Influence of water vapor on the process of new particle formation during monoterpene ozonolysis

This study was focused on the investigation of the influence of water vapor on the size distribution of the newly formed aerosol particles during the reaction of monoterpenes and ozone measured by a scanning mobility particle sizer (TSI 3936). Measurements made during reactions of selected exocyclic monoterpenes W-pinene and sabinene, 1 ppmv) with ozone (0.5 ppmv) showed a decrease of the particle number concentration and total aerosol volume with increasing water vapor. On the contrary, number concentration and total aerosol volume were not affected or less affected by the presence of water vapor during similar experiments with the endocyclic monoterpenes alpha-pinene and Delta(3)-carene. However, when the reactant concentrations of alpha-pinene and ozone were lowered to 50 and 110 ppbv, a similar decreasing effect of water vapor on the nucleation was observed as found in the exocyclic monoterpene reactions, whereas an increase of the produced aerosol volume was measured. These observations contradict the assumption that the dicarboxylic acids, such as pinic acid in the case of alpha- and beta-pinene, produced by the unimolecular decomposition of the excited Criegee intermediate, are responsible for the observed nucleation. The dicarboxylic acids should therefore be independent of the concentration of water vapor. On the contrary, we bring evidence that new particle formation proceeds via the stabilized Criegee intermediate. Furthermore, the intermolecularly (e.g., beta-pinene) or intramolecularly (e.g., alpha-pinene) formation of secondary ozonides acting as nucleation precursors explains the observed effect of water vapor. The results of similar experiments with added formic acid and carbonyl compounds are supportive of this assumption.