EGU General Assembly 2020
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.

Combined clumped isotope measurements resolve kinetic biases in carbonate formation temperatures

David Bajnai1,2, Weifu Guo3, Niklas Löffler1,4, Katharina Methner4, Emilija Krsnik4, Tyler B. Coplen5, Eberhard Gischler1, Maximilian Hansen6, Daniela Henkel7, Gregory D. Price8, Jacek Raddatz1, Denis Scholz6, and Jens Fiebig1
David Bajnai et al.
  • 1Institute of Geosciences, Goethe University Frankfurt, Frankfurt am Main, Germany
  • 2Institute of Geology and Mineralogy, University of Cologne, Cologne, Germany
  • 3Department of Geology and Geophysics, Woods Hole Oceanographic Institution, Woods Hole, MA, USA
  • 4Senckenberg Biodiversity and Climate Research Centre (SBiK-F), Frankfurt am Main, Germany
  • 5U.S. Geological Survey, Reston, VA, USA
  • 6Institute of Geosciences, Johannes Gutenberg University Mainz, Mainz, Germany
  • 7GEOMAR Helmholtz Centre for Ocean Research, Kiel, Germany
  • 8School of Geography, Earth and Environmental Sciences, University of Plymouth, Plymouth, UK

Reaction kinetics involved in the precipitation of carbonates can introduce large scatter and inaccuracies in the temperatures derived from their δ18O and ∆47 values. Advances in mass spectrometry instrumentation recently enabled high-precision analysis of the 18O–18O clumping in carbonate minerals (48), despite the relatively low natural abundance of 12C18O18O, the main isotopologue contributing to the 48 signal (1). Measurements of 48, when combined with 47, can yield additional insights into kinetic effects and the carbonate formation environment (2).

Here we report high-precision 47 and 48 values of speleothem carbonates, modern coral skeletons, a brachiopod, and a belemnite. We constrained equilibrium in 47 vs 48 space by anchoring empirically derived 47 vs temperature and 48 vs temperature relationships to a Devils Hole mammillary calcite, known to be precipitated at extremely slow rates at a constant 33.7(±0.8) °C and water oxygen isotope composition. Our results, compared to theoretical predictions, provide the most substantial evidence to date that the isotopic disequilibrium commonly observed in speleothems and scleractinian coral skeletons is inherited from the dissolved inorganic carbon pool of their parent solutions. Data from an ancient belemnite imply it precipitated near isotopic equilibrium and confirm the warmer-than-present temperatures at Early Cretaceous southern high latitudes. The presence of similar kinetic departure in a brachiopod but not in a belemnite suggests that the current discrepancy between belemnite and brachiopod-based temperature estimates in the geologic record is most likely related to a greater kinetic bias in the isotopic composition of brachiopod shells.

We demonstrate that the combined clumped isotope method makes it possible to identify carbonates that did not precipitate in thermodynamic equilibrium from their parent water. Our results highlight the potential that the combined clumped isotope analyses hold for accurate paleoclimate reconstructions and the identification of the kinetic fractionation processes dominant in carbonate (bio)mineralisation.

(1) Fiebig et al. (2019),

(2) Guo, W. (2020),

How to cite: Bajnai, D., Guo, W., Löffler, N., Methner, K., Krsnik, E., Coplen, T. B., Gischler, E., Hansen, M., Henkel, D., Price, G. D., Raddatz, J., Scholz, D., and Fiebig, J.: Combined clumped isotope measurements resolve kinetic biases in carbonate formation temperatures, EGU General Assembly 2020, Online, 4–8 May 2020, EGU2020-3051,, 2020.


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