Inter-comparison of laboratory smog chamber and flow reactor systems on organic aerosol yield and composition

Abstract. A variety of tools are used to simulate atmospheric aging, including smog chambers and flow reactors. Traditional, large-scale smog chambers age emissions over the course of hours to days, whereas flow reactors rapidly age emissions using high oxidant concentrations to reach higher degrees of oxygenation than typically attained in smog chamber experiments. The atmospheric relevance of the products generated under such rapid oxidation warrants further study. However, no previously published studies have compared the yields and chemical composition of products generated in flow reactors and smog chambers from the same starting mixture. The yields and composition of the organic aerosol formed from the photo-oxidation of α-pinene and of wood combustion emissions were determined using aerosol mass spectrometry in a smog chamber (SC) and two flow reactors: a potential aerosol mass reactor (PAM) and a micro-smog chamber (MSC). Reactants were sampled from the SC and aged in the MSC and PAM using a range of hydroxyl radical (OH) concentrations and then photo-chemically aged in the SC. The maximum yields/emission factors and the chemical composition of the products in both the α-pinene and wood combustion systems determined with the PAM and SC agreed reasonably well. High OH exposures have been shown previously to lower yields by breaking carbon-carbon bonds and forming higher volatility species, which reside largely in the gas phase, however, fragmentation in the PAM was not observed. The yields determined using the PAM for the α-pinene system were slightly lower than in the SC, possibly from increased wall losses of gas-phase species due to the higher surface area to volume ratios in the PAM, even when offset with better isolation of the sampled flow from the walls. The α-pinene SOA results for the MSC were not directly comparable, as particles were smaller than the optimal AMS transmission range. For the wood combustion system, emission factors measured by the MSC were typically lower than those from the SC, possibly due to nucleation mode particles not observed by the AMS or the condensational loss of gases to the walls inside or after the MSC. The chemical composition of products in the flow reactors and SC were in reasonable agreement in both systems. The emission factors determined using the flow reactors increased relative to the SC when the wood combustion emissions contained higher fractions of aromatic compounds, suggesting that the performance of the flow reactors may be dependent on the chemical composition of the reactants.