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An analytical method using high-performance liquid chromatography (HPLC) with fluorescence (FL) detection was developed for simultaneously analyzing 10 polycyclic aromatic hydrocarbons (PAHs) and 18 nitro-derivatives of PAHs (NPAHs). The two-dimensional HPLC system consists of an on-line clean-up and reduction for NPAHs in the 1st dimension, and separation of the PAHs and the reduced NPAHs and their FL detection in the 2nd dimension after column-switching. To identify an ideal clean-up column for removing sample matrix that may interfere with detection of the analytes, the characteristics of 8 reversed-phase columns were evaluated. The nitrophenylethyl (NPE)-bonded silica column was selected because of its shorter elution band and larger retention factors of the analytes due to strong dipole-dipole interactions. The amino-substituted PAHs (reduced NPAHs), PAHs and deuterated internal standards were separated on polymeric octadecyl-bonded silica (ODS) columns and by dual-channel detection within 120 min including clean-up and reduction steps. The limits of detection were 0.1-9.2 pg per injection for PAHs and 0.1-140 pg per injection for NPAHs. For validation, the method was applied to analyze crude extracts of fine particulate matter (PM2.5) samples and achieved good analytical precision and accuracy. Moreover, the standard reference material (SRM1649b, urban dust) was analyzed by this method and the observed concentrations of PAHs and NPAHs were similar to those in previous reports. Thus, the method developed herein has the potential to become a standard HPLC-based method, especially for NPAHs.

Total suspended particulates (TSP) in the atmosphere were collected for 2 weeks during winter in Muroran, Hokkaido, Japan, a typical iron-manufacturing city. The concentrations of polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) in TSP were determined by high-performance liquid chromatography (HPLC) using fluorescence and chemiluminescence detectors, respectively. No relationship was observed between the atmospheric PAH and NPAH concentration, or the atmospheric PAH and TSP concentration. However, there was a tendency that the atmospheric PAH concentration was higher when the wind blew from the coke-oven plant. Furthermore, the concentration ratios of 1-nitropyrene to pyrene, which is a suitable indicator of the contribution made by automobiles and coal combustion systems to urban air particulates, were smaller in Muroran and the values were close to those observed in particulates from coal combustion systems. Therefore, these results show that the PAH and NPAH compositions for Muroran are characteristic of an iron-manufacturing city.

首都圏3地点(野毛、九段、つくば)において、野毛および九段では2006～2013年まで、つくばでは2010～2013年までの夏と冬の大気粉塵を捕集し、多環芳香族炭化水素 (PAH) 9種類およびニトロ多環芳香族炭化水素 (NPAH) 3種類をそれぞれHPLC-蛍光検出法、HPLC-化学発光検出法で測定し、その濃度の変遷を明らかにした。PAH濃度は野毛、九段で2006年から2008年の間の冬に低下傾向が認められた。NPAH濃度は、野毛では2006年から2011年の間の夏と冬、九段では2007年から2009年の間の夏および2006年から2011年の間の冬に低下傾向が認められた。つくばでは観測期間が2010年から2013年と短く、PAHとNPAHのいずれについても明確な変動傾向は認められなかった。また野毛および九段で[1-NP]/[Pyr]値の低下が確認され、PAH、NPAH濃度低下の要因の一つとして自動車排ガス規制による粉塵およびNOx排出量の減少が考えられた。 Airborne particulates were collected in Noge and Kudan, Japan, in the summer and winter from 2006 to 2013 and in Tsukuba, Japan, in the summer and winter from 2010 to 2013. The polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) were determined by HPLC with fluorescence and chemiluminescence detections, respectively. The decreasing tendencies of the total concentrations of nine PAHs were observed at Noge and Kudan in the winter from 2006 to 2008. The decreasing tendencies of the total concentrations of three NPAHs were observed in both the summer and winter in Noge from 2006 to 2011. The decreasing tendencies of the NPAH concentrations were also observed in Kudan in the winter from 2006 to 2011 and in the summer from 2007 to 2009. The concentration ratio of 1-nitropyrene to pyrene also decreased in Noge and Kudan. As the main reason for the decrease in the urban atmospheric PAH and NPAH concentrations, the Japanese regulation of exhaust gas/particulates from automobiles was considered.

