Minnesota Pollution Control Agency Decabromodiphenyl Ether (Deca-BDE) A Report to the Minnesota Legislature January 15, 2008 Azra Kovacevic and Cathy O’Dell of the Minnesota Pollution Control Agency (MPCA) Environmental Analysis and Outcomes Division prepared this report, with advice and assistance from Laura Solem, Summer Streets, Paul Hoff and Marvin Hora. The MPCA would also like to thank Carl Herbrandson, Patricia McCann and Pamela Shubat of the Minnesota Department of Health for their consultation and review assistance during preparation of this report. Cost to prepare this report: Total staff hours: 530 Salary and fringe costs: $20,998.01 Production costs: $201.00 An electronic version of this report can be found on the MPCA web site at: Legislative Reports - Minnesota Pollution Control Agency This report can be made available in other formats, including Braille, large type or audiotape upon request. This report is printed on paper with at least 30 percent post-consumer recycled paper. i TABLE OF CONTENTS Page EXECUTIVE SUMMARY .......................................................................................................... 1 INTRODUCTION ........................................................................................................................ 4 ABOUT FLAME RETARDANTS............................................................................................... 6 USES OF DECA-BDE ................................................................................................................. 8 FIRE SAFETY AND FLAME RETARDANTS ........................................................................ 10 Fire Safety Standards for Electronics ................................................................................... 10 Fire Safety Standards for Textiles......................................................................................... 11 Fire Safety Standards for Transportation.............................................................................. 11 PBDES, THE ENVIRONMENT AND HUMAN HEALTH (EMPHASIS ON DECA-BDE).. 12 Chemistry of PBDEs............................................................................................................. 12 PBDEs and the Environment ................................................................................................ 14 PBDEs and Human Health.................................................................................................... 15 Summary of Concerns about PBDEs and Deca-BDE........................................................... 21 FINDINGS AND RECOMMENDATIONS ON PBDES AND DECA-BDE BY U.S. STATES AND THE EUROPEAN UNION, AND ADOPTED REGULATIONS.................................... 24 Findings and Recommendations on PBDEs and Deca-BDE by US States, the European Union and Canada………………………………………………………………………..... 24 Regulations on PBDEs…………………………………………………………………….. 25 ALTERNATIVES TO DECA-BDE........................................................................................... 29 Alternative Chemical Flame Retardants ............................................................................... 29 Voluntary Market Changes................................................................................................... 33 SUMMARY OF KEY FINDINGS............................................................................................. 35 REFERENCES ........................................................................................................................... 38 APPENDICES lrp-ei-2sy08 i LISTS OF FIGURES, TABLES AND APPENDICES Figures Page Figure 1: General Structure of PBDEs........................................................................................ 12 Figure 2: Two Congeners of Penta-BDE.................................................................................... 13 Figure 3: Deca-BDE (a.k.a. BDE-209)....................................................................................... 13 Figure 4: Temporal Trends of PBDE Concentrations in Human Tissues in US and Europe ..... 16 Figure 5: PBDE Concentrations Measured in Blood Serum of 35 Volunteers from Alaska, Connecticut, Illinois, Massachusetts, Michigan, Minnesota, and New York............................. 17 Figure 6: PBDE Dietary Intake of U.S. Population by Age and Food Group ............................ 18 Figure 7: Trends of PBDEs in Human Milk ............................................................................... 22 Tables Page Table 1: BFR Volume Estimates in 2001 and 2003 in Metric Tons (MT)................................... 7 Table 2: Resin Systems for Electronic Enclosures ....................................................................... 