite that was found may have formed by injection of molten sulfide droplets into the metal followed by subsolidus diffusion of Ga from the metal into the sulfide. The latter may occur because of Ga supersaturation in the metal during progressive sulfuration and its decreased affinity for the metal phase during cooling below the taenite-kamacite transition point.
NASA Astrophysics Data System (ADS)
Sun, Xiang; Zheng, Youye; Pirajno, Franco; McCuaig, T. Campbell; Yu, Miao; Xia, Shenlan; Song, Qingjie; Chang, Huifang
2018-03-01
Several Au, Sb, Sb-Au, Pb-Zn, and Sb-Pb-Zn-Ag deposits are present throughout the North Himalaya in southern Tibet, China. The largest Sb-Pb-Zn-Ag deposit is Zhaxikang (18 Mt at 0.6 wt% Sb, 2.0 wt% Pb, 3.5 wt% Zn, and 78 g/t Ag). Zhaxikang veins are hosted within N-S trending faults, which crosscut the Early-Middle Jurassic Ridang Formation consisting of shale interbedded with sandstone and limestone deposited on a passive continental margin. Ore paragenesis indicates that Zhaxikang mineralization occurred in two main phases composed of six total stages. The initial phase was characterized by assemblages of fine-grained Mn-Fe carbonate + arsenopyrite + pyrite + sphalerite (stage 1), followed by relatively coarse-grained Mn-Fe carbonate + Fe-rich sphalerite + galena + pyrite (stage 2). The second phase was marked by assemblages of quartz + pyrite + Fe-poor sphalerite and Ag-rich galena + tetrahedrite + sericite (stage 3), quartz + Sb-Pb sulfosalt minerals mainly composed of boulangerite and jamesonite (stage 4), quartz + stibnite ± cinnabar (stage 5), and quartz ± calcite (stage 6). Sulfides of stage 2 have δ34SV-CDT of 8.4-12.0‰, 206Pb/204Pb ratios of 19.648 to 19.659, 207Pb/204Pb ratios of 15.788 to 15.812, and 208Pb/204Pb ratios of 40.035 to 40.153. Sulfides of stage 3 have similar δ34SV-CDT of 6.1-11.2‰ and relatively more radiogenic lead isotopes (206Pb/204Pb = 19.683-19.792). Stage 4 Sb-Pb sulfosalt minerals have δ34SV-CDT of 5.0-7.2‰ and even more radiogenic lead (206Pb/204Pb = 19.811-19.981). By contrast, stibnite of stage 5 has δ34SV-CDT of 4.5-7.8‰ and less radiogenic lead (206Pb/204Pb = 18.880-18.974). Taken together with the geological observations that the Pb-Zn-bearing Mn-Fe carbonate veins were crosscut by various types of quartz veins, sphalerite and galena of stage 2 underwent dissolution and remobilization, and that Sb-Pb(-Fe) sulfosalts formed at the expense of Pb from stage 2 galena and of Fe from stage 2 sphalerite, we argue that the early Pb-Zn veins were overprinted by later Sb-rich fluids. Stage 2 fluids were likely acidic and oxidized and leached lead from high-grade metamorphic rocks of the Greater Himalayan crystalline complex (GHC) and sulfur from reduced rocks, such as slate of the Ridang Formation, along N-S trending faults, leading to precipitation of Pb-Zn sulfides and Mn-Fe carbonate and formation of solution collapse breccias. Later Sb-rich fluids leached Pb from the GHC and the pre-existing sulfides and deposited Fe-poor sphalerite, Ag-rich galena, tetrahedrite, Sb-Pb sulfosalts, and stibnite in quartz veins that cut pre-existing Pb-Zn-bearing Mn-Fe carbonate veins. The Sb-rich fluids also likely leached Pb from Early Cretaceous gabbro and formed stibnite at shallow levels where early Pb-Zn-bearing Mn-Fe carbonate veins are absent. A sericite 40Ar-39Ar plateau age of 17.9 ± 0.5 Ma from stage 3 veins represents the timing of the onset of stage 3 mineralization.
An experimental study of Pb and Zn as a function of HCl at 300 and 500°C
NASA Astrophysics Data System (ADS)
Rock, M.; Frank, M. R.
2017-12-01
Hydrothermal galena (PbS) and sphalerite (ZnS) deposits are important sources of Pb and Zn and can be related to low-temperature Mississippi Valley (MVT), moderate temperature massive sulfides (VMS), and higher-temperature porphyry type deposits). Lead and Zn are thought to complex with chloride (PbCl2 and ZnCl2) in the hydrothermal fluid and can precipitate through a decrease in temperature, an increase in pH, or through the addition of reduce sulfur. There is, however, a dearth of data on the solubility of galena and sphalerite in acidic and sulfur-rich hydrothermal fluids over a range temperature that spans the MVT to porphyry systems The experiments were conducted in René 41 cold-seal pressure vessels at 300 and 500°C and 100 MPa to determine the concentrations of Pb and Zn in hydrothermal fluids as a function of HCl. Platinum capsules were loaded with natural galena and sphalerite and an aqueous fluid of 13-15 wt.% NaCl (eq.) containing HCl + NaCl. The [Na/H] of the aqueous fluid was varied from 1.75 to 340. The aqueous fluids were captured at the conclusion of the experiment and Pb and Zn concentrations were determined by using AA and ICP-OES. The data illustrate that the concentration of Pb and Zn in the fluid increased directly with temperature and total chloride while indirectly with [Na/H]. Lead and Zn concentrations at 300°C were highest at a [Na/H] of 1.75 with concentrations of 84 μg/g and 2200 ± 600 μg/g, respectively, and decreased to 4 μg/g and 241 μg/g, respectively, at a [Na/H] of 295. At 500°C, lead concentrations were 7600 ± 1600 μg/g at a [Na/H] of 1.75 and decreased to 1170 μg/g at a [Na/H] of 340. Zinc concentrations at 500°C were 1700 μg/g at a [Na/H] of 30 and 640 μg/g at a [Na/H] of 100. Decreasing acidity (increasing [Na/H]) and temperature are especially efficient at inducing the precipitation of galena and sphalerite and could produce variable Pb:Zn values in a given system depending on if temperature or acidity was more variable. Thus, galena and sphalerite can precipitate from a reduced sulfur-bearing fluid provided the acidity of the fluid was sufficiently high during transportation. Further, the variable Pb:Zn ratios observed in some ore-bearing systems could be a result of differences in the rate of change of temperature, acidity, and reduced sulfur and not from separate pulses of distinct mineralizing fluids.
Kelley, Karen D.; Leach, David L.; Johnson, Craig A.
2000-01-01
Stratiform shale-hosted massive sulfide deposits, sulfidebearing concretions and vein breccias, and barite deposits are widespread in sedimentary rocks of Late Devonian to Permian age in the northern Brooks Range. All of the sulfide-bearing concretions and vein breccias are hosted in mixed continental-marine clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. The clastic rocks and associated sulfide occurrences underlie chert and shale of Mississippian-Pennsylvanian(?) age that contain large stratiform massive sulfide deposits like that at Red Dog. The relative stratigraphic position of the vein breccias, as well as previously published mineralogical, geochemical, and lead-isotope data, suggest that the vein breccias formed coevally with overlying shale-hosted massive sulfide deposits and that they may represent pathways of oreforming hydrothermal fluids. Barite deposits are hosted either in Mississippian chert and limestone (at essentially the same stratigraphic position as the shale-hosted massive sulfide deposits) or Permian chert and shale. Although most barite deposits have no associated base-metal mineralization, barite occurs with massive sulfide deposits at the Red Dog deposit.Galena and sphalerite from most vein breccias have δ34S values from –7.3 to –0.7‰ (per mil) and –5.1 to 3.6‰, respectively; sphalerite from sulfide-bearing concretions have δ34S values of 0.7 and 4.7‰. This overall range in δ34S values largely overlaps with the range previously determined for galena and sphalerite from shale-hosted massive sulfide deposits at Red Dog and Drenchwater. The Kady vein-breccia occurrence is unusual in having higher δ34S values for sphalerite (12.1 to 12.9‰) and pyrite (11.3‰), consistent with previously published values for the shale-hosted Lik deposit. The correspondence in sulfur isotopic compositions between the stratiform and vein-breccia deposits suggests that they share a common source of reduced sulfur, or derived reduced sulfur by similar geochemical processes. Most likely, the reduced sulfur was derived by biogenic sulfate reduction (BSR) or thermochemical sulfate reduction (TSR) of seawater sulfate during Devonian-Mississippian time.The δ18O values of quartz from the vein breccias are between 16.6 and 19.9‰. Using the sphalerite-galena sulfur isotopic temperature of 188°±25°C, the calulated hydrothermal fluids had δ18O values of 4.2 to 7.5‰. The calculated range of δ18O values of the fluids is similar to that of pore fluids in equilibrium with sedimentary rocks during diagenesis at 100°– 190°C.
Todoran, R; Todoran, D; Szakács, Zs
2016-01-05
In this work we propose optical luminescence measurements as a method to evaluate the kinetics of adsorption processes. Measurement of the intensity of the integral optical radiation obtained from the mineral-xanthate interface layer, stimulated with a monochromatic pulsating optical signal, as a function of time were made. The luminescence radiation was obtained from the thin interface layer formed at the separation surface between the sphalerite natural mineral and potassium ethyl xanthate solution, for different solution concentrations and pH-es at the constant industry standard temperature. This method enabled us to determine the time to achieve dynamic equilibrium in the formation of the interface layer of approximately 20min, gaining information on the adsorption kinetics in the case of xanthate on mineral surface and leading to the optimization of the industrial froth flotation process. Copyright © 2015 Elsevier B.V. All rights reserved.
Stibnite vein from Dębowina near Bardo (polish Sudetes)
NASA Astrophysics Data System (ADS)
Kotula, Piotr
2013-09-01
In the contact zone of the Bardo Structure and Kłodzko-Złoty Stok Intrusion and Kłodzko Metamorphic, metasomatic orebearing quartz-carbonate veins rich in Sb, Zn, Cu, Ag, Au, Pb are present. In 1771 the mine ,,Reiche Silber Gluck” within stibnite vein was founded in Dębowina near Bardo. Its entrance was discovered again in 2007. The stibnite vein is mainly build of stibnite and sphalerite and of quartz and dolomite rich in Mn. Stibnite crystallizes as columnar or forming radiate centres and aciculars. Its crystals reach size to 2 mm. Sphalerite appears as individual anhedral and polymineralic grained concentrations reaching size to 2,5 mm. Earlier pyrite and arsenopyrite crystallized - they occur locally in this deposit. There were found also in the deposit tetrahedrite rich in Ag, what wasn't reported earlier in studies from the mine in Dębowina.
Speciation And Bioavailability Of Zinc In Amended Sediments
The speciation and bioavailability of zinc (Zn) in smelter-contaminated sediments was investigated as a function of phosphate (apatite) and organic amendment loading rate. Zinc species identified in preamendment sediment were zinc hydroxide-like phases, sphalerite, and zinc sorbe...
NASA Astrophysics Data System (ADS)
Potra, A.
2015-12-01
The Ozark region of the U.S. midcontinent is one of the world's most important provinces of MVT mineralization, hosting world-class ore deposits. The ores in the Tri-State (TS) and Northern Arkansas (NA) districts, dominated by sphalerite, are mainly hosted by platform carbonate rocks and vary in age from Ordovician and Mississippian for NA and Mississippian for TS. The deposits are considered to have formed from a regional hydrothermal flow system consisting of sedimentary brines discharged from the Arkoma basin and adjacent platform during the Late Pennsylvanian to Early Permian Ouachita orogeny. New MC-ICP-MS Pb isotope analyses of sphalerites are presented in order to compare and contrast the isotopic signature of ores from the NA and TS districts with those from other MVT districts from central and eastern US and trace metal sources. The Pb isotope ratios of ores from the TS District (208Pb/204Pb between 40.7443 and 41.2626; 207Pb/204Pb between 15.8633 and 15.9571; 206Pb/204Pb between 21.8373 and 22.1956) plot in an area that is superimposed on the Pb isotope field defined by samples from the Central Missouri District, suggesting similar metal sources. The sphalerites are less radiogenic than samples from the Upper Mississippi Valley District, but more radiogenic than samples from any other MVT district. Sphalerites from the NA District have lower Pb isotope values (208Pb/204Pb between 39.4633 and 40.8863; 207Pb/204Pb between 15.8216 and 15.9176; 206Pb/204Pb between 20.2396 and 21.6438) than the TS District ores; they plot below the field defined by samples from the Illinois-Kentucky district and overlap the field defined by ores from the Southeast Missouri (Viburnum and Old Lead Belt) district, implying similar metal sources. Current data suggest that basement of Grenvillian age (1 - 1.2 by), thought to be present in Arkansas, to the south of the Viburnum Trend, may be a likely source of the radiogenic Pb component. Pb data from ores in the NA and the Southeast Missouri districts are collinear with data from the TS and Central Missouri districts.
NASA Astrophysics Data System (ADS)
Yun, Seong-Taek; So, Chil-Sup; Choi, Sang-Hoon; Shelton, Kevin L.; Koo, Ja-Hak
1993-04-01
The Wolyu mine is one of the largest vein-type gold-silver-bearing epithermal systems in the Youngdong district and is the first gold-silver deposit in Korea found to contain significant germanium, in the form of argyrodite (Ag8GeS6). Mineralized veins (78.9 ± 1.2 Ma) crosscutting Late Cretaceous hostrock tuff and quartz porphyry (81.5 ± 1.8 Ma) consist of three stages of quartz and carbonates, the first of which contains pyrite, basemetal sulfides and Au-Ag-minerals. Stage I Au-Ag-Ge-mineralized veins show a systematic variation of mineral assemblage with time: (1) quartz + pyrite; (2) quartz + pyrite + sphalerite + electrum + argentite; (3) carbonate + quartz + sphalerite + electrum + argentite; (4) carbonate + native silver + argentite + Ag-sulfosalts + argyrodite + sphalerite. Calculated values of temperature and sulfur activity are: assemblage (1), 360-280°C and 10-7-10-10; (2), 280-210°C and 10-10-10-14; (3), 210-180°C and 10-14-10-16; (4), 180-155°C and 10-17-10-18. These data, the frequent association of gold with sulfides, and the abundance of pyrite in alteration zones indicate that decreasing sulfur activity and cooling were important in triggering gold deposition. Hydrogen and oxygen isotope compositions of ore fluids display a systematic variation with increasing time. Within the main Ag-Au-Ge mineralization, δD and δ 18O values decrease with the transition from quartz to carbonate deposition (from -78 and -2.8% to -90 and -8.7%., respectively), indicating increasing involvement (mixing) of less evolved meteoric water which resulted in progressive cooling and dilution of ore fluids in the shallow (≈ 370 600 m) Wolyu epithermal system.
NASA Astrophysics Data System (ADS)
Bestemianova, K. V.; Grinev, O. M.
2017-12-01
Zmeinogorsky ore district is located in the northwest part of Ore Altai megatrough, which has long-lasting history of its development and complicated geological structure. Within the ore district, which is the northwest part of the devonian Zmeinogorsk-Bystrushinsky trough, ore mineralization is associated with the system of northwest border faults and cross branch faults. There were four main stages and five phases of minerogenesis. The first stage is the stage of oregenesis beginning and quartz-chlorite-sericite wall-rock alteration rocks formation. Ore deposition and intense tectonics took place during the second stage. The third stage is the most longstanding and productive ore formation stage. There are five distinct minerogenesis phases within this stage. The fourth stage expressed in erosion development and supergene alteration of already formed ore bodies with oxidation zone formation. Main ore minerals are pyrite, chalcopyrite, sphalerite and galena. Minor minerals are tetrahedrite, bornite, tennantite and chalcocite. Precious metals minerals are acanthite, gold, electrum, gold and silver amalgams. Barren minerals are barite, quartz, calcite, gypsum. According to obtained data average isotopic composition of third stage sulphides is: pyrite -0,2‰, chalcopyrite 0‰, galena +0,5‰, sphalerite -1,2‰ for the first complex; chalcopyrite -1,9‰, galena -3,4‰, sphalerite -2,3‰, tetrahedrite -3,7‰ for the second complex; tennantite -12,8‰, bornite -8,9‰ for the third complex. Sulfur isotopic compoisiton variations indicate source inhomogeneity. Thus, there was dominant source change from mantle one in the beginning to crustal one in the end. Main oregenesis stages took place in the range of temperatures between 170 and 210°С and in the mineral-forming solutions salinity range between 3 and 10 wt % NaCl equiv.
NASA Astrophysics Data System (ADS)
Bustos Rodríguez, H.; Rojas Martínez, Y.; Oyola Lozano, D.; Pérez Alcázar, G. A.; Fajardo, M.; Mojica, J.; Molano, Y. J. C.
2005-02-01
In this work a study on gold mineral samples is reported, using optical microscopy, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The auriferous samples are from the El Diamante mine, located in Guachavez-Nariño (Colombia) and were prepared by means of polished thin sections. The petrography analysis registered the presence, in different percentages that depend on the sample, of pyrite, quartz, arsenopyirite, sphalerite, chalcopyrite and galena. The XRD analysis confirmed these findings through the calculated cell parameters. One typical Rietveld analysis showed the following weight percent of phases: 85.0% quartz, 14.5% pyrite and 0.5% sphalerite. In this sample, MS demonstrated the presence of two types of pyrite whose hyperfine parameters are δ 1 = 0.280 ± 0.002 mm/s and Δ 1 = 0.642 ± 0.002 mm/s, δ 2 = 0.379 ± 0.002 mm/s and Δ 2 = 0.613 ± 0.002 mm/s.
Field-assisted sintering and phase transition of ZnS-CaLa 2S 4 composite ceramics
DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Yiyu; Zhang, Lihua; Kisslinger, Kim
In the present study, zinc sulfide (ZnS) and calcium lanthanum sulfide (CaLa 2S 4, CLS) composite ceramics were consolidated via field-assisted sintering of 0.5ZnS-0.5CLS (volume ratio) composite powders at 800–1050 °C. Through sintering curve analyses and microstructural observations, it was determined that between 800 and 1000 °C, grain boundary diffusion was the main mechanism controlling grain growth for both the ZnS and CLS phases within the composite ceramics. The consolidated composite ceramics were determined to be composed of sphalerite ZnS, wurtzite ZnS and thorium phosphate CLS. The sphalerite-wurtzite phase transition of ZnS was further demonstrated to be accompanied by themore » formation of stacking faults and twins in the ceramics. Furthermore, it was also found that the addition of the CLS phase improved the indentation hardness of the ceramics relative to pure ZnS by homogeneous dispersion of ZnS and CLS small grains.« less
Field-assisted sintering and phase transition of ZnS-CaLa 2S 4 composite ceramics
Li, Yiyu; Zhang, Lihua; Kisslinger, Kim; ...
2017-07-17
In the present study, zinc sulfide (ZnS) and calcium lanthanum sulfide (CaLa 2S 4, CLS) composite ceramics were consolidated via field-assisted sintering of 0.5ZnS-0.5CLS (volume ratio) composite powders at 800–1050 °C. Through sintering curve analyses and microstructural observations, it was determined that between 800 and 1000 °C, grain boundary diffusion was the main mechanism controlling grain growth for both the ZnS and CLS phases within the composite ceramics. The consolidated composite ceramics were determined to be composed of sphalerite ZnS, wurtzite ZnS and thorium phosphate CLS. The sphalerite-wurtzite phase transition of ZnS was further demonstrated to be accompanied by themore » formation of stacking faults and twins in the ceramics. Furthermore, it was also found that the addition of the CLS phase improved the indentation hardness of the ceramics relative to pure ZnS by homogeneous dispersion of ZnS and CLS small grains.« less
New Gallium End-Member in Epidote Group
NASA Astrophysics Data System (ADS)
Soboleva, A. A.; Varlamov, D.; Mayorova, T.
2011-12-01
Unique ultrahigh-Ga (Ga up to 14.5 wt. %) mineral of epidote group is discovered in Tykatlova gold-sulfure ore occurrence in the eastern slope of the Subpolar Urals, Russia. It is the first find of the Ga silicate mineral in the world. Only five Ga minerals are presented in the IMA official list. Generally, two unique deposites in Africa contain Ga minerals - Tsumeb in Namibia and Kipushi in DR Congo. Tykatlova occurrence is situated in early Ordovician rhyolites and rhyodacites metamorphosed in greenschist facies, sulfide mineralization is located in fault zones. Ga-phases were found out in sphalerite-pyrite-galena assemblage with chalcopyrite and minor Ag-bearing bornite, tetrahedrite-tennantite, various Ag and Cu sulfides and sulfosalts. Secondary ore minerals are anglesite, cerussite, lead and zinc hydroxides. Vein minerals are quartz, calcite, Zn-Mn carbonates, anhydrite (or gypsum). Ga-minerals are usually inclusions (common in sphalerite, sometimes in pyrite and galena), they are rarely located between grains of sulfides or quartz. Ga-phases are assigned to epidote group due to morphology of grains, their chemical composition (EPMA using EDS and WDS), stoichiometry and Raman data. Their grains are elongated, roundish or well-shaped, they are 30-60 up to 100 μm in length, with complex zonality. The general sequence of zones from the core to rims: a) "epidote-(Ga)" with 6-20 wt.% Ga2O3, REE are almost absent; b) high Ga allanite-(Ce) with 3-11 wt.% Ga2O3, 3-20 wt.% REE (calculated as oxide); c) allanite-(Ce) with 0.0-2.0 wt.% Ga2O3, 4-19 wt.% REE; d) epidote-allanite rims without Ga, 0-6 wt.% REE. Empirical formula of phases mostly enriched in Ga: (Ca1.88Mg0.15Mn0.03)2.06(Al1.77Ga0.97Fe3+0.26)3.00(Si2.91Al0.09)3O12(OH) (Ca1.85Mg0.11Mn0.02)1.98(Al1.89Ga1.03Fe3+0.19)3.11(Si2.93Al0.07)3O12(OH). Crystal chemistry of Ga-epidote isn't clear yet, but we assume that Ga substitutes Fe3+ rather than Al. Correlation factor in Fe3+-Ga pair (core zones of grains) reaches -0.92. Decrease of Ga toward to grain rims "allows" occurrence of REE in the epidote structure, as Ga ceases to occupy a large octahedron where bivalent ions (Fe2+, Mg, Mn2+) can enter for compensation of trivalent REE cations. Raman spectra of the Ga-phases shows a high convergence with epidote spectra. Detectable Ga concentrations (0.048-0.058 wt.%, WDS) have been established only in sphalerite that includes grains of epidote-allanite enriched in Ga. So, the most probable source of Ga is Ga-enriched sphalerite. Growth of Ga phases might take place during greenschist facies metamorphism. However, we can't exclude vice versa variant - increase of Ga concentration in sphalerite in result of decomposition of primary high-Ga silicates. Conclusions: (1) A unique high-Ga mineral of the epidote group was discovered in the Subpolar Urals. (2) It is the first find of high-Ga silicate mineral in the world. Presumably it is new member of epidote group that could be named "epidote-(Ga)" (as it is recommended by the IMA Commission). Financial support by RFBR, grant 11-05-01087-a.
Plumlee, Geoffrey S.; Heald Whitehouse-Veaux, Pamela
1994-01-01
The Bulldog Mountain vein system, Creede district, Colorado, is one of four major epithermal vein systems from which the bulk of the district's historical Ag-Pb-Zn-Cu production has come. Ores deposited along the vein system were discovered in 1965 and were mined from 1969 to 1985.Six temporally gradational mineralization stages have been identified along the Bulldog Mountain vein system, each with a characteristic suite of minerals deposited or leached and a characteristic distribution within the vein system; some of these stages are also strongly zoned within the vein system. Stage A was dominated by deposition of rhodochrosite along the lower levels of the Bulldog Mountain ore zone. Stage B in the northern parts of the ore zone is characterized by abundant fine-grained sphalerite and galena, with lesser tetrahedrite and minor chlorite and hematite. With increasing elevation to the south, stage B ores become progressively more barite and silver rich, with alternating barite and fine-grained sphalerite + galena generations; native silver + or - acanthite assemblages are also locally abundant within southern stage B barite sulfide ores, whereas chalcopyrite and other Cu and Ag sulfides and sulfosalts are present erratically in minor amounts. Stage C in the upper and northern portions of the ore zone is characterized by abundant quartz and fluorite, minor adularia, hematite, Mn siderite, sphalerite, and galena, and major leaching of earlier barite; to the south, some barite and sulfides may have been deposited. Stage D sphalerite and galena were deposited in the upper and northern portions of the ore zone; a barite- and silver-rich facies of this stage may also be present in the southern portions of the vein system. Late in stage D, mineralogically complex assemblages containing chalcopyrite, tetrahedrite, polybasite, bornite, pyrargyrite, and a variety of other sulfides and sulfosalts were deposited in modest amounts throughout the vein system. This complex assemblage marked the transition to stage E. During stage E, the final sulfide stage, abundant botryoidal pyrite and marcasite with lesser stibnite, sphalerite, and sulfosalts were deposited primarily along the top of the Bulldog Mountain ore zone. Stage F, the final mineralization stage along the vein system, is marked by wire silver and concurrent leaching of earlier sulfides and sulfosalts; this stage may reflect the transition to a supergene environment.The sequence of mineralization stages identified in this study along the Bulldog Mountain system can be correlated with corresponding stages identified by other researchers along the OH and P veins, and the southern Amethyst vein system. Mineral zoning patterns identified along the Bulldog Mountain vein system also parallel larger scale zoning patterns across the central and southern Creede district.The complex variations in mineral assemblages documented in time and space along the Bulldog Mountain vein system were produced by the combined effects of many processes. Large-scale changes in vein mineralogy over time produced discrete mineralization stages. Short-term mineralogical fluctuations produced complex interbanding of mineralogically distinct generations. Fluid chemistry evolution within the vein system produced large-scale lateral zoning patterns within certain stages. Hypogene leaching substantially modified the distributions of some minerals. Finally, structural activity, mineral deposition, and mineral leaching modified fluid flow pathways repeatedly during mineralization, and so added to the complex mineral distribution patterns within the vein system.
Relationship between the Porco, Bolivia, Ag-Zn-Pb-Sn deposit and the Porco Caldera
Cunningham, C.G.
1994-01-01
The Porco Ag-Zn-Pb-Sn deposit, a major Ag producer in the 16th century and currently the major Zn producer in Bolivia, consists of a swarm of fissure-filling veins in the newly recognized Porco caldera. The caldera measures 5 km by 3 km and formed in response to the eruption of the 12 Ma crystal-rich dacitic Porco Tuff. The mineralization is associated with, and is probably genetically related to, the 8.6 Ma Huayna Porco stock. The Porco deposit consists of steeply dipping irregular and curvilinear veins that cut the intracaldera Porco Tuff about 1 km east of the Huayna Porco stock. Most of the veins are aligned along the structural margin (ring fracture) of the caldera. The ore deposit is zoned around the Huayna Porco stock. The primary Ag minerals are most abundant in the upper parts of the viens. Fluid inclusions in sphalerite stalactites have homogenization temperatures of about 225??C and salinities of about 8 wt% NaCl equiv. The stalactites and the presence of sparse vapor-rich inclusions suggest deposition of sphalerite under boiling conditions. -from Authors
Howe, S.S.
1985-01-01
The Devonian massive sulfide orebodies of the West Shasta district in N California are composed primarily of pyrite, with lesser amounts of other sulfide and gangue minerals. Examination of polished thin sections of more than 100 samples from the Mammoth, Shasta King, Early Bird, Balaklala, Keystone, and Iron Mountain mines suggests that mineralization may be divided into 6 paragenetic stages, the last 5 each separated by an episode of deformation: 1) precipitation of fine-grained, locally colloform and framboidal pyrite and sphalerite; 2) deposition of fine-grained arsenopyrite and coarse-grained pyrite; 3) penetration and local replacement of sulfide minerals of stages 1 and 2 along growth zones and fractures by chalcopyrite, sphalerite, galena, tennantite, pyrrhotite, bornite, and idaite; 4) recrystallization and remobilization of existing minerals; 5) deposition of quartz, white mica, chlorite, and calcite; and 6) formation of bornite, digenite, chalcocite, and covellite during supergene enrichment of several orebodies at the Iron Mountain mine. Mineralogic and textural evidence do not support a second major episode of massive sulfide mineralization during the Permian. -from Author
Zn mobility and geochemistry in surface sulfide mining soils from SE Spain.
Garcia, G; Peñas, J M; Manteca, J I
2008-03-01
The extraction of metallic minerals and the mineral dressing operations in concentrators produced a high impact in soils and sediments. Heavy metals in soils constitute a high risk of pollution, not only for mining areas, but also for agriculture and villages placed in subsidiary areas. This research has been focused on the assessment of the real environmental and health hazards of Zn in relation to geochemistry and metal mobility in surface soils from a mining area in SE Spain, under semiarid weather conditions. Mineralogy of the studied soils revealed major presence of quartz, but also of other silicates, sulfates, carbonates, and sulfides. Regarding Zn minerals, the presence of sphalerite as the main Zn sulfide, and of goslarite as Zn sulfate, and of smithsonite as Zn carbonate should be highlighted. Soil pH ranged between 4.4 and 4.9 and the electrical conductivity between 55 and 85 microS/cm. By using the sequential extraction procedure, the achieved results show that zinc is not only mainly associated to primary but also to secondary sulfides. Total concentration of the non-available fractions rises up to 98.45% of total Zn in the studied soils. On the other hand, available Zn fraction did not exceed more than 1.55% in percentage and less than 2000 ppm in absolute terms, and when referred to more easily available fraction (water-soluble and exchangeable fractions), these values are not more than 0.44% and then 800 ppm. Therefore, although there is a significant pollution level in this area, immediate hazard for the environment can be assessed as moderate. Finally it should be highlighted that these surface soils have undergone concentration processes of sphalerite, whose mechanisms should be related to the ascending flow of capillary water and the dragging of sphalerite crystals and Zn salts by electrokinetic and colloidal processes These processes seem to occur based on environmental pollution by wind and water erosion, and therefore directly associated to environmental pollution and risks by free metals.
Trace, Robert Denny
1962-01-01
The fault systems of the Levias-Keystone and Dike-Eaton areas, in the Kentucky-Illinois fiuorspar district, are a complex northeastward-trending sys- tem and a simple northwestward-trending system of steeply dipping normal faults, associated in part with a lamprophyre dike. Fluorspar mining started in the area about 1900 and, as of 1945, more than 200,000 tons of crude ore probably has been mined; most of the ore was from the Levias-Keystone area. A small quantity of zinc and lead ore also is present in the Dike-Eaton area. The deposits are localized along faults that displace fiat-lying or low-dipping limestones, sandstones, and shales of the Meramec and Chester series of Missis- sippian age. Movement along most of the faults was principally vertical, with displacement as much as 600 feet. Some horizontal movement occurred along at least one fault. Geologic mapping of the surface and data from underground workings have revealed 13 faults in an area of four-fifths of a square mile. Only a few of these faults are known to contain economically important deposits of fiuorspar. The most abundant vein minerals are calcite and fiuorite with subordinate quantities of sphalerite, galena, barite, and quartz. Some weathering products of sphalerite and galena are present also. The veins are dominantly calcite that contains fiuorite lenses but in places are mainly fiuorite having lesser quantities of calcite. Sphalerite- and galena-bearing deposits are present in the Dike-Eaton area. The ore bodies mainly are the result of fissure filling and replacement of calcite by fiuorite; in addition a small amount of limestone wallrock probably has been replaced. Residual concentrations of high-grade fluorspar in the overburden above faults have yielded some so-called gravel fiuorspar. The position of the veins within the faults may be related to one or more factors such as type of wallrock, change in dip of the fault, and amount of displacement.
Pfaff, Katharina; Hildebrandt, Ludwig H.; Leach, David L.; Jacob, Dorrit E.; Markl, Gregor
2010-01-01
The Mississippi Valley-type (MVT) Zn-Pb-Ag deposit in the Wiesloch area, Southwest Germany, is controlled by graben-related faults of the Upper Rhinegraben. Mineralization occurs as vein fillings and irregular replacement ore bodies consisting of sphalerite, banded sphalerite, galena, pyrite, sulfosalts (jordanite and geocronite), barite, and calcite in the Middle Triassic carbonate host rock. Combining paragenetic information, fluid inclusion investigations, stable isotope and mineral chemistry with thermodynamic modeling, we have derived a model for the formation of the Wiesloch deposit. This model involves fluid mixing between ascending hot brines (originating in the crystalline basement) with sedimentary formation waters. The ascending brines originally had a near-neutral pH (around 6) and intermediate oxidation state, reflecting equilibrium with granites and gneisses in the basement. During fluid ascent and cooling, the pH of the brine shifted towards more acidic (around 4) and the oxidation state increased to conditions above the hematite-magnetite buffer. These chemical characteristics contrast strongly with those of the pore and fracture fluid residing in the limestone aquifer, which had a pH between 8 and 9 in equilibrium with calcite and was rather reduced due to the presence of organic matter in the limestone. Mixing between these two fluids resulted in a strong decrease in the solubility of silver-bearing sphalerite and galena, and calcite. Besides Wiesloch, several Pb-Zn deposits are known along the Upper Rhinegraben, including hydrothermal vein-type deposits like Badenweiler and the Michael mine near Lahr. They all share the same fluid origin and formation process and only differ in details of their host rock and fluid cooling paths. The mechanism of fluid mixing also seems to be responsible for the formation of other MVT deposits in Europe (e.g., Reocin, Northern Spain; Treves, Southern France; and Cracow-Silesia, Poland), which show notable similarities in terms of their age, mineralogy, and mineral chemistry to the MVT deposit near Wiesloch.
Campbell, W.R.; Barton, P.B.
2005-01-01
The rate at which ore deposits form is one of the least well established parameters in all of economic geology. However, increased detail in sampling, improved technology of dating, and sophistication in modeling are reducing the uncertainties and establishing that ore formation, at least for the porphyry copper-skarn-epithermal base and precious metals deposit package, may take place in surprisingly brief intervals. This contribution applies another approach to examine the duration of mineralization. The degree to which compositional gradients within single crystals has flattened through solid-state diffusion offers a measure of the thermal dose (that is temperature combined with time) that the crystals have been subjected to since deposition. Here we examine the steepness of gradients in iron content within individual single sphalerite crystals from the epithermal silver-lead-zinc deposit in the OH vein at Creede, Colorado. Two initial textures are considered: growth-banded crystals and compositionally contrasting overgrowths that succeed crosscutting dissolution or fractured surfaces. The model used estimates the maximum possible time by assuming a perfectly sharp original compositional step, and it asks how long it would take at a known temperature for the gradient measured today to have formed. Applying the experimentally determined diffusion rates of Mizuta (1988a) to compositional gradients (ranging from 0.4-2.2 mol % FeS/??m) measured by the electron microprobe in 2-??m steps on banded sphalerite formed early in the paragenetic history yields a maximum duration of less than ???10,000 yr. Sphalerite from a solution unconformity in a position midway through the paragenetic sequence is indistinguishable from instantaneous deposition, supporting the conclusion of rapid ore formation. While this formation interval seems very brief, it is consistent with less well constrained estimates using entirely different criteria. ?? 2005 Society of Economic Geologists, Inc.
NASA Astrophysics Data System (ADS)
Akaryali, Enver; Akbulut, Kübra
2016-03-01
The Eastern Pontide Orogenic Belt (EPOB) constitutes one of the best examples of the metallogenic provinces in on the Alpine-Himalayan belt. This study focuses on the genesis of the Ünlüpınar Pb-Zn ± Au deposit in the southern part of the Eastern Pontide Orogenic Belt. The main lithological units in the study area are the Early Carboniferous Kurtoğlu Metamorphic Complex the Late Carboniferous Köse Granitoid and the Early-Middle Jurassic Şenköy Formation. The studied deposit is hosted by the Şenköy Formation, which consists predominantly of basaltic-andesitic rocks and associated pyroclastic rocks that are calc-alkaline in composition. Silicic, sulfidic, argillic, chloritic, hematitic, carbonate and limonite are the most obvious alteration types observed in the deposit site. Ore microscopy studies exhibit that the mineral paragenesis in deposits includes pyrite, chalcopyrite, sphalerite, galena, gold, quartz and calcite. Electron microprobe analyses conducted on sphalerite indicate that the Zn/Cd ratio varies between 84 and 204, and these ratios point at a hydrothermal deposit related to granitic magmas. Fluid inclusion studies in calcite and quartz show that the homogenization temperature of the studied deposit ranges between 90-160 °C and 120-330 °C respectively. The values of sulfur isotope analysis of pyrite, sphalerite and galena minerals vary between 1.6‰ and 5.7‰, and the results of oxygen and carbon isotope analysis range between 8.4‰ and 18‰ and -5‰ and -3.6‰, respectively. The average formation temperature of the ore was calculated as 264 °C with a sulfur isotope geothermometer. All of the data indicate that the Ünlüpınar deposit is an epithermal vein-type mineralization that was formed depending on the granitic magmatism.
El Zrelli, Radhouan; Rabaoui, Lotfi; Daghbouj, Nabil; Abda, Heithem; Castet, Sylvie; Josse, Claudie; van Beek, Pieter; Souhaut, Marc; Michel, Sylvain; Bejaoui, Nejla; Courjault-Radé, Pierre
2018-05-01
Since the establishment of the coastal industrial complex in Gabes city (Gulf of Gabes, SE Tunisia), hundred million tons of untreated phosphogypsum have been discharged in the open sea causing serious environmental problems. To better understand the dynamic and behavior of phosphate/phosphogypsum contaminants from raw ores to marine environment, a chemical, organic, mineralogical, and morphological characterization of phosphate rock and phosphogypsum was conducted using several sophisticated techniques. The chemical analysis showed that phosphate and phosphogypsum contain high loads of trace elements and that the transfer factors of pollutants varied from 5.83% (U) to 140% (Hg). Estimated annual flows of phosphogypsum contaminants into the marine environment ranged between 0.05 (Re) and 87,249.60 (F) tons. The phosphate rock was found to be formed by carbonate fluorapatite, calcite, dolomite, natural gypsum, quartz, calcite-Mg, apatite, pyrite, fluorite, and sphalerite-Cd and phosphogypsum by synthetic gypsum and sphalerite-Cd. The phosphate was found to be richer in organic compounds compared to phosphogypsum. Based on this work, the Tunisian phosphogypsum has a high mining potential and encourages the development of an economically beneficial and environmentally friendly phosphogypsum-treating industry.
Genetic characteristics of fluid inclusions in sphalerite from the Silesian-Cracow ores, Poland
Kozlowski, A.; Leach, D.L.; Viets, J.G.
1996-01-01
Fluid inclusion studies in sphalerite from early-stage Zn-Pb mineralization in the Silesian-Cracow region (southern Poland), yielded homogenization temperatures (Th) from 80 to 158??C. Vertical thermal gradient of the parent fluids was 6 to 10??C, and the ore crystallization temperature ranges varied from <10??C at deep levels to 25??C at shallow levels. The peculiarities of formation of primary and secondary fluid inclusions from organic-matter-bearing water-dominated medium, position of the inclusions in crystals, features of secondary inclusions, the inclusion refilling phenomena, their formation on recrystallization of ores, and Th distribution in single fissure fillings were considered. The ore-forming fluids were liquid-hydrocarbon-bearing aqueous solutions of Na-Ca-Cl type with lower Ca contents in the south and higher Ca contents in the north of the region. The ore-forming fluids had salinities from nul to about 23 weight percent of NaCl equivalent. Three types of fluids were recognized, that mixed during ore precipitation: a) ascending fluids of low-to-moderate salinity and high, b) formation brines of high salinity and moderate Th, and c) descending waters of low salinity and low-to-moderate Th.
NASA Astrophysics Data System (ADS)
Ilboudo, Hermann; Lompo, Martin; Wenmenga, Urbain; Napon, Salif; Naba, Seta; Ngom, Papa Malick
2017-05-01
Twenty years after the discovery of the Perkoa Znsbnd Ag deposit, another type of Znsbnd Cusbnd Pb ± Ag Volcanogenic Massive Sulfide (VMS) subgroup of occurrences forming a district has been highlighted within the Paleoproterozoic Birimian Greenstone Belts of the West African Craton in Burkina Faso. The geology of the area is characterized by a series of dominantly mafic volcanic rocks with intercalated black shales which increase in proportion upwards in the stratigraphy. This stratigraphic package is overlain by a felsic volcanic sequence comprising reworked tuff and rhyolite. Although mineralization is locally associated with sedimentary rocks, it is more commonly found in rhyolites. The metamorphic grade is dominantly greenschist facies. The main lithologies in the mafic sequence range from basalt to andesite with associated gabbro. The felsic sequence consists of dacite to rhyolite with associated granitoids (granite-granodiorite-tonalite). The volcanic rocks are commonly tholeiitic (Zr/Y = 2-4.5) with relatively high Zr and Y content, although a limited number of samples plot in transitional (Zr/Y = 4.5-7) or calc-alkaline (Zr/Y = 7-25) fields. Rhyolites, which constitute the main mineralized rocks at Tiébélé, have similar key trace element signatures to other rhyolites-related known VMS systems worldwide. Both have low Zr/Y (<7) and low LaN/YbN (<6), which suggests low crustal residence times of magmas in extensional settings. Detailed investigations identified at least four VMS targets notably at Koubongo, Nabenia, Loubel and AVV (Aménagement de la Vallée des Voltas) extending over an area of 332 km2. Typical mineral assemblages defining VMS occurrences are mainly hosted by meta-sedimentary rocks and rhyolite but are also found as veins in tonalite. These assemblages can be grouped into four different styles: (i) Variably banded massive sulfides dominated by sphalerite over galena, pyrite, and chalcopyrite within metasediments; (ii) Pyrite-rich or pyrrhotite banded type associated with sphalerite, chalcopyrite, and galena within silicified and carbonatized units; (iii) Disseminated and finely oriented sulfides, including pyrite - pyrrhotite - magnetite ± sphalerite within quartz-phyric rhyolite; and (iv) Fracture filling pyrrhotite-rich - magnetite - sphalerite mineralization possibly within tonalite. Irrespective of the style of the mineralization, chemistry of altered and least altered rhyolite reveals a significant increase in Mg ± Fe and H2O, and a loss of K within mineralization associated alteration. This may suggest sea water leaching of underlying (?) mafic and sedimentary rocks, with Mgsbnd Fe transfer into the rhyolites concomitant with the loss of K. This paper highlights the features of new occurrences of VMS mineralization type within the Birimian system of West Africa. We think this could help for new discoveries along the belts. Exploration based upon ground mapping, geochemistry and geophysics is highly recommended.
NASA Astrophysics Data System (ADS)
Maulana, Adi; Jaya, Asri; Imai, Akira
2018-02-01
Uluwai Prospect is located in the northern part of South Arm of Sulawesi along the eastern part of the Kalosi Fold Belt and Latimojong Mountain. The area is generally characterized by moderate to rugged topography area with elevation in the range of 700 to 1400 m above sea level in the mountainous complex called Latimojong Mountain Complex. The mineralization is characterized by a relatively simple sulphide ore mineral assemblage consists of pyrite, sphalerite and chalcopyrite. Samples were collected in areas showing abundant sulphide minerals where younger faults cut the bedding and foliation of country rocks. A number of silicified zones have been observed, as well as float material containing disseminated pyrite, chalcopyrite, and sphalerite with hematite, goethite and limonite. Some alteration types have been observed including sericitization, albitization, carbonatization and silisification. The samples collected indicated that the mineralisation is contained within metasedimentary (sandstone to mudstone) and greenschist. Geochemical analyses from 16 samples including 5 stream sediment samples indicated that the most promising mineralization occur in the prospect area are copper (Cu) and zinc (Zn). This is also supported by the abundance of chalcopyrite and sphalerite in some highly altered samples. Assaying of the collected samples revealed most of samples contain relatively low gold (Au) concentration. However, two samples contain 0.007 and 0.01 ppm of Au. In the mineralized area, Zn concentrations are up to 134 ppm, Cu up to 120 ppm and Pb up to 18 ppm and As up to 70 ppm. There is no clear relationship that exists between Au and the base metals except that one of the samples with highest Au values tend to have high Zn and As. This unclear pattern also shown by Cu, Pb and Zn. Base metal concentration in stream sediment samples show a relatively stable pattern than in rock samples. Arsenic tends to be elevated in base metal rich samples. Sb and Mo are relatively low in all sample type. However, Mo values will be high in the samples which contain highest Cu and Zn.
NASA Astrophysics Data System (ADS)
Çelebi, E. Ender; Öncel, M. Salim
2016-12-01
Weathering of sulfide minerals is a major source of acid production in nature and especially in mining territories. Pyrite is not the only principal mineral that generates acid drainage: other sulfide minerals (sphalerite, galena, chalcopyrite, etc.) may also be responsible for acid production. In addition to massive sulfide minerals, sulfide-bearing mine tailings may also produce acid drainage due to oxidation and hydrolysis reactions in waste dumps. The lead/zinc (Pb/Zn) mining region in Balya and Balıkesir, in Turkey, has operated mines intensively since the 1860s; so that characterization of the sulfide minerals and tailings situated and formed around the mining site is of great importance to secure a sustainable environment. For this purpose, acid production and neutralization potentials of massive sulfide ores of the region, and in the Pb/Zn process facility mine tailings from ten different points of tailings dam, have been determined by applied conventional Acid-Base Accounting (ABA) and Net Acid Generation (NAG) static tests after chemical and mineralogical analysis. The NAG pH and net acid production potential (NAPP) values were compared on a chart in order to classify the samples as either acid generating or non-acid generating. According to the comparisons, the sulfide minerals were classified as potentially acid forming (PAF). Massive pyrite had the highest NAPP and NAG pH value of 1966.6 kg H2SO4/ton and 1.91, respectively and the galena had the lowest NAPP value of 558.9 kg H2SO4/ton. However, the sphalerite NAG leachate pH value of 4.30 was the highest in sulfide minerals so that the sphalerite plotted near the uncertainty reference border in the PAF zone. In the mine tailings, NAPP values of 105.9 kg H2SO4/ton on average and the NAG pH values of over 7.5 were determined. In addition to these tests, water leaching (agitation test) was carried out on tailings in order to generate more information. The tailings did not generate acidic leachates as they lie on limestone bed rock which neutralized the acidity.
Kelley, K.D.; Hudson, T.
2007-01-01
Zinc-lead-silver mineral deposits in the Wulik River region, Alaska, contain an enormous accumulation of Zn. In addition to the giant deposits at Red Dog, at least nine other deposits are known. Natural weathering of these deposits has dispersed metals over a wide region over a long period of time (c. 10 000 years) through transport by stream and groundwater, stream sediments, formation of soils, and perhaps wind-blown atmospheric deposition from weathering of naturally enriched Pb-Zn surface deposits. Anthropogenic input also contributes metals to the environment. Mining of the Red Dog deposit, which began in 1989, produces fine-grained galena and sphalerite concentrates that are transported from the mine site by truck to a storage port facility. Wind-blown dispersion of concentrate dust along the road and around the port facility has been a source of local metal-rich surficial materials. Geochemical and mineralogical characteristics provide a means of distinguishing the natural versus anthropogenic metal sources. Soils over deposits have patterns of increasing metal contents with depth and proximity to the metal-bearing source, whereas ore concentrate dust is localized at the surface. The acidity produced by weathering of the sulphide deposits creates an environment in which elements such as Se and Mo are stable whereas Ca is not. Consequently, high Mo (up to 29 ppm) and Se (up to 17 ppm) and low Ca (<0.4%) concentrations characterize surficial materials near natural deposits. Acidic conditions also yield high Pb-Zn ratios (up to 70) because sphalerite is preferentially dissolved and Zn is mobilized during chemical weathering. In natural materials, secondary jarosite and anglesite are developed, and minor galena is etched and rounded due to a history of chemical and mechanical weathering. In contrast, dust-bearing samples have Pb/Zn ratios that are 0.4 or less, Ca contents are higher (0.2 to 3.6%), and Mo (<10 ppm) and Se (not detected) concentrations are low. Furthermore, galena and sphalerite grains are angular and secondary minerals are lacking. ?? 2007 AAG/Geological Society of London.
Mineral resource of the month: zinc
Tolcin, Amy C.
2009-01-01
The article provides information on zinc, the fourth most-widely consumed metal. It traces the first use of zinc with the Romans' production of brass. It describes the presence of zinc in Earth's crust and the importance of sphalerite as a source of zinc and other some minor metal production. The production and consumption of zinc as well as the commercial and industrial uses of this metal are also discussed.
Re-Os sulfide geochronology of the Red Dog sediment-hosted Zn-Pb-Ag deposit, Brooks Range, Alaska
Morelli, R.M.; Creaser, R.A.; Selby, D.; Kelley, K.D.; Leach, D.L.; King, A.R.
2004-01-01
The Red Dog sediment-hosted deposit in the De Long Mountains of northern Alaska is the largest Zn producer in the world. Main stage mineralization is characterized by massive sulfide ore and crosscutting subvertical veins. Although the vein mineralization is clearly younger than the massive ore, the exact temporal relationship between the two is unclear. Re-Os geochronology of pyrite is used to determine the absolute age of main stage ore at Red Dog. A 10-point isochron on both massive and vein pyrite yields an age of 338.3 ?? 5.8 Ma and is interpreted to represent the age of main stage ore. The Re-Os data indicate that both massive and vein ore types are coeval within the resolution of the technique. Formation of the Red Dog deposit was associated with extension along a passive continental margin, and therefore the Re-Os age of main stage ore constrains the timing of rifting as well as the age of the host sedimentary rocks. Sphalerite from both massive and vein ore yields imprecise ages and shows a high degree of scatter compared to pyrite. We suggest that the Re-Os systematics of sphalerite can be disturbed and that this mineral is not reliable for Re-Os geochronology. ?? 2004 by Economic Geology.
NASA Astrophysics Data System (ADS)
Seccombe, P. K.
1990-10-01
Fluid inclusion and sulphur isotope data for the discordant, metasediment-hosted massive sulphide deposit at Elura are consistent with a syntectonic origin of the orebodies. Thermometric and laser Raman microprobe analyses indicate that two-phase, primary fluid inclusions are low salinity and H2O-CO2-CH4 types. Inclusion fluids from quartz in ore yield homogenisation temperatures (Th) ranging from 298 ° to 354 °C (mean 320 °C). They are likely to have been trapped close to the solvus of the H2O-CO2-(CH4-NaCl) system and thus should give temperatures of the mineralising fluid. An additional, low Th population of later fluid inclusions is recognised in quartz from ore and syntectonic extension veins in the adjacent wallrock. Th's for these low CO2bearing inclusions range from 150 to 231 °C (mean 190 °C), and should be considerably lower than true trapping temperatures. Sulphur isotopic composition (δ34S) of pyrite, sphalerite, pyrrhotite and galena ranges from 4.7 to 12.6% and indicates a sulphur source from underlying Cobar Supergroup metasediments. An average temperature of 275 °C from the sphalerite-galena sulphur isotopic thermometer suggests isotopic re-equilibration below peak metamorphic temperatures.
Viets, J.G.; Hofstra, A.H.; Emsbo, P.; Kozlowski, A.
1996-01-01
The composition of fluids extracted from ore and gangue sulfide minerals that span most of the paragenesis of the Silesian-Cracow district was determined using a newly developed ion chromatographic (IC) technique. Ionic species determined were Na+, NH+4, Ca2+, Mg2+, K+, Rb+, Sr2+, Ba2+, Cl-, Br-, F-, I-, PO3-4, CO2-3, HS-, S2O2-3, SO2-4, NO-3, and acetate. Mineral samples included six from the Pomorzany mine and one from the Trzebionka mine which are hosted in the Triassic Muschelkalk Formation, and two samples of drill core from mineralized Upper Devonian strata. Nine paragenetically identifiable sulfide minerals occur throughout the Silesian-Cracow district. These include from earliest to latest: early iron sulfides, granular sphalerite, early galena, light-banded sphalerite, galena, dark-banded sphalerite, iron sulfides, late dark-banded sphalerite with late galena, and late iron sulfides. Seven of the minerals were sampled for fluid inclusion analysis in this study. Only the early iron sulfides and the last galena stage were not sampled. Although the number of analyses are limited to nine samples and two replicates and there is uncertainty about the characteristics of the fluid inclusions analyzed, the data show clear temporal trends in the composition of the fluids that deposited these minerals. Fluid inclusions in minerals deposited later in the paragenesis have significantly more K+, Br-, NH+4, and acetate but less Sr2+ than those deposited earlier in the paragenesis. The later minerals are also characterized by isotopically lighter sulfur and significantly more Tl and As in the solid minerals. The change in ore-fluid chemistry is interpreted to reflect a major change in the hydrologic regime of the district. Apparently, the migrational paths of ore fluids from the Upper Silesian basin changed during ore deposition and the fluids which deposited early minerals reacted with aquifers with very different geochemical characteristics than those that deposited late minerals. The early fluids may have reacted primarily with Devonian and Lower Carboniferous carbonate aquifers deeper in the basin, whereas the later fluids appear to have had extensive contact with organic-rich rocks, probably the shallower Middle and Upper Carboniferous flysch associated with coal measures. High concentrations of toxic Tl and As occur in the readily oxidized marcasite and pyrite minerals deposited by the later fluids. In general, the geochemistry of both the early and late fluids may be explained by an evaporite related origin or by water-rock modification of a saline basinal brine. When compared to the composition of fluid inclusions in Mississippi Valley-type (MVT) ore minerals from the Ozark region of the United States, fluid inclusions in minerals from Silesian-Cracow are fundamentally different, containing more Ca2+, Mg2+, NH+4, Br-, Sr2+ and acetate in all mineral stages with significantly more K+ in later stage minerals. The differences in ore fluid chemistry between the two regions are consistent with the lithologic differences of the respective basins thought to be the source of the mineralizing brines.
JPRS Report, Science & Technology, USSR: Materials Science
1988-07-11
MATERIALY, No 2, Mar-Apr 88) , 19 Formation of Multilayer Polytypes Based on Diamond or Sphaleritic Boron Nitride Under High Pressures at High...in Compact Modifications of Boron Nitride (V. B, Shipilo, et al,; SVERKHTVERDYYE MATERIALY, No 2, Mar-Apr 88) 20 Change in Electrical...25CrMnNiMoTi alloy steel were first refined by heat treatment and then, covered with a heat-absorbent MnP04 coating , treated with a laser beam
Skierszkan, E K; Mayer, K U; Weis, D; Beckie, R D
2016-04-15
The stable isotope composition of molybdenum (Mo) and zinc (Zn) in mine wastes at the Antamina Copper-Zn-Mo mine, Peru, was characterized to investigate whether isotopic variation of these elements indicated metal attenuation processes in mine drainage. Waste rock and ore minerals were analyzed to identify the isotopic composition of Mo and Zn sources, namely molybdenites (MoS2) and sphalerites (ZnS). Molybdenum and Zn stable isotope ratios are reported relative to the NIST-SRM-3134 and PCIGR-1 Zn standards, respectively. δ(98)Mo among molybdenites ranged from -0.6 to +0.6‰ (n=9) while sphalerites showed no δ(66)Zn variations (0.11±0.01‰, 2 SD, n=5). Mine drainage samples from field waste rock weathering experiments were also analyzed to examine the extent of isotopic variability in the dissolved phase. Variations spanned 2.2‰ in δ(98)Mo (-0.1 to +2.1‰) and 0.7‰ in δ(66)Zn (-0.4 to +0.3‰) in mine drainage over a wide pH range (pH2.2-8.6). Lighter δ(66)Zn signatures were observed in alkaline pH conditions, which was consistent with Zn adsorption and/or hydrozincite (Zn5(OH)6(CO3)2) formation. However, in acidic mine drainage Zn isotopic compositions reflected the value of sphalerites. In addition, molybdenum isotope compositions in mine drainage were shifted towards heavier values (0.89±1.25‰, 2 SD, n=16), with some overlap, in comparison to molybdenites and waste rock (0.13±0.82‰, 2 SD, n=9). The cause of heavy Mo isotopic signatures in mine drainage was more difficult to resolve due to isotopic heterogeneity among ore minerals and a variety of possible overlapping processes including dissolution, adsorption and secondary mineral precipitation. This study shows that variation in metal isotope ratios are promising indicators of metal attenuation. Future characterization of isotopic fractionation associated to key environmental reactions will improve the power of Mo and Zn isotope ratios to track the fate of these elements in mine drainage. Copyright © 2015 Elsevier B.V. All rights reserved.
Kelley, K.D.; Kelley, D.L.
2003-01-01
The Lik deposit in northern Alaska is a largely unexposed shale-hosted Zn-Pb-Ag massive sulphide deposit that is underlain by continuous permafrost. Residual soils overlying the mineralized zone have element enrichments that are two to six times greater than baseline values. The most prominent elements are Ag, Mo, P, Se, Sr, V by total 4-acid digestion and Tl by a weak partial digestion (Enzyme Leach or EL) because they show multi-point anomalies that extend across the entire mineralized zone, concentration ranges are 0.5-2.6 ppm Ag, 4-26 ppm Mo, 0.1-0.3% P, 3-22 ppm Se, 90-230 ppm Sr, 170-406 ppm V, and 1.6-30 ppb Tl. Lead, Sb, and Hg are also anomalous (up to 178 ppm, 30 ppm, and 1.9 ppm, respectively), but all are characterized by single point anomalies directly over the mineralized zone, with only slightly elevated concentrations over the lower mineralized section. Zinc (total) has a consistent baseline response of 200 ppm, but it is not elevated in soils overlying the mineralized zone. However, Zn by EL shows a distinct single-point anomaly over the ore zone that suggests it was highly mobile and partly adsorbed on oxides or other secondary phases during weathering. In situ analyses (by laser ablation ICP-MS) of pyrite and sphalerite from drill core suggest that sphalerite is the primary residence for Ag, Cd, and Hg in addition to Zn, and pyrite contains As, Fe, Sb, and Tl. The level and degree of oxidation, and the proportion of reacting pyrite and carbonate minerals are two factors that affected the mobility and transport of metals. In oxidizing conditions, Zn is highly mobile relative to Hg and Ag, perhaps explaining the decoupling of Zn from the other sphalerite-hosted elements in the soils. Soils are acidic (to 3.9 pH) directly over the deposit due to the presence of acid-producing pyrite, but acid-neutralizing carbonate away from the mineralized zone yield soils that are near neutral. The soils therefore formed in a complex system involving oxidation and weathering (mechanical and chemical) of sulphide minerals, dissolution of carbonate minerals, and precipitation of iron and manganese oxide minerals.
NASA Astrophysics Data System (ADS)
Mishra, Biswajit; Bernhardt, Heinz-Jurgen
2009-02-01
Located adjacent to the Banded Gneissic Complex, Rampura-Agucha is the only sulfide ore deposit discovered to date within the Precambrian basement gneisses of Rajasthan. The massive Zn-(Pb) sulfide orebody occurs within graphite-biotite-sillimanite schist along with garnet-biotite-sillimanite gneiss, calc-silicate gneisses, amphibolites, and garnet-bearing leucosomes. Plagioclase-hornblende thermometry in amphibolites yielded a peak metamorphic temperature of 720-780°C, whereas temperatures obtained from Fe-Mg exchange between garnet and biotite (580-610°C) in the pelites correspond to postpeak resetting. Thermodynamic considerations of pertinent silicate equilibria, coupled with sphalerite geobarometry, furnished part of a clockwise P- T- t path with peak P- T of ˜6.2 kbar and 780°C, attained during granulite grade metamorphism of the major Zn-rich stratiform sedimentary exhalative deposits orebody and its host rocks. Arsenopyrite composition in the metamorphosed ore yielded a temperature [and log f( S 2)] range of 352°C (-8.2) to 490°C (-4.64), thus indicating its retrograde nature. Contrary to earlier research on the retrogressed nature of graphite, Raman spectroscopic studies on graphite in the metamorphosed ore reveal variable degree of preservation of prograde graphite crystals (490 ± 43°C with a maximum at 593°C). The main orebody is mineralogically simple (sphalerite, pyrite, pyrrhotite, arsenopyrite, galena), deformed and metamorphosed while the Pb-Ag-rich sulfosalt-bearing veins and pods that are irregularly distributed within the hanging wall calc-silicate gneisses show no evidence of deformation and metamorphism. The sulfosalt minerals identified include freibergite, boulangerite, pyrargyrite, stephanite, diaphorite, Mn-jamesonite, Cu-free meneghinite, and semseyite; the last three are reported from Agucha for the first time. Stability relations of Cu-free meneghinite and semseyite in the Pb-Ag-rich ores constrain temperatures at >550°C and <300°C, respectively. Features such as (1) low galena-sphalerite interfacial angles, (2) presence of multiphase sulfide-sulfosalt inclusions, (3) microcracks filled with galena (±pyrargyrite) without any hydrothermal alteration, and (4) high contents of Zn, Ag (and Sb) in galena, indicate partial melting in the PbS-Fe0.96S-ZnS-(1% Ag2S ± CuFeS2) system, which was critical for metamorphic remobilization of the Rampura-Agucha deposit.
Granitoid-associated gold mineralization in Egypt: a case study from the Atalla mine
NASA Astrophysics Data System (ADS)
Zoheir, Basem; Deshesh, Fatma; Broman, Curt; Pitcairn, Iain; El-Metwally, Ahmed; Mashaal, Shabaan
2018-06-01
Gold-bearing sulfide-quartz veins cutting mainly through the Atalla monzogranite intrusion in the Eastern Desert of Egypt are controlled by subparallel NE-trending brittle shear zones. These veins are associated with pervasive sericite-altered, silicified, and ferruginated rocks. The hosting shear zones are presumed as high-order structures of the Najd-style faults in the Central Eastern Desert ( 615-585 Ma). Ore minerals include an early pyrite-arsenopyrite (±pyrrhotite) mineralization, partly replaced by a late pyrite-galena-sphalerite-chalcopyrite (±gold/electrum ± tetrahedrite ± hessite) assemblage. Gold occurs as small inclusions in pyrite and arsenopyrite, or more commonly as intergrowths with galena and sphalerite/tetrahedrite in microfractures. Arsenopyrite geothermometry suggests formation of the early Fe-As-sulfide mineralization at 380-340 °C, while conditions of deposition of the late base metal-gold assemblage are assumed to be below 300 °C. Rare hessite, electrum, and Bi-galena are associated with sphalerite and gold in the late assemblage. The early and late sulfide minerals show consistently a narrow range of δ34S ‰ (3.4-6.5) that overlaps with sulfur isotopic values in ophiolitic rocks. The Au-quartz veins are characterized by abundant CO2 and H2O ± CO2 ± NaCl inclusions, where three-dimensional clusters of inclusions show variable aqueous/carbonic proportions and broad range of total (bimodal) homogenization temperatures. Heterogeneous entrapment of immiscible fluids is interpreted to be caused by unmixing of an originally homogenous, low salinity ( 2 eq. mass % NaCl) aqueous-carbonic fluid, during transition from lithostatic to hydrostatic conditions. Gold deposition occurred generally under mesothermal conditions, i.e., 1.3 kbar and 280 °C, and continued during system cooling to < 200 °C and pressure decrease to 0.1 kbar. Based on the vein textures, sulfur isotope values, composition of ore fluids, and conditions of ore formation, we suggest that the Atalla monzogranite intrusion acted only as a competent structural host for ore deposition from shear-related, metal-rich fluids migrated up from depth. This model is also presumed for most granitoid-associated Au deposits in the region, considering the similarity in their structural control, alteration pattern and mineralogy, and chemistry of the ore fluids.
Invisible and microscopic gold in pyrite: Methods and new data for massive sulfide ores of the Urals
NASA Astrophysics Data System (ADS)
Vikentyev, I. V.
2015-07-01
Au speciation in sulfides (including "invisible" Au), which mostly controls the loss of Au during ore dressing, is discussed. Modern methods of analysis of Au speciation, with discussion of limitations by locality and sensitivity, are reviewed. The results of sulfide investigation by the methods of scanning and transmission electron microscopy, mass spectrometric analysis with laser ablation (LA-ICP-MS), the thermochemical method (study of ionic Au speciation), and automated "quantitative mineralogy," are demonstrated for weakly metamorphosed VHMS deposits of the Urals (Galkinsk and Uchaly). Significant content of Au is scattered in sulfides, such as pyrite, chalcopyrite, and sphalerite, with quantitative predomination of pyrite. The portion of such "invisible" gold ranges from <10% (Galkinsk deposit) to 85% (Uchaly deposit). Major part of "invisible" gold occurs as micron- to nanoscale particles of Au minerals. The portion of gold structurally bound in pyrite lattice (from the bulk concentration of Au in pyrite) is estimated to be from few % (the Galkinsk deposit) to 20-25% (the Uchaly deposit). The presence of As and Sb in pyrite and sphalerite, as well as other trace elements (Te, Co, Mn, Cu, Hg, and Ag in both as well as Fe in sphalerite) stimulates the incorporation of Au in sulfide, but mostly in defect-associated, not isomorphic form. Micron particles of Ag sulfosalts (pyrargyrite, freibergite, stephanite, polybasite, pyrostilpnite, argentotetrahedrite, pearceite, proustite), Au-Ag alloys (from gold of high fineness to küstelite), Ag and Au-Ag tellurides (hessite, empressite, calaverite), and occasional Au-Ag sulfides (petrovskaite, uytenbogaardtite) were registered in the areas of Au enrichment of both deposits; selenotelluride (kurilite) particles were found on the Galkinsk deposit. Nanoscale (1-50 nm) native gold (spherical and disk-shaped particles, flakes) with a monocrystal diffraction pattern of some particles and a ring diffraction pattern of other particles was registered in the ores of these deposits by the methods of transmission electron microscopy. The low degree (or absence) of metamorphic recrystallization results in (1) predomination of thin intergrowths of sulfides, which is the main reason for the bad concentration of ores (especially for the Galkinsk deposit) and (2) the high portion of "invisible" gold in the massive sulfide ores, which explains the low yield of Au in copper and zinc concentrates, since it is lost in tailings with predominating pyrite.
Research support for cadmium telluride crystal growth
NASA Technical Reports Server (NTRS)
Rosenberger, Franz
1995-01-01
The growth of single crystals of zinc selenide was carried out by both closed ampoule physical vapor transport and effusive ampoule physical vapor transport (EAPVT). The latter technique was shown to be a much more efficient method for the seeded growth of zinc selenide, resulting in higher transport rates. Furthermore, EAPVT work on CdTe has shown that growth onto (n 11) seeds is advantageous for obtaining reduced twinning and defect densities in II-VI sphalerite materials.
Moore, Frank R.; Butler, C.R.
1952-01-01
Pitchblende has been mined in commercial quantities from four gold- and silver-bearing pyrite-sphalerite-galena veins that occur in an area about one-half mile square on the south side of Quartz Hill, Central City district, Gilpin County, Colo. These veins are the Kirk, the German-Belcher, the Wood, and the Calhoun. Two of these veins, the Wood and the Calhoun, were studied in an attempt to determine the geologic factors favorable for pitchblende deposition. All accessible workings at the Wood and East Calhoun mines were mapped by tape and compass, and the distribution of radioactivity was studied in the field. Channel and chip samples were taken for chemical assay to compare radioactivity with uranium content. The pitchblende-bearing veins cat both pre-Cambrian granite gneiss and quartz-biotite schist; however, the gneiss was the more favorable host rock. Two bostonite porphyry dikes of Tertiary(?) age were crosscut by the Wood and Calhoun veins. The pitchblende occurs in lenses erratically distributed along the veins and in stringers extending outward from the veins. In the lenses it forms hard'. masses, but elsewhere it is Soft and powdery. The pitchblende is contemporaneous with the pyrite bat earlier than the sphalerite and galena in the same vein. All the observed pitchblende was at depths of less than 400 ft. The veins probably cannot be mined profitably for the pitchblende alone under present conditions.
Peng, Xingxing; Ng, Tsz Wai; Huang, Guocheng; Wang, Wanjun; An, Taicheng; Wong, Po Keung
2017-01-01
A 5-L reactor was designed and used to enhance the sunlight/visible-light-driven (VLD) photocatalytic disinfection efficiency towards Gram-negative bacterium (Escherichia coli). Natural magnetic sphalerite (NMS) was used as the photocatalyst, which could be easily recycled by applying a magnetic field. Results showed that NMS with irradiation by the blue light emitting diode (LED) lamp could completely inactivate 1.5 × 10 5 cfu/mL of E. coli within 120 min in the first three runs. However, the inactivation efficiency of E. coli started to decrease in the 4th Run, while in the 5th run, the E. coli with the initial concentration of 5 logs was inactivated to 3.3 (blue-light) and 3.5 logs (sunlight), respectively. Moreover, the stability and deactivation mechanism of NMS during subsequent runs were also studied. The results showed that the decline of the photocatalytic activity was possibly attributed to adsorption of the bacterial decomposed compounds on the active sites. In addition, photocatalytic bactericidal mechanism of the NMS in the photocatalytic system was investigated by using multiple scavengers to remove the specific reactive species. Moreover, various Gram-positive bacteria including Staphylococcus aureus, Microbacterium barkeri, and Bacillus subtilis could also be efficiently inactivated in the photocatalytic system. Copyright © 2016 Elsevier Ltd. All rights reserved.
The Balmat-Edwards zinc-lead deposits-synsedimentary ore from Mississippi valley-type fluids.
Whelan, J.F.; Rye, R.O.; Delorraine, W.
1984-01-01
The Balmat-Edwards Zn-Pb district in New York is in Mid-Proterozoic Grenville marbles. Tabular to podiform, generally conformable massive sphalerite-galena orebodies occur at various horizons in the approx 1 km-thick marbles. Metamorphism obscured or obliterated most primary characteristics, whose reconstruction is attempted through detailed S, C, and O isotope studies of the Fowler orebody, and trace element and S isotope studies of sphalerite concentrates and composite ore samples from 22 orebodies. Sulphur isotope data reflect equilibration at near peak metamorphism with some indication of re-equilibration during retrograde metamorphism. The carbon and oxygen isotope composition of gangue carbonates suggests derivation from the host marbles. The oxygen isotope composition of gangue quartz is compatible with a chert origin or metamorphism-equilibration with other minerals. Sulphur and lead isotopes and sulphide mineralogy suggests that the ore fluids were evolved basin brines, chemically like those responsible for Mississippi Valley-type deposits. The large stratigraphic span (> 600 m) of the Balmat orebodies may be due to basin dewatering of million-year intervals. Stratigraphically increasing 34S values of evaporite-anhydrite are postulated to record hydrothermal events and to imply bacterial sulphate reduction on an unusually large scale. Such a stratigraphic increase may be a general exploration guide where sediment-hosted exhalative deposits or Mississippi Valley-type deposits occur.-G.J.N.
NASA Astrophysics Data System (ADS)
Hovakimyan, Samvel; Moritz, Robert; Tayan, Rodrik; Rezeau, Hervé
2016-04-01
The Lesser Caucasus belongs to the Central segment of the Tethyan metallogenic belt and it is a key area to understand the metallogenic evolution between the Western & Central parts of the Tethyan belt and its extension into Iran. Zangezur is the most important mineral district in the southernmost Lesser Caucasus. It is a component of the South Armenian block, and it was generated during the convergence and collision of the southern margin of the Eurasian plate and the northern margin of the Arabian plate, and terranes of Gondwana origin (Moritz et al., in press). The Zangezur ore district consists of the Tertiary Meghri-Ordubad composite pluton, which is characterized by a long-lasting Eocene to Pliocene magmatic, tectonic and metallogenic evolution. It hosts major porphyries Cu-Mo and epithermal Au - polymetallic deposits and occurrences, including the giant world class Kadjaran porphyry Cu-Mo deposit (2244 Mt reserves, 0.3% Cu, 0.05% Mo and 0.02 g/t Au). The Kadjaran deposit is hosted by a monzonite intrusion (31.83±0.02Ma; Moritz et al., in press). Detailed field studies of the porphyry stockwork and veins of the different mineralization stages, their crosscutting and displacement relationships and the age relationship between different paragenetic mineral associations were the criteria for distinction of the main stages of porphyry mineralization at the Kadjaran deposit. The economic stages being: quartz- molybdenite, quartz-molybdenite-chalcopyrite, and quartz-chalcopyrite. The main paragenetic association of the Kadjaran porphyry deposit includes pyrite, molybdenite, chalcopyrite, bornite, chalcocite, pyrrhotite, covellite, sphalerite, and galena. Recent field observations in the Kadjaran open pit revealed the presence of epithermal veins with late vuggy silica and advanced argillic alteration in the north-eastern and eastern parts of the deposit. They are distributed as separate veins and have also been recognized in re-opened porphyry veins and in stockwork. One of them is the east-west-oriented 6th vein zone in the northern part of the deposit, which contains quartz-molybdenite veins and late quartz-galena-sphalerite veins. This is interpreted as a telescoping between porphyry and epithermal environments. It is supported by microscopic studies of mineral paragenesis, which reveal the presence of enargite and tennantite-tetrahedrite, luzonite, sphalerite, and galena, generally in a gangue of quartz, followed by a late carbonate and gypsum stage. On-going fluid inclusion studies are being carried out on quartz samples from the different mineralization stages. Five types of fluid inclusions were distinguished according to their nature, bubble size, and daughter mineral content: vapor-rich, aqueous-carbonic, brine, polyphase brine and liquid-rich inclusions. Cathodoluminescence images from the porphyry veins reveal four generations of quartz. Molybdenite and chalcopyrite are associated with two different dark luminescent quartz generations, which contain typical brine, aqueous-carbonic and vapour-rich H2O fluid inclusions, with some of them coexisting locally as boiling assemblages. Epithermal veins are mainly characterized by liquid-rich H2O fluid inclusions. Microthermometric studies of fluid inclusions reveal a major difference in homogenisation temperatures between the early quartz-molybdenite- chalcopyrite stage (Thtotal between 3600 and 4250C) and the late quartz-galena-sphalerite vein stage (Thtotal 300-2700C), which is attributed to the transition from a porphyry to an epithermal environment in the Kadjaran deposit.
The geology, mineralogy and paragenesis of the Castrovirreyna lead-zinc-silver deposits, Peru
Lewis, Richard Wheatley
1964-01-01
The Castrovirreyna mining district lies in the Andean Cordillera of South Central Peru, and has been worked sporadically since its discovery in 1591. Supergene silver ores were first mined. Currently the district produces about 20,000 tons of lead-zinc ore and 5000 tons of silver ore annually. The district is underlain by Tertiary andesitic rocks interbedded with basalts and intruded by small bodies of quartz latite porphyry. The terrane reflects recent glaciation and is largely covered by glacial debris. The ore deposits are steeply dipping veins that strike N. 60? E. to S. 50? E., and average 60 centimeters wide and 300 meters long. The principal veins are grouped around three centers, lying 5 kilometers apart along a line striking N. 55? E. They are, from east to west: San Genaro, Caudalosa, and La Virreyna. A less important set of veins, similarly aligned, lies 2 kilometers to the north. Most of the veins were worked to depths of about 30 meters, the limit of supergene enrichment; but in the larger veins hypogene ores have been worked to depths of over 150 meters. Galena, sphalerite, chalcopyrite, and tetrahedrite are common to all veins, but are most abundant in the westernmost veins at La Virreyna. In the center of the district, around Caudalosa, land sulfantimonides are the commonest ore minerals, and at the eastern end, around San Genaro and Astohuaraca, silver sulfosalts predominate. Supergene enrichment of silver is found at shallow depths in all deposits. Silver at San Genaro, however, was concentrated towards the surface by migration along hypogene physico-chemical gradients in time and space, as vein material was reworked by mineralizing fluids. The pattern of wallrock alteration throughout the district grades from silicification and scricitization adjacent to the veins, through argillization and propylitization, to widespread chloritization farther away. Mineralization can be divided into three stages: 1) Preparatory stage, characterized by silicification and pyritization; 2) Depositional stage, characterized by the deposition of base-metal sulfides; and 3) Reworking stage, characterized by the formation of lead sulfantimonides from galena at Caudalosa, and the deposition of silver sulfide and sulfosalts at San Genaro. Maximum temperatures, indicated by the wurtzite-sphalerite, famatinite-energite and chalcopyrite-sphalerite assemblages, did not exceed 350? C. The low iron content of sphalerite suggests that most of the base-metal sulfides were deposited below 250? C. The colloidal habits of pyrite and quartz in the preparatory and reworking stages imply relatively low temperatures of deposition, probably between 50? C and 100? C. Mineralization was shallow and pressures ranged from 17 atmospheres in the silver deposits to over 45 atmospheres in the lead sulfantimonide deposits. Mineralization at Castrovirreyna represents an open chemical system in which mineralizing fluids constantly modified the depositional environment while they themselves underwent modification. The deposits formed under nonequilibrium conditions from fluids containing complex ions and colloids. Reworking and migration along persistent physico-chemical gradients in time and space, from a deep source to the west concentrated base-metal sulfides in the western half, lead-antimony minerals in the center, and silver-antimony minerals in the eastern part of the district. Silver, antimony, and bismuth were kept in solution as complex ions until low temperature and pressure prevailed. They document in situ reworking by reacting with existing minerals. Physico-chemical gradients controlled the type of minerals deposited, whereas vein structure controlled the quantity deposited. Vein fissures formed by the equivalent of from east-west compression during Andean orogenesis and mineralization probably came from the underlying Andean Batholith.
Growth of zinc selenide crystals by physical vapor transport in microgravity
NASA Technical Reports Server (NTRS)
Rosenberger, Franz
1995-01-01
The growth of single crystals of zinc selenide was carried out by both closed ampoule physical vapor transport and effusive ampoule physical vapor transport (EAPVT). The latter technique was shown to be a much more efficient method for the seeded growth of zinc selenide, resulting in higher transport rates. Furthermore, EAPVT work on CdTe has shown that growth onto /n11/ seeds is advantageous for obtaining reduced twinning and defect densities in II-VI sphalerite materials.
Observation of > 5 wt % zinc at the Kimberley outcrop, Gale crater, Mars
Lasue, J.; Clegg, Samuel M.; Forni, O.; ...
2016-03-12
Zinc-enriched targets have been detected at the Kimberley formation, Gale crater, Mars, using the Chemistry Camera (ChemCam) instrument. The Zn content is analyzed with a univariate calibration based on the 481.2 nm emission line. The limit of quantification for ZnO is 3 wt % (at 95% confidence level) and 1 wt % (at 68% confidence level). The limit of detection is shown to be around 0.5 wt %. As of sol 950, 12 targets on Mars present high ZnO content ranging from 1.0 wt % to 8.4 wt % (Yarrada, sol 628). Those Zn-enriched targets are almost entirely located atmore » the Dillinger member of the Kimberley formation, where high Mn and alkali contents were also detected, probably in different phases. Zn enrichment does not depend on the textures of the rocks (coarse-grained sandstones, pebbly conglomerates, and resistant fins). The lack of sulfur enhancement suggests that Zn is not present in the sphalerite phase. Zn appears somewhat correlated with Na 2O and the ChemCam hydration index, suggesting that it could be in an amorphous clay phase (such as sauconite). On Earth, such an enrichment would be consistent with a supergene alteration of a sphalerite gossan cap in a primary siliciclastic bedrock or a possible hypogene nonsulfide zinc deposition where Zn, Fe, Mn would have been transported in a reduced sulfur-poor fluid and precipitated rapidly in the form of oxides.« less
Observation of > 5 wt % zinc at the Kimberley outcrop, Gale crater, Mars
NASA Astrophysics Data System (ADS)
Lasue, J.; Clegg, S. M.; Forni, O.; Cousin, A.; Wiens, R. C.; Lanza, N.; Mangold, N.; Le Deit, L.; Gasnault, O.; Maurice, S.; Berger, J. A.; Stack, K.; Blaney, D.; Fabre, C.; Goetz, W.; Johnson, J.; Le Mouélic, S.; Nachon, M.; Payré, V.; Rapin, W.; Sumner, D. Y.
2016-03-01
Zinc-enriched targets have been detected at the Kimberley formation, Gale crater, Mars, using the Chemistry Camera (ChemCam) instrument. The Zn content is analyzed with a univariate calibration based on the 481.2 nm emission line. The limit of quantification for ZnO is 3 wt % (at 95% confidence level) and 1 wt % (at 68% confidence level). The limit of detection is shown to be around 0.5 wt %. As of sol 950, 12 targets on Mars present high ZnO content ranging from 1.0 wt % to 8.4 wt % (Yarrada, sol 628). Those Zn-enriched targets are almost entirely located at the Dillinger member of the Kimberley formation, where high Mn and alkali contents were also detected, probably in different phases. Zn enrichment does not depend on the textures of the rocks (coarse-grained sandstones, pebbly conglomerates, and resistant fins). The lack of sulfur enhancement suggests that Zn is not present in the sphalerite phase. Zn appears somewhat correlated with Na2O and the ChemCam hydration index, suggesting that it could be in an amorphous clay phase (such as sauconite). On Earth, such an enrichment would be consistent with a supergene alteration of a sphalerite gossan cap in a primary siliciclastic bedrock or a possible hypogene nonsulfide zinc deposition where Zn, Fe, Mn would have been transported in a reduced sulfur-poor fluid and precipitated rapidly in the form of oxides.
Observation of > 5 wt % zinc at the Kimberley outcrop, Gale crater, Mars
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lasue, J.; Clegg, Samuel M.; Forni, O.
Zinc-enriched targets have been detected at the Kimberley formation, Gale crater, Mars, using the Chemistry Camera (ChemCam) instrument. The Zn content is analyzed with a univariate calibration based on the 481.2 nm emission line. The limit of quantification for ZnO is 3 wt % (at 95% confidence level) and 1 wt % (at 68% confidence level). The limit of detection is shown to be around 0.5 wt %. As of sol 950, 12 targets on Mars present high ZnO content ranging from 1.0 wt % to 8.4 wt % (Yarrada, sol 628). Those Zn-enriched targets are almost entirely located atmore » the Dillinger member of the Kimberley formation, where high Mn and alkali contents were also detected, probably in different phases. Zn enrichment does not depend on the textures of the rocks (coarse-grained sandstones, pebbly conglomerates, and resistant fins). The lack of sulfur enhancement suggests that Zn is not present in the sphalerite phase. Zn appears somewhat correlated with Na 2O and the ChemCam hydration index, suggesting that it could be in an amorphous clay phase (such as sauconite). On Earth, such an enrichment would be consistent with a supergene alteration of a sphalerite gossan cap in a primary siliciclastic bedrock or a possible hypogene nonsulfide zinc deposition where Zn, Fe, Mn would have been transported in a reduced sulfur-poor fluid and precipitated rapidly in the form of oxides.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Serviss, C.R.; Grout, C.M.; Hagni, R.D.
1985-01-01
Ore microscopic examination of uncommon silver-rich ores from the Edwards mine has detected three silver minerals, native silver, freibergite, and argentite, that were previously unreported in the literature from the Balmat-Edwards district. The zinc-lead ore deposits of the Balmat-Edwards District in northern New York are composed of very coarse-grained massive sulfides, principally sphalerite, galena, and pyrite. The typical ores contain small amounts of silver in solid solution galena. Galena concentrates produced from those ores have contained an average of 15 ounces of silver per ton of 60% lead concentrates. In contrast to the typical ore a silver-rich pocket, that measuredmore » three feet by three feet on the vertical mine face and was the subject of this study, contained nearly 1% silver in a zinc ore. Ore microscopic study shows that this ore is especially characterized by abundant, relatively fine-grained chalcopyrite with anhedral pyrite inclusions. Fine-grained sphalerite, native silver, argentite, freibergite and arsenopyrite occur in association with the chalcopyrite and as fracture-fillings in gangue minerals. Geochemically anomalous amounts of tin, barium, chromium, and nickel also are present in the silver-rich pocket. The silver-rich pocket may mark the locus of an early feeder vent or alternatively it may record a hydrothermal event that was superimposed upon the event responsible for the metamorphic ore textures.« less
Metallogeny of The Sierra de Guanajuato Range, Central México
NASA Astrophysics Data System (ADS)
Pedro F., Z. D.
2004-12-01
The Sierra de Guanajuato Range (SGR), trending N315° at Central México, is an orographic feature extending over a distance of 80 km. SGR comprises three well defined lithostratigraphic units: (1) a cretaceous basement including an arc-derived terrane named Guanajuato Arc (GA) made of gabbro, diorite and basaltic pillowed lava, and volcano-sedimentary rocks belonging to Arperos fore-arc basin which are geochemically anomalous in Au (0.15 ppm), Ag (3 ppm), Cu (40 ppm), Pb (50 ppm) and Zn (15 ppm); (2) Early Tertiary intrusive rocks, e.g., Comanja Granite which is affected by the presence of tourmalinized (schörl) aplito-pegmatite dykes mineralized with rare earths elements, and (3) Eocene redbeds (1,500-2000 m) and Oligocene-Miocene volcanics cover. The metallogeny of the SGR shows a multiple origin in time and space: volcano-sedimentary, granitic and volcanic, being possible to define three metallogenic epochs: cretaceous, paleocene and oligocene. Cretaceous epoch includes: (a) volcanogenic massive sulphide deposits (VMS) of bimodal-siliclastic type belonging to León-Guanajuato district; wallrock of VMS is made of felsic-internediate volcanics and black argillite; at Los Gavilanes deposit paragenesis is next: chalcopyrite > sphalerite > galena, pyrite > pyrrhotite > marcasite; grade is as follows: Au: .02-.07 g/t; Ag: 157-18.5 g/t; Cu: 2.24-0.81%, Pb: 4.16-0.03%; Zn: 10.35-3.02 %; (b) lens-shaped stratiform bodies of massive pyrite (i. ex., San Ignacio prospect; ˜ 4,000 ton) of exhalative-sedimentary origin with chalcopyrite and sphalerite microveins. Paleocene epoch includes both quartz-cordierite-sanidine veins and replacement bodies of hydrothermal metamorphic filliation (W +Se-Bi, Pb, Zn, Cu), and pyrometasomatic bodies [Cu, Pb, Zn (Ag), W] which genetically are linked to Comanja Granite emplacement. The wallrock at El Maguey mine (35,000 ton; 0.6% WO3) is made of hornfel and the vein (1.8-3.2m width) has a banding structure made of : \\{quartz & K-feldspar\\}, \\{(schörl) & specular hematite\\} and epidote alternating bands; ore minerals are scheelite and tetradymite. Oligocene epoch includes quartz-calcite-adulaire epithermal veins (Ag-Au) of geothermal-volcanic filliation. At Guanajuato mining District; ore minerals are: Au, electrum, acanthite, aguilarite, naumannite, polybasite, proustite, fischesserite (?); chalcopyrite, sphalerite and galena. Ore grade at Las Torres mine are: Ag 300 g/t, Au 2 g/t. At El Cubo mine because of the presence of rhyolitic domes gold grade reaches 100 g/t. Since Early Cretaceous Epoch, metallogenic concepts of heritage and permanence are valid in SG ore deposits.
NASA Astrophysics Data System (ADS)
Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.
2016-08-01
The Bou Jaber Ba-F-Pb-Zn deposit is located at the edge of the Bou Jaber Triassic salt diapir in the Tunisia Salt Diapir Province. The ores are unconformity and fault-controlled and occur as subvertical column-shaped bodies developed in dissolution-collapse breccias and in cavities within the Late Aptian platform carbonate rocks, which are covered unconformably by impermeable shales and marls of the Fahdene Formation (Late Albian-Cenomanian age). The host rock is hydrothermally altered to ankerite proximal to and within the ore bodies. Quartz, as fine-grained bipyramidal crystals, formed during hydrothermal alteration of the host rocks. The ore mineral assemblage is composed of barite, fluorite, sphalerite, and galena in decreasing abundance. The ore zones outline distinct depositional events: sphalerite-galena, barite-ankerite, and fluorite. Fluid inclusions, commonly oil-rich, have distinct fluid salinities and homogenization temperatures for each of these events: sphalerite-galena (17 to 24 wt% NaCl eq., and Th from 112 to 136 °C); ankerite-barite (11 to 17 wt% NaCl eq., and Th from 100 to 130 °C); fluorite (19 to 21 wt% NaCl eq., Th from 140 to 165 °C). The mean temperature of the ore fluids decreased from sphalerite (125 °C) to barite (115 °C) and increased during fluorite deposition (152 °C); then decreased to ˜110 °C during late calcite precipitation. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of fluid inclusions in fluorite are metal rich (hundreds to thousands ppm Pb, Zn, Cu, Fe) but the inclusions in barite are deficient in Pb, Zn, Cu, Fe. Inclusions in fluorite have Cl/Br and Na/Br ratios of several thousand, consistent with dissolution of halite while the inclusions analysed in barite have values lower than seawater which are indicative of a Br-enriched brine derived from evaporation plus a component of halite dissolution. The salinity of the barite-hosted fluid inclusions is less than obtained simply by the evaporation of seawater to halite saturation and requires a dilution of more than two times by meteoric water. The higher K/Na values in fluid inclusions from barite suggest that the brines interacted with K-rich rocks in the basement or siliciclastic sediments in the basin. Carbonate gangue minerals (ankerite and calcite) have δ13C and δ18O values that are close to the carbonate host rock and indicate fluid equilibrium between carbonate host rocks and hydrothermal brines. The δ34S values for sphalerite and galena fall within a narrow range (1 to 10 ‰) with a bulk value of 7.5 ‰, indicating a homogeneous source of sulfur. The δ34S values of barite are also relatively homogeneous (22 ‰), with 6 ‰ higher than the δ34S of local and regional Triassic evaporites (15 ‰). The latter are believed to be the source of sulfate. Temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate via hydrocarbons produced probably from Late Cretaceous source rocks. The 87Sr/86Sr ratio in the Bou Jaber barite (0.709821 to 0.711408) together with the lead isotope values of Bou Jaber galena (206Pb/204Pb = 18.699 to 18.737; 207Pb/204Pb = 15.635 to 15.708 and 208Pb/204Pb = 38.321 to 38.947) show that metals were extracted from homogeneous crustal source(s). The tectonic setting of the Bou Jaber ore deposit, the carbonate nature of the host rocks, the epigenetic style of the mineralization and the mineral associations, together with sulfur and oxygen isotope data and fluid inclusion data show that the Bou Jaber lead-zinc mineralization has the major characteristics of a salt diapir-related Mississippi Valley-type (MVT) deposit with superimposed events of fluorite and of barite deposition. Field relations are consistent with mineral deposition during the Eocene-Miocene Alpine orogeny from multiple hydrothermal events: (1) Zn-Pb sulfides formed by mixing of two fluids: one fluid metal-rich but reduced sulfur-poor and a second fluid reduced sulfur-rich; (2) barite precipitation involved the influx of a meteoric water component that mixed with a barium-rich fluid; and (3) fluorite precipitated from a highly saline fluid with higher temperatures.
Infrared spectra of some sulfides and their analogs of binary composition in the long-wave region
NASA Technical Reports Server (NTRS)
Povarennykh, A. S.; Sidorenko, G. A.; Solntseva, L. S.; Solntsev, B. P.
1981-01-01
The far infrared spectra (500-60/cm) of some simple sulfides and their analogs were studied. In all, 22 minerals with different structure types were investigated, out of which 14 are sulfides (galena, alabandite, pyrrhotite, sphalerite, wurtzite, cinnabar, realgar, orpiment, getchelite antimonite, molybdenite, pyrite, marcasite and heazlewoodite) 6 arsenides (niccolite, domeykite, arsenopyrite, lollingite, rammelsbergite and skutterudite), one telluride (tetradymite) and native arsenic. The main bands of infrared absorption spectra of the minerals are compared with the relative strength of the interatomic bonds and their interpretation is given.
The zinc stable isotope signature of waste rock drainage in Arctic Canada
NASA Astrophysics Data System (ADS)
Matthies, Romy; Blowes, David
2014-05-01
Leachate emerging from a pilot-scale waste rock pile of the Diavik diamond mine, Northwest Territories, was monitored. The well-characterized waste rock consists of granite, pegmatitic granite and biotite schist with an average total sulfur and carbonate carbon concentration of 0.053 and 0.027 wt. %, respectively. During the field seasons of 2011 and 2012, the Zn stable isotope footprint was characterized alongside standard monitoring parameters. pH ranged between 4.3 and 6.8 and carbonate alkalinity was low or undetectable. Al and Fe concentrations averaged 6.78 mg L-1 and 175 µg L-1, respectively. The pH and metal mobility were governed by sulfide oxidation and sorption and co-precipitation onto iron and aluminium hydroxides. The main processes controlling zinc mobility in the range of 0.4 and 4.7 mg L-1 was the oxidative dissolution of sphalerite (ZnS) in the biotite schist and the attenuation of zinc onto secondary iron and aluminium hydroxides and desorption upon the pH declining below the pHpzc. The isotope ratios between -0.16 and +0.19 ‰ (δ66Zn, avg = +0.05 ‰, n = 43) are consistent with values reported from other sphalerite containing deposits. Zn isotope ratios and concentrations were largely uncorrelated suggesting that the processes affecting Zn mobility had little or no impact on the Zn isotope signature. Data indicate, that the Zn isotope ratios of the waste rock leachate may be used as a fingerprint to track anthropogenic, mine-derived Zn sources under varying environmental conditions.
NASA Astrophysics Data System (ADS)
Rogulina, L. I.; Moiseenko, V. G.; Odarichenko, E. G.; Voropayeva, E. N.
2018-03-01
The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag-Pb-Zn deposits of the region. It was pointed out that the δ34S modal values range from-1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ34S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.
Rye, Robert O.; Hall, W.E.; Cunningham, C.G.; Czamanske, G.K.; Afifi, A.M.; Stacey, J.S.
1983-01-01
The Mahd adh Dhahab mine, located about 280 km northeast of Jiddah, Kingdom of Saudi Arabia, has yielded more than 2 million ounces of gold from periodic production during the past 3,000 years. A new orebody on the southern side of the ancient workings, known as the South orebody, is being developed by Gold Fields-Mahd adh Dhahab Limited. A suite of samples was collected from the newly exposed orebody for preliminary mineralogic, stable isotope, fluid inclusion, and geochemical studies. The Mahd adh Dhahab deposit is in the carapace of a Proterozoic epizonal rhyolite stock that domed pyroclastic and metasedimentary rocks of the Proterozoic Halaban group. Ore of gold, silver, copper, zinc, tellurium, and lead is associated with north-trending, steeply dipping quartz veins in a zone 1,000 m long and 400 m wide. The veins include an assemblage of quartz-chlorite-pyrite-hematite-chalcopyrite-sphalerite-precious metals, which is similar to the mineral assemblage at the epithermal deposit at Creede, Colorado. The primary ore contains abundant chalcopyrite, sphalerite, and pyrite in addition to a complex precious metal assemblage. Gold and silver occur principally as minute grains of telluride minerals disseminated in quartz-chlorite-hematite and as inclusions in chalcopyrite and sphalerite. Telluride minerals include petzite, hessite, and sylvanite. Free gold is present but not abundant. All of the vein-quartz samples contained abundant, minute inclusions of both low-density, vapor-rich fluids and liquid-rich fluids. Primary fluid inclusions yielded homogenization temperatures of from 110? to 238? C. Preliminary light-stable isotope studies of the sulfide minerals and quartz showed that all of the d34S values are between 1.2 and 6.3 per mil, which is a typical range for hydrothermal sulfide minerals that derive their sulfur from an igneous source. The data-suggest that the sulfide sulfur isotope geochemistry was controlled by exchange with la large sulfur isotope reservoir at depth. The d18O values of all stages of vein quartz in the South orebody range between 8.5 and 11.1 per mil. This range is similar to that for quartz from the North orebody and indicates that the hydrothermal system consisted of dominantly exchanged meteoric water, which was uniform in temperature and d18O content throughout the area during the entire period of mineralization. Lead isotope analyses of two galena samples indicate that the lead in the South orebody is less radiogenic than that from the North orebody and confirm that the lead was derived from oceanic crust approximately 700 Ma ago.
NASA Astrophysics Data System (ADS)
Venturi, Stefania; Tassi, Franco; Gould, Ian R.; Shock, Everett L.; Hartnett, Hilairy E.; Lorance, Edward D.; Bockisch, Christiana; Fecteau, Kristopher M.; Capecchiacci, Francesco; Vaselli, Orlando
2017-10-01
Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this process.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kyle, J.R.; Misi, A.
1991-03-01
Carbonate strata of the Una Group represent late Proterozoic platform sedimentation in the Irece basin of north-central Brazil. Stratabound sulfide- and phosphate-rich units occur within a 50-m thick tidal flat sequence of dolomitic limestone and cherty dolomite. Three types of primary phosphate concentrations are present: columnar stromatolitic, laminar stromatolitic, and intraclastic. Resedimented phosphate clasts and phosphatic units interbedded with non phosphatic dolomites suggest early diagenetic replacement of algal carbonate units. Local stratabound Zn-Pb-Ag sulfide concentrations at the Tres Irmas prospect occur within silty dolomite with shallow water sedimentary structures and local disturbed laminae, synsedimentary faults, and breccias. Sulfide minerals includemore » pyrite, sphalerite, galena, marcasite, jordanite, tetrahedrite, and covellite. Pyrite crystal aggregates commonly show bladed forms. Nodular aggregates of length-slow quartz are locally associated with sulfides. Sulfur isotope analyses indicate relatively uniform heavy {delta}{sup 34}S values. Barite shows a {delta}{sup 34}S range from +25.2 to +29.6{per thousand}, CDT. Pyrite and sphalerite representative of a variety of textural types have a {delta}{sup 34}S range of +20.2 to +22.6{per thousand}. Late Proterozoic evaporite sulfates show a wide range of {delta}{sup 34} S values from about +10 to +28{per thousand}. Thus, the {delta}{sup 34}S values for Irece barite could reflect original seawater sulfate values. However, the relatively heavy {delta}{sup 34}S values of the associated sulfides suggests that the original seawater sulfate was modified by bacterial sulfate reduction processes in shallow sea floor sediments. Textural and {delta}{sup 34}S evidence suggests that a later stage of metallic mineralization scavenged sulfur from preexisting sulfides or from direct reduction of evaporitic sulfate minerals.« less
Removal of arsenic in flotation of galena and sphalerite
NASA Astrophysics Data System (ADS)
Yu, Dae-hwan; Kim, Min-kyu; Han, Oh-hyung; Park, Chul-hyun
2017-04-01
In Korea, Janggun mine that produces the concentrate of galena (PbS) /sphalerite (ZnS) containing arsenic of 1.3% charges a penalty of US 3/ton to LS-Nikko smelter. Hence in this work, flotation tests for removal of arsenopyrite (FeAsS) from sulfide minerals were carried out using lab scale flotation cell, which maintain grade and recovery of PbS and ZnS in comparison to flotation plant. Particularly, this study was focused on investigating the combination of several chemical reagents such as depressant, collector, activator and etc. that affect flotation performance. In the straight differential flotation for PbS, a PbS grade of 67.80% and a recovery of 80.2% could be obtained with FeAsS removal of 84.1% (0.2% As) under the conditions of 20% feed solids concentration, pH 8.5, 50g/t frother (AF65), 50g/t collector (AP242) and 600g/t As depressant (NaHSO3) and 600g/t Zn depressant (ZnSO4). In the ZnS flotation, the maximum separation achievable for ZnS has been shown to be a grade of 50.27% and a recovery of 88.7%. At this time, FeAsS removal of 87.8% (0.16% As) could be successfully accomplished under pH 11, and 1.2kg/t Zn activator (CuSO4), 100g/t frother (AF65), 100g/t collector (AP211) and 400g/t As depressant (NaHSO3). Acknowledgments This work was supported by the Energy and Resources Engineering Program Grant funded by the Ministry of Trade, Industry and Energy, Korea
Silberman, Miles L.; Csejtey, Bela; Smith, James G.; Lanphere, Marvin A.; Wilson, Frederic H.
1978-01-01
The now largely abandoned Willow Creek mining district, southern Talkeetna Mountains, Alaska, produced nearly $18,000,000 in gold and minor silver between 1909 and the early 1950's. Mineralized quartz veins, which contain gold and silver along with minor quantities of base metals (in pyrite, galena, chalcopyrite, sphalerite, molybdenite, and arsenopyrite), cut Late Cretaceous and early Tertiary tonalite and quartzmica schist of probable Jurassic age (Ray, 1954; Silberman and others, 1976; Bela Csejtey, Jr., unpub. data, 1978).
NASA Astrophysics Data System (ADS)
Vikentev, I.
2016-04-01
During processing the most of Au, Ag, Se, Te, Pb, Bi, Sb, Hg as well as notable part of Cu, Zn and Cd fail for tailings and became heavy metal pollutants. Modes of occurrence of Au, Ag, Te and Se covers two giant VMS deposits: Uchaly (intensively deformed) and Uzelginsk (altered by late hydrothermal processes) as well as middle-sized Molodezn and West Ozern deposits (nondeformed) have been studied. Mineral forms of these elements as well as their presence in disperse mode in common ore minerals (pyrite, chalcopyrite, sphalerite) have been studied using SEM, EPMA, INAA, ICP-MS and LA-ICP-MS.
Ayuso, Robert; Foley, Nora K.; Brown, C. Erwin
1987-01-01
The present study of fluid inclusions and lead isotopes was done to understand better the nature and possible source of the mineralizing solutions for both vertical and gash veins and the possible origin of the lead and zinc mineralization. Large deposits of essentially syngenetic sphalerite with minor to trace galena occur in the Proterozoic rocks of this region (e.g., Balmat-Edwards, New York). Although none of these deposits are known in the immediate vicinity of Rossie veins, the possibility that Rossie veins contain remobilized metals from these older deposits was considered.
1986-01-01
at 579.1 nm. These materials have high dispersion. 96 TABLE 14 OXIDES IN TELLEJRITE GLASSES .- Add it ive n TeO 2 -BaO TeO2 Wo 3 %*- La 2O 3 1.63...13 PbDeO3 and PbSiO 3 96 14 Oxides in Tellurite Glasses 97 15 Wurtzite Structure 98 16 Rocksalt Structure Chalcogenides 99 17 Zincblende or Sphalerite...alumina in glasses , SiO 2, was reported by Zuther, et al. who studied the glass system Ga 203-GeO 2-’v1 O5.56 The refractive indices of the monoclinic
Geology and ore deposits of the Mahd Adh Dhahab District, Kingdom of Saudi Arabia
Luce, Robert W.; Bagdady, Abdulaziz; Roberts, Ralph Jackson
1976-01-01
The principal ore minerals are pyrite, chalcopyrite, sphalerite, galena, and minor tetrahedrite, argentite, and native gold and silver. The gold and silver occurs finely disseminated in the veins and in the altered selvages of the veins. Widespread potassic and propylitic alteration accompanied the ore-forming processes. Potassium feldspar was introduced during an early stage of vein formation. Isotopic analyses of lead in vein potassium feldspar and galena yield a model age of about 900-1050 million years with the possibility of the original lead source having been remobilized about 600 million years ago. Chlorite and carbonate are also prominent vein minerals.
