Secondary organic aerosol formation from the oxidation of a series of sesquiterpenes: α-cedrene, β-caryophyllene, α-humulene and α-farnesene with O3, OH and NO3 radicals

Abstract

Environmental context Sesquiterpenes, chemicals emitted by terrestrial vegetation, are oxidised in the ambient atmosphere leading to the formation of secondary organic aerosol. Although secondary organic aerosol can have significant effects on air quality from local to global scales, considerable gaps remain in our understanding of their various sources and formation mechanisms. We report studies on the oxidation of sesquiterpenes aimed at improving aerosol parameterisation for these reactions for incorporation into future air quality models. Abstract A series of sesquiterpenes (SQT) were individually oxidised under a range of conditions, including irradiation in the presence of NOx, reactions with O3 or reactions with NO3 radicals. Experiments were conducted in either static mode to observe temporal evolution of reactants and products or in dynamic mode to ensure adequate collection of aerosol at reasonably low reactant concentrations. Although some measurements of gas-phase products have been made, the focus of this work has been particle phase analysis. To identify individual products, filter samples were extracted, derivatised and analysed using gas chromatography mass spectrometry techniques. The results indicate that secondary organic aerosol (SOA) is readily formed from SQT oxidation. The high reactivity of these systems and generally high conversion into SOA products gives rise to high SOA levels. SOA yields (ratio of SOA formed to hydrocarbon reacted) averaged 0.53 for ozonolysis, 0.55 for photooxidation and 1.19 for NO3 reactions. In select experiments, SOA was also analysed for the organic matter/organic carbon (OM/OC) ratio, and the effective enthalpy of vaporisation (ΔHvapeff). The OM/OC ranged from 1.8 for ozonolysis and photooxidation reactions to 1.6 for NO3 reactions, similar to that from SOA generated in monoterpene systems. ΔHvapeff was measured for β-caryophyllene–NOx, β-caryophyllene–O3, β-caryophyllene–NO3, α-humulene–NOx and α-farnesene–NOx systems and found to be 43.9, 41.1, 44.9, 48.2 and 27.7 kJ mol–1. Aerosol yields and products identified in this study are generally in good agreement with results from several studies. A detailed examination of the chamber aerosol for the presence of chemical tracer compounds was undertaken. Only β-caryophyllinic acid, observed mainly under β-caryophyllene photooxidation and ozonolysis experiments, was detected in ambient aerosol. Chemical analysis yielded compounds having oxygen and nitrogen moieties present, which indicates continued evolution of the particles over time and presents high dependence on the SQT–oxidant system studied. This study suggests that SOA from laboratory ozonolysis experiments may adequately represent ambient aerosol in areas with SQT emissions.