Are sulfur isotope ratios sufficient to determine the antiquity of sulfate reduction

Sulfur isotope fractionation values have been measured in sedimentary sulfides of varying ages, The Antiquity and evolutionary status of bacterial sulfate reduction... has been inferred from these measurements by Schidlowski (1979). However, under experimental conditions, the isotope values vary widely due to inadequately controlled variables. Thus the direct extrapolation of sulfur isotope fractionation values measured in the laboratory to those measured in sedimentary rocks is unwarranted. New sulfur transforming microbes have been described and recent measurements indicate that inorganic processes affect sulfur isotope fractionation values. This information is summarized here; at present sulfur isotope fractionation values are insufficient to determine the antiquity of sulfate reduction.     

In situ S‐isotope compositions of sulfate and sulfide from the 3.2 Ga Moodies Group,South Africa: A record of oxidative sulfur cycling

Sulfate minerals are rare in the Archean rock record and largely restricted to the occurrence of barite (BaSO₄). The origin of this barite remains controversially debated. The mass‐independent fractionation of sulfur isotopes in these and other Archean sedimentary rocks suggests that photolysis of volcanic aerosols in an oxygen‐poor atmosphere played an important role in their formation. Here, we report on the multiple sulfur isotopic composition of sedimentary anhydrite in the ca. 3.22 Ga Moodies Group of the Barberton Greenstone Belt, southern Africa. Anhydrite occurs, together with barite and pyrite, in regionally traceable beds that formed in fluvial settings. Variable abundances of barite versus anhydrite reflect changes in sulfate enrichment by evaporitic concentration across orders of magnitude in an arid, nearshore terrestrial environment, periodically replenished by influxes of seawater. The multiple S‐isotope compositions of anhydrite and pyrite are consistent with microbial sulfate reduction. S‐isotope signatures in barite suggest an additional oxidative sulfate source probably derived from continental weathering of sulfide possibly enhanced by microbial sulfur oxidation. Although depositional environments of Moodies sulfate minerals differ strongly from marine barite deposits, their sulfur isotopic composition is similar and most likely reflects a primary isotopic signature. The data indicate that a constant input of small portions of oxidized sulfur from the continents into the ocean may have contributed to the observed long‐term increase in Δ³³S_sulfate values through the Paleoarchean.     

Sulfur isotopes in sulfate in the inputs and outputs of a Canadian Shield watershed

The isotopic composition of sulfur in sulfate from precipitation, stream inflows and outflow of the Lake 239 watershed at the Experimental Lakes Area, northwestern Ontario, was monitored for four years, 1982–1985. Rainfall had ³⁴S of 3–9and a three year mean value weighted by the mass of sulfate of 4.8 Sulfur in streams ranged from 5–15 and displayed a pronounced seasonal pattern in which ³⁴S showed significant negative correlations with both streamflows and sulfate concentrations. Outflow values were much more constant and averaged 6.4 over the three year period. Sulfate reduction or sorption favoring retention of the lighter isotope in the watershed was the probable cause of the isotopic variation of the sulfur isotopes in the streams. A sulfur isotope budget for the lake balanced within 1     

Methane production and sulfate reduction in two Appalachian peatlands

Anaerobic carbon mineralization was evaluated over a 1-year period in two Sphagnum-dominated peatlands, Big Run Bog, West Virginia, and Buckle's Bog, Maryland. In the top 35 cm of peat, mean rates of methane production, anaerobic carbon dioxide production, and sulfate reduction at Big Run Bog were 63,406 and 146 mol L^-1 d^-1, respectively, and at Buckle's Bog were 18, 486 and 104 mol L^-1 d^-1. Annual anaerobic carbon mineralization to methane and carbon dioxide at Big Run Bog and Buckle's Bog was 52.8 and 57.2 mol m^-2, respectively. Rates of methane production were similar to rates reported for other freshwater peatlands, but methane production accounted for only 11.7 and 2.8%, respectively, of the total anaerobic carbon mineralization at these two sites. Carbon dioxide production, resulting substantially from sulfate reduction, dominated anaerobic carbon mineralization. Considerable sulfate reduction despite low instantaneous dissolved sulfate concentrations (typically < 300 mol L^-1 of substrate) was apparently fueled by oxidation and rapid turnover of the reduced inorganic sulfur pool.The coincidence of high sulfate inputs to the Big Run Bog and Buckle's Bog watersheds through acid precipitation with the unexpected importance of sulfate reduction leads us to suggest a new hypothesis: peatlands not receiving high sulfate loading should exhibit low rates of anaerobic decomposition, and a predominance of methane production over sulfate reduction; however, if such peatlands become subjected to high rates of sulfur deposition, sulfate reduction may be enhanced as an anaerobic mineralization pathway with attendant effects on carbon balance and peat accumulation.     

