Microbial Sulfate Reduction Research Articles

The mechanism of microbial sulfate reduction in high concentration sulfate wastewater enhanced by maifanite

Excessive sulfate levels in water bodies pose a dual threat to the ecological environment and human health. The microbial removal of sulfate encounters challenges, particularly in environments with high sulfate concentrations, where the gradual accumulation of sulfide hampers microbial activity. This study focuses on elucidating the mechanisms underlying the enhancement of microbial sulfate reduction in high-concentration sulfate wastewater through a comparative analysis of maifanite and zeolite biostimulants. The investigation reveals that zeolite primarily facilitates microbial growth by providing attachment sites, while maifanite augments sulfate-reducing bacteria (SRB) activity through the release of active substances such as Mo, Ca, and Cu. The addition of maifanite proves instrumental in enhancing microbial activity, manifesting as increased microbial load and protein production, augmented extracellular polymer generation, accelerated electron transfer, and facilitated microbial growth and biofilm formation. Noteworthy is the observation that the combined application of maifanite and zeolite exhibited a synergistic effect, resulting in a 167 % and 68 % increase in sulfate reduction rate compared to the utilization of maifanite (0.12 d−1) or zeolite (0.19 d−1) in isolation. Within this synergistic context, the relative abundance of Desulfobacteraceae reaches a peak of 15.4 %. The outcomes of this study corroborate the distinct promotion mechanisms of maifanite and zeolite in microbial sulfate reduction, offering novel insights into the application of maifanite in the context of high-concentration sulfate removal.

A one-dimensional diffusive transport model to evaluate H2S generation in salt caverns hydrogen storage sites

Salt caverns are considered a potential hydrogen storage site given the ductility, tightness, and chemical inertness of halite. In addition, unlike porous media, salt caverns require less cushion gas and allow more cycles of injection and production within a year. However, hydrogen is an electron donor for many hydrogenotrophic microorganisms including halophilic sulfate-reducing microbes (SRM) and hydrogen sulfide (H2S) can be generated in a cavern once sulfate and hydrogen become available in the aqueous phase. As salt deposits are often associated with large amounts of impurities such as anhydrite and gypsum, their dissolution during the leaching phase can release the required sulfate ions for SRMs to produce H2S once hydrogen diffuses and dissolves in the brine at the bottom of the cavern. In this study, a one-dimensional diffusive transport model was developed using PHREEQC to simulate sulfate reduction and H2S generation in a cavern at the gas-brine interface. The solution of Fick's diffusion equation was used to calculate the hydrogen concentration at each level of the 1D model while the kinetic rates of reactions were derived from reported experimental and field site observations of brine samples taken from salt caverns. The results obtained indicated that hydrogen consumption at the gas-brine interface can trigger H2S and methane formations. This is followed by a reduction in sulfate and carbonate concentration and a slight increase in pH due to the reduction of protons in the solution. It was also observed that the presence of Fe2+ ions can reduce the amount of the hydrogen sulfide production while Ca2+ ions slightly favour sulfate reduction due to the production of methane. Although the kinetic reaction rate of the reactions in the model is subject to a certain degree of uncertainty, the workflow and results this study can serve as a guide for the future storage of hydrogen in salt caverns.

Energy flux couples sulfur isotope fractionation to proteomic and metabolite profiles in Desulfovibrio vulgaris.

Microbial sulfate reduction is central to the global carbon cycle and the redox evolution of Earth's surface. Tracking the activity of sulfate reducing microorganisms over space and time relies on a nuanced understanding of stable sulfur isotope fractionation in the context of the biochemical machinery of the metabolism. Here, we link the magnitude of stable sulfur isotopic fractionation to proteomic and metabolite profiles under different cellular energetic regimes. When energy availability is limited, cell-specific sulfate respiration rates and net sulfur isotope fractionation inversely covary. Beyond net S isotope fractionation values, we also quantified shifts in protein expression, abundances and isotopic composition of intracellular S metabolites, and lipid structures and lipid/water H isotope fractionation values. These coupled approaches reveal which protein abundances shift directly as a function of energy flux, those that vary minimally, and those that may vary independent of energy flux and likely do not contribute to shifts in S-isotope fractionation. By coupling the bulk S-isotope observations with quantitative proteomics, we provide novel constraints for metabolic isotope models. Together, these results lay the foundation for more predictive metabolic fractionation models, alongside interpretations of environmental sulfur and sulfate reducer lipid-H isotope data.

