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.

Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry

Abstract

The evolution of the Earth’s atmosphere is marked by a transition from an early atmosphere with very low oxygen content to one with an oxygen content within a few per cent of the present atmospheric level. Placing time constraints on this transition is of interest because it identifies the time when oxidative weathering became efficient, when ocean chemistry was transformed by delivery of oxygen and sulphate, and when a large part of Earth’s ecology changed from anaerobic to aerobic1. The observation of non-mass-dependent sulphur isotope ratios in sedimentary rocks more than 2.45 billion years (2.45 Gyr) old and the disappearance of this signal in younger sediments is taken as one of the strongest lines of evidence for the transition from an anoxic to an oxic atmosphere around 2.45 Gyr ago1,2,3,4,5. Detailed examination of the sulphur isotope record before 2.45 Gyr ago also reveals early and late periods of large amplitude non-mass-dependent signals bracketing an intervening period when the signal was attenuated5,6,7,8,9. Until recently, this record has been too sparse to allow interpretation, but collection of new data has prompted some workers8 to argue that the Mesoarchaean interval (3.2–2.8 Gyr ago) lacks a non-mass-dependent signal, and records the effects of earlier and possibly permanent oxygenation of the Earth’s atmosphere. Here we focus on the Mesoarchaean interval, and demonstrate preservation of a non-mass-dependent signal that differs from that of preceding and following periods in the Archaean. Our findings point to the persistence of an anoxic early atmosphere, and identify variability within the isotope record that suggests changes in pre-2.45-Gyr-ago atmospheric pathways for non-mass-dependent chemistry and in the ultraviolet transparency of an evolving early atmosphere.

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

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Figure 1: Compilation of Δ 33 S versus age for rock samples.
Figure 2: Plot of Δ 33 S versus δ 34 S that illustrates the fields defined by pre- and post-2.45-Gyr-ago samples.
Figure 3: Plot of Δ 36 S versus Δ 33 S for mass-dependent and mass-independent data.

References

  1. Holland, H. D. The oxygenation of the atmosphere and oceans. Phil. Trans. R. Soc. B 361, 903–915 (2006)

    CAS  Article  Google Scholar 

  2. Farquhar, J., Savarino, J., Airieau, S. & Thiemens, M. H. Observation of wavelength-sensitive mass-independent sulfur isotope effects during SO2 photolysis: Implications for the early atmosphere. J. Geophys. Res. E 106, 32829–32839 (2001)

    ADS  CAS  Article  Google Scholar 

  3. Pavlov, A. A. & Kasting, J. F. Mass-independent fractionation of sulfur isotopes in Archean sediments: Strong evidence for an anoxic Archean atmosphere. Astrobiology 2, 27–41 (2002)

    ADS  CAS  Article  Google Scholar 

  4. Zahnle, K., Claire, M. & Catling, D. The loss of mass-independent fractionation in sulfur due to a Palaeoproterozoic collapse of atmospheric methane. Geobiology 4, 271–283 (2006)

    CAS  Article  Google Scholar 

  5. Farquhar, J., Bao, H. & Thiemens, M. Atmospheric influence of Earth’s earliest sulfur cycle. Science 289, 756–758 (2000)

    ADS  CAS  Article  Google Scholar 

  6. Ono, S. et al. New insights into Archean sulfur cycle from mass-independent sulfur isotope records from the Hamersley Basin, Australia. Earth Planet. Sci. Lett. 213, 15–30 (2003)

    ADS  CAS  Article  Google Scholar 

  7. Ono, S., Beukes, N. J., Rumble, D. & Fogel, M. L. Early evolution of atmospheric oxygen from multiple sulfur and carbon isotope records of the 2.9 Ga Mozaan Group of the Pongola Supergroup, Southern Africa. South Afr. J. Geol. 109, 97–108 (2006)

