EPA Document # EPA-740-R1-8002
June 2018
United States Office of Chemical Safety and
LbiI Jfm Environmental Protection Agency Pollution Prevention
Exposure and Use Assessment of Five
Persistent, Bioaccumulative and Toxic
Chemicals
Peer Review Draft
June 2018
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Contents
TABLES 7
FIGURES 7
1. EXECUTIVE SUMMARY 15
2. BACKGROUND 15
3. APPROACH 17
4. DECABROMODIPHENYL ETHER (DECABDE) 21
4.1. Chemistry and Physical-Chemical Properties 21
4.2. Uses 21
4.3. Characterization of Expected Environmental Partitioning 24
4.4. Overview of Lifecycle and Potential Sources of Exposure 25
4.4.1. Background and Brief Description of Lifecycle 25
4.4.2. Manufacturing 26
4.4.3. Imported Articles 27
4.4.4. Processing: Incorporated into Formulation, Mixture, or Reaction Products and Incorporation
into Article Components 27
4.4.5. Processing: Recycling 28
4.4.6. Industrial/Commercial Use: Fabrics, Textiles and Apparel (textile manufacturing) 28
4.4.7. Industrial/Commercial Use: Incorporation into Plastic Articles (wire and cable coatings) 28
4.4.8. Industrial/Commercial Use Articles - Complex articles 28
4.4.9. Consumer Articles 29
4.4.10. Qualitative Trends Over Time for Releases and Occupational Exposures 29
4.5. Environmental Monitoring 29
4.5.1. Indoor Dust 32
4.5.2. Indoor Air 35
4.5.3. Ambient Air 36
4.5.4. Surface Water 37
4.5.5. Drinking Water 38
4.5.6. Soil 38
4.5.7. Sediment 40
4.5.8. Sludge/Biosolids 43
4.5.9. Influent/Effluent 44
4.5.10. Landfill Leachate 44
4.5.11. Vegetation/Diet 45
4.5.12. Other 45
4.6. Biomonitoring 46
4.6.1. Human blood (serum) 48
4.6.2. Human (other) 50
4.6.3. Aquatic invertebrates 52
4.6.4. Fish 53
4.6.5. Aquatic mammals 54
4.6.6. Terrestrial invertebrates 54
4.6.7. Birds 55
4.6.8. Terrestrial mammals 56
4.6.9. Other 56
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4.7. Trends in Monitoring Data 56
4.7.1. Indoor Dust 57
4.7.2. Ambient Air 57
4.7.3. Soils 58
4.7.4. Sediments 59
4.7.5. Biosolids 59
4.7.6. Humans 60
4.7.7. Aquatic Invertebrates 60
4.7.8. Fish 61
4.7.9. Birds 61
4.8. Modeled Intake and Dose Data 62
4.9. Overview of Existing Exposure Assessments 64
4.10. Representative Exposure Scenarios 68
4.11. Summary of Review Articles 70
4.11.1. Dust 71
4.11.2. Soil 71
4.11.3. Surface Water and Sediments 72
4.11.4. Human Biomonitoring 72
4.11.5. Dose 73
5. HEXACHLOROBUTADIENE (HCBD) 73
5.1. Chemistry and Physical-Chemical Properties 73
5.2. Uses 74
5.3. Characterization of Expected Environmental Partitioning 75
5.4. Overview of Lifecycle and Potential Sources of Exposure 76
5.4.1. Background and Brief Description of Lifecycle 76
5.4.2. Manufacturing and Import 77
5.4.3. Processing: Plastic Additive and Chemical Intermediate 77
5.4.4. Industrial/Commercial Use: Solvent as an Analytical Standard 77
5.4.5. Industrial/Commercial Use: Waste Fuel 78
5.4.6. Consumer Use: Consumer Products 78
5.4.7. Qualitative Trends Over Time for Releases and Occupational Exposures 78
5.5. Environmental Monitoring 79
5.5.1. Indoor Dust 80
5.5.2. Indoor Air 81
5.5.3. Ambient Air 81
5.5.4. Surface Water 82
5.5.5. Drinking Water 83
5.5.6. Soil 84
5.5.7. Sediment 85
5.5.8. Sludge/Biosolids 86
5.5.9. Influent/Effluent 86
5.5.10. Landfill Leachate 87
5.5.11. Vegetation/Diet 87
5.5.12. Other 87
5.6. Biomonitoring 87
5.6.1. Human blood (serum) 88
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5.6.2. Aquatic invertebrates 89
5.6.3. Fish 90
5.6.4. Aquatic mammals 91
5.6.5. Terrestrial invertebrates 91
5.6.6. Birds 91
5.6.7. Terrestrial mammals 92
5.7. Trends in Monitoring Data 92
5.7.1. Ambient Air 92
5.7.2. Soils 93
5.7.3. Sediments 94
5.7.4. Influent/Effluents 97
5.7.5. Aquatic Invertebrates 98
5.7.6. Fish 100
5.7.7. Aquatic Mammals 102
5.8. Modeled Intake and Dose Data 103
5.9. Overview of Existing Exposure Assessments 103
5.10. Representative Exposure Scenarios 104
5.11. Summary of Review Articles 105
6. PHENOL, ISOPROPYLATED, PHOSPHATE (3:1)-PIP (3:1) 106
6.1. Chemistry and Physical-Chemical Properties 106
6.2. Uses 107
6.3. Characterization of Expected Environmental Partitioning 110
6.4. Overview of Lifecycle and Potential Sources of Exposure 112
6.4.1. Background and Brief Description of Lifecycle 112
6.4.2. Manufacturing 112
6.4.3. Processing: Incorporation into Formulation, Mixture, or Reaction Products 113
6.4.4. Processing: Incorporation into Articles 113
6.4.5. Industrial Use: Hydraulic Fluid / Lubricants and Greases 114
6.4.6. Industrial/Commercial Use: Paints and Coatings /Adhesives and Sealants 115
6.4.7. Consumer Use: Complex Articles / Plastic Articles / Other 115
6.4.8. Qualitative Trends Over Time for Releases for Releases and Occupational Exposures 115
6.5. Environmental Monitoring 115
6.5.1. Indoor Dust 118
6.5.2. IndoorAir 119
6.5.3. Ambient Air 119
6.5.4. Soil 119
6.5.5. Sediment 120
6.5.6. Other 120
6.6. Biomonitoring 120
6.6.1. Human blood (serum) 122
6.6.2. Human (other) 122
6.6.3. Birds 123
6.6.4. Terrestrial mammals 123
6.6.5. Other 123
6.7. Trends in Monitoring Data 123
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6.8. Modeled Intake and Dose Data 123
6.9. Overview of Existing Exposure Assessments 125
6.10. Representative Exposure Scenarios 126
6.11. Summary of Review Articles 127
7. 2, 4, 6-TRIS(TERT-BUTYL) PHENOL (2, 4, 6-TTBP) 127
7.1. Chemistry and Physical-Chemical Properties 127
7.2. Uses 128
7.3. Characterization of Expected Environmental Partitioning 131
7.4. Overview of Lifecycle and Potential Sources of Exposure 132
7.4.1. Background and Brief Description of Lifecycle 132
7.4.2. Manufacturing and Processing as a Reactant/Chemical Intermediate 133
7.4.3. Processing: Incorporation into Formulation, Mixture, or Reaction Products 134
7.4.4. Industrial, Commercial, and Consumer Use: Fuel and Related Products (fuel additives) 134
7.4.5. Industrial, Commercial, and Consumer Use: Motor Vehicle Repair, Lubricating Agents and
Additives in the Transportation Sector (lubricating grease, cleaning/washing agents and other
additives) 134
7.4.6. Industrial/Commercial Use: Other Uses (e.g., laboratory research) 135
7.4.7. Qualitative Trends Over Time for Releases for Releases and Occupational Exposures 135
7.5. Environmental Monitoring 135
7.5.1. Indoor Dust 137
7.5.2. IndoorAir 137
7.5.3. Ambient Air 137
7.5.4. Surface Water 138
7.5.5. Sediment 138
7.5.6. Influent/Effluent 138
7.5.7. Other 139
7.6. Biomonitoring 139
7.6.1. Fish 140
7.6.2. Other 140
7.7. Trends in Monitoring Data 140
7.7.1. Surface Water 140
7.7.2. Fish 141
7.8. Modeled Intake and Dose Data 141
7.9. Overview of Existing Exposure Assessments 142
7.10. Representative Exposure Scenarios 143
7.11. Summary of Review Articles 144
8. PENTACHLOROTHIOPHENOL (PCTP) 144
8.1. Chemistry and Physical-Chemical Properties 144
8.2. Uses 144
8.3. Characterization of Expected Environmental Partitioning 146
8.4. Overview of Lifecycle and Potential Sources of Exposure 147
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8.4.1. Background and Brief Description ofLifecycle 147
8.4.2. Manufacturing and Import 148
8.4.3. Processing: Cross-linking Agent for Rubber Manufacturing 149
8.4.4. Industrial/Commercial Use: Golf Equipment Manufacturing (golf balls) 149
8.4.5. Industrial/Commercial Use: Other Uses (e.g. laboratory research) 149
8.5. Environmental Monitoring 150
8.6. Biomonitoring 150
8.6.1. Human (other) 151
8.6.2. Other 151
8.7. Trends in Monitoring Data 151
8.8. Modeled Intake and Dose Data 151
8.9. Overview of Existing Exposure Assessments 152
8.10. Representative Exposure Scenarios 152
8.11. Summary of Review Articles 152
9. REFERENCES 152
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Tables
Table 3-1. Overview of Qualitative and Quantitative Exposure Information used in this Exposure
Assessment 20
Table 4-1. Use Categories and Subcategories for DecaBDE 22
Table 4-2. CDR Production Volumes 2010-2015 27
Table 4-3. Summary of DecaBDE Monitoring Data from the Peer-Reviewed Literature 30
Table 4-4. Summary of DecaBDE Biomonitoring Data from the Peer-Reviewed Literature and
Monitoring Databases 46
Table 4-5. Total Adult Intake Estimates of DecaBDE (U.S. EPA, 2010), Sorted Highest to Lowest 65
Table 4-6. Intakes of DecaBDE by Children Estimated by Hays and Pyatt (2006) 66
Table 4-7. Estimated Exposure of the General Population to DecaBDE from Health Canada Assessment
(Health Canada, 2012) 67
Table 5-1. Use Categories and Subcategories for HCBD 74
Table 5-2. Summary of HCBD Monitoring Data from the Peer-Reviewed Literature and Monitoring
Databases 79
Table 5-3. Summary of HCBD Biomonitoring Data from the Peer-Reviewed Literature and Monitoring
Databases 88
Table 5-4. Estimated Exposure of the General Population to HCBD (Environment Canada and Health
Canada (2000) 104
Table 6-1. Use Categories and Subcategories for PIP (3:1) 108
Table 6-2. Production Volume of Phenol, Isopropylated, Phosphate (3:1) 113
Table 6-3. Summary of PIP (3:1) and TPP Monitoring Data from the Peer-Reviewed Literature 116
Table 6-4. Summary of TPP, a Surrogate for PIP (3:1), Biomonitoring Data from the Peer-Reviewed
Literature 121
Table 7-1. Use Categories and Subcategories for 2,4,6 TTBP 130
Table 7-2. Summary of 2,4,6 TTBP and BHT Monitoring Data from Peer-Reviewed Literature 136
Table 7-3. Summary of 2,4,6 TTBP Biomonitoring Data from the Peer-Reviewed Literature and
Monitoring Databases 139
Table 8-1. Use Categories and Subcategories for PCTP 146
Table 8-2. Summary of PCTP Biomonitoring Data from the Peer-Reviewed Literature 150
Figures
Figure 4-1. Lifecycle Diagram for DecaBDE 26
Figure 4-2. Frequency of peer-reviewed publications identified that contained DecaBDE monitoring
data 31
Figure 4-3. Concentration of DecaBDE (ng/g) in indoor dust for commercial (2008 to 2017) and
residential (2016 and 2017) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported
central tendency estimates are shown as a separate dark color within 32
Figure 4-4. Concentration of DecaBDE (ng/g) in indoor dust for residential locations (2009 to 2016).
