Cited by 209Geology and Paleoclimatology ResearchPaleontology and Stratigraphy of FossilsGeological and Geochemical Analysis

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

Open access
Petersen, S. V., Defliese, W. F., Saenger, C., Daëron, M., Huntington, K. W., John, C. M., Kelson, J. R., Bernasconi, S. M. +22 more·2019·Geochemistry, Geophysics, Geosystems

Abstract

The clumped isotopic composition of carbonate‐derived CO 2 (denoted Δ 47 ) is a function of carbonate formation temperature and in natural samples can act as a recorder of paleoclimate, burial, or diagenetic conditions. The absolute abundance of heavy isotopes in the universal standards VPDB and VSMOW (defined by four parameters: R 13 VPDB , R 17 VSMOW , R 18 VSMOW , and λ ) impact calculated Δ 47 values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ 47 relationship. Using the updated parameters, we reprocess 14 published calibration data sets measured in 11 different laboratories, representing many mineralogies, bulk compositions, sample types, reaction temperatures, and sample preparation and analysis methods. Exploiting this large composite data set ( n = 1,253 sample replicates), we investigate the possibility for a “universal” clumped isotope calibration. We find that applying updated parameters improves the T‐Δ 47 relationship (reduces residuals) within most labs and improves overall agreement but does not eliminate all interlaboratory differences. We reaffirm earlier findings that different mineralogies do not require different calibration equations and that cleaning procedures, method of pressure baseline correction, and mass spectrometer type do not affect interlaboratory agreement. We also present new estimates of the temperature dependence of the acid digestion fractionation for Δ 47 (Δ* 25‐X ), based on combining reprocessed data from four studies, and new theoretical equilibrium values to be used in calculation of the empirical transfer function. Overall, we have ruled out a number of possible causes of interlaboratory disagreement in the T‐Δ 47 relationship, but many more remain to be investigated.

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.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.1029/2018gc008127

Cites

89 of 91 references verified0 citation errors · 0 not checkable

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.

A few free checks a day · papers already verified open instantly · results are public

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • The Petersen et al. (2019) CDES-referenced calibration is a compilation and recalculation of existing data spanning 4-800°C, with n=132 samples and >1,200 replicate analyses from 11 laboratories, generated prior to I-CDES.

    “The CDES-referenced calibration of Petersen et al. (2019) is a compilation and recalculation of existing data [n = 132 samples (>1,200 replicate analyses) from 11 laboratories] spanning 4-800°C generated prior to the establishment of I-CDES.”

    From Frontiers of Carbonate Clumped Isotope Thermometry (2023) · cites this paper as Petersen et al. 2019

    Data Selection (p. 6) confirms that the authors reprocessed published data from 11 laboratories, including 132 synthetic samples. But the composite synthetic calibration uses 451 replicates (section 3.4, p. 15); the more than 1,200 replicates refer to all sample types (section 3.4, p. 16). The retrieved text does not establish the precise 4–800°C range or call the calibration CDES-referenced. (LLM, conf=0.86)

    Experimental — accuracy not yet measured
  • The contribution from TΔi calibration uncertainty is small compared to the contribution from sample and reference frame measurements.

    “The contribution from Ti calibration uncertainty is small compared to the contribution from sample and reference frame measurements (e.g., Petersen et al. 2019, figure 8).”

    From Frontiers of Carbonate Clumped Isotope Thermometry (2023) · cites this paper as Petersen et al. 2019

    Section 3.9 (pp. 20–21, Figure 8) says that, for a well-constrained calibration with more than 30 replicates, uncertainty in the calibration slope and intercept is much smaller than analytical error. It does not separately compare calibration uncertainty with uncertainty from reference-frame measurements, and the citing sentence omits the well-constrained-calibration condition. (LLM, conf=0.85)

    Experimental — accuracy not yet measured
  • Up to 1-2°C external precision (2 standard error of the mean) can be achieved with extensive replication.

    “Up to 1-2°C external precision (2 standard error of the mean) can be achieved with extensive replication (e.g., Petersen et al. 2019).”

    From Frontiers of Carbonate Clumped Isotope Thermometry (2023) · cites this paper as Petersen et al. 2019

    Section 2.3 (p. 10) states that external standard error decreases with the square root of the number of replicates, and section 3.9 (pp. 20–21) discusses how replication affects reconstructed-temperature error. But the paper does not establish the claimed 1–2°C precision at 2 standard errors; it says temperature error varies with formation temperature and also discusses calibration uncertainty. (LLM, conf=0.84)

    Experimental — accuracy not yet measured
  • Theoretical equilibrium i values of clumped molecules increase with decreasing temperature.

