Search

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.

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...

A method for the simultaneous quantitative determination of deoxynivalenol (DON), T-2 toxin (T-2), HT-2 toxin (HT-2) and zearalenone (ZEN) in wheat and biscuit by liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) coupled with immunoaffinity extraction is described. A clean-up was carried out using a DZT MS-PREP® immunoaffinity column (IAC), and the effect of the sample dilution rate and sample loading was investigated. Furthermore, the effects of ion suppression of a multifunctional column (MFC) and the IAC in the clean-up were compared. The results with the DZT MS-PREP® IAC showed that it is possible to make the sample dilution rate low, and indicated a higher solvent-tolerance than usual with an IAC. Sample loading was optimized at 0.25 g. Ion suppression was lowered by purification of the toxins using the DZT MS-PREP® IAC. Recoveries of each mycotoxin from wheat and biscuit samples spiked at two levels ranged from 78 to 109%. The limits of detection in wheat and biscuit was in the range of 0.03–0.33 ng·g−1. From these studies, it is suggested that use of an IAC is effective in the clean-up of each mycotoxin, and, when combined with LC/ESI-MS/MS, it is good for the determination of mycotoxins in foodstuffs due to its rapidity and high sensitivity. Copyright © 2010 John Wiley & Sons, Ltd.

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.

Iprodione is an agricultural fungicide that is difficult to detect in foods by HPLC because it coelutes with natural compounds in the food. We previously showed that food matrix could be degraded with titanium dioxide powder (TP). Here we describe an improved method for detection of iprodione using silica gel supported titanium dioxide (SGT). To synthesize SGT, titania-sol was mixed with diethanolamine, 2-propanol, and titanium tetraisopropoxide. After titania-sol was infiltrated into the silica gel (particle diameter 4 mm), the mixture was dried and then heated. Crude basil extract containing iprodione was mixed with SGT in a quartz vial, and the vial was irradiated with a UV light to selectively decompose the matrix interfering with the iprodione determination. In HPLC chromatograms of the treated solution, the interference peak decreased 35 times faster with SGT than with TP. When SGT (11 g) was added to the extract (20 mL) of dry basil (2 g), black light irradiation for 30 min was enough to quantify iprodione. The recovery rate of iprodione was 99.1%. Thus, the photocatalytic cleanup method using SGT is effective for analyzing residual iprodione in dry basil.

Fusarium species, a plant pathogenic fungus of wheat and other cereals, produces toxic metabolites such as nivalenol (NIV) and deoxynivalenol (DON). Control of contamination by these toxins is very difficult, and a continuous survey of the occurrence is necessary for these toxins. Thus, the accurate and convenient determination of the cereals contaminated with these toxins is important for the supply of safe foods. A selective analytical method based on high-performance liquid chromatography, combined with atmospheric pressure photoionization (APPI) mass spectrometry, has been developed for simultaneous determination of NIV and DON. The parameters investigated for the optimization of APPI were the ion source parameters fragmentor voltage, capillary voltage, and vaporizer temperature, and also mobile phase composition and flow rate. Furthermore, chemical noise and signal suppression of analyte signals due to sample matrix interference were investigated for APPI. The results indicated that APPI provides lower matrix effect and the correlation coefficient of NIV and DON in the range 0.2-100 ng x mL(-1) was above 0.999. Recoveries of NIV and DON in wheat ranged from 86 to 107% and limits of detection of NIV and DON were 0.20 ng x g(-1) and 0.39 ng x g(-1), respectively. In addition, the proposed method was applied for the analysis of naturally contaminated wheat samples. APPI was found to offer lower matrix effect and was a convenient technique for routine analysis of NIV and DON residues in wheat at trace levels.

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.

