Tracing Earth’s O2 evolution using Zn/Fe ratios in marine carbonates

Abstract

Through Earth history, atmospheric oxygen has increased from initial values near zero to its present day level of about 21% by volume; concomitantly, changes in ocean redox conditions have fundamentally altered global biogeochemical cycles. While there is a reasonable understanding of where oxygen history begins and ends, the quantitative timetable of oxygenation that links the endpoints has proven contentious. Equilibrium between marine surface environments and the overlying atmosphere suggests that carbonate-based redox proxies could refine paleoredox records in time and space. Here we explore the use of Zn/Fe ratios to infer the evolution of atmospheric O2 through time, based on marine carbonate rocks that are well characterized in terms of depositional age, environmental setting, and diagenetic history. While Fe and Zn in the shallow ocean is mainly sourced from hydrothermal inputs, their redox sensitivities differ significantly, so that geological intervals with higher O2 would be characterized by stepped increases in Zn/Fe as preserved in shallow marine carbonates. Therefore, Zn/Fe analyses of ancient carbonates allow us to constrain past atmospheric pO2 levels, providing a secular record of atmospheric O2 over the past 3.5 billion years. In particular, we corroborate an earlier proposal that for much of the Proterozoic Eon, O2 levels were as low as 0.1-1% of present atmospheric level. We conclude that Zn/Fe in shallow marine carbonate rocks has potential to provide a quantitative tracer for the long-term redox evolution of the oceans and the rise of atmospheric O2.