Carbonate clumped isotope variability in shallow water corals: Temperature dependence and growth-related vital effects

Abstract

Geochemical variations in shallow water corals provide a valuable archive of paleoclimatic information. However, biological effects can complicate the interpretation of these proxies, forcing their application to rely on empirical calibrations. Carbonate clumped isotope thermometry (Δ47) is a novel paleotemperature proxy based on the temperature dependent “clumping” of 13C–18O bonds. Similar Δ47-temperature relationships in inorganically precipitated calcite and a suite of biogenic carbonates provide evidence that carbonate clumped isotope variability may record absolute temperature without a biological influence. However, large departures from expected values in the winter growth of a hermatypic coral provided early evidence for possible Δ47 vital effects. Here, we present the first systematic survey of Δ47 in shallow water corals. Sub-annual Red Sea Δ47 in two Porites corals shows a temperature dependence similar to inorganic precipitation experiments, but with a systematic offset toward higher Δ47 values that consistently underestimate temperature by ∼8°C. Additional analyses of Porites, Siderastrea, Astrangia and Caryophyllia corals argue against a number of potential mechanisms as the leading cause for this apparent Δ47 vital effect including: salinity, organic matter contamination, alteration during sampling, the presence or absence of symbionts, and interlaboratory differences in analytical protocols. However, intra- and inter-coral comparisons suggest that the deviation from expected Δ47 increases with calcification rate. Theoretical calculations suggest this apparent link with calcification rate is inconsistent with pH-dependent changes in dissolved inorganic carbon speciation and with kinetic effects associated with CO2 diffusion into the calcifying space. However, the link with calcification rate may be related to fractionation during the hydration/hydroxylation of CO2 within the calcifying space. Although the vital effects we describe will complicate the interpretation of Δ47 as a paleothermometer in shallow water corals, it may still be a valuable paleoclimate proxy, particularly when applied as part of a multi-proxy approach.