珠江三角洲大气挥发性羰基化合物的时空分布特征研究
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摘要
羰基化合物是大气环境和室内空气中常见的挥发性有机污染物，主要包括醛类和酮类化合物。羰基化合物既是大气光化学反应的产物，又能通过光化学反应生成羧酸、羟基自由基、臭氧和过氧乙酰硝酸酯。由于其在大气光化学反应过程中的重要作用及对人体健康的影响而受到越来越多地关注。
本文采用自制的2，4-二硝基苯肼(DNPH)涂布的硅胶吸附管，吸附空气中的羰基化合物，建立了17种醛酮化合物的的DNPH柱前衍生—高效液相色谱分析方法。然后采取区域观测和加强观测的方法，较为系统地研究了珠江三角洲区域大气挥发性羰基化合物的含量水平及时空分布规律。
研究表明：
1．自行研制采样管可以有效地采集空气中的17种醛酮类化合物，其回收率在97.35％以上，达到商品管同等效果，大大降低了实验成本。
2．珠三角区域大气中甲醛和乙醛两种醛类化合物浓度相对较高，分别是7.75μg／m~3和8.18μg／m~3，酮类化合物中丙酮较高，浓度为12.06μg／m~3，其他羰基化合物含量较低。与世界上许多城市相比，珠三角大气环境中羰基化合物污染处于中等偏上水平。
3．羰基化合物白天平均浓度高于夜晚，12：00～16：00其总浓度达到最高，凌晨4：00达到最低。地面采样点的羰基化合物浓度高于7楼和15楼的采样点，而7楼和15楼的采样点羰基化合物的浓度差别不大。
4．珠三角区域大气中甲醛／乙醛为0.97，得出羰基化合物来源主要是人为污染，而乙醛／丙醛为8.51，说明植物也能释放出大量的羰基化合物。甲醛、乙醛和丙醛与其他羰基化合物的之间具有较好的相关性，表明这些化合物有共同的来源，但是丁烯醛与其他羰基化合物的相关性比较差。
5．广州市区交通干道旁空气中乙醛浓度高于甲醛，比值达1.73，原因是使用乙醇和甲基叔丁基醚(MTBE)的汽油导致大量的乙醛的生成。甲醛／乙醛和乙醛／丙醛值都很低，反映出广州市区机动车尾气排放中醛酮类化合物的污染特征。
Carbonyls are some kinds of volatile organic pollutants and include aldehydes and ketonescompounds, can be easily measured both in indoor and outdoor air. They are formed byatmospheric photochemistry reaction, and could product OH radical, alkyl radical, ozone,carboxylic acid peroxyacetyl nitrates by atmospheric photochemistry reaction. Carbonyls havereceived more and more attention due to their adverse health effects and their important role inthe atmospheric chemistry.
A method of measuring the volatile carbonyls in atmosphere by high performance liquidchromatography was established in this study. Firstly, a self-made packed absorbent column wasinvented to sample the volatile carbonyls, with the saturated solution of2,4-dinitrophenylhydrazine(DNPH) in silica gel column, which could react quickly withcarbonyls to generate DNPH derivatives. Then these derivatives were determined by HPLC.Then, the method was used for sampling and analyzing carbonyls in the atmosphere of PearlRiver Delta. Their concentrations and spatial-temporal distribution were studied in full-scale.
In these studies, main conclusions were gained as following:
1. Self-made cartridge successfully, collected carbonyls in the air, the average recovery ratios wereover 97.35%. The Self-made cartridge could acquire comparably effect as commercial cartridge, and belower sample cost consumedly.
2. The concentration of formaldehyde and acetaldehyde were 7.75μg/m~3 and 8.18μg/m~3, whichwere respectively higher than other aldehydes compounds in the atmosphere of Pearl River Delta,and acetone was 12.06μg/m~3 higher in ketones compotmds. The concentrations of otherscarbonyls were very low. Compared with the data from other studies on urban areas worldwide,the carbonyls in the atmosphere of PRD were over middle level.
3. The even concentration of carbonyls in daytime was higher than what at night, it reachedtiptop during from middy to 4 p.m and reach undermost at 4 a.m. The concentration of carbonylsat ground site was higher than 7th and 15th floor site, but the concentration at 7th sites was asmuch as 15th floor.
