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Atmospheric quinoid polycyclic aromatic hydrocarbons (PAHQs) have adverse health effects as redox-active species in particulate matter (PM). Several PAHQs are known to be very reactive in the dithiothreitol (DTT) assay; however, it is unclear if pyrenequinones, their parent pyrene is one of the most abundant polycyclic aromatic hydrocarbons (PAHs) in the atmosphere, contribute to the loss of DTT in PM extracts. Herein, by employing the DTT assay, we evaluated oxidative potentials of three pyrenequinone isomers (4, 5-pyrenequinone [4, 5-PyQ] and a mixture of 1, 6-/1, 8-pyrenequinones [1, 6-/1, 8-PyQ]), along with 9, 10-phenanthrenequinone (PQN), 1, 2-naphthoquinone (1, 2-NQ), and 1, 4-naphthoquinone (1, 4-NQ), of which DTT loss rates were examined previously. Our results demonstrate that the DTT consumption by ortho-type PAHQs is fast, particularly by 4, 5-PyQ. The order of DTT loss rate by the PAHQs tested in this study was as follows: 4, 5-PyQ ∼ PQN > 1, 2-NQ > 1, 4-NQ ∼ 1, 6-/1, 8-PyQ. 4, 5-PyQ was confirmed to be active in the DTT assay for the first time in this study. The DTT consumption rate by 4, 5-PyQ is 14.6 ± 0.8 mol/min/PAHQ-mol, which is comparable to that of PQN (14.4 ± 0.1 mol/min/PAHQ-mol) known as the most active PAHQs by the DTT assay so far.

PM2.1 was collected at urban and suburban elementary schools in Shanghai during two sampling periods in cold and warm seasons in 2007. Nine polycyclic aromatic hydrocarbons (PAHs) and ten nitro-polycyclic aromatic hydrocarbons (NPAHs) in PM2.1 were determined. During both seasons, the concentrations of PAHs and NPAHs at urban and suburban schools were not significantly different (p>0.05) and were higher in the cold period than in the warm period. According to the diagnostic ratios, PAHs and NPAHs at both schools were subject to the mixed effects of vehicle emission and coal combustion during both periods. Moreover, the results of the backward trajectory showed that PAHs and NPAHs were more susceptible to external polluted air masses in the cold period. At both urban and suburban schools, the inhalation cancer risk of PAHs and NPAHs in PM2.1 for children during elementary period was dozens of times of the acceptable risk level regulated by the U.S.EPA, highlighting the adverse impact of exposure to PAHs and NPAHs on the healthy development of children.

Airborne particulates were collected at an urban site (site 1) from 2004 to 2010 and at a suburban site (site 2) in 2010 in Beijing. Nine polycyclic aromatic hydrocarbons (PAHs) and five nitropolycyclic aromatic hydrocarbons (NPAHs) in the airborne particulates were determined by HPLC with fluorescence and chemiluminescence detection, respectively. The concentrations of PAHs and NPAHs were higher in heating season than in non-heating season at the two sites. Both the concentrations of PAHs and NPAHs decreased in the non-heating season but only the concentrations of NPAHs decreased in heating season at site 1, from 2004 to 2010. These findings suggest that source control measures implemented by the city of Beijing helped to reduce air pollution in Beijing. The concentrations of PAHs increased at site 1 in 2010, possibly because of the transport of emissions from windward other areas, such as Shanxi province. Several diagnostic ratios of PAHs and NPAHs showed that the different sources contributed to Beijing's air pollution, although coal combustion was the main source in the heating season and vehicle emission was the main source in the non-heating season. An analysis of physical parameters at Beijing showed that high wind speed can remove atmospheric PAHs and NPAHs in the heating season and that high relative humidity can remove them in the non-heating season. © 2017 Elsevier Ltd, Embargo Period 12 months

The concentrations of functionalized polycyclic aromatic hydrocarbons (PAHs), i.e., oxygenated PAHs (OPAHs), nitrated PAHs (NPAHs), and chlorinated PAHs (ClPAHs), in soluble organic fractions of automobile exhaust particles (NIST SRM 1975 and NIES CRM No.8) and airborne particles (NIST SRM1648a and PM₂.₅ collected at Kyoto, Japan) were simultaneously determined using gas chromatography–mass spectrometry with negative chemical ionization (GC–NCI–MS). The concentrations of PAH derivatives in standard reference materials determined by GC–NCI–MS were in good agreement with the certified and literature values. Ten OPAHs, 12 NPAHs, and 12 ClPAHs were detected in ambient PM₂.₅ collected in Kyoto, Japan by the proposed analytical method., The 25th International Symposium on Polycyclic Aromatic Compounds (ISPAC 25)

