The use of δ 13C in CO to determine removal of CH4 by Cl radicals in the atmosphere *

Abstract

The reaction of CH4 with chlorine (Cl) radicals in the atmosphere is associated with an extraordinarily strong isotopic fractionation, where 12CH4 reacts about 70 ‰ faster with Cl than 13CH4. Therefore, although the Cl-based sink of CH4 constitutes only a small contribution to its total removal rate, the uncertainty in this small sink has been identified as one of the two largest uncertainties of isotope-based CH4 source apportionment at the global scale. The uncertainty arises from the fact that Cl levels in the atmosphere are so low that they cannot be detected directly. One very sensitive indirect method to identify and quantify the CH4 + Cl reaction in the atmosphere is the detection of the extremely 13C-depleted reaction product carbon monoxide (CO) from this reaction. This article reviews the concept of this approach, its successful application in the atmosphere, its challenges and opportunities for identifying and quantifying Cl-based removal of CH4 at the regional and global scale and its potential to detect and evaluate possible attempts to enhance CH4 removal from the atmosphere.