OSPAR Priority Substances Series ---------------------------------------------------------------------------------------------------------------------------------
Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane
OSPAR Commission 2001 (2004 Update)
OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane __________________________________________________________________________________________________________
The Convention for the Protection of the Marine Environment of the North-East Atlantic (the “OSPAR Convention”) was opened for signature at the Ministerial Meeting of the former Oslo and Paris Commissions in Paris on 22 September 1992. The Convention entered into force on 25 March 1998. It has been ratified by Belgium, Denmark, Finland, France, Germany, Iceland, Ireland, Luxembourg, Netherlands, Norway, Portugal, Sweden, Switzerland and the United Kingdom and approved by the European Community and Spain.
La Convention pour la protection du milieu marin de l'Atlantique du Nord-Est, dite Convention OSPAR, a été ouverte à la signature à la réunion ministérielle des anciennes Commissions d'Oslo et de Paris, à Paris le 22 septembre 1992. La Convention est entrée en vigueur le 25 mars 1998. La Convention a été ratifiée par l'Allemagne, la Belgique, le Danemark, la Finlande, la France, l’Irlande, l’Islande, le Luxembourg, la Norvège, les Pays-Bas, le Portugal, le Royaume-Uni de Grande Bretagne et d’Irlande du Nord, la Suède et la Suisse et approuvée par la Communauté européenne et l’Espagne.
© OSPAR Commission, 2001. Permission may be granted by the publishers for the report to be wholly or partly reproduced in publications provided that the source of the extract is clearly indicated. © Commission OSPAR, 2001. La reproduction de tout ou partie de ce rapport dans une publication peut être autorisée par l’Editeur, sous réserve que l’origine de l’extrait soit clairement mentionnée. ISBN 0 946956 70 7
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane
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Executive summary Récapitulatif 1
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Identification of sources and pathways to the marine environment 1.1
Brominated flame retardants
1.2
PBDEs production and use
1.3
PBBs production and use
1.4
HBCDD production and use
1.5
Waste and recycling of brominated flame retardants
1.6
Pathways to the marine environment
Monitoring data and quantification of sources 2.1
PBDEs
contents
2.1.1 Monitoring data 2.1.2 Releases 2.1.3 Exposure to pentaBDE 2.1.4 Exposure to octo- and decaBDE 2.2
PBB
2.3
HBCDD 2.3.1 Monitoring data 2.3.2 Releases
2.4
Further considerations
3
Desired reduction
4
Identification of possible measures
5
4.1
Ongoing activities
4.2
Alternatives
Choice for action/measures
References Appendix 1: Monitoring strategy for Certain Brominated Flame Retardants
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane
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Executive Summary Brominated flame retardants are a diverse group of chemicals, whose common points are that they all contain bromine and are all use to retard the combustibility of commercial goods. Two substances – decabromodiphenyl ether (DecaDBE) and Tetrabromobisphenol A (TBBP-A; this will be the subject of a separate Background Document) – account for about 50% of world use of brominated flame retardants. Two other polybrominated diphenyl ethers (PolyBDE) – octabromodiphenyl ether (OctaDBE) and pentabromodiphenyl ether (PentaDBE) – are used commercially, but in much smaller quantities than DecaBDE. Hexabromocyclododecane (HBCDD) is also used in large volumes. Polybrominated biphenyls (PBB) have also been used, but production was stopped in September 2000. Some PolyBDE are toxic, especially those with smaller molecules. PentaDBE may disrupt the oestrogenic system. PBB have similar effects to polychlorinated biphenyls, and may also produce hypothyroidism. Some of these chemicals are bioaccumulated. Brominated flame retardants were given priority in the 1992 OSPAR Action Plan, and therefore included in 1998 in the List of Chemicals for Priority Action. The quantities of PolyB DE used in the EU in 1994 were estimated as: DecaBDE (8 210 tonnes) as a general-purpose flame retardant, especially in polymers, polypropylene fabric and other textiles (other than clothing fabrics); OctaBDE (2 550 tonnes) in acrylonitrile-butadiene-styrene plastics (often used for casings of electrical and electronic equipment), nylon and other plastics and in adhesives and coatings; PentaBDE (125 tonnes) mainly in flexible polyurethane foam for furniture, as well as epoxy and phenolic resins, some polyesters and textiles. About 9 200 tonnes of HBCDD was used in the EU in 1999, 85% of it in polystyrene. Since the products containing these chemicals are widely dispersed, their possible release from waste disposal routes may be of concern, together with their potential role in producing dioxins and furans during waste incineration. The degradation of DecaBDE to the more toxic and bioaccumulative lower levels of PolyBDE is also of concern. The overwhelming majority of samples of marine biota have not shown detectable quantities of DecaBDE; however, OctaBDE has been found in fish and molluscs (up to 325µg/kg wet weight) and PentaBDE has been found in fish and marine mammals (up to 7 700µg/kg in white-beaked dolphins). All these chemicals have been found in river or marine sediments. Action so far has been mainly through voluntary commitments by industry within the framework of the OECD. The risk assessment for PentaBDE under the EC existing substances regulation has concluded that risk reduction measures are needed. The PolyBDEs are proposed to be included as priority hazardous substances in the list of priority substances under the EC Water Framework Directive. The action recommended is: to support the inclusion of PBB in the draft EC Directive on Waste from Electrical and Electronic Equipment; to support early EC harmonised restrictions on PentaBDE; to await the completion of the EC risk assessment of OctaBDE, DecaBDE and HBCDD and seek appropriate riskreduction strategies in the light of it; to support appropriate provision on PolyBDE in the draft EC Directives on Waste from Electric and Electronic Equipment and on Restrictions on Certain Hazardous Substances in Electric and Electronic Equipment; to develop an OSPAR monitoring strategy for these chemicals; to review by OSPAR in 2003 of the need for further OSPAR measures to supplement the eventual EC measures; and to ask other relevant international forums to take account of the background document. A monitoring strategy for Certain Brominated Flame Retardants has been added to this background document.
