典型工业园污染源羰基化合物排放特征研究
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摘要
选取中国华东地区某工业园新区典型行业企业进行现场采样,利用PFPH衍生化-GC/MS联用技术进行羰基化合物(CBCs)的组成特征和含量水平检测,研究其排放特征。结果表明,在该工业园新区内共检出22种CBCs,各化合物的质量浓度为0.008~239.4μg/m~3,各企业CBCs总质量浓度均值为(437.62±64.45)μg/m~3,工业污染源排放贡献率由高至低顺序依次为涂料制造>橡胶制造>医药制造>化学品制造>金属制造>电子元件制造。根据各物质化学反应活性及大气化学寿命,获得该工业园新区典型的CBCs分子标志物为甲醛、乙醛、丙酮、丙醛、2-丁酮、丁醛、己醛、环己酮和苯甲醛,它们占总CBCs含量的80.01%,其中乙醛含量最高,质量浓度均值高达(95.42±71.48)μg/m3。最后,建立了6种典型工业污染源CBCs成分谱。
An observation was conducted at typical industrial enterprises of a industrial park in East China,using the PFPH-GC/MS method to analyze the composition and the concentration of carbonyl compounds,and investigate the emission characteristics of pollutants.The results were as follows:22 kinds of carbonyl compounds were detected with a concentration range of 0.008-239.4 μg/m~3,the mean value of total concentration in all industrial enterprises was(437.62±64.45) μg/m~3.The contribution ratio of each industrial pollution source was decreased in an order of coating manufacture,rubber manufacturer,pharmaceutical manufacturing,chemical manufacturer,metal manufacturing,electronic manufacture.The atmospheric chemical reactivity and lifetime of these compounds was used to research molecular markers of industrial pollution sources,formaldehyde,acetaldehyde,acetone,propionaldehyde,2-butanone,butyraldehyde,hexaldehyde,cyclohexanone and benzaldehyde were found to be molecular markers with their percentage of total carbonyls up to 80.01%,acetaldehyde was the most abundant carbonyl species with an average concentration of(95.42±71.48) μg/m~3.Finally,6 source profile was established for industrial pollution sources.
An observation was conducted at typical industrial enterprises of a industrial park in East China,using the PFPH-GC/MS method to analyze the composition and the concentration of carbonyl compounds,and investigate the emission characteristics of pollutants.The results were as follows:22 kinds of carbonyl compounds were detected with a concentration range of 0.008-239.4 μg/m~3,the mean value of total concentration in all industrial enterprises was(437.62±64.45) μg/m~3.The contribution ratio of each industrial pollution source was decreased in an order of coating manufacture,rubber manufacturer,pharmaceutical manufacturing,chemical manufacturer,metal manufacturing,electronic manufacture.The atmospheric chemical reactivity and lifetime of these compounds was used to research molecular markers of industrial pollution sources,formaldehyde,acetaldehyde,acetone,propionaldehyde,2-butanone,butyraldehyde,hexaldehyde,cyclohexanone and benzaldehyde were found to be molecular markers with their percentage of total carbonyls up to 80.01%,acetaldehyde was the most abundant carbonyl species with an average concentration of(95.42±71.48) μg/m~3.Finally,6 source profile was established for industrial pollution sources.
引文
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[24]唐孝炎,张远航,邵敏,等.大气环境化学[M].北京:高等教育出版社,2006:169-172.
[25]GEISS O,CACHO C,BARRERO-MORENO J,et al.Photocatalytic Degradation of Organic Paint ConstituentsFormation of Carbonyls[J].Building and Environment,2012,48:107-112.
[26]于海涛,康汝洪,欧阳兴梅.α,β-不饱和羰基化合物的选择还原研究进展[J].有机化学,2000,20(4):441-453.YU Haitao,KANG Ruhong,OUYANG Xingmei.Recent Development in the Selective Reduction ofα,β-Usnaturated Carbonyl Compounds[J].Chinese Journal of Organic Chemistry,2000,20(4):444-453.
[27]FENG Y L,WEN S,CHEN Y J,et al.Ambient Levels of Carbonyl Compounds and their Sources in Guangzhou,China[J].Atmospheric Environment,2005,39(10):1 789-1 800.
[28]SHAO M,WANG B,LU S H,et al.Effects of Beijing Olympics Control Measures on Reducing Reactive Hydrocarbon Species[J].Environment science&Technology,2011,45:514-519.
[2]MAHMOUD A A,ALAN W G,DOUGLAS H L,et al.A Preliminary Apportionment of the Sources of Ambient PM10,PM2.5,and VOCs in Cairo[J].Atmospheric Environment,2002,36(35):5 549-5 557.
[3]MAO T,WANG Y S,JIANG J,et al.The Vertical Distributions of VOCs in the Atmosphere of Beijing in Autumn[J].Science of The Total Environment,2008,390(1):97-108.
[4]MURALEEDHARAN T R,RADOJEVIC M,WAUGH A,et al.Chemical Characterisation of the Haze in Brunei Darussalam during the 1998 Episode[J].Atmospheric Environment,2000,34(17):2 725-2 731.
[5]LU H X,CAI Q Y,WEN S,et al.Carbonyl Compounds in the Ambient air of Hazy Days and Clear Days in Guangzhou,China[J].Atmospheric Research,2009,94(3):363-372.
