Diurnal and seasonal variations in water-soluble inorganic ions and nitrate dual isotopes of PM2.5: Implications for source apportionment and formation processes of urban aerosol nitrate

Abstract

Recently, increasing urban aerosol NO3− deposition have aroused widespread attention. To reveal its sources and formation processes, the water-soluble inorganic ions (WSIIs) and NO3− dual isotopes (i.e., δ15N and δ18O) were measured in fine particles (i.e., PM2.5), which were collected during rush hours in the morning and afternoon, and non-rush hours at noon, discretely in winter and in summer at urban Guiyang, southwest China. Results showed the sulfate, nitrate, and ammonium together accounted for more than 90% of the total WSIIs in both seasons. Both NO3− and its dual isotopes were distinctly higher in winter than in summer. While only NO3− and δ15N were observed significantly higher during rush hours than the non-rush hours in summer, which could be potentially controlled by the temperature, relative humidity and ambient NH3 contents. The gradual but insignificant increase of δ18O during from morning to afternoon were ascribed to the decreasing contributions of •OH oxidation pathway. By using the Bayesian isotope mixing model, we revealed the coal combustion and biomass burning accounted for the predominant NOx sources in contributing to the particulate NO3− in winter, followed by vehicular and soil biogenic emissions. Whereas in summer, biomass burning played the most important role, since the coal combustion proportion sharply decreased. Moreover, the particle NO3− source contributions showed minor difference during diurnal periods in winter, while the difference was larger in summer, especially for that during between morning rush and noon non-rush hours, which were likely due to the changes of NOx emissions (e.g. from vehicular and soil biogenic source), as well as the meteorological conditions.