天津夏季大气降水中低分子有机酸研究
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摘要
低分子有机酸是大气中普遍存在的挥发性有机物,它对酸雨的形成具有较为重要的贡献。该研究采集了天津2013-2015年夏季大气降水,用离子色谱测定样品中低分子有机酸以及常规无机阴离子。实验结果表明:甲酸、乙酸和草酸是天津市降水中主要有机酸,它们加权平均浓度分别为12.53、3.45、0.64μmol/L,分别占有机酸的75.39%、20.76%和3.85%。天津降水中甲酸、乙酸和草酸对雨水自由酸的贡献明显小于无机酸,它们对总自由酸的贡献分别为2.45%、0.47%和0.14%;与南方酸雨城市相比,北方城市降水中有机酸对雨水酸度的贡献偏小。用[F/A]T法判断天津市降水中有机酸可能主要来自于植物和蚂蚁直接排放,以及不饱和烃类和醛类的光化学氧化作用。
Low molecular weight carboxylic acids are ubiquitous volatile organic compounds in the troposphere and play an important role in the acidification of precipitation. The rainfall samples were collected from 2013 to 2015 in Tianjin. The carboxylic acids and inorganic anions in the samples were determined using an ion chromatography. The results show that formic acid, acetic acid and oxalic acid were the main carboxylic acids in summer precipitation in Tianjin. Their volume weighted average(VWA) concentrations were 12.53、3.45 and 0.64μmol/L, respectively. They accounting for 75.39%,20.76% and 3.85%of carboxylic acids, respectively. The contribution of formic acid, acetic acid and oxalic acid to the free acidity was obviously lower than that of inorganic acids in precipitation. Formic acid, acetic acid and oxalic acid contributed 2.45%, 0.47% and0.14% of the free acidity, respectively. The contribution of carboxylic acids to precipitation acidity in northern China was marked lower than that in southern cities. Formic-to-acetic acids ratio(F/A), an indicator of sources of these carboxylic acids,suggest that the emission from vegetation and ants, photochemical oxidation of unsaturated hydrocarbons and aldehydes might be dominant sources.
Low molecular weight carboxylic acids are ubiquitous volatile organic compounds in the troposphere and play an important role in the acidification of precipitation. The rainfall samples were collected from 2013 to 2015 in Tianjin. The carboxylic acids and inorganic anions in the samples were determined using an ion chromatography. The results show that formic acid, acetic acid and oxalic acid were the main carboxylic acids in summer precipitation in Tianjin. Their volume weighted average(VWA) concentrations were 12.53、3.45 and 0.64μmol/L, respectively. They accounting for 75.39%,20.76% and 3.85%of carboxylic acids, respectively. The contribution of formic acid, acetic acid and oxalic acid to the free acidity was obviously lower than that of inorganic acids in precipitation. Formic acid, acetic acid and oxalic acid contributed 2.45%, 0.47% and0.14% of the free acidity, respectively. The contribution of carboxylic acids to precipitation acidity in northern China was marked lower than that in southern cities. Formic-to-acetic acids ratio(F/A), an indicator of sources of these carboxylic acids,suggest that the emission from vegetation and ants, photochemical oxidation of unsaturated hydrocarbons and aldehydes might be dominant sources.
引文
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[18]Zhang Y L,Li Q X,Cao F.Chemical characteristics and sources of organic acids in precipitation at a semi-urban site in Southwest China[J].Atomspheric Environment,2011,45:413-419.
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[20]龙晓娟,王雪梅,朱圣洁,等.鼎湖山降水有机酸的变化特征及影响因素分析[J].环境化学,2011,30(9):1611-1619.Long Xiaojuan,Wang Xuemei,Zhu Shengjie,et al.Variation and source analysis of atmospheric organic acids from precipitation at Dinghu Mountain[J].Environmental Chemistry,2011,30(9):1611-1619.
