Modeling of soot aggregate formation and size distribution in a laminar ethylene/air coflow diffusion flame with detailed PAH chemistry and an advanced sectional aerosol dynamics model

Soot aggregate formation and size distribution in a laminar ethylene/air coflow diffusion flame is modeled with a PAH-based soot model and an advanced sectional aerosol dynamics model. The mass range of solid soot phase is divided into 35 discrete sections and two variables are solved for in each section. The coagulation kernel of soot aggregates is calculated for the entire Knudsen number regime. Radiation from gaseous species and soot are calculated by a discrete-ordinate method with a statistical narrow-band correlated-k based band model. The discretized sectional soot equations are solved simultaneously to ensure convergence. Parallel computation with the domain decomposition method is used to save computational time. The flame temperature, soot volume fraction, primary particle size and number density are well reproduced. The number of primary particles per aggregate is overpredicted. This discrepancy is presumably associated with the unitary coagulation efficiency assumption in the current sectional model. Along the maximum soot volume fraction pathline, the number-based and mass-based aggregate size distribution functions are found to evolve from unimodal to bimodal and finally to unimodal again. The different shapes of these two aggregate size distribution functions indicate that the total number and mass of aggregates are dominated by aggregates of different sizes. The PAH-soot condensation efficiency γ is found to have a small effect on soot formation when γ is larger than 0.5. However, the soot level and primary particle number density are significantly overpredicted if the PAH-soot condensation process is neglected. Generally, larger γ predicts lower soot level and primary particle number density. Further study on soot aggregate coagulation efficiency should be pursued and more experimental data on soot aggregate structure and size distribution are needed for improving the current sectional soot model and for better understanding the complex soot aggregation phenomenon.     

对利用动态光散射法测量颗粒粒径和液体黏度的改进

光散射技术通过测量悬浮液中布朗运动颗粒的平移扩散系数,得到颗粒流体力学直径或液体黏度.本文由单参数模型入手,建立了低颗粒浓度下,单颗粒平移扩散系数与颗粒集体平移扩散系数和颗粒浓度之间的线性依存关系并将其引入光散射法中,从而对现有的测量方法进行了改进.改进后的测量方法可实现纳米尺度球型颗粒标称直径的测量和液体黏度的绝对法测量.以聚苯乙烯颗粒+水和二氧化硅颗粒+乙醇两个分散系为参考样本,通过实验,验证了改进后方法的可行性.此外,还针对上述两个分散系,实验探讨了温度和颗粒浓度对颗粒集体平移扩散系数的影响规律,发现聚苯乙烯颗粒+水分散系中,颗粒间相互作用表现为引力;二氧化硅颗粒+乙醇分散系中,颗粒间相互作用表现为斥力.讨论了颗粒集体平移扩散系数随颗粒浓度变化规律与第二渗透维里系数的关系.     

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。     

Anomalous diffraction approximation method for retrieval of spherical and spheroidal particle size distributions in total light scattering

Using total light scattering technique to measure the particle size distribution has advantages of simplicity in measurement principle and convenience in the optical arrangement. However, the calculation of extinction efficiency based on Mie theory for a spherical particle is expensive in both time and resources. Thus, a simple but accurate approximation formula for the exact extinction efficiency may be very desirable. The accuracy and limitations of using the anomalous diffraction approximation (ADA) method for calculating the extinction efficiency of a spherical particle are investigated. Meanwhile, the monomodal and bimodal particle size distributions of spherical particles are retrieved using the genetic algorithm in the dependent model. Furthermore, the spheroidal model in the retrieval of non-spherical particle size distribution is also discussed, which verifies the non-sphericity has a significant effect on the retrieval of particle size distribution compared with the assumed homogeneous isotropic sphere. Both numerical computer simulations and experimental results illustrate that the ADA can be successfully applied to retrieve the particle size distributions for spherical and spheroidal particles with high stability even in the presence of random noise. The method has advantages of simplicity, rapidity, and suitability for in-line particle size measurement.     

Weighted Flow Algorithms (WFA) for stochastic particle coagulation

Stochastic particle-resolved methods are a useful way to compute the time evolution of the multi-dimensional size distribution of atmospheric aerosol particles. An effective approach to improve the efficiency of such models is the use of weighted computational particles. Here we introduce particle weighting functions that are power laws in particle size to the recently-developed particle-resolved model PartMC-MOSAIC and present the mathematical formalism of these Weighted Flow Algorithms (WFA) for particle coagulation and growth. We apply this to an urban plume scenario that simulates a particle population undergoing emission of different particle types, dilution, coagulation and aerosol chemistry along a Lagrangian trajectory. We quantify the performance of the Weighted Flow Algorithm for number and mass-based quantities of relevance for atmospheric sciences applications.     

