BFR—governmental testing programme

Environment International 29 (2003) 781 – 792 www.elsevier.com/locate/envint

BFR—governmental testing programme Sabine Kemmlein a,*, Dorte Herzke b, Robin J. Law c a

Federal Institute for Materials Research and Testing (BAM), IV.22, Unter den Eichen 44-46, Berlin D-12200, Germany b Norwegian Institute for Air Research (NILU), N-9296 Tromsø, Norway c CEFAS Burnham Laboratory, Centre for Environment, Fisheries and Aquaculture Science, Remembrance Avenue, Burnham on Crouch, Essex CM0 8HA, UK

Abstract As a consequence of results from recent studies, indicating increasing concentrations of polybrominated diphenyl ethers (PBDEs) in a wide range of environmental samples, governments have begun to consider the need to restrict the production and use of this compound group. Within the EU, it has been decided to cease production and use of the pentamix PBDE formulation, and the industry has already moved to alternative compounds. In Asia, the Japanese industries restrict voluntarily the production and use of polybrominated biphenyls (PBBs), hexabromodiphenyl ether and tetrabromodiphenyl ether. In North America, no such decisions have been taken as yet, and production of the pentamix continues. Ecolabelling and ecological product declarations are also being used in order to accelerate the phase-out process of brominated flame retardant (BFR). They restrict to different degrees the use of BFR in plastic, textiles, flexible floorings and insulating materials. Many governments have also initiated studies intended to provide more information on the octamix and decamix PBDE formulations, and the replacement compounds hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA), regarding their significance as environmental contaminants and to inform the need for further regulatory action. These studies are summarised below. D 2003 Elsevier Science Ltd. All rights reserved. Keywords: Brominated flame retardant; Polybrominated biphenyl; Polybrominated diphenyl ether

1. Introduction The subject of brominated flame retardants (BFRs) presents a dilemma to governments in the industrialised countries. On the one hand, governmental intervention in economic processes supports reductions in the production and use of persistent, xenobiotic substances and the protection of the environment from possible hazardous consequences. On the other hand, though, they do need to protect people from the dangers of domestic fires. Accordingly, some countries (e.g. the UK and the USA) have developed regulations for fillings and furniture in order to ensure that they meet specified performance requirements for resistance to ignition. Brominated flame retardants (BFRs) are now acknowledged to be widespread environmental contaminants. This results from their manufacture over a period of decades, and releases into the environment following production and use. The differing toxicological, chemical and physical behav-

* Corresponding author. Tel.: +49-30-83-22-1891; fax: +49-30-83-221892. E-mail address: [email protected] (S. Kemmlein).

iour of BFRs, some of which are used as technical mixtures (formulations) containing a number of individual compounds, makes it difficult to fully assess their impact on humans and the environment. Depending on these differences in properties, BFRs are also classified differently within the executive branches of the EU. Currently, worldwide research is mainly focused on the polybrominated diphenyl ethers (PBDEs), but studies of the compounds tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) are now also underway. The pentamix formulation of PBDEs has been classified as hazardous to the environment on the basis of existing data and the present criteria which are applied (European Council Regulation (EEC) No. 793/93, 1993). The octamix and decamix PBDE formulations have been evaluated, provisionally at least, as not being of health concern, although studies continue. The aim of this paper is to document the research undertaken by governmental organisations in the main fields of application of BFRs. Most of the data presented here are derived from databases provided or supported by national and international administrative institutions. The paper focuses on measures, restrictions and directives initiated or decreed within both the national and international fields. In

0160-4120/03/$ - see front matter D 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0160-4120(03)00112-0

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addition, ecolabelling, as a soft regulation measure, is also described.

2. International activities The main focus with respect to BFRs was initially concentrated on PBBs in consequence of an accident that happened in Michigan, USA, in 1973, in which polybrominated biphenyls (PBBs) were accidentally mixed with animal feedstuffs (WHO, 1994). As a consequence of that incident, the production of PBBs was prohibited in the USA in 1976, and in Europe in 1980. In the latter case, there was one known temporary limited exception, in France until 2000 for the production of decabromobiphenyl (deca-BB formulation). In addition, the use of PBB in textiles coming into contact with skin has been prohibited since 1983, and the use and import of PBBs have been prohibited or banned in Switzerland and Austria (UBA, 1999). In 1989, the Association of the German Chemical Industry (VCI) and the Association of Plastic Manufacturers in Germany (VKE) voluntary agreed to discontinue the production and application of PBDEs and PBBs in Germany (UBA, 1999). In 1994, a proposed prohibition of the production of PBDE in the European Union could not be passed, and so in Germany, the contents of PBDE in products and formulations were regulated by setting a maximum limit for PBDD and PBDF under the German Ban on Chemicals Ordinance (UBA, 1999). In 1991, the OECD’s Risk Reduction Programme began to investigate BFR and their report was produced in 1994 (OECD, 1994). Aspects such as the commercial and environmental life cycle of these substances, as well as any risk reduction measures implemented in member countries, were taken into consideration. In 1995/1996, also within the framework of the OECD, the international flame retardant producers agreed in the OECD Voluntary Industry Commitment (VIC) to focus their production and application on the three main technical PBDE formulations, the penta-, octaand decamixes. This obligation also provided that contamination with lower brominated congeners and isomers in the technical octamix and decamix PBDE formulations should be avoided during the manufacturing process (UBA, 1999). As a result of the OECD meeting held in Switzerland in 2002, the OECD clearing house countries (UK, Sweden, Switzerland, Netherlands) will each receive questionnaires concerning a call for action on BFRs. Based on the questionnaires, a discussion paper was prepared and submitted to the OECD Chemicals Joint Meeting, held in November 2002. Within the framework of activities undertaken by the Oslo and Paris Commissions (OSPAR Commission) for the protection of the maritime environment, all BFRs and not only specified compounds are included. On the OSPAR list of chemicals for priority action, BFRs are listed, and their status has been confirmed by both OSPAR and HELCOM, in 1998 and 2000, respectively. Sweden originally proposed

