Barite in hydrothermal environments as a recorder of subseafloor processes: a multiple‐isotope study from the Loki's Castle vent field

Barite chimneys are known to form in hydrothermal systems where barium‐enriched fluids generated by leaching of the oceanic basement are discharged and react with seawater sulfate. They also form at cold seeps along continental margins, where marine (or pelagic) barite in the sediments is remobilized because of subseafloor microbial sulfate reduction. We test the possibility of using multiple sulfur isotopes (δ³⁴S, Δ³³S, ?³⁶S) of barite to identify microbial sulfate reduction in a hydrothermal system. In addition to multiple sulfur isotopes, we present oxygen (δ¹⁸O) and strontium (⁸⁷Sr/⁸⁶Sr) isotopes for one of numerous barite chimneys in a low‐temperature (~20 °C) venting area of the Loki's Castle black smoker field at the ultraslow‐spreading Arctic Mid‐Ocean Ridge (AMOR). The chemistry of the venting fluids in the barite field identifies a contribution of at least 10% of high‐temperature black smoker fluid, which is corroborated by ⁸⁷Sr/⁸⁶Sr ratios in the barite chimney that are less radiogenic than in seawater. In contrast, oxygen and multiple sulfur isotopes indicate that the fluid from which the barite precipitated contained residual sulfate that was affected by microbial sulfate reduction. A sulfate reduction zone at this site is further supported by the multiple sulfur isotopic composition of framboidal pyrite in the flow channel of the barite chimney and in the hydrothermal sediments in the barite field, as well as by low SO₄ and elevated H₂S concentrations in the venting fluids compared with conservative mixing values. We suggest that the mixing of ascending H₂‐ and CH₄‐rich high‐temperature fluids with percolating seawater fuels microbial sulfate reduction, which is subsequently recorded by barite formed at the seafloor in areas where the flow rate is sufficient. Thus, low‐temperature precipitates in hydrothermal systems are promising sites to explore the interactions between the geosphere and biosphere in order to evaluate the microbial impact on these systems.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

Unprecedented 34S‐enrichment of pyrite formed following microbial sulfate reduction in fractured crystalline rocks

In the deep biosphere, microbial sulfate reduction (MSR) is exploited for energy. Here, we show that, in fractured continental crystalline bedrock in three areas in Sweden, this process produced sulfide that reacted with iron to form pyrite extremely enriched in ³⁴S relative to ³²S. As documented by secondary ion mass spectrometry (SIMS) microanalyses, the δ³⁴S_pyrite values are up to +132‰V‐CDT and with a total range of 186‰. The lightest δ³⁴S_pyrite values (?54‰) suggest very large fractionation during MSR from an initial sulfate with δ³⁴S values (δ³⁴S_sulfate,0) of +14 to +28‰. Fractionation of this magnitude requires a slow MSR rate, a feature we attribute to nutrient and electron donor shortage as well as initial sulfate abundance. The superheavy δ³⁴S_pyrite values were produced by Rayleigh fractionation effects in a diminishing sulfate pool. Large volumes of pyrite with superheavy values (+120 ± 15‰) within single fracture intercepts in the boreholes, associated heavy average values up to +75‰ and heavy minimum δ³⁴S_pyrite values, suggest isolation of significant amounts of isotopically light sulfide in other parts of the fracture system. Large fracture‐specific δ³⁴S_pyrite variability and overall average δ³⁴S_pyrite values (+11 to +16‰) lower than the anticipated δ³⁴S_sulfate,0 support this hypothesis. The superheavy pyrite found locally in the borehole intercepts thus represents a late stage in a much larger fracture system undergoing Rayleigh fractionation. Microscale Rb–Sr dating and U/Th–He dating of cogenetic minerals reveal that most pyrite formed in the early Paleozoic era, but crystal overgrowths may be significantly younger. The δ¹³C values in cogenetic calcite suggest that the superheavy δ³⁴S_pyrite values are related to organotrophic MSR, in contrast to findings from marine sediments where superheavy pyrite has been proposed to be linked to anaerobic oxidation of methane. The findings provide new insights into MSR‐related S‐isotope systematics, particularly regarding formation of large fractions of ³⁴S‐rich pyrite.     

