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1.
Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ34SSO4) and sulfide (δ34SH2S) were similar to trends observed in the Black Sea water column: δ34SH2S and δ34SSO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in 34S relative to sulfate. Near the oxic-anoxic interface, however, the δ34SH2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ34SH2S and Δ33SH2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ34SSO4 values near the interface suggests ‘readdition’ of 34S-depleted sulfate during sulfide oxidation. A slight increase in δ34SSO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of 34S-depleted sulfur during sulfide production through SR. Our δ34SH2S and Δ33SH2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ34S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.  相似文献   

2.
An anomalous enrichment in marine sulfate δ34SSO4 is preserved in globally-distributed latest Ediacaran-early Cambrian strata. The proximity of this anomaly to the Ediacaran-Cambrian boundary and the associated evolutionary radiation has invited speculation that the two are causally related. Here we present a high-resolution record of paired sulfate (δ34SSO4) and pyrite (δ34Spyr) from sediments spanning ca. 547-540 million years ago (Ma) from the Ara Group of the Huqf Supergroup, Sultanate of Oman. We observe an increase in δ34SSO4 from ∼20‰ to ∼42‰, beginning at ca. 550 Ma and continuing at least through ca. 540 Ma. There is a concomitant increase in δ34Spyr over this interval from ∼ −15‰ to 10‰. This globally correlative enrichment, here termed the Ara anomaly, constitutes a major perturbation to the sulfur cycle. The absolute values of δ34Spyr reported here and in equivalent sections around the world, require the isotopic composition of material entering the ocean (δ34Sin) to be significantly more enriched than modern (∼3‰) values, likely in excess of 12‰ during the late Ediacaran-early Cambrian. Against this background of elevated δ34Sin, the Ara anomaly is explained not by increased fractionation between sulfate and pyrite (Δδ34S), but by an increase in pyrite burial (fpyr), most likely driven by enhanced primary production and sequestration of organic carbon, consistent with earlier reports of elevated organic carbon burial and widespread phosphorite deposition.  相似文献   

3.
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   

4.
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   

5.
Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ34SΣs of 0.7 ± 0.1 ‰. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ± 1.5‰. On the other hand, the concentration and δ34SΣs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and ?0.8 ± 0.2‰, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the ?o2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt.The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have δ34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ34S values (+5 to +6%.o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.  相似文献   

6.
Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ34SSO4 and δ18OSO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ18OH2O and initial δ18OSO4, all strains show 34S enrichment, whereas only six strains show significant 18O enrichment. The remaining six show no (or minimal) change in δ18OSO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO32−), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.  相似文献   

7.
Stable SO4 isotopes (δ34S-SO4 and δ18O-SO4), and more occasionally δ15N-NO3 were studied in groundwater from seven hard-rock aquifer catchments. The sites are located in Brittany (France) and all are characterized by intensive agricultural activity. The purpose of the study was to investigate the potential use of these isotopes for highlighting the fate of both SO4 and NO3 in the different aquifer compartments. Nitrate-contaminated groundwater occurs in the regolith; δ34S fingerprints the origin of SO4, such as atmospheric deposition and fertilizers, and δ18O-SO4 provides evidence of the cycling of S within soil. The correlation between the δ18O-SO4 of sulfates and the δ15N-NO3 of nitrates suggests that S and N were both cycled in soil before being leached to groundwater. Autotrophic and heterotrophic denitrification was noted in fissured aquifers and in wetlands, respectively, the two processes being distinguished on the basis of stable SO4 isotopes. During autotrophic denitrification, both δ34S-SO4 and δ18O-SO4 decrease due to the oxidation of pyrite and the incorporation of O from the NO3 molecule in the newly formed SO4. Within wetlands, fractionation occurs of O isotopes on SO4 in favour of lighter isotopes, probably through reductive assimilation processes. Fractionation of S isotopes is negligible as the redox conditions are not sufficiently reductive for dissimilatory reduction. δ34S-SO4 and δ18O-SO4 data fingerprint the presence of a NO3-free brackish groundwater in the deepest parts of the aquifer. Through mixing with present-day denitrified groundwater, this brackish groundwater can contribute to significantly increase the salinity of pumped water from the fissured aquifer.  相似文献   