NASA Astrophysics Data System (ADS)
Saintilan, Nicolas J.; Spangenberg, Jorge E.; Samankassou, Elias; Kouzmanov, Kalin; Chiaradia, Massimo; Stephens, Michael B.; Fontboté, Lluís
2016-06-01
The current study has aimed to refine the previously proposed two-fluid mixing model for the Laisvall (sphalerite Rb-Sr age of 467 ± 5 Ma) and Vassbo Mississippi Valley-type deposits hosted in Ediacaran to Cambrian sandstone, Sweden. Premineralization cements include authigenic monazite, fluorapatite, and anatase in the Upper Sandstone at Laisvall, reflecting anoxic conditions during sandstone burial influenced by the euxinic character of the overlying carbonaceous middle Cambrian to Lower Ordovician Alum Shale Formation ( δ 13Corg = -33.0 to -29.5 ‰, δ 15Norg = 1.5 to 3.3 ‰, 0.33 to 3.03 wt% C, 0.02 to 0.08 wt% N). The available porosity for epigenetic mineralization, including that produced by subsequent partial dissolution of pre-Pb-Zn sulfide calcite and barite cements, was much higher in calcite- and barite-cemented sandstone paleoaquifers (29 % by QEMSCAN mapping) than in those mainly cemented by quartz (8 %). A major change in the Laisvall plumbing system is recognized by the transition from barite cementation to Pb-Zn sulfide precipitation in sandstone. Ba-bearing, reduced, and neutral fluids had a long premineralization residence time (highly radiogenic 87S/86Sr ratios of 0.718 to 0.723) in basement structures. As a result of an early Caledonian arc-continent collision and the development of a foreland basin, fluids migrated toward the craton and expelled Ba-bearing fluids from their host structures into overlying sandstone where they deposited barite upon mixing with a sulfate pool ( δ 34Sbarite = 14 to 33 ‰). Subsequently, slightly acidic brines initially residing in pre-Ediacaran rift sediments in the foredeep of the early Caledonian foreland basin migrated through the same plumbing system and acquired metals on the way. The bulk of Pb-Zn mineralization formed at temperatures between 120 and 180 °C by mixing of these brines with a pool of H2S ( δ 34S = 24 to 29 ‰) produced via thermochemical sulfate reduction (TSR) with oxidation of hydrocarbons in sandstone. Other minor H2S sources are identified. Upward migration and fluctuation of the hydrocarbon-water interface in sandstone below shale aquicludes and the formation of H2S along this interface explain the shape of the orebodies that splay out like smoke from a chimney and the conspicuous alternating layers of galena and sphalerite. Intimate intergrowth of bitumen with sphalerite suggests that subordinate amounts of H2S might have been produced by TSR during Pb-Zn mineralization. Gas chromatograms of the saturated hydrocarbon fraction from organic-rich shale and from both mineralized and barren sandstone samples indicate that hydrocarbons migrated from source rocks in the overlying Alum Shale Formation buried in the foredeep into sandstone, where they accumulated in favorable traps in the forebulge setting.
NASA Astrophysics Data System (ADS)
San Liou, Ying; Liu, Yi Chang
2017-04-01
Ancient glass beads with different colors, shapes, and stylistics unearthed from the archaeological sites of eastern Taiwan, dating back to approximately 1850-310 BP, have been investigated. It is generally known that glass bead is alien to invade into Taiwan along with metal ware, glass, agate, etc. since the Metal Age of Taiwan. Nevertheless, souring provenance and trade routes still remain controversial. Micro-Raman spectroscopy and μ-XRF have been applied on fifty-six ancient glass beads to reveal the mineralogical and chemical compositions and to help decipher the raw materials used and souring provenance. Micro-Raman measurements indicate the presence of hematite, zincite, siderite, sphalerite, lead tin yellow type II, quartz, feldspar, anatase, rutite, ankerite, graphite, calcite, etc. Among them, hematite, zincite, siderite, sphalerite, lead tin yellow type II, and rutile were found to be colorants/opacifiers. Moreover, crystalline phases such as lead tin yellow type II (PbSn1-xSixO3), zincite (ZnO), tricalcium diphosphate (Ca2(PO4)2), sphalerite ((Zn, Fe)S) and ankerite (Ca(Fe, Mg, Mn)(CO3)2) were detected in ancient glass beads unearthed from Taiwan for the first time. The chemical results obtained by μXRF show SiO2, Al2O3, Na2O, K2O, MgO, CaO, and PbO as the most abundant oxides. Na2O, K2O, Al2O3, MgO, and PbO could be the main/minor fluxes and colorants. In general, results of mineralogical and chemical analyses are compatible. According to chemical results, ancient glass beads can be classified as mineral soda alumina glass (m-Na-Al glass), soda plant ash glass (v-Na-Ca glass), lead silicate glass, and some less well known types. Mineral soda alumina and soda plant ash glass beads, as well as lead silicate glass beads are generally believed to be the distinct phases of production and exchange in Southeast Asia and China, respectively. In terms of chronology of glass bead, beads excavated from sites of 1850-930 BP are mineral soda alumina glass (m-Na-Al glass) and soda plant ash glass (v-Na-Ca glass). On the other hand, beads from sites of <930 BP are belonging to lead silicate glass. It is indicated that the souring provenance of ancient beads of eastern Taiwan is probably a multiple sources, i.e., in earlier time, glass beads were brought into Taiwan through the maritime exchange and/or trade activities between Taiwan and Southeast Asia; at the later period, lead silicate glass beads were imported from China. However, some mineral soda alumina and soda plant ash glass beads were found in a later period, it might be attributed to glass beads reuse or trade route between Taiwan and Southeast Asia is successive since ca. 1850 BP.
NASA Astrophysics Data System (ADS)
Antoshkina, A. I.; Ryabinkina, N. N.
2018-02-01
Complex modern micro- and spectroscopic methods for study of siderite concretions in the Lower Carboniferous terrigenous strata on the Kozhym River (Subpolar Urals) have shown that its formation was caused by destruction of clay minerals due to the activity of bacterial communities. The abundance of these bacteria was caused by gas-fluid seeps and bacterial methanogenesis processes in bottom deposits. In basins with normal marine fauna, this led to local desalination, hydrogen sulfide contamination, mass collapse of primary organisms, and the development of element-specific bacteria. The occurrence of these bacteria caused the formation of specific authigenic mineralization in the concretion of sideritic bacteriolites: the framboidal pyrite, sphalerite, galenite, barite, sulfoselenides, and tellurides.
NASA Astrophysics Data System (ADS)
Essaifi, Abderrahim; Ballèvre, Michel; Marignac, Christian; Capdevila, Ramon
2001-10-01
A zincian ilmenite paragenesis is found in metapelites from a contact metamorphic zone (central Jebilet, Morocco) induced by the emplacement of microgranitic intrusions. The zincian ilmenite is mainly preserved in syntectonic andalusite porphyroblasts. The growth of zincian ilmenite is related either to sphalerite breakdown during prograde metamorphism, or to the pervasive flow of a mineralizing fluid within the metapelites. The chlorine-rich fluid carried zinc and other metals leached in the microgranites, during its flow to discharge zones which were probably the Jebilet sulfide deposits.
Allcott, Glenn H.
1970-01-01
The mineralized zone at the remotely located Ash Sha'ib ancient mine contains only a small tonnage of moderately low grade sulfide- bearing rock. Based on present data the gross value of the deposit, with a value of $25.00 or more per ton, is $20,000,000. A belt of metasedimentary rocks, intruded by gabbro to the south and granite to the north, was the host for fissure vein-replacement type mineralization. Most of the mineralization is in a siliceous dolomite transected by fissures. The main sulfide mineral is sphalerite, but minor amounts of chalcopyrlte and argentlferous galena contribute to the value of the mineralized sections.
Evidence for microbial activity in the formation of carbonate-hosted Zn-Pb deposits
NASA Astrophysics Data System (ADS)
Kucha, H.; Raith, J.
2009-04-01
*Kucha H **Raith J *University of Mining and Metallurgy, Faculty of Geology, Geophysics and Environmental Protection, Mickiewicza 30, PL-30-059 Krakow, Poland. ** University of Leoben, Department of Applied Geosciences and Geophysics, A-8700 Leoben, Peter Tunner Str. 5, Austria Evidence for microbial activity in the formation of carbonate-hosted Zn-Pb deposits To date evaluation of bacterial processes in the formation of carbonate-hosted Zn-Pb deposits is largely based on sulphur isotope evidence. However, during a past few years, textural criteria, have been established, which support the bacterial origin of many of these deposits. This has received a strong support from micro-, and nano-textures of naturally growing bacterial films in a flooded tunnel within carbonates that host the Piquette Zn-Pb deposit (Druschel et al., 2002). Bacterial textures, micro- and nano textures found in carbonate-hosted Zn-Pb deposits are: i)wavy bacterial films up to a few mm thick to up to a few cm long composed of peloids, ii)semimassive agglomeration of peloids in the carbonate matrix, and iii)solitary peloids dispersed in the carbonate matrix. Peloids are usually composed of a distinct 50-90um core most often made up of Zn-bearing calcite surrounded by 30-60um thick dentate rim composed of ZnS. Etching of Zn-carbonate cores reveals 1 - 2um ZnS filaments, and numerous 15 to 90nm large ZnS nano-spheres (Kucha et al., 2005). In massive ore composite Zn-calcite - sphalerite peloids are entirely replaced by zinc sulphide, and form peloids ghosts within banded sulphide layers. Bacterially derived micro- and nano-textures have been observed in the following carbonate-hosted Zn-Pb deposits: 1)Irish-type Zn-Pb deposits. In the Navan deposit the basic sulphur is isotopically light bacteriogenic S (Fallick at al., 2001). This is corroborated by semimassive agglomerations of composite peloids (Zn-calcite-ZnS corona or ZnS core-melnikovite corona). Etching of Zn-calcite core reveals globular 0.5 to 1um large fossilised bacteria with some nano-size spheres as well (Kucha et al., 1990). In the Silvermines and Ballinalack ores wavy bacterial film-like textures composed of peloids made up of Zn-calcite or Zn-siderite cores and ZnS rims are known (Kucha et al., 1990). 2) Alpine Zn-Pb deposits. Bleiberg sulphides, Austria, Zn-Pb ores display the δ34S‰ values from -32 to -2 (n=284), with mean close to 20‰ (Schroll & Rantitsch, 2005). Cardita and Crest ores contain wavy bacterial films (-28.84 to -27.91‰). Semimassive globular sphalerite with globules varying in size from 90 to 180um is a basic ZnS type in the Bleiberg ores with light sulphur from (-30.49 to -26.4‰). Based on sulphur isotope data, um-sized bacterial filaments, and spherical nano-textures seen in etched ZnS globules, sulphate reducing bacteria (SRB) involvement is suggested (Kucha et al. 2005). ZnS globules were formed by replacement of original peloids (i.e. bacterial colonies) and/or by agglomeration of original 10-15nm ZnS spheres secreted by SRB. The growth of peloids was promoted by unbalanced electric charges on the surfaces of these ZnS nano-spheres. 3) Upper Silesian MVT Zn-Pb deposits. Sulphur isotopes vary between 2 and 12‰, (mean 5‰) for early stage sulphides, main stage sulphides are characterised by S signature -2 to -15‰. Redeposition of ZnS from the horst to graben structures produced "pulvery" sphalerite with -19‰ (Haranczyk, 1993). Sulphide stalactites containing oxysulphides have δS‰ vales of -23.7. Bacterial microtextures occur mainly within oxysulphides and at the contact between Fe-smithsonite replaced by banded sphalerite (Kucha et al., 1990). 4) La Calamine and Engis, Belgium, contain bacterial micro- and nano-textures in ores related to karst cavities, and paleoweathering crusts (Kucha et al., 1990). The biogenic textures are represented by clumps of peloids, and bacterial mats occurring in banded sphalerite composed of replaced peloids. Peloids are composed of Zn-calcite cores and ZnS rims, oxysulphides, thiosulphates, vaesite and chalcedonic silica. Bacterial microtextures in all of the above mentioned deposits are as a rule associated with oxysulphides i.e. compounds with mixed and intermediate sulphur valences (Kucha et al., 1989). The origin of oxysulphides is probably related either directly to incomplete bacterial reduction of the sulphatic sulphur, or reaction of bacterial H2S with sulphatic S present in the fluids. Some of peloids are composed of oxysulphides (Kucha & Stumpfl, 1992; Kucha, 2003). Therefore, an interpretation of the S isotopic signature of bacterial textures should consider not only microbial community structure, but also the oxidative part of the sulphur cycle proceeding through compounds with mixed sulphur valences. References Druschel GK, Labrenz M, Thomsen-Ebert T, Fowler DA, Banfield JF (2002) Geochemical modelling of ZnS in biofilms: An example of ore depositional processes. Economic Geology, v 97, 1319-1329. Fallick, AE, Ashton JH, Boyce AJ, Ellam RM, Russell MJ (2001) Bacteria were responsible fort he magnitude of the world-class hydrothermal base metal sulphide orebody at Navan, Ireland. Economic Geology, v 96, 885 - 890. Haranczyk Cz (1993) Sulphur isotope models of genesis of the Silesian-Cracov Zn-Pb ore deposits. Geological Quarterly, v 37, 307 - 322. Kucha H (1988) Biogenic and non-biogenic concentration of sulfur and metals in the carbonate-hosted Ballinalack Zn-Pb deposit, Ireland. Min. Pet., 38, 171-187. Kucha H, Wouters R, Arkens O (1989) Determination of sulfur and iron valence by microprobe. Scanning Microscopy, 3, no 1, 89-97. Kucha H, Van der Biest J, Viaene W (1990) Peloids in strata bound Zn-Pb deposits and their genetic importance. Min. Deposita, 25, 132-139. Kucha H, Stumpfl EF (1992) Thiosulphates as precursors of banded sphalerite and pyrite at Bleiberg, Austria. Min. Mag., 56, 165-172. Kucha H (2003) Mississippi Valley Type Zn-Pb deposits of Upper Silesia, Poland, 253-272. In: Kelly, J., G., Andrew, C., J., Ashton, J., H., Boland, M., B., Earls, E., Fusciardi, L., Stanley, G. (eds) Europe's Major Base Metal Deposits, Irish Association for Economic Geology, Printed by Colour Books Ltd, Dublin 2003, 551 pp. Kucha H, Schroll E, Stumpfl EF (2005) Fossil sulphate-reducing bacteria in the Bleiberg lead-zinc deposit, Austria. Mineralium Deposita, v 40, 123-126. Schroll E, Rantitsch G (2005) Sulfur isotope patterns in the Bleiberg deposit (Eastern Alps) and their implications for genetically affiliated. Mineralogy and Petrology 148: 1-18.
Dai, S.; Ren, D.; Li, D.; Chou, C.-L.; Luo, K.
2006-01-01
Mineralogy and geochemistry of the No. 11 Coal bed were investigated by using inductively-coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF), scanning electron microscopy equipped with energy-dispersive X-ray (SEM-EDX), sequential chemical extraction procedure (SCEP), and optical microscopy. The results show that the No. 11 Coal bed has very high contents of veined quartz (Vol. 11.4%) and veined ankerite (Vol. 10.2 %). The veined ankerite was generally coated by goethite and the veined quartz embraced chalcopyrite, sphalerite, and selenio-galena. In addition, a trace amount of kaolinite was filled in the veins. These seven minerals often occur in the same veins. The formation temperatures of the veined ankerite and quartz are 85??C and 180??C respectively, indicating their origins of iron-rich calcic and siliceous low-temperature hydrothermal fluids in different epigenetic periods. Studies have also found that the veined quartz probably formed earlier than the veined ankerite, and at least three distinct ankerite formation stages were observed by the ration of Ca/Sr and Fe/Mn of ankerite. The mineral formation from the early to late stage is in order of sulfide, quartz, kaolinite, ankerite, and goethite. The veined ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn, which are as high as 0.09%, 74.0 ??g/g, 33.6 ??g/g, 185 ??g/g, and 289 ??g/g in this coal seam, respectively. However, the veined quartz is the main carrier of Pd, Pt, and Ir, which are 1.57 ??g/g, 0.15 ??g/g, and 0.007 ??g/g in this coal seam, respectively. In addition, chalcopyrite, sphalerite, and selenio-galena of hydrothermal origin were determined in the veined quartz, and these three sulfide minerals are also important carriers of Cu, Zn and Pb in the No. 11 Coal bed.
Diagenetic evidence for an epigenetic origin of the Courtbrown Zn-Pb deposit, Ireland
NASA Astrophysics Data System (ADS)
Reed, Christopher P.; Wallace, Malcolm W.
2001-08-01
Mineralisation at the Courtbrown deposit in south-western Ireland is concentrated in the basal section of the Chadian Waulsortian Limestone, immediately above the Courceyan Ballysteen Limestone. Two episodes of sulphide deposition have been identified: an early stage of minor pyrite precipitation, and a later base-metal-rich mineralisation event. Sphalerite, galena and pyrite of the later mineralisation event occur predominantly as replacement phases along stylolites, dissolution seams, and within the micritic matrix of the host limestone. These sulphide minerals also occur as cements within late stage fractures. The following diagenetic phases are present in the Waulsortian and Ballysteen Limestones in the Courtbrown area (from oldest to youngest): non-luminescent synsedimentary calcite cements, non-luminescent equant calcite cements, bright luminescent calcite cement, dull luminescent calcite cement, planar dolomite cement and replacement dolomite (regional dolomite), saddle dolomite cement, and fibrous dull luminescent calcite cement filling pressure-shadows around the sulphide minerals. Homogenisation temperatures for primary fluid inclusions within dull luminescent calcite cements (precipitated penecontemporaneously with base-metal mineralisation) range from 160 to 200 °C, with a mode at 170-180 °C. These values are unlikely to be representative of mineralisation temperatures as the fluid inclusions may have been significantly affected by heating and/or deformation during late burial (maximum paleotemperatures from Ro and CAI data around 310 °C). The observed paragenetic sequence indicates that mineralisation is completely epigenetic. As the earliest mineralisation is hosted by macro-stylolites, the sequence must have obtained a minimum burial depth of around 800 m prior to the onset of mineralisation. A burial depth of 800 m would correspond to an approximate early Chadian age for the Courtbrown area. Pressure-shadows around sphalerite further indicate that mineralisation preceded the major phase of Variscan deformation. Therefore, the base-metal mineralisation at Courtbrown is epigenetic, and the age of mineralisation is in the range of 350 to 307 Ma.
NASA Astrophysics Data System (ADS)
Noku, Shadrach K.; Espi, Joseph O.; Matsueda, Hiroharu
2015-01-01
We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu-Zn-Au-Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite-marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from -4.5 to +7.0 ‰ ( n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of -1.9 to +4.7 ‰ ( n = 16). The mineralizing stage these correspond to had moderately saline (5.9-8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of -36.1 to -33.8 ‰ ( n = 2), which suggest an organic source for S. Pyrite-marcasite and chalcopyrite from Federal Flag show δ34S values of -2.4 to -1.9 ‰ ( n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic-hydrothermal fluids. The very narrow range and near-zero δ34S values (-1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.
Geology of the Wood and East Calhoun mines, Central City District, Gilpin County, Colorado
Drake, Avery Ala
1955-01-01
The Wood-East Calhoun mine area is underlain by complexly folded Precambrian gneiss and pegmatite. The major fold in the area is an anticline that trends about N. 60° E. The Precambrian rocks are intruded by bostonite porphyry dikes of Tertiary age. All the rocks are cut by east- to northeast - trending faults that have been filled by precious metal-sulfide veins which have been worked chiefly for gold. The Wood vein occurs in an east-trending fault; the Calhoun vein occurs in a northeast-trending fault. Much of the uranium production of the Central City district has come from the Wood vein on Quartz Hill. The veins consist chiefly of quartz; pyrite is the chief metallic mineral and chalcopyrite is next in abundance. Sphalerite, galena, tetrahedrite-tennantite, and pitchblende are locally present. Deposition began with alteration-stage quartz and pyrite followed in order by pitchblend, light-yellow pyrite, massive quartz, yellow pyrite, shalerite, comb quartz, chalcopyrite, tetrahedrite-tennantite, galena, chalcopyrite, pyrite, and gray to light-brown fine-grained quartz. The veins of the Central City district are zoned, with quartz-pyrite veins near the center and galena-sphalerite veins on the periphery. The known pitchblende bodies are in the transition between these, but paragenetically, the pitchblende is earlier than all other metallic minerals. A trace element study of the ore indicates an association of zirconium and molybdenum with uranium, of bismuth, antimony, and arsenic with copper, and of cadmium with zinc. The pitchblende and other ore minerals are concentrated in ore shoots. The shoots are in open spaces controlled by the competency of the wall rocks, the presence of a prevailing direction of weakness in the rocks, and changes in strike and dip of the vein. The pitchblende is thought to be a local constituent of the quartz-pyrite ores and to owe its origin to residual solutions from the quartz bostonite magma.
Wanty, Richard B.; Podda, F.; De Giudici, Giovanni; Cidu, R.; Lattanzi, Pierfranco
2013-01-01
The Rio Naracauli in SW Sardinia drains part of the Ingurtosu Zn–Pb mining district, and contains extreme concentrations of dissolved Zn at near-neutral pH. In the upper reaches of the stream, pH, alkalinity and Zn concentrations are such that hydrozincite [Zn5(CO3)2(OH)6] precipitates in a biologically mediated process facilitated by a microalga (Chlorella sp.) and a cyanobacterium (Scytonema sp.). Values of δ66Zn in water and solid samples ranged from − 0.35‰ to + 0.5‰ relative to the JMC 3-0749-Lyon standard, and closely follow a mass-dependent fractionation line. Two composite samples of sphalerite, the primary ore mineral in the Ingurtosu deposits, had an average δ66Zn of + 0.15‰, similar to sphalerite measured elsewhere in hydrothermal mineral deposits. Zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope, 66Zn, in the hydrozincite relative to 64Zn. Synthetic hydrozincites produced without added bacteria have δ66Zn identical to the dissolved Zn, thus suggesting a biologically mediated mineralization process in Rio Naracauli. The average fractionation, Δhdz-water, is 0.35‰, the magnitude of which is consistent with other studies, and suggests an extracellular mechanism of the biomineralization process. Zinc concentration and dissolved δ66Zn steadily decrease in the reach of the stream where the biomineralization occurs. The biomineralization process also leads to the sequestration of Pb, Cu and Ni in the hydrozincite lattice, and the coeval precipitation of an amorphous CdCO3 solid, prompting the suggestion that if optimized, the biomineralization process might represent a feasible passive remediation strategy for streams with high Zn and other metals, and with near-neutral pH.
Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.
2012-01-01
Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation of ZnS by O 2, an estimated 8% of sulfate-oxygen was derived from O 2, which is enriched in 18O relative to water, thus resulting in a larger apparent ?? 18OSO 4-H 2O value of 9.5???. Based on the data presented we hypothesize that the similar ?? 18OSO 4-H 2O values of ~8??? from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite (SO3-) intermediate and H 2O. Our results indicate that the ??18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ?? 18OSO 4-H 2O values of ~8??? measured here are distinctly higher than ?? 18OSO 4-H 2O values of ~4??? previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured ?? 18OSO 4 values. ?? 2011 Elsevier Ltd.
NASA Astrophysics Data System (ADS)
Barriga, F. J.; Fonseca, R.; Dias, S.; Cruz, I.; Carvalho, C.; Relvas, J. M.; Pedersen, R.
2010-12-01
The Loki’s Castle hydrothermal vent field was discovered in the summer of 2008 during a cruise led by the Centre of Geobiology of the University of Bergen, integrated in the H2Deep Project (Eurocores, ESF; see Pedersen et al., 2010, AGU Fall Meeting, Session OS26). Fresh volcanic glasses analyzed by EPMA are basalts. The vent site is composed of several active, over 10 m tall chimneys, producing up to 320 C fluid, at the top of a very large sulfide mound (estimated diameter 200 m). Mineralogy: The main sulfide assemblage in chimneys consists of sphalerite (Sp), pyrite (Py) and pyrrhotite, with lesser chalcopyrite (Ccp). Sulphide-poor selected samples collected at the base of chimneys are mostly composed of anhydrite (Anh), gypsum and talc (Tlc). Association of quartz, anhydrite, gypsum and barite were also found in some of the samples. The sulphide-poor samples from the base of the chimneys denote seawater interaction with the hydrothermal fluid and consequent decrease in temperature, precipitating sulfates. Sphalerite compositions are Zn(0.61-0.70)Fe(0.39-0.30)S. The variations in Fe content are consistent with those of hot, reduced hydrothermal fluids. The observed sulfide assemblage is consistent with the temperature of 320C measured in Loki’s Castle vents. Compositional zonation in sphalerites suggests different pulses of activity of the hydrothermal system, with higher contents of Zn in the center of the crystals. Geochemistry: Here we report preliminary data part of a major analytical task of sequential extraction of metals from sediments in the vicinity of Loki’s Castle, in an attempt to detect correlations with microbial populations and/or subseafloor mineralized intervals. The abundances of Cu, Pb, Ni, Cr, Zn, Fe, Mn and Co in sediments were determined by aqua regia extraction on subsamples from 7 gravity cores. Several anomalous intervals were sampled, in which Cu<707ppm, Ni shows many weak peaks (<50ppm), Cr shows 6 peaks (<121ppm), Zn shows 4 well-defined peaks (<234ppm). Fe varies up to ~9% and Mn, not surprisingly, is enriched in the upper few centimeters of each core. Co shows hardly any peaks. The various metals show variable degrees of intercorrelation. Cores GC6 and GC7, both located ~25 km to the SW of Loki’s Castle, contain the most anomalous intervals. Some intervals contain clusters of anomalous values of most analyzed metals, in others the anomalies are scattered vertically through both cores. The variations in metal contents along the GC6 and GC7 cores indicate oscillation in hydrothermal activity during sediment formation, suggesting different pulses of activity of the hydrothermal field. These two cores also reveal an enrichment in Mn in the upper layers, which could indicate either oxyhydroxide precipitation directly under the seafloor, due to the gradual mixing of the hydrothermal plumes with seawater (cooler and more oxidizing). Collectively, these data suggest both layered and cross-cutting metal-enriched intervals. The latter may correspond to hydrothermal upflow of mineralized solutions through the sediments.
Foley, Nora K.; Bethke, Philip M.; Rye, Robert O.
1989-01-01
The unusually high contrast between the salinities of the ore-depositing fluids and the ground water overlying the ore zone allowed recognition of this phenomenon at Creede. It is likely, however, that Creede is not unique. Similar phenomena may be common in shallow ore zones where rapid fluctuation of an interface between a deep, high-temperature thermal plume and an overlying, cooler ground water may be expected to occur. Careful study of the origins of fluid inclusions, particularly in quartz, is essential to characterize the primary ore fluids and to assess the role of ground water in the hydrology of shallow ore deposits.
Geochemical survey of the Lusk Creek Roadless Area, Pope County, Illinois
Klasner, John S.; Day, Gordon W.
1984-01-01
The Lusk Creek Roadless Area (Index map) lies along the western edge of the Illinois-Kentucky fluorspar district in which flourite deposits occur as lenticular-type veins emplaced along fult zones or as tratiform-shaped bedding-replacement deposits that occur along fault zones (Grogan and Bradbury, 1967; Trace, 1974). Although mineralogy varies between deposits, Trace (1974) points out that the principal minerals are fluorite (CaF) and calcite (CaCO3), and associated with these minerals are lesser amounts of sphalerite (ZnS), galena (PbS), and barite (BaSO4). Minor quantites of iron-rich dolomite (CaMg(CO3)2), pyrite (FeS2), and alteration products of zinc, lead, and copper minerals also are found.
Rust in the Apollo 16 rocks. [hydration and oxidation processes in lunar environment
NASA Technical Reports Server (NTRS)
Taylor, L. A.; Mao, H. K.; Bell, P. M.
1973-01-01
Apollo 16 samples of all four rock types and from all stations contain evidence for hydration and oxidation - i.e., the presence of hydrated iron oxide, probably goethite. Rock 66095 contains native FeNi grains with a characteristic intergrowth of schreibersite and, to lesser extents, of cohenite. Troilite also contains sphalerite. The goethite contains 1.5-4.6 wt.% chlorine and occurs mainly on the edges of FeNi metal, causing a rust color in the cracks and space around the native metal grains, which also contain abundant chlorine. This observation suggests the presence of lawrencite (FeCl2), a phase that deliquesces and oxidizes very rapidly upon exposure to water or to a moist atmosphere.
Deformation, geochemistry, and origin of massive sulfide deposits, Gossan lead district, Virginia.
Gair, J.E.; Slack, J.F.
1984-01-01
Lenses and layers of massive sulphides comprise a discontinuous horizon in the late Proterozoic metasedimentary Ashe formation. The folded and brecciated sulphides include pyrrhotite, minor chalcopyrite, sphalerite and pyrite, and rare arsenopyrite and galena. The deposits were mined for supergene copper, later for gossan iron, and finally for sulphur. The Ashe formation is interpreted to be marine turbidites, and contains lenses of mafic rocks of probable tholeiitic basalt parentage. Mineralogically and chemically distinctive rocks - for the Ashe formation - are interbedded with the sulphides and may represent metamorphosed alteration zones and/or mixed chemical and clastic sediments. The sulphide deposits are interpreted as syngenetic sediments, modified by deformation during metamorphism. Their deposition occurred in a deep, elongate marine basin overlying a crustal rift zone.-G.J.N.
Geology of the Huron River pitchblende occurrence, Baraga County, Michigan
Vickers, R.C.
1955-01-01
Pitchblende and secondary uranium minerals occur as very small, discontinuous stringers and pods in calcite and quartz cementing the breccia within a low-angle shear zone that dips about 10 degrees to the southwest. The shear zone has a thickness of 10 to 30 feet and cuts black, locally carbonaceous slates of the upper Huronian Precambrian Michigamme slate. Mineral deposition during two hypogene stages and one supergene stage was identified in polished sections. The first phase consisted of the introduction of quartz and minor hematite into the sheared slate. After fracturing of the quartz the second stage was initiated by deposition of calcite, pyrite, rutile, pitchblende, bornite, sphalerite, chalcopyrite, galena, and greenockite. The supergene stage consisted of the development of metatyuyamunite, chalcopyrite, chalcocite, covellite, cuprite, volborthite, malachite, and goethite.
Epitaxial relationship of semipolar s-plane (1101) InN grown on r-plane sapphire
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dimitrakopulos, G. P.
2012-07-02
The heteroepitaxy of semipolar s-plane (1101) InN grown directly on r-plane sapphire by plasma-assisted molecular beam epitaxy is studied using transmission electron microscopy techniques. The epitaxial relationship is determined to be (1101){sub InN} Parallel-To (1102){sub Al{sub 2O{sub 3}}}, [1120]{sub InN} Parallel-To [2021]{sub Al{sub 2O{sub 3}}}, [1102]{sub InN}{approx} Parallel-To [0221]{sub Al{sub 2O{sub 3}}}, which ensures a 0.7% misfit along [1120]{sub InN}. Two orientation variants are identified. Proposed geometrical factors contributing to the high density of basal stacking faults, partial dislocations, and sphalerite cubic pockets include the misfit accommodation and reduction, as well as the accommodation of lattice twist.
Te-Rich argyrodite occurrence in Roşia Montană ore deposit, Apuseni Mountains, Romania
NASA Astrophysics Data System (ADS)
Bailly, Laurent; Tămaş, Călin-Gabriel; Minuţ, Adrian
2005-06-01
A new argyrodite occurrence has been discovered in the Roşia Montană ore deposit located in the South Apuseni Mountains, Romania. Argyrodite is associated with common base metal sulfides and sulfosalts (galena, sphalerite, chalcopyrite, tetrahedrite ± alabandite, pyrite, and marcasite), tellurides (hessite, altaite, sylvanite) and rare electrum grains in the Ag-rich Cârnicel vein hosted by an extracraterial phreatomagmatic breccia within the Cârnic massif. SEM and EPMA analyses revealed that this argyrodite is Te-rich and a mean Ag 8.04Ge 0.9Te 2.07S 3.77 formula was calculated. This phase could be the germaniferous equivalent of the previously-described Te-rich canfieldite. To cite this article: L. Bailly et al., C. R. Geoscience 337 (2005).
The Genesis of Precious and Base Metal Mineralization at the Miguel Auza Deposit, Zacatecas, Mexico
NASA Astrophysics Data System (ADS)
Findley, A. A.; Olivo, G. R.; Godin, L.
2009-05-01
The Miguel Auza mine located in Zacatecas State, Mexico, is a vein-type polymetallic epithermal deposit hosted in deformed argillite, siltstone and, greywacke of the Cretaceous Caracol Formation. Silver-rich base metal veins (0.2 m to >1.5 m wide) are spatially associated with the NE-striking, steeply SE- dipping (70-80°) Miguel Auza fault over a strike length of 1.6 km and a depth of 460 m. A 2 km2 monzonitic stock located in the proximity of the mineralized zones, has previously been interpreted as the source of the mineralizing fluids. Four distinct structural stages are correlated with hydrothermal mineral deposition: (I) The Pre-ore stage is characterized by normal faulting, fracturing of host rock, and rotation of bedding planes. This stage consists of quartz, illite, chlorite, +/- pyrite alteration of sedimentary wall rocks. (II) The Pyrite-vein stage is associated with reverse-sense reactivation of early normal faults, dilation of bedding planes/fractures, and deposition of generally barren calcite + pyrite veinlets. (III) The Main-ore stage is related to the development of reverse-fault- hosted massive sulphide veins. During this stage three phases of mineral deposition are recorded: early pyrite and arsenopyrite, intermediate chalcopyrite, pyrite, arsenopyrite, and base metals, and late base metals and Ag-bearing minerals. Associated gangue minerals during the main ore stage are quartz, muscovite, calcite and chlorite. (IV) The Post-ore stage involves late NW-SE striking block faulting, brecciation and calcite veining. Later supergene oxidation of veins led to deposition of Fe-oxides and hydroxides, commonly filling fractures or replacing early-formed sulphide assemblages. The various vein types display classic epithermal textures including open space filling, banding, comb quartz and brecciation. The Ag-bearing minerals comprise pyrargyrite [Ag3(Sb,As)S3], argentotennantite [(Cu,Ag)10(Zn,Fe)2(Sn,As)4S13], polybasite-pearceite [(Ag,Cu)16(Sb,As)2S11], and acanthite [AgS2]; associated sulphides include galena, sphalerite, chalcopyrite, arsenopyrite and pyrite. In the main ore zone, base metal sulphides are commonly intergrown with the Ag-bearing sulfosalts. Analyses of galena show no significant silver values indicating that silver grades are exclusively associated with the Ag-bearing sulfosalts and sulphides. The distribution of the Sb/(Sb + As) ratios in the silver sulfosalts indicate that the ore forming fluid(s) was consistently antimony-rich during the Ag-rich ore deposition with no significant variation laterally, vertically, or along strike of the vein systems. However, Ag/(Ag + Cu) values in argentotennantite decrease along-strike from NE to SW and with depth. Compositions of argentotennantite + pyrargyrite + sphalerite indicate a primary depositional temperature around 325-350° C for the late phase of the Main-ore stage. Compositions of sphalerite also show an increasing trend in FeS (mol %) along strike of the deposit from NE to SW. The geometric relationship between the various structures, vein types, and the regional Miguel Auza fault zone suggest episodic reverse-sense reactivation of normal faults. It is argued that the structural evolution of the area, and, in particular, the Main-ore stage, provided transport pathways for metal-rich fluids and controlled the orientations of ore-bearing veins. Variations in mineral chemistry suggest that the rocks in the NE sector interacted with hotter fluids than in the SW part of the deposit.
Layered hydrothermal barite-sulfide mound field, East Diamante Caldera, Mariana volcanic arc
Hein, James R.; de Ronde, Cornel E. J.; Koski, Randolph A.; Ditchburn, Robert G.; Mizell, Kira; Tamura, Yoshihiko; Stern, Robert J.; Conrad, Tracey; Ishizuka, Osamu; Leybourne, Matthew I.
2014-01-01
East Diamante is a submarine volcano in the southern Mariana arc that is host to a complex caldera ~5 × 10 km (elongated ENE-WSW) that is breached along its northern and southwestern sectors. A large field of barite-sulfide mounds was discovered in June 2009 and revisited in July 2010 with the R/V Natsushima, using the ROV Hyper-Dolphin. The mound field occurs on the northeast flank of a cluster of resurgent dacite domes in the central caldera, near an active black smoker vent field. A 40Ar/39Ar age of 20,000 ± 4000 years was obtained from a dacite sample. The mound field is aligned along a series of fractures and extends for more than 180 m east-west and >120 m north-south. Individual mounds are typically 1 to 3 m tall and 0.5 to 2 m wide, with lengths from about 3 to 8 m. The mounds are dominated by barite + sphalerite layers with the margins of each layer composed of barite with disseminated sulfides. Rare, inactive spires and chimneys sit atop some mounds and also occur as clusters away from the mounds. Iron and Mn oxides are currently forming small (<1-m diam, ~0.5-m tall) knolls on the top surface of some of the barite-sulfide mounds and may also drape their flanks. Both diffusely and focused fluids emanate from the small oxide knolls. Radiometric ages of the layered barite-sulfide mounds and chimneys vary from ~3,920 to 3,350 years. One layer, from an outcrop of 10- to 100-cm-thick Cu-rich layers, is notably younger with an age of 2,180 years. The Fe-Mn oxides were <5 years old at the time of collection in 2009.Most mound, chimney, and layered outcrop samples are dominated by barite, silica, and sphalerite; other sulfides, in decreasing order of abundance, are galena, chalcopyrite, and rare pyrite. Anglesite, cerussite, and unidentified Pb oxychloride and Pb phosphate minerals occur as late-stage interstitial phases. The samples contain high Zn (up to 23 wt %), Pb (to 16 wt %), Ag (to 487 ppm), and Au (to 19 ppm) contents. Some layered outcrop samples are dominated by chalcopyrite resulting in ≤4.78 wt % Cu in a bulk sample (28 wt % for a single lens), with a mean of 0.28 wt % for other samples. Other significant metal enrichments are Sb (to 1,320 ppm), Cd (to 1,150 ppm), and Hg (to 55 ppm).The East Diamante mound field has a unique set of characteristics compared to other hydrothermal sites in the Mariana arc and elsewhere. The geochemical differences may predominantly reflect the distribution of fractures and faults and consequently the rock/water ratio, temperature of the fluid in the upper parts of the circulation system, and extensive and prolonged mixing with seawater. The location of mineralization is controlled by fractures. Following resurgent doming within the caldera, mineralization resulted from focused flow along small segments of linear fractures rather than from a point source, typical of hydrothermal chimney fields. Based on the mineral assemblage, the maximum fluid temperatures were ~260°C, near the boiling point for the water depths of the mound field (367–406 m). Lateral fluid flow within the mounds precipitated interstitial sphalerite, silica, and Pb minerals within a network of barite with disseminated sulfides; silica was the final phase to precipitate. The current low-temperature precipitation of Fe and Mn oxides and silica may represent rejuvenation of the system.
Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.
2008-01-01
The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.
Dusel-Bacon, Cynthia; Foley, Nora K.; Slack, John E.; Koenig, Alan E.; Oscarson, Robert L.
2012-01-01
Volcanogenic massive sulfide (VMS) Zn-Pb-Cu-Ag-Au deposits of the Bonnifield mining district formed during Late Devonian-Early Mississippian magmatism along the western edge of Laurentia. The largest deposits, Dry Creek and WTF, have a combined resource of 5.7 million tonnes at 10% Zn, 4% Pb, 0.3% Cu, 300 grams per tonne (g/t) Ag, and 1.6 g/t Au. These polymetallic deposits are hosted in high field strength element (HFSE)- and rare-earth element (REE)-rich peralkaline (pantelleritic) metarhyolite, and interlayered pyritic argillite and mudstone of the Mystic Creek Member of the Totatlanika Schist Formation. Mystic Creek metarhyolite and alkali basalt (Chute Creek Member) constitute a bimodal pair that formed in an extensional environment. A synvolcanic peralkaline quartz porphyry containing veins of fluorite, sphalerite, pyrite, and quartz intrudes the central footwall at Dry Creek. The Anderson Mountain deposit, located ~32 km to the southwest, occurs within calc-alkaline felsic to intermediate-composition metavolcanic rocks and associated graphitic argillite of the Wood River assemblage. Felsic metavolcanic rocks there have only slightly elevated HFSEs and REEs. The association of abundant graphitic and siliceous argillite with the felsic volcanic rocks together with low Cu contents in the Bonnifield deposits suggests classification as a siliciclastic-felsic type of VMS deposit. Bonnifield massive sulfides and host rocks were metamorphosed and deformed under greenschist-facies conditions in the Mesozoic. Primary depositional textures, generally uncommon, consist of framboids, framboidal aggregates, and spongy masses of pyrite. Sphalerite, the predominant base metal sulfide, encloses early pyrite framboids. Galena and chalcopyrite accompanied early pyrite formation but primarily formed late in the paragenetic sequence. Silver-rich tetrahedrite is a minor late phase at the Dry Creek deposit. Gold and Ag are present in low to moderate amounts in pyrite from all of the deposits; electrum inclusions occur in Dry Creek sphalerite. Contents and ratios of trace elements in graphitic argillite that serve as proxies for the redox state of the bottom waters in the basin indicate that Dry Creek mineralization took place in suboxic to periodically anoxic bottom waters. Trace element data show higher contents of Tl-Mn-As in pyrite from the Anderson Mountain deposit compared to the Dry Creek or WTF deposits and thus suggest that Anderson Mountain may have formed at lower temperatures or under slightly more oxidizing conditions. No exact modern analogue for the tectonic setting of the Bonnifield VMS deposits is known, although the back-arc regions of the Okinawa Trough and Woodlark Basin satisfy the requirement for a submarine, extensional setting adjacent to a continental margin. Limited occurrences of peralkaline volcanic rocks occur in these two potential analogues, but the peralkalinity of those rocks is much less than that of the Mystic Creek Member metarhyolites in the Bonnifield district. The highly elevated trace element (e.g., Zr, Nb) contents of Mystic Creek metarhyolites suggest that a better analogue may be a submarine rifted continental margin. The calc-alkaline composition of the host rocks to the Anderson Mountain deposit suggests that mineralization there formed in a continental margin arc, outboard of the extended continental margin setting of the peralkaline-hosted Dry Creek and WTF deposits.
Silver-bearing minerals in the Xinhua hydrothermal vein-type Pb-Zn deposit, South China
NASA Astrophysics Data System (ADS)
Wang, Minfang; Zhang, Xubo; Guo, Xiaonan; Pi, Daohui; Yang, Meijun
2018-02-01
Electron probe microanalysis (EPMA) results are reported for newly identified silver-bearing minerals from the Xinhua deposit, Yunkaidashan area, South China. The Xinhua deposit is a hydrothermal vein-type Pb-Zn deposit and is hosted in the Pubei Complex, which consists of a cordierite-biotite granite with a U-Pb zircon age of 244.3 ± 1.8-251.9 ± 2.2 Ma. The mineralization process is subdivided into four mineralization stages, characterized by the following mineral associations: mineralization stage I with quartz, pyrite, and sphalerite; mineralization stage II with siderite, galena, and tetrahedrite; mineralization stage III with quartz and galena; and mineralization stage IV with quartz, calcite, and baryte. Tetrahedrite series minerals, such as freibergite, argentotetrahedrite, and tennantite are the main Ag-bearing minerals in the Xinhua deposit. The greatest concentration of silver occurs in phases from mineralization stage II. Microscopic observations reveal close relationship between galena and tetrahedrite series minerals that mostly occur as irregular inclusions within galena. The negative correlation between Cu and Ag in the lattices of tetrahedrite series minerals suggests that Cu sites are occupied by Ag atoms. Zn substitution for Fe in argentotetrahedrite and Cd substitution for Pb in tetrahedrite are also observed. Micro-thermometric data reveal that both homogenization temperatures and calculated salinities of hydrothermal fluids decrease progressively from the early to the later mineralization stages. The metal ions, such as Ag+, Cu+, Pb2+, and Zn2+, are transported as chlorine complex ions in the early mineralization stage and as bisulfide complex ions in the late mineralization stage, caused by changes in oxygen fugacity, temperature, and pH of the hydrothermal fluids. Because of the varying solubility of different metal ions, Pb2+, Zn2+, and Cu2+ ions are initially precipitated as galena, sphalerite, and chalcopyrite, respectively. With decreasing temperature of the fluids, Pb2+ ions are incorporated along with Cu+, Sb3+, and As3+ ions into sulfosalt minerals, and Ag+ ions are coprecipitated with Cu+, Sb3+, and As3+ ions forming tetrahedrite series minerals or replacing earlier sulfides and sulfosalts.
S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides
Ono, Shuhei; Shanks, Wayne C.; Rouxel, O.J.; Rumble, D.
2007-01-01
Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different ??33S (?????33S-0.515 ??34S) values of up to 0.04??? even if ??34S values are identical. Detection of such small ??33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006??? (2??). Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10??N, 13??N, and 21??S and Mid-Atlantic Ridge (MAR) 37??N yield ??33S values ranging from -0.002 to 0.033 and ??34S from -0.5??? to 5.3???. The combined ??34S and ??33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13??N and marcasite from MAR 37??N are in isotope disequilibrium not only in ??34S but also in ??33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low ??33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles. ?? 2006 Elsevier Inc. All rights reserved.
Duration of mineralization and fluid-flow history of the Upper Mississippi Valley zinc-lead district
Rowan, E.L.; Goldhaber, M.B.
1995-01-01
Studies of fluid inclusions in sphalerite and biomarkers from the Upper Mississippi Valley zinc district show homogenization temperatures to be primarily between 90 and 150??C, yet show relatively low levels of thermal maturity. Numerical calculations are used to simulate fluid and heat flow through fracture-controlled ore zones and heat transfer to the adjacent rocks. Combining a best-fit path through fluid-inclusion data with measured thermal alteration of biomarkers, the time interval during which mineralizing fluids circulated through the Upper Mississippi Valley district was calculated to be on the order of 200 ka. Cambrian and Ordovician aquifers underlying the district, principally the St. Peter and Mt. Simon Sandstones, were the source of the mineralizing fluid. The duration of mineralization thus reflects the fluid-flow history of these regional aquifers. -from Authors
Enhancement of Au-Ag-Te contents in tellurium-bearing ore minerals via bioleaching
NASA Astrophysics Data System (ADS)
Choi, Nag-Choul; Cho, Kang Hee; Kim, Bong Ju; Lee, Soonjae; Park, Cheon Young
2018-03-01
The purpose of this study was to enhance the content of valuable metals, such as Au, Ag, and Te, in tellurium-bearing minerals via bioleaching. The ore samples composed of invisible Au and Au paragenesis minerals (such as pyrite, chalcopyrite, sphalerite and galena) in combination with tellurium-bearing minerals (hessite, sylvanite and Tellurobismuthite) were studied. Indigenous microbes from mine drainage were isolated and identified as Acidithiobacillus ferrooxidans, which were used in bioleaching after adaption to copper. The effect of the microbial adaption on the bioleaching performance was then compared with the results produced by the non-adaptive process. The microbial adaption enhanced the Au-Ag-Te contents in biological leaching of tellurium-bearing ore minerals. This suggests that bioleaching with adapted microbes can be used both as a pretreatment and in the main recovery processes of valuable metals.
Petrology, Mineralogy, and Trace Element Geochemistry of Yuanyang
NASA Astrophysics Data System (ADS)
Wang, H. Y.; Xu, W. B.
2016-09-01
Yuanyang was found in Yunnan in 2010. Yuanyang has a rusted surface, and there are also some corroded materials inside. The major phases in Yuanyang are kamacite (Ni 4.88-6.21 wt%) and taenite (Ni 26.13-50.27 wt%). The minor ones are schreibersite, sphalerite, and carlsbergite. Yuanyang is a coarse octahedrite with a high content of kamacite (80 vol%). No silicate inclusions are found in Yuanyang. The instrumental neutron activation analysis (INAA) of Yuanyang reveals that it is a low-Ni (7 wt%) and low-Au (1.565 ppm) iron. Yuanyang is an IAB-MG iron. The Ir content (1.00 ppm) of Yuanyang is relatively low compared to other IAB-MG irons. This is probably due to the partial melting of Ir-rich phase in its parent body during an impact event.
Volatile metal deposits on lunar soils: Relation to volcanism
NASA Technical Reports Server (NTRS)
Reed, G. W., Jr.; Allen, R. O., Jr.; Jovanovic, S.
1977-01-01
Parallel leaching and volatilization experiments conducted on lunar samples and similar experiments on sphalerite do not supply the information needed to resolve the question of the chemical nature of pb 204, Zn, Bi and Tl deposits on lunar soil surfaces. It is proposed that in Apollo 17 mare and terra soils and fractions of pb 204, Zn and Tl that are insoluble under mild, hot pH 5HNO3, leaching conditions and involatile at 600 C were originally surface deposits which became immobilized by migration into the silicate substrate or by chemisorption. Only Bi is predominantly indigenous. The implication is also that the soils over their respective times of evolution were exposed to heavy metal vapors or that an episodic exposure occurred after they had evolved. A sequence of events is proposed to account for orange 74220 and black 74001 glasses by lava fountaining and for soil 74241 as tephra from an explosive volcanic eruption.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vashistha, Indu B., E-mail: indu-139@yahoo.com; Sharma, S. K.; Sharma, Mahesh C.
2015-08-28
In order to find the suitable alternative of toxic CdS buffer layer, deposition of pure ZnS and doped with Al by chemical bath deposition method have been reported. Further as grown pure and doped thin films have been annealed at 150°C. The structural and surface morphological properties have been characterized by X-Ray diffraction (XRD) and Atomic Force Microscope (AFM).The XRD analysis shows that annealed thin film has been polycrystalline in nature with sphalerite cubic crystal structure and AFM images indicate increment in grain size as well as growth of crystals after annealing. Optical measurement data give band gap of 3.5more » eV which is ideal band gap for buffer layer for solar cell suggesting that the obtained ZnS buffer layer is suitable in a low-cost solar cell.« less
Mizoguchi, T; Ishii, H
1980-06-01
Sulphate in sulphate ores, e.g., alunite, anglesite, barytes, chalcanthite, gypsum, manganese sulphate ore, is reduced to hydrogen sulphide by the hypophosphite-tin metal-CPA method, if a slight modification is made. Sulphide ores, e.g., galena, sphalerite, are quantitatively decomposed with CPA alone to give hydrogen sulphide. Suitable reducing agents must be used for the quantitative recovery of hydrogen sulphide from pyrite, nickel sulphide, cobalt sulphide and cadmium sulphide, or elemental sulphur is liberated. Iodide must be used in the decomposition of chalcopyrite; the copper sulphide is too stable to be decomposed by CPA alone. Molybdenite is not decomposed in CPA even if reducing agents are added. The pretreatment methods for the determination of sulphur in sulphur oxyacids and elemental sulphur have also been investigated.
Chemical characterization of individual particles (PM10) from ambient air in Guiyang City, China.
Xie, R K; Seip, H M; Leinum, J R; Winje, T; Xiao, J S
2005-05-01
PM10 samples were collected during 5 days in Guiyang, China in July 2003. A total of about 2300 particles was analyzed by an automated Scanning Electron Microscope with Energy-Dispersive Spectrometer (SEM-EDS). Hierarchical cluster analysis (HCA) was used to identify different particle types that occurred in the aerosol. Seventeen particle types were identified and presented in the order of decreasing number abundance as: silicomanganese slag, soil and fly ash, coal burning, silicomanganese, quartz, syngenite, S-bearing iron, calcium rich, gypsum, sphalerite, dolomite, iron, alloy, lead sulfate, zinc rich, sulfur-rich particles and aluminum manufacturing dust. The majority of the particles in the studied size range are of anthropogenic origin, especially from metallurgical industry. The study illustrates the complexity of particle pollution in air of an industrial Chinese city and the results should be useful in planning mitigation measures.
Slack, J.F.; Wei-Teh, Jiang; Peacor, D.R.; Okita, P.M.
1992-01-01
Berthierine, a 7 A?? Fe-Al member of the serpentine group, occurs in the footwall stringer zone of the Archean Kidd Creek massive sulfide deposit, associated with quartz, muscovite, chlorite, pyrite, sphalerite, chalcopyrite, and local tourmaline, cassiterite, and halloysite. Petrographic and scanning electron microscopic (SEM) studies reveal different types of berthierine occurrences, including interlayers within the rims on deformed chlorite, intergrowths with muscovite and halloysite, and discrete coarse grains. This is the first reported occurrence of berthierine from volcanogenic massive sulfide deposits. Textural relations suggest that most of the berthierine formed as a primary hydrothermal mineral at relatively high temperatures (~350??C) in the footwall stringer zone, probably by the replacement of a pre-existing aluminous phase such as muscovite or chlorite. However, the intergrowth textures observed by SEM and TEM suggest that some of the berthierine originated by syn- or post-metamorphic replacement of chlorite. -from Authors
An ore genetic model for the Lubin—Sieroszowice mining district, Poland
NASA Astrophysics Data System (ADS)
Wodzicki, A.; Piestrzyński, A.
1994-04-01
The Lubin-Sieroszowice mining district is a world-class copper-silver, stratabound ore deposit that lies near the Lower-Upper Permian boundary. It transgresses the Werra dolomite, the Kupferschiefer organicrich shale and the Weissliegendes sandstone, which overlie barren Rotliegendes sandstone. On the basis of underground and microscope observations and light stable isotope data, and thermodynamic calculations, a new ore genesis model is proposed whereby ore minerals were deposited in the following stages: Stage 0 was synsedimentary or earliest diagenetic and contains 100s ppm of base metals trapped by clay minerals, and minor sulphides. Stage I was early diagenetic and contains 1000s ppm base metals. It is characterized by bornite and overlying chalcopyrite + pyrite that lie a short distance above the Rotliegendes/Weissliegendes contact. The sulphides were deposited near the interface between an overlying, buffered, reducing fluid (1), largely derived from the Kupferschiefer, and an oxidizing fluid (2) in the Rotliegendes. Stage II is the main ore-forming stage. This stage is late diagenetic, peneconcordant, lies near the Kupferschiefer/Weissliegendes contact, and contains several percent base metals.It is associated with the hematite-bearing Rote Fäule facies and is characterized by vertical zonation. A central chalcocite zone is flanked above and below by bornite and chalcopyrite. Silver occurs with all the above sulphides. Galena and sphalerite occur mainly just above copper zone, whereas pyrite is usually present in the upper part of the copper zone and together with galena and sphalerite. Metals were transported in a copper-rich oxidizing fluid (3), which probably originated deep in the Permian basin, reacted with organic matter in the Kupferschiefer, and mixed with reducing fluid (1) in the Weissliegendes, resulting in the observed mineral zonation. Stage III is late diagenetic, discordant and is represented by massive and dispersed chalcocite ore present on the peripheries and below anhydrite-cemented Weissliegendes sandstone. It resulted from redistribution of earlier copper and silver minerals by descending, reduced, sulphur-rich fluids (4). Stage IV consists of rare polymetallic veins of no economic importance that cut the stratigraphy and are probably related to Alpine tectonism. The richest and thickest ore is in the Weissliegendes, 10-15 km east of the Rote Fäule facies (Fig. 1). It probably occupies structures that trapped fluid (1) which was the main precipitant of metals in the sandstone.
Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite.
Voegelin, Andreas; Jacquat, Olivier; Pfister, Sabina; Barmettler, Kurt; Scheinost, Andreas C; Kretzschmar, Ruben
2011-01-01
The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.
NASA Astrophysics Data System (ADS)
Jiang, Si-Hong; Chen, Chun-Liang; Bagas, Leon; Liu, Yuan; Han, Ning; Kang, Huan; Wang, Ze-Hai
2017-08-01
The Xing-Mong Orogenic Belt (XMOB) is located in the eastern part of the Central Asian Orogenic Belt (CAOB) and has experienced multiple tectonic events. The Baiyinnuoer Pb-Zn deposit may be a rare case that documents two periods of mineralization in the tectonically complex XMOB. There are two types of Pb-Zn mineralization in the deposit: (1) skarn-type ore, hosted by the skarn in the contact zone between marble and granodiorite and within the marble and (2) vein-type ore, hosted by crystal tuff and feldspar porphyry. This study revealed that the host rocks, mineral assemblages, mineralization occurrences, S-Pb isotopes, and ages between the two types of ore are notably different. Zircon U-Pb dating indicates that the granodiorite was emplaced in the Early Triassic (244 ± 1 to 242 ± 1 Ma), the crystal tuff was deposited in the Early Cretaceous (140 ± 1 to 136 ± 1 Ma), and the feldspar porphyry was intruded in the Early Cretaceous (138 ± 2 to 136 ± 2 Ma). The first skarn mineralization occurred at ∼240 Ma and the second vein-type Pb-Zn mineralization took place between 136 and 129 Ma. Thus the Triassic orebodies were overprinted by Early Cretaceous mineralization. The sphalerite and galena from the skarn mineralization have higher δ34S values (-4.7 to +0.3‰) than the sphalerite, galena and aresenopyrite from the vein-type mineralization (-7.5 to -4.2‰), indicating different sulfur sources or ore-forming processes for the two types of mineralization. The Pb isotopic compositions of the two types of ore are very similar, suggesting similar lead sources. Geochemistry and Nd-Pb-Hf isotopic systematics of the igneous rocks in the region show that the Triassic granodiorite was generated from hybridization of mafic and felsic magmas due to strong crust-mantle interaction under the collisional setting that resulted following the closure of the Paleo-Asian Ocean and the collision of North China and Siberian cratons at the end of the Permian; while the Cretaceous igneous rocks at Baiyinnuoer originated from the partial melting of a juvenile lower crust with minor input from the crust caused by the underplating of mafic magma in an extensional setting.
Wilmarth, V.R.; Vickers, R.C.
1953-01-01
Uranium deposits that contain uraniferous pyrobitumen of possible hydrothermal origin occur at the Weatherly and Robinson properties near Placerville, San Miguel County, Colo. These deposits were mined for copper, silver, and gold more than 50 years ago and were developed for uranium in 1950. The Robinson property, half a mile east of Placerville, consists of the White Spar, New Discovery Lode, and Barbara Jo claims. The rocks in this area are nearly horizontal sandstones, shales, limestones, and conglomerates of the Cutler formation of Permian age and the Dolores formation of Triassic and Jurassic (?) age. These rocks have been faulted extensively and intruded by a Tertiary (?) andesite porphyry dike. Uranium-bearing pyrobitumen associated with tennantite, tetrahedrite, galena, sphalerite, chalcopyrite, bornite, azurite, malachite, calcite, barite, and quartz occurs in a lenticular body as much as 40 feet long and 6 feet wide along a northwest-trending, steeply dipping normal fault. The uranium content of eleven samples from the uranium deposit ranges from 0.001 to 0.045 percent uranium and averages about 0.02 percent uranium. The Weatherly property, about a mile northwest of Placerville, consists of the Black King claims nos. 1, 4, and 5. The rocks in this area include the complexly faulted Cutler formation of Permian age and the Dolores formation of Triassic and Jurassic (?) age. Uranium-bearing pyrobitumen arid uranophane occur, along a northwest-trending, steeply dipping normal fault and in the sedimentary rocks on the hanging wall of the fault. Lens-shaped deposits in the fault zone are as much as 6 feet long and 2 feet wide and contain as much as 9 percent uranium; whereas channel samples across the fault zone contain from 0.001 to 0.014 percent uranium. Tetrahedrite, chalcopyrite, galena, sphalerite, fuchsite, malachite, azurite, erythrite, bornite, and molybdite in a gangue of pyrite, calcite, barite, and quartz are associated with the uraniferous material. In the sedimentary rocks on the hanging wall, uranium-bearing pyrobitumen occurs in replacement lenses as much as,8 inches wide and 6 feet long, and in nodules as much as 6 inches in diameter for approximately 100 feet away from the fault. Pyrite and calcite are closely associated with the uraniferous material in the sedimentary rocks. Samples from the replacement bodies contain from 0. 007 to 1.4 percent uranium.
Foley, Nora K.; Jaskula, Brian W.; Kimball, Bryn E.; Schulte, Ruth F.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.
2017-12-19
Gallium is a soft, silvery metallic element with an atomic number of 31 and the chemical symbol Ga. Gallium is used in a wide variety of products that have microelectronic components containing either gallium arsenide (GaAs) or gallium nitride (GaN). GaAs is able to change electricity directly into laser light and is used in the manufacture of optoelectronic devices (laser diodes, light-emitting diodes [LEDs], photo detectors, and solar cells), which are important for aerospace and telecommunications applications and industrial and medical equipment. GaAs is also used in the production of highly specialized integrated circuits, semiconductors, and transistors; these are necessary for defense applications and high-performance computers. For example, cell phones with advanced personal computer-like functionality (smartphones) use GaAs-rich semiconductor components. GaN is used principally in the manufacture of LEDs and laser diodes, power electronics, and radio-frequency electronics. Because GaN power transistors operate at higher voltages and with a higher power density than GaAs devices, the uses for advanced GaN-based products are expected to increase in the future. Gallium technologies also have large power-handling capabilities and are used for cable television transmission, commercial wireless infrastructure, power electronics, and satellites. Gallium is also used for such familiar applications as screen backlighting for computer notebooks, flat-screen televisions, and desktop computer monitors.Gallium is dispersed in small amounts in many minerals and rocks where it substitutes for elements of similar size and charge, such as aluminum and zinc. For example, gallium is found in small amounts (about 50 parts per million) in such aluminum-bearing minerals as diaspore-boehmite and gibbsite, which form bauxite deposits, and in the zinc-sulfide mineral sphalerite, which is found in many mineral deposits. At the present time, gallium metal is derived mainly as a byproduct of the processing of bauxite ore for aluminum; lesser amounts of gallium metal are produced from the processing of sphalerite ore from three types of deposits (sediment-hosted, Mississippi Valley-type, and volcanogenic massive sulfide) for zinc. The United States is expected to meet its current and expected future needs for gallium through imports of primary, recycled, and refined gallium, as well as through domestic production of recycled and refined gallium. The U.S. Geological Survey estimates that world resources of gallium in bauxite exceed 1 billion kilograms, and a considerable quantity of gallium could be present in world zinc reserves.
Duuring, P.; Hagemann, S.G.; Cassidy, K.F.; Johnson, C.A.
2004-01-01
Tarmoola is a structurally controlled Archean orogenic gold deposit hosted in greenschist facies metamorphosed komatiite and trondhjemite in the Leonora district of the Eastern Goldfields province, Yilgarn craton. High-grade (>1 g/t Au) orebodies are located in komatiite wall rock adjacent to the eastern and northeastern margins of the asymmetrical, north-south-striking, Tarmoola trondhjemite intrusion. Gold-bearing veins post-date trondhjemite emplacement (ca. 2700 Ma), quartz diorite dikes (ca. 2667 Ma), and regional greenschist facies metamorphism. Textures and crosscutting relationships in gold-bearing veins indicate two stages of hydrothermal fluid infiltration associated with a single gold-related hydrothermal event: a volumetrically dominant, but gold-poor, stage I fluid and a gold-rich stage II fluid. Gold-bearing veins contain stage I milky quartz and pyrite that are overprinted by stage II quartz-ankerite-muscovite-chalcopyrite-sphalerite-galena-gold-tellurides ?? albite ?? chlorite ?? fuchsite ?? epidote ?? scheelite. Stage I hydrothermal alteration assemblages are different in trondhjemite and komatiite due to contrasting reactions between a common ore fluid and disparate wall-rock chemistry. Stage II fluid-wall rock interaction was minor compared to stage I and is indicated by the overprinting of stage I mineral assemblages by stage II microveins. Wall-rock alteration proximal to veins in trondhjemite is characterized by replacement of igneous plagioclase, amphibole, biotite, and metamorphic chlorite by hydrothermal quartz, muscovite, ankerite, calcite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold, whereas in proximal alteration in komatiite, metamorphic chlorite and talc are replaced by ankerite, quartz, muscovite, albite, chlorite, fuchsite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold. The stage II fluid was enriched in H2O, CO2, Si, Ca, K, Na, S, Au, Ag, Cu, Pb, W, Bi, As, Mo, Zn, and Te. Based on fluid inclusion studies and stage II mineral equilibria, gold deposited from a homogeneous, neutral to slightly alkaline (pH 5.1-5.5), reduced, low-salinity (<5.5 wt % NaCl equiv) fluid that had a bulk composition of 78 mole percent H2O and 21 mole percent CO2, and trace amounts of CH4, C2H6, H2, Ar, H2S, and He. Gold deposition occurred at 300?? ?? 50??C and 0.5 to 3.0 kbars. Assuming lithostatic fluid pressures, gold precipitated at a 2- to 10-km depth. Stage II gray quartz ??18Ofluid values range from 5.9 to 7.5 per mil, whereas ??Dfluid values calculated from the dehydration of muscovite grains and measured directly from bulk fluid inclusion analyses of stage II gray quartz have ranges of -9 to -35 and -27 to -28 per mil, respectively. Hydrothermal ore fluids were transported from greater crustal depths to the site of gold deposition during the district-scale D3 event by shallowly W dipping, reverse brittle-ductile shear zones in supracrustal rock and along the steeply east dipping trondhjemite contact. Associated subhorizontal east-west shortening caused the reactivation of the eastern trondhjemite margin and subparallel foliation, which facilitated the transport of hydrothermal fluids and the generation of gold-bearing veins and hydrothermal alteration zones in komatiite. East-west-striking fractures in trondhjemite aided the lateral migration of ore fluids away from trondhjemite margins and the formation of east-west-striking gold-bearing veins and broad alteration zones. Gold was most likely transported in the stage II fluid as bisulfide complexes. The sulfidation of trondhjemite and komatiite wall rock by the stage II fluid caused the destabilization of An bisulfide complexes and gold deposition. Potassium, Ca, and CO2 metasomatism of komatiite wall rock may have enhanced gold deposition via the acidification of the stage II fluid. The physicochemical characteristics of the Tarmoola ore fluid and relative timing of gold mineralization are consistent with the Yilgarn-wide,
NASA Astrophysics Data System (ADS)
Fornadel, Andrew P.; Voudouris, Panagiotis Ch.; Spry, Paul G.; Melfos, Vasilios
2012-05-01
The Fakos porphyry Cu and epithermal Au-Te deposit, Limnos Island, Greece, is hosted in a ~20 Ma quartz monzonite and shoshonitic subvolcanic rocks that intruded middle Eocene to lower Miocene sedimentary basement rocks. Metallic mineralization formed in three stages in quartz and quartz-calcite veins. Early porphyry-style (Stage 1) metallic minerals consist of pyrite, chalcopyrite, galena, bornite, sphalerite, molybdenite, and iron oxides, which are surrounded by halos of potassic and propylitic alteration. Stage 2 mineralization is composed mostly of quartz-tourmaline veins associated with sericitic alteration and disseminated pyrite and molybdenite, whereas Stage 3, epithermal-style mineralization is characterized by polymetallic veins containing pyrite, chalcopyrite, sphalerite, galena, enargite, bournonite, tetrahedrite-tennantite, hessite, petzite, altaite, an unknown cervelleite-like Ag-telluride, native Au, and Au-Ag alloy. Stage 3 veins are spatially associated with sericitic and argillic alteration. Fluid inclusions in quartz from Stage 1 (porphyry-style) mineralization contain five types of inclusions. Type I, liquid-vapor inclusions, which homogenize at temperatures ranging from 189.5°C to 403.3°C have salinities of 14.8 to 19.9 wt. % NaCl equiv. Type II, liquid-vapor-NaCl, Type III liquid-vapor-NaCl-XCl2 (where XCl is an unknown chloride phase, likely CaCl2), and Type IV, liquid-vapor-hematite ± NaCl homogenize to the liquid phase by liquid-vapor homogenization or by daughter crystal dissolution at temperatures of 209.3 to 740.5 °C, 267.6 to 780.8 °C, and 357.9 to 684.2 °C, respectively, and, Type V, vapor-rich inclusions. Stage 2 veins are devoid of interpretable fluid inclusions. Quartz from Stage 3 (epithermal-style) veins contains two types of fluid inclusions, Type I, liquid-vapor inclusions that homogenize to the liquid phase (191.6 to 310.0 °C) with salinities of 1.40 to 9.73 wt. % NaCl equiv., and Type II, vapor-rich inclusions. Mixing of magmatic fluids with meteoric water in the epithermal environment is responsible for the dilution of the ore fluids that formed Stage 3 veins. Eutectic melting temperatures of -35.4 to -24.3 °C for Type I inclusions hosted in both porphyry- and epithermal-style veins suggest the presence of CaCl2, MgCl2, and/or FeCl2 in the magmatic-hydrothermal fluids. Sulfur isotope values of pyrite, galena, sphalerite, and molybdenite range from δ34S = -6.82 to -0.82 per mil and overlap for porphyry and epithermal sulfides, which suggests a common sulfur source for the two styles of mineralization. The source of sulfur in the system was likely the Fakos quartz monzonite for which the isotopically light sulfur isotope values are the result of changes in oxidation state during sulfide deposition (i.e., boiling) and/or disproportionation of sulfur-rich magmatic volatiles upon cooling. It is less likely that sulfur in the sulfides was derived from the reduction of seawater sulfate or leaching of sulfides from sedimentary rocks given the absence of primary sulfides in sedimentary rocks in the vicinity of the deposit. Late-stage barite (δ34S = 10.5 per mil) is inferred to have formed during mixing of seawater with magmatic ore fluids. Petrological, mineralogical, fluid inclusion, and sulfur isotope data indicate that the metallic mineralization at Fakos Peninsula represents an early porphyry system that is transitional to a later high- to intermediate-sulfidation epithermal gold system. This style of mineralization is similar to porphyry-epithermal metallic mineralization found elsewhere in northeastern Greece (e.g., Pagoni Rachi, St. Demetrios, St. Barbara, Perama Hill, Mavrokoryfi, and Pefka).
Structure of the sulfur K x-ray emission spectrum: influence of the oxidation state
NASA Astrophysics Data System (ADS)
Pérez, P. D.; Carreras, A. C.; Trincavelli, J. C.
2012-01-01
The sulfur K x-ray emission was studied in pure sulfur, anhydrite (CaSO4) and sphalerite (ZnS) samples. The ionizations were induced by electron impact and the spectra were recorded with a wavelength dispersive spectrometer. The spectral processing was performed through a methodology based on the optimization of atomic and experimental parameters. Energies and intensities of diagram and satellite lines were determined for a set of transitions in the Kα and Kβ groups. The lines studied include Kα22, Kα2, Kα1, Kα‧, Kα3, Kα4, Kα5, Kα6, Kβ1,3, Kβ-RAE, KβIII, KβIV, Kβx, Kβ‧ and Kβ″. The main spectral differences between the three oxidation states were analysed, considering the influence of the ligand atoms. The results were compared with data published by other authors and the origin of certain lines was discussed on the basis of data available in the literature.
NASA Astrophysics Data System (ADS)
Pati, J. K.; Panigrahi, M. K.; Chakarborty, M.
2014-06-01
The dominantly high-K, moderate to high SiO2 containing, variably fractionated, volcanic-arc granitoids (± sheared) from parts of Bundelkhand craton, northcentral India are observed to contain molybdenite (Mo) in widely separated 23 locations in the form of specks, pockets, clots and stringers along with quartz ± pyrite ± arsenopyrite ± chalcopyrite ± bornite ± covellite ± galena ± sphalerite and in invisible form as well. The molybdenite mineralization is predominantly associated with Bundelkhand Tectonic Zone, Raksa Shear Zone, and localized shear zones. The incidence of molybdenite is also observed within sheared quartz and tonalite-trondhjemite-granodiorite (TTG) gneisses. The fluid inclusion data show the presence of bi-phase (H2O-CO2), hypersaline and moderate temperature (100°-300°C) primary stretched fluid inclusions suggesting a possible hydrothermal origin for the Mo-bearing quartz occurring within variably deformed different granitoids variants of Archean Bundelkhand craton.
Structural variations in indium tin tellurides and their thermoelectric properties
NASA Astrophysics Data System (ADS)
Neudert, Lukas; Schwarzmüller, Stefan; Schmitzer, Silvia; Schnick, Wolfgang; Oeckler, Oliver
2018-02-01
Indium-doped tin tellurides are promising and thoroughly investigated thermoelectric materials. Due to the low solubility of In2Te3 in SnTe and vice versa, samples with the nominal composition (SnTe)3-3x(In2Te3)x with 0.136 ≤ x ≤ 0.75 consist of a defect-rocksalt-type Sn-rich and a defect-sphalerite-type In-rich phase which are endotaxially intergrown and form nanoscale heterostructures. Such nanostructures are kinetically inert and become more pronounced with increasing overall In content. The vacancies often show short-range ordering. These phenomena are investigated by temperature-dependent X-ray diffraction and HRTEM as well as STEM with element mapping by X-ray spectroscopy. The combination of real-structure effects leads to very low lattice thermal conductivity from room temperature up to 500 °C. Thermoelectric figures of merit ZT of heterostructured materials with x = 0.136 reach ZT values up to 0.55 at 400 °C.
Volatile metal deposits on lunar soils - Relation to volcanism
NASA Technical Reports Server (NTRS)
Reed, G. W., Jr.; Jovanovic, S.; Allen, R. O., Jr.
1977-01-01
Parallel leaching and volatilization experiments conducted on lunar samples and similar experiments on sphalerite do not supply the information needed to resolve the question of the chemical nature of Pb-204, Zn, Bi, and Tl deposits on lunar soil surfaces. It is proposed that in Apollo 17 mare and terra soils the fractions of Pb-204, Zn, and Tl that are insoluble under mild, hot pH 5 HNO3, leaching conditions and involatile at 600 C were originally surface deposits which became immobilized by migration into the silicate substrate or by chemisorption. Most of the Bi does not seem to be the result of such a deposit. The implication is also that the soils, over their respective times of evolution, were exposed to heavy metal vapors or that an episodic exposure occurred after they had evolved. A sequence of events is proposed to account for orange 74220 and black 74001 glasses by lava fountaining and for soil 74241 as tephra from an explosive volcanic eruption.
Michalski, T.C.
1984-01-01
Of the 20 or so amethyst localities reported in Colorado, four are described in some detail and comments are given on their geology. The Crystal Hill mine, near La Garita, Saguache County, contains rock crystal (long slender prisms with small rhombohedral terminations) and pale lavender amethyst (generally <3 in. in length). The deposit was worked as early as the 1800's as a gold mine and also contains abundant manganese oxides. Amethyst, associated with argentiferous galena, sphalerite and chalcopyrite, occurs in the Amethyst mine, in the Creede district, on West Willow Creek, Mineral County. The specimens here consist of small pale pinkish-purple crystals interlayered with milky quartz, some as banded forms ("sowbelly agate') and as geode-like vugs. Amethyst also occurs in Unaweep Canyon south of Grand Junction in Mesa County. Pale to very dark amethyst occurs as crystals dominated by large rhombohedra and small prisms (approx 1 in. across). At Red Feather Lakes, Larimer County, amethyst crystals are medium to dark purple and have prism and rhombohedral faces nearly equally developed; some are doubly terminated. -R.S.M.
NASA Astrophysics Data System (ADS)
Soler, A.; Ayora, C.; Cardellach, E.; Delgado, J.
1990-12-01
Several varieties of skarn outcrop have been found to develop along the contact between the Andorra granite and the Devonian limestones. The skarns contain variable amounts of gold ranging up to 5 g/t, always associated with sulphides. The sulphides in the skarn include arsenopyrite and pyrrhotite with lesser amounts of chalcopyrite, galena, sphalerite and Bi-minerals. Geothermometric and geobarometric data indicate the skarns formed at about 2 kbar and temperatures ranging from 500 ° to 350 °C from CO2-free polysaline brines at a slightly acidic pH and oxygen fugacity which decreases with time from the pyrite-pyrrhotite-magnetite towards the QFM buffer. Available data on gold solubility suggest that sufficient quantities of gold to form an ore deposit could have been transported as AuCl{2/-}at the high temperatures and salinities under which the skarns formed. Both gold deposition and sulphide precipitation could have occurred due to a decrease in temperature and/or oxygen fugacity.
Normark, W.R.
1986-01-01
The submersible Alvin was used to investigate 3 active hydrothermal discharge sites along the S Juan de Fuca Ridge in September 1984. The hydrothermal zones occur within a 10-30m-deep, 30-50m-wide cleft marking the center of the axial valley. This cleft is the eruptive locus for the axial valley. The hydrothermal vents coincide with the main eruptive vents along the cleft. Each hydrothermal zone has multiple discharge sites extending as much as 500m along the cleft. Sulfide deposits occur as clusters (15-100m2 area) of small chimneys (= or <2m high) and as individual and clustered fields of large, branched chimneys (= or <10m high). Recovered sulfide samples are predominantly the tops of chimneys and spires and typically contain more than 80% sphalerite and wurtzite with minor pyrrhotite, pyrite, marcasite, isocubanite, chalcopyrite, anhydrite, anhydrite, and amorphous silica. The associated hydrothermal fluids have the highest chlorinity of any reported to date.-Authors
Lizárraga-Mendiola, L; González-Sandoval, M R; Durán-Domínguez, M C; Márquez-Herrera, C
2009-08-01
The geochemical behavior of zinc, lead and copper from sulfidic tailings in a mine site with potential to generate acidic drainage (pyrite (55%) and sphalerite (2%)) is reported in this paper. The mining area is divided in two zones, considering the topographic location of sampling points with respect to the tailings pile: (a) outer zone, out of the probable influence of acid mine drainage (AMD) pollution, and (b) inner zone, probably influenced by AMD pollution. Maximum total ions concentrations (mg/L) measured in superficial waters found were, in the outer zone: As (0.2), Cd (0.9), Fe (19), Mn (39), Pb (5.02), SO4(2-) (4650), Zn (107.67), and in the inner zone are As (0.1), Cd (0.2), Fe (88), Mn (13), Pb (6), SO4(2-) (4,880), Zn (46). The presence of these ions that exceeding the permissible maximum limits for human consume, could be associated to tailings mineralogy and acid leachates generated in tailings pile.
Chemical dissolution of sulfide minerals
Chao, T.T.; Sanzolone, R.F.
1977-01-01
Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.
SiN-SiC nanofilm: A nano-functional ceramic with bipolar magnetic semiconducting character
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Jiahui; Li, Xingxing; Yang, Jinlong, E-mail: jlyang@ustc.edu.cn
2014-04-28
Nowadays, functional ceramics have been largely explored for application in various fields. However, magnetic functional ceramics for spintronics remain little studied. Here, we propose a nano-functional ceramic of sphalerite SiN-SiC nanofilm with intrinsic ferromagnetic order. Based on first principles calculations, the SiN-SiC nanofilm is found to be a ferromagnetic semiconductor with an indirect band gap of 1.71 eV. By mean field theory, the Curie temperature is estimated to be 304 K, close to room temperature. Furthermore, the valence band and conduction band states of the nanofilm exhibit inverse spin-polarization around the Fermi level. Thus, the SiN-SiC nanofilm is a typical bipolar magneticmore » semiconductor in which completely spin-polarized currents with reversible spin polarization can be created and controlled by applying a gate voltage. Such a nano-functional ceramic provides a possible route for electrical manipulation of carrier's spin orientation.« less
Mineralogy of ash of some American coals: variations with temperature and source
Mitchell, R.S.; Gluskoter, H.J.
1976-01-01
Ten samples of mineral-matter residue were obtained by the radio-frequency low-temperature ashing of subbituminous and bituminous coals. The low-temperature ash samples were then heated progressively from 400 ??C to 1400 ??C at 100 ??C intervals. Mineral phases present at each temperature interval were determined by X-ray diffraction analyses. The minerals originally present in the coals (quartz, kaolinite, illite, pyrite, calcite, gypsum, dolomite, and sphalerite) were all altered to higher temperature phases. Several of these phases, including kaolinite, metakaolinite, mullite, anhydrite, and anorthite, were found only in limited temperature ranges. Therefore the temperature of formation of the ashes in which they occur may be determined. Mineralogical differences were observed between coal samples from the Rocky Mountain Province, the Illinois Basin, and the Appalachians; and as a result of these mineralogical differences, different high-temperature phases resulted as the samples were heated. However, regional generalizations cannot be made until a greater number of samples have been studied. ?? 1976.
Electron microscopy and positron annihilation study of CdSe nanoclusters embedded in MgO
NASA Astrophysics Data System (ADS)
van Huis, M. A.; van Veen, A.; Schut, H.; Eijt, S. W. H.; Kooi, B. J.; De Hosson, J. Th. M.
2004-06-01
CdSe nanoclusters are created in MgO by means of co-implantation of 280 keV, 1 × 10 16 Cd ions cm -2 and 210 keV, 1 × 10 16 Se ions cm -2 in single crystals of MgO(0 0 1) and subsequent thermal annealing at a temperature of 1300 K. The structural properties and the orientation relationship between the CdSe and the MgO are investigated using cross-sectional transmission electron microscopy (XTEM). The crystal structure of the nanoclusters depends on their size. The smallest nanoclusters with a size below 5 nm have the cubic rocksalt crystal structure. The larger nanoclusters have a different (most likely the cubic sphalerite) crystal structure. The defect evolution in the sample after ion implantation and during thermal annealing is investigated using Doppler broadening positron beam analysis (PBA). The defect evolution in samples co-implanted with Cd and Se is compared to the defect evolution in samples implanted with only Cd or only Se ions.
Selective Sulfidation of Lead Smelter Slag with Sulfur
NASA Astrophysics Data System (ADS)
Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing
2016-02-01
The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.
Geology of the Bir Nifazi Quadrangle, Kingdom of Saudi Arabia
Quick, James E.; Bosch, Paul S.
1990-01-01
A north-trending, 10-km-long belt of gossans crops out within the ophiolite beneath the upper-basalt sequence at Jabal Mardah. Reconnaissance drilling indicates that one of the larger gossans is underlain by a steeply dipping, 15-m-thick, sulfide-rich volcanic wacke that averages 1 percent nickel locally. The ore is composed of pyrite, millerite, polydymite, and minor sphalerite that fill interstices between clasts of the wacke and are intimately intergrown with quartz and nickel-rich epidote and chlorite. These textures and assemblages suggest that the sulfides crystallized in situ from infiltrating hydrothermal fluids. Tuffs and basalt flows appear to have acted as impermeable barriers that channeled the hydrothermal fluids through the more permeable wacke where sulfides were deposited. Carbonate-replaced serpentinized peridotite at the base of the ophiolite is considered a potential source for the nickel. In contrast to most nickel deposits, the mineralized rocks at Jabal Mardah have extremely high Ni/Cu (130 to 260) and negligible concentrations (< 5 ppb) of platinum-group elements.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lemoine, Pierric, E-mail: pierric.lemoine@univ-rennes1.fr; Bourgès, Cédric; Barbier, Tristan
Ternary copper-containing sulfides Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu{sub 12}Sb{sub 4}S{sub 13} decomposes above ≈792 K into Cu{sub 3}SbS{sub 3}, and (ii) Cu{sub 4}Sn{sub 7}S{sub 16} decomposes above ≈891 K into Sn{sub 2}S{sub 3} and amore » copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu{sub 3}SnS{sub 4} stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu{sub 12}Sb{sub 4}S{sub 13} are in fair agreement with recent published data, the decomposition behavior of Cu{sub 4}Sn{sub 7}S{sub 16} differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu{sub 4}Sn{sub 7}S{sub 16} and tetrahedrite Cu{sub 12}Sb{sub 4}S{sub 13} phases at 300 K, and for the high temperature form of skinnerite Cu{sub 3}SbS{sub 3} at 843 K. - Graphical abstract: In situ neutron powder diffraction data (heating rate of 2.5 K/min) indicates that (i) the ternary Cu{sub 12}Sb{sub 4}S{sub 13} phase is stable up to 792 K and decomposes at higher temperature into Cu{sub 3}SbS{sub 3} and Cu{sub 1.5}Sb{sub 0.5}S{sub 2}, and (ii) the Cu{sub 4}Sn{sub 7}S{sub 16} phase is stable up to 891 K and decomposes at higher temperature into Sn{sub 2}S{sub 3} and a cubic phase of sphalerite ZnS-type structure. Sulfur volatilization likely occurs in order to balance the overall stoichiometry.« less
Thermomagnetic identification of manganese and iron minerals present in soils and industrial dusts
NASA Astrophysics Data System (ADS)
Wawer, Małgorzata; Rachwał, Marzena; Jabłońska, Mariola; Krzykawski, Tomasz; Magiera, Tadeusz
2017-04-01
Many industries (e.g. metallurgy, power, cement, and coking plants) constitute a sources of industrial dusts containing technogenic magnetic particles (TMP). TMP are mostly iron oxides with ferrimagnetic or antiferromagnetic properties, therefore their presence in dusts, soils and sediments can be easily detected by magnetic susceptibility measurements. TMP, thanks their specific mineral and magnetic properties, and well developed specific surface area, are characterized by a chemical affinity for some elements like heavy metals. The main objective of this study was identification of manganese and iron (hydro)oxides occurring in industrial dusts and soils being under their deposition for long time period. In principle, Mn and Fe (hydro)oxides present in these samples originate from high-temperature technological processes. Soils samples (collected from different soil horizons) taken from surroundings of power station, iron/steel and non-ferrous plants as well as metallurgical dusts and fly ashes from power stations were subjected to investigation. During the studies temperature dependent magnetic susceptibility measurements and X-ray powder diffraction analyses were applied. Thermomagnetic analyses (K-T) revealed differences between samples from particular industries, however an inflexion at 450-500°C of all curves was observed indicating a probable occurrence of maghemite- or titanomagnetite-like phases. The curves of TMP emitted by power plants have inflection at 580 °C indicating that magnetite was the main magnetic phase. In case of TMP originated from non-ferrous metal smelting additional curve deflection at 130 and 210 °C occurred relating to intermediate titanomagnetite or iron sulfides. X-ray diffraction proved the occurrence of magnetite and maghemite in almost all samples, especially connected with power industry and iron/steel metallurgy. Mineral analysis revealed that kind of industrial process influenced on the dominating mineral forms found in polluted soils and specific industrial dusts. Fly ashes were composed mainly of anhydrite (2-46%), quartz (18-33%), muscovite (0-8%), feldspar (0-8%) and hematite (2-8%), while different spinels (19-53%), hematite (0-38%), wüstite (0-40%) and additives of calcite, halite, sylvine and graphite are the components of metallurgical dusts. Dusts from non-ferrous metal smelting contain Pb and Zn minerals: zincite (1-95%), lanarkite (0-45%), gordaite (0-10%), challacoloite and sphalerite. Additionally, some rare minerals were found in these dusts, such as: anglesite, sphalerite, galena, metasideronatrite and in soil, coronadite. Acknowledgements: The research project received funding from the National Science Centre of Poland on the basis of the decision number DEC-2013/09/B/ST10/02227.
Mass-dependent cadmium isotopic variations in nature with emphasis on the marine environment
NASA Astrophysics Data System (ADS)
Schmitt, Anne-Désirée; Galer, Stephen J. G.; Abouchami, Wafa
2009-01-01
We report a survey of natural mass-dependent cadmium isotope fractionation measured by thermal ionization mass spectrometry using a double-spike technique (DS-TIMS). Over sixty samples of natural terrestrial Cd from diverse environments, including MORB, OIB, continental loess, hydrogenic and hydrothermal ferromanganese deposits, and sphalerites (both oceanic and from major continental ore deposits) were analysed. Our results are expressed in terms of ɛ 112/110Cd, which are deviations in 112Cd/ 110Cd from our in-house JMC Cd standard in parts per 10 4. The total ɛ 112/110Cd variation is relatively small, with a range of only 5 ɛ-units, and is one-to-two orders of magnitude smaller than that previously found in meteorites. The MORB, OIB and loess ɛ 112/110Cd values are similar and provide a good estimate for the bulk silicate Earth (BSE) value which is - 0.95 ± 0.12 relative to our Cd standard (ɛ 112/110Cd = + 0.16 relative to Münster JMC Cd). Taken together, these data suggest little Cd isotope fractionation takes place during crust-mantle segregation. Cd isotopic compositions of continental sphalerite (ZnS) deposits worldwide and high-temperature oceanic hydrothermal sulphides show remarkably similar ɛ 112/110Cd values, consistent with our estimate for the BSE. In contrast, mid-temperature oceanic sulphides from a single extinct hydrothermal chimney display over 4 ɛ-units variation — along with the most negative values. These variations are most probably caused by precipitation/redissolution of sulphide phases en route within the hydrothermal system. The ɛ 112/110Cd variability found in worldwide marine Fe-Mn deposits reflects the seawater Cd isotope signal upon precipitation from ambient seawater. A decrease in ɛ 112/110Cd is observed in passing from shallow-water Fe-Mn deposits to those from deeper waters (> 2000 m depth). This shift is explained by biological fractionation related to the uptake of dissolved seawater Cd by phytoplankton in the upper water column. The relatively uniform ɛ 112/110Cd values close to zero at great depths are consistent with regeneration and remineralization of Cd at depth. Our data suggest that Cd isotopes - much like the Cd/Ca ratio in foraminifera - could potentially serve as a proxy for past changes in biological productivity. The temporal Cd isotope record in a Fe-Mn crust archive at 2000 m depth from the NE Atlantic suggests no gross long-term changes in Cd cycling took place over the past 8 Ma.
Johnson, C.A.; Cardellach, E.; Tritlla, J.; Hanan, B.B.
1996-01-01
The Cierco Pb-Zn-Ag vein deposits, located in the central Pyrenees of Spain, crosscut Paleozoic metasedimentary rocks and are in close proximity to Hercynian granodiorite dikes and plutons. Galena and sphalerite in the deposits have average ??34S values of -4.3 and -0.8 per mil (CDT), respectively. Coexisting mineral pairs give an isotopic equilibration temperature range of 89?? to 163??C which overlaps with the 112?? to 198??C range obtained from primary fluid inclusions. Coexisting quartz has a ??18O value of 19 ?? 1 per mil (VSMOW). The fluid which deposited these minerals is inferred to have had ??18OH2o and ??34SH2s values of 5 ?? 1 and -1 ?? 1 per mil, respectively. Chemical and microthermometric analyses of fluid inclusions in quartz and sphalerite indicate salinities of 3 to 29 wt percent NaCl equiv with Na+ and Ca2+ as the dominant cations in solution. The Br/Cl and I/Cl ratios differ from those characteristic of magmatic waters and pristine seawater, but show some similarity to those observed in deep ground waters in crystalline terranes, basinal brines, and evaporated seawater, Barite, which postdates the sulfides, spans isotopic ranges of 13 to 21 per mil, 10 to 15 per mil, and 0.7109 to 0.7123 for ??34S, ??18O, and 87Sr/86Sr, respectively. The three parameters are correlated providing strong evidence that the barites are products of fluid mixing. We propose that the Cierco deposits formed along an extensional fault system at the margin of a marine basin during the breakup of Pangea at some time between the Early Triassic and Early Cretaceous. Sulfide deposition corresponded to an upwelling of hydrothermal fluid from the Paleozoic basement and was limited by the amount of metals carried by the fluid. Barite deposition corresponded to the waning of upward flow and the collapse of sulfate-rich surface waters onto the retreating hydrothermal plume. Calcite precipitated late in the paragenesis as meteoric or marine waters descended into the fault system, possibly during a regression in the overlying basin. There are other deposits resembling Cierco elsewhere in the Iberian peninsula. Taken as a group, they are evidence that hydrothermal circulation systems were widespread during Mesozoic extension. Differences among the deposits can be related to the fact that H2S and other solutes had local and variable sources.
NASA Astrophysics Data System (ADS)
Panfili, Frédéric; Manceau, Alain; Sarret, Géraldine; Spadini, Lorenzo; Kirpichtchikova, Tatiana; Bert, Valérie; Laboudigue, Agnès; Marcus, Matthew A.; Ahamdach, Noureddine; Libert, Marie-Françoise
2005-05-01
The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (A grostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg -1, [P 2O 5] = 7000 mg kg -1, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra. In the untreated and unvegetated sediment, Zn was distributed as ˜50% (mole ratio of total Zn) sphalerite, ˜40% Zn-ferrihydrite, and ˜10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (˜30˜40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate (˜40-60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (˜20-40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogeneous precipitation on mineral surface.
Selective Inhibition of the Oxidation of Ferrous Iron or Sulfur in Thiobacillus ferrooxidans
Harahuc, Lesia; Lizama, Hector M.; Suzuki, Isamu
2000-01-01
The oxidation of either ferrous iron or sulfur by Thiobacillus ferrooxidans was selectively inhibited or controlled by various anions, inhibitors, and osmotic pressure. Iron oxidation was more sensitive than sulfur oxidation to inhibition by chloride, phosphate, and nitrate at low concentrations (below 0.1 M) and also to inhibition by azide and cyanide. Sulfur oxidation was more sensitive than iron oxidation to the inhibitory effect of high osmotic pressure. These differences were evident not only between iron oxidation by iron-grown cells and sulfur oxidation by sulfur-grown cells but also between the iron and sulfur oxidation activities of the same iron-grown cells. Growth experiments with ferrous iron or sulfur as an oxidizable substrate confirmed the higher sensitivity of iron oxidation to inhibition by phosphate, chloride, azide, and cyanide. Sulfur oxidation was actually stimulated by 50 mM phosphate or chloride. Leaching of Fe and Zn from pyrite (FeS2) and sphalerite (ZnS) by T. ferrooxidans was differentially affected by phosphate and chloride, which inhibited the solubilization of Fe without significantly affecting the solubilization of Zn. PMID:10698768
Use of bioassays for testing soils and/or sediments contaminated by mining activities
NASA Astrophysics Data System (ADS)
Pérez-Sirvent, C.; Martínez-Sánchez, M. J.; García-Lorenzo, M. L.; Molina, J.
2009-04-01
Ecotoxicity tests measure the bioavailability of the contaminants and the effects of the chemically not measured toxic compounds on the members of the soil community. Therefore, ecotoxicological testing may be a useful approach for assessing the toxicity as a complement to chemical analysis. They are solid phase tests based on terrestrial methods and tests performed on water extracts using aquatic test protocols. The extent and degree of heavy metal contamination around mines may vary depending on geochemical characteristics, the mineralization of tailings, physico-chemical conditions and the processes used to extract metals. Portman Bay was subject to mining from the time of the Roman Empire to 1991 when the activity ceased. Since 1957, the wastes from mining operations were discharged directly into the sea. These wastes mainly consisted of clay, quartz, siderite, magnetite, remains of sphalerite, pyrite and galena and residues of the chemical reagents used in floatation. In our study two methods of environmental toxicological tests were compared and applied to sediments of the Portman Bay (SE, Spain): the standardized toxicological test based on inhibition of luminescence employing Microtox
NASA Astrophysics Data System (ADS)
Johnson, Aaron W.; Shelton, Kevin L.; Gregg, Jay M.; Somerville, Ian D.; Wright, Wayne R.; Nagy, Zsolt R.
2009-05-01
This study provides a regional framework within which studies of ore-related dolomite and dolomite cements may be placed. Fluid inclusion data indicate the presence of three distinct fluids following early dolomitization: 1) a ubiquitous low-temperature, higher salinity fluid found in saddle dolomite; 2) a low-temperature, lower salinity fluid limited to sub-Waulsortian and Waulsortian carbonates; and 3) a higher temperature, lower salinity fluid found in Waulsortian and supra-Waulsortian rocks. Similar fluids have been reported in ore-associated minerals and postmineralization dolomite (Type 1) and in ore-stage carbonates and sphalerite (Types 2 and 3). The halogen geochemistry of included fluids indicates genesis from evaporated seawater. Type 1 fluids are enriched in chloride relative to bromide, reflecting a component of salinity derived via dissolution of halite or from dehydration of seawater. These data suggest that dolomitization and mineralization of Mississippian rocks in the Midlands requires both regionally extensive and localized fluid flow.
Modes of occurrence of potentially hazardous elements in coal: levels of confidence
Finkelman, R.B.
1994-01-01
The modes of occurrence of the potentially hazardous elements in coal will be of significance in any attempt to reduce their mobilization due to coal combustion. Antimony and selenium may be present in solid solution in pyrite, as minute accessory sulfides dispersed throughout the organic matrix, or in organic association. Because of these modes of occurrence it is anticipated that less than 50% of these elements will be routinely removed by conventional coal cleaning procedures. Arsenic and mercury occur primarily in late-stage coarse-grained pyrite therefore physical coal cleaning procedures should be successful in removing substantial proportions of these elements. Cadmium occurs in sphalerite and lead in galena. Both of these minerals exhibit a wide range of particle sizes and textural relations. Depending on the particle size and textural relations, physical coal cleaning may remove as little as 25% of these elements or as much as 75%. Manganese in bituminous coal occurs in carbonates, especially siderite. Physical coal cleaning should remove a substantial proportion of this element. More information is needed to elucidate the modes of occurrence of beryllium, chromium, cobalt, and nickel. ?? 1994.
NASA Astrophysics Data System (ADS)
Vančo, Ľubomír; Kadlečíková, Magdaléna; Breza, Juraj; Čaplovič, Ľubomír; Gregor, Miloš
2013-01-01
In this paper we studied the material composition of the ground layer of a neoclassical painting. We used Raman spectroscopy (RS) as a prime method. Thereafter scanning electron microscopy combined with energy dispersive spectroscopy (SEM-EDS) and X-ray powder diffraction (XRD) were employed as complementary techniques. The painting inspected was of the side altar in King St. Stephen's Church in Galanta (Slovakia), signed and dated by Jos. Chr. Mayer 1870. Analysis was carried out on both covered and uncovered ground layers. Four principal compounds (barite, lead white, calcite, dolomite) and two minor compounds (sphalerite, quartz) were identified. This ground composition is consistent with the 19th century painting technique used in Central Europe consisting of white pigments and white fillers. Transformation of lead white occurred under laser irradiation. Subdominant Raman peaks of the components were measured. The observed results elucidate useful partnership of RS and SEM-EDS measurements supported by X-ray powder diffraction as well as possibilities and limitations of non-destructive analysis of covered lower layers by RS.
Leach, D.; Macquar, J.-C.; Lagneau, V.; Leventhal, J.; Emsbo, P.; Premo, W.
2006-01-01
The Trèves zinc–lead deposit is one of several Mississippi Valley-type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ34S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to −21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur-rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore-forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault-controlled and mineralogically similar MVT deposits in the Cévennes region.
NASA Astrophysics Data System (ADS)
Kelley, Karen D.; Selby, David; Falck, Hendrik; Slack, John F.
2017-03-01
Stratiform Zn-Pb deposits hosted in unmetamorphosed carbonaceous and siliceous mudstones of the Ordovician to Silurian Duo Lake Formation define the Howards Pass district in Yukon Territory and Northwest Territories, western Canada. Collectively, the deposits are amongst the largest in the world, containing drill-indicated and inferred resources of 423 Mt at 4.84 % Zn and 1.59 % Pb. Sulphide textures include (a) fine-scale laminations of sphalerite, galena, and pyrite from <0.05 mm to 1 cm thick, interbedded with carbonaceous sedimentary rock; (b) layers of coarse sulphide that are structurally controlled by microfolds; and (c) veins that cut bedding and sulphide laminations. The finely interlaminated nature of sulphides with mudstone has been used as evidence for syngenetic mineralizing processes, whereas paleomagnetic data determined on coarse layered sulphides suggest a Middle Jurassic age of mineralization. Here, we present new rhenium-osmium (Re-Os) isotopic data for 12 pyrite separates obtained from 4 laminated sulphide-rich samples from the XY Central (XYC) and Don (DON) deposits and for 1 unmineralized organic-rich mudstone ˜20 m stratigraphically below the sulphide-bearing zone. Pyrite separates that lack mudstone inclusions ("pure") from the XYC deposit contain 2.2 to 4.0 ppb Re and 93.4 to 123.4 ppt Os; pure pyrite from the DON deposit is significantly more enriched in Re and Os (34-37 ppb Re; 636.8-694.9 ppt Os). The 187Re/188Os values of pure pyrite separates from the XYC and DON deposits range from 137.6 to 197 and 182.1 to 201.4, respectively. Regression of all pure pyrite Re-Os data from both deposits yields an isochron age of 442 ± 14 Ma (MSWD = 7.4) and an initial 187Os/188Os (Osi) value of 0.71 ± 0.07. The Re-Os age indicates that the early phase of pyrite precipitation (and by inference, sphalerite and galena) occurred during the early Silurian, consistent with biostratigraphic ages of the host rocks. The Osi value of ˜0.8 for earliest Silurian seawater recorded from organic-rich shale in the basal Silurian Global Stratotype Section and Point (GSSP) at Dobs Linn, Scotland is very similar to that provided by the Howards Pass pyrite regression and hence suggests a hydrogenous (seawater) source of Os for the pyrite. Therefore, two possible sources of Os are (1) the Zn- and Pb-bearing hydrothermal fluid that leached Os from footwall sedimentary rocks, which were deposited in seawater, or (2) directly from seawater during precipitation of the pyrite, which suggests that the Os content of the hydrothermal fluid was minor relative to that of seawater.
Slack, John F.; Shanks, Wayne C.; Karl, Susan M.; Gemery, Pamela A.; Bittenbender, Peter E.; Ridley, W. Ian
2007-01-01
Stratabound volcanogenic massive sulfide (VMS) deposits on Prince of Wales Island and vicinity, southeastern Alaska, occur in two volcanosedimentary sequences of Late Proterozoic through Cambrian and of Ordovician through Early Silurian age. This study presents geochemical data on sulfide-rich samples, in situ laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of sulfide minerals, and sulfur-isotopic analyses of sulfides and sulfates (barite) for identifying and distinguishing between primary sea-floor signatures and later regional metamorphic overprints. These datasets are also used here in an attempt to discriminate the VMS deposits in the older Wales Group from those in the younger Moira Sound unit (new informal name). The Wales Group and its contained VMS deposits have been multiply deformed and metamorphosed from greenschist to amphibolite grade, whereas the Moira Sound unit and related VMS deposits are less deformed and generally less metamorphosed (lower to middle greenschist grade). Variations in the sulfide mineral assemblages and textures of the VMS deposits in both sequences reflect a combination of processes, including primary sea-floor mineralization and sub-sea-floor zone refining, followed by metamorphic recrystallization. Very coarse grained (>1 cm diam) sulfide minerals and abundant pyrrhotite are restricted to VMS deposits in a small area of the Wales Group, at Khayyam and Stumble-On, which record high-grade metamorphism of the sulfides. Geochemical and sulfur-isotopic data distinguish the VMS deposits in the Wales Group from those in the Moira Sound unit. Although base- and precious-metal contents vary widely in sulfide-rich samples from both sequences, samples from the Moira Sound generally have proportionately higher Ag contents relative to base metals and Au. In situ LA-ICP-MS analysis of trace elements in the sulfide minerals suggests that primary sea-floor hydrothermal signatures are preserved in some samples (for example, Mn, As, Sb, and Tl in pyrite from the Moira Sound unit), whereas in other samples the signatures are varyingly annealed, owing to metamorphic overprinting. A limited LA-ICP-MS database for sphalerite indicates that low-Fe sphalerite is preferentially associated with the most Au rich deposits, the Niblack and Nutkwa. Sulfur-isotopic values for sulfide minerals in the VMS deposits in the Wales Group range from 5.9 to 17.4 permil (avg 11.5?2.7 permil), about 5 to 6 permil higher than those in the Moira Sound unit, which range from -2.8 to 10.4 permil (avg 6.1?4.0 permil). This difference in 34Ssulfide values reflects a dominantly seawater sulfate source of the sulfides and is linked to the 34S values of contemporaneous seawater sulfate, which were slightly higher during the Late Proterozoic through Cambrian than during the Ordovician through Early Silurian.
Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico
NASA Astrophysics Data System (ADS)
Jimenez, A.
2012-04-01
Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico Abigail Jimenez-Franco1*, Pura Alfonso Abella2, Carles Canet3, Eduardo González-Partida4 1 Posgrado en Ciencias de la Tierra, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 2 Departament d'Enginyeria Minera i Recursos Naturals, Universitat Politècnica de Catalunya, Av de Les Bases de Manresa 61-73, 08242 Manresa. 3Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 4Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico The Velardeña mining district is located in north-eastern part of the state of Durango, in northern of Mexico. The ore deposit is a lead-zinc, garnet-rich skarn developed at the contact between granite porphyry dikes (Eocene) and well-laminated limestones with interbedded chert (Albian-Cenomanian). A study of sulfur isotopes has been carried out in various sulfide minerals of the ores of Velardeña, in order to: (a) constrain the possible sources of sulfur and, therefore, better understand the sulfide mineralizing processes, and (b) to estimate the temperature of the ore-forming stage of the skarn. Sulfur isotope analyses were performed in 21 pure fractions of sulfide minerals of the ore mineralization (pyrite, chalcopyrite, sphalerite and galena). The mineral separation was performed using a series of sieves, and the purity of the samples was verified under a binocular microscope. Isotopic analyses were done on a Finnigan MAT Delta C flow elemental analyzer coupled to a TC-EA, according with the method of Giesemann et al. (1974). The δ34S values of the analyzed sulfides range mostly between -0.6 and +2.6 ‰ (relative to the CDT standard). These values are indicative of a magmatic source of sulfur. A single analysis falls outside the common range of magmatic sulfur; it corresponds to a sphalerite crystal with δ34S of -3.9 ‰. This negative value could be explained by the incorporation of sulfur leached from the sedimentary host rocks. Pyrite and galena in paragenesis were analyzed from one sample (CO-9F); the isotope fractionation equation of Ohmoto and Rye (1979) was applied for geothermometry purposes. This calculation yields a temperature of 346° ±25° C, from fractionation Δpyrite-galena of 2.66 ‰.
NASA Astrophysics Data System (ADS)
Hammerli, J.; Rusk, B.; Spandler, C.; Oliver, N. H. S.; Emsbo, P.
2012-04-01
Chlorine and bromine are highly conservative elements, and are therefore widely used to trace the origin of fluids in sedimentary and hydrothermal/magmatic systems (e.g. Hanor & McIntosh, 2007; Nahnybida et al., 2009). Halogens are important ligands for metal transport in hydrothermal solutions and thus their behavior in hydrothermal environments is crucial for comprehending ore-forming processes. Besides fluid inclusions, scapolite-group minerals hold great potential as a tracer of igneous, metamorphic, and hydrothermal processes, as no Cl/Br fractionation in scapolite has been observed and therefore halogen ratios in scapolite are thought to mirror the halogen ratios in coexisting melts and fluids (Pan & Dong, 2003). Hence, Cl/Br ratios in fluid inclusions and minerals can be utilized to trace the origin of fluids and fluid-rock interaction pathways. Due to their high ionization energies, bromine and chlorine are not routinely measured by LA-ICP-MS and suitable standards are rare. Little is known about the potential interferences and analytical limitations of in-situ chlorine and bromine analysis by LA-ICP-MS. Nevertheless, Seo et al. (2011) showed that quantification of Br and Cl in single synthetic and natural fluid inclusions is possible. In this study, we have analyzed several scapolite grains of known bromine and chlorine concentrations by LA-ICP-MS and assess the capabilities and limitations of this method. The results show that Cl/Br ratios measured by LA-ICP-MS closely reproduce known values determined by microprobe (Cl), the Noble Gas Method (Br) and INAA (Br) (Kendrick, 2011; Lieftink et al., 1993) using laser ablation spot sizes from 24-120 μm. The well-characterized scapolite grains cover bromine concentrations from 50-883 ppm and chlorine concentrations from 3 to 4 wt.%. In order to further assess the method, we analyzed Cl/Br ratios in natural fluid inclusions hosted in sphalerite that were previously characterized by crush and leach ion chromatography. This is the first time that bulk crush and leach Cl/Br analyses can be compared with Cl/Br ratios within individual fluid inclusions. Our LA-ICP-MS measurements are in good agreement with bulk crush and leach analyses. For instance, molar Cl/Br ratios of single fluid inclusions (183±33) in sphalerite form East Tennessee match those obtained by crush and leach (206±8) Additionally, scapolite in samples from dykes of the Burstall granite, associated banded skarns and metasediments from the Mary Kathleen Fold Belt, Queensland, Australia are being studied. Scapolite is highly luminescent and therefore, cathodoluminescence images resolve chemical zoning in scapolite group minerals that, in combination with in-situ Cl/Br analyses, is a powerful tool to better understand fluid sources and fluid-rock interaction within various geological environments.
NASA Astrophysics Data System (ADS)
Li, Tiegang; Wu, Guang; Liu, Jun; Wang, Guorui; Hu, Yanqing; Zhang, Yunfu; Luo, Dafeng; Mao, Zhihao; Xu, Bei
2016-09-01
The large Chaganbulagen Pb-Zn-Ag deposit is located in the Derbugan metallogenic belt of the northern Great Xing'an Range. The vein-style orebodies of the deposit occur in the NWW-trending fault zones. The ore-forming process at the deposit can be divided into three stages: an early quartz-pyrite-arsenopyrite-pyrrhotite-sphalerite-galena-chalcopyrite stage, a middle quartz-carbonate-pyrite-sphalerite-galena-silver-bearing minerals stage, and a late quartz-carbonate-pyrite stage. The sericite sample yielded a 40Ar -39Ar plateau age of 138 ± 1 Ma and an isochron age of 137 ± 3 Ma, and the zircon LA-ICP-MS U-Pb age of monzogranite porphyry was 143 ± 2 Ma, indicating that the ages of mineralization and monzogranite porphyry in the Chaganbulagen deposit should be the Early Cretaceous, and that the mineralization should be slightly later than the intrusion of monzogranite porphyry. There are only liquid inclusions in quartz veins of the Chaganbulagen deposit. Homogenization temperatures, densities, and salinities of the fluid inclusions from the early stage are 261-340 °C, 0.65-0.81 g/cm3, and 0.7-6.3 wt.% NaCl eqv., respectively. Fluid inclusions of the middle stage have homogenization temperatures, densities, and salinities of 209-265 °C, 0.75-0.86 g/cm3, and 0.5-5.7 wt.% NaCl eqv., respectively. For fluid inclusions of the late stage, their homogenization temperatures, densities, and salinities are 173-219 °C, 0.85-0.91 g/cm3, and 0.4-2.7 wt.% NaCl eqv., respectively. The ore-forming fluids of the deposit are generally characterized by moderate temperature and low salinity and density, and belong to an H2O-NaCl ± CO2 ± CH4 system. The δ18Owater values calculated for ore-bearing quartz vary from - 17.9‰ to - 10.8‰, and the δDV-SMOW values from bulk extraction of fluid inclusion waters vary from - 166‰ to - 127‰, suggesting that the ore-forming fluids consist dominantly of meteoric water. The δ34SV-CDT values range from 1.4‰ to 4.1‰. The 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb values of the ore minerals are in the ranges of 18.302-19.037, 15.473-15.593, and 38.110-38.945, respectively. The data for the S and Pb isotopic systems indicate that the ore-forming metals and sulfur came from Mesozoic magma. The Chaganbulagen deposit is a low-sulfidation epithermal Pb-Zn-Ag deposit, and the temperature decrease is the dominant mechanism for the deposition of ore-forming materials.
Geology of the Copper King Mine area, Prairie Divide, Larimer County, Colorado (Part 1)
Sims, Paul Kibler; Phair, George
1952-01-01
The Copper King mine, in Larimer County, Colo., in the northern part of the Front Range of Colorado, was operated for a short time prior to World War II for copper and zino, but since 1949, when pitchblende was discovered on the mine dump, it has been worked for uranium. The bedrock in the mine area consists predominantly of pre-Cambrian (Silver Plums) granite with minor migmatite and metasediments--biotite-quartz-plagioclase gneiss, biotite schist, quartzite, amphibolite, amphibole skarn, and biotite skols. The metasediments occur as inclusions that trend northeast in the granite. This trend is essentially parallel to the prevailing foliation in the granite. At places the metasediments are crosscut sharply by the granite to form angular, partly discordant, steep-walled bodies in the granite. Faults, confined to a narrow zone that extends through the mine, cut both the pre-Cambrian rocks and the contained sulfide deposits. The Copper King fault, a breccia zone, contains a deposit of pitchblende; the other faults are believed to be later than the ore. The two types of mineral deposits--massive sulfide and pitchblende deposits--in the mine area, are of widely different mineralogy, age, and origin. The massive sulfide deposits are small and consist of pyrite, sphalerite, chalcopyrite, pyrrhotite, and in places magnetite in amphibole skarn, mice skols, and quartzite. The deposit at the Copper King mine has yielded small quantities of high-grade sphalerite ore. The massive sulfides are pyrometasomatic deposits of pre-Cambrian age. The pitchblende at the Copper King mine is principally in the Copper King vein, a tight, hard breccia zone that cuts through both granite and the massive sulfide deposit. A small part of the pitchblende is in small fractures near the vein and in boxwork pyrite adjacent to the vein; the post-ore faults, close to their intersection with the Copper King vein, contain some radioactive material, but elsewhere, so far as is known, they are barren. The pitchblende in the deposit forms a steeply plunging ore shoot that has a horizontal length of more than 50 feet and a vertical height of about 85 feet. The thickness of the ore shoot averages about 2 feet, but it ranges from a feather edge to about 4 feet. The hard pitch-blende is intimately intergrown with siderite; other gangue minerals include pyrite, quartz, and finely comminuted fragments of the wall rocks. The vein was repeatedly reopened during mineral deposition as shown by several stages of brecciation and recommended by the vein matter. The pitchblende deposit probably formed at intermediate temperatures and depths and, according to the Pb/U ratio, is about 60 million years old--an early Tertiary age.
Evolution of the Bucium Rodu and Frasin magmatic-hydrothermal system, Metaliferi Mountains, Romania
NASA Astrophysics Data System (ADS)
Iatan, Elena Luisa; Berbeleac, Ion; Visan, Madalina; Minut, Adrian; Nadasan, Laurentiu
2013-04-01
The Miocene Bucium Rodu and Frasin maar-diatreme structures and related Au-Ag epithermal low sulfidation with passing to mesothermal mineralizations are located in the Bucium-Rosia Montana-Baia de Aries metallogenetic district, within so called the "Golden Quatrilaterum", in the northeastern part of the Metaliferi Mountains. These structures are situated at about 5 km southeast from Rosia Montana, the largest European Au-Ag deposit. The total reserves for Bucium Rodu-Frasin are estimated at 43.3 Mt with average contents of 1.3 g/t Au and 3 g/t Ag. The Miocene geological evolution of Bucium Rodu and Frasin magmatic-hydrothermal system took place in closely relationships with tectonic, magmatic and metallogenetic activity from Bucium-Rosia Montana-Baia de Aries district in general, and adjacent areas, in special. The hydrothermal alteration is pervasive; adularia followed by phyllic, carbonatization and silicification alterations, usually show a close relationship with the mineralizations. Propylitic alteration occurs dominantly towards the depth; argillic alteration shows a local character. The mineralization occurs in veins, breccias, stockworks and disseminations and is hosted within two volcanic structures emplaced into a sequence of Cretaceous sediments in closely genetically relations with the Miocene phreatomagmatic fracturing and brecciation events. Within Rodu maar-diatreme structure the mineralizations follow especially the contact between the diatreme and Cretaceous flysch. The vein sets with low, moderately and near vertical dippings, cover 400x400m with N-S trend. The most important mineralization style is represented by veins, accompanied by hydrothermal breccias and disseminations. The veins spatial distribution relives as "en echelon" tension veins. They carry gold, minor base metal sulphides (pyrite, chalcopyrite, sphalerite, galena, tetrahedrite, arsenopyrite). Gangue is represented by carbonates (calcite, dolomite, ankerite, siderite, rhodochrosite) and quartz. In contrast, in Frasin maar-diatreme structure, the mineralizations are focused especially along the northeastern contact between the andesite dome and polimictic breccias. Stockwork is the main style of mineralization and consists of pyrite, small amounts of chalcopyrite, sphalerite, galena, arsenopyrite and gold within a gangue of quartz and carbonates similar to Rodu mineralizations. The ore minerals deposition from hydrothermal fluids have pulsated character with a three stage evolution and mineral assemblages: 1) magnetite (hematite) - pyrite (marcasite) - quartz in the first stage, epithermal low sulfidation with passing to mesothermal; 2) arsenopyrite (Au) - (-base metal sulfides) - quartz, "Chinga" (pyrite (Au)-quartz-adularia) - carbonates (calcite, aragonite, dolomite, ankerite, ± rhodochrosite ± kutnahorite) - quartz - adularia in the second stage, epithermal low sulfidation and 3) pyrite - marcasite - carbonates - quartz, (Au) - carbonates (dominant rhodochrosite) - quartz - adularia and alabandite - rhodochrosite - quartz in the third stage, epithermal low sulfidation. The mineralizing hydrothermal fluids had near neutral pH with the gold transported probably as a bisulfide complex; boiling seems to be the main way of gold precipitation.
NASA Astrophysics Data System (ADS)
Maurya, Sandeep Kumar; Liu, Ya; Xu, Xiaojie; Woods-Robinson, Rachel; Das, Chandan; Ager, Joel W., III; Balasubramaniam, K. R.
2017-12-01
p-type transparent conducting Cu alloyed ZnS thin films from Cu{x} Zn{1-x} S targets (x = 0.1 , 0.2, 0.3, 0.4, and 0.5) were deposited on glass substrates via radio frequency sputtering. x-ray diffraction and TEM-SAED analysis show that all the films have sphalerite ZnS as the majority crystalline phase. In addition, films with 30% and 40% Cu show the presence of increasing amounts of crystalline Cu2S phase. Conductivity values ⩾400 S cm-1 were obtained for the films having 30% and 40% Cu, with the maximum conductivity of 752 S cm-1 obtained for the film with 40% Cu. Temperature dependent electrical transport measurements indicate metallic as well as degenerate hole conductivity in the deposited films. The reflection-corrected transmittance of this Cu alloyed ZnS (40% Cu) film was determined to be ⩾75% at 550 nm. The transparent conductor figure of merit (ΦTC ) of the Cu alloyed ZnS (40% Cu), calculated with the average value of transmittance between 1.5 to 2.5 eV, was ≈276 μS .
Fang, Zhibin; Weng, Sunxian; Ye, Xinxin; Feng, Wenhui; Zheng, Zuyang; Lu, Meiliang; Lin, Sen; Fu, Xianzhi; Liu, Ping
2015-07-01
ZnS is among the superior photocatalysts for H2 evolution, whereas the wide bandgap restricts its performance to only UV region. Herein, defect engineering and phase junction architecture from a controllable phase transformation enable ZnS to achieve the conflicting visible-light-driven activities for H2 evolution. On the basis of first-principle density functional theory calculations, electron spin resonance and photoluminescence results, etc., it is initially proposed that the regulated sulfur vacancies in wurtzite phase of ZnS play the key role of photosensitization units for charge generation in visible light and active sites for effective electron utilization. The symbiotic sphalerite-wurtzite phase junctions that dominate the charge-transfer kinetics for photoexciton separation are the indispensable configuration in the present systems. Neither ZnS samples without phase junction nor those without enough sulfur vacancies conduct visible-light photocatalytic H2 evolution, while the one with optimized phase junctions and maximum sulfur vacancies shows considerable photocatalytic activity. This work will not only contribute to the realization of visible light photocatalysis for wide-bandgap semiconductors but also broaden the vision on the design of highly efficient transition metal sulfide photocatalysts.
Synthesis of CuInSe2 nanocrystals using a continuous hot-injection microreactor
NASA Astrophysics Data System (ADS)
Jin, Hyung Dae; Chang, Chih-Hung
2012-10-01
A very rapid and simple synthesis of CuInSe2 nanocrystals (NCs) was successfully performed using a continuous hot-injection microreactor with a high throughput per reactor volume. It was found that copper-rich CuInSe2 with a sphalerite structure was formed initially followed by the formation of more ordered CuInSe2 at longer reaction times along with the formation of Cu2Se and In2Se3. Binary syntheses were performed and the results show a much faster formation rate of Cu2Se than In2Se3. The rate limiting step in the formation of CuInSe2 is forming the In2Se3 intermediate. Rapid synthesis of stoichiometric CuInSe2 NCs using a continuous-flow microreactor was accomplished by properly adjusting the Cu/In precursor ratio. Tuning the ratio of coordinating solvents can cause size differences from 2.6 to 4.1 nm, bandgaps from 1.1 to 1.3 eV, and different production yields of NCs. The highest production yield as determined by weight was achieved up to 660 mg/h using a microreactor with a small volume of 3.2 cm3.
Rye, R.O.; Roberts, R.J.; Snyder, W.S.; Lahusen, G.L.; Motica, J.E.
1984-01-01
The Big Mike deposit is a massive sulphide lens entirely within a carbonaceous argillite of the Palaeozoic Havallah pelagic sequence. The massive ore contains two generations of pyrite, a fine- and a coarse-grained variety; framboidal pyrite occurs in the surrounding carbonaceous argillite. Coarse grained pyrite is largely recrystallized fine-grained pyrite and is proportionately more abundant toward the margins of the lens. Chalcopyrite and sphalerite replace fine-grained pyrite and vein-fragmented coarse-grained pyrite. Quartz fills openings in the sulphide fabric. S-isotope data are related to sulphide mineralogy and textures. Isotopically light S in the early fine-grained pyrite was probably derived from framboidal biogenic pyrite. The S-isotope values of the later coarse-grained pyrite and chalcopyrite probably reflect a combination of reduced sea-water sulphate and igneous S. Combined S- and O-isotope and textural data accord with precipitation of fine-grained pyrite from a hydrothermal plume like those at the East Pacific Rise spreading centre at lat. 21oN. The primary material was recystallized and mineralized by later fluids of distinctly different S-isotope composition. -G.J.N.
Foley, Nora; Jaskula, Brian W.
2013-01-01
Gallium is a soft, silvery metallic element with an atomic number of 31 and the chemical symbol Ga. The French chemist Paul-Emile Lecoq de Boisbaudran discovered gallium in sphalerite (a zinc-sulfide mineral) in 1875 using spectroscopy. He named the element "gallia" after his native land of France (formerly Gaul; in Latin, Gallia). The existence of gallium had been predicted in 1871 by Dmitri Mendeleev, the Russian chemist who published the first periodic table of the elements. Mendeleev noted a gap in his table and named the missing element "eka-aluminum" because he determined that its location was one place away from aluminum in the table. Mendeleev thought that the missing element (gallium) would be very much like aluminum in its chemical properties, and he was right. Solid gallium has a low melting temperature (~29 degrees Celsius, or °C) and an unusually high boiling point (~2,204 °C). Because of these properties, the earliest uses of gallium were in high-temperature thermometers and in designing metal alloys that melt easily. The development of a gallium-based direct band-gap semiconductor in the 1960s led to what is now one of the most well-known applications for gallium-based products--the manufacture of smartphones and data-centric networks.
Electronic structure and linear optical properties of ZnSe and ZnSe:Mn.
Su, Kang; Wang, Yuhua
2010-03-01
As an important wide band-gap II-VI semiconductor, ZnSe has attracted much attention for its various applications in photo-electronic devices such as blue light-emitting diodes and blue-green diode lasers. Mn-doped ZnSe is an excellent quantum dot material. The electronic structures of the sphalerite ZnSe and ZnSe:Mn were calculated using the Vienna ab initio Simulation Package with ultra-soft pseudo potentials and Material Studio. The calculated equilibrium lattice constants agree well with the experimental values. Using the optimized equilibrium lattice constants, the densities of states and energy band structures were further calculated. By analyzing the partial densities of states, the contributions of different electron states in different atoms were estimated. The p states of Zn mostly contribute to the top of the valence band, and the s states of Zn and the s states of Se have major effects on the bottom of the conduction band. The calculated results of ZnSe:Mn show the band gap was changed from 2.48 to 1.1 eV. The calculated linear optical properties, such as refractive index and absorption spectrum, are in good agreement with experimental values.
Heyl, Allen Van; Lyons, Erwin J.; Agnew, Allen F.
1951-01-01
The U. S. Geological Survey in cooperation with the Wisconsin Geological and Natural History Survey explored the Prairie du Chien group in the main productive area of the Wisconsin zinc-lead district during 1949-50. Eight properties--Crow Branch diggings, Leix, Harris, Spitzbarth, Kennedy, James, Raisbeck and Vinegar Hill Roaster--were explored using both diamond and churn drills. Twenty holes were drilled that totaled 8,582 feet in depth. The objectives of the exploration were to determine if the Prairie du Chien and other formations below the principal ore-bearing strata (Galena, Decorah, and Platteville formations) of the district are favorable for ore deposits, and to determine the type of ore deposits, if present. Lean deposits of sphalerite, marcasite, and pyrite were found in the Prairie du Chien on five properties--Crow Branch, Leix, Harris, Spitzbarth, and Vinegar Hill 1%ouster-and also in the Franconia sandstone on the Leix property. In the drilled area the sulfides in the Prairie du Chien group occur in certain more brittle or soluble dolomite beds that contain cavities formed by brecciation or solution.
Aqueous pyrite oxidation by dissolved oxygen and by ferric iron
Moses, Carl O.; Nordstrom, D. Kirk; Herman, Janet S.; Mills, Aaron L.
1987-01-01
Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.
NASA Astrophysics Data System (ADS)
Ball, T. K.; Basham, I. R.
1984-01-01
The Bosworgey granite cusp forms an apical portion of the concealed northern extension of the Tregonning-Godolphin granite ridge. It is characterised by unusually high values of B, P, Mn, Fe, As, Cu, Nb, Ta, Bi, Sn, W, U and S which are present largely as tourmaline, apatite, pyrite, arsenopyrite, chalcopyrite, bismuth, columbite, cassiterite, wolframite and uraninite; and low levels of Zr, Hf, Ti and REE present in zircon, ilmenite and monazite. The granite is classified as Sn and W “specialised” (Tischendorf, 1974) and it belongs to the ilmenite series of Japanese workers. The classification of Chappell and White (1974) (“S” and “I” type granites) is shown to be inapplicable to Cornubian rocks although the Bosworgey samples show characteristics of “S” type granites. The accessory mineral assemblages are typical of high temperature lodes (cassiterite, wolframite, arsenopyrite, chalcopyrite) and the assamblage is concluded to be the cusp analogue of hypothermal lodes produced by extreme differentiation and concentration of volatiles. It is speculated that such granites could provide the parent material for the mesothermal crosscourse mineralisation (pitchblende, bismuth, pyrite, galena, sphalerite).
Mauk, Jeffrey L.; Skinner, Erin G; Fyfe, Sarah J; Menzies, Andrew H; Lowers, Heather A.; Koenig, Alan E.
2016-01-01
The Waihi district in the Hauraki Goldfield of New Zealand contains adularia-sericite epithermal gold-silver veins that have produced more than 7.7 Moz gold. The outermost veins of the district (Martha, Favona, Moonlight, and Cowshed) contain abundant colloform, cherty, and black quartz fill textures, with minor crustiform and massive quartz. The central veins (Amaranth, Trio, and Union) contain predominantly massive and crustiform textures, and these veins are also commonly coarser grained than outermost veins. Pyrite, sphalerite, galena, chalcopyrite, electrum, and acanthite occur in both outermost and central veins; base metal sulfide minerals typically increase in abundance in deeper samples. Antimony-, arsenic-, and selenium-bearing minerals are most abundant in the Favona and Moonlight veins, whereas base metal sulfide minerals are more abundant in the central veins at Correnso. Throughout the Waihi vein system, electrum is by far the most widespread, abundant, and significant gold-bearing mineral, but LA-ICP-MS analyses show that arsenian pyrite also contains some gold. Mineralogical and textural data are consistent with the central veins forming at a deeper structural level, or from hydrothermal fluids with different chemistry, or both.
Establishing the environmental risk of metal contaminated river bank sediments
NASA Astrophysics Data System (ADS)
Lynch, Sarah; Batty, Lesley; Byrne, Patrick
2016-04-01
Climate change predictions indicate an increase in the frequency and duration of flood events along with longer dry antecedent conditions, which could alter patterns of trace metal release from contaminated river bank sediments. This study took a laboratory mesocosm approach. Chemical analysis of water and sediment samples allowed the patterns of Pb and Zn release and key mechanisms controlling Pb and Zn mobility to be determined. Trace metal contaminants Pb and Zn were released throughout flooded periods. The highest concentrations of dissolved Pb were observed at the end of the longest flood period and high concentrations of dissolved Zn were released at the start of a flood. These concentrations were found to exceed environmental quality standards. Key mechanisms controlling mobility were (i) evaporation, precipitation and dissolution of Zn sulphate salts, (ii) anglesite solubility control of dissolved Pb, (iii) oxidation of galena and sphalerite, (iv) reductive dissolution of Mn/Fe hydroxides and co-precipitation/adsorption with Zn. In light of climate change predictions these results indicate future scenarios may include larger or more frequent transient 'pulses' of dissolved Pb and Zn released to river systems. These short lived pollution episodes could act as a significant barrier to achieving the EU Water Framework Directive objectives.
NASA Astrophysics Data System (ADS)
Jaques, Luís; Pascal, Christophe
2017-09-01
Paleostress tensor restoration methods are traditionally limited to reconstructing geometrical parameters and are unable to resolve stress magnitudes. Based on previous studies we further developed a methodology to restore full paleostress tensors. We concentrated on inversion of Mode I fractures and acquired data in Panasqueira Mine, Portugal, where optimal exposures of mineralized quartz veins can be found. To carry out full paleostress restoration we needed to determine (1) pore (paleo)pressure and (2) vein attitudes. The present contribution focuses specifically on the determination of pore pressure. To these aims we conducted an extensive fluid inclusion study to derive fluid isochores from the quartz of the studied veins. To constrain P-T conditions, we combined these isochores with crystallisation temperatures derived from geochemical analyses of coeval arsenopyrite. We also applied the sphalerite geobarometer and considered two other independent pressure indicators. Our results point to pore pressures of ∼300 MPa and formation depths of ∼10 km. Such formation depths are in good agreement with the regional geological evolution. The obtained pore pressure will be merged with vein inversion results, in order to achieve full paleostress tensor restoration, in a forthcoming companion paper.
Synthesis of Zn-In-S Quantum Dots with Tunable Composition and Optical Properties.
Wang, Xianliang; Damasco, Jossana; Shao, Wei; Ke, Yujie; Swihart, Mark T
2016-03-03
II-III-VI semiconductors are of interest due to their chemical stability and composition-tunable optical properties. Here, we report a methodology for the synthesis of monodisperse zinc-indium-sulfide (ZIS) alloy quantum dots (QDs, mean diameter from ∼2 to 3.5 nm) with an In content substantially below that of the stoichiometric ZnIn2 S4 compound. The effects of indium incorporation on the size, lattice constant, and optical properties of ZIS QDs are elucidated. In contrast to previous reports, we employ sulfur dissolved in oleic acid as the sulfur donor rather than thioacetamide (TAA). The size of the ZIS QDs and their crystal lattice constant increased with increasing In incorporation, but they maintained the cubic sphalerite phase of ZnS, rather than the hexagonal phase typical of ZnIn2 S4 . The QDs' absorbance onset at UV wavelengths red-shifts with increasing In content and the accompanying increase in NC size. The ZIS NCs and related materials, whose synthesis is enabled by the approach presented here, provide new opportunities to apply II-III-VI semiconductors in solution-processed UV optoelectronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Influence of Cobalt Doping on the Physical Properties of Zn0.9Cd0.1S Nanoparticles
2010-01-01
Zn0.9Cd0.1S nanoparticles doped with 0.005–0.24 M cobalt have been prepared by co-precipitation technique in ice bath at 280 K. For the cobalt concentration >0.18 M, XRD pattern shows unidentified phases along with Zn0.9Cd0.1S sphalerite phase. For low cobalt concentration (≤0.05 M) particle size, dXRDis ~3.5 nm, while for high cobalt concentration (>0.05 M) particle size decreases abruptly (~2 nm) as detected by XRD. However, TEM analysis shows the similar particle size (~3.5 nm) irrespective of the cobalt concentration. Local strain in the alloyed nanoparticles with cobalt concentration of 0.18 M increases ~46% in comparison to that of 0.05 M. Direct to indirect energy band-gap transition is obtained when cobalt concentration goes beyond 0.05 M. A red shift in energy band gap is also observed for both the cases. Nanoparticles with low cobalt concentrations were found to have paramagnetic nature with no antiferromagnetic coupling. A negative Curie–Weiss temperature of −75 K with antiferromagnetic coupling was obtained for the high cobalt concentration. PMID:20672097
Influence of Cobalt Doping on the Physical Properties of Zn0.9Cd0.1S Nanoparticles.
Singhal, Sonal; Chawla, Amit Kumar; Gupta, Hari Om; Chandra, Ramesh
2009-11-17
Zn0.9Cd0.1S nanoparticles doped with 0.005-0.24 M cobalt have been prepared by co-precipitation technique in ice bath at 280 K. For the cobalt concentration >0.18 M, XRD pattern shows unidentified phases along with Zn0.9Cd0.1S sphalerite phase. For low cobalt concentration (≤0.05 M) particle size, dXRDis ~3.5 nm, while for high cobalt concentration (>0.05 M) particle size decreases abruptly (~2 nm) as detected by XRD. However, TEM analysis shows the similar particle size (~3.5 nm) irrespective of the cobalt concentration. Local strain in the alloyed nanoparticles with cobalt concentration of 0.18 M increases ~46% in comparison to that of 0.05 M. Direct to indirect energy band-gap transition is obtained when cobalt concentration goes beyond 0.05 M. A red shift in energy band gap is also observed for both the cases. Nanoparticles with low cobalt concentrations were found to have paramagnetic nature with no antiferromagnetic coupling. A negative Curie-Weiss temperature of -75 K with antiferromagnetic coupling was obtained for the high cobalt concentration.
NASA Astrophysics Data System (ADS)
Hooper, R. L.; Mahoney, J. B.
2001-12-01
The lower Coeur d'Alene River Valley of northern Idaho is the site of extensive lead and zinc contamination resulting from both direct riverine tailings disposal and flood remobilization of contaminated sediments derived from the Coeur d'Alene mining district upstream. Variations in the hydrologic regime, redox conditions, porosity/permeability, organic content and microbial activity results in complicated metal transport pathways. Documentation of these pathways is a prerequisite to effective remediation, and requires accurate analysis of lateral and vertical variations. An analytical approach combining sequential extraction, electron microscopy, and microanalysis provides a comprehensive assessment of particulate speciation in this complex hydrologic system. Rigorously controlled sample preparation and a new sequential extraction protocol provide unprecedented insight into the role of metal sequestration in fluvial subenvironments. Four subenvironments were investigated: bedload, overbank (levee), marsh, and lacustrine. Periodic floods remobilize primary ore minerals and secondary minerals from upstream tailings (primarily oxyhydroxides, sulfides and carbonates). The bedload in the lower valley is a reducing environment and acts as a sink for detrital carbonates and sulfides moving downstream. In addition, authigenic/biogenic Fe, Pb and Zn sulfides and phosphates are common in bedload sediments near the sediment/water interface. Flood redistribution of oxide, sulfide and carbonate phases results in periodic contaminant recharge generating a complex system of metal dissolution, mobilization, migration and precipitation. In levee environments, authigenic sulfides from flood scouring are quickly oxidized resulting in development of oxide coated grain surfaces. Stability of detrital minerals on the levee is variable depending on sediment permeability, grain size and mineralogy resulting in a complex stratigraphy of oxide zones mottled with zones dominated by detrital and authigenic carbonate and sulfide phases. Marshes subjected to periodic subaerial exposure/flooding are even more complex and dominated by authigenic and biogenic mineralization. Lacustrine environments are dominated by nanocrystalline inorganic and biogenic sulfide minerals in the upper third of the contaminated sediment column with increasing amounts of silt sized detrital sulfides (especially sphalerite) closer to the premining surface. In pH-neutral subenvironments within the wetlands and lateral lakes of the lower Coeur d'Alene River Valley, microbial fixation plays a critical role in sequestering metals. Complex metal oxyhydroxide phases provided via flood recharge to river edge, marsh and lacustrine environments rapidly dissolve upon encountering anoxic conditions. Microbial activity is extremely effective in removing heavy metals from the water column, producing a nanocrystalline biofilm substrate characterized by ZnS (sphalerite) and non-stoichiometric PbS, FeS, and mixed metal sulfides. These solid phases are inherently unstable, and the sequestered metals become readily available through changes in redox or pH conditions, particularly dam-controlled annual fluctuations in base level, or during removal by bottom-feeding aquatic water fowl. The recognition of the inherent complexity and instability of microbially produced sulfidic material in a pH-neutral environment has important implications for remediation efforts utilizing wetland filtration methods.
NASA Astrophysics Data System (ADS)
Saintilan, Nicolas J.; Stephens, Michael B.; Spikings, Richard; Schneider, Jens; Chiaradia, Massimo; Spangenberg, Jorge E.; Ulianov, Alexey; Fontboté, Lluís
2017-08-01
The Åkerlandet, Järvsand, and Laisvall deposits in Sweden are calcite-fluorite-sulfide vein deposits and occurrences located close to the current erosional front of the Caledonian orogen and hosted by crystalline basement rocks in the Fennoscandian Shield. At Laisvall, basement-hosted veinlets occur beneath Ediacaran to Cambrian sandstones that host a strata-bound Pb-Zn deposit. The mineralized fractures at Åkerlandet and Järvsand occur along fault systems oriented N-S to NNW-SSE. Veins or veinlets strike NNW-SSE and NW-SE at Åkerlandet, NNE-SSW at Järvsand, and NNW-SSE and NNE-SSW to NE-SW at Laisvall. At Åkerlandet and Järvsand, fractures acted as conduits for hydrothermal fluids of variable composition and formed during separate tectonic events. At Åkerlandet, the fault zone with NNW-SSE strike shows kinematic indicators consistent with NE-SW bulk horizontal extension. At Järvsand, the calcite-fluorite-galena veins formed along R-Riedel shears related to the host N-S to NNW-SSE fault system. The kinematic indicators are consistent with NW-SE bulk horizontal extension, similar to the extensional deformation during the later part of the Caledonian orogeny (Silurian to Devonian). At Åkerlandet, adularia-quartz deposition was followed by sphalerite ± galena and finally by precipitation of fluorite and calcite. 40Ar-39Ar thermochronology of a single adularia sample did not yield a well-defined plateau age but the gas released at higher temperatures suggests an early Tonian (980 to 950 Ma) crystallization age, i.e., during the later part of the Sveconorwegian orogeny, although the data do not exclude other less likely interpretations. Previous fluid inclusion microthermometry and geochronological studies and new petrographic and geochemical results suggest that sphalerite ± galena mineralization formed from saline, relatively oxidizing, moderate-temperature, and slightly acidic hydrothermal fluids, either during the Ediacaran or the Middle Ordovician. Metals and H2S were derived from local basement rocks. Based on petrographic evidence, rare earth element composition, and S, C, and O isotope data, fluorite and calcite precipitated under near neutral and relatively reducing conditions. Occurrence of solid bitumen in veins at Åkerlandet and C and O isotope data of calcite at Åkerlandet and in the Laisvall basement veinlets suggest that the precipitation of calcite and fluorite was triggered by interaction of hot and evolved hydrothermal fluids (87Sr/86Sr = 0.718-0.732) with organic matter. Structural, petrographic, and geochemical data at Laisvall suggest that the basement structures hosting calcite-fluorite ± pyrite veinlets were utilized in the Middle Ordovician as the plumbing system for the oxidizing, slightly acidic, metal-bearing brines that caused the economic Pb-Zn mineralization in the overlying sandstones.
Ansari, T M; Marr, I L; Coats, A M
2001-02-01
This study was carried out to characterise the mineralogical forms of barium and the trace heavy metal impurities in commercial barytes of different origins using electron probe microanalysis (EPMA), X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS). Qualitative EPMA results show the presence of typically eight different minerals in commercial barytes including barite (BaSO4), barium feldspar, galena (PbS), pyrite (FeS2), sphalerite (ZnS), quartz (SiO2), and silicates, etc. Quantitative EPMA confirms that the barite crystals in the barytes contain some strontium and a little calcium, whereas trace heavy metals occur in the associated minerals. Analysis of aqua regia extracts of barytes samples by ICP-MS has shown the presence of a large number of elements in the associated minerals. Arsenic, copper and zinc concentrations correlate closely in all 10 samples. The findings suggest that barytes is not, as traditionally thought, an inert mineral, but is a potentially toxic substance due to its associated heavy metal impurities, which can be determined by an aqua regia digest without the need for complete dissolution of the barite itself. X-ray powder diffraction was not informative as the complex barite pattern masks the very weak lines from the small amounts of associated minerals.
NASA Astrophysics Data System (ADS)
Verhaert, Michèle; Bernard, Alain; Dekoninck, Augustin; Lafforgue, Ludovic; Saddiqi, Omar; Yans, Johan
2017-10-01
In the Moroccan High Atlas, two sulfide deposits hosted by Jurassic dolostones underwent significant weathering. In the Cu deposit of Jbel Klakh, several stages of supergene mineralization are distinguished: (1) the replacement of hypogene sulfides in the protolith (chalcopyrite) by secondary sulfides in the cementation zone (bornite, digenite, chalcocite, covellite), (2) the formation of oxidized minerals in the saprolite (malachite, azurite, brochantite) where the environment becomes more oxidizing and neutral, and (3) the precipitation of late carbonates (calcite) and iron (hydr-)oxides in the laterite. The precipitation of carbonates is related to the dissolution of dolomitic host rocks, which buffers the fluid acidity due to the oxidation of sulfides. In the Jbel Haouanit Pb-Zn deposit, the mineral assemblage is dominated by typical calamine minerals, Cu minerals (chalcocite, covellite, malachite), and a Cu-Pb-Zn vanadate (mottramite). Galena is successively weathered in anglesite and cerussite. Sphalerite is weathered in smithsonite, which is rapidly replaced by hydrozincite. Late iron (hydr-)oxides are mainly found at the top of both deposits (laterite). Both deposits are thus characterized by specific mineral zoning, from laterite to protolith, related to variations in the mineralogy and ore grades and probably caused by varying Eh-pH conditions.
Recovery of NORM from scales generated by oil extraction.
Al Attar, Lina; Safia, Bassam; Ghani, Basem Abdul; Al Abdulah, Jamal
2016-03-01
Scales, containing naturally occurring radioactive materials (NORM), are a major problem in oil production that lead to costly remediation and disposal programmes. In view of environmental protection, radio and chemical characterisation is an essential step prior to waste treatment. This study focuses on developing of a protocol to recover (226)Ra and (210)Pb from scales produced by petroleum industry. X-ray diffractograms of the scales indicated the presence of barite-strontium (Ba0.75Sr0.25SO4) and hokutolite (Ba0.69Pb0.31SO4) as main minerals. Quartz, galena and Ca2Al2SiO6(OH)2 or sphalerite and iron oxide were found in minor quantities. Incineration to 600 °C followed by enclosed-digestion and acid-treatment gave complete digestion. Using (133)Ba and (210)Pb tracers as internal standards gave recovery ranged 87-91% for (226)Ra and ca. 100% for (210)Pb. Radium was finally dissolved in concentrated sulphuric acid, while (210)Pb dissolved in the former solution as well as in 8 M nitric acid. Dissolving the scales would provide better estimation of their radionuclides contents, facilitate the determination of their chemical composition, and make it possible to recycle NORM wastes in terms of radionuclides production. Copyright © 2015 Elsevier Ltd. All rights reserved.
Selenium content in sulfide ores from the Chalkidiki peninsula, Greece.
Nicolaidou, A E
1998-01-01
Selenium (Se) was assessed in galena, sphalerite, and pyrite samples. These are components of mixed sulfide ores from the Olympias and Madem Lakkos-Mavres Petres deposits and the Skouries porphyry-copper deposit. We used atomic absorption spectroscopy (AAS) with a hydride generator system. The highest concentration of Se (516 ppm) was found in the fine-grained galena at the -135 level of the Olympias deposits. In the Madem Lakkos-Mavres Petres deposit, the highest concentration of Se (33 ppm) was found in the pyrites of the level 30. The concentration of Se in the arsenopyrites and chalcopyrites is lower than the detection limit of the analytical method (< 100 ppb). The concentrated chalcopyrite from the porphyry copper deposit at Skouries exhibits a significant Se content (average 200 ppm) in contrast to the chalcopyrite from the Olympias and the Madem Lakkos-Mavres Petres. Variations in the Se content of the sulfide minerals studied could be caused by redox-pH and/or temperature conditions, as well as by the difference in crystal structure. The Se found in the areas studied may positively affect the environment. Sulfide minerals are oxidized by microorganisms, infiltrate in the soil-water in the form of selenate or selenite ion, and directly or indirectly influence the human organism.
Mineralogy and origin of atmospheric particles in the industrial area of Huelva (SW Spain)
NASA Astrophysics Data System (ADS)
Bernabé, J. M.; Carretero, M. I.; Galán, E.
The mineralogy of atmospheric particles at the confluence of the Tinto and Odiel rivers, south of Huelva (a highly industrialized city in the SW Spain), was characterized in view to identify source origins. In spite of the small amount of sample collected, mineralogical characterization was performed by X-ray diffraction, polarized light microscopy and scanning electron microscopy with EDS analysis system, using an adequate sample preparation methodology. Sedimentable (SP) and aerosols particles were sampled an one-week basis every two months for one year. Quartz, calcite and feldspars were found to be the major minerals in both fractions, and phyllosilicates, dolomite and gypsum were also identified in lower content. Minor mineral particles included barite, apatite, sphalerite and pyrite. SEM studies revealed the additional presence of chalcopyrite in both SP and aerosols, and of chalcocite-covellite, halite and sylvite in the latter. Siderite, hematite and ankerite were only detected in the SP fraction. The concentrations of the previous minerals increased in summer by effect of the limited rain and the resulting scarcity of atmosphere washing. Non-mineral particles detected by SEM in SP and aerosol fractions included spherical, biological and compositionally complex particles. The main source of mineral particles was found to be the soil suspension in addition to the metallurgical and fertilizer production industries in the area.
Onwudiwe, Damian C; Ajibade, Peter A
2011-01-01
The synthesis of II-VI semiconductor nanoparticles obtained by the thermolysis of certain group 12 metal complexes as precursors is reported. Thermogravimetric analysis of the single source precursors showed sharp decomposition leading to their respective metal sulfides. The structural and optical properties of the prepared nanoparticles were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) UV-Vis and photoluminescence spectroscopy. The X-ray diffraction pattern showed that the prepared ZnS nanoparticles have a cubic sphalerite structure; the CdS indicates a hexagonal phase and the HgS show the presence of metacinnabar phase. The TEM image demonstrates that the ZnS nanoparticles are dot-shaped, the CdS and the HgS clearly showed a rice and spherical morphology respectively. The UV-Vis spectra exhibited a blue-shift with respect to that of the bulk samples which is attributed to the quantum size effect. The band gap of the samples have been calculated from absorption spectra and werefound to be about 4.33 eV (286 nm), 2.91 eV (426 nm) and 4.27 eV (290 nm) for the ZnS, CdS and HgS samples respectively.
Onwudiwe, Damian C.; Ajibade, Peter A.
2011-01-01
The synthesis of II-VI semiconductor nanoparticles obtained by the thermolysis of certain group 12 metal complexes as precursors is reported. Thermogravimetric analysis of the single source precursors showed sharp decomposition leading to their respective metal sulfides. The structural and optical properties of the prepared nanoparticles were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) UV-Vis and photoluminescence spectroscopy. The X-ray diffraction pattern showed that the prepared ZnS nanoparticles have a cubic sphalerite structure; the CdS indicates a hexagonal phase and the HgS show the presence of metacinnabar phase. The TEM image demonstrates that the ZnS nanoparticles are dot-shaped, the CdS and the HgS clearly showed a rice and spherical morphology respectively. The UV-Vis spectra exhibited a blue-shift with respect to that of the bulk samples which is attributed to the quantum size effect. The band gap of the samples have been calculated from absorption spectra and werefound to be about 4.33 eV (286 nm), 2.91 eV (426 nm) and 4.27 eV (290 nm) for the ZnS, CdS and HgS samples respectively. PMID:22016607
Full paleostress tensor reconstruction: case study of the Panasqueira Mine, Portugal.
NASA Astrophysics Data System (ADS)
Pascal, C.; Jaques Ribeiro, L. M.
2017-12-01
Paleostress tensor restoration methods are traditionally limited to reconstructing geometrical parameters and are unable to resolve stress magnitudes. Based on previous studies we further developed a methodology to restore full paleostress tensors. We concentrated on inversion of Mode I fractures and acquired data in Panasqueira Mine, Portugal, where optimal 3D exposures of mineralised quartz veins can be found. To carry out full paleostress restoration we needed to determine (1) pore (paleo)pressure and (2) vein attitudes. To these aims we conducted an extensive fluid inclusion study to derive fluid isochores from the quartz of the studied veins. To further constrain P-T conditions, we combined these isochores with crystallisation temperatures derived from geochemical analyses of coeval arsenopyrite. We also applied the sphalerite geobarometer and considered two other independent pressure indicators. Our results point to pore pressures of 300 MPa and formation depths of 10 km. As a second step, we measured 600 subhorizontal quartz veins in all the levels of the mine. The inversion of the attitudes of the veins allowed for reconstructing the orientations of the principal axes of stress, the unscaled Mohr circle and the relative pore pressure. After merging these results with the previously obtained absolute pore pressure we reconstructed the six parameters of the paleostress tensor.
NASA Astrophysics Data System (ADS)
Paganoni, Matteo; Al Harthi, Amena; Morad, Daniel; Morad, Sadoon; Ceriani, Andrea; Mansurbeg, Howri; Al Suwaidi, Aisha; Al-Aasm, Ihsan S.; Ehrenberg, Stephen N.; Sirat, Manhal
2016-04-01
Bed-parallel stylolites are a widespread diagenetic feature in Lower Cretaceous limestone reservoirs, Abu Dhabi, United Arab Emirates (UAE). Diagenetic calcite, dolomite, kaolin and small amounts of pyrite, fluorite, anhydrite and sphalerite occur along and in the vicinity of the stylolites. Petrographic observations, negative δ18OVPDB, fluid inclusion microthermometry, and enrichment in 87Sr suggest that these cements have precipitated from hot basinal brines, which migrated along the stylolites and genetically related microfractures (tension gashes). Fluid migration was presumably related to lateral tectonic compression events related to the foreland basin formation. The low solubility of Al3 + in formation waters suggests that kaolin precipitation was linked to derivation of organic acids during organic matter maturation, probably in siliciclastic source rocks. The mass released from stylolitization was presumably re-precipitated as macro- and microcrystalline calcite cement in the host limestones. The flanks of the oilfield (water zone) display more frequent presence and higher amplitude of stylolites, lower porosity and permeability, higher homogenization temperatures and more radiogenic composition of carbonates compared to the crest (oil zone). This indicates that oil emplacement retards diagenesis. This study demonstrates that stylolitization plays a crucial role in fluid flow and diagenesis of carbonate reservoirs during basin evolution.
Occurrence and significance of stalactites within the epithermal deposits at Creede, Colorado
Campbell, W.R.; Barton, P.B.
1996-01-01
In addition to the common and abundant features in karst terranes, stalactites involving a wide variety of minerals have also been found in other settings, including epigenetic mineral deposits, but these are almost always associated with supergene stages. Here we describe a different mode of occurrence from the Creede epithermal ore deposits, in Colorado, wherein stalactites of silica, sphalerite, galena, or pyrite formed in a vapor-dominated setting, below the paleo-water table, and except possibly for pyrite, as part of the hypogene mineralization. Axial cavities may, or may not, be present. No stalagmites have been recognized. The stalactites are small, from a few millimeters to a few centimeters long and a few millimeters in outer diameter. They represent only a small fraction of one percent of the total mineralization, and are covered by later crystals. Their growth orientation usually is unobservable; however, the parallel arrangement of all stalactites in a given specimen, consistency with indicators of gravitational settling, and the common presence of axial structures make the stalactitic interpretation almost unavoidable. In contrast with common carbonate stalactites, the growth mechanism for the sulfide and silica stalactites requires extensive evaporation. Stalactitic forms have also been reported from other deposits, mostly epithermal or Mississippi-Valley-type occurrences, but we caution that stalactite-like features can form by alternative processes.
Invisible gold in Colombian auriferous soils
NASA Astrophysics Data System (ADS)
Bustos Rodriguez, H.; Oyola Lozano, D.; Rojas Martínez, Y. A.; Pérez Alcázar, G. A.; Balogh, A. G.
2005-11-01
Optic microscopy, X-ray diffraction (XRD), Mössbauer spectroscopy (MS), Electron microprobe analysis (EPMA) and secondary ions mass spectroscopy (SIMS) were used to study Colombian auriferous soils. The auriferous samples, collected from El Diamante mine, located in Guachavez-Nariño (Colombia), were prepared by means of polished thin sections and polished sections for EPMA and SIMS. Petrography analysis was made using an optical microscope with a vision camera, registering the presence, in different percentages, of the following phases: pyrite, quartz, arsenopyrite, sphalerite, chalcopyrite and galena. By XRD analysis, the same phases were detected and their respective cell parameters calculated. By MS, the presence of two types of pyrite was detected and the hyperfine parameters are: δ 1 = 0.280 ± 0.01 mm/s and Δ Q 1 = 0.642 ± 0.01 mm/s, δ 2 = 0.379 ± 0.01 mm/s and Δ Q 2 = 0.613 ± 0.01 mm/s. For two of the samples MS detected also the arsenopyrite and chalcopyrite presence. The mean composition of the detected gold regions, established by EPMA, indicated 73% Au and 27% Ag (electrum type). Multiple regions of approximately 200 × 200 μm of area in each mineral sample were analyzed by SIMS registering the presence of “invisible gold” associated mainly with the pyrite and occasionally with the arsenopyrite.
Chaffee, M.A.; Hill, R.H.
1989-01-01
The Hodson mining district is in the westernmost foothills of the Sierra Nevada in California, about 17 km west of the town of Angels Camp. This district is part of the West Gold Belt, which lies about 12-16 km west of, and generally parallel to, the better known Mother Lode Gold Belt in central California. The district produced several million dollars worth of Au between about 1890 and 1940.The geologic setting and mineral deposits in the West Gold Belt are generally similar to those in the Mother Lode Gold Belt. Rocks in the study area are of Jurassic age and consist of a mixture of (1) fine-grained, generally thin-bedded, clastic sedimentary rocks that have been metamorphosed to slates, schists, and phyllites, and (2) massive volcanic flows and welded tuffs that have been metamorphosed to metabasalts and metatuffs. All rocks were intensely faulted and folded during the Late Cretaceous Nevadan orogeny; northnorthwest- and northwest-trending faults dominate. Mining in the area was of low-grade gold-pyrite ores occurring principally in the carbonatized wall rocks adjacent to the major northwest-trending Hodson fault and its splays. Minor amounts of other sulfide minerals (principally chalcopyrite, arsenopyrite, sphalerite, and galena) are locally associated with the Au deposits.
The enhancing of Au-Ag-Te content in tellurium-bearing ore mineral by bio-oxidation-leaching
NASA Astrophysics Data System (ADS)
Kim, PyeongMan; Kim, HyunSoo; Myung, EunJi; Kim, YoonJung; Lee, YongBum; Park*, CheonYoung
2015-04-01
The purpose of this study is to enhance the content of valuable metals such as Au-Ag-Te in tellurium-bearing minerals by bio-oxidation-leaching. It was confirmed that pyrite, chalcopyrite, sphalerite and galena were produced together with tellurium-bearing minerals including hessite, sylvanite and tellurobismuthite from ore minerals and concentrates through microscopic observation and SEM/EDS analysis. In a bio-oxidation-leaching experiment, with regard to Au, Ag, Te, Cu and Fe, the changes in the amount of leaching and the content of leaching residues were compared and analyzed with each other depending on the adaptation of an indigenous microbe identified as Acidithiobacillus ferrooxidans. As a result of the experiment, the Au-Ag-Te content in tellurium-bearing ore mineral was enhanced in the order of physical oxidation leaching, physical/non-adaptive bio-oxidation-leaching and physical/adaptive biological leaching. It suggests that the bio-oxidation-leaching using microbes adapted in tellurium-bearing ore mineral can be used as a pre-treatment and a main process in a recovery process of valuable metals. "This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"
Hode, Tomas; von Dalwigk, Ilka; Broman, Curt
2003-01-01
The Siljan ring structure (368 +/- 1.1 Ma) is the largest known impact structure in Europe. It isa 65-km-wide, eroded, complex impact structure, displaying several structural units, including a central uplifted region surrounded by a ring-shaped depression. Associated with the impact crater are traces of a post-impact hydrothermal system indicated by precipitated and altered hydrothermal mineral assemblages. Precipitated hydrothermal minerals include quartz veins and breccia fillings associated with granitic rocks at the outer margin of the central uplift, and calcite, fluorite, galena, and sphalerite veins associated with Paleozoic carbonate rocks located outside the central uplift. Two-phase water/gas and oil/gas inclusions in calcite and fluorite display homogenization temperatures between 75 degrees C and 137 degrees C. With an estimated erosional unloading of approximately 1 km, the formation temperatures were probably not more than 10-15 degrees C higher. Fluid inclusion ice-melting temperatures indicate a very low salt content, reducing the probability that the mineralization was precipitated during the Caledonian Orogeny. Our findings suggest that large impacts induce low-temperature hydrothermal systems that may be habitats for thermophilic organisms. Large impact structures on Mars may therefore be suitable targets in the search for fossil thermophilic organisms.
Corral, Isaac; Cardellach, Esteve; Corbella, Merce; Canals, Angels; Griera, Albert; Gomez-Gras, David; Johnson, Craig A.
2017-01-01
Cerro Quema is a high sulfidation epithermal Au-Cu deposit with a measured, indicated and inferred resource of 35.98 Mt. @ 0.77 g/t Au containing 893,600 oz. Au (including 183,930 oz. Au equiv. of Cu ore). It is characterized by a large hydrothermal alteration zone which is interpreted to represent the lithocap of a porphyry system. The innermost zone of the lithocap is constituted by vuggy quartz with advanced argillic alteration locally developed on its margin, enclosed by a well-developed zone of argillic alteration, grading to an external halo of propylitic alteration. The mineralization occurs in the form of disseminations and microveinlets of pyrite, chalcopyrite, enargite, tennantite, and trace sphalerite, crosscut by quartz, barite, pyrite, chalcopyrite, sphalerite and galena veins.Microthermometric analyses of two phase (L + V) secondary fluid inclusions in igneous quartz phenocrysts in vuggy quartz and advanced argillically altered samples indicate low temperature (140–216 °C) and low salinity (0.5–4.8 wt% NaCl eq.) fluids, with hotter and more saline fluids identified in the east half of the deposit (Cerro Quema area).Stable isotope analyses (S, O, H) were performed on mineralization and alteration minerals, including pyrite, chalcopyrite, enargite, alunite, barite, kaolinite, dickite and vuggy quartz. The range of δ34S of sulfides is from − 4.8 to − 12.7‰, whereas δ34S of sulfates range from 14.1 to 17.4‰. The estimated δ34SΣS of the hydrothermal fluid is − 0.5‰. Within the advanced argillic altered zone the δ34S values of sulfides and sulfates are interpreted to reflect isotopic equilibrium at temperatures of ~ 240 °C. The δ18O values of vuggy quartz range from 9.0 to 17.5‰, and the δ18O values estimated for the vuggy quartz-forming fluid range from − 2.3 to 3.0‰, indicating that it precipitated from mixing of magmatic fluids with surficial fluids. The δ18O of kaolinite ranges from 12.7 to 18.1‰ and δD from − 103.3 to − 35.2‰, whereas the δ18O of dickite varies between 12.7 and 16.3‰ and δD from − 44 to − 30. Based on δ18O and δD, two types of kaolinite/dickite can be distinguished, a supergene type and a hypogene type. Combined, the analytical data indicate that the Cerro Quema deposit formed from magmatic-hydrothermal fluids derived from a porphyry copper-like intrusion located at depth likely towards the east of the deposit. The combination of stable isotope geochemistry and fluid inclusion analysis may provide useful exploration vectors for porphyry copper targets in the high sulfidation/lithocap environment.
Metal mobilization under alkaline conditions in ash-covered tailings.
Lu, Jinmei; Alakangas, Lena; Wanhainen, Christina
2014-06-15
The aim of this study was to determine element mobilization and accumulation in mill tailings under alkaline conditions. The tailings were covered with 50 cm of fly ash, and above a sludge layer. The tailings were geochemically and mineralogically investigated. Sulfides, such as pyrrhotite, sphalerite and galena along with gangue minerals such as dolomite, calcite, micas, chlorite, epidote, Mn-pyroxene and rhodonite were identified in the unoxidized tailings. The dissolution of the fly ash layer resulted in a high pH (close to 12) in the underlying tailings. This, together with the presence of organic matter, increased the weathering of the tailings and mobilization of elements in the uppermost 47 cm of the tailings. All primary minerals were depleted, except quartz and feldspar which were covered by blurry secondary carbonates. Sulfide-associated elements such as Cd, Fe, Pb, S and Zn and silicate-associated elements such as Fe, Mg and Mn were released from the depletion zone and accumulated deeper down in the tailings where the pH decreased to circum-neutral. Sequential extraction suggests that Cd, Cu, Fe, Pb, S and Zn were retained deeper down in the tailings and were mainly associated with the sulfide phase. Calcium, Cr, K and Ni released from the ash layer were accumulated in the uppermost depletion zone of the tailings. Copyright © 2014 Elsevier Ltd. All rights reserved.
Molybdenite Mineral Evolution: A Study Of Trace Elements Through Time
NASA Astrophysics Data System (ADS)
McMillan, M. M.; Downs, R. T.; Stein, H. J.; Zimmerman, A.; Beitscher, B. A.; Sverjensky, D. A.; Papineau, D.; Armstrong, J. T.; Hazen, R. M.
2010-12-01
Mineral evolution explores changes through time in Earth’s near-surface mineralogy, including diversity of species, relative abundances of species, and compositional ranges of major, minor and trace elements. Such studies elucidate the co-evolution of the geosphere and biosphere. Accordingly, we investigated trace and minor elements in molybdenite (MoS2) with known ages from 3 billion years to recent. Molybdenite, the commonest mineral of Mo, may prove to be a useful case study as a consequence of its presence in Earth’s early history, the effects of oxidation on Mo mobility, and the possible role of Mo mineral coevolution with biology via its role in the nitrogen fixation enzyme nitrogenase. We employed ICPMS, SEM and electron microprobe analyses to detect trace and minor elements. We detected significant amounts of Mn and Cu (~100 ppm) and greater amounts of Fe, W, and Re (to ~4000 ppm). Molybdenites commonly contain micro inclusions, resulting in local concentrations in otherwise homogeneous samples. Inhomogeneities in Fe, Zn and Sn concentrations, for example, point to the presence of pyrite, sphalerite and cassiterite inclusions, respectively. Analyses examined as a function of time reveal that samples containing significant concentrations (>200 ppm, compared to average values < 100 ppm) of W and Re formed primarily within the last billion years. These trends may reflect changes in the mobility of W and Re in oxic hydrothermal fluids at shallow crustal conditions following the Great Oxidation Event.
Facile production of ZnS quantum dot nanoparticles by Saccharomyces cerevisiae MTCC 2918.
Sandana Mala, John Geraldine; Rose, Chellan
2014-01-20
Microbial synthesis of nanoparticles is a green route towards ecofriendly measures to overcome the toxicity and non-applicability of nanomaterials in clinical uses obtained by conventional physical and chemical approaches. Nanoparticles in the quantum regime have remarkable characteristics with excellent applicability in bioimaging. Yeasts have been commercially exploited for several industrial applications. ZnS nanoparticles as semiconductor quantum dots have mostly been synthesized by bacterial species. Here in, we have attempted to produce ZnS nanoparticles in quantum regime by Saccharomyces cerevisiae MTCC 2918 fungus and characterize its size and spectroscopic properties. Intracellular ZnS nanoparticles were produced by a facile procedure and freeze thaw extraction using 1mM zinc sulfate. The ZnS nanoparticles showed surface plasmon resonance band at 302.57nm. The ZnS nanoparticles were in low yield and in the size range of 30-40nm. Powder XRD analysis revealed that the nanoparticles were in the sphalerite phase. Photoluminescence spectra excited at 280nm and 325nm revealed quantum confinement effects. This suggests that yeasts have inherent sulfate metabolizing systems and are capable fungal sources to assimilate sulfate. Further insights are required to identify the transport/reducing processes that may have caused the synthesis of ZnS nanoparticles such as an oxidoreductase enzyme-mediated mechanism. Copyright © 2013 Elsevier B.V. All rights reserved.
The role of intrusions in the formation of Irish-type mineralisation
NASA Astrophysics Data System (ADS)
McCusker, Jim; Reed, Christopher
2013-08-01
The Stonepark Prospect is located in County Limerick, south-central Ireland. Multiple zones of Zn-Pb mineralisation have been identified at Stonepark and these are approximately 5 km west of the Pallas Green Prospect. At Stonepark, the sulphide bodies are hosted within the Waulsortian Limestone and closely resemble other Irish-type deposits. The mineralisation is composed of pyrite-marcasite, sphalerite and galena with gangue Fe-dolomite and calcite cements. A key difference at Stonepark is the presence of Chadian-aged volcanic rocks (Knockroe Volcanics) that intrude into and overlie the Waulsortian Limestone. Subsequent hydrothermal brecciation of the Waulsortian Limestone and Knockroe intrusions resulted in the formation of tabular polymict breccia bodies containing mixed carbonate and clasts of intrusive rocks. These have then been overprinted by massive sulphide mineralisation. Further syn-mineralisation brecciation has overprinted the earlier breccias. Drilling has demonstrated a spatial relationship between the volume of intrusive rocks (dykes and polymict breccias) and Zn-Pb mineralisation. This association suggests that the intrusive rocks provided a mechanism for the introduction of the mineralising fluids into the breccia bodies. This is significant as to date no large controlling fault has been identified, as is seen at other Irish-type deposits. Further work is required to understand the alteration process of the intrusive rocks and how this may relate to the mineralising process.
NASA Astrophysics Data System (ADS)
Yalikun, Yaxiaer; Xue, Chunji; Symons, D. T. A.
2018-02-01
The Jinding Zn-Pb deposit is located in the Lanping-Simao basin, Yunnan, China. Paleomagnetic results are reported from the Beichang, Jiayashan, and Nanchang mineralization zones that are hosted in the Lower Cretaceous Jinxing and Upper Paleocene Yunlong Formations. The timing of formation of the Zn-Pb mineralization has not been previously defined but is geologically constrained to be younger than Upper Paleocene. Paleomagnetic analyses of 645 specimens from 42 sites using mostly thermal and then alternating field step demagnetization isolated a stable characteristic remanent magnetization (ChRM) for 29 mineralized sites. Step demagnetization and rock magnetic analyses of Zn and Pb concentrates and tailings show that the main remanence carriers are pyrrhotite and magnetite or low Ti titanomagnetite inclusions in sphalerite and galena. Randomly oriented ChRM directions for 18 clast specimens collected from site 40 provide a conglomerate test that shows that the clasts have not been remagnetized by a metamorphic event. A paleomagnetic fold test on the mineralized specimens is negative, showing that the mineralization is epigenetic because its ChRM substantially postdates the major thrust folding event that formed the dome structure of the Jinding deposit. Using extensive regional geologic and paleomagnetic data from other studies with the Jinding paleomagnetic data yields a mean age of 23 ± 3 Ma for the mineralization.
Hydrometallurgical Extraction of Zinc and Copper A 57Fe-Mössbauer and XRD Approach
NASA Astrophysics Data System (ADS)
Mulaba-Bafubiandi, A. F.; Waanders, F. B.
2005-02-01
The most commonly used route in the hydrometallurgical extraction of zinc and copper from a sulphide ore is the concentrate roast leach electro winning process. In the present investigation a zinc copper ore from the Maranda mine, located in the Murchison Greenstone Belt, South Africa, containing sphalerite (ZnS) and chalcopyrite (CuFeS2), was studied. The 57Fe-Mössbauer spectrum of the concentrate yielded pyrite, chalcopyrite and clinochlore, consistent with XRD data. Optimal roasting conditions were found to be 900°C for 3 h and the calcine produced contained according to X-ray diffractometry equal amounts of franklinite (ZnFe2O4) and zinc oxide (ZnO) and half the amount of willemite (Zn2SiO4). The Mössbauer spectrum showed predominantly franklinite (59%), hematite (6%) and other Zn- or Cu-depleted ferrites (35%). The latter could not be detected by XRD analyses as peak overlapping with other species occurred. Leaching was done with HCl, H2SO4 and HNO3, to determine which process would result in maximum recovery of Zn and Cu. More than 80% of both were recovered by using either one of the three techniques. From the residue of the leaching, the Fe-compounds were precipitated and <1% of the Zn and Cu was not recovered.
NASA Astrophysics Data System (ADS)
Wang, Han; Jin, Tingting; Zheng, Xing; Jiang, Bo; Zhu, Chaosheng; Yuan, Xiangdong; Zheng, Jingtang; Wu, Mingbo
2016-11-01
Hollow cadmium sulfide (CdS) nanospheres of about 260 nm average diameters and about 30 nm shell thickness can be easily synthesized via a sonochemical process, in which polystyrene (PS) nanoparticles were employed as templates. In order to remove the PS templates, both etching and calcination were applied in this paper. The influence of the two different template removal methods on the surface micromorphology, crystal structure, and photocatalytic activity of hollow CdS nanospheres was carefully performed a comparative study. Results of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray, FT-IR, thermogravimetric analysis, Brunauer-Emmett-Teller, diffused reflectance spectra, and decolorization experiments showed that the different template removal methods exhibited a significant influence on the surface micromorphology, crystal structure, and photocatalytic activity of hollow CdS nanospheres. The CdS hollow nanospheres as-prepared by etching had pure cubic sphalerite structure, higher -OH content, less defects and exhibited good photocatalytic activity for rhodamine-B, Methylene Blue and methyl orange under UV-vis light irradiation. However, CdS hollow nanospheres obtained by calcination with a hexagonal crystal structure, less -OH content, more defects have shown worse photocatalytic activity. This indicated that surface micromorphology and crystalline phase were mainly factors influencing photocatalytic activity of hollow CdS nanospheres.
Tin-tungsten mineralizing processes in tungsten vein deposits: Panasqueira, Portugal
NASA Astrophysics Data System (ADS)
Lecumberri-Sanchez, P.; Pinto, F.; Vieira, R.; Wälle, M.; Heinrich, C. A.
2015-12-01
Tungsten has a high heat resistance, density and hardness, which makes it widely applied in industry (e.g. steel, tungsten carbides). Tungsten deposits are typically magmatic-hydrothermal systems. Despite the economic significance of tungsten, there are no modern quantitative analytical studies of the fluids responsible for the formation of its highest-grade deposit type (tungsten vein deposits). Panasqueira (Portugal) is a tungsten vein deposit, one of the leading tungsten producers in Europe and one of the best geologically characterized tungsten vein deposits. In this study, compositions of the mineralizing fluids at Panasqueira have been determined through combination of detailed petrography, microthermometric measurements and LA-ICPMS analyses, and geochemical modeling has been used to determine the processes that lead to tungsten mineralization. We characterized the fluids related to the various mineralizing stages in the system: the oxide stage (tin and tungsten mineralization), the sulfide stage (chalcopyrite and sphalerite mineralization) and the carbonate stage. Thus, our results provide information on the properties of fluids related with specific paragenetic stages. Furthermore we used those fluid compositions in combination with host rock mineralogy and chemistry to evaluate which are the controlling factors in the mineralizing process. This study provides the first quantitative analytical data on fluid composition for tungsten vein deposits and evaluates the controlling mineralization processes helping to determine the mechanisms of formation of the Panasqueira tin-tungsten deposit and providing additional geochemical constraints on the local distribution of mineralization.
Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits
Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong
2016-01-01
Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits. PMID:27121538
Abandoned mine slags analysis by EPMA WDS X-ray mapping
NASA Astrophysics Data System (ADS)
Guimarães, F.; Rosado, L.; Morais, C.; Candeias, A. E.; Pinto, A. P.; Mirão, J.
2010-02-01
Mining activity on the Iberian Pyritic Belt (Portugal and Spain) started before Phoenician times, became particularly intense during the Roman occupation of the Iberian Peninsula (for gold), and after the industrial revolution (for gold, copper, zinc, lead and sulphur). The commonest ore of this region is a massive polymetalic sulphide accumulation, where pyrite (FeS2) is the main mineral, with variable concentrations of chalcopyrite (CuFeS2), sphalerite (ZnS), galena (PbS), arsenopyrite (FeAsS2), other sulphides and sulfosalts which include minor elements like Mn, Co, Ni, Se, Cd, Sb, Te, Hg and Bi. Some of the main and minor elements of these ores are hazardous and the drainage basins of pollutant source areas often induce health concerns in the resident population. Electron probe microanalysis study followed previous optical and XRD analysis of the slags. The study focused on the identification of phases how sulphide and metallic phases are distributed within the material and infer about leachable elements during weathering. Electron probe X-ray maps show evidences of different behaviour between the elements: Ca and Zn are completely leached; iron is retained in oxyhydroxides, lead and arsenic precipitate as sulphates. Electron probe microanalysis studies are essential to understand complex materials as earth materials. Nevertheless, care is required to a correct interpretation of data and most quantitative compositional data are not trustworthy.
Mercury dispersion in soils of an abandoned lead-zinc-silver mine, San Quintín (Spain)
NASA Astrophysics Data System (ADS)
Esbrí, José Maria; Martín-Crespo, T.; Gómez-Ortiz, D.; Monescillo, C. I.; Lorenzo, S.; Higueras, P.
2010-05-01
The mine considered on this work, namely San Quintín, is a filonian field with hydrothermal ores exploited during almost fifty years (1887-1934), producing 550.000Tm of galena, 550Tm of silver and 5.000 of sphalerite. Some rewashing works of tailings muds was achieved in recent times (1973-1985), including flotation tests of cinnabar ore from Almadén mines. The main problems remaining on the site are an active acid mine drainage (with pH ~ 2) and heavy metal dispersion on soils including gaseous mercury emissions. We present here results of a survey including soils sampling with mercury analysis and other pedological parameters, as well as determinations of mercury inmission in the atmosphere, using a common sampling grid. Analysis of soils samples has been carried out using an atomic absorption spectrometer AMA254, while air determinations were made by the same technique, using a Lumex RA-915+. The maps have been obtained by means of SURFER 8 software, as well as by ArcGIS software, and puts forward dispersion of mercury from cinnabar ore dump (108 ?g×g-1) to nearby soils (0.3 ?g×g-1 at 700 m of distance). The dispersion of mercury vapor exceed WHO level for chronic exposure (200 ng×m-3) in a small area (250 meters from cinnabar dump).
NASA Astrophysics Data System (ADS)
Choi, Y.; Lee, I.; Choi, B.; KIM, Y.; Moon, I.
2017-12-01
The Central Seruyan Pb-Zn deposit is located in Seruyan, Central Kalimantan Province in Indonesia. This deposit has been developed since last year and is still being investigated. The Pb-Zn deposit consists of two formations, Pinoh and Kuayan formation. The former is a metamorphic unit hosting schist, phyllite and gneiss, and the latter is a pyroclastic and volcanic unit includes intermediate volcanic rocks such as dacite, tuff and breccia. Most host rocks of the deposit is composed of the silicified porphyritic dacite and silicified phyllite and covered by silicified tuff. The joints and fractures within the wall rock has E-W trends. The Seruyan Pb-Zn deposit is considered as hydrothermal breccia type.In this study, we observe ore minerals and host rocks to understand the genesis of the Pb-Zn deposit with geochemical data. Pyrite, chalcopyrite, sphalerite and galena are major ore minerals and covellite and bornite are also observed as minor sulfide minerals. These ore minerals, except pyrite, usually occur within quartz or calcite veins indicating the influence of hydrothermal fluid. In the host rocks, dacite, has the altered minerals like sericite, chlorite, epidote and some clay minerals of hydrothermal origin. All minerals occur as massive form. Only some pyrites have an euhedral form. Small amount of Au, Ag and Mo are detected in major ore minerals in the EPMA (electron probe X-ray microanalyzer) analyses.
Seal, R.R.; Hammarstrom, J.M.; Johnson, A.N.; Piatak, N.M.; Wandless, G.A.
2008-01-01
The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.
Belkin, H.E.; Luo, K.
2008-01-01
The Ni-Mo Huangjiawan mine, Guizhou Province, People's Republic of China, occurs in Lower Cambrian black shale (stone coal) in an area where other mines have recently extracted ore from the same horizon. Detailed electron microprobe (EMPA) and scanning electron microscope (SEM) analyses of representative thin sections have revealed a complex assemblage of sulfides and sulfarsenides. Early sulfidic and phosphatic nodules and host matrix have been lithified, somewhat fractured, and then mineralized with later-stage sulfides and sulfarsenides. Gersdorffite, millerite, polydymite, pyrite, sphalerite, chalcopyrite, galena, and clausthalite have been recognized. EMPA data are given for the major phases. Pyrite trace-element distributions and coeval Ni-, As-sulfides indicate that in the main ore layer, the last sulfide deposition was Ni-As-Co-rich. Mo and V deposition were early in the petrogenesis of these rocks. The assemblages gersdorffite-millerite-polydymite (pyrite) and millerite-gersdorffite (pyrite) and the composition of gersdorffite indicate a formation temperature of between 200?? and 300??C suggesting that the last solutions to infiltrate and mineralize the samples were related to hydrothermal processes. Environmentally sensitive elements such as As, Cd, and Se are hosted by sulfides and sulfarsenides and are the main source of these elements to residual soil. Crops grown on them are enriched in these elements, and they may be hazardous for animal and human consumption. ?? Springer-Verlag 2007.
Çelebi, Emin Ender; Öncel, Mehmet Salim; Kobya, Mehmet
2018-01-01
Weathering of sulfide minerals is a principal source of acid generation. To determine acid-forming potentials of sulfide-bearing materials, two basic approaches named static and kinetic tests are available. Static tests are short-term, and easily undertaken within a few days and in a laboratory. In contrast, kinetic tests are long-term procedures and mostly carried out on site. In this study, experiments were conducted over a medium-term period of 2 months, not as short as static tests and also not as long as kinetic tests. As a result, pH and electrical conductivity oscillations as a function of time, acid-forming potentials and elemental contents of synthetically prepared rainwater leachates of massive sulfides and sulfide-bearing lead-zinc tailings from abandoned and currently used deposition areas have been determined. Although the lowest final pH of 2.70 was obtained in massive pyrite leachate, massive chalcopyrite leachate showed the highest titrable acidity of 1.764 g H 2 SO 4 /L. On the other hand, a composite of currently deposited mine tailings showed no acidic characteristic with a final pH of 7.77. The composite abandoned mine tailing leachate had a final pH of 6.70, close to the final pH of massive galena and sphalerite leachates, and produced a slight titrable acidity of 0.130 g H 2 SO 4 /L.
Base and precious metal occurrences along the San Andreas Fault, Point Delgada, California
McLaughlin, Robert J.; Sorg, D.H.; Ohlin, H.N.; Heropoulos, Chris
1979-01-01
Previously unrecognized veins containing lead, zinc, and copper sulfide minerals at Point Delgada, Calif., are associated with late Mesozoic(?) and Tertiary volcanic and sedimentary rocks of the Franciscan assemblage. Sulfide minerals include pyrite, sphalerite, galena, and minor chalcopyrite, and galena-rich samples contain substantial amounts of silver. These minerals occur in a quartz-carbonate gangue along northeast-trending faults and fractures that exhibit (left?) lateral and vertical slip. The sense of fault movement and the northeasterly strike are consistent with predicted conjugate fault sets of the present San Andreas fault system. The sulfide mineralization is younger than the Franciscan rocks of Point Delgada and King Range, and it may have accompanied or postdated the inception of San Andreas faulting. Mineralization largely preceded uplift, the formation of a marine terrace, and the emplacement of landslide-related debris-flow breccias that overlie the mineralized rocks and truncate the sulfide veins. These field relations indicate that the sulfide mineralization and inception of San Andreas faulting were clearly more recent than the early Miocene and that the mineralization could be younger than about 1.2 m.y. The sulfide veins at Point Delgada may be of economic significance. However, prior to any exploitation of the occurrence, economic and environmental conflicts of interest involving private land ownership, the Shelter Cove home development, and proximity of the coast must be resolved.
NASA Astrophysics Data System (ADS)
Iatan, E. L.; Popescu, Gh. C.
2012-04-01
Rosia Poieni is the largest porphyry copper (±Au±Mo) deposits associated with Neogene magmatic rocks from the South Apuseni Mountains, being located approximately 8 km northeast of the town of Abrud. During a recent examination of some epithermal mineralized veins, crosscutting the porphyry mineralization from the Roşia Poieni deposit, two species of tellurides and one tellurosulfide minerals were identified. The studied samples were collected from the + 1045 m level, SW side of the open pit and are represented by epithermal veins, crosscutting the porphyry copper mineralized body. The thickness of the veins is almost 4 cm. Following reflected-polarized light microscopy to identify the ore-mineral assemblages, the polished sections were studied with a Scanning Electron Microscope (SEM) equipped with a back-scattered electron (BSE) detector to study fine-sized minerals. Quantitative compositional data were determined using a Cameca SX 50 electron microprobe (EMP). Based on optical microscopy, SEM and EMPA three mineral associations have been separated inside the epithermal vein, from the margins to the centre: 1. quartz+tennantite-tetrahedrite+goldfieldite+pyrite+sphalerite; 2. quartz+pyrite+tellurobismutite; 3. chalcopyrite+hessite+vivianite. Goldfieldite occurs in anhedral grains and it is associated with tennantite-tetrahedrite and quartz. The electron microprobe analysis gave a variable content in Te between 13.28-13.39 wt.%, 43.34 wt.% Cu, 0.1 wt. % Fe, 0.2 wt.% Zn, 14.68 wt.% As, 4.35 wt.% Sb and 24.84 wt.% S. The calculated formula for the goldfieldite is Cu11.8Te1.8(Sb,As)4S13.4. The EPM analyses on tetrahedrite-tennantite revealed a low content in Te (0.02-0.03 wt.%) and 42.23 wt.% Cu, 2.67 wt.% Fe, 7.34 wt.% Zn, 0.04 wt.% Sb, 19.28 wt.% As and 28.4 wt.% S. The calculated formula is Cu9.8(Fe,Zn)2.4(Sb,As,Te)3.8S13. The variable ratio of the Te content may reflect a variable content of Te in the hydrothermal fluids from which the tellurian tetrahedrite precipitated. Hessite lies close to the grain boundary between the calchopyrite grains, which is associated with vivianite. Electron microprobe analysis gave 57.73 wt.% Ag and 42.27 wt.% Te with calculated stoichiometric formula Ag1.9Te1.1 . Tellurobismuthite it forms irregular grains and it is associated with quartz and pyrite. Electron microprobe analysis gave 57.20 wt.% Bi and 42.80 wt.% Te with calculated stoichiometric formula Bi2.2Te2.8. Based on the mineral assemblages separated inside the ore vein and on the ratio of the Te content for the different identified tellurium bearing minerals, we can conclude that the Te content of the fluids from which they precipitated, increased from the margins to the centre of the vein. In summary, this study of specimens from Rosia Poieni porphyry copper deposit, has resulted in the recognition of some tellurium-bearing minerals, not reported by previous workers. These minerals are represented by tellurobismutite, hessite and goldfieldite and they are associated with epithermal vein mineralization (pyrite, chalcopyrite, sphalerite, tennantite-tetrahedrite, quartz, vivianite). The presence of tellurium indicates the transition between porphyry-style mineralization to epithermal vein mineralization. Acknowledgements: This work was supported by the strategic grant POSDRU/89/1.5/S58852, Project "Postdoctoral program for training scientific researches" co-financed by the European Social Found within the Sectorial Operational Program Human Resources Development 2007-2013".
Tormanen, T.O.; Koski, R.A.
2005-01-01
High gold contents (to 10.1 ppm, avg 1.4 ppm, n = 34) occur in pyrrhotite-rich massive sulfide samples from the sediment-covered floor of the Escanaba trough, the slow-spreading, southernmost segment of Gorda Ridge. These concentrations reflect the presence of primary gold, formed during high-temperature hydrothermal activity in mounds and chimneys, and secondary gold deposited during sea-floor weathering of massive sulfide. Primary gold occurs as fine-grained (2 ??m) secondary gold grains have a porous, flaky morphology and occur in samples in which pyrrhotite is oxidized and replaced by Fe oxyhydroxides, Fe sulfate, and sulfur. Mounds and chimneys dominated by pyrrhotite and containing lesser amounts of isocubanite, chalcopyrite, and Fe-rich sphalerite were formed by high-temperature (estimated range 325??-275??C), reduced, low-sulfur vent fluids. The mineral and fluid compositions during this main stage of hydrothermal venting reflect subsurface interaction between circulating hydrothermal fluids and turbiditic sediment containing as much as 1.1 percent organic carbon. As the deposition of pyrrhotite, Cu-Fe sulfides, and sphalerite waned, a volumetrically minor suite of sulfarsenide, arsenide, Bi, and Au minerals was deposited from highly reduced, late main-stage fluids diffusing through mounds and chimneys. The low solubility of Au as a bisulfide complex and the absence of fluid mixing during this stage of hydrothermal activity apparently inhibited the precipitation of gold directly from solution. Instead, gold precipitation is thought to be linked to elevated concentrations of Bi in the late main-stage fluids. The textural relationships of Au and Bi minerals in pyrrhotite-rich samples, low melting point of native bismuth (271.4??C), and recent experimental results on Au and Bi in hydrothermal fluids contribute to the hypothesis that gold was effectively scavenged from the Escanaba trough vent fluids by coexisting droplets of liquid bismuth. Additional phase relationships of alloys in the Au-Bi system indicate that deposition of native bismuth and maldonite occurred at temperatures as low as 241??C. Bismuth droplets trapped in void space between main-stage mineral grains scavenged gold from ambient hydrothermal fluid to a greater extent than bismuth enclosed by late-forming pyrrhotite. The limited solid solution of Au in Bi can explain the apparent exsolution texture in which gold blebs are hosted by native bismuth. The electrum, native bismuth (with gold inclusions), and galena represent the last traces of gold mineralization from late main-stage fluids. During sea-floor weathering and the oxidation of pyrrhotite in the mounds and chimneys, secondary gold formed as aggregates of colloidal particles along pH gradients between acidic pore waters and ambient seawater. Gold was mobilized from earlier formed primary gold minerals and transported as aqueous chloride complexes. The reduction of Au(III) by residual Fe2+ in partly altered pyrrhotite and adsorption of colloids by Fe oxyhydroxides may have influenced the location of secondary gold grains within the alteration front. Solubility differences between gold and silver chloride complexes at low temperature account for the low Ag content of secondary gold grains. The high concentrations of Bi, and thus the association of Au and Bi minerals in pyrrhotite-rich massive sulfide, can be ascribed to the extensive interaction of hydrothermal fluids with sediment in the Escanaba trough. In contrast, the absence of the Au-Bi association in massive sulfides at other ridges, including other sediment-covered sites at Middle Valley and the Guaymas basin
Rowan, E. Lanier; Goldhaber, Martin B.
1996-01-01
The Upper Mississippi Valley zinc-lead district is hosted by Ordovician carbonate rocks at the northern margin of the Illinois Basin. Fluid inclusion temperature measurements on Early Permian sphalerite ore from the district are predominantly between 90?C and I50?C. These temperatures are greater than can be explained by their reconstructed burial depth, which was a maximum of approximately 1 km at the time of mineralization. In contrast to the temperatures of mineral formation derived from fluid inclusions, biomarker maturities in the Upper Mississippi Valley district give an estimate of total thermal exposure integrated over time. Temperatures from fluid inclusions trapped during ore genesis with biomarker maturities were combined to construct an estimate of the district's overall thermal history and, by inference, the late Paleozoic thermal and hydrologic history of the Illinois Basin. Circulation of groundwater through regional aquifers, given sufficient flow rates, can redistribute heat from deep in a sedimentary basin to its shallower margins. Evidence for regional-scale circulation of fluids is provided by paleomagnetic studies, regionally correlated zoned dolomite, fluid inclusions, and thermal maturity of organic matter. Evidence for igneous acti vity contemporaneous with mineralization in the vicinity of the Upper Mississippi Valley district is absent. Regional fluid and heat circulation is the most likely explanation for the elevated fluid inclusion temperatures (relative to maximum estimated burial depth) in the Upper Mississippi Valley district. One plausible driving mechanism and flow path for the ore-forming fluids is groundwater recharge in the late Paleozoic Appalachian-Ouachita mountain belt and northward flow through the Reelfoot rift and the proto- Illinois Basin to the Upper Mississippi Valley district. Warm fluid flowing laterally through Cambrian and Ordovician aquifers would then move vertically upward through the fractures that control sphalerite mineralization in the Upper Mississippi Valley district. Biomarker reactant-product measurements on rock extracts from the Upper Mississippi Valley district define a relatively low level ofthermal maturity for the district, 0.353 for sterane and 0.577 for hopane. Recently published kinetic constants permit a time-temperature relationship to be determined from these biomarker maturities. Numerical calculations were made to simulate fluid heat flow through the fracture-controlled ore zones of the Thompson-Temperly mine and heat transfer to the adjacent rocks where biomarker samples were collected. Calculations that combine the fluid inclusion temperatures and the biomarker constraints on thermal maturity indicate that the time interval during which mineralizing fluids circulated through the Upper Mississippi Valley district is on the order of 200,000 years. Fluid inclusion measurements and thermal maturities from biomarkers in the district reflect the duration of peak temperatures resulting from regional fluid circulation. On the basis of thermal considerations, the timing of fluorite mineralization in southern Illinois, and the northward-decreasing pattern of fluorine enrichment in sediments, we hypothesize that the principal flow direction was northward through the Cambrian and Ordovician aquifers of the Illinois Basin. A basin-scale flow system would result in mass transport (hydrocarbon migration, transport of metals in solution) and energy (heat) transport, which would in turn drive chemical reactions (for example, maturation of organic matter, mineralization, diagenetic reactions) within the Illinois Basin and at its margins.
Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria
NASA Astrophysics Data System (ADS)
Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej
2015-04-01
The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur isotopic compositon of 14 sulfides as galena, sphalerite, pyrite and native sulfure were determined as well, with values ranging between -17.5 and 2.8 ‰ (CDT). For the investigated sulfates, the sulfur isotopic values show generally low values, which are characteristic for the late Permian. The broad distribution of sulfide values point toward bacterial reduction, fact also reflected by some higher isotopic values of sulfates. The oxygen values show a larger scatter from 9 to 23‰, which is even larger than that found for the Zechstein anhydrites of northern Germany, north-eastern Italian Alps or western Poland. The associated carbonates, as calcite, dolomite and magnesite are in disequilibrium with the sulfates indicating rather primary marine isotopic signature than re-equlibration with the sulfates at higher temperatures. References Leitner, C., Neubauer, F., Genser, J., Borojevic-Sostaric, B., Rantitsch, G., 2013. 40Ar/39Ar ages of recrystallization of rock-forming polyhalite in Alpine rocksalt deposits. In Jordan, F., Mark, D.F., Verati C. (eds.) Advances in 40Ar/39Ar Dating: from Archaeology to Planetary Sciences. Geological Society, London, Special Publications, 378, 207-244. Kirchner, E., 1987: Die Mineral- und Gesteinsvorkommen in den Gipslagerstätten der Lammermasse, innerhalb der Hallstattzone, Salzburg. Jahrbuch Haus der Natur. 10, 156-167. Postl, W., 1990. Enargit und Parnauit aus dem Gips- und Anhydritbergbau Tragöß-Oberort, Steiermark. In: Niedermayr, G. et al. (1990): Neue Mineralfunde aus Österreich XXXIX. Carinthia II, 180/100, 277. Tollmann, A., 1977. Geologie von Österreich. Band 1. Die Zentralalpen. Deuticke, Wien, 766 pp.
NASA Astrophysics Data System (ADS)
Shettigar, Nayana; Pramodini, S.; Kityk, I. V.; Abd-Lefdil, M.; Eljald, E. M.; Regragui, M.; Antony, Albin; Rao, Ashok; Sanjeev, Ganesh; Ajeyakashi, K. C.; Poornesh, P.
2017-11-01
We report the third-order nonlinear optical properties of electron beam treated Indium doped ZnO (Zn1-xInxO (x = 0.03) thin films at different dose rate. Zn1-xInxO (x = 0.03) thin films prepared by spray pyrolysis deposition technique were irradiated using 8 MeV electron beam at dose rates ranging from 1 kGy to 4 kGy. X-ray diffraction patterns were obtained to examine the structural changes, The transformation from sphalerite to wurtzite structure of ZnO was observed which indicates occurrence of structural changes due to irradiation. Morphology of irradiated thin films examined using atomic force microscopy (AFM) technique indicates the surface roughness varying with irradiation dose rate. The switching over from Saturable Absorption (SA) to Reverse Saturable Absorption (RSA) behaviour was noted when the irradiation dose rate was increased from 1 kGy to 4 kGy. The significant changes observed in the third-order nonlinear optical susceptibility χ(3) of the Zn1-xInxO (x = 0.03) thin films is attributed mainly due to electron beam irradiation. The study indicates that nonlinear optical parameters can be controlled by electron beam irradiation by choosing appropriate dose rate which is very much essential for device applications. Hence Zn1-xInxO (x = 0.03) materialize as a promising material for use in nonlinear optical device applications.
Reactive flow models of the Anarraaq Zn-Pb-Ag deposit, Red Dog district, Alaska
Schardt, C.; Garven, G.; Kelley, K.D.; Leach, D.L.
2008-01-01
The Red Dog ore deposit district in the Brooks Range of northern Alaska is host to several high-grade, shale-hosted Zn + Pb deposits. Due to the complex history and deformation of these ore deposits, the geological and hydrological conditions at the time of formation are poorly understood. Using geological observations and fluid inclusion data as constraints, numerical heat and fluid flow simulations of the Anarraaq ore deposit environment and coupled reactive flow simulations of a section of the ore body were conducted to gain more insight into the conditions of ore body formation. Results suggest that the ore body and associated base metal zonation may have formed by the mixing of oxidized, saline, metal-bearing hydrothermal fluids (<200??C) with reducing, HS-rich pore fluids within radiolarite-rich host rocks. Sphalerite and galena concentrations and base metal sulfide distribution are primarily controlled by the nature of the pore fluids, i.e., the extent and duration of the HS- source. Forward modeling results also predict the distribution of pyrite and quartz in agreement with field observations and indicate a reaction front moving from the initial mixing interface into the radiolarite rocks. Heuristic mass calculations suggest that ore grades and base metal accumulation comparable to those found in the field (18% Zn, 5% Pb) are predicted to be reached after about 0.3 My for initial conditions (30 ppm Zn, 3 ppm Pb; 20% deposition efficiency). ?? Springer-Verlag 2008.
Pannalal, S.J.; Symons, David T. A.; Leach, D.L.
2007-01-01
Zinc-lead mineralization in the Metaline mining district of northeastern Washington, USA, is hosted by the Cambrian Metaline Formation and is classified into Yellowhead-type (YO) and Josephine-type (JO) ore based on texture and mineralogy. Paleomagnetic results are reported for four Cambrian Metaline Formation sites, one Ordovician Ledbetter slate site, 12 YO and 13 JO (including two breccia sites) mineralization sites in the Pend Oreille Mine, and eight sites from the nearby Cretaceous Kaniksu granite batholith. Thermal and alternating field step demagnetization, saturation isothermal remanence analysis, and synthetic specimen tests show that the remanence in the host carbonates and Zn-Pb mineralization is carried mostly by pseudosingle (PSD) to single domain (SD) pyrrhotite and mostly by PSD to SD magnetite in the Kaniksu granite. Based on thermomagnetic measurements, sphalerite and galena concentrates and tailings from the mine's mill contain hexagonal and monoclimc pyrrhotite. The postfolding characteristic remanent magnetization (ChRM), known thermal data, and paleoarc method of dating suggest that the Zn-Pb mineralization carries a primary chemical remanent magnetization (CRM), and Metaline Formation carbonates a secondary CRM that were acquired during the Middle Jurassic (166 ??6 Ma) during the waning stages of the Nevadan orogeny. A paleomagnetic breccia test favours a solution-collapse origin for the Josephine breccia. Finally, the Kaniksu paleopole is concordant with the North American Cretaceous reference paleopole, suggesting the Kootenay terrane has not been rotated since emplacement of the batholith at ???94 Ma. ?? 2007 NRC Canada.
NASA Astrophysics Data System (ADS)
Wu, Shenghua; Mao, Jingwen; Yuan, Shunda; Dai, Pan; Wang, Xudong
2018-01-01
The Shizhuyuan polymetallic deposit is located in the central part of the Nanling region, southeastern China, and consists of proximal W-Sn-Mo-Bi skarns and greisens and distal Pb-Zn-Ag veins. The sulfides and sulfosalts in the distal veins formed in three distinct stages: (1) an early stage of pyrite and arsenopyrite, (2) a middle stage of sphalerite and chalcopyrite, and (3) a late stage of galena, Ag-, Sn-, and Bi-bearing sulfides and sulfosalts, and pyrrhotite. Combined sulfide and sulfosalt geothermometry and fluid inclusion analyses indicate that the early stage of mineralization occurred at a temperature of 400 °C and involved boiling under hydrostatic pressure ( 200 bar), with the temperature of the system dropping during the late stage to 200 °C. Laser Raman analysis indicates that the fluid inclusions within the studied minerals are dominated by H2O, although some contain carbonate solids and CH4 gas. Vein-hosted sulfides have δ34S values of 3.8-6.3‰ that are interpreted as indicative of a magmatic source of sulfur. The mineralization process can be summarized as follows: an aqueous fluid exsolved on final crystallization of the Qianlishan pluton, ascended along fracture zones, cooled to <400 °C, and boiled under hydrostatic conditions, and with decreasing temperature and sulfur fugacity, sulfide and sulfosalt minerals precipitated successively from the Ag-Cu-Zn-Fe-Pb-Sb-As-S-bearing fluid system.
NASA Astrophysics Data System (ADS)
Carrillo-Rosúa, J.; Morales-Ruano, S.; Morata, D.; Boyce, A. J.; Belmar, M.; Fallick, A. E.; Fenoll Hach-Alí, P.
2008-03-01
The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47'S Lat., 70°43'W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06-0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21-0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ18O and δD for the hydrothermal fluids were between 3 and 10‰ and between -95 and -75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit.
NASA Astrophysics Data System (ADS)
Xiao, Jian-Hua; Huang, Wei-Qing; Hu, Yong-sheng; Zeng, Fan; Huang, Qin-Yi; Zhou, Bing-Xin; Pan, Anlian; Li, Kai; Huang, Gui-Fang
2018-02-01
High photocatalytic activity and photostability are the pursuit of the goal for designing promising photocatalysts. Herein, using ZnO to encapsulate ZnS nanoparticles is proposed as an effective strategy to enhance photocatalytic activity and anti-photocorrosion. The ZnS/ZnO core/shell heterostructures are obtained via an annealing treatment of ZnS nanoparticles produced by a facile wet chemical approach. Due to its small size, the nascent cubic sphalerite ZnS (s-ZnS) converts into a hexagonal wurtzite ZnS (w-ZnS)/ZnO core/shell structure after annealing treatment. In situ oxidation leads to increasing ZnO, simultaneously decreasing the w-ZnS content in the resultant w-ZnS/ZnO with thermal annealing time. The w-ZnS/ZnO core/shell heterostructures show high photocatalytic activity, demonstrated by the photodegradation rate of methylene blue being up to ten-fold and seven-fold higher than that of s-ZnS under UV and visible light irradiation, respectively, and the high capability of degrading rhodamine B. The enhanced photocatalytic activity may be attributed to the large specific surface and improved charge carrier separation at the core/shell interface. Moreover, it displays high photostability owing to the protection of the ZnO shell, greatly inhibiting the photocorrosion of ZnS. This facile in situ oxidation is effective and easily scalable, providing opportunities for developing novel core/shell structure photocatalysts with high activity and photostability.
NASA Astrophysics Data System (ADS)
Drysdall, Alan R.; Douch, Colin J.
A composite sill of mineralized and highly radioactive microgranite—microsyenite caps Jabal Tawlah, a low ridge in the extreme NW of the Arabian Shield. The leucocratic composition, distribution of quartz and low K 2O:Na 2O ratios indicate that deuteric processes, including separation of a silica-rich phase and albitization, played a major role. Mineralization is in the form of a disseminated enrichment in Nb, Ta, Sn, Th, Y, heavy REE and Zr. Four Y- and heavy REE-bearing minerals, gagarinite [NaCaY(F,Cl) 6], fergusonite [(Y,Er,Ce,Fe)(Nb,Ta,Ti)O 4], xenotime and yttrian fluorite, as well as zircon, columbite, thorite, sphalerite, galena, pyrite, ilmenite, hematite, limonite, magnetite, goethite, siderite, possible chrysocolla and an MnO-bearing mineral have been identified. The geochemical signature of the mineralization is similar to that which distinguishes alkali granites from other granitic rocks. Jabal az Zuhd, a major plutonic complex consisting largely of alkali granite, crops out only 5 km NW of Jabal Tawlah. However, there is no other evidence of possible derivation from a parental alkali granite magma. Reserves indicated by outcrop dimensions and three drill-hole intersections are 6.4 million tonnes to an average depth of 65 m below wadi level, grading 0.34% Nb, 0.52% Y, 0.47% Zn and approximately 4% zircon (plus 175 ppm Ta, 380 ppm Sn, 700 ppm Th and heavy REE).
Xu, Xiaojie; Bullock, James; Schelhas, Laura T; Stutz, Elias Z; Fonseca, Jose J; Hettick, Mark; Pool, Vanessa L; Tai, Kong Fai; Toney, Michael F; Fang, Xiaosheng; Javey, Ali; Wong, Lydia Helena; Ager, Joel W
2016-03-09
P-type transparent conducting films of nanocrystalline (CuS)x:(ZnS)1-x were synthesized by facile and low-cost chemical bath deposition. Wide angle X-ray scattering (WAXS) and high resolution transmission electron microscopy (HRTEM) were used to evaluate the nanocomposite structure, which consists of sub-5 nm crystallites of sphalerite ZnS and covellite CuS. Film transparency can be controlled by tuning the size of the nanocrystallites, which is achieved by adjusting the concentration of the complexing agent during growth; optimal films have optical transmission above 70% in the visible range of the spectrum. The hole conductivity increases with the fraction of the covellite phase and can be as high as 1000 S cm(-1), which is higher than most reported p-type transparent materials and approaches that of n-type transparent materials such as indium tin oxide (ITO) and aluminum doped zinc oxide (AZO) synthesized at a similar temperature. Heterojunction p-(CuS)x:(ZnS)1-x/n-Si solar cells were fabricated with the nanocomposite film serving as a hole-selective contact. Under 1 sun illumination, an open circuit voltage of 535 mV was observed. This value compares favorably to other emerging heterojunction Si solar cells which use a low temperature process to fabricate the contact, such as single-walled carbon nanotube/Si (370-530 mV) and graphene/Si (360-552 mV).
The influence of doping element on structural and luminescent characteristics of ZnS thin films
NASA Astrophysics Data System (ADS)
Kryshtab, T.; Khomchenko, V. S.; Andraca-Adame, J. A.; Rodionov, V. E.; Khachatryan, V. B.; Tzyrkunov, Yu. A.
2006-10-01
For the fabrication of green and blue emitting ZnS structures the elements of I, III, and VII groups (Cu, Al, Ga, Cl) are used as dopants. The influence of type of impurity, doping technique, and type of substrate on crystalline structure and surface morphology together with luminescent properties was investigated. The doping of thin films was realized during the growth process and/or post-deposition thermal treatment. ZnS thin films were deposited by physical (EBE) and chemical (MOCVD) methods onto glass or ceramic (BaTiO 3) substrates. Closed spaced evaporation and thermodiffusion methods were used for the post-deposition doping of ZnS films. X-ray diffraction (XRD) techniques, atomic force microscopy (AFM), and measurements of photoluminescent (PL) spectra were used for the investigations. It was shown that the doping by the elements of I (Cu) and III (Al, Ga) groups does not change the crystal structure during the thermal treatment up to 1000 ∘C, whereas simultaneous use of the elements of I (Cu) and VII (Cl) groups leads to decrease of the phase transition temperature to 800 ∘C. The presence of impurities in the growth process leads to a grain size increase. At post-deposition treatment Ga and Cl act as activators of recrystallization process. The transition of ZnS sphalerite lattice to wurtzite one leads to the displacement of the blue emission band position towards the short-wavelength range by 10 nm.
Removal of groundwater arsenic using a household filter with iron spikes and stainless steel.
