Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Evidence from massive siderite beds for a CO2-rich atmosphere before ~ 1.8 billion years ago

Abstract

It is generally thought that, in order to compensate for lower solar flux and maintain liquid oceans on the early Earth, methane must have been an important greenhouse gas before 2.2 billion years (Gyr) ago1,2,3,4,5. This is based upon a simple thermodynamic calculation that relates the absence of siderite (FeCO3) in some pre-2.2-Gyr palaeosols to atmospheric CO2 concentrations that would have been too low to have provided the necessary greenhouse effect1. Using multi-dimensional thermodynamic analyses and geological evidence, we show here that the absence of siderite in palaeosols does not constrain atmospheric CO2 concentrations. Siderite is absent in many palaeosols (both pre- and post-2.2-Gyr in age) because the O2 concentrations and pH conditions in well-aerated soils have favoured the formation of ferric (Fe3+)-rich minerals, such as goethite, rather than siderite. Siderite, however, has formed throughout geological history in subsurface environments, such as euxinic seas, where anaerobic organisms created H2-rich conditions. The abundance of large, massive siderite-rich beds in pre-1.8-Gyr sedimentary sequences and their carbon isotope ratios indicate that the atmospheric CO2 concentration was more than 100 times greater than today, causing the rain and ocean waters to be more acidic than today. We therefore conclude that CO2 alone (without a significant contribution from methane) could have provided the necessary greenhouse effect to maintain liquid oceans on the early Earth.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Proposed models for the evolution of atmospheric CO2 and CH4.
Figure 2: Thermodynamic conditions for the formation of siderite.
Figure 3: Comparison of the carbon isotopic compositions (δ13C values) of carbonates in various rocks.

Similar content being viewed by others

References

  1. Rye, R., Kuo, P. & Holland, H. D. Atmospheric carbon dioxide concentrations before 2.2 billion years ago. Nature 378, 603–605 (1995)

    Article  ADS  CAS  Google Scholar 

  2. Rye, R. & Holland, H. D. Paleosols and the evolution of atmospheric oxygen: A critical review. Am. J. Sci. 298, 621–672 (1998)

    Article  ADS  CAS  Google Scholar 

  3. Catling, D., Zahnle, K. & McKay, C. Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth. Science 293, 839–843 (2001)

    Article  ADS  CAS  Google Scholar 

  4. Pavlov, A. A., Brown, L. L. & Kasting, J. F. UV shielding of NH3 and O2 by organic hazes in the Archean atmosphere. J. Geophys. Res. 106, 23267–23287 (2001)

    Article  ADS  CAS  Google Scholar 

  5. Pavlov, A. A., Kasting, J. F., Eigenbrode, J. L. & Freeman, K. H. Organic haze in Earth's early atmosphere: Source of low-13C Late Archaean kerogens? Geology 29, 1003–1006 (2001)

    Article  ADS  CAS  Google Scholar 

  6. Kasting, J. Theoretical constraints on oxygen and carbon dioxide concentrations in the Precambrian atmosphere. Precambr. Res. 34, 205–229 (1987)

    Article  ADS  CAS  Google Scholar 

  7. Ohmoto, H. Evidence in pre-2.2 Ga paleosols for the early evolution of atmospheric oxygen and terrestrial biota. Geology 24, 1135–1138 (1996)

    Article  ADS  CAS  Google Scholar 

  8. Langumuir, D. Aqueous Environmental Geochemistry 600 (Prentice-Hall, Upper Saddle River, 1997)

    Google Scholar 

  9. Panahi, A., Young, G. M. & Rainbird, R. H. Behavior of trace elements (including REE) during pedogenesis and diagenetic alteration of an Archean granite near Ville Marie, Quebéc, Canada. Geochim. Cosmochim. Acta 64, 2199–2220 (2000)

    Article  ADS  CAS  Google Scholar 

  10. Marmo, J. S. in Early Organic Evolution (ed. Schidlowski, M.) 41–66 (Springer, Berlin, 1992)

    Book  Google Scholar 

  11. Beukes, N. J., Dorland, H., Gutzmer, J., Nedachi, M. & Ohmoto, H. Tropical laterites, life on land, and the history of atmospheric oxygen in the paleoproterozoic. Geology 30, 491–494 (2002)

    Article  ADS  CAS  Google Scholar 

  12. Watanabe, Y., Stewart, B. W. & Ohmoto, H. Organic- and carbonate-rich soil formation 2.6 billion years ago at Schagen, East Transvaal district, South Africa. Geochim. Cosmochim. Acta 68, 2129–2151 (2004)

    Article  ADS  CAS  Google Scholar 

  13. Knauth, L. P. & Lowe, D. R. High Archean climatic temperature inferred from oxygen isotope geochemistry of cherts in the 3.5 Ga Swaziland Supergroup, South Africa. Geol. Soc. Am. Bull. 115, 566–580 (2003)

    Article  ADS  CAS  Google Scholar 

  14. Moore, S. E., Ferrell, R. E. & Aharon, P. Diagenetic siderite and other ferroan carbonates in a modern subsiding marsh sequence. J. Sedim. Petrol. 62, 357–366 (1992)