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane __________________________________________________________________________________________________________
Récapitulatif Les retardateurs de flamme au brome représentent un groupe de produits chimiques diversifié, dont les points communs sont qu’ils contiennent tous du brome et servent tous à retarder la combustion de produits vendus dans le commerce. Deux substances – l’éther décabromodiphénylique (DecaDBE) et le tétrabromobisphénol A (TBBPA – lequel fera l’objet d’un document de fond distinct) – représentent environ 50% de la consommation mondiale de retardateurs de flamme au brome. Deux autres éthers polybromodiphényliques (PolyBDE) – l’éther octabromodiphénylique (OctaDBE) et l’éther pentabromodiphénylique (PentaDBE) – sont utilisés dans le commerce, mais en quantités nettement inférieures au DecaBDE. L’hexabromocyclododécane (HBCDD) est aussi utilisé en gros volumes. Les polybromobiphényls (PBB) ont aussi été utilisés, mais leur fabrication a été arrêtée en septembre 2000. Les PolyBDE sont toxiques, surtout ceux dont les molécules sont petites. Le PentaDBE est susceptible de perturber le système œstrogénique. Les PBB ont des effets analogues à ceux des polychorobiphényls, et peuvent aussi provoquer une hyperthyroïdie. Le HBCDD est aussi toxique. Tous ces produits chimiques ont tendance à s’accumuler biologiquement. La priorité a été donnée aux retardateurs de flamme au brome dans le Plan d’action OSPAR 1992, et ils ont donc été inscrits en 1998 sur la Liste des produits chimiques devant faire l’objet de mesures prioritaires. Les quantités de PolyBDE consommées en 1994 dans l’Union européenne ont été estimées comme suit : DecaBDE (8 210 tonnes), comme agent ignifuge général, surtout dans les polymères, les tissus de polypropylène et autres textiles (autres que les tissus d’habillement) ; OctaBDE (2 550 tonnes) dans les matières plastiques acrylonitrile-butadiène-styrène (dont sont souvent faits les boîtiers dans le matériel électrique et électronique), le nylon et autres matières plastiques ainsi que dans les adhésifs et revêtements ; PentaBDE (125 tonnes) surtout dans la mousse de polyuréthane souple destinée au mobilier, ainsi que dans les résines époxy et les résines phénoliques, certains polyesters et textiles. Environ 9 200 tonnes de HBCDD ont été consommées dans l’Union européenne en 1999, dont 85% dans du polystyrène. Les produits contenant ces produits chimiques étant très répandus, leurs émissions par les voies d’élimination des déchets sont très préoccupantes, ceci parallèlement au fait qu’ils sont susceptibles de produire des dioxines et des furanes pendant l’incinération des déchets. La dégradation du DecaBDE jusqu’aux niveaux inférieurs de PolyBDE, plus toxiques et s’accumulant plus dans les tissus biologiques, est elle aussi préoccupante. Dans la très vaste majorité des cas, l’on n’a pas constaté la présence de DecaBDE en quantités décelables dans les échantillons de biote marin ; toutefois, l’on a observé la présence d’OctaBDE chez le poisson et les mollusques (pouvant atteindre 325 µg /kg du poids à l’état humide) de même que du PentaBDE chez les poissons et dans les mammifères marins (jusqu’à 7 700 µg/kg chez les lagénorhynques à bec blanc. La présence de tous ces produits chimiques a été constatée dans des sédiments fluviaux ou marins. Les mesures prises jusqu’à présent consistent surtout en engagements volontaires de l’industrie, contractés dans le cadre de l’OCDE. Le résultat de l’évaluation des risques suscités par les PentaBDE, effectuée en conséquence du Règlement communautaire européen sur les substances existantes, est qu’il a été conclu que des mesures de réduction des risques s’imposaient. Il est proposé d’inscrire les PolyBDE comme substances prioritaires dangereuses sur la Liste des substances prioritaires dans le contexte de la Directive communautaire européenne cadre relative aux eaux. Les mesures recommandées sont les suivantes : soutien à l’inscription des PBB dans le projet de Directive communautaire européenne relative aux déchets de matériel électrique et électronique ; soutien aux restrictions harmonisées qu’il convient d’imposer rapidement au niveau communautaire aux PentaBDE ; attendre que l’évaluation communautaire des risques suscités par les OctaBDE, les DecaBDE et les HBCDD soit achevée, et à la lumière de ses conclusions, étudier la mise en place de stratégies de réduction des risques ; soutien à une disposition appropriée visant les PolyBDE dans les projets de directives communautaires relatives aux déchets de matériel électrique et électronique ainsi que relatives aux restrictions imposées à certaines substances dangereuses dans le matériel électrique et électronique ; élaboration d’une stratégie OSPAR de surveillance de ces produits chimiques ; en 2003, examen, par OSPAR, de la question de savoir si de nouvelles mesures OSPAR s’imposent pour compléter les mesures