Unraveling the Coupled Dynamics between DOM Transformation and Arsenic Mobilization in Aquifer Systems during Microbial Sulfate Reduction: Evidence from Sediment Incubation Experiment

Geogenic arsenic (As)-rich groundwater poses a significant environmental challenge worldwide, yet our understanding of the interplay between dissolved organic matter (DOM) transformation and arsenic mobilization during microbial sulfate reduction remains limited. This study involved microcosm experiments using As-rich aquifer sediments from the Singe Tsangpo River basin (STR) and Jianghan Plain (JHP), respectively. The findings revealed that microbial sulfate reduction remarkably increased arsenic mobilization in both STR and JHP sediments compared to that in unamended sediments. Moreover, the mobilization of As during microbial sulfate reduction coincided with increases in the fluorescence intensity of two humic-like substances, C2 and C3 (R = 0.87/0.87 and R = 0.73/0.66 in the STR and JHP sediments, respectively; p < 0.05), suggesting competitive desorption between DOM and As during incubation. Moreover, the transformations in the DOM molecular characteristics showed significant increases in CHOS molecular and low-O/C-value molecular intensities corresponding to the enhancement of microbial sulfate reduction and the possible occurrence of methanogenesis processes, which suggests a substantial bioproduction contribution to DOM components that is conducive to As mobilization during the microbial sulfate reduction. The present results thus provide new insights into the co-evolution between As mobilization and DOM transformations in alluvial aquifer systems under strong microbial sulfate reduction conditions.

Biological and paleoceanographic controls on the postglacial sulfur isotope records in Arctic shelf sediments

The Arctic Ocean has experienced environmental fluctuations during the Pleistocene glacial-interglacial cycles. Since the last deglaciation, the reinundation of the Bering Strait and regional transgression have led to dramatic changes in the western Arctic Ocean, affecting coastal landscapes, depositional processes, marine ecosystem, and, inherently, biogeochemical element cycles. Here, we investigate the records of sulfur, carbon, and iron cycles in the Chukchi Sea of the western Arctic, with a primary focus on microbial sulfate reduction and subsequent pyrite formation. Variations in the pyrite abundance and sulfur isotopic composition, derived from a 10-m sediment core, demonstrate that dynamic changes in the factors governing pyrite formation – organic electron donor, reactive iron, and sulfate – are closely linked to the regional environmental conditions. In the early Holocene sediment, pyrite precipitation was impeded by the lack of organic matter, even in the presence of abundant sulfate and reactive iron. In the overlying sediment, pyrite contents increased due to vigorous microbial sulfate reduction fueled by enhanced availability of organic substrate and additional methane from the sulfate-methane transition zone. In general, the increased supply of organic matter to the Chukchi Shelf sediments can be attributed to the resumed inflow of nutrient-rich Pacific Water through the flooded Bering Strait. The increase in pyrite content, however, does not correlate exactly with either the increase in TOC or the opening of the Bering Strait, both of which precede the increased pyrite formation. These lags reflect the balance between marine primary production and terrestrial carbon sources, as well as the balance between the Pacific Inflow and the Beaufort Gyre. While a comparable increase in pyrite and TOC contents during the Holocene deglaciation has also been reported in the Black and Baltic Sea sediments, their distinct sulfur isotope records, contingent upon the availability of sulfate and reactive iron, highlight that pyrite can serve as a valuable proxy for tracking past climate and environmental change, especially in barren sedimentary records such as those found in the Arctic Ocean.

Carbon-Sulfur isotope and major and trace element variations across the Permian–Triassic boundary on a shallow platform setting (Xiejiacao, South China)

