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1.
The sulfur isotopic composition of the Herrin (No. 6) Coal from several localities in the Illinois Basin was measured. The sediments immediately overlying these coal beds range from marine shales and limestones to non-marine shales. Organic sulfur, disseminated pyrite, and massive pyrite were extracted from hand samples taken in vertical sections.The values from low-sulfur coals (< 0.8% organic sulfur) underlying nonmarine shale were +3.4 to +7.3%0 for organic sulfur, +1.8 to +16.8%0 for massive pyrite, and +3.9 to +23.8%0 for disseminated pyrite. In contrast, the (> 0.8% organic sulfur) underlying marine sediments were more variable: organic sulfur, ?7.7 to +0.5%0, pyrites, ?17.8 to +28.5%0. In both types of coal, organic sulfur is typically enriched in 34S relative to pyritic sulfur.In general, δ 34S values increased from the top to the base of the bed. Vertical and lateral variations in δ 34S are small for organic sulfur but are large for pyritic sulfur. The sulfur content is relatively constant throughout the bed, with organic sulfur content greater than disseminated pyrite content. The results indicate that most of the organic sulfur in high-sulfur coals is derived from post-depositional reactions with a 34S-depleted source. This source is probably related to bacterial reduction of dissolved sulfate in Carboniferous seawater during a marine transgression after peat deposition. The data suggest that sulfate reduction occurred in an open system initially, and then continued in a closed system as sea water penetrated the bed.Organic sulfur in the low-sulfur coals appears to reflect the original plant sulfur, although diagenetic changes in content and isotopic composition of this fraction cannot be ruled out. The wide variability of the δ 34S in pyrite fractions suggests a complex origin involving varying extents of microbial H2S production from sulfate reservoirs of different isotopic compositions. The precipitation of pyrite may have begun soon after deposition and continued throughout the coalification process. 相似文献
2.
The stable enrichment of pyrite from magnesite ores in δ34S isotope (from 5.4 to 6.9‰) compared with pyrite from the host (sedimentary and igneous) rocks was established in the classical Satka sparry magnesite ore field. Concretionary segregations of fine-grained pyrite in dolomite are depleted in the heavy sulfur isotope (δ34S, from–9.1 to–5.8‰). Pyrite from dolerite is characterized by δ34S values (–1.1 and 1.7‰) close to the meteorite sulfur. The δ34S values in barite from the underlying dolomite horizon vary in the range of 32.3–41.4‰. The high degree of homogeneity of the sulfur isotope composition in pyrite from magnesite is a result of thermochemical sulfate reduction during the syngenetic crystallization of pyrite and magnesite from epigenetic brines, formed during dissolution of evaporite sulfate minerals at the stage of early catagenesis of the Riphean deposits.
相似文献3.
Yaofa Jiang Erika R. Elswick Maria Mastalerz 《International Journal of Coal Geology》2008,73(3-4):273-284
Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ34S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ34S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in 34S relative to those from the parent coal (average 7.5‰). The δ34S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ34S values for SO4− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion. 相似文献
4.
