Microbial Sulfate Reduction Rates Research Articles

Microbial anabolic and catabolic utilization of hydrocarbons in deep subseafloor sediments of Guaymas Basin.

Guaymas Basin, located off the Gulf of California, is a hydrothermally active marginal basin. Due to steep geothermal gradients and localized heating by sill intrusions, microbial substrates like short-chain fatty acids and hydrocarbons are abiotically produced from sedimentary organic matter at comparatively shallow depths. We analyzed the effect of hydrocarbons on uptake of hydrocarbons by microorganisms via nanoscale secondary ion mass spectrometry (NanoSIMS) and microbial sulfate reduction rates (SRR), using samples from two drill sites sampled by IODP Exp. 385 (U1545C and U1546D). These sites are in close proximity of each other (ca. 1km) and have very similar sedimentology. Site U1546D experienced the intrusion of a sill that has since then thermally equilibrated with the surrounding sediment. Both sites currently have an identical geothermal gradient, despite their different thermal history. The localized heating by the sill led to thermal cracking of sedimentary organic matter and formation of potentially bioavailable organic substrates. There were low levels of hydrocarbon and nitrogen uptake in some samples from both sites, mostly in surficial samples. Hydrocarbon and methane additions stimulated SRR in near-seafloor samples from Site U1545C, while samples from Site U1546D reacted positively only on methane. Our data indicate the potential of microorganisms to metabolize hydrocarbons even in the deep subsurface of Guaymas Basin.

Estimating the effect of elemental sulfur disproportionation on the sulfur-isotope signatures in sediments

Experimental studies with pure and enrichment cultures have shown that microbial disproportionation of sulfur intermediates can increase the sulfur isotopic difference between dissolved sulfate and sulfide produced by microbial sulfate reduction. However, few studies have quantified the isotope effect of disproportionation in natural settings. Here we describe a conceptual model to quantify the contribution of elemental sulfur disproportionation to the isotopic difference between dissolved sulfate and sulfide. Our results show that disproportionation increases the isotopic difference between sulfate and sulfide, but the effect is less pronounced than suggested by culture experiments. The resulting isotopic difference depends on the ratio of the rate of microbial sulfate reduction to that of disproportionation. It can be shown that in natural sediments, this relationship can be expressed as a function of the isotope enrichment during disproportionation multiplied by the fraction of sulfide that escapes burial in the form of metal sulfides. This implies that in many natural sediments, the sulfur isotope effect is limited to a few permil (mUr) or less.

Sediment mineralogy influences the rate of microbial sulfate reduction in marine sediments

Sedimentary microbial communities play a critical role in the global carbon cycle, oxidizing deposited organic carbon and thus influencing the type of carbon buried from Earth's surface. The rate of microbial metabolism within sedimentary microbial communities is often linked to the lability and amount of organic carbon deposited. Here we show that, in pure culture, for sulfate-reducing bacteria (Desulfovibrio bizertensis) the rate of microbial sulfate reduction is a function of the proportion of clay minerals present in the incubation vials. We argue that the presence of clay minerals stimulates the growth of the sulfate-reducing bacteria and the rate at which sulfate is consumed; we conclude that this is not linked to nutrients and carbon on the clay minerals but rather is a function of the high specific surface area of clay minerals. We further use a global compilation of sedimentary pore fluid data to demonstrate that these observations can be seen in marine sediments, that is pore fluid sulfate concentration gradients in marine sediments correlate with the percentage of clay minerals in the sediment. Our findings suggest that sediment mineralogy influences the rate of microbial activity in marine sediments, which has heretofore not been considered.

