Assessment of the impact of large changes in the ratio of photolysis rate of nitrate to that of gas nitric acid on HONO concentrations simulated by a 3-D chemical transport model

Some studies show that photolysis of nitrate and deposited nitrate and gas nitric acid (HNO₃) on the ground surface is much faster than that of HNO₃. The former mechanism has been considered as a possible daytime HONO source and discussed in many laboratory and field studies. Although this mechanism is also coupled into some three-dimensional chemical transport models, the effect of large changes in the ratio of photolysis rate of nitrate to that of HNO₃ (RAT) on HONO concentrations has not been assessed and will be discussed here by using the updated WRF-Chem model. Simulations indicate that in the morning, this mechanism only resulted in a HONO increase of a few ppt, while the heterogeneous reaction of NO₂ enhanced HONO by about 150 ppt; in the afternoon, however, this mechanism led to a significant HONO increase, with its contribution to HONO concentrations being close to the contribution of the heterogeneous reaction of NO₂. In some heavily nitrate-polluted areas, this mechanism contributed more than 80% of HONO concentrations during the afternoon. Large changes in RAT produced a substantial impact on HONO concentrations. When RAT was altered from 15 to 100, increase of HONO concentrations was enhanced by about 6 times. Our results suggest that more laboratory and field studies on the photolysis rates of nitrate and deposited nitrate and HNO₃ on the ground surface are still needed.