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1.
Edward M. Ripley 《Contributions to Mineralogy and Petrology》1979,69(4):345-354
Sulfide minerals in amounts up to 3 vol% are found in basal, chilled marginal zones of two layered peridotite-pyroxenite-gabbro sills in the Early Precambrian Deer Lake Complex, northcentral Minnesota. The sulfides occur interstitially to silicate minerals, and consist of pyrrhotite with minor exsolved cobaltian pentlandite, chalcopyrite, gersdorffite, and marcasite±pyrite as an alteration product of pyrrhotite.The basal chilled units (3–6 m) of the sills are divisable into three zones based primarily on textures. The lowermost zone is an equigranular basalt, whereas the overlying zone is characterized by skeletal, spinifex-like actinolite after clinopyroxene. The upper zone of the basal margins contains elongate and swallow tail plagioclase, and is barren of sulfide minerals.Electron microprobe analyses of sulfide minerals and modal data suggest that sulfide bulk compositions at 1,100–1,000 ° C represent a pyrrhotite solid solution and a coexisting Cu-rich sulfide liquid. Cooling of the Cu-rich liquid and low temperature transformations are thought to have produced chalcopyrite or chalcopyrite plus pyrrhotite. The sulfide minerals have reequlibrated to temperatures near 300 ° C or less.Analyses of sulfur content and 34S values suggest that assimilation of sulfur from adjacent country rocks was the principal mechanism responsible for anomalous concentrations of sulfides in the basal chilled margins. The distribution of sulfides in the peridotite-pyroxenite-gabbro portions of the sills, and calculations of settling rate preclude an origin involving gravitational settling of immiscible droplets through the magma body. 相似文献
2.
根据开放体系条件下的瑞利分馏原理,并考虑岩浆中可能溶解的合碳和含硫组分,从理论上定量模式了岩浆去气作用对火成岩碳、硫同位素组成的影响。结果表明,岩浆CO2去气作用能够导致岩石中碳酸盐显着亏损13C,其δ13C值能够从原始-5‰变化到-20‰(PDB);岩浆CH4去气作用则导致岩石中碳酸盐相对富集13C,其δ13C值能够从原始-5‰变化到+4‰。岩浆SO2去气作用可以导致岩石中硫化物显着亏损34S,其δ34S值能够从0‰变化到-8‰(CDT);岩浆H2S去气作用则导致岩石中的硫化物相对富集4S,其δ34S值能够从0‰变化到+6‰。因此,除源岩原始同位素不均一性和地壳物质混染能引起火成岩的碳、硫同位素组成发生较大变化外,岩浆去气作用也是重要原因之一。 相似文献
3.
Marc Peters Harald Strauss Sven Petersen Nicolai-Alexeji Kummer Christophe Thomazo 《Chemical Geology》2011,280(1-2):217-231
The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ34S range between ?29.8 and + 10.2‰ and Δ33S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ34SCRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ34S and Δ33S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ34S and Δ33S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ34S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO2 contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface. 相似文献
4.
The Poyi Cu-Ni deposit is hosted by the Early Permian Pobei mafic-ultramafic complex along the northern margin of the Tarim Plate. This series of multiple intrusions in the Poyi deposit can be divided into four lithologies: gabbro, dunite, hornblende peridotite, and wehrlite. The ore body consists mainly of disseminated sulfides hosted by hornblende peridotite. All the Poyi deposit sulfides show positive Δ33S values from 0.004 to 0.221‰ and negative δ34S values from −0.8 to −3.5‰. High Ni contents occur in the hornblende peridotites, which exhibit the highest Δ33S value of 0.221‰ and the lowest δ34S value of −3.5‰, indicating contamination by sulfides from Archean sedimentary rocks. This contamination was important during sulfide saturation in the Poyi intrusions and likely occurred at depth before the emplacement of the Poyi intrusions. The intrusions incorporated country rocks during their emplacement and consolidation, and the degree of assimilation increases from the central lithofacies (i.e., the hornblende peridotite) to the marginal lithofacies (i.e., the wehrlite, dunite, olivine gabbro, and gabbro). Higher Ni contents are correlated with lower degrees of contamination; thus, we infer that the contamination by the country Paleoproterozoic rocks, which contain significant amounts of gneiss and marble, hindered sulfide saturation.The whole-rock Ni content is negatively correlated with the MgO and Fo contents in the olivine and positively correlated with the FeO and MnO contents in the olivine. During crystallization, olivine becomes gradually richer in FeO but poorer in MgO, and Mn tends to be enriched in the late stages of the melt. We infer that the fractional crystallization of olivine was an important factor during sulfide saturation. 相似文献
5.
