A high-resolution Sulphur Isotope Record of Neoarchean Atmospheric Chemistry: Deciphering the Driver of Atmospheric Bi-stability in the Prelude to the GOE.

Gareth James Izon, University of St Andrews, St Andrews, KY16, United Kingdom, Aubrey Zerkle, University of St Andrews, St Andrews, United Kingdom, Robert Newton, University of Leeds, School of Earth and Environment, Leeds, United Kingdom, Simon Poulton, University of Leeds, Leeds, United Kingdom, Jennifer L Eigenbrode, NASA Goddard Space Flight Center, Greenbelt, MD, United States, James Farquhar, University of Maryland College Park, Department of Geology, College Park, United States and Mark Claire, University of St Andrews, Department of Earth and Environmental Sciences, St Andrews, KY16, United Kingdom
Abstract:
Quantitative estimates of the composition of the Late Archean atmosphere are integral to deciphering the drivers of planetary oxygenation in the early Paleoproterozoic. However, the majority of geochemical proxies from marine sediments only inform on planetary redox via inference, making direct constraints on the ancient atmosphere difficult to place. Fortunately, the quadruple S-isotope (QSI) record (δ34S, Δ33S, and Δ36S) is implicitly tied to the composition of the ancient atmosphere.

We have generated coupled QSI and δ13COrg records from two cores through the Transvaal basin in South Africa (GKF01 and BH1-Sacha) and from three time-equivalent cores through the Hammersley basin in Western Australia. These records reveal similar, apparently synchronous, co-variation between deviations from “typical” Neoarchean Δ36S/Δ33S values and negative δ13COrg values (C-S anomalies). We have interpreted these trends to reflect increased incorporation of 13C-depleted substrates (methane) into sedimentary matter following apparently episodically enhanced methanogenesis in the prelude to the GOE. These records suggest the terminal Neoarchean atmosphere operated in a bi-stable fashion, oscillating between a clear skies and organic-rich hazy state (Zerkle et al., 2010; Izon et al., in review).

We speculate that these C-S anomalies reflect enhanced nutrient availability, facilitating the proliferation of an oxygenic photosynthetic/methanogenic biosphere, concomitantly amplifying biogenic CH4 and O2 fluxes and altering atmospheric chemistry. Here we present a new S- and C-isotope data set, derived at unprecedented resolution, encompassing the youngest C-S anomaly identified in core GKF01. These analyses will be combined with Fe-speciation and trace-metal data to elucidate whether atmospheric methane levels were regulated by climatically driven changes in nutrient fluxes to the marine biosphere. Taken together, our research serves as an initial foray to determine how, and why, the early Earth redox balance shifted, initiating oxygenation and ultimately spawning a habitable planet capable of supporting macroscopic life.

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