8.
The sulfur isotope composition of tholeiitic basalts, olivine alkali basalts and alkalirich undersaturated basalts were investigated. A method of preparation was devised
  1. for the extraction of the small amounts of sulfur contained in the rock samples (about 100 ppm S),
  2. for the separation of sulfide- and sulfate-sulfur.
Tholeiitic and olivine alkali basalts show a predominance of sulfide-sulfur. Alkali-rich undersaturated basalts show sulfide- and sulfate-sulfur. The oxidation potential of the magma is reflected in the proportions of sulfide- and sulfate-sulfur. Differences in the conditions of oxidation are also the cause of the sulfur isotope fractionation observed. The mean in the isotope composition of the sulfur in the olivine alkali basalts (with the exception of two samples which show extreme deviation) is δ 34S= +1.3 per mil. The values for the olivine alkali basalts are concentrated around this mean in a remarkable way, showing only small deviation for the individual samples. When the tholeiitic basalts deviate from this mean, it is only with a relative enrichment in the 32S isotope. With a pronounced variation of the individual values, the mean for the sulfide-sulfur is δ 34S=?0.3 per mil. The few sulfate values of both types of basalt are without significance for the discussion of their origin. However, this does not apply to the alkali-rich undersaturated basalts. Due to the higher water content, this basaltic magma had a higher oxygen partial pressure which favoured the formation of SO2 and SO 4 2? besides H2S while pressure was released during the ascent of the magma. The sulfur isotope fractionation connected with this oxidation led to a total enrichment of 34S in the rock, (δ 34S for total sulfur: +3.1 per mil) with particular favouring the sulfate (δ 34S=+4.2 per mil). It is accepted that the sulfur of all three types of basalts derives directly from the mantle. The olivine alkali basalts show the least deviation from the mantle value, which, in the place of origin of the basalts from the region investigated, would probably have been δ 34S=+1.3(±0.5) per mil. From this it may be concluded that the olivine alkali basalts — the most frequent type of basalt in this region — had their origin in the partial melting of the mantle without further differentiation. From the sulfur isotope data we concluded that the primary isotope composition of the continental tholeiitic basalts probably corresponds to that of the olivine-alkali basalts, and to that of the mantle. However, due to degasing in the layers near to the surface, some samples lost 34S, which may be related to the formation of SO2 during the release of pressure. There is no positive indication of a differentiation in shallow depths (<15 km — in the sense of Green and Ringwood, 1967). The reason for the obvious isotopic fractionation of the alkali-rich undersaturated basalts may be seen in their higher primary water content. This is a pronounced indication of the origin of this type of magma. Bultitude and Green (1968) proved by experiment, that the formation of alkali-rich undersaturated basaltic magma is possible in the mantle in the presence of water. Only a small amount of water is available for the formation of magma in the mantle. With a water content higher than normal for basalts, only small amounts of magma can be formed, but at lower temperatures this would allow the melting of a larger fraction of mantle material. By reaction with the wall rock, these magmas could be enriched in those components of mantle minerals which have the lowest melting point. This may help to explain their geochemical characteristics.  相似文献   

9.
Statistical evaluation of 3056 δ13C measurements in carbonate rocks and fossils shows that they record a 2‰ 13C depletion from the late Proterozoic to the early Paleozoic, a 2.5‰ enrichment to the Permian, and a 1.5‰ depletion to the Cenozoic. These variations, not controlled primarily by facies or alteration phenomena, correlate negatively with the δ34S sulfate secular trend, as confirmed by collation of 1083 δ34S measurements. The correlation suggests that the biologically mediated redox fluxes of the C and S cycles have been approximately balanced through this long span of geological time, generally levelling available oxygen. Such a redox system is consistent with the controlling mechanism proposed by Garrels and Perry (1974). Consequently, the sedimentary reservoirs of Corganic as well as Sbacteriological'have varied through geological time.  相似文献   

