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.

Experimental study of the mesospheric removal of NF3 by neutral meteoric metals and Lyman-α radiation.

NF3 is a potent anthropogenic greenhouse gas with increasing industrial usage. It is characterized by a large global warming potential due in part to its large atmospheric lifetime. The estimated lifetime of about 550 years means that potential mesospheric destruction processes of NF3 should also be considered. The reactions of NF3 with the neutral metal atoms Na, K, Mg and Fe, which are produced by meteoric ablation in the upper mesosphere, were therefore studied. The observed non-Arrhenius temperature dependences of the reactions between about 190 and 800 K are interpreted using quantum chemistry calculations of the relevant potential energy surfaces. The NF3 absorption cross section at the prominent Lyman-α solar emission line (121.6 nm) was determined to be (1.59 ± 0.10) × 10(-18) cm(2) molecule(-1) (at 300 K). In the mesosphere above 60 km, Lyman-α photolysis is the dominant removal process of NF3; the reactions with K and Na are 1-2 orders of magnitude slower. However, the atmospheric lifetime of NF3 is largely controlled by reaction with O((1)D) and photolysis at wavelengths shorter than 190 nm; these processes dominate below 60 km.