Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 5 4 2005 10.5194/acp-5-1027-2005 http://www.atmos-chem-phys.net/5/1027/2005/ http://www.atmos-chem-phys.net/5/1027/2005/acp-5-1027-2005.html http://www.atmos-chem-phys.net/5/1027/2005/acp-5-1027-2005.pdf 1027 1038 2005-03-29 Modelling the impact of noctilucent cloud formation on atomic oxygen and other minor constituents of the summer mesosphere B. J. Murray J. M. C. Plane School of Environmental Sciences, University of East Anglia, Norwich, UK NR4 7TJ now at: Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada V6T 1Z1 The formation, evolution and eventual sublimation of noctilucent clouds (NLC) may have a significant effect on the odd oxygen and hydrogen chemistry of the high latitude summer mesosphere. Three mechanisms are considered here: the direct uptake of atomic oxygen on the surface of the ice particles; the redistribution of water vapour, which changes the photochemical source of odd hydrogen species; and the direct photolysis of the ice particles themselves to produce odd hydrogen species in the gas phase. A 1-D photochemical model is employed to investigate the potential importance of these mechanisms. This shows, using the recently measured uptake coefficients of O on ice, that the heterogeneous removal of O on the surface of the cloud particles is too slow by at least a factor of 5x10³ to compete with gas-phase O chemistry. The second and third mechanisms involve the solar Lyman-α photolysis of H₂O in the gas and solid phase, respectively. During twilight, Lyman-α radiation is severely attenuated and these mechanisms are insignificant. In contrast, when the upper mesosphere is fully illuminated there is a dramatic impact on the O profile, with depletion of O at the base of the cloud layer of close to an order of magnitude. A correspondingly large depletion in O₃ is also predicted, while H, OH, HO₂ and H₂O₂ are found to be enhanced by factors of 3-5. In fact, rocket-borne mass spectrometer measurements during summer have revealed local H₂O₂ enhancements in the region of the clouds. Rocket-borne measurements of atomic O and O₃ profiles in the presence of mesospheric clouds in the daytime are highly desirable to test the predictions of this model and our understanding of the genesis of mesospheric clouds.