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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.

Ambient particulate matter (PM) epidemiologically exacerbates respiratory and immune health, including allergic rhinitis (AR) and bronchial asthma (BA). Although fine and coarse particles can affect respiratory tract, the differences in their effects on the upper and lower respiratory tract and immune system, their underlying mechanism, and the components responsible for the adverse health effects have not been yet completely elucidated. In this study, ambient fine and coarse particles were collected at three different locations in Japan by cyclone technique. Both particles collected at all locations decreased the viability of nasal epithelial cells and antigen presenting cells (APCs), increased the production of IL-6, IL-8, and IL-1β from bronchial epithelial cells and APCs, and induced expression of dendritic and epithelial cell (DEC) 205 on APCs. Differences in inflammatory responses, but not in cytotoxicity, were shown between both particles, and among three locations. Some components such as Ti, Co, Zn, Pb, As, OC (organic carbon) and EC (elemental carbon) showed significant correlations to inflammatory responses or cytotoxicity. These results suggest that ambient fine and coarse particles differently affect nasal and bronchial epithelial cells and immune response, which may depend on particles size diameter, chemical composition and source related particles types.

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.

CCl4 liquid-phase reaction kinetics of polycyclic aromatic compounds (PACs), including chrysene (CHRY), benz[a]anthracene (BaA), and benzanthrone (BA), with NO3 radicals were investigated at 273 K using a relative rate method with naphthalene (NA) as the reference compound. The obtained relative reaction rates of CHRY, BaA, and BA to NA were 1.76 ± 0.08, 2.27 ± 0.20, 0.75 ± 0.01, respectively. CHRY, BaA, and BA are semi-volatile PACs with four aromatic rings. They are chemically modified into mutagenic nitropolycyclic aromatic compounds via gas-phase OH or NO3 radical-initiated reactions. Based on the PACs relative reactivity in the CCl4 liquid phase-system, the rate constants at 298 K for the gas-phase reaction of CHRY, BaA, and BA with OH radicals and those of CHRY, BaA, and BA with NO3 radicals were estimated to be (in cm3molecule−1s−1): CHRY, (4.4 ± 0.3) × 10−11 and (9.2 ± 3.2) × 10−28 [NO2]; BaA, (5.3 ± 0.5) × 10−11 and (1.3 ± 0.5) × 10−27 [NO2]; BA, (2.3 ± 0.1) × 10−11 and (3.1 ± 1.1) × 10−2...

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.

Polycyclic aromatic hydrocarbon quinones (PAHQs) are components in airborne particulate matter (PM) and generate reactive oxygen species (ROS) in a redox cycling process. 9,10-Phenanthrenequinone (9,10-PQ) is a PAHQ found in diesel exhaust particulates and PM. When inhaled, it produces much more ROS than other PAHQs. We hypothesized that urinary metabolites of 9,10-PQ could serve as biomarkers of PAHQ exposure. Here, we describe methods for pretreating urine samples and analyzing 9,10-PQ metabolites by liquid chromatography with tandem mass spectrometry (LC-MS/MS). In urine from rats intraperitoneally injected with 9,10-PQ, the monoglucuronide of 9,10-dihydroxyphenanthrene (9,10-PQHG) was found to be a major metabolite of 9,10-PQ. 9,10-PQHG was also identified in the urine of a nonoccupationally exposed human by its retention time and MS/MS spectra. Furthermore, the urine contained hardly any free (unmetabolized) 9,10-PQ, but treating it with hydrolytic enzymes released 9,10-PQ from conjugated metabolites such as 9,10-PQHG. The concentrations of 9,10-PQHG in urine samples from nonoccupationally exposed subjects who lived in a suburban area were 2.04-19.08 nmol/mol creatinine. This study is the first to demonstrate the presence of 9,10-PQHG in human urine. Determination of urinary 9,10-PQHG should be useful for determining 9,10-PQ exposure.

