The Kinetics of Solid-State Isotope-Exchange Reactions for Clumped Isotopes: A Study of Inorganic Calcites and Apatites from Natural and Experimental Samples
Open accessAbstract
Carbonate clumped-isotope geothermometry is a tool used to reconstruct formation or (re)equilibration temperatures of carbonate bearing minerals, including carbonate groups substituted into apatite. It is based on the preference for isotopologues with multiple heavy isotopes (for example, ^13^C^16^O~2~^18^O^2−^ groups) to be more abundant at equilibrium than would be expected if all isotopes were randomly distributed amongst all carbonate groups. Because this preference is only a function of temperature, excesses of multiply substituted species can be used to calculate formation temperatures without knowledge of the isotopic composition of water from which the mineral precipitated or other phases with which it may have equilibrated. However, the measured temperature could be modified after mineral growth if exchange of isotopes amongst carbonate groups within the mineral has occurred through internal isotope-exchange reactions. Because these exchange reactions occur through thermally activated processes, their rates depend on temperature and increase at higher temperatures. Thus internal isotope-exchange reactions could lead to effective re-equilibration at high temperatures, overprinting the original temperatures recorded during mineral growth. We measured clumped-isotope temperatures in carbonate bearing minerals (including apatites) from several carbonatites to constrain the kinetics of these internal isotope-exchange reactions. We observe two key trends for clumped-isotope temperatures in carbonatites: (*i*) clumped-isotope temperatures of apatites and carbonate-bearing minerals decrease with increasing intrusion depth and (*ii*) apatites record lower clumped-isotope temperatures than carbonate minerals from the same intrusion. We additionally conducted heating experiments at different temperatures to derive the temperature dependence for the rate constants that describe the alteration of clumped-isotope temperatures with time in calcites and apatites. We find that calcites exhibit complex kinetics as has been seen in previous studies. To quantify these results, we constructed a model that incorporates both diffusion of isotopes through the crystal lattice and isotope-exchange reactions between adjacent carbonate groups. We tested this model through comparison to previous measurements of optical calcites and brachiopods and to samples with known cooling histories and find that the model is able to reasonably capture kinetic data from previous experiments and the observed clumped-isotope temperatures of calcites assuming geologically reasonable cooling rates. A similar model for apatite over-predicts the observed clumped-isotope temperatures found in natural samples; we hypothesize this discrepancy is the result of annealing of radiation damage in our experiments, which lowers the diffusivity and rate of isotope exchange of carbonate groups compared to damaged natural samples. Finally, we constructed models to explore how heating can alter recorded clumped-isotope temperatures. Our model predicts that samples change in clumped-isotope temperatures in two stages. The first stage changes the recorded clumped isotope temperatures by \<1 °C if held at 75 °C for 100 million years and by up to ∼40 °C if held at 120 °C, but the clumped-isotope temperatures does not reach ambient values through this low-temperature mechanism. A second, slower change becomes effective at temperatures above 150 °C and can take the measured clumped-isotope temperature up to the true ambient temperature. This result implies that old (hundreds of million years) samples that have only experienced mild (\<100-125 °C) thermal histories could exhibit small but measurable (order 10 °C) changes in their clumped-isotope temperatures. We compared this heating model to clumped-isotope measurements from paleosol samples from the Siwalik Basin in Nepal, which were buried up to 5 km and then rapidly exhumed to the surface; these samples often do not give reasonable surface temperatures. The modeled temperatures agree with measured temperatures of these samples, suggesting that partial re-equilibration during shallow crustal burial is responsible for their elevated clumped-isotope temperatures.
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The blocking temperature is independent of the original crystallisation temperature and peak burial temperature.
“This blocking temperature is independent of the original crystallisation temperature and peak burial temperature [7,22].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
In “Modeling and Interpretation of Apparent Equilibrium Temperatures During Heating” (page unavailable), the paper predicts that burial at about 80–100 °C can change the recorded apparent equilibrium temperature, and that higher burial temperatures can bring it toward the ambient temperature. Its cooling model assumes prior equilibration at 350 °C rather than establishing independence from crystallisation or peak burial temperature. The claimed unconditional independence is therefore contrary to the paper’s treatment of burial history. (LLM, conf=0.81)
Checked by a reasoning model — may be wrong.
Experimental — accuracy not yet measuredNo geological process is known to reduce TΔ47 values.
“Because no geological process is known to reduce T Δ47 values (7, 23-25)”
From Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the "dolomite problem" (2020) · cites this paper as [25]
In “Modeling and Interpretation of Apparent Equilibrium Blocking Temperatures During Cooling” (page unavailable), the paper models calcite initially equilibrated at 350 °C and then cooled, predicting recorded apparent equilibrium temperatures of 145–235 °C. It also compares those predictions with natural carbonatites. Cooling is therefore a geological process the paper describes as reducing recorded TΔ47, contrary to the claim. (LLM, conf=0.88)
Checked by a reasoning model — may be wrong.
Experimental — accuracy not yet measuredPost-depositional alteration of ∆47 values due to burial and exhumation, including diagenetic modification via dissolution-precipitation recrystallisation, is a concern, particularly in rock-buffered (closed) systems.
