Precise kinetic parameters for thermal resetting of clumped isotope signatures in biogenic and abiogenic calcites
Open accessPublished version of a preprint
Abstract
Carbonate clumped isotope (∆ 47 ) thermometry is a powerful tool to reconstruct paleotemperatures. However, episodes of heating or cooling can alter original ∆ 47 values through diffusive C O bond reordering—i.e., isotopic exchange between neighboring carbonate groups within the mineral lattice—and/or oxygen-isotope exchange between carbonate groups and water (collectively termed “thermal resetting”). Nevertheless, if precise kinetic constraints are available, altered ∆ 47 values can be utilized to reconstruct thermal histories of sedimentary basins or to restore primary ∆ 47 values from carbonates which experienced thermal resetting in their geological history. Here, we present new high-resolution heating experiments on optical (abiogenic) and belemnite (biogenic) calcite. By capturing early signals and conducting experiments at lower temperatures than in previous studies, we derive new precise disordered kinetic parameters for both materials [optical calcite: µ E = 216.47 ± 6.95 kJ mol -1 , σ E = 14.51 ± 1.22 kJ mol -1 , and v 0 = 28.61 ± 1.12 ln(min) -1 ; belemnite calcite: µ E = 180.15 ± 7.94 kJ mol -1 , σ E = 22.24 ± 2.62 kJ mol -1 , and v 0 = 27.76 ± 1.43 ln(min) -1 ]. Additionally, we present new FTIR data on pristine and heated belemnite calcite that confirms the presence of intracrystalline water and organic matter that is suggested to facilitate its faster thermal resetting. Complementary “snapshot” experiments on a diverse suite of materials reveal a systematic difference in thermal resetting behavior between biogenic and abiogenic calcites, highlighting the importance of structural and compositional characteristics in controlling resetting kinetics. These snapshot experiments can complement petrographic and geochemical methods in assessing the pristine nature of calcite samples and provide guidance for selecting the appropriate kinetic parameters for thermal modeling of different calcites.
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Cites
Sample criteria for testing outlying observations
Grubbs, F. E. (1950) · The Annals of Mathematical Statistics · doi:10.1214/aoms/1177729885 · Cited by 1,631 · see citing works
The Bending Mode of Water: A Powerful Probe for Hydrogen Bond Structure of Aqueous Systems
Seki, T., Chiang, K.-Y., Yu, C., Yu, X., Okuno, M., Hunger, J., Nagata, Y., & Bonn, M. (2020) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.0c01259 · Cited by 500 · see citing works
Bernasconi, S. M., Daëron, M., Bergmann, K. D., Bonifacie, M., Meckler, A. N., Affek, H. P., Anderson, N., Bajnai, D., Barkan, E., Beverly, E., et al. (2021) · Geochemistry Geophysics Geosystems · doi:10.1029/2020gc009588 · Cited by 340 · see citing works
Self-citationEquilibrium thermodynamics of multiply substituted isotopologues of molecular gases
Wang, Z., Schauble, E. A., & Eiler, J. M. (2004) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2004.05.039 · Cited by 338 · see citing works
Carbonate clumped isotope bond reordering and geospeedometry
Passey, B. H., & Henkes, G. A. (2012) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2012.07.021 · Cited by 326 · see citing works
Anderson, N. T., Kelson, J. R., Kele, S., Daëron, M., Bonifacie, M., Horita, J., Mackey, T. J., John, C. M., Kluge, T., Petschnig, P., et al. (2021) · Geophysical Research Letters · doi:10.1029/2020gl092069 · Cited by 323 · see citing works
Self-citationBernasconi, S. M., Müller, I. A., Bergmann, K. D., Breitenbach, S. F. M., Fernandez, A., Hodell, D. A., Jaggi, M., Meckler, A. N., Millan, I., & Ziegler, M. (2018) · Geochemistry, Geophysics, Geosystems · doi:10.1029/2017gc007385 · Cited by 301 · see citing works
Self-citationTemperature limits for preservation of primary calcite clumped isotope paleotemperatures
Henkes, G. A., Passey, B. H., Grossman, E. L., Shenton, B. J., Pérez-Huerta, A., & Yancey, T. E. (2014) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2014.04.040 · Cited by 284 · see citing works
