The Sensitivity of Aragonite U/Ca Ratio to Seawater Carbonate Ion Concentration: Insight From Abiogenic Precipitation Experiments and Application to Coral Biomineralization

Abstract:

The U/Ca ratio of aragonite coral skeleton has been shown to correlate with both temperature and seawater carbonate chemistry. However, U/Ca has not been conclusively linked to carbonate chemistry and/or temperature in laboratory experiments. We have performed abiogenic precipitation experiments designed to evaluate the sensitivity of U partitioning between aragonite and seawater to temperature, pH, and the concentration of carbonate ion in seawater. Aragonite was precipitated from seawater by addition of carbonate alkalinity at rates set to maintain stable carbonate chemistry during precipitation. Experiments were conducted between 20-40 °C, pH 7.8-9.0, and carbonate ion concentration 600-2600 µmol kg^-1. Mineralogies of the precipitates were identified by Raman spectrometry and U/Ca ratios of the bulk precipitate and fluid were determined by solution ICP-MS. Our results show that the U/Ca ratio of aragonite precipitated from an infinite reservoir of seawater decreases with increasing carbonate ion concentration, and is independent of pH and temperature. Using our abiogenic results as a basis for interpreting coral skeletal chemistry, we model the coral biomineralization process to show that the U/Ca ratio of coral skeleton reflects a calcifying fluid with carbonate ion concentration of at least 1000 µmol kg^-1, several times greater than ambient seawater. Further, we show that the coral biomineralization response to environmental changes can be linked to changes in calcifying fluid composition via skeletal U/Ca ratios.