广州冬季气溶胶中水溶性有机物和类腐殖质的吸光性和荧光光谱特性
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摘要
利用紫外-可见光谱与三维荧光-平行因子分析法(EEM-PARAFAC),研究了广州市2014年12月～2015年1月大气气溶胶中水溶性有机物(WSOC)和类腐殖质(HULIS)的吸光性和荧光光谱特征.结果表明,广州冬季气溶胶中HULIS的芳香性(SUVA254)、腐殖化程度(HIX)和光吸收效率(MAE365)均高于WSOC.利用EEM-PARAFAC从WSOC和HULIS解析出了类富里酸(C1)、类腐殖酸(C2)和类蛋白(C3)这3种荧光组分.其中类腐殖质组分(C1+C2)分别占WSOC和HULIS中总荧光组分的78%和85%,说明类腐殖荧光组分是WSOC和HULIS的最主要组成,且HULIS富集了更多的WSOC中主要的类腐殖组分.另外,灰霾期的WSOC和HULIS表现出更高的芳香性、腐殖化程度和C2组分,说明灰霾期有助于大分子量吸光性有机质的形成.相关性分析结果显示,WSOC和HULIS的C1组分相对含量与HIX、MAE365、OCsec、K+、SO_4~(2-)和NH_4~+呈现极显著的负相关关系,而C2与它们之间存在极显著的正相关关系.由此说明,WSOC和HULIS中C1的降低和C2的增加会引起它们的腐殖化程度和光吸收能力的增强;同时生物质燃烧排放和二次气溶胶过程可能有助于C2组分的增加.
The light absorption and fluorescence characteristics of atmospheric water-soluble organic compounds( WSOC) and humiclike substances( HULIS) during the winter season in Guangzhou were examined using UV-vis spectroscopy and excitation-emission matrix spectroscopy combined with parallel factor analysis( EEM-PARAFAC). The results showed that the SUVA254,HIX,and MAE365 values of HULIS were higher than those of WSOC,suggesting that the former had higher aromaticity,humification,and lightabsorption capacity in winter atmospheric PM_(2.5) in Guangzhou. EEM-PARAFAC analysis identified three fluorescence components,including fulvic-like acid( C1),humic-like acid( C2),and protein-like( C3) components. The total humic-like components( C1 +C2) accounted for 78% and 85% for WSOC and HULIS,respectively,which indicated that humic-like fluorescence components were the major components for both WSOC and HULIS and that HULIS were enriched with the dominant humic-like fluorophores. In addition,the aromaticity,humification,light-absorbing capacity,and C2 levels of WSOC and HULIS during the haze episode were significantly higher than those in the non-haze episode. This suggested that the water-soluble organics with higher molecular weights and stronger light-absorption capacities tended to form during the haze episode. The correlations analysis revealed strong negative correlations between C1 levels of WSOC and HULIS and HIX,MAE365,OCsec,K+,SO_4~(2-),and NH_4~+. Additionally,strong positive correlations were observed between C2 levels and the same factors. These results implied that the decrease in C1 and increase in C2 might lead to increased humification and light-absorption in WSOC and HULIS,and biomass burning and secondary organic aerosols might contribute to the C2 component.
The light absorption and fluorescence characteristics of atmospheric water-soluble organic compounds( WSOC) and humiclike substances( HULIS) during the winter season in Guangzhou were examined using UV-vis spectroscopy and excitation-emission matrix spectroscopy combined with parallel factor analysis( EEM-PARAFAC). The results showed that the SUVA254,HIX,and MAE365 values of HULIS were higher than those of WSOC,suggesting that the former had higher aromaticity,humification,and lightabsorption capacity in winter atmospheric PM_(2.5) in Guangzhou. EEM-PARAFAC analysis identified three fluorescence components,including fulvic-like acid( C1),humic-like acid( C2),and protein-like( C3) components. The total humic-like components( C1 +C2) accounted for 78% and 85% for WSOC and HULIS,respectively,which indicated that humic-like fluorescence components were the major components for both WSOC and HULIS and that HULIS were enriched with the dominant humic-like fluorophores. In addition,the aromaticity,humification,light-absorbing capacity,and C2 levels of WSOC and HULIS during the haze episode were significantly higher than those in the non-haze episode. This suggested that the water-soluble organics with higher molecular weights and stronger light-absorption capacities tended to form during the haze episode. The correlations analysis revealed strong negative correlations between C1 levels of WSOC and HULIS and HIX,MAE365,OCsec,K+,SO_4~(2-),and NH_4~+. Additionally,strong positive correlations were observed between C2 levels and the same factors. These results implied that the decrease in C1 and increase in C2 might lead to increased humification and light-absorption in WSOC and HULIS,and biomass burning and secondary organic aerosols might contribute to the C2 component.