“concerns about post-depositional alteration of the ∆ 47 values, as a result of the effects of burial and exhumation, including diagenetic modification via dissolution-precipitation recrystallisation, have emerged, particularly in rock-buffered (i.e., closed) systems [7,8,11,18,20,21].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
The Abstract (page unavailable) identifies recrystallization and closed-system isotope exchange as ways an original clumped-isotope signature can be reset. The “Modeling and Interpretation of Apparent Equilibrium Temperatures During Heating” section (page unavailable) also describes changes during burial. Our copy does not specifically identify dissolution–precipitation recrystallisation as a closed-system process or say that alteration is particularly a concern in rock-buffered systems. (LLM, conf=0.84)
Experimental — accuracy not yet measuredRecalculated δ18Ofluid values show that all samples formed in low water-rock ratios, fitting isotope exchange reactions via solid-state clumped isotope bond reordering.
“The recalculated δ 18 O fluid values show that all of our samples are formed in low water-rock ratios, fitting the isotope exchange reactions via solid-state clumped isotope bond reordering [7,8,18,20,21].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
The Abstract (page unavailable) describes clumped-isotope bond reordering through closed-system isotope-exchange reactions, supporting the proposed mechanism. The cited paper does not report the citing authors’ recalculated δ18Ofluid values or establish that all of their samples formed at low water–rock ratios; its Carbonatites section (page unavailable) discusses oxygen-isotope compositions of its own samples instead. (LLM, conf=0.85)
Experimental — accuracy not yet measuredThe ∆47 values measured for calcite and dolomite in Jabal Akhdar represent blocking (apparent equilibrium) temperatures sensitive only to the cooling rate, not maximum burial temperatures.
“The ∆ 47 values measured for calcite and dolomite in Jabal Akhdar do not represent maximum burial temperatures but the blocking, or apparent equilibrium temperatures, which are sensitive only to the cooling rate [7,8,22].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
The section ‘Modeling and Interpretation of Apparent Equilibrium Blocking Temperatures During Cooling’ (page unavailable) shows that modeled calcite blocking temperatures vary with cooling rate, supporting the general interpretation that such temperatures need not record a thermal maximum. It does not examine Jabal Akhdar samples or establish that their calcite and dolomite values depend only on cooling rate; it also notes that calcite and dolomite may have distinct kinetics. (LLM, conf=0.86)
Experimental — accuracy not yet measured
Original TΔ47 signatures are subject to secondary alteration via meteoric diagenesis, recrystallization, and solid-state reordering during geological burial, all of which shift values to higher-than-original TΔ47 values.
“Original T Δ47 signatures are subject to secondary alteration via meteoric diagenesis, recrystallization, and solid-state reordering during geological burial, all of which result in shifts to higher-than-original T Δ47 values (7,(23)(24)(25).”
From Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the "dolomite problem" (2020) · cites this paper as [25]
The paper’s Modeling and Interpretation of Apparent Equilibrium Temperatures During Heating section reports that solid-state isotope exchange during burial can raise apparent TΔ47 above formation temperature. Its introductory discussion also identifies recrystallization as a way to alter an original clumped-isotope signature, but does not establish that recrystallization or meteoric diagenesis invariably shifts TΔ47 higher. The burial effect is itself conditional on thermal history, rather than an inevitable increase. (LLM, conf=0.85)
Experimental — accuracy not yet measuredUnderstanding of the kinetics of bond reordering at elevated temperature has increased significantly through experimental and modeling studies and through studies in natural laboratories.
“Understanding of the kinetics of bond reordering at elevated temperature has increased significantly through experimental and modeling studies (e.g., Passey & Henkes 2012, Stolper & Eiler 2015, Brenner et al. 2018, Lloyd et al. 2018, Chen et al. 2019, Hemingway & Henkes 2021) and by studies in natural laboratories (e.g., Henkes et al. 2014, Shenton et al. 2015, Lloyd et al. 2017, Brenner et al. 2”
From Frontiers of Carbonate Clumped Isotope Thermometry (2023) · cites this paper as Stolper & Eiler 2015
Solid-state reordering during exhumation can drive ∆47 values to record the apparent equilibrium or blocking temperature of the mineral, which is related to the cooling rate of the strata.
“Solid-state reordering during the exhumation process can drive the ∆ 47 values to record the apparent equilibrium or blocking temperature of the mineral [7,8,22], which is related to the cooling rate of the strata [8,23].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
Even if no recrystallisation occurs, ∆47 values may be reset during solid-state reordering.
“Even if no recrystallisation occurs, the ∆ 47 values may be reset during a process known as solid-state reordering [7,8,11,18,20,21].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
Kinetic parameters have been evaluated in calcite, dolomite, and aragonite using controlled heating experiments.
“Using controlled heating experiments, kinetic parameters have been evaluated in calcite [7,8,20,24], dolomite [21], and aragonite [25,26].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
The paired-diffusion model attributes the change in ∆47 to neighboring singly substituted carbonate group pair interactions, where the group can then diffuse through the crystal lattice to exchange isotopes.
“This paired reaction-diffusion model attributes the change in ∆ 47 to the neighboring singly substituted carbonate group pair interactions, where the group can then diffuse through the crystal lattice to exchange isotopes [7].”
