石家庄秋季PM_(2.5)中低分子量有机酸组成特征及来源解析
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摘要
为探讨石家庄秋季PM_(2.5)中低分子量有机酸组成特征与来源,于2017年9—10月对石家庄PM_(2.5)进行采样并测定了3种低分子量有机酸(甲酸、乙酸、草酸)浓度,还测定了水溶性无机离子(Cl~-、NO_3~-、SO_4~(2-)、K~+、Na~+、Ca~(2+)、Mg~(2+)、NH_4~+)辅助讨论有机酸来源。结果发现,石家庄秋季PM_(2.5)中草酸浓度高于甲酸和乙酸,而甲酸和乙酸浓度接近,甲酸、乙酸和草酸的质量浓度分别为20~240、50~280、60~1 130ng/m~3。石家庄秋季PM_(2.5)中低分子量有机酸受自然源和人为源的混合影响,以人为源占主导,其中甲酸和乙酸的同源性较高。甲酸的可能来源为工业燃煤、交通汽车尾气排放、生物质燃烧、土壤和扬尘。乙酸的可能来源为工业燃煤、交通汽车尾气排放、生物质燃烧、生活污水、土壤和扬尘。草酸的可能来源为交通汽车尾气排放、大气氧化反应、生物质燃烧、土壤和扬尘、生活污水。
In order to study the composition characteristic and sources of low molecular weight organic acids in PM_(2.5)of Shijiazhuang autumn,PM_(2.5)samples were collected in Shijiazhuang from September to October of 2017.The concentrations of low molecular weight organic acids(formic acid,acetic acid and oxalic acid)were determined,and dissolved inorganic ions(Cl~-,NO_3~-,SO_4~(2-),K~+,Na~+,Ca~(2+),Mg~(2+)and NH_4~+)were used to assist discussion of sources.Results showed that oxalic acid was more abundant than formic acid and acetic acid while the latter two were similar.The mass concentrations of formic acid,acetic acid and oxalic acid were 20-240,50-280and 60-1 130ng/m~3,respectively.The 3organic acids influenced by both natural sources and anthropogenic sources,but mainly the latter,among which formic acid and acetic acid had similar sources.Formic acid might come from industrial coal combustion,vehicle exhaust,biomass burning,soil and dust.Acetic acid might come from industrial coal combustion,vehicle exhaust,biomass burning,municipal wastewater,soil and dust.Oxalic acid might come from vehicle exhaust,atmospheric oxidation,biomass burning,municipal wastewater,soil and dust.
In order to study the composition characteristic and sources of low molecular weight organic acids in PM_(2.5)of Shijiazhuang autumn,PM_(2.5)samples were collected in Shijiazhuang from September to October of 2017.The concentrations of low molecular weight organic acids(formic acid,acetic acid and oxalic acid)were determined,and dissolved inorganic ions(Cl~-,NO_3~-,SO_4~(2-),K~+,Na~+,Ca~(2+),Mg~(2+)and NH_4~+)were used to assist discussion of sources.Results showed that oxalic acid was more abundant than formic acid and acetic acid while the latter two were similar.The mass concentrations of formic acid,acetic acid and oxalic acid were 20-240,50-280and 60-1 130ng/m~3,respectively.The 3organic acids influenced by both natural sources and anthropogenic sources,but mainly the latter,among which formic acid and acetic acid had similar sources.Formic acid might come from industrial coal combustion,vehicle exhaust,biomass burning,soil and dust.Acetic acid might come from industrial coal combustion,vehicle exhaust,biomass burning,municipal wastewater,soil and dust.Oxalic acid might come from vehicle exhaust,atmospheric oxidation,biomass burning,municipal wastewater,soil and dust.
引文
[1] BOUROTTE C,CURI A P,FORTI M C,et al.Association between ionic composition of fine and coarse aerosol soluble fraction and peak expiratory flow of asthmatic patients in S2o Paulo city(Brazil)[J].Atmospheric Environment,2007,41(10):2036-2048.