    CAS  Article  Google Scholar 

  8. Ohmoto, H., Watanabe, Y., Ikemi, H., Poulson, S. R. & Taylor, B. E. Sulphur isotope evidence for an oxic Archaean atmosphere. Nature 442, 908–911 (2006)

    ADS  CAS  Article  Google Scholar 

  9. Kasting, J. F. & Ono, S. Palaeoclimates: the first two billion years. Phil. Trans. R. Soc. B 361, 917–929 (2006)

    CAS  Article  Google Scholar 

  10. Farquhar, J. et al. Multiple sulfur isotopic interpretations of biosynthetic pathways. Geobiology 1, 27–36 (2003)

    CAS  Article  Google Scholar 

  11. Johnston, D. T. et al. Active microbial sulfur disproportionation in the Mesoproterozoic. Science 310, 1477–1479 (2005)

    ADS  CAS  Article  Google Scholar 

  12. Bekker, A. et al. Dating the rise of atmospheric oxygen. Nature 427, 117–120 (2003)

    ADS  Article  Google Scholar 

  13. Romero, A. B. & Thiemens, M. H. Mass-independent sulfur isotopic compositions in present-day sulfate aerosols. J. Geophys. Res. D 108 doi: 10.1029/2003JD003660 (2003)

  14. Savarino, J., Romero, A., Cole-Dai, J., Bekki, S. & Thiemens, M. H. UV induced mass-independent sulfur isotope fractionation in stratospheric volcanic sulfate. Geophys. Res. Lett. 30 doi: 10.1029/2003GL018134 (2003)

  15. Baroni, M., Thiemens, M. H., Delmas, R. J. & Savarino, J. Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions. Science 315, 84–87 (2007)

    ADS  CAS  Article  Google Scholar 

  16. Ono, S., Wing, B., Johnston, D., Farquhar, J. & Rumble, D. Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles. Geochim. Cosmochim. Acta 70, 2238–2252 (2006)

    ADS  CAS  Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

  18. Farquhar, J., Savarino, J., Jackson, T. L. & Thiemens, M. H. Evidence of atmospheric sulphur in the martian regolith from sulphur isotopes in meteorites. Nature 404, 50–52 (2000)

    ADS  CAS  Article  Google Scholar 

  19. Ono, S., Shanks, W. C., Rouxel, O. J. & Rumble, D. 33S constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides. Geochim. Cosmochim. Acta 71, 1170–1182 (2007)

    ADS  CAS  Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

  21. Farquhar, J., Bao, H. M., Thiemens, M. H., Hu, G. X. & Rumble, D. Questions regarding Precambrian sulfur isotope fractionation — Response. Science 292, U6–U7 (2001)

    Google Scholar 

  22. Farquhar, J. & Wing, B. A. in Mineral Deposits and Earth Evolution (eds McDonald, I., Boyce, A. J., Butler, I. B., Herrington, R. J. & Polya, D. A.) 167–177 (Spec. Publ. 248, Geological Society, London, 2005)

    Google Scholar 

  23. Whitehouse, M. J. et al. Integrated Pb- and S-isotope investigation of sulphide minerals from the early Archaean of southwest Greenland. Chem. Geol. 222, 112–131 (2005)

    ADS  CAS  Article  Google Scholar 

  24. Papineau, D., Mojzsis, S. J., Coath, C. D., Karhu, J. A. & McKeegan, K. D. Multiple sulfur isotopes of sulfides from sediments in the aftermath of Paleoproterozoic glaciations. Geochim. Cosmochim. Acta 69, 5033–5060 (2005)

    ADS  CAS  Article  Google Scholar 

  25. Mojzsis, S. J., Coath, C. D., Greenwood, J. P., McKeegan, K. D. & Harrison, T. M. Mass-independent isotope effects in Archean (2.5 to 3.8 Ga) sedimentary sulfides determined by ion microprobe analysis. Geochim. Cosmochim. Acta 67, 1635–1658 (2003)

