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
ity
Rep
rod
uct
ive
Dev
elo
pm
enta
l
Neu
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Rep
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d D
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Sk
in S
ensi
tiza
tion
Res
pir
ato
ry
Sen
siti
zati
on
Eye
Irri
tati
on
Der
mal
Irri
tati
on
Acu
te
Ch
ron
ic
Per
sist
ence
Bio
acc
um
ula
tion
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
te T
oxic
ity
Carc
ino
gen
icit
y
Gen
oto
xic
ity
Rep
rod
uct
ive
Dev
elo
pm
enta
l
Neu
rolo
gic
al
Rep
eate
d D
ose
Sk
in S
ensi
tiza
tio
n
Res
pir
ato
ry
Sen
siti
zati
on
Eye
Irri
tati
on
Der
mal
Irri
tati
on
Acu
te
Ch
ron
ic
Per
sist
ence
Bio
acc
um
ula
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
oto
xic
ity
Rep
rod
uct
ive
Dev
elop
men
tal
Neu
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gic
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Rep
eate
d D
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Sk
in S
ensi
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tio
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Res
pir
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Sen
siti
zati
on
Eye
Irri
tati
on
Der
mal
Irri
tati
on
Acu
te
Ch
ron
ic
Per
sist
ence
Bio
acc
um
ula
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
oto
xic
ity
Rep
rod
uct
ive
Dev
elop
men
tal
Neu
rolo
gic
al
Rep
eate
d D
ose
Sk
in S
ensi
tiza
tio
n
Res
pir
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Sen
siti
zati
on
Eye
Irri
tati
on
Der
mal
Irri
tati
on
Acu
te
Ch
ron
ic
Per
sist
ence
Bio
acc
um
ula
tion
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
ity
Rep
rod
uct
ive
Dev
elop
men
tal
Neu
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Rep
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d D
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Sk
in S
ensi
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tio
n
Res
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Sen
siti
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on
Eye
Irri
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Der
mal
Irri
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on
Acu
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Ch
ron
ic
Per
sist
ence
Bio
acc
um
ula
tion
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
15
16
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
19
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)
20
21
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
22
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
23
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.
26
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
202-564-0951
Opinions expressed are those of the author and do not necessarily reflect Agency policy.