Partitioning of Organonitrates in the Production of Secondary Organic Aerosols from α-Pinene Photo-Oxidation

The chemical pathways for the production of secondary organic aerosols (SOA) are influenced by the concentration of nitrogen oxides (NO_x), including the production of organonitrates (ON). Herein, a series of experiments conducted in an environmental chamber investigated the production and partitioning of total organonitrates from α-pinene photo-oxidation from <1 to 24 ppb NO_x. Gas-phase and particle-phase organonitrates (gON and pON, respectively) were measured by laser-induced fluorescence (LIF). The composition of the particle phase and the particle mass concentration were simultaneously characterized by online aerosol mass spectrometry. The LIF and MS measurements of pON concentrations had a Pearson correlation coefficient of 0.91 from 0.3 to 1.1 μg m^-3. For 1-6 ppb NO_x, the yield of SOA particle mass concentration increased from 0.02 to 0.044 with NO_x concentration. For >6 ppb NO_x, the yield steadily dropped, reaching 0.034 at 24 ppb NO_x. By comparison, the yield of pON steadily increased from 0.002 to 0.022 across the range of investigated NO_x concentrations. The yield of gON likewise increased from 0.005 to 0.148. The gas-to-particle partitioning ratio (pON/(pON + gON)) depended strongly on the NO_x concentration, changing from 0.27 to 0.13 as the NO_x increased from <1 to 24 ppb. In the atmosphere, there is typically a cross-over point between clean and polluted conditions that strongly affects SOA production, and the results herein quantitatively identify 6 ppb NO_x as that point for α-pinene photo-oxidation under these study conditions, including the production and partitioning of organonitrates. The trends in SOA yield and partitioning ratio as a function of NOx occur because of the changes in pON volatility. © 2022 American Chemical Society. All rights reserved.