Near Equilibrium 13C18O Bonding During Inorganic Calcite Precipitation Under Chemo‐Stat Conditions
Open accessAbstract
We report results of 13 C/12 C, 18 O/16 O, and 13 C18 O “clumped” isotope analyses from a series of calcite precipitation experiments from aqueous solutions under laboratory conditions. Chemo‐stat precipitation experiments were performed to synthetically form calcite from aqueous solution onto 43 Ca‐labeled calcite seed crystals. Formation rate was controlled during the experiments to investigate the effect of precipitation rate and temperature on 13 C18 O bonding in calcite, where rates ranged from 10−6.88 to 10−8.20 mol m−2 s−1 at three temperatures (10, 20, and 30°C). No relation was observed between precipitation rate and 13 C18 O bonding proportion over the range of precipitation rates used. The relation between Δ 47 and temperature produced was comparable to calibration studies which report a relatively high sensitivity of 13 C18 O bonding to temperature over the range investigated. Comparing solution conditions across multiple experimental data sets indicates an inverse relation between saturation state and 13 C18 O bonding, where high super‐saturation conditions are likely to be furthest from equilibrium 13 C18 O partitioning. Carbon fractionation between calcite and was found to be a temperature independent value of +1.6‰. The temperature‐dependent calcite‐water 18 O/16 O fractionation relation determined in this study is slightly different (larger value) than those measured in several previous investigations. Significantly, we observe a dependence of the 18 O/16 O isotope fractionation factor on growth rate. Taken together, these findings suggest carbonate growth in our experiments approached equilibrium more closely than previous experiments of this type, yet did not achieve full O isotope equilibrium.
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Full attainment of oxygen-isotope equilibrium might not be achievable in laboratory experiments, so one must instead turn to natural minerals precipitated very slowly from slightly supersaturated environments.
“Both theory23,27 and empirical results28 suggest that full attainment of oxygen-isotope equilibrium might not be achievable in laboratory experiments, so that one must instead turn to natural minerals precipitated very slowly from slightly supersaturated environments.”
From Most Earth-surface calcites precipitate out of isotopic equilibrium (2019) · cites this paper as [28]
Section 4.2 (page unavailable) says complete oxygen-isotope equilibrium may be difficult to attain even in the authors’ low-saturation laboratory experiments. It also describes very slowly precipitated Devils Hole calcite as a natural equilibrium reference; Section 4.3 gives its saturation state as 1.5 ± 0.09. The paper favors calibrations resembling that natural reference, but does not say researchers must turn to natural minerals instead of laboratory experiments. (LLM, conf=0.84)
Experimental — accuracy not yet measuredThe slope of the Δ47 regression is statistically indistinguishable from those obtained by several recent Δ47 calibration studies.
“The slope of this regression is statistically indistinguishable from those obtained by several recent Δ47 calibration studies28,38–40.”
From Most Earth-surface calcites precipitate out of isotopic equilibrium (2019) · cites this paper as [28]
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- Authors
- Levitt, N. P., Eiler, J. M., Romanek, C. S., Beard, B. L., Xu, H., & Johnson, C. M.
- Affiliations
- University of Wisconsin–Madison (US)
- California Institute of Technology (US)
- NASA Astrobiology Institute (US)
- Corresponding author
- Levitt, Nicholas P.
- Venue
- Geochemistry, Geophysics, Geosystems
- Publisher
- American Geophysical Union (AGU)
- Published
- 2018-03
- Volume
- 19
- Issue
- 3
- Pages
- 901-920
- ISSN
- 1525-2027 (ISSN-L)
- OpenAlex
- W2788511281
- Cited by
- 48
- References
- 91
- Citations by year
- 2026: 2 · 2025: 1 · 2024: 8 · 2023: 2 · 2022: 9 · 2021: 8 · 2020: 5 · 2019: 10 · 2018: 3
- FWCI
- 2.10
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- Geochemistry Geophysics Geosystems (publishedVersion)
- CaltechAUTHORS (California Institute of Technology) (submittedVersion)
- Funders
- National Aeronautics and Space Administration (NNX13AP40H, NNA13AA94A)
- Topics
- Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
- Physical Sciences › Environmental Science › Environmental Engineering › CO2 Sequestration and Geologic Interactions
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Keywords
- calcite precipitation, clumped isotopes, precipitation rate, temperature dependence, carbon isotope fractionation, saturation state, supersaturation
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