Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999

Pine needle samples collected at ten spatially distant sites around Tokyo Bay in 1999 indicated a widespread lower troposphere pollution with ultra-trace dioxin-like compounds such as chlorodibenzo-p-dioxins (PCDDs), -furans (PCDFs), non-ortho- and mono-ortho-chlorobiphenyls (pPCBs), and -naphthalenes (PCNs). Elevated concentration of planar PCBs and the total PCNs were found at the sites which are located innermost to the Bay, suggesting the regional importance of the evaporative nature of the source of pollution by those compounds over this vast area. The concentrations and profiles for PCDDs and PCDFs remained largely uniform. An exception was the site near the town of Tateyama in the Chiba Prefecture, which is the southernmost but also relatively separate from the inner Bay. The site near Tateyama showed somehow background contamination with all compound groups and highly different profiles of PCNs. The principal component analysis (PCA) of the data matrix has revealed that around the Tokyo Bay, apart from the evaporative emission sources for PCNs and PCBs, combustion related processes also play an important role as sources of the ambient air contamination not only with PCDDs/Fs but also with chloronaphthalenes and planar chlorobiphenyls.     

Source characterization and risk of exposure to atmospheric polychlorinated biphenyls (PCBs) in Ghana

With recent evidence that persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) are emerging in environmental media in some developing countries that otherwise have sparing production and usage history, it has become important to identify such contemporary source factors of PCBs and the risks this may pose, in line with the global consensus on POP management and elimination. The present study investigated contaminations from atmospheric PCBs in Ghana, deciphered source factors, and accessed risk of exposure to dioxin-like PCBs (DL-PCBs). Atmospheric PCBs were monitored by deployment of PUF-disk passive air samplers (PAS) at several sites across Ghana for 56 days. Atmospheric ∑₁₉₀PCB concentration in Ghana ranged from 0.28 ng/m³ in Kumasi to 4.64 ng/m³ at Agbogbloshie, a suburb in Accra noted for informal electronic waste (e-waste) recycling activities. As high as 11.10 ng/m³ of PCB concentration was measured in plumes from uncontrolled open burning of e-wastes at Agbogbloshie. Applying statistical source characterization tools, it emerged that e-wastes were a major contributor to the environmental burden of atmospheric PCBs in Ghana. The risk of DL-PCB toxicity via inhalation in the Agbogbloshie area was 4.2 pg TEQ/day, within similar order of magnitude of an estimated risk of 3.85 pg TEQ/day faced by e-waste workers working averagely for 8 h per day. It is suggested that elimination of e-waste sites would help to significantly reduce PCB-related toxicity issues in Ghana.

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Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice plants: possible contaminated pathways

Uptake of dioxins was confirmed in rice plants. We determined (i) dioxin concentrations and isomer profiles in leaf+stem samples of rice plants grown in three soils with different dioxin concentrations and isomer profiles and (ii) temporal changes in dioxin concentrations and isomer profiles in rice grown in a paddy field on which agricultural chemicals containing dioxin impurities had been used in previous years. Principal-component and chemical mass-balance analyses of the data showed that dioxin concentrations and isomer profiles in the rice grown in the different soils were similar, even though the dioxin concentrations and isomer profiles of the soils were different. However, the dioxin concentrations in the rice were influenced by dioxin levels in the atmospheric gas phase. Changes in dioxin levels during the growing period of the rice were also strongly influenced by adhesion of the soil to plant components during the early stage of growth, but gradually the influence of the atmospheric gas phase became predominant. Calculated dietary uptake estimates indicated that, even in rice grown in Japan on soil contaminated with high concentrations of dioxins, the amount of dioxins ingested by humans from rice is extremely small, and the amount of dioxins ingested by livestock from forage rice is similar to that for other forage crops.     

Isomer-specific analysis of chlorinated biphenyls,naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.     

Effects of Asian dust events on atmospheric bacterial communities at different distances downwind of the source region

Aeolian dust particles arising from arid and semiarid zones are known to carry microbes by air currents. The effect of wind-borne bacteria on atmospheric bacterial population at various downwind distances from the dust source regions must be clarified, but has not yet been reported. This study monitored the bacterial abundance and community composition in outdoor aerosol samples in Beijing, China, which is close to the Asian dust source regions, and compared them with the results obtained in a distant region(Osaka, Japan).The Asian dust collected in Beijing contained(4 ± 3) × 10~4 bacterial cells/m~3, approximately~4 times higher than in Osaka. On 15 April 2015, Beijing experienced severe Asian dust events with a 1000-fold increase in bacterial abundance, relative to non-Asian dust days. Dominant bacterial phyla and classes in Asian dust collected in Beijing were Actinobacteria, Bacilli and Acidobacteria, and the bacterial community composition varied more widely than in Osaka.The bacterial community compositions differed between the Beijing and Osaka dusts, even for the same Asian dust events. These results indicated that aerosol bacterial communities nearer the dust source are more affected by eolian dust than their distant counterparts.     