10.
《Applied Geochemistry》2005,20(4):789-805
Mineralogical, hydrochemical and S isotope data were used to constrain hydrogeochemical processes that produce acid mine drainage from sulfidic waste at the historic Mount Morgan Au–Cu mine, and the factors controlling the concentration of SO4 and environmentally hazardous metals in the nearby Dee River in Queensland, Australia. Some highly contaminated acid waters, with metal contents up to hundreds of orders of magnitude greater than the Australia–New Zealand environmental standards, by-pass the water management system at the site and drain into the adjacent Dee River.Mine drainage precipitates at Mt. Morgan were classified into 4 major groups and were identified as hydrous sulfates and hydroxides of Fe and Al with various contents of other metals. These minerals contain adsorbed or mineralogically bound metals that are released into the water system after rainfall events. Sulfate in open pit water and collection sumps generally has a narrow range of S isotope compositions (δ34S = 1.8–3.7‰) that is comparable to the orebody sulfides and makes S isotopes useful for tracing SO4 back to its source. The higher δ34S values for No. 2 Mill Diesel sump may be attributed to a difference in the source. Dissolved SO4 in the river above the mine influence and 20 km downstream show distinctive heavier isotope compositions (δ34S = 5.4–6.8‰). The Dee River downstream of the mine is enriched in 34S (δ34S = 2.8–5.4‰) compared with mine drainage possibly as a result of bacterial SO4 reduction in the weir pools, and in the water bodies within the river channel. The SO4 and metals attenuate downstream by a combination of dilution with the receiving waters, SO4 reduction, and the precipitation of Fe and Al sulfates and hydroxides. It is suggested here that in subtropical Queensland, with distinct wet and dry seasons, temporary reducing environments in the river play an important role in S isotope systematics.  相似文献   

11.
The δ34S values of dissolved sulfide and the sulfur isotope fractionations between dissolved sulfide and sulfate species in Floridan ground water generally correlate with dissolved sulfate concentrations which are related to flow patterns and residence time within the aquifer. The dissolved sulfide derives from the slow in situ biogenic reduction of sulfate dissolved from sedimentary gypsum in the aquifer. In areas where the water is oldest, the dissolved sulfide has apparently attained isotopic equilibrium with the dissolved sulfate (Δ34S = 65 per mil) at the temperature (28°C) of the system. This approach to equilibrium reflects an extremely slow reduction rate of the dissolved sulfate by bacteria; this slow rate probably results from very low concentrations of organic matter in the aquifer.In the reducing part of the Edwards aquifer, Texas, there is a general down-gradient increase in both dissolved sulfide and sulfate concentrations, but neither the δ34S values of sulfide nor the sulfide-sulfate isotope fractionation correlates with the ground-water flow pattern. The dissolved sulfide species appear to be derived primarily from biogenic reduction of sulfate ions whose source is gypsum dissolution although upgradient diffusion of H2S gas from deeper oil field brines may be important in places. The sulfur isotope fractionation for sulfide-sulfate (about 38 per mil) is similar to that observed for modern oceanic sediments and probably reflects moderate sulfate reduction in the reducing part of the aquifer owing to the higher temperature and significant amount of organic matter present; contributions of isotopically heavy H2S from oil field brines are also possible.  相似文献   

12.
A diffusion-diagenesis model of the sulfur cycle is developed to calculate theoretical distributions of stable sulfur isotopes in marine sediments. The model describes the depth variation in δ34S of dissolved sulfate and H2S. and of pyrite. The effects of sulfate reduction, sulfate and H2S diffusion. and of sedimentation are considered as well as the bacterial isotope fractionation and the degree of pyrite formation. Under open system conditions of sulfur diagenesis the isotopic difference, ΔSO2?4 — H2S, tends to increase with depth being smaller than the bacterial fractionation factor near the sediment surface and larger in deeper layers. The two isotopes in SO2?4 or in H2S do not diffuse in the same proportion as they occur in the porewater. This explains why sulfur, which is incorporated from seawater sulfate by diffusion and precipitation as pyrite, can be enriched in 32S relative to the seawater sulfate. The model calculations demonstrate the importance of taking the whole dynamic sulfur cycle into account before drawing conclusions about sulfur diagenesis from the stable isotope distribution.  相似文献   