Exposures to particulate matter (PM) of both 10-2.5 microm (PM(10-2.5)) and below 2.5 microm (PM(2.5)) were measured for a cohort of taxi drivers in Shenyang, China, during August 2007. PM samples were collected inside and outside the taxi during the drivers' workshifts, and also inside the drivers' homes when they were off-shift. Ambient PM samples were also collected at a stationary location in Shenyang. Elemental carbon (EC) and organic carbon (OC) were also measured in PM collected on quartz filters inside the taxis as well as at the stationary site. Concentrations of three nitro-polycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (1NP), 2-nitropyrene (2NP), and 2-nitrofluoranthene (2NFl), were determined in extracts of the PM samples by using a 2D-HPLC-MS/MS method. The 2NP and 2NFl concentrations did not change substantially with sampling location, but the 1NP concentrations were much higher in samples collected inside and outside the taxis as compared with sampling locations that were more removed from traffic. Concentration ratios of specific NPAHs were used to assess the atmospheric conditions in Shenyang during the sampling period. The relatively high ratios of 2NFl/1NP ( approximately 8-50) indicate an important contribution from secondary NPAH formation to ambient NPAH levels, especially for the nontaxi samples. The ratios of 2NFl/2NP (2.5-4.3) indicate that 2NFl is primarily formed via the hydroxyl-initiated reaction.

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...

金沢大学医薬保健研究域薬学系, To evaluate human exposure to polycyclic aromatic hydrocarbons (PAHs), we developed a rapid, simple and sensitive method for determining 1-hydroxypyrene-glucuronide (1-OHP-G) in human urine. To improve precision, a deuterated glucuronide was used as an internal standard. The method requires only 1 mL of urine. The urine was treated with a mixed-mode anion-exchange and reversed-phase solid-phase extraction cartridge (Oasis MAX). The analytes were analyzed with a C18 reversed-phase column with a gradient elution, followed by tandem mass spectrometry with electrospray ionization in negative ion mode. The detection limit of 1-OHP-G (corresponding to a signal-to-noise ratio of 3) was 0.13 fmol/injection. Urinary concentrations of 1-OHP-G determined by this method were strongly correlated (r2 = 0.961) with concentrations of 1-hydroxypyrene by conventional HPLC with fluorescence detection. © 2008 Elsevier B.V. All rights reserved.

Endocrine disrupting activities of three isomers of monohydroxylated 1-nitropyrene (1-NP) [3-, 6-, and 8-hydroxy-1-nitropyrenes (OHNPs)] were evaluated for the first tim eb y yeast two-hybrid assay. OHNPs, which are not only metabolites of 1-NP but are also found in airborne particles, did not exhibit androgenic activity but exhibited estrogenic, antiestrogenic, and antiandrogenic activities. 6-OHNP showed the strongest estrogenic activity among the three OHNP isomers examined in this study. Concentrations of the OHNP isomers that gave 10% of activity of 1.0 × 10 −6 M1 7β-estradiol (E2 )w ere as follows: 3-OHNP, 6.0 × 10 −7 M; 6-OHNP, 6.0 × 10 −8 M; 8-OHNP, 9.0 × 10 −7 M. On the contrary, 8-OHNP exhibited the strongest antiestrogenic and antiandrogenic activities of the three isomers. 1.0 × 10 −6 Mo f 8-OHNP inhibited 32 and 90% of β-galactosidase activity induced by 1.0 × 10 −9 Mo f E2 and 1.0 × 10 −8 M of 5α-dihydrotestosterone (DHT), respectively. These findings point out the necessity for detailed investigation of environmental sources and distributions of OHNPs as well as the parent 1-NP.

Airborne particulate matters contain many kinds of organic pollutants. Among them, polycyclic aromatic hydrocarbons (PAH), nitropolycyclic aromatic hydrocarbons (NPAH) and quinoid PAHs were reported to have several human health effects. We collected airborne particulates in Kitakyushu, Japan and Tieling, China in summer and winter, and analyzed the PAH and NPAH to evaluate the direct- and indirect-acting mutagenicities and generating activities of reactive oxygen species (ROS). The concentrations of PAHs and NPAHs in Tieling were much higher than in Kitakyushu, with seasonal variations. The mutagenicity level was higher in winter while the ROS generation activity was higher in summer. These results suggest that concentrations of PAH and NPAH didn't correlate with mutagenicity and ROS generation activity. More studies are needed on the environmental behaviors of compounds other than PAHs and NPAHs, such as quinoid PAHs, and their biological activities.

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.

Estrogenic/antiestrogenic activities of 14 polycyclic aromatic hydrocarbons (PAHs) and 63 monohydroxylated PAHs (OHPAHs) having 2 to 6 rings were evaluated by yeast two-hybrid assay expressing human estrogen receptor α. Relative effective potencies of estrogenic and antiestrogenic activities were calculated as the inverse values of the relative concentration of the test compound that gave the same activities of E2 and 4-hydroxytamoxifen, respectively. PAHs did not show any estrogenic/antiestrogenic activity, but several OHPAHs having 3 to 5 rings showed activities. Especially, OHPAHs having 4 rings such as 3-, 4- and 10-hydroxybenz[a]anthracenes (3-, 4- and 10-OHBaAs) and 2-hydroxychrysene (2-OHCh) showed strongly estrogenic activity. Several other OHPAHs having 4 rings such as 2- and 3-hydroxybenzo[c]phenanthrenes (2-, 3- OHBcPhs), 2-OHBaA and 3-OHCh showed strongly antiestrogenic activity. The length-to-breadth (L/B) ratios of the rectangular van der Walls planes surrounding the ring molecules of estrogenic OHPAHs were in the narrow range from 1.599 to 1.734. The distances between the oxygen atom of the phenol group and farthest hydrogen atom (O-H distance) of the estrogenic OHPAHs ranged from 10.825 A° to 11.738 A°. The L/B ratios and O-H distances of antiestrogenic OHPAHs were in the wider ranges from 1.277 to 1.734 and from 8.47 A° to 11.681 A°, respectively. The partial charges (atomic unit) of the phenol group of both estrogenic and antiestrogenic OHPAHs were in the range from 0.250 atmic unit (au) to 0.253 au. The similarity of these values to those of E2 and diethylstilbestrol suggested that the compositions of estrogenic OHPAHs were similar to them and that the compositional conditions of estrogenic OHPAHs were much smaller than those of antiestrogenic OHPAHs. These results raise the possibility of predicting the estrogenic/antiestrogenic activities of OHPAHs from their structural characteristics, although using only the above three parameters might not be enough for accurate estimations.

1-Nitropyrene (1-NP) is enriched in diesel exhaust particulate matter (DPM) relative to other sources of particulate matter (PM), and has been proposed as a marker for DPM. However, in ambient air, 1-NP concentrations are typically in the low pg/m 3 range. Therefore, collection of large volume air samples coupled with extensive sample clean-up procedures has been required to achieve adequate detection limits to measure 1-NP in ambient samples. We report here an improved LC–MS/MS method suitable for the detection and quantification of 1-NP in low volume ambient PM samples. The method involves ultrasonic extraction of ambient PM in organic solvent, concentration of the sample under reduced pressure, and two-dimensional HPLC analysis of the extract. 1-NP is isolated on the first HPLC column, then converted to 1-aminopyrene (1-AP) via online reduction in a column packed with a Pt/Rh catalyst. The 1-AP containing fraction from the first column is refocused on a trapping column, then eluted through a second HPLC column prior to MS/MS detection. Deuterated ( d 9 ) 1-NP (1-dNP) is added to each sample prior to extraction as an internal standard for quantification of 1-NP. The accuracy and precision of the assay, as applied to ambient particulate standard reference materials are 110 ± 5.7% for SRM 1650b, 116 ± 7.1% for SRM 2975, 108 ± 5.8% for SRM 1649a, and 53 ± 9.2% for SRM 1648. The analytical limit of detection was 152 fg on column, and analytical limit of quantitation 221 fg on column. To our knowledge, the sensitivity of this method is comparable with GC–NICI–MS methods while having the advantage of considerably less extensive sample preparation. This method is an approximately 10-fold improvement in sensitivity over HPLC methods utilizing fluorescence and/or chemiluminescence detection.

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.

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 ...

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.

Polycyclic aromatic hydrocarbons (PAHs) and chlorinated PAHs (ClPAHs) are ubiquitous contaminants that bind to the aryl hydrocarbon receptor (AhR) and exhibit mutagenic potential. It is difficult to monitor human exposure levels to ClPAHs because the exposure routes are complicated, and environmental concentrations are not always correlated with the levels of PAHs. Urinary PAH metabolites are useful biomarkers for evaluating PAH exposure, and ClPAH metabolites may therefore contribute to the estimation of ClPAH exposure. One of the most abundant ClPAHs present in the environment is 1-chloropyrene (ClPyr), and urinary ClPyr metabolites have the potential to be good biomarkers to evaluate the level of exposure to ClPAHs. Since the metabolic pathways involving ClPAHs are still undetermined, we investigated the effect of human cytochrome P450 enzymes on ClPyr and identified three oxidative metabolites by liquid chromatography-tandem mass spectrometry and nuclear magnetic resonance. We found that ClPyr was metabolized most efficiently by the P450 1A1 enzyme, followed by the 1B1 and 1A2 enzymes. Similar to ClPyr, these metabolites were shown to have agonist activity for the human AhR. We detected these metabolites when ClPyr reacted with a pooled human liver S9 fraction as well as in human urine samples. These results suggest that the metabolites may be used as biomarkers to evaluate the extent of exposure to ClPAHs.

