Flame Retardant Evaluations at USEPAEmma T. Lavoie

US Environmental Protection Agency

TURA Continuing Education Conference

April 9, 2015

Opinions expressed are those of the author and do not necessarily reflect Agency policy.

ALTERNATIVES ASSESSMENT

• Identify and compare functional alternatives

• Simple communication of results

− high, moderate, or low hazard for human & ecological toxicity

& fate

• Chemical details, data summaries and use information

• Include diverse stakeholders

• Consider potential trade-offs, green chemistry needs

Higher HazardModerate

Hazard

Lower

Hazard

ALTERNATIVES ASSESSMENT – HAZARD BASED APPROACHES

INCLUDE EXPOSURE ASSESSMENT

Functional UseComparing chemicals with similar use patterns

yields similar exposure patterns

Life Cycle ConsiderationsWhere in life-cycle are major exposures?

Environmental Fate AssessmentPersistence and bioaccumulation potential

Bioavailability

ALTERNATIVES ASSESSMENT FRAMEWORK

1. Need for information (e.g., PBDE replacement)

2. Stakeholder input

3. Identify alternatives

4. Gather information

5. Apply criteria

6. Present results

7. Inform substitution – include hazard assessment in

performance and cost assessment

DECABROMODIPHENYL ETHER (DECABDE)

ALTERNATIVES ASSESSMENT

• 2009: PBDE Action Plan; FR manufacturers in USA voluntarily

ceasing production by 2013; information on alternatives is

valuable

• Identified stakeholders; developed scope based on polymers;

identified viable alternative FRs

‒ Discrete, polymeric, halogen, phosphorus, nitrogen,

inorganic

• Draft report released 31 July 2012; 15 sets of public comments

• January 2014: Final report released http://www.epa.gov/dfe/pubs/projects/decaBDE/deca-report-complete.pdf

**

Br

Br

n

OH Mg

OH

O

O P

O

O

O O P O

O

n

O

BrBr

Br Br

Br

Br

Br

Br

Br

Br

HAZARD ASSESSMENT CRITERIA

• Define very low, low, moderate, high, very high

• More distinguishing for some endpoints than standard

regulatory thresholds of concern

DecaBDE Assessment results I:

DecaBDE & Discrete Halogenated Alternatives

CASRN

Human Health Effects Aquatic

Toxicity**

Environmental

Fate

Acu

te T

oxic

ity

Carc

ino

gen

icit

y

Gen

oto

xic

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Rep

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Dev

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DecaBDE and Halogenated Flame Retardant Alternatives

DecaBDE and Discrete Halogenated FR Alternatives

Bis(hexachlorocyclopentadie

no) Cyclooctane13560-89-9 L M§ M§ VL VL L M L VL L L L VH H

Brominated

Poly(phenylether)Confidential L L¤ L VL¤ M¤ L¤ L¤ L L VL L L¤ VHT HT¤

Decabromodiphenyl Ethane 84852-53-9 L M§ L L H§ L L L VL VL L L VH H

Decabromodiphenyl Ether 1163-19-5 L M L L H L M L L L L L VH H

Ethylene Bis-

Tetrabromophthalimide32588-76-4 L M L L M§ L L L VL VL L L VH H

Tetrabromobisphenol A Bis

(2,3-dibromopropyl) Ether21850-44-2 L M M M M L M L L L L L VH H

Tris(tribromoneopentyl)

Phosphate19186-97-1 M M L M M H L L L L L L H M

Tris(tribromophenoxy)

Triazine25713-60-4 L L L L L L L L L VL L L VH H

DecaBDE Assessment results II:

Brominated Polymeric Alternatives

Chemical CASRN

Human Health Effects Aquatic

Toxicity**

Environmental

Fate

Acu

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oxic

ity

Carc

ino

gen

icit

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Gen

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tion

Halogenated Flame Retardant Alternatives Continued

Polymeric Halogenated FR AlternativesP

Brominated Epoxy Polymers 68928-70-1 L L♦♦♦♦ L L♦♦♦♦ L♦♦♦♦ L L♦♦♦♦d L ♦♦♦♦ L L L♦♦♦♦ L♦♦♦♦ VH L♦♦♦♦

