1University of California, Riverside, Department of Chemical and Environmental Engineering, Riverside, USA
2College of Engineering – Center for Environmental Research and Technology (CE-CERT), Riverside, USA
3University of California, Riverside, Department of Chemistry, Riverside, USA
4University of California, Riverside, Air Pollution Research Center, Riverside, USA
Received: 17 Oct 2011 – Discussion started: 15 Nov 2011
Abstract. This study evaluates the significance of glyoxal acting as an intermediate species leading to secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH4)2SO4 seed particles is observed in agreement with previous studies; however, glyoxal did not partition significantly to SOA (with or without aqueous seed) during aromatic hydrocarbon photooxidation within an environmental chamber (RH less than 80%). Rather, glyoxal influences SOA formation by raising hydroxyl (OH) radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1) increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2) glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase SOA volume under dark; (3) SOA formation from toluene + NOx photooxidation with and without deliquesced (NH4)2SO4 seed resulted in similar SOA growth, consistent with a minor contribution from glyoxal uptake onto deliquesced seed and organic coatings; and (4) the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS) in SOA from 2-tert-butylphenol (BP) oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol during the oxidation of aromatic hydrocarbons is more limited than previously thought.
Revised: 17 Apr 2012 – Accepted: 17 Apr 2012 – Published: 03 May 2012
Nakao, S., Liu, Y., Tang, P., Chen, C.-L., Zhang, J., and Cocker III, D. R.: Chamber studies of SOA formation from aromatic hydrocarbons: observation of limited glyoxal uptake, Atmos. Chem. Phys., 12, 3927-3937, doi:10.5194/acp-12-3927-2012, 2012.