The source apportionment and main formation pathway of nitrate aerosols in China are not yet fully understood. In this study, PM2.5 samples were collected in Shanghai in the summer and winter of 2019. Water-soluble inorganic ions and isotopic signatures of stable nitrogen (δ15N-NO3-) and stable oxygen (δ18O-NO3-) in PM2.5 were determined. The results showed that NO3- was less important in summer (NO3-/SO42- = 0.4 ± 0.8), while it became the dominant species in winter (52.1 %). The average values of δ15N-NO3- and δ18O-NO3- in summer were + 2.0 ± 6.1 and 63.3 ± 9.4 respectively, which were significantly lower than those in winter (+7.2 ± 3.4 and 88.3 ± 12.1 ), indicating discrepancies between NOx sources and nitrate formation pathways. Both δ15N-NO3- and δ18O-NO3- were elevated at night, demonstrating that N2O5 hydrolysis contributed to the nocturnal nitrate increase even in summer. The contribution of the OH oxidation pathway to nitrate aerosols averaged at 70.5 ± 17.0 % in summer and N2O5 hydrolysis dominated the nitrate production in winter (approximately 80 %). On average, vehicle exhaust, coal combustion, natural gas burning, and soil emission contributed 50.7 %, 21.5 %, 15.9 %, and 11.9 %, respectively, to nitrate aerosols in summer, and contributed 56.8 %, 23.9 %, 13.6 %, and 5.7 %, respectively, to nitrate production in winter. Notably, natural gas burning is a non-negligible source of nitrate aerosols in Shanghai. In contrast to an inverse correlation between δ15N-NO3- and PM2.5, the value of δ18O-NO3- was positively correlated with nitrate concentration and aerosol liquid water content (ALWC) in winter, suggesting that explosive growth of nitrate was driven by continuous accumulation of N-depleted NOx and rapid N2O5 hydrolysis under calm and humid conditions. To continuously improve air quality, priority control should be given to vehicle emissions as the dominant source of NOx and volatile organic compounds (VOCs) in Shanghai.
Elemental composition of PM2.5 dispersed in the atmosphere has received increasing attention due to its health effect and catalytic activities. In this study, the characteristics and source apportionment of PM2.5-bound elements were investigated using hourly measurements. K is the most abundant metal element, followed by Fe > Ca > Zn > Mn > Ba > Pb > Cu > Cd. With an average of 8.8 ± 4.1 ng m-3, Cd was the only element whose pollution level exceeded the limits of Chinese standards and WHO guidelines. The concentrations of As, Se, and Pb doubled in December compared to November, indicating a large increase in coal consumption in winter. The enrichment factors of As, Se, Hg, Zn, Cu, Cd, and Ag were larger than 100, indicating that anthropogenic activities greatly affected them. Ship emissions, coal combustion, soil dust, vehicle emissions, and industrial emissions were identified as major sources of trace elements. In November, the pollution from coal burning and industrial activities was significantly reduced, demonstrating the remarkable achievement of coordinated control measures. For the first time, hourly measurements of PM2.5-bound elements and secondary sulfate and nitrate were used to investigate the development of dust and PM2.5 events. During a dust storm event, secondary inorganic salts, potentially toxic elements, and crustal elements sequentially reached peak concentrations, indicating different source origins and formation mechanisms. During the winter PM2.5 event, the sustained increase of trace elements was attributed to the accumulation of local emissions, while regional transport was responsible for the explosive growth before the end of the event. This study highlights the important role of hourly measurement data in distinguishing local accumulation from regional and long-range transport.
