1 Identification of Flame Retardants in Polyurethane Foam Collected 1 from Baby Products 2 3 Heather M. Stapleton 1 , Susan Klosterhaus 2 , Alex Keller 1 , P. Lee Ferguson 1 , Saskia van 4 Bergen 3 , Ellen Cooper 1 , Thomas F. Webster 4 and Arlene Blum 5 5 6 1- Nicholas School of the Environment, Duke University, Durham, NC, USA; 7 2- San Francisco Estuary Institute, Oakland, CA, USA; 8 3- East Bay Municipal Utility District, Oakland, CA, USA; 9 4-Department of Environmental Health, Boston University School of Public Health, Boston, MA, 10 USA; 11 5- Department of Chemistry, University of California, and Green Science Policy Institute, 12 Berkeley, CA, USA; 13 14 *corresponding author: [email protected]15 16 Key Words: Flame Retardants, Polyurethane Foam, XRF, PBDEs, TDCPP, Firemaster 17 18 19 ABSTRACT 20 21 With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in 22 polyurethane foam to meet flammability standards. However, insufficient information is 23 available on the identity of the flame retardants currently in use. Baby products containing 24 polyurethane foam must meet California state furniture flammability standards, which likely 25 affects use of flame retardants in baby products throughout the U.S. However, it is unclear which 26 products contain flame retardants, and at what concentrations. In this study we surveyed baby 27 products containing polyurethane foam to investigate how often flame retardants were used in 28 these products. Information on when the products were purchased and whether they contained a 29 label indicating that the product meets requirements for a California flammability standard were 30 recorded. When possible, we identified the flame retardants being used, and their concentrations 31 in the foam. Foam samples collected from 101 commonly used baby products were analyzed. 32 Eighty samples contained an identifiable flame retardant additive and all but one of these was 33 either chlorinated or brominated. The most common flame retardant detected was tris (1,3- 34
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Identification of Flame Retardants in Polyurethane Foam Collected 1 from Baby Products 2
3 Heather M. Stapleton 1, Susan Klosterhaus 2, Alex Keller 1, P. Lee Ferguson1, Saskia van 4 Bergen3, Ellen Cooper 1, Thomas F. Webster4 and Arlene Blum 5 5 6 1- Nicholas School of the Environment, Duke University, Durham, NC, USA; 7 2- San Francisco Estuary Institute, Oakland, CA, USA; 8 3- East Bay Municipal Utility District, Oakland, CA, USA; 9 4-Department of Environmental Health, Boston University School of Public Health, Boston, MA, 10 USA; 11 5- Department of Chemistry, University of California, and Green Science Policy Institute, 12 Berkeley, CA, USA; 13 14 *corresponding author: [email protected] 15 16 Key Words: Flame Retardants, Polyurethane Foam, XRF, PBDEs, TDCPP, Firemaster 17 18 19 ABSTRACT 20 21
With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in 22
polyurethane foam to meet flammability standards. However, insufficient information is 23
available on the identity of the flame retardants currently in use. Baby products containing 24
polyurethane foam must meet California state furniture flammability standards, which likely 25
affects use of flame retardants in baby products throughout the U.S. However, it is unclear which 26
products contain flame retardants, and at what concentrations. In this study we surveyed baby 27
products containing polyurethane foam to investigate how often flame retardants were used in 28
these products. Information on when the products were purchased and whether they contained a 29
label indicating that the product meets requirements for a California flammability standard were 30
recorded. When possible, we identified the flame retardants being used, and their concentrations 31
