On the interference of ⁸⁶Kr²⁺ during carbon isotope analysis of atmospheric methane using continuous flow combustion – isotope ratio mass spectrometry

Abstract

Abstract. Stable carbon isotope analysis of methane (δ13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography isotope ratio mass spectrometry coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton can severely interfere during the mass spectrometric measurement leading to significant biases in δ13C of CH4 if krypton is not sufficiently separated during the analysis. The effect comes about by the lateral tailing of the peak of doubly charged 86Kr in the neighbouring m/z, 44, 45, and 46 Faraday cups. Accordingly, the introduced bias is dependent on the chromatographic separation, the Kr to CH4 mixing ratio in the sample, the mass spectrometer source tuning as well as the detector configuration and can amount to up to several permil in δ13C. Apart from technical solutions to avoid this interference we present correction routines to a posteriori remove the bias.