Nitro-polycyclic aromatic hydrocarbon concentrations and sources in urban and suburban atmospheres of the Mid-Atlantic region

Gas and particle phase concentrations of 26 nitro-PAHs were quantified in ambient air collected in downtown Baltimore, MD, an urban region, and in Fort Meade, MD, a suburban area 20 km south-southeast of Baltimore, during January and July 2001. Total (gas+particle) concentrations for individual nitro-PAH compounds varied by as much as five times from sample to sample within each month. 2-Nitrofluoranthene and 9-nitroanthracene were the most abundant of the nitro-PAHs quantitatively analyzed in the air at both sites, accounting for approximately half of the total nitro-PAH concentrations during January and July. Concentrations at Baltimore were on average two to three times higher than those measured at the Fort Meade site. Concentrations for most nitro-PAHs were higher in January than in July, suggesting a reduction in photodecay of nitro-PAHs during January promoted the accumulation of nitro-PAHs. Concentrations of nitro-PAHs produced from gas-phase reactions were significantly correlated with concentrations of oxides of nitrogen (NOx) measured simultaneously at the Fort Meade site. 3-Nitrophenanthrene and 4-nitrophenanthrene were negatively correlated with NOx and were the only nitro-PAHs correlated with O3, suggesting a different formation mechanism for these compounds compared to the other nitro-PAHs found in this study. The relative contribution of gas-phase reactions and primary emission sources of nitro-PAHs were evaluated using source specific concentration ratios of 2-nitrofluoranthene and 1-nitropyrene (2-NF/1-NP). The mean ratios of 2-NF/1-NP at both sites were statistically higher in July than January, indicating gas-phase reactions were an important source of 2-nitrofluoranthene in the summer. However, in January, gas-phase reactions were reduced, the NO3-initiated reaction in particular, and primary emissions may significantly contribute to ambient nitro-PAH levels. The two dominant gas-phase production pathways of nitro-PAHs from the OH and NO3-initiated reactions were investigated using concentration ratios of 2-nitrofluoranthene and 2-nitropyrene (2-NF/2-NP). At both sites, 2-NF/2-NP ratios indicated that the daytime OH-initiated reaction was the dominant gas-phase formation pathway. The estimated contributions of nitro-PAHs produced through gas-phase reactions via the OH pathway during July were >45% and during January were >83% at both Fort Meade and Baltimore.