in the foam. Foam samples collected from 101 commonly used baby products were analyzed. 32
Eighty samples contained an identifiable flame retardant additive and all but one of these was 33
either chlorinated or brominated. The most common flame retardant detected was tris (1,3-34
2
dichloroisopropyl) phosphate (TDCPP; detection frequency 36%), followed by components 35
typically found in the Firemaster®550 commercial mixture (detection frequency 17%). Five 36
460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 Figure 2. Identification of a previously unreported flame retardant, 2,2-bis(chloromethyl)propane-1,3-diyl tetrakis(1-485 chloropropan-2-yl) bis(phosphate) “U-OPFR”, and TCPP, in a sample from an infant changing table pad by LTQ-Orbitrap 486 high resolution mass spectrometry. Inset demonstrates a comparison of the observed and predicted high-resolution mass 487 spectra (MS) for U-OPFR. 488 489
529 Figure 3. Correlation between GC/MS and XRF measured bromine (A) and chlorine (B). 530 531
XRF
Mea
sure
men
t (%
Hal
ogen
)
0
1
2
3
4
5
6
GC/EI-MS (% Halogen by Weight)0 2 4 6
0
5
10
15
20
● - FM 550▲ - PentaBDE
r = 0.90p <0.0001
r = 0.15p = 0.33
A) Bromine
B) Chlorine
▲TCPP♦ TCEP● TDCPP■Mixed Cl OPFRs
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Table 1. Description of baby products included in this study and the flame retardants detected in these products at levels of 532 more than 1 mg/g foam. 533
534 a- The brominated compounds present in FM 550. All samples containing TBB/TBPH also contained TPP. 535 b- Infers either no detection of chemicals or peaks were unidentifiable. 536
N/M – indicates not measured due to absence of calibration standard. 537
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References 538 1. Tullo, A., Great Lakes to phase out flame retardants. Chemical & Engineering News 539 2003, 81, (45), 13-13. 540 2. EU, Directive 2003/11/EC of the European Parliament and of the Council. In 541 Official Journal of the European Union: 2001; Vol. Directive 76/769/EEC, pp 45-46. 542 3. Stapleton, H. M.; Klosterhaus, S.; Eagle, S.; Fuh, J.; Meeker, J. D.; Blum, A.; 543 Webster, T. F., Detection of Organophosphate Flame Retardants in Furniture Foam and 544 US House Dust. Environmental Science & Technology 2009, 43, (19), 7490-7495. 545 4. Stapleton, H. M.; Allen, J. G.; Kelly, S. M.; Konstantinov, A.; Klosterhaus, S.; 546 Watkins, D.; McClean, M. D.; Webster, T. F., Alternate and new brominated flame 547 retardants detected in US house dust. Environmental Science & Technology 2008, 42, (18), 548 6910-6916. 549 5. Requirements, test procedure and apparatus for testing the flame retardance of 550 resilient filling materials used in upholstered furniture. . In California Department of 551 Consumer Affairs: North Highlands, CA, 2000. 552 6. Weil, E. D.; Levchik, S. V., Commercial flame retardancy of polyurethanes. Journal 553 of Fire Sciences 2004, 22, (3), 183-210. 554 7. Hites, R. A., Polybrominated diphenyl ethers in the environment and in people: A 555 meta-analysis of concentrations. Environmental Science & Technology 2004, 38, (4), 945-956. 556 8. Hale, R. C.; Alaee, M.; Manchester-Neesvig, J. B.; Stapleton, H. M.; Ikonomou, M. 557 G., Polybrominated diphenyl ether flame retardants in the North American environment. 558 Environment International 2003, 29, (6), 771-779. 559 9. Chen, S. J.; Ma, Y. J.; Wang, J.; Chen, D.; Luo, X. J.; Mai, B. X., Brominated 560 Flame Retardants in Children's Toys: Concentration, Composition, and Children's 561 Exposure and Risk Assessment. Environmental Science & Technology 2009, 43, (11), 4200-562 4206. 563 10. Lorber, M., Exposure of Americans to polybrominated diphenyl ethers. Journal of 564 Exposure Science and Environmental Epidemiology 2008, 18, (1), 2-19. 