title: Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface.
abstract: We report on experiments that probe photosensitized chemistry at the air/water interface, a region that does not just connect the two phases but displays its own specific chemistry. Here, we follow reactions of octanol, a proxy for environmentally relevant soluble surfactants, initiated by an attack by triplet-state carbonyl compounds, which are themselves concentrated at the interface by the presence of this surfactant. Gas-phase products are determined using PTR-ToF-MS, and those remaining in the organic layer are determined by ATR-FTIR spectroscopy and HPLC-HRMS. We observe the photosensitized production of carboxylic acids as well as unsaturated and branched-chain oxygenated products, compounds that act as organic aerosol precursors and had been thought to be produced solely by biological activity. A mechanism that is consistent with the observations is detailed here, and the energetics of several key reactions are calculated using quantum chemical methods. The results suggest that the concentrating nature of the interface leads to its being a favorable venue for radical reactions yielding complex and functionalized products that themselves could initiate further secondary chemistry and new particle formation in the atmospheric environment.
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.|§Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Shanghai 200433, China.|⊥Collaborative Innovation Center of Atmospheric Environment and Equipment Technology (CICAEET), Nanjing 210044, China.
authors.forename: Hongbo
authors.initials: H
authors.lastname: Fu
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Raluca
authors.initials: R
authors.lastname: Ciuraru
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Yoan
authors.initials: Y
authors.lastname: Dupart
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Monica
authors.initials: M
authors.lastname: Passananti
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Liselotte
authors.initials: L
authors.lastname: Tinel
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Rossignol
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Sebastien
authors.initials: S
authors.lastname: Perrier
authors.affiliation: ∥Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario M5S 3H6, Canada.
authors.forename: D James
authors.initials: DJ
authors.lastname: Donaldson
authors.affiliation: §Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Shanghai 200433, China.
authors.forename: Jianmin
authors.initials: J
authors.lastname: Chen
authors.affiliation: †Université de Lyon 1, Lyon, F-69626, France.|‡CNRS, UMR5256, IRCELYON, Institut de Recherches Sur la Catalyse et l'Environnement de Lyon, Villeurbanne, F-69626, France.
authors.forename: Christian
authors.initials: C
authors.lastname: George