Flame Retardant Contamination at Fire Scenes

Barbara M. Alexander, Ph.D., PE University of Cincinnati Department of Environmental Health October 10, 2014

Contact: NIOSH/DART, 1090 Tusculum Ave., Cincinnati, OH 45226 BAlexander@cdc.gov

Flame Retardant Chemicals in the News

• Chicago Tribune - 8/29/14 • WGN-TV - 8/5/14 •  Philly.com – 8/17/14 • Boulder Weekly – 8/28/14 • Bangor Daily News – 8/13/14 •  The Missoulian – 8/26/14 •  The Oregonian – 8/26/14 • Saskatoon Star-Phoenix – 8/28/14

NY Times Blog1 – 7/8/14 •  Flame retardant contamination is found

worldwide: ▫  Antarctic penguins ▫  Arctic killer whales ▫  Spanish bird eggs ▫  Canadian fish ▫  Honey from Brazil, Morocco, Spain and Portugal ▫  Baby products ▫  Camping tents ▫  Airplanes, trains and automobiles

How did we get here? •  1953 – Federal Flammable Fabrics Act ▫  1967 – Amended to include interior furnishings. ▫  Requires lighted cigarette test of mattresses. ▫  2006 – Incorporated open flame test.

•  1972 – California requires all upholstered furniture to be flame retardant.

•  1972 – Federal Motor Vehicle Safety Standard 302 (49 CFR 571.302) – Flammability of Interior Materials – requires open flame test of materials (amended most recently in 1998).

•  1975 – Federal Standards for the Flammability of Children’s Sleepwear (amended in 1996).

•  1975 – California Technical Bulletin 117 (TB 117) becomes law. ▫  Included open flame test and smoldering ignition test for cushion filler

materials. •  12/31/13 – Open flame test removed from TB 117.

Firefighter Health

• Sudden cardiac death is the number one cause of on-duty death. • An elevated risk of certain cancers is

recognized. • Chemical exposures may be to blame for

adverse health effects.

California Firefighter Study2

•  Included 12 San Francisco firefighters. •  Had responded to a fire within the previous 24

hours. •  Blood serum samples obtained. •  Polybrominated diphenyl ether (PBDE) levels 2 to

3 times the level in the general US population measured. ▫  PBDE-28, -47, -100 and -153 in 100% of samples. ▫  PBDE-99 in 92% of samples. ▫  PBDE-209 in 67% of samples.

•  Tetrabromobisphenol A was not detected.

Polybrominated Diphenyl Ethers (PBDEs) • Congeners (209) – numbered according to

the number and location of bromine atoms. • Mixtures used as flame retardants.

http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~9i4x4C:3

Polybrominated Diphenyl Ethers (PBDEs)3

•  Flame-retardant chemicals •  Persistent in the environment • Adverse health effects include

neurotoxicity and endocrine disruption • Suspected of thyroid toxicity and

carcinogenicity.

http://toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~9i4x4C:3

PentaBDE4,5

• Made up of: ▫  50 – 60% penta-brominated (largely PBDE-99) ▫  24 – 38% tetra-brominated (largely PBDE-47) ▫  4 – 8% hexa-brominated (largely PBDE-153) •  Used in polyurethane foam. •  Banned in California in 2003, EU in 2004, and

no longer manufactured in the US by 2005.

OctaBDE6,7 •  Made up of: ▫  ≤0.5% pentabrominated ▫  ≤12% hexabrominated ▫  ≤45% heptabrominated ▫  ≤33% octabrominated ▫  ≤10% nonabrominated ▫  ≤0.7% decabrominated •  Used in plastic housings for office equipment. •  Banned in the EU in 2004, no longer

manufactured in the US, EU or Pacific Rim since 2004.

DecaBDE7,8

• > 97% PBDE-209. • Used in electrical and electronic

equipment, and as a backing in textiles. •  In late 2009, the two US producers of

decaBDE agreed to phase out production, importation and sales. • All US uses of decaBDE were to end at the

end of 2013.

Alternatives to DecaBDE • 1/2014 – US EPA’s “An Alternatives

Assessment for the Flame Retardant Decabromodiphenyl Ether (DecaBDE)”9 is published. ▫  Twenty-nine alternatives assessed. ▫  Most flame retardants must be stable, and

so have high or very high environmental persistence. ▫  No one alternative is a perfect substitute in

all applications.

What Flame Retardants will Replace PBDEs?

•  Phosphate-based flame retardants • Brominated flame retardants

Current Study • Obtained samples of unused and used

firefighter personal protective gear.

