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.

Compositions, ages, and diagenetic histories of the carbonate, sulfide, oxide, and phosphatic concretions at Gay Head, Massachusetts

USGS Publications Warehouse

Poppe, L.J.; Commeau, R.F.; O'Leary, Dennis W.

1988-01-01

The calcite/ankerite concretions were formed in a hot, seasonally arid, caliche-prone environment of early Raritan age; the pyrite, marcasite, and siderite concretions precipitated in sediments deposited in low-energy, marshy, estuarine environments of late Raritan age. The phosphate concretions formed in a middle to inner shelf environment. The goethite and lepidocrocite concretions are secondary oxidation or alteration products of the prexistent Cretaceous concretions that were excavated during the Pleistocene and incorporated into the glacial drift. -from Authors

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.

Arsenic-bearing pyrite and marcasite in the Fire Clay coal bed, Middle Pennsylvanian Breathitt Formation, eastern Kentucky

USGS Publications Warehouse

Ruppert, L.F.; Hower, J.C.; Eble, C.F.

2005-01-01

Arsenic concentrations determined on 11 lithotype samples from the Middle Pennsylvanian Breathitt Group Fire Clay coal bed, Leslie County, KY, range from 1 to 418 ppm (whole coal basis). The 11 lithotype samples, which vary in thickness from 4 to 18 cm, were sampled from a continuous 1.38 m channel sample, and were selected based on megascopic appearance (vitrain-rich versus attrital-rich). A lithotype that contains 418 ppm As is located near the top of the coal bed and is composed of 10.5 cm of bright clarain bands containing fusain that, within short distances, grade laterally into Fe sulfide bands. To determine the mode of occurrence of As in this lithotype, the coal was examined with scanning electron microscopy and analyzed by energy dispersive X-ray fluorescence. Massive, framboidal, cell filling, cell-wall replacement, and radiating forms of Fe sulfide were observed in the high As lithotype; many of the radiating Fe sulfide forms, and one of the cell-wall replacements contained As. Examination of the grains with optical light microscopy shows that the majority of radiating morphologies are pyrite, the remainder are marcasite. Selected Fe sulfide grains were also analyzed by electron microprobe microscopy. Arsenic concentrations within individual grains range from 0.0 wt.% to approximately 3.5 wt.%. On the basis of morphology, these Fe sulfides are presumed to be of syngenetic origin and would probably be removed from the coal during physical coal cleaning, thus eliminating a potential source of As from the coal combustion process. However, because the grains are radiating and have high surface area, dissolution and release of As could occur if the pyrite is oxidized in refuse ponds.

Chemical and mineralogical analysis of devonian black-shale samples from Martin County, Kentucky; Carroll and Washington counties, Ohio; Wise County, Virginia; and Overton County, Tennessee, U.S.A.

USGS Publications Warehouse

Leventhal, J.S.; Hosterman, J.W.

1982-01-01

Core samples of Devonian shales from five localities in the Appalachian basin have been analyzed chemically and mineralogically. The amounts of major elements are similar; however, the minor constituents, organic C, S, phosphate and carbonate show ten-fold variations in amounts. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As and Mn show variations in amounts that can be related to the minor constituents. All samples contain major amounts of quartz, illite, two types of mixed-layer clays, and chlorite in differing quantities. Pyrite, calcite, feldspar and kaolinite are also present in many samples in minor amounts. Dolomite, apatite, gypsum, barite, biotite and marcasite are present in a few samples in trace amounts. Trace elements listed above are strongly controlled by organic C with the exception of Mn which is associated with carbonate minerals. Amounts of organic C generally range from 3 to 6%, and S is in the range of 2-5%. Amounts of trace elements show the following general ranges in ppm (parts per million): Co, 20-40; Cu, 40-70; U, 10-40; As, 20-40; V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, and the organic C and sulfide S together created an environment that immobilized and preserved these trace elements. Closely spaced samples showing an abrupt transition in color also show changes in organic C, S and trace-element contents. Several associations exist between mineral and chemical content. Pyrite and marcasite are the only minerals found to contain sulfide-S. In general, the illite-chlorite mixed-layer clay mineral shows covariation with organic C if calcite is not present. The enriched trace elements are not related to the clay types, although the clay and organic matter are intimately associated as the bulk fabric of the rock. ?? 1982.

Use of variations in unit cell length, reflectance and hardness for determining the origin of Fe disulphides in sedimentary rocks

NASA Astrophysics Data System (ADS)

Dill, H. G.; Eberhard, E.; Hartmann, B.

1997-01-01

Fe disulphides are common opaque accessories in sedimentary rocks. Both marcasite and pyrite may shed some light on the depositional environment and help determine the diagenesis of their host rocks. Quantitative ore microscopy (reflectance measurements, Vickers hardness numbers) and X-ray diffraction methods, supplemented with scanning electron microscopy and chemical analyses, were applied to pyrite (and some marcasite) hosted by sedimentary rocks spanning the interval from the Devonian to the Pliocene, and formed in various marine and continental environments. Quantitative ore microscopy of pyrites of sedimentary origin does not seem to be an efficient tool for analyzing the environment owing to the inhomogeneous nature of sulphide aggregates when viewed under the ore microscope, and the variable amounts of minor elements (e.g., As, Ni, and Co) that control the reflectance values (RV) and Vickers hardness numbers (VHN) of the host sulphides. However, such parameters as crystal habit and unit cell length of pyrite, which correlate with FeS x, are useful for environmental analysis. The redox conditions and the presence of organic remains during formation are the main factors determining these crystallographic parameters. Differences in these parameters from those of pure, ideal FeS 2 can be related to substitution of, e.g., wustite in the pyrite lattice, reflecting moderate oxidation (i.e. in the microenvironment). As far as crystal habit and length of the cell edge are concerned, late stage diagenesis is obviously less important than the microenvironment attending initial formation. The environment of deposition (i.e. the macroenvironment) of pyrite-bearing rocks has no influence on the crystal morphology or the length of the unit cell of Fe disulphide. X-ray diffraction measurements demonstrate that this method provides useful evidence on the microenvironment of sulphide precipitation around a single, equant pyrite, as well as around pyritized fossils.

Involvement of magmatic fluids at the Laloki and Federal Flag massive sulfide Cu-Zn-Au-Ag deposits, Astrolabe mineral district, Papua New Guinea: sulfur isotope evidence

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.

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).

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

Minor element distribution in iron disulfides in coal: a geochemical review

USGS Publications Warehouse

Kolker, Allan

2012-01-01

Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe3S4), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to the environment through coal mining and use, as well as for potential reduction by coal preparation, and for delineating diagenetic compositional changes throughout and after coal formation.

S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

USGS Publications Warehouse

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hower, J.C.; Ferm, J.C.; Cobb, J.C.

This project consists of three specific areas of coal petrology: spectral fluorescence of liptinite macerals; properties of semi-inert macerals; and size/form/microlithotype association of pyrite/marcasite. Techniques developed in the first three areas were used in additional research on Mannington and Dunbar coals in western Kentucky and the Alma coal zone in eastern Kentucky. Some of the findings are: percent variations (pseudovitrinite-vitrinite/vitrinite X100) indicate greater dispersions in Vicker's microhardness values, MH(v), of vitrinite and pseudovitrinite from eastern Kentucky coals than those of western Kentucky coals; reflectance data confirm a previously suspected rank increase from eastern Knott and Magoffin Counties to eastern Pikemore » County; microhardness investigation of Upper Elkhorn 2 coal in eastern Kentucky indicates that pseudovitrinite is consistently harder than vitrinite; and of the western coals studied, Dunbar and Lead Creek, there appears to be some correlations between vitrinite, ash, sulfur, and thickness. 6 tables.« less

Suggested nomenclature change and new reference locality for Dequeen Formation, Pike County, Arkansas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ham, T.L.; Landry, R.J.

1983-09-01

The DeQueen Formation of the Trinity Group, Comanchean Cretaceous, crops out in southwestern Arkansas and southeastern Oklahoma. The outcrop, located in the Highland gypsum quarry of Pike County, southwestern Arkansas, is described in detail in this paper and presented as a reference locality. Data from the locality provide the basis for a nomenclature change from the DeQueen Limestone Member to the DeQueen Formation. The formation consists of 64.23% clastic sediments, 24.72% gypsum, and 11.05% limestone. Hopper salt casts, ripple marks, scattered pyrite and marcasite nodules, celestite, and chickenwire gypsum can also be found. The DeQueen Formation is underlain by claysmore » and the Ultima Thule Gravel lentil, while the top is unconformably overlain by Upper Cretaceous Tokio gravels. The general paleoenvironment represents a normally low-energy subtidal environment ranging from brackish to normal to hypersaline waters in a lagoonal setting that shallows upward.« less

Sedimentary sulfur geochemistry of the Paleogene Green River Formation, western USA: Implications for interpreting depositional and diagenetic processes in saline alkaline lakes

USGS Publications Warehouse

Tuttle, M.L.; Goldhaber, M.B.

1993-01-01

The sulfur geochemistry of the lacustrine Paleogene Green River Formation (Colorado, Utah, and Wyoming, USA) is unlike that of most marine and other lacustrine rocks. Distinctive chemical, isotopic, and mineralogical characteristics of the formation are pyrrhotite and marcasite, high contents of iron mineral sulfides strikingly enriched in 34S, cyclical trends in sulfur abundance and ??34S values, and long-term evolutionary trends in ??34S values. Analyses that identified and quantified these characteristics include carbonate-free abundance of organic carbon (0.13-47 wt%), total iron (0.31-13 wt%), reactive iron (>70% of total iron), total sulfur (0.02-16 wt%), acid-volatile monosulfide (SAv), disulfide (SDi > 70% of total sulfur), sulfate (SSO4) and organosulfur (SOrg); isotopic composition of separated sulfur phases (??34SDi,Av up to +49???); and mineralogy, morphology and paragenesis of sulfide minerals. Mineralogy, morphology, ??34SDi,Av, and ??34SOrg have a distinctive relation, reflecting variable and unique depositional and early diagenetic conditions in the Green River lakes. When the lakes were brackish, dissimilatory sulfate-reducing bacteria in the sediment produced H2S, which initially reacted with labile iron to form pyrite framboids and more gradually with organic matter to form organosulfur compounds. During a long-lived stage of saline lake water, the amount of sulfate supplied by inflow decreased and alkalinity and pH of lake waters increased substantially. Extensive bacterial sulfate reduction in the water column kept lake waters undersaturated with sulfate minerals. A very high H2S:SO4 ratio developed in stagnant bottom water aided by the high pH that kinetically inhibited iron sulfidization. Progressive removal of H2S by coeval formation of iron sulfides and organosulfur compounds caused the isotopic composition of the entire dissolved sulfur reservoir to evolve to ??34S values much greater than that of inflow sulfate, which is estimated to have been +20??? A six-million-year interval within Lake Uinta cores records this evolution as well as smaller systematic changes in ??34S, interpreted to reflect ~ 100,000-year lake-level cycles. When porewater was exceptionally reducing, unstable FeS phases eventually recrystallized to pyrrhotite during diagenesis. A much later reaction related to weathering altered pyrrhotite to marcasite. ?? 1993.

Submarine fissure eruptions and hydrothermal vents on the southern Juan de Fuca Ridge: preliminary observations from the submersible Alvin

USGS Publications Warehouse

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

Weathering of post-impact hydrothermal deposits from the Haughton impact structure: implications for microbial colonization and biosignature preservation.

PubMed

Izawa, M R M; Banerjee, Neil R; Osinski, G R; Flemming, R L; Parnell, J; Cockell, C S

2011-01-01

Meteorite impacts are among the very few processes common to all planetary bodies with solid surfaces. Among the effects of impact on water-bearing targets is the formation of post-impact hydrothermal systems and associated mineral deposits. The Haughton impact structure (Devon Island, Nunavut, Canada, 75.2 °N, 89.5 °W) hosts a variety of hydrothermal mineral deposits that preserve assemblages of primary hydrothermal minerals commonly associated with secondary oxidative/hydrous weathering products. Hydrothermal mineral deposits at Haughton include intra-breccia calcite-marcasite vugs, small intra-breccia calcite or quartz vugs, intra-breccia gypsum megacryst vugs, hydrothermal pipe structures and associated surface "gossans," banded Fe-oxyhydroxide deposits, and calcite and quartz veins and coatings in shattered target rocks. Of particular importance are sulfide-rich deposits and their associated assemblage of weathering products. Hydrothermal mineral assemblages were characterized structurally, texturally, and geochemically with X-ray diffraction, micro X-ray diffraction, optical and electron microscopy, and inductively coupled plasma atomic emission spectroscopy. Primary sulfides (marcasite and pyrite) are commonly associated with alteration minerals, including jarosite (K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6), rozenite FeSO(4)·4(H(2)O), copiapite (Fe,Mg)Fe(4)(SO(4))(6)(OH)(2)·20(H(2)O), fibroferrite Fe(SO(4))(OH)·5(H(2)O), melanterite FeSO(4)·7(H(2)O), szomolnokite FeSO(4)·H(2)O, goethite α-FeO(OH), lepidocrocite γ-FeO(OH) and ferrihydrite Fe(2)O(3)·0.5(H(2)O). These alteration assemblages are consistent with geochemical conditions that were locally very different from the predominantly circumneutral, carbonate-buffered environment at Haughton. Mineral assemblages associated with primary hydrothermal activity, and the weathering products of such deposits, provide constraints on possible microbial activity in the post-impact environment. The initial period of active hydrothermal circulation produced primary mineral assemblages, including Fe sulfides, and was succeeded by a period dominated by oxidation and low-temperature hydration of primary minerals by surface waters. Active hydrothermal circulation can enable the rapid delivery of nutrients to microbes. Nutrient availability following the cessation of hydrothermal circulation is likely more restricted; therefore, the biological importance of chemical energy from hydrothermal mineral deposits increases with time. Weathering of primary hydrothermal deposits and dissolution and reprecipitation of mobile weathering products also create many potential habitats for endolithic microbes. They also provide a mechanism that may preserve biological materials, potentially over geological timescales. © Mary Ann Liebert, Inc.

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.

Exploratory drilling in the Prairie du Chien group of the Wisconsin zinc-lead districts by the U.S. Geological Survey in 1949-1950

USGS Publications Warehouse

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.

On the origin of a phosphate enriched interval in the Chattanooga Shale (Upper Devonian) of Tennessee-A combined sedimentologic, petrographic, and geochemical study

NASA Astrophysics Data System (ADS)

Li, Yifan; Schieber, Juergen

2015-11-01

The Devonian Chattanooga Shale contains an uppermost black shale interval with dispersed phosphate nodules. This interval extends from Tennessee to correlative strata in Kentucky, Indiana, and Ohio and represents a significant period of marine phosphate fixation during the Late Devonian of North America. It overlies black shales that lack phosphate nodules but otherwise look very similar in outcrop. The purpose of this study is to examine what sets these two shales apart and what this difference tells us about the sedimentary history of the uppermost Chattanooga Shale. In thin section, the lower black shales (PBS) show pyrite enriched laminae and compositional banding. The overlying phosphatic black shales (PhBS) are characterized by phosbioclasts, have a general banded to homogenized texture with reworked layers, and show well defined horizons of phosphate nodules that are reworked and transported. In the PhBS, up to 8000 particles of P-debris per cm2 occur in reworked beds, whereas the background black shale shows between 37-88 particles per cm2. In the PBS, the shale matrix contains between 8-16 phosphatic particles per cm2. The shale matrix in the PhBS contains 5.6% inertinite, whereas just 1% inertinite occurs in the PBS. The shale matrix in both units is characterized by flat REE patterns (shale-normalized), whereas Phosbioclast-rich layers in the PhBS show high concentrations of REEs and enrichment of MREEs. Negative Ce-anomalies are common to all samples, but are best developed in association with Phosbioclasts. Redox-sensitive elements (Co, U, Mo) are more strongly enriched in the PBS when compared to the PhBS. Trace elements associated with organic matter (Cu, Zn, Cd, Ni) show an inverse trend of enrichment. Deposited atop a sequence boundary that separates the two shale units, the PhBS unit represents a transgressive systems tract and probably was deposited in shallower water than the underlying PBS interval. The higher phosphate content in the PhBS is interpreted as the result of a combination of lower sedimentation rates with reworking/winnowing episodes. Three types of phosphatic beds that reflect different degrees of reworking intensity are observed. Strong negative Ce anomalies and abundant secondary marcasite formation in the PhBS suggests improved aeration of the water column, and improved downward diffusion of oxygen into the sediment. The associated oxidation of previously formed pyrite resulted in a lowering of pore water pH and forced dissolution of biogenic phosphate. Phosphate dissolution was followed by formation of secondary marcasite and phosphate. Repeated, episodic reworking caused repetitive cycles of phosphatic dissolution and reprecipitation, enriching MREEs in reprecipitated apatite. A generally "deeper" seated redox boundary favored P-remineralization within the sediment matrix, and multiple repeats of this process in combination with wave and current reworking at the seabed led to the formation of larger phosphatic aggregates and concentration of phosphate nodules in discrete horizons.