For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 33
Figure 4-5. Concentration of DecaBDE (ng/g) in indoor dust for residential locations (2007 and 2008)
and vehicles (2008 to 2017). For each year, the range of values reported is presented by
the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within 34
Figure 4-6. Concentration of DecaBDE (ng/m3) in indoor air for commercial locations (2012 to 2016),
residential locations (2011 to 2016), vehicles (2008 to 2013), and modeled data (2014).
For each year, the range of values reported is presented by the entire length of the bar.
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The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 35
Figure 4-7. Concentration of DecaBDE (ng/m3) in ambient air for background locations (2001 to 2017),
near facility locations (2007 to 2014), and particulate data (2016 and 2017). For each
year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 36
Figure 4-8. Concentration of DecaBDE (ng/m3) in ambient air for particulate data (2014) and modeled
data (2014 to 2017). For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within 37
Figure 4-9. Concentration of DecaBDE (ng/L) in surface water for background locations (2004 to
2016), near facility locations (2008 and 2013), and modeled data (2017). For each year,
the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark
color within 37
Figure 4-10. Concentration of DecaBDE (ng/g) in soil for background (2007 to 2017) and near facility
(2014 to 2016) locations. For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within 38
Figure 4-11. Concentration of DecaBDE (ng/g) in soil for near facility locations from 1979 to 2013. For
each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 39
Figure 4-12. Concentration of DecaBDE (ng/g) in sediment for background locations from 2013 to
2017. For each year, the range of values reported is presented by the entire length of the
bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 40
Figure 4-13. Concentration of DecaBDE (ng/g) in sediment for background (2006 to 2012) and near
facility (2010 to 2016) locations. For each year, the range of values reported is presented
by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within 41
Figure 4-14. Concentration of DecaBDE (ng/g) in sediment for near facility locations from 2007 to
2010. For each year, the range of values reported is presented by the entire length of the
bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 42
Figure 4-15. Concentration of DecaBDE (ng/g) in sludge/biosolids for near facility locations from 2004
to 2017. For each year, the range of values reported is presented by the entire length of
the bar. The minimum and maximum of reported central tendency estimates are shown
as a separate dark color within 43
Figure 4-16. Concentration of DecaBDE (ng/L) in influent/effluent for near facility locations from 2004
to 2016. For each year, the range of values reported is presented by the entire length of
the bar. The minimum and maximum of reported central tendency estimates are shown
as a separate dark color within 44
Figure 4-17. Concentration of DecaBDE (ng/L) in landfill leachate for near facility locations in 2013.
For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 44
Figure 4-18. Concentration of DecaBDE (ng/g) in vegetation/diet for background (2008 to 2017) and
near facility (2008 to 2014) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported
central tendency estimates are shown as a separate dark color within 45
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Figure 4-19. Concentration of DecaBDE (ng/g) in incinerator waste for near facility locations in 2016.
The range of values reported is presented by the entire length of the bar 45
Figure 4-20. Concentration of DecaBDE (ng/L) in seawater for background locations in 2005 and 2012.
The range of values reported is presented by the entire length of the bar 45
Figure 4-21. Frequency of peer-reviewed publications identified that contained DecaBDE
biomonitoring data 47
Figure 4-22. Concentration of DecaBDE (ng/g) in human blood (serum) for consumer (2008), general
(2007 to 2017), high-end (2006 to 2013), and occupational (2002 to 2017) populations,
as well as monitoring database results (MDI, 2002). For each year/database, the range of
values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 48
Figure 4-23. Concentration of DecaBDE (ng/L) in human blood (serum) for the general population in
2014. The range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 49
Figure 4-24. Concentration of DecaBDE (ng/g) in human (other) for general (2007 to 2016), high-end
(2009 to 2015), and occupational (2012 to 2014) populations. For each year/database,
the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark
color within 50
Figure 4-25. Concentration of DecaBDE (ng/g) in human (other) for occupational populations in 2011,
as well as monitoring database results. For each year/database, the range of values
reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within 51
Figure 4-26. Concentration of DecaBDE (ng/cm2) in dermal wipes for the general population in 2017.
The minimum and maximum of reported central tendency estimates are shown 51
Figure 4-27. Concentration of DecaBDE (ng/wipe) in dermal wipes from a monitoring database (CTD).
The range of values reported is presented by the entire length of the bar 51
Figure 4-28. Concentration of DecaBDE (ng/g) in aquatic invertebrates for background locations from
2007 to 2016. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within 52
Figure 4-29. Concentration of DecaBDE (ng/g) in fish for background locations from 2006 to 2017. For
each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 53
Figure 4-30. Concentration of DecaBDE (ng/g) in aquatic mammals for background locations in 2009.