[2] ROGGE W F,MAZUREK M A,HILDEMANN L M,et al.Quantification of urban organic aerosols at a molecular level:identification,abundance and seasonal variation[J].Atmospheric Environment,1993,27(8):1309-1330.
[3] BROOKS AVERY G,KIEBER R J,WITT M,et al.Rainwater monocarboxylic and dicarboxylic acid concentrations in southeastern North Carolina,USA,as a function of air-mass backtrajectory[J].Atmospheric Environment,2006,40(9):1683-1693.
[4] HARA K,OSADA K,MATSUNAGA K,et al.Concentration trends and mixing states of particulate oxalate in arctic boundary layer in winter/spring[J].Journal of Geophysical Research:Atmospheres,2002,107(D19):AAC 12-1-AAC 12-14.
[5] LEFER B L,TALBOT R W,HARRISS R H,et al.Enhancement of acidic gases in biomass burning impacted air masses over Canada[J].Journal of Geophysical Research:Atmospheres,1994,99(D1):1721-1737.
[6] KAWAMURA K,NG L L,KAPLAN I R.Determination of organic acids(C1-C10)in the atmosphere,motor exhausts,and engine oils[J].Environmental Science&Technology,1985,19(11):1082-1086.
[7] PAULOT F,WUNCH D,CROUNSE J D,et al.Importance of secondary sources in the atmospheric budgets of formic and acetic acids[J].Atmospheric Chemistry&Physics,2011,11(10):1989-2013.
[8] KHARE P,KUMAR N,KUMARI K M,et al.Atmospheric formic and acetic acids:an overview[J].Reviews of Geophysics,1999,37(2):227-248.
[9]生态环境部.2017全国生态环境状况公报[R].北京:生态环境部,2018.
[10] WANG Y,ZHUANG G,CHEN S,et al.Characteristics and sources of formic,acetic and oxalic acids in PM2.5and PM10aerosols in Beijing,China[J].Atmospheric Research,2007,84(2):169-181.
[11] YANG H,YU J Z,HO S S H,et al.The chemical composition of inorganic and carbonaceous materials in PM2.5in Nanjing,China[J].Atmospheric Environment,2005,39(20):3735-3749.
[12] YAO X,CHAN C K,FANG M,et al.The water-soluble ionic composition of PM2.5in Shanghai and Beijing,China[J].Atmospheric Environment,2002,36(26):4223-4234.
[13] YAO X,CHAN F C K,HO K F,et al.Characterization of dicarboxylic acids in PM2.5in Hong Kong[J].Atmospheric Environment,2004,38(7):963-970.
[14] RHRL A,LAMMEL G.Low-molecular weight dicarboxylic acids and glyoxylic acid:seasonal and air mass characteristics[J].Environmental Science&Technology,2001,35(1):95-101.
[15] SOUZA S R,VASCONCELLOS P C,CARVALHO L R F.Low molecular weight carboxylic acids in an urban atmosphere:winter measurements in S2o Paulo City,Brazil[J].Atmospheric Environment,1999,33(16):2563-2574.
[16] KARTHIKEYAN S,BALASUBRAMANIAN R.Rapid extraction of water soluble organic compounds from airborne particulate matter[J].Analytical Sciences,2005,21(12):1505-1508.
[17] VERMA N,SATSANGI A,LAKHANI A,et al.Low molecular weight monocarboxylic acids in PM2.5and PM10:quantification,seasonal variation and source apportionment[J].Aerosol&Air Quality Research,2017,17(2):485-498.
[18] FORNARO A,GUTZ I G R.Wet deposition and related atmospheric chemistry in the S2o Paulo metropolis Brazil:Part2-contribution of formic and acetic acids[J].Atmospheric Environment,2003,37(1):117-128.
[19] TALBOT R W,BEECHER K M,HARRISS R C,et al.Atmospheric geochemistry of formic and acetic acids at a midlatitude temperate site[J].Journal of Geophysical Research:Atmospheres,1988,93(D2):1638-1652.
