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1.
Groundwater and sediment samples (∼ 1 m depth) at sites representative of different groundwater pathways were collected to determine the aqueous speciation of sulfur and the fractionation of sulfur isotopes in aqueous and solid phases. In addition, selected sediment samples at 5 depths (from oxic to anoxic layers) were collected to investigate the processes controlling sulfur biogeochemistry in sedimentary layers. Pyrite was the dominant sulfur-bearing phase in the capillary fringe and groundwater zones where anoxic conditions are found. Low concentrations of pyrite (< 5.9 g kg− 1) coupled with high concentrations of dissolved sulfide (4.81 to 134.7 mg L− 1) and low concentrations of dissolved Fe (generally < 1 mg L− 1) and reducible solid-phase Fe indicate that availability of reactive Fe limits pyrite formation. The relative uniformity of down-core isotopic trends for sulfur-bearing mineral phases in the sedimentary layers suggests that sulfate reduction does not result in significant sulfate depletion in the sediment. Sulfate availability in the deeper sediments may be enhanced by convective vertical mixing between upper and lower sedimentary layers due to evaporative concentration. The large isotope fractionation between dissolved sulfate and sedimentary sulfides at Owens Lake provides evidence for initial fractionation from bacterial sulfate reduction and additional fractionation generated by sulfide oxidation followed by disproportionation of intermediate oxidation state sulfur compounds. The high salinity in the Owens Lake brines may be a factor controlling sulfate reduction and disproportionation in hypersaline conditions and results in relatively constant values for isotope fractionation between dissolved sulfate and total reduced sulfur.  相似文献   

2.
Sulfur isotope fractionation during microbial sulfate reduction in brackish estuarine sediments was studied using an experimental flow-through reactor approach designed to preserve the in situ physical, geochemical and microbial structure of the sediment. Concurrent measurements of potential sulfate reduction rates and 34S/32S fractionations were carried out using intact sediment slices (2 cm thick, 4.2 cm diameter) from unvegetated, intertidal sites adjoining a salt marsh along the Scheldt estuary, The Netherlands. A total of 30 reactor experiments were performed with sediments collected in February, May and October 2006. The effects of incubation temperature (10, 20, 30 and 50 °C) and sediment depth (0-2, 4-6 and 8-10 cm) were investigated. Sulfate was supplied in non-limiting concentrations via the reactor inflow solutions; no external electron donor was supplied. Isotope fractionations (ε values) were calculated from the measured differences in sulfate δ34S between in- and outflow solutions of the reactors, under quasi-steady state conditions. Potential sulfate reduction rates (SRR) varied over one order of magnitude (5-49 nmol cm−3 h−1) and were highest in the 30 °C incubations. They decreased systematically with depth, and were highest in the sediments collected closest to the vegetated marsh. Isotope fractionations ranged from 9‰ to 34‰ and correlated inversely with SRR, as predicted by the standard fractionation model for enzymatic sulfate reduction of Rees (1973). The ε versus SRR relationship, however, varied between sampling times, with higher ε values measured in February, at comparable SRRs, than in May and October. The observed ε versus SRR relationships also deviated from the previously reported inverse trend for sediments collected in a marine lagoon in Denmark (Canfield, 2001b). Thus, isotope fractionation during sulfate reduction is not uniquely determined by SRR, but is site- and time-dependent. Factors that may affect the ε versus SRR relationship include the structure and size of the sulfate-reducing community, and the nature and accessibility of organic substrates. Whole-sediment data such as those presented here provide a link between isotopic fractionations measured with pure cultures of sulfate-reducing prokaryotes and sulfur isotopic signatures recorded in sedimentary deposits.  相似文献   

3.
海洋天然气水合物系统硫同位素研究进展   总被引:2,自引:2,他引:0  
在海洋天然气水合物的地质系统中,甲烷的渗漏作用形成了独特的地球化学微环境。渗漏的甲烷在硫酸根-甲烷氧化还原界面与硫酸根之间发生厌氧氧化反应,同时硫酸盐发生还原反应,形成具有特殊同位素组成的自生碳酸盐、硫化物(AVS、黄铁矿等)和硫酸盐(重晶石、石膏)等。反应过程中硫酸盐还原菌的作用使得产物中硫的同位素发生了强烈分馏,具体表现为低δ34S值的硫化物矿物和高δ34S值的硫酸盐矿物的形成。沉积物中这种独特的硫同位素特征与海洋天然气水合物系统中独特地球化学微环境有关,是硫酸盐还原反应过程中细菌控制的硫酸盐分馏和厌氧细菌对硫的歧化反应(disproportionation)的共同作用结果。  相似文献   

