LC-MS analysis of aerosol particles from the oxidation of α-pinene by ozone and OH-radicals

Abstract. The time resolved chemical composition of aerosol particles, formed by the oxidation of alpha-pinene has been investigated by liquid chromatography/mass spectrometry (LC-MS) using negative and positive ionisation methods (ESI(-) and APCI(+)). The experiments were performed at the EUPHORE facility in Valencia (Spain) under various experimental conditions, including dark ozone reactions, photosmog experiments with low NO_x mixing ratios and reaction with OH radicals in the absence of NO_x (H₂O₂-photolysis). Particles were sampled on PTFE f ilters at different stages of the reaction and extracted with methanol. The predominant products from alpha-pinene in the particulate phase are cis-pinic acid, cis-pinonic acid and hydroxy-pinonic acid isomers. Another major compound with molecular weight 172 was detected, possibly a hydroxy-carboxylic acid. These major compounds account for 50% to 80% of the identified aerosol products, depending on the time of sampling and type of experiment. In addition, more than 20 different products have been detected and structures have been tentatively assigned based on their molecular weight and responses to the different ionisation modes. The different experiments performed showed that the aerosol formation is mainly caused by the ozonolysis reaction. The highest aerosol yields were observed in the dark ozone experiments, for which also the highest ratios of mass of identified products to the formed aerosol mass were found (30% to 50%, assuming a density of 1 g cm^-3).