Furniture Flame Retardancy Partnership:
Environmental Profiles of Chemical Flame-Retardant
Alternatives for Low-Density Polyurethane Foam
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EXECUTIVE SUMMARY
Issue
Efforts to improve the fire safety of furniture protect property and save lives. Fires involving
ignition of residential upholstered furniture constitute a leading cause of fire deaths and serious
injuries associated with consumer products. According to the Consumer Product Safety
Commission staff, the average annual fire losses for the years 1995-1999 were 460 deaths, 1,110
injuries and $130 million in property damage (CPSC, 2004). Flame retardants delay ignition and
have proven to save lives. While benefits achieved through enhanced fire safety are critical, they
should be achieved in a manner that minimizes risk to human health and the environment. The
work summarized in this report arose from concern over potential human health and
environmental impacts from the use of pentabromodiphenyl ether (pentaBDE). This chemical
flame retardant has been used in the manufacture of low-density, flexible polyurethane foam for
upholstered furniture (residential, business and institutional), mattresses, bedding, carpet
underlay and other articles. Studies around the world have found pentaBDE to be widespread in
the environment and in human tissues. Recently the use of pentaBDE has been banned in the
European Union, and legislation has been passed to restrict its use in Hawaii and California in
2006 (January 1 and June 1, respectively).
In late 2003, Great Lakes Chemical Corporation, the sole U.S. manufacturer of the commercial
mixture known as pentaBDE, announced a voluntary phase-out of this chemical in the United
States by December 31, 2004. This phase-out, along with anticipated implementation of more
stringent national fire safety standards in residential upholstered furniture, has made finding
alternatives to pentaBDE a critical priority for the furniture industry and all parties involved.
Partnership and Scope
EPA's Design for the Environment Program and Region IX have joined with a broad set of
stakeholders to form the Furniture Flame Retardancy Partnership. Key players involved in the
Partnership include members of the furniture industry, chemical manufacturers, environmental
groups, fire safety advocates, the Consumer Product Safety Commission and the National
Institute of Standards and Technology.
The Partnership is working to identify and assess environmentally safer chemical alternatives to
pentaBDE and to investigate other technologies for improving furniture fire safety. The primary
purpose of this report is to provide up-to-date and objective information that will allow the
furniture industry and chemical manufacturers to factor human health and environmental
considerations into decision-making when identifying replacements for pentaBDE. The hazard,
exposure and environmental assessment of chemical flame-retardant alternatives in this report is
intended to be a first step in providing information that will serve as a basis for making
decisions. Additional objectives of this report are to inform the reader of some considerations to
take into account when selecting a replacement for pentaBDE and to introduce alternative
technologies that may impact future methods of flame-retarding furniture.
The Partnership recognizes that no single alternative is expected to provide an ideal solution to
address every issue. Rather, the project members hope to provide the best available information
on the human health and environmental attributes of the leading chemical alternatives to
pentaBDE so that individual companies and consumers can make educated decisions that will
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best suit their needs. Some information on alternative technologies, e.g. barrier fabrics, for
flame-retarding furniture is provided, but not extensively discussed in this report.
Results
This report is the first product of the Furniture Flame Retardancy Partnership. To provide
information for decision-making, the Partnership evaluated the leading chemical alternatives for
flame retarding low-density flexible polyurethane foam. Leading U.S. flame-retardant chemical
manufacturers identified 14 chemical formulations that are potentially viable substitutes for
pentaBDE in large-scale production of low-density flexible polyurethane foam. EPA assessed the
hazards, potential exposures and tendency to bioaccumulate and persist in the environment for
the chemicals in each formulation. Section 4 of this report is a summary of EPA's qualitative
assessment, which is based on known or estimated effects on various toxicological and
environmental endpoints. This section includes a summary chart (Table 4-1) with information on
potential routes of exposure, based on physical and chemical properties. Section 4 also includes
an explanation of how the information in the chart was developed.
Conclusions
This report summarizes the level of potential hazard associated with relevant endpoints for the
chemical formulations. Table 4-1 provides the best available information for making educated
decisions about these alternative chemical products.
The Partnership plans to develop and implement a process to identify additional toxicological
data needed for adequately assessing the flame-retardant alternatives in Table 4-1. Industry will
support this process and develop data to satisfy these needs over time for endpoints that have a
moderate or high level of concern. Those flame-retardant products that emerge as the most
popular replacement products for pentaBDE deserve this greater level of scrutiny based on their
potential for exposure to humans and the environment during manufacture, use and disposal. The
stakeholders in this Partnership will use the data summarized in Table 4-1 to affirm short-term
decisions. EPA has developed this alternatives assessment to serve as a model for addressing
emerging chemical concerns.
Next Steps
In the future, the Partnership intends to evaluate additional chemical flame retardants and other
materials that may be necessary to meet planned national fire safety standards. The Partnership
would also like to develop a furniture design challenge to encourage the safest means (new
designs, chemicals and materials) to meet furniture fire safety standards. Finally, the Partnership
would like to stimulate innovation by providing EPA recognition for next-generation, safer
chemical flame retardants and safer non-chemical technologies.
Updated information on the Furniture Flame Retardancy Partnership will be available on EPA's
Design for the Environment website: http://www.epa.gov/dfe/projects/flameret/index.htm.
11
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TABLE OF CONTENTS
Volume 1
Executive Summary i
List of Acronyms v
About the Partnership vii
1.0 Introduction 1-1
1.1 Purpose of the PentaBDE Alternatives Analysis 1-1
1.2 Scope of the PentaBDE Alternatives Analysis 1-3
2.0 Types of Chemical Flame Retardants 2-1
2.1 General Characteristics of Chemical Flame Retardants 2-1
2.1.1 General Mechanisms of Flame Retardancy 2-1
2.1.2 Additive and Reactive Flame Retardants 2-2
2.1.3 Flame-Retardant Synergists 2-3
2.2 Flame-Retardant Chemicals Currently Used in Foam 2-4
3.0 Exposure to Flame-Retardant Chemicals in Foam 3-1
3.1 Exposure Pathways and Routes (General) 3-1
3.2 Industrial Releases and Exposures 3-3
3.2.1 Chemical Manufacturing 3-5
3.2.2 Foam Manufacturing 3-7
3.2.3 Furniture Manufacturing 3-10
3.3 Consumer and General Population Exposures 3-12
3.3.1 Physical and Chemical Properties Affecting Exposure 3-12
3.3.2 Consumer Use and End-of-Life Analysis 3-15
4.0 Flame-Retardant Alternatives Evaluations 4-1
4.1 Summary of Flame-Retardant Chemical Alternatives 4-1
4.1.1 Explanation of Toxicological and Environmental Endpoints Rating 4-5
4.1.2 Explanation of Exposure Route Rating 4-9
4.2 Chemical Summary Assessments 4-12
4.2.1 Triphenyl Phosphate 4-12
4.2.2 Tribromoneopentyl alcohol 4-16
4.2.3 Tris(l,3-dichloro-2-propyl) Phosphate 4-20
4.2.4 Proprietary A 4-25
4.2.5 Proprietary B 4-30
4.2.6 Proprietary C 4-35
4.2.7 Proprietary D 4-40
4.2.8 Proprietary E 4-44
4.2.9 Proprietary F 4-48
4.2.10 Proprietary G 4-52
4.2.11 Proprietary H 4-57
4.2.12 Proprietary I 4-61
4.2.13 Proprietary! 4-65
4.2.14 Proprietary K 4-69
4.2.15 Proprietary L 4-73
5.0 Considerations for Selecting a Replacement for PentaBDE 5-1
5.1 Positive Environmental Attributes 5-1
iii
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5.2 Aesthetic and Performance Considerations 5-3
5.3 Process and Equipment Considerations 5-3
5.4 Economic Viability 5-4
5.5 Alternatives Technologies (General) 5-4
5.5.1 Barrier Technologies 5-4
5.5.2 Graphite Impregnated Foams 5-6
5.5.3 Surface Treatments 5-6
5.6 Methods for Selecting Chemical Flame Retardants 5-6
6.0 References 6-1
Appendix A PentaBDE Facts
Appendix B Interpretive Guidance
Appendix C Chemical Regulations List
Volume 2 Chemical Hazard Reviews http://www.epa.gov/dfe/projects/flameret/index.htm
LIST OF TABLES
Table 1-1 Potential Flame-Retardant Chemical Formulations 1-4
Table 4-1 Screening Level Toxicology and Exposure Summary 4-2
Table 4-2 Definitions of Toxicological and Environmental Endpoints 4-5
Table 4-3 Criteria Used to Assign Concern Levels 4-6
Table 4-4 Information for Estimating Half-Life 4-6
LIST OF FIGURES
Figure 1-1 Pentabromodiphenyl Ether (pentaBDE), Where m+n = 5 1-2
Figure 3-1 Simplified Life Cycle for a Flame-Retardant Chemical 3-2
Figure 3-2 Generic Chemical Manufacturing Process Flow Diagram 3-6
Figure 3-3 Typical Slabstock Foam Production for Flexible Polyurethane Foam 3-8
Figure 3-4 Typical Molded Foam Production Line for Flexible Polyurethane Foam 3-9
Figure 3-5 Process Flow Diagram: Furniture Manufacturing 3-11
IV
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LIST OF ACRONYMS
ADDpot Potential Average Daily Dose
ADRpot Potential Acute Dose Rate
AFMA American Furniture Manufacturers Association
AFSC American Fire Safety Council
AHFA American Home Furnishings Alliance
APP Ammonium Polyphosphate
ATSDR Agency for Toxic Substances and Disease Registry
BCF Bioconcentration Factor
BIFMA The Business and Institutional Furniture Manufacturer's Association
BFR Brominated Flame Retardant
CBI Confidential Business Information
ChV Chronic Value
CCRIS Chemical Carcinogenesis Research Information System
CIS Chemical Information Systems
COC Concentration of Concern
CPA Clean Production Action
CPSC Consumer Product Safety Commission
DART Developmental and Reproductive Toxicology
DecaBDE Decabromodiphenyl Ether
DfE Design for the Environment
ECDB Existing Chemicals Database
ECOSAR Ecological Structure Activity Relationships
EFED Environmental Fate and Effects Division
ELISA Enzyme-Linked Immunosorbent Assay
EMIC Environmental Mutagen Information Center
EPA Environmental Protection Agency
EPIWIN Estimations Program Interface for Windows
ETIC Environmental Teratology Information Center
EU European Union
FDA Food and Drug Administration
GIF Graphite Impregnated Foam
HLC Henry's Law Constant
HMTC Hazardous Materials Technical Center
HPV High Production Volume Chemicals
HSDB Hazardous Substances Data Bank
IARC International Agency for Research on Cancer
IRIS Integrated Risk Information System
KI Krueger International, Inc.
Koc Soil Adsorption Coefficient
Kow Octanol-Water Partition Coefficient
LADDpot Lifetime Average Daily Dose
LOAEC Lowest Observable Adverse Effect Concentration
LOAEL Lowest-Observed Adverse-Effect-Level
MA TURI Massachusetts Toxics Use Reduction
MDI Methyl Diphenyl Diisocyanate
MOE Margin of Exposure
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NIOSH National Institute for Occupational Safety and Health
NIST National Institute of Standards and Technology
NOAEC No Observable Adverse Effect Concentration
NOAEL No-Observed Adverse-Effect-Level
NTE Neurotoxic Esterase
NTP National Toxicology Program
OctaBDE Octabromodiphenyl Ether
OECD Organization for Economic Cooperation and Development
OPPT Office of Pollution Prevention and Toxics
PBDE Polybrominated Diphenyl Ether
PEC Predicted Environmental Concentration
PentaBDE Pentabromodiphenyl Ether
PESTAB Pesticides Abstracts
PFC Plaque-Forming Cell
PPBIB Poisonous Plants Bibliography
SIC Standard Industrial Classification
SNUR Significant New Use Rule
SWC Surface Water Concentration
TCPP Tris (2-chloroisopropyl) Phosphate
TDCPP Tris (l,3-dichloro-2-propyl) Phosphate
TDI Toluene Diisocyanate
TSCA Toxic Substances Control Act
TSCATS Toxic Substances Control Act Test Submissions
UFAC Upholstered Furniture Action Council
USGS U.S. Geological Survey
VCCEP Voluntary Children's Chemical Evaluation Program
VI
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ABOUT THE PARTNERSHIP
U.S.EPA*
U.S. EPA's Design for the Environment (DfE) Program is a results-oriented voluntary
partnership program. It achieves risk reduction through pollution prevention and applying
Agency expertise and technical tools.
Designing for the environment is incorporating environmental considerations into business
decision making. The EPA DfE Program collaborates with industry sectors to help businesses
design or redesign products, processes and management systems that are cleaner, more cost-
effective and safer for the worker and the public.
The Furniture Flame Retardancy Partnership is a joint effort among the U.S. EPA DfE Program,
U.S. EPA Region IX, all segments of the furniture industry supply chain, government and non-
government groups to identify environmentally safer solutions for meeting current and future
furniture fire safety requirements.
Steering Committee Members:
American Home Furnishings Alliance (AHFA) (formerly AFMA)
"AHFA understands and supports the long range nature of this project and encourages
EPA to remain engaged with private sector stakeholders to develop environmentally sound
solutions to fire safety."
100 Years
AH FA
Business and Institutional Furniture Manufacturer's Association (BIFMA)
International
"BIFMA is committed to promoting sustainable work environments and business practices
based on sound economics, environmental protection, and social responsibility."
American Fire Safety Council (AFSC)
"AFSC is committed to improving fire safety standards and saving lives...We expect this
partnership to lead to the implementation of safe and environmentally sound approaches
to fire safety."
GreenBlue
"GreenBlue is attracted to this partnership because of the rare opportunity to
reconceive design criteria for flame-retardant products."
B FMA
AFSC
O
vn
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Partners:
FURNITURE MANUFACTURERS
American Home Furnishings Alliance
(AHFA) (formerly AFMA)
Business and Institutional Furniture
Manufacturer's Association (BIFMA)
International
Berkline/Benchcraft
Brayton International
Herman Miller
HNI Corporation (formerly Hon
Industries)
Krueger International, Inc. (KI)
Steelcase
CHEMICAL MANUFACTURERS
American Fire Safety Council (AFSC)
Albemarle Corporation
Ameribrom, Inc. (ICL Industrial
Products)
Great Lakes Chemical Corporation
Para Chem
Supresta (formerly Akzo Nobel)
FABRIC/BARRIER MANUFACTURERS
Craftex Mills
Culp
Felters
Glen Raven
Microfibres
National Textile Association
Quaker
NON-GOVERNMENTAL
ORGANIZATIONS
Clean Production Action (CPA)
GreenBlue
Massachusetts Toxics Use Reduction
Institute (MA TURI)
GOVERNMENTAL ORGANIZATIONS:
U.S. Environmental Protection Agency (EPA) - Design for the Environment Program
Consumer Product Safely Commission (CPSC)
National Institute of Standards and Technology (NIST) - Building and Fire Research Laboratory
Vlll
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1.0 INTRODUCTION
This volume contains the purpose and scope of the assessment, a description of the general
characteristics of flame retardants, a general overview of exposure pathways and routes for flame
retardants used in flexible polyurethane foam and the results of the assessments of 14
formulations of flame-retardant products most likely to replace commercially available
pentabromodiphenyl ether (pentaBDE).
A second volume, subtitled, "Chemical Hazard Reviews," consists of the complete data sets for
each of the chemicals of the 14 formulations of flame-retardant products evaluated in this study.
Volume 2 is available under a separate cover at
http ://www. epa. gov/dfe/proj ects/flameret/index.htm.
1.1 Purpose of the PentaBDE Alternatives Analysis
A significant quantity of the residential upholstered furniture sold in the United States contains
low-density, flexible polyurethane foam. Without some form of fire protection, the foam is
highly flammable. To address this safety issue, mandatory flammability standards and
regulations have been enacted for residential upholstered furniture in California. California,
Illinois, and Ohio have flammability standards for commercial furniture as well. The Upholstered
Furniture Action Council (UFAC), an all-industry group, has also implemented voluntary
standards for resistance to ignition from smoldering cigarettes. Most foam and furniture
flammability standards and regulations (domestic and foreign) are performance based and do not
specify particular chemicals or methods to achieve flame retardancy. Therefore, chemicals are
not specifically required; rather, any method (chemical or product design) that achieves the
standard is acceptable. Historically, halogenated flame-retardant chemicals, both brominated and
chlorinated, have been used as a cost-effective method to meet standards without compromising
product quality.
Polybrominated diphenyl ethers (PBDEs) make up a category of structurally similar chemical
flame retardants, which are used in a variety of applications. The application of the individual
PBDE varies according to the number and location of bromine atoms attached to the diphenyl
ether. There are ten possible sites for bromine to bind, decabromodiphenyl ether representing full
saturation. The structure for pentaBDE contains five bromine atoms (C^HsBrsO). The bromine
atoms can be bound to any of the carbon atoms, resulting in several possible isomers of
pentaBDE (some of which are much more chemically stable than others). Figure 1-1 shows a
generic figure for all PBDEs, where "m" and "n" refer to the number of bromine atoms bound to
each aromatic ring. 1fm + n = 5, the resulting structure is a pentaBDE isomer.
Commercially available pentaBDE is actually a mixture of PBDE congeners where the primary
component is pentaBDE. The remaining congeners typically include triBDE (0 to 1 percent),
tetraBDE (24 to 38 percent), and hexaBDE (4 to 12 percent) (European Chemicals Bureau,
2001). For these congeners, m + n = 3, 4, and 6 respectively. Unless otherwise noted, all
references in this report refer to the commercial pentaBDE mixture rather than the pure
pentaBDE chemical.
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Brn Brm
Figure 1-1 Pentabromodiphenyl Ether (pentaBDE), where m+n = 5
Brominated flame retardants (BFRs), such as pentaBDE, act by chemical interaction to prevent
the spread of a fire. Combustion is typically propagated by a series of chemical reactions, where
oxygen combines with chemicals in the burning product. BFRs interrupt some of these reactions
by volatilizing halogen radicals to react with the product in place of oxygen, slowing
combustion.
PentaBDE has been the primary flame retardant for low-density, flexible polyurethane foam in
residential furniture and mattresses for several years. About 8,500 metric tons (18.7 million
pounds) of pentaBDE is used each year worldwide (Peltola and Yla-Mononen, 2000) with
approximately 98 percent of that being consumed in North America (Environ International
Corp., 2003). Although pentaBDE saves lives by retarding fires, there is growing concern over
the persistence and bioaccumulation of pentaBDE that may originate from foam manufactured
with this chemical. Information on the presence of pentaBDE in the environment and biota, and
its effects can be found in Appendix A of this report. More information on pentaBDE can be
found in the Agency for Toxic Substances and Diseases Registry (ATSDR) Toxicological Profile
for Polybrominated Biphenyls and Polybrominated Diphenyl Ethers (Update) (ATSDR, 2004)
and the Voluntary Children's Chemical Evaluation Program (VCCEP) Pentabromodiphenyl
Ether Peer Consultation Meeting Report (TERA, 2004).
The European Union (EU) banned the use and sale of pentaBDE as of August 2004.
Subsequently, the sole U.S. manufacturer of pentaBDE voluntarily phased out its production on
December 31, 2004. In addition to the voluntary phase-out, legislation has been passed to
prohibit the manufacturing, processing, or sale of substances or articles containing more than 0.1
percent by mass of pure pentaBDE in Hawaii and California in 2006 (January 1 and June 1,
respectively).
The phase-out of production presents the need for alternatives to pentaBDE that are
environmentally safer, economically feasible, satisfy fire safety requirements and meet industry's
performance needs. In addition, the U.S. Consumer Product Safety Commission (CPSC) plans to
implement new national fire safety standards regarding residential upholstered furniture that may
lead to an increased need for flame-retardant furniture materials and an increased use of chemical
flame retardants. The Furniture Flame Retardancy Partnership was formed as a result of this
increased need to find practical alternatives that will suit the needs of all parties.
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1.2 Scope of the PentaBDE Alternatives Analysis
Industry is actively exploring alternative methods to meet current and proposed fire safety
standards. The Furniture Flame Retardancy Partnership is a project in which industry leaders
have teamed with EPA and non-governmental environmental groups to evaluate each alternative
based on human health, environmental, performance and cost considerations. The Furniture
Flame Retardancy Partnership will identify the characteristics of the alternatives and anticipates
that industry will choose flame retardants that perform well in each of these areas as full-scale
replacements for pentaBDE.
To date, the Furniture Flame Retardancy Partnership has evaluated available toxicological
information for replacements for pentaBDE in low-density, flexible polyurethane foam. These
are flame retardants that are viable options for meeting the performance requirements of
California's TB117 standard. This report includes information prepared for this short-term goal
and presents it in a common format that will be directly useful to industry as replacement flame
retardants are selected.
The Furniture Flame Retardancy Partnership also has longer-term goals that are not included in
this report. The next phase of this project will look at flame-retardant options for meeting the
planned CPSC flammability standard for residential upholstered furniture. In the future, the
Furniture Flame Retardancy Partnership intends to develop a process to identify additional
toxicological data needed for adequately assessing the pentaBDE alternatives that attain a
significant market share. This effort will help industry to develop a common level of
toxicological information for such flexible foam flame retardants. The Partnership also intends to
encourage development of safer flame retardants through high-level EPA recognition.
Alternative flame retardants can be separated into two categories: alternative chemicals and
alternative technologies. The ideal chemical alternative would be a drop-in replacement that has
similar physical and chemical properties to pentaDBE formulations such that existing storage
and transfer equipment as well as foam production equipment can be used without significant
modification. Most pentaBDE formulations are liquid, so most U.S. foaming operations are
currently equipped to use liquid streams in the production of foam. Any chemical substitute that
is not a liquid or is extremely viscous will require most U.S. operations to alter existing
equipment - at significant cost - to accommodate the new chemical. If the alternative is not
compatible with existing process equipment at foam manufacturing facilities, the plants will be
forced to modify their processes and potentially have to purchase new equipment. Holding cost
and feasibility as significant considerations, this report has focused on evaluating several of these
potential drop-in chemicals.
Four chemical manufacturers have identified viable formulations for EPA review. These
formulations are listed in Table 1-1. The chemicals in each formulation were screened for
potential toxicological and environmental hazards as well as for potential exposure. A summary
of the evaluations of this data is organized in Table 4-1 in Section 4.
The data presented on the formulations provide a means for comparison and allow the reader to
conduct a screening-level hazard evaluation for each chemical alternative. Chemical release
points and associated exposure routes and pathways for flame-retardant chemical manufacturing
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facilities, foam manufacturing facilities and furniture manufacturing facilities are included in
Section 3 of this report.
Table 1-1 Potential Flame-Retardant Chemical Formulations
Albemarle
Corporation
SAYTEX® RX-8500
SAYTEX® RZ-243
ANTIBLAZE® 195
ANTIBLAZE®205
ANTIBLAZE® 180
ANTIBLAZE® V-500
ANTIBLAZE® 182
Ameribrom, Inc. (ICL
Industrial Products)
FR513
Great Lakes Chemical
Corporation
Firemaster® 550
Firemaster® 552
Supresta
(Akzo Nobel)
Fyrol® FR-2
AB053
AC003
AC073
Non-chemical alternatives that eliminate the need for pentaBDE are addressed in Section 5.5 of
this report. Though these technologies may not be considered feasible for immediate
implementation or application for flame retarding foam, these alternative technologies are being
considered for further investigation by the Furniture Flame Retardancy Partnership. Three
currently available, alternative technologies for flame retarding furniture include barrier
technologies, graphite impregnated foam and surface treatment. There is considerable interest in
future applications of these technologies for the furniture industry.
This report is intended to provide information that will allow industry and other stakeholders to
evaluate environmentally safer alternatives for flame retarding furniture. The report is organized
as follows:
• Section 1 (Introduction): This section provides a background to the
Furniture Flame Retardancy project including the purpose and scope of the
Partnership and of this report.
• Section 2 (ChemicalFlame Retardants): This section describes
characteristics of the flame-retardant chemicals currently used in flexible
polyurethane foam and the mechanisms by which they suppress fires.
• Section 3 (Exposure): This section provides a general discussion of
exposure concerns that should be evaluated when conducting an
environmental risk assessment and identifies exposure pathways and
routes associated with flame-retardant chemicals used in furniture
manufacturing.
• Section 4 (Alternatives Evaluations): This section contains EPA's
exposure and hazard assessments on a chemical-specific and formulation-
specific basis for the flame-retardant formulations being evaluated.
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Section 5 (Considerations): This section addresses considerations for
selecting a replacement for pentaBDE based on environmental and
economic feasibility. It also includes alternative technologies that may
serve as alternatives to chemical flame retardants.
1-5
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2.0 TYPES OF CHEMICAL FLAME RETARDANTS
Publicly available scientific literature contains a wealth of information about various mechanisms of
flame retardancy and characteristics of flame retardants. This section summarizes the general
characteristics associated with flame retardants and associated mechanisms of flame retardancy.
2.1 General Characteristics of Chemical Flame Retardants
Some general characteristics of flame-retardant chemicals mandate how they interact with and flame
retard the substrate in which they are used. This section defines some of these important characteristics,
including:
• General mechanisms of flame retardancy;
• Additive and reactive flame-retardant chemicals; and
• Flame-retardant synergists.
2.1.1 General Mechanisms of Flame Retardancy
In general, flame retardants act in one of two ways; either by preventing ignition or preventing the
spread of a fire. First, the ignition susceptibility of a product lowers when the flame retardant increases
the net heat capacity of the product. Second, once a fire has already begun, flame retardants can reduce
the tendency of the fire to spread by reacting with the product and forming a less flammable char or
noncombustible gaseous layer along the boundary of the fire.
Within these two general flame-retardant mechanisms, Kirk-Othmer's Encyclopedia of Chemical
Technology (Kirk-Othmer, 2001) provides a more detailed summary of five specific mechanisms by
which flame retardancy may occur: physical dilution, chemical interaction, inert gas dilution, thermal
quenching and protective coatings.
• Physical dilution: The flame retardant can act as a thermal sink, increasing the
heat capacity of the product or reducing the fuel content to a level below the
lower limit of flammability. Inert fillers such as glass fibers and microspheres and
minerals such as talc act by this mechanism.
• Chemical interaction: The flame retardant dissociates into radical species that
compete with chain propagating and branching steps in the combustion process.
This is the general flame-retarding mechanism by which brominated flame
retardants operate.
• Inert gas dilution: Flame-retardant additives produce large volumes of
noncombustible gases when the product decomposes during combustion. The
gases dilute the oxygen supply to the flame or dilute the fuel concentration below
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the flammability limit. Metal hydroxides, metal carbonates and some nitrogen
producing compounds function in this way when used as flame retardants.
• Thermal quenching: Endothermic degradation of the flame retardant results in
thermal quenching. Metal hydroxides and carbonates act in this way.
• Protective coatings: Some flame retardants function by forming a protective
liquid or char barrier that acts as an insulating layer to reduce the heat transfer
from the flame to the combusting product. Phosphorous compounds that
decompose to give phosphoric acid and intumescent systems operate by this
mechanism.
BFRs such as pentaBDE react chemically to prevent the spread of a fire. In products without BFRs,
combustion is propagated by a series of chemical reactions that occur in the gas phase, where oxygen
combines with chemicals in the burning product. BFRs interrupt some of these reactions by introducing
the volatilized halogens to react with the product in place of oxygen, slowing combustion.
