Fractionation of sulfur isotopes during bacterial sulfate reduction in deep ocean sediments at elevated temperatures

Rudnicki, M.D.; Elderfield, Henry; Spiro, Baruch

doi:10.1016/s0016-7037(00)00579-2

Cited by 158 publications

(98 citation statements)

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“…Above and below the sulfidic zone, elemental sulfur, and iron monosulfide phases build up, a process that is fueled by sulfide oxidation, which yields S 0 and ferrous iron and induces the precipitation of iron monosulfides through reaction with ferrous iron. Because of the distinct locations of these processes with respect to the center of the SMT, the produced sulfur phases record sulfur isotope signatures for sulfide that are representative for the isotope trends observed in the SMTthat is, a strong enrichment in 34 S from the top to the bottom of the SMT (e.g., Rudnicki et al, 2001;Brunner et al, 2016;Turchyn et al, 2016). These distinct isotope signatures allow the reconstruction of the complex history of biogeochemical sulfur cycling in dynamic sediments.…”

Section: Discussionmentioning

confidence: 99%

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Riedinger

Brunner

Krastel³

et al. 2017

Front. Earth Sci.

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The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope-a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory-conditions that result in low organoclastic sulfate reduction rates (SRR). Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS).Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper Riedinger et al.Non-steady State Subsurface Sulfur Cycling sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

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Section: Discussionmentioning

confidence: 99%

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Riedinger

Brunner

Krastel³

et al. 2017

Front. Earth Sci.

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“…The few early experiments that were performed using H 2 as the electron donor yielded ε 34 S values ranging from Ϫ3 to Ϫ19‰ (22,38,39), which appear to correlate with the csSRR (39 (14) but is not consistent with the lack of significant fractionation observed during oxidative reactions (29). To explain the ⌬ 34 S values of Ϫ55 to Ϫ77‰ reported to occur in interstitial pore waters from 100-to 300-m-deep, hypersulfidic ocean sediments (51,64,67), where the presence of a S-oxidative cycle is unlikely, an alternative, elaborate model of the SO 4 2Ϫ -reducing pathway has been proposed by Brunner and Bernasconi (9 (23), with a corresponding cell turnover rate greater than 1,000 years (37).…”

Section: Dissimilatory Somentioning

confidence: 96%

Sulfur Isotope Enrichment during Maintenance Metabolism in the Thermophilic Sulfate-Reducing Bacterium Desulfotomaculum putei

Davidson

Bisher

Pratt

et al. 2009

Appl Environ Microbiol

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Values of ⌬ 34S SO4 indicate the differences in the isotopic compositions of the HS ؊ and SO 4 2؊ in the eluent, respectively) for many modern marine sediments are in the range of ؊55 to ؊75‰, much greater than the ؊2 to ؊46‰ 34 S (kinetic isotope enrichment) values commonly observed for microbial sulfate reduction in laboratory batch culture and chemostat experiments. It has been proposed that at extremely low sulfate reduction rates under hypersulfidic conditions with a nonlimited supply of sulfate, isotopic enrichment in laboratory culture experiments should increase to the levels recorded in nature. We examined the effect of extremely low sulfate reduction rates and electron donor limitation on S isotope fractionation by culturing a thermophilic, sulfate-reducing bacterium, Desulfotomaculum putei, in a biomass-recycling culture vessel, or "retentostat." The cell-specific rate of sulfate reduction and the specific growth rate decreased progressively from the exponential phase to the maintenance phase, yielding average maintenance coefficients of 10 ؊16 to 10 ؊18 mol of SO 4 cell ؊1 h ؊1 toward the end of the experiments. Overall S mass and isotopic balance were conserved during the experiment. The differences in the ␦ 34 S values of the sulfate and sulfide eluting from the retentostat were significantly larger, attaining a maximum ⌬ 34 S of ؊20.9‰, than the ؊9.7‰ observed during the batch culture experiment, but differences did not attain the values observed in marine sediments. Dissimilatory SO 42Ϫ reduction is a geologically ancient, anaerobic, energy-yielding metabolic process during which SO 4 2Ϫ -reducing bacteria (SRB) reduce SO 4 2Ϫ to H 2 S while oxidizing organic molecules or H 2 . SO 4 2Ϫ reduction is a dominant pathway for organic degradation in marine sediments (23) and in terrestrial subsurface settings where sulfur-bearing minerals dominate over Fe 3ϩ -bearing minerals. For example, at depths greater than 1.5 km below land surface in the fractured sedimentary and igneous rocks of the Witwatersrand Basin of South Africa, SO 4 2Ϫ reduction is the dominant electron-accepting process (3,26,46,48,61).The enrichment of S pyrite and ␦ 34 S barite/gypsum are the isotopic compositions of pyrite and barite or gypsum) increases from Ϫ10‰ in the 3.47-billion-year-old North Pole deposits to Ϫ30‰ in late-Archaean deposits (55), to Ϫ75‰ in Neoproterozoic to modern sulfide-bearing marine sediments (13).The kinetic isotopic enrichment, ε 34 S, deduced from trends in the ␦ 34 S values of SO 4 2Ϫ and HS Ϫ in batch culture microbial SO 4 2Ϫ reduction experiments using the Rayleigh relationship, ranges from Ϫ2‰ to Ϫ46‰ (6,7,11,17,22,27,28,30,31,38,39). The variation in ε 34 S values has been attributed to the SO 4 2Ϫ concentration, the type of electron donor and its concentration, the SO 4 2Ϫ reduction rate per cell (csSRR) (22), temperature, and species-specific isotope enrichment effects. In these laboratory experiments, doubling times are on the order of hours and csSRRs range from to 0.1 to 18 fmol cell Ϫ1 h Ϫ1 ...