A new method for the analysis of selected nitropolycyclic aromatic hydrocarbons (NPAHs) at ultra-trace levels in water samples is proposed. Particulate NPAHs were collected on a GC glass fiber filter. Soluble NPAHs were collected on a C18 Empore disk. After simple clean-up and concentration of NPAHs in both phases, the NPAHs were analyzed using HPLC equipped with clean-up, reducer, concentration and chemiluminescence detection units. The proposed method showed good linear calibration curves with correlation coefficients (r(2)) ranging from 0.9954 to 0.9998. The limits of detection ranged from 0.013 to 0.15 nmol/L (soluble NPAHs) and from 0.01 to 0.13 nmol/L (particulate NPAHs) for 5 NPAHs [(9-nitroanthracene, 1-nitropyrene, 6-nitrochrysene (6-NC), 7-nitrobenz[a]anthracene and 6-nitrobenzo[a]pyrene] having 3 to 5 rings analyzed, when 1.5 L of water sample was used. The repeatability for soluble NPAHs ranged between 4.2 and 6.8% (n=5), while for particulate NPAHs, it varied between 2.2 and 2.8% (n=5). The proposed method successfully determined the above NPAHs expect 6-NC in river water samples, suggesting that this method is suitable for the ultra-trace analysis of NPAHs in water samples.

Urban air contains various kinds of organic pollutants. Among them, several polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) are carcinogenic and/or endocrine disrupting. PAHs and NPAHs in the atmosphere mainly originate from imperfect combustion of organic matter, such as petroleum and coal. In this study, total suspended particles (TSP) were collected in three different particulate size fractions by using Andersen low-volume air samplers in Shenyang, Shanghai and Fuzhou, China, in the winter and summer seasons in 2010. Nine PAHs and twelve NPAHs in the extracts from the TSP were analyzed by HPLC with fluorescence detection and chemiluminescence detection, respectively. The mean concentrations of the sums of the nine PAHs and twelve NPAHs were highest in Shenyang and lowest in Fuzhou. In each city, more than 80% of the total PAHs and total NPAHs were found in the fine particulate fraction (

Airborne particulate matter (PM) has been collected at four cities in Japan starting in the late 1990s, at five or more major cities in China, Korea and Russia starting in 2001 and at the Noto Peninsula starting in 2004. Nine polycyclic aromatic hydrocarbons (PAHs) and eleven nitropolycyclic aromatic hydrocarbons (NPAHs) were determined by HPLC with fluorescence and chemiluminescence detections, respectively. Annual concentrations of PAHs and NPAHs were in the order, China>Russia≫Korea=Japan, with seasonal change (winter>summer). During the observation period, concentrations of PAHs and NPAHs in Japanese cities significantly decreased but the increases in the PAH concentration were observed in Chinese and Russian cities. Concentrations of PAHs and NPAHs were higher in the Northern China than those in the Southern China. At the Noto peninsula, which is in the main path of winter northwest winds and a year-round jet stream that blow from the Asian continent to Japan, the concentrations were high in winter and low in summer every year. A cluster analysis and back trajectory analysis indicated that PAHs and NPAHs were long-range transported from Northeastern China, where coal burning systems such as coal-heating boilers are considered to be the major contributors of PAHs and NPAHs. A dramatic change in atmospheric concentrations of PAHs and NPAHs in East Asia suggests the rapid and large change of PM2.5 pollution in East Asia. Considering the adverse health effects of PM2.5, continuous monitoring of atmospheric PAHs and NPAHs is necessary in this area.

石川県金沢市藤江の幹線道路脇において12年間（1999～2010年）の夏と冬の大気粉塵を捕集し、多環芳香族炭化水素（PAH）6種類（pyrene、benz[a]anthracene、chrysene、benzo[b]fluoranthene、benzo[k]fluoranthene、benzo[a]pyrene）およびニトロ多環芳香族炭化水素（NPAH）7種類（1,3-、1,6-、1,8-dinitropyrenes、1-nitropyrene、6-nitrochrysene、7-nitrobenz[a]anthracene、6-nitrobenzo[a]pyrene）をそれぞれHPLC-蛍光検出法、HPLC-化学発光検出法で測定し、その変遷を明らかにした。この間に、PAH濃度は冬63.9％、夏75.6％減少、NPAH濃度は冬88.0％、夏89.2％減少した。また[1-NP]/[Pyr]値は冬と夏ともに著しく減少した。自動車排ガス規制の強化によって排出源としての自動車の寄与率が低下したことが、大気中PAH、NPAH濃度および[1-NP]/[Pyr]値が顕著に減少した主要因と考えられた。 Airborne particulates were collected at a roadside site in Kanazawa, Japan, in the summer and winter, 1999, 2004/2005, 2007/2008 and 2010. The polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) were determined by HPLC with fluorescence and chemiluminescence detections, respectively. The total concentration of six PAHs (pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene and benzo[a]pyrene) decreased by the factor of 63.9% in the winter and 75.6% in the summer from 1999 to 2010. The total concentration of seven NPAHs (1,3-, 1,6-, 1,8-dinitropyrenes, 1-nitropyrene, 6-nitrochrysene, 7-nitrobenz[a]anthracene and 6-nitrobenzo[a]pyrene) significantly decreased by the factor of 88.0% in the winter and 89.2% in the summer during the same period. The concentration ratio of 1-nitropyrene to pyrene also significantly decreased in this period, suggesting a decrease in the emission amount. As the main reason for the significant decrease in the PAHs and NPAHs, the regulation of exhaust gas/particulates from automobiles was considered.

化石燃料の燃焼に伴って二酸化炭素の他にも種々の化学物質が発生し、気候変動の要因となるばかりでなくヒトの健康や生態系にも影響を及ぼしている。こうした有害化学物質の一つに多環芳香族炭化水素（PAH）及びニトロ多環芳香族炭化水素（NPAH）がある。以前からPAH、NPAHに発がん性を有するものが多いことは知られていたが、最近、これらの酸化体である水酸化体やキノン体のなかに、内分泌かく乱作用や活性酸素過剰産生作用を示すものがあることも明らかになり、肺がんだけでなく、喘息などのアレルギー疾患や心疾患などとの関連も疑われるようになった。著者は、20年ほど前にHPLC-化学発光検出法による超高感度なNPAH分析法を開発したことを契機に、我が国のみならず、日本海を挟む中国、韓国、ロシアの研究者と協力して大気PAH/NPAHモニタリングネットワークを組織した。そして、今日まで10年以上にわたって、これらの国々の都市とバックグラウンド地点で大気粉塵を継続捕集し、PAH、NPAHを追跡し、汚染レベルや発生源の変化、大気反応、長距離輸送などを追跡してきた。そこで、本大気環境学会賞総説では、著者の東アジアにおけるPAH、NPAHに関する研究成果を中心に、分析法や毒性にも触れながら紹介する。With the increase of consumption of fossil fuels, large amounts of pollutants released into the atmosphere cause serious health problems. Polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) are one of the atmospheric hazardous pollutants. The mutagenicities of several NPAHs are much stronger than those of PAHs, but the concentrations of NPAHs are much lower than those of PAHs in the environment. However, the progress of the study on the environmental behaviors and health effects of NPAHs have been much slower than that of PAHs, because of the lack of sensitive analytical methods for trace NPAHs. I developed a highly sensitive determination method for NPAHs by using HPLC with chemiluminescence detection. We organized an atmospheric PAHs and NPAHs monitoring network which covered East-Asian countries surrounding the Japan Sea (Japan, China, Korea and Russia) to collect air samples and applied the above method for the determination of PAHs and NPAHs. This review deals with analytical methods, behaviors and toxicities of PAHs and NPAHs in East Asia.

