太原市环境空气中挥发性芳香烃碳同位素组成及来源
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摘要
利用Tenax TA吸附管采集太原市不同排放源及不同功能区环境空气样品,色谱-质谱、同位素质谱联用技术测定了其挥发性芳香烃化合物的碳同位素组成,并分析了其组成特征.结果表明,柴油挥发源、汽油挥发源、溶剂挥发源、机动车尾气源和民用燃煤源排放的挥发性芳香烃化合物中稳定碳同位素值(δ~(13)C)测定范围依次为:(-30. 79±0. 98)‰～(-29. 10±0. 14)‰、(-30. 96±0. 88)‰～(-28. 02±1. 77)‰、(-32. 13±0. 59)‰～(-27. 67±0. 49)‰、(-27. 58±0. 16)‰～(-25. 50±0. 75)‰和(-25. 14±0. 93)‰～(-23. 44±1. 32)‰,民用燃煤源显著富集13C.仅在民用燃煤源排放烟气中检出苯乙烯,δ~(13)C值为(-23. 44±1. 32)‰.太原市4个不同功能区采样分析显示,居民交通混合区环境空气中挥发性芳香烃的δ~(13)C值为(-25. 61±2. 20)‰～(-23. 91±0. 78)‰,较其他区域富集13C;工业区δ~(13)C检测值为(-29. 15±1. 06)‰～(-24. 53±1. 07)‰,较其他区域贫13C.将环境空气中挥发性芳香烃δ~(13)C值与排放源δ~(13)C值比较可发现,太原市4个环境空气点位的挥发性芳香烃主要来源是机动车尾气源和民用燃煤源,工业区受溶剂挥发影响较大.
This study used Tenax TA absorption tubes to sample volatile aromatic compounds from different emission sources and functional zones in Taiyuan City,Shanxi Province,China. Thermal desorption-gas chromatography-isotope ratio mass spectrometry( TD-GC-IRMS) was subsequently employed to analyze the stable carbon isotope characteristics of the volatile aromatic compounds. The results revealed that the stable carbon isotope ratio( δ~(13)C) of the volatile aromatic compounds emitted through diesel,gasoline,and solvent volatilization,vehicle exhaust,and domestic coal combustion ranged from(-30. 79 ± 0. 98) ‰ to(-29. 10 ± 0. 14) ‰,(-30. 96 ± 0. 88) ‰ to(-28. 02 ± 1. 77) ‰,(-32. 13 ± 0. 59) ‰ to(-27. 67 ± 0. 49) ‰,(-27. 58 ± 0. 16) ‰ to(-25. 50 ±0. 75) ‰,and(-25. 14 ± 0. 93) ‰ to(-23. 44 ± 1. 32) ‰,respectively. The δ~(13)C value of styrene was(-23. 44 ± 1. 32) ‰,which was only detected in the fumes emitted through domestic coal combustion. Additionally,the sample analysis based on data collected from four different functional zones of Taiyuan City revealed the following: ① the δ~(13)C values of the atmospheric volatile aromatic compounds in the mixed residential and traffic zone ranged from(-25. 61 ± 2. 20) ‰ to(-23. 91 ± 0. 78) ‰. Compared with other functional zones,the emissions in this zone were enriched with13 C; and ② the δ~(13)C values measured in the industrial zone ranged from(-29. 15 ± 1. 06) ‰ to(-24. 53 ± 1. 07) ‰; the emissions in this functional zone were relatively low in13 C compared with other zones. A comparison of the δ~(13)C values of the atmospheric volatile aromatic compounds and emission sources indicated that the main sources of volatile aromatic compounds at the four sampling points in Taiyuan were vehicle exhausts and domestic coal combustion,while the air sampled in the industrial functional zone was heavily affected by the volatilization of solvents.
This study used Tenax TA absorption tubes to sample volatile aromatic compounds from different emission sources and functional zones in Taiyuan City,Shanxi Province,China. Thermal desorption-gas chromatography-isotope ratio mass spectrometry( TD-GC-IRMS) was subsequently employed to analyze the stable carbon isotope characteristics of the volatile aromatic compounds. The results revealed that the stable carbon isotope ratio( δ~(13)C) of the volatile aromatic compounds emitted through diesel,gasoline,and solvent volatilization,vehicle exhaust,and domestic coal combustion ranged from(-30. 79 ± 0. 98) ‰ to(-29. 10 ± 0. 14) ‰,(-30. 96 ± 0. 88) ‰ to(-28. 02 ± 1. 77) ‰,(-32. 13 ± 0. 59) ‰ to(-27. 67 ± 0. 49) ‰,(-27. 58 ± 0. 16) ‰ to(-25. 50 ±0. 75) ‰,and(-25. 14 ± 0. 93) ‰ to(-23. 44 ± 1. 32) ‰,respectively. The δ~(13)C value of styrene was(-23. 44 ± 1. 32) ‰,which was only detected in the fumes emitted through domestic coal combustion. Additionally,the sample analysis based on data collected from four different functional zones of Taiyuan City revealed the following: ① the δ~(13)C values of the atmospheric volatile aromatic compounds in the mixed residential and traffic zone ranged from(-25. 61 ± 2. 20) ‰ to(-23. 91 ± 0. 78) ‰. Compared with other functional zones,the emissions in this zone were enriched with13 C; and ② the δ~(13)C values measured in the industrial zone ranged from(-29. 15 ± 1. 06) ‰ to(-24. 53 ± 1. 07) ‰; the emissions in this functional zone were relatively low in13 C compared with other zones. A comparison of the δ~(13)C values of the atmospheric volatile aromatic compounds and emission sources indicated that the main sources of volatile aromatic compounds at the four sampling points in Taiyuan were vehicle exhausts and domestic coal combustion,while the air sampled in the industrial functional zone was heavily affected by the volatilization of solvents.
引文
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[2]陈天增,葛艳丽,刘永春,等.我国机动车排放VOCs及其大气环境影响[J].环境科学,2018,39(2):478-492.Chen T Z,Ge Y L,Liu Y C,et al. VOCs emission from motor vehicles in China and Its impact on the atmospheric environment[J]. Environmental Science,2018,39(2):478-492.
[3]罗达通,高健,王淑兰,等.上海秋季大气挥发性有机物特征及污染物来源分析[J].中国环境科学,2015,35(4):987-994.Luo D T,Gao J,Wang S L,et al. Characteristics of volatile organic compounds and relative pollutants observed in autumn Shanghai[J]. China Environmental Science,2015,35(4):987-994.
[4] Yan Y L,Peng L, Li R M, et al. Concentration, ozone formation potential and source analysis of volatile organic compounds(VOCs)in a thermal power station centralized area:a study in Shuozhou,China[J]. Environmental Pollution,2017,223:295-304.
[5]杨帆,闫雨龙,戈云飞,等.晋城市冬季环境空气中挥发性有机物的污染特征及来源解析[J].环境科学,2018,39(9):4042-4050.Yang F,Yan Y L,Ge Y F,et al. Characteristics and source apportionment of ambient volatile organic compounds in winter in Jincheng[J]. Environmental Science,2018,39(9):4042-4050.
[6]王鸣,陈文泰,陆思华,等.我国典型城市环境大气挥发性有机物特征比值[J].环境科学,2018,39(10):4393-4399.Wang M,Chen W T,Lu S H,et al. Ratios of volatile organic compounds in ambient air of various cities of China[J].Environmental Science,2018,39(10):4393-4399.
[7]李斌,张鑫,李娜,等.北京市春夏挥发性有机物的污染特征及源解析[J].环境化学,2018,37(11):2410-2418.Li B,Zhang X,Li N,et al. Pollution characteristics and source analysis of volatile organic compounds in spring and summer in Beijing[J]. Environmental Chemistry,2018,37(11):2410-2418.
[8] Huang L H,Qian H,Deng S X,et al. Urban residential indoor volatile organic compounds in summer, Beijing:profile,concentration and source characterization[J]. Atmospheric Environment,2018,188:1-11.
[9]王鸣,项萍,牛其恺,等.南阳市冬春交替期大气VOCs污染特征及来源解析[J].环境科学学报,2018,38(6):2233-2241.Wang M,Xiang P,Niu Q K,et al. Characteristics and source apportionment of ambient VOCs during alternating period between winter and spring in Nanyang City,Henan Province[J]. Acta Scientiae Circumstantiae,2018,38(6):2233-2241.
[10] 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.
[11]陆思华,白郁华,张广山,等.大气中挥发性有机化合物(VOCs)的人为来源研究[J].环境科学学报,2006,26(5):757-763.Lu S H,Bai Y H,Zhang G S,et al. Source apportionment of anthropogenic emissions of volatile organic compounds[J]. Acta Scientiae Circumstantiae,2006,26(5):757-763.
[12]张会敏.环境空气中非甲烷烃的碳同位素组成及其来源研究[D].太原:太原理工大学,2009.
[13]陈颖军,蔡伟伟,黄国培,等.典型排放源黑碳的稳定碳同位素组成研究[J].环境科学,2012,33(3):673-678.Chen Y J,Cai W W,Huang G P,et al. Stable carbon isotope of black carbon from typical emission sources in China[J].Environmental Science,2012,33(3):673-678.
[14] Rudolph J,Lowe D C,Martin R J,et al. A novel method for compound specific determination ofδ13C in volatile organic compounds at ppt levels in ambient air[J]. Geophysical Research Letters,1997,24(6):659-662.
[15] Rudolph J,Czuba E,Norman A L,et al. Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere[J]. Atmospheric Environment,2002,36(7):1173-1181.
[16] Kawashima H,Murakami M. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography,combustion,and isotope ratio mass spectrometry coupled with thermal desorption[J]. Atmospheric Environment,2014,89:140-147.
[17] von Eckstaedt C V,Grice K,Ioppolo-Armanios M,et al.δD andδ13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry[J]. Journal of Chromatography A,2011,1218(37):6511-6517.
[18] von Eckstaedt C V,Grice K,Ioppolo-Armanios M,et al.δ13C andδD of volatile organic compounds in an alumina industry stack emission[J]. Atmospheric Environment,2011,45(31):5477-5483.
[19] von Eckstaedt C D V,Grice K,Ioppolo-Armanios M,et al.Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes[J]. Chemosphere,2012,89(11):1407-1413.
[20]白慧玲,刘效峰,宋翀芳.太原市采暖期PM10中PAHs的碳同位素组成及源贡献率[J].中国环境科学,2014,34(1):7-13.Bai H L,Liu X F,Song C F. Carbon isotope compositions and source apportionments of PAHs in PM10of Taiyuan City during heating period[J]. China Environmental Science,2014,34(1):7-13.
[21]曹润芳,闫雨龙,郭利利,等.太原市大气颗粒物粒径和水溶性离子分布特征[J].环境科学,2016,37(6):2034-2040.Cao R F,Yan Y L,Guo L L,et al. Distribution characteristics of water-soluble ions in size-segregated particulate matters in Taiyuan[J]. Environmental Science,2016,37(6):2034-2040.
[22]任照芳,彭林,张建强,等.兰州市大气中NMHCs的稳定碳同位素组成及来源[J].北京大学学报(自然科学版),2010,46(3):313-318.Ren Z F,Peng L,Zhang J Q,et al. Stable carbon isotopic composition and Source of nonmethane hydrocarbons in urban air,Lanzhou[J]. Acta Scientiarum Naturalium Universitatis Pekinensis,2010,46(3):313-318.
[23] Rudolph J,Czuba E,Huang L,et al. The stable carbon isotope fractionation for reactions of selected hydrocarbons with OHradicals and its relevance for atmospheric chemistry[J]. Journal of Geophysical Research:Atmospheres,2000, 105(D24):29329-29346.
[24] Rudolph J, Czuba E. On the use of isotopic composition measurements of volatile organic compounds to determine the“photochemical age”of an air mass[J]. Geophysical Research Letters,2000,27(23):3865-3868.
[25]白慧玲,彭林,刘效峰,等.太原市工、商业区PM10中PAHs碳同位素组成及来源[J].环境科学研究,2013,26(12):1276-1282.Bai H L,Peng L,Liu X F,et al. Carbon isotope compositions and source apportionment of PAHs associated with PM10of industrial and commercial districts in Taiyuan city[J]. Research of Environmental Sciences,2013,26(12):1276-1282.
[26] Widory D. Combustibles,fuels and their combustion products:a view through carbon isotopes[J]. Combustion Theory and Modelling,2006,10(5):831-841.
[27]白慧玲.环境空气颗粒物中烃类物质的稳定碳、氢同位素组成研究[D].太原:太原理工大学,2014.
