Microbial Denitrification: Active Site and Reaction Path Models Predict New Isotopic Fingerprints.

Autor: Boettger JD; Department of Earth, Environmental, and Resource Sciences, The University of Texas at El Paso, El Paso, Texas 79968, United States., Neubauer C; Department of Geological Sciences & Institute of Arctic and Alpine Research, University of Colorado, Boulder, Colorado 80303, United States., Kopf SH; Department of Geological Sciences & Institute of Arctic and Alpine Research, University of Colorado, Boulder, Colorado 80303, United States., Kubicki JD; Department of Earth, Environmental, and Resource Sciences, The University of Texas at El Paso, El Paso, Texas 79968, United States.
Jazyk: angličtina
Zdroj: ACS earth & space chemistry [ACS Earth Space Chem] 2022 Nov 17; Vol. 6 (11), pp. 2582-2594. Date of Electronic Publication: 2022 Oct 20.
DOI: 10.1021/acsearthspacechem.2c00102
Abstrakt: The study of isotopic fingerprints in nitrate (δ 15 N, δ 18 O, Δ 17 O) has enabled pivotal insights into the global nitrogen cycle and revealed new knowledge gaps. Measuring populations of isotopic homologs of intact NO 3 - ions (isotopologues) shows promise to advance the understanding of nitrogen cycling processes; however, we need new theory and predictions to guide laboratory experiments and field studies. We investigated the hypothesis that the isotopic composition of the residual nitrate pool is controlled by the N-O bond-breaking step in Nar dissimilatory nitrate reductase using molecular models of the enzyme active sites and associated kinetic isotope effects (KIEs). We integrated the molecular model results into reaction path models representing the reduction of nitrate under either closed-system or steady-state conditions. The predicted intrinsic KIE ( 15 ε and 18 ε) of the Nar active site matches observed fractionations in both culture and environmental studies. This is what would be expected if the isotopic composition of marine nitrate were controlled by dissimilatory nitrate reduction by Nar. For a closed system, the molecular models predict a pronounced negative 15 N- 18 O clumping anomaly in residual nitrate. This signal could encode information about the amount of nitrate consumed in a closed system and thus constrain initial nitrate concentration and its isotopic composition. Similar clumped isotope anomalies can potentially be used to distinguish whether a system is open or closed to new nitrate addition. These mechanistic predictions can be tested and refined in combination with emerging ESI-Orbitrap measurements.
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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