Comprehensive Study about the Photolysis of Nitrates on Mineral Oxides

Nitrates formed on mineral dust through heterogeneous reactions in high NOx areas can undergo photolysis to regenerate NOx and potentially interfere in the photochemistry in the downwind low NOx areas. However, little is known about such renoxification processes. In this study, photolysis of various nitrates on different mineral oxides was comprehensively investigated in a flow reactor and in situ diffuse reflectance Fourier-transform infrared spectroscopy (in situ DRIFTS). TiO2 was found much more reactive than Al2O3 and SiO2 with both NO2 and HONO as the two major photolysis products. The yields of NO2 and HONO depend on the cation basicity of the nitrate salts or the acidity of particles. As such, NH4NO3 is much more productive than other nitrates like Fe(NO3)3, Ca(NO3)2, and KNO3. SO2 and water vapor promote the photodegradation by increasing the surface acidity due to the photoinduced formation of H2SO4/sulfate and H+, respectively. O2 enables the photo-oxidation of NOx to regenerate nitrate and thus inhibits the NOx yield. Overall, our results demonstrated that the photolysis of nitrate can be accelerated under complex air pollution conditions, which are helpful for understanding the transformation of nitrate and the nitrogen cycle in the atmosphere.