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Full propagation of analytical uncertainties in Δ47 measurements

Daëron, Mathieu·2021
DOI 10.1002/essoar.10505298.2

Preprint — published as 10.1029/2020gc009592

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Abstract

Clumped-isotope measurements in CO2 and carbonates (Δ47) present a number of technical challenges and require correcting for various sources of analytical non-linearity. For now we lack a formal description of the analytical errors associated with these correction steps, which are not accounted for in most data processing methods currently in use. Here we formulate a quantitative description of Δ47 error propagation, fully taking into account standardization errors and their properties. We find that standardization errors are highly sensitive to the isotopic compositions (δ47, Δ47) of unknown samples relative to the standards used for analytical corrections, and in many cases constitute a non-negligible source of uncertainty, causing true measurements errors to exceed traditionally reported error estimates by a factor of 1.5 (typically) to 3.5 (in extreme cases). Using Monte Carlo simulations based on the full InterCarb data set, we find that this model yields accurate error estimates in spite of small non-Gaussian effects which remain entirely negligible in practice. We also describe various standardization strategies, along with the assumptions they rely on, in the context of this model, and propose a new, “pooled” standardization approach designed to yield more robust/accurate corrections. Among other uses, the mathematical framework described here may be helpful to improve standardization protocols (e.g., anchor/unknown ratios) and inform future efforts to define community reference materials. What’s more, these models imply that the inter-laboratory scatter (N = 5329) observed in the InterCarb exercise [Bernasconi et al., 2021] can be entirely explained as the effects of current standardization procedures. Based on these findings, we recommend that future studies systematically report full analytical uncertainties taking standardization errors into account. In line with this recommendation, we provide user-friendly online resources and an open-source Python library designed to facilitate the use of these error models.

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  1. Anderson, N. T., Kelson, J. R., Kele, S., Daëron, M., Bonifacie, M., Horita, J., et al. (2021). A unified clumped isotope thermometer calibra- tion (0.5°C -1,100°C) using carbonate-based standardization. Geophysical Research Letters, 48. https://doi.org/10.1029/2020GL092069 · DOI · Paper page
  2. Bernasconi, S. M., Daëron, M., Bergmann, K. D., Bonifacie, M., Meckler, A. N., et al. (2021). InterCarb: A community effort to improve inter-laboratory standardization of the carbonate clumped isotope thermometer using carbonate standards. Geochemistry, Geophysics, Geosystems. https://doi.org/10.1029/2020GC009588 · DOI · Paper page
  3. Bernasconi, S. M., Hu, B., Wacker, U., Fiebig, J., Breitenbach, S. F. M., & Rutz, T. (2013). Background effects on Faraday collectors in gas- source mass spectrometry and implications for clumped isotope measurements. Rapid Communications in Mass Spectrometry, 27(5), 603-612. https://doi.org/10.1002/rcm.6490 · DOI · Paper page
  4. Bernasconi, S. M., Müller, I. A., Bergmann, K. D., Breitenbach, S. F. M., Fernandez, A., Hodell, D. A., et al. (2018). Reducing uncertainties in carbonate clumped isotope analysis through consistent carbonate-based standardization. Geochemistry, Geophysics, Geosystems, 19, 2895-2914. https://doi.org/10.1029/2017GC007385 · DOI · Paper page
  5. Bonifacie, M., Calmels, D., Eiler, J. M., Horita, J., Chaduteau, C., Vasconcelos, C., et al. (2017). Calibration of the dolomite clumped isotope thermometer from 25°C to 350°C, and implications for a universal calibration for all (Ca, Mg, Fe)CO 3 carbonates. Geochimica et Cosmo- chimica Acta, 200, 255-279. https://doi.org/10.1016/j.gca.2016.11.028 · DOI · Paper page
  6. Daëron, M. & Blamart, D. (2016). Uncertainties and standardization in the absolute reference frame. Abstract, Fifth International Clumped Isotope Workshop. url. 02492075 https://hal.archives-ouvertes.fr/hal- Daëron, M., Blamart, D., Peral, M., & Affek, H. P. (2016). Absolute isotopic abundance ratios and the accuracy of Δ 47 measurements. Chem- ical Geology, 442, 83-96. https://doi.org/10.1016/j.chemgeo.2016.08.014 · DOI · Paper page
  7. Dennis, K. J., Affek, H. P., Passey, B. H., Schrag, D. P., & Eiler, J. M. (2011). Defining an absolute reference frame for "clumped" isotope studies of CO 2 . Geochimica et Cosmochimica Acta, 75, 7117-7131. https://doi.org/10.1016/j.gca.2011.09.025 · DOI · Paper page
  8. Eiler, J. M. (2013). The isotopic anatomies of molecules and minerals. Annual Review of Earth and Planetary Sciences, 41(1), 411-441. https://doi.org/10.1146/annurev-earth-042711-105348 · DOI · Paper page
  9. Eiler, J. M., & Schauble, E. (2004). 18 O 13 C 16 O in Earth's atmosphere. Geochimica et Cosmochimica Acta, 68(23), 4767-4777. https://doi. org/10.1016/j.gca.2004.05.035 · DOI · Paper page
  10. Fernandez, A., Müller, I. A., Rodríguez-Sanz, L., van Dijk, J., Looser, N., & Bernasconi, S. M. (2017). A reassessment of the precision of carbonate clumped isotope measurements: Implications for calibrations and paleoclimate reconstructions. Geochemistry, Geophysics, Geosystems, 18(12), 4375-4386. https://doi.org/10.1002/2017gc007106 · DOI · Paper page
  11. Ghosh, P., Adkins, J., Affek, H., Balta, B., Guo, W., Schauble, E. A., et al. (2006). 13 C-18 O bonds in carbonate minerals: A new kind of pale- othermometer. Geochimica et Cosmochimica Acta, 70, 1439-1456. https://doi.org/10.1016/j.gca.2005.11.014 · DOI · Paper page
  12. He, B., Olack, G. A., & Colman, A. S. (2012). Pressure baseline correction and high-precision CO 2 clumped-isotope (Δ 47 ) measurements in bellows and micro-volume modes. Rapid Communications in Mass Spectrometry, 26, 2837-2853. https://doi.org/10.1002/rcm.6436 · DOI
  13. Huntington, K. W., Eiler, J. M., Affek, H. P., Guo, W., Bonifacie, M., Yeung, L. Y., et al. (2009). Methods and limitations of "clumped" CO 2 isotope (Δ 47 ) analysis by gas-source isotope ratio mass spectrometry. Journal of Mass Spectrometry, 44(9), 1318-1329. https://doi. org/10.1002/jms.1614 · DOI · Paper page
  14. John, C. M., & Bowen, D. (2016). Community software for challenging isotope analysis: First applications of "Easotope" to clumped iso- topes. Rapid Communications in Mass Spectrometry, 30, 2285-2300. https://doi.org/10.1002/rcm.7720 · DOI · Paper page
  15. Kocken, I. J., Müller, I. A., & Ziegler, M. (2019). Optimizing the use of carbonate standards to minimize uncertainties in clumped isotope data. Geochemistry, Geophysics, Geosystems, 20(11), 5565-5577. https://doi.org/10.1029/2019gc00854510.1029/2019gc008545 · DOI
  16. Levenberg, K. (1944). A method for the solution of certain nonlinear problems in least squares. Quarterly of Applied Mathematics, 2, 164-168. https://doi.org/10.1090/qam/10666 · DOI
  17. Marquardt, D. W. (1963). An algorithm for least-squares estimation of nonlinear parameters. Journal of the Society for Industrial and Ap- plied Mathematics, 11, 431-441. https://doi.org/10.1137/0111030, http://www.jstor.org/stable/2098941 · DOI · Paper page
  18. Massey, F. J. (1951). The Kolmogorov-Smirnov test for goodness of fit. Journal of the American Statistical Association, 46(253), 68-78. https://doi.org/10.1080/01621459.1951.10500769 · DOI · Paper page
  19. Meckler, A. N., Ziegler, M., Millán, M. I., Breitenbach, S. F. M., & Bernasconi, S. M. (2014). Long-term performance of the Kiel carbonate device with a new correction scheme for clumped isotope measurements. Rapid Communications in Mass Spectrometry, 28, 1705-1715. https://doi.org/10.1002/rcm.6949 · DOI · Paper page
  20. Olack, G., & Colman, A. S. (2019). Modeling the measurement: Δ 47 , corrections, and absolute ratios for reference materials. Geochemistry, Geophysics, Geosystems, 20, 3569-3587. https://doi.org/10.1029/2018gc008166 · DOI
  21. Petersen, S. V., Defliese, W. F., Saenger, C., Daëron, M., Huntington, K. W., John, C. M., et al. (2019). Effects of improved 17 O correction on interlaboratory agreement in clumped isotope calibrations, estimates of mineral-specific offsets, and temperature dependence of acid digestion fractionation. Geochemistry, Geophysics, Geosystems., 20, 3495-3519. https://doi.org/10.1029/2018gc008127 · DOI · Paper page
  22. Schauble, E. A., Ghosh, P., & Eiler, J. M. (2006). Preferential formation of 13 C-18 O bonds in carbonate minerals, estimated using first-prin- ciples lattice dynamics. Geochimica et Cosmochimica Acta, 70, 2510-2529. https://doi.org/10.1016/j.gca.2006.02.011 · DOI · Paper page
  23. Schauer, A. J., Kelson, J., Saenger, C., & Huntington, K. W. (2016). Choice of 17 O correction affects clumped isotope (Δ 47 ) values of CO 2 measured with mass spectrometry. Rapid Communications in Mass Spectrometry, 30(24), 2607-2616. https://doi.org/10.1002/rcm.7743 · DOI · Paper page
  24. Schmid, T. W., & Bernasconi, S. M. (2010). An automated method for 'clumped-isotope' measurements on small carbonate samples. Rapid Communications in Mass Spectrometry, 24(14), 1955-1963. https://doi.org/10.1002/rcm.4598 · DOI · Paper page
  25. Tellinghuisen, J. (2001). Statistical error propagation. Journal of Physical Chemistry A, 105, 3917-3921. https://doi.org/10.1021/jp003484u · DOI

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Metadata

Authors
Daëron, M.
Affiliations
Laboratoire des Sciences du Climat et de l'Environnement, LSCE/IPSL, CEA-CNRS-UVSQ, Université Paris-Saclay
ORCID
Daëron, Mathieu
Publisher
Wiley
Published
2021-03-05
DOI
10.1002/essoar.10505298.2
Cited by
1
References
0
Type
Preprint

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