Polyphenylenesulfide, noxon® an ozone scavenger for the analysis of oxygenated terpenes in air

During sampling, oxygenated terpenes may undergo decomposition through reaction with atmospheric ozone. We have studied their ozonolytic decomposition during preconcentration on Tenax. The saturated. terpenoids 1,8-cineole, bornyl acetate nopinone and pinonaldehyde are practically unaffected by ozone in the range of 8 to 120 ppbv. Compounds which contain one or more C----C double bonds are decomposed in the order: linalool ≈ citronellal ≈ 6-methyl-5-hepten-2-one > citral > 4-acetyl-1-methyl-cyclohexane > 3-(1-methylethenyl)-6-oxo-heptanal > myrtenal ≈ 2-methyl-3-buten-2-ol. The degree of decomposition varies from 0 to 5% for the least reactive to 80 to 90% for the most reactive compounds. A broad range of material was investigated as potential ozone scavengers. By using the polymer noXon (polyphenylenesulfide) all the investigated compounds could be sampled with quantitative recoveries even at high ozone mixing ratios (95–110 ppbv). This ozone scrubber was tested for sampling of terpene oxidation products on Tenax and dinitrophenylhydrazine impregnated C18-silicagel cartridges. Recoveries from 85 to 110% were obtained for all investigated compounds. The method was used for the analysis of oxidation products of terpenes in ambient air in three campaigns. Attention was focused on nopinone from β-pinene, pinonaldehyde from α-pinene, 3-(1-methylethenyl)-6-oxo-heptanal and 4-acetyl-1-methyl-cyclohexane from limonene, and 5-(1-methylethyl)-bicyclo[3.1.0] hexan-2-one from sabinene. Nopinone was the only product which could be frequently detected in ratios from 0 to 90% of the measured β-pinene concentrations. Pinonaldehyde was encountered only once (30% of α-pinene) while the other products were not found. These data have to be seen as a first attempt to measure terpene oxidation products in the troposphere.