Subaqueous carbonate speleothems as paleotemperature archives – clumped isotope thermometry and stable isotope compositions of inclusion-hosted water

Clumped isotope measurements of carbonates and stable isotope analyses of water trapped in fluid inclusions are both promising techniques to determine carbonate formation temperatures. Cave-hosted carbonate deposits (speleothems) are excellent targets for such studies, but kinetic fractionations and diagenetic influences frequently deteriorate the temperature data obtained from these methods. However, subaqueous carbonate deposits may provide reliable data, as kinetic fractionations are less significant in underwater environments. In this study, subaqueous speleothems, whose formation temperatures were directly measured in the water, were investigated. Additionally, temperatures calculated from the oxygen isotope fractionations between calcite and fluid inclusion-hosted water were compared with clumped isotope temperatures obtained for subaqueous carbonate formations in cave-hosted lakes. The clumped isotope temperatures fit the measured and calculated fluid inclusion temperatures within the analytical precisions. Carbonate deposits formed at elevated temperatures (~50°C or above) may undergo post-formational calcite-water oxygen isotope exchange, altering the composition of the inclusion-hosted water. In contrast, subaqueous speleothems formed at about 20-25°C appear to preserve the primary isotopic compositions. Our study shows that subaqueous carbonate speleothems are useful targets for clumped isotope and inclusion water analyses, making them valuable paleotemperature archives.