In order to study temporal and spatial variations of atmospheric CH
4 quantitatively, we originally improved a measurement system for carbon and hydrogen isotopic ratios (δ
13C and δD) of CH
4 to attain high-precision measurements. By analyzing 100 mL aliquots of an ambient air sample, the precision of our system is 0.080‰ for δ
13C and 2.20‰ for δD(1σ), which are one of the highest precisions reported so far. The system consists mainly of aCH
4 preconcentration device and a continuous-flow gas chromatograph isotope ratio mass spectrometer equipped with a combustion furnace and a pyrolysis furnace for measurements of δ
13C and δD. The preconcentration trap temperature was maintained at -130 ± 1°C during collection of CH4 from the air sample by passing it through the trap, then at -83 ± 1°C while remaining air components such as N
2 and O
2 except for CH
4 escaped, and finally at 100 ± 1°C for CH
4 elusion. The isotopic values are measured on a mass spectrometer, relative to respective reference gases. For this study, the δ
13C and δD values of the reference gases were calibrated against our primary standards provided by the IAEA: our δ
13C primary standard is NBS18, whereas our δD primary standards are V-SMOW and SLAP. To ensure the long-term stability and reproducibility of our measurement system, a calibrated whole air stored in a high-pressure cylinder, which was called “test gas,” was measured at least twice on each day when sample measurements were made. To measure small air samples, such as those extracted from ice cores, we also examined the relation between the sample size and the measured value of δ
13C and δD: gradual enrichment of the δ
13C occurred with decreasing CH
4 content less than 8 nmol whereas no such effect could be seen for the δD. Furthermore, preliminary results of latitudinal distributions of δ
13C and δdD were discussed along with CH
4 concentrations obtained by our shipboard air-sampling program.
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