A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2

• Published in: Atmospheric chemistry and physics Vol. 15; no. 21; pp. 12267 - 12281
• Main Authors: Draper, D C, Farmer, D K, Desyaterik, Y, Fry, J L
• Format: Journal Article
• Language: English
• Published: Katlenburg-Lindau Copernicus GmbH 05.11.2015; Copernicus Publications
• Subjects: 3-Carene; Aerosol concentrations; Aerosol production; Aerosols; Anthropogenic factors; Atmosphere; Concentration (composition); Constraining; Experiments; Formations; High-performance liquid chromatography; HPLC; Human influences; Kinetics; Laboratories; Limonene; Liquid chromatography; Mass; Molecular weight; Monoterpenes; Night; Night-time; Nighttime; Nitrogen dioxide; Oligomerization; Oligomers; Organic compounds; Oxidants; Oxidation; Oxidizing agents; Ozonolysis; Reaction kinetics; Secondary aerosols; Studies; Terpenes; VOCs; Volatile organic compounds; Yield; α-Pinene; United States > US
• ISSN: 1680-7316; 1680-7324
• DOI: 10.5194/acp-15-12267-2015

The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of alpha -pinene, beta -pinene, Delta 3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first-generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. alpha -Pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. beta -Pinene and Delta 3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW > 400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. alpha -Pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of alpha -pinene's near 0 % yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the volatile organic compound precursor, is essential in predicting nighttime aerosol production.