Dual Separation of Krypton and Argon from Environmental Samples for Radioisotope Dating

The noble gas radioisotopes ⁸⁵Kr, ⁸¹Kr, and ³⁹Ar are nearly ideal environmental tracers because of their chemical inertness and simple transport mechanisms. Recent advances in Atom Trap Trace Analysis have enabled measurements of ⁸⁵Kr and ⁸¹Kr using 10-20 kg of water or ice, and ³⁹Ar in only a few kilograms, making these tracers available to be applied in the earth sciences on a large-scale. To meet the resulting increase in demand, we have developed an automated process for the dual separation of krypton and argon from environmental samples based on titanium gettering and gas chromatography. 0.5-4 L STP air samples have been purified, demonstrating purities and recoveries of >90% for krypton and >99% for argon within 90-120 min of processing time. Samples of high methane admixtures, a challenge regularly encountered in groundwater applications, have been purified by exploiting the full potential of titanium gettering at high temperatures (>1000 °C). Samples with 0.4-48 L STP of methane admixture are processed in 2-5 h without compromising purity or recovery. The applicability of the purification system is further demonstrated using actual groundwater samples with carbon dioxide and methane content in the extracted gas up to 16 L STP and 42 L STP, respectively.