title: Characterization of polar organosulfates in secondary organic aerosol from the green leaf volatile 3-Z-hexenal.
abstract: Evidence is provided that the green leaf volatile 3-Z-hexenal serves as a precursor for biogenic secondary organic aerosol through the formation of polar organosulfates (OSs) with molecular weight (MW) 226. The MW 226 C6-OSs were chemically elucidated, along with structurally similar MW 212 C5-OSs, whose biogenic precursor is likely related to 3-Z-hexenal but still remains unknown. The MW 226 and 212 OSs have a substantial abundance in ambient fine aerosol from K-puszta, Hungary, which is comparable to that of the isoprene-related MW 216 OSs, known to be formed through sulfation of C5-epoxydiols, second-generation gas-phase photooxidation products of isoprene. Using detailed interpretation of negative-ion electrospray ionization mass spectral data, the MW 226 compounds are assigned to isomeric sulfate esters of 3,4-dihydroxyhex-5-enoic acid with the sulfate group located at the C-3 or C-4 position. Two MW 212 compounds present in ambient fine aerosol are attributed to isomeric sulfate esters of 2,3-dihydroxypent-4-enoic acid, of which two are sulfated at C-3 and one is sulfated at C-2. The formation of the MW 226 OSs is tentatively explained through photooxidation of 3-Z-hexenal in the gas phase, resulting in an alkoxy radical, followed by a rearrangement and subsequent sulfation of the epoxy group in the particle phase.
authors.affiliation: Department of Pharmaceutical Sciences, University of Antwerp , BE-2610 Antwerp, Belgium.
authors.forename: Mohammad Safi
authors.initials: MS
authors.lastname: Shalamzari
authors.forename: Ariane
authors.initials: A
authors.lastname: Kahnt
authors.forename: Reinhilde
authors.initials: R
authors.lastname: Vermeylen
authors.forename: Tadeusz E
authors.initials: TE
authors.lastname: Kleindienst
authors.forename: Michael
authors.initials: M
authors.lastname: Lewandowski
authors.forename: Filip
authors.initials: F
authors.lastname: Cuyckens
authors.forename: Willy
authors.initials: W
authors.lastname: Maenhaut
authors.forename: Magda
authors.initials: M
authors.lastname: Claeys
mesh_terms: D000336:Aerosols / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry; D002853:Chromatography, Liquid; D006591:Hexobarbital / Q000032:analysis* / Q000737:chemistry; D006814:Hungary; D013058:Mass Spectrometry; D008970:Molecular Weight; D018515:Plant Leaves / Q000737:chemistry*; D013431:Sulfates / Q000737:chemistry*; D055549:Volatile Organic Compounds / Q000032:analysis*
chemical_list: D000336:Aerosols; D013431:Sulfates; D055549:Volatile Organic Compounds; D006591:Hexobarbital