High Sulfate Reduction Rates Research Articles

Sedimentary geochemistry in P-limited freshwater drained marshes (Charente-Maritime, France): Original drivers for phosphorus mobilization

Phosphorus bioavailability is a major issue in aquatic environments, where it generally limits primary production. In this work, the analysis of the pore water and the solid phase of the sediment was carried out over a 9-month monitoring period between February 2020 and April 2021 in two drained marshes (Marans and Genouillé, France) distinct by their uses and management tools. Soluble reactive phosphorus (SRP) enrichment in the sediment was intimately controlled by iron oxide dissolution. The latter seemed highly controlled by seasonal nitrate inputs (winter and early spring) that favoured denitrification as a major benthic mineralization process promoting iron curtain development and stability. Following benthic mitigation of nitrate other anaerobic metabolisms developed such as iron dissolutive reduction promoting P recycling and planktic bioavailability. Surprisingly, sulphur cycle seemed to affect P dynamics, especially in the absence of nitrate. The absence of NO3− triggered high sulphate reduction rates in the two first centimeters depth, reaching −8.9 E−03 ± 0.5 E−03 and -5.0 E−03 ± 0.2 E−03 nmol cm−3 s−1 in August and July at Marans and Genouillé respectively. These values placed this process at higher rates than the denitrification (maximum in May at Marans with −5.0 E−03 ± 1.1 E−03 nmol cm−3 s−1) and reduced iron production (maximum in July at Genouillé with 0.5 E−03 ± 0.1 E−03 nmol cm−3 s−1). The rapidity with which process changes occur (monthly scale) testified to the dynamism of these systems. The similarity in geochemical patterns regarding NO3− pressure at both sites underlines the importance of diffuse pollution in coastal systems for nitrogen mitigation and phosphorus trapping. The results obtained in this study could lead to the development of a generalized diagenetic operating model for temperate systems with high agricultural pressure. This would enable to target management efforts to both optimize the purification function and limit eutrophication risks in these systems.

The low-temperature germinating spores of the thermophilic Desulfofundulus contribute to an extremely high sulfate reduction in burning coal seams.

Burning coal seams, characterized by massive carbon monoxide (CO) emissions, the presence of secondary sulfates, and high temperatures, represent suitable environments for thermophilic sulfate reduction. The diversity and activity of dissimilatory sulfate reducers in these environments remain unexplored. In this study, using metagenomic approaches, in situ activity measurements with a radioactive tracer, and cultivation we have shown that members of the genus Desulfofundulus are responsible for the extremely high sulfate reduction rate (SRR) in burning lignite seams in the Altai Mountains. The maximum SRR reached 564 ± 21.9 nmol S cm-3 day-1 at 60°C and was of the same order of magnitude for both thermophilic (60°C) and mesophilic (23°C) incubations. The 16S rRNA profiles and the search for dsr gene sequences in the metagenome revealed members of the genus Desulfofundulus as the main sulfate reducers. The thermophilic Desulfofundulus sp. strain Al36 isolated in pure culture, did not grow at temperatures below 50°C, but produced spores that germinated into metabolically active cells at 20 and 15°C. Vegetative cells germinating from spores produced up to 0.738 ± 0.026 mM H2S at 20°C and up to 0.629 ± 0.007 mM H2S at 15°C when CO was used as the sole electron donor. The Al36 strain maintains significant production of H2S from sulfate over a wide temperature range from 15°C to 65°C, which is important in variable temperature biotopes such as lignite burning seams. Burning coal seams producing CO are ubiquitous throughout the world, and biogenic H2S may represent an overlooked significant flux to the atmosphere. The thermophilic spore outgrowth and their metabolic activity at temperatures below the growth minimum may be important for other spore-forming bacteria of environmental, industrial and clinical importance.