    ADS  CAS  Article  Google Scholar 

  26. Hu, G. X., Rumble, D. & Wang, P. L. An ultraviolet laser microprobe for the in situ analysis of multisulfur isotopes and its use in measuring Archean sulfur isotope mass-independent anomalies. Geochim. Cosmochim. Acta 67, 3101–3118 (2003)

    ADS  CAS  Article  Google Scholar 

  27. Ono, S., Wing, B., Johnston, D., Farquhar, J. & Rumble, D. Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles. Geochim. Cosmochim. Acta 70, 2238–2252 (2006)

    ADS  CAS  Article  Google Scholar 

  28. Cates, N. L. & Mojzsis, S. J. Chemical and isotopic evidence for widespread Eoarchean metasedimentary enclaves in southern West Greenland. Geochim. Cosmochim. Acta 70, 4229–4257 (2006)

    ADS  CAS  Article  Google Scholar 

  29. Papineau, D. & Mojzsis, S. J. Mass-independent fractionation of sulfur isotopes in sulfides from the pre-3770 Ma Isua Supracrustal Belt, West Greenland. Geobiology 4, 227–238 (2006)

    CAS  Article  Google Scholar 

  30. 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)

    CAS  Article  Google Scholar 

  31. Ohmoto, H., Watanabe, Y., Ikemi, H., Poulson, S. R. & Taylor, B. E. Sulphur isotope evidence for an oxic Archaean atmosphere. Nature 442, 908–911 (2006)

    ADS  CAS  Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

  33. Farquhar, J. et al. Multiple sulfur isotopic interpretations of biosynthetic pathways Geobiology . 1, 27–36 (2003)

  34. Johnston, D. T. et al. Active microbial sulfur disproportionation in the Mesoproterozoic. Science 310, 1477–1479 (2005)

    ADS  CAS  Article  Google Scholar 

  35. Ono, S., Shanks, W. C., Rouxel, O. J. & Rumble, D. 33S constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides. Geochim. Cosmochim. Acta 71, 1170–1182 (2007)

    ADS  CAS  Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

  37. Thiemens, M. H. Atmosphere science — Mass-independent isotope effects in planetary atmospheres and the early solar system. Science 283, 341–345 (1999)

    ADS  CAS  Article  Google Scholar 

  38. Thiemens, M. H. History and applications of mass-independent isotope effects. Annu. Rev. Earth Planet. Sci. 34, 217–262 (2006)

    ADS  CAS  Article  Google Scholar 

  39. Hulston, J. R. & Thodem, H. G. Variations in S33, S34 and S36 contents of meteorites and their relation to chemical and nuclear effects. J. Geophys. Res. 70, 3475–3484 (1965)

    ADS  CAS  Article  Google Scholar 

  40. Gao, X. & Thiemens, M. H. systematic study of sulfur isotopic composition in iron-meteorites and the occurrence of excess 33S and 36S. Geochim. Cosmochim. Acta 55, 2671–2679 (1991)

    ADS  CAS  Article  Google Scholar 

  41. Farquhar, J., Savarino, J., Airieau, S. & Thiemens, M. H. Observation of wavelength-sensitive mass-independent sulfur isotope effects during SO2 photolysis: Implications for the early atmosphere. J. Geophys. Res. 106, 32829–32839 (2001)

    ADS  CAS  Article  Google Scholar 

Download references

Acknowledgements

This study was supported by funds from the NSF EAR, NASA NAI and NASA EXB progammes (to J.F.), and revisions were undertaken while J.F. was supported by a visiting appointment at the IPG of Paris. Other support for this work came from NSF (A.J.K.) and the DFG (H.S.). The manuscript was improved by reviews and comments from P. Knauth and H. Ohmoto. P. Cartigny is thanked for reading and commenting on the manuscript.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to James Farquhar.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Table 1, Supplementary Notes and additional references. (PDF 67 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Farquhar, J., Peters, M., Johnston, D. et al. Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry. Nature 449, 706–709 (2007). https://doi.org/10.1038/nature06202

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature06202

Further reading

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