引文
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[9] Hoffer A,Gelencsér A,Guyon P,et al. Optical properties of humic-like substances(HULIS)in biomass-burning aerosols[J]. Atmospheric Chemistry and Physics,2006,6(11):3563-3570.
[10] Du Z Y,He K B,Cheng Y,et al. A yearlong study of watersoluble organic carbon in Beijing II:Light absorption properties[J]. Atmospheric Environment,2014,89:235-241.
[11] Santos P S M,Otero M,Duarte R M B O,et al. Spectroscopic characterization of dissolved organic matter isolated from rainwater[J]. Chemosphere,2009,74(8):1053-1061.
[12] Santos P S M,Santos E B H,Duarte A C. First spectroscopic study on the structural features of dissolved organic matter isolated from rainwater in different seasons[J]. Science of the Total Environment,2012,426:172-179.
[13] Chen Q C,Miyazaki Y,Kawamura K,et al. Characterization of chromophoric water-soluble Organic matter in urban,forest,and marine aerosols by HR-ToF-AMS analysis and excitation-emission matrix spectroscopy[J]. Environmental Science&Technology,2016,50(19):10351-10360.
[14] Yan G,Kim G. Speciation and sources of brown carbon in precipitation at seoul,Korea:Insights from excitation-emission matrix spectroscopy and carbon isotopic analysis[J].Environmental Science&Technology,2017,51(20):11580-11587.
[15] Fan X J,Song J Z,Peng P A. Comparison of isolation and quantification methods to measure humic-like substances(HULIS)in atmospheric particles[J]. Atmospheric Environment,2012,60:366-374.
[16] Baduel C, Voisin D, Jaffrezo J L. Seasonal variations of concentrations and optical properties of water soluble HULIS collected in urban environments[J]. Atmospheric Chemistry and Physics,2010,10(9):4085-4095.
[17] Fan X J,Song J Z,Peng P A. Temporal variations of the abundance and optical properties of water soluble Humic-Like Substances(HULIS)in PM2. 5at Guangzhou, China[J].Atmospheric Research,2016,172-173:8-15.
[18]梁俭,江韬,魏世强,等.夏、冬季降雨中溶解性有机质(DOM)光谱特征及来源辨析[J].环境科学,2015,36(3):888-897.Liang J,Jiang T,Wei S Q,et al. Absorption and fluorescence characteristics of dissolved organic matter(DOM)in rainwater and sources analysis in summer and winter season[J].Environmental Science,2015,36(3):888-897.
[19] Stedmon C A,Bro R. Characterizing dissolved organic matter fluorescence with parallel factor analysis:a tutorial[J].Limnology and Oceanography:Methods,2008,6(11):572-579.
[20] Matos J T V,Freire S M S C,Duarte R M B O,et al. Natural organic matter in urban aerosols:Comparison between water and alkaline soluble components using excitation-emission matrix fluorescence spectroscopy and multiway data analysis[J].Atmospheric Environment,2015,102:1-10.
[21]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.Huang Z S,Xiu G L,Cai J,et al. Seasonal characterization of water-soluble organic carbon and humic-like substance carbon in atmospheric PM2. 5[J]. Acta Scientiae Circumstantiae,2013,33(10):2664-2670.
[22]谭吉华,段菁春,赵金平,等.广州市灰霾期间大气颗粒物中有机碳和元素碳的粒径分布[J].环境化学,2009,28(2):267-271.
[23] Qiao T,Zhao M F,Xiu G L,et al. Seasonal variations of water soluble composition(WSOC,Hulis and WSIIs)in PM1and its implications on haze pollution in urban Shanghai,China[J].Atmospheric Environment,2015,123:306-314.