The simultaneous sampling of total suspended particles was performed at 14 sites in Japan during July 2008-June 2009. The spatial correlativity of each particulate composition toward Osaka was obtained for nine selected sites to overview the chemical composition and geographical distribution of particulate components across a wide range of areas nationwide. The spatial correlatives of atmospheric particulate components were extended to an even wider range of areas up to 950 km distance (meso-alpha scale region, >200 km) for a far-reaching distance analysis unique in the literature. Overall, the spatial correlations of ionic species and both organic and elemental carbons were significant, suggesting their shared advections, including their long-range transport from East Asia. Although sulfate ions are widely dispersed across Japan, such is not necessarily correlated with organic and elemental carbon, possibly indicating that the sulfate emission source, including long-range transport, differs from that of carbonaceous particulates. By contrast, the characteristics of spatial correlatives of metallic constituents vary; for example, particulate Pb and Cd show a significantly wide range of spatial correlatives to Osaka, while Mn-though limited to cities neighboring Osaka-shows significant spatial correlations. Other metallic constituents showed no significant spatial correlatives, indicating the effects of local pollutants. Moreover, the extent of the spatial dispersion of the particulate components and the relationships among chemical components were analyzed via factor analysis to highlight the effects of long-range inflow and local original emissions. In this treatment, 13 particulate components among the 19 measured were implicated in long-range transport.

We previously demonstrated that monohydroxylated polycyclic aromatic hydrocarbons (OHPAHs), which are metabolites of polycyclic aromatic hydrocarbons (PAHs), act on calcified tissue and suppress osteoblastic and osteoclastic activity in the scales of teleost fish. The compounds may possibly influence other calcified tissues. Thus, the present study noted the calcified spicules in sea urchins and examined the effect of both PAHs and OHPAHs on spicule formation during the embryogenesis of sea urchins. After fertilization, benz[a]anthracene (BaA) and 4-hydroxybenz[a]anthracene (4-OHBaA) were added to seawater at concentrations of 10− 8 and 10− 7 M and kept at 18 °C. The influence of the compound was given at the time of the pluteus larva. At this stage, the length of the spicule was significantly suppressed by 4-OHBaA (10− 8 and 10− 7 M). BaA (10− 7 M) decreased the length of the spicule significantly, while the length did not change with BaA (10− 8 M). The expression of mRNAs (spicule matrix protein and transcription factors) in the 4-OHBaA (10− 7 M)-treated embryos was more strongly inhibited than were those in the BaA (10− 7 M)-treated embryos. This is the first study to demonstrate that OHPAHs suppress spicule formation in sea urchins.

Airborne particulates were collected in seven cities in the Pan–Japan Sea countries, Shenyang (China), Vladivostok (Russia), Seoul (South Korea), Kitakyushu, Kanazawa, Tokyo and Sapporo (Japan), in winter and summer from 1997 to 2002. In addition, particulates from domestic coal-burning heaters and diesel engine automobiles were collected in Shenyang and Kanazawa, respectively. Nine polycyclic aromatic hydrocarbons (PAHs) and four nitropolycyclic aromatic hydrocarbons (NPAHs) in the extracts from the particulates were analysed by HPLC with fluorescence and chemiluminescence detections, respectively. The PAHs were fluoranthene, pyrene (Pyr), benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene, and NPAHs were 1,3-, 1,6-, 1,8-dinitropyrenes, and 1-nitropyrene (1-NP). Mean atmospheric concentrations of PAHs in Shenyang and Vladivostok were substantially higher than those in Seoul, Tokyo, Sapporo, Kitakyushu and Kanazawa. However, the mean atmospheric concentrations of NPAHs were at the same levels in all cities except Kitakyushu. The expected seasonal variations (greater PAH and NPAH concentrations in winter than in summer) were observed in all cities. In order to study the major contributors of atmospheric PAHs and NPAHs, both cluster analysis and factor analysis were used and three large clusters were identified. Furthermore, the concentration ratios of 1-NP to Pyr were significantly smaller in Shenyang, Vladivostok and Kitakyushu and the values were close to those observed in particulates from coal stove exhaust. By contrast, in Seoul, Kanazawa, Tokyo and Sapporo the [1-NP]/[Pyr] ratio reached values similar to those of particulates released from diesel-engine automobiles. The [1-NP]/[Pyr] concentration ratio seemed to be a suitable indicator of the contribution made by diesel-engine vehicles and coal combustion to urban air particulates.

