Improving carbonate clumped isotope thermometry for application to foraminifera-based paleoceanography

Abstract:

Carbonate clumped isotope thermometry has great potential for solving long-standing questions in paleoceanography as it provides temperature estimates that are independent from assumptions regarding the isotopic or elemental composition of seawater. However, the application to foraminifera, which would allow reconstructing surface and deep-sea temperatures through the Cenozoic and beyond, is currently hampered by the relatively large sample amount requirements. Normally, several aliquots of 3-10 mg carbonate are needed to arrive at a precision of around 2 °C.

At ETH we have worked towards decreasing the sample requirements by employing the Kiel carbonate preparation device. The Kiel system improves the gas use efficiency and allows balancing sample amount and precision for each sample due to the fact that multiple small aliquots are analyzed. Per measurement we normally use 8-10 aliquots of 150-200 µg carbonate each. With three such measurements (i.e., 4.5-6 mg carbonate) we typically arrive at a precision of around 2 °C (Meckler et al., RCM, 2014), and better precision can be achieved with an increased number of replicates.

We are currently testing ways to reduce sample size and/or increase gas use efficiency further. Recent tests have shown that the size of individual aliquots can be reduced to 100 µg, suggesting that useful temperature estimates (± 2 °C) can be derived with as little as 2.5 mg carbonate.

Uncertainties still exist in the temperature calibration of the carbonate clumped isotope thermometer, which seem at least in part to be associated with differences in the methodology applied by different laboratories. We have therefore derived calibrations for the Kiel method based on synthetic and natural calcites. Current and planned applications of the improved Kiel clumped isotope method to paleoceanography focus on long-term trends and major events during the Cenozoic.