Iron-dependent nitrogen cycling in a ferruginous lake and the nutrient status of Proterozoic oceans

Nitrogen limitation during the Proterozoic has been inferred from the great expanse of ocean anoxia under low-O-2 atmospheres, which could have promoted NO3- reduction to N-2 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 N-2 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 off set 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 mu M) 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.