Large rounded pyrite grains (>1 mm), commonly referred to as “buckshot” pyrite grains, are a characteristic feature of the auriferous conglomerates (reefs) in the Witwatersrand and Ventersdorp supergroups, Kaapvaal Craton, South Africa. Detailed petrographic analyses of the reefs indicated that the vast majority of the buckshot pyrite grains are of reworked sedimentary origin, i.e., that the pyrite grains originally formed in the sedimentary environment during sedimentation and diagenesis. Forty-one of these reworked sedimentary pyrite grains from the Main, Vaal, Basal, Kalkoenkrans, Beatrix, and Ventersdorp Contact reefs were analyzed for their multiple sulfur isotope compositions (δ34S, Δ33S, and Δ36S) to determine the source of the pyrite sulfur. In addition, five epigenetic pyrite samples (pyrite formed after sedimentation and lithification) from the Middelvlei and the Ventersdorp Contact reefs were measured for comparison. The δ34S, Δ33S, and Δ36S values of all 41 reworked sedimentary pyrite grains indicate clear signatures of mass-dependent and mass-independent fractionation and range from ?6.8 to +13.8?‰, ?1.7 to +1.7?‰, and ?3.9 to +0.9?‰, respectively. In contrast, the five epigenetic pyrite samples display a very limited range of δ34S, Δ33S, and Δ36S values (+0.7 to +4.0?‰, ?0.3 to +0.0?‰. and ?0.3 to +0.1?‰, respectively). Despite the clear signatures of mass-independent sulfur isotope fractionation, very few data points plot along the primary Archean photochemical array suggesting a weak photolytic control over the data set. Instead, other factors command a greater degree of influence such as pyrite paragenesis, the prevailing depositional environment, and non-photolytic sulfur sources. In relation to pyrite paragenesis, reworked syngenetic sedimentary pyrite grains (pyrite originally precipitated along the sediment-water interface) are characterized by negative δ34S and Δ33S values, suggesting open system conditions with respect to sulfate supply and the presence of microbial sulfate reducers. On the contrary, most reworked diagenetic sedimentary pyrite grains (pyrite originally precipitated below the sediment-water interface) show positive δ34S and negative Δ33S values, suggesting closed system conditions. Negligible Δ33S anomalies from epigenetic pyrite suggest that the sulfur was sourced from a mass-dependent or isotopically homogenous metamorphic/hydrothermal fluid. Contrasting sulfur isotope compositions were also observed from different depositional environments, namely fluvial conglomerates and marine-modified fluvial conglomerates. The bulk of the pyrite grains from fluvial conglomerates are characterized by a wide range of δ34S values (?6.2 to +4.8?‰) and small Δ33S values (±0.3?‰). This signature likely represents a crustal sulfate reservoir derived from either volcanic degassing or from weathering of sulfide minerals in the hinterland. Reworked sedimentary pyrite grains from marine-modified fluvial conglomerates share similar isotope compositions, but also produce a positive Δ33S/δ34S array that overlaps with the composition of Archean barite, suggesting the introduction of marine sulfur. These results demonstrate the presence of multiple sources of sulfur, which include atmospheric, crustal, and marine reservoirs. The prevalence of the mass-dependent crustal sulfur isotope signature in fluvial conglomerates suggests that sulfate concentrations were probably much higher in terrestrial settings in comparison to marine environments, which were sulfate-deficient. However, the optimum conditions for forming terrestrial sedimentary pyrite were probably not during fluvial progradation but rather during the early phases of flooding of low angle unconformities, i.e., during retrogradational fluvial deposition, coupled in some cases with marine transgressions, immediately following inflection points of maximum rate of relative sea level fall. 相似文献
5.
The S-isotope composition (δ34SCDT) of 213 samples of sulfides, sulfates and native sulfur from the pyrite mineralizations of southern Tuscany and associated country rocks were determined. The sulfur isotopic composition of pyrite is quite homogeneous and similar for all studied ore bodies, with an average δ34S value near +9,5‰. Pyrite disseminated within the Filladi di Boccheggiano formation, and thought to be authigenic, shows a much larger range of δ34S values (-13.1 to +14.5‰). The isotopic compositions of other sulfides associated with pyrite in the deposits show that isotopic equilibrium among sulfides was approached on a regional scale, but seldom fully attained. Isotopic data suggest that sedimentary marine sulfate was the ultimate source of sulfur in ores. Sulfates (mostly anhydrite) from the sulfate-carbonate lenses associated with both the Filladi di Boccheggiano and the Calcare Cavernoso formations also have similar and homogeneous compositions (average δ34S=+15–16‰). Coexisting sulfates and sulfides are not in isotopic equilibrium. In the light of the isotopic data, among the many proposed genetic models for the largest stratabound pyrite bodies the two following alternatives appear the most likely: 1) in agreement with recently suggested hypotheses, the ore bodies are older than the emplacement of the Mio-Pliocenic granitoids in the area, and are probably hydrothermal-sedimentary in origin, coeval with associated country rocks; 2) the ore bodies were formed as a consequence of bacterial reduction of anhydrite in low-temperature convection systems related to the early stages of the Mio-Pliocenic thermal anomaly. In both cases, the emplacement of the Mio-Pliocenic granitoids caused metamorphism and remobilization of the pre-existing ores, producing smaller discordant mineralized bodies. 相似文献
6.
