REVIEWS ON ENVIRONMENTAL HEALTH VOLUME 25, No. 4, 2010

Halogenated Flame Retardants: Do the Benefits Justify the Risks?

Susan D. Shaw,1 Arlene Blum,2 Roland Weber,3'4 Kurunthachalam Kannan,5 David Rich,6 Donald Lucas,7 Catherine P. Koshland,8 Dina Dobraca,9 Sarah Hanson10 and Linda S. Birnbaum"

'Marine Environmental Research Institute, Center for Marine Studies, Blue Hill, ME 04614 USA; 2Dept of Chemistry, University of , Berkeley, CA 94720 USA;3MTM Research Center, Örebro University, SE 701 82 Örebro, Sweden; 4POPs Environmental Consulting, D-73035, Goeppingen, Germany; 3Wadsworth Center, New York State Dept of Health, and Dept of Environmental Health Sciences, School of Public Health, State University of New York at Albany, NY 12201-0509 USA; 6Combustion and Fire Processes Laboratory, University of California; 7Lawrence Berkeley National Laboratory, Berkeley, CA 94720 USA;HEnvironmental Health Science, School of Public Health, University of California, Berkeley, CA 94720, USA; 9 Council of State and Territorial Epidemiologists, Atlanta, GA 30341, USA; l0Green Science Policy Institute, Berkeley, CA, 94708, USA; "National Cancer Institute, National Institutes of Health, Department of Health and Human Services, Research Triangle Park, NC 27709 USA

Abstract: Since the 1970s, an increasing number of regulations have expanded the use of brominated and chlorinated flame retardants. Many of these chemicals are now recognized as global contaminants and are associated with adverse health effects in animals and humans, including endocrine and disruption, immunotoxicity, reproductive toxicity, cancer, and adverse effects on fetal and child development and neurologic function. Some flame retardants such as polybrominated diphenyl ethers (PBDEs) have been banned or voluntarily phased out by manufacturers because of their environmental persistence and toxicity, only to be replaced by other organohalogens of unknown toxicity. Despite restrictions on further production in some countries, consumer products previously treated with banned retardants are still in use and continue to release toxic chemicals into the environment, and the worldwide use of organohalogen retardants continues to increase. This paper examines major uses and known toxic effects of commonly-used organohalogen flame retardants, replacements for those that have been phased out, their by-products, and their effectiveness at reducing fire hazard. Policy and other solutions to maintain fire safety while reducing toxicity are suggested. The major conclusions are: (1) Flammability regulations can cause greater adverse environmental and health impacts than fire safety benefits. (2) The current options for end-of-life disposal of products treated with organohalogens retardants are problematic. (3) Life-cycle analyses evaluating benefits and risks should consider the health and environmental effects of the chemicals, as well as their fire safety impacts. (4) Most fire deaths and most fire injuries result from inhaling monoxide, irritant gases, and soot. The incorporation of organohalogens can increase the yield of these toxic by-products during combustion. (5) Fire-safe cigarettes, fire-safe candles, child-resistant lighters, sprinklers, and detectors can prevent fires without the potential adverse effects of flame retardant chemicals. (6) Alternatives to organohalogen flame retardant chemicals include using less flammable materials, design changes, and safer chemicals. To date, before evaluating their health and environmental impacts, many flame retardant chemicals have been produced and used, resulting in high levels of human exposure. As a growing literature continues to find adverse impacts from such chemicals, a more systematic approach to their regulation is needed. Before implementing new flammability standards, decision-makers should evaluate the potential fire safety benefit versus the health and environmental impacts of the chemicals, materials, or technologies likely to be used to meet the standard. Reducing the use of toxic or untested flame retardant chemicals in consumer products can protect human and animal health and the global environment without compromising fire safety.

©2010 Freund Publishing House, Limited. 261

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Keywords: Brominated flame retardants, chlorinated flame retardants, pentaBDE, octaBDE, decaBDE, PBDE, HBCD, TBBPA, PBDD/F, TDCPP, chlorinated Tris, brominated Tris, chlorinated paraffins, flammability standards, flame retardant regulations, fire safety, fire toxicity, replacement flame retardants, Technical Bulletin 117

Correspondence: Susan Shaw, Marine Environmental Research Institute, Center for Marine Studies, Blue Hill, ME 04614 USA; e-mail: [email protected]

Table of Contents 6.1 California Home Furniture Standards: 1. Introduction Technical Bulletins 117 and 116 2. Major Uses, Regulatory Restrictions, and 6.2 California Technical Bulletin 133 (TB133) for Replacement Flame Retardants Public Occupancies 2.1 Major Uses 6.3 CPSC Staff Furniture Standard 2.2 Regulatory Restrictions and Replacement 6.4 CPSC Mattress Standard 16 CFR 1633 Flam«; Retardant Chemicals 6.5 Standards for Electronics Enclosures 3. Health Effects of Halogenated Flame Retardants 6.6 Building/Insulation Flammability Standards in Animals and Humans 6.7 Motor Vehicle Standards 3.1 Polybrominated Diphenyl Ethers (PBDEs) 7. Fire Safety Benefits of Halogenated Flame 3.1.1. Laboratory Animals Retardants in Consumer Products 3.1.2 Humans 7.1 Home Furniture (Technical Bulletin 117) 3.1.3 Wildlife: Fish, Birds, Marine Mammals 7.2 Standards for Electronic Enclosures 3.2 (TBBPA) 7.3 Building/Insulation Flammability Standards 3.3 Hexabromocyclododecane (HBCD) 7.4 Effect of Halogenated Flame Retardants on 3.4 Short-Chain Chlorinated Paraffins (SCCPs) Fire Effluent Toxicity 3.5 PentaBDE Replacements: Firemaster 550 8. Safer Alternatives to Chemical Flame Components and Chlorinated Tris (TDCPP) Retardants 4. Brominated Flame Retardants Unintentionally 8.1 Fire-Safe Cigarettes Produce Brominated Dioxins and Furans 8.2 Fire-Safe Candles 4.1 Environmental, Food, and Human 8.3 Alternate Designs and Materials Contamination 8.4 Safer Replacement Chemical Flame Retardants 4.2 Toxicity of Brominated Dioxins and Furans 9. Discussion: Policy Implications and Suggestions 4.3 Formation and Release of Brominated Dioxins 9.1 Reevaluating California TBI 17 to Maintain and Furans During the Life Cycle of Brominated Fire Safety While Reducing the Use of Flame Retardants Halogenated Flame Retardants 5. End-of-Life Considerations for Halogenated 9.2 Reconsideration of Small Open Flame Flame Retarded Materials Requirements for TV Sets in the EU and US 5.1 Recycling of Brominated Flame Retarded 9.3 Production of Two Kinds of , Materials With and Without Added HBCD 5.2 Combustion of Materials Containing 9.4 Life Cycle Analysis before Using Flame Halogenated Flame Retardants Retardants 5.3 Landfilling and Release of Halogenated 9.5 Reducing Exposure, Legacy Problems, and Flame Retardants from Landfills Product End-Of-Life for Flame Retardants 6. Flammability Standards and Their 9.6 Chemical Regulation Implementation 10. Conclusions

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Fig. 1: Chemicals structures of brominated flame retardants PBDEs, HBCD, and TBBPA, and related halogenated chemicals including the polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), and brominated/chlorinated dioxins and furans

1. INTRODUCTION or fully understood. Furthermore, when selecting flame retardant materials, the primary criteria of Since the 1970s, an increasing number of the manufacturer are cost and . regulations have rapidly expanded the global usage The five brominated flame retardants (BFRs) of brominated and chlorinated flame retardants. that have been used most extensively are tetra- Manufacturers add halogenated organic chemicals bromobisphenol A (TBBPA), hexabromocyclo- to a wide range of products to increase their flame dodecane (HBCD), and three commercial mixtures ignition resistance III. Brominated and chlorinated of polybrominated diphenyl ethers (PBDEs)— chemicals are the least expensive way to meet (decaBDE), octabromo- flammability requirements. When the regulations diphenyl ether (octaBDE), and pentabromo- leading to their use were implemented, the diphenyl ether (pentaBDE) (Figure 1). Although potential adverse health and environmental impacts penta and octaBDE have been withdrawn from the of flame retardant chemicals were not recognized market and decaBDE is being phased out, the

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Dechlorane plus (anti) C12-chlorinated paraffin

Fig 2: Chemical structures of chlorinated flame retardants in current use: TDCPP, [tris(l,3-dichloro-2-propyi) phosphate] also called TDCP or chlorinated Tris; TCEP or tris(2-chloroethyl) phosphate; TCPP or tris(l-chloro-2-propyl) phosphate, Dechlorane Plus, and chlorinated paraffins overall production of halogenated flame retardants million pounds of TDCPP were produced in 2006 (HFRs) continues to rise rapidly /2,3/. Between in the U.S. The total chlorinated paraffin use in the 2001 and 2008, the volume of BFRs produced U.S. is approximately 150 million pounds per year, worldwide doubled from approximately 200,000 to divided among short chain (33 million pounds), 410,000 metric tons (mt) annually and between medium chain (67 million pounds), and long chain 2005 and 2008 CFRs increased from 82,000 to (50 million pounds) 111. In China the manufacture 190,000 mt 12,31. In Asia, BFR output nearly of chlorinated paraffins as flame retardants and for doubled during 2005-2008, increasing from other uses is growing exponentially /8/. 139,000 to 246,000 mt and CFRs increased more Halogenated flame retardants enter the than fivefold from 10,000 to 53,000 mt /3/. environment through multiple pathways, such as The chlorinated flame retardants in current use emission during manufacturing, from products in in the United States (U.S.) include TDCPP, use, and combustion, leaching from landfills, or [tris(l,3-dichloro-2-propyl) phosphate] also called recycling at the end of the product's life. Since TDCP or chlorinated Tris; TCEP or tris(2- their introduction, HFRs have become widespread chloroethyl) phosphate; TCPP or tris(l-chloro-2- global contaminants and have been detected propyl) phosphate, Dechlorane Plus, and chlorinated throughout the world in air, , soil, sediment, paraffins /4-6/ (Figure 2). The Chemical Substance sludge, dust, bivalves, crustaceans, fish, Inventory 111 reports that between 10 and 50 amphibians, reptiles, birds, mammals, and human

