Secondary organic aerosol formation from the photooxidation of isoprene, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene under high NO<sub>x</sub> conditions

Abstract

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-1-13 C, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene is investigated for high NO x conditions. The SOA yield measured in the 1,3-butadiene/NO x /H 2 O 2 irradiation system (0.089-0.178) was close to or slightly higher than that measured with isoprene under similar NO x 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 Correspondence to: D. R. Cocker III (dcocker@engr.ucr.edu) starting diene. These oligomers are possible sources of the 2-methyltetrols found in ambient aerosol samples collected under high NO x 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.

AMS and LC/MS analyses of SOA from the photooxidation of benzene and 1,3,5-trimethylbenzene in the presence of NO<sub>x</sub>: effects of chemical structure on SOA aging

“…The SOA yield from benzene was higher than that from highly methylated 1,3,5-TMB. Sato et al (2011) reported that the SOA yield from a highly methylated conjugated diene is much lower than that from non-methylated 1,3butadiene. This previous result mirrors the present results for aromatic hydrocarbons.…”

Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

“…With respect to aerosol formation, 1,3-butadiene is also of interest as a structural analog for isoprene. SOA formation from 1,3-butadiene has been examined in a number of recent studies (Angove at al., 2006;Sato, 2008;Sato et al, 2011;Jaoui et al, 2014), although with only limited consideration of the effects of aerosol acidity.…”

Oligomer formation in the troposphere: from experimental knowledge to 3-D modeling

“…The oxidation of isoprene by hydroxyl radicals leads to the formation of methyl vinyl ketone and methacrolein (Pandis et al, 1991, Paulot et al, 2009, which in turn produces tetrols and methylglyceric acid (Claeys et al, 2004;Surratt et al, 2006;Kleindienst et al, 2009) that are aliphatic compounds. Although oligomer formation from the oxidation of isoprene has been shown to occur in smog chambers (e.g., Sato et al, 2011;Nguyen et al, 2011a, b;Liu et al, 2012a;Tan et al, 2012;Lin et al, 2014), the oligomer formation process is likely to differ significantly from that from aromatics as measured by Kalberer et al (2004). Second, since this kinetic constant only stands for an average reactivity, Kalberer et al (2004), during their experiments, could only observe the fact that 50 % of the total organic mass was conversed to oligomer-like species.…”

“…In CHIMERE, a sectional aerosol module provides the evolution of the concentrations of seven particulate groups of species: primary PM, nitrate, sulfate, ammonium, biogenic SOA, anthropogenic SOA and water (Schmidt et al, 2001;Bessagnet et al, 2004Bessagnet et al, , 2009. The size distribution of aerosol particles is represented using eight size sections ranging from 10 nm to 40 µm.…”