A NEW METHOD FOR ANALYZING 14C OF METHANE IN ANCIENT AIR EXTRACTED FROM GLACIAL ICE

ABSTRACT. We present a new method developed for measuring radiocarbon of methane (14CH4) in ancient air samples extracted from glacial ice and dating 11,000–15,000 calendar years before present. The small size (~20 µg CH4 carbon), low CH4 concentrations ([CH4], 400–800 parts per billion [ppb]), high carbon monoxide concentrations ([CO]), and low 14C activity of the samples created unusually high risks of contamination by extraneous carbon. Up to 2500 ppb CO in the air sam-ples was quantitatively removed using the Sofnocat reagent. 14C procedural blanks were greatly reduced through the construc-tion of a new CH4 conversion line utilizing platinized quartz wool for CH4 combustion and the use of an ultra-high-purity iron catalyst for graphitization. The amount and 14C activity of extraneous carbon added in the new CH4 conversion line were determined to be 0.23 ± 0.16 µg and 23.57 ± 16.22 pMC, respectively. The amount of modern (100 pMC) carbon added during the graphitization step has been reduced to 0.03 µg. The overall procedural blank for all stages of sample handling was 0.75 ± 0.38 pMC for ~20-µg, 14C-free air samples with [CH4] of 500 ppb. Duration of the graphitization reactions for small (<25 µg C) samples was greatly reduced and reaction yields improved through more efficient water vapor trapping and the use of a new iron catalyst with higher surface area. 14C corrections for each step of sample handling have been determined. The resulting overall 14CH4 uncertainties for the ancient air samples are ~1.0 pMC