A sulfate reducing bioreactor controlled by an electrochemical system enables near-zero chemical treatment of metallurgical wastewater

Metallurgical wastewaters are characterized by a low pH (<4), high concentrations of sulfate (15 gSO42− L−1), and metal(loid)s. Current treatment requires the consumption of chemicals such as alkali and high levels of waste sludge generation. In this study, we have shown that combining water electrolysis and sulfate reducing bioreactors enables the in-situ generation of base and H2, eliminating the need for base and electron donor addition, resulting in the near-zero treatment of metallurgical wastewater. By extracting cations from the effluent of the system to the bioreactor, the bioreactor pH could be maintained by the in-situ production of alkali. The current for pH control varied between 112–753 mol electrons per m³ wastewater or 5–48 A m−2 electrode area. High concentrations of sulfate in the influent and addition of CO2 increased the current required to maintain a steady bioreactor pH. On the other hand, a high sulfate reduction rate and increased influent pH lowered the current required for pH control. Moreover, the current efficiency varied from 14% to 91% and increased with higher pH and cation (Na+, NH4+, K+, Mg2+, Ca2+) concentrations in the middle compartment of the electrochemical cell. The salinity was lowered from 70–120 mS cm−1 in the influent to 5–20 mS cm−1 in the system effluent. The energy consumption of the electrochemical pH control varied between 10 and 100 kWh m−3 and was affected by the conductivity of the wastewater. Industrial wastewater was treated successfully with an average energy consumption of 39 ± 7 kWh m−3, removing sulfate from 15 g SO42− L−1 to 0.5 ± 0.5 g SO42− L−1 at a reduction rate of 20 ± 1 gSO42− L−1 d−1..Metal(loid)s such as As, Cd, Cu, Pb, Te, Tl, Ni and Zn were removed to levels of 1–50 µg L−1.

Antibiotic-Resistant Desulfovibrio Produces H2S from Supplements for Animal Farming.

Sulphate-reducing bacteria, primarily Desulfovibrio, are responsible for the active generation of H2S in swine production waste. The model species for sulphate reduction studies, Desulfovibrio vulgaris strain L2, was previously isolated from swine manure characterized by high rates of dissimilatory sulphate reduction. The source of electron acceptors in low-sulphate swine waste for the high rate of H2S formation remains uncertain. Here, we demonstrate the ability of the L2 strain to use common animal farming supplements including L-lysine-sulphate, gypsum and gypsum plasterboards as electron acceptors for H2S production. Genome sequencing of strain L2 revealed the presence of two megaplasmids and predicted resistance to various antimicrobials and mercury, which was confirmed in physiological experiments. Most of antibiotic resistance genes (ARG) are carried by two class 1 integrons located on the chromosome and on the plasmid pDsulf-L2-2. These ARGs, predicted to confer resistance to beta-lactams, aminoglycosides, lincosamides, sulphonamides, chloramphenicol and tetracycline, were probably laterally acquired from various Gammaproteobacteria and Firmicutes. Resistance to mercury is likely enabled by two mer operons also located on the chromosome and on pDsulf-L2-2 and acquired via horizontal gene transfer. The second megaplasmid, pDsulf-L2-1, encoded nitrogenase, catalase and type III secretion system suggesting close contact of the strain with intestinal cells in the swine gut. The location of ARGs on mobile elements allows us to consider D. vulgaris strain L2 as a possible vector transferring antimicrobials resistance determinants between the gut microbiote and microbial communities in environmental biotopes.

The ikaite to calcite transformation: Implications for palaeoclimate studies

Marine sedimentary ikaite is the parent mineral to glendonite, stellate pseudomorphs found throughout the geological record which are most usually composed of calcite. Ikaite is known to be metastable at earth surface temperatures and pressures, readily breaking down to more stable carbonate polymorphs when exposed to warm (ambient) conditions. Yet the process of transformation of ikaite to calcite is not well understood, and there is an ongoing debate as to the palaeoclimatic significance of glendonites in the geological record. This study uses a combination of techniques to examine the breakdown of ikaite to calcite, outside of the ikaite growth medium, and to assess the palaeoclimatic and palaeoenvironmental significance of stable and clumped isotope compositions of ikaite-derived calcite. Powder X-ray diffraction shows that ikaite undergoes a quasi- solid-state transformation to calcite during heating of samples in air, yet when ikaite transforms under a high temperature differential, minor dissolution-recrystallisation may also occur with the ikaite structural waters. No significant isotopic equilibration to transformation temperature is observed in the resulting calcite. Therefore, in cases of transformation of ikaite in air, clumped and stable isotope thermometry can be used to reconstruct ikaite growth temperatures. In the case of ancient glendonites, where transformation of the ikaite occurred in contact with the interstitial waters of the host sediments over unknown timescales, it is uncertain whether the reconstructed clumped isotope temperatures reflect ikaite crystallisation or its transformation temperatures. Yet clumped and stable isotope thermometry may still be used conservatively to estimate an upper limit for bottom water temperatures.Furthermore, stable isotope along with element/Ca ratios shed light on the chemical environment of ikaite growth. Our data indicate that a range of (bio)geochemical processes may act to promote ikaite formation at different marine sedimentary sites, including bacterial sulphate reduction and anaerobic oxidation of methane. The colours of the ikaites, from light brown to dark brown, indicate a high organic matter content, favouring high rates of bacterial sulphate reduction as the main driver of ikaite precipitation. Highest Mg/Ca ratios are found in the most unstable ikaites, indicating that Mg acts to destabilise ikaite structure.