2.1.2 Additive and Reactive Flame Retardants
Flame retardants are categorized as either additive or reactive. Additive flame-retardant chemicals can
be added to a manufactured product without bonding or reacting with the product. They are incorporated
and dispersed evenly throughout the product, but are not chemically bound to it. Reactive flame-
retardant chemicals may be incorporated into the product during manufacture of the plastic raw
materials. They are chemically bound to the raw materials that are used to make the final product.
The basic mechanisms of flame retardancy (discussed earlier) will vary depending on the specific flame
retardant and substrate. Additive and reactive flame-retardant chemicals can function in the vapor or
condensed phase. Depending on the specific chemical, any of the mechanisms previously discussed may
be utilized. Due to specific physical and chemical properties of the flame retardant and its effects on the
substrate, most are used exclusively as either reactive or additive.
Additive Flame Retardants
Most flame retardants are used as additive flame retardants. Commercial pentaBDE is added at the time
the polymer is formed. In general, additive flame retardants react when heated and either (a) emit
substances that displace the oxygen needed for a fire to burn, (b) form a protective coating on the
surface of a flammable substrate, thereby limiting access of the fire to fuel sources, or (c) do a
combination of both. Halogenated flame retardants act in the gas phase by releasing chlorine- and/or
bromine-containing radicals. In contrast, other flame retardants quench the flame by forming an
intumescent, resinous char on the surface of the polymer. This char insulates and protects the polymer
from further decomposition. The flame retardant in the system then expands, helping to form an
insulating barrier that limits further damage to the polymeric material.
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Additive flame retardants used in foam and other plastics are typically incorporated after manufacture of
the polymer and during the manufacture of the end product (at the final product manufacturing facility).
These additives are mixed into the polymer in common processing equipment concurrently with other
ingredients such as stabilizers, pigments and processing aids. This is most likely to occur during a very
preliminary stage at the end-product manufacturing facility (typically during the compounding step).
Reactive Flame Retardants
Reactive flame retardants are chemically bound to polymer products either by incorporating them into
the polymer backbone during the polymerization reaction or by grafting them onto it. This is most likely
to occur at the foam manufacturing facility. Therefore, reactive flame retardants are typically already
incorporated in the raw materials that are purchased and received by the furniture manufacturers
Note that because they are chemically bound to the substrate, reactive flame retardants tend to exert a
much greater effect than additive flame retardants on the properties of the polymer they are incorporated
into.
2.1.3 Flame-Retardant Synergists
Many flame-retardant synergists do not have significant flame-retardant properties by themselves;
however, their use increases the overall effectiveness of the flame-retardant system.
While char formation in the condensed phase and halogen interference in the vapor phase take place
when flame retardants are used alone, the presence of a synergist can dramatically increase the flame
retardant's effectiveness, lowering the quantity of the flame retardant needed to meet the required
standard. Since high levels of flame retardants often affect product quality, a synergist to reduce the
amount of flame retardant is often used. Additionally, the cost of flame retardants can be significant;
therefore, any method to decrease the quantity of flame retardants needed is advantageous.
As an example of synergistic mechanisms, some synergists retard fire via two processes. In the
condensed phase, a char layer is formed during the reaction with the synergistic compound, the flame
retardant and the polymer. As discussed above, this char acts as a shield as it reduces the rate of
decomposition of the polymer; therefore, less fuel is available for the flame. In the vapor phase, the
chemical reaction is slowed down. This adds to the flame retardant's inhibitory effects on combustion by
allowing it to react more completely with free radicals of oxygen and hydrogen, which are necessary for
combustion to occur (Kirk-Othmer, 2001).
As an example of how synergists can be used, consider organophosphorous flame retardants. When used
alone, organophosphorous flame-retardant concentrations may need to be extremely high. These
concentrations of the flame retardant often adversely affect the properties of the product. Testing has
shown that adding inorganic synergists can dramatically increase the flame-retardant efficiency.
Therefore, a significantly smaller quantity of the flame retardant is required. The synergistic effect on
flame retardancy, coupled by the reduction in adverse effects on the product from the flame retardant is
attractive to flame-retardant and end-product manufacturers.
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2.2 Flame-Retardant Chemicals Currently Used in Foam
A wide variety of flame-retardant chemicals are currently in use throughout the world to meet fire safety
standards for various types of foam. Many of these chemicals could theoretically be used to meet U.S.
fire safety standards for low-density, flexible polyurethane foam. However, their use will result in trade
offs. Some, for example, require high loadings that result in an effect on foam quality. Others are cost
prohibitive. Still others will require significant modifications in the handling and process equipment
that is currently used in most U.S. foam manufacturing facilities. The environmental assessments
presented in this report correspond to 14 specific formulations that chemical companies presented as the
most viable large-scale substitutes for pentaBDE. However, other chemicals (besides these 14
formulations) are currently used for other types of foam and in niche markets for low-density
polyurethane foam.
PentaBDE is an additive flame retardant that was used as a liquid formulation, typically blended with
isopropylphenyl diphenyl phosphate/triphenyl phosphate and other additives. The commercial
PentaBDE products have been used to flame retard low-density, flexible polyurethane foam (Weil and
Levchik, 2004). Great Lakes Chemical Corporation was the sole manufacturer of pentaBDE in the
United States, but Akzo Nobel and Great Lakes produced pentaBDE flame-retardant products prior to its
phase-out. PentaBDE composition in products is proprietary.
The remainder of this section briefly discusses three of the most commonly used chemicals that various
reports have suggested may be viable alternatives to pentaBDE. The chemicals are used domestically
and abroad to flame retard high-density, flexible polyurethane foam. Chemical companies and foam
manufacturing facilities have experimented with their use in low-density flexible foams with moderate
success. Generally the use of these chemicals either results in scorching of the foam (an aesthetic effect
unless severe) or a negative effect on the physical properties of foam. Also, many formulations of these
chemicals are available only as solids; making them less desirable as drop in substitutes for pentaBDE.
Melamine
There are numerous international manufacturers of melamine. Melamine and its derivatives are non-
halogenated flame retardants, typically used as a crystalline powder. Flame retardants based on
melamine are currently used in flexible polyurethane foams, intumescent coatings, polyamides and
thermoplastic polyurethanes (Special Chemicals, 2004). They are used effectively in Europe in high-
density flexible polyurethane foams but require 30 to 40 percent melamine per weight of the polyol.
Tris (l,3-dichloro-2-propyI) phosphate (TDCPP)
TDCPP is a chlorinated phosphate ester that is often used in polyurethane foam formulations. TDCPP
comprises approximately 12 percent of the weight of the polyol in the final foam product (Weil and
Levchik, 2004). It is used in high-density foam domestically and abroad and has been used domestically
in low-density foams when light scorching (discoloration) is not a primary concern (Akzo Nobel, 2002).
Note that TDCPP has been mistakenly referred to as tris (chloropropyl) phosphate (TCPP) in many
reports.
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Ammonium Polyphosphate (APP)
APP is an additive flame retardant containing nitrogen and phosphorus, typically used in a crystalline
form. It is currently used to flame retard flexible and rigid polyurethane foams, as well as in intumescent
laminations, molding resins, sealants and glues (Leisewitz et al., 2001). APP formulations comprise
approximately 4 to 10 parts per hundred parts polyol in flexible foam, and 20 to 45 parts per hundred
parts polyol in rigid foam.
APP is included in this section because it has been listed in multiple sources as a flame retardant for
several products, including flexible, polyurethane foam. However, chemical manufactures and foam
manufacturing trade groups do not consider it to be an alternative for pentaBDE on a large scale.
Reasons for this are that APP is typically incorporated as a solid, it has adverse effects on foam
properties and processing and it is not considered to be as effective as a fire retardant compared to other
alternatives (U.S. EPA, 2002).
These chemicals have been used in the United States and around the world to flame retard flexible
polyurethane foam. However, only pentaBDE is capable of achieving flame retardancy and non-
scorching requirements in the low-density foam that is manufactured in the United States. While other
flame retardants have historically been used and will continue to be used to flame retard higher-density
foams, these flame retardants result in scorching in many low-density foam formulations. These
chemicals are potential alternatives for pentaBDE, but scorching and other drawbacks must be addressed
before large-scale use is feasible.
Scorching results in foam that has a color gradient but unless severe, it will not adversely affect flame
retardancy or foam performance. White foam has become the industry standard for flame-retarded, low-
density foam in the mattress and bedding industries, and in many upholstered furniture applications in
the United States. The color of the foam, however, is not a determinant of its flame retardancy. Greater
acceptance of darkened foams would allow manufacturers to choose from a wider variety of alternative
flame retardants.
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3.0 EXPOSURE TO FLAME-RETARDANT CHEMICALS IN FOAM
To evaluate the risk to human health and the environment that is associated with any of the
alternatives to pentaBDE, many factors must be considered. Risk is a function of two parameters,
hazard and exposure. If there is very little exposure, then even the most hazardous chemicals
pose minimal risk. However, if exposure is not well characterized, it cannot be assumed that
there is no risk. The purpose of this section is to identify the highest priority routes of exposure
to flame retardant chemicals used in foam that need to be further assessed and quantified. This
section should be considered with the chemical-specific hazard analysis presented in Section 4.
This section provides: general background regarding exposure pathways, discusses factors that
affect exposure potential in an industrial setting, provides process descriptions for the industrial
operations involved in the furniture manufacturing supply chain (identifying the primary release
points and exposure pathways) and discusses consumer and environmental exposures.
Exposures to specific chemicals are not discussed; rather, the purpose is to provide information
such that the reader can identify and characterize potential exposures based on the physical and
chemical properties of any pentaBDE alternative.
Exposure can occur at many points in the life cycle of a flame-retardant chemical. There is a
potential for occupational exposures during industrial operations; exposure to consumers while
the flame-retarded product is being used; and exposure to the general population and
environment when releases occur from product disposal or from manufacturing facilities. Figure
3-1 presents a simplified life cycle for a flame-retardant chemical used in low-density
polyurethane foam.
3.1 Exposure Pathways and Routes (General)
There are multiple ways people and the environment can be exposed to chemicals and the
different types of exposures can impact the effect of the hazard. For instance, the toxicological
effects from exposure to skin are different than those from exposures from swallowing or
inhaling a chemical. Because of this, exposure is typically characterized by different pathways
and routes.
An exposure pathway is the physical course a chemical takes from the source of release to the
organism that is exposed (how the chemical gets to the individual). The exposure route is a
description of how the chemical gets into the organism. The three primary routes of exposure
are: inhalation, dermal absorption and ingestion.
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Industrial
Manufacturing
and Use
Chemical
Manufacturing
Foam
Manufacturing
Furniture
Manufacturing
—*• Material Stream
>• Recycle Stream
-->• Chemical Stream
Off-Spec and Scrap Foam
Carpet Cushion
Manufacturing
Scrap Foam
--
Occupational
Exposure
Consumer Use
Residential
Furniture
Mattresses
Carpet Cushion
Volatilization and
Deposition onto
Dust in Homes
(Consumer
Exposure)
Post Consumer Use
(Product End-of-Life)
Landfill
Incineration
Recycling
Migration to Surfacewater and Groundwater Combustion Byproduct Formation and Release Additional Occupational
(Environmental and General Population Exposure) (Environmental and General Population Exposure) Exposures
Figure 3-1 Simplified Life Cycle for a Flame-Retardant Chemical
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Expected environmental releases and potential occupational exposures are dependent upon the
physical and chemical properties of the chemical of concern. For example, a highly volatile
liquid will readily evaporate from mix tanks and open transfer operations, potentially resulting in
significant fugitive air releases and occupational exposures to workers that breathe the vapors.
Conversely, chemicals that are manufactured and formulated as solids do not typically result in
exposure to vapors, but may result in inhalation exposure to fugitive dust.
As noted above, risk is a function of the hazardous effects of an environmental toxicant and the
level of exposure to it. Depending on the effects, exposure from only one or perhaps all three
routes may result in significant risk. Therefore, each potential route should be evaluated
independently along with an evaluation of appropriate endpoints. Endpoints are the specific
toxicological effect, such as cancer, reproductive harm, organ/tissue damage or death.
There are circumstances when a chemical has serious effects for endpoint; however, its physical
and chemical properties as well as environmental fate minimize the potential for it to be
transported from the release point through the environment. This may essentially eliminate a
potential pathway and route of exposure and eliminate the associated risk. For example, some
chemicals are only hazardous if they are inhaled. If the chemical is non-volatile, the likelihood of
breathing vapors containing the chemical is very low. This only generally applies to inhalation
exposure from volatilization of liquid chemicals. If the chemical is solid, there is potential
inhalation exposure associated with breathing dust. In another example, if the primary concern is
due to skin sensitization, then a requirement for workers to wear appropriate gloves may reduce
or mitigate the risk.
3.2 Industrial Releases and Exposures
This section provides process descriptions and identifies the corresponding release and exposure
points for the unit operations that are involved within the furniture manufacturing supply chain.
It should be noted that many of the potential occupational exposures identified here could be
reduced or eliminated by the use of engineering controls and personal protective equipment.
Also, some releases will only result in exposure to workers, while other releases result in
exposures to the environment and the general population. The level of exposure between workers
and the general population will vary considerably. Therefore, a risk evaluation should address
occupational exposures separately from environmental and general population exposure.
Factors to consider when identifying and assessing potential pathways and routes of exposure are
discussed below. Examples provided are occupational exposures. A more in-depth review of
occupational exposures, consumer and general population exposures follows.
Inhalation Exposures
The physical state of the chemical during chemical manufacturing and downstream processing
has a significant effect on the potential for inhalation exposure to workers. In particular, the
physical state can result in three types of inhalation exposures that should be evaluated:
Dust: Chemicals that are manufactured, processed and used as solids have the potential to result
in occupational exposure to fugitive dusts. The potential for significant dust formation depends
on whether the solid chemical is handled in the crystalline form, as an amorphous solid, or a fine
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powder. Formation and handling of crystals and amorphous solids results in significantly less
dust than powders. If there is exposure to dust, the level of exposure is directly proportional to
the concentration of chemical in the particulate form. Therefore, a flame retardant that is used at
a lower concentration results in a decreased exposure from this pathway and route (assuming an
equivalent amount of dust is inhaled).
When assessing occupational exposures to pentaBDE alternatives, it is important to note the
physical state of the chemical at the potential point of release and contact. The pure chemical
may be manufactured as a solid powder, indicating a potential exposure to dust. However, it may
be formulated into solution before any workers come in contact with it; thereby eliminating
inhalation exposure to dust as a potential route.
Vapor: Exposure to vapors can occur when liquid chemicals evaporate during manufacturing,
processing and use. Most chemical manufacturing operations occur in closed systems such that
vapors are contained. However, fugitive emissions are expected during open mixing operations,
transfer operations and loading/unloading of raw materials. More volatile chemicals evaporate
more quickly and result in greater fugitive releases and higher occupational exposures than less
volatile chemicals. Therefore, vapor pressure is the best indicator of potential occupational
exposures to vapors. Studies have indicated that in some situations there is a potential for
chemicals to volatilize from foam during the use of the consumer product (Wilford et al., 2003).
Mist: Non-volatile liquids can result in inhalation exposure if manufacturing or use operations
result in the formation of mist. Therefore, risk assessors always address the potential for
exposure from this pathway. It is unlikely that flame-retardant chemicals used as alternatives to
pentaBDE on a large scale will be applied as a mist. However, some flame retardants that are
applied as surface treatments can be spray applied. In these situations, exposure to mist will
occur and should be evaluated.
Dermal Exposures
Occupational dermal exposure is also affected by the physical state of the chemical at the point
of release and contact. For example, the likelihood of liquids being splashed or spilled during
sampling and drumming operations is different than similar operations involving polymerized
solids, powders, or pellets.
Dermal exposure is also generally assumed to be proportional to the concentration of chemical in
the formulation. For instance, the dermal exposure from contacting a pure chemical is greater
than the exposure from contacting a solution that contains only 10 percent of the chemical.
Screening-level evaluations of occupational dermal exposure can be based on the worker
activities involving the chemical. For example, there may be significant exposure when workers
handle bags of solid materials during loading and transfer operations. Maintenance and cleanup
activities during shut down procedures, connecting transfer lines, and sampling activities also
result in potential dermal exposures.
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Ingestion
Occupational exposures via this route typically occur unintentionally when workers eat food or
drink water that has become contaminated with chemicals. Two pathways should be considered.
First, dust particles may spread throughout the facility and settle (or deposit) on tables,
lunchroom surfaces, or even on food itself that is consumed. Vapors similarly spread throughout
the facility and can adsorb into food and drinking water.
Another potential pathway for ingestion occurs from dust particles that are too large to be
absorbed through the lungs. These "non-respirable particles" are often swallowed, resulting in
exposures from this route.
While ingestion is considered to be a realistic route of exposure to workers, it is often considered
less significant when compared to inhalation and dermal exposures, based on the relative
exposure quantities. Ingestion during consumer use and to the general population is often as
significant as or more important than the inhalation and dermal routes. If persistent and
bioaccumulative compounds get into the environment and build up in the food chain, they can
become a significant exposure concern.
The unit operations associated with each industry sector of the furniture supply chain result in a
unique set of potential release points and occupational exposures to flame retardant chemicals.
Sections 3.2.1 through 3.2.3 present an overview of typical manufacturing processes for these
industry sectors. Potential release points and associated exposure concerns are noted, as
appropriate.
3.2.1 Chemical Manufacturing
The specific unit operations, operating conditions, transfer procedures and packaging operations
vary with the manufacture of different flame-retardant chemicals. The expected releases and
occupational exposures depend on these parameters, the chemical's physical state upon release
and its physical and chemical properties. While it is outside the scope of this report to identify
and quantify the releases and exposures associated with individual chemicals, this section
presents a description of a typical chemical manufacturing process, identifies the potential
releases and notes those that are most variable based on the flame-retardant chemicals produced.
Figure 3-2 presents a generic chemical manufacturing process flow diagram and identifies the
primary release and occupational exposure points.
The first step in most chemical manufacturing processes is to load or charge raw materials into
some type of reactor or mix tank. Production volumes and batch sizes associated with flame-
retardant chemicals typically require the raw materials to be stored in large tanks or drums until
use. Large-quantity liquids are typically pumped into the reactor, and solids are weighed and
transferred via conveyorized, mechanical systems. Small-quantity raw materials may be
manually introduced or carefully metered via automated systems. Releases and exposures are
expected from these operations, but they are associated with the raw materials, not the finished
flame-retardant product.
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Fugitive Air Emission
Raw Materials
Reactor
Fugitive
Air
Emission
Samples*
Fugitive Dust
Emissions
Sample
Equipment*
Fugitive Air
Emission
Separation
(Distillation
Column or
Filtration Unit)
1
Drying Operations
(e.g., drying oven
or spray dryer)
Temporary
Storage and
Filling Operations*
Spent Filters
Separation Waste
and Filtrate
Occupational Exposure Expected
Air Releases
"^ Liquid Releases
->. Solid Releases
Miscellaneous:
•Equipment
Cleaning
•Area Washdowns
Figure 3-2 Generic Chemical Manufacturing Process Flow Diagram
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Crude or intermediate products may be transferred through a series of reactors, distillation
columns, filtration systems, drying ovens, spray dryers and other unit operations. These
processes typically occur in closed systems, with engineering controls that serve both to regulate
operating parameters such as temperature and pressure as well as to minimize fugitive releases.
However, there is potential for a variety of solid and liquid releases from these operations, from
cleaning process equipment and from sampling activity. Additionally, crude or finished products
may be stored on-site in drums, day-tanks, or more permanent storage vessels until the flame-
retardant formulation is packaged and shipped to customers (e.g., foam and textile
manufacturers). The transfer and packaging operations are expected to result in releases of and
exposures to the flame-retardant chemicals. Finally, miscellaneous operations, such as routine
and unplanned maintenance activities, can result in considerable releases and exposures.
After the flame retardant is manufactured, it may need to be formulated into a solution, slurry, or
mixture prior to introduction into the commercial flame-retardant formulation. For example, fine
powders of a chemical may be formulated into an agglomerated powder or into a solution. The
formulation steps usually occur at the chemical manufacturing facility, but additional mixing
steps can occur at the foam manufacturing plant.
Release points from manufacturing and formulating can include:
• Transfer and packaging operations involving handling a chemical product;
• Routine and unplanned maintenance activities;
• Leaks from pumps and pipelines;
• Fugitive emissions from equipment;
• Product sampling; and
• Equipment and transport and storage vessel cleaning.
3.2.2 Foam Manufacturing
Flexible polyurethane foam is manufactured as slabstock foam or molded foam. The typical
process used to manufacture each of these is described below. Rigid polyurethane foam is not
discussed here because pentaBDE is used exclusively in flexible foam.
Slabstock Foam
The majority of flexible polyurethane foam is manufactured in slabstock operations. The
slabstock manufacturing process is a continuous process that produces long, rectangular,
continuous slabs of foam, called "buns". Buns are cut into the desired configuration for an
application, such as in furniture padding, bedding, automobile padding and seats, packaging
materials and carpet padding.
The typical commercial process for slabstock foam production consists of a single unit operation,
operated in batches. Figure 3-3 presents a generic diagram for this process. The raw materials
include diisocyanates, polyol, water, auxiliary blowing agents, filler, chain modifying agents and
other additives (including flame retardants).
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PolyoE
TDI
ABA
Water
Surfactant
Catalyst
To Sales -4
Bun Curing and Storage
1 - Chemical Storage
2 - Multiple-stream metering and mixing head
3 - Traversing dispersing head (if used)
4 - Feed trough (Maxfoam)
5 - Conveyer enclosure with exhaust fans
and stacks
6 - Top surface wrapping rolls (optional)
7 - Side paper takeoff rolls
8 - Bottom liner paper roll
9 - Bun saw exhaust hood
10 - Bun saw and operator station
Figure 3-3 Typical Slabstock Foam Production for Flexible Polyurethane Foam
First, the raw materials and additives are metered into a single mix head, which dispenses the
mixed materials to an enclosed conveyor system. Within a few minutes of leaving the mix head,
the raw materials begin to create foam-producing reactions, producing the polyurethane foam on
the conveyor. Most foam manufacturers have computerized controls at the mix head metering
system that allow the raw materials mixture to be changed mechanically, without worker
exposure to the chemicals.
The foam mixture moves down the conveyor at approximately 15 feet per minute. The conveyor
is housed in a tunnel that is ventilated to remove the gases that are given off in the foam reaction.
The foam reaches its full height of 2 to 4 feet in approximately 1 to 2 minutes. After 5 to 10
minutes, polymerization reactions are complete enough for the foam to be handled and cut.
Workers typically enter the tunnel during startup and shutdown procedures or during upset
conditions and usually wear appropriate personal protective equipment. Therefore, this potential
occupational exposure point may be mitigated. Gases are often channeled away from the
workplace and out the facility roof. Therefore, this is a potential environmental release point.
The use of activated carbon filters or other organic vapor control devices on this stream can
reduce releases from this exhaust stream.
-------
A "flying saw" is often used to cut foam on the production line. This is an overhead saw that
moves at the same rate as the conveyor while cutting the foam, in order to produce a straight cut.
Each cut of foam is removed from the conveyor and moved to a curing area. Typically, buns are
cured for 24 hours before further fabrication or shipping. Off gassing may occur during this step.
Therefore, there is potential for inhalation exposure to volatile chemicals from curing operations.
Fabrication includes cutting and slicing the foam to meet the specifications of the customer. A
machine called a slitter cuts large buns into a desired thickness. Vertical bandsaws or hand
cutting tools are used to convert slabs of foam into smaller components for the desired end use
(e.g., furniture). Dermal exposure and exposure to particulates may occur during this step.
Molded Foam
Molded flexible foam is produced when the foam polymerization reaction occurs in a closed
mold resembling the final product. Molded foam is used in the transportation industry for seat
cushions and interior trim, furniture, bedding, packaging materials, toys and novelty items.
The typical commercial process for molded foam production consists of a circular production
line containing multiple molds and process stations. Figure 3-4 presents a diagram of this
process.
Mold Closing
Poiyol
Diisocyanate
Water
Catalyst
Surfactant
Curing Oven
Raw Chemical
Dispensing
Application of Release Agent Mold Conditioning
1
Cell Crushing
Mold Opening and Emptying
Foam
Potential
| Emission Point
Product
Figure 3-4 Typical Molded Foam Production Line for Flexible Polyurethane Foam
Raw materials include polyol, diisocyanates, water, catalyst, surfactant and other additives (e.g.,
flame-retardant formulation). The raw materials are pumped to a common mix head above the
production line. Many ingredients are premixed to minimize the streams being fed to the head
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and to ensure precise measurement. The mix head dispenses a measured amount of the mixture
into each mold and the molds are then heated to accelerate foam curing. Heating takes place
either by passing the mold through a curing oven or passing heated water through tubes in the
mold. Then, the mold is opened and emptied. The mold continues through the process line to be
conditioned for the next product.
Primary release points and corresponding occupational exposures occur from fugitive emissions
during transfer operations and opening/closing the molds. Additional releases and exposures
occur from frequent equipment cleaning operations.
3.2.3 Furniture Manufacturing
Upholstered furniture manufacturers typically receive foam on site, and do not directly handle
flame-retardant chemical formulations. The primary modes of exposure and releases are due to
worker contact with the treated foam. Primary activities where exposure and releases may occur
are during receipt of the foam, cutting and trimming and the placement on the furniture. Figure
3-5 presents a simplified process flow diagram for furniture manufacturing processes. A
significant release may occur from flame-retarded scrap foam. Foam scrap from cutting and
trimming operations is usually sold and utilized in the manufacture of carpet pad foaming.
Otherwise the scrap is disposed of in landfills or by incineration.
Occupational Exposures
Occupational exposures during furniture manufacturing operations may occur due to inhalation
of airborne fibers from handling operations and dust generated during cutting and dermal contact
with treated foam. Workers will be directly exposed to foam that contains flame retardants on a
regular basis as they handle the foam when it is received from suppliers, during incorporation
into furniture and during cutting and cleanup activities.
Releases to Water
Furniture assembly is a dry process; therefore, there are no process water releases that are
expected to contain flame retardants. Additionally, flame retardants are not expected to be
formulated or applied at furniture manufacturing facilities unless the facility elects to use a post-
manufacturing surface treatment alternative. Therefore, waste from container residue or
equipment cleaning is not expected to contain flame retardants.
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Flame Retarded Foam and Fabric
Receive and
Unload
Foam and
Fabric*
Cutting and
Trimming
Apply Foam
and Fabric to
Furniture*
Finished
Upholstery
Product
ugitive Dust and Vapors
Fugitive Dust
and Vapors
Scrap Fabric
Scrap Foam
Handling
ive Dust
and Vapors
Carpet Disposal
Padding (Landfill or
Incineration)
Occupational Exposure
Air
Solid
Figure 3-5 Process Flow Diagram: Furniture Manufacturing
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Releases to Air
It is possible that dust or vapors will be generated and emitted as stack or fugitive emissions as a
result of cutting operations during furniture assembly. Although some air emissions of fugitive
dust containing flame retardants from the facility are possible, the quantity of dust generated and
released to workplace and ambient environments has not been reported.
Releases to Land
The primary potential source of flame-retardant releases to land is scrap from cutting and
trimming operations and floor sweepings. The foam from this waste source is typically collected
and recycled in carpet cushion manufacturing, but may be sent to a landfill.
