廊坊开发区秋季VOCs污染特征及来源解析
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摘要
使用ZF-PKU-1007大气挥发性有机物(VOCs)在线连续监测系统,于2018年09月25日～10月18日在廊坊市经济技术开发区对99种VOCs进行了在线连续观测.结果显示,观测期间VOCs浓度为69.56×10~(-9),烷烃、烯烃、芳香烃、醛酮类及卤代烃体积分数占VOCs比例分别为53.2%、5.9%、7.6%、10.5%和19.3%;使用OH消耗速率L_(OH)和臭氧生成潜势(OFP)估算了观测期间VOCs大气化学反应活性,结果表明醛酮类、芳香烃和烯烃是主要的活性物质;使用气溶胶生成系数法(FAC)估算了VOCs对二次有机气溶胶(SOA)的贡献,得出VOCs对SOA浓度的贡献值为1.13μg/m~3,其中芳香烃对SOA生成贡献占比为94.3%,间/对-二甲苯、甲苯为优势物种;使用PMF模型对VOCs进行了来源解析,识别了5个主要来源,分别为溶剂使用及挥发源(39.6%)、机动车源(22.5%)、固定燃烧源(17.6%)、石化工业源(11.1%)及植物排放源(9.4%),因此,溶剂使用及挥发源、机动车源及燃烧源应为廊坊开发区秋季大气VOCs控制的重点.
A continuous measurement was conducted in Langfang development zones from 25~(st)September to 18~(st)October, 2018, and a total of 99 VOCs species were detected by ZF-PKU-1007. The resulted showed VOCs average concentration was 69.56×10~(-9) during research period, and the average proportions of alkane, alkene, aromatic, aldehydes and ketones, chlorinated hydrocarbon were 53.2%、5.9%、7.6%、10.5%和 19.3%; The ozone formation potential(OFP) and the OH radical loss rate(L_(OH)) were applied to assess chemical reactivity of VOCs, result showed aldehydes and ketones, aromatic, and alkene were most active components. Fractional aerosol coefficients(FAC) was used to estimate the potential formation of secondary organic aerosol(SOA), and resulted showed the SOA concentration values was 1.13μg/m~3, aromatic contributed 94.3% to the total SOA formation potential and M-p-xylene and toluene were the dominant species. By applying the positive matrix factorization(PMF) model, five major sources were extracted to identify the sources of VOCs, including solvent usage and evaporation sources(39.6%), vehicle emission sources(22.5%), combustion sources(17.6%), petrochemical industry sources(11.1%) and plant emission sources(9.4%). Hence, solvent usage and evaporation, vehicle emission and combustion emission should be listed as priority of air pollution control strategy for Langfang development zones in autumn.
A continuous measurement was conducted in Langfang development zones from 25~(st)September to 18~(st)October, 2018, and a total of 99 VOCs species were detected by ZF-PKU-1007. The resulted showed VOCs average concentration was 69.56×10~(-9) during research period, and the average proportions of alkane, alkene, aromatic, aldehydes and ketones, chlorinated hydrocarbon were 53.2%、5.9%、7.6%、10.5%和 19.3%; The ozone formation potential(OFP) and the OH radical loss rate(L_(OH)) were applied to assess chemical reactivity of VOCs, result showed aldehydes and ketones, aromatic, and alkene were most active components. Fractional aerosol coefficients(FAC) was used to estimate the potential formation of secondary organic aerosol(SOA), and resulted showed the SOA concentration values was 1.13μg/m~3, aromatic contributed 94.3% to the total SOA formation potential and M-p-xylene and toluene were the dominant species. By applying the positive matrix factorization(PMF) model, five major sources were extracted to identify the sources of VOCs, including solvent usage and evaporation sources(39.6%), vehicle emission sources(22.5%), combustion sources(17.6%), petrochemical industry sources(11.1%) and plant emission sources(9.4%). Hence, solvent usage and evaporation, vehicle emission and combustion emission should be listed as priority of air pollution control strategy for Langfang development zones in autumn.
引文
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[13]杨笑笑,汤莉莉,胡丙鑫,等.南京城区夏季大气VOCs的来源及对SOA的生成研究——以亚青和青奥期间为例[J].中国环境科学,2016,36(10):2896-2902.Yang X X, Tang L L, Hu B X, et al. Sources apportionment of volatile organic compounds VOCs in summertime Nanjing and their potential contribution to secondary organic aerosols(SOA)[J]. China Environmental Science, 2016,36(10):2896-2902.
[14]王扶潘,朱乔,冯凝,等.深圳大气中VOCs的二次有机气溶胶生成潜势[J].中国环境科学, 2014,34(10):2449-2457.Wang F P, Zhu Q, Feng N, et al.The generation potential of secondary organic aerosol of atmospheric VOCs in Shenzhen[J]. China Environmental Science, 2014,34(10):2449-2457.
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[19] Grosjean D. In situ organic aerosol formation during a smog episode:estimated production and chemical functionality[J]. Atmospheric Environment. Part A. General Topics, 1992,26(6):953-963.
[20] Grosjean D, Seinfeld J H. Parameterization of the formation potential of secondary organic aerosols[J]. Atmospheric Environment(1967),1989,23(8):1733-1747.
[21] Gary N, Ram V. EPA Positive Matrix Factorization(PMF)3.0Fundamentals&User Guide[Z]. USA:EPA, 2008.
[22]解鑫,邵敏,刘莹,等.大气挥发性有机物的日变化特征及在臭氧生成中的作用——以广州夏季为例[J].环境科学学报, 2009,29(1):54-62.Xie X, Shao M, Liu Y, et al. 2009, The diurnal variation of ambient VOCs and their role in ozone formation:case study in summer in Guang zhou[J]. Acta Scientiae Circumstantiae, 2009,29(1):54-62.
[23] Sillman S. The relation between ozone, NOx and hydrocarbons in urban and polluted rural environments[J]. Atmospheric Environment,1999,33(12):1821-1845.
[24] Jacobson M C, Hansson H C, Noone K J, et al.Organic atmospheric aerosols:Review and state of the science[J]. Reviews of Geophysics,2000,38(2):267-294.
[25] Kroll J H, Ng N L, Murphy S M, et al. Secondary organic aerosol formation from isoprene photo oxidation under high-NOx conditions[J]. Geophysical Research Letters, 2005,32(18).
[26] Jang M, Czoschke N M, Lee S, et al. Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions[J].Science, 2002,298:814-817.
[27]王倩,王红丽,周来东,等.成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献[J].环境污染与防治,2015,37(7):6-12.Wang Q, Wang H L, Zhou L D, et al. Pollution of volatile organic compounds and their contribution to the secondary organic aerosol formation in summer of Chengdu[J]. Environmental Pollution&Control, 2015,37(7):6-12.
[28]吕子峰,郝吉明,段菁春,等.北京市夏季二次有机气溶胶生成潜势的估算[J].环境科学, 2009,30(4):969-975.Lv Z F, Hao J M, Duan J C, et al. Estimate of the formation potential of secondary organic aerosol in Beijing summertime[J].Environmental Science, 2009,30(4):969-975.
[29]王志辉,张树宇,陆思华,等.北京地区植物VOCs排放速率的测定[J].环境科学, 2003,24(2):7-12.Wang Z H, Zhang S Y, Lu S H, et al. Screenings of 23plant species in Beijing for volatile organic compound emissions[J]. Environmental Science, 2003,24(2):7-12.
[30] Guenther A, Geron C, Pierce T, et al. Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America[J]. Atmospheric Environment,2000,34(12-14):2205-2230.
[31] Chan L Y, Chu K W, Zou S C, et al. Characteristics of non-methane hydrocarbons(NMHCs)in industrial, industrial urban, and industrial-suburban atmospheres of the Pearl River Delta(PRD)region of south China[J]. Journal of Geophysical Research Atmospheres, 2006,111:D11304.
[32] Batterman S A, Peng C Y, James B, et al. Levels and composition of volatile organic compounds on commuting routes in Detroit, Michigan[J]. Atmospheric Environment, 2002,36(39/40):6015-6030.
[33] Chiang P C, Ching Y C, Ching E E. Characterization of hazardous air pollution emitted from motor vehicles[J]. Toxicological Environmental Chemistry, 1996,56(1-4):85-104.
[34] Cai C J, Geng F H, Tie X X, et al. Characteristics and source apportionment of VOCs measured in Shanghai, China[J].Atmospheric Environment, 2010,44(38):5005-5014.
[35] Shao P, An J L, Xin J Y, et al. Source apportionment of VOCs and the contribution to photochemical ozone formation during summer in the typical industrial area in the Yangtze River Delta, China[J].Atmospheric Research, 2016,176/177:64-74.
[36] Liu Y, Shao M, Fu L L, et al. Source profiles of volatile organic compounds(VOCs)measured in China:part I[J]. Atmospheric Environment, 2008,42(25):6247-6260.
[37] Yuan B, Shao M, Lu S H, et al. Source profiles of volatile organic compounds associate with solvent use in Beijing, China[J].Atmospheric Environment, 2010,44(15):1919-1926.
[38]魏巍,王书肖,郝吉明.中国涂料应用过程挥发性有机物的排放计算及未来发展趋势预测[J].环境科学, 2009,30(10):2809-2815.Wei W, Wang S X, Hao J M. Estimation and Forecast of Volatile Organic Compounds Emitted from Paint Uses in China[J].Environmental Science, 2009,30(10):2809-2815.
