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Evidence of magnetic isotope effects during thermochemical sulfate reduction.

ABSTRACT: Thermochemical sulfate reduction experiments with simple amino acid and dilute concentrations of sulfate reveal significant degrees of mass-independent sulfur isotope fractionation. Enrichments of up to 13‰ for (33)S are attributed to a magnetic isotope effect (MIE) associated with the formation of thiol-disulfide, ion-radical pairs. Observed (36)S depletions in products are explained here by classical (mass-dependent) isotope effects and mixing processes. The experimental data contrasts strongly with multiple sulfur isotope trends in Archean samples, which exhibit significant (36)S anomalies. These results support an origin other than thermochemical sulfate reduction for the mass-independent signals observed for early Earth samples.

SUBMITTER: Oduro H

PROVIDER: S-EPMC3203815 | biostudies-literature | 2011 Oct

REPOSITORIES: biostudies-literature

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Evidence of magnetic isotope effects during thermochemical sulfate reduction.

Oduro Harry H Harms Brian B Sintim Herman O HO Kaufman Alan J AJ Cody George G Farquhar James J

Proceedings of the National Academy of Sciences of the United States of America 20111012 43

Thermochemical sulfate reduction experiments with simple amino acid and dilute concentrations of sulfate reveal significant degrees of mass-independent sulfur isotope fractionation. Enrichments of up to 13‰ for (33)S are attributed to a magnetic isotope effect (MIE) associated with the formation of thiol-disulfide, ion-radical pairs. Observed (36)S depletions in products are explained here by classical (mass-dependent) isotope effects and mixing processes. The experimental data contrasts strongl ...[more]

PMID: 21997216

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Project description:The sulfur isotope record provides key insight into the history of Earth's redox conditions. A detailed understanding of the metabolisms driving this cycle, and specifically microbial sulfate reduction (MSR), is crucial for accurate paleoenvironmental reconstructions. This includes a precise knowledge of the step-specific sulfur isotope effects during MSR. In this study, we aim at resolving the cellular-level fractionation factor during dissimilatory sulfite reduction to sulfide within MSR, and use this measured isotope effect as a calibration to enhance our understanding of the biochemistry of sulfite reduction. For this, we merge measured isotope effects associated with dissimilatory sulfite reduction with a quantitative model that explicitly links net fractionation, reaction reversibility, and intracellular metabolite levels. The highly targeted experimental aspect of this study was possible by virtue of the availability of a deletion mutant strain of the model sulfate reducer Desulfovibrio vulgaris (strain Hildenborough), in which the sulfite reduction step is isolated from the rest of the metabolic pathway owing to the absence of its QmoABC complex (?Qmo). This deletion disrupts electron flux and prevents the reduction of adenosine phosphosulfate (APS) to sulfite. When grown in open-system steady-state conditions at 10% maximum growth rate in the presence of sulfite and lactate as electron donor, sulfur isotope fractionation factors averaged -15.9‰ (1 ? = 0.4), which appeared to be statistically indistinguishable from a pure enzyme study with dissimilatory sulfite reductase. We coupled these measurements with an understanding of step-specific equilibrium and kinetic isotope effects, and furthered our mechanistic understanding of the biochemistry of sulfite uptake and ensuing reduction. Our metabolically informed isotope model identifies flavodoxin as the most likely electron carrier performing the transfer of electrons to dissimilatory sulfite reductase. This is in line with previous work on metabolic strategies adopted by sulfate reducers under different energy regimes, and has implications for our understanding of the plasticity of this metabolic pathway at the center of our interpretation of modern and palaeo-environmental records.

Dataset Information

Evidence of magnetic isotope effects during thermochemical sulfate reduction.

Publications

Evidence of magnetic isotope effects during thermochemical sulfate reduction.

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