Active chlorine in the remote marine boundary layer: Modeling anomalous measurements of δ13C in methane

Abstract

Measurements of δ13C in methane in the marine boundary layer (MBL) of the extratropical Southern Hemisphere imply a kinetic isotope fractionation much larger than would be expected if the hydroxyl radical were the only tropospheric methane sink. We use a simple chemical box model to show that the assumption of a MBL active chlorine (Cl•) sink can explain these anomalous observations provided there is a seasonal cycle in the Cl• sink with a summer-winter concentration difference ∼ 6 . 103 cm-3. The required summer maximum and yearly mean Cl• concentrations are plausible, and imply a global Cl• sink strength for methane of < 5 Tg yr-1. Choice of a Cl• sink seasonal cycle linked to the nonsinusoidal dimethyl sulfide seasonal cycle gives the observed fractionation with a smaller yearly mean Cl• concentration than equivalent sinusoidal Cl• cycles.