The minimum and maximum of reported central tendency estimates are shown 54
Figure 4-31. Concentration of DecaBDE (ng/g) in terrestrial invertebrates for background locations in
2011 and 2017. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within 54
Figure 4-32. Concentration of DecaBDE (ng/g) in birds for background locations from 2007 to 2017.
For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 55
Figure 4-33. Concentration of DecaBDE (ng/g) in terrestrial mammals for background locations from
2006 to 2017. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within 56
Figure 4-34. Concentration of DecaBDE (ng/g) in amphibians for background locations in 2011 and
2016. For each year, the range of values reported is presented by the entire length of the
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bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 56
Figure 4-35. Concentration of DecaBDE (ng/g) in indoor dust from 2004 to 2010 57
Figure 4-36. Concentration of DecaBDE (ng/m3) in ambient air from 1997 to 1999 58
Figure 4-37. Concentration of DecaBDE (ng/g) in soils from 2008 to 2009 58
Figure 4-38. Concentration of DecaBDE (ng/g dry weight) in sediments from 1974 to 2005 59
Figure 4-39. Concentration of DecaBDE (ng/m3) in human blood from 1996 to 2010 60
Figure 4-40. Concentration of DecaBDE (ng/g) in aquatic invertebrates from 2004 to 2006. For each
year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
color within (dark blue) 60
Figure 4-41. Concentration of DecaBDE (ng/g) in fish from 2000 to 2012. For each year, the range of
values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate color within
(dark blue) 61
Figure 4-42. Concentration of DecaBDE (ng/g Iw) in bird eggs from 1974 to 2014 62
Figure 4-43. Estimated average daily dose (ng/kg/day) of DecaBDE for inhalation (blue), ingestion
(orange), dermal (grey), and total (gold) exposure. Data are presented for infants,
toddlers, children, and adults. If available, information on the age range, exposure
media, and location of exposure are provided in the x axis description. The study year
and HERO ID (diagonal text below the year) are also provided 63
Figure 4-44. Estimated average intake (ng/day) of DecaBDE for inhalation (blue), ingestion (orange),
dermal (grey), and total (gold) exposure. Data are presented for infants, toddlers,
children, and adults. If available, information on the age range, exposure media, season,
and location of exposure are provided in the x axis description. The study year and HERO
ID (diagonal text below the year) are also provided 64
Figure 5-1. Lifecycle Diagram for HCBD 76
Figure 5-2. Frequency of peer-reviewed publications identified that contained HCBD monitoring data 80
Figure 5-3. Concentration of HCBD (ng/m3) in indoor air for residential locations (2004) and modeled
data (2005). For each year, the range of values reported is presented by the entire length
of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within 81
Figure 5-4. Concentration of HCBD (ng/m3) in ambient air for near facility locations (1976 to 2006),
modeled data (1979), and from monitoring databases (EPA AMTIC). For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 81
Figure 5-5. Concentration of HCBD (ng/L) in surface water for background locations (1983 to 2007),
near facility locations (1984 to 1997), and from monitoring databases (IPCHEM). For each
year/database, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 82
Figure 5-6. Concentration of HCBD (ng/L) in surface water from monitoring databases (IPCHEM,
USGS). For each database, the range of values reported is presented by the entire length
of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within 83
Figure 5-7. Concentration of HCBD (|u,g/L) in drinking water for background locations (2013) and
modeled data (1979). For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within 83
Figure 5-8. Concentration of HCBD (ng/g) in soil for background locations (2003 and 2014), near
facility locations (1976 to 2017), modeled data (1982), and from monitoring databases
(USGS). For each year/database, the range of values reported is presented by the entire
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length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within 84
Figure 5-9. Concentration of HCBD (ng/g) in sediment for background locations (1983 to 2010, near
facility locations (1985 to 2000), suspended sediments (1983 to 1997), and from
monitoring databases (ICES, IPCHEM). For each year/database, the range of values
reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within 85
Figure 5-10. Concentration of HCBD (ng/g) in sediment from monitoring databases (IPCHEM, USGS,
EPA GLENDA). For each year/database, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within 86
Figure 5-11. Concentration of HCBD (ng/g) in sludge/biosolids for near facility locations in 2014. The
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 86
Figure 5-12. Concentration of HCBD (ng/L) in influent/effluent from monitoring databases (EPA DMR).
For each database, the range of values reported is presented by the entire length of the
bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 86
Figure 5-13. Concentration of HCBD (ng/g) in vegetation/diet for near facility locations in 1975. The
range of values reported is presented by the entire length of the bar 87
Figure 5-14. Concentration of HCBD (ng/L) in seawater for near facility locations in 1975. The range of
values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 87
Figure 5-15. Frequency of peer-reviewed publications identified that contained HCBD biomonitoring
data 88
Figure 5-16. Concentration of HCBD (ng/g) in aquatic invertebrates for background locations (1983 to
2004) and from monitoring databases (IPCHEM, ICES, USGS). For each year/database,
the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark
color within 89
Figure 5-17. Concentration of HCBD (ng/g) in fish for background locations (1975 to 2014) and from
monitoring databases (ICES, IPCHEM, USGS). For each year/database, the range of values
reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within 90
Figure 5-18. Concentration of HCBD (ng/g) in aquatic mammals from one monitoring database (ICES).