Potentially hazardous elements in coal: Modes of occurrence and summary of concentration data for coal components

USGS Publications Warehouse

Kolker, A.; Finkelman, R.B.

1998-01-01

Mode-of-occurrence data are summarized for 13 potentially hazardous elements (Be, Cr, Mn, Co, Ni, As, Se, Cd, Sb, Hg, Pb, Th, U) in coal. Recent work has refined mode-of-occurrence data for Ni, Cr, and As, as compared to previous summaries. For Cr, dominant modes of occurrence include the clay mineral illite, an amorphous CrO(OH) phase, and Cr-bearing spinels. Nickel is present in Fe-sulfides (pyrite and marcasite) and is also organically bound. Arsenic-bearing pyrite may be the dominant host of As in bituminous coals. Concentration data for the 13 HAPs, obtained primarily by quantitative microanalysis techniques, are compiled for mineral and organic portions of coal. HAPs element concentrations are greatest in Fe-sulfides, and include maxima of 2,300 ppm (Co), 4,500 ppm (Ni), 4.9wt.% (As), 2,000 ppm (Se), 171 ppm (Hg), and 5,500 ppm (Pb). Trace-element microanalysis is a significant refinement over bulk methods, and shows that there is considerable trace-element variation on a fine scale for a given coal, and from one coal to another. ?? 1998 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.

Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bugaris, Daniel E.; Malliakas, Christos D.; Shoemaker, Daniel P.

2014-09-15

Using metal fluxes, crystals of the binary osmium dipnictides OsPn(2) (Pn = P, As, Sb) have been grown for the first time. Single-crystal X-ray diffraction confirms that these compounds crystallize in the marcasite structure type with orthorhombic space group Pnnm. The structure is a three-dimensional framework of corner- and edge-sharing OsPn(6) octahedra, as well as [Pn(2)(-4)] anions. Raman spectroscopy shows the presence of PP single bonds, consistent with the presence of [Pn(2)(-4)] anions and formally Os4+ cations. Optical-band-gap and high-temperature electrical resistivity measurements indicate that these materials are narrow-band-gap semiconductors. The experimentally determined Seebeck coefficients reveal that nominally undoped OsP2more » and OsSb2 are n-type semiconductors, whereas OsAs2 is p-type. Electronic band structure using density functional theory calculations shows that these compounds are indirect narrow-band-gap semiconductors. The bonding p orbitals associated with the Pn(2) dimer are below the Fermi energy, and the corresponding antibonding states are above, consistent with a PnPn single bond. Thermopower calculations using Boltzmann transport theory and constant relaxation time approximation show that these materials are potentially good thermoelectrics, in agreement with experiment.« less

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bachhuber, F.; School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland; Rothballer, J.

2013-12-07

In the course of the recent advances in chemical structure prediction, a straightforward type of diagram to evaluate phase stabilities is presented based on an expedient example. Crystal structures and energetic stabilities of dipnictides NiPn{sub 2} (Pn = N, P, As, Sb, Bi) are systematically investigated by first principles calculations within the framework of density functional theory using the generalized gradient approximation to treat exchange and correlation. These dipnictides show remarkable polymorphism that is not yet understood systematically and offers room for the discovery of new phases. Relationships between the concerned structures including the marcasite, the pyrite, the arsenopyrite/CoSb{sub 2},more » and the NiAs{sub 2} types are highlighted by means of common structural fragments. Electronic stabilities of experimentally known and related AB{sub 2} structure types are presented graphically in so-called stability diagrams. Additionally, competing binary phases are taken into consideration in the diagrams to evaluate the stabilities of the title compounds with respect to decomposition. The main purpose of the stability diagrams is the introduction of an image that enables the estimation of phase stabilities at a single glance. Beyond that, some of the energetically favored structure types can be identified as potential new phases.« less

Manganese and iron geochemistry in sediments underlying the redox-stratified Fayetteville Green Lake

NASA Astrophysics Data System (ADS)

Herndon, Elizabeth M.; Havig, Jeff R.; Singer, David M.; McCormick, Michael L.; Kump, Lee R.

2018-06-01

Manganese and iron are redox-sensitive elements that yield clues about biogeochemistry and redox conditions both in modern environments and in the geologic past. Here, we investigated Mn and Fe-bearing minerals preserved in basin sediments underlying Fayetteville Green Lake, a redox-stratified lake that serves as a geochemical analogue for Paleoproterozoic oceans. Synchrotron-source microprobe techniques (μXRF, μXANES, and μXRD) and bulk geochemical analyses were used to examine the microscale distribution and speciation of Mn, Fe, and S as a function of depth in the top 48 cm of anoxic lake sediments. Manganese was primarily associated with calcite grains as a manganese-rich carbonate that precipitated in the chemocline of the water column and settled through the euxinic basin to collect in lake sediments. Iron was preserved in framboidal iron sulfides that precipitated in euxinic bottom waters and underwent transformation to pyrite and marcasite in the sediments. Previous studies attribute the formation of manganese-rich carbonates to the diagenetic alteration of manganese oxides deposited in basins underlying oxygenated water. Our study challenges this paradigm by providing evidence that Mn-bearing carbonates form in the water column and accumulate in sediments below anoxic waters. Consequently, manganoan carbonates preserved in the rock record do not necessarily denote the presence of oxygenated bottom waters in ocean basins.

Anaerobic Nitrogen Fixers on Mars

NASA Astrophysics Data System (ADS)

Lewis, B. G.

2000-07-01

The conversion of atmospheric nitrogen gas to the protein of living systems is an amazing process of nature. The first step in the process is biological nitrogen fixation, the transformation of N2 to NH3. The phenomenon is crucial for feeding the billions of our species on Earth. On Mars, the same process may allow us to discover how life can adapt to a hostile environment, and render it habitable. Hostile environments also exist on Earth. For example, nothing grows in coal refuse piles due to the oxidation of pyrite and marcasite to sulfuric acid. Yet, when the acidity is neutralized, alfalfa and soybean plants develop root nodules typical of symbiotic nitrogen fixation with Rhizobium species possibly living in the pyritic material. When split open, these nodules exhibited the pinkish color of leghemoglobin, a protein in the nodule protecting the active nitrogen-fixing enzyme nitrogenase against the toxic effects of oxygen. Although we have not yet obtained direct evidence of nitrogenase activity in these nodules (reduction of acetylene to ethylene, for example), these findings suggested the possibility that nitrogen fixation was taking place in this hostile, non-soil material. This immediately raises the possibility that freeliving anaerobic bacteria which fix atmospheric nitrogen on Earth, could do the same on Mars.

Impact of hydrothermal alteration on time-dependent tunnel deformation in Neogene volcanic rock sequence in Japan: Petrology, Geochemistry and Geophysical investigation

NASA Astrophysics Data System (ADS)

Yamazaki, S.; Okazaki, K.; Niwa, H.; Arai, T.; Murayama, H.; Kurahashi, T.; Ito, Y.

2017-12-01

Time-dependent tunnel deformation is one of remaining geological problems for mountain tunneling. As a case study of time-dependent tunnel deformation, we investigated petrographical, mineral and chemical compositions of boring core samples and seismic exploration along a tunnel that constructed into Neogene volcanic rock sequence of andesite to dacite pyroclastic rocks and massive lavas with mafic enclaves. The tunnel has two zones of floor heaving that deformed time-dependently about 2 month after the tunnel excavation. The core samples around the deformed zones are characterized secondary mineral assemblages of smectite, cristobalite, tridymite, sulfides (pyrite and marcasite) and partially or completely reacted carbonates (calcite and siderite), which were formed by hydrothermal alteration under neutral to acidic condition below about 100 °C. The core samples also showed localized deterioration, such as crack formation and expansion, which occurred from few days to months after the drilling. The deterioration could be explained as a result of the cyclic physical and chemical weathering process with the oxidation of sulfide minerals, dissolution of carbonate mineral cementation and volumetric expantion of smectite. This weathering process is considered as a key factor for time-dependent tunnel deformation in the hydrothermally altered volcanic rocks. The zones of time-dependent deformation along a tunnel route can be predicted by the variations of whole-rock chemical compositions such as Na, Ca, Sr, Ba and S.

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.

Mineralogical gradients associated with alvinellids at deep-sea hydrothermal vents

NASA Astrophysics Data System (ADS)

Zbinden, Magali; Le Bris, Nadine; Compère, Philippe; Martinez, Isabelle; Guyot, François; Gaill, Françoise

2003-02-01

Alvinella pompejana and Alvinella caudata live in organic tubes on active sulphide chimney walls at deep-sea hydrothermal vents. These polychaete annelids are exposed to extreme thermal and chemical gradients and to intense mineral precipitation. This work points out that mineral particles associated with Pompeii worm ( A. pompejana and A. caudata) tubes constitute useful markers for evaluating the chemical characteristics of their micro-environment. The minerals associated with these worm tubes were analysed on samples recovered from an experimental alvinellid colony, at different locations in the vent fluid-seawater interface. Inhabited tubes from the most upper and lower parts of the colony were analysed by light and electron microscopies, X-ray microanalysis and X-ray diffraction. A change was observed from a Fe-Zn-S mineral assemblage to a Zn-S assemblage at the millimeter scale from the outer to the inner face of a tube. A similar gradient in proportions of minerals was observed at a decimeter scale from the lower to the upper part of the colony. The marcasite/pyrite ratio of iron disulphides also displays a steep decrease along the few millimeters adjacent to the external tube surface. The occurrence of these gradients indicates that the micro-environment within the tube differs from that outside the tube, and suggests that the tube wall acts as an efficient barrier to the external environment.

Preliminary investigation of the elemental variation and diagenesis of a tabular uranium deposit, La Sal Mine, San Juan County, Utah

USGS Publications Warehouse

Brooks, Robert A.; Campbell, John A.

1976-01-01

Ore in the La Sal mine, San Juan County, Utah, occurs as a typical tabular-type uranium deposit of the-Colorado Plateau. Uranium-vanadium occurs in the Salt Wash Member of the Jurassic Morrison Formation. Chemical and petrographic analyses were used to determine elemental variation and diagenetic aspects across the orebody. Vanadium is concentrated in the dark clay matrix, which constitutes visible ore. Uranium content is greater above the vanadium zone. Calcium, carbonate carbon, and lead show greater than fifty-fold increase across the ore zone, whereas copper and organic carbon show only a several-fold increase. Large molybdenum concentrations are present in and above the tabular layer, and large selenium concentrations occur below the uranium zone within the richest vanadium zone. Iron is enriched in the vanadium horizon. Chromium is depleted from above the ore and strongly enriched below. Elements that vary directly with the vanadium content include magnesium, iron, selenium, zirconium, strontium, titanium, lead, boron, yttrium, and scandium. The diagenetic sequence is as follows: (1) formation of secondary quartz overgrowths as cement; (2) infilling and lining of remaining pores with amber opaline material; (3) formation of vanadium-rich clay matrix, which has replaced overgrowths as well as quartz grains; (4) replacement of overgrowths and detrital grains by calcite; (5) infilling of pores with barite and the introduction of pyrite and marcasite.

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.

Genesis of the Doğankuzu and Mortaş Bauxite deposits, Taurides, Turkey: separation of Al, Fe, and Mn and implications for passive margin metallogeny

USGS Publications Warehouse

Öztürk, Hüseyin; Hein, James R.; Hanilçi, Nurullah

2002-01-01

The Taurides region of Turkey is host to a number of important bauxite, Al-rich laterite, and Mn deposits. The most important bauxite deposits, Doğankuzu and Mortaş, are karst-related, unconformity-type deposits in Upper Cretaceous limestone. The bottom contact of the bauxite ore is undulatory, and bauxite fills depressions and sinkholes in the footwall limestone, whereas its top surface is concordant with the hanging-wall limestone. The thickness of the bauxite varies from 1 to 40 m and consists of böhmite, hematite, pyrite, marcasite, anatase, diaspore, gypsum, kaolinite, and smectite. The strata-bound, sulfide- and sulfate-bearing, low-grade lower part of the bauxite ore bed contains pyrite pseudomorphs after hematite and is deep red in outcrop owing to supergene oxidation. The lower part of the bauxite body contains local intercalations of calcareous conglomerate that formed in fault-controlled depressions and sinkholes. Bauxite ore is overlain by fine-grained Fe sulfide-bearing and calcareous claystone and argillaceous limestone, which are in turn overlain by massive, compact limestone of Santonian age. That 50-m-thick limestone is in turn overlain by well-bedded bioclastic limestone of Campanian or Maastrichtian age, rich with rudist fossils. Fracture fillings in the bauxite orebody are up to 1 m thick and consist of bluish-gray-green pyrite and marcasite (20%) with böhmite, diaspore, and anatase. These sulfide veins crosscut and offset the strata-bound sulfide zones. Sulfur for the sulfides was derived from the bacterial reduction of seawater sulfate, and Fe was derived from alteration of oxides in the bauxite. Iron sulfides do not occur within either the immediately underlying or overlying limestone. The platform limestone and shale that host the bauxite deposits formed at a passive margin of the Tethys Ocean. Extensive vegetation developed on land as the result of a humid climate, thereby creating thick and acidic soils and enhancing the transport of large amounts of organic matter to the ocean. Alteration of the organic matter provided CO2 that contributed to formation of a relatively 12C-rich marine footwall limestone. Relative sea-level fall resulted from strike-slip faulting associated with closure of the ocean and local uplift of the passive margin. That uplift resulted in karstification and bauxite formation in topographic lows, as represented by the Doğankuzu and Mortaş deposits. During stage 1 of bauxite formation, Al, Fe, Mn, and Ti were mobilized from deeply weathered aluminosilicate parent rock under acidic conditions and accumulated as hydroxides at the limestone surface owing to an increase in pH. During stage 2, Al, Fe, and Ti oxides and clays from the incipient bauxite (bauxitic soil) were transported as detrital phases and accumulated in the fault-controlled depressions and sinkholes. During stage 3, the bauxitic material was concentrated by repeated desilicification, which resulted in the transport of Si and Mn to the ocean through a well-developed karst drainage system. The transported Mn was deposited in offshore muds as Mn carbonates. The sulfides also formed in stage 3 during early diagenesis. Transgression into the foreland basin resulted from shortening of the ocean basin and nappe emplacement during the latest Cretaceous. During that time bioclastic limestone was deposited on the nappe ramp, which overlapped bauxite accumulation.

Mineralogy and geochemistry of El Dorado epithermal gold deposit, El Sauce district, central-northern Chile

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.

