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

Sep 23, 2016 | Atmospheric Chemistry, References and publications

Place of publication

Atmos. Chem. Phys., 16, 11823–11836, 2016

Field

Atmospheric Chemistry

Keywords

Atmospheric Chemistry; radical formation; Photochemistry; NO; NOx; NO2

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Instrument used for NO, NO₂ and NOx measurements

ECO PHYSICS 77 AM and ECO PHYSICS CLD 88

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Abstract

The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its lightabsorbing 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. PHO2 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 PHO2 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 NOx in aerosol flow tube experiments, confirming significant PHO2 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.

DOI

https://doi.org/10.5194/acp-16-11823-2016

Link

www.atmos-chem-phys.net/16/11823/2016/

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