The range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark
color within 91
Figure 5-19. Concentration of HCBD (ng/g) in terrestrial invertebrates for background locations from
1975 to 1987. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within 91
Figure 5-20. Concentration of HCBD (ng/g) in birds for background locations in 1975 and 2004. For
each year, the range of values reported is presented by the entire length of the bar 91
Figure 5-21. Concentration of HCBD (ng/g) in terrestrial mammals for background locations in 1975
and 2004. For each year, the range of values reported is presented by the entire length
of the bar 92
Figure 5-22. Concentration of HCBD (ng/m3) in ambient air from 1990 to 2014. For each row of data,
the entire length of the bar represents the range of values reported. The darker color
within the bar shows the minimum and maximum of reported central tendency
estimates 93
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Figure 5-23. Concentration of HCBD (ng/g) in soils from 1990 to 2015. For each year, the range of
values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate color within
(dark brown) 94
Figure 5-24. Concentration of HCBD (ng/g) in sediments from 1985 to 2004. For each year, the range
of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 95
Figure 5-25. Concentration of HCBD (ng/g) in sediments from 2004 to 2009. For each year, the range
of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate color within
(darker color) 96
Figure 5-26. Concentration of HCBD (ng/g) in sediments from 2009 to 2016. For each year, the range
of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 97
Figure 5-27. Concentration of HCBD (ng/g) in influent/effluents from 2007 through 2017. For each
year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 98
Figure 5-28. Concentration of HCBD (ng/g) in aquatic invertebrates from 2000 through 2011. For each
year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 99
Figure 5-29. Concentration of HCBD (ng/g) in aquatic invertebrates from 2011 through 2016. For each
year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 100
Figure 5-30. Concentration of HCBD (ng/g) in fish from 1998 through 2012. For each year, the range
of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 101
Figure 5-31. Concentration of HCBD (ng/g) in fish from 2012 through 2016. For each year, the range
of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 102
Figure 5-32. Concentration of HCBD (ng/g) in aquatic mammals in 1999 and 2000. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color
within 102
Figure 5-33. Estimated average daily dose (ng/kg/day) of HCBD for dermal exposure. Data are
presented for adults and two groups of children between 2-6 and 7-16 years of age 103
Figure 6-1. Lifecycle Diagram for PIP (3:1) 112
Figure 6-2. Frequency of peer-reviewed publications identified that contained PIP (3:1) and TPP
monitoring data 117
Figure 6-3. Concentration of PIP (3:1) and TPP (ng/g) in indoor dust for commercial locations 2012 to
2018), residential locations (2009 to 2018), and vehicles (2014 and 2017). For each year,
the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark
color within 118
Figure 6-4. Concentration of PIP (3:1) and TPP (ng/m3) in indoor air for commercial (2007 to 2018)
and residential (2004 to 2014) locations. For each year, the range of values reported is
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presented by the entire length of the bar. The minimum and maximum of reported
central tendency estimates are shown as a separate dark color within 119
Figure 6-5. Concentration of PIP (3:1) and TPP (ng/m3) in ambient air for background (2014) and
occupational (2016) locations. For each year, the range of values reported is presented
by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within 119
Figure 6-6. Concentration of PIP (3:1) and TPP (ng/g) in soil for near facility (1999 and 2015) locations.
For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within 119
Figure 6-7. Concentration of PIP (3:1) and TPP (ng/g) in sediment for commercial (2018), near facility
(2015), and residential (2018) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported
central tendency estimates are shown as a separate dark color within 120
Figure 6-8. Frequency of peer-reviewed publications identified that contained TPP, a surrogate for PIP
(3:1), biomonitoring data 121
Figure 6-9. Concentration of TPP (ng/g), a surrogate for PIP (3:1), in human blood (serum) for the
general population in 2017. The minimum and maximum of reported central tendency
estimates are shown 122
Figure 6-10. Concentration of TPP (ng/L), a surrogate for PIP (3:1), in human (other) for the general
population in 2014 and 2015. For each year, the range of values reported is presented by
the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within 122
Figure 6-11. Concentration of TPP (ng/wipe), a surrogate for PIP (3:1), in dermal wipes for the general
(2017 and 2018) and occupational (2016) populations. For each year, the range of values
reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within 122
Figure 6-12. Concentration of TPP (ng/g), a surrogate for PIP (3:1), in birds for background locations in
2015. The range of values reported is presented by the entire length of the bar 123
Figure 6-13. Concentration of TPP (ng/g), a surrogate for PIP (3:1), in terrestrial mammals for
background locations in 2017. The minimum and maximum of reported central tendency
estimates are shown 123
Figure 6-14. Estimated average daily dose (ng/kg/day) of TPP, a closely related chemical to PIP (3:1),
for inhalation (blue), ingestion (orange), dermal (grey), and total (gold) exposure. Data
are presented for infants, toddlers, children, and adults. If available, information on the
age range and location of exposure are provided in the x axis description. The study year
and HERO ID (diagonal text below the year) are also provided. Error bars represent the
average daily dose estimated using maximum concentrations in dust samples 124
Figure 6-15. Estimated average intake (ng/day) of TPP, a closely related chemical to PIP (3:1), for total
exposure. Data are presented for workers, drivers, non-workers, and stay-at-home
toddlers 125
Figure 7-1. Lifecycle Diagram for 2, 4, 6 TTBP 133
Figure 7-2. Frequency of peer-reviewed publications identified that contained 2,4,6 TTBP monitoring
data 136
Figure 7-3. Concentration of 2,4,6 TTBP and BHT (ng/g) in indoor dust for residential locations in
2017. The range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within 137
Figure 7-4. Concentration of 2,4,6 TTBP and BHT (ng/m3) in indoor air for commercial locations in
1989. The minimum and maximum of reported central tendency estimates are shown 137
Figure 7-5. Concentration of 2,4,6 TTBP and BHT (ng/m3) in ambient air for background locations in
2010. The range of values reported is presented by the entire length of the bar 137
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Figure 7-6. Concentration of 2,4,6 TTBP and BHT (ng/L) in surface water for background locations in
1999 and 2011. For each year, the range of values reported is presented by the entire
length of the bar 138
Figure 7-7. Concentration of 2,4,6 TTBP and BHT (ng/g) in sediment for background locations from
2004 to 2010. For each year, the range of values reported is presented by the entire
length of the bar 138
Figure 7-8. Concentration of 2,4,6 TTBP and BHT (ng/L) in influent/effluent for near facility locations
in 2012. The range of values reported is presented by the entire length of the bar 138
Figure 7-9. Concentration of 2,4,6-tris(tert-butyl) phenol (ng/g) in fish from one monitoring database
(USGS). The minimum and maximum of reported central tendency estimates are shown 140
Figure 7-10. Concentration of 2,4,6 TTBP (ng/L) in surface water from 1994 to 1996 141
Figure 7-11. Concentration of 2,4,6 TTBP (ng/g) in fish from 1998 through 2003. Only central
tendencies (dark blue) were reported 141
Figure 7-12. Estimated average daily dose (ng/kg/day) of the sum of seven synthetic phenolic
antioxidant analogues, which are used as a surrogate for 2,4,6 TTBP, for total exposure.