Microbiological and biogeochemical processes in a pockmark of the Gdansk depression,Baltic Sea

Comprehensive microbiological and biogeochemical investigation of a pockmark within one of the sites of gas-saturated sediments in the Gdansk depression, Baltic Sea was carried out during the 87th voyage of the Professor Shtokman research vessel. Methane content in the near-bottom water and in the underlying sediments indicates stable methane flow from the sediment into the water. In the 10-m water layer above the pockmark, apart from methane anomalies, elevated numbers of microorganisms and enhanced rates of dark CO₂ fixation (up to 1.15 µmol C/(l day)) and methane oxidation (up to 2.14 nmol CH₄/(l day)) were revealed. Lightened isotopic composition of suspended organic matter also indicates high activity of the near-bottom microbial community. Compared to the background stations, methane content in pockmark sediments increased sharply from the surface to 40–60 ml/dm³ in the 20–30 cm horizon. High rates of bacterial sulfate reduction (SR) were detected throughout the core (0–40 cm); the maximum of 74 µmol S/(dm³ day) was located in subsurface horizons (15–20 cm). The highest rates of anaerobic methane oxidation (AMO), up to 80 µmol/dm³ day), were detected in the same horizon. Good coincidence of the AMO and SR profiles with stoichiometry close to 1: 1 is evidence in favor of a close relation between these processes performed by a consortium of methanotrophic archaea and sulfate-reducing bacteria. Methane isotopic composition in subsurface sediments of the pockmark (from ?53.0 to ?56.5‰) does not rule out the presence of methane other than the biogenic methane from the deep horizons of the sedimentary cover.     

Effects of sulfate concentration in the overlying water on sulfate reduction and sulfur storage in lake sediments

We investigated the effects of sulfate concentration on sulfate reduction and net S storage in lake sediments using³⁴S as a tracer. The water overlying intact sediment cores from the hypolimnion of Mares Pond, MA, was replaced with two Na₂ ³⁴SO₄ solutions at either ambient (70 M) or elevated (260 M) sulfate concentrations. The ³⁴S of the added sulfate was 4974 . Over two months, the net sulfate reduction rate in the ambient sulfate treatment was zero, while the net rate for the high sulfate treatment was 140 moles/m²/d. The water overlying the cores was kept under oxic conditions and the sediment received no fresh carbon inputs, thus the net rate reported may underestimate the in situ rate. Gross sulfate reduction rates calculated by isotope dilution were approximately 350 moles/m²/d for both treatments. While the calculation of gross sulfate reduction rates in intact sediment cores can be complicated by differential diffusion of³⁴S and³²S, isotopic fractionation, and the possible formation of ester sulfates, we believe these effects to be small. The results suggest that sulfate reduction is not strongly sulfate-limited in Mares Pond. The difference in net sulfate reduction rates between treatments resulted from a decrease in sulfide oxidation and suggests the importance of reoxidation in controlling net S storage in lake sediments. In both treatments the CRS and organic S fractions were measurably labelled in³⁴S. Below the sediment surface, the CRS fraction was the more heavily labelled storage product for reduced sulfides.     

Antiquity and evolutionary status of bacterial sulfate reduction: Sulfur isotope evidence