Discrimination among iron sulfide species formed in microbial cultures.

PubMed

Popa, R; Kinkle, B K

2000-10-01

A quantitative method for the study of iron sulfides precipitated in liquid cultures of bacteria is described. This method can be used to quantify and discriminate among amorphous iron sulfide (FeS(amorph)), iron monosulfide minerals such as mackinawite or greigite (FeS(min)), and iron disulfide minerals such as pyrite or marcasite (FeS(2min)) formed in liquid cultures. Degradation of iron sulfides is performed using a modified Cr(2+) reduction method with reflux distillation. The basic steps of the method are: first, separation of FeS(amorph); second, elimination of interfering species of S such as colloidal sulfur (S(c) degrees ), thiosulphate (S(2)O(3)(2-)) and polysulfides (S(x)(2-)); third, separation of FeS(min); and fourth, separation of FeS(2min). The final product is H(2)S which is determined after trapping. The efficiency of recovery is 96-99% for FeS(amorph), 76-88% for FeS(min), and >97% for FeS(2min). This method has a high reproducibility if the experimental conditions are rigorously applied and only glass conduits are used. A well ventilated fume hood must be used because of the toxicity and volatility of several reagents and products. The advantage relative to previously described methods are better resolution for iron sulfide species and use of the same bottles for both incubation of cultures and acid degradation. The method can also be used for Fe/S stoichiometry with sub-sampling and Fe analysis.

Thallium-rich pyrite ores from the Apuan Alps, Tuscany, Italy:constraints for their origin and environmental concerns

NASA Astrophysics Data System (ADS)

D'Orazio, Massimo; Biagioni, Cristian; Dini, Andrea; Vezzoni, Simone

2017-06-01

The southern sector of the Apuan Alps (AA) massif, Tuscany, Italy, is characterized by the occurrence of a series of baryte-pyrite-iron oxide orebodies whose Tl-rich nature was recognized only recently. The geochemistry of the pyrite ore was investigated through inductively coupled plasma mass spectrometry. In addition, lead isotope data for selected pyrite ores from AA were collected. Pyrite ores are characterized by a complex geochemistry, with high concentrations of Tl (up to 1100 μg/g) coupled with high As and Sb contents; the Co/Ni ratio is always <1. Geochemical data of pyrite and marcasite ore samples from other mining districts of Tuscany have been collected in order to compare them with those from the AA. These samples usually have very low Tl content (less than 2 μg/g) and high to very high Co/Ni and As/Sb ratios. Only some samples from the Sb-Hg ore deposits showed very high Tl concentrations (up to 3900 μg/g). Another difference is related to the lead isotope composition, with pyrite ores from AA markedly less radiogenic than those from the other deposits from Tuscany. Geochemical data of pyrite ores from AA give new insights on the genesis of the baryte-pyrite-iron oxide orebodies, relating their formation to low-temperature hydrothermal systems active during early Paleozoic; in addition, these data play a fundamental role in assessing the environmental impact of these deposits.

Methods for synthesis of some jarosites

USGS Publications Warehouse

Driscoll, Rhonda; Leinz, Reinhard

2005-01-01

Experimental procedures in this report summarize attempts to synthesize potassium-, hydronium-, sodium-, and mixed-composition (hydronium-bearing) jarosites. After experimentation, some acceptable combinations of chemical and physical factors were found to routinely synthesize chemically different jarosites, which were used as part of a characterization study of some natural and synthetic jarosites. Jarosite is a sulfate mineral that is common in geologic settings where iron sulfide minerals such as pyrite or marcasite are subject to oxidative weathering. The presence of jarosite is a hallmark of acidic conditions. Jarosite forms as a secondary mineral in weathered sulfidic ores, coal mine wastes, on oxidizing mine wastes, and in streams affected by acid mine drainage. Jarosite also forms in acid-sulfate soils, as an alteration product of sulfidic shales, and in hydrothermal environments. Because of its important role in earth surface processes, the USGS is conducting mineralogical, geochemical, and remote sensing studies to characterize natural jarosites and to elucidate its stability range and conditions of formation. The presence of jarosite is not limited to the Earth. The recent identification of jarosite in the rocks at the Meridiani Planum on Mars has given planetary geologists reason to think that jarosite may be evidence of relict lacustrine (lake systems) or hydrothermal (water enriched magma emanations) systems on the Martian surface. USGS scientists are currently developing jarosite detection systems that can be placed on orbiting spectrometers. One day these systems may guide Mars landers to sites abundant in jarosite, sites most likely to have sheltered ancient Martian life.

Mineralogy and fluid inclusions study of carbonate-hosted Mississippi valley-type Ain Allega Pb-Zn-Sr-Ba ore deposit, Northern Tunisia

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.

Formation and use of coal combustion residues from three types of power plants burning Illinois coals

USGS Publications Warehouse

Demir, I.; Hughes, R.E.; DeMaris, P.J.

2001-01-01

Coal, ash, and limestone samples from a fluidized bed combustion (FBC) plant, a pulverized coal combustion (PC) plant, and a cyclone (CYC) plant in Illinois were analyzed to determine the combustion behavior of mineral matter, and to propose beneficial uses for the power plant ashes. Pyrite and marcasite in coal were converted during combustion to glass, hematite and magnetite. Calcite was converted to lime and anhydrite. The clay minerals were altered to mullite and glass. Quartz was partially altered to glass. Trace elements in coal were partially mobilized during combustion and, as a result, emitted into the atmosphere or adsorbed on fly ash or on hardware on the cool side of the power plants. Overall, the mobilities of 15 trace elements investigated were lower at the FBC plant than at the other plants. Only F and Mn at the FBC plant, F, Hg, and Se at the PC plant and Be, F, Hg, and Se at the CYC plant had over 50% of their concentrations mobilized. Se and Ge could be commercially recovered from some of the combustion ashes. The FBC ashes could be used as acid neutralizing agents in agriculture and waste treatment, and to produce sulfate fertilizers, gypsum wall boards, concrete, and cement. The PC and CYC fly ashes can potentially be used in the production of cement, concrete, ceramics, and zeolites. The PC and CYC bottom ashes could be used in stabilized road bases, as frits in roof shingles, and perhaps in manufacturing amber glass. ?? 2001 Elsevier Science Ltd. All rights reserved.

Alteration Mineralogy and Geochemical Characteristics of Porphyry Cu-Mo Mineralization in Domaniç (Kütahya) Area

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.

A preliminary study of older hot spring alteration in Sevenmile Hole, Grand Canyon of the Yellowstone River, Yellowstone Caldera, Wyoming

USGS Publications Warehouse

Larson, Peter B.; Phillips, Allison; John, David A.; Cosca, Michael A.; Pritchard, Chad; Andersen, Allen; Manion, Jennifer

2009-01-01

Erosion in the Grand Canyon of the Yellowstone River, Yellowstone Caldera (640 ka), Wyoming, has exposed a cross section of older hydrothermal alteration in the canyon walls. The altered outcrops of the post-collapse tuff of Sulphur Creek (480 ka) extend from the canyon rim to more than 300 m beneath it. The hydrothermal minerals are zoned, with an advanced argillic alteration consisting of an association of quartz (opal) + kaolinite ± alunite ± dickite, and an argillic or potassic alteration association with quartz + illite ± adularia. Disseminated fine-grained pyrite or marcasite is ubiquitous in both alteration types. These alteration associations are characteristic products of shallow volcanic epithermal environments. The contact between the two alteration types is about 100 m beneath the rim. By analogy to other active geothermal systems including active hydrothermal springs in the Yellowstone Caldera, the transition from kaolinite to illite occurred at temperatures in the range 150 to 170 °C. An 40Ar/39Ar age on alunite of 154,000 ± 16,000 years suggests that hydrothermal activity has been ongoing since at least that time. A northwest-trending linear array of extinct and active hot spring centers in the Sevenmile Hole area implies a deeper structural control for the upflowing hydrothermal fluids. We interpret this deeper structure to be the Yellowstone Caldera ring fault that is covered by the younger tuff of Sulphur Creek. The Sevenmile Hole altered area lies at the eastern end of a band of hydrothermal centers that may mark the buried extension of the Yellowstone Caldera ring fault across the northern part of the Caldera.

Localized sulfate-reducing zones in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Coates, J.D.; Schoonen, M.A.A.

1999-01-01

High concentrations of dissolved iron in ground water of coastal plain or alluvial aquifers contribute to the biofouling of public supply wells for which treatment and remediation is costly. Many of these aquifers, however, contain zones in which microbial sulfate reduction and the associated precipitation of iron-sulfide minerals decreases iron mobility. The principal water-bearing aquifer (Magothy Aquifer of Cretaceous age) in Suffolk County, New York, contains localized sulfate-reducing zones in and near lignite deposits, which generally are associated with clay lenses. Microbial analyses of core samples amended with [14C]-acetate indicate that microbial sulfate reduction is the predominant terminal-electron-accepting process (TEAP) in poorly permeable, lignite-rich sediments at shallow depths and near the ground water divide. The sulfate-reducing zones are characterized by abundant lignite and iron-sulfide minerals, low concentrations of Fe(III) oxyhydroxides, and by proximity to clay lenses that contain pore water with relatively high concentrations of sulfate and dissolved organic carbon. The low permeability of these zones and, hence, the long residence time of ground water within them, permit the preservation and (or) allow the formation of iron-sulfide minerals, including pyrite and marcasite. Both sulfate-reducing bacteria (SRB) and iron-reducing bacteria (IRB) are present beneath and beyond the shallow sulfate-reducing zones. A unique Fe(III)-reducing organism, MD-612, was found in core sediments from a depth of 187 m near the southern shore of Long Island. The distribution of poorly permeable, lignite-rich, sulfate-reducing zones with decreased iron concentration is varied within the principal aquifer and accounts for the observed distribution of dissolved sulfate, iron, and iron sulfides in the aquifer. Locating such zones for the placement of production wells would be difficult, however, because these zones are of limited aerial extent.

Origin of nickel in water solution of the chalk aquifer in the north of France and influence of geochemical factors

NASA Astrophysics Data System (ADS)

Bernard, Daniel; El Khattabi, Jamal; Lefevre, Emilie; Serhal, Hani; Bastin-Lacherez, Sabine; Shahrour, Isam

2008-01-01

In the north of France, high registers of nickel are sometimes recorded within the chalk aquifer. In a confined context, the presence of pyrite in the covering clays or in the marcasite nodules encrusted in the clay may constitute a natural source of trace metals. With an objective of sanitary control, the limits of chemical contents regulating the quality of water destined for human consumption have been lowered by the European Framework Directive in the field of water policy (2000/60/EC). As a result, nickel limits have been reduced from 50 to 20 μg/l. The analyses, carried out on three water catchment fields in our area of study, were centred on variable parameters (Eh, O2(d), pH, Conductivity, T°), major elements (SO4, NO3) and metals (Fe, Ni, Mn, Co). The acquired data enabled us to identify from one hand, the conditions which are presented within the site, special thanks to the evolution of nitrate and iron contents and on the other hand, the natural origin (geological) of nickel for two of the three sites studied based essentially on the evaluation of the Nickel/Cobalt ratio. Thus, on the first site, the evolution of nickel content and nitrate content showed the influence of the phenomenon of denitrification on the re-mobilisation of the nickel. Whereas on the second site, a high variation of total iron content and oxygen dissolved in solution highlighted a particular phenomenon of oxidation of the pyrite through molecular oxygen. Finally, the correlation with the sulphates clearly showed behaviour of the nickel, once released, that was entirely dependent on the phenomenon of adsorption on the iron and manganese hydroxides.

Hydrology of area 4, Eastern Coal Province, Pennsylvania, Ohio, and West Virginia

USGS Publications Warehouse

Roth, Donald K.; Engelke, Morris J.; ,

1981-01-01

Area 4 (one of the 24 hydrologic areas defining the Eastern Coal Province) is located at the northern end of the Eastern Coal Province in eastern Ohio, northern West Virginia, and western Pennsylvania. It is part of the upper Ohio River basin, which includes the Beaver, Mahoning, and Shenango Rivers. The area is underlain by rocks of the Pottsville, Allegheny, Conemaugh, Monongahela Groups (or Formations) and Dunkard Group. Area 4 has a temperate climate with an annual average rainfall of 38 to 42 inches, most of its area is covered by forest. The soils have a high erosion potential where the vegetation cover is removed. In response to Public Law 95-87, 132 sites were added to the existing surface-water data-collection network in area 4. At these added sites, collected data includes discharge, water quality, sediment, and biology. The data are available from computer storage through the National Water Data Exchange (NAWDEX) or the published annual Water Resources Data reports for Ohio, Pennsylvania, and West Virginia. Hydrologic problems related to mining are: (1) Erosion and increased sedimentation, and (2) degradation of water quality. Erosion and sedimentation are associated chiefly with surface mining. Sediment yields increase drastically when vegetation is removed from the highly erosive soils. Degradation of water quality can be caused by acid-mine drainage from underground and surface mining. More than half the acid-mine drainage effluent in area 4 comes from underground mines. The rest seeps from abandoned surface mines. Usually in reclaimed surface mines the overburden is replaced in such a short time after the coal is taken out that oxidation of acid-forming minerals, commonly pyrite or marcasite, is not complete or is neutralized by the buffering action of calcareous minerals in the soils. (USGS)

Iron mineralogy and aqueous alteration from Husband Hill through Home Plate at Gusev Crater, Mars: Results from the Mössbauer instrument on the Spirit Mars Exploration Rover

NASA Astrophysics Data System (ADS)

Morris, R. V.; Klingelhöfer, G.; Schröder, C.; Fleischer, I.; Ming, D. W.; Yen, A. S.; Gellert, R.; Arvidson, R. E.; Rodionov, D. S.; Crumpler, L. S.; Clark, B. C.; Cohen, B. A.; McCoy, T. J.; Mittlefehldt, D. W.; Schmidt, M. E.; de Souza, P. A.; Squyres, S. W.

2008-12-01

Spirit's Mössbauer (MB) instrument determined the Fe mineralogy and oxidation state of 71 rocks and 43 soils during its exploration of the Gusev plains and the Columbia Hills (West Spur, Husband Hill, Haskin Ridge, northern Inner Basin, and Home Plate) on Mars. The plains are predominantly float rocks and soil derived from olivine basalts. Outcrops at West Spur and on Husband Hill have experienced pervasive aqueous alteration as indicated by the presence of goethite. Olivine-rich outcrops in a possible mafic/ultramafic horizon are present on Haskin Ridge. Relatively unaltered basalt and olivine basalt float rocks occur at isolated locations throughout the Columbia Hills. Basalt and olivine basalt outcrops are found at and near Home Plate, a putative hydrovolcanic structure. At least three pyroxene compositions are indicated by MB data. MB spectra of outcrops Barnhill and Torquas resemble palagonitic material and thus possible supergene aqueous alteration. Deposits of Fe3+-sulfate soil, located at Paso Robles, Arad, and Tyrone, are likely products of acid sulfate fumarolic and/or hydrothermal activity, possibly in connection with Home Plate volcanism. Hematite-rich outcrops between Home Plate and Tyrone (e.g., Montalva) may also be products of this aqueous activity. Low water-to-rock ratios (isochemical alteration) are implied during palagonite, goethite, and hematite formation because bulk chemical compositions are basaltic (SO3-free basis). High water-to-rock ratios (leaching) under acid sulfate conditions are implied for the high-SiO2 rock and soil in Eastern Valley and the float rock FuzzySmith, which has possible pyrite/marcasite as a hydrothermal alteration product.

Origin of sulfide and phosphate deposits in Upper Proterozoic carbonate strata, Irece basin, Bahia, Brazil

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

Characteristics of Hydrothermal Mineralization in Ultraslow Spreading Ridges

NASA Astrophysics Data System (ADS)

Zhou, H.; Yang, Q.; Ji, F.; Dick, H. J.

