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ACS Earth and Space Chemistry: What Fractionates Oxygen Isotopes During Respiration? Insights from Multiple Isotopologue Measurements and Theory

Jeanine L. Ash, Huanting Hu, and Laurence Y. Yeung

Abstract

The precise mass dependence of respiratory O2 consumption underpins the “oxygen triple-isotope” approach to quantifying gross primary productivity in modern and ancient environments. Yet, the physical-chemical origins of the key 18O/16O and 17O/16O covariations observed during respiration have not been tied to theory; thus the approach remains empirical. First-principles calculations on enzyme active-site models suggest that changes in the O-O bond strength upon electron transfer strongly influence respiratory isotopic fractionation. However, molecular diffusion may also be important. Here, we use measurements of the relative abundances of rare isotopologues 17O18O and 18O18O as additional tracers of mass dependence during dark respiration experiments of lacustrine water. We then compare the experimental results to first-principles calculations of O2 interacting with heme-oxidase analogues. We find a significantly steeper mass dependence, supported by theory, than has been previously observed. Enrichments of 17O18O and 18O18O in the O2 residue suggest that θ values are strongly influenced by chemical processes, rather than being dominated by physical processes (i.e. by bond alteration rather than diffusion). In contrast, earlier data are inconsistent with theory, implying that analytical artifacts may have biased those results. Implications for quantifying primary productivity are discussed.

doi: 10.1021/acsearthspacechem.9b00230

Geochemical Perspectives Letters: Exchange catalysis during anaerobic methanotrophy revealed by 12CH2D2 and 13CH3D in methane

Jeanine L. Ash, Matthias Egger, Tina Treude, Issaku Kohl, Barry Cragg, R. John Parkes, Caroline Slomp, Barbara Sherwood Lollar and Edward D. Young

Abstract:  The anaerobic oxidation of methane (AOM) is a crucial component of the methane cycle, but quantifying its role in situ under dynamic environmental conditions remains challenging. We use sediment samples collected during IODP Expedition 347 to the Baltic Sea to show that relative abundances of 12CH2Dand 13CH3D in methane remaining after microbial oxidation are in internal, thermodynamic isotopic equilibrium, and we attribute this phenomenon to the reversibility of the initial step of AOM. These data suggest that 12CH2Dand 13CH3D together can identify the influence of anaerobic methanotrophy in environments where conventional bulk isotope ratios are ambiguous, and these findings may lead to new insights regarding the global significance of enzymatic back reaction in the methane cycle.