Abstract
Given their environmental abundances, it has been long hypothesized that geochemical interactions between reactive forms of manganese and nitrogen may play important roles in the cycling of these elements. Indeed, recent studies have begun shedding light on the possible role of soluble, ligand-bound Mn(III) in promoting abiotic transformations under environmentally relevant conditions. Here, using the kinetic data of Karolewski et al. (Geochim Cosmochim Acta 293:365–378, 2021), we provide the chemical mechanism for the abiotic oxidation of nitrite (NO2−) by Mn(III)-pyrophosphate, MnIIIPP, to form nitrate (NO3−). Nitrous acid (HNO2), not NO2−, is the reductant in the reaction, based on thermodynamic and kinetic considerations. As soluble Mn(III) complexes react in a one-electron transfer reaction, two one-electron transfer steps must occur. In step one, HNO2 is first oxidized to nitrogen dioxide, ·NO2, a free radical via a hydrogen atom transfer (HAT) reaction. We show that this inner sphere reaction process is the rate-limiting step in the reaction sequence. In step two, ·NO2 reacts with a second MnIIIPP complex to form the nitronium ion (NO2+), which is isoelectronic with CO2. Unlike the poor electron-accepting capability of CO2, NO2+ is an excellent electron acceptor for both OH− and H2O, so NO2+ reacts quickly with water to form the end-product NO3− (step 3 in the reaction sequence). Thus, water provides the O atom in this nitrification reaction in accordance with the O-isotope data. This work provides mechanistic perspective on a potentially important interaction between Mn and nitrogen species, thereby offering a framework in which to interpret kinetic and isotopic data and to further investigate the relevance of this reaction under environmental conditions.
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Acknowledgements
This work was supported by NSF Geobiology and Low-Temperature Geochemistry grant EAR1826940 to SDW and CMH, by NASA Earth and Space Science Fellowship NNX15AR62H and Agouron Institute Geobiology Postdoctoral Fellowship to KMS, and by NSF Chemical Oceanography grant OCE-1558738 to GWL. All original rate and isotope data can be found at https://doi.org/10.1016/j.gca.2020.11.004. We thank the anonymous reviewers for their constructive comments.
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Luther III, G.W., Karolewski, J.S., Sutherland, K.M. et al. The Abiotic Nitrite Oxidation by Ligand-Bound Manganese (III): The Chemical Mechanism. Aquat Geochem 27, 207–220 (2021). https://doi.org/10.1007/s10498-021-09396-0
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DOI: https://doi.org/10.1007/s10498-021-09396-0