Contribution of nitrated polycyclic aromatic hydrocarbons to the mutagenicity of ultrafine particles in the roadside atmosphere

This is the first report of the quantification of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in ultrafine particles in the roadside atmosphere and their contribution to the direct-acting mutagenicity of ultrafine particles. The detailed size distributions of six nitro-PAHs (2-nitrofluoranthene, 1-nitropyrene, 6-nitrobenzo[a]pyrene, 1,3-dinitropyrene, 1,6-dinitropyrene, and 1,8-dinitropyrene) were measured by highly sensitive gas chromatography–negative ion chemical ionization tandem mass spectrometry. Direct-acting mutagenicity of size-fractionated particulate matter (PM) was determined by the Ames test using Salmonella typhimurium strains TA98 and YG1024. The amounts of nitro-PAHs per unit mass of ultrafine particles (<0.12 μm) were significantly higher than those of accumulation mode particles (0.12–2.1 μm) and of coarse particles (>2.1 μm). Therefore, more than 20% of each nitro-PAH, with the exception of 2-nitrofluoranthene, was observed in the ultrafine particle fraction, although the contribution of ultrafine particles to the total PM mass in the roadside atmosphere was only 2.3%. Also, in both tester strains TA98 and YG1024, the mutagenicity per unit mass of ultrafine particles was significantly higher than those of accumulation mode particles or coarse particles. The contributions of 2-nitrofluoranthene, 1-nitropyrene, 1,3-dinitropyrene, 1,6-dinitropyrene, and 1,8-dinitropyrene to the direct-acting mutagenicity of ultrafine particles were 0.56, 1.5, 0.57, 2.2, and 9.2%, respectively, in the TA98 strain, and 0.54, 1.1, 0.71, 5.0, and 17%, respectively, in the YG1024 strain, while the contribution of 6-nitrobenzo[a]pyrene was less than 0.01% in both strains. 1,8-Dinitropyrene was the largest contributor to the mutagenicity not only of ultrafine particles but also of accumulation mode particles in both strains. Only five nitro-PAHs accounted for as much as 14 and 24% of the direct-acting mutagenicity of ultrafine particles in the roadside atmosphere in the TA98 strain and the YG1024 strain, respectively. This result indicated that nitro-PAHs, especially 1,8-dinitropyrene, were important contributors to the high direct-acting mutagenicity of ultrafine particles in the roadside atmosphere.