Reactivity of Monoterpene Criegee Intermediates at Gas-Liquid Interfaces

摘要

Biogenic monoterpenes are major sources of Criegee intermediates (CIs) in the troposphere. Recent studies underscored the importance of their heterogeneous chemistry. The study of monoterpene CI reactions on liquid surfaces, however, is challenging due to the lack of suitable probes. Here, we report the first mass spectrometric detection of the intermediates and products, which include labile hydroperoxides, from reactions of CIs of representative monoterpenes (alpha-terpinene, gamma-terpinene, terpinolene, D-limonene, alpha-pinene) with water, cis-pinonic acid (CPA) and octanoic acid (OA) on the surface of liquid microjets. Significantly, the relative yields of alpha-hydroxy-hydroperoxides production from CIs hydration at the gas-liquid interface-alpha-terpinene (1.00) D-limonene (0.18) gamma-terpinene (0.11) similar to terpinolene (0.10) alpha-pinene (0.01)-do not track the rate constants of their gas-phase ozonolyses. Notably, in contrast with the inertness of the other CIs, the CIs derived from a-terpinene ozonolysis readily react with CPA and OA to produce C-20 and C-18 ester hydroperoxides, respectively. Present results reveal hitherto unknown structural effects on the reactivities of CIs at aqueous interfaces.