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. 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 (?Hvapeff). 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. ?Hvapeff was measured for ß-caryophyllene–NOx, ß-caryophyllene–O3, ß-caryophyllene–NO3, a-humulene–NOx and a-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 ß-caryophyllinic acid, observed mainly under ß-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.

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM − KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM − KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from biogenic epoxides (AQCHEM − KMTI), normalized mean error and bias statistics are slightly improved for 2-methyltetrols and 2-methylglyceric acid at the Research Triangle Park measurement site in North Carolina during the Southern Oxidant and Aerosol Study (SOAS) period. The added in-cloud chemistry leads to a monthly average increase of 11–18 % in cloud SOA at the surface in the eastern United States for June 2013.