[24] Fan X J,Song J Z,Peng P A. Comparative study for separation of atmospheric humic-like substance(HULIS)by ENVI-18,HLB,XAD-8 and DEAE sorbents:elemental composition,FTIR,1H NMR and off-line thermochemolysis with tetramethylammonium hydroxide(TMAH)[J]. Chemosphere,2013,93(9):1710-1719.
[25] Baduel C,Voisin D,Jaffrezo J L. Comparison of analytical methods for Humic Like Substances(HULIS)measurements in atmospheric particles[J]. Atmospheric Chemistry and Physics,2009,9(16):5949-5962.
[26] Baduel C, Monge M E, Voisin D, et al. Oxidation of atmospheric humic like substances by ozone:a kinetic and structural analysis approach[J]. Environmental Science&Technology,2011,45(12):5238-44.
[27] Wong J P S,Nenes A,Weber R J. Changes in light absorptivity of molecular weight separated brown carbon due to photolytic aging[J]. Environmental Science&Technology,2017,51(15):8414-8421.
[28]程玉婷,王格慧,孙涛,等.西安冬季非灰霾天与灰霾天PM2. 5中水溶性有机氮污染特征比较[J].环境科学,2014,35(7):2468-2476.Cheng Y T,Wang G H,Sun T,et al. Characteristics of watersoluble organic nitrogen of PM2. 5in Xi'an during wintertime nonhaze and haze periods[J]. Environmental Science,2014,35(7):2468-2476.
[29]闫才青,郑玫,张远航.大气棕色碳的研究进展与方向[J].环境科学,2014,35(11):4404-4414.Yan C Q, Zheng M, Zhang Y H. Research progress and direction of atmospheric brown carbon[J]. Environmental Science,2014,35(11):4404-4414.
[30]支国瑞,蔡竟,杨俊超,等.棕色碳气溶胶来源、性质、测量与排放估算[J].环境科学研究,2015,28(12):1797-1814.Zhi G R, Cai J, Yang J C, et al. Origin, properties,measurement and emission estimation of brown carbon aerosols[J]. Research of Environmental Sciences,2015,28(12):1797-1814.
[31] Park S S,Yu J. Chemical and light absorption properties of humic-like substances from biomass burning emissions under controlled combustion experiments[J]. Atmospheric Environment,2016,136:114-122.
[32] Yuan J F,Huang X F,Cao L M,et al. Light absorption of brown carbon aerosol in the PRD region of China[J].Atmospheric Chemistry and Physics,2016,16(3):1433-1443.
[33] Han H,Kim G. Significant seasonal change in optical properties by atmospheric humic-like substances(HULIS)in water-soluble organic carbon aerosols[J]. Atmospheric Chemistry and Physics Discussion,2017,doi:10. 5194/acp-2017-554.
[34] Fan X J,Wei S Y,Zhu M B,et al. Molecular characterization of primary humic-like substances in fine smoke particles by thermochemolysis-gas chromatography-mass spectrometry[J].Atmospheric Environment,2018,180:1-10.
[35] Song J Z,Li M J,Jiang B,et al. Molecular characterization of water-soluble humic like substances in smoke particles emitted from combustion of biomass materials and coal using ultrahighresolution electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Environmental Science&Technology,2018,52(5):2575-2585.
[36] Santos G T A D,Santos P S M,Duarte A C. Vanillic and syringic acids from biomass burning:Behaviour during Fentonlike oxidation in atmospheric aqueous phase and in the absence of light[J]. Journal of Hazardous Materials,2016,313:201-208.
[37] Santos P S M,Domingues M R M,Duarte A C. Fenton-like oxidation of small aromatic acids from biomass burning in atmospheric water and in the absence of light:Identification of intermediates and reaction pathways[J]. Chemosphere,2016,154:599-603.
[2] Zheng G J,He K B,Duan F K,et al. Measurement of humiclike substances in aerosols:a review[J]. Environmental Pollution,2013,181:301-314.
[3] Feng Y,Ramanathan V,Kotamarthi V R. Brown carbon:a significant atmospheric absorber of solar radiation?[J].Atmospheric Chemistry and Physics,2013,13(17):8607-8621.
[4] Liu J,Scheuer E,Dibb J,et al. Brown carbon aerosol in the North American continental troposphere:sources,abundance,and radiative forcing[J]. Atmospheric Chemistry and Physics,2015,15(14):7841-7858.