Particulate air pollutants and mineral fibers activate inflammatory cells to release oxidants, which contribute to inflammation and injury in the lower respiratory tract. Our aim was to compare the role of silica particle size with mineral fiber length and width in the ability to induce superoxide release from rat alveolar macrophages. We estimated the ability of four types of silica particle samples, with different mode diameter, and three types of mineral fiber samples, with different geometric mean lengths and widths, to induce lucigenin-dependent chemiluminescence (CL) from the cells per number of dust particles (i.e., silica particles and mineral fibers). A close positive correlation was observed between dust size and the ability to induce CL in silica as well as mineral fiber samples. Moreover, the ability of silica samples to induce CL was weaker than that of long mineral fiber sample. This ability increased at a larger rate in small silica particle and thin mineral fiber samples than in large silica particle and thick mineral fiber samples at the initial stage of administration. These results suggest that the kinetics of the induction superoxide release from macrophages is similar between silica particles and mineral fibers; moreover, this depends on silica particle size and mineral fiber geometry. Finally, large silica particles were more active than small ones.

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 developed a sensitive and selective method to simultaneously analyze 37 polycyclic aromatic hydrocarbon quinones (PAHQs) with GC-MS/MS and applied the method to the analysis of standard atmospheric particulate matter samples. PAHQs were reduced with zinc granules and dithiothreitol (DTT) and the reductants were immediately converted to their silylated derivatives in a test tube. Two trimethylsilyl (TMS) groups were introduced into PAHQs through the one-pot reductive TMS derivatization. The PAHQs were derivatized with a mixed silylation reagent (BSA+TMCS+TMSI; (3:2:3)), which is one of the combinations of TMS-derivatization reagents with the highest reactivity. The derivatives produced different fragmentation between o-PAHQs and p-PAHQs. Therefore, isomers that have the same molecular weight are difficult to separate on a column were separated by the selected reaction monitoring (SRM) mode using the characteristic fragmentations, allowing separation and detection of all PAHQ derivatives in less than 30min. The instrumental detection limit (IDL) of each PAHQ was 1.2-29fg/injection and the method quantification limit (MQL) was 0.8-78μg/kg sample. For quantification, six deuterated PAHQs were used as internal standards to achieve high analytical precision. We applied the developed method to four standard atmospheric particulate matter samples. Results showed that out of 37 PAHQs, 33 compounds were identified and quantified. Moreover, from the 33 PAHQs, 14 were detected for the first time. Similar values were observed for the concentrations of PAHQs that have been quantified in previous reports. This method has the highest practicality in monitoring PAHQs in atmosphere, combustion exhaust gas, and toxicity evaluation. Thus, the method has the potential to become a standard analytical method for such applications.

Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) is a widely used noninvasive biomarker of oxidative stress. A selective, sensitive and rapid method for determining 8-OHdG in human urine was developed using hydrophilic interaction chromatography-tandem mass spectrometry (HILIC-MS/MS) with electrospray ionization. 8-OHdG and isotopically labeled 8-OHdG (internal standard) were separated on a HILIC column with a mobile phase of 10. mM ammonium acetate: acetonitrile (1:9, v/v) within 10. min and detected by using a positive electrospray ionization interface under the selected reaction monitoring mode. The detection limits of 8-OHdG (corresponding to a signal-to-noise ratio of 3) for the HILIC-MS/MS system and the conventional method using a reversed-phase column with MS/MS were 1.0 and 26.0. fmol/injection, respectively. The proposed method makes it possible to monitor the basal level of urinary 8-OHdG from non-exposed healthy subjects and can be used for large-scale human studies. © 2012 Elsevier B.V.

An ultraweak chemiluminescence (CL) was observed when sodium hydrosulfite (NaHSO(3)) reacts with hydrogen peroxide (H(2)O(2)) and was enhanced 70 times by adding 10 pmol benzo[a]pyrene-7,10-quinone (7,10-BaPQ). The CL reaction is fast, and it reached maximum intensity in 0.1 s, and then decayed to baseline in 3 s. Mechanism of NaHSO(3)-7,10-BaPQ-H(2)O(2) system were investigated by CL spectrum, radical scavengers and electron spin resonance (ESR). Hydroxyl radical ((•)OH), super oxide anion radical ((•)O(2)(-)), and sulfite radical ((•)SO(3)(-)) were generated in the NaHSO(3)-7, 10-BaPQ-H(2)O(2) system. Reduction of 7,10-BaPQ by (•)O(2)(-) radical gave excited semiquinone, which showed strong CL emission when decayed to its ground state. Maximum CL emission wavelength was located at 440 nm, which may belong to the excited semiquinone. This CL system was developed as post column detection of high performance liquid chromatography for the determination of 7,10-BaPQ. Linearity ranged from 50 fmol to 20 pmol (R(2) = 0.9995) with limit of detection of 30 fmol (S/N = 3). The proposed method was used to determine 7,10-BaPQ in airborne particulates. Average atmospheric concentrations of 7,10-BaPQ in Kanazawa in December 2010 and Wajima in October 2007 were 2.0 and 1.6 pg/m(3), respectively.

The formation of hydroxynitrofluoranthene (OHNF) via photochemical reactions of 2-nitrofluoranthene (2-NF) was demonstrated using a UV irradiation system. The photoreaction of 2-NF in acetonitrile/water (3/1, v/v) gave a product that was hydroxynitro-substituted. Moreover, we detected an OHNF isomer, which was found in the 2-NF photoreaction products, in soluble organic fractions of ambient airborne particles collected in Kanazawa, Japan. The atmospheric concentration of the OHNF isomer was estimated to be less than 2 fmol m−3, which was comparable to that of 1-hydroxy-3-nitropyrene, but lower than that of 1-hydroxy-6-nitropyrene by a factor of 10. The results suggests that atmospheric OHNF is partly formed via secondary formation processes, i.e., photochemical reactions of 2-NF appear to have a significant effect on the occurrence of OHNF in the atmosphere.

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 ...

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants, and generate various types of PAH derivatives, such as nitrated PAHs, hydroxylated PAHs, and PAH quinones through chemical reactions in the atmosphere. PAHs are well known to activate the aryl hydrocarbon receptor (AhR), followed by the induction of metabolizing enzymes mainly in the liver, while biological responses to PAH derivatives are not understood well. In this study, we investigated the induction patterns of gene expression of CYP1 family and Phase II metabolizing enzymes in rat H4IIE cells exposed to PAH quinones and their parent PAHs for 24 h. Dibenz[a,h]anthracene and benzo[a]pyrene dramatically induced mRNA expression of CYP1 family, such as cytochrome P450 (Cyp) 1a1, Cyp1a2, and Cyp1b1, and PAH quinones, especially 1,4-chrysenequinone, possess a high potential to induce CYP1 family. As for Phase II enzymes, PAHs induced NAD(P)H: quinone oxidoreductase 1 (Nqo1) and UDP-glucuronosyltransferase (Ugt)1a6, and their i...

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.

1-Nitropyrene (1-NP), 2-NP and 2-nitrofluoranthene (2-NFR) are useful markers for studying the atmospheric behaviors of polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs). However, present methods for measuring trace levels of these compounds are less-sensitive and laborious. Here we describe several improvements to a previously reported high-performance liquid chromatography-chemiluminescence detection system that allows it to determine trace levels of 1-, 2-NPs and 2-NFR. The proposed system was equipped with a reducer column packed with Pt/Rh instead of zinc whose life-time was limited. The combination of Cosmosil MS-II (monomeric ODS) and AR-II (polymeric ODS) columns was used instead of polymeric ODS columns as the separator column to improve the separation. An ethanol mixture with acetate buffer (pH 5.5) was used in place of an acetonitrile mixture with the same buffer to activate the reducer column. The same ethanol mixture was used as the mobile phase for the clean-up column. The switching time of the column switching valve was optimized to concentrate the amino-derivatives of above NPAHs quantitatively on the concentrator column. The concentrations of bis(2,4,6-trichlorophenly) oxalate and hydrogen peroxide in the chemiluminescence reagent solution were optimized to 0.4 mM and 30 mM, respectively, to increase the sensitivity. Under the above conditions, the detection limits (S/N=3) of 1-, 2-NPs and 2-NFR were 1 fmol (0.25 pg), 10 fmol (2.5 pg) and 4 fmol (1 pg), respectively. The proposed system was effectively used to determine trace levels of 1-, 2-NPs and 2-NFR in airborne particulates collected at Noto Peninsula. The atmospheric concentrations of 1-, 2-NPs and 2-NFR were not more than sub pg m-3 levels. They were higher in winter (January) than in summer (July). In both seasons, the concentrations were in decreasing order, [2-NFR]>[1-NP]>[2-NP].