4.
Rates of sulfate reduction, oxygen uptake and carbon dioxide production in sediments from a short Spartina alterniflora zone of Great Sippewissett Marsh were measured simultaneously during late summer. Surface sediments (0–2 cm) were dominated by aerobic metabolism which accounted for about 45% of the total carbon dioxide production over 0–15 cm. Rates of sulfate reduction agreed well with rates of total carbon dioxide production below 2 cm depth indicating that sulfate reduction was the primary pathway for sub-surface carbon metabolism. Sulfate reduction rates were determined using a radiotracer technique coupled with a chromous chloride digestion and carbon disulfide extraction of the sediment to determine the extent of formation of radiolabelled elemental sulfur and pyrite during shortterm (48 hr) incubations. In the surface 10 cm of the marsh sediments investigated, about 50% of the reduced radiosulfur was recovered as dissolved or acid volatile sulfides, 37% as carbon disulfide extractable sulfur, and only about 13% was recovered in a fraction operationally defined as pyrite. Correlations between the extent of sulfate depletion in the marsh sediments and the concentrations of dissolved and acid volatile sulfides supported the results of the radiotracer work. Our data suggest that sulfides and elemental sulfur may be major short-term end-products of sulfate reduction in salt marshes.  相似文献   

5.
As is less toxic than Hg, Cd, Pb, Se, Zn, and Cu. The As clarke for clays and shales is 10 ppm. Our samples of bottom sediments from Kurshskii Bay were determined to contain from 15 to 26 ppm As and up to 34 ppm As in the vicinity of the Neman River mouth. Elevated As concentrations (50–114 ppm) were detected in four columns of subsurface bottom sediments (at depths of 10–65 cm) from the Vistula Lagoon. Elevated As concentrations (50–180 ppm) were also found in a few surface samples of sand from the Gdansk Deep near oil platform D-6. These sediments are either partly contaminated with anthropogenic As or contain Fe sulfides and glauconite, which can concentrate As and contain its elevated concentrations. The As concentration in columns of bottom sediments from the Gulf of Finland were at the natural background level (throughout the columns) typical of the area (9–34 ppm). We repeatedly detected very high As concentrations (up to 227 ppm As) in pelitic ooze from Bornholm Deep, in the vicinity of the sunken vessel with chemical weapons. The sources of elevated As concentrations in the Baltic Sea are the following: (1) chemical weapon (CW) material buried in the floor of the Baltic Sea; (2) As-bearing pesticides, agricultural mineral fertilizers, and burned coal and other fuels; (3) kerogen-bearing Ordovician rocks exposed on the bottom; and (4) As-rich Fe sulfides brought to the area together with construction sand and gravel. This mixture was used in paper production and for the construction of hydraulic engineering facilities in the Vistula Lagoon in the early 20th century and later caused the so-called lagoon disease.  相似文献   

6.
Sulfate reduction rates were measured over the course of a year in the sediments of aJuncus roemerianus marsh located in coastal Alabama. Sulfate reduction rates were typically highest in the surface 0–2 cm and at depths corresponding to peak belowground biomass of the plants. The highest volume-based sulfate reduction rate measured was 1,350 μmol liter-sediment−1 d−1 in September 1995. Areal sulfate reduction rates (integrated to 20 cm depth) were strongly correlated to sediment temperature and varied seasonally from 15.2 mmol SO 4 2− m−2 d−1 in January 1995 to 117 mmol SO 4 2− m−2 d−1 in late August 1995. Despite high sulfate reduction rates porewater dissolved sulfide concentrations were low (<73 μM), indicating rapid sulfide oxidation or precipitation. Sulfate depletion data indicated that net oxidation of sediment sulfides occurred in March through May, following a period of infrequent tidal flooding and during a period of high plant production. Porewater Fe(II) reached very high levels (maximum of 969 μM; mean for all dates was 160 μM), particularly during periods of high sulfate reduction. The annual sulfate reduction rate integrated over the upper 20 cm of sediment was 22.0 mol SO 4 2− m−2 yr−1, which is among the highest rates measured in a wetland ecosystem. Based on literature values of net primary production inJ. roemerianus marshes, we estimate that an amount equivalent to 16% to 90% of the annual belowground production may be remineralized through sulfate reduction.  相似文献   

