Articles | Volume 15, issue 21
Atmos. Chem. Phys., 15, 12267–12281, 2015
Atmos. Chem. Phys., 15, 12267–12281, 2015

Research article 05 Nov 2015

Research article | 05 Nov 2015

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

D. C. Draper1,a, D. K. Farmer2, Y. Desyaterik3, and J. L. Fry1 D. C. Draper et al.
  • 1Department of Chemistry, Reed College, Portland, OR, USA
  • 2Department of Chemistry, Colorado State University, Fort Collins, CO, USA
  • 3Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA
  • acurrent address: Department of Chemistry, University of California Irvine, Irvine, CA, USA

Abstract. The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-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. α-Pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-Pinene and Δ3-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. α-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 α-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.

Short summary
The addition of NO2 to atmospheric particle formation simulations based on ozone reactions with tree-emitted monoterpenes results in changing particle composition and mass yields, with effects that vary across the range of studied monoterpenes. For alpha-pinene, a dominantly emitted terpene in the United States, NO2 addition suppresses particle formation, while for others, particle yields remain high.
Final-revised paper