Sulfate-reducing bioreactors subjected to high sulfate loading rate or acidity: variations in microbial consortia

Sulfate-reducing bioreactors are used in e.g. the mining industry to remove sulfate and harmful metals from process waters. These bioreactors are expected to be run for extended periods of time and may experience variations in the influent quality, such as increasing sulfate loading rate and decrease in pH, while being expected to function optimally. In this study we followed the sulfate removal rate and variation in microbial communities over a period of up to 333 days in three different up-flow anaerobic sludge blanket (UASB) bioreactors being submitted to increasing sulfate loading rate or decreasing pH. Sodium lactate was used as the sole carbon source and electron donor. All three bioreactors contained highly diverse microbial communities containing archaea, fungi and bacteria. Sulfurospirillum and Desulfovibrio were the most prominent bacterial genera detected in the bioreactors receiving the highest sulfate loading rates, and the greatest relative abundance of methanogenic archaea and the fungal genus Cadophora coincided with the highest sulfate reduction rates. In contrast, Sulfuricurvum was dominant in the bioreactor receiving influent with alternating pH, but its relative abundance receded in response to low pH of the influent. All bioreactors showed excellent sulfate removal even under extreme conditions in addition to unique responses in the microbial communities under changing operational conditions. This shows that a high diversity in the microbial consortia in the bioreactors could make the sulfate removal process less sensitive to changing operational conditions, such as variations in influent sulfate loading rate and pH.

About the issue of cleaning exhaust gases from tpps and metallurgical enterprises from so2: regeneration of carbonate-sulfate melt with natural gas

General concept is proposed for a technology of purifying waste gases of TPPs and metallurgical enterprises from SO2 and CO2 . The fundamental possibility of carrying out the process of regeneration of carbonate-sulfate melt with natural gas is shown. Based on experimental work it has been established that the process of regeneration of a carbonate-sulfate melt with natural gas provides high rates of sulfate reduction and the achievement of maximum up to 99% sulfur recovery from the melt in the form of H2 S. It has been determined that the removal of sulfur from a carbonate-sulfate melt by bubbling with natural gas can be carried out in the operating temperature range of an absorption column for purifying exhaust gases as 500-550 ºС. It is shown that the process of regeneration of a carbonate-sulfate melt with natural gas is a relatively simple one-stage process that proceeds at a high rate. This allows the regeneration column to be integrated with an absorption column where sulfur is captured from the exhaust gases. The removal of sulfur in the form of H2 S provides considerable range of choice in terms of the final commercial product: either sulfuric acid (by dry combustion of H2 S) or elemental sulfur (by the Claus process), both have significant commercial value. The proposed method for the regeneration of a carbonate-sulfate melt simplifies the technology of purifying waste gases from sulfur dioxide with a carbonate melt of alkali metals. Moreover, it can be easily integrated into the general technological scheme of existing metallurgical enterprises without special material and energy costs.

Weakened resilience of benthic microbial communities in the face of climate change

Increased ocean temperature associated with climate change is especially intensified in coastal areas and its influence on microbial communities and biogeochemical cycling is poorly understood. In this study, we sampled a Baltic Sea bay that has undergone 50 years of warmer temperatures similar to RCP5-8.5 predictions due to cooling water release from a nuclear power plant. The system demonstrated reduced oxygen concentrations, decreased anaerobic electron acceptors, and higher rates of sulfate reduction. Chemical analyses, 16S rRNA gene amplicons, and RNA transcripts all supported sediment anaerobic reactions occurring closer to the sediment-water interface. This resulted in higher microbial diversities and raised sulfate reduction and methanogenesis transcripts, also supporting increased production of toxic sulfide and the greenhouse gas methane closer to the sediment surface, with possible release to oxygen deficient waters. RNA transcripts supported prolonged periods of cyanobacterial bloom that may result in increased climate change related coastal anoxia. Finally, while metatranscriptomics suggested increased energy production in the heated bay, a large number of stress transcripts indicated the communities had not adapted to the increased temperature and had weakened resilience. The results point to a potential feedback loop, whereby increased temperatures may amplify negative effects at the base of coastal biochemical cycling.

