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SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿O.I. KALANTZI, P.A. SISKOSPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Environmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zografos, Athens, GreecePOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Email: okalantzichem.uoa.grPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿EXTENDED ABSTRACTPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Polybrominated diphenyl ethers (PBDEs) are a class of widely used flame retardants that are incorporated into a wide range of consumer products such as household appliances, plastics, textiles and computers, to prevent fire. They were first introduced in the environment in the 1970s and their concentrations have been increasing ever since. Their persistence in the environment, widespread distribution and bioaccumulation in humans and wildlife has rendered them chemicals of concern. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿The main route of entry of these chemicals into the human body is via the food web, but occupational exposure may also occur in the workplace during handling, repair and dismantling of flame retarded goods. Inhalation of indoor air may also be another important route of entry of PBDEs into humans.POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿PBDEs structural similarities to better known and studied chemicals like PCBs are causes for concern. Individual PBDE congeners have been associated with neurotoxic effects following neonatal exposure in animals and effects on thyroid hormone function. PBDEs have also been associated with non-Hodgkins lymphoma in humans and a variety of cancers in rodents. They do not appear to be genotoxic, however, there are still many toxicity gaps, including their carcinogenic potential and human effects.POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿This paper reviews the sources and exposure of humans to PBDEs, highlighting recent scientific data.POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Key words: polybrominated diphenyl ethers, environmental levels, human exposure sourcesPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿1.INTRODUCTIONPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿In the last century a large number of chemicals were introduced into the environment. Organochlorine pesticides such as 2,2-bis(4-chlorophenyl)-1,1-trichroloethane (DDT), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) have all been widely used at various times from the 1920s onwards. These three classes of compounds all belong to a larger family of chemicals known as persistent organic pollutants (POPs). They have low water solubilities, high lipophilicity and tend to bioaccumulate in fatty tissues and persist in the environment. While concentrations of PCBs and DDT have been decreasing in the environment as a result of their restriction and/or ban, PBDE levels are rapidly increasing.POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿PBDEs are the most widely used additive flame retardants. They are blended with the polymeric material, which makes them more likely to leach out and volatilise into the environment 1. PBDEs are mainly used in polyurethane foams, television sets, computers, radios, textiles, paints and plastics to reduce fire risk. Their mechanism of action is decomposition before the matrix of the polymer following heat application, achieving the prohibition of flammable gas formation 2. PBDEs were first detected in biota in fish from Sweden 3 and their concentrations have been shown to increase in the environment during the 1980s, 90s and 00s 4. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿PBDEs are structurally similar to PCBs and consist of two diphenyl rings joined with an oxygen atom. Like PCBs, there are 209 BDE congeners, produced by brominating diphenyl ether in the presence of a catalyst 5. They have low vapour pressures and water solubility (both inversely proportional to the degree of bromination), high lipophilicity and are persistent in the environment 6. Over the last two decades there have been indications of increased environmental PBDE concentrations, although their levels are still generally lower than those of PCBs 6.POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Exposure to PBDEs gives rise to adverse effects in experimental in vivo models, such as developmental neurotoxicity, altered thyroid hormone homeostasis, foetal toxicity/teratogenicity in rats and rabbits and morphological effects in the thyroid, liver and kidney of adult animals. Little is known about the human effects and toxicokinetics of PBDEs, as well as their carcinogenicity 7. Most toxicological studies however involve the commercial mixtures, rather than individual congeners, which represent human exposure. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿PBDE metabolism studies have concentrated on experimental rodents (rats and mice) and few aquatic organisms (fish, mussels and bacteria). Oxidative metabolism of PBDEs is likely to be taking place, as indicated by the presence of detectable residues of OH-PBDEs in the blood of PBDE exposed wildlife 8. Thyroid hormone-like OH-PBDE congeners have been shown to bind competitively with human transthyretin (TTR), a transport protein for thyroid hormones 9. In rats and fish oxidative debromination of BDE-209 and/or BDE-99 is also occurring 10. Although photolytic debromination has been observed in experimental conditions 11, it is still unknown whether this occurs in the environment. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿2.PRODUCTION AND USEPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿PBDEs were first manufactured and used in the early 1970s. They are typically produced at three different degrees of bromination: penta- (penta-BDE), octa- (octa-BDE) and decabromodiphenyl ether (deca-BDE). Deca-BDE is mainly used in polymers such as polycarbonates, polyester resins, polyolefins, polyvinyl chloride and rubber, octa-BDE in ABS resins and penta-BDE in polyurethane foam and textiles 12. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Commercial penta-BDE consists of 50-62% penta-BDE, 24-38% tetra-BDE and 4-8% hexa-BDE, whereas the commercial octa-BDE consists of 43-44% hepta-BDE, 31-35% octa-BDE, 10-12% hexa-BDE and 9-11% nona-BDE. Commercial deca-BDE is typically composed of 97-98% deca-BDE and 0-1% octa-BDE 13. In terms of individual congeners, more than 70% of penta-BDE is composed of BDEs 47 and 99, with BDEs 28, 100, 153 and 154 contributing smaller amounts 12. BDE-183 is the major congener found in the octa-BDE formulation and deca-BDE consists almost entirely of BDE-209 12.POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Deca-BDE is by far the most widely used PBDE in Europe and the rest of the world. In Asia and the Americas 23,000 tonnes of deca-BDE are consumed annually, whereas in Europe 7,500 tonnes. Octa-BDE and penta-BDE are mostly used in Asia and the Americas, followed by Europe. Asia accounts for 56.2% of global PBDE production, the Americas for 29% and Europe for 15%, 10% of which is consumed in the United Kingdom 14. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿DecaBDE may be the most commonly used PBDE mixture, but it is poorly absorbed and does not bioaccumulate. However, it can be photolytically decomposed to lower brominated congeners, such as BDE-47. The latter is the most commonly occurring congener in the environment and an important constituent of the penta-BDE mixture, mostly used in flame-retarding polyurethane foam in furniture. In the European Union, both penta- and octa-BDE have recently been banned under Directive 76/769 on restrictions of marketing and use 15. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿3.ENVIRONMENTAL LEVELSPOLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿Environmental release of PBDEs may occur at any time during the manufacture, recycling, disposal or incineration of flame-retarded products. Unfortunately, little information is available from the industry on PBDE emissions, so any attempts to quantify releases into the environment are difficult. Since they are not chemically bound to the products they are used in, PBDEs are prone to leaching out and volatilising in the environment. Once released, they can be transported by air to such remote and far away from point sources regions like the Arctic and the Antarctic 16, 17. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿The environmental distribution and partitioning of PBDEs varies according to their individual physicochemical properties. More brominated and heavier congeners such as BDE-209 tend to stay in soil, sediments and sewage sludge, whereas the lighter and less brominated congeners such as BDE-47 are deposited in plants and re-volatilise and can bioaccumulate up the foodchain. Congener composition varies in different matrices. In biota BDEs 47, 99, 100, 153 and 154 usually make up about 75% of the total PBDE levels, whereas in air and sediments BDE-209 is the predominant congener. The higher up the foodchain, the larger the % certain congeners make up in an organism due to biomagnification. POLYBROMINATED DIPHENYL ETHERS IN HUMANSSOURCES AND EXPOSUREPOLYBROMINATED DIPHENYL ETHERS IN HUMANS SOURCES AND EXPOSUREO.I. KALANTZI, P.A. SISKOSEnvironmental Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimioupoli, 157 71 Zog匪箭烷荣辨夷荷伶褐狗宜纹豌氟泰次妥发儒跌拱汝刃固蜜登宽午述海七扎膳舌谷从两邹瑶隙面篓帚橱兴姐毛咀哼抖艺龚馁专学脏耽棚割左煎殃睬簿PBDEs were first detected in sewage sludge

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