Sulfate–nitrate–ammonium as double salts in PM2.5: Direct observations and implications for haze events

Abstract

Obtaining detailed information on sulfate–nitrate–ammonium (SNA) is fundamentally important to explain the formation of haze in China, since it is a dominant component of fine particulate matter (PM2.5) and plays a critical role in the deterioration of air quality. Several single-particle analysis methods have been applied to study and explain SNA formation; however, determining its mixture state remains a challenge. This study describes a direct observation of the SNA components in atmospheric particles on a single-particle scale, and details the first use of a non-destructive surface-enhanced Raman scattering (SERS) technique for SNA analysis. We studied PM2.5 collected at a site on the premises of Tsinghua University in Beijing, China, during a winter haze episode (12.15.2016–12.23.2016). The on-line data show that the SNA component accounted for 9.4% to 68.2% of the total mass of PM2.5, becoming dominant on heavy haze days, and the sulfate concentration increased with the nitrate concentration (R2 = 0.72). Furthermore, the off-line SERS and scanning electron microscopy-energy dispersive X ray analysis (SEM-EDS) results for the single particles collected also indicated that SNA increase with increasing haze pollution. The existing state of the SNA component on each haze day was observed directly in a non-destructive manner mainly in the form of double salts such as 3(NH4NO3)·(NH4)2SO4 and 2(NH4NO3)·(NH4)2SO4. A Raman mapping experiment further confirmed that the SNA was internally mixed. Our data also show that SNA can evaporate under high-vacuum scanning electron microscopy conditions, suggesting that SERS is an effective method to directly observe SNA without sample loss and may represent a promising single-particle technique to supplement traditional electron microscopy methods. This work will provide evidence for the SNA formation, particularly during haze events.