Formation and Evolution of aqSOA from Aqueous-Phase Reactions of Phenolic Carbonyls : Comparison between Ammonium Sulfate and Ammonium Nitrate Solutions

We investigate the effects of sulfate and nitrate on the formation and evolution of secondary organic aerosol formed in the aqueous phase (aqSOA) from photooxidation of two phenolic carbonyls emitted from wood burning. AqSOA was formed efficiently from the photooxidation of both syringaldehyde (C₉H₁₀O₄) and acetosyringone (C₁₀H₁₂O₄) in ammonium sulfate and ammonium nitrate solutions, with mass yields ranging from 30% to 120%. Positive matrix factorization on the organic mass spectra acquired by an Aerosol Mass Spectrometer revealed a combination of functionalization, oligomerization and fragmentation processes in the chemical evolution of aqSOA. Functionalization and oligomerization dominated in the first 4 hours of reaction, with phenolic oligomers and their derivatives significantly contributing to aqSOA formation; andoxidation of the first-generation products led to an abundance of oxygenated ring-opening products. Degradation rates of syringaldehyde and acetosyringone in nitrate solutions were 1.5 and 3.5 times faster than rates in sulfate solutions, and aqSOA yields in nitrate experiments are twice as high as in sulfate experiments. Nitrate likely promoted the reactions because it is a photolytic source of OH radicals, while sulfate is not, highlighting the importance of aerosol-phase nitrate in the formation of aqSOA by facilitating the photooxidation of organic precursors.