4. From the ratio of formaldehyde/acetaldehyde which was 0.97, we concluded that anthropogenicemissions was the major source in the atmosphere of the Pearl River Delta, and the plant alsocould release lots of carbonyls from the ratio of acetaldehyde/propanal which was 8.51. Good correlations was found between formaldehyde, acetaldehyde, propanal and other carbonyls compounds,that concluded these compounds had common sources, but the correlations betweencrotonaldehyde and others was bad.
5. The concentration of acetaldehyde was higher than formaldehyde at roadside air in Guangzhou,because the usage of the gasoline that mixed with ether and MTBE caused a great deal ofacetaldehyde. Both formaldehyde/acetaldehyde and acetaldehyde/propanal were low, whichexpressed that the main source of carbonyls at roadside air of Guangzhou was the motorvehicular.
本文采用自制的2，4-二硝基苯肼(DNPH)涂布的硅胶吸附管，吸附空气中的羰基化合物，建立了17种醛酮化合物的的DNPH柱前衍生—高效液相色谱分析方法。然后采取区域观测和加强观测的方法，较为系统地研究了珠江三角洲区域大气挥发性羰基化合物的含量水平及时空分布规律。
研究表明：
1．自行研制采样管可以有效地采集空气中的17种醛酮类化合物，其回收率在97.35％以上，达到商品管同等效果，大大降低了实验成本。
2．珠三角区域大气中甲醛和乙醛两种醛类化合物浓度相对较高，分别是7.75μg／m~3和8.18μg／m~3，酮类化合物中丙酮较高，浓度为12.06μg／m~3，其他羰基化合物含量较低。与世界上许多城市相比，珠三角大气环境中羰基化合物污染处于中等偏上水平。
3．羰基化合物白天平均浓度高于夜晚，12：00～16：00其总浓度达到最高，凌晨4：00达到最低。地面采样点的羰基化合物浓度高于7楼和15楼的采样点，而7楼和15楼的采样点羰基化合物的浓度差别不大。
4．珠三角区域大气中甲醛／乙醛为0.97，得出羰基化合物来源主要是人为污染，而乙醛／丙醛为8.51，说明植物也能释放出大量的羰基化合物。甲醛、乙醛和丙醛与其他羰基化合物的之间具有较好的相关性，表明这些化合物有共同的来源，但是丁烯醛与其他羰基化合物的相关性比较差。
5．广州市区交通干道旁空气中乙醛浓度高于甲醛，比值达1.73，原因是使用乙醇和甲基叔丁基醚(MTBE)的汽油导致大量的乙醛的生成。甲醛／乙醛和乙醛／丙醛值都很低，反映出广州市区机动车尾气排放中醛酮类化合物的污染特征。
Carbonyls are some kinds of volatile organic pollutants and include aldehydes and ketonescompounds, can be easily measured both in indoor and outdoor air. They are formed byatmospheric photochemistry reaction, and could product OH radical, alkyl radical, ozone,carboxylic acid peroxyacetyl nitrates by atmospheric photochemistry reaction. Carbonyls havereceived more and more attention due to their adverse health effects and their important role inthe atmospheric chemistry.
A method of measuring the volatile carbonyls in atmosphere by high performance liquidchromatography was established in this study. Firstly, a self-made packed absorbent column wasinvented to sample the volatile carbonyls, with the saturated solution of2,4-dinitrophenylhydrazine(DNPH) in silica gel column, which could react quickly withcarbonyls to generate DNPH derivatives. Then these derivatives were determined by HPLC.Then, the method was used for sampling and analyzing carbonyls in the atmosphere of PearlRiver Delta. Their concentrations and spatial-temporal distribution were studied in full-scale.
In these studies, main conclusions were gained as following:
1. Self-made cartridge successfully, collected carbonyls in the air, the average recovery ratios wereover 97.35%. The Self-made cartridge could acquire comparably effect as commercial cartridge, and belower sample cost consumedly.
