Highly Oxygenated Organic Molecules Produced by the Oxidation ofBenzene and Toluene in a Wide Range of OH Exposure and NO x Conditions

Abstract. Oxidation of aromatic volatile organic compounds (VOCs) leads to the formation of tropospheric ozone and secondary organic aerosol, for which gaseous oxygenated products are important intermediates. We show herein experimental results of highly oxygenated organic molecules (HOMs) produced by the oxidation of benzene and toluene in a wide range of OH exposure and NOx conditions. The results suggest multi-generation OH oxidation plays an important role in the product distribution, which likely proceeds more preferably via H subtraction than OH addition for early-generation products from light aromatics. Our experimental conditions promote the formation of more oxygenated products than previous flow-tube studies. The formation of dimeric products however was suppressed and might be unfavorable under conditions of high OH exposure and low NOx in toluene oxidation. Under high-NOx conditions, nitrogen-containing multifunctional products are formed, while the formation of other HOMs is suppressed. Products containing two nitrogen atoms become more important as the NOx level increases, and the concentrations of these compounds depend significantly on NO2. The highly oxygenated nitrogen-containing products might be peroxyacylnitrates, implying a prolonged effective lifetime of RO2 that facilitates regional pollution. Our results call for further investigation on the roles of high-NO2 conditions in the oxidation of aromatic VOCs.