To clarify the alteration of androgenic and antiandrogenic activities by diesel engine conditions, we collected diesel exhaust particles (DEP) samples emitted from a diesel-engine truck under different conditions of engine loads and vehicle speeds, and DEP extract (DEPE) samples were prepared from each. The androgenic and antiandrogenic activities of the DEPE samples were examined using a prostate specific antigen (PSA) promoter-luciferase reporter gene assay in PC3/AR human prostate cancer cells. While all DEPE samples did not exhibit androgenic effects, the antiandrogenic effects were enhanced by higher engine load but not by higher vehicle speed. In this study, significant correlations between antiandrogenic and aryl hydrocarbon receptor (AhR) agonistic activities were demonstrated in PC3/AR cells by 16 polycyclic aromatic compounds and β-naphthoflavone. Yeast two-hybrid assay and cytochrome P450 (CYP) 1A1 promoter-luciferase reporter gene assay showed that the antiandrogenic constituents acting as androgen receptor (AR) antagonists and AhR agonists were increased by only the higher engine load. In conclusion, the antiandrogenic effects of DEPE samples were enhanced by a higher engine load which resulted in DEPC samples with elevated AhR agonistic and AR antagonistic activities.

We examined endocrine disruptors in diesel exhaust particulates (DEP) emitted from a diesel engine under different engine loads. The antiandrogenic and aryl hydrocarbon receptor (AhR) agonistic activity of DEP extracts (DEPE) were evaluated using PC-3/AR human prostate cancer cells transiently transfected with androgen- or AhR agonist-regulated luciferase reporter plasmids, respectively. The antiandrogenic and AhR agonistic activities were enhanced by higher engine load. The AhR antagonist α-naphthoflavone reversed the antiandrogenic activity of DEPE as seen through a reduction in AhR agonistic activity. The concentrations of polycyclic aromatic hydrocarbons (PAHs) with four or more rings, which are AhR agonists in DEPE, increased with higher engine load. Therefore, the enhanced antiandrogenic activity of DEPE is due in part to the increase in AhR agonists such as PAHs with higher engine load.

2-Hydroxyfluorene (2-OHF) and 1-hydroxypyrene (1-OHP) in urine samples of smokers and nonsmokers were determined separately by using two high-performance liquid chromatography (HPLC) systems with fluorescence detection. Urine samples were collected from the subjects who lived in Japan and Thailand, and were not occupationally exposed to polycyclic aromatic hydrocarbons (PAHs). The mean concentrations of 2-OHF and 1-OHP of Thai smokers (0.75 and 3.03 μmol/mol creatinine) and nonsmokers (0.22 and 0.91 μmol/mol creatinine) were both higher than those of Japanese smokers (0.26 and 0.12 μmol/mol creatinine) and nonsmokers (0.04 and 0.06 μmol/mol creatinine), respectively. The difference between smokers and nonsmokers was more significant for 2-OHF than for 1-OHP, reflecting the higher intake of fluorene in the vapor phase by the smoking. Moreover, the higher urinary levels of both 2-OHF and 1-OHP were observed in Thai nonsmokers than those in Japanese nonsmokers, suggesting the higher background exposure to PA...