The assessment of occupational exposure to diesel exhaust (DE) is important from an epidemiological perspective. Urinary biomarkers of exposure have been proposed as a novel approach for measuring exposure to DE. In this study, we measured the concentrations of two urinary metabolites of 1-nitropyrene (1NP), a nitrated polycyclic aromatic hydrocarbon that has been suggested as a molecular marker of diesel particulate matter. These two metabolites, 6-hydroxy-1-nitropyrene and 8-hydroxy-1-nitropyrene, were determined in urine samples (10mL) from a small group of workers who were occupationally-exposed to vehicle exhaust in Trujillo, Peru, before and after their workshifts. Workshift exposures to 1NP, as well as PM2.5, 2-nitropyrene and 2-nitrofluoranthene, were also measured. Exposures to 1NP were similar in all studied workers, averaging 105±57.9pg/m3 (±standard deviation). Median urinary concentrations of the average of the pre- and post-exposure samples for 6-hydroxy-1-nitropyrene and 8-hydroxy-1-nitropyrene, were found to be 3.9 and 2.3pgmetabolite/mg creatinine, respectively in the group of occupationally-exposed subjects (n=17) studied. A direct relationship between workshift exposure to 1NP and urinary 1NP metabolites concentrations was not observed. However, the 1NP exposures and the creatinine-corrected urinary concentrations of the hydroxynitropyrene metabolites in these Peruvian traffic workers were similar to occupationally-exposed taxi drivers in Shenyang, China, and were higher than biomarker levels in office workers from Trujillo without occupational exposure to vehicle exhaust. This study provides further evidence that urinary metabolites of 1NP are associated with exposure to DE and may serve as a useful exposure biomarker.

Surface water samples were collected at 15 sampling sites in the southeastern Japan Sea along the Japanese Archipelago for analysis of polycyclic aromatic hydrocarbons (PAHs). Water samples were fractionated by filtration through a glass fiber membrane (pore size 0.5 µm) and analyzed by high-performance liquid chromatography with fluorescence detection. Thirteen PAHs having 3 to 6 rings were found in the dissolved phase (DP) and 12 were found in the particulate phase (PP). The total (DP+PP) PAH concentration ranged from 6.83 to 13.81 ng/L with the mean±standard deviation (S.D.) concentration of 9.36±1.92 ng/L. The mean±S.D. PAH concentration in the DP and PP was 5.99±1.80 and 3.38±0.65 ng/L, respectively. Three-ring PAHs predominated in the DP, while the proportion of 4-ring PAHs was higher in the PP. The mean total PAH concentration in the southeastern Japan Sea was higher than the concentration in the northwestern Japan Sea (8.5 ng/L). The Tsushima Current, which originates from the East China Sea with higher PAH concentration, is considered to be responsible for this higher concentration.

Total suspended particulates were collected at a Japanese remote background site (Noto Air Monitoring Station; NAMS) on the Noto Peninsula from September 2004 to June 2014. Nine polycyclic aromatic hydrocarbons (PAHs) in the particulates (fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene) were determined by HPLC with fluorescence detection. The mean total concentrations of the nine PAHs in the cold season (November to May for the years 2004-2014) was 670 pg m-3 (range 37-4100 pg m-3). The mean total concentration in the warm season (June to October for the same period) was 170 pg m-3 (range 31-960 pg m-3). The atmospheric PAH level at NAMS decreased in recent years, although no significant change was found in the warm season. An analysis of meteorological conditions showed that the atmospheric PAHs at NAMS were long range transported from Northeast China in the cold seasons and were contributed to by Japanese domestic sources in the warm seasons. Lower concentration ratios of reactive PAHs to their isomers at NAMS also supported these results. Activities associated with the Beijing Olympic and Paralympic Games in 2008 and reconstruction after the 2007 Noto Hanto earthquake may have contributed to the yearly variations of atmospheric PAH levels at NAMS during the period 2007-2009. Source control measures implemented by the Chinese and Japanese governments appear to have been effective in decreasing the atmospheric PAH levels at NAMS in recent years. © 2015 Elsevier Ltd., Embargo Period 24 months

Polycyclic aromatic compounds are ubiquitous atmospheric pollutants with toxic, mutagenic, and carcinogenic properties. They are produced from the chemical reactions of their parent or related compounds in the atmosphere as well as from a wide variety of anthropogenic sources, such as fuel combustion. In this chapter, chemical reaction pathways for the atmospheric secondary formation of several polycyclic aromatic hydrocarbon (PAH) derivatives, i.e., gas-phase formation of mutagenic 1- and 2-nitrotriphenylene via OH or NO3 radical-initiated reactions of the parent triphenylene, formation of carcinogenic 1-nitropyrene from heterogeneous nitration of pyrene on mineral dust aerosols, atmospheric formation of hydroxynitropyrenes from a photochemical reaction of 1-nitropyrene, and photochemical degradation of selected nitrated and oxygenated PAHs on airborne particles under simulated solar UV irradiation, are addressed.