The presently available sedimentary sulfur isotope record for the Precambrian seems to allow the following conclusions: (1) In the Early Archaean, sedimentary ^{3 4} patterns attributable to bacteriogenic sulfate reduction are generally absent. In particular, the ^{3 4} spread observed in the Isua banded iron formation (3.7×10⁹ yr) is extremely narrow and coincides completely with the respective spreads yielded by contemporaneous rocks of assumed mantle derivation. Incipient minor differentiation of the isotope patterns notably of Archaean sulfates may be accounted for by photosynthetic sulfur bacteria rather than by sulfate reducers. (2) Isotopic evidence of dissimilatory sulfate reduction is first observed in the upper Archaean of the Aldan Shield, Siberia (3.0×10⁹ yr) and in the Michipicoten and Woman River banded iron formations of Canada (2.75×10⁹ yr). This narrows down the possible time of appearance of sulfate respirers to the interval 2.8–3.1×10⁹ yr. (3) Various lines of evidence indicate that photosynthesis is older than sulfate respiration, the SO ₄ ^2– utilized by the first sulfate reducers deriving most probably from oxidation of reduced sulfur compounds by photosynthetic sulfur bacteria. Sulfate respiration must, in turn, have antedated oxygen respiration as O₂-respiring multicellular eucaryotes appear late in the Precambrian. (4) With the bulk of sulfate in the Archaean oceans probably produced by photosynthetic sulfur bacteria, the accumulation of SO ₄ ^2– in the ancient seas must have preceded the buildup of appreciable steady state levels of free oxygen. Hence, the occurrence of sulfate evaporites in Archaean sediments does not necessarily provide testimony of oxidation weathering on the ancient continents and, consequently, of the existence of an atmospheric oxygen reservoir.Paper presented at the Fourth College Park Colloquium on Chemical Evolution, Limits of Life, October 18–20, 1978.     

The effects of sediment slurrying on microbial processes,and the role of amino acids as substrates for sulfate reduction in anoxic marine sediments

In sediment slurry experiments with anoxic marine sediments collected in Cape Lookout Bight, NC, and a site in mid-Chesapeake Bay, the rates of sulfate reduction and ammonium production decrease with increasing dilution of sediment with oxygen-free sea-water. The effect of sediment dilution on the rates of these processes can be described by a simple mathematical relationship, and when these rates are corrected for sediment dilution they yield values which agree well with direct measurements of these processes.In sediment slurry studies of amino acid utilization in Cape Lookout Bight sediments, the fermentative decarboxylation of glutamic acid (to -aminobutyric acid) or aspartic acid (to alanine or -alanine) did not occur when either of these amino acids were added to Cape Lookout Bight slurries. The addition of glutamic acid did however lead to a small (1) transient build-up of -aminoglutaric acid. Measured rates of glutamic acid uptake in these slurries also decreased with increasing sediment dilution.Molybdate inhibition experiments demonstrated that dissolved free amino acids represent 1–3% of the carbon sources/electron donors used for sulfate reduction in Cape Lookout Bight sediments. The direct oxidation of amino acids by sulfate reducing bacteria also accounts for 13–20% of the total ammonium produced. Glutamic acid, alanine, -aminoglutaric acid, aspartic acid and asparagine are the major amino acids oxidized by sulfate reducing bacteria in Cape Lookout Bight sediments.     

Biogeochemical cycling of sulfur and iron in sediments of a south-east Asian mangrove,Phuket Island,Thailand

Benthic sulfate reduction and sediment pools of sulfur and iron were examined during January 1992 at 3 stations in the Ao Nam Bor mangrove, Phuket, Thailand. Patterns of sulfate reduction rates (0–53 cm) reflected differences in physical and biological conditions at the 3 stations, and highest rates were found at the vegetated site within the mangrove (Rhizophora apiculata) forest. Due to extended oxidation of mangrove sediments, a large portion of the added³⁵S-label was recovered in the chromium reducible pools (FeS₂ and S⁰) (41–91% of the reduced sulfur). Pyrite was the most important inorganic sulfur component, attaining pool sizes 50–100 times higher than acid volatile pools (FeS). HCl-extractable (0.5 M HCl) iron pools, including Fe(II)_HCl and Fe(III)_HCl, were generally low and Fe(III)_HCl was only present in the upper surface layers (0–5 cm). Maximum concentrations of dissolved Fe²⁺ (35–285 M) occurred just about the depth where dissolved H₂S accumulated. Furthermore Fe²⁺ and H₂S coexisted only where concentrations of both were low. There was an accumulation of organic sulfur in the deep sediment at 2 stations in the inner part of the mangrove. The reoxidation of reduced sulfides was rapid, and storage of sulfur was minor in the upper sediment layers, where factors like bioturbation, the presence of roots, or tidal mixing enhance oxidation processes.Author of correspondence.     