We examined microbialites deposited near the Permian–Triassic boundary (PTB) at the Xiejiacao section of South China, including the size and morphology of pyrite framboids, carbonate carbon isotopes (δ13Ccarb), carbonate associated sulfur isotope (δ34SCAS), major and trace elements, and total organic carbon (TOC) concentrations. The microbialite unit is much thicker than the PTB beds in deeper water sections, providing more detailed geochemical records from that time. A prominent negative δ13Ccarb excursion was recognized in association with the second phase of the Permian–Triassic mass extinction (PTME), comparable with that of several other shallow platform facies sections worldwide. δ34SCAS stratigraphic profiles also show a negative excursion, with minimum values occurring slightly later than those of δ13Ccarb. The minimum peak can be calibrated to the middle part of the conodont Isarcicella staeschei Zone, corresponding to the second phase of PTME. Over all, the carbon and sulfur isotopes demonstrate a coupled long-term relationship with large negative excursions during the Permian–Triassic transition followed by gradual recovery in the lowest Triassic, represented an extremely low concentration of sulfate in the ocean during this period. In contrast, the CS isotopes are strongly decoupled within the microbialite unit, which could be linked with the oxygen-poor conditions and microbial sulfate reduction (MSR: Sulfate reducing microorganisms facilitated the precipitation of sulfide and carbonate, such as SO42− + 2CH2O → H2S + 2HCO3−). The second phase of PTME was calibrated to the top of the microbialite unit, which was marked by the second δ13Ccarb-δ34SCAS negative excursions. The distinct marine oxygen deficiency was indicated by the small pyrite framboids, relatively high values of UEF (>1) and Ce/Ce* (>0.8). Combined with the previous biostratigraphic work, we propose that continuous volcanic activity induced intensified marine anoxia, leading to biotic mortality in the second phase of the PTME. Overall, our isotopic and geochemical data, integrated with results of previous studies, provided a new explanation for the carbon and sulfur isotope variations and additional evidences into the concurrent environmental changes during the Permian–Triassic transition.

Sequential hydrotalcite precipitation, microbial sulfate reduction and in situ hydrogen sulfide removal for neutral mine drainage treatment

This study proposed and examined a new process flowsheet for treating neutral mine drainage (NMD) from an open-pit gold mine. The process consisted of three sequential stages: (1) in situ hydrotalcite (HT) precipitation; (2) low-cost carbon substrate driven microbial sulfate reduction; and (3) ferrosol reactive barrier for removing biogenic dissolved hydrogen sulfide (H2S). For concept validation, laboratory-scale columns were established and operated for a 140-days period with key process performance parameters regularly measured. At the end, solids recovered from various depths of the ferrosol column were analysed for elemental composition and mineral phases. Prokaryotic microbial communities in various process locations were characterised using 16S rRNA gene sequencing. Results showed that the Stage 1 HT-treatment substantially removed a range of elements (As, B, Ba, Ca, F, Zn, Si, and U) in the NMD, but not nitrate or sulfate. The Stage 2 sulfate reducing bioreactor (SRB) packed with 70 % (v/v) Eucalyptus woodchip, 1 % (w/v) ground (<1 mm) dried Typha biomass, and 10 % (w/v) NMD-pond sediment facilitated complete nitrate removal and stable sulfate removal of ca. 50 % (50 g-SO4 m−3 d−1), with an average H2S generation rate of 10 g-H2S m−3d−1. The H2S-removal performance of the Stage 3 ferrosol column was compared with a synthetic amorphous Fe-oxyhydroxide-amended sand control column. Although both columns facilitated excellent (95–100 %) H2S removal, the control column only enabled a further ca. 10 % sulfate reduction, giving an overall sulfate removal of 56 %. In contrast, the ferrosol enabled an extra 99.9 % sulfate reduction in the SRB effluent, leading to a near complete sulfate removal. Overall, the process successfully eliminated a range of metal/metalloid contaminants, nitrate, sulfate (2500 mg-SO4 L−1 in the NMD to <10 mg-SO4 L−1 in the final effluent) and H2S (>95 % removal). Further optimisation is required to minimise release of ferrous iron from the ferrosol barrier into the final effluent.

Molybdenum Isotope Fingerprinting of Microbial Sulfate Reduction in Seep Carbonate Rocks

AbstractUnderstanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments.

