羟基自由基浓度对二次有机气溶胶形成的影响

在烟雾腔中光照甲苯/亚硝酸甲酯(CH3ONO)/NO混合物,模拟了羟基自由基(OH·)启动甲苯光氧化反应生成二次有机气溶胶的过程.结果表明,二次有机气溶胶的生成数量随着CH3ONO的浓度增加而增加;在CH3ONO浓度为225.4μL/L时,二次有机气溶胶的生成数量达到最大;此后,增加CH3ONO的浓度反而会降低二次有机气溶胶的粒子密度.因此,对于二次有机气溶胶的形成过程来说,存在一个羟基自由基浓度的最佳值.     

光化学烟雾箱的表征及初步应用

介绍了一套自制的用于光化学臭氧和二次有机气溶胶生成研究的室内烟雾箱系统,对该烟雾箱系统进行了一系列表征实验,包括活性物种的壁损失速率常数的测定,以及由CO-NOx光氧化实验确定的反应器内·OH源,并进行了乙烯-NOx和苯-NOx光氧化的初步实验.结果表明,O3和NO2在新反应袋中壁损失受湿度影响很小,而在旧反应袋中影响...     

酸性硫酸铵种子气溶胶对甲苯二次有机气溶胶形成和组分的影响研究

酸性硫酸铵是中国城市大气中常见的亚微米气溶胶颗粒,它在二次有机气溶胶（SOA）的形成中起着至关重要的作用.本文利用自制的烟雾腔系统开展了酸性硫酸铵种子气溶胶对甲苯SOA形成和化学组分的影响研究,采用PM_2.5粒子检测仪、高效液相色谱质谱仪和紫外-可见分光光度计测量反应产生的SOA粒子的浓度和组分.实验结果表明,酸性硫酸铵种子气溶胶能够显著促进甲苯SOA的形成.相比于没有种子气溶胶存在时,甲苯SOA中检测到的羧酸组分,甲苯光氧化产生的二醛化合物在酸性硫酸铵颗粒表面上发生非均相反应产生的咪唑类化合物是酸性硫酸铵种子气溶胶存在时甲苯SOA的主要组分.气相二醛化合物能在高浓度酸性硫酸铵种子气溶胶表面快速发生非均相酸催化反应产生咪唑类产物.这为研究高浓度酸性无机细粒子背景下,大气咪唑类含氮有机物棕色碳的形成机制研究提供了实验依据.     

氨与甲苯SOA形成含氮有机物的影响因素研究

利用自制的烟雾腔系统使臭氧光解产生OH自由基,启动甲苯光氧化产生二次有机气溶胶（SOA）粒子,在不同的实验条件下研究甲苯SOA与氨反应形成的含氮有机物,并采用紫外-可见分光光度计测量反应产物溶液在205和270nm处的吸光度,探究光照时间、甲苯、氨、臭氧浓度和相对湿度等环境因素对含氮有机物形成的影响规律.结果表明,有机酸铵和咪唑类产物的生成浓度随着紫外光照时间的延长,甲苯、氨和臭氧的浓度的增加而逐渐增大.但是当臭氧浓度超过一定值后,光解生成的高浓度OH自由基能够使甲苯光氧化产物变成更多的挥发性化合物,从而不利于含氮有机物的生成.水分子的增加会使臭氧光解产生的OH自由基浓度减少,从而导致有机酸铵和咪唑类产物的生成浓度随着相对湿度的增大而降低.这为研究人为源SOA颗粒中含氮有机物棕色碳的形成提供了实验依据.     

用于汽车尾气光氧化的烟雾箱研究及其表征实验

大气中光氧化反应是造成大气中复合污染,加剧中国大气环境污染的重要因素。为了研究汽车尾气在大气中的光氧化反应,设计制作了一套用于汽车尾气光氧化反应的较大容积的室内烟雾箱实验系统,该系统主要包括反应系统、进样系统和检测分析系统。反应系统采取了移动式对箱设置,尾气进样系统考虑了汽车尾气的排放特点,检测系统采取了负压采气装置。通过对该烟雾箱的光强分布、光解实验、NO_2及O_3衰减等系列的表征实验表明,该烟雾箱系统的一些性能较国内已有的烟雾箱有一定程度的提高,而且更适合于模拟汽车尾气的光氧化反应,同时,该系统具有采样方便、两箱对比和可模拟多种环境等特点。     

挥发性有机物生成二次有机气溶胶影响因素的研究进展

二次有机气溶胶(SOA)的生成不仅受前体物排放量的影响,还与一些环境因素有关。为了更为科学地提出SOA污染防治对策,可以采用烟雾箱对SOA生成的影响因素进行模拟研究。介绍了近年来烟雾箱的设计与表征方法,分析了温度、相对湿度、光照强度、种子气溶胶、SO_2、NO_x等典型影响因素的研究现状。指出了现有研究的不足,认为SOA生成过程的模拟工具升级、定性分析和复合影响因素探讨是今后研究的重点。     

氯化铁细粒子对苯二次有机气溶胶化学组分和光学性质的影响

铁离子是大气气溶胶中常见的重金属离子，它能够影响二次有机气溶胶（SOA）的化学组分和光学性质.本文利用烟雾腔系统研究氯化铁细粒子对苯SOA化学组分和光学性质的影响.与无细粒子条件相比，氯化铁细粒子存在时，苯SOA粒子的激光解吸附电离质谱出现m/z=164的离子峰，提取液的紫外可见吸收光谱在396 nm和700 nm附近存在吸收峰，电喷雾电离质谱含有m/z=234和272的质谱峰.综合这些谱图信息表明，苯光氧化产生的邻苯二酚等气相产物在细粒子表面与铁离子发生络合、氧化还原反应，产生苯醌类产物和二氯邻苯二酚合铁（Ⅲ）离子和二邻苯二酚合铁（Ⅲ）离子等金属有机物络合离子.这些产物具有较强的吸光能力，导致苯SOA粒子在200～1000 nm范围内的平均质量吸收系数（）值明显增大，并随着氯化铁细粒子浓度的增大而逐渐增大.这为重金属细粒子存在下金属有机络合物的形成机理和光学性质研究提供了实验依据.     

有机气溶胶的来源与形成研究现状

介绍了有机气溶胶来源与形成的研究现状,从有机气溶胶的化学组成特征、一次有机气溶胶的来源和二次有机气溶胶的形成机制论述其研究进展.一次有机气溶胶主要来源于烹调油烟、机动车排放、生物质燃烧、工业或民用燃油锅炉释放出的有机物,还有道路扬尘、沥青、刹车尘、轮胎屑、室外香烟烟雾、以及高等植物蜡、细菌活动和草本植物等.大气中的半挥发性有机物可通过物理和化学吸附形成二次有机气溶胶,一些挥发性有机物可通过气相化学反应转化为低挥发性的物质并形成二次有机气溶胶,其主要前体物是芳香族化合物,如苯、甲苯、二甲苯,以及烯烃、烷烃、环烷烃、萜烯和生物排放的非饱和氧化物.     

在线表征萘二次有机气溶胶硝基多环芳烃

硝基多环芳烃(NPAHs)广泛存在于大气气溶胶中,是棕色碳的重要组成部分.萘和其他多环芳烃是NPAHs的重要前体物.为研究NO₂对NPAHs形成的影响,本文利用气溶胶激光飞行时间质谱仪(ALTOFMS)在线测定不同NO₂浓度下萘光氧化形成的二次有机气溶胶(SOA)的NPAHs组分.实验结果表明,NO₂对NPAHs的产生和萘SOA的形成有促进作用.通过ALTOFMS在线检测、模糊C均值(FCM)聚类分析,结合离线电喷雾电离质谱验证,测得萘酚和羰基化合物是不存在NO₂时萘SOA粒子主要成分,而通过OH-萘加合物和萘酚硝化产生的硝基萘、二硝基萘、硝基萘酚和二硝基萘酚及其衍生物是NO₂存在时萘SOA粒子的主要组分.这为城市大气高浓度NO_x背景下,研究NPAHs的化学组分和形成机理提供了实验依据.     