西秦岭阳山金矿带硫同位素特征:成矿环境与物质来源约束 总被引：13，自引：9，他引：4
阳山金矿带成岩期的黄铁矿主要为立方体-他形,反映出一种较低温度(<200℃)、成岩流体的过饱和度低、快速冷却、氧逸度和硫逸度低、物质供应不足的成岩条件,δ34S值变化范围较大(-4.2‰～12.5‰),反映了硫源自于泥盆系地层,其中灰岩中黄铁矿硫源自于海水中硫酸根离子的还原作用,千枚岩中黄铁矿经历了细菌还原作用。成矿期黄铁矿具有多种晶形,但立方体单晶较少,指示成矿系统处于中-低温(200～300℃)、成矿流体的过饱和度高、缓慢冷却、氧逸度和硫逸度高、物质供应充分的成矿有利条件。成矿早阶段和主阶段硫化物的δ34S值变化范围为-4.2‰～3‰,接近于岩浆硫范围,其中成矿主阶段的黄铁矿以五角十二面体、八面体和立方体形成的聚形更常见,且聚形黄铁矿的硫同位素值变化范围更窄(-2.1‰～1.2‰),更符合岩浆硫来源特征;成矿晚阶段辉锑矿的δ34S值变化范围为-6.6‰～-4.5‰,而与其共生的黄铁矿δ34S值分别是7.6‰和-12.1‰,反映晚阶段除岩浆岩硫源外,浅变质的泥盆系地层也提供了部分硫源。 相似文献
7.
Ad. A. Aliev V. Yu. Lavrushin S. V. Kokh E. V. Sokol O. L. Petrov 《Lithology and Mineral Resources》2017,52(5):358-368
Geochemical studies of pyrite crystals from the mud volcanic ejecta in Azerbaijan were studied. It is shown that all of them have cubic shape. Determination of the sulfur isotope composition revealed a wide variation range of δ34S values from–27.0 to +26.4‰. Signs of spatial zonation were recorded in the distribution of δ34S values—lower values are confined to the present-day coastline of the Caspian Sea. Appearance of pyrite with a high share of 34S is attributed to sulfate reduction that takes place in an environment with excess organic matter. It is supposed that the isotopically heavy sulfides represent the “neck” facies that are formed at the periphery of mud volcanic conduits at the contact of the hydrocarbon-rich mud volcanic fluids with stratal waters of host sediments. 相似文献
8.
The typical for marine sediments decrease in the amount of sulfate ion in interstitial solutions with increasing depth owing to sulfate reduction and attenuation of the diffusion of near-bottom waters is manifested as the basic-to-acid zonation in the sulfur isotope composition of the diagenetic pyrite nodules (increase of δ34S values from the center to edge). In sandstones of the Early Carboniferous Emyaksin Formation, which is developed at middle reaches of the Vilyui River (Sakha-Yakutia), we detected a peculiar sulfide nodule. In contrast to common nodules, this nodule is marked by the δ34S value decreasing from 7.5…8.6‰ at the center to –30…–31.4‰ at the edge. Such acid-to-basic zonation is attributed to the origin of nodule in a freshened basin (delta) with a sulfate-depleted environment, which gave way to a sulfate-enriched environment owing to the expulsion brines from the underlying gypsiferous sequences. 相似文献
9.
10.
The Jinding Zn–Pb deposit located in the Mesozoic-Cenozoic Lanping Basin of southwest China has ore reserves of ∼ 220 Mt with an average grade of 6.1% Zn and 1.3% Pb. The mineralization is hosted by sandstone in the Early Cretaceous Jingxing Formation and limestone breccia in the Paleocene Yunlong Formation. Mineralization in both types of host rocks is characterized by a paragenetic sequence beginning with marcasite–sphalerite (Stage 1) followed by pyrite–marcasite–sphalerite–galena (Stage 2), and then galena–sphalerite–pyrite–sulfate–carbonate (Stage 3). Pyrite from these stages have different δ33S compositions with pyrite from Stage 1 averaging − 9.6‰, Stage 2 averaging − 8.9‰, and Stage 3 averaging + 0.3‰. Sphalerite hosted by the sandstone has similar δ66Zn values ranging from 0.10 to 0.30‰ in all stages of the mineralization, but sphalerite samples from the limestone breccia-hosted ore show variable δ66Zn values between − 0.03 and 0.20‰. Our data on sphalerite precipitated during the earlier stages of mineralization has a constant δ66Zn value and cogenetic pyrite displays a very light sulfur isotope signature, which we believe to reflect a sulfur source that formed during bacterial sulfate reduction (BSR). The Stage 3 sphalerite and pyrite precipitated from a late influx of metal-rich basinal brine, which had a relatively constant variable δ66Zn isotopic composition due to open system isotope fractionation, and a near zero δ33S composition due to the influence of abiotic thermochemical sulfate reduction from observed sulfates in the host rock. 相似文献
11.
