Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 7 4 2007 10.5194/acpd-7-11973-2007 http://www.atmos-chem-phys-discuss.net/7/11973/2007/ http://www.atmos-chem-phys-discuss.net/7/11973/2007/acpd-7-11973-2007.html http://www.atmos-chem-phys-discuss.net/7/11973/2007/acpd-7-11973-2007.pdf 11973 12009 2007-08-14 Reversible and irreversible processing of biogenic olefins on acidic aerosols J. Liggio john.liggio@ec.gc.ca S.-M. Li Air Quality Research Division, Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario, M3H 5T4, Canada Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA); however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ester formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. 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