Dioxins are present as impurities in agrochemicals applied to the soil. To examine the possibility that dioxins end up in the atmosphere, we compare the homologue composition and some characteristic isomer distributions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in air and soil samples collected at sites in Ishikawa Prefecture, Japan. Tetrachloro dibenzo-p-dioxin (TeCDD) was the most abundant PCDD homologue in the air samples, while octachloro dibenzo-p-dioxin (OCDD) was the most abundant PCDD homologue in the soil samples. However, at several site, the most predominant homologue in the soil sample was not OCDD but TeCDD. The mean ratio of TeCDDs to PCDDs in the air samples was significantly smaller in winter than in other seasons, but no such seasonal variation was observed in the distribution of PCDF homologues. The abundance of PCDF homologues was inversely related to the number of chlorine substitutions in the air samples. The contribution of each toxic isomer (2,3,7,8-chlorine-substituted) to the total toxicity equivalency quantity (TEQ) in the air samples tended to be intermediate between their contributions to the TEQs in the soil and cinder samples. This result suggested that the air samples were influenced by both soil/dust suspension and combustion. In order to clarify the contributions of agrochemicals to dioxins in the air, we focused on the ratios of several characteristic isomers that are indicators of agrochemicals (chloronitrophen: CNP and pentachlorophenol: PCP) to their homologues. Significant decreases in the ratios of the isomers to their homologues in the air samples were observed only in winter, probably as a result of suppression of dust suspension by the snow cover. Therefore, the contribution of combustion to the dioxin concentration in the air was thought to be relatively large in winter.

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in maternal blood and fetuses from Fischer 344 rats exposed to diesel exhaust (DE) during pregnancy, and in breast milk from rats exposed to DE during pregnancy and lactation using high performance liquid chromatography with fluorescence detection. Concentrations of phenanthrene (Phe), anthracene (Ant) and benz[a]anthracene (BaA) were significantly higher in maternal blood of the DE group than those of the control group. Concentration of Phe in fetuses of the DE group was significantly higher than those of the control group. Concentrations of fluorene, Ant, fluoranthene (Flu), pyrene (Pyr), BaA and chrysene (Chr) tended to be higher in fetuses of the DE group. The levels of Ant, Flu, Pyr and Chr in breast milk from the DE group were significantly higher than those of the control group. These results indicate that PAHs taken into mother rat by the inhalation of DE are transferred into fetuses via placenta and into breast milk. This is the first report to clarify the transportation of inhaled PAHs into fetuses and breast milk from mother rats.

An automatic HPLC system for analyzing nitropolycyclic aromatic hydrocarbons (NPAHs, nitroarenes) in airborne particulates was previously described (Anal. Chim. Acta, 2001, 445, 20). Some problems with this system were that it generated a peak originating from an ascorbic acid solution that elutes at a retention time close to that of 1,6-dinitropyrene (DNP), and that it was able to analyze only 1,3-, 1,6-, 1,8-DNPs and 1-nitropyrene (1-NP). Here, we describe an improved system that effectively removes the interfering peak by introducing an ODS column just after the pump for the ascorbic acid solution, and which is capable of analyzing several additional compounds (2-, 4-NPs, 2-nitrofluorene, 6-nitrochrysene, 7-nitrobenz[a]anthracene, 3-nitroperylene and 6-nitrobenzo[a]pyrene etc.). ). The improved sensitivities were achieved by concentrating the compounds in a benzene-ethanol extract from airborne particulates, by increasing the loading time of the sample solution from 20 to 38 min, and by increasing the flow rate of an ascorbic acid solution from 1.3 to 1.8 mL/min.

A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with four perdeuterated PAHs as internal standards. After 50 mg hair samples were washed with n-hexane to remove external contamination of PAHs, the samples were digested in 2.5 M sodium hydroxide. The digests were extracted with n-hexane and then analyzed by HPLC. Eleven kinds of PAHs were identified in hair samples of 20 subjects, and 10 kinds of PAHs were eventually quantified using the internal standards. For anthracene, chrysene and benzo[k]fluoranthene, significant differences were observed between smokers and non-smokers. Although benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were observed in the particulates of indoor and outdoor air, they were not detected in all hair samples. The analysis of PAHs in human hair should be useful as a new biomarker to evaluate the exposure to PAHs.

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

A high-performance liquid chromatographic method has been developed for the quantification of 1-hydroxypyrene (1-OHP) in human urine using deuterated 1-hydroxypyrene ([2H9]1-OHP) as an internal standard with fluorescence detection. [2H9]1-OHP was prepared enzymatically from deuterated pyrene ([2H10]Pyr) with cytochrome P450 1A1. It eluted immediately prior to non-deuterated 1-OHP on alkylamide-type reversed-phase columns and had nearly the same fluorescence characteristics as non-deuterated 1-OHP. The detection limit was 0.1 microg/L and the calibration range was from 1 to 100 nmol/L. Urine sample treatment involved enzymatic hydrolysis followed by solid-phase extraction using Sep-Pak C18 cartridges. The proposed method was used to determine urinary 1-OHP in smokers and non-smokers.

