单颗粒气溶胶飞行时间质谱仪在细颗粒物研究中的应用和进展

单颗粒气溶胶质谱技术起源于20世纪70年代,在近二十年得到了快速的发展.单颗粒气溶胶飞行时间质谱仪具有高时间分辨率,且同时测量大气中单个细颗粒物粒径、多种化学组分和混合状态的特点,在大气细颗粒物监测和科学研究中逐渐得到了广泛应用.本文对单颗粒气溶胶飞行时间质谱仪的发展历程进行了介绍,对目前已商品化的单颗粒气溶胶飞行时间质谱仪ATOFMS和SPAMS的原理、数据分析方法、结果输出方式以及在环境监测和研究中的主要应用进行了总结,并指出单颗粒气溶胶飞行时间质谱仪的发展方向.     

若干气溶胶单粒子化学成分的实时测量

利用激光解吸附电离飞行时间质谱技术获得了若干已知化学成分的气溶胶粒子的飞行时间质谱,分析标识了各类气溶胶粒子的特征离子谱峰,并对一些特征峰的形成机理进行了探讨。在此基础上,对烟花火药以及纸张燃烧产生的烟气气溶胶粒子进行了实时在线测量,通过对质谱图的分析,获得了有关此两类燃烧过程产生的烟气气溶胶单粒子的化学组成信息。     

基于单颗粒气溶胶质谱的人体呼出颗粒物粒径分布与化学成分的分析方法研究

人体呼出气中内源性颗粒物和外源性颗粒物的粒径和化学成分信息可为肺部疾病诊断、环境暴露评价等研究提供参考。该文初步考察了单颗粒气溶胶质谱(Single particle aerosol mass spectrometry,SPAMS)同时获取人体呼出气中颗粒物(Exhaled breath particles,EBPs)粒径分布和化学成分的可行性。结果表明,健康成人的EBPs数浓度为227~1 043个/L,获取具有统计意义的粒径分布所需的EBPs检出限为2 500个颗粒物,粒径范围为200~1 000 nm,峰值出现在460 nm。与环境空气颗粒物的粒径分布相比,EBPs更多分布在200~300 nm和440~660 nm,从化学成分来看,这两段粒径范围内的EBPs含有更多的碳元素,不易在体内发生吸湿增长,提高了被呼出的概率。EBPs的化学成分可能反映内源性颗粒物和外源性颗粒物组成,如HSO_4~-、PO_3~-、CN~-、CNO~-和C_xH_yO_z~+(x=1~3,y=1~7,z=1~3)可能与内源性颗粒物中的蛋白含量、磷酸酯酰甘油等成分有关,碳簇峰C_3~-、C_4~-、C~+、C_3~+、C_3H~+和C_4~+推测与外源性颗粒物中的碳元素有关。     

单光子电离飞行时间质谱仪对香烟新鲜主流烟气的在线检测

利用单光子电离飞行时间质谱仪对吸烟模拟装置中的新鲜主流烟气进行实时在线检测,共测得40多种挥发性有机化合物,获得不同物质在逐口吸烟过程中含量的变化情况以及不同通风率的香烟烟气中的化合物含量情况。与此同时,使用主成分分析法对不同通风率的香烟种类的新鲜烟气的谱图进行分析,结果表明,在PCA散点图中,PC1=94%,PC2=3%,PC2=1%,三者之和达到98%,不同通风率的香烟的差异显著。实现了对逐口吸烟产生的新鲜主流烟中的有机成分进行在线检测分析。     

用自组织特征映射神经网络对飞行时间质谱采集的大气气溶胶单粒子进行分类

气溶胶飞行时间质谱仪(ATOFMS)在对气溶胶粒子的测量过程中,产生大量包含单粒子化学成分和粒径信息的数据。本研究采用具备矢量量化与数据降维能力的自组织特征映射网络(SOM),对自制的气溶胶飞行时间质谱仪24 h采集到的室内大气气溶胶质谱数据进行聚类分析。获得"含钙"、"盐类和二次气溶胶"、"二次颗粒"、"有机胺"、"富含钾有机物"、"无机盐"和"土壤"等20类颗粒。相比于其它聚类方法,SOM可进行可视化分析,对神经元进行再次聚类,聚类中心多。这些分类信息将有助于评估气溶胶粒子的反应和毒性,以及鉴别气溶胶粒子的起源。     

卷烟主流烟气气溶胶中酚类物质的粒径分布研究

为研究酚类物质在卷烟主流烟气气溶胶中的粒径分布,采用单通道吸烟机-电子低压撞击器(ELPI),通过12级聚酯薄膜捕集烟气气溶胶粒相物,采用超高效液相色谱-荧光检测方法测定了14种酚类在不同粒径气溶胶中的分布。实验结果表明,本方法捕集得到气溶胶粒相物质量的相对标准偏差小于10%,具有较好的稳定性;超高效液相色谱-荧光检测方法测定14种酚类的线性相关系数R2均大于0.9959,检出限低于1.2 ng/cig,回收率在80.1%~115.0%之间,方法简单快速,准确可靠。采用本方法研究了卷烟主流烟气气溶胶中14种酚类物质含量和浓度的粒径分布,发现除了4-乙基愈创木酚在捕集的气溶胶中未检出外,其它13种酚类物质在不同粒径气溶胶粒相物中的含量分布随粒径增加呈现先增加后减小的趋势,与粒相物质量分布一致,并主要集中在中等粒径(0.261~0.722μm)的粒相物中,在粒径0.431μm的粒相物中含量最高;不同酚类物质在不同粒径气溶胶中的浓度分布趋势有差异,苯酚和单取代苯酚类的浓度分布有特异性,其浓度随着粒径增加呈现先增加后减小的趋势,在中等粒径的粒相物中(0.261~0.722μm)浓度最高;苯二酚类和单取代苯二酚的浓度在0.144~1.166μm的粒相物中分布无明显差异,二取代苯酚类的浓度随着粒径的变化无明显差异。     

单颗粒气溶胶质谱仪串联热稀释器在线测量单个气溶胶颗粒的挥发性

颗粒挥发性可以影响颗粒在大气中的寿命,对大气颗粒物中二次气溶胶的形成机制研究有一定的参考价值。以往研究测量颗粒挥发性采用的是热熔蚀器,其活性炭吸附器一旦老化后,在较高温度下可能会释放出活性炭,造成测量失真。本研究针对热熔蚀器的上述缺点,以稀释器替代活性炭吸附器部分,与单颗粒气溶胶质谱仪(SPAMS)连接,建立了一种在线分析单个气溶胶颗粒挥发性的测量方法。气溶胶颗粒分别通过两个通道进入SPAMS分析颗粒信息。通道1,气溶胶颗粒由管路进入加热器,被加热至不同的温度,颗粒挥发产生的气体和挥发后的颗粒内核进入稀释器部分,利用干净干燥冷的稀释气对加热挥发后的气体和颗粒进行稀释,使颗粒温度降低并短时间内不与气体发生冷凝,最后进入SPAMS进行检测。通道2为单独硅胶管,其长度与通道1相同,气溶胶颗粒通过通道2直接进入SPAMS检测。通过对比通道1和通道2获得的颗粒信息(粒径、数目和质谱信息等),得到气溶胶颗粒在不同温度下的挥发性。实验室用标准物质进行评估测试,结果表明,采用稀释器可以避免活性炭吸附器使用时间变长而失效,防止挥发性物质冷凝回到颗粒中。应用本方法初步测定了广州市春季气溶胶的挥发性,表明春季气溶胶多为高度挥发性和中度挥发性物质。     

高效液相色谱-串联质谱法分析硫酸特布他林雾化气溶胶含量及空气动力学粒径分布EI北大核心CSCD

建立了一种高效液相色谱-三重四极杆串联质谱法测定雾化吸入装置中硫酸特布他林雾化液气溶胶含量和分析空气动力学粒径分布情况的方法。确定50%甲醇水为最优提取溶剂。采用BEH C18色谱柱分离,0.1%甲酸水和乙腈为流动相进行等度洗脱,分析时间为2 min,正离子模式下多反应监测模式测定。采用该方法对雾化5 min和25 min气溶胶的平均药物浓度和空气动力学粒径分布进行了分析。结果显示,硫酸特布他林在0.5~600 ng/mL范围内线性关系良好(r>0.999),定量限为0.5 ng/mL;硫酸特布他林日内及日间相对标准偏差(RSD)分别为0.3%~4.5%和0.8%~4.8%。雾化气溶胶的平均提取回收率为98.5%,RSD为2.6%。抽气采集法下雾化5 min和25 min气溶胶的平均药物含量分别为15.8和15.9 mg/m^(3),总体RSD为2.5%,撞击器采集法下雾化5 min和25 min时的平均药物含量分别为16.2和16.8 mg/m^(3),平均质量中值空气动力学粒径(MMAD)分别为2.32和2.28μm。本方法用于硫酸特布他林雾化气溶胶的浓度测定和空气动力学粒径分布分析,在吸入装置中雾化5 min后药物浓度即达到均一。随着雾化时间延长,雾化装置内硫酸特布他林雾化气溶胶的空气动力学粒径分布相对稳定。     

显微拉曼光谱用于研究大气单颗粒表面非均相反应

大气单颗粒表面的非均相反应研究因更接近大气实际条件,避免了堆积态研究中人为引入的误差,能够得到真实的反应过程与机理,获得反映大气实际条件的动力学参数.本研究建立了使用显微拉曼光谱研究大气单颗粒非均相反应的研究方法,并初步用于研究NO2与单颗粒CaCO3的非均相反应.研究结果表明显微拉曼光谱可同时获得颗粒物的化学组成和形貌变化,并能得到化学环境如相态的信息,对于研究反应过程很有帮助;而颗粒物沉降在基质上得到的拉曼光谱因不受形貌共振影响,有利于获得高质量的光谱.此外,将拉曼光谱研究单颗粒的方法与其他单颗粒非均相反应的研究方法进行了综合比较,表明显微拉曼光谱技术在单颗粒非均相反应研究中具有重要的特点和应用价值.     

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.     

7种生物碱在不同粒径卷烟主流烟气气溶胶中的分布研究

建立了烟气气溶胶中7种生物碱的气相色谱-质谱(GC-MS)测定方法,并采用电子低压撞击器(ELPI)分12级捕集烟气气溶胶粒相物,研究了卷烟主流烟气气溶胶中7种生物碱含量和浓度的粒径分布。捕集的气溶胶样品加入氢氧化钠溶液和二氯甲烷进行碱法提取,提取液经DB-5MS弹性毛细管柱分离,选择离子监测模式测定,内标法定量。结果表明:该法检测主流烟气气溶胶中7种生物碱的相对标准偏差(RSD)为2.1%~6.4%,检出限为0.39~14.84 ng/cig,加标回收率为85.5%~124.8%。7种生物碱主要分布于0.144~0.722μm的中等粒径气溶胶粒相物中,在粒径0.431μm的粒相物中含量最高,与捕集的粒相物质量分布一致。7种生物碱在不同粒径气溶胶粒相物中的浓度基本趋于一致,其浓度随气溶胶粒径的分布无特异性。     

基质与分析物的摩尔比和激光能量对分析物离子信号的影响

A method of aerosol introduction for matrix-assisted laser desorption/ionization (MALDI) is described. The aerosol particles containing matrix and analyte enter directly into the aerosol time-of-flight mass spectrometer (ATOFMS) at atmospheric pressure. The scattered light signals from the aerosol particles are collected by a photomultiplier tube (PMT) and are passed on to an external electronic timing circuit, which determines particle size and is used to trigger a 266 nm pulsed Nd:YAG laser. The aerosol MALDI mass spectra and aerodynamic diameter of single particles can be obtained in real-time. Compared with other methods of liquid sample introduction, this method realizes detection of single particles and, more importantly, the sample consumption is lower. The effects of matrix-to-analyte ratio and laser pulse energy on analyte ion yield are examined. The optimal matrix-to-analyte ratio and laser energy are 50-110:1 and 200-400 μJ respectively.     

气溶胶单粒子化学成分的实时测量

自行设计了国内第一台可实时测量气溶胶单粒子化学成分的气溶胶飞行时间质谱仪,并用该仪器对两类燃烧过程产生的气溶胶粒子进行了实时测量。实验结果展示了本仪器能够同时实现实时在线测量和单粒子检测,从而克服了传统的离线检测方法如色谱法、化学方法的局限性。     

乙苯光氧化产生二次有机气溶胶的化学成分及反应机理分析

在自制的烟雾腔内,研究羟基自由基(OH·)启动的乙苯的光氧化反应和一系列后续反应,产生了二次有机气溶胶. 采用空气动力学直径粒谱分析仪分析了气溶胶粒子的尺寸分布;并用自制的气溶胶飞行时间质谱仪快速、实时地测量了单个二次有机气溶胶粒子的分子组分. 初步探讨了这些组分的可能反应机理.     

Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol

The kinetics of heterogeneous reactions involving supercooled organic droplets is reported for the first time. Reactions between ozone and internally-mixed sub-micrometre particles containing an unsaturated alkenoic acid, oleic acid, and an n-alkanoic acid, myristic acid, were studied as a simple model for the oxidation of meat-cooking aerosol. The reactions were followed by monitoring the rate of oleic acid loss using an Aerosol CIMS (chemical ionization mass spectrometry) instrument for real-time particle analysis. Evidence of as much as 32 degrees C supercooling at room temperature was observed depending on particle composition. FTIR spectra of the aerosol also demonstrate features indicative of supercooling. Particles in which crystallization was induced by cooling below room temperature demonstrated decreased reactivity by a factor of 12 compared to supercooled particles of the same composition. This drastic difference in reactivity could have significant implications for the lifetimes of reactive species in ambient aerosol as well as for the accurate source apportionment of particulate matter.     

气相色谱法测定电子烟烟液及气溶胶中双乙酰和乙酰丙酰

建立气相色谱法氢火焰离子化检测器测定电子烟烟液和气溶胶中双乙酰和乙酰丙酰含量的方法。样品以20 mL乙醇为萃取剂,涡旋振荡萃取10 min,采用气相色谱外标法进行定量分析。双乙酰和乙酰丙酰质量浓度在0.5~50 μg/mL范围内与色谱峰面积呈良好的线性关系,相关系数分别为0.999 6、0.999 4,方法检出限分别为0.044、0.052 μg/mL。烟液中双乙酰和乙酰丙酰测定结果的相对标准偏差为2.5%~4.3%(n=6),样品加标回收率为95.0%~102.5%;气溶胶中双乙酰和乙酰丙酰测定结果的相对标准偏差为3.1%~4.6%(n=6),样品加标回收率为92.7%~102.3%。气溶胶中双乙酰和乙酰丙酰理论浓度与实测浓度具有较强的相关性(对于双乙酰r~2=0.990 1,对于乙酰丙酰r~2=0.994 7),说明双乙酰、乙酰丙酰烟液通过雾化直接转移至气溶胶中。该方法准确度高,重现性好,检出限低,可满足电子烟样品的检测需求。     

Detecting trace pesticides in real time using single particle aerosol mass spectrometry

Pesticides are toxic substances and may cause unintentional harm if improperly used. The ubiquitous nature of pesticides, with frequent use in agriculture and the household, and the potential for harm that pesticides pose to non-target organisms such as wildlife, humans, and pets, demonstrate the need for rapid and effective detection and identification of these compounds. In this study, single particle aerosol mass spectrometry (SPAMS) was used to rapidly detect compounds from four classes of pesticides commonly used in agricultural and household applications. These include permethrin (pyrethroid class), malathion and dichlorvos (organophosphate class), imidacloprid (chloronicotinyl class), and carbaryl (carbamate class). Analytical standards of each compound were diluted and aerosolized using a nebulizer to create particles for analysis in the SPAMS instrument. The resultant dual-polarity time-of-flight mass spectra were then analyzed to identify the characteristic peaks of the compound in each sample. In addition, samples of commercial products containing pesticides, a commercial insecticide spray, containing permethrin, and a canine flea collar, containing carbaryl, were analyzed in their original form using SPAMS without any significant sample preparation. The characteristic mass spectral peaks of the active pesticides in these samples were identified using the mass spectra obtained earlier from the pesticide analytical standards. By successfully identifying pesticides in analytical standards and in commercial products, it is demonstrated herein that the SPAMS system may be capable of pesticide detection in numerous environmental and agricultural situations.     

Laser Microprobe Mass Analysis of Individual Antarctic Aerosol Particles

Abstract

Individual Antarctic aerosol particles in the 0.5–4 μm aerodynamic diameter range were analyzed using laser microprobe mass analysis (LAMMA). As they were sampled near the ocean, the great majority consists of seasalt, transformed to various degrees in the atmosphere. Major alterations include the association of an excess sulfate and methane sulfonate with these particles. Sulfate-rich particles containing little or no chloride were found mostly in the smallest size fraction (0.5–1 μm), where they account for some 5% of all particles: they are most likely highly transformed seasalt. Aluminosilicates, on the other hand, only appear among the coarser particles: they represent 2% of the particulates in the 2–4 μm range. The remainder of the aerosol consists of organic, Fe-rich, K-rich and Zn-rich particles. The latter groups have very low abundances: always less than 1% of the population of the impactor stage(s) onto which they were collected.     

Analytical study of cigarette smoke enriched in benzo[a]pyrene for use in model animal studies

Cigarette smoke has been significantly enriched in benzo[a]pyrene (BAP) by injecting 200 μl of a cyclohexane solution, containing a total of 40 μg of BAP, into a cigarette. After injection, the cigarette is conditioned and smoked according to standard protocol. When the cigarette smoke condensate is analyzed by fluorescence spectroscopy, liquid scintillation counting, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry, it is found that the level of BAP has increased by 1000 times with respect to levels reported for unenriched cigarette smoke. No chemical transformation of the BAP has been detected, and the BAP-enriched fraction does not appear to be perturbed to a detectable degree. Approximately 28% of the BAP is measured in the mainstream smoke, 46–48% in the sidestream smoke from the burning end of the cigarette, and 7% in the butt and ash. Correcting for analytical losses, about 10% appears to escape in the gaseous state. This material may prove suitable for model animal studies.