Oxygen isotope fractionation between calcite and fluid as a function of growth rate and temperature: An in situ study

Rinat I. Gabitov, E. Bruce Watson, Aleksey Sadekov

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100 Citations (Scopus)


The 18O content of carbonates (expressed as δ 18O) is widely used in paleothermometry, yet it is clear from comparison of experimental results and natural carbonate samples that chemical (isotopic) equilibrium is not always achieved in nature. This observation underscores the importance of exploring possible effects of growth rate on isotopic fractionation, which is the focus of this study. In situ Secondary Ion Mass Spectrometry (SIMS) analyses of δ 18O were performed on single crystals of experimentally grown calcite. The change in growth rate (V) over time within each crystal was monitored by addition of multiple rare earth element (REE) spikes into the fluid from which the calcite grew. The values of δ 18O in bulk calcites and experimental fluids were measured by stable isotope ratio mass spectrometers. The average SIMS δ 18O overlaps with those determined by conventional mass spectrometry within analytical uncertainty. The fractionation factor expressed as δ 18O approaches its equilibrium value in slowly grown calcites (V<0.02nm/s) and decreases by 1.5‰ with increasing growth rate from 10 -3 to 0.34nm/s. Here δ 18O=10 3{dot operator}ln(α 18O), and α 18O=( 18O/ 16O) calcite/( 18O/ 16O) fluid. Our results provide the first in situ evidence that under equilibrium conditions 18O may be depleted in the near-surface region of calcite relative to the bulk crystal lattice, and that this 18O-depleted zone can be "captured" during rapid crystal growth. Crystal growth rate is therefore a potentially important consideration when using δ 18O in natural carbonates as a proxy for ocean and terrestrial temperature.

Original languageEnglish
Pages (from-to)92-102
Number of pages11
JournalChemical Geology
Publication statusPublished - 4 May 2012
Externally publishedYes


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