Environmental insights from high‐resolution (SIMS) sulfur isotope analyses of sulfides in Proterozoic microbialites with diverse mat textures

In modern microbial mats, hydrogen sulfide shows pronounced sulfur isotope (δ³⁴S) variability over small spatial scales (~50‰ over <4 mm), providing information about microbial sulfur cycling within different ecological niches in the mat. In the geological record, the location of pyrite formation, overprinting from mat accretion, and post‐depositional alteration also affect both fine‐scale δ³⁴S patterns and bulk δ³⁴S_pyrite values. We report μm‐scale δ³⁴S patterns in Proterozoic samples with well‐preserved microbial mat textures. We show a well‐defined relationship between δ³⁴S values and sulfide mineral grain size and type. Small pyrite grains (<25 μm) span a large range, tending toward high δ³⁴S values (?54.5‰ to 11.7‰, mean: ?14.4‰). Larger pyrite grains (>25 μm) have low but equally variable δ³⁴S values (?61.0‰ to ?10.5‰, mean: ?44.4‰). In one sample, larger sphalerite grains (>35 μm) have intermediate and essentially invariant δ³⁴S values (?22.6‰ to ?15.6‰, mean: ?19.4‰). We suggest that different sulfide mineral populations reflect separate stages of formation. In the first stage, small pyrite grains form near the mat surface along a redox boundary where high rates of sulfate reduction, partial closed‐system sulfate consumption in microenvironments, and/or sulfide oxidation lead to high δ³⁴S values. In another stage, large sphalerite grains with low δ³⁴S values grow along the edges of pore spaces formed from desiccation of the mat. Large pyrite grains form deeper in the mat at slower sulfate reduction rates, leading to low δ³⁴S_sulfide values. We do not see evidence for significant ³⁴S‐enrichment in bulk pore water sulfide at depth in the mat due to closed‐system Rayleigh fractionation effects. On a local scale, Rayleigh fractionation influences the range of δ³⁴S values measured for individual pyrite grains. Fine‐scale analyses of δ³⁴S_pyrite patterns can thus be used to extract environmental information from ancient microbial mats and aid in the interpretation of bulk δ³⁴S_pyrite records.     

Effect of increased sediment sulfide concentrations on the composition of stable sulfur isotopes (δS) and sulfur accumulation in the seagrasses Zostera marina and Posidonia oceanica

The effect of increased sediment sulfide concentrations on the sulfur isotopic composition (δ³⁴S), total sulfur (TS) and elemental sulfur (S⁰) concentrations in plant tissues was studied for the two seagrasses Zostera marina (3 weeks in laboratory) and Posidonia oceanica (4 months in situ). Porewater sulfide concentrations were experimentally regulated and plants exposed to high sediment sulfide concentrations had δ³⁴S signals closer to the δ³⁴S of sulfide, whereas plants exposed to no / low sulfide concentrations had δ³⁴S signals closer to the δ³⁴S of seawater sulfate, indicating a higher sulfide invasion in plants exposed to high sulfide concentrations. The δ³⁴S varied between the plant tissues in both species with the leaves having more positive δ³⁴S signals than roots and rhizomes, indicating that sulfide was invading into the roots and moved to the other tissues through the lacunae. TS and S⁰ concentrations were higher in plants exposed to sulfide in both experiments suggesting that sulfur derived from sediment sulfide accumulated in the plants. The δ³⁴S signal in S⁰ was similar to sediment sulfide verifying that S⁰ found in the seagrasses originated from sediment sulfide. Direct comparisons of δ³⁴S in the two different seagrasses and across the treatments were not possible due to large differences in δ³⁴S of the sulfur sources. F_sulfide adjusted for these differences and may be a useful alternative, when δ³⁴S of the sulfur sources varies between study sites. There were no significant effects of sulfide exposure on plant growth and mortality in Z. marina and P. oceanica after 3 weeks and 8 weeks exposure, respectively, but P. oceanica showed indications of reduced growth and higher mortality after 16 weeks of sulfide exposure probably due to sulfide invasion/toxicity.     