13.
Evaporite outcrops are rare in the Basque Cantabrian basin due to a rainy climate, but saline springs with total dissolved solids ranging from 0.8 to 260 g/L are common and have long been used to supply spas and salterns. New and existing hydrochemistry of saline springs are used to provide additional insight on the origin and underground extent of their poorly known source evaporites. Saline water hydrochemistry is related to dissolution of halite and gypsum from two evaporitic successions (Triassic “Keuper” and Lower Cretaceous “Wealden”), as supported by rock samples from outcrops and oil exploration drill cuttings. The δ34S value of gypsum in the Keuper evaporites and sulfate in the springs is δ34SSO4 = 14.06 ± 1.07‰ and δ18OSO4 = 13.41 ± 1.44‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 124 and 288 ppm. The δ34S value of gypsum in the Wealden evaporites and sulfate in the springs is δ34SSO4 = 19.66 ± 1.76‰, δ18OSO4 = 14.93 ± 2.35‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 15 and 160 ppm. Wealden evaporites formed in a continental setting after the dissolution of Keuper salt. Gypsum δ34SSO4 and δ18OSO4 modification from Keuper to Wealden evaporites was due mainly to bacterial SO4 reduction in an anoxic, organic matter-rich environment. Saline springs with Wealden δ34SSO4 values are present in a 70 × 20 km wide area. Saline water temperatures, their δ2HH2O and δ18OH2O values, and the geological structure defines a hydrogeological model, where meteoric water recharges at heights up to 620 m above spring levels and circulates down to 720 m below them, thereby constraining the height range of evaporite dissolution. Groundwater flow towards saline springs is driven by gravity and buoyancy forces constrained by a thrust and fault network.  相似文献   

14.
Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε18OSO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent εSO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. δ34SSO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ34SSO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.  相似文献   

15.
The δ34S-values of total sulfur in the Jurassic tholeiite flows on Mt. Falla in Antarctica range from ?1.45 to +11.73‰. The concentrations of sulfur range from 80 to 480 ppm, which is typical of subaerial lava flows that lose varying proportions of sulfur by out-gassing of SO2. The concentrations of magnetite range from less than 1% to more than 4% and appear to correlate inversely with the total Fe content of the flows. However, the five flows which are anomalously enriched in 34S also have elevated magnetite concentrations. We suggest that the elevated magnetite concentrations and the 34S enrichment were both caused by high oxygen fugacities (fO2) in the melt. The magnetite concentrations are affected by the fugacity of oxygen through equilibrium in the FMQ buffer whereas the enrichment of the flows in 34S resulted from outgassing of SO2 at fO2 greater than ~ 10?8 atm. The dependence of δ34S and the magnetite concentrations of the flows on fO2 is supported by the stratigraphic variation of these parameters and by their direct linear correlation.  相似文献   

16.
《Applied Geochemistry》2005,20(7):1427-1444
Very high S oils (up to 14.7%) with H2S contents of up to 92% in the associated gas have been found in the Tertiary in the Jinxian Sag, Bohai Bay Basin, PR China. Several oil samples were analyzed for C and S stable isotopes and biomarkers to try to understand the origin of these unusual oil samples.The high S oils occur in relatively shallow reservoirs in the northern part of the Jinxian Sag in anhydrite-rich reservoirs, and are characteristic of oils derived from S-rich source rocks deposited in an enclosed and productive stratified hypersaline water body. In contrast, low S oils (as low as 0.03%) in the southern part of the Jinxian Sag occur in Tertiary lacustrine reservoirs with minimal anhydrite. These southern oils were probably derived from less S-rich source rocks deposited under a relatively open and freshwater to brackish lake environment that had larger amounts of higher plant inputs.The extremely high S oil samples (>10%) underwent biodegradation of normal alkanes resulting in a degree of concentration of S in the residual petroleum, although isoprenoid alkanes remain showing that biodegradation was not extreme. Interestingly, the high S oils occur in H2S-rich reservoirs (H2S up to 92% by volume) where the H2S was derived from bacterial SO4 reduction, most likely in the source rock prior to migration. Three oils in the Jinxian Sag have δ34S values from +0.3‰ to +16.2‰ and the oil with the highest S content shows the lightest δ34S value. This δ34S value for that oil is close to the δ34S value for H2S (∼0‰). It is possible that H2S was incorporated into functionalized compounds within the residual petroleum during biodegradation at depth in the reservoir thus accounting for the very high concentrations of S in petroleum.  相似文献   

