Formation of nitroanthracene and anthraquinone from the heterogeneous reaction between NO2 and anthracene adsorbed on NaCl particles.

Oxidative derivatives of polycyclic aromatic hydrocarbons (PAHs), that is, nitro-PAHs and quinones, are classed as hazardous semivolatile organic compounds but their formation mechanism from the heterogeneous reactions of PAHs adsorbed on atmospheric particles is not well understood. The heterogeneous reaction of NO2 with anthracene adsorbed on NaCl particles under different relative humidity (RH 0-60%) was investigated under dark conditions at 298 K. The formation of the major products, 9,10-anthraquinone (9,10-AQ) and 9-nitroanthracene (9-NANT), were determined to be second-order reactions with respect to NO2 concentration. The rate of formation of 9,10-AQ under low RH (0-20%) increased as the RH increased but decreased when the RH was further increased in high RH (40-60%). In contrast, the rate of formation of 9-NANT across the whole RH range (0-60%) decreased significantly with increasing RH. Two different reaction pathways are discussed for the formation of 9,10-AQ and 9-NANT, respectively, and both are considered to be coupled to the predominant reaction of NO2 with the NaCl substrate. These results suggest that relative humidity, which controls the amount of surface adsorbed water on NaCl particles, plays an important role in the heterogeneous reaction of NO2 with adsorbed PAHs.