Isotope Systematics of Sulfate-oxygen and Sulfate-sulfur in Six European Peatlands

Oxygen (O) and sulfur (S) isotope systematics in bog water sulfates were determined for six Sphagnum dominated wetlands located in the British Isles and the Czech Republic, Central Europe. Comparison of a polluted and unpolluted site showed that 4 times higher atmospheric S inputs led to 3 times higher bog water sulfate concentrations and substrate S concentrations, 3 times increased ranges of substrate S concentrations, and 3 times increased ranges of δ³⁴S values. Sites with elevated atmospheric S inputs exhibited greater geochemical variability in wetland S species. Sulfate O–S isotope composition of bog pore water at a depth of 40 cm below surface differed from that of surface bog water, indicating that dissimilatory bacterial sulfate reduction, a process known to discriminate against the heavier isotopes ¹⁸O and ³⁴S, occurred in surface peat layers. While bacterial sulfate reduction remained to be one of the main isotope-selective processes for sulfate in peat, it could not fully explain the O–S isotope systematics of peat waters. The ‘residual’ sulfate was not simultaneously enriched in the heavier isotopes ¹⁸O and ³⁴S. Mixing of residual sulfate following bacterial sulfate reduction with the product of S²⁻ reoxidation, cleavage of esters, and isotope exchange reactions may have contributed to the decoupling of the δ³⁴S_so4 and δ¹⁸S_so4 values. Large within-site differences in δ¹⁸S_so4 and δ³⁴S_so4 (up to 13 and 15‰, respectively) indicated little communication between the 0 and 40 cm peat depth at some sites. Extremely high δ¹⁸S_so4 and δ³⁴S_so4 values found in several peat bog water samples from Connemara (Ireland), Thorne Moors (England) and Ocean (Czech Republic) were not seen in streams draining the wetlands. Direct runoff of atmogenic sulfate constituted a significant portion of the bog outflow. At the wetland scale, zones of dissimilatory bacterial sulfate reduction form pockets whose lateral hydrological fluxes are small.     

34S tracer study of pollutant sulfate behaviour in a lowland peatland

Field experiments were carried out in order to assess the practicality and application of ³⁴SO₄ ^2? as a tracer of the physical and geochemical fate of aerially derived sulfur in peat. Six enclosures were isolated in a lowland peat with high historical acid sulfate inputs at Thorne Moors, UK, and treated with regular additions of 99.9% pure ³⁴SO₄ ^2? for 12 months. The total ³⁴S sulfate addition resulted in negligible change to the sulfate concentration, but allowed unequivocal change to the isotopic composition of sulfate inputs relative to pre-experiment control data set. Migration and biogeochemical transformations of the ³⁴S tracer were monitored via depth-specific sampling of surface and pore-waters every 6 weeks, and sacrificial sampling of solid peat at 12, 24, and 48 week intervals. Tracer incorporation into the various sulfur forms within the surface and pore-waters, vegetation, organic and inorganic fractions of the peat was apparent through strong positive deviation of δ³⁴S from natural values (in comparison with 18 months control data set for the same site). Consistency within enclosures is good and a detailed model of sulfur cycling within each enclosure can be established but natural variability in the control data and differences between replicate enclosures prevents more quantitative assessment. The ³⁴S tracer was initially rapidly removed from surface waters. The majority of uptake was by living vegetation (5.7–33% of tracer added, mean 17.6%), or through transformation to the organic fraction of the upper peat (25 cm) after rapid bacterial reduction of sulfate to sulfide. Despite penetration of ³⁴S labelled sulfate to deeper pore-waters over time, there was no significant reduction to sulfide or subsequent incorporation into organic or inorganic fraction at these depths (>25 cm); organic and inorganic sulfur, and pore-water sulfide retained their initial unlabelled isotopic compositions. This limitation on sulfur cycling at relatively shallow depth may be attributed to diminished labile organic matter inhibiting the activity of sulfate reducing bacteria or poisoning of sulfate reducers by high dissolved sulfide, after long-term sulfur pollution of this ecosystem.     

