title: A new atmospherically relevant oxidant of sulphur dioxide.
abstract: Atmospheric oxidation is a key phenomenon that connects atmospheric chemistry with globally challenging environmental issues, such as climate change, stratospheric ozone loss, acidification of soils and water, and health effects of air quality. Ozone, the hydroxyl radical and the nitrate radical are generally considered to be the dominant oxidants that initiate the removal of trace gases, including pollutants, from the atmosphere. Here we present atmospheric observations from a boreal forest region in Finland, supported by laboratory experiments and theoretical considerations, that allow us to identify another compound, probably a stabilized Criegee intermediate (a carbonyl oxide with two free-radical sites) or its derivative, which has a significant capacity to oxidize sulphur dioxide and potentially other trace gases. This compound probably enhances the reactivity of the atmosphere, particularly with regard to the production of sulphuric acid, and consequently atmospheric aerosol formation. Our findings suggest that this new atmospherically relevant oxidation route is important relative to oxidation by the hydroxyl radical, at least at moderate concentrations of that radical. We also find that the oxidation chemistry of this compound seems to be tightly linked to the presence of alkenes of biogenic origin.
authors.affiliation: University of Helsinki, Department of Physics, FI-00014 Helsinki, Finland. roy.mauldin@helsinki.fi
authors.forename: R L
authors.initials: RL
authors.lastname: Mauldin
authors.forename: T
authors.initials: T
authors.lastname: Berndt
authors.forename: M
authors.initials: M
authors.lastname: Sipilä
authors.forename: P
authors.initials: P
authors.lastname: Paasonen
authors.forename: T
authors.initials: T
authors.lastname: Petäjä
authors.forename: S
authors.initials: S
authors.lastname: Kim
authors.forename: T
authors.initials: T
authors.lastname: Kurtén
authors.forename: F
authors.initials: F
authors.lastname: Stratmann
authors.forename: V-M
authors.initials: VM
authors.lastname: Kerminen
authors.forename: M
authors.initials: M
authors.lastname: Kulmala
mesh_terms: D000475:Alkenes / Q000378:metabolism; D001272:Atmosphere / Q000737:chemistry*; D005387:Finland; D005609:Free Radicals / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry; D016877:Oxidants / Q000737:chemistry* / Q000378:metabolism; D010126:Ozone / Q000737:chemistry; D013458:Sulfur Dioxide / Q000032:analysis / Q000737:chemistry*; D013729:Terpenes / Q000737:chemistry / Q000378:metabolism; D014197:Trees / Q000378:metabolism; D055549:Volatile Organic Compounds / Q000032:analysis / Q000737:chemistry / Q000378:metabolism
chemical_list: D000475:Alkenes; D005609:Free Radicals; D016877:Oxidants; D013729:Terpenes; D055549:Volatile Organic Compounds; D013458:Sulfur Dioxide; D017665:Hydroxyl Radical; D010126:Ozone