Carbon and sulfur cycling across the Silurian-Devonian boundary in the Qujing Basin, South China

During the late Silurian – Early Devonian there were significant changes in the biosphere and environment. However, there are few integrated studies of carbon and sulfur cycling in the Qujing Basin, in South China, which has extremely well-preserved sarcopterygian fossils. Here we report C-isotopic data of organic carbon (δ13Corg) and multiple S-isotopes of pyrite (δ34S and Δ33S) from two sections in the Qujing Basin. Our δ13Corg data show an increase of ~4‰ near the Silurian-Devonian boundary which can be correlated globally. We suggest that this rise in δ13Corg near the Silurian-Devonian boundary may have resulted from the weathering of the 13C-enriched carbonate platform, rather than from oceanic anoxia. This interpretation may explain why there is little evidence of a mass extinction near the Silurian-Devonian boundary in the Qujing Basin. Our S-isotopic data show positive δ34S values with either positive or negative Δ33S values, and most of the δ34S and Δ33S data can be explained by microbial sulfate reduction and Rayleigh distillation processes. The S-isotopic data from both sections suggest that seawater sulfate concentrations were very low in the Qujing Basin during the late Silurian – Early Devonian.

A volatile sulfur sink aids in reconciling the sulfur isotope mass balance of closed basin lakes

Sedimentary rocks from the early Eocene Green River Formation comprise the largest known lacustrine oil shale deposits, contain remarkably well-preserved fossils, and provide a unique record of climate evolution across the Early Eocene Climate Optimum, a period of high atmospheric CO2. The depositional environment of these intermountain lakes spanned from relatively fresh and fluvially influenced to expanded and stratified saline closed basin lakes under the influence of the Laramide orogeny and alternating humid and arid climatic conditions. As the surface area of the lakes expanded, alkalinity and salinity increased, with depositional cycles that linked to evaporative cycles and marked by an increasing abundance of organic matter-rich shales (TOC > 10 wt%). Simultaneously, an intriguing 20 ‰ positive shift in the sulfur isotope composition of sulfide minerals and organic sulfur is observed. Given that this trend cannot be simply explained by a change in the source of sulfate delivered to the basin, the evolution of biogeochemical sulfur cycling and the balance of fluxes in response to basin evolution remain unresolved. Here, we combine the sulfur isotope compositions of pyrite, organic sulfur, and carbonate-associated sulfate and molecular proxies of euxinia in samples from the Uinta basin's depocenter. We find that organic matter-rich sediments reflect deposition in a stratified water column with enhanced burial of pyrite and sulfurized organic matter, while organic-lean facies present evidence of, at least transiently, euxinic conditions reaching the photic zone during arid conditions presumably because of evaporation. As the lake became both saline-stratified and euxinic, we observe that δ34S values of all measured sulfur-bearing sedimentary proxies increase and evolve along a 1:1 line, a trend independent of facies that we interpret as reflecting a sulfate-limited system despite saline conditions. The isotopic mass balance of sulfur fluxes implies the existence of a sink of sulfur depleted in 34S that is spatially decoupled from burial in the depocenter. Modeling sulfur biogeochemical processes in a saline stratified lake system allows us to estimate that at least 50 % of the sulfur entering the lake could have been lost from the upper part of the euxinic water column where the fractionation factor imparted by microbial sulfate reduction is expressed. We propose that the overall isotopic enrichment of the system was caused by H2S degassing during arid climate intervals, presumably enhanced by transient water column mixing events. Further, episodic intrusion of euxinic bottom waters into the upper part of the water column might have triggered mass fish and plankton mortality, consequently facilitating the formation of these exceptionally fossiliferous and organic matter-rich rocks. Our study finds that volatile outgassing may be an underappreciated mechanism for the sulfur mass balance of stratified lacustrine systems.

Hydrothermal activity fuels microbial sulfate reduction in deep and distal marine settings along the Arctic Mid Ocean Ridges

Microbial sulfate reduction is generally limited in the deep sea compared to shallower marine environments, but cold seeps and hydrothermal systems are considered an exception. Here, we report sulfate reduction rates and geochemical data from marine sediments and hydrothermal vent fields along the Arctic Mid Ocean Ridges (AMOR), to assess the significance of basalt-hosted hydrothermal activity on sulfate reduction in a distal deep marine setting. We find that cored marine sediments do not display evidence for sulfate reduction, apart from low rates in sediments from the Knipovich Ridge. This likely reflects the overall limited availability of reactive organic matter and low sedimentation rates along the AMOR, except for areas in the vicinity of Svalbard and Bear Island. In contrast, hydrothermal samples from the Seven Sisters, Jan Mayen and Loki’s Castle vent fields all demonstrate active microbial sulfate reduction. Rates increase from a few 10s to 100s of pmol SO42- cm-3 d-1 in active high-temperature hydrothermal chimneys, to 10s of nmol SO42- cm-3 d-1 in low-temperature barite chimneys and up to 110 nmol cm-3 d-1 in diffuse venting hydrothermal sediments in the Barite field at Loki’s Castle. Pore fluid and sediment geochemical data suggest that these high rates are sustained by organic compounds from microbial mats and vent fauna as well as methane supplied by high-temperature hydrothermal fluids. However, significant variation was observed between replicate hydrothermal samples and observation of high rates in seemingly inactive barite chimneys suggests that other electron donors may be important as well. Sediment sulfur isotope signatures concur with measured rates in the Barite field and indicate that microbial sulfate reduction has occurred in the hydrothermal sediments since the recent geological past. Our findings indicate that basalt-hosted vent fields provide sufficient electron donors to support microbial sulfate reduction in high- and low-temperature hydrothermal areas in settings that otherwise show very low sulfate reduction rates.

