OH自由基启动甲苯光氧化产物的质谱

在烟雾腔系统内,辐照甲苯/CH₃ONO/NO/空气混合系统,启动甲苯的光氧化反应. 利用同步辐射光电离质谱在线检测甲苯光氧化气相产物,并用气溶胶飞行时间质谱实时测量甲苯光氧化形成的二次有机气溶胶粒子. 实验结果表明,呋喃、甲基乙二醛,2-甲基呋喃、苯甲醛、甲基酚和苯甲酸是甲苯光氧化反应形成的气体相和粒子相的主要产物,而乙二醛、2-羟基-3-氧代-丁醛、硝基甲苯和甲基硝基酚只存在粒子相.     

有机种子对异戊二烯光氧化反应形成二次有机气溶胶的粒谱演化和形成速率的影响

基于室内烟雾箱实验平台,研究了在有机种子气溶胶下,来自OH启动异戊二烯光氧化反应形成的二次有机气溶胶的动力学. 探究了二次有机气溶胶的粒谱分布分别与来自室内大气中痕量碳氢化合物光氧化反应产生的种子颗粒物浓度以及前体物异戊二烯浓度的依赖关系. 研究结果表明在高浓度种子气溶胶和低浓度异戊二烯条件下(对应于典型城市大气条件),光化学反应形成的二次有机产物凝聚到种子颗粒物表面而造成的颗粒物增长起主导作用;而在低浓度种子气溶胶和相对高浓度异戊二烯条件下(对应于典型偏远地区大气条件),二次有机气溶胶粒谱分布出现双模式结构,分别对应于来自均相成核的新粒子生成和二次有机产物在种子颗粒物上的凝聚增长. 此外,还研究了有机种子颗粒物浓度对二次有机气溶胶形成的影响,评估了在不同种子浓度下二次有机气溶胶粒谱分布的演化和相应新粒子的形成速率.     

基于模糊聚类算法的苯系物二次有机气溶胶质谱数据分析

OH自由基启动苯系物光氧化形成的二次有机气溶胶能够影响气候变化,降低大气能见度,危害人类健康。我们实验室自行研制的气溶胶飞行时间质谱仪能够用于二次有机气溶胶的实时检测研究。该仪器在检测过程中产生大量的实验数据,对这些数据快速、自动处理并提取有价值的信息是整机系统的关键之一。本文介绍模糊聚类算法在苯系物二次有机气溶胶单粒子聚类分析中的成功运用。利用该算法对OH自由基启动1,3,5-三甲苯光氧化形成的二次有机气溶胶单粒子质谱数据进行了聚类分析,在得到的五个聚类中包含了芳香醛、酚类化合物、硝基酚和羧酸等重要的光氧化产物,为研究苯系物光氧化机理提供了新的信息。     

用于大气化学反应和二次有机气溶胶研究的实验室烟雾箱系统的搭建、测试与初步实验

为了从本质上认识和了解大气氧化反应进程以及二次有机气溶胶的形成机制,设计并搭建了一套实验室模拟烟雾箱系统．将质子转移反应质谱、同步辐射光电离质谱及气溶胶激光飞行时间质谱等特色质谱检测系统与烟雾箱结合,用于大气氧化反应气相和粒子相产物的定量与定性分析．通过一系列表征实验获得了该系统的基本参数,如烟雾箱内温度和光强特征,气体化合物和颗粒物的壁损耗速率,零空气的背景反应性及实验结果的可重复性．臭氧氧化α-蒎烯定量化实验和OH启动异戊二烯光氧化反应的定性检测结果进一步表明了该系统能够满足大气化学反应过程中气相和粒子相化学成分的定性分析及二次有机气溶胶的定量化研究的需要.     

激光解吸电离技术在线测量苯水相二次有机气溶胶

利用气溶胶激光飞行时间质谱仪激光解吸电离技术开展了苯水相二次有机气溶胶在线测量研究。实验结果表明,苯水相光氧化反应形成的二次有机气溶胶粒子粒径小于1.0μm,激光解吸电离质谱中存在醛类m/z 29(CHO~+)、57(CHOCO~+),羧酸m/z 44(COO~+),苯环m/z 77(C_6H~+_5)、65(C_5H~+_5)和酚类化合物m/z 93(C_6H_5O~+)特征裂解碎片峰。醛类、羧酸和酚类化合物是苯水相SOA粒子的化学组分,各类型组分含量大小关系为:醛类化合羧酸酚类化合物。气溶胶激光飞行时间质谱仪激光解吸电离技术能够用于水相SOA粒子化学组分的在线测量,可用于水相SOA形成机理和过程的研究。     

二苯乙烯在CdS胶体界面和醇溶液中光氧化反应的ESR研究

采用ＥＳＲ方法研究了二苯乙烯在硫化镉超微纳米粒子界面光氧化过程产生的中间体及转化机理，并与均相直接光氧化和在甲基紫精存在下的光氧化进行了比较。结果表明，二苯乙烯的界面光氧化经历了超氧阴离子基和二苯乙烯正离子基的生成过程而且在ＣＤＳ胶粒表面有Ｈ原子的生成；羟基在Ｈ原子产生过程中起着重要的作用。     

孔隙率对气溶胶凝聚粒子光学特性的影响

采用Monte-Carlo方法,对气溶胶凝聚粒子进行了模拟,讨论了凝聚粒子的孔隙特性,分析了空间结构、原始粒子数目对凝聚粒子孔隙率和等效折射率的影响。结合物质的电结构,将气溶胶凝聚粒子离散为一系列偶极子,利用离散偶极子近似方法,数值计算了不同孔隙率气溶胶凝聚粒子的散射、吸收和消光截面各种取向的统计平均值。结果表明,气溶胶凝聚粒子的孔隙率明显取决于其空间形状和所含原始微粒的数目;气溶胶凝聚粒子的等效折射率、吸收、散射和消光截面则随孔隙率的增加而减小。研究结果可为全面理解气溶胶粒子光学特性提供参考;也可为某些涂层材料光学性能的改变提供参考,通过改变涂层材料中凝聚粒子的孔隙率来改变涂层材料的等效折射率,进而改变涂层材料对光的散射和吸收。     

气溶胶凝聚粒子散射特性的数值计算

利用Cluster-cluster aggregation (CCA)模型,模拟了由相同数目球形原始微粒凝聚而成的四种随机取向气溶胶凝聚粒子.根据物质的电结构,将气溶胶凝聚粒子离散为一系列偶极子,结合离散偶极子近似方法,在获得每一个偶极子的电偶极矩之后,数值计算了气溶胶凝聚粒子散射强度的角分布,并分析了散射强度随入射光入射角度和气溶胶凝聚粒子尺寸参数变化的规律.结果显示:当散射角较小时,气溶胶凝聚粒子取向和入射光的入射角度对散射强度影响不大,当散射角增大时,散射强度则明显依赖于气溶胶凝聚粒子取向和入射光的入射角度;对于不同尺寸参数的气溶胶凝聚粒子,在同一角度入射情况下,随尺寸参数的增加,气溶胶凝聚粒子的散射主要集中于前向散射.     

气溶胶凝聚粒子散射特性的数值计算

利用Cluster-cluster aggregation (CCA)模型,模拟了由相同数目球形原始微粒凝聚而成的四种随机取向气溶胶凝聚粒子．根据物质的电结构,将气溶胶凝聚粒子离散为一系列偶极子,结合离散偶极子近似方法,在获得每一个偶极子的电偶极矩之后,数值计算了气溶胶凝聚粒子散射强度的角分布,并分析了散射强度随入射光入射角度和气溶胶凝聚粒子尺寸参数变化的规律．结果显示：当散射角较小时,气溶胶凝聚粒子取向和入射光的入射角度对散射强度影响不大,当散射角增大时,散射强度则明显依赖于气溶胶凝聚粒子取向和入射光的入射角度;对于不同尺寸参数的气溶胶凝聚粒子,在同一角度入射情况下,随尺寸参数的增加,气溶胶凝聚粒子的散射主要集中于前向散射．     

影响异戊二烯大气光解形成二次有机气溶胶的环境因素研究

通过自制的烟雾腔系统研究羟基启动的异戊二烯光解形成二次有机气溶胶(SOA)过程中环境因素的影响.使用气溶胶粒径光谱仪测量了SOA的粒径分布,通过光解实验研究了光照时间、反应物浓度以及CH3ONO浓度对异戊二烯光解形成SOA的影响.结果表明,异戊二烯光解形成的SOA空气动力学直径在0.4 mm～1.4 mm之间,这些粒子的直径小于2.5μm的微细粒子很容易沉积在人体肺泡内,对人体健康产生很大危害;不管是SOA粒子的粒子数浓度还是质量数浓度都随着反应时间的增长、光照强度的增强和反应物浓度的增加而增加.该研究为大气颗粒物排放源的外场测量提供了非常有用的信息.     

The Formation of Carbon in Combustion and how to Quantify the Impact on Human Health

We summarize our current research on combustion aerosols. First, sampling devices for the analyses of flame gases are described. The flame gas samples are investigated by mass spectroscopy and by standard aerosol techniques. Time-of-flight mass spectroscopy is well suited to study formation and growth of soot precursor molecules. Fullerenes can also be seen in some mass spectra of flame gases. Presumably, the fullerenes are evaporated from small soot particles in the mass spectrometer by the ionizing laser. Size spectra of soot particles from the flame are presented. The flame is optionally seeded with palladium aerosol to demonstrate that the particle size distribution is not altered during the sampling procedure. It is found that soot particles are already present low in the flame where large molecules are absent.Photoemission is applied to study surface properties of soot particles from the flame. It is shown that the surface of the particles is covered with polycyclic aromatic hydrocarbons (PAH). The PAH can be removed by heating and the properties of the carbon core are revealed. One can thereby distinguish a soot growth from a soot burnout region in the flame. Time-resolved desorption experiments of perylene (a PAH) from model aerosol particles are presented. It is shown that they follow a first order rate law. The photoelectric PAH sensor is introduced as a personal air quality monitor. The danger from inhaling combustion aerosol can be expressed in units of standard cigarettes.     

The effect of an external DC electric field on bipolar charged aerosol agglomeration

A direct-current (DC) electric field was exerted in a bench-scale electrostatic precipitator (ESP) to induce the agglomeration of bipolar charged aerosol particles. The test aerosol particles were generated from water with an atomizer and their average diameter was 7.71 μm. A phase doppler anemometer (PDA) was used to measure the size distribution and the number concentration of the particles. Systematic experiments were conducted to investigate the agglomeration efficiency of the system. The percentage decrease in number of sub-micron sized particles was found to be about 10.7%.     

Catalytic behavior of nickel nanoparticles: gasborne vs. supported state

To study the pure catalytic activity of metallic nanoparticles, the formation of methane on gasborne Ni nanoparticles, so called aerosol catalysis experiments, were performed. Beside effects typical for the methanation such as poisoning of the particle surface at temperatures above 385°C, the maximum of the catalytic activity was observed for Ni particles of about 14 nm, i.e. in a size range, which is quite uncommon for typical nanoeffects of metallic particles. To clarify, which catalytic phenomena are related to the aerosol state, the same reaction was performed on supported Ni nanoparticles, which were also generated and conditioned in the gas phase and deposited on a SiO₂ surface by thermophoresis. For these supported particles, the same reaction conditions were established as before for the gasborne Ni nanoparticles. However, differences in the mass transport characteristics of educt and product molecules to the particles were encountered and led to lower overall reaction rates. While qualitatively poisoning kinetics and activation energies agreed for both cases, significant differences were observed for the size dependence of the catalytic activity and for the sintering kinetics. The observed shift of the optimum size for the methanation from 14 nm (aerosol) to 25 nm (on support) can be explained by different adsorption enthalpies of the educt gases on aerosol and supported Ni nanoparticles, respectively.     

Vacuum Ultraviolet Photoionization Mass Spectra of Typical Organics Contained in Ambient Aerosols

This paper reports an investigation on typical organics contained in ambient aerosols with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The VUV-ATOFMS utilizes a vacuum ultraviolet krypton lamp as an ionization source. The single- and multi-constituent particles generated with typical atmospheric organics (n-eicosane, n-triacontane, 1-pentadecanol, 1-eicosanol, hexanoic acid, decanoic acid, heptadecanoic acid, oleic acid, succinic acid, pyrene, vanillin, benzoic acid, terephthalic acid, and D-galactose) are analyzed with VUV-ATOFMS. The time-of-flight mass spectra of all organic particles are obtained except hexanoic acid. The mass spectra reveal that the detection efficiencies for a certain compound contained in multi-constituent and single-constituent particles are different. These discrepancies may result from the different evaporation dynamics of aerosols in both atomization and vaporization processes. The pyrene has the strongest signal intensity in single- or multi-constituent aerosols, indicating that the VUV-ATOFMS performs well in detecting polycyclic aromatic hydrocarbons. These experimental results present a view on the VUV-photoionization mass spectra of the 14 typical organics contained in ambient aerosols.     

Novel optical techniques for measurements of light extinction,scattering and absorption by single aerosol particles

Aerosol particles play important roles in a broad range of scientific disciplines, from atmospheric chemistry and physics, to the delivery of fuels for combustion and drugs to the lungs, and extending to industrial processes such as spray drying. Measurements of the light extinction, scattering and absorption by ensembles of aerosol particles can be used to non‐intrusively characterise aerosol particle samples. However, such measurements often lead to ambiguity in interpreting the properties and processes occurring on individual particles. In this review, recent developments in the use of laser based techniques to isolate and manipulate single particles and to characterise them will be highlighted. In particular, the use of cavity ring down spectroscopy, Bessel beams and optical tweezers for investigating light extinction, scattering and absorption, respectively, will be considered. The prospects for using optical techniques to interrogate the fundamental processes occurring in aerosol at the single particle level are discussed.     

双光路DOAS系统获取大气颗粒物粒谱分布方法研究

当前大气复合污染日趋严重,造成大气氧化性增强,气体向颗粒物的转化加快。大气颗粒物粒径大小及谱分布决定其在大气中的行为,以差分吸收光谱法（DOAS）为基础,结合双光路设计技术,开展实时、在线、获取近地面大气气溶胶颗粒物的粒谱分布的光谱方法研究。首先构建低噪声性能稳定的宽带氙弧灯为光源的双光路差分吸收光谱系统,基于干净天气条件下大气的能见度数据对系统进行校准,通过两个不同光路获得的光谱信号强度之比获取近地面紫外-近红外波段的大气总宽波段消光系数。基于宽波段消光系数,在去除瑞利散射以及气体吸收对消光系数的影响后,解析出气溶胶颗粒物的消光系数。基于核函数准则,利用均匀球型粒子的电磁场Mie理论来反演气溶胶物理特性,获得气溶胶粒子在该测量谱段的体积谱分布,利用体积谱与数密度谱的关系,反演出气溶胶粒子的数密度谱分布。开展利用直方图方法来表现颗粒物的粒谱分布方法研究,首先将DOAS测量波段近似等分为若干谱段,利用谱段处平均值,获取气溶胶粒谱直方分布图。最后把该系统和方法应用于外场实验,获得了气溶胶颗粒物在300～650 nm范围内的消光系数,将测量波段等分为11个谱段,反演了颗粒物的在0.1～1.25 μm粒径范围的数密度谱分布。该研究为整治我国灰霾天气,研究大气气相/粒子非均相化学反应提供科学依据。同时将推动DOAS技术的进一步发展和应用。