DfE Assessments: DecaBDE and Other Ongoing Efforts - Pinfa-NA

DfE Assessments:
DecaBDE and Other Ongoing Efforts
Pinfa-NA
Seattle, April 2014
Emma Lavoie, Ph.D., US EPA
The opinions expressed in this presentation are those of the author and are not necessarily US EPA policy.
Contents
1. OPPT Work Plan Status
2. DfE Alternatives Assessments
3. DecaBDE AA
4. TBBPA AA
5. HBCD AA
6. Furniture Flame Retardants AA
7. ChemView
• March 2012, EPA identified a Work Plan of 83 chemicals
– 7 for risk assessment in 2012
– 18 chemicals for assessment in 2013 and 2014
– 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.
Flame Retardant Chemical Groups
CAS RN
Chemical
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 or (2ethylhexyl)-3,4,5,6 tetrabromophthalate (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
Alternatives Assessment Program
– Identify and compare functional alternatives
– Simple communication of results – high, moderate,
or low hazard for human and eco toxicity and fate
– Chemical details, data summaries and use
information
– Include diverse stakeholders
– Consider potential trade-offs, green chemistry needs
1330-78-5
Phosphoric acid, tris(methylphenyl) ester
Tricresyl phosphate; Disflamoll
TKP; TMPHP
C21H21O4P
IPPP; ITP; IPTPP;
Isopropylated triphenyl
phosphate; Isopropylated
phenol phosphate; TIPPP
C27H33O4P
TBPP; tris(4-(tert-butyl)phenyl
phosphate; tert-butylphenyl
diphenyl phosphate; bis(4-(tertbutyl)phenyl) phenyl
phosphate; TTBPHP
C30H39O4P
O
O P O
O
Representative structure
68937-41-7
Phenol, isopropylated, phosphate (3:1)
Commercial product may include mono-, di-,
tri- and higher substitutions with appropriate
CAS numbers.
Formula for
tri-propyl
substitution
O
O P O
O
Representative structure
78-33-1
Phenol, 4-(1,1-dimethylethyl)-, 1,1',1''phosphate
Includes mono-, di-, tri-, and higher
substitutions with appropriate CAS numbers.
Formula for
tri-butylated
substitution
O
P
O
O
O
Representative structure
Three levels of results; chemical details and data summaries
1
2
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) EPA, 2005; NICNAS, 2012
in the presence and absence of metabolic activation
Gene Mutation in vivo
Chromosomal Aberrations in vitro
No data located.
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
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
3
DNA Damage and Repair
Other in vitro
Reported in a secondary source with limited study
details.
Reported in a secondary source. Guideline study.
Performed according to current EPA, OECD
guidelines, and GLP.
No data located.
Negative, mouse micronucleus test
EPA, 2005
Doses: 0, 500, 1,000 or 2,000 mg/kg in dimethyl sulfoxide
(DMSO)
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.
Reported in a secondary source. Guideline study.
Performed according to current EPA, OECD
guidelines and GLP.
Academics
NGOs
Flame Retardant
Manufacturers
Compounders and Resin
Manufacturers
Automotive Industry
Aviation Industry
Military
Electronics Industry
Textile Industry
Recyclers
U.S. Federal Government
State and Local
Governments
International
Representatives
Consultants
Potential trade-offs/GC needs
O
O
O
H
S N
H3C
O
O
CH3
S
O
O
S
O
HO
N
H
O
O
O
S
O
O
O H
n
Chronic
Bioaccumulation
Fate
Acute
Respiratory
Sensitization
Dermal Irritation
Eye Irritation
H
Skin Sensitizer
H
Repeated Dose
Developmental
L M L
Neurological
Reproductive
CASRN
Genotoxicity
Chemical
OH
Acute Toxicity
HO
Carcinogenicity
Human Health Effects
Environmental
Persistence
Aquatic
Toxicity
M M M M
H
H
L M M
M L L VL
V
VH VH L
H
L
L‡
BPA alternatives in thermal paper
Bisphenol A
2,2-bis(phydroxyphenyl)propane
80-05-7
Pergafast 201