7.
Geochemistry of Peruvian near-surface sediments   总被引:6,自引:0,他引:6  
Sixteen short sediment cores were recovered from the upper edge (UEO), within (WO) and below (BO) the oxygen minimum zone (OMZ) off Peru during cruise 147 of R/V Sonne. Solids were analyzed for major/trace elements, total organic carbon, total inorganic carbon, total sulfur, the stable sulfur isotope composition (δ34S) of pyrite, and sulfate reduction rates (SRR). Pore waters were analyzed for dissolved sulfate/sulfide and δ34S of sulfate. In all cores highest SRR were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and/or diffusion of sulfate from bottom water. δ34S of dissolved sulfate showed only minor downcore increases. Strong 32S enrichments in sedimentary pyrite (to −48‰ vs. V-CDT) are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. Manganese and Co are significantly depleted in Peruvian upwelling sediments most likely due to mobilization from particles settling through the OMZ, whereas release of both elements from reducing sediments only seems to occur in near-coastal sites. Cadmium, Mo and Re are exceptionally enriched in WO sediments (<600 m water depth). High Re and moderate Cd and Mo enrichments are seen in BO sediments (>600 m water depth). Re/Mo ratios indicate anoxic and suboxic conditions for WO and BO sediments, respectively. Cadmium and Mo downcore profiles suggest considerable contribution to UEO/WO sediments by a biodetrital phase, whereas Re presumably accumulates via diffusion across the sediment-water interface to precipitation depth. Uranium is distinctly enriched in WO sediments (due to sulfidic conditions) and in some BO sediments (due to phosphorites). Silver transfer to suboxic BO sediments is likely governed by diatomaceous matter input, whereas in anoxic WO sediments Ag is presumably trapped due to sulfide precipitation. Cadmium, Cu, Zn, Ni, Cr, Ag, and T1 predominantly accumulate via biogenic pre-concentration in plankton remains. Rhenium, Sb, As, V, U and Mo are enriched in accordance with seawater TE availability. Lead and Bi enrichment in UEO surface sediments is likely contributed by anthropogenic activity (mining). Accumulation rates of TOC, Cd, Mo, U, and V from Peruvian and Namibian sediments exceed those from the Oman Margin and Gulf of California due to enhanced preservation off Peru and Namibia.  相似文献   

8.
A synthesis of previous results, which we dub the “standard model,” provides a prediction as to how isotope fractionation during sulfate reduction should respond to physiological variables such as specific rate of sulfate reduction and environmental variables such as substrate availability and temperature. The standard model suggests that isotope fractionation should decrease with increasing specific rates of sulfate reduction (rate per cell). Furthermore, the standard model predicts that low fractionations should be found at both high and low temperatures whereas the highest fractionations should be found in the intermediate temperature range. These fractionation trends are controlled, as a function of temperature, by the balance between the transfer rates of sulfate into and out of the cell and the exchange between the sulfur pools internal to the organism. We test this standard model by conducting experiments on the growth physiology and isotope fractionation, as a function of temperature, by the sulfate-reducing bacterium Desulfovibrio desulfuricans (DSMZ 642). Our results contrast with the “standard model” by showing a positive correlation between specific rates of sulfate reduction and fractionation. Also by contrast with the standard model, we found the highest fractionations at low and high temperatures and the lowest fractionations in the intermediate temperature range. We develop a fractionation model which can be used to explain both our results as well as the results of the “standard model.” Differences in fractionation with temperature relate to differences in the specific temperature response of internal enzyme kinetics as well as the exchange rates of sulfate in and out of the cell. It is expected that the kinetics of these processes will show strain-specific differences.  相似文献   