565 11. Wu, N.; Herrmann, T.; Paepke, O.; Tickner, J.; Hale, R.; Harvey, E.; La Guardia, 566 M.; McClean, M. D.; Webster, T. F., Human exposure to PBDEs: Associations of PBDE 567 body burdens with food consumption and house dust concentrations. Environmental 568 Science & Technology 2007, 41, (5), 1584-1589. 569 12. Allen, J. G.; McClean, M. D.; Stapleton, H. M.; Webstert, T. F., Linking PBDEs in 570 house dust to consumer products using X-ray fluorescence. Environmental Science & 571 Technology 2008, 42, (11), 4222-4228. 572 13. Harrad, S.; de Wit, C. A.; Abdallah, M. A. E.; Bergh, C.; Bjorklund, J. A.; Covaci, 573 A.; Darnerud, P. O.; De Boer, J.; Diamond, M. L.; Huber, S.; Leonards, P.; Mandalakis, 574 M.; Ostman, C.; Haug, L. S.; Thomsen, C.; Webster, T. F., Indoor Contamination with 575 Hexabromocyclododecanes, Polybrominated Diphenyl Ethers, and Perfluoralkyl 576 Compounds: An Important Exposure Pathway for People? Environmental Science & 577 Technology 2010, 44, (9), 3221-3231. 578 14. Chemtura Material Safety Data Sheet for Firemaster 550; 2006; pp 1-8. 579 15. EPA, Furniture Flame Retardancy Partnership: Environmental Profiles of 580 Chemical Flame Retardant Alternatives. In EPA 742-R-05-002A.: 2005. 581
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16. EC, Risk Assessment Report on 2,2-bis(chloromethyl)trimethylene bis[bis(2-582 chloroethyl)phosphate] (V6). In Risks, S. C. o. H. a. E., Ed. European Comission: Brussels, 583 2007. 584 17. EPA, U., Inventory Update Reporting. In 2010. 585 18. Mack, A. G.; Chai, Z. Phosphate-Containing Flame Retardants. 2008. 586 19. Hale, R. C.; La Guardia, M. J.; Harvey, E.; Mainor, T. M., Potential role of fire 587 retardant-treated polyurethane foam as a source of brominated diphenyl ethers to the US 588 environment. Chemosphere 2002, 46, (5), 729-735. 589 20. Babich, M. A., CPSC Staff Preliminary Risk Assessment of Flame Retardant (FR) 590 Chemicals in Upholstered Furniture Foam. In Commission, U. C. P. S., Ed. USCPSC: 591 2006; Vol. Bethesda, MD 20814, p 129. 592 21. Weschler, C. J.; Nazaroff, W. W., Semivolatile organic compounds in indoor 593 environments. Atmospheric Environment 2008, 42, (40), 9018-9040. 594 22. Hughes, M. F.; Edwards, B. C.; Mitchell, C. T.; Bhooshan, B., In vitro dermal 595 absorption of flame retardant chemicals. Food and Chemical Toxicology 2001, 39, (12), 596 1263-1270. 597 23. Blum, A.; Gold, M. D.; Ames, B. N.; Kenyon, C.; Jones, F. R.; Hett, E. A.; 598 Dougherty, R. C.; Horning, E. C.; Dzidic, I.; Carroll, D. I.; Stillwell, R. N.; Thenot, J. P., 599 Children Absorb Tris-Bp Flame-Retardant from Sleepwear - Urine Contains Mutagenic 600 Metabolite, 2,3-Dibromopropanol. Science 1978, 201, (4360), 1020-1023. 601 24. Gold, M. D.; Blum, A.; Ames, B. N., Another Flame-Retardant, Tris-(1,3-Dichloro-602 2-Propyl)-Phosphate, and Its Expected Metabolites Are Mutagens. Science 1978, 200, 603 (4343), 785-787. 604 25. NRC, Toxicological Risks of Selected Flame-Retardant Chemicals. National Academy 605 Press: Washington DC, 2000. 606 26. Dishaw, L. V.; Powers, C. M.; Ryde, I. T.; Roberts, S. C.; Seidler, F. J.; Slotkin, T. 607 A.; Stapleton, H. M., Is the PentaBDE Replacement, Tris (1,3-dichloro-2-propyl) 608 Phosphate (TDCPP), a Developmental Neurotoxicant? Studies in PC12 Cells. Toxicology 609 and Applied Pharmacology 2011, doi: 10.1016/j.taap.2011.02.005. 610 27. Meeker, J. D.; Stapleton, H. M., House Dust Concentrations of Organophosphate 611 Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. 612 Environmental Health Perspectives 2010, 118, (3), 318-323. 613 28. 793/93, C. R. E. N. Tris (2-chloroethyl)phosphate, TCEP, Summary Risk Assessment 614 Report; Federal Institute for Occupational Safety and Health: Dormund, Germany, 2008. 615 616 617