苯水相光氧化反应形成二次有机气溶胶的实验研究
|
摘要
来源于机动车尾气的苯能溶于大气水滴、云雾等水相中并发生水相光氧化反应,在水分蒸发后,产物保留在颗粒相中形成二次有机气溶胶(SOA)粒子.本文采用雾化器将羟基启动苯水相光氧化反应溶液雾化产生气溶胶粒子,通过扩散干燥管除去水蒸气后产生SOA粒子,采用气溶胶激光飞行时间质谱仪进行在线检测,利用紫外可见吸收光谱仪、红外光谱仪和液相色谱串联质谱仪离线测量SOA的化学组分.实验结果表明,激光解吸附质谱中存在醛类(m/z=29(CHO~+)、57(CHOCO~+))、羧酸(m/z=44(COO~+))和苯环(m/z=39(C_3H~+_3)、65(C_5H~-_5))特征裂解碎片峰.SOA粒子的红外光谱图中存在苯环C—H和C=C双键,以及C=O双键、C—O、O—H和C—O—C键的伸缩振动吸收峰,电喷雾电离质谱中存在m/z高达915的离子峰.这表明醛类、羧酸、酚类、芳香醚类产物和酚类产物发生聚合形成的高分子量化合物是SOA粒子的主要化学组分.这为研究人为源挥发性有机化合物水相反应形成SOA的机理提供了实验依据.
Benzene derived from the exhaust of the motor vehicle can dissolve and undergo photooxidation in water droplets, clouds and other aqueous phase.After evaporation of water, the product remains in the particle phase to form secondary organic aerosol(SOA) particles. The atomizer is used to atomize the solution emerged from the OH—initiated aqueous photooxidation of benzene to form aerosol particles, and SOA particles are generated by removing the water vapor through the diffusion drying tube, its chemical composition is on-line detected by aerosol laser time-of-flight mass spectrometer, and off-line measured with ultraviolet-visible absorption spectrometer, infrared spectrometer and liquid chromatography tandem mass spectrometer, respectively. The experimental results shown that the characteristic fragmentation peaks of aldehydes of m/z=29(CHO~+), 57(CHOCO~+), carboxylic acid of m/z=44(COO~+), and benzene ring of m/z=39(C_3H~+_3), 65(C_5H~-_5) were found in laser desorption mass spectra of SOA particles. The infrared spectrum of SOA particles has stretching vibration absorption peaks of C—H and C=C double bonds of benzene ring, C=O double bonds, C—O, O—H and C—O—C bonds. What is more, the highest ion peak of m/z=915 was existed in the electrospray ionization mass spectra of SOA particles. These results indicate that aldehydes, carboxylic acids, phenolic compounds, aromatic ethers, and high molecular weight compounds formed from the polymerization of phenolic products are the major chemical components of SOA particles. These provide experimental basis for studying the formation mechanism of SOA formed from aqueous reaction of anthropogenic volatile organic compounds.
Benzene derived from the exhaust of the motor vehicle can dissolve and undergo photooxidation in water droplets, clouds and other aqueous phase.After evaporation of water, the product remains in the particle phase to form secondary organic aerosol(SOA) particles. The atomizer is used to atomize the solution emerged from the OH—initiated aqueous photooxidation of benzene to form aerosol particles, and SOA particles are generated by removing the water vapor through the diffusion drying tube, its chemical composition is on-line detected by aerosol laser time-of-flight mass spectrometer, and off-line measured with ultraviolet-visible absorption spectrometer, infrared spectrometer and liquid chromatography tandem mass spectrometer, respectively. The experimental results shown that the characteristic fragmentation peaks of aldehydes of m/z=29(CHO~+), 57(CHOCO~+), carboxylic acid of m/z=44(COO~+), and benzene ring of m/z=39(C_3H~+_3), 65(C_5H~-_5) were found in laser desorption mass spectra of SOA particles. The infrared spectrum of SOA particles has stretching vibration absorption peaks of C—H and C=C double bonds of benzene ring, C=O double bonds, C—O, O—H and C—O—C bonds. What is more, the highest ion peak of m/z=915 was existed in the electrospray ionization mass spectra of SOA particles. These results indicate that aldehydes, carboxylic acids, phenolic compounds, aromatic ethers, and high molecular weight compounds formed from the polymerization of phenolic products are the major chemical components of SOA particles. These provide experimental basis for studying the formation mechanism of SOA formed from aqueous reaction of anthropogenic volatile organic compounds.
引文
Ahmed J,Fahmida A,Sohini R C,et al.2018.Prospects and challenges of volatile organic compound (VOC) sensors in human healthcare[J].ACS Sensors,3:1246-1263
Aljawhary D,Zhao R,Lee A K Y,et al.2016.Kinetics,mechanism,and secondary organic aerosol yield of aqueous phase photo-oxidation of α-pinene oxidation products[J].Journal of Physical Chemistry A,120(9):1395-1407
Ao X L,Liu W J.2017.Degradation of sulfamethoxazole by medium pressure UV and oxidants:Peroxymonosulfate,persulfate,and hydrogen peroxide[J].Chemical Engineering Journal,313(1):629-637
曹军骥,李建军.2016.二次有机气溶胶的形成及其毒理效应[J].地球环境学报,7(5):431-441
Carlton A G,Turpin B J,Altieri K E,et al.2007.Atmospheric oxalic acid and SOA production from glyoxal:Results of aqueous photooxidation experiments[J].Atmospheric Environment,41(35):7588-7602
Chang J L,Thompson J E.2010.Characterization of colored products formed during irradiation of aqueous solutions containing H2O2 and phenolic compounds[J].Atmospheric Environment,44(4):541-551
陈天增,葛艳丽,刘永春,等.2018.我国机动车排放VOCs及其大气环境影响[J].环境科学,39(2):478-492
陈文泰,邵敏,袁斌,等.2013.大气中挥发性有机物(VOCs)对二次有机气溶胶(SOA)生成贡献的参数化估算[J].环境科学学报,33(1):163-172
冯状状,黄明强,徐俊,等.2018.羟基启动苯液相光氧化产物的傅里叶变换红外光谱研究[J].红外,39(8):40-45
Haan D O D,Corrigan A L,Smith K W,et al.2009.Secondary organic aerosol-forming reactions of glyoxal with amino acids[J].Environmental Science & Technology,43(8):2818-2824
Haan D O D,Corrigan A L,Tolbert M A,et al.2009.Secondary organic aerosol formation by self-reactions of methylglyoxal and glyoxal in evaporating droplets[J].Environmental Science & Technology,43(21):8184- 8190
Haan D O D,Hawkins L N,Welsh H G,et al.2017.Brown carbon production in ammonium- or amine-containing aerosol particles by reactive uptake of methylglyoxal and photolytic cloud cycling[J].Environmental Science & Technology,51(13):7458-7466
Heath A A,Ehrenhauser F S,Valsaraj K T.2013.Effects of temperature,oxygen level,ionic strength,and pH on the reaction of benzene with hydroxyl radicals in aqueous atmospheric systems[J].Journal of Environmental Chemical Engineering,1(4):822-830
Huang M Q,Hao L Q,Guo X Y,et al.2013.Characterization of secondary organic aerosol particles using aerosol laser time-of-flight mass spectrometer coupled with FCM clustering algorithm[J].Atmospheric Environment,64:85-94
Huang M Q,Lin Y H,Huang X Y,et al.2014.Chemical analysis of aged benzene secondary organic aerosol using aerosol laser time-of-flight mass spectrometer[J].Journal of Atmospheric Chemistry,71(3):213-224
Huang M Q,Xu J,Cai S Y,et al.2018.Characterization of brown carbon constituents of benzene secondary organic aerosol aged with ammonia[J].Journal of Atmospheric Chemistry,75(2):205-218
Kameel F R,Hoffmann M R,Colussi A J.2013.OH radical-initiated chemistry of isoprene in aqueous media.Atmospheric implications[J].Journal of Physical Chemistry A,117(24):5117-5123
Kampf C J,Jakob R,Hoffmann T.2012.Identification and characterization of aging products in the glyoxal/ammonium sulfate system-implications for light-absorbing material in atmospheric aerosols[J].Atmospheric Chemistry and Physics,12(14):6323-6333
Laskin A,Laskin J,Nizkorodov S A.2015.Chemistry of atmospheric brown carbon[J].Chemical Reviews,115(10):4335-4382
Lee A K Y,Zhao R,Gao S S,et al.2011.Aqueous-phase OH oxidation of glyoxal:application of a novel analytical approach employing aerosol mass spectrometry and complementary off-line techniques[J].Journal of Physical Chemistry A,115(38):10517-10526
李红霞,张俊杰,唐桂芬.2000.因子分析-紫外吸光光度法同时测定苯酚甲苯酚和间苯二酚[J].理化检验(化学分册),36(5):193-194+197
李建权,沈成银,王鸿梅,等.2008.质子转移反应质谱动态测量苯系物的亨利常数[J].物理化学学报,24(4):705-708
Liao C H,Gurol M D.1995.Chemical oxidation by photolytic decomposition of hydrogen peroxide[J].Environmental Science and Technology,29(12):3007-3014
Lin P,Laskin J,Nizkorodov S A,et al.2015.Revealing brown carbon chromophores produced in reactions of methylglyoxal with ammonium sulfate[J].Environmental Science & Technology,49(24):14257-14266
Matsumoto K,Matsumoto K,Mizuno R,et al.2010.Volatile organic compounds in ambient aerosols[J].Atmospheric Research,97(1/2):124-128
Mullaugh K M,Hamilton J M,Avery G B,et al.2015.Temporal and spatial variability of trace volatile organic compounds in rain water[J].Chemosphere,134:203-209
祁骞,周学华,王文兴.2014.二次有机气溶胶的水相形成研究[J].化学进展,26(Z1):458-466
Sun Y L,Zhang Q,Anastasio C,et al.2010.Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry[J].Atmospheric Chemical & Physics,10(2):4809-4822
王光辉,熊少祥.2005.有机质谱解析[M].北京:化学化工出版社
Wang L M,Wu R R,Xu C.2013.Atmospheric oxidation mechanism of benzene.Fates of alkoxy radical intermediates and revised mechanism[J].Journal of Physical Chemistry A,117(51):14163-14168
吴瑾光.1994.近代傅里叶变换红外光谱技术及应用(第1版)[M].北京:科学技术文献出版社
徐俊,黄明强,冯状状,等.2018.氨对甲苯二次有机气溶胶形成和化学组分的影响研究[J].环境科学学报,38(8):3243-3251
叶招莲,瞿珍秀,马帅帅,等.2018.气溶胶水相反应生成二次有机气溶胶研究进展[J].环境科学,39(8):3954-3964
曾泳淮.2010.分析化学(仪器分析部分)(第4版)[M].北京:高等教育出版社
Zhang H,Surratt J D,Lin Y H,et al.2011.Effect of relative humidity on SOA formation from isoprene/NO photooxidation:enhancement of 2-methylglyceric acid and its corresponding oligoesters under dry conditions[J].Atmospheric Chemistry Physics,11(13):6411-6424
周欢,冯艳丽,姜知明,等.2016.大气中二羰基化合物及其生成的二次有机气溶胶[J].上海大学学报(自然科学版),22(2):159-171
Aljawhary D,Zhao R,Lee A K Y,et al.2016.Kinetics,mechanism,and secondary organic aerosol yield of aqueous phase photo-oxidation of α-pinene oxidation products[J].Journal of Physical Chemistry A,120(9):1395-1407
Ao X L,Liu W J.2017.Degradation of sulfamethoxazole by medium pressure UV and oxidants:Peroxymonosulfate,persulfate,and hydrogen peroxide[J].Chemical Engineering Journal,313(1):629-637
曹军骥,李建军.2016.二次有机气溶胶的形成及其毒理效应[J].地球环境学报,7(5):431-441
Carlton A G,Turpin B J,Altieri K E,et al.2007.Atmospheric oxalic acid and SOA production from glyoxal:Results of aqueous photooxidation experiments[J].Atmospheric Environment,41(35):7588-7602
Chang J L,Thompson J E.2010.Characterization of colored products formed during irradiation of aqueous solutions containing H2O2 and phenolic compounds[J].Atmospheric Environment,44(4):541-551
陈天增,葛艳丽,刘永春,等.2018.我国机动车排放VOCs及其大气环境影响[J].环境科学,39(2):478-492
陈文泰,邵敏,袁斌,等.2013.大气中挥发性有机物(VOCs)对二次有机气溶胶(SOA)生成贡献的参数化估算[J].环境科学学报,33(1):163-172
冯状状,黄明强,徐俊,等.2018.羟基启动苯液相光氧化产物的傅里叶变换红外光谱研究[J].红外,39(8):40-45
Haan D O D,Corrigan A L,Smith K W,et al.2009.Secondary organic aerosol-forming reactions of glyoxal with amino acids[J].Environmental Science & Technology,43(8):2818-2824
Haan D O D,Corrigan A L,Tolbert M A,et al.2009.Secondary organic aerosol formation by self-reactions of methylglyoxal and glyoxal in evaporating droplets[J].Environmental Science & Technology,43(21):8184- 8190
Haan D O D,Hawkins L N,Welsh H G,et al.2017.Brown carbon production in ammonium- or amine-containing aerosol particles by reactive uptake of methylglyoxal and photolytic cloud cycling[J].Environmental Science & Technology,51(13):7458-7466
Heath A A,Ehrenhauser F S,Valsaraj K T.2013.Effects of temperature,oxygen level,ionic strength,and pH on the reaction of benzene with hydroxyl radicals in aqueous atmospheric systems[J].Journal of Environmental Chemical Engineering,1(4):822-830
Huang M Q,Hao L Q,Guo X Y,et al.2013.Characterization of secondary organic aerosol particles using aerosol laser time-of-flight mass spectrometer coupled with FCM clustering algorithm[J].Atmospheric Environment,64:85-94
Huang M Q,Lin Y H,Huang X Y,et al.2014.Chemical analysis of aged benzene secondary organic aerosol using aerosol laser time-of-flight mass spectrometer[J].Journal of Atmospheric Chemistry,71(3):213-224
Huang M Q,Xu J,Cai S Y,et al.2018.Characterization of brown carbon constituents of benzene secondary organic aerosol aged with ammonia[J].Journal of Atmospheric Chemistry,75(2):205-218
Kameel F R,Hoffmann M R,Colussi A J.2013.OH radical-initiated chemistry of isoprene in aqueous media.Atmospheric implications[J].Journal of Physical Chemistry A,117(24):5117-5123
Kampf C J,Jakob R,Hoffmann T.2012.Identification and characterization of aging products in the glyoxal/ammonium sulfate system-implications for light-absorbing material in atmospheric aerosols[J].Atmospheric Chemistry and Physics,12(14):6323-6333
Laskin A,Laskin J,Nizkorodov S A.2015.Chemistry of atmospheric brown carbon[J].Chemical Reviews,115(10):4335-4382
Lee A K Y,Zhao R,Gao S S,et al.2011.Aqueous-phase OH oxidation of glyoxal:application of a novel analytical approach employing aerosol mass spectrometry and complementary off-line techniques[J].Journal of Physical Chemistry A,115(38):10517-10526
李红霞,张俊杰,唐桂芬.2000.因子分析-紫外吸光光度法同时测定苯酚甲苯酚和间苯二酚[J].理化检验(化学分册),36(5):193-194+197
李建权,沈成银,王鸿梅,等.2008.质子转移反应质谱动态测量苯系物的亨利常数[J].物理化学学报,24(4):705-708
Liao C H,Gurol M D.1995.Chemical oxidation by photolytic decomposition of hydrogen peroxide[J].Environmental Science and Technology,29(12):3007-3014
Lin P,Laskin J,Nizkorodov S A,et al.2015.Revealing brown carbon chromophores produced in reactions of methylglyoxal with ammonium sulfate[J].Environmental Science & Technology,49(24):14257-14266
Matsumoto K,Matsumoto K,Mizuno R,et al.2010.Volatile organic compounds in ambient aerosols[J].Atmospheric Research,97(1/2):124-128
Mullaugh K M,Hamilton J M,Avery G B,et al.2015.Temporal and spatial variability of trace volatile organic compounds in rain water[J].Chemosphere,134:203-209
祁骞,周学华,王文兴.2014.二次有机气溶胶的水相形成研究[J].化学进展,26(Z1):458-466
Sun Y L,Zhang Q,Anastasio C,et al.2010.Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry[J].Atmospheric Chemical & Physics,10(2):4809-4822
王光辉,熊少祥.2005.有机质谱解析[M].北京:化学化工出版社
Wang L M,Wu R R,Xu C.2013.Atmospheric oxidation mechanism of benzene.Fates of alkoxy radical intermediates and revised mechanism[J].Journal of Physical Chemistry A,117(51):14163-14168
吴瑾光.1994.近代傅里叶变换红外光谱技术及应用(第1版)[M].北京:科学技术文献出版社
徐俊,黄明强,冯状状,等.2018.氨对甲苯二次有机气溶胶形成和化学组分的影响研究[J].环境科学学报,38(8):3243-3251
叶招莲,瞿珍秀,马帅帅,等.2018.气溶胶水相反应生成二次有机气溶胶研究进展[J].环境科学,39(8):3954-3964
曾泳淮.2010.分析化学(仪器分析部分)(第4版)[M].北京:高等教育出版社
Zhang H,Surratt J D,Lin Y H,et al.2011.Effect of relative humidity on SOA formation from isoprene/NO photooxidation:enhancement of 2-methylglyceric acid and its corresponding oligoesters under dry conditions[J].Atmospheric Chemistry Physics,11(13):6411-6424
周欢,冯艳丽,姜知明,等.2016.大气中二羰基化合物及其生成的二次有机气溶胶[J].上海大学学报(自然科学版),22(2):159-171
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |