LAUSR

Nitrogen limitation during the Proterozoic has been inferred from the great expanse of ocean anoxia under low-O2 atmospheres, which could have promoted NO3− reduction to N2 and fixed N loss from the ocean. The deep oceans were Fe rich (ferruginous) during much of this time, yet the dynamics of N cycling under such conditions remain entirely conceptual, as analogue environments are rare today. Here we use incubation experiments to show that a modern ferruginous basin, Kabuno Bay in East Africa, supports high rates of NO3− reduction. Although 60% of this NO3− is reduced to N2 through canonical denitrification, a large fraction (40%) is reduced to NH4+, leading to N retention rather than loss. We also find that NO3− reduction is Fe dependent, demonstrating that such reactions occur in natural ferruginous water columns. Numerical modelling of ferruginous upwelling systems, informed by our results from Kabuno Bay, demonstrates that NO3− reduction to NH4+ could have enhanced biological production, fuelling sulfate reduction and the development of mid-water euxinia overlying ferruginous deep oceans. This NO3− reduction to NH4+ could also have partly offset a negative feedback on biological production that accompanies oxygenation of the surface ocean. Our results indicate that N loss in ferruginous upwelling systems may not have kept pace with global N fixation at marine phosphorous concentrations (0.04–0.13 μM) indicated by the rock record. We therefore suggest that global marine biological production under ferruginous ocean conditions in the Proterozoic eon may thus have been P not N limited. Fixed nitrogen is lost from oxygen minimum zones. Experimental data from an anoxic lake show that the presence of Fe(II) limits this loss, suggesting that ancient anoxic and iron-rich oceans may not have been nitrogen limited.