氯化钙种子气溶胶对甲苯二次有机气溶胶与氨形成含氮有机物的影响

苯系物光氧化反应形成的二次有机气溶胶(SOA)是大气细粒子的重要组成部分.SOA羧酸和二元醛组分能与氨反应形成有机酸铵和咪唑类含氮有机物,它们能够吸收205 nm和270 nm的紫外辐射,是棕色碳的主要组分.氯化钙等无机种子气溶胶具有较大的比表面积,可为气相羰基化合物和氨提供凝结与反应载体,从而影响含氮有机物的形成.基于此,本文利用烟雾腔研究氯化钙种子气溶胶存在时甲苯SOA与氨的反应,采用紫外-可见分光光度计测量产物溶液在205 nm和270 nm处的吸光度,并定性研究不同浓度、湿度和酸度的氯化钙种子气溶胶对含氮有机物形成的影响.结果表明:氯化钙种子气溶胶能够促进甲苯SOA含氮有机物的形成;含氮有机物的生成浓度随着氯化钙种子气溶胶浓度和pH值的增加而逐渐增大.但当氯化钙种子气溶胶为碱性时,OH~-会与凝结的有机酸发生酸碱中和反应并抑制二元醛化合物水合形成四醇产物,从而不利于含氮有机物的生成;水分子的增加占据了氯化钙种子气溶胶表面的吸附活性位点,氨被吸附和凝结的量减少,从而导致含氮有机物的生成浓度随着相对湿度的增大而降低.本研究可为人为源SOA棕色碳的形成机制和化学组成研究提供实验依据.     

Effect of illumination intensity and light application time on secondary organic aerosol formation from the photooxidation of α-pinene

Secondary organic aerosol (SOA) formation from hydroxyl radical (OH.) initiated photooxidation of α-pinene was investigated in a home-made smog chamber. The size distribution of SOA particles was measured using aerodynamic particle sizer spectrometer. The effects of illumination intensity and light application time on SOA formation for α-pinene were evaluated. Experimental results show that the concentration of SOA particles increased significantly with an increasing of illumination intensity, and the light...     

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.     

大气模拟烟雾箱系统的研究进展

烟雾箱是研究大气光化学反应的主要工具.30年来国内外有多个研究机构建立了烟雾箱,并对各种光化学反应进行了研究,以收集数据来发展和检验大气光化学反应机理.从系统构造、配置仪器及所进行的光化学实验几个方面,综述了国内外烟雾箱系统的研究进展,其中背景影响较小的烟雾箱能为评价化学反应机理提供精度较高的数据,二次有机气溶胶(secondary organic aerosol,SOA)的形成机理成为目前的研究热点.     

Assessing the influence of environmental conditions on secondary organic aerosol formation from a typical biomass burning compound

The atmospheric chemistry in complex air pollution remains poorly understood. In order to probe how environmental conditions can impact the secondary organic aerosol (SOA) formation from biomass burning emissions, we investigated the photooxidation of 2,5-dimethylfuran (DMF) under different environmental conditions in a smog chamber. It was found that SO₂ could promote the formation of SOA and increase the amounts of inorganic salts produced during the photooxidation. The formation rate of SOA and the corresponding SOA mass concentration increased gradually with the increasing DMF/OH ratio. The addition of (NH₄)₂SO₄ seed aerosol accelerated the SOA formation rate and significantly shortened the time for the reaction to reach equilibrium. Additionally, a relatively high illumination intensity promoted the formation of OH radicals and, correspondingly, enhanced the photooxidation of DMF. However, the enhancement of light intensity accelerated the aging of SOA, which led to a gradual decrease of the SOA mass concentration. This work shows that by having varying influence on atmospheric chemical reactions, the same environmental factor can affect SOA formation in different ways. The present study is helpful for us to better understand atmospheric complex pollution.     

Chemical composition and size distribution of secondary organic aerosol formed from the photooxidation of isoprene

Photooxidation of isoprene leads to the formation of secondary organic aerosol (SOA). In this study, the chemical composition of SOA formed from OH-initiated photooxidation of isoprene has been investigated with gas chromatography/mass spectrometry (GC/MS) and a home-made aerosol time-of-flight mass spectrometer. Sampling particles generated in a home-made smog chamber. The size distribution of SOA particles was detected by a TSI 3321 aerodynamic particle size spectrometer in real time. Results showed that SOA created by isoprene photooxidation was predominantly in the form of fine particles, which have diameters less than 2.5 m. The obtained mass spectra of individual particles show that products of the OH-initiated oxidation of isoprene contain methyl vinyl ketone, methacrolein, formaldehyde, and some other hydroxycarbonyls. The possible reaction mechanisms leading to these products were also discussed.     

