大气复合污染及灰霾形成中非均相化学过程的作用

城市和区域大气复合污染的特征为污染源排放的一次污染物通过大气中的化学反应生成高浓度的氧化剂(臭氧等)及细颗粒物等二次污染物,它们在静稳天气下积累,导致低能见度的灰霾现象并严重影响人体健康和气候.大气复合污染中同时存在高浓度的一次排放和二次转化的气态及颗粒污染物,这为细颗粒表面非均相反应提供了充足的反应物;而气态污染物在细颗粒表面的非均相反应可改变大气氧化性及颗粒物的化学组分、物化性质和光学性质,从而可能对大气复合污染和灰霾的形成起到促进的作用.利用漫反射红外傅里叶变换光谱和单颗粒显微拉曼原位在线技术,我们对大气气态污染物NO2、SO2、O3、甲醛在CaCO3、高岭石、蒙脱石、NaCl、海盐、Al2O3和TiO2等大气主要颗粒物表面的反应进行了系统的反应动力学和机制研究,我们发现反应主要产物为硫酸盐、硝酸盐或甲酸盐,它们可极大改变颗粒物吸湿性和消光性质.通过分析这些非均相反应的动力学过程,我们识别出NO2-颗粒物-H2O、SO2-颗粒物-O3、有机物/SO2-颗粒物-光照等三元反应体系的协同作用机制,这些协同机制对于阐明大气复合污染及灰霾形成的反馈机制和非线性过程提供了实验证据和理论依据.

The roles of heterogeneous chemical processes in the formation of an air pollution complex and gray haze

Urban and regional air pollutions are characterized by high concentrations of secondary pollutants such as photo-oxidants（mainly ozone） and fine particulate matter,which are formed through chemical reactions of the primary pollutants emitted from various sources.The accumulation of these pollutants under stagnant meteorological conditions results in the formation of gray haze,reducing visibility and causing major impacts on human health and climate.In an air pollution complex,the coexistence of high concentrations of primary and secondary gaseous and particulate pollutants provides a large amount of reactants for heterogeneous reactions on the surface of fine particles;these reactions change the oxidizing capacity of the atmosphere,as well as chemical compositions along with the physicochemical and optical properties of particulate matter,thereby accelerating formation of the air pollution complex and gray haze.Using in situ technologies,such as diffuse reflectance infrared Fourier-transform spectroscopy and single-particle Raman spectroscopy,we systematically investigated the reaction kinetics and mechanisms of gaseous pollutants（i.e.,NO2,SO2,O3,and formaldehyde） on the surfaces of the major components of atmospheric particles such as CaCO3,kaolinite,montmorillonite,NaCl,sea salt,Al2O3,and TiO2.We found that the main reaction products were sulfate,nitrate,or formate,which can change the hygroscopicity and extinction parameters of those particles significantly.By analyzing the reaction kinetics of these heterogeneous reactions,we identified synergetic mechanisms of the three ternary reaction systems,i.e.,NO2 particles-H2O,SO2 particles-O3,and organics/SO2/NOx-particles-UV illumination.These synergetic mechanisms can provide experimental and theoretical bases for understanding the feedback mechanisms and nonlinear processes in the formation of an air pollution complex and gray haze.