2014-12-01

Hydrothermal activity is a major component of the processes that shape the composition and structure of the ocean crust, providing a major pathway for the exchange of heat and elements between the Earth's crust and oceans, and a locus for intense biological activity on the seafloor and underlying crust. In other hand, the structure and composition of hydrothermal systems are the result of complex interactions between heat sources, fluids, wall rocks, tectonic controls and even biological processes. Ultraslow spreading ridges, including the Southwest Indian Ridge, the Gakkel Ridge, are most remarkable end member in plate-boundary structures (Dick et al., 2003), featured with extensive tectonic amagmatic spreading and frequent exposure of peridotite and gabbro. With intensive surveys in last decades, it is suggested that ultraslow ridges are several times more effective than faster-spreading ridges in sustaining hydrothermal activities. This increased efficiency could attributed to deep mining of heat and even exothermic serpentinisation (Baker et al., 2004). Distinct from in faster spreading ridges, one characteristics of hydrothermal mineralization on seafloor in ultraslow spreading ridges, including the active Dragon Flag hydrothermal field at 49.6 degree of the Southwest Indian Ridge, is abundant and pervasive distribution of lower temperature precipitated minerals ( such as Fe-silica or silica, Mn (Fe) oxides, sepiolite, pyrite, marcasite etc. ) in hydrothermal fields. Structures formed by lower temperature activities in active and dead hydrothermal fields are also obviously. High temperature precipitated minerals such as chalcopyrite etc. are rare or very limited in hydrothermal chimneys. Distribution of diverse low temperature hydrothermal activities is consistence with the deep heating mechanisms and hydrothermal circulations in the complex background of ultraslow spreading tectonics. Meanwhile, deeper and larger mineralization at certain locations along the ultraslow spreading ridges is also presumable.

Mineral matter and potentially hazardous trace elements in coals from Qianxi Fault Depression Area in southwestern Guizhou, China

USGS Publications Warehouse

Zhang, Jiahua; Ren, D.; Zhu, Y.; Chou, C.-L.; Zeng, R.; Zheng, B.

2004-01-01

Mineralogy, coal chemistry and 21 potentially hazardous trace elements (PHTEs) of 44 coal samples from the Qianxi Fault Depression Area (QFDA) in southwestern Guizhou province, China have been systematically studied. The major minerals in coals studied are quartz, kaolinite, illite, pyrite, calcite, smectite, marcasite and accessory minerals, including rutile, dolomite, siderite, gypsum, chlorite, melanterite, apatite, collophane and florencite. The SiO2 content shows a broad variation (0.8-30.7%). A high SiO2 content in Late Permian coals reflects their enrichment in quartz. The Al2O3 content varies from 0.8% to 13.4%, Fe2O3 from 0.2% to 14.6%, CaO from Al>K>Ti>Na>Mg>Ca>Fe>S. A comparison with World coal averages shows that the Late Permian coals in QFDA are highly enriched in As, Hg, F and U, and are slightly enriched in Mo, Se, Th, V and Zn. The Late Triassic coals in QFDA are highly enriched in As and Hg, and are slightly enriched in Mo, Th and U. The concentrations of As, Hg, Mo, Se, Tl and Zn in the QFDA coal are higher than other Guizhou coal and Liupanshui coal nearby. The QFDA is an area strongly affected by the low-temperature hydrothermal activity during its geologic history (Yanshanian Age, about 189 Ma). The coals in QFDA are enriched in volatile PHTEs, including As, Hg, Se, Sb, Mo, among others. The regions where the coals are enriched in As, Hg and F have been mapped. The regions of coals enriched in volatile PHTEs overlap with the regions of noble metal ore deposits. These coals are located in the cores of anticline and anticlinorium, which are connected with the profound faults through the normal faults. Coals are enriched in volatile PHTEs as a result of the low-temperature hydrothermal activity associated with tectonic faulting. ?? 2003 Elsevier B.V. All rights reserved.

Lateral variation in geochemistry, petrology, and palynology in the Elswick coal bed, Pike County, Kentucky

USGS Publications Warehouse

Hower, J.C.; Ruppert, L.F.; Eble, C.F.

2007-01-01

The Middle Pennsylvanian/Langsettian (Westphalian A) Elswick coal bed, correlative to the Upper Banner of Virginia, is a rare example of a mined high-sulfur (> 2%) coal in Eastern Kentucky, a region known for low-sulfur coals. To characterize lateral variation in the geochemistry, petrography, and palynology of the Elswick coal bed, three sites were sampled along a southeast-northwest transect within a single mine. At the southeastern site, the lower 101??cm of the 116-cm thick coal is dull, generally dominated by durain and dull clarain. While all benches at this site fit within the previously-defined "mixed palynoflora - moderate/low vitrinite group," suggesting a stressed environment of deposition, the palynology of the benches of the dull interval show greater diversity than might be expected just from the petrology. Lithology is generally similar between the sites, but each site has some differences in the petrology. Overall, the coal bed shows significant lateral variation in properties at the mine scale, some of which can be attributed to the gain or loss of upper and lower lithologies, either through an actual physical merging or through the change in character of lithotypes. Sulfur content varies between the three sites examined for this study. Site 3, located in the northwestern portion of the study area is characterized by a strikingly high sulfur zone (7.45%) in the middle of the coal bed, a feature missing at the other sites. Pyrite and marcasite, in a mid-seam lithotype at the northwestern site (site 3), show signs of overgrowths, indicating multiple generations of sulfide emplacement. The high-sulfur site 3 lithologies all have massive overgrowths of euhedral and framboidal pyrite, fracture- and cleat-fill pyrite, and sulfide emplacement in fusinite lumens. Sulfur is high throughout the mine area, but variations are evident in the extent of secondary growth of sulfides. ?? 2006 Elsevier B.V. All rights reserved.

Gold ores related to shear zones, West Santa Comba-Fervenza Area (Galicia, NW Spain): A mineralogical study

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.

Distribution and speciation of metals in soils of the former mining district of Touiref (Northwest Tunisia)

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.

Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bachhuber, Frederik; School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland; Krach, Alexander

2015-03-15

Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine theirmore » stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.« less

Arsenic occurrence, mobility, and retardation in sandstone and dolomite formations of the Fox River Valley, Eastern Wisconsin.

PubMed

Thornburg, Katie; Sahai, Nita

2004-10-01

Elevated levels of groundwater arsenic (approximately 100 microg L(-1) = 1.3 x 10(-6) M) are found in the Fox River Valley, eastern Wisconsin. The goals of this study were to identifythe sources of As contamination and to determine the reactions responsible for As mobilization and retardation in areas lacking a discrete zone of As-enriched sulfides, shown previouslyto cause elevated arsenic in groundwater. Detailed mineralogical and chemical analyses were conducted on samples from the Sinnipee Group dolomite and St. Peter sandstone in eastern Wisconsin. Solution chemistry was monitored in batch reactions of dolomite, quartz, and sulfide mineral fractions with a 0.01 M CsCl solution at pH 7 for 3 weeks in air. Results indicate that arsenic is present in isomorphous substitution with pyrite/marcasite (FeS2), which occurs as disseminated veins, grains, and nodules in the dolomite and sandstone. The released As subsequently sorbs on the ferric oxyhydroxides formed or coprecipitates in a scorodite-like phase. Significantly, oxidative dissolution of the disseminated As-rich FeS2 grains and nodules is sufficient to explain the elevated As levels observed in eastern Wisconsin groundwater. Although complete uptake of As is observed in the batch experiments, persistent elevated As levels with spatial and temporal variations in regional groundwaters are attributed to differences in the type of sulfide occurrence (discrete horizon vs dispersed grains, veins, and nodules), variations in the dissolved oxygen content of the groundwater, and variable (limited) buildup of reacted surface layers on sulfide grains in the natural flow-through system. Discrete nanoparticulate As phases, As surface precipitates on sulfides, and sorbed As on dolomite and quartz are eliminated as major sources, and sorption of arsenic on dolomite and quartz is deemed less important than association with ferric oxyhydroxides for retardation in the regional system.

Detailed mineral and chemical relations in two uranium-vanadium ores

USGS Publications Warehouse

Garrels, Robert M.; Larsen, E. S.; Pommer, A.M.; Coleman, R.G.

1956-01-01

Channel samples from two mines on the Colorado Plateau have been studied in detail both mineralogically and chemically. A channel sample from the Mineral Joe No. 1 mine, Montrose County, Colo., extends from unmineralized rock on one side, through a zone of variable mineralization, into only weakly mineralized rock. The unmineralized rock is a fairly clean quartz sand cemented with gypsum and contains only minor amounts of clay minerals. One boundary between unmineralized and mineralized rock is quite sharo and is nearly at right angles to the bedding. Vanadium clay minerals, chiefly mixed layered mica-montmorillonite and chlorite-monmorillonite, are abundant throughout the mineralized zone. Except in the dark "eye" of the channel sample, the vanadium clay minerals are accompanied by hewettite, carnotite, tyuyamunite, and probably unidentified vanadates. In the dark "eye," paramontroseite, pyrite, and marcasite are abundant, and bordered on each side by a zone containing abundant corvusite. No recognizable uranium minerals were seen in the paramontroseite zone although uranium is abundant there. Coaly material is recognizable throughout all of the channel but is most abundant in and near the dark "eye." Detailed chemical studies show a general increase in Fe, Al, U, and V, and a decrease in SO4 toward the "eye" of the channel. Reducing capacity studies indicate that V(IV) and Fe(II) are present in the clay mineral throughout the channel, but only in and near the "eye" are other V(IV) minerals present (paramontroseite and corvusite). The uranium is sexivalent, although its state of combination is conjectural where it is associated with paramontroseite. Where the ore boundary is sharp, the boundary of introduced trace elements is equally sharp. Textural and chemical relations leave no doubt that the "eye: is a partially oxidized remnant of a former lower-valence ore, and the remainder of the channel is a much more fully oxidized remnant. A channel sample from the Virgin No. 3 mine, Montrose County, Colo., extends from weakly mineralized sandstone on both sides through a strongly mineralized central zone. The weakly mineralized zone is a poorly sorted sandstone with common detrital clay partings; chlorite and mixed layer mica-montmorrillonite are abundant interstitial to the quartz grains. No distinct vanadium or uranium minerals are recognizable, although the clay minerals are vanadium bearing. Euherdral pyrite grains and selenian galena are present but rare. The strongly mineralized rock is separated from the weakly mineralized rock by a narrow transition zone which only apporiximates the bedding planes. It contains abundant vanadium-bearing clay minerals (predominantly chlorite) interstitial to the quartz grains, and apparently replacing them. Paramontroseite is common and is intergrown with the clay minerals. Pyrite and marcasite are present, chiefly in or near the abundant blebs and fragments of carbonaceous material. Selenian galena is rarely present, and generally in or near carbonaceous material. Coffinite is the only uranium mineral idenitified; it is extremely fine grained and was identified only in X-ray diffraction patterns of heavy separates. Distribution of trace elements is not clear; some are consistently high in the strongly mineralized rocks, and some are consistently low. The trace element composition of the unmineralized rock is not known. Chemical studies show a very abrupt rise in the total U, V, and Fe from the weakly mineralized to strongly mineralized rock. Reducing-capacity studies indicate that most of the vanadium is present as V(IV), but some is present as V(V); that iron is present as both Fe(II) and Fe(III), the latter believed to have been present in the primary clays of the unmineralized rock; and that come of the uranium is present as U(VI) in addition to the U(IV) in the coffinite. All evidence points to weak oxidation of an ore once having a somewhat lower valence state. The channel samples from both the Mineral Joe No. 1 mine and the Virgin No. 3 mine are believe to have been essentially identical in mineralogy prior to oxidation by weathering: vanadium was present as V(III) in montroseite and V(IV) in the vanadium clays; uranium was present largely as U(IV) in coffinite and/or uraninite. The Mineral Joe No. 1 mine channel sample is now more fully oxidized. Vanadium clays are unquestionably formed abundantly during the primary mineralization, and they persist with a minimum of alteration during much of the weathering. They suggest that the vanadium is carried as V(IV) in the ore-forming fluids; it seems likely too that the uranium is carried as a U(VI) ion.

MINERALOGY, PETROGRAPHY, AND RADIOACTIVITY OF REPRESENTATIVE SAMPLES OF CHATTANOOGA SHALE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bates, T.F.; Strahl, E.O.

1957-01-01

Qualitative and quantitative mineralogical studies of the Chattanooga Shale are in progress. Problems of separation and analysis of mineral and organic components are difficult because the rock is fine-grained. However, the applicaiion of light and electron microscopy, x-ray diffraction, nuclear-track study, and other methods has provided data of interest. Megascopically, the shalc is a massive chocolate-brown sediment which displays faint indications of lamination. Some pyrite lenses, nodules, and crystals and a few mica flakes are large enough to be seen with a hand lens. In thin section the rock is seen to consist of grains of quartz and feldspar inmore » a matrix of yellow to red--brown organic material, which incorporates shreds of mica and probably clay particles and is dotted by small clusters of pyrite. Larger organic fragments with associated pyrite are common and take various forms. Individual mineral particles range from pyrite cubes less than 0.15 micron on a side to quartz and feldspar grains as large as 0.10 mm. X-ray studies show the clay minerals to be illite, kaolinite, and chlorite in decreasing order of abundance. Tourmaline, zircon, and apatite are the characteristic heavy minerals of the sediment. Quantitative studies, accomplished by a combination of chemical and mineralogical methods, have shown the composition of a batch sample of this rock to be approxiinately: 22% quartz, 9% feldspar, 31% illite and kaolinite, 22% organic matter, 11% pyrite and marcasite, 2% chlorite, 2% iron oxides, and l% tourmaline, zircon, and apatite. Alphatrack studies of cniulsion-covered thin sections indicate that no uranium mineral is present. Approximately 70% of the uranium atoms is randomly distributed throughout the finegrained matrix of the rock, whereas another 25% is concentrated in organic-pyrite-clay complexes such as pyrite nodules and discrete organic bodies. In unweathered samples there is no relationship between uranium distribution and textural fcatures such as bedding. The data indicate that the uranium was precipitated from sea water under reducing conditions and has not been redistributed following compaction of the sediment. (auth)« less

Geologic setting, sedimentary architecture, and paragenesis of the Mesoproterozoic sediment-hosted Sheep Creek Cu-Co-Ag deposit, Helena embayment, Montana

USGS Publications Warehouse

Graham, Garth; Hitzman, Murray W.; Zieg, Jerry

2012-01-01

The northern margin of the Helena Embayment contains extensive syngenetic to diagenetic massive pyrite horizons that extend over 25 km along the Volcano Valley-Buttress fault zone and extend up to 8 km basinward (south) within the Mesoproterozoic Newland Formation. The Sheep Creek Cu-Co deposit occurs within a structural block along a bend in the fault system, where replacement-style chalcopyrite mineralization is spatially associated mostly with the two stratigraphically lowest massive pyrite zones. These mineralized pyritic horizons are intercalated with debris flows derived from synsedimentary movement along the Volcano Valley-Buttress fault zone. Cominco American Inc. delineated a geologic resource of 4.5 Mt at 2.5% Cu and 0.1% Co in the upper sulfide zone and 4 Mt at 4% Cu within the lower sulfide zone. More recently, Tintina Resources Inc. has delineated an inferred resource of 8.48 Mt at 2.96% Cu, 0.12% Co, and 16.4 g/t Ag in the upper sulfide zone. The more intact upper sulfide zone displays significant thickness variations along strike thought to represent formation in at least three separate subbasins. The largest accumulation of mineralized sulfide in the upper zone occurs as an N-S–trending body that thickens southward from the generally E trending Volcano Valley Fault and probably occupies a paleograben controlled by normal faults in the hanging wall of the Volcano Valley Fault. Early microcrystalline to framboidal pyrite was accompanied by abundant and local barite deposition in the upper and lower sulfide zones, respectively. The sulfide bodies underwent intense (lower sulfide zone) to localized (upper sulfide zone) recrystallization and overprinting by coarser-grained pyrite and minor marcasite that is intergrown with and replaces dolomite. Silicification and paragenetically late chalcopyrite, along with minor tennantite in the upper sulfide zone, replaces fine-grained pyrite, barite, and carbonate. The restriction of chalcopyrite to inferred synsedimentary E- and northerly trending faults and absence of definitive zonation with respect to the Laramide Volcano Valley Fault in the lower sulfide zone suggest a diagenetic age related to basin development for the Sheep Creek Cu-Co-Ag deposit.

