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1.
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   

2.
Acid sulfate-chloride thermal water samples collected together with fumarolic gases from various volcanic areas in northeastern Japan were studied chemically and isotogdically. δ34S (COT) values of sulfate and hydrogen sulfide from these volcanic hot springs range from +4.0 to +31 and from ?15.0 to ?2.0% respectively, with δ34Sys value of +2.5 to +31. The δ34S of the sulfate in the more saline waters tends to become smaller with increasing ratio of SO4 to Cl, although the chemical and isotopic composition of acid thermal water within some areas may be altered by secondary processes during the discharge of the thermal waters. This trend can be explained by the reaction of the volcanic gases, having S/Cl of 4 ~ 7 and total sulfur of ~0% in δ34S, with ground water at 200°C, and/or the removal of sulfide phase depleted in 34S from the acid thermal water formed by the disproportionation of volcanic sulfur. The sulfur species in acid sulfate-chloride thermal water are shown to be volcanic exhalations.  相似文献   

3.
Concentrations of oceanic and atmospheric oxygen have varied over geologic time as a function of sulfur and carbon cycling at or near the Earth’s surface. This balance is expressed in the sulfur isotope composition of seawater sulfate. Given the near absence of gypsum in pre-Phanerozoic sediments, trace amounts of carbonate-associated sulfate (CAS) within limestones or dolostones provide the best available constraints on the isotopic composition of sulfate in Precambrian seawater. Although absolute CAS concentrations, which range from those below detection to ∼120 ppm sulfate in this study, may be compromised by diagenesis, the sulfur isotope compositions can be buffered sufficiently to retain primary values.Stratigraphically controlled δ34S measurements for CAS from three mid-Proterozoic carbonate successions (∼1.2 Ga Mescal Limestone, Apache Group, Arizona, USA; ∼1.45-1.47 Ga Helena and Newland formations, Belt Supergroup, Montana, USA; and ∼1.65 Ga Paradise Creek Formation, McNamara Group, NW Queensland, Australia) show large isotopic variability (+9.1‰ to +18.9‰, −1.1‰ to +27.3‰, and +14.1‰ to +37.3‰, respectively) over stratigraphic intervals of ∼50 to 450 m. This rapid variability, ranging from scattered to highly systematic, and overall low CAS abundances can be linked to sulfate concentrations in the mid-Proterozoic ocean that were substantially lower than those of the Phanerozoic but higher than values inferred for the Archean. Results from the Belt Supergroup specifically corroborate previous arguments for seawater contributions to the basin. Limited sulfate availability that tracks the oxygenation history of the early atmosphere is also consistent with the possibility of extensive deep-ocean sulfate reduction, the scarcity of bedded gypsum, and the stratigraphic δ34S trends and 34S enrichments commonly observed for iron sulfides of mid-Proterozoic age.  相似文献   

4.
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   

5.
Sulfur isotope compositions of pumice and adsorbed volatiles on ash from the first historical eruption of Anatahan volcano (Mariana arc) are presented in order to constrain the sources of sulfur erupted during the period 10-21 May, 2003. The isotopic composition of S extracted from erupted pumice has a narrow range, from δ34SV-CDT +2.6‰ to +3.2‰, while the composition of sulfur adsorbed onto ash has a larger range (+2.8‰ to +5.3‰). Fractionation modeling for closed and open system scenarios suggests that degassing of SO2 raised the δ34SV-CDT value of S dissolved in the melt from an initial composition of between +1.6‰ and +2.6‰ for closed-system degassing, or between −0.5‰ and +1.5‰ for open-system degassing, however closed-system degassing is the preferred model. The calculated values for the initial composition of the magma represent a MORB-like (δ34SV-CDT ∼ 0‰) mantle source with limited contamination by subducted seawater sulfate (δ34SV-CDT +21‰). Modeling also suggests that the δ34SV-CDT value of SO2 gas in closed-system equilibrium with the degassed magma was between +0.9‰ and +2.5‰. The δ34SV-CDT value of sulfate adsorbed onto ash in the eruption plume (+2.8‰ to +5.1‰) is consistent with sulfate formation by oxidation of magmatic SO2 in the eruption column. The sulfur isotope composition of sulfate adsorbed to ash changes from lower δ34S values for ash erupted early in the eruption to higher δ34S values for ash erupted later in the eruption. We interpret the temporal/stratigraphic change in sulfate isotopic composition to primarily reflect a change in the isotopic composition of magmatic SO2 released from the progressively degassing magma and is attributed to the expulsion of an accumulated gas phase at the beginning of the eruption. More efficient oxidation of magmatic SO2 gas to sulfate in the early water-rich eruption plume probably contributed to the change in S isotope compositions observed in the ash leachates.  相似文献   