[21]刘辰,何凌燕,牛文,等.深圳降水中低分子量有机酸对降水酸性的贡献[J].环境科学研究,2007,20(5):20-25.Liu Chen,He Lingyan,Niu Wen,et al.Wet deposition of low molecular weighe carboxylic acids in Shenzhen[J].Research of Environmental Sciences,2007,20(5):20-25.
[22]牛彧文,顾骏强,俞向明,等.有机酸对长江三角洲大气背景区降水酸化的影响[J].中国环境科学,2010,30(2):150-154.Niu Yuwen,Gu Junqiang,Yu Xiangming,et al.Impact of organic acids on rainwater acidification in the background air of the Yangtze River Delta[J].China Environmental Science,2010,30(2):150-154.
[23]胡敏,张静,吴志军.北京降水化学组成特征及其对大气颗粒物的去除作用[J].中国科学:B辑化学,2005,35(2):169-176.Hu Min,Zhang Jing,Wu Zhijun.Characteristics of precipitation chemical composition and removal of atmospheric particulates in Beijing[J].Science in China:Ser.B Chemistry,2005,35(2):169-176.
[24]郭雪清,王英峰,施燕支,等.采暖期北京大气气溶胶中有机酸的测定[J].分析测试学报,2007,26(S1):181-183,186.Guo Xueqing,Wang Yingfeng,Shi Yanzhi,et al.Determination of organic acids in atmospheric aerosol during heating period in Beijing[J].Journal of Instrumental Analysis,2007,26(S1):181-183,186.
[25]王晓霞,徐宗学,阮本清.天津市降水量变化趋势的时空分布特征[J].干旱区资源与环境,2008,22(9):92-96.Wang Xiaoxia,Xu Zongxue,Ruan Benqing.Spatiotemporal trend of precipitation in Tianjin City[J].Journal of Arid and Resources and Environment,2008,22(9):92-96.
[26]QX/T 372-2017,酸雨和酸雨标准[S].2017.QX/T 372-2017,Grade of acid rain and acid rain area[S].2017.
[27]Kawamura K,Steinberg S,Lai N,et al.Wet deposition of low molecular weight mono-and dicarboxylic acids,aldehydes and inorganic species in Los Angeles[J].Atmospheric Environment,2001,35(23):3917-3926.
[28]Keene W C,Galloway J N.Organic acidity in precipitation of North America[J].Atmospheric Environment,1984,18:2491-2497.
[29]Sakugawa H,Kaplan R,Shepard L.Measurements of H2O2,aldehydes and organic acids in Los Angeles rainwater:their sourcesand deposition rates[J].Atmospheric Environment,1993,27:203-219.
[30]Keene W C,Galloway JN.Considerations regarding the sources for formic and acetic acids in the troposphere[J].Journal of Geophysical Research,1986,91:14466-14474.
[31]Talbot R W,Beecher K M,Harriss R C,et al.Atmospheric geochemistry of formic and acetic acidsa at a mid-latitude temperate site[J].Journal Geophysical Research,1988,93(D2):1638-1652.
[32]Kumar N,Kulshrestha U C,Saxena A,et al.Formate and acetate levels compared in monsoon and winter rainwater at Dayalbagh,Agra(India)[J].J Atmos Chem,1996,23:81-87.
[33]Katherine M M,Jade N B,Avery Jr G B,et al.Characterization of carbohydrates in rainwater from the Southeastern North Carolina[J].Chemosphere,2014,107:51-57.
[34]Graedel T E,Eiser T.Atmospheric formic acid from formicine ants:apreliminary assessment[J].Tellus B:Chemical and Physical Meteorology,1988,40:335-339.
[2]Li Z J,Song L L,Ma J Z,et al.The characteristics changes of pH and Ec of atmospheric precipitation and analysis on the source of acid rain in the source area of the Yangtze River from 2010 to 2015[J].Atmospheric Environment,2017,156:61-69.
[3]王苗,王凯,刘敏.2014年湖北省酸雨若干特征及其与霾关系分析[J].环境科学与技术,2016,39(4):149-153.Wang Miao,Wang Kai,Liu Min.Characteristics of acid rain of Hubei province in 2014 and relationship between acid rain and smog[J].Environmental Science&Technology,2016,39(4):149-153.