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.

The mutagenicities and endocrine-disrupting activities of two isomers of mononitrated 1-hydroxypyrene [1-hydroxy-x-nitropyrenes (1-OH-x-NPs); x = 2 and 5], which are not only photoreaction products of 1-nitropyrene (1-NP) but also constituent of ambient airborne particles, were evaluated for the first time using the Ames plate incorporation assay and the yeast two-hybrid assay, respectively. The mutagenicity of 1-OH-5-NP was weakly positive in the absence of rat liver S9, but was enhanced up to 3-fold with the metabolic activation by S9. On the contrary, 1-OH-2-NPdid not exhibit significant mutagenicity in the presence or absence of S9. 1-OH-5-NP showed weak estrogenic activity, but 1-OH-2-NP did not show any estrogenic activity. The concentration of 1-OH-5-NP that gave 10% of activity of 1.0 × 10-6M 17ß- estradiol (E2) was 5.4 × 10-7M. 1-OH-5-NP exhibited stronger antiestrogenic and antiandrogenic activities than 1-OH-2-NP. 1-OH-5-NP at a concentration of 1.0 × 10-6M inhibited 71 and 90%of ß-galactosidase activity induced by 1.0 × 10-9Mof E2 and 1.0 × 10-8M of 5a-dihydrotestosterone (DHT), respectively. On the other hand, 1.0 × 10-6M of 1-OH-2-NP inhibited 16 and 43% of ß-galactosidase activity induced by 1.0 × 10-9M of E2 and 1.0 × 10-8M of DHT, respectively. These findings point out the need for determining the environmental sources and distribution of 1-OH-2-NP and 1-OH-5-NP as well as the other hydroxynitropyrene isomers. © 2011 The Pharmaceutical Society of Japan.

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

金沢大学医薬保健研究域薬学系, To measure the actual exposure of a person to 1-nitropyrene (1-NP) in airborne particulate matter, it is considered more accurate to collect air samples with a portable air sampler than to sample at a fixed location. However, because the portable samplers can sample only small volumes, a sensitive method is needed to analyze the compounds that are collected on a filter. Here we describe a high-performance liquid chromatographic (HPLC) method with fluorescence detection that is sensitive and precise enough for use with portable air samplers. The developed column-switching system successfully removed the interfering substances in the samples with only a simple pretreatment. To improve the precision of the measurement, deuterated 1-NP was used as an internal standard, and it eluted immediately prior to 1-NP with sufficient resolution (Rs, 1.50). The detection limit was 0.32 fmol/injection, and the calibration range was from 2 to 100 fmol. The proposed method was applied to determining 1-NP in fine airborne particulate matter (PM2.5) at two sites with low pollution levels. 1-NP was detected in all samples at concentrations in the low fmol/m3 range. The proposed method has enough sensitivity and precision to determine 1-NP in the limited air volume of the portable sampler. © 2009 Elsevier B.V. All rights reserved.

Binding activities and estrogenic/antiestrogenic activities of polycyclic aromatic hydrocarbons (PAHs) and hydroxylated PAHs (OHPAHs) having 2 to 6 rings were evaluated by competition assay and yeast two-hybrid assay expressing human estrogen receptor (hER), respectively. PAHs did not bind to hER and did not show any activity. On the other hand, OHPAHs bound to hER and several OHPAHs showed estrogenic or antiestrogenic activity. Relative estrogenic activity (REP E ) and antiestrogenic activity (REP AE ) were calculated from the values of E 2 and 4-hydroxytamoxyfen as positive controls, respectively. Several OHPAHs having 4 rings showed strongly estrogenic activity. 4-Hydroxybenzo[a]anthracene exhibited the strongest estrogenic activity (REP E = 7.5 × 10−3 ) followed by 3-hydroxybenzo[a]anthracene and 2-hydroxychrysene (REP E = 4.2 × 10−3 ). Several other 4-ring OHPAHs showed strongly antiestrogenic activity. 3-Hydroxybenzo[c]phenanthrene exhibited the strongest antiestrogenic activity (REP AE = 190) follo...