Nitrates
formed on mineral dust through heterogeneous reactions
in high NO
x
areas can undergo photolysis
to regenerate NO
x
and potentially interfere
in the photochemistry in the downwind low NO
x
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 NO
x
to regenerate nitrate and thus inhibits the NO
x
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.
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