{"id":16103,"date":"2020-12-14T19:02:42","date_gmt":"2020-12-15T03:02:42","guid":{"rendered":"https:\/\/www.darkenergybiosphere.org\/?post_type=publication&#038;p=16103"},"modified":"2021-01-03T14:06:34","modified_gmt":"2021-01-03T22:06:34","slug":"what-fractionates-oxygen-isotopes-during-respiration-insights-from-multiple-isotopologue-measurements-and-theory","status":"publish","type":"publication","link":"https:\/\/www.darkenergybiosphere.org\/publication\/what-fractionates-oxygen-isotopes-during-respiration-insights-from-multiple-isotopologue-measurements-and-theory\/","title":{"rendered":"What Fractionates Oxygen Isotopes during Respiration? Insights from Multiple Isotopologue Measurements and Theory"},"content":{"rendered":"<p>The precise mass dependence of respiratory O<sub>2<\/sub>\u00a0consumption underpins the \u201coxygen triple-isotope\u201d approach to quantifying gross primary productivity in modern and ancient environments. Yet, the physical-chemical origins of the key\u00a0<sup>18<\/sup>O\/<sup>16<\/sup>O and\u00a0<sup>17<\/sup>O\/<sup>16<\/sup>O 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\u2013O 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\u00a0<sup>17<\/sup>O<sup>18<\/sup>O and\u00a0<sup>18<\/sup>O<sup>18<\/sup>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<sub>2<\/sub>\u00a0interacting with heme-oxidase analogues. We find a significantly steeper mass dependence, supported by theory, than has been previously observed. Enrichments of\u00a0<sup>17<\/sup>O<sup>18<\/sup>O and\u00a0<sup>18<\/sup>O<sup>18<\/sup>O in the O<sub>2<\/sub>\u00a0residue suggest that \u03b8 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.<\/p>\n","protected":false},"template":"","tags":[],"publication_type":[19],"_links":{"self":[{"href":"https:\/\/www.darkenergybiosphere.org\/wp-json\/wp\/v2\/publication\/16103"}],"collection":[{"href":"https:\/\/www.darkenergybiosphere.org\/wp-json\/wp\/v2\/publication"}],"about":[{"href":"https:\/\/www.darkenergybiosphere.org\/wp-json\/wp\/v2\/types\/publication"}],"wp:attachment":[{"href":"https:\/\/www.darkenergybiosphere.org\/wp-json\/wp\/v2\/media?parent=16103"}],"wp:term":[{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.darkenergybiosphere.org\/wp-json\/wp\/v2\/tags?post=16103"},{"taxonomy":"publication_type","embeddable":true,"href":"https:\/\/www.darkenergybiosphere.org\/wp-json\/wp\/v2\/publication_type?post=16103"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}