Data are presented for children and adults, separated by urban and rural regions 142
Figure 8-1. Lifecycle Diagram for PCTP 148
Figure 8-2. Frequency of peer-reviewed publications identified that contained PCTP biomonitoring
data 151
Figure 8-3. Concentration of PCTP (ng/L) in human (other) for the general (1992) and high-end (2000)
populations. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within 151
Acknowledgement
This report was developed by the United States Environmental Protection Agency (U.S. EPA),
Office of Chemical Safety and Pollution Prevention (OCSPP), Office of Pollution Prevention and
Toxics (OPPT). The OPPTTeam acknowledges support and assistance from EPA contractors ICF
(Contract No. EP-C-14-001), ERG (Contract No. EP-W-12-006), and SRC (Contract No. EP-W-17-
008).
Disclaimer
Reference herein to any specific commercial products, process or service by trade name,
trademark, manufacturer or otherwise does not constitute or imply its endorsement,
recommendation or favoring by the U.S. Government.
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1. Executive Summary
Section 6(h) of the Toxic Substance Control Act (TSCA), as amended by the Frank R. Lautenberg
Chemical Safety for the 21st Century Act, directs the U.S. Environmental Protection Agency
(EPA) to take expedited action to propose rules under TSCA with respect to chemicals identified
in EPA's 2014 Update of the TSCA Work Plan for Chemical Assessments and meeting criteria
relating to persistence, bioaccumulation and toxicity (PBT) and other factors. EPA must issue a
proposed rule no later than June 22, 2019, with a final rule to follow no more than 18 months
later.
EPA has developed this Exposure and Use Assessment for the five chemical substances it has
identified for proposed action under TSCA section 6(h) ("PBT chemicals"). This Exposure and
Use Assessment will be used by EPA in determining, under TSCA section 6(h)(1)(B), whether
exposure to each identified PBT is likely.
EPA conducted a comprehensive literature review to identify, screen, extract, and evaluate
exposure information for the five PBT chemicals addressed in this document. EPA also compiled
physical-chemical properties and information on uses. Exposure information was categorized as
core and/or supplemental. Core exposure data were defined as any environmental monitoring,
biomonitoring, modeled environmental concentration, or modeled dose data. Supplemental
exposure data were defined as any environmental fate or engineering data that provided
information related to potential exposure sources and environmental pathways.
This document presents available exposure information and integrates the information by
environmental media or biological matrix. EPA also provides some context for the sources and
environmental pathways that may have contributed to concentrations detected in
environmental and biological monitoring studies. EPA generated qualitative exposure scenarios
for identified uses for these five PBT chemicals.
2. Background
Under the Toxic Substances Control Act (TSCA), as amended by the Frank R. Lautenberg
Chemical Safety for the 21st Century Act, EPA has new authorities to regulate existing chemical
substances. Section 6(h) of TSCA directs EPA to take expedited regulatory action under section
6(a) for certain PBT chemicals.
Chemical substances subject to TSCA section 6(h) are those:
Identified in the 2014 update of the TSCA Work Plan for Chemical Assessments;
That the Administrator has a reasonable basis to conclude are toxic and that, with
respect to persistence and bioaccumulation, score high for one and either high or
moderate for the other, under the 2012 TSCA Work Plan Chemicals Methods Document
(or a successor scoring system);
That are not a metal or a metal compound;
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For which the Administrator has not completed Work Plan Problem Formulation,
initiated a review under section 5 (new chemicals), or entered into a consent agreement
under section 4 (testing), prior to June 22, 2016;
Exposure to which under the conditions of use is likely to the general population, to a
potentially exposed or susceptible subpopulation, or the environment, on the basis of
an exposure and use assessment; and
That are not designated as a high priority substance by EPA and are not the subject of a
manufacturer request for a risk evaluation.
Taking the above criteria into account, EPA has identified the following five PBT chemicals for
proposed action under TSCA section 6(h):
Decabromodiphenyl ether (DecaBDE) (CASRN 1163-19-5)
o Scored high for hazard, high for persistence, and high for bioaccumulation on the
2014 update
Hexachlorobutadiene (HCBD) (CASRN 87-68-3)
o Scored high for hazard, high for persistence, and high for bioaccumulation on the
2014 update
Phenol, isopropylated, phosphate (3:1) (PIP (3:1)) (CASRN 68937-41-7)
o Scored high for hazard, high for persistence, and high for bioaccumulation on the
2014 update
2,4,6-Tris(tert-butyl) phenol (2,4,6 TTBP) (CASRN 732-26-3)
o Scored high for hazard, moderate for persistence, and high for bioaccumulation on
the 2014 update
Pentachlorothiophenol (PCTP) (CASRN 133-49-3)
o Scored high for hazard, high for persistence, and high for bioaccumulation on the
2014 update
This assessment follows the publication of and public comment on use documents for each of
the five chemicals. The use documents were published by EPA in August 2017 and provide an
overview of the Agency's information on uses of each chemical at the time. Relevant
information from those use documents and the public comments is presented in each
chemical's section in this document. The use documents and the public comments in response
are in each chemical's docket.