Avilés, M; Garrido, S E; Esteller, M V; De la Paz, J S; Najera, C; Cortés, J
2013-12-15
Arsenic (As) in groundwater for domestic use poses a worldwide threat to public health, most notably in rural areas. The aims of this study were: first, determine groundwater composition in a mining area in central Mexico (Huautla); second, assess As exposure through human groundwater consumption and; third, develop and test a household filter to obtain drinking water for these rural communities. From the 17th century through the 1990s, mines in the area produced Ag-galena and sphalerite from volcanic rock. Groundwater flooded the mines when they were abandoned due to low silver prices. Local households now use the water to meet domestic needs. Water from the mines was found to have high As content (0.04-0.26 mg L(-1)) and Fe, Mn, Pb and Cd were also above Mexican drinking water standards and WHO guidelines. All the population in the Huautla community was exposed to the metalloid through water used in food preparation. The best As removal was obtained with a filter using oxidized commercial fiber (HCl 2N as oxidant). Concentrations in the effluent were below Mexican drinking water standards (0.025 mg As L(-1) water) during the 105-day (2520 h) filter operation, with a maximum As removal efficiency of 95.4%. The household filter was simple, low-cost and may be very attractive for As removal in rural areas in developing countries. Copyright © 2013 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Zhao, Baojun; Hayes, Peter C.; Jak, Evgueni
2011-10-01
The phase equilibria in the ZnO-"FeO"-Al2O3-CaO-SiO2-S system have been determined experimentally in equilibrium with metallic iron. A pseudoternary section of the form ZnO-"FeO"-(Al2O3+CaO+SiO2) for CaO/SiO2 = 0.71 (weight), (CaO+SiO2)/Al2O3 = 5.0 (weight), and fixed 2.0 wt pct S concentration has been constructed. It was found that the addition of 2.0 wt pct S to the liquid extends the spinel primary phase field significantly and decreases the size of the wustite primary phase field. The liquidus temperature in the wustite primary phase field is decreased by approximately 80 K and the liquidus temperature in the spinel primary phase field is decreased by approximately 10 K with addition of 2.0 wt pct S in the composition range investigated. It was also found that iron-zinc sulfides are present in some samples in the spinel primary phase field, which are matte appearing at low zinc concentrations and sphalerite (Zn,Fe)S at higher zinc concentrations. The presence of sulfur in the slag has a minor effect on the partitioning of ZnO between the wustite and liquid phases but no effect on the partitioning of ZnO between the spinel and liquid phases.
A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA
NASA Astrophysics Data System (ADS)
Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.
2017-03-01
The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.
Taeniolite, an uncommon lithium-mica from Coyote Peak, Humboldt County, California.
Erd, Richard C.; Czamanske, G.K.; Meyer, C.E.
1983-01-01
Taeniolite has been found in a late pegmatitic clot in a mafic alkalic diatreme at Coyote Peak; associated species are natrolite, pectolite, aegirine, barytolamprophyllite, rasvumite and sphalerite. The taeniolite is green-brown with sp. gr. (meas.) 2.85(1) and H. 31/2. Optically it is biaxial (-) with alpha 1.541(2), beta = gamma 1.570(2), 2V approx 0o and moderate pleochroism with gamma = beta reddish-brown, alpha pale greenish brown. Single-crystal precession photographs show it to be of the 1M type, with a 5.254(2), b 9.110(4), c 10.187(2) A, beta 99.85(4)o and V = 480.4(1) A3. Combined microprobe and ion probe analyses gave SiO2 53.5, Al2O3 3.00, TiO2 1.06, FeO 3.35, MnO 0.21, MgO 18.3, Li2O 2.4, K2O 11.3, Na2O 0.27, F 6.3 = 99.69; SrO and BaO are both <0.04 wt.%; B, Be, Ca and Cl were not detected. Assuming (F + OH) = 2 and assigning 1.30 wt.% H2O gives 409(K1.01Na0.04)(Al0.01Ti0.06Fe2+0.20Mn0.01Mg1.92Li0.68)(Si3.76Al0.24)O10- (F1.40OH0.60).-G.W.R.
Remediation of metal-contaminated urban soil using flotation technique.
Dermont, G; Bergeron, M; Richer-Laflèche, M; Mercier, G
2010-02-01
A soil washing process using froth flotation technique was evaluated for the removal of arsenic, cadmium, copper, lead, and zinc from a highly contaminated urban soil (brownfield) after crushing of the particle-size fractions >250microm. The metal contaminants were in particulate forms and distributed in all the particle-size fractions. The particle-by-particle study with SEM-EDS showed that Zn was mainly present as sphalerite (ZnS), whereas Cu and Pb were mainly speciated as various oxide/carbonate compounds. The influence of surfactant collector type (non-ionic and anionic), collector dosage, pulp pH, a chemical activation step (sulfidization), particle size, and process time on metal removal efficiency and flotation selectivity was studied. Satisfactory results in metal recovery (42-52%), flotation selectivity (concentration factor>2.5), and volume reduction (>80%) were obtained with anionic collector (potassium amyl xanthate). The transportation mechanisms involved in the separation process (i.e., the true flotation and the mechanical entrainment) were evaluated by the pulp chemistry, the metal speciation, the metal distribution in the particle-size fractions, and the separation selectivity indices of Zn/Ca and Zn/Fe. The investigations showed that a great proportion of metal-containing particles were recovered in the froth layer by entrainment mechanism rather than by true flotation process. The non-selective entrainment mechanism of the fine particles (<20 microm) caused a flotation selectivity drop, especially with a long flotation time (>5 min) and when a high collector dose is used. The intermediate particle-size fraction (20-125 microm) showed the best flotation selectivity. Copyright 2009 Elsevier B.V. All rights reserved.
Iowa State Mining and Mineral Resources Research Institute
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1990-08-01
This final report describes the activities of the Iowa State Mining and Mineral Resources Research Institute (ISMMRRI) at Iowa State University for the period July 1, 1989, to June 30, 1990. Activities include research in mining- and mineral-related areas, education and training of scientists and engineers in these fields, administration of the Institute, and cooperative interactions with industry, government agencies, and other research centers. During this period, ISMMRRI has supported research efforts to: (1) Investigate methods of leaching zinc from sphalerite-containing ores. (2) Study the geochemistry and geology of an Archean gold deposit and of a gold-telluride deposit. (3) Enchancemore » how-quality aggregates for use in construction. (4) Pre-clean coal by triboelectric charging in a fluidized-bed. (5) Characterize the crystal/grain alignment during processing of yttrium-barium-copper-perovskite (1-2-3) superconductors. (5) Study the fluid inclusion properties of a fluorite district. (6) Study the impacts of surface mining on community planning. (7) Assess the hydrophobicity of coal and pyrite for beneficiation. (8) Investigate the use of photoacoustic absorption spectroscopy for monitoring unburnt carbon in the exhaust gas from coal-fired boilers. The education and training program continued within the interdepartmental graduate minor in mineral resources includes courses in such areas as mining methods, mineral processing, industrial minerals, extractive metallurgy, coal science and technology, and reclamation of mined land. In addition, ISMMRRI hosted the 3rd International Conference on Processing and Utilization of High-Sulfur Coals in Ames, Iowa. The Institute continues to interact with industry in order to foster increased cooperation between academia and the mining and mineral community.« less
Theodore, Ted G.; Orris, Greta J.; Hammerstrom, Jane M.; Bliss, James D.
1991-01-01
In recent years, a significant proportion of the mining industry's interest has been centered on discovery of gold deposits; this includes discovery of additional deposits where gold occurs in skarn, such as at Fortitude, Nevada, and at Red Dome, Australia. Under the classification of Au-bearing skarns, we have modeled these and similar gold-rich deposits that have a gold grade of at least 1 g/t and exhibit distinctive skarn mineralogy. Two subtypes, Au-skarns and byproduct Au-skarns, can be recognized on the basis of gold, silver, and base-metal grades, although many other geological factors apparently are still undistinguishable largely because of a lack of detailed studies of the Au-skarns. Median grades and tonnage for 40 Au-skarn deposits are 8.6 g/t Au, 5.0 g/t Ag, and 213,000 t. Median grades and tonnage for 50 byproduct and Au-skarn deposits are 3.7 g/t Au, 37 g/t Ag, and 330,000 t. Gold-bearing skarns are generally calcic exoskarns associated with intense retrograde hydrosilicate alteration. These skarns may contain economic amounts of numerous other commodities (Cu, Fe, Pb, Zn, As, Bi, W, Sb, Co, Cd, and S) as well as gold and silver. Most Au-bearing skarns are found in Paleozoic and Cenozoic orogenic-belt and island-arc settings and are associated with felsic to intermediate intrusive rocks of Paleozoic to Tertiary age. Native gold, electru, pyrite, pyrrhotite, chalcopyrite, arsenopyrite, sphalerite, galena, bismuth minerals, and magnetite or hematite are the most common opaque minerals. Gangue minerals typically include garnet (andradite-grossular), pyroxene (diopside-hedenbergite), wollastonite, chlorite, epidote, quartz, actinolite-tremolite, and (or) calcite.
High temperature neutron powder diffraction study of the Cu12Sb4S13 and Cu4Sn7S16 phases
NASA Astrophysics Data System (ADS)
Lemoine, Pierric; Bourgès, Cédric; Barbier, Tristan; Nassif, Vivian; Cordier, Stéphane; Guilmeau, Emmanuel
2017-03-01
Ternary copper-containing sulfides Cu12Sb4S13 and Cu4Sn7S16 have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu12Sb4S13 and Cu4Sn7S16 phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu12Sb4S13 decomposes above ≈792 K into Cu3SbS3, and (ii) Cu4Sn7S16 decomposes above ≈891 K into Sn2S3 and a copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu3SnS4 stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu12Sb4S13 are in fair agreement with recent published data, the decomposition behavior of Cu4Sn7S16 differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu4Sn7S16 and tetrahedrite Cu12Sb4S13 phases at 300 K, and for the high temperature form of skinnerite Cu3SbS3 at 843 K.
NASA Astrophysics Data System (ADS)
Miler, M.; Gosar, M.
2010-02-01
Stream sediment reflects the rock structure of the catchment area, its geochemical characteristics and possible recent contamination upstream of the sampling point and thus, it is most frequently used in geochemical researches of heavy metal pollution. Stream sediment samples were collected along the Meža River and its tributaries and the Drava River, located in the NNE part of Slovenia. Previous geochemical studies have shown that these sediments are heavily polluted with heavy metals as a consequence of past mining of Pb-Zn ore and steelworks activities. Conventional geochemical analyses (ICP-MS, AAS, etc.) provided limited information on mineralogy, morphology and sources of heavy metal-bearing phases therefore SEM/EDS was utilized. Several problems were confronted with during EDS analysis, which are related to identification and quantification of light elements, identification of elements due to peak overlaps and quantification of spectra from unpolished samples. These problems were successfully dealt with. SEM/EDS enabled successful identification of heavy metal-bearing phases in stream sediments. Ore mineral phases, such as cerussite, sphalerite, smithsonite and galena, different heavy metal-bearing Fe-alloys, Fe-oxides and spherical particles and common rock-forming and accessory mineral phases, such as barite, rutile, ilmenite, zircon and monazite, were identified using solely SEM/EDS. These results were used for subsequent geochemical interpretation and source apportionment of heavy metals, according to associations of different heavy metal-bearing phases. Heavy metal-bearing phases were arranged by their source and genesis into three groups, denoted as geogenic/technogenic, technogenic and geogenic.
NASA Astrophysics Data System (ADS)
Dias, S.; Cruz, I.; Fonseca, R.; Barriga, F. J.; Pedersen, R.
2010-12-01
The Jan Mayen vent fields were discovered in the Mohns Ridge during an expedition with the Norwegian research vessel "G.O. Sars" in July 2005. They comprise two main active areas: (1) Soria Moria and (2) Gallionella Garden & Trollveggen. The Trollveggen vent field is located at depths of 700-750 m. Venting takes place mainly through white smoker chimneys with fluid temperatures reaching up to 260-270°C. Here we present mineralogical and geochemical data from vent chimneys and metalliferous sediments collected at the Trollveggen vent field with an ROV. Cross-sections of chimneys present evident mineralogical zonation, showing acicular barite crystals in the outer parts and sulfide enrichments in the interior (Sph + Cpy +/- Py - Po). Sediments are mainly formed by vent fragments but also by minerals precipitated by diffuse fluid circulation, showing a mineral assemblage similar to that of chimneys. Microprobe analyses were obtained both in sulfates and sulphides revealing a particular sphalerite composition, characterized by low Fe (< 2%) and high total trace metal contents (up to 4%, including Cu, Ag and Au). Geochemical profiles of gravity cores collected in the area surrounding Jan Mayen were also performed in order to investigate the presence of additional hydrothermal activity in the area. Total geochemical analyses showed a slight enrichment in trace metals, such as Cu, Zn and Fe, with exception of one core that reached 85 ppm for Cu, 150 ppm for Zn and 20% for Fe. The metal enrichment in this core suggests hydrothermal activity in the neighboring area.
A contribution to improve the calculation of the acid generating potential of mining wastes.
Chopard, Aurélie; Benzaazoua, Mostafa; Bouzahzah, Hassan; Plante, Benoît; Marion, Philippe
2017-05-01
Mine wastes from sulfide-bearing ore extraction and processing are often stored at the surface of mine sites and could generate mine drainage. Prediction tests are completed to predict the water quality associated with the deposition of mining wastes. Static tests can quickly assess the acid-generating potential (AP) and the neutralization potential (NP). Whereas some studies recommend to take into account a mineral reactivity factor for the NP determination, the reactivity rates of acidifying minerals are not considered in the AP calculation. The aim of this study is to bring contribution to the improvement of the static test determination by adding kinetic factors in the AP determination. Eight sulfides (pyrite, Ni-pyrite, pyrrhotite, Ni-pyrrhotite, chalcopyrite, galena, sphalerite, arsenopyrite) and a sulfosalt (gersdorffite) were separately submitted to kinetic tests in modified weathering cells. This test was selected for its rapidity of results and for the low amount of material used, as it is somewhat difficult to obtain pure minerals samples. Five synthetic tailings were composed by mixing pure sulfides in various proportions and submitted to the same kinetic tests. The oxidation rates of synthetic tailings were compared with the weighted combined oxidation rates of individual pure sulfides. The oxidation rates of the synthetic tailings calculated from those of pure sulfides are within the same order of magnitude than those obtained through the kinetic experiments. The AP of synthetic tailings were calculated according to standard equations of the literature and compared with the new method. Copyright © 2017 Elsevier Ltd. All rights reserved.
Harrington, Andrea D.; Smirnov, Alexander; Tsirka, Stella E.; Schoonen, Martin A.A.
2014-01-01
The inhalation of mineral particulates and other earth materials, such as coal, can initiate or enhance disease in humans. Workers in occupations with high particulate exposure, such as mining, are particularly at risk. The ability of a material to generate an inflammatory stress response (ISR), a measure of particle toxicity, is a useful tool in evaluating said exposure risk. ISR is defined as the upregulation of cellular reactive oxygen species (ROS) normalized to cell viability. This study compares the ISR of A549 human lung epithelial cells after exposure to well-characterized common metal-sulfide ore mineral separates. The evaluation of the deleterious nature of ore minerals is based on a range of particle loadings (serial dilutions of 0.002 m2/mL stock) and exposure periods (beginning at 30 minutes and measured systematically for up to 24 hours). There is a wide range in ISR values generated by the ore minerals. The ISR values produced by the sphalerite samples are within the range of inert materials. Arsenopyrite generated a small ISR that was largely driven by cell death. Galena showed a similar, but more pronounced response. Copper-bearing ore minerals generated the greatest ISR, both by upregulating cellular ROS and generating substantial and sustained cell death. Chalcopyrite and bornite, both containing ferrous iron, generated the greatest ISR overall. Particles containing Fenton metals as major constituents produce the highest ISR, while other heavy metals mainly generate cell death. This study highlights the importance of evaluating the chemistry, oxidation states and structure of a material when assessing risk management. PMID:25107347
NASA Astrophysics Data System (ADS)
Abidi, R.; Slim-Shimi, N.; Somarin, A.; Henchiri, M.
2010-05-01
The Ain Allega Pb-Zn-Sr-Ba ore deposit is located in the flysch zone on the Eastern edge of the Triassic diapir of Jebel Hamra. It is part of the extrusive Triassic evaporate formation along the Ghardimaou-Cape Serrat faults. The ore body consists of argilic-dolomite breccias surrounded by argilo-gypsum Triassic formation, which forms the hanging wall of the deposit, and rimmed by the Paleocene marls. The ore minerals show a cap-rock type mineralization with different styles particularly impregnation in dolomite, cement of breccias, replacement ore and open space filling in the dissolution cavities and fractures. Ore minerals include sphalerite, galena, marcasite and pyrite. Principal gangue minerals are composed of barite, celestite, calcite, dolomite and quartz. The ore minerals are hosted by the Triassic carbonate rocks which show hydrothermal alteration, dissolution and brecciation. X-ray - crystallographic study of barite-celestite mineral series shows that pure barite and celestite are the abundant species, whereas strontianiferous barite (85-96.5% BaSO 4) and barian-celestite (95% SrSO 4) are minor. Primary and secondary mono-phase (liquid only) fluid inclusions are common in celestite. Microthermometric analyses in two-phases (liquid and vapour) fluid inclusions suggest that gangue and ore minerals were precipitated by a low-temperature (180 °C) saline (16.37 wt.% NaCl equivalent) solution originated possibly from a basinal brine with some input from magmatic or metamorphic fluid. Based on geology, mineralogy, texture and fluid characteristics, the Ain Allega deposit is classified as a carbonate-hosted Mississippi valley-type deposit.
Neil S. Fishman,; Sven O. Egenhoff,; Boehlke, Adam; Lowers, Heather A.
2015-01-01
The organic-rich upper shale member of the upper Devonian–lower Mississippian Bakken Formation (Williston Basin, North Dakota, USA) has undergone significant diagenetic alteration, irrespective of catagenesis related to hydrocarbon generation. Alteration includes precipitation of numerous cements, replacement of both detrital and authigenic minerals, multiple episodes of fracturing, and compaction. Quartz authigenesis occurred throughout much of the member, and is represented by multiple generations of microcrystalline quartz. Chalcedonic quartz fills radiolarian microfossils and is present in the matrix. Sulfide minerals include pyrite and sphalerite. Carbonate diagenesis is volumetrically minor and includes thin dolomite overgrowths and calcite cement. At least two generations of fractures are observed. Based on the authigenic minerals and their relative timing of formation, the evolution of pore waters can be postulated. Dolomite and calcite resulted from early postdepositional aerobic oxidation of some of the abundant organic material in the formation. Following aerobic oxidation, conditions became anoxic and sulfide minerals precipitated. Transformation of the originally opaline tests of radiolaria resulted in precipitation of quartz, and quartz authigenesis is most common in more distal parts of the depositional basin where radiolaria were abundant. Because quartz authigenesis is related to the distribution of radiolaria, there is a link between diagenesis and depositional environment. Furthermore, much of the diagenesis in the upper shale member preceded hydrocarbon generation, so early postdepositional processes were responsible for occlusion of significant original porosity in the member. Thus, diagenetic mineral precipitation was at least partly responsible for the limited ability of these mudstones to provide porosity for storage of hydrocarbons.
Exoplanet Classification and Yield Estimates for Direct Imaging Missions
NASA Astrophysics Data System (ADS)
Kopparapu, Ravi Kumar; Hébrard, Eric; Belikov, Rus; Batalha, Natalie M.; Mulders, Gijs D.; Stark, Chris; Teal, Dillon; Domagal-Goldman, Shawn; Mandell, Avi
2018-04-01
Future NASA concept missions that are currently under study, like the Habitable Exoplanet Imaging Mission (HabEx) and the Large Ultra-violet Optical Infra Red Surveyor, could discover a large diversity of exoplanets. We propose here a classification scheme that distinguishes exoplanets into different categories based on their size and incident stellar flux, for the purpose of providing the expected number of exoplanets observed (yield) with direct imaging missions. The boundaries of this classification can be computed using the known chemical behavior of gases and condensates at different pressures and temperatures in a planetary atmosphere. In this study, we initially focus on condensation curves for sphalerite ZnS, {{{H}}}2{{O}}, {CO}}2, and {CH}}4. The order in which these species condense in a planetary atmosphere define the boundaries between different classes of planets. Broadly, the planets are divided into rocky planets (0.5–1.0 R ⊕), super-Earths (1.0–1.75 R ⊕), sub-Neptunes (1.75–3.5 R ⊕), sub-Jovians (3.5–6.0 R ⊕), and Jovians (6–14.3 R ⊕) based on their planet sizes, and “hot,” “warm,” and “cold” based on the incident stellar flux. We then calculate planet occurrence rates within these boundaries for different kinds of exoplanets, η planet, using the community coordinated results of NASA’s Exoplanet Program Analysis Group’s Science Analysis Group-13 (SAG-13). These occurrence rate estimates are in turn used to estimate the expected exoplanet yields for direct imaging missions of different telescope diameters.
NASA Astrophysics Data System (ADS)
Choulet, Flavien; Barbanson, Luc; Buatier, Martine; Richard, James; Vennemann, Torsten; Ennaciri, Aomar; Zouhair, Mohamed
2017-10-01
Willemite (Zn2SiO4) usually reported in hypogene non-sulfide deposits is described as the main ore mineral in the carbonate-hosted Bou Arhous zinc deposit. This deposit is located in the High Atlas intracontinental range that formed during the Tertiary. Based on a set of microscopic observations, it was possible to establish that willemite replaces primary sphalerite. On the basis of cathodoluminescence imaging, three successive generations of willemite are distinguished, with evidence of dissolution-reprecipitation processes. Willemite is also variably enriched in Ge (up to 1000 ppm), while Ge contents lower than 100 ppm are reported in the primary sulfide minerals. Depending on the willemite generation, this substitution was positively or negatively correlated to the Zn-Pb substitution. According to the nature of zoning (sector versus oscillatory), the incorporation of Ge was either controlled by crystallographic factors or by the nature of the mineralizing fluids. Willemite is associated with other oxidation-related mineral species, like cerussite (PbCO3) but is not in isotopic equilibrium and therefore not considered to be cogenetic. Oxygen isotope compositions support the formation of willemite at temperatures below 130 °C, from mixed meteoric and deeper, hydrothermal fluids. The formation of the High Atlas Belt during the Tertiary has contributed to the exhumation of the sulfide minerals and the development of vertical conduits for percolation of meteoric water and ascending hydrothermal fluids. In addition to a local contribution of silicate minerals of the host limestone, hydrothermal fluids probably transported Si and Ge that are incorporated in willemite.
NASA Astrophysics Data System (ADS)
Sariiz, K.; Sendir, H.
2012-04-01
The study area is located at 30 km northwest of Domaniç (Kütahya) and covers on approximately 250 square kilometers. The Devonian (Paleozoic) schists which are composed of gneiss, mica schist and chlorite schist is the oldest unit of the study area. This units are overlain unconformably by the Permian Allıkaya Marbles. Eocene granodioritic intrusives cut other rock series and located as a batholite. Magmatic units present porphyric and holocrystalline textures. Granodioritic intrusions are represented by tonalite, tonalite porphyr, granodiorite, granodiorite porphyr, granite, diorite, diorite porphyries. Potassic, phyllitic and prophyllitic hydrothermal alteration zones are determined in host rocks and wallrocks. Mineralizations are observed as disseminated, and stockwork types within the granodioritic rocks. Ore minerals are pyrotine, pyrite, chalcopyrite, molybdenite, rutile, bornite, sphalerite, marcasite and limonite. Geochemically, it is of sub-alkaline affinity, belongs to the high-K, calc-alkaline series and displays features of typical I-type affinity. They show enrichment in large-ion lithophile elements (LIL) and depletion Nb and Ti indicating a subduction zone related magmatic signature for their origin. δ18O (quartz) values range from 8,8 to 12,1 ‰. δ18O (biotite) and δD (biotite) values range from 2,6 to 6,1 ‰ and -87 - -125 (SMOW). These values indicate that mixture magmatic-meteoric of hydrothermal solutions origin which are potassic to propylitic zones. δ13C (calcite) values range from 1,9 to 3,3 ‰ (PDB). Calcite values within the marine carbonates in the study area.
NASA Astrophysics Data System (ADS)
Basori, Mohd Basril Iswadi; Gilbert, Sarah; Large, Ross Raymond; Zaw, Khin
2018-06-01
The Bukit Botol volcanic-hosted massive sulphide (VHMS) deposit is located in the Central Belt of Peninsular Malaysia. The deposit occurs in a package of Permian-aged coherent felsic volcanic and volcaniclastic rocks which have a geochemical signature indicative of a volcanic arc tectonic setting. Mineralisation shows distinct ore zonation, forming a stringer to massive sulphide zone at the footwall followed by barite lenses and exhalite layers (Fe-Mn ore) at the top. Mineralogy is characterised by pyrite as the major sulphide mineral, with minor chalcopyrite, sphalerite, and rare galena; traces of gold, silver- and tin-bearing minerals also occur in the massive sulphide and barite ores. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis combined with the textural characteristics of pyrite provides evidence for significant variations of trace elements in different pyrite types at Bukit Botol, having three types of pyrite in the paragenetic sequence. The concentrations of As, Se, Te, Cu, Zn and Pb decrease from the early pyrite 1 to the late stage pyrite 3, and the Co/Ni ratios vary for the three pyrite types. The combined textural and compositional data of pyrite suggest that the hydrothermal fluid responsible for mineralisation evolved from an early, high temperature, reduced, low pH and desulphurized fluid to more S-rich, oxidized, high pH and cooler fluid. Available sulphur isotope data from the Bukit Botol deposit point to reduced seawater, along with a possible magmatic contribution, as the most probable sources for the ore-forming fluids.
Graham, G.E.; Kelley, K.D.; Slack, J.F.; Koenig, A.E.
2009-01-01
The Zn-Pb-Ag metallogenic province of the western and central Brooks Range, Alaska, contains two distinct but mineralogically similar deposit types: shale-hosted massive sulphide (SHMS) and smaller vein-breccia occurrences. Recent investigations of the Red Dog and Anarraaq SHMS deposits demonstrated that these deposits are characterized by high trace-element concentrations of As, Ge, Sb and Tl. This paper examines geochemistry of additional SHMS deposits (Drenchwater and Su-Lik) to determine which trace elements are ubiquitously elevated in all SHMS deposits. Data from several vein-breccia occurrences are also presented to see if trace-element concentrations can distinguish SHMS deposits from vein-breccia occurrences. Whole-rock geochemical data indicate that Tl is the most consistently and highly concentrated characteristic trace element in SHMS deposits relative to regional unmineralized rock samples. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of pyrite and sphalerite indicate that Tl is concentrated in pyrite in SHMS. Stream sediment data from the Drenchwater and Su-Lik SHMS show that high Tl concentrations are more broadly distributed proximal to known or suspected mineralization than As, Sb, Zn and Pb anomalies. This broader distribution of Tl in whole-rock and particularly stream sediment samples increases the footprint of exposed and shallowly buried SHMS mineralization. High Tl concentrations also distinguish SHMS mineralization from the vein-breccia deposits, as the latter lack high concentrations of Tl but can otherwise have similar trace-element signatures to SHMS deposits. ?? 2009 AAG/Geological Society of London.
NASA Astrophysics Data System (ADS)
Watanabe, Y.; Ohmoto, H.
2010-12-01
As part of the Archean Biosphere Drilling Project (ABDP), we have determined the multiple sulfur isotope ratios and examined the mineralogical and geochemical characteristics of the sulfur-bearing minerals (e.g., pyrite, sphalerite, barite) and the host rocks (e.g., major and trace element chemistry; Corg, Ccarb and S contents; δ13Corg and δ13Ccarb) of >100 samples of sedimentary rocks from five ABDP drill cores in the Pilbara Craton, Western Australia. The total ranges of Δ33S and δ34S values of the studied samples are -0.9 to +1.2‰ and -4 to +8‰, respectively. We have found that the Δ33S and δ34S relationships show unique values depending on their depositional environment: (1) Pyrites in the 3.46 Ga Marble Bar Chert Member (ABDP #1), which were formed by submarine hydrothermal fluids, show no AIF-S (anomalously fractionated sulfur isotope) signatures: Δ33S = -0.08 to +0.08‰ and δ34S = -3.3 to +0.6‰ (n = 5). This indicates that the H2S presented in the submarine hydrothermal fluid, which was partly generated through seawater sulfate reduction by Fe2+, did not possess AIF-S signatures. (2) Pyrites in organic C-poor lacustrine shales of the 2.76 Ga Hardey Formation (ABDP #3) also show no or very little AIF-S signatures: Δ33S = -0.38 to +0.25‰ and δ34S = -2.7 to +1.9‰ (n = 18). (3) Pyrites in organic C-poor marine shales of the 2.92 Ga Mosquito Creek Formation (ABDP#5) show no or small negative AIF-S signatures: Δ33S = -0.59 to 0.19 ‰ and all positive δ34S = +1.4 to +7.7‰ (n = 24). (4) Pyrites in organic C-rich (> 1 wt%) and hydrothermally altered marine shales in the 3.46 Ga Panorama Formation (ABDP #2) show constant and small positive AIF-S signatures (+0.44 to +0.61‰) and the smallest variation in δ34S (-1.1 to +1.6‰) (n = 35). In contrast, pyrites in organic C-rich shales in the 2.72 Ga Mt. Roe Basalt show negative Δ33S = -0.50 to -0.10‰ and δ34S = -3.7 to 1.8‰ (n = 10). (5) Pyrites in stromatolitic carbonates of the 2.7 Ga Tumbiana Formation (ABDP #10), which deposited in shallow evaporating marine basins, possess the largest variation in AIF-S signatures among five ABDP cores: Δ33S = -0.86 to 1.19‰ and δ34S = -3.2 to +1.5‰ (n = 10). (6) Compared to the negative Δ33S values (-1.28 to -0.47‰) of barites in the 3.2 Ga Dresser Formation (e.g., Ueno et al., 2009), Δ33S values of barites in the 3.46 Ga Panorama Formation (ABDP #2) are all positive (+0.55 to +0.61‰) and identical to those of reduced sulfur species (sphalerite and pyrite) in the same sample. The observed relationships between AIF-S signatures and depositional environments, and the abundance of samples with no AIF-S signatures, are difficult to explain by the current popular model that links AIF-S to atmospheric UV reactions. However, the data can be best explained by our model that links AIF-S to thermochemical sulfate reduction (TSR) by various solid phases and S-bearing aqueous/gaseous species (e.g., TSR by organic matter; replacement of iron oxides by pyrite) under hydrothermal conditions in a local and/or regional (basin wide) scale. Therefore, the AIF-S record of sedimentary rocks may be linked to the Earth’s thermal and biological evolution, rather than to the atmospheric evolution.
NASA Astrophysics Data System (ADS)
Martín-Crespo, Tomás.; Gómez-Ortiz, David; Martínez-Pagán, Pedro; Martín-Velázquez, Silvia; de Ignacio, Cristina; Lillo, Javier; Faz, Angel
2010-05-01
Mine tailings constitute an environmental issue of public concern because they represent accumulations and emission sources of heavy metals and acid mine drainage by sulphide oxidation. In this work, two geophysical methods, electrical resistivity tomography (ERT) and ground-penetrating radar (GPR), as well as mineralogical and geochemical techniques have been used in order to obtain a geo-environmental characterization of two dry riverbeds in a mining district. The abandoned San Cristóbal and Los Perules mining group (Mazarrón, Murcia) has generated a huge amount of sludge from the Ag, Pb and Zn extraction operations. These tailings were piled up in ponds or directly dumped to the San Cristóbal dry riverbed located at the mining site, and Las Moreras dry riverbed, where San Cristóbal flows into a few meters downstream. Furthermore, Las Moreras watercourse flows into the Mediterranean Sea five kilometres downstream. Samples from two boreholes have been analyzed in order to obtain thickness, mineralogical and chemical composition of tailings and watercourse sedimentary materials affected by them. San Cristóbal sampling point shows a thickness of 3,5 m of mine tailings, 2 m of sedimentary materials, and the in situ volcanic rocks to 5,5 m depth. Las Moreras site shows a thickness of 2 m of a mine tailings deposit, 4 m of sedimentary materials, and the in situ metamorphic rocks 6 m depth. In both sites, significant amounts of pyrite (15-20 wt %), sphalerite (10-15 wt %) and galena (5-10 wt %) have been determined, and secondary oxides (hematite) and sulphates (gypsum, jarosite) minerals have been also identified. Ag, As, Cd, Co, Cu, Sb, V, Pb and Zn contents are also significant in all studied samples from tailings samples, and acid mine drainage has been clearly detected affecting the San Cristóbal dry riverbed. Regarding the alluvial materials from the riverbeds, pyrite, sphalerite and galena have been only identified in the San Cristóbal sampling point, probably due to its location at the mining site. Furthermore, heavy metal content of both dry riverbeds show significant amounts of Ag, As, Cu, Sb, Pb, V and Zn, indicating an important process of contamination from the surficial tailings to the natural sediments and watercourses. Water from Las Moreras riverbed has also been analysed. Its pH is about 8 and it exhibit higher values in conductivity and TDS, together with the concentrations of major metallic ions, mainly Cu, Ni, Fe and Zn, most of them beyond the established limits for this kind of natural waters. ERT and GPR techniques have provided estimations of both thickness and internal structure of the dry riverbeds infilling. For San Cristóbal site, ERT indicates a ~6 m thick sedimentary sequence, in good agreement with borehole data. An upper unit of 30 ohm.m extending up to 1.5 m depth, and a lower unit of resistivity values lower than 5 ohm.m up to 6 m depth can be distinguished. The first unit corresponds to upper part of the tailing, characterized by sand texture, whereas the lower one corresponds to tailing with silty-clay texture and sedimentary material with high metal contents. For Las Moreras site a 2 m thick upper unit of low (< 5 ohm-m) resistivity values and a 4 m thick lower one of ~20-30 ohm.m are distinguished, in good agreement with the surficial tailings and lower sedimentary materials obtained in the borehole. Joint application of geophysical and geochemical techniques has revealed itself as very useful for obtaining a complete characterization of abandoned mine deposits, previously to a future reclamation of these dangerous tailings.
Changes in zinc speciation with mine tailings acidification in a semi-arid weathering environment
Hayes, Sarah M.; O’Day, Peggy A.; Webb, Sam M.; Maier, Raina M.; Chorover, Jon
2011-01-01
High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semi-arid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6,000 to 450 mg kg−1) and plant-available (590 to 75 mg kg−1) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and micro-focused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn0.8talc), Zn sorbed to ferrihydrite (ZnadsFeOx), and zinc sulfate (ZnSO4·7H2O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly-crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Micro-scale analyses identified hetaerolite (ZnMn2O4), hemimorphite (Zn4Si2O7(OH)2·H2O) and sphalerite (ZnS) as minor phases. Bulk and micro-focused spectroscopy complement the chemical extraction results and highlight the importance of using a multi-method approach to interrogate complex tailings systems. PMID:21761897
Hydrothermal processes in the Edmond deposits, slow- to intermediate-spreading Central Indian Ridge
NASA Astrophysics Data System (ADS)
Cao, Hong; Sun, Zhilei; Zhai, Shikui; Cao, Zhimin; Jiang, Xuejun; Huang, Wei; Wang, Libo; Zhang, Xilin; He, Yongjun
2018-04-01
The Edmond hydrothermal field, located on the Central Indian Ridge (CIR), has a distinct mineralization history owing to its unique magmatic, tectonic, and alteration processes. Here, we report the detailed mineralogical and geochemical characteristics of hydrothermal metal sulfides recovered from this area. Based on the mineralogical investigations, the Edmond hydrothermal deposits comprise of high-temperature Fe-rich massive sulfides, medium-temperature Zn-rich sulfide chimney and low-temperature Ca-rich sulfate mineral assemblages. According to these compositions, three distinctive mineralization stages have been identified: (1) low-temperature consisting largely of anhydrite and pyrite/marcasite; (2) medium-high temperature distinguished by the mineral assemblage of pyrite, sphalerite and chalcopyrite; and (3) low-temperature stage characterized by the mineral assemblage of colloidal pyrite/marcasite, barite, quartz, anglesite. Several lines of evidence suggest that the sulfides were influenced by pervasive low-temperature diffuse flows in this area. The hydrothermal deposits are relatively enriched in Fe (5.99-18.93 wt%), Zn (2.10-10.00 wt%) and Ca (0.02-19.15 wt%), but display low Cu (0.28-0.81 wt%). The mineralogical varieties and low metal content of sulfides in the Edmond hydrothermal field both indicate that extensive water circulation is prevalent below the Edmond hydrothermal field. With regard to trace elements, the contents of Pb, Ba, Sr, As, Au, Ag, and Cd are significantly higher than those in other sediment-starved mid-ocean ridges, which is indicative of contribution from felsic rock sources. Furthermore, the multiphase hydrothermal activity and the pervasive water circulation underneath are speculated to play important roles in element remobilization and enrichment. Our findings deepen our understanding about the complex mineralization process in slow- to intermediate-spreading ridges globally.
Fey, David L.; Desborough, George A.; Finney, Christopher J.
2000-01-01
IntroductionMetal-mining related wastes in the Boulder River basin study area in northern Jefferson County, Montana, have been implicated in their detrimental effects on water quality with regard to acid generation and toxic-metal solubilization during snow melt and storm water runoff events. This degradation of water quality is defined chiefly by the “Class 1 Aquatic Life Standards” that give limits for certain dissolved metal concentrations according to water alkalinity.Veins enriched in base- and precious metals were explored and mined in the Basin, Cataract Creek, and High Ore Creek drainages over a period of more than 70 years. Extracted minerals included galena, sphalerite, pyrite, chalcopyrite, tetrahedrite and arsenopyrite. Most of the metal-mining wastes in the study area were identified and described by the Montana Bureau of Mines and Geology. In 1997, the U.S. Geological Survey collected 20 composite samples of mine-dump or tailings waste from ten sites in the Basin and Cataract Creek drainages, and two samples from one site in the High Ore Creek drainage. Desborough and Fey presented data concerning acid generation potential, mineralogy, concentrations of certain metals by energy-dispersive X-ray fluorescence (EDXRF), and trace-element leachability of mine and exploration wastes from the ten sites of the Basin and Cataract Creek drainages. The present report presents total-digestion major- and trace-element analyses, net acid production (NAP), and results from the EPA-1312 synthetic precipitation leach procedure (SPLP) performed on the same composite samples from the ten sites from the Basin and Cataract Creek drainages, and two composite samples from the site in the High Ore Creek drainage.
NASA Astrophysics Data System (ADS)
Peng, Ning-Jun; Jiang, Shao-Yong; Xiong, Suo-Fei; Pi, Dao-Hui
2018-02-01
The Dalingshang W-Cu deposit is located in the North section of the Dahutang ore field, northern Jiangxi Province, South China. Vein- and breccia-style tungsten-copper mineralization is genetically associated with Mesozoic S-type granitic rocks. Infrared and conventional microthermometric studies of both gangue and ore minerals show that the homogenization temperatures for primary fluid inclusions in wolframite ( 340 °C) are similar to those in scheelite ( 330 °C), but about 40 °C higher than those of apatite ( 300 °C) and generally 70 °C higher than those in coexisting quartz ( 270 °C). Laser Raman analysis identifies CH4 and N2 without CO2 in fluid inclusions in scheelite and coexisting quartz, while fluid inclusions in quartz of the sulfide stage have variable CO2 content. The ore-forming fluids overall are characterized by high- to medium-temperature, low-salinity, CH4, N2, and/or CO2-bearing aqueous fluids. Chalcopyrite, muscovite, and sphalerite are the most abundant solids recognized in fluid inclusions from different ores. The H-O-S-Pb isotope compositions favor a dominantly magmatic origin for ores and fluids, while some depleted δ34S values (- 14.4 to - 0.9‰) of sulfides from the sulfide stage are most likely produced by an increase of oxygen fugacity, possibly caused by inflow of oxidized meteoric waters. The microthermometric data also indicate that a simple cooling process formed early scheelite and wolframite. However, increasing involvement of meteoric waters and fluid mixing may trigger a successive deposition of base metal sulfides. Fluid-rock interaction was critical for scheelite mineralization as indicated by in-situ LA-ICP-MS analysis of trace elements in scheelite.
Harrington, Andrea D.; Smirnov, Alexander; Tsirka, Stella E.; ...
2014-07-10
The inhalation of mineral particulates and other earth materials, such as coal, can initiate or enhance disease in humans. Workers in occupations with high particulate exposure, such as mining, are particularly at risk. The ability of a material to generate an inflammatory stress response (ISR), a measure of particle toxicity, is a useful tool in evaluating said exposure risk. ISR is defined as the upregulation of cellular reactive oxygen species (ROS) normalized to cell viability. This study compares the ISR of A549 human lung epithelial cells after exposure to well-characterized common metal-sulfide ore mineral separates. The evaluation of the deleteriousmore » nature of ore minerals is based on a range of particle loadings (serial dilutions of 0.002 m 2/mL stock) and exposure periods (beginning at 30 min and measured systematically for up to 24 h). There is a wide range in ISR values generated by the ore minerals. The ISR values produced by the sphalerite samples are within the range of inert materials. Arsenopyrite generated a small ISR that was largely driven by cell death. Galena showed a similar, but more pronounced response. Copper-bearing ore minerals generated the greatest ISR, both by upregulating cellular ROS and generating substantial and sustained cell death. Chalcopyrite and bornite, both containing ferrous iron, generated the greatest ISR overall. Particles containing Fenton metals as major constituents produce the highest ISR, while other heavy metals mainly generate cell death. Furthermore, this study highlights the importance of evaluating the chemistry, oxidation states and structure of a material when assessing risk management.« less
Occurence of ore metals in some terrestrial geothermal systems
DOE Office of Scientific and Technical Information (OSTI.GOV)
Browne, P.
1984-02-01
Drilling programs and the study of active geothermal systems have shown that the reservoir rocks in many fields contain minor quantities of base and precious metals. Commonly, base-metal sulfides occur in the subsurface but, where present, Au, Ag, Hg, As, Tl and Sb rich precipitates deposit near, or at, the surface. Although in some fields (Geysers, Larderello, Tongonan) some of the ore minerals (and others) are relict, there is evidence that they are now depositing in a few systems. Recent work on active hydrothermal systems in New Zealand shows that: (1) Sphalerite, galena, chalcopyrite (forming veins and disseminated discrete crystals)more » plus rare pentlandite, cobaltite and arsenopyrite, occur at Broadlands, NZ. Rare quantities of base-metal sulfides also occur in cores and cuttings from the geothermal fields of Waiotapu, Kawerau, Tauhara, and Ngawha. Further, Kakimoto (1983) has identified cassiterite, native silver, and trace gold in cores from Tauhara, in the south-eastern part of the Wairakei field. Bore temperatures at the depths from which these minerals were recovered are mostly between 220/sup 0/ and 300/sup 0/C, but at Broadlands are locally as low as 120/sup 0/C. The host rocks are Quaternary calc-alkali, silicic lavas and pyroclastic rocks, andesites, dacite and deep Mesozoic greywackes and argillites; however, there is no obvious relationship between mineralization and stratigraphy, permeability or well output. The deposition of amorphous precious metal precipitates (Au, Ag, Hg, As, Sb, Tl) from hot springs and well discharges has taken place at Broadlands, Waiotapu and Rotokawa; it also occurs at Kawerau. Water discharging from Frying Pan Lake, Waimangu, is presently depositing siliceous sinter containing up to 4.1% tungsten.« less
NASA Astrophysics Data System (ADS)
Tanner, D.; McDonald, I.; Harmer, R. E. J.; Hughes, H. S. R.; Muir, D. D.
2017-12-01
The Volspruit deposit is a zone of disseminated magmatic sulphides carrying Ni-PGE (platinum-group element) mineralization in the Northern Limb of the Bushveld Complex, South Africa. It is one of the few known PGE prospects hosted by the lower ultramafic portion of a layered intrusion and the only known example in the Bushveld Complex. Volspruit therefore provides a unique insight into the processes governing mineralisation early in the Bushveld magmatic system. This study presents a detailed analysis from the northern portion of the Volspruit orebody combining mineralogical and textural observations with sulphide mineral trace element compositions. Electron microscopy reveals a diverse assemblage of Pt-, Pd- and Rh- dominant platinum-group minerals (PGM), electrum, Ag tellurides, Pb-chlorides, Pb-sulphides, U-oxide and monazite. Laser ablation ICP-MS has demonstrated that the Volspruit base metal sulphides have elevated PGE tenors but a range of S/Se values 1414-19319 - greater than other magmatic sulphide deposits in the northern Bushveld. The S/Se values are typical of crustal S and in agreement with previous S isotope data. These data imply a magma with initially high tenor sulphide liquid experienced local contamination from sedimentary S, leading to reduced tenors and elevated S/Se in sulphides coupled with a propensity of Pb- and Zn-bearing minerals (e.g., Pb-sulphide, Pb-chloride and sphalerite) in association with archetypal orthomagmatic sulphide assemblages. Our data demonstrate that assimilation of sedimentary rocks can modify sulphide melt evolution through the addition of metals such as Pb and Zn, not just contamination by sulphur. The Volspruit deposit illustrates the complexity of multi-stage processes governing mineralisation in the ultramafic portions of layered mafic intrusions.
Gillerman, Elliot; Whitebread, Donald H.
1953-01-01
The Black Hawk (Bullard Peak) district, Grant County, N. Mex., is 21 miles by road west of Silver City. From 1881 to 1893 more than $1,000,000.00 of high-grade silver ore is reported to have been shipped from the district. Since 1893 there has been no mining in the district except during a short period in 1917 when the Black Hawk mine was rehabilitated. Pre-Cambrian quartz diorite gneiss, which contains inclusions of quartzite, schist, monzonite, and quartz monzonite, is the most widespread rock in the district. The quartz diorite gneiss is intruded by many pre-Cambrian and younger rocks, including diorite granite, diabase, monzonite porphyry and andesite and is overlain by the Upper Cretaceous Beartooth quartzite. The monzonite porphyry, probably of late Cretaceous or early Tertiary age, forms a small stock along the northwestern edge of the district and numerous dikes and irregular masses throughout the district. The ore deposits are in fissure veins that contain silver, cobalt, and uranium. The ore minerals, which include native silver, niccolite, millerite, skutterudite, nickel skutterudite, bismuthinite, pitchblende, and sphalerite, are in a carbonate gangue in narrow, persistent veins, most of which trend northeasterly. Pitchblende has been identified in the Black Hawk and the Alhabra deposits and unidentified radioactive minerals were found at five other localities. The deposits that contain the radioactive minerals constitude a belt 600 to 1,500 feet wide that trends about N. 45° E., and is approximately parallel to the southeastern boundary of the monzonite porphyry stock. All the major ore deposits are in the quartz diorite gneiss in close proximity to the monzonite porphyry. The ore deposits are similar to the deposits at Great Bear Lake, Canada, and Joachimstahl, Czechoslovakia.
Dings, M.G.; Schafer, Max
1953-01-01
During the summer of 1952 most of the mines and prospects in the Garfield and Taylor Park quadrangles of west-central Colorado were examined radiometrically by the U. S. Geological Survey to determine the extent, grade, and mode of occurrence of radioactive substances. The region contains a relatively large number of rock types, chiefly pre-Cambrian schists, gneisses, and granites; large and small isolated areas of sedimentary rocks of Paleozoic and Mesozoic ages; and a great succession of intrusive rocks of Tertiary age that range from andesite to granite and occur as stocks, chonoliths, sills, dikes, and one batholith. The prevailing structures are northwest-trending folds and faults. Ores valued at about $30,000,000 have been produced from this region. Silver, lead, zinc, and gold have accounted for most of this value, but small tonnages of copper, tungsten, and molybdenum have also been produced. The principal ore minerals are sphalerite, silver-bearing galena, cerussite, smithsonite, and gold-bearing pyrite and limonite; they occur chiefly as replacement bodies in limestone and as shoots in pyritic quartz veins. Anomalous radioactivity is uncommon and the four localities at which it is known are widely separated in space. The uranium content of samples from these localities is low. Brannerite, the only uranium-bearing mineral positively identified in the region, occurs sparingly in a few pegmatites and in one quartz-beryl-pyrite vein. Elsewhere radioactivity is associated with (l) black shale seams in the Manitou dolomite, (2) a quartz-pyrite-molybdenite vein, (3) a narrow border zone of oxidized material surrounding a small lead zinc ore body in the Manitou dolomite along a strong fault zone.
NASA Astrophysics Data System (ADS)
Cao, Hua-Wen; Zhang, Shou-Ting; Santosh, M.; Zheng, Luo; Tang, Li; Li, Dong; Zhang, Xu-Huang; Zhang, Yun-Hui
2015-11-01
The Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore district is located in the East Qinling metallogenic belt on the southern margin of the North China Craton. Two ore fields (Nannihu and Yuku) are recognized in the district, and three types of deposits are identified from the two ore fields as follows: (1) the 6 proximal porphyry-skarn type Mo-W deposits occurring at the inner contact zone of the granite porphyries, (2) the 3 middle skarn-hydrothermal type Zn deposits, and (3) the 8 distal hydrothermal type Pb-Zn-Ag deposits at the periphery of the porphyry. We present C-H-O isotope compositions of hydrothermal quartz and calcite, S-Pb isotope compositions of sulfide minerals, and sphalerite Rb-Sr isochron ages from the 17 deposits. The geochemical and geochronological data from the two ore fields all show systematic temporal and spatial variation, and primarily lead to the following inferences. (1) The temperatures and salinities of the ore-forming fluids decreased during mineralization. The ore-forming fluids gradually evolved from magmatic water to mixed magmatic-meteoric water. (2) The metallogenic components were primarily derived from igneous rocks, with increasing proportions of the materials from the ore-bearing rocks. (3) The mineralization ages of these deposits are close (147-136 Ma), which correspond to the emplacement of the granite intrusions. (4) The three types of deposits and the ore-related late Mesozoic intrusives constitute a unified magmatic-hydrothermal-mineralization system. Finally, we also suggest exploration strategies for the Luanchuan ore district.
Geology and mineral deposits of the Minnie Moore and Bullion mineralized areas, Blaine County, Idaho
Link, Paul Karl; Worl, Ronald G.
2001-01-01
In the early 1880?s the discovery of rich ores in the Minnie Moore and Bullion mineralized areas sparked a rush to settle and develop the Wood River valley. Silver and lead discoveries in these areas spurred the boom in mining after completion of the Oregon Short Line Railroad to Hailey in 1883. In both areas the ore comprises galena, sphalerite, and tetrahedrite in a gangue of siderite, calcite, or quartz. Minor goldbearing quartz veins are also present. The ore is in fissure and replacement veins along fracture systems that formed in Late Cretaceous time, after intrusion of nearby granodiorite or quartz diorite stocks. The ore formed under mesothermal conditions and heat was supplied by the nearby plutons. In the Minnie Moore area, the mineralized veins are cut by low-angle normal faults that are of probable Eocene age. In the Minnie Moore mineralized area, the host rock is the middle part of the Devonian Milligen Formation, (the informal Lucky Coin limestone and Triumph argillite), which is the same stratigraphic level as the host ore in the rich Triumph mine northeast of Hailey. In the Bullion mineralized area, the ore is hosted by the lower member of the Middle Pennsylvanian to Lower Permian Dollarhide Formation. Rich ore was mined in several tunnels that reached the Mayflower vein, a northwest-striking mineralized shear zone. The deposits are thought to be mainly mesothermal veins that formed in association with Cretaceous magmatism. The syngenetic stratiform model of ore formation has often been applied to these deposits, however, no evidence of syngenetic mineralization was found in this study. Faulting has displaced most of the major orebodies and thus has made mining these deposits a challenge.
Automated Mineral Analysis to Characterize Metalliferous Mine Waste
NASA Astrophysics Data System (ADS)
Hensler, Ana-Sophie; Lottermoser, Bernd G.; Vossen, Peter; Langenberg, Lukas C.
2016-10-01
The objective of this study was to investigate the applicability of automated QEMSCAN® mineral analysis combined with bulk geochemical analysis to evaluate the environmental risk of non-acid producing mine waste present at the historic Albertsgrube Pb-Zn mine site, Hastenrath, North Rhine-Westphalia, Germany. Geochemical analyses revealed elevated average abundances of As, Cd, Cu, Mn, Pb, Sb and Zn and near neutral to slightly alkaline paste pH values. Mineralogical analyses using the QEMSCAN® revealed diverse mono- and polymineralic particles across all samples, with grain sizes ranging from a few μm up to 2000 μm. Calcite and dolomite (up to 78 %), smithsonite (up to 24 %) and Ca sulphate (up to 11.5 %) are present mainly as coarse-grained particles. By contrast, significant amounts of quartz, muscovite/illite, sphalerite (up to 10.8 %), galena (up to 1 %), pyrite (up to 3.4 %) and cerussite/anglesite (up to 4.3 %) are present as fine-grained (<500 μm) particles. QEMSCAN® analysis also identified disseminated sauconite, coronadite/chalcophanite, chalcopyrite, jarosite, apatite, rutile, K-feldspar, biotite, Fe (hydr) oxides/CO3 and unknown Zn Pb(Fe) and Zn Pb Ca (Fe Ti) phases. Many of the metal-bearing sulphide grains occur as separate particles with exposed surface areas and thus, may be matter of environmental concern because such mineralogical hosts will continue to release metals and metalloids (As, Cd, Sb, Zn) at near neutral pH into ground and surface waters. QEMSCAN® mineral analysis allows acquisition of fully quantitative data on the mineralogical composition, textural characteristics and grain size estimation of mine waste material and permits the recognition of mine waste as “high-risk” material that would have otherwise been classified by traditional geochemical tests as benign.
DOE Office of Scientific and Technical Information (OSTI.GOV)
King, D.E.; Meyers, W.J.
1985-02-01
The Lower Carboniferous Waulsortian Limestones, eastern Midlands, Republic of Ireland, contain 7 distinct luminescent zones in clear calcite cements that overlie inclusion-rich, marine cements in cavities and also fill fractures and aragonite-skeleton molds. The luminescent sequence, which records precipitation from increasingly reducing pore waters, is regionally and stratigraphically consistent over an interval more than 1200 ft thick. Zone 1 cements are nonluminescent; zone 2 cements are brightly luminescent; and zones 3-7 cements are ferroan with a moderate to dull luminescence. Zone 1 cements (mean -2.6% delta/sup 18/O/ +3.3% delta/sup 13/C PDB) are slightly depleted in oxygen relative to radiaxial-fibrous cementsmore » (mean -1.8% delta/sup 18/O/ +3.5% delta/sup 13/C PDB) which have a composition that reflects Lower Carboniferous seawater. Zone 4 cements (mean -4.1% delta/sup 18/O/ +3.1% delta/sup 13/C PDB) are depleted in oxygen relative to zone 1, whereas zone 5 cements (mean -11.8% delta/sup 18/O/ +1.1 delta/sup 13/C PDB) are extremely depleted in oxygen and somewhat in carbon. Locally intense dolomitization includes 2 regionally extensive generations of ferroan saddle dolomite. Petrographic relationships demonstrate these dolomite generations were replaced by zone 5 cement. Sulfide mineralization, principally pyrite and sphalerite, occurred after the precipitation of zone 5 cement. Much of diagenesis occurred during a brief period in the Lower Carboniferous. Zones 1-6 and saddle dolomites are contained in Chadian (upper Osagean), shallow-marine facies overlying the Waulsortian. Fractures filled by zone 5 cements are truncated at the margins of Waulsortian clasts contained in a conglomerate overlying an early Arundian (early Meramecian) unconformity.« less
NASA Astrophysics Data System (ADS)
Kubač, Alexander; Chovan, Martin; Koděra, Peter; Kyle, J. Richard; Žitňan, Peter; Lexa, Jaroslav; Vojtko, Rastislav
2018-03-01
The Au-Ag-Pb-Zn-Cu epithermal deposit Banská Hodruša of intermediate-sulphidation type is located in the Middle Miocene Štiavnica stratovolcano on the inner side of the Carpathian arc in Slovakia. This deposit represents an unusual subhorizontal multi-stage vein system, related to processes of underground cauldron subsidence and exhumation of a subvolcanic granodiorite pluton. Veins are developed on a low-angle normal shear zone, possibly representing a detachment zone in andesitic wall rocks that formed during emplacement and exhumation of the granodiorite pluton. The deposit consists of two parts, separated by a thick sill of quartz-diorite porphyry. The eastern part is currently mined, and the western part has already been depleted. The Banská Hodruša mineralization was formed during four stages: (1) low-grade silicified breccia at subhorizontal structures at the base of the deposit; (2) stockwork of steep veins with rhodonite-rhodochrosite, quartz-sulphide-carbonate and quartz-gold assemblages; (3) thin quartz-gold veins with medium dip in tension cracks inside the shear zone and complementary detachment hosted quartz-base metals-gold veins; (4) Post-ore veins. Gold and electrum (920-730) occur as intergrowths with base metal sulphides or hosted in quartz and carbonates, accompanied by Au-Ag tellurides (hessite, petzite). Rare Te-polybasite and Cu-cervelleite result from re-equilibration of early Te-bearing minerals during cooling. Sulphide minerals include low Fe sphalerite ( 1.25 wt%), galena, chalcopyrite, and pyrite. The wall rock alteration is represented mostly by adularia, illite, chlorite, quartz, calcite and pyrite. Precipitation of gold, Au-Ag tellurides, Mn-bearing minerals and adularia resulted from boiling of fluids due to hydraulic fracturing, as well as opening of dilatational structures within the shear zone.
Changes in zinc speciation with mine tailings acidification in a semiarid weathering environment.
Hayes, Sarah M; O'Day, Peggy A; Webb, Sam M; Maier, Raina M; Chorover, Jon
2011-09-01
High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kerimova, T. G., E-mail: taira-kerimova@mail.ru; Abdullaev, N. A.; Mamedova, I. A.
The Raman spectra of CdGa{sub 2}S{sub 4x}Se{sub 4(1-x)} alloys (x = 0.1, 0.2, Horizontal-Ellipsis 0.9) are studied. Both the singlemode and double-mode behavior of optical phonons are observed in CdGa{sub 2}S{sub 4x}Se{sub 4(1-x)} alloys. The observed optical mode at 138 cm{sup -1} is independent of the composition. It seems likely that this mode is the 'breathing mode' and is caused by atomic motion in the anion sublattice relative to vacancies. It is shown that the high-frequency modes of symmetry B{sub 1}(LO, TO) and B{sub 2}(LO, TO) are caused by the in-phase motion of atoms in the anion sublattice along themore » tetragonal axis c relative to trivalent Ga atoms. The doubly degenerate symmetry modes E{sub 1}(LO, TO) and E{sub 2}(LO, TO) are caused by the in-phase motion of atoms in the anion sublattice relative to trivalent Ga atoms of the cation sublattice in the xy plane (dipole 2Ga-4C), where C is S, Se. The optical symmetry modes B{sub 3}(LO, TO) and B{sub 4}(LO, TO) are associated with the motion of atoms in the anion sublattice relative to Cd atoms along the tetragonal axis c. The doubly degenerate modes E{sub 3}(LO, TO) and E{sub 4}(LO, TO) are associated with the motion of atoms in the anion sublattice relative to Cd atoms (dipole Cd-4C). The low-frequency modes B{sub 5}(LO, TO) and E{sub 5}(LO, TO) are the analogs of acoustic phonons at the edge of the Brillouin zone of sphalerite.« less
NASA Astrophysics Data System (ADS)
Cocker, Helen A.; Mauk, Jeffrey L.; Rabone, Stuart D. C.
2013-02-01
The 7.1 Ma Broken Hills adularia-sericite Au-Ag deposit is currently the only producing rhyolite-hosted epithermal deposit in the Hauraki Goldfield of New Zealand. The opaque minerals include pyrite, electrum, acanthite (Ag2S), sphalerite, and galena, which are common in other adularia-sericite epithermal deposits in the Hauraki Goldfield and elsewhere worldwide. Broken Hills ores also contain the less common minerals aguilarite (Ag4SeS), naumannite (Ag2Se), petrovskaite (AuAgS), uytenbogaardtite (Ag3AuS2), fischesserite (Ag3AuSe2), an unnamed silver chloride (Ag2Cl), and unnamed Ag ± Au minerals. Uytenbogaardtite and petrovskaite occur with high-fineness electrum. Broken Hills is the only deposit in the Hauraki Goldfield where uytenbogaardtite and petrovskaite have been identified, and these phases appear to have formed predominantly from unmixing of a precursor high-temperature phase under hypogene conditions. Supergene minerals include covellite, chalcocite, Au-rich electrum, barite, and a variety of iron oxyhydroxide minerals. Uytenbogaardtite can form under supergene and hypogene conditions, and textural relationships between uytenbogaardtite and associated high-fineness electrum may be similar in both conditions. Distinguishing the likely environment of formation rests principally on identification of other supergene minerals and documenting their relationships with uytenbogaardtite. The presence of aguilarite, naumannite, petrovskaite, and fischesserite at Broken Hills reflects a Se-rich mineral assemblage. In the Hauraki Goldfield and the western Great Basin, USA, Se-rich minerals are more abundant in provinces that are characterized by bimodal rhyolite-andesite volcanism, but in other epithermal provinces worldwide, the controls on the occurrences of Se-bearing minerals remain poorly constrained, in spite of the unusually high grades associated with many Se-rich epithermal deposits.
NASA Astrophysics Data System (ADS)
Valkama, M.; Sundblad, K.; Cook, N. J.; Ivashchenko, V. I.
2016-08-01
The historic mining district of Pitkäranta in the Ladoga region, Fennoscandian Shield, was exploited for Fe, Cu, Zn, Pb, Sn and Ag in the nineteenth to twentieth centuries. The Pitkäranta region is dominated by Palaeoproterozoic supracrustal rocks, which, together with gneissic Archaean dome structures, constitute an allochthonous terrane complex that amalgamated to the Archaean continent during the Svecokarelian orogeny at 1.9-1.8 Ga. This crustal complex was intruded by 1.8 Ga Late orogenic granites, 1.54 Ga anorogenic rapakivi granites and 1.45 Ga dolerites. The polymetallic skarn ores of Pitkäranta extend over a 25-km-long zone in Palaeoproterozoic supracrustal rocks and formed from hydrothermal solutions, which emanated from the anorogenic rapakivi granites and reacted with marble layers. Four major ore types are recognised after the dominating metal: Fe, Cu, Sn and Zn, respectively. These types are not restricted to individual mines or mine fields but represent end members in zonation patterns within each ore body. Pitkäranta was the second discovery site in the world for indium but has been without modern documentation for more than 75 years. The indium contents in the ores are up to 600 ppm, in most cases sphalerite-hosted. The only roquesite-bearing sample in this study had an indium grade of 291 ppm and an In/Zn ratio of 51 (close to the criteria for the limiting conditions for creating an In-rich mineral). The Pitkäranta ores have a potential for future small-scale exploitation, but all such plans are hampered by high contents if Bi, Cd and As.
Source Identification of Zn Contamination around a Zn-smelting Facility in Korea
NASA Astrophysics Data System (ADS)
Lee, S.; Jeon, S. K.
2016-12-01
With massive production of Zn for various industrial purposes, Zn release into the environment becomes highly possible, some of which might require a proper countermeasure depending on the residual concentration in environmental media. In order to set up an effective countermeasure, identification of contaminant source should be essential for determining the target object to be managed, and delineating the extent of necessary remedial work. In this study, we focus on a Zn-smelting facility located in eastern Korea where Zn concentrations in surrounding soils have been reported to exceed the contamination criteria. An abandoned mine which had been explored for Zn ores was located adjacent to the facility, and background concentration of Zn in the area was naturally high. The objective of the present study is to identify the major source of Zn contamination in the area, and to estimate the relative contributions of multiple sources, if so. In order to achieve these goals, we analyzed and compared the stable isotope ratios of Pb in the soil samples collected at different distances from the facility and the Zn concentrates (ZnS, sphalerite) of raw material in the facility. The Pb isotope ratios were further investigated by performing sequential extraction for each sample and comparing the isotopes ratios observed in each fraction of soil. In addition, possible presence of ZnS in the samples, which could be an evidence of Zn contamination by the smelting facility, was estimated by X-ray diffraction (XRD) analysis and scanning electron microscopy equipped with energy dispersive X-ray spectrometry (SEM-EDS) after separating the soil sample into the fractions with different particle sizes
Leonard, B.F.; Christian, R.P.
1987-01-01
Silver is an accessory element in gold, antimony, and tungsten deposits of the caldera complex. Most of the deposits are economically of low grade and genetically of xenothermal or epithermal character. Their gold- and silver-bearing minerals are usually disseminated, fine grained, and difficult to study. Sparsely disseminated pyrite and arsenoprite are common associates. Identified silver minerals are: native silver and electrum; the sulfides acanthite, argentite (the latter always inverted to acanthite), and members of the Silberkies group; the sulfosalts matildite, miargyrite, pyrargyrite, argentian tetrahedrite, and unnamed Ag-Sb-S and Ag-Fe-Sb-S minerals; the telluride hessite and the selenide naumannite; halides of the cerargyrite group; and the antimonate stetefeldtite. Suspected silver minerals include the sulfide uytenbogaardtite and the sulfosalts andorite, diaphorite, and polybasite. Electrum, acanthite, and argentian tetrahedrite are common, though nowhere abundant. The other silver minerals are rare. Silver is present as a minor element in the structure of some varieties of other minerals. These include arsenopyrite, chalcopyrite, chalcostibite, covelline, digenite, galena, sphalerite, and stibnite. The search for adventitious Ag in most of these minerals has been cursory. The results merely indicate that elemental silver is not confined to discrete silver minerals and is, therefore, an additional complication for the recovery of silver-bearing material from some deposits. Silver occurs cryptically in some plants of the region. At Red Mountain, for example, the ashed sapwood of Douglas-fir (Pseudotsuga menziesii) contains 2 to 300 ppm Ag. Silver in the ashed wood is roughly 100 times as abundant as it is in soil. The phenomenon, useful in biogeochemical exploration, deserves the attention of mineralogists. ?? 1987 Springer-Verlag.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Harrington, Andrea D.; Smirnov, Alexander; Tsirka, Stella E.
The inhalation of mineral particulates and other earth materials, such as coal, can initiate or enhance disease in humans. Workers in occupations with high particulate exposure, such as mining, are particularly at risk. The ability of a material to generate an inflammatory stress response (ISR), a measure of particle toxicity, is a useful tool in evaluating said exposure risk. ISR is defined as the upregulation of cellular reactive oxygen species (ROS) normalized to cell viability. This study compares the ISR of A549 human lung epithelial cells after exposure to well-characterized common metal-sulfide ore mineral separates. The evaluation of the deleteriousmore » nature of ore minerals is based on a range of particle loadings (serial dilutions of 0.002 m 2/mL stock) and exposure periods (beginning at 30 min and measured systematically for up to 24 h). There is a wide range in ISR values generated by the ore minerals. The ISR values produced by the sphalerite samples are within the range of inert materials. Arsenopyrite generated a small ISR that was largely driven by cell death. Galena showed a similar, but more pronounced response. Copper-bearing ore minerals generated the greatest ISR, both by upregulating cellular ROS and generating substantial and sustained cell death. Chalcopyrite and bornite, both containing ferrous iron, generated the greatest ISR overall. Particles containing Fenton metals as major constituents produce the highest ISR, while other heavy metals mainly generate cell death. Furthermore, this study highlights the importance of evaluating the chemistry, oxidation states and structure of a material when assessing risk management.« less
First Evidence of Epithermal Gold Occurrences in the SE Afar Rift, Republic of Djibouti
NASA Astrophysics Data System (ADS)
Moussa, Nima; Fouquet, Yves; Caminiti, Antoine Marie; Le Gall, Bernard; Rolet, Joel; Bohn, Marcel; Etoubleau, Joel; Delacourt, Christophe; Jalludin, Mohamed
2010-05-01
The Republic of Djibouti, located at the SE part of the Afar volcanic Triangle, is characterized by intense tectonic and bimodal volcanic activity, and is emplaced over an earlier magmatic rift system, as old as 25-30 Ma. Each magmatic event is accompanied by hydrothermal activity. Few works have been so far published on hydrothermal mineralization in the Afar area. Mineralization generally occur as veins and are mainly associated with acidic volcanic intrusions along the fractures at the edges of grabens established during the last 4 Ma. Eighty samples from hydrothermal quartz ± carbonate veins and breccias were studied on 9 different sites representative of 4 main volcanic events ranging in age from early Miocene up to Present. Gold was found in excess of 200 ppb in 30% of the samples. Mineralogical analyses based on optical reflected light microscopy, X-Ray diffractometry, X-Ray fluorescence, inductively coupled plasma mass spectroscopy and electron microprobe, led us to identify two types of gold mineralization (i) native gold, electrum, hessite and sulfides (chalcopyrite, pyrite, bornite, ± sphalerite, and galena) in massive quartz breccias and banded chalcedony, (ii) gold, electrum, hematite, magnetite, trace minerals (argentite) and adularia in banded chalcedony. Another group without gold is characterized by quartz, pyrite ± goethite. Secondary minerals are characterized by goethite, native silver and native copper. Arsenic is enriched in pyrite in samples with a high gold content. The bimodal volcanism, the occurrence of adularia, the native gold and electrum in banded silica veins, are classically observed in neutral epithermal systems. The discovery of this type of mineralization in a recent-active continental rift system supplies new insights about hydrothermal processes associated with volcanic activity in a spreading context. Keywords: Republic of Djibouti, Afar Triangle, Hydrothermal, Epithermal system, Gold
NASA Astrophysics Data System (ADS)
Zhuravkova, T. V.; Palyanova, G. A.; Kravtsova, R. G.
2015-07-01
The chemical compositions of acanthite, naumannite, and associated ore minerals have been studied from the samples of polychronous Au-Ag ores at the Rogovik deposit. The following admixtures have been detected: S in naumannite (0-2.9 wt %), Se in acanthite (0-7.45 wt %), argyrodite (~4.8 wt %), and galena (~3.1 wt %), and Fe in sphalerite (~1.2 wt %). The physicochemical parameters of ore formation have been reconstructed on the basis of mineralogical and geochemical data and thermodynamic calculations. Eh-pH (25°C, 1 bar), log fO2-pH, log fS2- T, log fSe2- T, and log fS2-log fSe2 (100-300°C, 1-300 bars) diagrams for the Ag-S-Se-H2O system with the stability fields of Ag sulfoselenides Ag2S1- x Se x of various composition (step x = 0.25, where 0 ≤ x ≤ 1) have been calculated for the first time. It has been established that Ag sulfoselenides of the naumannite series from polychronous ores of the Rogovik deposit precipitated below 70-133°C under reductive conditions (log fO2 =-65…-50) from near-neutral solutions containing elevated Se and relatively lowered S. It has been established that Ag sulfoselenides of acanthite series were formed later then naumannite but in the same range of log fO2 values at temperatures below 110-177°C from solutions with high S concentration and relatively lowered concentration of Se. The complex composition of the studied Au-Ag ores, whose characteristic feature is extremely variable mineralogy, is confirmed.
Valencia-Avellan, Magaly; Slack, Rebecca; Stockdale, Anthony; Mortimer, Robert John George
2017-08-16
Point and diffuse pollution from metal mining has led to severe environmental damage worldwide. Mine drainage is a significant problem for riverine ecosystems, it is commonly acidic (AMD), but neutral mine drainage (NMD) can also occur. A representative environment for studying metal pollution from NMD is provided by carboniferous catchments characterised by a circumneutral pH and high concentrations of carbonates, supporting the formation of secondary metal-minerals as potential sinks of metals. The present study focuses on understanding the mobility of metal pollution associated with historical mining in a carboniferous upland catchment. In the uplands of the UK, river water, sediments and spoil wastes were collected over a period of fourteen months, samples were chemically analysed to identify the main metal sources and their relationships with geological and hydrological factors. Correlation tests and principal component analysis suggest that the underlying limestone bedrock controls pH and weathering reactions. Significant metal concentrations from mining activities were measured for zinc (4.3 mg l -1 ), and lead (0.3 mg l -1 ), attributed to processes such as oxidation of mined ores (e.g. sphalerite, galena) or dissolution of precipitated secondary metal-minerals (e.g. cerussite, smithsonite). Zinc and lead mobility indicated strong dependence on biogeochemistry and hydrological conditions (e.g. pH and flow) at specific locations in the catchment. Annual loads of zinc and lead (2.9 and 0.2 tonnes per year) demonstrate a significant source of both metals to downstream river reaches. Metal pollution results in a large area of catchment having a depleted chemical status with likely effects on the aquatic ecology. This study provides an improved understanding of geological and hydrological processes controlling water chemistry, which is critical to assessing metal sources and mobilization, especially in neutral mine drainage areas.
Light in the darkening on Naica gypsum crystals
NASA Astrophysics Data System (ADS)
Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Fuentes-Montero, M. E.; Esparza-Ponce, H. E.; Carreno-Márquez, J.; Reyes-Cortes, M.; Montero-Cabrera, M. E.
2015-07-01
Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe2O3), β-MnO2, Mn2O3, MnO and/or MnCO3, PbS, PbCO3 and/or PbSO4, ZnO4, ZnS and/or smithsonite (ZnCO3), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.
Houghton, J.L.; Shanks, Wayne C.; Seyfried, W.E.
2004-01-01
The Bent Hill massive sulfide deposit and ODP Mound deposit in Middle Valley at the northernmost end of the Juan de Fuca Ridge are two of the largest modern seafloor hydrothermal deposits yet explored. Trace metal concentrations of sulfide minerals, determined by laser-ablation ICP-MS, were used in conjunction with mineral paragenetic studies and thermodynamic calculations to deduce the history of fluid-mineral reactions during sulfide deposition. Detailed analyses of the distribution of metals in sulfides indicate significant shifts in the physical and chemical conditions responsible for the trace element variability observed in these sulfide deposits. Trace elements (Mn, Co, Ni, As, Se, Ag, Cd, Sb, Pb, and Bi) analyzed in a representative suite of 10 thin sections from these deposits suggest differences in conditions and processes of hydrothermal alteration resulting in mass transfer of metals from the center of the deposits to the margins. Enrichments of some trace metals (Pb, Sb, Cd, Ag) in sphalerite at the margins of the deposits are best explained by dissolution/reprecipitation processes consistent with secondary remineralization. Results of reaction-path models clarify mechanisms of mass transfer during remineralization of sulfide deposits due to mixing of hydrothermal fluids with seawater. Model results are consistent with patterns of observed mineral paragenesis and help to identify conditions (pH, redox, temperature) that may be responsible for variations in trace metal concentrations in primary and secondary minerals. Differences in trace metal distributions throughout a single deposit and between nearby deposits at Middle Valley can be linked to the history of metal mobilization within this active hydrothermal system that may have broad implications for sulfide ore formation in other sedimented and unsedimented ridge systems. ?? 2004 Elsevier Ltd.
Thermal and chemical variations of the Nigerian Benue trough lead-zinc-barite-fluorite deposits
NASA Astrophysics Data System (ADS)
Ogundipe, Ibukun Emmanuel
2017-08-01
The Benue trough is an intra-continental rift initiated in the Cretaceous during the opening of the South Atlantic Ocean. Lead-zinc-barite-fluorite mineralization occurs along the 600 km axis of the trough in three discrete sub-basins which coincide with the lower, middle and upper mineral districts of the Benue Valley. Lithologically these sub-basins are dominated by black carbonaceous shale in the Lower Benue, platform carbonates in the Middle Benue and sandstones in the Upper Benue. Micro-thermometric analysis of fluid inclusions in sphalerite, fluorite, barite and quartz have shown that each mineral district has its own unique thermal and chemical imprint. For example, the temperature can be bracketed between 109 °C and 160 °C for lower Benue, 89 °C-144 °C for the Middle Benue and 176 °C-254 °C for the Upper Benue. Chemical differentiation also exists between each mineral district with the Lower Benue having 22 wt % equivalent NaCl while the Middle and Upper Benue have 18 and 16 wt % equivalent NaCl respectively. This study shows that inter-district thermal and chemical variations exist between the ore-stage sulfide and post-sulfide gangue minerals of the entire Benue Valley. Similarly, intra-district thermal and chemical variations have also been observed among all the paragenetic minerals of each district. The thermal variations may be as a result of variations in the geothermal gradient accompanying continental rifting from one district to the other. The variations in the chemistry between the Lower Benue and the Upper Benue paragenic minerals may be as a result of the distinct lithological differences across the Benue Trough.
Kuva, J; Sammaljärvi, J; Parkkonen, J; Siitari-Kauppi, M; Lehtonen, M; Turpeinen, T; Timonen, J; Voutilainen, M
2018-04-01
We set out to study connected porosity of crystalline rock using X-ray microtomography and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) with caesium chloride as a contrast agent. Caesium is an important radionuclide regarding the final deposition of nuclear waste and also forms dense phases that can be readily distinguished by X-ray microtomography and SEM-EDS. Six samples from two sites, Olkiluoto (Finland) and Grimsel (Switzerland), where transport properties of crystalline rock are being studied in situ, were investigated using X-ray microtomography and SEM-EDS. The samples were imaged with X-ray microtomography, immersed in a saturated caesium chloride (CsCl) solution for 141, 249 and 365 days and imaged again with X-ray microtomography. CsCl inside the samples was successfully detected with X-ray microtomography and it had completely penetrated all six samples. SEM-EDS elemental mapping was used to study the location of caesium in the samples in detail with quantitative mineral information. Precipitated CsCl was found in the connected pore space in Olkiluoto veined gneiss and in lesser amounts in Grimsel granodiorite. Only a very small amount of precipitated CsCl was observed in the Grimsel granodiorite samples. In Olkiluoto veined gneiss caesium was found in pinitised areas of cordierite grains. In the pinitised areas caesium was found in notable excess compared to chloride, possibly due to the combination of small pore size and negatively charged surfaces. In addition, elevated concentrations of caesium were found in kaolinite and sphalerite phases. The findings concerning the location of CsCl were congruent with X-ray microtomography. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.
Kelly, Karen; Slack, John; Selby, David
2009-01-01
The Brooks Range contains enormous accumulations of zinc and copper, either as VMS or sediment-hosted deposits. The Ruby Creek and Omar deposits are Cu-Co stratabound deposits associated with dolomitic breccias. Numerous volcanogenic Cu-Zn (+/-Ag, Au) deposits are situated ~20 km north of the Ruby Creek deposit. The carbonate-hosted deposits consist of chalcopyrite and bornite that fill open spaces, replace the matrix of the breccias, and occur in later cross-cutting veins. Cobaltiferous pyrite, chalcocite, minor tennantite-tetrahedrite, galena, and sphalerite are also present. At Ruby Creek, phases such as carrollite, renierite, and germanite occur rarely. The deposits have undergone post-depositional metamorphism (Ruby Creek, low greenschist facies; Omar, blueschist facies). The unusual geochemical signature includes Cu-Co +/- Ag, As, Au, Bi, Ge, Hg, Sb, and U with sporadic high Re concentrations (up to 2.7 ppm). New Re-Os data were obtained for chalcopyrite, bornite, and pyrite from the Ruby Creek deposit (analyses of sulfides from Omar are in progress). The data show extremely high Re abundances (hundreds of ppb, low ppm) and contain essentially no common Os. The Re-Os data provide the first absolute ages of ore formation for the Ruby Creek deposit and demonstrate that the Re-Os systematics of pyrite, chalcopyrite, and bornite are unaffected by greenschist metamorphism. The Re-Os data show that the main phase of Cu mineralization occurred at 384 +/-4.2 Ma, which coincides with zircon U-Pb ages from igneous rocks that are spatially and genetically associated with VMS deposits. This suggests a temporal link between regional magmatism and hydrothermal mineralization.
NASA Astrophysics Data System (ADS)
Rezeau, Hervé; Moritz, Robert; Beaudoin, Georges
2017-03-01
The Lac Herbin deposit consists of a network of mineralized, parallel steep-reverse faults within the synvolcanic Bourlamaque granodiorite batholith at Val-d'Or in the Archean Abitibi greenstone belt. There are two related quartz-tourmaline-carbonate fault-fill vein sets in the faults, which consist of subvertical fault-fill veins associated with subhorizontal veins. The paragenetic sequence is characterized by a main vein filling ore stage including quartz, tourmaline, carbonate, and pyrite-hosted gold, chalcopyrite, tellurides, pyrrhotite, and cubanite inclusions. Most of the gold is located in fractures in deformed pyrite and quartz in equilibrium with chalcopyrite and carbonates, with local pyrrhotite, sphalerite, galena, cobaltite, pyrite, or tellurides. Petrography and microthermometry on quartz from the main vein filling ore stage reveal the presence of three unrelated fluid inclusion types: (1) gold-bearing aqueous-carbonic inclusions arranged in three-dimensional intragranular clusters in quartz crystals responsible for the main vein filling stage, (2) barren high-temperature, aqueous, moderately saline inclusions observed in healed fractures, postdating the aqueous-carbonic inclusions, and considered as a remobilizing agent of earlier precipitated gold in late fractures, and (3) barren low-temperature, aqueous, high saline inclusions in healed fractures, similar to the crustal brines reported throughout the Canadian Shield and considered to be unrelated to the gold mineralization. At the Lac Herbin deposit, the aqueous-carbonic inclusions are interpreted to have formed first and to represent the gold-bearing fluid, which were generated contemporaneous with regional greenschist facies metamorphism. In contrast, the high-temperature aqueous fluid dissolved gold from the main vein filling ore stage transported and reprecipitated it in late fractures during a subsequent local thermal event.
Ayuso, R.A.; Kelley, K.D.; Leach, D.L.; Young, L.E.; Slack, J.F.; Wandless, G.; Lyon, A.M.; Dillingham, J.L.
2004-01-01
Pb and Sr isotope data were obtained on the shale-hosted Zn-Pb-Ag Red Dog deposits (Qanaiyaq, Main, Aqqaluk, and Paalaaq), other shale-hosted deposits near Red Dog, and Zn-Pb-Ag sulfide and barite deposits in the western and central Brooks Range. The Red Dog deposits and other shale-hosted Zn-Pb-Ag deposits near Red Dog are hosted in the Mississippian Kuna Formation, which is underlain by a sequence of marine-deltaic clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. Ag-Pb-Zn vein-breccias are found in the Endicott Group. Galena formed during the main mineralization stages in the Red Dog deposits and from the Anarraaq and Wulik deposits have overlapping Pb isotope compositions in the range 206Pb/204Pb = 18.364 to 18.428, 207Pb/204Pb = 15.553 to 15.621, and 208Pb/204Pb = 38.083 to 38.323. Galena and sphalerite formed during the main ore-forming stages in the Red Dog deposits define a narrow field on standard uranogenic and thorogenic Pb isotope diagrams. Lead in sulfides of the Red Dog district is less radiogenic (238U/204Pb: ?? = 9.51-9.77) than is indicated by the average crustal lead evolution model (?? = 9.74), a difference consistent with a long history of evolution at low ratios of ?? before the Carboniferous. The homogeneous regional isotopic reservoir of Pb may indicate large-scale transport and leaching of minerals with various ?? ratios and Th/Pb ratios. Younger and genetically unrelated fluids did not significantly disturb the isotopic compositions of galena and sphalerite after the main mineralization event in the Red Dog district. Some pyrite shows evidence of minor Pb remobilization. The overall lead isotope homogeneity in the shale-hosted massive sulfide deposits is consistent with three types of control: a homogeneous regional source, mixing of lead during leaching of a thick sedimentary section and fluid transport, or mixing at the site of deposition. Isotopic variability of the hydrothermal fluids, as represented by galena in the Red Dog district, appears to be consistent with a simple mixing system. Evidence indicates that galena was deposited from largely similar hydrothermal solutions throughout the Red Dog district. A shared regional isotopic reservoir is also supported by the correspondence of Pb isotope compositions of galena in deposits of the Red Dog district and galena in clastic rocks (vein-breccias). Leaching of metals and progressive extraction of radiogenic lead from the clastic rocks in the Endicott Group may account for the trend of increasing 206Pb/204Pb in galena of the Red Dog district. Galena in the Red Dog deposits is unlikely to have been derived entirely from the same isotopic reservoir as that represented by the lead in the Kuna Formation or from the igneous rocks in the Red Dog district. Sr isotope data for barite, calcite, and witherite from the Red Dog deposits are compared with data from regional barite that is associated with sulfides and from barite in sulfide-poor occurrences. Fluids with heterogeneous Sr isotope signatures are indicated. Barite in the Main deposit extends to higher ratios of 87Sr/86Sr (0.709034-0.709899) than barite in the Anarraaq deposit (0.708615-0.709256). All barite is more radiogenic than Carboniferous seawater. Other Mississippian(?) shale-hosted deposits and mineral occurrences containing barite in the Red Dog district and barite in regional occurrences east of Red Dog in the western and central Brooks Range also have heterogeneous 87Sr/86Sr ratios. Carbonate (87Sr/86Sr = 0.710319-0.713637) and witherite (87 Sr/86 Sr = 0.710513) in the Main deposit are more radiogenic than barite. In contrast, carbonate (87Sr/86Sr = 0.708196-0.709740) intergrown with massive sulfides at Anarraaq has isotopic compositions similar to that of barite. Paragenetic and isotop ic studies suggest that early barite is similar to barite typically formed in cold seeps along continental margins. This early fine-grained barite formed before the main mineralizat
Hearn, P.P.; Sutter, J.F.; Belkin, H.E.
1987-01-01
Many Lower Paleozoic limestones and dolostones in the Valley and Ridge province of the central and southern Appalachians contain 10 to 25 weight percent authigenic potassium feldspar. This was considered to be a product of early diagenesis, however, 40Ar 39Ar analyses of overgrowths on detrital K-feldspar in Cambrian carbonate rocks from Pennsylvania, Maryland, Virginia, and Tennessee yield Late Carboniferous-Early Permian ages (278-322 Ma). Simple mass balance calculations suggest that the feldspar could not have formed isochemically, but required the flux of multiple pore volumes of fluid through the rocks, reflecting regional fluid migration events during the Late-Paleozoic Alleghanian orogeny. Microthermometric measurements of fluid inclusions in overgrowths on detrital K-feldspar and quartz grains from unmineralized rocks throughout the study area indicate homogenization temperatures from 100?? to 200??C and freezing point depressions of -14?? to -18.5??C (18-21 wt.% NaCl equiv). The apparent similarity of these fluids to fluid inclusions in ore and gangue minerals of nearby Mississippi Valley-type (MVT) deposits suggests that the regional occurrences of authigenic K-feldspar and MVT mineralization may be genetically related. This hypothesis is supported by the discovery of authigenic K-feldspar intergrown with sphalerite in several mines of the Mascot-Jefferson City District, E. Tennessee. Regional potassic alteration in unmineralized carbonate rocks and localized occurrences of MVT mineralization are both explainable by a gravity-driven flow model, in which deep brines migrate towards the basin margin under a hydraulic gradient established during the Alleghanian orogeny. The authigenic K-feldspar may reflect the loss of K during disequilibrium cooling of the ascending brines. MVT deposits are probably localized manifestations of the same migrating fluids, occurring where the necessary physical and chemical traps are present. ?? 1987.
Germanium geochemistry and mineralogy
Bernstein, L.R.
1985-01-01
Germanium is enriched in the following geologic environments: 1. (1) iron meteorites and terrestrial iron-nickel; 2. (2) sulfide ore deposits, particularly those hosted by sedimentary rocks; 3. (3) iron oxide deposits; 4. (4) oxidized zones of Ge-bearing sulfide deposits; 5. (5) pegmatites, greisens, and skarns; and 6. (6) coal and lignitized wood. In silicate melts, Ge is highly siderophile in the presence of native iron-nickel; otherwise, it is highly lithophile. Among silicate minerals, Ge is concentrated in those having less polymerized silicate tetrahedra such as olivine and topaz. In deposits formed from hydrothermal solutions, Ge tends to be enriched mostly in either sulfides or in fluorine-bearing phases; it is thus concentrated both in some hydrothermal sulfide deposits and in pegmatites, greisens, and skarns. In sulfide deposits that formed from solutions having low to moderate sulfur activity, Ge is concentrated in sphalerite in amounts up to 3000 ppm. Sulfide deposits that formed from solutions having higher sulfur activity allowed Ge to either form its own sulfides, particularly with Cu, or to substitute for As, Sn, or other metals in sulfosalts. The Ge in hydrothermal fluids probably derives from enrichment during the fractional crystallization of igneous fluids, or is due to the incorporation of Ge from the country rocks, particularly from those containing organic material. Germanium bonds to lignin-derivative organic compounds that are found in peat and lignite, accounting for its common concentration in coals and related organic material. Germanium is precipitated from water together with iron hydroxide, accounting for its concentration in some sedimentary and supergene iron oxide deposits. It also is able to substitute for Fe in magnetite in a variety of geologic environments. In the oxidized zone of Ge-bearing sulfide deposits, Ge is concentrated in oxides, hydroxides, and hydroxy-sulfates, sometimes forming its own minerals. It is particularly enriched in some iron- and manganese-bearing oxides and hydroxides, including goethite (up to 5300 ppm) and hematite (up to 7000 ppm). ?? 1985.
The geology and ore deposits of Upper Mayflower Gulch, Summit County, Colorado
Randall, John Alexander
1958-01-01
Upper Mayflower Gulch is on the highly glaciated western side of the Tenmile Range near Kokomo in central Colorado. Somewhat less than $500,000 in silver and gold has been produced from the area since the first mining in the 1880' s. In the mapped area high grade regional metamorphism has produced two varieties of gneiss and a granulite. Total thickness of the rocks is about 5,000 feet. Relict bedding is preserved in compositional banding which strikes north to N. 20 ? E. and dips 70 ? to 80 ? southeast. No significant folding was observed. Normal faulting has occurred since the Precambrian; two major sets of faults are recognizable: (1) a set striking N. 70 ? to 85 ? E. and dipping 75?-85 ? NW; and (2) a set striking N. 70?-50 ? W. and dipping 50?-60 ? SW. Tabular bodies of pegmatite and retrogressively metamorphosed schist along many faults indicate Precambrian movement. The Mayflower fault, a 90 to 300 foot wide zone of siltification and shattered rock, strikes about N. 40 ? W. It extends the entire length of the gulch and appears to form the northern terminus for the northeast trending Mosquito Fault. The Mayflower fault shows repeated movement since the Precambrian, totaling about 3,000 feet of apparent dip slip and 640 feet of apparent strike slip. Faulting during the Tertiary includes both additional movement along Precambrian faults and development of shears trending N. to N. 20 ? E. The shears served as channels for the intrusion of two varieties of quartz latite porphyry dikes. Specular hematite and base-metal sulfide mineralization followed intrusion of the porphyry dikes; the minerals were deposited in open fault zones by high temperature solutions in a low pressure environment. The principal metallic minerals in order of deposition are: hematite, pyrite, chalcopyrite, sphalerite, galena, and rarer argentite. The major mines are the Gold Crest, Payrock, Nova Scotia Boy, and Bird's Nest.
Uranium deposits in the Eureka Gulch area, Central City district, Gilpin County, Colorado
Sims, P.K.; Osterwald, F.W.; Tooker, E.W.
1954-01-01
The Eureka Gulch area of the Central City district, Gilpin County, Colo., was mined for ores of gold, silver, copper, lead, and zinc; but there has been little mining activity in the area since World War I. Between 1951 and 1953 nine radioactive mine dumps were discovered in the area by the U.S. Geological Survey and by prospectors. the importance of the discoveries has not been determined as all but one of the mines are inaccessible, but the distribution, quantity, and grade of the radioactive materials found on the mine dumps indicate that the area is worth of additional exploration as a possible source of uranium ore. The uranium ans other metals are in and near steeply dipping mesothermal veins of Laramide age intrusive rocks. Pitchblende is present in at least four veins, and metatorbernite, associated at places with kosolite, is found along two veins for a linear distance of about 700 feet. The pitchblends and metatorbernite appear to be mutually exclusive and seem to occur in different veins. Colloform grains of pitchblende were deposited in the vein essentially contemporaneously with pyrite. The pitchblende is earlier in the sequence of deposition than galena and sphalerite. The metatorbernite replaces altered biotite-quartz-plagioclase gneiss and altered amphibolite, and to a lesser extent forms coatings on fractures in these rocks adjacent to the veins; the kasolite fills vugs in highly altered material and in altered wall rocks. Much of the pitchblende found on the dumps has been partly leached subsequent to mining and is out of equilibrium. Selected samples of metatorbernite-bearing rock from one mine dump contain as much as 6.11 percent uranium. The pitchblende is a primary vein mineral deposited from uranium-bearing hydrothermal solutions. The metatorbernite probably formed by oxidation, solution, and transportation of uranium from primary pitchblende, but it may be a primary mineral deposited directly from fluids of different composition from these that deposited pitchblende.
Guo, Qi; Wei, Hai-Zhen; Jiang, Shao-Yong; Hohl, Simon; Lin, Yi-Bo; Wang, Yi-Jing; Li, Yin-Chuan
2017-12-19
Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ 109 Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65 Cu 40 Ar + to 105 Pd, 208 Pb 2+ to 104 Pd, and 67 Zn 40 Ar + to 107 Ag + ) and space charge effects dramatically shift the measured δ 109 Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ 109 Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ 109 Ag (or ε 109 Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.
NASA Astrophysics Data System (ADS)
Bower, D. M.; Steele, A.; Ackerson, M. R.; Bullock, E. S.; Green, O. R.; Fries, M.; Conrad, P. G.
2017-12-01
Many terrestrial cherts contain compelling microtextures and mineral phases that are indicative of ancient life in hydrothermal systems on early Earth. In volcanically-derived hydrothermal deposits, cherts have undergone multiple alteration events often resulting in separate generations of quartz veins that are much younger than the host rocks. In some cases, multiple episodes of hydrothermal alteration obscure otherwise syngenetic biosignatures and likewise create false signatures in the form of secondary carbon emplacement or diagenetic phase changes. To better identify possible biosignatures in hydrothermal deposits and understand their origins, we used confocal micro Raman spectroscopy, electron probe microanalysis, and cathodoluminescence (CL) imaging to characterize the quartz fabrics, mineral phases, trace elements, and macromolecular carbon (MMC) in quartz veins from the 3.46 Ga Apex Basalt chert samples. MMC, anatase (TiO2), pyrite (Fe2S), jarosite-alunite (KFe3(SO4)2(OH)6 - Kal3(SO4)2(OH)6), chamosite-phyllosilicates, and Fe-oxides all occur in close association in multiple generations of quartz veins throughout the sample suite. Mineral phases xenotime (YPO4), scorodite (FeAsO4 . H2O), apatite (CaPO4), pentlandite ((Fe,Ni)9S8), barite (BaSO4), sphalerite ((Zn,Fe)S), dolomite ((CaMg(CO3)2) and halides occur in specific generations of quartz. Trace elements (Cr, Mn, Mo, Cu, Sc, Va, Sb, and Co) are heterogeneously distributed within individual samples and likely occur due to fluid scavenging of the host basalts. CL imaging of quartz demonstrates that the majority of silicate material in the Apex cherts underwent recrystallization. This could result in the alteration of MMC and associated mineral assemblages. The biogencity and true origins of morphological features and chemical signatures in the Apex cherts are hotly debated, yet discovering the causes and nature of these puzzling attributes will be key for determining the usefulness of interrogating hydrothermal silica-rich deposits on other planetary environments.
NASA Astrophysics Data System (ADS)
Wang, Jialin; Gu, Xuexiang; Zhang, Yongmei; Zhou, Chao; He, Ge; Liu, Ruiping
2018-03-01
The Sanfengshan copper deposit, located in the Beishan orogenic belt, Northwestern China, is hosted in the lower member of the Hongliuyuan Formation, an early Carboniferous metavolcanic-sedimentary sequence. Mineralization occurs as stratiform, stratiform-like and lenticular orebodies, and comprises of laminated, brecciated, banded, massive, and disseminated ores. The mineralogy is dominated by pyrite, chalcopyrite and sphalerite. Fe-Mn chert is widely distributed and generally occurs as massive, laminated, bands or lenses, which are consistent with the orebody. Alteration at Sanfengshan displays a clear concentric zoning pattern and the footwall alteration is more intense and somewhat thicker than the hanging-wall alteration. Systematic geochemical investigation on the volcanic rocks in this area shows that the basalts of the Hongliuyuan Formation (HLY) are predominantly tholeiites with nearly flat rare earth element (REE) pattern, insignificant negative anomalies of high field strength elements (HFSEs), and low Ti/V and Th/Nb ratios. They were most likely derived from partial melting of depleted asthenospheric mantle and formed in a fore-arc setting during initiation of the southward subduction of the Paleo-Asian Ocean. The basalts of the Maotoushan Formation (MTS) display a calc-alkaline nature and are enriched in large ion lithophile elements (LILEs) and depleted in HFSEs, suggesting an active continental margin setting. Sulfur isotope (δ34S) values of the sulfide and sulfate minerals vary between 0‰ and 5.4‰, which are consistent with sulfur derivation from leaching of the host volcanic rocks, although a direct magmatic contribution cannot be ruled out. The Re-Os isotope data of pyrite yield an isochron age of 353 ± 35 Ma, consistent with the age of the host HLY basalts. Thus, a syngenetic (volcanogenic massive sulfide) model is proposed and it is concluded that the Sanfengshan copper deposit is a typical Cyprus-type VMS deposit that formed in an early Carboniferous fore-arc setting in the Beishan orogenic belt.
Experimental dynamic metamorphism of mineral single crystals
Kirby, S.H.; Stern, L.A.
1993-01-01
This paper is a review of some of the rich and varied interactions between non-hydrostatic stress and phase transformations or mineral reactions, drawn mainly from results of experiments done on mineral single crystals in our laboratory or our co-authors. The state of stress and inelastic deformation can enter explicitly into the equilibrium phase relations and kinetics of mineral reactions. Alternatively, phase transformations can have prominent effects on theology and on the nature of inelastic deformation. Our examples represent five types of structural phase changes, each of which is distinguished by particular mechanical effects. In increasing structural complexity, these include: (1) displacive phase transformations involving no bond-breaking, which may produce anomalous brittle behavior. A primary example is the a-?? quartz transition which shows anomalously low fracture strength and tertiary creep behavior near the transition temperature; (2) martensitic-like transformations involving transformation strains dominated by shear deformation. Examples include the orthoenstatite ??? clinoenstatite and w u ??rtzite ??? sphalerite transformations; (3) coherent exsolution or precipitation of a mineral solute from a supersaturated solid-solution, with anisotropy of precipitation and creep rates produced under nonhydrostatic stress. Examples include exsolution of corundum from MgO ?? nAl2O3 spinels and Ca-clinopyroxene from orthopyroxene; (4) order-disorder transformations that are believed to cause anomalous plastic yield strengthening, such as MgO - nAl2O3 spinels; and (5) near-surface devolatilization of hydrous silicate single-crystals that produces a fundamental brittleness thought to be connected with dehydration at microcracks at temperatures well below nominal macroscopic dehydration temperatures. As none of these interactions between single-crystal phase transformations and non-hydrostatic stress is understood in detail, this paper serves as a challenge to field structural geologists to test whether interactions of these types occur in nature, and to theoreticians to reach a deeper understanding of the complex relations between phase transformations, the local state of stress and associated deformation and deformation rates. ?? 1993.
Paleomagnetism of the Red Dog Zn-Pb massive sulfide deposit in northern Alaska
Lewchuk, Michael T.; Leach, D.L.; Kelley, K.D.; Symons, David T. A.
2004-01-01
Paleomagnetic methods have isolated two ancient magnetizations in and around the Paleozoic shale-hosted Red Dog ore deposit in northern Alaska. A high-latitude, westerly magnetization carried by magnetite, termed characteristic remanent magnetization A, was found in rocks that have barite and/or substantial quartz replacement of barite. An intermediate- to low-latitude, southerly magnetization (characteristic remanent magnetization B) is carried by pyrrhotite and was found in rocks dominated by galena and sphalerite. The ages the two components are constrained by their relationship with geochemistry, radiometric age dating, and hypotheses for the Mesozoic tectonic history of the Brooks Range. Characteristic remanent magnetization A fails the fold test so it must postdate the end of Brookian orogenesis (??? 150 Ma). It is always found with replacement quartz that has a radiometric date (white mica from a vug, 39Ar/40Ar) of 126 Ma. The paleolatitude for characteristic remanent magnetization B is too shallow to be Mesozoic or younger, regardless of the model for the tectonic origin of northern Alaska, and must predate Brookian orogenesis. Geologic mapping suggests that most of the ore is syngenetic, formed at 330 to 340 Ma, and a radiometric date (Re-Os on pyrite) yields an age of 338 Ma. Since characteristic remanent magnetization B predates deformation, is found in mineralized rocks and is carried by pyrrhotite, it was probably acquired during the mineralizing process as well. The combined radiometric ages and paleomagnetic data sets can be best interpreted by assuming that northern Alaska was part of an accreted terrane that was translated northward by about 30?? into its current location relative to the rest of North America and then rotated counterclockwise by 50?? to 70??. This tectonic interpretation yields plausible magnetization ages for both characteristic remanent magnetization A and B. Geologic evidence, isotopic ages, and paleomagnetic data indicate formation of the deposit at a paleolatitude that is much lower than today. ?? 2004 by Economic Geology.
NASA Astrophysics Data System (ADS)
Castroviejo, R.
1990-12-01
Recent research has discovered high-grade Au ores in NNE-SSW trending shear zones in metamorphic proterozoic and palaeozoic terranes, some 40 km NW of Santiago de Compostela (NW Spain). The orebodies are bound to late-stage Hercynian structures, mainly due to brittle deformation, which are superimposed on earlier ductile shear zones, cutting through various catazonal lithologies, including ortho- and paragneisses, amphibolites, eclogites, and granites. Ore mineralogy, alteration, and ore textures define a frame whose main features are common to all prospects in the area. Main minerals are arsenopyrite and pyrite — accompanied by quartz, adularia, sericite, ± (tourmaline, chlorite, carbonates, graphite), as main gangue minerals -with subordinate amounts of boulangerite, bismuthinite, kobellite, jamesonite, chalcopyrite, marcasite, galena, sphalerite, rutile, titanite, scheelite, beryl, fluorite, and minor native gold, electrum, native bismuth, fahlore, pyrrhotite, mackinawite, etc., defining a meso-catathermal paragenesis. Detailed microscopic study allows the author to propose a general descriptive scheme of textural classification for this type of ore. Most of the ores fill open spaces or veins, seal cracks or cement breccias; disseminated ores with replacement features related to alteration (mainly silicification, sericitization, and adularization) are also observed. Intensive and repeated cataclasis is a common feature of many ores, suggesting successive events of brittle deformation, hydrothermal flow, and ore precipitation. Gold may be transported and accumulated in any of these events, but tends to be concentrated in later ones. The origin of the gold ores is explained in terms of hydrothermal discharge, associated with mainly brittle deformation and possibly related to granitic magmas, in the global tectonic frame of crustal evolution of West Galicia. The mineralogical and textural study suggests some criteria which will be of practical value for exploration and for ore processing. Ore grades can be improved by flotation of arsenopyrite. Non-conventional methods, such as pressure or bacterial leaching, may subsequently obtain a residue enriched in gold.
NASA Astrophysics Data System (ADS)
Othmani, M. A.; Soussi, F.; Ferreira da Silva, E.; Moussi, A.; Oueslati, W.; Jebali, R.