3.3 Consumer and General Population Exposures
Exposures to consumers and the environment are different from exposures to workers and should
be evaluated separately for a number of reasons. Occupational exposures typically result from
direct contact with chemicals at relatively high concentrations while workers are conducting
specific tasks. Conversely, consumers may be exposed over a much longer period, but to a much
smaller level because the chemical is incorporated into the product. Also, the general population
and the environment will be exposed via different pathways and routes than workers and
consumers. For example, a person that does not own a flame-retarded furniture product may still
be exposed if the chemical leaches from the disposed product into the drinking water supply.
Once in the water supply, groundwater, or surface water, it can be ingested by people or
consumed by fish and other animals. Similarly, if the chemical is released to the atmosphere
during manufacture, use or disposal, it may settle out on food crops and be ingested directly by
people, or by cattle or other livestock. If the chemical is bioaccumulative, it may concentrate in
the animal and reach people through the food chain. For these reasons, exposure to the
environment and the general population should be assessed independently from occupational
exposure.
A quantitative exposure assessment is outside the scope of this report. However, the primary
pathways and routes from environmental, general population and consumer exposures are
discussed in the following sections. Important chemical-specific factors that may help the reader
compare exposure concerns between various pentaBDE alternatives are also discussed.
3.3.1 Physical and Chemical Properties Affecting Exposure
As previously discussed, the physical and chemical properties of a chemical often determine the
potential (or at least the most likely) pathways and routes of exposure. In addition, the chemical
properties dictate how the chemical will become distributed in the environment once it is
released. These interactions in turn dictate the potential for the chemical to be transported from
the release point to the receptor, and the availability for uptake into our bodies.
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Additive vs. Reactive Chemicals
Regardless of the specific chemical composition, flame retardants are often categorized as either
additive or reactive. Reactive flame retardants are chemically bound to the raw materials that are
used to make the final product (i.e., bound to monomers and polymers that make up foam
products). Additive flame retardants are incorporated and dispersed evenly throughout the foam,
but are not chemically bound to it.
Depending on the product and its end use, additive flame retardants can eventually wash off
(e.g., from textiles that are frequently cleaned), volatilize (e.g., from some plastic and foam), or
leach from furniture after it has been disposed of in a landfill. This results in potential exposures
to consumers, the environment and the general population because the furniture itself can be a
source of release. Each furniture article may release very small amounts of the chemical over a
period of several years. However, the combined effect of millions of articles may be very
significant.
Reactive flame retardants are chemically bound to the foam either by incorporating them into the
polymer backbone during the polymerization reaction or by grafting them onto it. This is most
likely to occur at the foam manufacturing facility. Therefore, reactive flame retardants are
typically already incorporated in the foam that is purchased and received by furniture
manufacturers.
Because reactive flame retardants are chemically bound to the foam, it is far less likely they will
be released. It should be noted that even reactive chemicals or close analogues can be released
from the finished article, either when they are liberated from the polymer backbone or because
some of the chemical was not completely reacted during the polymerization process. Also, note
that because they are chemically bound to the substrate, reactive flame retardants tend to exert a
much greater effect than additive flame retardants on the properties of the polymer they are
incorporated into.
Properties Affecting Transport in the Environment (Vapor Pressure, Water Solubility)
If a chemical is released into the environment, either from the finished foam article or directly
from an industrial facility, there still may not be significant exposures unless there is a potential
for it to travel from the source to the receptor. Primary mechanisms of transport include the
water supply and air dispersion. Many factors affect movements of chemicals throughout these
media. However, a few chemical properties can provide a good screening-level indication of
which pathway(s) a chemical is likely to take.
Water solubility is an indicator of the amount of chemical that will dissolve in aqueous solutions.
Chemicals with high water solubility will readily dissolve. This indicates a potential for the
chemical to be transported long distances in rain water and surface water runoff from the point of
release. High water solubility also means the chemical is less likely to settle or precipitate as a
solid at the bottom of a receiving stream; it may become dispersed throughout a drinking water
supply that is eventually ingested by the general population. Water solubility is one of the criteria
used in Section 4 to determine the potential for aquatic exposure and exposure to the general
population via ingestion.
3-13
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The octanol-water partition coefficient (LogKow) is a chemical-specific parameter that reflects
the hydrophobicity of the chemical, meaning the tendency for the chemical to partition from
water to organic phases (e.g. organic matter in soil or water, or lipids in organisms like fish).
Some chemicals may initially be released on the ground; however, they are quickly absorbed by
organic materials in the soil. In this instance, the chemical may never be transported to a water
supply. Chemicals that readily dissolve in water are more likely to find their way to an
underground water supply. The octanol-water partition coefficient is also used in Section 4 to
evaluate aquatic exposure and general population exposure via ingestion. A high partition
coefficient value means that the chemical is more soluble in octanol than in water while a low
partition coefficient value means that the chemical is more soluble in water than in octanol.
Vapor pressure can be used to assess the amount of chemical that vaporizes into the gas phase
(from solution or from a finished article). Similarly, the Henry's Law Constant indicates the
amount of chemical that will volatilize from an aqueous solution. A high vapor pressure and
Henry's Law Constant indicates a higher potential for the chemical to enter the vapor phase and
be transported long distances through ambient air. These parameters are used in Section 4 to
evaluate potential general population exposure via inhalation.
Persistence and Bioaccumulation
If a chemical is released, there still may be little or no potential for environmental and general
population exposures. This potential is affected by the fate of the chemical in the environment
and its ability for uptake by the receptor organism. Two parameters affecting fate components of
the exposure pathway are persistence and bioaccumulation.
Persistence
Many natural phenomena can degrade or destroy chemicals. Factors that can contribute to
degradation include exposure to light, reactivity with air and water and microbial activity. The
ability of a chemical to persist in the environment can be measured by its half-life. This is the
amount of time required for half of the chemical to be degraded. The half-life can be measured
(or estimated) for different media (e.g., half-life in air and half-life in water). Chemicals with a
very long half-life are said to be persistent. Half-life is used in Section 4 to describe the
persistence of pentaBDE alternatives, as well as their expected degradation products.
Bioaccumulation
The toxicological effects exhibited for some endpoints depend on the ability of the chemical to
be absorbed in tissue, and remain for extended periods of time. This general concept is referred
to as bioaccumulation. Chemicals that are highly bioaccumulative pose greater concerns.
Bioaccumulation can be measured or estimated by analyzing a number of parameters, including
the fish bioconcentration factor (BCF). BCFs are used in Section 4 to evaluate the
bioaccumulation potential of each pentaBDE alternative.
3-14
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3.3.2 Consumer Use and End-of-Life Analysis
Currently, there is uncertainty regarding the exposure pathways and routes associated with flame
retardant chemicals such as pentaBDE. A significant amount of research is being conducted to
assess their fate and transport from release points and consumer products to human and
environmental receptors. The Furniture Flame Retardancy Partnership will evaluate the results of
flame retardant exposure research as it is completed. This section very briefly discusses the
potential pathways and routes of exposure associated with consumer uses and end-of-life
(disposal) of flexible polyurethane foam.
Primary Consumer Uses (Furniture, Carpet Cushion and Mattresses)
In the United States today, pentaBDE is primarily used in flexible polyurethane foam for
residential upholstered furniture and mattresses. A significant, secondary market for pentaBDE
foam includes carpet cushion (rebond) manufacturing because large quantities of off-spec and
recycled foam are used to manufacture this product. Millions of pounds of foam that is flame
retarded with pentaBDE or an alternative have been, and will be, sold and used in homes
throughout the United States as carpet cushions. Direct exposure to millions of consumers from
these sources is possible. Recent studies have reported PBDE congeners in house dust (Rudel et.
al., 2003; Stapleton et. al., 2004).
Inhalation Exposure
As discussed earlier, inhalation exposure can occur from dust, vapor and mist. Flame retardant
chemicals that are incorporated into polyurethane foam will not result in consumer exposure to
mist. However, recent studies of indoor air quality suggest that volatilization of PBDEs from
treated furniture foam results in human exposure to PBDEs via inhalation (Wilford et. al., 2003;
Harrad et.al., 2004). This poses a potential, long-term pathway for inhalation exposure. Reactive
flame retardants may result in a lower potential for exposure than additive flame retardants
because the flame retardant should be bound within the foam matrix and is expected to be less
available for release and subsequent exposure.
Dermal Exposure
Dermal exposure is also possible from direct contact with furniture, carpet padding and
mattresses that have been treated with flame retardant chemicals. This pathway and route for
flame retardants in foam is difficult to assess or quantify because foam is typically covered by
textiles or carpet. Still, there is potential for direct contact if the foam is exposed. Additionally, it
is expected that as carpet padding ages, foam dust will be generated and become airborne with
traffic on carpet. This presents a particular exposure potential for children, who spend time on
the floor. Dermal exposure is also possible when volatile chemicals deposit onto dust that
subsequently settles on household surfaces. This potential pathway is expected to be greater for
additive chemicals than for reactives.
3-15
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Ingestion
Ingestion is another route of exposure to consumers that should be considered during a risk
evaluation. As for dermal exposure, young children can be similarly exposed to household dust
containing flame retardants: children are known to ingest larger amounts of household dust than
adults. Mouthing of furniture, bedding and other materials are also possible routes of exposure
for young children.
Miscellaneous and Historical Consumer Uses (Automobiles)
PentaBDE and other flame retardants have been used in flexible and rigid foam seating and other
components of automobile interiors. Industry has been shifting from pentaBDE in this
application over the past several years. However, the foam in automobile seats must still meet
applicable fire safety standards. Therefore, flame retardants are still used. There is one additional
pathway and route of exposure associated with foam in automobile seating that has not been
previously discussed. Studies have shown that a phenomenon known as "fogging" occurs inside
vehicles when components of plastics and foam volatilize during use and deposit on windshields,
creating a film. This typically occurs due to the elevated temperatures in closed autos that are left
in direct sunshine during summer months. Additive chemicals vaporize from foam at these high
temperatures. Fogging is generally associated with plasticizers, but flame retardants and other
additives can also volatilize and contribute to this effect (Bradford et al., 1996).
3-16
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4.0 FLAME-RETARD ANT ALTERNATIVES EVALUATIONS
In order to evaluate chemical alternatives for flame retarding furniture foam, all of the factors
discussed in prior sections of this report must be considered, including toxicology, exposure,
type of flame-retardant chemical, efficacy of use within existing manufacturing systems,
availability and viability of non-chemical alternatives, cost and performance. This report does
not include information on performance testing or cost.
This section summarizes the toxicological and exposure characteristics of each chemical in
alternative flame-retardant formulations that are considered viable substitutes for pentaBDE use
in flexible polyurethane foam. Chemical components less than 1 percent by weight were not
considered in this assessment. The characteristics of the chemicals in each formulation are
summarized qualitatively in Section 4.1 using a relative ranking scheme and more detailed
characteristics of the chemicals in each formulation are presented in Section 4.2.
These evaluations of flame-retardants are not full risk assessments, but do provide screening-
level information on the hazard concerns and potential routes of exposure associated with the
chemical components. Chemical risk is composed of two parts: hazard and exposure. The
hazards evaluated in this report were the potential for human health effects and ecotoxicity.
Exposure refers to the amount of material to which workers, the community or the environment
come into contact. The toxicological information summarized in these evaluations is based on
existing information and will provide the basis for identifying unmet data needs. The exposure
potential is derived from simple criteria applied to the physical, chemical, and environmental fate
properties of the chemicals. A full exposure assessment would consider the quantity, frequency,
duration and route of exposure. Understanding the exposure routes and pathways is critical to
conducting an exposure assessment. The concentration of a chemical in the mixture would factor
into the overall exposure assessment and, therefore, the potential risk associated with the
commercial formulations of the flame retardant alternatives.
4.1 Summary of Flame-Retardant Chemical Alternatives
Table 4-1 presents a qualitative summary of toxicological and exposure characteristics of the
chemicals in each formulation considered in the alternatives analysis. The table qualitatively
summarizes toxicological endpoints and exposure routes for each chemical, including seven
human health effects, two ecotoxicity effects and two environmental endpoints and six routes of
occupational, general population and aquatic exposure. Each of these endpoints is explained in
Table 4-2.
Each toxicological endpoint in Table 4-1 is assigned a rating of L, M, or H to indicate whether
the chemical has a low (L), medium (M), or high (H) hazard concern. If the L, M, or H indicator
is bold or colored, then the assignment was made using experimental data on the chemical. If the
L, M, or H indicator is italicized, then experimental data were not available for that chemical and
the assignment was estimated using structure activity relationships (SAR) analysis involving
modeling techniques and professional judgment. Similarly, each exposure route is assigned a
rating of Y (yes) or N (no) to indicate whether that exposure route may occur for each chemical.
4-1
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Table 4-1 Screening Level Toxicology and Exposure Summary
L = Low hazard concern
M1 = Moderate hazard concern
H = High hazard concern
N = No
Y = Yes
P = Yes for pure chemical
"Ongoing studies may result in a change in this endpoint
APersistent degradation products expected2
L,M,orH = Endpoint assigned using estimated values and professional judgment (Structure Activity Relationships)
Company
Albemarle
Albemarle
Albemarle
Albemarle
ChemicaP
ANTIBLAZE 180 and
ANTIBLAZE 195
Tris(1,3-dichloro-2-propyl)Phosphate
CAS #13674-87-8
ANTIBLAZE 182 and
ANTIBLAZE 205
Proprietary A Chloroalkyl phosphate (1)
Proprietary B Aryl phosphate
Triphenyl Phosphate
CAS #115-86-6
ANTIBLAZE V500
Proprietary C Chloroalkyl phosphate (2)
Proprietary B Aryl phosphate
Triphenyl Phosphate
CAS #115-86-6
SAYTEX RX-8500
Proprietary D Reactive brominated
flame retardant
Proprietary B Aryl phosphate
Triphenyl Phosphate
CAS #115-86-6
CO
C
O
'2
D
E
o
LL.
C
s?
95%
Human Health Effects
Cancer Hazard
M
M
L
L
M
L
L
L
L
L
Skin Sensitizer
L
L
L
L
M
L
L
M
L
L
Reproductive
M
M
M*
L
M*
M*
L
L
M*
L
Developmental
M
M
M*
L
M*
M*
L
L
M*
L
Neurological
L
L
M
L
L
M
L
M
M
L
Systemic
M
M
M*
M
M
M*
M
M
M*
M
Genotoxicity
M
M
L
L
L
L
L
L
L
L
Ecotoxicity
»
I
M
M
H
H
M
H
H
M
H
H
Chronic
M
M
H
H
M
H
H
M
H
H
Environmental
Persistence
M
M
L
L
M
L
L
LA
L
L
Bioaccumulation
L
L
M
L
L
M
L
L
M
L
Potential Routes of Exposure
Worker
Inhalation
N
N
N
Y
N
N
Y
N
N
Y
Dermal
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
c
O
io
-------
Table 4-1 Screening Level Toxicology and Exposure Summary
L = Low hazard concern N = No
M4 = Moderate hazard concern Y = Yes
H = High hazard concern P = Yes for pure chemical
L, M\ orH= Endpoint assigned using estimated values and professional judgment (Structure Activity Relationships)
"Ongoing studies may result in a change in this endpoint
APersistent degradation products expected5
Company
Albemarle
Ameribrom
Great
Lakes
Great
Lakes
Chemical
SAYTEX RZ-243
Proprietary E Tetrabromophthalate diol
diester
Proprietary B Aryl phosphate
Triphenyl Phosphate
CAS #115-86-6
FR513
Tribromoneopentyl Alcohol
CAS # 36483-57-5
Firemaster 550
Proprietary F Halogenated aryl ester
Proprietary G Triaryl phosphate,
isopropylated
Triphenyl Phosphate
CAS #115-86-6
Proprietary H Halogenated aryl ester
Firemaster 552
Proprietary F Halogenated aryl ester
Proprietary G Triaryl phosphate,
isopropylated
Triphenyl Phosphate
CAS #115-86-6
Proprietary H Halogenated aryl ester
CD
C
o
'2
D
E
o
LL.
C
s?
Human Health Effects
Cancer Hazard
L
L
L
M
L
L
L
L
L
L
L
L
Skin Sensitizer
L
L
L
L
L
L
L
L
L
L
L
L
Reproductive
L*
M*
L
M
M
M*
L
M
M
M*
L
M
Developmental
L*
M*
L
M
M
M*
L
M
M
M*
L
M
Neurological
L
M
L
M
L
M
L
L
L
M
L
L
Systemic
M*
M*
M
M
M
M*
M
M
M
M*
M
M
Genotoxicity
L
L
L
M
L
L
L
L
L
L
L
L
Ecotoxicity
&
I
L
H
H
M
H
H
H
H
H
H
H
H
Chronic
H
H
H
M
H
H
H
H
H
H
H
H
Environmental
Persistence
LA
L
L
L
LA
L
L
LA
LA
L
L
LA
Bioaccumulation
L
M
L
L
L
M
L
L
L
M
L
L
Potential Routes of Exposure
Worker
Inhalation
N
N
Y
Y
N
N
Y
N
N
N
Y
N
Dermal
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
c
O
io
-------
Table 4-1 Screening Level Toxicology and Exposure Summary
L = Low hazard concern
M1 = Moderate hazard concern
H = High hazard concern
L, M\ orH= Endpoint assigned using
N = No "Ongoing studies may result in a change in this endpoint
Y = Yes APersistent degradation products expected2
P = Yes for pure chemical
estimated values and professional judgment (Structure Activity Relationships)
Company
Supresta
Supresta
Supresta
Supresta
Chemical
AB053
Tris(1,3-dichloro-2-propyl)Phosphate
CAS# 13674-87-8
AC003
Proprietary I Organic phosphate ester
Triphenyl Phosphate
CAS #115-86-6
AC073
Triphenyl Phosphate
CAS #115-86-6
Proprietary J Aryl phosphate
Proprietary K Aryl phosphate
Proprietary L Aryl phosphate
Fyrol FR-2
Tris(1,3-dichloro-2-propyl)phosphate
CAS# 13674-87-8
CO
C
O
'2
3
E
o
LL.
C
s?
92-99%
1-8%
38-48%
40-46%
12-18%
1-3%
99%
Human Health Effects
Cancer Hazard
M
L
L
L
L
L
L
M
Skin Sensitizer
L
L
L
L
L
L
L
L
Reproductive
M
L
L
L
L
L
L
M
Developmental
M
L
L
L
L
L
L
M
Neurological
L
L
L
L
L
L
L
L
Systemic
M
M
M
M
M
M
M
M
Genotoxicity
M
L
L
L
M*
L
L
M
Ecotoxicity
1
M
H
H
H
L
L
L
M
Chronic
M
H
H
H
H
L
L
M
Environmental
Persistence
M
H
L
L
L
L
L
M
Bioaccumulation
L
L
L
L
L
L
L
L
Potential Routes of Exposure
Worker
Inhalation
N
P
Y
Y
Y
P
P
N
Dermal
Y
Y
Y
Y
Y
Y
Y
Y
c
.g
-------
Table 4-2 Definitions of Toxicological and Environmental Endpoints
Toxicological
Category
Human Health Effects
Ecotoxicity
Environmental
Toxicological
Endpoint
Cancer Hazard
Skin Sensitizer
Reproductive
Developmental *
Neurological
Systemic
Genotoxicity
Definition
Any growth or tumor caused by abnormal and uncontrolled cell division.
Chemical that causes an allergic skin reaction characterized by the presence of
inflammation; may result in cell death.
Adverse effects on the reproductive systems of females or males, including
structural/functional alterations to the reproductive organs/system, the related
endocrine system, mating, or fertility /reproductive success.
Adverse effects on the developing organism (including structural abnormality,
altered growth, or functional deficiency or death) resulting from exposure prior
to conception (in either parent), during prenatal development, or postnatally up
to the time of sexual maturation.
Adverse effects on the central or peripheral nervous system.
Adverse effect (other than those listed separately) that is of either a generalized
nature or that occurs at a site distant from the point of entry of a substance: a
systemic effect requires absorption and distribution of the substance in the
body.
Induction of genetic changes in a cell as a consequence of gene sequence
changes (mutagenicity), or chromosome number/structure alterations.
Adverse effects observed in living organisms that typically inhabit the wild. The assessment focused
on effects in aquatic organisms (fish, invertebrates, algae).
Acute
Chronic
Persistence
Bioaccumulation*
Short-term, in relation to exposure or effect. Exposures are typically less than
96 hours.
Effects observed after repeated exposures.
Attribute of a substance that describes the length of time that the substance
remains in the environment before it is physically removed by chemical or
biological transformations.
Ability of living organisms to concentrate a substance obtained either directly
from the environment or indirectly through its food.
*REFERENCE: International Union of Pure and Applied Chemistry, Clinical Chemistry Division Commission on
Toxicology. Glossary for Chemists of Terms Used in Toxicology (IUPAC Recommendations, 1993).
4.1.1
Explanation of Toxicological and Environmental Endpoints Rating
The assessments combine data on flame-retardant alternatives from four sources: (1) publicly
available measured (experimental) data obtained from a comprehensive literature review; (2)
measured confidential data from EPA OPPT Confidential Business Information (CBI) databases;
(3) SAR-based estimations from EPA's New Chemical Program's P2 Framework and
Sustainable Futures predictive methods; (4) professional judgment of EPA staff who identified
experimental data on closely related analogs; and (5) confidential studies submitted by chemical
manufacturers. When experimental data were lacking, the expert judgment of scientists from
EPA's New Chemical Program was used to assess physical/chemical property, environmental
fate, aquatic toxicity and human health endpoints. The following abbreviations are used to
indicate sources of data presented in this assessment:
• M = Measured/experimental data contained in the open literature;
• MC = Measured/experimental confidential data contained in EPA OPPT
CBI databases or submitted by industry;
4-5
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E = Estimations obtained using predictive methodology; and
P = Professional judgment of subject matter experts.
Table 4-3 lists the criteria that were used to interpret the data collected in this document. These
criteria are used by the EPA New Chemicals Program to assign concern levels to new chemicals
submitted under the Toxic Substances Control Act (TSCA). EPA has published these criteria in
several sources including USEPA 1992, USEPA 1994, and USEPA 1995. EPA New Chemicals
Program persistence criteria have been published in the Federal Register (USEPA 1999).
Table 4-3 Criteria Used to Assign Concern Levels
Concern Level
High
Moderate
Low
Concern Level
High
Moderate
Low
Concern Level *
High
Moderate
Low
Concern Level
High
Moderate
Low
Persistence Criteria
Half-life in water, soil, or sediment > 180 days
Half-life in water, soil, or sediment between 60 and 180 days
Half-life in water, soil, or sediment < 60 days
Bioaccumulation Criteria
Bioconcentration factor (BCF) > 5000
BCF between 1,000 and 5,000
BCF < 1,000
Aquatic Toxicity Criteria
Value is < 1 mg/L (chronic value <0.1 mg/L)
Value is between 1 and 100 mg/L (chronic value 0.1 and 10 mg/L)
Value is > 100 mg/L (chronic value >10 mg/L) or log Kow is greater
than 8
Human Health Criteria
Evidence of adverse effects in human populations or conclusive
evidence of severe effects in animal studies
Suggestive animal studies, analog data, or chemical class known to
produce toxicity
No basis for concern identified
*If the water solubility is estimated, the chemical will not be considered to have "no effects at saturation" if the
estimated value is within a factor of 10 percent of the cutoff value. The concern level will be considered low if "no
effects at saturation" (below the solubility limit).
More information on the EPA New Chemicals Program criteria used to assign concern levels can
be found in the Sustainable Futures Pilot Project Interpretive Guidance Document (attached as
Appendix B to this document) or visit:
http://www.epa.gov/oppt/newchems/sustainablefutures.htm.
There are many other hazard classification systems which can be applied to the experimental
data listed in Section 4.2 and Volume II of this report. Examples of these systems include.
4-6
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• Globally Harmonized System of Classification and Labelling of
Chemicals (GHS)
http://www.unece.org/trans/danger/publi/ghs/ghs_revOO/OOfiles_e.html
• EPA's Office of Pesticide Programs (OPP)
A comparison of the OPP criteria and GHS criteria:
http ://www. epa. gov/oppfead 1/international/global/ghscriteria-
summary.pdf
• EU Dangerous Substance Directive (EU)
Links to the directive, annexes and all amendments can be found here:
http://europa.eu.int/comm/environment/dansub/main67 548/index en.htm
• Annex 6 lists the general labeling and classification requirements for
dangerous substances and preparations:
http://europa.eu.int/comm/environment/dansub/pdfs/annex6 en.pdf
• Canadian Hazardous Products Act (Canada)
The Consumer Chemical Container Regulations:
http://laws.iustice.gc.ca/en/H-3/SOR-2001-269/text.html
• The Controlled Products Regulations:
http://laws.justice.gc.ca/en/H-3/SOR-88-66/text.html
If measured data pertaining to these criteria are not available, they can be estimated based on use
of Structure Activity Relationships (SAR) analysis. SAR is the relationship of the molecular
structure of a chemical with a physicochemical property, environmental fate attribute, and/or
specific effect on human health or an environmental species. These correlations may be
qualitative (simple SAR) or quantitative (quantitative SAR, or QSAR). Information on EPA's
use of SAR analysis has been published in USEPA 1994.
SAR estimations for several physical and chemical properties were obtained using the models of
EPA's P2 Framework. The P2 Framework is an approach to risk-screening that incorporates
pollution prevention principles in the design and development of chemicals. These models are
screening level methods and are intended to be used when data are unavailable or to supplement
available data. They are not intended to replace data from well-designed studies. For
physical/chemical properties and environmental fate parameters, estimates were obtained from
the Estimations Program Interface for Windows (EPIWIN) suite methodology. These methods
were used to obtain melting point, boiling point, vapor pressure, octanol/water partition
coefficient, water solubility, Henry's Law constant, atmospheric oxidation rate, biodegradation
potential, soil adsorption coefficient, bioconcentration factor, hydrolysis rate, volatilization rates
and removal in a sewage treatment plant as applicable. For aquatic toxicity potential, EPA's
Ecological Structure Activity Relationships (ECOSAR) estimation program was used. This
methodology uses chemical structure to estimate toxicity of an industrial chemical to fish,
invertebrates, and algae in the surface water to which the chemical has been discharged. The
program determines both acute (short-term) toxicity and, when available, chronic (long-term or
delayed) toxicity. The potential for a chemical to cause cancer in humans was estimated using
OncoLogic. This program uses a decision tree based on the known carcinogenicity of chemicals
4-7
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with similar chemical structures, information on mechanisms of action, short-term predictive
tests, epidemiological studies, and expert judgment. All estimates obtained in this project were
reviewed by EPA scientists with expertise in the appropriate field.
The persistence of a chemical substance in a screening assessment is based on determining the
importance of removal processes that may occur once a chemical enters the environment. As
noted above, chemicals with a half-life of less than 60 days are expected to be of low concern for
persistence based on the criteria that were used to interpret the data collected in this document.
The persistence screening assessment does not directly address the pathways that a flame
retardant might enter the environment (e.g., volatilization or disposal in a land fill) and focuses
instead on the removal processes that are expected to occur once it is released to air, water, soil,
or sediment. Determining how a chemical enters the environment is typically a component of a
complete exposure assessment or life cycle analysis and is discussed in Section 3. Similarly, the
persistence screening assessment does not address what might happen to a chemical substance
throughout its life cycle, such as disposal during incineration of consumer or commercial
products (incineration is discussed briefly in Section 5.1).