Bacterial sulfate reduction and salinity: two controls on dolomite precipitation in Lagoa Vermelha and Brejo do Espinho (Brazil)

The hydrological system of Lagoa Vermelha, a dolomite-precipitating lagoon in Brazil, was investigated using hydrogen and oxygen stable isotopic composition of the water collected during an annual cycle (1996–1997). These data demonstrated that dolomite formed in May–June during high saline conditions. High salinity apparently provides the ions and saturation state necessary for dolomite precipitation. Ion concentrations in the lagoon water indicated an identical timing of dolomite precipitation and demonstrated that dolomite formed at decreased sulfate concentrations. In Brejo do Espinho, a neighbouring lagoon, the ion concentrations in the water column revealed that dolomite precipitates throughout the year, most likely due to its higher salinity than Lagoa Vermelha during the measured period. In Lagoa Vermelha, high ³⁴S of pore water sulfate and high sulfide concentrations correlated with dolomitic horizons, demonstrating the association of bacterial sulfate reduction with dolomite formation. In Brejo do Espinho high ³⁴S of pore water sulfate and high sulfide concentrations occurred throughout the dolomitic sedimentary column. We conclude that elevated salinity and sulfate reduction are the main factors inducing dolomite precipitation in these lagoons, confirming the microbial dolomite formation theory. These results suggest that there may be other settings where sulfate-reducing bacteria induce dolomite precipitation under saline conditions, such as deep-sea sediments or sabkhas, and imply that microbial dolomite may significantly contribute to the sedimentary carbonate budget, particularly in the earliest Earth's history when anoxic conditions were more prevalent.     

Oxygen isotopic composition of sulfate in deep sea pore fluid: evidence for rapid sulfur cycling

We present new data of oxygen isotopes in marine sulfate (δ¹⁸O_SO4) in pore fluid profiles through organic‐rich deep‐sea sediments from 11 ODP sites around the world. In almost all sites studied sulfate is depleted with depth, through both organic matter oxidation and anaerobic methane oxidation. The δ¹⁸O_SO4 increases rapidly near the top of the sediments, from seawater values of 9 to maxima between 22 and 25, and remains isotopically heavy and constant at these values with depth. The δ¹⁸O_SO4 in these pore fluid profiles is decoupled from variations in sulfur isotopes measured on the same sulfate samples (δ³⁴S_SO4); the δ³⁴S_SO4 increases continuously with depth and exhibits a shallower isotopic increase. This isotopic decoupling between the δ³⁴S_SO4 and the δ¹⁸O_SO4 is hard to reconcile with the traditional understanding of bacterial sulfate reduction in sediments. Our data support the idea that sulfate or sulfite and water isotopically exchange during sulfate reduction and that some of the isotopically altered sulfur pool returns to the environment. We calculate that the rapid increase in the δ¹⁸O_SO4 in the upper part of these sediments requires rates of this oxygen isotope exchange that are several orders of magnitude higher than the rates of net sulfate reduction calculated from the sulfate concentration profiles and supported by the δ³⁴S_SO4. We suggest several mechanisms by which this may occur, including ‘net‐zero’ sulfur cycling, as well as further experiments through which we can test and resolve these processes.     

Sulfate reduction in fine-grained sediments in the Eastern Scheldt,southwest Netherlands

Sulfate reduction and sulfide accumulation were examined in fine-grained sediments from rapidly accreting abandoned channels and mussel culture areas in the Eastern Scheldt, which covered 4 and 5% of the total surface area, respectively.Reduction rates were measured in batch experiments in which the SO₄ ^2– depletion was measured during anoxic incubation. The reduction rates in summer varied between 14–68 mmol SO₄ ^2– m^–2 day^–1 and were related to the sedimentation rate. In the most rapidly accreting channels, SO₄ ^2– was exhausted below 15–50 cm and methanogenesis became the terminal process of organic carbon oxidationOne-dimensional modelling of sulfate profiles in mussel banks indicated that the subsurface influx of SO₄ ^2– was almost of the same order as the diffusive flux at the sediment-seawater interface, during the initial stages of the mussel bank accretion. The energy dissipation of waves and tidal currents on the mussel bank surface increased the apparent sediment diffusivity up to 3-fold, especially in the winterThe results indicate that acid volatile sulfide (AVS) was the major, in-situ reduced, sulfur compound in the sediment. The sulfidation of easily extractable iron was nearly complete. Pyrite concentrations (40–80 M S cm^–3) were as high as the AVS concentrations, but there was apparently no in-situ transformation of AVS into pyrite. The detrital pyrite originated from eroding marine sediments elsewhere     

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.     