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM HALOGENATED FIRE RETARDANTS: RISKS VS BENEFITS 265 tissues /9-15/. The contamination patterns world- implementation, fire safety impacts, safer alter- wide reflect the consumption patterns of various natives, and policy implications of continued use. countries and regions. For example, North America has used 95% or more of the pentaBDE produced globally /16/, and pentaBDE levels in the North 2. MAJOR USES, REGULATORY American general population and biota are the RESTRICTIONS AND REPLACEMENT highest in the world /9,13/. FLAME RETARDANTS Exposure to HFRs is associated with a wide range of adverse effects in animals and humans, 2.1 Major Uses including endocrine disruption, immunotoxicity, reproductive toxicity, effects on fetal/child The major uses of halogenated flame retardant development, thyroid and neurologic function, and chemicals in North America are in (1) electronics, cancer/9,17-20/. (2) building materials, including insulation, At the end of life, hazardous flame retardants (3) transportation, and (4) home furnishings are often exported to developing countries and /1,9,17/. The chemicals are commonly used at countries in transition such as China in electronic levels up to 5% of the weight of foam waste (e-waste), second-hand electronics, and used in furniture and baby products and 20% or more of cars. Ε-waste is frequently recycled with primitive the weight of the of electronic housings technologies such as open burning, resulting in /27/. The highest-volume flame retardant world- severe human and environmental contamination by wide, TBBPA, is used mainly as a reactive flame PBDEs, other halogenated flame retardants, as well retardant in electronics, including printed circuit as their combustion products /21-24/. boards and several types of polymers 121. HBCD is are also exposed to such combustion products, an additive flame retardant used in polystyrene especially during cleanup after fires. Studies show foam insulation in buildings and to a lesser extent elevated rates of cancers that are thought to be in upholstery, textile coatings, cable, latex binders, related to dioxin exposure among firefighters and electrical equipment l\l. Chlorinated paraffins /25,26/. are widely used as secondary plasticizers and flame After 30 years of widespread use, several retardants in , primarily HFRs have been banned or phased out because of (PVC) 111. Other minor uses are as a plasticizer and their environmental persistence and toxicity, only flame retardant additive to rubber formulations, to be replaced by chemicals of similar structure paints and other coatings, and adhesives and and unknown toxicity /9,18/. Despite restrictions, sealants /28/. flame-retarded consumer and household products PentaBDE was added primarily to poly- will remain a reservoir for release into the urethane foams in furniture, baby products, and environment for years to come, and some automobile and aircraft interiors /1,17/. The main formulations, such as HBCD, TBBPA, and TDCP, use of octaBDE was in a variety of thermoplastic are still in high-volume global production and use. resins, in particular ABS (acrylonitrile-butadiene- In this paper we review the major uses of styrene) plastic, which can contain up to 12% by halogenated flame retardants, their regulatory weight octa-BDE 1291. DecaBDE, the most restrictions and chemical replacements, toxic widely used PBDE in all markets 121, is added to effects related to human and animal exposure, various plastic polymers such as polyvinyl hazards of toxic degradation products, end of life chloride, polycarbonates, and high-impact poly- considerations, flammability standards and their styrene, as well as back coating for textiles

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(commercial furniture, automobile fabrics, and in Europe in 2004, and withdrawn from carpets) l\l. Because of their high-volume use in commerce in the U.S. in 2004 /35/. In May 2009, consumer products over decades, PBDEs are the principle congeners of the commercial unique among toxic chemicals in that they can be products penta- and octaBDE were added to the found at pound levels in homes, public places, Stockholm Convention list of persistent organic and transportation. pollutants (POPs) /36/. These environmentally persistent, bioaccumulative, and toxic chemical 2.2 Regulatory Restrictions and Replacement mixtures are now banned from production. Flame Retardant Chemicals Furthermore, any remaining stockpiles must be eliminated or be subject to environmentally sound Because of their environmental persistence and management. toxicity, many HFRs have been banned or DecaBDE, the third commercial PBDE, can voluntarily phased out /9,17/. Manufacturers, break down into less brominated by-products that however, often replace a banned chemical with are more bioaccumulative and toxic /16,37-40/. another one having similar characteristics. For DecaBDE was banned in Sweden in 2007, example, in 1977 the U.S. Consumer Product followed by partial bans in four U.S. states Safety Commission (CPSC) banned brominated (, Maine, Oregon, and Vermont), the Tris or Tris-BP/tris (2,3-dibromopropyl) European Union (2008), and Canada (2009). In phosphate/ from children's sleepwear after the December 2009, the U.S. Environmental chemical was found to be a mutagen /30/. Protection Agency (EPA) announced a negotiated Brominated tris was also found to be absorbed into three-year phase-out of this flame retardant in children's bodies /31 /. The main replacement for U.S. consumer products by three major global brominated Tris was chlorinated Tris or TDCPP. producers /41/. After being found to be a mutagen as well /32/, Despite these restrictions, large amounts of chlorinated Tris was voluntarily removed from use upholstered furniture, juvenile products, and in sleepwear in 1978. Both compounds are also plastics containing PBDEs are still in use and probable human carcinogens /33,34/. Nevertheless, must be disposed of after their lifetimes, creating chlorinated Tris or TDCPP is currently used to outdoor reservoirs (e.g., landfills, wastewater meet California Technical Bulletin 117 (TBI 17), a treatment plants, recycling unique California flammability standard that facilities, or stockpiles of hazardous wastes) for requires polyurethane foam in furniture and the future dispersal of PBDEs to the environment. juvenile products to withstand exposure to a small Moreover, large volumes of these materials are in open flame for 12 seconds. the global recycling flow (e.g., plastic from waste Previously, from the 1980s until 2004, electronics or polyurethane foam recycled to pentaBDE was primarily used in furniture and carpet padding) and will continue to be used in juvenile product foam to meet the California consumer products for a considerable time. standard TBI 17, as well as in transportation. Major replacement chemicals for pentaBDE PentaBDE and other PBDEs are structurally commercial mixtures in furniture and juvenile similar to known human toxicants including poly- products (nursing pillows, baby carriers, high brominated biphenyls (PBBs), polychlorinated chairs) include Firemaster 550®, Firemaster 600® biphenyis (PCBs), dioxins, and furans (Figure 1). and TDCPP /4,42/. Firemaster 550®, contains: Because of environmental and public health (l)triphenyl phosphate (TPP); (2) triaryl phos- concerns, the penta- and octaBDE commercial phate isopropylated; (3) 2-ethylhexyl-2,3,4,5- formulations were banned in California in 2003, tetrabromobenzoate (TBB); and (4) Bis (2-ethyl

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM HALOGENATED FIRE RETARDANTS: RISKS VS BENEFITS 267 hexyl) tetrabromophthalate (TBPH) /43/. Two or higher than those of BDE-209 and appear to be Firemaster 550® components, TBB and TBPH, increasing after a comparatively short period of have been detected in from usage /54/, suggesting that DBDPE may be more wastewater treatment plants that discharge persistent and/or bioaccumulative than decaBDE. effluent into San Francisco Bay, California /44/, High concentrations of DBDPE have also been as well as in the blubber of dolphins and reported in captive pandas 1511 and waterbirds porpoises near flame retardant production /58/ from China's Pearl River Delta, where many facilities in south China /45/. Recent studies show e-waste recycling facilities are located. that chlorinated Tris and Firemaster 550® Another alternative to decaBDE in plastic components, as well as PBDEs, can migrate from enclosures is HBCD 1591. In recent years, the foam products into indoor house dust /42/. These global demand for HBCDs has increased in semi-volatile compounds can form thin films on Europe and Asia, and temporal studies show that walls and windows /46/. The inhalation and the levels of the most persistent stereoisomer, a- ingestion of contaminated dust has been shown to HBCD, are increasing in biota and humans be a major route of human exposure, especially /10,13,15,60/. HBCD is presently banned in for children /42,47-49/. Norway and was cited by the European Union A commonly used chlorinated flame retardant (EU) as one of the chemicals for priority action in the U.S. is chlorinated Tris or TDCPP, a /61/. In addition, the Stockholm Convention and pentaBDE replacement that was recently found in regulators in Canada, Australia, and Japan are furniture and juvenile product foam, as well as in evaluating its hazards /8/. dust at similar levels to those of pentaBDE /42/. TBBPA, the highest volume flame retardant Other chlorinated phosphate flame retardants in worldwide, is primarily a reactive BFR (90%) use include TCEP or tris(2-chloro-ethyl) covalently bound to the polymer structure and phosphate, which has been identified as a less likely to be released into the environment carcinogen by the World Health Organization /50/ than are additive flame retardants. TBBPA is of and listed under Proposition 65 by the State of high ecotoxicologic concern because of its acute California /51/, and TCPP or tris(l-chloro-2- and chronic toxicity in several biota /62/. TBBPA, propyl) phosphate, a common replacement for however, can be rapidly metabolized by TCEP in the EU. TCPP is over 200 times more mammalian liver and eliminated in bile, urine and volatile than TDCP or pentaBDE, and TCEP is 200 feces /63,64/ and therefore has a lower potential times more volatile than TCPP, making TCEP the for bioaccumulation. Nevertheless, TBBPA has most volatile of the three commonly used been detected in various environmental media and chlorinated phosphate flame retardants /52,53/. The biota including air, soils, water, sediment, and volatility data suggest that the exposure risk is bird muscle from e-waste regions of China highest from TCEP, followed by TCPP. /65,66/; in water and sediment from English lakes Replacements for the octaBDE and decaBDE /67/ and in bottlenose dolphins and bull sharks mixtures include l,2-Bis(2,4,6-tribromophenoxy) from the Florida Coast /13/. TBBPA can serve as ethane (BTBPE; trade named FF-680) and deca- a source of environmental (BPA), a bromodiphenylethane (DBDPE). Both BTBPE compound of increasing concern that has been and DBDPE have been reported in air, water, shown to break down in marine sediments /68,69/. Currently, no restrictions are placed on sewage sludge, sediment, mussels, fish, and the production and use of TBBPA. birds/14,54-56/, and in house dust from the U.S. /43/. Current concentrations of DBDPE in eggs of Chlorinated paraffins are commonly used as herring gulls from the Great Lakes are similar to flame retardants in plastics. Other minor uses are

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 268 S. SHAW ET AL. as flame retardants in rubber formulations, paints 3.1 Polybrominated Diphenyl Ethers (PBDEs) and coatings, and adhesives and sealants /28/. Short-chain chlorinated paraffins (SCCPs), which 3.1.1. Laboratory Animals. Experimental data have 10 to 13 , are persistent, bio- (both in vivo and in vitro) show that PBDEs have accumulative, and toxic to aquatic organisms at the potential to disrupt the endocrine system at low concentrations 11,101. SCCPs have been multiple target sites in amphibians, birds, fish, measured in air, sediment, surface , and mice, and rats, resulting in effects on thyroid, wastewater /70,71/, as well as in freshwater ovarian, and function /17,18,78,79/. aquatic species, marine mammals, and avian and Like other BFRs, one of the primary toxic effects terrestrial wildlife. In addition, SCCPs have been of PBDEs is thought to be disruption of thyroid detected in human breast milk from Canada and hormone homeostasis, and several mechanisms the United Kingdom, and in food from Japan and have been proposed—interference in the transport Europe /70/. Currently, the EPA is planning to of T4 via competitive binding to thyroid transport ban or restrict the manufacture, import, proteins (TTR) and thyroid hormone receptors; processing, or distribution of SCCPs 111. A global induction of thyroid hormone metabolic activity; ban on SCCPs is being considered under the and/or interference with the hypothalamus- Stockholm Convention /70/. pituitary-thyroid axis /80/. The disruption of The chlorinated flame retardant, Dechlorane thyroid homeostasis during development is of Plus, used in electrical wires, cable coatings, hard special concern because small changes in connectors in computers and plastic roofing maternal and fetal thyroid homeostasis cause materials, is a replacement for the flame retardant neurologic impairments, including decreases in Dechlorane, which is identical to the banned the IQ of offspring/17,18/. pesticide Mirex 1121. Dechlorane Plus has been Like other BFRs, many of the adverse health widely detected in sediment and biota in the Great effects of PBDEs result from developmental Lakes /72-74/ and has been measured in house- exposure /9,17,18/. In rodent models, the toxic hold dust 115,16/ raising concern about human effects following prenatal or neonatal exposure exposure. Considered a high production volume include effects on liver enzymes /81,82/, (HPV) compound in the U.S, Dechlorane Plus is endocrine disruption (altered thyroid hormone currently unregulated and therefore is subject to levels) /83/, reproductive damage /84-86/ the U.S. EPA's HPV challenge. Dechlorane Plus immunotoxicity /87,88/, and neurotoxic effects is included among Canada's 50 top priority /89,90/. Experiments conducted by Eriksson and compounds of environmental concern 1111. co-workers in mice developmentally exposed either to penta- or higher BDEs /89-95/ and in rats exposed to BDE-209 1961 during the period of 3. HE ALTH EFFECTS OF HALOGENATED rapid brain growth have shown neurotoxic effects, FLAME RETARDANTS IN ANIMALS AND including an impairment of spontaneous behavior, HUMANS cholinergic transmitter susceptibility, and habitu- ation capability. The deficits in learning and Exposure to HFRs has been associated with memory persisted into adulthood and worsened and/or causally related to numerous health effects with age. Rice et al. 1911 reported that neonatal in animals and humans, including endocrine exposure to decaBDE produces effects on disruption, immunotoxicity, reproductive toxicity, behavioral performance in aging but not in effects on fetal/child development, and cancer younger mice, possibly as a result of increased impulsivity in older animals. An earlier study in 79,17,18/.

