The Potential Influence of ClO·O2 on Stratospheric Ozone Depletion Chemistry

The inability to explain the observedoxygen suppression of chlorine photosensitized ozoneloss remains a gap in our understanding of thephotochemistry responsible for depletion of thestratospheric ozone layer. It has been suggested thatthe presence of a weakly bound ClO·O2complexcould explain this effect. The existence of thiscomplex would alter the chlorine budget of thestratosphere, perhaps reducing the chlorine availablefor catalytic ozone destruction. On the other hand,the chemistry of ClO·O2 provides two newpathwaysfor ClO dimer formation, which could increase the rateof catalytic ozone loss. In this paper, we constrainthe kinetic rate system of ClO·O2 tomatch themeasured Cly budget. It is shown thatClO·O2cannot be both fairly stable and rapidly form the ClOdimer, or the resulting partitioning of chlorinebecomes incompatible with observations of both ClO andtotal available chlorine. These constraints allow thateither: (1) the ClO·O2 is fairly stable,but doesnot significantly enhance ClO dimer formation andtherefore has a negligible effect on ozone loss rates,or (2) the ClO·O2 complex is only veryweaklystable, but does rapidly form the ClO dimer, andtherefore can influence stratospheric ozone depletion.Even at the ClO·O2 mixing ratios allowedunderthe assumption of weak stability, 0.1 to 0.2 ppbv,significant ozone loss rate enhancements werecalculated. Of course, the chlorine budget constraintalso allows for a thirdpossibility; that ClO·O2 is neither verystablenor forms Cl2O2 very rapidly. Measuredlimits on the reaction rates for ClO·O2to form the ClO dimer would greatly aid the resolution of thisissue. Since the uncertainties aboutClO·O2chemistry are so large, a potential role forClO·O2 in stratospheric ozone loss cannotbe ruled out at this time.