[20] HE K,YANG F,MA Y,et al.The characteristics of PM2.5in Beijing,China[J].Atmospheric Environment,2001,35(29):4959-4970.
[21]石家庄统计局,国家统计局石家庄调查队.石家庄统计年鉴2017[M].北京:中国统计出版社,2017.
[22] ALASTUEY A,QUEROL X,PLANA F,et al.Identification and chemical characterization of industrial particulate matter sources in southwest Spain[J].Journal of the Air&Waste Management Association,2006,56(7):993-1006.
[23] MKOMA S L,ROCHA G O,SILVA J D S,et al.Characteristics of low-molecular weight carboxylic acids in PM2.5and PM10 ambient aerosols from Tanzania[C]//ABDUL RAZZAK H.Atmospheric Aerosols.Novi Sad:Intech Prepress,2012.
[24] LEE E,CHAN C K,PAATERO P.Application of positive matrix factorization in source apportionment of particulate pollutants in Hong Kong[J].Atmospheric Environment,1999,33(19):3201-3212.
[25]唐喜斌.秸秆燃烧对灰霾天气的影响分析及其排放因子与颗粒物成分谱[D].上海:华东理工大学,2014.
[26]邱婷,周家斌,肖经汗,等.武汉市秋、冬季大气PM2.5中水溶性离子污染特征及来源分析[J].环境污染与防治,2015,37(4):17-20.
[27]刘忠马,徐义邦,樊孝俊,等.南昌市秋季大气PM2.5浓度及化学组分特征分析[J].环境污染与防治,2015,37(9):55-59.
[28]肖红伟,肖化云,唐从国,等.贵阳地区氨排放量估算[J].地球与环境,2010,38(1):21-25.
[29] XIAO H W,XIAO H Y,LONG A M,et al.Who controls the monthly variations of NH+4nitrogen isotope composition in precipitation?[J].Atmospheric Environment,2012,54:201-206.
[2] ROGGE W F,MAZUREK M A,HILDEMANN L M,et al.Quantification of urban organic aerosols at a molecular level:identification,abundance and seasonal variation[J].Atmospheric Environment,1993,27(8):1309-1330.
[3] BROOKS AVERY G,KIEBER R J,WITT M,et al.Rainwater monocarboxylic and dicarboxylic acid concentrations in southeastern North Carolina,USA,as a function of air-mass backtrajectory[J].Atmospheric Environment,2006,40(9):1683-1693.
[4] HARA K,OSADA K,MATSUNAGA K,et al.Concentration trends and mixing states of particulate oxalate in arctic boundary layer in winter/spring[J].Journal of Geophysical Research:Atmospheres,2002,107(D19):AAC 12-1-AAC 12-14.
[5] LEFER B L,TALBOT R W,HARRISS R H,et al.Enhancement of acidic gases in biomass burning impacted air masses over Canada[J].Journal of Geophysical Research:Atmospheres,1994,99(D1):1721-1737.
[6] KAWAMURA K,NG L L,KAPLAN I R.Determination of organic acids(C1-C10)in the atmosphere,motor exhausts,and engine oils[J].Environmental Science&Technology,1985,19(11):1082-1086.
[7] PAULOT F,WUNCH D,CROUNSE J D,et al.Importance of secondary sources in the atmospheric budgets of formic and acetic acids[J].Atmospheric Chemistry&Physics,2011,11(10):1989-2013.
[8] KHARE P,KUMAR N,KUMARI K M,et al.Atmospheric formic and acetic acids:an overview[J].Reviews of Geophysics,1999,37(2):227-248.
[9]生态环境部.2017全国生态环境状况公报[R].北京:生态环境部,2018.
[10] WANG Y,ZHUANG G,CHEN S,et al.Characteristics and sources of formic,acetic and oxalic acids in PM2.5and PM10aerosols in Beijing,China[J].Atmospheric Research,2007,84(2):169-181.