N-(p-Toluenesulfonyl)-N'(3-p232938-43-1
toluenesulfonyloxyphenyl)
urea
D-90
Phenol, 4,4’-sulfonylbis-,
polymer with 1,1’oxybis[2-chloroethane]
191680-83-8
L
L
L
L
L
L
L
L M VL
L‡
VL L
VH
‡
H10‡
DfE AA – functional use
Number of
substances or
products
Date
DecaBDE – many polymers; FR alternatives
in plastics
30
Final report
Jan 2014
HBCD – polystyrene building insulation
3
Draft report Sept 2013
Updated pentaBDE – flexible polyurethane
foam FRs
Potential alternatives
posted Sept 2013;
15 + 3 blends
expect report spring
2014
Updated Draft TBBPA and Alternatives in
Printed Circuit Boards
12
Draft 2008;
Revision spring 2014
12
2005
PentaBDE “FFR” – polyurethane foam for
furniture
Number of
substances or
products
• Bisphenol
A (BPA)
DfE AA – functional
use – thermal paper
Date
• 19
Final report
Bisphenol
A
(BPA)
–
thermal
paper
19
Jan 2014
• Final report
On hold pending release of
• Jan 2014
CPSC CHAP report and/or
Phthalates
~80
IRIS report
Nonylphenol and Nonylphenol
Ethoxylates (NP/NPE) – surfactants &
wetting agents
8 families
Final report
May 2012
TCE
tbd
tbd
Alternatives to decaBDE
• 2009: FR manufacturers voluntarily ceasing production; PBDE Action Plan;
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; completed revisions and responses to
15 sets of public comments received August-September 2012
• January 2014: Final report released:
OH
http://www.epa.gov/dfe/pubs/projects/decaBDE/deca-report-complete.pdf
Br
Br
O
Br
Br
n
*
HO Mg
Magnesium Hydroxide
*
Br
Br
O
O
Br Br
Br
Br
O P O
Br
Decabromodiphenyl Ether
O P
O
O
Br
Brominated PS
BAPP
O
n
Flame Retardant Alternatives for DecaBDE
CHEMICAL
CAS RN
DecaBDE and Discrete Halogenated FR Alternatives
Bis(hexachlorocyclopentadieno) Cyclooctane
Brominated Poly(phenylether)
Decabromodiphenyl Ethane
Decabromodiphenyl Ether
Ethylene Bis-Tetrabromophthalimide
Tetrabromobisphenol A Bis (2,3-dibromopropyl) Ether
Tris(tribromoneopentyl) Phosphate
Tris(tribromophenoxy) Triazine
13560-89-9
Confidential
84852-53-9
1163-19-5
32588-76-4
21850-44-2
19186-97-1
25713-60-4
Polymeric Halogenated FR Alternatives
Brominated Epoxy Polymers
Brominated Epoxy Polymer(s)
Mixture of brominated epoxy polymer(s) and
bromobenzyl acrylate
68928-70-1
Confidential
Confidential
Brominated Epoxy Resin End-Capped with Tribromophenol 135229-48-0
Brominated Polyacrylate
Brominated Polystyrene
59447-57-3
88497-56-7
Flame Retardant Alternatives for DecaBDE
CHEMICAL
CAS RN
Discrete PFR, NFR and P/NFR Alternatives
Substituted Amine Phosphate Mixture 1L
Confidential
Triphenyl Phosphate
115-86-6
Polymeric PFR and NFR Alternatives
Bisphenol A bis-(diphenyl phosphate); BAPP
Melamine Cyanurate1
Melamine Polyphosphate1
N-alkoxy Hindered Amine Reaction Products
181028-79-5
37640-57-6
15541-60-3
191680-81-6
Phosphonate Oligomer¥
Polyphosphonate
Phosphoric acid, mixed esters with [1,1'-bisphenyl-4,4'diol] and phenol; BPBP
Poly[phosphonate-co-carbonate]
68664-06-2
68664-06-2
Resorcinol Bis-Diphenylphosphate; RDP
125997-21-9
1003300-73-9
77226-90-5
15
Flame Retardant Alternatives for DecaBDE
CHEMICAL
CAS RN
Inorganic Flame Retardant Alternatives
Aluminum Diethylphosphinate
225789-38-8
Aluminum Hydroxide
Ammonium Polyphosphate
21645-51-2
68333-79-9
Antimony Trioxide1
1309-64-4
Magnesium Hydroxide
1309-42-8
Red Phosphorus
7723-14-0
Zinc Borate
1332-07-6
16
• Define very low, low, moderate, high, very high
• More distinguishing for some endpoints than standard
regulatory thresholds of concern
Endpoints in colored text (VL, L, M, H, and VH) were assigned based on empirical data. Endpoints in black italics
(VL, L, M, H, and VH) were assigned using values from predictive models and/or professional judgment.
