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.
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References
Holland, H. D. The oxygenation of the atmosphere and oceans. Phil. Trans. R. Soc. B 361, 903–915 (2006)
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)
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)
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)
Farquhar, J., Bao, H. & Thiemens, M. Atmospheric influence of Earth’s earliest sulfur cycle. Science 289, 756–758 (2000)
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)
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)
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)
Kasting, J. F. & Ono, S. Palaeoclimates: the first two billion years. Phil. Trans. R. Soc. B 361, 917–929 (2006)
Farquhar, J. et al. Multiple sulfur isotopic interpretations of biosynthetic pathways. Geobiology 1, 27–36 (2003)
Johnston, D. T. et al. Active microbial sulfur disproportionation in the Mesoproterozoic. Science 310, 1477–1479 (2005)
Bekker, A. et al. Dating the rise of atmospheric oxygen. Nature 427, 117–120 (2003)
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)
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)
Baroni, M., Thiemens, M. H., Delmas, R. J. & Savarino, J. Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions. Science 315, 84–87 (2007)
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)
Farquhar, J. & Wing, B. A. Multiple sulfur isotopes and the evolution of the atmosphere. Earth Planet. Sci. Lett. 213, 1–13 (2003)
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)
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)
Johnston, D. T. et al. Evolution of the oceanic sulfur cycle at the end of the Paleoproterozoic. Geochim. Cosmochim. Acta 70, 5723–5739 (2006)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
Johnston, D. T. et al. Evolution of the oceanic sulfur cycle at the end of the Paleoproterozoic. Geochim. Cosmochim. Acta 70, 5723–5739 (2006)
Farquhar, J. et al. Multiple sulfur isotopic interpretations of biosynthetic pathways Geobiology . 1, 27–36 (2003)
Johnston, D. T. et al. Active microbial sulfur disproportionation in the Mesoproterozoic. Science 310, 1477–1479 (2005)
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)
Farquhar, J. & Wing, B. A. Multiple sulfur isotopes and the evolution of the atmosphere. Earth Planet. Sci. Lett. 213, 1–13 (2003)
Thiemens, M. H. Atmosphere science — Mass-independent isotope effects in planetary atmospheres and the early solar system. Science 283, 341–345 (1999)
Thiemens, M. H. History and applications of mass-independent isotope effects. Annu. Rev. Earth Planet. Sci. 34, 217–262 (2006)
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)
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)
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)
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.
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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
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DOI: https://doi.org/10.1038/nature06202
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