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Theoretical estimates of sulfoxyanion triple-oxygen equilibrium isotope effects and their implications
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  • Jordon D Hemingway,
  • Madison L Goldberg,
  • Kevin M Sutherland,
  • David T Johnston
Jordon D Hemingway
ETH Zürich

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Madison L Goldberg
Harvard University
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Kevin M Sutherland
Harvard University
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David T Johnston
Harvard University
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Abstract

Triple-oxygen isotope (δ18O and Δ17O) analysis of sulfate is becoming a common tool to assess several biotic and abiotic sulfur-cycle processes, both today and in the geologic past. Multi-step sulfur redox reactions often involve intermediate sulfoxyanions such as sulfite, sulfoxylate, and thiosulfate, which can rapidly exchange oxygen atoms with surrounding water. Process-based reconstructions therefore require knowledge of equilibrium oxygen-isotope fractionation factors (18α and 17α) between water and each individual sulfoxyanion. Despite this importance, there currently exist only limited experimental 18α data and no 17α estimates due to the difficulty of isolating and analyzing short-lived intermediate species. To address this, we theoretically estimate 18α and 17α for a suite of sulfoxyanions—including several sulfate, sulfite, sulfoxylate, and thiosulfate isomers—using quantum computational chemistry. We determine fractionation factors for sulfoxyanion “water droplets”; using the B3LYP/6-31G+(d,p) method; we additionally determine higher-order method (CCSD/aug-cc-pVTZ and MP2/aug-cc-pVTZ) and anharmonic zero-point energy (ZPE) scaling factors using a suite of gaseous sulfoxy compounds and test their impact on resulting sulfoxyanion fractionation-factor estimates. When including redox state-specific CCSD/aug-cc-pVTZ and anharmonic ZPE scaling factors, our theoretical 18α predictions for protonated isomers closely agree with all existing experimental data, yielding root-mean-square errors of 1.8 ‰ for SO3(OH)-/H2O equilibrium (n = 18 experimental conditions), 2.2 ‰ for SO2(OH)-/H2O (n = 27), and 3.9 ‰ for S2O2(OH)-/H2O (n = 3). This result supports the idea that oxygen exchange occurs via isomers containing oxygen-bound protons. By combining 18α and 17α predictions, we additionally estimate that SO3(OH)-, SO2(OH)-, SO(OH)-, and S2O2(OH) exhibit Δ17O values as much as 0.167 ‰, 0.097 ‰, 0.049 ‰, and 0.153 ‰ more negative than equilibrated water at Earth-surface temperatures (reference line slope = 0.5305). This theoretical framework provides a foundation to interpret experimental and observational triple-oxygen isotope results of several sulfur-cycle processes including pyrite oxidation, microbial metabolisms (e.g., sulfate reduction, thiosulfate disproportionation), and hydrothermal anhydrite precipitation. We highlight this with several examples.