Shin-ichi Sakai

Environmental release and behavior of brominated flame retardants.

Recently, environmental problems relating to brominated flame retardants (BFRs) have become a matter of greater concern than ever before, because of the recent marked increase in levels of polybrominated diphenyl ethers (PBDEs) found in human milk in Sweden and North America. The question that arises is whether environmental levels of PBDEs and other BFRs will continue to increase, causing toxic effects to humans. In an attempt to elucidate the current state of the science of BFRs, we review the consumer demand for BFRs (mainly in Japan), the characteristics of waste flame-retarded products, sources of emission, environmental behavior, routes of exposure of humans, temporal trends, and thermal-breakdown products of BFRs. At present, flame-retarded consumer products manufactured 10-20 years ago, when PBDEs were frequently used, are being dumped. The possible major sources of emission of BFRs into the environment are effluent and flue gases from BFR factories and other facilities processing BFRs. With respect to the environmental behavior of BFRs, the lower brominated compounds are, on the whole, predicted to be more volatile, more water soluble, and more bioaccumulative than the higher brominated compounds. The most probable route for exposure of the general human population to PBDEs, especially the lower brominated congeners, is through the diet. The release of BFRs from consumer products treated with these compounds could also lead to human exposure. Temporal trends in PBDE levels in the environment and in humans worldwide seem to vary considerably, depending on the regions or country, with possible reflections of the historic and current use of PBDEs. The environment and the general human population are also exposed to the thermal-breakdown products of PBDEs, such as polybrominated and mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs and mixed PXDDs/DFs).

Brominated dioxin-like compounds: in vitro assessment in comparison to classical dioxin-like compounds and other polyaromatic compounds.

Recently, several countries agreed to adopt the Stockholm convention on persistent organic pollutants (POPs). One future obligation will be to add other POPs as new evidence becomes available. In vitro cell-based bioassays offer a rapid, sensitive, and relatively inexpensive solution to screen possible POP candidates. In the present study, we investigated the aryl hydrocarbon (Ah)-receptor activity of several dioxin-like POPs by using the Micro-EROD (Ethoxy-Resorufin-O-Deethylase) and DR-CALUX (Dioxin-Responsive-Chemical Activated Luciferase gene eXpression) bioassays, which are two state-of-the-art methods. The Micro-EROD system used in our study utilizes a wild-type rat liver cell line (rat liver H4IIEC3/T cells), while the DR-CALUX bioassay consists of a genetically modified rat hepatoma H4IIE cell line that incorporates the firefly luciferase gene coupled to dioxin-responsive elements (DREs) as a reporter gene. In the case of the DR-CALUX bioassay, we used an exposure time of 24 h, whereas we used a 72-h exposure time in the Micro-EROD bioassay. The aim of this study was to compare conventional dioxin-like POPs (such as polychlorinated dibenzodioxins and -furans, PCDD/Fs and coplanar polychlorinated biphenyls, PCBs) with several other classes of possible candidates to be added to the current toxicity equivalent factor (TEF) model in the future. Therefore, this study compares in vitro CYP1A1 (Micro-EROD bioassay) and firefly luciferase induction (DR-CALUX bioassay) in several mixed polyhalogenated dibenzodioxins and -furans (PXDD/Fs; X=Br, Cl, or F), alkyl-substituted polyhalogenated dibenzodioxins and -furans (PMCDD/Fs; M=methyl), polyhalogenated biphenyls (PXBs, X=Br, Cl ), polybrominated diphenyl ethers (PBDEs), pentabromophenols (PBPs), and tetrabromobisphenol-A (TBBP-A). We also evaluate congener-specific relative potencies (REPs) and efficacies (% of TCDD(max)) and discuss the dose-response curves of these compounds, as well as the dioxin-like potency of several other Ah-receptor agonists, such as those of the polyaromatic hydrocarbons (PAHs) and polychlorinated naphthalenes (PCNs). The highest REP values were found for several PXDD/F congeners, followed by some coplanar PXBs, trichlorinated PCDD/Fs, PAHs, PBDE-126, 1-6-HxCN, and some brominated flame retardants (TBBP-A). These in vitro investigations indicate that further research is necessary to evaluate more Ah-receptor agonists for dioxin-like potency.

