Characterization of Ambient VOCs in a Coal Chemical Industry Park and Their Contribution to Complex Air Pollution
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摘要: 为研究煤化工产业园区挥发性有机物(VOCs)污染特征及其对大气细颗粒物(PM2.5)和臭氧(O3)的贡献，本研究于2021年夏季利用气相色谱/质谱联用仪在某大型煤化工产业园区开展了环境空气115种VOCs的在线监测研究，分析了VOCs的浓度水平、组成特征、日变化特征、潜在来源及其对O3和PM2.5中二次有机气溶胶(SOA)的生成贡献. 结果表明：①观测期间，园区站点VOCs的平均体积分数为89.32×10−9±50.57×10−9，显著高于该园区所在城市的城区站点VOCs浓度水平. ②含氧VOCs (OVOCs)是该园区VOCs的主要特征污染物，占总VOCs体积分数的48.2%，乙醇、丙醛和甲醛是体积分数排名前三的物种. ③VOCs的臭氧生成潜势(OFP)为595.64 μg/m3，各组分对O3贡献潜势的大小表现为OVOCs>烯烃>芳香烃>烷烃>卤代烃>含硫VOC>炔烃. OFP排名前十的物种均为OVOCs、烯烃和芳香烃，其中丙醛对OFP的贡献占比最高，占总OFP的22.2%. ④间/对-二甲苯、邻二甲苯和乙苯等苯系物对二次有机气溶胶生成潜势(SOAFP)的贡献突出，其中间/对-二甲苯的SOAFP最大，占总SOAFP的29.6%，主导了SOA生成. 研究显示，煤化工产业园区中丙醛和甲醛等OVOCs、顺-2-丁烯等烯烃以及间/对-二甲苯与邻二甲苯等芳香烃对大气复合污染贡献较大，是开展PM2.5和O3污染协同控制重点关注的物种.
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关键词:
- 煤化工 /
- 挥发性有机物(VOCs) /
- 污染特征 /
- 大气复合污染 /
- 臭氧生成潜势(OFP) /
- 二次有机气溶胶生成潜势(SOAFP)
Abstract: In order to study the characteristics of volatile organic compounds (VOCs) and their contribution to atmospheric fine particulate matter (PM2.5) and ozone (O3), the measurements of 115 VOCs in the atmosphere were conducted by a gas chromatography coupled with a mass spectrometry in a large coal chemical industrial park during the summer of 2021. The levels, composition characteristics, diurnal variation, potential sources of VOCs, and their contributions to the formation of O3 and secondary organic aerosols (SOA) were analyzed. The results were shown as followed: (1) The total mixing ratio of VOCs was 89.32×10−9±50.57×10−9 in the coal chemical industrial park during the observed period, which was significantly higher than that detected at the urban site in the city where the coal chemical industrial park was located. (2) Oxygenated VOCs (OVOCs) were the most abundant VOCs, accounting for 48.2% of the total mixing ratio of VOCs. Ethanol, propionaldehyde and formaldehyde were the top three OVOCs species. (3) The total ozone formation potential (OFP) of VOCs was 595.64 μg/m3. The contributions of VOCs to OFP were OVOCs > alkenes > aromatics > alkanes > halogenated hydrocarbons > sulphur-containing VOC > alkyne. The top ten VOCs species contributing to OFP were OVOCs, alkenes and aromatics, of which propionaldehyde contributed the most (22.2%). (4) The top VOCs contributing to SOA formation potential (SOAFP) were m/p-xylene, o-xylene and ethylbenzene, of which m/p-xylene contributed the most (29.6%). Overall, OVOCs such as propionaldehyde and formaldehyde, alkenes such as cis-2-butene, and aromatics such as m/p-xylene and o-xylene contribute significant to the complex air pollution in the coal chemical industrial park, and are the VOCs species of key concern for carrying out PM2.5 and O3 synergistic control. -
图 2 研究区观测期间VOCs、常规污染物及气象参数时间序列
注：灰色阴影部分表示该时段PM2.5和O3浓度均较高.
Figure 2. Time series of VOCs, pollutants and meteorological parameters in the coal chemical industrial park during the observation period
图 3 研究区观测期间VOCs化学组成特征
Figure 3. Chemical compositions of VOCs monitored during the observation period
图 4 观测期间各VOCs组分的日变化情况
Figure 4. Diurnal variations of different categorized VOCs during the observation period
图 7 观测期间OFP排名前10位的VOCs物种
Figure 7. Top 10 VOCs species by OFP during the observation period
图 8 观测期间SOAFP排名前10位的VOCs物种
Figure 8. Top 10 VOCs species by SOAFP during the observation period
表 1 不同地区化工园区VOCs体积分数及特征对比
Table 1. Comparison of VOCs concentration and characteristics in chemical industrial parks in different regions
地区 物种个数 VOCs浓度/体积分数 主要组分(前10种) VOCSs种类
(按占比由高到低排序)观测时间 园区属性 数据来源 陕北地区 115 89.32×10−9±50.57×10−9 乙醇、丙醛、甲醛、二氯二氟甲烷、丙酮、乙醛、异丁烷、丙烷、正丁烷、乙烷 OVOCs、烷烃、卤代烃、烯烃、芳香烃、炔烃、含硫VOC 2021年5月1日—6月30日 煤化工园区 该研究 沈阳市 62 76.0×10−9 甲苯、间/对二甲苯、乙烯、苯乙烯、苯、正戊烷、异戊烷、丙烯、乙苯、1,3-丁二烯 烷烃、烯烃、芳香烃、炔烃和卤代烃 2018年11月9日—12月4日 油品制造、化学药品制造、轮胎制造、溶剂涂料制造和造纸 文献[15] 南京市 116 91.7×10−9±112.5×10−9 异戊烷、乙烷、正戊烷、丙烷、正丁烷、乙醛、乙烯、1,2-二氯乙烷、甲苯、甲基叔丁基醚 烷烃、OVOCs、烯烃、卤代烃、芳香烃、炔烃和含硫VOC 2020年3月28日—5月3日 石油化工 文献[12] 新疆维吾尔自治区 98 170.23×10−9±105.7×10−9 乙烷、丙烷、正丁烷、异丁烷、丙烯、乙烯、乙炔、苯、甲苯、乙苯 烷烃、烯烃、炔烃、芳香烃 2014年9月1日—11月30日 石油化工 文献[13] 长三角地区 98 381.92×10−9±183.62×10−9 二氯甲烷、甲苯、1,2-二氯甲烷、丙酮、2-甲基戊烷、乙腈、环己烷、2,3-二甲基戊烷、间/对-二甲苯、氯乙烷 卤代烃、烷烃、OVOCs、芳香烃、烯烃和炔烃 2018年3—12月 医药、染料制造、印染及化学品制造等行业 文献[40] 上海市 64 17.4~71.4 μg/m3 异丁烷、甲苯、正丁烷、乙烯、异戊烷、丙烷、环戊烷、苯、四氯化碳、间/对-二甲苯 烷烃、烯烃、芳香烃、卤代烃 2018年5月 石油化工 文献[18] 90 63.9×10−9±28.6×10−9 乙烯、丙烷、1,1-二氯乙烷、丙烯、三氯甲烷、三氯一氟甲烷、异戊二烯、甲苯、正丁烷、苯 烯烃、芳香烃、烷烃、卤代烃 2015年7月25—31日 油墨、医药/农药为主 文献[41] 21 260.71×10−9~1 086.42×10−9 乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷、丙烯、顺-2-丁烯、乙炔、苯 芳香烃、烷烃、烯烃、炔烃、卤代烃、含硫VOC 2015年12月21—27日 合成材料制造、涂料油墨、医药/农药为主 文献[16] 西安市 70 164.96~203.5 μg/m3 甲醛、乙醛、丙酮、2-丁酮、正丁烷、丙烷、乙烷、丙醛、异戊醛、正戊醛 烷烃、烯烃、炔烃、芳香烃、OVOCs 2020年7月30日—10月10日 半导体、软件信息等电子信息产业为核心 文献[20] 京津冀核心区 57 93.7×10−9±87.5×10−9 乙烯、丙烯、乙烷、正丁烷、丙烷、异丁烷、正己烷、异戊烷、甲苯、苯 烷烃、烯烃、炔烃、芳香烃 2018年6月1日—9月30日 石油化工 文献[14] 北京市 56 10.0×10−9~200.0×10−9 异丁烷、正丁烷、异戊烷、正戊烷、正己烷、C6支链烷烃、丙烯、1-丁烯、苯、甲苯 烷烃、烯烃、炔烃、芳香烃 2011年1月—9月1日 炼油厂 文献[19] 
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