V.V. Ryabov O.N. Simonov S.G. Snisar A.A. Borovikov 《Russian Geology and Geophysics》2018,59(8):945-961
The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ34S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ34S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ34S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ34S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ34S = 21.6‰), in sulfate veins cutting dolomites (δ34S = 33‰), and in subsidence caldera sulfates in basalts (δ34S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ34S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ34S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ34S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ34S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and Pch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation. 相似文献
6.
7.
《International Geology Review》2012,54(7):660-669
Neoproterozoic to Cambrian ultrapotassic (K2O up to 13 wt%) peralkalic alkali-feldspar-rich syenitic plutons were emplaced along the boundary between the Cachoeirinha-Salgueiro and Alto Pajeu tectonostratigraphic terranes of the Borborema structural province, northeastern Brazil. Syenite and alkalic pyroxenitic magmas coexisted in these plutons, which locally carry mica pyroxenite xenoliths. In the Triunfo batholith, the largest peralkalic pluton in the region, syenites and alkalic pyroxenites have high pyroxene-corrected δ18O values (+8.1 to + 8.5‰SMOW in the syenite and +7.6 to + 7.7‰ in the alkalic pyroxenite), high δ34S (+12.3‰CDT in syenite and + 11.2‰CDT in alkalic pyroxenite), high initial 87Sr/86Sr ratios (0.7098, syenite and alkalic pyroxenite data lying on the same Rb-Sr isochron), and low εNd (?15.3 to ?17.2 in syenite and ?16.1 in pyroxenite). Whole-rock δ18OSMOW for mica pyroxenite xenoliths varies from +7.5 to +8.0‰SMOW. Syenite, alkalic pyroxenite, and xenoliths all are enriched in large-ion lithophile elements (LILE). These geochemical and isotopic signatures suggest that the magmas were derived from an incompatible-element-enriched mantle source; this protolith probably resulted from hybridization by addition of crustal material via subduction at ～2.4 Ga, as estimated from Nd model ages. Partial melting of metasomatized material and magma emplacement at a late stage of the Brasiliano Orogeny (566 Ma) were controlled by mantle-deep shear zones during the amalgamation of the Cachoeirinha-Salgueiro and Alto Pajeu terranes. 相似文献
8.
The evolution of the global sulfur isotope curve was plotted based on the δ34S values of evaporates resultant from oceanic evaporation. In the long period of geological history the δ34S values showed obvious peaks for three times during the process of ancient oceans’ sulfur isotope evolution, namely the Early Cambrian (+30‰), the Late Devonian (+25‰) and the Permian-Triassic transition interval (+17‰), but the causes of the abnormal rise of sulfur isotopic values during the geological period are still in question. In this paper, 18 samples collected from a large Devonian barite deposit from Zhenning County were analyzed to determine their δ34S values, revealing that the 18 samples have very high δ34S values (δ34S=41.88‰-+68.39‰), with an average close to 56.30‰, which are higher than the isotopic values of contemporary sulfates (+17‰- +25‰). A comparative analysis was conducted of the emerging of high δ34S barite deposits (from Cambrian and Devonian) and the δ34S variation curves of the ancient oceans. The results indicate that the time when the obvious peaks of δ34S values appeared and the time of massive sedimentation of high δ34S barite deposits are very close to each other, which, in our opinion, is not a coincidence. There may exist some correlations between the sulfur isotope evolution of ancient oceans during the diverse periods of geological history and the massive sedimentation of high δ34S barite deposits. Therefore, it is inferred that perhaps it was the massive sedimentation of high δ34S barites that caused the sharp rise of δ34S values in a short period of time. 相似文献
9.