2012-04-01
The former mining district of Touiref (1901-1958), located North-West of Tunisia, and where the activities have stopped 50 years ago, gave rise to large volumes of mine (extraction, flotation) tailings containing sulphides (galena, sphalerite, jordanite, pyrite, marcasite) associated with a carbonate gangue. Analysis of a hundred samples of soil has been used to develop isoconcentration maps of Pb, Zn, Cd and As across the study area, beyond the local geochemical background (LGB). The drawing of these maps has allowed the delineation of the contaminated areas using Geographic Information Systems (GIS). In addition, the soils of the study area were characterized in terms physico-chemical (pH and Corg), grain size, mineralogical and chemical means. Their neutral to slightly alkaline pH is (7.91 to 8.81), and their clay (32 and 57%)-silt (26 and 42%) texture, are characteristic of soils developed on carbonate bedrocks. The percentages in organic carbon (Corg) are between 0.71 and 5.6%. From a mineralogical point of view, mainly Pb-Fe sulphides associated with their alteration products have been observed within these soils. The levels of Pb, Zn, Cd and As, may go up 0.99%, 1.99%, 140 ppm and 409 ppm, respectively. These high concentrations were recorded around the extraction, processing and storage sites on the one hand and through the flood zones and the prevailing wind direction (NW-SSE) on the other. These soils have also been subjected to sequential extraction tests in order to characterize the metal-bearing phases and assess the mobility and bioavailability of heavy metals. The results have shown that Pb is mainly associated with the acid-soluble fraction (carbonates) and to a lesser extent with the Fe-(oxy)hydroxides, whereas Zn and Cd are mainly associated with Fe-(oxy)hydroxides and to a lesser degree with sulphides. Metals associated with these phases can be easily mobilized in response to physico-chemical changes and become phytoaccessible.
NASA Astrophysics Data System (ADS)
KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.
2016-12-01
The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.
NASA Astrophysics Data System (ADS)
Wohlgemuth-Ueberwasser, Cora C.; Viljoen, Fanus; Petersen, Sven; Vorster, Clarisa
2015-06-01
The key for understanding the trace metal inventory of currently explored VHMS deposits lies in the understanding of trace element distribution during the formation of these deposits on the seafloor. Recrystallization processes already occurring at the seafloor might liberate trace elements to later hydrothermal alteration and removement. To investigate the distribution and redistribution of trace elements we analyzed sulfide minerals from 27 black smoker samples derived from three different seafloor hydrothermal fields: the ultramafic-hosted Logatchev hydrothermal field on the Mid-Atlantic Ridge, the basaltic-hosted Turtle Pits field on the mid-atlantic ridge, and the felsic-hosted PACMANUS field in the Manus basin (Papua New Guinea). The sulfide samples were analyzed by mineral liberation analyser for the modal abundances of sulfide minerals, by electron microprobe for major elements and by laser ablation-inductively coupled plasma-mass spectrometry for As, Sb, Se, Te, and Au. The samples consist predominantly of chalcopyrite, sphalerite, pyrite, galena and minor isocubanite as well as inclusions of tetrahedrite-tennantite. Laser ablation spectra were used to evaluate the solubility limits of trace elements in different sulfide minerals at different textures. The solubility of As, Sb, and Au in pyrite decreases with increasing degree of recrystallization. When solubility limits are reached these elements occur as inclusions in the different sulfide phases or they are expelled from the mineral phase. Most ancient VHMS deposits represent felsic or bimodal felsic compositions. Samples from the felsic-hosted PACMANUS hydrothermal field at the Pual ridge (Papua New Guinea) show high concentrations of Pb, As, Sb, Bi, Hg, and Te, which is likely the result of an additional trace element contribution derived from magmatic volatiles. Co-precipitating pyrite and chalcopyrite are characterized by equal contents of Te, while chalcopyrite that replaced pyrite (presumably during black smoker growth) is enriched in Te relative to pyrite. These higher Te concentrations may be related to higher fluid temperature.
NASA Astrophysics Data System (ADS)
Wang, Hao; Li, Xiaohu; Chu, Fengyou; Li, Zhenggang; Wang, Jianqiang; Yu, Xing; Bi, Dongwei
2018-04-01
The 15.2°S hydrothermal field is located at 15.2°S, 13.4°W within the Mid-Atlantic Ridge (MAR) and was initially discovered during Cruise DY125-22 by the Chinese expedition during R/V Dayangyihao in 2011. Here, we provide detailed mineralogical, bulk geochemical, and Sr-Pb isotopic data for massive sulfides and basalts from the 15.2°S hydrothermal field to improve our understanding of the mineral compositions, geochemical characteristics, type of hydrothermal field, and the source of metals present at this vent site. The samples include 14 massive sulfides and a single basalt. The massive sulfides are dominated by pyrite with minor amounts of sphalerite and chalcopyrite, although a few samples also contain minor amounts of gordaite, a sulfate mineral. The sulfides have bulk compositions that contain low concentrations of Cu + Zn (mean 7.84 wt%), Co (mean 183 ppm), Ni (mean 3 ppm), and Ba (mean 16 ppm), similar to the Normal Mid-Ocean Ridge Basalt (N-MORB) type deposits along the MAR but different to the compositions of the Enriched-MORB (E-MORB) and ultramafic type deposits along this spreading ridge. Sulfides from the study area have Pb isotopic compositions (206Pb/204Pb = 18.4502-18.4538, 207Pb/204Pb = 15.4903-15.4936, 208Pb/204Pb = 37.8936-37.9176) that are similar to those of the basalt sample (206Pb/204Pb = 18.3381, 207Pb/204Pb = 15.5041, 208Pb/204Pb = 37.9411), indicating that the metals within the sulfides were derived from leaching of the surrounding basaltic rocks. The sulfides also have 87Sr/86Sr ratios (0.708200-0.709049) that are much higher than typical MAR hydrothermal fluids (0.7028-0.7046), suggesting that the hydrothermal fluids mixed with a significant amount of seawater during massive sulfide precipitation.
NASA Astrophysics Data System (ADS)
Frias, S. M. P.; Takahashi, R.; Imai, A.; Blamey, N.
2017-12-01
The Kay Tanda epithermal deposit in Lobo, Batangas, Philippines is mainly hosted in quartz-rich hydrothermal breccia and quartz veins. These contain varying gold grades with some reaching bonanza gold grades as high as 200 ppm Au. They also contain varying amounts of base metal sulfides such as sphalerite, galena, chalcopyrite and pyrite whose abundances increase with depth. Petrographic analysis of the samples revealed different quartz textures such as colloform textures in quartz veins at shallow levels and feathery, flamboyant and mosaic textures in the matrix of hydrothermal breccias at deeper levels. These textures are indicative of boiling conditions. To elucidate the fluid conditions, fluid source, composition and processes during the formation of the deposit, fluid inclusion microthermometry, quantitative fluid inclusion gas analysis and laser Raman spectroscopy were conducted. Doubly polished thin wafers prepared from the quartz veins and quartz crystals in the matrix of hydrothermal breccias. Microthermometric analysis of primary fluid inclusions included measurements of the freezing temperature Tf, the temperature of ice melting Tm, and the homogenization temperature of the fluid phase by disappearance of vapor Th. Liquid-to-vapor (L-V) ratios are variable, thus, liquid-rich liquid-vapor inclusions and vapor-rich liquid-vapor inclusions coexist in some samples. The sizes of the primary fluid inclusions may reach 100 micrometers. The homogenization temperatures range 200 °C to 380 °C, with the mode around 250 °C to 280 °C. Salinities range from 2 to 7 wt% NaCl equivalent, with the mode around 4 to 5 wt% NaCl equivalent. Trends of the distribution of fluid inclusion populations based on their homogenization temperature and salinity suggest boiling which is consistent with the variable liquid to vapor ratios, i.e. coexistence of liquid-rich inclusions and vapor-rich inclusions.
Removal of arsenopyrite from complex sulfide minerals by froth flotation
NASA Astrophysics Data System (ADS)
Choi, Jin-young; Kim, Yang-soo; Kim, Dong-gyu; Han, Oh-hyung; Park, Chul-hyun
2016-04-01
Arsenic (As) is one of hazardous materials and a penalty element in metal concentrates and so metal concentrates containing arsenic of over 0.5% has been currently restricted in import and export trade. It also corrodes a smelting furnace as well as shortens its life cycle. In korea, Janggun mine that produces galena (PbS) /sphalerite (ZnS) concentrate containing arsenic of 1.78% charges a penalty of US 2/ton to LS-Nikko smelter. Hence in this work, flotation tests for removal of arsenopyrite (FeAsS) from sulfide mineral concentrates were carried out using lab scale flotation cell, which maintain grade and recovery of PbS and ZnS in comparison to flotation plant. Particularly, this study was focused on investigating the combination of several chemical reagents (depressant, collector, activator and etc.) that affect flotation performance. In the straight differential flotation for PbS, a PbS grade of 75.80% and a recovery of 90.12% could be obtained with FeAsS removal of 84.1% (0.2% As) under the conditions of 20% feed solids concentration, pH 8.5, 50g/t frother (AF65), 40g/t collector (AP242) and 800g/t As depressant (NaHSO3) and 600g/t Zn depressant (ZnSO4). In the ZnS flotation, the maximum separation achievable for ZnS using froth flotation has been shown to be a grade of 72.57% and a recovery of 95.43%. At this time, FeAsS removal of 87.8% (0.16% As) could be successfully accomplished under pH 11, and 800g/t Zn activator (CuSO4), 75g/t frother (AF65), 60g/t collector (AP211) and 600g/t As depressant (NaHSO3). Acknowledgments This work was supported by the Energy and Resources Engineering Program Grant funded by the Ministry of Trade, Industry and Energy, Korea
NASA Astrophysics Data System (ADS)
Morad, Daniel; Nader, Fadi H.; Gasparrini, Marta; Morad, Sadoon; Rossi, Carlos; Marchionda, Elisabetta; Al Darmaki, Fatima; Martines, Marco; Hellevang, Helge
2018-05-01
This petrographic, stable isotopic and fluid inclusion microthermometric study of the Upper Jurassic limestones of an onshore field, Abu Dhabi, United Arab Emirates (UAE) compares diagenesis in flanks and crest of the anticline. The results revealed that the diagenetic and related reservoir quality evolution occurred during three phases, including: (i) eogenesis to mesogenesis 1, during which reservoir quality across the field was either deteriorated or preserved by calcite cementation presumably derived from marine or evolved marine pore waters. Improvement of reservoir quality was due to the formation of micropores by micritization of allochems and creation of moldic/intragranular pores by dissolution of peloids and skeletal fragments. (ii) Obduction of Oman ophiolites and formation of the anticline of the studied field was accompanied by cementation by saddle dolomite and blocky calcite. High homogenization temperatures (125-175 °C) and high salinity (19-26 wt% NaCl eq) of the fluid inclusions, negative δ18OVPDB values (-7.7 to -2.9‰), saddle shape of dolomite, and the presence of exotic cements (i.e. fluorite and sphalerite) suggest that these carbonates were formed by flux of hot basinal brines, probably related to this tectonic compression event. (iii) Mesogenesis 2 during subsidence subsequent to the obduction event, which resulted in extensive stylolitization and cementation by calcite. This calcite cement occluded most of the remaining moldic and inter-/intragranular pores of the flank limestones (water zone) whereas porosity was preserved in the crest. This study contributes to: (1) our understanding of differences in the impact of diagenesis on reservoir quality evolution in flanks and crests of anticlines, i.e. impact of hydrocarbon emplacement on diagenesis, and (2) relating various diagenetic processes to burial history and tectonic events of foreland basins in the Arabian Gulf area and elsewhere.
Mineral exploration, Mahd adh Dhahab District, Kingdom of Saudi Arabia
Worl, Ronald G.
1978-01-01
Mahd adh Dhahab is the largest of numerous ancient gold mines scattered through the Precambrian shield of Saudi Arabia and the only one with recent production. During the period 1939-54, 765,768 fine ounces of gold and 1,002,029 ounces of silver were produced from the mines by the Saudi Arabian Mining Syndicate. Ore minerals at Mahd adh Dhahab include free gold and silver, tellurides, sphalerite, and chalcopyrite in and associated with a system of north-trending quartz veins and quartz veinlet stockworks. Pyrite is a common sulfide gangue mineral. Country rocks are a north dipping sequence of pyroclastic and transported pyroclastic rocks of the Hulayfah Group that are locally highly silicified and potassium-feldspathized. The prime target for this exploration program was a north-trending zone of quartz veins and breccias, faults, alteration, and metalization approximately 400 m wide and 1000 m long. The ancient and recent mine workings are located in the northern part of this zone. Although the quartz veins and alteration cut all lithologies, the major metalization is confined to the intersection of veins and agglomerate. Ten holes were diamond drilled to explore geochemical, geological, and geophysical targets in the area. A significant new zone of metalization was discovered 700 m south of the ancient and recent mine workings and within the same major zone of quartz veins, alteration, and faults. Metalization in this southern mineralized zone is at the intersection of the quartz veins and a distinctive and highly altered agglomerate. The total zone of vein and agglomerate intercept is potentially metalized and comprises a block of ground 40 m thick and 400 m wide along the strike of the agglomerate and projected downdip 250 m. Tonnage of this block is 17.2 million tons. The explored zone, approximately 25 percent of the potentially metalized rock, has a potential resource of 1.1 million tons containing 27 g/t gold and 73 g/t silver.
NASA Astrophysics Data System (ADS)
Sharman, Elizabeth R.; Taylor, Bruce E.; Minarik, William G.; Dubé, Benoît; Wing, Boswell A.
2015-06-01
We examine models for volcanogenic massive sulfide (VMS) mineralization in the ~2.7-Ga Noranda camp, Abitibi subprovince, Superior Province, Canada, using a combination of multiple sulfur isotope and trace element data from ore sulfide minerals. The Noranda camp is a well-preserved, VMS deposit-rich area that is thought to represent a collapsed volcanic caldera. Due to its economic value, the camp has been studied extensively, providing a robust geological framework within which to assess the new data presented in this study. We explore previously proposed controls on mineralization within the Noranda camp and, in particular, the exceptional Au-rich Horne and Quemont deposits. We present multiple sulfur isotope and trace element compositional data for sulfide separates representing 25 different VMS deposits and "showings" within the Noranda camp. Multiple sulfur isotope data for this study have δ34SV-CDT values of between -1.9 and +2.5 ‰, and Δ33SV-CDT values of between -0.59 and -0.03 ‰. We interpret the negative Δ33S values to be due to a contribution of sulfur that originated as seawater sulfate to form the ore sulfides of the Noranda camp VMS deposits. The contribution of seawater sulfate increased with the collapse and subsequent evolution of the Noranda caldera, an inference supported by select trace and major element analyses. In particular, higher concentrations of Se occur in samples with Δ33S values closer to 0 ‰, as well as lower Fe/Zn ratios in sphalerite, suggesting lower pressures and temperatures of formation. We also report a relationship between average Au grade and Δ33S values within Au-rich VMS deposits of the Noranda camp, whereby higher gold grades are associated with near-zero Δ33S values. From this, we infer a dominance of igneous sulfur in the gold-rich deposits, either leached from the volcanic pile and/or directly degassed from an associated intrusion.
Light in the darkening on Naica gypsum crystals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Esparza-Ponce, H. E.
2015-07-23
Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performedmore » at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe{sub 2}O{sub 3}), β-MnO{sub 2}, Mn{sub 2}O{sub 3}, MnO and/or MnCO{sub 3}, PbS, PbCO{sub 3} and/or PbSO4, ZnO{sub 4}, ZnS and/or smithsonite (ZnCO{sub 3}), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.« less
Isotope geochemistry of waters affected by acid mine drainage in old labour sites (SE, Spain).
NASA Astrophysics Data System (ADS)
Pérez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Garcia-Lorenzo, Maria Luz; Agudo, Ines; Hernandez-Cordoba, Manuel; Recio, Clemente
2015-04-01
The ore deposits of this zone have iron, lead and zinc as the main metal components. Iron is present in oxides, hydroxides, sulfides, sulfates, carbonates, and silicates; lead and zinc occur in sulfides (galena and sphalerite, respectively), carbonates, sulfates, and lead or zinc-bearing (manganese, iron) oxides. Mining started with the Romans and activity peaked in the second half of the 19th century and throughout the 20th century until the 1980's. From 1940 to 1957, mineral concentration was made by froth flotation and, prior to this, by gravimetric techniques. The mining wastes, or tailings, with a very fine particle size were deposited inland (tailings dams) and, since 1957, huge releases were made in directly the sea coast. The objective of this work was to evaluate processes affecting waters from abandoned mine sites by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. Several common chemical and physical processes, such as evaporation, water-rock interaction and mixing could alter water isotopic composition. Evaporation, which causes an enrichment in δD and δ18O in the residual water, is an important process in semiarid areas. The results obtained indicate that, for sites near the coast, waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by A. ferrooxidans, while at depth, sulfate reduction occurred.
Hammerli, Johannes; Rusk, Brian; Spandler, Carl; Emsbo, Poul; Oliver, Nicholas H.S.
2013-01-01
Bromine and chlorine are important halogens for fluid source identification in the Earth's crust, but until recently we lacked routine analytical techniques to determine the concentration of these elements in situ on a micrometer scale in minerals and fluid inclusions. In this study, we evaluate the potential of in situ Cl and Br measurements by LA-ICP-MS through analysis of a range of scapolite grains with known Cl and Br concentrations. We assess the effects of varying spot sizes, variable plasma energy and resolve the contribution of polyatomic interferences on Br measurements. Using well-characterised natural scapolite standards, we show that LA-ICP-MS analysis allows measurement of Br and Cl concentrations in scapolite, and fluid inclusions as small as 16 μm in diameter and potentially in sodalite and a variety of other minerals, such as apatite, biotite, and amphibole. As a demonstration of the accuracy and potential of Cl and Br analyses by LA-ICP-MS, we analysed natural fluid inclusions hosted in sphalerite and compared them to crush and leach ion chromatography Cl/Br analyses. Limit of detection for Br is ~8 μg g−1, whereas relatively high Cl concentrations (> 500 μg g−1) are required for quantification by LA-ICP-MS. In general, our LA-ICP-MS fluid inclusion results agree well with ion chromatography (IC) data. Additionally, combined cathodoluminescence and LA-ICP-MS analyses on natural scapolites within a well-studied regional metamorphic suite in South Australia demonstrate that Cl and Br can be quantified with a ~25 μm resolution in natural minerals. This technique can be applied to resolve a range of hydrothermal geology problems, including determining the origins of ore forming brines and ore deposition processes, mapping metamorphic and hydrothermal fluid provinces and pathways, and constraining the effects of fluid–rock reactions and fluid mixing.
Critical elements in Carlin, epithermal, and orogenic gold deposits
Goldfarb, Richard J.; Hofstra, Albert H.; Simmons, Stuart F.
2016-01-01
Carlin, epithermal, and orogenic gold deposits, today mined almost exclusively for their gold content, have similar suites of anomalous trace elements that reflect similar low-salinity ore fluids and thermal conditions of metal transport and deposition. Many of these trace elements are commonly referred to as critical or near-critical elements or metals and have been locally recovered, although typically in small amounts, by historic mining activities. These elements include As, Bi, Hg, In, Sb, Se, Te, Tl, and W. Most of these elements are now solely recovered as by-products from the milling of large-tonnage, base metal-rich ore deposits, such as porphyry and volcanogenic massive sulfide deposits.A combination of dominance of the world market by a single country for a single commodity and a growing demand for many of the critical to near-critical elements could lead to future recovery of such elements from select epithermal, orogenic, or Carlin-type gold deposits. Antimony continues to be recovered from some orogenic gold deposits and tellurium could potentially be a primary commodity from some such deposits. Tellurium and indium in sphalerite-rich ores have been recovered in the past and could be future commodities recovered from epithermal ores. Carlin-type gold deposits in Nevada are enriched in and may be a future source for As, Hg, Sb, and/or Tl. Some of the Devonian carbonaceous host rocks in the Carlin districts are sufficiently enriched in many trace elements, including Hg, Se, and V, such that they also could become resources. Thallium may be locally enriched to economic levels in Carlin-type deposits and it has been produced from Carlin-like deposits elsewhere in the world (e.g., Alsar, southern Macedonia; Lanmuchang, Guizhou province, China). Mercury continues to be recovered from shallow-level epithermal deposits, as well as a by-product of many Carlin-type deposits where refractory ore is roasted to oxidize carbon and pyrite, and mercury is then captured in air pollution control devices.
Drennan, Dina M; Almstrand, Robert; Ladderud, Jeffrey; Lee, Ilsu; Landkamer, Lee; Figueroa, Linda; Sharp, Jonathan O
2017-05-15
Sulfate-reducing bioreactors (SRBRs) represent a passive, sustainable, and long-term option for mitigating mining influenced water (MIW) during release. Here we investigate spatial zinc precipitation profiles as influenced by substrate differentiation, inorganic ligand availability (inorganic carbon and sulfide), and microbial community structure in pilot-scale SRBR columns fed with sulfate and zinc-rich MIW. Through a combination of aqueous sampling, geochemical digests, electron microscopy and energy-dispersive x-ray spectroscopy, we were able to delineate zones of enhanced zinc removal, identify precipitates of varying stability, and discern the temporal and spatial evolution of zinc, sulfur, and calcium associations. These geochemical insights revealed spatially variable immobilization regimes between SRBR columns that could be further contrasted as a function of labile (alfalfa-dominated) versus recalcitrant (woodchip-dominated) solid-phase substrate content. Both column subsets exhibited initial zinc removal as carbonates; however precipitation in association with labile substrates was more pronounced and dominated by metal-sulfide formation in the upper portions of the down flow columns with micrographs visually suggestive of sphalerite (ZnS). In contrast, a more diffuse and lower mass of zinc precipitation in the presence of gypsum-like precipitates occurred within the more recalcitrant column systems. While removal and sulfide-associated precipitation were spatially variable, whole bacterial community structure (ANOSIM) and diversity estimates were comparatively homogeneous. However, two phyla exhibited a potentially selective relationship with a significant positive correlation between the ratio of Firmicutes to Bacteroidetes and sulfide-bound zinc. Collectively these biogeochemical insights indicate that depths of maximal zinc sulfide precipitation are temporally dynamic, influenced by substrate composition and broaden our understanding of bio-immobilized zinc species, microbial interactions and potential operational and monitoring tools in these types of passive bioreactors. Copyright © 2017 Elsevier Ltd. All rights reserved.
Formation of the Vysoká-Zlatno Cu-Au skarn-porphyry deposit, Slovakia
NASA Astrophysics Data System (ADS)
Koděra, Peter; Lexa, Jaroslav; Fallick, Anthony E.
2010-12-01
The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu-Au skarn-porphyry mineralisation, related to granodiorite/quartz-diorite porphyry dyke clusters and stocks. Vysoká-Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg-Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na-Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31-70 wt.% NaCl eq. and temperatures of liquid-vapour homogenization (Th) of 186-575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1-31 wt.% NaCl eq. and Th of 320-360°C. Quartz-chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0-3 wt.% NaCl eq. and Th of 323-364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ18Ofluid 2.5-12.3‰) with a minor meteoric component. Corresponding low δDfluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile-brittle transition. The magma chamber at ˜5-6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid-vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.
NASA Astrophysics Data System (ADS)
Kiran Yildirim, Demet; Abdelnasser, Amr; Doner, Zeynep; Kumral, Mustafa
2016-04-01
The Halilar Cu-Pb (-Zn) mineralization that is formed in the volcanogenic metasediments of Bagcagiz Formation at Balikesir province, NW Turkey, represents locally vein-type deposit as well as restricted to fault gouge zone directed NE-SW along with the lower boundary of Bagcagiz Formation and Duztarla granitic intrusion in the study area. Furthermore, This granite is traversed by numerous mineralized sheeted vein systems, which locally transgress into the surrounding metasediments. Therefore, this mineralization closely associated with intense hydrothermal alteration within brecciation, and quartz stockwork veining. The ore mineral assemblage includes chalcopyrite, galena, and some sphalerite with covellite and goethite formed during three phases of mineralization (pre-ore, main ore, and supergene) within an abundant gangue of quartz and calcite. The geologic and field relationships, petrographic and mineralogical studies reveal two alteration zones occurred with the Cu-Pb (-Zn) mineralization along the contact between the Bagcagiz Formation and Duztarla granite; pervasive phyllic alteration (quartz, sericite, and pyrite), and selective propylitic alteration (albite, calcite, epidote, sericite and/or chlorite). This work, by using the mass balance calculations, reports the mass/volume changes (gain and loss) of the chemical components of the hydrothermal alteration zones associated with Halilar Cu-Pb (-Zn) mineralization at Balikesir area (Turkey). It revealed that the phyllic alteration has enrichments of Si, Fe, K, Ba, and LOI with depletion of Mg, Ca, and Na reflect sericitization of alkali feldspar and destruction of ferromagnesian minerals. This zone has high Cu and Pb with Zn contents represents the main mineralized zone. On the other hand, the propylitic zone is characterized by addition of Ca, Na, K, Ti, P, and Ba with LOI and Cu (lower content) referring to the replacement of plagioclase and ferromagnesian minerals by albite, calcite, epidote, and sericite with chlorite. Keywords: Mass balance calculations; hydrothermal alterations; Cu-Pb (-Zn) mineralization; Halilar area; NW Turkey
Rare Mineralogy in Alkaline Ultramafic Rocks, Western Kentucky Fluorspar District
NASA Astrophysics Data System (ADS)
Anderson, W.
2017-12-01
The alkaline ultramafic intrusive dike complex in the Western Kentucky Fluorspar District contains unusual mineralogy that was derived from mantle magma sources. Lamprophyre and peridotite petrologic types occur in the district where altered fractionated peridotites are enriched in Rare Earth Elements (REE) and some lamprophyre facies are depleted in incompatible elements. Unusual minerals in dikes, determined by petrography and X-ray diffraction, include schorlomite and andradite titanium garnets, astrophyllite, spodumene, niobium rutile, wüstite, fluoro-tetraferriphlogopite, villiaumite, molybdenite, and fluocerite, a REE-bearing fluoride fluorescent mineral. Mixing of MVT sphalerite ore fluids accompanies a mid-stage igneous alteration and intrusion event consistent with paragenetic studies. The presence of lithium in the spodumene and fluoro-tetraferriphlogopite suggests a lithium phase in the mineral fluids, and the presence of enriched REE in dikes and fluorite mineralization suggest a metasomatic event. Several of these rare minerals have never been described in the fluorspar district, and their occurrence suggests deep mantle metasomatism. Several REE-bearing fluoride minerals occur in the dikes and in other worldwide occurrences, they are usually associated with nepheline syenite and carbonatite differentiates. There is an early and late stage fluoride mineralization, which accompanied dike intrusion and was also analyzed for REE content. One fluorite group is enriched in LREE and another in MREE, which suggests a bimodal or periodic fluorite emplacement. Whole-rock elemental analysis was chondrite normalized and indicates that some of the dikes are slightly enriched in light REE and show a classic fractionation enrichment. Variations in major-element content; high titanium, niobium, and zirconium values; and high La/Yb, Zr/Y, Zr/Hf, and Nb/Ta ratios suggest metasomatized lithospheric-asthenospheric mantle-sourced intrusions. The high La/Yb ratios in some dikes in the titanium garnet facies suggest a magma melt trend toward the carbonation phase of a fractionated peridotite parent magma.
NASA Astrophysics Data System (ADS)
Höhn, S.; Frimmel, H. E.; Debaille, V.; Pašava, J.; Kuulmann, L.; Debouge, W.
2017-12-01
The stratiform Cu-Zn sulfide deposit at Kupferberg in Germany represents Bavaria's largest historic base metal producer. The deposit is hosted by Early Paleozoic volcano-sedimentary strata at the margin of a high-grade allochthonous metamorphic complex. The present paper reports on the first Cu and S isotope data as well as trace element analyses of pyrite from this unusual deposit. The new data point to syn-orogenic mineralization that was driven by metamorphic fluids during nappe emplacement. Primary Cu ore occurs as texturally late chalcopyrite within stratiform laminated pyrite in black shale in two different tectonostratigraphic units of very low and low metamorphic grade, respectively, that were juxtaposed during the Variscan orogeny. Trace element contents of different pyrite types suggest the presence of at least one hydrothermal pyrite generation (mean Co/Ni = 35), with the other pyrite types being syn-sedimentary/early diagenetic (mean Co/Ni = 3.7). Copper isotope analyses yielded a narrow δ65Cu range of -0.26 to 0.36‰ for all ore types suggesting a hypogene origin for the principal chalcopyrite mineralization. The ore lenses in the two different tectonostratigraphic units differ with regard to their δ34S values, but little difference exists between poorly and strongly mineralized domains within a given locality. A genetic model is proposed in which syn-sedimentary/early diagenetic pyrite with subordinate chalcopyrite and sphalerite formed in black shale beds in the two different stratigraphic units, followed by late-tectonic strata-internal, hydrothermal mobilization of Fe, Cu, and Zn during syn-orogenic thrusting, which concentrated especially Cu to ore grade. In agreement with this model, Cu distribution in stream sediments in this region shows distinct enrichments bound to the margin of the allochthonous complex. Thus, Kupferberg can be considered a rare example of a syn-orogenic Cu deposit with the Cu probably being derived from syn-sedimentary/early diagenetic pyrite contained in Early Paleozoic shale units.
Laser ablation ICP-MS applications using the timescales of geologic and biologic processes
NASA Astrophysics Data System (ADS)
Ridley, W. I.
2003-04-01
Geochemists commonly examine geologic processes on timescales of 10^4--10^9 years, and accept that often age relations, e.g., chemical zoning in minerals, can only be measured in a relative sense. The progression of a geologic process that involves geochemical changes may be assessed using trace element microbeam techniques, because the textural, and therefore spatial context, of the analytical scheme can be preserved. However, quantification requires appropriate calibration standards. Laser ablation ICP-MS (LA-ICP-MS) is proving particularly useful now that appropriate standards are becoming available. For instance, trace element zoning patterns in primary sulfides (e.g., pyrite, sphalerite, chalcopyrite, galena) and secondary phases can be inverted to examine relative changes in fluid composition during cycles of hydrothermal mineralization. In turn such information provides insights into fluid sources, migration pathways and depositional processes. These studies have only become possible with the development of appropriate sulfide calibration standards. Another example, made possible with the development of appropriate silicate calibration standards, is the quantitative spatial mapping of REE variations in amphibolite-grade garnets. The recognition that the trace and major elements are decoupled provides a better understanding of the various sources of elements during metamorphic re-equilibration. There is also a growing realization that LA-ICP-MS has potential in biochemical studies, and geochemists have begun to turn their attention in this direction, working closely with biologists. Unlike many geologic processes, the timescales of biologic processes are measured in years to centuries and are frequently amenable to absolute dating. Examples that can be cited where LA-ICP-MS has been applied include annual trace metal variations in tree rings, corals, teeth, bones, bird feathers and various animal vibrissae (sea lion, walrus, wolf). The aim of such studies is to correlate trace element variations with changes in environmental variables. Such studies are proving informative in climate change and habitat management. Again, such variations have been quantified with the availability of appropriate organic, carbonate and phosphate calibration standards.
Hochella, M.F.; Moore, J.N.; Putnis, C.V.; Putnis, A.; Kasama, T.; Eberl, D.D.
2005-01-01
Two sets of samples from riverbeds and adjacent floodplains, separated by 80 river kilometers, were collected from the Clark Fork River Superfund Complex, Montana, (the largest Superfund site in the United States), and studied primarily with transmission electron microscopy (TEM) with several supporting techniques to determine heavy metal-mineral association. Seven of the eight samples studied were strongly influenced by material that once resided in mining and smelting dumps and impoundments; this material was transported downstream sometime during the last century and a half from the Butte/Anaconda areas. The eighth sample was from a deeper floodplain level and dates to premining days. The TEM observations afford a direct look, down to the nanometer level, at secondary mineral formation as a result of the breakdown of sulfides and silicates in the acid environment of this massive mine-drainage system. In the shallow, oxic floodplain sediments, heavy metals of concern in this system (As, Cu, Pb, and Zn) are taken up by the formation of sulfates (particularly Pb in jarosite), as well as hydrous metal oxides (As, Cu, Pb, and Zn in and on ferrihydrite, and a possibly new vernadite-like mineral). The oxides are long-lived in these systems, as they were also found in the anoxic riverbeds. Metals are also taken up by the formation of sulfides in sulfate-reducing environments as observed in the formation of nanoclusters of chalcopyrite and sphalerite. In all samples, clays make up between 5 and 20% of the sediment and carry significant amounts of Cu and Zn. The hydrous oxides, secondary sulfides, and clays provide several routes for metal transport downstream over long distances. Besides the potential bioavailability of heavy metals exchanged on and off the hydrous metal oxides and clays, nanometer-sized sulfides may also be highly reactive in the presence of biologic systems. Copyright ?? 2005 Elsevier Ltd.
Quantitative Analysis of Piezoelectric and Seismoelectric Anomalies in Subsurface Geophysics
NASA Astrophysics Data System (ADS)
Eppelbaum, Lev
2017-04-01
The piezoelectric and seismo-electrokinetic phenomena are manifested by electrical and electromagnetic processes that occur in rocks under the influence of elastic oscillations triggered by shots or mechanical impacts (hits) (e.g., Neishtadt and Osipov, 1958; Neishtadt, 1961; Parkhomenko, 1971; Neishtadt et al., 1986; Maxwell et al., 1992; Butler et al., 1994; Kepic et al., 1995; Neishtadt et al., 1996; Mikhalov et al., 1997; Boulytchov, 2000; Dupuis et al., 2009; Schakel et al., 2011; Neishtadt and Eppelbaum, 2012; Jouniaux and Zyserman, 2016). The developed classification divides the above phenomena into the following types: (1) the seismo-electrokinetic (electrokinetic) phenomenon E, which occurs in polyphase media due to the mutual displacement of the solid and liquid phases; (2) the piezoelectric phenomenon, which occurs in rocks that contain piezoactive minerals; (3) the shot-triggered phenomenon, which is observed in rocks in the vicinity of a shot or hit point; (4) the seismoelectric phenomenon I, manifested by the change of the electric current passing through rocks, and (5) high-frequency impulse electromagnetic radiation, which is generated by massive base-metal bodies. This paper describes the above phenomena in detail, describing their nature, manifestation patterns, and registration techniques. Because the manifestation patterns of the above phenomena are different in different rocks, these phenomena can be used as a basis for geophysical exploration techniques. The piezoelectric method is an example of a successful application of piezoelectric and seismo-electrokinetic phenomena in exploration geophysics. It has been successfully applied in mineral exploration and environmental features research in Russia, USA, Canada, Australia, Belorussia, Azerbaijan, Georgia, Israel and other countries. This method uses comparatively new geophysical parameter - piezoelectric activity of rocks, ores, and minerals. It enables direct exploration for pegmatite, apatite-nepheline, essentially sphalerite, and ore-quartz deposits of gold, tin, tungsten, molybdenum, zinc, crystal, and other raw materials. This method also enables differentiation of rocks such as bauxites, kimberlites, etc., from the host rocks, by their electrokinetic properties. Classification of some rocks, ores, and minerals by their piezoactivity is given in Table 1. These objects (targets) transform wave elastic oscillations into electromagnetic ones. It should be taken into account that anomalous bodies may be detected not only by positive, but also by negative anomalies, if low-piezoactive body occurs in the higher piezoactive medium. The piezoelectric method is an example of successful application of piezoelectric and seismo-electrokinetic phenomena in exploration and environmental geophysics and designed for delineation of targets differing from the host media by piezoelectric properties (Neishtadt et al., 2006, Neishtadt and Eppelbaum, 2012). This method is employed in surface, downhole, and underground modes. Recent testing of piezeoelectric effects of archaeological samples composed from fired clay have shown values of 2.0 - 3.0 ṡ 10-14 C/N. However, absence of reliable procedures for solving the direct and inverse problems of piezoelectric anomalies (PEA), drastically hampers further progression of the method. Therefore, it was suggested to adapt the tomography procedure, widely used in the seismic prospecting, to the PEA modeling. Diffraction of seismic waves has been computed for models of circular cylinder, thin inclined bed and thick bed (Alperovich et al., 1997). As a result, spatial-time distribution of the electromagnetic field caused by the seismic wave has been found. The computations have shown that effectiveness and reliability of PEA analysis may be critically enhanced by considering total electro- and magnetograms as differentiated from the conventional approaches. Distribution of the electromagnetic field obtained by solving the direct problem was the basis for an inverse problem, i.e. revealing depth of a body occurrence, its location in a space as well as determining physical properties. At the same time, this method has not received a wide practical application taking into account complexity of real geological media. Careful analysis piezo- and seismoelectric anomalies shows the possibility of application of quantitative analysis of these effects advanced methodologies developed in magnetic prospecting for complex physical-geological conditions (Eppelbaum et al., 2000, 2001, 2010; Eppelbaum, 2010; 2011, 2015). Employment of these methodologies (improved modifications of tangents, characteristic points areal methods) for obtaining quantitative characteristics of ore bodies, environmental features and archaeological targets (models of horizontal circular cylinder, sphere, thin bed, thick bed and thin horizontal plate were utilized) have demonstrated their effectiveness. Case study at the archaeological site Tel Kara Hadid Field piezoelectric observations were conducted at the ancient archaeological site Tel Kara Hadid with gold-quartz mineralization in southern Israel within the Precambrian terrain at the northern extension of the Arabian-Nubian Shield (Neishtadt et al., 2006). The area of the archaeological site is located eight kilometers north of the town of Eilat, in an area of strong industrial noise. Ancient river alluvial terraces (extremely heterogeneous at a local scale, varying from boulders to silt) cover the quartz veins and complicate their identification. Piezoelectric measurements conducted over a quartz vein covered by surface sediments (approximately of 0.4 m thickness) produced a sharp (500 μV ) piezoelectric anomaly. Values recorded over the host rocks (clays and shales of basic composition) were close to zero. The observed piezoelectric anomaly was successfully interpreted by the use of methodologies developed in magnetic prospecting. For effective integration of piezo- and seismoelectric interpretation results with other geophysical methods, some schemes developed in theory of information (Eppelbaum, 2014) and wavelet theory (Eppelbaum et al., 2011) can be effectively applied. Table 1. Classification of some rocks, ores, and minerals by their piezoactivity d (10-14 Coulomb/Newton) (after Neishdadt et al., 2006 and Neishtadt and Eppelbaum, 2012, with modifications) Piezoactivity groupRock, Ore, Mineral dmin - dmaxdaver Quartz-tourmaline-cassiterite ore 0.8-28 15.7 Antimonite-quartz ore 0.2-1.35 0.6 I Apatite-nepheline ore 0-5 0.9 Galenite-sphalerite ore 0.2-7.7 3.3 Ijolite 0.1-8 1.2 Melteigite 0.2-5 1.6 Pegmatite 0.1-4.8 1.3 Skarn with galenite-sphalerite mineralization0.1-3 0.6 II Sphalerite-galenite ore 0.3-7.7 3.8 Turjaite 0.9-4.8 2.2 Urtite 0.1-32.5 3.4 Juvite 0.2-5.4 1.8 Aleurolite silicificated 0-0.5 0.2 Aplite 0-1.7 0.6 Breccia aleurolite-quartz 0.1-0.4 0.2 Gneiss 0-1.4 0.2 Granite 0-1.6 0.4 Granodiorite 0-0.2 0.1 Quartzite 0-3.3 0.6 III Pegmatite ceramic 0-1 0.15 Sandstone silicificated and tourmalinised 0.1-1.4 0.5 Feldspars 0-0.4 0.15 Porphyrite 0-0.3 0.1 Ristschorrite 0.3-0.9 0.5 Schist argillaceous 0-0.6 0.2 Hornfels 0-0.4 0.2 Skarn sphaleritic-garnet 0-1 0.3 Skarn pyroxene-garnet 0-0.2 0.1 Aleurolite, amphibolites, andesite, gabbro, 0-0.1 0.05 IV greisens, diabase, sandstone Argillite, beresite, dacite, diorite-porphyrite, 0 0 felsite-liparite, limestone, tuff, fenite I - highly active — piezo-activity of samples is greater than 5.0 ṡ 10-14 C/N II - moderately active — piezo-activity of samples is (0.5 - 5.0) ṡ 10-14 C/N III - weakly active — piezo-activity of samples is lower than 0.5 ṡ 10-14 C/N IV - non-active — piezo-activity of samples are near zero. REFERENCES Alperovich, L.S., Neishtadt, N.M., Berkovitch, A.L. and Eppelbaum, L.V., 1997. Tomography approach and interpretation of the piezoelectric data. Trans. of IX General Assembly of the European Geophysical Society. Strasbourg, France, 59/4P02, p. 546. Boulytchov, A., 2000, Seismic-electric effect method on guided and reflected waves. Physics and Chemistry of the Earth, Part A: Solid Earth and Geodesy, 25, No.4, 333-336. Butler, K.E., Russell, R.D., Kepic A.W. and Maxwell, M., 1994. Mapping of a stratigraphic boundary by its seismoelectric response. SAGEEP '94 Conference Proceedings, 689-699. Eppelbaum, L.V., 2010. Archaeological geophysics in Israel: Past, Present and Future. Advances in Geosciences, 24, 45-68. Dupuis, J.C., Butler, K.E., Kepic, A.W. and Harris, B.D., 2009. Anatomy of a seismoelectric conversion: Measurements and conceptual modeling in boreholes penetrating a sandy aquifer. Journal of Geophysical Research, 114, B10306, doi:10.1029/2008JB005939 Eppelbaum, L.V., 2011. Study of magnetic anomalies over archaeological targets in urban conditions. Physics and Chemistry of the Earth, 36, No. 16, 1318-1330. Eppelbaum, L.V., 2014. Geophysical observations at archaeological sites: Estimating informational content. Archaeological Prospection, 21, No. 2, 25-38. Eppelbaum, L.V., 2015. Quantitative interpretation of magnetic anomalies from thick bed, horizontal plate and intermediate models under complex physical-geological environments in archaeological prospection. Archaeological Prospection, 23, No. 2, 255-268. Eppelbaum, L.V., Alperovich, L., Zheludev, V. and Pechersky, A., 2011. Application of informational and wavelet approaches for integrated processing of geophysical data in complex environments. Proceed. of the 2011 SAGEEP Conference, Charleston, South Carolina, USA, 24, 24-60. Eppelbaum, L.V., Itkis, S.E. and Khesin, B.E., 2000. Optimization of magnetic investigations in the archaeological sites in Israel, In: Special Issue of Prospezioni Archeologiche "Filtering, Modeling and Interpretation of Geophysical Fields at Archaeological Objects", 65-92. Eppelbaum, L.V., Khesin, B.E. and Itkis, S.E., 2001. Prompt magnetic investigations of archaeological remains in areas of infrastructure development: Israeli experience. Archaeological Prospection, 8, No.3, 163-185. Eppelbaum, L.V., Khesin, B.E. and Itkis, S.E., 2010. Archaeological geophysics in arid environments: Examples from Israel. Journal of Arid Environments, 74, No. 7, 849-860. Jouniaux, L. and Zyserman, F., 2016. A review on electrokinetically induced seismo-electrics, electro-seismics, and seismo-magnetics for Earth sciences. Solid Earth, 7, 249-284. Kepic, A.W., Maxwell, M. and Russell, R.D., 1995. Field trials of a seismoelectric method for detecting massive sulfides. Geophysics, 60, 365-373. Maxwell, M., Russel, R.D., Kepic, A.W. and Butler, K.E., 1992. Electromagnetic responses from seismically excited targets: Non-Piezoelectric Phenomena. Exploration Geophysics, 23, 201-208. Mikhailov, O.V., Haarsten, M.W. and Toksoz, N., 1997. Electroseismic investigation of the shallow subsurface: Field measurements and numerical modeling. Geophysics, 62, No. 1, 97-105. Neishtadt, N.M., 1961. Searching pegmatites using seismo-electric effect of the second kind. Soviet Geology, No.1, 121-127. Neishtadt, N.M. and Eppelbaum, L.V., 2012. Perspectives of application of piezoelectric and seismoelectric methods in applied geophysics. Russian Geophysical Journal, Nos. 51-52, 63-80. Neishtadt, N., Eppelbaum, L. and Levitski, A., 2006. Application of seismo-electric phenomena in exploration geophysics: Review of Russian and Israeli experience. Geophysics, 71, No. 2, B41-B53. Neishdadt, N.M., Mazanova, Z.V., and Suvorov, N.D., 1986. The application of piezoelectric method for searching ore-quartz deposits in Yakutia. In: Seismic Methods of Studying Complex Media in Ore Regions. NPO Rudgeofizika, Leningrad, 109-116 (in Russian). Neishdadt, N.M., and Osipov, L.N., 1958. On using of seismoelectric effects of the second type observed by pegmatites searching. Trans. of VITR (All-Union Institute of Technical Prospecting Methods), 11, 63-71 (in Russian). Parkhomenko, E.I., 1971. Electrification Phenomena in Rocks. Plenum Press, New York. Schakel, M.D., Smeulders, D.M.J., Slob, E.C. and Heller, H.K.J., 2011. Seismoelectric interface response: Experimental results and forward model. Geophysics, 76, No. 4, p. N29-N36.
Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings.
Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A H
2015-01-01
Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal.
Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings
Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A. H.
2015-01-01
Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal. PMID:26295582
NASA Astrophysics Data System (ADS)
Kan, Tian; Zheng, Youye; Gao, Shunbao
2016-04-01
The Banbule Pb-Zn-Cu skarn deposit is located in the Longger-Gongbujiangda volcanic magma arc in the Gangdese-Nyainqentanglha Plate. It is the only lead-zinc polymetallic deposit discovered in the westernmost Nyainqentanglha metallogenic belt. The measured and indicated resources include 0.9 Mt of Pb+Zn (4.77% Pb and 4.74% Zn, respectively), 6499 t of Cu, and 178 t of Ag (18.75g/t Ag). The orebodies mainly occur as lenses, veins and irregular shapes in the contact zone between the quartz-porphyry and limestone of the Upper Permian Xiala Formation, or in the boundaries between limestone and sandstone. Pb-Zn-Cu mineralization in the Banbule deposit is closely associated with skarns. The ore minerals are dominated by galena, sphalerite, chalcopyrite, bornite, and magnetite, with subordinate pyrite, malachite, and azurite. The gangue minerals are mainly garnet, actinolite, diopside, quartz, and calcite. The ore-related quartz-porphyry displays LA-ICP-MS zircon U-Pb age of 77.31±0.74 Ma. The δ34S values of sulfides define a narrow range of -0.8 to 4.7‰ indicating a magmatic source for the ore-forming materials. Lead isotopic systematics yield 206Pb/204Pb of 18.698 to 18.752, 207Pb/204Pb of 15.696 to 15.760, and 208Pb/204Pb of 39.097 to 39.320. The data points are constrained around the growth curves of upper crust and orogenic belt according to the tectonic discrimination diagrams. The calculated Δβ - Δγ values plot within the magmatic field according to the discrimination diagram of Zhu et al. (1995). The S-Pb isotopic data suggest that Bangbule is a typical skarn deposit, and the Pb-Zn-Cu mineralization is genetically related to the quartz-porphyry in the mining district. The discovery of the Bangbule deposit indicates that there is metallogenic potential in the westernmost Nyainqentanglha belt, which is of great importance for the exploration work in this area.
Hydrothermal fluoride and chloride complexation of indium: an EXAFS study
NASA Astrophysics Data System (ADS)
Loges, Anselm; Testemale, Denis; Huotari, Simo; Honkanen, Ari-Pekka; Potapkin, Vasily; Wagner, Thomas
2017-04-01
Indium (In) is one of the geochemically lesser studied ore metals, and the factors that control the hydrothermal transport and deposition are largely unknown. It has no ore deposits of its own and is commonly mined as a by-product of Zn ores, and there are very few minerals that contain In as an essential structural component. Recently, industrial application of In in touch screen devices has drastically increased demand, which is projected to exceed supply from the current sources in the near future. Since the most relevant In sources are hydrothermal sphalerite ores and to a lesser extent hydrothermal greisen-type deposits in evolved granitic plutons, the aqueous geochemistry of In is of particular interest for understanding its ore forming processes. As a first step towards a comprehensive model for hydrothermal In solubility and speciation, we have studied In speciation in fluoride and chloride bearing solutions at 30-400˚ C and 500 bar using X-Ray Absorption Spectroscopy (XAS) measurements. The experiments were conducted in a unique hydrothermal autoclave setup at beamline BM30B-FAME at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. Our results show that the complexation of In changes dramatically between 30 and 400˚ C. Below ca. 200˚ C, fluoride complexes are the most stable ones, but they break down at higher temperatures. Chloride complexes on the other hand become increasingly stable with increasing temperature. This behavior has interesting consequences for natural ore forming systems. In Cl-rich systems (e.g. massive sulfide ores formed in sea floor environments), cooling can be an effective precipitating mechanism. In F-rich systems, fluoride complexation can extend In mobility to low temperatures and In will only precipitate when F is effectively removed from the fluid, e.g. by mixing with a Ca-rich fluid and precipitation of fluorite (CaF2) as is commonly observed in skarn or greisen-type deposits. Due to In complexing with both F and Cl, depending on temperature, In distribution also has great potential as a fluid chemistry/temperature indicator in a wide range of different hydrothermal ore-forming systems.
GEOLOGY, SULFUR ISOTOPES AND THE ORIGIN OF THE HEATH STEELE ORE DEPOSITS, NEWCASTLE, N.B., CANADA
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dechow, E.
The Heath Steele mine is located 35 miles northwest of Newcastle, New Brunswick, Canada. Middle Ordovician Tetagouche Group rocks, consisting of siliceous and basic volcanic rocks, and fine-grained quartz sericite schists and porphyry, have been folded into a steeply plunging recumbent anticline. The ore deposits of zinc, lead, and copper are associated with minor folding and/or sheared dilatent zones at or near the contact between porphyry and fine-grained senicitic schist. Mineralogically the sulfide bodies consist of early, euhedral arsenopyrite, magnetite, and pyrite, followed by interstitial pyrrhotite, sphalerite, chalcopyrite and galena. Minor minerals are ternantite-tetrahedrite, bismuthinite, marcasite, hematite, and some graphite.more » Supergene minerals consist of chalcocite, covellite, and marcasite with a little native silver. Little hypogene replacement has taken place between the minerals, which show a "porphyritic" texture. Sulfur isotope ratios were determined for over 150 sulfide and sulfate specimens from five of the seven ore bodies, and from granite, acid and basic volcanics, porphyry, and sediments. The results indicate that there is no detectable fractionation either during hypogene mineralization or supergene enrichment. The spread (21.82 to 22.02) covered by the ratios is narrow, and suggestive of a well homogenized source of mineral solutions. The enrichment of S/sup 34/ in the ore sulfides and the presence of graphite, evident from mineralographic studies and mass spectrometric analysis, suggests reduction of original sulfates (known to be enriched in S/sup 34/) by organic carbon at temperatures in excess of 500 deg C. A calculation based on the isotopic exchange reaction between sulfide and sulfate under equilibrium conditions and the spread of the ratios indicates a temperature of 700 to 800 deg C for the source. Finally the ratios determined for sulfides in a gneissic granite close to Heath Steele have the same ratio as the ore. These factors are considered to be diagnostic of a magmatic hydrothermal origin for the orp deposits. It is believed that an original source bed has been buried until suitable temperatures were reached to cause granitization, reduction of sulfates, and mobilization of the resulting sulfides to form ore deposits at favorable loci. (auth)« less
NASA Astrophysics Data System (ADS)
Gafarov, Ozarfar; Martyshkin, Dmitriy; Fedorov, Vladimir; Mirov, Sergey
2018-02-01
Middle-infrared (mid-IR) lasers enabling a wide range of scientific, medical, technological, and defense related applications continue to enjoy a strong demand. Transition metal (TM) doped II-VI chalcogenides are appealing mid-IR gain medial providing direct access to 1.8-6 μm spectral range. . II-VI chalcogenides are available in single crystal and in polycrystalline forms. With respect to single crystals, polycrystalline gain elements fabricated by postgrowth thermal diffusion of TM impurities in II-VI hosts feature better optical quality and enable superior laser characteristics. Despite significant progress in post-growth thermal diffusion technology, there are still some difficulties associated with the diffusion of certain TM ions in certain II-VI hosts. Specifically, the diffusion length Fe in ZnS during 1 month annealing at 950°C is of the order of 0.1 mm. In this work, enhancement of diffusion coefficient under Hot Isostatic Pressing, at temperature and pressure of 1350°C and 2000 atm, and effect of these extreme conditions on the overall optical quality of the crystal were studied. The high temperature was applied to increase the diffusion rate, and the high pressure was needed to suppress strong sublimation and sphalerite - wurtzite phase transition at elevated temperatures. Under these conditions, the diffusion coefficient Fe in ZnS was enhanced by 5500 times as compared to standard diffusion processes carried out at 950°C. It was also demonstrated that the grain size had grown from 30μm to 5.5mm, which is believed to be another reason for efficient diffusion besides the elevation of temperature. The XRD patterns were measured such that the X-ray beam falls on a single grain. The XRD patterns showed only peaks characteristic to single crystals with zinc blende structure. Lasing characterization was performed to investigate the optical quality of the crystal. Slope efficiencies of 23.2% and 15.4% were obtained for TM11 and TM00 modes of operation, respectively. The emission of the laser was demonstrated to be in the 3840-3920 nm.
NASA Astrophysics Data System (ADS)
Roberts, J.; Elmore, R. D.
2017-12-01
An oriented Woodford Shale core from the Ardmore Basin near the Ouachita thrust zone (Core B) was sampled to identify diagenetic events and interpret their origin, and to test if a magnetization was present that can be used to date the altering event(s). The shale is extensively altered, exhibiting a complex paragenesis with multiple fractures and brecciated intervals. Multiple hydrothermal minerals, including biotite, magnesite, norsethite, witherite, gorceixite, potassium feldspar, sphalerite, chalcopyrite, and saddle dolomite, are present in and around fractures and in the matrix. Vitrinite and bitumen reflectance measurements indicate VRo values of 1.82% ( 230°C). Two other Woodford Shale cores (A and C) from the Anadarko Basin also contain hydrothermal minerals. Vitrinite and bitumen reflectance data reveal trends between thermal maturity and the level of hydrothermal alteration, with Core A (0.80% VRo ( 125°C) displaying the lowest alteration, and Core C ( 1.5% VRo ( 210°C) displaying intermediate alteration compared to core B. Paleomagnetic analysis of Core B reveals the presence of a characteristic remanent magnetization (ChRM) with south-southeasterly declinations and shallow inclinations that is unblocked by 450°C and is interpreted to reside in magnetite. This ChRM is interpreted to be either a chemical remanent magnetization (CRM) or a thermochemical remanent magnetization (TCRM) acquired during the Late Permian based on the pole position. The presence of specimens with the CRM/TCRM in altered rock and high thermal maturities suggests that this CRM/TCRM originated from alteration by hydrothermal fluids. These results suggest that the Woodford Shale evolved into an open diagenetic system. In addition to causing heightened thermal maturities, these hydrothermal fluids both increased porosity through dissolution and decreased porosity through precipitation of minerals. The Late Permian timing agrees with the dating of hydrothermal alteration found within the Ouachita and Arbuckle Mountains in other studies. The timing for these events is postcollisional, and the most consistent model for the origin of the hydrothermal minerals is fluid flow as a result of faulting that accessed reservoir(s) of warm fluids.
NASA Astrophysics Data System (ADS)
Li, Ji-Lei; Gao, Jun; Klemd, Reiner; John, Timm; Wang, Xin-Shui
2016-09-01
The oxidized nature of the sub-arc mantle and hence arc magmas is generally interpreted as a result of the migration of subduction-related oxidizing fluids or melts from the descending slab into the mantle wedge. This is of particular importance seeing that the oxidization state of sub-arc magmas seems to play a key role in the formations of arc-related ore deposits. However, direct constraints on the redox state of subducted oceanic crust are sparse. Here, we provide a detailed petrological investigation on sulfide- and oxide-bearing eclogites, blueschists, micaschists, eclogite-facies and retrograde veins from the Akeyazi high-pressure (HP) terrane (NW China) in order to gain insight into the redox processes recorded in a subducting oceanic slab. Sulfides in these rocks are mainly pyrite and minor pyrrhotite, chalcopyrite, bornite, molybdenite, sphalerite and chalcocite, including exsolution textures of bornite-chalcopyrite intergrowth. Magnetite, ilmenite and pyrite occur as inclusions in garnet, whereas sulfides are dominant in the matrix. Large pyrite grains in the matrix contain inclusions of garnet, omphacite and other HP index minerals. However, magnetite replacing pyrite textures are commonly observed in the retrograded samples. The eclogite-facies and retrograde veins display two fluid events, which are characterized by an early sulfide-bearing and a later magnetite-bearing mineral assemblage, respectively. Textural and petrological evidences show that the sulfides were mainly formed during HP metamorphism. Mineral assemblage transitions reveal that the relative oxygen fugacity of subducted oceanic crust decreases slightly with increasing depths. However, according to oxygen mass balance calculations, based on the oxygen molar quantities ( nO2), the redox conditions remain constant during HP metamorphism. At shallow levels (<60 km) in the subduction channel, interaction with oxidized fluid seems to have caused an increase of the oxygen fugacity and the oxidation state of exhuming HP rocks. This study suggests that oxygen components are not released in significant amounts during HP metamorphism of subducted oceanic crust and, thus, cannot be responsible for oxidizing the mantle wedge and increasing the oxidation state of sub-arc mantle melts.
NASA Astrophysics Data System (ADS)
Zajzon, Norbert; Szentpéteri, Krisztián; Szakáll, Sándor; Kristály, Ferenc
2015-10-01
The Băiţa metallogenic district in the Bihor Mountains is a historically important mining area in Romania. Uranium mining took place between 1952 and 1998 from various deposits, but very little is known about the geology and mineralogy of these deposits. In this paper, we describe geology and mineralogy of uranium mineralization of the Avram Iancu uranium mine from waste dump samples collected before complete remediation of the site. Texturally and mineralogically complex assemblages of nickeline, cobaltite-gersdorffite solid solution, native Bi, Bi-sulfosalts, molybdenite, and pyrite-chalcopyrite-sphalerite occur with uraninite, "pitchblende," and brannerite in most of the ore samples. The association of nickel, cobalt, and arsenic with uranium is reminiscent of five-element association of vein type U-Ni-Co-Bi-As deposits; however, the Avram Iancu ores appear to be more replacement-type stratiform/stratabound. Avram Iancu ore samples contain multistage complex, skarn, uranium sulfide, arsenide assemblages that can be interpreted to have been formed in the retrograde cooling stages of the skarn hydrothermal system. This mineralizing system may have built-up along Upper Cretaceous-Paleogene "Banatite" intrusions of diorite-to-granite composition. The intrusions crosscut the underlying uraniferous Permian formations in the stacked NW-verging Biharia Nappe System. The mineralization forms stacked, multilayer replacement horizons, along carbonate-rich lithologies within the metavolcanic (tuffaceous) Muncel Series. Mineral paragenesis and some mineral chemistry suggest moderate-to-high <450, i.e., 350-310 °C, formation temperatures for the uranium sulfide stage along stratigraphically controlled replacement zones and minor veins. Uranium minerals formed abundantly in this early stage and include botryoidal, sooty and euhedral uraninite, brannerite, and coffinite. Later and/or lower-temperature mineral assemblages include heterogeneous, complexly zoned arsenide-sulfarsenide solid solutions associated with minute but abundant uranium minerals. Within the later arsenide-sulfarsenide mineral assemblage, there is great variation in Ni, Co, and S content with generally increasing arsenic content. Uranium minerals in this late-stage assemblage include very fine euhedral uraninite and brannerite inclusions in arsenide-sulfarsenide minerals. Native bismuth and Bi-sulfosalt krupkaite are observed in this As-S-rich assemblage strongly associated with cobaltite.
NASA Astrophysics Data System (ADS)
Sarkar, S. C.; Dasgupta, Somnath
1980-07-01
The present study is confined to the northern part of the Khetri copper belt that extends for about 100 km in northern Rajasthan. Mineralization is more or less strata-bound and is confined to the garnetiferous chlorite schist and banded amphibolite quartzite, occurring towards the middle of the Proterozoic Delhi Supergroup. Preserved sedimentary features and re-estimation of the composition of the pre-metamorphic rocks suggest that the latter were deposited in shallow marine environment characterized by tidal activity. Cordierite-orthoamphibole-cummingtonite rock occurring in the neighbourhood of the ores is discussed, and is suggested to be isochemically metamorphosed sediment. The rocks together with the ores were deformed in two phases and metamorphosed in two progressive and one retrogressive events of metamorphism. Study of the host rocks suggests that the maximum temperature and pressure attained during metamorphism are respectively 550 600°C and < 5.5 kb. Principal ore minerals in Madan Kudan are chalcopyrite, pyrrhotite, pyrite and locally magnetite. In Kolihan these are chalcophyrite, pyrrhotite and cubanite. Subordinate phases are sphalerite, ilmenite, arsenopyrite, mackinawite, molybdenite, cobaltite and pentlandite. The last two are very rare. Gangue minerals comprise quartz, chlorite, garnet, amphiboles, biotite, scapolite, plagioclase and graphite. The ores are metamorphosed at temperatures > 491°C. Sulfide assemblages are explained in terms of fS 2 during metamorphism. Co-folding of the ore zone with the host rocks, confinement of the ores to the carbonaceous pelites or semi-pelitic rocks, strata-bound and locally even stratiform nature of the orebodies, lack of finite ‘wall rock alteration’, metamorphism of the ores in the thermal range similar to that for the host rocks, absence of spatial and temporal relationship with the granitic rocks of the region led the authors to conclude that the entire mineralization was originally sedimentary-diagenetic. Any loss of primitive features and development of incongruency are due to subsequent deformation and metamorphism to which the ores and their hosts were together subjected.
Characterization of feed coal and coal combustion products from power plants in Indiana and Kentucky
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brownfield, M.E.; Affolter, R.H.; Cathcart, J.D.
1999-07-01
The US Geological Survey, Kentucky Geological Survey, and the University of Kentucky Center for Applied Energy Research are collaborating with Indiana and Kentucky utilities to determine the physical and chemical properties of feed coal and coal combustion products (CCP) from three coal-fired power plants. These three plants are designated as Units K1, K2, and I1 and burn high-, moderate-, and low-sulfur coals, respectively. Over 200 samples of feed coal and CCP were analyzed by various chemical and mineralogical methods to determine mode of occurrence and distribution of trace elements in the CCP. Generally, feed coals from all 3 Units containmore » mostly well-crystallized kaolinite and quartz. Comparatively, Unit K1 feed coals have higher amounts of carbonates, pyrite and sphalerite. Unit K2 feed coals contain higher kaolinite and illite/muscovite when compared to Unit K1 coals. Unit I1 feed coals contain beta-form quartz and alumino-phosphates with minor amounts of calcite, micas, anatase, and zircon when compared to K1 and K2 feed coals. Mineralogy of feed coals indicate that the coal sources for Units K1 and K2 are highly variable, with Unit K1 displaying the greatest mineralogic variability; Unit I1 feed coal however, displayed little mineralogic variation supporting a single source. Similarly, element contents of Units K1 and K2 feed coals show more variability than those of Unit I1. Fly ash samples from Units K1 and K2 consist mostly of glass, mullite, quartz, and spines group minerals. Minor amounts of illite/muscovite, sulfates, hematite, and corundum are also present. Spinel group minerals identified include magnetite, franklinite, magnesioferrite, trevorite, jacobisite, and zincochromite. Scanning Electron Microscope analysis reveals that most of the spinel minerals are dendritic intergrowths within aluminum silicate glass. Unit I1 fly ash samples contain glass, quartz, perovskite, lime, gehlenite, and apatite with minor amounts of periclase, anhydrite, carbonates, pyroxenes, and spinels. The abundant Ca mineral phases in the Unit I1 fly ashes are attributed to the presence of carbonate, clay and phosphate minerals in the coal.« less
Fey, David L.; Church, Stan E.; Driscoll, Rhonda L.; Adams, Monique G.
2011-01-01
Eleven acid-sulphate and quartz-sericite-pyrite altered mine waste samples from the Animas River watershed in SW Colorado were subjected to a series of 5 to 6 successive leaches using the US EPA 1312 leach protocol to evaluate the transport of metals and loss of acidity from mine wastes as a function of time. Multi-acid digestion ICP-AES analyses, X-ray diffraction (XRD) mineral identification, total sulphur, and net acid potential (NAP) determinations were performed on the initial starting materials. Multiple leaching steps generally showed a 'flushing' effect, whereby elements loosely bound, presumably as water-soluble salts, were removed. Aluminum, Cd, Fe, Mg, Mn, Sr, Zn, and S showed decreasing concentration trends, whereas Cu concentrations showed initially decreasing trends, followed by increasing trends in later steps. Concentrations of Zn in the first leach step were independent of whole-sample Zn content. Lead and Ba concentrations consistently increased with each step, indicating that anglesite (PbSO4) and barite (BaSO4), respectively, were dissolving in successive leach steps. Comparison of Fe content with NAP resulted in a modest correlation. However, using the S analyses and XRD identification of sulphide minerals to apportion S amongst enargite, barite, anglesite/galena, and sphalerite, and assigning the remaining S to pyrite, provided a useful correlation between estimated pyrite content and NAP. Whole-sample mass loss correlated well with NAP, but individual elements' behaviors varied between positive correlation (e.g. Al, Fe, Mg), no apparent correlation (Ca, Cd, Pb, Zn), and negative correlation (Cu). Comparison of the summed titrated acidities of the leachates with the whole-sample NAP values yielded an estimate of the fraction of NAP consumed, and led to an estimate of the time it would take to consume the sample acidity by weathering. We estimate, on the basis of these experiments, the acidity in the upper 30 cm would be consumed in 200–1000 years. In addition, calculations suggest that the acidity would be depleted before the complete store of the metals Cu-Cd-Zn in these mine wastes would be released to the environment.
Fey, D.L.; Church, S.E.; Driscoll, R.L.; Adams, M.G.
2011-01-01
Eleven acid-sulphate and quartz-sericite-pyrite altered mine waste samples from the Animas River watershed in SW Colorado were subjected to a series of 5 to 6 successive leaches using the US EPA 1312 leach protocol to evaluate the transport of metals and loss of acidity from mine wastes as a function of time. Multi-acid digestion ICP-AES analyses, X-ray diffraction (XRD) mineral identification, total sulphur, and net acid potential (NAP) determinations were performed on the initial starting materials. Multiple leaching steps generally showed a 'flushing' effect, whereby elements loosely bound, presumably as water-soluble salts, were removed. Aluminum, Cd, Fe, Mg, Mn, Sr, Zn, and S showed decreasing concentration trends, whereas Cu concentrations showed initially decreasing trends, followed by increasing trends in later steps. Concentrations of Zn in the first leach step were independent of whole-sample Zn content. Lead and Ba concentrations consistently increased with each step, indicating that anglesite (PbSO4) and barite (BaSO4), respectively, were dissolving in successive leach steps. Comparison of Fe content with NAP resulted in a modest correlation. However, using the S analyses and XRD identification of sulphide minerals to apportion S amongst enargite, barite, anglesite/galena, and sphalerite, and assigning the remaining S to pyrite, provided a useful correlation between estimated pyrite content and NAP. Whole-sample mass loss correlated well with NAP, but individual elements' behaviors varied between positive correlation (e.g. Al, Fe, Mg), no apparent correlation (Ca, Cd, Pb, Zn), and negative correlation (Cu). Comparison of the summed titrated acidities of the leachates with the whole-sample NAP values yielded an estimate of the fraction of NAP consumed, and led to an estimate of the time it would take to consume the sample acidity by weathering. We estimate, on the basis of these experiments, the acidity in the upper 30 cm would be consumed in 200-1000 years. In addition, calculations suggest that the acidity would be depleted before the complete store of the metals Cu-Cd-Zn in these mine wastes would be released to the environment. ?? 2011 AAG/Geological Society of London.
Metal mobilisation in hydrothermal sediments at the TAG Hydrothermal Field (MAR, 26°N)
NASA Astrophysics Data System (ADS)
Dutrieux, A. M.; Lichtschlag, A.; Martins, S.; Barriga, F. J.; Petersen, S.; Murton, B. J.
2017-12-01
Metalliferous sediments in the vicinity of hydrothermal systems are enriched in base metals, but few studies have addressed their potential as mineral resources. These metalliferous sediments have been accumulated by different processes and reflect modifications of the primary mineral deposits by: oxidation of the chimney materials, in situ precipitation of low-temperature minerals and mass wasting. To understand the post-formation processes in metalliferous sediments, we investigated sub-seafloor metal mobilisation in different geological environments. This presentation focuses on the TAG Hydrothermal Field (Mid-Atlantic Ridge, 26°N) and explores sediment and pore water compositions using ICP-MS and ICP-OES. We use reactive transport modelling to interpret the degree of metal remobilisation and to identify the most important geochemical reactions in the different sediments. The pore water concentrations measured in sediments above inactive sulphide mounds present constant major elements composition that indicates this environment is dominated by complete exchange with seawater. The sediments, that are mainly composed of hematite and goethite formed during the oxidation of sulphides, have low Cu concentrations (< 0.1%) and the main part of their primary Cu and Zn content has likely been mobilized. Cu concentrations increase at the edges of the mounds (up to wt. 20%) or in distal depositionary channels (up to wt.10%) where sulphide minerals (e.g. pyrite, chalcopyrite and sphalerite) are still present in the sediments and capped by more recent sediment slumping. In the depositionary channels, pore waters show metal concentrations affected by diagenesis and redox-sensitive metals are released at depth (e.g. Mn2+ and Cu2+). The leaching of the primary sulphides (e.g. deprecated grains of chalcopyrite), and metal mobilisation lead to an enrichment of Cu and Zn at shallower depth. Here, some stratigraphic horizons scavenge metallic cations back into solid phases and form Mn-oxide crusts between 30 and 60 cm, in which Cu concentrations also increase. Our results demonstrate that metal mobilisation differs depending on the geological environment and their related accumulation processes, causing the absence of Cu on the top of inactive hydrothermal mounds but enriched in more distal sediment basins.
NASA Astrophysics Data System (ADS)
Ernawati, Rika; Idrus, Arifudin; TBMP, Himawan
2017-06-01
Lamuntet is one of gold ore mining area carried out by the Artisanal Small scale Gold Mining (ASGM) located in West Sumbawa, Indonesia. Most of the miners at this area are not the local miners but also those from other regions. Mineralization of this area is strong identified as low sulfidation epithermal system. There are two blocks of this mining location, namely, Ngelampar block with an area of 0.164 km2 and Song block with an area of 0.067 km2. This study was focused on Ngelampar block. The characteristic of epithermal system is the existence of quartz vein with comb, vuggy, and sugary texture. The aim of this research was to analyze the gold grade and other metals, such as Cu, Ag, Pb, As, Zn, and Hg. The research methods included literature study from previous researches, field work, laboratory work, and interpretation. The literature study was performed on previous researches with similar study area. The field work comprised of direct observation and sampling. Fieldwork was done for a week to obtain gold ore/vein. Sixteen samples were analyzed to obtain the grade of ore/metal. The Hg laboratory analysis was then performed on the six samples with the highest gold grade. Laboratory works were conducted at Intertek Jakarta by using Fire Assay (FA) for gold grade and Atomic Absorption Spectrophotometry (AAS) for Cu, Ag, Pb, As, Zn, and Hg. Results of the analysis showed the range of Au was grade (0.1 ppm - 27.8 ppm), Cu was 26 ppm -1740 ppm, Pb was 101 ppm- >4000 ppm, Zn of 73 ppm- >10,000 ppm, Ag of 3 ppm -185 ppm, As was 150 ppm-6530 ppm, and Hg of 0.08 ppm - 1.89 ppm. L1 and L15 had high grade for all values (Au, Ag, Zn, Cu, As, and Hg). Gold mineralization was formed as electrum because of Ag content is higher than 20%. Associated minerals of the samples in the study area were galena, sphalerite, arsenopyrite, and chalcopyrite which showed the characteristic of rich base metal of Pb, Zn, and Cu at LS epithermal.
NASA Astrophysics Data System (ADS)
Abd El Monsef, Mohamed; Salem, Ibrahim; Slobodník, Marek; Ragab, Ahmed
2018-07-01
Scanning electron microscope (SEM), Electron microprobe (EMPA) and fluid inclusion studies of the ore body, as well as geochemical analyses of country rocks were performed to determine the nature and characteristics of the mineralizing fluid responsible for Au-Cu deposits in Um Balad area, Northern Eastern Desert of Egypt. The Um Balad Au-Cu deposits are confined to well developed-quartz veins and veinlets cutting through the hosting country rocks. Petrographic and geochemical investigations of the hosting rocks distinguished between two main rock units; 1) metagabbro-diorite rocks with tholeiitic nature derived in island arc/continental margin tectonic regime, and 2) granodiorite rocks formed from calc-alkaline magma in continental margin regime. Wallrock alterations are represented by propylitic and argillic types. The mineralized quartz veins are striking in NE-SW direction and dipping between (35°-45°) in SE direction, other mineralized mafic dykes enriched with auriferous quartz veinlets are trending NE-SW and dipping 70°/SE. The main ore minerals are represented by gold, chalcopyrite, pyrite, sphalerite, malachite, covellite and goethite. While, geffroyite, cuprite, chrysocolla, pseudomalachite, britholite, wolframite, scheelite, hematite and rutile are detected as minor constituents. Fluid inclusions microthermometry and isochore calculations combined with chlorite geothermometry revealed that the Um Balad deposits were formed at temperature ranging from 305 °C to 325 °C and pressure between (100-500 bar). The mineralization had been developed in the shallow levels, beneath the water table at depth of 350-1760 m, rather than common mesothermal vein-type deposits in Egypt. Magmatic water have been suggested as the main source for the mineralized fluid. The transportation of the gold metal seems to be happen as bisulfide complexes in moderately acidic environment. The deposition was resulted from combination of changes in physico-chemical parameters, temperature and pressure plus the instability of the reduced sulfur complexes. A contamination with metamorphic and/or meteoric water was also proposed that has strong influence during the depositional process.
Trace elements and isotope data of the Um Garayat gold deposit, Wadi Allaqi district, Egypt
NASA Astrophysics Data System (ADS)
Zoheir, Basem; Emam, Ashraf; Pitcairn, Iain K.; Boskabadi, Arman; Lehaye, Yann; Cooper, Matthew J.
2018-04-01
Trace element composition of sulfides and O, C, Sr and S isotopic data are assessed to constrain the evolution and potential fluid and metal sources of the Um Garayat gold deposit. Ore microscopy and BSE investigations of quartz veins show blocky arsenopyrite and pyrite replaced in part by pyrrhotite, chalcopyrite, sphalerite, galena, and gersdorffite. Free-milling gold occurs commonly in close association with the late sulfides, and along fractures in pyrite. On the other hand, recrystallized pyrite is disseminated in host metavolcaniclastic/metasedimentary rocks that commonly contain carbonaceous material. In situ LA-ICP-MS analysis of sulfides shows the recrystallized pyrite enriched in most trace elements, while blocky pyrite contains only some traces of arsenic. Detected concentrations of gold (up to 17 ppm) were only reported in arsenopyrite disseminated in quartz veins. The δ34S values of blocky pyrite and pyrrhotite in quartz veins define a narrow range (1.6 to 3.7‰), suggesting a homogenous sulfur source which is consistent with the dominantly mafic host rocks. The recrystallized pyrite has a distinctive sulfur isotope composition (δ34S - 9.3 to - 10.6‰), which is rather comparable to diagenetic sulfides. Hydrothermal carbonate in quartz veins and wallrock have nearly constant values of δ18O (10.5 to 11.9‰) and δ13C (- 4.2 to - 5.5‰). Based on constraints from mineral assemblages and chlorite thermometry, data of six samples indicate that carbonate precipitation occurred at 280 °C from a homogenous hydrothermal fluid with δ18OH2O 4.4 ± 0.7‰ and δ13C = 3.7 ± 0.8‰. Strontium isotope values of two samples (87Sr/86Sr = 0.7024 and 0.7025) are similar to the initial 87Sr/86Sr ratios of island arc metabasalts ( 710 Ma) in the South Eastern Desert. The generally homogenous sulfur, C, O, Sr isotope data are suggestive of metamorphogenic fluids, likely produced from dominantly mafic volcanic rocks at the greenschist-amphibolite facies transition.
Nordstrom, D. Kirk
2008-01-01
The U.S. Geological Survey, in cooperation with the New Mexico Environment Department and supported by Molycorp, Inc (currently Chevron Minerals), has completed a 5-year investigation (2001-2006) to determine the pre-mining ground-water quality at Molycorp's Questa molybdenum mine in northern New Mexico. Current mine-site ground waters are often contaminated with mine-waste leachates and no data exists on premining ground-water quality so that pre-mining conditions must be inferred. Ground-water quality undisturbed by mining is often worse than New Mexico standards and data are needed to help establish closure requirements. The key to determining pre-mining conditions was to study the hydrogeochemistry of a proximal natural analog site, the Straight Creek catchment. Main rock types exposed to weathering include a Tertiary andesite and the Tertiary Amalia tuff (rhyolitic composition), both hydrothermally altered to various degrees. Two types of ground water are common in mineralized areas, acidic ground waters in alluvial debris fans with pH 3-4 and bedrock ground waters with pH 6-8. Siderite, ferrihydrite, rhodochrosite, amorphous to microcrystalline Al(OH)3, calcite, gypsum, barite, and amorphous silica mineral solubilities control concentrations of Fe(II), Fe(III), Mn(II), Al, Ca, Ba, and SiO2, depending on pH and solution composition. Concentrations at low pH are governed by element abundance and mineral weathering rates. Concentrations of Zn and Cd range from detection up to about 10 and 0.05 mg/L, respectively, and are derived primarily from sphalerite dissolution. Concentrations of Ni and Co range from detection up to 1 and 0.4 mg/L, respectively, and are derived primarily from pyrite dissolution. Concentrations of Ca and SO4 are derived from secondary gypsum dissolution and weathering of calcite and pyrite. Metal:sulfate concentration ratios are relatively constant for acidic waters, suggesting consistent weathering rates, independent of catchment. These trends, combined with lithology, mineralogy, and mineral solubility controls, provide useful constraints on pre-mining ground-water quality for the mine site where the lithology is known.
Hindar, Atle; Nordstrom, D. Kirk
2015-01-01
The Highway E18 between the cities of Grimstad and Kristiansand, southern Norway, constructed in the period 2006–2009, cuts through sulfide-bearing rock. The geology of this area is dominated by slowly-weathering gneiss and granites, and oxidation of fresh rock surfaces can result in acidification of surface water. Sulfide-containing rock waste from excavations during construction work was therefore deposited in three waste rock deposits off-site. The deposits consist of 630,000–2,360,000 metric tons of waste rock material. Shell sand and limestone gravel were added in layers in adequate amounts to mitigate initial acid runoff in one of the deposits. The shell sand addition was not adequate in the two others. The pH in the effluents from these two was reduced from 4.9–6.5 to 4.0–4.6, and Al concentrations increased from below 0.4 mg/L to 10–20 mg/L. Stream concentrations of trace metals increased by a factor of 25–400, highest for Ni, and then in decreasing order for Co, Mn, Cd, Zn and Cu. Concentrations of As, Cr and Fe remained unchanged. Ratios of Co/Ni and Cd/Zn indicate that the metal sources for these pair of metals are sphalerite and pyrite, respectively. Based on surveys and established critical limits for Al, surface waters downstream became toxic to fish and invertebrates. The sulfur release rates were remarkably stable in the monitoring period at all three sites. Annual sulfur release was 0.1–0.4% of the total amount of sulfur in the deposit, indicating release periods of 250–800 years. Precipitates of Al-hydroxysulfates, well-known from mining sites, were found at the base of the deposits, in streams and also along the ocean shore-line. The effects of added neutralization agents in the deposits and in treatment areas downstream gradually decreased, as indicated by reduced stream pH over time. Active measures are needed to avoid harmful ecological effects in the future.
NASA Astrophysics Data System (ADS)
Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong
2018-04-01
We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes.
Othmani, Mohamed Ali; Souissi, Fouad; Bouzahzah, Hassan; Bussière, Bruno; da Silva, Eduardo Ferreira; Benzaazoua, Mostafa
2015-02-01
The underground extraction of Pb-Zn mineralization in the Touiref area stopped in 1958. A large volume of flotation tailings (more than 500 Mt) containing sulfides were deposited in a tailings impoundment. The goals of this study are to evaluate the neutralization capacity of the unoxidized and oxidized tailings, to assess the speciation of metals between the different components of the tailings material, and to assess the mobility of metals and the secondary minerals' precipitation in pore waters using geochemical modeling. To accomplish these objectives, representative samples from both fresh and oxidized zones were collected along a vertical profile through the tailings pile. Physical, chemical (ICP-MS), and mineralogical characterization (X-ray diffraction (XRD), reflected light microscopy, scanning electron microscope (SEM)) of these samples was performed. Grain size analysis shows that the tailings are dominated by silt- to sand-sized fractions. The microscopic observation highlights the presence of pyrite, marcasite, galena, and sphalerite as primary minerals in a carbonated matrix. The study reveals also the presence of secondary minerals represented by cerussite, smithsonite, anglesite, and Fe oxi-hydroxides as important scavengers for trace elements. The static tests show that the presence of calcite in the tailing samples ensures acid-neutralizing capacity (ANC), which is significantly greater than the acidity potential (PA). The geochemical characterization of the unoxidized samples shows higher Cd, Pb, and Zn concentrations than the oxidized samples containing the highest values for Fe and SO4. Sequential extraction tests show that significant percentages of metals are distributed between the acid-soluble fractions (Cd, Pb, and Zn) and the reducible one (Zn). Pore water analysis indicates that Ca is the dominant cation (8,170 and 6,200 mg L(-1), respectively), whereas sulfate is the principal anion (6,900 and 5,100 mg L(-1), respectively). Saturation index (SI) calculations of minerals in pore water extracted from both the oxidized and unoxidized samples are indicative of gypsum (SI >0) and Fe(III) oxides (SI ≫0) precipitation. The latter controls the Fe concentration in solution.
The mechanisms of pyrite oxidation and leaching: A fundamental perspective
NASA Astrophysics Data System (ADS)
Chandra, A. P.; Gerson, A. R.
2010-09-01
Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh and reacted pyrite surfaces is needed to identify site specific chemical processes. Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) are two synchrotron based surface spectromicroscopic and microspectroscopic techniques that use XPS- and XANES-imaging to correlate chemistry with topography at a submicron scale. Recent data collected with these two techniques suggests that species are heterogeneously distributed on the surface and oxidation to be highly site specific.
NASA Astrophysics Data System (ADS)
Abrosimova, Natalya; Bortnikova, Svetlana
2017-12-01
The study was conducted on the example of sulphide-containing mine tailings with a varying amount of sulphide and arsenide minerals, from three distinct tailings dumps situated in Russia: Karabash Mine Site, South Ural; Komsomolsk tailings impoundment, Kemerovo region; Khovu-Aksy mine site, Tuva Republic. The aim of the study was to compare the mobility of anionogenic elements (As, Sb, Mo, Se, S, P, N, Cl, F, C) and their role in migration, precipitation, and concentration of metals during the water-tailings interaction depending on the physicochemical parameters (pH, Eh) of the medium and the mineral composition of the waste material. Using slightly acidic leaching experiments the quantitative estimation of mobile forms of elements is given. Based on the compositions of the obtained water leaching solutions, aqueous speciation of chemical elements and saturation index of key minerals in the experimental solutions were calculated. The results of calculating forms of chemical elements made it possible to construct series of mobility of metals and metalloids in solutions with different physicochemical parameters. In the alkaline conditions, Sb>As>Cd>Cu>Zn>Fe>Pb, when the medium is acidified, the series changes, As>Cd>Cu>Zn>Pb>Sb>Fe in weakly alkaline conditions, Sb>Mn>As>Zn>Fe however, when the medium is acidified, the series changes to Cd>Mn>Pb>Cu>Zn>Sb>Ni>Fe>As under acidic conditions Cd>Cu>Zn>Pb>Mn>Fe>Se>Mo>Sb>As>Ni. The mineral composition of the tailings was investigated, which will allow to determine the sources of toxic elements and to understand the processes of secondary mineral formation in technogenic objects. Arsenopyrite and pyrite predominate in the heavy fraction of the Komsomolsk tailings impoundment, arsenopyrite grains are often corroded, Sb contained in Sb oxide and Sb sulfide. The pyrite and barite are determined in the solid matter of the Karabash Mine Site and chalcopyrite, sphalerite, tennantite Cu3AsS3, and tetrahedrite (Cu,Fe)12Sb4S13 are determined in the form of inclusions in grains of pyrite.
Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.
Kharaka, Y.K.; Maest, A.S.; Carothers, W.W.; Law, L.M.; Lamothe, P.J.; Fries, T.L.
1987-01-01
Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70-120??C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are NaCaCl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H2S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H2S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl42- and ZnCl42-, respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters. ?? 1988.
Clark, Robert J.; Meier, A.L.; Riddle, G.; ,
1990-01-01
One objective of the International Falls and Roseau, Minnesota, CUSMAP projects was to develop a means of conducting regional-scale geochemical surveys in areas where bedrock is buried beneath complex glacially derived overburden. Partial analysis of B-horizon soils offered hope for detecting subtle hydromorphic trace-element dispersion patterns. An enzyme-based partial leach selectively removes metals from oxide coatings on the surfaces of soil materials without attacking their matrix. Most trace-element concentrations in the resulting solutions are in the part-per-trillion to low part-per-billion range, necessitating determinations by inductively coupled plasma/mass spectrometry. The resulting data show greater contrasts for many trace elements than with other techniques tested. Spatially, many trace metal anomalies are locally discontinuous, but anomalous trends within larger areas are apparent. In many instances, the source for an anomaly seems to be either basal till or bedrock. Ground water flow is probably the most important mechanism for transporting metals toward the surface, although ionic diffusion, electrochemical gradients, and capillary action may play a role in anomaly dispersal. Sample sites near the Rainy Lake-Seine River fault zone, a regional shear zone, often have anomalous concentrations of a variety of metals, commonly including Zn and/or one or more metals which substitute for Zn in sphalerite (Cd, Ge, Ga, and Sn). Shifts in background concentrations of Bi, Sb, and As show a trend across the area indicating a possible regional zoning of lode-Au mineralization. Soil anomalies of Ag, Co, and Tl parallel basement structures, suggesting areas that may have potential for Cobalt/Thunder Baytype silver viens. An area around Baudette, Minnesota, which is underlain by quartz-chlorite-carbonate-altered shear zones, is anomalous in Ag, As, Bi, Co, Mo, Te, Tl, and W. Anomalies of Ag, As, Bi, Te, and W tend to follow the fault zones, suggesting potential for lode-Au deposits. Soil anomalies of Co, Mo, and Tl appear to follow northwest-striking structures that cross the shear zones, suggesting that Thunder Bay-type mineralization may have overprinted earlier mineralization along the shear zones.
Petrology of the axial ridge of the Mariana Trough backarc spreading center
NASA Astrophysics Data System (ADS)
Hawkins, J. W.; Lonsdale, P. F.; Macdougall, J. D.; Volpe, A. M.
1990-10-01
The axial ridge of the Mariana Trough backarc basin, between 17°40'N and 18°30'N rises as much as 1 km above the floor of a 10-15 km wide rift valley. Physiographic segmentation, with minor ridge offsets and overlaps, coincides with a petrologic segmentation seen in trace element and isotope chemistry. Analyses of 239 glass and 40 aphyric basalt samples, collected with ALVIN and by dredging, show that the axial ridge is formed largely of (olivine) hypersthene-normative tholeiitic basalt. About half of these are enriched in both LIL elements and volatiles, but are depleted in HFS elements like other rocks found throughout much of the Mariana Trough. The LIL enrichments distinguish these rocks from N-MORB even though Nd and Sr isotope ratios indicate that much of the crust formed from a source similar to that for N-MORB. In addition to LIL-enriched basalt there is LIL depleted basalts even more closely resembling N-MORB in major and trace elements as well as Sr, Nd and Pb isotopes. Both basalt varieties have higher Al and lower total Fe than MORB at equivalent Mg level. Mg# ranges from relatively "primitive" (e.g. Mg# 65-70) to more highly fractionated (e.g. Mg# 45-50). Highest parts of the axial ridge are capped by pinnacles with elongated pillows of basaltic andesite (e.g. 52-56%) SiO 2. These are due to extreme fractional crystallization of basalts forming the axial ridge. Active hydrothermal vents with chimneys and mats of opaline silica, barite, sphalerite and lesser amounts of pyrite, chalcopyrite and galena formed near these silicic rocks. The vents are surrounded by distinctive vent animals, polychaete worms, crabs and barnacles. Isotope data indicate that the Mariana Trough crust was derived from a heterogeneous source including mantle resembling the MORB-source and an "arc-source" component. The latter was depleted in HFS elements in previous melting events and later modified by addition of H 2O and LIL elements.
CdS/ZnS nanocomposites: from mechanochemical synthesis to cytotoxicity issues.
Baláž, Peter; Baláž, Matej; Dutková, Erika; Zorkovská, Anna; Kováč, Jaroslav; Hronec, Pavol; Kováč, Jaroslav; Čaplovičová, Mária; Mojžiš, Ján; Mojžišová, Gabriela; Eliyas, Alexander; Kostova, Nina G
2016-01-01
CdS/ZnS nanocomposites have been prepared by a two-step solid-state mechanochemical synthesis. CdS has been prepared from cadmium acetate and sodium sulfide precursors in the first step. The obtained cubic CdS (hawleyite, JCPDS 00-010-0454) was then mixed in the second step with the cubic ZnS (sphalerite, JCPDS 00-005-0566) synthesized mechanochemically from the analogous precursors. The crystallite sizes of the new type CdS/ZnS nanocomposite, calculated based on the XRD data, were 3-4 nm for both phases. The synthesized nanoparticles have been further characterized by high-resolution transmission electron microscopy (HRTEM) and micro-photoluminescence (μPL) spectroscopy. The PL emission peaks in the PL spectra are attributed to the recombination of holes/electrons in the nanocomposites occurring in depth associated with Cd, Zn vacancies and S interstitials. Their photocatalytic activity was also measured. In the photocatalytic activity tests to decolorize Methyl Orange dye aqueous solution, the process is faster and its effectivity is higher when using CdS/ZnS nanocomposite, compared to single phase CdS. Very low cytotoxic activity (high viability) of the cancer cell lines (selected as models of living cells) has been evidenced for CdS/ZnS in comparison with CdS alone. This fact is in a close relationship with Cd(II) ions dissolution tested in a physiological solution. The concentration of cadmium dissolved from CdS/ZnS nanocomposites with variable Cd:Zn ratio was 2.5-5.0 μg.mL(-1), whereas the concentration for pure CdS was much higher - 53 μg.ml(-1). The presence of ZnS in the nanocrystalline composite strongly reduced the release of cadmium into the physiological solution, which simulated the environment in the human body. The obtained CdS/ZnS quantum dots can serve as labeling media and co-agents in future anti-cancer drugs, because of their potential in theranostic applications. Copyright © 2015 Elsevier B.V. All rights reserved.
Peters, S.G.; Jiazhan, H.; Zhiping, L.; Chenggui, J.
2007-01-01
Sedimentary rock-hosted Au deposits in the Dian-Qian-Gui area in southwest China are hosted in Paleozoic and early Mesozoic sedimentary rocks along the southwest margin of the Yangtze (South China) Precambrian craton. Most deposits have characteristics similar to Carlin-type Au deposits and are spatially associated, on a regional scale, with deposits of coal, Sb, barite, As, Tl, and Hg. Sedimentary rock-hosted Au deposits are disseminated stratabound and(or) structurally controlled. The deposits have many similar characteristics, particularly mineralogy, geochemistry, host rock, and structural control. Most deposits are associated with structural domes, stratabound breccia bodies, unconformity surfaces or intense brittle-ductile deformation zones, such as the Youjiang fault system. Typical characteristics include impure carbonate rock or calcareous and carbonaceous host rock that contains disseminated pyrite, marcasite, and arsenopyrite-usually with ??m-sized Au, commonly in As-rich rims of pyrite and in disseminations. Late realgar, orpiment, stibnite, and Hg minerals are spatially associated with earlier forming sulfide minerals. Minor base-metal sulfides, such as galena, sphalerite, chalcopyrite, and Pb-Sb-As-sulphosalts also are present. The rocks locally are silicified and altered to sericite-clay (illite). Rocks and(or) stream-sediment geochemical signatures typically include elevated concentrations of As, Sb, Hg, Tl, and Ba. A general lack of igneous rocks in the Dian-Qian-Gui area implies non-pluton-related, ore forming processes. Some deposits contain evidence that sources of the metal may have originated in carbonaceous parts of the sedimentary pile or other sedimentary or volcanic horizons. This genetic process may be associated with formation and mobilization of petroleum and Hg in the region and may also be related to As-, Au-, and Tl-bearing coal horizons. Many deposits also contain textures and features indicative of strong structural control by tectonic domes or shear zones and also suggest syndeformational ore deposition, possibly related to the Youjiang fault system. Several sedimentary rock-hosted Au deposits in the Dian-Qian-Gui area also are of the red earth-type and Au grades have been concentrated and enhanced during episodes of deep weathering. ?? 2006 Elsevier B.V. All rights reserved.
Combustion and leaching behavior of elements in the argonne premium coal samples
Finkelman, R.B.; Palmer, C.A.; Krasnow, M.R.; Aruscavage, P. J.; Sellers, G.A.; Dulong, F.T.
1990-01-01
Eight Argonne Premium Coal samples and two other coal samples were used to observe the effects of combustion and leaching on 30 elements. The results were used to infer the modes of occurrence of these elements. Instrumental neutron activation analysis indicates that the effects of combustion and leaching on many elements varied markedly among the samples. As much as 90% of the selenium and bromine is volatilized from the bituminous coal samples, but substantially less is volatilized from the low-rank coals. We interpret the combustion and leaching behavior of these elements to indicate that they are associated with the organic fraction. Sodium, although nonvolatile, is ion-exchangeable in most samples, particularly in the low-rank coal samples where it is likely to be associated with the organic constituents. Potassium is primarily in an ion-exchangeable form in the Wypdak coal but is in HF-soluble phases (probably silicates) in most other samples. Cesium is in an unidentified HNO3-soluble phase in most samples. Virtually all the strontium and barium in the low-rank coal samples is removed by NH4OAc followed by HCl, indicating that these elements probably occur in both organic and inorganic phases. Most tungsten and tantalum are in insoluble phases, perhaps as oxides or in organic association. Hafnium is generally insoluble, but as much as 65% is HF soluble, perhaps due to the presence of very fine grained or metamict zircon. We interpret the leaching behavior of uranium to indicate its occurrence in chelates and its association with silicates and with zircon. Most of the rare-earth elements (REE) and thorium appear to be associated with phosphates. Differences in textural relationships may account for some of the differences in leaching behavior of the REE among samples. Zinc occurs predominantly in sphalerite. Either the remaining elements occur in several different modes of occurrence (scandium, iron), or the leaching data are equivocal (arsenic, antimony, chromium, cobalt, and nickel). The results of these combustion and leaching experiments indicate that some previously held assumptions concerning modes of occurrence of elements in coal should be reconsidered.
Böhlke, J.K.; Radtke, A.S.; Heropoulos, Chris; Lamothe, P.J.
1981-01-01
Samples of cuttings from three drill holes in the Gibellini claims were analyzed by emission spectroscopic techniques for a large suite of major and trace elements. Unoxidized siliceous "black shale" from drill hole NGA 7 is strongly enriched in Cd, Mo, Sb, Se, V, and Zn, and also contains relatively high concentrations of As, Ba, Cu, Ni, and Tl compared with nonmetalliferous shales. Analyses of 103 samples plotted against depth in drill holes NGA, NG31, and NGA7, and selected XRD data, show the following: 1. Groups of elements with distinct distribution patterns define most of major mineralogic components of the rocks. The "normal shale" component, which includes several detrital and authigenic phases, is indicated by covariations among Ti, Al, Fe, Na, Mg, K, B, Be, Co, Cr, Ga, La, Sc, Sr, and Zr. The shale component is diluted by varying amounts of the following minerals (and associated elements): silica (Si); dolomite (Mg, Ca, Mn, Sr); apatite (Ca, Be, Cr, La, Sr, Y); barite (Ba, Sr); sphalerite (Zn, Cd, Fe?); smithsonite (Cd, Co, Mn, Ni, Zn); bianchite (Cd, Ni, Zn) ; and bokite (V). Pyrite, gypsum, and jarosite were also identified.2. The highly siliceous kerogenous metalliferous Gibellini facies is underlain by argillaceous and (or) dolomitic rocks. The transition zone deduced from the chemical data is not well defined in all instances, but probably represents the bottom of the black shale deposit. 3. Oxidation has reached to variable depths up to at least 150 ft, and has caused profound changes in the distributions of the enriched metals. Molybdenum, Se, and V have been partially removed from the upper parts of the sections and are concentrated near or slightly above the base of the Gibellini facies. Cadmium, Ni, and Zn have been strongly leached and now occur at or below the base of the Gibellini facies. The variable depth of oxidation, the redistribution and separation of the metals, and the complex mineralogy of the deposit may make development of the claim complicated.
NASA Astrophysics Data System (ADS)
Myung, EunJi; Cho, Kang Hee; Kim, Hyun Soo; Park, Cheon Young
2016-04-01
Many sulfides of metal such as galena, sphalerite, chalcopyrite, and pyrite, are semiconductors. When two kinds of such minerals contact each other in an electrolyte, a galvanic couple, where the mineral of lower rest potential as anode, and that of higher rest potential as cathode forms. Manganese dioxide is also a semiconductor with much higher rest potential than all sulfides mentioned above, so that a galvanic couple in which both the minerals would dissolve simultaneously can form, when it contacts with any of the sulfides. The aim of this study was to investigate the improvement in grade of minerals using the simultaneous bio-oxidation of deep-sea manganese crust and invisible gold concentrate. The samples(deep-sea manganese crust and invisible gold concentrate) were characterized by chemical and XRD analysis. The primary components of the invisible gold concentrate was pyrite and quartz and the deep-sea manganese crust was amorphous material, as detected using XRD. The result of chemical analysis showed that Au, Ag, Te contents in the invisible gold concentrate 130.2, 954.1 and 1,043.6 mg/kg, respectively. and that Mn, Ni, Co contents in the deep-sea manganese crust 19,501.5, 151.9, 400.4 mg/kg, respectively. In order to increase the bacteria's tolerance of heavy metals, the bacteria using bio-oxidation experiments were repeatedly subcultured in an Cu adaptation-medium containing of 382.98 mg/l for 20 periods of 21 days. The improvement in grade of samples of in present adapted bacteria condition was greater than another conditions(control and in present non-adapted bacteria). The Au-Ag-Te contents in the invisible gold concentrate was enhanced in the order of physical oxidation, simultaneous/non-adaptive bio-oxidation, adaptive/bio-oxidation, simultaneous/adaptive bio-oxidation. If the bacteria is adapted to heavy metal ions and an optimization of conditions is found in future bio-oxidation-leaching processes. Acknowledgment : "This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"
Whitney, P.R.
1981-01-01
Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic matter. ?? 1981.
Geological controls on refractory ore in an orogenic gold deposit, Macraes mine, New Zealand
NASA Astrophysics Data System (ADS)
Petrie, B. S.; Craw, D.; Ryan, C. G.
2005-07-01
The Macraes mine is hosted in an orogenic (mesothermal) gold deposit in metasedimentary rocks of the Otago Schist belt. Much gold occurs within altered schist with minimal silica-addition, and this study focuses on altered schist ore types. The unmineralized host schists are chemically and mineralogically uniform in composition, but include two end-member rock types: feldspathic schist and micaceous schist. Both rock types have undergone hydrothermal alteration along a shallow-dipping foliation-parallel shear zone, but their different rheological properties have affected the style of mineralisation. Micaceous schist has been extensively recrystallized and hydrothermally altered during ductile deformation, to form ores characterized by abundant, disseminated millimetre-scale pyrite cubes (typically 1 2 wt% S) and minor silicification. The earliest pyrite contained Ni and/or As in solid solution and no gold was imaged in these pyrites or later arsenopyrite grains. The ore type is refractory and gold recovery by cyanide leaching is less than 50%, with lowest recovery in rocks that have been less affected by later brittle deformation. In contrast, hydrothermally altered feldspathic schist is characterized by mineralised black microshears and veinlets formed during shear-zone related brittle deformation. Microsheared ore has relatively low sulphur content (<0.7 wt%) and muscovite has been illitised during hydrothermal alteration. Pyrite and arsenopyrite in microshears are fractured and deformed, and contain 1 10 μm blebs of gold. Later pyrite veinlets also contain micron- to submicron-scale inclusions of sphalerite, chalcopyrite, galena, and gold (≤10 microns). Gold in microsheared ore is more readily recoverable than in the refractory ore, although encapsulation of the fine gold grains inhibits cyanidation. Both microsheared ore and disseminated pyritic ore pass laterally into mineralised black shears, which contain hydrothermal graphite and late-stage cataclastic sulphides. This black, sheared ore releases gold readily, but the gold is then adsorbed on to gangue minerals (preg-robbed) and net cyanidation recovery can be less than 50%. Hence, low gold recovery during cyanidation results from (1) poor liberation of gold encapsulated in microcrystalline quartz and unfractured sulphide grains, and (2) preg-robbing of liberated gold during cyanidation. Introduction of pressure-oxidation of ore prior to cynidation has mitigated these issues.
Antunes, I M H R; Gomes, M E P; Neiva, A M R; Carvalho, P C S; Santos, A C T
2016-11-01
The mining complex of Murçós belongs to the Terras de Cavaleiros Geopark, located in Trás-os-Montes region, northeast Portugal. A stockwork of NW-SE-trending W>Sn quartz veins intruded Silurian metamorphic rocks and a Variscan biotite granite. The mineralized veins contain mainly quartz, cassiterite, wolframite, scheelite, arsenopyrite, pyrite, sphalerite, chalcopyrite, galena, rare pyrrhotite, stannite, native bismuth and also later bismuthinite, matildite, joseite, roosveltite, anglesite, scorodite, zavaritskite and covellite. The exploitation produced 335t of a concentrate with 70% of W and 150t of another concentrate with 70% of Sn between 1948 and 1976. The exploitation took place mainly in four open pit mines as well as underground. Three lakes were left in the area. Remediation processes of confination and control of tailings and rejected materials and phytoremediation with macrophytes from three lakes were carried out between 2005 and 2007. Stream sediments, soils and water samples were collected in 2008 and 2009, after the remediation process. Most stream sediments showed deficiency or minimum enrichment for metals. The sequential enrichment factor in stream sediments W>Bi>As>U>Cd>Sn=Ag>Cu>Sb>Pb>Be>Zn is mainly associated with the W>Sn mineralizations. Stream sediments receiving drainage of a mine dump were found to be significantly to extremely enriched with W, while stream sediments and soils were found to be contaminated with As. Two soil samples collected around mine dumps and an open pit lake were also found to be contaminated with U. The waters from the Murçós W>Sn mine area were acidic to neutral. After the remediation, the surface waters were contaminated with F(-), Al, As, Mn and Ni and must not be used for human consumption, while open pit lake waters must also not be used for agriculture because of contamination with F(-), Al, Mn and Ni. In most waters, the As occurred as As (III), which is toxic and is easily mobilized in the drainage system. The remediation promoted a decrease in metals and As concentrations of soils and waters, however the applied processes were not enough to rehabilitate the area. Copyright © 2016 Elsevier Inc. All rights reserved.