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane _________________________________________________________________________________________________________
communautaires européennes éventuelles ; et demander aux autres instances internationales compétentes de prendre le document de fond en considération. Une stratégie de surveillance sur certains retardateurs de flamme au brome a été ajoutée à ce document de fond.
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane __________________________________________________________________________________________________________
1.
Identification of sources and pathways to the marine environment
1.1
Brominated flame retardants
1. Brominated flame retardants are a chemically diverse group of substances. Brominated flame retardants as a class include aromatic diphenyl ethers, cyclic aliphatics, phenolic derivatives, aliphatics, phthalic anhydride derivatives and others. Their major common points are that they are used to flame retard items in commerce and all contain bromine. Two brominated flame retardants, decabromodiphenyl ether (decaBDE) and tetrabromobisphenol A (TBBP-A), account for approximately 50% of all brominated flame retardants usage globally. The remaining 50% of the global volume of brominated flame retardants is composed of a number of different brominated flame retardant structural types and includes the two other commercial polybrominated diphenyl ether (PBDE) flame retardants: octabromodiphenyl ether (octaBDE) and pentabromodiphenyl ether (pentaBDE). OctaBDE and pentaBDE are produced and used in substantially smaller quantities than decaBDE. Substances that are used in large volumes are polybrominated diphenyl ethers (PBDE), hexabromo cyclododecane (HBCDD) and tetrabromobisphenol A (TBBP-A). The production of polybrominated biphenyls (PBB) ceased in September 2000. This background document covers the first three substances while a separate background document is being prepared by the United Kingdom (UK) for TBBP-A.
1.2
PBDEs production and use
2. The world production of PBDEs has been estimated at 40 000 tonnes in 1992 (including 4 000 tonnes of pentaBDE). The use of PBDEs in the European Union (EU) in 1994 was estimated at 11 000 tonnes. In its risk assessments carried out under Council Regulation (EEC) No 793/93 of 23 March 1993 on the evaluation and control of the risks of existing substances, the UK (Member State Rapporteur) has assumed the following EU quantities for the individual PBDEs: pentaBDE 125 tonnes/year, octaBDE 2 550 tonnes/year, and decaBDE 8 210 tonnes/year. The Bromine Science and Environmental Forum estimated total market demand for major brominated flame retardants for 1999. In Europe the demand was estimated to be: pentaBDE 210 tonnes/year, octaBDE 450 tonnes/year and decaBDE 7 500 tonnes/year. The total demand for PBDEs in the world was estimated to about 67 000 tonnes/year. PBDEs are used in many different applications, which may give rise to diffuse losses of the substances in the “technosphere”, for example in electrical and electronic equipment, furniture, and cars. 3. The major use of pentaBDE is as a flame retardant additive in flexible polyurethane foam for furniture and upholstery. Other reported uses include as a flame retardant additive in epoxy resins, phenolic resins (e.g. in printed circuit boards), unsaturated polyesters and textiles. It is no longer used for textile applications in the EU. 4. Around 95% of the octaBDE supplied in the EU is used as a flame retardant in acrylonitrilebutadiene-styrene (ABS) plastics (often used in covers and casings for electrical or electronic equipment). Other reported uses include nylon and low density polyethylene, polycarbonate, phenol-formaldehyde resins and unsaturated polyesters and in adhesives and coatings. 5. DecaBDE is used as a flame retardant, mostly in applications in the plastics and textile industries. It is a general purpose flame retardant and is thus used in a variety of polymer applications. Industry information indicates that decaBDE is widely used for flame retarding polypropylene drapery and upholstery fabric. DecaBDE may also be used in some synthetic carpets. It is not used as a flame retardant in textiles used for clothing. In the UK it is thought that around 95% of all upholstery materials are flame retarded, and estimated that over 50% of the total PBDE use is in the textile industry. In most other countries the amounts used in this application would be much lower.