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neonatal mice 798/ found that decaBDE exposure than in rodents: a significant reduction of T3 was resulted in developmental delays, changes in observed in all male and female mink, despite a spontaneous locomotor activity, and a dose- compensatory increase of T4 in females /107/. related reduction in serum T4 concentrations. The Developmental immunotoxicity (increased splenic results of that study suggest that the neuro- germinal center development and inci-dence of B- developmental effects of PBDEs might be related cell hyperplasia) was observed in ranch mink to perturbations in thyroid hormone homeostasis exposed to a high dose (10 μg g"1) of DE-71 in the in the neonate. In male rats, hepatocellular diet /88,107/. Significant body weight reductions degeneration is a high-dose effect of decaBDE were found in mink fed 5 and 10 μg PBDE g"1 exposure 1991. The developmental effects of /88/. The exposure doses of 5 and 10 μg PBDE g"1 PBDEs are exacerbated by co-exposure to PCBs diet for 8 weeks affected several immunologic in rats /i 00/. endpoints, including lymphocyte counts, in mink As endocrine disruptors of adipocyte /88/. Dietary exposure of mink to PBDEs resulted metabolism, PBDEs can predispose animals to in accumulation in the brain, demonstrating that obesity /101 /. Exposure to pentaBDE results in PBDEs can cross the blood-brain barrier/107/. increased lipolysis and reduced insulin-stimulated 3.1.2 Humans. Human internal and external metabolism in rat adipocytes—the hallmark exposure to PBDEs has been recently reviewed features of obesity, insulin resistance, and type 2 /9,47,108/. About 20% of exposure to PBDEs in diabetes. Certain PBDEs are also potent anti- Americans is estimated to derive from the diet, /102,103/, which may explain delays in with the highest levels found in butter, seafood, puberty and effects on gonads. and meat /109/. The remaining 80% of exposure DecaBDE is the only PBDE that has been is assumed to derive from the ingestion/inhalation tested for carcinogenicity. In two-year studies in of PBDE-contaminated dust /48/. The PBDE rats and mice, decaBDE exposure caused liver concentrations in the North American general and thyroid tumors /104/. The National population—mean -30-40 ng g~' lipid weight (lw) Toxicology Program is currently conducting two- in serum—are 10 to 40-times higher than the year studies on DE-71, a commercial pentaBDE concentrations reported for populations in Europe mixture /105/. and other parts of the world /9,12,48,110-113/. 1 Dosing studies using captive mink (Mustela The highest concentration of PBDEs (9630 ng g" vison) indicate that mink are more sensitive than lw) in human adipose tissue was reported in a rodents to the reproductive, endocrine-disrupting, sample collected from New York /110/ In the and developmental effects of PBDEs /106/. The U.S., infants are exposed at higher levels than effects of environmentally relevant doses of DE-71 adults through the ingestion of breast milk and by on mink reproductive performance and the the ingestion of dust due to their frequent hand-to- development of offspring exposed perinatally and mouth contact /114,115/. A significant positive post-weaning were recently investigated /107/. correlation between PBDE concentrations in Dietary PBDE concentrations that caused no house dust and breast milk has been shown /49/. effects on reproduction in rodents (2.5^g g"1 DE- In California, populations have been shown to be 71) resulted in complete reproductive failure in disproportionately exposed to PBDEs, likely due mink. Developmental effects in offspring were to the state's unique fire regulation TBI 17 that evident in 33-week-old juveniles, which were more has led to high usage of HFRs in furniture, sensitive to the effects than their respective dams. mattresses, sleepwear, and baby products. In Juvenile thyroid hormone homeostasis was also California, breast milk, serum, and house dust much more sensitive to PBDE exposure in mink samples contain high concentrations of PBDEs

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/76,116,117/. Serum PBDE levels in children are such as premature delivery, low birth weight, and 2.5 times higher than those in similar-aged stillbirth among the infants of pregnant women children across the U.S., 2-10 times higher than in involved in e-waste recycling in Guiyu, China. U.S. adults, and 10-100 times higher than in Whereas most human tissues showed a pentaBDE similar aged children in Europe and Mexico /118/. 'signature' dominated by tetra-BDE-47, BDE-209 Numerous adverse effects have been dominated the PBDE congener profiles in the associated with human exposure to PBDEs, Guiyu women. An earlier study reported that including endocrine disruption, reproductive elevated levels of PBDEs in breast milk of effects, diabetes, and effects on fetal/child pregnant Taiwanese women were significantly somatic and neurodevelopment /9,17,119,120/. associated with adverse birth outcomes including Increasing evidence suggests that PBDE exposure weight, length, and chest circumference of their adversely affects the developing nervous system infants /124/. In both studies, the effects were in children. In a recent study, exposure to observed at levels lower than the average PBDE pentaBDEs in umbilical cord blood was levels in the adult U.S. population. associated with substantial neurodevelopmental In a study of mother-son pairs from Denmark deficits 1201. Children in the highest 20% of the and Finland, elevated PBDE levels in breast milk exposure distribution showed lower IQ perfor- correlated with cryptorchidism (undescended mance scores (ranging from 5 to 8 points lower) testicles) in the boys /125/. The PBDE levels at ages 1, 2, 3, 4, and 6. In Dutch children, associated with cryptorchidism were also prenatal exposure to pentaBDE and HBCDs was positively correlated with serum luteinizing associated with significant adverse effects on hormone (LH) concentrations in the infants, motor, cognitive, and behavioral outcomes /121/. which suggested a possible compensatory PentaBDE congeners appear to profoundly affect mechanism to achieve normal testosterone levels the development of fetal human neural progenitor and is consistent with the anti-androgenic effects cells via the endocrine disruption of cellular of PBDEs observed in experimental animals. A thyroid hormone signaling /122/. These studies pilot study conducted by Japanese researchers are the first to provide biological plausibility for reported that elevated blood levels of BDE-153 in vivo studies reporting behavioral and IQ correlated with decreased sperm count and deficits following developmental exposures. decreased testes size /126/. Adverse human reproductive/developmental The importance of house dust as a major outcomes related to PBDE exposure have been exposure route for PBDEs in humans has been recently reported. Harley et al. /19/ reported an highlighted /47,48,113/, and a recent study in the association between PBDE exposure and reduced U.S. reported a relationship between altered fertility in women from a predominantly hormone levels in men and PBDE levels in house Mexican-immigrant community in California. dust /127/. The findings included significant Increasing serum levels of pentaBDE were inverse associations between PBDEs in house significantly associated with longer time to dust and serum concentrations of the free . Prenatal PBDE exposure of the infants androgen index, LH, and follicle-stimulating of these women was associated with low birth hormone (FSH) and positive associations between weight, altered cognitive behavior, and PBDEs and sex-hormone binding globulin significantly reduced plasma levels of TSH /120/. (SHBG) and free T4. A study by Wu et al. /123/ reported that elevated Significant relationships between PBDEs and PBDE concentrations in umbilical cord blood elevated thyroid hormone levels have been were associated with adverse birth outcomes, reported in other human studies. Turyk et al. 7128/

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM HALOGENATED FIRE RET ARD ANTS: RISKS VS BENEFITS 271 reported an association between PBDEs and subgroups of NHL. The incidence of thyroid elevated T4 levels and thyroglobulin antibodies in cancer has been increasing in the U.S. during the the blood of adult male consumers of Great Lakes past several decades, especially among women sport fish. The effects were observed at PBDE and in newborn babies (congenital hypo- levels comparable to those found in the general thyroidism), and part of the observed increase in U.S. population and were independent of PCB thyroid cancer rates is hypothesized to be related exposure and sport fish consumption. A recent to the increasing population exposure to PBDEs study of Inuit adults /129/ reported that plasma and other thyroid hormone disrupting compounds concentrations of BDE-47 were related to /80,115/.

increasing total T3 levels. Yuan et al. /130/ found 3.1.3. Wildlife. In North America, PBDE an association between serum levels of PBDEs levels in wildlife are the highest in the world and and elevated TSH in persons living near or are increasing /9,12,132-135/. In some areas, working at an electronic waste dismantling site in PBDEs are rivaling PCBs and organochlorine southeast China. Elevated TSH levels may be a pesticides as the top contaminant in tissue /16/. compensation for the reduction of circulating Although the threshold levels for PBDE-related and are also indicative of stress effects in wildlife are not understood, PBDE on the thyroid system. exposure at environmentally relevant levels has As endocrine-disruptors, some PBDEs are been associated with an array of adverse effects in reported to cause disturbances in glucose and numerous species 191. lipid metabolism in adipose tissue of Sprague- 3.1.3.1. Fish. In fish, PBDE exposure may Dawley rats, which is characteristic of metabolic affect thyroid hormone homeostasis, sperm obesity and type-2 diabetes /101 /, but few studies production, disease resistance, and neuro- have examined the relationships between PBDEs development 19,136-138/. In juvenile lake trout and diabetes in humans. Turyk et al. /128/ {Salvelinus namaycush) exposed to 13 PBDE reported a non-significant association between congeners at environmentally relevant levels, PBDE exposure and diabetes in Great Lakes sport plasma Tt levels were significantly reduced /13 8/. fish consumers with hypothyroid disease. A In male fathead minnows (Pimephales promelas), recent study in U.S. adults examined the repeated oral exposure to BDE-47 reduced sperm association between diabetes and PBDEs /119/. production /139/. Low-dose embryonic exposure of Serum concentrations of the hexaBDE congener- killifish (Fundulus heteroclitis) to a pentaBDE 153 were significantly related to metabolic mixture resulted in neurobehavioral effects and a obesity syndrome and diabetes prevalence at subtle developmental asymmetry of tail curvature background concentrations, suggesting that direction, with a J-shaped dose-response curve PBDEs may contribute to diabetes in the general suggestive of thyroid hormone disruption /140/. population. Similarly, exposure of zebrafish (Danio rerio) The carcinogenicity of PBDEs has not been embryos to high doses of BDE-47 resulted in adequately addressed in animals or humans. A developmental effects, including morphologic, study by Hardell et al. /131 / reported an cardiac, and neural deficits that impaired later association between BDE-47 concentrations and survivorship in the fish larvae /141/. Juvenile an increased risk for non-Hodgkin's lymphoma zebrafish chronically exposed to ecologically (NHL). In the highest risk/highest exposure relevant levels of BDE-47 exhibited altered group, BDE-47 was also significantly correlated locomotion behavior /137/. Dietary exposure of with elevated titers to Epstein Barr IgG, a human juvenile Chinook salmon (Oncorhynchus herpes ν irus that has been associated with certain tshasytscha) to environmentally relevant levels of