Analysis of the Formation Mechanism of Hydrogen Sulfide in the 13# Coal Seam of Shaping Coal Mine.

In order to accurately predict the law of occurrence and migration of hydrogen sulfide (H2S) in the underground and effectively solve the problem of excessive concentration of H2S gas, laboratory experiments on the content of various forms of sulfur in coal, sulfur isotopes, thermal evolution history, and coal seam water samples were carried out by applying the theories of coal mine geology, microbiology, and analytical chemistry, and based on the experimental results, the cause of H2S gas was explored. Through the analysis of the geological conditions of the coal seam mined, it can be seen that the coal mine experienced the alternation of marine and continental phases in the process of coal formation and that there was no magma intrusion. The experimental results showed that iron sulfide in coal accounts for 73.25% of the total sulfur, indicating that the coal seam was rich in pyrite. The results of the isotope test showed that the sulfur isotopes in coal samples were all negative, indicating that the sulfur isotope fractionation in coal was large, the loss was serious, and the coal seam was greatly affected by seawater. According to the experimental results of vitrinite reflectance, it can be concluded that the highest temperature during the thermal evolution of the coal seam is 108.12 °C, which has not reached the temperature condition of sulfate thermochemical reduction. Comparing the concentration of acid ions in coal seam water and tap water, it was found that the concentration of SO42- in coal seam water is low, while the concentration of HCO3- is high. According to the experimental results and theoretical analysis, the H2S gas in the high-sulfur coal mine was caused by microbial sulfate reduction. Finally, the transformation path of sulfur in the coal seam was deduced and analyzed. The results showed that sulfur in coal is positively correlated with H2S gas concentration.

In situ sulfur isotope analysis of pyrite from the Ezuri Kuroko‐type volcanogenic massive sulfide deposit, northeastern Japan: Contribution of microbial sulfate reduction to initial sulfide mineralization

AbstractVolcanogenic massive sulfide (VMS) deposits are ancient analogues of seafloor massive sulfide (SMS) deposits. The importance and contribution of microbial activity during initial mineralization has recently been recognized in both VMS and SMS deposits. Here, we report in situ sulfur isotope compositions (δ34S) of pyrite from the Ezuri Kuroko‐type VMS deposit in northeastern Japan as determined by secondary ion mass spectrometry. During the evolutionary process of sulfide mineralization, pyrite textures changed from framboidal to colloform to euhedral. Initial framboidal pyrite had highly negative δ34S values down to −31.8‰ (average ± 1SD = −18.8‰ ± 13.0‰; n = 21), banded colloform pyrite exhibited medium δ34S values (−11.7‰ ± 10.4‰; n = 8), and euhedral pyrite displayed the highest average δ34S value of +2.7‰ ± 1.6‰ (n = 5); thus, δ34S varied as different textures of pyrite were produced during mineralization. The maximum isotopic fractionation between framboidal pyrite and past seawater sulfate (δ34S ca. +20‰) is −52‰; such values can be produced only by microbial sulfate reduction (MSR) in an open system. Framboidal pyrite with a low δ34S value is observed at the centers of sulfide‐rich areas within polished sections and has often been replaced by later sulfide minerals (sphalerite, galena, and chalcopyrite); thus, our S isotope data from the Ezuri pyrite reveal that sulfur derived from MSR induced and acted as a nucleation point for later sulfide mineral growth. Combined with previously reported data, our results endorse the importance and universality of MSR‐derived sulfur during the initial mineralization stage of both VMS and SMS deposits.