• Samples were sent to an analytical lab ▫  Analyzed for the presence of 5 different

flame retardants ▫  Possible replacements for PBDEs.

Phosphate-Based Flame Retardants •  In use for over 150 years. •  In this study: ▫  Triphenyl Phosphate (TPP) ▫  Tris(1,3-Dichloro-2-Propyl) Phosphate

(TDCPP) ▫  Tris(2-Chloroisopropyl) Phosphate (TCPP)

Firemaster 550 (FM 550)10

• Mixture of brominated and phosphate-based flame retardants, including 3 of the study chemicals: ▫  2-Ethylhexyl-2,3,4,5-Tetrabromobenzoate

(TBB) ▫  Bis-(2-Ethylhexyl) Tetrabromophthalate

(TBPH) ▫  Triphenyl Phosphate (TPP)

Triphenyl Phosphate (TPP)11,12

• Used in PVC. • Health effects: ▫  Causes contact dermatitis ▫  Effects on immunological system ▫  Possible neurotoxicity ▫  Significant estrogenic effect

Tris(1,3-Dichloro-2-Propyl) Phosphate (TDCPP)11 - 15 •  Added to resins, latexes and foams. •  In recent studies, most commonly detected

flame retardant in foam samples from furniture and baby products. •  Health effects: ▫  Toxic on inhalation ▫  Skin irritant ▫  Neurotoxicity ▫  Estrogenic Effects ▫  Classified by the World Health Organization

(WHO) as a carcinogen

Tris(2-Chloroisopropyl) Phosphate (TCPP)11 • Often added to polyurethane foams and

electronic equipment • Health effects: ▫  Not acutely toxic ▫  Accumulates in the liver and kidneys ▫  Potentially carcinogenic

http://webbook.nist.gov/cgi/cbook.cgi?ID=13674-84-5&Units=SI

Firemaster 550 (FM 550)10 • Health effects (rat study): ▫  Endocrine disruptor ▫  Offspring had increased fatty tissue ▫  Early puberty in female offspring ▫  Behavioral effects

2-Ethylhexyl-2,3,4,5-Tetrabromobenzoate (TBB)16, 17 • Health Effects ▫  Slight anti-estrogenic effect ▫  Increased synthesis of cortisol and

aldosterone in testicular cells

Bis-(2-Ethylhexyl) Tetrabromophthalate (TBPH)17 -19 • Health effects ▫  Increased production of sex hormones by

testicular cells. ▫  Low toxicity observed in chicken embryos. ▫  Metabolite exposure causes: � Developmental effects �  Thyroid dysfunction �  Liver dysfunction � Obesity

Analysis for Flame Retardants

Analysis Method – Flame Retardants • Samples approximately 2” x 2”. • Analyzed by EPA method SW8270C. • Extracted with methylene chloride. •  Flame retardants quantitated using gas

chromatography/mass spectroscopy (GC/MS).

Flame Retardant Contamination in Firefighter Gloves (µg/g)

0

5

10

15

20

25

30

35

40

45

50

Unused Glove - Inner

Unused Glove - Middle

Unused Glove - Outer

Glove 1 - Inner Glove 1 - Middle Glove 1 - Outer

PBDE 28

PBDE 47

PBDE 100

PBDE 99

PBDE 153

PBDE 209

LOD range for 5 flame retardants

Flame Retardant Contamination in Firefighter Gloves (µg/g) – Comparison to Reported Levels in House Dust

0

5

10

15

20

25

30

35

40

45

50

Unused Glove - Inner

Unused Glove - Middle

Unused Glove - Outer

Glove 1 - Inner

Glove 1 - Middle

Glove 1 - Outer

House Dust - Stapleton et

al.12

Total PBDEs TBB

TBPH

TPP

TDCPP

TCPP

LOD range for 5 flame retardants

Flame Retardant Contamination in Firefighter Hoods (µg/g)

0

5

10

15

20

25

30

35

40

45

50

Unused Hood Hood 2* Hood 3*

PBDE 28

PBDE 47

PBDE 100

PBDE 99

PBDE 153

PBDE 209

LOD range for 5 flame retardants

Flame Retardant Contamination in Firefighter Hoods (µg/g) – Comparison to Reported Levels in House Dust

0

10

20

30

40

50

60

Unused Hood Hood 2* Hood 3* House Dust - Stapleton et al.12

Total PBDEs

TBB

TBPH

TPP

TDCPP

TCPP

LOD range for 5 flame retardants

Chromatograms of unused and used Firefighter Hoods

Comparison of Chromatogram of used Firefighter Hood to TCPP standard

Semivolatile contaminants were found previously on firefighter personal protective clothing20 - 22

