Theoretical estimates of sulfoxyanion triple-oxygen equilibrium isotope
effects and their implications
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.