Stolper, D. A., & Eiler, J. M. (2015) · American Journal of Science · doi:10.2475/05.2015.01 · Cited by 257 · see citing works
John, C. M., & Bowen, D. (2016) · Rapid Communications in Mass Spectrometry · doi:10.1002/rcm.7720 · Cited by 247 · see citing works
Meckler, A. N., Ziegler, M., Millán, M. I., Breitenbach, S. F. M., & Bernasconi, S. M. (2014) · Rapid Communications in Mass Spectrometry · doi:10.1002/rcm.6949 · Cited by 239 · see citing works
Self-citationAnisotropic lattice distortions in biogenic calcite induced by intra-crystalline organic molecules
Pokroy, B., Fitch, A. N., Marin, F., Kapon, M., Adir, N., & Zolotoyabko, E. (2006) · Journal of Structural Biology · doi:10.1016/j.jsb.2006.03.008 · Cited by 212 · see citing works
Infrared spectra of water. I. Effect of temperature and of H/D isotopic dilution
Maréchal, Y. (1991) · The Journal of Chemical Physics · doi:10.1063/1.461630 · Cited by 207 · see citing works
Physical and Biological Determinants of the Fabrication of Molluscan Shell Microstructures
Checa, A. G. (2018) · Frontiers in Marine Science · doi:10.3389/fmars.2018.00353 · Cited by 176 · see citing works
Bernasconi, S. M., Hu, B., Wacker, U., Fiebig, J., Breitenbach, S. F. M., & Rutz, T. (2013) · Rapid Communications in Mass Spectrometry · doi:10.1002/rcm.6490 · Cited by 166 · see citing works
Self-citationThe Microstructure of Biogenic Calcite: A View by High‐Resolution Synchrotron Powder Diffraction
Pokroy, B., Fitch, A. N., & Zolotoyabko, E. (2006) · Advanced Materials · doi:10.1002/adma.200600714 · Cited by 147 · see citing works
Soluble Organic Matrices of the Calcitic Prismatic Shell Layers of Two Pteriomorphid Bivalves
Dauphin, Y. (2003) · Journal of Biological Chemistry · doi:10.1074/jbc.m204375200 · Cited by 139 · see citing works
Müller, I., Fernandez, A., Radke, J., van Dijk, J., Bowen, D. A., Schwieters, J., & Bernasconi, S. (2017) · Rapid Communications in Mass Spectrometry · doi:10.1002/rcm.7878 · Cited by 138 · see citing works
Self-citationLinking crystal structure with temperature-sensitive vibrational modes in calcium carbonate minerals
Xu, B., & Poduska, K. M. (2014) · Physical Chemistry Chemical Physics · doi:10.1039/c4cp01772b · Cited by 133 · see citing works
Oxygen self-diffusion in calcite: Dependence on temperature and water fugacity
Farver, J. R. (1994) · Earth and Planetary Science Letters · doi:10.1016/0012-821x(94)90092-2 · Cited by 130 · see citing works
A robust calibration of the clumped isotopes to temperature relationship for foraminifers
Meinicke, N., Ho, S. L., Hannisdal, B., Nürnberg, D., Tripati, A., Schiebel, R., & Meckler, A. N. (2020) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.11.022 · Cited by 121 · see citing works
Li, H., Xin, H. L., Kunitake, M. E., Keene, E. C., Muller, D. A., & Estroff, L. A. (2011) · Advanced Functional Materials · doi:10.1002/adfm.201002709 · Cited by 115 · see citing works
Carbon and oxygen diffusion in calcite: Effects of Mn content and P H2O
Kronenberg, A. K., Yund, R. A., & Giletti, B. J. (1984) · Physics and Chemistry of Minerals · doi:10.1007/bf00309248 · Cited by 106 · see citing works
Fernandez, A., Müller, I. A., Rodríguez‐Sanz, L., van Dijk, J., Looser, N., & Bernasconi, S. M. (2017) · Geochemistry, Geophysics, Geosystems · doi:10.1002/2017gc007106 · Cited by 101 · see citing works
Self-citationExperimental calibration of clumped isotope reordering in dolomite
Lloyd, M. K., Ryb, U., & Eiler, J. M. (2018) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2018.08.036 · Cited by 100 · see citing works
Fellin, M. G., Reiners, P. W., Brandon, M. T., Wüthrich, E., Balestrieri, M. L., & Molli, G. (2007) · Tectonics · doi:10.1029/2006tc002085 · Cited by 97 · see citing works
Differences between Bond Lengths in Biogenic and Geological Calcite
Zolotoyabko, E., Caspi, E. N., Fieramosca, J. S., Von Dreele, R. B., Marin, F., Mor, G., Addadi, L., Weiner, S., & Politi, Y. (2010) · Crystal Growth & Design · doi:10.1021/cg901195t · Cited by 94 · see citing works