[2] Ding X, Wang X M, Gao B, et al. Tracer-based estimation of secondary organic carbon in the Pearl River Delta, south China[J].Journal of Geophysical Research:Atmospheres, 2012,117(D5).
[3] Shao M, Zhang Y, Zeng L, et al. Ground-level ozone in the Pearl River Delta and the roles of VOC and NOx in its production[J].Journal of Environmental Management, 2009,90(1):512-518.
[4] Guo S, Hu M, Guo Q F, et al. Primary sources and secondary formation of organic aerosols in Beijing, China[J]. Environmental Science and Technology, 2012,46(18):9846-9853.
[5] USEPA(United States Environmental Protection Agency).Carcinogenic effects of benzene:an update[R]. Washington:Prepared by the National Center for Environmental Health, Office of Research and Development, 2002.
[6]周裕敏,郝郑平,王海林.北京城乡结合地空气中挥发性有机物健康风险评价[J].环境科学, 2011,32(12):3566-3570.Zhou Y M, Hao Z P, Wang H L. Health risk assessment of atmospheric volatile organic compounds in Urban-rural Juncture Belt Area[J].Environmental Science, 2011,32(12):3566-3570.
[7] Guo H, Ling Z H, Cheng H R, et al. Tropospheric volatile organic compounds in China[J]. Science of the Total Environment, 2017,574:1021-1043.
[8] Barthelmie R J, Pryor S C. Secondary organic aerosols:formation potential and ambient data[J]. Science of the Total Environment,1997,205(2/3):167-178.
[9] Dechapanya W, Russell M, Allen D T. Estimates of anthropogenic secondary organic aerosol formation in Houston, Texas[J]. Aerosol Science and Technology, 2004,38(S1):156-166.
[10]刘奇琛,黄婧,郭新彪.北京市大气挥发性有机物(VOCs)的污染特征及来源[J].生态毒理学报, 2017,12(3):49-61.Liu Q C, Huang J, Guo X B. Pollution characteristics and sources of ambient volatile organic compounds(VOCs)in Beijing[J]. Asian Journal of Ecotoxicology, 2017,12(3):49-61.
[11]于艳,王秀艳,杨文.天津市机动车二次有机气溶胶生成潜势的估算[J].中国环境科学, 2015,35(2):381-386.Yu Y, Wang X Y, Yang W. Estimate of vehicles generation of secondary organic aerosols of Tianjin[J]. China Environmental Science, 2015,35(2):381-386.
[12]王倩,陈长虹,王红丽,等.上海市秋季大气VOCs对二次有机气溶胶的生成贡献及来源研究[J].环境科学, 2013,34(2):424-433.Wang Q, Chen C H, Wang H L, et al. Forming potential of secondary organic aerosols and sources apportionment of VOCs in autumn of Shanghai, China[J]. Environmental Science, 2013,34(2):424-433.
[13]杨笑笑,汤莉莉,胡丙鑫,等.南京城区夏季大气VOCs的来源及对SOA的生成研究——以亚青和青奥期间为例[J].中国环境科学,2016,36(10):2896-2902.Yang X X, Tang L L, Hu B X, et al. Sources apportionment of volatile organic compounds VOCs in summertime Nanjing and their potential contribution to secondary organic aerosols(SOA)[J]. China Environmental Science, 2016,36(10):2896-2902.
[14]王扶潘,朱乔,冯凝,等.深圳大气中VOCs的二次有机气溶胶生成潜势[J].中国环境科学, 2014,34(10):2449-2457.Wang F P, Zhu Q, Feng N, et al.The generation potential of secondary organic aerosol of atmospheric VOCs in Shenzhen[J]. China Environmental Science, 2014,34(10):2449-2457.
[15]廊坊市生态环境局.廊坊市环境质量概要(2017年)[EB/OL].http://sthj.lf.gov.cn/Item/5495.aspx.LangFang Ecology and Environment Bureau. Langfang environmental quality overview(2017)[EB/OL]. http://sthj.lf.gov.cn/Item/5495.aspx.
[16]廊坊市生态环境局.廊坊市环境质量概要(2016年)[EB/OL].http://sthj.lf.gov.cn/Item/3946.aspx.LangFang Ecology and Environment Bureau. Langfang environmental quality overview(2016)[EB/OL]. http://sthj.lf.gov.cn/Item/5495.aspx.
[17] Carter W P L. Development of ozone reactivity scales for volatile organic compounds[J]. Air&Waste, 1994,44(7):881-899.
[18]虞小芳,程鹏,古颖纲,等.广州市夏季VOCs对臭氧及SOA生成潜势的研究[J].中国环境科学, 2018,38(3):830-837.Yu X F, Cheng P, Gu Y G, et al. Formation potential of ozone and secondary organic aerosol from VOCs oxidation in summer in Guangzhou, China[J]. China Environmental Science, 2018,38(3):830-837.
[19] Grosjean D. In situ organic aerosol formation during a smog episode:estimated production and chemical functionality[J]. Atmospheric Environment. Part A. General Topics, 1992,26(6):953-963.
[20] Grosjean D, Seinfeld J H. Parameterization of the formation potential of secondary organic aerosols[J]. Atmospheric Environment(1967),1989,23(8):1733-1747.
[21] Gary N, Ram V. EPA Positive Matrix Factorization(PMF)3.0Fundamentals&User Guide[Z]. USA:EPA, 2008.
[22]解鑫,邵敏,刘莹,等.大气挥发性有机物的日变化特征及在臭氧生成中的作用——以广州夏季为例[J].环境科学学报, 2009,29(1):54-62.Xie X, Shao M, Liu Y, et al. 2009, The diurnal variation of ambient VOCs and their role in ozone formation:case study in summer in Guang zhou[J]. Acta Scientiae Circumstantiae, 2009,29(1):54-62.
[23] Sillman S. The relation between ozone, NOx and hydrocarbons in urban and polluted rural environments[J]. Atmospheric Environment,1999,33(12):1821-1845.
[24] Jacobson M C, Hansson H C, Noone K J, et al.Organic atmospheric aerosols:Review and state of the science[J]. Reviews of Geophysics,2000,38(2):267-294.
[25] Kroll J H, Ng N L, Murphy S M, et al. Secondary organic aerosol formation from isoprene photo oxidation under high-NOx conditions[J]. Geophysical Research Letters, 2005,32(18).
[26] Jang M, Czoschke N M, Lee S, et al. Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions[J].Science, 2002,298:814-817.
[27]王倩,王红丽,周来东,等.成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献[J].环境污染与防治,2015,37(7):6-12.Wang Q, Wang H L, Zhou L D, et al. Pollution of volatile organic compounds and their contribution to the secondary organic aerosol formation in summer of Chengdu[J]. Environmental Pollution&Control, 2015,37(7):6-12.
[28]吕子峰,郝吉明,段菁春,等.北京市夏季二次有机气溶胶生成潜势的估算[J].环境科学, 2009,30(4):969-975.Lv Z F, Hao J M, Duan J C, et al. Estimate of the formation potential of secondary organic aerosol in Beijing summertime[J].Environmental Science, 2009,30(4):969-975.
[29]王志辉,张树宇,陆思华,等.北京地区植物VOCs排放速率的测定[J].环境科学, 2003,24(2):7-12.Wang Z H, Zhang S Y, Lu S H, et al. Screenings of 23plant species in Beijing for volatile organic compound emissions[J]. Environmental Science, 2003,24(2):7-12.
[30] Guenther A, Geron C, Pierce T, et al. Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America[J]. Atmospheric Environment,2000,34(12-14):2205-2230.
[31] Chan L Y, Chu K W, Zou S C, et al. Characteristics of non-methane hydrocarbons(NMHCs)in industrial, industrial urban, and industrial-suburban atmospheres of the Pearl River Delta(PRD)region of south China[J]. Journal of Geophysical Research Atmospheres, 2006,111:D11304.
[32] Batterman S A, Peng C Y, James B, et al. Levels and composition of volatile organic compounds on commuting routes in Detroit, Michigan[J]. Atmospheric Environment, 2002,36(39/40):6015-6030.
[33] Chiang P C, Ching Y C, Ching E E. Characterization of hazardous air pollution emitted from motor vehicles[J]. Toxicological Environmental Chemistry, 1996,56(1-4):85-104.
[34] Cai C J, Geng F H, Tie X X, et al. Characteristics and source apportionment of VOCs measured in Shanghai, China[J].Atmospheric Environment, 2010,44(38):5005-5014.
[35] Shao P, An J L, Xin J Y, et al. Source apportionment of VOCs and the contribution to photochemical ozone formation during summer in the typical industrial area in the Yangtze River Delta, China[J].Atmospheric Research, 2016,176/177:64-74.
[36] Liu Y, Shao M, Fu L L, et al. Source profiles of volatile organic compounds(VOCs)measured in China:part I[J]. Atmospheric Environment, 2008,42(25):6247-6260.
[37] Yuan B, Shao M, Lu S H, et al. Source profiles of volatile organic compounds associate with solvent use in Beijing, China[J].Atmospheric Environment, 2010,44(15):1919-1926.
[38]魏巍,王书肖,郝吉明.中国涂料应用过程挥发性有机物的排放计算及未来发展趋势预测[J].环境科学, 2009,30(10):2809-2815.Wei W, Wang S X, Hao J M. Estimation and Forecast of Volatile Organic Compounds Emitted from Paint Uses in China[J].Environmental Science, 2009,30(10):2809-2815.