Sample records for ankerite

  1. Mineralogical anomalies and their influences on elemental geochemistry of the main workable coal beds from the Dafang Coalfield, Guizhou, China

    USGS Publications Warehouse

    Dai, S.; Ren, D.; Li, D.; Chou, C.-L.; Luo, K.

    2006-01-01

    Mineralogy and geochemistry of the No. 11 Coal bed were investigated by using inductively-coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF), scanning electron microscopy equipped with energy-dispersive X-ray (SEM-EDX), sequential chemical extraction procedure (SCEP), and optical microscopy. The results show that the No. 11 Coal bed has very high contents of veined quartz (Vol. 11.4%) and veined ankerite (Vol. 10.2 %). The veined ankerite was generally coated by goethite and the veined quartz embraced chalcopyrite, sphalerite, and selenio-galena. In addition, a trace amount of kaolinite was filled in the veins. These seven minerals often occur in the same veins. The formation temperatures of the veined ankerite and quartz are 85??C and 180??C respectively, indicating their origins of iron-rich calcic and siliceous low-temperature hydrothermal fluids in different epigenetic periods. Studies have also found that the veined quartz probably formed earlier than the veined ankerite, and at least three distinct ankerite formation stages were observed by the ration of Ca/Sr and Fe/Mn of ankerite. The mineral formation from the early to late stage is in order of sulfide, quartz, kaolinite, ankerite, and goethite. The veined ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn, which are as high as 0.09%, 74.0 ??g/g, 33.6 ??g/g, 185 ??g/g, and 289 ??g/g in this coal seam, respectively. However, the veined quartz is the main carrier of Pd, Pt, and Ir, which are 1.57 ??g/g, 0.15 ??g/g, and 0.007 ??g/g in this coal seam, respectively. In addition, chalcopyrite, sphalerite, and selenio-galena of hydrothermal origin were determined in the veined quartz, and these three sulfide minerals are also important carriers of Cu, Zn and Pb in the No. 11 Coal bed.

  2. Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: Influence from siliceous and iron-rich calcic hydrothermal fluids

    USGS Publications Warehouse

    Dai, S.; Chou, C.-L.; Yue, M.; Luo, K.; Ren, D.

    2005-01-01

    This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, Rr =2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 ??C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed. The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 ??g/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 ??g/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 ??g/g Pd, 1.23 ??g/g Pt, and 0.05 ??g/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids. ?? 2004 Elsevier B.V. All rights reserved.

  3. ASTER spectral analysis and lithologic mapping of the Khanneshin carbonatite volcano, Afghanistan

    USGS Publications Warehouse

    Mars, John C.; Rowan, Lawrence C.

    2011-01-01

    Advanced Spaceborne Thermal and Reflection Radiometer (ASTER) data of the early Quaternary Khanneshin carbonatite volcano located in southern Afghanistan were used to identify carbonate rocks within the volcano and to distinguish them from Neogene ferruginous polymict sandstone and argillite. The carbonatitic rocks are characterized by diagnostic CO3 absorption near 11.2 μm and 2.31–2.33 μm, whereas the sandstone, argillite, and adjacent alluvial deposits exhibit intense Si-O absorption near 8.7 μm caused mainly by quartz and Al-OH absorption near 2.20 μm due to muscovite and illite.Calcitic carbonatite was distinguished from ankeritic carbonatite in the short wave infrared (SWIR) region of the ASTER data due to a slight shift of the CO3 absorption feature toward 2.26 μm (ASTER band 7) in the ankeritic carbonatite spectra. Spectral assessment using ASTER SWIR data suggests that the area is covered by extensive carbonatite flows that contain calcite, ankerite, and muscovite, though some areas mapped as ankeritic carbonatite on a preexisting geologic map were not identified in the ASTER data. A contact aureole shown on the geologic map was defined using an ASTER false color composite image (R = 6, G = 3, B = 1) and a logical operator byte image. The contact aureole rocks exhibit Fe2+, Al-OH, and Fe, Mg-OH spectral absorption features at 1.65, 2.2, and 2.33 μm, respectively, which suggest that the contact aureole rocks contain muscovite, epidote, and chlorite. The contact aureole rocks were mapped using an Interactive Data Language (IDL) logical operator.A visible through short wave infrared (VNIR-SWIR) mineral and rock-type map based on matched filter, band ratio, and logical operator analysis illustrates: (1) laterally extensive calcitic carbonatite that covers most of the crater and areas northeast of the crater; (2) ankeritic carbonatite located southeast and north of the crater and some small deposits located within the crater; (3) agglomerate that primarily covers the inside rim of the crater and a small area west of the crater; (4) a crater rim that consists mostly of epidote-chlorite-muscovite–rich metamorphosed argillite and sandstone; and (5) iron (Fe3+) and muscovite-illite–rich rocks and iron-rich eolian sands surrounding the western part of the volcano. The thermal infrared (TIR) rock-type map illustrates laterally extensive carbonatitic and mafic rocks surrounded by quartz-rich eolian and fluvial reworked sediments. In addition, the combination of VNIR, SWIR, and TIR data complement one another in that the TIR data illustrate more laterally extensive rock types and the VNIR-SWIR data distinguish more specific varieties of rocks and mineral mixtures.

  4. Calibration of carbonate composition using micro-Raman analysis: application to planetary surface exploration.

    PubMed

    Rividi, Nicolas; van Zuilen, Mark; Philippot, Pascal; Ménez, Bénédicte; Godard, Gaston; Poidatz, Emmanuel

    2010-04-01

    Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquantitative estimates of solid solutions in the Ca-Mg-Fe(+Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy analysis was performed on a set of carbonate standards (calcite, ankerite, dolomite, siderite, and magnesite) of known composition. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solutions display a well-defined positive correlation (r(2) > 0.9) with the Mg# = 100 x Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chemical composition of carbonates. Raman analysis of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of carbonates on planetary surfaces.

  5. Compositional Evolution of Pyrochlore-Group Minerals in Carbonatites of the Belaya Zima Pluton, Eastern Sayan

    NASA Astrophysics Data System (ADS)

    Khromova, E. A.; Doroshkevich, A. G.; Sharygin, V. V.; Izbrodin, L. A.

    2017-12-01

    Pyrochlore-group minerals are the main concentrators of niobium in carbonatites of the Belaya Zima alkaline pluton. Fluorcalciopyrochlore, kenopyrochlore and hydropyrochlore were identified in chemical composition. Their main characteristics are given: compositional variation, morphology, and zoning. During evolution from early calcite to late ankerite carbonatites, the UO2, TiO2, REE, and Y contents gradually increased. All carbonatite types are suggested to contain initial fluorcalciopyrochlore. However, in calcite-dolomite and ankerite carbonatites, it is partially or completely hydrated due to hydrothermal processes at the late stage of the pluton. This hydration resulted in the appearance of kenopyrochlore and hydropyrochlore due to removal of Ca, Na and F, and input of Ba, H2O, K, Si, Fe, and probably U and REE. At the last stage of the pluton, this hydrated pyrochlore was replaced by Fe-bearing columbite.

  6. Geochemistry of autochthonous and hypautochthonous siderite-dolomite coal-balls (Foord Seam, Bolsovian, Upper Carboniferous), Nova Scotia, Canada

    USGS Publications Warehouse

    Zodrow, E.L.; Lyons, P.C.; Millay, M.A.

    1996-01-01

    The 11-13 m thick Foord Seam in the fault-bounded Stellarton Basin, Nova Scotia, is the thickest seam from the Euramerican floral province known to contain coal-balls. In addition to the first discovery of autochthonous coal-balls in the Foord Seam, Nova Scotia, its shale parting also contains hypautochthonous coal-balls with histologically preserved plant structures. The coal-ball discovery helps fill a stratigraphic gap in coal-ball occurrences in the upper Carboniferous (Bolsovian) of Euramerica. The autochthonous and hypautochthonous coal-balls have a similar mineralogical composition and are composed of siderite (81-100%), dolomite-ankerite (0-19%), minor quartz and illite, and trace amounts of 'calcite'. Similar is also their permineralizing mineralogy, which consists of dolomite-ankerite and siderite. Their low pyrite content and carbonate mineralogy, and nonmarine origin, differentiates the Foord Seam coal-balls from other Euramerican coal-ball occurrences. A preliminary geochemical model, which is based on oxygen and carbon isotopic data, indicates that siderite in both the autochthonous and hypautochthonous coal-balls is of very early diagenetic (nonmarine) origin from 13C-enriched bicarbonate derived from bacterial methanogenesis of organic matter.

  7. Wall-rock control of cortain pitchblende deposits in Golden Gate Canyon, Jefferson County, Colorado

    USGS Publications Warehouse

    Adams, John W.; Stugard, Frederick

    1954-01-01

    Carbonate veins cutting pre-Cambrian metamorphic rocks in Golden Gate Canyon contain pitchblende and base-metal sulfides. The veins occupy extensive faults of Laramide age but normally contain pitchblende only where the cut hornblende gneiss. At the Union Pacific prospect, which was studied in detail, pitchblende, hermatite, and some ankerite formed in advance of sulfides, except possibly for minor pyrite. Base-metal sulfides and the bulk of ankerite-calcite vein-filling were deposited after the pitchblende. Chemical analyses show a high ferrous iron content in the hornblende gneiss in contrast to low ferrous iron in the adjacent biotite gneiss. It is hypothesized that ferrous iron released by alteration of hornblende was partly oxidized to hematite by the ore-bearing solutions and, contemporaneously, uranium was reduced and deposited as pitchblende. In other veins, biotite or iron sulfides may have been similarly effective in precipitating pitchblende. Apparently both the ferrous ion and the sulfide ion can serve as reducing agents and control pitchblende deposition. It is suggested that conditions particularly favorable for uranium deposition are present where uranium-bearing solutions had access to rocks rich in ferrous iron or pre-existing sulfides.

  8. The thermal and chemical evolution of hydrothermal vent fluids in shale hosted massive sulphide (SHMS) systems from the MacMillan Pass district (Yukon, Canada)

    NASA Astrophysics Data System (ADS)

    Magnall, J. M.; Gleeson, S. A.; Blamey, N. J. F.; Paradis, S.; Luo, Y.

    2016-11-01

    At Macmillan Pass (YT, Canada), the hydrothermal vent complexes beneath two shale-hosted massive sulphide (SHMS) deposits (Tom, Jason) are well preserved within Late Devonian strata. These deposits provide a unique opportunity to constrain key geochemical parameters (temperature, salinity, pH, fO2, ΣS) that are critical for metal transport and deposition in SHMS systems, and to evaluate the interaction between hydrothermal fluids and the mudstone host rock. This has been achieved using a combination of detailed petrography, isotopic techniques (δ34S, δ13C and δ18O values), carbonate rare earth element analysis (LA-ICP-MS), fluid inclusion analysis (microthermometry, gas analysis via incremental crush fast scan mass spectrometry), and thermodynamic modelling. Two main paragenetic stages are preserved in both vent complexes: Stage 1 comprises pervasive ankerite alteration of the organic-rich mudstone host rock and crosscutting stockwork ankerite veining (±pyrobitumen, pyrite and quartz) and; Stage 2 consists of main stage massive sulphide (galena-pyrrhotite-pyrite ± chalcopyrite-sphalerite) and siderite (±quartz and barytocalcite) mineralisation. Co-variation of δ18O and δ13C values in ankerite can be described by temperature dependent fractionation and fluid rock interaction. Together with fluid inclusion microthermometry, this provides evidence of a steep thermal gradient (from 300 to ∼100 °C) over approximately 15 m stratigraphic depth, temporally and spatially constrained within the paragenesis of both vent complexes and developed under shallow lithostatic (<1 km; 250 bars) to hydrostatic (<400 m; 40 bars) conditions. There is evidence of mixing between diagenetic and hydrothermal fluids recorded in chondrite-normalised rare earth element (REE) profiles of ankerite and siderite. Middle REE enrichments and superchondritic Y/Ho ratios (>28), characteristic of diagenetic fluids, are coupled with positive europium anomalies and variable light REE depletion, which are more consistent with chloride complexation in hot (>250 °C) hydrothermal fluids. In this shallow sub-seafloor setting, thermal alteration of organic carbon in the immature, chemically reactive mudstones also had an important role in the evolution of fluid chemistry. Reduced sulphur generation via thermochemical reduction of Late Devonian seawater sulphate produced positive δ34S values in sulphide minerals (+7.5‰ to +19.5‰), coupled with a suite of volatile components (CO2, CH4, C1-C4 hydrocarbons, N2) trapped in Stage 2 quartz. Many of these geochemical features developed during the final stages of fluid ascent, in a system where the fluid cooled close to the site of mineralisation. Using this information, we have modelled the metal transporting capacity of the deep hydrothermal fluid, which even at modest salinities (6 wt.% NaCl) was high (≫100 ppm Pb, Zn), owing to the combined effects of high temperature and low pH (⩽4.5). Therefore in SHMS systems, enhanced geothermal gradients and rapid fluid ascent (with minimal fluid cooling) are considered to be the most important factors for transporting high concentrations of base metals to the site of mineralisation.

  9. Change in stress with seismic cycles identified at an out of sequence thrust in an on-land accretionary complex: The Nobeoka thrust, Shimanto Belt, Kyusyu, SW Japan

    NASA Astrophysics Data System (ADS)

    Yamaguchi, M.; Hashimoto, Y.; Yamaguchi, A.; Kimura, G.

    2011-12-01

    Seismic surveys along accretionary prisms have revealed that the out-of sequence thrusts (OSTs) are commonly developed within accretionary wedges branching from seismogenic subduction plate boundaries. The OSTs are also recognized in on-land accretionary complexes as large thrust faults cutting paleo-thermal structures. The OSTs are thought to play a role in tsunami genesis at a coseismic event. Stress history on OSTs is significant to understand the OSTs' role in seismic cycles. We estimated, thus palaeostresses from micro-faults along an OST in an on-land accretionary complexes. We focused on the Nobeoka fault which is an OST in an on-land accretionary complex, the Shimato Belt, Kyusyu, SW Japan. A gap in paleothermal temperature (up to 70 degree C) is observed at the fault. The Nobeoka thrust strikes almost EW at coastline. The Cretaceous Makimine formation and Paleogene Kitagawa formation are located at the hanging wall of the fault, comprising mainly of pelitic schist. The footwall of the fault is the Paleogene Hyuga formation composed mainly of shale. A lot of micro-faults are well developed just below the thrust for a few hundred meters to the south. Those micro faults are considered to be related to the Nobeoka thurst because slip direction and sense of the micro-faults are consistent with that of the Nobeoka thrust. The micro-faults are commonly accompanied by mineral veins of quartz and ankerite. Yamaguchi et al. (2010) suggested that the differences of mineral veins are possibly related to the seismic cycle. In this study, we conducted stress inversion analysis for the micro-faults to examine the change in stress between them, which might be related to the seismic cycle. We divided the micro-fault into two as a micro-fault with quartz veins and that with ankerite veins. Slip direction from slicken fibers and slip sense by slicken steps were obtained. HIM (hough inversion method) by Yamaji et al. (2006) was used to estimate the stress. Two stress states and three stress states are identified in the results for ankerite veins and quartz veins, respectively. For ankerite veins, SE oriented and relatively higher dipping sigma3 with axial extension and SE oriented and relatively lower dipping sigma1 with axial compression are recognized. For quartz veins, SE oriented and relatively higher dipping sigma3 with axial extension, NE oriented and almost horizontal sigma1 with triaxial stress ratio, and NW oriented and lower dipping sigma1 with axial compression are observed. While NW-SE axial stress states are observed both from ankelite and quatz veins, NE oriented triaxial stress is identified only from quartz veins. The change in stress states from NW-SE axial stress to NE triaxial stress might be explained by the dynamic Coulomb wedge model suggested by Wang and Hu (2006). The model predicts that the stress within accretionary wedge can be change with seismic cycle, horizontal sigma1 with axial compression at the co-seismic slip and relatively higher dipping sigma1 with triaxial stress in inter-seimsic period.

  10. Hydrothermal alteration of felsic volcanic rocks at the Helen Siderite Deposit, Wawa, Ontario

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

    Morton, R.L.; Nebel, M.L.

    1984-09-01

    Felsic lavas and pyroclastic rocks, underlying the Archean Helen iron-formation, have been variably altered by hydrothermal solutions which, when discharged onto the sea floor, formed the Helen siderite deposit. Within the footwall volcanic sequence five chemically and mineralogically distinct alteration types have been defined: least altered, sericite, chlorite chloritoid, and ankerite. Based on mineralogy and chemistry of the altered rocks and on the geometry of the alteration zones, an alteration model is proposed.

  11. Carbon Dioxide Tucked into Basalt Converts to Rock

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

    McGrail, Pete

    2016-11-18

    Carbon Sequestration or storing carbon dioxide underground may be one approach to reducing atmospheric levels of the greenhouse gas. Storing it in basalt formations creates a chemical reaction in which the CO2 is transformed into a mineral similar to limestone enabling permanent storage underground. A field study by researchers at the Department of Energy’s Pacific Northwest National Laboratory shows that chemical happens quickly. Within two years, CO2 injected underground in Washington state had converted to the carbonate mineral ankerite.

  12. Carbon Dioxide Tucked into Basalt Converts to Rock

    ScienceCinema

    McGrail, Pete

    2018-06-13

    Carbon Sequestration or storing carbon dioxide underground may be one approach to reducing atmospheric levels of the greenhouse gas. Storing it in basalt formations creates a chemical reaction in which the CO2 is transformed into a mineral similar to limestone enabling permanent storage underground. A field study by researchers at the Department of Energy’s Pacific Northwest National Laboratory shows that chemical happens quickly. Within two years, CO2 injected underground in Washington state had converted to the carbonate mineral ankerite.

  13. Final Remedial Investigation Report Area of Contamination (AOC) 57. Volume I. Text Sections 1 Through 10, Figures and Tables

    DTIC Science & Technology

    2000-06-01

    duckweed ( Lemna minor ), and bur-reed (Sparganium sp.). The forested wetland to the southeast of Cold Spring Brook has a sparse canopy cover of red...FORMATION (Lower Devonian and Silurian) Carbonaceous slate and phyllite, with minor metagraywacke to the west (Zen, 1983; Peck, 1975). Bedding is...Allmendinger (1975). So OAKDALE FORMATION (Silurian) Metasiltstone and phyllite. It is fine- grained and consists of quartz and minor feldspar and ankerite, and

  14. High resolution cathodoluminescence spectroscopy of carbonate cementation in Khurmala Formation (Paleocene-L. Eocene) from Iraqi Kurdistan Region, Northern Iraq

    NASA Astrophysics Data System (ADS)

    Omer, Muhamed F.; Omer, Dilshad; Zebari, Bahroz Gh.

    2014-12-01

    A combination of high resolution cathodoluminsecnce-spectroscopy (HRS-CL) with spatial electron microprobe analysis and optical microscopy is used to determine paragenesis and history of cementation in the limestones and dolostones of Khurmala Formation which is exposed in many parts of Northern Iraq. Khurmala Formation was subjected to different diagenetic processes such as micritization, compaction, dissolution, neomorphism, pyritization and cementation that occurred during marine to shallow burial stages and culminated during intermediate to deep burial later stages. Five dolomite textures are recognized and classified according to crystal size distribution and crystal-boundary shape. Dolomitization is closely associated with the development of secondary porosity that pre-and postdates dissolution and corrosion; meanwhile such porosity was not noticed in the associated limestones. Microprobe analysis revealed three types of cement, calcite, dolomite and ankerite which range in their luminescence from dull to bright. Cathodoluminescence study indicated four main texture generations. These are (1) unzoned microdolomite of planar and subhedral shape, with syntaxial rim cement of echinoderm that show dull to red luminescence, (2) equant calcite cements filling interparticle pores which shows dull luminescence and weak zonal growth, (3.1) homogenous intrinsic blue stoichiometric calcite with dull luminescence and without activators, (3.2) coarse blocky calcite cement with strong oscillatory zoning and bright orange luminescence which postdates other calcite cements, (4) ankerite cement with red to orange, non-luminescence growth zonation which is the last formed cement.

  15. Diagenesis of an 'overmature' gas reservoir: The Spiro sand of the Arkoma Basin, USA

    USGS Publications Warehouse

    Spotl, C.; Houseknecht, D.W.; Burns, S.J.

    1996-01-01

    The Spiro sand is a laterally extensive thin sandstone of earliest Atokan (Pennsylvanian) age that forms a major natural gas reservoir in the western Arkoma Basin, Oklahoma. Petrographic analysis reveals a variety of diagenetic alterations, the majority of which occurred during moderate to deep burial. Early diagenetic processes include calcite cementation and the formation of Fe-clay mineral peloids and coatings around quartz framework grains. These clays, which underwent transformation to well-crystallized chamosite [polytype Ib(?? = 90??)] on burial, are particularly abundant in medium-grained channel sandstones, whereas illitic clays are predominant in fine-grained interchannel sandstones. Subsequent to mechanical compaction, saddle ankerite precipitated in the reservoir at temperatures in excess of 70??C. Crude oil collected in favourable structural locations during and after ankeritization. Whereas hydrocarbons apparently halted inorganic diagenesis in oil-saturated zones, cementation continued in the underlying water-saturated zones. As reservoir temperatures increased further, hydrocarbons were cracked and a solid pyrobitumen residue remained in the reservoir. At temperatures exceeding ???140-150??C, non-syntaxial quartz cement, ferroan calcite and traces of dickite(?) locally reduced the reservoir quality. Local secondary porosity was created by carbonate cement dissolution. This alteration post-dated hydrocarbon emplacement and is probably related to late-stage infiltration of freshwater along 'leaky' faults. The study shows that the Spiro sandstone locally retained excellent porosities despite deep burial and thermal conditions that correspond to the zone of incipient very low grade metamorphism.

  16. 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

  17. The Bowland Basin, NW England: Base metal mineralisation and its relationship to basin evolution

    NASA Astrophysics Data System (ADS)

    Gaunt, Jonathan Mark

    The Bowland Basin of NW England is a Carboniferous half graben. The Basin was initiated in the Devonian and actively extended during the Carboniferous until the late Westphalian. From the late Westphalian to the early Permian the Bowland Basin underwent inversion in response to Hercynian collision tectonics. Renewed subsidence commenced in the Permian and continued until inversion in the Cenozoic. The sedimentary succession of the Bowland Basin is dominated by Carboniferous strata, but some Permo-Triassic strata are present. The basal sedimentary succession may be comprised of Devonian to early Dinantian syn-rift clastics. The main Dinantian succession is comprised of interbedded limestones, calcareous mudstones and clastic strata. The Dinantian strata include the Waulsortian-facies Clitheroe Limestone and the Limekiln Wood Limestone, both of which host mineralisation. The overlying Namurian is comprised of shales and sandstones. The diagenetic history of the Limekiln Wood Limestone and Waulsortian-facies Clitheroe Limestone in the Cow Ark-Marl Hill Moor district is a function of changes in the burial environment during the Carboniferous. Both exhibit a pre-basin inversion diagenetic sequence that changes with time from shallow to moderate burial depth cements. Late Carbonifeous basin inversion resulted in the formation of tectonic stylolites. Tectonic stylolitisation was postdated by dolomitisation and silicification. Dolomitisation and silicification are suggested to have taken place in the deep burial environment. The base metal mineralisation studied in this work comes from the Cow Ark- Marl Hill Moor district, which is sited on the present basin inversion axis. Mineralisation occurs as four distinct episodes (Period 1, Period 2, Period 3 and Post-Period 3) within a complex multigeneration vein suite. The vein suite, which postdates tectonic stylolitisation and hence end-Carboniferous basin inversion, is comprised of calcite, baroque dolomite, baroque ankerite and siderite. The veins, which are often spatially associated with faults, exhibit a variety of morphologies, and are largely hosted by hydraulic shear fractures. Compositional variations between the different vein carbonates occur with time and the calcites, baroque dolomites, baroque ankerites and siderites are interpreted to have had several different fluid sources. Fluids precipitating siderite, baroque dolomite and baroque ankerite may have been produced by clay mineral transformations and decarboxylation of organic matter within the calcareous strata. The multiple vein calcite generations belong to three MnO:FeO compositional classes, each occupying a specific paragenetic position. The trend from ferroan to manganoan calcite with time may be a consequence of calcite-forming fluids being derived from successively shallower depths within the sedimentary succession, or of increased permeation by meteoric fluids. (Abstract shortened by ProQuest.).

  18. Geochemistry of precambrian carbonates. II. Archean greenstone belts and Archean sea water

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

    Veizer, J.; Hoefs, J.; Lowe, D.R.

    1989-04-01

    Carbonate rocks with geological attributes of marine sediments are a minor component of the Archean greenstone belts. Despite their relative scarcity, these rocks are important because they record chemical and isotopic properties of coeval oceans. The greenstones containing such carbonates appear to cluster at {approximately}2.8 {plus minus} 0.2 and {approximately}3.5 {plus minus} 0.1 Ga ago. The samples for the younger group are from the Abitibi, Yellowknife, Wabigoon, Michipicoten and Uchi greenstone belts of Canada and the Upper Greenstones of Zimbabwe. The older group includes the Swaziland Supergroup of South Africa, Warrawoona Group of Australia and the Sargur marbles of India.more » Mineralogically, the carbonates of the younger greenstones are mostly limestones and of the older ones, ferroan dolomites (ankerites); the latter with some affinities to hydrothermal carbonates. In mineralized areas with iron ores, the carbonate minerals are siderite {plus minus} ankerite, irrespective of the age of the greenstones. Iron-poor dolomites represent a later phase of carbonate generation, related to post-depositional tectonic faulting. The original mineralogy of limestone sequences appears to have been an Sr-rich aragonite. The Archean carbonates yield near-mantle Sr isotopic values, with ({sup 87}Sr/{sup 86}Sr){sub o} of 0.7025 {plus minus} 0.0015 and 0.7031 {plus minus} 0.0008 for younger and older greenstones, respectively. The mineralogical and chemical attributes of Archean carbonates are consistent with the proposition that the composition of the coeval oceans may have been buffered by a pervasive interaction with the mantle, that is, with the oceanic crust and the coeval ubiquitous volcanosedimentary piles derived from mantle sources.« less

  19. Ferroan dolomites in Miocene sediments of the Xisha Islands and their genetic model

    NASA Astrophysics Data System (ADS)

    Xu, Hong; Zhang, Weiwei; Wei, Kai; He, Qingkun; Jiang, Yunshui; Xu, Tingting; Jiang, Xuejun; Yan, Guijing; Song, Hongying; Wang, Jianghai

    2018-01-01

    Carbonate rocks are important reservoirs for global petroleum exploration. The largest oilfield in the South China Sea, Liuhua 11-1, is distributed in the massive carbonate reef area of the Zhujiang (Pearl) River Mouth Basin. Previous studies showed that one 802.17-m-long core from well Xichen-1 in the South China Sea mainly consisted of white and light gray-white organic reefs. Recently, a Miocene whole core (161.9 m long) of well Xiyong-2, near well Xichen-1, was found to contain six layers of yellowish brown, light yellowish gray, iron black, or light yellowish gray-white organic reefs. Scanning electron microscope images of these layers reveal a typical ferroan dolomite rich in Fe (up to 29%), with the high concentrations of Mn, Cu, W, Zn, Cr, Ni, and Co. Systematic X-ray powder diffraction analysis yields a 1.9-6.1 match in phase ratio with ankerite, 5.4-26.9 with dolomite, and zero with calcite, which indicate that the samples can be classified as ferroan dolomite. The iron and heavy metals are inferred to be originated from multiple volcanic eruptions of Gaojianshi Island in the Dongdao Atoll during the middle-late Miocene. These elements were dissolved in seawater, likely as a sol, and carried to Yongxing Island in the Xuande Atoll by sea currents and tides enhanced by prevailing winds, and deposited as a part of the sedimentation process in the study area. The ferroan dolomite has Sr content of (125-285)×10-6, which is lower than the accepted Sr boundary value of dolomite. This finding suggests that dolomitization occurred during large-scale global glacial regression in the late Miocene. The isolated Xisha carbonate platform, exposed to air, underwent freshwater leaching and dolomitization induced by mixed water, and caused the extensive Fe-Mg exchange along the organic reef profile to form ankerite and ferroan dolomite. These results may help to understand paleoceanographic environmental changes in the South China Sea during the Miocene.

  20. Multiple episodes of dolomitization and dolomite recrystallization during shallow burial in Upper Jurassic shelf carbonates: eastern Swabian Alb, southern Germany

    NASA Astrophysics Data System (ADS)

    Reinhold, C.

    1998-10-01

    The Upper Jurassic of the eastern Swabian Alb is composed of oolitic platform sands with associated microbe-siliceous sponge mounds at the platform margins. They are surrounded by argillaceous or calcareous mudstones and marl-limestone alternations, deposited in adjacent marl basins. Partial to complete dolomitization is predominantly confined to the mound facies. Six types of dolomite, as well as one type of ankerite, document a complex diagenetic history during shallow burial with multiple episodes of dolomite formation and recrystallization. The earliest massive matrix dolomitization is Ca-rich, has slightly depleted oxygen isotope values relative to Late Jurassic seawater, and carbon isotopic values in equilibrium with Late Jurassic seawater. This initial massive matrix dolomitization occurred during latest Jurassic to earliest Cretaceous and is related to pressure dissolution during very shallow burial at temperatures of at least 50°C. Hydrologic conditions and mass-balance calculations indicate that burial compaction provided sufficient fluids for dolomitization. Mg is derived from negligibly modified seawater, that was expelled from the adjacent off-reef strata into the mound facies. Position of the mounds along the platform margins controlled the distribution of the shallow-burial dolomite. Covariant trends between textural modification, increasing stoichiometry, partial changes in trace element content (Mn, Fe, Sr) and depletion in stable isotopes as well as distinctive CL pattern illustrate two recrystallization phases of the precursor matrix dolomite during further burial at elevated temperatures. Strong Sr enrichment of the second phase of recrystallized dolomite is ascribed to Sr-rich meteoric waters descending from overlying aragonite-bearing reef limestones or evaporite-bearing peritidal carbonates. Late-stage coarsely crystalline dolomite cements occur as vug and fracture fillings and formed during burial. Ankerite, associated with sulphide and sulphate minerals, and saddle dolomite are assumed to have formed from hydrothermal waters that moved to higher stratigraphic levels along fracture conduit systems that developed during Late Cretaceous to Tertiary Alpine orogenesis.

  1. Structural setting of Fimiston- and Oroya-style pyrite-telluride-gold lodes, Paringa South mine, Golden Mile, Kalgoorlie: 1. Shear zone systems, porphyry dykes and deposit-scale alteration zones

    NASA Astrophysics Data System (ADS)

    Mueller, Andreas G.

    2017-07-01

    The Golden Mile in the 2.7 Ga Eastern Goldfields Province of the Yilgarn Craton, Western Australia, has produced 385 million tonnes of ore at a head grade of 5.23 g/t gold (1893-2016). Gold-pyrite ore bodies (Fimiston Lodes) trace kilometre-scale shear zone systems centred on the D2 Golden Mile Fault, one of three northwest striking sinistral strike-slip faults segmenting upright D1 folds. The Fimiston shear zones formed as D2a Riedel systems in greenschist-facies (actinolite-albite) tholeiitic rocks, the 700-m-thick Golden Mile Dolerite (GMD) sill and the Paringa Basalt (PB), during left-lateral displacement of up to 12 km on the D2 master faults. Pre-mineralisation granodiorite dykes were emplaced into the D2 shear zones at 2674 ± 6 Ma, and syn-mineralisation diorite porphyries at 2663 ± 11 Ma. The widespread infiltration of hydrothermal fluid generated chlorite-calcite and muscovite-ankerite alteration in the Golden Mile, and paragonite-ankerite-chloritoid alteration southeast of the deposit. Fluid infiltration reactivated the D2 shear zones causing post-porphyry displacement of up to 30 m at principal Fimiston Lodes moving the southwest block down and southeast along lines pitching 20°SE. D3 reverse faulting at the southwest dipping GMD-PB contact of the D1 Kalgoorlie Anticline formed the 1.3-km-long Oroya Shoot during late gold-telluride mineralisation. Syn-mineralisation D3a reverse faulting alternated with periods of sinistral strike-slip (D2c) until ENE-WSW shortening prevailed and was accommodated by barren D3b thrusts. North-striking D4 strike-slip faults of up to 2 km dextral displacement crosscut the Fimiston Lodes and the barren thrusts, and control gold-pyrite quartz vein ore at Mt. Charlotte (2651 ± 9 Ma).