E. M. Ripley 《Mineralium Deposita》1983,18(1):3-15
The Deer Lake Complex, located in north-central Minnesota, consists of a series of layered peridotite-pyroxenite-gabbro sills. Sulfide minerals occur as fine disseminations throughout pyroxenite and gabbro units, and occur more sporadically in peridotite and basal chilled margin units. Sulfide volume percentage rarely exceeds 0.5. A distinct zonation in sulfide mineralogy and sulfur isotopic composition characterizes the sills. Cobaltian pentlandite is the dominant sulfide mineral in peridotite (pd) units, with Ni-enrichment most likely linked to the serpentinization process. δ34Spd values are variable, ranging from ?3.5 to +2.8‰. Sulfide assemblages in pyroxenite (px) and lower gabbro units consist of chalcopyrite, pyrrhotite, and minor pentlandite. δ34Spx values range from ?1 to +1 ‰. Pyrite is the principal sulfide mineral in upper gabbro (μg) units. Its origin may be related to increased f02 conditions of the remaining melt and to reaction between a S-bearing volatile phase and mafic silicates. δ34Sug values range from 1 to 3.5 ‰. Sulfur isotopic values of chilled margin (2–9 ‰) and peridotite units, together with the erratic spatial distribution of sulfide minerals in these zones, suggests that the parent magma was not initially saturated with sulfur, and that local sulfide concentrations are the result of incorporation of sulfur derived from metasedimentary country rocks. Sulfide saturation was more uniformly reached during pyroxenite formation, with contained sulfur being of magmatic origin. Enrichment in 34S of pyrite from upper gabbro may be explained by buildup of isotopically heavy sulfur following a Rayleigh process, coupled with possible involvement of a SO2-rich fluid phase during hydrothermal alteration. 相似文献
12.
More than 200 analyses of the sulfur isotopic composition of sulfides from various terrigenous and intrusive host rocks, metasomatically altered wall rocks, and gold lodes of the Upper Kolyma region are presented. In accessory pyrite of the metaterrigenous rocks, δ34S varies from ?23.1 to +5.7‰ δ34S of pyrite and arsenopyrite from gold-quartz mineralization is within the range ?10.6 to ?0.4‰ and is close to the average δ34S of pyrite from the metaterrigenous rocks (?4.4‰). In the intrusive rocks, δ34S of pyrite varies from ?3.8 to +2.6‰ (+0.7‰, on average) and drastically differs from δ34S of arsenopyrite from postmagmatic gold-rare-metal mineralization (?7.9 to ?2.7‰; ?5.2‰, on average). The comparison of the δ34S of accessory sulfides from the host rocks with δ34S of sulfides from the gold deposits suggests that sulfur mobilized from the terrigenous sequences participated in the hydrothermal process. The results obtained are consistent with the metamorphic model of the formation of gold-quartz deposits in the Upper Kolyma region. 相似文献
13.
14.