A disordered kinetic model for clumped isotope bond reordering in carbonates
Hemingway, J. D., & Henkes, G. A. (2021) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2021.116962 · Cited by 93 · see citing works
Self-citationHudson, J. D., & Martill, D. M. (1994) · Journal of the Geological Society · doi:10.1144/gsjgs.151.1.0113 · Cited by 80 · see citing works
Staudigel, P. T., & Swart, P. K. (2016) · Chemical Geology · doi:10.1016/j.chemgeo.2016.09.013 · Cited by 76 · see citing works
Understanding biomineralization in the fossil record
Pérez‐Huerta, A., Coronado, I., & Hegna, T. A. (2018) · Earth-Science Reviews · doi:10.1016/j.earscirev.2018.02.015 · Cited by 67 · see citing works
Munnecke, A., Wright, V. P., & Nohl, T. (2023) · Earth-Science Reviews · doi:10.1016/j.earscirev.2023.104366 · Cited by 59 · see citing works
Frisia, S., Borsato, A., & Hellström, J. (2018) · Earth-Science Reviews · doi:10.1016/j.earscirev.2018.01.014 · Cited by 58 · see citing works
Chen, S., Ryb, U., Piasecki, A. M., Lloyd, M. K., Baker, M. B., & Eiler, J. M. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.05.018 · Cited by 55 · see citing works
Fernandez, A., Korte, C., Ullmann, C. V., Looser, N., Wohlwend, S., & Bernasconi, S. M. (2021) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2020.10.005 · Cited by 50 · see citing works
Self-citationMarine temperatures underestimated for past greenhouse climate
Vickers, M. L., Bernasconi, S. M., Ullmann, C. V., Lode, S., Looser, N., Morales, L. F. G., Price, G. D., Wilby, P. R., Hougård, I. W., Hesselbo, S. P., et al. (2021) · Scientific Reports · doi:10.1038/s41598-021-98528-1 · Cited by 43 · see citing works
Self-citationInfluence of water on clumped-isotope bond reordering kinetics in calcite
Brenner, D. C., Passey, B. H., & Stolper, D. A. (2018) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2017.12.026 · Cited by 41 · see citing works
Revisiting Oxygen‐18 and Clumped Isotopes in Planktic and Benthic Foraminifera
Daëron, M., & Gray, W. R. (2023) · Paleoceanography and Paleoclimatology · doi:10.1029/2023pa004660 · Cited by 40 · see citing works
Looser, N., Petschnig, P., Hemingway, J., Fernández, Á., Morales, L. F. G., Pérez‐Huerta, A., Vickers, M. L., Price, G. D., Schmidt, M. W., & Bernasconi, S. M. (2023) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2023.03.030 · Cited by 31 · see citing works
Self-citationStaudigel, P. T., Davies, A., Bernecker, M., Tagliavento, M., van der Lubbe, J. J. L., Nooitgedacht, C. W., Looser, N., Bernasconi, S. M., Vonhof, H., Price, G. D., et al. (2023) · Geochemistry Geophysics Geosystems · doi:10.1029/2022gc010766 · Cited by 30 · see citing works
Self-citationDavies, A. J., & John, C. M. (2017) · Rapid Communications in Mass Spectrometry · doi:10.1002/rcm.7902 · Cited by 30 · see citing works
Diffusion of C and O in calcite from 0.1 to 200 MPa
Labotka, T. C., Cole, D. R., Riciputi, L. R., & Fayek, M. (2004) · American Mineralogist · doi:10.2138/am-2004-5-614 · Cited by 28 · see citing works
An experimental study of the diffusion of C and O in calcite in mixed CO2-H2O fluid
Labotka, T. C., Cole, D. R., Fayek, M., & Chacko, T. (2011) · American Mineralogist · doi:10.2138/am.2011.3738 · Cited by 27 · see citing works
Nooitgedacht, C. W., van der Lubbe, J. J. L., de Graaf, S., Ziegler, M., Staudigel, P. T., & Reijmer, J. J. G. (2021) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2020.12.008 · Cited by 27 · see citing works
Price, G. D., Hart, M. B., Wilby, P. R., & Page, K. N. (2015) · Palaios · doi:10.2110/palo.2014.106 · Cited by 26 · see citing works
Self-citationRyb, U., Lloyd, M. K., & Eiler, J. M. (2021) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2021.116964 · Cited by 22 · see citing works
Perez-Beltran, S., Zaheer, W., Sun, Z., Defliese, W. F., Banerjee, S., & Grossman, E. L. (2023) · Science Advances · doi:10.1126/sciadv.adf1701 · Cited by 21 · see citing works
Coccolith crystals: Pure calcite or organic-mineral composite structures?
