A gas chromatography/combustion/isotope ratio mass spectrometry system for high-precision δ13C measurements of atmospheric methane extracted from ice core samples

Abstract

Past atmospheric composition can be reconstructed by the analysis of air enclosures in polar ice cores which archive ancient air in decadal to centennial resolution. Due to the different carbon isotopic signatures of different methane sources high-precision measurements of δ13CH 4 in ice cores provide clues about the global methane cycle in the past. We developed a highly automated (continuous-flow) gas chromatography/ combustion/isotope ratio mass spectrometry (GC/C/IRMS) technique for ice core samples of ∼200 g. The methane is melt-extracted using a purge-and-trap method, then separated from the main air constituents, combusted and measured as CO2 by a conventional isotope ratio mass spectrometer. One CO 2 working standard, one CH4 and two air reference gases are used to identify potential sources of isotope fractionation within the entire sample preparation process and to enhance the stability, reproducibility and accuracy of the measurement. After correction for gravitational fractionation, pre-industrial air samples from Greenland ice (1831 ± 40 years) show a δ13CVPDB of -49.54 ± 0.13‰ and Antarctic samples (1530 ± 25 years) show a δ13CVPDB of -48.00 ± 0.12‰ in good agreement with published data. Copyright © 2008 John Wiley & Sons, Ltd.