9 Table 3: General composition of PBDE Commercial Products.................................................. 13 Table 4: Lowest Observed Adverse Effect Levels (LOAEL) in Deca-BDE Animal Toxicity Studies......................................................................................................................................... 20 Table 5: Non-Cancer Oral Reference Dose (RfD) for Deca-BDE ............................................. 21 Table 6: Cancer/Oral Risk for Deca-BDE .................................................................................. 21 Table 7: Estimated Daily PBDE Intake from Food (mg/kg/day) ............................................... 23 Table 8: States with Regulations that Place Limitations on PBDEs........................................... 26 Table 9: States with Proposed Legislation on PBDEs in 2007................................................... 26 Table 10: List of Commonly Cited Non-Halogenated Alternatives to Deca-BDE .................... 31 Table 11: List of Commonly Cited Halogenated Alternatives to Deca-BDE............................. 32 Appendices A. Key Stakeholders B. 2005 MPCA Background Paper on PBDEs (web link) C. Materials and Products Containing PBDEs D. Available Information on PBDEs in the Environment (emphasizing Deca-BDE) E. Available Information on PBDEs and Human Health (emphasizing Deca-BDE F. Release of PBDEs to the Environment (emphasizing Deca-BDE) G. Available Information about Proposed Alternatives to Deca-BDE H. Executive Summaries from PBDE Reviews Undertaken by Other States and the European Union ii ACRONYMS AND ABBREVIATIONS ABS Acrylonitrile-butadiene-styrene ACS American Chemical Society ATO Antimony oxide ATSDR Agency for Toxic Substances and Disease Registry BAPP, BPADP, Bisphenol A diphosphate BDP BFR Brominated Flame Retardant BFRIP Brominated Flame Retardant Industry Panel BSEF Bromine Science and Environmental Forum CA California CA BHFTI State of California Bureau of Home Furnishings and Thermal Insulation CEPA Canada Environmental Protection Act CFR Chlorinated Flame Retardants CPCS Consumer Product Safety Commission DCP Diphenyl cresol phosphate Deca-BDE Decabromodiphenyl ether EBTPI Ethylene bistetrabromo phthalimide EPA Environmental Protection Agency EPDM Ethylene-propylene terpolymer EU European Union FAA Federal Aviation Authority FMVSS Federal Motor Vehicle Safety Standards FR Flame Retardant HBCD Hexabromocyclododecane Hepta-BDE Heptabromodiphenyl Ether Hexa-BDE Hexabromodiphenyl Ether HI Hawaii HIPS High-impact polystyrene HIPS/PPO High impact polystyrene/Polyphenylene ether IL Illinois IRIS Integrated Risk Information System IUPAC International Union for Pure and Applied Chemistry LCD Liquid Crystal Desplay LOAEL Loves Observed Adverse Effect Level MD Maryland ME Maine MI Michigan MN Minnesota MPCA Minnesota Pollution Control Agency NEC National Electric Code NFPA National Fire Protection Association NHTSA National Highway Traffic Safety Administration iii NOAEL No Observed Adverse Effect Level Nona-BDE Nonabromdiphenyl Ether NY New York Octa-BDE Octabromodiphenyl ether OR Oregon P,B,T Persistent, Bioaccumulative, Toxic PA Polyamide PBB Polybrominated biphenyls PBDE Poly-brominated diphenyl ethers PBT Polybutylene terephthalate PC/ABS Polycarbonate/Acrylonitrile-butadiene-styrene PC/PS Polycarbonate/Polystyrene PCB Polychlorinated biphenyls Penta-BDE Pentabromodiphenyl ether PP Polypropylene PPE Polypropylene ether PVC Polyvinyl chloride RDP Resorcinol bis diphenylphosphate RfD Reference Dose RI Rhode Island RoHS Restriction of Hazardous Substances (EU) SARA Superfund Amendments and Reauthorization Act SNUR Significant New Use Rule TBBPA Tetrabromobisphenol A Tetra-BDE Tetrabromodiphenyl Ether TRI Toxic Release Inventory TSCA Toxic Substances Control Act TTP Triphenyl phosphate UL Underwriter Laboratories USFA United States Fire Association VCCEP Voluntary Children’s Chemical Evaluation Program VECAP Voluntary Emissions Control Action Program VECAP NAPR VECAP North American Progress Report WA Washington WEEE Waste Electrical and Electronic Equipment WHO World Health Organization iv EXECUTIVE SUMMARY Flame retardants are chemicals that are added to a variety of consumer and commercial products to improve their resistance to fire. Brominated flame retardants (BFRs) are the highest use flame retardants globally because they are both inexpensive and highly efficient. A class of BFRs known as polybrominated diphenyl ethers (PBDEs) has received increasing attention from scientists and policymakers. This attention is due to the high rate of use of PBDEs and their increasing concentration in the environment, in wildlife, and in people. Since PBDEs were introduced in the 1960s, PBDE concentrations in human tissue have increased exponentially, with concentrations doubling