¹ M.A. van Zuilen,¹ P. Philippot,² M.J. Whitehouse,^3,4 A. Lepland

¹ Géobiosphère Actuelle & Primitive, Institut de Physique du Globe de Paris, Sorbonne Paris Cité, UnivParis Diderot, UMR 7154 CNRS, F-75005 Paris, France
² Swedish Museum of Natural History, Box 50007, SE104-05 Stockholm, Sweden
³ Geological Survey of Norway, Leiv Eirikssons vei 39, 7491 Trondheim, Norway
⁴ Tallinn University of Technology, Institute of Geology, 19086 Tallinn, Estonia

Theoretical and experimental studies have shown that atmospheric SO2 isotopologue self-shielding effects in the 190-220 nm region of the solar spectrum are the likely cause for mass independent fractionation of sulfur isotopes (S-MIF). The main products of this photochemical reaction – SO3 and S0 – typically define a compositional array of ca. Δ33S/δ34S = 0.06-0.14. This is at odds with the generally observed trend in Archean sulfides, which broadly defines an array of ca. Δ33S/δ34S = 0.9. Various explanations have been proposed, including a diminution of δ34S caused by chemical and biogenic mass-dependent fractionation of sulfur isotopes (S-MDF), mixing with photolytic products produced during felsic volcanic events, or partial blocking of the low-wavelength part of the spectrum due to the presence of reduced atmospheric gases or an organic haze. Early in Earth history large meteorite impacts would have ejected dust and gas clouds into the atmosphere that shielded solar radiation and affected global climate. It is thus likely that at certain time intervals of high meteorite flux the atmosphere was significantly perturbed, having an effect on atmospheric photochemistry and possibly leaving anomalous sulfur isotopic signatures in the rock record. Here we describe the sulfur isotopic signatures in sulfides of spherule beds S2, S3 and S4 of the Barberton Greenstone Belt, South Africa. In particular, in spherule bed S3 – and to a lesser extent S4 – a trend of ca. Δ33S/δ34S = 0.23 is observed that closely follows the expected trend for SO2-photolysis in the 190-220 nm spectral range. This suggests that an impact dust cloud (deposited as spherule beds), which sampled the higher region of the atmosphere, specifically incorporated products of SO2 photolysis in the 190-220 nm range, and blocked photochemical reactions at higher wavelengths (250-330 nm band). By implication, the generally observed Archaean trend appears to be the result of mixing of different MIF-S sources arising from a variety of photochemical reactions that took place in the lower part of the atmosphere.

Reference
van Zuilen P, Philippot P, Whitehouse MJ, Lepland A (2014) Sulfur Isotope Mass-Independent Fractionation in Impact Deposits of the 3.2 Billion-year-old Mapepe Formation, Barberton Greenstone Belt, South Africa. Geochimica et Cosmochimica Acta (in Press).

Link to Article [DOI: 10.1016/j.gca.2014.07.018]

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