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PBDEs increased susceptibility to pathogenic Johansson et al. /145/ reported a negative microorganisms /136/. relationship between EPBDEs and reproductive 3.1.3.2 Birds. PBDEs are detected at high success in peregrine falcons from Sweden. PBDE concentrations in birds of prey, such as peregrine concentrations in eggs were negatively related to falcons (Falco peregrinus) and common kestrels the average number of young produced from (F. tinnunculus), and studies have shown that individual breeding females over a 2-7 year PBDEs may exert DDT-like endocrine-disrupting period. Van den Steen et al. /147/ observed and reproductive effects in several species. In negative effects of PBDEs on reproductive captive American kestrels (F. sparverius), Fernie performance in European starlings (Sturnus et al. /142/ reported decreased plasma T4 and vulgaris) implanted with silastic tubes containing vitamin A levels, as well as indications of environmentally relevant concentrations of oxidative stress in kestrels dosed with PBDEs. A recent field study in the U.S. /148/ environmentally relevant levels of DE-71, both in reported a negative relationship between ovo and post-hatch. In a separate study, DE-71 reproductive performance and PBDEs in eggs of exposure had a negative impact on the timing and wild ospreys (Pandion haliaetus) at two locations frequency of courtship behaviors that are essential in the highly contaminated Columbia River valley for successful reproduction /143/. In a follow-up of Oregon and Washington, and suggested that experiment, exposure to DE-71 and unintentional concentrations of -1000 ng g"1 ww may reduce exposure to α-HBCD resulted in delayed egg reproductive performance in ospreys. Many North laying, reduced egg size, eggshell thinning, and American osprey populations have PBDE levels reduced fertility and reproductive success in exceeding 1000 ng g_1 ww and thus may be at kestrels /144/. Egg laying was delayed with increased risk for contaminant-induced repro- increasing concentrations of BDEs-153, -154, -28, ductive impairment. and -17, and multiple effects of DE-71 exposure 3.1.3.4. Marine mammals. Marine mammals on egg quality (egg size and mass) were observed. are long-lived, apex predators that can accumulate Delayed egg laying, thinner eggshells, and poorer extremely high concentrations of PBDEs and fledgling success were associated with BDE-153, other POPs through the marine food chain. While the dominant congener recently found in kestrels the main exposure route for adults is the and peregrine falcons /145/, whereas eggshell consumption of contaminated fish, placental and thinning was consistently inversely associated lactation exposure is significant for young with the majority of congeners in the DE-71 animals. Marine mammals from the California mixture, especially BDE-153, and -154, and -28, coast contain the highest reported PBDE levels in as well as α-HBCD. Fernie et al. /144/ concluded the world 191. The highest concentrations on that these changes in the reproductive success of record were detected in blubber of adult male captive kestrels, particularly eggshell thinning California sea lions (mean 55300 ng g~l lw) /149/ associated with reduced hatching success, may and transient killer whales (Orcinus orca) (up to partially explain the decline of American kestrels 12600 ng g_1 lw), as well as in resident killer across North America. McKernan et al. /146/ whales from the Puget Sound-Strait of Georgia reported decreased pipping and hatching success Basin (mean 7500 and 6800 ng g~' lw in females in American kestrel embryos following the air and males, respectively) /150,151/. On the U.S. cell injection of DE-71 at concentrations of 10 Atlantic coast, relatively high PBDE concen- ! and 20 μg g~ , suggesting that the observable trations (mean 3000-4000 ng g~' lw) were effect level (LOEL) may be as low as 1800 ng g ' reported in young harbor seals (Phoca vitulina ww (based on the uptake rate). Similarly, concolor) /152/ and in juvenile bottlenose

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dolphins from the Charleston Harbor estuary, mental exposure to PCBs. Behavioral alterations North Carolina (mean 6000-8000 ng g~l lw) /153/. were reported in perinatally exposed mice /165/. Adverse health effects in marine mammals co- TBBPA can act as an , and exposed to PBDEs and PCBs have been reported, both estrogenic and androgenic effects have been including thyroid hormone alterations in gray reported. Hydroxylated TBBPA metabolites have seals (Halichoerus grypus) /154/ and harbor seals been shown to inhibit sulfotransferase (Phoca vitulina) /155/, and thymic atrophy and activity in vitro /166/, which could decrease splenic depletion in harbor porpoises (Phocoena estrogen clearance and result in elevated levels of phocoera) from the North and Baltic Seas /156/. circulating . Environmentally relevant A study of infectious diseases in California sea TBBPA concentrations decreased reproductive otters {Enhydra lutris) co-exposed to PBDEs and success in zebra fish /167/ and inhibited estradiol PCBs suggested possible synergistic interactions metabolism in lake trout/168/. between these contaminant groups /157/. A recent Disruption of thyroid hormone homeostasis is study reported, however, that PBDEs alone proposed to be the primary toxic effect of TBBPA significantly reduced the probability of first year and many other BFRs. TBBPA has an even closer

survival in gray seals /158/. structural relation to thyroxin (T4) than PCBs, and TBBPA toxicity to the thyroid might be related to

3.2 Tetrabromobisphenol A (TBBPA) its effects on the transport of T4 in the blood. In vitro assays demonstrated that the binding affinity TBBPA, a cytotoxicant, immunotoxicant, and of TBBPA to human (TTR) is greater thyroid hormone agonist, has the potential to than that of T4 (up to 10 times more potent than T4) disrupt estrogen signaling /17,159/ TBBPA is /169,170/. TBBPA can act as a thyroid hormone toxic to primary hepatocytes, destroys mito- agonist, antagonist, potentiator, or have no effect chondria, and results in membrane dysfunction in /169,172-174/. Rana rugosa tadpoles co-exposed liver cells and inhibition of a key mixed function to (T3) and TBBPA exhibited oxidase enzyme (cytochrome P450 2C9) /160/. suppression of T3-induced tail shortening, Studies of toxic effects using cell lines indicating a thyroid hormone antagonist effect demonstrated that TBBPA interferes with cellular /172/. A reproductive developmental feeding study signaling pathways, reducing cell viability and in rats reported an increase in T3 in TBBPA- proliferation /161/. TBBPA is also highly exposed female rat offspring and a reduction in immunotoxic in vitro /162/ and inhibits T-cell circulating total T4 in both genders /175/. The activation by blocking the expression of CD25 developmental effects also included increased proteins that are essential for the proliferation of testis and pituitary weight. activated Τ cells. Thus, TBBPA may have a profound effect on an organism's immune- 3.3 Hexabromocyclododecane (HBCD) mediated defense against bacteria, viruses, and possibly cancer. TBBPA is also neurotoxic in rat Experimental evidence indicates that HBCD, brain cells, where it causes oxidative stress, the second most used flame retardant, exerts a inhibits dopamine uptake, and generates free range of endocrine disrupting and reproductive radicals /163/. Recent in vivo studies have shown developmental effects in animals /10,17/. that neonatal TBBPA exposure causes hearing Although the acute toxic effects are low /176/, deficits in rat offspring /164/, including changes oral exposure to HBCD induces drug- in hearing latency and hearing threshold that are metabolizing enzymes in rats and fish /177,178/ similar to changes observed following develop- and can induce malignant transformation in

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 274 S. SHAW ET AL. mammalian cells by a non-mutagenic mechanism pre- and postnatal exposure resulted in reduced /179/ HBCD isomers are endocrine disruptors fetal body weight, reduced pup body weight, and with anti-androgenic properties that inhibit reduced pup survival at higher doses /194/. aromatase and interact with steroid hormone Although they exhibit low acute toxicity in receptors /169,180/. Like other BFRs, HBCDs humans, SCCPs are classified as carcinogens may disrupt thyroid hormone homeostasis /176/, under Proposition 65 by the State of California resulting in decreased levels of T4 and increased /51/. The National Cancer Institute lists SCCPs as levels of thyroid stimulating hormone (TSH) reasonably anticipated to be human carcinogens, /177,181-183/ and affect thyroid hormone based on sufficient experimental evidence /193/. receptor-mediated gene expression /184/. The SCCPs are classified by the IARC as Group Many effects of HBCDs occur during 2B—possibly carcinogenic to humans /195/. The development. Low-dose reproductive develop- potential for SCCPs to exert adverse impacts on mental studies in rats have shown that HBCDs children and other vulnerable populations is decrease bone density and retinoids, and enhance currently under review 111. immune responses to sheep red blood cells /185/. Following neonatal exposure in rats, the 3.5 PentaBDE Replacements: Firemaster 550® developmental neurotoxic effects include Components and Chlorinated Tris (TDCPP) aberrations in spontaneous behavior and learning, and memory deficits /186,187/. The HBCDs are Although replacement flame retardants, such neurotoxic to rat cerebellar granule cells /188/, as Firemaster 550® and chlorinated Tris, are in inhibit the depolarization-evoked intracellular high-volume use, few studies have been conducted calcium and release /189/, and in animals or humans on the health effects of these alter the normal uptake of in rat chemicals. Firemaster 550® components TBB and brain /190/. Lilienthal et al. /191/ reported that TBPH are genotoxic in fish, causing significant HBCD exposure caused hearing deficits in males DNA damage (increased DNA strand breaks from and catalepsy (a dopamergic effect) in females. liver cells) in orally exposed fish /196/. Triphenyl The effects differed from those observed after phosphate (TPP) is toxic to aquatic organisms exposure to TBBPA or the pentaBDE-99. including Daphnia 11911, rainbow trout, and The human health effects of HBCDs have not fathead minnows /198/. Triaryl phosphate been studied. Although levels in humans are still isopropylated is a reproductive/ developmental relatively low, HBCD has the potential to bio- toxin at mid- to high doses in rats /198/. accumulate and persist in the environment. There Histopathologic changes were observed in female is concern about the increasing levels of HBCD in reproductive organs and adrenals at all doses. wildlife and humans, especially in Asia/15/. Studies have reported that chlorinated Tris (TDCPP) is mutagenic /32,33/ and carcinogenic in 3.4 Short-Chain Chlorinated Paraffins (SCCPs) rats /33,34/. TDCPP is also absorbed by humans /199/. The U.S. Consumer Product Safety SCCPs are recognized by the Stockholm Commission (CPSC) considers TDCPP a probable Convention as highly toxic to aquatic organisms human carcinogen and estimates a lifetime cancer at low concentrations /70/. In rodent models, risk from TDCPP-treated furniture foam is up to SCCPs are toxic to the liver and kidney, and 300 cancer cases/million /33/. However, we should thyroid gland, and carcinogenic in rats and mice note that this risk assessment focused entirely on of both genders /192,193/. SCCPs are also dermal exposure and did not take into account developmental toxins; studies have shown that exposure resulting from the escape of TDCPP from