Seasonality of sulfate reduction and pore water solutes in a marine fish farm sediment: the importance of temperature and sedimentary organic matter

Sulfate reduction and pore water solutes related to sulfur cycling and anaerobic processes (short chain fatty acids (SCFA), SO₄ ^2–, TCO₂, NH₄ ⁺, dissolved sulfides (H₂S) and CH₄) were examined during one year at a marine fish farm. Mineralization of fish farm waste products was rapid in this non-bioturbated, organic rich sediment. Stimulation of sulfate reduction rates (SRR) occurred primarily in the surface layers where the organic matter was deposited. Acetate was the most important (<99%) of the measured SCFA attaining high concentrations during summer months (up to 4.7 mM). The acetate profiles exhibited distinct seasonal cycles, where periods with high concentrations in the pore waters were found coincident with a high pool of particulate organic matter in the surface sediments and a low activity of the sulfate reducing bacteria (early spring and late summer). Periods with low acetate pools occurred when sulfate reduction rates were high in early summer and in winter were pools of particulate organic matter were decreasing. Methane production was observed concurrent with sulfate reduction in the microbial active surface layers in late summer. Subsurface peaks of SO₄ ^2–, TCO₂, NH₄ ⁺ and H₂S were evident in July and August due to rapid mineralization in these surface layers. With decreasing autumn water temperatures mineralization rates declined and subsurface peaks of these solutes disappeared. A strong relationship was found between pore water TCO₂, and NH₄ ⁺. Ratios between TCO₂, and NH₄ ⁺ were low compared to a control site, attaining minimum values in mid-summer. This indicated rapid nitrogen mineralization of nitrogen rich labile substrates in the fish farm sediment during the entire season.     

Effect of sulfur supply on sulfate uptake,and alkaline sulfatase activity in free-living and symbiotic bradyrhizobia

The effect of sulfur limitation on sulfate transport and metabolism was studied in four bradyrhizobia strains using sulfur-limited and sulfur-excess chemostat cultures. Characteristics of bradyrhizobia associated with sulfurlimitation were determined and these parameters used to bioassay the sulfur status of bacteroids in nodules on sulfur adequate or sulfur deficient soybean and peanut plants. Sulfur-limited cells took up sulfate 16- to 100-fold faster than sulfur-rich cells. The sulfate-uptake system appeared similar in all strains with apparent K _m values ranging from 3.1 M to 20 M sulfate with maximum activities between 1.6 and 10 nmol·min^-1·mg^-1 protein of cells. Sulfate-limited cells of all strains derepressed the enzyme alkaline sulfatase in parallel with the derepression of the sulfate transport system. Similarly, the initial enzyme of sulfate assimilation (ATP sulfurylase) was fully derepressed in sulfur-limited cultures. Bacteroids isolated from sulfur adequate and sulfur deficient soybean and peanut possessed very limited sulfate uptake activity and low levels of activity of ATP sulfurylase as well as lacking alkaline sulfatase activity. These results indicate bacteriods have access to adequate sulfur to meet their requirements even when the host plant is sulfur-deficient.Abbreviations CCCP Carbonyl cyanide m-chlorophenylhydrazone - DCCD N,N-dicyclohexyl carbodiimide     

Sedimentary anaerobic microbial biogeochemistry in the Gulf of Trieste, northern Adriatic Sea: Influences of bottom water oxygen depletion

Sediment samples from two locationsin the Gulf of Trieste (northern Adriatic Sea) werecollected during periods of maximum and minimumtemperatures for two years. Both sites were rich incarbonate material and inhabited by a diverse benthicinfaunal community. However, Site F exhibited adeeper dwelling faunal community, higher content ofcarbonate minerals, and larger grained sediments thanat site MA, which was closer to shore. Depth profilesof sulfate reduction and potential rates of iron andmanganese reduction were determined together withmeasurements of pore water and solid phase chemistry. Bottom waters at all sites were nearly saturated withoxygen for all of the dates sampled except forSeptember 1993 when bottom waters at site F were lessthan 50% saturated. Sulfate reduction rates were ashigh as 400 nmol ml^-1 day^-1 during latesummer and fall when temperatures were >20 °C,while rates during March (8 °C) were <30 nmolml^-1 day^-1. Potential rates of ironreduction, as determined by the accumulation of bothdissolved and acid-soluble reduced iron, were high insurficial sediments at each site except at site F whenbottom waters were partially depleted in oxygen. In the latter instance, sulfate reduction overwhelmedmetal reduction. Although the portion of metalreduction due directly to enzymatic use by bacteriawas not determined, the potential rate data suggestedthat Fe and perhaps Mn reduction were significantcomponents of anaerobic carbon degradation in thesesediments during much of the year. Both sitesappeared to support active metal-reducing bacterialcommunities. However, occasional depletion of oxygenin bottom waters appeared to cause a decrease inirrigation/reworking activity by infauna whichdepressed redox cycling of elements enhancing theimportance of sulfate reduction. A shift from metalreduction to sulfate reduction potentially exacerbatestoxic effects of oxygen depletion on fauna byincreasing the accumulation of toxic sulfide.     

