A clumped isotope calibration of coccoliths at well-constrained culture temperatures for marine temperature reconstructions

Numerous recent studies have tested the clumped isotope (Delta 47) thermometer on a variety of biogenic carbonates such as foraminifera and bivalves and showed that most follow a common calibration. However, there may be a difference between biogenic-carbonate-based calibrations and the most recent inorganic carbonate calibrations that are assumed to have formed close to isotopic equilibrium. Biogenic calibrations such as those based on foraminifera from seafloor sediments suffer from uncertainties in the determination of the calcification temperatures. Therefore, well-constrained laboratory cultures without temperature uncertainty can help resolve these discrepancies. Although the sample size requirements for a reliable Delta 47 measurement have decreased over the years, the availability and preservation of many biogenic carbonates are still limited and/or require substantial time to be extracted from sediments in sufficient amounts. Coccoliths, on the other hand, are abundant and often well-preserved in sediments, and they are a potential interesting target for palaeoceanography. We thus determined the Delta 47-temperature relationship for coccoliths due to their relative ease of growth in the laboratory. The carbon and oxygen isotopic compositions of coccolith calcite have limited use in palaeoenvironmental reconstructions due to physiological effects that cause variability in the carbon and oxygen isotopic fractionation during mineralization. However, the relatively limited data available suggest that clumped isotopes may not be significantly influenced by these effects. We cultured three species of coccolithophores under controlled carbonate system conditions with CO2(aq) concentrations between 5 and 45 mu M, pH between 7.9 and 8.6 units, and temperatures between 6 and 27 degrees C.Our well-constrained results agree with a previous culture study that there are no apparent species- or genus-specific vital effects on the Delta 47-temperature relationship in coccolithophores despite significant deviations from equilibrium in the C and O isotopic composition. We find that while varying environmental parameters other than temperature does not have a significant effect on Delta 47, changing the parameters yields coccolith Delta 47-temperature calibrations that agree within 1.2 ppm. Our coccolith-specific Delta 47-temperature calibration with well-constrained temperatures shows a consistent, positive offset of 2-3 degrees C to the inorganic carbonate calibrations, which point to as yet unknown coccolith-specific disequilibrium effects.Thus, we suggest the use of our coccolith-specific calibration for further coccolith palaeoceanographic studies and that calibrations derived from laboratory-grown biogenic carbonates are desirable to reinforce the confidence of clumped-isotope-based temperature reconstructions in palaeoceanography.