9.
Organic sulfur in marine sediment is 34S enriched relative to the co-existing pyrite. This phenomenon is still enigmatic. Timing of the sulfur incorporation, immobilization and different sulfur species involved are part of the explanations. The reduced sulfur species incorporation into organic matter (OM) is generally assumed to have negligible δ34S fractionation. This assumption has never been confirmed by laboratory experimental data. The present study measures the δ34S changes resulting from reduced sulfur species (sulfides and polysulfide anions) incorporation into organic model compounds in an aquatic and low temperature (25 °C) system that simulates diagenetic marine environment. In addition, we also investigate the δ34S fractionation and the isotope chemical mixing in the formation of polysulfide anions produced from elemental sulfur and sulfide anions. The results showed total isotope mixing between the two species in the formation of polysulfides. Acidification of the polysulfides solution caused δ34S fractionation between the released elemental sulfur and H2S. The incorporation of polysulfides and sulfides into carbonyl groups, caused 34S enrichment relative to the starting polysulfides and sulfide of 4–5‰. The 34S enrichment of the sulfurized carbonyl groups showed a minimal effect by temperature (0–70 °C) and is not affected by salinity, polysulfides composition, reaction time or solubility in water. The incorporation of polysulfides and sulfides into brominated organic compounds was negligibly 34S enriched. The chemical mechanisms controlling the polysulfides incorporation into OM depend mostly on the functional groups and determine the 34S enrichment of the sulfurized OM. The results presented in this study can explain part of the difference between pyrite δ34S and sulfurized OM δ34S in natural marine sediments.  相似文献   

10.
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   

11.
Five temperate seagrasses (Amphibolis antartica, Halophila ovalis, Posidonia australis, Posidonia sinuosa and Zostera nigricaulis) were surveyed along the south-west coast of Western Australia. These morphological different seagrasses grow in contrasting sediments with large variations in sedimentary organic matter, carbonate and iron contents. We tested if sulfur composition in the plants responded to sulfur dynamics in the sediments and if plant morphology affected the sulfur composition of the plants. The sediments were characterized by low sulfate reduction rates (<9 mmol m?2day?1), low concentrations of dissolved sulfides in the pore waters (<74 μM) and low burial of sulfides (total reducible sulfur <0.8 mol m?2) in the sediments. However, all seagrasses showed high intrusion in the below-ground parts with up to 84 % of the sulfur derived from sedimentary sulfides. There were no direct links between sulfur in the plants and sulfur dynamics in the sediments, probably due to low iron contents in the sediments limiting the buffering capacity of the sediments and exposing the plants to sulfides despite low rates of production and low pools of sulfides. The intrusion was linked between plant compartments (roots, rhizomes and leaves) for the two small species (H. ovalis and Z. nigricaulis), whereas the intrusion into the leaves was limited for the larger species (P. australis and P. sinuosa) and for A. antarctica, where extensive rhizomes and roots and the long stem for A. antarctica separate the leaves from the sediment compartment. Elevated intrusion was observed at two study locations, where natural deposition of organic matter or nutrient enrichment may be contributing factors to enhanced sulfide pressure.  相似文献   

12.
Multiple sulfur isotope ratios (^34S/^33S/^32S) of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation (MIF) signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL (the present atmosphere level). The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide (-2.30‰ to --0.25‰) show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values (-0.5‰ to -‰) indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL (mass dependent fractionation line) on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.  相似文献   

13.
To examine and compare historical accumulation of metal(loid)s in Mexican lakes and reservoirs, 210Pb and 137Cs dated sediment cores were evaluated: two from the remote Zempoala and Miramar Lagoons and three from Lake Pátzcuaro, and the Intermedia and Silva dams that are affected by human activities. Sediment ecotoxicology was assessed using consensus-based sediment quality guidelines for freshwater ecosystems. The +100 a sediment core from the remote Miramar Lagoon had the highest concentrations of Cr and Ni these being higher than the Probable Effect Levels (PELs). Zinc concentrations were also higher in the Miramar Lagoon compared to the other lakes and reservoirs, with concentrations higher than the Threshold Effect Level (TEL). Mercury concentrations from this lagoon were comparable to those for the Intermedia dam that receives water from urban, industrial and agricultural areas. The higher metal concentrations in the core from the Miramar Lagoon suggest that metal concentrations in the rocks of the watershed are high. Another explanation for the higher metal concentrations is the slow sediment accumulation that causes metals to be accumulated over longer time-periods at the sediment–water interface. A decrease in the concentration of As in the Intermedia dam was observed in sediments corresponding to the last decades. This may be due to an increase in sediment accumulation rate or to the reduction in sources of this metalloid in the watershed. In the Miramar Lagoon, an increase was observed in concentrations of As and Cr in more recent sediments, probably related to increased deforestation in the area or the eruption of El Chichonal volcano in 1982. Concentrations of Pb showed a decreasing tendency over the past decades in the Lake Pátzcuaro, Miramar and Zempoala Lagoons sediment cores while such behavior was not be observed for the Intermedia dam. This reduction in concentrations of Pb was attributed to the decrease in use of leaded gasoline.  相似文献   