Reduction of Sulfur Compounds in the Sediments of a Eutrophic Lake Basin

Concentrations of various sulfur compounds (SO₄²⁻, H₂S, S⁰, acid-volatile sulfide, and total sulfur) were determined in the profundal sediments and overlying water column of a shallow eutrophic lake. Low concentrations of sulfate relative to those of acid-volatile sulfide and total sulfur and a decrease in total sulfur with sediment depth implied that the contribution of dissimilatory sulfur reduction to H₂S production was relatively minor. Addition of 1.0 mM Na₂³⁵SO₄ to upper sediments in laboratory experiments resulted in the production of H₂³⁵S with no apparent lag. Kinetic experiments with ³⁵S demonstrated an apparent K_m of 0.068 mmol of SO₄²⁻ reduced per liter of sediment per day, whereas tracer experiments with ³⁵S indicated an average turnover time of the sediment sulfate pool of 1.5 h. Total sulfate reduction in a sediment depth profile to 15 cm was 15.3 mmol of sulfate reduced per m² per day, which corresponds to a mineralization of 30% of the particulate organic matter entering the sediment. Reduction of ³⁵S⁰ occurred at a slower rate. These results demonstrated that high rates of sulfate reduction occur in these sediments despite low concentrations of oxidized inorganic compounds and that this reduction can be important in the anaerobic mineralization of organic carbon.     

Diversity decoupled from sulfur isotope fractionation in a sulfate‐reducing microbial community

The extent of fractionation of sulfur isotopes by sulfate‐reducing microbes is dictated by genomic and environmental factors. A greater understanding of species‐specific fractionations may better inform interpretation of sulfur isotopes preserved in the rock record. To examine whether gene diversity influences net isotopic fractionation in situ, we assessed environmental chemistry, sulfate reduction rates, diversity of putative sulfur‐metabolizing organisms by 16S rRNA and dissimilatory sulfite reductase (dsrB) gene amplicon sequencing, and net fractionation of sulfur isotopes along a sediment transect of a hypersaline Arctic spring. In situ sulfate reduction rates yielded minimum cell‐specific sulfate reduction rates < 0.3 × 10^?15 moles cell^?1 day^?1. Neither 16S rRNA nor dsrB diversity indices correlated with relatively constant (38‰–45‰) net isotope fractionation (ε³⁴S_{sulfide‐sulfate}). Measured ε³⁴S values could be reproduced in a mechanistic fractionation model if 1%–2% of the microbial community (10%–60% of Deltaproteobacteria) were engaged in sulfate respiration, indicating heterogeneous respiratory activity within sulfate‐reducing populations. This model indicated enzymatic kinetic diversity of Apr was more likely to correlate with sulfur fractionation than DsrB. We propose that, above a threshold Shannon diversity value of 0.8 for dsrB, the influence of the specific composition of the microbial community responsible for generating an isotope signal is overprinted by the control exerted by environmental variables on microbial physiology.     

Sedimentary pyrite sulfur isotope compositions preserve signatures of the surface microbial mat environment in sediments underlying low-oxygen cyanobacterial mats

The sedimentary pyrite sulfur isotope (δ³⁴S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ³⁴S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ³⁴S geochemistry. Pyrite δ³⁴S values often capture δ³⁴S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ³⁴S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ³⁴S trends and δ³⁴S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment–water interface of this sinkhole hosts a low-oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ³⁴S signatures in early Earth environments. Porewater sulfide δ³⁴S values vary by up to ~25‰ throughout the day due to light-driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ³⁴S variability, instead of variations in average cell-specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ³⁴S values of pyrite are similar to porewater sulfide δ³⁴S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ³⁴S signatures of pyrite deposited in organic-rich, iron-poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis.     

Linking sedimentary sulfur and iron biogeochemistry to growth patterns of a cold‐water coral mound in the Porcupine Basin,S.W. Ireland (IODP Expedition 307)

Challenger Mound, a 150‐m‐high cold‐water coral mound on the eastern flank of the Porcupine Seabight off SW Ireland, was drilled during Expedition 307 of the Integrated Ocean Drilling Program (IODP). Retrieved cores offer unique insight into an archive of Quaternary paleo‐environmental change, long‐term coral mound development, and the diagenetic alteration of these carbonate fabrics over time. To characterize biogeochemical carbon–iron–sulfur transformations in the mound sediments, the contents of dithionite‐ and HCl‐extractable iron phases, iron monosulfide and pyrite, and acid‐extractable calcium, magnesium, manganese, and strontium were determined. Additionally, the stable isotopic compositions of pore‐water sulfate and solid‐phase reduced sulfur compounds were analyzed. Sulfate penetrated through the mound sequence and into the underlying Miocene sediments, where a sulfate–methane transition zone was identified. Small sulfate concentration decreases (<7 mm ) within the top 40 m of the mound suggested slow net rates of present‐day organoclastic sulfate reduction. Increasing δ³⁴S‐sulfate values due to microbial sulfate reduction mirrored the decrease in sulfate concentrations. This process was accompanied by oxygen isotope exchange with water that was indicated by increasing δ¹⁸O‐sulfate values, reaching equilibrium with pore‐water at depth. Below 50 mbsf, sediment intervals with strong ³⁴S‐enriched imprints on chromium‐reducible sulfur (pyrite S), high degree‐of‐pyritization values, and semi‐lithified diagenetic carbonate‐rich layers characterized by poor coral preservation, were observed. These layers provided evidence for the occurrence of enhanced microbial sulfate‐reducing activity in the mound in the past during periods of rapid mound aggradation and subsequent intervals of non‐deposition or erosion when geochemical fronts remained stationary. During these periods, especially during the Early Pleistocene, elevated sulfate reduction rates facilitated the consumption of reducible iron oxide phases, coral dissolution, and the subsequent formation of carbonate cements.     

Inorganic sulfur turnover in oligohaline estuarine sediments

Inorganic sulfur turnover was examined in oligohaline (salinity < 2 g kg^-1) Chesapeake Bay sediments during the summer. Cores incubated for < 3 hr exhibited higher sulfate reduction (SR) rates (13–58 mmol m^-2 d^-1) than those incubated for 3–8 hr (3–8 mmol m^-2 d^-1). SR rates (determined with³⁵SO ₄ ^2- ) increased with depth over the top few cm to a maximum at 5 cm, just beneath the boundary between brown and black sediment. SR rates decreased below 5 cm, probably due to sulfate limitation (sulfate < 25 μM). Kinetic experiments yielded an apparent half-saturating sulfate concentration (K_s) of 34 μM, ≈ 20-fold lower than that determined for sediments from the mesohaline region of the estuary. Sulfate loss from water overlying intact cores, predicted on the basis of measured SR rates, was not observed over a 28-hr incubation period. Reduction of³⁵SO ₄ ^2- during diffusion experiments with intact core segments from 0–4 and 5–9 cm horizons was less than predicted by non-steady state diagenetic models based on³⁵SO ₄ ^2- reduction in whole core injection experiments. The results indicate that net sulfate flux into sediments was an order of magnitude lower than the gross sulfur turnover rate. Solid phase reduced inorganic sulfur concentrations were only 2–3 times less than those in sediments from the mesohaline region of the Bay, despite the fact that oligohaline bottom water sulfate concentrations were 10-fold lower. Our results demonstrate the potential for rapid SR in low salinity estuarine sediments, which are inhabited by sulfate-reducing bacteria with a high affinity for sulfate, and in which sulfide oxidation processes replenish the pore water sulfate pool on a time scale of hours.     

34S/32S and 18O/16O Fractionation During Sulfur Disproportionation by Desulfobulbus propionicus