[4]吴文婷,郭青,林涛.梅州城区酸雨特征及成因分析[J].环境科学与技术,2017,40(S1):33-37.Wu Wenting,Guo Qing,Lin Tao.Characteristics and cause of acid rain in Meizhou City[J].Environmental Science&Technology,2017,40(S1):33-37.
[5]Galloway J N,Likens G E,Edgerton E S,et al.Acid precipitation in the Northeastern United States:pH and acidity[J].Science,1976,194:722-724.
[6]Khare P,Kumar N,Kumari K M,et al.Atmospheric formic and acetic acids:an overview[J].Reviews of Geophysics,1999,37:227-248.
[7]何晓欢,徐晓斌,于晓岚,等.我国14个站点降水中甲酸和乙酸浓度及对酸性的贡献[J].环境科学,2010,31(4):858-864.He Xiaohuan,Xu Xiaobin,Yu Xiaolan,et al.Concentrations and acidity contributions of acetate and formate in precipitation at 14 stations of China[J].Environmental Science,2010,31(4):858-864.
[8]Durana N,Casado H,García C,et al.Organic acids in precipitation in the Basque Country(North of Spain)[J].Atmospheric Research,1992,28:93-10.
[9]Fornaro A,Gutz I G R.Wet deposition and related atmospheric chemistry in the S?o Paulo metropolis,Brazil.Part2-contribution of formic and acetic acids[J].Atmospheric Environment,2003,37:117-128.
[10]Willeya J D,Glinskia D A,Southwella M,et al.Decadal variations of rainwater formic and acetic acid concentrationsin Wilmington,NC,USA[J].Atmospheric Environment,2011,45:1010-1014.
[11]Song F,Gao Y.Chemical characteristics of precipitation at metropolitan Newark in the US East Coast[J].Atomspheric Environment,2009,43:4903-4913.
[12]Hu P G,Balasubramanian R,Wu C D.Chemical characterization of rainwater at Singapore[J].Chemosphere,2001,51:747-755.
[13]Pe?a R M,Garcia S,Herrero C,et al.Organic acids andaldehydes in rainwater in a northwest region of Spain[J].Atmospheric Environment,2002,36(34):5277-5288.
[14]Avery G B Jr,Tang Y,Kieber R J,et al.Impact of recent urbanization on formic and acetic acid concentrations in coastal North Carolina rainwater[J].Atomspheric Environment,2001,35:3353-3359.
[15]Avery B G,Kieber J R,Witt M,et al.Rain water monocarboxylic and dicarboxylic acid concentrations insoutheastern North Carolina,USA,as a function of air-massback-trajectory[J].Atmospheric Environment,2006,40(9):1683-1693.
[16]Khare P,Satsangi S G,Kumar N,et al.HCHO,HCOOH and CH3COOH in air and rain water at a rural tropical site in northcentral India[J].Atmospheric Environment,1997,31(23):3867-387.
[17]俞绍才,毕木天,贾欣,等.广州白云山春季降水及广西苗儿山云雾中有机弱酸的研究[J].环境科学学报,1991,11(1):25-30.Yu Shaocai,Bi Mutian,Jia Xin,et al.Organic acids in precipitation from Baiyun Mountain,Guangzhou and in fog from Miaoer Mountain,Guangxi[J].Acta Scientiae Circumstantiae,1991,11(1):25-30.
[18]Zhang Y L,Li Q X,Cao F.Chemical characteristics and sources of organic acids in precipitation at a semi-urban site in Southwest China[J].Atomspheric Environment,2011,45:413-419.
[19]Xu G,Li X Q,Lyu Y C,et al.Seasonal variations of carboxylic acids and their contributions to the rainwater acidity:acase study of Guiyang City and Shangzhong Town,China[J].Chinese Science Bulletin,2010,55(16):1667-1673.