Late Variscan vein-type mineralization in the Iberian Pyrite Belt, related to the rejuvenation of pre-existing fractures during late Variscan extensional tectonism, comprises pyrite–chalcopyrite, quartz–galena–sphalerite, quartz–stibnite–arsenopyrite, quartz–pyrite, quartz–cassiterite–scheelite, fluorite–galena–sphalerite–chalcopyrite, and quartz–manganese oxide mineral assemblages. Studies of fluid inclusions in quartz, stibnite, and barite as well as the sulfur isotopic compositions of stibnite, galena, and barite from three occurrences in the central part of the Iberian Pyrite Belt reveal compelling evidence for there having been different sources of sulfur and depositional conditions. Quartz–stibnite mineralization formed at temperatures of about 200 °C from fluids which had undergone two-phase separation during ascent. Antimony and sulfide are most probably derived by alteration of a deeper lying, volcanic-hosted massive sulfide mineralization, as indicated by δ34S signatures from ?1.45 to ?2.74‰. Sub-critical phase separation of the fluid caused extreme fractionation of chlorine isotopes (δ37Cl between ?1.8 and 3.2‰), which correlates with a fractionation of the Cl/Br ratios. The source of another high-salinity fluid trapped in inclusions in late-stage quartz from quartz–stibnite veins remains unclear. By contrast, quartz–galena veins derived sulfide (and metals?) by alteration of a sedimentary source, most likely shale-hosted massive sulfides. The δ34S values in galena from the two study sites vary between ?15.42 and ?19.04‰. Barite which is associated with galena has significantly different δ34S values (?0.2 to 6.44‰) and is assumed to have formed by mixing of the ascending fluids with meteoric water. 相似文献
15.
Pedro J. Marenco Frank A. Corsetti Douglas E. Hammond Alan J. Kaufman David J. Bottjer 《Chemical Geology》2008,247(1-2):124-132
The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ34S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ34S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ34S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ34Spyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe3+ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H2O, not O2. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition. 相似文献
16.
B. G. Pokrovskii 《Lithology and Mineral Resources》2009,44(3):258-266
Dolomites from the productive Osa horizon (upper subformation of the Lower Cambrian Bilir Formation) in the Talakan petroleum field show a prominent 1–2‰ decrease in δ18O (from 23–24 to 21–22‰), which presumably marks a zone of relatively high water/rock ratios. Productive boreholes are characterized by moderate δ34S values (from 25.1 to 30.6‰) and negative correlation between δ34S in anhydrite and δ18O in associated dolomite, which points to a partial sulfate reduction during catagenesis. In nonproductive borehole, δ34S values increase significantly (from 31.4 to 35.6‰) and show positive correlation with δ18O in dolomite. Rocks recovered by nonproductive borehole possibly recrystallized during early diagenesis, and, correspondingly lost their permeability and capacity to form pores. Limestones and dolomites of the Osa horizon have a carbon isotopic composition within the range of normal marine carbonates (δ13C = 0 ± 1 ‰), which does not indicate a significant role of organic matter in postsedimentary recrystallization of carbonate sediments. A positive δ13C excursion up to 4.5‰ recorded in the lower subformation of the Bilir Formation presumably occurred at the sedimentation stage under conditions of high rates of bioproductivity and organic matter burial in sediments. 相似文献
17.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite. 相似文献
18.
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
19.
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
20.
Mruganka K. Panigrahi Dinseh Pandit Rajesh K. Naik Shunso Ishihara 《Resource Geology》2013,63(1):110-116
δ34S values of pyrite, molybdenite and chalcopyrite were determined from the Malanjkhand copper deposit. These minerals constitute the primary sulfide phases that were deposited after the initial magnetite deposition in the main orebody and host granitoid. Pyrite exhibits a depleted range of values (?2.63 to ?0.56‰), chalcopyrite, a very narrow range of values around zero (?0.039 to 0.201‰) and molybdenite furnishes a range of enriched values (0.68 to 1.98‰). On back calculation of the δ34S values of H2S in the fluid from which the minerals were likely to have precipitated, using standard expressions for equilibrium fractionation at the temperature range obtained from fluid inclusion and mineral fluid equilibria, it is observed that H2S in the fluid at pyrite deposition was depleted and gradually became enriched towards molybdenite and chalcopyrite deposition. This trend is best explained as being due to inorganic reduction of SO42? in the fluid and is very much in agreement with the paragenetic sequence indicating increasing activity of H2S in the fluid. The very restricted range in the δ34S values of sulfide minerals in the fluid does indicate a single, possibly magmatic, source of sulfur that also agrees well with the earlier deduced model of genesis of the deposit as an ancient geothermal system associated with granitic magmatism. 相似文献