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Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes

Nature volume 461, pages 250–253 (2009)Cite this article

Abstract

Geochemical data1,2,3,4 suggest that oxygenation of the Earth’s atmosphere occurred in two broad steps. The first rise in atmospheric oxygen is thought to have occurred between ∼2.45 and 2.2 Gyr ago1,5, leading to a significant increase in atmospheric oxygen concentrations and concomitant oxygenation of the shallow surface ocean. The second increase in atmospheric oxygen appears to have taken place in distinct stages during the late Neoproterozoic era (∼800–542 Myr ago)3,4, ultimately leading to oxygenation of the deep ocean ∼580 Myr ago3, but details of the evolution of atmospheric oxygenation remain uncertain. Here we use chromium (Cr) stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of the Earth’s atmosphere–hydrosphere system. The geochemical behaviour of Cr is highly sensitive to the redox state of the surface environment because oxidative weathering processes produce the oxidized hexavalent [Cr(VI)] form. Oxidation of reduced trivalent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. Our fractionated Cr isotope data indicate the accumulation of Cr(VI) in ocean surface waters ∼2.8 to 2.6 Gyr ago and a likely transient elevation in atmospheric and surface ocean oxygenation before the first great rise of oxygen 2.45–2.2 Gyr ago (the Great Oxidation Event)1,5. In ∼1.88-Gyr-old BIFs we find that Cr isotopes are not fractionated, indicating a decline in atmospheric oxygen. Our findings suggest that the Great Oxidation Event did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, we observe strong positive fractionations in Cr isotopes (δ53Cr up to +4.9‰), providing independent support for increased surface oxygenation at that time, which may have stimulated rapid evolution of macroscopic multicellular life3,4,6.

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Figure 1: Schematic of the surface chemistry of chromium.
Figure 2: Graph showing the key aspects of the Precambrian history of hexavalent chromium in sea water.
Figure 3: Stratigraphy of the Gunflint Formation and its transition into the Rove Formation 29 and sample horizons.

References

  1. Bekker, A. et al. Dating the rise of atmospheric oxygen. Nature 427, 117–120 (2004)

    Article  CAS  Google Scholar 

  2. Rouxel, O. J., Bekker, A. & Edwards, K. J. Iron isotope constraints on the Archean and Paleoproterozoic ocean redox state. Science 307, 1088–1091 (2005)

    Article  CAS  Google Scholar 

  3. Canfield, D. E., Poulton, S. W. & Narbonne, G. M. Late-Neoproterozoic deep-ocean oxygenation and the rise of animal life. Science 315, 92–95 (2007)

    Article  CAS  Google Scholar 

  4. Fike, D. A. et al. Oxidation of the Ediacaran Ocean. Nature 444, 744–747 (2006)

    Article  CAS  Google Scholar 

  5. Bekker, A. & Kaufman, A. Oxidative forcing of global climate change: a biogeochemical record across the oldest Paleoproterozoic ice age in North America. Earth Planet. Sci. Lett. 258, 486–499 (2007)

    Article  CAS  Google Scholar 

  6. Canfield, D. E. & Teske, A. Late Proterozoic rise in atmospheric oxygen concentration inferred from phylogenetic and sulphur-isotope studies. Nature 382, 127–132 (1996)

    Article  CAS  Google Scholar 

  7. Oze, C., Bird, D. K. & Fendorf, S. Genesis of hexavalent chromium from natural sources in soil and groundwater. Proc. Natl Acad. Sci. USA 104, 6544–6549 (2007)

    Article  CAS  Google Scholar 

  8. Campbell, J. A. & Yeats, P. A. Dissolved chromium in the northwest Atlantic Ocean. Earth Planet. Sci. Lett. 53, 427–433 (1981)

    Article  CAS  Google Scholar 

  9. Sikora, E. R., Johnson, T. M. & Bullen, T. D. Microbial mass-dependent fractionation of chromium isotopes. Geochim. Cosmochim. Acta 72, 3631–3641 (2008)