Biological Sulfate Reduction in Deep Subseafloor Sediment of Guaymas Basin

Sulfate reduction is the quantitatively most important process to degrade organic matter in anoxic marine sediment and has been studied intensively in a variety of settings. Guaymas Basin, a young marginal ocean basin, offers the unique opportunity to study sulfate reduction in an environment characterized by organic-rich sediment, high sedimentation rates, and high geothermal gradients (100–958°C km−1). We measured sulfate reduction rates (SRR) in samples taken during the International Ocean Discovery Program (IODP) Expedition 385 using incubation experiments with radiolabeled 35SO42− carried out at in situ pressure and temperature. The highest SRR (387 nmol cm−3 d−1) was recorded in near-surface sediments from Site U1548C, which had the steepest geothermal gradient (958°C km−1). At this site, SRR were generally over an order of magnitude higher than at similar depths at other sites (e.g., 387–157 nmol cm−3 d−1 at 1.9 mbsf from Site U1548C vs. 46–1.0 nmol cm−3 d−1 at 2.1 mbsf from Site U1552B). Site U1546D is characterized by a sill intrusion, but it had already reached thermal equilibrium and SRR were in the same range as nearby Site U1545C, which is minimally affected by sills. The wide temperature range observed at each drill site suggests major shifts in microbial community composition with very different temperature optima but awaits confirmation by molecular biological analyses. At the transition between the mesophilic and thermophilic range around 40°C–60°C, sulfate-reducing activity appears to be decreased, particularly in more oligotrophic settings, but shows a slight recovery at higher temperatures.

Dynamic anaerobic membrane bioreactor coupled with sulfate reduction (SrDMBR) for saline wastewater treatment

This study investigated organic removal performance, characteristics of the membrane dynamics, membrane fouling and the effects of biological sulfate reduction during high-salinity (1.0%) and high-sulfate (150 mgSO42--S/L) wastewater treatment using a laboratory-scale upflow anaerobic sludge bed reactor integrated with cross-flow dynamic membrane modules. Throughout the operational period, dynamic membrane was formed rapidly (within 5–10 min) following each backwashing cycle (21–16 days), and the permeate turbidity of <5–7 NTU was achieved with relatively high specific organic conversion (70–100 gTOC/kgVSS·d) and specific sulfate reduction (50–70 gSO42--S/kgVSS·d) rates. The sulfide from sulfate reduction can be reused for downstream autotrophic denitrification. 16S rRNA gene amplicon sequencing revealed that the microbial communities enriched in the sludge were different than those accumulated on the dynamic layer. Overall, this study demonstrates that the anaerobic dynamic membrane bioreactor coupled with sulfate reduction (SrDMBR) shows promising applicability in saline wastewater treatment.

Continuous removal of sulfate and metals from acidic mining-impacted waters at low temperature using a sulfate-reducing bacterial consortium

The aim of this study was to develop a biological method for the simultaneous removal of sulfate and metals from acidic low-temperature mining effluents. A mixed consortium of cold-tolerant sulfate-reducing bacteria (SRB) and other microorganisms was immobilized on glass beads and exploited in an up-flow biofilm reactor for the continuous treatment of actual and synthetic mining-impacted waters (MIWs) with initial sulfate concentrations between 1580 and 5350 mg L-1. The proton acidity of the mine waters was neutralized by microbial sulfidogenesis. Metals present in the MIWs were precipitated either off-line or in-line, inside the reactor vessel. High sulfate reduction rates (SRRs), from 1000 to 4500 mg L-1 d-1 at a temperature of 11.7 ± 0.2 °C, were achieved (sulfate removal 43–87%). The bacterial consortium was found to be robust and resistant to changes in growth conditions during the bioreactor experiment. The relative abundance of SRB and the SRR increased at higher sulfate concentrations. Sulfidogenic bioreactors have the potential for treatment of acid mine drainage even at low temperature. It was demonstrated that neutral reactor conditions and high SRRs were maintained when acidic influent was fed into the reactor.

