ALBERT

Description: Identification of particulate organosulfates in three megacities at the middle and lower reaches of the Yangtze River Atmospheric Chemistry and Physics Discussions, 15, 21415-21448, 2015 Author(s): X. K. Wang, S. Rossignol, Y. Ma, L. Yao, M. Y. Wang, J. M. Chen, C. George, and L. Wang PM 2.5 filter samples have been collected in three megacities i.e., Wuhan (WH), Nanjing (NJ), and Shanghai (SH) at the middle and lower reaches of the Yangtze River, respectively. Analysis of those samples using an ultra-high performance liquid chromatography (UHPLC) coupled to an orbitrap mass spectrometer (MS) allowed detection of about two hundred particulate organosulfates (OSs), including dozens of nitrooxy-organosulfates, at each location. While aliphatic OSs represented more than 78 % of the detected OSs at the three locations, aromatic OSs were much less abundant. OSs with two to four isomers accounted for about 50 % of the total OSs on average in these megacities, and the percentage of OSs with six and more isomers in WH was more significant than those in SH and NJ. The average molecular weight, and the degrees of oxidation and saturation of OSs in the WH summer samples were greater than those in WH winter samples. In SH, the average molecular weight and the degree of oxidation of OSs in summer samples were greater than those in winter samples, but the degree of saturation was similar between the two seasons. In summer, the average molecular weight, and the degrees of oxidation and unsaturation of OSs were smallest in WH among the three cities. Between NJ and SH, the average molecular weight and the degree of saturation of OSs were close and the degree of oxidation of OSs in NJ was smaller. Kendrick mass defect diagrams and Van Krevelen diagrams indicated that the characteristics of identified OSs between in NJ and in SH shared better similarity. In addition, the identity and abundance of OSs in SH showed clear seasonal and diurnal variations. OSs in summer were more abundant than they were in winter due to stronger photochemical reactions in summer. The relative abundance of OSs at night was greater than that in the daytime and more nitrooxy-OSs existed at night, probably because of active NO 3 radical chemistry at night. In SH summer samples, OSs with 5 and 10 carbons (C 5 and C 10 ) were the most abundant, indicating the importance of isoprene and monoterpenes as precursors of OSs, whereas the relative abundances of OSs with 8, 9, and more than 14 carbons (C 8 , C 9 , and C 14+ ) were also high in SH winter samples, urging the need to further understand the precursors of OSs.