The verification of the Taylor-expansion moment method for the nanoparticle coagulation in the entire size regime due to Brownian motion

The closure of moment equations for nanoparticle coagulation due to Brownian motion in the entire size regime is performed using a newly proposed method of moments. The equations in the free molecular size regime and the continuum plus near-continuum regime are derived separately in which the fractal moments are approximated by three-order Taylor-expansion series. The moment equations for coagulation in the entire size regime are achieved by the harmonic mean solution and the Dahneke??s solution. The results produced by the quadrature method of moments (QMOM), the Pratsinis??s log-normal moment method (PMM), the sectional method (SM), and the newly derived Taylor-expansion moment method (TEMOM) are presented and compared in accuracy and efficiency. The TEMOM method with Dahneke??s solution produces the most accurate results with a high efficiency than other existing moment models in the entire size regime, and thus it is recommended to be used in the following studies on nanoparticle dynamics due to Brownian motion.     

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.     

Surface deposition and coagulation efficiency of combustion generated nanoparticles in the size range from 1 to 10 nm

The size distribution of the nanoparticles formed in premixed ethylene–air flames and collected thermophoretically on mica cleaved substrates is obtained by atomic force microscopy (AFM). The distribution function extends from 1 to about 5 nm in non-sooting flames and in the soot pre-inception region of the richer flames, while it becomes bimodal and larger particles are formed in the soot inception region of the slightly sooting flames. The distribution is compared with the size distribution of nano-sized organic carbon (NOC) and soot particles, obtained by “in situ” multi-wavelength extinction and light scattering methods. The deposition efficiency is estimated from the differences between these two size distribution functions as a function of the equivalent diameter of the nanoparticles. Furthermore, the coagulation coefficient of particles in flame is obtained from the temporal evolution of the number concentration of the nanoparticles inside the flames. NOC particles, which are rapidly produced in locally rich combustion regions, have peculiar properties since their sticking coefficient both for coagulation and adhesion result to be orders of magnitudes lower than that expected by larger aerosols, like soot particles. The experimental results are interpreted by modelling the van der Waals interactions of the nanoparticles in terms of Lennard-Jones potentials and in the framework of the gas kinetic theory. The estimated adhesion and coagulation efficiencies are in good agreement with those calculated from AFM and optical data. The very low efficiency values observed for the smaller particles could be ascribed to the high energy of these particles due to their Brownian motion, which causes thermal rebound effects prevailing over adhesion mechanisms due to van der Waals forces.     

自由分子区布朗凝并作用下的颗粒尺寸分布变化

对于燃烧过程中生成的亚微米颗粒,其一次颗粒的长大过程主要是通过碰撞凝并实现的。本文通过对颗粒的初始分布作出一个合理的正态对数分布的假设,运用矩方法(Moment Method)研究了自由分子区的颗粒在布朗碰撞作用下的颗粒尺寸分布的变化情况。所得到的长时间碰撞凝并结果符合布朗碰撞凝并过程的自保持特性。数值结果还表明,颗粒初始的宽粒径分布会显著提高粒子云的在凝并初期的凝并速率和生成粒子的平均直径,且最终生成的粒子尺寸都是宽分布的。这说明在预报微细颗粒的迁移和长大过程中有必要考虑粒子的宽分布特性。     

水云增长过程中的云滴谱及散射特性分析

基于大气物理学研究了水云云滴增长过程中的粒谱及散射特性.研究结果表明,凝结增长使粒谱半高宽和有效半径不断增加,碰并增长使粒谱出现多峰分布,有效半径增加.在凝结增长和碰并增长共同作用下,有效半径的平均增长速率为8 nm/s.凝结增长和碰并增长单独作用下,消光系数和散射系数随时间呈线性变化.在二者共同作用下,除3.2 mm波长外,消光系数和散射系数随时间呈指数增长;1.064, 2.2, 3.7, 12和22μm波长的不对称因子逐渐趋于稳定,200μm的不对称因子呈指数增长,3.2 mm的不对称因子基本保持不变;1.064和2.2μm波长的雷达比在20 sr附近波动,3.7μm波长的雷达比呈大幅振荡.云滴增长过程中,水云在1.064, 2.2和3.7μm波长的单次散射反照率逐渐降低,在12μm, 22μm, 200μm和3.2 mm波长的单次散射反照率逐渐增加,波长指数的绝对值逐渐减小.研究结果可为天气预报、地气辐射平衡研究和遥感数据校正提供重要的参考.     

Evidence for particle size–shape correlations in the optical properties of silicate clay aerosol

Accurate modeling of the optical properties of atmospheric mineral dust is important for climate modeling calculations and remote sensing data retrievals. Atmospheric mineral dust in the accumulation mode size range is often rich in silicate clays including kaolinite and illite. This is important because dust optical properties depend on particle shape, and fundamental clay particles are known to consist of very thin flakes.In this combined laboratory and modeling study, we investigate the optical properties (IR extinction and visible light scattering) of two samples of silicate clay dust aerosol, kaolinite and illite. Particle size distributions are measured simultaneously with the optical properties. T-Matrix theory based simulations using a spheroidal particle approximation are compared with experimental data. We find that the full range of visible scattering and polarimetry data, and IR extinction profiles are not well fit by assuming a single size–shape distribution for the aerosol. In contrast, a simple bimodal distribution model that treats small particles (fundamental clay flakes) in the distribution as highly eccentric oblate spheroids with axial ratio parameters ≥5, but approximates larger particles by a more moderate shape distribution with axial ratio parameters <3, gives better agreement with the full range of experimental data. These conclusions are consistent with mineralogical data on the dimensions of fundamental clay particles.     

空间垂直方向气溶胶消光特性的研究

在已知大气气溶胶折射率和气溶胶谱分布的基础上,对空间垂直方向的气溶胶消光特性进行了研究。文章利用Mie散射理论计算讨论了气溶胶的消光、散射、吸收系数随各参数的变化,并在MATLAB中对变化情况进行了仿真。结果表明,粒子半径与入射波长大小相近时气溶胶的消光最强,并且随着能见度的增大,气溶胶衰减系数减小。这些结论可以为红外辐射的大气衰减计算和分析提供依据。     

Iteration method for the inversion of simulated multiwavelength lidar signals to determine aerosol size distribution

A new method is proposed to derive the size distribution of aerosol from the simulated multiwavelength lidar extinction coefficients. The basis for this iteration is to consider the extinction efficiency factor of particles as a set of weighting function covering the entire radius region of a distribution. The weighting functions are calculated exactly from Mie theory. This method extends the inversion region by subtracting some extinction coefficient. The radius range of simulated size distribution is 0.1－10.0μm, the inversion radius range is 0.1－2.0μm, but the inverted size distributions are in good agreement with the simulated one.     

Influence of polydisperse distributions of both primary particle and aggregate size on soot temperature in low-fluence LII

An improved aggregate-based low-fluence laser-induced incandescence (LII) model has been developed. The shielding effect in heat conduction between aggregated soot particles and the surrounding gas was modeled using the concept of the equivalent heat transfer sphere. The diameter of such an equivalent sphere was determined from direct simulation Monte Carlo calculations in the free molecular regime as functions of the aggregate size and the thermal accommodation coefficient of soot. Both the primary soot particle diameter and the aggregate size distributions are assumed to be lognormal. The effective temperature of a soot particle ensemble containing different primary particle diameters and aggregate sizes in the laser probe volume was calculated based on the ratio of the total thermal radiation intensities of soot particles at 400 and 780 nm to simulate the experimentally measured soot particle temperature using two-color optical pyrometry. The effect of primary particle diameter polydispersity is in general important and should be considered. The effect of aggregate size polydispersity is relatively unimportant when the heat conduction between the primary particles and the surrounding gas takes place in the free-molecular regime; however, it starts to become important when the heat conduction process occurs in the near transition regime. The model developed in this study was also applied to the re-determination of the thermal accommodation coefficient of soot in an atmospheric pressure laminar ethylene diffusion flame. PACS 44.05.+e; 61.46.Df; 65.80.+n     

模拟颗粒凝并过程的快速Monte Carlo方法

对常规异权值Monte Carlo(MC)方法进行改进,基于强核函数思想,通过颗粒群单重遍历即可求得强核函数最大值,采用接受-拒绝法随机搜寻凝并对,并利用搜寻过程中拒绝和接受的所有凝并对的信息来估计凝并事件的等待时间(时间步长),从而避免颗粒群的双重遍历,以提高MC的效率.对典型工况的模拟结果显示该快速方法计算代价仅为O(N_s),能够显著提高计算效率,同时保持足够的计算精度,较好地协调计算代价与计算精度之间的矛盾.     

Brownian dynamics simulations of a cubic haematite particle suspension with a more effective treatment of steric layer interactions

We have proposed a new repulsive layer model for describing the interaction between steric layers of coated cubic particles. This approach is an effective technique applicable to particle-based simulations such as a Brownian dynamics simulation of a suspension composed of cubic particles. 3D Brownian dynamics simulations employing this repulsive interaction model have been performed in order to investigate the equilibrium aggregate structures of a suspension composed of cubic haematite particles. It has been verified that Brownian dynamics employing the present steric interaction model are in good agreement with Monte Carlo results with respect to particle aggregate structures and particle orientational characteristics. From the viewpoint of developing a surface modification technology, we have also investigated a regime change in the aggregate structure of cubic particle in a quasi-2D system by means of Brownian dynamics simulations. If the magnetic particle–particle interaction strength is relatively strong, in zero applied magnetic field the particles aggregate in an offset face-to-face configuration. As the magnetic field strength is increased, the offset face-to-face structure is transformed into a more direct face-to-face contact configuration that extends throughout the whole simulation region.     

Telephotometer measurements and retrieved mass increase coefficients of the aerosol size distribution

Summary A non-linear iterative procedure is applied to the spectral sets of aerosol extinction coefficients, which were measured with the University of Vienna telephotometer during the Southern California Air Quality Study in Los Angeles (SCAQS), to obtain the mass size distribution of at least the accumulation mode aerosol at ambient relative humidity. The retrieved distributions show the expected shift of their mean diameters with changing relative humidity. The effect of advection of the Los Angeles plume to an upwind receptor region can also be seen very well from the inversions. Successive size distributions inverted from extinction measurements at different humidities are used to estimate the mass increase coefficient μ of the H?nel humidity model. The shift of the retrieved size distributions with humidity is used to trace the humidity behaviour of particles of a certain dry radius and convert the radius change to the μ. The results indicate that it is indeed possible to obtain information on μ if the aerosol stays in a steady state during the measurement period, if the dilution effect caused by the rise of the mixing height with increasing insolation is known with sufficient accuracy to be included quantitatively in the retrieval process for μ, and if the humidity and extinction measurements have the same temporal resolution.     

Inversion of visible optical extinction data for spheroid particle size distribution based on PCA

The problem of light scattering properties of spheroid particles is studied, and a general approach is presented for calculating the single particle light scattering of spheroids. In this approach, the extinction efficiency of spheroid particles can be calculated by combining the spline interpolation of T matrix method and ADA (anomalous diffraction approximation) theory. Furthermore, the retrieval of spheroid particle size distribution is performed in the dependent mode and a selection method about the optical extinction data is proposed based on PCA (principle component analysis) of first derivative corresponding to the raw optical extinction. By calculating the contribution rate of first derivative corresponding to the raw optical extinction, the optical extinction with more significant features can be selected as the inversion optical extinction data. In this way, the selected optical extinction has less information redundancy and higher capacity of resisting noise disturbance. Simulation experiments indicate that the spheroid particle size distributions obtained with the proposed method coincide fairly well with the given distributions, which provides a simple, reliable and efficient method to retrieve the spheroid particle size distribution using the optical extinction data.     

近红外波段气溶胶的衰减特性研究

在已知大气气溶胶折射率和气溶胶谱分布的基础上, 对近红外波段的气溶胶衰减特性进行了研究。利用Mie散射理论计算并讨论了气溶胶的消光、散射、吸收效率因子随尺度参数的变化和消光系数随半径和波长的变化, 并且在MATLAB中对各种变化情况进行了仿真。结果表明, 三种气溶胶粒子的消光和散射能力依次为沙尘性粒子, 水溶性粒子, 烟煤。消光系数在粒子半径和入射波长相近时达到最大, 并且粒子半径对消光、散射、吸收系数的影响比入射波长更明显。这些结论可以为红外辐射在大气中的衰减计算和分析提供依据。     

Diffusional coagulation of superparamagnetic particles in the presence of an external magnetic field

In this paper, we investigate the diffusional coagulation of colloidal superparamagnetic (SP) latex particles that are under the influence of an external magnetic field. The cluster size distributions (CSDs) that evolve with time were determined using an optical set-up that permits the direct visualization of particle clusters. Following the dynamic scaling analysis of van Dongen and Ernst (Phys. Rev. Lett. 54 (1985) 1396), we find that the CSDs all collapse onto a master curve when properly scaled. The bell-shape of this master curve indicates that large clusters preferentially scavenge small clusters in our system. From the time evolution of the average cluster size we infer that the reactivity between large clusters diminishes with increasing cluster size. These results are consistent with a simple mathematical formulation of the coagulation rate constant, or kernel, for the Brownian coagulation of magnetic particles. Moreover, our results support a growing body of evidence that the dynamic scaling theory developed by van Dongen and Ernst is a useful framework with which to study the microscale processes governing particle coagulation.