Preliminary analysis of polycyclic aromatic hydrocarbons in air particles (PM10) in Amritsar, India: sources, apportionment, and possible risk implications to humans.

Preliminary analysis was performed to assess human health risks of exposure to 16 polycyclic aromatic hydrocarbons (PAHs) by way of inhalation by children and adults living in urban area of Amritsar, Punjab, India. In particular, the United States Environmental Protection Agency's (USEPA's) 16 priority PAH compounds were analyzed in air particulate matter (PM10) from different geographical locations by high-volume air sampler. Sum concentrations of PAHs (37-274 ng m(-3)) were comparable with those of other cities in India as well many cities on a global scale. Pyrene, naphthalene, acenaphthene, acenaphthylene, fluoranthene, fluorene, and dibenzo(a,h)anthracene accounted for >80% of ∑16PAH concentrations. Furthermore, the contribution of seven carcinogenic PAHs accounted for 12% of ∑16PAHs. The estimated carcinogenicity of PAHs in terms of benzo(a)pyrene toxic equivalency (BaPTEQ) was assessed and confirmed that dibenzo(a,h)anthracene was the dominant PAH contributor (88.7%) followed by benzo(a)pyrene (6.67%). Homolog pattern and diagnostic ratios of PAHs suggested that mixed pyrogenic sources--including biomass burning, coal combustion, and petrogenic sources, such as vehicular emissions--are dominant PAH sources in Amritsar. Health risk of adults and children by way of PAHs was assessed by estimating the lifetime average daily dose (LADD) and corresponding incremental lifetime cancer risk (ILCR) using USEPA guidelines. The assessed cancer risk (ILCR) was found to be within the acceptable range (10(-6)-10(-4)).

Perfluoroalkyl substances in the blood of wild rats and mice from 47 prefectures in Japan: use of samples from nationwide specimen bank.

Numerous studies have reported on the global distribution, persistence, fate, and toxicity of perfluoroalkyl and polyfluoroalkyl substances (PFASs). However, studies on PFASs in terrestrial mammals are scarce. Rats can be good sentinels of human exposure to toxicants because of their habitat, which is in close proximity to humans. Furthermore, exposure data measured for rats can be directly applied for risk assessment because many toxicological studies use rodent models. In this study, a nationwide survey of PFASs in the blood of wild rats as well as surface water samples collected from rats' habitats from 47 prefectures in Japan was conducted. In addition to known PFASs, combustion ion chromatography technique was used for analysis of total fluorine concentrations in the blood of rats. In total, 216 blood samples representing three species of wild rats (house rat, Norway rats, and field mice) were analyzed for 23 PFASs. Perfluorooctanesulfonate (PFOS; concentration range <0.05-148 ng/mL), perfluorooctane sulfonamide (PFOSA; <0.1-157), perfluorododecanoate (<0.05-5.8), perfluoroundecanoate (PFUnDA; <0.05-51), perfluorodecanoate (PFDA; <0.05-9.7), perfluorononanoate (PFNA; <0.05-249), and perfluorooctanoate (PFOA) (<0.05-60) were detected >80 % of the blood samples. Concentrations of several PFASs in rat blood were similar to those reported for humans. PFSAs (mainly PFOS) accounted for 45 % of total PFASs, whereas perfluoroalkyl carboxylates (PFCAs), especially PFUnDA and PFNA, accounted for 20 and 10 % of total PFASs, respectively. In water samples, PFCAs were the predominant compounds with PFOA and PFNA found in >90 % of the samples. There were strong correlations (p < 0.001 to p < 0.05) between human population density and levels of PFOS, PFNA, PFOA, and PFOSA in wild rat blood.

Concentrations and profiles of urinary polycyclic aromatic hydrocarbon metabolites (OH-PAHs) in several Asian countries.