Since the publication of the Use Documents in August 2017, EPA received public comments on
the Use Document and communicated with companies, industry groups, chemical users, and
other stakeholders to aid in identifying and verifying conditions of use for the five chemicals.
These interactions and comments further informed EPA's understanding of the uses for the five
chemicals. The information and input received from the public comments and stakeholder
engagement has been incorporated into this document to the extent appropriate.
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3. Approach
EPA used the following information for this exposure assessment. This information, where
available, is presented for each of the five PBT chemicals:
Chemistry and physical-chemical properties,
Use descriptions,
Expected environmental partitioning,
Lifecycle and potential sources,
Environmental monitoring,
Biomonitoring,
Modeled intake and doses,
Trends,
Information from completed exposure assessments and review articles, and
Qualitative exposure scenarios.
This information helps to identify potential exposure scenarios which are the combination of
sources/uses, environmental pathways, and receptors.
An exposure scenario is a set of facts, assumptions, and inferences about how exposure takes
place that aids the exposure assessor in evaluating, estimating, or quantifying exposure U.S.
EPA (2016b). A scenario is made up of combinations of the following:
Sources/Context of Use: Conditions of use, translated into specific lifecycle stage and
use descriptors
Environmental Pathway: Information about presence of a chemical within media,
transport form source to receptor and the route of exposure
Receptor: Information about presence of a chemical within a receptor (e.g., human workers or
general population) or environmental (e.g. aquatic or terrestrial)
Questions that help refine exposure scenarios include:
Sources/Context of Use: What specifically is being manufactured, produced or used and in
what manner? Has this changed over time? Is it an ongoing use? Is it a use that is
generally controlled by existing environmental regulations? Which lifecycle stage(s)
does the use apply to and how does that information provide context about the location
of who is exposed during that use?
Environmental Pathway/Media: Within the context of the use, how does the chemical
reach the receptor and enter the human body or organism? What environmental media
are most likely to contribute to exposure? What are the associated routes of exposure
(oral, inhalation, dermal) for these media?
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Receptor: Who specifically may be exposed? Could the exposed receptor include specific
susceptible subpopulations? How might the demographic or behavioral variability affect
exposure?
An overview of the approach taken for each section is presented below.
Chemistry information was primarily obtained from EPA's Chemistry Dashboard (U.S. EPA.
2018a). The CAS number, structure, molecular formula, and select synonyms are presented.
Note, EPA used a broader array of chemical synonyms in its search strategy and those chemical
synonyms are listed in the Supplemental Exposure document. Physical-chemical property
information was obtained through a combination of measured and estimated data. EPA's EPI-
Suite model was used for estimation, when empirical data was not available (U.S. EPA. 2012).
EPA presents the following physical-chemical properties for each chemical substance: molecular
weight, density, molar volume, octanol-water partition coefficient Log Kow, octanol-air partition
coefficient Log Koa, octanol-carbon partition coefficient Log Koc, vapor pressure, Henry's law
constant, and water solubility.
EPA compiled preliminary information on manufacturing, processing, distribution, use, and
disposal for each of the five PBT chemicals in August 2017. Since that time, EPA reviewed public
comments and engaged with many stakeholders which further informed EPA's understanding
of uses. Use descriptions can be considered holistically to inform how a chemical is used in a
given application across its lifecycle (manufacturing, processing, use, and disposal).
From these use descriptions, EPA developed lifecycle diagrams for each of the five PBT
chemicals. EPA also completed a qualitative assessment describing relative potential for
occupational exposure and relative potential for release to different media from industrial
operations.
From available physical-chemical property information, EPA developed a qualitative assessment
of expected environmental partitioning should a chemical be released to a given media. This
section assumes that processes described in this section occur after release to all media.
However, EPA notes that uses and processes for each of these five PBT chemicals are not
expected to result in releases to all media.
EPA completed a comprehensive literature search and evaluation for environmental monitoring
and biomonitoring data. Studies that contained primary, quantitative, readily extractable data
in environmental media and in matrices of biological organisms were evaluated and integrated
into this assessment. Note that for the five PBT chemicals found in air and water, no distinction
was made during data extraction for chemical bound to particulate matter versus free chemical
in air/water. For PIP (3:1) and 2,4,6 TTBP, few monitoring studies were reported. Consequently,
EPA conducted a supplemental search on closely related chemicals with similar structures and
physical-chemical properties. The list of closely related chemicals is provided in the
Supplemental Exposure Document. Of this list, Triphenyl Phosphate (TPP) and Butyl
Hydroxytoluene (BHT) were used as surrogate or read-across chemicals for PIP (3:1) and 2,4,6-
TTBP, respectively.
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EPA also completed a comprehensive literature search for and evaluation of studies reporting
modeled intake or dose. Studies that contained primary, quantitative, readily extractable,
modeled estimates of intake (mass chemical per day) or dose (mass chemical per mass body
weight per day) of the five PBT chemicals were evaluated and integrated into this assessment.
Articles that contained spatial or temporal trend data were also evaluated and integrated into
this assessment. Natural language processing algorithms were run to identify those that
contained the words "temporal, time trend, time-trend, time varying, time-varying, time-
dependent, time dependent, time activity, trend, spatiotemporal, or spatio-temporal" within
either the title or abstract. These articles were then reviewed to determine if they contained
spatial or temporal trend data. Additionally, various publicly available databases on
environmental monitoring data previously identified by EPA were searched for data on the
chemicals of interest; where this data was reported temporally, it was included with the
extracted data identified in the systematic review. Note that some databases provided chemical
concentrations by country. Monitoring data from developed countries with well-established
and enforced environmental regulations may be more relevant for the U.S.
