The relative importance of competing pathways for the formation of high-molecular-weight peroxides in the ozonolysis of organic aerosol particles
1Division of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA
2Institute of Low Temperature Science, Hokkaido University, Sapporo, 060-0819, Japan
3Aerodyne Research, Inc., Billerica, MA 08121, USA
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. Criegee intermediates are formed by the ozonolysis of the double bond in methyl oleate. An aerosol flow tube coupled to an Aerodyne quadrupole aerosol mass spectrometer is employed for the studies. The relative importance of different HMW organic peroxides, including secondary ozonides (SOZ's), α-acyloxyalkyl hydroperoxides and α-acyloxyalkyl alkyl peroxides (αAAHP-type compounds), diperoxides, and monoperoxide oligomers, is determined for the ozonolysis of different mixing mole fractions of MO in DOA and MA. Two SOZ's are identified as the HMW products of the ozonolysis of pure methyl oleate. Changes in the mobility and vacuum aerodynamic diameters of the particles indicate that up to 67% of the product mass remains in the particles, with the balance evaporating. In mixed particles, SOZ's form within 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 initial MO mole fractions under 0.5, 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 suggest that SCI's formed by the ozonolysis of unsaturated organic molecules in atmospheric particles could lead to the transformation of carboxylic acids and other protic groups into HMW organic peroxides.