Environmental
Fate
Aquatic
Toxicity
Dermal
Irritation
Acute
Chronic
Persistence
Bioaccumulation
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
32588-76-4
L
M
L
L
M§
L
L
L
VL
VL
L
L
VH
H
21850-44-2
L
M
M
M
M
L
M
L
L
L
L
L
VH
H
Tris(tribromoneopentyl) Phosphate 19186-97-1
M
M
L
M
M
H
L
L
L
L
L
L
H
M
Tris(tribromophenoxy) Triazine
L
L
L
L
L
L
L
L
L
VL
L
L
VH
H
Respiratory
Sensitization
L
Skin
Sensitization
VL
Repeated Dose
VL
Neurological
M§
Developmental
M§
Reproductive
L
Genotoxicity
13560-89-9
CASRN
Carcinogenicity
Bis(hexachlorocyclopentadieno)
Cyclooctane
Chemical
Acute Toxicity
Eye Irritation
Human Health Effects
DecaBDE and Halogenated Flame Retardant Alternatives
Ethylene BisTetrabromophthalimide
Tetrabromobisphenol A Bis (2,3dibromopropyl) Ether
25713-60-4
http://www.epa.gov/dfe/pubs/projects/decaBDE/deca_fullreport.pdf
TBBPA and 10
alternatives
Draft report released
2008
Combustion
experiments
completed 2012;
report in preparation
Hazard profiles to be
updated
http://www.epa.gov/dfe/pubs/projects/pcb/index.htm
Flame Retardants in Printed Circuit Boards 2008
Human Health
Hazard Concern
Ecotoxicity
Hazard Concern
Environmental
Concern
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)
PBDD/Fs Emission Factors
PBDD/Fs Emission Factors
3.50E+00
PBDD/Fs, ng/g
3.00E+00
2.50E+00
2.00E+00
1.50E+00
1.00E+00
5.00E-01
0.00E+00
Sample Description
PAH Emission Factors
PAH Emission Factors
6.00E+00
100
50
5.00E+00
SH
PAHs, g/kg
4.00E+00
3.00E+00
2.00E+00
1.00E+00
0.00E+00
Sample Description
LH
Total Smoke Release
Total Smoke Release
800.00
SH
Smoke Release, m2/m2
700.00
600.00
100
50
500.00
400.00
300.00
200.00
100.00
0.00
Sample Description
LH
AA for Hexabromocyclododecane
•
•
•
•
Started April 2011
Assessed HBCD and two alternatives for EPS and XPS building insulation
Draft report for public comment Sept – Dec 2013
Currently preparing final report and response to comments
Br
Br
Br
Br
O
O
Br
Br
Br
Br
Br
Br
Br
Br
Br
HBCD
butadiene styrene
brominated copolymer
Br
Br
TBBPA-bis (2,3-dibromopropyl)
ether
Br
O
Br
Br
Br
Br
O
Br
Br
TBBPA-bis brominated ether derivative
• 2005
• Furniture Flame Retardancy
Partnership
• Alternatives to pentaBDE in
polyurethane foam
• Started 2003, final report released 2005
• Update initiated in 2013
• Update will assess:
– FRs from the 2005 report still in commerce
– FRs used or marketed for use in upholstered PUF since
2005
• 15 chemicals & 3 mixtures
• Will not assess textiles, FR barriers, or other alternative
technologies
http://www.epa.gov/dfe/pubs/projects/flameret/about.htm
The update will “identify flame retardant chemicals used to meet fire
safety requirements for upholstered consumer products containing
polyurethane foam; and update their health and environmental
profiles with current science and DfE’s most current hazard criteria.”
Overlap with workplan: This scope includes TBB and TBPH; TDCPP, TCEP, TCPP.
Expands scope of the 2005 report to include baby/children’s products.
The tailored report will also have relevance for
• Office/hotel/restaurant furniture
• Automotive seats
• Aviation seats
CHEMICAL
CASRN
Halogenated Flame Retardant Alternatives
Firemaster® 550 Components
Firemaster® 550*
Mixture
Benzoic acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl ester (TBB) ¥
183658-27-7
Di(2-ethylhexyl) tetrabromophthalate (TBPH) ^ ¥
26040-51-7
Isopropylated triphenyl phosphate (IPTPP) ^
68937-41-7
Triphenyl phosphate (TPP) ^
115-86-6
Chlorinated Phosphorus Alternatives
Tris (2-chloroethyl) phosphate (TCEP)
115-96-8
13674-84-5;
Tris (2-chloro-1-methylethyl) phosphate (TCPP)
6145-73-9
Tris (1,3-dichloro-2-propyl) phosphate (TDCPP)
Phosphoric acid, P,P'-[2,2-bis(chloromethyl)-1,3-propanediyl] P,P,P',P'-tetrakis(2chloroethyl) ester (V6)
13674-87-8
38051-10-4
CHEMICAL
CASRN
Non-Halogenated Flame Retardant Alternatives
Inorganic/Other Alternatives
Ammonium polyphosphate (APP) ¥
68333-79-9
Expandable graphite ¥
12777-87-6
Melamine
108-78-1
Non-Halogenated Flame Retardant Alternatives continued
Phosphate Alternatives
Triphenyl phosphate (TPP) †
115-86-6
Tricresyl phosphate (TCP) 1
1330-78-5
Isopropylated triphenyl phosphate (IPTPP) †
68937-41-7
Tris (p-t-butylphenyl) phosphate (TBPP)
Diethyl bis(2-hydroxyethyl)aminomethylphosphonate
Oligomeric ethyl ethylene phosphate
78-33-1
11/5/2781
184538-58-7
New-to-Market Proprietary Mixtures
Emerald Innovation™ NH-1*
Proprietary
Fyrol™ HF-5 *
Proprietary
Click to view the Hazard
Characterization
information.
www.epa.gov/chemview/
33
DfE: http://www.epa.gov/dfe
http://www.epa.gov/dfe/alternative_assessments.html
[email protected]
202-564-0951
The opinions expressed in this presentation are those of the author
and are not necessarily US EPA policy.
34

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