From Clumped Isotope Reordering and Kinetic Differences in Co-Hosted Calcite and Dolomite Minerals throughout Burial Diagenesis and Exhumation (2023) · cites this paper as [7]
Solid-state reordering of carbonates randomizes primary 13C-18O bonds through exchange of oxygen and/or carbon atoms among carbonate ion groups in the crystal lattice, resulting in lower Δ47 and higher TΔ47 values.
“Solidstate reordering of carbonates is a process occurring at elevated temperatures that randomizes primary 13 C-18 O bonds through the exchange of oxygen and/or carbon atoms among carbonate ion groups in the crystal lattice, thus resulting in lower Δ 47 and higher T Δ47 values (25).”
From Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the "dolomite problem" (2020) · cites this paper as [25]
The extent of C-O bond reordering is a function of the temperature-time history of a sample.
“The extent of C-O bond reordering is a function of the temperature-time history of a sample (25).”
From Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the "dolomite problem" (2020) · cites this paper as [25]
Some reactions involve no mass transfer and do not affect trace element compositions and d18O values but can completely or partially reset clumped isotope compositions.
“Some reactions, however, involve no mass transfer and do not affect trace element compositions and d 18 O values (Henkes et al., 2014;Stolper and Eiler, 2015) but they can completely or partially reset clumped isotope compositions.”
From Reconstructing the magnitude of Early Toarcian (Jurassic) warming using the reordered clumped isotope compositions of belemnites (2021) · cites this paper as Stolper and Eiler, 2015
The limit of preservation of D47 for geological timescales is between 80 and 120 °C.
“which for geological timescales is thought to be between 80-120 °C”
From Reconstructing the magnitude of Early Toarcian (Jurassic) warming using the reordered clumped isotope compositions of belemnites (2021) · cites this paper as Stolper and Eiler, 2015
The maximum burial temperatures at Aubach (>90 °C) are higher than the threshold where solid state reordering is thought to begin (80-120 °C for Ma timescales).
“the maximum burial temperatures at Aubach (>90 °C) are higher than the threshold where solid state reordering is thought to begin (80-120 °C for Ma timescales; Henkes et al., 2014;Stolper and Eiler, 2015).”
From Reconstructing the magnitude of Early Toarcian (Jurassic) warming using the reordered clumped isotope compositions of belemnites (2021) · cites this paper as Stolper and Eiler, 2015
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The quantitative determination of calcite associated with the carbonate-bearing apatites
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Analytical Methods in Diffusion Studies
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THE ROLE OF GEOTHERMAL GRADIENTS IN HYDROCARBON EXPLORATION IN PAKISTAN
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Kinetics of CO2(g)–H2O(1) isotopic exchange, including mass 47 isotopologues
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Self-citationDiffusion of C and O in calcite from 0.1 to 200 MPa
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An experimental study of the diffusion of C and O in calcite in mixed CO2-H2O fluid
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Primary textural-structural features of carbonatites and their metamorphic evolution
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THE ORIGIN OF EARLY CALCITIC CARBONATITES
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Cited by
Sorted by citations
Bonifacie, M., Calmels, D., Eiler, J. M., Horita, J., Chaduteau, C., Vasconcelos, C., Agrinier, P., Katz, A., Passey, B. H., Ferry, J. M., et al. (2017) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2016.11.028 · Cited by 233 · see citing works
Self-citationPetersen, S. V., Defliese, W. F., Saenger, C., Daëron, M., Huntington, K. W., John, C. M., Kelson, J. R., Bernasconi, S. M., Colman, A. S., Kluge, T., et al. (2019) · Geochemistry, Geophysics, Geosystems · doi:10.1029/2018gc008127 · Cited by 209 · see citing works
“Eliminated studies are both synthetic (Dennis & Schrag, 2010; Falk & Kelemen, 2015; Ghosh et al., 2006; Stolper & Eiler, 2015; Zaarur et al., 2013) and biogenic/natural (Affek et al., 2008; Came et al., 2007, 2014; Daëron et al., 2011; Douglas et al., 2014; Eagle et al., 2010, 2013, 2015; Ghosh et…”
The rise and demise of the Paleogene Central Tibetan Valley
Xiong, Z., Liu, X., Ding, L., Farnsworth, A., Spicer, R. A., Xu, Q., Valdes, P. J., He, S., Zeng, D., Wang, C., et al. (2022) · Science Advances · doi:10.1126/sciadv.abj0944 · Cited by 179 · see citing works
Evaporitic carbonates in the pre-salt of Santos Basin – Genesis and tectonic implications
Farias, F. A., Szatmari, P., Bahniuk, A. M., & França, A. B. (2019) · Marine and Petroleum Geology · doi:10.1016/j.marpetgeo.2019.04.020 · Cited by 178 · see citing works
Henkes, G. A., Passey, B. H., Grossman, E. L., Shenton, B. J., Yancey, T. E., & Pérez-Huerta, A. (2018) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2018.02.001 · Cited by 176 · see citing works
Advancing Scientific Understanding of the Global Methane Budget in Support of the Paris Agreement
Ganesan, A. L., Schwietzke, S., Poulter, B., Arnold, T., Lan, X., Rigby, M., Vogel, F., van der Werf, G. R., Janssens‐Maenhout, G., Boesch, H., et al. (2019) · Global Biogeochemical Cycles · doi:10.1029/2018gb006065 · Cited by 161 · see citing works
“…thermodynamic processes, and the small number of natural sample measurements to date has detected a range in clumped isotope ratios (Douglas et al., 2017; Haghnegahdar et al., 2017; Stolper et al., 2014; Stolper & Eiler, 2015; Wang et al., 2015; Whitehill et al., 2017; Young et al., 2016, 2017).”