  2. A salt diapir-related Mississippi Valley-type deposit: the Bou Jaber Pb-Zn-Ba-F deposit, Tunisia: fluid inclusion and isotope study

    NASA Astrophysics Data System (ADS)

    Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.

    2016-08-01

    The Bou Jaber Ba-F-Pb-Zn deposit is located at the edge of the Bou Jaber Triassic salt diapir in the Tunisia Salt Diapir Province. The ores are unconformity and fault-controlled and occur as subvertical column-shaped bodies developed in dissolution-collapse breccias and in cavities within the Late Aptian platform carbonate rocks, which are covered unconformably by impermeable shales and marls of the Fahdene Formation (Late Albian-Cenomanian age). The host rock is hydrothermally altered to ankerite proximal to and within the ore bodies. Quartz, as fine-grained bipyramidal crystals, formed during hydrothermal alteration of the host rocks. The ore mineral assemblage is composed of barite, fluorite, sphalerite, and galena in decreasing abundance. The ore zones outline distinct depositional events: sphalerite-galena, barite-ankerite, and fluorite. Fluid inclusions, commonly oil-rich, have distinct fluid salinities and homogenization temperatures for each of these events: sphalerite-galena (17 to 24 wt% NaCl eq., and Th from 112 to 136 °C); ankerite-barite (11 to 17 wt% NaCl eq., and Th from 100 to 130 °C); fluorite (19 to 21 wt% NaCl eq., Th from 140 to 165 °C). The mean temperature of the ore fluids decreased from sphalerite (125 °C) to barite (115 °C) and increased during fluorite deposition (152 °C); then decreased to ˜110 °C during late calcite precipitation. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of fluid inclusions in fluorite are metal rich (hundreds to thousands ppm Pb, Zn, Cu, Fe) but the inclusions in barite are deficient in Pb, Zn, Cu, Fe. Inclusions in fluorite have Cl/Br and Na/Br ratios of several thousand, consistent with dissolution of halite while the inclusions analysed in barite have values lower than seawater which are indicative of a Br-enriched brine derived from evaporation plus a component of halite dissolution. The salinity of the barite-hosted fluid inclusions is less than obtained simply by the evaporation of seawater to halite saturation and requires a dilution of more than two times by meteoric water. The higher K/Na values in fluid inclusions from barite suggest that the brines interacted with K-rich rocks in the basement or siliciclastic sediments in the basin. Carbonate gangue minerals (ankerite and calcite) have δ13C and δ18O values that are close to the carbonate host rock and indicate fluid equilibrium between carbonate host rocks and hydrothermal brines. The δ34S values for sphalerite and galena fall within a narrow range (1 to 10 ‰) with a bulk value of 7.5 ‰, indicating a homogeneous source of sulfur. The δ34S values of barite are also relatively homogeneous (22 ‰), with 6 ‰ higher than the δ34S of local and regional Triassic evaporites (15 ‰). The latter are believed to be the source of sulfate. Temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate via hydrocarbons produced probably from Late Cretaceous source rocks. The 87Sr/86Sr ratio in the Bou Jaber barite (0.709821 to 0.711408) together with the lead isotope values of Bou Jaber galena (206Pb/204Pb = 18.699 to 18.737; 207Pb/204Pb = 15.635 to 15.708 and 208Pb/204Pb = 38.321 to 38.947) show that metals were extracted from homogeneous crustal source(s). The tectonic setting of the Bou Jaber ore deposit, the carbonate nature of the host rocks, the epigenetic style of the mineralization and the mineral associations, together with sulfur and oxygen isotope data and fluid inclusion data show that the Bou Jaber lead-zinc mineralization has the major characteristics of a salt diapir-related Mississippi Valley-type (MVT) deposit with superimposed events of fluorite and of barite deposition. Field relations are consistent with mineral deposition during the Eocene-Miocene Alpine orogeny from multiple hydrothermal events: (1) Zn-Pb sulfides formed by mixing of two fluids: one fluid metal-rich but reduced sulfur-poor and a second fluid reduced sulfur-rich; (2) barite precipitation involved the influx of a meteoric water component that mixed with a barium-rich fluid; and (3) fluorite precipitated from a highly saline fluid with higher temperatures.

  3. Geology of the Alaska-Juneau lode system, Alaska

    USGS Publications Warehouse

    Twenhofel, William Stephens

    1952-01-01

    The Alaska-Juneau lode system for many years was one of the worlds leading gold-producing areas. Total production from the years 1893 to 1946 has amounted to about 94 million dollars, with principal values in contained gold but with some silver and lead values. The principal mine is the Alaska-Juneau mine, from which the lode system takes its name. The lode system is a part of a larger gold-bearing belt, generally referred to as the Juneau gold belt, along the western border of the Coast Range batholith. The rocks of the Alaska-Juneau lode system consist of a monoclinal sequence of steeply northeasterly dipping volcanic, state, and schist rocks, all of which have been metamorphosed by dynamic and thermal processes attendant with the intrusion of the Coast Range batholith. The rocks form a series of belts that trend northwest parallel to the Coast Range. In addition to the Coast Range batholith lying a mile to the east of the lode system, there are numerous smaller intrusives, all of which are sill-like in form and are thus conformable to the regional structure. The bedded rocks are Mesozoic in age; the Coast Range batholith is Upper Jurassic and Lower Cretaceous in age. Some of the smaller intrusives pre-date the batholith, others post-date it. All of the rocks are cut by steeply dipping faults. The Alaska-Juneau lode system is confined exclusively to the footwall portion of the Perseverance slate band. The slate band is composed of black slate and black phyllite with lesser amounts of thin-bedded quartzite. Intrusive into the slate band are many sill-like bodies of rocks generally referred to as meta-gabbro. The gold deposits of the lode system are found both within the slate rocks and the meta-gabbro rocks, and particularly in those places where meta-gabbro bodies interfinger with slate. Thus the ore bodies are found in and near the terminations of meta-gabbro bodies. The ore bodies are quartz stringer-lodes composed of a great number of quartz veins from 6 inches to 3 feet wide and extending along their strike and dip for several tens to hundreds of feet. In addition to quartz, the only other vein gangue mineral is ankerite. It occurs in small amounts along the borders of the quartz veins. Metallic vein minerals, in addition to native gold, are, in order of decreasing abundance, pyrrhotite, galena, sphalerite, and arsenopyrite. In the aggregate the metallic minerals comprise only 1 to 2 percent of the total amount of vein material. The wall rock, particularly the meta-gabbro, was profoundly altered by the vein-forming processes. The principal effects on the meta-gabbro were the addition of large amounts of soda, potash, titanium, carbon dioxide, and phosphorous, and the removal of considerable quantities of iron, magnesia, lime, and combined water. Silica also may have been decreased. The mineralogical changes involved in the alteration were the development of biotite and ankerite at the expense of original hornblende and feldspar, resulting in a brown-colored biotite- and ankerite-rich rock. The slates are relatively unaffected by the vein-forming processes. Because of their small size, relatively low grade, and discontinuity, no attempt has been made to mine any individual vein. The prevailing practice has been to mine large blocks of ground by a system of modified block-caving, followed by hand sorting to remove the barren country rock from the gold-bearing quartz prior to milling.

  4. Biogeochemical processes controlling authigenic carbonate formation within the sediment column from the Okinawa Trough

    NASA Astrophysics Data System (ADS)

    Li, Jiwei; Peng, Xiaotong; Bai, Shijie; Chen, Zhiyan; Van Nostrand, Joy D.

    2018-02-01

    Authigenic carbonates are one type of conspicuous manifestation in seep environments that can provide long-term archives of past seepage activity and methane cycling in the oceans. Comprehensive investigations of the microbial community functional structure and their roles in the process of carbonate formation are, however, lacking. In this study, the mineralogical, geochemical, and microbial functional composition were examined in seep carbonate deposits collected from the west slope of the northern section of the Okinawa Trough (OT). The aim of this work was to explore the correspondence between the mineralogical phases and microbial metabolism during carbonate deposit formation. The mineralogical analyses indicated that authigenic carbonate minerals (aragonite, magnesium-rich calcite, dolomite, ankerite and siderite) and iron-bearing minerals (limonite, chlorite, and biotite) were present in these carbonate samples. The carbon and oxygen isotopic values of the carbonate samples varied between -51.1‰ to -4.7‰ and -4.8‰ to 3.7‰, respectively. A negative linear correlation between carbon and oxygen isotopic compositions was found, indicating a mixture of methane-derived diagenetic (low δ13C/high 18O) carbonates and detrital origin (high δ13C/low 18O) carbonates at the OT. GeoChip analyses suggested that various metabolic activities of microorganisms, including methanogenesis, methane oxidation, sulfite oxidation, sulfate reduction, and metal biotransformations, all occurred during the formation process. On the basis of these findings, the following model for the methane cycle and seep carbonate deposit formation in the sediment column at the OT is proposed: (1) in the upper oxidizing zone, aerobic methane oxidation was the main way of methane consumption; (2) in the sulfate methane transition zone, sulfate-dependent AOM (anaerobic oxidation of methane) consumes methane, and authigenic minerals such as aragonite, magnesium-calcite, and sulfide minerals precipitate; (3) in the underlying sulfate depleted zone, the presence of iron-oxides supplied by hydrothermal fluids and terrestrial inputs created thermodynamically favorable conditions for Fe-dependent AOM to consume methane, and dolomite and siderite/ankerite precipitate in this zone.

  5. From Carbonatite to Ikaite: How high-T carbonates are transformed into low-T carbonate minerals in SW Greenland

    NASA Astrophysics Data System (ADS)

    Stockmann, G. J.; Tollefsen, E.; Ranta, E.; Skelton, A.; Sturkell, E.; Lundqvist, L.

    2015-12-01

    The 1300 Ma Grønnedal-Íka igneous complex in southwest Greenland comprises nepheline syenites and carbonatites. It belongs to a suite of intrusions formed 1300-1100 Ma ago referred to as the Gardar period. In modern time (the last ca. 8000 years), fluid-rock interactions involving the nepheline syenites and carbonatites gives rise to about one thousand submarine columns made of the rare low-T mineral ikaite (CaCO3x6H2O). The columns are found in a shallow, narrow fjord named Ikka Fjord and their distribution clearly follows the outcrop of the Grønnedal-Íka complex. When meteoric water percolates through the highly fractured complex, a sodium carbonate solution of pH 10 is formed through hitherto unknown fluid-rock reactions. This basic solution seeps up through fractures at the bottom of Ikka Fjord and when mixed with seawater, the mineral ikaite is formed. As the seepage water has a lower density than seawater, there is an upwards flow that creates columns. What is peculiar about ikaite is its limited stability making it unstable above +6 °C. Isotopic studies of ikaite reveal a seawater origin for the Ca2+ ions, and the carbonatite being the most likely source for the CO32- ions. The carbonatite is mainly of søvite composition (CaCO3) with high contents of siderite and ankerite in certain areas. The nepheline syenites contain Na,K-rich minerals like nepheline, alkali-feldspar, aegirine-augite, katophorite and biotite. Nepheline is mainly replaced by muscovite, and aegirine-augite partly by chlorite, which could release sodium into solution. A dolerite dyke of unknown age prompted extensive mineralization of magnetite by activating hydrothermal fluid convection. The fluid interacted with the carbonatite, replacing siderite and ankerite by magnetite and later hematite. In a newly launched project at Stockholm University, we are trying to unravel the chemical reactions taking place inside the Grønnedal-Íka igneous complex leading to the formation of the sodium carbonate solution issuing in Ikka Fjord.

  6. Natural diamond formation by self-redox of ferromagnesian carbonate

    NASA Astrophysics Data System (ADS)

    Chen, Ming; Shu, Jinfu; Xie, Xiande; Tan, Dayong; Mao, Ho-kwang

    2018-03-01

    Formation of natural diamonds requires the reduction of carbon to its bare elemental form, and pressures (P) greater than 5 GPa to cross the graphite–diamond transition boundary. In a study of shocked ferromagnesian carbonate at the Xiuyan impact crater, we found that the impact pressure–temperature (P-T) of 25–45 GPa and 800–900 °C were sufficient to decompose ankerite Ca(Fe2+,Mg)(CO3)2 to form diamond in the absence of another reductant. The carbonate self-reduced to diamond by concurrent oxidation of Fe2+ to Fe3+ to form a high-P polymorph of magnesioferrite, MgFe3+2O4. Discovery of the subsolidus carbonate self-reduction mechanism indicates that diamonds could be ubiquitously present as a dominant host for carbon in the Earth’s lower mantle.

  7. Phase transformations of siderite ore by the thermomagnetic analysis data

    NASA Astrophysics Data System (ADS)

    Ponomar, V. P.; Dudchenko, N. O.; Brik, A. B.

    2017-02-01

    Thermal decomposition of Bakal siderite ore (that consists of magnesium siderite and ankerite traces) was investigated by thermomagnetic analysis. Thermomagnetic analysis was carried-out using laboratory-built facility that allows automatic registration of sample magnetization with the temperature (heating/cooling rate was 65°/min, maximum temperature 650 °C) at low- and high-oxygen content. Curie temperature gradually decreases with each next cycles of heating/cooling at low-oxygen content. Curie temperature decrease after 2nd cycle of heating/cooling at high-oxygen content and do not change with next cycles. Final Curie temperature for both modes was 320 °C. Saturation magnetization of obtained samples increases up to 20 Am2/kg. The final product of phase transformation at both modes was magnesioferrite. It was shown that intermediate phase of thermal decomposition of Bakal siderite ore was magnesiowustite.

  8. Wallula Basalt Pilot Demonstration Project: Post-injection Results and Conclusions

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

    McGrail, Bernard Pete; Schaef, Herbert T.; Spane, Frank A.

    Deep underground geologic formations are emerging as a reasonable option for long-term storage of CO 2, including large continental flood basalt formations. At the GHGT-11 and GHGT-12 conferences, progress was reported on the initial phases for Wallula Basalt Pilot demonstration test (located in Eastern Washington state), where nearly 1,000 metric tons of CO 2 were injected over a 3-week period during July/August 2013. The target CO 2 injection intervals were two permeable basalt interflow reservoir zones with a combined thickness of ~20 m that occur within a layered basalt sequence between a depth of 830-890 m below ground surface. Duringmore » the two-year post-injection period, downhole fluid samples were periodically collected during this post-injection monitoring phase, coupled with limited wireline borehole logging surveys that provided indirect evidence of on-going chemical geochemical reactions/alterations and CO 2 disposition. A final detailed post-closure field characterization program that included downhole fluid sampling, and performance of hydrologic tests and wireline geophysical surveys. Included as part of the final wireline characterization activities was the retrieval of side-wall cores from within the targeted injection zones. These cores were examined for evidence of in-situ mineral carbonization. Visual observations of the core material identified small globular nodules, translucent to yellow in color, residing within vugs and small cavities of the recovered basalt side-wall cores, which were not evident in pre-injection side-wall cores obtained from the native basalt formation. Characterization by x-ray diffraction identified these nodular precipitates as ankerite, a commonly occurring iron and calcium rich carbonate. Isotopic characterization (δ 13C, δ 18O) conducted on the ankerite nodules indicate a distinct isotopic signature that is closely aligned with that of the injected CO 2. Both the secondary mineral nodules and injected CO 2 are measurably different from the isotopic content of basalt, injection zone groundwater and for naturally occurring calcite. Final post-injection wireline geophysical logging results also indicate the presence of free-phase CO 2 at the top of the two injection interflow zones, with no vertical migration of CO 2 above the injection horizons. Furthermore, these findings are significant and demonstrate the feasibility of sequestering CO 2 in a basalt formation.« less

  9. Wallula Basalt Pilot Demonstration Project: Post-injection Results and Conclusions

    DOE PAGES

    McGrail, Bernard Pete; Schaef, Herbert T.; Spane, Frank A.; ...

    2017-08-18

    Deep underground geologic formations are emerging as a reasonable option for long-term storage of CO 2, including large continental flood basalt formations. At the GHGT-11 and GHGT-12 conferences, progress was reported on the initial phases for Wallula Basalt Pilot demonstration test (located in Eastern Washington state), where nearly 1,000 metric tons of CO 2 were injected over a 3-week period during July/August 2013. The target CO 2 injection intervals were two permeable basalt interflow reservoir zones with a combined thickness of ~20 m that occur within a layered basalt sequence between a depth of 830-890 m below ground surface. Duringmore » the two-year post-injection period, downhole fluid samples were periodically collected during this post-injection monitoring phase, coupled with limited wireline borehole logging surveys that provided indirect evidence of on-going chemical geochemical reactions/alterations and CO 2 disposition. A final detailed post-closure field characterization program that included downhole fluid sampling, and performance of hydrologic tests and wireline geophysical surveys. Included as part of the final wireline characterization activities was the retrieval of side-wall cores from within the targeted injection zones. These cores were examined for evidence of in-situ mineral carbonization. Visual observations of the core material identified small globular nodules, translucent to yellow in color, residing within vugs and small cavities of the recovered basalt side-wall cores, which were not evident in pre-injection side-wall cores obtained from the native basalt formation. Characterization by x-ray diffraction identified these nodular precipitates as ankerite, a commonly occurring iron and calcium rich carbonate. Isotopic characterization (δ 13C, δ 18O) conducted on the ankerite nodules indicate a distinct isotopic signature that is closely aligned with that of the injected CO 2. Both the secondary mineral nodules and injected CO 2 are measurably different from the isotopic content of basalt, injection zone groundwater and for naturally occurring calcite. Final post-injection wireline geophysical logging results also indicate the presence of free-phase CO 2 at the top of the two injection interflow zones, with no vertical migration of CO 2 above the injection horizons. Furthermore, these findings are significant and demonstrate the feasibility of sequestering CO 2 in a basalt formation.« less

  10. Experimental investigation of CO2-brine-rock interactions at simulated in-situ conditions

    NASA Astrophysics Data System (ADS)

    Słomski, Piotr; Lutyński, Marcin; Mastalerz, Maria; Szczepański, Jacek; Derkowski, Arkadiusz; Topór, Tomasz

    2017-04-01

    Geological sequestration of carbon dioxide (CO2) in deep formations (e.g. saline aquifers, oil and gas reservoirs and coalbeds) is one of the most promising options for reducing concentration of this anthropogenic greenhouse gas in the atmosphere. CO2 injected into the rock formations can be trapped by several mechanisms including structural and stratigraphic trapping, capillary CO2 trapping, dissolution trapping and mineral trapping. During dissolution trapping, CO2 dissolves in the formation brine and sinks in the reservoir as the CO2-enriched brine has an increased density. In comparison, in mineral trapping, CO2 is bound by precipitating new carbonate minerals. The latter two mechanisms depend on the temperature, pressure, and the mineralogy of the reservoir rock and the chemical composition of the brine. This study discusses laboratory scale alterations of Ordovician and Silurian shale rocks from potential CO2 sequestration site B1 in the Baltic Basin. In the reported experiment, rocks submerged in brine in specially constructed reactors were subjected to CO2 pressure of 30-35 MPa for 30-45 days at temperature of 80 oC. Shale samples were analyzed in terms of mineral composition and mesopore surface area and volume, before and after experiments, by means of X-ray diffraction and N2 low-pressure adsorption, respectively, for possible CO2 induced changes. Comparison of mineral composition before and after experiments demonstrated subtle mineral changes. The most conspicuous was a release of Fe in the form of Fe-oxyhydroxides, most probably related to the decomposition of Fe-bearing minerals like pyrite, chlorite and, less frequently, ankerite. With regard to porosity, interestingly, the most significant increase in mesopore surface area and mesopore volume was observed in samples with the largest drop of chlorite amount. The less significant mineral changes were associated with formation of kaolinite related to breakdown of feldspars and dissolution of carbonate minerals represented by calcite, dolomite, and ankerite. In the analyzed samples, no new carbonate minerals were formed during the experiments. An increase of carbonates was recorded only in three out of 13 samples. However, concentration of carbonates in these three samples is too low to conclude CO2 mineral trapping in new carbonate phases. Acknowledgments: the study was supported from grant SHALESEQ (No PL12-0109) funded by the National Centre for Research and Development.

  11. A high-pyrite semianthracite of Late Permian age in the Songzao Coalfield, southwestern China: Mineralogical and geochemical relations with underlying mafic tuffs

    USGS Publications Warehouse

    Dai, S.; Wang, X.; Chen, W.; Li, D.; Chou, C.-L.; Zhou, Y.; Zhu, Chen; Li, H.; Zhu, Xudong; Xing, Y.; Zhang, W.; Zou, J.

    2010-01-01

    The No. 12 Coal (Late Permian) in the Songzao Coalfield, Chongqing, southwestern China, is characteristically high in pyrite and some trace elements. It is uniquely deposited directly above mafic tuff beds. Samples of coal and tuffs have been studied for their mineralogy and geochemistry using inductively coupled plasma-mass spectrometry, X-ray fluorescence, plasma low-temperature ashing plus powder X-ray diffraction, and scanning electron microscopy equipped with energy-dispersive X-ray analysis.The results show that the minerals of the No. 12 Coal are mainly composed of pyrite, clay minerals (kaolinite, chamosite, and illite), ankerite, calcite, and trace amounts of quartz and boehmite. Kaolinite and boehmite were mainly derived from sediment source region of mafic tuffs. Chamosite was formed by the reaction of kaolinite with Fe-Mg-rich fluids during early diagenesis. The high pyrite (Sp,d=8.83%) in the coal was related to marine transgression over peat deposits and abundant Fe derived from the underlying mafic tuff bed. Ankerite and calcite were precipitated from epigenetic fluids.Chemical compositions of incompatible elements indicate that the tuffs were derived from enriched mantle and the source magmas had an alkali-basalt character. Compared to other coals from the Songzao Coalfield and common Chinese coals, the No. 12 Coal has a lower SiO2/Al2O3 (1.13) but a higher Al2O3/Na2O (80.1) value and is significantly enriched in trace elements including Sc (13.5??g/g), V (121??g/g), Cr (33.6??g/g), Co (27.2??g/g), Ni (83.5??g/g), Cu (48.5??g/g), Ga (17.3??g/g), Y (68.3??g/g), Zr (444??g/g), Nb (23.8??g/g), and REE (392??g/g on average). Above mineralogical compositions, as well as similar ratios of selected elements (e.g., SiO2/Al2O3 and Al2O3/Na2O) and similar distribution patterns of incompatible elements (e.g., the mantle-normalized diagram for incompatible elements and chondrite-normalized diagram for rare earth elements) of coal and tuff, indicated that enriched trace elements above were largely derived from mafic tuffs, in addition to a minor amount from the Kandian Oldland. ?? 2010 Elsevier B.V.

  12. Hydrothermal alteration, ore fluid characteristics, and gold depositional processes along a trondhjemite-komatiite contact at Tarmoola, Western Australia

    USGS Publications Warehouse

    Duuring, P.; Hagemann, S.G.; Cassidy, K.F.; Johnson, C.A.

    2004-01-01

    Tarmoola is a structurally controlled Archean orogenic gold deposit hosted in greenschist facies metamorphosed komatiite and trondhjemite in the Leonora district of the Eastern Goldfields province, Yilgarn craton. High-grade (>1 g/t Au) orebodies are located in komatiite wall rock adjacent to the eastern and northeastern margins of the asymmetrical, north-south-striking, Tarmoola trondhjemite intrusion. Gold-bearing veins post-date trondhjemite emplacement (ca. 2700 Ma), quartz diorite dikes (ca. 2667 Ma), and regional greenschist facies metamorphism. Textures and crosscutting relationships in gold-bearing veins indicate two stages of hydrothermal fluid infiltration associated with a single gold-related hydrothermal event: a volumetrically dominant, but gold-poor, stage I fluid and a gold-rich stage II fluid. Gold-bearing veins contain stage I milky quartz and pyrite that are overprinted by stage II quartz-ankerite-muscovite-chalcopyrite-sphalerite-galena-gold-tellurides ?? albite ?? chlorite ?? fuchsite ?? epidote ?? scheelite. Stage I hydrothermal alteration assemblages are different in trondhjemite and komatiite due to contrasting reactions between a common ore fluid and disparate wall-rock chemistry. Stage II fluid-wall rock interaction was minor compared to stage I and is indicated by the overprinting of stage I mineral assemblages by stage II microveins. Wall-rock alteration proximal to veins in trondhjemite is characterized by replacement of igneous plagioclase, amphibole, biotite, and metamorphic chlorite by hydrothermal quartz, muscovite, ankerite, calcite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold, whereas in proximal alteration in komatiite, metamorphic chlorite and talc are replaced by ankerite, quartz, muscovite, albite, chlorite, fuchsite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold. The stage II fluid was enriched in H2O, CO2, Si, Ca, K, Na, S, Au, Ag, Cu, Pb, W, Bi, As, Mo, Zn, and Te. Based on fluid inclusion studies and stage II mineral equilibria, gold deposited from a homogeneous, neutral to slightly alkaline (pH 5.1-5.5), reduced, low-salinity (<5.5 wt % NaCl equiv) fluid that had a bulk composition of 78 mole percent H2O and 21 mole percent CO2, and trace amounts of CH4, C2H6, H2, Ar, H2S, and He. Gold deposition occurred at 300?? ?? 50??C and 0.5 to 3.0 kbars. Assuming lithostatic fluid pressures, gold precipitated at a 2- to 10-km depth. Stage II gray quartz ??18Ofluid values range from 5.9 to 7.5 per mil, whereas ??Dfluid values calculated from the dehydration of muscovite grains and measured directly from bulk fluid inclusion analyses of stage II gray quartz have ranges of -9 to -35 and -27 to -28 per mil, respectively. Hydrothermal ore fluids were transported from greater crustal depths to the site of gold deposition during the district-scale D3 event by shallowly W dipping, reverse brittle-ductile shear zones in supracrustal rock and along the steeply east dipping trondhjemite contact. Associated subhorizontal east-west shortening caused the reactivation of the eastern trondhjemite margin and subparallel foliation, which facilitated the transport of hydrothermal fluids and the generation of gold-bearing veins and hydrothermal alteration zones in komatiite. East-west-striking fractures in trondhjemite aided the lateral migration of ore fluids away from trondhjemite margins and the formation of east-west-striking gold-bearing veins and broad alteration zones. Gold was most likely transported in the stage II fluid as bisulfide complexes. The sulfidation of trondhjemite and komatiite wall rock by the stage II fluid caused the destabilization of An bisulfide complexes and gold deposition. Potassium, Ca, and CO2 metasomatism of komatiite wall rock may have enhanced gold deposition via the acidification of the stage II fluid. The physicochemical characteristics of the Tarmoola ore fluid and relative timing of gold mineralization are consistent with the Yilgarn-wide,

  13. Field Validation of Supercritical CO 2 Reactivity with Basalts

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

    McGrail, B. Peter; Schaef, Herbert T.; Spane, Frank A.

    2017-01-10

    Continued global use of fossil fuels places a premium on developing technology solutions to minimize increases in atmospheric CO 2 levels. CO 2 storage in reactive basalts might be one of these solutions by permanently converting injected gaseous CO 2 into solid carbonates. Herein we report results from a field demonstration where ~1000 MT of CO 2 was injected into a natural basalt formation in Eastern Washington State. Following two years of post-injection monitoring, cores were obtained from within the injection zone and subjected to detailed physical and chemical analysis. Nodules found in vesicles throughout the cores were identified asmore » the carbonate mineral, ankerite Ca[Fe, Mg, Mn](CO 3) 2. Carbon isotope analysis showed the nodules are chemically distinct as compared with natural carbonates present in the basalt and clear correlation with the isotopic signature of the injected CO 2. These findings provide field validation of rapid mineralization rates observed from years of laboratory testing with basalts.« less

  14. Mössbauer study of Fe mineralogy with respect to rank, type and Colombian carboniferous zone

    NASA Astrophysics Data System (ADS)

    Caballero, F. Reyes; Martínez Ovalle, S. A.; Díaz Lagos, M.; Gómez, O. P.; Blandón, A.

    2017-11-01

    The transmission mode of Fe-57 Mössbauer spectroscopy was used to identify iron bearing minerals and establish relationships between and among these minerals and the ranks and types of various carboniferous zones in Colombia. Maceral and mineral compositions vary significantly among Colombian carboniferous zones. These variations determine some of the final characteristics and potential uses of coal, and therefore significantly contribute to defining coal quality. A comparison of spectroscopy results shows that the thermal maturity of the Colombian coals ranges from lignite to semianthracite. Similarities and differences exist with respect to conventional parameters. The coals of Córdoba and Cauca have higher sulfur contents > 2 % ash contents. Iron bearing minerals identified included pyrite, which was, found everywhere, and illite, ankerite, siderite, iron sulfates were found in particular areas. Coals from Valle del Cauca, Córdoba, Caldas and Santander are characterized by oxidation of pyrite and its transformation into ferrous or ferric sulfate.

  15. Formation of the world's largest REE deposit through protracted fluxing of carbonatite by subduction-derived fluids

    PubMed Central

    Ling, Ming-Xing; Liu, Yu-Long; Williams, Ian S.; Teng, Fang-Zhen; Yang, Xiao-Yong; Ding, Xing; Wei, Gang-Jian; Xie, Lu-Hua; Deng, Wen-Feng; Sun, Wei-Dong

    2013-01-01

    Rare Earth Elements (REE) are essential to modern society but the origins of many large REE deposits remain unclear. The U-Th-Pb ages, chemical compositions and C, O and Mg isotopic compositions of Bayan Obo, the world's largest REE deposit, indicate a protracted mineralisation history with unusual chemical and isotopic features. Coexisting calcite and dolomite are in O isotope disequilibrium; some calcitic carbonatite samples show highly varied δ26Mg which increases with increasing Si and Mg; and ankerite crystals show decreases in Fe and REE from rim to centre, with highly varied REE patterns. These and many other observations are consistent with an unusual mineralisation process not previously considered; protracted fluxing of calcitic carbonatite by subduction-released high-Si fluids during the closure of the Palaeo-Asian Ocean. The fluids leached Fe and Mg from the mantle wedge and scavenged REE, Nb and Th from carbonatite, forming the deposit through metasomatism of overlying sedimentary carbonate.

