Direct Formation of Electronic Excited NO 2 Contributes to the High Yield of HONO during Photosensitized Renoxification.

Photosensitized renoxification of HNO 3 is found to produce HONO in an unexpectedly high yield, which has been considered an important source for atmospheric HONO. Conventionally, the production of HONO is ascribed to the secondary photolysis of the primarily formed NO 2 . In this study, by using humic acid (HA) as a model environmental photosensitizer, we provide evidence of the direct formation of NO 2 in its electronic excited state (NO 2 *) as a key intermediate during the photosensitizing renoxification of HNO 3 . Moreover, the high HONO yield originates from the heterogeneous reaction of the primarily formed NO 2 * with the co-adsorbed water molecules on HA. Such a mechanism is supported by the increase of the product selectivity of HONO with relative humidity. Further luminescence measurements demonstrate clearly the occurrence of an electronic excited state (NO 2 *) from photolysis of adsorbed HNO 3 on HA. This work deepens our understanding of the formation of atmospheric HONO and gives insight into the transformation of RNS.