BackgroundChang, B., Li, C., Liu, D., Foster, I., Tripati, A., Lloyd, M. K., Maradiaga, I., Luo, G., An, Z., She, Z., et al. (2020) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1916673117 · Cited by 152 · see citing works
“The extent of C–O bond reordering is a function of the temperature–time history of a sample (25).”
BackgroundOxygen isotope composition of the Phanerozoic ocean and a possible solution to the dolomite problem
Ryb, U., & Eiler, J. M. (2018) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1719681115 · Cited by 129 · see citing works
“In contrast, calcite begins partial reordering during burial to ∼100 °C and fully reequilibrates at temperatures of ∼160–200 °C (28, 29).”
BackgroundSelf-citationCarbonate clumped isotope thermometry in continental tectonics
Huntington, K. W., & Lechler, A. R. (2015) · Tectonophysics · doi:10.1016/j.tecto.2015.02.019 · Cited by 127 · see citing works
Ingalls, M., Rowley, D. B., Olack, G. A., Currie, B. S., Li, S., Schmidt, J. L., Tremblay, M. M., Polissar, P. J., Shuster, D. L., Ding, L., et al. (2017) · Geological Society of America Bulletin · doi:10.1130/b31723.1 · Cited by 107 · see citing works
Experimental 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
“The kinetics of carbonate clumped isotope reordering have been determined in apatite and a variety of calcites by observing the time-dependent changes in ∆47 values as lowtemperature configurations approach high-temperature equilibrium while held in furnaces at fixed temperatures between 385 and 692 °C (Henkes et al.,…”
BackgroundResultInfluentialSelf-citationBergmann, K., Finnegan, S., Creel, R. C., Eiler, J. M., Hughes, N. C., Popov, L. E., & Fischer, W. W. (2017) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2017.11.015 · Cited by 98 · see citing works
Self-citationA 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
Shallow burial alteration of dolomite and limestone clumped isotope geochemistry
Winkelstern, I. Z., & Lohmann, K. C. (2016) · Geology · doi:10.1130/g37809.1 · Cited by 87 · see citing works
Wierzbowski, H., Bajnai, D., Wacker, U., Rogov, M. A., Fiebig, J., & Tesakova, E. M. (2018) · Global and Planetary Change · doi:10.1016/j.gloplacha.2018.05.014 · Cited by 76 · 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
What controls the duration and intensity of ocean anoxic events in the Paleozoic and the Mesozoic?
Reershemius, T., & Planavsky, N. J. (2021) · Earth-Science Reviews · doi:10.1016/j.earscirev.2021.103787 · Cited by 80 · see citing works
Stolper, D., Lawson, M., Formolo, M., Davis, C., Douglas, P., & Eiler, J. (2017) · Special Publications · doi:10.1144/sp468.3 · Cited by 64 · see citing works
“Such blocking temperatures have been studied previously for carbonate clumped isotopes (e.g. Ghosh et al. 2006; Dennis & Schrag 2010; Passey & Henkes 2012; Stolper & Eiler 2015).”
BackgroundSelf-citationMangenot, X., Gasparrini, M., Rouchon, V., & Bonifacie, M. (2017) · Sedimentology · doi:10.1111/sed.12427 · Cited by 70 · see citing works
“O bonds within the mineral lattice (Passey & Henkes, 2012; Henkes et al., 2014; Stolper & Eiler, 2015) and thus compromise the determination of the d18Owater of the parent fluid.”
BackgroundClumped isotope thermometry of calcite and dolomite in a contact metamorphic environment
Lloyd, M. K., Eiler, J. M., & Nabelek, P. I. (2017) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2016.10.037 · Cited by 68 · see citing works
“…calibration is particularly poorly understood at high temperature, where calibration datasets are few, and small differences in ∆47 can amount to predicted temperature differences of many tens of degrees (Bonifacie et al., 2011; Kluge et al., 2015; Passey and Henkes, 2012, Stolper and Eiler, 2015).”