[6]DUAN J C,GUO S J,TAN J H,et al.Characteristics of Atmospheric Carbonyls during Haze Days in Beijing,China[J].Atmospheric Research,2012,114/115:17-27.
[7]GROJEAN E,WILLIAMS II E,GROSJEAN D,et al.Ambient Levels of Formaldehyde and Acetaldehyde in Atlanta,Georgia[J].Journal of the Air&Waste Management Association,1993,43:469-474.
[8]CARTER W P L.Computer Modeling of Environmental Chamber Measurements of Maximum Incremental Reactivities of Volatile Organic Compounds[J].Atmospheric Environment,1995,29(18):2 513-2 527.
[9]BAKEAS E B,ARGYRIS D I,SISKOS P A,et al.Carbonyl Compounds in the urban Environment of Athens,Greece[J].Chemosphere,2003,52(5):805-813.
[10]VAIRAMUTHY A,ROBERT J M,NEWMAN L.Methods for Determination of Low Molecular Weight Carbonyl Coumpounds in the Atmosphere:A Review[J].Atmospheric Environment,1992,26A:1 965-1 993.
[11]SEIBER J N.Toxic Air Contaminants in Urban Atmospheres:Experience in California[J].Atmospheric Environment,1996,30(5):751-756.
[12]CARLIER P,HANNACHI H,Mouvier G.The Chemistry of Carbonyl Compounds in the Atmosphere-a review[J].Atmospheric Environment,1986,20(11):2 079-2 099.
[13]World Health Organization(WHO).Guidelines for Air Quality[R].Geneva:WHO,2000.
[14]KIM K H,HONG Y J,PAL R,et al.Investigation of Carbonyl Compounds in Air from Various Industrial Emission Sources[J].Chemosphere,2008,70(5):807-820.
[15]SANTARSIERO A,FUESLLI S.Indoor and Outdoor Air Carbonyl Compounds Correlation Elucidated by Principal Component Analysis[J].Environmental Research,2008,106(2):139-147.
[16]TSAI J H,CHANG S Y,CHIANG H C,et al.Volatile Organic Compounds from the Exhaust of LightDuty Diesel Vehicles[J].2012,61(61):499-506.
[17]YUAN C S,LIN Y C,TSAI C H,et al.Reducing Carbonyl Emissions from a Heavy-Duty Diesel Engine at US Transient Cycle Test by Use of Paraffinic/Biodiesel Blends[J].Atmospheric Environment,2009,43:6 175-6 181.
[18]GUO H,WANG T,BLAKE D R,et al.Regional and Local Contributions to Ambient Non-Methane Volatile Organic Compounds at a Polluted Rural/Coastal Site in Pearl River Delta,China[J].Atmos Environ,2006,40,2 345-2 359.
[19]LIU Y,SHAO M,LU S H,et al.Source Apportionmentof Ambient Volatile organic Compounds in the Pearl River Delta,China:Part II[J].Atmos Environ,2008,42:6 261-6 274.
[20]WANG H K,HUANG C H,CHEN K S,et al.Measurement and Source Characteristics of Carbonyl Compounds in the Atmosphere in Kaohsiung City,Taiwan[J].Journal of Hazardous Materials,2010,179:1 115-1 121.
[21]WEI W,WANG S X,HAO J M,Projection of Anthropogenic Volatile Organic Compounds(VOCs)Emissions in China for the Period 2010-2020[J].Atmospheric environment,2011,45:6 863-6 871.
[22]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):2 179-2 189.MO Ziwei,SHAO Min,LU Sihua.Review on Volatile Organic Compounds(VOCs)Source Profiles Measured in China[J].Acta Scientiae Circumstantiae,2014,34(9):2 179-2 189.
[23]周咪,王伯光,赵德骏,等.城市污水处理厂恶臭挥发性羰基化合物的排放特征[J].环境科学,2011,32(12):110-115.ZHOU Mi,WANG Boguang,ZHAO Dejun,et al.Source Emission Characteristics of Malodorous Volatile Organic Carbonyls from a Municipal Sewage Treatment Plant[J].Environmental Science,2011,32(12):110-115.
[24]唐孝炎,张远航,邵敏,等.大气环境化学[M].北京:高等教育出版社,2006:169-172.
[25]GEISS O,CACHO C,BARRERO-MORENO J,et al.Photocatalytic Degradation of Organic Paint ConstituentsFormation of Carbonyls[J].Building and Environment,2012,48:107-112.
[26]于海涛,康汝洪,欧阳兴梅.α,β-不饱和羰基化合物的选择还原研究进展[J].有机化学,2000,20(4):441-453.YU Haitao,KANG Ruhong,OUYANG Xingmei.Recent Development in the Selective Reduction ofα,β-Usnaturated Carbonyl Compounds[J].Chinese Journal of Organic Chemistry,2000,20(4):444-453.
[27]FENG Y L,WEN S,CHEN Y J,et al.Ambient Levels of Carbonyl Compounds and their Sources in Guangzhou,China[J].Atmospheric Environment,2005,39(10):1 789-1 800.
[28]SHAO M,WANG B,LU S H,et al.Effects of Beijing Olympics Control Measures on Reducing Reactive Hydrocarbon Species[J].Environment science&Technology,2011,45:514-519.