Multiphase reactivity of gaseous hydroperoxide oligomers produced from isoprene ozonolysis in the presence of acidified aerosols

Publication Type:

Journal Article

Source:

Atmospheric Environment, Volume 152, p.314-322 (2017)

Abstract:

Ozonolysis of alkenes results in the formation of primary ozonides (POZs), which can subsequently decompose into carbonyl compounds and stabilized Criegee intermediates (sCls). The sCIs generated from isoprene ozonolysis include the simplest congener, formaldehyde oxide (CH2OO), and isomers of C-4-sCI. Although the bimolecular reaction with H2O is expected to be the main fate of sCis, it was reported that sCis can also react with carboxylic acids and/or organic hydroperoxides leading to gas-phase oligomeric compounds. While the impact of the gas-phase composition (H2O, sCI scavenger) on the formation of such products was recently studied, their fate remains unclear. In the present work, formation of oligomeric hydroperoxides from isoprene ozonolysis, proposed as reaction products composed of the sCI as a chain unit and formed from the insertion of sCI into a hydroperoxide or a carboxylic acid, was systematically examined in the presence of aerosol with varying compositions. The effect of hydroxyl (OH) radicals on the gas- and particle-phase compositions was investigated using diethyl ether as an 011 radical scavenger. Thirty-four oligomeric compounds resulting from the insertion of sCls into organic hydroperoxides or carboxylic acids were identified using iodide chemical ionization high-resolution mass spectrometry. Large reactive uptake onto acidified sulfate aerosol was observed for most of the characterized gaseous oligomeric species, whereas the presence of organic coatings and the lack of aerosol water significantly reduced or halted the reactive uptake of these species. These results indicate that highly oxidized molecules, such as hydroperoxides, could undergo multiphase reactions, which are significantly influenced by the chemical composition of seed aerosol. Furthermore, in addition to functionalization and accretion, decomposition and re-volatilization should be considered in SOA formation.