17.
The paper presents the results of determinations of stable S and O isotopes of dissolved sulfates and O and H stable isotopes of waters from three ponds, that is, Marczakowe Do?y acid pond, Marczakowe Do?y fish pond and Podwi?niówka acid pit pond, located in the Holy Cross Mountains (south-central Poland). The δ34SV-CDT and δ18OV-SMOW of SO4 2? in waters of three ponds (n = 14) varied from ?16.2 to ?9.5 ‰ (mean of ?13.6 ‰) and from ?8.1 to ?3.2 ‰ (mean of ?4.8 ‰), respectively. The mean δ34S–SO4 2? values were closer to those of pyrite (mean of ?25.4 ‰) and efflorescent sulfate salts (mean of ?25.6 ‰), recorded previously in the Podwi?niówka quarry, than to sulfates derived from other anthropogenic or soil and bedrock sources. The SO4 2? ions formed by bacterially induced pyrite oxidation combined with bacterial (dissimilatory) dissolved sulfate reduction, and presumably with subordinate mineralization of carbon-bonded sulfur compounds, especially in both Marczakowe Do?y ponds. In addition, the comparison of δ18O–SO4 2? and δ18O–H2O values indicated that 75–100 % of sulfate oxygen was derived from water. Due to the largest size, the Podwi?niówka acid pit pond revealed distinct seasonal variations in both δ18O–H2O (?9.2 to ?1.6) and δD–H2O (?29.7 to ?71.3) values. The strong correlation coefficient (r 2 = 0.99) was noted between δ18O–H2O and δD–H2O values, which points to atmospheric precipitation as the only source of water. The sediments of both acid ponds display different mineral inventory: the Marczakowe Do?y acid pond sediment consists of schwertmannite and goethite, whereas Podwi?niówka acid pit pond sediment is composed of quartz, illite, chlorite and kaolinite with some admixture of jarosite reflecting a more acidic environment. Geochemical modeling of two acid ponds indicated that the saturation indices of schwertmannite and nanosized ε-Fe2O3 (Fe3+ oxide polymorph) were closest to thermodynamic equilibrium state with water, varying from ?1.44 to 3.05 and from ?3.42 to 6.04, respectively. This evidence matches well with the obtained mineralogical results.  相似文献   

18.
19.
《Applied Geochemistry》1997,12(3):305-319
An analysis of the S and O isotopic compositions and concentrations of dissolved S04 in river-and lake-water from 7 major catchments of the North and South Islands, New Zealand, allows the distinction between natural (geological, geothermal and volcanic) and anthropogenic S sources.The Buller and the Wairau, relatively pristine rivers in the South Island, show two end-member mixing between34S- and18O-rich rain-water S04 (relatively enriched isotope values) and relatively depleted S04 from oxidation of bedrock sulfide. Tertiary sediments contribute the isotopically most depleted S (down to δ34SCDT−15‰) to the river-water S04, whereas Mesozoic greywacke contributes S with slightly positive δ34S values. River-water S04δ18OSMOW values range from 0 to + 5‰ most probably depending on the micro-environment of the oxidising zone. South Island rivers with S04δ34S> + 5‰ have low S04 concentrations (< 3 mgl−1) and are dominantly composed of rain-water S04 which is principally sea-water derived. In the North Island, the Hutt River S04 samples also lie on an isotopic mixing trend from “greywacke bedrock” to rain-water S04, the latter with δ34S and δ18O values up to + 16 and + 6‰ respectively and a So4/SO4 + Cl fraction of 0.15 (sea-water is 0.12. Although dominated by greywacke, some samples in the Wairarapa area have relatively enriched δ18Sand δ34S values and elevated S04 concentrations (up to 16 mgl), together with higher SO4/SO4 + Cl fraction ratios. This suggests input of fertilizer S04 (δ34S+ 17.2‰andδ18O+ 12.7‰) in the rivers of this agricultural area. The fertilizer loading of the Ruamahanga river can be estimated by its graphical offset from a deduced baseline for bedrockrainfall derived S04 on a S versus O isotope plot. The fertilizer loading represents about 20% of the S04 in the river. Extrapolation of this figure to the annual river discharge indicates that approximately 18% of the amount applied within the catchment is lost to the river.The source of the Whangaehu river is the Ruapehu crater lake (active volcano) with high S04 concentrations and very enriched S04 isotopic signatures (δ34S> + 17‰andδ18O> + 12‰). Downstream this water is diluted by tributaries with lower S04 concentration and isotope signatures of Tertiary sediments similar to the rivers in the South Island. Both geothermal and rain-water S04 inputs to the streams flowing into Lakes Taupo and Rotorua were identified isotopically; in particular waters flowing out from Lake Rotorua have a higher geothermal derived S04 content than the inflows, indicating that there must be a considerable underwater geothermal input to the lake.  相似文献   

20.
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   

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