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM HALOGENATED FIRE RETARDANTS: RISKS VS BENEFITS 275 products into dust. The U.S. EPA considers chlorinated furans and dioxin-like PCBs /207, TDCPP a moderate hazard for cancer and 208/. In the UK, brominated and brominated- reproductive/developmental effects /200/. chlorinated dioxins and furans contribute about A recent study showed that men living in 30% of the dioxin-like toxicity in food /211,212/. homes with high amounts of the Brominated dioxins have been detected in human (OP) flame retardants TPP and TDCPP in tissue /213-215/ and in biota /216,217/. A recent household dust had reduced sperm counts and study of Swedish adipose tissue samples altered levels of hormones related to fertility and suggested that they contributed up to 14% of the thyroid function /201/. High levels of TPP in dust total dioxin toxic equivalency (TEQ) /215/. were associated with a substantial (19%) Brominated dioxins also contribute to dioxin-like reduction of sperm concentrations and a 10% toxicity in human milk /214/, adding to the increase in prolactin levels. Increased prolactin is exposure of infants worldwide to chlorinated considered a marker of decreased neuroendocrine/ dioxins and furans and dioxin-like PCBs, which dopamine activity and may be associated with exceeds the WHO recommended tolerable daily erectile dysfunction as well 12021. High levels of intake by more than an order of magnitude /218/. TDCPP in dust were associated with a 17% Workers involved in the production and increase in prolactin and a 3% decline in free recycling of BFRs are exposed to brominated thyroid hormone levels. The possible synergistic dioxins and furans /219/. People living near or additive effects of the numerous flame primitive e-waste recycling facilities are also at retardar.t chemicals in use have not been studied high risk for exposure to HFRs and halogenated in animals or humans. dioxins and furans /23,220,221/. Firefighters have elevated exposure to brominated and chlorinated dioxins and furans 12221, both during and while 4. BROMINATED FLAME RETARDANTS cleaning up after fires /26,223/. High levels are UNINTENTIONALLY PRODUCE formed during accidental fires under uncontrolled BROMINATED DIOXINS AND FURANS combustion conditions in the presence of BFRs /204,224/. The significantly elevated rates of Brominated flame retardants, especially cancer reported in firefighters comprise four types PBDEs, and PBBs, are a major source of toxic that are potentially related to exposure to dioxins tetra- to octa-brominated dioxin and furan and furans—multiple myeloma, non-Hodgkin's contamination /203-208/. Brominated dioxins and lymphoma, prostate, and testicular cancer 125,261. furans are unintentionally released during the entire life cycle of these flame retardants. 4.2 Toxicity of Brominated Dioxins and Furans

4.1 Environmental, Food, and Human Brominated dioxins and furans have toxicities Contamination similar to their chlorinated counterparts in human cell lines and mammalian species /222,225-227/. Brominated and mixed brominated-chlorinated Thymic atrophy, wasting of body mass, lethality, dioxins and furans are major contaminants, both teraterogenesis, reproductive effects, chloracne, indoors and in the environment. Brominated immunotoxicity, enzyme induction, decreases in furans have been found in house dust globally T4 and vitamin A, and increased hepatic /22,207,209,210/. In Japan, brominated furans are porphyrins have been observed in animal studies the major contributors to dioxin-like toxicity in of both brominated and chlorinated dioxins and house dust and exceed the amount contributed by furans /203,222,227/. In vitro responses are

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 276 S. SHAW ET AL. similar, including enzyme induction, anti-estrogen 5. END-OF-LIFE CONSIDERATIONS FOR activity in human breast cancer cells, and HALOGENATED FLAME RETARDED transformation of mouse macrophages into tumor MATERIALS cells /203/. The end-of-life management for products treated with PBDEs and other HFRs is critical 4.3 Formation and Release of Brominated /204,234/. The three main options are: (1) Dioxins and Furans during the Life Cycle reuse/recycling, (2) incineration combustion, and of Brominated Flame Retardants (3) landfilling. Different management schemes are needed for different materials, such as flame- Halogenated dioxins are formed uninten- retarded plastic in e-waste or cars, polyurethane tionally during the production of halogenated foam in furniture or cars, and textiles. aromatic compounds. Brominated dioxins and furans have been found as contaminants in such 5.1 Recycling of Brominated Flame-Retarded commercial BFRs as PBDEs, decabromobiphenyl, Materials l,2-bis(tribromophenoxy)ethane, TBBPA, and bromophenols /203,228/. Brominated dioxins and From an energy efficiency life cycle furans are also formed in the production of BFR- perspective, the preferred method for end-of-life retardec1 plastics in thermal processes like treatment of flame-retarded materials is molding and extrusion /205,224,229/. For PBDEs, mechanical recycling because it reduces the need the levels of dioxin and furan contamination for new materials /204,234/. Toxicity and increase during the life span because of photolytic potential health effects also have to be considered, conversion, which can take place in plastic however /204,234/. Materials containing halo- matrices /230/ or treated textiles /231/. The largest genated flame retardants and other toxic amounts are formed in the end-of-life stage chemicals are often exported to developing and during primitive recycling of e-waste /22,24,206/, transition countries to be recycled, resulting in secondary metal industry processes /232/, and environmental and human contamination /21,23, during non-BAT (best available technology) 220,235-237/. Similarly, workers in industrial incineration of e-waste /204,205/. The primitive countries can be exposed to high levels of PBDEs recycling of thousands of tons of PBDEs and other toxics during the recycling of e-waste or contained in e-waste is estimated to release tons polyurethane foam /204,234,238,239/. of brominated and brominated-chlorinated dioxin/ Another critical drawback of recycling PBDE- furans into the environment /206/. In open containing materials is the formation of bromi- burning e-waste areas in China, the measured nated furans during the recycling operations such levels of these compounds in soil exceeded as extrusion and molding /205,229,240/. Recycled allowable soil standards for dioxin worldwide PBDE-containing plastics can be contaminated /24/. PBDEs were shown to be the major with brominated dioxins and furans, often precursor chemicals for this severe contamination exceeding allowable limits /204,241/. The /206/. Similarly, in industrial countries, chemical industry does not recommend the brominated dioxins and furans are released from mechanical recycling of some of the bromine- uncontrolled burning of BFR-containing wastes containing plastic waste /241,242/. and the resulting emissions contribute substantially Furthermore, some BFRs can degrade the to total dioxin-like toxicity 7204,233/. mechanical properties of recycled engineering

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM HALOGENATED FIRE RETARDANTS: RISKS VS BENEFITS 277 plastics /243/. If the properties of recycled destruction of HFR materials in cement kilns and materials are not comparable to the original metal industry and associated releases needs plastic, then the plastic will be 'downcycled' into further assessment. less-demanding applications. Recent studies showing that PBDEs and other flame retardants 5.3 Landfllling and Release of Halogenated are present in household goods /244/, videotape Flame Retardants from Landfills casings /245/, and children toys /246/ revealed that such downcycling is taking place without A large portion of the products treated with controlling BFR-contaminated plastic streams. HFRs ends up in landfills. This practice is common Such practices lead to unnecessary human in developing, transition, and industrial countries exposure to BFRs from recycled materials. that lack adequate thermal waste treatment options. For example, substantial amounts of flame- 5.2 Combustion of Materials Containing retarded waste are landfilled in California /252/ Halogenated Flame Retardants and in Australia, a countiy that has no waste incineration capacity. Brominated flame retardants A large proportion of BFR materials are leach from landfills to contaminate the environ- eventually burned. Depending on the quality of ment /253-256/. Significant PBDE emissions in combustion, high levels of brominated dioxins leachates have been detected from landfills in and furans can be formed and released /205,247/. industrial countries /253,255,256/. In various In particular, the open burning of e-waste in regions of Canada, high concentrations of PBDEs developing and transition countries release large were present in the soil adjacent to all landfills and amounts of halogenated dioxins and furans /206/. dumpsites /253/. A mechanistic mass-balance Brominated dioxins and furans are also emitted model was developed to study the migration of from open burning of municipal waste /233/ and PBDEs from waste streams to landfills and into the from accidental fires in houses, cars and other environment /257/. Recently, PBDE-contamination transport /224/. Large amounts of e-waste, cars, in ground-water has been reported at several South and other products containing BFRs are treated in African landfill sites /254/. melting furnaces for recovery of metals. These With engineered landfills with bottom liners, operations can include incomplete combustion leachates can be collected and treated to reduce processes resulting in the emission of halogenated the flow of contaminants to ground and surface dioxins and furans and HFRs /232,248/. water for some time /258/. Such treatments are Brominated flame retardants can be destroyed expensive, however, and the resulting solids from with high efficiency in Best Available Techniques the adsorption of pollutants need further treatment (BAT) incinerators operated according best or deposition. Because of their persistence, environmental practice (BEP) /205,247,249/. For PBDEs and other POPs will remain in landfills BAT incineration, however, the costs for and leach into the environment for decades. Over incinerated material are about $100/ton, hence these extended time frames, landfill engineering such facilities are too costly for developing and systems, including basal and capping liners, gas transition countries /250/. Even in BAT grate and leachate collection systems, will inevitably incinerators, elevated brominated dioxin/furan degrade and lose their ability to contain the levels were found in the bottom ashes /251/, most contaminants /253,257,258/. Therefore, Iandfilling probably due to particle matter falling through the does not appear to be a sustainable solution for grate not subjected to a complete combustion. The long-term containment of POP-containing waste.

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All three above options for end-of-life 6.1 California Home Furniture Standards: treatments for HFR-containing materials result in Technical Bulletins 117 and 116 environmental contamination and potential human exposure. The waste management of materials California TBI 17, implemented in 1975, containing hazardous HFRs in current use must requires flexible polyurethane foam and other be globally addressed and significantly improved. filling materials in furniture and juvenile products to withstand exposure to a small open flame for 12 seconds /260/. This standard is most 6. FLAMMABILITY STANDARDS AND economically and conveniently met by adding THEIR IMPLEMENTATION organohalogen flame retardant chemicals to the filling materials. Despite considerable research Flame retardants are primarily used to meet showing adverse health impacts from the flammability standards, commonly developed by halogenated chemicals commonly used to meet standards bodies such as the International Electro- TBI 17 as described in Section 3, most national technical Commission (IEC), International furniture manufacturers increasingly apply the Organization for Standardization (ISO), Under- standard for furniture sold across North America. writers Laboratory (UL), International Codes For many juvenile products, such as nursing Conference (ICC), American National Standards pillows, high chairs, strollers, and baby carriers, Institute (ANSI), and the American Society for manufacturers make only one line of products and Testing and Materials (ASTM). National, state, follow the California standard across the U.S. and and local government agencies and bureaus such Canada. Thus, TBI 17 is becoming a de facto as the U.S. Consumer Product Safety Commission national standard, with organohalogen flame (CPSC), and the California Bureau of Electronic retardants being found in many baby products and Appliance Repair, Home Furnishings and containing polyurethane foam. Thermal Insulation (the Bureau) may include California Technical Bulletin 116 (TBI 16), the compliance with one or more of these standards companion standard for fabric flammability, is a as part of the regulatory requirements for voluntary cigarette smolder test and rarely manufacturers. followed. In addition, TBI 17 requires that fabrics Fires are complex and can vary enormously. A pass the Federal CS 191-53 flame-spread standard, material's performance, as required to meet a a standard designed to remove the most dangerous flammability standard, will depend on the design flammable materials from the clothing market. of the standard, including the source of ignition According to some sources, this standard is so and the duration and location of a flame or heat weak that tissue and newspaper can pass it /261/. source. In some cases, the individual components As discussed in section 7.1, the lack of an effective of an article, such as the foam and the fabric are fabric standard is one weakness of TBI 17. tested separately. Other 'composite tests' are performed on a whole manufactured article. A 6.2 California Technical Bulletin 133 (TB133) piece of furniture meeting a particular standard can for Public Occupancies behave in different ways under varied circumstances. For example, fires may strike TBI33 is a flammability standard for the different surfaces with different results. Standards composite testing of seating furniture for use in that are designed to prevent a small open flame high risk public occupancies in California 12621. from igniting uncovered foam may not reflect the In most applications, TBI33 compliance is not flammability of a complete upholstered chair /259/. required in public buildings with active sprinkler

