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The precise mass dependence of respiratory O 2 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 18 O/ 16 O and 17 O/ 16 O covariations observed during respiration have not been tied to theory; thus, the approach remains empirical. Firstprinciples 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 17 O 18 O and 18 O 18 O as additional tracers of mass dependence during dark respiration experiments of lacustrine water. We then compare the experimental results to first-principles calculations of O 2 interacting with heme-oxidase analogues. We find a significantly steeper mass dependence, supported by theory, than has been previously observed. Enrichments of 17 O 18 O and 18 O 18 O in the O 2 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.

Upper-atmospheric chemistry and biological N2 cycling engage in a planetary-scale tug-of-war seen in 15N15N of air.

Accurate measurements of isotopic variations are essential to biogeochemistry and for testing theoretical models of isotope effects. PBLs are probably ubiquitous, contributing to the interlaboratory disagreements in triple-isotope compositions of materials differing greatly in δ O values. Moreover, they may lead to inaccurate determination of triple-isotope compositions and fractionation factors, which has implications for isotopic studies in hydrology and biogeochemistry.