the prohibition of BFR within the framework of the Oslo and Paris Commissions in 1994 (UBA, 1999). At the Fourth International Conference on North Sea Protection (INK) held in Esbjerg in 1995, the possible substitution of BFRs and the development of more environmentally friendly alternatives was recommended (UBA, 1999). The disposal of wastes containing PBDE is regulated by the existing substance regulation (EC Regulation No. 793/ 93/EEC). Due to the production levels of PBDE, the commercial products (the penta-, octa- and decamixes) are included within the first and second EU priority lists. Since 1997, the EU and OECD have discussed PBDE within the framework of the European substances regulations. Currently, risk assessment reports for the evaluation of risks to human health and the environment posed by the substances HBCD and the three PBDE formulations are either complete or are in preparation (EEC/793/93). Furthermore, the Council of the European Union discussed a guideline for the marketing and use of the pentamix of PBDEs with a maximum content of 0.1% in materials and formulations in 2001 (European Directive 76/769/EWG, 2001). With global UNEP POP Convention (signed in 2001) and the POP protocol of the UNECE Convention on Long-Range Transboundary Air Pollution (signed in 1998), we now have two international instruments aiming at restricting the use and releases of persistent organic pollutants (POPs) (Peltola and Yla¨-Mononen, 2002). BFRs were not included within the initial substance lists under these two conventions, but the pentamix PBDE formulation seems to fulfil the screening criteria set for the inclusion of new substances within both POP frameworks. This product was proposed as a new candidate at the third meeting of the United Nations Economic Commissions for Europe (UNECE), which took place in June 2002. The corresponding expert group reviewed a preliminary dossier provided by Yla¨-Mononen (Finland) and Johanssen (Sweden), prepared for the Nordic Council of Ministers. The dossier concludes that the pentamix formulation meets the criteria due to its characteristic properties (potential for long-range atmospheric transport; persistence in water, soil and sediment; bioaccumulation; toxicity and ecotoxicity) (UNECE, 2002). The most practical way to restrict releases of this product would be to restrict use, both regionally and globally (Peltola and Yla¨-Mononen, 2002). A ‘‘guidance document for the collection, assembly and evaluation of data on sources, environmental levels and impacts of persistent toxic substances’’ was established in 2000 within the framework of the Inter-Organisation Programme for the Sound Management of Chemicals (IOMC) also discussing PBDE. The report was produced as part of a Project Development Facility (PDF-B) grant provided by the Global Environment Facility (GEF). The IOMC have been funded by UNEP, ILO, FAO, WHO, UNIDO, UNITAR and OECD following the recommendations by the 1992 UN Conference on Environment and Development (IOMC, 2000). BFRs were also discussed in the ‘‘Regionally Based

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Assessment of Persistent Toxic Substances’’ Mediterranean Region held in Barcelona in 2001 (UNEP, 2001). The International Council for the Exploration of the Sea (ICES) is responsible for the promotion, coordination, and dissemination of research on the physical, chemical and biological systems in the North Atlantic and works with experts from 19 member countries. The Council Resolutions arising from the 1999 Annual Science Conference also include the implementation of a research programme on cause –effect relationship between contaminants and individual effects in harbour, grey, and ringed seal according to the plans detailed in the 1999 report of the Working group on Marine Mammal Habitats. The research programme covers nine groups of compounds focusing also on polybrominated flame retardants (ICES-report, 2002). In addition, the European Commission has adopted proposals for a Directive on Waste Electrical and Electronic Equipment (WEEE), concerning restrictions on the use of certain hazardous substances in electrical and electronic equipment, which also requires the substitution of BFR in new electrical and electronic goods from 1 January 2008 (EC, 2000). To avoid any long-term deterioration of freshwater quality and quantity, the EU adopted with the Water Framework Directive (2000/60/EC) a programme of actions (EU Water Framework Directive, 2000). The ultimate aim of this directive is to achieve the elimination of priority hazardous substances and to contribute to achieving concentrations in the marine environment near background values for naturally occurring substances. The final agreement divided Annex X substances into three categories: priority hazardous substances, priority substances (under review) and priority substances. This list will be reviewed every 4 years. Releases of priority hazardous compounds are ceased or phased out to the aquatic environment within a 20-year period. Pentabromodiphenyl ether was recognised as a priority hazardous substance, with no limitation to a single isomer (there are 46 isomers with this structure).

