Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO₂ radical formation and aerosol growth

Abstract. The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO₂ radicals (P_HO2) was measured indirectly by converting gas-phase NO into NO₂. We report on experiments that relied on measurements of NO₂ formation, NO loss and HONO formation. P_HO2 was found to be a linear function of (1) the [IC]  ×  [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 %  <  RH  <  63 %) and of (4) the O₂ ∕ N₂ ratio (15 %  <  O₂ ∕ N₂  <  56 %) was observed, most likely indicating competing effects of dilution, HO₂ mobility and losses in the film. The maximum P_HO2 was observed at 25–55 % RH and at ambient O₂ ∕ N₂. The HO₂ radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O₂ to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO₂ in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NO_x in aerosol flow tube experiments, confirming significant P_HO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO₂ production, aerosol growth and ageing in the atmosphere.