In the present study, coupled stable sulfur and oxygen isotope fractionation during elemental sulfur disproportionation according to the overall reaction: 4H₂O + 4S^? → 3H₂S + SO₄ ^{2 ?} + 2H⁺, was experimentally investigated for the first time using a pure culture of the sulfate reducer Desulfobulbus propionicus at 35^?C. Bacterial disproportionation of elemental sulfur is an important process in the sulfur cycle of natural surface sediments and leads to the simultaneous formation of sulfide and sulfate. A dual-isotope approach considering both sulfur and oxygen isotope discrimination has been shown to be most effective in evaluating specific microbial reactions. The influence of iron- and manganese bearing-solids (Fe(II)CO₃, Fe(III)OOH, Mn(IV)O₂) acting in natural sediments as scavengers for hydrogen sulfide, was considered, too. Disproportionation of elemental sulfur was observed in the presence of iron solids at a cell-specific sulfur disproportionation rate of about 10^{? 9.5± 0.4} μ mol S^? cell^{? 1} h^{? 1}. No disproportionation, however, was observed with MnO₂. In the presence of iron solids, newly formed sulfate was enriched in ¹⁸ O compared to water by about +21‰ (≡ ? _H2O ), in agreement with a suggested oxygen isotope exchange via traces of intra- or extracellular sulfite that is formed as a disproportionation intermediate. Dissolved sulfate was also enriched in ³⁴S compared to elemental sulfur by up to +35%. Isotope fractionation by Desulfobulbus propionicusis highest for all disproportionating bacteria investigated, so far, and may impact on the development of isotope signals at the redox boundary of surface sediments.     

Abundance and activity of microorganisms at the water-sediment interface and their effect on the carbon isotopic composition of suspended organic matter and sediments of the Kara Sea

At ten stations of the meridian profile in the eastern Kara Sea from the Yenisei estuary through the shallow shelf and further through the St. Anna trough, total microbial numbers (TMN) determined by direct counting, total activity of the microbial community determined by dark CO₂ assimilation (DCA), and the carbon isotopic composition of organic matter in suspension and upper sediment horizons (δ¹³C, ‰) were investigated. Three horizons were studied in detail: (1) the near-bottom water layer (20–30 cm above the sediment); (2) the uppermost, strongly hydrated sediment horizon, further termed fluffy layer (5–10 mm); and (3) the upper sediment horizon (1–5 cm). Due to a decrease in the amount of isotopically light carbon of terrigenous origin with increasing distance from the Yenisei estuary, the TMN and DCA values decreased, and the δ¹³C changed gradually from ?29.7 to ?23.9‰. At most stations, a noticeable decrease in TMN and DCA values with depth was observed in the water column, while the carbon isotopic composition of suspended organic matter did not change significantly. Considerable changes of all parameters were detected in the interface zone: TMN and DCA increased in the sediments compared to their values in near-bottom water, while the 13C content increased significantly, with δ¹³C of organic matter in the sediments being at some stations 3.5–4.0‰ higher than in the near-bottom water. Due to insufficient illumination in the near-bottom zone, newly formed isotopically heavy organic matter (δ¹³C ～ ?20‰) could not be formed by photosynthesis; active growth of chemoautotrophic microorganisms in this zone is suggested, which may use reduced sulfur, nitrogen, and carbon compounds diffusing from anaerobic sediments. High DCA values for the interface zone samples confirm this hypothesis. Moreover, neutrophilic sulfur-oxidizing bacteria were retrieved from the samples of this zone.     

Microbiological fractionation of stable sulfur isotopes: A review and critique

Microbiological transformations of sulfur compounds discriminate to various degrees between the stable sulfur isotopes ³²S and ³⁴S. Comparatively little is known on isotopic effects associated with sulfur‐oxidizing organisms, and the interpretation of results is complicated since the sulfur pathways are poorly defined and compounds containing two or more sulfur atoms at different oxidation states may be involved. Dissimilatory reduction of sulfate, and sulfite reduction by certain assimilatory microorganisms, causes particularly marked isotopic effects, the expression of which depends on the extent of reaction and other incompletely defined environmental conditions. Models have been proposed to account for these effects based on current knowledge of the reduction pathways. Many of the trends observed during dissimilatory sulfate reduction in the laboratory can also be found in the modern environment leaving little doubt that microbiological factors play a significant role in determining sulfur isotope distributions in nature. However, unusually large isotopic effects, rarely approached in the laboratory, are often observed in nature. The reasons for this are not entirely clear, but in sediments it is possible that diffusional isotopic effects are imposed on biological effects.     

