Mineral-catalysed formation of marine NO and N₂O on the anoxic early Earth

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.