Mesospheric removal of very long-lived greenhouse gases SF6 and CFC-115 by metal reactions, Lyman-α photolysis, and electron attachment.

The fluorinated gases SF6 and C2F5Cl (CFC-115) are chemically inert with atmospheric lifetimes of many centuries which, combined with their strong absorption of IR radiation, results in unusually high global warming potentials. Very long lifetimes imply that mesospheric sinks could make important contributions to their atmospheric removal. In order to investigate this, the photolysis cross sections at the prominent solar Lyman-α emission line (121.6 nm), and the reaction kinetics of SF6 and CFC-115 with the neutral meteoric metal atoms Na, K, Mg, and Fe over large temperature ranges, were measured experimentally. The Na and K reactions exhibit significant non-Arrhenius behavior; quantum chemistry calculations of the potential energy surfaces for the SF6 reactions indicate that the Na and K reactions with SF6 are probably activated by vibrational excitation of the F-SF5 (v3) stretching mode. A limited set of kinetic measurements on Na + SF5CF3 are also presented. The atmospheric removal of these long-lived gases by a variety of processes is then evaluated. For SF6, the removal processes in decreasing order of importance are electron attachment, VUV photolysis, and reaction with K, Na, and H. For CFC-115, the removal processes in decreasing order of importance are reaction with O((1)D), VUV photolysis, and reaction with Na, K, and H.