[20]龙晓娟,王雪梅,朱圣洁,等.鼎湖山降水有机酸的变化特征及影响因素分析[J].环境化学,2011,30(9):1611-1619.Long Xiaojuan,Wang Xuemei,Zhu Shengjie,et al.Variation and source analysis of atmospheric organic acids from precipitation at Dinghu Mountain[J].Environmental Chemistry,2011,30(9):1611-1619.
[21]刘辰,何凌燕,牛文,等.深圳降水中低分子量有机酸对降水酸性的贡献[J].环境科学研究,2007,20(5):20-25.Liu Chen,He Lingyan,Niu Wen,et al.Wet deposition of low molecular weighe carboxylic acids in Shenzhen[J].Research of Environmental Sciences,2007,20(5):20-25.
[22]牛彧文,顾骏强,俞向明,等.有机酸对长江三角洲大气背景区降水酸化的影响[J].中国环境科学,2010,30(2):150-154.Niu Yuwen,Gu Junqiang,Yu Xiangming,et al.Impact of organic acids on rainwater acidification in the background air of the Yangtze River Delta[J].China Environmental Science,2010,30(2):150-154.
[23]胡敏,张静,吴志军.北京降水化学组成特征及其对大气颗粒物的去除作用[J].中国科学:B辑化学,2005,35(2):169-176.Hu Min,Zhang Jing,Wu Zhijun.Characteristics of precipitation chemical composition and removal of atmospheric particulates in Beijing[J].Science in China:Ser.B Chemistry,2005,35(2):169-176.
[24]郭雪清,王英峰,施燕支,等.采暖期北京大气气溶胶中有机酸的测定[J].分析测试学报,2007,26(S1):181-183,186.Guo Xueqing,Wang Yingfeng,Shi Yanzhi,et al.Determination of organic acids in atmospheric aerosol during heating period in Beijing[J].Journal of Instrumental Analysis,2007,26(S1):181-183,186.
[25]王晓霞,徐宗学,阮本清.天津市降水量变化趋势的时空分布特征[J].干旱区资源与环境,2008,22(9):92-96.Wang Xiaoxia,Xu Zongxue,Ruan Benqing.Spatiotemporal trend of precipitation in Tianjin City[J].Journal of Arid and Resources and Environment,2008,22(9):92-96.
[26]QX/T 372-2017,酸雨和酸雨标准[S].2017.QX/T 372-2017,Grade of acid rain and acid rain area[S].2017.
[27]Kawamura K,Steinberg S,Lai N,et al.Wet deposition of low molecular weight mono-and dicarboxylic acids,aldehydes and inorganic species in Los Angeles[J].Atmospheric Environment,2001,35(23):3917-3926.
[28]Keene W C,Galloway J N.Organic acidity in precipitation of North America[J].Atmospheric Environment,1984,18:2491-2497.
[29]Sakugawa H,Kaplan R,Shepard L.Measurements of H2O2,aldehydes and organic acids in Los Angeles rainwater:their sourcesand deposition rates[J].Atmospheric Environment,1993,27:203-219.
[30]Keene W C,Galloway JN.Considerations regarding the sources for formic and acetic acids in the troposphere[J].Journal of Geophysical Research,1986,91:14466-14474.
[31]Talbot R W,Beecher K M,Harriss R C,et al.Atmospheric geochemistry of formic and acetic acidsa at a mid-latitude temperate site[J].Journal Geophysical Research,1988,93(D2):1638-1652.
[32]Kumar N,Kulshrestha U C,Saxena A,et al.Formate and acetate levels compared in monsoon and winter rainwater at Dayalbagh,Agra(India)[J].J Atmos Chem,1996,23:81-87.
[33]Katherine M M,Jade N B,Avery Jr G B,et al.Characterization of carbohydrates in rainwater from the Southeastern North Carolina[J].Chemosphere,2014,107:51-57.
[34]Graedel T E,Eiser T.Atmospheric formic acid from formicine ants:apreliminary assessment[J].Tellus B:Chemical and Physical Meteorology,1988,40:335-339.