The relative importance of competing pathways for the formation of high-molecular-weight peroxides in the ozonolysis of organic aerosol particles

Abstract. High-molecular-weight (HMW) organic compounds are an important component of atmospheric particles, although their origins, possibly including in situ formation pathways, remain incompletely understood. This study investigates the formation of HMW organic peroxides through reactions involving stabilized Criegee intermediates (SCI's). The model system is methyl oleate (MO) mixed with dioctyl adipate (DOA) and myristic acid (MA) in submicron aerosol particles, and Criegee intermediates are formed by the ozonolysis of the double bond in methyl oleate. An aerosol flow tube coupled to a quadrupole aerosol mass spectrometer (AMS) is employed to determine the relative importance of different HMW organic peroxides following the ozonolysis of different mixing mole fractions of MO in DOA and MA. Possible peroxide products include secondary ozonides (SOZ's), α-acyloxyalkyl hydroperoxides and α-acyloxyalkyl alkyl peroxides (αAAHP-type compounds), diperoxides, and monoperoxide oligomers. Of these, the AMS data identify two SOZ's as major HMW products in the ozonolysis of pure methyl oleate as well as in an inert matrix of DOA to as low as 0.04 mole fraction MO. In comparison, in mixed particles of MO and MA, αAAHP-type compounds form in high yields for MO mole fractions of 0.5 or less, suggesting that SCI's efficiently attack the carboxylic acid group of myristic acid. The reactions of SCI's with carboxylic acid groups to form αAAHP-type compounds therefore compete with those of SCI's with aldehydes to form SOZ's, provided that both types of functionalities are present at significant concentrations. The results therefore suggest that SCI's in atmospheric particles contribute to the transformation of carboxylic acids and other protic groups into HMW organic peroxides.