Iodine to calcium ratios in marine carbonate as a paleo-redox proxy during oceanic anoxic events

Periods of globally distributed extreme oxygen depletion, so-called oceanic anoxic events (OAEs), have been recognized in the Mesozoic geological record and appear to be characteristic of episodes of extreme warmth. Here we explore the application of iodine/calcium ratios (I/Ca) in marine carbonate as a new geochemical proxy to constrain seawater redox change, and provide additional insights into the response of ocean chemistry to ancient climatic warming. Iodine has long been known as a redox-sensitive and biophilic element, mainly present as iodate and iodide in seawater, iodate converting to iodide under anoxic conditions. Laboratory experiments growing calcite crystals from solutions spiked with iodate show that this is the ionic species incorporated into the carbonate structure, likely substituting for the CO(3)(2-)ion. A fall in the I/Ca ratio measured in carbonates formed in shallow water by marine calcifiers during the early Toarcian and Cenomanian-Turonian OAEs is interpreted both as a response to a decrease in the iodate/iodide ratio in ocean waters and the drawdown of the global iodine inventory under conditions of accelerated organic-matter burial. The results suggest that I/Ca ratios in carbonates may be used to monitor seawater oxidation levels throughout Earth history.