3. Governmental studies—review Administrative bodies have been adopting different basic approaches worldwide in order to evaluate and reduce the potential risks posed by BFRs used in plastics, textiles and other materials. In the following section, research projects, which were supported, initiated or financed by the governmental authorities within the scope of regional activities, are described. 3.1. European countries Brominated flame retardants were first detected in sediment and fish downstream of plastics and textile industries in Sweden (Andersson and Blomkvist, 1981). Following that discovery, several Swedish institutes began to develop

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analytical methods, and subsequently conducted studies to investigate the fate, distribution and toxicology of a variety of BFRs (Haglund et al., 1997; Jansson et al., 1993; Nore´n ¨ rn et al., 1996; Sellstro¨m et al., and Meironyte´, 2000; O 1993, 1997; Sjodin et al., 1998). Since Sweden has a long tradition of environmental protection, the Swedish government had decided as early as 1990 to prohibit the most harmful brominated flame retardants. The Swedish government commissioned the National Chemicals Inspectorate (KemI) to investigate how to phase out the brominated flame retardants PBDE and PBB. After some voluntary efforts from branch organisations and companies, KemI proposed that the government should prohibit the marketing and use of PBDE and PBB, as well as the marketing of goods containing these substances, in 1999 (phase out of PBDE and PBB). Sweden continues to work within the EU for a Europe-wide prohibition, and also makes efforts to influence regulatory authorities worldwide (The Swedish National Chemicals Inspectorate, 1999). Ecolabelling, ecological product declarations (no PBDE or PBB in plastic parts weighing more than 25 g), rules on public procurement, and the introduction of producer liability was all used in order to accelerate the phase-out process. As a result, a newly established Nordic Environmental Council for Trade will introduce corresponding systems in Norway and Denmark (The Swedish National Chemicals Inspectorate, 1999). In 1996, the Chemicals Policy Committee was established, proposing the banning by 2007 of all products, including chemicals, containing persistent and bioaccumulating substances, as well as any substances that give rise to serious or irreversible effects on health or the environment. Additionally, by 2012, production processes should have been developed to the extent that they meet the same requirements. Draft Swedish EPA regulations on the environmentally sound treatment of WEEE recommend the separate handling of plastics containing the brominated flame retardants PBB or PBDE. These regulations were planned to come into effect at the same time as the producer responsibility requirements and Section 25 of the Ordinance on Waste Collection and Disposal, i.e. 1 July 2001. In 1999, the ‘‘NewS’’ program was launched (‘‘A new strategy for the risk management of chemicals’’), financed by MISTRA, the Swedish Council for Work Life Research, the Swedish EPA and The Swedish National Chemicals Inspectorate. Within this programme, brominated flame retardants will be used as model substances (Bishop et al., 2002). Eleven research projects will focus on the reproductive and developmental toxicology of these compounds, and also address ecotoxicological problems connected with the Baltic Sea. Beside PBDE, several other additive and reactive brominated flame retardants will also be investigated. Coordinated by the Swedish EPA, a health-related environmental monitoring programme has been launched in order to measure and estimate human exposure to substan-

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ces that are hazardous to health, including BFR. The Laboratory for Analytical Environmental Chemistry (ITM) at the University of Stockholm is engaged in The National Monitoring Program with several other projects, for example, the environmental monitoring of PBDE and HBCD in the freshwater and marine environments, including the identification of any temporal trends in concentration. In connection with this, herring, cod and eelpout liver, and guillemot eggs were investigated in 2000. Additionally, a project was initiated in 2000 with the aim of investigating the spread of TBBPA from several discrete sources. Sediment, fish and air samples were studied, together with sewage sludge. Within the national network for groundwater, fish samples from 18 lakes are stored in a specimen bank each year. With the cooperation of the Swedish University of Agricultural Sciences (SLU), the national Board of Fisheries (FiV), the Institute for Applied Environmental Research (ITM) and the Swedish Museum of National History (NRM), the concentrations of BFRs are monitored in fish from two lakes. Beginning in 2000, BFRs were measured within the framework of screening activities (Hedlund, 1998). The National Food Administration carried out PBDE measurements in breast milk of primiparous mothers from the Uppsala region of Sweden. No relation to food intake, body mass index, smoking habits or PC work could be found in this study (Atuma et al., 1999; Darnerud et al., 2001). In the follow-up study, Lind et al. (2001) confirmed these findings. During the project Riktsmaten 1997 – 1998, the uptake of PBDE from the diet was investigated. Based on concentrations in food determined in 1999, the dietary intake of PBDE for individuals in Sweden has been estimated to be 51 ng/day (Darnerud et al., 2001). By signing the European Economic Agreement (EEA), Norway has agreed to implement the EU legislation on chemicals. Norway follows the EU directive 79/663/EEC that prohibits the use of tris(2,3-dibromopropyl)-phosphate in textiles, as well as the use of PBB in textiles which are in contact with skin. Additionally, TBBPA, HBCD, and the penta- and octa-PBDE formulations were placed on the observation list for hazardous substances of the Norwegian Pollution Control Agency (SFT), following the lists of priority of the EU program for risk assessment. This includes a requirement for a substantial reduction of emissions by 2010 (Reports to the Storting, 1997). To achieve this goal, a material flow analysis was ordered by the Norwegian Pollution Control Agency in 1999 in order to assess the amounts of BFR circulating within the Norwegian community (Juhl, 1999). In 2002, the Norwegian Pollution Control Agency (SFT) instructed the Norwegian Institute for Air Research to screen the Norwegian environment for BFR. The focus was placed on risk locations as well as waste dumping sites, and also in the marine environment so as to investigate the long-range atmospheric transport characteristics of BFR. Beside PBDE and PBB, HBCD and TBBPA were also investigated (Schlabach et al., 2003).

