Particulate Nitrate Formation in a Highly Polluted Urban Area: A Case Study by Single-Particle Mass Spectrometry in Shanghai

An aerosol time-of-flight mass spectrometer was deployed in August 2007 to characterize the 0.1−2.0 μm diameter particles in Shanghai to examine nitrate-containing particles. About 39% of the mass spectra of single particles contained nitrate ion peaks. The relative intensity of nitrate signals showed a pronounced diurnal profile, peaking in the late night or early morning during highly polluted days, and is closely correlated with the ambient relative humidity (RH). However, during the sampling days with good air quality, the diurnal pattern of nitrate changed by showing much lower signal intensity of nitrate with irregular variation. Poor correlation between the signals of ammonium and nitrate in the mass spectra excluded the possibility of NH4NO3 as a major form of particulate nitrate, whose formation is favored by high RH and low temperature. The peak intensities of nitrate during the nighttime and high concentrations of O3 and NO2 strongly suggest that the heterogeneous reactions of N2O5 and NO3 on the aerosol surface dominated the particulate nitrate formation on polluted days.