Mass-independent fractionation of sulfur isotopes in sulfides from the pre-3770 Ma Isua Supracrustal Belt, West Greenland

Redox chemistry of the coupled atmosphere–hydrosphere system has coevolved with the biosphere, from global anoxia in the Archean to an oxygenated Proterozoic surface environment. However, to trace these changes to the very beginning of the rock record presents special challenges. All known Eoarchean ( c . 3850–3600 Ma) volcanosedimentary successions (i.e. supracrustal rocks) are restricted to high-grade gneissic terranes that seldom preserve original sedimentary structures and lack primary organic biomarkers. Although complicated by metamorphic overprinting, sulfur isotopes from Archean supracrustal rocks have the potential to preserve signatures of both atmospheric chemistry and metabolic fractionation from the original sediments. We present a synthesis of multiple sulfur isotope measurements ( 32 S, 33 S and 34 S) performed on sulfides from amphibolite facies banded iron-formations (BIFs) and ferruginous garnet-biotite (metapelitic) schists from the pre-3770 Ma Isua Supracrustal Belt (ISB) in West Greenland. Because these data come from some of the oldest rocks of interpretable marine sedimentary origin, they provide the opportunity to (i) explore for possible biosignatures of sulfur metabolisms in early life; (ii) assess changes in atmospheric redox chemistry from ∼ 3.8 Ga; and (iii) lay the groundwork to elucidate sulfur biogeochemical cycles on the early Earth. We find that sulfur isotope results from Isua do not unambiguously indicate microbially induced sulfur isotopic fractionation at that time. A significantly expanded data set of ∆ 33 S analyses for Isua dictates that the atmosphere was devoid of free oxygen at time of deposition and also shows that the effects of post-depositional metamorphic remobilization and/or dilution can be traced in mass-independently fractionated sulfur isotopes. Received 1 February 2006; accepted 7 July 2006 Corresponding author: D. Papineau. Tel.: 202-478-8917; fax: 202-478-8901; e-mail: [email protected].