  16. The Gifford Creek Ferrocarbonatite Complex, Gascoyne Province, Western Australia: Associated fenitic alteration and a putative link with the ~ 1075 Ma Warakurna LIP

    NASA Astrophysics Data System (ADS)

    Pirajno, Franco; González-Álvarez, Ignacio; Chen, Wei; Kyser, Kurt T.; Simonetti, Antonio; Leduc, Evelyne; leGras, Monica

    2014-08-01

    The Gifford Creek Ferrocarbonatite Complex (GFC), located in the Neoarchean-Palaeoproterozoic Gascoyne Province, Western Australia, comprises sills, dykes, and veins of ferrocarbonatite intruding the Pimbyana Granite and Yangibana Granite of the Durlacher Supersuite and metasedimentary rocks of the Pooranoo Metamorphics. The ferrocarbonatites are associated with complex and irregularly distributed zones of fenitic alteration. These ferrocarbonatites and fenites are also associated with a swarm of ironstone veins, containing magnetite, hematite and goethite. The GFC and associated fenite outcrops are distributed within a ~ 700 km2 area, north of the Lyons River Fault. Ferrocarbonatite sills and dykes are predominant in a northwest-trending belt, along the southern margin of the complex; whereas ferrocarbonatite veins tend to be distributed in a series of sub-parallel west-northwest-trending linear belts, generally associated with the Fe oxide veins with sinuous trends. These veins have margins of Fe-rich carbonates associated with zones of alteration that have a fenitic character. The fenitic haloes are characterised by the presence of Na-K-feldspars and/or Na-amphiboles and magnetite. In some cases monomineralic feldspar zones (orthoclasite) are present. Fenitic alteration is spatially associated with the carbonatites, but it can also form discrete veins and veinlets in basement granitic rocks (Pimbyana and Yangibana Granites). Petrographic, XRD and SEM analyses show that the ferrocarbonatites are dominantly composed of ankerite-dolomite, magnetite, arfvedsonite-riebeckite, and lesser calcite. Alkali amphibole has compositions ranging from potassian magnesio-arfvedsonite to magnesio-riebeckite. Sills and dykes north of the Lyons River, are characterised by a carbonate-rich matrix, containing > 50 vol.% ankerite-dolomite, with accessory quantities of apatite, barite, monazite, and phlogopite. In-situ U-Pb age determination of apatite grains by LA-ICP-MS on a sample of ferrocarbonatite was performed and an average age of 1075 ± 35 Ma was obtained. This age is within the range of ages (~ 1078-1070 Ma) of the Warakurna Large Igneous Province (WLIP) and we suggest that the GFC is related to the mantle plume event that generated the WLIP. This is a significant outcome, because it may lead to the recognition or discovery of other carbonatites within the area covered by the WLIP. In addition, monazite from fenitic rocks associated with the ironstones yielded an age of 1050 ± 25 Ma, suggesting that a second phase of carbonatite magmatism occurred, resulting in the emplacement of the carbonatite-ironstone veins swarm. A model is proposed to explain the formation of the GFC system.

  17. How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

    NASA Astrophysics Data System (ADS)

    Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György

    2017-04-01

    Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an unexpectedly high proportion of total amount of CO2. Further results enlightened that other carbonates, ankerite, calcite and siderite have precipitated in two generations, the first before and the second after the CO2 flooding. Further laboratory analysis and geochemical models allow us to estimate the ratio of these two generations and also to understand how far the reservoir rock is in the CO2 mineral trapping process.

  18. Genesis of the Sb-W-Au deposits at Ixtahuacan, Guatemala: evidence from fluid inclusions and stable isotopes

    NASA Astrophysics Data System (ADS)

    Guillemette, N.; Williams-Jones, A. E.

    1993-06-01

    The Ixtahuacan Sb-W deposits are hosted by upper Pennsylvanian to Permian metasedimentary rocks of the central Cordillera of Guatemala. The deposits consist of gold-bearing arsenopyrite, stibnite and scheelite. Arsenopyrite and scheelite are early in the paragenesis, occurring as disseminations in pyritiferous black shale/sandstone and in argillaceous limestone, respectively. Some stibnite is disseminated, but the bulk of the stibnite occurs as massive stratabound lenses in black shales and in quartz-ankerite veins and breccias, locally containing scheelite. Microthermometric measurements on fluid inclusions in quartz and scheelite point to a low temperature (160 190°C) and low to moderate salinity (5 15 wt% NaCl eq.) aqueous ore fluid. Abundant vapour-rich inclusions suggest that the fluid boiled. Carbon dioxide was produced locally as a result of interaction of the aqueous fluid with the argillaceous limestone. Bulk leaching experiments and SEM-EDS analyses of decrepitated fluid inclusion residues indicate that the ore-bearing solution was NaCl-dominated. The δ18O values of quartz, ankerite and scheelite from mineralized veins range from 19.7 to 20.5‰, 18.1 to 20.0‰ and 7.0 to 8.4‰ respectively. The average temperature calculated from quartz-scheelite oxygen isotopic fractionation is 170°C. The oxygen isotopic composition of the fluid, interpreted to have been in equilibrium with these minerals, ranged from 5.7 to 7.6‰, and is considered to represent an evolved meteoric water. Diagenetic or syngenetic pyrite has a sulphur isotopic composition of 0.5±0.3‰ which is consistent with bacterial reduction of sulphate. The δ34S values of arsenopyrite and stibnite range from -2.8 to 2.0‰ and -2.7 to -2.3‰ respectively, and are though to reflect sulphur derived from pyrite. The Ixtahuacan deposits are interpreted to have formed at low temperature (<200°C) and a depth of a few hundred metres from a low fO2 (10-49-10-57), high pH (7 8) fluid. Arsenic was probably transported as arsenious acid, antimony and gold as thio-complexes and tungsten as the complex HWO{4/-}. A model is proposed in which a meteoric fluid, heated by a felsic intrusion at depth, was focused to shallow levels along faults. The interaction of the fluid with pyritiferous beds caused the deposition of arsenopyrite as a result of sulphidation and/or decreasing fO2; gold probably co-precipitated with As or was adsorbed onto the arsenopyrite. The precipitation of stibnite was caused by boiling. Scheelite deposited in response to the increase in Ca2+ activity which accompanied interaction of the ore fluid with the argillaceous limestones.

  19. 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.

  20. A magmatic-hydrothermal lacustrine exhalite from the Permian Lucaogou Formation, Santanghu Basin, NW China - The volcanogenic origin of fine-grained clastic sedimentary rocks

    NASA Astrophysics Data System (ADS)

    Jiao, Xin; Liu, Yiqun; Yang, Wan; Zhou, Dingwu; Li, Hong; Nan, Yun; Jin, Mengqi

    2018-05-01

    Shales in the middle Permian Lucaogou Formation in the intracontinental Santanghu rift basin have been considered as "typical" organic-rich profundal shales for decades. Our study of well cores using petrographic microscope and scanning electron microscopy suggests an otherwise complex hydrovolcanic and hydrothermal origin. This paper describes characteristics of a particular type of the shales, composed of fine-grained detrital minerals and lithic grains. Some of them are orthopyroxene, calcite, peralkaline feldspars, and analcime that are interpreted as derived from peralkaline-alkaline carbonatite, pyroxenite, analcime phonolite, and andesite, whereas others are quartz, dolomite, ankerite, serpentine, and calcite that were precipitated from syndepositional or penecontemporary hydrothermal fluids. Grain size ranges from 0.001 to 2 mm, mostly 0.01-0.1 mm. Well-developed laminae are mostly 0.5-3 mm thick and alternate with tuffaceous dolomicrite. The rocks are interpreted as sublacustrine hydrovolcanic deposits, which had been altered by syndepositional hydrothermal fluids. The interpretation is substantiated by abundant cone-shaped stratigraphic buildups on seismic sections in the basin. This study shows an ancient example of volcanic-hydrothermal deposits in a rift basin.

  1. Micro-Raman spectroscopy and μ-XRF in the investigation of ancient glass beads from the archaeological sites, eastern Taiwan

    NASA Astrophysics Data System (ADS)

    San Liou, Ying; Liu, Yi Chang

    2017-04-01

    Ancient glass beads with different colors, shapes, and stylistics unearthed from the archaeological sites of eastern Taiwan, dating back to approximately 1850-310 BP, have been investigated. It is generally known that glass bead is alien to invade into Taiwan along with metal ware, glass, agate, etc. since the Metal Age of Taiwan. Nevertheless, souring provenance and trade routes still remain controversial. Micro-Raman spectroscopy and μ-XRF have been applied on fifty-six ancient glass beads to reveal the mineralogical and chemical compositions and to help decipher the raw materials used and souring provenance. Micro-Raman measurements indicate the presence of hematite, zincite, siderite, sphalerite, lead tin yellow type II, quartz, feldspar, anatase, rutite, ankerite, graphite, calcite, etc. Among them, hematite, zincite, siderite, sphalerite, lead tin yellow type II, and rutile were found to be colorants/opacifiers. Moreover, crystalline phases such as lead tin yellow type II (PbSn1-xSixO3), zincite (ZnO), tricalcium diphosphate (Ca2(PO4)2), sphalerite ((Zn, Fe)S) and ankerite (Ca(Fe, Mg, Mn)(CO3)2) were detected in ancient glass beads unearthed from Taiwan for the first time. The chemical results obtained by μXRF show SiO2, Al2O3, Na2O, K2O, MgO, CaO, and PbO as the most abundant oxides. Na2O, K2O, Al2O3, MgO, and PbO could be the main/minor fluxes and colorants. In general, results of mineralogical and chemical analyses are compatible. According to chemical results, ancient glass beads can be classified as mineral soda alumina glass (m-Na-Al glass), soda plant ash glass (v-Na-Ca glass), lead silicate glass, and some less well known types. Mineral soda alumina and soda plant ash glass beads, as well as lead silicate glass beads are generally believed to be the distinct phases of production and exchange in Southeast Asia and China, respectively. In terms of chronology of glass bead, beads excavated from sites of 1850-930 BP are mineral soda alumina glass (m-Na-Al glass) and soda plant ash glass (v-Na-Ca glass). On the other hand, beads from sites of <930 BP are belonging to lead silicate glass. It is indicated that the souring provenance of ancient beads of eastern Taiwan is probably a multiple sources, i.e., in earlier time, glass beads were brought into Taiwan through the maritime exchange and/or trade activities between Taiwan and Southeast Asia; at the later period, lead silicate glass beads were imported from China. However, some mineral soda alumina and soda plant ash glass beads were found in a later period, it might be attributed to glass beads reuse or trade route between Taiwan and Southeast Asia is successive since ca. 1850 BP.

  2. The Raman spectrum of Ca-Mg-Fe carbonates; Applications in geobiology

    NASA Astrophysics Data System (ADS)

    van Zuilen, M. A.; Rividi, N.; Ménez, B.; Philippot, P.

    2012-04-01

    Carbonates form a very important mineral group in geobiological studies. They are a common mineral matrix for putative carbonaceous microfossils in Archean greenstone belts, form an important chemical deposit in seafloor hydrothermal systems, and are a common product in biomineralization processes. In many geobiological studies there is a specific need for simple characterization of carbonate composition while avoiding complex sample preparation or sample destruction. Raman spectroscopy is a highly versatile non-destructive technique enabling in-situ characterization of minerals and carbonaceous materials. It can be combined with confocal microscopy enabling high-resolution Raman mapping of entire rock thin sections, or can be integrated in submersibles and potentially Mars-rovers for direct field-based mineral identification. It is thus important that well-established spectral databases exist which enable unambiguous identification of a wide variety of carbonate minerals. The most common carbonates in the Ca-Mg-Fe system include the CaCO3 polymorphs calcite, aragonite, and vaterite, as well as the solid solutions CaMg(CO3)2-CaFe(CO3)2 (dolomite-ankerite) and MgCO3-FeCO3 (magnesite-siderite). Although various carbonate end-members have been studied exhaustively by Raman spectroscopy, a simple protocol for rapid distinction of various carbonate solid solutions is still lacking. Here we present a detailed study of Raman shifts in various carbonate standards of known composition in the Ca-Mg-Fe system. Carbonates with rhombohedral symmetry display a Raman spectrum with six characteristic vibrational modes - four of these represent vibrations within the (CO3)2- unit and two represent external vibrations of the crystal lattice. We show that Raman band shifts of internal mode 2ν2 (range 1725-1765 cm-1), and external modes T (range 170-215 cm-1) and L (range 285-330 cm-1) for siderite-magnesite and ankerite-dolomite solid solutions display distinct and well defined positive correlations with Mg number (Mg/Mg+Fe+Mn+Ca). Raman shifts calibrated as a function of Mg number were used in turn to evaluate the chemical composition of natural carbonate samples. In particular it is shown that detailed micron-resolution Raman maps can be generated of carbonate crystal-zonation in hydrothermally altered sedimentary deposits from Archean greenstone belts. Large spectral-range analysis (140-2000 cm-1) in static-mode (centered at 1150 cm-1) allows for combined Raman mapping of both carbonate-composition (2ν2, T, L modes) as well as kerogen structural ordering (D1-D4 and G modes in the range 1100-1700 cm-1), and therefore allows for simultaneous characterization of putative organic microfossils and associated carbonate matrix in metamorphosed Archean rock samples. Finally, it will be shown that these carbonate solid solutions can be distinguished from other end-member carbonates such as calcite, vaterite and the orthorhombic polymorph aragonite.

  3. Distribution and Characteristics of Seafloor Seepage Features in the Active Margin Offshore of SW Taiwan

    NASA Astrophysics Data System (ADS)

    Chen, T. T.; Hsu, H. H.; Liu, C. S.; Su, C. C.; Paull, C. K.; Chen, Y. H.; Caress, D. W.; Gwiazda, R.; Lundsten, E. M.

    2017-12-01

    In the active margin offshore of southwest (SW) Taiwan, west-vergent imbricated thrusts, folds and dipping strata are the main structural features. This is also the area where gas hydrates are widely distributed beneath the seafloor. Fluids from deep strata may migrate upwards along porous dipping layers or faults and then vent out to form seafloor seepage features in many of the gas hydrate prospects. A joint survey was conducted in May 2017 using MBARI mapping AUV and miniROV to investigate the seafloor seepage features. Numerous comet-shaped depressions (CSD) are mapped along flanks of several anticlinal ridges, and four carbonate mounds around CSD are observed from the ultra-high-resolution (1-m lateral resolution) bathymetry data collected by AUV. Samples of the carbonate mounds were collected by the mini-ROV, and their mineral compositions contain dolomite and ankerite. The AUV collected chirp sonar profiles and previously collected surface ship multichannel seismic reflection profiles across these seafloor features show that potential fluid migration pathways connect free gas trapped below the base of gas hydrate stability zone and the seafloor in the vicinity of these features. Our study suggests that the CSD could be an indicator of seafloor seepage and may be distribution widely in the active margin setting.

  4. The Laramide Caborca orogenic gold belt of northwestern Sonora, Mexico; white mica 40Ar/39Ar geochronology from gold-rich quartz veins

    USGS Publications Warehouse

    Izaguirre, Aldo; Kunk, Michael J.; Iriondo, Alexander; McAleer, Ryan J.; Caballero-Martinez, Juan Antonio; Espinosa-Arámburu, Enrique

    2016-02-12

    The COGB is approximately 600 kilometers long and 60 to 80 km wide, trends northwest, and extends from west-central Sonora to southern Arizona and California. The COGB contains mineralized gold-rich quartz veins that contain free gold associated with white mica (sericite), carbonate minerals (calcite and ankerite), and sulfides such as pyrite and galena. Limited geochronologic studies exist for parts of the COGB, and previous work was concentrated in mining districts. These previous studies recorded mineralization ages of approximately 70 to 40 Ma. Therefore, some workers proposed that the orogenic gold mineralization in the region occurred during a single pulse that was associated with the Laramide Orogeny that took place during the Cretaceous to early Eocene in the western margin of North America. However, the geochronologic dataset was quite limited, making any regional interpretations tenuous. Accordingly, one of the objectives of this geochronology study was to get a better representative sampling of the COGB in order to obtain a more complete record of the mineralization history. The 63 samples presented in this work are broadly distributed throughout the area of the COGB and allow us to better test the hypothesis that mineralization occurred in a single pulse.

  5. The Berriasian-Valanginian boundary interval based on calpionellids from the Taraises Formation, Cuencamé de Ceniceros, Durango, NW Mexico: Biostratigraphic, paleoecologic and paleobiogeographic significance

    NASA Astrophysics Data System (ADS)

    Omaña, Lourdes; González-Arreola, Celestina; Núñez-Useche, Fernando

    2017-12-01

    A section from the lower part of the Taraises Formation located in the central-east part of Durango State, northern Mexico was studied. The succession consists of a grey and reddish limestone interstratified with marl levels. The calcareous strata provide a microfossil assemblage that consists of calpionellids, planktonic and benthonic foraminifera, and radiolarians. Based on the first appearance of Calpionellites darderi the Berriasian-Valanginian boundary was defined for the first time from the Taraises Formation. Also, the zones and subzones of this interval were described, the Calpionellopsis Zone, Oblonga Subzone and Praecalpionellites murgeanui Subzone for the late Berriasian and the Calpionellites Zone, Darderi and Major Subzones for the early Valanginian. The paleoenvironmental changes in the studied section are documented from the microfaunal association and mineralogical composition. The abundant occurrence of radiolarians in the early Valanginian might suggest an increase in nutrient input. In addition, the presence of tiny barite crystals, ankerite, siderite and dolomite rhombs confirms high fertility, implying oxygen-depleted conditions that could be considered a prelude of the mid-Valanginian Weissert Event. The predominant wackestone texture along with the occurrence of calpionellids and planktonic foraminifera indicate a pelagic basin environment. The microfaunal association is characteristic of the Tethys Realm.

  6. Mineralogy and origin of atmospheric particles in the industrial area of Huelva (SW Spain)

    NASA Astrophysics Data System (ADS)

    Bernabé, J. M.; Carretero, M. I.; Galán, E.

    The mineralogy of atmospheric particles at the confluence of the Tinto and Odiel rivers, south of Huelva (a highly industrialized city in the SW Spain), was characterized in view to identify source origins. In spite of the small amount of sample collected, mineralogical characterization was performed by X-ray diffraction, polarized light microscopy and scanning electron microscopy with EDS analysis system, using an adequate sample preparation methodology. Sedimentable (SP) and aerosols particles were sampled an one-week basis every two months for one year. Quartz, calcite and feldspars were found to be the major minerals in both fractions, and phyllosilicates, dolomite and gypsum were also identified in lower content. Minor mineral particles included barite, apatite, sphalerite and pyrite. SEM studies revealed the additional presence of chalcopyrite in both SP and aerosols, and of chalcocite-covellite, halite and sylvite in the latter. Siderite, hematite and ankerite were only detected in the SP fraction. The concentrations of the previous minerals increased in summer by effect of the limited rain and the resulting scarcity of atmosphere washing. Non-mineral particles detected by SEM in SP and aerosol fractions included spherical, biological and compositionally complex particles. The main source of mineral particles was found to be the soil suspension in addition to the metallurgical and fertilizer production industries in the area.

  7. Evidence for long term deep CO2 confinement below thick Jurassic shales at Montmiral site (SE Basin of France)

    NASA Astrophysics Data System (ADS)

    Rubert, Y.; Ramboz, C.; Le Nindre, Y. M.; Lerouge, C.; Lescanne, M.

    2009-04-01

    Studies of natural CO2 analogues bring key information on the factors governing the long term (>1My) stability/instability of future anthropogenic CO2 storages. The main objective of this work is to trace the deep-origin CO2 migrations in fractures in the Montmiral CO2 deep natural occurrence (Valence Basin, SE France). The final objective is to document the reservoir feeding and the possible leakages through overlying series. The CO2 reservoir is hosted within a horst controlled by a N-S fault network. From the Triassic to Eocene, the Montmiral area was part of the South-East Basin of France. This period is marked by the Tethysian extension phase (Triassic-Cretaceous) followed by the closure of the basin which culminated during the Pyrenean compressive phase (Eocene). Then, from the late Eocene, the Valence Basin was individualised in particular during the Oligocene E-W rifting affecting the West of Europe. Finally the eastern border of the Basin was overthrusted by Mesozoic formations during the Alpine orogenesis (Miocene). The Montmiral CO2 reservoir is intersected by the currently productive V.Mo.2 well, drilled through Miocene to Triassic sedimentary formations, and reaching the Palaeozoic substratum at a depth of 2771 meters. The CO2 is trapped below a depth of 2340 meters, at the base of sandy, evaporitic and calcareous formations (2340-2771m), Triassic to Sinemurian in age. These units are overlain by a 575 m-thick Domerian to Oxfordian marly sequence which seals the CO2 reservoir. Above these marls, calcareous strata (1792-1095 m), Oxfordian to Cretaceous in age, and sandy clayey formations (1095-0 m), Oligocene and Miocene in age, are deposited. The various stratigraphic levels from the Miocene to the basement were cored over a total length of ~100m. From bottom to top, three lithological units, which exhibit well characterised contrasted diagenetic evolution, record various stages and effects of the CO2 migration: - Lower unit: Palaeozoic metamorphic basement; - Middle unit: Triassic-Liassic reservoir; - Upper unit: late Jurassic to Cretaceous. The middle unit (reservoir) and the upper unit are separated by the thick, tight seal, Domerian to Oxfordian in age. The definition of these lithological units was made using combined petrographic techniques (cathodoluminescence CL, fluorescence, Raman spectroscopy, crushing tests), geochemical techniques (C and O isotopes) and microthermometry. Lower unit: Paleozoïc basement - In the metamorphic basement, aquo-carbonic and CO2-dominant fluids are trapped as primary fluid inclusions in hydrothermal barite and fluoroapatite, and as secondary fluid inclusions in extensionnal microcracks crosscutting metamorphic quartz. All these fluids, trapped in the two-phase stability field, indicate firstly a limited phase separation at 300°C and 400-500 bars evolving toward wider CO2-H2O unmixing at 200°C and 200 bars. Basinal saline brines (10 and 15-25 wt % eq. NaCl and 70

  8. Palaeoredox indicators from the organic-rich Messinian early post-evaporitic deposits of the Apennines (Central Italy)

    NASA Astrophysics Data System (ADS)

    Sampalmieri, G.; Iadanza, A.; Cipollari, P.; Cosentino, D.; Lo Mastro, S.

    2009-04-01

    Bottom redox conditions in marine and lacustrine ancient basins are often inferred by the occurrence of peculiar sedimentological structures and microfaunal assemblages. The co-occurrence, in such environments, of authigenic uranium, framboidal pyrite, barite and Fe-Mn nodules and encrustations, provides a good constraint for palaeo reconstructions. Authigenic uranium is a common constituent of hydrocarbon source rocks: it forms at the sediment-water interface under oxygen-deficient conditions and accumulates together with organic matter (OM). Its precipitation is triggered by the reduction of the soluble U6+ion in seawater to insoluble U4+. With respect to black shales, uranium content has even been used to estimate the TOC. Also authigenic pyrite forms under anoxic conditions and replaces organic matter: 1) the increase in pyrite content and in organic matter are directly correlated; 2) the size distribution of framboidal pyrite (consistent with sulphate-reducing bacterial activity) is considered a measure of redox conditions within the sediment. Barite is an authigenic mineral related to Corg content, since its organic precipitation is triggered by sulphate-reduction processes occurring in decaying OM-bearing microenvironments. Finally, also Fe-Mn oxyhydroxide are typical indicators of redox conditions. About 6 My ago the Mediterranean Sea underwent a giant event of concentration referred to as Messinian Salinity Crisis, which can be roughly subdivided into an evaporitic and a post evaporitic phase. The post evaporitic phase (p-ev; 5.61-5.33 Ma) developed in a context of humid conditions and can be further distinguished into two steps: p-ev1 (early post evaporitic phase) and p-ev2 (late post evaporitic phase). Previous works focused on pev2, which is interpreted to represent the establishment of brackish water conditions (Lago-Mare biofacies). In other respects, the palaeoenvironment of p-ev1 deposits, mostly represented by resedimented evaporitic deposits or barren laminated sediments, hasn't been thoroughly clarified yet. The aim of the present study, dealing with messinian p-ev1 deposits from Marche and Maiella successions, is to provide more details in the definition of the environment developed during the early post-evaporitic phase. Since the lamination and the absence of benthic fauna suggest the occurrence of anoxic conditions, the following indirect proxies for the detection of organic matter have been investigated: 1) sedimentary fabric and microfacies; 2) framboidal pyrite size distribution; 3) natural radioactivity (authigenic uranium values, Th/U ratios). Natural radioactivity has been achieved through gamma spectrometry, with field and laboratory specific techniques. In the Maccarone section (Marche region), p-ev1 deposits are constituted by: barren greyish shales; laminated black shales interbedded with calcitic and ankeritic horizons; thin intercalations of sandstones. Organic-matter and framboidal pyrite commonly occur. Size analysis of framboids populations yielded a mean diameter of 4÷8 m, typical of disaerobic facies. Microfacies analysis yielded also the presence of crystals aggregates of barite, up to 50 m in size, and of isolated detrital (silicilastic) crystals. Without considering γ-ray values of the volcaniclastic layer (52-65 Cps) occurring within the p-ev1 interval, black shales horizons revealed the maximum natural radioactivity (NRD of about 50 Cps) recorded inthe studied section. Lower γ-activity characterizes the calcitic layers (i.e. "Colombacci") and the ankerites. Field NRD spectra acquired on different lithologies, showed variable contributions of 238U, 232Th and 40K. Both the blue-greyish shales and the black shales are characterized by total NRD related to the three main radioelements: 40K is associated to abundant 238U content (Thppm/Uppm 1). The 238U content is primarily referable to processes of organic matter enrichment (authigenic uranium) and secondarily to the input of detrital grains. In contrast, 40K and 232Th are entirely ascribed to the clastic fraction. P-ev1 deposits from Maiella section consist of thinly-laminated grey-brownish pelites, enclosing carbonatic lenses and interrupted horizons. The pelitic fraction contains Fe-Mn-Ni encrustated micronodules. The carbonate portion is made up of locally brecciated calcitic limestones, associated with calcitic concretions and discontinuous laminae. Traces of organic matter and bitumen have been observed in thin section. Framboidal pyrite occurs both as single element and as aggregate, reaching dimensions up to about 10 m. Barite and celestite occur as well. NRD measurements yielded high values of radioactivity both in carbonates (20-63 Cps) and in terrigenous sediments (21-70 Cps). Limestones NRD-spectra showed a 238U-dominant (5 ppm in content) radioactivity. 238U is totally referable to an authigenic origin, since the γ-activity of limestones is devoid of contributions from 40K and 232Th (proxies for the detritic fraction). In the latest Messinian frame, authigenic uranium, barite, ankerite, Fe-Mn oxyhydroxide and framboidal pyrite indicate strongly palaeoredox conditions (from disaerobic to fully anoxic). In particular, with respect to NRD data, this peculiar environment is confirmed by the Th/U ratio, mostly

  9. Mineralisation footprints and regional timing of the world-class Siguiri orogenic gold district (Guinea, West Africa)

    NASA Astrophysics Data System (ADS)

    Lebrun, Erwann; Thébaud, Nicolas; Miller, John; Roberts, Malcolm; Evans, Noreen

    2017-04-01

    Siguiri is a world-class orogenic gold district hosted in the weakly metamorphosed Upper Birimian to Lower Tarkwa Group sedimentary rocks of the Siguiri Basin (Guinea). The district is characterised by a protracted deformation history associated with four main deformation events: D1S is a N-S compression; D2S is an E-W compression progressively evolving into an early-D3S transpression and then into a late-D3S NNW-SSE transtension and D4S is a NE-SW compression. Field observations, petrography and geochemistry at three key deposits of the Siguiri district (Bidini, Sintroko PB1 and Kosise) suggest a polyphase hydrothermal history that can be subdivided into four hydrothermal events. The first hydrothermal event was associated with the development of barren bedding-parallel and en-echelon V2S quartz-dominated-(pyrite) veins. The second hydrothermal event is characterised by the development of V3A pyrite-ankerite veins late during D3S. Laser ablation-ICP-MS data show that this vein set contains high gold contents of up to 43.3 ppm, in substitution in pyrite crystal lattice, representing a minor first gold mineralisation event. The third and most prominently developed hydrothermal event is late D3S and represents the second and principal gold mineralisation event. This mineralisation event led to two distinct mineralisation textures. The first texture is best exposed in the Kosise deposit and is characterised by gold-bearing quartz-ankerite-arsenopyrite conjugate V3B veins. Although the bulk of the gold is hosted in native gold grains in V3B veins, LA-ICP-MS analyses show that gold also substitutes in the arsenopyrite crystal lattice (up to 55.5 ppm). The second mineralisation texture is best expressed in the Sanu Tinti deposit and consists of disseminated barren pyrite hosted in a polymict conglomerate. The second and third hydrothermal events are both structurally controlled by a series of early-D3S N-S, NE-SW, WNW-ESE and E-W sub-vertical incipient structures expressed as fracture zones of higher V3S vein density. A composite geochemical cross section across fracture zones from the Kosise deposit indicates that gold mineralisation in the Siguiri district is associated with enrichments in Ag, Au, As, Bi, Co, Mo, (Sb), S, Te and W relative to background. Geochemical variations associated with the ore shoots in the Siguiri district are consistent with petrographic observations and highlight an albite-carbonate-sulphide-sericite alteration. The fourth and last hydrothermal event is associated with the development of a late penetrative S4S cleavage during D4S deformation, which overprints all pre-existing hydrothermal features and is associated with the deposition of free gold, chalcopyrite and galena along fractures in V3A pyrite and V3B pyrite and arsenopyrite. Mineralogical and geochemical footprints as well as timing of the gold-mineralising events in the Siguiri district, when compared with other deposits of the West African Craton, highlight the synchronicity of gold mineralisation in Siguiri (syn-D3S and syn-D4S events) with other similar events in this part of the craton, such as the early Au-Sb-Bi-(Te-W) mineralisation at the Morila deposit in Southeast Mali. Our results support the hypothesis that late Eburnean-age gold mineralisation in the Siguiri district and in the West African Craton as a whole was polyphase.

  10. Crystallization process of zircon and fergusonite during hydrothermal alteration in Nechalacho REE deposit, Thor Lake, Canada

    NASA Astrophysics Data System (ADS)

    Hoshino, M.; Watanabe, Y.; Murakami, H.; Kon, Y.; Tsunematsu, M.

    2012-04-01

    The core samples of two drill holes, which penetrate sub-horizontal mineralized horizons at Nechalacho REE deposit in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify magmatic and hydrothermal processes that enriched HFSE (e.g. Zr, Nb, Y and REE). Zircon is the most common REE minerals in Nechalacho REE deposit. The zircon is divided into five types as follows: Type-1 zircon occurs as single grain in phlogopite and the chondrite-normalized REE pattern is characterized by a steeply-rising slope from the LREE to the HREE with a positive Ce-anomaly and negative Eu-anomaly. This chemical characteristic is similar to that of igneous zircon. Type-2 zircon consists of HREE-rich magmatic porous core and LREE-Nb-F-rich hydrothermal rim. This type zircon is mostly included in phlogopite and fluorite, and occasionally in microcline. Type-3 zircon is characterized by euhedral to anhedral crystal, occurring in a complex intergrowth with REE fluorocarbonates. Type-3 zircons have high contents of REE, Nb and fluorine. Type-4 zircon consists of porous-core and -rim zones, but their chemical compositions are similar to each other. This type zircon is a subhedral crystal rimmed by fergusonite. Type-5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircons are filled by fergusonite. Type-4 and -5 zircons show low REE and Nb contents. Occurrences of these five types of zircon are different according to the depth and degree of the alteration by hydrothermal solutions rich in F- and CO3 of the two drill holes, which permit a model for evolution of the zircon crystallization in Nechalacho REE deposit as follows: (1) type-1 (single magmatic zircon) is formed in miaskitic syenite. (2) LREE-Nb-F-rich hydrothermal zircon formed around HREE-rich magmatic zircon (type-2 zircon); (3) type-3 zircon crystallized thorough F and CO3-rich hydrothermal alteration of type-2 zircon which formed the complex intergrowth with REE fluorocarbonates; (4) the CO3-rich hydrothermal fluid corroded type-3, forming Nb-REE-poor zircons (type-3). Niobium and REE was no longer stable in the zircon structure and crystallized as fergusonite around the REE-Nb-leached zircon (type-4); (5) type-5 zircons are formed from more CO3-rich hydrothermal alteration of type-3 zircon. Therefore, type-4 and -5 zircons are often included in ankerite. Type 3-5 zircons at Nechalacho REE deposit were formed by leaching and/or dissolution of type-2 zircon in the presence of F- and/or CO3-rich hydrothermal fluid. The above mineral association indicates that three hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (1) F-rich hydrothermal stage caused the crystallization of REE-Nb-rich zircon (type-2 rim and type-3), with abundant formation of phlogophite and fluorite, (2) F-CO3-rich hydrothermal stage led to the replacement of a part of REE-Nb-F-rich zircon by REE fluorocarbonate and (3) hydrothermal stage rich in CO3 resulted in crystallization of REE-Nb-F-poor zircon and fergusonite, with ankerite. Increases of HFSE contents, REE-Nb-F-poor zircon (type-4 and -5) and fergusonite contents during progress of hydrothermal alteration show that REE and Nb in hydrothermal fluid in the Nechalacho REE deposit were finally concentrated into fergusonite by way of zircon.

