OH-Initiated Oxidation of Acetylacetone: Implications for Ozone and Secondary Organic Aerosol Formation.
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Acetylacetone (AcAc) is a common atmospheric oxygenated volatile organic compound due to broad industrial applications, but its atmospheric oxidation mechanism is not fully understood. We investigate the mechanism, kinetics, and atmospheric fate of the OH-initiated oxidation for the enolic and ketonic isomers of AcAc using quantum chemical and kinetic rate calculations. OH addition to enol-AcAc is more favorable than addition to keto-AcAc, with the total rate constant of 1.69 × 10-13 exp(1935/T) cm3 molecule-1 s-1 over the temperature range of 200-310 K. For the reaction of the enol-AcAc with OH, the activation energies of H-abstraction are at least 4 kcal mol-1 higher than those of OH-addition, and the rate constants for OH-addition are by 2-3 orders of magnitude higher than those for H-abstraction. Oxidation of AcAc is predicted to yield significant amounts of acetic acid and methylglyoxal, larger than those are currently recognized. A lifetime of less than a few hours for AcAc is estimated throughout the tropospheric conditions. In addition, we present field measurements in Beijing and Nanjing, China, showing significant concentrations of AcAc in the two urban locations. Our results reveal that the OH-initiated oxidation of AcAc contributes importantly to ozone and SOA formation under polluted environments.
author list (cited authors)
Ji, Y., Zheng, J., Qin, D., Li, Y., Gao, Y., Yao, M., ... Zhang, R.