Nature 427, 117 - 120 (08 January 2004); doi:10.1038/nature02260

Dating the rise of atmospheric oxygen

A. BEKKER¹, H. D. HOLLAND¹, P.-L. WANG², D. RUMBLE III², H. J. STEIN³, J. L. HANNAH³, L. L. COETZEE⁴ & N. J. BEUKES⁴

¹ Department of Earth and Planetary Sciences, 20 Oxford Street, Harvard University, Cambridge, Massachusetts 02138, USA
² Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road, Washington DC 20015, USA
³ AIRIE Program, Department of Geosciences, Colorado State University, Fort Collins, Colorado 80523-1482, USA
⁴ Department of Geology, Rand Afrikaans University, Auckland Park 2006, Johannesburg, South Africa

Correspondence and requests for materials should be addressed to A.B. (abekker@fas.harvard.edu).

Several lines of geological and geochemical evidence indicate that the level of atmospheric oxygen was extremely low before 2.45 billion years (Gyr) ago, and that it had reached considerable levels by 2.22 Gyr ago. Here we present evidence that the rise of atmospheric oxygen had occurred by 2.32 Gyr ago. We found that syngenetic pyrite is present in organic-rich shales of the 2.32-Gyr-old Rooihoogte and Timeball Hill formations, South Africa. The range of the isotopic composition of sulphur in this pyrite is large and shows no evidence of mass-independent fractionation, indicating that atmospheric oxygen was present at significant levels (that is, greater than 10^-5 times that of the present atmospheric level) during the deposition of these units. The presence of rounded pebbles of sideritic iron formation at the base of the Rooihoogte Formation and an extensive and thick ironstone layer consisting of haematitic pisolites and oölites in the upper Timeball Hill Formation indicate that atmospheric oxygen rose significantly, perhaps for the first time, during the deposition of the Rooihoogte and Timeball Hill formations. These units were deposited between what are probably the second and third of the three Palaeoproterozoic glacial events.