Formation of oxidized products from the reaction of gaseous phenanthrene with the OH radical in a reaction chamber

The reaction of gas phase phenanthrene (Phen) with the OH radical in the presence of NO_x was studied in a reaction chamber. A number of oxidation products were identified by two dimensional gas chromatography-time of flight mass spectrometry (GC × GC-TOFMS). Identified products included 9-fluorenone, 1,2-naphthalic anhydride, 2,2'-diformylbiphenyl, dibenzopyranone, 1, 2, 3, 4 and 9-phenanthrols, 2, 3, 4 and 9-nitrophenanthrenes, 1,4-phenanthrenequinone, 9,10-phenanthrenequinone, and 2- and 4-nitrodibenzopyranones. This is the first study to identify 1,2-naphthalic anhydride and 1,4-phenanthrenequinone as products of the gas phase reaction of Phen with the OH radical. Eight more products were tentatively identified by their mass spectral fragmentation patterns and based on the typical OH radical initiated photochemical reaction mechanisms of simple aromatic compounds and naphthalene. In the reaction chamber, particle formation of products as a function of irradiation time was measured. Phenanthrenequinones, phenanthrol, nitrophenanthrene and nitrobenzopyranone were observed predominantly in the particle phase. This implies that these oxidized products formed from the reaction of Phen with the OH radical in the chamber would be associated with particles in the atmosphere and may, therefore, have an impact on human health. Possible pathways for the formation of these products are suggested and discussed.