The rise of oxygen on the early Earth (about 2.4 billion years ago)1 caused a reorganization of marine nutrient cycles2,3, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records4 lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales5 of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event)6. Our data fill a gap of about 400 million years in the temporal 15N/14N record4 and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.
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This study was supported financially by a Natural Environment Research Council Fellowship (number NE/H016805 to A.L.Z.). We thank the Council for Geoscience in South Africa and the staff at the National Core Library in Donkerhoek for facilitating access to the core materials, and M. Yun for assistance with stable isotope analyses at the University of Manitoba.
The authors declare no competing financial interests.
Extended data figures and tables
See Methods. ‘R-TH’ represents the Rooihoogte and Timeball Hill formations (this study). Prandom is the ‘false-positive’ probability that the two sample sets separated by each pivot-age arise from populations of the same mean and variance. As discussed in the text, this value reaches an extreme of −31 when the sample sets are split into the time periods 0.70–2.71 Gyr ago and 2.75–3.80 Gyr ago (not shown).
The location of drill core EBA-2 is shown. The core is currently stored at the National Core Library at Donkerhoek, which is managed by the Council for Geoscience in South Africa. Gp, group. Image adapted from ref. 43, Geological Society of South Africa.
a, Kerogen δ15N (δ15Norg, in ‰) versus kerogen N abundance (% Norg). b, δ15Norg versus organic δ13C (δ13Corg, in ‰). c, Total organic carbon (% TOC) versus organic δ13C. For all data points, errors are within the size of the symbols.
a, Bulk-rock δ15N (δ15Nbulk, in ‰) versus total nitrogen (% TN). b, δ15Nbulk versus TOC:TN atomic ratios. c, % TN versus K2O content (%). d, δ15Nbulk versus K2O content. For all data points, errors are within the size of the symbols.
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Zerkle, A., Poulton, S., Newton, R. et al. Onset of the aerobic nitrogen cycle during the Great Oxidation Event. Nature 542, 465–467 (2017). https://doi.org/10.1038/nature20826
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