Bouabdellah, M.; Beaudoin, G.; Leach, D.L.; Grandia, F.; Cardellach, E.
2009-01-01
The Assif El Mal Zn-Pb (Cu-Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn-Pb (Cu-Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid-vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit Th mean values ranging from 104??C to 198??C. Final ice-melting temperatures range from -8.1??C to -12.8??C, corresponding to salinities of ???15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75??C to 150??C. The ??18O and ??D fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low ??13CVPDB values ranging from -7.5??? to -7.7??? indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn-Pb (Cu-Ag) veins. The calculated ??34SH2S values for reduced sulfur (22.5??? to 24.3???) are most likely from reduction of SO42- in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO2 which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid-rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean. ?? Springer-Verlag 2009.
NASA Astrophysics Data System (ADS)
Delibaş, Okan; Moritz, Robert; Chiaradia, Massimo; Selby, David; Ulianov, Alexey; Revan, Mustafa Kemal
2017-12-01
The Pınarbaşı Mo-Cu prospect is hosted within the Pınarbaşı intrusion, which is exposed together with the NW-SE-trending Koyunoba, Eğrigöz, and Baklan plutons along the northeastern border of the Menderes massif. The Pınarbaşı intrusion predominantly comprises monzonite, porphyritic granite, and monzodiorite. All units of the Pınarbaşı intrusion have sharp intrusive contacts with each other. The principal mineralization style at the Pınarbaşı prospect is a porphyry-type Mo-Cu mineralization hosted predominantly by monzonite and porphyritic granite. The porphyry type Mo-Cu mineralization consists mostly of stockwork and NE- and EW-striking sub-vertical quartz veins. Stockwork-type quartz veins hosted by the upper parts of the porphyritic granite within the monzonite, are typically enriched in chalcopyrite, molybdenite, pyrite, and limonite. The late NE- and EW-striking normal faults cut the stockwork vein system and control the quartz-molybdenite-chalcopyrite-sphalerite-fahlore-galena veins, as well as molybdenite-hematite-bearing silicified zones. Lithogeochemical and whole-rock radiogenic isotope data (Sr, Nd and Pb) of the host rocks, together with Re-Os molybdenite ages (18.3 ± 0.1 Ma - 18.2 ± 0.1 Ma) reveal that the monzonitic and granitic rocks of the Pınarbaşı intrusion were derived from an enriched lithospheric mantle-lower crust during Oligo-Miocene post-collisional magmatism. The lithospheric mantle was metasomatised by fluids and subducted sediments, and the mantle-derived melts interacted with lower crust at 35-40 km depth. This mechanism explains the Mo and Cu enrichments of the Pınarbaşı intrusion during back-arc magmatism. We conclude that the melt of the Pınarbaşı intrusion could have rapidly ascended to mid-crustal levels, with only limited crustal assimilation along major trans-lithospheric faults as a result of thinning of the middle to upper crust during regional extension, and resulted in the development of porphyry-style mineralization during the early Miocene (˜18 Ma). The subsequent exhumation history of the Mo-Cu-bearing Pınarbaşı intrusion is attributed to regional-scale uplift, and further exhumation along detachment faults of the associated core complexes during the middle to late Miocene.
NASA Astrophysics Data System (ADS)
Lüders, Volker; Romer, Rolf L.; Gilg, H. Albert; Bodnar, Robert J.; Pettke, Thomas; Misantoni, Dean
2009-05-01
Deposition of quartz-molybdenite-pyrite-topaz-muscovite-fluorite and subsequent hübnerite and sulfide-fluorite-rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz-molybdenite-pyrite-topaz-muscovite-fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO2-bearing, moderately saline (7.5-12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry-Cu-Au-Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO2-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ34S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ18O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable 87Sr/86Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wenrich, K.J.; Hlava, P.F.
An extensive suite of Ni-Co-Fe-Cu sulfides and arsenides lies within the matrix of solution-collapse breccias buried deep within the plateaus of the Grand Canyon region. Ceilings over large caverns in the Redwall collapsed, brecciating the overlying sandstone and forming cylindrical breccia pipes up to 300 ft in diameter that extend vertically as much as 3,000 ft. These highly permeable breccias served as a host for the precipitation of a suite of over 100 minerals, including uraninite, sphalerite, galena and various copper phases, in addition to the Ni-Co-bearing-phase discussed here. Intricately zoned crystals of small (<1 mm), euhedral Ni-Co-Fe-As-S minerals weremore » the first to form during the second major episode of mineralization in these pipes. Several of these phases replace minerals, such as barite and anhydrite, from the first episode. Extensive microprobe work has been done on samples from two breccia pipe mines, the Hack 2 and Orphan, which are about 50 miles apart. Mineral compositions are similar except that no copper is found in the Ni-Co-Fe phases from the Hack 2 mine, while pyrites containing 1 wt % Cu are common from the Orphan, which was mined for copper. In some of these pyrites', Cu is dominant and the mineral is actually villamaninite. Pyrites from both mines characteristically contain 0.5 to 3 wt % As. Metal contents in zones pyrite-bravoite-vaesite (M[sub 1]S[sub 2]) crystals at the Hack 2 mine range from Fe[sub 1] to Fe[sub .12], Ni[sub 0] to Ni[sub .86], and Co[sub 0] to Co[sub .10]. The metal content for polydymite-siegenite-violarite averages about (Ni[sub 2.33]Co[sub .39]Fe[sub .23])(S[sub 3.9]As[sub .1]). Orphan mine pyrite-bravoite-vaesite-villamaninite ranges in composition from pure FeS[sub 2] to (Ni[sub .6]Fe[sub .21]Co[sub .17])S[sub 2], and (Cu[sub .46]Ni[sub .27]Fe[sub .21]Co[sub .13])S[sub 2]. Of all the sulfides or arsenides found in these breccia pipes, only nickeline consistently occurs as the pure end member.« less
Geochemistry of Standard Mine Waters, Gunnison County, Colorado, July 2009
Verplanck, Philip L.; Manning, Andrew H.; Graves, Jeffrey T.; McCleskey, R. Blaine; Todorov, Todor I.; Lamothe, Paul J.
2009-01-01
In many hard-rock-mining districts water flowing from abandoned mine adits is a primary source of metals to receiving streams. Understanding the generation of adit discharge is an important step in developing remediation plans. In 2006, the U.S. Environmental Protection Agency listed the Standard Mine in the Elk Creek drainage basin near Crested Butte, Colorado as a superfund site because drainage from the Standard Mine enters Elk Creek, contributing dissolved and suspended loads of zinc, cadmium, copper, and other metals to the stream. Elk Creek flows into Coal Creek, which is a source of drinking water for the town of Crested Butte. In 2006 and 2007, the U.S. Geological Survey undertook a hydrogeologic investigation of the Standard Mine and vicinity and identified areas of the underground workings for additional work. Mine drainage, underground-water samples, and selected spring water samples were collected in July 2009 for analysis of inorganic solutes as part of a follow-up study. Water analyses are reported for mine-effluent samples from Levels 1 and 5 of the Standard Mine, underground samples from Levels 2 and 3 of the Standard Mine, two spring samples, and an Elk Creek sample. Reported analyses include field measurements (pH, specific conductance, water temperature, dissolved oxygen, and redox potential), major constituents and trace elements, and oxygen and hydrogen isotopic determinations. Overall, water samples collected in 2009 at the same sites as were collected in 2006 have similar chemical compositions. Similar to 2006, water in Level 3 did not flow out the portal but was observed to flow into open workings to lower parts of the mine. Many dissolved constituent concentrations, including calcium, magnesium, sulfate, manganese, zinc, and cadmium, in Level 3 waters substantially are lower than in Level 1 effluent. Concentrations of these dissolved constituents in water samples collected from Level 2 approach or exceed concentrations of Level 1 effluent suggesting that water-rock interaction between Levels 3 and 1 can account for the elevated concentration of metals and other constituents in Level 1 portal effluent. Ore minerals (sphalerite, argentiferous galena, and chalcopyrite) are the likely sources of zinc, cadmium, lead, and copper and are present within the mine in unmined portions of the vein system, within plugged ore chutes, and in muck piles.
NASA Astrophysics Data System (ADS)
Cathalot, C.; Laes-Huon, A.; Pelleter, E.; Maillard, L.; Chéron, S.; Boissier, A.; Waeles, M.; Cotte, L.; Pernet-Coudrier, B.; Gayet, N.; Sarrazin, J.; Sarradin, P. M.
2016-12-01
Despite the importance of trace metals for marine ecosystems and in the global carbon cycle, dissolved metal sources in the deep ocean and their export mechanism are, today, still unconstrained. The historical view that dissolved metals are largely removed from hydrothermal plumes through precipitation of a range of iron-bearing minerals is now being challenged. Several potential mechanisms for the delivery of hydrothermally sourced metals to the open ocean have been suggested and require a thorough documentation of the early mixing processes between the hydrothermal fluids and the ambient seawater. The geochemistry of a plume, and specially the rising plume, is dictated by the nature and composition of the host rock, fluid temperature, phase separation at depth and subsurface mixing processes, and thus can vary in temperature, pH, metal and dissolved gases content between spatially close hydrothermal vents. Here, we present in situ chemical conditions during the early mixing gradient between hydrothermal fluids and seawater at the Lucky Strike site (Mid-Atlantic Ridge), using a multi proxy approach targeting both the dissolved and particulate phase and combining in situ measurements and analysis back in the lab. Indeed, in situ O2, H2S and temperature measurements were performed at a 1Hz frequency, coupled to lower frequency analysis of in situ Fe2+. In addition, particulate material filtered in situ was analyzed using Inductive Coupled Plasma - Mass Spectrometry, X-Ray Diffraction, X-Ray Fluorescence and Scanning Electron Microscopy and provided useful insights regarding the reactivity of metals during the mixing processes. Our results show different behavior within the Lucky Strike vent field. Fe and S co-precipitation through chalcopyrite formation at the newly discovered Capelinhos site seem to be the main process. At the White Caste site, on the other hand, wurzite and sphalerite precipitation seems to dominate the dilution processes, H2S being rapidly titrated with the available Zinc early in the mixing. Our results indicate a clear control by subsurface mixing processes, at a very local scale: within a single vent field, temperature outflow of the hydrothermal fluid clearly drives Cu, Fe and Zn scavenging in the particulate phase, and controlling hence the iron stability and export.
Classification of mineral deposits into types using mineralogy with a probabilistic neural network
Singer, Donald A.; Kouda, Ryoichi
1997-01-01
In order to determine whether it is desirable to quantify mineral-deposit models further, a test of the ability of a probabilistic neural network to classify deposits into types based on mineralogy was conducted. Presence or absence of ore and alteration mineralogy in well-typed deposits were used to train the network. To reduce the number of minerals considered, the analyzed data were restricted to minerals present in at least 20% of at least one deposit type. An advantage of this restriction is that single or rare occurrences of minerals did not dominate the results. Probabilistic neural networks can provide mathematically sound confidence measures based on Bayes theorem and are relatively insensitive to outliers. Founded on Parzen density estimation, they require no assumptions about distributions of random variables used for classification, even handling multimodal distributions. They train quickly and work as well as, or better than, multiple-layer feedforward networks. Tests were performed with a probabilistic neural network employing a Gaussian kernel and separate sigma weights for each class and each variable. The training set was reduced to the presence or absence of 58 reported minerals in eight deposit types. The training set included: 49 Cyprus massive sulfide deposits; 200 kuroko massive sulfide deposits; 59 Comstock epithermal vein gold districts; 17 quartzalunite epithermal gold deposits; 25 Creede epithermal gold deposits; 28 sedimentary-exhalative zinc-lead deposits; 28 Sado epithermal vein gold deposits; and 100 porphyry copper deposits. The most common training problem was the error of classifying about 27% of Cyprus-type deposits in the training set as kuroko. In independent tests with deposits not used in the training set, 88% of 224 kuroko massive sulfide deposits were classed correctly, 92% of 25 porphyry copper deposits, 78% of 9 Comstock epithermal gold-silver districts, and 83% of six quartzalunite epithermal gold deposits were classed correctly. Across all deposit types, 88% of deposits in the validation dataset were correctly classed. Misclassifications were most common if a deposit was characterized by only a few minerals, e.g., pyrite, chalcopyrite,and sphalerite. The success rate jumped to 98% correctly classed deposits when just two rock types were added. Such a high success rate of the probabilistic neural network suggests that not only should this preliminary test be expanded to include other deposit types, but that other deposit features should be added.
NASA Astrophysics Data System (ADS)
Salvi, Stefano; Williams-Jones, Anthony E.
1990-09-01
The Strange Lake Zr, Y, REE, Nb, and Be deposit is hosted by a small, high-level, Late-Proterozoic peralkaline granite stock that intruded into high-grade metamorphic gneisses on the Quebec-Labrador border. The stock is extensively altered. Early alteration is manifested by the replacement of arfvedsonite with aegirine. Later alteration involved Ca-Na exchange. Zr, Ti, Y, REEs, Nb, and Be are concentrated in Ca-bearing minerals that, together with quartz, commonly pseudomorph Na-bearing minerals. Fluid inclusions in pseudomorphs comprise several distinct types: high-salinity (13 to 24 wt% NaCl eq.), Ca-rich aqueous inclusions that homogenize to liquid between 135 and 195°C; mixed aqueousmethane inclusions; methane inclusions; and solid-bearing inclusions. Aqueous-methane inclusions represent heterogeneous entrapment of immiscible high-salinity aqueous liquid and methane. Bastnäsite (tentatively identified by SEM analysis) occurs as a daughter mineral. Other daughter or trapped minerals include a Y, HREE-bearing mineral, possibly gagarinite, and hematite, galena, sphalerite, fluorite, pyrochlore, kutnahorite (?), and griceite (?). The first three inclusion types also occur in quartz in pegmatites and veins together with lower-temperature, lower-salinity, Na-dominated aqueous inclusions. The entrapment temperature inferred for the aqueous inclusions from microthermometry and the Na-K-Ca geothermometer range from 155 to 195°C for the higher-salinity inclusions and 100 to 165°C for the low-salinity inclusions. A model is proposed in which the intrusion of a peralkaline granite to high crustal levels initiated a ground/formational water-dominated hydrothermal system in adjacent gabbroic, calc-silicate, and graphitic gneisses. Reaction of the high-salinity, Ca-rich liquid with the graphitic gneisses led to the production of an immiscible methane gas. Subsequent interaction of this liquid with the granite led to extensive replacement of sodic minerals by calcium analogues at temperatures of less than 200°C. Some time after the onset of Ca metasomatism the high-salinity liquid mixed with a Ca-poor, low-salinity, low-temperature liquid that had leached F and rare metals from the granite. Yttrium and REE mineral deposition occurred as a result of the decreased ligand concentration that accompanied fluorite deposition during mixing of the Ca-rich and Ca-poor aqueous liquids.
NASA Astrophysics Data System (ADS)
Yalçin, Cihan; Hanilçi, Nurullah; Kumral, Mustafa; Abdelnasser, Amr
2016-04-01
Göçükdibi Cu-Pb-Zn mineralization is located 3 km north west of Gökçedoǧan village where is 30 km east of the Kargı, Çorum. The geology of the mineralization area is represented by Mesozoic and Upper Pliocene lithostratigraphic units in different origin. These units with respect to their structural locations have identified as autochthonous and allachtonous. The autochthonous units which are the basement of the region are represented by Bekirli Metamorphites (Triassic-Liassic) and Beşpınar formation (Upper Cretaceous-Lower Eocene) which overlies the Bekirli Metamorphites as angular discordance. The allachtonous units are represented by Saraycık formation belongs to Kargı Ophioltic Melange, and located on the autochthonous units as tectonically. These allocthonous units are the product of the Neotethyan Ocean. The autochthonous and allachtonous units are overlaid by Upper Pliocene Ilgaz Formation and Plio-Quaternary stream sediments. The Cu-Pb-Zn mineralization is located in northwest of the Gökçedoǧan village within the Bekirli Metamorphites. The ore zone has N80E direction, 5 m wide and 120 m in length. The mineralizations which follow NE-SW trending structural line occurred as alternation with quartz-chlorite schists of the Bekirli Metamorphites. The mineralization is generally concordant to the foliation of schist's and also occurred as disseminated in the wall rocks. The ore paragenesis comprises with pyrite, chalcopyrite, sphalerite and galenit as the main sulphide minerals, and the malachite, azurite and limonite as the production of the oxidation. Preliminary data such as relationship between the ore and host rock, inner-structure of the ore and indicate that the Gökçedoǧan Cu-Pb-Zn mineralization was likely to have originated syngenetic. In addition, the geochemical behaviour of rare earth elements (REE) of the altered and mineralized samples collected from the alteration zone show that light REE enrichment with fair depletion of heavy REE during the alteration processes with positive Eu anomalies. As well as there is a positive correlation between K2O index and LREE that reveal the addition of K and La and the sericitization is the main alteration associated with the studied deposit. Key Words: Cu-Pb-Zn mineralization, Syngenetic, Bekirli Metamorphites, Gökçedoǧan.
NASA Astrophysics Data System (ADS)
Scheffer, Christophe; Tarantola, Alexandre; Vanderhaeghe, Olivier
2016-04-01
At the crustal scale, the ductile-brittle transition (DBT) might correspond to a physical barrier that separates a deep reservoir of metamorphic and magmatic fluids from a shallow reservoir of surficial fluids. Rock rheology, and thus the location of the DBT, is mainly governed by lithology, temperature and the presence/absence of fluids. Accordingly, the position of the DBT potentially evolves during orogenic evolution owing to thermal evolution and fluid circulation. In turn rocks are transferred across it during burial and exhumation. These processes induce connections between fluid reservoirs which might play a role on ore deposition. In this contribution, we discuss the impact of lithological heterogeneities on deformation, fluid flow and ore deposition based on the example of the Lavrion low-angle top-to-the-SSW detachment accommodating gravitational collapse of the Hellenides orogenic belt in Greece. The Lavrion peninsula, localized along the western boundary of the Attic-Cycladic Metamorphic Core Complex, is characterized by Pb-Zn-Fe-Cu-Ag ore mineralization mainly concentrated along a lithological contact (marble/schists) below and within a detachment shear zone. The mylonitic marble below the detachment shear zone is composed of white layers of pure marble alternating with blue layers containing impurities (SiO2, Al2O3, organic matter…). Development of the mylonitic fabric in competent impure blue marble is associated with its preferred dolomitization related to focused fluid infiltration. This mylonitic marble is cross-cut by several cataclastic horizons preferentially developed within the more competent impure blue marble and newly-crystallized dolomitic horizon. These cataclasites are invaded by fluorite and calcite gangue minerals showing locally Mn, Pb, Zn, Fe oxides and/or hydroxides, sphalerite, Ag-galena, Ag-sulfur and native Ag. Oxygen and carbon stable isotopes performed on marble sections point out decarbonation with magmatic contribution and fluid-rock interactions including organic matter present in the whole-rock during ore precipitation. These features show the positive feedback between localization of ductile-brittle deformation-recrystallization, fluid circulation and ore deposition. Accordingly, during orogenic gravitational collapse, the activation of mylonitic-cataclastic low-angle detachments, controlled at first order by temperature, are, at second order, influenced by lithologic heterogeneities that are determinant at localizing fluid circulation, allowing thus a multi-localization of the DBT and ore deposition.
U-Pb Dating of Calcite to Constrain Basinal Brine Flux Events: An Example from the Upper Midwest USA
NASA Astrophysics Data System (ADS)
Rasbury, T.; Luczaj, J.
2017-12-01
Calcite forms in a variety of settings and can be the product of surface to deep basinal fluids. As such, this mineral can uniquely record details of the fluids responsible for its formation. The forms of calcium carbonates and their stratigraphic relationships from the thin section to the regional scale give important insights on pulses of fluids. A fundamental question is the age of such fluid pulses. While calcite excludes uranium (U) from its crystal structure, some is incorporated and depending on the U/Pb ratio, this provides an opportunity for radiometric dating. Calcite crystals of various sizes and crystal habits are found in Paleozoic carbonate rocks throughout the region from the western Michigan basin to the upper Mississippi valley. These are typically associated with Mississippi Valley-type (MVT) mineralization, including galena, sphalerite, and iron sulfides, but typically post-date the main MVT event. We have analyzed a variety of these calcites and find multiple generations of calcite, separated by tens of millions of years. The initial Pb isotope ratios are similar to the isotope ratios of nearby galena, strongly suggesting a genetic relationship. Our oldest ages are 200 Ma, and we find ages ranging into the Cenozoic. Based on the Paleozoic-hosted galena Pb-isotope isoscapes from the region, the fluids may have been sourced from both the Michigan and Illinois basins. An important and unanswered question is what would cause significant fluid movement out of the basins substantially after Appalachian orogenesis. Noble gas data from brines in the Michigan Basin have a mantle component and have been suggested to be responsible for recognized elevated temperatures across the basin (Ma et al., 2009). Multiple thermal events during the Paleozoic and Mesozoic eras may have an internal heat source related to reactivation of faults of the Keweenawan Rift system below the Michigan Basin. Perhaps a mantle heat source from below episodically fluxes into the basins and displaces brines with important ore metals out of the basin. More work on the calcites will help to establish the geographic extent of the various fluid pulses in the region, which will lead to an improved understanding of the sources and paths of these fluids.
NASA Astrophysics Data System (ADS)
Bilohuščin, Vladimír; Uher, Pavel; Koděra, Peter; Milovská, Stanislava; Mikuš, Tomáš; Bačík, Peter
2017-09-01
Borate minerals of the ludwigite group (LGM) and szaibélyite in association with hydroxylclinohumite, clinochlore, a serpentine mineral, magnesian magnetite, spinel, magnesite, dolomite and sulphide minerals, occur in a magnesian exoskarn in the R-20 borehole located in the Vysoká - Zlatno Cu-Au porphyry-skarn deposit, located within the Štiavnica Neogene stratovolcano, Western Carpathians, central Slovakia. The skarn is developed along the contact of Miocene granodiorite to quartz-diorite porphyry and a Middle-Upper Triassic dolomite-shale-psammite-anhydrite sedimentary sequence. The boron minerals were investigated by electron probe micro-analyser (EPMA) and micro-Raman techniques. The source of boron could have been from the granodiorite/quartz diorite intrusion; however some supply of B from adjacent evaporite-bearing sediments is also possible. Based on textural and compositional data, the minerals originated during two stages. (1) An early high-temperature, contact-metamorphic and metasomatic stage comprises coarse-crystalline aggregate of LGM (types 1 to 3) in association with hydroxylclinohumite, magnetite, and rarely spinel inclusions in LGM. Compositional variations of LGM show a crystallization sequence from early azoproite [≤17 wt% TiO2; 0.40 atoms pre formula unit (apfu) Ti, which correspond to ≤79 mol% of the Mg2(Mg0.5Ti0.5)O2(BO3) end-member], Ti-Al-rich members of LGM, "aluminoludwigite "[≤14 wt% Al2O3; ≤0.53 apfu, ≤53 mol% of Mg2AlO2(BO3) end-member] and Al-rich ludwigite in the central zone of crystals, to Ti-Al-poor ludwigite in outer parts of crystals. (2) Minerals of the late retrograde serpentinization and hydrothermal stage form irregular veinlets and aggregates, including partial alteration of hydroxylclinohumite to the serpentine-group mineral and clinochlore, replacement of LGM by szaibélyite, formation of the latest generation of Fe-rich, Ti-Al poor ludwigite in veinlets (type 4), and precipitation of dolomite, magnesite and sulphide minerals (valleriite, sphalerite, chalcopyrite). The distinct compositional zoning of the LGM documents a complex evolution of the skarn beginning with a high-temperature stage 1 and ending with a low-temperature overprint, stage 2.
Zhang, Wen; Hu, Zhaochu; Günther, Detlef; Liu, Yongsheng; Ling, Wenli; Zong, Keqing; Chen, Haihong; Gao, Shan
2016-12-15
In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of 204 Hg on 204 Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for 20x Pb/ 204 Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for 20x Pb/ 206 Pb and <0.06% (RSD, k = 2) for 20x Pb/ 204 Pb with the exception of 20x Pb/ 204 Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g -1 ) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g -1 ). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability and robustness of our analytical protocol. Copyright © 2016 Elsevier B.V. All rights reserved.
Geological and geochemical studies in the Wadi Bidah District, Kingdom of Saudi Arabia
Smith, C.W.; Waters, B.C.; Naqvi, M.; Worl, R.G.; Helaby, A.M.; Flanigan, V.J.; Sadek, H.S.; Samater, R.M.
1983-01-01
Geological and geochemical followup studies of airborne electromagnetic anomalies in the Wadi Bidah district, southwestern Saudi Arabia, did not reveal metals of economic grade. Investigation of an anomaly enclosing the Rabathan ancient mine disclosed tightly folded and sheared Proterozoic tuffaceous rocks interlayered mostly with chert, dolomite, carbonaceous rocks, and volcanic wacke including cherty iron-manganese formations slightly anomalous in copper and zinc. Three drill holes placed to test anomalies within these formations yielded negative results. Studies of a long, narrow anomaly north of the Rabathan area indicated a similar geological environment. This northern area also contains limited zones that are highly anomalous in copper and zinc and extensive zones that are slightly anomalous in those metals. Drilling was not undertaken in this area. The Bilajimah airborne electromagnetic anomaly west of Wadi Bidah coincides with a broad synclinorium of layered felsic turfs and gossans. Geochemical studies indicated slightly anomalous copper, zinc, and silver values in gossans within the anomaly area. Two drill holes intersected carbonaceous rock that contained approximately 15 percent pyrrhotite and traces of sphalerite and chalcopyrite. Two geophysically anomalous areas west of Wadi Bidah surround ancient mines at Mahawiyah and Khayal al Masna'ah. Results of geochemical sampling at these workings were positive. An airborne electromagnetic anomaly located in the Assifar area in the southwestern corner of the Wadi Bidah district is underlain principally by metasedimentary rocks that include large linear zones of cherty iron-manganese formation and a few gossans .containing secondary base metal minerals. Detailed mapping and sampling of the Mulhal ancient mine, located west of Wadi Bidah, revealed two types of polymetallic gossans : (1) stratiform deposits interlayered with ignimbrites and mafic volcanic rocks and (2) barite-bearing gossanous material in shear zones that grade into hydrothermally altered shear zones and extend beyond the mine area. The gossans and gossanous shear zones contain anomalous amounts of gold, silver, lead, copper, zinc, barium, and selenium. Two gossans west of Wadi Bidah were mapped and sampled in detail; both gossans are interlayered, with siliceous volcanic rocks. Although the gossan at Jabal Mohr covers a large area, it contains low amounts of precious and base metals. The gossan at Mulhal No. 2 contains moderate to high amounts of gold, silver, copper, lead, and zinc.
Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria
NASA Astrophysics Data System (ADS)
Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.
2012-04-01
Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7 ± 0.3‰) when sulfate concentrations rose above 0.5 mM and sulfide concentrations had became negligible.
NASA Astrophysics Data System (ADS)
Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel
2002-05-01
Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.
The Biogeochemistry of Indium, Gallium, and Germanium in Mine Wastes
NASA Astrophysics Data System (ADS)
White, S. J.; Schaider, L. A.; Shine, J. P.
2017-12-01
Indium (In), gallium (Ga), and germanium (Ge) are metals important in new energy technologies, and use of these metals is expanding dramatically. Humans are significantly impacting their natural cycling. Mining and smelting appear to be currently the largest sources of these metals to the environment, primarily because In, Ga, and Ge are byproducts of lead and zinc mining. The life cycle of these metals is poorly understood, including partitioning and speciation during mining processes, environmental behavior, and toxicity. The Tar Creek Superfund Site in Oklahoma, USA, is an abandoned Mississippi Valley-type lead and zinc mining area, containing sphalerite (ZnS) and galena (PbS). 30 major tailings piles remain in the area; elevated concentrations of lead (Pb), zinc (Zn), and cadmium (Cd) in these wastes have caused human health concerns. In order to better understand the biogeochemical cycling of In, Ga, and Ge associated with mining processes, we conducted geochemical and biological extractions of size-fractionated mine tailings from the Tar Creek site. Small tailings particles (<2.5 μm) contain higher concentrations of In, Ga, and Ge than large particles (>0.5 mm); a similar enrichment has been shown previously for Pb, Zn, and Cd. Ge is highly elevated in the mine wastes at this site; small particles contain up to 40x crustal concentrations. Ga and In are not significantly higher than crustal. (Crustal concentrations: Ge 1.4 mg/kg; Ga 14 mg/kg; In 100 mg/kg) While Pb, Zn, and Cd have been shown previously to be highly labile, and thus significantly re-worked from the original sulfide ore, sequential extractions suggest that In, Ga, and Ge are in less labile forms. In and Ga are liberated primarily from solutions that target semi-labile amorphous sulfides, Fe- and Mn-oxyhydroxides, and crystalline sulfide phases. By contrast, over 85% of the Ge in mine wastes from this site is bound in a residual mineral fraction (e.g. silicates) that is not liberated by a hot nitric acid leach. The bioaccessibility of In, Ga, and Ge also is significant - simulated gastric fluid extractions release 41-84% of each metal, suggesting that they do not reside in the ZnS or PbS phases. Future studies will further explore the cycling of Ga, Ge, and In at the Tar Creek site, including differences in speciation, mobility, and bioaccessibility of each.
Genesis of the Abu Marawat gold deposit, central Eastern Desert of Egypt
NASA Astrophysics Data System (ADS)
Zoheir, Basem A.; Akawy, Ahmed
2010-06-01
Gold mineralisation at the Abu Marawat mine, central Eastern Desert of Egypt, is related to a system of massive and sheared, milky quartz veins cutting a sequence of Neoproterozoic island arc metavolcanic/volcaniclastic rocks and related banded iron formation (BIF). Sulphide-bearing quartz veins and related hydrothermal breccia bodies display a range of textures including sheared, boudinaged and recrystallised quartz, open space filling and microbreccia. These variable textures imply a complex history of crack-seal mechanism characterising the relation between mineral deposition and a major N-S-trending shear zone, during a late brittle-ductile deformation event which affected the area at about 550 Ma. Gold-base metal mineralisation is associated with brecciation and fracturing of the iron ore bands, close to silicified shears and related quartz veins. The auriferous quartz lodes are characterised by the occurrence of visible pyrite-chalcopyrite ± pyrrhotite ± sphalerite ± galena mineralisation. Gold is refractory in pyrite and chalcopyrite, but rare visible gold/electrum and telluride specks were observed in a few samples. Hydrothermal alteration includes pervasive silicification, pyritisation, sericitisation, carbonatisation confined to a delicate set of veins and altered shears, and a more widespread propylitic alteration assemblage (quartz + chlorite + pyrite + calcite ± epidote). Fluid inclusion petrography and microthermometric studies suggest heterogeneous trapping of a low-salinity (1.4-6.7 wt.% eq. NaCl) aqueous solution and a carbonic fluid. Evidence for fluid immiscibility during ore formation includes variable liquid/vapour ratios in inclusions along individual trails and bulk inclusion homogenisation into liquid and occasionally to vapour at comparable temperatures. The trapping conditions of intragranular aqueous-carbonic inclusions approximate 264-378 °C at 700-1300 bar. Similar temperature estimates have been obtained from Al-in-chlorite geothermometry of chlorite associated with sulphides in the mineralised quartz veins. Fracturing enhanced fluid circulation through the wallrock and related BIF, allowing reaction of the S-bearing ore fluid with iron oxides. This caused pyrite formation and concomitant Au precipitation, enhanced by fluid immiscibility as H 2S partitioned preferentially into the carbonic phase. The ore fluids may have originated from granitoid intrusions (likely the post-Hammamat felsites, whereas gold and base metals might have been leached from the Abu Marawat basic metavolcanics.
Mineralogy of the Chaparra IOCG deposit, southern Peru
NASA Astrophysics Data System (ADS)
Yáñez, Juan; Alfonso, Pura
2014-05-01
The Chaparra IOCG, located in southern Peru, near Chala, is mined and exploited by small-scale miners for gold, however, it has not been studied until now. Here we present a preliminary geological and mineralogic study of this deposit. Powder X ray diffraction, electron microscopy and electron microprobe were used to characterize the mineralization. This deposit is hosted in magmatic rocks from the Coastal Batholith. Host rocks belong to the Linga Super-unit, of Upper Cretaceous age and are mainly constituted by monzonites, monzogabbros and diorites. Major alterations are the propylitic (chlorite - albite - quartz), advanced argillic (jarosite - natrojarosite) and sericitic (muscovite-sericite-quartz). Gypsum and other alteration minerals such as potassium feldspar and phlogopite, vermiculite and natrolite are widespread. Mineralization occurs mainly in quartz veins up to 1 m thick, emplaced filling fractures. Ore mineralogy is mainly composed of hematite, goethite, and sulphides (mainly pyrite, chalcopyrite and covellite). Gold and REE-rich minerals also occur. Native gold can reach up to 1 mm in size, but usually is few μm in size. Its composition is 82-92 wt% Au, up to 12 wt% of Ag and Fe can reach up to 4 wt%. The paragenetic sequence in the Chaparra deposit was divided into three stages: (I) primary mineralization, (II) Fracture filling, and (III) supergene alteration. The sequence begins with the crystallization of magnetite, quartz, pyrrhotite and pyrite. Subsequently, native gold, native Bismuth and uraninite crystallices together with the former minerals, in which are enclosed. Later, monacite is formed, being enclosed in quartz. Pyrite also presents small grains of chalcopyrite inside. Galena, sphalerite and arsenopyrite also are formed, whether included in pyrite or outside. Scarce grains of sakuraiite also occur in this stage. Structural formula of sakuraiie from this deposit is Cu 01.78-1.90 Zn 0.07-12Fe 1.16-124In 0.22-0.26Sn 0.79-082S4). Indium content of this mineral is between 5.43 and 6.41 wt%. At the end of this stage hematite and Cu-rich minerals, mainly tetrahedrite and covellite are formed. In addition, other sulphosalts, as tennantite and annivite are generated. Rrutile, zircon, apatite and subsequently ferrocordierite are also formed. In the stage (II) fractures are produced and filled by tetrahedrite, garavellite and native bismuth. Finally, in the stage (III) supergene alteration generates goethite, jarosite, gypsum, scorodite and yodargirite.
Kelley, K.D.; Kelley, D.L.
1992-01-01
A reconnaissance geochemical survey was conducted in the southern Killik River quadrangle, central Brooks Range, northern Alaska. The Brooks Range lies within the zone of continuous permafrost which may partially inhibit chemical weathering and oxidation. The minus 30-mesh and nonmagnetic heavy-mineral concentrate fractions of sediment samples were chosen as the sample media for the survey so that mechanical rather than chemical dispersion patterns would be enhanced. A total of 263 sites were sampled within the southern half of the Killik River quadrangle at an average sample density of approximately one sample per 12 km2. All samples were submitted for multi-element analyses. In the western and central Brooks Range, several known sediment-hosted Zn-Pb-Ag(-Ba) deposits occur within a belt of Paleozoic rocks of the Endicott Mountains allochthon. Exploration for this type of deposit in the Brook Range is difficult, due to the inherently high background values for Ba, Zn and Pb in shale and the common occurrence of metamorphic quartz-calcite veins, many of which contain traces of sulfide minerals. Stream sediments derived from these sources produce numerous geochemical anomalies which are not necessarily associated with significant mineralization. R-mode factor analysis provides a means of distinguishing between element associations related to lithology and those related to possible mineralization. Factor analysis applied to the multi-element data from the southern Killik River quadrangle resulted in the discovery of two additional Zn-Pb-Ag mineral occurrences of considerable areal extent which are 80-100 km east of any previously known deposit. These have been informally named the Kady and Vidlee. Several lithogeochemical element associations, or factors, and three factors which represent sulfide mineralization were identified: Ag-Pb-Zn (galena and sphalerite) and Fe-Ni-Co-Cu (pyrite ?? chalcopyrite) in the concentrate samples and Cd-Zn-Pb-As-Mn in the sediment samples. The distribution of high scores for each individual mineralization factor outlined several relatively large (200-250 km2) geochemically favorable areas. When the distribution of high scores for all three factors were superimposed, samples characterized by high scores for one or both of the concentrate mineralization factors and the mineralization factor in sediments define basin areas of approximately 48 and 64 km2 surrounding Kady and Vidlee, respectively. ?? 1992.
Hower, J.C.; Calder, J.H.; Eble, C.F.; Scott, A.C.; Robertson, J.D.; Blanchard, L.J.
2000-01-01
Five coals of Westphalian A (early Middle Pennsylvanian) age were sampled from the Joggins Formation section exposed along Chignecto Bay at Joggins, Nova Scotia. Coal beds along the bay were mined beginning in the early 17th century, yet there have been few detailed published investigation of the coal beds of this classic section. The lowermost coal, the Upper Coal 28 (Upper Fundy), is a high-vitrinite coal with a spore assemblage dominated by arboreous lycopsid spores with tree ferns subdominant. The upper portions of the coal bed have the highest ratio of well-preserved to poorly-preserved telinite of any of the coals investigated. Coal 19 ('clam coal') has 88% total vitrinite but, unlike the Fundy coal bed, the telinite has a poor preservation ratio and half the total vitrinite population comprises gelocollinite and vitrodetrinite. The latter coal bed is directly overlain by a basin-wide limestone bed. The Lower Kimberly coal shows good preservation of vitrinite with relatively abundant telinite among the total vitrinite. The Middle Kimberly coal, which underlies the tetrapod-bearing lycopsid trees found by Lyell and Dawson in 1852, exhibits an upward decrease in arboreous lycopod spores and an upward increase in the tree fern spore Punctatisporites minutus. Telinite preservation increases upwards in the Middle Kimberly but overall is well below the preservation ratio of the Upper Fundy coal bed. The coals all have high sulfur contents, yielding up to 13.7% total sulfur for the lower lithotype of the Upper Fundy coal bed. The Kimberly coals are not only high in total and pyritic sulfur, but also have high concentrations of chalcophile elements. Zinc, ranging up to 15,000 ppm (ash basis), is present as sphalerite in fusain lumens. Arsenic and lead each exceed 6000 ppm (ash basis) in separate lithotypes of the Kimberly coals. Together these data are consistent with elevated pH in planar mires. The source of the elemental enrichment in this presumed continental section is enigmatic. (C) 2000 Elsevier Science B.V. All rights reserved.Five coals of Westphalian A (early Middle Pennsylvanian) age were sampled from the Joggins Formation section exposed along Chigneto Bay at Joggins, Nova Scotia. All the coals were found to have high sulfur contents. Overall, the data obtained are consistent with elevated pH in planar mires.
Foose, M.P.; Slack, J.F.; Casadevall, T.
1980-01-01
The Hamme tungsten district is composed of a series of steeply dipping quartz-wolframite veins in the Piedmont of North Carolina. Veins are concentrated near the border of the lower Paleozoic Vance County pluton, along its western contact with green-schist-facies metapelites and metavolcanic rocks of the Carolina slate belt. One of these quartz veins, the Snead-Walker, hosts the Tungsten Queen deposit. The vein is 0 to 10 m thick and trends N 35 degrees E for approximately 3,500 m through slate belt rocks and the granitic pluton. The deposit has been worked to a depth of nearly 520 m and contains eight en echelon ore lodes that plunge 42 degrees to 65 degrees between S 10 degrees E and S 10 degrees W. Ore lodes commonly are encased in thin lenses of quartz-sericite greisen. The principal ore mineral is huebnerite and is accompanied by scattered occurrences of pyrite, sphalerite, galena, chalcopyrite, and tetrahedrite. The gangue is predominantly quartz with minor amounts of fluorite, sericite, and carbonate.Studies of minor structures and mineral textures indicate that both the wall rock and the ore and gangue minerals within the vein have been deformed by at least two events. The first event produced relatively gentle, open, and shallow-plunging folds; later, an intense episode of right-lateral shearing developed steeply plunging, tight folds and numerous northeast-trending shears. This latter deformation also developed a prominent alignment of ore and gangue minerals oblique to the vein walls and may have formed the en echelon distribution of ore lodes.In relatively undeformed parts of the vein, clusters of euhedral huebnerite crystals are oriented perpendicular to vein layering. Some prismatic crystals have terminations with cappings of sulfides and in polished thin section show concentric growth zones. These features are similar to textures found in unmetamorphosed tungsten-bearing hydrothermal vein deposits such as those at Pasto Bueno, Peru; Carrock Fell, England; and Panasqueria, Portugal. The relationships of mineral textures and minor structures indicate that the Tungsten Queen deposit formed by open-space fillings of linear faults or fractures and was subsequently deformed by at least two episodes of folding and shearing.
Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate
Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon
2015-01-01
Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface. PMID:26549929
NASA Astrophysics Data System (ADS)
Maghfouri, Sajjad; Rastad, Ebrahim; Mousivand, Fardin; Lin, Ye; Zaw, Khin
2016-08-01
The southwest Sabzevar basin is placed in the southwestern part of a crustal domain known as the Sabzevar zone, at the north of Central Iranian microcontinent. This basin hosts abundant mineral deposits; particularly of the Mn exhalative and Cu-Zn volcanogenic massive sulfide (VMS) types. The evolution of this basin is governed by the Neo-tethys oceanic crust subduction beneath the Central Iranian microcontinent and by the resulting continental arc (Sanandaj-Sirjan) and back-arc (Sabzevar-Naien). This evolution followed two major sequences: (I) Lower Late Cretaceous Volcano-Sedimentary Sequence (LLCVSS), which is indicated by fine-grained siliciclastic sediments, gray basic coarse-grained different pyroclastic rocks and bimodal volcanism. During this stage, tuff-hosted stratiform, exhalative Mn deposits (Nudeh, Benesbourd, Ferizy and Goft), oxide Cu deposits (Garab and Ferizy) and Cu-Zn VMS (Nudeh, Chun and Lala) deposits formed. (II) Upper Late Cretaceous Sedimentary Dominated Sequence (ULCSS), including pelagic limestone, marly tuff, silty limestone and marl with minor andesitic tuff rocks. The economically most important Mn (Zakeri and Cheshmeh-sefid) deposits of Sabzevar zone occur within the marly tuff of this sequence. The Nudeh Cu-Zn volcanogenic massive sulfide (VMS) deposit is situated in the LLCVSS. The host-rock of deposits consists of alkali olivine basalt flow and tuffaceous silty sandstone. Mineralization occurs as stratiform blanket-like and tabular orebodies. Based on ore body structure, mineralogy, and ore fabric, we recognize three different ore facies in the Nudeh deposit: (1) a stringer zone, consisting of a discordant mineralization of sulfides forming a stockwork of sulfide-bearing quartz veins cutting the footwall volcano-sedimentary rocks; (2) a massive ore, consisting of massive replacement pyrite, chalcopyrite, sphalerite and Friedrichite with magnetite; (3) bedded ore, with laminated to disseminated pyrite, and chalcopyrite. Chloritization, silicification, sericitization and epidotization are the main wall-rock alterations; alteration intensity increases towards the stringer zone. The δ34S composition of the sulfides ranges from -1.5‰ to +3.69‰ with a general increase of δ34S ratios of massive ore facies to stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones. Sulfur isotopes, along with sedimentological, textural, petrological, mineralogical, and geochemical evidences, suggest that this deposit should be classified as a Besshi-type VMS ore deposit.
The age and thermal history of Cerro Rico de Potosi, Bolivia
Cunningham, C.G.; Zartman, R.E.; McKee, E.H.; Rye, R.O.; Naeser, C.W.; Sanjines, V.O.; Ericksen, G.E.; Tavera, V.F.
1996-01-01
Cerro Rico de Potosi, Bolivia, is the world's largest silver deposit and has been mined since the sixteenth century for silver, and for tin and zinc during the twentieth century, together with by-product copper and lead. The deposit consists primarily of veins that cut an altered igneous body that we interpret to be a dacitic volcanic dome and its underlying tuff ring and explosion breccia. The deposit is compositionally and thermally zoned, having a core of cassiterite, wolframite, bismuthinite, and arsenopyrite surrounded by a peripheral, lower-temperature mineral assemblage consisting principally of sphalerite, galena, lead sulfosalt, and silver minerals. The low-temperature assemblage also was superim-posed on the high-temperature assemblage in response to cooling of the main hydrothermal system. Both the dacite dome and the ore fluids were derived from a larger magmatic hydrothermal source at depth. The dome was repeatedly fractured by recurrent movement on the fault system that guided its initial emplacement. The dome was extruded at 13.8 ?? 0.2 Ma (2??), based on U-Th-Pb dating of zircon. Mineralization and alteration occurred within about 0.3 my of dome emplacement, as indicated by a 40Ar/39Ar date of 13.76 ?? 0.10 Ma (1??) for sericite from the pervasive quartz-sericite-pyrite alteration associated with the main-stage, high-temperature, mineralization. The last thermal event able to reset zircon fission tracks occurred no later than 12.5 ?? 1.1 Ma (1??). as indicated by fission-tract dating. Minor sericite. and magmatic-steam alunite veins, were episodically formed around 11 Ma and between 8.3 and 5.7 Ma; the younger episodes occurring at the time of extensional fracturing at Cerro Rico and widespread volcanism in the adjacent Los Frailes volcanic field. None of these younger events appear to be signific-ant thermal/mineralizing events: the exceptionally flat thermal release pattern of 39Ar from sericite and the results of the fission-tract dating of zircon show that none of the younger events was hot enough, and lasted long enough, to cause significant loss of Ar or annealing of zircon fission tracks. U-Th-Pb dating of zircon cores dicates a Precambrian progenitor for some zircons, and REE analyses of dated samples of hydrothermally altered dacite show the presence of a prominent positive Eu anomaly, which constrains interpretations of the origin and evolution of the magmatic/hydrothermal system.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Eskelsen, Jeremy R.; Xu, Jie; Chiu, Michelle Y.
The dissolution of metal sulfides, such as ZnS, plays an important role in the fate of metal contaminants in the environment. Here we have examined the dissolution behavior of ZnS nanoparticles synthesized via several abiotic and biological pathways. Specifically, the biogenic ZnS nanoparticles were produced by an anaerobic, metal-reducing bacterium Thermoanaerobacter sp. X513 in a Zn-amended, thiosulfate-containing growth medium, whereas the abiogenic ZnS nanoparticles were produced by mixing an aqueous Zn solution with either H 2S-rich gas or Na 2S solution. For biogenic synthesis, we prepared two types of samples, in the presence or absence of trace silver (Ag). Themore » size distribution, crystal structure, aggregation behavior, and internal defects of the synthesized ZnS nanoparticles were primarily examined using high-resolution transmission electron microscopy coupled with X-ray energy dispersive spectroscopy. The characterization results show that both the biogenic and abiogenic samples were dominantly composed of sphalerite. In the absence of Ag, the biogenic ZnS nanoparticles were significantly larger (i.e., ~10 nm) than the abiogenic ones (i.e., ~3–5 nm) and contained structural defects (e.g., twins and stacking faults). The presence of trace Ag showed a restraining effect on the particle size of the biogenic ZnS, resulting in quantum-dot-sized nanoparticles (i.e., ~3 nm). In situ dissolution experiments for the synthesized ZnS were conducted with a liquid-cell coupled to a transmission electron microscope (LCTEM), and the primary factors (i.e., the presence or absence structural defects) were evaluated for their effects on the dissolution behavior using the biogenic and abiogenic ZnS nanoparticle samples with the largest average particle size. Analysis of the dissolution results (i.e., change in particle radius with time) using the Kelvin equation shows that the defect-bearing biogenic ZnS nanoparticles (γ = 0.799 J/m 2) have a significantly higher surface energy than the abiogenic ZnS nanoparticles (γ = 0.277 J/m 2), suggesting that larger defect-bearing ZnS nanoparticles may be more reactive than the smaller quantum-dot-sized ZnS nanoparticles. These findings provide new insight into the factors that govern the dissolution of metal sulfide nanoparticles in relevant natural and engineered scenarios, and have implication for tracking the fate of zinc at contaminated sites. Moreover, our study exemplified the use of an in situ method (i.e., LCTEM) to investigate nanoparticle behavior (e.g., dissolution) in aqueous solutions.« less
NASA Astrophysics Data System (ADS)
Biel, C.; Subías, I.; Acevedo, R. D.; Yusta, I.; Velasco, F.
2012-04-01
The Arroyo Rojo Zn-Pb-Cu volcanogenic massive sulfide deposit is the main deposit of the Fin del Mundo District in the Fuegian Andes, Argentina. This deposit is hosted by a Middle Jurassic volcanic and volcanoclastic sequence forming the Lemaire Formation. The latter consists, from the base up, of the following: rhyolitic and dacitic porphyritic rocks, ignimbrite, tuff, and flow. It is underlain by a pre-Jurassic basement and overlain by the hyaloclastic andesites of the Yahgán Formation. The Arroyo Rojo consists of stacked lenticular lenses that are associated with disseminated mineralization in both the footwall and the hanging wall. The internal structure of the ore lenses is marked by the occurrence of massive, semi-massive and banded facies, along with stringer and brecciated zones and minor ore disseminations. The mineral assemblage comprises mainly pyrite and sphalerite, with minor amounts of galena and chalcopyrite and rare pyrrhotite, arsenopyrite, tetrahedrite and bournonite. The ores and the volcanic host rocks have metamorphosed to greenschist facies and were overprinted by a penetrative tectonic foliation, which led to the development of mylonitic, and cataclastic textures, recrystallization and remobilization. Primary depositional characteristics and regional and hydrothermal alteration patterns were preserved despite deformation and metamorphism. Therefore, primary banding was preserved between facies boundaries. In addition, some remnants of magmatic origin are recognizable in preserved phenocrysts and volcaniclastic phenoclasts. Most of the volcanic and volcaniclastic rocks of the host sequence show a rhyolitic to rhyo-dacitic composition. Regional seafloor alteration, characterized by the presence of clinozoisite, Fe-chlorite and titanite, along with quartz and albite, is partially obliterated by hydrothermal alteration. The hydrothermal alteration is stratabound with the following assemblages, which developed from the base to top: (1) Quartz-Chlorite ± Sericite, (2) Quartz-Chlorite, (3) Chlorite ± Quartz-Sericite-Calcite, (4) Quartz-Chlorite ± Calcite and (5) Sericite + Quartz ± Chlorite ± Calcite. Magnesium-chlorite and phengitic white mica typically occur in the vicinity of the Arroyo Rojo ore lenses. To provide field criteria for exploration vectoring, the chemical composition of chlorite and the phengitic and paragonitic content of the white mica were determined and correlated with PIMA Fe-OH and Al-OH absorption wavelengths, respectively, relative to their proximity to the mineralized lenses. The results of this study can be used to help identify (1) felsic proximal facies associations, (2) ore horizons and (3) favorable hydrothermal alteration zones in other parts of the Fin del Mundo district.
Finkelman, Robert B.; Fiene, F.L.; Miller, R.N.; Simon, F.O.
1984-01-01
Approximately 20 kg of the Herrin (No. 6) coal was collected from a strip mine in St. Clair County, Ill. A 10-kg portion was ground to -60 mesh, homogenized, and riffled into 128 splits of 70-80 g each. Homogeneity of these splits was confirmed by moisture, ash, and sulfur analyses of six randomly selected splits. Results of these analyses were within the ASTM (American Society for Testing and Materials) guidelines for interlaboratory precision. Splits of the Herrin (No. 6) coal were then transmitted to more than 30 laboratories for analysis. Low-temperature plasma oxidation was used to isolate inorganic matter for quantitative chemical and mineralogical analysis. Despite a wide variation in ashing conditions, only minor variations in ash yields were obtained; these variations were attributed to differences in operating temperature and moisture content. Mineralogical analyses of low-temperature ash (LTA) concentrates prepared by five different laboratories indicated variations within the limits of analytical error. The mean values, in weight percent, for the major minerals are as follows: calcite, 9; quartz, 20; pyrite, 23; kaolinite, 14; and illite+mixed-layer clays, 31. Normative mineralogical calculations and Fourier transform infrared analysis (FTIR) yielded results similar to those obtained from X-ray diffraction (XRD). Choosing appropriate mineral standards was found to be critical for the proper use of analytical techniques such as XRD and FTIR. Good interlaboratory agreement was obtained for most major, minor, and trace elements despite differences in analytical procedures and in the type of sample analyzed (coal, high-temperature ash, or LTA). Discrepancies between analyses for zinc, strontium, manganese, and iron may be attributed to sampling inhomogeneity problems. Mossbauer spectroscopy showed that approximately 44 percent of the pyritic sulfur was lost through weathering in the first year after preparation of the interlaboratory sample. Szomolnokite and possibly coquimbite and jarosite were also identified. Scanning electron microscopy studies indicated ubiquitous pyrite framboids and, less commonly, euhedral crystals, skeletal grains, irregularly shaped particles, and vein fillings. Minor accessory minerals such as rare-earth phosphates and possibly silicates, zircon, barium sulfate, titanium oxide, and sphalerite were also found. The textural evidence indicates that the minerals in the banded material are detrital whereas the minerals occurring as vein and pore fillings are authigenic. Magnetic measurements indicate that coal crushed in a steel pulverizer is contaminated by small quantities of abrasion fragments from the crusher, which seriously affect the measured magnetic properties of the coal.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gao, X.; Schulze, D
2010-01-01
The chemical and mineralogical forms of As, Pb, Cr, and Cd were studied in a metal-contaminated organic soil (Histosol) that received runoff and seepage water from a site that was once occupied by a lead smelter. Soil samples were collected from different depth intervals during both wet and dry seasons and analyzed using bulk powder X-ray diffraction (XRD), synchrotron-based micro X-ray diffraction ({mu}-XRD), and micro X-ray fluorescence ({mu}-SXRF) spectroscopy. There was a clear pattern of mineral distribution with depth that indicated the presence of an intense redox gradient. The oxidized reddish brown surface layer (0-10 cm) was dominated by goethitemore » ({alpha}-FeOOH) and poorly crystalline akaganeite ({beta}-FeOOH). Lead and arsenic were highly associated with these Fe oxides, possibly by forming inner-sphere surface complexes. Gypsum (CaSO{sub 4} {center_dot} 2H{sub 2}O) was abundant in the layer as well, particularly for samples collected during dry periods. Fe(II)-containing minerals, such as magnetite (Fe{sub 3}O{sub 4}) and siderite (FeCO{sub 3}), were identified in the intermediate layers (10-30 cm) where the reductive dissolution of Fe(III) oxides occurred. A number of high-temperature minerals, such as mullite (3Al{sub 2}O{sub 3} {center_dot} 2Si{sub 2}O), corundum ({alpha}-Al{sub 2}O{sub 3}), hematite ({alpha}-Fe{sub 2}O{sub 3}), and wustite (FeO) were identified in the subsurface and they probably formed as a result of a burning event. Several sulfide minerals were identified in the most reduced layers at depths > 30 cm. They included realgar (AsS), alacranite (As{sub 4}S{sub 4}), galena (PbS), and sphalerite (Zn, Fe{sup 2+})S, and a series of Fe sulfides, including greigite (Fe{sup 2+}Fe{sub 2}{sup 3+} S{sub 4}), pyrrhotite (Fe{sub 1-x}S), mackinawite (FeS), marcasite (FeS{sub 2}), and pyrite (FeS{sub 2}). Most of these minerals occurred as almost pure phases in sub-millimeter aggregates and appeared to be secondary phases that had precipitated from solution. Despite the elevated levels of Cd in the soil, no specific Cd phases were identified. The complex mineralogy has important implications for risk assessment and the design of in-situ remediation strategies for this and similar metal-contaminated sites.« less
NASA Astrophysics Data System (ADS)
Saito, S.; Sanada, Y.; Moe, K.; Kido, Y. N.; Hamada, Y.; Kumagai, H.; Nozaki, T.; Takai, K.; Suzuki, K.
2015-12-01
A scientific drilling expedition was conducted at an active hydrothermal field on the Iheya-North Knoll by D/V Chikyu in 2014 (Expedition 907) as a part of "Next-generation Technology for Ocean Resources Survey" of the Cross-ministerial Strategic Innovation Promotion Program. During the expedition logging while drilling (LWD) was deployed to constrain the area of the fluid reservoir beneath seafloor followed by three coring holes down to 150 meter below the seafloor (mbsf). The LWD system is composed of arcVISION for resistivity and natural gamma ray measurement and TeleScope for real-time transmission of drilling parameters and arcVISION data. Five sites (C9011-15) at the Iheya-North Original Site and one site (C9016) at Aki Site were drilled with LWD. At C9012 and C9016, the arcVISION detected temperature anomaly up to 84℃ at 234 mbsf and up to 39℃ at 80 mbsf, respectively. The temperature quickly increases at that depth and it would reflect the existence of high-temperature heat source along borehole. Due to the continuous fluid circulation during drilling, the measured temperature does not indicate in-situ temperature, but it reflects the heat disturbed by the cold circulated water instead. High quality resistivity and natural gamma ray data were acquired at six sites. The log curves at Site C9016 show characteristic response; the natural gamma ray log exhibits extremely high radiation (>500 gAPI) at 7-13 and 23-31 mbsf (Zone A). In the underlying interval of 31-40 mbsf, the resistivity log exhibits extremely low value (<0.2 ohm-m) (Zone B). Then the resistivity log exhibits higher value (~10 ohm-m) and the natural gamma ray log shows very low radiation (<50 gAPI) at the interval of 41-48 mbsf (Zone C). The log characteristics in Zone A, B, and C can be interpreted as a series of K-rich alteration zone, sulfide zone, and low-K hard (silicified) sediments, respectively. The LWD-based lithological interpretation was confirmed by the following core description. Zones A and B can be correlated to altered clay zone and sulfide zone including sphalerite, galena, chalcopyrite, and pyrite. Our results show that LWD is a powerful tool for the identification and characterization of submarine hydrothermal deposits and LWD survey enhances the successful recovery of sulfide samples.
Orogenic-type copper-gold-arsenic-(bismuth) mineralization at Flatschach (Eastern Alps), Austria
NASA Astrophysics Data System (ADS)
Raith, Johann G.; Leitner, Thomas; Paar, Werner H.
2015-10-01
Structurally controlled Cu-Au mineralization in the historic Flatschach mining district (Styria, Austria) occurs in a NE-SW to NNE-WSW oriented vein system as multiple steep-dipping calcite-(dolomite)-quartz veins in amphibolite facies metamorphic rocks (banded gneisses/amphibolites, orthogneisses, metagranitoids) of the poly-metamorphosed Austroalpine Silvretta-Seckau nappe. Vein formation postdated ductile deformation events and Eoalpine (Late Cretaceous) peak metamorphism but predated Early to Middle Miocene sediment deposition in the Fohnsdorf pull-apart basin; coal-bearing sediments cover the metamorphic basement plus the mineralized veins at the northern edge of the basin. Three gold-bearing ore stages consist of a stage 1 primary hydrothermal (mesothermal?) ore assemblage dominated by chalcopyrite, pyrite and arsenopyrite. Associated minor minerals include alloclasite, enargite, bornite, sphalerite, galena, bismuth and matildite. Gold in this stage is spatially associated with chalcopyrite occurring as inclusions, along re-healed micro-fractures or along grain boundaries of chalcopyrite with pyrite or arsenopyrite. Sericite-carbonate alteration is developed around the veins. Stage 2 ore minerals formed by the replacement of stage 1 sulfides and include digenite, anilite, "blue-remaining covellite" (spionkopite, yarrowite), bismuth, and the rare copper arsenides domeykite and koutekite. Gold in stage 2 is angular to rounded in shape and occurs primarily in the carbonate (calcite, Fe-dolomite) gangue and less commonly together with digenite, domeykite/koutekite and bismuth. Stage 3 is a strongly oxidized assemblage that includes hematite, cuprite, and various secondary Cu- and Fe-hydroxides and -carbonates. It formed during supergene weathering. Stage 1 and 2 gold consists mostly of electrum (gold fineness 640-860; mean = 725; n = 46), and rare near pure gold (fineness 930-940; n = 6). Gold in stage 3 is Ag-rich electrum (fineness 350-490, n = 12), and has a high Hg content (up to 11 mass %). The Cu-Au deposits in the Flatschach area show similarities with meso- to epizonal orogenic lode gold deposits regarding the geological setting, the structural control of mineralization, the type of alteration, the early (stage 1) sulfide assemblage and composition of gold. Unique about the Flatschach district is the lower-temperature overprint of copper arsenides (domeykite and koutekite) and copper sulfides (djurleite, yarrowite/spionkopite) on earlier formed sulfide mineralization. Based on mineralogical considerations temperature of stage 2 mineralization was between about 70 °C and 160 °C. Gold was locally mobilized during this low-temperature hydrothermal overprint as well as during stage 3 supergene oxidation and cementation processes.
U-Pb isotope systematics and age of uranium mineralization, Midnite mine, Washington.
Ludwig, K. R.; Nash, J.T.; Naeser, C.W.
1981-01-01
Uranium ores at the Midnite mine, near Spokane, Washington, occur in phyllites and calcsilicates of the Proterozoic Togo Formation, near the margins of an anomalously uraniferous, porphyritic quartz monzonite of Late Cretaceous age. The present geometry of the ore zones is tabular, with the thickest zones above depressions in the pluton-country rock contact. Analyses of high-grade ores from the mine define a 207 Pb/ 204 Pb- 235 U/ 204 Pb isochron indicating an age of mineralization of 51.0 + or - 0.5 m.y. This age coincides with a time of regional volcanic activity (Sanpoil Volcanics), shallow intrusive activity, erosion, and faulting. U-Th-Pb isotopic ages of zircons from the porphyritic quartz monzonite in the mine indicate an age of about 75 m.y., hence the present orebodies were formed about 24 m.y. after its intrusion. The 51-m.y. time of mineralization probably represents a period of mobilization and redeposition of uranium by supergene ground waters, perhaps aided by mild heating and ground preparation and preserved by a capping of newly accumulated, impermeable volcanic rocks. It seems most likely that the initial concentration of uranium occurred about 75 m.y. ago, probably from relatively mild hydrothermal fluids in the contact-metamorphic aureole of the U-rich porphyritic quartz monzonite.Pitchblende, coffinitc, pyrite, marcasite, and hisingerite are the most common minerals in the uranium-bearing veinlets, with minor sphalerite and chalcopyrite. Coffinitc with associated marcasite is paragenetically later than pitchblende, though textural and isotopic evidence suggests no large difference in the times of pitchblende and colfinite formation.The U-Pb isotope systematics of total ores and of pitchblende-coffinite and pyrite-marcasite separates show that whereas open system behavior for U and Pb is essentially negligible for large (200-500 g) ore samples, Pb migration has occurred on a scale of 1 to 10 mm (out of pitchblende and coffinite and into pyrite and marcasite). Also, long-term continuous leakage of radioactive daughters of 238 U (probably 222 Rn) has occurred on scales of from approximately 100 mu m approximately 10 cm. The isotopic composition of unsupported radiogenic Pb in pyrite-marcasite seems to depend on the mineralogical microenvironment of the grains, so that the radiogenic Pb in pyrite-marcasite intimately intermixed with pitchblende-coffinite tends to be deficient in 206 Pb, and the radiogenic Pb in pyrite-marcasite in gangue tends to have excess 206 Pb. These systematics probably reflect differences between the average distances of Pb and 222 Rn diffusion since the formation of the ores.
Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements
Tuttle, M.L.W.; Breit, G.N.; Goldhaber, M.B.
2009-01-01
During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.
NASA Astrophysics Data System (ADS)
Hofstra, A. H.; Rusk, B. G.; Manning, A. H.; Hunt, A. G.; Landis, G. P.
2017-12-01
Recent studies suggest that volatiles released from mafic intrusions may be important sources of heat, sulfur, and metals in porphyry Cu-Mo-Au and epithermal Au-Ag deposits associated with intermediate to silicic stocks. The huge Cu-Mo porphyry and Main Stage polymetallic vein deposits at Butte are well suited to test this hypothesis because there is no geologic or isotopic evidence of basaltic intrusions in the mine or drill holes. The Butte porphyry-vein system is associated with quartz monzonite stocks and dikes within the southwest part of the Late Cretaceous Boulder batholith. The Boulder batholith was emplaced into Mesoproterozoic to Mesozoic sedimentary rocks and Late Cretaceous volcanic rocks. The Boulder batholith and Butte intrusions have Sri and eNd values indicative of crustal contamination. Eu and Ce anomalies in zircon from Butte intrusions provide evidence of oxidation due to magma degassing. To ascertain the source of volatiles in this system, 11 samples from the Cu-Mo porphyry and 16 from Main Stage veins were selected. The isotopic composition of Ar, Ne, and He extracted from fluid inclusions in quartz, magnetite, pyrite, chalcopyrite, sphalerite, galena, enargite, and covellite were determined. Helium isotopes exceed blank levels in all samples and Ne and Ar in some samples. On a 38Ar/36Ar vs. 40Ar/36Ar diagram, data plot near air. On a 20Ne/22Ne vs. 21Ne/22Ne diagram, data extend from air along the trajectories of OIB and MORB. On a 36Ar/4He vs. 3He/4He RA diagram, data extend from crust toward the air-mantle mixing line. The maximum 3He/4He RA values in the Cu-Mo porphyry (2.86) and Main Stage veins (3.46) are from pyrite and these values correspond to 36 and 43 % mantle helium. The Ne and He results show that fluid inclusions contain volatiles discharged from mantle magmas and that these volatiles were diluted by groundwater containing He derived from country rocks. Despite the lack of mafic intrusions in the Butte magmatic center, noble gas isotopes show that volatiles derived from concealed mafic intrusions were present in the hydrothermal system. Discharge of hot volatiles from mafic magma chambers at depth may be required to prevent the overlying magma column from quenching and, thus, allow for the repeated buildup and release of sulfur- and metal-bearing fluids from apical intrusions.
NASA Astrophysics Data System (ADS)
Darling, J. R.; Storey, C. D.; Hawkesworth, C. J.; Lightfoot, P. C.
2012-12-01
Laser-ablation (LA) multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is ideally suited to in situ determination of isotope ratios in sulphide minerals. Using samples of magmatic sulphide ore from the Sudbury impact structure, we test LA-MC-ICPMS analytical protocols that aim to meet a range of analytical challenges in the analysis of Pb isotopes. These include: potential matrix sensitive isotopic fractionation; interferences on Pb isotopes; low melting points of many sulphide minerals; the availability of standards. Magmatic sulphides of wide ranging mineralogy (pyrrhotite, pentlandite, chalcopyrite, pyrite and sphalerite) were analysed for Pb isotopic composition, using the silicate glass NIST SRM 610 as an external standard to correct for instrumental mass-fractionation. Despite matrix sensitive melting and re-deposition around ablation pits, several lines of evidence indicate that all analyses are accurate, within typical analytical uncertainties of 0.003-2% (2σ), and that the defined approach is insensitive to compositional diversity in sample matrix: (a) laser ablation and dissolution based measurements of sulphide powders are in agreement; (b) analyses from each sample define isochron ages within uncertainty of the known crystallization age (1850 Ma); (c) the results of sulphide measurements by laser ablation are consistent with age-corrected feldspar analyses from the same samples. The results have important implications for ore formation in Sudbury. The Pb isotope data regressions are consistent with age corrected feldspar analyses from each respective sample, which together with time integrated Th/U ratios that match whole rock values (3.1, 4.0 and 6.1 for the Worthington, Copper Cliff and Parkin Offset Dykes, respectively) indicate chemical equilibrium between the silicate and sulphide systems during ore formation. The sulphides within each respective sample have indistinguishable model initial Pb isotope ratios (207Pb/204Pbm), irrespective of mineralogy or texture, indicating a common origin for ores within each of three different Offset Dykes. Furthermore, variations between Offset Dykes (e.g., 207Pb/204Pbm = 15.514 ± 0.012, 15.399 ± 0.009 and 15.275 ± 0.003) show that the ores have differing crustal sources on previously unrecognized scales. Mass balance considerations, particularly for MgO, Ni and Cu, indicate that the spatial distribution of mafic target rocks played a significant role in controlling the mineralization potential in different parts of the melt sheet.
NASA Astrophysics Data System (ADS)
Bubnova, Tatyana; Skamnitskaya, Lubov; Gorbunova, Elena; Chertov, Alexandr
2017-12-01
The use of muscovite is determined by its industrial look and quality. Sheet mica is traditionally used as electrically insulating material. Crushed mica dry or wet grinding and scrap (waste from the production of sheet mica) are used as electrical insulating material (for example, mica paper), filler in the manufacture of various kinds of fillers, grout and paint etc. In addition, today there is a steady demand for micronized muscovite for the production of decorative coatings and cosmetics. On the territory of the Republic of Karelia (Russian Federation) there is a significant number of deposits and occurrences moscoviticarum rocks. Promising target small iron-poor Muscovite is the manifestation of the Eastern Hitware identified in 1999. The average mineral composition of rocks of the productive series: quartz - 10-71%; Muscovite - 8-42%; plagioclase - 1,5-28%; kyanite - 2-13,5%; biotite, and 0.1-8%; ore (pyrite, sphalerite) and 1.5 - 11%. Enrichment of this type of mineral raw materials may be carried out using traditional methods - gravity, magnetic separation, flotation. Textural-structural and mineralogical features, a high degree of secondary changes (thin intergrowths of muscovite with graphite, ferritization, the decrease of the strength characteristics) and the availability of areas and dedicated silicification abundant pyrite mineralization and its vein type significantly impoverish muscovite ore, necessitate the adjustment of technological schemes and modes of enrichment. Possibilities of improvement of processes of pretreatment and subsequent enrichment is possible using the methods of pre-sorting that represent rational and cost-effective alternative to traditional beneficiation processes. To explore the possibility of using the optical methods being preconcentration, experimental study of the contrast of properties of samples of the original ore. The study was carried out on crushed material, graded by size: -10+5; -20+10; -40+20 -60 and+40 mm. the results revealed the main search area colour shades in images of mineral samples in the colour system HLS - grey, brown, bright yellow-orange and purple. The correlation between the colour characteristics of the individual pieces and the content of muscovite. To implement the sort method of photometric separation, the threshold separation can be determined by one of the highlighted areas of the gamut or in their entirety. Next, the sorted ore with the same mineralogical and structural properties can effectively be enriched with gravitational methods. In the complex process of enrichment, it is possible to obtain, in addition to muscovite, quartz and kyanite products, which undoubtedly will increase the output of marketable products.
Stillings, Lisa L.; Amacher, Michael C.
2010-01-01
Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyritess) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe2 and organo-selenides.Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q, from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ⁎ Q) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q. Se release (mg/L) follows a first order reaction with a rate constant, k, = 1.35 – 6.35e−3 h− 1 (11.8–55.6 yr− 1).Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ∼ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e−3 h− 1 (19.2 yr− 1).Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump.
Progress report on the Happy Jack mine, Which Canyon area, San Juan county, Utah
Trites, Albert F.; Chew, Randall T.
1954-01-01
The Happy Jack mine is in the White Canyon area, San Juan county, Utah. Production is from high-grade uranium deposits in the Shinarump conglomerate of the Triassic age. In this area the Shinarump beds range from about 16 to 40 feet in thickness and the lower part of these beds fills an east-trending channel this is note than 750 feet wide and 10 feet deep. The Shinarump conglomerate consists of beds of coarse- to fine-grained quartzose sandstone, conglomerate, siltstone, and claystone. Carbonized wood is abundant in these beds, and in the field it was classified as mineral charcoal and coal. Intra-Shinarump channels, cross-stratification, current lineation, and slumping and compaction structures have been recognized in the mine. Steeply dipping fractures have dominant trends in four directions -- N 65°W, N 60°E, N 85°E, and due north. Uranium occurs as bedded deposits, as replacement bodies in accumulations of "trash", and as replacements of larger fragments of wood. An "ore shoot" is formed where the three types of uranium deposits occur together; these ore shoots appear to be elongate masses with sharp boundaries. Uranium minerals include uraninite, sooty pitchblende(?), and the sulfate--betazippeite, johannite, and uranopilite. Associated with the uraninite are the sulfide minerals covellite, bornite, chalcopyritw, and pyrite. Galena and sphalerite have been found in close association with uranium minerals. The gaunge minerals include: limonite and hematite present in most of the sandstone beds throughout the deposit, jarosite that impregnates much of the sandstone in the outer parts of the mine workings, gypsum that fills many of the fractures, and barite that impregnates the sandstone in at least one part of the mine. Secondary copper minerals, mainly copper sulfates, occur throughout the mine, but most abundant near the adits in the outermost 30 feet of the workings. The minerals comprising the bulk of the country rock include quartz, feldspar, and clay minerals. The amount of uranium minerals deposited in a sandstone bed is believed to have been determined by the position of the bed in the channel, the permeability of the sandstone in the bed, and the amount of carbonized wood and plant remains within the bed. The beds considered most favorable for uranium deposition contain an abundance of claystone and siltstone both as matrix filling and as fragments and pebbles. Suggested exploration guides from uranium ore bodies include the following: (1) interbedded siltstone lenses, (2) claystone and siltstone cement and pabbles, (3) concentrations of "trash", (4) covelllite and bornite, (5) chalcopyrite, and (6) carbonized wood.
NASA Astrophysics Data System (ADS)
Espejel-Garcia, D.; Wenglas-Lara, G.; Villalobos-Aragon, A.; Espejel-Garcia, V. V.
2012-12-01
Steel slags are stored in piles or stocks around or near the smelter site. Currently, there is an increasing interest in the use of waste materials, especially in the construction industry, to replace natural aggregates, help the environment and reduce the costs. Slags are being used widely as road ballast, road base or sub-base material, sandblasting agents or cement additives, but normally contain high concentrations of potentially toxic metals. Although these metals are associated with glass, silicate and oxide minerals, with slow solubilities in water, a characterization of the leaching behavior is essential in environmental evaluation for reuse scenarios. The state of Chihuahua is located in northern Mexico, and mining has been an important economic activity since the 18th century. In the early 1900's, a lead smelter operated in Avalos, Chihuahua (in the southern surroundings of Chihuahua city), and left considerable slag piles after their closure in the 1980's. In this study, this material has been geochemically analyzed to identify the metals contained in it, and used in "tank tests" experiments, to assess its leaching behavior. The slags from Chihuahua contain Pb (0.5 - 4 wt.%), Zn (15-35 wt.%) and As (0.6 wt.%) in different minerals such as hardystonite (Ca2ZnSi2O7), melanotekite (Pb2Fe3+3O2Si2O7), kentrolite (Pb2Mn2Si2O9) and sphalerite (ZnS) or trapped in the glass. Major elements are present in phases such as monticellite (CaMgSiO4), kirschsteinite (CaFe2+SiO4), hedenbergite (CaFeSi2O6), babingtonite (Fe2Si3O9), magnetite (Fe3O4), and calcite (CaCO3). The leaching experiments were performed for 6, 24, 168 and 360 hours in mixtures of 30 and 50% of slags with natural road base material using distilled water at a pH 5 and 8 to recreate acidic and alkaline waters. The amounts of leached Pb ranges from 0.1 to 0.5 ppm, Zn from 0.1 to 0.6 ppm, As from 0 to 0.09 ppm, and Ca from 40 to 180 ppm, being the acidic experiments the ones that leached out the highest amounts of metals. Based on the results of analyses and experiments, it is recommended to use the waste material (slags) as aggregates in road construction, but only as minor constituent (<30%) in base materials.
NASA Astrophysics Data System (ADS)
Gamyanin, G. N.; Vikent'eva, O. V.; Prokof'ev, V. Yu.; Bortnikov, N. S.
2015-11-01
The formation sequence of orebodies, chemical composition of gangue and ore minerals, fluid inclusions, REE patterns, 40Ar/39Ar isotopic age, and relationships of stable isotopes (C, O, S) in minerals of the Arkachan gold-bismuth-siderite-sulfide deposit have been studied. The deposit has been localized in the Kuranakh Anticlinorium of the Verkhoyansky Fold-Nappe Belt at the intersection of the near-meridional Kygyltas and the NE-trending North Tirekhtyakh faults. The orebodies are extended (>2 km) and steeply dipping zones of veins and veinlets are hosted in Carbonaceous and Permian sandstones and siltstones deformed in anticlines and cut through by dikes pertaining to diorite-granodiorite-granite association. The deposit was formed during hydrothermal-metamorphic, productive main gold, silver-polymetallic, and silver-antimony stages. The orebodies are largely composed of quartz and siderite; arsenopyrite, pyrite, and pyrrhotite are widespread; bismuthinite, chalcopyrite, sphalerite, galena, and bismuth sulfosalts (gustavite, cosalite, matildite) are less abundant. The REE patterns of carbonates and quartz are characterized by a negative Eu anomaly. Three types of fluid inclusions (FI) in quartz and carbonates are distinguished: (I) liquid H2O + CO2 ± CH4 + NaCl, (II) gaseous CO2 ± CH4, and (III) aqueous salt solutions. The homogenization temperature and salinity of FI I vary from 385 to 280°C and 18.8 to 26.2 wt % NaCl equiv, respectively, whereas in FI III these parameters vary from 261 to 324°C and 3.7 to 9.5 wt % NaCl equiv. The pressure is estimated at 1830 to 1060 bar. The δ18O of quartz II associated with siderite I, native gold, and sulfosalts changes from +13.6 to 16.3‰(SMOW); δ18O and δ13C of siderite I related to gold-ore stage vary from +13.6 to +17.7‰ (SMOW) and from-6.0 to-3.0 (PDB). A wide range of δ34S from-5.7 to 16.0‰ (CDT) has been obtained for sulfides. The isotopic 40Ar/39Ar age of muscovite is 101.9 ± 1.4 Ma. The isotopic compositions of C, O, and S in fluids and their REE patterns suggest that magmatic components are predominant. Metamorphic H2O, CO2, and occasionally CH4 are derived from the apical part of a hidden intrusion, whereas sulfur is delivered from country rocks as a result of heating.
Preliminary zoning for risk assessment and remediation purposes in Portman Bay.
NASA Astrophysics Data System (ADS)
Pérez-Sirvent, Carmen; Martínez-Sanchez, MJose; Garcia-Lorenzo, MariLuz; Hernandez-Cordoba, Manuel; Molina, Jose; Gonzalez, Eva; Perez-Espinosa, Victor
2014-05-01
Portman bay is a singular point of mining impact in the Mediterranean area. The site is located in the province of Murcia, south-eastern Spain, and was completely inundated with more than 63 million tonnes of mining waste discharged through a huge washing plant. Wastes from mining activities mainly consisted of ore materials (galena, pyrite and sphalerite), phyllosilicates, in addition to siderite, iron oxides and sometimes alteration products such as jarosite, alunite, kaolinite and greenalite. These materials were submitted to a concentration process by floatation with sea water and as a result of the discharge, the whole of the bay was filled up with wastes which also extended into the Mediterranean Sea. In the last years of activity, wastes were even poured alternatively in the sea or over the sediments filling the bay. These actions have produced a very high heterogeneity in the sediments. Although after the end of the discharges it has been possible to reach a certain degree of balance, the sediments, especially those closest to the sea, are subjected to marine dynamics and the effects of rainfall and runoffs. In 2007, a recuperation pilot project was developed and financed by the Spanish Government. In the first step of this project, the complete physical, chemical and mineralogical characterization of sediments, both in surface and at depth was carried out. Twenty surface samples were collected (<1 m) and twelve sediment cores were also collected at the same time. To determine the total trace element content, zinc and iron levels were determined by flame atomic absorption spectrometry, while lead, cadmium and copper levels were determined by electrothermal atomization atomic absorption spectrometry. The arsenic content was measured by atomic fluorescence spectrometry using an automated continuous flow hydride generation spectrometer. The reliability of the results was verified by analyzing standard reference materials. The mineralogical composition was determined using Cu-Kα radiation with an X-ray Diffractometer and appropriate software. Data for metal leached, Acid-volatile sulphide (AVS) and simultaneously extracted metals (SEM) were also obtained. The results allowed two types of materials to be differentiated. The first one with a fine particle size, is related with the direct discharge of wastes and contains jarosite and other minerals resulting of supergenic alteration. The pH is low and both the level of heavy metals and chemical reactivity are high. The second, different material is black sand, a sediment of coarse texture in which stable minerals, phylosilicates, iron oxides and hydroxides, siderite, pyrite and quartz predominate. The pH is close to neutrality and despite a high heavy metals level, the chemical reactivity is low. The data allowed a preliminary zoning of the risk in the area to be established, and this was the starting point to outline the remediation project.
Eskelsen, Jeremy R; Xu, Jie; Chiu, Michelle; Moon, Ji-Won; Wilkins, Branford; Graham, David E; Gu, Baohua; Pierce, Eric M
2018-02-06
The dissolution of metal sulfides, such as ZnS, is an important biogeochemical process affecting fate and transport of trace metals in the environment. However, current studies of in situ dissolution of metal sulfides and the effects of structural defects on dissolution are lacking. Here we have examined the dissolution behavior of ZnS nanoparticles synthesized via several abiotic and biological pathways. Specifically, we have examined biogenic ZnS nanoparticles produced by an anaerobic, metal-reducing bacterium Thermoanaerobacter sp. X513 in a Zn-amended, thiosulfate-containing growth medium in the presence or absence of silver (Ag), and abiogenic ZnS nanoparticles were produced by mixing an aqueous Zn solution with either H 2 S-rich gas or Na 2 S solution. The size distribution, crystal structure, aggregation behavior, and internal defects of the synthesized ZnS nanoparticles were examined using high-resolution transmission electron microscopy (TEM) coupled with X-ray energy dispersive spectroscopy. The characterization results show that both the biogenic and abiogenic samples were dominantly composed of sphalerite. In the absence of Ag, the biogenic ZnS nanoparticles were significantly larger (i.e., ∼10 nm) than the abiogenic ones (i.e., ∼3-5 nm) and contained structural defects (e.g., twins and stacking faults). The presence of trace Ag showed a restraining effect on the particle size of the biogenic ZnS, resulting in quantum-dot-sized nanoparticles (i.e., ∼3 nm). In situ dissolution experiments for the synthesized ZnS were conducted with a liquid-cell TEM (LCTEM), and the primary factors (i.e., the presence or absence structural defects) were evaluated for their effects on the dissolution behavior using the biogenic and abiogenic ZnS nanoparticle samples with the largest average particle size. Analysis of the dissolution results (i.e., change in particle radius with time) using the Kelvin equation shows that the defect-bearing biogenic ZnS nanoparticles (γ = 0.799 J/m 2 ) have a significantly higher surface energy than the abiogenic ZnS nanoparticles (γ = 0.277 J/m 2 ). Larger defect-bearing biogenic ZnS nanoparticles were thus more reactive than the smaller quantum-dot-sized ZnS nanoparticles. These findings provide new insight into the factors that affect the dissolution of metal sulfide nanoparticles in relevant natural and engineered scenarios, and have important implications for tracking the fate and transport of sulfide nanoparticles and associated metal ions in the environment. Moreover, our study exemplified the use of an in situ method (i.e., LCTEM) to investigate nanoparticle behavior (e.g., dissolution) in aqueous solutions.
Preliminary Results on Mineralogy and Geochemistry of Loki's Castle Arctic Vents and Host Sediments
NASA Astrophysics Data System (ADS)
Barriga, Fernando; Carvalho, Carlos; Inês Cruz, M.; Dias, Ágata; Fonseca, Rita; Relvas, Jorge; Pedersen, Rolf
2010-05-01
The Loki's Castle hydrothermal vent field was discovered in the summer of 2008, during a cruise led by the Centre of Geobiology of the University of Bergen, integrated in the H2Deep Project (Eurocores, ESF). Loki's Castle is the northernmost hydrothermal vent field discovered to date. It is located at the junction between the Mohns Ridge and the South Knipovich Ridge, in the Norwegian-Greenland Sea, at almost 74°N. This junction shows unique features and apparently there is no transform fault to accommodate the deformation generated by the bending of the rift valley from WSW-ENE to almost N-S. The Knipovich Rigde, being a complex structure, is an ultra-slow spreading ridge, with an effective spreading rate of only ~ 6 mm/y. It is partly masked by a substantial cover of glacial and post-glacial sediments, estimated to be between 12 and 20 ky old, derived from the nearby Bear Island fan, to the East of the ridge. The Loki's Castle vent site is composed of several active, over 10 m tall chimneys, producing up to 320°C fluid, at the top of a very large sulphide mound, which is estimated to be around 200 m in diameter. About a dozen gravity cores were obtained in the overall area. From these we collected nearly 200 subsamples. Eh and pH were measured in all subsamples. The Portuguese component of the H2Deep project is aimed at characterizing, chemically and mineralogically, the sulphide chimneys and the collected sediments around the vents (up to 5 meters long gravity cores). These studies are aimed at understanding the ore-forming system, and its implications for submarine mineral exploration, as well as the relation of the microbial population with the hydrothermal component of sediments. Here we present an overview of preliminary data on the mineralogical assemblage found in the analyzed sediments and chimneys. The identification of the different mineral phases was obtained through petrographic observations of polished thin sections under the microscope (with both transmitted and reflected light, for a clear identification of the ore paragenesis), X-Ray diffraction and electron microprobe analyses. The analyses were conducted in the geology labs of the University of Lisbon. The sulphide assemblage most commonly present in the samples consists of sphalerite (which seems also the most abundant), pyrite and pyrrhotite, with minor amounts of chalcopyrite. Sulphide-poor selected samples collected at the base of chimneys are mostly composed of halite, anhydrite, gypsum and talc. In sediment cores clays are largely predominant, mainly smectite and ilite, as well as chlorite. Combinations of quartz, calcite, anhydrite, gypsum and barite were also found in some of the samples.
Bouabdellah, M.; Sangster, D.F.; Leach, D.L.; Brown, A.C.; Johnson, C.A.; Emsbo, P.
2012-01-01
The Mississippi Valley-type deposits of the Touissit-Bou Beker district are hosted by a 25 m thick sequence of diagenetically and hydrothermally dolomitized carbonate platform rocks of Aalenian-Bajocian age. The sulfide mineralization consists principally of galena and sphalerite and occurs as open-space fillings of voids and moderate to massive replacement of the medium- to coarse-grained host dolostone. Five types of dolomite have been distinguished, two of which (D 1 and D 2) are of replacement origin, whereas HD 1, HD 2, HD 3 occurring as open-space filling are of hydrothermal affiliation. Main ore controls include stratigraphy and lithology, carbonate dissolution, paleogeography, faults or faulted rocks, and availability of organic matter. Fluid inclusion data, along with Na-Cl-Br leachate, indicate that the ore-forming fluids correspond to evolved NaCl-CaCl 2-KCl-MgCl 2 basin-derived hot (100?? ?? 20??C) saline brines (>20 wt% NaCl equiv) that acquired their high salinities and Ca/Na ratios through evaporation of seawater, and subsequent dolomitization and fluid-rock interactions. Stable isotope data for replacement and hydrothermal dolomites are tightly clustered and overlapping, with ?? 18O and ?? 13C values from 20.5 to 21.2 and 0.2 to 0.7%, respectively. Similarly, sulfides yield ?? 34S values between 11.2 and 1.9%, whereas those corresponding to the nearby Triassic gypsum cluster yield around 14%. Altogether, these isotopic compositions are consistent with a basinal-type fluid with reduced sulfur very likely being derived through thermochemical reduction of dissolved sulfate, resulting in metal precipitation, and carbon of mainly marine Aalenian-Bajocian carbonate origin with a minor biogenic component. 87Sr/ 86Sr values of replacement dolostone are similar to those of ore-related hydrothermal dolomites, ranging from 0.70746 to 0.70833 and from 0.70769 to 0.70828, respectively, and are different from those of the Visean rhyodacite (0.71849-0.72167). Lead isotope ratios ( 206Pb/ 204Pb = 18.319-18.390; 207Pb/ 204Pb = 15.620. 15.680; 208Pb/ 204Pb = 38.452-38.650) of sulfides are consistent with Pb being derived from the Visean rhyodacite and associated volcaniclastic rocks. The intimate link between faults and mineralization suggests the strong possibility of brine flow along both ENE-trending regional-scale faults and NW-SW-trending local-scale faults. The data suggest that MVT mineralization was emplaced during the late Neogene-Quaternary (i.e., ca. 15.0 Ma), possibly as a result of subsurface gravity-driven fluid flow in response to the collision between the African and Eurasian plates. ?? 2012 Society of Economic Geologists, Inc.
Bouabdellah, Mohammed; Sangster, Donald F.; Leach, David L.; Brown, Alex C.; Johnson, Craig A.; Emsbo, Poul
2012-01-01
The Mississippi Valley-type deposits of the Touissit-Bou Beker district are hosted by a 25 m thick sequence of diagenetically and hydrothermally dolomitized carbonate platform rocks of Aalenian-Bajocian age. The sulfide mineralization consists principally of galena and sphalerite and occurs as open-space fillings of voids and moderate to massive replacement of the medium- to coarse-grained host dolostone. Five types of dolomite have been distinguished, two of which (D1 and D2) are of replacement origin, whereas HD1, HD2, HD3 occurring as open-space filling are of hydrothermal affiliation. Main ore controls include stratigraphy and lithology, carbonate dissolution, paleogeography, faults or faulted rocks, and availability of organic matter. Fluid inclusion data, along with Na-Cl-Br leachate, indicate that the ore-forming fluids correspond to evolved NaCl-CaCl2-KCl-MgCl2 basin-derived hot (100° ± 20°C) saline brines (>20 wt % NaCl equiv) that acquired their high salinities and Ca/Na ratios through evaporation of seawater, and subsequent dolomitization and fluid-rock interactions. Stable isotope data for replacement and hydrothermal dolomites are tightly clustered and overlapping, with δ18O and δ13C values from 20.5 to 21.2 and 0.2 to 0.7‰, respectively. Similarly, sulfides yield δ34S values between 11.2 and 1.9‰, whereas those corresponding to the nearby Triassic gypsum cluster yield around 14‰. Altogether, these isotopic compositions are consistent with a basinal-type fluid with reduced sulfur very likely being derived through thermochemical reduction of dissolved sulfate, resulting in metal precipitation, and carbon of mainly marine Aalenian-Bajocian carbonate origin with a minor biogenic component. 87Sr/86Sr values of replacement dolostone are similar to those of ore-related hydrothermal dolomites, ranging from 0.70746 to 0.70833 and from 0.70769 to 0.70828, respectively, and are different from those of the Visean rhyodacite (0.71849–0.72167). Lead isotope ratios (206Pb/204Pb = 18.319–18.390; 207Pb/204Pb = 15.620–15.680; 208Pb/204Pb = 38.452–38.650) of sulfides are consistent with Pb being derived from the Visean rhyodacite and associated volcaniclastic rocks. The intimate link between faults and mineralization suggests the strong possibility of brine flow along both ENE-trending regional-scale faults and NW-SW-trending local-scale faults. The data suggest that MVT mineralization was emplaced during the late Neogene-Quaternary (i.e., ca. 15–0 Ma), possibly as a result of subsurface gravity-driven fluid flow in response to the collision between the African and Eurasian plates.
Taylor, Cliff D.
2003-01-01
Detailed descriptions of some of the more significant mineral occurrences in the Stikine Airborne Geophysical Survey Project Area are presented based upon site-specific examinations by the U.S. Geological Survey in May of 1998. Reconnaissance geochemical data on unmineralized igneous and sedimentary host rocks, and mineralized rocks are also presented and are accompanied by a brief analysis of geochemical signatures typical of each occurrence. Consistent with the stated goal of the geophysical survey; to stimulate exploration for polymetallic massive sulfides similar to the Greens Creek deposit, the majority of the described occurrences are possible members of a belt of Late Triassic mineral deposits that are distributed along the eastern edge of the Alexander terrane in southeastern Alaska. Many of the described occurrences in the Duncan Canal-Zarembo Island area share similarities to the Greens Creek deposit. When considered as a whole, the geology, mineralogy, and geochemistry of these occurrences help to define a transitional portion of the Late Triassic mineral belt where changes in shallow to deeper water stratigraphy and arc-like to rift-related igneous rocks are accompanied by concomitant changes in the size, morphology, and metal endowments of the mineral occurrences. As a result, Late Triassic mineral occurrences in the area appear as: 1) small, discontinuous, structurally controlled stockwork veins in mafic volcanic rocks, 2) small, irregular replacements and stratabound horizons of diagenetic semi-massive sulfides in dolostones and calcareous shales, and as 3) larger, recognizably stratiform accumulations of baritic, semi-massive to massive sulfides at and near the contact between mafic volcanic rocks and overlying sedimentary rocks. Empirical exploration guidelines for Greens Creek-like polymetallic massive sulfide deposits in southeastern Alaska include: 1) a Late Triassic volcano-sedimentary host sequence exhibiting evidence of succession from tectonic activity to quiescence (such as conglomeratic and/or mafic volcaniclastics or flows overlain by platform carbonate or shale sequences), 2) presence and proximity to Late Triassic mafic-ultramafic intrusions, 3) presence of quartz-carbonate-fuchsite altered ultramafic bodies, 4) pyritic, graphitic shales, 5) presence of barite and/or iron-manganese-rich carbonates, 6) low-iron sphalerite and antimony-rich sulfosalt minerals, 7) a geochemical signature including Fe-Zn-Pb-Cu-Ag-Au-Sb-Hg-As-Cd-Ba-Mn-Mo-Tl and the ultramafic-related suite of elements Ni-Cr-Co, and 8) a geophysical signature characterized by the coincidence of a sharp resistivity contrast with evidence for buried intrusive rocks. Critical factors for the development of larger, economic orebodies are significant thickness of pyritic, graphitic shale indicating that a locally reducing sedimentary setting was established and that accumulation of an insulating shale blank occurred, and proximity to Late Triassic aged hypabyssal mafic-ultramafic intrusive rocks.
Ilyukhinite (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 • 3H2O, a New Mineral of the Eudialyte Group
NASA Astrophysics Data System (ADS)
Chukanov, N. V.; Rastsvetaeva, R. K.; Rozenberg, K. A.; Aksenov, S. M.; Pekov, I. V.; Belakovsky, D. I.; Kristiansen, R.; Van, K. V.
2017-12-01
A new eudialyte-group mineral, ilyukhinite, ideally (H3O,Na)14Ca6Mn2Zr3Si26O72(OH)2 · 3H2O, has been found in peralkaline pegmatite at Mt. Kukisvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. It occurs as brownish orange, with vitreous luster anhedral grains up to 1 mm across in hydrothermally altered peralkaline rock, in association with aegirine, murmanite, albite, microcline, rhabdophane-(Ce), fluorite, sphalerite and molybdenite. The Mohs hardness is 5; cleavage is not observed. D meas 2.67(2), D calc 2.703 g/cm3. Ilyukhinite is optically uniaxial (-): ω = 1.585(2), ɛ = 1.584(2). The IR spectrum is given. The average chemical composition of ilyukhinite (wt %; electron microprobe, ranges given in parentheses; H2O determined by gas chromatography) is as follows: 3.07 (3.63-4.43) Na2O, 0.32 (0.28-0.52) K2O, 10.63 (10.26-10.90) CaO, 3.06 (2.74-3.22) MnO, 1.15 (0.93-1.37) FeO, 0.79 (0.51-0.89) La2O3, 1.21 (0.97-1.44) Ce2O3, 0.41 (0.30-0.56) Nd2O3, 0.90 (0.77-1.12) TiO2, 10.94 (10.15-11.21) ZrO2, 1.40 (0.76-1.68) Nb2O5, 51.24 (49.98-52.28) SiO2, 1.14 (0.89-1.37) SO3, 0.27 (0.19—0.38) Cl, 10.9(5 )H2O,-0.06-O = C1, total is 98.27. The empirical formula is H36.04(Na3.82K0.20)(Ca5.65Ce0.22La0.14Nd0.07)(Mn1.285Fe0.48)(Zr2.645Ti0.34)Nb0.31Si25.41S0.42Cl0.23O86.82. The crystal structure has been solved ( R = 0.046). Ilyukhinite is trigonal, R3 m; a = 14.1695(6) Å, b = 31.026(1) Å, V = 5394.7(7) Å3, Z = 3. The strongest XRD reflections [ d, Å (I, %) ( hkl)] are 11.44 (82) (101), 7.09 (70) (110), 6.02 (44) (021), 4.371 (89) 205), 3.805 (47) (303, 033), 3.376 (41) (131), 2.985 (100) (315, 128), 2.852 (92) (404). Ilyukhinite was named in memory of Vladimir V. Ilyukhin (1934-1982), an outstanding Soviet crystallographer. The type specimen of ilyukhinite has been deposited in the collection of the Natural History Museum, University of Oslo, Norway.
NASA Astrophysics Data System (ADS)
Márquez-Zavalía, M. Florencia; Heinrich, Christoph A.
2016-10-01
Alto de la Blenda is a ˜6.6-Ma intermediate-sulphidation epithermal vein system in the Farallón Negro Volcanic Complex, which also hosts the 7.1-Ma porphyry-Cu-Au deposit of Bajo de la Alumbrera. The epithermal vein system is characterised by a large extent and continuity (2 km × 400 m open to depth × 6 m maximum width) and an average gold grade of ˜8 g/t. The vein is best developed within an intrusion of a fine-grained equigranular monzonite, interpreted as the central conduit of a stratovolcano whose extrusive activity ended prior to porphyry-Cu-Au emplacement at Bajo de la Alumbrera, which is in turn cut by minor epithermal veins. The Alto de la Blenda vein consists predominantly of variably Mn-rich carbonates and quartz, with a few percent of pyrite, sphalerite, galena and other sulphide and sulphosalt minerals. Four phases of vein opening, hydrothermal mineralisation and repeated brecciation can be correlated between different vein segments. Stages 2 and 3 contain the greatest fraction of sulphide and gold. They are separated by the emplacement of a polymictic breccia containing clasts of quartz feldspar porphyry as well as basement rocks. Fluid inclusions in quartz related to stages 2 to 4 are liquid rich with 2-4 wt% NaCl(eq). They homogenise between 160 and 300 °C, with very consistent values within each assemblage. Vapour inclusions are practically absent in the epithermal vein. Quartz fragments in the polymictic breccia contain inclusions of intermediate to vapour-like density and similar low salinity (˜3 wt% NaCl(eq)), besides rare brine inclusions containing halite. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analyses of epithermal inclusions indicate high concentrations of K, Fe, As, Sb, Cs, and Pb that significantly vary within and through subsequent vein stages. Careful consideration of detection limits for individual inclusions shows high gold concentrations of ˜0.5 to 3 ppm dissolved in the ore fluid, which contains variably high sulphur concentrations in excess over Fe and other chalcophile metals. Compositional variations are interpreted to reflect cooling and contraction of lower-density magmatic fluids at depth, like those preserved in porphyry clasts that were mechanically transported up by the polymictic breccia. Ore mineral precipitation from the magmatic fluid occurred by further cooling and possibly minor mixing with surface-derived water, leading to sulphide saturation, de-sulphidation of the magmatic fluid and consequent gold precipitation. The absence of flash boiling and/or reduction by carbonaceous host rocks has led to relatively modest but constant gold grades in the carbonate-base metal-gold veins of Alto de la Blenda.
Greenstone-hosted lode-gold mineralization at Dungash mine, Eastern Desert, Egypt
NASA Astrophysics Data System (ADS)
Zoheir, Basem; Weihed, Pär
2014-11-01
The auriferous quartz ± carbonate veins at Dungash mine, central Eastern Desert of Egypt, are confined to ∼E-trending dilation zones within variably foliated/sheared metavolcanic/volcaniclastic rocks. The vein morphology and internal structures demonstrate formation concurrent with a dextral shear system. The latter is attributed to flexural displacement of folded, heterogeneous rock blocks through transpression increment, late in the Neoproterozoic deformation history of the area. Geochemistry of the host metavolcanic/metavolcaniclastic rocks from the mine area suggests derivation from a low-K, calc-alkaline magma in a subduction-related, volcanic arc setting. In addition, chemistry of disseminated Cr-spinels further constrain on the back-arc basin setting and low-grade metamorphism, typical of gold-hosting greenstone belts elsewhere. Mineralogy of the mineralized veins includes an early assemblage of arsenopyrite-As-pyrite-gersdorffite ± pyrrhotite, a transitional pyrite-Sb-arsenopyrite ± gersdorffite assemblage, and a late tetrahedrite-chalcopyrite-sphalerite-galena-gold assemblage. Based on arsenopyrite and chlorite geothermometers, formation of gold-sulfide mineralization occurred between ∼365 and 280 °C. LA-ICP-MS measurements indicate the presence of refractory Au in arsenian pyrite (up to 53 ppm) and Sb-bearing arsenopyrite (up to 974 ppm). Abundant free-milling gold associated with the late sulfide assemblage may have been mobilized and re-distributed by circulating, lower temperature ore fluids in the waning stages of the hydrothermal system. Based on the isotopic values of vein quartz and carbonate, the calculated average δ18OH2O values of the ore fluids are 5.0 ± 1.4‰ SMOW for quartz, and 3.3 ± 1.4‰ for vein carbonate. The measured carbonate δ13C values correspond to ore fluids with δ13CCO2 = -6.7 ± 0.7‰ PDB. These results suggest a mainly metamorphic source for ore fluids, in good agreement with the vein morphology, textures and hydrothermal alteration. The calculated δ34SH2S values for early, transitional, and late sulfide assemblages define three distinct ranges (∼1.5-3.6‰), (∼0.4-1.0‰), and (-3.7‰ to -1.9‰), respectively. The systematic evolution towards lighter δ34S values may be attributed to recrystallization, or to ore fluid buffering under variable physicochemical conditions. The shear zone-related setting, mineralogy and isotopic characteristics of gold mineralization in Dungash mine are comparable with other orogenic gold deposits in the region (e.g., Barramiya deposit), which may suggest a regional setting controlling gold metallogeny of the region. This setting should guide future exploration programs in the central Eastern Desert province.
NASA Astrophysics Data System (ADS)
Holdsworth, Bob; Dempsey, Eddie; Selby, David; Le Cornu, Chris; Young, Brian
2015-04-01
The North Pennines Orefield (NPO) is centred on the Alston block, a structural high of fractured Carboniferous sedimentary rocks that unconformably overlie a Devonian age (ca. 399 Ma) granite pluton buried at shallow depths (<0.5 km). The orefield has long been considered to be a classic example of a Mississippi Valley Type (MVT) deposit where the source of the metals and sulphur are derived by hydrothermal leaching of the host sedimentary (carbonate-rich) rocks. The vein-hosted part of the orefield consists of linked systems of shear and tensile fractures with a variety of regionally recognised orientations (ESE-WNW Quarter Point, NE-SW, NW-SE Cross Veins). These are associated with lead (galena), iron (pyrite, pyrrhotite, marcasite), copper (chalcopyrite), zinc (sphalerite), fluorite, barite and quartz mineralization. New Rhenium-Osmium (Re-Os) isotope geochemical analysis of the vein-hosted pyrite mineralization suggests that: (i) the metalliferous ores of the NPO formed ca. 294Ma (earliest Permian); and (ii) that they carry an initial Os ratio indicative of a mantle source similar to that indicated by the initial Os ratio of the Whin Sill dolerite suite (emplacement ages ca. 297-294 Ma). New field observations and stress inversion analyses show that at least two regional deformation events are recognised in the Carboniferous host rocks of the NPO. A initial phase of Late Carboniferous ('Variscan') N-S compression pre-dates mineralisation and leads to formation of the NW-SE fractures, initiation of the Burtreeford Disturbance as a N-S fault and compressional reactivation of the previously extensional E-W Lunedale Fault. A later phase of dextral transtension (NNE-SSW extension, ESE-WNW compression) leads to the formation of the ESE-WNW and NE-SW veins, together with compressional reactivation of the Burtreeford Disturbance and Lunedale Fault. Field and microstructural analyses show that the transtensional deformation is synchronous with the main phases of NPO mineralisation and also with emplacement of the Whin Sill and associated intrusions. We conclude that: (i) the main phase of NPO mineralization occurred synchronously with regional dextral transtension during the earliest Permian; (ii) that mineralization is genetically linked to a mantle source and (iii) that the genesis of the NPO is closely linked to that of the broadly penecontemporaneous Whin Sill and associated intrusions in northern England. Our new findings are consistent with structural histories recognised in adjacent regions (e.g. Dent-Pennine Fault systems; Northumberland Basin) and point to a major regional phase of mantle-sourced mineralization, igneous intrusion and transtensional deformation in the early Permian. Previous models suggesting that the NPO is a classic example of a MVT mineral deposit or that the mineralizing fluids are related to the influx of Mesozoic brines are largely incorrect.
