Tracing Earth's O-2 evolution using Zn/Fe ratios in marine carbonates

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 palaeoredox records in time and space. Here we explore the use of Zn/Fe ratios to infer the evolution of atmospheric O-2 through time, based on marine carbonate rocks that are well characterised in terms of depositional age, environmental setting, and diagenetic history. While Fe and Zn in the shallow ocean are mainly sourced from hydrothermal inputs, their redox sensitivities differ significantly, so that geological intervals with higher O-2 would be characterised 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 pO(2) levels, providing a secular record of atmospheric O-2 over the past 3.5 billion years. In particular, we corroborate an earlier proposal that for much of the Proterozoic Eon, O-2 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 longterm redox evolution of the oceans and the rise of atmospheric O-2.