Sedimentary pyrite sulfur isotopes track the local dynamics of the Peruvian oxygen minimum zone

Sulfur cycling is ubiquitous in sedimentary environments, where it mediates organic carbon remineralization, impacting both local and global redox budgets, and leaving an imprint in pyrite sulfur isotope ratios (δ34Spyr). It is unclear to what extent stratigraphic δ34Spyr variations reflect local aspects of the depositional environment or microbial activity versus global sulfur-cycle variations. Here, we couple carbon-nitrogen-sulfur concentrations and stable isotopes to identify clear influences on δ34Spyr of local environmental changes along the Peru margin. Stratigraphically coherent glacial-interglacial δ34Spyr fluctuations (>30‰) were mediated by Oxygen Minimum Zone intensification/expansion and local enhancement of organic matter deposition. The higher resulting microbial sulfate reduction rates led to more effective drawdown and 34S-enrichment of residual porewater sulfate and sulfide produced from it, some of which is preserved in pyrite. We identify organic carbon loading as a major influence on δ34Spyr, adding to the growing body of evidence highlighting the local controls on these records.

Active microbial sulfate reduction in fluids of serpentinizing peridotites of the continental subsurface

Serpentinization of peridotites in Earth’s mantle is associated with the generation of hydrogen and low molecular weight organics that could support subsurface life. Studies of microbial metabolisms in peridotite-hosted environments have focused primarily on methanogenesis, yet DNA sequences, isotopic composition of sulfides and thermodynamic calculations suggest there is potential for microbial sulfate reduction too. Here, we use a sulfate radiotracer-based method to quantify microbial sulfate reduction rates in serpentinization fluids recovered from boreholes in the Samail Ophiolite, Oman and the California Coast Range Ophiolite, USA. We find that low levels of sulfate reduction occur at pH up to 12.3. These low levels could not be stimulated by addition of hydrogen, methane or small organic acids, which indicates that this metabolism is limited by factors other than substrate availability. Cellular activity drops at pH > 10.5 which suggests that high fluid pH exerts a strong control on sulfate-reducing organisms in peridotites.

Modelling the Effects of Non-Steady State Transport Dynamics on the Sulfur and Oxygen Isotope Composition of Sulfate in Sedimentary Pore Fluids

We present the results of an isotope-enabled reactive transport model of a sediment column undergoing active microbial sulfate reduction to explore the response of the sulfur and oxygen isotopic composition of sulfate under perturbations to steady state. In particular, we test how perturbations to steady state influence the cross plot of δ34S and δ18O for sulfate. The slope of the apparent linear phase (SALP) in the cross plot of δ34S and δ18O for sulfate has been used to infer the mechanism, or metabolic rate, of microbial metabolism, making it important that we understand how transient changes might influence this slope. Tested perturbations include changes in boundary conditions and changes in the rate of microbial sulfate reduction in the sediment. Our results suggest that perturbations to steady state influence the pore fluid concentration of sulfate and the δ34S and δ18O of sulfate but have a minimal effect on SALP. Furthermore, we demonstrate that a constant advective flux in the sediment column has no measurable effect on SALP. We conclude that changes in the SALP after a perturbation are not analytically resolvable after the first 5% of the total equilibration time. This suggests that in sedimentary environments the SALP can be interpreted in terms of microbial metabolism and not in terms of environmental parameters.

Marine carbon and sulfur cycling across the Ediacaran-Cambrian boundary in Tarim Block and its implications for paleoenvironmental changes

The Ediacaran-Cambrian transition was a critical period of Earth history because of the coincidence among climate change, bioevolution, and tectonic activity. The nature of carbon and sulfur-cycling processes spanning the Ediacaran-Cambrian boundary remains debatable. This study considers high-resolution stable isotope chemostratigraphy of the Sugetbrak and Yutixi sections of the Keping area of the Tarim Basin, northwestern China. The sections display a pronounced negative δ13Ccarb shift (the Basal Cambrian Carbon Isotope Excursion) that spans the Ediacaran-Cambrian boundary. Deposits overlying the negative excursion are characterized by heavier δ13Ccarb values ranging from −7.8‰ to +4.1‰. The biostratigraphically calibrated δ13Ccarb profiles likely reflect widespread perturbation of the global oceanic carbon cycle and associated mass extinction and subsequent biological evolution. The δ34Spy profiles of the studied sections display a wide distribution of values, ranging from −16.4‰ to 23.8‰. The variable δ34Spy signatures of these sections are partially controlled by microbial sulfate reduction rates, which are sensitive to local sulfate concentration, availability of organic matter and the marine redox state. The strong coupling between enhanced organic carbon and pyrite burial, the appearance of Cambrian-type animals and a shift to a more oxidizing marine environment might suggest a temporal causality of higher oxygen levels of the atmosphere-ocean realm with bio-events during the Ediacaran–Cambrian transition. The development of ecosystems across the Ediacaran–Cambrian transition may have significantly impacted the oceanic carbon and sulfur biogeochemical processes in Earth's history and, in turn, affecting themselves.