    Article  CAS  Google Scholar 

  10. Ellis, A. S., Johnson, T. M. & Bullen, T. D. Chromium isotopes and the fate of hexavalent chromium in the environment. Science 295, 2060–2062 (2002)

    Article  CAS  Google Scholar 

  11. Eary, L. E. & Rai, D. Kinetics of chromate reduction by ferrous-ions derived from hematite and biotite at 25°C. Am. J. Sci. 289, 180–213 (1989)

    Article  CAS  Google Scholar 

  12. Fendorf, S. E. Surface-reactions of chromium in soils and waters. Geoderma 67, 55–71 (1995)

    Article  CAS  Google Scholar 

  13. Sass, B. M. & Rai, D. Solubility of amorphous chromium(III)-iron(III) hydroxide solid-solutions. Inorg. Chem. 26, 2228–2232 (1987)

    Article  CAS  Google Scholar 

  14. Eary, L. E. & Rai, D. Chromate removal from aqueous wastes by reduction with ferrous ion. Environ. Sci. Technol. 22, 972–977 (1988)

    Article  CAS  Google Scholar 

  15. Schauble, E., Rossman, G. R. & Taylor, H. P. Theoretical estimates of equilibrium chromium-isotope fractionations. Chem. Geol. 205, 99–114 (2004)

    Article  CAS  Google Scholar 

  16. Izbicki, J. A. et al. Chromium, chromium isotopes and selected elements, western Mojave Desert, USA. Appl. Geochem. 23, 1325–1352 (2008)

    Article  CAS  Google Scholar 

  17. Ellis, A. S., Johnson, T. M. & Bullen, T. D. Using chromium stable isotope ratios to quantify Cr(VI) reduction: lack of sorption effects. Environ. Sci. Technol. 38, 3604–3607 (2004)

    Article  CAS  Google Scholar 

  18. Schoenberg, R. et al. The stable Cr isotope inventory of solid Earth reservoirs determined by double spike MC-ICP-MS. Chem. Geol. 249, 294–306 (2008)

    Article  CAS  Google Scholar 

  19. Anbar, A. D. et al. A whiff of oxygen before the Great Oxidation Event? Science 317, 1903–1906 (2007)

    Article  CAS  Google Scholar 

  20. Kaufman, A. et al. Late Archean biosheric oxygenation and atmospheric evolution. Science 317, 1900–1903 (2007)

    Article  CAS  Google Scholar 

  21. Wille, M. et al. Evidence for a gradual rise of oxygen between 2.6 and 2.5 Ga from Mo isotopes and Re-PGE signatures in shales. Geochim. Cosmochim. Acta 71, 2417–2435 (2007)

    Article  CAS  Google Scholar 

  22. Kamber, B. S. & Whitehouse, M. J. Micro-scale sulphur isotope evidence for sulphur cycling in the late Archean shallow ocean. Geobiology 5, 5–17 (2007)

    Article  CAS  Google Scholar 

  23. Isley, A. E. & Abbott, D. H. Plume-related mafic volcanism and the deposition of banded iron formation. J. Geophys. Res. 104, 15461–15477 (1999)

    Article  CAS  Google Scholar 

  24. Canfield, D. E. The early history of atmospheric oxygen: homage to Robert A. Garrels. Annu. Rev. Earth Planet. Sci. 33, 1–36 (2005)

    Article  CAS  Google Scholar 

  25. Johnston, D. T. et al. Evolution of the oceanic sulfur cycle at the end of the Paleoproterozoic. Geochim. Cosmochim. Acta 70, 5723–5739 (2006)

    Article  CAS  Google Scholar 

  26. Farquhar, J. & Wing, B. A. Multiple sulfur isotopes and the evolution of the atmosphere. Earth Planet. Sci. Lett. 213, 1–13 (2003)