Concentrations of 12 hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) were determined in 306 urine samples collected from seven Asian countries (China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam) by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The total concentrations of OH-PAHs found in the seven Asian countries were in the following increasing order: Malaysia (median: 2260 pg/mL) < Japan (4030 pg/mL) < China (5770 pg/mL) < India (6750 pg/mL) < Vietnam (8560 pg/mL) < Korea (9340 pg/mL) < Kuwait (10170 pg/mL). The measured urinary concentrations of 1-hydroxypyrene (1-PYR) in samples from Malaysia, Korea, and Japan (∼ 100 pg/mL) were similar to those reported for North America and Western Europe. The concentrations of 1-PYR in urine samples from China, India, and Vietnam were 4-10 times higher than those reported for other countries, thus far. Among the 12 OH-PAH compounds analyzed, hydroxynaphthalene (NAP: sum of 1-hydroxynaphthalene and 2-hydroxynaphthalene) was the dominant compound (accounting for 60-90% of total OH-PAHs), followed by hydroxyphenanthrene (PHEN: sum of 2-hydroxyphenanthrene, 3-hydroxyphenanthrene, 4-hydroxyphenanthrene, and 9-hydroxyphenanthrene [3-16%]), 2-hydroxyfluorene (3-20%), and 1-PYR (2-8%). The total daily intakes (DIs) of PAHs were estimated based on the urinary concentrations of their metabolites. The DIs of naphthalene were found to be higher for populations in Korea, Kuwait, and Vietnam (> 10 µg/day) than those of the other countries studied (∼ 5 µg/day). The DIs of phenanthrene and pyrene (> 10 µg/day) in the populations of China, India, and Vietnam were higher than those estimated for the populations in the other countries studied (∼ 5 µg/day).

Perfluorinated compounds in river water, river sediment, market fish, and wildlife samples from Japan.

Perfluorinated organic compounds (PFCs) such as PFOS, PFOA, PFBS, PFHxS, PFOSA and PFDoA were determined in river water, river sediment, liver of market fish and liver of wildlife samples from Japan. Concentrations of PFOA and PFOS in water samples were 7.9-110 and <5.2-10 ng/L. Only PFOA were detected in sediment from Kyoto river at 1.3-3.9 ng/g dry wt. Among fish, only jack mackerel showed PFOA and PFOS at 10 and 1.6 ng/g wet wt. Wildlife liver contained PFOSA, PFOS, PFDoA, PFOA and PFHxS in the range of 0.31-362, 0.15-238, <0.03-28, >0.07-7.3 and <0.03-1.5, respectively, on ng/g wet wt. Cormorants showed maximum accumulation followed by eagle, raccoon dog and large-billed crow.

Levels and concentration ratios of polychlorinated biphenyls and polybrominated diphenyl ethers in serum and breast milk in Japanese mothers.

Blood and/or breast milk have been used to assess human exposure to various environmental contaminants. Few studies have been available to compare the concentrations in one matrix with those in another. The goals of this study were to determine the current levels of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Japanese women, with analysis of the effects of lifestyle and dietary habits on these levels, and to develop a quantitative structure-activity relationship (QSAR) with which to predict the ratio of serum concentration to breast milk concentration. We measured PBDEs and PCBs in 89 paired samples of serum and breast milk collected in four regions of Japan in 2005. The geometric means of the total concentrations of PBDE (13 congeners) in milk and serum were 1.56 and 2.89 ng/g lipid, respectively, whereas those of total PCBs (15 congeners) were 63.9 and 37.5 ng/g lipid, respectively. The major determinant of total PBDE concentration in serum and milk was the geographic area within Japan, whereas nursing duration was the major determinant of PCB concentration. BDE-209 was the most predominant PBDE congener in serum but not in milk. The excretion of BDE 209 in milk was lower than that of BDE 47 and BDE 153. QSAR analysis revealed that two parameters, calculated octanol/water partition and number of hydrogen-bond acceptors, were significant descriptors. During the first weeks of lactation, the predicted partitioning of PBDE and PCB congeners from serum to milk agreed with the observed values. However, the prediction became weaker after 10 weeks of nursing.

Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry.

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.

Risk assessment of short-chain chlorinated paraffins in Japan based on the first market basket study and species sensitivity distributions.

