Influence of the heterogeneous reaction HCL + HOCl on an ozone hole model with hydrocarbon additions
- Los Alamos National Lab., NM (United States)
- Univ. of California, Irvine, CA (United States)
- Univ. of California, Los Angeles, CA (United States); and others
Injection of ethane or propane has been suggested as a means for reducing ozone loss within the Antarctic vortex because alkanes can convert active chlorine radicals into hydrochloric acid. In kinetic models of vortex chemistry including as heterogeneous processes only the hydrolysis and HCl reactions of ClONO{sub 2} and N{sub 2}O{sub 5}, parts per billion by volume levels of the light alkanes counteract ozone depletion by sequestering chlorine atoms. Introduction of the surface reaction of HCl with HOCl causes ethane to deepen baseline ozone holes and generally works to impede any mitigation by hydrocarbons. The increased depletion occurs because HCl + HOCl can be driven by HO{sub x} radicals released during organic oxidation. Following initial hydrogen abstraction by chlorine, alkane breakdown leads to a net hydrochloric acid activation as the remaining hydrogen atoms enter the photochemical system. Lowering the rate constant for reactions of organic peroxy radicals with ClO to 10{sup {minus}13} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} does not alter results, and the major conclusions are insensitive to the timing of the ethane additions. Ignoring the organic peroxy radical plus ClO reactions entirely restores remediation capabilities by allowing HO{sub x} removal independent of HCl. Remediation also returns if early evaporation of polar stratospheric clouds leaves hydrogen atoms trapped in aldehyde intermediates, but real ozone losses are small in such cases. 95 refs., 4 figs., 7 tabs.
- OSTI ID:
- 136154
- Journal Information:
- Journal of Geophysical Research, Vol. 99, Issue D2; Other Information: PBD: 20 Feb 1994
- Country of Publication:
- United States
- Language:
- English
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