Dual clumped isotope thermometry of coral carbonate

Abstract

The stable (δ18O and δ13C) and clumped (Δ47) isotope compositions of coral carbonate are valuable archives for paleoclimate reconstructions. However, the Δ47-temperature relationships of warm and cold-water corals deviate from that of inorganic carbonate precipitated at equilibrium. Dual clumped isotope thermometry of carbonates (i.e., simultaneous Δ47 and Δ48 measurements on a single carbonate) has the potential to achieve more accurate paleotemperature reconstruction, identifying and correcting for kinetically driven isotopic disequilibrium. Here we present the first extensive dual clumped isotope dataset of coral carbonate, spanning a broad range of cold and warm-water coral species. We confirm that corals are enriched in Δ47 and depleted in Δ48 relative to equilibrium, a pattern corresponding to the mixing of an equilibrium DIC pool with kinetically derived HCO3– produced by hydration and hydroxylation of CO2. Dual clumped isotope measurements of cold-water corals fall on the initial linear portion of model (IsoDIC) predicted departure from equilibrium. The dual clumped isotope composition of cold-water corals, corrected by the model-predicted Δ47/Δ48 offset slope (−0.78), yield accurate reconstruction of coral growth temperature with a precision of <3 °C at the 68% confidence level. In contrast, disequilibrium offsets in the Δ47 and Δ48 of warm-water corals correspond to precipitation from a more equilibrated DIC pool, which we attribute to the action of carbonic anhydrase in the calcifying fluid. It may be possible to correct warm-water coral growth temperatures, using an empirically derived correction (Δ47/ Δ48 offset slope of −0.4). Dual clumped isotope thermometry of coral carbonate opens new possibilities to reconstruct both sea surface temperatures and ocean dynamics of intermediate to deep water masses.