SO2-NO2-NH3-H2O四元反应体系中气溶胶的生成特性

通过烟雾箱实验,研究了SO₂-NO₂-NH₃-H₂O四元反应体系在气-粒转化过程中新形成颗粒物数浓度与粒径分布的变化.研究发现,SO₂-NO₂-NH₃-H₂O四元反应体系具有显著的成核能力,且其成核强度大,持续时间短.当SO₂、NO₂浓度为200mg/m³,NH₃浓度为12x10^-6时,反应体系的气溶胶总个数浓度在2min时达到峰值2.5x10⁶cm^-3.缺少任一种气体均会使气溶胶成核强度下降.SO₂、NO₂及NH₃浓度分别为0的工况下气溶胶总个数浓度峰值分别下降了41.0%、83.6%及98.5%.在电厂污染气体排放浓度区间内,NO₂对气溶胶生成影响大于SO₂.燃煤电厂控制NO_x排放浓度对改善烟囱出口气溶胶数浓度更有效.在实验基础上,对颗粒物成核特性进行拟合,反应体系在气-粒转化过程中产生的新颗粒物总个数浓度及中值粒径与气态前体物浓度线性相关;采用布朗团聚模型对气溶胶成核后的团聚过程总个数浓度及粒径变化进行模拟计算,根据给定的燃煤电厂SO₂、NO₂、NH₃排放浓度,给出预测气溶胶颗粒成核速率、粒径分布及总个数浓度变化的方法.     

Eperimental study of photooxidation products of ethylbenzene

Smog chamber experiments were performed to investigate the composition of products formed from photooxidation of aromatic hydrocarbon ethylbenzene.Vacuum ultraviolet photoionization mass spectrometer and aerosol time-of-flight mass spectrometer were used to measure the products in the gas and particle phases in real-time.Experimental results demonstrated that ethylphenol,methylglyoxal,phenol,benzaldehyde,and 2-ethylfurane were the predominant photooxidation products in both the gas and particle phases.However,there were some differences between detected gas phase products and those of particle phase,for example,2-ethylfurane,ethylglyoxylie acid,nitroethylbenzene,3,4-dioxopentanal and ethyl-nitrophenol were only existing in the particle-phase.The possible reaction mechanisms leading to these products were also discussed and proposed.     

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.     

京津冀PM2.5浓度控制目标可达性分析

雾霾污染已成为京津冀地区最突出的环境问题,国务院颁布了《大气污染防治行动计划》,明确提出了京津冀地区雾霾治理的浓度目标和减排措施。但是这些减排措施能否够实现PM2.5的浓度目标呢?本文基于数据分析方法,量化了2013—2014年京津冀地区PM2.5浓度与污染物排放量的关系,预测了现有减排措施可以达到的PM2.5浓度以及实现既定的PM2.5浓度目标的大气污染物减排要求,对"大气十条"减排政策的有效性进行了科学评估。结果显示,现有的减排措施难以实现PM2.5浓度控制目标,天津和河北的大多数地市需要进一步加大污染物减排力度。河北的部分地市即使实现了PM2.5浓度下降25%的目标,PM2.5浓度仍然过高,应改下降百分比为绝对值目标。北京的污染物减排率过高,减排难度较大,可以考虑一个现实合理的PM2.5浓度目标和污染物减排计划。由于污染物减排行动涉及区域经济和民生保障,PM2.5浓度受到风力等自然因素的影响较大,京津冀地区的雾霾治理应确定现实可行的浓度控制目标,并制定相应的污染物排放量管理目标。     

Smog chamber study on the evolution of fume from residential coal combustion

Domestic coal stoves are widely used in countryside and greenbelt residents in China for heating and cooking, and emit considerable pollutants to the atmosphere because of no treatment of their exhaust, which can result in deteriorating local air quality. In this study, a dynamic smog chamber was used to investigate the real-time emissions of gaseous and particulate pollutants during the combustion process and a static smog chamber was used to investigate the fume evolution under simulate light irradiation. The real-time emissions revealed that the total hydrocarbon (THC) and CO increased sharply after ignition, and then quickly decreased, indicating volatilization of hydrocarbons with low molecular weight and incomplete combustion at the beginning stage of combustion made great contribution to these pollutants. There was evident shoulder peak around 10 min combustion for both THC and CO, revealing the emissions from vitrinite combustion. Additionally, another broad emission peak of CO after 30 min was also observed, which was ascribed to the incomplete combustion of the inertinite. Compared with THC and CO, there was only one emission peak for NOx, SO₂ and particular matters at the beginning stage of combustion. The fume evolution with static chamber simulation indicated that evident consumption of SO₂ and NOx as well as new particle formation were observed. The consumption rates for SO₂ and NOx were about 3.44% hr^-1 and 3.68% hr^-1, the new particle formation of nuclei particles grew at a rate of 16.03 nm/hr during the first reaction hour, and the increase of the diameter of accumulation mode particles was evident. The addition of isoprene to the diluted mixture of the fume could promote O₃ and secondary particle formation.     

浅析光化学烟雾的污染问题

光化学烟雾频繁发生的罪魁祸首是工业废气和机动车尾气污染。本文在简要分析了光化学烟雾的形成机理、生成条件及对生物体的危害后,提出从控制污染源着手来预防光化学烟雾频发的对策。     

Characterization of products from photooxidation of toluene

Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer （FTIR）. Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups （C-O）, hydroxyl groups （-OH）, carboxylic acid （- COOH）, C-C bonding, N O bonding and C-H bonding （C H）, was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer （ATOFMS）. It was found that there are some differcnccs between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while kctoncs, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.     

Ground-level ozone in the Pearl River Delta and the roles of VOC and NO(x) in its production

In many regions of China, very rapid economic growth has been accompanied by air pollution caused by vehicle emissions. In one of these regions, the Pearl River Delta, the variations of ground-level ozone and its precursors were investigated. Overall, the ambient concentrations of NO(2) increased quickly between 1995 and 1996, but then slightly decreased due to stringent nitrogen oxide (NO(x)) emission controls. Nonetheless, ambient NO(2) levels in the Pearl River Delta remained high. The regional average concentrations of volatile organic compounds (VOCs) were 290 ppbC in summer and 190 ppbC in autumn. Local emissions and long-distance transportation of pollutants play important roles in the regional distribution of VOCs. Ambient O(3) production is significant in urban areas and also downwind of cities. The relative incremental reactivities (RIRs), determined by an observation-based model, showed that ground-level ozone formation in the Guangzhou urban area is generally limited by the concentrations of VOCs, but there are also measurable impacts of NO(x).     

相对速率法测OH自由基与几种低碳醇的反应速率常数

在 2 99± 2K温度下 ,以甲醇为参照物 ,采用相对速率方法得到了几种醇与OH自由基在气相中的反应速率常数 ,这些速率常数分别为 (单位为 :10 5m3·mol-1·s-1) :乙醇k1=17 6 ,正丙醇k2 =35 2 ,2 丙醇k3=31 2 ,正丁醇k4 =48 2 ,2 甲基—1 丙醇k5=6 2 0 ,2 甲基— 2 丙醇k6=5 36 ,正戊醇k7=5 1 4,3 甲基— 1 丁醇k8=6 8 6 .其中 2 甲基— 1 丙醇的速率常数在本文中是首次报道 .根据各自的反应速率常数计算得到它们在大气中的平均寿命分别为 :τ1=95 1h ,τ2 =47 5h ,τ3=5 3 6h ,τ4 =34 7h ,τ5=2 7 0h ,τ6=312h ,τ7=32 6h ,τ8=2 4 4h .     

硫酸铵气溶胶对甲苯-NOx-空气体系光化学反应的影响

利用大气模拟烟雾箱,研究了硫酸铵气溶胶对甲苯-NO_x-空气体系光化学反应的影响.结果表明,硫酸铵作为气溶胶种子,其存在可以加快反应过程中颗粒物（particle matter, PM）的生成速度,并提高甲苯的气溶胶产率.在高浓度的硫酸铵气溶胶种子条件下,其初始浓度对反应过程中NO_x、NO和O₃的浓度变化没有明显的影响,但对二次有机气溶胶（secondary organic aerosol, SOA）的生成有显著影响.在硫酸铵气溶胶种子浓度小于160 μg·m^-3时,SOA的产率随初始气溶胶种子浓度的增大而增大,从最小7.2％到最大11.7％,其增幅超过60％.