Atmospheric Photo-Oxidation of 2-Ethoxyethanol: Autoxidation Chemistry of Glycol Ethers.

We investigate the gas-phase photo-oxidation of 2-ethoxyethanol (2-EE) initiated by the OH radical with a focus on its autoxidation pathways. Gas-phase autoxidation─intramolecular H-shifts followed by O 2 addition─has recently been recognized as a major atmospheric chemical pathway that leads to the formation of highly oxygenated organic molecules (HOMs), which are important precursors for secondary organic aerosols (SOAs). Here, we examine the gas-phase oxidation pathways of 2-EE, a model compound for glycol ethers, an important class of volatile organic compounds (VOCs) used in volatile chemical products (VCPs). Both experimental and computational techniques are applied to analyze the photochemistry of the compound. We identify oxidation products from both bimolecular and autoxidation reactions from chamber experiments at varied HO 2 levels and provide estimations of rate coefficients and product branching ratios for key reaction pathways. The H-shift processes of 2-EE peroxy radicals (RO 2 ) are found to be sufficiently fast to compete with bimolecular reactions under modest NO/HO 2 conditions. More than 30% of the produced RO 2 are expected to undergo at least one H-shift for conditions typical of modern summer urban atmosphere, where RO 2 bimolecular lifetime is becoming >10 s, which implies the potential for glycol ether oxidation to produce considerable amounts of HOMs at reduced NO x levels and elevated temperature. Understanding the gas-phase autoxidation of glycol ethers can help fill the knowledge gap in the formation of SOA derived from oxygenated VOCs emitted from VCP sources.