[5] Fan X J, Wei S Y, Zhu M B, et al. Comprehensive characterization of humic-like substances in smoke PM2. 5emitted from the combustion of biomass materials and fossil fuels[J].Atmospheric Chemistry and Physics,2016,16(20):13321-13340.
[6] Cheng Y,He K B,Zheng M,et al. Mass absorption efficiency of elemental carbon and water-soluble organic carbon in Beijing,China[J]. Atmospheric Chemistry and Physics,2011,11(22):11497-11510.
[7] Cheng Y,He K B,Du Z Y,et al. The characteristics of brown carbon aerosol during winter in Beijing[J]. Atmospheric Environment,2016,127:355-364.
[8]黄欢,毕新慧,彭龙,等.广州城区秋冬季大气颗粒物中WSOC吸光性研究[J].环境科学,2016,37(1):16-21.Huang H,Bi X H,Peng L,et al. Light absorption properties of water-soluble organic carbon(WSOC)associated with particles in autumn and winter in the urban area of Guangzhou[J].Environmental Science,2016,37(1):16-21.
[9] Hoffer A,Gelencsér A,Guyon P,et al. Optical properties of humic-like substances(HULIS)in biomass-burning aerosols[J]. Atmospheric Chemistry and Physics,2006,6(11):3563-3570.
[10] Du Z Y,He K B,Cheng Y,et al. A yearlong study of watersoluble organic carbon in Beijing II:Light absorption properties[J]. Atmospheric Environment,2014,89:235-241.
[11] Santos P S M,Otero M,Duarte R M B O,et al. Spectroscopic characterization of dissolved organic matter isolated from rainwater[J]. Chemosphere,2009,74(8):1053-1061.
[12] Santos P S M,Santos E B H,Duarte A C. First spectroscopic study on the structural features of dissolved organic matter isolated from rainwater in different seasons[J]. Science of the Total Environment,2012,426:172-179.
[13] Chen Q C,Miyazaki Y,Kawamura K,et al. Characterization of chromophoric water-soluble Organic matter in urban,forest,and marine aerosols by HR-ToF-AMS analysis and excitation-emission matrix spectroscopy[J]. Environmental Science&Technology,2016,50(19):10351-10360.
[14] Yan G,Kim G. Speciation and sources of brown carbon in precipitation at seoul,Korea:Insights from excitation-emission matrix spectroscopy and carbon isotopic analysis[J].Environmental Science&Technology,2017,51(20):11580-11587.
[15] Fan X J,Song J Z,Peng P A. Comparison of isolation and quantification methods to measure humic-like substances(HULIS)in atmospheric particles[J]. Atmospheric Environment,2012,60:366-374.
[16] Baduel C, Voisin D, Jaffrezo J L. Seasonal variations of concentrations and optical properties of water soluble HULIS collected in urban environments[J]. Atmospheric Chemistry and Physics,2010,10(9):4085-4095.
[17] Fan X J,Song J Z,Peng P A. Temporal variations of the abundance and optical properties of water soluble Humic-Like Substances(HULIS)in PM2. 5at Guangzhou, China[J].Atmospheric Research,2016,172-173:8-15.
[18]梁俭,江韬,魏世强,等.夏、冬季降雨中溶解性有机质(DOM)光谱特征及来源辨析[J].环境科学,2015,36(3):888-897.Liang J,Jiang T,Wei S Q,et al. Absorption and fluorescence characteristics of dissolved organic matter(DOM)in rainwater and sources analysis in summer and winter season[J].Environmental Science,2015,36(3):888-897.
[19] Stedmon C A,Bro R. Characterizing dissolved organic matter fluorescence with parallel factor analysis:a tutorial[J].Limnology and Oceanography:Methods,2008,6(11):572-579.
[20] Matos J T V,Freire S M S C,Duarte R M B O,et al. Natural organic matter in urban aerosols:Comparison between water and alkaline soluble components using excitation-emission matrix fluorescence spectroscopy and multiway data analysis[J].Atmospheric Environment,2015,102:1-10.
[21]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.Huang Z S,Xiu G L,Cai J,et al. Seasonal characterization of water-soluble organic carbon and humic-like substance carbon in atmospheric PM2. 5[J]. Acta Scientiae Circumstantiae,2013,33(10):2664-2670.
[22]谭吉华,段菁春,赵金平,等.广州市灰霾期间大气颗粒物中有机碳和元素碳的粒径分布[J].环境化学,2009,28(2):267-271.
[23] Qiao T,Zhao M F,Xiu G L,et al. Seasonal variations of water soluble composition(WSOC,Hulis and WSIIs)in PM1and its implications on haze pollution in urban Shanghai,China[J].Atmospheric Environment,2015,123:306-314.
[24] Fan X J,Song J Z,Peng P A. Comparative study for separation of atmospheric humic-like substance(HULIS)by ENVI-18,HLB,XAD-8 and DEAE sorbents:elemental composition,FTIR,1H NMR and off-line thermochemolysis with tetramethylammonium hydroxide(TMAH)[J]. Chemosphere,2013,93(9):1710-1719.
[25] Baduel C,Voisin D,Jaffrezo J L. Comparison of analytical methods for Humic Like Substances(HULIS)measurements in atmospheric particles[J]. Atmospheric Chemistry and Physics,2009,9(16):5949-5962.
[26] Baduel C, Monge M E, Voisin D, et al. Oxidation of atmospheric humic like substances by ozone:a kinetic and structural analysis approach[J]. Environmental Science&Technology,2011,45(12):5238-44.
[27] Wong J P S,Nenes A,Weber R J. Changes in light absorptivity of molecular weight separated brown carbon due to photolytic aging[J]. Environmental Science&Technology,2017,51(15):8414-8421.
[28]程玉婷,王格慧,孙涛,等.西安冬季非灰霾天与灰霾天PM2. 5中水溶性有机氮污染特征比较[J].环境科学,2014,35(7):2468-2476.Cheng Y T,Wang G H,Sun T,et al. Characteristics of watersoluble organic nitrogen of PM2. 5in Xi'an during wintertime nonhaze and haze periods[J]. Environmental Science,2014,35(7):2468-2476.
[29]闫才青,郑玫,张远航.大气棕色碳的研究进展与方向[J].环境科学,2014,35(11):4404-4414.Yan C Q, Zheng M, Zhang Y H. Research progress and direction of atmospheric brown carbon[J]. Environmental Science,2014,35(11):4404-4414.
[30]支国瑞,蔡竟,杨俊超,等.棕色碳气溶胶来源、性质、测量与排放估算[J].环境科学研究,2015,28(12):1797-1814.Zhi G R, Cai J, Yang J C, et al. Origin, properties,measurement and emission estimation of brown carbon aerosols[J]. Research of Environmental Sciences,2015,28(12):1797-1814.
[31] Park S S,Yu J. Chemical and light absorption properties of humic-like substances from biomass burning emissions under controlled combustion experiments[J]. Atmospheric Environment,2016,136:114-122.
[32] Yuan J F,Huang X F,Cao L M,et al. Light absorption of brown carbon aerosol in the PRD region of China[J].Atmospheric Chemistry and Physics,2016,16(3):1433-1443.
[33] Han H,Kim G. Significant seasonal change in optical properties by atmospheric humic-like substances(HULIS)in water-soluble organic carbon aerosols[J]. Atmospheric Chemistry and Physics Discussion,2017,doi:10. 5194/acp-2017-554.
[34] Fan X J,Wei S Y,Zhu M B,et al. Molecular characterization of primary humic-like substances in fine smoke particles by thermochemolysis-gas chromatography-mass spectrometry[J].Atmospheric Environment,2018,180:1-10.
[35] Song J Z,Li M J,Jiang B,et al. Molecular characterization of water-soluble humic like substances in smoke particles emitted from combustion of biomass materials and coal using ultrahighresolution electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Environmental Science&Technology,2018,52(5):2575-2585.
[36] Santos G T A D,Santos P S M,Duarte A C. Vanillic and syringic acids from biomass burning:Behaviour during Fentonlike oxidation in atmospheric aqueous phase and in the absence of light[J]. Journal of Hazardous Materials,2016,313:201-208.
[37] Santos P S M,Domingues M R M,Duarte A C. Fenton-like oxidation of small aromatic acids from biomass burning in atmospheric water and in the absence of light:Identification of intermediates and reaction pathways[J]. Chemosphere,2016,154:599-603.