Calibration of the carbonate `clumped isotope' paleotemperature proxy using mollusc shells and benthic foraminiferal tests

It has recently been shown that the carbonate `clumped isotope' thermometer can provide temperature constraints that depend only on the isotopic composition of carbonate (in particular, on the proportion of 13C and 18O that form bonds with each other), and that do not require assumptions about the isotopic composition of the water in which the carbonate formed (Ghosh et al., 2006). Furthermore, this novel method permits the calculation of seawater δ18O based on the clumped isotope temperature estimates and the simultaneously obtained δ18O of carbonate, thereby enabling the extraction of global ice volume estimates for both the recent and distant geologic past. Here we present clumped isotope analyses of several naturally occurring marine carbonates that calcified at known temperatures in the modern ocean. First, we analyzed benthic foraminiferal tests from six high-quality multicore tops collected in the Florida Strait, spanning a temperature range of 9.3-20.2 degrees C. Second, we analyzed shallow-water mollusc shells from a variety of different climate regimes, spanning a temperature range of 2.5-26.0 degrees C. We find that the calcitic foraminiferal species Cibicidoides spp. agrees well with the inorganic calcite precipitation experiments of Ghosh et al. (2006), while the aragonitic species Hoeglundina elegans is significantly offset. Similarly, clumped isotope results obtained from aragonitic mollusc shells also reveal an offset from the Ghosh et al. (2006) trend, although the offset observed in mollusc aragonite is quite different in nature from that observed in foraminiferal aragonite. Assuming our estimates of the growth temperatures of these naturally occurring organisms are correct, these results suggest that there are vital effects associated with the stable isotope compositions of the aragonite-precipitating organisms examined in this study; further work will be required to determine their cause. Nevertheless, the internal coherence of trends for these materials indicates that clumped isotope analyses of aragonitic molluscs and the tests of the benthic foraminiferal species Cibicidoides spp. and Hoeglundina elegans can be used to reconstruct bottom water temperatures, seawater δ18O values, and global ice volumes.