14.
Here, we present new measurements of 32S, 33S, 34S, and 36S in sedimentary sulfides and couple these measurements with modeling treatments to study the sulfur cycle of a late Paleoproterozoic marine basin. We target the transition in ocean chemistry from the deposition of Paleoproterozoic iron formations (Gunflint Formation, Biwabik Formation, Trommald Formation, and Mahnomen iron formations) to the inferred sulfidic ocean conditions recorded by overlying shale (Rove Formation). The data suggest that certain features of the global sulfur cycle, such as a control by sulfate reducing prokaryotes, and low (mM) concentrations of oceanic sulfate, were maintained across this transition. This suggests that the transition was associated with changes in the structure of the basin-scale sulfur cycle during deposition of these sediments. Sulfide data from the iron formations are interpreted to reflect sedimentary sulfides formed from microbial reduction of pore-water sulfate that was supplied through steady-state exchange with an overlying oceanic sulfate reservoir. The sulfide data for the euxinic Rove Formation shales reflect the operation of a sulfur cycle that included the loss of sulfide by a Rayleigh-like process. We suggest that the prevalence of large and variable heavy isotope enrichments observed in Rove Formation sulfide minerals reflect a sustained and significant net loss of sulfide from the euxinic water column, either as a result of a shallow chemocline and degassing to the atmosphere or as a result of a water column pyrite sink. The inclusion of 36S measurements (in addition to 32S, 33S, and 34S) illustrates the mass-dependent character of these sedimentary environments, ruling out contributions from the weathering of Archean sulfides and pointing to at least modest levels of sustained atmospheric oxygen (>10−5 present atmospheric levels of O2).  相似文献   

15.
《Applied Geochemistry》2003,18(1):25-36
The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO4 and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l−1) and SO4 (1.3–22 mmol l−1). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm−3 a−1) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO4 and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.  相似文献   

16.
为了揭示油气盆地埋藏环境中碳酸盐岩和硫酸盐岩共生时的岩溶发育机制, 以硫酸盐岩为研究对象, 采用室内模拟实验与野外实测资料相结合的方法, 分析了温度、SO42-浓度和时间等因素对水-岩-细菌封闭系统内稳定硫同位素的影响, 并指出硫同位素对地球化学作用的指示意义.结果表明, 细菌硫酸盐还原形成的H2S中硫同位素分馏明显, 并受系统的温度和开放性等因素影响.结合鄂尔多斯盆地奥陶系风化壳中充填的黄铁矿硫同位素特征, 提出了鄂尔多斯盆地奥陶系岩溶的生物成因模式; 揭示了风化壳顶部的黄铁矿化与风化壳下部压释水岩溶共生的机制, 建立了生物岩溶发育的硫同位素地球化学标志.研究成果拓宽了岩溶的压释水成因机制.   相似文献   

17.
Stable sulfur isotope analyses show that rooted estuarine plants growing in anoxic sediments incorporate substantial amounts of 34S-depleted sulfides, or oxidation products thereof. In roots, this incorporation predominates over sulfate uptake from interstitial porewater. Either the plants incorporate normally toxic sulfides, or they are creating and using a specialized nutrient pool of oxidized sulfides at the root-sediment interface.  相似文献   