Environmental removal processes are generally divided into two categories: chemical and
biological. One of the most important chemical degradation processes is hydrolysis. The
importance of hydrolysis can be determined from experimental data (on both the compound of
interest and closely related analogs) and by using the half-life obtained from the models within
EPIWIN. Photolysis may also be an important environmental removal process and was
considered in this assessment when experimental data were available. Estimation methods for
photolysis are not available within EPA's Sustainable Future pilot project.
Biodegradation is also considered in determining the persistence of a chemical substance in the
environment. If experimental data on the biodegradation of a chemical substance are not
available, then the potential of the chemical to undergo this process can be assessed from the
results of the EPIWIN models. These models fall into three classes:
1. Probability of rapid biodegradation models based on linear and non-linear
regressions that estimate the probability that a chemical substance will
degrade fast;
2. Expert survey models - semi-quantitative models that determine the rate
of ultimate and primary biodegradation; and
3. Probability of ready biodegradability.
The first set of models are useful for determining if a chemical substance has the potential to
biodegrade quickly in the environment, but do not provide a quantitative indication of its half-
life. If a chemical is likely to biodegrade quickly its half-life is expected to be less than 60 days
and, therefore, it is expected to have a low concern for persistence. The results of the estimates
from the first set of models are used in concert with the semi-quantitative output from the second
set of models, which include an ultimate and primary survey model for evaluating persistence.
These models provide a numeric result, ranging from 1 to 5, to provide an indication of the
amount of time required for complete mineralization (ultimate degradation) and removal of the
parent substance (primary degradation) of the test compound. The numeric result is converted to
4-8
-------
a more meaningful time frame for removal for the user based on the scheme presented in the
following table. The results from the ultimate degradation model can also be used to estimate
the half-life for a chemical, which is also provided in Table 4-4.
Table 4-4 Information for Estimating Half-Life
Model Results for Primary
and Ultimate
>4.75
4.75 to >4.25
4.25 to >3. 75
3. 75 to >3. 25
3.25to>2.75
2.75 to >2.25
2.25 to >1. 75
<1.75
Time for Removal
Hours
Hours to Days
Days
Days to Weeks
Weeks
Weeks to Months
Months
Recalcitrant
Approximate Half-Life (Days,
Based on ultimate)
0.17
1.25
2.33
8.67
15
37.5
60
180
The third set of models (also known as MITI models), and the ready biodegradability test that
they correspond to, are more applicable to determining a chemical's potential for removal in a
sewage treatment plant than its persistence in the environment.
When determining environmental persistence, screening assessments also consider the potential
persistence of breakdown products resulting from biodegradation and chemical removal
processes. This assessment is performed because of the potential for human and environmental
exposure to persistent breakdown products. Breakdown products resulting from hydrolysis can
be determined experimentally or by using professional judgment based on analogs with similar
functional groups. Breakdown products may also be reported in experimental biodegradation
tests or can be determined using professional judgment. When the rate for ultimate degradation is
much slower than that for primary degradation, the potential for persistent breakdown products
exists.
4.1.2
Explanation of Exposure Route Rating
Six exposure routes are presented for each chemical, including two occupational exposure routes,
three general population exposure routes and one aquatic exposure route. Each of these potential
routes is assigned a Y (yes, exposure may occur) or an N (no, exposure is not likely to occur).
The potential for occupational exposure is determined by the physicochemical properties of the
pure material. If the flame retardant is commonly manufactured or formulated as a liquid and the
vapor pressure indicates that it is not expected to volatilize, then a "P" indicates that the potential
for worker inhalation exposure is expected to be limited to those situations when the material is
in a purified form that could contribute to dust-related exposure. The exposure routes are based
on the state of the pure compound or representative pure compound unless further use
information has been provided. The thresholds for each exposure route were adapted from EPA's
New Chemicals Program, except as noted.
4-9
-------
Occupational Exposure
Inhalation
Liquids4: If a liquid has a vapor pressure amenable to volatilization, then the liquid will
evaporate and present the potential for a person to inhale the vapor. Occupational exposure may
occur when the vapor pressure is greater than 1 x 10"06 mm Hg at 25 degrees Celsius. Liquids
may also be inhaled as a mist if the liquid chemical is sprayed during transfer or application
operations.
Solids5: Occupational exposure may occur in all cases when processing or handling solids.
Solid-state chemicals may be used in a crystalline, packed, or powder form. In all cases, a solid
chemical may produce particulate dust as a byproduct of manufacturing or use operations. When
this occurs, a worker may inhale the dust particles while working with the chemical.
Gases6: Occupational exposure may occur in all cases when processing or handling gases.
Gaseous chemicals should always be contained in cylinders to enable their use; however, if they
are uncontained, gaseous chemicals result in exposure to workers. Routine exposure to gaseous
chemicals is not expected unless there is an accident. However, fugitive releases may occur when
connecting transfer lines.
Dermal
Dermal exposures may occur to workers while handling liquid or solid flame-retardant
chemicals. In general, workers handling liquid chemicals may be exposed to the chemical by full
hand immersion, splashing, or spraying depending upon the manufacturing processes utilized at a
facility. Workers handling solid chemicals can be exposed on the surface of their hands as well
as from particulate dust that may settle onto their skin. All chemicals are expected to present a
dermal exposure to workers in this report. The use of personal protective equipment may
mitigate these exposures.
Ingestion
Exposures associated with ingestion are not included for the purposes of this screening level
assessment; however, workers may incidentally ingest flame-retardant chemicals through
ingestion of contaminated food and water. Ingestion may occur if the chemical is suspended in
air as a particulate or a mist as part of manufacturing, and then recondenses or flocculates into
food or drinking sources. Alternatively, secondary ingestion may occur as a result of inhaling the
mist or dust form of the chemical, and then swallowing residual chemical in the nasal or
esophageal passageways.
4 Liquids are substances that have a melting point less than 25 degrees Celsius and a boiling point greater than 25
degrees Celsius.
5 Solids are substances that have a melting point of greater than 25 degrees Celsius.
6 Gases are substances that have a boiling point less than 25 degrees Celsius.
4-10
-------
General Population Exposure
Inhalation
Liquids7: If the liquid has a vapor pressure amenable to volatilization from the product in which
the chemical is carried, a person may inhale the liquid as a vapor while in contact with the
product or substance carrying the chemical. For this report, general population exposure may
occur if the chemical vapor pressure is greater than 1 x 10"06 mm Hg at 25 degrees Celsius and if
the chemical is additive, not reactive8.
Solids9: General population exposure may occur if the vapor pressure is greater than 1 x 10"06
mm Hg at 25 degrees Celsius and if the chemical is not reactive. Although not included in this
screening level assessment, as foam products age and break down, particulate (matter) may be
released from the foam products which may contain flame-retardant chemicals. This flame-
retardant foam dust may be present in carpets or in flame-retardant furniture and could represent
an exposure to the general population.
Gases10: General population exposure is not expected to occur if the chemical is a gas, since
gases would not be intentionally contained outside of the manufacturing arena (excluding
accidental releases).
Dermal
Dermal exposures may occur to the general population while handling products or substances
containing the flame-retardant chemical, if the flame-retardant chemical is not reactive.
Ingestion
The general population may be exposed to a flame-retardant chemical if the chemical has water
solubility greater than 1 x 10"06 grams/liter, is dispersible, or has the potential to leach. These
would indicate that the chemical is easily absorbed in water and may be found in surface and
groundwater sources as a result of disposal and environmental releases of the chemical.
Aquatic Exposure
The flame-retardant chemical may present an aquatic exposure if the water solubility of the
compound is greater than 1 x 10"06 grams/liter or the compound is dispersible in water.
7 Liquids are substances that have a melting point less than 25 degrees Celsius and a boiling point greater than 25
degrees Celsius.
8 Reactive chemicals (as opposed to additive chemicals) are those that are incorporated into the foam by new
chemical bonds that are formed between the substrate and the flame retardant. Therefore, they are not assumed to be
available for exposure.
9 Solids are substances that have a melting point of greater than 25 degrees Celsius.
10 Gases are substances that have a boiling point less than 25 degrees Celsius.
4-11
-------
4.2
Chemical Summary Assessments
The following subsections (4.2.1 through 4.2.19) contain summaries of the toxicity and exposure
data for 15 chemicals that are components of the flame retardant formulations assessed in this
report. These summary data were used to develop the hazard concern and exposure conclusions
that are presented in Table 4-1. The studies from which these data were derived are summarized
in Volume 2 of this report, entitled Chemical Hazard Reviews.
4.2.1
Triphenyl Phosphate
Record ID: Triphenyl Phosphate CAS No. 115-86-6
t v
/ \
\\ //
v — f4 0
OP 0
/^/o y^\
CT o
MW: 326.29
MF: Ci8Hi504P
Physical Forms:
Neat: Solid
As Formulated:
Use: Flame retardant,
additive
SMILES : c 1 ccccc 1 OP(=O)(Oc2ccccc2)Oc3 cccccS
Name: Phosphoric acid, triphenyl ester
Synonyms: Triphenyl phosphate; TPP
ASSESSMENT SUMMARY:
Persistence
Bioconcentration
Cancer Health Hazard
Non-Cancer Health Hazard
Aquatic Toxicity Hazard
Is the chemical predicted to be a PBT by
PBT Profiler?
Overall Hazard Concern
Concern Level
HIGH MODERATE
X°
X
No
LOW
X
X
X
Human Health Hazard: Moderate
Aquatic Hazard: High
Based on systemic effects and eye irritation.
4-12
-------
Record ID: Triphenyl Phosphate CAS No. 115-86-6
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
50.5 (M)
245 @ 1 1 mm Hg (M); 389 (E)
6.3xlO'6 (M)
1.9xlO'3(M)
4.59 (M)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC (atm-
m3/mole)
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
1.2x 10'5(M)
2514-3561 (M)
132-264 (Rainbow Trout); 218-1743 (Fathead
Minnow) (M)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
93.8% removal as DOC in OECD 3 03 A over 20
days; 50-100% removal within 8 days in river
die-away; 83-84% over 28 days using MITI II;
10.3% removal in 40 days under anaerobic
conditions in river sediment
Weeks-months (E)
Days (E)
12 hours (E)
Half-life at 20 degrees C: 366 days@ pH 3; 406
days @ pH 7, <5 days @ pH 9 (M)
13 days (E)
152 days (E)
61% (E)
Ready biodegradable (M)
Byproducts
Degradation Products
Metabolites
Diphenyl phosphate, phenol (M)
4-13
-------
Record ID: Triphenyl Phosphate CAS No. 115-86-6
ECOTOXICITY:
ECOSAR Class
Comments
Esters-phosphate
* = based on geometric mean of experimental
values
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae EC50
96-h LCSO, 0.870 mg/L (M)
48-hLC50, 1.2 mg/L (MC)
48-hLC50, 1.1 mg/L*(M)
96-h EC50, 2.0 mg/L (M)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for Aquatic
Toxicity
0.140 mg/L (MC); 0.09 (F96/ACR10)(E)
0.1 mg/L (D48/ACR10) (E)
>0. 140 mg/L (E)
< 0.600 mg/L (M)
0.5 mg/L (A96/ACR4) (E)
HIGH
HEALTH EFFECTS:
Absorption
Poor thru skin as neat solid, moderate thru skin in
solution; moderate thru lungs and GI tract based
on closely related analogs (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Marginal (E)
LOW
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Low; Rat, mouse, rabbit, oral, LD50 > 5000
mg/kg (M); Mammal, dermal, LD50 > 8000
mg/kg (MC); rabbit, dermal, LD50 > 7900 mg/kg
(M)
Moderate; Mild eye irritation, rabbits (M, MC)
Low; Negative, rabbits (M)
Low; negative in guinea pigs (MC), very low
incidence in humans (M)
4-14
-------
Record ID: Triphenyl Phosphate
CAS No. 115-86-6
Reproductive Effects
Low; 91-112-d reproductive
(incomplete)/developmental study, rats, diet, no
reproductive effects, NOAEL = 690 mg/kg/day
'(M)
Developmental Effects
Low; 91-112-d reproductive/developmental
study, rats, diet, no developmental effects,
NOAEL = 690 mg/kg/day, maternal LOAEL =
690 mg/kg/day (1%) (M)
Immune System Effects
Low; 120-d repeated-dose study, rats, diet, no
immune system effects, NOAEL = 700
mg/kg/day (1%) (M)
Neurotoxicity
Low; negative in delayed neurotoxicity studies in
the hen at up to 10,000 mg/kg/day (oral, 6 dosing
days) and in the cat at 700 mg/kg (subcutaneous,
single dose) (M); 120-d repeated-dose
neurotoxicity screening study, rats, diet, no
neurobehavioral effects, NOAEL = 711
mg/kg/day (1.0%) (M)
Genotoxicity/Mutagenicity
Low; Negative in Ames assay and Negative in
forward mutation assay, mouse lymphoma cells
in vitro., with and without metabolic activation
(M); Negative in mitotic gene conversion assay
in Saccharomyces cerevisiae with and without
activation (M)
Systemic Effects
Moderate; 35-d repeated-dose study (inadequate),
rats, diet, increased relative liver weight at 0.5%,
NOAEL = 0.1%; 120-d repeated-dose
(neurotoxicity screening) study, rats, diet,
decreased body weight gain without decreased
food consumption, NOAEL =161 mg/kg/day
(0.25%), LOAEL = 345 mg/kg/day (1%); 21-d
repeated-dose study (inadequate), rabbits, dermal,
systemic effects (M)
Overall Hazard Concern for Non-Cancer
Health Effects
MODERATE
4-15
-------
4.2.2
Tribromoneopentyl alcohol
Record ID: Tribromoneopentyl alcohol CAS No. 36483-57-5
Br
C /\^Br
(
Br
MW: 324.84
MF: C5H9Br3O
Physical Forms:
Neat: Solid
As Formulated:
Use: Flame retardant,
reactive
SMILES: OCC(CBr)(CBr)CBr
Name: 1-Propanol, 2,2-dimethyl-, tribromo derivative (FRA-12)
Synonyms: Tribromoneopentyl alcohol
ASSESSMENT SUMMARY:
Persistence
Bioconcentration
Cancer Health Hazard
Non-Cancer Health Hazard
Aquatic Toxicity Hazard
Is the chemical predicted to be a PBT by
PBT Profiler?
Overall Hazard Concern
Concern Level
HIGH MODERATE
X
X°
X
No
LOW
X
X
Human Health Hazard: Moderate
Aquatic Hazard: Moderate
° Based on reproductive effects, developmental effects, neurotoxicity, genotoxicity/mutagenicity,
systemic effects, eye irritation, and skin irritation.
4-16
-------
Record ID: Tribromoneopentyl alcohol CAS No. 36483-57-5
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
62-67 (M)
300 (E)
760 (E)
6.2xlO'5 (E)
2(M)
1.9 at 20.1 degrees C (MC)
2.6 (MC)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
1.14 xlO'10 atm-m3/mole (E)
22.9 (E)
10.8 (E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
2.5% CO2 evolution over 28 days in OECD 310
test (MC); 77% removal as DOC using OECD
302B in 36 days after a 10-day lag period (MC)
Weeks-months (E)
Days-weeks (E)
25 hours (E)
Negligible (E)
Negligible (E)
2.55% (E)
Not ready biodegradable (MC)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-17
-------
Record ID: Tribromoneopentyl alcohol
ECOTOXICITY:
ECOSAR Class
CAS No. 36483-57-5
Haloalcohols
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LC50=32 mg/L (MC)
48-h EC50=64 mg/L (MC)
72-h EC50=28 mg/L (MC)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
3.2 mg/L (F96/ACR 10) (E)
6.4 mg/L (D48/ACR10) (E)
7 mg/L (GA72/ACR4) (E)
MODERATE
HEALTH EFFECTS:
Absorption
Nil thru skin as neat material; moderate thru skin when in
solution; good absorption expected thru lungs and GI tract (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Moderate by analogy to a closely related compound; 2-yr study,
male/female, rats, mice, neoplasms in multiple organs (P)
Moderate
MODERATE
4-18
-------
Record ID: Tribromoneopentyl alcohol CAS No. 36483-57-5
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Low; Rat oral LD50 = 1630 to >2000 mg/kg (M,MC), effects on
bladder (M); Rat dermal LD50 >2000 mg/kg (MC); Rat 7-h
inhalation LCso > 714 mg/m3 (mixture, inadequate study) (M)
Moderate; Mild eye irritant in rabbits (M);
moderate eye irritant in rabbits (MC)
Moderate; Mild skin irritant in rabbits 24 hr exposure (M) but
not 4 hour exposure (MC)
Low; negative in mouse local lymph node assay (MC)
Moderate by analogy to a closely related compound;
repro/fertility study, mice, diet, 141, 274, 589 mg/kg/day,
decreased fertility and litter size, increased gestation length,
LOAEL =141 mg/kg/day (P)
Moderate by analogy to a closely related compound;
repro/fertility study, mice, diet, 141, 274, 589 mg/kg/day,
decreased pup weight, NOAEL =141 mg/kg/day (P)
Moderate based on bromo substituents (P)
Moderate; Positive, mutagenic in L5178Y mouse lymphoma
cells with activation by rat S9 (MC); Positive, chromosomal
aberrations, in vitro (MC); Positive, mouse micronucleus assay,
females (MC); Positive, Salmonella with activation from
hamster S9 (M, MC); Negative, Salmonella without activation or
with activation by rat S9 (M, MC); Negative, yeast, mitotic gene
conversion assay with or without activation (M)
Moderate; 30-d repeated-dose study, rats, oral, diet, 10, 30, 100,
300 mg/kg/day, kidney, ureter, bladder, blood changes,
NOAEL = 30 mg/kg/day (M,P)
MODERATE
4-19
-------
4.2.3
Tris(l,3-dichloro-2-propyl) Phosphate
Record ID: Tris(l,3-dichloro-2-propyl) Phosphate
CAS No. 13674-87-8
Cl
MW: 430.91
Cl
o )
o-p-o
/
/
•(
ci
MF:
Cl
Physical Forms:
Neat: Liquid
As Formulated:
Cl
Cl
Use: Flame retardant,
additive
SMILES: C1CC(CC1)OP(=O)(OC(CC1)CC1)OC(CC1)CC1
Name: 2-Propanol, 1,3-dichloro-, phosphate (3:1)
Synonyms: Tris(l,3-dichloro-2-propyl) Phosphate, TDCPP; TDCP
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Moderate
0 Based on reproductive effects, developmental effects, genotoxicity/mutagenicity, systemic
effects, eye irritation, and skin irritation.
4-20
-------
Record ID: Tris(l, 3 -dichloro-2-propyl) Phosphate CAS No. 13674-87-8
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
-58 (M)
236-237 @ 5 mm Hg (M); Slowly decomposes
>200 (M)
<10'6 (E)
0.042 (M)
0.018 (MC)
2.40 (M)
3.69(MC)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC (atm-m3/mol)
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
2.61xlO'9 (E)
9222 (E)
3-5 (Goldfish); 3-113 (Killifish) (M)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
0% CO2 uptake over 28 days in OECD 301B test;
1% by BOD over 28 days in MITI test; 0% by 02
uptake over 28 days in OECD 302C test; 0-
18.5% 02 uptake over 7-14 days in river die-away
(M)
Recalcitrant (E)
Weeks (E)
7.1 hours (E)
>1 year @ pH 7
Negligible (E)
Negligible (E)
3% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-21
-------
Record ID: Tris(l, 3 -dichloro-2-propyl) Phosphate CAS No. 13674-87-8
ECOTOXICITY:
ECOSAR Class
Comments
Esters - phosphate
* = based on geometric mean of experimental values
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae EC50
96-h LCSO, 1.9 mg/L* (M,MC)
48-h LCSO, 3.8 mg/L (E)
96-h EC50, 12.0 mg/L (M)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
0.200 mg/L* (F96/ACR10) (E)
0.400 mg/L (D48/ACR10) (E)
6.0 mg/L (M)
MODERATE
HEALTH EFFECTS:
Absorption
Good absorption and reaction, all routes
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
2-yr chronic toxicity/carcinogenicity study, rats, diet, 5, 20, 80
mg/kg/day, increased benign adrenal cortex tumors, testicular
interstitial cell tumors, and hepatocellular adenomas at 20 and 80
mg/kg/day (M)
Moderate
MODERATE
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Low; Mouse oral LD50= (male) 2670 & (female) 2250 mg/kg;
Rat oral LD50 = 3 160 mg/kg;
Rabbit oral LD50 = 6800 mg/kg;
Rabbit dermal (24-hr) LDso >4640 mg/kg (no death, clinical signs
or gross necropsy lesions)(M)
Moderate; Mild reversible conjunctival irritant or negative, rabbits
(M)
Moderate; 4 Hrs: non-irritant; 24 hrs: mild skin irritant, rabbits (M)
Low; Negative in guinea pigs (MC); Uncertain concern for
sensitization as substance is a potential alkylating agent (P)
4-22
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Record ID: Tris(l,3-dichloro-2-propyl) Phosphate
CAS No. 13674-87-8
Reproductive Effects
Moderate; Male reproduction study, rabbits, gavage, 12-wk
exposure, no effects on male fertility or spermatogenesis, NOAEL
= 200 mg/kg/day (M); 2-yr chronic toxicity/carcinogenicity study,
rats, diet, 5, 20, 80 mg/kg/day, anomalies of the testes and seminal
vesicles, NOAEL = 5 mg/kg/day (M)
Developmental Effects
Moderate; Developmental toxicity study, gavage, rats, gd 6-15, 25,
100, 400 mg/kg/day, increased resorptions, decreased fetal
viability, weight, and length, NOAEL =100 mg/kg/day.
Developmental toxicity study, gavage, rats, gd 7-19, 25, 50, 100,
200, 400 mg/kg/day, decreased fetal viability, NOAEL = 200
mg/kg/kday (M).
Immune System Effects
Low; Uncertain concern for immunotoxicity because substance is
potentially an alkylating agent;
Immunotoxicity assay, subcutaneous, mouse, 4 consecutive days,
0.25, 2.5, 25 mg/kg/day; lymphoid depletion of thymus, reduced
responses to T-cell & B-cell antigens, NOAEL 0.25 mg/kg/day
(M)
Neurotoxicity
Low; Acute delayed neurotoxicity study, hens, gavage, no
significant inhibition of brain neurotoxic esterase (NTE) activity at
10,000 mg/kg; 90-d study, hens, gavage, no behavioral effects or
histopathological changes indicative of neurotoxicity, NOAEL =
100 mg/kg/day;
In developmental toxicity assay, rats, gavage gd 7-19, no adverse
effect on postnatal neurobehavioral tests of sensory and motor
function, NOAEL = 200 mg/kg/day (M)
Genotoxicity/ Mutagenicity
Moderate; Positive, mutagenicity, Salmonella, with metabolic
activation; Negative, mutagenicity, mouse lymphoma cells with or
without activation & hamster lung cells with activation, in vitro;
Negative, sex-linked recessive lethal, Drosophila in vivo (M)
Positive only with activation, chromosomal aberrations, in vitro,
human lymphocytes (MC) & mouse lymphoma cells (M);
Negative, chromosomal aberrations, in vitro, Chinese hamster
ovary cells (MC); Negative, sister chromatid exchange, in vitro,
cell line not reported (MC); Positive with or without activation,
sister chromatid exchange, in vitro, mouse lymphoma cell;
Negative, unscheduled DNA synthesis, in vivo, in rat hepatocytes
(M, MC); Negative, chromosomal aberrations, in vivo, mice (M);
Negative, micronucleus assay in vivo, mice (MC)
4-23
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Record ID: Tris(l, 3 -dichloro-2-propyl) Phosphate CAS No. 13674-87-8
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Moderate; 2-yr chronic toxicity/carcinogenicity study, rats, diet, 5,
20, 80 mg/kg/day, increased mortality, decreased body weight,
anemia, anomalies of the liver, kidneys, testes, seminal vesicles,
renal cortex, and adrenal cortex, LOAEL = 5 mg/kg/day.
Inadequate 90-day dietary study, mice, 0.01, 0.04, 0.13, 0.42 and
1.33% in diet; increased mortality, decreased body weight,
anemia, increased liver & kidney weight, liver histopathology;
NOAEL= 0.01% dietary level (M)
MODERATE
4-24
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4.2.4
Proprietary A
Record ID: Proprietary A: Chloroalkyl phosphate (1)
CAS No.
MW:
MF:
Physical Forms:
Neat: Liquid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Chloroalkyl phosphate (1)
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Moderate
0 Based on reproductive effects, developmental effects, genotoxicity/mutagenicity, systemic
effects, eye irritation, and skin irritation.
4-25
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Record ID: Proprietary A: Chloroalkyl phosphate (1) CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
-58 (M)
236-237 @ 5 mm Hg (M); Slowly decomposes
>200 (M)
<10'6 (E)
0.042 (M)
0.018 (MC)
2.40 (M)
3.69(MC)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC (atm-m3/mol)
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
2.61xlO'9 (E)
9222 (E)
3-5 (Goldfish); 3-113 (Killifish) (M)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
0% CO2 uptake over 28 days in OECD 301B test;
1% by BOD over 28 days in MITI test; 0% by 02
uptake over 28 days in OECD 302C test; 0-
18.5% 02 uptake over 7-14 days in river die-away
(M)
Recalcitrant (E)
Weeks (E)
7.1 hours (E)
>1 year @ pH 7
Negligible (E)
Negligible (E)
3% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-26
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Record ID: Proprietary A: Chloroalkyl phosphate (1) CAS No.
ECOTOXICITY:
ECOSAR Class
Comments
Esters - phosphate
* = based on geometric mean of experimental values
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae EC50
96-h LCSO, 1.9 mg/L* (M,MC)
48-h LCSO, 3.8 mg/L (E)
96-h EC50, 12.0 mg/L (M)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
0.200 mg/L* (F96/ACR10) (E)
0.400 mg/L (D48/ACR10) (E)
6.0 mg/L (M)
MODERATE
HEALTH EFFECTS:
Absorption
Good absorption and reaction, all routes
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
2-yr chronic toxicity/carcinogenicity study, rats, diet, 5, 20, 80
mg/kg/day, increased benign adrenal cortex tumors, testicular
interstitial cell tumors, and hepatocellular adenomas at 20 and 80
mg/kg/day (M)
Moderate
MODERATE
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Low; Mouse oral LD50= (male) 2670 & (female) 2250 mg/kg;
Rat oral LD50 = 3 160 mg/kg;
Rabbit oral LD50 = 6800 mg/kg;
Rabbit dermal (24-hr) LDso >4640 mg/kg (no death, clinical signs
or gross necropsy lesions)(M)
Moderate; Mild reversible conjunctival irritant or negative, rabbits
(M)
Moderate; 4 Hrs: non-irritant; 24 hrs: mild skin irritant, rabbits (M)
Low; Negative in guinea pigs (MC); Uncertain concern for
sensitization as substance is a potential alkylating agent (P)
4-27
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Record ID: Proprietary A: Chloroalkyl phosphate (1)
CAS No.
Reproductive Effects
Moderate; Male reproduction study, rabbits, gavage, 12-wk
exposure, no effects on male fertility or spermatogenesis, NOAEL
= 200 mg/kg/day (M); 2-yr chronic toxicity/carcinogenicity study,
rats, diet, 5, 20, 80 mg/kg/day, anomalies of the testes and seminal
vesicles, NOAEL = 5 mg/kg/day (M)
Developmental Effects
Moderate; Developmental toxicity study, gavage, rats, gd 6-15, 25,
100, 400 mg/kg/day, increased resorptions, decreased fetal
viability, weight, and length, NOAEL =100 mg/kg/day.
Developmental toxicity study, gavage, rats, gd 7-19, 25, 50, 100,
200, 400 mg/kg/day, decreased fetal viability, NOAEL = 200
mg/kg/kday (M).
Immune System Effects
Low; Uncertain concern for immunotoxicity because substance is
potentially an alkylating agent;
Immunotoxicity assay, subcutaneous, mouse, 4 consecutive days,
0.25, 2.5, 25 mg/kg/day; lymphoid depletion of thymus, reduced
responses to T-cell & B-cell antigens, NOAEL 0.25 mg/kg/day
(M)
Neurotoxicity
Low; Acute delayed neurotoxicity study, hens, gavage, no
significant inhibition of brain neurotoxic esterase (NTE) activity at
10,000 mg/kg; 90-d study, hens, gavage, no behavioral effects or
histopathological changes indicative of neurotoxicity, NOAEL =
100 mg/kg/day;
In developmental toxicity assay, rats, gavage gd 7-19, no adverse
effect on postnatal neurobehavioral tests of sensory and motor
function, NOAEL = 200 mg/kg/day (M)
Genotoxicity/ Mutagenicity
Moderate; Positive, mutagenicity, Salmonella, with metabolic
activation; Negative, mutagenicity, mouse lymphoma cells with or
without activation & hamster lung cells with activation, in vitro;
Negative, sex-linked recessive lethal, Drosophila in vivo (M)
Positive only with activation, chromosomal aberrations, in vitro,
human lymphocytes (MC) & mouse lymphoma cells (M);
Negative, chromosomal aberrations, in vitro, Chinese hamster
ovary cells (MC); Negative, sister chromatid exchange, in vitro,
cell line not reported (MC); Positive with or without activation,
sister chromatid exchange, in vitro, mouse lymphoma cell;
Negative, unscheduled DNA synthesis, in vivo, in rat hepatocytes
(M, MC); Negative, chromosomal aberrations, in vivo, mice (M);
Negative, micronucleus assay in vivo, mice (MC)
4-28
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Record ID: Proprietary A: Chloroalkyl phosphate (1) CAS No.
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Moderate; 2-yr chronic toxicity/carcinogenicity study, rats, diet, 5,
20, 80 mg/kg/day, increased mortality, decreased body weight,
anemia, anomalies of the liver, kidneys, testes, seminal vesicles,
renal cortex, and adrenal cortex, LOAEL = 5 mg/kg/day.
Inadequate 90-day dietary study, mice, 0.01, 0.04, 0.13, 0.42 and
1.33% in diet; increased mortality, decreased body weight,
anemia, increased liver & kidney weight, liver histopathology;
NOAEL= 0.01% dietary level (M)
MODERATE
4-29
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4.2.5
Proprietary B
Record ID: Proprietary B: Aryl phosphate CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated: Liquid
Use: Flame retardant,
additive
SMILES:
Name: Aryl phosphate
Synonyms:
ASSESSMENT SUMMARY:
Persistence
Bioconcentration
Cancer Health Hazard
Non-Cancer Health Hazard
Aquatic Toxicity Hazard
Is the chemical predicted to be a PBT by
PBT Profiler?
Overall Hazard Concern
Concern Level
HIGH MODERATE
X
X°
X
No
LOW
X
X
Human Health Hazard: Moderate
Aquatic Hazard: High
° Based on reproductive effects, developmental effects, neurotoxicity, systemic effects, and eye
irritation.
4-30
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Record ID: Proprietary B: Aryl phosphate CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
90 (E)
>400 (E)
760 (E)
<10'6(E)
<10'6(E)
6.16 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
7.74xlO"8 atm-m3/mole (E)
2.6xl04(E)
1820(E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
46% ThOD after 28 days in OECD 301F (MC)
Weeks -months (E)
Days-weeks (E)
9.3 hours (E)
605 days (E)
Negligible (E)
93% (E)
Not ready biodegradable (MC)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-31
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Record ID: Proprietary B: Aryl phosphate
ECOTOXICITY:
ECOSAR Class
CAS No.
Ester-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, NES (No effects at saturation) (E)
48-h LCSO, NES (E)
96-h ECSO, NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern
for Aquatic Toxicity
NES(E)
NES(E)
NES(E)
HIGH (chronic toxicity and only when 1 or 2 isopropyls are
present)
HEALTH EFFECTS:
Absorption
Nil thru skin as neat solid; poor thru skin when in solution; poor
thru lungs and GI tract by analogy to closely related compounds
(P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern
for Carcinogenicity
Marginal (E)
LOW
4-32
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Record ID: Proprietary B: Aryl phosphate CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Low in mixtures; Rat oral LD50 >5000 mg/kg (no deaths),
>20,000 mg/kg (4/10 deaths); Rat 1-hr inhalation LC50 > 200
mg/L; Rat dermal LD0 > 2000 mg/kg (no deaths)(M)
Moderate in mixtures; Rabbits, very slight eye irritation (M)
Low in mixtures; Not irritating to intact or abraded skin in rabbits
(M)
Low by analogy to a closely related compound (P)
Preliminary results of an unfinished 39-41-day combined
subchronic plus reproductive/developmental toxicity screening
test suggest that the reproductive hazard may be moderate, rat,
oral gavage, ovarian weight effect at >25 mg/kg/day, epididymal
weight effect and reduced fertility at 100 and 400 mg/kg/day
(MC)
Preliminary results of an unfinished 39-41-day combined
subchronic plus reproductive/developmental toxicity screening
test suggests the developmental hazard may be moderate; rat, oral
gavage, reduced pre- and post-natal survival at 400 mg/kg/day
(MC)
Moderate in mixtures; acute delayed neurotoxicity assay, hens,
oral gavage, NOAEL =12 mg/kg/day for neurotoxic esterase
(NTE) inhibition, LOAEL = 1000 mg/kg/day; delayed oral
neurotoxicity, hens, 2 oral treatments 3 weeks apart, transient
dose-related gait impairment (LOAEL =12 mg/kg/day), but no
neurohistopathology at doses as high as 1 1,700 mg/kg/day (M);
Also by analogy to closely related compounds and professional
judgment; neurotoxicity study, hens, oral gavage, 3, 5, 7, 9 g/kg,
ataxia, neuropathological lesions, LOAEL = 3000 mg/kg;
neurotoxicity study, hens, oral gavage, 10, 20, 90, 270
mg/kg/day, ataxia, nerve degeneration, NOAEL = 20 mg/kg/day;
NTE inhibition (M,P)
Low by analogy to a closely related compound; Negative, Ames
assay (P)
Moderate in mixture (liver effects); 28-d repeated-dose study
(inadequate), rats, diet, 0.1%, 0.5%, 1.0%, liver effects all doses,
LOAEL = 0.1%(M);
Preliminary results of an unfinished a 39-41-day combined
subchronic toxicity with reproductive/developmental screening
test suggest that there may be a moderate hazard for subchronic
toxicity (adrenal and liver effects), rat, oral gavage, adrenal
weight effect in females, LOAEL = 25 mg/kg/day (MC)
4-33
-------
Record ID: Proprietary B: Aryl phosphate CAS No.
Overall Hazard Concern
for Non-Cancer Health
Effects
MODERATE
4-34
-------
4.2.6
Proprietary C
Record ID: Proprietary C: Chloroalkyl phosphate (2)
CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated: Liquid
Use: Flame retardant,
additive
SMILES:
Name: Chloroalkyl phosphate (2)
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Moderate
0 Based on reproductive effects, developmental effects, systemic effects, eye irritation, skin
irritation, and skin sensitizer.
4-35
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Record ID: Proprietary C: Chloroalkyl phosphate (2) CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
< 20 (P)
>400 (E)
760 (E)
<10'6(MC)
0.23 (MC)
2.83 (MC)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
2.74xlO'14 atm-m3/mole (E)
l.lx!04(MC);6.07xl06(E)
6.64 (E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
37% oxygen uptake after 28 days in OECD 302C
(MC); 5% degradation in modified Sturm test,
28 days (MC); 8-15% inhibition to activated
sludge (MC)
Recalcitrant (E)
Weeks (E)
1.6 hours (E)
Half-life is greater than 1 year (MC)
Negligible (E)
Negligible (E)
44.7% (E)
Not ready biodegradable (MC)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-36
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Record ID: Proprietary C: Chloroalkyl phosphate (2) CAS No.
ECOTOXICITY:
ECOSAR Class
Ester-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, 9.6 mg/L (E)
96-h LCSO, 52.2 mg/L (MC)
48-h ECSO, 30.0 mg/L (E)
48-hEC50, 41.9 mg/L (MC)
96-h ECSO, 1.5 mg/L (E)
96-h ECSO (growth rate inhibition), 38.5 mg/L (MC)
96-h ECSO (growth inhibition), 20.1 mg/L (MC)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
1.0 mg/L (E)
3.0 mg/L, (E)
23-d ECSO (parental mortality), 7.31 mg/L (MC)
LOEC (impaired reproduction), > 3.68 mg/L (MC)
NOEC (impaired reproduction), > 3.68 mg/L (MC)
1.2 mg/L (E)
MODERATE
HEALTH EFFECTS:
Absorption
Poor absorption via all routes (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Moderate by analogy to a closely related compound; 2-yr chronic
toxicity/carcinogenicity study, rats, diet, 5, 20, 80 mg/kg/day,
increased benign adrenal cortex tumors and hepatocellular
adenomas at 20 and 80 mg/kg/day (P)
Low-moderate (E)
MODERATE
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Low; Rat oral LD50 between 2000 and 5000 mg/kg (M), >2000
mg/kg (MC); Rat inhalation LC50 >1.65 mg/L (no death) (MC);
Rat dermal LDso > 2000 mg/kg (no deaths or clinical signs)(M,
MC)
Moderate; Slight eye (conjunctival) irritation (M, MC)
Moderate, rabbits; No skin irritation (M); slight irritation
(erythema) (MC); mild irritation (erythema, edema) (MC)
4-37
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Record ID: Proprietary C: Chloroalkyl phosphate (2)
CAS No.
Skin Sensitizer
Moderate; guinea pig, no sensitization (M), mild sensitization
(MC)
Reproductive Effects
A 4-wk oral gavage study in rats reported no histopathology of
reproductive organs in either sex at a NOAEL of 600 mg/kg/day,
but the study duration was short (MC);
Moderate by analogy to a closely related compound; 12-wk male
reproduction study, rabbits, gavage, no effects on male fertility or
spermatogenesis, NO AEL = 200 mg/kg/day; 2-yr chronic
toxicity/carcinogenicity study, rats, diet, 5, 20, 80 mg/kg/day,
anomalies of the testes and seminal vesicles, NO AEL = 5
mg/kg/day (P)
Developmental Effects
Moderate by analogy to closely related compound;
Developmental toxicity study on one analog, gavage, rats, gd 6-
15, 25, 100, 400 mg/kg/day, increased resorptions, decreased
fetal viability, weight, and length, fetal NO AEL =100 mg/kg/day
(P);
Developmental toxicity study on another analog, gavage, rats, 15,
50, 150, 500 mg/kg/day, maternal deaths at 150 mg/kg/day,
maternal NO AEL = 50 mg/kg/day, fetal NO AEL = 15 mg/kg/day
(P)
Immune System Effects
Neurotoxicity
Low, neurotoxicity screening battery after 4-week oral gavage,
rats, no behavioral effects or neurohistopathology, NO AEL = 600
mg/kg/day (MC).
Also by analogy to a closely related compound; Acute study,
hens, gavage, delayed neurotoxicity, no inhibition of brain
neurotoxic esterase (NTE) activity, NO AEL = 10,000 mg/kg; 90-
d study, hens, gavage, no behavioral effects or histopathological
changes indicative of neurotoxicity, NO AEL =100 mg/kg/day
(P)
Genotoxicity/Mutagenicity
Low, Negative, mutagenicity in mouse lymphoma (M, MC) and
Ames test (MC); Negative, chromosomal aberrations in vitro
(human lymphocytes) (MC); Negative, bone marrow
micronucleus assay in mice (oral gavage) (MC)
Moderate for genotoxic effects other than mutagenicity by
analogy to closely related compounds: Positive, chromosomal
aberrations, in vitro, human lymphocytes; Positive, rat dominant
lethal assay (P);
4-38
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Record ID: Proprietary C: Chloroalkyl phosphate (2) CAS No.
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Moderate, 4-week oral gavage study, rats (liver effects),
NOAEL = 15 mg/kg,day, LOAEL = 150 mg/kg/day (MC);
Also by analogy to a closely related compound; 2-yr chronic
toxicity/carcinogenicity study, rats, diet, 5, 20, 80 mg/kg/day,
increased mortality, decreased body weight, anomalies of the
liver, kidneys, testes, seminal vesicles, renal cortex, and adrenal
cortex, NOAEL = 5 mg/kg/day (P)
MODERATE
4-39
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4.2.7
Proprietary D
Record ID: Proprietary D: Reactive brominated flame retardant
CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated: Liquid
Use: Flame retardant,
reactive
SMILES:
Name: Reactive brominated flame retardant
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Moderate
A Likely brominated hydrolysis product is expected to be persistent.
0 Based on neurotoxicity, systemic effects, eye irritation, and skin sensitizer.
4-40
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Record ID: Proprietary D: Reactive brominated flame retardant CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
< 20 (P)
>400 (E)
760 (E)
<10'6 (E)
0.007 to 0.1 5 (E)
3.83 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
2.23xlO'21 atm-m3/mole (E)
10 (E)
39 (E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
Months (E)
Weeks (E)
4.2 hours (E)
19 hrs @ pH 8; 7 days @ pH 7 (E)
Negligible (E)
Negligible (E)
23% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Brominated hydrolysis product (P)
4-41
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Record ID: Proprietary D: Reactive brominated flame retardant CAS No.
ECOTOXICITY:
ECOSAR Class
Ester-phthalate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, < 67.0 mg/L (E)
48-h LCSO, < 280.0 mg/L (E)
96-h ECSO, < 5. 4 mg/L (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for Aquatic
Toxicity
< 7.0 mg/L (E)
< 30.0 mg/L (E)
< 4.2 mg/L (E)
MODERATE
HEALTH EFFECTS:
Absorption
Poor all routes (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Marginal (E)
LOW
4-42
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Record ID: Proprietary D: Reactive brominated flame retardant CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for Non-Cancer
Health Effects
Low; Rat oral LD50 >1 0,000 mg/kg (no deaths);
Rabbit dermal LD50 >20,000 mg/kg (no deaths);
Rat 1-hr inhalation LC50 >0.008 mg/L (no
deaths) (M); Low by analogy to a closely related
compound; Rat oral LD50 = 2874 (P)
Moderate, mild reversible conjunctival irritant or
not an eye irritant in rabbits (M)
Low, not an irritant to intact skin, mild reversible
irritation of abraded skin in rabbits (M)
Moderate by analogy to a closely related
compound (P)
Moderate by analogy to a closely related
compound: Acute oral study, rats, brain
hemorrhages (P)
Low, Negative in Ames assay with or without
metabolic activation (M); Low also by analogy
to a closely related compound; Negative in Ames
assay (P)
Moderate by analogy to closely related
compounds: 28-d, rats, oral, 160, 400, 1000
mg/kg/day, renal effects at all doses; 21-d
repeated-dose study, rats, inhalation, 2-8 mg/L,
adrenal, thyroid, lung, and liver effects; 28-d
repeated-dose study, rabbits, dermal, 5000
mg/kg, kidney, liver, blood effects (P)
MODERATE
4-43
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4.2.8
Proprietary E
Record ID: Proprietary E: Tetrabromophthalate diol diester CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated: Liquid
Use: Flame retardant,
additive
SMILES:
Name: Tetrabromophthalate diol diester
Synonyms:
ASSESSMENT SUMMARY:
Persistence
Bioconcentration
Cancer Health Hazard
Non-Cancer Health Hazard
Aquatic Toxicity Hazard
Is the chemical predicted to be a PBT by
PBT Profiler?
Overall Hazard Concern
Concern Level
HIGH MODERATE
X°
No
LOW
x-
X
X
Human Health Hazard: Moderate
Aquatic Hazard:
A Likely brominated hydrolysis product is expected to be persistent.
0 Based on systemic effects.
4-44
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Record ID: Proprietary E: Tetrabromophthalate diol diester CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
< 20 (P)
>400 (E)
760
<10'6 (E)
0.002 (E)
5.57 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
<10"8 atm-m3/mole (E)
27,000 (E)
3,903 (E); Low, hydrolyzes
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
Recalcitrant (E)
Weeks (E)
3.2hours(E)
8 days @ p-H 7; 19 hours @ pH 8 (E)
Negligible (E)
Negligible (E)
89% (E)
Not Ready Biodegradable (E)
Byproducts
Degradation Products
Metabolites
Tetrabromophthalate by hydrolysis (P)
4-45
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Record ID: Proprietary E: Tetrabromophthalate diol diester CAS No.
ECOTOXICITY:
ECOSAR Class
Ester-phthalate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, NES (No effects at saturation) (E)
48-h LCSO, NES (E)
96-h ECSO, NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
0.040 or NES (E)
0.030 or NES (E)
0. 100 or NES (E)
HIGH (chronic toxicity only)
HEALTH EFFECTS:
Absorption
Absorption of LMW fraction is expected to be poor by all
routes based on physicochemical properties (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Cannot be run in OncoLogic
LOW
4-46
-------
Record ID: Proprietary E: Tetrabromophthalate diol diester CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye/Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Moderate by analogy to closely related compounds; kidney
toxicity, NOAEL = 400 mg/kg (M); liver toxicity based on
brominated phenyl moiety (P)
MODERATE
4-47
-------
4.2.9
Proprietary F
Record ID: Proprietary F: Halogenated aryl ester
CAS No.
MW:
MF:
Physical Forms:
Neat: Liquid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Halogenated aryl ester
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
Xz
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Low
A Likely halogenated degradation product is expected to be persistent.
0 Based on reproductive effects, developmental effects, and systemic effects.
4-48
-------
Record ID: Proprietary F: Halogenated aryl ester CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
Log Kow
< 20 (P)
>400 (E)
760 (E)
28,840 (MC)
1. 7-6.2 (MC)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
Half-life of 3.5 days in water shake flask die-
away test, 8.5 days in sediment (MC);
6% biodegradation after 28 days in closed bottle
test (MC)
Months (E)
Weeks (E)
12 hours (E)
>1 year @ pH 4, 7, and 9 (MC)
8 days (E)
98 days (E)
90% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Halogenated aryl acid
4-49
-------
Record ID: Proprietary F: Halogenated aryl ester CAS No.
ECOTOXICITY:
ECOSAR Class
Esters
Acute Toxicity
Fish LC50
Daphnid LC50
Green Algae ECso
96 hr NOEC, NES (No effects at saturation) (MC)
24 hr ECSO, 1.2 mg/L; 48 hr ECSO, 0.42 mg/L (MC)
96 hr ECSO, NES (MC)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
NES(E)
0.04 (D48/ACR10) (E)
NES(E)
HIGH
HEALTH EFFECTS:
Absorption
Poor absorption via all routes (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Uncertain by analogy to a closely related chemical classes (P)
LOW
4-50
-------
Record ID: Proprietary F: Halogenated aryl ester CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Low; Rat oral LD50 >2000 mg/kg (M)
Moderate by analogy to a closely related compound (P)
Moderate by analogy to a closely related compound (P)
Moderate concern for liver effects by analogy to a closely
related compound (P)
MODERATE
4-51
-------
4.2.10
Proprietary G
Record ID: Proprietary G: Triaryl phosphate, isopropylated CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated: Liquid
Use: Flame retardant,
additive
SMILES:
Name: Triaryl phosphate, isopropylated
Synonyms:
ASSESSMENT SUMMARY:
Persistence
Bioconcentration
Cancer Health Hazard
Non-Cancer Health Hazard
Aquatic Toxicity Hazard
Is the chemical predicted to be a PBT by
PBT Profiler?
Overall Hazard Concern
Concern Level
HIGH MODERATE
X
X°
X
No
LOW
X
X
Human Health Hazard: Moderate
Aquatic Hazard: High
° Based on reproductive effects, developmental effects, neurotoxicity, systemic effects, and eye
irritation.
4-52
-------
Record ID: Proprietary G: Triaryl phosphate, isopropylated CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
90 (E)
>400 (E)
760 (E)
<10'6(E)
<10'6(E)
6.16 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
7.74xlO"8 atm-m3/mole (E)
2.6xl04(E)
1820(E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
46% ThOD after 28 days in OECD 301F (MC)
Weeks -months (E)
Days-weeks (E)
9.3 hours (E)
605 days (E)
Negligible (E)
93% (E)
Not ready biodegradable (MC)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-53
-------
Record ID: Proprietary G: Triaryl phosphate, isopropylated
ECOTOXICITY:
ECOSAR Class
CAS No.
Ester-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, NES (No effects at saturation) (E)
48-h LCSO, NES (E)
96-h ECSO, NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern
for Aquatic Toxicity
NES(E)
NES(E)
NES(E)
HIGH (chronic toxicity and only when 1 or 2 isopropyls are
present)
HEALTH EFFECTS:
Absorption
Nil thru skin as neat solid; poor thru skin when in solution; poor
thru lungs and GI tract by analogy to closely related compounds
(P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern
for Carcinogenicity
Marginal (E)
LOW
4-54
-------
Record ID: Proprietary G: Triaryl phosphate, isopropylated CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Low in mixtures; Rat oral LD50 >5000 mg/kg (no deaths),
>20,000 mg/kg (4/10 deaths); Rat 1-hr inhalation LC50 > 200
mg/L; Rat dermal LD0 > 2000 mg/kg (no deaths)(M)
Moderate in mixtures; Rabbits, very slight eye irritation (M)
Low in mixtures; Not irritating to intact or abraded skin in rabbits
(M)
Low by analogy to a closely related compound (P)
Preliminary results of an unfinished 39-41-day combined
subchronic plus reproductive/developmental toxicity screening
test suggest that the reproductive hazard may be moderate, rat,
oral gavage, ovarian weight effect at >25 mg/kg/day, epididymal
weight effect and reduced fertility at 100 and 400 mg/kg/day
(MC)
Preliminary results of an unfinished 39-41-day combined
subchronic plus reproductive/developmental toxicity screening
test suggests the developmental hazard may be moderate; rat, oral
gavage, reduced pre- and post-natal survival at 400 mg/kg/day
(MC)
Moderate in mixtures; acute delayed neurotoxicity assay, hens,
oral gavage, NOAEL =12 mg/kg/day for neurotoxic esterase
(NTE) inhibition, LOAEL = 1000 mg/kg/day; delayed oral
neurotoxicity, hens, 2 oral treatments 3 weeks apart, transient
dose-related gait impairment (LOAEL =12 mg/kg/day), but no
neurohistopathology at doses as high as 1 1,700 mg/kg/day (M);
Also by analogy to closely related compounds and professional
judgment; neurotoxicity study, hens, oral gavage, 3, 5, 7, 9 g/kg,
ataxia, neuropathological lesions, LOAEL = 3000 mg/kg;
neurotoxicity study, hens, oral gavage, 10, 20, 90, 270
mg/kg/day, ataxia, nerve degeneration, NOAEL = 20 mg/kg/day;
NTE inhibition (M,P)
Low by analogy to a closely related compound; Negative, Ames
assay (P)
Moderate in mixture (liver effects); 28-d repeated-dose study
(inadequate), rats, diet, 0.1%, 0.5%, 1.0%, liver effects all doses,
LOAEL = 0.1%(M);
Preliminary results of an unfinished a 39-41-day combined
subchronic toxicity with reproductive/developmental screening
test suggest that there may be a moderate hazard for subchronic
toxicity (adrenal and liver effects), rat, oral gavage, adrenal
weight effect in females, LOAEL = 25 mg/kg/day (MC)
4-55
-------
Record ID: Proprietary G: Triaryl phosphate, isopropylated CAS No.
Overall Hazard Concern
for Non-Cancer Health
Effects
MODERATE
4-56
-------
4.2.11
Proprietary H
Record ID: Proprietary H: Halogenated aryl ester
CAS No.
MW:
MF:
Physical Forms:
Neat: Liquid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Halogenated aryl ester
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
Xz
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard-
X
Is the chemical predicted to be a PBT
by PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Low
A Likely halogenated degradation product is expected to be persistent.
0 Based on reproductive effects, developmental effects, and systemic effects.
4-57
-------
Record ID: Proprietary H: Halogenated aryl ester CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
< 20 (P)
>400 (E)
760 (E)
28,840 (MC)
1. 7-6.2 (MC)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
Half-life of 3.5 days in water shake flask die-
away test, 8.5 days in sediment (MC);
6% biodegradation after 28 days in closed bottle
test (MC)
Months (E)
Weeks (E)
6 hours (E)
>1 year @ pH 4, 7, and 9 (MC)
211 days(E)
2310days(E)
90% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Halogenated aryl acid
4-58
-------
Record ID: Proprietary H: Halogenated aryl ester CAS No.
ECOTOXICITY:
ECOSAR Class
Esters
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96 hr NOEC, NES (No effects at saturation) (MC)
24 hr ECSO, 1 .2 mg/L; 48 hr ECSO, 0.42 mg/L
(MC)
96 hr ECSO, NES (MC)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for Aquatic
Toxicity
NES(E)
0.04 (D48/ACR10) (E)
NES(E)
HIGH
HEALTH EFFECTS:
Absorption
Poor absorption via all routes (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Uncertain by analogy to a closely related chemical
classes (P)
LOW
4-59
-------
Record ID: Proprietary H: Halogenated aryl ester CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for Non-Cancer
Health Effects
Low; Rat oral LD50 >2000 mg/kg (M)
Moderate by analogy to a
Moderate by analogy to a
closely related
compound (P)
closely related
compound (P)
Moderate concern for liver effects by analogy to a
closely related compound (P)
MODERATE
4-60
-------
4.2.12
Proprietary I
Record ID: Proprietary I: Organic phosphate ester
CAS No
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Organic phosphate ester
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
Yes
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: High
Based on systemic effects and eye irritation.
4-61
-------
Record ID: Proprietary I: Organic phosphate ester CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm
Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
< 20 (P)
>300 (MC)
760 (MC)
<10'6 (MC)
8xlO'4(MC,P)
6.89 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient -
KOC
Bioconcentration Factor -
BCF
4.89xlO'14 atm-m3/mole (E)
5.0xl07(E)
245 (MC)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for
Model River
Volatilization Half-life for
Model Lake
Removal in Sewage Treatment
Plant
Ready Biodegradability
2.3% degradation after 28 days MITI-II (MC); 30% in 28
days and 52% in 140 days - closed bottle test (MC)
Months (E)
Days (E)
2.1 hours (E)
Half-life of 20 days at pH 9 and 25 deg C (MC)
Negligible (E)
Negligible (E)
94% (E)
Not Ready Biodegradable (MC)
Byproducts
Degradation Products
Degradation products are expected to be less persistent than
the parent compound
4-62
-------
Record ID: Proprietary I: Organic phosphate ester CAS No.
