珠三角典型地区大气细颗粒物中有机物质的化学组成研究
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摘要
本文主要利用热解-气相色谱质谱联用技术(Py-GC/MS)对珠三角典型区域的大气颗粒物的化学特征进行研究,讨论了不同地区样品的化学和来源组成。结果显示,不同样品热解产物的组成具有一定的类似性。这些化合物均以脂肪烃(24. 6%～52. 2%)、脂肪酸(5. 0%～43. 6%)、芳香化合物(14. 7%～36. 3%)为主,另外还包括苯酚类化合物(0. 68%～11. 5%)、呋喃类化合物(0. 26%～5. 86%)、含N化合物(4. 80%～10. 2%)和含S化合物(NA～0. 67%)等,表明这些样品主要由芳香碳和脂肪链结构组成,连接有含氧、氮等杂原子基团。同时不同地区的气溶胶样品的热解产物也具有一定的差异性,反映了气溶胶中有机质的组成、来源是有差异的,如从化样品中植物来源贡献是最多的,其次是珠海,广州最少。另外不同季节采集的气溶胶样品的热解产物也表现出一定的差异性,一般情况下夏季样品中生物质来源贡献更多,而冬季样品中则是老化的气溶胶更多。
In this study,the chemical characteristics of fine particles collected in different regions of the Pearl River Delta( PRD)were studied with the pyrolysis-gas chromatography-mass spectrometry( Py-GC-MS),and chemical compositions and sources of these fine particles were discussed. The results showed that the pyrolysis products of fine particles obtained in different sites and seasons were quite similar,mainly contain aliphatic hydrocarbons( 24. 6%-52. 2%),fatty acids( 5. 0%-43. 6%) and aromatic compounds( 14. 7%-36. 3%) with minor contents of phenolic compounds( 0. 68%-11. 5%),furans( 0. 26%-5. 86%),N-containing compounds( 4. 8%-10. 2%) and S-containing compounds( NA-0. 67%). These data suggested that these organic particulate samples are mainly composed of aromatic and aliphatic structures,connected with oxygen,nitrogen and other heteroatom groups. However,differences,which may reflect the differences in chemical composition and source of these organic aerosols,were also founded among of the pyrolysis products of aerosol samples collected in different sites,for example,aerosol samples in the Conghua site exhibited the highest plant-derived characteristics,followed by Zhuhai samples and then Guangzhou samples. In addition,differences were also identified for aerosol samples collected in summer or winter,the pyrolysis products of summer samples usually contained relative high content of plant-derived contributions,while the winter samples contained more aging aerosol components.
In this study,the chemical characteristics of fine particles collected in different regions of the Pearl River Delta( PRD)were studied with the pyrolysis-gas chromatography-mass spectrometry( Py-GC-MS),and chemical compositions and sources of these fine particles were discussed. The results showed that the pyrolysis products of fine particles obtained in different sites and seasons were quite similar,mainly contain aliphatic hydrocarbons( 24. 6%-52. 2%),fatty acids( 5. 0%-43. 6%) and aromatic compounds( 14. 7%-36. 3%) with minor contents of phenolic compounds( 0. 68%-11. 5%),furans( 0. 26%-5. 86%),N-containing compounds( 4. 8%-10. 2%) and S-containing compounds( NA-0. 67%). These data suggested that these organic particulate samples are mainly composed of aromatic and aliphatic structures,connected with oxygen,nitrogen and other heteroatom groups. However,differences,which may reflect the differences in chemical composition and source of these organic aerosols,were also founded among of the pyrolysis products of aerosol samples collected in different sites,for example,aerosol samples in the Conghua site exhibited the highest plant-derived characteristics,followed by Zhuhai samples and then Guangzhou samples. In addition,differences were also identified for aerosol samples collected in summer or winter,the pyrolysis products of summer samples usually contained relative high content of plant-derived contributions,while the winter samples contained more aging aerosol components.
引文
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[24]Bandowe B A,Meusel H,Huang R J,et al.PM2.5-bound oxygenated PAHs,nitro-PAHs and parent-PAHs from the atmosphere of a Chinese megacity:Seasonal variation,sources and cancer risk assessment[J].Science of the Total Environment,2014,473-474(3):77-87.