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systems. In these buildings, compliance with use of flame retardants in furniture and baby TBI 17 is required. TBI33 is a composite test, products across North America. meaning that individual furniture components cannot he tested independently of other materials 6.4 CPSC Mattress Standard 16 CFR 1633 used in the furniture's construction. Compliance with this open-flame standard is typically CPSC standard 16 CFR 1633 is a severe achieved in one of two ways: (1) by inserting a federal flammability standard for mattresses, fireproof barrier fabric or batting (such as implemented in 2007 /266/. The standard is fiberglass or "Kevlar" based materials) between commonly met with a barrier technology rather foam and fabric; or (2) with a combination of fire- than the addition of flame retardants to foam. retarded upholstery fabric or inherently fire- Typical barrier technologies include the use of retardant wool fabric and foam specifically ignition resistant fiber batting and/or the use of an designed for high risk use. The only domestically ignition resistant fabric beneath the cover produced foam that fits this criterion is made with material. a high level of solid powered melamine (up to During flammability testing, the vertical 45% b> weight) along with organohalogen flame surface of the mattress is subjected to 50 seconds retardants /263/. Because the TB133 test burns of intense flame exposure from large propane full-size products and requires that all component burners and the horizontal surface to 70 seconds. variations be tested, the standard is not practical The standard requires that: (1) During the next 30 for residential furniture. minutes, the peak rate of heat release for the mattress set must not exceed 200 kilowatts, and 6.3 CPSC Staff Draft Furniture Standard (2) the total heat release must not exceed 15 MJ during the first 10 minutes of the test. The barrier Smoldering ignition requirements for fabrics materials used by manufacturers to achieve are also important as 90% or more of residential compliance are primarily inherently combustion upholstered furniture fire deaths are caused by resistant polymeric fibers or -treated cigarette ignition /264/. In February 2008, the cotton. According to the polyurethane foam U.S. CPSC replaced a draft small open flame test industry, flame retardant chemicals are not standard for furniture foam (similar to usually used in mattress foams in the U.S. Were California's TBI 17) with a draft 'smolder test' barriers not used, achieving the level of (or cigarette ignition resistance) standard for flammability required by the standard would lead furniture fabric. This draft standard can be met to very high levels of foam fire retardants, which with smolder-resistant cover fabrics or interior could be expensive and could cause unacceptable fire-resistant barriers rather than chemicals. characteristics in the mattress foam. In a statement on the 2008 Notice of Proposed Rulemaking the CPSC, Commissioner Nancy 6.5 Standards for Electronics Enclosures Nord said the new standard would address furniture fires without requiring the use of fire- The current rigorous standards governing the retardar.t chemicals /265/. This CPSC draft safe internal functioning of electronic equipment standard has been moving through the develop- prevent fires, electric shock, and other harm. ment process since 2008. If proposed and Recently proposed 'candle' standards would have implemented, this standard, which regulates fabric mandated that the outer housings of consumer flammability rather than foam flammability, could electronic products be resistant to external ignition preempt California TBI 17 and greatly reduce the from a small open flame. Such requirements could

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 280 S. SHAW ET AL. result in the addition of up to 30% by weight of phosphate (TCPP), and other halogenated organohalogen, , or other flame retarding phosphate esters are often used with polyurethane chemicals to the housings /267/. and polyisocyanurate (polyiso) insulation. HBCD For example, IEC-Standard 62368 AudioVideo, is a persistent organic pollutant, and the other Information and Communication Technology organohalogens used with insulation have known Equipment - Safety Requirements developed by the toxic properties or lack adequate health data. The International Electrotechnical Commission's use of energy efficient insulation materials, such as (IEC) TCI08 included such a candle flame polystyrene and polyurethane, treated with requirement. The standard was voted down in organohalogens, means that energy efficient 2008 by a majority of delegates from 31 'green' buildings can contain toxic chemicals. countries, based on a lack of proven fire safety benefit, as well as health, environmental, and 6.7 Motor Vehicle Standards other concerns. Several other similar proposed candle flammability standards from the IEC, The U.S. Federal Motor Vehicle Safety Underwriters Laboratory (UL) and the Canadian Standard (FMVSS 302), established in 1972, is an Standards Association (CSA) were also voted international flammability standard for the down in 2008. Nonetheless, a candle flame occupant compartments of motor vehicles. ignition requirement for television housings in the According to the National Highway Traffic Safety EU (CENELEC EN 60065) passed in 2009. Administration, the purpose of the standard is to reduce deaths and injuries to motor vehicle 6.6 Building/Insulation Flammability Standards occupants caused by vehicle fires, especially those from matches or cigarettes. Essentially the Polystyrene, polyisocyanurate, and polyure- same test is embodied in ISO 3795, BS AU 169 thane are insulation materials that increase energy [United Kingdom (U.K.)], ST 18-502 (France), efficiency and whose use in buildings, especially DIN 75200 (Germany), JIS D 1201 (Japan), SAE energy-efficient buildings, is growing rapidly. J369 (automotive industry) and, dealing with The ASTM International and the National Fire plastics flammability, ASTM D 5132. Protection Association (NFPA) set flammability Studies of brominated flame-retardant levels standards for the ignition, burning, and com- of cars have indicated the presence of PBDEs, bustion characteristics of insulation and other TBBPA, and HBCD in air and dust within the building materials. Chapter 26 of the Uniform cabins and trunks in the U.K. /268/ and in Boston, Building Code 2603.3 (see test ASTM Ε 84 in Massachusetts in the U.S. /269/ where section 1.5) states that foam plastic insulation extraordinarily high levels of chlorinated tris or shall have a flame-spread index of 75 or less and TDCP were also observed. Despite the use of a smoke-developed index of 450 or less. These halogenated flame retardants, motor vehicle flammaoility standards are instrumental in the flammability remains a serious problem /268/. establishment of building codes, insurance requirements, and other fire regulations for building materials. 7. FIRE SAFETY BENEFITS OF Flame retardant chemicals are added to HALOGENATED FLAME RETARDANTS insulation materials to meet such building codes. IN CONSUMER PRODUCTS Polystyrene insulation in the U.S. is always treated with HBCD. Halogenated chemicals, such Flame retardants are used in a wide variety of as 1-Bromopropane, Tris(l-chloro-2-propyl) products and assumed to provide a fire safety

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM HALOGENATED FIRE RETARDANTS: RISKS VS BENEFITS 281 benefit. As will be discussed below, this benefit Table 1. California's decline in fire death rate from has not been demonstrated for small open flame 1980-1984 to 2000-2004 was similar to that of the flammability standards for home furniture, baby other seven largest states in the U.S., which do not products, and electronic enclosures, and some have fire safety regulations for furniture /287/ uses of building insulation. State % Reduction 7.1 Home Furniture (Technical Bulletin 117) California 40 Georgia 36 The California flammability standard TB117 Illinois 45 has led to the use of pentaBDE and other organo- Michigan 38 flame retardants in consumer products for New York 48 more than 30 years. Yet, whether this standard Ohio 41 has been effective in preventing fires and fire Pennsylvania 41 deaths is not certain. An analysis of fire data from Texas 37 1980 to 2005 by the NFPA shows that the rate of reduction of fire deaths in California is similar to that of seven other large population states that do not have a furniture flammability standard (Table 15,000 lives would have been saved /271/. 1). NFPA data comparing California with the Laboratory research on TB 117 supports this entire U.S. does not show a greater reduction in lack of measurable fire safety benefit. A study at the rate of fire deaths in California (Figure 3) the National Bureau of Standards in 1983 showed between 1980 and 2005. According to the NFPA, that following ignition, the important fire hazard U.S. fire data are not detailed or complete enough indicators (peak heat release rate and the time to to show whether adding flame-retardant peak) were the same in TBI 17-compliant chemicals to furniture foam in California furniture where the foam was treated with since 1980 has made a measurable difference in chemical flame retardants and in non-treated fire deaths in that state /270/. This report could be furniture /272Λ A small flame was able to ignite contrasted with an NFPA press release estimating both regular furniture and furniture meeting the that if fire safe cigarettes had been required 20 TBI 17 standard—once ignited, the fire hazard years earlier was essentially identical for both types /273/.

2.5

a § 1.5 αο %S 1 a 0.5 Caffornia r—i—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—> 1981 1983 1985 1987 1989 1991 1993 1995 1 997 1999 2001 2003 2005

Fig. 3: Residential fire and flame death rates in the U.S. and California 1981-2005. Trend data and linear regression lines are shown /299/. Prepared by California Department of Public Health, EPIC Branch

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A 1995 report from the Proceedings of the of research discussed above is that TBI 17 does not Polyurethane Foam Association provides further appear to increase fire safety. This outcome is not evidence that TBI 17 does not improve fire safety. unexpected because in a fire, the fabric will ignite Small open flame and cigarette ignition tests were first, exposing the foam to a large flame. Because it performed separately on 15 fabrics covering is designed to resist small flames, TBI 17 does not TB 117 type polyurethane foam, conventional prevent foam ignition from larger flames. A more polyurethane foam, and polyester fiber wrap effective flammability standard would address the between the fabric cover and the foam cores. The flammability of the covering material and/or the study found no improvement in ignition or flame structure of the upholstered furniture as opposed to spread from a small open flame or cigarette considering only the impact of a small flame on the ignition propensity using TBI 17-compliant foam interior foam. 121 AL Furthermore, CPSC research demonstrates 7.2 Standards for Electronic Enclosures that these types of small scale fire testing do not accurately predict large scale fire behavior. These Proposals for flammability standards for plastic researchers reported that "The component tests in housings around television (TV) and other TBI 17 did not satisfactorily predict composite electronic equipment often cite papers by ignition behavior. Fabrics and fillings that Simonson and colleagues /278-280/ showing a comply with TBI 17 often ignited when tested as large fire-safety benefit from the use of flame finished chairs. TBI 17 would not, if federally retardant chemicals in TV enclosures. The mandated, ensure a substantial reduction in the Simonson model in these papers consists of a life- risk of small open flame ignition of finished cycle study comparing TV sets with and without articles of furniture''' 111 SI. flame retardants. The model compares emissions Ignition and fire-growth tests in the from TV production, flame retardant production, Babrauskas et al. 12161 study in 1988 provide the and TV incineration, but does not include health or basis for a frequently quoted statement that flame environmental effects of the chemical flame retarded materials offer a 15-fold greater escape retardants themselves. For example, the model time for occupants during a fire. The Babrauskas considers the chemicals emitted when a TV burns, study, however, did not examine any TB 117 foam but is limited to , polycyclic but rather only formulations of much higher aromatic hydrocarbons, dioxins, and furans. The percentage of added flame retardant chemicals model does not consider the effects of exposures than used to meet TBI 17. Furthermore, the room that are due to the migration of flame retardants, tests were fully-furnished rooms in which such as decaBDE or HBCD, from the plastic TV numerous combustibles were burned and not tests enclosures into household dust, humans, animals, of upholstered furniture items alone. An earlier water, and the food chain /46,210/. In view of the study by Babrauskas /273/ found the time-to-peak recent significant increase in knowledge about the results for non-flame retarded and TBI 17 foams health and ecologic effects of flame retardants were identical, to within the data scatter of the (Section 3), the Simonson model would benefit apparatus. from considering other inputs across the life cycle Based on his research discussed above, of the products. These effects would include health Babrauskas 12111 concluded that TB 117 is an effects from exposures occurring during ineffective test that does not accomplish its manufacturing and use of the product, as well as intended purpose of averting furniture ignitions toxicity to humans and the environment during and from small flaming sources. The cumulative result after disposal.

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Table 2. Annual estimated TV fires per million TVs in the U.S. and Europe that breach the TV enclosure

Estimate TV fires/million Ignition Source Reference Europe - Simonson3 165 100 internal, 65 external /274/ U.S. - Simonsonb 13 internal, external /275/ Europe - DTI° 18.2 12.2 internal, 6, external 7279/

a Based on 8 reported TV fires in a Stockholm suburb in 1994;b NFPA National 1990-1994 data based on surveys and fire incident data from the U.S. Fire Administration;c UK Department of Trade and Industry (DTI) 1996 report based on fire brigade data and a review of fire statistics across Europe

As detailed in Table 2, the Simonson model and Industry (DTI) review of fire brigade data also uses dissimilar data sources for comparing from across Europe found 12.2 European TV fires the annual fire rates in TV enclosures without per million TVs by internal ignition plus 6 TV flame retardants (Europe) and to those with flame fires per million TVs by external ignition /283/. retardants (U.S.). For Europe, the model input The Simonson estimate, based on data from one extrapolates from eight TV fire incidents during Stockholm suburb, gives results an order of 1994 in one suburb of Stockholm, Sweden to an magnitude higher than European fire brigade data, estimate of 165 TV fires per million TVs annually which are more representative and comparable to across all of Europe /278,279/. The 1994 in-depth the U.S. data reported by the NFPA (Table 2). review used a broad definition of a TV fire, which The DTI review suggests a similar rate of TV included very small fires. A detailed critique of fire incidents in Europe, where flame retardant extrapolating from such a small, unrepresentative chemicals have not been used, as that in the U.S., sample to fire data for all of Europe has been where TV enclosures contain decaBDE and other previously published /281/. flame retardants. Annual U.S. TV fire data as reported by the The end-of-life emissions calculations in the NFPA was based on fire-department surveys and Simonson model also used different inputs and fire- incident data from the U.S. Fire Admini- methodologies for the U.S. and Europe. The model stration from across the country /282/. The data assumes that all disassembled TV enclosures will were normalized to 13 TV fires per million TV be incinerated, which overestimates the extent of sets, from both internal and external ignition incineration of European TVs. The non-treated 12191. The Simonson model then assumed that plastics in European TVs can be reused repeatedly only a fraction of the U.S. TV fires reported by without degradation and account for 87% of the NFPA were due to internal ignition and recycled electronics plastics /243/. Plastic restricted further analysis to only the internal enclosures manufactured with flame retardants ignition fires (reducing the number of annual U.S. (U.S. TVs) are not recommended for recycling, as fires from 13 TV fires per million TVs to 5 TV combining flame-retardant-containing recycled fires per million TVs) /279,280/. In contrast, the plastics with new product in manufacturing can model does not restrict European TV fires to result in dioxin and furan concentrations in the internal ignition fires. The dissimilar data sources plastic enclosures above legal limits /242/. The are based on different definitions and sizes of TV model underestimates incineration emissions by fires, potentially leading to an unrealistically high assuming that 100% of incinerated plastic estimate for European television fires and a enclosures are used for energy recovery. In Europe correspondingly low one for the U.S. and the U.S., only a small percentage of plastic By comparison, a U.K. Department of Trade waste (31% in Europe, 14% in the U.S.) is

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 284 S. SHAW ET AL. incinerated with energy recovery /284/. Also not release of a material, this practice can also accounted for in the model are the emissions from increases the yield of such toxic fire effluents uncontrolled incineration, such as landfill fires or during combustion /286,287/. open pit burning of plastic waste after disassembly. Halogenated flame retardants act by replacing Such unregulated incineration of TVs treated with the most reactive hydrogen (H·) and hydroxyl (H·) flame retardants emits toxic brominated dioxins free radicals in a flame with more stable chlorine and furans into the environment. (CI·) or bromine (Br-) free radicals. The OH· Conducting life-cycle analyses to evaluate the , however, is required for the conversion of benefits and risks of adding flame retardants to carbon monoxide to carbon dioxide. plastic enclosures can provide useful information CO + OH—> C0 + H· to policy makers. As described above, however, 2 the Simonson analysis would benefit from In the presence of brominated or chlorinated incorporating public health and environmental flame retardants, this reaction is prevented, impacts of commonly used flame retardant resulting in more carbon monoxide (CO) /288/. chemicals as well as using comparable data Thus, the same flame retardant action that reduces sources for the model inputs and end-of-life heat release is also responsible for much higher pollution related to disposal. yields of CO. In addition, the flame-quenching action of Br· and CI· radicals prevents the 7.3 Building/Insulation Flammability Standards oxidation of other like hydrocarbons and

aldehydes, to carbon dioxide (C02) and water, Insulation materials containing halogenated and significantly increases the smoke yield. flame retardants can add to the toxicity of a Increased CO, incapacitating irritants, and smoke building. The toxicity could be reduced by the use hinder an escape from the fire. of such nonflammable materials as mineral or Fire effluents from the combustion of glass wool or by stopping the use of flame materials containing halogenated flame retardants retardart chemicals in insulation materials in will be more toxic for three reasons: situations when no fire hazard exists. This 1. The effluents will contain more carbon includes insulation between building foundations monoxide. and the soil, and between two outer wall layers of 2. The effluents will contain powerful irritant concrete. In these situations, despite the lack of acid gases ( or hydrogen fire danger, all polystyrene insulation is treated bromide). with HBCD. Having two well-labeled varieties of 3. The effluents will contain a cocktail of polystyrene, one that is flame retarded and one respiratory irritants comprising unburned and that is not, would reduce the use of HBCD for partially burned hydrocarbons, resulting from applications for which no fire hazard exists. stopping the burning process midway.

7.4 Effect of Halogenated Flame Retardants on In addition, as discussed, combustion of organo- Fire Effluent Toxicity halogen compounds leads to the formation of brominated and chlorinated dioxins and furans. Most fire deaths and most fire injuries result When flame retardants are present, the reduced from the inhalation of fire effluents, such as risk from increased time to ignition and reduced carbon monoxide, irritant gases, and soot /285/. heat release rate during a fire should be balanced Although the incorporation of halogenated flame against the increased hazard from CO, irritant retardants may reduce the ignitability and heat gases, and particulates like soot or smoke particles.

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8. SAFER ALTERNATIVES TO CHEMICAL surface (for example, a couch or mattress), a fire- FLAME RETARDANTS safe cigarette will normally extinguish itself in a few minutes when it reaches a speed bump of Reducing the sources of ignition can prevent thicker paper, rather than smoldering for as long as fires without adding potentially hazardous 45 minutes and potentially starting a fire. Fire-safe chemicals to consumer products. A 60% decrease cigarettes should reduce the potential benefit of in fire deaths in the U.S. since 1980 parallels the flame retardants in furniture and other products. decrease in per capita cigarette consumption /289,290/. An increased enforcement of improved 8.2 Fire-Safe Candles building, fire, and electrical codes and increased use of smoke detectors and sprinkler systems in New voluntary safety standards for fire-safe new construction have contributed to an increase in candles have been adopted by the candle fire safely. An estimated 65% of reported home industries in the U.S. /294,295/. Research leading fire deaths in 2000-2004 resulted from fires in to these standards was initiated after U.S. candle homes without working smoke alarms /291 /. consumption increased 350% from 1990 to 1998. Although candle-related fire injuries and deaths 8.1 Fire-Safe Cigarettes increased at much slower rates of 13% and 42%, respectively, improving candle fire safety became The leading cause of fire fatalities in the U.S. a joint objective of the candle industry and the is cigarette smoking. A large majority of CPSC. residential fire deaths in which upholstered The ASTM standards were developed to furniture was the first item ignited are caused by address candle fire safety issues based on research cigarette ignition 12921. Between 1980 and 2005, on the root causes of candle fires. The Society smoking-related fire deaths in the U.S. have developed candle manufacturing standards for declined from 2,000 to 800 annually /264/. The labeling about candle hazards, glass container most recent data show a continued decline to 720 material requirements to eliminate shattering due deaths in 2007 12921. The reduction of smoking, to candle heat, and improved candle design to through a combination of education, taxation, and minimize the four major causes of candle fires location restriction policies has proven the single (excessive flame height, secondary ignition, end of most effective fire safety strategy. useful life, and stability). Complying with these Smoking rates in the U.S. had declined to 21% standards requires a manufacturer to produce by 2004. The recent passage in all 50 states of candles (a) with warning labels, (b) with a legislation requiring the manufacture and sale of maximum wick length, (c) without combustible reduced ignition propensity (RIP) or 'fire-safe' decorative materials, (d) that will self-extinguish cigarettes /293/, should further reduce fire deaths. without incident when they have burned down, and The ASTM E2187-09 test method for measuring (e) that will be proportioned not to tip over easily. the ignition propensity of cigarettes is referenced in Ninety percent of U.S. candle manufacturers laws of all 50 states. Many such laws are just have pledged to comply with these standards. The beginning to be implemented. Fire-safe cigarettes ASTM is working with importers to ensure that contain internal 'speed bumps' of thicker paper these safety specifications are also met by imported that block the flow of oxygen to the rest of a lit candles. As a result, the ASTM estimates that the cigarette that is no longer being smoked. If a majority of all candles sold in the U.S. are in cigarette is accidentally dropped on an ignitable compliance with these fire safely standards. In

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Europe, a committee for standardization (CEN) printed circuit boards to deliver (particularly) task force for candles in Europe is similarly filament power. The benefits and costs of UL1410 defining standards and working with European could be revisited by evaluating the fire hazard candle producers to improve safety. The from current TV technology, as well as the impact implementation of these standards should reduce of the chemicals and materials used to meet this candle fire injuries and deaths. standard.

8.3 Alternate Designs and Materials 8.4 Safer Replacement Chemical Flame Retardants Design alternatives, such as making components of metal, glass, or ceramics instead Green chemistry—the design and use of safer of plastics, can reduce flammability without materials and processes with minimal adverse chemicals /36/. Fire-retardant barriers, usually impact on human health and the environment— made of polymeric materials like those used in should be used to design a new generation of mattresses, could be investigated for use around alternative flame retardant chemicals that are not foam in furniture and juvenile products. Avoiding based on bromine or chlorine. Currently, several low density polyurethane foam, which is halogen-free compounds have been shown to be relatively flammable, will reduce the fire hazard effective flame retardants, and almost all from a small open flame. High-density foam and production polymers (such as nylon, polypropylene, other filling materials such as polyester (which polyester, or polyurethane) have halogen-free melts rather than flames) can sometimes meet formulations that will meet current fire safety TB117 without the addition of chemicals. standards. The alternatives include mineral fillers, A discussion of the use of flame retardant which absorb heat and give off water, such as chemicals in TV enclosures provides an example aluminum trihydrate (ATH); low melting glasses in which changes in technology have reduced and ceramics, which seal the surface from the flammability and the need for flame retardants. flame; char promoters that protect the surfaces by Such chemicals were first added to TV enclosures the formation of a carbonaceous layer; and in the mid-1970s to meet UL 1410, which intumescent coatings, which swell to form a barrier protected against internally-initiated fires 12961. some distance from the polymer surface. The likelihood of such fires was far greater at that Reactive flame retardants that are bonded to time with the very high voltages required by early the substrate are safer substitutes than additive cathode ray tube technology. Today's technology chemicals that are not bonded and can migrate out eliminates this hazard. High voltages are now into the environment. Tetrabromobisphenol A, the contained in the ballast of fluorescent lamps that most commonly used flame retardant, is found backlight the LCD display /297/ or within the bonded to the substrate inside electronics to protect individual cells of a plasma display /298/. The against internal fires. The use of reactive TBBPA voltages are so low that arcing is not a potential inside electronics should present a lower health and hazard. environmental hazard than TBBPA used as an This new technology also eliminates such additive flame retardant in the plastic housing of hazards as internal heat sources like the tube electronics. Still, brominated dioxins and furans are filaments, rectification and plate voltages that produced upon combustion of electronics could reach as high as several hundred volts, and containing TBPPA. A life cycle approach should related high currents that were required in the be used in evaluating replacement chemicals.

