石化企业周边采暖季大气VOCs污染特征及化学反应活性
Pollution characteristics and effects to atmospheric chemistry of VOCs in heating period surrounding petrochemical enterprise
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摘要: 采集济南市石化企业周边采暖季环境空气中挥发性有机化合物（volatile organic compounds，VOCs）在线数据，进行了大气VOC成分组成及化学反应活性的分析.结果表明，2017年冬季采暖季期间，石化企业周边VOCs日均质量浓度为（57.82±49.79）μg·m-3，其中烷烃占比最高为61.53%，其次为芳香烃.日均质量浓度前三位的单体的分别是丙烷、乙烷和乙烯.MCM模拟结果表明，特殊污染日O3净生成反应速率为1.01（μg·m-3）·h-1，HO2+NO和RO2（除CH3O2外）+NO两大反应控制O3生成；而NO2+OH反应控制O3消耗.增量反应活性RIR和臭氧生成潜势OFP计算结果表明∑VOCs和NOx共同控制O3生成，且VOCs中的芳香烃和烯烃对O3的生成影响较大；对二次有机气溶胶生成贡献率最大的VOCs物种是芳香烃类，其贡献率高达94.05%，贡献率最高单体物质是甲苯，其次为乙苯.因此控制芳香烃类VOCs物种排放不仅可以减轻石化企业周边的冬季臭氧污染，同时对济南市的冬季灰霾污染有一定的控制.PMF源解析结果表明工业污染源、汽油挥发源和机动车尾气排放源是石化企业周边采暖季大气中VOCs的主要来源，控制这三类污染源排放是目前治理石化企业周边采暖季VOCs污染的主要途径.Abstract: Online data regarding volatile organic compounds (VOCs) in ambient air surrounding petrochemical enterprises during the heating period in Jinan were collected, and the composition characteristics of VOCs and their chemical reaction activities were analyzed. Results showed that the total average concentration of VOCs was (57.82±49.79) μg·m-3. Alkane was among the most abundant compounds, comprising as high as 61.53% of the total observed VOCs, followed by aromatic hydrocarbon. The top three VOCs were propane, ethane, and ethylene. The master chemical mechanism (MCM)simulation results showed that the average net reaction rate of O3 formation on a special polluted day was 1.01 (μg·m-3)·h-1. The photochemical formation of O3 was controlled by two reactions: HO2 + NO and RO2 (except CH3O2) + NO. The chemical loss of O3 was dominated by NO2 + OH reaction. Relative incremental reactivity (RIR) calculation and ozone formational potential (OFP) analysis showed that ∑VOCs and NOx cooperatively controlled the O3 formation with the key VOC species i.e., aromatic and alkene compounds. In addition, aromatic compounds dominated secondary organic aerosol formation with contribution rates as high as 94.05%. Therefore, controlling the emission of aromatic compounds would not only mitigate winter ozone pollution, but also control haze pollution around petrochemical enterprises. The PMF source analysis was conducted to obtain a better understanding of the sources of VOCs. The results suggested that industrial emission, gasoline volatilization, and vehicle exhaust were the main sources of VOCs during the heating period in the petrochemical enterprise sites of Jinan. Overall, reducing the VOCs pollution in Jinan is an important way of controlling industrial gas emissions,gasoline volatilization, and vehicle exhaust emissions.
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