18.
In order to reconstruct paleo-environmental conditions for the saline playa lakes of the Rio Grande Rift, we investigated sediment sulfate sources using sulfur isotope compositions of dissolved ions in modern surface water, groundwater, and precipitated in the form of gypsum sediments deposited during the Pleistocene and Holocene in the Tularosa and Estancia Basins. The major sulfate sources are Lower and Middle Permian marine evaporites (δ34S of 10.9-14.4‰), but the diverse physiography of the Tularosa Basin led to a complex drainage system which contributed sulfates from various sources depending on the climate at the time of sedimentation. As inferred from sulfur isotope mass balance constraints, weathering of sulfides of magmatic/hydrothermal and sedimentary origin associated with climate oscillations during Last Glacial Maximum contributed about 35-50% of the sulfates and led to deposition of gypsum with δ34S values of −1.2‰ to 2.2‰ which are substantially lower than Permian evaporates. In the Estancia Basin, microbial sulfate reduction appears to overprint sulfur isotopic signatures that might elucidate past groundwater flows. A Rayleigh distillation model indicates that about 3-18% of sulfates from an inorganic groundwater pool (δ34S of 12.6-13.8‰) have been metabolized by bacteria and preserved as partially to fully reduced sulfur-bearing minerals species (elemental sulfur, monosulfides, disulfides) with distinctly negative δ34S values (−42.3‰ to −20.3‰) compared to co-existing gypsum (−3.8‰ to 22.4‰). For the Tularosa Basin microbial sulfate reduction had negligible effect on δ34S value of the gypsiferous sediments most likely because of higher annual temperatures (15-33 °C) and lower organic carbon content (median 0.09%) in those sediments leading to more efficient oxidation of H2S and/or smaller rates of sulfate reduction compared to the saline playas of the Estancia Basin (5-28 °C; median 0.46% of organic carbon).The White Sands region of the Tularosa Basin is frequently posited as a hydrothermal analogue for Mars. High temperatures of groundwater (33.3 °C) and high δ18O(H2O) values (1.1‰) in White Sands, however, are controlled predominantly by seasonal evaporation rather than the modern influx of hydrothermal fluids. Nevertheless, it is possible that some of the geochemical processes in White Sands, such as sulfide weathering during climate oscillations and upwelling of highly mineralized waters, might be considered as valid terrestrial analogues for the sulfate cycle in places such as Meridiani Planum on Mars.  相似文献   

19.
Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments (e.g., the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979).  相似文献   

20.
We present a 3-year study of concentrations and sulfur isotope values (δ34S, Δ33S, and Δ36S) of sulfur compounds in the water column of Fayetteville Green Lake (NY, USA), a stratified (meromictic) euxinic lake with moderately high sulfate concentrations (12-16 mM). We utilize our results along with numerical models (including transport within the lake) to identify and quantify the major biological and abiotic processes contributing to sulfur cycling in the system. The isotope values of sulfide and zero-valent sulfur across the redox-interface (chemocline) change seasonally in response to changes in sulfide oxidation processes. In the fall, sulfide oxidation occurs primarily via abiotic reaction with oxygen, as reflected by an increase in sulfide δ34S at the redox interface. Interestingly, S isotope values for zero-valent sulfur sampled at this time still reflect production and recycling by phototrophic S-oxidation. In the spring, sulfide S isotope values suggest an increased input from phototrophic oxidation, consistent with a more pronounced phototroph population at the chemocline. This trend is associated with smaller fractionations between sulfide and zero-valent sulfur, suggesting a metabolic rate control on fractionation similar to that for sulfate reduction. Comparison of our data with previous studies indicates that the S isotope values of sulfate and sulfide in the deep waters are remarkably stable over long periods of time, with consistently large fractionations of up to 58‰ in δ34S. Models of the δ34S and Δ33S trends in the deep waters (considering mass transport via diffusion and advection along with biological processes) require that these fractionations are a consequence of sulfur compound disproportionation at and below the redox interface in addition to large fractionations during sulfate reduction. The large fractionations during sulfate reduction appear to be a consequence of the high sulfate concentrations and the distribution of organic matter in the water column. The occurrence of disproportionation in the lake is supported by profiles of intermediate sulfur compounds and by lake microbiology, but is not evident from the δ34S trends alone. These results illustrate the utility of including minor S isotopes in sulfur isotope studies to unravel complex sulfur cycling in natural systems.  相似文献   

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