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane _________________________________________________________________________________________________________
1.3
PBBs production and use
6. DecaBBs were produced in France until 30 September 2000. The use of PBB will cease when the stock has been consumed. The yearly production was around 1 000 tonnes. PBBs are sold exclusively as technical decaBB, which consists of at least 94% decaBB and up to 6% nonaBB, with traces of octaBB. PBBs are used mainly for electrical and electronic equipment. PBBs are used in many different applications, which may give rise to diffuse losses of the substances.
1.4
HBCDD production and use
7. HBCDD is both manufactured in and imported into the EU. HBCDD is used industrially as an additive flame retardant in polymers. End products containing HBCDD are used both professionally and by consumers. The EU use of HBCDD in 1999 was 9 200-tonnes/year according to the draft Swedish risk assessment. 85% of HBCDD is used in polystyrene (PS). The predominant use of PS is in rigid insulation panels/blocks for building construction; 10% is used in textile back coating and 5% is used in high impact polystyrene (HIPS) in electric housings, e.g. housings for videocassette recorders.
1.5
Waste and recycling of brominated flame retardants
8. The waste stage is a source of at least losses of PBDE and PBB both into the working environment and into the natural environment. Once an article has reached the end of its service life, it can be recycled, incinerated or landfilled. In most countries large quantities of PBDE and PBB occur in plastic parts in electric and electronic equipment. There are various modes of disposal. In the case of goods handled by electronics disposal firms, covers are often burned in incineration plants. There may be a risk of the formation of halogenated dioxins. Printed circuit boards can be sent to metal smelting plants or treated in connection with fragmentation. There are insufficient data to assess the magnitude of the various flows of PBDE and PBB and the resulting releases.
1.6
Pathways to the marine environment
9. A detailed analysis of the specific pathways to the marine environment of the sources mentioned above in paragraphs 1.2 to 1.5 is generally beyond the scope of this background document. Brominated flame retardants reach the marine environment from these sources generally via rivers and via the atmosphere. However, there is a lack of data. It has not been possible to estimate which is the dominant pathway.
2.
Monitoring data and quantification of sources
2.1
PBDEs
2.1.1
Monitoring data
10.
The UK risk assessments contain several monitoring data that are summarised below.
Concentrations in the marine environment PentaBDE 11. No levels of pentaBDE have been reported in water. In Japan, water samples have been analysed for hexaBDE, but it has not been detected in any sample.
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OSPAR Commission, 2001: Certain Brominated Flame Retardants – Polybrominated Diphenylethers, Polybrominated Biphenyls, Hexabromo Cyclododecane __________________________________________________________________________________________________________
12. Components of commercial pentaBDE have been measured in sediments in several EU countries and also in Japan. The results are reported for various isomers of the commercial mixtures. Thus the measured results can be used only to obtain an approximate indication of the levels found in sediment. 13. Levels of commercial pentaBDE of 561-1 271 mg/kg dry weight have been measured in a river and heavily industrialised estuary close to a pentaBDE production site in the UK. The highest levels were found in the heavily industrialised estuary, which may indicate that sources other than the production site contribute to these levels. No production currently occurs in the EU. Higher levels of 1 400 mg/kg dry weight have been measured near to a factory in Sweden. Surficial sediment samples taken from the southern part of the Baltic Sea (Baltic Proper) were found to contain 0,21 to 1,1 mg/kg dry weight as the sum of two congeners. PentaBDE was not detected in samples taken from the northern part of the Baltic Sea (Bothnian Bay). OctaBDE 14.
The levels of octaBDE in water have been analysed in Japan, but it has not been detected.
15. Levels of octaBDE of up to 3 030 mg/kg dry weight (wt) have been detected in sediments in industrialised areas in the UK. The measured levels in other industrialised areas are generally 20-200 mg/kg dry wt. DecaBDE 16. DecaBDE has not been reported in water samples, which is consistent with its low water solubility (
