Multi-proxy assessment of brachiopod shell calcite as a potential archive of seawater temperature and oxygen isotope composition
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Abstract
Abstract. Most of our knowledge of past seawater temperature history is based on δ18O values of calcium carbonate fossil shells. However, the determination of past temperatures using this proxy requires the knowledge of past seawater δ18O values, which is generally poorly constrained. Other paleothermometers using carbonate archives, such as Mg/Ca ratios and clumped isotopes (Δ47), have been developed to allow for paleotemperatures to be estimated independently and to allow past ocean δ18O values to be calculated using various groups of calcifying organisms. Articulated brachiopod shells are some of the most commonly used archives in studies of past oceanic geochemistry and temperature. They are abundant in the fossil record since the Cambrian, and for decades, their low Mg–calcite mineralogy has been considered relatively resistant to diagenetic alteration. Here, we investigate the potential of brachiopod shells as recorders of seawater temperatures and seawater δ18O values using new brachiopod shell geochemical data by testing multiple well-established or suggested paleothermometers applied to carbonate archives. Modern articulated brachiopod shells covering a wide range of temperatures (−1.9 to 25.5 ∘C), depths (5 to 3431 m) and salinities (33.4 to 37.0 PSU) were analysed for their stable isotope compositions (δ13C, δ18O and Δ47) and their elemental ratios (Mg/Ca, Sr/Ca, Na/Ca and Li/Ca). Our data allowed us to propose a revised oxygen isotope fractionation equation between modern-brachiopod shell calcite and seawater: (1) T = - 5.0 ( ± 0.2 ) ( δ 18 O c - δ 18 O sw ) + 19.4 ( ± 0.4 ) , where δ18Oc is in ‰ VPDB, δ18Osw is in ‰ VSMOW, and T is in ∘C. Our results strongly support the use of clumped isotopes as an alternative temperature proxy but confirm significant offsets relative to the canonical relationship established for other biogenic and abiogenic calcium carbonate minerals. Brachiopod shell Mg/Ca ratios show no relationship with seawater temperatures, indicating that this ratio is a poor recorder of past changes in temperatures, an observation at variance with several previous studies. Despite significant correlations with brachiopod living temperature, brachiopod shell Sr/Ca, Na/Ca and Li/Ca values indicate the influence of environmental and biological factors unrelated to temperature, which undermines their potential as alternative temperature proxies. Kinetic effects (growth rates) could explain most of the deviation of brachiopod shell calcite from expected isotopic equilibrium with seawater and part of the distribution of Sr/Ca, Na/Ca and Li/Ca ratios.
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BRACHIOPOD-BASED OXYGEN-ISOTOPE THERMOMETER: UPDATE AND REVIEW
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Revisiting Oxygen‐18 and Clumped Isotopes in Planktic and Benthic Foraminifera
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Self-citationLi/Ca of modern brachiopods: A potential paleoseawater thermometer
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Self-citationRecent Efforts to Improve the Accuracy and Precision of Carbonate Clumped‐Isotope Analysis
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Biodiversity and characteristics of antarctic brachiopods sampled during the CEAMARC expedition
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Arctic brachiopods: shell chemistry shaped by biological factorsPreprint
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- Authors
- Letulle, T., Gaspard, D., Daëron, M., Arnaud-Godet, F., Vinçon-Laugier, A., Suan, G., & Lécuyer, C.
- Affiliations
- Lyon 1 Université (FR)
- Centre National de la Recherche Scientifique (FR)
- Corresponding author
- Letulle, Thomas
- Venue
- Biogeosciences
- Publisher
- Copernicus GmbH
- Published
- 2023-04-12
- Volume
- 20
- Issue
- 7
- Pages
- 1381-1403
- ISSN
- 1726-4170 (ISSN-L)
- 1726-4189
- OpenAlex
- W4367667821
- Cited by
- 28
- References
- 115
- Citations by year
- 2026: 8 · 2025: 6 · 2024: 10 · 2023: 4
- FWCI
- 5.66
- Type
- journal article
- Language
- en
- Open access
- gold
- doi.org
- Licence
- Locations
- Biogeosciences (publishedVersion, cc-by)
- HAL (submittedVersion, other-oa)
- Institutional Archive of Ifremer (French Research Institute for Exploitation of the Sea) (submittedVersion, cc-by)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- Funders
- Agence Nationale de la Recherche (ANR-18-CE31-0020)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Geology and Paleoclimatology Research
- Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
- Keywords
- shells, seawater temperature, oxygen isotope fractionation, clumped isotopes, paleothermometry, Mg/Ca ratio, Sr/Ca ratio, Na/Ca ratio, diagenetic alteration, carbonate geochemistry, paleoclimate proxies
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.
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