Mineral dust contains material such as TiO2 that is well known to have photocatalytic activity. In this laboratory study, mixed TiO2‐SiO2, Saharan dust and Arizona Test Dust were exposed to NO2 in a coated wall flow tube reactor. While uptake in the dark was negligible, photoenhanced uptake of NO2 was observed on all samples. For the mixed TiO2‐SiO2, the uptake coefficients increased with increasing TiO2 mass fraction, with BET uptake coefficients ranging from 0.12 to 1.9 × 10−6. HONO was observed from all samples, with varying yields, e.g., 80% for Saharan dust. Three‐dimensional modeling indicates that photochemistry of dust may reduce the NO2 level up to 37% and ozone up to 5% during a dust event in the free troposphere.
[1] The nitrate formation on dust particles is considered as a sink for atmospheric NO y (such as HNO 3 ). However mineral dust is shown here to be an effective photocatalyst for transformation of nitrate anions into NO and NO 2 , without involving its photolysis. The photodecomposition of NO 3 À at the surface of synthetic mineral dust samples of SiO 2 , TiO 2 , mixed TiO 2 -SiO 2 and authentic sand doped with 6% NO 3 À was studied by means of a flow-tube at 298 K with UVillumination in the 340 -420 nm range at relative humidities between 5 and 80%. Both NO and NO 2 are observed during irradiation of films composed of either mixed TiO 2 -SiO 2 , pure TiO 2 and authentic minerals from the Sahara. The relative humidity strongly affects the concentration of NO x released into the gas phase. The photoinduced nitrate conversion into NO x is discussed as being a potential renoxification process of the atmosphere.
The ozone decomposition onto mineral surfaces prepared with traces of solid TiO2 in a matrix of SiO2 in order to mimic mineral dust particles has been investigated using a coated-wall flow-tube system at room temperature and atmospheric pressure. The ozone uptake coefficients were measured both under dark conditions and irradiation using near UV-light. While uptake in the dark was negligible, a large photoenhanced ozone uptake was observed. For TiO2/SiO2 mixtures under irradiation, the uptake coefficients increased with increasing TiO2 mass fraction (from 1 to 3 wt %), and the corresponding uptake coefficient based on the geometric surfaces ranged from 3 x 10(-6) to 3 x 10(-5). The uptake kinetics was also observed to increase with decreasing ozone concentration between 290 and 50 ppbv. Relative humidity influenced the ozone uptake on the film, and a reduced ozone loss was observed for relative humidity above 30%. The experimental results suggest that under atmospherically relevant conditions the photochemistry of dust can represent an important sink of ozone inside the dust plume.
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