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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. Access through your institution Buy or subscribe This is a preview of subscription content, access via your institution ACCESS OPTIONS Access through
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support SIMILAR CONTENT BEING VIEWED BY OTHERS ANOMALOUS Δ15N VALUES IN THE NEOARCHEAN ASSOCIATED WITH AN ABUNDANT SUPPLY OF HYDROTHERMAL AMMONIUM Article Open access 22 February 2025
MACKINAWITE PARTIAL OXIDATION TO GREEN RUST PRODUCES A LARGE, ABIOTIC URANIUM ISOTOPE FRACTIONATION Article Open access 08 February 2025 EXTENSIVE PRIMARY PRODUCTION PROMOTED THE RECOVERY OF
THE EDIACARAN SHURAM EXCURSION Article Open access 10 January 2022 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. REFERENCES * Ader, M. et al. Interpretation of the nitrogen isotopic composition of Precambrian sedimentary rocks: assumptions and perspectives.
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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 * Laboratoire Biogéosciences, UMR CNRS 6282, Université de Bourgogne, Dijon, France Alice
Pellerin & Christophe Thomazo * Institut Universitaire de France (IUF), Paris, France Christophe Thomazo * Institut de Physique du Globe de Paris, Université Paris-Cité, CNRS, Paris,
France Magali Ader & Vincent Busigny * Dipartimento di Scienze Chimiche e Geologiche, Università degli studi di Cagliari, Cagliari, Italy Camille Rossignol * Scripps Institution of
Oceanography, Geosciences Research Division, University of California, San Diego, La Jolla, CA, USA Eric Siciliano Rego * Géosciences Montpellier, Université de Montpellier, CNRS,
Montpellier, France Pascal Philippot * Departamento de Geofísica, Instituto de Astronomia, Geofísica e Ciências Atmosféricas, Universidade de São Paulo, São Paulo, Brazil Pascal Philippot
Authors * Alice Pellerin View author publications You can also search for this author inPubMed Google Scholar * Christophe Thomazo View author publications You can also search for this
author inPubMed Google Scholar * Magali Ader View author publications You can also search for this author inPubMed Google Scholar * Camille Rossignol View author publications You can also
search for this author inPubMed Google Scholar * Eric Siciliano Rego View author publications You can also search for this author inPubMed Google Scholar * Vincent Busigny View author
publications You can also search for this author inPubMed Google Scholar * Pascal Philippot View author publications You can also search for this author inPubMed Google Scholar 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. CORRESPONDING AUTHOR Correspondence to Alice Pellerin. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. PEER REVIEW PEER REVIEW
INFORMATION _Nature_ thanks Timothy Lyons and Eva Stüeken for their contribution to the peer review of this work. Peer reviewer reports are available. ADDITIONAL INFORMATION PUBLISHER’S NOTE
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. 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. SUPPLEMENTARY INFORMATION PEER REVIEW FILE
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Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Pellerin, A., Thomazo, C., Ader, M. _et al._ Neoarchaean oxygen-based nitrogen cycle en route to the Great Oxidation Event.
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