•  Particulate matter •  Metals •  Polycyclic aromatic hydrocarbons (PAHs) ▫  Products of incomplete combustion ▫  Some are carcinogens •  Phthalates ▫  Plasticizers and additives in personal care products ▫  Range of adverse health effects

Photo by J. Keener, ©City of Prescott, http://www.cityofprescott.net/services/fire/photos.php?id=7

Decontamination of Firefighter Personal Protective Gear

• Covered by NFPA Standard 1851.23

• Spot cleaning or industrial washing machine only. • No home laundering. • No dry cleaning. • Drying by air or industrial machine. • * Only about 1/3 of fire departments have

extra sets of turnout gear.24

Conclusions •  No conclusion can be drawn about the levels of the

five flame retardants studied on firefighter personal protective clothing. •  Significant levels of PBDEs and other semivolatile

contaminants were found in previous investigations. •  Contaminants accumulate on personal protective

clothing with use. •  A rapid method for field decontamination of firefighter

personal protective gear would be a significant innovation. •  More toxicity testing of alternative flame retardants is

needed.

Future Research • Biological samples from firefighters should

be tested for the presence of metabolites of semivolatile contaminants. •  The contribution of dermal exposure

should be evaluated. • A rapid field decontamination method for

firefighters should be developed.

References 1.  Blum, D., Flame Retardants are Everywhere, New York Times. (2014),

available at http://well.blogs.nytimes.com/2014/07/01/flame-retardants-are-everywhere/ (accessed July 16, 2014; it also appeared in print in the New York edition on July 8, 2014).

2.  Shaw, S.D., Berger, M.L., Harris, J.H., Yun, S.H., Wu, Q., Liao, C., Blum, A., Stefani, A., Kurunthachalam, K., Persistent Organic Pollutants Including Polychlorinated and Polybrominated Dibenzo-p-dioxins and Dibenzofurans in Firefighters from Northern California, Chemosphere, 91(10), 1386-1394 (2013).

3.  Siddiqi, M.A., Laessig, R.H. and Reed, K.D., Polybrominated Diphenyl Ethers (PBDEs): New Pollutants-Old Diseases, Clin. Med.Res. 1(4), 281-290 (2003).

4.  Stapleton, H.M., Klosterhaus, S., Keller, A., Ferguson, P.L., van Bergen, S., Cooper, E., Webster, T.F., and Blum, A., Identification of Flame Retardants in Polyurethane Foam Collected from Baby Products, Environmental Science & Technology, 45, 5323-5331 (2011).

5.  Key, P.B., Chung, K.W., Hoguet, J., Shaddrix, B., Fulton, M. H., Toxicity and physiological effects of b rominated flame retadant PBDE-47 on two life stages of grass shrimp, Palaemonetes pugio, Science of the Total Environment 399, 28-32 (2008).

(cont.)

References (cont.) 6.  Stockholm Convention on Persistent Organic Pollutants, Persistent Organic

Pollutants Review Committee, Draft Risk Profile for Commercial Octabromodiphenyl Ether, http://www.pops.int/documents/meetings/poprc/drprofile/drp/DraftRiskProfile_OctaBDE.pdf, accessed 10/2/13.

7.  Birnbaum, L.S., and Staskal, D.F., Brominated Flame Retardants: Cause for Concern?, Environmental Health Perspectives, 112(1), 9-17 (2004).

8.  US Environmental Protection Agency, DecaBDE Phase-out Initiative, available at http://www.epa.gov/opptintr/existingchemicals/pubs/actionplans/deccadbe.html, accessed September 4, 2014.

9.  US Environmental Protection Agency, An Alternatives Assessment for the Flame Retardant Decabromodiphenyl ether (DecaBDE), available at http://www.epa.gov/dfe/pubs/projects/decaBDE/deca-report-complete.pdf, accessed September 4, 2014.

10. Patisaul, H.B., Roberts, S.C., Mabrey, N., McCaffrey, K.A., Gear, R.B., Braun, J., Belcher, S.M., and Stapleton, H.M., Accumulation and Endocrine Disrupting Effects of the Flame Retardant Mixture Firemaster 550 in Rats: An Exploratory Assessment, J. Biochem. Mol. Toxic. 27(2): 124 – 136 (2013).

(cont.)

References (cont.) 11.  van der Veen, I., de Boer, J., Phosphorus flame retardants: Properties,

production, environmental occurrence, toxicity and analysis, Chemosphere 88: 1119 – 1153 (2012).

