杭州市主城区VOCs污染特征及影响因素
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摘要
采用在线气相色谱仪,2013年在杭州市主城区对56种挥发性有机物(VOCs)开展1年的连续观测.研究VOCs组成、季节变化特征和日变化规律,总VOCs年均体积分数为42.1×10~(-9),其中烷烃占54.0%,烯烃占23.4%,芳香烃占14.4%,炔烃占8.2%.日变化规律表现为夜晚体积分数高于白天,在14:00达到全天最低值.分析VOCs特征物种发现,机动车尾气可能是主城区VOCs的主要来源.丙烯等效体积分数和臭氧生成潜势(OFP)均表明,VOCs反应活性较大的是烯烃,对OH活性和OFP的贡献率均超过60%,其次芳香烃和烷烃.分析气象要素与VOCs体积分数关系发现,在11～40°C下VOCs体积分数随着温度的升高而降低,与湿度有明显的正相关.光照对VOCs体积分数的影响较大,降水对VOCs的冲刷不明显.杭州全年以东风、北风为主导风向,但不同风向下的VOCs体积分数分布规律不明显.不论是主导还是非主导风向,VOCs体积分数始终随着风速的增大而减小,对于不同季节,风速影响幅度依次是秋季>冬季>春季>夏季.
Measurements of 56 volatile organic compounds(VOCs) species were obtained using online GC-FID/PID through one-year observation in urban Hangzhou in 2013. The VOCs composition, seasonal variation and diurnal cycles were analyzed. The annually averaged total VOCs was 42.1×10~(-9), with alkane accounting for 54%, followed by alkene(23.4%), aromatic(14.4%) and acetylene(8.2%). The diurnal cycles of VOCs showed lower values in daytime than nighttime, with minimum value at 14:00. Further analysis on typical species showed that the vehicle emissions were possibly regarded as the major VOCs source in urban Hangzhou. Both propene-equivalent concentration and ozone formation potential(OFP) analysis indicated that alkenes contributed over 60% of total VOCs reactivity. Associated meteorological effects showed that VOCs volume fractions were negative to temperature in 11-40 °C, while positive to relative humidity. Solar radiation has significant impact on VOCs values,while wet removal effect was not obvious. Eastern and northern winds were dominated for the whole year, but the volume fraction distribution of VOCs in different wind directions was not obvious. The VOCs volume fractions decreased as wind speed increased, regardless any wind direction. For different seasons, the impact extent of wind speed followed order as autumn>winter>spring>summer.
Measurements of 56 volatile organic compounds(VOCs) species were obtained using online GC-FID/PID through one-year observation in urban Hangzhou in 2013. The VOCs composition, seasonal variation and diurnal cycles were analyzed. The annually averaged total VOCs was 42.1×10~(-9), with alkane accounting for 54%, followed by alkene(23.4%), aromatic(14.4%) and acetylene(8.2%). The diurnal cycles of VOCs showed lower values in daytime than nighttime, with minimum value at 14:00. Further analysis on typical species showed that the vehicle emissions were possibly regarded as the major VOCs source in urban Hangzhou. Both propene-equivalent concentration and ozone formation potential(OFP) analysis indicated that alkenes contributed over 60% of total VOCs reactivity. Associated meteorological effects showed that VOCs volume fractions were negative to temperature in 11-40 °C, while positive to relative humidity. Solar radiation has significant impact on VOCs values,while wet removal effect was not obvious. Eastern and northern winds were dominated for the whole year, but the volume fraction distribution of VOCs in different wind directions was not obvious. The VOCs volume fractions decreased as wind speed increased, regardless any wind direction. For different seasons, the impact extent of wind speed followed order as autumn>winter>spring>summer.
引文
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[13]邹宇,邓雪娇,王伯光,等.广州番禺大气成分站挥发性有机物的污染特征[J].中国环境科学,2013,33(5):808-813.ZOU Yu,DENG Xue-jiao,WANG Bo-guang,et al.Pollution characteristics of volatile organic compounds in Panyu Composition Station[J].China Environmental Science,2013,33(5):808-813.
[14]施能,马丽,袁晓玉,等.近50a浙江省气候变化特征分析[J].大气科学学报,2001,24(2):207-213.SHI Neng,MA Li,YUAN Xiao-yu,et al.Climate variation features over Zhejiang province in the last50 years[J].Transactions of Atmospheric Sciences,2001,24(2):207-213.
[15]印红玲,袁桦蔚,叶芝祥,等.成都市大气中挥发性有机物的时空分布特征及臭氧生成潜势研究[J].环境科学学报,2015,35(2):386.YIN Hong-ling,YUAN Hua-wei,YE Zhi-xiang,et al.Temporal and spatial distribution of VOCs and their OFP in the atmosphere of Chengdu[J].Acta Scientiae Circumstantiae,2015,35(2):386.
[16]LIU Y,SHAO M,FU L,et al.Source profiles of volatile organic compounds(VOCs)measured in China:Part I[J].Atmospheric Environment,2008,42(25):6247-6260.
[17]莫梓伟,邵敏,陆思华.中国挥发性有机物(VOCs)排放源成分谱研究进展[J].环境科学学报,2014,34(9):2179-2189.MO Zi-wei,SHAO Min,LU Si-hua.Review on volatile organic compounds(VOCs)source profiles measured in China[J].Acta Scientiae Circumstantiae,2014,34(9):2179-2189.
[18]杨辉.南京北郊VOCs及其来源和光化学特征研究[D].南京:南京信息工程大学,2014.YANG Hui.The study of the source apportionment and photochemical properties of VOCs in the northern suburb of Nanjing[D].Nanjing:Nanjing University of Information Science and Technology,2014.
[19]CHAN C Y,CHAN L Y,WANG X M,et al.Volatile organic compounds in roadside microenvironments of metropolitan Hong Kong[J].Atmospheric Environment,2002,36(12):2039-2047.
[20]王琴,刘保献,张大伟,等.北京市大气VOCs的时空分布特征及化学反应活性[J].中国环境科学,2017,37(10):3636-3646.WANG Qin,LIU Bao-xian,ZHANG Da-wei,et al.Temporal and spatial distribution of VOCs and their role in chemical reactivity in Beijing[J].China Environmental Science,2017,37(10):3636-3646.
[21]段佳鹏,梁胜文,李蒲,等.武汉城区秋季大气挥发性有机物污染特征及部分物种来源的初步分析[J].环境监测管理与技术,2017,29(4):23-27.DUAN Jia-peng,LIANG Sheng-wen,LI Pu,et al.Preliminary analysis on characteristics and source of volatile organic compounds pollution in autumn in Wuhan City[J].The Administration and Technique of Environmental Monitoring,2017,29(4):23-27.
[22]OU J,ZHENG J,LI R,et al.Speciated OVOC and VOC emission inventories and their implications for reactivity-based ozone control strategy in the Pearl River Delta region,China[J].Science of the Total Environment,2015,530:393-402.
[23]JENKIN M E.Analysis of sources and partitioning of oxidant in the UK-Part 1:the NOX-dependence of annual mean concentrations of nitrogen dioxide and ozone[J].Atmospheric Environment,2004,38(30):5117-5129.
[24]刘侃侃.典型城市交通道路机动车排放CO污染特征研究[D].北京:北京林业大学,2010.LIU KAN-kan.The study on the characteristics of CO pollution of motor vehicle emissions in typical urban roads[D].Beijing:Beijing Forestry University,2010.
[25]邹宇,邓雪娇,李菲,等.广州大气中异戊二烯体积分数变化特征,化学活性和来源分析[J].环境科学学报,2015,35(3):647.ZOU Yu,DENG Xue-jiao,LI Fei,et al.Variation characteristics,chemical reactivity and sources of isoprene in the atmosphere of Guangzhou[J].Acta Scientiae Circumstantiae,2015,35(3):647.
[26]CARTER W P.Development of ozone reactivity scales for volatile organic compounds[J].Air and Waste,1994,44(7):881-899.
[27]齐冰,牛彧文,杜荣光,等.杭州市近地面大气臭氧体积分数变化特征分析[J].中国环境科学,2017,37(2):443-451.QI Bing,NIU Yu-wen,DU Rong-guang,et al.Characteristics of surface ozone concentration in urban site of Hangzhou[J].China Environmental Science,2017,37(2):443-451.
[2]唐孝炎,张远航,邵敏,等.大气环境化学[M].2版.北京:高等教育出版社,2006.
[3]邵敏,付琳琳,刘莹,等.北京市大气挥发性有机物的关键活性组分及其来源[J].中国科学:D辑,2005,35(A01):123-130.SHAO Min,FU Lin-lin,LIU Ying,et al.Key volatile organic compounds in Beijing and their sources[J].Science China:Series D,2005,35(A01):123-130.
[4]王伯光,张远航,邵敏.珠江三角洲大气环境VOCs的时空分布特征[J].环境科学,2004,25(增1):7-15.WANG Bo-guang,ZHANG Yuan-hang,SHAO Min.Special and temporal distribution character of VOCs in the ambient air of Peal River Delta region[J].Environmental Science,2004,25(Suppl.1):7-15.
[5]邓雪娇,王新明,赵春生,等.珠江三角洲典型过程VOCs的平均体积分数与化学反应活性[J].中国环境科学,2010,30(9):1153-1161.DENG Xue-jiao,WANG Xin-ming,ZHAO Chunsheng,et al.The mean concentration and chemical reactivity of VOCs of typical processes over Pearl River Delta Region[J].China Environmental Science,2010,30(9):1153-1161.
[6]卢学强,韩萌,冉靓,等.天津中心城区夏季非甲烷有机化合物组成特征及其臭氧产生潜力分析[J].环境科学学报,2011,31(2):373-380.LU Xue-qiang,HAN Meng,RAN Liang,et al.Characteristic of nonmethane organic compounds and their ozone formation potentials in downtown Tianjin in summer[J].Acta Scientiae Circumstantiae,2011,31(2):373-380.
[7]陈长虹,苏雷燕,王红丽,等.上海市城区VOCs的年变化特征及其关键活性组分[J].环境科学学报,2012,32(2):367-376.CHEN Chang-hong,SU Lei-yan,WANG Hong-li,et al.Variation and key reactive species of ambient VOCs in the urban area of Shanghai,China[J].Acta Scientiae Circumstantiae,2012,32(2):367-376.
[8]林旭,朱彬,安俊琳,等.南京北郊VOCs对臭氧和二次有机气溶胶潜在贡献的研究[J].中国环境科学,2015,35(4):976-986.LIN Xu,ZHU Bin,AN Jun-lin,et al.Potential contribution of secondary organic aerosols and ozone of VOCs in the northern suburb of Nanjing[J].China Environmental Science,2015,35(4):976-986.
[9]洪盛茂,焦荔,何曦,等.杭州典型区域C2-12质量体积分数变化及臭氧潜势量分析[J].环境科学研究,2009(8):938-943.HONG Sheng-mao,JIAO Li,HE Xi,et al.Variations in mass concentrations and ozone formation potentials of C2-12 hydrocarbons in typical areas of Hangzhou,China[J].Research of Environmental Sciences,2009(8):938-943.
[10]应方,包贞,杨成军,等.杭州市道路空气中挥发性有机物及其大气化学反应活性研究[J].环境科学学报,2012,32(12):3056.YING Fang,BAO Zhen,YANG Cheng-jun,et al.Analysis of volatile organic compounds(VOCs)and their atmospheric chemical reactivity in ambient air around urban traffic roads in Hangzhou[J].Acta Scientiae Circumstantiae,2012,32(12):3056.
[11]LI K,CHEN L,YING F,et al.Meteorological and chemical impacts on ozone formation:a case study in Hangzhou,China[J].Atmospheric Research,2017,196:40-52.
[12]朱少峰,黄晓锋,何凌燕,等.深圳大气VOCs体积分数的变化特征与化学反应活性[J].中国环境科学,2012,32(12):2140-2148.ZHU Shao-feng,HUANG Xiao-feng,HE Ling-yan,et al.Variation characteristics and chemical reactivity of ambient VOCs in Shenzhen[J].China Environmental Science,2012,32(12):2140-2148.
[13]邹宇,邓雪娇,王伯光,等.广州番禺大气成分站挥发性有机物的污染特征[J].中国环境科学,2013,33(5):808-813.ZOU Yu,DENG Xue-jiao,WANG Bo-guang,et al.Pollution characteristics of volatile organic compounds in Panyu Composition Station[J].China Environmental Science,2013,33(5):808-813.