The chemical risks of short-chain chlorinated paraffins (SCCPs) to human health and ecological species in Japan were assessed in this study. SCCPs are used as extreme pressure additives in metal-working fluids and flame retardant agents in plastic materials. The first market basket study with a high resolution gas chromatography and mass spectrometry with electron capture negative ionization is reported. Total daily food intakes for Japanese residents of different ages were estimated using Latin Hypercube simulations, and the highest 95th percentile intake is 6.8 x 10(2) ng/kg/day for a 1-year-old child. Based on the reported no-observed-adverse-effect-level (NOAEL) and the estimated exposure mainly from food, it was concluded thatSCCPs are not posing risks to humans in Japan. Ecological risks to aquatic and sediment organisms were estimated using species sensitivity distributions. The 95th percentiles of the distributions obtained by fitting several environmental SCCP concentration data of river water and sediment were 41.8 ng/L and 558 ng/g wet weight as the possible highest concentrations, respectively. No-observed-effect-concentrations (NOEC) were determined by calculating the fifth percentiles of a species sensitivity distribution, which were 2.2 microg/L for aquatic organisms and 1.7 to 13.5 mg/ kg wet weight for sediment organisms. While it is likely that there is no imminent environmental chemical risk for aquatic organisms at a regional level in Japan, this study concluded that a more detailed risk assessment is necessary for sediment organisms.

Impact of FEBRA (fermented brown rice with Aspergillus oryzae) intake and concentrations of PCDDs, PCDFs and PCBs in blood of humans from Japan.

Impact of FEBRA (fermented brown rice with Aspergillus oryzae, a rich dietary fiber) intake on the concentrations of polychlorinated-biphenyls (PCBs), -dioxin-like polychlorinated biphenyls (DLPCBs), -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) in blood of nine married Japanese were studied for 2 years. Concentrations of total PCBs (average+/-standard deviation) were greater 326,000+/-263,000 and 207,000+/-89,000 in FEBRA-intake and non-FEBRA-intake groups, respectively, on pg/g lipid (from now onwards data expressed on pg/g lipid). DLPCBs were second major contaminants 94,000+/-77,000 and 60,000+/-28,000, orderly in FEBRA-intake and non-FEBRA-intake groups. The concentrations of PCDD/DFs were several orders of magnitude lower than those of PCBs, whereas PCDDs were greater (433+/-233 and 512+/-511, in FEBRA-intake and non-FEBRA-intake groups, respectively) than PCDFs (56+/-50 and 43+/-35). Calculated toxic equivalency (TEQ) concentrations were 34+/-24 and 23+/-10 in FEBRA-intake and non-FEBRA-intake groups, respectively. In order to corroborate the impact of FEBRA, the changes of PCDD/DFs and PCB concentrations for 0.5-year, 1-year, 1.5-year, and 2-year samples were estimated from average concentration of 1-day before study commences and 1-week study samples. The results explicit FEBRA-intake group eliminated 7%, 33%, 45%, 36%, and 26% and non-FEBRA-intake group eliminated 8%, 28%, 36%, 31%, and 20% of DLPCBs, PCDDs, PCDFs, PCDD/DF TEQ and total TEQ, respectively. This study is the first of its kind showing the possible elimination of PCDDs, PCDFs and their TEQ in humans from Japan after the consumption of FEBRA.

Impact of fermented brown rice with Aspergillus oryzae (FEBRA) intake and concentrations of polybrominated diphenylethers (PBDEs) in blood of humans from Japan.