Accumulation of polychlorinated naphthalenes in domestic animal related samples

Concentrations of polychlorinated naphthalene (PCN) congeners were measured in domestic animal related samples such as feed ingredients, mixed feed and animal fat. Mean concentrations of total PCNs in feed ingredients ranged from 500 to 1500 pg g(-1) lipid wt with a high concentration found in fish meal. Total PCN concentrations were similar among mixed feeds, which ranged from 98 to 110 pg g(-1) lipid wt. The total PCN concentration in chickens was more than twice the amount in pigs. Tetra-CNs were the predominant homologues in all samples. Biomagnification of higher chlorinated PCN congeners, especially penta- and hexa-CNs, was a few fold greater in chickens compared to pigs. The estimated concentrations of 2,3,7,8-tetrachloro dibenzo-p-dioxin equivalents (TEQs) of some selected PCNs in feed ingredients, mixed feeds, chickens and pigs were 0.008 to 0.063, 0.001 to 0.002, 0.033 and 0.011 pg g(-1) lipid wt, respectively. Based on predicted luciferase inducing potency for each PCN congener, the estimated PCN-TEQs in feed ingredients and animal fat were similar to those that were estimated from selected PCNs.     

Evaluation of the impact of matrix effects in LC/MS measurement on the accurate quantification of neonicotinoid pesticides in food by isotope-dilution mass spectrometry

The use of isotope-labeled internal standards is the most widely accepted approach to overcome the matrix effects on quantification of pesticides in food by LC/MS. We evaluated the impact of the matrix effects on quantification of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam, in food by using deuterated internal standards. The calibration curves for each pesticide were obtained by using matrix-free and matrix-matched calibration solutions with blank brown rice, carrot, and green onion extracts. For brown rice and carrot, the matrix effects were not observed. In contrast, the slopes of calibration curves for each pesticide were influenced by presence of green onion extracts in calibration solutions (variability of the slopes was 4–9%), because the ratios of peak area for native pesticide to those for internal standards were influenced by matrix. The spike-and-recovery test with green onion was also performed. The analytical values obtained by using matrix-free calibration solution were biased from the spiked concentration, whereas those obtained by using matrix-matched calibration solution were comparable to the spiked concentration. These results indicate that matrix-matched calibration solution should be used for accurate quantification of neonicotinoid pesticides in food by LC/MS using deuterated internal standards.     

Determination of PCDD/Fs and dioxin-like PCBs in fish oils for feed ingredients by congener-specific chemical analysis and CALUX bioassay

The present research was intended to determine the suitability of the CALUX assay as a screening method for dioxins in fish oil used as a feed ingredient in Japan. Alteration of TEQ in fish oil according to newly proposed toxic equivalency factors (TEF) is also discussed. In the analysis, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 fish oil samples were determined by using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and CALUX bioassay. The mean TEQ values derived from 1998 WHO-TEF of PCDD/Fs and DL-PCBs were 2.6 and 9.9 pg g(-1) (ww), respectively. The levels of TEQ derived from the recently re-evaluated 2005 WHO-TEF were slightly lower than those of the former in both groups. Notably, the contribution of mono-ortho DL-PCBs to total 2005 WHO-TEQ was considerably decreased compared to the case of 1998 WHO-TEQ, resulting from the reduction in its TEF values, while the non-ortho DL-PCBs contribution was increased. The mean TEQ determined by CALUX assay for PCDD/Fs was approximately three times higher, whereas DL-PCBs was approximately two times lower than WHO-TEQ determined by HRGC/HRMS; the sum of PCDD/Fs and DL-PCBs was very similar by both methods. The correlation coefficients of TEQ between the CALUX assay and HRGC/HRMS analysis were 0.84, 0.89, and 0.90 for PCDD/Fs, DL-PCBs, and the sum, respectively. These results suggest that the CALUX assay is a very useful method for the screening of dioxin-related compounds in fish oils.     

Passive air monitoring of PCBs and PCNs across East Asia: a comprehensive congener evaluation for source characterization

A comprehensive congener specific evaluation of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in the atmosphere was conducted across East Asia in spring 2008, applying polyurethane foam (PUF) disk passive air sampler (PAS) as monitoring device. Mean concentrations derived for Japan, China and Korea were 184 ± 24, 1100 ± 118, and 156 ± 20 pg m⁻³ for ∑₂₀₂ PCBs, and 9.5 ± 1.5, 61 ± 6, and 16 ± 2.4 pg m⁻³ for ∑₆₃ PCNs, respectively. Relative to reported data from 2004, the present results suggest that air PCBs concentrations have not changed much in Japan and Korea, while it has increased by one order of magnitude in China. From principal component analysis, combustion emerged highly culpable in contemporary emissions of both PCBs and PCNs across the East Asian sub-region. Another factor derived as important to air PCBs was re-emissions/volatilization. Signals from PCBs formulations were also picked, but their general importance was virtually consigned to the re-emissions/volatilization tendencies. On the contrary, counterpart PCNs formulations did not appear to contribute much to air PCNs.     

Mass balance and long-term fate of PCDD/Fs in a lagoon sediment and paddy soil, Niigata, Japan

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in a sediment core and in samples of surface sediment and paddy soil collected from the Toyano lagoon and Kameda basin in Niigata, Japan, were analyzed to elucidate the temporal trends of their concentrations in the lagoon sediment and the relationship between the sediment and the paddy soil. The mass balance of these pollutants was also estimated to determine their long-term fate in surface waters. An analysis by chemical mass balance identified the agrochemicals pentachlorophenol and 2,4,6-trichlorophenyl 4-nitrophenyl ether as the major sources of PCDD/Fs. On the basis of the findings regarding the mass balance in the Kameda basin over the last 40 years, we estimate that more than half the input of PCDD/Fs to the Kameda basin has disappeared. We suggest that the PCDD/Fs that flowed out from the paddy fields have been transferred to the lower basin.