长沙市大气挥发性有机物的组成与来源
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摘要
在长沙市一个国家空气质量监测站附近采用罐采样方法采集环境全空气样品,利用三级冷阱预浓缩-GC/Dean-switch/FID/FID技术分析59种非甲烷碳氢化合物,同步采用2,4-二硝基苯肼(DNPH)-高效液相色谱法测定醛酮类化合物,研究非甲烷碳氢化合物及醛酮类化合物的组成与来源.结果表明,大气非甲烷碳氢化合物的总平均体积分数为(43.31±33.86)×10~(-9),其中异戊烷的体积分数最大;醛酮类化合物总浓度为(9.17±3.16)μg·m~(-3),主要为丙酮、甲醛和乙醛且其贡献了总浓度的90%以上.结合主成分分析法分析非甲烷碳氢化合物的来源,结果表明,汽油挥发、尾气排放及溶剂使用是大气非甲烷碳氢化合物的主要来源,分别对总浓度贡献了16.65%、16.61%、22.65%;进一步利用比值分析法表明苯系物的主要来源是汽车排放,醛酮类化合物符合城区的比值特征.
In this study, whole air samples were collected with stainless steel canister in Changsha. The mixing ratios of 59 ambient volatile organic compounds(VOCs) were analyzed by GC/Dean-switch/FID/FID coupled with a three-stage preconcentration, and concentrations of carbonyl were obtained using high-performance liquid chromatography as the 2,4-dinitrophenylhydrazine derivative. The composition and source of non-methane hydrocarbons and carbonyls were characterized and apportioned. The results showed that the total average mixing ratio of non-methane hydrocarbons was(43.31±33.86)×10~(-9), and the total concentration of carbonyl was(9.17±3.16) μg·m~(-3). In order of abundance, acetone, formaldehyde and acetaldehyde were the top three species, which contributed more than 90% of the total concentration of carbonyl. Sources apportionment using principal component analysis showed that gasoline volatilization, vehicle emissions, and solvent use were the main sources of atmospheric non-methane hydrocarbons in this area, which contributed 16.65%, 16.61%, and 22.65% of the total concentration. In addition, the results from species ratio analysis show that vehicle emission was the main source of aromatic, and the carbonyl pollutants mainly came from urban emissions.
In this study, whole air samples were collected with stainless steel canister in Changsha. The mixing ratios of 59 ambient volatile organic compounds(VOCs) were analyzed by GC/Dean-switch/FID/FID coupled with a three-stage preconcentration, and concentrations of carbonyl were obtained using high-performance liquid chromatography as the 2,4-dinitrophenylhydrazine derivative. The composition and source of non-methane hydrocarbons and carbonyls were characterized and apportioned. The results showed that the total average mixing ratio of non-methane hydrocarbons was(43.31±33.86)×10~(-9), and the total concentration of carbonyl was(9.17±3.16) μg·m~(-3). In order of abundance, acetone, formaldehyde and acetaldehyde were the top three species, which contributed more than 90% of the total concentration of carbonyl. Sources apportionment using principal component analysis showed that gasoline volatilization, vehicle emissions, and solvent use were the main sources of atmospheric non-methane hydrocarbons in this area, which contributed 16.65%, 16.61%, and 22.65% of the total concentration. In addition, the results from species ratio analysis show that vehicle emission was the main source of aromatic, and the carbonyl pollutants mainly came from urban emissions.
引文
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[17] 戴天有, 王玮, 任丽红, 等. 国产小汽车尾气非甲烷烃排放特征[J]. 中国科学:化学, 2010, 40(1):76-85.DAI T Y, WANG W, REN L H, et al. Emissions of non-methane hydrocarbons from cars in China[J]. Scientia Sinica Chimica, 2010, 40(1):76-85(in Chinese).
[18] 何小朗, 谭吉华, 郭送军, 等. 2014年北京APEC期间大气醛酮污染物的污染特征与来源分析[J]. 环境科学, 2016, 37(3): 801-806.HE X L, TAN, J H, GUO S J, et al. Chemical characteristics and sources of atmospheric carbonyls during the 2014 Beijing APEC [J]. Environmental Science, 2016, 37(3): 801-806 (in Chinese).
[19] 谭培功, 于彦彬, 蒋海威, 等. 青岛市大气中醛酮类化合物的分析及浓度变化[J].中国环境科学, 2002, 22(5): 451-455.TAN P G, YU Y B, JIANG H W, et al. Analysis and concentration variability of carbonyl compounds in Qingdao atmosphere[J]. China Environmental Science 2002, 22(5): 451-455(in Chinese).