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9. DISCUSSION: POLICY IMPLICATIONS When flammability regulations for consumer AND SUGGESTIONS products were originally introduced in the 1970s, the health and environmental impacts of the Since the introduction of halogenated flame chemicals being used to meet them were not well- retardants in the 1970s, many hundreds of peer- known or considered. Nevertheless, the use of reviewed scientific papers have documented the these chemicals increased 50% between 2005 and environmental persistence and toxicity of these 2008 ß/, despite a growing knowledge of the compounds in animals and humans. After decades adverse impacts of halogenated flame retardants of high-volume use, pounds of halogenated flame on health and the environment. Alternative retardants can be found in consumer products methods for achieving fire safety without the use inside a typical home, school, or office. These of organohalogen flame retardants are available semi-volatile chemicals leach out of products into for most applications and should be considered dust, which is a major exposure route for humans when drafting new flammability standards. and animals /48/. All 21 chemicals banned by the Stockholm 9.1 Reevaluating California TBI 17 to Maintain Convention are organohalogens, and several are Fire Safety while Reducing the Use of halogenated flame retardants or their degradation Halogenated Flame Retardants products. In the U.S., human levels of the banned flame retardant pentaBDE are approaching those After 35 years, California TBI 17 has not been that are known to cause harm in animals /85/. Of proven to have increased fire safety. As great concern is the increasing number of studies previously discussed, however, pentaBDE and finding adverse health impacts associated with other flame retardants used to meet the standard exposure, such as reduced IQ scores in children are toxic and/or global pollutants. Thus, TBI 17 and increased time to conception in humans. Of should be revised to consider the health and further concern is the lack of necessary health environmental impacts of the chemicals used to information on PBDE replacements to determine meet it. Furniture design, smolder resistant fabric, if they are an improvement. denser foam, and fire resistant barriers around the The fire safety benefit of using halogenated foam can all contribute to increasing fire safety chemicals has not been well documented. with reduced toxicity. A revised TBI 17 could be Currently, fire deaths are decreasing. One could modeled after the CPSC staff draft furniture argue that the use of halogenated flame retardants standard for fabric, which maintains fire safety in consumer products is contributing to this without the use of flame retardants in decrease; yet, no data exist to demonstrate a fire polyurethane foam /265/. safety benefit from incorporating these chemicals. For example, according to NFPA data, states 9.2 Reconsideration of Small Open-Flame without a furniture flammability requirement Requirements for TV Sets in the EU and show a similar decrease in fire deaths as that of the U.S. California, which uniquely follows TBI 17 /291/. More likely is that the decrease in smoking, the A new EU standard for small open-flame increased use of smoke detectors and sprinklers, requirements for TVs enclosures (CENELEC EN improved electrical product safely standards, a 60065) and the current U.S. standard (UL60065) decrease in open fires and other lifestyle changes are met with flame retardant chemicals at levels have been the major contributors to reduced fire up to 30% by weight. These standards should be deaths across the U.S. evaluated for their fire safety benefit as well as

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 288 S. SHAW ET AL. their effects on health, environment, and care, so that the two sorts of polystyrene could be recycling. used appropriately. If building codes do not Currently, in the U.S., TV sets are required to currently allow this exception, a reduced use of have fire-retardant enclosures due to internally HBCD should be proposed. New, safer flame initiated ignition threats rather than externally retardants should be developed for use with initiated ignition threats. After the earlier polystyrene as well as less flammable alternatives transition from vacuum tube to solid state to plastic insulation materials. technology occurred, cathode ray tube TVs are becoming nearly extinct and are being replaced by 9.4 Life Cycle Analysis before Using Flame LCD panel and plasma display-based technology. Retardants The new technology has resulted in reduced and contained high voltage, lower power, and Given the documented adverse health effects shallower products. New TV sets cannot function of halogenated flame retardants in consumer as shelves, nor can materials such as candles products, the authors believe that independent easily be placed to lean against them. The set can researchers at institutions such as the NAS, NIST, also be wall-mounted, further reducing an already CPSC and/or universities should perform in-depth low potential for candle ignition. Television analyses of the fire safety benefits from the use of manufacturers could further redesign their flame retardants, as well as the health and products to eliminate the use of fire retardants in environmental costs. A life-cycle approach should the enclosures without compromising fire safety. be used, with emphasis on end-of-life issues, including the health and safety of workers, those 9.3 Production of Two Kinds of Polystyrene, living near chemical production facilities, and the With and Without Added HBCD general population, as well as ecological effects. For example, new small open-flame and One option for reducing the use of HBCD- candle-ignition standards for electronic housings treated polystyrene would be to remove the flame continue to be proposed despite an undocumented retardant for applications in which it is not fire safety benefit. If implemented, such standards needed. Currently, all polystyrene sold as building could result in the addition of large volumes of insulation carries at least a Class Β designation flame retarding chemicals to the plastic enclosures for flame-spread and smoke development. This of electronics worldwide each year, thereby classification is required for above-grade making recycling more difficult and expensive. A applications, and many believe that the Class Β detailed life-cycle analysis of the impact of such category is a universal requirement. The candle standards should be conducted with International Residential Code and the significant input from the health and environmental International Building Code, however, appear to effects communities, as well as the fire and exempt foam insulation that will be separated combustion communities. This life-cycle analysis from the building interior by at least one inch (25 could determine the overall impact of the proposed mm) of masonry or concrete /299/. In below- standard to the entire envelope of materials and grade, exterior applications, foam insulation may systems. In addition, such an analysis could foster also be exempt from flammability standards. communications among the health, environment, Manufacturers could offer non-treated and fire safety communities and could serve as a polystyrene insulation for such below-grade platform for additional input from labor unions, installations. Polystyrene without flame retardants occupational health organizations, water quality, should cost less, but would require labeling and and other environmental and community bodies.

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9.5 Reducing Exposure, Legacy Problems, and 9.6 Chemical Regulation Product End-of-Life for Flame Retardants Several flame retardant chemicals have been PentaBDE and octaBDE have not been produced and used with high levels of human produced in the U.S. since 2004, yet millions of exposure before evaluations of their health and pounds of these and other toxic or untested flame environmental impact have been conducted. As retardants mixed with foam and plastic are in the literature has grown on the adverse impact of consumer products. These flame retardants are such chemicals, a more systematic approach to semi-volatile and escape from products into dust. their testing and regulation is needed. Such a Hand washing, vacuuming with a HEPA filter, policy is being initiated in Europe through the and wet mopping should reduce individual Registration, Evaluation, and Authorization of exposuie to dust and the flame retardants it Chemicals initiative, or REACH. Current U.S. contains. Further research is needed on pathways Congressional efforts, supported by a wide of exposure and the effectiveness of dust variety of non-government organizations (NGOs), reduction strategies. users of chemicals, and other stakeholders to The three current main end-of-life options for revise the Toxic Substance and Control Act halogenated flame retardants mixed with foam or (TSCA) should contribute to a sound and plastic are all problematic because: (a) combustion comprehensive U.S. chemicals policy. This policy can create dioxins and furans; (b) the chemicals could include provisions such as the following: can leach from landfills into the environment and • Health and environmental data required end up in the food supply; and (c) recycling can before the use of chemicals; contaminate the non-flame retarded plastic stream • Disclosure and labeling of which chemicals with the chemicals and their combustion products. are in products; PBDE-containing products will remain a reservoir • Questioning replacement chemicals that are for releases for many years to come. According to nearly identical to regulated toxics; the furniture industry, the average lifetime for • Life-cycle analyses, including the impact on foam-containing household furniture is 30 years, workers and the environment of chemical suggesting that only a fraction of the total PBDEs production, as well as end-of-life leaching used in furniture has reached the outdoor and combustion products; environment. The indoor reservoir of PBDEs has • Persistent, bioaccumulative, and/or toxic been termed an environmental "time bomb" /300/. chemicals with high potential for human One prediction is that the main exposure route for exposure, such as flame retardants in humans will eventually shift from the indoor consumer products, should be prioritized for environment to the food supply /300/. evaluation and regulation. As pentaBDE-treated furniture continues to be replaced and the older, used furniture is purchased by low-income households, PBDE 10. CONCLUSIONS exposure could become an environmental justice issue. Already one study found that girls of color In the U.S., neither federal nor state had higher PBDE levels than Caucasian girls environmental protection agencies have sufficient /301/. Research is urgently needed to determine authority to require that manufacturers ensure that responsible methods of identifying and disposing their flame retardant chemicals are safe for human of products containing PBDEs and other health. Thus, in consumer products a series of halogenated flame retardants. brominated and chlorinated flame retardant

Brought to you by | Johns Hopkins University Authenticated Download Date | 6/9/15 4:12 PM 290 S. SHAW ET AL. chemicals continue to be used without thorough flammability standards, as well as possible consideration Of their possible adverse effects. modifications to current standards. The PBBs, PCBs, brominated tris, Halon, asbestos, and uncontrolled burning of products containing PBDEs are flame retardant materials that only after organohalogens should not be allowed because extensive use were found to have serious long-term byproducts such as brominated and chlorinated negative effects on human health and/or the dioxins and furans are often more toxic and environment. Moreover, many of the current persistent than the parent compounds. Landfills replacement chemicals are proprietary mixtures, with major containment analogous to those protected by confidential business information required for radioactive waste constitute one regulations, whereas others lack adequate toxicity possible solution. Complete destruction in waste- information, making difficult the accurate to-energy facilities, without the formation of assessment of their potential hazards. Producers significant quantities of brominated dioxins or should be required to provide health and toxicity furans, is another possible scenario. More data about flame retardants and replacement research is urgently needed to develop and refine chemicals before such materials are marketed. sustainable end-of-life solutions. Although pentaBDE is no longer being This paper raises questions about the validity manufactured, a substantial fraction of the of certain flammability tests that purport to show pentaBDE commercial mixtures ever produced is a benefit from flame retardants in preventing still present in furniture, carpet padding, auto- ignition or slowing fire growth. An additional mobiles, and seating in mass transportation. The study, such as a definitive review of the previous identification and responsible disposal of research, possibly accompanied by modeling, is pentaBDE-treated products is essential to prevent needed. The authors question the use of halo- its future dispersal into the environment and the genated flame retardants that lack a demonstrated food supply. Already, PBDEs are widespread fire safety benefit and that have a high potential contaminants in remote areas, such as the polar for adverse effects on health and the environment. regions and the deep oceans, and are considered an For the future, flammability standards for environmental 'time bomb' because the com- manufactured household and commercial products pounds continue to migrate from indoor reservoirs could be designed to be met without added into the environment /9,300/. Furniture, electronics, chemicals. Flame retardant chemicals can pose a and other products containing PBDEs must be potentially greater hazard than the risk from the identified and disposed of responsibly. The recent fires they are supposed to prevent. Reducing the listing of pentaBDE and octaBDE as POPs under use of toxic and untested halogenated flame the Stockholm Convention should help with the retardants will protect human and animal health tracking and phasing out of these chemicals from and the global environment. Decision-makers the global recycling flow /302/. Doing so will should use peer-reviewed science to evaluate the prevent the further PBDE contamination of food fire safety benefits as well as the health and webs and human tissues worldwide. environmental risks before promulgating new Firemaster 550® and TDCPP, two commonly requirements leading to the use of flame retardant used pentaBDE replacements produced to meet chemicals. California standard TBI 17, appear to share some of the persistence and toxic qualities of ACKNOWLEDGMENTS pentaBDE. Policy makers should consider the potential impact of contamination by pentaBDE The authors wish to thank many colleagues and its replacements as they consider new whose expertise in science and policy has informed

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