Polycyclic aromatic hydrocarbons (PAHs) are known as carcinogenic and/or mutagenic substances, and are present at high concentration in polluted environments. It has recently been reported that spore-forming bacteria (e.g., Bacillus spp.) can be transported long distances alive in the atmosphere, which raises the possibility that some of the transported bacteria could have adverse effects on human health. There is thus a need for filters that can remove gaseous PAHs from the air that people breathe and that can inhibit bacterial growth on the filters. We focused on metallophthalocyanine derivatives (M-Pc) which are known to adsorb PAHs as well as to inhibit the growth of bacteria as a potential filtering agent. In this study, we developed different types of M-Pc-supported rayon fibers by changing central metals, functional groups, concentrations of M-Pc and rayon types, and evaluated their removal effects by measuring adsorption rates of 3- and 4-ring PAHs with a HPLC and growth curves of Bacillus sp. with a spectrophotometer. The results showed that both the effects depended on functional groups and concentrations of M-Pc, and rayon types. The most effective combination was observed in Fe-Pc with sulfo group supported on cationized rayon fiber at the concentration of 2 to 3.3 wt%. Central metal species of M-Pc were influenced only on the antibacterial properties. This fiber would be applicable to filtering agents and textiles.

Chiang Mai and several other provinces in northern Thailand have been annually facing air pollution problems during the dry season. Ten polycyclic aromatic hydrocarbons (PAHs); 19 nitropolycyclic aromatic hydrocarbons (NPAHs); and levoglucosan (LG), a marker for biomass burning, were quantified in total suspended particulates (TSP) collected in Chiang Mai during the dry, transition, and wet seasons in 2010. The concentrations of PAHs and NPAHs in the dry season were significantly higher than in the wet season. The [Benzo[a]pyrene (BaP)] – [benzo[ghi]perylene (BghiPe)] ratio, as an indicator of traffic, and the correlations of PAHs and NPAHs with LG showed that biomass burning significantly contributes to air pollution in the dry season. 9-Nitroanthracene (9-NA) was the most abundant NPAH which suggests that 9-NA is generated from biomass burning. We proposed the [9-NA] – [1-nitropyrene (1-NP)] ratio as a new indicator for assessing the contribution of biomass burning. Biomass burning was a major source of PAHs and NPAHs in the dry season, whereas vehicle exhaust was the main contribution in the wet season. The high carcinogenic risks in the dry season correlate with more harmful air conditions during this season. Thus, it is important to control biomass burning to reduce air-pollution-related health risks during the dry season in northern Thailand.

We determined eleven PAHs and four NPAHs in particulates and regulated pollutants (CO, CO2, HC, NOx, PM) exhausted from motorcycles to figure out the characteristics of motorcycle exhausts. Fluoranthene and pyrene accounted for more than 50% of the total detected PAHs. Among four detected NPAHs, 6-nitrochrysene and 7-nitrobenz[a]anthracene were the predominant NPAHs and were highly correlated relationship with their parent PAHs (R = 0.93 and 0.97, respectively). The PM and HC emissions tended to be close to the PAH emissions. NOx and NPAHs were negatively correlated. Despite their small engine size, motorcycles emitted much more PM and PAHs, showed stronger PAH-related carcinogenicity and indirect-acting mutagenicity, but weaker NPAH-related direct-acting mutagenic potency than automobiles. This is the first study to analyze both PAHs and NPAHs emitted by motorcycles, which could provide useful information to design the emission regulations and standards for motorcycles such as PM.

Polycyclic aromatic hydrocarbons (PAHs) are included in various environmental pollutants such as airborne particles and have been reported to induce a variety of toxic effects. On the other hand, PAH derivatives are generated from PAHs both through chemical reaction in the atmosphere and metabolism in the body.PAH derivatives have become known for their specific toxicities such as estrogenic/antiestrogenic activities and oxidative stress, and correlations between the toxicities and structures of PAH derivatives have been shown in recent studies. These studies are indispensable for demonstrating the health effects of PAH derivatives, since they would contribute to the comprehensive toxicity prediction of many kinds of PAH derivatives.

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.

Atmospheric nitrated polycyclic aromatic hydrocarbons (NPAHs), which have been shown to have adverse health effects such as carcinogenicity, are formed in part through nitration reactions of their parent polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. However, little is known about heterogeneous nitration rates of PAHs by gaseous NO2 on natural mineral substrates, such as desert dust aerosols. Herein by employing kinetic experiments using a flow reactor and surface analysis by Fourier transform infrared spectroscopy with pyridine adsorption, we demonstrate that the reaction is accelerated on acidic surfaces of mineral dust, particularly on those of clay minerals. In support of this finding, we show that levels of ambient particle-associated NPAHs in Beijing, China, significantly increased during heavy dust storms. These results suggest that mineral dust surface reactions are an unrecognized source of toxic organic chemicals in the atmosphere and that they enhance the toxicity of mineral dust aerosols in urban environments.

We investigated polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) in airborne particulates collected at two sites (I and T) in Hanoi city, a typical city where traffic jams were caused by many motorbikes. The mean total concentration of 10 PAHs having 4–6 rings at sites I and T ranged from 9.6–63.7 pmol m−3 and from 24.8–41.9 pmol m−3, respectively. The predominant PAHs determined were 6-ring PAHs: benzo[ghi]perylene (BghiPe), indeno[1,2,3-cd]pyrene (IDP) and 5-ring PAHs: benzo[b]fluoranthene (BbF), benzo[a]pyrene (BaP). The NPAHs with the highest mean concentrations were 9-nitroanthracene (9-NA) (297 ± 134 fmol m−3) at site I and 1-nitropyrene (1-NP) (331 ± 103 fmol m−3) at site T. Both PAH and NPAH concentrations were higher in winter at site I but higher in summer at site T. Diagnostic markers indicated that motorbikes strongly contributed to atmospheric PAHs and NPAHs in Hanoi city. The contribution of PAHs having 6 rings and 7-NBaA in Hanoi city was larger and ...

Twenty-one data sets composed of readings collected by atmospheric ozone monitors worn by individuals on their clothing and installed outside their home or office were collected using Ogawa passive ozone samplers in southeastern Hyogo prefecture, Japan from September 12 to 13, 2011. The concentrations of personal and outdoor ozone ranged from not detectable to 23.2 ppb and from 4.7 to 38.3 ppb, respectively. The mean concentration of personal exposure to ozone was 3.7 ppb and was significantly lower than that of outdoor ozone (18.5 ppb). This suggests that the concentrations of outdoor ozone affect personal ozone exposure. However, in this study, we found no correlation between the concentrations of personal ozone and the total time spent outdoors or the time of day the individual was outside. In contrast, the mean concentrations of outdoor ozone were similar to those of ozone measured at the 12 nearest Ambient Monitoring Stations (AMSs). However, when the AMS was situated near a main road, the regional ozone levels were underestimated.

Airborne particulates were collected in three size fractions by using Anderson low-volume air samplers in Shenyang, China, in winter and summer in 2007. Compared with data obtained in 2001 at the same sites, the total concentrations of nine polycyclic aromatic hydrocarbons (PAHs) in winter decreased by 67% at one site and decreased by 40% at the other site, while the total concentrations of four nitropolycyclic aromatic hydrocarbons (NPAHs) did not decrease. This suggests that environmental countermeasures begun in 2001 were effective in decreasing the concentration of PAHs. However, in summer, the concentrations of PAHs and NPAHs rose by the factors of 4 and 5, respectively, possibly because of an increase in the number of motor vehicles. © 2011 Taylor and Francis Group, LLC.

Polycyclic aromatic hydrocarbons (PAHs) and selected nitrated derivatives (NPAHs) in air were determined at two sites, El Dokki (a traffic site) and El Teppen (an industrial site) in Greater Cairo, Egypt, during the winter and summer seasons. The sites were selected to represent areas with different activities of Greater Cairo. The concentrations of fifteen PAHs having two to six rings were determined by using HPLC with florescence detection, while the concentrations of two NPAHs, 1-nitropyrene (1-NP) and 6-nitrocrysene (6-NC), were determined using HPLC with chemilumencence detection. Both the PAH and NPAH concentrations in El Teppen were higher than those in El Dokki. The total average concentrations of the fifteen PAHs over the investigated sites were 45.98 pmol m −3 in El Dokki and 77.01 pmol m −3 in El Teppen. All PAH and NPAH concentrations were higher in winter than in summer. The total average concentration of PAHs ranged from 21.9 pmol m −3 in summer to 63.74 pmol m −3 in winter. PAHs having four to six rings were the predominant compounds in particulate matters. The total average concentrations of the two NPAHs (1-NP and 6-NC) were 30.2 and 12.4 fmol m −3 , respectively, in El Dokki, and 39.5 and 15.6 fmol m −3 respectively, in El Teppen. The total average concentrations of 1-NP and 6-NC were 36.99 and 15.43 fmol m −3 , respectively, in winter, and 29.76 and 10.56 fmol m −3 , respectively, in summer. These concentrations were compared with those of several cities in Asia that have been undergoing rapid economic and industrial development. The major sources and secondary reactions of PAHs and NPAHs were estimated based on the [NPAH]/[PAH] and [PAH]/SPM ratios.

Polycyclic aromatic hydrocarbons (PAHs) and dioxins have several toxic properties, including mutagenicity, carcinogenicity and reproductive toxicity. PAHs mainly originate from the burning of petroleum and coal, while dioxins originate mainly from waste incineration and agrochemicals. Both PAHs and dioxins have aryl hydrocarbon receptor (AhR) binding activity which is related to toxicity of PAHs and dioxins. In this study, we evaluated AhR binding activity of airborne particles collected in Beijing, China and Kanazawa, Japan by DR-CALUX and the contribution of PAHs and dioxins to this activity. AhR binding activity of airborne particles in Beijing (1,200 ng • m-3) was four hundred times higher than in Kanazawa (2.7 ng • m-3). The composition of PAHs didn′t show large difference in Beijing and Kanazawa. The contribution of the PAHs to CALUX-TEQ was higher than dioxins and especially high in Kanazawa (10.4 %). These results suggest that PAHs show large contribution to the toxicity of airborne particles, and other kinds of PAH and PAH related compounds will also contribute to that toxicity. The difference of concentration and composition of these compounds result in the different level of toxicity of airborne particles in each city.