Brominated Epoxy Polymer(s) Confidential L L♦♦♦♦ L♦♦♦♦ L♦♦♦♦ L♦♦♦♦ L L♦♦♦♦d L♦♦♦♦ ♦♦♦♦ L L L♦♦♦♦ L♦♦♦♦ VH L♦♦♦♦

Mixture of brominated epoxy

polymer(s) and bromobenzyl acrylate Confidential L L♦♦♦♦ L♦♦♦♦ L♦♦♦♦ L♦♦♦♦ L L♦♦♦♦

d L♦♦♦♦ ♦♦♦♦ L L L♦♦♦♦ L♦♦♦♦ VH L♦♦♦♦

Brominated Epoxy Resin End-

Capped with Tribromophenol135229-48-0 L L L L L L Ld L L VL L L VH L

Brominated Polyacrylate 59447-57-3 L L L L L L Ld L L L L L VH L

Brominated Polystyrene 88497-56-7 L L L L L L Ld L L L L L VH L

♦ Different formulations of the commercial product are available. One of these many formulations has an average MW of ~1,600 and

contains significant amounts of lower MW components. These lower MW components have hazard designations different than the

polymeric flame retardant, as follows: HIGH (estimated) for bioaccumulation; HIGH (experimental) for acute aquatic toxicity; HIGH

estimated for chronic aquatic toxicity; MODERATE (experimental) for developmental; and MODERATE (estimated) for carcinogenicity,

genotoxicity, repeated dose, reproductive, and skin and respiratory sensitization toxicity.

DecaBDE Assessment results III:

Discrete Phosphorus- and Nitrogen- based

Alternatives

Chemical CASRN

Human Health Effects Aquatic

Toxicity**

Environmental

Fate

Acu

te T

oxic

ity

Carc

inog

enic

ity

Gen

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tion

Organic Phosphorus or Nitrogen Flame Retardant (PFR or NFR) Alternatives

Discrete PFR, NFR and P/NFR Alternatives

Substituted Amine Phosphate

Mixture 1Confidential H M M M M L M L M§ M VL M L H L

Triphenyl Phosphate 115-86-6 L M L L L L H L L VL VH VH L M

Polymeric PFR and NFR Alternatives

Bisphenol A bis-(diphenyl

phosphate); BAPP181028-79-5 L M L L L§ L§ L L L L L L H H◊◊◊◊

Melamine Cyanurate1 37640-57-6 L M M M§ M§ L H L L L L L VH L

Melamine Polyphosphate1 15541-60-3 L M M L§ L L§ M L L VL L L H L

N-alkoxy Hindered Amine Reaction

Products 191680-81-6 L M L H H L H L L VL H H H H‡

DecaBDE Assessment results IV:

Polymeric Phosphorus- and Nitrogen- based

Alternatives

Chemical CASRN

Human Health Effects Aquatic

Toxicity**

Environmental

Fate

Acu

te T

oxic

ity

Carc

inogen

icit

y

Gen

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Rep

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Organic Phosphorus or Nitrogen Flame Retardant (PFR or NFR) Alternatives Continued

Polymeric PFR and NFR Alternatives

Phosphonate Oligomer¥ 68664-06-2 L M L§ L¥ L¥ M‡ L§¥ L§¥ M‡¥ M‡ L¥ H‡ VH H‡

Polyphosphonate 68664-06-2 L L L L L L Ld L L L L L VH L

Phosphoric acid, mixed esters with

[1,1'-bisphenyl-4,4'-diol] and phenol;

BPBP

1003300-73-9 L M L L§ L§ L L L VL VL H§ H§ H M‡

Poly[phosphonate-co-carbonate] 77226-90-5 L L L L L L Ld L L L L L VH L

Resorcinol Bis-Diphenylphosphate;