A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals

Ever since the interest in organic environmental contaminants first emerged 50years ago, there has been a need to present discussion of such chemicals and their transformation products using simple abbreviations so as to avoid the repetitive use of long chemical names. As the number of chemicals of concern has increased, the number of abbreviations has also increased dramatically, sometimes resulting in the use of different abbreviations for the same chemical. In this article, we propose abbreviations for flame retardants (FRs) substituted with bromine or chlorine atoms or including a functional group containing phosphorus, i.e. BFRs, CFRs and PFRs, respectively. Due to the large number of halogenated and organophosphorus FRs, it has become increasingly important to develop a strategy for abbreviating the chemical names of FRs. In this paper, a two step procedure is proposed for deriving practical abbreviations (PRABs) for the chemicals discussed. In the first step, structural abbreviations (STABs) are developed using specific STAB criteria based on the FR structure. However, since several of the derived STABs are complicated and long, we propose instead the use of PRABs. These are, commonly, an extract of the most essential part of the STAB, while also considering abbreviations previously used in the literature. We indicate how these can be used to develop an abbreviation that can be generally accepted by scientists and other professionals involved in FR related work. Tables with PRABs and STABs for BFRs, CFRs and PFRs are presented, including CAS (Chemical Abstract Service) numbers, notes of abbreviations that have been used previously, CA (Chemical Abstract) name, common names and trade names, as well as some fundamental physico-chemical constants.

Combustion of brominated flame retardants and behavior of its byproducts.

The substance flow rate of PBDDs/DFs into flue gas and incineration residues from incineration of three types of waste samples containing brominated flame retardants were examined. The samples used consisted of PBDEs (a typical retardant), used TV casing materials (actual waste materials), and waste printed circuit boards. PBDDs/DFs concentrations in the experimental samples of PBDEs/PE, waste TV casing materials and printed circuit boards ranged between 3000 and 130,000 ng/g. These values are very high when compared to other investigations. The increase of chlorine concentration in input sample reduced the ratio of PBDDs/DFs in flue gas and raised the ratio of PCDDs/DFs. With adequate combustion control and flue gas treatment, the amount of PBDDs/DFs released from the incineration of resin containing brominated flame retardants was lower than the input amount. The presence of PBDDs/DFs in incineration residues dominated the total amount of dioxins released. When PBDDs/DFs, PCDDs/DFs and PXDDs/DFs were considered as a total, the total amount released was lower than the total amount input.

Municipal solid waste incinerator residue recycling by thermal processes

The melting technology makes incinerator residues, bottom ash and fly ash, stable and non-toxic. Moreover, this type of treatment allows the melted slag to be used as a resource again. In Japan, the melting process was developed in the 1980s and has been in practical operation at around 24 municipal solid waste (MSW) incineration facilities including scheduled ones. By the melting process, PCDDs/PCDFs in residues are decomposed at a temperature of approximately 1400°C in the furnace and volatile heavy metals are concentrated in the fly ash of the melting process.

World terends in municipal solid waste management

The philosophy of the Waste Management Hierarchy (prevention/minimization, materials recovery, incineration and landfill) has been adopted by most industrialized nations as the menu for developing municipal solid waste (MSW) management strategies. The extent to which any one option is used within a given country (or region) varies depending on a large number of factors, including topography, population density, transportation infrastructures, socioeconomics and environmental regulations. Recognizing these differences, the International Ash Working Group (IAWG) compiled available waste data from Canada, Denmark, Germany, Japan, the Netherlands, Sweden and the United States of America, for presentation at the Seminar on Cycle and Stabilization Technologies of MSW Incineration Residues held in March 1996.

Flame retardants in indoor dust and air of a hotel in Japan

Occurrence of flame retardants (FRs) in the indoor environment of highly flame-retarded public facilities is an important concern from the viewpoint of exposure because it is likely that FRs are used to a greater degree in these facilities than in homes. For this study, brominated flame-retardants (BFRs) and organophosphate flame-retardants and plasticizers (OPs), and brominated dibenzo-p-dioxins/furans (PBDD/DFs) were measured in eight floor dust samples taken from a Japanese commercial hotel that was assumed to have many flame-retardant materials. Concentrations of polybrominated diphenylethers (PBDEs) and hexabromocyclododecanes (HBCDs) varied by about two orders of magnitude, from 9.8-1700 ng/g (median of 1200 ng/g) and from 72-1300 ng/g (median of 740 ng/g), respectively. Concentrations of the two types of BFRs described above were most dominant among the investigated BFRs in the dust samples. It is inferred that BFR and PBDD/DF concentrations are on the same level as those in house and office dust samples reported based on past studies. Regarding concentrations of 11 OPs, 7 OPs were detected on the order of micrograms per gram, which are equivalent to or exceed the BFR concentrations such as PBDEs and HBCDs. Concentrations of the investigated compounds were not uniform among dust samples collected throughout the hotel: concentrations differed among floors, suggesting that localization of source products is associated with FR concentrations in dust. Passive air sampling was also conducted to monitor BFRs in the indoor air of hotel rooms: the performance of an air cleaner placed in the room was evaluated in terms of reducing airborne BFR concentrations. Monitoring results suggest that operation of an appropriate air cleaner can reduce both gaseous and particulate BFRs in indoor air.