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.

Spatiotemporal evolution and causes of marine euxinia in the early Cambrian Nanhua Basin (South China)

Marine redox conditions and their dynamic variations in the early Cambrian are thought to have strongly influenced the evolution of early animals. However, the patterns and mechanisms of contemporaneous marine redox variation remain poorly understood. The Nanhua Basin (South China) was a failed rift basin located between the Yangtze Block (NW margin) and Cathaysia Block (SE margin) in the early Cambrian. In this study, we conducted a comprehensive study of marine redox conditions, sulfur cycling, and chemical weathering intensity of source areas for the lower Cambrian shales of the Qingxi Formation in the basinal Shimensuidao section, which was geographically close to the Cathaysia Block. We integrated these results with previously published data from the nearby Silikou section as well as the coeval inner-shelf Xiaotan, upper-slope Daotuo, lower-slope Longbizui, and basinal Zhalagou sections, where were closer to the Yangtze Block. At Shimensuidao, iron species and redox-sensitive trace element data suggest dominantly euxinic conditions for the organic-rich black shale interval (lower member; LM) and variable redox conditions (oxic-ferruginous-euxinic) for the overlying organic-lean shales (upper member; UM) of the Qingxi Formation. Integrated redox results show a similar lessening of euxinic conditions from LM to UM across the entire basin and that euxinia developed along both the Yangtze and Cathaysia basin margins, but it was mainly in upper-slope areas (e.g., Daotuo) on the Yangtze margin and reached basinal areas (e.g., Silikou and Shimensuidao) on the Cathaysia margin. A decline of δ34Spy from LM to UM was observed at Shimensuidao and other sections, which can be explained by decreasing microbial sulfate reduction rates due to decreasing organic availability and increasing riverine sulfate flux at study sections. Lower δ34Spy values in shallow-marine relative to deep-marine areas suggest increased terrestrial sulfate availability to the shallower sites. Chemical index of alteration (CIA) values at Shimensuidao are uniformly high for both the LM (CIAcorr1: 82.5 ± 0.4, CIAcorr2: 88.6 ± 0.5) and UM (CIAcorr1: 80.2 ± 2.3, CIAcorr2: 86.2 ± 2.5) compared with the low-to moderate values at Daotuo (CIAcorr2: 61.9 ± 3.9 for LM, 71.3 ± 4.8 for UM). This pattern is consistent with intense chemical weathering of source areas on the Cathaysia Block and weaker chemical weathering of source areas on the Yangtze Block. Based on these observations, we propose that strong chemical weathering of the Cathaysia Block led to regionally high terrigenous sulfate fluxes, resulting in expansion of mid-depth euxinia into deep basinal areas on the Cathaysia margin of the Nanhua Basin. In contrast, weak chemical weathering of the Yangtze Block yielded lower terrigenous sulfate fluxes, limiting euxinia to upper slope areas on the Yangtze margin of the basin. Weaker euxinia during UM deposition may have been due to its decreasing organic availability and/or small seawater sulfate reservoir caused by persistent euxinic consumption during LM deposition. Our results highlight the complex controls and the key role of continental weathering and resulting terrigenous sulfate fluxes in marine euxinic variations in early Cambrian marginal seas, providing new insights into the co-evolution of continents, oceans, and early animals.

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.

Modeling of biogeochemical processes in a barrier island freshwater lens (Spiekeroog, Germany)

Freshwater lenses present valuable water resources on barrier islands. Yet, the biogeochemical processes that control the groundwater quality of these freshwater lenses and how they are affected by the prevailing groundwater dynamics is largely unexplored. In this study we investigated the biogeochemistry of a barrier island freshwater lens with a focus on understanding and quantifying organic matter mineralization, sulfur cycling, and chemical fluxes to the land-ocean interface. We analyzed a comprehensive set of hydrogeochemical field data from Spiekeroog Island (Germany), including stable sulfur isotope signatures of dissolved sulfur species, with a reactive transport modeling approach. Tritium-Helium groundwater ages were used to constrain the hydrogeochemistry as a function of residence time. Our results revealed that freshwater lenses can act as archives for anthropogenic pollution, conserving the high sulfur loads associated with historic atmospheric deposition. We observed two distinct (hydro)biogeochemical patterns, which we attribute to a heterogeneous distribution of reactive organic matter. Those patterns were well replicated by two separate reactive transport models that considered the variations in organic matter reactivity. Simulation and field results demonstrated that net sulfur cycling is dominated by microbial sulfate reduction and subsequent iron sulfide precipitation. In the absence of dissolved oxidants, we attribute the observed high stable sulfur isotope fractionation between dissolved sulfate and sulfide of up to 67‰ to low (<20 pmol mL−1 d−1) microbial sulfate reduction rates. We show that older groundwater becomes progressively enriched in ammonium and phosphate due to the mineralization of organic matter, and we speculate that lens-derived nutrient fluxes may be important for the benthic zone at local groundwater discharge sites, at least seasonally in spring and summer.

Decoupling between sulfate reduction and the anaerobic oxidation of methane in the shallow methane seep of the Black sea

Methane seepages are widespread in the Black Sea. However, microbiological research has been carried out only at the continental shelf seeps. The present work dealt with coastal gas seepages of the Kalamit Bay (Black Sea). High-throughput 16S rRNA gene sequencing and radiotracer analysis (14С and 35S) were used to determine the composition of the microbial community and the rates of microbial sulfate reduction and methane oxidation. The phylum Proteobacteria, represented mainly by sulfate reducers of the class Deltaproteobacteria, was the predominant in sequence dataset. Bacteroidetes and Planctomycetes were other numerous phyla. Among archaea, the phylum Woesearchaeota and Marine Benthic Group B were predominant in the upper horizons. Relative abundance of Euryarchaeota of the families Methanomicrobiaceae and Methanosarcinaceae (including ANME-3 archaea) increased in deeper sediment layers. Sulfate reduction rate (up to 2.9 mmol/L×day) was considerably higher than the rate of anaerobic methane oxidation (up to 43.4 μmol/L×day), which indicated insignificant contribution of anaerobic methane oxidation to the total sulfide production.

Iron dynamics in a subtropical estuarine tidal marsh: effect of season and vegetation

