Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene.

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m smog chamber. The presence of FeSO or Fe(SO) seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO or (NH)SO. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO or Fe(SO) seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.