As a result of the Fourth North Sea Conference (Fourth NSC Ministerial Declaration, Section 67), the program for the Harmonised Quantification and Reporting Procedures for Hazardous substances (HARP-HAZ) was initiated by SFT, assisted by DGXI of the European Commission and the European Environment Agency (EEA). Under the umbrella of this program, guidance documents on BFRs as hazardous substances have been developed, with Sweden as the lead country. The selection was based on the OSPAR List of Priority Substances and North Sea Ministerial Declarations. In the Revision of Observation of Environmental Pollutants by the Directorate for Environment (Miljødirektoraten) in 2000, BFRs are defined as a compound class for which continued surveillance is recommended, either because of their potential for harmful effects on environment and health, or because national or international regulations require it (Ministry of the Environment, 1999). In the late 1990s, Norwegian institutes began to investigate the extent of the contamination of the marine and terrestrial environment by BFRs. The National Institute of Public Health, the Norwegian Institute for Air Research, the Norwegian Polar Institute and the Norwegian Veterinary Institute are involved in this research. BFRs were detected even in samples from the Norwegian Arctic, as is also the case for other Arctic regions such as northern Canada (Ikonomou et al., 2002a; Law et al., 2003, this volume). The Norwegian Research Council funded several projects, focusing on the environmental concentrations and effects of BFR. In 2001, the project ‘‘BFR and polychlorinated alkanes in terrestrial and freshwater environment of Norway’’ began as a collaboration between the Norwegian Institute for Air Research (NILU), the Norwegian Institute for Water analyses (NIVA), the Norwegian Institute for Nature Research (NINA), the University of Oslo and the Norwegian Defence Research Establishment (FFI). During this 3-year project, sources such as municipal incinerators and sewage treatment plants will be investigated. Later, time trend and atmospheric transport studies will be carried out, focusing on archived and actual air samples from different areas of Norway, and collected from 1961 to the present day. As a third aspect, BFR in tissue samples from terrestrial animals (reindeer, moose, deer hare, willow grouse, badger and lynx) and freshwater (fish and semipermeable membrane devices (SPMDs)) will be analysed in order to identify regional trends (NFR141202/720). NINA and NILU began a second collaborative project in 2001, ‘‘Investigation of bioaccumulative and toxic compounds and their transformation products in eggs of Norwegian bird of prey’’, which includes the quantification of several BDE and BB congeners, as well the identification of their biotransformation products, in the eggs of five different species of birds of prey (NFR 140666/720). This is a follow-up study of the project ‘‘Determination and quantification of new organic pollutants in eggs from selected Norwegian bird of prey species’’ (NFR 134455/720), where evidence of BFR contamination in eight bird of prey

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species (merlin, white-tailed sea eagle, goshawk, golden eagle, peregrine falcon, osprey, gyrfalcon, sparrow hawk) could be found (Herzke et al., 2001). At the Norwegian Polar Institute, a research project is determining the concentrations and effects of organochlorines and PBDE in glaucous gulls. The extent of any correlation between the concentrations of PBDE and organochlorine pollutants will be investigated. Both free-living and captive glaucous gull chicks will be used to seek an association between their immune responses and exposure to PBDEs. In a recent study financed by the Norwegian State Pollution Control Authority, (TA-1781/2001) and the Norwegian Research Council (135604/720) undertaken in 2000, BFRs were analysed in liver from glaucous gull from the Norwegian Arctic (Svalbard archipelago and Bjørnøya) (Herzke et al., 2003). As a part of the Global Learning and Observation to Benefit the Environment (GLOBE) Program, a project entitled ’’GLOBE Arctic: New POPs in the Arctic’’ was launched in 2001. Students from the Arctic territories (Canada, USA/Alaska, Russia, Finland, Sweden, Norway, Iceland) collected biological samples, which were analysed by NILU for BDE47 and BDE99 as representatives of the BFRs, in addition to PCBs. The students will contribute to the documentation of PBDE distribution in the Arctic, learn more about pollutants in the environment and appropriate sampling techniques, as well as cooperating with students from other countries and research programs. In Germany, the Federal Environmental Agency (UBA), the Federal Environment Ministry (BMU) and other authorities have commissioned several studies with respect to BFR within the framework of the UFOPLAN. UFOPLAN is an annual programme established by the BMU in response to current research requirements suggested by the UBA, the Federal Agency for Nuclear Safety (BfS) and the Federal Agency for Nature Conversation (BfN) (UBA, 2002). Current projects are directed towards gathering data to supplement existing data and fill perceived gaps, and to establish a database. Studies are being conducted on the levels and trends of BFR concentrations in various environmental compartments, as well as those concerning toxicological and ecotoxicological effects. Initial studies have focussed on the formation and release of PBDD and PBDF during the incineration of flame retarded plastics and textiles, and possible pollution by PBDD/F resulting from the production of flame-proof plastics (Hutzinger, 1990; Theisen et al., 1991; Ball et al., 1991; Kieper, 1996). Additionally, the toxicological effects of PBDD and PBDF were examined (Hutzinger, 19891991). Further studies were performed on newly developed flame retarded products with the aim of substituting halogenated compounds, or at least to reduce their use in materials like polyurethane foam and duroplastics (Hesselbach, 1990-1993; Markert, 1995). Within the framework of the electronic scrap ordinance, it is suggested that electric and electronic units should be