BackgroundMethodInfluentialSelf-citationClumped isotope fractionation during phosphoric acid digestion of carbonates at 70 °C
Müller, I. A., Violay, M. E. S., Storck, J.-C., Fernandez, A., van Dijk, J., Madonna, C., & Bernasconi, S. M. (2017) · Chemical Geology · doi:10.1016/j.chemgeo.2016.11.030 · Cited by 64 · see citing works
Frontiers of Carbonate Clumped Isotope Thermometry
Huntington, K. W., & Petersen, S. V. (2023) · Annual Review of Earth and Planetary Sciences · doi:10.1146/annurev-earth-031621-085949 · Cited by 66 · see citing works
Pan, L., Shen, A., Zhao, J., Hu, A., Hao, Y., Liang, F., Feng, Y., Wang, X., & Jiang, L. (2020) · Sedimentary Geology · doi:10.1016/j.sedgeo.2020.105728 · Cited by 64 · see citing works
Clumped-isotope palaeothermometry and LA-ICP-MS U–Pb dating of lava-pile hydrothermal calcite veins
MacDonald, J., Faithfull, J., Roberts, N. M. W., Davies, A., Holdsworth, C., Newton, M., Williamson, S., Boyce, A. J., & John, C. M. (2019) · Contributions to Mineralogy and Petrology · doi:10.1007/s00410-019-1599-x · Cited by 61 · see citing works
“Stolper and Eiler (2015) proposed different mechanisms: an initial rapid change of ~ 1–40 °C at ambient temperatures of ~ 75–120 °C sustained for ~ 100 Myr due to the diffusion of isotopes through the crystal lattice; after a period of stability, a secondary stage of slow isotope exchange reactions…”
BackgroundMethodInfluentialRitter, A., Mavromatis, V., Dietzel, M., Kwiecien, O., Wiethoff, F., Griesshaber, E., Casella, L. A., Schmahl, W. W., Koelen, J., Neuser, R. D., et al. (2017) · Sedimentology · doi:10.1111/sed.12356 · Cited by 61 · see citing works
“…these results confirms earlier studies showing that metastable aragonite is more susceptible than calcite to bond reordering (Passey & Henkes, 2012; Stolper & Eiler, 2015; Staudigel & Swart, 2016) and that fossil aragonite material will only preserve an original signature if the burial fluid…”
ResultVeillard, C., John, C. M., Krevor, S. C. M., & Najorka, J. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.02.012 · Cited by 62 · see citing works
Lawson, M. J., Shenton, B. J., Stolper, D. A., Eiler, J. M., Rasbury, E. T., Becker, T. P., Phillips-Lander, C. M., Buono, A., Becker, S. P., Pottorf, R., et al. (2017) · Geological Society of America Bulletin · doi:10.1130/b31656.1 · Cited by 58 · see citing works
“The details of this model can be found in the study of Stolper and Eiler (2015).”
BackgroundMethodInfluentialSelf-citationStolper, D. A., Eiler, J. M., & Higgins, J. A. (2018) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2018.01.037 · Cited by 56 · see citing works
“…temperature cut off as, for calcite, the influence of solid-state isotope-exchange reactions on clumped-isotope compositions becomes increasingly important to consider at burial temperatures above 100 C (Passey and Henkes, 2012; Henkes et al., 2014; Stolper and Eiler, 2015; Shenton et al., 2015).”
BackgroundMethodInfluentialSelf-citationChen, 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
Self-citationFernandez, 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
Guo, Y., Deng, W., & Wei, G. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.01.012 · Cited by 50 · see citing works
Mangenot, X., Bonifacie, M., Gasparrini, M., Götz, A., Chaduteau, C., Ader, M., & Rouchon, V. (2017) · Chemical Geology · doi:10.1016/j.chemgeo.2017.10.011 · Cited by 51 · see citing works
Vickers, M. L., Fernandez, A., Hesselbo, S. P., Price, G. D., Bernasconi, S. M., Lode, S., Ullmann, C. V., Thibault, N., Hougaard, I. W., & Korte, C. (2020) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2020.116401 · Cited by 49 · see citing works
Clumped-isotope thermometry of magnesium carbonates in ultramafic rocks
García del Real, P., Maher, K., Kluge, T., Bird, D. K., Brown, G. E., & John, C. M. (2016) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2016.08.003 · Cited by 50 · see citing works
Hoareau, G., Crognier, N., Lacroix, B. J., Aubourg, C., Roberts, N. M. W., Niemi, N. A., Branellec, M., Beaudoin, N. E., & Ruiz, I. S. (2020) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2020.116636 · Cited by 49 · see citing works
Ingalls, M., Frantz, C. M., Snell, K. E., & Trower, E. J. (2020) · Geobiology · doi:10.1111/gbi.12386 · Cited by 46 · see citing works
“Most previous work has sought to explain negative ∆47 anomalies away from Earth surface precipitation conditions, such as high temperature burial diagenesis (e.g., Stolper & Eiler, 2015) and the effects of anaerobic oxidation of methane on the DIC system (Loyd et al., 2016).”
BackgroundA 600-Million-Year Carbonate Clumped-Isotope Record from the Sultanate of Oman
Bergmann, K. D., Al Balushi, S. A. K., Mackey, T. J., Grotzinger, J. P., & Eiler, J. M. (2018) · Journal of Sedimentary Research · doi:10.2110/jsr.2018.51 · Cited by 46 · see citing works
“…le su it e fo ll o w s a d ia g en et ic tr aj ec to ry ch ar ac te ri ze d b y lo w w at er :r o ck ra ti o s. driven by isotopic exchange without dissolution and reprecipitation of new carbonate cements (Dennis and Schrag 2010; Passey and Henkes 2012; Henkes et al. 2014; Stolper and Eiler 2015).”