6.
This study investigates the sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and works to reconcile the relationships between the oxygen and sulfur isotopic and elemental systems. We report results of experiments with natural populations of sulfate-reducing bacteria using sediment and seawater from a marine lagoon at Fællestrand on the northern shore of the island of Fyn, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45‰ for 34S/32S) with higher δ18O accompanying higher δ34S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of 17O-labeled water and the 17O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The 17O data provides evidence for recycling of sulfur from metabolic intermediates and for an 18O/16O fractionation of ∼25-30‰ for dissimilatory sulfate reduction. The close correlation between the 17O data and the sulfur isotope data suggests that isotopic exchange between cell water and external water (reactor water) was rapid under experimental conditions. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. This value is slightly lower than observed in studies of natural ecosystems [e.g., Wortmann U. G., Chernyavsky B., Bernasconi S. M., Brunner B., Böttcher M. E. and Swart P. K. (2007) Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130). Geochim. Cosmochim. Acta71, 4221-4232]. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96%), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate and released back to the external sulfate pool (∼70%), and also that a fraction of the sulfur intermediates between sulfite and sulfide were recycled to sulfate. These parameters can be constrained because of the independent information provided by δ18O, δ34S, δ17O labels, and Δ33S.  相似文献   

7.
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   

8.
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   

9.
The discovery of 33S anomalies in Archean sedimentary rocks has established that the early Earth before ∼2.2 Ga (billion years ago) had a very different sulfur cycle than today. The origin of the anomalies and the nature of early sulfur cycle are, however, poorly known and debated. In this study, we analyzed the total sulfur and oxygen isotope compositions, the δ18O, Δ17O, δ34S, Δ33S, and Δ36S, for the >3.2 Ga Fig Tree barite deposits from the Barberton Greenstone Belt, South Africa. The goal is to address two questions: (1) was Archean barite sulfate a mixture of 33S-anomalous sulfate of photolysis origin and 33S-normal sulfate of other origins? (2) did the underlying photochemical reactions that generated the observed 33S anomalies for sulfide and sulfate also generate 17O anomalies for sulfate?We developed a new method in which pure barite sulfate is extracted for oxygen and sulfur isotope measurements from a mixture of barite sands, cherts, and other oxygen-bearing silicates. The isotope data reveal that (1) there is no distinct 17O anomaly for Fig Tree barite, with an average Δ17O value the same as that of the bulk Earth (−0.02 ± 0.07‰, N = 49); and (2) the average δ18O value is +10.6 ± 1.1‰, close to that of the modern seawater sulfate value (+9.3‰). Evidence from petrography and from the δ18O of barites and co-existing cherts suggest minimum overprinting of later metamorphism on the sulfate’s oxygen isotope composition. Assuming no other processes (e.g., biological) independently induced oxygen isotope exchange between sulfate and water, the lack of reasonable correlation between the δ18O and Δ33S or between the δ34S and Δ33S suggests two mutually exclusive scenarios: (1) An overwhelming majority of the sulfate in the Archean ocean was of photolysis origin, or (2) The early Archean sulfate was a mixture of 33S-normal sulfates and a small portion (<5%?) of 33S-anomalous sulfate of photolysis origin from the atmosphere. Scenario 1 requires that sulfate of photolysis origin must have had only small 33S or 36S anomalies and no 17O anomaly. Scenario 2 requires that the photolysis sulfate have had highly negative δ34S and Δ33S values, recommending future theoretical and experimental work to look into photochemical processes that generate sulfate in Quadrant I and sulfide in Quadrant III in a δ34S (X)-Δ33S (Y) Cartesian plane. A total sulfur and oxygen isotope analysis has provided constraints on the underlying chemical reactions that produced the observed sulfate isotope signature as well as the accompanying atmospheric, oceanic, and biological conditions.  相似文献   

