Aging of secondary organic aerosol from α-pinene ozonolysis: Roles of hydroxyl and nitrate radicals

Abstract

This work investigates the oxidative aging of preformed secondary organic aerosol (SOA) derived from α-pinene ozonolysis (~100 ppbv hydrocarbon [HCx] with excess of O3) within the University of California-Riverside Center for Environmental Research and Technology environmental chamber that occurs after introduction of additional hydroxyl (OH) and nitrate (NO3) radicals. Simultaneous measurements of SOA volume concentration, hygroscopicity, particle density, and elemental chemical composition (C:O:H) reveal increased particle wall-loss-corrected SOA formation (1.5%, 7.5%, and 15.1%), increase in oxygen-to-carbon ratio (O/C; 15.6%, 8.7%, and 8.7%), and hydrophilicity (4.2%, 7.4%, and 1.4%) after addition of NO (ultraviolet [UV] on), H2O2 (UV on), and N2O5 (dark), respectively. The processing observed as an increase in O/C and hydrophilicity is attributed to OH and NO3 reactions with first-generation vapor products and UV photolysis. The rate of increase in O/C appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) on a day time scale even at the raised chamber radical concentrations. The additional processing with UV irradiation without addition of NO, H2O2, or N2O5 is observed, adding 5.5% wall-loss-corrected volume. The photolysis-only processing is attributed to additional OH generated from photolysis of the nitrous acid (HONO) offgasing from chamber walls. This finding indicates that OH and NO3 radicals can further alter the chemical composition of SOA from α-pinene ozonolysis, which is proved to consist of first-generation products.Secondary organic aerosol (SOA) may undergo aging processes once formed in the atmosphere, thereby altering the physicochemical and toxic properties of aerosol. This study discusses SOA aging of a major biogenic volatile organic compound (VOC; α-pinene) after it initially forms SOA. Aging of the α-pinene ozonolysis system by OH (through NO or H2O2 injection), NO3 (through N2O5 injection), and photolysis is observed. Although the reaction rate appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) level of oxygenation on a 1-day scale, it is important that SOA aging be considered in ambient air quality models. Aging in this study is attributed to further oxidation of gas-phase oxidation products of α-pinene ozonolysis.Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for information on the referenced α-pinene ozonolysis reaction and chamber reactor temperature. © 2012 Copyright 2012 A&WMA.