在线单粒子质谱研究进展

单粒子质谱(SPMS)能够在线测量气溶胶粒子的粒径和化学组成,在大气化学研究、环境污染监测等方面有广泛的应用前景。一般的在线单粒子质谱主要由进样系统,粒径测量系统和化学组分分析系统三部分组成。气溶胶粒子来源广泛,组成复杂,对于不同类型的气溶胶粒子需要采用不同的电离方式。用于研究气溶胶颗粒的单粒子质谱种类繁多,激光电离单粒子质谱和电子轰击电离单粒子质谱是最早出现也是目前发展较为成熟的两种仪器。近年来出现了一些采用软电离技术的新型单粒子质谱,能够对气溶胶的化学组分进行定量分析。随着科技的不断发展,提高仪器的性能以扩展仪器的应用范围,仪器的商品化将是单粒子质谱仪发展的主要趋势。     

单颗粒气溶胶质谱仪自动粒径校正方法

单颗粒气溶胶质谱仪通常采用空气动力学透镜进样,通过测量透镜出口每一个颗粒物的速度来推算颗粒物的空气动力学直径。然而,颗粒物速度受透镜前端压力的影响较大,该压力发生微小变化就会导致颗粒物粒径检测发生偏差。本研究提出一种适用于单颗粒气溶胶质谱仪的自动粒径校正方法,预先记录几组一定透镜前端压力范围内的粒径校准参数,然后根据进样压力的变化,使软件自动通过插值算法拟合相应的粒径校正方程对颗粒物粒径测量值进行校正,从而保证在指定的压力波动范围内粒径测量结果的准确性。实验结果表明,当透镜前端压力在164.92~352.45 Pa范围变化时,该方法对于152~3100 nm颗粒物的测径偏差大部分都在10 nm以内。模拟结果表明,该方法能够保证仪器在海拔8 km范围内粒径测量的准确性,可以应用到所有采用空气动力学进样及激光颗粒物粒径测量的仪器中,能够极大地增加仪器对外界环境的适应性并提高数据结果的可靠性。     

气溶胶在线质谱仪及其在汽车尾气中的应用

汽车排放的颗粒气溶胶和有害气体严重影响着大气环境和人们的健康。我们研制了一台能够在线监测气溶胶粒径分布和气体组成成分的气溶胶在线质谱仪。此仪器具有响应时间快,性能稳定,自动化程度高和移动性好等特点。仪器采用了软电离方式,避免了碎片离子峰的形成,便于对污染环境中挥发性有机物的解析。实验结果表明仪器对挥发性有机物的检测下限为25ppb量级,并能实时测量尾气中气溶胶的浓度,在工厂废气以及污染场所气溶胶的测定方面有广阔的应用前景。     

在线测量气溶胶大小和化学组分的质谱技术与应用

介绍了在线连续监测大气单粒子气溶胶的粒径和化学组分的飞行时间质谱仪。本装置采用喷嘴加两个skimmer构成的差分真空进样,双光束空气动力学测量技术,激光解吸附电离和双极飞行时间质谱技术。利用这套装置对室内外的空气进行了实际的测量,该技术可以在线测量气溶胶的粒径分布,并同时对气溶胶的化学组分进行实时监测。     

基于FPGA的单粒子气溶胶质谱时序控制系统

在单粒子气溶胶的粒径分布和化学组分实时分析的激光质谱系统中，应用现场可编程门阵列技术，讨论了高速数字电路中的精确定时问题，并研制了一套测量系统，对实际大气中气溶胶粒子进行粒径大小的统计分布和质谱的测定。     

高速大容量气溶胶粒子分类计数存储器的设计实现

摘要：空气动力学粒谱仪能够同时测量气溶胶粒子的空气动力学粒径和光学粒径。本文采用多道存储技术,结合大规模可编程逻辑芯片及高速大容量双端口内存芯片,设计了高速大容量气溶胶粒子分类计数存储器。主要特色是：单一脉冲计数器与特征信号分类计数器有机结合,存储容量高达65535道,每道可计数65535个,典型操作速度可达15nS,且线路简单。该存储器作为本研究所自行研发的空气动力学粒谱仪的关键存储部件,完全满足仪器连续、实时、在线监测对存储速度和容量的要求。     

气溶胶颗粒折射率在光学粒径测量中的影响

针对单颗粒光散射测量方法中被测颗粒折射率会影响测量结果的问题,根据Mie理论和光辐射能通量计算公式,对13种常见气溶胶颗粒,在不同采光中心角θ和采光接收半角β下的散射光辐射能通量F与粒径D关系曲线进行了计算,提出一种基于相对测量误差平均值的评价标准,依据该评价标准定量分析了13种折射率对测量的影响。通过对模拟结果的分析,得出采光结构接收到的光辐射能通量包含前向散射光的条件下,13种颗粒的F-D曲线较为接近,折射率对测量结果的影响相对较小。     

SPAMS打击率影响因素与仪器状态分析

在北京市环境保护监测中心空气质量综合观测实验室,使用气溶胶单颗粒飞行时间质谱（SPAMS）对2013年1~12月空气颗粒物开展综合观测。实验结果表明,SPAMS打击率与测径颗粒数（siz）、大气相对湿度、颗粒物组分以及粒径有关。仪器状态正常时,打击率在siz数量小、大气相对湿度低时较高,与含K⁺、HSO₄^-、OCEC、NO₃^-的颗粒物以及粒径为0.2~0.3 μm、0.3~0.4 μm、0.4~0.5 μm的颗粒物数量呈正相关,与0.1~0.2 μm、0.5~0.6 μm、0.6~0.7 μm的颗粒物数量呈负相关,含NH₄⁺、SiO₃^-颗粒物数量的关系与污染特征及其他环境有关。本研究通过分析打击率数值及打击率与各影响因素的关系判断仪器状态是否正常,这为提前发现常规方法难以发现的仪器故障提供了一种思路。     

颗粒密度对声发射法粒径测量的影响

基于单颗粒碰撞声发射信号的粒径测量研究是实现声发射法粒径在线测量的基础,有助于进一步理解声发射粒径测量的机理。设计并搭建了单颗粒碰撞实验装置,分别采用0.4 mm、0.6 mm和0.8 mm的玻璃珠和钢珠撞击波导杆,分析不同密度颗粒碰撞产生的声发射信号特征。分析结果表明,颗粒密度增大,相同颗粒粒径和碰撞速度下产生的声发射信号的幅值与持续时间也增加。同时,根据非弹性碰撞理论,建立颗粒粒径的反演模型,并比较了不同密度颗粒的粒径测量结果。实验结果表明,颗粒密度对声发射法粒径测量结果的影响较小,大部分测量结果的平均相对误差在8%以内。     

高速大容量气溶胶粒子分类计数存储器的设计

为实现气溶胶颗粒物的空气动力学粒径及其光学粒径的同时测量,对颗粒物按粒径大小进行分类计数,利用电子学多道存储技术,结合大规模可编程逻辑电路和高速大容量双端口内存芯片,设计了一种高速大容量粒子分类计数存储器。该存储器实现了单一脉冲计数器与特征信号分类计数器的有机结合,其存储容量高达65535道,每道可计数65535个,操作速度可达15ns;而且线路简单,整个电子学多道电路只需要两片MACH435和两片IDT7009芯片。用设计的存储器对空气中空气动力学粒径为0.5～20μm的气溶胶颗粒物进行计数,得到了颗粒物的粒谱分布。该存储器已应用于本研究所自行研发的空气动力学粒谱仪,完全满足仪器连续、实时、在线监测时对存储速度和容量的要求。     

Effect of the Normal Load on the Release of Aerosol Wear Particles During Abrasion

A study highlighting the aspect of the generation of aerosol wear particles during abrasion is presented. The substrate chosen is a masonry brick which is reinforced with TiO₂ nanoparticles. This is done using a pin on plate arrangement. The material removal mechanism via fracturing is first understood. The parameter chosen for the study is the normal load. The formed aerosols are then characterized by their number concentration, particle size distribution, individual particle shape, size and chemical composition. Having irregular shapes, the aerosol wear particles have unimodal size distributions with 5–7 % (in mass) of Ti content. The size mode increases with the increase in normal load. However, at higher normal loads, while there is an unexpected increase in the wear mass, the maximum concentration of the aerosol particles saturates. During the whole study, no free nanoparticles of TiO₂ were found.     

用于纳米气溶胶质谱仪的毛细管进样接口传输特性研究

采用自制的X射线离子诱导成核纳米颗粒物生成装置,通过纳米扫描迁移率颗粒物粒径谱仪（Nano-SMPS）测量纳米颗粒物通过毛细管之前、之后的粒谱分布,获得了纳米颗粒物穿透率随毛细管的内径、长度及进样流量的变化曲线,并对纳米颗粒物在毛细管中的传输损耗进行实验探究。同时,结合气溶胶颗粒物传输沉积模型,对纳米颗粒物的穿透率进行理论计算,并与实验测量值进行比较和讨论。结果表明,对于粒径小于10 nm的纳米颗粒物,受布朗运动等因素的影响,其穿透率与毛细管的尺寸及进样流量有较强的相关性。此外,采用毛细管进样接口结合激光电离气溶胶飞行时间质谱仪对部分纳米颗粒物的化学成分进行检测,获得了初步的实验结果。     

Aerosol laser time-of-flight mass spectrometer for the on-line measurement of secondary organic aerosol in smog chamber

An aerosol laser time of flight mass spectrometer (ALTOFMS) that can be used for real-time measurement of the size and composition of individual aerosol particles has been designed and utilized to provide on-line measurement of secondary organic aerosol (SOA) particles resulted from Cl-initiated oxidation of toluene in smog chamber. Both the size and chemical compositions of individual aerosol particles were obtained in real-time. According to a large number of single aerosol diameters and mass spectra, the size distribution and chemical composition of aerosol were determined statistically. Experimental results indicate that aerosol particles produced from Cl-initiated oxidation of toluene were predominantly in the form of PM 2.5 particles, and nine positive laser desorption/ionization mass spectra peaks: m/z 18, 29, 30, 44, 46, 52, 65, 77, and 94 may come from the fragment ions of the products of the SOA: aromatic aldehydes, aromatic acids, phenolic compounds, and nitrogenated organic compounds. These results were in good agreement with those ones from previous Cl-initiated oxidation of toluene. These were demonstrated that ALTOFMS is a useful tool to reveal the formation and transformation processes of SOA particles in smog chamber.     

毛细管进样-激光解吸电离气溶胶飞行时间质谱仪检测超细纳米颗粒物化学成分

采用毛细管大气压进样接口，结合激光多光子解吸、电离等技术，自行研制了毛细管进样-激光解吸电离气溶胶飞行时间质谱仪，用于在线测量超细纳米颗粒物的化学成分。应用商品化的气溶胶发生器和自制的离子诱导成核反应器，在实验室内分别产生了KCl、NaCl、NaI/NaBr混合物和Air/H₂O/SO₂混合气体成核反应的粒径小于100 nm的超细纳米颗粒物，并通过质谱仪获得了它们的化学成分信息。结果表明，相对于具有较大粒径的颗粒物，超细纳米颗粒物在激光多光子电离过程中更容易完全原子化电离，但通过改善激光的聚焦条件可以获得超细纳米颗粒物成分的分子信息。实验测量了毛细管大气压进样接口传输超细纳米颗粒物的效率，为0.33%，与国际同行采用类似大气压进样接口传输气体分子的效率一致。     

Novel in situ setup to study the formation of nanoparticles in the gas phase by small angle x-ray scattering

An in-house built aerosol generator setup for in situ gas phase studies of aerosol and nanoparticles is described. The aerosol generator with an ultrasonic ceramic disk mist maker provides high enough particle concentrations for structural gas phase analysis by synchrotron small angle x-ray scattering (for water approximately 4 x 10(8) droplets/s with a droplet size of approximately 2.5 microm). The working principle was proved by scattering of gold nanoparticles. For evaporation induced self-assembly studies of nanostructured particles, an additional thermal treatment chamber was included in the setup. The first on-line gas phase data with our setup for mesostructured silica particles are presented for different thermal treatments. Scanning electron microscope imaging revealed the average particle size to be approximately 1 microm. Furthermore, to quantify their internal nanostructure, diffraction experiments of deposited silica aerosols were carried out and the corresponding electron density map indicates a silica wall thickness of about 1 nm.     

Atomic force and scanning electron microscopy of atmospheric particles

Atomic force microscopy (AFM) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) have been used for both morphological and elemental mass analysis study of atmospheric particles. As part of the geometrical particle analysis, and in addition to the traditional height profile measurement of individual particles, AFM was used to measure the volume relative to the projection area for each particle separately, providing a particle shape model. The element identification was done by the EDS analysis, and the element mass content was calculated based on laboratory calibration with particles of known composition. The SEM-EDS mass measurements from two samples collected at 150 and 500 m above the surface of the Mediterranean Sea were found to be similar to mass calculations derived from the AFM volume measurements. The AFM results show that the volume of most of the aerosols that were identified as soluble marine sulfate and nitrate aerosol particles can be better estimated using cylindrical shapes than spherical or conical geometry.