12.  Zhang, Q., Lu, M., Dong, X., Wang, C., Zhang, C., Liu, W., and Zhao, M., Potential Estrogenic Effects of Phosphorus-Containing Flame Retardants, Environ. Sci. Technol., 48: 6995 – 7001 (2014).

13.  Stapleton, H.M., Klosterhaus, S., Eagle, S., Fuh, J., Meeker, J.D., Blum, A. and Webster, T.F., Detection of Organophosphate Flame Retardants in Furniture Foam and U.S. House Dust, Environ. Sci. Technol., 43, 7490-7495 (2009).

14.  Stapleton, H.M., Klosterhaus, S., Keller, A., Ferguson, P.L., van Bergen, S., Cooper, E., Webster, T.F., and Blum, A., Identification of Flame Retardants in Polyurethane Foam Collected from Baby Products, Environmental Science & Technology, 45, 5323-5331 (2011).

15.  World Health Organization (WHO), Report No. EHC 209: Flame Retardants: Tris(Chloropropyl) Phosphate and Tris(2-Chloroethyl) Phosphate, WHO: Geneva, Switzerland (1998).

(cont.)

References (cont.) 16.  Saunders, D. M., Higley, E. B., Hecker, M., Mankidy, R., & Giesy, J. P. In vitro

endocrine disruption and TCDD-like effects of three novel brominated flame retardants: TBPH, TBB, & TBCO. Toxicol Lett, 223(2), 252-259 (2013).

17.  Mankidy, R., Ranjan, B., Honaramooz, A., & Giesy, J. P. Effects of novel brominated flame retardants on steroidogenesis in primary porcine testicular cells. Toxicol Lett, 224(1), 141-146 (2014).

18.  Egloff, C., Crump, D., Chiu, S., Manning, G., McLaren, K. K., Cassone, C. G., Letcher, R.J., Gauthier, L.T. & Kennedy, S. W. In vitro and in ovo effects of four brominated flame retardants on toxicity and hepatic mRNA expression in chicken embryos. Toxicol Lett, 207(1) (2011).

19.  Springer, C., Dere, E., Hall, S. J., McDonnell, E. V., Roberts, S. C., Butt, C. M., Stapleton, H. M., Watkins, D. J., McClean, M. D., Webster, T. F., Schlezinger, J. J. & Boekelheide, K. Rodent thyroid, liver, and fetal testis toxicity of the monoester metabolite of bis-(2-ethylhexyl) tetrabromophthalate (tbph), a novel brominated flame retardant present in indoor dust. Environ Health Perspect, 120(12), 1711-1719 (2012).

20.  Stull, J.O., Dodgen, C.R., Connor, M.B., & McCarthy, R.T., Evaluating the effectiveness of different laundering approaches for decontaminating structural firefighting protective clothing. ASTM Special Technical Publication, 1237, 447-468 (1996).

References (cont.) 21.  Baxter CS, Ross CS, Fabian T, Borgerson JL, Shawon J, Gandhi PD, Dalton JM,

Lockey JE, Ultrafine particle exposure during fire suppression--is it an important contributory factor for coronary heart disease in firefighters?, J Occup Environ Med. 52(8):791-6 (2010).

22.  Lacey, S., Alexander, B. M., & Baxter, C. S. (2014). Plasticizer contamination of firefighter personal protective clothing - a potential factor in increased health risks in firefighters. J Occup Environ Hyg, 11(5), D43-48.

23.  National Fire Protection Association (NFPA), Standard 1851: Standard on Selection, Care, and Maintenance of Protective Ensembles for Structural Fire Fighting and Proximity Fire Fighting, NFPA: Quincy, MA (2014).

24.  Kashmanian, P. and Grant, C.C., Data Collection Summary for PPE Care and Maintenance, Fire Protection Research Foundation: Quincy, MA (2014).

Acknowledgements •  This research study was supported by the

National Institute for Occupational Safety and Health Pilot Research Project Training Program of the University of Cincinnati Education and Research Center Grant #T42/OH008432-07.

•  I wish to thank Dr. Stuart Baxter for his help and support with this research.

•  I am grateful to the firefighters of the Cincinnati Fire Department for their cooperation and interest in this study.

Identification of PBDE Congeners

Congener   Polybrominated diphenyl ether (PBDE)  28   2,4,4'-tribromodiphenyl ether  47   2,2',4'4'-tetrabromodiphenyl ether  

100   2,2',4,4',6-pentabromodiphenyl ether  99   2,2',4,4',5-pentabromodiphenyl ether  

153   2,2',4,4',5,5'-hexabromodiphenyl ether  209   2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether