Journal
ATMOSPHERIC CHEMISTRY AND PHYSICS
Volume 16, Issue 18, Pages 11823-11836Publisher
COPERNICUS GESELLSCHAFT MBH
DOI: 10.5194/acp-16-11823-2016
Keywords
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Funding
- US National Science Foundation [ATM-847793, AGS-1452317]
- Chateaubriand Fellowship
- EU [265307]
- Swiss National Science Foundation [163074]
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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 (PHO2) 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] x [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 O-2/N-2 ratio (15% < O-2/N-2 < 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 O-2/N-2. 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 O-2 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 NOx 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.
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