Sulfur geochemistry of the Salitre Formation phosphorites: Implications for the role of microbial ecology and sulfur cycling in phosphogenesis on an Ediacaran carbonate platform

The distribution and activity of polyphosphate-accumulating sulfide oxidizing bacteria within marine sediments control the spatial distribution of sedimentary phosphorite formation in the modern ocean. In modern phosphogenetic settings, the concerted effect of microbial sulfide oxidation and microbial sulfate reduction in sediment pore waters is preserved in the sulfur isotope composition of trace sulfate in authigenic and early-stage diagenetic carbonate cements and phosphatic cements, as well as that of authigenic pyrite. If such variations in microbial sulfur metabolism controlled the spatial distribution of early phosphate mineralization in the geologic past, then one would expect to find differences between the sulfur isotope composition of cement-forming minerals in phosphatic and non-phosphatic facies of ancient sedimentary phosphate deposits. Here, we present paired measurements of the sulfur isotope composition of structural sulfate and structural sulfide in pore cements from co-occurring phosphatic and non-phosphatic facies of the Ediacaran Salitre Formation (Northeastern Brazil). The difference between δ34S of trace structural sulfate in carbonate cements (CAS) or phosphate cements (PAS) and δ34S of structural sulfide in pyrite or chromium-reducible sulfur (CRS), defined as Δ34S, provides a constraint on sulfur cycling within the pore waters from which the cements precipitated. In carbonate-cemented textures of the Salitre Formation, Δ34S = 12 to 31 ‰. In phosphate-cemented textures, however, PAS and pyrite crystals had more similar sulfur isotope compositions: Δ34S = −5–12 ‰. These values support the hypothesis that microbial sulfide oxidation was more prevalent in pore waters where phosphate mineralization occurred compared to pore waters where carbonate mineralization occurred – suggesting that microbial sulfide oxidation may have enabled the formation of sedimentary phosphorite on an Ediacaran carbonate platform, just as in modern phosphogenetic sites.

A clumped isotope diagenetic framework for the Ediacaran dolomites: Insights to fabric‐specific geochemical variabilities

AbstractWhile marine dolomites formed under near surface conditions have been considered to be potentially reliable archives of past oceanic conditions, this interpretation comes with significant challenges because diagenetic alteration frequently produces diverse fabrics with large geochemical variability. It has been suggested that the Ediacaran dolomites in South China (Hamajing Member, Dengying Formation) recorded the oceanic conditions present at the time they formed, yet these dolomites are composed of five different fabrics (stromatolitic, micritic, oolitic, saddle dolomites and fibrous–radial dolomite cements) and show large variations in multiple geochemical isotope proxies (carbon, oxygen, clumped, magnesium and the sulphur of carbonate‐associated sulphate). This study establishes a paragenetic sequence for these dolomites by combining the clumped and the oxygen isotopic compositions, thereby assessing whether they are geochemically representative of the original seawater. Using this diagenetic framework, the micritic and stromatolitic dolomites show a closed‐system behaviour (low water–rock ratios; &lt;0.3) and are largely resistant to the hydrothermal alteration during late diagenesis. In contrast, the ooid and cement fabrics have been affected by the hydrothermal fluid precipitating saddle dolomite in the open‐system condition with the high stimulated water–rock ratios (&gt;1). Furthermore, in a closed‐system environment, the elevated δ24Mg and δ34S values in the stromatolitic dolomite reflect the isotopic Rayleigh fractionation that enriches the 26Mg and 34S through rock‐buffered recrystallization, coupled with microbial sulphate reduction. These results demonstrate that the complex signals in early marine dolomite should be carefully evaluated when used as a palaeoproxy.

