Globally asynchronous sulphur isotope signals require re-definition of the Great Oxidation Event

Abstract

The Great Oxidation Event (GOE) has been defined as the time interval when sufficient atmospheric oxygen accumulated to prevent the generation and preservation of mass-independent fractionation of sulphur isotopes (MIF-S) in sedimentary rocks. Existing correlations suggest that the GOE was rapid and globally synchronous. Here we apply sulphur isotope analysis of diagenetic sulphides combined with U-Pb and Re-Os geochronology to document the sulphur cycle evolution in Western Australia spanning the GOE. Our data indicate that, from ~2.45 Gyr to beyond 2.31 Gyr, MIF-S was preserved in sulphides punctuated by several episodes of MIF-S disappearance. These results establish the MIF-S record as asynchronous between South Africa, North America and Australia, argue for regional-scale modulation of MIF-S memory effects due to oxidative weathering after the onset of the GOE, and suggest that the current paradigm of placing the GOE at 2.33-2.32 Ga based on the last occurrence of MIF-S in South Africa should be re-evaluated.

Fig. 1

New age-calibrated correlation of Late Archaean to Paleoproterozoic sedimentary successions. The Re-Os sulphide age from this study is shown as 2.31 Ga*. Other age constraints are labelled accordingly. Ages with no reference can be found in Rasmussen et al.. The inferred Great Oxidation Event (GOE*) from this study is shown as a ~300 Myr interval based on combined age, sulphur isotope and stratigraphic data. Other GOEs inferred from previous studies are labelled accordingly. The vertical arrow labelled Makganyene refers to the range of age inferred for the Makganyene glacial deposit based on a new U-Pb age of the Ongeluk Volcanics, Transvaal Supergroup, South Africa. MIF, mass-independent fractionation of sulphur isotopes; MDF, mass-dependent fractionation of sulphur isotopes. The mixed light blue-red domain labelled (MDF) shown at the top of the Turee Creek Group (this study), in the Whaleback Member of the Brockman Formation and McRae Shale Formation of the Hamersley Group, and at the base of the Huronian sedimentary column^–, corresponds to sedimentary horizons in which strongly attenuated Δ³³S and Δ³³S/Δ³⁶S systematics are attributed to increases in pO₂ above 10^–5 to 10⁻² PAL (see text). Hamersley Basin: McRS, McRae Shale Formation, Br, Brockman Formation, WW, Weeli Wolli Formation, Wo, Woongarra Rhyolite, Boo, Boolgeeda Iron Fm., Kun, Kungarra Fm., MBM, Meteorite Bore Member, Ko, Koolbye Fm., Ka, Kazput Fm., BRG, Beasley River Quartzite, CSB, Cheela Springs Basalt. Huronian Supergroup: Li, Livingstone Creek Fm., Th, Thessalon Fm., Ma, Matinenda Fm., McK, McKim Fm., RL, Ramsay Lake Fm., Pe, Pecors Fm., Mi, Mississagi, Fm., Br, Bruce Fm., Es, Espanola Fm., Se, Serpent Fm., Go, Gowganda Fm., Lo, Lorrain Fm., GL, Gordon Lake Fm., BR, Bar River Fm. Eastern Transvaal Basin: Mal, Malmani Fm., Pen, Penge Iron Fm., To, Tongwane Fm., Dui, Duitschland Fm., TH, Timeball Hill Fm., Bo, Boshoek Fm., HV, Hekpoort Volcanics

Fig. 2

Sulphur content and δ³⁴S and Δ³³S profiles of sulphides in the Turee Creek drill cores and associated δ³⁴S-Δ³³S and Δ³³S-Δ³⁶S compositional diagrams. Red dots, bulk analysis; white dots, mean value of in situ analysis for each sample; grey dots, individual spot analysis using the SHRIMP-SI (error bars are standard deviation of 1σ, see Methods). The grey shaded areas in the δ³⁴S and Δ³³S profiles represent the range of individual spot analysis for each sample. The two blue-shaded areas labelled (i) below 130 m depth in T1 and (ii) below 145 m depth in T3 are discussed in the text. ARA, Archaean Reference Array. MDF, mass-dependent fractionation of sulphur isotopes. The stratigraphic section of the Turee Creek Group on the left is modified after Van Kranendonk and Mazumder. Re-Os age of 2312.7 ± 5.6 Ma is from this study. Other age constraints are labelled accordingly. Abbreviations associated with the stratigraphic section are as follows: WR, Woongarra Rhyolite, B Fm, Boolgeeda Iron Fm., Kun, Kungarra Fm., MBM1 and 2, two diamictite horizons of the Meteorite Bore Member, KFm, Koolbye Fm., Ka, Kazput Fm., BRQ, Beasley River Quartzite, CSB, Cheela Springs Basalt

Fig. 3

δ³⁴S and Δ³³S profiles of sulphides in drill core T1 and associated δ³⁴S-Δ³³S and Δ³³S-Δ³⁶S compositional diagrams. a, b Samples of the Boolgeeda and Kungarra Formations characterized by a limited range of δ³⁴S values, small ³³S-anomalies and plotting on the Archaean reference array (ARA) with a slope of approximately −1 in a Δ³³S-Δ³⁶S diagram. c–f Sedimentary intervals (151.59–153.56 and 158.98–160.57) or individual samples (130.39 and 172.2) showing variable δ³⁴S values, near-zero Δ³³S values and plotting on the MDF Δ³³S-Δ³⁶S array of slope approximately −7 (light blue areas labelled c–f on the δ³⁴S and Δ³³S profiles). Red dots, bulk analysis; white dots, mean value of in situ analysis for each sample; grey dots, individual spot analysis using the SHRIMP-SI (error bars are standard deviation of 1σ, see Methods). Black and grey dots in c correspond to core and rim S-isotope composition, respectively (see text). The grey shaded areas in the δ³⁴S and Δ³³S profiles represent the range of individual spot analysis for each sample. The stratigraphic column below 130 m depth (Boolgeeda IF) corresponds to the domain (i) discussed in the text and shown in Fig. 2

Fig. 4

δ³⁴S and Δ³³S profiles of sulphides in drill core T3 and associated δ³⁴S-Δ³³S and Δ³³S-Δ³⁶S compositional diagrams. Red dots, bulk analysis; white dots, mean value of in situ analysis for each sample; grey dots, individual spot analysis using the SHRIMP-SI (error bars are standard deviation of 1σ, see Methods). The grey shaded areas in the δ³⁴S and Δ³³S profiles represent the range of individual spot analysis for each sample. ARA, Archaean Reference Array, MDF, mass-dependent fractionation of sulphur isotopes, KFm, quartzite of the Koolbye Formation. The stratigraphic column below 145 m depth corresponds to the domain (ii) discussed in the text and shown in Fig. 2

Fig. 5

δ³⁴S and Δ³³S profiles of sulphides in drill core T2 and associated δ³⁴S-Δ³³S and Δ³³S-Δ³⁶S compositional diagrams. Red dots, bulk analysis; white dots, mean value of in situ analysis for each sample; grey dots, individual point analysis using the SHRIMP-SI (error bars are standard deviation of 1σ, see Methods). The grey shaded areas in the δ³⁴S and Δ³³S profiles represent the range of individual point analysis for each sample. ARA, Archaean Reference Array, MDF, mass-dependent fractionation of sulphur isotopes. Sulphide Re-Os date of 2312.7 ± 5.6 Ma is from this study. Zircon U-Pb date of 2340 ± 22 Ma is from Caquineau et al.. The black and blue stars adjacent to the lithologic column correspond to the samples used for Re-Os (blue) and U-Pb (black) dating