Heterogeneous Ozonolysis of Squalene: Gas-Phase Products Depend on Water Vapor Concentration

Previous work examining the condensed-phase products of squalene particle ozonolysis found that an increase in water vapor concentration led to lower concentrations of secondary ozonides, increased concentrations of carbonyls, and smaller particle diameter, suggesting that water changes the fate of the Criegee intermediate. To determine if this volume loss corresponds to an increase in gas-phase products, we measured gas-phase volatile organic compound (VOC) concentrations via proton-transfer-reaction time-of-flight mass spectrometry. Studies were conducted in a flow-tube reactor at atmospherically relevant ozone (O₃) exposure levels (5-30 ppb h) with pure squalene particles. An increase in water vapor concentration led to strong enhancement of gas-phase oxidation products at all tested O₃ exposures. An increase in water vapor from near zero to 70% relative humidity (RH) at high O₃ exposure increased the total mass concentration of gas-phase VOCs by a factor of 3. The observed fraction of carbon in the gas-phase correlates with the fraction of particle volume lost. Experiments involving O₃ oxidation of shirts soiled with skin oil confirms that the RH dependence of gas-phase reaction product generation occurs similarly on surfaces containing skin oil under realistic conditions. Similar behavior is expected for O₃ reactions with other surface-bound organics containing unsaturated carbon bonds.