Bioremediation of acid mine drainage using sulfate-reducing wetland bioreactor: Filling substrates influence, sulfide oxidation and microbial community

Two sulfate-reducing wetland bioreactors (SRB-1 filled with lignocellulosic wastes and SRB-2 with river sand) were applied for synthetic acid mine drainage treatment with bio-waste fermentation liquid as electron donor, and the influence of filling substrates on sulfate reduction, sulfur transformation and microbial community was studied. The presence of lignocellulosic wastes (mixture of cow manure, bark, sawdust, peanut shell and straw) in SRB-1 promoted sulfate reduction efficiency (68.9%), sulfate reduction rate (42.1 ± 11 mg S/(L·d)), dissolved sulfide production rate (27.4 ± 7 mg S/(L·d)), and particularly caused high conversion ratio of sulfate reduction into dissolved sulfide (66.4%). In comparison, the relatively low sulfate reduction efficiency (42.9%), sulfate reduction rate (27.0 ± 10 mg S/(L·d)), dissolved sulfide production rate (5.6 ± 3 mg S/(L·d)) and low dissolved sulfide conversion efficiency (21.2%) occurred in SRB-2. Mixed organic substrates including easily assimilated electron donors (in manure) and lignocellulosic matter were effective to promote quick start and long-term microbial sulfate reduction. More than 98% of produced dissolved sulfide was oxidized dominantly by photoautotrophic green sulfur bacteria (genera Chlorobium and Chlorobaculum), of which 64.6% and 54.5% was converted into elemental sulfur for SRB-1 and SRB-2. The oxidation of sulfide into elemental sulfur for potential recovery rather than sulfate is preferred. Diverse sulfate reducing bacteria and sulfide oxidizing bacteria co-existed in the treatment system, which led to a sustainable sulfur transformation. High metal removal efficiency for Fe (99.6%, 92.5%), Cd (99.9%, 99.9%), Zn (99.4%, 98.5%), Cu (94.5%, 94.6%) except for Mn (9.3%, 3.6%) was achieved, and effluent pH increased to 6.5–7.7 and 6.7–7.7 for SRB-1 and SRB-2, respectively. Microbial community was regulated by filling substrates. Synergism between lignocellulosic decomposing bacteria and sulfate reducing bacteria played a vital role in lignocellulosic bioreactor treating AMD, in addition to fermentation liquid serving as effective electron donor.

Discerning the sulfur geochemical features of turbidites and methane-rich sediments from the South China sea

Upward diffusion of dissolved methane and associated anaerobic oxidation of methane (AOM) coupled with microbial sulfate reduction (MSR) are widespread in normal hemipelagic sediments of continental margins. The occurrence of authigenic sulfur enrichment in such sediments is usually regarded as an indicator of AOM; however, extensive MSR and authigenic iron sulfide generation also occur in turbidites. Therefore, research attention should be directed toward determining the geochemical features of authigenic sulfur mineralization in methane-rich background sediments and turbidites. Here we report the sedimentology and geochemical composition of sediments from four piston cores (CL30, CL44, CL47, and CL3A) containing turbidite layers from methane-rich areas of the South China Sea. The turbidite layers were deposited at 17–15 kyr BP or earlier during the last glacial period and were located above the present sulfate–methane transition zone (SMTZ). The median grain size, proportion of sand-sized grains, and Si, Ti, K, and Zr contents show marked elevation in the turbidite layers compared with the background sediments, indicating the input of large amounts of terrigenous detrital matter with coarser grains. High total sulfur (TS) contents and low δ34SAIS values (AIS: acid-insoluble sulfur) (−35.2‰ to −26.1‰) are observed within turbidite layers relative to the background hemipelagic sediments in core CL44. These results suggest that intensive sulfidization occurred as a result of enhanced organoclastic sulfate reduction rates in turbidite horizons, which were probably caused by the resultant decrease in downward oxygen flux and waning bioturbation after rapid deposition of turbidites. In comparison, TS contents are higher and δ34SAIS values are positive (0.2‰–46.8‰) within the SMTZ on account of the rapid consumption of sulfate and build-up of isotopically heavier hydrogen sulfide pools via intensive AOM. Moreover, authigenic barium (Ba) enrichments commonly occur in the depth interval immediately above the SMTZ rather than within turbidite layers; therefore, they serve as a useful indicator of the position of the SMTZ. This study presents distinct differences in the geochemical compositions of turbidity deposits and methane-rich background sediments and highlights that a multi-proxy approach including sedimentological and geochemical analyses should be used to constrain the types of MSR in deep-sea sediments, given the common occurrence of turbidites and subsurface methane release in marginal deep-sea areas. It is also suggested that if applied with caution, S–C–Ba geochemical patterns can be used to identify palaeo-SMTZs and palaeo methane-rich zones in turbidite-containing strata.

The application of dual clumped isotope thermometer (Δ47 and Δ48) to the understanding of dolomite formation

Abstract Although several studies have shown the possibility of kinetic isotopic effects during the precipitation of carbonates using the dual clumped isotope proxy (Δ47 and Δ48), this approach has not yet been applied to the study of dolomite. We present Δ47 and Δ48 values of two types of Cenozoic Bahamian dolomites formed by distinctly different mechanisms. One dolomite, present in a core drilled on the island of San Salvador, is believed to have formed from normal seawater in the open system, while the other, taken from the Clino core drilled on the margin of the Great Bahama Bank, was precipitated associated with microbial sulfate reduction in the closed system. The Δ48-derived temperatures of San Salvador dolomites are consistent with their Δ47-temperatures, which are in turn close to the expected value of normal seawater. In contrast, dolomites from Clino show slightly elevated Δ47-derived temperatures (~15 °C higher than the expected) and significantly increased Δ48-temperatures (~145 °C) that are positively correlated with the sulfur isotopes of carbonate associated sulfate, in excess of +30‰. Such an association suggests a non-equilibrium process driven by microbial sulfate reduction, which elevates the alkalinity and depresses the pH of dolomitizing fluids. Notably, the greater amplitude of disequilibrium in Δ48 relative to Δ47 values demonstrates the sensitivity of the Δ48 proxy to kinetic isotope effects in dolomite. Conclusively, this study shows the potential of the dual clumped isotope proxy to identify microbial-mediated dolomitization in modern and ancient records.

Arctic Permafrost Thawing Enhances Sulfide Oxidation

AbstractPermafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw‐induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO2) is relatively unconstrained. Resolving this uncertainty is important as thaw‐driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean‐atmosphere system and increase pCO2, producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate () sulfur (34S/32S) and oxygen (18O/16O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact on pCO2. Calculations found that approximately 80% of in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover, 34S/32S ratios, 13C/12C ratios of dissolved IC, and sulfur X‐ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values of pCO2 over timescales shorter than carbonate compensation (∼104 yr) and, for mainstem samples, higher values of pCO2 over timescales longer than carbonate compensation but shorter than the residence time of marine (∼107 yr). Furthermore, the absolute concentrations of and Mg2+ in the Koyukuk River, as well as the ratios of and Mg2+ to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale‐dependent feedback on warming.

Large sulfur isotope fractionation during abiotic consumption of hydrogen sulfide after cessation of bacterial growth in batch culture experiments of sulfate reducing bacteria

Microbial sulfate reduction is a key process in the oceanic sulfur cycle and imparts a large sulfur isotope fractionation. The mechanism of sulfur isotope fractionation during microbial sulfate reduction has been studied from the geochemical and biochemical aspects since the 1950s. Recently, however, the large sulfur isotope fractionation, exceeding 47‰, has been observed in some pure culture experiments of sulfate reducing bacteria and the tentative understanding of microbial sulfur isotope fractionation has not well explained the mechanism. Here we quantified growth phase dependent sulfur isotope fractionation of a type sulfate reducer Desulfovibrio desulfuricans (DSM642) and revealed that the magnitude of isotope fractionation increased from -13.4 ± 3.6‰ in early exponential phase to -65.9 ± 21.0‰ in later exponential phase having clear negative correlation with cell specific sulfate reduction rate. Our results show the importance of cells growth phase and states that control cell specific sulfate reduction rate and sulfur isotope fractionation. Although microbial sulfate reduction likely continued to stationary phase of cells, microbial sulfur isotope fractionation could not be quantified because of the decreasing total dissolved sulfide (ΣH2S: H2S, HS−, and S2−) concentration after stationary phase. A non-microbial ΣH2S-consuming reaction is interpreted to have occurred during the stationary phase and this had large sulfur isotope fractionations, -10.5 ± 1.1‰ and -45.6 ± 12.4‰. Besides, the non-microbial ΣH2S-consuming reaction decreased Δ33S’ value of the ΣH2S. While the end-product of the non-microbial ΣH2S-consuming reaction in the stationary phase remains unidentified, we observed precipitates of some sulfide minerals and organic sulfur in the stationary phase media. Regardless of the end-product, the reaction increases the sulfur isotopic composition of dissolved ΣH2S, which can account for the high sulfur isotopic compositions of ΣH2S compared to pyrite and organic sulfur observed in some modern marine sediments.