BackgroundInfluentialSelf-citationFormation of Magnesium Carbonates on Earth and Implications for Mars
Scheller, E. L., Swindle, C., Grotzinger, J. P., Barnhart, H. A., Bhattacharjee, S., Ehlmann, B. L., Farley, K. A., Fischer, W. W., Greenberger, R. N., Ingalls, M., et al. (2021) · Journal of Geophysical Research Planets · doi:10.1029/2021je006828 · Cited by 47 · see citing works
“…thermal perturbation, kinetic effects, shock effects, biological effects, and later heating events above the equilibrium blocking temperature (~145°C–235°C for calcites, Lloyd et al., 2018; Stolper & Eiler, 2015) can also affect the clumped isotopic signatures and require further study.”
BackgroundShuai, Y., Douglas, P., Zhang, S., Stolper, D. A., Ellis, G. S., Lawson, M. J., Lewan, M. D., Formolo, M. J., Mi, J., He, K., et al. (2017) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2017.11.024 · Cited by 46 · see citing works
“…CH4, C2H6, N2O and O2 (e.g., Eiler, 2007, Affek et al., 2008, Daëron et al., 2011, Passey and Henkes, 2012, Saenger et al., 2012, Clog et al., 2014, Stolper and Eiler, 2015, Stolper et al., 2015, Tripati et al., 2015, Wang et al., 2015, Wang et al., 2016, Yeung et al., 2015, Douglas et al., 2017,…”
BackgroundSelf-citationBeaudoin, N. E., Olivier Lacombe, F., Hoareau, G., & Callot, J. (2022) · Geological Magazine · doi:10.1017/s0016756822001327 · Cited by 43 · see citing works
“The method is limited indeed to samples that have not been brought to temperature exceeding c. 180 °C, at which the solid-state reordering by isotopic diffusion of 13C and 18O becomes stochastic (Stolper & Eiler, 2015).”
MethodThe clumped-isotope geochemistry of exhumed marbles from Naxos, Greece
Ryb, U., Lloyd, M. K., Stolper, D. A., & Eiler, J. M. (2017) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2017.04.026 · Cited by 41 · see citing works
“Stolper and Eiler (2015) have called this lock-in temperature the ‘apparent equilibrium blocking temperature’, and used ‘apparent temperatures’ when measured temperatures did not refer to any specific process.”
BackgroundMethodInfluentialSelf-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
“…1 °C/10 years, 1 °C/100 years, 1 °C/ka, 1 °C/10 ka, 1 °C/100 ka, and 1 °C/1 Ma (c) curves for the same cooling rates as (a) but based on the pair exchange-diffusion model of Stolper and Eiler (2015), (d) same as (c) but showing detail for slower cooling rates of 1 °C/month, 1 °C/year,…”
BackgroundMethodInfluentialSelf-citationInternal Water Facilitates Thermal Resetting of Clumped Isotopes in Biogenic Aragonite
Nooitgedacht, C. W., van der Lubbe, J. J. L., Ziegler, M., & Staudigel, P. T. (2021) · Geochemistry Geophysics Geosystems · doi:10.1029/2021gc009730 · Cited by 41 · see citing works
“…that was first ascribed to annealing of crystalline defects (Passey & Henkes, 2012) and later to solid-state isotope exchange between neighboring carbonate ions (Stolper & Eiler, 2015), may be influenced by the mechanism described here in carbonates with internal water available for exchange.”
BackgroundA tropically hot mid-Cretaceous North American Western Interior Seaway
Jones, M. M., Petersen, S. V., & Curley, A. N. (2022) · Geology · doi:10.1130/g49998.1 · Cited by 40 · see citing works
Calibration of dolomite clumped isotope thermometry
Winkelstern, I. Z., Kaczmarek, S. E., Lohmann, K. C., & Humphrey, J. D. (2016) · Chemical Geology · doi:10.1016/j.chemgeo.2016.09.021 · Cited by 40 · see citing works
Briard, J., Pucéat, E., Vennin, E., Daëron, M., Chavagnac, V., Jaillet, R., Merle, D., & de Rafélis, M. (2020) · Palaeogeography Palaeoclimatology Palaeoecology · doi:10.1016/j.palaeo.2019.109582 · Cited by 24 · see citing works
In-situ preservation of nitrogen-bearing organics in Noachian Martian carbonates
Koike, M., Nakada, R., Kajitani, I., Usui, T., Tamenori, Y., Sugahara, H., & Kobayashi, A. (2020) · Nature Communications · doi:10.1038/s41467-020-15931-4 · Cited by 60 · see citing works
A calibration equation between Δ 48 values of carbonate and temperature
Swart, P. K., Lu, C., Moore, E. W., Smith, M. E., Murray, S. T., & Staudigel, P. T. (2021) · Rapid Communications in Mass Spectrometry · doi:10.1002/rcm.9147 · Cited by 40 · see citing works
He, S., Wang, T., Spicer, R. A., Farnsworth, A., Mulch, A., Widdowson, M., Zhang, Q., Cai, F., Valdes, P. J., Wang, C., et al. (2025) · Science Advances · doi:10.1126/sciadv.adr9417 · Cited by 38 · see citing works