Geology and Isotope Geochemistry of the Yinchanggou-Qiluogou Pb-Zn Deposit, Sichuan Province, Southwest China 总被引：1，自引：0，他引：1
The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD_(H2O-SMOW) and δ~(18)O_(H2O-SMOW) values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H_2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ~(13)C_(PDB) values ranging from-6.2‰ to-4.1‰ and δ~(18)O_(SMOW) values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ~(34)S_(CDT) values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The ~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates. 相似文献
10.
Hassan Baioumy 《Chemie der Erde / Geochemistry》2010,70(1):61-67
Jurassic high-sulfur coals from the Maghara area in Egypt were analyzed for the abundance and isotopic composition of different forms of sulfur. Analyses indicated that the sulfur occurs in the form of organic, pyrite, and sulfate forms. Pyrite sulfur represents the major fraction, while sulfate sulfur is minor and could be formed during sample preparation for the analyses.The δ34S CDT values of the organic sulfur are positive ranging between 1.0‰ and 13.5‰ with an average of 9.1‰. Pyrite δ34S values are also positive ranging between 1.5‰ and 15.4‰ with an average of 6.6‰. The high δ34S values of the organic sulfur in the Maghara coals suggest a freshwater origin of the organic components of these coals. The lack of correlation between pyrite and organic sulfur isotopes implies different incorporation mechanisms of sulfur. The high-sulfur contents along with the positive and high δ34S values suggest a marine origin of pyrite sulfur and support the geological interpretation of marine invasion after the peat formation that was responsible for the incorporation of the pyrite sulfur.The occurrence of pyrite as euhedral crystals as well as the high and positive δ34S values of the pyrite sulfur indicates the formation of pyrite during diagenesis as a result of marine water invasion of the preexisting peat in a brackish coastal plain environment. 相似文献
11.
H-O-S-Cu-Pb Isotopic Constraints on the Origin of the Nage Cu-Pb Deposit, Southeast Guizhou Province, SW China 总被引：1，自引：0，他引：1
The Nage Cu-Pb deposit,a new found ore deposit in the southeast Guizhou province,southwest China,is located on the southwestern margin of the Jiangnan Orogenic Belt.Ore bodies are hosted in slate and phyllite of Neoproterozoic Jialu and Wuye Formations,and are structurally controlled by EW-trending fault.It contains Cu and Pb metals about 0.12 million tonnes with grades of 0.2 wt% to 3.4 wt% Cu and 1.1 wt% to 9.27 wt% Pb.Massive and disseminated Cu-Pb ores from the Nage deposit occur as either veinlets or disseminations in silicified rocks.The ore minerals include chalcopyrite,galena and pyrite,and gangue minerals are quartz,sericite and chlorite.The H-O isotopic compositions of quartz,S-Cu-Pb isotopic compositions of sulfide minerals,Pb isotopic compositions of whole rocks and ores have been analyzed to trace the sources of ore-forming fluids and metals for the Nage Cu-Pb deposit.The δ65CuNBS values of chalcopyrite range from-0.09% to +0.33‰,similar to basic igneous rocks and chalcopyrite from magmatic deposits.δ65CuNBS values of chalcopyrite from the early,middle and final mineralization stages show an increasing trend due to63Cu prior migrated in gas phase when fluids exsolution from magma.δ34SCDT values of sulfide minerals range from 2.7‰ to +2.8‰,similar to mantle-derived sulfur(0±3‰).The positive correlation between δ65CuNBS and δ34SCDT values of chalcopyrite indicates that a common source of copper metal and sulfur from magma.δDH2OSMOW and δ18OH2O-SMOW values of water in fluid inclusions of quartz range from 60.7‰ to 44.4‰ and +7.9‰ to +9.0‰(T=260°C),respectively and fall in the field for magmatic and metamorphic waters,implicating that mixed sources for H2O in hydrothermal fluids.Ores and sulfide minerals have a small range of Pb isotopic compositions(208Pb/204Pb=38.152 to 38.384,207Pb/204Pb=15.656 to 17.708 and 206Pb/204Pb=17.991 to 18.049) that are close to orogenic belt and upper crust Pb evolution curve,and similar to Neoproterozoic host rocks(208Pb/204Pb=38.201 to 38.6373,207Pb/204Pb=15.648 to 15.673 and 206Pb/204Pb=17.820 to 18.258),but higher than diabase(208Pb/204Pb=37.830 to 38.012,207Pb/204Pb=15.620 to 15.635 and206Pb/204Pb=17.808 to 17.902).These results imply that the Pb metal originated mainly from host rocks.The H-O-S-Cu-Pb isotopes tegather with geology,indicating that the ore genesis of the Nage Cu-Pb deposit is post-magmatic hydrothermal type. 相似文献
12.
