Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Bajnai, D., Guo, W., Spötl, C., Coplen, T. B., Methner, K., Löffler, N., Krsnik, E., Gischler, E., Hansen, M., Henkel, D., Price, G. D., Raddatz, J., Scholz, D., & Fiebig, J. Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures. Nature Communications, 11(1), (2020): 4005, doi:10.1038/s41467-020-17501-0.Surface temperature is a fundamental parameter of Earth’s climate. Its evolution through time is commonly reconstructed using the oxygen isotope and the clumped isotope compositions of carbonate archives. However, reaction kinetics involved in the precipitation of carbonates can introduce inaccuracies in the derived temperatures. Here, we show that dual clumped isotope analyses, i.e., simultaneous ∆47 and ∆48 measurements on the single carbonate phase, can identify the origin and quantify the extent of these kinetic biases. Our results verify theoretical predictions and evidence that the isotopic disequilibrium commonly observed in speleothems and scleractinian coral skeletons is inherited from the dissolved inorganic carbon pool of their parent solutions. Further, we show that dual clumped isotope thermometry can achieve reliable palaeotemperature reconstructions, devoid of kinetic bias. Analysis of a belemnite rostrum implies that it precipitated near isotopic equilibrium and confirms the warmer-than-present temperatures during the Early Cretaceous at southern high latitudes.This work became possible through DFG grant “INST 161/871-1” and the Investment in Science Fund at Woods Hole Oceanographic Institution. The authors would like to thank Sven Hofmann and Manuel Schumann for their assistance in the joint Goethe University – Senckenberg BiK-F Stable Isotope Facility at the Institute of Geosciences, Goethe University Frankfurt. K.M. acknowledges funding through “DFG ME 4955/1-1”, E.K. through “DFG MU 2845/6-1”, D.S. through “DFG SCHO 1274/8-1” and “DFG SCHO 1274/11-1”, and M.H. through “DFG HA 8694/1-1”. C.S. acknowledges funding from the University of Innsbruck. A review of the manuscript by David Evans on behalf of the USGS is acknowledged