[11] YANG H,YU J Z,HO S S H,et al.The chemical composition of inorganic and carbonaceous materials in PM2.5in Nanjing,China[J].Atmospheric Environment,2005,39(20):3735-3749.
[12] YAO X,CHAN C K,FANG M,et al.The water-soluble ionic composition of PM2.5in Shanghai and Beijing,China[J].Atmospheric Environment,2002,36(26):4223-4234.
[13] YAO X,CHAN F C K,HO K F,et al.Characterization of dicarboxylic acids in PM2.5in Hong Kong[J].Atmospheric Environment,2004,38(7):963-970.
[14] RHRL A,LAMMEL G.Low-molecular weight dicarboxylic acids and glyoxylic acid:seasonal and air mass characteristics[J].Environmental Science&Technology,2001,35(1):95-101.
[15] SOUZA S R,VASCONCELLOS P C,CARVALHO L R F.Low molecular weight carboxylic acids in an urban atmosphere:winter measurements in S2o Paulo City,Brazil[J].Atmospheric Environment,1999,33(16):2563-2574.
[16] KARTHIKEYAN S,BALASUBRAMANIAN R.Rapid extraction of water soluble organic compounds from airborne particulate matter[J].Analytical Sciences,2005,21(12):1505-1508.
[17] VERMA N,SATSANGI A,LAKHANI A,et al.Low molecular weight monocarboxylic acids in PM2.5and PM10:quantification,seasonal variation and source apportionment[J].Aerosol&Air Quality Research,2017,17(2):485-498.
[18] FORNARO A,GUTZ I G R.Wet deposition and related atmospheric chemistry in the S2o Paulo metropolis Brazil:Part2-contribution of formic and acetic acids[J].Atmospheric Environment,2003,37(1):117-128.
[19] TALBOT R W,BEECHER K M,HARRISS R C,et al.Atmospheric geochemistry of formic and acetic acids at a midlatitude temperate site[J].Journal of Geophysical Research:Atmospheres,1988,93(D2):1638-1652.
[20] HE K,YANG F,MA Y,et al.The characteristics of PM2.5in Beijing,China[J].Atmospheric Environment,2001,35(29):4959-4970.
[21]石家庄统计局,国家统计局石家庄调查队.石家庄统计年鉴2017[M].北京:中国统计出版社,2017.
[22] ALASTUEY A,QUEROL X,PLANA F,et al.Identification and chemical characterization of industrial particulate matter sources in southwest Spain[J].Journal of the Air&Waste Management Association,2006,56(7):993-1006.
[23] MKOMA S L,ROCHA G O,SILVA J D S,et al.Characteristics of low-molecular weight carboxylic acids in PM2.5and PM10 ambient aerosols from Tanzania[C]//ABDUL RAZZAK H.Atmospheric Aerosols.Novi Sad:Intech Prepress,2012.
[24] LEE E,CHAN C K,PAATERO P.Application of positive matrix factorization in source apportionment of particulate pollutants in Hong Kong[J].Atmospheric Environment,1999,33(19):3201-3212.
[25]唐喜斌.秸秆燃烧对灰霾天气的影响分析及其排放因子与颗粒物成分谱[D].上海:华东理工大学,2014.
[26]邱婷,周家斌,肖经汗,等.武汉市秋、冬季大气PM2.5中水溶性离子污染特征及来源分析[J].环境污染与防治,2015,37(4):17-20.
[27]刘忠马,徐义邦,樊孝俊,等.南昌市秋季大气PM2.5浓度及化学组分特征分析[J].环境污染与防治,2015,37(9):55-59.
[28]肖红伟,肖化云,唐从国,等.贵阳地区氨排放量估算[J].地球与环境,2010,38(1):21-25.
[29] XIAO H W,XIAO H Y,LONG A M,et al.Who controls the monthly variations of NH+4nitrogen isotope composition in precipitation?[J].Atmospheric Environment,2012,54:201-206.