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。     

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。     

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。     

高灵敏VOCs在线真空紫外单光子电离飞行时间质谱仪的研制

研制了一种高灵敏度在线膜进样真空紫外电离源飞行时间质谱仪（MI-SPI-TOF MS）用于检测低浓度挥发性有机物（VOCs）。仪器包括真空系统、膜进样接口、真空紫外单光子电离源、垂直加速反射式飞行时间质量分析器和数据采集系统等。该仪器使用聚二甲基硅氧烷（PDMS）膜作为大气压下直接进样的接口,膜的选择透过性能直接、快速地富集大气中VOCs,可实现快速在线进样检测。真空紫外单光子灯作为电离源,能将电离能低于10.6 eV的VOCs电离,形成分子离子峰。结果表明,该仪器的分辨率优于750 FWHM,对苯、甲苯、二甲苯和氯苯的检测限达10^-12 mol/mol级别,检测速度达秒级,可用于低浓度VOCs的实时在线检测。     

真空紫外光电离质谱及其在大气化学中的应用研究

大气环境污染成因复杂，往往涉及一系列复杂的化学反应过程，且包含众多的挥发性有机物气体分子、自由基和气溶胶颗粒物等，在线检测是大气化学领域的难点和热点问题。真空紫外光电离质谱技术使分子吸收单个光子能量后，在其电离能阈值附近“软”电离，可以获得分子离子质量信息，具有质谱图简洁、碎片离子少和易于解析等特点，能够从分子层面上在线测量大气化学反应过程中关键的化学成分，揭示复杂的大气化学反应机理，在大气化学领域具有较好的应用前景。本文介绍了基于真空紫外激光、同步辐射光源、自由电子激光和真空紫外放电灯等多种光源的真空紫外光电离质谱技术，阐述了近年来该技术在大气挥发性有机物、自由基以及气溶胶颗粒物化学成分检测方面的进展，并展望真空紫外光电离质谱技术的发展方向。     

大气压离子源真空接口的研制及其在电喷雾电离飞行时间质谱仪上的应用

研制了一种大气压离子源真空接口,并已将其用于自制高分辨率垂直引入式电喷雾电离飞行时间质谱仪.初步研究了该接口的性能,包括射频四极杆、进样片对仪器灵敏度的影响.利用该接口检测了利血平样品.结果表明,接口能有效地提高离子的传输效率,使飞行时间质谱仪达到较高的灵敏度.     

基于叠型场线性离子阱的便携式质谱仪研制与应用

介绍了自行研制的基于叠型场线性离子阱的便携式质谱仪结构,以及初步的应用测试。该质谱仪的质量分析器采用叠型场线性离子阱,离子源采用辉光放电电子轰击电离源和介质阻挡放电离子源。仪器重10 kg,功耗低于100 W,体积33 cm×20 cm×20 cm,可以对气体、固体和液体进行检测。挥发性有机气体通过膜进样接口实现大气压直接进样,采用内置的辉光放电电子轰击电离源对其电离。介质阻挡放电离子源作为大气压离子源,通过非连续大气压接口实现质谱的大体积进样,及对枪击残留物DDU和去痛片等的快速检测。     

基于ICP-MS的二氧化硅亚微米粒子特征参数分析

将电感耦合等离子体质谱仪（ICP-MS）配合外部质谱信号采集存储装置,用于研究表征亚微米颗粒粒径和浓度参数。在模拟采集模式下,以300~2 000 nm粒径的SiO₂粒子为例,通过优化进样系统及仪器的工作参数,分析了样品提取速率和雾化气流速对单颗粒质谱信号强度的影响。在优化的实验条件下,SiO₂颗粒粒径部分检测限为233 nm,对300~900 nm粒径粒子测量的线性相关系数大于0.99,但对1 500、2 000 nm粒径粒子的检测结果出现明显偏差。论证了利用样品传输效率测量悬浮液粒子浓度的可行性,并将ICP-MS的粒径测量结果与扫描电镜法（SEM）、光子相关光谱法（PCS）的测量结果进行比较,3种方法对于粒径小于900 nm粒子的测定结果基本一致,且具有相似的测量精度。该方法分析速度快、结果准确,可用于SiO₂亚微米粒子粒径、浓度参数的测量。     

激光共振电离质谱法选择性电离铀钚混合物中的痕量钚

利用实验室开发的激光共振电离质谱仪,初步建立了激光共振电离质谱测定钚同位素比值的方法。通过扫描测量钚原子的自电离态能级,获得了一种具有较大电离截面的三色三光子共振电离方案。对铀钚混合物模拟样品,钚元素相对于铀元素的选择性在5×10⁶以上,²⁴⁰Pu/²³⁹Pu比值测量结果的相对标准偏差为1.1%。结果表明,激光共振电离质谱技术能有效避免同量异位素干扰以及其他元素带来的强峰拖尾干扰。     

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。     

实时在线单颗粒气溶胶飞行时间质谱仪的研制

针对大气气溶胶单颗粒粒径及成分同时检测的要求,自行研制了一台实时在线单颗粒气溶胶飞行时间质谱仪,并对仪器各部分的原理和结构进行了描述。用实验室产生的标准气溶胶粒子对仪器进行粒径和质量数校正,同时考察激光能量对邻苯二甲酸二辛脂(DOP)气溶胶颗粒的打击效率及其谱图的影响。室内气溶胶颗粒采样证明了该仪器具有较高的同位素测量精度及质量分辨率。     

单颗粒气溶胶实时在线监测飞行时间质谱仪的研制

介绍国内第一台采用空气动力学透镜进样系统的质谱仪。这种系统有效地提高进样效率和检测效率。本仪器优化双光束测径装置和激光解析电离装置的空间结构,缩短气溶胶漂移空间从而提高小颗粒的检测极限。     

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.     

Real-time single particle mass spectrometry: a historical review of a quarter century of the chemical analysis of aerosols

Real-time single particle mass spectrometry, or continuous aerosol mass spectrometry, was originally developed in the 1970s for the purpose of identifying the chemical composition of airborne particulate matter in real-time. Although this technique has continued to evolve throughout the following decades, the fundamental characteristic of this method remains the same, involving the continuous introduction of solid particle or liquid droplets directly into the ion source region of a mass spectrometer. Continuous sample introduction allows for the chemical analysis of single airborne particles in real-time. A number of mass analyzers have been employed in real-time single particle mass spectrometry. The original real-time single particle mass spectrometer used a magnetic sector mass analyzer. Quadrupole, double-focusing, and ion trap mass spectrometers have also been utilized. The majority of the current real-time single particle mass spectrometry techniques use time-of-flight mass spectrometry. In the literature, a variety of general names have been applied to real-time single particle mass spectrometry methods. These names include direct-inlet mass spectrometry, on-line laser microprobe mass spectrometry, particle analysis by mass spectrometry, particle beam mass spectrometry, and rapid-single particle mass spectrometry. This review covers real-time single particle mass spectrometry techniques that were developed from 1973 through 1998, specifically for analyzing airborne particulate matter, including environmental aerosols, biological aerosols, and clean-room aerosols. Because the majority of the historical and current real-time single particle mass spectrometers have been employed for atmospheric aerosols, this topic is the primary focus of this review. This review does not include on-line mass spectrometry methods that are employed as a detector for other instrumental methods, such as liquid chromatography.     

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.     

空气中苯、甲苯、乙苯等有害气体的质谱在线监测

Benzene, toluene, ethylbenzene, heptane, oxygen, nitrogen and carbon dioxide in air were simultaneously quantative analyzed with a home-made quadrupole mass spectrometer using capillary sample inlet system. The cross interferences of toluene and ethylbenzene was eliminated with calibration factor matrix.     

A homemade high-resolution orthogonal-injection time-of-flight mass spectrometer with a heated capillary inlet

We describe a homemade high-resolution orthogonal-injection time-of-flight (O-TOF) mass spectrometer combing a heated capillary inlet. The O-TOF uses a heated capillary tube combined with a radio-frequency only quadrupole (rf-only quadrupole) as an interface to help the ion transmission from the atmospheric pressure to the low-pressure regions. The principle, configuration of the O-TOF, and the performance of the instrument are introduced in this paper. With electrospray ion source, the performances of the mass resolution, the sensitivity, the mass range, and the mass accuracy are described. We also include our results obtained by coupling atmospheric pressure matrix-assisted laser deporption ionization with this instrument.