Prehistoric cooking versus accurate palaeotemperature records in shell midden constituents
Müller, P., Staudigel, P., Murray, S., Vernet, R., Barusseau, J., Westphal, H., & Swart, P. (2017) · Scientific Reports · doi:10.1038/s41598-017-03715-8 · Cited by 32 · see citing works
Reconsidering the uplift history and peneplanation of the northern Lhasa terrane, Tibet
Ingalls, M., Rowley, D. B., Currie, B. S., & Colman, A. S. (2020) · American Journal of Science · doi:10.2475/06.2020.01 · Cited by 38 · see citing works
Ritter, A., Kluge, T., Berndt, J., Richter, D., John, C. M., Bodin, S., & Immenhauser, A. (2015) · Chemical Geology · doi:10.1016/j.chemgeo.2015.10.008 · Cited by 35 · see citing works
Lacroix, B. J., & Niemi, N. A. (2018) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2018.12.016 · Cited by 32 · see citing works
Bilau, A., Bienveignant, D., Rolland, Y., Schwartz, S., Godeau, N., Guihou, A., Deschamps, P., Mangenot, X., Brigaud, B., Boschetti, L., et al. (2022) · Earth-Science Reviews · doi:10.1016/j.earscirev.2022.104270 · Cited by 31 · see citing works
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Final inversion of the Midcontinent Rift during the Rigolet Phase of the Grenvillian Orogeny
Hodgin, E. B., Swanson‐Hysell, N. L., DeGraff, J. M., Kylander-Clark, A. R. C., Schmitz, M. D., Turner, A. C., Zhang, Y., & Stolper, D. A. (2022) · Geology · doi:10.1130/g49439.1 · Cited by 31 · see citing works
Self-citationRapid and precise measurement of carbonate clumped isotopes using laser spectroscopy
Yanay, N., Wang, Z., Dettman, D. L., Quade, J., Huntington, K. W., Schauer, A. J., Nelson, D. D., McManus, J. B., Thirumalai, K., Sakai, S., et al. (2022) · Science Advances · doi:10.1126/sciadv.abq0611 · Cited by 31 · see citing works
“Samples were then heated to the desired temperature for 21, 9, 13, and 4 days (for 450°, 500°, 550°, and 600°C, respectively) for solid-state reequilibration, following ( 28 ).”
van Dijk, J., Fernandez, A., Storck, J. C., White, T. S., Lever, M., Müller, I. A., Bishop, S., Seifert, R. F., Driese, S. G., Krylov, A., et al. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.03.018 · Cited by 29 · see citing works
Atom probe tomography (APT) of carbonate minerals
Pérez‐Huerta, A., Laiginhas, F., Reinhard, D. A., Prosa, T. J., & Martens, R. (2015) · Micron · doi:10.1016/j.micron.2015.10.001 · Cited by 30 · see citing works
Ingalls, M. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.02.005 · Cited by 30 · 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
Came, R. E., Azmy, K., Tripati, A., & Olanipekun, B.-J. (2017) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2016.10.028 · Cited by 29 · see citing works
Gallagher, T. M., Sheldon, N. D., Mauk, J. L., Petersen, S. V., Gueneli, N., & Brocks, J. J. (2017) · Precambrian Research · doi:10.1016/j.precamres.2017.03.022 · Cited by 29 · see citing works
Staudigel, 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
“…in a conservative manner (i.e., it cannot saturate a fluid and become “rock buffered” with respect to ∆47) and clumped isotope bonds can be reset via internal exchange processes without requiring exchange with external media (Hemingway & Henkes, 2021; Passey & Henkes, 2012; Stolper & Eiler, 2015).”
BackgroundInfluentialQiao, Z., Shen, A., Zhang, S., Hu, A., Liang, F., Luo, X., Shao, G., Wang, Y., Zhao, J., Cao, P., et al. (2023) · AAPG Bulletin · doi:10.1306/11152219193 · Cited by 29 · 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
Kendrick, M. A., Plümper, O., Zhao, J., Feng, Y., Defliese, W. F., Müller, I. A., & Ziegler, M. (2022) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2022.117474 · Cited by 28 · see citing works
Dietzel, M., Purgstaller, B., Kluge, T., Leis, A., & Mavromatis, V. (2020) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2020.02.032 · Cited by 28 · see citing works
Coogan, L. A., Daëron, M., & Gillis, K. M. (2019) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2018.12.014 · Cited by 26 · see citing works
The effect of soil temperature seasonality on climate reconstructions from paleosols
Gallagher, T. M., Hren, M., & Sheldon, N. D. (2019) · American Journal of Science · doi:10.2475/07.2019.02 · Cited by 29 · see citing works
“Heating experiments have suggested that carbonate clumped isotope signatures are likely stable on geologic timescales assuming that burial temperatures do not exceed 75 to 100 °C (Henkes and others, 2014; Stolper and Eiler, 2015).”
BackgroundClog, M., Lindgren, P., Modestou, S., McDonald, A., Tait, A., Donnelly, T., Mark, D. F., & Lee, M. (2024) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2024.01.023 · Cited by 26 · see citing works
Cong, F., Tian, J., Hao, F., Licht, A., Liu, Y., Cao, Z., & Eiler, J. M. (2021) · Journal of Geophysical Research Solid Earth · doi:10.1029/2020jb020636 · Cited by 27 · see citing works
“…comparatively small differences in peak temperature, especially in the window of 120-180 ℃ where the rates of calcite ∆47 reordering are quite uncertain (Stolper and Eiler, 2015), are making it challenging to constrain thermal anomaly events with confidence using calcite ∆47 reordering models…”
BackgroundMethodResultInfluentialSelf-citationA Decrease to Low Carbonate Clumped Isotope Temperatures in Cryogenian Strata
Mackey, T., Jost, A. B., Creveling, J. R., & Bergmann, K. (2020) · AGU Advances · doi:10.1029/2019av000159 · Cited by 28 · see citing works
“…reordering, however, is a product of the time‐temperature path through burial and exhumation (e.g., Henkes et al., 2014; Lloyd et al., 2018; Stolper & Eiler, 2015), which varies regionally (e.g., Lacroix & Niemi, 2019; Naylor et al., 2019), rather than on the m‐scale stratigraphically or…”
BackgroundInfluentialClumped isotope acid fractionation factors for dolomite and calcite revisited: Should we care?
Lu, C., Murray, S. T., Koeshidayatullah, A., & Swart, P. K. (2021) · Chemical Geology · doi:10.1016/j.chemgeo.2021.120637 · Cited by 25 · see citing works
MacDonald, J., John, C. M., & Girard, J. (2017) · Geological Society London Special Publications · doi:10.1144/sp468.7 · Cited by 25 · see citing works
“It is, however, important to address the potential for closed-system bond reordering (Passey & Henkes 2012; Henkes et al. 2014; Stolper & Eiler 2015) to have occurred.”
BackgroundInfluentialTowards a better understanding of the geochemical proxy record of complex carbonate archives
Mueller, M., Walter, B. F., Giebel, R. J., Beranoaguirre, A., Swart, P. K., Lu, C., Riechelmann, S., & Immenhauser, A. (2024) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2024.04.029 · Cited by 24 · see citing works
Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes
Stolper, D. A., & Eiler, J. M. (2016) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2016.02.030 · Cited by 24 · see citing works
“, the approximate temperature above which solid-state atomic mobility 635 can reset the apparent temperature) may be as low as ~70 to 80°C in carbonate groups in 636 apatite (Stolper and Eiler, 2015).”
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“In this case, the measured TΔ47 reflects an apparent temperature ranging between the original crystallization temperature and the maximum temperature experienced during burial (Henkes et al., 2014; Stolper & Eiler, 2015).”
BackgroundLi, H., Liu, X., Arnold, A., Elliott, B. M., Flores, R., Kelley, A. M., & Tripati, A. (2021) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2021.116840 · Cited by 23 · see citing works
Ryb, 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
Self-citationFossil eggshells of amniotes as a paleothermometry tool
Choi, S. H., Park, Y. C., Kweon, J. J., Kim, S., Jung, H., Lee, S. K., & Lee, Y. (2021) · Palaeogeography Palaeoclimatology Palaeoecology · doi:10.1016/j.palaeo.2021.110376 · Cited by 21 · 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
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Nardini, N., Muñoz‐López, D., Cruset, D., Cantarero, I., Martín‐Martín, J. D., Benedicto, A., Gómez-Rivas, E., John, C. M., & Travé, A. (2019) · Minerals · doi:10.3390/min9020117 · Cited by 21 · see citing works
“Clumped isotopes can potentially be reset by recrystallization and by open-system to closed-system isotope-exchange reactions and diffusion within the mineral lattice [110,111].”
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Huang, W., Lippert, P. C., Reiners, P. W., Quade, J., Kapp, P., Ganerød, M., Guo, Z., & van Hinsbergen, D. J. J. (2022) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2022.117390 · Cited by 20 · see citing works
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Self-citationShear heating and clumped isotope reordering in carbonate faults
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CONTINENTAL PALEOTEMPERATURES FROM AN EARLY CRETACEOUS DOLOMITIC LAKE, GANSU PROVINCE, CHINA
Suarez, M. B., Ludvigson, G. A., González, L. A., & You, H. (2017) · Journal of Sedimentary Research · doi:10.2110/jsr.2017.31 · Cited by 18 · see citing works
- Authors
- Stolper, D. A., & Eiler, J. M.
- Affiliations
- California Institute of Technology (US)
- Corresponding author
- Stolper, D. A.
- Venue
- American Journal of Science
- Publisher
- American Journal of Science (AJS)
- Published
- 2015-05-01
- Volume
- 315
- Issue
- 5
- Pages
- 363-411
- ISSN
- 0002-9599 (ISSN-L)
- OpenAlex
- W2273208516
- Cited by
- 257
- References
- 84
- Citations by year
- 2026: 14 · 2025: 20 · 2024: 27 · 2023: 30 · 2022: 42 · 2021: 30 · 2020: 21 · 2019: 21 · 2018: 17 · 2017: 15 · 2016: 14 · 2015: 6
- FWCI
- 16.74
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- American Journal of Science (publishedVersion)
- CaltechAUTHORS (California Institute of Technology) (submittedVersion)
- eScholarship (California Digital Library) (submittedVersion)
- Funders
- National Science Foundation
- California Institute of Technology
- Topics
- Physical Sciences › Earth and Planetary Sciences › Geophysics › Geological and Geochemical Analysis
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Groundwater and Isotope Geochemistry
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Keywords
- clumped isotopes, calcite, apatite, carbonatites, intrusion depth, kinetic modeling, radiation damage annealing, brachiopods, cooling history, rate constants
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