Treatment of neutral gold mine drainage by sequential in situ hydrotalcite precipitation, and microbial sulfate and cyanide removal

This study proposed and validated a method integrating in situ hydrotalcite precipitation (Virtual Curtain™ (VC) technology) with bioprocess for treating a cyanide (CN)-augmented (ca. 5 mg-CN L−1) sulfate-laden neutral mine drainage, from a waste rock dump (WD2) of an Australian gold mine. Efficacies of various carbon (C) sources (ethanol, lactate, and two natural substrates; Eucalyptus wood sawdust (EW) and Typha biomass (TB)) for promoting microbial reduction in both: CN-augmented WD2 water and VC-treated CN-augmented WD2 water were assessed in a 60-days microcosms study at 30 °C. The microcosms were monitored over time for pH, redox potential, dissolved hydrogen sulfide, chloride, nitrite, nitrate, sulfate, phosphate, biogas production, dissolved organic carbon, total dissolved nitrogen, and dissolved CN. The VC treatment removed a range of metals (Mg, Ni and Zn) and metalloid Se from the CN-augmented WD2 water to below detection. Other elements substantially reduced in concentration included Ba, F, Si and U. However, the VC treatment did not remove substantial nitrate, sulfate or CN. Microcosm trials revealed that the indigenous microbial community in WD2 could effectively denitrify and reduce sulfate, with TB was the most efficient C source for promoting sulfate and CN removal; whereas, EW facilitated only marginally higher sulfate reduction compared with controls. The highest sulfate reduction rate (76 g-SO42− m−3 d−1) was achieved with VC-treated water amended with TB, indicating that VC pre-treatment was beneficial. Further, all treatments amended with external C, facilitated 100% removal of dissolved CN after 60 days, whereas only partial (65%) CN removal was recorded in the control. Overall, the proposed integrated method appears a viable option for treating neutral gold mine drainage.

Polychaete Invasion May Lead to Biogeochemical Change in Host Marine Environment

Marine invasive species may modify their host environment by altering ecosystem biogeochemistry. We hypothesized that the invasive polychaete Marenzelleria viridis in Baltic Sea areas increases sulfate reduction (SR) in sediment micro-zones surrounding its burrow. Consequently, higher free porewater sulfide (H2S) is expected in sediments dominated by M. viridis than in corresponding sediments inhabited by the native polychaete Hediste diversicolor. In a thin-aquaria experiment, we found high SR rates (220 to 539 nmol cm−3 d−1) around the burrow walls of M. viridis as well as in surface and subsurface sediments with overall rates 2-fold higher than in defaunated control sediment. Similarly, an in situ survey revealed subsurface porewater H2S peaks moving upward towards the sediment surface in M. viridis inhabited areas. Accordingly, 50–85% higher porewater H2S was found almost year-round in these areas compared with H. diversicolor inhabited areas, suggesting that the invasion of M. viridis probably led to a substantial change in sediment biogeochemistry. In conclusion, M. viridis stimulates SR in sediment micro-zones and increases H2S in coastal sediments. Such change to more reducing conditions after the invasion may have critical environmental implications on, e.g., the distribution of H2S intolerant flora and fauna species.

Effect of hydraulic residence time on biological sulphate reduction and elemental sulphur recovery in a single-stage hybrid linear flow channel reactor

Biological sulphate reduction and partial sulphide oxidation, occurring simultaneously within the hybrid linear flow channel reactor (LFCR) were evaluated, under controlled conditions at laboratory scale, as a function of hydraulic residence time (HRT) using a synthetic media containing 1 g/L sulphate. The hybrid LFCR comprises a rectangular channel containing carbon microfibers as a support matrix for attachment of sulphate-reducing bacteria and an exposed air-liquid interface to facilitate the formation of a floating sulphur biofilm. Exposure to decreasing HRT, from 3 days to 12 h, resulted in an increase in the volumetric sulphate reduction rate (0.14 to 0.63 mmol/L.h), achieving levels typically associated with active reactors. Sulphate conversion was highest (97 %) at a 3 day HRT, decreasing to 73 % at 12 h. The highest sulphide removal efficiency (82 %) and accompanying sulphur recovery through harvesting of the floating sulphur biofilm (FSB) was observed at a 2 day HRT. The sulphur fraction not recovered through the biofilm was predominantly released within the effluent as colloidal elemental sulphur and fragments of the sulphur-rich biofilm, with minimal re-oxidation to sulphate occurring in the reactor. The hybrid LFCR technology was able to achieve high rates of sulphate reduction and effective sulphide removal within a single, semi-passive reactor unit.

