Atmospheric Chemistry and Physics, vol. 13, issue 17 (2013) pp. 8651-8667
Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C-2), methylglyoxal (C-3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (similar to 10(-6)-similar to 10(-3) M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are similar to 120% for glyoxal and similar to 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (similar to 10 M), the major oxidation products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are similar to 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.
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