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recycled. A study was performed to improve the treatment and utilisation of electronic waste considering the interfering contents of BFR and bromine in housings and in epoxy resins in particular (Fraunhofer ICT, 1999). In addition, the effects of recycling and sanitation of electronic waste and flame retarded plastics have been tested (Teller and Gustmann, 1995). With the support of the Industrial and Material Technologies (Brite-Euram III), the project ‘‘Supercritical fluids to extract and / or degrade organic waste materials especially flame retardants’’ (SCOW) carried out since 1998 by institutes in Germany, Belgium, France and Austria, with the German Fraunhofer Institute for Chemical Technology as project coordinator, is aimed at the development of a highly effective process for adequate treatment of mass consumer and industrial waste with special regard to BFR (Fraunhofer Institut fu¨r Chemische Technologie, 2002). Another aspect of the research concentrated on the pollution relevance of small electric devices. Based on the idea of pre-sorting a specified amount of electronic waste into representative high and low contaminated fractions, PBDE, along with polychlorinated biphenyls, naphthalenes and paraffins (PCB, PCN, PCA), were considered to be the most relevant pollutants. This project was initiated in 1996 in cooperation with the Federal Environment Agency, the Ministry of Environment in Lower Saxony and the Regional Authority for Ecology, also based in Lower Saxony, and was performed by the University of Hanover (Doedens, 1998). Within the German framework of the Recycling and Disposal Act (Kreislaufwirtschafts- und Abfallgesetz) studies are underway to evaluate and optimise different recycling processes with respect to the formation of pollutants and the reaction behaviour of the commonly used FRs (van Eldik, 1999). The Association of Technical Inspection (Gesellschaft fu¨r ¨ V Nord) carried out the investigation of Umweltschutz TU the emission behaviour of volatile (VOC) and semivolatile (SVOC) organic compounds, including BFRs from electronic products like video recorders and TV sets. Brominated compounds were represented by hexabromobenzene, pentabromotoluene and one unidentified tetrabromodiphenyl ether congener (Wensing, 1999). In 2000, the German UBA published the report ‘‘Substituting environmentally relevant flame retardants: Assessment fundamentals’’. The corresponding study examined the status of the use of flame retardants in selected product sectors like construction, electronics, electrical engineering and rail vehicles, as well as textiles/upholstery and alternatives (potentials for substitution and reduction of use). Additionally, the study characterises 13 different flame retardants in terms of material flows, applications and usage and toxicology/ecotoxicology (Leisewitz et al., 2000). As part of the UFOPLAN, a project has been initiated by the UBA examining possible emissions of flame retardants from consumer products and building materials, and has

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been conducted by the Federal Institute of Materials Research and Testing (BAM) since 2001. Preliminary results indicate that emissions of several phosphorus-based FRs, HBCD and PBDE (up to hexabrominated compounds) are quantifiable using special emission test chamber as a reference method (Kemmlein et al., 2002). Within a study with the aim of verifying the environmental fate of accumulating hazardous organic compounds, BFRs were determined in sewer film. Among other compounds, a number of brominated organic compounds were detected, including brominated diphenyl ethers, two polybrominated phenyl alkyl ethers and bromocyclene (Sauer et al., 1997). Water samples, sediments, effluents and sludges from sewage treatment plants (STP) from various locations in the southwest of Germany were also analysed (Kuch et al., 2001). An additional collaborative study (PBDE-NTOX) started in 2000 with the aim of investigating the possible neurotoxicological effects of developmental exposure of animals to PBDE, and is performed by laboratories in Germany, Sweden, Italy, Switzerland and Spain. Project coordinator is the German Medical Institute of Environmental Hygiene (Universita¨t Zu¨rich, 2001). In order to examine time trends and to monitor levels of PBDE in human blood samples, a study was conducted using samples collected over a period of 14 years (1985 – 1999) (Pa¨pke et al., 2000). Due to the lack of data regarding toxicological effects due to long-term exposure to BFRs, the study ‘‘Toxicological aspects of flame retardants’’ has been initiated to assess the potential risks posed by waste disposal and the utilisation of electronic goods (Boecker et al., 2002). In order to investigate the neurotoxicological impact of endocrine disrupting pollutants on rats with special regard to PBDE, a study was initiated by the BMU and UBA in 2000 and is being performed by the University of Du¨sseldorf. To investigate the human exposure, the Federal Institute for Health Protection of Consumer and Medicine (BGVV) initiated the study: ‘‘Residual analysis of polybrominated flame retardants in mothers’ milk from Germany particularly with regard to polybrominated diphenyl ethers (PBDE)’’. Based on the results, the exposure and potential health effects for babies via nursing should be estimated. Additionally, the time response and the change of congener/isomer pattern during the nursing period will be determined including the influence of nutrition (vegetarian, nonvegetarian), age, body mass index, and occupation. Levels in blood and milk of the baby and mother will be compared, expressed on a lipid basis. This project will start in 2002 and represents an observation study. No interventions are planned (Vieth, 2001). Austria has banned the use and production of PBBs for all applications. In 2000, the Austrian government initiated a study regarding the use of BFRs in Austria. The study was a collaborative project undertaken by the Federal Ministry of Agriculture Forestry Environment and Water Manage-