Interpretation of sulfur cycling in two catchments in the Black Forest (Germany) using stable sulfur and oxygen isotope data

The isotopic composition of SO ₄ ^2- in bulk precipitation, canopy throughfall, seepage water at three different soil depths, stream water, and groundwater was monitored in two forested catchments in the Black Forest (Germany) between November 1989 and February 1992. Isotope measurements on aqueous sulfate were complemented by ³⁴S-analyses on SO₂ in the air, total sulfur and inorganic sulfate in the soil, and bedrock sulfur, in order to identify sources and biogeochemical processes affecting S cycling in catchments with base poor, siliceous bedrock. Stable S isotope data indicated that atmospheric deposition and not mineral weathering is the major source of S in both catchments since ³⁴S-values for sulfate in the soil, in seepage water, and in stream water were generally found to be similar to the mean ³⁴S-values of precipitation SO ₄ ^2- (+2.1. However, ¹⁸O-values of seepage water SO ₄ ^2- at 30 cm and especially at 80 cm depth were depleted by several per mil with respect to those of the atmospheric deposition (+7.5 to +13.5. This indicates that in both catchments a considerable proportion of the seepage water SO ₄ ^2- is derived from mineralization of carbon-bonded soil S and must therefore have cycled through the organic soil S pool. ³⁴S-values for different S compounds in the solid soil were found to differ markedly depending on S fraction and soil depth. Since atmospheric S deposition with rather constant ³⁴S-values was identified as the dominant S source in both catchments, this is interpreted as a result ofin situ isotope fractionation rather than admixture of isotopically different S. The differences between the ³⁴S-values of seepage water and soil sulfate and those of organic soil S compounds are consistent with a model in which SO ₄ ^2- uptake by vegetation and soil microorganisms favours³⁴SO ₄ ^2- slightly, whereas during mineralization of organic soil S to aqueous SOSO ₄ ^2- ,³²S reacts preferentially. However, the data provide evidence for negligible isotope fractionation during physico-chemical S transformations such as adsorption/desorption in aerated forest soils.     

Sulfur stable isotope signature identifies the source of reduced sulfur in benthic communities in macrophyte zones of Lake Biwa, Japan

Carbon, nitrogen and sulfur stable isotope ratios (δ¹³C, δ¹⁵N and δ³⁴S) were measured from water column sulfate, sediments, particulate organic matter (POM), macrophytes, periphyton, macroinvertebrates and fish, sampled from the littoral, open water and macrophyte zones of Lake Biwa. In most of the littoral zones, the δ¹³C and δ¹⁵N values of organisms indicated that POM and periphyton support the consumers. However, in the dysoxic interior macrophyte (IM) zone, the δ¹³C values of Sinotaia quadrata histrica, Propsilocerus akamusi and Anodonta woodiana were lower than that of all resources. The δ¹⁵N values of S. quadrata histrica were lower than those of P. akamusi and A. woodiana. δ¹³C and δ¹⁵N values thus failed to distinguish the foods of these consumers. The δ³⁴S values of sediment and S. quadrata histrica were lower than those of water column sulfate, suggesting that this consumer incorporated reduced sulfur derived from sulfate reduction in the sediment by ingesting detritus. In contrast, the δ³⁴S values of P. akamusi and A. woodiana were higher than that of S. quadrata histrica, suggesting that they incorporated sulfur derived from water column sulfate by ingesting POM. Consequently, δ¹³C, δ¹⁵N and δ³⁴S signatures provide complementary estimates of foods for consumers in this freshwater lake.     

The use of stable sulfur isotope labelling to elucidate sulfur metabolism by Clostridium pasteurianum

An unique stable isotope labelling experiment was conducted whereby mixtures of sulfate and sulfite of different isotopic compositions were metabolized by Clostridium pasteurianum. The results showed during reduction of 1 mM SO ₃ ⁼ plus 1 mM SO ₄ ⁼ , essentially all evolved H₂S arose from the sulfite whereas in the case of cellular sulfur, 85% was derived from sulfite and the remainder from sulfate.     

