HPLC-MS determination of the oxidation products of the reaction between alpha- and beta-pinene and OH radicals

Biogenic non-methane hydrocarbons such as isoprene, alpha-pinene, and beta-pinene, are emitted by forests in very large quantities. To evaluate the role of alpha- and beta-pinene and their contribution to the global production of trace gases and especially aerosol precursors, a study of the oxidation mechanism of alpha- and beta-pinene with hydroxyl radicals must be conducted. The degradation products of both monoterpenes with hydroxyl radicals were identified and quantified in a fast-flow reactor. The products were collected on a liquid-nitrogen trap coated with a 2,4-DNPH solution to which two internal standards (benzaldehyde-2,4-DNPH and tolualdehyde-2,4-DNPH) had been added. The collection method was based on the in situ conversion of aldehyde and/or ketone compounds to their 2,4-dinitrophenylhydrazone derivatives. The derivatives were analyzed by HPLC-MS using APCI(-). TIC chromatograms and mass spectral data for the various oxidation products are presented. For alpha-pinene, pinonaldehyde is the most important degradation product, with smaller amounts of acetone, formaldehyde, campholenealdehyde, and acetaldehyde. For beta-pinene, nopinone and formaldehyde are the most abundant products, of almost equal importance, whereas acetone and acetaldehyde are minor compounds.