ment (BMLFUW), the Federal Environment Agency and the Inspectorate of Chemicals. 64 consumer products including electronic devices and accessories, textiles and building materials were checked for BFR. Deca-BDE, HBCD and octa-BDE were found to be the most relevant FRs in these samples. Insulating boards had the highest content of BFRs (Lorbeer and Hanus-Illnar, 2001). In the Netherlands, a risk assessment of polybrominated flame retardants carried out by the Dutch Ministry of Housing, Spatial Planning and the Environment in 1990 was reevaluated in 1994 in the light of new information available at that time. This report focused on the possible increase in PBDD/F formation in MWI plants as a consequence of the growing use of BFR in plastics, on deca-BDE and its environmental behaviour and, as a third aspect, on the biomagnification of compounds from the pentamix PBDE formulation (Plassche et al., 1994). Both in 1991 and in 1993, the Netherlands proposed banning the use of PBB and PBDE with only a few exceptions. On both occasions, the proposal was withdrawn and is not yet in effect. Within the framework of the Dutch National Investigation on Estrogenic Compounds, a project (LOES project) was initiated by the Institute for Inland Water Management and Waste Water Treatment (RIZA), the National Institute for Coastal and Marine Management (RIKZ), the Association of River Waterworks (RIWA) and others. In this study, PBDEs and PBBs were examined in biota as well as in STP influents and effluents, sediments and suspended particulate matter (SPM) from various locations in the Netherlands. In connection with the Community Programme of Research on Environmental Hormones and Endocrine Disruptors (COMPREHEND) programme, possible estrogenic effects in organisms sampled at the same sites were investigated (De Boer et al., 2000). In 2002, a programme began with the aim of certifying BFR (including PBDE, TBBPA and HBCD) in candidate reference materials, sediment and flounder. These efforts are conducted within the EU founded framework of the feasibility study ‘‘Biological Reference Materials for Organic Contaminants’’ (BROC; contract number: G9RD-CT-200100518) with the Netherlands Institute for Fisheries Research as project coordinator. Participating countries beside the Netherlands are Sweden, Ireland, UK, Germany, Switzerland, Belgium, Norway, Czech Republic, France, Spain and USA. In 1999, the Danish EPA prepared a draft action plan intended to curb the use of BFR in Denmark (Danish EPA, 2001). Within the framework of the action plan, the occurrence and use of BFR in Denmark has been researched in detail. In addition, the emission and disposal of BFR to the environment, as well as substance flow balance for BFR, have been discussed. This survey also included an assessment of possible alternatives to BFR (Lassen et al., 1999). The action plan will serve as an establishment for future regulations of BFR in Denmark and proposes measures like the phasing out of problematic FRs in the EU and other

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countries. Additionally, knowledge about other BFR and alternatives should be enhanced and the use of PBB and PBDE should be discontinued within a few years in the Danish manufacturing industry (Danish EPA, 2001). Further objectives are to conduct investigations on source emissions of BFR and the risk assessment of TBBPA, in particular. Due to the fact that BFRs are not generally permitted in ecolabelled products, the Danish EPA also will continue to work towards ensuring that BFR with harmful effects to the environment and health are not present in products certified by ecolabel criteria. Based on the results of the substance flow analysis project, the existing knowledge about the environmental and health risks of the BFR has been summarised and a toxicological and ecotoxicological data screening conducted (Simonsen et al., 2000). Another project was initiated for compiling available data on the environmental and health properties of selected FRs in order to search for alternatives to BFR (Stuer-Lauridsen et al., 2000). European Flame Retardants Association (EFRA) subsequently provided additional information and some revisions were made (Stuer-Lauridsen, 2001). Within the framework of the International Arctic Monitoring Assessment Programme (AMAP) and the Danish Cooperation for Environment in the Artic (Dancea) several studies have been initiated. PBDE concentrations in biota from different locations in Denmark were determined within one study. As high levels were detected close to populated areas, the results suggested that local sources were important in addition to long-range atmospheric transport (Christensen et al., 2001). Initial screening of BFR was performed by the National Environmental Research Institute in sediments collected in the Danish marine and freshwater environment (Platz and Christensen, 2001). The Danish Implementation Plan (1997 –2000) for AMAP Phase II in Greenland and the Faroe Islands included a number of projects funded by the Danish EPA under the Dancea programme. Based on the results of AMAP’s first assessment, the implementation of AMAP Phase II in Greenland will give priority to monitoring of POPs, including flame retardants and heavy metals. Another project is focusing on the development of analytical methods for the determination of BFR in marine biota (Platz, 1999). Only sparse information is available concerning BFR research in Switzerland. Since the electronic scrap ordinance (VREG) came into force in 1998, electric and electronic goods have to be either professionally disposed of or exported from the country. In this connection, the presence of BFR in electric and electronic products has been investigated to gain more information about their use in Switzerland (Wegmann, 1999). A study was initiated in 2001 by the BUWAL (Swiss Agency of the Environment, Forests and Landscape) in order to analyse, compare and evaluate the material flow of TBBPA, penta-BDE, octa-BDE and decaBDE on the basis of available data provided by industry, governmental institutes, and a literature review (Morf et al., 2002).

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The occurrence of BFR in the environment, and the potential human exposure to these compounds is a matter of particular interest to the authorities. In 2000, the Swiss Federal Council ratified the National Research Programme 50 (NRP 50) in order to develop scientific strategies for the assessment of risks and hazards posed by endocrine disruptors. This programme also includes selected BFR compounds and the determination of environmental concentrations of BFRs and their transformation products, as well as animal and human exposure. The research projects began in 2002 (SNF, 2001). To our knowledge, the Belgian authorities have not been initiating testing programmes with the aim of assessing the potential hazards posed by BFR. In addition, the Belgian government have taken no risk reduction actions concerning BFR to date. In cooperation with other institutes, the Brussels Scientific Institute of Public Health has initiated an investigation of the toxicological aspects of BFR (Van Overmeire et al., 2001). In 1995, the Department of the Environment of UK funded a pilot study with the aim of investigating the extent to which flame retardant compounds were present in the UK environment as a result of their manufacture and use in the UK. Samples of sediment and fish were collected in the vicinity, and downstream, of suspected sources, and from the River Tweed as a reference site (Allchin et al., 1999). These data were fed into the EU risk assessment for the pentamix formulation. The UK Department of Trade and Industry (UK DTI) Consumer Safety Unit commissioned the report ‘‘Risks and benefits in the use of flame retardants in consumer products’’, published by the Polymer Research Centre, University of Surrey in 1999 (Stevens and Mann, 1999). The aims of the study were to review the available data on the use, utility and toxicity of flame retardants used in the UK. The report concluded that, despite falls in the number of fire deaths over the years, losses from fire are still a significant problem worldwide, particularly in dwellings. There was no evidence that flame retardants contribute to the direct human health risks arising from toxic gas effects. Information available suggested that the benefits of many flame retardants in reducing the risk from fire outweighed the risks to human health. It was recognised, however, that an exhaustive toxicological analysis of all flame retardant compounds and combustion products was not possible within the scope of this report. 3.2. North America The USA currently has no plans to regulate the use of flame retardants, other than PBB which is already prohibited. Testing of BFRs with special regard to deca-BDE, octa-BDE and penta-BDE under the EPA—industry Voluntary Children’s Chemical Evaluation Program (VCCEP) is planned (Beveridge & Diamond, 2001).