[25]Zakaria M P,Takada H,Tsutsumi S,et al.Distribution of polycyclic aromatic hydrocarbons(PAHs)in rivers and estuaries in Malaysia:A widespread input of petrogenic PAHs[J].Environmental Science and Technology,2002,36(9):1907-1918.
[26]Chen S J,Luo X J,Mai B X,et al.Distribution and mass inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in sediments of the Pearl River Estuary and the northern South China Sea[J].Environmental Science and Technology,2006,40(3):709-714.
[27]Khoddami A,Wilkes M A,Roberts T H.Techniques for analysis of plant phenolic compounds[J].Molecules,2013,18(2):2328-2375.
[28]Yue Z,Fraser M P.Polar organic compounds measured in fine particulate matter during Tex AQS 2000[J].Atmospheric Environment,2004,38(20):3253-3261.
[29]Cheng Y,Li S M,Leithead A,et al.Characterizations of-pinonic acid and n-fatty acids on fine aerosols in the Lower Fraser Valley during pacific2001 air quality study[J].Atmospheric Environment,2004,38(34):5789-5800.
[30]Schauer J J,Fraser M P,Cas G R,et al.Source reconciliation of atmospheric gas-phase and particle phase pollutants during a severe photochemical smog episode[J].Environmental Science and Technology,2002,36(17):3806-3814.
[31]Ballus C A,Meinhart A D,Oliveira A F D,et al.A quantitative study on the phenolic compound,tocopherol and fatty acid contents of monovarietal virgin olive oils produced in the southeast region of Brazil[J].Food Research International,2014,62(8):74-83.
[32]Huang X F,He L Y,Hu M,et al.Annual variation of particulate organic compounds in PM2.5in the urban atmosphere of Beijing[J].Atmospheric Environment,2006,40(14):2449-2458.
[33]Van M D,Brown S C,Philp R P,et al.Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogens precursors[J].Geochimica et Cosmochimica Acta,1980,44(7):999-1013.
[34]Monlau F,Sambusiti C,Barakat A,et al.Do furanic and phenolic compounds of lignocellulosic and algae biomass hydrolyzate inhibit anaerobic mixed cultures?A comprehensive review[J].Biotechnology Advances,2014,32(5):934-951.
[35]Zhou P,Xiong S,Zhang Y,et al.Study on the nitrogen transformation during the primary pyrolysis of sewage sludge by Py-GC/MS and Py-FTIR[J].International Journal of Hydrogen Energy,2017,42(29):18181-18188.
[36]Simoneit B R T,Rushdi A I,Binabas M B,et al.Alkyl amides andnitriles as novel tracers for biomass burning[J].Environmental Science and Technology,2003,37(1):16-21.
[37]Hendricker A D,Voorhees K J.Amino acid and oligopeptide analysis using curie-point pyrolysis mass spectrometry with in-situ thermal hydrolysis and methylation:Mechanistic considerations[J].Journal of Analytical and Applied Pyrolysis,1998,48(1):17-33.
[38]Komiya M,Shimoyama A.Organic compounds from insoluble organic matter isolated from the Murchison carbonaceous chondrite by heating experiments[J].Bulletin of Chemical Society Japan,1996,69(1):53-58.
[39]Rogge W F,Medeiros P M,Simoneit B R T.Organic marker compounds for surface soil and fugitive dust from open lot dairies and cattle feedlots[J].Atmospheric Environment,2006,40(1):27-49.
[40]Guo Z G,Sheng L F,Feng J L,et al.Seasonal variation of solvent extractable organic compounds in the aerosols in Qingdao,China[J].Atmospheric Environment,2003,37(13):1825-1834.
[41]Yu G G,Wang T G,Wang J,et al.The use of hydrocarbons in source analysis of aerosol[J].Ecology and Environment,2007,16(1):210-215.
[42]Rommerskirchen F,Plader A,Egliton G,et al.Chemotaxonomic significance of distribution and stable carbon isotopic composition of long-chain alkanes and alkan-1-ols in C4 grass waxes[J].Organic Geochemistry,2006,37(10):1303-1332.
[2]Burnett R T,Pope C A,Ezzati M,et al.An integrated risk function for estimating the global burden of disease attributable to ambient fine particulate matter exposure[J].Environmental Health Perspectives,2014,122(4):397-403.
