Hemispheric average Cl atom concentration from ¹³C/¹²C ratios in atmospheric methane

Abstract. Methane is a significant atmospheric trace gas in the context of greenhouse warming and climate change. The dominant sink of atmospheric methane is the hydroxyl radical (OH). Recently, a mechanism for production of chlorine radicals (Cl) in the marine boundary layer (MBL) via bromine autocatalysis has been proposed. The importance of this mechanism in producing a methane sink is not clear at present because of the difficulty of in-situ direct measurement of Cl. However, the large kinetic isotope effect of Cl compared with OH produces a large fractionation of ¹³C compared with ¹²C in atmospheric methane. This property can be used to estimate the likely minimum size of the methane sink attributable to MBL Cl. By taking account of the mixing of MBL air into the free troposphere, we estimate that the global methane sink due to reaction with Cl atoms in the MBL could be as large as 19Tgyr^-1, or about 3.3% of the total CH₄ sink. However, its impact on the methane stable carbon isotope budget is large and warrants further attention.