Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 5 2009 10.5194/acpd-9-20881-2009 http://www.atmos-chem-phys-discuss.net/9/20881/2009/ http://www.atmos-chem-phys-discuss.net/9/20881/2009/acpd-9-20881-2009.html http://www.atmos-chem-phys-discuss.net/9/20881/2009/acpd-9-20881-2009.pdf 20881 20911 2009-10-05 Hydroxyl radical reactivity at the air-ice interface T. F. Kahan R. Zhao D. J. Donaldson jdonalds@chem.utoronto.ca Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, M5S 3H6 Ontario, Canada Department of Physical and Environmental Sciences, University of Toronto at Scarborough, Toronto, M1C 1A4 Ontario, Canada Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at the air-ice interface, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH) anthracene at the air-water interface, but no loss was observed at the air-ice interface. 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