A. V. Nikiforov A. V. Bolonin B. G. Pokrovsky A. M. Sugorakova A. V. Chugaev D. A. Lykhin 《Geology of Ore Deposits》2006,48(4):256-276
The Rb-Sr isochron age of igneous ankerite-calcite and siderite carbonatites in central Tuva is estimated at 118 ± 9 Ma. The following ranges of initial values of O, C, Sr, and sulfide and S isotopic compositions were established: δ18Ocarb = +(8.8?14.7)‰, δ13Ccarb = ?(3.6?4.9)‰, δ18Oquartz = +(11.6?13.7)‰, δ34Spyrite = +(0.3?1.1)‰, and (87Sr/86Sr)i =0.7042?0.7048 for ankerite-calcite carbonatite and δ18Osid = +(9.2?12.4)‰, δ13Csid = ?(3.9?5.9)‰, δ18Oquartz = +(11.2?11.4)‰, δ34Spyrite = ?(4.4–1.8)‰, δ34Ssulfate = +(8.6?14.5)‰, and (87Sr/86Sr)i = 0.7042?0.7045 for siderite carbonatite. The obtained isotopic characteristics indicate that both varieties of carbonatites are cognate and their mantle source is comparable with the sources of Late Mesozoic carbonatites in the western Transbaikal region and Mongolia. The revealed heterogeneity of isotopic compositions of carbonatites is caused by their contamination with country rocks, replacement with hydrothermal celestine, and supergene alteration. 相似文献
13.
E. E. Amplieva 《Geology of Ore Deposits》2008,50(5):404-422
The sequence of orebody formation at the Talgan massive sulfide deposit; morphology of sulfide orebodies; mineralogy, texture, and structure of ore; chemical composition of minerals; and fluid inclusions and relationships between stable isotopes (S, C, O) in sulfides from ores and carbonate rocks are discussed. The deposit is localized in the Uzel’ga ore field of the northern Magnitogorsk Megazone. The sulfide ore is hosted in the upper felsic sequence of the Middle Devonian Karamalytash Formation, composed of basalt, basaltic andesite, and rhyodacite. Orebodies are irregular lenses lying conformably with host rocks. Pyrite, chalcopyrite, sphalerite, and fahlore are the major ore minerals; galena, bornite, and hematite are of subordinate abundance. Sulfide mineralization bears attributes of deposition under subseafloor conditions. The carbonate and rhyolite interlayers at the roofs of orebodies and the supraore limestone sequence served as screens. Zoning typical of massive sulfide deposits was not established. The study of fluid inclusions has shown that the temperature of the hydrothermal solution varied from 375 to 110°C. δ34S‰ ranges from ?2.4 to +3.2‰ in pyrite, from ?1.2 to +2.8‰ in chalcopyrite, and from ?3.5 to +3.0‰ in sphalerite (CDT). These parameters correspond to an isotopic composition of magmatic sulfur without a notable percentage of sulfate sulfur. δ13C and δ18O of carbonates vary from ?18.1 to +5.9‰ (PDB) and from +13.7 to +27.8‰ (SMOW), respectively. The carbon and oxygen isotopic compositions of carbonates from ores and host rocks markedly deviate from the field of marine carbonates; a deep source of carbon is suggested. The results obtained show that the main mass of polysulfide ore at the Talgan deposit was formed beneath the floor of a paleoocean. The ore-forming system was short-lived and its functioning did not give rise to the formation of zonal orebodies. Magmatic fluid played the leading role in mineral formation. 相似文献
14.
