The oxygen isotope equilibrium fractionation between sulfite species and water

Müller, Inigo A.; Brunner, Benjamin; Breuer, Christian; Coleman, Max; Bach, Wolfgang

doi:10.1016/j.gca.2013.06.037

Cited by 39 publications

(34 citation statements)

References 69 publications

(82 reference statements)

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“…Net sulfur isotope fractionation (expressed as 34 ε: the isotopic offset between sulfate and sulfide) ranged from 17.2 to 56.5‰ for the high sulfate, variable rate experiments. For the low sulfate experiments, 34 ε varied from 0.1 to 11.4‰ for D. alaskensis and from 24.2 to 27.5‰ for D. vulgaris ( Fig. 2 and S2).…”

Section: Resultsmentioning

confidence: 99%

“…The two isotope systems (sulfur and oxygen) share core biochemistries, yet, a modified reaction network is required to better represent the oxygen isotope system. Various equilibria with water play key roles in the oxygen isotope composition of intracellular species: the near instantaneous sulfite-water isotopic equilibrium is perhaps the most crucial [29,34]. Any potential oxygen isotope exchange between more reduced sulfur intermediates downstream from sulfite (S 2 O 3 2− , S 3 O 6 2− , etc., as has been reported before, giving rise to the so-termed "trithionate pathway" [40]), or sulfide reoxidation reactions would effectively be erased at the sulfite stage.…”

Section: The Biochemical Network Of Msrmentioning

confidence: 99%

“…We aim to quantitatively link the MSR biogeochemistry and its oxygen isotope effect. Mathematical frameworks have been developed to establish quantitative links between cell-specific parameters (i.e., rate [17,19,20,24]) and the temperature and pH-sensitive [31] equilibrium oxygen isotope exchange between intracellular sulfur species and ambient water [29,[32][33][34][35]. This equilibrium oxygen isotope effect places a critical oxygen isotope equilibration step within the dissimilatory sulfate reduction pathway ( Fig.…”

Section: Introductionmentioning

confidence: 99%

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Oxygen isotope effects during microbial sulfate reduction: applications to sediment cell abundances

et al. 2020

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The majority of anaerobic biogeochemical cycling occurs within marine sediments. To understand these processes, quantifying the distribution of active cells and gross metabolic activity is essential. We present an isotope model rooted in thermodynamics to draw quantitative links between cell-specific sulfate reduction rates and active sedimentary cell abundances. This model is calibrated using data from a series of continuous culture experiments with two strains of sulfate reducing bacteria (freshwater bacterium Desulfovibrio vulgaris strain Hildenborough, and marine bacterium Desulfovibrio alaskensis strain G-20) grown on lactate across a range of metabolic rates and ambient sulfate concentrations. We use a combination of experimental sulfate oxygen isotope data and nonlinear regression fitting tools to solve for unknown kinetic, step-specific oxygen isotope effects. This approach enables identification of key isotopic reactions within the metabolic pathway, and defines a new, calibrated framework for understanding oxygen isotope variability in sulfate. This approach is then combined with porewater sulfate/sulfide concentration data and diagenetic modeling to reproduce measured 18 O/ 16 O in porewater sulfate. From here, we infer cell-specific sulfate reduction rates and predict abundance of active cells of sulfate reducing bacteria, the result of which is consistent with direct biological measurements.

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Section: Resultsmentioning

confidence: 99%

Section: The Biochemical Network Of Msrmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Oxygen isotope effects during microbial sulfate reduction: applications to sediment cell abundances

et al. 2020

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“…δ 18 O signatures do not follow a Rayleigh fractionation model but rather appear to be dominated by the rapid equilibration of oxygen in the sulfite intermediate species with water-oxygen (Mangalo et al, 2007; Brunner et al, 2012; Müller et al, 2013). As such, this gives us a measurement that is complementary to sulfur isotopes and has the potential for teasing out additional information about dynamic sulfur cycling in oil reservoirs (Hubert et al, 2009).…”

Section: Discussionmentioning

confidence: 99%

Isotopic insights into microbial sulfur cycling in oil reservoirs

et al. 2014

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Microbial sulfate reduction in oil reservoirs (biosouring) is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM) is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of −30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures.

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“…In contrast, the d 18 O SO 4 during microbial sulfate reduction tends to reach oxygen isotope equilibrium with ambient water (Fritz et al, 1989;Brunner et al, 2005;Wortmann et al, 2007). Although sulfate does not readily exchange its oxygen atoms with water, it has been shown that intermediate-valence-state sulfur species that are formed during microbial sulfate reduction exchange their oxygen atoms with water (e.g., Wankel et al, 2014;Müller et al, 2013). If these sulfur intermediates are reoxidized back to sulfate, the oxygen isotope signature of the water will be observed in the extracellular aqueous sulfate pool.…”

Section: Introductionmentioning

confidence: 99%

A unique isotopic fingerprint of sulfate-driven anaerobic oxidation of methane

Antler

Turchyn

Herut

et al. 2015

Geology

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The largest reservoir of the powerful greenhouse gas methane is in marine sediments, and catastrophic release of this methane has been invoked to explain climate perturbations throughout Earth history. Marine methane oxidation is mainly coupled anaerobically to microbial sulfate reduction, which both limits and controls the release of methane from this sedimentary reservoir to the rest of Earth's surface. Methane can be transported within the pore space of marine sediments either via diffusion or as bubbles. When methane travels in bubbles, these bubbles often are not completely oxidized and reach the overlying water where the methane emerges from the sediment in cold seeps. Although paleo-cold seeps can be identified by geological features such as carbonate mounds, a geochemical signature for cold seeps remains elusive. We demonstrate, using the sulfur and oxygen isotope composition of sulfate, that a unique isotopic signature emerges during microbial sulfate reduction coupled to methane oxidation in bubbling cold seeps. This isotope signature differs from that when sulfate is reduced by either organic matter oxidation or by the slower, diffusive flux of methane within marine sediments. We also show, through a comparison with the literature, that this unique isotope fingerprint is preserved in the rock record in authigenic buildups of barite associated with methane cold seeps. δ Figure 3. The d 18 O SO 4 versus d 34 S SO 4 data from cold methane seeps and seeps analogues (gray symbols) and barite deposits associated with cold methane seeps (white symbols) from the Gulf of Mexico (rhombus, Fu and Aharon, 1997; squares, Feng and Roberts, 2011) and from the Sea of Okhotsk (circles, Greinert et al., 2002). VCDT-Vienna Canyon Diablo troilite; VSMOW-Vienna standard mean ocean water.as

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The oxygen isotope equilibrium fractionation between sulfite species and water

Cited by 39 publications

References 69 publications

Oxygen isotope effects during microbial sulfate reduction: applications to sediment cell abundances

Oxygen isotope effects during microbial sulfate reduction: applications to sediment cell abundances

Isotopic insights into microbial sulfur cycling in oil reservoirs

A unique isotopic fingerprint of sulfate-driven anaerobic oxidation of methane

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