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Sulphur isotope evidence for an oxic Archaean atmosphere


The presence of mass-independently fractionated sulphur isotopes (MIF-S) in many sedimentary rocks older than 2.4 billion years (Gyr), and the absence of MIF-S in younger rocks, has been considered the best evidence for a dramatic change from an anoxic to oxic atmosphere around 2.4 Gyr ago1,2,3,4,5,6,7,8,9. This is because the only mechanism known to produce MIF-S has been ultraviolet photolysis of volcanic sulphur dioxide gas in an oxygen-poor atmosphere. Here we report the absence of MIF-S throughout 100-m sections of 2.76-Gyr-old lake sediments and 2.92-Gyr-old marine shales in the Pilbara Craton, Western Australia. We propose three possible interpretations of the MIF-S geologic record: (1) the level of atmospheric oxygen fluctuated greatly during the Archaean era; (2) the atmosphere has remained oxic since 3.8 Gyr ago, and MIF-S in sedimentary rocks represents times and regions of violent volcanic eruptions that ejected large volumes of sulphur dioxide into the stratosphere; or (3) MIF-S in rocks was mostly created by non-photochemical reactions during sediment diagenesis, and thus is not linked to atmospheric chemistry.

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Figure 1: MIF-S record.
Figure 2: Stratigraphy of the Pilbara Craton.
Figure 3: S and organic C.
Figure 4: δ 33 S versus δ 34 S relationships.


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We are grateful to D. Walizer, J. McGrorey, A. Klarke, D. Bevacqua and T. Otake for laboratory assistance; to D. Rumble, S. Ono, J. Farquhar, B. Wing and T. Kakegawa for technical advice during the development of analytical techniques; to M. Nedachi, A. Hickman, M. Barley and A. Marshall for their leadership during drilling operations to recover samples for this study; to the Geological Survey of Western Australia for facilitating access to the drilling sites; to T. Engelder for the Devonian black shale samples; to A. Lasaga, T. Fujii, J. Kasting, A. Hickman, S. Kesler, K. Yamaguchi, T. Lyons, B. Runnegar, A. Anbar, H. Naraoka, K. Spangler, P. Knauth and E. Altinok for discussions and review of an earlier manuscript; and to K. Ohmoto and R. Grymes for encouragement. This study was supported by grants to H.O. from the NASA Astrobiology Institute, NASA Exobiology Program and the NSF. Author Contributions H.O. and Y.W. conceived this study; Y.W. and H.I. carried out the analyses in collaboration with S.P. and B.T.; all authors co-wrote the paper.

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Correspondence to Hiroshi Ohmoto.

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Supplementary Notes

This file comprises with 5 sections: The Archaean Biosphere Drilling Project (ABDP); Geologic Setting of Samples; Methods of Analyses; Results of Isotopic, Chemical and Mineralogical Analyses; and Discussion on the Origins of Pyrite Crystals in the Studied Samples. This file also contains Supplementary Figures 1–4 and Supplementary Tables 1 and 2. (PDF 2705 kb)

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Ohmoto, H., Watanabe, Y., Ikemi, H. et al. Sulphur isotope evidence for an oxic Archaean atmosphere. Nature 442, 908–911 (2006).

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