  11. Preliminary reactive geochemical transport simulation study on CO2 geological sequestration at the Changhua Coastal Industrial Park Site, Taiwan

    NASA Astrophysics Data System (ADS)

    Sung, R.; Li, M.

    2013-12-01

    Mineral trapping by precipitated carbonate minerals is one of critical mechanisms for successful long-term geological sequestration (CGS) in deep saline aquifer. Aquifer acidification induced by the increase of carbonic acid (H2CO3) and bicarbonate ions (HCO3-) as the dissolution of injected CO2 may induce the dissolution of minerals and hinder the effectiveness of cap rock causing potential risk of CO2 leakage. Numerical assessments require capabilities to simulate complicated interactions of thermal, hydrological, geochemical multiphase processes. In this study, we utilized TOUGHREACT model to demonstrate a series of CGS simulations and assessments of (1) time evolution of aquifer responses, (2) migration distance and spatial distribution of CO2 plume, (3) effects of CO2-saline-mineral interactions, and (4) CO2 trapping components at the Changhua Costal Industrial Park (CCIP) Site, Taiwan. The CCIP Site is located at the Southern Taishi Basin with sloping and layered heterogeneous formations. At this preliminary phase, detailed information of mineralogical composition of reservoir formation and chemical composition of formation water are difficult to obtain. Mineralogical composition of sedimentary rocks and chemical compositions of formation water for CGS in deep saline aquifer from literatures (e.g. Xu et al., 2004; Marini, 2006) were adopted. CGS simulations were assumed with a constant CO2 injection rate of 1 Mt/yr at the first 50 years. Hydrogeological settings included porosities of 0.103 for shale, 0.141 for interbedding sandstone and shale, and 0.179 for sandstone; initial pore pressure distributions of 24.5 MPa to 28.7 MPa, an ambient temperature of 70°C, and 0.5 M of NaCl in aqueous solution. Mineral compositions were modified from Xu et al. (2006) to include calcite (1.9 vol. % of solid), quartz (57.9 %), kaolinite (2.0 %), illite (1.0 %), oligoclase (19.8 %), Na-smectite (3.9 %), K-feldspar (8.2 %), chlorite (4.6 %), and hematite (0.5 %) and were assumed throughout the simulation domain. Comparisons among simulated results with different mesh systems of nested meshes and non-nested meshes and considerations of multiphase reactive transport and physical transport were demonstrated in this study. Preliminary results of injection CO2 for 50 years are: (1) about 7 wt.% of injected CO2 was trapped as carbonate minerals mainly as ankerite; (2) porosities were decreased by 0.014 % and increased by 0.102 % at the injection point and beneath the cap rock, respectively, and were subsequently decreased with time due to minerals precipitation mostly as illite and ankerite; (3) differences of simulated aquifer responses between reactive transport and physical transport were insignificant; and (4) projected CO2 plumes with the nested meshes was smaller than those by the non-nested meshes after cease of CO2 injection. Keywords: CO2-Saline-Mineral Interaction, Reactive Geochemical Transport, TOUGHREACT, Mineral Trapping Assessment, Changhua Costal Industrial Park Site, Taiwan Reference: Marini, L., 2006, Geological Sequestration of Carbon Dioxide, Volume 11: Thermodynamics, Kinetics, and Reaction Path Modeling, Elsevier Science, pp.470. Xu, T., J. A. Apps and K. Pruess, 2004, Numerical simulation of CO2 disposal by mineral trapping in deep aquifers, Applied Geochemistry, Vol. 19:917-936.

  12. Aragonite-calcite precipitation in vertical fractures of the "Erzberg" siderite deposit (Austria): Hydrogeochemical and neotectonic implications

    NASA Astrophysics Data System (ADS)

    Boch, Ronny; Wang, Xianfeng; Kluge, Tobias; Kurz, Walter; Leis, Albrecht; Lin, Ke; Pluch, Hannes; Mittermayr, Florian; Dietzel, Martin

    2017-04-01

    The ore deposit "Erzberg" represents the worldwide largest FeCO3 occurrence and is amongst Austria's most prominent geological places due to its historic, economic and scientific value. The iron-ore (siderite/ankerite) bearing Devonian carbonates of the open pit mine locally host sequential aragonite-calcite precipitates infilling vertical fractures. These typically laminated carbonates are referred to as erzbergite in mineral collections. To study their formation conditions we recovered samples on-site, i.e. from the rare veins being cm to dm in horizontal and tenths of meters in vertical extension. Additionally, samples from our university collection and private collectors were investigated. Some of the fractures filled with aragonite/calcite further exhibit cataclastic sediments, damage zones and slickenside striations. Modern water samples were collected from fractures currently accessible to conduct hydrochemical analyses and modeling. Selected precipitates were analyzed applying microscopic techniques, XRD, electron microprobe elemental mapping, stable and clumped isotopes, and 238U-234U-230Th radiometric dating. Erzbergite veins show either uni- or bidirectional growth, i.e. on one or both fracture/fault planes toward complete infilling depending on vadose water flow. The laminated precipitates are dominated by aragonite relative to pristine as well as partially diagenetic (Mg)-calcite. Intercalated and recurrent brownish Fe-rich layers consisting of goethite, quartz, muscovite are probably of detrital origin. Stable C and O isotopes of the precipitates reveal pronounced spatiotemporal variations in which low δ18O values (-10.4 to -5.1 ‰ VPDB) reflect a meteoric origin and low temperatures of the erzbergite depositing solutions. Carbonate clumped isotope measurements verify formation temperatures ≤25 °C. High δ13C values (-0.7 to +6.8 ‰ VPDB) of the precipitates indicate an origin from dissolution of local ankerite and limestone, without a significant proportion from soil CO2. Prominently high δ13C in DIC (≤+3.8 ‰) were also measured in modern fracture waters next to elevated sulfate (up to 226 mg/l) and high total dissolved solid contents (up to 1273 mg/l). These results suggest intense water-rock interaction based on sulfide oxidation and sulfuric acid evolution providing an efficient mechanism for host rock dissolution, mobilization and typically rapid aragonite-calcite mineralization. Sulfide accessories are widespread at Erzberg and the brownish Fe-rich layers within erzbergite could be explained by corrosion of Fe-sulfides and/or Fe-carbonates. The aragonite-calcite lamination is interpreted as an event lamination (not annual), i.e. variable aqueous Mg2+/Ca2+ ratios and CaCO3 supersaturation states triggering the polymorphism. U-Th analyses yielded surprisingly young ages for erzbergite dated so far, i.e. late Pleistocene and mostly younger than the last glacial maximum. A 4 cm thick sample composed of aragonite exclusively and filling a tenths of meters extending fracture formed 10.4 ±0.2 (sample base, initiation) to 1.03 ±0.04 kyr BP (top, fracture filled). Another 25 cm laminated aragonite-calcite precipitate covers 14.2 ±0.2 to 5.0 ±0.2 kyr. Thus, the precipitates support geologically young and rather short time intervals of infilling and we consider it unlikely that the fractures are much older. An intimate connection with neotectonic activity entailing new vadose water flow routes and fresh reaction surfaces in fractures would be in accordance with our hydrogeochemical and field observations.

  13. Hydrothermal karst and associated breccias in Neoproterozoic limestone from the Barker-Villa Cacique area (Tandilia belt), Argentina

    NASA Astrophysics Data System (ADS)

    Dristas, Jorge A.; Martínez, Juan C.; van den Kerkhof, Alfons M.; Massonne, Hans-Joachim; Theye, Thomas; Frisicale, María C.; Gregori, Daniel A.

    2017-07-01

    In the Barker-Villa Cacique area (Tandilia belt), remarkable megabreccias, limestone breccias and phosphate-bearing breccias hosted in black limestone and along the contact with the upper section of the sedimentary succession are exposed. These rocks are the result of extensive hydrothermal alteration of the original micritic limestone and other fine-grained clastic sediments. Typical alteration minerals are sericite, chlorite, interstratified chlorite/K-white mica, kaolinite, dickite, pyrite, chalcopyrite, goethite, quartz, calcite, Fe-calcite, dolomite, ankerite, fluor-apatite, barite and aluminium-phosphate-sulfate (APS) minerals. Quartz and calcite cements from hydraulic breccias in the limestone contain low-salinity aqueous fluid inclusions. Corresponding homogenization temperatures display 200-220 °C and 110-140 °C in hydrothermal quartz, and 130-150 °C in late calcite cement. Carbon and oxygen stable isotope analyses of carbonates from the Loma Negra quarry (LNQ) support the major role of hydrothermal activity. A significant difference was found between δ18Ocar values from unaltered micritic limestone (ca. 23.8‰ SMOW) and secondary calcite (ca. 18.5‰ SMOW). The lower δ18Ocar values are interpreted as a result of calcite precipitation from hot hydrothermal fluids. At a late stage, the hydrothermal fluid containing H2S mixed with descending and oxidizing meteoric waters. Circulation of the ensuing acid fluids resulted in the partly dissolution and collapse brecciation of the Loma Negra Formation. The hydrothermal stage can be tentatively dated ca. 590-620 Ma corresponding to the Brasiliano orogeny.

  14. 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.

  15. New data on carbonatites of the Il'mensky-Vishnevogorsky alkaline complex, the southern Urals, Russia

    NASA Astrophysics Data System (ADS)

    Nedosekova, I. L.

    2007-04-01

    Carbonatites that are hosted in metamorphosed ultramafic massifs in the roof of miaskite intrusions of the Il’mensky-Vishnevogorsky alkaline complex are considered. Carbonatites have been revealed in the Buldym, Khaldikha, Spirikha, and Kagan massifs. The geological setting, structure of carbonatite bodies, distribution of accessory rare-metal mineralization, typomorphism of rock-forming minerals, geochemistry, and Sr and Nd isotopic compositions are discussed. Dolomite-calcite carbonatites hosted in ultramafic rocks contain tetraferriphlogopite, richterite, accessory zircon, apatite, magnetite, ilmenite, pyrrhotite, pyrite, and pyrochlore. According to geothermometric data and the composition of rock-forming minerals, the dolomite-calcite carbonatites were formed under K-feldspar-calcite, albite-calcite, and amphibole-dolomite-calcite facies conditions at 575-300°C. The Buldym pyrochlore deposit is related to carbonatites of these facies. In addition, dolomite carbonatites with accessory Nb and REE mineralization (monazite, aeschynite, allanite, REE-pyrochlore, and columbite) are hosted in ultramafic massifs. The dolomite carbonatites were formed under chlorite-sericite-ankerite facies conditions at 300-200°C. The Spirikha REE deposit is related to dolomite carbonatite and alkaline metasomatic rocks. It has been established that carbonatites hosted in ultramafic rocks are characterized by high Sr, Ba, and LREE contents and variable Nb, Zr, Ti, V, and Th contents similar to the geochemical attributes of calcio-and magnesiocarbonatites. The low initial 87Sr/86Sr = 0.7044-0.7045 and ɛNd ranging from 0.65 to -3.3 testify to their derivation from a deep mantle source of EM1 type.

  16. Exploration for gold mineralization in the Arabo Nubian Shield: Using remote sensing Approach

    NASA Astrophysics Data System (ADS)

    Ramadan, Talaat

    2013-04-01

    In the southern part of the Eastern Desert of Egypt, Landsat Thematic Mapper (ETM+) data and fieldwork was combined with mineralogical and geochemical investigations in order to detect and characterize alteration zones within Pan-African rocks. The processing of Landsat ETM+ data using ratioing (bands 5/7,5/1,4/3 in Red, Green, Blue) showed two different types of alteration zones (type l and 2). Type 1 is close to the ophiolitic ultramafic rocks and type 2 is located within island-arc related metavolcanic rocks at the study areas. Both of these alteration zones are concordant with the main NW-SE structural trend. Mineralogical studies indicate that the alteration zones of type 1 consist mainly of calcite, ankerite, magnesite, dolomite and quartz. Chromian spinel, pyrite, and Ni-bearing sulphides (gersdorffite, pentlandite and polydymite) are the main ore minerals within this zone. Alteration zones of type 2 are strongly potassium-enriched and pyrophyllite, kaolinite, illite, gypsum and quartz occur. The brecciated quartz-veins associated with theses alteration zones consist of quartz, Fe-hydroxides, hematite and native gold. The gold content reaches up to 5 g/t in the alteration zone, while it extends up to 50 g/t in the quartz veins. This study presents a mineralogical characterization of such zones and demonstrates the utility of orbital remote sensing for finding unknown alteration zones in the Eastern Desert and other arid areas with similar host rock lithologies.

  17. Dissolution and secondary mineral precipitation in basalts due to reactions with carbonic acid

    NASA Astrophysics Data System (ADS)

    Kanakiya, Shreya; Adam, Ludmila; Esteban, Lionel; Rowe, Michael C.; Shane, Phil

    2017-06-01

    One of the leading hydrothermal alteration processes in volcanic environments is when rock-forming minerals with high concentrations of iron, magnesium, and calcium react with CO2 and water to form carbonate minerals. This is used to the advantage of geologic sequestration of anthropogenic CO2. Here we experimentally investigate how mineral carbonation processes alter the rock microstructure due to CO2-water-rock interactions. In order to characterize these changes, CO2-water-rock alteration in Auckland Volcanic Field young basalts (less than 0.3 Ma) is studied before and after a 140 day reaction period. We investigate how whole core basalts with similar geochemistry but different porosity, permeability, pore geometry, and volcanic glass content alter due to CO2-water-rock reactions. Ankerite and aluminosilicate minerals precipitate as secondary phases in the pore space. However, rock dissolution mechanisms are found to dominate this secondary mineral precipitation resulting in an increase in porosity and decrease in rigidity of all samples. The basalt with the highest initial porosity and volcanic glass volume shows the most secondary mineral precipitation. At the same time, this sample exhibits the greatest increase in porosity and permeability, and a decrease in rock rigidity post reaction. For the measured samples, we observe a correlation between volcanic glass volume and rock porosity increase due to rock-fluid reactions. We believe this study can help understand the dynamic rock-fluid interactions when monitoring field scale CO2 sequestration projects in basalts.

  18. Diagenetic contrast of sandstones in hydrocarbon prospective Mesozoic rift basins (Ethiopia, UK, USA)

    NASA Astrophysics Data System (ADS)

    Wolela, A.

    2014-11-01

    Diagenetic studied in hydrocarbon-prospective Mesozoic rift basins were carried out in the Blue Nile Basin (Ethiopia), Ulster Basin (United Kingdom) and Hartford Basin (United States of America). Alluvial fan, single and amalgamated multistorey meandering and braided river, deep and shallow perennial lake, shallow ephemeral lake, aeolian and playa mud-flat are the prominent depositional environments. The studied sandstones exhibit red bed diagenesis. Source area geology, depositional environments, pore-water chemistry and circulation, tectonic setting and burial history controlled the diagenetic evolution. The diagenetic minerals include: facies-related minerals (calcrete and dolocrete), grain-coating clay minerals and/or hematite, quartz and feldspar overgrowths, carbonate cements, hematite, kaolinite, illite-smectite, smectite, illite, chlorite, actinolite, laumontite, pyrite and apatite. Diversity of diagenetic minerals and sequence of diagenetic alteration can be directly related to depositional environment and burial history of the basins. Variation in infiltrated clays, carbonate cements and clay minerals observed in the studied sandstones. The alluvial fan and fluviatile sandstones are dominated by kaolinite, illite calcite and ferroan calcite, whereas the playa and lacustrine sandstones are dominated by illite-smectite, smectite-chlorite, smectite, chlorite, dolomite ferroan dolomite and ankerite. Albite, pyrite and apatite are predominantly precipitated in lacustrine sandstones. Basaltic eruption in the basins modified mechanically infiltrated clays to authigenic clays. In all the studied sandstones, secondary porosity predominates over primary porosity. The oil emplacement inhabited clay authigenesis and generation of secondary porosity, whereas authigenesis of quartz, pyrite and apatite continued after oil emplacement.

  19. Mineral dissolution and precipitation during CO 2 injection at the Frio-I Brine Pilot: Geochemical modeling and uncertainty analysis

    DOE PAGES

    Ilgen, A. G.; Cygan, R. T.

    2015-12-07

    During the Frio-I Brine Pilot CO 2 injection experiment in 2004, distinct geochemical changes in response to the injection of 1600 tons of CO 2 were recorded in samples collected from the monitoring well. Previous geochemical modeling studies have considered dissolution of calcite and iron oxyhydroxides, or release of adsorbed iron, as the most likely sources of the increased ion concentrations. We explore in this modeling study possible alternative sources of the increasing calcium and iron, based on the data from the detailed petrographic characterization of the Upper Frio Formation “C”. Particularly, we evaluate whether dissolution of pyrite andmore » oligoclase (anorthite component) can account for the observed geochemical changes. Due to kinetic limitations, dissolution of pyrite and anorthite cannot account for the increased iron and calcium concentrations on the time scale of the field test (10 days). However, dissolution of these minerals is contributing to carbonate and clay mineral precipitation on the longer time scales (1000 years). The one-dimensional reactive transport model predicts carbonate minerals, dolomite and ankerite, as well as clay minerals kaolinite, nontronite and montmorillonite, will precipitate in the Frio Formation “C” sandstone as the system progresses towards chemical equilibrium during a 1000-year period. Cumulative uncertainties associated with using different thermodynamic databases, activity correction models (Pitzer vs. B-dot), and extrapolating to reservoir temperature, are manifested in the difference in the predicted mineral phases. Furthermore, these models are consistent with regards to the total volume of mineral precipitation and porosity values which are predicted to within 0.002%.« less

  20. Mineralogy and source rock evaluation of the marine Oligo-Miocene sediments in some wells in the Nile Delta and North Sinai, Egypt

    NASA Astrophysics Data System (ADS)

    El sheikh, Hassan; Faris, Mahmoud; Shaker, Fatma; Kumral, Mustafa

    2016-06-01

    This paper aims to study the mineralogical composition and determine the petroleum potential of source rocks of the Oligocene-Miocene sequence in the Nile Delta and North Sinai districts. The studied interval in the five wells can be divided into five rock units arranged from the top to base; Qawasim, Sidi Salem, Kareem, Rudeis, and Qantara formations. The bulk rock mineralogy of the samples was investigated using X-Ray Diffraction technique (XRD). The results showed that the sediments of the Nile Delta area are characterized by the abundance of quartz and kaolinite with subordinate amounts of feldspars, calcite, gypsum, dolomite, and muscovite. On the other hand, the data of the bulk rock analysis at the North Sinai wells showed that kaolinite, quartz, feldspar and calcite are the main constituents associated with minor amounts of dolomite, gypsum, mica, zeolite, and ankerite. Based on the organic geochemical investigations (TOC and Rock-Eval pyrolysis analyses), all studied formations in both areas are thermally immature but in the Nile delta area, Qawasim, Sidi Salem and Qantara formations (El-Temsah-2 Well) are organically-rich and have a good petroleum potential (kerogen Type II-oil-prone), while Rudeis Formation is a poor petroleum potential source rock (kerogen Type III-gas-prone). In the North Sinai area, Qantara Formation has a poor petroleum potential (kerogen Type III-gas-prone) and Sidi Salem Formation (Bardawil-1 Well) is a good petroleum potential source rock (kerogen Type II-oil-prone).

  1. Chemical compositions and precipitation timing of basement carbonate vein from fossil spreading ridge of South China Sea

    NASA Astrophysics Data System (ADS)

    Ding, W.; Chen, Y.

    2016-12-01

    Eighteen calcium carbonate veins within the igneous basement recovered close to the fossil spreading ridge of the South China Sea during the Integrated Ocean Drilling Program (IODP) Expedition 349 were investigated. These carbonates are of primarily either calcite or aragonite, or some mixed aragonite and calcite, with rarely ankerite. The chemical (Ca, Mg, Sr, Mn, Fe) contents and isotopic (87Sr/86Sr, δ18O, δ18C) compositions of the veins were determined to study the evolving chemistry of hydrothermal fluids and to constrain the timing of vein formation. The carbonate δ18O values range from -5.0 to -0.2 ‰ PDB, indicating these are typical low temperature basement carbonates. Chemical analyses show distinct Mg/Ca and Sr/Ca ratios for aragonite and calcite. 87Sr/86Sr ratios show negative correlations with both the depth and δ18O-calculated formation temperature, and are independent of mineralogy with both aragonite and calcite, indicating more geochemically evolved carbonated have precipitated from warmer fluids. The hightest 87Sr/86Sr ratios of vein samples at each drill site are believed to reflect the contemporaneous seawater compositions when carbonates precipitated. No unambiguous precipitation ages can be constrained by correlating 87Sr/86Sr ratios with the global seawater Sr isotope evolution. However, based on correlations of vein chemical composition with depth and formation temperature, as well as the Neogene post-spreading magmatism, we hypothesize 10 Ma is a particular time favoring the formation of carbonate veins in our study area.

  2. Geochemistry of rare earth elements within waste rocks from the Montviel carbonatite deposit, Québec, Canada.

    PubMed

    Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Pelletier, Mia

    2018-04-01

    Several rare earth element (REE) mine projects around the world are currently at the feasibility stage. Unfortunately, few studies have evaluated the contamination potential of REE and their effects on the environment. In this project, the waste rocks from the carbonatites within the Montviel proterozoic alkaline intrusion (near Lebel-sur-Quévillon, Quebec, Canada) are assessed in this research. The mineralization is mainly constituted by light REE (LREE) fluorocarbonates (qaqarssukite-Ce, kukharenkoite-Ce), LREE carbonates (burbankite, Sr-Ba-Ca-REE, barytocalcite, strontianite, Ba-REE-carbonates), and phosphates (apatite, monazite). The gangue minerals are biotites, chlorite, albite, ankerite, siderite, and calcite. The SEM-EDS analyses show that (i) the majority of REE are associated with the fine fraction (< 106 μm), (ii) REE are mainly associated with carbonates, (iii) all analyzed minerals preferably contain LREE (La, Ce, Pr, Nd, Sm, Eu), (iv) the sum of LREE in each analyzed mineral varies between ~ 3 and 10 wt%, (v) the heavy REE (HREE) identified are Gd and Yb at < 0.4 wt%, and (vi) three groups of carbonate minerals were observed containing variable concentrations of Ca, Na, and F. Furthermore, the mineralogical composition of REE-bearing minerals, REE mobility, and REE speciation was investigated. The leachability and geochemical behavior of these REE-bearing mine wastes were tested using normalized kinetic testing (humidity cells). Leachate results displayed higher LREE concentrations, with decreasing shale-normalized patterns. Thermodynamical equilibrium calculations suggest that the precipitation of secondary REE minerals may control the REE mobility.

  3. Depositional systems and diagenesis of Travis Peak tight gas sandstone reservoirs, Sabine Uplift Area, Texas

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

    Fracasso, M.A.; Dutton, S.P.; Finley, R.J.

    The Travis Peak formation (lower Cretaceous) in the eastern East Texas basin is a fluvio-deltaic depositional system divided into large-scale facies packages: a middle sandstone-rich fluvial and delta-plain sequence that is gradationally overlain and underlain by a marine-influenced delta-fringe zone with a higher mudstone content. Domes and structural terraces on the west flank of the Sabine Uplift influenced deposition of Travis Peak sediments, and most Travis Peak gas production in this area is from thin sandstones (<25 ft(<7.6 m) thick) in the upper delta-fringe facies. The trapping mechanism is stratigraphic pinch-out of sandstones or porosity zones within sandstone, or both,more » on the flanks of structures. Detailed mapping of producing sandstone sequences in the uppermost upper delta-fringe on the western flank of the Bethany structure has delineated fluvial channelways, distributary or tidal channels, and barrier of distributary-mouth bars. Most Travis Peak gas production in the Bethany West area is from the bases of channel sandstones in a marine-influenced facies belt. Travis Peak sandstones in the eastern East Texas basin have undergone a complex series of diagenetic modifications. Precipitation of authigenic quartz, ankerite, dolomite, illite, and chlorite and the introduction of reservoir bitumen were the most important causes of occlusion of primary porosity and reduction of permeability. Permeability decreases with depth in the Travis Peak, which suggests that the diagenetic processes that caused extensive cementation and resultant low permeability throughout most of the formation operated less completely on sediments deposited near the top of the succession.« less

  4. Fluvial/lacustrine diagenesis: Significance for hydrocarbon production and entrapment in the carboniferous Albert Fm, Moncton basin, NB

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

    Noble, J.P.A.; Chowdhury, A.H.; Yu, H.

    1996-12-31

    The Carboniferous Horton Group Albert Formation sediments include lacustrine source-rock oil shales and fluvial porous reservoir sandstones. The petrography, stable isotopes, fluid inclusions, cathodoluminescence and mirror/trace element chemistry of these sandstones are used to establish the diagenetic history and controlling factors. Early diagenetic calcite, quartz and albite cements with minor chlorite and kaolinite are variably present and related to depositional mineralogy and lake levels winch controlled the porewater chemistry. Antitaxial veins occurring preferentially in shales are shown, from heavy {delta}C{sup 13} values and fluid inclusions, to be related to methanogenesis in overpressured zones at shallow depths. Later burial calcite andmore » extensive albitisation are related to mineral reactions during the phase of rapid subsidence at temperatures of 80{degrees} to 150{degrees} in the deepest segment of the basin, together with significant dissolution of carbonates and feldspars related mainly to organic acids generated by organic maturation processes. Mass balance calculations indicate that not enough organic matter was present to account for all the estimated secondary porosity and some evidence suggests that reactions between kaolinite and calcite/ankerite to produce chlorite, and mixed layer illite-smectite ordering reactions, produced significant secondary porosity. Burial history reconstructions and thermal modelling of the Albert Fm. sediments using Arrhenius type maturity models and reflectance and rock-eval data suggest locally variable maturation and reservoir production related to the locally different fault tectonic histories characteristic of strike-slip lacustrine segmented basins. The Horton depositional cycle was followed by major dextral transpression with local faulting and inversion and vein cementation.« less

  5. Fluvial/lacustrine diagenesis: Significance for hydrocarbon production and entrapment in the carboniferous Albert Fm, Moncton basin, NB

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

    Noble, J.P.A.; Chowdhury, A.H.; Yu, H.

    1996-01-01

    The Carboniferous Horton Group Albert Formation sediments include lacustrine source-rock oil shales and fluvial porous reservoir sandstones. The petrography, stable isotopes, fluid inclusions, cathodoluminescence and mirror/trace element chemistry of these sandstones are used to establish the diagenetic history and controlling factors. Early diagenetic calcite, quartz and albite cements with minor chlorite and kaolinite are variably present and related to depositional mineralogy and lake levels winch controlled the porewater chemistry. Antitaxial veins occurring preferentially in shales are shown, from heavy [delta]C[sup 13] values and fluid inclusions, to be related to methanogenesis in overpressured zones at shallow depths. Later burial calcite andmore » extensive albitisation are related to mineral reactions during the phase of rapid subsidence at temperatures of 80[degrees] to 150[degrees] in the deepest segment of the basin, together with significant dissolution of carbonates and feldspars related mainly to organic acids generated by organic maturation processes. Mass balance calculations indicate that not enough organic matter was present to account for all the estimated secondary porosity and some evidence suggests that reactions between kaolinite and calcite/ankerite to produce chlorite, and mixed layer illite-smectite ordering reactions, produced significant secondary porosity. Burial history reconstructions and thermal modelling of the Albert Fm. sediments using Arrhenius type maturity models and reflectance and rock-eval data suggest locally variable maturation and reservoir production related to the locally different fault tectonic histories characteristic of strike-slip lacustrine segmented basins. The Horton depositional cycle was followed by major dextral transpression with local faulting and inversion and vein cementation.« less

  6. Some chemical aspects of diagenetic carbonates from the Miocene of Sitakund, Bangladesh

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

    Akhter, S.H.; Chowdhury, S.Q.; Kandaker, N.I.

    1990-05-01

    A preliminary chemical and petrological study was done of the Miocene limestone and its comparison with surrounding and overlying marine shales. The material for these studies was obtained from the Miocene Surma sediments exposed in Sitakund region, Cluttagong, Bangladesh. These limestones occur in a predominantly marine shale sequence and show an apparent angular structural relationship with respect to the host marine shales. Three types of carbonates are recognized: banded limestone, dark laminated limestone, and argillaceous limestone. These are devoid of any skeletal remains and often show recrystallization phenomena. Carbonate mineral phases included calcite, aragonite, dolomite, and more rarely magnesite andmore » ankerite. Noncarbonate fraction shows quartz, although very fine grained, is intricately intergrown, indicating that it is at least recrystallized, if not authigenic. Petrographic study of these carbonates show a great variability in terms of texture and composition and suggest a complex multistep and presumably continuous diagenesis. Relatively high REE (rare earth elements) abundances in these carbonates are most likely due to diagenesis and incorporation of mobile REE from local detrital phases into diagenetic carbonates. The anomalously low abundances of cerium in all the carbonates indicates a predominantly marine source for the REE. Recrystallization of carbonate resulted in the extensive exchange of Sr and O between carbonate and diagenetic fluid, the latter being low in REE/Ca ratios. Associated marine shales have quite dissimilar trace-element signatures. This may reflect uncommon crustal sources of REE for the carbonates and clastics. The enrichment of Ni and Zn in marine shales are related to the proximality of local bedrock source areas and clay minerals in the marine sediments.« less

  7. Piedramuelle Limestone in the building heritage of Oviedo, Spain, and adjacent towns.

    NASA Astrophysics Data System (ADS)

    Cardenes Van den Eynde, Victor; Mateos, Felix Javier; Valdeon, Luis; Rojo, Araceli

    2017-04-01

    The Piedramuelle limestone has a very important representation in the building heritage of Oviedo, historical capital of Asturias (Spain) and surrounding towns. This argillaceous limestone has been quarried since the High Middle Ages until the beginning of the XX century. The main mineralogical components are carbonates (mainly calcite and sometimes ankerite, 70-90%), quartz (5-15%), terrigenous minerals (6-15%) and iron oxides (<5%). Two different facies, with different constructive uses, can be clearly distinguished depending on the grain size: fine-grained facies and coarse-grained facies. The fine-grained facies has color ranging from red to yellow, slightly higher content in carbonates, higher terrigenous components and a micro crystalline texture. The coarse-grained facies is mainly yellow, with detrital clastic texture. The open porosity is higher for the coarse-grained facies (16-20%), while for the fine-grained facies it ranges between 5 and 15%. The fine-grained facies is more vulnerable to weathering than the coarse-grained one, and it is used in the building heritage mainly for ornamental details, while the coarse-grained one is found in the bigger blocks and ashlars of the buildings. Some of the buildings constructed with Piedramuelle limestone are the Cathedral, the Old University and the Palaces from the XVII and XVIII centuries. The ambiance and historical architecture of Oviedo and adjacent towns is closely linked with the textures and colors of this stone. Nowadays, the Piedramuelle limestone is not exploited anymore, being the quarries exhausted. This represents an issue from a conservation point of view, since there is not a suitable stone for replacement. In order to preserve and maintain the building heritage of these towns, it is very important to prospect and protect the remaining outcrops still able to supply this characteristic stone.

  8. Diagenetic evaluation of Pannonian lacustrine deposits in the Makó Trough, southeastern Hungary

    NASA Astrophysics Data System (ADS)

    Szőcs, Emese; Milovský, Rastislav; Gier, Susanne; Hips, Kinga; Sztanó, Orsolya

    2017-04-01

    The Makó Trough is the deepest sub-basin of the Pannonian Basin. As a possible shale gas and tight gas accumulation the area was explored by several hydrocarbon companies. In this study, we present the preliminary results on the diagenetic history and the porosity evolution of sandstones and shales. Petrographic (optical microscopy, CL, blue light microscopy) and geochemical methods (SEM-EDX, WDX, O and C stable isotopes) were applied on core samples of Makó-7 well (3408- 5479 m). Processes which influenced the porosity evolution of the sandstones were compaction, cementation, mineral replacement and dissolution. The most common diagenetic minerals are carbonates (non-ferroan and Fe-bearing calcite, dolomite and ankerite), clay minerals (kaolinite, mixed layer illite-smectite and chlorite) and other silicates (quartz and feldspar). Initial clay mineral and ductile grain content also influences reservoir quality. The volumetrically most significant diagenetic minerals are calcite and clay minerals. The petrography of calcite is variable (bright orange to dull red luminescence color, pore-filling cement, replacive phases which are occasionally scattered in the matrix). The δ13 C-PDB values of calcite range from 1.7 ‰ to -5.5 ‰, while δ18 O-PDB values range from 0.5 ‰ to -9.1 ‰, no depth related trend was observed. These data suggest that calcite occurs in more generations, i.e. eogenetic pre-compactional and mesogenetic post-compactional. Kaolinite is present in mottles in size similar to detrital grains, where remnants of feldspars can be seen. This indicates feldspar alteration via influx of water rich in organic derived carbon dioxide. Secondary porosity can be observed in carbonates and feldspars at some levels, causing the improvement of the reservoir quality.

  9. Analysis of mineral matrices of planetary soil analogues from the Utah Desert

    NASA Astrophysics Data System (ADS)

    Kotler, J. M.; Quinn, R. C.; Foing, B. H.; Martins, Z.; Ehrenfreund, P.

    2011-07-01

    Phyllosilicate minerals and hydrated sulphate minerals have been positively identified on the surface of Mars. Studies conducted on Earth indicate that micro-organisms influence various geochemical and mineralogical transitions for the sulphate and phyllosilicate minerals. These minerals in turn provide key nutrients to micro-organisms and influence microbial ecology. Therefore, the presence of these minerals in astrobiology studies of Earth-Mars analogue environments could help scientists better understand the types and potential abundance of micro-organisms and/or biosignatures that may be encountered on Mars. Bulk X-ray diffraction of samples collected during the EuroGeoMars 2009 campaign from the Mancos Shale, the Morrison and the Dakota formations near the Mars Desert Research Station in Utah show variable but common sedimentary mineralogy with all samples containing quantities of hydrated sulphate minerals and/or phyllosilicates. Analysis of the clay fractions indicate that the phyllosilicates are interstratified illite-smectites with all samples showing marked changes in the diffraction pattern after ethylene glycol treatment and the characteristic appearance of a solvated peak at ˜17 Å. The smectite phases were identified as montmorillonite and nontronite using a combination of the X-ray diffraction data and Fourier-Transform Infrared Spectroscopy. The most common sulphate mineral in the samples is hydrated calcium sulphate (gypsum), although one sample contained detectable amounts of strontium sulphate (celestine). Carbonates detected in the samples are variable in composition and include pure calcium carbonate (calcite), magnesium-bearing calcium carbonate (dolomite), magnesium, iron and manganese-bearing calcium carbonate (ankerite) and iron carbonate (siderite). The results of these analyses when combined with organic extractions and biological analysis should help astrobiologists and planetary geologists better understand the potential relationships between mineralogy and microbiology for planetary missions.

  10. Oscillation of mineral compositions in Core SG-1b, western Qaidam Basin, NE Tibetan Plateau

    PubMed Central

    Fang, Xiaomin; Li, Minghui; Wang, Zhengrong; Wang, Jiuyi; Li, Jiao; Liu, Xiaoming; Zan, Jinbo

    2016-01-01

    Uplift of the Tibetan Plateau since the Late Miocene has greatly affected the nature of sediments deposited in the Qaidam Basin. However, due to the scarcity of continuously dated sediment records, we know little about how minerals responded to this uplift. In order to understand this response, we here present results from the high-resolution mineral profile from a borehole (7.3–1.6 Ma) in the Basin, which shows systematic oscillations of various evaporite and clay minerals that can be linked to the variation of regional climate and tectonic history. In particular, x-ray diffraction (XRD) analyses show that carbonate minerals consist mainly of calcite and aragonite, with minor ankerite and dolomite. Evaporates consist of gypsum, celesite and halite. Clay minerals are principally Fe-Mg illite, mixed layers of illite/smectite and chlorite, with minor kaolinite and smectite. Following implications can be drawn from the oscillations of these minerals phases: (a) the paleolake was brackish with high salinity after 7.3 Ma, while an abrupt change in the chemical composition of paleolake water (e.g. Mg/Ca ratio, SO42− concentration, salinity) occurred at 3.3 Ma; (b) the three changes at ~6.0 Ma, 4.5–4.1 Ma and 3.3 Ma were in response to rapid erosions/uplift of the basin; (c) pore water or fluid was Fe/Mg-rich in 7.3–6.0 Ma, Mg-rich in 6.0–4.5 Ma, and K-rich in 4.1–1.6 Ma; and (d) evaporation rates were high, but weaker than today’s. PMID:27625177

  11. Mobilization of Ag, heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería, SE Spain)

    NASA Astrophysics Data System (ADS)

    Navarro, A.; Cardellach, E.

    2009-02-01

    We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg-1), Ba (mean 2.5%), Fe (mean 114,000 mg kg-1), Sb (mean 342.5 mg kg-1), Pb (mean 1,229.8 mg kg-1), Zn (mean 493 mg kg-1), Mn (mean 4,321.1 mg kg-1), Cd (mean 1.2 mg kg-1) and Eu (mean 4.0 mg kg-1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)3, which controls the solubility of Eu in the pH-Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.

  12. Agricolaite, a new mineral of uranium from Jáchymov, Czech Republic

    NASA Astrophysics Data System (ADS)

    Skála, Roman; Ondruš, Petr; Veselovský, František; Císařová, Ivana; Hloušek, Jan

    2011-11-01

    The new mineral agricolaite, a potassium uranyl carbonate with ideal formula K4(UO2)(CO3)3, occurs in vugs of ankerite gangue in gneisses in the abandoned Giftkiesstollen adit at Jáchymov, Czech Republic. The name is after Georgius Agricola (1494-1555), German scholar and scientist. Agricolaite occurs as isolated equant irregular translucent grains to 0.3 mm with yellow color, pale yellow streak, and vitreous luster. It is brittle with uneven fracture and displays neither cleavage nor parting. Agricolaite is non-fluorescent. Mohs hardness is ~4. It is associated with aragonite, brochantite, posnjakite, malachite, rutherfordine, and "pseudo-voglite". Experimental density is higher than 3.3 g.cm-3, Dcalc is 3.531 g. cm-3. The mineral is monoclinic, space group C2/ c, with a 10.2380(2), b 9.1930(2), c 12.2110(3) Å, β 95.108(2)°, V 1144.71(4) Å3, Z = 4. The strongest lines in the powder X-ray diffraction pattern are d( I)( hkl): 6.061(55)(002), 5.087(57)(200), 3.740(100)(202), 3.393(43)(113), 2.281(52)(402). Average composition based on ten electron microprobe analyses corresponds to (in wt.%) UO3 48.53, K2O 31.49, CO2(calc) 22.04 which gives the empirical formula K3.98(UO2)1.01(CO3)3.00. The crystal structure was solved from single-crystal X-ray diffraction data and refined to R 1 = 0.0184 on the basis of the 1,308 unique reflections with F o > 4 σF o. The structure of agricolaite is identical to that of synthetic K4(UO2)(CO3)3 and consists of separate UO2(CO3)3 groups organized into layers parallel to (100) and two crystallographically non-equivalent sites occupied by K+ cations. Both the mineral and its name were approved by the IMA-CNMNC.

  13. Process for Making Single-Domain Magnetite Crystals

    NASA Technical Reports Server (NTRS)

    Golden, D. C.; Ming, Douglas W.; Morris, Richard V.; Lofgren, Gary E.; McKay, Gordan A.; Schwandt, Craig S.; Lauer, Howard V., Jr.; Socki, Richard A.

    2004-01-01

    A process for making chemically pure, single-domain magnetite crystals substantially free of structural defects has been invented as a byproduct of research into the origin of globules in a meteorite found in Antarctica and believed to have originated on Mars. The globules in the meteorite comprise layers of mixed (Mg, Fe, and Ca) carbonates, magnetite, and iron sulfides. Since the discovery of the meteorite was announced in August 1996, scientists have debated whether the globules are of biological origin or were formed from inorganic materials by processes that could have taken place on Mars. While the research that led to the present invention has not provided a definitive conclusion concerning the origin of the globules, it has shown that globules of a different but related chemically layered structure can be grown from inorganic ingredients in a multistep precipitation process. As described in more detail below, the present invention comprises the multistep precipitation process plus a subsequent heat treatment. The multistep precipitation process was demonstrated in a laboratory experiment on the growth of submicron ankerite crystals, overgrown by submicron siderite and pyrite crystals, overgrown by submicron magnesite crystals, overgrown by submicron siderite and pyrite. In each step, chloride salts of appropriate cations (Ca, Fe, and Mg) were dissolved in deoxygenated, CO2- saturated water. NaHCO3 was added as a pH buffer while CO2 was passed continuously through the solution. A 15-mL aliquot of the resulting solution was transferred into each of several 20 mL, poly(tetrafluoroethylene)-lined hydrothermal pressure vessels. The vessels were closed in a CO2 atmosphere, then transferred into an oven at a temperature of 150 C. After a predetermined time, the hydrothermal vessels were removed from the oven and quenched in a freezer. Supernatant solutions were decanted, and carbonate precipitates were washed free of soluble salts by repeated decantations with deionized water.

  14. SHRIMP U-Pb ages of xenotime and monazite from the Spar Lake red bed-associated Cu-Ag deposit, western Montana: Implications for ore genesis

    USGS Publications Warehouse

    Aleinikoff, John N.; Hayes, Timothy S.; Evans, Karl V.; Mazdab, Frank K.; Pillers, Renee M.; Fanning, C. Mark

    2012-01-01

    Xenotime occurs as epitaxial overgrowths on detrital zircons in the Mesoproterozoic Revett Formation (Belt Supergroup) at the Spar Lake red bed-associated Cu-Ag deposit, western Montana. The deposit formed during diagenesis of Revett strata, where oxidizing metal-bearing hydrothermal fluids encountered a reducing zone. Samples for geochronology were collected from several mineral zones. Xenotime overgrowths (1–30 μm wide) were found in polished thin sections from five ore and near-ore zones (chalcocite-chlorite, bornite-calcite, galena-calcite, chalcopyrite-ankerite, and pyrite-calcite), but not in more distant zones across the region. Thirty-two in situ SHRIMP U-Pb analyses on xenotime overgrowths yield a weighted average of 207Pb/206Pb ages of 1409 ± 8 Ma, interpreted as the time of mineralization. This age is about 40 to 60 m.y. after deposition of the Revett Formation. Six other xenotime overgrowths formed during a younger event at 1304 ± 19 Ma. Several isolated grains of xenotime have 207Pb/206Pb ages in the range of 1.67 to 1.51 Ga, and thus are considered detrital in origin. Trace element data can distinguish Spar Lake xenotimes of different origins. Based on in situ SHRIMP analysis, detrital xenotime has heavy rare earth elements-enriched patterns similar to those of igneous xenotime, whereas xenotime overgrowths of inferred hydrothermal origin have hump-shaped (i.e., middle rare earth elements-enriched) patterns. The two ages of hydrothermal xenotime can be distinguished by slightly different rare earth elements patterns. In addition, 1409 Ma xenotime overgrowths have higher Eu and Gd contents than the 1304 Ma overgrowths. Most xenotime overgrowths from the Spar Lake deposit have elevated As concentrations, further suggesting a genetic relationship between the xenotime formation and Cu-Ag mineralization.

  15. Diagenetic Carbonates Related to Hydrocarbon-rich Fluid Seepage in the Nile Deep Sea Fan (East Mediterranean Sea)

    NASA Astrophysics Data System (ADS)

    Pierre, C.; Gontharet, S.; Blanc-Valleron, M. M.; Bayon, G.; Dupré, S.; Mascle, J.

    2017-12-01

    During the NAUTINIL (September-October 2003), MIMES (July 2004), BIONIL (October 2006) and MEDECO2 (November 2007) cruises, coring and submersible dives were realized in the Nile Deep Sea Fan (NDSF) area. Active fluid venting sites were identified by the presence of living benthic organisms and by methane plumes in the bottom waters above the seeping structures. At all sites, hard carbonate crusts cover irregularly the sea floor. The sediments from the venting areas are organic-rich, contain sometimes carbonate concretions and have a strong H2S smell indicative of active sulfate reduction. The mineralogy of carbonate crusts is dominated by aragonite and Mg-calcite; the mineralogy of concretions is more complex, with mixtures of Mg-calcite, dolomite and ankerite. The oxygen and carbon isotopic compositions of the carbonate from crusts and concretions exhibit large variations (-2.8< δ18O ‰ VPDB <+9.5; -42.6< δ13C ‰ VPDB <+22.4). The wide range of δ18O values reflects variable sources of fluids. Most of the authigenic carbonates from the NDSF were precipitated in isotopic equilibrium with the Mediterranean bottom water. The carbonate crusts and concretions from the brine seeps of the north-western NDSF are enriched in 18O indicating that a source of 18O-rich fluids originated from depth. Differently, a few crusts and concretions from the eastern NDSF exhibit relatively low δ18O values, which are due to precipitation at warm temperatures. The very low δ13C values of the diagenetic carbonates indicate that methane and possibly other heavier hydrocarbons were the major source of carbon that was oxidized as bicarbonate mostly through bacterial sulfate reduction coupled with anaerobic methane oxidation within the anoxic sediment. The very positive δ13C values of the diagenetic carbonates from many carbonate concretions are related to the production of 13C-rich CO2 during methanogenesis within the sub-seafloor sediments.

  16. A modeling study of the long-term mineral trapping in deep saline marine sands aquifers (Invited)

    NASA Astrophysics Data System (ADS)

    Aagaard, P.; Pham, V.; Hellevang, H.

    2009-12-01

    Simulation of geochemical processes due to CO2 injection and storage are dependent on sediment petrography and the kinetics of mineral fluid reactions. Mineral trapping of CO2 in the Utsira sand and similar marine sand reservoirs have been revisited based on critical review of rate data and geochemical constraints on formation waters. Reaction paths calculations were done with the PHREEQC modeling software at relevant reservoir conditions covering a temperature range of 30-100 °C and corresponding reservoir pressures. Initial CO2 saturation was determined by the fluid fugacity corresponding with reservoir conditions. The mineral dissolution kinetics was expressed with a chemical affinity term (Aagaard & Helgeson,1982) while a critical super-saturation for mineral growth was included in the precipitation rate expression. The redox conditions and the H2S fugacity in the simulations were constrained by the acetic/propionic acid buffer trend and the magnetite-pyrite buffer (Aagaard et al. 2001) respectively. We used a revised mineralogical composition for the Utsira sand also performed a sensitivity analyses with respect to mineral content. The simulations were run over a period of 10000 years. The main simulation results included dissolution of glauconite, smectite, pyrite, muscovite and albite, with precipitation of the carbonates siderite, ankerite, and minor dawsonite, as well as kaolinite, silica (either chalcedony or quartz), and K-feldspar. The uncertainties in the simulations are specially connected with initial mineral abundances. The effect of critical super-saturation and reactive surface area for precipitation needs to be further evaluated and tested. Aagaard, P. and H.C. Helgeson (1982). Thermodynamic and Kinetic Constraints on Reaction Rates among Minerals and Aqueous Solutions. I. Theoretical Considerations. Am. J. Sci., v. 282, p. 257-285. P. Aagaard, J. Jahren & S.N. Ehrenberg (2001) H2S controling reactions in clastic hydrocarbon reservoirs from the Norwegian Shelf and Gulf Coast, in Cidu, R.(ed) Water-Rock Interaction, WRI-10, Balkema, p. 129-132.

  17. Isotopically zoned carbonate cements in Early Paleozoic sandstones of the Illinois Basin: δ18O and δ13C records of burial and fluid flow

    NASA Astrophysics Data System (ADS)

    Denny, Adam C.; Kozdon, Reinhard; Kitajima, Kouki; Valley, John W.

    2017-11-01

    SEM/SIMS imaging and analysis of δ18O and δ13C in sandstones from a transect through the Illinois Basin (USA) show systematic μm-scale isotopic zonation of up to 10‰ in both carbonate and quartz cements of the middle-Ordovician St. Peter and Cambrian Mt. Simon formations. Quartz δ18O values are broadly consistent with the model of Hyodo et al. (2014), wherein burial and heating in the Illinois Basin is recorded in systematically zoned quartz overgrowths. Observations of zoned dolomite/ankerite cements indicate that they preserve a more extended record of temperature and fluid compositions than quartz, including early diagenesis before or during shallow burial, and late carbonates formed after quartz overgrowths. Many carbonate cements show innermost dolomite with δ18O values (21-25‰ VSMOW) that are too low to have formed by deposition at low temperatures from ancient seawater (δ18O > - 3‰) and most likely reflect mixing with meteoric water. A sharp increase in Fe content is commonly observed in zoned carbonate cements to be associated with a drop in δ18O and an abrupt shift in δ13C to higher or lower values. These changes are interpreted to record the passage of hot metal-rich brines through sandstone aquifers, that was associated with Mississippi-Valley Type (MVT) Pb-Zn deposits (ca. 270 Ma) of the Upper Mississippi Valley. Local variability and individual trends in δ13C are likely controlled by the sources of carbon and the degree to which carbon is sourced from adjacent carbonate units or thermal maturation of organic matter. Quartz overgrowths in sandstones provide an excellent record of conditions during burial, heating, and pressure-solution, whereas carbonate cements in sandstones preserve a more-extended record including initial pre-burial conditions and punctuated fluid flow events.

  18. Fluid-rock interaction recorded in fault rocks of the Nobeoka Thrust, fossilized megasplay fault in an ancient accretionary complex

    NASA Astrophysics Data System (ADS)

    Hasegawa, R.; Yamaguchi, A.; Fukuchi, R.; Kitamura, Y.; Kimura, G.; Hamada, Y.; Ashi, J.; Ishikawa, T.

    2017-12-01

    The relationship between faulting and fluid behavior has been in debate. In this study, we clarify the fluid-rock interaction in the Nobeoka Thrust by major/trace element composition analysis using the boring core of the Nobeoka Thrust, an exhumed analogue of an ancient megasplay fault in Shimanto accretionary complex, southwest Japan. The hanging wall and the footwall of the Nobeoka Thrust show difference in lithology and metamorphic grade, and their maximum burial temperature is estimated from vitrinite reflectance analysis to be 320 330°C and 250 270°C, respectively (Kondo et al., 2005). The fault zone was formed in a fluid-rich condition, as evidenced by warm fluid migration suggested by fluid inclusion analysis (Kondo et al., 2005), implosion brecciation accompanied by carbonate precipitation followed by formation of pseudotachylyte (Okamoto et al., 2006), ankerite veins coseismically formed under reducing conditions (Yamaguchi et al., 2011), and quartz veins recording stress rotation in seismic cycles (Otsubo et al., 2016). In this study, first we analyzed the major/trace element composition across the principal slip zone (PSZ) of the Nobeoka Thrust by using fragments of borehole cores penetrated through the Nobeoka Thrust. Many elements fluctuated just above the PSZ, whereas K increase and Na, Si decrease suggesting illitization of plagioclase, as well as positive anomalies in Li and Cs were found within the PSZ. For more detail understanding, we observed polished slabs and thin sections of the PSZ. Although grain size reduction of deformed clast and weak development of foliation were observed entirely in the PSZ by macroscopic observation, remarkable development of composite planar fabric nor evidence of friction melting were absent. In this presentation, we show the result of major/trace element composition corresponding to the internal structure of PSZ, and discuss fluid-rock interaction and its impact to megasplay fault activity in subduction zones.

  19. Diagenesis and reservoir quality of the Lower Cretaceous Quantou Formation tight sandstones in the southern Songliao Basin, China

    NASA Astrophysics Data System (ADS)

    Xi, Kelai; Cao, Yingchang; Jahren, Jens; Zhu, Rukai; Bjørlykke, Knut; Haile, Beyene Girma; Zheng, Lijing; Hellevang, Helge

    2015-12-01

    The Lower Cretaceous Quantou Formation in the southern Songliao Basin is the typical tight oil sandstone in China. For effective exploration, appraisal and production from such a tight oil sandstone, the diagenesis and reservoir quality must be thoroughly studied first. The tight oil sandstone has been examined by a variety of methods, including core and thin section observation, XRD, SEM, CL, fluorescence, electron probing analysis, fluid inclusion and isotope testing and quantitative determination of reservoir properties. The sandstones are mostly lithic arkoses and feldspathic litharenites with fine to medium grain size and moderate to good sorting. The sandstones are dominated by feldspar, quartz, and volcanic rock fragments showing various stages of disintegration. The reservoir properties are quite poor, with low porosity (average 8.54%) and permeability (average 0.493 mD), small pore-throat radius (average 0.206 μm) and high displacement pressure (mostly higher than 1 MPa). The tight sandstone reservoirs have undergone significant diagenetic alterations such as compaction, feldspar dissolution, quartz cementation, carbonate cementation (mainly ferrocalcite and ankerite) and clay mineral alteration. As to the onset time, the oil emplacement was prior to the carbonate cementation but posterior to the quartz cementation and feldspar dissolution. The smectite to illite reaction and pressure solution at stylolites provide a most important silica sources for quartz cementation. Carbonate cements increase towards interbedded mudstones. Mechanical compaction has played a more important role than cementation in destroying the reservoir quality of the K1q4 sandstone reservoirs. Mixed-layer illite/smectite and illite reduced the porosity and permeability significantly, while chlorite preserved the porosity and permeability since it tends to be oil wet so that later carbonate cementation can be inhibited to some extent. It is likely that the oil emplacement occurred later than the tight rock formation (with the porosity close to 10%). However, thicker sandstone bodies (more than 2 m) constitute potential hydrocarbon reservoirs.

  20. Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings.

    PubMed

    Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A H

    2015-01-01

    Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal.

  1. Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings

    PubMed Central

    Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A. H.

    2015-01-01

    Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal. PMID:26295582

  2. Lithologically controlled invisible gold, Yukon, Canada

    NASA Astrophysics Data System (ADS)

    MacKenzie, Doug; Craw, Dave; Finnigan, Craig

    2015-02-01

    The newly discovered Cretaceous Coffee orogenic gold deposit (>4 Moz resource) consists of an extensive oxidised zone developed on primary sulphidic rock. The primary mineralised rock is characterised by invisible gold in arsenian pyrite that has replaced biotite in selected host rocks. The deposit has a cryptic surface expression and is an example of an extremely subtle exploration target. Hydrothermal emplacement was controlled by extensional fractures, with breccias, but most mineralisation was focused on biotite-bearing granitic gneiss, metasedimentary gneisses, and younger biotite granite. Fine-grained (<0.1 mm) arsenian pyrite replaced biotite along mineral cleavage planes and followed biotite-rich metamorphic and post-metamorphic structural fabrics. Arsenian pyrite also formed overgrowths on earlier coarse-grained (up to 2 mm) barren hydrothermal pyrite. Arsenian pyrite is concentrically zoned on the 1-10-μm scale with respect to As, Sb, and Au contents and typically contains ˜5 wt% As, ˜500 mg/kg Sb, and ˜500 mg/kg Au, in solid solution. Biotite replacement was accompanied by sericitisation, silicification, and ankerite impregnation. Hydrothermal alteration involved dilution and localised depletion of K, Na, and Al in silicified host rocks, but most Ca, Mg, and Fe concentrations remained broadly constant. Magnesium-rich ultramafic host rocks were only weakly mineralised with auriferous arsenian pyrite and have fuchsite and magnesite alteration. Near-surface oxidation has liberated nanoparticulate and microparticulate supergene gold, which remains essentially invisible. Varying degrees of oxidation extend as deep as 250 m below the present subdued topographic surface, well beyond the present vadose zone, and this deep oxidation may have occurred during post-mineralisation uplift and erosion in the Cretaceous. Oxidation has leached some As from the surficial mineralised rocks, decreasing the geochemical signal, which is also obscured by the localised presence of high background As (up to 100 mg/kg) in metasedimentary quartzites in the region. Antimony provides more reliable soil anomalies than As, but most Sb anomalies are <100 mg/kg. The persistence of invisible gold into the extensive supergene zone, with little gold particle size enhancement, has ensured that no placer deposits have formed in nearby streams, further restricting the surface footprint and Au dispersal halo of this subtle exploration target.

  3. On the potential for CO2 mineral storage in continental flood basalts – PHREEQC batch- and 1D diffusion–reaction simulations

    PubMed Central

    2012-01-01

    Continental flood basalts (CFB) are considered as potential CO2 storage sites because of their high reactivity and abundant divalent metal ions that can potentially trap carbon for geological timescales. Moreover, laterally extensive CFB are found in many place in the world within reasonable distances from major CO2 point emission sources. Based on the mineral and glass composition of the Columbia River Basalt (CRB) we estimated the potential of CFB to store CO2 in secondary carbonates. We simulated the system using kinetic dependent dissolution of primary basalt-minerals (pyroxene, feldspar and glass) and the local equilibrium assumption for secondary phases (weathering products). The simulations were divided into closed-system batch simulations at a constant CO2 pressure of 100 bar with sensitivity studies of temperature and reactive surface area, an evaluation of the reactivity of H2O in scCO2, and finally 1D reactive diffusion simulations giving reactivity at CO2 pressures varying from 0 to 100 bar. Although the uncertainty in reactive surface area and corresponding reaction rates are large, we have estimated the potential for CO2 mineral storage and identified factors that control the maximum extent of carbonation. The simulations showed that formation of carbonates from basalt at 40 C may be limited to the formation of siderite and possibly FeMg carbonates. Calcium was largely consumed by zeolite and oxide instead of forming carbonates. At higher temperatures (60 – 100 C), magnesite is suggested to form together with siderite and ankerite. The maximum potential of CO2 stored as solid carbonates, if CO2 is supplied to the reactions unlimited, is shown to depend on the availability of pore space as the hydration and carbonation reactions increase the solid volume and clog the pore space. For systems such as in the scCO2 phase with limited amount of water, the total carbonation potential is limited by the amount of water present for hydration of basalt. PMID:22697910

  4. Hydrothermal Alteration of the Mt Unzen Conduit (Shimabara/Japan)

    NASA Astrophysics Data System (ADS)

    Yilmaz, T. I.; Mayer, K.; Hess, K. U.; Janots, E.; Gilg, H. A.; Dingwell, D. B.

    2016-12-01

    Investigations were carried out on hydrothermally altered coherent dacitic dykes samples from (USDP-4) drill core at Mt Unzen stratovolcano (Shimabara/Japan). XRF, XRD, EMPA, and C-O-isotope analysis led to insights concerning chemistry, mineralogy, and intensity of alteration as well as the origin of carbonate-precipitating fluids. Additionally a textural characterization of the occurring replacement features in the magma conduit zone was performed. The occurrence of the main secondary phases such as chlorite, pyrite, carbonates, and R1 (Reichweite parameter) illite-smectite indicate a weak to moderate propylitic to phyllic hydrothermal alteration. The dacitic samples of the dykes show different hydrothermal alteration features: (i) carbonate pseudomorphs after hornblende as well as core and zonal textures due to replacement of plagioclase by R1 illite-smectite, (ii) colloform banded fracture fillings and fillings in dissolution vugs, and (iii) chlorite and R1 illite-smectite in the groundmass. Carbonates in fractures comprise iron-rich dolomite solid solutions ("ankerite") and calcite. Isotopic values of d13Cvpdb = -4.59 ± 0.6‰ and d18Ovpdb = -21.73 ± 0.5‰ indicate a hydrothermal-magmatic origin for the carbonate formation. The chlorite-carbonate-pyrite index (CCPI) and the Ishikawa alteration index (AI), applied to the investigated samples show significant differences (CCPI=52.7-57.8; AI=36.1-40.6) indicating their different degree of alteration. According to Nakada et al., 2005, the C13 to C16 dykes represent the feeder dyke from the latest eruption (1991-1995) whereas C8 represents an earlier dyke feeder dyke from an older eruption. Weakest conduit alteration, which was obtained in samples C16-1-5 and C13-2-5, correlates with the alteration degree of the pristine dome rocks. Highest CCPI value was determined for sample C14-1-5 and the highest AI value was determined for sample C15-2-6. The degrees of alteration do not indicate highest alteration of the samples C8-1-2 and C8-2-1 from the older dykes.

  5. Mineralogy and Isotopic Records of Carbonate and Silicate Cementation of the Siliciclastic Sediments of the New Jersey Shelf (IODP Expedition 313)

    NASA Astrophysics Data System (ADS)

    Pierre, C.; Blanc-Valleron, M. M.; Lofi, J.

    2016-12-01

    The New Jersey continental shelf extends up to 150 km away from the shoreline. During IODP Expedition 313 the siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631 mbsf, 669 mbsf and 700 mbsf at the three sites 27A, 28A, 29A respectively, in very shallow water depth (33.5 to 36 m). Pore water salinities display multilayered fresh-salty-brine units 10 to 170 m thick, where freshwater is preferentially stored in fine-grained sediments (van Geldern et al 2013 ; Lofi et al 2013). The sharp boundaries of these buried aquifers are often marked by hardly cemented layers a few centimeters thick. The mineralogy and SEM observations of these layers show two phases of cementation by authigenic minerals : (1) the early carbonate cement is made of Fe-dolomite, ankerite and occasionally calcite, frequently associated with pyrite (2) the late silicate cement (silica, K-Fe-rich clay minerals, zeolites) fills in the residual porosity. The isotopic compositions of the carbonate cements vary in wide ranges : -2.4 < δ18O‰ VPDB < +2.8 ; -15.1< δ13C ‰ VPDB <+15.6. The δ18O values indicate carbonate precipitation with pore waters more or less depleted in 18O of the buried aquifers. The δ13C values of carbonate are related to organic matter diagenesis providing 13C-depleted DIC during bacterial sulphate reduction (with pyrite as a by-product of the reaction) and 13C-rich DIC during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO2-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The temperature estimated (18 ± 4°C) for the precipitation of carbonate indicates that cementation occurred at moderate burial depths, i.e. probably very soon after deposition. Lofi J et al 2013. Geosphere, 9, 4, 1009-1024 Van Geldern R et al 2013. Geosphere, 9, 1, 96-112

  6. Isotopic and geothermometric constraints on the structural and metamorphic evolution of Homestake gold deposit, Black Hills, South Dakota (USA)

    NASA Astrophysics Data System (ADS)

    Terry, M.; Dahl, P.; Frei, R.

