Effects of pH on Interfacial Ozonolysis of α-Terpineol.

Acidity changes the physical properties of atmospheric aerosol particles and the mechanisms of reactions that occur therein and on the surface. Here, we used surface-sensitive pneumatic ionization mass spectrometry to investigate the effects of pH on the heterogeneous reactions of aqueous α-terpineol (CHOH), a representative monoterpene alcohol, with gaseous ozone. Rapid (≤10 μs) ozonolysis of α-terpineol produced Criegee intermediates (CIs, zwitterionic/diradical carbonyl oxides) on the surface of water microjets. We studied the effects of microjet bulk pH (1-11) on the formation of functionalized carboxylate and α-hydroxy-hydroperoxide chloride adduct (HH-Cl) products generated by isomerization and hydration of α-terpineol CIs, respectively. Compared with the signal at pH ≈ 6, the mass spectral signal of HH-Cl was less intense under both basic and more acidic conditions, whereas the intensity of the functionalized carboxylate signal increased with increasing pH up to 4 and then remained constant. The decrease of HH-Cl signals at bulk pH values of >6 is attributable to the accumulation of OH at the air-water interface that suppresses the relative abundance of hydrophilic HH and Cl. The present study suggests that α-terpineol in ambient aqueous organic aerosols will be converted into much lower volatile and potentially toxic organic hydroperoxides during the heterogeneous ozonolysis.