    “Theoretical equilibrium i values of clumped molecules increase with decreasing temperature (T ).”

    From Frontiers of Carbonate Clumped Isotope Thermometry (2023) · cites this paper as Petersen et al. (2019)

    Section 3.9 (p. 20) says Δ47 decreases as temperature increases, supporting the inverse temperature relationship. Section 3.1 (p. 11) identifies theoretical equilibrium Δ47 values for CO2, but the paper does not establish the claim for clumped molecules generally or for other Δi values. (LLM, conf=0.79)

    Experimental — accuracy not yet measured
  • The Petersen et al. (2019) CDES-referenced T-47 calibration and Anderson et al. (2021) I-CDES-referenced calibration are offset from each other by 3°C near 25°C and 7°C near 100°C and show a similar temperature dependence as the 47 theoretical equilibrium calculations of Schauble et al. (2006) and Hill et al. (2014), with a difference of about 2°C at Earth surface temperatures.

    “These two calibrations are offset from each other by 3°C near 25°C and 7°C near 100°C and show a similar temperature dependence as the 47 theoretical equilibrium calculations of Schauble et al. (2006) and Hill et al. (2014) (difference of ∼2°C at Earth surface temperatures).”

    From Frontiers of Carbonate Clumped Isotope Thermometry (2023) · cites this paper as Petersen et al. (2019)

    Split into 2 atoms — 0 confirmed, 1 partially supported, 0 disputed, 0 misattributed, 1 unverifiable. Expand the claim to see per-atom verdicts.

    Experimental — accuracy not yet measured

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

Flagged first, then by citations

Cited by

Sorted by citations

Authors
Petersen, 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., Olack, G. A., Schauer, A. J., Bajnai, D., Bonifacie, M., Breitenbach, S. F. M., Fiebig, J., Fernandez, A. B., Henkes, G. A., Hodell, D., Katz, A., Kele, S., Lohmann, K. C., Passey, B. H., Peral, M. Y., Petrizzo, D. A., Rosenheim, B. E., Tripati, A., Venturelli, R., Young, E. D., & Winkelstern, I. Z.
Affiliations
  • University of Michigan (US)
  • University of California, Los Angeles (US)
  • University of Washington (US)
  • Laboratoire des Sciences du Climat et de l'Environnement (FR)
  • Imperial College London (GB)
  • ETH Zurich (CH)
  • University of Chicago (US)
  • Heidelberg University (DE)
  • Goethe University Frankfurt (DE)
  • Institut de physique du globe de Paris (FR)
  • University of Cambridge (GB)
  • Department of Earth Sciences ETH‐Zurich Zurich Switzerland
  • Stony Brook University (US)
  • Institute for Geological and Geochemical Research (HU)
  • Jet Propulsion Laboratory (US)
  • University of South Florida St. Petersburg (US)
  • Grand Valley State University (US)
Corresponding author
Petersen, S. V.
Venue
Geochemistry, Geophysics, Geosystems
Published
2019-07
Volume
20
Issue
7
Pages
3495-3519
ISSN
1525-2027 (ISSN-L)
OpenAlex
W2947366632
Cited by
209
References
89
Citations by year
2026: 16 · 2025: 14 · 2024: 32 · 2023: 28 · 2022: 35 · 2021: 45 · 2020: 23 · 2019: 16
FWCI
11.89
Type
journal article
Language
en
Open access
Locations
  • Geochemistry Geophysics Geosystems (publishedVersion, other-oa)
  • Northumbria Research Link (Northumbria University) (acceptedVersion, other-oa)
  • Repository of the Academy's Library (Library of the Hungarian Academy of Sciences) (acceptedVersion)
  • Digital Commons - University of South Florida (University of South Florida) (submittedVersion, other-oa)
  • HAL (submittedVersion, other-oa)
  • Deep Blue (University of Michigan) (submittedVersion, other-oa)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion, other-oa)
  • HAL Portal Artxiker (Hindustan Aeronautics Limited (India)) (submittedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
  • VUBIR (Vrije Universiteit Brussel) (submittedVersion)
Funders
  • National Science Foundation (1156134, 1713275, 0923831)
  • U.S. Department of Energy (DE‐SC0010288)
  • Nemzeti Kutatási Fejlesztési és Innovációs Hivatal (KH 125584)
  • Natural Environment Research Council (NE/M003752/1)
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, interlaboratory agreement, empirical transfer functions, carbonate diagenesis

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