Microbial denitrification converts fixed nitrogen species into gases in extant oceans. However, it is unclear how such transformations occurred within the early nitrogen cycle of the Archaean. Here we demonstrate under simulated Archaean conditions mineral-catalysed reduction of nitrite via green rust and magnetite to reach enzymatic conversion rates. We find that in an Fe2+-rich marine environment, Fe minerals could have mediated the formation of nitric oxide (NO) and nitrous oxide (N2O). Nitrate did not exhibit reactivity in the presence of either mineral or aqueous Fe2+; however, both minerals induced rapid nitrite reduction to NO and N2O. While N2O escaped into the gas phase (63% of nitrite nitrogen, with green rust as the catalyst), NO remained associated with precipitates (7%), serving as a potential shuttle to the benthic ocean. Diffusion and photochemical modelling suggest that marine N2O emissions would have sustained 0.8–6.0 parts per billion of atmospheric N2O without a protective ozone layer. Our findings imply a globally distributed abiotic denitrification process that feasibly aided early microbial life to accrue new capabilities, such as respiratory metabolisms.
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The code for the photochemical model will be shared by the corresponding author upon request.
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We thank M. Kirven-Brooks and C. P. McKay for support during the initial experimental phase at the NASA Ames Research Center. We are grateful to K. Weiss, S. Phrasavath, E. Soignard and A. Smith for help with the mineral analytics. We also thank J. G. Lopez for discussions on the diffusion modelling and A. D. Anbar, C. M. Ostrander, J. B. Glass, A. Kappler, M. J. Russell and S. Yoon for feedback on the manuscript. H.C.-Q. and S.B. were supported by the National Aeronautics and Space Administration’s (NASA’s) Nexus for Exoplanet System Science (NExSS) research coordination network at Arizona State University led by S. J. Desch (NNX-15AD53G) and sponsored by NASA’s Science Mission Directorate. S.B. and H.I. received critical funding through the NASA Astrobiology Institute (NAI) Early Career Collaboration Award. H.I. also received funding for this work from the NASA Exoplanets Research Program and NExSS grant NNX-15AQ73G. The research was carried out in part at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with NASA (80NM0018D0004). R.H. was supported in part by NASA’s Exoplanets Research Program grant 80NM0018F0612. S.J.R. acknowledges support from NASA Exobiology (award 80NSSC19K0474) and the National Science Foundation Sedimentary Geology and Paleobiology Program (award 1733598).
The authors declare no competing interests.
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Buessecker, S., Imanaka, H., Ely, T. et al. Mineral-catalysed formation of marine NO and N2O on the anoxic early Earth. Nat. Geosci. 15, 1056–1063 (2022). https://doi.org/10.1038/s41561-022-01089-9
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