[Characteristics and Sources of VOCs at Different Ozone Concentration Levels in Tianjin]

To further study the effect of volatile organic compounds (VOCs) on ozone pollution, the characteristics and sources of VOCs at different ozone (O₃) concentration levels were analyzed, using high-resolution online monitoring data obtained from Tianjin in the summer of 2019. Results showed that VOCs concentrations were 32.94, 38.10, 42.41, and 47.12 μg ·m^-3, when the O₃ concentration levels were categorized as excellent, good, light pollution, and moderate pollution, respectively. VOCs were composed of alkanes, alkenes, alkynes and aromatics, which accounted for 61.72%-63.36%, 14.96%-15.51%, 2.73%-4.13%, and 18.53%-19.10%, respectively, of VOCs concentrations at different O₃ concentration levels. Among them, the proportion of alkanes was slightly higher when O₃ concentration was categorized as good or light pollution, alkenes and alkynes accounted for the highest proportion when O₃ concentration was excellent, and the proportion of aromatics was highest during periods of moderate pollution. The main VOCs species were propane, ethane, ethylene, toluent, n-butane, isopentane, m/p-xylene, propylene, acetylene, n-hexane, isobutene, benzene, n-pentane, isoprene, and 1,2,3-trimethylbenzene. The concentration percentage of isopentane, n-pentane, benzene, ethylene, propylene, n-butane, and isobutane increased gradually as O₃ concentration increased. Significant increases in isoprene and 1,2,3-trimethylbenzene were observed during periods of light and moderate pollution. Alkenes and aromatics had higher ozone formation potential (OFP), and the contribution of alkenes to OFP declined as the O₃ level rose, whereas that of aromatics increased. Ethylene, propylene, m/p-xylene, 1,2,3-trimethylbenzene, toluene, isoprene, trans-2-butene, and cis-2-pentene were the key species for O₃ generation, and the contribution ratio of 1,2,3-trimethylbenzene, isoprene, propylene, and ethylene to OFP increased significantly during light or moderate O₃ pollution. Positive matrix factorization was applied to estimate the source contributions of VOCs. Automobile exhaust, solvent usage, liquefied petroleum gas (LPG)/gasoline evaporation, combustion, petrochemical industrial emissions, natural sources, and other industrial emissions were identified as major sources of VOCs in summer. As O₃ concentration level rose, the contribution percentage of automobile exhaust, LPG/gasoline evaporation, petrochemical industrial emissions, and natural sources increased gradually, whereas the contribution of combustion and other industrial emissions decreased overall. The contribution of solvent usage was lower when O₃ levels indicated light or moderate pollution than when it was good.