New technique for high-precision, simultaneous measurements of CH4, N2O and CO2 concentrations: isotopic and elemental ratios of N-2, O-2 and Ar; and total air content in ice cores by wet extraction

Air in polar ice cores provides unique information on past climatic and atmospheric changes. We developed a new method combining wet extraction, gas chromatography and mass spectrometry for high-precision, simultaneous measurements of eight air components (CH4, N2O and CO2 concentrations; delta N-15, delta O-18, delta O-2/N-2 and delta Ar/N-2; and total air content) from an ice-core sample of similar to 60 g. The ice sample is evacuated for similar to 2 h and melted under vacuum, and the released air is continuously transferred into a sample tube at 10K within 10 min. The air is homogenized in the sample tube overnight at room temperature and split into two aliquots for mass spectrometric and gas chromatographic measurements. Care is taken to minimize (1) contamination of greenhouse gases by using a long evacuation time, (2) consumption of oxygen during sample storage by a passivation treatment on sample tubes, and (3) fractionation of isotopic ratios with a long homogenization time for splitting. Precision is assessed by analyzing standard gases with artificial ice and duplicate measurements of the Dome Fuji and NEEM ice cores. The overall reproducibility (1 SD) of duplicate ice-core analyses are 3.2 ppb, 2.2 ppb and 2.9 ppm for CH4, N2O and CO2 concentrations; 0.006 %, 0.011 %, 0.09% and 0.12% for delta N-15, delta O-18, delta O-2/N-2 and delta Ar/N-2; and 0.63mL(STP) kg(-1) for total air content, respectively. Our new method successfully combines the high-precision, small-sample and multiple-species measurements, with a wide range of applications for ice-core paleoenviron-mental studies.