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The statistics regarding environmental releases of decaBDE indicate a decline in environmental releases from use and manufacturing. In April 2000, the US National Academy of Sciences (NAS) completed a review of 16 flame retardants, among them deca-BDE and HBCD (National Research Council, 2000). A toxicity study on BFR is under way under the auspices of the US EPA. The Neurotoxicology and Experimental Toxicology Division of the National Health and Environmental Effects Research Laboratory (NHEERL) is studying the potential health effects of PBDE, with special regard to their possible endocrine disrupting function (US EPA, 2001). An overview study initiated by the National Centre for Environmental Economics (NCEE) concerning research on BFRs will start in 2002. All available information that would be useful for conducting a risk assessment of PBDE is to be reviewed and summarised (US EPA, 2002). Several studies on BFR have also been implemented by the US Department of Agriculture (Garber et al., 2001; Hakk et al., 2001). The Hazardous Materials Laboratory, which is part of the Department of Toxic Substances Control, California EPA, has been conducting monitoring of PBDE levels in California citizens (adipose tissue, blood) and in marine mammals (She et al., 2002). Furthermore, a human health risk assessment was performed in order to predict chronic daily intakes of penta-DBE, octa-DBE and deca-BDE for different age groups associated with eight different exposure pathways (Wenning, 2001). A study was performed investigating the mobility, sorption and fate of TBBPA in loam soil and sand (Larsen et al., 2001). The US EPA and the New York State Department of Environmental Conservation (NYSDEC) are collaborators in the Great Lakes National Program Office within which several monitoring and research activities have been initiated, focussing on BFR. PBDE have recently been added to the list of analytes in the Great Lakes Fish Monitoring Program, as well as TBBPA (Luckey et al., 2001). Sewage sludges destined for land application were collected from four different regions of the USA. In this study, conducted by the Department of Environmental Science, Virginia Institute of Marine Science, the decamix and pentamix formulations were analysed (Hale et al., 2001). Systematic studies on occurrence of BFR, and of PBDEs in particular, began in Canada in 1997, when a proposal to study the background levels of PBDEs and other chemicals in Canadian environment was funded by the Canadian Department of Fisheries and Oceans under their Toxic Chemicals Program. As a result of recent amendments to the Canadian Environmental Protection Act, 1999, all chemicals that are on the Domestic Substances List are subject to categorization and screening level risk assessments (SLRAs). Polybrominated diphenyl ethers (PBDEs) are currently being assessed, and have been accorded a high priority. The assessment should be completed during 2002.

Canada’s National Water Research Institute has hosted three international workshops at which scientists from private laboratories, government and university participated to exchange knowledge about BFR. The federal government, through Environment Canada, together with Fisheries and Oceans Canada, Health Canada and the Universities of Guelph and Trent, has been involved in a multi-year investigation of the impact of PBDE in Canada. The participating laboratories determined concentrations in human milk, biota, bird eggs, sediment and air in different parts of the country, confirming the ubiquitous contamination of the Canadian environment with PBDE and PBB (Alaee and Wenning, 2002; Alaee et al., 2001; Ikonomou et al., 2002a; Palm et al., 2002). A study, financially supported by the Department of Fisheries and Oceans under the Toxic Chemicals Program and the Government of Canada through the Toxic Substances Research Initiative (TSRI), jointly managed by Health Canada and Environment Canada, investigated the spatial distribution of PBDE and PBB in lake trout from the Laurentian Great Lakes (Ikonomou et al., 2002b; Luross et al., 2001). In another study, financed by the Environmental Science Strategic Research Fund (ESSRF) of the Department of Fisheries and Oceans and by TSRI, PBDE were analysed in environmental samples from coastal British Columbia. Under the umbrella of the Northern Contaminants Program (NCP), led by Indian and Northern Affairs Canada, several projects researching BFR have been initiated: Time trends of PBDEs and PBBs will be investigated in a study of contaminants in beluga and ringed seals from the Canadian Arctic. By determining the contaminant levels in Arctic marine mammals, the exposure to people living in the Arctic who consume them as part of their diet can also be assessed. Another study involves a retrospective survey of POPs in Arctic seabird eggs. Archived Arctic seabird eggs (thick-billed murre, black-legged kittiwake, northern fulmars) will be analysed for PBDE, in order to determine whether there is a time trend from 1975 to 1998. To cover new persistent chemicals in the Arctic environment, PBDE were analysed during 2001/2002 in composite air samples from the Canadian and the Russian Arctic (Tagish, Alert and Dunai), sampled in 1994 and 1995. NCP research is conducted by federal departments (Indian and Nothern Affairs Canada, Health Canada, Environment Canada, Fisheries and Oceans Canada), the three territorial government departments (Yukon, Northwest territories, Nunavut), northern Aboriginal people’s organisations (Council of Yukon First Nations, Dene Nation, Inuit Tapirisat of Canada, Inuit Circumpolar Conference) and university researchers (Indian and Northern Affairs Canada, 2001). The Marine Environment and Habitat Science Division of Fisheries and Oceans Canada supports two projects, focusing on the impact of PBDE on the Canadian Environment and Health of Canadians as a part of a national program administered by Health Canada. The main objective is the investigation of sources, pathways and fate of

