Precise oxygen and hydrogen isotope determination in nanoliter quantities of speleothem inclusion water by cavity ring-down spectroscopic techniques

Speleothem inclusion-water isotope compositions are a promising new climatic proxy, but their applicability is limited by their low content in water and by analytical challenges. We have developed a precise and accurate isotopic technique that is based on cavity ring-down spectroscopy (CRDS). This method features a newly developed crushing apparatus, a refined sample extraction line, careful evaluation of the water/carbonate adsorption effect. After crushing chipped speleothem in a newly-developed crushing device, released inclusion water is purified and mixed with a limited amount of nitrogen gas in the extraction line for CRDS measurement. We have measured 50-260 nL of inclusion water from 77 to 286 mg of stalagmite deposits sampled from Gyokusen Cave, Okinawa Island, Japan. The small sample size requirement demonstrates that our analytical technique can offer high-resolution inclusion water-based paleoclimate reconstructions. The 1σ reproducibility for different stalagmites ranges from ±0.05 to 0.61‰ for δ18O and ±0.0 to 2.9‰ for δD. The δD vs. δ18O plot for inclusion water from modern stalagmites is consistent with the local meteoric water line. The 1000 ln α values based on calcite and fluid inclusion measurements from decades-old stalagmites are in agreement with the data from present-day farmed calcite experiment. Combination of coeval carbonate and fluid inclusion data suggests that past temperatures at 9-10 thousand years ago (ka) and 26 ka were 3.4 ± 0.7 °C and 8.2 ± 2.4 °C colder than at present, respectively.