Metabolites
ECOTOXICITY:
ECOSAR Class
Ester-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae EC50
96-h LCSO, NES (No effects at saturation) (E)
96-h LCSO, 0.205 mg/L (MC)
48-h LCSO, NES (E)
48-h LCSO, > 0.846 mg/L (MC)
96-h EC50, NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
0.200 or NES (E)
LOEC (reduced larval survival and growth), 0.088 mg/L (MC)
0.070 or NES (E)
LOEC (reduced reproduction and growth), 0.147 mg/L (MC)
0.140 or NES (E)
HIGH (chronic toxicity only)
HEALTH EFFECTS:
Absorption
Poor all routes by analogy to closely related compounds and
physicochemical properties (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Marginal (E)
LOW
4-63
-------
Record ID: Proprietary I: Organic phosphate ester
CAS No
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Low; rat oral LD50 > 5 g/kg
; rabbit dermal LD50 > 5 g/kg;
LC50>1.55mg/L(MC)
Moderate; mild and transient eye irritation, rabbits; no eye
irritation, rabbits (MC)
Low; no
skin irritation in rabbits (MC)
Low; no skin sensitization in guinea pigs (MC)
Low; NOAEL>1000 mg/kg/day in reproductive/developmental
screening test in rats (MC)
Low; NOAEL>1000 mg/kg/day in reproductive/developmental
screening test in rats (MC)
Low by analogy to a closely related compound; 42-d
neurotoxicity test, hens, NOAEL = 5 g/kg/day (P)
Low; Negative, mouse micronucleus assay, in vivo, i.p.;
Negative, chromosomal aberrations in vitro; Negative Ames
assay, Salmonella and E. coli; Negative mouse lymphoma assay
(MC)
Moderate by analogy to a closely related compound; 28-d
repeated-dose study, rat, oral gavage, slight liver toxicity,
NOAEL = 300 mg/kg/day, LOAEL = 1000 mg/kg/day (P)
MODERATE
4-64
-------
4.2.13
Proprietary J
Record ID: Proprietary J: Aryl phosphate
CAS No.
MW:
MF:
Physical Forms:
Neat: Liquid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Aryl phosphate
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: High
Based on systemic effects and eye irritation.
4-65
-------
Record ID: Proprietary J: Aryl phosphate CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
-21 (M)
425 (M)
760 (M)
1.4xlO'6(M)
0.0032 (M)
5.12(M)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
8.48xlO"7 atm-m3/mole (M)
3.7xl04(E)
290 (E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
43-90% CO2 evolution in 28 days with activated
sludge inoculum; 50% removal in 1 1 days in
river die away; half life of 0.44 days in pond
water and 39 days in pond sediment
Weeks-months (E)
Days-weeks (E)
8.2 hours (E)
54 days (E)
594 days (E)
81.2%(E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-66
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Record ID: Proprietary J: Aryl phosphate CAS No.
ECOTOXICITY:
ECOSAR Class
Ester-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, NES (No effects at saturation) (E)
48-h LCSO, NES (E)
96-h ECSO, 0.020 mg/L or NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
0.003 mg/L (E)
0.002 mg/L (E)
0.020 mg/L (E)
HIGH (chronic toxicity only)
HEALTH EFFECTS:
Absorption
Nil thru skin as neat solid; poor thru skin when in solution;
poor thru lungs and GI tract by analogy to closely related
compounds (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Marginal (E)
LOW
4-67
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Record ID: Proprietary J: Aryl phosphate CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Low; Rat oral LD50 > 5000 mg/kg; Rat dermal LD50 > 2000
mg/kg (M)
Low; Rabbits, no eye irritation (M)
Moderate; Rabbits, mild skin irritation (M)
Low by analogy to a closely related compound (P)
Low, 90-day oral toxicity (diet), rats, no effect on
histopathology or weights of reproductive organs in males or
females, NOAEL = 1600 ppm (M)
Low, delayed neurotoxicity; 5-d study, hens, oral gavage,
5000 mg/kg/day, no evidence of delayed neurotoxicity; 90-day
oral toxicity (diet), rats, no neurohistopathology in males or
females, NOAEL = 1600 ppm (M);
Also by analogy to a closely related compound (P)
Studies on poorly defined mixtures suggest negative results for
mutagenicity (Salmonella typhimurium, Saccharomyces
cerevisiae, mouse lymphoma cells), chromosomal aberration in
vitro (mouse lymphoma cells) and sister chromatid exchange in
vitro (mouse lymphoma cells) (M)
Moderate, based on studies identifying liver as potential target
organ. 90-day oral toxicity (diet), rats, at 1600 ppm (125
mg/kg/day), increased absolute and relative liver weights (both
sexes) and adrenal weights (females), no histopathological
lesions, but not tested at limit dose, NOAEL = 400 ppm,
LOAEL = 1600 ppm (M); Also by analogy to closely related
compounds (liver effects); 28-d repeated-dose study
(inadequate), rats, diet, increased relative liver weight (no
histopathology data available) at 0.5%, NOAEL = 0.1% (P)
MODERATE
4-68
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4.2.14
Proprietary K
Record ID: Proprietary K: Aryl phosphate
CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Aryl phosphate
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Low
Based on systemic effects.
4-69
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Record ID: Proprietary K: Aryl phosphate CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
90 (E)
>400 (E)
760 (E)
<10'6 (E)
<10'6 (E)
8.52 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
2.65xlO"7 atm-m3/mole (E)
2.7xl05 (E)
89 (E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model River
Volatilization Half-life for Model Lake
Removal in Sewage Treatment Plant
Ready Biodegradability
Months (E)
Days-weeks (E)
9.7 hours (E)
193 days (E)
Negligible (E)
94% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
Degradation products are expected to be less
persistent than the parent compound
4-70
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Record ID: Proprietary K: Aryl phosphate CAS No.
ECOTOXICITY:
ECOSAR Class
Ester-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, NES (No effects at saturation) (E)
48-h LCSO, NES (E)
96-h ECSO, NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
NES(E)
NES(E)
NES(E)
LOW
HEALTH EFFECTS:
Absorption
Nil thru skin as neat solid; poor thru skin when in solution;
poor thru lungs and GI tract by analogy to closely related
compounds (P)
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Marginal (E)
LOW
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Record ID: Proprietary K: Aryl phosphate
CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye/Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/Mutagenicity
Systemic Effects
Overall Hazard Concern for
Non-Cancer Health Effects
Low by analogy to a
closely related compound (P)
Low by analogy to a
closely related compound (P)
Moderate by analogy to closely related compounds (liver
effects); 28-d repeated-dose study (inadequate), rats, diet,
liver effects at 0.5%, NOAEL = 0. 1% (P)
MODERATE
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4.2.15
Proprietary L
Record ID: Proprietary L: Aryl phosphate
CAS No.
MW:
MF:
Physical Forms:
Neat: Solid
As Formulated:
Use: Flame retardant,
additive
SMILES:
Name: Aryl phosphate
Synonyms:
ASSESSMENT SUMMARY:
Concern Level
HIGH
MODERATE
LOW
Persistence
X
Bioconcentration
X
Cancer Health Hazard
X
Non-Cancer Health Hazard
Xc
Aquatic Toxicity Hazard
X
Is the chemical predicted to be a PBT by
PBT Profiler?
No
Overall Hazard Concern
Human Health Hazard: Moderate
Aquatic Hazard: Low
Based on systemic effects.
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Record ID: Proprietary L: Aryl phosphate CAS No.
PHYSICAL/CHEMICAL PROPERTIES
Melting Point (deg C)
Boiling Point (deg C)
Boiling Point Pressure (mm Hg)
Vapor Pressure (mm Hg)
Water Solubility (g/L)
LogKoW
90 (E)
>400 (E)
760 (E)
<10'6 (E)
<10'6 (E)
10.43 (E)
ENVIRONMENTAL TRANSPORT AND FATE:
Transport
Henry's Law Constant - HLC
(atm-m3/mole)
Soil Adsorption Coefficient - KOC
Bioconcentration Factor - BCF
6.85xlO'7(E)
1.9xl06(E)
3-1 (E)
Persistence
Experimental Biodeg Tests
Ultimate Biodeg Model
Primary Biodeg Model
BOD or COD
Atmospheric Half-life
Hydrolysis Half-life
Volatilization Half-life for Model
River
Volatilization Half-life for Model
Lake
Removal in Sewage Treatment
Plant
Ready Biodegradability
Recalcitrant (E)
Weeks (E)
8.8 hours (E)
79 days (E)
Negligible (E)
94% (E)
Not ready biodegradable (E)
Byproducts
Degradation Products
Metabolites
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Record ID: Proprietary L: Aryl phosphate CAS No.
ECOTOXICITY:
ECOSAR Class
Esters-phosphate
Acute Toxicity
Fish LC50
Daphnid LCso
Green Algae ECso
96-h LCSO, NES (No effects at saturation) (E)
48-h LCSO, NES (E)
96-h ECSO, NES (E)
Chronic Toxicity
Fish ChV
Daphnid ChV
Green Algae ChV
Overall Hazard Concern for
Aquatic Toxicity
NES(E)
NES(E)
NES(E)
LOW
HEALTH EFFECTS:
Absorption
Nil thru skin as neat solid, poor thru skin in solution; poor
thru lungs and GI tract, based on closely related analogs
CANCER HEALTH EFFECTS:
Experimental data
OncoLogic Results
Overall Hazard Concern for
Carcinogenicity
Marginal
LOW
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Record ID: Proprietary L: Aryl phosphate
CAS No.
NON-CANCER HEALTH EFFECTS:
Acute Toxicity
Eye Irritation
Skin Irritation
Skin Sensitizer
Reproductive Effects
Developmental Effects
Immune System Effects
Neurotoxicity
Genotoxicity/ Mutagenicity
Systemic Effects
Overall Hazard Concern for Non-
Cancer Health Effects
Low, concern for sensitization by analogy to closely
related compounds (P)
Low; Not neurotoxic by analogy to a closely related
compound which yielded negative results in all reliable
oral assays for delayed acute neurotoxicity in hens and
subchronic neurobehavioral assays in rats (M);
Proprietary L lacks structural motifs associated with
neurotoxicity (P)
Moderate, systemic effects by analogy to closely related
compounds, including 28-d repeated-dose study
(inadequate), rats, diet, liver effects at 0.5%, NOAEL =
0.1% (P)
MODERATE
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5.0 CONSIDERATIONS FOR SELECTING A REPLACEMENT FOR PENTABDE
Multiple factors must be considered when selecting an appropriate chemical flame retardant. In
addition to flame retardancy properties and health and environmental considerations, the flame
retardant's use cannot negatively affect the quality of the foam (either physical characteristics or
aesthetics that would reduce its desirability in the market place). This is a concern because the
chemical will be incorporated in large amounts that may have effects on the foam product (e.g.,
pentaBDE formulations can make up as much as 8 percent by weight of the final foam product
and other flame-retardant formulations have been used at concentrations above 10 percent).
Additionally, it must be practical to use the chemical during production and processing of the
foam and furniture with existing equipment. Finally, the chemical cannot be cost prohibitive.
The Furniture Flame Retardancy Partnership recognizes the significance of considering practical
alternatives. The information in this report is focused on environmental attributes and can be
weighed with cost and performance information when selecting alternatives.
5.1 Positive Environmental Attributes
This section identifies a set of positive attributes that companies should consider when
formulating or selecting a flame retardant, or flame-retarded raw materials (e.g., foam and
textiles) that will meet or exceed existing flammability standards. These attributes are linked to
different aspects of what might happen to a chemical substance during its life cycle. While
ensuring that fire-safety standards are met, the following environmentally desirable chemical
characteristics and attributes, relevant to many flame-retardant chemicals, should be considered
general "rules of thumb".
Aerobic Degradation
Biodegradation and incineration are both forms of aerobic degradation or aerobic oxidation of
the chemical. Biodegradation is mediated by living organisms and generally slow compared to
incineration which is abiotic on a rapid time line. Environmental oxidation can be an abiotic
form of aerobic degradation which is generally very slow for most chemicals. Abiotic oxidative
processes addressed here occur in the absence of light. For the purposes of this report, two
categories of aerobic degradation are being discussed: biodegradation and incineration.
Attributes and considerations associated with these categories are discussed in more detail
below.
Readily Biodegradable: Low Persistence
Typically, the environmental profile of a chemical improves with its rate of
biodegradation. According to the Organization for Economic Cooperation and
Development (OECD), a chemical is readily biodegradable if, in a 28-day test, it
biodegrades 60 percent or more within 10 days of the time when degradation first reaches
10 percent (70% for DOC-based tests). There are two main features of readily
biodegradable substances. Hydrophobic components composed of unsaturated linear
alkyl chains (straight chain carbon molecules) biodegrade more rapidly under aerobic
conditions in sewage treatment plants and the environment than highly branched chains.
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Also, hydrophobic and hydrophilic components that are linked by an easily biodegradable
group like a carboxylic acid ester will separate the hydrophobe from the hydrophile
during the first step through aerobic biodegradation (i.e., ester hydrolysis).
Keep in mind that while the rate of biodegradation is important, it is equally important to
be aware of the byproducts formed through the degradation process. In some cases, the
products of biodegradation might be more toxic and persistent than the parent compound.
Incineration: Consideration of Combustion Byproducts
A concern with chemicals introduced into foam products is the formation of hazardous
combustion byproducts either during a residential fire or if the consumer product is
ultimately disposed to an incinerator. For example, halogenated flame retardants have the
potential to combine with other organic compounds during combustion and form
halogenated dioxins and furans. The formation of other hazardous combustion
byproducts should also be considered.
Low Bioaccumulation Potential and Low Unavailability: High log KOW (>8); Large
Molecule
The ability of a chemical to accumulate is often measured by the bioconcentration factor (BCF).
A high BCF indicates a high potential to bioaccumulate. Quantified, chemical-specific BCFs are
often not available; however, this property can be estimated by correlating it with another
readily-available parameter - the octanol-water partition coefficient (Kow). In general, a log Kow
of 3.5 to 5 corresponds to BCFs of approximately 1,000 to 5,000. Both ranges represent a
moderate to high bioaccumulation potential. Note that as the log Kow increases above 8, the
bioaccumulation potential decreases.
The potential for a molecule to be absorbed and harm an organism is less when the molecule is
larger than a certain size. Molecules with the following characteristics are not available for
passive uptake through the respiratory membranes of aquatic organisms: (a) molecules with
hydrophilic components having large cross-sectional diameters, at least twice as large as
hexabromobenzene (i.e., greater than 10 A), or (b) neutral and anionic surfactants with molecular
weights greater than 1,000 daltons. (Large diameters or high molecular weights will limit
toxicity to surface effects only and will prevent systemic effects.)
In addition, high molecular weight molecules (greater than 1,000 daltons) tend to be less volatile
and therefore, may exhibit less of a potential for inhalation exposure to vapors during
manufacturing and processing of foam and textiles. If exposure occurs high molecular weight
molecules are less likely to be absorbed, therefore limiting potential for adverse effects to be
expressed.
Reactive Flame Retardants: Even if a chemical has the potential to bioaccumulate, the
environmental concerns may be reduced or mitigated if the chemical is permanently incorporated
into a commercial product. In this case, the potential for exposure to the chemical is greatly
decreased. Reactive flame retardants are generally incorporated into the product (e.g., foam or
textile) during the early stages of manufacturing. Additives are mixed throughout the
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formulation, but are not chemically bound. Therefore, these additives have a much higher
potential to migrate, or leach, from the product into the environment under normal conditions.
Low Toxicity: Effects on several human health endpoints should be minimized. These effects
include: cancer hazard, skin sensitization, reproductive effects, developmental effects,
neurological effects, systemic effects and mutagenicity. Section 4 discusses methods to
characterize these effects and presents results of the screening level evaluations for the 14
formulations assessed in this report.
5.2 Aesthetic and Performance Considerations
Scorching is a primary concern in the manufacture of flexible polyurethane foam in general, and
is a particular concern for low-density foams. Light scorching results in discoloration or
yellowing of the foam, while severe scorching can cause decomposition resulting in permanent
damage to the foam. This phenomenon occurs because of the high temperatures that are
generated during production of the foam bun.
Scorching is more prevalent in low-density foams because of the necessity to use toluene
diisocyanate (TDI), which enables the foam to achieve low densities, better firmness and better
support. Methyl diphenyl diisocyanate (MDI) is used to manufacture higher density foams as
well as memory foams. The use of TDI causes a more exothermic (heat generating) reaction than
the use of MDI. Therefore, a higher thermally resistant flame retardant is required for
manufacturing low-density foams.
PentaBDE allows for the manufacture of low-density flame-retarded foam that is "snow white"
in color. Because of its aesthetic desirability, it became the industry standard in mattresses and
bedding products, as well as in many upholstered furniture applications. Greater acceptance of
off-white foams could allow manufacturers to choose from a wider variety of alternative flame
retardants. Barrier fabrics are allowing mattress manufacturers to mask the color of foam so that
it will not be visible to the consumer. Other characteristics of foam that can be affected by the
choice of flame retardants include firmness, durability and flexibility.
5.3 Process and Equipment Considerations
Another important consideration when selecting an alternative for pentaBDE is the feasibility of
using the new chemical in an industrial setting. Ideally the alternative should be compatible with
existing process equipment at foam manufacturing facilities. If it is not, the plants will be forced
to modify their processes and potentially to purchase new equipment. The ideal alternative would
be a drop-in replacement that has similar physical and chemical properties such that existing
storage and transfer equipment as well as foam production equipment can be used without
significant modifications.
For example, most U.S. foam facilities are equipped to store and process liquid flame-retardant
formulations through pipes, metering systems and pumps. A solid alternative may require foam
plants to make significant investments for conveyorized transfer, dust control systems and solid
weighing apparatus. These modifications are feasible, from an engineering point of view, but
may be cost prohibitive in certain circumstances.
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Similarly, many foam "recipes" and manufacturing procedures are based on the addition of
liquid flame-retardant chemicals. Addition of a solid flame retardant may require changes such
as additional mixing steps and alteration of the process times. In some cases, these changes can
have significant effects on foam quality or cost-effectiveness of manufacture.
5.4 Economic Viability
Foam manufacturing is a very competitive market in the United States and around the world. A
flame-retardant alternative that is either more expensive per pound, or requires more flame
retardant per linear foot to meet the fire safety standards will increase the foamer's raw material
costs. In this situation, a foam manufacturer will attempt to pass the cost on to their customers
(e.g., the furniture manufacturer), who will subsequently pass the cost to consumers. If this
increase causes a significant market share loss, the foam manufacturer may not be able to
compete and may be forced to discontinue use of the alternative, making the alternative
economically unfeasible.
5.5 Alternatives Technologies (General)
Potential alternatives for pentaBDE can be separated into two categories: (1) alternative
chemicals, and (2) alternative technologies. Chemical alternatives are the focus of this report;
however this section provides a brief discussion of three currently-available alternative
technologies being considered for further investigation by the Furniture Flame Retardancy
Partnership: barrier technologies, graphite impregnated foam and surface treatment. Graphite
impregnated foam and surface treatments have limited commercial uses; therefore, they are only
briefly discussed. Barrier technologies are predominantly used in mattress manufacturing rather
than residential upholstered furniture. However, there is considerable interest in future
applications for furniture. Future partnership activities may focus on barrier technologies if
appropriate.
In addition to the following technologies, it should be noted that some furniture designs exclude
the use of filling materials, and even fabric altogether. Design therefore, should be considered
when evaluating alternative means for achieving flame retardancy in furniture.
5.5.1 Barrier Technologies
Flame-retardant barrier materials can be a primary defense in protecting padding for furniture
and mattresses. Manufacturers can layer barrier materials to improve the flame retardancy of
their products. This layering approach allows a product to maintain its fire resistance even if one
layer is compromised.
There are many types of barrier materials available. Fabrics composed of natural fibers such as
cotton that are chemically treated to make them flame retardant are flame-retardant barrier
materials. The hazards of these chemical treatments have not been assessed in this report. Fabrics
composed of synthetic fibers that are inherently flame retardant are also flame-retardant barrier
materials. Plastic films derived from flame-retardant resins are also flame-retardant barrier
materials. These materials are designed and manufactured to meet specific flammability
standards. This also explains the large number of flame-retardant barrier materials that are
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available. Flame-retardant barrier materials can be characterized by cost, resulting in three
primary groups.
The first group of flame-retardant materials is the chemically treated, primarily boric acid
treated, cotton-based materials. These materials are the least expensive flame-retardant barrier
materials available. Mattress manufacturers that base their material decisions predominantly on
cost prefer these flame retardants.
The second group of flame-retardant materials is a blend of inexpensive natural fibers and
expensive synthetic fibers. Synthetic fibers used in these blends include VISIL, Basofil,
Polybenzimidazole, KEVLAR, NOMEX and fiberglass. Smaller manufacturers of furniture and
mattresses in niche markets use these materials. These blends are commonly used in bus and
airplane seating.
The third group of flame-retardant materials is composed solely of expensive, high-performance
synthetic fibers. They are generally used in industrial or high-performance applications such as
firemen's coats and astronaut space suits.
Barrier materials can also be divided into woven or nonwoven fabrics. Woven fabrics tend to use
general weaving technology to manufacture the fabrics. Manufacturers can customize fabrics to
meet specific customer needs. Nonwoven fabrics are created using quite different technologies.
Thermally bonded fabrics are a type of nonwoven fabrics. These materials consist of a core,
typically cotton, which is fed with one or two outer layers of melt blown and/or spunbond
polypropylene webs. The polypropylene web serves as the binder in this process. The core and
the web pass between a smooth and a patterned calendar. The calendars are heated and thermally
bind the core to the web. This process creates thermally bonded laminates. Another type of
nonwoven fabrics is needle-punched nonwovens. In this process, a spun bonded or carded web
passes under a needle board that contains thousands of needles. As the needle passes into the
web, a barb catches a fiber and passes it through the web, interlocking the fibers.
One unique group of barrier materials is flame-retardant films. The films do not have the strength
or texture to be used as an external barrier. The film can be used to wrap the foam cushions or it
can be quilted with flame-retardant fabrics for added support and an extra layer of fire protection.
Neoprene film is a common flame-retardant film. One type of material that competes with
neoprene film is fiberglass fabric.
Mattress manufacturers are now using barrier technology to meet new fire safety standards in the
state of California (California Technical Bulletin 603).
More information on barrier fabrics can be found in the following sources:
Decabromodiphenylether: An Investigation of Non-Halogen Substitutes in Electronic Enclosure
and Textile Applications (Lowell, 2005)
Survey and Technical Assessment of Alternatives to Decabromodiphenyl Ether (decaBDE) in
Textile Applications (Posner, 2004)
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5.5.2 Graphite Impregnated Foams
Graphite impregnated foam (GIF) can be considered an "inherently flame-resistant foam" that is
self-extinguishing and highly resistant to combustion. It is a relatively new technology and is
largely used in niche markets such as for general aircraft seating. GIF technology produces foam
that can meet airline fire safety standards for the seats with a reduced dependency on flame-
retarded fabric. By minimizing the expense associated with flame-retardant fabric, GIF modified
foams can be priced competitively.
GIF technology reportedly allows the design and fabrication of complex, comfortable and
aesthetically pleasing seating for private aircraft. While GIF foam seating promises the
possibility of eliminating the need for barrier fabrics, there are tradeoffs. When the barrier is
removed, comprehensive composite flammability testing will be required on each new seat
design to meet current fire safety standards (Federal Airways Regulation Part 25 Appendix F).
5.5.3 Surface Treatments
Surface treatments are also used in some applications and niche markets and may be appropriate
for some textile manufacturing and furniture manufacturing readers of this document. However,
surface treatments may not be viable as industry-wide replacements for pentaBDE for use in
low-density foam for the following reasons:
There have been many proposals to achieve good resistance to ignition by post impregnation of
foam with a variety of additives including borates, phosphates, various ammonium salts, etc.
In addition to durability concerns (many surface treatments wash off or degrade over time), there
are other considerations that limit their use.
The main concern is difficulty in achieving uniform impregnation of a foam cushion, which may
be 5 or 6 inches thick. In addition, many of these systems are water-based and the impregnated
pieces then have to be dried, which is a slow and expensive process. The drying process also
tends to produce a thin crust of the additive on the surface of the flexible polyurethane foam
cushion. A variation of this approach has been to surface treat the finished upholstered cushion.
This process must occur at the furniture assembly plants, which are not typically equipped for
chemical processing. Some surface treatments can also leave an undesirable coating on the fabric
cover or the cushion that is subject to disruption by friction during use.
5.6 Methods for Selecting Chemical Flame Retardants
The Partnership designed this report to provide stakeholders with the ability to impose their own
values on which chemicals to select and weigh information based on multiple considerations,
focusing on environmental and human health attributes. Various governmental, commercial and
non-governmental organizations have developed tools and methods to assist with complex
decision-making, some of it specific to creating chemical rankings.
The Analytic Hierarchy Process (AHP) is a widely used technique for multi-attribute decision
making. The process was developed by TL Saaty (The Analytical Hierarchy Process, McGraw-
Hill, 1980), and uses a complex weighting system for comparing pairwise criteria, which can be
further broken down into sub-criteria. A useful guide for investigating MCA tools is OECD's
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Technical Guidance Document on the Use of Socio-Economic Analysis in Chemical Risk-
Management Decision Making. Another useful guide is found at
http://farmweb.jrc.cec.eu.int/ci/S6_weighting.htm.
Due to the complexity of the calculations, commercial software has been developed to assist
analysts (www.expertchoice.com), though the calculations can be done without specialized
software (http://mdm.gwu.edu/forman/Reproducing%20AHP%20calculations.pdf).
Two resources specific to creating chemical rankings, and which are applicable to the data
generated from this report are:
1. CARS - Chemical Assessment and Ranking System found at:
http: //www. zero waste. org/cars/
2. Substitution of PBT (persistent, bioaccumulative, toxic) substances in products and
processed. Guidance for the use of environmentally sound substances.
A. www.umweltdaten.de/umweltvertraegliche-stoffe-e/partl.pdf
B. www.umweltdaten.de/umweltvertraegliche-stoffe-e/part2.pdf
The methodology in the second web site is particularly relevant. While it is written to address
chemicals relevant to the aquatic environment, it could be modified to add concerns for releases
to air as well.
Regulations that restrict the use of particular chemicals may also be useful to stakeholders when
making decisions about flame retardancy methods. Appendix C provides a list of regulations that
readers may reference to locate sources of information.
The information in this report is intended to aid industry in incorporating environmental
information into their decision-making processes. Consumer groups may also find this
information useful. While the information in this report is static, the Partnership will continue to
work together to update this information and identify environmentally preferable options for both
furniture and mattress fire safety. Current information on the Partnership is available on the web
at http://www.epa.gov/dfe/proiects/flameret/index.htm.
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"Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work
Environments." Environmental Science & Technology. 35(3): 448-454.
29. Stapleton, H.M., RJ. Letcher, and I.E. Baker. 2004. "Debromination of Polybrominated
Diphenyl Ether Congeners BDE 99 and BDE 183 in the Intestinal Tract of the Common
Carp (Cyprinus carpio)." Environmental Science & Technology. 38(4): 1054-1061.
30. Stapleton, H.M., N.G. Dodder, J.H. Offenberg, M.M. Schantz, S.A. Wise. 2005.
"Polybrominated Diphenyl Ethers in House Dust and Clothes Dryer Lint." Environmental
Science & Technology. 39(4): 925-931.