Sediment-hosted micro-disseminated gold mineralization constrained by basin paleo-topographic highs in the Youjiang basin, South China

NASA Astrophysics Data System (ADS)

Liu, Jianming; Ye, Jie; Ying, Hanlong; Liu, Jiajun; Zheng, Minghua; Gu, Xuexiang

2002-06-01

The Youjiang basin is a Devonian-Triassic rift basin on the southern margin of the Yangtze Craton in South China. Strong syndepositional faulting defined the basin-and-range style paleo-topography that further developed into isolated carbonate platforms surrounded by siliciclastic filled depressions. Finally, thick Triassic siliciclastic deposits covered the platforms completely. In the Youjiang basin, numerous sediment-hosted, micro-disseminated gold (SMG) deposits occur mainly in Permian-Triassic chert and siliciclastic rocks. SMG ores are often auriferous sedimentary rocks with relatively low sulfide contents and moderate to weak alteration. Similar to Carlin-type gold ores in North America, SMG ores in the Youjiang basin are characterized by low-temperature mineral assemblages of pyrite, arsenopyrite, realgar, stibnite, cinnabar, marcasite, chalcedony and carbonate. Most of the SMG deposits are remarkably distributed around the carbonate platforms. Accordingly, there are platform-proximal and platform-distal SMG deposits. Platform-proximal SMG deposits often occur in the facies transition zone between the underlying platform carbonate rocks and the overlying siliciclastic rocks with an unconformity (often a paleo-karst surface) in between. In the ores and hostrocks there are abundant synsedimentary-syndiagenetic fabrics such as lamination, convolute bedding, slump texture, soft-sediment deformation etc. indicating submarine hydrothermal deposition and syndepositional faulting. Numerous fluid-escape and liquefaction fabrics imply strong fluid migration during sediment basin evolution. Such large-scale geological and fabric evidence implies that SMG ores were formed during basin evolution, probably in connection with basinal fluids. It is well known that basinal fluids (especially sediment-sourced fluids) will migrate generally (1) upwards, (2) towards basin margins or basin topographic highs, (3) and from thicker towards thinner deposits during basin evolution. The isolated carbonate platform (as a basin paleo-high) and related syndepositional fault system, together with the unconformity-related facies succession, may have controlled the migration pathway of ore-forming basinal fluids and subsequently determined the location of SMG deposits in the Youjiang basin. Unlike Carlin-type gold deposits, SMG mineralization in the Youjiang basin may represent an integral aspect of the dynamic evolution of extensional basins along divergent continental margins.

The flotation tailings of the former Pb-Zn mine of Touiref (NW Tunisia): mineralogy, mine drainage prediction, base-metal speciation assessment and geochemical modeling.

PubMed

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 carbonaceous phyllite rock-hosted Pedra Verde copper mine, Borborema Province, Brazil: Stable isotope constraints, structural controls and metallogenic evolution

NASA Astrophysics Data System (ADS)

da Silva Nogueira de Matos, José Henrique; Saraiva dos Santos, Ticiano José; Virgínia Soares Monteiro, Lena

2017-12-01

The Pedra Verde Copper Mine is located in the Viçosa do Ceará municipality, State of Ceará, NE Brazil. The copper mineralization is hosted by the Pedra Verde Phyllite, which is a carbonaceous chlorite-calcite phyllite with subordinate biotite. It belongs to the Neoproterozoic Martinópole Group of the Médio Coreaú Domain, Borborema Province. The Pedra Verde deposit is stratabound and its ore zoning is conspicuous, according to the following sequence, from bottom to top: marcasite/pyrite, native silver, chalcopyrite, bornite, chalcocite, native copper and hematite. Barite and carbonaceous material are reported in ore zones. Zoning reflects the ore formation within a redox boundary developed due to the interaction between oxidized copper- and sulfate-bearing fluids and the reduced phyllite. Structural control on mineralization is evidenced by the association of the ore minerals with veins, hinge folds, shadow pressures, and mylonitic foliation. It was mainly exercised by a dextral transcurrent shear zone developed during the third deformational stage identified in the Médio Coreaú Domain between 590 Ma and 570 Ma. This points to the importance of epigenetic, post-metamorphic deformational events for ore formation. Oxygen isotopic composition (δ18OH2O = 8.94 to 11.28‰, at 250 to 300 °C) estimated for the hydrothermal fluids in equilibrium with calcite indicates metamorphic or evolved meteoric isotopic signatures. The δ13CPDB values (-2.60 to -9.25‰) obtained for hydrothermal calcite indicate mixing of carbon sources derived from marine carbonate rocks and carbonaceous material. The δ34SCDT values (14.88 to 36.91‰) of sulfides suggest evaporites as sulfate sources or a closed system in relation to SO42- availability to form H2S. Carbonaceous matter had a key role in thermochemical sulfate processes and sulfide precipitation. The Pedra Verde Copper Mine is considered the first stratabound meta-sedimentary rock-hosted copper deposit described in Brazil and shares similarities with the syn-orogenic copper deposits of the Congo-Zambian Copperbelt formed during the Gondwana amalgamation.

Geology of the Midnite uranium mine, Stevens County, Washington; a preliminary report

USGS Publications Warehouse

Nash, J. Thomas; Lehrman, Norman J.

1975-01-01

The Midnite mine is one of only two mines in the United States currently producing uranium from discordant deposits in crystalline host rocks. Ore bodies are in metamorphosed steeply dipping Precambrian pelitic and calcareous rocks of a roof pendant adjacent to a Cretaceous(?) porphyritic quartz monzonite pluton. Production during 14 years, of operation has been about 8 million pounds of U3O8 from oxidized and reduced ores averaging 0.23 percent U3O8. Uranium deposits are generally tabular in form and dimensions range up to 380 m long, 210 m wide, and 50 m thick. Deposits are bounded on at least one side by unmineralized intrusive ribs of granitic rock, and thickest mineralized zones invariably occur at depressions in the intrusive contact. Upper limits of some deposits are nearly horizontal, and upper elevations of adjacent mineralized zones separated by ribs of granite are similar. Near surface ore is predominantly autunite, but ore at depth consists of pitchblende and coffinite with abundant pyrite and marcasite. Uranium minerals occur as .disseminations along foliation, replacements, and stockwork fracture-fillings. No stratigraphic controls on ore deposition are recognized. Rather, mineralized zones cut across lithologic boundaries if permeability is adequate. Most ore is in muscovite schist and mica phyllite, but important deposits occur in calc-silicate hornfels. Amphibolite sills and mid-Tertiary dacite dikes locally, carry ore where intensely fractured. High content of iron and sulfur, contained chiefly in FeS2, appear to be an important feature of favorable host rocks. Geometry of deposits, structural, and geochemical features suggest that uranium minerals were deposited over a span of time from late Cretaceous to late Tertiary. Ore occurs in but is not offset by a shear zone that displaces mid-Tertiary rocks.. Economic zones of uranium are interpreted to have been secondarily enriched in late Tertiary time by downward and lateral migration of uranium into permeable zones where deposition was influenced by ground water controls and minerals that could reduce or neutralize uranium-bearing solutions.

Sedimentary rock-hosted Au deposits of the Dian-Qian-Gui area, Guizhou, and Yunnan Provinces, and Guangxi District, China

USGS Publications Warehouse

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.

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9-10°N

USGS Publications Warehouse

Rouxel, O.; Shanks, Wayne C.; Bach, W.; Edwards, K.J.

2008-01-01

In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9–10°N to better constrain processes affecting Fe-isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) Is there significant Fe-isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S-isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between − 0.11 to − 0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (− 0.6 ± 0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42− followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower-temperature, Fe-depleted vents.

Geochemical element mobility during the hydrothermal alteration in the Tepeoba porphyry Cu-Mo-Au deposits at Balikesir, NW Turkey

NASA Astrophysics Data System (ADS)

Abdelnasser, Amr; Kiran Yildirim, Demet; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Tepeoba porphyry Cu-Mo-Au deposit represents one of the important copper source and mineral deposits in the Anatolian tectonic belt at Balikesir province, NW Turkey. It considered as a vein-type deposit locally associated with intense hydrothermal alteration within the brecciation, quartz stockwork veining, and brittle fracture zones in the main host rock that represented by hornfels, as well as generally related to the shallow intermediate to silicic intrusive Eybek pluton. Based on the field and geologic relationships and types of ore mineral assemblages and the accompanied alteration types, there are two mineralization zones; hypogene (primary) and oxidation/supergene zones are observed associated with three alteration zones; potassic, phyllic, and propylitic zones related to this porphyry deposit. The phyllic and propylitic alterations locally surrounded the potassic alteration. The ore minerals related to the hypogene zone represented by mostly chalcopyrite, Molybdenite, and pyrite with subordinate amount of marcasite, enargite, and gold. On the other hand they include mainly cuprite with chalcopyrite, pyrite and gold as well as hematite and goethite at the oxidation/supergene zone. This study deals with the quantitative calculations of the mass/volume changes (gains and losses) of the major and trace elements during the different episodes of alteration in this porphyry deposit. These mass balance data reveal that the potassic alteration zone that the main Cu- and Mo-enriched zone, has enrichment of K, Si, Fe, and Mg, and depletion of Na referring to replacement of plagioclase and amphibole by K-feldspar, sericite and biotite. While the propylitic alteration that is the main Mo- and Au-enriched zone is accompanied with K and Na depletion with enrichment of Si, Fe, Mg, and Ca forming chlorite, epidote, carbonate and pyrite. On the other hand the phyllic alteration that occurred in the outer part around the potassic alteration, characterized by less amount of Cu and Mo mineralization having addition of Si and K with removal of Fe, Mg, Ca, and Na. Keywords: Mass balance calculation; Tepeoba porphyry Cu-Mo-Au deposits; Balikesir; Turkey

A Conspicuous Clay Ovoid in Nakhla: Evidence for Subsurface Hydrothermal Alteration on Mars with Implications for Astrobiology

PubMed Central

Haigh, Sarah; Lyon, Ian

2014-01-01

Abstract A conspicuous biomorphic ovoid structure has been discovered in the Nakhla martian meteorite, made of nanocrystalline iron-rich saponitic clay and amorphous material. The ovoid is indigenous to Nakhla and occurs within a late-formed amorphous mesostasis region of rhyolitic composition that is interstitial to two clinopyroxene grains with Al-rich rims, and contains acicular apatite crystals, olivine, sulfides, Ti-rich magnetite, and a new mineral of the rhoenite group. To infer the origin of the ovoid, a large set of analytical tools was employed, including scanning electron microscopy and backscattered electron imaging, wavelength-dispersive X-ray analysis, X-ray mapping, Raman spectroscopy, time-of-flight secondary ion mass spectrometry analysis, high-resolution transmission electron microscope imaging, and atomic force microscope topographic mapping. The concentric wall of the ovoid surrounds an originally hollow volume and exhibits internal layering of contrasting nanotextures but uniform chemical composition, and likely inherited its overall shape from a preexisting vesicle in the mesostasis glass. A final fibrous layer of Fe-rich phases blankets the interior surfaces of the ovoid wall structure. There is evidence that the parent rock of Nakhla has undergone a shock event from a nearby bolide impact that melted the rims of pyroxene and the interstitial matter and initiated an igneous hydrothermal system of rapidly cooling fluids, which were progressively mixed with fluids from the melted permafrost. Sharp temperature gradients were responsible for the crystallization of Al-rich clinopyroxene rims, rhoenite, acicular apatites, and the quenching of the mesostasis glass and the vesicle. During the formation of the ovoid structure, episodic fluid infiltration events resulted in the precipitation of saponite rinds around the vesicle walls, altered pyrrhotite to marcasite, and then isolated the ovoid wall structure from the rest of the system by depositing a layer of iron oxides/hydroxides. Carbonates, halite, and sulfates were deposited last within interstitial spaces and along fractures. Among three plausible competing hypotheses here, this particular abiotic scenario is considered to be the most reasonable explanation for the formation of the ovoid structure in Nakhla, and although compelling evidence for a biotic origin is lacking, it is evident that the martian subsurface contains niche environments where life could develop. Key Words: Biomorph—Clays—Search for life (biosignatures)—Martian meteorites—Hydrothermal systems. Astrobiology 14, 651–693. PMID:25046549

Microbial sulfate reduction and the sulfur budget for a complete section of altered oceanic basalts, IODP Hole 1256D (eastern Pacific)

USGS Publications Warehouse

Alt, Jeffrey C.; Shanks, Wayne C.

2011-01-01

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155ppm sulfur and are more oxidized, have high SO4/ΣS ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative δ34Ssulfide-S values (down to -30 °) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940ppm S, and with δ34S shifted to -6.0‰) from the mantle value (0 ‰). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 X1010molSyr-1, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 X 10-8molcm-2yr-1 over 15m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 X 1011moly-1, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Origin of the Mariano Lake uranium deposit, McKinley County, New Mexico

USGS Publications Warehouse

Fishman, Neil S.; Reynolds, Richard L.

1982-01-01

The Mariano Lake uranium deposit, hosted by the Brushy Basin Member of the Jurassic Morrison Formation, occurs in the trough of an east-west trending syncline at the western end of the Smith Lake-Mariano Lake group of uranium deposits near Crownpoint, New Mexico. The orebody, which contains abundant amorphous organic material, is situated on the reduced side of a regional reduction-oxidation (redox) interface. The presence of amorphous organic material suggests the orebody may represent a tabular (primary) deposit, whereas the close proximity of the orebody to the redox interface is suggestive that uranium was secondarily redistributed by oxidative processes from pre-existing tabular orebodies. Uranium contents correlate positively with both organic carbon and vanadium contents. Petrographic evidence and scanning electron microscope-energy dispersive analyses point to uranium residence in the epigentically introduced amorphous organic material, which coats detrital grains and fills voids. Uranium mineralization was preceded by the following diagenetic alterations: precipitation of pyrite (d34S values ranging from-11.0 to-38.2 per mil); precipitation of mixed-layer smectite-illite clays; partial dissolution of some of the detrital feldspar population; and precipitation of quartz and adularia overgrowths. Alterations associated with uranium mineralization include emplacement of amorphous organic material (possibly uranium bearing); destruction of detrital iron-titanium oxide grains; coprecipitation of chlorite and microcrystalline quartz, and precipitation of pyrite and marcasite (d34S values for these sulfides ranging from -29.4 to -41.6 per mil). After mineralization, calcite, dolomite, barite, and kaolinite precipitated, and authigenic iron disulfides were replaced by ferric oxides and hydroxides. Geochemical data (primarily the positive correlation of uranium content to both organic carbon and vanadium contents) and petrographic observations (epigentically introduced amorphous organic matter and uranium residence in this organic matter) indicate that the Mariano Lake orebody is a tabular-type uranium deposit. Oxidative processes have not noticeably redistributed and reconcentrated primary uranium in the immediate vicinity of the deposit nor have they greatly modified geochemical characteristics in the ore. Preservation of the Mariano Lake deposit may not only be related to its position along the synclinal trough, where oxidative destruction of the orebody has been inhibited by stagnation of oxidizing ground waters by the structure, but also due to the deflection of ground waters (resulting from low orebody porosity) around the orebody.