    2003-04-01

    The Homestake Deposit, located in the northern Black Hills and host for 40 million ounces of gold, shows evidence for extensive remobilization of gold related to regional metamorphism deformation associated with the Early Proterozoic assembly of supercontinent Laurentia. Field and petrographic evidence for gold remobilization includes the occurrence of abundant quartz veins associated with selvages of chlorite-siderite-ankerite-pyrrhotite-arsenopyrite-gold in the Homestake Fm. The deposit is located on the western limb of a major anticlinorium that coincides with a vertical N-S-striking garnet isograd, and garnet-biotite geothermometry of metapelites sampled across the anticlinorium indicates a steep metamorphic field gradient of 150^oC/km (east side warmer). This gradient is mirrored by a pronounced fractionation of oxygen isotopes observed in the vein quartz, with δ18O ranging from 10 to 18 ppm. The isograd is parallel with a major N-S-striking shear zone, and kinematic indicators predominantly indicate oblique sinistral motion with east-side up. Garnet was separated from a subsurface sample of the Homestake Fm. collected from the nose of the so-called "main ledge" synform and subjected to Pb stepwise leaching (PbSL) to determine the age of garnet growth and thus metamorphism. PbSL analysis revealed a 207Pb/206Pb age of 1746 ± 10 Ma (± 2σ). Recent work in the southern Black Hills indicates that almandine does not contain sufficient Pb to be dated directly by this method; instead, the PbSL result represents the bulk age of abundant allanite inclusions observed in the garnet. Thus, 1746 Ma is interpreted as a maximum age of prograde garnet growth during regional thermotectonism. Mineral assemblages from selvages in Main Ledge indicate that mineralization occurred at or after peak metamorph, which indicates that 1746 Ma also represents a maximum age for gold remobilization. A minimum 1715 Ma age of these events is indicated by published ages of post-tectonic leucogranite in the Black Hills. Regionally, the N-S orientation, 1746--1715 Ma timing, and sinistral-transpressive motion combine to suggest that this major shear zone in the northern Black Hills represents a northerly extension of the Hartville fault, which is exposed in SE Wyoming, ˜200 km SSW. Correlation of these shear zones would have important implications for Proterozoic terrane assembly in this part of Laurentia.

  7. Geology and geochemistry of the shear-hosted Julie gold deposit, NW Ghana

    NASA Astrophysics Data System (ADS)

    Amponsah, Prince Ofori; Salvi, Stefano; Béziat, Didier; Siebenaller, Luc; Baratoux, Lenka; Jessell, Mark W.

    2015-12-01

    The Leo Man Craton in West Africa is host to numerous economic gold deposits. If some regions, such as the SW of Ghana, are well known for world-class mineralizations and have been extensively studied, gold occurrences elsewhere in the craton have been discovered only in the last half a century or so, and very little is known about them. The Julie gold deposit, located in the Paleoproterozoic Birimian terrane of NW Ghana, is one such case. This deposit is hosted in a series of granitoid intrusives of TTG composition, and consists of a network of deformed, boudinaged quartz lodes (A-type veins) contained within an early DJ1 E-W trending shear zone with dextral characteristics. A conjugate set of veins (C-type) perpendicular to the A-type veins contains low grade mineralization. The main ore zone defines a lenticular corridor about 20-50 m in width and about 3.5 km along strike, trending E-W and dipping between 30 and 60°N. The corridor is strongly altered, by an assemblage of sericite + quartz + ankerite + calcite + tourmaline + pyrite. This is surrounded by a second alteration assemblage, consisting of albite + sericite + calcite + chlorite + pyrite + rutile, which marks a lateral alteration that fades into the unaltered rock. Mass balance calculations show that during alteration overall mass was conserved and elemental transfer is generally consistent with sulfidation, sericitization and carbonatization of the host TTG. Gold is closely associated with pyrite, which occurs as disseminated grains in the veins and in the host rock, within the mineralized corridor. SEM imagery and LA-ICP-MS analyses of pyrites indicate that in A-type veins gold is associated with bismuth, tellurium, lead and silver, while in C-type veins it is mostly associated with silver. Pyrites in A-type veins contain gold as inclusions and as free gold on its edges and fractures, while pyrites from C-type veins contains mostly free gold. Primary and pseudosecondary fluid inclusions from both type veins indicate circulation in the system of an aqueous-carbonic fluid of low to moderate salinity, which entered the immiscibility PT region of the H2O-CO2-NaCl system, at about 220 °C and <1 kbar.

  8. Age and geochemistry of the Newania dolomite carbonatites, India: implications for the source of primary carbonatite magma

    NASA Astrophysics Data System (ADS)

    Ray, Jyotiranjan S.; Pande, Kanchan; Bhutani, Rajneesh; Shukla, Anil D.; Rai, Vinai K.; Kumar, Alok; Awasthi, Neeraj; Smitha, R. S.; Panda, Dipak K.

    2013-12-01

    The Newania carbonatite complex of India is one of the few dolomite-dominated carbonatites of the world. Intruding into Archean basement gneisses, the rocks of the complex have undergone limited diversification and are not associated with any alkaline silicate rock. Although the magmatic nature of the complex was generally accepted, its age of emplacement had remained equivocal because of the disturbed nature of radioisotope systems. Many questions about the nature of its mantle source and mode of origin had remained unanswered because of lack of geochemical and isotopic data. Here, we present results of our effort to date the complex using 147Sm-143Nd, 207Pb-206Pb and 40Ar-39Ar dating techniques. We also present mineral chemistry, major and trace element geochemistry and Sr-Nd isotopic ratio data for these carbonatites. Our age data reveal that the complex was emplaced at ~1,473 Ma and parts of it were affected by a thermal event at ~904 Ma. The older 207Pb-206Pb ages reported here (~2.4 Ga) and by one earlier study (~2.3 Ga; Schleicher et al. Chem Geol 140:261-273, 1997) are deemed to be a result of heterogeneous incorporation of crustal Pb during the post-emplacement thermal event. The thermal event had little effect on many magmatic signatures of these rocks, such as its dolomite-magnesite-ankerite-Cr-rich magnetite-magnesio-arfvedsonite-pyrochlore assemblage, mantle like δ13C and δ18O and typical carbonatitic trace element patterns. Newania carbonatites show fractional crystallization trend from high-Mg to high-Fe through high-Ca compositions. The least fractionated dolomite carbonatites of the complex possess very high Mg# (≥80) and have similar major element oxide contents as that of primary carbonatite melts experimentally produced from peridotitic sources. In addition, lower rare earth element (and higher Sr) contents than a typical calcio-carbonatite and mantle like Nb/Ta ratios indicate that the primary magma for the complex was a magnesio-carbonatite melt and that it was derived from a carbonate bearing mantle. The Sr-Nd isotopic data suggest that the primary magma originated from a metasomatized lithospheric mantle. Trace element modelling confirms such an inference and suggests that the source was a phlogopite bearing mantle, located within the garnet stability zone.

  9. An integrated geochemical, geophysical and mineralogical study of river sediments in alpine area and soil samples near steel plant, in Austria

    NASA Astrophysics Data System (ADS)

    Irfan, M. I.; Meisel, T.

    2012-04-01

    Concentration of nickel and chromium in any part of the ecosystem is important for environmental concerns in particular human health due to the reason that some species of them can cause health problem e.g. dermatitis and cancer. Sediment samples collected form a river Vordernberger Bach (Leoben, Austria) in an alpine region and soil samples collected in an area adjacent to steel production unit in same narrow valley were investigated. In previous studies a correlation between magnetic susceptibility values and concentration of nickel and chromium showed that a magnetic susceptibility meter can be used to point out the contaminated areas as in-situ device. The purpose of the whole study is to understand the real (point or diffuse, anthropogenic or geogenic) sources of contamination of soils, water and river sediments through heavy metal deposition. Unseparated, magnetic and non-magnetic fractions of soil samples were investigated for geochemical and mineralogical aspects with XRF, ICP-MS, EMPA, Multi-Functional Kappabridge (MFK1) and laser ablation coupled with ICP-MS. Mineralogical study of sediment samples for several sampling points with higher Ni and Cr content was performed. Sediment samples were sieved below 1.4 mm and then a concentrate of heavy minerals was prepared in the field through panning. Concentrated heavy minerals were then subjected for heavy liquid separation in the laboratory. Separated magnetic and non-magnetic fractions below 0.71/0.1 mm and density greater than 2.9 g/cm3 were selected for mineralogical investigation. The abundance of typical anthropogenic particles, e.g., spherical, tinder, roasted ores, iron and steel mill slag was observed under the microscope. Magnetite (mostly anthropogenic), maghemite, chromspinel, chromite (type I & II), (Ca,Al)-ferrite, wustite, apatite (anthropogenic), olivine mixed crystals, calcium silicate and spinel (anthropogenic) are found in magnetic fraction. Non-magnetic fractions contain hematite, siderite, ankerite, corundum (anthropogenic), garnet, chlorite, titanium oxide minerals (ilmenite, rutile, titanite) and amphibole etc. The observed significant increase in heavy metal content from the source region of the Vordernberger Bach at 1500 m above sea level to the confluence of the Vordernberger Bach with the Mur River at 540 m AMSL can be attributed to anthropogenic influence. As expected, the anthropogenic input is more pronounced in the vicinity of historic and current iron and steel production.

  10. New insights to the formation of modern dolomite in a terrestrial low-temperature environment

    NASA Astrophysics Data System (ADS)

    Zünterl, Andrea; Baldermann, Andre; Boch, Ronny; Dietzel, Martin

    2017-04-01

    Although dolomite [CaMg(CO3)2] is a rock-forming mineral in ancient carbonate platforms, its occurrence in modern-marine carbonate-depositing settings and in particular in terrestrial, low-temperature environments is scarce - an enigma that is referred to as the "dolomite problem". At present, it is generally accepted that microbial activity, bacterially-mediated sulfate reduction, high aqueous Mg/Ca ratios and anoxic conditions favour the nucleation and crystal growth of dolomite; albeit the precise reaction paths causing the formation of dolomite at low temperatures remain questionable. Here, we present a novel study about the environmental controls and reaction mechanisms leading to the formation of authigenic Mg-Ca carbonates in (active) fault zones of the Erzberg (Styria, Austria) - Europe's largest iron ore opencast mine. Our petrographic and mineralogical results revealed the presence of ˜2-20 cm thick laminated successions of embedded needle-shaped, radiating aragonite and blocky low-Mg calcite (a repetitive sequence also-called "erzbergite") and subsequently deposited (Ca-rich) non-stoichiometric dolomite, which is clogging former voids and unconsolidated sediment in the heavily deteriorated fault zone. First U-Th age determinations of the respective aragonite layers indicate its formation at ˜19,000-13,000 years BP, also suggesting a "young" age of the sedimentary dolomite. Based on the combination of X-ray diffraction and electron microprobe analyses we identified two types of matrix-replacing dolomite: type 1 dolomite is nearly stoichiometric (˜51 mol% CaCO3) and shows a high degree of cation ordering (0.4-0.6), whereas type 2 dolomite is characterized by Ca-excess (˜55 mol% CaCO3) and a low degree of ordering (<0.3). Both types of dolomite grow on the extent of matrix minerals, such as detrital low-Mg calcite, ankerite, siderite, quartz, goethite, chlorite and illitic clay minerals, implying a low-temperature origin of the Ca-excess dolomite and its formation through replacement of CaCO3 precursor phases at high aqueous Mg/Ca ratios of the mineralizing (meteroric) fluids. Further analysis of the δ18O, δ13C, δ26Mg and clumped isotopic (Δ47) signatures of the authigenic Ca-Mg carbonates will give new insights to the physicochemical conditions and reaction paths causing dolomitization in such an exotic, terrestrial environment.

  11. Diagenesis of Upper Carboniferous rocks in the Ouachita foreland shelf in mid-continent USA: an overview of widespread effects of a Variscan-equivalent orogeny

    USGS Publications Warehouse

    Walton, A.W.; Wojcik, K.M.; Goldstein, R.H.; Barker, C.E.

    1995-01-01

    Diagenesis of Upper Carboniferous foreland shelf rocks in southeastern Kansas took place at temperatures as high as 100-150?? C at a depth of less than 2 km. High temperatures are the result of the long distance (hundreds of kilometers) advection of groundwater related to collisional orogeny in the Ouachita tectonic belt to the south. Orogenic activity in the Ouachita area was broadly Late Carboniferous, equivalent to the Variscan activity of Europe. Mississippi Valley-type Pb-Zn deposits and oil and gas fields in the US midcontinent and elsewhere are commonly attributed to regional groundwater flow resulting from such collisional events. This paper describes the diagenesis and thermal effects in sandstone and limestone of Upper Carboniferous siliciclastic and limestone-shale cyclothems, the purported confining layer of a supposed regional aquifer. Diagenesis took place in early, intermediate, and late stages. Many intermediate and late stage events in the sandstones have equivalents in the limestones, suggesting that the causes were regional. The sandstone paragenesis includes siderite cement (early stage), quartz overgrowths (intermediate stage), dissolution of feldspar and carbonates, followed by minor Fe calcite, pore-filling kaolinite and sub-poikilotopic Ca ankerite (late stage). The limestone paragenesis includes calcite cement (early stage); megaquartz, chalcedony, and Fe calcite spar (intermediate stage); and dissolution, Ca-Fe dolomite and kaolinite (late stage). The Rm value of vitrinite shows a regional average of 0.6-0.7%; Rock-Eval TmaX suggests a comparable degree of organic maturity. The Th of aqueous fluid inclusions in late stage Ca-Fe-Mg carbonates ranges from 90 to 160?? and Tmice indicates very saline water (>200000 ppm NaCl equivalent); ??18O suggests that the water is of basinal origin. Local warm spots have higher Rm, Tmax, and Th. The results constrain numerical models of regional fluid migration, which is widely viewed as an artesian flow from recharge areas in the Ouachita belt across the foreland basin onto the foreland shelf area. Such models must account for heating effects that extend at least 500 km from the orogenic front and affect both supposed aquifer beds and the overlying supposed confining layer. Warm spots indicate either more rapid or more prolonged flow locally. Th and Tmice data show the highest temperatures coincided with high salinity fluids. ?? 1995 Springer-Verlag.

  12. Experiment and simulation study on the effects of cement minerals on the water-rock-CO2 interaction during CO2 geological storage

    NASA Astrophysics Data System (ADS)

    Liu, N.; Cheng, J.

    2016-12-01

    The CO2 geological storage is one of the most promising technology to mitigate CO2 emission. The fate of CO2 underground is dramatically affected by the CO2-water-rock interaction, which are mainly dependent on the initial aquifer mineralogy and brine components. The cement minerals are common materials in sandstone reservoir but few attention has been paid for its effects on CO2-water-rock interaction. Five batch reactions, in which 5% cement minerals were assigned to be quartz, calcite, dolomite, chlorite and Ca-montmorillonite, respectively, were conducted to understanding the cement minerals behaviors and its corresponding effects on the matrix minerals alterations during CO2 geological storage. Pure mineral powders were selected to mix and assemble the 'sandstone rock' with different cement components meanwhile keeping the matrix minerals same for each group as 70% quartz, 20% K-feldspar and 5% albite. These `rock' reacted with 750ml deionized water and CO2 under 180° and 18MPa for 15 days, during which the water chemistry evolution and minerals surface micromorphology changes has been monitored. The minerals saturation indexes calculation and phase diagram as well as the kinetic models were made by PHREEQC to uncover the minerals reaction paths. The experiment results indicated that the quartz got less eroded, on the contrary, K-feldspar and albite continuously dissolved to favor the gibbsite and kaolinite precipitations. The carbonates cement minerals quickly dissolved to reach equilibrium with the pH buffered and in turn suppressed the alkali feldspar dissolutions. No carbonates minerals precipitations occurred until the end of reactions for all groups. The simulation results were basically consistent with the experiment record but failed to simulate the non-stoichiometric reactions and the minerals kinetic rates seemed underestimated at the early stage of reactions. The cement minerals significantly dominated the reaction paths during CO2 geological storage and its effects on the CO2-water-rock interaction should be focused no matter for the benefit of injection sustainability or carbon sequestration capability. And more cement minerals such as ankerite should be included and the reservoir quality changes should also be taken consideration in the further study.

  13. Chemistry, mineralogy and alteration intensity of hydrothermal altered Mt Unzen conduit rocks (Shimabara/Japan)

    NASA Astrophysics Data System (ADS)

    Hess, Kai-Uwe; Yilmaz, Tim; Gilg, H. Albert; Janots, Emilie; Mayer, Klaus; Nakada, Setsuya; Dingwell, Donald

    2017-04-01

    Investigations were carried out on hydrothermally altered coherent dacitic dykes samples from (USDP-4) drill core at Mt Unzen stratovolcano (Shimabara/Japan). XRF, XRD, EMPA, C-O-isotope, hot-cathode CL and SEM analysis led to insights concerning chemistry, mineralogy, and intensity and type of alteration as well as the origin of carbonate-precipitating fluids. Additionally a textural characterization of the occurring replacement features in the volcanic conduit rocks was performed. The occurrence of the main secondary phases such as chlorite, pyrite, carbonates, and R1 (Reichweite parameter) illite-smectite and kaolinite group minerals indicate a weak to moderate propylitic to phyllic hydrothermal alteration. The dacitic samples of the dykes show different hydrothermal alteration features: (i) carbonate and chlorite pseudomorphs after hornblende as well as core and zonal textures due to replacement of plagioclase by R1 illite-smectite as well as kaolinite group minerals, (ii) colloform banded fracture fillings and fillings in dissolution vugs, and (iii) chlorite, R1 illite-smectite as well as kaolinite group minerals in the groundmass. Late chlorite veins crosscut precipitates of R1 illite-smectite as well as kaolinite group minerals. Carbonates in fractures and in pseudomorphs after hornblende comprise iron-rich dolomite solid solutions ("ankerite") and calcite. Isotopic values indicate a hydrothermal-magmatic origin for the carbonate formation. The chlorite-carbonate-pyrite index (CCPI) and the Ishikawa alteration index (AI), applied to the investigated samples show significant differences (CCPI=52.7-57.8; AI=36.1-40.6) indicating their different degree of alteration. According to Nakada et al., 2005, the C13 to C16 dykes represent the feeder dyke from the latest eruption (1991-1995) whereas C8 represents an earlier dyke feeder dyke from an older eruption. Weakest alteration, which was obtained in samples C16-1-5 and C13-2-5, correlates with the alteration degree of the pristine dome rocks. The highest CCPI value was determined for sample C14-1-5 and the highest AI value was determined for sample C15-2-6. The degrees of alteration do not indicate highest alteration of the samples C8-1-2 and C8-2-1 from the older dykes.

  14. CO2 release from variable carbonate compositions via thermal breakdown and magmatic assimilation at mid-crustal depths

    NASA Astrophysics Data System (ADS)

    Carter, L. B.; Dasgupta, R.

    2017-12-01

    Assimilation of crustal limestone in intruding magma has been found to release potentially significant [1-2] but varying amounts of CO2 to the exogenic system depending on pressure, temperature and magma composition [3-4]. However, most natural carbonates range from impure calcite to dolomite or ankerite and their behavior during hydrothermal processes and magma intrusion are less known [2,5-6]. We experimentally investigated both the thermal stability and reactions with hydrous basaltic and dacitic magmas at 800-1200 °C at 0.5 GPa for 3 Fe-bearing dolomite-calcite solid solutions. Dolomite breaks down into Fe-Mg oxides and CO2 at ≤800 °C. With increasing carbonate Ca/Mg, higher temperature is needed to reach similar decarbonation levels and the transition from Fe-dolomite + Mg-calcite as stable carbonate phases to only the latter. In the presence of magmas, carbonate is Mg-calcite or calcite, in addition to minerals seen in previous pure dolomite studies and natural systems [2-4,7-9], including ferropericlase, diopside, olivine with dolomite, anorthite with calcic carbonate, and wollastonite with rhyolitic melts. Thermal breakdown and assimilation increase with Mg/Ca ratios in the starting carbonate (<50% breakdown & <60% assimilation, respectively). At identical conditions, dolomite assimilation by dacite can release 4 times as much CO2 as limestone, surpassing basalt-dolomite. Though greater than other dacite-carbonate reactions, basalt releases a similar amount regardless of carbonate composition. With Mg/Ca≥0.48, release of CO2 from destabilization even at low temperature (≥900 °C) exceeds that from assimilation (≥1000 °C). Thus magma-carbonate interaction may have contributed several times the current arc output [10] to Earth's past atmosphere, which necessitates cataloging carbonate compositions globally for consideration in climate modeling. [1] Aiuppa et al. 2017 ESciRev (168)24-47; [2] Lee and Lackey 2015 Elem (11)125-130; [3] Carter and Dasgupta 2015 EPSL (427) 202-214; [4] Carter and Dasgupta 2016 G3 (17)3893-3916; [5] Warren 2000 ESciRev (52)1:81; [6] Franzolin et al. 2011 CMP (161)213-227; [7] Jolis et al. 2013 CMP (166)1335-1353; [8] Iacono-Marziano et al. 2008 CMP (155)719-738; [9] Mollo et al. 2010 Lithos (114)503-514; [10] Burton et al 2013 RevMinGeochem (75) 323-254.

  15. Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

    PubMed Central

    Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

    2015-01-01

    Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface. PMID:26549929

  16. Reactive Transport Models with Geomechanics to Mitigate Risks of CO2 Utilization and Storage

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

    Deo, Milind; Huang, Hai; Kweon, Hyukmin

    2016-03-28

    Reactivity of carbon dioxide (CO 2), rocks and brine is important in a number of practical situations in carbon dioxide sequestration. Injectivity of CO 2 will be affected by near wellbore dissolution or precipitation. Natural fractures or faults containing specific minerals may reactivate leading to induced seismicity. In this project, we first examined if the reactions between CO 2, brine and rocks affect the nature of the porous medium and properties including petrophysical properties in the timeframe of the injection operations. This was done by carrying out experiments at sequestration conditions (2000 psi for corefloods and 2400 psi for batchmore » experiments, and 600°C) with three different types of rocks – sandstone, limestone and dolomite. Experiments were performed in batch mode and corefloods were conducted over a two-week period. Batch experiments were performed with samples of differing surface area to understand the impact of surface area on overall reaction rates. Toughreact, a reactive transport model was used to interpret and understand the experimental results. The role of iron in dissolution and precipitation reactions was observed to be significant. Iron containing minerals – siderite and ankerite dissolved resulting in changes in porosity and permeability. Corefloods and batch experiments revealed similar patterns. With the right cationic balance, there is a possibility of precipitation of iron bearing carbonates. The results indicate that during injection operations mineralogical changes may lead to injectivity enhancements near the wellbore and petrophysical changes elsewhere in the system. Limestone and dolomite cores showed consistent dissolution at the entrance of the core. The dissolution led to formation of wormholes and interconnected dissolution zones. Results indicate that near wellbore dissolution in these rock-types may lead to rock failure. Micro-CT images of the cores before and after the experiments revealed that an initial high-permeability pathway facilitated the formation of wormholes. The peak cation concentrations and general trends were matched using Toughreact. Batch reactor modeling showed that the geometric factors obtained using powder data that related effective surface area to the BET surface area had to be reduced for fractured samples and cores. This indicates that the available surface area in consolidated samples is lower than that deduced from powder experiments. Field-scale modeling of reactive transport and geomechanics was developed in parallel at Idaho National Laboratory. The model is able to take into account complex chemistry, and consider interactions of natural fractures and faults. Poroelastic geomechanical considerations are also included in the model.« less

  17. Late-stage anhydrite-gypsum-siderite-dolomite-calcite assemblages record the transition from a deep to a shallow hydrothermal system in the Schwarzwald mining district, SW Germany

    NASA Astrophysics Data System (ADS)

    Burisch, Mathias; Walter, Benjamin F.; Gerdes, Axel; Lanz, Maximilian; Markl, Gregor

    2018-02-01

    The majority of hydrothermal vein systems of economic interest occur at relatively shallow crustal levels, although many of them formed at significantly greater depths. Their present position is a consequence of uplift and erosion. Although, many aspects of their formation are well constrained, the temporal chemical evolution of such systems during uplift and erosion is still poorly understood. These vein minerals comprise calcite, dolomite-ankerite, siderite-magnesite, anhydrite and gypsum forming the last gangue assemblages in Jurassic and Tertiary sulphide-fluorite-quartz-barite veins of the Schwarzwald mining district, SW Germany. Mineral textures of samples from nine localities reveal that in these sequences, mineral precipitation follows a recurring pattern: early calcite is followed by anhydrite or gypsum, siderite and/or dolomite. This succession may repeat up to three times. In-situ (LA-ICP-MS) U-Pb age dating of 15 carbonates from three subsequent generations of the late-stage vein assemblage yield robust ages between 20 and 0.6 Ma. Each mineral sequence forms in a distinctive period of about 2-5 Ma. These ages clearly relate these late-stage mineral phases to the youngest geological episode of the Schwarzwald, which is associated with the Cenozoic Rhine Graben rifting and basement uplift. Based on thermodynamic modelling, the formation of the observed mineral assemblages required an deeply sourced Mg-, Fe- and SO4-rich fluid (b), which was episodically mixed with a shallow crustal HCO3-rich fluid (a). As a consequence of fluid mixing, concentrations of Mg, Fe and SO4 temporarily increased and initiated the formation of the observed sulphate-carbonate mineral sequences. This discontinuous large-scale vertical fluid mixing was presumably directly related to episodes of active tectonics associated with the Cenozoic strike-slip regime of the Upper Rhine Graben. Analogously, episodic fluid mixing is a major key in the formation of older (Jurassic to early Tertiary) Pb-Zn-fluorite-quartz-barite assemblages in the same specific vein systems, albeit involving different fluid compositions. Late-stage hydrothermal (∼20-70 °C) vein assemblages reported in this study record the transition from deep (>2 km) to very shallow (0-1 km) crustal conditions. As a consequence of successive uplift, increasing proportions of shallower and cooler (∼50-70 °C) fluids could take part in such mixing processes. Associated changes in the fluid composition caused the vein mineralogy to change from sulphide-quartz-fluorite-barite to calcite-anhydrite/gypsum-siderite-dolomite, as the system passively ascended closer to the surface.

  18. Silicate and Carbonatite Melts in the Mantle: Adding CO2 to the pMELTS Thermodynamic Model of Silicate Phase Equilibria

    NASA Astrophysics Data System (ADS)

    Antoshechkina, P. M.; Shorttle, O.

    2016-12-01

    The current rhyolite-MELTS algorithm includes a mixed H2O-CO2 vapor phase, and a self-consistent speciation model for CO2 and CaCO3 in the silicate liquid (Ghiorso & Gualda 2012; 2015). Although intended primarily to model crustal differentiation and degassing, GG15 captures much of the experimentally-observed melting behavior of CO2-rich mafic lithologies, including generation of small-degree carbonatite melts, a miscibility gap between carbonatite and silicate liquids at low P and a smooth transition to a single carbonated-silicate melt at high P (e.g. Dasgupta et al. 2007). However, solid and liquid carbonate phases were not used in calibration of GG15, and it is suitable only for P < 3 GPa. We present a preliminary model, based on pMELTS (Ghiorso et al. 2002), for melting of nominally-anhydrous carbonated peridotite and pyroxenite. In Antoshechkina et al. (2015; and references therein) we developed a scheme for calibration of molar volumes that directly interfaces with a MySQL database, adapted from LEPR (Hirschmann et al. 2008). Here, we further extend our database, e.g. to include multiple carbonate phases, and combine the calibration scheme with the libalphaMELTS interface to the rhyolite-MELTS, pMELTS, and H2O-CO2 fluid thermodynamic models (see magmasource.caltech.edu/alphamelts). We use a Monte-Carlo type calibration approach to fit the observed phases and compositions, though stop short of a fully Bayesian formulation. The CO2-fluid experimental database has been updated to include more recent and higher P studies, adding approximately 40 pure fluid plus liquid constraints that conform to the selection criteria used in GG15. To further expand the database, we plan to use some or all of: solid carbonate-bearing experiments; coexisting silicate and carbonatite liquids; phase-present, and phase-absent constraints. As a first approximation, we include four carbonate phases: pure calcite and aragonite, and binary solutions for dolomite-ankerite and magnesite-siderite. Following GG15, we have adopted the CO2 fluid model of Duan & Zhang (2006) and added CO2 and CaCO3 species to the pMELTS liquid model. A key question that we hope to address during calibration is whether a Na2CO3 liquid species is justified instead of, or in addition to, CaCO3 for the range over which pMELTS is calibrated (1 < P < 4 GPa).

  19. Melting phase relation of nominally anhydrous, carbonated pelitic-eclogite at 2.5-3.0 GPa and deep cycling of sedimentary carbon

    NASA Astrophysics Data System (ADS)

    Tsuno, Kyusei; Dasgupta, Rajdeep

    2011-05-01

    We have experimentally investigated melting phase relation of a nominally anhydrous, carbonated pelitic eclogite (HPLC1) at 2.5 and 3.0 GPa at 900-1,350°C in order to constrain the cycling of sedimentary carbon in subduction zones. The starting composition HPLC1 (with 5 wt% bulk CO2) is a model composition, on a water-free basis, and is aimed to represent a mixture of 10 wt% pelagic carbonate unit and 90 wt% hemipelagic mud unit that enter the Central American trench. Sub-solidus assemblage comprises clinopyroxene + garnet + K-feldspar + quartz/coesite + rutile + calcio-ankerite/ankeritess. Solidus temperature is at 900-950°C at 2.5 GPa and at 900-1,000°C at 3.0 GPa, and the near-solidus melt is K-rich granitic. Crystalline carbonates persist only 50-100°C above the solidus and at temperatures above carbonate breakdown, carbon exists in the form of dissolved CO2 in silica-rich melts and as a vapor phase. The rhyodacitic to dacitic partial melt evolves from a K-rich composition at near-solidus condition to K-poor, and Na- and Ca-rich composition with increasing temperature. The low breakdown temperatures of crystalline carbonate in our study compared to those of recent studies on carbonated basaltic eclogite and peridotite owes to Fe-enrichment of carbonates in pelitic lithologies. However, the conditions of carbonate release in our study still remain higher than the modern depth-temperature trajectories of slab-mantle interface at sub-arc depths, suggesting that the release of sedimentary carbonates is unlikely in modern subduction zones. One possible scenario of carbonate release in modern subduction zones is the detachment and advection of sedimentary piles to hotter mantle wedge and consequent dissolution of carbonate in rhyodacitic partial melt. In the Paleo-NeoProterozoic Earth, on the other hand, the hotter slab-surface temperatures at subduction zones likely caused efficient liberation of carbon from subducting sedimentary carbonates. Deeply subducted carbonated sediments, similar to HPLC1, upon encountering a hotter mantle geotherm in the oceanic province can release carbon-bearing melts with high K2O, K2O/TiO2, and high silica, and can contribute to EM2-type ocean island basalts. Generation of EM2-type mantle end-member may also occur through metasomatism of mantle wedge by carbonated metapelite plume-derived partial melts.

  20. A brittle-ductile high- and low-angle fault related to the Kea extensional detachment (W Cyclades., Greece)

    NASA Astrophysics Data System (ADS)

    Rockenschaub, M.; Grasemann, B.; Iglseder, C.; Rice, A. H. N.; Schneider, D.; Zamolyi, A.