31. State of California. 2004. Assembly Bill No. 2587. September 21.
http://www.leginfo.ca. gov/pub/03 -04/bill/asm/ab_25 51 -
2600/ab 2587 bill 20040921 chaptered.pdf
32. State of Hawai'i. 2004. House Bill No. 2013. June 24.
http://www.capitol.hawaii.gov/session2004/bills/hb2013_cdl_.htm
33. Toxicology Excellence for Risk Assessment (TERA). 2004. Report of the Peer
Consultation Meeting on Pentabromodiphenyl Ether. Voluntary Children's Chemical
Evaluation Program (VCCEP) Peer Consultation Meeting on Octabromodiphenyl Ether
and Pentabromodiphenyl Ether, June 3-5, 2003, Cincinnati, OH.
http://www.tera.org/peer/VCCEP/OctaPenta/OctaPentaWelcome.html
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34. U.S. EPA. 1992. Classification Criteria for Environmental Toxicity and Fate of
Industrial Chemicals. Office of Prevention, Pesticides and Toxics, Chemical Control
Division. Washington, DC.
35. U.S. EPA. 1994. US EPA/EC Joint Project on the Evaluation of (Quantitative) Structure
Activity Relationships. Office of Prevention, Pesticides and Toxic Substances. EPA 743-
R-94-001. Washington, DC. http://www.epa.gov/oppt/newchems/21 ecosar.htm
36. U.S. EPA. 1999. "Category for Persistent, Bioaccumulative, and Toxic New Chemical
Substances" Federal Register. 64(213): 60194-60204. November 4.
http://www.epa.gov/fedrgstr/EPA-TOX/1999/November/Dav-04/t28888.htm
37. U.S. EPA. 2000. "Revision to CEB's Method for Screening-Level Assessments of
Dermal Exposure." Memorandum to CEB staff and contractors. Office of Prevention,
Pesticides and Toxics, Economics, Exposure and Technology Division, Chemical
Engineering Branch. Washington, DC.
38. Wagner, P.M., J.V. Nabholz, RJ. Kent. 1995. "The New Chemicals Process at the
Environmental Protection Agency (EPA): Structure-Activity Relationships for Hazard
Identification and Risk Assessment." Toxicology Letters. 79: 67-73.
39. Watanabe, I, and S. Sakai. 2003. "Environmental release and behavior of brominated
flame retardants." Environment International. 29: 665-682.
40. Weil, E., and S. Levchik. 2004. "Commercial Flame Retardancy of Polyurethanes."
Journal of Fire Sciences. 22(3): 183-210.
41. Wilford, B.H., G.O. Thomas, R.E. Alcock, K.C. Jones, and D.R. Anderson. 2003.
"Polyurethane Foam as a Source of PBDEs to the Environment." Organohalogen
Compounds. 61:219-222.
42. Wilford, B.H., T. Harner, J. Zhu, M. Shoeib, and K.C. Jones. 2004. "Passive Sampling
Survey of Polybrominated Diphenyl Ether Flame Retardants in Indoor and Outdoor Air
in Ottawa, Canada: Implications for Sources and Exposure." Environmental Science &
Technology. 38(20): 5312-5318.
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Appendix A
PentaBDE Facts
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Summary of USEPA's Understanding of PBDEs
Polybrominated diphenylethers (PBDEs) are members of a broader class of brominated
chemicals used as flame retardants; these are called brominated flame retardants, or BFRs. There
are commercial mixtures of PBDEs with different average amounts of bromination: penta-, octa-,
and decaBDE. These chemicals are major components of commercial formulations often used as
fire retardants in furniture foam (pentaBDE), plastics for TV cabinets, consumer electronics,
wire insulation, backcoatings for draperies and upholstery (decaBDE) and plastics for personal
computers and small appliances (octaBDE). The value of these chemicals is their ability to slow
ignition and rate of fire growth, and as a result increase available escape time in the event of a
fire involving the above consumer products.
Although use of these chemicals is intended to save lives and property, there have been
unintended consequences. Environmental monitoring programs in Europe, Asia, North America,
and the Arctic have detected several PBDEs in human breast milk, fish, aquatic birds and
elsewhere in the environment. Tetra- to hexabrominated diphenyl ethers are the PBDEs most
frequently detected in wildlife and humans. The exact mechanisms or pathways by which the
PBDEs end up in the environment and humans are not known yet, but would include releases
from manufacturing or processing of the chemicals into products like plastics or textiles, aging
and wear of the end consumer products and direct exposure during use (e.g., from furniture).
EPA is not only interested in responding to monitoring data, however. The Agency
continually looks for pollution prevention opportunities; the Pollution Prevention Act of 1990
and EPA's Pollution Prevention Strategy establish that pollution should be prevented or reduced
at the source whenever feasible. The Agency has also made protection of children's health a
fundamental goal of public health and environmental protection in the United States.
In general, the human health and environmental concerns are higher for the lower
brominated mixtures (i.e., pentaBDE and octaBDE), and data suggest that higher brominated
forms such as decaBDE can be altered to form more lexicologically active lower brominated
forms. The limited toxicity test data that is currently available indicate the potential for adverse
effects to humans and environmental organisms, especially for lower brominated mixtures, but
existing hazard and exposure information on PBDEs is incomplete. More needs to be understood
about the environmental fate and the exposure pathways that lead to PBDE presence in wildlife
and people. PBDEs appear to be persistent and bioaccumulative in the environment. EPA
believes an improved understanding of potential risks posed by the different PBDE mixtures in
their various use applications is needed. EPA is addressing PBDE information needs with a
three-pronged approach, which includes:
Efforts to better understand the environmental properties, exposure pathways and how
these chemicals are getting into human tissue;
Research and detailed testing to determine health and environmental effects; and
Evaluation of potential substitutes, which includes the analysis of technical performance,
cost-effectiveness and risk-risk trade-offs related to fire prevention and toxicity.
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EPA offices and regions are working with fire safety advocates, industry, environmental
and public health groups, other federal agencies, state governments and other national
governments to answer the key questions and provide a basis for informed risk reduction
decisions, including potential regulatory and voluntary actions. In November 2003, Great Lakes
Chemical Corp., the only U.S. manufacturer of pentaBDE and octaBDE, announced a voluntary
phase out of both those chemicals by the end of 2004.
Toxicity
There are commercial mixtures of PBDEs with different average amounts of
bromination: penta-, octa- and decaBDE. In general, the human health and environmental
concerns are greater for the lower brominated mixtures.
Penta- and OctaBDE
Effects on induction of hepatic enzymes were the basis of the EPA Integrated Risk Information
System (IRIS) assessments of commercial pentaBDE and octaBDE mixtures which were
completed in 1990. However, although liver enzyme induction was used as the basis for the RfD
then, based on current methodology, this endpoint would not now be used as the basis of an RfD
given the absence of other negative liver effects or histopathology. An update of the IRIS
assessment for PBDE's is in progress. Several recent studies in young laboratory animals (rats
and mice) exposed to commercial pentaBDE or to several individual congeners during gestation
have shown some evidence of alterations in several behavioral parameters, deficits in learning
and memory, and delays in the onset of puberty. Prenatal exposure to octaBDE mixtures in
laboratory animals has resulted in reductions in fetal body weight, and delays in ossification - a
longer than normal period before hardening of the bones. PentaBDE and octaBDE mixtures and
individual congeners have also been shown to disrupt normal thyroid hormone levels in adult
rats and mice. This could have possible concerns for developmental neurotoxic effects since it is
well-established that disruption of thyroid hormone levels in the pregnant female may affect
brain development in the fetus. The National Toxicology Program (an interagency program
consisting of relevant toxicology activities of the Centers for Disease Control, Food and Drug
Administration and National Institutes of Health) plans to conduct both chronic and subchronic
toxicity studies on the commercial pentaBDE mixture, as well as the individual congeners
appearing in greatest concentration in the mixture.
DecaBDE
Less is known about the potential toxicity of decaBDE. However, in contrast to penta- and
octaBDE, decaBDE is poorly absorbed which may limit its potential toxicity. Some studies have
shown thyroid and liver toxicity. Prenatal developmental toxicity studies in animals have been
equivocal. A recent study in mice has provided some evidence of behavioral alterations. The
European Commission will be requiring a more complete developmental neurotoxicity study in
rodents to help clarify the potential for decaBDE exposure to result in developmental
neurotoxicity. In addition, exposure to very high doses of decaBDE has been shown to cause
tumors in laboratory animals.
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Exposure
PBDEs have been measured in breast milk, adipose tissue and blood serum from human
populations in Sweden, Finland, Germany, Japan, Spain, Canada and the United States. PBDE
concentrations have steadily increased over 20 years of monitoring conducted in Sweden and
Germany. In Sweden, PBDE levels in breast milk had doubled every 5 years between 1972 and
1997, with a decreasing trend since 1997. North American data are limited and additional
studies are ongoing to determine relative levels in breast milk and blood serum compared to
those found in Europe. However, average levels as measured in 23 human adipose tissue samples
and 32 serum samples from among California women and 50 breast milk samples from Canada
were higher than PBDE levels measured in Sweden.
Limited monitoring studies have found PBDEs in air, water, sediment, biota and sewage
sludge throughout North America. The highest concentrations are generally associated with
locations near facilities manufacturing or processing PBDEs. Concentrations of PBDEs are
higher in municipal sewage sludge than in other environmental media. Recently reported PBDE
concentrations in the United States and Canada are greater than those reported in Europe and
Asia.
Different congeners are found at different levels in environmental media and wildlife.
Generally the highest measured concentrations are for the tetra (>50%), penta (20-30%), hexa
(15-20%) and hepta and octa brominated (< 20%) congeners. Which congeners are found and
their relative and absolute concentrations vary from site to site.
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Questions and Answers on PBDEs
1. What are PBDEs?
Polybrominated diphenylethers (PBDEs) are members of a broader class of brominated
chemicals used as flame retardants; these are called brominated flame retardants, or BFRs. There
are three commercial mixtures of PBDEs with differing average amounts of bromination: penta-,
octa-, and decaBDE.
2. What are PBDEs used for?
These chemicals are major components of commercial formulations often used as flame
retardants in furniture foam (pentaBDE), plastics for TV cabinets, consumer electronics, wire
insulation, and backcoatings for draperies and upholstery (decaBDE), and plastics for personal
computers and small appliances (octaBDE). The benefit of these chemicals is their ability to
slow ignition and rate of fire growth, and as a result increase available escape time in the event
of a fire.
3. What are concerns associated with PBDEs?
Although use of flame retardants saves lives and property, there have been unintended
consequences. There is growing evidence that PBDEs persist in the environment and accumulate
in living organisms, as well as toxicological testing that indicates these chemicals may cause
liver toxicity, thyroid toxicity, and neurodevelopmental toxicity. Environmental monitoring
programs in Europe, Asia, North America, and the Arctic have found traces of several PBDEs in
human breast milk, fish, aquatic birds, and elsewhere in the environment. Particular congeners ,
tetra- to hexabrominated diphenyl ethers, are the forms most frequently detected in wildlife and
humans. The mechanisms or pathways through which PBDEs get into the environment and
humans are not known yet, but could include releases from manufacturing or processing of the
chemicals into products like plastics or textiles, aging and wear of the end consumer products,
and direct exposure during use (e.g., from furniture).
4. What is the Agency doing to better understand the possible risks from exposure to
PBDEs?
EPA is currently evaluating a risk assessment and data needs analysis on PBDEs that was
developed by industry for the Voluntary Children's Chemical Evaluation Program (VCCEP).
This assessment evaluates the potential risks to children and prospective parents from all
potential exposure scenarios. EPA will be releasing its views of the assessment, including any
further VCCEP data needs, in the next few months.
Directly or through grant mechanisms, EPA has been supporting research aimed at a range of
topics related to PBDEs, including measuring PBDE levels in umbilical cord blood from
newborn U.S. infants, mothers' blood, house dust, food, breast milk, and children; potential
thyroid toxicity and developmental neurotoxicity; and the environmental fate of the PBDEs upon
their release during production or after disposal of products that contain these chemicals.
EPA's Office of Research and Development, National Center for Environmental Assessment, is
enhancing its Integrated Risk Information System (IRIS) database on the PBDEs. IRIS is a
database of human health effects that may result from exposure to substances found in the
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environment. The Agency developed IRIS to provide consistent information on chemical
substances for use in risk assessments, decision-making and regulatory activities. The
information in IRIS is intended for those without extensive training in toxicology, but with some
knowledge of health sciences.
5. How does this action complement the decision by the sole US manufacturer to phase out
production by December 31, 2004?
This action builds on the November 3, 2003, announcement by the Great Lakes Chemical
Corporation, the only U.S. manufacturer of these chemicals, who agreed to voluntarily phase-out
production by December 31, 2004. In 2003, EPA commended Great Lakes Chemical
Corporation for taking this responsible action. EPA is concerned that manufacture or import
could be reinstated in the future, and thus believes it is necessary to have the opportunity to
evaluate any new manufacture or import associated with these chemicals.
6. Why are these chemical important and are there substitutes?
These chemicals provide a very important benefit because of their ability to save lives and
property by slowing ignition and rate of fire growth, and therefore increase available escape time
in the event of a fire. However, EPA also believes both the phase out and the Significant New
Use rule will further spur the development of safer alternatives.
EPA has been working to ensure that following the phasing out of these two chemicals,
acceptable alternatives are available to industry. Such alternatives would need to meet
technological requirements of industry users, flame retardancy requirements in US standards,
and present lower hazards than the chemicals for which they are substituting. To promote these
goals and to explore the safety of alternative flame retardant chemicals, EPA has convened a
group of stakeholders in its Furniture Flame Retardancy Partnership, including chemical
manufacturers and users, the furniture industry, government agencies, and consumer groups, who
will work together to evaluate possible alternatives to PentaBDE.
7. Should consumers discard any products that might contain PentaBDE or Octa?
No, the EPA does not believe that there is a need to remove or replace products that may contain
these chemicals. EPA has not concluded that PBDEs pose an unreasonable risk to human health
or the environment. However, due to growing concerns, EPA believes that the phase out and the
regulatory action taken in this announcement are useful steps to minimize and ultimately help
prevent further exposure to these chemicals.
8. What are PBDEs commonly used for?
The PBDEs are major components of commercial formulations often used as fire retardants in
furniture foam, plastics for TV cabinets, consumer electronics, wire insulation, and back-
coatings for draperies and upholstery, and plastics for personal computers and small appliances.
These chemicals slow ignition and rate of fire growth, and, as a result, increase available escape
time in the event of a fire involving the above consumer products.
9. How are people exposed to PBDEs?
PBDEs are not chemically bound to plastics, foam, fabrics, or other products in which they are
used, making them more likely to leach out of these products. PBDEs may enter the air, water
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and soil during their manufacture and use in consumer products. The primary route of human
exposure is currently unclear.
10. What is the Agency doing to better understand the occurrence of PBDEs in the
environment?
EPA is addressing PBDE information needs with a three-pronged approach which includes: 1)
efforts to better understand the environmental properties, exposure pathways, and how these
chemicals are getting into human tissue; 2) research and detailed testing to determine health and
environmental effects from exposure to PBDEs; and 3) evaluation of potential PBDE substitutes,
which includes the analysis of technical performance, cost-effectiveness, and risk-risk trade-offs
related to fire prevention and toxicity.
11. What efforts are underway to discourage continued use of the PBDEs?
In November 2003, the Great Lakes Chemical Corporation announced a voluntary phase out of
PentaBDE and OctaBDE by the end of 2004. Great Lakes is the only U.S. manufacturer of these
PBDEs. To follow up on this voluntary action, EPA is working with chemical manufacturers and
end users to facilitate an orderly transition to safer substitutes. The State of California has
enacted a law banning use of PentaBDE and OctaBDE by January 2008 (recently changed to
June 1, 2006) and other states (including Maine, Hawaii, Washington, and New York) are also
considering or have passed similar legislation. In Europe, the European Union enacted a ban on
PentaBDE and OctaBDE in all products which took effect on August 15, 2004.
EPA is also working with the fire safety advocates, chemical manufacturers, manufacturers of
end products such as furniture or plastics for electronics, environmental and public health
groups, other federal agencies, state governments, and other nations to answer key questions and
help people make informed decisions based on risk. EPA is considering both regulatory and
voluntary actions.
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Appendix B
Interpretive Guidance
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Interpretive Guidance Document for Sustainable Futures Summary Assessment
Updated September 2004
This document was developed to help interpret results from the Sustainable Futures / P2 Framework
models. Information is also included here which helps assign concern levels to results based on
criteria from U.S. EPA OPPT's New Chemicals Program
http://www.epa.gov/oppt/newchems/index.htm. Information contained in this document is presented
in greater detail in the P2 Framework Manual. For more information on the models, estimations
provided, and interpretation of results, please check the manual, which can be downloaded from
http ://www. epa. gov/oppt/p2framework/docs/p2manua.htm.
Physical/Chemical Properties and Environmental Fate Estimations 2
EPISuiteJ - Entering Data 2
Interpreting Results from EPISuiteJ 2
Hazard Estimations 5
Aquatic Toxicity Hazard - ECOSAR 5
Human Health Hazard - Cancer - OncoLogic 6
Human Health Hazard - Non-Cancer 7
PBT Potential Estimation 7
Exposure Estimations 8
Aquatic Exposure - E-FAST 8
Human Exposure - ChemSTEER and E-FAST 8
Risk Estimations 9
Estimating Aquatic Risk 9
Aquatic Risk Summary 11
Estimating Human Health Non-Cancer Risk 11
Human Health Risk Summary 13
Occupational Risk Summary 14
Estimating Human Health Cancer Risk 14
References Cited 15
Model Availability
• EPISuite™ - download at no cost from http://www.epa.gov/opptintr/exposure/docs/episuite.htm
• ECOSAR - download at no cost from http://www.epa.gov/oppt/newchems/21 ecosar.htm
• PBT Profiler - use on-line at no cost at www.pbtprofiler.net
• Cancer Expert System / OncoLogic - contact Bill Waugh, waugh.bill@epa.gov for information.
U.S. EPA has purchased the commercial rights to OncoLogic and plans to make the model
publicly available.
• E-FAST - download at no cost from http://www.epa.gov/opptintr/exposure/docs/efast.htm
• ChemSTEER - download at no cost from
http ://www. epa. gov/opptintr/exposure/docs/chemsteer.htm
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Physical/Chemical Properties and Environmental Fate Estimations
EPISuite™ - Entering Data
The chemical structure can be entered using SMILES notation - or - if the chemical has a CAS
Registry Number, the CAS numbers may be entered and the structure will be retrieved from the
EPISuite™ built-in database if available. There is also a name lookup function that allows the user
to retrieve chemical information without knowing the chemical structure or CAS number.
If any experimental data are available for the chemical, then all data should be entered into the input
screen for EPISuite™.
For chemicals that are known liquids with no experimental MP data, enter 20 deg C as an
experimental MP into the input screen for all EPISuite™ predictions.
Interpreting Results from EPISuite™
Melting Point and Boiling Point - Estimated by MPBPWIN
MP < 25 deg C = Liquid MP > 25 deg C = Solid BP < 25 deg C = Gas
Vapor Pressure - Estimated by MPBPWIN
> 10"4 = Vapor (gas) phase 10"5 - 10"7 = Vapor and particulate phase < 10"8 = Solid phase
For chemicals with a VP < 10"6, there is low concern for inhalation exposure.
Water Solubility (mg/L) - Estimated by WSKOWWIN
> 10,000 Very soluble
> 1,000 - 10,000 Soluble
> 100 - 1,000 Moderate solubility
> 0.1-100 Slightly soluble
< 0.1 Insoluble
Log K™ (Log P) - Estimated by KOWWIN
< 1 Highly soluble in water (hydrophilic)
> 4 Not very soluble in water (hydrophobic)
> 8 Not readily bioavailable
> 10 Not bioavailable - difficult to measure experimentally
Henry's Law Constant (atm-m3/mole) - Estimated by HENRYWIN
> 10"1 Very volatile from water
10"1 - 10"3 Volatile from water
10"3 - 10"5 Moderately volatile from water
10"5 - 10"7 Slightly volatile from water
< 10"7 Nonvolatile
If experimental vapor pressure and water solubility data are available and entered as input data into
EPISuite™, then the VP/Wsol estimate (instead of the bond or group estimation method) should be
used.
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Atmospheric Oxidation Half-life - Estimated by AOPWIN
< 2 hours Rapid
2 hrs - < 1 day Moderate
> 1 day-< 10 days Slow
>10 days Negligible
>2 days Has potential for long range transport in air
Hydrolysis Rates - Estimated by HYDROWIN
- Only Esters, Carbamates, Epoxides, Halomethanes, and certain Alkyl Halides are estimated in
HYDROWIN.
Biodegradation - Estimated by BIOWIN: 3 Models available in EPISuite™
1. Probability of Rapid Biodegradation (BIOWIN):
BIOWIN Linear and BIOWIN Nonlinear
> 0.50 Likely to biodegrade fast < 0.50 Not likely to biodegrade fast
2. Expert Survey Biodegradation (Primary/Ultimate):
Calculated Time Required Predicted Time Required
Rating for Biodegradation Rating for Biodegradation
5.0 Hours 5.0 Hours
4.5 Hours - days 4.0 Days
4.0 Days 3.0 Weeks
3.5 Days - weeks 2.5 Weeks - months
2.0 Months
1.0 Longer
3. Ready Biodegradability Model (MITI):
MITI Linear and MITI Nonlinear
> 0.50 Ready Biodegradable < 0.50 Not Ready Biodegradable
Soil Adsorption Coefficient (Log KoC) - Estimated by PCKOCWIN
> 4.5 Very strong sorption to soil and sediment, negligible migration potential to groundwater
3.5 - 4.4 Strong sorption to soil and sediment, negligible to slow migration potential to
groundwater
2.5-3.4 Moderate sorption to soil and sediment, slow migration potential to groundwater
1.5 - 2.4 Low sorption to soil and sediment, moderate migration potential to groundwater
< 1.5 Negligible sorption to soil and sediment, rapid migration potential to groundwater
Bioconcentration Factors - Estimated by BCFWIN
> 5000 High bioconcentration potential
1000 - 5000 Moderate bioconcentration potential
< 1000 Low bioconcentration potential
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STPWIN - Percent Removal in Sewage Treatment Plants
- Gives an indication of the percent removed from biodegradation (Bio P), sludge adsorption (Bio
S), and aeration (Bio A) in a POTW or Sewage Treatment Plant.
- Negligible biodegradation (half-life = 10,000 hours) is the default value for the primary clarifier
(P), aeration vessel (A), and final settling tank (S) unless otherwise specified in the input screen
for EPISuite™. If data are available for the chemical, these half-lives can be changed in the
input screen using the following guidance:
1 hour = for chemicals with data suggesting rapid biodegradation potential
3 hours = for chemicals with data suggesting moderate biodegradation potential
30 hours = for chemicals with data showing slow biodegradation potential
10,000 hours = default rate for chemical with unknown biodegradation potential
LEV3EPI - Fugacity Model
- Provides an indication of which environmental compartment the chemical is expected to partition
to and calculates an approximate persistence time.
WVOL - Volatilization from Water
- Uses molecular weight, Henry's Law Constant, and water solubility to estimate an upper limit
for volatilization from a body of water. The model does not take into account potential
adsorption to sediment and suspended organic matter when the Koc is high, which can increase
the volatilization half-life dramatically. Therefore, if the Koc for a given chemical is high, the
volatilization half-lives for a model river and model lake are expected to be significantly higher
than predicted in WVOL.
Persistence
U.S. EPA describes Persistence criteria in the PBT category for Premanufacture Notices in the
Category for Persistent, Bioaccumulative, and Toxic New Chemical Substances at
http://www.epa.gov/tri/pbt-fmal_rule.pdfhttp://www.epa.gov/fedrgstr/EPA-
TOX/1999/November/Dav-04/t28888.htm and in the final rule for TRI reporting of PBT Chemicals
http://www.epa.gov/tri/pbt-final_rule.pdf. These criteria are used by the PBT Profiler (described in
this document) to estimate environmental persistence potential of chemicals. These Persistence
criteria are:
PERSISTENCE
Water, Soil, Sediment*
Air**
Not Persistent
<60d
. 2d
Persistent
. 60 d
>180d
>2d
* New Chemical Program Criteria
** TRI Reporting Criteria
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Hazard Estimations
Aquatic Toxicity Hazard - ECOSAR
Develop Full Standard Aquatic Toxicity Profile
The standard aquatic toxicity profile consists of 3 acute values (fish LCso, daphnid LCso, and algae
EC50) and 3 chronic values (fish ChV, daphnid ChV, and algae ChV). Examples of toxicity values
that are generally used to fulfill the standard aquatic toxicity profile are provided below.
Organism
Fish
Daphnid (Aquatic Invertebrate)
Algae
Acute Toxicity Values
96-hour LC50
48-hour LC50
72- or 96-hour EC50
Chronic Toxicity Values
30-day ChV
ChV or 16-day EC50
ChV
A full standard profile for each chemical should be created using either predicted or experimental
data. If no predicted or experimental data are available for the chemical of interest, then analog data
may be used. If a single measured or predicted toxicity value is available for a species but the
corresponding acute or chronic value is not, then an acute to chronic ratio (ACR) can be used to
estimate the corresponding acute or chronic toxicity value:
Chronic toxicity estimate = (acute toxicity value) / (ACR)
Acute toxicity estimate = (chronic toxicity value) x (ACR)
An ACR of 10 is commonly applied to fish and daphnids and an ACR of 4 is commonly applied to
algae. Example calculations are provided below.
Fish LC50 = 0.10 mg/L -»• extrapolated fish ChV = (0.10 mg/L)/10 = 0.01 mg/L (ppm)
Algae ChV = 0.02 mg/L -> extrapolated algae EC50 = (0.02 mg/L) x 4 = 0.08 mg/L (ppm)
A full toxicity profile needs to be developed to perform an aquatic toxicity assessment. If an acute
or chronic toxicity endpoint cannot be determined for one or more species from measured data on
the chemical or analog or from predicted data, then category data can be used to fulfill the endpoint.
For example, a fish or daphnid toxicity value can be estimated using the fish-to-daphnid toxicity
ratio of chemicals within the same category (e.g., acrylates). Use data from multiple chemicals if
possible. All assumptions and toxicity data used for the estimation need to be documented in the
Sustainable Futures Summary Assessment.
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The following guidance can be used to assign aquatic toxicity concern levels:
SF Concern
ECOSAR Results
Low
All 3 acute values are >100 mg/L, AND all three chronic values are >10.0 mg/L, or there
are No Effects at Saturation (NES). NES occurs when a chemical is not soluble enough to
reach the effect concentration, i.e., the water solubility is lower than an effect
concentration, or, for liquids, when Kow criteria are exceeded for an endpoint. For solids,
NES is expected ifKow exceeds the specific SAR Kow cutoffs, or the effect concentration is
more than one order of magnitude (>_10X) less than water solubility.
Moderate
Any of the 3 acute values are >1.0 mg/L and <100 mg/L, OR any of the chronic values are
>0.1 mg/L and <10.0 mg/L
High
Any of the 3 acute values are <1.0 mg/L, OR any of the chronic values are <0.1 mg/L
(except for substances with very low solubility (NES))
NOTE: Kow cutoffs are specific to each SAR used in ECOSAR. The criteria can be found on the
bottom of the results screen for ECOSAR or in the ECOSAR User's Manual available for download
at http://www.epa.gov/oppt/newchems/sarman.pdf
NOTE: Guidance on the evaluation of polymers can be found in
Boethling R.S. and J. V. Nabholz. 1997. "Environmental assessment of polymers under the U.S.
Toxic Substances Control Act". In: Hamilton, J.D. and R. Sutcliffe, eds. Ecological assessment of
polymers: Strategies for product stewardship and regulatory programs. New York, NY: Van
Nostrand Reinhold, 187-234. ISBN 0-442-02328-6.