[20] CHENG Y, LEE S C, HUANG Y, et al. Diurnal and seasonal trends of carbonyl compounds in roadside, urban, and suburban environment of Hong Kong[J]. Atmospheric Environment. 2014, 89: 43-51.
[21] 王伯光, 刘灿, 吕万明, 等. 广州大气挥发性醛酮类化合物的污染特征及来源研究[J]. 环境科学, 2009. 30(3): 631-636.WANG B G, LIU C, LV W M, et al. Character of volatile carbonyl compounds and their source in Guangzhou ambient air [J]. Environmental Science, 2009. 30(3): 631-636(in Chinese).
[22] POSSANZIN M, DIPALO V, PETRICCA M, et al. Measurements of lower carbonyls in Rome ambient air [J]. Atmospheric Environment. 1996, 30(22): 3757-3764.
[23] ZHANG J F, HE Q C, LIOY P J. Characteristics of aldehydes-concentrations, sources, and exposures for indoor and outdoor residential microenvironments[J]. Environmental Science & Technology, 1994, 28(1): 146-152.
[24] JACOB D J, WOFSY S C. Photochemistry of biogenic emissions over the Amazon forest[J]. Journal of Geophysical Research-Atmospheres, 1988, 93(D2): 1477-1486.
[25] GROSJEAN D, GROSJEAN E, GERTLER A W. On-road emissions of carbonyls from light-duty and heavy-duty vehicles[J]. Environmental Science & Technology, 2001, 35(1): 45-53.
[26] BROCCO D, FRATARCANGELI R, LEPORE L, et al. Determination of aromatic hydrocarbons in urban air of Roma [J]. Atmospheric Environment, 1997, 31(4): 557-566.
[27] PERRY R, GEE I L. Vehicle emissions in relation to fuel composition [J]. Science of the Total Environment, 1995, 169(1-3): 149-156.
[2] 李俊义, 田梁宇, 伦小秀, 等. 北京地区植物源挥发性有机物(BVOCs) 排放清单[J]. 环境化学, 2017, 36(4): 776-786. LI J Y, TIAN L Y, LUN X X, et al. Emission inventory of botanical volatile organic compounds (BVOCs) in Beijing[J]. Environmental Chemistry, 2017, 36(4): 776-786 (in Chinese).
[3] 路成伟, 周子航, 刘合凡, 等. 基于动态模型的四川盆地植物挥发性有机物排放[J]. 环境化学, 2018, 37(4):836-842.LU C W, ZHOU Z H, LIU H F, et al. Emission of biogenic volatile organic compounds in Sichuan Basin using a dynamic model [J]. Environmental Chemistry, 2018, 37(4): 836-842 (in Chinese).
[4] 安俊琳, 王跃思, 孙杨. 非甲烷挥发性有机物对北京大气臭氧产生的影响[J]. 生态环境学报, 2009, 18(4): 1318-1324.AN J L, WANG Y S, SUN Y. Effects of nonmethane hydrocarbons on ozone formation in Beijing [J]. Ecology and Environmental Sciences, 2009, 18(4): 1318-1324 (in Chinese).
[5] 李用宇, 朱彬, 安俊琳, 等. 南京北郊秋季VOCs及其光化学特征观测研究[J]. 环境科学, 2013, 24(8): 2933-2942. LI Y Y, ZHU B, AN J L, et al. Characteristics of VOCs and their photochemical reactivity in autumn in Nanjing northern suburb[J]. Environmental Science, 2013, 24(8): 2933-2942 (in Chinese).
[6] HAAGENSMIT A J. The air pollution problem in Los Angeles [J]. Engineering and Science 1950, 14: 7-13.
[7] HAAGENSMIT A J, FOX M M. Photochemical ozone formation with hydrocarbons and automobile exhaust [J]. Air Repair, 1952, 4(3): 105-136.
[8] BARLETTA B, MEINARDI S, ROWLAND FS, et al. Volatile organic compounds in 43 Chinese cities [J]. Atmospheric Environment, 2005, 39(32): 5979-5990.
[9] ZHANG J G, WANG Y S, WU K F, et al. Nonmethane hydrocarbon measurements at a suburban site in Changsha City, China [J]. Science of the Total Environment, 2009, 408(2): 312-317.
[10] 蒋朝晖, 王玉娇, 郑玄, 等. 张家界森林大气中醛酮类化合物浓度变化特征 [J]. 环境科学研究, 2016, 29(9): 1272-1278.JIANG Z H, WANG Y J, ZHENG X, et al. Variation characteristics of atmospheric carbonyl compounds in Zhangjiajie Forest [J]. Research of Environmental Sciences, 2016, 29(9): 1272-1278(in Chinese).
