Reactions Of Hydroxyl Radicals With Oxygenated Hydrocarbons In The Gas Phase A Laser Photolysis Laser Induced Fluorescence Study PDF Download

We have also measured the kinetics and products of a reaction between gas-phase ozone and anthracene adsorbed at the air-aqueous interface. The reactions at the "uncoated" air-water interface and at an interface consisting of a monolayer of various organic compounds were studied. In all the cases, the reaction follows a Langmuir-Hinshelwood mechanism, in which ozone first adsorbs to the air-aqueous interface, and then reacts with adsorbed anthracene. For typical atmospheric ozone concentrations, the estimated reactive uptake coefficient ranges from 2 x 10-8 to 3 x 10-7 depending on the nature of the air-aqueous interface. Smaller (C4, C6) carboxylic acids at the interface inhibit the reaction (compared to the "clean" water surface); 1-octanol enhances it. Under some circumstances, oxidation by ozone on aqueous surfaces may be more important in the atmosphere than gas phase oxidation by OH radicals. The fate of atmospheric semi-volatile organic compounds (SOCs) such as polycyclic aromatic hydrocarbons (PAHs) depends, in part, on their distribution between the gas phase and particulate phases, and oxidation reactions. In the daytime troposphere, photochemically produced OH radicals dominate these reactions, whereas chlorine atoms may contribute to the oxidation of certain PAHs in coastal areas. In the dark, oxidation by nitrate radicals (NO3) may also be important, whereas ozone can contribute to the oxidation both during the day and at night. We have developed a laser-induced fluorescence (LIF) method to study adsorption and oxidation of PAHs at the air-aqueous interface. This method allows to directly probe the mechanisms and extent of PAH uptake on aqueous surfaces. The kinetics of the adsorption of anthracene and pyrene onto "pure" water and water coated with an organic film were measured. The surface uptake coefficients of both PAHs are estimated to be on the order of 10-5, and increase by a factor of 2--3 for uptake to the 1-octanol coated water surface. However, the surface uptake of pyrene to a hexanoic-acid-coated aqueous surface does not display this enhancement. Resolved fluorescence spectra of pyrene adsorbed onto 1-octanol-coated surfaces indicate that pyrene is in a less polar environment than when adsorbed at the hexanoic-acid-coated surfaces.