    Article  CAS  Google Scholar 

  27. Canfield, D. E. A new model for Proterozoic ocean chemistry. Nature 396, 450–453 (1998)

    Article  CAS  Google Scholar 

  28. Scott, C. et al. Tracing the stepwise oxygenation of the Proterozoic ocean. Nature 452, 456–459 (2008)

    Article  CAS  Google Scholar 

  29. Poulton, S. W., Fralick, P. W. & Canfield, D. E. The transition to a sulphidic ocean similar to 1.84 billion years ago. Nature 431, 173–177 (2004)

    Article  CAS  Google Scholar 

  30. Gaucher, C. et al. Acritarchs of Las Ventanas Formation (Ediacaran, Uruguay): implications for the timing of coeval rifting and glacial events in western Gondwana. Gondwana Res. 13, 488–501 (2008)

    Article  Google Scholar 

  31. Connelly, J. N. et al. A method for purifying Lu and Hf for analyses by MC-ICP-MS using TODGA resin. Chem. Geol. 233, 126–136 (2006)

    Article  CAS  Google Scholar 

  32. Kalsbeek, F. & Frei, R. The Mesoproterozoic Midsommerso dolerites and associated high-silica intrusions, North Greenland: crustal melting, contamination and hydrothermal alteration. Contrib. Mineral. Petrol. 152, 89–110 (2006)

    Article  CAS  Google Scholar 

  33. Ball, J. W. & Bassett, R. L. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis. Chem. Geol. 168, 1–2 (2000)

    Article  Google Scholar 

  34. Frei, R. & Rosing, M. T. Search for traces of the late heavy bombardment on Earth—results from high precision chromium isotopes. Earth Planet. Sci. Lett. 236, 28–40 (2005)

    Article  CAS  Google Scholar 

  35. Shields, W. R. et al. Absolute isotopic abundance ratios and atomic weight of a reference sample of chromium. J. Res. Natl Bureau Standards A70, 193–197 (1966)

    Article  Google Scholar 

Download references

Acknowledgements

This study was funded by the Danish Agency for Science, Technology and Innovation and by the Danish National Research Foundation (Danmarks Grundforskningsfond).We thank R. Schoenberg for sharing his Cr double spike with us and for contributions during many thematic and analytical discussions. To add to our own collection, critical samples were provided by C. Klein, A. Polat, P. S. Dahl, S. K. Mondal, H.-J. Hansen and E. F. Duke. Help with the clean-laboratory chemical separation procedures by T. Larsen is acknowledged. T. Leeper helped with the mass spectrometry and kept the mass spectrometer in excellent condition.

Author Contributions R.F. and C.G. collected critical Neoproterozoic samples during fieldwork in Uruguay in 2006. D.E.C. and S.W.P. provided the important sediment samples from the Gunflint and Rove formations. Methods development and thermal ionization mass spectrometer analytical work was conducted by R.F. The manuscript was produced by significant contributions by R.F., D.E.C., S.W.P. and C.G. Furthermore, D.E.C. and S.W.P. provided deeper insights into Proterozoic atmospheric and deep ocean oxygenation models and stimulated discussion of the early Earth system evolution.

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Authors and Affiliations

  1. Institute of Geography and Geology and Nordic Center for Earth Evolution (NordCEE), University of Copenhagen, Øster Voldgade 10, 1350 Copenhagen, Denmark ,

    Robert Frei & Claudio Gaucher

  2. Departamento de Geología, Facultad de Ciencias, Iguá 4225, 11400 Montevideo, Uruguay,

    Claudio Gaucher

  3. School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK ,

    Simon W. Poulton

  4. Nordic Center for Earth Evolution (NordCEE) and Institute of Biology, University of Southern Denmark, Campusvej 55, 5230 Odense, Denmark

    Don E. Canfield

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  1. Robert Frei
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  4. Don E. Canfield
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Correspondence to Robert Frei.

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Frei, R., Gaucher, C., Poulton, S. et al. Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes. Nature 461, 250–253 (2009). https://doi.org/10.1038/nature08266

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