Artifact peroxides produced during cryogenic sampling of ambient air

Peroxides were found to be produced as artifacts during cryogenic sampling with Horibe traps. Cryogenic trap sampling was compared to collection with a wet effluent diffusion denuder and a Nafion membrane diffusion denuder. Hydrogen peroxide and hydroxymethyl hydroperoxide measured in the cryogenic trap samples were significantly higher. In comparison, no evidence of artifact methyl hydroperoxide production was found. The amount of artifact H 2 O 2 and HMHP produced increased with decreasing trap temperature. Spiking ambient air with ethene or isoprene showed that these hydrocarbons, in the presence of ozone, can be responsible for the artifact production of peroxides. Our results clearly suggest that the peroxide data obtained by cryogenic sampling and reported in the literature should be interpreted with caution.