Airborne particulates were collected at a site near a group of factories in Kitakyushu, one of the most industrialized cities in Japan, and at downtown sites in Sapporo and Tokyo, typical large commercial cities. We determined the levels of polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs), which are known to be carcinogenic and/or mutagenic. The atmospheric concentrations of most PAHs with 4-, 5-, and 6-rings were higher in Kitakyushu and Tokyo than in Sapporo. On the other hand, atmospheric concentrations of the strongly mutagenic NPAHs were the highest in Sapporo, intermediate in Tokyo, and lowest in Kitakyushu. The atmospheric concentrations of 1-nitropyrene (1-NP) in Kitakyushu were one order of magnitude lower than those in the two commercial cities. Therefore the concentration ratios of NPAHs to their nucleus PAHs were significantly smaller in Kitakyushu than in the two commercial cities. This result suggested that the atmospheric levels of NPAHs in Kitakyushu were comparatively low, although the air in Kitakyushu was as heavily polluted with PAHs as the air in Tokyo. The concentration ratio of dinitropyrenes (DNPs) to 1-NP in Kitakyushu was much higher than that in the other two cities. A possible reason for the above two differences between the two types of cities is the contribution of chimney exhaust of steel manufacturing plants in Kitakyushu, which contains high concentrations of PAHs.

A liquid chromatographic (LC) method has been developed for the separation of 11 monohydroxybenzo[a]pyrenes (OH BaPs) positional isomers, and for their detection using electrospray ionization mass spectrometry (ESI-MS). All OH BaPs isomers were separated on an octadecylsilyl (C18)-bonded amorphous organosilica column utilizing gradient elution with acetonitrile–water and triethylamine (TEA) at pH 11.0 and determined by MS, except 2- and 8-OH BaPs which were coeluted. The lower detection limits were in the range from 1.6 µg/L for 12-OH BaP to 12 µg/L for 5-OH BaP without any sample enrichment. The relative standard deviations of area response were in the range from 1.8% (9-OH BaP) to 4.9% (12-OH BaP) except for 9.4% (7-OH BaP). The developed method was successfully applied to incubation mixtures of BaP and CYP1A1/epoxide hydrolase. This method identified 1-, 3- and 9-OH BaPs as the major metabolites, and 2- (and/or 8-) and 12-OH BaPs as the minor metabolites in the incubation mixture. Copyright © 2002 John Wiley & Sons, Ltd.

Diesel exhaust particulate matter (DEP) was collected from three commercial diesel engine vehicles and DEP extracts (DEPEs) were prepared from each. The estrogenic and antiestrogenic activities of the DEPE samples were examined using an estrogen response element (ERE)-driven luciferase reporter gene assay in MCF-7 human breast cancer cells. While DEPE samples did not exhibit significant estrogen agonist activity alone, they suppressed 17 g -estradiol (E 2 )-induced luciferase activity without decreasing cell viability. Several polycyclic aromatic hydrocarbons (PAHs) acting as aryl hydrocarbon receptor (AhR) agonists were detected in the DEPEs and their concentrations were higher in DEPE samples with higher antiestrogenic activity. DEPE samples elevated cytochrome P450 (CYP) 1A1 activity. f -Naphthoflavone, an AhR antagonist, and SKF-525A, a nonselective CYP inhibitor, reversed and enhanced the antiestrogenic activity of DEPE samples, respectively. These results demonstrate that DEPE has antiestrogenic act...

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.

A multi-nozzle layered mesh inertial filter, developed by the authors based on inertial filter technology for separating ultrafine particles (UFPs) at a moderate pressure drop, was investigated in an attempt to improve the steepness of the separation efficiency curve by combining an inertial filter and an impactor. In this system, the separation curves overlap each other, while maintaining about a 100 nm difference in cutoff size d p50. Such a combination, which we refer to as a 'hybrid inertial filter', was validated for a single nozzle geometry. Using a multi nozzle geometry, it was scaled up to a high volume air sampling flow rate of 400 l min−1 at a pressure drop of 300 nm, a steeper collection efficiency curve and less pressure drop than those of a previous type of inertial filter. The ambient PM0.13 evaluated for the present unit was found to be in good agreement with values obtained for 2 different types of cascade air samplers.