Seasonal temperature changes obtained from carbonate clumped isotopes of annually laminated tufas from Japan: discrepancy between natural and synthetic calcites

Carbonate clumped isotopes provide a novel paleo-thermometer that does not require knowledge of the isotopic compositions of environmental water. Despite considerable effort, there are substantial inter-laboratory disagreements in empirical calibrations between the abundance anomaly of the clumped isotopes (Δ47) and absolute temperature, and discrepancies in paleo-temperature estimates from natural samples. In this study, clumped isotopes using two types of 17O corrections were analyzed for two sample sets of synthetic calcites and tufas collected monthly from two sites in southwest Japan with known δ18O values and temperatures of parent water. These measurements form the basis for two new temperature calibrations of carbonate clumped isotopes, the first from our Kyushu University laboratory in Japan. The calcites synthesized at four different temperatures (2.9–61.0 °C) yield a temperature-Δ47 relationship of Δ47=0.0354±0.0013×106/T2+0.290±0.015 (R2 = 0.986), which is indistinguishable from the calibrations of other recent studies based on acid digestion experiments at high temperature (70–100 °C).