    2010-05-01

    Roll-back of the African Plate within the Eurasian-African collision zone since the Oligocene/Miocene led to extension in the Cyclades along low-angle normal fault zones and exhumation of rocks from near the brittle-ductile transition zone. On the island of Kea (W Cyclades), which represents such a crustal scale low-angle fault zone with top-to-SSW kinematics, remote sensing analysis of brittle fault lineaments in the Pissis area (W Kea) demonstrates two dominant strike directions: ca. NE-SW and NW-SE. From the north of Pisses southwards, the angle between the two main fault directions changes gradually from a rhombohedral geometry (ca. 50°/130° angle between faults, with the acute angle facing westwards) to an orthogonal geometry. The aim of this study is the development of this fault system. We investigate, if this fault system is related to the Miocene extension or if it is related to a later overprinting event (e.g. the opening of the Corinth) Field observations revealed that the investigated lineaments are high-angle (50-90° dip) brittle/ductile conjugate, faults. Due to the lack of marker layers offsets could only rarely be estimated. Locally centimetre thick marble layers in the greenschists suggest a displacement gradient along the faults with a maximum offset of less than 60 cm. Large displacement gradients are associated with a pronounced ductile fault drag in the host rocks. In some instances, high-angle normal faults were observed to link kinematically with low-angle, top-to-SSW brittle/ductile shear bands. Both the high- and the low-angle faults have a component of ductile shear, which is overprinted by brittle deformation mechanisms. In thin-section, polyphase mode-2 cracks are filled mainly with calcite and quartz (ultra)cataclasites, sometimes followed by further opening with fluid-related iron-rich carbonate (ankeritic) precipitation. CL analysis reveals several generations of cements, indicating multiple phases of cataclastic deformation and fluid infiltration. Ar/Ar white mica data from Pisses constrain ductile deformation to ca. 20 Ma. Since the high-angle faults show a continuum from ductile to brittle deformation, the Ar/Ar cooling ages suggest that faulting must have occurred in the Miocene. Consequently the high-angle faulting was genetically related to the SSW-directed low-angle extensional event and does not represent a later overprint related to a different kinematic event.

  1. Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements

    PubMed Central

    Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

    2016-01-01

    Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, PCO2, variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide. PMID:27907043

  2. Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

    NASA Astrophysics Data System (ADS)

    Lerouge, C.; Grangeon, S.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Guerrot, C.; Widory, D.; Fléhoc, C.; Wille, G.; Ramboz, C.; Vinsot, A.; Buschaert, S.

    2011-05-01

    The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ 34S (-38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (-38‰ to -22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ 34S values (-14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ 34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/ 86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ 18O consistent with a marine environment. Its δ 13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ 18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ 18O values (˜+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.

  3. Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements.

    PubMed

    Duan, Yiping; Feng, Mingshi; Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

    2016-01-01

    Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, [Formula: see text], variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide.

  4. A subtle diagenetic trap in the Cretaceous Glauconite Sandstone of Southwest Alberta

    USGS Publications Warehouse

    Meshri, I.D.; Comer, J.B.

    1990-01-01

    Despite the long history of research which documents many studies involving extensive diagenesis, there are a few examples of a fully documented diagenetic trap. In the context of this paper, a trap is a hydrocarbon-bearing reservoir with a seal; because a reservoir without a seal acts as a carrier bed. The difficulty in the proper documentation of diagenetic traps is often due to the lack of: (a) extensive field records on the perforation and production histories, which assist in providing the depth of separation between hydrocarbon production and non-hydrocarbon or water production; and (b) the simultaneous availability of core data from these intervals, which could be studied for the extent and nature of diagenesis. This paper provides documentation for the existence of a diagenetic trap, based on perforation depths, production histories and petrologic data from the cored intervals, in the context of the geologic and stratigraphic setting. Cores from 15 wells and SP logs from 45 wells were carefully correlated and the data on perforated intervals was also acquired. Extensive petrographic work on the collected cores led to the elucidation of a diagenetic trap that separates water overlying and updip from gas downdip. Amoco's Berrymore-Lobstick-Bigoray fields, located near the northeastern edge of the Alberta Basin, are prolific gas producers. The gas is produced from reservoir rock consisting of delta platform deposits formed by coalescing distributary mouth bars. The overlying rock unit is composed of younger distributary channels; although it has a good reservoir quality, it contains and produces water only. The total thickness of the upper, water-bearing and lower gas-bearing sandstone is about 40 ft. The diagenetic seal is composed of a zone 2 to 6 ft thick, located at the base of distributary channels. This zone is cemented with 20-30% ankerite cement, which formed the gas migration and is also relatively early compared to other cements formed in the water zone. In addition to this barrier to vertical flow, a barrier to lateral flow is formed by the merging of the upper sandstone containing 14% kaolinite and the lower sandstone containing 20% siderite. The measured core permeabilities in these zones vary from 0.0002 to 0.001 milli-darcies. This spatial configuration of diagenetic cements causing porous and non-porous zones is a result of the process of geochemical self-organization. The spatial and temporal patterns of diagenesis are a complex result of coupling of natural processes involving fluid flow, fluid composition, mineral composition and mineral dissolution rates under the conditions of varying pressure and temperature in the subsurface. ?? 1990.

  5. 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.

  6. Structural-Diagenetic Controls on Fracture Opening in Tight Gas Sandstone Reservoirs, Alberta Foothills

    NASA Astrophysics Data System (ADS)

    Ukar, Estibalitz; Eichhubl, Peter; Fall, Andras; Hooker, John

    2013-04-01

    In tight gas reservoirs, understanding the characteristics, orientation and distribution of natural open fractures, and how these relate to the structural and stratigraphic setting are important for exploration and production. Outcrops provide the opportunity to sample fracture characteristics that would otherwise be unknown due to the limitations of sampling by cores and well logs. However, fractures in exhumed outcrops may not be representative of fractures in the reservoir because of differences in burial and exhumation history. Appropriate outcrop analogs of producing reservoirs with comparable geologic history, structural setting, fracture networks, and diagenetic attributes are desirable but rare. The Jurassic to Lower Cretaceous Nikanassin Formation from the Alberta Foothills produces gas at commercial rates where it contains a network of open fractures. Fractures from outcrops have the same diagenetic attributes as those observed in cores <100 km away, thus offering an ideal opportunity to 1) evaluate the distribution and characteristics of opening mode fractures relative to fold cores, hinges and limbs, 2) compare the distribution and attributes of fractures in outcrop vs. core samples, 3) estimate the timing of fracture formation relative to the evolution of the fold-and-thrust belt, and 4) estimate the degradation of fracture porosity due to postkinematic cementation. Cathodoluminescence images of cemented fractures in both outcrop and core samples reveal several generations of quartz and ankerite cement that is synkinematic and postkinematic relative to fracture opening. Crack-seal textures in synkinematic quartz are ubiquitous, and well-developed cement bridges abundant. Fracture porosity may be preserved in fractures wider than ~100 microns. 1-D scanlines in outcrop and core samples indicate fractures are most abundant within small parasitic folds within larger, tight, mesoscopic folds. Fracture intensity is lower away from parasitic folds; intensity progressively decreases from the faulted cores of mesoscopic folds to their forelimbs, with lowest intensities within relatively undeformed backlimb strata. Fracture apertures locally increase adjacent to reverse faults without an overall increase in fracture frequency. Fluid inclusion analyses of crack-seal quartz cement indicate both aqueous and methane-rich inclusions are present. Homogenization temperatures of two-phase inclusions indicate synkinematic fracture cement precipitation and fracture opening under conditions at or near maximum burial of 190-210°C in core samples, and 120-160°C in outcrop samples. In comparison with the fracture evolution in other, less deformed tight-gas sandstone reservoirs such as the Piceance and East Texas basins where fracture opening is primarily controlled by gas generation, gas charge, and pore fluid pressure, these results suggest a strong control of regional tectonic processes on fracture generation. In conjunction with timing and rate of gas charge, rates of fracture cement growth, and stratigraphic-lithological controls, these processes determine the overall distribution of open fractures in these reservoirs.

  7. Structural-Diagenetic Controls on Fracture Opening in Tight Gas Sandstone Reservoirs, Alberta Foothills

    NASA Astrophysics Data System (ADS)

    Ukar, E.; Eichhubl, P.; Fall, A.; Hooker, J. N.

    2012-12-01

    In tight gas reservoirs, understanding the characteristics, orientation and distribution of natural open fractures, and how these relate to the structural and stratigraphic setting are important for exploration and production. Outcrops provide the opportunity to sample fracture characteristics that would otherwise be unknown due to the limitations of sampling by cores and well logs. However, fractures in exhumed outcrops may not be representative of fractures in the reservoir because of differences in burial and exhumation history. Appropriate outcrop analogs of producing reservoirs with comparable geologic history, structural setting, fracture networks, and diagenetic attributes are desirable but rare. The Jurassic to Lower Cretaceous Nikanassin Formation from the Alberta Foothills produces gas at commercial rates where it contains a network of open fractures. Fractures from outcrops have the same diagenetic attributes as those observed in cores <100 km away, thus offering an ideal opportunity to 1) evaluate the distribution and characteristics of opening mode fractures relative to fold cores, hinges and limbs, 2) compare the distribution and attributes of fractures in outcrop vs. core samples, 3) estimate the timing of fracture formation relative to the evolution of the fold-and-thrust belt, and 4) estimate the degradation of fracture porosity due to postkinematic cementation. Cathodoluminescence images of cemented fractures in both outcrop and core samples reveal several generations of quartz and ankerite cement that is synkinematic and postkinematic relative to fracture opening. Crack-seal textures in synkinematic quartz are ubiquitous, and well-developed cement bridges abundant. Fracture porosity may be preserved in fractures wider than ~100 microns. 1-D scanlines in outcrop and core samples indicate fractures are most abundant within small parasitic folds within larger, tight, mesoscopic folds. Fracture intensity is lower away from parasitic folds; intensity progressively decreases from the faulted cores of mesoscopic folds to their forelimbs, with lowest intensities within relatively undeformed backlimb strata. Fracture apertures locally increase adjacent to reverse faults without an overall increase in fracture frequency. Fluid inclusion analyses of crack-seal quartz cement indicate both aqueous and methane-rich inclusions are present. Homogenization temperatures of two-phase inclusions indicate synkinematic fracture cement precipitation and fracture opening under conditions at or near maximum burial of 190-210°C in core samples, and 120-160°C in outcrop samples. In comparison with the fracture evolution in other, less deformed tight-gas sandstone reservoirs such as the Piceance and East Texas basins where fracture opening is primarily controlled by gas generation, gas charge, and pore fluid pressure, these results suggest a strong control of regional tectonic processes on fracture generation. In conjunction with timing and rate of gas charge, rates of fracture cement growth, and stratigraphic-lithological controls, these processes determine the overall distribution of open fractures in these reservoirs.

  8. Origin of the diagenetic carbonate crusts and concretions from the mud volcanoes of the Nile deep-sea fan

    NASA Astrophysics Data System (ADS)

    Gontharet, S.; Pierre, C.; Blanc Valleron, M.; Rouchy, J.; Fouquet, Y.; Bayon, G.

    2004-12-01

    During the NAUTINIL cruise (September -October 2003), 22 submersible dives have been realized in the Nile deep-sea fan area to investigate by a multidisciplinary approach, selected mud volcanoes which are very abundant and of various morphologies in the whole area (Loncke et al., 2004). The deepest site (3019 m) located in the western part of the deep-sea fan, corresponds to a large caldera (about 8 km of diameter) where brines are seeping along the flanks of the structure and are sometimes collected in pools and lakes. The other sites in the central and eastern parts of the Nile deep-sea fan correspond respectively to pock-marks located at 2120 m and to a mud volcano located at 1130 m where active fluid ventings were identified by the presence of living benthic organisms (mainly vestimentiferan worms; rarely bivalves). At these three sites, hard carbonate crusts cover irregularly the sea floor and are sometimes present as dispersed fragments within the topmost sediments. The sediments from the venting areas are organic-rich and have a strong H2S smell which is indicative of active sulfate reduction. Petrographic observations and XRD analyses of the carbonate crusts indicate that aragonite, calcite, Mg-calcite are the dominant authigenic carbonate phases with a minor contribution of dolomite ; small concretions of ankerite occur occasionally in the sediments of the eastern delta. Millimeter sized barite concretions have also been discovered in the pock-marks sediments. The oxygen and carbon isotopic compositions of the bulk carbonate from crusts and concretions exibit large variations : -0.67 < \\delta18O\\permil PDB < 4.66 -44.17< \\delta13C \\permil PDB < 3.10 The distribution of the isotopic values is explained by the mixing of the authigenic carbonates with the sedimentary matrix which corresponds itself to a mixture of pelagic sediments and mud breccia issued from the mud volcano activity. The rather large range of \\delta18O values might reflect variable sources of diagenetic fluids. Typically, the very low \\delta13C values of the authigenic carbonates indicate that CH4 was the major source of carbon which was oxidized as CO2, either through bacterial sulfate reduction within the sediment, or via bacterial aerobic oxidation at the sea floor. Similar isotopic values were previously measured in the diagenetic carbonate crusts from the mud volcanoes of the Mediterranean Ridge area (Aloisi et al., 2000) as well as in other areas of cold seeps outside the Mediterranean sea (for instance Gulf of Mexico, Cascadia margin, Barbados prism). References: Aloisi G., Pierre C., Rouchy J.M., Foucher J.P., Woodside J. and the Medinaut Scientific Party, 2000. E.P.S.L., 184, 321-338. Loncke L., Gaullier V., Bellaiche G., and Mascle J., 2004. A.A.P.G. Bull

  9. Thorium and rare earth minerals in the Powderhorn district, Gunnison County, Colorado

    USGS Publications Warehouse

    Olson, Jerry C.; Wallace, Stewart R.

    1954-01-01

    Thorium has been found since 1949 in at least 33 deposits in an area 6 miles wide and 20 miles long in the Powderhorn district, Gunnison County, Colo. The district is composed largely of pre-Jurassic metamorphic and igneous rocks, which are chiefly if not entirely pre-Cambrian in age. The metamorphic and igneous rocks are overlain by sandstone of the Morrison formation of Jurassic age, and by volcanic rocks of the Alboroto group and Hinsdale formation of Miocene and Pliocene (?) age, respectively. The thorium deposits occur in or near alkalic igneous rocks in which such elements as titanium, rare earths, barium, strontium, and niobium occur in greater-than-average amounts. The greatest mass of the alkalic igneous rocks the Iron Hill composite stoc,- occupies an area of 12 square miles in the southeastern part of the district. The age of the thorium deposits, like that of the alkalic igneous rocks, is not known other than pre-Jurassic. The thorium veins and mineralized shear zones range from a few inches to 18 feet in thickness and from a few feet to 3,500 feet in length. The veins are composed of calcite,.dolomite, siderite, ankerite, quartz, barite, pyrite, sphalerite, galena, goethite,. apatite, alkali feldspar, and many other minerals. The thorium occurs at least partly in thorite or hydrothorite. Sparse xenotime has been tentatively identified in one deposit. Several minerals containing rare earths of the cerium group as major constituents are found in carbonate veins near Iron Hill. Bastnaesite has been identified by X-ray methods, and cerite and synchisite are probably present also.The fluorapatite in some veins and in parts of the carbonate rock mass that occupies 2 square miles in the central part of the Iron Hill complex contains rare earths of the cerium group, generally in amounts of a fraction of a percent of the rock. The radioactivity of the deposits appears to be due almost entirely to thorium and its daughter products The ThO2 content of selected highgrade samples from the Little Johnnie vein is as much as 4 percent. The ThO2 content of the veins is generally less than 1 percent, however, and is only 0.05 to 0.1 percent in many of the veins studied. The little Johnnie vein, which was mapped in detail, can be traced discontinuously for a distance of more than 3,500 feet. The thoriumbearing material occurs as irregular veinlets and thin films introduced into the fault zone. The mineralized shear zone ranges from less than 6 inches to 5 feet in thickness. Near its west end the vein is broken by many faults in a zone that marks the edge of a roughly circular fault block, 11/2.miles in diameter, that has dropped 1,000 feet or more since the deposition of Miocene volcanic-rocks that now floor the Milkranch basin.

  10. Coupled Reactive Transport Modeling of CO2 Injection in Mt. Simon Sandstone Formation, Midwest USA

    NASA Astrophysics Data System (ADS)

    Liu, F.; Lu, P.; Zhu, C.; Xiao, Y.

    2009-12-01

    CO2 sequestration in deep geological formations is one of the promising options for CO2 emission reduction. While several large scale CO2 injections in saline aquifers have shown to be successful for the short-term, there is still a lack of fundamental understanding on key issues such as CO2 storage capacity, injectivity, and security over multiple spatial and temporal scales that need to be addressed. To advance these understandings, we applied multi-phase coupled reactive mass transport modeling to investigate the fate of injected CO2 and reservoir responses to the injection into Mt. Simon Formation. We developed both 1-D and 2-D reactive transport models in a radial region of 10,000 m surrounding a CO2 injection well to represent the Mt. Simon sandstone formation, which is a major regional deep saline reservoir in the Midwest, USA. Supercritical CO2 is injected into the formation for 100 years, and the modeling continues till 10,000 years to monitor both short-term and long-term behavior of injected CO2 and the associated rock-fluid interactions. CO2 co-injection with H2S and SO2 is also simulated to represent the flue gases from coal gasification and combustion in the Illinois Basin. The injection of CO2 results in acidified zones (pH ~3 and 5) adjacent to the wellbore, causing progressive water-rock interactions in the surrounding region. In accordance with the extensive dissolution of authigenic K-feldspar, sequential precipitations of secondary carbonates and clay minerals are predicted in this zone. The vertical profiles of CO2 show fingering pattern from the top of the reservoir to the bottom due to the density variation of CO2-impregnated brine, which facilitate convection induced mixing and solubility trapping. Most of the injected CO2 remains within a radial distance of 2500 m at the end of 10,000 years and is sequestered and immobilized by solubility and residual trapping. Mineral trapping via secondary carbonates, including calcite, magnesite, ankerite and dawsonite, is predicted, but only constituting a minor component as compared to other trapping mechanisms. The mineral alteration induced by CO2 injection results in changes in porosity/permeability due to these complex mineral dissolution and precipitation reactions. Increases in porosity (from 15% to 16.2%) occur in the low-pH zones due to the acidic dissolution of minerals. However, within the carbonate mineral trapping zone, porosity reduction occurs. Co-injection of H2S causes relatively limited modification from the CO2 alone case while significantly higher water-rock reactivity is associated with the SO2 co-injection. Although co-injection of CO2 with H2S and SO2 could potentially reduce separation and injection cost, it may lead to some uncertainty and risks and therefore require further investigation.

  11. Assessing Biogenecity of Stromatolites: Return to the Facies

    NASA Astrophysics Data System (ADS)

    Shapiro, R. S.; Jameson, S.; Rutter, A.; McCarthy, K.; Planavsky, N. J.; Severson, M.

    2013-12-01

    The discovery of richly microfossiliferous cherty stromatolites near Schreiber and Kakabeka Falls, Ontario, in the 1.9 Ga Gunflint Iron Formation, firmly established the field of pre-Cambrian paleontology. In the half-century since this discovery, paradigm shifts in the ecology of the microfossils as well as the utility of stromatolites as biological markers has caused a re-evaluation of our understanding of the pre-Cambrian fossil record. This research summarizes facies evaluation of the two stromatolite marker beds in the Gunflint-correlative Biwabik Iron Formation of Minnesota. The centimeter-scale microstratigraphy of cores drilled through the central and eastern Mesabi Iron Range was coupled with field descriptions of outcrops and mines in both the Biwabik and Gunflint iron formations. Eight lithologic facies associated with the stromatolites are identified: A) Pebble conglomerate clasts ranging in size of 0.5-3 cm, syneresis cracks, and septarian nodules with medium to coarse grain matrix; B) siltstone with subparallel sub-mm to 5 cm magnetitic and non-magnetic bands; C) stromatolitic boundstone comprising stratiform, pseudocolumnar, domal, undulatory, flat-laminated, dendritic, columnar, and mico-digitate forms and oncoids 0.5 to 2 cm diameter; D) grainstone with medium to coarse siliceous and carbonate ooids and peloids; E) massive green crystalline beds with bands of magnetite, quartz, calcite, disseminated pyrite and localized ankerite; F) autobreccicated fabric of 0.3 to 10 mm clasts; G) medium to coarse sandstone; H) quartzite. Correlation between 11 cores near Hoyt Lakes and 9 cores through the basal stromatolite layer at the MinnTac Mine near Virginia revealed that stromatolites formed both on conglomerate and medium quartz sandstone. Multiple forms of stromatolite may occur in a vertical succession (flat-laminated to undulatory to psuedocolumnar to columnar) or a core may be dominated by one type, typically columnar-stratiform. Where stromatolites do not occur, the interval is autobrecciated with many clasts containing syneresis cracks. Flow-banded iron oxides in these layers are not stromatolitic but likely formed from fluid flow at the boundary between well- and poorly-cemented lithofacies. Mesostructure is similar between collection sites that are essentially unaltered, low-grade diagenetic, and amphibolite-grade metamorphic. Furthermore, mesostructure is consistent in most stromatolites throughout both layers in the Biwabik as well as the Gunflint. These new results provide a much broader context then previous studies and demonstrate that the upper and lower stromatolite horizons in the Biwabik and Gunflint iron ranges are formed in similar facies. Complexity in stromatolite forms occurs on the sub-meter scale, as would be expected for a nearshore, microbially mediated system. However, there appears to be a gradient in the degree of microbial control of stromatolite morphology, with both ';biogenic' and ';abiogenic' forms present. More broadly, this work highlights the importance of field and regional context when deciphering the significance of microbialites.

  12. Mass transfer and fluid evolution in late-metamorphic veins, Rhenish Massif (Germany): insight from alteration geochemistry and fluid-mineral equilibria modeling

    NASA Astrophysics Data System (ADS)

    Marsala, Achille; Wagner, Thomas

    2016-08-01

    Element mobility and fluid-rock interaction related to the formation of late-metamorphic quartz veins have been studied by combination of mineral chemistry, whole-rock geochemistry, mass balance analysis and fluid-mineral equilibria modeling. The quartz veins are hosted by very low-grade metasedimentary rocks of the fold-and-thrust belt of the Rhenish Massif (Germany). The veins record two stages of evolution, a massive vein filling assemblage with elongate-blocky quartz, chlorite, apatite and albite, and a later open space filling assemblage with euhedral crystals of quartz, ankerite-dolomite and minor calcite and sulfides. Detailed mass balance analysis of an alteration profile adjacent to a representative quartz vein demonstrates that element mobility is restricted to the proximal zone. The most important element changes are gain of Ca, Fe, Mg, Mn, P and CO2, and loss of Si, K and Na. The data demonstrate that wall-rock carbonation is one of the main alteration features, whereas mobility of Si, K and Na are related to dissolution of quartz and destruction of detrital feldspar and muscovite. The whole-rock geochemical data, in conjunction with fluid composition data and pressure-temperature estimates, were used as input for fluid-mineral equilibria modeling in the system Si-Al-Fe-Mg-Ca-Na-K-C-S-O-H-B-F-Cl. Modeling involved calculation of rock-buffered fluid compositions over the temperature interval 100-500 °C, and reaction-path simulations where a rock-buffered high-temperature fluid reacts with fresh host-rocks at temperatures of 400, 300 and 200 °C. Calculated rock-buffered fluid compositions demonstrate that retrograde silica solubility is a strong driving force for quartz leaching in the temperature-pressure window of 380-450 °C and 0.5 kbar. These conditions overlap with the estimated temperatures for the initial stage of vein formation. Reaction-path models show that high-temperature alteration can produce the observed silica leaching, suggesting that fast advection of external hot fluids from deeper crustal levels was essential for the early stage of vein formation. Fluid advection must have occurred as multiple pulses, which allowed for periods of influx of fluids that leached quartz, alternating with periods of cooling and quartz precipitation in the veins. Reaction-path models at high temperatures (300-400 °C) do not produce carbonate alteration, whereas fluid-rock reaction at 200 °C produces carbonate alteration, consistent with the temperature estimates for the late-stage vein carbonate assemblage. Comparison between modeling results and geochemical data suggests that the observed alteration features are the product of fluid-rock reaction under conditions where the external fluid gradually cooled down and evolved with time. The results of this study highlight the importance of late-orogenic fluid migration for the formation of quartz vein arrays in fold-and-thrust belts.

  13. Stratabound copper-silver deposits of the Mesoproterozoic Revett formation, Montana and Idaho

    USGS Publications Warehouse

    Boleneus, David E.; Appelgate, Larry M.; Stewart, John H.; Zientek, Michael L.

    2005-01-01

    The western Montana copper belt in western Montana and northern Idaho contains several large stratabound copper-silver deposits in fine- to medium-grained quartzite beds of the Revett Formation of the Mesoproterozoic (1,470-1,401 Ma) Belt Supergroup. Production from the deposits at the Troy Mine and lesser production from the Snowstorm Mine has yielded 222,237 tons Cu and 1,657.4 tons Ag. Estimates of undeveloped resources, mostly from the world-class Rock Creek-Montanore deposits, as well as lesser amounts at the Troy Mine, total more than 2.9 million tons Cu and 2,600 tons Ag in 406 million tons of ore.The Rock Creek-Montanore and Troy deposits, which are currently the most significant undeveloped resources identified in the copper belt, are also among the largest stratabound copper-silver deposits in North America and contain about 15 percent of the copper in such deposits in North America. Worldwide, stratabound copper-silver deposits contain 23 percent of all copper resources and are the second-most important global source of the metal after porphyry copper deposits.The Revett Formation, which consists of subequal amounts of argillite, siltite, and quartzite, is informally divided into lower, middle, and upper members on the basis of the proportions of the dominant rock types. The unit thickness increases from north to south, from 1,700 ft near the Troy Mine, 55 mi north of Wallace, Idaho, to more than 5,300 ft at Wallace, Idaho, in the Coeur d'Alene Trough south of the Osburn Fault, a major right-lateral strike-slip fault.Mineral deposits in the Revett Formation occur mostly in the A-D beds of the lower member and in the middle quartzite of the upper member. The deposits are concentrated along a preore pyrite/hematite interface in relatively coarse grained, thick quartzite beds that acted as paleoaquifers for ore fluids. The deposits are characterized by mineral zones (alteration-mineral assemblages) that are a useful guide to the locations of mineral deposits. In particular, the gradational zone between the chalcopyrite-ankerite and pyrite-calcite zones is the site of most mineral deposits. Detailed information on the geology and mineral deposits of the Revett Formation is presented in the accompanying files that include (1) a tab-delimited text file providing details of the geologic and mineral-resource data for 57 Revett-subtype stratabound copper-silver deposits, occurrences, and prospects; (2) the stratigraphic records of 40 diamond-drill cores and 86 measured sections, totaling 150,752 ft of true thickness, which are provided in Excel spreadsheet and Adobe Portable Document Format files; and (3) spatial geologic data consisting of geologic maps of the Revett Formation, the subsurface locations of resources in Revett-subtype stratabound copper-silver deposits based on diamond-drill-core data, and the locations of diamond-drill holes and measured sections. The spatial data are contained in Arc/Info interchange files. Spatial information derived from these data includes the locations of mineral zones, a digital database showing untested exploration areas, and a digital database of permissive tracts for undiscovered mineral deposits.

  14. The interplay of evolved seawater and magmatic-hydrothermal fluids in the 3.24 Ga panorama volcanic-hosted massive sulfide hydrothermal system, North Pilbara Craton, Western Australia

    USGS Publications Warehouse

    Drieberg, Susan L.; Hagemann, Steffen G.; Huston, David L.; Landis, Gary; Ryan, Chris G.; Van Achterbergh, Esmé; Vennemann, Torsten

    2013-01-01

    The ~3240 Ma Panorama volcanic-hosted massive sulfide (VHMS) district is unusual for its high degree of exposure and low degree of postdepositional modification. In addition to typical seafloor VHMS deposits, this district contains greisen- and vein-hosted Mo-Cu-Zn-Sn mineral occurrences that are contemporaneous with VHMS orebodies and are hosted by the Strelley granite complex, which also drove VHMS circulation. Hence the Panorama district is a natural laboratory to investigate the role of magmatic-hydrothermal fluids in VHMS hydrothermal systems. Regional and proximal high-temperature alteration zones in volcanic rocks underlying the VHMS deposits are dominated by chlorite-quartz ± albite assemblages, with lesser low-temperature sericite-quartz ± K-feldspar assemblages. These assemblages are typical of VHMS hydrothermal systems. In contrast, the alteration assemblages associated with granite-hosted greisens and veins include quartz-topaz-muscovite-fluorite and quartz-muscovite (sericite)-chlorite-ankerite. These vein systems generally do not extend into the overlying volcanic pile. Fluid inclusion and stable isotope studies suggest that the greisens were produced by high-temperature (~590°C), high-salinity (38–56 wt % NaCl equiv) fluids with high densities (>1.3 g/cm3) and high δ18O (9.3 ± 0.6‰). These fluids are compatible with the measured characteristics of magmatic fluids evolved from the Strelley granite complex. In contrast, fluids in the volcanic pile (including the VHMS ore-forming fluids) were of lower temperature (90°–270°C), lower salinity (5.0–11.2 wt % NaCl equiv), with lower densities (0.88–1.01 g/cm3) and lower δ18O (−0.8 ± 2.6‰). These fluids are compatible with evolved Paleoarchean seawater. Fluids that formed the quartz-chalcopyrite-sphalerite-cassiterite veins, which are present within the granite complex near the contact with the volcanic pile, were intermediate in temperature and isotopic composition between the greisen and volcanic pile fluids (T = 240°–315°C; δ18O = 4.3 ± 1.5‰) and are interpreted to indicate mixing between the two end-member fluids. Evidence of mixing between evolved seawater and magmatic-hydrothermal fluid within the granite complex, together with the lack of evidence for a magmatic component in fluids from the volcanic pile, suggest partitioning of magmatic-hydrothermal from evolved seawater hydrothermal systems in the Panorama VHMS system. This separation is interpreted to result from either the swamping of a relatively small magmatic-hydro-thermal system by evolved seawater or density contrasts precluding movement of magmatic-hydrothermal fluids into the volcanic pile. Variability in the salinity of fluids in the volcanic pile, combined with evidence for mixing of low- and high-salinity fluids in the massive sulfide lens, is interpreted to indicate that phase separation occurred within the Panorama hydrothermal system. Although we consider this phase separation to have most likely occurred at depth within the system, as has been documented in modern VHMS systems, the data do not allow the location of the inferred phase separation to be determined.

  15. Geologic setting of the Mountain Pass rare earth deposits, San Bernardino County, California

    USGS Publications Warehouse

    Olson, Jerry Chipman

    1952-01-01

    The Mountain Pass district is in a block of pre-Cambrian metamorphic rocks bounded on the east and south by the alluvium of Ivanpah Valley. This block is separated from Paleozoic and Mesozoic sedimentary and volcanic rocks on the west by the Clark Mountain normal fault, and the northern boundary of the district is a prominent transverse fault. The pre-Cambrian metamorphic complex comprises a great variety of lithologic types including garnetiferous mica gneisses and schists; biotite-garnet-sillimenite gneiss; hornblende gneiss, schist, and amphibolite; biotite gneiss and schist; granitic gneisses and migmatites; pegmatites; and minor amounts of foliated mafic rocks. The rare earth-bearing carbonate rocks are related to potash-rich igneous rocks, of uncertain age, that cut the metamorphic complex. The larger potash-rich intrusive masses, 300 or more feet wide, comprise one granite, two syenite, and four composite shonkinite-syenite bodies. One of the shonkinite-syenite stocks is more than a mile long. Several hundred relatively thin dikes of these potash-rich rocks range in composition, and generally decreasing age, from biotite shonkinite through syenite to granite. A few thin fine-grained shonkinite dikes cut the granite. These potash-rich rocks are cut by east-trending andesitic dikes and by faults. Veins of carbonate rock are most abundant in and near the southwest side of the largest shonkinite-syenite body. Although most veins are less than 6 feet thick, one mass of carbonate rock near the Sulphide Queen min4e is 600 feet in maximum width and 2,400 feet long. About 200 veins have been mapped in the district; their aggregate surface area is probably less than one-tenth that of the large carbonate mass. The carbonate materials, which make up about 60 percent of the veins and the large carbonite body, are chiefly calcite, dolomite, ankerite, and siderite. The other constituents are barite, bastnaesite and perisite, quartz, and variable small quantities of crocidolite, biotite, phlogopite, chlorite, muscovite, apatite, iron oxides, fluorite, monazite, galena, allanite, sphene, pyrite, chalcopyrite, tetrahedrite, malachite, azurite, corussite, wulfenite, aragonite, and thorite. The rare earth oxide content in most of the carbonate rock is less than 13 percent, but in some local concentrations of bastnaesite the content is as high as 40 percent. The origin of the carbonate rocks and related potash-rich igneous rocks is considered in the light of similar associations of carbonate and alkalinic rocks in Sweden, Norway, Russia, South Africa, and the United States. The carbonate rock may have originated (1) as a pre-Cambrian limestone or evaporate sequence in the gneisses; (2) by reaction between magma and the Paleozoic dolomite and limestone overlying the pre-Cambrian complex; (3) by alteration of pre-Cambrian gneisses by emanations from an unknown deep-seated source; or (4) by differentiation of an alkaline magma from shonkinite to syenite to granite, leading to a final carbonate-rich fraction, containing the rare elements, which was emplaced either as a concentrated or a dilute solution. The fourth hypothesis is considered the most plausible.