[14]施能,马丽,袁晓玉,等.近50a浙江省气候变化特征分析[J].大气科学学报,2001,24(2):207-213.SHI Neng,MA Li,YUAN Xiao-yu,et al.Climate variation features over Zhejiang province in the last50 years[J].Transactions of Atmospheric Sciences,2001,24(2):207-213.
[15]印红玲,袁桦蔚,叶芝祥,等.成都市大气中挥发性有机物的时空分布特征及臭氧生成潜势研究[J].环境科学学报,2015,35(2):386.YIN Hong-ling,YUAN Hua-wei,YE Zhi-xiang,et al.Temporal and spatial distribution of VOCs and their OFP in the atmosphere of Chengdu[J].Acta Scientiae Circumstantiae,2015,35(2):386.
[16]LIU Y,SHAO M,FU L,et al.Source profiles of volatile organic compounds(VOCs)measured in China:Part I[J].Atmospheric Environment,2008,42(25):6247-6260.
[17]莫梓伟,邵敏,陆思华.中国挥发性有机物(VOCs)排放源成分谱研究进展[J].环境科学学报,2014,34(9):2179-2189.MO Zi-wei,SHAO Min,LU Si-hua.Review on volatile organic compounds(VOCs)source profiles measured in China[J].Acta Scientiae Circumstantiae,2014,34(9):2179-2189.
[18]杨辉.南京北郊VOCs及其来源和光化学特征研究[D].南京:南京信息工程大学,2014.YANG Hui.The study of the source apportionment and photochemical properties of VOCs in the northern suburb of Nanjing[D].Nanjing:Nanjing University of Information Science and Technology,2014.
[19]CHAN C Y,CHAN L Y,WANG X M,et al.Volatile organic compounds in roadside microenvironments of metropolitan Hong Kong[J].Atmospheric Environment,2002,36(12):2039-2047.
[20]王琴,刘保献,张大伟,等.北京市大气VOCs的时空分布特征及化学反应活性[J].中国环境科学,2017,37(10):3636-3646.WANG Qin,LIU Bao-xian,ZHANG Da-wei,et al.Temporal and spatial distribution of VOCs and their role in chemical reactivity in Beijing[J].China Environmental Science,2017,37(10):3636-3646.
[21]段佳鹏,梁胜文,李蒲,等.武汉城区秋季大气挥发性有机物污染特征及部分物种来源的初步分析[J].环境监测管理与技术,2017,29(4):23-27.DUAN Jia-peng,LIANG Sheng-wen,LI Pu,et al.Preliminary analysis on characteristics and source of volatile organic compounds pollution in autumn in Wuhan City[J].The Administration and Technique of Environmental Monitoring,2017,29(4):23-27.
[22]OU J,ZHENG J,LI R,et al.Speciated OVOC and VOC emission inventories and their implications for reactivity-based ozone control strategy in the Pearl River Delta region,China[J].Science of the Total Environment,2015,530:393-402.
[23]JENKIN M E.Analysis of sources and partitioning of oxidant in the UK-Part 1:the NOX-dependence of annual mean concentrations of nitrogen dioxide and ozone[J].Atmospheric Environment,2004,38(30):5117-5129.
[24]刘侃侃.典型城市交通道路机动车排放CO污染特征研究[D].北京:北京林业大学,2010.LIU KAN-kan.The study on the characteristics of CO pollution of motor vehicle emissions in typical urban roads[D].Beijing:Beijing Forestry University,2010.
[25]邹宇,邓雪娇,李菲,等.广州大气中异戊二烯体积分数变化特征,化学活性和来源分析[J].环境科学学报,2015,35(3):647.ZOU Yu,DENG Xue-jiao,LI Fei,et al.Variation characteristics,chemical reactivity and sources of isoprene in the atmosphere of Guangzhou[J].Acta Scientiae Circumstantiae,2015,35(3):647.
[26]CARTER W P.Development of ozone reactivity scales for volatile organic compounds[J].Air and Waste,1994,44(7):881-899.
[27]齐冰,牛彧文,杜荣光,等.杭州市近地面大气臭氧体积分数变化特征分析[J].中国环境科学,2017,37(2):443-451.QI Bing,NIU Yu-wen,DU Rong-guang,et al.Characteristics of surface ozone concentration in urban site of Hangzhou[J].China Environmental Science,2017,37(2):443-451.