Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM<sub>2.5</sub>

Abstract

Abstract. Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H 2 O 2 or NO x . Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gasand particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivativebased methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, dthreonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM 2.5 samples, and could potentially serve as organic markers of 13BD. Furthermore, a series of oligoesters were detected and found to be produced through chemical reactions occurring in the aerosol phase between compounds bearing alcoholic groups and compounds bearing acidic groups.SOA was analyzed for organic mass to organic carbon (OM / OC) ratio, effective enthalpy of vaporization ( H eff vap ), and aerosol yield. The average OM / OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average H eff vap was −26.08 ± 1.46 kJ mol −1 , a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 µg m −3 was 0.025 ± 0.011, a value consistent with the literature (0.021-0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been examined.The contribution of SOA products from 13BD oxidation to ambient PM 2.5 was investigated by analyzing a series of ambient PM 2.5 samples collected in several locations around the United States. In addition to the occurrence of several organic compounds in field and laboratory samples, glyceric acid, dthreitol, erythritol, erythrose, and threonic acid were found to originate only from the oxidation of 13BD based on our previous experiments involving chamber oxidation of a series of hydrocarbons. Initial attempts have been made to quantify the concentrations of these compounds. The average concentrations of these compounds in ambient PM 2.5 samples from the California Research at the Nexus of Air Quality and Climate Change (CalNex) study ranged from 0 to approximately 14.1 ng m −3 . The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from 13BD oxidation could contribute to the ambient aerosol mainly in areas with high 13BD emission rates.

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

“…This could represent a substituent effect that influences the sensitivity of the gas-phase precursors to reaction by the acidic sulfate nucleophile, but further organic analysis of the aerosol-phase constituents would be required to examine this possibility in detail. Although recent studies have compared the reaction pathways and products formed for 1,3-butadiene oxidation vs. isoprene oxidation (Jaoui et al, 2014), these studies did not focus on acid-influenced reactions or organosulfate formation. Table 4 provides the initial conditions for the two isoprene/NO experiments designed to examine changes in SOC formation and yields resulting from changes in humidity.…”

“…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.…”

Chemical Composition of PM<sub>2.5</sub> in October 2017 Northern California Wildfire Plumes

“…For instance, malic acid and tartaric acid were found in aged wood smoke in oxidation experiments (Hartikainen et al, 2020). However, they can be produced in the oxidation of 1,3-butadinene and isoprene (Claeys et al, 2004;Jaoui et al, 2014). Malic acid can also be produced by the hydroxylation of succinic acid, an oxidation product of long-chain unsaturated fatty acids (Kawamura et al, 1996;Kawamura and Ikushima, 1993).…”

Kinetic and Mechanistic Studies for the Gas-phase Reaction of Ozone with 2, 3-Dimethyl-2-Butene and 1, 3-Butadiene

“…In addition, there is evidence for the importance of chlorine atom reactions with various alkanes and alkyl nitrates in the arctic troposphere during springtime [9,10]. 1,3-butadiene, and 2,3-dimethyl-2butene among those VOC emitted into the troposphere principally from many sources like fuel combustion and from refinery industry and biomass burning as well as many other sources of burning and forest fires [11,12]. However, the reactions of 1,3-Butadiene in the troposphere with OH radicals, NO 3 radicals, and O 3 can participate in the removal processes of 1,3-Butadiene from this layer.…”

“…Because of OH high concentrations, its reaction with 1,3-Butadiene dominates in the atmosphere during the daytime, while the loss processes through the reactions with ozone and NO 3 still doing its part in the overall removal process of 1,3-Butadiene from the atmosphere. Acrolein and formaldehyde have been noticed as the initial products from those reactions and considerably furan from the reaction with OH, and nitrates from the reaction with NO 3 [5,11]. There were some studies suggested that a possible reaction of 2,3-dimethyl 2butene with bromine may be participated in elimination of this compound from the atmosphere [13].…”