NASA Astrophysics Data System (ADS)
Wiche, Oliver; Moschner, Christin; Székely, Balázs
2017-04-01
A geochemical mapping study was conducted to investigate the spatial distribution and chemical fractionation of germanium (Ge) and selected rare earth elements (REEs) in topsoils and soil-grown plants under different land use types (moist grassland, mesic grassland, arable land) in the area of Freiberg (Saxony, Germany). The area of Freiberg is characterized by the mining of polymetallic sulphide deposits (Pb, As, Zn, Cd) which led to the pollution of top soils with metals and metalloids due to local emissions from metal smelting plants that occur widespread in the area. Since Ge often appears to be associated to sulphide ores like sphalerite, galenite and argyrodite, (post-)mining areas such as the Freiberg region are paradigmatic for phytomining research. The study area covers approximately 1,000 km2 in the south of Central Saxony, and 138 samples from 46 sampling sites were examined. Additionally, at each sampling site plant samples were collected. On arable soils the plant samples represented the cultivated crop species. On sites in mesic and moist grassland, samples from the most dominant plant species were taken and measured with ICP-MS. Ge and REEs in soils were partitioned by a sequential extraction procedure into mobile/exchangeable (Fraction 1), acid soluble (Fraction 2), bound to organic matter (Fraction 3), amorphous Fe/Mn-oxides (Fraction 4), crystalline Fe/Mn-oxides (Fraction 5) and residual fractions (Fraction 6). Total concentrations of Ge and REEs in soil varied considerably ranging from 1.0 µg g-1 to 4.3 µg g-1 for Ge and 97 µg g-1 to 402 µg g-1 for total REE concentrations. Elements in potentially plant available fractions (sums of Fraction 1 - Fraction 4) represented 8% of total Ge and 30% of total REEs, respectively. Soils on moist grasslands contained significantly higher total concentrations of Ge and REEs and higher concentrations of Ge and REEs in potentially plant available soil fractions compared to soils of mesic grasslands and arable land. Highest concentrations of Ge could be measured in plant species growing on moist grassland. The results of this study indicate that moist grasslands may act as sinks for Ge and REEs. In these soils high amounts of soil organic matter may foster the formation of labile element pools, increasing the availability of Ge and REEs. These studies have been carried out in the framework of the PhytoGerm project, financed by the Federal Ministry of Education and Research, Germany. BS contributed as an Alexander von Humboldt Research Fellow. The authors are grateful to students and laboratory assistants contributing in the field work and sample preparation.
Anomalous metal concentrations in soil and till at the Ballinalack Zn-Pb deposit, Ireland
NASA Astrophysics Data System (ADS)
Kalveram, Ann-Kristin; McClenaghan, Seán H.; Kamber, Balz S.
2017-04-01
Metals such as zinc, iron, arsenic and lead are commonly found in low concentrations within soils. These signatures may occur as a result of natural dispersion from metal-bearing geological formations and (or) from anthropogenic sources. Prior to investigating any high or anomalous concentrations of metals in the surficial environment, it is important to reconcile potential sources of metals and verify whether element anomalies are in response to buried mineralization. Here we show how to distinguish true elevated concentrations from naturally occurring variations within a soil system. The research area is situated above the limestone-hosted Ballinalack Zn-Pb deposit in the central Irish Midlands. To investigate the pedogenesis and its related geochemical signature, top of the till and the BC soil horizon were sampled. Although the area can be described as pasture land, it does not preclude previous anthropogenic influences from former agricultural use and local small scale peat harvesting. For the soil BC horizon as well as in the top of the till, aqua regia-digestible element concentrations vary significantly and locally reach anomalous levels: Zn (median: 104 ppm; range: 27 - 13150 ppm), Pb (median: 16 ppm; range: 2 - 6430 ppm), As (median: 7.7 ppm; range: 1.4 - 362 ppm), Ag (median: 0.12 ppm; range: 0.04 - 19.9 ppm), Ba (median: 40 ppm; range: 10 - 1230 ppm), Cd (median: 1.5 ppm; range: 0.2 - 68 ppm), Co (median: 7.3 ppm; range: 0.5 - 22 ppm), Ni (median: 37 ppm; range: 3 - 134 ppm), Fe (median: 17900 ppm; range: 5000 - 52300 ppm), Ga (median: 2.4 ppm; range: 0.3 - 7.6 ppm), Sb (median: 1.2 ppm; range: 0.1 - 197 ppm) and Tl (median: 0.3 ppm; range: 0.02 - 8.6 ppm). Comparison with background levels from the area and grouped according to underlying geology, enrichment factor calculations (against Nb and Zr) indicate an elemental response to metalliferous-bearing bedrock. These results confirm that soil anomalies of Zn, Pb, As, Ag, Ba, Cd, Ni, Sb and Tl, are consistent with the characteristics of buried Waulsortian-hosted sulphide mineralization; furthermore, Mo, Se, Sn and V are anomalous. Principal component analysis reveals a strong geochemical relationship between Ag, As, Ba, Cd, Pb, Sb, Tl and Zn in soils, representing metal dispersion from a shallow sulphide lens underneath till and soil horizons. Results of laser ablation ICP-MS analyses of pyrite and sphalerite from the Ballinalack deposit confirm this geochemical relationship. These outcomes have helped to distinguish between true geological anomalies and possible anthropogenic inputs, an important consideration for any mineral exploration activities on cultivated land.
Remediation of acid mine drainage from the Santa Fe tin mine, Bolivia
NASA Astrophysics Data System (ADS)
Calvo, Daniel; Zamora Echenique, Gerardo; Alfonso, Pura; Casado, Jordi; Trujillo, Elvys; Jiménez-Franco, Abigail; Garcia-Valles, Maite
2015-04-01
The Santa Fe mine, department of Oruro, is located in the Andean Tin belt, is exploited for tin, zinc, lead and silver. This in an underground mine mined up to the -108 level. Today it is only mined up to the -50 level. Under this level the table water covers the mine. Water reaches the surface with a very acidic composition, with a high content in potentially toxic elements. This water drains directly to the Santa Fe River and contribute to the pollution present in this river that directly affect to the aquatic communities. In addition, population of this area have problems in the supply of drinking water, so remediation by obtaining cleaning water is a priority for this area. This study presents a neutralization-precipitation treatment with lime to the acid water inside the mine. The ore mineralogy of the Santa Fe mined deposit consists mainly in cassiterite, pyrite, sphalerite, galena, arsenopyrite argentite and sulphosalts. The host mineral is mainly quartz, with a minor content in feldspars and tourmaline. Alteration minerals as alunite, goethite and pumbojarosite are abundant and indicate the occurrence of reactions that lead to the formation of acid mine drainage. The mean pH of water drained from the Santa Fe mine is 2.2 and chemical analyses show high contents in potentially toxic elements: 27-295 ppm Zn, 0.05-0.2 ppm Pb, 0.06-0.09 ppm Cd, 04-0.12 ppm Cu, 113-165 ppm Fe, 4 ppm Mn and 564-664 ppm S. As and Sb were under 0.5 ppm. A settler tank inside the mine was designed by means of seal a selected gallery to clean the mine water. The function of this gallery is to sediment the sludge resulting from the neutralization - precipitation treatment process to obtain a clear water overflow continuously to the outside. The neutralization tests indicate that 0.65g/L of lime and 2ml of flocculant should be added to neutralize water up to pH 6-7. A flow rate of 80 L /s was considered. After a geotechnical study, a chamber located in the mine was selected to locate the settler. The volume of the settling tank was determined from sedimentation tests in order to obtain the adequate sedimentation time. According to these results and the availabolity of galleries the dimensions of the settler tank will be 160x1.8x1.9m. Sludges will be treated by a process of solidification and used to provide physical stability to the gallery. Acknowledgements: This work was partly financed by the project AECID: A3/042750/11, the SGR 2009SGR-00444 and the Centre de Cooperació al Desenvolupament (CCD-UPC).
NASA Astrophysics Data System (ADS)
Martínez-Sanchez, Maria Jose; Garcia-Lorenzo, Mari Luz; Martínez, Salvadora; Gonzalez, Eva; Molina, Jose; Hernández, Carmen; Pérez-Sirvent, Carmen
2013-04-01
The aim of this work was to assess the suitability of limestone-based technosols for decreasing the toxicity of the leachates caused by rain in sites contaminated by heavy metals. For such a purpose, 64 technosols were prepared in containers of 0.75m3, filled with 4 types of sediments collected from Portman Bay and subjected to different stabilizer proportions (limestone filler), different thickness of a drainage layer and presence/absence of a topsoil cover. The technosols were then submitted to different humidity/dryness cycles simulating the usual rain conditions in the zone. Portman bay is situated close to the mining region of La Unión. The entire area around the bay was subject to mining from the time of the Roman Empire to 1991. Since 1957, the wastes from mining operations were discharged directly into the sea in the inner part of the bay, while later on, they were also discharged to sea at a distance of the shore. These wastes mainly consisted in ore materials (galena, pyrite and sphalerite), phyllosilicates, in addition to siderite, iron oxides and sometimes alteration products such as jarosite, alunite, kaolinite and greenalite. These materials have suffered a concentration process by floatation with sea water and as a result of the discharge, the whole of the bay has filled up with wastes which also extend into the Mediterranean Sea. The pH and the electrical conductivity (EC) was determined in obtained percolates, together with major ion content, determined by ionic chromatography. The Zn, Pb, Cd and Cu content was determined by electrothermal atomization atomic absorption spectrometry (ETAAS). The As content was measured by atomic fluorescence spectrometry. In addition, the mineralogical composition was determined in the evaporated samples by X-Ray diffraction. A battery of bioassays was applied for the ecotoxicological screening of obtained percolates . Particularly, the toxicity was evaluated by using three assays: microtox bioassay (Vibrio fischeri), embryogenesis assay in sea urchin (Paracentrotus lividus) and survival in estuarine amphipods (Gammarus aequicauda). The obtained results suggest that selected remediation technique reduces significantly the toxicological effect of the percolate to the tested organisms. The ecotoxicological testing may be a useful approach for assessing the toxicity as a complement to chemical analysis. In addition, the use of a battery of bioassays allows diminishing problems related to false positive results. The use of limestone filler constitutes an excellent option in sediments polluted by trace elements, because of risk for human health or ecosystems does not exist after the intervention. in addition, the designed experience allow to optimize stabilizer quantities, and may suppose a big cost-saving project in areas affected by mining activities.
An Example of Cyprus type Volcanogenic Massive Sulfide Deposit in the Southeast of Turkey
NASA Astrophysics Data System (ADS)
Kang, J.; Lee, I.; Donmez, C.; Yildirim, N.; Chang, S.
2013-12-01
Ortaklar mineral deposit of Gaziantep province in Turkey is located in the Southeast Anatolian orogenic belt which was developed as a result of closure of Neotethyan ocean, between Tauride (at north) and Arabian platform (at south), during upper Cretaceous-Miocene periods. Copper mineralization is in spilitic basalt and pillow lavas of Kocali complex. The complex includes oceanic fragments that represent serpentinite, mafic and ultramafic cumulates, isotropic gabbros, sheeted dyke complexes, spilitic basalt, pillow lavas, and radiolarian chert. The deposit is generally parallel to the thrust lines (E-W/30-60 North). Ore minerals occur in massive form and also as stockwork or disseminated forms at subsurface. Oxidized zone appears about 1 km in width at surface. The orebody is underlain and contacted with radiolarian chert. The samples mainly have been collected from open pit but also include some core samples. The samples were examined with unaided eyes and under microscope. In basalts, clino-pyroxenes subophitically enclose laths of plagioclases. Amygdales are filled with calcite in spilitic basalts and it is heavily chloritized and cut by calcite veins. In some parts of basalt, crystobalite is intergrowth with plagioclas. Globules between laths of plagioclase are also observed due to liquid immiscibility. Cherts have spherical radiolaria skeletons and their long thin spines. A lot of carbonate veinlets are developed as well. Few samples of cherts have radialfibrous quartz, known as chalcedonic quartz. Serpentinites in the study area are divided into two types on the basis of the existence of relics of the original minerals. One has relict crystals of olivine or pyroxene within the network of serpenitine and the other has no mineral remnants. Both types have opaque iron oxides with some brown stains among small blocks by numerous veinlets. Major ore minerals consist of chalcopyrite, pyrite, magnetite, and hematite. Minor ore minerals are composed of bornite, covellite, chalcocite, sphalerite, and Fe-oxide. Pyrite occurs as a typical cube shape or shows cataclastic texture. And intergrowth of chalcopyrite with magnetite and massive chalcopyrite are observed in the samples. Goethite and lepidocrocite occur in needle or lath shape in the samples from the iron cap as the secondary minerals. It is also shown that pyrite and chalcopyrite are replaced by anhedral bornite and chalcocite. Sulfide textures also indicate grain-coarsening and crystallization under hydrothermal conditions. Electron microprobe was used to identify several minerals and to find out the difference of trace elements such as Cr, Ni, Co, As, Zn, and Pb within mineral grains. Ortaklar copper deposit in Gaziantep resembles Cyprus type volcanogenic massive sulfide deposit based on ore mineralogy, mineral assemblages, textures, and host rock relationship. To investigate more detail characteristics of the deposit, trace elements and rare earth elements were analyzed using inductively coupled plasma mass spectrometer.
NASA Astrophysics Data System (ADS)
James, Rachael H.; Green, Darryl R. H.; Stock, Michael J.; Alker, Belinda J.; Banerjee, Neil R.; Cole, Catherine; German, Christopher R.; Huvenne, Veerle A. I.; Powell, Alexandra M.; Connelly, Douglas P.
2014-08-01
The East Scotia Ridge is an active back-arc spreading centre located to the west of the South Sandwich island arc in the Southern Ocean. Initial exploration of the ridge by deep-tow surveys provided the first evidence for hydrothermal activity in a back-arc setting outside of the western Pacific, and we returned in 2010 with a remotely operated vehicle to precisely locate and sample hydrothermal sites along ridge segments E2 and E9. Here we report the chemical and isotopic composition of high- and low-temperature vent fluids, and the mineralogy of associated high-temperature chimney material, for two sites at E2 (Dog’s Head and Sepia), and four sites at E9 (Black & White, Ivory Tower, Pagoda and Launch Pad). The chemistry of the fluids is highly variable between the ridge segments. Fluid temperatures were ∼350 °C at all vent sites except Black & White, which was significantly hotter (383 °C). End-member chloride concentrations in E2 fluids (532-536 mM) were close to background seawater (540 mM), whereas Cl in E9 fluids was much lower (98-220 mM) indicating that these fluids are affected by phase separation. Concentrations of the alkali elements (Na, Li, K and Cs) and the alkaline earth elements (Ca, Sr and Ba) co-vary with Cl, due to charge balance constraints. Similarly, concentrations of Mn and Zn are highest in the high Cl fluids but, by contrast, Fe/Cl ratios are higher in E9 fluids (3.8-8.1 × 10-3) than they are in E2 fluids (1.5-2.4 × 10-3) and fluids with lowest Cl have highest Cu. Although both ridge segments are magmatically inflated, there is no compelling evidence for input of magmatic gases to the vent fluids. Fluid δD values range from 0.2‰ to 1.5‰, pH values (3.02-3.42) are not especially low, and F concentrations (34.6-54.4 μM) are lower than bottom seawater (62.8 μM). The uppermost sections of conjugate chimney material from E2, and from Ivory Tower and Pagoda at E9, typically exhibit inner zones of massive chalcopyrite enclosed within an outer zone of disseminated sulphide, principally sphalerite and pyrite, in an anhydrite matrix. By contrast, the innermost part of the chimneys that currently vent fluids with lowest Cl (Black & White and Launch Pad), is dominated by anhydrite. By defining and assessing the controls on the chemical composition of these vent fluids, and associated mineralisation, this study provides new information for evaluating the significance of hydrothermal processes at back-arc basins for ocean chemistry and the formation of seafloor mineral deposits.
Shanks, W.C. Pat; Kimball, Bryn E.; Tolcin, Amy C.; Guberman, David E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.
2017-12-19
Germanium and indium are two important elements used in electronics devices, flat-panel display screens, light-emitting diodes, night vision devices, optical fiber, optical lens systems, and solar power arrays. Germanium and indium are treated together in this chapter because they have similar technological uses and because both are recovered as byproducts, mainly from copper and zinc sulfides.The world’s total production of germanium in 2011 was estimated to be 118 metric tons. This total comprised germanium recovered from zinc concentrates, from fly ash residues from coal burning, and from recycled material. Worldwide, primary germanium was recovered in Canada from zinc concentrates shipped from the United States; in China from zinc residues and coal from multiple sources in China and elsewhere; in Finland from zinc concentrates from the Democratic Republic of the Congo; and in Russia from coal.World production of indium metal was estimated to be about 723 metric tons in 2011; more than one-half of the total was produced in China. Other leading producers included Belgium, Canada, Japan, and the Republic of Korea. These five countries accounted for nearly 95 percent of primary indium production.Deposit types that contain significant amounts of germanium include volcanogenic massive sulfide (VMS) deposits, sedimentary exhalative (SEDEX) deposits, Mississippi Valley-type (MVT) lead-zinc deposits (including Irish-type zinc-lead deposits), Kipushi-type zinc-lead-copper replacement bodies in carbonate rocks, and coal deposits.More than one-half of the byproduct indium in the world is produced in southern China from VMS and SEDEX deposits, and much of the remainder is produced from zinc concentrates from MVT deposits. The Laochang deposit in Yunnan Province, China, and the VMS deposits of the Murchison greenstone belt in Limpopo Province, South Africa, provide excellent examples of indium-enriched deposits. The SEDEX deposits at Bainiuchang, China (located in southeastern Yunnan Province), and the Dabaoshan SEDEX deposit (located in the Nanling region of China) contain indium-enriched sphalerite. Another major potential source of indium occurs in the polymetallic tin-tungsten belt in the Eastern Cordillera of the Andes Mountains of Bolivia. Deposits there occur as dense arrays of narrow, elongate, indium-enriched tin oxide-polymetallic sulfide veins in volcanic rocks and porphyry stocks.Information about the behavior of germanium and indium in the environment is limited. In surface weathering environments, germanium and indium may dissolve from host minerals and form complexes with chloride, fluoride, hydroxide, organic matter, phosphate, or sulfate compounds. The tendency for germanium and indium to be dissolved and transported largely depends upon the pH and temperature of the weathering solutions. Because both elements are commonly concentrated in sulfide minerals, they can be expected to be relatively mobile in acid mine drainage where oxidative dissolution of sulfide minerals releases metals and sulfuric acid, resulting in acidic pH values that allow higher concentrations of metals to be dissolved into solution.
Symonds, R.B.; Rose, William I.; Reed, M.H.; Lichte, F.E.; Finnegan, David L.
1987-01-01
Condensates, silica tube sublimates and incrustations were sampled from 500-800??C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.-Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 105 in Se, Re, Bi and Cd; 104-105 in Au, Br, In, Pb and W; 103-104 in Mo, Cl, Cs, S, Sn and Ag; 102-103 in As, Zn, F and Rb; and 1-102 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 106 grams/day ( g d) of S, Cl and F; 104-106 g/d of Al, Br, Zn, Fe, K and Mg; 103-104 g d of Pb, As, Mo, Mn, V, W and Sr; and less than 103 g d of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500??C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915??C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit. ?? 1987.
A Late Variscan Sn province: the Arburese region (SW Sardinia, Italy)
NASA Astrophysics Data System (ADS)
Naitza, Stefano; Secchi, Francesco; Oggiano, Giacomo; Cuccuru, Stefano
2015-04-01
Late Variscan Sn - rich European provinces (e. g. Erzgebirge, Cornwall) are of particular relevance as they offer key insights into crustal evolution, intrusive processes and ore genesis. In Sardinia (Italy), small Sn deposits are only known in the Arburese historical mining region (SW Sardinia), hosted in low-grade metamorphics close to the contacts with intrusives. This region is characterised by two late variscan intrusions, which differ in age and composition: the Arbus and the Monte Linas pluton, aging 304 ± 1 Ma, and 289 ± 1 Ma respectively. They emplaced at shallow crustal levels and crosscut the basal thrust between the alloctonous prism and the foreland of the Variscan belt of Sardinia. The Arbus Pluton (AP) is a composite intrusion of piroxene- and amphibole- granodiorites hosting minor amounts of monzogabbroic rocks and cordierite-bearing granites with a wide core of leuco-monzogranites. Tourmaline greisens and pegmatites garnish the contact between the border facies and the host metamorphic rocks. The Monte Linas Pluton (MLP) has biotite monzogranite composition. The pluton is internally zoned, from medium grained monzogranite in the core to hololeucocratic fine-grained rock-types at the top, where often F-greisen, fayalite-pegmatite pods and sill are common. In both plutons the igneous associations are high-K ilmenite series, suggesting derivation from low- fO2 magmas possibly linked to a common crustal contribution; however, in the Linas Pluton magnetite in the fine-grained facies may indicate an increase in oxygen fugacity. The AP-related Sn ores consist of high-temperature As-Sn quartz veins. They are vertically zoned, from quartz-chlorite-cassiterite to large quartz-arsenopyrite veins. Ore microscopy and SEM-EDS analyses evidenced a vein texture made of thick idiomorphic and frequently twinned cassiterite crystals, alternated with several generations of banded/geodic quartz. Chlinoclore aggregates are included into the quartz. The arsenopyrite ore shows alternating bands of microgranular to crystalline millimetric arsenopyrite with quartz. Field and analytical data suggest genetic mechanisms dominated by mobilization of residual Sn by chloride and other complexes in reducing, As- and S- rich, low- fO2 juvenile fluids. Cassiterite and successive arsenopyrite precipitation occurred under changing physicochemical conditions (e.g. oxygen contents; temperature decrease; pH). The MLP Sn metallogeny include Sn- Pb-Zn-Cu veins (Canale Serci old mine). Cassiterite occurs as fine-grained corroded crystals. Optical and SEM-EDS analyses evidence a high-temperature oxide stage (quartz-chlorite- cassiterite) followed, after brecciation, by mesothermal sulfide stages, with progressive deposition of sphalerite, pyrite, chalcopyrite, tetrahedrite, galena, marcasite. Arsenopyrite is strikingly absent. These evidences indicate possible derivation of the ore from residual, reducing juvenile fluids, capable to carry Sn- complexes from monzogranite magmas from which cassiterite precipitated in consequence of an increasing in fO2. Despite their limited amount, the Sn ores of SW Sardinia have high metallogenic relevance, indicating the persistence, of geochemical conditions,which lasted 15 Ma, favorable to the genesis of a Sn metallogenic province.
NASA Astrophysics Data System (ADS)
Smith-Schmitz, Sarah E.; Appold, Martin S.
2018-03-01
Knowledge of the concentrations of Zn and Pb in Mississippi Valley-type (MVT) ore fluids is fundamental to understanding MVT deposit origin. Most previous attempts to quantify the concentrations of Zn and Pb in MVT ore fluids have focused on the analysis of fluid inclusions. However, these attempts have yielded ambiguous results due to possible contamination from secondary fluid inclusions, interferences from Zn and Pb in the host mineral matrix, and uncertainties about whether the measured Zn and Pb signals represent aqueous solute or accidental solid inclusions entrained within the fluid inclusions. The purpose of the present study, therefore, was to try to determine Zn and Pb concentrations in MVT ore fluids using an alternate method that avoids these ambiguities by calculating Zn and Pb concentrations in MVT ore fluids theoretically based on their solid solution concentrations in calcite. This method was applied to the Illinois-Kentucky and Central Tennessee districts, which both contain ore-stage calcite. Experimental partition coefficient (D) values from Rimstidt et al. (1998) and Tsusue and Holland (1966), and theoretical thermodynamic distribution coefficient (KD) values were employed in the present study. Ore fluid concentrations of Zn were likely most accurately predicted by Rimstidt et al. (1998) D values, based on their success in predicting known fluid inclusion concentrations of Mg and Mn, and likely also most accurately predicted ore fluid concentrations of Fe. All four of these elements have a divalent ionic radius smaller than that of Ca2+ and form carbonate minerals with the calcite structure. For both the Illinois-Kentucky and the Central Tennessee district, predicted ore fluid Zn and Fe concentrations were on the order of up to 10's of ppm. Ore fluid concentrations of Pb could only be predicted using Rimstidt et al. (1998) D values. However, these concentrations are unlikely to be reliable, as predicted ore fluid concentrations of Sr and Ba, which like Pb also have a divalent ionic radius larger than that of Ca2+ and form carbonate minerals with the aragonite structure, did not consistently agree well with known concentrations of Sr and Ba in fluid inclusions. The ore fluid Zn concentrations predicted in the present study lie within the range of Zn concentrations typical of modern sedimentary brines and are high enough to allow deposition of the observed amounts of Zn in the Illinois-Kentucky and Central Tennessee districts within ranges of geologically reasonable times and ore fluid flow velocities. If the pH of the Illinois-Kentucky and Central pH ore fluids was as low as current evidence suggests to be possible, then these ore fluids could simultaneously have transported enough sulfide with their Zn to account for the observed amounts of sphalerite in the districts.
NASA Astrophysics Data System (ADS)
Abd El Monsef, Mohamed
2015-04-01
The orogenic gold deposits are a distinctive type of deposits that revealed unique temporal and spatial association with an orogeny. Where, the system of gold veins and related ore minerals was confined to hydrothermal solutions formed during compressional to transpressional deformation processes at convergent plate margins in accretionary and collisional orogens, with the respect to ongoing deep-crustal, subduction-related thermal processes. In Egypt, most of vein-type and dyke-type gold mineralization are restricted to granitic rocks or at least near of granitic intrusion that seems to have had an important influence on gold mineralization. Shear zone-related, mesothermal gold deposits of Fatira and Gidami mines in the northern Eastern Desert of Egypt are found within granitic bodies or at the contact between granites and metavolcanic rocks. The hosting-granitic rocks in Fatira and Gidami areas are mainly of granodioritic composition (I-Type granite) which is related to calc-alkaline magmatic series. However, Fatira granitoids were developed within island arc tectonic settings related to mature island arc system (Late-orogenic stage), at relatively low temperature (around 660° C) and medium pressure between (5 - 10 Kbar). On the other hand, Gidami granitoids were developed during the collision stage in continental arc regime related to active continental margin (Syn-orogeny), which were crystallized at relatively high temperature (700-720° C) and low pressure (around 0.1 Kbar). The ore mineralogy includes pyrite, chalcopyrite, sphalerite, covellite, ilmenite, goethite ± pyrrhotite ± pentlandite ± galena ± molybdenite. Native gold is detected only in Gidami mineralization as small inclusions within pyrite and goethite or as tiny grains scattered within quartz vein (in close proximity to the sulfides). In Fatira deposits, it is detected only by microprobe analysis within the crystal lattice of pyrite and jarosite. Fluid inclusions study for the mineralized ores revealed two main groups of fluid inclusions in both areas: A) Aqueous inclusions (H2O-NaCl±KCl system), and B) Carbonic inclusions (H2O-CO2-NaCl±CH4). A drop of pressure during the migration of these fluids to shallower depths along the shear zones was the main reason for phase separation. Isochores calculation from microthermometric results proved that, the P-T boundary conditions outlined for Fatira gold deposits are of 275° to 297° C and between (0.2 - 1.2 Kbar); and of 277° to 300° C and between (0.2 - 1 Kbar) for Gidami gold deposits. The normalization Chondrite patterns of rare earth elements (REEs) for the gold-ore deposits with the surrounding I-type granitic rocks exhibit an obvious similarity and positive correlation. The geological, mineralogical, geochemical and fluid inclusions studies revealed a genetic link between gold mineralization and intrusion of calc-alkaine granitic magma. Whereas, The granitic magma acts as a supplier for the ore-bearing fluid and as a heat source for metamorphic processes, leading to hydrothermal convection currents.
Seal, Robert R.; Ayuso, Robert A.; Foley, Nora K.; Clark, Sandra H.B.
2001-01-01
The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110 metric tons of gold over the past 10 years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite–barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The δ34S values of massive barite cluster tightly between 25.0 and 28.0‰, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The δ34S values of massive sulfide range from 1.0 to 5.3‰ and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, δ34S values for finer-grained, intergrown pyrite (5.1–6.8‰) and barite (21.0–23.9‰) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite–pyrite pairs (Δ=15.9–17.1‰) range from 332–355 °C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for 206Pb/204Pb from 18.005–18.294, for 207Pb/204Pb from 15.567–15.645, and for 208Pb/204Pb from 37.555–38.015. The data indicate derivation of the ore leads from the country rocks, which themselves show evidence for contributions from relatively unradiogenic, mantle-like lead, and more evolved or crustal lead. Geological relationships, and stable and radiogenic isotopic data, suggest that the Barite Hill gold deposit formed on the Late Proterozoic seafloor through exhalative hydrothermal processes similar to those that were responsible for the massive sulfide deposits of the Kuroko district, Japan. On the basis of similarities with other gold-rich massive sulfide deposits and modern seafloor hydrothermal systems, the gold at Barite Hill was probably introduced as an integral part of the formation of the massive sulfide deposit.
NASA Astrophysics Data System (ADS)
Bergamin, Luisa; Capello, Marco; Carbone, Cristina; Magno, Maria Celia; Consani, Sirio; Cutroneo, Laura; Ferraro, Luciana; Pierfranceschi, Giancarlo; Romano, Elena
2016-04-01
Benthic foraminiferal assemblages react in short time to natural and anthropogenic environmental changes and, for this, they are considered as reliable indicators of environmental quality. An interesting application of these indicators is the study of their response to environmental changes in coastal marine areas, affected by dismissed mines and dump areas. The Libiola Fe-Cu sulphide mine was intensively exploited in 19th and 20th centuries, and the activity ended in 1962. The sulphide mineral assemblages consist of pyrite and chalcopyrite, with minor sphalerite and pyrrhotite, in a gangue of quartz and chlorite. The sulphide ore occurs within the Jurassic ophiolites of the Northern Apennines which were subjected to metamorphic and tectonic processes during the subsequent Apennine orogenesis. Waters circulating in the Libiola mine area, and discharging in the adjacent streams and creeks, are strongly polluted due to the diffuse occurrence of Acid Mine Drainage processes. The Gromolo torrent collects these acidic waters enriched of heavy metals which flow into Ligurian Sea. The study area is characterised by a shelf with a gentle slope, mainly constituted by sediment supplied by Entella torrent. The general circulation has trend from East to West and the coastal drift is generally eastwards. A total of 15 marine sediment samples (upper 2 cm) were collected by means of Van Veen grab in the coastal zone close to the Gromolo mouth and analyzed for living (rose Bengal stained) and dead benthic foraminifera, together with grain size, metals and trace elements, and metal fractioning. Quantitative foraminiferal parameters, like as abundance, species diversity, heterogeneity and assemblage composition, were determined and evaluated for environmental purpose. Additionally, possible increase above the natural background level of deformed specimens was considered as indicative of metal contamination. The grain-size analyses highlighted mainly sandy sediments, characterized by a small pelitic fraction, ranging from 0.5% to 28%. Sediments are greyish, usually very fine-grained, with infrequent organogenic fraction. The mineralogical composition is based on dark green grains of serpentine nature, sometimes fibrous, with spread inclusions of magnetite, associated with lithic sandstone, dark gray shales, gabbros, fragments of quartz, feldspar, serpentine and chlorite. Metal concentration shows, in the whole study area, high concentrations of As, Cr, and Ni while, in the samples close to the Gromolo mouth, high values also for Cu, Co, Zn, Pb, Hg, and Cd were recorded. The foraminiferal study highlighted several samples with very low abundance, especially in the coastal belt between Gromolo and Entella torrents. Slightly higher abundance was recorded close to the Gromolo mouth, where sediments are strongly characterized by Ammonia. Both living and dead assemblages displayed low diversity and high dominance with Ammonia beccarii which accounts up to 66% of total abundance. Moreover, percentage of deformed specimens generally exceeded the natural background reaching 5%. All these aspects are clear evidence of an environmental stress.
Thorium and rare earth minerals in the Powderhorn district, Gunnison County, Colorado
Olson, Jerry C.; Wallace, Stewart R.
1954-01-01
Thorium has been found since 1949 in at least 33 deposits in an area 6 miles wide and 20 miles long in the Powderhorn district, Gunnison County, Colo. The district is composed largely of pre-Jurassic metamorphic and igneous rocks, which are chiefly if not entirely pre-Cambrian in age. The metamorphic and igneous rocks are overlain by sandstone of the Morrison formation of Jurassic age, and by volcanic rocks of the Alboroto group and Hinsdale formation of Miocene and Pliocene (?) age, respectively. The thorium deposits occur in or near alkalic igneous rocks in which such elements as titanium, rare earths, barium, strontium, and niobium occur in greater-than-average amounts. The greatest mass of the alkalic igneous rocks the Iron Hill composite stoc,- occupies an area of 12 square miles in the southeastern part of the district. The age of the thorium deposits, like that of the alkalic igneous rocks, is not known other than pre-Jurassic. The thorium veins and mineralized shear zones range from a few inches to 18 feet in thickness and from a few feet to 3,500 feet in length. The veins are composed of calcite,.dolomite, siderite, ankerite, quartz, barite, pyrite, sphalerite, galena, goethite,. apatite, alkali feldspar, and many other minerals. The thorium occurs at least partly in thorite or hydrothorite. Sparse xenotime has been tentatively identified in one deposit. Several minerals containing rare earths of the cerium group as major constituents are found in carbonate veins near Iron Hill. Bastnaesite has been identified by X-ray methods, and cerite and synchisite are probably present also.The fluorapatite in some veins and in parts of the carbonate rock mass that occupies 2 square miles in the central part of the Iron Hill complex contains rare earths of the cerium group, generally in amounts of a fraction of a percent of the rock. The radioactivity of the deposits appears to be due almost entirely to thorium and its daughter products The ThO2 content of selected highgrade samples from the Little Johnnie vein is as much as 4 percent. The ThO2 content of the veins is generally less than 1 percent, however, and is only 0.05 to 0.1 percent in many of the veins studied. The little Johnnie vein, which was mapped in detail, can be traced discontinuously for a distance of more than 3,500 feet. The thoriumbearing material occurs as irregular veinlets and thin films introduced into the fault zone. The mineralized shear zone ranges from less than 6 inches to 5 feet in thickness. Near its west end the vein is broken by many faults in a zone that marks the edge of a roughly circular fault block, 11/2.miles in diameter, that has dropped 1,000 feet or more since the deposition of Miocene volcanic-rocks that now floor the Milkranch basin.
Geological Assessment of Cores from the Great Bay National Wildlife Refuge, New Hampshire
Foley, Nora K.; Ayuso, Robert A.; Ayotte, Joseph D.; Montgomery, Denise L.; Robinson, Gilpin R.
2007-01-01
Geological sources of metals (especially arsenic and zinc) in aquifer bedrock were evaluated for their potential to contribute elevated values of metals to ground and surface waters in and around Rockingham County, New Hampshire. Ayotte and others (1999, 2003) had proposed that arsenic concentrations in ground water flowing through bedrock aquifers in eastern New England were elevated as a result of interaction with rocks. Specifically in southeastern New Hampshire, Montgomery and others (2003) established that nearly one-fifth of private bedrock wells had arsenic concentrations that exceed the U.S. Environmental Protection Agency (EPA) maximum contamination level for public water supplies. Two wells drilled in coastal New Hampshire were sited to intersect metasedimentary and metavolcanic rocks in the Great Bay National Wildlife Refuge. Bulk chemistry, mineralogy, and mineral chemistry data were obtained on representative samples of cores extracted from the two boreholes in the Kittery and Eliot Formations. The results of this study have established that the primary geologic source of arsenic in ground waters sampled from the two well sites was iron-sulfide minerals, predominantly arsenic-bearing pyrite and lesser amounts of base-metal-sulfide and sulfosalt minerals that contain appreciable arsenic, including arsenopyrite, tetrahedrite, and cobaltite. Secondary minerals containing arsenic are apparently limited to iron-oxyhydroxide minerals. The geologic source of zinc was sphalerite, typically cadmium-bearing, which occurs with pyrite in core samples. Zinc also occurred as a secondary mineral in carbonate form. Oxidation of sulfides leading to the liberation of acid, iron, arsenic, zinc, and other metals was most prevalent in open fractures and vuggy zones in core intervals containing zones of high transmissivity in the two units. The presence of significant calcite and lesser amounts of other acid-neutralizing carbonate and silicate minerals, acting as a natural buffer to reduce acidity, forced precipitation of iron-oxyhydroxide minerals and the removal of trace elements, including arsenic and lead, from ground waters in the refuge. Zinc may have remained in solution to a greater extent because of complexing with carbonate and its solubility in near-neutral ground and surface waters. The regional link between anomalously high arsenic contents in ground water and a bedrock source as established by Ayotte and others (1999, 2003) and Montgomery and others (2003) was confirmed by the presence of some arsenic-bearing minerals in rocks of the Kittery and Eliot Formations. The relatively low amounts of arsenic and metals in wells in the Great Bay National Wildlife Refuge as reported by Ayotte and others (U.S. Geological Survey Water Resources Data, 2005) were likely controlled by local geochemical environments in partially filled fractures, fissures, and permeable zones within the bedrock formations. Carbonate and silicate gangue minerals that line fractures, fissures, and permeable zones likely limited the movement of arsenic from bedrock to ground water. Sources other than the two geologic formations might have been required to account for anomalously high arsenic contents measured in private bedrock aquifer wells of Rockingham County.
NASA Astrophysics Data System (ADS)
Feng, Caixia; Bi, Xianwu; Liu, Shen; Hu, Ruizhong
2014-05-01
The Baiyangping Cu-Ag polymetallic ore district is located in the northern part of the Lanping-Simao foreland fold belt, which lies between the Jinshajiang-Ailaoshan and Lancangjiang faults in western Yunnan Province, China. The source of ore-forming fluids and materials within the eastern ore zone were investigated using fluid inclusion, rare earth element (REE), and isotopic (C, O, and S) analyses undertaken on sulfides, gangue minerals, wall rocks, and ores formed during the hydrothermal stage of mineralization. These analyses indicate: (1) The presence of five types of fluid inclusion, which contain various combinations of liquid (l) and vapor (v) phases at room temperature: (a) H2O (l), (b) H2O (l) + H2O (v), (c) H2O (v), (d) CmHn (v), and (e) H2O (l) + CO2 (l), sometimes with CO2 (v). These inclusions have salinities of 1.4-19.9 wt.% NaCl equivalents, with two modes at approximately 5-10 and 16-21 wt.% NaCl equivalent, and homogenization temperatures between 101 °C and 295 °C. Five components were identified in fluid inclusions using Raman microspectrometry: H2O, dolomite, calcite, CH4, and N2. (2) Calcite, dolomitized limestone, and dolomite contain total REE concentrations of 3.10-38.93 ppm, whereas wall rocks and ores contain REE concentrations of 1.21-196 ppm. Dolomitized limestone, dolomite, wall rock, and ore samples have similar chondrite-normalized REE patterns, with ores in the Huachangshan, Xiaquwu, and Dongzhiyan ore blocks having large negative δCe and δEu anomalies, which may be indicative of a change in redox conditions during fluid ascent, migration, and/or cooling. (3) δ34S values for sphalerite, galena, pyrite, and tetrahedrite sulfide samples range from -7.3‰ to 2.1‰, a wide range that indicates multiple sulfur sources. The basin contains numerous sources of S, and deriving S from a mixture of these sources could have yielded these near-zero values, either by mixing of S from different sources, or by changes in the geological conditions of seawater sulfate reduction to sulfur. (4) The C-O isotopic analyses yield δ13C values from ca. zero to -10‰, and a wider range of δ18O values from ca. +6 to +24‰, suggestive of mixing between mantle-derived magma and marine carbonate sources during the evolution of ore-forming fluids, although potential contributions from organic carbon and basinal brine sources should also be considered. These data indicate that ore-forming fluids were derived from a mixture of organism, basinal brine, and mantle-derived magma sources, and as such, the eastern ore zone of the Baiyangping polymetallic ore deposit should be classified as a “Lanping-type” ore deposit.
NASA Astrophysics Data System (ADS)
Dziggel, A.; Wulff, K.; Kolb, J.; Meyer, F. M.
2009-08-01
The Navachab gold deposit in the Damara belt of central Namibia is hosted by a near-vertical sequence of amphibolite facies shelf-type metasediments, including marble, calc-silicate rock, and biotite schist. Petrologic and geochemical data were collected in the ore, alteration halos, and the wall rock to evaluate transport of elements and interaction between the wall rock and the mineralizing fluid. The semi-massive sulfide lenses and quartz-sulfide veins are characterized by a complex polymetallic ore assemblage, comprising pyrrhotite, chalcopyrite, sphalerite, and arsenopyrite, native bismuth, gold, bismuthinite, and bismuth tellurides. Mass balance calculations indicate the addition of up to several orders of magnitude of Au, Bi, As, Ag, and Cu. The mineralized zones also record up to eightfold higher Mn and Fe concentrations. The semi-massive sulfide lenses are situated in the banded calc-silicate rock. Petrologic and textural data indicate that they represent hydraulic breccias that contain up to 50 vol.% ore minerals, and that are dominated by a high-temperature (T) alteration assemblage of garnet-clinopyroxene-K-feldspar-quartz. The quartz-sulfide veins crosscut all lithological units. Their thickness and mineralogy is strongly controlled by the composition and rheological behavior of the wall rocks. In the biotite schist and calc-silicate rock, they are up to several decimeters thick and quartz-rich, whereas in the marble, the same veins are only a few millimeters thick and dominated by sulfides. The associated alteration halos comprise (1) an actinolite-quartz alteration in the biotite schist, (2) a garnet-clinopyroxene-K-feldspar-quartz alteration in the marble and calc-silicate rock, and (3) a garnet-biotite alteration that is recorded in all rock types except the marble. The hydrothermal overprint was associated with large-scale carbonate dissolution and a dramatic increase in CO2 in the ore fluid. Decarbonation of wall rocks, as well as a low REE content of the ore fluid resulted in the mobilization of the REE, and the decoupling of the LREE from the HREE. The alteration halos not only parallel the mineralized zones, but may also follow up single layers away from the mineralization. Alteration is far more pronounced facing upward, indicating that the rocks were steep when veining occurred. The petrologic and geochemical data indicate that the actinolite-quartz- and garnet-clinopyroxene-K-feldspar-quartz alterations formed in equilibrium with a fluid (super-) saturated in Si, and were mainly controlled by the composition of the wall rocks. In contrast, the garnet-biotite alteration formed by interaction with a fluid undersaturated in Si, and was mainly controlled by the fluid composition. This points to major differences in fluid-rock ratios and changes in fluid composition during alteration. The alteration systematics and geometry of the hydrothermal vein system are consistent with cyclic fluctuations in fluid pressure during fault valve action.
NASA Astrophysics Data System (ADS)
Hein, J. R.; de Ronde, C. E.; Ditchburn, R.; Leybourne, M. I.; Tamura, Y.; Stern, R. J.; Conrad, T. A.; Nichols, A. R.; Shukuno, H.; Embley, R. W.; Bloomer, S. H.; Ishizuka, O.; Hirahara, Y.; Senda, R.; Nunokawa, A.; Jordan, E.; Wada, I.
2010-12-01
An elongate field of hydrothermal mounds was discovered along the NE flank of a cluster of resurgent dacite domes in East Diamante Caldera using the ROV Hyper-Dolphin aboard the R.V. Natsushima in June 2009 and July 2010. East Diamante seamount lies about 80 km north of Saipan and is the northernmost volcano of the Southern Seamount Province of the Mariana magmatic arc. East Diamante is an irregular caldera about 10 km x 4 km that is breached on the north and south sides. The caldera floor has a maximum water depth of about 700 m. After caldera collapse, dacitic domes intruded into the center of the caldera providing the heat source for production and circulation of hydrothermal fluids that generated the large mounds field and two nearby chimney fields, one active and one inactive, found in 2004 during a NOAA Ring-of-Fire cruise. The mounds field is more than 100 m long and about 25-30 m wide and occurs along a NE-SW rift valley at water depths of about 365-400 m b.s.l. Individual hydrothermal mounds and ridges along this trend vary in size and the bases of the mounds are buried beneath hydrothermal sediment so that only minimum dimensions can be determined. Mounds are typically 1-3 m tall and 0.5-2 m wide, with lengths of about 3 to more than 5 m. The sulfide/sulfate mounds are layered and an iron- and manganese-oxide subsidiary mound venting low-temperature fluids caps some of them. Some mounds also support inactive sulfide/sulfate chimneys and spires; chimneys rarely occur as independent structures within the mounds field. The mounds are composed primarily of barite layers and sphalerite (high cadmium, low iron) plus galena layers with up to 470 ppm silver and 3 ppm gold. The subsidiary mounds are composed of 7A manganate and goethite that occur around a delicate network of 2-10 mm diameter anastomosing channels. Similar oxides cover the seabed throughout the mounds field and precipitated from diffuse fluid flow throughout the region, but formed by both diffuse and focused flow on top of the layered mounds. Several age dates for one mound show the layered section to have formed about 4,000 years ago while the subsidiary oxides formed during the past 4 years. Mineralization appears to be controlled by proximity to the NE-SW rift or fracture zone. Focused flow occurred along a line source rather than a point source that is typical of most hydrothermal chimney fields. Diffuse flow occurred adjacent to the rift and through the sulfide/sulfate mounds deposited atop the conduit. This field may be in a waning stage of activity with higher temperature fluids having been involved in construction of the main mounds several millennia ago. Alternatively, the present low-temperature activity may represent rejuvenation of the system.
NASA Astrophysics Data System (ADS)
Periferakis, Argyrios; Voudouris, Panagiotis; Melfos, Vasilios; Mavrogonatos, Constantinos; Alfieris, Dimitrios
2017-04-01
Lesvos Island is located at the NE part of the Aegean Sea and mostly comprises post-collisional Miocene volcanic rocks of shoshonitic to calc-alkaline geochemical affinities. In the northern part of the Island, the Stypsi Cu-Mo±Au porphyry prospect, part of the Stypsi caldera, is hosted within hydrothermally altered intrusives and volcanics [1]. Porphyry-style mineralization is developed in a microgranite porphyry that has intruded basaltic trachyandesitic lavas. Propylitic alteration occurs distal to the mineralization, whereas sodic-calcic alteration related to quartz-actinolite veinlets, and a phyllic overprint associated with a dense stockwork of banded black quartz±carbonate veinlets, characterizes the core of the system. Alunite-kaolinite advanced argillic alteration occurs at higher topographic levels and represents a barren lithocap to the porphyry mineralization. Intermediate-sulfidation (IS) milky quartz-carbonate veins overprint the porphyry mineralization along a NNE-trending fault that extends further northwards to Megala Therma, where it hosts IS base metal-rich Ag-Au mineralization [2]. New mineralogical data from the Megala Therma deposit suggest Ag-famatinite, Te-polybasite and Ag-tetrahedrite as the main carriers of Ag in the mineralization. Porphyry-style ores at Stypsi consist of magnetite postdated by pyrite and then by chalcopyrite, molybdenite, sphalerite, galena and bismuthinite within the black quartz stockworks or disseminated in the wallrock [1]. The dark coloration of quartz in the veinlets is due to abundant vapor-rich fluid inclusions. Quartz is granular and fine-grained and locally elongated perpendicular to the vein walls. Botryoidal textures are continuous through quartz grains, suggesting quartz recrystallization from a silica gel, a feature already described by [3] from banded quartz veinlets in porphyry Au deposits at Maricunga, Chile. Bulk ore analyses from porphyry-style mineralization at Stypsi displayed similar geochemical anomalies to those previously reported by [1] but also provide additional information in a series of elements: Cu (up to 843 ppm), Mo (up to 76 ppm), Au (up to 120 ppb), Pb (up to 339ppm), Zn (up to 815ppm), Se (up to 10ppm), Te (up to 4 ppm), Bi (up to 4 ppm) and Sn (up to 23 ppm). The Lesvos Island may be interpreted as the westward extension of the Eocene-Miocene Biga peninsula Cu-Au porphyry belt, with potential for future discoveries of Cu-Mo±Au deposits in the Aegean area. [1] Voudouris P, Alfieris D (2005) New porphyry-Cu±Mo occurrences in northeastern Aegean/Greece: Ore mineralogy and transition to epithermal environment. In: Mao J, Bierlein FP (eds) Mineral deposit research: Meeting the global challenge. Springer Verlag, 473-476; [2] Kontis E, Kelepertsis AE, Skounakis S (1994) Geochemistry and alteration facies associated with epithermal precious metal mineralization in an active geothermal system, northern Lesvos, Greece. Min Deposita, 29:430-433; [3] Muntean JL, Einaudi MT (2000) Porphyry Gold Deposits of the Refugio District, Maricunga Belt, Northern Chile. Econ. Geology, 95, 1445-1472.
Johnson, C.A.; Skinner, B.J.
2003-01-01
The New Jersey Highlands terrace, which is an exposure of the Middle Proterozoic Grenville orogenic belt located in northeastern United States, contains stratiform zinc oxide-silicate deposits at Franklin and Sterling Hill and numerous massive magnetite deposits. The origins of the zinc and magnetite deposits have rarely been considered together, but a genetic link is suggested by the occurrence of the Furnace magnetite bed and small magnetite lenses immediately beneath the Franklin zinc deposit. The Furnace bed was metamorphosed and deformed along with its enclosing rocks during the Grenvillian orogeny, obscuring the original mineralogy and obliterating the original rock fabrics. The present mineralogy is manganiferous magnetite plus calcite. Trace hydrous silicates, some coexisting with fluorite, have fluorine contents that are among the highest ever observed in natural assemblages. Furnace bed calcite has ??13C values of -5 ?? 1 per mil relative to Peedee belemnite (PDB) and ??18O values of 11 to 20 per mil relative to Vienna-standard mean ocean water (VSMOW). The isotopic compositions do not vary as expected for an original siderite layer that decarbonated during metamorphism, but they are consistent with nearly isochemical metamorphism of an iron oxide + calcite protolith that is chemically and minerlogically similar to iron-rich sediments found near the Red Sea brine pools and isotopically similar to Superior-type banded iron formations. Other magniferous magnite + calcite bodies occur at approximately the same stratigraphic position as far 50 km from the zinc deposits. A model is presented in which the iron and zinc deposits formed along the western edge of a Middle Proterozoic marine basin. Zinc was transported by sulfate-stable brines and was precipitated under sulfate-stable conditions as zincian carbonates and Fe-Mn-Zn oxides and silicates. Whether the zincian assemblages settled from the water column or formed by replacement reactions in shallowly buried sediments is uncertain. The iron deposits formed at interfaces between anoxic and oxygenated waters. The Furnace magnetite bed resulted from seawater oxidation of hydrothermally transported iron near a brine conduit. Iron deposits also formed regionally on the basin floor at the interface betveen anoxic deep waters and oxygenated shallower waters. These deposits include not only manganiferous magnetite + calcite bodies similar to the Furnace magnetite bed but also silicate-facies deposits that formed by iron oxide accumulation where detrital sediment was abundant. A basin margin model can be extended to Grenvillian stratiform deposits in the northwest Adirondacks of New York and the Mont Laurier basin of Quebec. In these areas iron deposits (pyrite or magnetite) are found basinward of marble-hosted sphalerite deposits, such as those in the Balmat-Edwards district. Whether the iron and zinc precipitated as sulfide assemblages or carbonate-oxide-silicate assemblages depended on whether sufficient organic matter or other reductants were available in local sediments or bottom waters to stabilize H2S.
The Third Dimension of an Active Back-arc Hydrothermal System: ODP Leg 193 at PACMANUS
NASA Astrophysics Data System (ADS)
Binns, R.; Barriga, F.; Miller, D.
2001-12-01
This first sub-seafloor examination of an active hydrothermal system hosted by felsic volcanics, at a convergent margin, obtained drill core from a high-T "smoker" site (penetrated to sim200 mbsf) and a low-T site of diffuse venting (~400mbsf). We aimed to delineate the lateral and vertical variability in mineralisation and alteration patterns, so as to understand links between volcanological, structural and hydrothermal phenomena and the sources of fluids, and to establish the nature and extent of microbial activity within the system. Technological breakthroughs included deployment of a new hard-rock re-entry system, and direct comparison in a hardrock environment of structural images obtained by wireline methods and logging-while-drilling. The PACMANUS hydrothermal site, at the 1700m-deep crest of a 500m-high layered sequence of dacitic lavas, is notable for baritic massive sulfide chimneys rich in Cu, Zn, Au and Ag. Below an extensive cap 5-40m thick of fresh dacite-rhyodacite, we found unexpectedly pervasive hydrothermal alteration of vesicular and flow-banded precursors, accompanied by variably intense fracturing and anhydrite-pyrite veining. Within what appears one major hydrothermal event affecting the entire drilled sequence, there is much overprinting and repetition of distinctly allochemical argillaceous (illite-chlorite), acid-sulfate (pyrophyllite-anhydrite) and siliceous assemblages. The alteration profiles include a transition from metastable cristobalite to quartz at depth, and are similar under low-T and high-T vent sites but are vertically condensed in a manner suggesting higher thermal gradients beneath the latter. The altered rocks are surprisingly porous (average 25%). Retention of intergranular pore spaces and open vesicles at depth implies elevated hydrothermal pressures, whereas evidence from fluid inclusions and hydrothermal brecciation denotes local or sporadic phase separation. A maximum measured temperature of 313 degC measured 8 days after drilling (360 mbsf at the diffuse venting site), if indicative of thermal gradient, suggests the presence of a very shallow ( ~1.5 km below seafloor) magmatic heat source. While isotopic characteristics of anhydrite suggest an irregularly varying component of magmatic fluid, the abundance of this mineral implies a substantial role for circulating seawater within the subsurface hydrothermal system. Other than the near-ubiquitous, fine grained disseminated pyrite in altered rocks, we found little sulfide mineralisation. Pyritic vein networks and breccias are extensive in the rapidly penetrated, but poorly recovered, interval down to 120 mbsf within our "high-T end-member" hole spudded on a mound surmounted by active (280 degC) chimneys. Anhydrite and open cavities possibly dominate this interval, from which a possible example of subhalative semi-massive sulfide containing chalcopyrite and some sphalerite was recovered near 30 mbsf. At the low-T and high-T vent sites respectively, anaerobic microbes were recorded by direct counting at depths down to 99 and 78 mbsf, and in 90 degC cultivation experiments at 69-107 and 99-129 mbsf. >http://www-odp.tamu.edu/publications/prelim/193
NASA Astrophysics Data System (ADS)
Magnall, J. M.; Gleeson, S. A.; Blamey, N. J. F.; Paradis, S.; Luo, Y.
2016-11-01
At Macmillan Pass (YT, Canada), the hydrothermal vent complexes beneath two shale-hosted massive sulphide (SHMS) deposits (Tom, Jason) are well preserved within Late Devonian strata. These deposits provide a unique opportunity to constrain key geochemical parameters (temperature, salinity, pH, fO2, ΣS) that are critical for metal transport and deposition in SHMS systems, and to evaluate the interaction between hydrothermal fluids and the mudstone host rock. This has been achieved using a combination of detailed petrography, isotopic techniques (δ34S, δ13C and δ18O values), carbonate rare earth element analysis (LA-ICP-MS), fluid inclusion analysis (microthermometry, gas analysis via incremental crush fast scan mass spectrometry), and thermodynamic modelling. Two main paragenetic stages are preserved in both vent complexes: Stage 1 comprises pervasive ankerite alteration of the organic-rich mudstone host rock and crosscutting stockwork ankerite veining (±pyrobitumen, pyrite and quartz) and; Stage 2 consists of main stage massive sulphide (galena-pyrrhotite-pyrite ± chalcopyrite-sphalerite) and siderite (±quartz and barytocalcite) mineralisation. Co-variation of δ18O and δ13C values in ankerite can be described by temperature dependent fractionation and fluid rock interaction. Together with fluid inclusion microthermometry, this provides evidence of a steep thermal gradient (from 300 to ∼100 °C) over approximately 15 m stratigraphic depth, temporally and spatially constrained within the paragenesis of both vent complexes and developed under shallow lithostatic (<1 km; 250 bars) to hydrostatic (<400 m; 40 bars) conditions. There is evidence of mixing between diagenetic and hydrothermal fluids recorded in chondrite-normalised rare earth element (REE) profiles of ankerite and siderite. Middle REE enrichments and superchondritic Y/Ho ratios (>28), characteristic of diagenetic fluids, are coupled with positive europium anomalies and variable light REE depletion, which are more consistent with chloride complexation in hot (>250 °C) hydrothermal fluids. In this shallow sub-seafloor setting, thermal alteration of organic carbon in the immature, chemically reactive mudstones also had an important role in the evolution of fluid chemistry. Reduced sulphur generation via thermochemical reduction of Late Devonian seawater sulphate produced positive δ34S values in sulphide minerals (+7.5‰ to +19.5‰), coupled with a suite of volatile components (CO2, CH4, C1-C4 hydrocarbons, N2) trapped in Stage 2 quartz. Many of these geochemical features developed during the final stages of fluid ascent, in a system where the fluid cooled close to the site of mineralisation. Using this information, we have modelled the metal transporting capacity of the deep hydrothermal fluid, which even at modest salinities (6 wt.% NaCl) was high (≫100 ppm Pb, Zn), owing to the combined effects of high temperature and low pH (⩽4.5). Therefore in SHMS systems, enhanced geothermal gradients and rapid fluid ascent (with minimal fluid cooling) are considered to be the most important factors for transporting high concentrations of base metals to the site of mineralisation.
A multi proxy reconstruction of paleoproductivity of Cleland Lake British Columbia, Canada
NASA Astrophysics Data System (ADS)
Mihindukulasooriya, L. N.; Pompeani, D. P.; Ortiz, J. D.; Steinman, B. A.; Abbott, M. B.
2013-12-01
In small closed-basin lakes in semi arid regions, variations in precipitation/evaporation (P/E) balance affect the physical, biological, and chemical composition of the lake water and sediment. This study presents color reflectance, XRF derived elemental concentrations and δ18O values of carbonates (δ18Ocarb) in sediment cores from Cleland Lake, British Columbia to provide insight into paleolimnological variations during the past 7500 years. Principal Component (PC) 1 of the reflectance data, i.e, Illite+ sphalerite is used as a clay mineral proxy, and PC 4, diatoms+ cyanobacteria, is used as a paleoproductivity proxy. Lake paleoproductivity history is divided into three temporal periods, 400 to 2500 (denoted as P1), 2500 to 5000 (P2) and 5000 to 7500 (P3) calibrated years before present (Cal yr BP). Fe and Mn concentrations gradually increase during P3, reach high values during P2 and rapidly drop to the lowest values after 2600 Cal yr BP. Diatom abundances have a positive correlation with illite (r= 0.79, n=73 α=0.01) throughout the record. In contrast, negative correlations (table 1) exists between δ18Ocarb and diatom abundances during P2 and P3, indicating higher diatom abundance during wet periods. After 3000 cal yr BP, the correlation reverses (table 1), indicating low diatom abundance during wet periods. Variability in diatom abundances is greater than that of the δ18Ocarb values, indicating that factors other than the P/E balance affects phytoplankton abundance. P 1 is characterized by three periods (centered at 2500, 2100 and 1400 Cal yr BP) of predominantly low diatom abundance that occur simultaneously with low Mn and Cr concentrations. Low Mn and Cr levels may indicate intense reducing conditions, while the observed peaks in Ni and Cu concentration might indicate reducing conditions resulting from high rates of organic matter decomposition (Tribovillard et al., 2006). Contemporaneous with the abrupt δ18Ocarb depletion around 2600 Cal yr BP, trace metal concentrations (Fe, Cu, Ni and Zn) as well as nutrient (P, S) levels increase, suggesting a higher rate of groundwater inflow and mineral delivery. Despite these increases, diatom abundance remains low. This may indicate the competitive appearance of Cyanobacteria in place of diatoms. Three rapid increases in diatom abundances centered at 1500, 900 and 700 Cal yr BP are associated with peaks in Cr and δ18Ocarb. Cr enrichment and low Mn may indicate reducing conditions in the absence of free H2S (Tribovillard et al., 2006). Such conditions can develop due to restricted water mass renewal in a well stratified lake (Tribovillard et al., 2006). In contrast, around 900 Cal yr BP P, S and Si levels increase. Relatively high δ18Ocarb values at this time do not provide support for a groundwater associated inflow of nutrients to the lake. Therefore it is possible that this peak could have resulted from other climatic factors including higher wind speeds and a greater flux of fine clastic material.Table 1
NASA Astrophysics Data System (ADS)
Rottier, Bertrand; Kouzmanov, Kalin; Casanova, Vincent; Bouvier, Anne-Sophie; Baumgartner, Lukas P.; Wälle, Markus; Fontboté, Lluís
2018-01-01
Cerro de Pasco (Peru) is known for its large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) mineralization emplaced at shallow level, a few hundred meters below the paleo-surface, at the border of a large diatreme-dome complex. Porphyry-style veins crosscutting hornfels and magmatic rock clasts are found in the diatreme breccia and in quartz-monzonite porphyry dikes. Such mineralized veins in clasts allow investigation of high-temperature porphyry-style mineralization developed in the deep portions of magmatic-hydrothermal systems. Quartz in porphyry-style veins contains silicate melt inclusions as well as fluid and solid mineral inclusions. Two types of high-temperature (> 600 °C) quartz-molybdenite-(chalcopyrite)-(pyrite) veins are found in the clasts. Early, thin (1-2 mm), and sinuous HT1 veins are crosscut by slightly thicker (up to 2 cm) and more regular HT2 veins. The HT1 vein quartz hosts CO2- and sulfur-rich high-density vapor inclusions. Two subtypes of the HT1 veins have been defined, based on the nature of mineral inclusions hosted in quartz: (i) HT1bt veins with inclusions of K-feldspar, biotite, rutile, and minor titanite and (ii) HT1px veins with inclusions of actinolite, augite, titanite, apatite, and minor rutile. Using an emplacement depth of the veins of between 2 and 3 km (500 to 800 bar), derived from the diatreme breccia architecture and the supposed erosion preceding the diatreme formation, multiple mineral thermobarometers are applied. The data indicate that HT1 veins were formed at temperatures > 700 °C. HT2 veins host assemblages of polyphase brine inclusions, generally coexisting with low-density vapor-rich inclusions, trapped at temperatures around 600 °C. Rhyolitic silicate melt inclusions found in both HT1 and HT2 veins represent melt droplets transported by the ascending hydrothermal fluids. LA-ICP-MS analyses reveal a chemical evolution coherent with the crystallization of an evolved rhyolitic melt. Quartz from both HT1 and HT2 veins also contains secondary, low-temperature ( 300 °C) brine and aqueous fluid inclusions that record the cooling of the system. Both vein types are locally crosscut and/or reopened by a pre-diatreme polymetallic event consisting of pyrite, sphalerite with "chalcopyrite disease," galena, chalcopyrite, tetrahedrite-tennantite, and minor quartz. LA-ICP-MS analyses of mineral and high-temperature fluid inclusions hosted in HT1 and HT2 veins and in situ secondary-ion mass spectrometry oxygen isotope analyses of vein quartz indicate a magmatic signature for the mineralizing fluids with no major meteoric water input and allow reconstruction of the source and chemical evolution of fluids that formed these porphyry-style veins as snapshots of the early and deep mineralizations at Cerro de Pasco. This detailed study of the porphyry-type mineralization hosted in clasts offers a unique opportunity to reconstruct the late magmatic and early hydrothermal evolutions of porphyry mineralization underlying the world-class Cerro de Pasco epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) deposit.
Drieberg, Susan L.; Hagemann, Steffen G.; Huston, David L.; Landis, Gary; Ryan, Chris G.; Van Achterbergh, Esmé; Vennemann, Torsten
2013-01-01
The ~3240 Ma Panorama volcanic-hosted massive sulfide (VHMS) district is unusual for its high degree of exposure and low degree of postdepositional modification. In addition to typical seafloor VHMS deposits, this district contains greisen- and vein-hosted Mo-Cu-Zn-Sn mineral occurrences that are contemporaneous with VHMS orebodies and are hosted by the Strelley granite complex, which also drove VHMS circulation. Hence the Panorama district is a natural laboratory to investigate the role of magmatic-hydrothermal fluids in VHMS hydrothermal systems. Regional and proximal high-temperature alteration zones in volcanic rocks underlying the VHMS deposits are dominated by chlorite-quartz ± albite assemblages, with lesser low-temperature sericite-quartz ± K-feldspar assemblages. These assemblages are typical of VHMS hydrothermal systems. In contrast, the alteration assemblages associated with granite-hosted greisens and veins include quartz-topaz-muscovite-fluorite and quartz-muscovite (sericite)-chlorite-ankerite. These vein systems generally do not extend into the overlying volcanic pile. Fluid inclusion and stable isotope studies suggest that the greisens were produced by high-temperature (~590°C), high-salinity (38–56 wt % NaCl equiv) fluids with high densities (>1.3 g/cm3) and high δ18O (9.3 ± 0.6‰). These fluids are compatible with the measured characteristics of magmatic fluids evolved from the Strelley granite complex. In contrast, fluids in the volcanic pile (including the VHMS ore-forming fluids) were of lower temperature (90°–270°C), lower salinity (5.0–11.2 wt % NaCl equiv), with lower densities (0.88–1.01 g/cm3) and lower δ18O (−0.8 ± 2.6‰). These fluids are compatible with evolved Paleoarchean seawater. Fluids that formed the quartz-chalcopyrite-sphalerite-cassiterite veins, which are present within the granite complex near the contact with the volcanic pile, were intermediate in temperature and isotopic composition between the greisen and volcanic pile fluids (T = 240°–315°C; δ18O = 4.3 ± 1.5‰) and are interpreted to indicate mixing between the two end-member fluids. Evidence of mixing between evolved seawater and magmatic-hydrothermal fluid within the granite complex, together with the lack of evidence for a magmatic component in fluids from the volcanic pile, suggest partitioning of magmatic-hydrothermal from evolved seawater hydrothermal systems in the Panorama VHMS system. This separation is interpreted to result from either the swamping of a relatively small magmatic-hydro-thermal system by evolved seawater or density contrasts precluding movement of magmatic-hydrothermal fluids into the volcanic pile. Variability in the salinity of fluids in the volcanic pile, combined with evidence for mixing of low- and high-salinity fluids in the massive sulfide lens, is interpreted to indicate that phase separation occurred within the Panorama hydrothermal system. Although we consider this phase separation to have most likely occurred at depth within the system, as has been documented in modern VHMS systems, the data do not allow the location of the inferred phase separation to be determined.
Bacterial and Thermochemical Sulfate Reduction in Diagenetic Settings - Old and New Insights
NASA Astrophysics Data System (ADS)
Machel, H.
2006-12-01
The association of dissolved sulfate and hydrocarbons is thermodynamically unstable in virtually all diagenetic environments. Hence, redox-reactions occur, whereby sulfate is reduced by hydrocarbons either bacterially (bacterial sulfate reduction = BSR) or inorganically (thermochemical sulfate reduction = TSR). Based on empirical evidence, BSR and TSR occur in two mutually exclusive thermal regimes, i.e., low-T and high-T diagenetic environments, respectively. BSR is common in diagenetic settings at T = 0 - 80 ° C. Above this T range, almost all sulfate reducers cease to metabolize. Those few types of hyperthermophiles that can form H2S at higher T appear to be very rare and do not normally occur and/or metabolize in geologic settings that are otherwise conducive to BSR. TSR appears to be common in geologic settings at T = 100 - 140 ° C, but in some settings T up to 180 ° C appears to be necessary. TSR does not have a sharply defined, generally valid minimum T because the onset and rate of TSR are governed by several factors that vary from place to place, i.e., the composition of the available organic reactants, kinetic inhibitors and/or catalysts, anhydrite dissolution rates, wettability, as well as migration and diffusion rates of the major reactants. A well- defined, specific minimum T for TSR can be expected only where the reservoir conditions are fairly homogeneous on the scale of a field or a play. BSR is geologically instantaneous in most geologic settings. Rates of TSR are much lower, but still geologically significant. TSR may form sour gas reservoirs and/or MVT deposits in several tens of thousands to a few million years at T = 100 - 140 ° C. BSR and TSR may be exothermic or endothermic, depending mainly on the presence or absence of specific organic reactants. The main organic reactants for BSR are organic acids and other products of aerobic or fermentative biodegradation, and those for TSR are branched and n-alkanes, followed by cyclic and mono-aromatic species, in the gasoline range. Sulfate is derived almost invariably from the dissolution of gypsum and/or anhydrite, which may be primary or secondary deposits at or near the redox-reaction site(s). The products of BSR and TSR are similar, but their relative amounts vary widely and are determined by a number of locally variable factors, including availability of reactants, formation water chemistry, and wettability. The primary inorganic reaction products in both thermal regimes are H2S (HS-) and HCO3- (CO2). The presence of alkali earth metals often results in the formation of carbonates, particularly calcite and dolomite. Iron sulfides, galena, and sphalerite form as by-products of H2S generation, if the respective transition or base metals are present or transported to a BSR/TSR reaction site. Elemental sulfur may accumulate as a volumetrically significant net reaction product, usually when the system runs out of reactive hydrocarbons. Solid bitumen may form as a by-product of both BSR and TSR.
NASA Astrophysics Data System (ADS)
Romano, Elena; Bergamin, Luisa; Maggi, Chiara; Ausili, Antonella
2016-04-01
Benthic foraminifera are increasingly used to assess environmental quality of present and past marine environments. They are suitable for the study of ancient environments because their hard and small shells are preserved and abundant in sediment and an adequate number of them can be collected by small samples of sediment cores, supplying reliable data for a statistical approach. The study of foraminiferal assemblages, associated to sediment abiotic parameters, allows to define the anthropogenic impact along the time; reference conditions may be recognized in deep uncontaminated levels. The Sulcis Iglesiente Guspinese area (SW Sardinia, Italy) was affected in past times by intensive mining, which started in mid 19th century and ceased in 1990s. The marine area of Cala Domestica is located few kilometers from the mining district, where mainly galena and sphalerite were exploited. The area houses buildings for storage of minerals receives drainage material from mineral dumps determining a strong enrichment for several metals in the coastal sediments. Sediment core SI/69 was collected by means of vibrocorer in front of Cala Domestica beach, during a vast sampling survey aimed to environmental characterization of marine sediments. The core was subsampled in the laboratory, and a total of 28 levels were collected. Microfaunal, grain size and chemical (As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn) analyses were carried out on different aliquots of the same level. The quantitative analysis on benthic foraminifera was based on the count of at least 300 specimens per sample. Faunal parameters such as Foraminiferal Number (FN i.e. number of specimens / 1 g dry sediment) and species diversity (- index and H-index) were considered as potential indicators of environmental status. Principal Component Analysis (PCA) showed a group of strongly correlated metals (Ba, Cd, Cu, Hg, Mn, Pb and Zn), associated to the superficial samples. These elements displayed a typical profile along core depth, characterized by low steady concentration in the lower part of the core, and increased values in the upper 20 cm. This pattern, which displays for most elements the highest concentrations in the top level, may be considered as influenced by anthropogenic enrichment. Quantitative faunal data were compared with concentrations by means of Canonical Correspondence Analysis (CCA) to highlight the effects of contamination on biota. It highlighted the pollution-tolerant character of some foraminiferal species, which are nearly exclusively present in the upper 20 cm core interval. Moreover, CCA demonstrated that FN was negatively affected by the anthropogenically enriched metals. Foraminiferal assemblages do not show major changes along core depth and high species diversity would suggest, in general, a good environmental status through time. Nevertheless, the comparison of assemblages from the contaminated upper core interval with reference conditions of the pre impacted interval, reveals that heavy metal pollution determined the increase of the pollution-tolerant taxa and a great decrease of foraminiferal abundance. Consequently, a comprehensive degradation of the ecological status referable to mining activity and dumping was recognized in this study.
Bove, Dana J.; Caine, Jonathan S.; Lowers, Heather
2012-01-01
The surface and subsurface geology, hydrothermal alteration, and mineralogy of the Handcart Gulch area was studied using map and drill core data as part of a multidisciplinary approach to understand the hydrology and affects of geology on acid-rock drainage in a mineralized alpine watershed. Handcart Gulch was the locus of intense hydrothermal alteration that affected an area of nearly 3 square kilometers. Hydrothermal alteration and accompanied weak mineralization are spatially and genetically associated with small dacite to low-silica rhyolite stocks and plugs emplaced about 37-36 Ma. Felsic lithologies are commonly altered to a quartz-sericite-pyrite mineral assemblage at the surface, but alteration is more variable in the subsurface, ranging from quartz-sericite-pyrite-dominant in upper core sections to a propylitic variant that is more typical in deeper drill core intervals. Late-stage, hydrothermal argillic alteration [kaolinite and(or) smectite] was superimposed over earlier-formed alteration assemblages in the felsic rocks. Smectite in this late stage assemblage is mostly neoformed resulting from dissolution of chlorite, plagioclase, and minor illite in more weakly altered rocks. Hydrothermally altered amphibolites are characterized by biotitic alteration of amphibole, and subsequent alteration of both primary and secondary biotite to chlorite. Whereas pyrite is present both as disseminations and in small veinlets in the felsic lithologies, it is mostly restricted to small veinlets in the amphibolites. Base-metal sulfides including molybdenite, chalcopyrite, sphalerite, and galena are present in minor to trace amounts in the altered rocks. However, geologic data in conjunction with water geochemical studies indicate that copper mineralization may be present in unknown abundance in two distinct areas. The altered rocks contain an average of 8 weight percent fine pyrite that is largely devoid of metals in the crystal structure, which can be a significant source of trace metals in other areas with acid rock drainage. Thus, elevated base-metal concentrations in the trunk stream and discrete springs in the study area, as determined in previous studies, are likely derived from discrete metal-rich sources, rather than the abundant pyrite veins or disseminations. Pyrite is oxidized in nearly all outcrops examined. Drill core data show that zones of pyrite oxidation range in depth from 100 meters below the surface at higher elevations to just a few meters depth at the lowest elevations in the study area. However, discrete pyrite oxidation zones are present in drill core to depths of several hundred meters below the pervasive near-surface oxidation zones. These deeper discrete oxidation zones, which are present where fresh pyrite predominates, are spatially associated with fractures, small faults, and breccias. Quartz-sericite-pyrite-altered rocks containing unoxidized pyrite likely have the highest acid-generating capacity of all alteration assemblages in the study area. Hydrothermal alteration has left these rocks base-cation leached and thus acid-neutralizing potential is negligible. In contrast, propylitic-altered felsic rocks commonly contain trace to minor calcite and abundant chlorite, which provide some amount of acid-neutralization despite the presence of a few percent pyrite.
NASA Astrophysics Data System (ADS)
Anikina, E. Yu.; Bortnikov, N. S.; Klubnikin, G. K.; Gamyanin, G. N.; Prokof'ev, V. Yu.
2016-05-01
The succession of mineral assemblages, chemistry of gangue and ore minerals, fluid inclusions, and stable isotopes (C, O, S) in minerals have been studied in the Mangazeya silver-base-metal deposit hosted in terrigenous rocks of the Verkhoyansk Fold-Thrust Belt. The deposit is localized in the junction zone of the Kuranakh Anticlinorium and the Sartanga Synclinorium at the steep eastern limb of the Endybal Anticline. The deposit is situated at the intersection of the regional Nyuektame and North Tirekhtyakh faults. Igneous rocks are represented by the Endybal massif of granodiorite porphyry 97.8 ± 0.9 Ma in age and dikes varying in composition. One preore and three types of ore mineralization separated in space are distinguished: quartz-pyrite-arsenopyrite (I), quartz-carbonate-sulfide (II), and silver-base-metal (III). Quartz and carbonate (siderite) are predominant in ore veins. Ore minerals are represented by arsenopyrite, pyrite, sphalerite, galena, fahlore, and less frequent sulfosalts. Three types of fluid inclusions in quartz differ in phase compositions: two- or three-phase aqueous-carbon dioxide (FI I), carbon dioxide gas (FI II), and two-phase (FI III) containing liquid and a gas bubble. The homogenization temperature and salinity fall within the ranges of 367-217°C and 13.8-2.6 wt % NaCl equiv in FI I; 336-126°C and 15.4-0.8 wt % NaCl equiv in FI III. Carbon dioxide in FI II was homogenized in gas at +30.2 to +15.3°C and at +27.2 to 29.0°C in liquid. The δ34S values for minerals of type I range from-1.8 to +4.7‰ (V-CDT); of type II, from-7.4 to +6.6‰; and of type III, from-5.6 to +7.1‰. δ13C and δ18O vary from-7.0 to-6.7‰ (V-PDB) and from +16.6 to +17.1 (V-SMOW) in siderite-I; from-9.1 to-6.9‰ (V-PDB) and from +14.6 to +18.9 (V-SMOW) in siderite-II; from-5.4 to-3.1‰ (V-PDB) and from +14.6 to +19.5 (V-SMOW) in ankerite; and from-4.2 to-2.9‰ (V-PDB) and from +13.5 to +16.8 (V-SMOW) in calcite. The data on mineral assemblages, fluid inclusions, and ratios of stable isotopes allow us to speak about the formation of the Mangazeya deposit in relation to the activity of the hydrothermal-magmatic system. The latter combines emplacement of subvolcanic granitic stocks and involvement of fluids variable in salinity and temperature in ore deposition zone. The fluids released from crystallizing felsic magma and were formed in a convective cell by heating of meteoric and marine waters. The mechanism of ore deposition is related to phase separation (boiling) and mixing of fluids.
Bargar, K.E.
1991-01-01
The Platanares geothermal area in western Honduras consists of more than 100 hot springs that issue from numerous hot-spring groups along the banks or within the streambed of the Quebrada de Agua Caliente (brook of hot water). Evaluation of this geothermal area included drilling a 650-m deep PLTG-1 drill hole which penetrated a surface mantling of stream terrace deposits, about 550 m of Tertiary andesitic lava flows, and Cretaceous to lower Tertiary sedimentary rocks in the lower 90 m of the drill core. Fractures and cavities in the drill core are partly to completely filled by hydrothermal minerals that include quartz, kaolinite, mixed-layer illite-smectite, barite, fluorite, chlorite, calcite, laumontite, biotite, hematite, marcasite, pyrite, arsenopyrite, stibnite, and sphalerite; the most common open-space fillings are calcite and quartz. Biotite from 138.9-m depth, dated at 37.41 Ma by replicate 40Ar/39 Ar analyses using a continuous laser system, is the earliest hydrothermal mineral deposited in the PLTG-1 drill core. This mid-Tertiary age indicates that at least some of the hydrothermal alteration encountered in the PLTG-1 drill core occured in the distant past and is unrelated to the present geothermal system. Furthermore, homogenization temperatures (Th) and melting-point temperatures (Tm) for fluid inclusions in two of the later-formed hydrothermal minerals, calcite and barite, suggest that the temperatures and concentration of dissolved solids of the fluids present at the time these fluid inclusions formed were very different from the present temperatures and fluid chemistry measured in the drill hole. Liquid-rich secondary fluid inclusions in barite and caicite from drill hole PLTG-1 have Th values that range from about 20??C less than the present measured temperature curve at 590.1-m depth to as much as 90??C higher than the temperature curve at 46.75-m depth. Many of the barite Th measurements (ranging between 114?? and 265??C) plot above the reference surface boiling-point curve for pure water assuming hydrostatic conditions; however, the absence of evidence for boiling in the fluid inclusions indicates that at the time the minerals formed, the ground surface must have been at least 80 m higher than at present and underwent stream erosion to the current elevation. Near-surface mixed-layer illite-smectite is closely associated with barite and appears to have formed at about the same temperature range (about 120?? to 200??C) as the fluid-inclusion Th values for barite. Fluid-inclusion Th values for calcite range between about 136?? and 213??C. Several of the calcite Th values are significantly lower than the present measured temperature curve. The melting-point temperatures (Tm) of fluid-inclusion ice yield calculated salinities, ranging from near zero to as much as 5.4 wt. % NaCl equivalent, which suggest that much of the barite and calcite precipitated from fluids of significantly greater salinity than the present low salinity Platanares hot-spring water or water produced from the drill hole. ?? 1991.
The Case of Carpathian (Transylvanian) Gold and its Use for Archaeological Items
NASA Astrophysics Data System (ADS)
Stan, D.; Constantinescu, B.; Vasilescu, A.; Radtke, M.; Reinholz, U.; Pop, D.; Ionescu, C.
2009-04-01
Romania was one of Europe's main gold-producing areas since the antiquity, especially through the ore deposits in the "Golden Quadrilateral" of the Western Carpathians. The Babeş-Bolyai University in Cluj-Napoca hosts a gold collection consisting of about 500 samples, most of them from Roşia Montană. The geochemical investigation of Romanian gold by using SR-XRF and micro-PIXE is currently in progress; some preliminary results point to interesting features. The goal of the study is to verify if Transylvanian gold was used to manufacture Romanian archaeological objects. This is realized by using information related to trace elements: Sb, Te, Pb - recognized fingerprints for Carpathian Mountains mines and Sn characteristic for the panned river-bed (alluvional) gold. To solve these issues, samples (grains, nuggets, fine gold "sand") from various Transylvanian mines and rivers and some very small (few milligrams) fragments of archaeological objects are measured. Another outcome of this SR-XRF experiment is to obtain the elemental characterization (Au, Ag and Cu) of representative gold mines, subject of interest for the assignement of any other archaeological artifacts to one of the Central European gold sources. During the experiment, point spectra for 22 natural gold samples and 18 "micronic" samples from archaeological objects were acquired at 34 keV excitation SR energy, using a spatially resolved SR-XRF set-up mounted for analyses at the hard X-ray beam line - BAMline at BESSY, Berlin. A summary for the characterization of Transylvanian native gold is the following: high (8 - 30%) Ag amounts and low (0.2 - 1%) Cu amounts; placer deposits contain as fingerprint Sn (150-300 ppm) - most probably from river bed cassiterite; primary deposits present as fingerprints Te (200-2000 ppm), Sb (150-300 ppm) - however, the samples are very inhomogeneous. The micro-PIXE experiment was performed at the AN 2000 Van de Graaff accelerator of Laboratori Nazionali di Legnaro. Elemental maps of gold samples were obtained, complemented by nuclear microprobe point analyses in selected areas of the mapped gold crystals. At Roşia Montană, the mapping evidenced a peculiar microfabric consisting of mm-sized laths of a Zn-S rich phase (with minor Cu and Fe). Au content shows a wide compositional range: 36-57%. A clear chemical inhomogeneity of the Au/Ag ratio, as well as of the local concentration of other elements (Cu, As, Sb, Te, Pb, Fe) was noticed at submilimeter scale. The presence of associated mineral phases (such as Cu, Ag, chalcopyrite, galena, sphalerite, arsenopyrite, pyrite/marcasite and non-metallic minerals) at microscopic scale could be thus illustrated. As concerning the archaeological samples, for "koson" dacian coins, the type "with monogram" is made from refined (more than 97%) gold with no Sb, Te or Sn traces (remelted gold) and the type "without monogram" is clearly made from alluvial gold, partially combined with primary Transylvanian gold (Sn and Sb traces detected). The greek "pseudolysimachus" type staters (contemporary with "kosons") are made from refined remelted gold (no Sn, Sb, Te presence).
NASA Astrophysics Data System (ADS)
Jin, Xiao-ye; Li, Jian-wei; Hofstra, Albert H.; Sui, Ji-xiang
2017-08-01
The Xiahe-Hezuo district in the West Qinling orogen contains numerous Au-(As-Sb) and Cu-Au-(W) deposits. The district is divided into eastern and western zones by the Xiahe-Hezuo Fault. The western zone is exposed at a shallow level and contains sediment-hosted disseminated Au-(As-Sb) deposits, whereas the eastern zone is exposed at a deeper level and contains Cu-Au-(W) skarn and lode gold deposits within or close to granitic intrusions. The Laodou gold deposit in the eastern zone consists of auriferous quartz-sulfide-tourmaline and minor quartz-stibnite veins that are structurally controlled by fault zones transecting the Laodou quartz diorite porphyry stock and enveloped by potassic and phyllic alteration. Both the veins and alteration halos commonly contain quartz, sericite, tourmaline, pyrite, and arsenopyrite, with minor galena, sphalerite, chalcopyrite, tetrahedrite, and enargite. Gold occurs mainly as invisible gold in pyrite or arsenopyrite and locally as inclusions less than 50 μm in diameter. The zircon U-Pb age of 247.6 ± 1.3 Ma (2 σ) on the host quartz diorite porphyry and the sericite 40Ar/39Ar plateau ages of 249.1 ± 1.6 and 249.0 ± 1.5 Ma (2 σ) on two ore-related hydrothermal sericite samples are within analytical errors of one another. At the formation temperature (275 °C) inferred from microthermometric measurements of fluid inclusion, sericite and tourmaline yield calculated δDH2O values of -70 to -45‰ and δ 18OH2O of 5.8 to 9.7‰, while quartz yields calculated δ 18OH2O values of 5.1˜5.7‰. Hydrothermal tourmaline in quartz-sulfide-tourmaline veins has δ 11B of -11.2 to -0.9‰ (mean of -6.3‰) that are similar to the values of magmatic tourmaline (-8.9 to -5.5‰ with a mean of -6.8‰) in the host quartz diorite porphyry. The δ 34S values of sulfide minerals range from -5.9 to +5.8‰ with a mean of -0.6‰ that is typical of magmatic sulfur. Pyrite from hydrothermally altered quartz diorite porphyry and quartz-sulfide-tourmaline veins have relatively homogeneous lead isotopic compositions, compatible with granitic intrusions in the district. The geochronological and isotopic data combined support a magmatic origin for the Laodou gold deposit, most likely formed from fluids exsolved from the Laodou quartz diorite porphyry or associated intrusive phases at deeper levels beneath the stock. Orogenic and Carlin-like gold deposits in the West Qinling orogen have been commonly thought to have formed from metamorphic fluids. This study, however, highlights the role of magmatic-derived fluids in the formation of lode gold deposits. Synthesis of geochronological, geological, and geochemical data on magmatic rocks and ore deposits in and surrounding the Xiahe-Hezuo district indicates that gold mineralization predominantly occurred within a subduction-related magmatic arc prior to collision between the Yangtze and North China cratons that produced the West Qinling orogen.
NASA Astrophysics Data System (ADS)
Qiu, Kun-Feng; Deng, Jun; Taylor, Ryan D.; Song, Kai-Rui; Song, Yao-Hui; Li, Quan-Zhong; Goldfarb, Richard J.
2016-05-01
The NWW-striking North Qilian Orogenic Belt records the Paleozoic accretion-collision processes in NW China, and hosts Paleozoic Cu-Pb-Zn mineralization that was temporally and spatially related to the closure of the Paleo Qilian-Qinling Ocean. The Wangdian Cu deposit is located in the eastern part of the North Qilian Orogenic Belt, NW China. Copper mineralization is spatially associated with an altered early Paleozoic porphyritic granodiorite, which intruded tonalites and volcaniclastic rocks. Alteration zones surrounding the mineralization progress outward from a potassic to a feldspar-destructive phyllic assemblage. Mineralization consists mainly of quartz-sulfide stockworks and disseminated sulfides, with ore minerals chalcopyrite, pyrite, molybdenite, and minor galena and sphalerite. Gangue minerals include quartz, orthoclase, biotite, sericite, and K-feldspar. Zircon LA-ICPMS U-Pb dating of the ore-bearing porphyritic granodiorite yielded a mean 206Pb/238U age of 444.6 ± 7.8 Ma, with a group of inherited zircons yielding a mean U-Pb age of 485 ± 12 Ma, consistent with the emplacement age (485.3 ± 6.2 Ma) of the barren precursor tonalite. Rhenium and osmium analyses of molybdenite grains returned model ages of 442.9 ± 6.8 Ma and 443.3 ± 6.2 Ma, indicating mineralization was coeval with the emplacement of the host porphyritic granodiorite. Rhenium concentrations in molybdenite (208.9-213.2 ppm) suggest a mantle Re source. The tonalities are medium-K calc-alkaline. They are characterized by enrichment of light rare-earth elements (LREEs) and large-ion lithophile elements (LILEs), depletion of heavy rare-earth elements (HREEs) and high-field-strength elements (HFSEs), and minor negative Eu anomalies. They have εHf(t) values in the range of +3.6 to +11.1, with two-stage Hf model ages of 0.67-1.13 Ga, suggesting that the ca. 485 Ma barren tonalites were products of arc magmatism incorporating melts from the mantle wedge and the lithosphere. In contrast, the 40-m.y.-younger ore-bearing porphyritic granodiorite is sub-alkaline and peraluminous. They are enriched in LREEs and LILEs, depleted in HFSEs, and show weak negative Eu anomalies. They display εHf(t) values of captured or inherited zircons in the range of +8.5 to +10.0, and younger two-stage Hf model ages of 0.78 Ga and 0.86 Ga, similar to those of ca. 485 Ma tonalite. The ca. 445 Ma zircons have εHf(t) values of -2.1 to +9.9, with two-stage Hf model ages of 0.75-1.27 Ga. Moreover, they have relatively high oxygen fugacity than that of the precursor barren tonalite. The ca. 445 Ma magmas at Wangdian thus formed in a subduction setting, and incorporated melts from the subduction-modified lithosphere that had previously been enriched by additions of chalcophile and siderophile element-rich materials by the earlier magmatism and metasomatism during the Paleo Qilian-Qinling Ocean subduction event.
NASA Astrophysics Data System (ADS)
Majzlan, Juraj; Berkh, Khulan; Kiefer, Stefan; Koděra, Peter; Fallick, Anthony E.; Chovan, Martin; Bakos, František; Biroň, Adrián; Ferenc, Štefan; Lexa, Jaroslav
2018-02-01
In this contribution, we report new data on mineralogy, alteration patterns, geochemistry, fluid properties and source of fluids for the deposit Nová Baňa, one of the smaller epithermal deposits in the Middle Miocene Štiavnica andesite stratovolcano (Western Carpathians, Slovakia). Ore veins and the associated rocks were studied in samples from outcrops and old mines, grab samples, and bore holes from the central part of the deposit (ore structures Althandel, Jozef, Jakub, Vavrinec), northern part (Freischurf), SE part (Gupňa) and SW part (Šibeničný vrch). Pervasive hydrothermal alteration transformed the rock-forming minerals into a mixture of adularia and fine-grained quartz, with lesser amount of pyrite, Ti oxides and Fe oxides. This assemblage was further altered to omnipresent interstratified illite/smectite that was used in this study as a geothermometer, corroborating the results from the fluid inclusion work. Ore minerals comprise predominantly pyrite, sphalerite, galena but all sulfides are relatively sparse in the samples studied. Minerals of precious metals are electrum, Ag-tetrahedrite, acanthite, members of the polybasite-pearceite and pyrargyrite-proustite solid solution, and rare miargyrite, Hg-Ag tetrahedrite, and diaphorite. In the central part, we have found also some stibnite. In the SE part of the deposit, acanthite, uytenbogaardtite, and petrovskaite occur and seem to be related to supergene enrichment of the ores. In bulk ore samples, Zn usually dominates over Pb and Cu. The average Ag:Au ratio for the entire deposit is 64:1. The concentrations of precious metals in the grab samples reach maxima of 50 ppm Au and 570 ppm Ag in the SE part and 116 ppm Au and 1110 ppm Ag in the central part of the deposit. Fluid inclusions show signs of trapping of a heterogeneous fluid. In the central, northern and SE parts of the deposit, homogenization temperatures of 190-260 °C and consistently low salinities of <5 wt% NaCl eq were recorded. In the SW part, primary fluid inclusions gave homogenization temperatures of 160-180 °C and similar low salinities. The secondary inclusions, however, show salinities up to 24 wt% NaCl eq., interpreted as fluid boiling almost to dryness. Isotopic composition of quartz and clay minerals is recalculated to fluid composition of -5.6 to -0.6 ‰ δ18Ofluid and -80 to -36 ‰ δDfluid, indicating mixed character of hydrothermal fluids falling between the compositions of magmatic and meteoric waters, with predominance of meteoric waters. Assuming hydrostatic pressure in the fluids, the measured data suggest paleodepths of ore formation of 50-170 m in the SW part of the ore deposit, 130-420 m in the SE and N parts, and a range of 120-470 m for the central part. These observations, comparison with other epithermal deposits in the Central Slovak volcanic field, and additional data from published literature show that Nová Baňa is a low- to intermediate sulfidation epithermal deposit, genetically associated to late rhyolitic volcanic activity in this area.
NASA Astrophysics Data System (ADS)
Dietrich, Andreas; Gutierrez, Ronald; Nelson, Eric P.; Layer, Paul W.
2012-03-01
The San José district is located in the northwest part of the Deseado massif and hosts a number of epithermal Ag-Au quartz veins of intermediate sulfidation style, including the Huevos Verdes vein system. Veins are hosted by andesitic rocks of the Bajo Pobre Formation and locally by rhyodacitic pyroclastic rocks of the Chon Aike Formation. New 40Ar/39Ar constraints on the age of host rocks and mineralization define Late Jurassic ages of 151.3 ± 0.7 Ma to 144.7 ± 0.1 Ma for volcanic rocks of the Bajo Pobre Formation and of 147.6 ± 1.1 Ma for the Chon Aike Formation. Illite ages of the Huevos Verdes vein system of 140.8 ± 0.2 and 140.5 ± 0.3 Ma are 4 m.y. younger than the volcanic host rock unit. These age dates are among the youngest reported for Jurassic volcanism in the Deseado massif and correlate well with the regional context of magmatic and hydrothermal activity. The Huevos Verdes vein system has a strike length of 2,000 m, with several ore shoots along strike. The vein consists of a pre-ore stage and three main ore stages. Early barren quartz and chalcedony are followed by a mottled quartz stage of coarse saccharoidal quartz with irregular streaks and discontinuous bands of sulfide-rich material. The banded quartz-sulfide stage consists of sulfide-rich bands alternating with bands of quartz and bands of chlorite ± illite. Late-stage sulfide-rich veinlets are associated with kaolinite gangue. Ore minerals are argentite and electrum, together with pyrite, sphalerite, galena, chalcopyrite, minor bornite, covellite, and ruby silver. Wall rock alteration is characterized by narrow (< 3 m) halos of illite and illite/smectite next to veins, grading outward into propylitic alteration. Gangue minerals are dominantly massive quartz intergrown with minor to accessory adularia. Epidote, illite, illite/smectite, and, preferentially at deeper levels, Fe-chlorite gangue indicate near-neutral pH hydrothermal fluids at temperatures of >220°C. Kaolinite occurring with the late sulfide-rich veinlet stage indicates pH < 4 and a temperature of <200°C. The Huevos Verdes system has an overall strike of 325°, dipping on average 65° NE. The orientations of individual ore shoots are controlled by vein strike and intersecting north-northwest-striking faults. We propose a structural model for the time of mineralization of the San José district, consisting of a conjugate shear pair of sinistral north-northwest- and dextral west-northwest-striking faults that correspond to R and R' in the Riedel shear model and that are related to master faults (M) of north-northeast-strike. Veins of 315° strike can be interpreted as nearly pure extensional fractures (T). Variations in vein strike predict an induced sinistral shear component for strike directions of >315°, whereas strike directions of <315° are predicted with an induced dextral strike-slip movement. The components of the structural model appear to be present on a regional scale and are not restricted to the San José district.
NASA Astrophysics Data System (ADS)
Sack, Richard O.
2000-11-01
An updated thermodynamic database for Ag 2S-Cu 2S-ZnS-Sb 2S 3-As 2S 3 sulfides and sulfosalts applicable to temperatures above 119°C is developed to calculate phase relations for polybasite-pearceite- and fahlore-bearing assemblages. It is based on pre-existing and new constraints on activity-composition, Ag-Cu and As-Sb partitioning, and other relations, and on experiments (200-300°C, evacuated silica tubes) conducted to define the stability of the polybasite-pearceite [(Ag 1- x,Cu x) 16(Sb 1- y,As y) 2S 11] + ZnS sphalerite assemblage with respect to assemblages containing (Ag,Cu) 2S sulfides coexisting with (Cu, Ag) 10Zn 2(Sb,As) 4S 13 fahlore sulfosalts. It was found that the thermodynamics of mixing of bcc- and hcp-(Ag,Cu) 2S solutions, which are fast-ion conductors, may be described by using site multiplicities of metals α Ag,Cu > 2 and temperature-dependent regular solution parameters. We obtained estimates for the Gibbs energies of formation for Ag 16Sb 2S 11 and Cu 16Sb 2S 11 polybasite endmembers from the simple sulfides (Ag 2S, Cu 2S, and Sb 2S 3) of -30.79 and -4.07 kJ/gfw at 200°C, and -32.04 and -0.59 kJ/gfw at 400°C, respectively, that are about one half kJ/gfw more positive and about 6 kJ/gfw more negative than those estimated by Harlov and Sack (1995b). The corresponding estimates for formation energies of Ag 10Zn 2Sb 4S 13 and Cu 10Zn 2Sb 4S 13 fahlores (-20.29 and -105.29 kJ/gfw at 200°C and -23.72 and -105.76 kJ/gfw at 400°C) are comparable to, and roughly 110 kJ/gfw more positive than, the corresponding estimates of Ebel and Sack (1994). We also determined that the Gibbs energies of the As-Sb exchange reactions: 1/4Ag 10Zn2Sb4S13+1/2Ag 16As2S11=1/2Ag 16Sb2S11+1/4Ag 10Zn2As4S13Sb-fahlorepearceitepolybasiteAs-fahlore and Ag3SbS3+1/2Ag 16As2S11=1/2Ag 16Sb2S11+Ag3AsS3pyrargyritepearceitepolybasiteproustite are, respectively, 8.75 and 0.40 kJ/gfw in the range 150-350°C, and these predictions are consistent with As-Sb partitioning relations observed in nature and produced in laboratory studies. Finally, we obtain estimates for the Gibbs energies of formation of Cu 10Fe 2Sb 4S 13 and Ag 10Fe 2Sb 4S 13 fahlores (-63.92 and +11.46 kJ/gfw at 200°C and -75.73 and -3.31 kJ/gfw at 400°C).
Mobility of gold during metamorphism of the Dalradian in Scotland
NASA Astrophysics Data System (ADS)
Pitcairn, I. K.; Skelton, A. D. L.; Wohlgemuth-Ueberwasser, C. C.
2015-09-01
Mobility of Au and related metals during metamorphism has been suggested to be the source of metals enriched in orogenic Au deposits. This study investigates the mobility of Au, As, and Sb during metamorphism of the Dalradian metasedimentary rocks of Scotland. The metamorphic processes in the Dalradian of Scotland are extremely well studied, and the terrane is an ideal area to investigate mobility of these metals. Our results show that of the 25 major and trace elements analysed, only Au, As, Sb, S and volatile contents as shown by loss on ignition (LOI) values show systematic variation with the metamorphic grade of the samples. Average Au concentrations decrease from 1.1 ± 0.55 ppb and 0.72 ± 0.34 ppb in chlorite and biotite zone rocks down to 0.4 ± 0.22 ppb and 0.34 ± 0.13 ppb in kyanite and sillimanite zone rocks. Average As concentrations decrease from 4.8 ppm (range 0.5 to 17.8 ppm) and 1.96 ± 1.9 ppm in chlorite and biotite zone rocks down to 0.24 ± 0.15 ppm and 0.2 ± 0.12 ppm in kyanite and sillimanite zone rocks. Average Sb concentrations decrease from 0.18 ± 0.15 ppm and 0.11 ± 0.10 ppm in chlorite and biotite zone rocks down to 0.04 ± 0.02 ppm in both kyanite and sillimanite zone rocks. Sulphur and LOI concentrations also show significant decreases. Mass balance calculations indicate that compared to chlorite and biotite zone samples, sillimanite zone samples have an average mass loss of 62 ± 14%, 94 ± 4% and 74 ± 14% for Au, As, and Sb respectively. Every 1 km3 of chlorite-biotite zone mixed psammitic-pelitic protolith rock that is metamorphosed to sillimanite zone conditions would release 1.5 t Au, 8613 t As, 270 t Sb, and 1.02 Mt S. The mobility of these elements is strongly controlled by the paragenesis of sulphide minerals. Pyrite, sphalerite, galena and cobaltite (as well as gersdorffite) decrease in abundance with increasing metamorphic grade in the Dalradian metasedimentary rocks. A critical aspect of the sulphide paragenesis is the transition of pyrite to pyrrhotite. This transition is complete by mid greenschist facies in the Loch Lomond samples but is more gradual at Glen Esk occurring between biotite and sillimanite zones. The Au, As, and Sb content of the sulphide assemblage also decreases with increasing metamorphic grade, and we suggest that this is a controlling factor on the mobility of these metals from the Dalradian metasedimentary rocks during metamorphism. Chlorite may be an important host mineral for As in the greenschist facies rocks. Breakdown of chlorite indirectly drives the mobility of Au, As, and Sb, as this produces the bulk of metamorphic fluid that drives transition between pyrite and pyrrhotite. We suggest that there is potential for significant undiscovered mineralisation in the Central and SW Highlands of Scotland. However, as the total mass of gold mobilised is lower than observed in other metasedimentary terranes such as the Otago and Alpine Schist's, New Zealand, very efficient fluid focussing and trapping mechanisms would be required to form large deposits in the Dalradian of Scotland.
NASA Astrophysics Data System (ADS)
Magnall, J. M.; Gleeson, S. A.; Stern, R. A.; Newton, R. J.; Poulton, S. W.; Paradis, S.