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“…Objective 2 will additionally be addressed by the examination of isotopic composition of sulfur species and phosphate, including multiple-sulfur-isotope approaches and dual-isotope analysis of sulfur and oxygen in sulfate and oxygen in phosphate. Recent studies (Ono et al, 2012;Rudnicki et al, 2001;Sim et al 2011) suggest that multiple-sulfur-isotope measurements are a powerful tool to trace the extent and temperature of microbial sulfate reduction. Likewise, oxygen isotope ratios of sulfate and phosphate will provide critical temperature information because oxygen isotope exchange is very slow below ~250°C; therefore, at low temperatures equilibrium-like fractionations for…”

Section: Electron Acceptors Nutrients and Major Anions And Cationsmentioning

confidence: 99%

Untitled

2016

International Ocean Discovery Program Scientific Prospectus

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Determining factors that limit the biomass, diversity, and activity of subseafloor microbial communities is one of the major scientific goals to be addressed by scientific ocean drilling. In the International Ocean Discovery Program (IODP) T-Limit Project, we will drill and core at new boreholes in the immediate vicinity of Ocean Drilling Program (ODP) Sites 1173, 1174, and 808 off Cape Muroto, Japan, in the central Nankai Trough, where anomalously high heat flow regimes result in temperatures of 110° to 140°C at the sediment/basement interface. Because of their location in the trench (Site 1173) and landward protothrust zone of the Nankai Trough accretionary prism (Sites 808 and 1174), the sites have different geotectonic and thermal histories that have resulted in contrasting (bio)geochemical modes of hydrocarbon gas production and consumption. Although the upper temperature limit appears well constrained at relatively energy-rich hydrothermal vent systems at just above 120°C, it is unknown in energy-starved sedimentary subseafloor settings but is generally presumed to be lower and thus expected to be covered by our target sites. During the IODP TLimit Project, we aim to• Comprehensively study the factors that control biomass, activity, and diversity of microbial communities in a subseafloor environment where temperatures increase from ~30° to ~130°C and thus likely encompasses the biotic-abiotic transition zone; and • Determine geochemical, geophysical, and hydrogeological characteristics in sediment and the underlying basaltic basement and elucidate if the supply of fluids containing thermogenic and/or geogenic nutrient and energy substrates may support subseafloor microbial communities in the Nankai accretionary complex.Because of the D/V Chikyu's schedule, these scientific objectives cannot be achieved within a single expedition. During the first TLimit expedition (370), we will drill and retrieve core samples from sedimentary sections (200-1210 m below seafloor) and basement basalt (1210-1260 m below seafloor) at the protothrust site near ODP Site 1174 and measure temperatures in situ.

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Fractionation of sulfur isotopes during bacterial sulfate reduction in deep ocean sediments at elevated temperatures

Cited by 158 publications

References 45 publications

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Sulfur Isotope Enrichment during Maintenance Metabolism in the Thermophilic Sulfate-Reducing Bacterium Desulfotomaculum putei

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