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

Abstract

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.