RDP125997-21-9 L M§ L L M M M L L VL VH VH M H‡

DecaBDE Assessment results V:

Inorganic Alternatives

Chemical CASRN

Human Health Effects Aquatic

Toxicity**

Environmental

Fate

Acu

te T

oxic

ity

Carc

inogen

icit

y

Gen

oto

xic

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Rep

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Inorganic Flame Retardant Alternatives

Aluminum Diethylphosphinate 225789-38-8 L L L VL M M M L L VL M M HR L

Aluminum Hydroxide 21645-51-2 L L L L L M M L VL VL M M HR L

Ammonium Polyphosphate 68333-79-9 L L L L L L Ld L VL L L L VH L

Antimony Trioxide1 1309-64-4 L M* M M L L H L L M H M HR L

Magnesium Hydroxide 1309-42-8 L L L L L L L L M L L L HR L

Red Phosphorus 7723-14-0 L L M L L L L L M M L L H L

Zinc Borate 1332-07-6 L L H M M H L L L L H H HR L

AA FOR HEXABROMOCYCLODODECANE

12

BrBr

BrBr

Br

BrHBCD

butadiene styrene

brominated copolymer

TBBPA-bis brominated ether derivatives

Br

Br

OBr

O

Br

Br

Br

BrBr

Br

Br

O

Br

O

Br

Br

Br

Br

Br

• Started April 2011

• Assessed HBCD and two alternatives for EPS and XPS building

insulation

• Draft report for public comment Sept – Dec 2013

• Final report June 2014

HBCD – example of data communication

Three levels of data communication

Genotoxicity LOW: Based on negative results for gene mutations in bacterial cells, a lack of chromosomal aberrations in human peripheral blood lymphocyte cells in

vitro, and negative results in recombination and mouse micronucleus tests.

Gene Mutation in vitro Negative in Salmonella typhimurium (strains not

specified) in the presence and absence of metabolic

activation

EPA, 2005; NICNAS, 2012 Reported in a secondary source with limited study

details.

Gene Mutation in vivo No data located.

Chromosomal Aberrations in vitro Negative, mammalian chromosomal aberration test with

human peripheral blood lymphocytes in the presence and

absence of metabolic activation

Doses: 10, 19, 38, 75, 150, 300 and 600 µg/mL

EPA, 2005; NICNAS, 2012 Reported in a secondary source. Guideline study.

Performed according to current EPA, OECD

guidelines, and GLP.

DNA Damage and Repair No data located.

Other in vitro Positive, intragenic recombination test in Sp5/V79 and

SPD8 hamster cells; cell lines developed by study authors

Doses: 2-20 µg/mL

EPA, 2005; NICNAS, 2012 Reported in a secondary source. Non-guideline

study. Not a standard test used by regulatory

agencies to assess genotoxicity. Reliability and

predictive ability is unknown.

Negative, mouse micronucleus test

Doses: 0, 500, 1,000 or 2,000 mg/kg in dimethyl

sulfoxide (DMSO)

EPA, 2005 Reported in a secondary source. Guideline study.

Performed according to current EPA, OECD

guidelines and GLP.

1

2

3

COMPARE TRADE-OFFS; IDENTIFY SAFER CHEMISTRY

FURNITURE FLAME RETARDANTS

• 2005 Furniture

Flame Retardancy

Partnership

• Alternatives to

pentaBDE in

polyurethane foam

• Updated June 2014

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Flame Retardants used in flexible polyurethane foam – draft 2014

FRS IN PRINTED CIRCUIT BOARDS 2006+

TBBPA and 10

alternatives

Draft report released

2008; revised 2014

Combustion

experiments

completed 2012; data

shared 2013

Hazard profiles updated

17http://www.epa.gov/dfe/pubs/projects/pcb/index.htm

18

Flame Retardants used in printed circuit boards I – 2014 Draft

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Flame Retardants used in printed circuit boards II – 2014 Draft

COMBUSTION TESTING

What are the combustion by-products of Br and non-Br flame retarded laminates for PCBs?