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.     

Microbial Processes of the Carbon and Sulfur Cycles in Lake Shira (Khakasia)

Microbiological and biogeochemical studies of the meromictic saline Lake Shira (Khakasia) were conducted. In the upper part of the hydrogen-sulfide zone, at a depth of 13.5–14 m, there was a pale pink layer of water due to the development of purple bacteria (6 × 10⁵ cells/ml), which were assigned by their morphological and spectral characteristics toLamprocystis purpurea (formerly Amoebobacter purpureus). In August, the production of organic matter (OM) in Lake Shira was estimated to be 943 mg C/(m²day). The contribution of anoxygenic photosynthesis was insignificant (about 7% of the total OM production). The share of bacterial chemosynthesis was still less (no more than 2%). In the anaerobic zone, the community of sulfate-reducing bacteria played a decisive role in the terminal decomposition of OM. The maximal rates of sulfate reduction were observed in the near-bottom water (114 g S/(l day)) and in the surface layer of bottom sediments (901 g S/(dm³ day)). The daily expenditure of C_org for sulfate reduction was 73% of C_org formed daily in the processes of oxygenic and anoxygenic photosynthesis and bacterial chemosynthesis. The profile of methane distribution in the water column and bottom sediments was typical of meromictic reservoirs. The methane content in the water column increased beginning with the thermocline (7–8 m) and reached maximum values in the near-bottom water (17 l/l). In bottom sediments, the greatest methane concentrations (57 l/l) were observed in the surface layer (0–3 cm). The integral rate of methane formation in the water column and bottom sediments was almost an order of magnitude higher than the rate of its oxidation by aerobic and anaerobic methanotrophic microorganisms.     

Factors influencing uranium reduction and solubility in evaporation pond sediments

Evaporation ponds in the San Joaquin Valley (SJV), CA, USA that are used for the disposal of irrigation drainage waters, contain elevated levels of U that may be a threat to pond wildlife. The ponds support euryhaline algae, which become incorporated in the sediments as depositional organic matter (OM) – facilitating reducing conditions. Our earlier studies have shown that U in one SJV sediment was primarily present as the highly soluble U(VI) species (as opposed to the less soluble U(IV) species), despite the presence of volatile sulfides. In this research, we investigated the effects of native pond algae (Chlorella) and potential reducing agents on U redox chemistry of SJV pond sediments. San Joaquin Valley pond sediments were equilibrated with natural and synthetic pond inlet waters containing approximately 10 mg U(VI) L-1 to which reducing agents (acetate, sucrose, and alfalfa shoot) were added. The equilibrations were done under oxic (Chlorella only) and O2-limiting conditions (remaining treatments). Sediments were examined for changes in average U oxidation state by X-ray near- edge absorption structure (XANES) spectroscopy and U concentration by ICP-MS.For the alfalfa treatments, a 95 percent loss of U(VI) from solution, the presence of sulfides, and results from the XANES studies suggest U(VI) was reduced to U(IV). Upon exposure to air, the precipitated U was readily oxidized, suggesting the reduced U is susceptible to oxidation. Much less reduction of U(VI) was observed in the other 3 treatments and the solid phase was dominated by U(VI) as in the natural pond sediments. A second study was conducted with pond sediment-water suspensions to determine the effects of controlled PCO2 and low redox potential (Eh) on U solubility. These suspensions were equilibrated at 0.22 and 5.26 kPa PCO2 and allowed to free-drift from an oxidized to a reduced state. At high Eh and high PCO2, dissolved U concentrations were higher than in the low PCO2 systems due to greater complexation with CO3. Dissolved U concentrations decreased only under intense sulfate reducing conditions, even at low Eh conditions. It appears that U reduction occurred by chemical reduction via sulfide ion. Comparing the XANES data of the pond sediments with the laboratory-produced solids we conclude that biosorption by algae and bacteria is the dominant mechanism depositing U in the sediments. Even though there are organisms that can use U(VI) as a terminal electron acceptor, we found that sulfate reduction was preferred in these high- SO4 waters. Mixed oxidation state U-solids were preferentially formed in the pond sediments and in the lab except under intense SO4 reducing conditions.     

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.