Aerosol-chamber study of the α-pinene/O3 reaction:: influence of particle acidity on aerosol yields and products

a-Pinene ozonolysis was carried out in the presence of ammonium sulfate or sulfuric acid seed particles in a 9 m 3 Teflon chamber at the mixing ratios of 100ppbv for alpha-pinene and about 70 ppbv for ozone. The evolution of size distribution was measured by means of a differential mobility particle sizer (DMPS). The resulting secondary organic aerosol (SOA) was sampled by a denuder/quartz fiber filter combination for the determination of the total organic carbon concentration (TOC) in the particle phase, using a thermographic method and by a denuder/PTFE filter combination for the analysis of individual chemical species in the particle phase using capillary electrophoresiselectrospray ionization-mass spectrometry (CE-ESI-MS). cis-Pinic acid (m/z 185) and another species tentatively identified at m/z 171 and 199 were the major particle phase species for both seed particles although the product yields were different, indicating the influence of seed particle acidity. A thermographic method for the determination of TOC showed an increase of particle phase organics by 40% for the experiments with higher acidity. CE-ESI-MS analysis showed a large increase in the concentration of compounds with M-w > 300 from the experiments with sulfuric acid seed particles. These results suggest that the seed particle acidity enhances the yield of SOA and plays an important role in the formation of larger molecules in the particle phase. Our results from direct particle phase chemical analysis suggest for the first time that condensation of smaller organics takes place by polymerization or aldol condensation following the formation of aldehydes, such as pinonaldehyde from the terpene ozonolysis. (C) 2003 Elsevier Ltd. All rights reserved.