2016-05-01
Highly positive δ34S values in sulphide minerals are a common feature of shale hosted massive sulphide deposits (SHMS). Often this is attributed to near quantitative consumption of seawater sulphate, and for Paleozoic strata of the Selwyn Basin (Canada), this is thought to occur during bacterial sulphate reduction (BSR) in a restricted, euxinic water column. In this study, we focus on drill-core samples of sulphide and barite mineralisation from two Late Devonian SHMS deposits (Tom and Jason, Macmillan Pass, Selwyn Basin), to evaluate this euxinic basin model. The paragenetic relationship between barite, pyrite and hydrothermal base metal sulphides has been determined using transmitted and reflected light microscopy, and backscatter electron imaging. This petrographic framework provides the context for in-situ isotopic microanalysis (secondary ion mass spectrometry; SIMS) of barite and pyrite. These data are supplemented by analyses of δ34S values for bulk rock pyrite (n = 37) from drill-core samples of un-mineralised (barren), siliceous mudstone, to provide a means by which to evaluate the mass balance of sulphur in the host rock. Three generations of barite have been identified, all of which pre-date hydrothermal input. Isotopically, the three generations of barite have overlapping distributions of δ34S and δ18O values (+22.5‰ to +33.0‰ and +16.4‰ to +18.3‰, respectively) and are consistent with an origin from modified Late Devonian seawater. Radiolarian tests, enriched in barium, are abundant within the siliceous mudstones, providing evidence that primary barium enrichment was associated with biologic activity. We therefore propose that barite formed following remobilisation of productivity-derived barium within the sediment, and precipitated within diagenetic pore fluids close to the sediment water interface. Two generations of pyrite are texturally associated with barite: framboidal pyrite (py-I), which has negative δ34S values (-23‰ to -28‰; n = 9), and euhedral pyrite (py-II), which has markedly more positive δ34S values (+8‰ to +26‰; n = 86). We argue that stratiform pyrite and barite developed along diagenetic redox fronts, where the isotopic relationships (δ34Spyrite ≈ δ34Sbarite) are explained by anaerobic oxidation of methane coupled to sulphate reduction (AOM-SR). Furthermore, the relatively narrow distribution of δ34Sbarite values is consistent with an open system model of sulphate reduction, in which reduced sulphur generation occurred with a reduced isotopic fractionation (ε34S = <15‰) linked to higher rates of sulphate reduction and AOM-SR. Importantly, hydrothermal sulphides (pyrite, sphalerite and galena) all post-date this diagenetic barite-pyrite assemblage, and textural and mineralogical evidence indicates barite replacement to be an important process during hydrothermal mineralisation. Neither the textures nor the documented isotopic relationships can be produced by processes operating in a euxinic water column, which represents a major departure from the conventional model for SHMS formation at Macmillan Pass. We suggest that positive δ34S values in sulphides, a common feature of SHMS systems both in the Selwyn Basin and throughout the geologic record, could be linked to AOM-SR. At Macmillan Pass, positive δ34Spyrite values developed during open system diagenesis, which was critical for rapid sulphur cycling and the development of an effective metal trap.
Grauch, Richard I.; Desborough, George A.; Meeker, Gregory P.; Foster, A.L.; Tysdal, Russell G.; Herring, J. R.; Lowers, Heather A.; Ball, B. A.; Zielinski, Robert A.; Johnson, E.A.
2004-01-01
The Meade Peak Phosphatic Shale Member of the Permian Phosphoria Formation hosts the ore mined by the phosphate industry of southeast Idaho. It also hosts environmentally sensitive elements (ESE) such as Se, As, Hg, Ni, Cd, Zn, and Cr. Primary chemistry, elemental distribution patterns, and mineralogy within the Meade Peak were modified by element migration and possibly the introduction of elements. Fluids moved within the Meade Peak throughout its history, although the passage of fluids was highly variable in space and time, resulting in small domains of different rock chemistry and different mineralogy. Timing of major events affecting the Meade Peak and mineral habit are used to differentiate among detrital, diagenetic, epigenetic, and supergene mineral assemblages. Cross-cutting relationships among minerals are too rare to provide much paragenetic infor- mation. Carbonate fluorapatite (CFA) occurs in several forms, but dominantly as pelloids, some of which may have formed in situ during diagenesis. The other volumetrically signifi- cant form of CFA is interstitial cement that formed during diagenesis. Beginning during diagenesis and continuing intermittently, multiple generations of carbonate (dolomite and calcite) formed overgrowths and texturally complex carbonate cements. Movement and precipitation of silica followed a similar pattern. The ammonium feldspar buddingtonite, which generally rims orthoclase, also formed during diagenesis. Bacteria apparently played a significant role during diagenesis as well as during supergene processes, resulting in extreme fractionation of S isotopes and the possible bacterially mediated formation of minerals such as glauconite and sphalerite.Catagenesis, apparently culminating in oil generation, was the last significant diagenetic change. Thrusting accompanied by fluid (oil and brine) migration began during catagenesis in the Late Jurassic or Cretaceous and continued into the early Eocene.Fluorite ± carbonate ± barite± bitumen veins formed as a result of brittle deformation and accompanying fluid movement. This fracturing event may have been associated with a period of extension and normal faulting (Neogene to Holocene). Passage of the Yellowstone hot spot to the north of the area during the Neogene is marked by silicic domes and basaltic flows. The enrichment of Hg in fracture coatings might be the result of deposition from warm fluids associated with the emplacement of the silicic domes or a generally elevated, regional thermal gradient associated with the volcanism.Many of the fracture systems are still open and continue to provide fluid pathways that are the primary depositional sites for a wide variety of supergene minerals (such as Se, efflorescent salts) and element associations (such as Hg, Cd-S, Fe-Cr-O) in which many of the ESE are concentrated. Native Se is the most commonly identified host of Se in the studied samples. The largest concentration of Se occurs in open-fracture systems that cross-cut waste rock and ore units. The age(s) of native Se formation is not known; how- ever, the latest period of Se mobility is the present. Direct measurement of efflorescent “salts” forming on new mine faces indicate that several ESE, including both Se and Zn, are concentrated on the faces soon after they are exposed. Zinc is present as hydrous sulfates, but the residence of Se in these “salts” is unknown.
NASA Astrophysics Data System (ADS)
Michalski, Krzysztof; Nejbert, Krzysztof; Domańska-Siuda, Justyna; Manby, Geoffrey
2014-05-01
A group of 42 independently oriented palaeomagnetic samples from 7 sites located in central part of the West Spitsbergen Thrust and Fault Belt has been investigated. The samples were collected from 5 distinct metadolerite sheets intruded into the Proterozoic - Lower Paleozoic metamorphic complex of Western Oscar II Land (Western Svalbard Caledonian Terrane - Harland, 1997 division). All analyzed metadolerite samples were metamorphosed under greenschist facies metamorphism. The metamorphic assemblage consist of hornblende, biotite, actinolite, chlorite, epidote, stilpnomelane, titanite, albite, and quartz. Calcite, associated with pyrrhotite, pyrite chalcopyrite, sphalerite, and covellite, that occurs as irregular intergrowths or thin veins, document high activity of H2O-CO2-rich fluids during metamorphism. Primary magmatic phases represented by clinopyroxene occur rarely, and only in thick metadolerite dykes. Accessory oxides change their mineralogical and chemical composition during metamorphism. In all examined samples primary Ti-magnetite and oxy-exsolved hematite break-down completely into titanite or have been dissolved. The ilmenite are also replaced by titanite, but in metadolerites at contact with host metapelites, slightly altered ilmenite grains with preserved hematite exsolution were documented. Basing on mineralogical observations it should be expected that metamorphic processes have almost completely reset the paleomagnetic data record from the time of dolerite crystallization. This stage can document only rare hematite oxy-exsolution preserved within ilmenite, and presumably small inclusion of magnetite still preserved within unaltered clinopyroxene. The paleomagnetic record of metamorphic stage is probably recorded by pyrrhotite, hematite, goethite, and late Ti-free magnetite that can grow during breakdown of pyrrhotite to pyrite (Ramdohr. 1980). The NRM (Natural Remanent Magnetisation) intensities of the palaeomagnetic samples exceed the minimum 10 mA/m. The first AF/thermal demagnetizations have revealed a stable NRM structure. ChRM (Characteristic Remanent Magnetisation) components can be extracted precisely from Zijderveld diagrams (precision parameter - ASD max. 10º). The following magnetic procedures have been applied to identify the ferromagnetic carriers of the samples: SIRM (saturation isothermal remanent magnetization) decay curves (procedure after Kadziałko-Hofmokl & Kruczyk, 1976) and the three-component IRM (isothermal remanent magnetization) procedure described by Lowrie (1990). Experimental work has revealed the dominance of pyrrhotite and magnetite phases as carriers with soft-medium coercivity (samples are saturated in 0.2-0.4 T) and distinct unblocking temperatures around 320-350 ºC and 575-600 ºC respectively. Presented study is the part of PALMAG project 2012-2015: "Integration of palaeomagnetic, isotopic and structural data to understand Svalbard Caledonian Terranes assemblage" (see also Michalski et al. 2012), funded by Polish National Science Centre. References: HARLAND,W.B. 1997. The Geology of Svalbard. Geological Society of London, Memoir 17, 521 pp. KĄDZIOŁKO-HOFMOKL,M. & KRUCZYK,J. 1976. Complete and partial self-reversal of natural remanent magnetization of basaltic rocks from Lower Silesia, Poland. Pure and Applied Geophysics 110, 2031-40. LOWRIE,W. 1990. Identification of ferromagnetic minerals in a rock by coercivity and unblocking temperature properties. Geophysical Research Letters 17, 159-62. MICHALSKI,K., LEWANDOWSKI,M., MANBY,G.M. 2012. New palaeomagnetic, petrographic and 40Ar/39Ar data to test palaeogeographic reconstructions of Caledonide Svalbard. Cambridge University Press. Geological Magazine 149 (4), 696-721. RAMDOHR,P. 1980. The ore minerals and their intergrowths. Pergamon Press, Oxford.
NASA Astrophysics Data System (ADS)
Evans, Guy N.; Tivey, Margaret K.; Seewald, Jeffrey S.; Wheat, C. Geoff
2017-10-01
This study investigates the morphology, mineralogy, and geochemistry of seafloor massive sulfide (SMS) deposits from six back-arc hydrothermal vent fields along the Eastern Lau Spreading Center (ELSC) and Valu Fa Ridge (VFR) in the context of endmember vent fluid chemistry and proximity to the Tonga Subduction Zone. To complement deposit geochemistry, vent fluid analyses of Cu, Zn, Ba, Pb and H2,(aq) were completed to supplement existing data and enable thermodynamic calculations of mineral saturation states at in situ conditions. Results document southward increases in the abundance of mantle-incompatible elements in hydrothermal fluids (Ba and Pb) and SMS deposits (Ba, Pb, As, and Sb), which is also expressed in the abundance of barite (BaSO4) and galena (PbS) in SMS deposits. These increases correspond to a decrease in distance between the ELSC/VFR and the Tonga Subduction Zone that correlates with a change in crustal lithology from back-arc basin basalt in the north to mixed andesite, rhyolite, and dacite in the south. Barite influences deposit morphology, contributing to the formation of horizontal flanges and squat terraces. Results are also consistent with a regional-scale lowering of hydrothermal reaction zone temperatures from north to south (except at the southernmost Mariner vent field) that leads to lower-temperature, higher-pH vent fluids relative to mid-ocean ridges of similar spreading rates (Mottl et al., 2011). These fluids are Cu- and Zn-poor and the deposits formed from these fluids are Cu-poor but Zn-rich. In contrast, at the Mariner vent field, higher-temperature and lower pH vent fluids are hypothesized to result from higher reaction zone temperatures and the localized addition of acidic magmatic volatiles (Mottl et al., 2011). The Mariner fluids are Cu- and Zn-rich and vent from SMS deposits that are rich in Cu but poor in Zn with moderate amounts of Pb. Thermodynamic calculations indicate that the contrasting metal contents of vent fluids and SMS deposits can be accounted for by vent fluid pH. Wurtzite/sphalerite ((Zn, Fe)S) and galena (PbS) are saturated at higher temperatures in higher-pH, Zn-, Cu-, and Pb-poor ELSC/VFR vent fluids, but are undersaturated at similar temperatures in low-pH, Zn-, Cu-, and Pb-rich vent fluids from the Mariner vent field. Indicators of pH in the ELSC and VFR SMS deposits include the presence of co-precipitated wurtzite and chalcopyrite along conduit linings in deposits formed from higher pH fluids, and different correlations between concentrations of Zn and Ag in bulk geochemical analyses. Significant positive bulk geochemical Zn:Ag correlations occur for deposits at vent fields where hydrothermal fluids have a minimum pH (at 25 °C) < 3.3, while correlations of Zn:Ag are weak or negative for deposits at vent fields where the minimum vent fluid pH (at 25 °C) > 3.6. Data show that the compositions of the mineral linings of open conduit chimneys (minerals present, mol% FeS in (Zn,Fe)S) that precipitate directly from hydrothermal fluids closely reflect the temperature and sulfur fugacity of sampled hydrothermal fluids. These mineral lining compositions thus can be used as indicators of hydrothermal fluid temperature and composition (pH, metal content, sulfur fugacity).
Schmidt, D.L.; Puffett, W.P.; Campbell, W.L.; Al-Koulak, Z. H.
1981-01-01
An ancient gold placer at Jabal Mokhyat (lat 20?12.2'N., long 43?28'E.), about 90 km east of Qalat Bishah in the southern Najd Province, Kingdom of Saudi Arabia, was studied in 1973. Seven hundred and twenty-eight samples in 25 measured sections were collected along trenches and pits 2.5 m in depth and 2,600 m in total length. Alluvium was thicker than the excavation depth along about 50 percent of the trench length. The average gold content was 4.4 mg per m3, and the highest grade trench contained 40 mg gold per m 3. Because fine particulate gold is rare in the alluvium, a few large particles, 1 to 5 mm in diameter, greatly affected the sampling results. The ancient placer diggings are in small headwater wadis distributed over a 30-km 2 area, and the total dug area is about 1.2 km2. The placer produced an estimated 50 kg of gold and was worked about 2,600 + 250 years ago. The potential for a present-day placer operation is small. The gold is sparsely distributed in locally derived, flood-deposited, immature gravels throughout a stratigraphic section that consists of 1) calichified, saprolitic bedrock of Precambrian age; 2) basal, intensely calichified, saprolitic gravel (0-3 m thick) of Pleistocene age; 3) disconformable, slightly consolidated gravel and sand (0-1 m thick) of late Pleistocene age containing sparse, disseminated caliche; 4) firm loessic silt (0-1 m thick) of early Holocene age; and 5) loose sand and gravel (0.3-1 m thick) of late Holocene age. The loessic silt accumulated during the Holocene pluvial. The top of the loessic silt unit is dated at about 6,000 years B.P. by using charcoal from hearths of ancient man. Following the Holocene pluvial, the climate became arid, and extreme desiccation resulted in abundant eolian sand that progressively diluted the late Holocene gravels. The remnants of the pre-Holocene stratigraphy suggest similar climatic cycles during the Pleistocene. Abundant, sparsely mineralized, gold-bearing quartz veins (0-1 m wide) were the source of the placer gold. These late Proterozoic veins have hydrothermally altered wall-rock zones (1-5 m wide). The veins are dispersed over an area of 50 km 2. Though many veins were prospected in ancient times and some were slightly worked, only the Mokhyat ancient mine, located on a quartz-vein zone 30 m wide by 200 m long, was extensively worked. The quartz contains chalcopyrite, galena, sphalerite, tetrahedrite, an unidentified bismuth mineral, and small amounts of dispersed gold. The fissure quartz veins lie at the complexly splayed, terminal end of a small northwest-trending Najd fault that elsewhere along strike has ii km of left-lateral displacement. Most large veins are in north-trending vertical fractures where the stresses were distributed along an older, north-trending structural grain in andesitic greenstone terrane. Subhorizontal fracture sets contain conspicuous, well-developed gold-bearing quartz veins and associated alteration zones. These attest to the shallowness and youthfulness of mineralization during latest Precambrian time. Late Precambrian granitic plutons (625-600 m.y. old) had been deeply eroded before the gold minerals were emplaced; hence, the gold is not related to granitic plutonism. Abundant, widely distributed diabasic dikes associated with the Najd faulting event of latest Precambrian age were probably the heat source for the hydrothermal convection system and possibly the source of the gold.
NASA Astrophysics Data System (ADS)
Theodoridou, Stella; Melfos, Vasilios; Voudouris, Panagiotis; Miskovic, Aleksandar
2016-04-01
Although intrusion-related systems have not been previously recognized in the European segment of the Tethyan Metallogenic Belt, the Rhodope metallogenic province of SE Balkan peninsula hosts numerous such occurrences. The Kimmeria hydrothermal system incorporates two styles of ore mineralization: i) a massive Au-bearing magnetite-pyrrhotite skarn and ii) a Mo-Cu-Bi-W quartz vein-hosted mineralization, both of which are related to the Oligocene Xanthi pluton (25.5±1.2 to 30±1 My, K-Ar in hornblende and biotite). The Xanthi pluton, consisting of I-type gabbros, monzonites and amphibole-biotite granodiorites, intrudes the basement gneisses, mica schists, amphibolites and marbles of the Southern Rhodope Core Complex; a dome that has gradually exhumed from Paleocene/mid Eocene to Miocene (starting between 65 and >42 to 10 My). The Xanthi pluton emplacement and the magmatically derived hydrothermal fluid circulation were controlled by two major regional structures: the low-angle Kavala-Xanthi-Komotini detachment fault and the Nestos thrust fault. The Kimmeria Au-Cu-Fe skarn mineralization features a well-preserved aureole at the contact between the granodiorite and the surrounding marbles. It consists of two paragenetic stages comprising magnetite and pyrrhotite-rich assemblages. Alteration minerals comprise chlorite and sericite. Bulk chemical analyses of the skarn mineralization revealed relatively high concentration of Cu (1 wt.%), Pb (288 ppm) and Zn (0.74 wt.%). The mineralization is also enriched in As (< 75.8 ppm), W (< 82.1 ppm), Bi (<10.1 ppm), Sb (<331.9 ppm), Ag (< 15.9 ppm), and Sn (< 50 ppm). Te and Au are found in low concentrations of less than 2 ppm and 0.4 ppm, respectively. The Kimmeria Mo-Cu-Bi-W vein-type mineralization comprises a system of cross-cutting and sheeted quartz veins within the granodiorite, with pyrite, chalcopyrite and molybdenite as dominant sulfides. Minor sphalerite, tetrahedrite-tennantite, galena and rutile are also present, while sericite and chlorite as the alteration minerals. The Cu and Mo content of the vein type mineralization exceed 1.0 and 0.2 wt.% respectively, along with < 2.7 ppm Au, 1.3 to 79.5 ppm W and 0.6 to 456 ppm Bi. A first approach fluid study has revealed small variations in δ34S values of sulfides (0 - 2.3 ‰ VCDT) from both types of mineralization suggesting a magmatic source of sulfur. Silicate δ18O values of quartz show a narrow range between 10.3 and 11.2 ‰ (VSMOW) suggesting similar quartz formation for both mineralization types, at relatively low temperatures and probably from the same fluid. Oxygen isotopes values in calcite from the unmineralized marbles and ore specimens are scattered over a wide range from 12.1 to 41.7 ‰ (V-SMOW). They have relatively low carbon isotopic values (-4.8 to 2.1 ‰ V-PDB), indicative of a magmatic δ13C signature and a restricted isotopic exchange with hydrothermal fluids. Primary fluid inclusion studies have revealed the presence of CO2 in the ore fluid, which might have played an important role during the ore genesis irrespective of the mineralization style. This work was financially supported by the Western Tethyan Metallogeny Project (MDRU - The University of British Columbia).
Geology and geochemistry of the Reocín zinc-lead deposit, Basque-Cantabrian Basin, Northern Spain
Velasco, Francisco; Herrero, Jose Miguel; Yusta, Inaki; Alonso, Jose Antonio; Seebold, Ignacio; Leach, David
2003-01-01
The Reoci??n Zn-Pb deposit, 30 km southwest of Santander, Spain, occurs within Lower Cretaceous dolomitized Urgonian limestones on the southern flank of the Santillana syncline. The Reoci??n deposit is one of the largest known strata-bound, carbonate-hosted, zinc-lead deposits in Europe. The total metal endowment of the deposit, including past production and remaining reserves, is 62 Mt of ore grading 8.7 percent Zn and 1.0 percent Pb. The epigenetic mineralization consists of sphalerite and galena, with lesser marcasite and trace pyrite with dolomite as gangue. Microprobe analyses of different generations of dolomite revealed nonstoichiometric compositions with various amounts of iron (up to 14 mol % of FeCO3). Replacement of host dolomite, open-space filling of fractures, and cementation of breccias derived from dissolution collapse are the principal types of ore occurrence. Detailed cross-section mapping indicates a stratigraphic and structural control on the deposit. A stratiform morphology is present in the western part of the orebody (Capa Sur), whereas mineralization in the eastern part is highly discordant but strata bound (Barrendera). Stratigraphic studies demonstrate that synsedimentary tectonic activity, related to the rifting of the North Atlantic (Bay of Biscay), was responsible for variation in sedimentation, presence of unconformities (including paleokarsts), local platform emergence and dolomitization along the N60 fault trend. In the Reoci??n area, two stages of dolomitization are recognized. The first stage is a pervasive dolomitization of the limestone country rocks that was controlled by faulting and locally affected the upper part of the Aptian and the complete Albian sequence. The second dolomitization event occurred after erosion and was controlled by karstic cavities. This later dolomitization was accompanied by ore deposition and, locally, filling of dolomite sands and clastic sediments in karstic cavities. The circulation of hydrothermal fluids responsible for sulfide deposition and the infilling of karst cavities were broadly contemporaneous, indicating a post-Albian age. Vitrinite reflectance data are consistent with previously measured fluid inclusion temperatures and indicate temperatures of ore deposition that were less than 100??C. Carbon and oxygen isotopic data from samples of regional limestone, host-rock dolostone and ore-stage dolomite suggest an early hydrothermal alteration of limestone to dolostone. This initial dolomitization was followed by a second period of dolomite formation produced by the mixing of basinal metal-rich fluids with local modified seawater. Both dolomitization events occurred under similar conditions from fluids exhibiting characteristics of basinal brines. The ??34S values of sulfides are between -1.8 and +8.5 per mil, which is consistent with thermochemical sulfate reduction involving organic matter as the main source of reduced sulfur. Galena lead isotope compositions are among the most radiogenic values reported for Zn-Pb occurrences in Europe, and they are distinct from values reported for galena from other Basque-Cantabrian deposits. This suggests that a significant part of the lead was scavenged from the local underlying Asturian sediments. The stratigraphic and structural setting, timing of epigenetic mineralization, mineralogy, and isotopic geochemistry of sulfide and gangue minerals of the Reoci??n deposit are consistent with the features of most of Mississippi Valley-type ore deposits.
How metallic is the binding state of indium hosted by excess-metal chalcogenides in ore deposits?
NASA Astrophysics Data System (ADS)
Ondina Figueiredo, Maria; Pena Silva, Teresa; Oliveira, Daniel; Rosa, Diogo
2010-05-01
Discovered in 1863, indium is nowadays a strategic scarce metal used both in classical technologic fields (like low melting-temperature alloys and solders) and in innovative nano-technologies to produce "high-tech devices" by means of new materials, namely liquid crystal displays (LCDs), organic light emitting diodes (OLEDs) and the recently introduced transparent flexible thin-films manufactured with ionic amorphous oxide semiconductors (IAOS). Indium is a typical chalcophile element, seldom forming specific minerals and occurring mainly dispersed within polymetallic sulphides, particularly with excess metal ions [1]. The average content of indium in the Earth's crust is very low but a further increase in its demand is still expected in the next years, thus focusing a special interest in uncovering new exploitation sites through promising polymetallic sulphide ores - e.g., the Iberian Pyrite Belt (IPB) [2] - and in improving recycling technologies. Indium recovery stands mostly on zinc extraction from sphalerite, the natural cubic sulphide which is the prototype of so-called "tetrahedral sulphides" where metal ions fill half of the available tetrahedral sites within the cubic closest packing of sulphur anions where the double of unfilled interstices are available for further in-filling. It is worth remarking that such packing array is particularly suitable for accommodating polymetallic cations by filling closely located interstitial sites [3] as happens in excess-metal tetrahedral sulphides - e.g. bornite, ideally Cu5FeS4, recognized as an In-carrying mineral [4]. Studying the tendency towards In-In interactions able of leading to the formation of polycations would efficiently contribute to understand indium crystal chemistry and the metal binding state in natural chalcogenides. Accordingly, an X-ray absorption near-edge spectroscopy (XANES) study at In L3-edge was undertaken using the instrumental set-up of ID21 beamline at the ESRF (European Synchrotron Radiation Facility, in Grenoble/France). Polymetallic chalcogenide minerals and various model compounds displaying distinct bonding situations of indium to other ligands (oxygen and halides) were studied. Encouraging results from a first experiment [5] showed the presence of a "white line" in the XANES spectra collected from InF3 and from In-hosting bornite; however, the impossibility of clearly identifying the nanoscale phase hosting indium in sulphide ore samples has hindered a full interpretation of X-ray absorption data. The crystal chemistry of indium in natural chalcogenides is now reanalysed and XANES results obtained so far for polymetallic sulphides are accordingly re-evaluated, disclosing a challenging clue for indium binding state in these host minerals within sulphide ores. [1] M.O. Figueiredo et al. (2007) Procd. 9th Biennial SGA Mtg., Dublin/Ireland, edt. C. Andrew et al., 1355-1357. [2] O.C. Gaspar (2002) Canad. Miner. 40, 611-636. [3] M.O. Figueiredo & T.P. Silva (2009) ICANS 23, 23rd Int. Conf. Amorphous & Nano-crystalline Semiconductors, Netherlands, August 23-28. Poster ID 229 (abstract). [4] T. Seifert & D. Sandmann (2002) Ore Geol. Reviews 28, 1-31. [5] M.O. Figueiredo & T.P. Silva (2009) XVIII Int. Mater. Res. Congr., Mexico, August 16-20. Symp. 20, Poster nr. 1 (abstract). * Work developed within the research project PTDC/CTE-GIN/67027/2006 financed by the Portuguese Foundation for Science & Technology (FCT/MCTES). The financial support from EU to perform the experiments at the ESRF is also acknowledged.
Two Vent Fields Discovered at the Ultraslow Spreading Arctic Ridge System
NASA Astrophysics Data System (ADS)
Pedersen, R. B.; Thorseth, I. H.; Hellevang, B.; Schultz, A.; Taylor, P.; Knudsen, H. P.; Steinsbu, B. O.
2005-12-01
Two high-temperature vent fields were discovered at the Mohns Ridge during an expedition with the Norwegian research vessel "G.O. Sars" in July 2005. Both vent fields are located within the southernmost segment of the Mohns Ridge approximately 50 km north of the West Jan Mayen Fracture Zone. Water depths along this segment range from 3800 meters close to the fracture zone to ~500 meters at the segment centre where the vent fields are located. The largest field - named "Gallionella Garden" - is situated within a rift graben where high- and low-temperature venting occurs along ridge-parallel normal faults and fissures. Presently we have documented high- and low-temperature venting along more then 2 km of the fault and fissure system in the area. The high-temperature venting takes place at around 550 mbsl at the base of a 100 meter high fault wall and was traced ~500 meters along strike. The field consists of at least 10 major vent sites, each composed of multiple chimneys that are up to 5-10 meters tall. There are also large areas of diffuse flow. The temperature of the vent fluids was measured to be above 260°C at a chimney orifice. This is at the boiling point of seawater at these water depths, and gas bubbling was observed at several of the vent sites. A sample of the top of a chimney consists of anhydrite, barite, sphalerite and pyrite. Outside the high-temperature vent area mounds of ferric iron are abundant. Such deposits have presently been traced along ~2 km of the faults and fissure system in the area. The deposits are predominantly made up of branching and twisted stalks comparable to those formed by the iron oxidizing bacteria Gallionella ferruginea showing that the precipitation is mediated by microbial activity. The temperatures below the upper crust of a mound were measured to be one degree above the ambient water temperature. The Fe-oxyhydroxides show Nd-isotope compositions similar to the basaltic crust and Sr-isotope compositions close to that of seawater, and may have formed from fluids composed of 90 percent seawater and 10 percent of an end-member hydrothermal fluid. Nd-concentrations suggest Fe-precipitate/fluid ratio of one to a million (ie. that 1 kg of Fe-deposits scavenged neodymium from one million litres of fluids). A second vent field was discovered 5 km southwest of "Gallionella Garden" at ~700 mbsl. The "Soria Moria" field is located at a volcanic ridge composed of recent lava flows and is about 100 meters across. The field consists of numerous chimneys emitting buoyant white smoker fluids, as well as irregular shaped mounds with flange structures discharging fluids of higher density then the ambient waters. White bacterial mats cover the seafloor and chimneys at both fields, and shrimp, sea spiders and colonies of sea anemones, crinoids and hydroids are associated with the vent fields. The hydrothermal plumes were detected acoustically using the exceptionally sensitive scientific echo sounders on "G.O.Sars". The acoustic backscatters images show that the hydrothermal plume above "Gallionella Garden" perturb the upper hydrographical layers, implying that this shallow vent field may "fertilize" the productive hydrographical layers in the area.
NASA Astrophysics Data System (ADS)
Grew, E. S.; Dymek, R. F.; De Hoog, J. C.; Harley, S. L.; Hazen, R. M.; Yates, M. G.
2013-12-01
The distribution and mineralogical context of trace elements in Earth's oldest rocks provide insights on Earth's accretion, differentiation, and primordial evolution. One example is boron, which is highly concentrated in Earth's crust and oceans relative to primitive mantle, and, thus the amount of boron on Earth's surface should increase with increasing volume of crust. The earliest B mineral reported in the geological record is metamorphic tourmaline in the Isua Supracrustal Belt, where its abundance belies the notion of there being less boron in the Eoarchean than in more recent time. Chaussidon & Appel (1997, Chem. Geol., 136, 171-180) reported δ11B = --17.3 to --25.0‰ in tourmaline in Isua metachert ("conglomerate"), and δ11B = --12.6 to +5.8 ‰ on tourmaline in Isua metamorphosed mafic volcaniclastics. The large range in the latter rocks was attributed to fractionation during hydrothermal reworking, whereas the more negative values in the metacherts suggested metamorphic tourmaline formed from breakdown of clays with an average δ11B calculated to be about -8 × 7‰ deposited in an ocean having δ11B = +27×11‰, compared to +40 ‰ today, consistent with δ11B = +28‰ calculated from the Chaussidon & Albarède (1992, EPSL, 108, 229-241) model relating increase in sea-water δ11B to proportion of B extracted from Earth's mantle into the oceans and crust. This estimate of Eoarchean seawater δ11B is consistent with fractionation associated with illitization of smectite formed in a marine environment (estimated to be about --35‰) and with crystallization of metamorphic tourmaline from intergranular fluid having the same δ11B as the host metachert (another --2‰ at 500 °C based on tourmaline-water fractionation from Meyer et al. 2008, Contrib. Mineral. Petrol., 156, 259-267). However, this scenario does not adequately explain three rock types in the Isua supracrustals: (1) a tourmaline-quartz lens with ~50% modal tourmaline; (2) a dolomite-tourmaline lens with ~20% modal tourmaline containing accessory chromite, chalcopyrite and gersdorffite, (Ni,Co,Fe)AsS; (3) 'green-mica' schist containing Cr- and Ba-bearing muscovite and accessory tourmaline, sphalerite, chalcopyrite, galena, pentlandite, arsenopyrite and gersdorffite. These sulfides suggest that hydrothermal fluid associated with volcanism introduced B, As and Pb into sedimentary rocks together with Cr, Co and Ni remobilized from associated ultramafic rocks. Crystallization of tourmaline in (1) with δ11B =--22‰ (Swihart & Moore, 1989, Geochim. Cosmochim. Acta, 53, 911-916) implies δ11B of --17 ‰ to--19 ‰ in the hydrothermal fluid from which it crystallized (assuming tourmaline-water fractionation at 200-350 °C based on Meyer et al. 2008). These fluid δ11B suggest a continental source of the boron, since δ11B of continental detritus averages -10 × 5‰, i.e., more negative (lighter) than oceanic crust (Leeman & Sisson, 1996, Rev. Mineral., 33, 645-707). As the tourmaline-bearing rocks are part of the younger (ca. 3700 Ma) of two terranes in the Isua supracrustal belt (Nutman & Friend, 2009, Precamb. Res., 172, 189-211), we suggest that boron isotopic composition and abundance resulted from recycling of boron in supracrustal rocks of the older (ca. 3800 Ma) terrane and its remobilization in a volcanic system prior to precipitation as tourmaline in rocks of the younger terrane.
New observations on the Ni-Co ores of the southern Arburese Variscan district (SW Sardinia, Italy)
NASA Astrophysics Data System (ADS)
Naitza, Stefano; Secchi, Francesco; Oggiano, Giacomo; Cuccuru, Stefano
2015-04-01
Among the European Variscan regions, the Arburese district, located in the Paleozoic basement of SW Sardinia (Italy) is remarkable for its metallogenic complexity, and offers good opportunities to investigate time/space and genetic links between post-collisional Variscan intrusive magmatism and mineral deposits. The district hosts a large variety of mineral deposits and occurrences, which include the Pb-Zn (Cu, Ag) mesothermal veins of the Montevecchio Lode System, one of the largest and richest Variscan hydrothermal ore deposit of Europe, now exhausted. Ore deposits are genetically related to the emplacement of the Late Variscan (304±1 Ma) Arbus Pluton, a granitoid composite intrusion ranging from monzogabbroic to granodioritic and to peraluminous leucogranitic rock-types. After more than a century of geological studies in the area, several metallogenic issues are still unresolved; among them, the occurrence in the southern sectors of little known polymetallic Ni-Co-(Pb-Zn-Cu-Ag-Bi) veins, a kind of mineralization quite unusual for the Sardinian basement. These hydrothermal deposits are hosted by very low-grade metamorphic rocks at short distance from the intrusion, where contact effect generate also hornfels. Spatial, structural and textural characters of the hydrothermal system are coherent and in apparent continuity with those of the Montevecchio Lode System. Ni-Co ores are hosted by a system of parallel, 1-2 m thick high-angle veins that discontinuously follow the southwestern and southern contacts of the Arbus Pluton for about 7 km. They constantly dip SSW, sideways with respect to the pluton contact, and show a prevalence of fracture infilling (banded and brecciated) textures, with alternating quartz and siderite bands, cockades and frequent inclusions of wallrock fragments. Wallrocks are usually silicified, bleached and/or sericitized. Systematic studies of ore textures and parageneses from different veins along the system have been performed by standard ore microscopy and SEM-EDS. Ore minerals associations include Ni-Co (Fe, Sb) arsenides/sulfoarsenides (nickeline, rammelsbergite, skutterudite, safflorite, gersdorffite, breithauptite, lollingite, cobaltite), Pb-Zn-Cu-Ag-Bi sulfides (galena, sphalerite, chalcopyrite, tetrahedrite/freibergite, bismuthinite, proustite/pyrargirite, stephanite), native Bi and native Ag. Ore textures and mineral phases relationships allow to envisage the following paragenetic sequence: 1) deposition of quartz (I) and a Ni monoarsenide (nickeline), and antimonide (breithauptite) followed by 2) Ni-,Ni-Co, Co- and Fe- di-, tri- arsenides and sulfoarsenides (rammelsbergite, skutterudite, safflorite, löllingite, cobaltite), with bismuthinite and native Bi; 3) deposition of abundant siderite, with quartz (II), Pb-Zn-Cu-Ag sulfides and sulfosalts and rare native Ag, followed at last by 4) calcite. This sequence depicts a polyphased evolution with alternating gradual and abrupt changes of the physicochemical parameters of a mesothermal fluid initially characterized by Ni-As-(Sb) contents, subsequently evolved to higher contents of As, Co and Bi, and, finally, enriched in S, allowing Pb, Zn, Cu deposition as sulfides and sulfosalts.Thus, the fine alternating rims of pure nickeline (NiAs) and breithauptite (NiSb) in nickeline individuals, detected by SEM-EDS, may be explained by repeated compositional re-equilibrations due to variable As and Sb contents of the fluids; increases in As, and, moreover, the sudden appearance of siderite and sulfides after brecciations indicate further re-opening of the system, related to hydrothermal fracturing and syn-depositional tectonics.
Getahun, A.; Reed, M.H.; Symonds, R.
1996-01-01
Intensely altered wall rock was collected from high-temperature (640??C) and low-temperature (375??C) vents at Augustine volcano in July 1989. The high-temperature altered rock exhibits distinct mineral zoning differentiated by color bands. In order of decreasing temperature, the color bands and their mineral assemblages are: (a) white to grey (tridymite-anhydrite); (b) pink to red (tridymite-hematite-Fe hydroxide-molysite (FeCl3) with minor amounts of anhydrite and halite); and (c) dark green to green (anhydrite-halite-sylvite-tridymite with minor amounts of molysite, soda and potash alum, and other sodium and potassium sulfates). The alteration products around the low-temperature vents are dominantly cristobalite and amorphous silica with minor potash and soda alum, aphthitalite, alunogen and anhydrite. Compared to fresh 1986 Augustine lava, the altered rocks exhibit enrichments in silica, base metals, halogens and sulfur and show very strong depletions in Al in all alteration zones and in iron, alkali and alkaline earth elements in some of the alteration zones. To help understand the origins of the mineral assemblages in altered Augustine rocks, we applied the thermochemical modeling program, GASWORKS, in calculations of: (a) reaction of the 1987 and 1989 gases with wall rock at 640 and 375??C; (b) cooling of the 1987 gas from 870 to 100??C with and without mineral fractionation; (c) cooling of the 1989 gas from 757 to 100??C with and without mineral fractionation; and (d) mixing of the 1987 and 1989 gases with air. The 640??C gas-rock reaction produces an assemblage consisting of silicates (tridymite, albite, diopside, sanidine and andalusite), oxides (magnetite and hercynite) and sulfides (bornite, chalcocite, molybdenite and sphalerite). The 375??C gas-rock reaction produces dominantly silicates (quartz, albite, andalusite, microcline, cordierite, anorthite and tremolite) and subordinate amounts of sulfides (pyrite, chalcocite and wurtzite), oxides (magnetite), sulfates (anhydrite) and halides (halite). The cooling calculations produce: (a) anhydrite, halite, sylvite; (b) Cu, Mo, Fe and Zn sulfides; (c) Mg fluoride at high temperature (> 370??C); (d) chlorides, fluorides and sulfates of Mn, Fe, Zn, Cu and Al at intermediate temperature (170-370??C); and (e) hydrated sulfates, liquid sulfur, crystalline sulfur, hydrated sulfuric acid and water at low temperature ( 0.41 (> 628??C). This is followed by precipitation of sulfates of Fe, Cu, Pb, Zn and Al at lg/a ratios between 0.41 and -0.4 (628-178??C). At a lg/r ratio of < - 0.4 (178??C), anhydrous sulfates are replaced by their hydrated forms and hygroscopic sulfuric acid forms. At these low g/a ratios, hydrated sulfuric acid becomes the dominant phase in the system. Comparison of the thermochemical modeling results with the natural samples suggests that the alteration assemblages include: (1) minerals that precipitate from direct cooling of the volcanic gas; (2) phases that form by volcanic gases mixing with air; and (3) phases that form by volcanic gas-air-rock reaction. A complex interplay of the three processes produces the observed mineral zoning. Another implication of the numerical simulation results is that most of the observed incrustation and sublimate minerals apparently formed below 700??C.
Desborough, George A.; Poole, F.G.; Hose, R.K.; Radtke, A.S.
1979-01-01
A kerogen-rich sequence of siliceous mudstone, siltstone, and chert as much as 60 m thick on ridge 7129 in the southern Fish Creek Range, referred to as Gibellini facies of the Woodruff Formation, has been evaluated on the surface and in drill holes principally for its potential resources of vanadium, zinc, selenium, molybdenum, and syncrude oil content. The strata are part of a strongly deformed allochthonous mass of eugeosynclinal Devonian marine rocks that overlie deformed allochthonous Mississippian siliceous rocks and relatively undeformed autochthonous Mississippian Antler flysch at this locality. The vanadium in fresh black rocks obtained from drill holes and fresh exposures in trenches and roadcuts occurs chiefly in organic matter. Concentrations of vanadium oxide (V2O5) in unoxidized samples range from 3,000 to 7,000 ppm. In oxidized and bleached rock that is prevalent at the surface, concentrations of vanadium oxide range from 6,000 to 8,000 ppm, suggesting a tendency toward enrichment due to surficial weathering and ground-water movement. Zinc occurs in sphalerite, and selenium occurs in organic matter; molybdenum appears to occur both in molybdenite and in organic matter. Concentrations of zinc in unoxidized rock range from 4,000 to 18,000 ppm, whereas in oxidized rock they range from 30 to 100 ppm, showing strong depletion due to weathering. Concentrations of selenium in unoxidized rock range from 30 to 200 ppm, whereas in oxidized rock they range from 200 to 400 ppm, indicating some enrichment upon weathering. Concentrations of molybdenum in unoxidized rock range from 70 to 960 ppm, whereas in oxidized rock they range from 30 to 80 ppm, indicating strong depletion upon weathering. Most fresh black rock is low-grade oil shale, and yields as much as 12 gallons/short ton of syncrude oil. Metahewettite is the principal vanadium mineral in the oxidized zone, but it also occurs sparsely as small nodules and fillings of microfractures in unweathered strata. In fresh rock, bluish-white opaline-like silica (chalcedonic quartz) fills microfractures, and is believed to have originated by diagenetic mobilization of opaline silica from radiolarian tests and sponge spicules. As revealed by microscopic study, the Gibellini facies originally consisted of siliceous muds, slimes, and oozes high in organic constituents. The organic matter is amorphous flaky and stringy sapropel, and probably includes remains of bacteria, phytoplankton, zooplankton, and minor higher plants. Recognizable organic remnants include radiolarian tests, sponge spicules, conodonts, brachiopod shells, algae, and humic debris. Diagnostic radiolarians indicate a Late Devonian age for the Gibellini facies of the Woodruff Formation. Some pyrite is disseminated through the rock and may be primary (syngenetic) but significant pyrite and marcasite occur in chalcedonic quartz veinlets and appear to be diagenetic. In fresh rock, black solid bitumen and liquid oil fill voids and microfractures. These early phase hydrocarbons probably were released during diagenesis from complex nonhydrocarbon molecular structures originating from living organisms, and formed without any major thermal degradation of the kerogen. Gas chromatographic analysis of the saturated hydrocarbon fraction indicates a very complex mixture dominated by branched and cyclic compounds. Conodont and palynomorph color alteration, vitrinite reflectance, and other organic geochemical data suggest that the organic matter in the rock is thermally immature and has not been subjected to temperatures greater than 60?C since deposition in Devonian time. All of these characteristics are consistent with the interpretation of a relatively low temperature and a shallow-burial history for the Gibellini facies on ridge 7129.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Han,W.Q.
Boron nitride (BN) is a synthetic binary compound located between III and V group elements in the Periodic Table. However, its properties, in terms of polymorphism and mechanical characteristics, are rather close to those of carbon compared with other III-V compounds, such as gallium nitride. BN crystallizes into a layered or a tetrahedrally linked structure, like those of graphite and diamond, respectively, depending on the conditions of its preparation, especially the pressure applied. Such correspondence between BN and carbon readily can be understood from their isoelectronic structures [1, 2]. On the other hand, in contrast to graphite, layered BN ismore » transparent and is an insulator. This material has attracted great interest because, similar to carbon, it exists in various polymorphic forms exhibiting very different properties; however, these forms do not correspond strictly to those of carbon. Crystallographically, BN is classified into four polymorphic forms: Hexagonal BN (h-BN) (Figure 1(b)); rhombohedral BN (r-BN); cubic BN (c-BN); and wurtzite BN (w-BN). BN does not occur in nature. In 1842, Balmain [3] obtained BN as a reaction product between molten boric oxide and potassium cyanide under atmospheric pressure. Thereafter, many methods for its synthesis were reported. h-BN and r-BN are formed under ambient pressure. c-BN is synthesized from h-BN under high pressure at high temperature while w-BN is prepared from h-BN under high pressure at room temperature [1]. Each BN layer consists of stacks of hexagonal plate-like units of boron and nitrogen atoms linked by SP{sup 2} hybridized orbits and held together mainly by Van der Waals force (Fig 1(b)). The hexagonal polymorph has two-layered repeating units: AA'AA'... that differ from those in graphite: ABAB... (Figure 1(a)). Within the layers of h-BN there is coincidence between the same phases of the hexagons, although the boron atoms and nitrogen atoms are alternatively located along the c-axis. The rhombohedral system consists of three-layered units: ABCABC..., whose honeycomb layers are arranged in a shifted phase, like as those of graphite. Reflecting its weak interlayer bond, the h-BN can be cleaved easily along its layers, and hence, is widely used as a lubricant material. The material is stable up to a high temperature of 2300 C before decomposition sets in [2] does not fuse a nitrogen atmosphere of 1 atm, and thus, is applicable as a refractory material. Besides having such properties, similar to those of graphite, the material is transparent, and acts as a good electric insulator, especially at high temperatures (10{sup 6} {Omega}m at 1000 C) [1]. c-BN and w-BN are tetrahedrally linked BN. The former has a cubic sphalerite-type structure, and the latter has a hexagonal wurtzite-type structure. c-BN is the second hardest known material (the hardest is diamond), the so-called white diamond. It is used mainly for grinding and cutting industrial ferrous materials because it does not react with molten iron, nickel, and related alloys at high temperatures whereas diamond does [1]. It displays the second highest thermal conductivity (6-9 W/cm.deg) after diamond. This chapter focuses principally upon information about h-BN nanomaterials, mainly BN nanotubes (BNNTs), porous BN, mono- and few-layer-BN sheets. There are good reviews book chapters about c-BN in [1, 4-6].« less
The Thermal History of Enstatite Chondrites
NASA Astrophysics Data System (ADS)
Zhang, Y.; Benoit, P. H.; Sears, D. W. G.
1992-07-01
In an attempt to decipher the complicated thermal history of the enstatite chondrites, the CaS enstatite (Larimer and Buseck, 1974; Fogel et al., 1989), cubic sulfide (Skinner and Luce, 1971) and sphalerite (Kissin, 1989; El Goresy and Ehlers, 1989) systems have been applied, but the results have not been straightforward. The CaS-En thermometer gives metamorphic temperatures which appear reasonable, but which do not correlate well with petrologic type. The cubic sulfides yield reasonable temperatures for the EH chondrites, but the values for EL chondrites are very low. To some extent, the problem has been the lack of low petrologic type EL chondrites. Here we discuss data for the recently discovered EL3 chondrites (Chang et al., 1992) and we examine the applicability of the Fe-Ni-P system for thermometry. The CaS-En thermometer uses three reactions including equilibria between metal, CaS, SiO2, enstatite and FeS. The method is crucially dependent on the activity coefficients for Si and CaSiO3 which are in solid solutions with metal and enstatite, respectively. The cubic sulfide thermometer uses the solubility of FeS in MgS and MnS, while the ZnS thermometer (which is pressure-dependent) uses the solubility of FeS in ZnS. Current equilibration temperature estimates for enstatite chondrites including the EL3 chondrites are listed in Table 1. Table 1. Estimates of equilibration temperatures (degrees C) for enstatite chondrites.* Petrologic type EH EL System 3 4 5 6 3 4 5 6 En-CaS 1030 950 830 - 830 - - 1025 Cubic sulf 400 680 600 - <<400 - - <400 ZnS 410 (1859)+ - - 500 - - 550 Fe-Ni-P <450 500 550 - <<450 - - <450 *Literature data (see text), present data (bold type). +Heavily shocked. In an attempt to use the Fe-Ni-P system as a thermometer for enstatite chondrites, we used the phase diagram of Doan and Goldstein (1970). Like the other systems, this required extrapolation to lower temperatures (Fig. 1). The temperatures calculated from this system mirror those of the sulfides, suggesting major differences in the thermal history of the EL and EH chondrites. Two points may be made from the data in Table 1. The EH3 and EL3 chondrites have similar En-CaS equilibration temperatures to those of the higher petrologic types which we suspect reflect pre-metamorphic equilibria. Second, both the cubic sulfides and the phosphides yield metamorphic temperatures for the EH chondrites which are similar to those for ordinary chondrites, while EL chondrites yield very low temperatures. The EL chondrite parent body must have cooled at especially slow rates, perhaps because it was much larger than the EH parent body, or maybe the cooling rate on EL body was governed by the attenuation of the heat source rather than burial depth. Chang Y., Benoit P.H. and Sears D.W.G. (1992) Lunar and Planet. Sci. 23, 217-218. Doan A.S. and Goldstein J.I. (1970) Met. Trans. 1, 1759-1767. El Goresy A. and Ehlers K (1989) Geochim. Cosmochim. Acta 53, 1657-1668. Fogel R.A., Hess P.C. and Rutherford M.C. (1989) Geochim. Cosmochim. Acta 53, 2735-2746. Kissin S.A.(1989) Geochim. Cosmochim. Acta 53, 1649-1655. Larimer J.W. and Buseck P.R. (1974) Geochim. Cosmochim. Acta 38, 471-477. Skinner B.J. and Luce F.D. (1971) Amer. Min. 56, 1269-1296. Figure 1, which in the hard copy appears here, shows isotherm from the Fe-Ni-P phase diagram with data for enstatite chondrites superimposed.
Qiu, Kun-Feng; Deng, Jun; Taylor, Ryan D.; Song, Kai-Rui; Song, Yao-Hui; Li, Quan-Zhong; Goldfarb, Richard J.
2016-01-01
The NWW-striking North Qilian Orogenic Belt records the Paleozoic accretion–collision processes in NW China, and hosts Paleozoic Cu–Pb–Zn mineralization that was temporally and spatially related to the closure of the Paleo Qilian-Qinling Ocean. The Wangdian Cu deposit is located in the eastern part of the North Qilian Orogenic Belt, NW China. Copper mineralization is spatially associated with an altered early Paleozoic porphyritic granodiorite, which intruded tonalites and volcaniclastic rocks. Alteration zones surrounding the mineralization progress outward from a potassic to a feldspar-destructive phyllic assemblage. Mineralization consists mainly of quartz-sulfide stockworks and disseminated sulfides, with ore minerals chalcopyrite, pyrite, molybdenite, and minor galena and sphalerite. Gangue minerals include quartz, orthoclase, biotite, sericite, and K-feldspar. Zircon LA-ICPMS U–Pb dating of the ore-bearing porphyritic granodiorite yielded a mean 206Pb/238U age of 444.6 ± 7.8 Ma, with a group of inherited zircons yielding a mean U–Pb age of 485 ± 12 Ma, consistent with the emplacement age (485.3 ± 6.2 Ma) of the barren precursor tonalite. Rhenium and osmium analyses of molybdenite grains returned model ages of 442.9 ± 6.8 Ma and 443.3 ± 6.2 Ma, indicating mineralization was coeval with the emplacement of the host porphyritic granodiorite. Rhenium concentrations in molybdenite (208.9–213.2 ppm) suggest a mantle Re source. The tonalities are medium-K calc-alkaline. They are characterized by enrichment of light rare-earth elements (LREEs) and large-ion lithophile elements (LILEs), depletion of heavy rare-earth elements (HREEs) and high-field-strength elements (HFSEs), and minor negative Eu anomalies. They have εHf(t) values in the range of +3.6 to +11.1, with two-stage Hf model ages of 0.67–1.13 Ga, suggesting that the ca. 485 Ma barren tonalites were products of arc magmatism incorporating melts from the mantle wedge and the lithosphere. In contrast, the 40-m.y.-younger ore-bearing porphyritic granodiorite is sub-alkaline and peraluminous. They are enriched in LREEs and LILEs, depleted in HFSEs, and show weak negative Eu anomalies. They displayεHf(t) values of captured or inherited zircons in the range of +8.5 to +10.0, and younger two-stage Hf model ages of 0.78 Ga and 0.86 Ga, similar to those of ca. 485 Ma tonalite. The ca. 445 Ma zircons have εHf(t) values of −2.1 to +9.9, with two-stage Hf model ages of 0.75–1.27 Ga. Moreover, they have relatively high oxygen fugacity than that of the precursor barren tonalite. The ca. 445 Ma magmas at Wangdian thus formed in a subduction setting, and incorporated melts from the subduction-modified lithosphere that had previously been enriched by additions of chalcophile and siderophile element-rich materials by the earlier magmatism and metasomatism during the Paleo Qilian-Qinling Ocean subduction event.
Geology of the Alaska-Juneau lode system, Alaska
Twenhofel, William Stephens
1952-01-01
The Alaska-Juneau lode system for many years was one of the worlds leading gold-producing areas. Total production from the years 1893 to 1946 has amounted to about 94 million dollars, with principal values in contained gold but with some silver and lead values. The principal mine is the Alaska-Juneau mine, from which the lode system takes its name. The lode system is a part of a larger gold-bearing belt, generally referred to as the Juneau gold belt, along the western border of the Coast Range batholith. The rocks of the Alaska-Juneau lode system consist of a monoclinal sequence of steeply northeasterly dipping volcanic, state, and schist rocks, all of which have been metamorphosed by dynamic and thermal processes attendant with the intrusion of the Coast Range batholith. The rocks form a series of belts that trend northwest parallel to the Coast Range. In addition to the Coast Range batholith lying a mile to the east of the lode system, there are numerous smaller intrusives, all of which are sill-like in form and are thus conformable to the regional structure. The bedded rocks are Mesozoic in age; the Coast Range batholith is Upper Jurassic and Lower Cretaceous in age. Some of the smaller intrusives pre-date the batholith, others post-date it. All of the rocks are cut by steeply dipping faults. The Alaska-Juneau lode system is confined exclusively to the footwall portion of the Perseverance slate band. The slate band is composed of black slate and black phyllite with lesser amounts of thin-bedded quartzite. Intrusive into the slate band are many sill-like bodies of rocks generally referred to as meta-gabbro. The gold deposits of the lode system are found both within the slate rocks and the meta-gabbro rocks, and particularly in those places where meta-gabbro bodies interfinger with slate. Thus the ore bodies are found in and near the terminations of meta-gabbro bodies. The ore bodies are quartz stringer-lodes composed of a great number of quartz veins from 6 inches to 3 feet wide and extending along their strike and dip for several tens to hundreds of feet. In addition to quartz, the only other vein gangue mineral is ankerite. It occurs in small amounts along the borders of the quartz veins. Metallic vein minerals, in addition to native gold, are, in order of decreasing abundance, pyrrhotite, galena, sphalerite, and arsenopyrite. In the aggregate the metallic minerals comprise only 1 to 2 percent of the total amount of vein material. The wall rock, particularly the meta-gabbro, was profoundly altered by the vein-forming processes. The principal effects on the meta-gabbro were the addition of large amounts of soda, potash, titanium, carbon dioxide, and phosphorous, and the removal of considerable quantities of iron, magnesia, lime, and combined water. Silica also may have been decreased. The mineralogical changes involved in the alteration were the development of biotite and ankerite at the expense of original hornblende and feldspar, resulting in a brown-colored biotite- and ankerite-rich rock. The slates are relatively unaffected by the vein-forming processes. Because of their small size, relatively low grade, and discontinuity, no attempt has been made to mine any individual vein. The prevailing practice has been to mine large blocks of ground by a system of modified block-caving, followed by hand sorting to remove the barren country rock from the gold-bearing quartz prior to milling.
NASA Astrophysics Data System (ADS)
Sonntag, Iris; Hagemann, Steffen
2010-05-01
Detailed petrographic as well as hyperspectral analyses using PIMA (Portable Infrared Mineral Analyser) and geochemical (major, trace and rare earth elements) studies were conducted on samples of the epithermal, low sulfidation Co-O mine (47,869 ounces gold produced in 2009 with an average grade of 13.3 g/t gold) and district in Eastern Mindanao (Philippines). The aims of the study were to unravel the petrogenetic origin of the various volcanic (host rocks) and intrusive rocks (potential fluid driver) as well as their relationship and influence on the hydrothermal alteration zoning and fluid chemistry. The auriferous veins at the Co-O mine were formed during two hydrothermal stages associated with the district wide D1 and D2 deformation events. Gold in stage 1 quartz veins is in equilibrium with galena and sphalerite, whereas in stage 2 it is associated with pyrite. Auriferous quartz veins of stage 1 reflect temperatures below 250° C or strong variations in pH and fO2 at higher temperatures, due to potential involvement of acidic gas or meteoric water. Cathodoluminescense studies revealed strong zonation of quartz associated with Au, presumably related to changes in the Al content, which is influenced by the pH. Plumose textures indicate times of rapid deposition, whereas saccharoidal quartz grains are related to potential calcite replacement. The geology of the Co-O mine and district is dominated by Miocene volcanic rocks (basic to intermediate flows and pyroclastics units), which are partly covered by Pliocene volcanic rocks and late Oligocene to Miocene limestones. The Miocene units are intruded by diorite (presumably Miocene in age). The epithermal mineralization event may be related to diorite intrusions. The geochemistry of all igneous rocks in the district is defined by a sub-alkaline affinity and is low to medium K in composition. Most units are related to a Miocene subduction zone with westward subduction, whereas the younger Pliocene rocks are related to the currently active east dipping subduction zone. At the Co-O mine the proximal hydrothermal alteration zone is defined by phyllic to argillic alteration displayed in sericitized to carbonated feldspar, quartz and chloritized amphiboles surrounded by a distal alteration halo displaying propylitic alteration. The alteration geochemistry of these hydrothermal altered rocks is defined by an increase in K2O and Na2O and decrease in Al2O3. However, adularia usually associated with hydrothermal alteration in low epithermal Au quartz veins, has so far not been described, which points to a K-poor magma system. PIMA hydrothermal alteration studies indicate the dominant presence of smectite rather than white mica, which supports the involvement of a K-poor hydrothermal fluid. The epithermal Co-O mine and district displays low to medium potassic magma series and a hydrothermal alteration mineralogy that is K-poor. However, the Co-O mine hosts significant amounts of epithermal gold mineralization. The recognition of poor K melts and hydrothermal alteration mineralogy associated with distinct low-sulfidation epithermal gold mineralization has important implication for exploration in the Co-O district and, potentially, also in other areas in the Philippines and worldwide.
Mineralogy and ore fluid chemistry of the Roc Blanc Ag deposit, Jebilet Hercynian massif, Morocco
NASA Astrophysics Data System (ADS)
Essarraj, Samira; Boiron, Marie-Christine; Cathelineau, Michel; Tarantola, Alexandre; Leisen, Mathieu; Hibti, Mohamed
2017-03-01
The Roc Blanc Ag deposit is located about 20 km north of Marrakesh city (Morocco) in the Jebilet Hercynian massif. The ore bodies consist of N-S to NE-SW quartz (±carbonates) veins hosted by the Sarhlef marine sediments. These series, deposited in a Devonian-Carboniferous rift basin context, were deformed during the Hercynian orogeny, and submitted to low-grade regional metamorphism. Two major stages of fluid circulation and metal deposition are distinguished on the basis of mineralogical and paleo-fluid studies carried out on quartz and dolomite (microthermometry, Raman spectroscopy, LA-ICP-MS on individual inclusions, and O, H stable isotope data): (i) an early Fe-As stage, characterized by the circulation of metamorphic aqueous-carbonic fluids, under P-T conditions lower than 200 MPa ± 20 MPa and 400 °C respectively, along N-S structures; (ii) the ore stage, characterized by the circulation of a Na-Mg-K ± Ca high salinity brine, poor in gas but rich in metals such as Fe, Sr, Ba, Zn, Pb, ± Cu (salinity ranging from 19.6 wt% to likely more than 30 wt% NaCl equiv.) and the deposition of a sphalerite/dolomite-calcite assemblage; such a fluid likely evolved to a Na-K-(Ca-Mg)-Ag brine, with significant Pb and Sb concentrations and lower Sr, Ba and Zn concentrations than in the preceding fluid (salinity up to 19.4 wt% NaCl equiv.). The Ag content of the second mineralizing brine ranges from 0.9 mmol/kg to 9.4 mmol/kg solution (100 ppm-1000 ppm), whereas the base metal brine is generally Ag poor (up to 1.3 mmol/kg solution: 140 ppm). Dilution of the Ag brine by low salinity fluids (<6 wt% NaCl equiv., and Th from 130° to 230 °C) seems to be the main driving mechanism for the Ag ore deposition at Roc Blanc, with a possible involvement of cooling and reduction reactions in black schists. Base metal and Ag fluids may have circulated at average temperatures around 200 ± 30 °C or slightly higher and under hydrostatic pressures, along dominant E-W structures. The ore forming model proposed for the Roc Blanc deposit is: (i) the penetration of sedimentary brines coming from the adjacent basins into the basement (i.e. Hercynian formations), where they extracted Ag probably from abundant mafic rocks; ii) the ore deposition in structural traps below the post Hercynian unconformity thanks to brine mixing with low salinity fluids. The fluid circulation probably is related to the Atlasic rifting coeval with the Atlantic Triassic opening. Such a model contrasts with the previous one relating the Roc Blanc to the Hercynian granitic intrusions in the Jebilet. Ag deposition occurred during reworking of the early structures associated with the Hercynian orogenic events and metamorphic fluid circulation which led to the early Fe-As uneconomic stages forming the main N-S quartz veins. Similarities between The Roc Blanc Ag deposit and the major Ag deposits from Anti-Atlas south of Morocco strongly suggest that they resulted from a unique and large fluid circulation event and a major period of metal deposition.
Monitorization of technosols in old mining sites treated with calcareous fillers
NASA Astrophysics Data System (ADS)
Martínez-Sanchez, MJose; Perez-Sirvent, Carmen; Garcia-Lorenzo, MariLuz; Gonzalez, Eva; Perez-Espinosa, Victor; Martínez-Lopez, Salvadora; Hernandez, Carmen; Molina, Jose; Martínez, Lucia B.
2014-05-01
A large number of soils around the world are contaminated by heavy metals due to mining activities, generating adverse effects on human health and the environment. In response to these negative effects, a variety of technologies to remediate soils affected by heavy metals have been developed. Among them, in situ immobilization by means of soil amendment is a non-intrusive and cost effective alternative, that transforms the highly mobile toxic heavy metals to physico-chemically stable forms, reducing their mobility and environmental risks. Limestone filler is a good selection for such a purpose, because of its low permeability and low solubility, due to its high degree of physical-chemical stability and because is a non-toxic material with a high finely divided calcium carbonate content. In addition, the use of this amendment could revalorize the residues, reducing the costs of the process. The objective of this work was to evaluate the effectiveness of a immobilization technique in sediments contaminated by heavy metals as a results of mining activities. The study area was Portman bay, located close to the mining region of La Unión and subjected to mining from the time of the Roman Empire to 1991. Wastes from mining activities mainly consisted in ore materials (galena, pyrite and sphalerite), phyllosilicates, in addition to siderite, iron oxides and sometimes alteration products such as jarosite, alunite, kaolinite and greenalite. These materials have suffered a concentration process by floatation with sea water and, as a result of the discharge, the whole of the bay has filled up with wastes which also extend into the Mediterranean Sea. Two experimental areas, approximately 1 Ha each one, were selected and technosols were developed as follows: original sediments from the bay, sediments mixed with limestone filler in a 1:1 proportion, gravel to avoid capillary and natural soil to allow plant growth. After the remediation technique was applied, monitorization of experimental areas was done in 18 sampling points in which sediment and water samples were collected and analyzed. Monitorization was carried out during a 4 years period, samples being obtained at two month intervals. The pH and the electrical conductivity were determined, in naddition to the heavy metal concentration. The Zn content was determined by flame atomic absorption spectrometry. The Pb, Cd and Cu content was determined by electrothermal atomization atomic absorption spectrometry. The As content was measured by atomic fluorescence spectrometry using an automated continuous flow hydride generation spectrometer. In addition, Microtox bioassay was applied in order to study ecotoxicity of collected water samples. Sediments before the remediation technique showed acidic pH, high EC values and high trace elements content. The results obtained after the immobilization showed that sediment samples had neutral pH (average value of 8.3) low electrical conductivity (1.32 dS m-1) and low trace elements concentration, in some cases below the detection limit. When water samples obtained in the piezometers were evaluated, the results indicated that these samples correspond to rainfall waters and were characterized by neutral pH and trace elements concentration below the detection limit. In addition, none of them showed toxicity when submitted to the selected bioassay Then, we can conclude that the use of limestone filler constitutes an excellent option in sediments polluted by trace elements, because of risk for human health or ecosystem does not exist or is decreased in a large extent after the intervention. In addition, the designed experience allows stabilizer proportion to be optimized and may suppose a big cost-saving in the project in areas affected by mining activities.
The Russell gold deposit, Carolina Slate Belt, North Carolina
Klein, T.L.; Cunningham, C.G.; Logan, M.A.V.; Seal, R.R.
2007-01-01
Gold deposits have been mined in the Carolina slate belt from the early 1800s to recent times, with most of the production from large mines in South Carolina. The Russell mine, one of the larger producers in North Carolina, is located in the central Uwharrie Mountains, and produced over 470 kg of gold. Ore grades averaged about 3.4 grams per tonne (g/ t), with higher-grade zones reported. The Russell deposit is interpreted to be a sediment-hosted, gold-rich, base-metal poor, volcanogenic massive sulfide deposit in which gold was remobilized, in part, during Ordovician metamorphism. The ore was deposited syngenetically with laminated siltstones of the late Proterozoic Tillery Formation that have been metamorphosed to a lower greenschist facies. The Tillery Formation regionally overlies subaerial to shallow marine rhyolitic volcanic and volcaniclastic rocks of the Uwharrie Formation and underlies the marine volcanic and sedimentary rocks of the Cid Formation. Recent mapping has shown that a rhyolitic dome near the Russell mine was extruded during the deposition of the lower part of the Tillery Formation, at about the same time as ore deposition. Relict mafic, rock fragments present in the ore zones suggest contemporaneous bimodal (rhyolite-basalt) volcanism. The maximum formation age of the Russell deposit is younger than 558 Ma, which is similar to that of the larger, well known Brewer, Haile, and Ridgeway deposits of South Carolina. Gold was mined from at least six zones that are parallel to the regional metamorphic foliation. These strongly deformed zones consist of northeast-trending folds, high-angle reverse faults, and asymmetric doubly plunging folds overturned to the southeast. The dominant structure at the mine is an asymmetric doubly plunging anticline with the axis trending N 45?? E, probably related to late Ordovician (456 ?? 2 Ma) regional metamorphism and deformation. Two stages of pyrite growth are recognized. Stage 1, primary, spongy pyrite, is present in thin massive sulfide layers parallel to bedding and intergrown with pyrrhotite, chalcopyrite, sphalerite, and sparse arsenopyrite. Stage 2, secondary pyrite, is present as euhedral, idiomorphic rims on spongy pyrite and as veinlets that parallel the regional foliation. Stage 1 pyrite was deposited syngenetically or diagenetically during or soon after sedimentation. Stage 2 pyrite overgrowths and veins resulted from recrystallization or remobilization of stage 1 pyrite, probably during deformation related to Ordovician regional metamorphism. It is proposed that the spongy texture of the stage 1 pyrite represents nucleation and growth of pyrite on organic matter, possibly of bacterial origin. Other textures, such as geometric voids in spongy pyrite, As-rich zones surrounding central voids, 60-??m ring structures composed of spongy pyrite, and layers of spongy pyrite interlayered with bedding laminations, also appear to indicate replacement of organic matter by pyrite. Stage 1 pyrite contains up to 0.06 wt percent gold. The ??34S values of pyrite in and near pyritic ore (3.5-4.5???), in the rhyolite dome (5.1-5.4???) and in the Tillery Formation (5.9-6.2???) are interpreted to reflect mixing of sulfur derived from igneous and seawater sources. Whole-rock ??18O values of nearby unaltered mudstone are about 11 per mil whereas those from altered mudstone at the deposit are 7.4 to 10.6 per mil. The lower ?? 18O values are interpreted to indicate possible high-temperature exchange between relatively low ??18O hydrothermal fluids and the wall rocks. Gold, As, K, and Mo are enriched relative to the regional background in both the ore zones and in pyrite veins and disseminations in the nearby rhyolite dome, suggesting a possible genetic link between the rhyolitic volcanism and the gold mineralization. ?? 2007 Society of Economic Geologists, Inc.
NASA Astrophysics Data System (ADS)
Lee, Sudarat
This dissertation presents the methodology and discussion of preparing nanostructured, high aspect ratio p-type phosphide-based binary and ternary semiconductors via "top-down" anodic etching, a process which creates nanostructures from a large parent entity, and "bottom-up" vapor-liquid-solid growth, a mechanism which builds up small clusters of molecules block-by-block. Such architecture is particularly useful for semiconducting materials with incompatible optical absorption depth and charge carrier diffusion length, as it not only relaxes the requirement for high-grade crystalline materials, but also increases the carrier collection efficiencies for photons with energy greater than or equal to the band gap. The main focus of this dissertation is to obtain nanostructured p-type phosphide semiconductors for photoelectrochemical (PEC) cell applications. Chapter II in the thesis describes a methodology for creating high-aspect ratio p-GaP that function as a photocathode under white light illumination. Gallium phosphide (GaP, band gap: 2.26 eV) is a suitable candidate for solar conversion and energy storage due to its ability to generate large photocurrent and photovoltage to drive fuel-forming reactions. Furthermore, the band edge positions of GaP can provide sufficient kinetics for the reduction of protons and carbon dioxide. The structure is prepared by anodic etching, and the resulting macroporous structures are subsequently doped with Zn by thermally driving in Zn from conformal ZnO films prepared by atomic layer deposition (ALD). The key finding of this work is a viable doping strategy involving ALD ZnO films for making functioning p-type GaP nanostructures. Chapter III compares the GaP nanowires grown from gold (Au) and tin (Sn) VLS catalysts in a benign solid sublimation growth scheme in terms of crystal structure and photoactivity. Sn is less noble than Au, allowing complete removal of Sn metal catalysts from the nanowires through wet chemical etching which found to be useful for subsequent thermal diffusion p-type doping without fear of contaminations like Au. The main finding of this work is Sn-seeded GaP nanowires although Sn was removed without any residues and the nanowires had less twin defects than Au-seeded GaP, the nanowires were degenerately n-doped. On the contrary, Au-seeded GaP nanowires exhibited n-type characteristics with orthogonalized light absorption and charge separation. Chapter IV describes the synthesis of zinc tin phosphide (ZSP), a ternary analog of GaP comprised of low-cost, earth-abundant elements in the nanowire form using Sn nanoparticles as the VLS growth seed. The as-prepared ZSP nanowire film is capable of sustaining stable cathodic photoresponse in aqueous electrolyte under white light illumination. The nanowires were crystalized in the stoichiometric sphalerite form and possessed a direct optical band gap of ˜ 1.5 eV instead of the chalcopyrite structure that has comparable band gap energy to GaP. The Sn nanoparticles acted as the VLS seed as well as Sn source for the ZnSnP 2 nanowires growth. Chapter V summarizes the progress and findings of p-GaP nanowire array films as well as a phase non-specific, persistent ALD dye attachment scheme that facilitates hole injection into p-GaP photocathodes, extending the photon absorption range beyond its band gap. Lastly, a separate work about undergraduate chemical education development is documented in Chapter VI of this thesis. Chapter VI details the efforts made in two distinct undergraduate laboratory coursework with the intention to introduce modern microfluidics and photovoltaic technologies including multidisciplinary research experience to the undergraduate students.
NASA Astrophysics Data System (ADS)
Seitz, Russell
1989-01-01
When, in the course of advancing the state of the art, one slams into a material barrier to the construction of one's appointed gadget, it is customary, and at times mandatory, to drop to one's knees and pray to DARPA for deliverance. Deliverance in the form of the right stuff. Something superbly strong, something utterly transparent, something remarkably light, and with dielectric properties rivaling a perfect vacuum. Ideally, this something should also be bulletproof, better at conducting heat than a silver spoon, insoluble in boiling acid, radiation hard, non-toxic, and cheap. Well, historically, nine out of ten isn't bad for a start. Indeed, it's better than nothing. So let me begin with some history. What we today call solid state physics began not as science but as technology. Victorian low technology to be exact. The first practical solid state electronic devices, demonstrated by Ferdinand Braun* at Leipzig on November 14, 1876, were based neither on theory nor on synthesis, nor on crystal growth. For in those days these things existed not. They were instead dug up, mined as lead ore. The performance of the galena (PbS) cat's whisker diode was marginal; it was rapidly superseded by the first, worse vacuum tube . So also, early infrared optics of rock salt gave way to synthetic crystals. But those early artifacts' performance demanded a physical explanation, and after a brief hiatus, in order for Willard Gibbs to break ground by inventing thermodynamics, the modern theory of solids arose to provide it. It all stemmed from the enterprise of explaining first the optical properties and then the electronic bebavior of crystals found in rocks. Today diamond, along perhaps with Iceland spar, remains the last optical material to be technically exploited as it is found in nature. It is a barbarous relic, a throwback to high technology's dim Neolithic past. For nowadays we are used to thinking about synthetic optical materials, like zinc sulfide or selenide, as being mature, as being just so much up market optical glass. They're stock items--you pay the money and the stuff shows up in big transparent slabs. That wasn't true even in 1970. Then, as with diamond, there was essentially none to be had. The first measurements of the non-linear refractive index of ZnS had to be made on a sample of zinc ore from a Harvard museum--a pale green crystal of sphalerite whose optical quality then represented the state, not of the art, which was then non-existent, but of nature at her best. So what can we do today when we're interested in a material that we are still learning to make as well as nature does? There are two maxims of the earth sciences that could be of service in the near term to the area of materials science that we are gathered here to discuss. One is: "The best geologist is the one who has seen the most rocks" the other is more germane still: "Rocks are just ceramics that happen to have been made by God." Diamond is no exception, for today more than ever before, ceramics aren't just common clay. So, naturally, there presently exist more shapes, forms, growth morphologies, surface textures, and degrees of optical quality in the diamonds of a good mineralogical collection than have, as of yet, been synthesized. Good, bad, and ugly, these varieties of natural diamond fall into two categories: the ones we have seen already synthesized and the ones that we will see. And the more we can find out about the natural history of the latter, the sooner we will see them synthetically reproduced.
Applied geochemistry, geology and mineralogy of the northernmost Carlin trend, Nevada
Theodore, T.G.; Kotlyar, B.B.; Singer, D.A.; Berger, V.I.; Abbott, E.W.; Foster, A.L.
2003-01-01
Investigations in the northernmost Carlin trend were undertaken to advance understanding of the geochemical signatures and genesis of precious metal deposits in the trend. Two fundamental geologic relationships near the trend significantly affect regional geochemical distributions: a remarkably intact lower Paleozoic stratigraphic sequence of siliceous rocks in the upper plate of the middle Paleozoic Roberts Mountains thrust, and the widespread repetition of rocks high in the upper plate during late Paleozoic thrusting that thickens the cover above mineralized rock in the lower plate. A compilation of previously published chemical analyses of 440 stream sediment samples and 115 rocks from two 7 1/2-minute quadrangles, as well as new chemical analyses of approximately 1,000 drill core samples in a 1,514 m (4,970 ft) hole through the Rodeo Creek deposit were used to construct three-dimensional element distribution models that highlight metal zonation in the mineralized systems. The Rodeo Creek deposit comprises deep Ag base-metal ?? Au-mineralized rock below the Roberts Mountains thrust and contains an unusually high Ag/Au ratio greater than 30. Stacked geochemical halos related to the deposit are confined to the lower plate of the Roberts Mountains thrust and include two horizons of Hg, Cu, and Zn anomalies-as much as 180 m above the deposit-that mostly result from mercurian sphalerite. Extremely subtle indications of mineralization in the upper plate of the Roberts Mountains thrust above the deposit include arsenopyrite overgrowths on small pyrite crystals in 50- to 75-??m-wide clay-carbonate veinlets that lack alteration halos, arsenical rims on small disseminated crystal of recrystallized diagenetic pyrite, and partial replacement of diagenetic pyrite by tennantite. Some of these minerals contain anomalously high Au. However, these As-(Au)-bearing rocks most likely represent another locus of largely untested mineralized rock rather than distal halos related to either the Rodeo Creek or the nearby Dee and Storm gold deposits. Application of micromineralogic techniques helped to identify mineral assemblages that are specific to mineralization and provided an empirical foundation for interpretations of geochemical halos in the Carlin trend. District-scale geochemical patterns of several elements in stream sediments and surface rocks coincide with the northernmost Carlin trend and can be used to explore for Carlin-type deposits. Concentrations of elevated As and Sb in stream sediments (as much as 54 ppm As) have northwest-elongate lobate patterns that clearly outline the trend across a width of approximately 4 km. Arsenic contents of exposed rocks (as much as 90 ppm As) strongly correlate with As contents of derivative stream sediments, and rock contents of Sb show a somewhat lesser but nonetheless strong and similar correspondence. Factor analysis of stream-sediment data shows that those factor scores that are correlated with As, Sb, Au, and Pb also are high along the trend and suggest that mineralized rocks may be present. Although As was not detected by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) studies in heavy mineral concentrates of high-As stream sediments in the Carlin trend, X-ray absorption near-edge spectra (XANES) of selected light fractions of stream sediment samples indicate that Al-bearing phases, such as gibbsite, amorphous Al oxyhydroxides, or aluminosilicate clay minerals host most of the As(V). The best fit, visually and in terms of the lowest residual, was obtained by a model compound of As(V) sorbed to gibbsite. Thus, most As in stream sediments derived from altered rock within the Carlin trend apparently is contained in light fractions. The geochemical character of young, unconsolidated, postmineral deposits that cover mineralized rocks on the Carlin trend partly results from mineralized sources along the trend. Concentration of As in the Miocene Carlin Formation shows an exceptio
NASA Astrophysics Data System (ADS)
Éric, Marcoux; Khadija, Nerci; Yannick, Branquet; Claire, Ramboz; Gilles, Ruffet; Jean-Jacques, Peucat; Ross, Stevenson; Michel, Jébrak
2015-07-01
Gold have been recently recognized in the Tighza (formerly Jebel Aouam) district, in the Hercynian belt of central Morocco. This district has long been known for its W mineralization, as well as major Pb-Ag-Zn, and minor Sb-Ba deposits, all geographically associated with late-Hercynian calc-alkaline magmatism. Gold mineralization in the district is mainly hosted by thick W-Au quartz veins located around the "Mine granite" small granitic plug. Within the veins, gold grade is highest (up to 70 g/t) close to the granite but rapidly decreases going outward from the granite, defining a perigranitic zoning. Anomalous gold grades have also been measured in hydrothermal skarn layers close to two other granitic plugs (Kaolin granite and Mispickel granite), associated with disseminated As-Fe sulfides. The paragenetic sequence for the W-Au quartz veins shows three stages: (1) an early oxidized stage with wolframite-scheelite associated with early quartz (Q1), (2) an intermediate Bi-As-Te-Mo-Au sulfide stage with loellingite, bismuth minerals and native gold with a later quartz (Q2), restricted to a narrow distance from the granite, and (3) a late lower temperature As-Cu-Zn-(Pb) stage with abundant massive pyrrhotite, arsenopyrite and sphalerite, locally forming independent veins ("pyrrhotite vein"). Both Q1 hyaline and Q2 saccharoidal gold-bearing quartz display aqua-carbonic fluids with minor H2S and Cu and an homogeneous composition (81 mole% H2O, 18 mole% CO2 and about 1 mole% NaCl). The trapping pressure is estimated to 1.5-2 kbar with temperature ranging from 300 to 350 °C. Q1 inclusions have exploded indicating an uplift of the Tighza block, that lead to saccharoidal Q2 quartz deposition with multiphase NaCl-saturated fluid inclusions. 40Ar/39Ar dating demonstrates that the "Mine granite", tungsten skarnoid, scheelite-molybdenite veins, and very likely gold-bearing veins are coeval, emplaced at 286 ± 1 Ma. Multiple and widespread metal sources are indicated by radiogenic isotope studies. Nd and Sr isotope compositions of scheelite and granites suggest the participation of a juvenile component while lead isotopes demonstrate a major participation of the basement. Both gold mineralization and zoning suggest that the system developed at the end of the magmatic activity, accompanying a major transition in magmatic fluid composition. The morphology of the gold-bearing mineralization is dependent of the permeability and the reactivity of host-rocks: focus circulation of fluids through pre-existing tectonic corridors, reactivated by late-Hercynian intrusions favor the formation of large W-type gold veins, while infiltration of fluid within reactive stratigraphic layers gives rise to skarn mineralization. A 40Ar/39Ar date (W1 north vein: 291.8 ± 0.3 Ma) indicates that hydrothermal circulation predates gold and tungsten deposition in open fractures as well as Mine granite emplacement. The W-Au mineralization preceded the onset of a large convective hydrothermal cell around the intrusion that led to the formation of the Pb-Ag-Zn mined veins. The Tighza polymetallic district displays numerous similarities with the R-IRG model that was defined in the American Cordillera, such as thermal and zonation patterns, carbonic hydrothermal fluids and chronology of intrusion and related deposits, but also provides new insight to the R-IRG model such as wide Au-quartz veins instead of sheeted Au-veins, oxidation state of the magma, and Sr-Nd isotopic data. These results establish a major magmatic contribution and discard a direct genetic relationship between gold mineralization and major neighboring Pb-Ag-Zn veins. A large number of classic Pb-Zn district of the Western Hercynides belong to the same clan.
Olson, J.C.; Hedlund, D.C.
1981-01-01
Alkalic igneous rocks and related concentrations of thorium, niobium, rare-earth elements, titanium, and other elements have long been known in the Powderhorn mining district and have been explored intermittently for several decades. The deposits formed chiefly about 570 m.y. (million years) ago in latest Precambrian or Early Cambrian time. They were emplaced in lower Proterozoic (Proterozoic X) metasedimentary, metavolcanic, and plutonic rocks. The complex of alkalic rocks of Iron Hill occupies 31 km 2 (square kilometers) and is composed of pyroxenite, uncompahgrite, ijolite, nepheline syenite, and carbonatite, in order of generally decreasing age. Fenite occurs in a zone, in places more than 0.6 km (kilometer) wide, around a large part of the margin of the complex and adjacent to alkalic dikes intruding Precambrian host rock. The alkalic rocks have a radioactivity, chiefly due to thorium, greater than that of the surrounding Powderhorn Granite (Proterozoic X) and metamorphic rocks. The pyroxenite, uncompahgrite, ijolite, and nepheline syenite, which form more than 80 percent of the complex, have fairly uniform radioactivity. Radioactivity in the carbonatite stock, carbonatite dikes, and the carbonatite-pyroxenite mixed rock zone, however, generally exceeds that in the other rocks of the complex. The thorium concentrations in the Powderhorn district occur in six types of deposits: thorite veins, a large massive carbonatite body, carbonatite dikes, trachyte dikes, magnetite-ilmeniteperovskite dikes or segregations, and disseminations in small, anomalously radioactive plutons chiefly of granite or quartz syenite that are older than rocks of the alkalic complex. The highest grade thorium concentrations in the district are in veins that commonly occur in steeply dipping, crosscutting shear or breccia zones in the Precambrian rocks. They range in thickness from a centimeter or less to 5 m (meters) and are as much as 1 km long. The thorite veins are composed chiefly of potassic feldspar, white to smoky quartz, calcite, barite, goethite, and hematite, and also contain thorite, jasper, magnetite, pyrite, galena, chalcopyrite, sphalerite, synchysite, apatite, fluorite, biotite, sodic amphibole, rutile, monazite, bastnaesite, and vanadinite. The Th0 2 content of the thorite veins ranges from less than 0.01 percent to as much as 4.9 percent in high-grade samples. The Th0 2 content is generally less than 1 percent, however, and is only 0.05 to 0.1 percent in many of the veins examined in the district. Samples of the dolomitic carbonatite of Iron Hill mostly range from 3 to 145 ppm (parts per million) thorium. Thirty samples of the carbonatite dikes, the most radioactive rocks within the complex of Iron Hill, contain about 30 to 3,200 ppm thorium and a trace to about 1.5 percent rare-earth oxides. The magnetite-ilmenite-perovskite rocks have a radioactivity of 2 to 12 times the background of Precambrian granite that is attributable chiefly to thorium substitution for calcium in the perovskite. In two analyses the perovskite contains 0.12 and 0.15 percent Th0 2 . Trachyte dikes as much as 25 m thick cut the Precambrian rocks; their radioactivity is generally about two to four times the background of typical Precambrian granite, is locally higher, but is low relative to other types of thorium concentrations. A finegrained granite that is anomalously radioactive occurs in thick, dikelike plutons as much as 1.2 km wide, or more. The thorium content varies widely within the granite bodies. Eight samples of the granite contain 32 to 281 ppm thorium (averaging 115 ppm). The economic potential of thorium in the Powderhorn district is related in part to other elements such as niobium, titanium, iron, and rare earths. The proportions of niobium and rare earths to thorium vary in different parts of the district. Within the carbonatite body of Iron Hill, the Nb 2 0 5 content greatly exceeds Th0 2 , but the Th0 2 -Nb 2 0 5
Dusel-Bacon, Cynthia; Slack, John F.; Aleinikoff, John N.; Mortensen, James K.
2009-01-01
We present here the initial results of a petrographic, geochemical, and isotopic study of Mesozoic intrusive rocks and spatially associated Zn-Pb-Ag-Cu-Au prospects in the Fortymile mining district in the southern Eagle quadrangle, Alaska. Analyzed samples include mineralized and unmineralized drill core from 2006 and 2007 exploration by Full Metal Minerals, USA, Inc., at the Little Whiteman (LWM) and Fish prospects, and other mineralized and plutonic samples collected within the mining district is part of the USGS study. Three new ion microprobe U-Pb zircon ages are: 210 +- 3 Ma for quartz diorite from LWM, 187 +- 3 Ma for quartz monzonite from Fish, and 70.5 +- 1.1 Ma for altered rhyolite porphyry from Fish. We also present 11 published and unpublished Mesozoic thermal ionization mass spectrometric U-Pb zircon and titanite ages and whole-rock geochemical data for the Mesozoic plutonic rocks. Late Triassic and Early Jurassic plutons generally have intermediate compositions and are slightly foliated, consistent with synkinematic intrusion. Several Early Jurassic plutons contain magmatic epidote, indicating emplacement of the host plutons at mesozonal crustal depths of greater than 15 km. Trace-element geochemical data indicate an arc origin for the granitoids, with an increase in the crustal component with time. Preliminary study of drill core from the LWM Zn-Pb-Cu-Ag prospect supports a carbonate-replacement model of mineralization. LWM massive sulfides consist of sphalerite, galena, and minor pyrite and chalcopyrite, in a gangue of calcite and lesser quartz; silver resides in Sb-As-Ag sulfosalts and pyrargyrite, and probably in submicroscopic inclusions within galena. Whole-rock analyses of LWM drill cores also show elevated In, an important metal in high-technology products. Hypogene mineralized rocks at Fish, below the secondary Zn-rich zone, are associated with a carbonate host and also may be of replacement origin, or alternatively, may be a magnetite-bearing Zn skarn. Cu-Zn-Pb-Ag-Au showings at the Oscar pros-pect occur in marble-hosted magnetite and pyrrhotite skarn that is spatially related to the stocks, dikes, and sills of the Early Jurassic syenite of Mount Veta. Mineralized rocks at the Eva Creek Ag-Zn-Pb-Cu prospect are within 1.5 km of the Mount Veta pluton, which is epidotized and locally altered along its contact with metamorphosed country rock east of the prospect. We report five new sulfide Pb-isotopic analyses from the LWM, Oscar, and Eva Creek prospects and compare these sulfide Pb-isotopic ratios with those for sulfides from nearby deposits and prospects in the Yukon-Tanana Upland and with feldspar Pb-isotopic ratios for Mesozoic plutons in the region. Disparities between the Pb-isotopic ratios for sulfides and igneous feldspars are consistent with a carbonate-replacement model for both the LWM and Eva Creek prospects. The presence in the Fortymile district of base-metal sulfides within both calc-silicate-rich skarns and the calc-silicate-free carbonate replacement deposits may reflect multistage mineralization by magmatic-hydrothermal systems during the emplacement of two or more magmatically unrelated igneous intrusions. Alternatively, all of the mineralized occurrences could be products of one regionally zoned system that formed during the intrusion of a single pluton. In addition to the likely origin of some of the base-metal occurrences by intrusion-related hydrothermal fluids, proximity of the LWM prospect to the northeast-striking, high-angle Kechumstuk Fault suggests that fluid flow along the fault also played an important role during carbonate-replacement mineralization.
Slack, J.F.; Kelley, K.D.; Anderson, V.M.; Clark, J.L.; Ayuso, R.A.
2004-01-01
Geochemical analyses of major, trace, and rare earth elements (REE) in more than 200 samples of variably silicified and altered wall rocks, massive and banded sulfide, silica rock, and sulfide-rich and unmineralized barite were obtained from the Main, Aqqaluk, and Anarraaq deposits in the Red Dog Zn-Pb-Ag district of northern Alaska. Detailed lithogeochemical profiles for two drill cores at Aqqaluk display an antithetic relationship between SiO2/Al2O3 and TiO2/Zr which, together with textural information, suggest preferential silicification of carbonate-bearing sediments. Data for both drill cores also show generally high Tl, Sb, As, and Ge and uniformly positive Eu anomalies (Eu/Eu* > 1.0). Similar high Tl, Sb, As, Ge, and Eu/Eu* values are present in the footwall and shallow hanging wall of Zn-Pb-Ag sulfide intervals at Anarraaq but are not as widely dispersed. Net chemical changes for altered wall rocks in the district, on the basis of average Al-normalized data relative to unaltered black shales of the host Kuna Formation, include large enrichments (>50%) of Fe, Ba, Eu, V, S, Co, Zn, Pb, Tl, As, Sb, and Ge at both Red Dog and Anarraaq, Si at Red Dog, and Sr, U, and Se at Anarraaq. Large depletions (>50%) are evident for Ca at both Red Dog and Anarraaq, for Mg, P, and Y at Red Dog, and for Na at Anarraaq. At both Red Dog and Anarraaq, wall-rock alteration removed calcite and minor dolomite during hydrothermal decarbonation reactions and introduced Si, Eu, and Ge during silicification. Sulfidation reactions deposited Fe, S, Co, Zn, Pb, Tl, As, and Sb; barite mineralization introduced Ba, S, and Sr. Light REE and U were mobilized locally. This alteration and mineralization occurred during Mississippi an hydrothermal events that predated the Middle Jurassic-Cretaceous Brookian orogeny. Early hydrothermal silicification at Red Dog took place prior to or during massive sulfide mineralization, on the basis of the dominantly planar nature of Zn-Pb veins, which suggests filling of fractures that developed in previously lithified rock. Uniformly low Ca and Mg and uniformly negative Ce anomalies in highly siliceous Red Dog wall rocks reflect hydrothermal decarbonation reactions and pervasive silicification owing to conductive cooling of oxidized metalliferous fluids. Similar Ca and Mg depletions are evident at Anarraaq but generally lack associated silicification, possibly because temperatures of the hydrothermal fluids were too low (<180??C) or because the thermal contrast between the fluids and wall rocks was smaller owing to the greater depth of alteration and mineralization there, compared with Red Dog. Chalcophile element anomalies (Fe, Zn, Pb, Tl, As, Sb) in wall rocks at both Red Dog and Anarraq are attributed to sulfidation reactions, coeval with subsurface Zn-Pb-Ag mineralization, during the mixing of oxidized metalliferous fluids with H2S-rich fluids derived locally within the Kuna Formation. Sedimentary wall rocks in the Red Dog district are characterized by a distinctive suite of geochemical anomalies, especially for Zn, Pb, Tl, As, Sb, Ge, and Eu/Eu*. At the Aqqaluk deposit, wall rocks without visible sphalerite or galena (<300 ppm Zn + Pb) have anomalous Eu/Eu*, Tl, Sb, and As for up to ???100 m stratigraphically below Zn-rich silica rock. At Anarraaq, the Tl anomaly is most extensively developed, and enrichment relative to unaltered black shale of the Kuna Formation is present up to 62 m above the highest Zn-Pb sulfide zones. The magnitude of the enrichment and systematic behavior of Tl in the district make Tl a promising geochemical exploration guide for Red Dog-type Zn-Pb-Ag deposits elsewhere. ?? 2004 by Economic Geology.
Piatak, Nadine M.; Seal, Robert R.; Hammarstrom, Jane M.; Kiah, Richard G.; Deacon, Jeffrey R.; Adams, Monique; Anthony, Michael W.; Briggs, Paul H.; Jackson, John C.
2006-01-01
The Pike Hill Copper Mine Superfund Site in the Vermont copper belt consists of the abandoned Smith, Eureka, and Union mines, all of which exploited Besshi-type massive sulfide deposits. The site was listed on the U.S. Environmental Protection Agency (USEPA) National Priorities List in 2004 due to aquatic ecosystem impacts. This study was intended to be a precursor to a formal remedial investigation by the USEPA, and it focused on the characterization of mine waste, mine drainage, and stream sediments. A related study investigated the effects of the mine drainage on downstream surface waters. The potential for mine waste and drainage to have an adverse impact on aquatic ecosystems, on drinking- water supplies, and to human health was assessed on the basis of mineralogy, chemical concentrations, acid generation, and potential for metals to be leached from mine waste and soils. The results were compared to those from analyses of other Vermont copper belt Superfund sites, the Elizabeth Mine and Ely Copper Mine, to evaluate if the waste material at the Pike Hill Copper Mine was sufficiently similar to that of the other mine sites that USEPA can streamline the evaluation of remediation technologies. Mine-waste samples consisted of oxidized and unoxidized sulfidic ore and waste rock, and flotation-mill tailings. These samples contained as much as 16 weight percent sulfides that included chalcopyrite, pyrite, pyrrhotite, and sphalerite. During oxidation, sulfides weather and may release potentially toxic trace elements and may produce acid. In addition, soluble efflorescent sulfate salts were identified at the mines; during rain events, the dissolution of these salts contributes acid and metals to receiving waters. Mine waste contained concentrations of cadmium, copper, and iron that exceeded USEPA Preliminary Remediation Goals. The concentrations of selenium in mine waste were higher than the average composition of eastern United States soils. Most mine waste was potentially acid generating because of paste-pH values of less than 4 and negative net-neutralization potentials (NNP). The processed flotation-mill tailings, however, had a near neutral paste pH, positive NNP, and a few weight percent calcite. Leachate tests indicated that elements and compounds such as Al, Cd, Cu, Fe, Mn, Se, SO4, and Zn were leached from mine waste in concentrations that exceeded aquatic ecosystem and drinking-water standards. Mine waste from the Pike Hill mines was chemically and mineralogically similar to that from the Elizabeth and Ely mines. In addition, metals were leached and acid was produced from mine waste from the Pike Hill mines in comparable concentrations to those from the Elizabeth and Ely mines, although the host rock of the Pike Hill deposits contains significant amounts of carbonate minerals and, thus, a greater acid-neutralizing capacity when compared to the host rocks of the Elizabeth and Ely deposits. Water samples collected from unimpacted parts of the Waits River watershed generally contained lower amounts of metals compared to water samples from mine drainage, were alkaline, and had a neutral pH, which was likely because of calcareous bedrock. Seeps and mine pools at the mine site had acidic to neutral pH, ranged from oxic to anoxic, and generally contained concentrations of metals, for example, aluminum, cadmium, copper, iron, and zinc, that exceeded aquatic toxicity standards or drinking-water standards, or both. Surface waters directly downstream of the Eureka and Union mines were acidic, as indicated by pH values from 3.1 to 4.2, and contained high concentrations of some elements including as much as 11,400 micrograms per liter (?g/L) Al, as much as 22.9 ?g/L Cd, as much as 6,790 ?g/L Cu, as much as 23,300 ?g/L Fe, as much as 1,400 ?g/L Mn, and as much as 3,570 ?g/L Zn. The concentrations of these elements exceeded water-quality guidelines. Generally, in surface waters, the pH increased and the concentrations of these elemen
Benkó, Zsolt; Mogessie, Aberra; Molnár, Ferenc; Krenn, Kurt; Poulson, Simon R.; Hauck, Steven; Severson, Mark; Arehart, Greg B.
2015-01-01
In the Neoarchean (~ 2.7 Ga) contact metamorphosed charnockitic footwall of the Mesoproterosoic (1.1 Ga) South Kawishiwi intrusion of the Duluth Complex, the primary metamorphic mineral assemblage and Cu–Ni–PGE sulfide mineralization is overprinted by an actinolite + chlorite + cummingtonite + prehnite + pumpellyite + quartz + calcite hydrothermal mineral assemblage along 2–3 cm thick veins. In calcite, hosted by the hydrothermal alteration zones and in a single recrystallized quartz porphyroblast, four different fluid inclusion assemblages are documented; the composition of these fluid inclusions provide p–T conditions of the fluid flow, and helps to define the origin of the fluids and evaluate their role in the remobilization and reprecipitation of the primary metamorphic sulfide assemblage. Pure CO2 fluid inclusions were found as early inclusions in recrystallized quartz porphyroblast. These inclusions may have been trapped during the recrystallization of the quartz during the contact metamorphism of the footwall charnockite in the footwall of the SKI. The estimated trapping pressure (1.6–2.0 kbar) and temperature (810–920 °C) conditions correspond to estimates based on felsic veins in the basal zones of the South Kawishiwi intrusion. Fluid inclusion assemblages with CO2–H2O–NaCl and CH4–N2–H2O–NaCl compositions found in this study along healed microfractures in the recrystallized quartz porphyroblast establish the heterogeneous state of the fluids during entrapment. The estimated trapping pressure and temperature conditions (240–650 bar and 120–150 °C for CO2–H2O–NaCl inclusions and 315–360 bar and 145–165 °C for CH4–N2–H2O–NaCl inclusions) are significantly lower than the p–T conditions (> 700 °C and 1.6–2 kbar) during the contact metamorphism, indicating that this fluid flow might not be related to the cooling of the Duluth Complex and its contact aureole. The presence of chalcopyrite inclusions in these fluid inclusions and in the trails of these fluid inclusion assemblages confirms that at least on local scale these fluids played a role in base metal remobilization. No evidences have been observed for PGE remobilization and transport in the samples. The source of the carbonic phase in the carbonic assemblages (CO2; CH4) could be the graphite, present in the metasedimentary hornfelsed inclusions in the basal zones of the South Kawishiwi intrusion. The hydrothermal veins in the charnockite can be characterized by an actinolite + cummingtonite + chlorite + prehnite + pumpellyite + calcite (I–II) + quartz mineral assemblage. Chlorite thermometry yields temperatures around 276–308 °C during the earliest phase of the fluid flow. In the late calcite (II) phase, high salinity (21.6–28.8 NaCl + CaCl2 equiv. wt.%), low temperature (90–160 °C), primary aqueous inclusions were found. Chalcopyrite (± sphalerite ± millerite), replacing and intersecting the early hydrothermal phases, are associated to the late calcite (II) phase. The composition of the formational fluids in the Canadian Shield is comparable with the composition of the studied fluid inclusions. This suggests that the composition of the fluids did not change in the past 2 Ga and base metal remobilization by formational fluids could have taken place any time after the formation of the South Kawishiwi intrusion. Sulfur isotope studies carried out on the primary metamorphic (δ34S = 7.4–8.9‰) and the hydrothermal sulfide mineral assemblage (δ34S = 5.5–5.7‰) proves, that during the hydrothermal fluid flow the primary metamorphic ores were remobilized. PMID:26594080
Geology and mineral deposits of the St. Regis-Superior area, Mineral County, Montana
Campbell, Arthur B.
1960-01-01
The St. Regis-Superior area occupies about 300 square miles in northwestern Montana and includes parts of the Squaw Peak Range and Coeur d'Alerie Mountains of the northern Rocky Mountains physiographic province. Nearly 50,000 feet of metasedimentary rocks of the Precambrian Belt series, chiefly varieties of quartzite and argillite, underlies most of the area. The Belt series is informally subdivided with reference to the top of the Wallace formation into lower and upper parts. In this area, the lower part of the Belt series is divided into the Prichard, Burke and Revett, St. Regis, and Wallace formations, in order of decreasing age, and the upper part of the Belt series or the Missoula group is divided »into the Spruce, Lupine, Sloway, and Bouchard formations, and an unnamed feldspathic quartzite at Rock Rabbit Ridge, also from oldest to youngest. Formations in the lower part of the Belt series are correlated with formations of the same names in the Coeur d'Alene district, and formations in the upper part of the Belt series are tentatively correlated in part with formations of the Missoula group in the vicinity of Missoula, Mont. Paleozoic quartzite, shale, limestone, and dolomite crop out in several localities in the southeastern part of the area. The limestone unit contains fragments of a single species of Glossopleura of early Middle Cambrian age which, together with lithologic similarities, has been used to correlate at least the quartzite, shale, and limestone part of this Paleozoic sequence with the Flathead sandstone, Gordon shale, and Damnation limestone sequence known elsewhere in northwestern Montana. Several small diabasic dikes and sills are present in the area, generally associated with northwestward-trending faults. The major faults generally trend northwestward and are considered to be part of the Lewis and Clark structural line. The Osburn fault, the major element of the Lewis and Clark line through the Coeur d'Alene district and western Mineral County, has been traced to the east edge of the St. Regis- Superior area, thus extending the mapped length of the fault to about 100 miles. Evidence indicates that this major fault has diminished in intensity in this area and that most of the stress has been relieved along the Boyd Mountain fault that apparently splits from the Osburn fault a few miles west of St. Regis. Stratigraphic and structural evidence indicates a strike-slip right-lateral movement of about 3 miles along the Osburn fault. Horizontal stratigraphic separation along the Boyd Mountain fault indicates a right-lateral movement of about 13 miles.Low-grade regional metamorphism of the sedimentary rocks in the area has caused the recrystallization of quartz grains and the formation of sericite. Argillite and quartzite have been converted to phyllite and foliated quartzite by dynamic metamorphism in a large area north of the central part of the Osburn fault. Some of the shear zones contain a large amount of introduced carbonate minerals. From 1901 through 1953 this area has produced 8,086,827 pounds of zinc, 7,932,958 pounds of lead, 2,053,715 pounds of copper, 584,168 fine ounces of silver, and 588 fine ounces of gold. The lead, sine, and silver have come chiefly from veins in highly foliated rocks near the Osburn fault zone. The attitudes of these veins are controlled in large part by the cleavage. The principal ore minerals are galena, sphalerite, tetrahedrite, and boulangerite, and the gangue minerals are quartz, carbonate minerals, and barite. Most of the copper has come from the Amador vein where chalcopyrite and bornite are the principal ore minerals, and the gangue minerals are pyrite, quartz, and carbonate minerals. The Amador vein occurs in a belt of copper deposits that extends westward into the Coeur d'Alene district. These copper deposits may be genetically associated with diorite dikes and sills lying within the same belt. Fluorspar has been found in three closely spaced prospects along a northward- trending zone of brecciation and small-scale folding in Dry Creek valley. Incomplete production records show that 781 tons of fluorspar has been shipped from 2 of these prospects.