Tracing Earth's O2 Evolution Using Zn/Fe Systematics in Carbonates

Redox-sensitive major and trace elements in iron formations and black shales have been developed as proxies to reconstruct paleoenvironmental history in deep time [1, 2]. Many Proterozoic successions, however, contain abundant limestone and dolomite, and so carbonate-based redox proxies could help greatly to expand the paleoredox record in time and space. Most paleoenvironmental research on sedimentary rocks focuses on individual stratigraphic successions; here, however, we adopt a complementary strategy, analyzing a large suite of Mesozoic, Paleozoic, and Precambrian samples that enables us to make global statistical statements about elemental abundances through time. Here we explore the use of Zn/Fe ratios as proxies to trace the evolution of redox profiles in marine basins, based on analysis of major and trace element concentrations in micro-drilled carbonate rocks that are well characterized in terms of stratigraphy, environmental setting, and petrology. Consistent with previous studies, we observed a two step increase of mean Zn/Fe ratios in carbonates through Earth history: at the Paleoproterozoic Great Oxidation Event and during the later Neoproterozoic Oxidation Event. Diagenetic alteration is always an issue for carbonate rocks, and so we carefully screened these carbonates for possible late diagenetic effects and hydrothermal alteration. Individual samples may still bear a trace element signature of early diagenesis, but our statistical approach indicates that despite diagenetic issues, meaningful trends can be discerned in the data. It is unlikely that changes in depositional environment, secular evolution of the mantle, and/or directional change in continental inputs greatly influenced the observed trace element behavior. Therefore, Zn/Fe ratios in shallow marine carbonates have the potential to provide a useful tracer for the redox evolution of the oceans and the rise of atmospheric O2. References:[1] Sahoo et al. (2012) Ocean oxygenation in the wake of the Marinoan glaciation. Nature 489:546-549. [2] Konhauser et al. (2009) Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event. Nature 458:750-753.