  16. Organic petrology and geochemistry of mudrocks from the lacustrine Lucaogou Formation, Santanghu Basin, northwest China: Application to lake basin evolution

    USGS Publications Warehouse

    Hackley, Paul C.; Fishman, Neil; Wu, Tao; Baugher, Gregory

    2016-01-01

    Exploration for tight oil in the frontier Santanghu Basin of northwest China has resulted in recent commercial discoveries sourced from the lacustrine Upper Permian Lucaogou Formation, already considered a “world class source rock” in the Junggar Basin to the west. Here we apply an integrated analytical program to carbonate-dominated mudrocks from the Lucaogou Formation in Santanghu Basin to document the nature of organic matter (OM) in the context of an evolving lake system. The organic-rich samples (TOC 2.8–11.4 wt%; n = 10) were widely spaced from an ~ 200 m cored section, interpreted from textural and mineralogical evidence to document transition from a lower under-filled to an overlying balanced-filled lake. Organic matter is dominated by moderate to strongly fluorescent amorphous material with Type I geochemical signature (HI values 510–755; n = 10) occurring in a continuum from lamellar stringers, 10–20 μm thick, some ≥ 1 mm in length (possible microbial mat; preserved only in lower under-filled section) to finely-disseminated amorphous groundmass intimately intermixed with mineral matrix. Biomarkers for methanotrophs and photosynthetic cyanobacteria indicate a complex microbial consortium. A unicellular prasinophyte green alga(?), similar to Tasmanites in marine rocks, is present as discrete flattened discs 50–100 μm in diameter. Type III OM including vitrinite (some fluorescent) and inertinite also is abundant. Solid bitumen, indicating local kerogen conversion, fills voids and occurs throughout the cored section. Vitrinite reflectance values are 0.47–0.58%, consistent with strong OM fluorescence but may be “suppressed”. Other proxies, e.g., biomarker parameters, indicate the Lucaogou Formation is in the early oil window at this location. On average, slightly more amorphous OM and telalginite are present in the lower section, consistent with a shallow, stratified, saline environment with low sediment dilution. More inertinite is present in the upper section, indicating greater terrestrial influx and consistent with higher quartz and plagioclase content (dominantly authigenic chalcedony and albite). Laminated mudstones in the upper section indicate anoxia prevented bioturbation from benthic grazing, also indicating stratified water column conditions. A decrease upsection in authigenic dolomite with reciprocal increase of ankerite/siderite is consistent with decreasing salinity, as is an overall decrease in gammacerane index values. These observations suggest evolution from a shallow, stratified evaporative (saline) setting to a deeper, stratified freshwater basin with higher water input during Lucaogou deposition. The evolution from an under-filled to balance-filled lake in Santanghu Basin is similar to Lucaogou deposition in Junggar Basin, suggesting similar tectonic and climatic controls. Paleoclimate interpretations from other researchers in this area suggested an evolution from semi-arid to humid conditions during the Roadian; we interpret that the evolution from an under-filled to balanced-filled lake seen in our data is in response to climate change, and may represent increased groundwater delivery to the Santanghu Basin.

  17. Investigations Using Laboratory Testbeds to Interpret Flight Instrument Datasets from Mars Robotic Missions

    NASA Technical Reports Server (NTRS)

    Ming, D. W.; Morris, R. V.; Sutter, B.; Archer, P. D., Jr.; Achilles, C. N.

    2012-01-01

    The Astromaterials Research and Exploration Science Directorate at the NASA Johnson Space Center (JSC) has laboratory instrumentation that mimic the capabilities of corresponding flight instruments to enable interpretation of datasets returned from Mars robotic missions. The lab instruments have been and continue to be applied to datasets for the Moessbauer Spectrometer (MB) on the Mars Exploration Rovers (MER), the Thermal & Evolved Gas Analyzer (TEGA) on the Mars Phoenix Scout, the CRISM instrument on the Mars Reconnaissance Orbiter Missions and will be applied to datasets for the Sample Analysis at Mars (SAM), Chemistry and Mineralogy (CheMin) and Chemistry & Camera (ChemCam) instruments onboard the Mars Science Laboratory (MSL). The laboratory instruments can analyze analog samples at costs that are substantially lower than engineering models of flight instruments, but their success to enable interpretation of flight data depends on how closely their capabilities mimic those of the flight instrument. The JSC lab MB instruments are equivalent to the MER instruments except without flight qualified components and no reference channel Co-57 source. Data from analog samples were critical for identification of Mg-Fe carbonate at Gusev crater. Fiber-optic VNIR spectrometers are used to obtain CRISM-like spectral data over the range 350-2500 nm, and data for Fephyllosilicates show irreversible behavior in the electronic transition region upon dessication. The MB and VNIR instruments can be operated within chambers where, for example, the absolute H2O concentration can be measured and controlled. Phoenix's TEGA consisted of a calorimeter coupled to a mass spectrometer (MS). The JSC laboratory testbed instrument consisted of a differential scanning calorimeter (DSC) coupled to a MS configured to operate under total pressure (12 mbar), heating rate (20 C/min), and purge gas composition (N2) analogous to the flight TEGA. TEGA detected CO2 release at both low (400-680 C) and high (725-820 C) temperature and an endothermic reaction in concert with the high temperature release. The high-temperature thermal decomposition is consistent with calcite, dolomite, or ankerite, (3-6 wt.%) or any combination of these phase based upon laboratory testbed experiments. Recent laboratory experiments suggest that the low temperature CO2 release was caused by a reaction between calcium carbonate and hydrated magnesium perchlorate; although, CO2 release by the oxidation of organic materials and Fe-/Mg-rich carbonates cannot be ruled out. MSL landed in Gale crater on August 5, 2012. Although numerous analog samples have been analyzed on the JSC laboratory testbeds, no SAM, CheMin, or ChemCam analyses have been acquired by MSL to date. The JSC SAM laboratory testbed consists of a thermal analyzer coupled with a MS configured to operate under total pressure (30 mbar), heating rate (35 C/min), and purge gas composition (He) analogous to the flight SAM. The CheMin and ChemCam laboratory testbeds were developed and built by inXitu, Inc. and Los Alamos National Laboratory, respectively, to acquire datasets relevant to the MSL CheMin and ChemCam flight instruments.

  18. The mangazeya Ag-Pb-Zn vein deposit hosted in sedimentary rocks, Sakha-Yakutia, Russia: Mineral assemblages, fluid inclusions, stable isotopes (C, O, S), and origin

    NASA Astrophysics Data System (ADS)

    Anikina, E. Yu.; Bortnikov, N. S.; Klubnikin, G. K.; Gamyanin, G. N.; Prokof'ev, V. Yu.

    2016-05-01

    The succession of mineral assemblages, chemistry of gangue and ore minerals, fluid inclusions, and stable isotopes (C, O, S) in minerals have been studied in the Mangazeya silver-base-metal deposit hosted in terrigenous rocks of the Verkhoyansk Fold-Thrust Belt. The deposit is localized in the junction zone of the Kuranakh Anticlinorium and the Sartanga Synclinorium at the steep eastern limb of the Endybal Anticline. The deposit is situated at the intersection of the regional Nyuektame and North Tirekhtyakh faults. Igneous rocks are represented by the Endybal massif of granodiorite porphyry 97.8 ± 0.9 Ma in age and dikes varying in composition. One preore and three types of ore mineralization separated in space are distinguished: quartz-pyrite-arsenopyrite (I), quartz-carbonate-sulfide (II), and silver-base-metal (III). Quartz and carbonate (siderite) are predominant in ore veins. Ore minerals are represented by arsenopyrite, pyrite, sphalerite, galena, fahlore, and less frequent sulfosalts. Three types of fluid inclusions in quartz differ in phase compositions: two- or three-phase aqueous-carbon dioxide (FI I), carbon dioxide gas (FI II), and two-phase (FI III) containing liquid and a gas bubble. The homogenization temperature and salinity fall within the ranges of 367-217°C and 13.8-2.6 wt % NaCl equiv in FI I; 336-126°C and 15.4-0.8 wt % NaCl equiv in FI III. Carbon dioxide in FI II was homogenized in gas at +30.2 to +15.3°C and at +27.2 to 29.0°C in liquid. The δ34S values for minerals of type I range from-1.8 to +4.7‰ (V-CDT); of type II, from-7.4 to +6.6‰; and of type III, from-5.6 to +7.1‰. δ13C and δ18O vary from-7.0 to-6.7‰ (V-PDB) and from +16.6 to +17.1 (V-SMOW) in siderite-I; from-9.1 to-6.9‰ (V-PDB) and from +14.6 to +18.9 (V-SMOW) in siderite-II; from-5.4 to-3.1‰ (V-PDB) and from +14.6 to +19.5 (V-SMOW) in ankerite; and from-4.2 to-2.9‰ (V-PDB) and from +13.5 to +16.8 (V-SMOW) in calcite. The data on mineral assemblages, fluid inclusions, and ratios of stable isotopes allow us to speak about the formation of the Mangazeya deposit in relation to the activity of the hydrothermal-magmatic system. The latter combines emplacement of subvolcanic granitic stocks and involvement of fluids variable in salinity and temperature in ore deposition zone. The fluids released from crystallizing felsic magma and were formed in a convective cell by heating of meteoric and marine waters. The mechanism of ore deposition is related to phase separation (boiling) and mixing of fluids.

  19. Sulfide-Sulfate Mineralizations in Verzino Area (Crotone Basin, Southern Italy): New insights on localized hydrothermal fluid circulations and their relationship with tectonics.

    NASA Astrophysics Data System (ADS)

    Berardi, Gabriele; Lucci, Federico; Cozzupoli, Domenico; Pizzino, Luca; Cantucci, Barbara; Quattrocchi, Fedora

    2010-05-01

    In this early stage of the work we present a preliminary study of hydrothermal mineralizations found in Verzino locality, Crotone Basin, Southern Appennines, (Calabria, Italy). Both geochemical and petrographic investigations were developed with the aim of understanding the genesis of the sulfide-sulfate associations present in the "Argille Marnose del Ponda" formation, deepening their relationship with fluids circulation. These mineralizations have been recognized only in two "Calanchi" morphostructures - Badlands like morphology developed by the differential erosional pattern of the "Argille Marnose del Ponda" fm. - and constituting the northwestern flank of a little valley evolved in the Miocene sedimentary sequence from "Conglomerato di S.Nicola" fm. to "Evaporiti Superiori" fm. The mineralizations are distributed along isooriented centimetric veins (with mean direction of N120) and in nodules diffused close to the veins. These hydrothermal mineralizations are constituted by an associations of Pyrite spherical nodules (millimetric to centimetric in radius with occurrences of well developed octahedral habit single crystals), sulphate crystals (Gypsum, Jarosite, NatroJarosite), Oxides (Goethite mainly), millimetric veins of Barite and micrometric Ankerite specimens. The data (mineral habits, semiquantitative compositions and x-Ray spectra), obtained by an integration of S.E.M and XRD investigations, permit us, at the current stage of the study, to hypothesize a possible hydrothermal origin (whose temperature range estimate needs further investigations) for the sulfide-sulfate mineral phases. At the moment, we exclude their primary or secondary sedimentary provenance. The comparison of our results with the previous scientific literature focused on hydrothermal sulfide-sulfate systems (Vinogradov and Stephanov, 1964; Kostov, 1968; Plummer 1971; Boles, 1978; Ferrini and Moretti 1998) allows us to propose a possible "thermal window" ranging in the interval 50°C-230°C, characterizing an exalative-ephitermal facies condition for the genesis of the here presented mineralizations. The supposed hydrothermal genesis, together with the localization and oriented distribution of the vein/nodule systems, suggest a strong control on the fluid circulation by the very local fault systems characterizing the tectonic of the investigated area. A very close relationship between faults and fluids in Calabria region has been recently claimed by Italiano et al (2010); the presence of thermal and sulphur-rich ground-waters farther south and west of the study area (Belvedere di Spinello, Verzino, Casabona and Cotronei), strongly supports our inferences. The study area (and in general the Crotone basin) has suffered two destructive earthquakes in 1638 and 1832, with an estimated magnitude of 6.5-6.8. Moreover, recent paleoseismological studies (Galli and Bosi, 2003; Galli et al., 2008) re-evaluated the seismic hazard of the area, by detecting some historical strong earthquakes along previously unknown fault systems. This work, with the reported results on mineral associations developed by important fluid/fault interactions, highlights the role and the timing of both localized stress and pore pressures cycles in an active tectonic setting, and may represent a new interpretation key and a clue reference for a deeper understanding of a not well known italian seismic area characterized, at least, by the presence of three regional active master faults: the Marchesato Fault, the Lakes fault the Cerenzia-San Nicola-Strongoli Line. Geochemical and isotopic analyses on mineralizations, host rock and spring fluids are in progress to better define and understand the local hydrothermal system and to propose a model of time and control of the tectonic on the fluid circulation.

  20. Origins of chromite and magnetite in sedimentary rocks deposited in a shallow water environment in the 3.2 Ga Moodies Group, South Africa

    NASA Astrophysics Data System (ADS)

    Otake, T.; Sakamoto, Y.; Itoh, S.; Yurimoto, H.; Kakegawa, T.

    2012-12-01

    *Otake, T. totake@eng.hokudai.ac.jp Div. of Sustainable Resources Engineering, Hokkaido Univ., Sapporo, Japan Sakamoto, Y. yu.sakamoto12@gmail.com Dep. of Earth Science, Tohoku Univ., Sendai, Japan Itoh, S. sitoh@ep.sci.hokudai.ac.jp Dep. of Natural History Sciences, Hokkaido Univ., Sapporo, Japan Yurimoto. H. yuri@ep.sci.hokudai.ac.jp Dep. of Natural History Sciences, Hokkaido Univ., Sapporo, Japan Kakegawa, T. kakegawa@m.tohoku.ac.jp Dep. of Earth Science, Tohoku Univ., Sendai, Japan Geochemical data from ferruginous chemical sedimentary rocks (e.g., Banded Iron Formation: BIF) have been used to reconstruct the surface environments of early Earth. However, only a few studies have investigated the geochemical characteristics of BIFs deposited in a shallow water environment during the Archean, which may have differed from those deposited in a deep water environment. Therefore, we investigated geological, petrographic and geochemical characteristics of ferruginous rocks deposited in a shallow water environment in the Moodies group, in the Barberton Greenstone Belt, South Africa. We obtained ferruginous rock samples in the Moodies group from both an outcrop and underground gold mine, and compared the characteristics of these samples. The 70 sedimentary rock samples were divided into groups based on the dominant Fe minerals they contain: Hematite-rich jaspilite (HM group), Magnetite-rich iron formation/shale/sandstone (MT group), and Siderite-rich sandstone (SD group). Samples in the HM group are predominantly composed of fine-grained quartz (< 20 μm) and hematite (< 5 μm), which are interpreted to be chemical precipitates. Samples in the MT group contain quartz, magnetite, siderite, ankerite, chlorite, biotite and chromite. The grain size of magnetite is much larger (20-150 μm) than that of hematite in the HM group. The magnetite is interpreted as a secondary mineral transformed from hematite during early diagenesis. Results of in situ oxygen isotope analysis by SIMS showed that magnetite in the Moodies group has similar δ18O values to those in the least metamorphosed BIFs. All chromite observed in the MT group is overgrown by magnetite. Samples in the SD group contain quartz, siderite, chlorite, biotite, and chromite; the chromite is included in Mg-rich siderite or silicate minerals (e.g., chlorite and biotite). Oxygen isotope compositions indicate that chromite in both the MT and SD groups, was hydrothermally altered. Results of geochemical analyses of the bulk outcrop samples showed that FeTotal/Ti and Cr/Ti ratios of outcrop samples increase concordantly in the ferruginous zone, particularly in the MT group. The Cr/Ti ratios of the underground samples also increase with increasing the Fetotal/Ti ratios. On the other hand, Th/U ratios of both the outcrop and underground samples decrease with increasing FeTotal/Ti ratios. The correlations of Fetotal/Ti ratios with U/Th and Cr/Ti ratios indicate that dissolved Cr and U species in the ocean were coprecipitated with ferric (hydr)oxides during the formation of ferruginous rocks of the Moodies Group. These results suggest that Cr and U were chemically mobile, possibly as oxidized species, in the Earth's surface environment at ~3.2 Ga.

  1. Petrophysical, Lithological and Mineralogical Characteristics of the Shale Strata of the Volga- Ural Region

    NASA Astrophysics Data System (ADS)

    Morozov, Vladimir P.; Plotnikova, Irina N.; Pronin, Nikita V.; Nosova, Fidania F.; Pronina, Nailya R.

    2014-05-01

    The objects of the study are Upper Devonian carbonate rocks in the territory of South-Tatar arch and Melekess basin in the Volga- Urals region. We studied core material of Domanicoid facies from the sediments of Mendymski and Domanik horizons of middle substage of Frasnian stage of the Upper Devonian. Basic analytical research methods included the following: study of the composition, structural and textural features of the rocks, the structure of their voids, filter and reservoir properties and composition of the fluid. The complex research consisted of macroscopic description of the core material, optical microscopy analysis, radiographical analysis, thermal analysis, x-ray tomography, electron microscopy, gas-liquid chromatography, chromate-mass spectrometry, light hydrocarbons analysis using paraphase assay, adsorbed gases analysis, and thermal vacuum degassing method. In addition, we performed isotopic studies of hydrocarbons saturating shale rocks. Shale strata are mainly represented by carbonate-chert rocks. They consist mainly of calcite and quartz. The ratio of these rock-forming minerals varies widely - from 25 to 75 percent. Pyrite, muscovite, albite, and microcline are the most common inclusions. Calcareous and ferruginous dolomite (ankerite), as well as magnesian calcite are tracked down as secondary minerals. While performing the tests we found out that the walls of open fractures filled with oil are stacked by secondary dolomite, which should be considered as an indication moveable oil presence in the open-cut. Electron microscopy data indicate that all the studied samples have porosity - both carbonates and carbonate-siliceous rocks. Idiomorphism of the rock-forming grains and pores that are visible under a microscope bring us to that conclusion. The analysis of the images indicates that the type of reservoir is either porous or granular. The pores are distributed evenly in the volume of rock. Their size is very unstable and varies from 0.5 microns to 100 microns. The lowest value are observed in long carbonate-siliceous rocks, the highest values are found in carbonate rocks. The latter is caused by the fact that there is a very strong recrystallization of calcite and its dolomite substitution in carbonates. Open porosity ranges from 0.65 to 7.98 percent, average value is 4.1percent . Effective porosity has an average value of 0.44 percent, ranging from 0.22 to 1.97. Permeability varies from 0.043 to 1.49 mD, average value is 0,191 mD. Organic matter was found in all samples. Its content varies within the section. The fluctuation range of from 1.0 to 20 percent. The lowest content of carbonates is found in carbonates, while the highest is observed in carbonate-siliceous rocks with a high content of chalcedony. Average organic matter content is 5-7 percent. According to Rock-Eval studies of the core, the catagenetic maturity of organic matter corresponds to MK1 - MK2 degree. We found a connection between the type of organic matter and the composition of adsorbed gas. We also could see that the samples with humic organics present in their organic matter and can be characterized by a fair dominance of methane over other gases. There is a clear relationship between organic matter content and the intensity of the gas saturation of the rock. Organic matter is characteristic mainly of the most siliceous formations. In "pure" carbonates, which are represented by micro-layers with different capacities, OM is not observed at all or its content is quite low.

  2. CaCO3-III and CaCO3-VI, high-pressure polymorphs of calcite: Possible host structures for carbon in the Earth's mantle

    NASA Astrophysics Data System (ADS)

    Merlini, M.; Hanfland, M.; Crichton, W. A.

    2012-06-01

    Calcite, CaCO3, undergoes several high pressure phase transitions. We report here the crystal structure determination of the CaCO3-III and CaCO3-VI high-pressure polymorphs obtained by single-crystal synchrotron X-ray diffraction. This new technical development at synchrotron beamlines currently affords the possibility of collecting single-crystal data suitable for structure determination in-situ at non-ambient conditions, even after multiphase transitions. CaCO3-III, observed in the pressure range 2.5-15 GPa, is triclinic, and it presents two closely related structural modifications, one, CaCO3-III, with 50 atoms in the unit cell [a=6.281(1) Å, b=7.507(2) Å, c=12.516(3) Å, α=93.76(2)°, β=98.95(2)°, γ=106.49(2)°, V=555.26(20) Å3 at 2.8 GPa], the second, CaCO3-IIIb, with 20 atoms [a=6.144(3) Å, b=6.3715(14) Å, c=6.3759(15) Å, α= 93.84(2)°, β=107.34(3)°, γ=107.16(3)°, V=224.33(13) Å3 at 3.1 GPa]. Different pressure-time experimental paths can stabilise one or the other polymorph. Both structures are characterised by the presence of non-coplanar CO3 groups. The densities of CaCO3-III (2.99 g/cm3 at 2.8 GPa) and CaCO3-IIIb (2.96 g/cm3 at 3.1 GPa) are lower than aragonite, in agreement with the currently accepted view of aragonite as the thermodynamically stable Ca-carbonate phase at these pressures. The presence of different cation sites, with variable volume and coordination number (7-9), suggests however that these structures have the potential to accommodate cations with different sizes without introducing major structural strain. Indeed, this structure can be adopted by natural Ca-rich carbonates, which often exhibit compositions deviating from pure calcite. Mg-calcites are found both in nature (Frezzotti et al., 2011) and in experimental syntheses at conditions corresponding to deep subduction environments (Poli et al., 2009). At these conditions, the low pressure rhombohedral calcite structure is most unlikely to be stable, and, at the same time, Mg and Fe solubility in aragonite is hindered energetically in the 9-fold coordination site. Above 15 GPa, and up to the maximum pressure investigated (40 GPa), we observe the high-pressure polymorph CaCO3-VI, triclinic [a=3.3187(12) Å, b=4.8828(14) Å, c=5.5904(14) Å, α=103.30(2)°, β=94.73(2)°, γ=89.21(2)°, V=87.86(20) Å3 at 30.4 GPa] with 10 atoms in the unit cell. It is characterised by coplanar CO3 groups but the structure is no longer layered, as in the lower pressure polymorphs. The density of the CaCO3-VI structure (3.78 g/cm3 at 30.4 GPa) is higher than aragonite. For this reason it could be supposed that a region may exist where this polymorph replaces aragonite in the Earth's intermediate mantle. The lower coordination number for the Ca site [7+2] instead of [9] in aragonite suggests that this structure could be easily adopted by an extended solid-solution range from calcite towards the dolomite [CaMg(CO3)2]-ankerite [CaFe(CO3)2] compositional join. The transitions from calcite to CaCO3-III, CaCO3-IIIb and CaCO3-VI are perfectly reversible and after pressure release we always observe the calcite structure, with the sample recovered as a single-crystal. Indeed, it is highly unlikely that these structures can be observed in samples recovered from high-pressure environments.

  3. Cockade-textured cataclasite and silica gel from damage zone in carbonated ultramafics: markers of cycles of seismic activity?

    NASA Astrophysics Data System (ADS)

    Scarsi, Marco; Crispini, Laura; Garofalo, Paolo; Capponi, Giovanni

    2016-04-01

    Shallow crustal processes occurring during seismic slips and generating fracture networks are of great interest due to their complex interplay with a spectrum of other geological processes . Our study focuses on faults with peculiar core textures, similar to those of "cockade breccia" (Genna et al., 1996) and "clast cortex grains" (Rempe et al., 2014), and on their relation with syntectonic hydrothermal alteration linked with Au bearing-quartz and chalcedony veins. Our work aims to study the enviromental conditions for the formation of such peculiar texture, their relation with the hydrothermal vein system and their potential as shallow seismic indicators. We present field, microstructural and petrochemical data of a peculiar damage zone of fault rocks located in carbonated peridotites and serpentinites of the Ligurian Alps (Voltri Massif, Italy). These are mainly reverse faults, which are coeval with syntectonic Au-bearing quartz veins and chalcedony veins (Giorza et al., 2010), in which lherzolites occupy the hangingwall of the faults and serpentinites the footwall. The fault rocks show evidence for carbonation, as olivine and serpentine are clearly transformed into an assemblage made of magnesite, dolomite and minor ankerite. The damage zones of the faults are serpentinite-rich and about 10 m in thickness, while the cataclasite cores are carbonate-rich and ca. 1 m thick. The top of the fault core shows the occurrence of a chalcedony shear veins with chatter marks and slikenlines on the surface. The "cockade breccia" is made of spherical aggregates of Fe-Mg carbonates and are 1 mm to 3 cm in size. These aggregates show cores of microcrystalline Fe-Mg carbonates, and concentric outer layers of relatively coarser Fe-Mg carbonates with radial or laminated texture. In some cases, these aggregates show evidence for rotation along secondary slip zones. We interpret all these features as the products of chemical interaction between the olivine and serpentine initially present within the fault rocks and the hydrothermal fluid that flowed within these faults. These interactions were probably similar to those occurring within the coeval Au- and chalcedony veins. Field evidence and theoretical considerations indicate that the reverse faults could have experienced stages of fault-valve behaviour (Sibson et al., 1998), which consisted in cycles of fluid pressure build-ups, fault opening, fluid flushing, and mineral precipitation during the seismic failure of the faults. These cycles varied transiently fault permeabilities. During the fluid pressure build up stage the radial coarse grains developed, while during the fluid flushing stage the clast cortex grains developed their laminated texture. The Au-quartz and chalcedony veins could have formed during the stages of fluid pressure drops following fault slip (Sibson et al., 1998, 2004). References Capponi G. & Crispini L., 1997, Progressive shear deformation in the metasediments of the Voltri Group (Ligurian Alps, Italy): occurence of structure recording extension parallel to the regional foliation, Boll. Soc. Geol. It., 116, 267-277. Genna A., Jébrack M., Marcoux E., Milési J.P., 1996, Genesis of cockade breccias in the tectonic evolution of the Cirotan epithermal gold system, West Java, Can. Journ. of Earth Sci., 33, 93-102. Giorza A., 2010, Late to post-metamorphic hydrotermalism in the Voltri Unit (Lavagnina Lakes Area, NW Alps). Structural-Petrological-Geochemical approach, PhD Thesis, University of Turin. Rempe M., Smith S. A. F., Ferri F., Mitchell T. M., 2014, Clast-cortex aggregates in experimental and natural calcite-bearing fault zones, Journ. Of Struct. Geol., 68, 142-157. Sibson R. H., 2004, Controls of maximum fluid overpressure defining conditions for mesozonal mineralization, Journ. of Struct. Geol., 26, 6-7, 1127-1136. Sibson R. H., Robert F., Poulsen H., 1998, High-angle reverse faults, fluid-pressure cycling, and mesothermal gold-quartz deposits, Geology, 16, 551-555. Spagnolo C., 2006, Late orogenic tectonics in the eastern sector of the Ligurian Alps, PhD Thesis, Univesity of Genoa.

  4. (S, C, O, Sr) isotopic constraints on the diagenetic evolution of the COX clay formations at the Bure URL site, Paris Basin)

    NASA Astrophysics Data System (ADS)

    Lerouge, C.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Widory, D.; Guerrot, C.; Buschaert, S.

    2009-04-01

    The Underground Research Laboratory of Bure, located in the Eastern part of the Paris Basin, was selected by ANDRA (French Agency for Nuclear Management) in order to study the feasibility of a nuclear waste disposal in the Callovian-Oxfordian thick clayey formation at 400 meters depth. Since 1994's, numerous investigations have been initiated to understand and predict the behaviour of the clay formation in time and in space, by constraining its stability, the chemical evolution of the porewaters, and solution transfers between the clayey formation and its adjacent limestone sequences during geological times (ANDRA, 2005). In that way, this study presents combined new mineralogical and isotopic data of the diagenetic mineral sequence to constrain the porewater chemistry of the rock at different stages of the sedimentary then burial history of the clayey formation. The petrological study of Callovian-Oxfordian claystones provided evidence of the following diagenetic mineral sequence: 1) Framboïdal pyrite ± micritic calcite in replacement of carbonate bioclasts and in bioturbations, 2) Iron-rich euhedral carbonates (ankerite, sideroplesite), Glauconite, 3) Sparry dolomite, celestite in residual porosity, 4) Chalcedony 5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (-38 to +74 permil/CDT), providing evidence of bacterial sulphate reduction processes. The lowest negative values (-38 to -22 permil) indicate precipitation of pyrite in a marine environment with a permanent recharge in sulphate, whereas the higher pyrite δ34S values (-14 up to +74 permil) show that pyrite precipitated in a system that closed for sulphate. Consequently the variations of pyrite δ34S in bioturbations along the lithostratigraphic profil indicate a change of sedimentation conditions from a deep marine environment to an environment with alternative recharge of marine sulphates; that is consistent with the transgression/regression cycle observed in the middle sequence of the formation. The δ34S values of celestite (+ 22 to +31 permil /CDT) reflect the last evolution stage of the system at which the bacterial activity ends, the celestite corresponding to the deposition of the residual dissolved sulphate anions in the diagenetic porewaters. The 87Sr/86Sr ratio of celestite (0.706872-0.707040) is consistent with a deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates (δ13C= +0.2 to +2.3 permil/PDB, δ18O= +27.7 to +28.7 permil/SMOW) whereas late diagenetic siderite is slightly 13C- depleted. The 13C-depletion could be attributed to a partial contribution in diagenetic porewaters of carbonate ions derived partially from the degradation of organic matter issue of the bacterial sulphate reduction. The δ18O values of late diagenetic chalcedony range between +27 and +31 permil(/SMOW), suggesting precipitation from marine-derived porewaters at temperatures of maximum burial (~40-50°C). Late calcite in veinlet reworking with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ18O values (~+19 permil/SMOW), suggesting they precipitated from meteoric fluids (δ18O ~ -6 permil), whose signature is close to present-day porewaters of the formation. To conclude, combined mineralogical and isotopic data show that pyrite, sulfates, calcite cement, euhedral iron-bearing carbonates and probably chalcedony are diagenetic phases precipitated from marine-derived porewaters in conditions controlled by bacterial sulphate reduction. A calcite veinlet reworking chalcedony and celestite (in the middle sequence of the formation) and euhedral quartz encrusting a vug in a limestone from the top of the clayey formation are the only mineral records of the introduction of meteoric fluid in the clay formation, and the only phases at isotopic equilibrium with present-day porewaters.

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