Photolysis of Nitric Acid and Nitrate on Natural and Artificial Surfaces

Photolysis of nitric acid and nitrate (HNO3/nitrate) was investigated on the surfaces of natural and artificial materials, including plant leaves, metal sheets, and construction materials. The surfaces were conditioned in the outdoor air prior to experiments to receive natural depositions of ambient HNO3/nitrate and other atmospheric constituents. The photolysis rate constant (J(HNO3(s))) of the surface HNO3/nitrate was measured based on the production rates of nitrous acid (HONG) and nitrogen oxides (NOx). The J(HNO3(s)) values, from 6.0 X 10(-6) s(-1) to 3.7 x 10(-4) s(-1), are 1 to 3 orders of magnitude higher than that of gaseous HNO3. The HONO was the major product from photolysis of HNO3/nitrate on most plant leaves, whereas NOx was the major product on most artificial surfaces. The J(HNO3(s)) values decreased with HNO3/nitrate surface density and could be described by a simple analytical equation. Within a typical range of HNO3/nitrate surface density in the low-NOx forested areas, photolysis of HNO3/nitrate on the forest canopy can be a significant source for HONO and NOx for the overlying atmosphere.