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.     

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（英文）

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0.4mm~1.4mm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.     

用激光解吸附电离法对三甲苯生成二次有机气溶粒子的分析

利用实验室烟雾腔,在不同的实验条件下研究了由羟基启动的三甲苯光氧化反应所产生的二次有机气溶胶,采用激光解吸附技术和气溶胶飞行时间质谱仪测量了产物的化学组分和粒子的粒径分布。结果表明:随着反应物三甲苯浓度的增加,所生成的二次有机气溶胶粒子数量增多;随着反应时间的延长,生成的粒子数目也增加,但是反应到一段时间后,检测到的粒子数目几乎保持不变;光照强度的增加有利于二次有机气溶胶的生成;通过对产物的化学成分分析,说明了在二次有机光氧化产物中粒子相产物主要是芳香的环保留产物、非芳香环保留产物和环断裂产物。     

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.     

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。     

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。     

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.     

差分吸收光谱技术监测大气气溶胶粒谱分布

介绍了利用双光路差分吸收光谱(DOAS)技术监测大气气溶胶并反演其粒谱分布的新方法.该方法解决了DOAS技术中光源绝对光强难以测量的难题，去除了由于光源自身波动造成的影响，在250—650nm范围内成功的反演出气溶胶的消光系数以及0.1—1.75μm谱段的粒谱分布.通过与光学粒子计数器的对比实验证实该方法的可行性. 关键词： 差分吸收光谱 双光路 气溶胶 粒谱分布     

多波段激光雷达颗粒物质量浓度探测方法

为了获得大气颗粒物的质量浓度廓线，提出一种基于多波段激光雷达回波信号的大气气溶胶消光系数与颗粒物质量消光效率相结合的新型算法。该方法利用覆盖紫外到近红外波段的激光雷达作为遥感探测工具，获取气溶胶的消光与后向散射系数，反演得到气溶胶粒子谱分布；同时，根据米散射理论算出气溶胶消光效率，结合粒子谱分布，提出颗粒物质量消光效率模型，从而建立基于消光系数与质量消光效率相结合的反演颗粒物质量浓度的新型数学模型与算法。采用该算法对两组不同天气条件多波段激光雷达实测数据进行反演，并与地表采用的颗粒物浓度对比，证明该方法的可行性，为实现颗粒物质量浓度空间分布的探测提供科学依据和方法论。     

基于宽范围粒径谱仪的气溶胶探测方法

通过改变基于宽范围粒径谱仪的温度控制方法,研究温度变化对气溶胶浓度的影响和作用.本文首先对宽范围粒径谱仪进样系统温度控制方法进行改进,即采用钽管加热器及不加热切换的温度控制方法来改变宽范围粒径谱仪进样部分温度,使用改进后的系统测量室内外大气气溶胶,对不同温度下大气气溶胶的浓度分布情况进行讨论与分析.结果表明室外粒子数浓度分布的峰值与室内粒子浓度分布的峰值相比,室内空气中粒子数浓度峰值明显要小,即室外大气中的粒径大的粒子更多.证实了宽范围粒径谱仪适用于大气气溶胶的检测,在环境检测中有广泛的应用前景.     

Particle Size Distributions Based on a Multipopulation Genetic Algorithm Used in Multiwavelength Lidar

Aerosols influence the radiation budget of the Earth’s atmospheric system. Aerosol particle size distribution is one of the major parameters used for characterizing aerosol influence on radiative forcing. The optical and microphysical properties of aerosol particles over Yinchuan, China, were measured with a multiwavelength lidar developed at Beifang University of Nationalities using backscatter and extinction coefficients at wavelengths of 1064, 532, and 355 nm. These data were used to retrieve particle size distributions. Given the disadvantages of the traditional regularization method, the innovative multipopulation genetic algorithm (MPGA) was used to retrieve the particle size distribution from the lidar data. To verify the feasibility of using the MPGA on multiwavelength lidar data, experiments were carried out under different atmospheric conditions, including a background sunny day, a cloudy day, and a foggy day. The particle size distributions obtained from the multiwavelength lidar data were compared with results retrieved from direct irradiance data from a sun photometer. Results showed that the MPGA is suitable for retrieving particle size distributions from multiwavelength lidar data.     

The Effect of Boundary Conditions on Gas-phase Synthesised Silver Nanoparticles

We have prepared spherical non-agglomerated silver nanoparticles by an evaporation–condensation–dilution/cooling technique. Silver was evaporated from a crucible in a tubular flow reactor. A porous tube diluter was used to quench the carrier gas at the outlet of the reactor to enhance the formation of small particles and to suppress agglomeration and other particle growth mechanisms. The number size distribution of the prepared particles was measured with a differential mobility analyser–condensation nucleus counter combination and the size and the shape of the particles were analysed with transmission electron microscope. The system was modelled using a sectional aerosol dynamics computer code to estimate the importance of different aerosol processes. In all conditions the particles obtained were non-agglomerated and spherical. The mean particle diameter varied from 4 to 10-nm depending on boundary conditions. From the modelling studies it can be concluded that the nucleation rate is the most important parameter controlling the final particle size.     

Inverse problem for particle size distributions of atmospheric aerosols using stochastic particle swarm optimization

As a part of resolving optical properties in atmosphere radiative transfer calculations, this paper focuses on obtaining aerosol optical thicknesses (AOTs) in the visible and near infrared wave band through indirect method by gleaning the values of aerosol particle size distribution parameters. Although various inverse techniques have been applied to obtain values for these parameters, we choose a stochastic particle swarm optimization (SPSO) algorithm to perform an inverse calculation. Computational performances of different inverse methods are investigated and the influence of swarm size on the inverse problem of computation particles is examined. Next, computational efficiencies of various particle size distributions and the influences of the measured errors on computational accuracy are compared. Finally, we recover particle size distributions for atmospheric aerosols over Beijing using the measured AOT data (at wavelengths λ=0.400, 0.690, 0.870, and 1.020 μm) obtained from AERONET at different times and then calculate other AOT values for this band based on the inverse results. With calculations agreeing with measured data, the SPSO algorithm shows good practicability.     

Research on bimodal particle extinction coefficient during Brownian coagulation and condensation for the entire particle size regime

The extinction coefficient of atmospheric aerosol particles influences the earth’s radiation balance directly or indirectly, and it can be determined by the scattering and absorption characteristics of aerosol particles. The problem of estimating the change of extinction coefficient due to time evolution of bimodal particle size distribution is studied, and two improved methods for calculating the Brownian coagulation coefficient and the condensation growth rate are proposed, respectively. Through the improved method based on Otto kernel, the Brownian coagulation coefficient can be expressed simply in powers of particle volume for the entire particle size regime based on the fitted polynomials of the mean enhancement function. Meanwhile, the improved method based on Fuchs–Sutugin kernel is developed to obtain the condensation growth rate for the entire particle size regime. And then, the change of the overall extinction coefficient of bimodal distributions undergoing Brownian coagulation and condensation can be estimated comprehensively for the entire particle size regime. Simulation experiments indicate that the extinction coefficients obtained with the improved methods coincide fairly well with the true values, which provide a simple, reliable, and general method to estimate the change of extinction coefficient for the entire particle size regime during the bimodal particle dynamic processes.     

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.     

大气气溶胶单粒子粒径和化学成分的LDI测量

介绍了当前应用较为广泛的大气气溶胶单粒子粒径与化学成分实时在线测量技术－激光解吸附电离（LDI）飞行时间质谱技术的原理和在气溶胶单粒子化学成分测量领域的应用。此外，还对气溶胶单粒子进样系统和气溶胶单粒子粒径的测量方法作了详细阐述。