Optimizing the Use of Carbonate Standards to Minimize Uncertainties in Clumped Isotope Data

Kocken, Ilja J.; Müller, Inigo A.; Ziegler, Martin

doi:10.1029/2019gc008545

Cited by 57Geology and Paleoclimatology ResearchPaleontology and Stratigraphy of FossilsGeological and Geochemical Analysis

Optimizing the Use of Carbonate Standards to Minimize Uncertainties in Clumped Isotope Data

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Kocken, Ilja J., Müller, Inigo A., Ziegler, Martin·2019·Geochemistry, Geophysics, Geosystems

DOI 10.1029/2019gc008545

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Abstract

Clumped isotopes provide a theory‐based proxy to reconstruct formation temperatures of carbonates. With the introduction of the empirical transfer function (ETF) and several carbonate standards, interlaboratory comparison has become achievable. Due to the rare occurrence of the multiply substituted isotopologues, the analytical precision of these measurements is very low. In order to improve precision, we investigate the optimal strategy for the conversion into the absolute reference frame using a simulation approach. We find that changing the relative proportions of the standards to include more standards that are closer to the unknown target Δ 47 value can greatly improve attainable precision. The inclusion of a hypothetical 4 °C standard results in only modest improvements in final temperature estimates for Earth surface temperature (0 and 40 °C) samples, indicating that the set of ETH‐1–3 standards is suitable for most applications. Full interpolation between two subsequent hypothetical standards, with Δ 47 values of CO 2 equilibrated at 1000 and 25 °C, results in modest improvements for samples with extreme Δ 47 values. With a more optimal distribution of standards it is possible to measure more sample replicates before the uncertainty derived from the ETF becomes limiting. We provide suggestions for the optimal distribution of standards for all target sample Δ 47 values and the R code to perform these simulations based on different laboratory settings. These optimizations can also be applied for ETFs using heated and equilibrated gases. We demonstrate numerically how optimizing the distribution and relative abundance of standards can increase measurement precision.

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Daëron (2021) and Kocken et al. (2019) suggest a ∼50:50 ratio of standard to sample replicates to keep standardization errors small.
“Daëron (2021) and Kocken et al. (2019) suggest ∼50:50 ratio of standard to sample replicates to keep standardization errors small.”
From InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards (2021) · cites this paper as Kocken et al. (2019)
The error increases for unknown samples whose compositions lie outside the "anchor triangle" defined by ETH-1/2/3.
“In addition, the error increases for unknown samples whose compositions lie outside the “anchor triangle” defined by ETH‐1/2/3.”
From InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards (2021) · cites this paper as Kocken et al., 2019
The number and distribution of standards in a measuring interval are important parameters to improve reproducibility and reduce errors.
“The number and distribution of standards in a measuring interval are also important parameters to improve reproducibility and reduce errors.”
From InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards (2021) · cites this paper as Kocken et al. (2019)
Carbonate standards with bulk and clumped-isotope compositions similar to those of unknowns should be analyzed with greater frequency than the other anchors, while preserving a minimal level of replication for each anchor.
“This has been discussed in detail by Kocken et al. (2019) and Daëron (2021) who both concluded that carbonate standards with bulk and clumped‐isotope compositions similar to those of unknowns should be analyzed with greater frequency than the other anchors, while preserving a minimal level of replication for each anchor.”
From InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards (2021) · cites this paper as Kocken et al. (2019)

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Vleeschouwer, D. D., Peral, M., Marchegiano, M., et al. (2021) · Climate of the past · doi:10.5194/cp-2021-151-rc1
Authors' reply to RC2
Vleeschouwer, D. D. (2022) · Climate of the past · doi:10.5194/cp-2021-151-ac2
Authors' reply to RC3
Vleeschouwer, D. D. (2022) · Climate of the past · doi:10.5194/cp-2021-151-ac1
Authors' reply to Clara Bolton (RC1)
Vleeschouwer, D. D. (2022) · Climate of the past · doi:10.5194/cp-2021-151-ac3
Issue Information
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Reducing Uncertainties in Carbonate Clumped Isotope Analysis Through Consistent Carbonate-Based Standardization
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Analytical effects on clumped isotope thermometry: Comparison of a common sample set analyzed using multiple instruments, types of standards, and standardization windows.
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Authors: Kocken, I. J., Müller, I. A., & Ziegler, M.
Affiliations: Utrecht University (NL)
Corresponding author: Kocken, Ilja J.
ORCID: Kocken, Ilja J.
Müller, Inigo A.
Ziegler, Martin
Venue: Geochemistry, Geophysics, Geosystems
Publisher: American Geophysical Union (AGU)
Published: 2019-11
Volume: 20
Issue: 11
Pages: 5565-5577
ISSN: 1525-2027 (ISSN-L)
DOI: 10.1029/2019gc008545
OpenAlex: W2980676598
Cited by: 57
References: 33
Citations by year: 2026: 3 · 2025: 4 · 2024: 12 · 2023: 12 · 2022: 12 · 2021: 11 · 2020: 1 · 2019: 2
FWCI: 2.58
Type: journal article
Language: en
Open access: hybrid
doi.org
Licence: cc-by
creativecommons.org/licenses/by/4.0/ (vor, 4 d)
Locations: Geochemistry Geophysics Geosystems (publishedVersion, cc-by)
Utrecht University Repository (Utrecht University) (submittedVersion, other-oa)
Funders: Nederlandse Organisatie voor Wetenschappelijk Onderzoek (016.161.365)
Topics: Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Geology and Paleoclimatology Research
Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
Physical Sciences › Earth and Planetary Sciences › Geophysics › Geological and Geochemical Analysis
Keywords: clumped isotopes, empirical transfer functions, Δ47, formation temperature, measurement precision, interlaboratory comparison, Earth surface temperature

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Optimizing the Use of Carbonate Standards to Minimize Uncertainties in Clumped Isotope Data

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