[3]Ki H K,Ehsanul K,Shamin K.A review on the human health impact of airborne particulate matter[J].Environment International,2015,74:136-143.
[4]黄晓锋,云慧,宫照恒,等.深圳大气PM2.5来源解析与二次有机气溶胶估算[J].中国科学(地球科学),2014,44(4):723-734.
[5]Liu J,Li J,Zhang Y,et al.Source apportionment using radiocarbon and organic tracers for PM2.5carbonaceous aerosols in Guangzhou,South China:Contrasting local-and regional-scale haze events[J].Environmental Science and Technology,2014,48(20):12002-12011.
[6]Simoneit B R T.Biomass burning-A review of organic tracers for smoke from incomplete combustion[J].Applied Geochemistry,2002,17(3):129-162.
[7]Chow J C,Lowenthal D H,Chen L W A,et al.Mass reconstruction methods for PM2.5:A review[J].Air Quality,Atmosphere and Health,2015,8(3):243-263.
[8]黄众思,修光利,蔡婧,等.大气PM2.5中水溶性有机碳和类腐殖质碳的季节变化特征[J].环境科学学报,2013,33(10):2664-2670.
[9]Choi J K,Ban S J,Kim Y P,et al.Molecular marker characterization and source appointment of particulate matter and its organic aerosols.[J].Chemosphere,2015,134:482-491.
[10]Turpin B J,Lim H J.Species contributions to PM2.5mass concentrations:Revisiting common assumptions for estimating organic mass[J].Aerosol Science and Technology,2001,35(1):602-610.
[11]Ma Z,Chen D,Gu J,et al.Determination of pyrolysis characteristics and kinetics of palm kernel shell using TGA-FTIR and model-free integral methods[J].Energy Conversion&Management,2015,89:251-259.
[12]Wang S,Ru B,Lin H,et al.Pyrolysis behaviors of four lignin polymers isolated from the same pine wood[J].Bioresource Technology,2015,182:120-127.
[13]Long J X,Xu Y,Wang T J,et al.Efficient base-catalyzed decomposition and in situ hydrogenolysis process for lignin depolymerization and char elimination[J].Applied Energy,2015,141:70-79.
[14]Anastasakis K,Ross A B,Jones J M.Pyrolysis behaviour of the main carbohydrates of brown macro-algae[J].Fuel,2011,90(2):598-607.
[15]Collard F X,Blin J.A review on pyrolysis of biomass constituents:Mechanisms and composition of the products obtained from the conversion of cellulose,hemicelluloses and lignin[J].Renewable&Sustainable Energy Reviews,2014,38(5):594-608.
[16]赵金平,彭平安,宋健中,等.干降尘中高分子有机质的组成及其来源[J].生态环境学报,2009,18(1):5-11.
[17]Zhao J P,Peng P A,Song J Z,et al.Characterization of humic acid-like substances extracted from atmospheric falling dust using Py-GC-MS[D].Aerosol and Air Quality Research,2012,12(1):83-92.
[18]郭送军,谭吉华,段菁春,等.广州市灰霾期PM10的化学组成对能见度的影响[J].环境监测管理与技术,2012,3(24):24-28.
[19]赖安琪,陈晓阳,刘一鸣,等.珠江三角洲PM2.5和O3复合污染过程的数值模拟[J].中国环境科学,2017,37(11):4022-4031.
[20]Zhang Y,Cao C,Li Y,et al.Pyrolysis of n-butylbenzene at various pressures:Influence of long side-chain structure on alkylbenzene pyrolysis[J].Energy&Fuels,2017,31(12):14270-14279.
[21]赵雅楠,闫秀懿,王伟,等.水热法降解聚苯乙烯塑料的实验研究[J].环境工程,2016(s1):773-775.
[22]Nierop K G J,Bergen P F V,Buurman P,et al.Na OH and Na4P2O7,extractable organic matter in two allophanic volcanic ash soils of the A-zores Islands-A pyrolysis GC/MS study[J].Geoderma,2005,127(1):36-51.
[23]Fels L E,Lemee L,Ambles A,et al.Identification and biotransformation of lignin compounds during co-composting of sewage sludge-palm tree waste using Py-GC/MS[J].International Biodeterioration and Biodegradation,2014,92:26-35.