The isotope dilution technique was applied for the analysis of new polybrominated diphenylethers (PBDEs) calibration standard (both labeled and non-labeled) using high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS). The relative response factor (RRF) and relative standard deviation (RSD) for new calibration standard in Finnigan Thermo Electron (MAT-95XL) and Micromass (Autospec Ultima) were more or less identical with mean RRF (0.9882), RSD (0.0865) and CV% of (8.75). The results also revealed for DeBDE-209 quantification; labeled DeBDE-209 is essential. Furthermore, we recommend on column injection technique with a thin film instead of splitless injection in order to reduce the thermal degradation of DeBDE-209 and formation of octabromodibenzofurans (OBDF). Besides, analysis of human blood (n = 156) of FEBRA-intake and non-FEBRA-intake individuals elucidated frequent detection of eighteen PBDE congeners. The average PBDE concentrations in non-FEBRA intake and FEBRA-intake humans were 6000-11,000 (mean: 8400) and 5400-15,000 (mean: 9900) respectively on pg/g fat basis. Although FEBRA-intake individuals showed slightly greater PBDEs, computer-normalized concentrations of TeBDE-47 corroborate FEBRA-intake individual from four family showed reduced concentrations. The contamination profiles of PBDEs varied in between family, gender as well as geography. International comparison with predominant PBDE congener (TeBDE-47) prevailed lower levels in Japan when compared to Korea, Germany and USA nevertheless, congener specific profiles were different which is in accordance with different technical PBDE usage in between countries.

Brominated organic contaminants in the liver and egg of the common cormorants (Phalacrocorax carbo) from Japan.

The contamination profiles of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs), biphenyls (PBBs), dibenzo-p-dioxins (PBDDs), and dibenzofurans (PBDFs) were determined in the liver and egg of common cormorants from Japan. PBDEs and PBBs were detected in all the samples; especially the former were detected at elevated levels. PBDDs/PBDFs were also detected in cormorants, albeit the concentrations were lower than those of the PBBs. The total concentration of PBDEs ranged from 330 to 2600 in the liver and from 600 to 3300 in the egg on a nanogram per gram of lipid basis. The concentration of PBBs was in the range from 3.0 to 33 (in the liver) and from 3.4 to 82 (in the egg) on a nanogram per gram of lipid basis. The 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) was the most predominant PBB congener in either organ, which corresponds to a major constituent of the BFR FireMaster BP-6. Concentrations of PBDDs/ PBDFs in the liver (range from 21 to 470) were slightly higher than in the egg (range from 31 to 160) on a picogram per gram of lipid basis. The results of this study imply that common cormorants accumulate a high level of PBDEs and PBBs. Comparing the concentrations of brominated organic compounds with those of chlorinated analogues, good relevance between PBBs and coplanar PCBs (r2 = 0.746 [liver] and 0.715 [egg]) was elucidated. To our knowledge, the present study demonstrates the first report of PBDEs, PBBs, and PBDDs/PBDFs in the common cormorant from Japan.

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana, U.S.A.

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations have existed in the past but have been extirpated. High mortality was observed during transport of mink from the source populations. In order to elucidate the potential effects of dioxin-like compounds on the survival and reproduction of mink, concentrations of total polychlorinated biphenyls (PCBs), p,p'-DDE, dioxin-like PCBs, polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) were measured in livers of mink collected from the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) for the South Carolina and Louisiana mink were 21 and 14 pg g(-1), wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranch mink. Therefore, any additional exposures of these populations to TEQs might adversely affect their populations.

Concentrations of perfluorinated acids in livers of birds from Japan and Korea.

Livers of birds collected from Japan and Korea (n = 83) were analyzed to determine the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), perfluorooctanoic acid (PFOA) and perfluorohexanesulfonate (PFHS). PFOS was found in the livers of 95% of the birds analyzed at concentrations greater than the limit of quantitation (LOQ) of 10 ng/g, wet weight. The greatest concentration of PFOS of 650 ng/g, wet weight, was found in the liver of a common cormorant from the Sagami River in Kanagawa Prefecture. Concentrations of PFOS in bird livers from Japan and Korea were within the ranges of values reported for those from the United States and certain European countries. PFOA and PFHS were found in 5-10% of the samples analyzed. The greatest concentrations of PFOA and PFHS in bird livers were 21 and 34 ng/g, wet weight, respectively. FOSA was found in all the samples (n = 10) of cormorants collected from the Sagami River in Japan. The greatest concentration of FOSA in cormorant liver was 215 ng/g, wet weight. There was no significant correlation between the concentrations of PFOS and FOSA in cormorants collected from the Sagami River. These results suggested that the distribution of FOSA is localized. No age- or gender-specific differences in fluorochemical concentrations could be discerned in birds.