10.
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   

11.
岩浆去气作用碳硫同位素效应   总被引：6，自引：0，他引：6       下载免费PDF全文
 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   

12.
喀斯特地表水和地下水的交换活跃,地下水系统容易受到地表污染物的污染。为了解喀斯特城市地表水—地下水系统污染特征和污染物质来源,对贵阳市地表水、地下水、雨水和城市排污污水的硫同位素和氯同位素组成变化进行了研究。贵阳市不同类型水体的δ37Cl值在-4.07‰～+2.03‰之间变化,δ34SSO4值变化为-20.4‰～+20.9‰。大气输入物质和城市排污污水的δ37Cl、δ34S及Cl-/SO42-比值与地表水和地下水的不同,稳定硫和氯同位素的结合研究为示踪地下水污染物来源提供了有效研究手段。贵阳市地下水中的Cl-和SO42-至少有4种来源,人为活动通过城市排污和大气输入向地下水系统大量输入了硫酸盐和氯离子。   相似文献   

13.
Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits   总被引：2，自引：0，他引：2  
Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ34S versus δ18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ34S versus δ18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.  相似文献   

14.
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   

15.
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   

16.
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   

17.
The sulfur isotopic composition (δ34S) of petroleum is believed to be affected mainly by sulfur incorporation reactions into the sedimentary organic matter during the early diagenesis. However, secondary processes could affect the original δ34S of oil under the effect of thermal maturity or of the microbial activity of biodegraded reservoirs. In this study, the different processes that may affect the δ34S of in-reservoir oils were assessed based on the sulfur content and isotopes of a series of oil and core samples coming from various reservoirs of the Lower Cretaceous Mannville Group, Western Canada Sedimentary Basin (WCSB). Based on the molecular study, these samples appear to have reached various levels of maturity and biodegradation, ranging from 0 to 6.5 on the biodegradation scale of Peters and Moldowan. In addition, mixing of organic matter coming from different source rocks was identified based on the comparison with extensive correlation studies performed in the WCSB.Investigation of the δ34S shows a trend that seems a priori correlated to the level of biodegradation. However, a careful interpretation of molecular and sulfur isotope data leads to the conclusion that the observed δ34S variations have rather to be ascribed to contributions of oils generated by various source rocks. Alternatively, variations of δ34S could neither be related to maturity differences nor to kinetic effects during organic sulfur compounds biodegradation. In the case of some specific core samples showing a common origin based on biomarker study, δ34S variations might not be related to different sources but to secondary sulfur incorporation/exchange processes occurring within the reservoir. These processes would involve reduced sulfur species from bacterial sulfate reduction formed in situ or migrated into Mannville reservoirs. This hypothesis is supported by laboratory experiments showing sulfur exchange/incorporation under plausible conditions for shallow reservoirs.  相似文献   