Review of the influencing factors of secondary organic aerosol formation and aging mechanism based on photochemical smog chamber simulation methods

The formation and aging mechanism of secondary organic aerosol (SOA) and its influencing factors have attracted increasing attention in recent years because of their effects on climate change, atmospheric quality and human health. However, there are still large errors between air quality model simulation results and field observations. The currently undetected components during the formation and aging of SOA due to the limitation of current monitoring techniques and the interactions among multiple SOA formation influencing factors might be the main reasons for the differences. In this paper, we present a detailed review of the complex dynamic physical and chemical processes and the corresponding influencing factors involved in SOA formation and aging. And all these results were mainly based the studies of photochemical smog chamber simulation. Although the properties of precursor volatile organic compounds (VOCs), oxidants (such as OH radicals), and atmospheric environmental factors (such as NO_x, SO₂, NH₃, light intensity, temperature, humidity and seed aerosols) jointly influence the products and yield of SOA, the nucleation and vapor pressure of these products were found to be the most fundamental aspects when interpreting the dynamics of the SOA formation and aging process. The development of techniques for measuring intermediate species in SOA generation processes and the study of SOA generation and aging mechanism in complex systems should be important topics of future SOA research.     

Size distribution of the secondary organic aerosol particles from the photooxidation of toluene

In a smog chamber, the photooxidation of toluene was initiated by hydroxyl radical （OH.） under different experimental conditions. The size distribution of secondary organic aerosol（SOA） particles from the above reaction was measured using aerodynamic particle sizer spectrometer. It was found from our experimental results that the number of SOA particles increased with increasing the concentration of toluene. As the reaction time prolonged, the sum of SOA particles was also increased. After a reaction time of 130 min, the concentration of secondary organic aerosol particles would be kept constant at 2300 particles/cm^3. Increasing illumination power of blacklamps could significantly induce a higher concentration of secondary organic aerosol particle. The density of SOA particles would also be increased with increasing concentration of CH30NO, however, it would be decreased as soon as the concentration of CH30NO was larger than 225.2 ppm. Nitrogen oxide with initial concentration higher than 30. 1 ppm was also found to have little effect on the formation of secondary organic aerosol.     

Ozone and secondary organic aerosol formation potential from anthropogenic volatile organic compounds emissions in China

Volatile organic compounds (VOCs) are major precursors for ozone and secondary organic aerosol (SOA), both of which greatly harm human health and significantly affect the Earth''s climate. We simultaneously estimated ozone and SOA formation from anthropogenic VOCs emissions in China by employing photochemical ozone creation potential (POCP) values and SOA yields. We gave special attention to large molecular species and adopted the SOA yield curves from latest smog chamber experiments. The estimation shows that alkylbenzenes are greatest contributors to both ozone and SOA formation (36.0% and 51.6%, respectively), while toluene and xylenes are largest contributing individual VOCs. Industry solvent use, industry process and domestic combustion are three sectors with the largest contributions to both ozone (24.7%, 23.0% and 17.8%, respectively) and SOA (22.9%, 34.6% and 19.6%, respectively) formation. In terms of the formation potential per unit VOCs emission, ozone is sensitive to open biomass burning, transportation, and domestic solvent use, and SOA is sensitive to industry process, domestic solvent use, and domestic combustion. Biomass stoves, paint application in industrial protection and buildings, adhesives application are key individual sources to ozone and SOA formation, whether measured by total contribution or contribution per unit VOCs emission. The results imply that current VOCs control policies should be extended to cover most important industrial sources, and the control measures for biomass stoves should be tightened. Finally, discrepant VOCs control policies should be implemented in different regions based on their ozone/aerosol concentration levels and dominant emission sources for ozone and SOA formation potential.     

光化学烟雾模拟实验系统

为开展光化学污染成因的敏感性分析,设计和建立了目前国内唯一的大型光化学烟雾模拟实验系统．该系统主要包括烟雾箱系统、空气充填置换系统、采样测试系统和记录显示控制系统等4个分系统．与国内外同类型实验系统相比,该系统具有烟雾箱在实验过程中受光均匀、换气系统快捷、效率高以及可实现两箱对比实验等特色．利用实验系统开展了光化学污染过程的模拟实验,得到了典型的污染特征．进行了同等条件的两箱对比实验,实验结果完全一致,表明该实验系统能够开展基于对比实验的敏感性分析研究,从而为进一步针对北京实际开展光化学污染的模拟研究奠定了良好的基础．     

Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

Secondary organic aerosol (SOA) formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber. The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer (ALTOFMS), respectively. According to a large number of single aerosol diameter and mass spectra, the size distribution and chemical composition of SOA were obtained statistically. Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles, which have diameters less than 2.5 m (i.e., PM2.5), and glyoxal, benzaldehyde, benzyl alcohol, benzoquinone, benzoic acid, benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA. The possible reaction mechanisms leading to these products are also proposed.