Abstract
Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO2−) reduction by Fe(II) or ‘chemodenitrification’, and its relevance to the production of nitrous oxide (N2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmental conditions. We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (∼8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO2−reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)–N reaction intermediates. N and O isotopic composition of product N2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO2− reduction by Fe(II) may represent an important abiotic source of environmental N2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO2− reduction and N2O formation, helping future studies constrain the relative roles of abiotic and biological N2O production pathways.