《Resource Geology》2018,68(3):227-243
As a newly discovered medium‐sized deposit (proven Pb + Zn resources of 0.23 Mt, 9.43% Pb and 8.73% Zn), the Dongzhongla skarn Pb–Zn deposit is located in the northern margin of the eastern Gangdese, central Lhasa block. Based on the geological conditions in this deposit of ore‐forming fluids, H, O, C, S, Pb, Sr, and noble gas isotopic compositions were analyzed. Results show that δ18OSMOW of quartz and calcite ranged from −9.85 to 4.17‰, and δDSMOW ranged from −124.7 to −99.6‰ (where SMOW is the standard mean ocean water), indicating magma fluids mixed with meteoric water in ore‐forming fluids. The δ13CPDB and δ18OSMOW values of calcite range from −1.4 to −1.1‰ and from 5.3 to 15.90‰, respectively, show compositions consistent with the carbonate limestone in the surrounding rocks, implying that the carbon was primarily sourced from the dissolution of carbonate strata in the Luobadui Formation. The ore δ34S composition varied in a narrow range of 2.8 to 5.7‰, mostly between 4‰ and 5‰. The total sulfur isotopic value δ34S was 4.7‰ with characteristics of magmatic sulfur. The 3He/4He values of pyrite and galena ranged from 0.101 to 5.7 Ra, lower than those of mantle‐derived fluids (6 ± 1 Ra), but higher than those of the crust (0.01–0.05 Ra), and therefore classified as a crust–mantle mixed source. The Pb isotopic composition for 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb values of the ores were in the ranges of 18.628–18.746, 15.698–15.802, and 39.077–39.430, respectively, consistent with the Pb isotopic composition of magmatic rocks in the deposit, classified as upper‐crust lead. The ore lead was likely sourced partially from the crustal basement of the Lhasa Terrane. The initial (87Sr/86Sr)i value from five sulfide samples ranged from 0.71732 to 0.72767, and associated ore‐forming fluids were mainly sourced from the partial melting of the upper‐crust materials. Pb isotopic compositions of ore sulfides from the Dongzhongla deposit are similar to that of the Yuiguila and Mengya'a deposit, indicating that they have similar sources of metal‐rich ore‐forming solution. According to basic skarn mineralogy, the economic metals, and the origin of the ore‐forming fluids, the Dongzhongla deposit was classified as a skarn‐type Pb–Zn deposit. 相似文献
15.
《International Geology Review》2012,54(6):565-576
In the Eastern Pontide Region of northeastern Turkey, volcanogenic Cu-Zn-Pb deposits of the Kuroko type are widespread within the dacitic series of the Liassic-Eocene volcano-sedimentary succession. Sulfide mineralization within the studied deposits shows four different depositional styles: disseminated ore; polymetallic stockwork ores; polymetallic massive ores; and disseminated pyrite in the hanging-wall tuff units. Only the stockwork and massive ores are economically important, and usually one or the other dominates in each ore body. The δ34S of sulfide minerals belonging to the various styles of mineralization are in the range from ?2.6 to +5.2% (VCDT): pyrite has the highest values and the galena lowest values in agreement with the usual isotopic-fractionation trends. Massive ores have heavier sulfur-isotope composition among the mineralization styles and the heaviest values are recorded in barite- and gypsum-rich deposits. The close similarity of the δ34S among the various mineralization episodes in some deposits indicates a single sulfur source having a stable and homogenous composition. The δ34S of sulfates fall into three groups: barites and primary gypsum (15.4 to 20.4%), close to coeval seawater sulfate; one value of barite (25.4%) heavier than coeval sea water; and values of secondary gypsum (2.2 to 8.0%) either very light compared to coeval seawater sulfate, or within the range recorded from sulfide minerals. The δ34S values of pyrite disseminated in the brecciated dacite tuff units are very close to zero and similar to the ones reported for magmatic rocks, suggesting a magmatic source for the sulfur of the earliest sulfide mineralization episode. These δ34S data are not sufficient to calculate the fraction of the reduced sulfur derived from seawater sulfate, as the associated fractionation factor cannot be constrained. 相似文献
16.