MEPS Marine Ecology Progress Series Contact the journal Facebook Twitter RSS Mailing List Subscribe to our mailing list via Mailchimp HomeLatest VolumeAbout the JournalEditorsTheme Sections MEPS 577:1-15 (2017) - DOI: https://doi.org/10.3354/meps12268 FEATURE ARTICLE Iron dynamics in a subtropical estuarine tidal marsh: effect of season and vegetation Min Luo1,2,3, Jiafang Huang3, Chuan Tong1,3,*, Yuxiu Liu3, Xun Duan2, Yin Hu2 1Postdoctoral Research Station for Ecology, Fujian Normal University, Fuzhou 350007, PR China 2School of Environment and Resources, Fuzhou University, Fuzhou 350116, PR China 3Key Laboratory of Humid Subtropical Eco-Geographical Processes, Ministry of Education, Fujian Normal University, Fuzhou 350007, PR China *Corresponding author: tongch@fjnu.edu.cn ABSTRACT: To better understand how seasonal change and the presence of plants affect biogeochemical iron (Fe) cycling in tidal marsh sediments, we examined the seasonal dynamics of microbial Fe reduction (FeR) and related Fe speciation from 2012 to 2014 using in situ vegetated and unvegetated mesocosms created with macrobenthos-proof enclosures. The pools of Fe(III) oxides, Fe sulfides, porewater Fe2+, and rates of microbial sulfate reduction (SR) peaked in summer (hot and wet), whereas rates of FeR and non-sulfidic Fe(II) levels peaked in winter (mild and dry). Sedge presence greatly increased the FeR rate, organic matter pools, and Fe(III) oxide levels, but decreased carbon:nitrogen ratios and sulfide abundances. FeR rates were mainly affected by the SR level, and temperature and plant primary productivity had comparable effects on SR rates. The dominant organic carbon mineralization pathway changed from SR in summer to FeR in winter in both vegetated and unvegetated mesocosms. FeR was more important in the vegetated mesocosms than in the unvegetated mesocosms, and seasonal change contributed more to the total variability of each anaerobic pathway than the presence of sedge. Our study reveals that temperature and plants both mediate variations in the organic carbon mineralization pathways of a subtropical estuarine tidal marsh. KEY WORDS: Seasonality · Sedge · Microbial iron reduction · Microbial sulfate reduction · Organic carbon mineralization · Tidal marsh · Min River estuary Full text in pdf format Information about this Feature Article NextCite this article as: Luo M, Huang J, Tong C, Liu Y, Duan X, Hu Y (2017) Iron dynamics in a subtropical estuarine tidal marsh: effect of season and vegetation. Mar Ecol Prog Ser 577:1-15. https://doi.org/10.3354/meps12268 Export citation RSS - Facebook - Tweet - linkedIn Cited by Published in MEPS Vol. 577. Online publication date: August 18, 2017 Print ISSN: 0171-8630; Online ISSN: 1616-1599 Copyright © 2017 Inter-Research.

Rates and Cycles of Microbial Sulfate Reduction in the Hyper-Saline Dead Sea over the Last 200 kyrs from Sedimentary δ34S and δ18O(SO4)

We report the 34S and 18O(SO4) values measured in gypsum, pyrite, and elemental sulfur through a 456-m thick sediment core from the center of the Dead Sea, representing the last ~200 kyrs, as well as from the exposed glacial outcrops of the Masada M1 section located on the margins of the modern Dead Sea. The results are used to explore and quantify the evolution of sulfur microbial metabolism in the Dead Sea and to reconstruct the lake’s water column configuration during the late Quaternary. Layers and laminae of primary gypsum, the main sulfur-bearing mineral in the sedimentary column, display the highest 34S and 18O(SO4) in the range of 13-28‰ and 13-30‰, respectively. Within this group, gypsum layers deposited during interglacials have lower 34S and 18O(SO4) relative to those associated with glacial or deglacial stages. The reduced sulfur phases, including chromium reducible sulfur, and secondary gypsum crystals are characterized by extremely low 34S in the range of -27 to +7‰. The 18O(SO4) of the secondary gypsum in the M1 outcrop ranges from 8 to 14‰. The relationship between 34S and 18O(SO4) of primary gypsum suggests that the rate of microbial sulfate reduction was lower during glacial relative to interglacial times. This suggests that the freshening of the lake during glacial wet intervals, and the subsequent rise in sulfate concentrations, slowed the rate of microbial metabolism. Alternatively, this could imply that sulfate-driven anaerobic methane oxidation, the dominant sulfur microbial metabolism today, is a feature of the hypersalinity in the modern Dead Sea. Sedimentary sulfides are quantitatively oxidized during epigenetic exposure, retaining the lower 34S signature; the 18O(SO4) of this secondary gypsum is controlled by oxygen atoms derived equally from atmospheric oxygen and from water, which is likely a unique feature in this hyperarid environment.