Reactive alteration of Mt. Simon sandstone during CO2-rich brine injection: A coupled experimental and modeling study

NASA Astrophysics Data System (ADS)

Dávila Ordoñez, M. G.; Zahasky, C.; Crandall, D.; Druhan, J. L.

2017-12-01

Thus far, one million metric tons of CO2 have been injected into the lower Mt. Simon formation as part of the Decatur CO2 Capture and Storage Project. Micro-seismic events were observed within the CO2 plume both during and after pressurization associated with the primary injection. The Mt. Simon reservoir rock consists of 76.5 wt.% quartz, 2.1 wt.% calcite, 17.3 wt.% K-feldspar, 1.1 wt.% chlorite, 0.7 wt.% illite and lesser extents of siderite, kaolinite, dolomite and marcasite, and is thus anticipated to become geochemically altered by exposure to acidified CO2-rich brine. However, the extent to which the geochemical reactivity contributes to structural weakening is unknown. To explore relationships between the principle geochemical reactions, evolution of fluid transport properties and physical alteration, we performed a series of flow-through experiments using Mt. Simon core (5 cm diameter, ranging from 4.3 - 8.6 cm length) and fluids representative of acidified reservoir brine. Experiments were operated under P = 1450 bar, Pconfining = 1900 - 3000 bar and T = 53 ºC conditions, and flow rates varied from 0.08 to 5.00 mL h-1 over a period of 166 h. A 2D reactive transport code (Crunch-Tope) was used to simulate these experiments, constrained by measured time series aqueous concentrations of Ca, Mg, S, Si, K and Fe and pH during the CO2-rich brine interaction. The model domain was divided into 30 nodes in x at a spacing of 0.12 cm, and 40 nodes in y at a spacing of 0.22 cm, and initial permeability measured for the core was specified and allowed to evolve over the course of the simulation using measured flow rate as a constraint. All relevant kinetic and thermodynamic reaction parameters were obtained from the literature. Solute time series from both experiments and simulations indicated that the acidified brine introduced continuously into the column promoted dissolution of K-feldspar, chloride, illite, pyrite and calcite, and the precipitation of Ca-, Fe- and Si -bearing secondary phases, resulting in a net porosity increase at the inlet. Despite this opening of the inlet pore space, permeability decreased over the length of the column (kfinal/kinitial = 0.76), thus altering local resistance to fluid phase pressure gradients.

Variable Seawater-Peridotite Interactions - First Insights From ODP Leg 209, MAR 15° N

NASA Astrophysics Data System (ADS)

Bach, W.; Garrido, C. J.; Harvey, J.; Paulick, H.; Rosner, M.; Odp Leg 193 Shipboard Science Party

2003-12-01

Serpentinization of peridotites at slow-spreading mid-ocean ridges has important consequences for the rheology of the oceanic lithosphere, geochemical budgets of the oceans, and microbial processes within, at, and above the seafloor. ODP Leg 209 recovered peridotites that show a remarkable variability of hydrothermal alteration reactions and intensities, including talc-tremolite alteration of pyroxenes associated with incipient serpentinization of olivine, complete alteration of peridotites to serpentine and magnetite followed by the destruction of magnetite and replacement of serpentine by talc, variable degrees of serpentine-brucite alteration, and replacement of brucite by iowaite. These rocks provide a unique opportunity to calibrate our observations against recent results from experimental/theoretical geochemical studies and further our understanding of serpentinization and its role in tectonic accretion and microbial colonization of oceanic lithosphere at slow and ultraslow spreading ridges. We propose that at temperatures above 250° C, pyroxenes react to form serpentine, talc, and tremolite, releasing Ca, Si, H2, and acidity to the reacting fluids that may cause rodingitization in adjacent gabbro bodies. Overall however, rodingites are rare, which may reflect the depleted nature of the mantle protoliths. In the absence of pyroxenes (in dunites) - or at temperatures below 250° C, where pyroxenes react very slowly - the fluids do not become enriched in Ca and Si and serpentine, magnetite, and brucite will form. Many serpentinites lack brucite, tremolite, and talc, because changes in fluid pH and silica activity of the interacting fluids, following the exhaustion of either olivine or pyroxene, caused reaction of these phases to serpentine. Extensive talc alteration of serpentinites and gabbros is usually observed at the intrusive contacts, but large-scale silica metasomatism (or Mg-loss) must be invoked to explain the overall abundance of talc at Site 1268. Significant pyrite/marcasite/hematite veining at Site 1268 indicates fairly oxidizing conditions consistent with the presence of sulfate in the interacting fluids. The first discovery of iowaite in mid-ocean ridge serpentinites (at Site 1272) and the abundant carbonate/Fe-oxyhydroxide alteration, locally extending down to 90 meters below seafloor, indicate that water-rock reactions continue at low temperatures and under strongly oxidizing conditions. Pore fluids from nontronite-bearing serpentine muds in fault gouges may provide information about the nature of these late-stage circulating fluids and potential microbial activity.

Chemical and Mineralogical Characterization of Arsenic, Lead, Chromium, and Cadmium in a Metal-contaminated Histosol

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

Redox Sensitive Trace Element Enrichments of Organic Matter Rich Rocks (Kürnüç-Göynük/Bolu, Turkey)

NASA Astrophysics Data System (ADS)

Engin, H.; Sarı, A.; Koç, Ş.

2012-04-01

The oil shale deposits of Himmetoğlu and Hatıldağ nearby Göynük (Bolu/Türkiye) are well known oil shale deposits in Turkey. However, there is no detailed study about shale and marl type organic matter rich rocks of Kürnüç (Göynük (Bolu/Türkiye) currently available in the literature. This study aims to determine the enrichment of redox sensitive trace elements of organic matter rich rocks deposited at Kürnüç. The Kızılçay formation which outcrops in the vicinity of Kürnüç contains organic matter-rich rocks of marl and shale type. TOC %wt contents of Kürnüç vicinity rocks varies between 2,52-8,38 with an average of 6,13. The enrichments of S and Fe in these rocks and S% vs Fe% plot indicate the presence of pyrite and/or marcasite occurrences (r = 0,56). Also C-Fe-S relationship for the Kürnüç vicinity organic rich rocks suggest oxic and partially suboxic conditions. Some information about redox conditions of depositional environment of organic-rich rocks are obtained using redox sensitive element ratios such as V/(V+Ni), Ni/Co, U/Th and V/Sc. V/(V+Ni) ratios came out to be between 0,44-0,67, indicating suboxic-anoxic conditions; Ni/Co values are between 4,08-11,76, which indicates oxic-suboxic conditions; U/Th values are between 0,46-6,00, indicating suboxic-anoxic conditions; V/Sc values are between 5,53-24,50, pointing out oxic-suboxic condition. According to these values, Kürnüç vicinity organic matter-rich rocks are generally deposited in oxic to anoxic redox conditions. The redox sensitive elements Ni (20 - 129 ppm, with an average of 51,73 ppm), Co (0,2 - 20,6 ppm, with an average of 10,29 ppm), Cr (0,002 - 0,068%, with an average of 0,01%), Th (0,5 - 7,1 ppm, with an average of 4,02 ppm), Sc (1 - 13 ppm, with an average of 7,51 ppm), V (8 - 153 ppm, with an average of 70,55 ppm), U (0,6 - 35 ppm, with an average of 3,49 ppm) are obtained from the organic matter rich rocks. These elements are enriched 1-10 times relative to Average Shale, Coast of Peru, UCC (Upper Continental Crust), PAAS (Post Archean Average Shale), NASC (North American Shale Composit).

Spectral and chemical characterization of jarosite in a palaeolacustrine depositional environment in Warkalli Formation in Kerala, South India and its implications

NASA Astrophysics Data System (ADS)

Singh, Mahima; Rajesh, V. J.; Sajinkumar, K. S.; Sajeev, K.; Kumar, S. N.

2016-11-01

Coastal cliffs fringing the Arabian Sea near Varkala exhibits the Warkalli Formation of the Tertiary sequence of Kerala, South India, with well-marked occurrence of jarosite associated with other hydrous mineral phases of phyllosilicate family in a palaeo-lacustrine depositional environment. Sandy phyllosilicates dominate the mineral assemblage, but jarosite occurs as a prominent secondary phase formed during acid-sulphate alteration of iron sulphide in this area. Here, we discuss about the potentiality of spectroscopic techniques to identify the possible mineral phases in the collected samples. The samples from the coastal cliffs have been characterized by hyperspectral analysis (VIS-NIR-SWIR), X-ray Diffraction (XRD), Fourier Transform Infra-red Reflectance (FTIR), Electron Probe Microanalysis (EPMA) and Laser Raman spectroscopy. The spectral and chemical analyses have confirmed the jarosite as natrojarosite and phyllosilicate as kaolinite. Other accessory phases have also been identified through XRD. FTIR spectroscopy has played a major role in identifying the major hydrous bonds between the minerals. VIS-NIR-SWIR spectra show several optimum spectral features at 910 nm, 1470 nm, 1849-1864 nm (in the form of a doublet), 1940 nm and 2270 nm, which could be utilised to locate jarosite in the remotely-sensed data. X-ray diffraction peaks helped in the identification of maximum number of minerals (kaolinite, smectite, quartz, feldspar, pyrite, marcasite and hematite) and the variation in jarosite content in the samples. We propose the formation of jarosite in the region by a seasonal, local and temporary development of acidic conditions. Abundance of organic matter in a fluvio-lacustrine environment has developed anaerobic conditions by removing available oxygen through decomposition of organic matter containing sulphur compounds. The sulphur thus liberated combines with hydrogen from water to develop acidic conditions and resulted in the formation of jarosite. The occurrence of jarosite in Warkalli Formation suggests on and off supply of water during diagenesis. Jarosite has been detected as a prominent deposit in several regions on Mars by Mars Exploration rover Opportunity and Mars Reconnaissance Orbiter-Compact Reconnaissance Imaging Spectrometer for Mars (CRISM). This study of jarosite formation in terrestrial environment will influence our understanding on the mineral precipitation, diagenesis and hydration processes on Mars. Additionally, it also shows the importance of spectroscopic techniques like Raman spectrometry to be used in future missions to Mars to further validate the results of orbital spectroscopy.

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.

Thermochemical Constraints For the Formation Conditions of the Hydrothermal Alteration Mineralogy of Home Plate and Columbia Hills

NASA Astrophysics Data System (ADS)

Filiberto, J.; Schwenzer, S. P.

2012-12-01

Home Plate is a plateau in the Columbia Hills of Gusev Crater. It is dominated by igneous minerals (olivine, pyroxene, and magnetite) with small amounts of alteration minerals (hematite and nanophase oxides). Surrounding Home Plate are deposits containing diverse secondary mineral assemblages: Fe3+-sulfates deposits at Paso Robles, Dead Sea, Shredded, Arad, Tyrone, and Troy; Hematite-rich outcrops between Home Plate and Tyrone; SiO2-rich deposits possibly containing pyrite and/or marcasite at Fuzzy Smith; SiO2-rich, possibly opaline silica, deposits at Northern Valley, Eastern Valley, and Tyrone; and Mg-Fe-carbonate outcrops at Comanche in the Columbia Hills [1-4]. Here, we focus on using thermochemical modeling to understand the secondary alteration mineralogy at the Home Plate outcrop and surrounding Columbia Hills region in Gusev Crater. We use CHILLER [5] to evaluate mineral assemblages that are likely to form from the Martian Home Plate, Barn-Hill class rock Fastball in contact with a dilute fluid at various pressures, temperatures, and water-rock ratios. For details see [6]. In our models, hematite dominates the alteration assemblage at high W/R at 150°C, but is generally produced at W/R above 10. Goethite only forms at low temperature and W/R above 40 with a maximum around 100 and again around 100,000. Pyrite is produced at all temperatures but only at relatively high W/R. These results imply intermediate to high W/R and low to intermediate temperatures during alteration of the Home Plate region. Additional acidic brine, while not strictly excluded, is not required to form many of the observed phases. In contrast, the phyllosilicates recently invoked from orbital observations [4] indicate neutral to alkaline conditions - either accompanying the silica precipitation or as a separate event. For future exploration, our results emphasize that the observation of assemblages is critically important to understand mineral formation conditions and that minor phases such as fluorite can give valuable insights into host rock chemistry and alteration conditions. REFS: [1] Ruff S.W. et al. (2011) JGR 116, doi.10.1029/2010je003767. [2] Morris R.V. et al. (2008) JGR 113, doi.10.1029/2008je003201. [3] Morris R.V. et al. (2010) Science 329, 421-424. [4] Carter J. and Poulet F. (2012) Icarus 219, 250-253. [5] Reed M.H. and Spycher N.F. (2006) User Guide for CHILLER: A Program for Computing Water-Rock Reactions, Boiling, Mixing, and Other Reaction Processes in Squeous-Mineral-Gas Systems and Minplot Guide (3rd ed.), Eugene, Oregon: University of Oregon. [6] Schwenzer S.P. and Kring D.A. (2009) Geology 37, 1091-1094.

Potential anthropogenic mobilisation of mercury and arsenic from soils on mineralised rocks, Northland, New Zealand.

PubMed

Craw, D

2005-02-01

Eroded roots of hot spring systems in Northland, New Zealand consist of mineralised rocks containing sulfide minerals. Marcasite and cinnabar are the dominant sulfides with subordinate pyrite. Deep weathering and leached soil formation has occurred in a warm temperate to subtropical climate with up to 3 m/year rainfall. Decomposition of the iron sulfides in natural and anthropogenic rock exposures yields acid rock drainage with pH typically between 2 and 4, and locally down to pH 1. Soils and weathered rocks developed on basement greywacke have negligible acid neutralisation capacity. Natural rainforest soils have pH between 4 and 5 on unmineralised greywacke, and pH is as low as 3.5 in soils on mineralised rocks. Roads with aggregate made from mineralised rocks have pH near 3, and quarries from which the rock was extracted can have pH down to 1. Mineralised rocks are enriched in arsenic and mercury, both of which are environmentally available as solid solution impurities in iron sulfides and phosphate minerals. Base metals (Cu, Pb, Zn) are present at low levels in soils, at or below typical basement rock background. Decomposition of the iron sulfides releases the solid solution arsenic and mercury into the acid rock drainage solutions. Phosphate minerals release their impurities only under strongly acid conditions (pH<1). Arsenic and mercury are adsorbed on to iron oxyhydroxides in soils, concentrated in the C horizon, with up to 4000 ppm arsenic and 100 ppm mercury. Waters emanating from acid rock drainage areas have arsenic and mercury below drinking water limits. Leaching experiments and theoretical predictions indicate that both arsenic and mercury are least mobile in acid soils, at pH of c. 3-4. This optimum pH range for fixation of arsenic and mercury on iron oxyhydroxides in soils is similar to natural pH at the field site of this study. However, neutralisation of acid soils developed on mineralised rocks is likely to decrease adsorption and enhance mobility of arsenic and mercury. Hence, development of farmland by clearing forest and adding agricultural lime may mobilise arsenic and mercury from underlying soils on mineralised rocks. In addition, arsenic and mercury release into runoff water will be enhanced where sediment is washed off mineralised road aggregate (pH 3) on to farm land (pH>6). The naturally acid forest soils, or even lower pH of natural acid rock drainage, are the most desirable environmental conditions to restrict dissolution of arsenic and mercury from soils. This approach is only valid where mineralised soils have low base metal concentrations.

