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Onset of the aerobic nitrogen cycle during the Great Oxidation Event


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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Figure 1: Secular trend in sedimentary δ15N over early Earth history.
Figure 2: Lithological and geochemical data for core EBA-2.


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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.

Author information

Authors and Affiliations



A.L.Z. and S.W.P. conceived the study. S.W.P. and A.B. collected the samples. A.L.Z., S.W.P., R.J.N., C.M. and C.K.J. processed samples and performed geochemical analyses. M.W.C. provided statistical analyses of the global database. A.L.Z. interpreted the data and wrote the manuscript with input from all coauthors.

Corresponding author

Correspondence to Aubrey L. Zerkle.

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Competing interests

The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 Results from statistical analysis of the δ15N database.

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).

Extended Data Figure 2 Stratigraphic context for the Rooihoogte and Timeball Hill formations within the Eastern Transvaal basin, South Africa, and associated ages.

‘MIF’ is the disappearance of the mass-independent fractionation of sulfur isotopes in the underlying Duitschland Formation (now known to reappear in the Rooihoogte Formation6). Fm, formation. Image adapted from ref. 5, Elsevier.

Extended Data Figure 3 Simplified geologic map of the Transvaal Supergroup outcrop area.

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.

Extended Data Figure 4 Additional data for kerogen analyses.

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.

Source data

Extended Data Figure 5 Additional data for bulk-rock analyses.

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).

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