Regional depositional changes and their controls on carbon and sulfur cycling across the Ordovician-Silurian boundary, northwestern Guizhou, South China

The controls of regional depositional environment on stable isotope records spanning the Ordovician-Silurian boundary on the Yangtze Platform have seldom been investigated. The objectives of this study include reconstruction of regional depositional settings and assessment of how sedimentary processes may have influenced carbon- and sulfur-isotopic fractionation. Seven shale facies have been recognized in the Wufeng-Longmaxi interval from two locations. Completely bioturbated claystone of the basal Wufeng Formation accumulated on a shallow oxygenated muddy shelf. Overlying faintly banded black siliceous shale suggests deposition under deep anoxic conditions interrupted by episodes of dysoxia. Muddy fossiliferous facies of the Guanyinqiao Formation reflects a glacial sea-level lowstand setting, and the observed proximal to distal heterogeneity of facies matrix supports shallowing in the proximal area. Overlying faintly banded black shale of the Longmaxi Formation tells of a post-glacial transgression. The carbonaceous deposits are overlain by banded gray and dark gray muddy siltstones and suggest a shoaling upward trend. The shallow-water facies display relatively heavier δ13Corg values, whereas deep-water facies are characterized by lower δ13Corg values. Discrepancies between Hirnantian positive δ13Corg excursions in proximal and distal areas probably reflect spatial gradient in seawater δ13CDIC induced by glacioeustasy. Deposits accumulated under oxic and physically dynamic conditions display strong positive δ34Ssulfide excursions, perhaps a consequence of diagenetic sulfate reduction occurred at some depth below the sediment-water interface and removed from the sulfate pool of overlying water column. Negative relationship between δ34Ssulfide and TOC indicates that redox conditions and physical reworking of sediment at the sediment-water interface controlled the rate of microbial sulfate reduction and sulfur isotope fractionation. Overall, co-variation of lithofacies and isotopic records suggests that local heterogeneity of seawater chemistry and sedimentary dynamics may exert partial controls on biogeochemical processes and amplify the magnitude of the Hirnantian isotopic excursions in the proximal area.

Combined 34S, 33S and 18O isotope fractionations record different intracellular steps of microbial sulfate reduction

Several enzymatic steps in microbial sulfate reduction (MSR) fractionate the isotope ratios of 33S/32S, 34S/32S and 18O/16O in extracellular sulfate, but the effects of different intracellular processes on the isotopic composition of residual sulfate are still not well quantified. We measured combined multiple sulfur (33S/32S, 34S/32S) and oxygen (18O/16O) isotope ratios of sulfate in pure cultures of a marine sulfate reducing bacterium Desulfovibrio sp. DMSS-1 grown on different organic substrates. These measurements are consistent with the previously reported correlations of oxygen and sulfur isotope fractionations with the cell-specific rate of MSR: faster reduction rates produced smaller isotopic fractionations for all isotopes. Combined isotope fractionation of oxygen and multiple sulfur isotopes are also consistent with the relationship between the rate limiting step during microbial sulfate reduction and the availability of the DsrC subunit. These experiments help reconstruct and interpret processes that operate in natural pore waters characterized by high 18O/16O and moderate 34S/32S ratios and suggest that some multiple isotope signals in the environment cannot be explained by microbial sulfate reduction alone. Instead, these signals support the presence of active, but slow sulfate reduction as well as the reoxidation of sulfide.

Activity and phylogenetic diversity of sulfate-reducing microorganisms in low-temperature subsurface fluids within the upper oceanic crust.

The basaltic ocean crust is the largest aquifer system on Earth, yet the rates of biological activity in this environment are unknown. Low-temperature (<100°C) fluid samples were investigated from two borehole observatories in the Juan de Fuca Ridge (JFR) flank, representing a range of upper oceanic basement thermal and geochemical properties. Microbial sulfate reduction rates (SRR) were measured in laboratory incubations with 35S-sulfate over a range of temperatures and the identity of the corresponding sulfate-reducing microorganisms (SRM) was studied by analyzing the sequence diversity of the functional marker dissimilatory (bi)sulfite reductase (dsrAB) gene. We found that microbial sulfate reduction was limited by the decreasing availability of organic electron donors in higher temperature, more altered fluids. Thermodynamic calculations indicate energetic constraints for metabolism, which together with relatively higher cell-specific SRR reveal increased maintenance requirements, consistent with novel species-level dsrAB phylotypes of thermophilic SRM. Our estimates suggest that microbially-mediated sulfate reduction may account for the removal of organic matter in fluids within the upper oceanic crust and underscore the potential quantitative impact of microbial processes in deep subsurface marine crustal fluids on marine and global biogeochemical carbon cycling.