Petrology, mineralogy and geochemistry of mined coals, western Venezuela

USGS Publications Warehouse

Hackley, Paul C.; Warwick, Peter D.; González, Eligio

2005-01-01

Upper Paleocene to middle Miocene coal samples collected from active mines in the western Venezuelan States of Táchira, Mérida and Zulia have been characterized through an integrated geochemical, mineralogical and petrographic investigation. Proximate, ultimate, calorific and forms of sulfur values, major and trace element, vitrinite reflectance, maceral concentrations and mineral matter content have been determined for 16 channel samples from 14 mines. Ash yield generally is low, ranging from < 1 to 17 wt.% (mean = 5 wt.%) on a dry basis (db). Total sulfur content is low to moderate, ranging from 1 to 6 wt.%, db (average = 1.7 wt.%). Calorific value ranges from 25.21 to 37.21 MJ/kg (10,840–16,000 Btu/lb) on a moist, mineral-matter-free basis (average = 33.25 MJ/kg, 14,300 Btu/lb), placing most of the coal samples in the apparent rank classification of high-volatile bituminous. Most of the coal samples exhibit favorable characteristics on the various indices developed to predict combustion and coking behavior and concentrations of possible environmentally sensitive elements (As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, Th and U) generally are similar to the concentrations of these elements in most coals of the world, with one or two exceptions. Concentrations of the liptinite maceral group range from < 1% to 70 vol.%. Five samples contain > 20 vol.% liptinite, dominated by the macerals bituminite and sporinite. Collotelinite dominates the vitrinite group; telinite was observed in quantities of ≤ 1 vol.% despite efforts to better quantify this maceral by etching the sample pellets in potassium permanganate and also by exposure in an oxygen plasma chamber. Inertinite group macerals typically represent < 10 vol.% of the coal samples and the highest concentrations of inertinite macerals are found in distantly spaced (> 400 km) upper Paleocene coal samples from opposite sides of Lago de Maracaibo, possibly indicating tectonic controls on subsidence related to construction of the Andean orogen. Values of maximum reflectance of vitrinite in oil (Ro max) range between 0.42% and 0.85% and generally are consistent with the high-volatile bituminous rank classification obtained through ASTM methods. X-ray diffraction analyses of low-temperature ash residues indicate that kaolinite, quartz, illite and pyrite dominate the inorganic fraction of most samples; plagioclase, potassium feldspar, calcite, siderite, ankerite, marcasite, rutile, anatase and apatite are present in minor or trace concentrations. Semiquantitative values of volume percent pyrite content show a strong correlation with pyritic sulfur and some sulfide-hosted trace element concentrations (As and Hg). This work provides a modern quality dataset for the western Venezuela coal deposits currently being exploited and will serve as the foundation for an ongoing coal quality research program in Venezuela.

A reappraisal of the age, origin and structural setting of sulphide mineralisation in the UK North Pennines Orefield

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.

Sulfur isotope patterns of iron sulfide and barite nodules in the Upper Cretaceous Chalk of England and their regional significance in the origin of coloured chalks

NASA Astrophysics Data System (ADS)

Jeans, Christopher V.; Turchyn, Alexandra V.; Hu, Xu-Fang

2016-06-01

The relationship between the development of iron sulfide and barite nodules in the Cenomanian Chalk of England and the presence of a red hematitic pigment has been investigated using sulfur isotopes. In southern England where red and pink chalks are absent, iron sulfide nodules are widespread. Two typical large iron sulfide nodules exhibit δ34S ranging from -48.6‰ at their core to -32.6‰ at their outer margins. In eastern England, where red and pink chalks occur in three main bands, there is an antipathetic relationship between the coloured chalks and the occurrence of iron sulfide or barite nodules. Here iron sulfide, or its oxidised remnants, are restricted to two situations: (1) in association with hard grounds that developed originally in chalks that contained the hematite pigment or its postulated precursor FeOH3, or (2) in regional sulfidization zones that cut across the stratigraphy. In the Cenomanian Chalk exposed in the cliffs at Speeton, Yorkshire, pyrite and marcasite (both iron sulfide) nodules range in δ34S from -34.7‰ to +40.0‰. In the lower part of the section δ34S vary from -34.8‰ to +7.8‰, a single barite nodule has δ34S between +26.9‰ and +29.9‰. In the middle part of the section δ34S ranges from +23.8‰ to +40.0‰. In the sulfidization zones that cut across the Cenomanian Chalk of Lincolnshire the iron sulfide nodules are typically heavily weathered but these may contain patches of unoxidised pyrite. In these zones, δ34S ranges from -32.9‰ to +7.9‰. The cross-cutting zones of sulfidization in eastern England are linked to three basement faults - the Flamborough Head Fault Zone, the Caistor Fault and the postulated Wash Line of Jeans (1980) - that have affected the deposition of the Chalk. It is argued that these faults have been both the conduits by which allochthonous fluids - rich in hydrogen sulfide/sulfate, hydrocarbons and possibly charged with sulfate-reducing bacteria - have penetrated the Cenomanian Chalk as the result of movement during the Late Cretaceous or Cenozoic. These invasive fluids are associated with (1) the reduction of the red hematite pigment or its praecursor, (2) the subsequent development of both iron sulfides and barite, and (3) the loss of overpressure in the Cenomanian Chalk and its late diagenetic hardening by anoxic cementation. Evidence is reviewed for the origin of the red hematite pigment of the coloured chalks and for the iron involved in the development of iron sulfides, a hydrothermal or volcanogenic origin is favoured.

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.

Controls on Weathering of Pyrrhotite in a Low-Sulfide, Granitic Mine-Waste Rock in the Canadian Arctic

NASA Astrophysics Data System (ADS)

Langman, J. B.; Holland, S.; Sinclair, S.; Blowes, D.

2013-12-01

Increased environmental risk is incurred with expansion of mineral extraction in the Arctic. A greater understanding of geochemical processes associated with hard-rock mining in this cold climate is needed to evaluate and mitigate these risks. A laboratory and in-situ experiment was conducted to examine mineral weathering and the generation of acid rock drainage in a low-sulfide, run-of-mine waste rock in an Arctic climate. Rock with different concentrations of sulfides (primarily pyrrhotite [Fe7S8] containing small amounts of Co and Ni) and carbonates were weathered in the laboratory and in-situ, large-scale test piles to examine leachate composition and mineral weathering. The relatively larger sulfide-containing rock produced sufficient acid to overcome carbonate buffering and produced a declining pH environment with concomitant release of SO4, Fe, Co, and Ni. Following carbonate consumption, aluminosilicate buffering stabilized the pH above 4 until a reduction in acid generation. Results from the laboratory experiment assisted in determining that after consumption of 1.6 percent of the total sulfide, the larger sulfide-concentration test pile likely is at an internal steady-state or maximal weathering rate after seven years of precipitation input and weathering that is controlled by an annual freeze-thaw cycle. Further weathering of the test pile should be driven by external factors of temperature and precipitation in this Arctic, semi-arid region instead of internal factors of wetting and non-equilibrium buffering. It is predicted that maximal weathering will continue until at least 20 percent of the total sulfide is consumed. Using the identified evolution of sulfide consumption in this Arctic climate, a variable rate factor can now be assessed for the possible early evolution and maximal weathering of larger scale waste-rock piles and seasonal differences because of changes in the volume of a waste-rock pile undergoing active weathering due to the freeze-thaw cycle. Such rate factors are necessary to predict acid rock drainage and implement best management practices to minimize environmental impacts. To better understand the early geochemical evolution of the waste rock, sulfide minerals from different periods in the experiments were analyzed for discrete mineral characteristics indicative of a weathered state. Element transfer from the mineral to aqueous phase is transport limited because of the formation of Fe-(oxy)hydroxide weathered rims that can be an inhibitor of dissolution. Application of various x-ray spectroscopy techniques indicated that pyrrhotite transforms to marcasite [FeS2] prior to formation of Fe(II)-(oxy)hydroxides and further to Fe(III)-hydroxide/oxides. Iron appears to migrate through the weathered rims leaving the S-rich layer behind, and oxygen likely is retarded from migrating inward with formation of Fe(III) species. As these Fe-mineral transformations occur, they influence the retention of the secondary metals such as Co and Ni that preferentially remain in the +2 oxidation state and may leave the system as hydroxides, oxides, and sulfates. Understanding mineral evolution in this climate assists in adjusting appropriate rate factors for temporal changes in element release from the weathering of the pyrrhotite.

Fluid inclusions and preliminary studies of hydrothermal alteration in core hole PLTG-1, Platanares geothermal area, Honduras

USGS Publications Warehouse

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).

The composition of fluid inclusions in ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type Zn-Pb deposits Poland: Genetic and environmental implications

USGS Publications Warehouse

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.

Continuous country rock contamination and hydrothermal alteration of the Ni-Cu-PGE sulphide-bearing (ultra-)basic Uitkomst Complex, South Africa

NASA Astrophysics Data System (ADS)

Gauert, Christoph; Globig, Jan

2014-05-01

This mineralized ultrabasic to basic igneous complex of Bushveld Complex age (De Waal et al., 2001) and with affinity to a Bushveld complex primary magma composition Gauert, 1998) deserves further investigation, since new drill core material became available. An intersection of the downdip extension of the complex of constant thickness reveals upper gabbronoritic units which are geochemically evolved and strongly contaminated with quartz by assimilation of country rocks. Hydrothermal, partly deuteric alteration is widespread over the complex, but pronounced in its lower and upper zones. Selective, connate to meteoric fluid ingress, controlled by contact metamorphism (Sarkar et al., 2008) and structure (Joubert, 2013), led to significant deuteric alteration. Highly talc-carbonate altered chromitiferous peridotite sections show formation of cube-shaped spinels, probably indicating auto-metamorphic conditions. Autometamorphism of the ultrabasic rocks produced a wide range of non-sulfide assemblages, despite the relatively restricted compositional range within each rock type; a crucial variable is the XCO2 of the metamorphic fluid. The sulphide mineralogy of the ultramafic-hosted deposit is influenced by the temperature and composition of the hydrothermal fluid. Reduction reactions associated with the serpentinization fronts in the dunitic adcumulates gave rise to Ni-Fe alloy and native Cu bearing assemblages. Greenschist facies hydration gave rise to serpentinites, hosting assemblages rich in pentlandite and in some cases violarite and marcasite, mackinawite, millerite, and valleriite. Oxidized fluids associated with low temperature talc-carbonate alteration in the chromitiferous peridotite formed Ni-sulphide minerals coexisting with pyrite and hematite. Both the sulfide and nickel components in the ore may contain substantial proportions of the total nickel budget. Low temperature alteration effectively redistributed the sulfide elements in serpentinites, leading to highly variable Cu/(Cu+Ni) ratios. In areas of thorough alteration nickel can almost completely reside in sulphide minerals. The country rock contamination in the marginal zones and the alteration appear to continue along the downdip extension with nearly constant intensity over a distance of at least 9 km towards north-west. References: De Waal, S.A., Maier, W., Armstrong, R. and Gauert, C.D.K., 2001. Chemical constraints on the differentiation and emplacement of the Uitkomst Complex, Mpumalanga Province, South Africa, Canadian Mineralogist: 39, 557-571. Gauert, C.D.K., 1998. The Petrogenesis of the Uitkomst Complex, Mpumalanga Province, South Africa. Unpublished Ph.D. thesis, University of Pretoria, 315p. Guenther, C., and Gauert, C., 2013 The spatial distribution and geochemical characteristics of the talc-carbonate alteration of the Uitkomst Complex. 12th biennial SGA meeting, Uppsala, Sweden. Proceedings: 3, 993-996. Joubert, P.L., 2013. Syn- to post-intrusive deformation in the Chromitiferous Harzburgite Unit of the Uitkomst Complex, Nkomati Mine, Mpumalanga Province. Unpublished M.Sc. thesis, University of the Free State, Bloemfontein, South Africa, 155p. Sarkar, A., Ripley, E.M., Li, C., Maier, W.D., 2008. Stable isotope, fluid inclusion, and mineral chemistry constraints on contamination and hydrothermal alteration in the Uitkomst Complex, South Africa. - Chemical Geology, v. 257: 129-138.

Isotope tools to support conceptual model building of the Carboniferous limestone aquifer of Northern France and Belgium

NASA Astrophysics Data System (ADS)

Gourcy, L.; Castres de Paulet, F.; Rorive, A.; Bastien, J.

2012-04-01

Since the beginning of the 20th century, the Carboniferous aquifer was known as a high potential limestone aquifer. Groundwater has been exploited for decades to provide drinkable water and supply heavy factories in north of France and Belgium. Over-pumped during the last century, the Carboniferous aquifer has seen its water level dramatically decreased between Lille (Fr), Mouscron and Tournai (Be). Since the end of industrial period and some agreements to reduce pumpings, groundwater consumption has declined and water table is now stabilized and slowly coming back to a more "natural" level in some areas. In order to sustainably manage this aquifer, French and Belgian environmental agencies and local authorities underlined the need of a better hydrogeological knowledge. Within the framework of the "Scaldwin" project (launched in 2008), a hydrogeological model will be built. To reach these objectives, existing data were compiled, updated and treated. Moreover, new data were collected since 2009: 11 boreholes were drilled, 2 piezometrical maps were drawn and 2 field sampling campaigns were carried out in March and November 2011 to collect groundwater for further analyses. As a first step, the conceptual hydrogeological map was reviewed considering new knowledge of the geometry and water levels of this aquifer. Then, the hydrogeochemical study was undertaken in order to dispel doubts on some specific aspects such as: relationships between the deep (carbonated Carboniferous) and the surface (chalky Cretaceous) aquifers, delineation of the southern Carboniferous aquifer limit, mechanisms of sulphate enrichment… Major and trace elements, dissolved gases (CFC-11, CFC-12, CFC-113, SF6) and various isotopes (δ2H, δ18O, δ11B, δ34S, δ18O-SO4, δ13C, 14C) were analysed in water sampled from 36 wells exploiting the Carboniferous limestones (16 in the French part and 20 in Belgium) and 4 waters from the chalk aquifer. Cation exchange process is playing an important role in the chemical evolution of water from the recharge to the discharge area. Age-dating tools confirmed the extension of the recharge area in the East and highlighted the presence of paleowater in the southern part of the aquifer. This sector is poor in boreholes and wells and seems to be hydrogeologically quite isolated from the rest of the Carboniferous aquifer. Groundwater are there enriched in sulphate. Sulphate isotopes showed that these compounds have two main sources within the aquifer. In the southern part (mainly old water), anhydrites dissolution has a more important fingerprint of groundwater as observed near Saint-Ghislain (Be) by various authors. In the recharge area and the northern part, pyrite/marcasite oxidation is the dominating process allowing the groundwater enrichment in SO4. Furthermore, bacterial reduction activity is influencing isotopic signatures. Stable water isotopes data confirmed the presence of old water. The stable isotopes values of the Carboniferous aquifer water are varying from -7 ‰ (present day recharge, such as the chalk aquifer) and -8.6 ‰ (paleowater) depending on their position along the main flow lines and possibly interaction between chalk and Carboniferous aquifers. All these chemical processes should be considered in building the future hydrogeological model.

Geology and geochemistry of the Reocín zinc-lead deposit, Basque-Cantabrian Basin, Northern Spain

USGS Publications Warehouse

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.

Mineralogy, paragenesis, and mineral zoning of the Bulldog Mountain vein system, Creede District, Colorado

USGS Publications Warehouse

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.

Metals in Devonian kerogenous marine strata at Gibellini and Bisoni properties in southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

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.

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

USGS Publications Warehouse

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.

Sinter-vein correlations at Buckskin Mountain, National district, Humboldt County, Nevada

USGS Publications Warehouse

Vikre, P.G.