David A. Fike Niko Finke Jessica Zha Tori M. Hoehler 《Geochimica et cosmochimica acta》2009,73(20):6187-6204
Substantial isotopic fractionations are associated with many microbial sulfur metabolisms and measurements of the bulk δ34S isotopic composition of sulfur species (predominantly sulfates and/or sulfides) have been a key component in developing our understanding of both modern and ancient biogeochemical cycling. However, the interpretations of bulk δ34S measurements are often non-unique, making reconstructions of paleoenvironmental conditions or microbial ecology challenging. In particular, the link between the μm-scale microbial activity that generates isotopic signatures and their eventual preservation as a bulk rock value in the geologic record has remained elusive, in large part because of the difficulty of extracting sufficient material at small scales. Here we investigate the potential for small-scale (∼100 μm-1 cm) δ34S variability to provide additional constraints for environmental and/or ecological reconstructions. We have investigated the impact of sulfate concentrations (0.2, 1, and 80 mM SO4) on the δ34S composition of hydrogen sulfide produced over the diurnal (day/night) cycle in cyanobacterial mats from Guerrero Negro, Baja California Sur, Mexico. Sulfide was captured as silver sulfide on the surface of a 2.5 cm metallic silver disk partially submerged beneath the mat surface. Subsequent analyses were conducted on a Cameca 7f-GEO secondary ion mass spectrometer (SIMS) to record spatial δ34S variability within the mats under different environmental conditions. Isotope measurements were made in a 2-dimensional grid for each incubation, documenting both lateral and vertical isotopic variation within the mats. Typical grids consisted of ∼400-800 individual measurements covering a lateral distance of ∼1 mm and a vertical depth of ∼5-15 mm. There is a large isotopic enrichment (∼10-20‰) in the uppermost mm of sulfide in those mats where [SO4] was non-limiting (field and lab incubations at 80 mM). This is attributed to rapid recycling of sulfur (elevated sulfate reduction rates and extensive sulfide oxidation) at and above the chemocline. This isotopic gradient is observed in both day and night enrichments and suggests that, despite the close physical association between cyanobacteria and select sulfate-reducing bacteria, photosynthetic forcing has no substantive impact on δ34S in these cyanobacterial mats. Perhaps equally surprising, large, spatially-coherent δ34S oscillations (∼20-30‰ over 1 mm) occurred at depths up to ∼1.5 cm below the mat surface. These gradients must arise in situ from differential microbial metabolic activity and fractionation during sulfide production at depth. Sulfate concentrations were the dominant control on the spatial variability of sulfide δ34S. Decreased sulfate concentrations diminished both vertical and lateral δ34S variability, suggesting that small-scale variations of δ34S can be diagnostic for reconstructing past sulfate concentrations, even when original sulfate δ34S is unknown. 相似文献
17.
Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ33S (≡δ33S-0.515 δ34S) values of up to 0.04‰ even if δ34S values are identical. Detection of such small Δ33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ33S values ranging from −0.002 to 0.033 and δ34S from −0.5‰ to 5.3‰. The combined δ34S and Δ33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ34S but also in Δ33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles. 相似文献
18.
Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78 m. Sphalerite has δ114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ34SCDT values ranging from 0.2 to 5.0‰. Although δ34SCDT and δ114/110Cd values in sphalerites have no regular spatial variations, the δ34SCDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130 °C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ34S∑S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0 ± 3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit. 相似文献
19.
V. I. Vinogradov 《Lithology and Mineral Resources》2007,42(1):1-14
Based on evaporite sequences of the Irkutsk amphitheater, it is shown that sulfur in the Vendian-Lower Cambrian sedimentary sulfates displays a very wide scatter of sulfur isotope ratios and enrichment in heavy sulfur up to average values of δ34S ≈ +(27–30)‰. These features are related to sulfate reduction, which is distinctly expressed like other secondary alterations in the studied sections. Average δ34S values reflect the dynamics of isotopic effects rather than the initial sulfur composition of the oceanic water. The Irkutsk amphitheater can be considered natural model of sulfur isotopic variations in ancient evaporites. Existing concepts of the sulfur isotopic composition of Cambrian oceans need to be revised. 相似文献
20.
Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ34S 0.0 to 9.6‰, avg. δ34S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ34S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (206Pb/204Pb 17.541 ± 0.004 to 19.268 ± 0.001, 207Pb/204Pb 15.451 ± 0.001 to 15.684 ± 0.001, 208Pb/204Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ34S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing. 相似文献