On the relation between stratospheric chlorine/bromine loading and short‐lived tropospheric source gases

Current methods for estimating the concentrations of inorganic chlorine/bromine species (Cly/Bry) in the stratosphere due to decomposition of tropospheric source gases assume that the Cly/Bry concentration in the stratosphere is determined mainly by the balance between production from in situ oxidation of the source gases in the stratosphere and removal by transport of Cly/Bry out of the stratosphere. The rationale being that for source gases whose lifetimes are of the order of several months or longer the concentration of Cly/Bry in the troposphere is small because they are produced at a relatively slow rate and also removed efficiently by washout processes. As a result of the small concentration, the rate at which Cly/Bry is transported to the stratosphere is expected to be small compared to the in situ stratospheric production. Thus the transport of Cly/Bry from the troposphere contributes little to the stratospheric concentration. In contrast, the origin of stratospheric Cly/Bry from reactive source gases with tropospheric lifetimes comparable to the washout lifetime of Cly/Bry (of the order of 10–30 days) in the troposphere is distinctly different. The in situ source in the stratosphere is expected to be significantly smaller because only a small portion of the source gas is expected to survive the troposphere to be transported into this region. At the same time these short‐lived source gases produce appreciable amounts of Cly/Bry in the troposphere such that transport to the stratosphere offers a larger source for stratospheric Cly/Bry than in situ production. Thus, for reactive source species, simple methods of estimating the concentration of stratospheric Cly/Bry that ignore the tropospheric contribution will seriously underestimate the loading. Therefore estimation of the stratospheric Cly/Bry loading requires not only measurements of tropospheric source gases but also measurements of Cly/Bry at the tropopause. This paper illustrates the mechanism by using results from a two‐dimensional chemistry‐transport model. However, in view of the importance of tropospheric transport on stratospheric loading the detailed values should be further evaluated using a three‐dimensional model with appropriate treatment of convective transport.