2007-01-01

At Buckskin Mountain (elev 2,650 m, 8,743 ft), Humboldt County, Nevada, a hydrothermal system, imposed on a middle Miocene volcanic sequence with contrasting permeabilities and tensile strengths, produced alteration assemblages controlled by elevation, from Hg-mineralized sinter to subjacent precious metal veins over a vertical distance exceeding 790 m. Sinter and epiclastic deposits, interpreted to be remnant paleosurface basinal strata enclosed by 16.6 to 16.1 Ma rhyolites, overlie older volcaniclastic basinal deposits and were part of a regional fluvial-lacustrine system developed among ca. 16 to 12 Ma basalt-rhyolite eruptive centers throughout the northern Great Basin. Because of contrasting erosional resistance among altered and unaltered rocks, Buckskin Mountain represents inverse topography with sinter and silicified epiclastic deposits at the summit. Sinter and veins, correlated by common elements, similar mineralogy, age constraints, textures, S isotope compositions, and fluid inclusion microthermometry, were deposited by sinter-vein fluid, the first of two sequential hydrothermal fluid regimes that evolved in response to magmatism, tectonism, hydrology, and topography. Thermal quenching of distally derived sinter-vein fluid in planar conduits caused deposition of banded quartz-silicate-selenide-sulfide veins ???270 to > 440 m below sinter at 16.1 Ma; vei??ns were initially enveloped by zoned selvages of proximal K-feldspar + K-mica + quartz + pyrite and distal illite + chlorite + calcite + pyrite. Mixing of sinter-vein fluid with local meteoric water in saturated basinal deposits caused deposition of silica, Hg-Se-S-Cl minerals, and precious metals in sinter and epiclastic deposits. Elevated ???Se/???S in sinter-vein fluid, and the relatively large stability fields of reduced aqueous selenide species in the temperature range of 250?? to <100??C, enabled (but was not the cause of) codeposition of selenide-sulfide minerals and common element associations in veins and sinter. Acid-sulfate fluid of the second fluid regime was derived from oxidation of H2S and other volatiles exsolved from sinter-vein fluid. Acid-sulfate fluid produced (1) a subhorizontal zone of partially leached basinal deposits and rhyolite from the paleosurface to a depth of ???60 m, and (2) laterally pervasive zones, ???100 to 200 m thick, of quartz + alunite ?? hematite and quartz + kaolinite + pyrite in volcaniclastic deposits immediately beneath partially leached rocks, but this fluid did not decompose selenide-sulfide-precious metal phases in sinter. Paragenetically late vein and wall-rock assemblages, including marcasite + pyrite, calcite, and kaolinite-replaced K minerals, record deeper transition of sinter-vein fluid into acid-sulfate fluid in vein conduits. This transition occurred as regional subsidence, manifested by the Goosey Lake depression immediately east of Buckskin Mountain, lowered the pieziometric surface at Buckskin Mountain, terminated sinter deposition, and caused boiling and/or degassing of sinter-vein fluid. The timing of subsidence is recorded by a decrease in alunite ages, from ca. 15.8 to 15.6 Ma, with depth below sinter. Lateral replacement of sinter and partially leached epiclastic deposits and rhyolite by opal-A marks the termination of the two hydrothermal regimes that lasted ???0.5 m.y. and followed rhyolitic volcanism of similar duration. Veins and sinter display textures that attest to plastic deformation, spalling, and gravitational settling, and indicate fluid-flow direction, velocity, and density stratification which, with conduit topology, may have influenced precious metal tenor in the veins. Components of sinter and veins were transported as colloids, formed in supersaturated sinter-vein fluid, that aggregated or coagulated as incompetent gelatinous layers in shallow pools and in underlying, near-vertical conduits in rhyolite and initially crystallized as opal and chalcedony. The low thermal conductivity of ho

Sulphide mineralization and wall-rock alteration in ophiolites and modern oceanic spreading centres

USGS Publications Warehouse

Koski, R.A.

1983-01-01

Massive and stockwork Fe-Cu-Zn (Cyprus type) sulphide deposits in the upper parts of ophiolite complexes represent hydrothermal mineralization at ancient accretionary plate boundaries. These deposits are probable metallogenic analogues of the polymetallic sulphide deposits recently discovered along modern oceanic spreading centres. Genetic models for these deposits suggest that mineralization results from large-scale circulation of sea-water through basaltic basement along the tectonically active axis of spreading, a zone of high heat flow. The high geothermal gradient above 1 to 2 km deep magma chambers emplaced below the ridge axis drives the convective circulation cell. Cold oxidizing sea-water penetrating the crust on the ridge flanks becomes heated and evolves into a highly reduced somewhat acidic hydrothermal solvent during interaction with basaltic wall-rock. Depending on the temperature and water/rock ratio, this fluid is capable of leaching and transporting iron, manganese, and base metals; dissolved sea-water sulphate is reduced to sulphide. At the ridge axis, the buoyant hydrothermal fluid rises through permeable wall-rocks, and fluid flow may be focussed along deep-seated fractures related to extensional tectonic processes. Metal sulphides are precipitated along channelways as the ascending fluid undergoes adiabatic expansion and then further cooling during mixing with ambient sub-sea-floor water. Vigorous fluid flow results in venting of reduced fluid at the sea-floor/sea-water interface and deposition of massive sulphide. A comparison of sulphide mineralization and wall-rock alteration in ancient and modern spreading centre environments supports this genetic concept. Massive sulphide deposits in ophiolites generally occur in clusters of closely spaced (< 1-5 km) deposits. Individual deposits are a composite of syngenetic massive sulphide and underlying epigenetic stockwork-vein mineralization. The massive sulphide occurs as concordant tabular, lenticular, or saucer-shaped bodies in pillow lavas and pillow-lava breccia; massive lava flows, hyalcoclastite, tuff, and bedded radolarian chert are less commonly associated rock types. These massive sulphide zones are as much as 700 m long, 200 m wide, and 50 m thick. The pipe-, funnel-, or keel-shaped stockwork zone may extend to a dehpth of 1 km in the sheeted-dike complex. Several deposits in Cyprus are confined to grabens or the hanging wall of premineralization normal faults. Polymetallic massive sulphide deposits and active hydrothermal vents at medium- to fast-rate spreading centres (the East Pacific Rise at lat. 21??N, the Galapagos Spreading Centre at long. 86??W, the Juan de Fuca Ridge at lat. 45??N., and the Southern Trough of Guaymas Basin, Gulf of California) have interdeposit spacings on a scale of tens or hundreds of metres, and are spatially associated with structural ridges or grabens within the narrow (< 5 km) axial valleys of the rift zones. Although the most common substrate for massive sulphide accumulations is stacked sequences of pillow basalt and sheet flows, the sea-floor underlying numerous deposits in Guaymas Basin consists of diatomaceous ooze and terrigenous clastic sediment that is intruded by diabase sills. Mound-like massive sulphide deposits, as much as 30 m wide and 5m high, occur over actively discharging vents on the East Pacific Rise, and many of these deposits serve as the base for narrow chimneys and spires of equal or greater height. Sulphides on the Juan de Fuca Ridge appear to form more widespread blanket deposits in the shallow axial-valley depression. The largest deposit found to date, along the axial ridge of the Galapagos Spreading Centre, has a tabular form and a length of 1000 m, a width of 200 m, and a height of 30 m. The sulphide assemblage in both massive and vein mineralization in Cyprus type deposits is characteristically simple: abundant pyrite or, less commonly, pyrrhotite accompanied by minor marcasite, chalcopyrite

Ceres' Yellow Spots - Observations with Dawn Framing Camera

NASA Astrophysics Data System (ADS)

Schäfer, Michael; Schäfer, Tanja; Cloutis, Edward A.; Izawa, Matthew R. M.; Platz, Thomas; Castillo-Rogez, Julie C.; Hoffmann, Martin; Thangjam, Guneshwar S.; Kneissl, Thomas; Nathues, Andreas; Mengel, Kurt; Williams, David A.; Kallisch, Jan; Ripken, Joachim; Russell, Christopher T.

2016-04-01

The Framing Camera (FC) onboard the Dawn spacecraft acquired several spectral data sets of (1) Ceres with increasing spatial resolution (up to 135 m/pixel with nearly global coverage). The FC is equipped with seven color filters (0.4-1.0 μm) plus one panchromatic ('clear') filter [1]. We produced spectral mosaics using photometrically corrected FC color filter images as described in [2]. Even early FC color mosaics obtained during Dawn's approach unexpectedly exhibited quite a diversity of surface materials on Ceres. Besides the ordinary cerean surface material, potentially composed of ammoniated phyllosilicates [3] or some other alteration product of carbonaceous chondrites [4], a large number of bright spots were found on Ceres [5]. These spots are substantially brighter than the average surface (exceeding its triple standard deviation), with the spots within Occator crater being the brightest and most prominent examples (reflectance more than 10 times the average of Ceres). We observed bright spots which are different by their obvious yellow color. This yellow color appears both in a 'true color' RGB display (R=0.65, G=0.55, B=0.44 μm) as well as in a false color display (R=0.97, G=0.75, B=0.44 μm) using a linear 2% stretch. Their spectra show a steep red slope between 0.44 and 0.55 μm (UV drop-off). On the contrary to these yellow spots, the vast majority of bright spots appears white in the aforementioned color displays and exhibit blue sloped spectra, except for a shallow UV drop-off. Thus, yellow spots are easily distinguishable from white spots and the remaining cerean surface by their high values in the ratio 0.55/0.44 μm. We found 8 occurrences of yellow spots on Ceres. Most of them (>70 individual spots) occur both inside and outside crater Dantu, where white spots are also found in the immediate vicinity. Besides Dantu, further occurrences with only a few yellow spots were found at craters Ikapati and Gaue. Less definite occurrences are found at 97°E/24°N, 205°E/22°S, 244°E/31°S, 213°E/37.5°S, and at Azacca crater. Often, the yellow spots exhibit well-defined boundaries, but sometimes we found a fainter diffuse yellow tinge around them, enclosing several individual yellow spots. Rarely, they are associated with mass wasting on steep slopes, most notably on the SE crater wall of Dantu. Recently acquired clear filter images with 35 m/pixel resolution indicate only a small number of yellow spots to be situated nearby craters. These craters could also be interpreted as pits probably formed by exhalation vents. More frequently, we found yellow spots linked to small positive landforms. Only a few of the yellow spots seem to be interrelated with crater floor fractures. As with white bright spots, which were interpreted as evaporite deposits of magnesium-sulfate salts [5], the yellow spots appear to emerge from the sub-surface as a result of material transport, possibly driven by sublimation of ice [5], where vents or cracks penetrate the insulating lag deposits. However, in contrast to the white spots, a different mineralogy seems to have emerged at yellow spots. First comparisons of FC spectra with laboratory spectra indicate pyrite/marcasite as a possible component. The relatively strong UV drop-off may at least indicate some kind of sulfide- or sulfur-bearing mixture. As identifications of minerals based on FC spectra are often ambiguous, further investigations by high-resolution data yet to come from Dawn's VIR spectrometer may shed light into the compositional differences between yellow and white bright spots. References: [1] Sierks, H. et al., Space Sci. Rev., 163, 263-327, 2011. [2] Schäfer, M. et al., EPSC, Vol. 10, #488, 2015. [3] De Sanctis, M. C. et al., Nature 528, 241-244, 2015. [4] Schäfer, T. et al., EGU, #12370, 2016. [5] Nathues, A. et al., Nature 528, 237-240, 2015.

Stratigraphic and geochemical controls on naturally occurring arsenic in groundwater, eastern Wisconsin, USA

NASA Astrophysics Data System (ADS)

Schreiber, M. E.; Simo, J. A.; Freiberg, P. G.

High arsenic concentrations (up to 12,000μg/L) have been measured in groundwater from a confined sandstone aquifer in eastern Wisconsin. The main arsenic source is a sulfide-bearing secondary cement horizon (SCH) that has variable thickness, morphology, and arsenic concentrations. Arsenic occurs in pyrite and marcasite as well as in iron oxyhydroxides but not as a separate arsenopyrite phase. Nearly identical sulfur isotopic signatures in pyrite and dissolved sulfate and the correlation between dissolved sulfate, iron, and arsenic concentrations suggest that sulfide oxidation is the dominant process controlling arsenic release to groundwater. However, arsenic-bearing oxyhydroxides can potentially provide another arsenic source if reducing conditions develop or if they are transported as colloids in the aquifer. Analysis of well data indicates that the intersection of the SCH with static water levels measured in residential wells is strongly correlated with high concentrations of arsenic in groundwater. Field and laboratory data suggest that the most severe arsenic contamination is caused by localized borehole interactions of air, water, and sulfides. Although arsenic contamination is caused by oxidation of naturally occurring sulfides, it is influenced by water-level fluctuations caused by municipal well pumping or climate changes, which can shift geographic areas in which contamination occurs. Résumé De fortes concentrations en arsenic, jusqu'à 12000μg/L, ont été mesurées dans l'eau souterraine d'un aquifère gréseux captif, dans l'est du Wisconsin. La principale source d'arsenic est un horizon à cimentation secondaire (SCH) comportant des sulfures, dont l'épaisseur, la morphologie et les concentrations en arsenic sont variables. L'arsenic est présent dans la pyrite et dans la marcassite, de même que dans des oxy-hydroxydes de fer, mais non pas dans une phase séparée d'arsénopyrite. Les signatures isotopiques du soufre presque identiques dans la pyrite et dans les sulfates dissous et la corrélation entre les concentrations en sulfates, en fer et en arsenic dissous laissent penser que l'oxydation des sulfures est le processus dominant contrôlant la libération de l'arsenic dans les eaux souterraines. Cependant, les oxy-hydroxydes contenant de l'arsenic sont susceptibles d'être une autre source d'arsenic si des conditions réductrices apparaissent ou s'ils sont transportés dans l'aquifère sous forme de colloïdes. L'analyse des données provenant de puits montre que l'intersection entre le SCH et les niveaux statiques des puits domestiques est fortement corrélée à de fortes concentrations en arsenic dans les eaux souterraines. Des données de terrain et de laboratoire conduisent à penser que la contamination en arsenic la plus forte est causée par l'interaction localisée aux forages entre l'air, l'eau et les sulfures. Bien que la contamination en arsenic soit causée par l'oxydation de sulfures présents naturellement, elle est influencée par les fluctuations du niveau piézométrique causées par les pompages du captage municipal ou par les variations climatiques, ce qui peut conduire au déplacement des zones géographiques où se produisent les contaminations. Resumen Se han medido concentraciones de arsénico muy altas (de hasta 12000μg/L) en las aguas subterráneas de un acuífero confinado, en areniscas, localizado en la parte oriental de Wisconsin (EEUU). La fuente principal de arsénico es un horizonte de cementación secundaria (SCH) con un alto contenido en sulfuros, y con una gran variabilidad en espesor, morfología y concentraciones de As. El arsénico aparece en piritas y marcasitas, además de en oxihidróxidos de hierro, pero no como una fase independiente de arsenopiritas. El hecho que la marca isotópica de piritas y sulfatos disueltos sea muy similar, y que exista una gran correlación entre las concentraciones de sulfato disuelto, hierro y arsénico sugiere que la oxidación de sulfuros es el proceso que controla la aportación de arsénico al agua subterránea. Sin embargo, los oxihidróxidos con alto contenido en arsénico podrían suponer otra fuente de arsénico si se llegaran a desarrollar condiciones reductoras o si se transportaran como coloides por el acuífero. De los datos procedentes de pozos, se ve una fuerte correlación entre la presencia de altas concentraciones de As en el agua y que el nivel freático intersecte el SCH. Los datos de campo y de laboratorio indican que los puntos con mayor contaminación de arsénico son debidos a interacciones de carácter local y en los propios pozos entre aire, agua y sulfuros. Aunque la contaminación por As está causada por la oxidación de sulfuros presentes de manera natural, también está muy influenciada por las fluctuaciones en los niveles freáticos causadas por bombeos o cambios climáticos.