Atmospheric Occurrence of Particle-associated Nitrotriphenylenes via Gas-phase Radical-initiated Reactions Observed in South Osaka, Japan

Abstract

Nitrotriphenylenes (NTPs), which include the highly mutagenic isomer 2-nitrotriphenylene (2-NTP), have been detected in airborne particles. From a public hygienic point of view, it is necessary to study the environmental occurrence of NTPs in detail. In this study, concentrations of five nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) including NTPs in airborne particles and of nitrogen oxides (NOx; NO+NO2) and carbon monoxide (CO), at a location in South Osaka, Japan, were measured at 3 h intervals. It was found that the diurnal variations in the concentrations of 1-nitropyrene (1-NP), NOx, and CO were similar, being high early in the morning and late in the evening. This finding indicates that the occurrence of 1-NP is affected significantly by primary emissions, particularly by automotive emissions. The concentration change in 1-nitrotriphenylene was similar to that of 2-nitropyrene produced by an atmospheric OH radicalinitiated reaction. On the contrary, the variations in the concentrations of 2-nitrofluoranthene (2-NF) and 2-NTP were significantly different from those of the other nitro-PAHs, i.e., their concentrations increased during the nighttime, suggesting that neither 2-NF nor 2-NTP was emitted from the primary sources, but were formed via the NO3 radicalinitiated nitration of the parent fluoranthene and triphenylene (TP) in the atmosphere. Based on the ambient concentration of 2-NTP and the reported rate constant for the reaction of TP with NO3 radicals, the yield of 2-NTP from the gas-phase NO3 radical-initiated reaction of TP was estimated to be 23%.