State Environmental Protection Key Laboratory of Urban Ambient Air Particulate Matter Pollution Prevention and Control, College of Environmental Science and Engineering , Nankai University , Tianjin , 300071 , China.
Laboratory of Atmospheric Processes and their Impacts, School of Architecture, Civil and Environmental Engineering , École Polytechnique Fédérale de Lausanne , Lausanne , CH-1015 , Switzerland.
Environ Sci Technol. 2019 Mar 19;53(6):3048-3057. doi: 10.1021/acs.est.8b06524. Epub 2019 Mar 7.
Nitrate is one of the most abundant inorganic water-soluble ions in fine particulate matter (PM). However, the formation mechanism of nitrate in the ambient atmosphere, especially the impacts of its semivolatility and the various existing forms of nitrogen, remain under-investigated. In this study, hourly ambient observations of speciated PM components (NO, SO, etc.) were collected in Tianjin, China. Source contributions were analyzed by PMF/ME2 (Positive Matrix Factorization using the Multilinear Engine 2) program, and pH were estimated by ISORROPIA-II, to investigate the relationship between pH and nitrate. Five sources (factors) were resolved: secondary sulfate (SS), secondary nitrate (SN), dust, vehicle and coal combustion. SN and pH showed a triangle-shaped relationship. When SS was high, the fraction of nitrate partitioning into the aerosol phase exhibits a characteristic "S-curve" relationship with pH for different seasons. An index ( I) is developed and combined with pH to explore the sensitive regions of "S-curve". Controlling the emissions of anions (SO, Cl), cations (Ca, Mg, etc.) and gases (NO , NH, SO, etc.) will change pH, potentially reducing or increasing SN. The findings of this work provide an effective approach for exploring the formation mechanisms of nitrate under different influencing factors (sources, pH, and I).
硝酸盐是细颗粒物(PM)中含量最丰富的无机水溶性离子之一。然而,环境大气中硝酸盐的形成机制,特别是其半挥发性和各种形态氮的影响,仍未得到充分研究。本研究在中国天津进行了每小时一次的 PM 成分(NO、SO 等)的环境观测。采用 PMF/ME2(多线性引擎 2 的正矩阵因子分解)程序分析源贡献,利用 ISORROPIA-II 估算 pH 值,以研究 pH 值与硝酸盐之间的关系。解析出五个来源(因子):二次硫酸盐(SS)、二次硝酸盐(SN)、扬尘、机动车和煤炭燃烧。SN 和 pH 值呈三角形关系。当 SS 含量较高时,硝酸盐在气溶胶相中的分配比例与不同季节的 pH 值呈特征性“S 型曲线”关系。本文提出了一个指数(I),并结合 pH 值来探索“S 型曲线”的敏感区域。控制阴离子(SO、Cl)、阳离子(Ca、Mg 等)和气体(NO、NH、SO 等)的排放将改变 pH 值,从而可能减少或增加 SN。本研究为探索不同影响因素(来源、pH 值和 I)下硝酸盐形成机制提供了一种有效方法。