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Elevated sulfate levels in eutrophic lakes have been observed to induce the release of endogenous phosphorus. While previous studies have predominantly examined its impact on iron-bound phosphorus (FeP), the influence on organic phosphorus (OP), a crucial active phosphorus component in sediments, remains poorly understood. In this study, mesocosms were established with lactate supplementation and varying sulfate concentrations to explore sulfate reduction and its impacts on phosphorus mobilization in freshwater sediments. Lactate addition induced hypoxia and provided substrates, thereby stimulating sulfate reduction with a decline of sulfate levels, an increase of sulfide concentrations, and fluctuations of sulfate-reducing bacteria. Meanwhile, concentrations of total dissolved phosphorus and phosphate were dramatically promoted during lactate decomposition, with a higher sulfate concentration associated with greater phosphorus elevation, correlating with the decrease of total phosphorus in sediment. The increase in phosphorus of the overlying water was partly attributed to FeP release from the sediment, confirmed by a decrease in its sediment content. FeP release was ascribed to dissimilatory reduction of iron oxides or chemical reduction mediated by sulfides in anoxic sediments, leading to the desorption and subsequent release of phosphorus. Evidences included the proliferation of iron-reducing bacteria, a decrease in Fe(II) concentrations in sediment pore- water, and the continuous accumulation of solid iron sulfides in surface sediments. Furthermore, OP mineralization in sediment also contributed to the increase in phosphorus in water columns, confirmed by a reduction in its content and the abundance of fermentation bacteria in surface sediment. Notably, the decrease in OP content accounted for >80 % of the total phosphorus reduction in surface sediment in the end. Thus, sulfur cycling plays a critical role in iron and phosphorus cycling, significantly stimulating not only the mobilization of FeP but also OP in sediments, with OP mineralization potentially being the primary contributor to endogenous phosphorus release.

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This research aims to investigate the influence of sulfate on the performance of microbial electrolysis cell-assisted anaerobic digester (MEC-AD) across varying sulfate conditions, including no sulfate and reduced COD/sulfate ratios from 20 to 1. The principal results indicate a gradual decline in methane yield in the MEC-AD from 78.7 ± 2.3 % under no sulfate conditions to 56.2 ± 2.0 % at a COD/sulfate ratio of 1, contrasting with a more substantial decrease in the control reactor (69.9 ± 3.6 % to 32.8 ± 1.5 %). The MEC-AD reactor exhibits heightened resilience to sulfide toxicity, showcasing higher specific methanogenic activities. Key findings suggest that the MEC-AD reactor maintains lower free sulfide concentrations, attributed to its higher pH and potential anodic sulfide oxidation. Additionally, the study reveals the promotion of syntrophic partnerships in the MEC-AD reactor, particularly between sulfate-reducing bacteria (SRB) such as Desulfovibrio, Desulfomicrobium, and Desulfobulbus, and other microbial groups, including hydrogenotrophic methanogens and electroactive bacteria. The integration of these mechanisms highlights the MEC-AD reactor's ability to effectively mitigate sulfate-induced challenges and enhance overall anaerobic digestion performance. This study presents a significant step forward in the development of resilient anaerobic digestion systems capable of efficiently handling sulfate stress.

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Soil contamination with heavy metals from industrial and mining activities poses significant environmental and public health risks, necessitating effective remediation strategies. This review examines the utilization of sulfate-reducing bacteria (SRB) for bioremediation of heavy metal-contaminated soils. Specifically, it focuses on SRB metabolic pathways for heavy metal immobilization, interactions with other microorganisms, and integration with complementary remediation techniques such as soil amendments and phytoremediation. We explore the mechanisms of SRB action, their synergistic relationships within soil ecosystems, and the effectiveness of combined remediation approaches. Our findings indicate that SRB can effectively immobilize heavy metals by converting sulfate to sulfide, forming stable metal sulfides, thereby reducing the bioavailability and toxicity of heavy metals. Nevertheless, challenges persist, including the need to optimize environmental conditions for SRB activity, address their sensitivity to acidic conditions and high heavy metal concentrations, and mitigate the risk of secondary pollution from excessive carbon sources. This study underscores the necessity for innovative and sustainable SRB-based bioremediation strategies that integrate multiple techniques to address the complex issue of heavy metal soil contamination. Such advancements are crucial for promoting green mining practices and environmental restoration.

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Landfill mining (LFM) has gained widespread recognition due to its benefits in terms of resource utilization of landfill waste and reuse of landfill sites. However, it is important to thoroughly assess the associated environmental risks. This study simulated the pressure release induced from LFM in small-scale batch anaerobic reactors subject to different initial pressures (0.2-0.6 MPa). The potential risk of hydrogen sulfide (H2S) pollution resulting from pressure release caused by LFM was investigated. The results demonstrated that the concentration of H2S significantly increased following the simulated pressure treatments. At the low (25 °C) and high (50 °C) temperatures tested, the peak H2S concentration reached 19366 and 24794 mg·m-3, respectively. Both of these concentrations were observed under highest initial pressure condition (0.6 MPa). However, the duration of H2S release was remarkably longer (>90 days) at the low temperature tested. Microbial diversity analysis results revealed that, at tested low temperature, the sulfate-reducing bacteria (SRB) communities of various pressure-bearing environments became phylogenetically similar following the pressure releases. In contrast, at the high temperature tested, specific SRB genera (Desulfitibacter and Candidatus Desulforudis) showed further enrichment. Moreover, the intensified sulfate reduction activity following pressure release was attributed to the enrichment of specific SRBs, including Desulfovibrio (ASV585 and ASV1417), Desulfofarcimen (ASV343), Candidatus Desulforudis (ASV24), and Desulfohalotomaculum (ASV506 and ASV2530). These results indicate that the pressure release associated with LFM significantly increases the amount of H2S released from landfills, and the SRB communities have different response mechanisms to pressure release at different temperature conditions. This study highlights the importance of considering the potential secondary environmental risks associated with LFM.

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Dual electron donor bioretention systems have emerged as a popular strategy to enhance dissolved nitrogen removal from stormwater runoff. Pyrite-woodchip mixotrophic bioretention systems showed a promoted and stabilized removal of dissolved nutrients under complex rainfall conditions, but the sulfate reduction process that can induce iron sulfide generation and reuse was overlooked. In this study, experiments and models were applied to investigate the effects of filler configuration and dissolved organic carbon (DOC) dissolution rate on treatment performance and iron sulfide generation in pyrite-woodchip bioretention systems. Key parameters govern that DOC dissolution and microbe-mediated processes were obtained by experiments. The water quality models that integrate one-dimensional constant flow, sorption and microbial transformation kinetics were used to predict the performance of bioretention systems. Results showed that the mixotrophic bioretention system with woodchip mixed in the vadose zone and pyrite in the saturated zone achieves a better performance in both nitrogen removal efficiency and by-product control. Comparably, woodchip and pyrite mixed in the saturated zone could encounter a high secondary pollution risk. The sensitivity coefficients of oxic/anoxic DOC dissolution rates to total nitrogen removal are 0.36 and -2.43 respectively. Iron sulfide generation was affected by DOC distribution and the competition between heterotrophic denitrifiers, autotrophic denitrifiers, and sulfate-reducing bacteria (SRB). DOC accumulation has an antagonistic effect on iron production and sulfate reduction. Extra DOC accumulation favors sulfate reduction while high DOC concentration inhibits pyrite-based denitrification and reduces Fe(III) production. The recycling of iron sulfide can improve the robustness and sustainability of bioretention systems.

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Sulfide produced from dissimilatory sulfate reduction can combine with hydrogen to form hydrogen sulfide, causing odor issues and environmental pollution. To address this problem, ferrihydrite-humic acid coprecipitate was added to improve assimilatory sulfate reduction (ASR), resulting in a decrease in sulfide production (190.2 ± 14.6 mg/L in the Fh-HA group vs. 246.3 ± 8.1 mg/L in the Fh group) with high sulfate removal. Humic acid, adsorbed on the surface of ferrihydrite, delayed secondary mineralization of ferrihydrite under sulfate reduction condition. Therefore, more iron-reducing species (e.g. Trichococcus, Geobacter) were enriched with ferrihydrite-humic acid coprecipitate to transfer more electrons to other species, which led to more COD reduction, an increase in electron transfer capacity, and a decrease in the NADH/NAD+ ratio. Metagenomic analysis also indicated that functional genes related to ASR was enhanced with ferrihydrite-humic acid coprecipitate. Thus, the addition of ferrihydrite-humic acid coprecipitate can be considered as a promising candidate for anaerobic sulfate wastewater treatment.

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Physico-chemical characteristics of groundwater are often impacted by agricultural practices such as land use, fertilizer types, and groundwater pumping. This study aimed to identify contaminant sources and redox processes controlling the hydrogeochemistry of groundwater in riparian zones influenced by intensive agricultural activities, focusing on sulfur species. Groundwater samples were collected bimonthly from March 2014 to March 2015 from groundwater wells in two zones in South Korea with different agricultural systems. The water isotopic compositions of the groundwater indicated that all groundwater originated from the same meteoric water. Groundwater samples affected by periodic groundwater pumping exhibited wide variations in Mn2+ (47.8 ± 18.2 µM) and Fe2+ (123 ± 61.0 µM) and elevated SO42-, while NO3- was below the detection limit. Groundwater chemistry was affected by fertilizer and manure, and denitrification. The oxidation of reduced sulfur compounds by oxygen and nitrate did not fully account for the elevated SO42- concentrations and isotopic composition of sulfate (δ34S and δ18O) in the investigated aquifers. Therefore, we postulate that water level change due to periodic groundwater pumping and recharge enabled oxidants (MnO2 and Fe3+) to also contribute to oxidation of reduced sulfur. Additionally, fertilizers with distinct δ34S values and bacterial sulfate reduction (BSR) affected groundwater chemistry and its sulfur species, including δ34SSO4 and δ18OSO4. Removal of sulfate from the aquifer during pumping limited BSR. Consequently, the agricultural practices may further increase sulfate concentrations in the groundwater. This environmental impact should be thoroughly managed because high sulfate concentrations in drinking water cause ingestion problems in humans.

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In the leachate-saturation zone of landfills, sulfate reduction is influenced by temperature and electron donors. This study assessed sulfate reduction behaviors under varied electron donor conditions by establishing multiple temperature variation scenarios based on stable temperature fields within the leachate-saturation zone. The results showed that temperature variations altered the microbial community structure and significantly influenced the sulfate reduction process. A more pronounced effect was observed with a temperature difference of 30 °C compared to one of 10 °C. In addition, sulfate reduction was influenced by the presence of electron donors and acceptors. In the middle and low-temperature regions (35 °C and 25 °C), sulfate reduction reaction of acidic organic matter was more significant, while alcohol and saccharide organic substances were more effective in promoting sulfate reduction at high-temperature regions (55 °C). Notably, a 30 °C temperature difference within the leachate-saturation zone significantly altered the microbial community structure, which influenced the sulfate reduction behavior. In particular, Firmicutes and Synergistota played essential roles in mediating the variance in sulfate reduction efficiency with a 30 °C decrease and 30 °C increase, respectively. The results also revealed that temperature changes within landfills were influenced by leachate migration, therefore, controlling leachate recharge can help prevent secondary risks associated with sulfate reduction processes.

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Carbon cycling in coastal wetland soil is controlled by a complex interplay between microbial processes and porewater chemistry that are often influenced by various external forcings like wind, river discharge, and sea-level changes, where most of the organic carbon is mineralized to its inorganic form by various aerobic and anaerobic respiration pathways. The export of this inorganic carbon (DIC) from coastal wetlands has long been recognized as a significant component of the global carbon cycle. The major objective of this work is to determine the relative contribution of various respiration pathways to seasonal DIC production in two contrasting marshes (brackish and salt). The DIC fluxes estimates for the brackish and salt marshes were found to range between 36.52 ± 5.81 and 33.98 ± 2.21 mmol m-2 d-1 in winter and 133.10 ± 102.60 and 82.37 ± 30.87 mmol m-2 d-1 during summer of 2020. For the brackish marsh, aerobic respiration and iron reduction were found to be the primary contributors to DIC production representing 17.91-35.21 % and 61.13-81.97 % of total measured organic matter (OM) respiration respectively. On the other hand, aerobic respiration and sulfate reduction were the primary contributors to DIC production in the salt marsh, accounting for 37.91-83.93 % and 15.87-62.04 % of the total measured OM respiration respectively. The Mississippi River Deltaic Plain experiences high relative sea level rise and expected to undergo rapid change in salinity regime in near future from additional changes in river discharge, proposed sediment diversion plans, and storm surge intensities. The current study represents the first attempt to concurrently estimate various respiration pathways in this region and more studies are needed to understand the trajectories of soil OM respiration pathways and its impact on coastal carbon cycling.

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To elucidate the spatial-temporal impact of invasive saltmarsh plant Spartina anglica on the biogeochemical processes in coastal wetlands, we investigated the rates and partitioning of organic carbon (Corg) mineralization in three representative benthic habitats: (1) vegetated sediments inhabited by invasive S. anglica (SA); vegetated sediments by indigenous Suaeda japonica; and (3) unvegetated mud flats. Microbial metabolic rates were greatly stimulated at the SA site during the active growing seasons of Spartina, indicating that a substantial amount of organic substrates was supplied from the high below-ground biomass of Spartina. At the SA site, sulfate reduction dominated the Corg mineralization pathways during the plant growing season, whereas iron reduction dominated during the non-growing season. Overall, due to its greater biomass and longer growing season than native Suaeda, the expansion of invasive Spartina is likely to greatly alter the Corg-Fe-S cycles and carbon storage capacity in the coastal wetlands.

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The continuous increase in sulfate (SO42-) concentrations discharged by anthropogenic activities lacks insights into their dynamics and potential impact on CH4 budgets in freshwater lakes. Here we conducted a field investigation in the lakes along the highly developed Yangtze River basin, China, additionally, we analyzed long-term data (1950-2020) from Lake Taihu, a typical eutrophic lake worldwide. We observed a gradual increase in SO42- concentrations up to 100 mg/L, which showed a positive correlation with the trophic state of the lakes. The annual variations indicated that eutrophication intensified the fluctuation of SO42- concentrations. A random forest model was applied to assess the impact of SO42- concentrations on CH4 emissions, revealing a significant negative effect. Synchronously, a series of microcosms with added SO42- were established to simulate cyanobacteria decomposition processes and explore the coupling mechanism between sulfate reduction and CH4 production. The results showed a strong negative correlation between CH4 concentrations and initial SO42- levels (R2 = 0.83), indicating that higher initial SO42- concentrations led to lower final CH4 concentrations. This was attributed to the competition for cyanobacteria-supplied substrates between sulfate reduction bacteria (SRB) and methane production archaea (MPA). Our study highlights the importance of considering the unexpectedly increasing SO42- concentrations in eutrophic lakes when estimating global CH4 emission budgets.

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Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.

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Mercury (Hg) analyses in species of fish are performed for two reasons: (1) to safeguard human health; and (2) to assess environmental quality, since different environmental changes may increase the Hg concentrations in fish. These analyses are important since both natural and human activities can increase these Hg concentrations, which can vary extensively, depending on the species, age and catching location. Hg-contaminated fish or other marine foodstuffs can be only detected by chemical analysis. If the aim of Hg analysis is to protect the health of marine food consumers, researcher workers must consider the location where the fish were caught and interpret the results accordingly. Health and environmental officials must appreciate that in specific places, local people may have a daily diet consisting entirely of fish or other marine foods, and these individuals should not be exposed to high concentrations of Hg. Regional and national health and environmental officials should follow the recent guidance of international organizations when drawing their final conclusions about whether the products are safe or unsafe to eat. Correct statistical calculations are not always carried out; so, too high Hg amounts could be presented, and fish eaters could be protected. This work has been conducted to show the differences in Hg concentrations between weighted (weighted with fish weights) and arithmetic means. Thus, the mean that is only weighted also includes the Hg content in fishes; so, the exposure to Hg can be evaluated.

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Climate change is rapidly transforming Arctic landscapes where increasing soil temperatures speed up permafrost thaw. This exposes large carbon stocks to microbial decomposition, possibly worsening climate change by releasing more greenhouse gases. Understanding how microbes break down soil carbon, especially under the anaerobic conditions of thawing permafrost, is important to determine future changes. Here, we studied the microbial community dynamics and soil carbon decomposition potential in permafrost and active layer soils under anaerobic laboratory conditions that simulated an Arctic summer thaw. The microbial and viral compositions in the samples were analyzed based on metagenomes, metagenome-assembled genomes, and metagenomic viral contigs (mVCs). Following the thawing of permafrost, there was a notable shift in microbial community structure, with fermentative Firmicutes and Bacteroidota taking over from Actinobacteria and Proteobacteria over the 60-day incubation period. The increase in iron and sulfate-reducing microbes had a significant role in limiting methane production from thawed permafrost, underscoring the competition within microbial communities. We explored the growth strategies of microbial communities and found that slow growth was the major strategy in both the active layer and permafrost. Our findings challenge the assumption that fast-growing microbes mainly respond to environmental changes like permafrost thaw. Instead, they indicate a common strategy of slow growth among microbial communities, likely due to the thermodynamic constraints of soil substrates and electron acceptors, and the need for microbes to adjust to post-thaw conditions. The mVCs harbored a wide range of auxiliary metabolic genes that may support cell protection from ice formation in virus-infected cells. IMPORTANCE: As the Arctic warms, thawing permafrost unlocks carbon, potentially accelerating climate change by releasing greenhouse gases. Our research delves into the underlying biogeochemical processes likely mediated by the soil microbial community in response to the wet and anaerobic conditions, akin to an Arctic summer thaw. We observed a significant shift in the microbial community post-thaw, with fermentative bacteria like Firmicutes and Bacteroidota taking over and switching to different fermentation pathways. The dominance of iron and sulfate-reducing bacteria likely constrained methane production in the thawing permafrost. Slow-growing microbes outweighed fast-growing ones, even after thaw, upending the expectation that rapid microbial responses to dominate after permafrost thaws. This research highlights the nuanced and complex interactions within Arctic soil microbial communities and underscores the challenges in predicting microbial response to environmental change.

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To determine contamination sources and pathways, the use of multiple isotopes, including metal isotopes, can increase the reliability of environmental forensic techniques. This study differentiated contamination sources in groundwater of a mine area and elucidated geochemical processes using Cu, Zn, S-O, and O-H isotopes. Sulfate reduction and sulfide precipitation were elucidated using concentrations of dissolved sulfides, δ34SSO4, δ18OSO4, and δ66Zn. The overlying contaminated soil was possibly responsible for the contamination of groundwater at <5 mbgl, which was suggested by low δ65Cu values (0.419-1.120‰) reflecting those of soil (0.279-1.115‰). The existence of dissolved Cu as Cu(I) may prevent the increase in δ65Cu during leaching of contaminated soil in the sulfate-reducing environment. In contrast, the groundwater at >5 mbgl seemed to be highly affected by the contamination plume from the adit water, which was suggested by high SO42- concentrations (407-447 mg L-1) and δ65Cu (0.252-2.275‰) and δ66Zn (-0.105‰-0.362‰) values at a multilevel sampler approaching those of the adit seepages. Additionally, the O-H isotopic ratios were distinguished between <5 mbgl and >5 mbgl. Using δ65Cu and δ66Zn to support the determination of groundwater contamination sources may be encouraged, particularly where the isotopic signatures are distinct for each source.

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To enhance the performance of the internal circulation (IC) reactor when treating high-sulfate organic wastewater, a laboratory-scale two-phase IC reactor with distinct phase separation capabilities was designed, and the sulfate reduction and methanogenesis processes were optimized by segregating the reactor into two specialized reaction zones. The results demonstrated that the first and second reaction areas of the two-phase IC reactor could be maintained at 4.5-6.0 and 7.5-8.5, respectively, turning them into the specialized phase for sulfate reduction and methanogenesis. Through phase separation, the two-phase IC reactor achieved a COD degradation and sulfate reduction efficiency of more than 80% when the influent sulfate concentration exceeded 5,000 mg/L, which were 32.32% and 16.04% higher than that before phase separation. Functional analyses indicated a greater activity of both the dissimilatory and assimilatory sulfate reduction pathways in the acidogenic phase, largely due to a rise in the relative abundance of the genera Desulfovibrio, Bacteroides, and Lacticaseibacillus, the primary carriers of sulfate reduction functional genes. In contrast, all the acetoclastic, hydrogenotrophic, and methylotrophic methanogenesis pathways were inhibited in the acidogenic phase but thrived in the methanogenic phase, coinciding with shifts in the genus Methanothrix, which harbors the mcrA, mcrB, and mcrG genes essential for the final transformation step of all three methanogenesis pathways.

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Groundwater contaminated by benzene and toluene is a common issue, posing a threat to the ecosystems and human health. The removal of benzene and toluene under sulfate-reducing condition is well known, but how the bacterial community shifts during this process remains unclear. This study aims to evaluate the shift in bacterial community structure during the biodegradation of benzene and toluene under sulfate-reducing condition. In this study, groundwater contaminated with benzene and toluene were collected from the field and used to construct three artificial samples: Control (benzene 50 mg/L, toluene 1.24 mg/L, sulfate 470 mg/L, and HgCl2 250 mg/L), S1 (benzene 50 mg/L, toluene 1.24 mg/L, sulfate 470 mg/L), and S2 (benzene 100 mg/L, toluene 2.5 mg/L, sulfate 940 mg/L). The contaminants (benzene and toluene), geochemical parameters (sulfate, ORP, and pH), and bacterial community structure in the artificial samples were monitored over time. By the end of this study (day 90), approximately 99% of benzene and 96% of toluene could be eliminated in both S1 and S2 artificial samples, while in the Control artificial sample the contaminant levels remained unchanged due to microbial inactivation. The richness of bacterial communities initially decreased but subsequently increased over time in both S1 and S2 artificial samples. Under sulfate-reducing condition, key players in benzene and toluene degradation were identified as Pseudomonas, Janthinobacterium, Novosphingobium, Staphylococcus, and Bradyrhizobium. The results could provide scientific basis for remediation and risk management strategies at the benzene and toluene contaminated sites.

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Bloom-induced macroalgal enrichment on the seafloor can substantially facilitate dissolved sulfide (DS) production through sulfate reduction. The reaction of DS with sedimentary reactive iron (Fe) is the main mechanism of DS consumption, which however usually could not effectively prevent DS accumulation caused by pulsed macroalgal enrichment. Here we used incubations to investigate the performance of Fe-rich red soil for buffering of DS produced from macroalgae (Ulva prolifera)-enriched sediment. Based on our results, a combination of red soil additions (6.8 kg/m2) before and immediately after pulsed macroalgal deposition (455 g/m2) can effectively cap DS within the red soil layer. The effective DS buffering is mainly due to ample Fe-oxide surface sites available for reaction with DS. Only a small loss (4 %) of buffering capacity after 18-d incubation suggests that the red soil is capable of prolonged DS buffering in macroalgae-enriched sediments.

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The activity of subsurface microorganisms can be harnessed for engineering projects. For instance, the Swiss radioactive waste repository design can take advantage of indigenous microorganisms to tackle the issue of a hydrogen gas (H2) phase pressure build-up. After repository closure, it is expected that anoxic steel corrosion of waste canisters will lead to an H2 accumulation. This occurrence should be avoided to preclude damage to the structural integrity of the host rock. In the Swiss design, the repository access galleries will be back-filled, and the choice of this material provides an opportunity to select conditions for the microbially-mediated removal of excess gas. Here, we investigate the microbial sinks for H2. Four reactors containing an 80/20 (w/w) mixture of quartz sand and Wyoming bentonite were supplied with natural sulfate-rich Opalinus Clay rock porewater and with pure H2 gas for up to 108 days. Within 14 days, a decrease in the sulfate concentration was observed, indicating the activity of the sulfate-reducing bacteria detected in the reactor, e.g., from Desulfocurvibacter genus. Additionally, starting at day 28, methane was detected in the gas phase, suggesting the activity of methanogens present in the solid phase, such as the Methanosarcina genus. This work evidences the development, under in-situ relevant conditions, of a backfill microbiome capable of consuming H2 and demonstrates its potential to contribute positively to the long-term safety of a radioactive waste repository.

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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.

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