Carbonic anhydrase, coral calcification and a new model of stable isotope vital effects

Abstract

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed “vital effects”. A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ¹⁸O and δ¹³C in a range of values that are depleted from inorganic calcite/aragonite. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO₂(aq)-HCO₃⁻ inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon (DIC) pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep-sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO₂(aq)-HCO₃⁻ inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ¹⁸O-δ¹³C correlation. Differences in CA activity in the biomineralization process can possibly explain the observed range of δ¹⁸O-δ¹³C slopes in different calcifying organisms. A mechanistic understanding of stable isotope vital effects with numerical models can help us develop better paleoceanographic tracers.