2. The concentration of formaldehyde and acetaldehyde were 7.75μg/m~3 and 8.18μg/m~3, whichwere respectively higher than other aldehydes compounds in the atmosphere of Pearl River Delta,and acetone was 12.06μg/m~3 higher in ketones compotmds. The concentrations of otherscarbonyls were very low. Compared with the data from other studies on urban areas worldwide,the carbonyls in the atmosphere of PRD were over middle level.
3. The even concentration of carbonyls in daytime was higher than what at night, it reachedtiptop during from middy to 4 p.m and reach undermost at 4 a.m. The concentration of carbonylsat ground site was higher than 7th and 15th floor site, but the concentration at 7th sites was asmuch as 15th floor.
4. From the ratio of formaldehyde/acetaldehyde which was 0.97, we concluded that anthropogenicemissions was the major source in the atmosphere of the Pearl River Delta, and the plant alsocould release lots of carbonyls from the ratio of acetaldehyde/propanal which was 8.51. Good correlations was found between formaldehyde, acetaldehyde, propanal and other carbonyls compounds,that concluded these compounds had common sources, but the correlations betweencrotonaldehyde and others was bad.
5. The concentration of acetaldehyde was higher than formaldehyde at roadside air in Guangzhou,because the usage of the gasoline that mixed with ether and MTBE caused a great deal ofacetaldehyde. Both formaldehyde/acetaldehyde and acetaldehyde/propanal were low, whichexpressed that the main source of carbonyls at roadside air of Guangzhou was the motorvehicular.
引文
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[2] 大气固定源的采样和分析编委会．大气固定源的采样和分析．北京：中国环境科学出版社，1993，502～508．
[3] 袁履冰．有机化学．高等教育出版社，1999：266～275．
[4] Carlier P, Hannachi H. and Mouvier G. The chemistry of carbonyl compounds in the atmosphere-a review. Atmosphereic Evironment, 1986, Vol. 20(11): 2079～2099.
[5] Fruekilde, P., Hjorth, J., N.R, Kotzias, D., Larsen, B. Ozonolysis at vegetation surfaces: a source of acetone, 4-oxopentanal, 6-methyl-5-hepten-2-one, and geranyl acetone in the troposphere. Atmos. Environ. 1998, 32: 1983～1902.
[6] Martin, P.,, neavner, D.L., Nelson, P.R.,Maiolo,K.C.,Risner, C.H.,Simmons,P.S., Morgan, W.T. and Ogden,M.W. Enviromental Tobacco Somke(ETS): A, Market Cigarette Study. Environmental International. 1997, 23: 75～90.
[7] Hellen,H., Hakola, H., Reissell,A., Ruuskanen, T.M..carbonyl compounds in boreal coniferous air in Hyytiala, Southern Finland. Atmos. Chem. Phys. 2004, 4: 1771～1780.
[8] Guenther, A., Hewitt, C.N., Erickson, D., Fall, R., Geron, C. A global model of natural volatile organic compound emissions. Journal of Geophsical Research. 1995, 100: 8873～8892.
[9] Atkinson, R., Arey, J.. Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review. Atmos. Environ. 2003, 37: S197～S219.
[10] Friedrich, R. and Obermeier, A. Anthropogenic emissions of volatile organic compounds, in: Reactive Hydraocarbons in the Atmosphere, edited by Hewitt,C.N.,academic Press, London, 1～39, 1999.
[11] USEPA. Motor vehicle-related air toxics study. April 1993.
[12] National Research Council,Board Toxicology and Environmental Health Hazards. Formaldehyde and other aldehydes. Washi ngton: National Academy Press. 1981.
[13] Grosjean D, Grosjean E and Gertler A W. On-road emission of carbonyls from light-duty and heavy-duty vehicles. Environ. Sci. Technol. 2001, 35: 45～53.
[14] Grosjean D, Grosjean E and Moreira L F R. Speciated ambient carbonyls in Rio de Janeiro, Brazil. Environ. Sci, Technol. 2002, 36: 1389～1395.
[15] Lee Y N, Zhou X, Hallock K. Atmosphereric carbonyls compounds at a rural southeastern United States sites. J. Geophys. Res. 1995, 100(D12): 25933～25944.
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