• Cone Calorimeter tests• 50 kW/m2 heat flux = open burn

• 100 kW/m2 heat flux = incinerator conditions

• Materials – ISOLA, Panasonic, Seagate

− Non Flame Retardant (NFR) Epoxy Laminates

− Brominated Flame Retardant (BFR) Epoxy Laminates

− Phosphorus Flame Retardant (PFR) Epoxy Laminates

− Halogenated FR Homogenized Component Powder (SH)

− Low Halogen Homogenized Component Powder (LH)

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0.00E+00

5.00E-01

1.00E+00

1.50E+00

2.00E+00

2.50E+00

3.00E+00

3.50E+00

PB

DD

/Fs,

ng

/g

Sample Description

PBDD/Fs Emission Factors

PBDD/Fs Emission Factors PBDD/Fs Emission Factors

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0.00E+00

1.00E+00

2.00E+00

3.00E+00

4.00E+00

5.00E+00

6.00E+00

PA

Hs,

g/k

g

Sample Description

PAH Emission Factors

PAH Emission Factors

100

SHLH

50

PAH Emission Factors

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Total Smoke Release

0.00

100.00

200.00

300.00

400.00

500.00

600.00

700.00

800.00

Sm

oke

Re

lea

se,

m2/m

2

Sample Description

Total Smoke Release

100

SH

LH50

Total Smoke Release

OECD TOOLBOX

Launch of online OECD Substitution and Alternatives

Assessment Toolbox 30 January 2015

Developed by the OECD Ad Hoc Group on Substitution

of Harmful Chemicals

Offers access to tools, data, chemical lists and

guidance documents for users with varying levels of

expertise to assist in the substitution of chemicals of

concern.

http://www.oecdsaatoolbox.org/

FINDINGS FROM FOUR AAS FOR FLAME RETARDANTS

1) Many flame retardants have inherent persistence

2) There is a spectrum of inherent hazards across the

broad class of chemicals:

neuro; developmental-neuro; repeated dose; aquatic toxicity;

bioaccumulation potential

3) Some flame retardants do have lower hazards

(e.g., some metal oxides and some very large polymers)

4) Flammability standards, performance and cost drive

chemical selection

25

RISK ASSESSMENT & MANAGEMENT

• March 2012, EPA identified a Work Plan of 83

chemicals

− 7 for risk assessment in 2012

− March 2013, announced 20 flame retardant

chemicals

• Assessment outcome may yield risk management.

• If negligible risks then no further work.

• Work Plan revisions if warranted.

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FLAME RETARDANT RISK ASSESSMENTS

EPA will conduct reviews on three groups of structurally similar chemicals, conducting full risk assessments on at least one chemical in the group. The following are slated for full risk assessment

Brominated Phthalates Group

183658-27-7 2-Ethylhexyl ester 2,3,4,5- tetrabromobenzoate (TBB)

26040-51-7 1,2- Ethylhexyl 3,4,5,6-tetrabromo-benzenedicarboxylate (TBPH)

Chlorinated Phosphate Esters Group

115-96-8 Tris(2-chloroethyl) phosphate (TCEP)

Cyclic Aliphatic Bromides Group

25637-99-4 and 3194-55-6

Hexabromocyclododecane (HBCD) and related congeners

27

ANTIMONY TRIOXIDE RISK ASSESSMENT

Addressed effects on ecological receptors from the

use of antimony trioxide (ATO) as a synergist in

halogenated flame retardants.

On August 28, 2014, EPA released the final risk

assessment that indicated no concern for this use of

ATO.

28

FOR FURTHER INFORMATION:

DfE Alternatives Assessments

http://www.epa.gov/dfe/alternatives_assessments.html

Lavoie.Emma@epa.gov

202-564-0951

Opinions expressed are those of the author and do not necessarily reflect Agency policy.