The East Asia countries including Japan, China, Korea and Russia have been undergoing a rapid increase of economic and industrial development. However, large amounts of pollutants are released into the air and water. The main energy source, economic stage and lifestale are different in the above four countries and these differences cause the current diverse situation of atmospheric and water pollution in East Asia. This view describes the present stage of atmospheric pollution and countermeasures in East Asia including the author's recent research results concerning polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons. ©2009 The Pharmaceutical Society of Japan.

Hazardous polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) are mainly originated from imperfect combustion of fossil fuels such as petroleum and coal. The consumptions of not only petroleum but also coal have been increasing in the East Asian countries. This review describes the result of international collaboration research concerning characteristics and major contributors of atmospheric PAHs and NPAHs in cities in Japan, Korea, China and Russia. We collected airborne particulates in ten cities in the above countries and six PAHs and eleven NPAHs were determined by HPLC methods using fluorescence and chemiluminescence detections. The total PAH concentrations were much higher in Chinese cities (Fushun, Tieling, Shenyang and Beijing) than those in other cities (Vladivostok, Busan, Kanazawa, Kitakyushu, Sapporo and Tokyo). The total NPAH concentrations were also higher in Chinese cities than those in the other cities. The [NPAH]/[corresponding PAH] ratios are much larger in diesel-engine exhaust particulates than those in coal-burning particulates. The [1-nitropyrene]/[pyrene] ratio of airborne particulates was much smaller in the four Chinese cities, suggesting that coal combustion systems such as coal heaters were the main contributors. On the other hand, the ratios were larger in Korean and Japanese cities, suggesting the large contribution of diesel-engine vehicles.

Many hazardous chemicals are absorbed into human body through respiration and have effects on human health. The 21st Century COE (center of excellence) "Environmental Monitoring and Prediction of Long- and Short-term Dynamics of Pan-Japan Sea Area-Construction of Monitoring Network and Assessment of Human Effects" (Leader : Kazuichi Hayakawa, Graduate School of Natural Science and Technology, Kanazawa University) concentrates on atmospheric pollution caused by human activities occurred in countries, Japan, China, Korea and Russia, surrounding Pan-Japan Sea as one of major projects. My talk focuses on atmospheric pollution caused by polycyclic aromatic hydrocarbon (PAH) and nitropolycyclic aromatic hydrocarbon (NPAH), which clearly exists in this area, and demonstrates the following aspects concerning this issue : 1) The 21st Century "Environmental Monitoring and Prediction of Long- and Short-term Dynamics of Pan-Japan Sea Area-Construction of Monitoring Network and Assessment of Human Effects," 2) Importance of PAH and NPAH as hazardous pollutants emitted from combustion of fossil fuels such as coal and oil, 3) Current status of atmospheric pollution of PAH and NPAH of Pan-Japan Sea Area, focusing on coal combustion systems such as heating in China and diesel-engine automobiles in Japan, and 4) Health effects of PAH and NPAH such as lung cancer and endocrine disruption.

Polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) are widespread carcinogenic compounds that arise from occupational, environmental and dietary sources. The metabolites of PAHs and NPAHs in biological fluids have been investigated as potential biomarkers for assessing human exposure to them, and, particularly, urinary metabolites are the excelle nt candidates due to the non-invasiveness and convenience of collecting the sample. Here we describe HPLC methods for accurately determining one type of these metabolites, monohydroxy PAHs (OHPAHs). The developed method was applied to the urine samples of non-smoker taxi drivers, traffic police officers and rural villagers of Chiang Mai, Thailand. The results showed higher urinary concentrations of OHPAHs in rural villagers, suggesting the higher respiratory exposure to PAHs contained in smoke from biomass burning. On the other hand, 1-nitropyrene (1-NP) is one of the most abundant NPAHs in diesel exhaust particulate matter (DEP). We also developed a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for determining urinary 1-NP metabolites. 1-NP metabolites were quantified in urine from healthy subjects. 6- and 8-Hydroxy-N-acetyl-1-aminopyrenes (OHNAAPs) an d6 -a nd 8-hydroxy-1-nitropyrenes (OHNPs) were the most abundant 1-NP metabolites in human urine. The presence of OHNAAPs and OHNPs in human urine was demonstrated for the first time.

Airborne particulates were collected simultaneously at Vladivostok, Kanazawa and Toyama. 1,3-, 1,6-, 1,8-Dinitropyrenes (DNPs), 1-, 2-, 4-nitropyrenes (NPs), 2-nitrofluorene and 6-nitrochrysene in the particulates were analyzed by HPLC with chemiluminescence detection. All compounds were detected not only in Kanazawa but also in Vladivostok and Toyama. Moreover, five unknown peaks which might be nitropolycyclic aromatic hydrocarbons were detected only in chromatograms of Vladivostok. The [DNPs]/[1-NP] ratios at all stations were near the value found in diesel-exhaust particulates, suggesting that one of the main contributors of these compounds was diesel-engine vehicles not only in Kanazawa and Toyama but also in Vladivostok. However, the difference in traffic volume at two stations in Vladivostok did not have a significant effect on the concentrations of DNPs and NPs in contrast to two stations in Kanazawa. These results suggested sources other than diesel-engine vehicles also contributing to DNPs and NPs in Vladivostok. Seasonal variations similar to those in Kanazawa were observed in Vladivostok and Toyama. As in Kanazawa, the [2-NP]/[1-NP] ratio in Vladivostok was larger at the lighter traffic station than that at heavier traffic station. This suggested that, as in Kanazawa, 2-NP was formed in the atmosphere in Vladivostok.

金沢大学医薬保健研究域薬学系, A simultaneous determination method for polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in airborne particulates was developed. Airborne particulates were extracted with benzene/ethanol, cleaned up by liquid-liquid partition, refluxed in the presence of NaSH and then the resultant solution was injected into an HPLC system. The system was hybridized into two systems with different optimum conditions for PAHs and NPAHs by introducing a switching valve and a mini separation column. Mobile phases were acetonitrile/water (75 : 25) for PAHs, and acetonitrile/imidazole HClO_4 buffer (1 : 1) for NPAHs and the postcolumn reagent solution for NPAHs was an acetonitrile solution containing bis(2,4,6-trichlorophenyl)oxalate and H_2O_2. By this method, four NPAHs (1,3-, 1,6-, 1,8-dinitropyrenes and 1-nitropyrene) and eight PAHs (fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene and coronene) in sub-milligram quantities of airborne particulates were determined chemilumigenically and fluorogenically, respectively using 2-fluoro-7-nitrofluorene as an internal standard within sixty minutes.

Methods developed for the analysis of the organic compounds adsorbed on diesel particulate are reviewed with special emphasis on the determination of polycyclic aromatic hydrocarbons (PAH), nitro PAH and oxy PAH. (ITA)

We developed a sampler for collecting atmospheric polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) by attaching a glass column packed with XAD-4 resin to the gas sampling port of a high-volume air sampler equipped with a filter. When the upper and bottom layers of the column were packed with 64 g and 32 g of XAD-4 resin, respectively, all PAHs and NPAHs in the gas phase were quantitatively collected in the XAD-4 resin column without any break through, while PAHs and NPAHs in the particle phase were collected on the filter. We collected air samples at suburban and downtown Kanazawa by using the proposed sampler. It was found that about 95% of 2-3 ring PAHs and more than 99% of 2-ring NPAHs existed chiefly in the gas phase, that 4-ring PAHs such as fluoranthene (FR) and pyrene (Pyr) and 3-ring NPAHs were in both the gas and particle phases and that the other PAHs and NPAHs having 4-rings or more except for FR and Pyr were almost completely in the particle phase. Our data also indicated that the adsorption of NPAHs to the particle phase in the atmosphere is controlled by the same mechanism as that of PAHs.