A stable and moderate nitrate pool in largely anoxic Mesoproterozoic oceans and implications for eukaryote evolution

The Mesoproterozoic (1.6–1.0 Ga) is a particularly important interval in Earth history that witnessed the initial radiation of eukaryotic life. Ocean anoxia and nutrient limitation has been invoked to explain the delayed expansion of more complex, multicellular eukaryotes during the Mesoproterozoic. However, pulsed oxygenation events and elevated nitrate availability have been identified in shallow marine settings. In deeper waters, however, nitrate availability and potential links to eukaryotic evolution remain poorly constrained. Here, we report an integrated geochemical study based on multiple proxies conducted on two new drill-core sections from the ∼1460 Ma Hongshuizhuang Formation and the ∼1380 Ma Xiamaling Formation, North China. Iron speciation and redox-sensitive trace element systematics suggest dominantly ferruginous to weakly euxinic water column conditions during deposition of both units. Our data are consistent with previous inferences of persistently anoxic deep water conditions in Mesoproterozoic oceans. Exclusively positive δ15N (+3.1 ± 0.8 ‰) values reveal the operation of partial denitrification in the water column, implying a relatively stable and moderate nitrate pool in offshore surface waters. Furthermore, a compilation of the Mesoproterozoic sedimentary δ15N record suggests a global nearshore to offshore oceanic nitrate gradient, with minimal but still bioavailable nitrate in offshore environments. The overall size of the nitrate pool was therefore apparently smaller than that of eukaryote-dominated modern oceans. Coupling Mesoproterozoic sedimentary δ15N data with fossil and biomarker records, we propose that this moderate level of nitrate may have been able to sustain a relatively low abundance of eukaryotic primary producers in the marine ecosystem, but was still not sufficient to trigger eukaryotic diversification and the rise of eukaryotes to ecological dominance.