18.
The coexistence of magmatic anhydrite and sulfide minerals in non-arc-related mafic magmas has only rarely been documented. Likewise the S isotope fractionation between sulfate and sulfide in mafic rocks has infrequently been measured. In the Kharaelakh intrusion associated with the world-famous Noril’sk ore district in Siberia coexisting magmatic anhydrite and sulfide minerals have been identified. Sulfur isotope compositions of the anhydrite-sulfide assemblages have been measured via both ion microprobe and conventional analyses to help elucidate the origin of the anhydrite-sulfide pairs. Magmatic anhydrite and chalcopyrite are characterized by δ34S values between 18.8‰ and 22.8‰, and 9.3‰ and 13.2‰, respectfully. Coexisting anhydrite and chalcopyrite show Δ values that fall between 8.5‰ and 11.9‰. Anhydrite in the Kharaelakh intrusion is most readily explained by the assimilation of sulfate from country rocks; partial reduction to sulfide led to mixing between sulfate-derived sulfide and sulfide of mantle origin. The variable anhydrite and sulfide δ34S values are a function of differing degrees of sulfate reduction, variable mixing of sulfate-derived and mantle sulfide, incomplete isotopic homogenization of the magma, and a lack of uniform attainment of isotopic equilibrium during subsolidus cooling. The δ34S values of sulfide minerals have changed much less with cooling than have anhydrite values due in large part to the high sulfide/sulfate ratio. Variations in both sulfide and anhydrite δ34S values indicate that isotopically distinct domains existed on a centimeter scale. Late stage hydrothermal anhydrite and pyrite also occur associated with Ca-rich hydrous alteration assemblages (e.g., thomsonite, prehnite, pectolite, epidote, xonotlite). δ34S values of secondary hydrothermal anhydrite and pyrite determined by conventional analyses are in the same range as those of the magmatic minerals. Anhydrite-pyrite Δ values are in the 9.1-10.1‰ range, and are smaller than anticipated for the low temperatures indicated by the silicate alteration assemblages. The small Δ values are suggestive of either sulfate-sulfide isotopic disequilibrium or closure of the system to further exchange between ∼550 and 600 °C. Our results confirm the importance of the assimilation of externally derived sulfur in the generation of the elevated δ34S values in the Kharaelakh intrusion, but highlight the sulfur isotopic variability that may occur in magmatic systems. In addition, our results confirm the need for more precise experimental determination of sulfate-sulfide sulfur isotope fractionation factors in high-T systems.  相似文献   

19.

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.

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20.
The Bleiberg Pb-Zn deposit in the Drau Range is the type locality of Alpine-type carbonate-hosted Pb-Zn deposits. Its origin has been the subject of on-going controversy with two contrasting genetic models proposed: (1) the SEDEX model, with ore forming contemporaneously with sedimentation of the Triassic host rocks at about 220 Ma vs. (2) the epigenetic MVT model, with ores forming after host rock sedimentation at about 200 Ma or later. Both models assume that, on a deposit or even district scale, a fixed paragenetic sequence of ore minerals can be established. The results of our detailed petrographic, chemical and sulfur isotope study of two key ore-samples from two major ore horizons in the Wetterstein Formation at Bleiberg (EHK02 Erzkalk horizon and Blb17 Maxer Bänke horizon) demonstrate that there is no fixed paragenetic sequence of ore minerals. Small-scale non-systematic variations are recorded in textures, sphalerite chemistry and δ34S. In each sample, texturally different sphalerite types (colloform schalenblende, fine- and coarse-grained crystalline sphalerite) co-occur on a millimeter to centimeter scale. These sphalerites represent multiple mineralization stages/pulses since they differ in their trace element inventory and in their δ34S. Nonetheless, there is some correspondence of sphalerite micro-textures, sulfur isotope and chemical composition between the two samples, with microcrystalline colloform schalenblende being Fe-rich, having high Fe/Cd (15 and 9, respectively) and a light sulfur isotope composition (δ34S −26.0 to −16.2‰). Cadmium-rich and Fe-poor sphalerite in both samples has relatively heavier sulfur isotope composition: in sample EHK02 this sphalerite has Fe/Cd of ∼0.5 and δ34S from −6.6 to −4.6‰; in sample Blb17 Fe/Cd is ∼0.1 and δ34S ranges from −15.0 to −1.5‰. Barite, which is restricted to sample EHK02, has δ34S ≈ 17‰. The large variations in δ34S recorded on the mm to cm-scale is consistent with variable contributions of reduced sulfur from two different sulfur reservoirs. The dominant reservoir with δ34S values <−20‰ likely results from local bacteriogenic sulfate reduction (BSR), whereas the second reservoir, with δ34S about −5‰ suggests a hydrothermal source likely linked with thermochemical sulfate reduction (TSR). Based on this small- to micro-scale study, no simple, deposit-wide paragenetic and sulfur isotope evolution with time can be established. In the Erzkalk ore (sample EHK02) an earlier Pb-Zn-Ba stage, characterized by heavy sulfur isotope values, is succeeded by a light δ34S-dominated Zn-Pb-F stage. In contrast, the several mineralization pulses identified in the stratiform Zn-Pb-F Maxer Bänke ore (sample Blb17) define a broad trend to heavier sulfur isotope values with time. The interaction documented in these samples between two sulfur reservoirs is considered a key mechanism of ore formation.  相似文献   

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