[28]彭林,白志鹏,朱坦,等.燃煤烟尘和机动车尾气中PAHs分子化合物的稳定碳同位素研究[J].中国矿业大学学报,2005,34(2):218-221.Peng L,Bai Z P,Zhu T,et al. Research on carbon isotopic compositions of individual PAH in vehicle exhaust and soot of coal combustion[J]. Journal of China University of Mining&Technology,2005,34(2):218-221.
[29]余化龙.燃煤过程中挥发性有机物排放特征研究[D].北京:华北电力大学,2018.
[30]赵锐,黄络萍,张建强,等.成都市典型溶剂源使用行业VOCs排放成分特征[J].环境科学学报,2018,38(3):1147-1154.Zhao R,Huang L P,Zhang J Q,et al. Emissions characteristics of volatile organic compounds(VOCs)from typical industries of solvent use in Chengdu City[J]. Acta Scientiae Circumstantiae,2018,38(3):1147-1154.
[2]陈天增,葛艳丽,刘永春,等.我国机动车排放VOCs及其大气环境影响[J].环境科学,2018,39(2):478-492.Chen T Z,Ge Y L,Liu Y C,et al. VOCs emission from motor vehicles in China and Its impact on the atmospheric environment[J]. Environmental Science,2018,39(2):478-492.
[3]罗达通,高健,王淑兰,等.上海秋季大气挥发性有机物特征及污染物来源分析[J].中国环境科学,2015,35(4):987-994.Luo D T,Gao J,Wang S L,et al. Characteristics of volatile organic compounds and relative pollutants observed in autumn Shanghai[J]. China Environmental Science,2015,35(4):987-994.
[4] Yan Y L,Peng L, Li R M, et al. Concentration, ozone formation potential and source analysis of volatile organic compounds(VOCs)in a thermal power station centralized area:a study in Shuozhou,China[J]. Environmental Pollution,2017,223:295-304.
[5]杨帆,闫雨龙,戈云飞,等.晋城市冬季环境空气中挥发性有机物的污染特征及来源解析[J].环境科学,2018,39(9):4042-4050.Yang F,Yan Y L,Ge Y F,et al. Characteristics and source apportionment of ambient volatile organic compounds in winter in Jincheng[J]. Environmental Science,2018,39(9):4042-4050.
[6]王鸣,陈文泰,陆思华,等.我国典型城市环境大气挥发性有机物特征比值[J].环境科学,2018,39(10):4393-4399.Wang M,Chen W T,Lu S H,et al. Ratios of volatile organic compounds in ambient air of various cities of China[J].Environmental Science,2018,39(10):4393-4399.
[7]李斌,张鑫,李娜,等.北京市春夏挥发性有机物的污染特征及源解析[J].环境化学,2018,37(11):2410-2418.Li B,Zhang X,Li N,et al. Pollution characteristics and source analysis of volatile organic compounds in spring and summer in Beijing[J]. Environmental Chemistry,2018,37(11):2410-2418.
[8] Huang L H,Qian H,Deng S X,et al. Urban residential indoor volatile organic compounds in summer, Beijing:profile,concentration and source characterization[J]. Atmospheric Environment,2018,188:1-11.
[9]王鸣,项萍,牛其恺,等.南阳市冬春交替期大气VOCs污染特征及来源解析[J].环境科学学报,2018,38(6):2233-2241.Wang M,Xiang P,Niu Q K,et al. Characteristics and source apportionment of ambient VOCs during alternating period between winter and spring in Nanyang City,Henan Province[J]. Acta Scientiae Circumstantiae,2018,38(6):2233-2241.
[10] 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.
[11]陆思华,白郁华,张广山,等.大气中挥发性有机化合物(VOCs)的人为来源研究[J].环境科学学报,2006,26(5):757-763.Lu S H,Bai Y H,Zhang G S,et al. Source apportionment of anthropogenic emissions of volatile organic compounds[J]. Acta Scientiae Circumstantiae,2006,26(5):757-763.
[12]张会敏.环境空气中非甲烷烃的碳同位素组成及其来源研究[D].太原:太原理工大学,2009.
[13]陈颖军,蔡伟伟,黄国培,等.典型排放源黑碳的稳定碳同位素组成研究[J].环境科学,2012,33(3):673-678.Chen Y J,Cai W W,Huang G P,et al. Stable carbon isotope of black carbon from typical emission sources in China[J].Environmental Science,2012,33(3):673-678.
[14] Rudolph J,Lowe D C,Martin R J,et al. A novel method for compound specific determination ofδ13C in volatile organic compounds at ppt levels in ambient air[J]. Geophysical Research Letters,1997,24(6):659-662.
[15] Rudolph J,Czuba E,Norman A L,et al. Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere[J]. Atmospheric Environment,2002,36(7):1173-1181.
[16] Kawashima H,Murakami M. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography,combustion,and isotope ratio mass spectrometry coupled with thermal desorption[J]. Atmospheric Environment,2014,89:140-147.
[17] von Eckstaedt C V,Grice K,Ioppolo-Armanios M,et al.δD andδ13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry[J]. Journal of Chromatography A,2011,1218(37):6511-6517.
[18] von Eckstaedt C V,Grice K,Ioppolo-Armanios M,et al.δ13C andδD of volatile organic compounds in an alumina industry stack emission[J]. Atmospheric Environment,2011,45(31):5477-5483.
[19] von Eckstaedt C D V,Grice K,Ioppolo-Armanios M,et al.Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes[J]. Chemosphere,2012,89(11):1407-1413.
[20]白慧玲,刘效峰,宋翀芳.太原市采暖期PM10中PAHs的碳同位素组成及源贡献率[J].中国环境科学,2014,34(1):7-13.Bai H L,Liu X F,Song C F. Carbon isotope compositions and source apportionments of PAHs in PM10of Taiyuan City during heating period[J]. China Environmental Science,2014,34(1):7-13.
[21]曹润芳,闫雨龙,郭利利,等.太原市大气颗粒物粒径和水溶性离子分布特征[J].环境科学,2016,37(6):2034-2040.Cao R F,Yan Y L,Guo L L,et al. Distribution characteristics of water-soluble ions in size-segregated particulate matters in Taiyuan[J]. Environmental Science,2016,37(6):2034-2040.
[22]任照芳,彭林,张建强,等.兰州市大气中NMHCs的稳定碳同位素组成及来源[J].北京大学学报(自然科学版),2010,46(3):313-318.Ren Z F,Peng L,Zhang J Q,et al. Stable carbon isotopic composition and Source of nonmethane hydrocarbons in urban air,Lanzhou[J]. Acta Scientiarum Naturalium Universitatis Pekinensis,2010,46(3):313-318.
[23] Rudolph J,Czuba E,Huang L,et al. The stable carbon isotope fractionation for reactions of selected hydrocarbons with OHradicals and its relevance for atmospheric chemistry[J]. Journal of Geophysical Research:Atmospheres,2000, 105(D24):29329-29346.
[24] Rudolph J, Czuba E. On the use of isotopic composition measurements of volatile organic compounds to determine the“photochemical age”of an air mass[J]. Geophysical Research Letters,2000,27(23):3865-3868.
[25]白慧玲,彭林,刘效峰,等.太原市工、商业区PM10中PAHs碳同位素组成及来源[J].环境科学研究,2013,26(12):1276-1282.Bai H L,Peng L,Liu X F,et al. Carbon isotope compositions and source apportionment of PAHs associated with PM10of industrial and commercial districts in Taiyuan city[J]. Research of Environmental Sciences,2013,26(12):1276-1282.
[26] Widory D. Combustibles,fuels and their combustion products:a view through carbon isotopes[J]. Combustion Theory and Modelling,2006,10(5):831-841.
[27]白慧玲.环境空气颗粒物中烃类物质的稳定碳、氢同位素组成研究[D].太原:太原理工大学,2014.
[28]彭林,白志鹏,朱坦,等.燃煤烟尘和机动车尾气中PAHs分子化合物的稳定碳同位素研究[J].中国矿业大学学报,2005,34(2):218-221.Peng L,Bai Z P,Zhu T,et al. Research on carbon isotopic compositions of individual PAH in vehicle exhaust and soot of coal combustion[J]. Journal of China University of Mining&Technology,2005,34(2):218-221.
[29]余化龙.燃煤过程中挥发性有机物排放特征研究[D].北京:华北电力大学,2018.
[30]赵锐,黄络萍,张建强,等.成都市典型溶剂源使用行业VOCs排放成分特征[J].环境科学学报,2018,38(3):1147-1154.Zhao R,Huang L P,Zhang J Q,et al. Emissions characteristics of volatile organic compounds(VOCs)from typical industries of solvent use in Chengdu City[J]. Acta Scientiae Circumstantiae,2018,38(3):1147-1154.
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