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Neoarchaean oxygen-based nitrogen cycle en route to the Great Oxidation Event

Nature volume 633, pages 365–370 (2024) Cite this article

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Abstract

The nitrogen isotopic composition of sedimentary rocks (δ15N) can trace redox-dependent biological pathways and early Earth oxygenation1,2. However, there is no substantial change in the sedimentary δ15N record across the Great Oxidation Event about 2.45 billion years ago (Ga)3, a prominent redox change. This argues for a temporal decoupling between the emergence of the first oxygen-based oxidative pathways of the nitrogen cycle and the accumulation of atmospheric oxygen after 2.45 Ga (ref. 3). The transition between both states shows strongly positive δ15N values (10–50‰) in rocks deposited between 2.8 Ga and 2.6 Ga, but their origin and spatial extent remain uncertain4,5. Here we report strongly positive δ15N values (>30‰) in the 2.68-Gyr-old shallow to deep marine sedimentary deposit of the Serra Sul Formation6, Amazonian Craton, Brazil. Our findings are best explained by regionally variable extents of ammonium oxidation to N2 or N2O tied to a cryptic oxygen cycle, implying that oxygenic photosynthesis was operating at 2.7 Ga. Molecular oxygen production probably shifted the redox potential so that an intermediate N cycle based on ammonium oxidation developed before nitrate accumulation in surface waters. We propose to name this period, when strongly positive nitrogen isotopic compositions are superimposed on the usual range of Precambrian δ15N values, the Nitrogen Isotope Event. We suggest that it marks the earliest steps of the biogeochemical reorganizations that led to the Great Oxidation Event.

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Fig. 1: Compilation of paired Precambrian sedimentary δ15N and δ13Corg data, including all lithologies.
The alternative text for this image may have been generated using AI.
Fig. 2: Carbon and nitrogen geochemical and isotopic profiles for drill cores GT13 and GT16.
The alternative text for this image may have been generated using AI.

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Data availability

All data are available in the main text or the supplementary materials, and at https://doi.org/10.25666/DATAUBFC-2024-06-27.

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Acknowledgements

For technical support, we would like to thank A.-L. Santoni and the GISMO platform (Université de Bourgogne, France) and G. Landais, R. Tchibinda, G. Bardoux and V. Rojas (Institut de Physique du Globe de Paris, France). Funding: Institut Universitaire de France (IUF) – project EVOLINES (C.T.); Observatoire des Sciences de l’Univers Terre Homme Environnement Temps Astronomie of Bourgogne-Franche-Comté (OSU THETA) – project NITROPAST (C.T.); Fundação de Amparo à Pesquisa do Estado de São Paulo, FAPESP projects 2019/16271-0, 2018/05892-0, 2015/16235-2, 2018/02645-2 and 2019/16066-7 (P.P.).

Author information

Authors and Affiliations

  1. Laboratoire Biogéosciences, UMR CNRS 6282, Université de Bourgogne, Dijon, France

    Alice Pellerin & Christophe Thomazo

  2. Institut Universitaire de France (IUF), Paris, France

    Christophe Thomazo

  3. Institut de Physique du Globe de Paris, Université Paris-Cité, CNRS, Paris, France

    Magali Ader & Vincent Busigny

  4. Dipartimento di Scienze Chimiche e Geologiche, Università degli studi di Cagliari, Cagliari, Italy

    Camille Rossignol

  5. Scripps Institution of Oceanography, Geosciences Research Division, University of California, San Diego, La Jolla, CA, USA

    Eric Siciliano Rego

  6. Géosciences Montpellier, Université de Montpellier, CNRS, Montpellier, France

    Pascal Philippot

  7. Departamento de Geofísica, Instituto de Astronomia, Geofísica e Ciências Atmosféricas, Universidade de São Paulo, São Paulo, Brazil

    Pascal Philippot

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  1. Alice Pellerin
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Contributions

Conceptualization: A.P., C.T., M.A., P.P. Investigation: A.P. Funding acquisition: C.T., P.P. Supervision: C.T., M.A. Writing—original draft: A.P. Review and editing: A.P., C.T., M.A., V.B., E.S.R., C.R., P.P.

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Correspondence to Alice Pellerin.

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Extended data figures and tables

Extended Data Fig. 1 Sedimentological logs of the drill cores GT13 and GT16 with photographs of the main facies and sedimentary structures.

Arrows point to the stratigraphic top. Top left, conglomerate with oriented clasts and sandy matrix; middle left, alternations of siltstone and fine sandstone; bottom left and middle, syn-sedimentary, centimetric-scale faults within fine sandstone to siltstone. Top right, sandstone with wave ripples, framboidal pyrite (blue circles) and load casts; middle right, normally graded conglomerate with rounded quartz pebbles and sub-angular sedimentary clasts, grading to coarse sandstone; bottom right, flat-pebble conglomerate comprising elongated and deformed intraformational clasts.

Extended Data Fig. 2 Cross-plots for drill cores GT13 (orange) and GT16 (red).

TOC (wt%) versus TN (ppm); δ15N (‰ versus air) versus TN (ppm); δ15N (‰ versus air) versus TOC/TN ratio and δ13Corg (‰ versus PDB) versus δ15N (‰ versus air).

Extended Data Fig. 3 Maps illustrating the location of the Carajás Basin.

a, Main tectonic elements of South America84. b, Geological map of the Carajás Basin85. c, Location of the drill cores.

Extended Data Fig. 4 Main sedimentary units of the Carajás Basin and age constraints.

1: ref. 86; 2,3: ref. 87; 4: ref. 88; 5: ref. 6; 6: ref. 28.

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Pellerin, A., Thomazo, C., Ader, M. et al. Neoarchaean oxygen-based nitrogen cycle en route to the Great Oxidation Event. Nature 633, 365–370 (2024). https://doi.org/10.1038/s41586-024-07842-x

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