Early Triassic seawater sulfate drawdown

The marine sulfur cycle is intimately linked to global carbon fluxes, atmospheric composition, and climate, yet relatively little is known about how it responded to the end-Permian biocrisis, the largest mass extinction of the Phanerozoic. Here, we analyze carbonate-associated-sulfate (CAS) from three Permo–Triassic sections in South China in order to document the behavior of the C–S cycle and its relationship to marine environmental changes during the mass extinction and its aftermath. We find that δ34SCAS varied from +9‰ to +44‰ at rates up to 100‰Myr−1 during the Griesbachian–Smithian substages of the Early Triassic. We model the marine sulfur cycle to demonstrate that such rapid variation required drawdown of seawater sulfate concentrations to ⩽4mM and a reduction in its residence time to ⩽200kyr. This shorter residence time resulted in positive covariation with δ13Ccarb due to strong coupling of the organic carbon and pyrite burial fluxes. Carbon and sulfur isotopic shifts were associated with contemporaneous changes in climate, marine productivity, and microbial sulfate reduction rates, with negative shifts in δ13Ccarb and δ34SCAS linked to warming, decreased productivity, and reduced sulfate reduction. Sustained cooling during the Spathian re-invigorated oceanic overturning circulation, reduced marine anoxia, and limited pyrite burial. As seawater sulfate built to higher concentrations during the Spathian, the coupling of the marine C and S cycles came to an end and a general amelioration of marine environmental conditions set the stage for a recovery of invertebrate faunas. Variation in seawater sulfate during the Early Triassic was probably controlled by climate change, possibly linked to major eruptive phases of the Siberian Traps.

Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record

Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O2 budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic-Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O2. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen.

Sulfur biogeochemistry of cold seeps in the Green Canyon region of the Gulf of Mexico

Cold seeps in the Gulf of Mexico provide a natural laboratory to study biogeochemical cycling of sulfur, carbon, and oxygen at hydrate- and hydrocarbon-rich deep marine settings with obvious additional relevance to studies of diverse modern and ancient seeps. Of particular interest are the sulfur isotope signatures of microbial sulfate reduction coupled to anaerobic oxidation of methane and other non-methane liquid and gaseous hydrocarbons.Whereas most of the published sulfur isotope data from cold seep systems pertain to pore-water species, our study integrates both solid and dissolved sulfur: acid-volatile sulfides (SAVS), pyrite (Spy), elemental sulfur (S°), dissolved sulfate and ΣH2S. Modeled and 35SO42− reduction rates and δ13C and δ18O data for authigenic carbonates are integrated within this sulfur framework. Our results indicate extreme variability over narrow spatial and temporal scales within short distances (meters) from active seeps. High rates of microbial sulfate reduction can lead to complete consumption of the sulfate within the upper few centimeters of burial, while meters away the sulfate profile shows little depletion. Such small-scale variability must reflect the structure and temporal dynamics of hydrocarbon migration in the presence of low amounts of background organic matter. Our past work demonstrated that electron donors other than methane drive significant levels of microbial activity at these seeps, and very recent work has demonstrated that oxidation of higher chain volatile hydrocarbons can contribute to the high levels of microbial activity. These findings are consistent with our new results.Elevated concentrations of pyrite and diagenetic carbonate relative to background sediments are diagnostic of active seepage, yet the S isotopes tell more complex stories. Low levels of the transient, ‘instantaneous’ products of S cycling—AVS and S°—show high δ34S values that increase with depth. Most of the pyrite formation, however, seems to be very early as limited by the availability of reactive Fe phases. As such, δ34S values for pyrite at ancient seeps can show consistently low δ34S values that undersell the full intensity of microbial sulfate reduction. Low sedimentation rates, and the resulting low detrital iron fluxes, may in fact limit our ability to recognize seeps in the geologic record using only δ34S compositions for pyrite.