仲丁醇对苯乙烯臭氧化反应生成二次有机气溶胶的影响:实验和模型研究

通过烟雾箱实验,研究了仲丁醇对苯乙烯臭氧化反应生成二次有机气溶胶(SOA)的影响.结果发现,在烟雾箱实验中,过量仲丁醇的加入导致生成SOA的产率明显下降.同时,结合MCM气相机理和气-粒分配理论,将Criegee中间体与醛类的双分子反应添加到箱式模型中模拟烟雾箱中SOA的生成过程.模拟结果表明,在没有仲丁醇存在的情况下,次级臭氧化物在SOA组分中占1/2左右的比例.仲丁醇的加入消耗了大量的·OH,同时使得[HO_2]/[RO_2]比值升高,影响自由基相关的反应机制,使得SOA产率下降.另外,研究发现,Criegee中间体与醛类反应的速率常数也是影响SOA生成模拟的一个重要参数,需要进一步开展相关的动力学实验和理论研究.     

Second organic aerosol formation from the ozonolysis of α-pinene in the presence of dry submicron ammonium sulfate aerosol

An indoor chamber facility is described for investigation of atmospheric aerosol chemistry. Two sets of α-pinene ozonolysis experiments were conducted in the presence of dry ammonium sulfate seed particle: ozone limited experiments and α-pinene limited experiments. The concentration of gas phase and particle phase species was monitored continuously by on-line instruments and recorded automatically by data sampling system. The evolution of size distribution was measured by a scanning mobility particle sizer ...     

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.     

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.     

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.     

Characterization of particulate products for aging of ethylbenzene secondary organic aerosol in the presence of ammonium sulfate seed aerosol

Aging of secondary organic aerosol(SOA) particles formed from OH– initiated oxidation of ethylbenzene in the presence of high mass(100–300 μg/m~3) concentrations of(NH_4)_2SO_4seed aerosol was investigated in a home-made smog chamber in this study.The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer(ALTOFMS) coupled with a Fuzzy C-Means(FCM) clustering algorithm.Experimental results showed that nitrophenol,ethyl-nitrophenol,2,4-dinitrophenol,methyl glyoxylic acid,5-ethyl-6-oxo-2,4-hexadienoic acid,2-ethyl-2,4-hexadiendioic acid,2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid,1H-imidazole,hydrated N-glyoxal substituted1H-imidazole,hydrated glyoxal dimer substituted imidazole,1H-imidazole-2-carbaldehyde,N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight(HMW) components were the predominant products in the aged particles.Compared to the previous aromatic SOA aging studies,imidazole compounds,which can absorb solar radiation effectively,were newly detected in aged ethylbenzene SOA in the presence of high concentrations of(NH_4)_2SO_4seed aerosol.These findings provide new information for discussing aromatic SOA aging mechanisms.     

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.     

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.     

硫酸铵细粒子对苯二次有机气溶胶光学特性的影响

苯系物光氧化产生的二次有机气溶胶(SOA)能够散射、吸收大气辐射,扰动区域气候变化.硫酸铵((NH4)2SO4)是大气中常见的无机细粒子,其大的比表面积可作为半挥发性化合物凝结和反应中心,进而影响SOA的化学组分和光学特性.本文采用烟雾箱研究(NH4)2SO4细粒子对苯SOA在200～600 nm范围内的平均质量吸收系...     

氨对甲苯二次有机气溶胶形成和化学组分的影响研究

氨(NH_3)是大气中常见的主要碱性污染气体,能够影响二次有机气溶胶(SOA)的形成和化学组分.本文利用自制的烟雾腔系统开展了NH_3对甲苯SOA形成和化学组分的影响研究,先后采用扫描移动粒径谱仪(SMPS)、气溶胶激光飞行时间质谱仪(ALTOFMS)、紫外-可见分光光度计(UV-Vis)、衰减全反射傅里叶变换红外光谱仪(ATR-FTIR)和荧光光谱仪(MF)测量反应产生的SOA粒子的物理化学性质.结果显示,在光照60 min的时间范围内,有NH_3条件下形成的SOA质量浓度和中心粒径相比于无NH_3条件下分别增加了50%和25%,这说明NH_3能够显著促进甲苯SOA的形成.与无NH_3条件下相比,NH_3存在时甲苯SOA化学组分的紫外可见吸收光谱在270 nm处有明显的吸收峰;红外吸收光谱出现了CN、C—N、N—H键的吸收峰;激光解吸附质谱图中含有m/z=67(C_3H_3N_2~+)、m/z=41(C_2H_2N~+)和m/z=28(CH2N+)碎片峰.这些谱图信息综合表明是NH_3和甲苯SOA中的二醛组分反应形成了咪唑类新产物.这为研究人为源SOA的形成机制提供了实验依据.     

大气中挥发性有机物(VOCs)对二次有机气溶胶(SOA)生成贡献的参数化估算

大气中二次有机气溶胶(SOA)是PM25中的重要组成部分,挥发性有机物(VOCs)的光化学氧化是其主要来源之一.从VOCs转化生成SOA的过程非常复杂,参数化方法是一种相对简化的估算方式,可以用于区分不同VOCs物种对SOA生成的贡献.本文介绍了基于二产物和基于挥发性分级两种常用的参数化估算方法,并总结分析文献报道的SOA估算结果.文章中也指出现在的参数化估算还存在一些问题,如何准确量化VOCs向SOA的转化过程将是大气化学未来的重要研究工作.     

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.     

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.     

用于模拟SOA形成的烟雾腔的构造和表征

为研究二次有机气溶胶的形成机理,设计制造了一种用于模拟二次有机气溶胶的形成过程烟雾腔实验系统,该系统主要包括样品进样系统,模拟反应系统即烟雾腔系统和产物检测系统三个部分,具有实时在线检测、效率高等优点。利用该实验装置模拟开展大气中含量较高的芳香烃化合物光氧化产生二次有机气溶胶的过程,使用TSI3321空气动力学直径测量系统、气溶胶飞行时间质谱等多种检测手段对二次有机气溶胶的形成进行表征。空白实验和羟基启动的光氧化实验结果表明烟雾腔内的气溶胶粒子是在黑光灯辐照下·OH自由基启动反应物光氧化产生的。实验结果表明研制的烟雾腔系统可以很好地实现对二次有机气溶胶形成过程的模拟和表征。     

成都秋季大气污染过程VOCs特征及SOA生成潜势

利用在线气相色谱-质谱（GC-FID/MS）监测系统,对成都市城区秋季典型大气污染期间环境空气中的77种挥发性有机物（VOCs）进行连续监测,分析了污染前期、污染中期、污染后期VOCs的污染特征、日变化规律.结果表明,成都市城区典型污染前期VOCs体积分数为38.9×10^-9;污染中期VOCs体积分数迅速增加,比污染前期高3.7倍,达到143.4×10^-9,污染后期VOCs体积分数为35.7×10^-9.污染前期VOCs日变化不明显,污染中期、后期VOCs日变化呈双峰性,分别出现在每天车流量高峰时段.此外,利用气溶胶生成系数（FAC）评估了不同污染阶段VOCs对二次有机气溶胶（SOA）的生成潜势,污染前期、污染中期、污染后期SOA浓度值分别为1.1,3.1,1.5 μg/m³,芳香烃是SOA的主要前体物.     

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.     

Emission factors, ozone and secondary organic aerosol formation potential of volatile organic compounds emitted from industrial biomass boilers

To evaluate the potential benefits of biomass use for air pollution control, this paper identified and quantified the emissions of major reactive organic compounds anticipated from biomass-fired industrial boilers. Wood pellets(WP) and straw pellets(SP) were burned to determine the volatile organic compound emission profiles for each biomass-boiler combination. More than 100 types of volatile organic compounds(VOCs) were measured from the two biomass boilers. The measured VOC species included alkanes, alkenes and acetylenes, aromatics, halocarbons and carbonyls. A single coal-fired boiler(CB) was also studied to provide a basis for comparison. Biomass boiler 1(BB1) emitted relatively high proportions of alkanes(28.9%–38.1% by mass) and alkenes and acetylenes(23.4%–40.8%),while biomass boiler 2(BB2) emitted relatively high proportions of aromatics(27.9%–29.2%)and oxygenated VOCs(33.0%–44.8%). The total VOC(TVOC) emission factors from BB1(128.59–146.16 mg/kg) were higher than those from BB2(41.26–85.29 mg/kg). The total ozone formation potential(OFP) ranged from 6.26 to 81.75 mg/m~3 with an average of 33.66 mg/m~3 for the two biomass boilers. The total secondary organic aerosol potential(SOAP) ranged from 61.56 to 211.67 mg/m~3 with an average of 142.27 mg/m~3 for the two biomass boilers.The emission factors(EFs) of TVOCs from biomass boilers in this study were similar to those for industrial coal-fired boilers with the same thermal power. These data can supplement existing VOC emission factors for biomass combustion and thus enrich the VOC emission inventory.     

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...     

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m³, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.