Trace element perspective into the ca. 2.1-billion-year-old shallow-marine microbial mats from the Francevillian Group, Gabon

The sedimentary fabrics of Precambrian mat-related structures (MRS) represent some of the oldest convincing evidence for early life on Earth. The ca. 2.1 billion-year (Ga) old MRS in the FB2 Member of the Francevillian basin in Gabon has received considerable attention not only because they contain remnants of microbial mats that colonized large areas in oxygenated, shallow-marine settings, but they also contain evidence for ancient multicellular organisms that thrived on these microbial mats using them as a food source. Despite these insights, what remains lacking is a full characterization of the geochemical composition of the MRS to test whether the bulk composition of fossilized MRS is distinct from the host sediments (sandstones and shales). Here, we show that the trace element (TE) content of microbial textures belonging to pyritized MRS, poorly pyritized MRS, and “elephant-skin” textures (EST) is highly variable and differs from that of the host sediments. The poorly pyritized MRS contain a unique matrix with embedded Ti- and Zr-rich minerals and syngenetically enriched in TE. The EST, some of which are developed along the same stratigraphic horizon as the poorly pyritized MRS, display a distinct distribution of TE-bearing heavy minerals, suggesting a local difference in physical conditions during sedimentation. Similarly, high chalcophile-element (CE) content in pyritized MRS relative to the host sediments of the FB2 Member further points to local bacterially influenced enrichments with high rates of microbial sulfate reduction during early diagenesis. The geochemical relationship between the MRS and the Francevillian sediments (e.g., FB, FC, and FD formations) indicates that specific biological pathways for CE enrichments (i.e., microbially controlled accumulation) are not apparent. Our findings highlight bulk-rock TE distinction between the 2.1-billion-year-old MRS and their host sediments, but also indicate that environmental conditions, such as hydrodynamic regime and water-column redox chemistry, may simply overwhelm any potential biological signal. Our data suggest that the microbial impact may have only passively influenced TE enrichment in the studied sediments, implying that TE concentrations in MRS are a poor biosignature. Importantly, this work indicates that bulk TE geochemistry does not unveil specific microbiological processes in the rock record, which is consistent with the observed patterns in modern analogues.

Iron cycling in Arctic methane seeps

Anoxic marine sediments contribute a significant amount of dissolved iron (Fe2+) to the ocean which is crucial for the global carbon cycle. Here, we investigate iron cycling in four Arctic cold seeps where sediments are anoxic and sulfidic due to the high rates of methane-fueled sulfate reduction. We estimated Fe2+ diffusive fluxes towards the oxic sediment layer to be in the range of 0.8 to 138.7 μmole/m2/day and Fe2+ fluxes across the sediment-water interface to be in the range of 0.3 to 102.2 μmole/m2/day. Such variable fluxes cannot be explained by Fe2+ production from organic matter–coupled dissimilatory reduction alone. We propose that the reduction of dissolved and complexed Fe3+ as well as the rapid formation of iron sulfide minerals are the most important reactions regulating the fluxes of Fe2+ in these cold seeps. By comparing seafloor visual observations with subsurface pore fluid composition, we demonstrate how the joint cycling of iron and sulfur determines the distribution of chemosynthesis-based biota.

Microbial and Reactive Transport Modeling Evidence for Hyporheic Flux‐Driven Cryptic Sulfur Cycling and Anaerobic Methane Oxidation in a Sulfate‐Impacted Wetland‐Stream System

AbstractThis study reexamines the common expectations that in freshwater systems, sulfur plays a minor role in carbon cycling, and aerobic processes dominate methane oxidation. In anoxic sediments of a sulfate‐impacted wetland‐stream system in Minnesota (USA), a reactive transport model calibrated to geochemical observations predicted sulfate reduction to be the major terminal electron accepting process, and it showed that anaerobic oxidation of methane predominantly coupled with sulfate reduction attenuated methane concentrations near the sediment‐water interface. Consistent with model results, 16S rRNA microbiome analysis revealed a high relative abundance of taxa capable of dissimilatory sulfate reduction. It further supported the conclusion that high simulated sulfate reduction rates could be maintained by a “cryptic” sulfur cycle coupled to iron and methane. Low relative abundance of known iron reducing bacteria raised the possibility of abiotic ferric iron (Fe) reduction driving sulfide reoxidation to intermediate‐valence sulfur forms; widespread potential for microbially mediated disproportionation, oxidation, and reduction of sulfur intermediates provided mechanisms for completing redox cycles; and archaea comprising up to 25% of the microbial community could include consortia capable of anaerobic oxidation of methane. These biogeochemical processes were found to be controlled by hyporheic fluxes. Lower‐magnitude fluxes in wetland compared to channel sediments created sharper geochemical gradients that generated greater heterogeneity in microbial distributions and reaction rates. Changes in upward flux caused fluctuations in sulfate concentrations that led to alternating simulations of methane production and transport. Our work supports the importance of hyporheic flux‐driven iron‐sulfur‐methane cycling in sulfate‐impacted wetlands and prompts further investigations under freshwater conditions.

The pyrite multiple sulfur isotope record of the 1.98 Ga Zaonega Formation: Evidence for biogeochemical sulfur cycling in a semi-restricted basin

The pyrite sulfur isotope record of the 1.98 Ga Zaonega Formation in the Onega Basin, NW Russia, has played a central role in understanding ocean-atmosphere composition and inferring worldwide fluctuations of the seawater sulfate reservoir during the pivotal times of the Paleoproterozoic Era. That, in turn, has led to a concept that Earth's atmospheric oxygen levels underwent global-scale changes. Here we present a steady-state isotope mass-balance model to gain insight into the mechanisms governing the sulfur cycle and sulfate reservoir during deposition of the organic-rich Zaonega Formation. We demonstrate that coupling between high microbial sulfate reduction rates and effective sulfate removal by pyrite precipitation can lead to Rayleigh distillation of the basinal sulfate reservoir and development of high amplitude positive δ34S excursions. This modelling approach illustrates that secular changes in sedimentary pyrite isotope trends can be explained by processes that reflect local (basin-scale) fluctuations in sulfur cycling rather than global mechanisms.

A dolomitization event at the oceanic chemocline during the Permian-Triassic transition: REPLY

The Permian-Triassic boundary (PTB) crisis caused major shortterm perturbations in ocean chemistry, as recorded by the precipitation of anachronistic carbonates. Here, we document for the first time a global dolomitization event during the Permian-Triassic transition based on Mg/(Mg + Ca) data from 22 sections with a global distribution representing shallow- to deep-marine environments. Ten of these sections show high Mg/(Mg + Ca) ratios bracketing the PTB, recording a short-term spike in dolomite formation. The dolomite consists mainly of micron-scale anhedral to subhedral crystals that are associated with abundant fossilized bacterial bodies and extracellular polymeric substances, suggesting that dolomite precipitation was induced by microbial metabolic activity. Sections showing a dolomite spike at the PTB are widely distributed geographically, but mostly encountered in mid-shelf to upper-slope settings. Because the dolomitization event coincided with a rapid expansion of oceanic anoxia and high rates of sulfate reduction, we hypothesize that it was triggered by enhanced microbial sulfate reduction within the oceanic chemocline.

Abundance and Biogeochemical Impact of Cable Bacteria in Baltic Sea Sediments.

Oxygen depletion in coastal waters may lead to release of toxic sulfide from sediments. Cable bacteria can limit sulfide release by promoting iron oxide formation in sediments. Currently, it is unknown how widespread this phenomenon is. Here, we assess the abundance, activity, and biogeochemical impact of cable bacteria at 12 Baltic Sea sites. Cable bacteria were mostly absent in sediments overlain by anoxic and sulfidic bottom waters, emphasizing their dependence on oxygen or nitrate as electron acceptors. At sites that were temporarily reoxygenated, cable bacterial densities were low. At seasonally hypoxic sites, cable bacterial densities correlated linearly with the supply of sulfide. The highest densities were observed at Gulf of Finland sites with high rates of sulfate reduction. Microelectrode profiles of sulfide, oxygen, and pH indicated low or no in situ cable bacteria activity at all sites. Reactivation occurred within 5 days upon incubation of an intact sediment core from the Gulf of Finland with aerated overlying water. We found no relationship between cable bacterial densities and macrofaunal abundances, salinity, or sediment organic carbon. Our geochemical data suggest that cable bacteria promote conversion of iron monosulfides to iron oxides in the Gulf of Finland in spring, possibly explaining why bottom waters in this highly eutrophic region rarely contain sulfide in summer.