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.     

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.     

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.     

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.     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

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.