Interfacial vs Bulk Ozonolysis of Nerolidol

This is the authors' abstract. We don't add key points for this paper.

Ozone readily reacts with olefins with the formation of more reactive Criegee intermediates (CIs). The transient CIs impact HOx cycles, and they play a role in new particle formation in the troposphere. Oxidation by O3 occurs both in the gas-phase, in the liquid phase, and at air–water and air–aerosol interfaces. In light of the importance of O3 in environmental and engineered chemical transformations, we have investigated the ozonolysis mechanisms of a triolefin C15-alcohol, nerolidol (Nero, a biogenic sesquiterpene), at the air–water interface in the presence of acetonitrile. Surface-sensitive pneumatic ionization mass spectrometric detection of α-hydroxy-hydroperoxides and functionalized carboxylates, generated by the hydration and isomerization of CIs, respectively, enables us to evaluate the relative reactivity of each C=C toward O3. In addition, we compare bulk-phase ozonolysis chemistry to similar reactions taking place at the air–water interface. Our experimental results show that O3 reacts primarily with the (CH3)2C=CH– and −(CH3)C=CH– moieties (>∼98%), while the O3 attack on the terminal −HC=CH2 site (<∼2%) is a minor pathway during both interfacial and bulk ozonolysis. The presence of functionalized-carboxylates on interfaces but not in bulk-phase reactions with O3 indicates that the isomerization of the CIs is not hindered at the air–water interface due to the lower availability of water .