Human Health Hazard - Cancer - OncoLogic
Interpretation of OncoLogic Results:
SF Concern
Low
Further Research
Needed
Moderate
High
OncoLogic Results
Low
Marginal
Low-Moderate
Moderate
Moderate-High
High
Definition - OncoLogic Result
Unlikely to be a carcinogen
Likely to have equivocal carcinogenic activity
Likely to be weakly carcinogenic
Likely to be moderately active carcinogen
Highly likely to be a moderately active carcinogen
Highly likely to be a potent carcinogen
B-f
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Interpretation of Experimental Data:
SF Concern
Low
Moderate
High
Definition - Experimental Data
Negative experimental data
Positive cancer bioassay in experimental
carcinogenic effects
Positive experimental data in humans (e.
animals or chemical class known to
g. epidemiology study)
produce
NOTE: Measured data from a properly conducted study on the SF chemical or a relevant analog
always takes precedence over predicted data.
Human Health Hazard - Non-Cancer
Criteria for Assigning Non-Cancer Hazard Concern Levels:
SF Concern
Low
Moderate
High
Definition - Experimental Data
No basis for concern identified
Suggestive animal studies for chemical or analog(s) or chemical class known to
produce toxicity
Evidence of adverse effects in humans or conclusive evidence of severe effects in
animal studies
NOTE: Regulatory decisions will be made based on the following human health effects:
reproductive; immune; developmental; neurotoxicity; and systemic.
NOTE: Guidance on the evaluation of non-cancer human health concerns of polymers can be found
in: P2 Framework Manual, Oct 2003 version, edited Jan 2004, pg. 169-170 at
http ://www. epa. gov/oppt/p2framework/docs/p2manua. htm
PBT Potential Estimation
PBT Profiler - U.S. EPA describes Persistence, Bioaccumulative, and Toxicity (PBT) criteria in the
PBT category for Premanufacture Notices in the Category for Persistent, Bioaccumulative, and
Toxic New Chemical Substances at
http://www.epa.gov/fedrgstr/EPA-TOX/1999/November/Dav-04/t28888.htm and in the final rule for
TRI reporting of PBT Chemicals http://www.epa.gov/tri/pbt-final_rule.pdf. These criteria are used
by the PBT Profiler to estimate PBT potential of chemicals.
These PBT criteria are:
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PERSISTENCE
Water, Soil, Sediment*
Air**
BIOACCUMULATION
Fish BCF*
TOXICITY
Fish ChV*
Not Persistent
<60d
<2d
Not Bioaccumulative
<1000
Not Toxic
> 10 mg/L or No Effects at
Saturation
Persistent
>60d
>180d
>2d
Bioaccumulative
>1000
>5000
Toxic
0.1-10 mg/L
< 0.1 mg/L
NOTE: The PBT Profiler is not appropriate for certain types of chemicals, such as metals. Before
using the PBT Profiler determine if the chemical being evaluated is appropriate for running in the
PBT Profiler. Extensive information is provided within the on-line model at www.pbtprofiler.net
* New Chemical Program Criteria
** TRI Reporting Criteria
IMPORTANT NOTE:
Evaluate exposure if a moderate or high hazard concern has been identified for any endpoint.
Exposure Estimations
Aquatic Exposure - E-FAST
Predicted Environmental Concentration (PEC):
Amount expected to be found in surface water after release from industrial processes; also called
surface water concentration (SWC).
Estimated values can be determined using E-FAST and found under the General SIC Code
Information tab in the results screen. The 10% percentile, 7Q10 stream concentrations (ug/L) are
used for an SF Assessment.
To run E-FAST you will need to determine a chronic Concentration of Concern (COC) based on
the toxicity values derived in the Aquatic Toxicity section. The COC is one of the inputs for the E-
F AST program and an explanation for the determination of a chronic COC can be found on the
following page of this document.
Human Exposure - ChemSTEER and E-FAST
For Occupational Exposure Doses:
LADD, ADD, and APDR values will be estimated by ChemSTEER
For General Population Exposure Doses:
LADDpot, ADDpot, and ADRpot values will be estimated by E-FAST. The 10% percentile values
(mg/kg/day) are used for an SF Assessment.
-------
Lifetime Average Daily Dose (LADD or LADDpot):
The predicted lifetime exposure used to determine cancer risk usually based on an average lifetime
of 70 - 75 years and a working lifetime of 30 - 40 years.
Potential Average Daily Dose (ADD or ADDpot):
The predicted dose that represents potential chronic exposure based on a duration of repeated
exposure usually approximating an average of 30 years.
Potential Acute Dose Rate (APDR or ADRpot):
The predicted acute dose rate that represents acute exposure usually based on a single 8 hour
working day exposure duration.
NOTE: For the purposes of an SF Assessment, the defaults for average lifetime, body weight,
exposure duration, and ingestion rate are pre-set in both ChemSTEER and E-FAST and should not
be changed unless accurate data for these inputs are available.
Risk Estimations Reminder: RISK = HAZARD x EXPOSURE
For chemicals with an identified hazard concern, the potential exposure must be determined to make
an assessment of risk. If a low concern for hazard is identified (hazard approx. = 0) or very low
exposure is identified (exposure approx. = 0), then there is an inherently low concern for risk
because of the mathematical relationship between hazard and exposure.
Estimating Aquatic Risk
Determine an Acute and Chronic Concentration of Concern (COC):
Concentration at which potential acute or chronic aquatic toxicity may be of concern for aquatic
species. Calculate a COC for every species in the full profile.
Acute COC:
Acute COC for fish = LC50 / (5) Acute COC for daphnia = EC50 / (5)
Acute COC for algae = ECso / (4) -OR- If an algae ChV value exists, use that value as the acute
COC and do not estimate the COC using an ECso value divided by a factor.
If a NOEC value is available from an acute study for any species, that value can be used
directly as the acute COC. (No assessment factor needed)
Chronic COC:
Chronic COC for fish = ChV / (10) Chronic COC for daphnia = ChV / (10)
Chronic COC for algae = ChV / (10)
If a NOEC value is available from a chronic study for any species, that value can be used
directly as the chronic COC. (No assessment factor needed)
Example calculations are provided below:
FishLCso = 0.10 mg/L ^calculated Acute COC = (0.10 mg/L)/5 = 0.02 mg/L (ppm)
Daphnid ChV = 0.02 mg/L -> calculated Chronic COC = (0.02 mg/L) 710 = 0.002 mg/L (ppm)
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NOTE: All COCs are rounded up to 1 significant digit (e.g., a COC of 1.75 ppb is rounded up to 2
ppb). All COC values less than 1 ppb are rounded up to 1 ppb for assessments due to limitations in
reliable analytical methods to test below 1 ppb should verification be needed.
No values less than 1 ppb (the realistic detection limit) should be reported!!
Estimating Acute Aquatic Risk
The potential for acute risk to aquatic organisms exists if the predicted environmental concentration
(PEC) is greater than the acute concentration of concern (COC).
If Acute COC > PEC Low concern for risk
If Acute COC < PEC Potential for risk
Estimating Chronic Aquatic Risk
The potential for chronic risk to aquatic organisms may exist if the COC is exceeded for 20 days or
more per year. There will be instances that you will determine a chronic COC exceeds the PEC, but
if it is not exceeded for 20 days or more per year, then there is low concern for risk. This is because
although there is a potential for the concentration of the chemical in the water to reach levels
exceeding the hazardous level, the levels are not exceeded for a sufficient duration of time to induce
any chronic effects.
The 20-day criterion is derived from partial life-cycle tests (daphnid chronic and fish early life- stage
tests) that typically range from 21 to 28 days in duration. Low concern for chronic risk exists if the
COC is exceeded on fewer than 20 days per year.
E-FAST will predict how many days per year the (PEC) exceeds the (COC). The number of days
the COC is exceeded can be found on the PDM SIC tab in the output screen of E-F AST.
Example Worksheet for Identification of Acute and Chronic Risk to Aquatic Organisms:
Acute Endpoint
Fish LC50
Daphnid LC50
Algae EC50
Value
0.079 ppm
0.11 ppm
0.083 ppm
Factor
5
5
4
Acute COC
0.02 ppm
0.02 ppm
0.07* ppm
PEC
0.055 ppm
0.055 ppm
0.055 ppm
Risk?
Yes
Yes
No
* Since an algae ChV value was available (see below), the ChV value was used as the algae acute
COC.
E-F AST indicated that the PEC exceeds the COC for 9.4 days per year
Chronic Endpoint
Fish ChV
Daphnid ChV
Algae ChV
Value
0.0 18 ppm
0.027 ppm
0.067 ppm
Factor
10
10
10
Chronic COC
0.002 ppm
0.003 ppm
0.007 ppm
PEC
0.055 ppm
0.055 ppm
0.055 ppm
Risk?
Yes
No
No
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Aquatic Risk Summary: There is potential for acute risk to the aquatic environment because the
PEC is greater than the acute COC (for fish and daphnids). There is low concern for chronic risk
because even though the PEC exceeds the chronic COC for fish, it is only exceeded for 9.4 days
according to E-FAST and under EPA guidelines, this is not a sufficiently long enough duration to
induce chronic effects.
Estimating Human Health Non-Cancer Risk
For the determination of risk to the human population from non-cancer human health effects, a
quantitative value called the Margin of Exposure (MOE) is calculated. This margin is essentially the
established safety buffer between the hazardous effects level (dose) and the predicted exposure dose.
The EPA OPPT office utilizes margins of exposure that they believe are sufficiently protective of
human health when assessing new chemicals. The calculated MOEs for each chemical are compared
to the MOE criteria used by the OPPT office and the results are evaluated to determine the potential
for risk. When referring to non-cancer effects, these margins of exposure or safety buffers must be
at least 100X or 1000X protective of human health depending on the type of non-cancer data
identified in the hazard assessment.
If hazard data for ANY of the non-cancer health effect endpoints have indicated a moderate or high
hazard concern, then an MOE for EACH moderate/high concern endpoint should be determined!
The lowest MOE value calculated from that group should be recorded for assessment purposes and
will be used as the quantitative value to determine the potential overall risk to human health from
non-cancer effects.
The lowest MOE will represent the worst-case scenario for the chemical and therefore, if the lowest
MOE does not indicate a risk, then there is an assumed low potential for risk for all other endpoints
which had mathematically larger MOE values.
However, if even one of the endpoints has a calculated MOE indicating the potential for risk, then
overall the chemical should be flagged as having potential risks to human health. The subsequent
pages give more in-depth guidance on the determination of MOE for acute and chronic risk from
occupational exposure and from exposures to the general population.
The following table shows the human health non-cancer endpoints and the corresponding
acute/chronic exposure values to use for calculation of an MOE:
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Endpoint
Exposure dose used for MOE calc.
Single Dose Studies
Acute Toxicity
ADRpot (acute)*
Repeated Dose Studies
Irritation
Skin Sensitizer
Reproductive Effects
Immune System Effect
Developmental Toxicity
Genotoxicity
Mutagenicity
Neurotoxicity
Systemic Effects
Can not be used to determine MOE
Can not be used to determine MOE
ADDpot (chronic)
ADDpot (chronic)
ADRpot (acute)
Can not be used to determine MOE
Can not be used to determine MOE
ADDpot (chronic)
ADDpot (chronic)
* Acute risk is ONLY assessed for chemicals with an LD50 value < 50
mg/kg.
Estimating Acute Risk to the General Population using an MOE:
NOTE: When the acute toxicity studies indicate LDso values > 50 mg/kg for a chemical, there is no
need to calculate a Margin of Exposure (MOE) for acute exposure and a low concern for acute risk is
assumed.
There is a potential acute hazard concern for chemicals with an LDso < 50 mg/kg. A MOE needs to
be calculated and the potential for acute risk to the general population needs to be assessed when
acute toxicity studies with LD50 values < 50 mg/kg have been identified.
Margin of Exposure (MOE) based on Acute Exposure:
Ratio of the identified effect level (LD50 value determined in health hazard section) to the estimated
acute dose rate (predicted from E-FAST).
MOEacute = LD50 (mg/kg) / ADRpot (from E-FAST)
MOE < 1000 indicates potential for risk
MOE > 1000 indicates low concern for risk
Estimating Chronic Risk to General Population or to Workers using an MOE:
NOTE: Regulatory decisions will be made based on the following human health effects:
reproductive; immune; developmental; neurotoxicity; and systemic.
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Margin of Exposure (MOE) based on Chronic Exposure:
An MOE is the ratio of the No-Observed Adverse-Effect-Level (NOAEL) or the Lowest-Observed
Adverse-Effect-Level (LOAEL) for the effect (determined in health hazard section) to the estimated
exposure value (predicted from exposure models). If both a NOAEL and LOAEL are available, then
the NOAEL value is used for calculation of the MOE.
MOE, Occupational = NOAEL or LOAEL(Non-Cancer) / APDR or ADD (from ChemSTEER)
MOE, General Population = NOAEL or LOAEL(Non-Cancer) /ADRpot or ADDpot (from E-FAST)
Human Health Risk Summary: There is a potential risk concern for chemicals with an MOE < 100
based on studies with NOAEL values and for chemicals with MOE < 1000 based on studies with
only LOAEL values. The preference is to identify a NOAEL value and use that value for your MOE
calculations. The average daily dose (ADD or ADDpot) is used to determine an MOE with one
exception; an MOE for developmental toxicity is based on the acute dose rate (APDR or ADRpot).
For Calculation based on NOAEL: For Calculation based on LOAEL:
MOE < 100 indicates potential for risk MOE < 1000 indicates potential for risk
MOE > 100 indicates low concern for risk MOE > 1000 indicates low concern for risk
For MOE values based on developmental toxicity data a body weight of 60 kg should be used as
input when determining the exposure values (ADD, ADR, LADD) instead of the default of 70 kg
because that particular endpoint is only assessed in females.
B-13
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Example Worksheet for Identification of the Potential for Acute and Chronic Risk to Human
Health based on a Non-Cancer MOE:
Population
Occupational
General
Population
Effect
Systemic
Neurotox
Systemic
Neurotox
NOAEL
40 mg/kg-d
40 mg/kg-d
40 mg/kg-d
40 mg/kg-d
LOAEL
200 mg/kg-d
200 mg/kg-d
200 mg/kg-d
200 mg/kg-d
Exposure
1.8 x 10"2 mg/kg-d ChemSTEER
ADD
1.8 x 10'2 mg/kg-d ChemSTEER
ADD
2. IxlO"6 mg/kg-d E-FAST ADDpot
2. 1 x 10'6 mg/kg-d E-FAST ADDpot
MOE
2222
2222
1.9xl07
1.9xl07
The MOE used to evaluate Risk from Occupational Exposure = 2222
The MOE used to evaluate Risk from General Population Exposure = 1.9 x 107
Occupational Risk Summary: There is low concern for risk from occupational exposure or
exposures to the general population because the MOE's are greater than 100 (based on studies with a
NOAEL).
Estimating Human Health Cancer Risk
US EPA has purchased the public rights to OncoLogic, the Cancer Expert System, and plans to make
it publicly available. When it becomes available information on interpreting results from that model
will be included in this document.
General Overview for a Cancer Risk Assessment:
For Occupational Exposure Doses: LADD will be calculated by ChemSTEER
For General Population Exposure Doses: LADDpot will be calculated by E-FAST.
Slope Factor = Slope Factor (mg/kg-day)"1 (Calculated)
A measure of individual's extra risk (increased likelihood) of developing cancer for each incremental
increase in exposure to a chemical. It approximates the upper bound of the slope of the dose-
response curve using the linearized multistage procedure at low doses. The calculation of a slope
factor requires tools that are not provided in the P2 Framework but can downloaded from the web
for free. The software package is called The Benchmark Dose Software (BMDS), can be found at:
http ://cfpub. epa.gov/ncea/
Cancer Risk = LADD or LADDpot x Slope Factor
-v-5
Generally, a cancer risk of > 1x10" (1 in 1,000,000) for the general population and > 1x10" (1 in
100,000) for worker exposure indicates the potential for risk.
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References Cited
* Boethling R.S. and J. V. Nabholz. 1997. Environmental assessment of polymers under the
U.S. Toxic Substances Control Act. In: Hamilton, J.D. andR. Sutcliffe, eds. Ecological
assessment of polymers: Strategies for product stewardship and regulatory programs. New
York, NY: VanNostrand Reinhold, 187-234. ISBN 0-442-02328-6.
• Ecological Assessment of Polymers: Strategies for Product Stewardship and Regulatory
Programs. John D. Hamilton (Editor), Roger Sutcliffe (Editor) ISBN: 0-471-28782-2.
• U.S. EPA. 1996. ECOSAR User's Manual. "Estimating Toxicity of Industrial Chemicals to
Aquatic Organisms Using Structure-Activity Relationships". R.G.Clements (Editor),
Contributors: R.G. Clements, J.V. Nabholz, M. Zeeman. Office of Pollution Prevention and
Toxics 7403M, U.S. Environmental Protection Agency, Washington, DC. 20460. Available
in PDF at: http://www.epa.gov/oppt/newchems/sarman.pdf
• U.S. EPA. 1999a. Category for Persistent, Bioaccumulative, and Toxic New Chemical
Substances, Federal Register: November 4, 1999 (Volume 64, Number 213), pages
60194-60204 Available at:
http://www.epa.gov/fedrgstr/EPA-TOX/1999/November/Dav-04/t28888.htm
• U.S. EPA. 1999b. Persistent Bioaccumulative Toxic (PBT) Chemicals; Lowering of
Reporting Thresholds for Certain PBT Chemicals; Addition of Certain PBT Chemicals;
Community Right-to-Know Toxic Chemical Reporting: Final rule, Federal Register: October
29, 1999 (Volume 64, Number 209), 58666-58753 Available in PDF at:
http://www.epa.gov/tri/pbt-final rule.pdf
U.S. EPA. 2004. The Pollution Prevention (P2) Framework, EPA-748-B-03-001. Office of
Pollution Prevention and Toxics 7403M, U.S. Environmental Protection Agency,
Washington, DC. 20460. October 2003 version updated in January 2004. Available at:
http ://www. epa. gov/opptintr/p2framework/docs/p2manua.htm
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Appendix C
Chemical Regulations List
-------
Chemical Regulations List
U.S. Federal
U.S. Environmental Protection Agency
1. Regulated Toxic, Explosive, or Flammable Substances (Clean Air Act)
— http ://www. epa. gov/ceppo/pubs/title3 .pdf
2. Criteria Air Pollutants (Clean Air Act)
— http ://www. epa. gov/airs/criteria.html
— http ://www. epa. gov/ttn/naaqs/
3. Hazardous Air Pollutants (Clean Air Act)
— http://www.epa.gov/ttn/atw/188polls.html
— http ://www. epa. gov/ttn/atw/atwsmod.html
4. Priority Pollutants (Clean Water Act)
— http://oaspub.epa.gov/wqsdatabase/wqsi_epa_criteria.rep_parameter
5. Registered Pesticides (Federal Insecticide, Fungicide, and Rodenticide Act)
— http://www.epa.gov/opppmsdl/PPISdata/
6. Maximum Contaminant Levels (Safe Drinking Water Act)
— http ://www. epa. gov/safewater/mcl. html
— http ://www. epa. gov/ost/drinking/standards/dwstandards.pdf
7. Extremely Hazardous Substances (Superfund)
— http ://www. epa. gov/ceppo/pubs/title3 .pdf
— http ://www. epa. gov/swercepp/ehs/ehslist.html
8. Hazardous Substances (Superfund)
— http ://www. epa. gov/ceppo/pubs/title3 .pdf
9. Toxic Release Inventory Chemicals
— http://www.epa.gov/triinter/chemical/chemlist2001.pdf
— http ://www. epa. gov/triinter/chemical/
— http://www.epa.gov/triinter/chemical/chemlistchanges02.pdf
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10. Banned or Severely Restricted Pesticides (U.S. Environmental Protection Agency)
— http ://www. epa. gov/oppfead 1 /international/us-unli st. htm
11. Bioaccumulative Chemicals of Concern (U.S. Environmental Protection Agency)
— http ://www. epa. gov/waterscience/GLI/index.html
12. Persistent, Bioaccumulative, and Toxic Chemicals (U.S. Environmental Protection Agency)
— http://www.epa.gov/tri/chemical/pbt_chem_list.htm
— http ://www. epa. gov/opptintr/pbt/cheminfo.htm
— http ://www. epa. gov/oppt/pbtprofiler/
— http://www.epa.gov/epaoswer/hazwaste/minimize/chemlist.htm
13. Great Lakes Binational Toxics Strategy Substances (U.S. and Canada)
— http://www.epa.gov/glnpo/p2/bns.html#Level I
— http://www.epa.gov/glnpo/bns/levelii/leviisubsus.html
U.S. Department of Transportation
14. Inhalation Hazard Chemicals (Department of Transportation)
— http ://www. access, gpo. gov/nara/cfr/waisidx_00/49cfr 172_00.html
U.S. Department of Energy
15. Hazardous Constituents (Resource Conservation and Recovery Act)
— http://www.eh.doe.gov/oepa/laws/rcra.html
U.S. Department of Labor
16. Air Contaminants (Occupational and Safety Health Act)
— http://www.osha-slc.gov/SLTC/pel/index.html
U.S. State
17. U.S. State and Territory Web Site List
— http ://www. epa. gov/epaoswer/osw/stateweb. htm
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California
18. California Air Toxics "Hot Spots" Chemicals (Assembly Bill 2588)
— http://www.arb.ca.gov/ab2588/ab2588.htm
— http://www.arb.ca.gov/ab2588/fmal96/guide96a.pdf
19. California Toxic Air Contaminants (Assembly Bill 1807)
— http://www.arb.ca.gov/toxics/id.htm
— http://www.arb.ca.gov/toxics/taclist.htm
20. Air Contaminants (California Occupational and Safety Health Act)
— http://www.dir.ca.gov/title8/339.html
21. Maximum Contaminant Levels (California Safe Drinking Water Act)
— http://www.dhs.ca.gov/ps/ddwem/publications/lawbook/dwregulations-06-01-04.pdf
— http ://www. dhs. ca. gov/org/ps/ddwem/chemicals/mcl/regextract.pdf
22. Public Health Goals and Action Levels (California Safe Drinking Water Act)
— http ://www. oehha. ca. gov/water.html
23. Known Carcinogens and Reproductive Toxicants (California Proposition 65)
— http://www.oehha.ca.gov/prop65/prop65_list/Newlist.html
Massachusetts
24. Hazardous Materials List (Massachusetts)
— http://www.mass.gov/dep/bwsc/files/mohmla.pdf
International
25. Persistent Organic Pollutants (United Nations)
— http://www.pops.int/documents/convtext/convtext en.pdf
— http://irptc.unep.ch/pops/indxhtms/assesO.html
26. Initial List of Prior Informed Consent Chemicals (United Nations)
— http://www.fao.org/ag/agp/agpp/pesticid/pic/piclist.htm
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27. Ozone Depleting Substances (Montreal Protocol)
— http://www.unep.ch/ozone/mont_t.htm
— http ://www. epa. gov/ozone/ods.html
— http ://www. epa. gov/ozone/ods2.html
28. Greenhouse Gases (Intergovernmental Panel on Climate Change)
— http://www.ipcc.ch/
— http://www.grida.no/climate/ipcc tar/wgl/index.htm
— http: //unfccc. int/re source/doc s/convkp/kpeng. html
Europe
29. Classification, Packaging and Labeling of Dangerous Substances (European Economic
Community)
— http://ecb.irc.it/Legislation/1967L0548EC.htm
30. List of chemicals banned or severely restricted in the European Union (The Safety, Health
and Welfare at Work Act)
— http://www.ilo.org/public/english/protection/safework/cis/products/safetytm/clasann6
.htm
31. Dangerous for the Environment (Nordic Council of Ministers. European Chemicals Bureau)
— http ://www.kemi. se/nclass/default. asp
32. European Inventory of Existing Commercial Chemical Substances
— http://ecb.irc.it/esis/esis.php?PGM=ein&DEPUIS=autre
33. European List of Notified Chemical Substances
— http://ecb.irc.it/esis/esis.php?PGM=ein&DEPUIS=autre
34. Swiss Giftliste 1 and Inventory of Notified New Substances
— http ://www.umwelt-
schweiz.ch/buwal/eng/fachgebiete/fg stoffe/recht/anmeldung/index.html
— http ://www.umwelt-
schweiz.ch/buwal/eng/fachgebiete/fg stoffe/recht/stoffverordnung/index.html
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Asia
35. Japanese Existing and New Chemical Substances
— http://www.oecd.Org/document/29/0.2340.en 2649 33713 1946781 1 1 1 1.00.ht
ml
36. Korean Existing Chemicals List (Toxic Chemicals Control Law)
— http: //stneasy. cas. org/db s s/chemli st/ecl. html
37. Philippines Inventory of Chemicals and Chemical Substances
— http://www.emb.gov.ph/eeid/PICCS.htm
38. Taiwan Toxic Chemical Substances List (Toxic Chemical Substances Management Act)
— http://law.epa.gov.tw/en/laws/808150657.html
Middle East
39. Proposed Israel Hazardous Substances List
— http://www.sviva.gov.il/Enviroment/Static/Binaries/odotHamisrad/haz man l.pdf
North America
40. Canadian Domestic/ Non-Domestic Substances List (Canadian Environmental Protection
Act)
— http://www.ee.gc.ca/CEPARegistry/subs_list/Domestic.cfm
— http://www.ee.gc.ca/CEPARegistry/subs_list/NonDomestic.cfm
41. Toxic Substances List (Canadian Environmental Protection Act)
— http://www.ee.gc.ca/CEPARegistry/subs_list/ToxicList.cfm
Oceania
42. Australian Inventory of Chemical Substances
— http://www.nicnas.gov.au/obligations/aics/
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Disclaimer
This document has not been through a formal external peer review process and does not
necessarily reflect all of the most recent policies of the U.S. Environmental Protection Agency
(EPA), in particular those now under development. The use of specific trade names or the
identification of specific products or processes in this document are not intended to represent an
endorsement by EPA or the U.S. Government. Discussion of environmental statutes is intended
for information purposes only; this is not an official guidance document and should not be relied
upon to determine applicable regulatory requirements.
For More Information
To learn more about the Design for the Environment (DfE) Furniture Flame Retardancy
Partnership or the DfE Program, please visit the DfE Program web site at: www.epa.gov/dfe
To obtain copies of DfE Program technical reports, pollution prevention case studies, and project
summaries, please contact:
National Service Center for Environmental Publications
U.S. Environmental Protection Agency
P.O. Box 42419
Cincinnati, OH 45242
Phone: (513) 489-8190, (800) 490-9198
Fax:(513)489-8695
E-mail: ncepimal@one.net
Acknowledgments
This alternatives assessment was prepared by Eastern Research Group and Syracuse Research
Corporation under funding from the U.S. Environmental Protection Agency's Design for the
Environment (DfE) Program in the Economics, Exposure, and Technology Division (EETD) of
the Office of Pollution Prevention and Toxics (OPPT) and Region IX.
This document was produced as part of the DfE Furniture Flame Retardancy Partnership, under
the direction of the project's steering committee. Special thanks to the Risk Assessment Division
of OPPT, for their assistance in evaluating the chemicals in the report. Many thanks also to all
the stakeholders who participated in the technical workgroups and who provided valuable input
for the report.
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United States
Environmental Protection Agency
Design for the Environment (7406M)
EPA742-R-05-002A
September 2005
www.epa.gov/dfe
US. EPA
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