1Bourns College of Engineering – Center for Environmental Research & Technology, University of California, Riverside, 1084 Columbia Ave., Riverside, CA 92507, USA
2Asian Environment Research Group, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki, 305-8506, Japan
3Department of Chemical and Environmental Engineering, University of California, Riverside, CA 92521, USA
*now at: Center for Regional Environmental Research, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki, 305-8506, Japan
Received: 25 Jan 2011 – Published in Atmos. Chem. Phys. Discuss.: 07 Feb 2011
Abstract. Secondary organic aerosol (SOA) formation from atmospheric oxidation of isoprene has been the subject of multiple studies in recent years; however, reactions of other conjugated dienes emitted from anthropogenic sources remain poorly understood. SOA formation from the photooxidation of isoprene, isoprene-1-13C, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene is investigated for high NOx conditions. The SOA yield measured in the 1,3-butadiene/NOx/H2O2 irradiation system (0.089–0.178) was close to or slightly higher than that measured with isoprene under similar NOx conditions (0.077–0.103), suggesting that the photooxidation of 1,3-butadiene is a possible source of SOA in urban air. In contrast, a very small amount of SOA particles was produced in experiments with 2,3-dimethyl-1,3-butadiene. Off-line liquid chromatography – mass spectrometry analysis revealed that the signals of oligoesters comprise a major fraction (0.10–0.33) of the signals of the SOA products observed from all dienes investigated. The oligoesters originate from the unsaturated aldehyde gas phase diene reaction products; namely, semi-volatile compounds produced by the oxidation of the unsaturated aldehyde undergo particle-phase oligoester formation. Oligoesters produced by the dehydration reaction between nitrooxypolyol and 2-methylglyceric acid monomer or its oligomer were also characterized in these experiments with isoprene as the starting diene. These oligomers are possible sources of the 2-methyltetrols found in ambient aerosol samples collected under high NOx conditions. Furthermore, in low-temperature experiments also conducted in this study, the SOA yield measured with isoprene at 278 K was 2–3 times as high as that measured at 300 K under similar concentration conditions. Although oligomerization plays an important role in SOA formation from isoprene photooxidation, the observed temperature dependence of SOA yield is largely explained by gas/particle partitioning of semi-volatile compounds.
Revised: 30 Jun 2011 – Accepted: 21 Jul 2011 – Published: 25 Jul 2011
Sato, K., Nakao, S., Clark, C. H., Qi, L., and Cocker III, D. R.: Secondary organic aerosol formation from the photooxidation of isoprene, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene under high NOx conditions, Atmos. Chem. Phys., 11, 7301-7317, doi:10.5194/acp-11-7301-2011, 2011.