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Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event

Nature volume 478, pages 369–373 (2011)Cite this article

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Abstract

The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth’s land surface1,2. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations3. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed—and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4–6)—marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(iii), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(iii) from ultramafic source rocks and residual soils7. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate8 and sulphide-hosted trace elements to the oceans around that time1,9. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

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Figure 1: Chromium in iron-rich sedimentary rocks through time.
Figure 2: Cr–Ti–Al systematics support the evolving nature of the marine Cr supply with time.
Figure 3: River/marine mixing model, indicating alteration pH necessary to supply sufficient Cr to account for Cr enrichment in the Timeball Hill Formation.

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  • 07 November 2011

    The scale bar in Fig. 2 appeared incorrectly in the PDF version of this paper but the print and HTML versions are correct. The PDF version has been corrected.

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Acknowledgements

This study was supported by the Natural Sciences and Engineering Research Council of Canada (K.O.K., S.V.L., A.B., P.W.F.), the National Science Foundation Division of Earth Sciences (T.W.L., O.J.R., L.R.K.), the National Science Foundation’s Graduate Research Program (N.J.P.), the Agouron Institute (E.P., T.W.L.), NASA’s Exobiology Program (T.W.L., S.J.M.), NASA’s Astrobiology Institute (T.W.L., L.R.K., N.J.P.), the Australian Research Council (M.E.B.), and the Conselho Nacional de Desenvolvimento Cientifico e Technológico (C.R.) We also thank V. Suckau (USIMINAS) for sample collection, G. Chen for assistance with LA-ICP-MS analyses, and J. Robbins for data compilation.

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Author notes

  1. Kurt O. Konhauser and Stefan V. Lalonde: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Earth & Atmospheric Sciences, University of Alberta, Edmonton, Alberta T6G 2E3, Canada

    Kurt O. Konhauser, Stefan V. Lalonde & Ernesto Pecoits

  2. Université Européene de Bretagne, Institut Universitaire Européen de la Mer, Plouzané 29280, France

    Stefan V. Lalonde & Olivier J. Rouxel

  3. Department of Earth Sciences, University of California, Riverside, 92521, California, USA

    Noah J. Planavsky & Timothy W. Lyons

  4. Department of Geological Sciences, University of Colorado at Boulder, Boulder, 80309, Colorado, USA

    Stephen J. Mojzsis

  5. IFREMER, Centre de Brest, Plouzané 29280, France

    Olivier J. Rouxel

  6. School of Earth and Environment, University of Western Australia, Crawley, Western Australia 6009, Australia

    Mark E. Barley

  7. Instituto de Geociências, Universidade Federal de Minas Gerais, Belo Horizonte, Minas Gerais 31270-91, Brazil

    Carlos Rosìere

  8. Department of Geology, Lakehead University, Thunder Bay, Ontario P7B 5E1, Canada

    Phillip W. Fralick

  9. Department of Geosciences, The Pennsylvania State University, University Park, 16827, Pennsylvania, USA

    Lee R. Kump

  10. Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2 Canada

    Andrey Bekker

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Contributions

Samples were provided by K.O.K., N.J.P., E.P., S.J.M., O.J.R., M.E.B., C.R., P.W.F. and A.B.; K.O.K. conceived the study; E.P. and N.J.P. performed the geochemical analyses; and S.L. conducted the data reduction and statistical analyses. K.O.K., S.V.L. and N.J.P. produced the manuscript with significant contributions from all co-authors. Specifically, insights into the geological setting for a number of samples were provided by E.P., M.E.B., C.R., P.W.F. and A.B.; use of geochemical proxies to assess Palaeoproterozoic weathering and seawater composition by T.W.L., O.J.R., L.R.K. and A.B.; and the timing and duration of the GOE by S.J.M., L.R.K. and A.B.

Corresponding author

Correspondence to Kurt O. Konhauser.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Figures 1-5 with legends, a legend for Supplementary Table 1 (see separate excel file), Supplementary Table 2, a Supplementary Discussion with Supplementary Notes and Data. There are also additional references throughout. (PDF 3399 kb)

Supplementary Table 1

This table shows Cr, Ti, and Al concentrations in iron formation (BIF and GIF) through time. Also included are Phanerozoic ironstones and hydrothermal marine precipitates. (XLS 286 kb)

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Konhauser, K., Lalonde, S., Planavsky, N. et al. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event. Nature 478, 369–373 (2011). https://doi.org/10.1038/nature10511

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