Walker, J. M., & Langer, G. (2021) · Acta Biomaterialia · doi:10.1016/j.actbio.2021.02.025 · Cited by 21 · see citing works
Fukuda, J., & Shimizu, I. (2019) · Earth Planets and Space · doi:10.1186/s40623-019-1117-4 · Cited by 16 · see citing works
A workflow and software solution for spatially resolved spectroscopic and numerical data (SpecXY)
Gies, N. B., Lanari, P., & Hermann, J. (2024) · Computers & Geosciences · doi:10.1016/j.cageo.2024.105626 · Cited by 12 · see citing works
Self-citationLooser, N., Aschwanden, L., Wohlwend, S., Guillong, M., Rickli, J., Schneeberger, R., & Bernasconi, S. M. (2025) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2025.119410 · Cited by 10 · see citing works
Self-citationSun, Z., Perez-Beltran, S., Zaheer, W., Defliese, W. F., Banerjee, S., & Grossman, E. L. (2023) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2023.118467 · Cited by 10 · see citing works
Adlan, Q., Kaczmarek, S., & John, C. (2023) · Minerals · doi:10.3390/min13121466 · Cited by 6 · see citing works
Rapid thermal resetting of clumped isotope in coral aragonite
Guo, Y., Guo, Y., Deng, W., & Wei, G. (2025) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2025.119519 · Cited by 3 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Internal water and organic matter increase calcite clumped isotope reactivity
Sun, Z., Cheng, J., Banerjee, S., & Grossman, E. L. (2026) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2026.07.038
- Authors
- Kueter, N., Looser, N., Hemingway, J. D., Gies, N. B., Price, G. D., Perez-Huerta, A., & Bernasconi, S. M.
- Affiliations
- ETH Zurich (CH)
- University of Bern (CH)
- University of Plymouth (GB)
- University of Alabama (US)
- Corresponding author
- Kueter, Nico
- Looser, Nathan
- ORCID
- Venue
- Earth and Planetary Science Letters
- Publisher
- Elsevier BV
- Published
- 2026-05
- Volume
- 682
- Pages
- 119955
- ISSN
- 0012-821X (ISSN-L)
- OpenAlex
- W7135373076
- Cited by
- 1
- References
- 54
- Citations by year
- 2026: 1
- FWCI
- 3.91
- Type
- journal article
- Language
- en
- Update notices
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Earth and Planetary Science Letters (publishedVersion, cc-by)
- PEARL (University of Plymouth) (submittedVersion, cc-by)
- Funders
- European Research Council
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung (200021-200977, 200021-169849, 200020\u2013196927)
- Horizon 2020 Framework Programme (946150)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geophysics › Geological and Geochemical Analysis
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Geology and Paleoclimatology Research
- Keywords
- carbonate clumped isotopes, thermal resetting, kinetic parameters, biogenic calcite, oxygen isotope exchange, organic matter, thermal history, paleotemperature, heating experiments
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
