Testing Novel pH Proxies through Inorganic Calcite Precipitations and K/Pg Foraminifera

Ocean pH proxies help constrain the carbon system in the paleocean and can be used to infer atmospheric CO2 when coupled with estimates of total alkalinity, aqueous pCO2 or dissolved inorganic carbon. This project investigates two novel pH proxies (cerium abundance and kinetically-controlled oxygen isotopes) through a series of precipitations of inorganic calcite, as well as the previously established boron isotope pH proxy. Precipitations are performed using varied pH and carbonate saturation states that span the range of typical ocean values as well as a 'free drift' that allows pH and saturation state to vary. The light rare earth element cerium speciates, depending on local oxidation-reduction conditions, between the soluble Ce3+ and highly insoluble Ce4+ ions, causing a relative depletion of cerium in ocean water. This project demonstrates how a suite rare earth elements, including cerium, partitions into inorganic calcite and how partitioning varies with changing pH and carbonate saturation state. Oxygen isotope fractionation is primarily controlled by temperature, but this project examines how pH and carbonate saturation state correlate with oxygen isotope values under kinetic conditions during the initial stage of precipitation. The effect of diagenesis on each proxy is simulated by dissolution of precipitated calcite in a pressure vessel. Results from the precipitations are used to inform a record of well-preserved benthic and planktonic foraminifera from DSDP Site 356 that range in age from the K/Pg boundary to the period when the δ13C gradient between the surface and deep ocean returned to pre-event levels. The pH record is used to infer the magnitude and length of the perturbation to the oceanic carbon system following the extinction event, particularly in terms of export productivity.