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PBDE, including molecular and aquatic toxicological experiments as a cooperative project between two universities and three governmental departments. In the other project, the trends, sources and amounts of PBDE in sediments from the Strait of Georgia will be investigated. The TSRI mandate came to end in March 2002; however, as a result of this investigation, a number of other studies, albeit on a smaller scale, have been initiated and funded by Northern Contaminants Program and other operating funds which enables the research on BFRs in the Canadian environment to continue. 3.3. Asia In Japan, PBBs are not commercially produced or imported under a voluntary agreement by the manufacturers and importers. Japanese industries have also voluntarily restricted the production and use of hexabromodiphenyl ether and tetrabromodiphenyl ether (Danish EPA, 1999). Only octa-BDE, deca-BDE and TBBPA are currently in use, imported, produced and sold inside and outside of Japan. Only limited data have been found regarding research projects with respect to BFR, which are supported, initiated or financed by the governmental authorities. Japanese governmental objectives have mainly been focussed on the formation, determination and toxicological impact of halogenated dioxins and furans. Reports published in 1989 and 1991 by the Japanese Environment Agency concluded that TBBPA could not be detected in fish sampled in 1987 and 1988 (detection limit of 1 Ag/kg wet weight) (Environment Agency Japan, 1989, 1991).

4. Ecolabels In general, ecolabels can actively contribute to reduce or inhibit the application of undesirable chemicals. They support the development of ecofriendly products and provide consumers with guidance in choosing those products that are the least hazardous to the environment. Currently, there exist a number of national and international ecolabelling systems. Since 1994, numerous electrical and electronic devices have been labelled with the Blue Angel in Germany, indicating the restriction of specified FRs and chemicals potentially forming dioxins and furans (Lassen et al., 1999). The Nordic Council of Ministers introduced the Nordic Swan in 1989, as the official label in Sweden, Denmark, Norway, Iceland and Finland for a voluntary and neutral seal of approval certification program. Electronic products such as computers, TV sets, textiles labelled with the Nordic Swan may not contain BFR in various component parts (Danish EPA, 1999). The EU Flower mark has been active since 1992 within the ecolabelling scheme for the EU. Under this scheme, deca-BB and mono-BDE to deca-BDE compounds are restricted in plastic components of greater than 25 g in

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weight that are used in personal computers, refrigerators, portable computers and televisions. In addition, FR classified as dangerous to the environment according to the Directive 67/548/EEC reference are excluded in the mentioned product groups and in mattresses, textiles and washing machines at contents more than 0.1% (European Community, 1967). TCO is a global environmental labelling scheme initiated by The Swedish Confederation of Professional Employees. The TCO’99 label also requires manufacturers to consider the environmental impact of personal computers and exclude organically bound bromine in parts heavier than 25 g (Danish EPA, 1999). The Austrian Federal Ministry of Agriculture Forestry Environment and Water Management initiated the Austrian ecolabel ‘‘Umweltzeichen’’ in 1991. Restrictions with regard to BFRs are taken into consideration for selected products such as in-duct laid pipeline made of plastic, textiles for office chairs, flexible floorings, and specified insulating boards (Bundesministerium fu¨r Land- und Forstwirtschaft, Umwelt und Wasserwirtschaft, 2000).

5. Conclusion Since the recognition during the 1980s that the production, use and release of PBDEs had resulted in widespread environmental contamination by these compounds, many governments around the world have initiated studies intended to provide more information regarding their significance and to inform the need for regulatory action. The differing rates at which these activities have proceeded have led to a situation where current practices are at variance across the world. In the case of the pentamix PBDE formulation, production and use has ceased within the EU in advance of a proposed ban, while in the USA, it is still extensively used. North America currently accounts for ca. 97% of the manufacture and use of this formulation, although recent data indicating the widespread distribution and accumulation of the BDE congeners in fish and sewage sludge from the USA suggest that regulatory action may be needed in the not too distant future (Hale et al., 2001). The need to provide fire retardant properties for products requires that alternative compounds are substituted for those deemed to present unacceptable environmental risks, and within the EU this has led to increases in the use of HBCD and TBBPA. The development of suitable analytical methods with which to gather data for future risk assessments of these compounds is underway, and study of the environmental distribution and effects of these compounds is now a high priority. As another side of the coin, bromine-free flame retardants (e.g. phosphorus organic compounds) are also being produced and used, and pose an unknown threat to the environment. New analytical methods are needed for these compounds also so as to assess their potential sources and sinks, as well as the extent of any contamination. The

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question once again is whether it will be only after accidental exposure of people to these compounds that investigations and research will be conducted, slowing the introduction of any restrictions that prove necessary, both nationally and internationally.

Acknowledgements Our thanks go to Mehran Alaee from the Aquatic Ecosystem Protection Research Branch National Water Research Institute in Canada contributing with information about Canadian projects. We also want to thank Oliver Hahn, also from BAM, for his efforts in supporting and providing us with data from USA. Special thanks to Daniel Bu¨rgi from Friedli Geotechnik, Zurich, and Georg Karlaganis, Bundesamt fu¨r Umwelt, Wald und Landschaft (BUWAL), for providing us with information with respect to projects and governmental regulations in Switzerland and within the OECD. Robin Law would like to acknowledge funding from the UK Department for Environment, Food and Rural Affairs (DEFRA) within its programme of marine environmental research.

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