Stable isotopes track biogeochemical processes under seasonal ice cover in a shallow,productive lake

Biogeochemical dynamics under seasonal ice cover were investigated in the shallow (<10 m) water column of highly productive Georgetown Lake, western Montana, USA. This high altitude (1,800 m) reservoir is well-mixed in summer, but becomes strongly stratified under ice cover (mid-November–mid-May). A rapid drop in dissolved oxygen (DO) concentration and rise in dissolved inorganic carbon (DIC) concentration was observed after the onset of ice, with a corresponding increase in δ¹⁸O-DO and decrease in δ¹³C-DIC, likely caused by respiration (R) of organic carbon. Photosynthesis/respiration ratios (P/R) estimated from simultaneous measurement of DO and δ¹⁸O-DO were near unity prior to ice formation but then systematically decreased with time and depth in the lake under ice cover. P/R in the water column was higher at a shallower monitoring site compared to a deeper site near the dam outlet, which may have been important for over-winter survival of salmonids. By March, the bottom 3 m of the water column at both sites was anoxic, with the bottom 1 m being euxinic. Elevated concentrations of dissolved sulfide, ammonium, phosphate, Fe²⁺, and Mn²⁺ in deep water suggest coupling of organic carbon degradation with reduction of a number of electron acceptors (e.g., Fe³⁺, \({\text{NO}}_{3}^{ - } ,\;{\text{SO}}_{4}^{2 - }\) ). The concentrations and δ³⁴S values of H₂S in the deep water and \({\text{SO}}_{4}^{2 - }\) in the shallow water were similar, indicating near-complete reduction of sulfate in the euxinic zone. Late in the winter, an influx of isotopically heavy DIC was noted in the deep water coincident with a buildup of dissolved CH₄ to concentrations >1 mM. These trends are attributed to acetoclastic methanogenesis in the benthic sediments. This pool of dissolved CH₄ was likely released from the lake to the atmosphere during spring ice-off and lake turnover.     

Dissolved oxygen and dissolved inorganic carbon stable isotope composition and concentration fluxes across several shallow floodplain aquifers and in a diffusion experiment

Recent studies have documented the occurrence of dissolved molecular oxygen (DO) in shallow groundwater that is isotopically lighter than can be explained by atmospheric gas exchange or by biogeochemical reactions that consume ¹⁶O¹⁶O faster than ¹⁶O¹⁸O. In the present study, spatial gradients in the isotopic composition of DO (δ¹⁸O-DO) and dissolved inorganic carbon (δ¹³C-DIC) were measured in three shallow floodplain aquifers: (1) the Nyack aquifer, of the Middle Fork of the Flathead River in northwest Montana; (2) the Silver Bow Creek floodplain in southwest Montana; and (3) the Umatilla River floodplain in northeast Oregon. The field data show general trends of increasing DIC concentration, decreasing δ¹³C-DIC, and decreasing DO concentration with increase in groundwater path length. These trends are consistent with consumption of DO and production of DIC by microbial respiration. Although the expected trend of an increase in δ¹⁸O-DO with increase in path length was found at an area adjacent to hyporheic recharge at the Nyack floodplain, the majority of groundwater samples collected at Nyack and from the other sites distal to recharge zones had anomalously low δ¹⁸O-DO values well below 24.2 ‰, the value corresponding to atmospheric isotopic equilibrium. At the Nyack site, ³H-³He dates were used to estimate groundwater travel time: all groundwater samples with apparent age >1 year had δ¹⁸O-DO<24.2 ‰. Previously it has been suggested that diffusion of O₂ could be a viable mechanism to explain the existence of isotopically light DO in shallow groundwater. To test this hypothesis, laboratory experiments were conducted to measure the isotopic fractionation of O₂ as it diffuses from air across a simulated capillary fringe (made from a floating layer of foam beads) into a stirred, initially anoxic, water column. As expected, ¹⁶O¹⁶O diffused faster than ¹⁶O¹⁸O, and the magnitude of isotope fractionation associated with diffusion increased with a decrease in temperature. Fractionation factors (α) calculated from these diffusion experiments were 1.0030 at 15–19 °C and 1.0048 at 8 °C. The combined field and laboratory data suggest that diffusion is an important mechanism to maintain aerobic conditions in shallow groundwater systems, allowing microbial respiration to continue at long distances (km scale) from the source of groundwater recharge.