Calibration of the carbonate ‘clumped isotope’ paleothermometer for otoliths

Paleothermometry is an essential tool for understanding past changes in climate. The ‘carbonate clumped isotope thermometer’ is a temperature proxy related to ordering of 13C and 18O in the carbonate lattice (based on measurements of 13C18O16O in CO2 produced by acid digestion of carbonate). This thermometer has been previously calibrated for inorganic calcite and aragonitic corals [Ghosh P., Adkins J., Affek H., Balta B., Guo W. F., Schauble E. A., Schrag D., and Eiler J. M. (2006) C-13–O-18 bonds in carbonate minerals: a new kind of paleothermometer. Geochim. Cosmochim. Acta70 (6), 1439–1456]. Here we determine the relationship between growth temperatures of aragonitic fish otoliths and abundances of 13C18O16O produced by acid digestion of those otoliths. Our calibration is based on analyses of otoliths from six species from four genera of modern fish sampled from a latitudinal transect of the Atlantic Ocean between 54° S and 65° N, plus one species from the tropical western Pacific. The temperatures at which fish otoliths precipitated were estimated by the mean temperature in the waters in which they lived, averaged over their estimated lifetimes. Estimated growth temperatures of our samples vary between 2 and 25 °C. Our results show that the abundance of 13C18O16O in CO2 produced by acid digestion of fish otolith aragonite is a function of growth temperature, following the relationship: Δ47=0.0568×106T2-0.0045, where Δ47 is the enrichment, in per mil, of 13C18O16O in CO2 relative to the amount expected for a stochastic (random) distribution of isotopes among all CO2 isotopologues, and T is the temperature in Kelvin. This relationship closely approaches that previously documented for inorganic calcite and aragonitic coral (Ghosh et al., 2006).