[24]Bandowe B A,Meusel H,Huang R J,et al.PM2.5-bound oxygenated PAHs,nitro-PAHs and parent-PAHs from the atmosphere of a Chinese megacity:Seasonal variation,sources and cancer risk assessment[J].Science of the Total Environment,2014,473-474(3):77-87.
[25]Zakaria M P,Takada H,Tsutsumi S,et al.Distribution of polycyclic aromatic hydrocarbons(PAHs)in rivers and estuaries in Malaysia:A widespread input of petrogenic PAHs[J].Environmental Science and Technology,2002,36(9):1907-1918.
[26]Chen S J,Luo X J,Mai B X,et al.Distribution and mass inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in sediments of the Pearl River Estuary and the northern South China Sea[J].Environmental Science and Technology,2006,40(3):709-714.
[27]Khoddami A,Wilkes M A,Roberts T H.Techniques for analysis of plant phenolic compounds[J].Molecules,2013,18(2):2328-2375.
[28]Yue Z,Fraser M P.Polar organic compounds measured in fine particulate matter during Tex AQS 2000[J].Atmospheric Environment,2004,38(20):3253-3261.
[29]Cheng Y,Li S M,Leithead A,et al.Characterizations of-pinonic acid and n-fatty acids on fine aerosols in the Lower Fraser Valley during pacific2001 air quality study[J].Atmospheric Environment,2004,38(34):5789-5800.
[30]Schauer J J,Fraser M P,Cas G R,et al.Source reconciliation of atmospheric gas-phase and particle phase pollutants during a severe photochemical smog episode[J].Environmental Science and Technology,2002,36(17):3806-3814.
[31]Ballus C A,Meinhart A D,Oliveira A F D,et al.A quantitative study on the phenolic compound,tocopherol and fatty acid contents of monovarietal virgin olive oils produced in the southeast region of Brazil[J].Food Research International,2014,62(8):74-83.
[32]Huang X F,He L Y,Hu M,et al.Annual variation of particulate organic compounds in PM2.5in the urban atmosphere of Beijing[J].Atmospheric Environment,2006,40(14):2449-2458.
[33]Van M D,Brown S C,Philp R P,et al.Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogens precursors[J].Geochimica et Cosmochimica Acta,1980,44(7):999-1013.
[34]Monlau F,Sambusiti C,Barakat A,et al.Do furanic and phenolic compounds of lignocellulosic and algae biomass hydrolyzate inhibit anaerobic mixed cultures?A comprehensive review[J].Biotechnology Advances,2014,32(5):934-951.
[35]Zhou P,Xiong S,Zhang Y,et al.Study on the nitrogen transformation during the primary pyrolysis of sewage sludge by Py-GC/MS and Py-FTIR[J].International Journal of Hydrogen Energy,2017,42(29):18181-18188.
[36]Simoneit B R T,Rushdi A I,Binabas M B,et al.Alkyl amides andnitriles as novel tracers for biomass burning[J].Environmental Science and Technology,2003,37(1):16-21.
[37]Hendricker A D,Voorhees K J.Amino acid and oligopeptide analysis using curie-point pyrolysis mass spectrometry with in-situ thermal hydrolysis and methylation:Mechanistic considerations[J].Journal of Analytical and Applied Pyrolysis,1998,48(1):17-33.
[38]Komiya M,Shimoyama A.Organic compounds from insoluble organic matter isolated from the Murchison carbonaceous chondrite by heating experiments[J].Bulletin of Chemical Society Japan,1996,69(1):53-58.
[39]Rogge W F,Medeiros P M,Simoneit B R T.Organic marker compounds for surface soil and fugitive dust from open lot dairies and cattle feedlots[J].Atmospheric Environment,2006,40(1):27-49.
[40]Guo Z G,Sheng L F,Feng J L,et al.Seasonal variation of solvent extractable organic compounds in the aerosols in Qingdao,China[J].Atmospheric Environment,2003,37(13):1825-1834.
[41]Yu G G,Wang T G,Wang J,et al.The use of hydrocarbons in source analysis of aerosol[J].Ecology and Environment,2007,16(1):210-215.
[42]Rommerskirchen F,Plader A,Egliton G,et al.Chemotaxonomic significance of distribution and stable carbon isotopic composition of long-chain alkanes and alkan-1-ols in C4 grass waxes[J].Organic Geochemistry,2006,37(10):1303-1332.
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