Combinatorial bio/chemical analysis of dioxin and dioxin-like compounds in waste recycling, feed/food, humans/wildlife and the environment

The present review describes international activities using bioassays/biomarkers in combination with chemical analysis to measure the effects of dioxin and dioxin-like compounds (DLCs) in the environment. The above authors reviewed already the state-of-art bioanalytical detection methods (BDMs) for dioxins and DLCs [Environ Int (2001)]. The aim of this study will be to review applications of these bioassays/biomarkers to evaluate potential dioxins and DLCs. The present literature study lists relative potencies (REPs) of polyhalogenated dibenzo-p-dioxins and -furans (PXDD/Fs; X = Cl, Br, F), their thio analogues polychlorinated dibenzothiophenes (PCDTs) and thianthrens (PCTAs), polyhalogenated biphenyls (PXBs), polychlorinated naphthalenes (PCNs) and other Ah receptor agonists measured by several biodetectors (Tier 3 screening). The authors will discuss some examples of the applications of some of these biodetectors in biomonitoring programmes and recently occurred dioxin crisis in feed/food. The diagnosis of the biopotency of these pollutants in technical processes like thermally treated waste, waste water treatment, landfill leachate treatment, commercial PCB-mixtures, the release into the environment (soil, air and water) and the final intake into wildlife and humans will be reviewed.

Transfer of brominated flame retardants from components into dust inside television cabinets

Television (TV) set components are highly flame resistant, with their added brominated compounds such as polybrominated diphenyl ethers (PBDEs). These compounds might be released indoors via dust, which presents a potential exposure pathway for humans in the home environment. In this study, we collected dust from inside TV sets and TV set component samples (parts of housing front cabinets, rear cabinets and circuit boards) of five sets used in Japan. We measured BFRs (i.e., PBDEs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs)) and polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/DFs). Analytical results of the TV components showed that the concentrations of PBDEs, TBBPA and PBDFs (48,000 microg/g, 19,000 microg/g and 9600 ng/g as mean values, respectively) were all highest in the rear cabinets. The SigmaPBDD concentrations (460 ng/g as a mean value) detected were highest in the circuit board samples. The respective SigmaPBDE and SigmaPBDF concentrations in the dust samples were 67-500 microg/g (mean 300 microg/g) and 180-650 ng/g (mean 410 ng/g). Such concentrations were 2-3 orders of magnitude higher than those previously reported for house dust samples, which suggests that the brominated compounds are transferred from TV components into dust. Comparison of congener patterns of the brominated compounds in the dust identified the components as the source of these BFRs.

Full-scale plant study on fly ash treatment by the acid extraction process

Abstract Fly ash discharged from a municipal refuse incineration plant is regulated, by 1992 legislation, to be treated to prevent leaching of heavy metals before final disposal. We have developed a stable and simple fly ash treatment method “Acid Extraction-Sulfide Stabilization Process (AES Process)”, in which the fly ash is acid-extracted and stabilized by NaHS to change the residual heavy metal into insoluble heavy metal sulfide. The results of many fundamental experiments and pilot tests indicate that it is important to consider the characteristics of fly ash (fine, scattering, moisture-absorbing, etc.) in designing the AES Process. Since 1977, seven municipal incineration plants with AES Process have been constructed. At one of these plants, the fly ash and waste water is treated together by the AES Process and evaporation/crystallization process. The fly ash is discharged as stabilized cake for final landfill disposal; solid salt is recycled to soda production plants and condensed water is recycled in the plant as cooling water. This plant discharges no waste water. Operating results of the AES Process is that the stabilized cake conforms to the standard for landfill disposal in T-Hg, Cd and Pb, and the recovered solid salt contains approximately 99% NaCl. The operation cost per ton of the fly ash is ¥3,840 per ton.