Hitoshi Kakimoto

Comparison of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons in airborne particulates collected in downtown and suburban Kanazawa, Japan

In this study, airborne particulates were collected at three sites, two in a downtown area and the other in a suburban area of Kanazawa, Japan in each season for 7 years. Two polycyclic aromatic hydrocarbons (PAHs), pyrene (Py) and benzo[a]pyrene (BaP) and four nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (NP) and 1,3-, 1,6-, and 1,8-dinitropyrenes (DNP) were determined by high-performance liquid chromatography with fluorescence and chemiluminescence detection. At the downtown sites, the mean concentration of each DNP was about two orders of magnitude lower than that of 1-NP and more than three orders of magnitude lower than those of Py and BaP. This tendency reflected the composition of PAHs and NPAHs in diesel-engine exhaust particulates. Concentrations of these PAHs and NPAHs were higher at the downtown sites than at the suburban site, suggesting the dilution of these compounds during the transportation from the downtown to the suburban area. The concentration ratios of NPAHs to PAHs were larger at the downtown sites than at the suburban site. Studies using UV light and sunlight showed that degradation of NPAHs was faster than that of PAHs. Thus, the lower concentrations of NPAHs in the suburban sites may be due to their being photodegraded faster than PAHs during the atmospheric transportation from the downtown area to the suburban area.

Comparison of Polycyclic Aromatic Hydrocarbons and Nitropolycyclic Aromatic Hydrocarbons in Airborne and Automobile Exhaust Particulates

Abstract Polycyclic aromatic hydrocarbons (PAH) and nitropolycyclic aromatic hydrocarbons (NPAH) in airborne particulates collected simultaneously at downtown and suburban sites and in exhaust particulates from diesel and gasoline engine vehicles were determined. The mean concentrations of all compounds in the atmosphere were lower at the suburban site. The differences between the two sites were smaller in airborne particulates than in the atmosphere. However, the difference in NPAH concentrations in particulates between the two sites was greater than the difference in PAH concentrations, suggesting that the NPAH were less stable than the PAH. The concentrations of 1-nitropyrene and 1,3-, 1,6- and 1,8-dinitropyrenes were generally much higher in automobile exhaust particulates than in airborne particulates because the former were collected directly. However, 2-nitrofluoranthene and 2-nitropyrene were observed in airborne particulates but not in automobile exhaust particulates. The diurnal concentrations showed that 2-nitrofluoranthene and 2-nitropyrene might be formed by a hydroxyl radical-initiated reaction followed by nitration.

Long term trends in atmospheric concentrations of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons: A study of Japanese cities from 1997 to 2014

Total suspended particulate matter (TSP) was collected during the summer and winter in five Japanese cities spanning Hokkaido to Kyushu (Sapporo, Kanazawa, Tokyo, Sagamihara and Kitakyushu) from 1997 to 2014. Nine polycyclic aromatic hydrocarbons (PAHs) with four to six rings, including pyrene (Pyr) and benzo[a]pyrene (BaP), were identified using high-performance liquid chromatography (HPLC) with fluorescence detection. Two nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (1-NP) and 6-nitrobenzo[a]pyrene (6-NBaP), were identified by HPLC with chemiluminescence detection. A comparison of PAH and NPAH concentrations and [NPAH]/[PAH] ratios such as [1-NP]/[Pyr] and [6-NBaP]/[BaP] revealed the following characteristics in the five cities: (1) In Sapporo, Kanazawa, Tokyo and Sagamihara, the concentrations of PAHs and NPAHs were high at the beginning of the sampling period and then steadily decreased, with NPAHs decreasing faster than PAHs. The large initial [1-NP]/[Pyr] ratios suggest that the major contributor was automobiles but subsequent decreases in this ratio suggest decreased automobile contributions. (2) By contrast, PAH concentrations in Kitakyushu did not decrease during the sampling period, though concentrations of NPAHs decreased. The consistently smaller [1-NP]/[Pyr] ratio and larger [6-NBaP]/[BaP] ratio in Kitakyushu suggests that the major contributor of PAHs was not automobiles but iron manufacturing which uses a large amount of coal. The sudden increase in atmospheric PAH concentrations in the winter of 2014 may also be due to iron manufacturing.