    CAS  Google Scholar 

  15. Mozley, P. & Wersin, P. Isotopic composition of siderite as an indicator of depositional environment. Geology 20, 817–820 (1992)

    Article  ADS  CAS  Google Scholar 

  16. Kimberley, M. M. Exhalative origins of iron formations. Ore Geol. Rev. 5, 13–145 (1989)

    Article  Google Scholar 

  17. Ohmoto, H. When did the atmosphere become oxic? Geochem. News 93, 12–13, 26–27 (1997)

    Google Scholar 

  18. Beukes, N. J., Klein, C., Kaufman, A. J. & Hayes, J. M. Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transistion from limestone to iron-formation deposition, Transvaal Supergroup, South Africa. Econ. Geol. 85, 663–690 (1990)

    Article  CAS  Google Scholar 

  19. Becker, R. H. & Clayton, R. N. Carbon isotope evidence for the origin of a banded iron-formation in western Australia. Geochim. Cosmochim. Acta 36, 577–595 (1972)

    Article  ADS  CAS  Google Scholar 

  20. Baur, M. E., Hayes, J. M., Studley, S. A. & Walter, M. R. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia. Econ. Geol. 80, 270–282 (1985)

    Article  CAS  Google Scholar 

  21. Goodwin, A. M., Thode, H. G., Chou, C.-L. & Karkhansis, S. N. Chemostratigraphy and origin of the late Archaean siderite-pyrite-rich Helen Iron Formation, Michipicoten belt, Canada. Can. J. Earth Sci. 22, 72–84 (1985)

    Article  ADS  CAS  Google Scholar 

  22. Carrigan, W. J. & Cameron, E. M. Petrological and stable isotope studies of carbonate and sulfide minerals from the Gunflint Formation, Ontario: evidence for the origin of early Proterozoic iron-formation. Precambr. Res. 52, 347–380 (1991)

    Article  ADS  CAS  Google Scholar 

  23. Winter, B. L. & Knauth, P. Stable isotope geochemistry of cherts and carbonates from the 2.0 Ga Gunflint Iron Formation: implications for the depositional setting, and the effects of diagenesis and metamorphism. Precambr. Res. 59, 283–313 (1992)

    Article  ADS  CAS  Google Scholar 

  24. Schidlowski, M. et al. in Early Organic Evolution (ed. Schidlowski, M.) 147–175 (Springer, Berlin, 1992)

    Google Scholar 

  25. Shields, G. & Veizer, J. Precambrian marine carbonate isotope database: Version 1.1. Geochem. Geophys. Geosyst. 3, 1–12 (2002)

    Article  Google Scholar 

  26. Hayes, J. M. in Early Life on Earth (ed. Bengtson, S.) 220–236 (Columbia Univ. Press, New York, 1994)

    Google Scholar 

  27. Pavlov, A. A., Hurtgen, M. T., Kasting, J. F. & Arthur, M. A. Methane-rich Proterozoic atmosphere? Geology 31, 87–90 (2003)

    Article  ADS  CAS  Google Scholar 

  28. Stumm, W. & Morgan, J. J. Aquatic Chemistry, Chemical Equilibria and Rates in Natural Waters 3rd edn 1022 (Wiley, New York, 1996)

    Google Scholar 

  29. Geochemist's Workbench Version 4 (RockWare Inc., Golden, 2002).

  30. Ohmoto, H. Redox state of the Archaean atmosphere: Evidence from detrital heavy minerals in ca. 3250–2750 Ma sandstones from the Pilbara Craton, Australia. Geology 27, 1151–1152 (1999)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

We are grateful to K. Hayashi and T. Kakegawa for assistance in petrographical and geochemical investigations of the siderite samples. We thank M. Arthur, H. Barnes, E. Bazilevskaya, P. Deines, L. Kump, A. Lasaga, K. Spangler and K. Yamaguchi for comments on earlier drafts. This work was supported by grants to H.O. from the NSF (Geochemistry Program) and NASA (Astrobiology and Exobiology programmes).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hiroshi Ohmoto.

Ethics declarations

Competing interests

The authors declare that they have no competing financial interests.

Supplementary information

Supplementary Table 1

This table lists the sample locality, stratigraphic position, chemical compositions (Ca, Mg, Fe and Mn ratios), isotopic compositions (δ13C & δ18O) and carbonate content of the 381 powdered samples of pre-1.8 Gyr Fe-rich carbonates that were analysed in this study. (XLS 74 kb)

Supplementary Table 2

This table lists the δ13C values of kerogen (organic matter) in eleven samples of pre-1.8 Gyr siderite-rich formations that were analysed in this study. (XLS 8 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ohmoto, H., Watanabe, Y. & Kumazawa, K. Evidence from massive siderite beds for a CO2-rich atmosphere before ~ 1.8 billion years ago. Nature 429, 395–399 (2004). https://doi.org/10.1038/nature02573

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature02573

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing