二次有机气溶胶的气体/粒子分配理论

本文重点评述了二次有机气溶胶形成的气体/粒子分配理论,简要介绍了它的发展和可能的应用.在大气中,气体有机物种的氧化可以产生半挥发性的有机化合物,二次有机气溶胶的形成可以用气体/粒子分配的吸收模型来评估.气体/粒子分配过程决定于半挥发性化合物的成分、浓度和蒸气压,以及吸收性材料的浓度和成分.在气体/粒子分配理论的基础上,人们又研究和开发出二次有机气溶胶的分子组分的气体/粒子分配的热力学模型,它可以用来预估气溶胶中液态水的含量、无机物的分布、亲水性和疏水性有机物的分布.二次有机气溶胶形成的化学机理和气体/粒子分配的热力学模型与加利福尼亚工学院三维都市/区域性大气模型相结合,可以用于气相和气溶胶相模拟.     

用气溶胶飞行时间质谱实时探测甲苯光氧化产生的单个二次有机气溶胶粒子

在烟雾腔内, 用紫外光照射甲苯、亚硝酸甲酯、一氧化氮和空气的混合物, 可以启动甲苯和羟基自由基(OH·)的光氧化反应和一系列的后续反应, 产生非挥发性和半挥发性有机化合物. 半挥发性有机化合物可以在气态和粒子态之间进行分配, 产生二次有机气溶胶粒子. 用自制的气溶胶飞行时间质谱仪, 快速、实时测量这些粒子的尺度、它们的分子成分和直径分布.     

二次有机气溶胶形成的化学过程

挥发性有机化合物的光氧化过程和光氧化产物的气态/粒子态均分过程是二次有机气溶胶形成的重要原因.二次有机气溶胶形成的化学机理主要涉及到挥发性有机化合物的光氧化过程及其一系列的后续反应,它们导致了对流层中臭氧浓度的增加和二次有机气溶胶的形成.本文将重点介绍二次有机气溶胶形成的重要化学过程和量子化学计算研究.     

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。     

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.     

二次有机气溶胶的水相形成研究

二次有机气溶胶是大气颗粒物中的主要成分,对大气环境、气候以及人类健康等有重要影响。近年来的研究表明,水相形成二次有机气溶胶与传统气相形成二次有机气溶胶对二次有机气溶胶的贡献相当,且能够解释用传统气相形成方法无法解释的野外观测与模型模拟以及野外观测与室内烟雾箱模拟二次有机气溶胶在颗粒大小、分布、浓度以及老化程度等方面的差异,因而成为研究的热点。本综述重点介绍了目前大气中二次有机气溶胶水相形成的实验室研究,包括黑暗条件下的非自由基反应(水合、缩醛/半缩醛、醇醛缩合和催化反应)和光照条件下的自由基反应。同时,对二次有机气溶胶水相形成研究的发展方向进行了展望。     

挥发性和半挥发性有机物向二次有机气溶胶转化的机制*

从近20年二次有机气溶胶形成机制的研究成果可发现,挥发性和半挥发性有机物转化为二次有机气溶胶的主要物理化学过程可概述为光化学氧化机制、成核过程、凝结和气/粒分配机制以及非均相反应机制。本文系统总结了这些物理化学反应的发生过程及其影响因素,重点阐述了异戊二烯和甲苯同系物的光氧化机制,总结了二次有机气溶胶气/粒分配的两种理论--吸收机制和吸附机制,评述了发生在颗粒相上的非均相反应对二次有机气溶胶形成的重要作用。最后,对二次有机气溶胶形成机制研究的发展方向进行了展望。     

基于气溶胶质谱的二次有机气溶胶识别

二次有机气溶胶(SOA)是大气气溶胶十分重要的组成部分,也是目前人们认识最为薄弱的气溶胶组分.由于有机气溶胶化学组成的复杂性,对SOA进行有效的识别和估算一直是国际气溶胶研究领域的热点和难点问题.本研究尝试使用一种新方法来定量识别深圳冬季大气中的SOA:利用气溶胶质谱仪在线观测的高时间分辨率优势和质谱中的特征碎片离子,应用正定矩阵因子解析(PMF)模型对细粒子组分的主要来源进行解析,识别出其中的二次有机物.结果表明:深圳冬季大气细粒子中SOA浓度平均为9.41±6.33μg/m3,占总有机物质量的39.9±21.8%;相比于一次有机气溶胶(POA),SOA浓度水平变化较为平缓,体现了区域性二次污染物的特征.SOA/BC比值具有鲜明的日变化规律,且与Ox(O3+NO2)的日变化规律相似,说明SOA的生成过程显著地受控于大气光化学活性.深圳冬季大气SOA生成最活跃的时段约为9～15时,期间SOA/BC比值增长了122%.本文为研究我国大气二次有机气溶胶提供了一种新的技术方法和思路.     

大气有机硫酸酯化合物的特征及形成机制

本文总结了大气二次有机气溶胶的重要组分——有机硫酸酯化合物的特征及其形成机制的研究进展,并对相关研究进行了展望。近年来,通过实验室模拟与欧美地区的实际大气气溶胶样品的分析对比,发现有机硫酸酯化合物多由异戊二烯、α-/β-蒎烯以及其他单萜烯和倍半萜烯等经OH自由基、NO₃自由基或臭氧氧化后的反应产物与硫酸或硫酸盐气溶胶进一步反应而形成。有机硫酸酯化合物也可以通过硫酸或硫酸盐气溶胶反应性获取乙二醛等羰基化合物而形成。硫酸盐气溶胶酸性的增强会促进有机硫酸酯化合物的生成。有机硫酸酯化合物在水溶液中比较稳定,强酸性条件下才会发生水解作用。目前有机硫酸酯化合物的有效检测手段是离线电喷雾电离质谱(electrospray ionization mass spectrometry, ESI-MS)或在线气溶胶质谱(aerosol mass spectrometry, AMS)方法。     

大气颗粒物中棕色碳的化学组成、来源和生成机制

大气颗粒物中棕色碳(BrC)在近紫外波段具有强吸光性,并因其显著的气候效应被广泛关注。BrC组成、来源、演变和光学性质的不确定性是造成气候模型估算气溶胶辐射强迫不确定性的重要因素。本文综述了大气颗粒物中BrC的化学组成、来源和生成机制,聚焦分子水平上BrC组成、二次生成机制和吸光间的关联。大气颗粒物中BrC的主要类别包括有机溶剂(甲醇)提取的碳质组分、水溶性有机碳及类腐殖质; 分子水平上,硝基芳香烃和含氮杂环有机物是BrC的主要发色团。BrC的来源包括生物质等不完全燃烧一次排放和挥发性有机物氧化二次生成; 二次生成途径主要包括人为源芳香烃氧化生成硝基芳香烃等含氮组分、羰基化合物与铵/胺反应生成含氮杂环组分或低聚物。前体物和反应条件影响二次生成BrC的组成和吸光性质; BrC在大气传输过程中还会发生“光漂白”现象。在分子水平上识别和阐明BrC的发色团、二次生成机制及其演变过程是未来该领域的重点研究方向。     

Low‐Molecular Weight and Oligomeric Components in Secondary Organic Aerosol from the Photooxidation of p‐Xylene

A laboratory study was performed to investigate the composition of secondary organic aerosol (SOA) products from photooxidation of the aromatic hydrocarbon p‐xylene. The experiments were conducted by irradiating p‐xylene/CH₃ONO/NO/air mixtures in a home‐made smog chamber. The aerosol time‐of‐flight mass spectrometer (ATOFMS) was used to measure the size and the chemical composition of individual secondary organic aerosol particles in real‐time. According to a large number of single aerosol diameters and mass spectra, the size distribution and chemical composition of SOA were determined statistically. Experimental results showed that aerosol created by p‐xylene photooxidation is predominantly in the form of fine particles, which have diameters less than 2.5 μm (i.e. PM2.5), and aromatic aldehyde, unsaturated dicarbonys, hydroxyl dicarbonys, and organic acid are major product components in the SOA after 2 hours photooxidation. After aging for more than 8 hours, about 10% of the particle mass consists of oligomers with a molecular mass up to 600 daltons. The possible reaction mechanisms leading to these products are also proposed.     

Chemical Composition and Reaction Mechanisms for Secondary Organic Aerosol from Photooxidation of Toluene

A laboratory study was carried out to investigate the secondary organic aerosol (SOA) products from photooxidation of the aromatic hydrocarbon toluene. The experiments were conducted by irradiating toluene/CH₃ONO/NO/air mixtures in a home‐made smog chamber. The aerosol time‐of‐flight mass spectrometer (ATOFMS) was used to measure the size and the chemical composition of individual secondary organic aerosol particles in real‐time. According to a large number of single aerosol diameters and mass spectra, we obtained the size distribution and chemical composition of SOA statistically. Expeperimental results showed that aerosol created by toluene photooxidation is predominantly in the form of fine particles, which have diameters less than 2.5 μm (i.e. PM2.5), and the predominant components of aerosol are furane, methyl glyoxylic acid, phenol, benzaldehyde, benzyl alcohol, cresol, 3‐hydroxy‐2,4‐dioxo‐pentanal, methyl nitrophenol, and 5‐hydroxy‐4,6‐dioxo‐2‐heptenal. The possible reaction mechanisms leading to these products were also discussed.     

Real-time detection of individual secondary organic aerosol particle from photooxidation of toluene using aerosol time of flight mass spectrometer

Aromatic hydrocarbons are air pollutants in urban atmosphere and mainly from anthropogenic sources, i.e., emission from automotive exhaust and productive process of industry, and they constitute an important fraction of total volatile organic compounds (VOCs). Photochemical ozone and secondary organic aerosols (SOA) could be formed from the photochemical proc- esses of aromatic hydrocarbons. SOA may impact visibility of air, formation of clouds, change of the climate, and human health serio…     

Real-time analysis of secondary organic aerosol particles formed from cyclohexene ozonolysis using a laser-ionization single-particle aerosol mass spectrometer.

A real-time analysis of secondary organic aerosol (SOA) particles formed from cyclohexene ozonolysis in a smog chamber was performed using a laser-ionization single-particle aerosol mass spectrometer (LISPA-MS). The instrument obtains both size and chemical compositions of individual aerosol particles with a high time-resolution (approximately 2 s at the maximum). Both positive and negative-ion mass spectra are obtained. Standard particles generated from dicarboxylic acid solutions using an atomizer were also analyzed. For both standard and SOA particles, the negative-ion mass spectra provided information about the molecular weights of the organic compounds in the particles, since the intense ions in the negative-ion mass spectra are mainly attributable to the molecular-related ions [M-H]-. It was demonstrated that the real-time single-particle analysis of SOA particles by the LISPA-MS technique can reveal the formation and transformation processes of SOA particle in smog chambers.     

Identification of secondary organic aerosols based on aerosol mass spectrometry

Secondary organic aerosol (SOA) is one of the major components of aerosols in the atmosphere and has not been well understood so far. Due to the complex chemical composition of organic aerosols, the identification of SOA has been a hotspot and difficult issue in the field of aerosol study. This study attempts to quantitatively identify SOA in winter of Shenzhen based on positive matrix factorization (PMF) analysis. Major sources were resolved and SOA was identified subsequently according to the characteristic ion fragments measured by highly time-resolved aerosol mass spectrometer measurement. It showed that in the winter of Shenzhen the average SOA concentration was 9.41 ± 6.33 μg/m³, accounting for 39.9 ± 21.8% of the total organic mass. Compared with primary organic aerosol (POA), the SOA concentrations had no large variation, suggestive of characteristics of regional secondary pollutants. The ratio of SOA/BC had pronounced diurnal variation, similar to that of O _x (O₃+NO₂), indicating SOA formation was significantly controlled by activity of photochemistry in the atmosphere. The most effective period for SOA formation was from 9 am ～3 pm since the SOA/BC ratio increased by 122% during this period. This study provides a new technical method and a new idea for SOA investigation.     

Secondary organic aerosol formation during the photooxidation of toluene: NOx dependence of chemical composition

The photooxidation of toluene is a potential source of secondary organic aerosol (SOA) in urban air, but only a small portion of the compounds present in SOA have been identified. In this study, we analyzed the chemical compositions of SOA produced by photoirradiation of the toluene/NOx/air system in laboratory chamber experiments by a combination of liquid chromatography-mass spectrometry, hybrid high-performance liquid chromatography-mass spectrometry, and iodometry-spectrophotometry. The dependence of the chemical composition on the initial NOx concentration was examined at initial NO concentrations ([NO]0) of 0.2 and 1 ppmv. Fifteen semivolatile products, including aromatic and ring-cleavage compounds, were quantified. However, the quantified products comprised only a small portion ( approximately 1 wt %) of the total aerosol mass. The total SOA yield ( approximately 13 wt %), the ratio of organic peroxides to total SOA mass ( approximately 17 wt %), and the density of SOA ( approximately 1.4 g cm-3) were independent of the NOx level, suggesting that the reaction mechanisms of the formation of major SOA products at [NO]0 = 0.2 and 1 ppmv are essentially the same. The negative-ion mass spectra of SOA samples showed that ion signals attributed to hemiacetal oligomers and/or decomposition products of peroxy hemiacetal oligomers were detected in the range of mass-to-charge ratios (m/z) between 200 and 500. The highest signals were detected at m/z = 155 and 177, and these were tentatively assigned to C7 unsaturated oxacyclic oxocarboxylic acids and C7 unsaturated oxacyclic dicarboxylic acids, respectively. We conclude that the major chemical components of the aerosol are hemiacetal and peroxy hemiacetal oligomers and low-molecular-weight dicarboxylic acids.     

Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition

The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.     

Products and mechanism of secondary organic aerosol formation from reactions of linear alkenes with NO3 radicals

Secondary organic aerosol (SOA) formation from reactions of linear alkenes with NO(3) radicals was investigated in an environmental chamber using a thermal desorption particle beam mass spectrometer for particle analysis. A general chemical mechanism was developed to explain the formation of the observed SOA products. The major first-generation SOA products were hydroxynitrates, carbonylnitrates, nitrooxy peroxynitrates, dihydroxynitrates, and dihydroxy peroxynitrates. The major second-generation SOA products were hydroxy and oxo dinitrooxytetrahydrofurans, which have not been observed previously. The latter compounds were formed by a series of reactions in which delta-hydroxycarbonyls isomerize to cyclic hemiacetals, which then dehydrate to form substituted dihydrofurans (unsaturated compounds) that rapidly react with NO(3) radicals to form very low volatility products. For the approximately 1 ppmv alkene concentrations used here, aerosol formed only for alkenes C(7) or larger. SOA formed from C(7)-C(9) alkenes consisted only of second-generation products, whereas for larger alkenes first-generation products were also present and contributions increased with increasing carbon number apparently due to the formation of lower volatility products. The estimated mass fractions of first- and second-generation products were approximately 50:50, 30:70, 10:90, and 0:100, for 1-tetradecene, 1-dodecene, 1-decene, and 1-octene SOA, respectively. This study shows that delta-hydroxycarbonyls play a key role in the formation of SOA in alkene-NO(3) reactions and are likely to be important in other systems because delta-hydroxycarbonyls can also be formed from reactions of OH radicals and O(3) with hydrocarbons.     

Mass Spectrometry Study of OH-initiated Photooxidation of Toluene

The composition of products formed from photooxidation of the aromatic hydrocarbon toluene was investigated. The OH-initiated photooxidation experiments were conducted by irradiating toluene/CH₃ONO/NO/air mixtures in a smog chamber, the gaseous products were detected under the supersonic beam conditions by utilizing vacuum ultraviolet pho-toionization mass spectrometer using synchrotron radiation in real-time. And an aerosol time-of-flight mass spectrometer was used to provide on-line measurements of the individ-ual secondary organic aerosol particle resulting from irradiating toluene. The experimen-tal results demonstrated that there were some differences between the gaseous products and that of particle-phase, the products of glyoxal, 2-hydroxyl-3-oxo-butanal, nitrotoluene, and methyl-nitrophenol only existed in the particle-phase. However, furane, methylglyoxal, 2-methylfurane, benzaldehyde, cresol, and benzoic acid were the predominant photooxidation products in both the gas phase and particle phase.