Polycyclic aromatic compounds are ubiquitous atmospheric pollutants with toxic, mutagenic, and carcinogenic properties. They are produced from chemical reactions of their parent compounds in the atmosphere as well as from a wide variety of anthropogenic sources such as fuel combustions. The present review is mainly concerned with several reaction pathways regarding secondary formation of atmospheric polycyclic aromatic hydrocarbon (PAH) derivatives, i.e., formation of mutagenic nitrated PAHs, 1- and 2-nitrotriphenylene, via gas-phase OH or NO3 radical-initiated reactions of the parent triphenylene, atmospheric formation of hydroxynitropyrenes from a photochemical reaction of 1-nitropyrene, and photochemical degradation of selected nitrated and oxygenated PAHs on airborne particles under simulated solar UV-irradiation.

A correction method for the determination of atmospheric monohydroxylated derivatives of 1-nitropyrene (hydroxy-1-nitropyrenes, OHNPs) based on their degradation rates during high volume air sampling was established. OHNPs adsorbed directly on a quartz fibre filter (QFF) or on airborne particles collected on a QFF were exposed to ambient air passively or actively in a high volume air sampling system. The influence of ozone flux and exposure time on the degree of degradation of OHNPs was investigated. Up to 50% of OHNPs degraded over 1 h of exposure to ambient air containing ∼60 ppbv of ozone in the active system. The degradation rate constants of OHNPs were found to correlate with the number of ozone molecules passing through the QFF in a unit time (NO3) during high volume air sampling. The chemical loss of OHNPs under high volume air sampling conditions was successfully evaluated by the exposure time and the pseudo-first-order rate constant for OHNP degradation estimated from the correlation with NO3. Co...

Particulates exhausted from two types of diesel engines (DEPs), burning-derived particulates from three types of coal (CBPs) and burning-derived particulates from three types of wood (WBPs) were separated into four fractions by silica-gel column chromatography using n -hexane, n -hexane–dichloromethane (3:1, v/v), dichloromethane and methanol, as the corresponding eluents. The indirect-acting mutagenicity of each fraction was assayed by the Ames test using the Salmonella typhimurium TA100 strain with S9 mix and the direct-acting mutagenicity was assayed using the S. typhimurium TA98 strain without S9 mix. The polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) of each fraction were determined by high-performance liquid chromatography (HPLC). Both direct- and indirect-acting of mutagenicities were the highest in samples of DEPs. The contributions of PAHs in samples of WBPs and NPAHs in DEPs were the largest, respectively.

Airborne particulate matter was collected at Wajima, the Noto Peninsula, Ishikawa, Japan by a high-volume air sampler with a quartz fiber filter every week from September 17, 2004 to September 16, 2005. The filter was newly changed every week. There are no major emission sources of atmospheric pollutants near the sampling site. Water-soluble fluoride anion extracted from the filters was analyzed by ion chromatography. The concentration of non-sea-salt fluoride was higher during the heating period of China (from October 15, 2004 to April 15, 2005), significantly higher during the period of Asian Dust (from the mid of April to the beginning of May in 2005), than that in the other seasons. This result suggests that the main contributor of fluoride in the period of Asian Dust was high-fluoride-concentrated soil from the and area of China. A noticeable positive correlation (r = 0.54, n = 28, p < 0.01) between the level of non-sea-salt fluoride and PAHs was observed, when only the data obtained during the period of Asian Dust was excluded. In view of the fact that PAHs emitted from Northeast China were long-range transported to Japan during the heating period of China, fluoride emitted from coal combustion long-range transported from the Asian continent to Japan during the same period appears to be another main source of fluoride. (c) 2009 Elsevier B.V. All rights reserved.

Airborne particulates were collected in three different size fractions (>7 μm; 2.1-7 μm

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.

Urban air pollution in many cities of the developing world in Asia, particularly in Vietnam, is increasing significantly. Atmospheric particulate matter pollution is dangerous to the health of millions of people and is a particular concern. In this study, two nitro-polycyclic aromatic hydrocarbons (nitro-PAHs), 1-nitropyrene (1-NP) and 2-nitrofluoranthene (2-NF) and several polycyclic aromatic hydrocarbons (PAHs)—highly carcinogenic and mutagenic compounds—were quantified in particulate matter (PM) collected at three ambient air sites (VNU, ITTE and DOSTE) in an urban area of Ho Chi Minh City, Vietnam, between January 2005 and March 2006. The DOSTE site was close to ground level on a street with a high traffic density. 2-NF was more abundant than 1-NP at all sampling sites. Concentrations of 1-NP and PAHs at the traffic site (DOSTE) were higher than those at the other sites (VNU and ITTE). The daytime/nighttime distribution of 2-NF and the 2-NF/1-NP ratios were used to evaluate the gas-phase formation of 2-NF and its formation route. The average ratios of 2-NF/1-NP at the VNU and ITTE sites were much higher than those at the DOSTE site, suggesting that the gas-phase reactions are an important source of 2-NF in the ambient air. The higher nighttime concentration of 2-NF observed at the VNU and ITTE sites and the converse result observed for the traffic site indicates that an NO3 radical-initiated reaction is the dominant route for 2-NF formation in ambient air, while the majority of 2-NF at the traffic site may be attributed to OH radical-initiated reactions.

Airborne particulate matter was collected at Wajima, on the Noto Peninsula, Ishikawa, Japan by a high-volume air sampler with a quartz filter every week from 17 September 2004 to 16 September 2005. Polycyclic aromatic hydrocarbons (PAHs) extracted from filters were analyzed by HPLC with fluorescence detection. The atmospheric concentrations of PAHs at Wajima were higher during the heating period of China (when coal is burned for heat) than during the no-heating period. A meteorological analysis indicated that the air samples collected in that heating period at Wajima were transported mainly from Northeast China over the Japan Sea. Principal component analysis of nine PAHs indicated a Chinese origin of the PAHs. These results strongly suggest that the high-level PAHs detected at Wajima were the result of long-range transport from China.

The purpose of this study was to characterize size distributions of atmospheric polycyclic aromatic hydrocarbons (PAHs) with 4–6 rings at the roadside in Ho Chi Minh City, Vietnam. Ten PAHs (fluoranthene, pyrene, triphenylene, benzo[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, benzo[ ghi ]perylene and indeno[1,2,3- cd ]pyrene) in atmospheric particulate matters (PM) at the roadside were measured in the dry and rainy seasons in 2005 at Ho Chi Minh City, using a low-pressure cascade impactor. The PM were separated into nine fractions by their aerodynamic diameter, i.e. >9.0, 9.0–5.8, 5.8–4.7, 4.7–3.3, 3.3–2.1, 2.1–1.1, 1.1–0.7, 0.7–0.4 and 2.1 μm). Generally, 5,6-ring PAHs associated mainly with fine particles and 4-ring PAHs spread out in both fine and coarse particles.

Airborne particulates were collected in nine size fractions by using Andersen low-volume air samplers in the cities of Shenyang, Fushun, and Tieling, Liaoning Province, in northeast China, during the period from July 2001 through December 2003. Nine polycyclic aromatic hydrocarbons (PAHs) and seven nitropolycyclic aromatic hydrocarbons (NPAHs) in the airborne particulates were determined. The mean concentrations of the sums of the nine PAHs and seven NPAHs were highest in Fushun, which is an industrial city, and lowest in Shenyang, which is a commercial city, although the consumption of petroleum and coal were largest in Shenyang. The nine fractions were grouped into three groups: > 7 μ m, 2.1–7 μ m and < 2.1 μ m. In each city, more than 50% of the total PAHs and total NPAHs were found in the fine particulate fraction (< 2.1 μ m). In each city, all PAHs and all NPAHs were clearly higher in winter than in summer. The concentration ratio of 1-nitropyrene to pyrene, which is a suitable indicator to identify ...

The association of the direct-acting mutagenicity of soluble organic fraction of airborne particles toward Salmonella typhimurium YG1024 strain with the direct emission was investigated at a roadside and at a residential area in Osaka, Japan. The direct-acting mutagenicity was evaluated as mutagenic activity per unit volume of ambient air (rev m −3 ) and/or that per airborne particulate weight collected on a filter (rev mg −1 ). The annual or diurnal changes of the mutagenicity of airborne particles at the residential site showed similar patterns to those of some gaseous pollutants such as NO 2 and SO 2 , which were emitted from combustion processes. This result indicates that the mutagenicity is mainly attributable to the primary emissions. From the analysis of the relationship between the wind sector and the mutagenic intensity, rev m −3 and rev mg −1 values were strongly affected by the emissions from the fixed sources and from the mobile sources, respectively. The rev m −3 value and concentration of 1-nitropyrene (1-NP) in unit per m 3 at the roadside were a factor of 2.6 and 2.8 higher than those at the residential site, respectively, but the rev mg −1 value and concentration of 1-NP in unit per mg at the roadside were substantially comparable to those at the residential area. These observations suggest that the characteristics of the airborne particles can be attributed to the automotive emissions even at the suburban area.

The direct-acting mutagenicity of soluble organic fraction (SOF) of airborne particles, and the concentration of five gaseous air pollutants and two nitroarenes, 1-nitropyrene (1-NP) and 2-nitrofluoranthene (2-NF) were determined to clarify their diurnal variation pattern by collecting airborne particles every 3 or 4 h in a slightly polluted residential area at southern Osaka, Japan. The direct-acting mutagenicity of SOF toward Salmonella typhimurium YG1024 strain, i.e. mutagenicity in the absence of microsomal activation, was high early in the morning and late in the evening, while it was low both in the daytime and in the nighttime. The diurnal variation pattern of the mutagenicity was similar to those of the concentration of NO, CO, and 1-NP, which were primarily emitted from combustion processes such as diesel-powered vehicles. On the other hand, a significant correlation was observed between diurnal variations of the concentration of 2-NF and hydroxyl radical in October. The concentration of 2-NF in airborne particles collected in July was comparable to that in October. Based on the specific mutagenic activity of 1-NP and 2-NF, their contribution to the total direct-acting mutagenicity of SOF toward YG1024 strain were estimated to be small as 0.03–0.06% and 0.2–1.1%, respectively. However, some of atmospherically formed nitroarenes would contribute to the direct-acting mutagenicity of the air in the daytime, when atmospheric formation of nitroarenes initiated by the reactions with radical species is expected to occur even since the mutagenicity originated from primarily emitted mutagens should be suppressed by photo-decomposition of the mutagens.

Concentrations of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and polycyclic aromatic hydrocarbons (PAHs) in airborne particles collected at two sites, a residential area and a roadside with high traffic density in Osaka, Japan, in summer and winter were quantified. Five nitro-PAHs, 1-nitropyrene (1-NP), 2-nitropyrene (2-NP), 2-nitrofluoranthene (2-NF), 3-nitrofluoranthene (3-NF), and 2-nitrotriphenylene (2-NTP) and five PAHs, pyrene (Py), fluoranthene (Fl), triphenylene (Tp), benzo[k]fluoranthene (B(k)F), and benzo[a]pyrene (B(a)P) were determined by high-performance liquid chromatography with chemiluminescence and fluorescence detection. At both sites, the mean concentration of 1-NP was higher in winter than in summer. On the contrary, the mean concentrations of 2-NF and 2-NP were higher in summer than in winter. Observed 2-NF/2-NP ratio in the range from 0.40 to 16 suggests that 2-NF and 2-NP were dominantly formed via OH radical initiated reaction in the atmosphere. Nitro-PAH and PAH concen...

Airborne particulates were collected at a background site (Wajima Air Monitoring Station; WAMS) on the Noto Peninsula, Japan from January 2006 to December 2007. 1-, 2-nitropyrenes (1-, 2-NPs) and 2-nitrofluoranthene (2-NFR), in the particulates were determined with a sensitive HPLC method with chemiluminescence detection. The average concentrations were higher in winter than in summer. A meteorological analysis indicated that the air samples collected in winter were transported mainly from Northeast China over the Japan Sea. Both the concentration ratios of 2-NFR to 1-NP and 1-NP to pyrene were similar to those in Shenyang in Northeast China which located along the air transportation route to WAMS, but not in Kanazawa which near WAMS. These results strongly suggest that most of the atmospheric 1-, 2-NPs and 2-NFR at WAMS in winter were long range transported from Northeast China. © 2014 Elsevier Ltd. All rights reserved.

Diesel exhaust (DE) is a significant contributor to the toxicity associated with particulate matter (PM). 1-Nitropyrene (1-NP) has been used as a molecular marker for DE, and the urinary metabolites of 1-NP have been proposed as biomarkers for exposure to DE. In this study, several urinary 1-NP metabolites were evaluated for their utility as markers of short-term exposures to DE. The study population was a cohort of 24 taxi drivers from Shenyang, China, who submitted urine samples collected before, after, and the next morning following their workshifts. The urinary metabolites studied were isomers of hydroxy-1-nitropyrene (3-, 6-, 8- OHNPs) and hydroxy-N-acetyl-1-aminopyrene (3-,6-, 8-OHNAAPs). Exposure to DE was estimated based on exposure to 1-NP in air samples collected during and after the driver's workshift; 6- and 8-OHNP, and 8-OHNAAP were consistently detected in the drivers' urine. Concentrations of the metabolites in the taxi drivers' urine were greater than metabolite levels previously reported in non-occupationally exposed subjects; however no associations were observed between subject-specific exposures to 1-NP and urinary metabolites measured at the end of the workshift or in the next morning void. Significant autocorrelation was observed in metabolite levels in successive urine samples, from which half-lives for urinary elimination of ~10-12 h were estimated. These observations suggest that, in an occupational setting, urinary 1-NP metabolites may be more suitable as markers of ongoing exposure (timescales of several days) rather than indicators of acute exposure associated with single workshifts.

The kinetics of CCl(4) liquid-phase reactions of ten kinds of polycyclic aromatic compounds (PACs) including triphenylene (TP) with NO(3) radicals have been investigated at 273K by a relative rate method using naphthalene (NA) as a reference compound. The obtained relative reaction rates of the tested PACs to NA in CCl(4) were as follows: 2.57±0.24 (acenaphthene), 2.11±0.30 (2,3-dimethylnaphthalene), 1.21±0.13 (fluoranthene), 0.56±0.07 (fluorene), 1.85±0.19 (1-methylnaphthalene), 1.77±0.12 (2-methylnaphthalene), 0.11±0.03 (1-nitronaphthalene), 1.59±0.23 (phenanthrene), 2.40±0.29 (pyrene), 0.22±0.04 (TP). TP is a semi-volatile PAC with four aromatic rings and it is chemically changed into mutagenic 2-nitrotriphenylene (2-NTP) via the gas-phase OH or NO(3) radical-initiated reactions. On the basis of the relative reactivity of the PACs in the CCl(4) liquid phase-system, the rate constants of the gas-phase reactions of TP with OH and NO(3) radicals at 298 K were predicted to be (8.6±1.2)×10(-12) cm(3) molecule(-1) s(-1) and (6.6±1.5)×10(-29)[NO(2)] cm(3) molecule(-1) s(-1), respectively. Based on the ambient concentrations of TP and 2-NTP and the obtained rate constant for the reaction of TP with OH radicals, the atmospheric loss rate of 2-NTP was also evaluated.

The formation of hydroxynitropyrene (OHNP) via a photochemical reaction of 1-nitropyrene (1-NP) was demonstrated using a UV irradiation system. The photoreaction of 1-NP in methanol gave products that were hydroxy-substituted at position 1 and mononitro-substituted at positions 2, 3, 5, 6, and 8 [1-hydroxy-x-nitropyrenes (1-OH-x-NPs); x = 2, 3, 5, 6, and 8]. 1-OH-2-NP and 1-OH-5-NP have been identified in ambient airborne particles for the first time. On the contrary, these two OHNP isomers were not found in standard reference materials (SRM) 1650b and SRM 1975, which are typical samples of diesel exhaust particles (DEPs). The concentrations of the other OHNP isomers in the DEP samples were much lower than the concentration of 1-NP, which is a representative nitro-derivative polycyclic aromatic hydrocarbon that is emitted directly from combustion sources. On the other hand, significantly higher concentration ratios of ∑OHNP (=1-OH-3-NP + 1-OH-6-NP + 1-OH-8-NP) to 1-NP were observed in ambient airborne particles than in the DEP samples. In ambient airborne particles, the mean ∑OHNP/1-NP concentration ratio of 1.4 was 35 times higher than that in SRM 1650b and 470 times higher than that in SRM 1975. The diurnal concentration of 1-NP, which was observed at a typical residential area in Osaka, Japan, increased early in the morning and late in the evening, suggesting that automotive emissions contributed to the occurrence of 1-NP. The OHNP concentrations also rose in the morning, and variations of OHNP concentrations similar to those of 1-NP were observed during the daytime. However, the concentrations of OHNPs did not increase in the evening rush hour, and were low at night, i.e., in the absence of sunlight. These results support the idea that atmospheric OHNPs are predominantly formed via secondary formation processes; i.e., photochemical reactions of 1-NP are expected to have a significant effect on the occurrence of OHNPs in the atmosphere.

Marine water is contaminated with polycyclic aromatic hydrocarbons (PAHs) from rivers and the atmosphere. Oil spilled from tankers or petroleum factories also causes marine pollution with PAHs. It is well known that PAHs, such as benzo[a]pyrene, show carcinogenicity and/or mutagenicity. In developing teleost fish, furthermore, it has been reported that spinal deformity was induced in Pacific herring and pink salmon by PAHs, although the detail mechanism of toxicity in teleosts is not elucidated yet. As a toxic pathway of PAHs in animals, the metabolic activation of PAHs in the presence of P450 is considered. In teleosts, as well as in mammals, it has been reported that PAHs are converted into monohydroxylated polycyclic aromatic hydrocarbons (OHPAHs) by an enzyme: cytochrome P4501A1. Thus, OHPAH might have a toxic effect in teleosts. In the present study, we examined the estrogenic activity of OHPAHs using the yeast-two hybrid assay system with human estrogen receptor ER) . As a result, we detected estrogenic activity in 4-hydroxybenz[a]anthracene (4OHBaA). Then, the direct effect of 4-OHBaA on osteoclasts and osteoblasts in teleosts was examined using the assay system with fish scales, which contain osteoclasts, osteoblasts, and the bone matrix of two layers (bony layer: a thin, well-calcified external layer; a fibrillary layer: a thick, partially calcified layer). When the scales of goldfish and wrasse were incubated with 4-OHBaA, which

Polycyclic aromatic hydrocarbons (PAHs), some of which are carcinogenic/mutagenic, are generated by combustion of fossil fuels and also released through tanker or oilfield accident to cause a large scale environmental pollution. PAHs concentration in China is especially high in East Asia because of many kinds of generation sources such as coal heating systems, vehicles and factories without exhaust gas/particulate treatment systems. So, the atmospheric pollution caused by PAHs in China has been seriously concerned from the view point of health effects. Like yellow sand and sulfur oxide, PAHs exhausted in China are also transported to Japan. Additionally, strongly mutagenic nitrated PAHs (NPAHs), estrogenic/antiestrogenic PAH hydroxides (PAHOHs) and reactive oxygen species-producing PAH quinones (PAHQs) are formed from PAHs by the chemical reaction during the transport. Furthermore these PAHOHs and PAHQs are produced by the metabolism in animal body. In the biological activities caused by the above PAH derivatives, the structure-activity relationship was observed. In this review, our recent results on the generation of PAH derivatives by atmospheric transport and metabolism are reported. Also, the existing condition of PAHs as atmospheric pollutants is considered.

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.