[11] USEPA. Compendium method TO-11A: Determination of formaldehyde in ambient air using adsorbent cartridge followed by high Performance Liquid Chromatography (HPLC) [S]. 1999.
[12] 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 Y, DENG X J, WANG B G, et al. Pollution characteristics of volatile organic compounds in Panyu Composition Station [J]. China Environmental Science, 2013, 33(5): 808-813(in Chinese).
[13] 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 X, ZHU B, AN J L, 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 (in Chinese).
[14] 张洲, 中国大气非甲烷碳氢化合物时空分布特征初步研究[D]. 北京, 中国科学院大学, 2016.ZHANG Z. Spatiotemporal patterns of ambient non-methane hydrocarbons in China[D]. Beijing: University of Chinese Academy of Science, 2016 (in Chinese).
[15] 黄海梅, 郭佳, 王章玮, 等. 贵阳市大气挥发性有机物的初步分析[J]. 环境化学, 2018,37(11): 2387-2396. HUANG H M, GUO J, WANG Z W, et al. Preliminary analysis of ambient volatile organic compounds in Guiyang, China[J]. Environmental Chemistry,2018,37(11): 2387-2396(in Chinese).
[16] 王丽红. 上海市大气挥发性有机物化学消耗与臭氧生成的关系[J]. 环境科学, 2015, 36(9): 3159-3167.WANG L H. Chemical loss of volatile organic compounds and its impact on the formation of ozone in Shanghai [J]. Environmental Science, 2015, 36(9):3159-3167 (in Chinese).
[17] 戴天有, 王玮, 任丽红, 等. 国产小汽车尾气非甲烷烃排放特征[J]. 中国科学:化学, 2010, 40(1):76-85.DAI T Y, WANG W, REN L H, et al. Emissions of non-methane hydrocarbons from cars in China[J]. Scientia Sinica Chimica, 2010, 40(1):76-85(in Chinese).
[18] 何小朗, 谭吉华, 郭送军, 等. 2014年北京APEC期间大气醛酮污染物的污染特征与来源分析[J]. 环境科学, 2016, 37(3): 801-806.HE X L, TAN, J H, GUO S J, et al. Chemical characteristics and sources of atmospheric carbonyls during the 2014 Beijing APEC [J]. Environmental Science, 2016, 37(3): 801-806 (in Chinese).
[19] 谭培功, 于彦彬, 蒋海威, 等. 青岛市大气中醛酮类化合物的分析及浓度变化[J].中国环境科学, 2002, 22(5): 451-455.TAN P G, YU Y B, JIANG H W, et al. Analysis and concentration variability of carbonyl compounds in Qingdao atmosphere[J]. China Environmental Science 2002, 22(5): 451-455(in Chinese).
[20] CHENG Y, LEE S C, HUANG Y, et al. Diurnal and seasonal trends of carbonyl compounds in roadside, urban, and suburban environment of Hong Kong[J]. Atmospheric Environment. 2014, 89: 43-51.
[21] 王伯光, 刘灿, 吕万明, 等. 广州大气挥发性醛酮类化合物的污染特征及来源研究[J]. 环境科学, 2009. 30(3): 631-636.WANG B G, LIU C, LV W M, et al. Character of volatile carbonyl compounds and their source in Guangzhou ambient air [J]. Environmental Science, 2009. 30(3): 631-636(in Chinese).
[22] POSSANZIN M, DIPALO V, PETRICCA M, et al. Measurements of lower carbonyls in Rome ambient air [J]. Atmospheric Environment. 1996, 30(22): 3757-3764.
[23] ZHANG J F, HE Q C, LIOY P J. Characteristics of aldehydes-concentrations, sources, and exposures for indoor and outdoor residential microenvironments[J]. Environmental Science & Technology, 1994, 28(1): 146-152.
[24] JACOB D J, WOFSY S C. Photochemistry of biogenic emissions over the Amazon forest[J]. Journal of Geophysical Research-Atmospheres, 1988, 93(D2): 1477-1486.
[25] GROSJEAN D, GROSJEAN E, GERTLER A W. On-road emissions of carbonyls from light-duty and heavy-duty vehicles[J]. Environmental Science & Technology, 2001, 35(1): 45-53.
[26] BROCCO D, FRATARCANGELI R, LEPORE L, et al. Determination of aromatic hydrocarbons in urban air of Roma [J]. Atmospheric Environment, 1997, 31(4): 557-566.
[27] PERRY R, GEE I L. Vehicle emissions in relation to fuel composition [J]. Science of the Total Environment, 1995, 169(1-3): 149-156.