Abstract

The early Earth was characterized by the absence of oxygen in the ocean–atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5–2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation1,2. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago3 in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen.

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Acknowledgements

N.J.P. acknowledges financial support from NSF EAR-PF; O.J.R. and D.A. from Europole Mer and ANR-10-LABX-19-01; A.H. and F.O.O. from the NRF of South Africa and Acclaim Exploration; S.V.L. from NSERC-PF and LabexMer-PF; K.O.K. from NSERC; N.J.P., T.W.L., C.T.R. and T.M.J. from NASA Exobiology; and T.W.L. from NSF EAR. C. Delvigne, J. Hancox and N. Hicks provided access to drill core and samples; E. Ponzevera and Y. Germain provided technical assistance.

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Affiliations

  1. Yale University, New Haven, Connecticut 06520, USA

    • Noah J. Planavsky
    •  & Xiangli Wang
  2. IFREMER, Plouzané 56470, France

    • Dan Asael
    •  & Olivier J. Rouxel
  3. University of Johannesburg, Johannesburg 2092, South Africa

    • Axel Hofmann
    • , Frantz Ossa Ossa
    • , Albertus J. B. Smith
    •  & Nicolas J. Beukes
  4. California Institute of Technology, Pasadena, California 91125, USA

    • Christopher T. Reinhard
  5. Institut Universitaire Européen de la Mer, Plouzané 29280, France

    • Stefan V. Lalonde
  6. Lawrence University, Appleton, Wisconsin 54911, USA

    • Andrew Knudsen
  7. University of Illinois, Urbana-Champaign, Illinois 61820, USA

    • Xiangli Wang
    •  & Thomas M. Johnson
  8. University of Alberta, Edmonton, Alberta T6G 2R3, Canada

    • Ernesto Pecoits
    •  & Kurt O. Konhauser
  9. University of California, Riverside, California 92521, USA

    • Andrey Bekker
    •  & Timothy W. Lyons

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Contributions

N.J.P. wrote the paper with input from all authors. N.J.P., D.A., O.J.R., A.K., S.V.L., F.O.O., E.P., X.W. and C.T.R. generated data. A.H. and N.J.P. provided samples. N.J.P. and C.T.R. designed the study with input from all authors.

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The authors declare no competing financial interests.

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Correspondence to Noah J. Planavsky.

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https://doi.org/10.1038/ngeo2122

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