During the development of the literature search strategy, existing exposure and risk
assessments were used as the basis for backwards searches to identify primary literature
sources. Existing assessments were identified for four of the five PBT chemicals. The results
from the assessments are summarized. Note, if these assessments summarized primary
monitoring data, those data sources are not reported under existing assessments and are
instead reported with other primary monitoring data. Secondary review articles were also
identified during EPA's systematic review. Data presented for review articles are limited to
those that reported additional information on potential sources and/or environmental
pathways in addition to environmental concentrations or doses. Note, if these review articles
summarized primary monitoring data, those data sources are not reported under review
articles are instead reported with other primary monitoring data.
EPA presented qualitative exposure scenarios for this exposure assessment. These qualitative
scenarios provide additional context for likely exposures. These exposure scenarios may have
relatively higher exposure potential and may represent a broader range of exposure scenarios.
However, they are not intended to be comprehensive of every possible exposure scenario for
these chemicals.
The literature search provides information about which of the data types are available and
usable for different sources, pathways, and receptors to inform generation of exposure
scenarios. Different types of data are needed to characterize the variety of chemical-specific
exposure scenarios. A range of qualitative and quantitative data was available and usable for
the five PBT chemicals in this exposure assessments across uses, releases, concentrations,
intakes, and doses. Quantitative data are summarized for components of exposure scenarios
while qualitative exposure scenario descriptions are provided.
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Table 3-1. Overview of Qualitative and Quantitative Exposure Information used in this
Exposure Assessment
Sources/Context of Use
Environmental Pathway
Receptor
Exposure Scenarios
Chemistry and physical-chemical
properties (quantitative)
Fate and transport
(qualitative)
Intake and uptake
(quantitative)
Qualitative
Use information (qualitative)
Environmental monitoring
data (quantitative)
Internal dose
(quantitative)
Emission/release information
(qualitative)
Modeled estimates
(quantitative)
Biomonitoring data
(quantitative)
In addition, EPA notes overarching uncertainties for consideration below.
Reported monitoring data does not necessarily reflect current or future conditions; but rather
the conditions that were present at the time when samples were collected. Even very recent
studies represent conditions when samples were collected, generally months to years before
the publication of the study. Monitoring data can be heterogeneous in its reporting of free
versus particle bound chemical concentrations in surface water and air. Supplementary
contextualizing data such as lipid content, sample location, and even level of detection are not
uniformly reported. There is uncertainty in both direct comparisons between two different
monitoring studies and overall comparison across all monitoring studies. There may be less
uncertainty, however, when comparing trends within one monitoring study.
Reported modeling data reflects the underlying assumptions about releases, environmental
transport, and uptake. Modeled data also provides evidence of exposures that can be tailored
to reflect many past, current, or future possible conditions and scenarios. EPA references
modeling conducted by others in this assessment, but did not conduct its own exposure
modeling from identified sources. Instead, EPA presents qualitative exposure scenarios and
separately presents monitored and estimated concentrations and doses.
There are different approaches to construct exposure scenarios. There is overlap between
qualitative exposure scenarios described by EPA and scenarios presented in completed
assessments for some chemicals. Comparison of exposure scenarios can involve source
attribution. The relative complexity of source attribution varies depending on the continuum of
available uses/sources and the media considered. For example, total dust concentrations in a
residence represent contributions from multiple different sources. Similarly, the internal dose
represents total exposure from multiple media and sources. This source attribution can be
qualitative or quantitative. EPA used qualifiers (e.g. higher, lower potential for exposure)
throughout the document to describe exposures. EPA focused on describing qualitative
exposure scenarios with higher potential. However, uncertainty is acknowledged when
describing relative comparisons across exposure scenarios.
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4. Decabromodiphenyl Ether (DecaBDE)
4.1. Chemistry and Physical-Chemical Properties
Chemical Name
Decabromodiphenyl Ether
CASRN
1163-19-5
Synonyms
DecaBDE, Deca, BDE209
Molecular Formula
Ci2BrioO
Structure
Br Br
1 I
0 Br
Br' ^ \ Blf Br
Br Br
MW
959.17
Density (g/cm3)
3.4 at 25ฐC (RSC. 2013)
Molar Volume (cm3/mol)
282 [Calculated based on the molar mass and density]
Log Kow
9.97 [(EU. 2002) citing (Watanabe and Tatsukawa. 1990)1
Log Koa
16 [Estimated using EPISuite v4.11 (U.S. EPA. 2012)1
Log Koc
6.5 [Kow method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Vapor Pressure (mm Hg)
3 x 10 s [Extrapolated from (RSC. 2013)1
Henry's Law atm-m3/mole
4.5 x 10 s [Group Method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Water Solubility (mg/L)
0.02 (Chemicals Inspection and Testing Institute. 1992)
Water Solubility (mol/L)
2.1 x 10 s [Calculated based on water solubility and molecular weight]
4.2. Uses
Since the publication of the Use Document in August 2017 for decabromodiphenyl ether
(DecaBDE), EPA received 12 public comments on the Use Document and communicated with
dozens of companies, industry groups, chemical users, and other stakeholders to aid in
identifying and verifying conditions of use of DecaBDE (U.S. EPA. 2017b). These interactions and
comments further informed EPA's understanding of the uses for DecaBDE. The information and
input received from the public comments and stakeholder engagement has been incorporated
into this document to the extent appropriate. Non-confidential public comments and
stakeholder meeting summaries are available in EPA's docket at EPA-HQ-QPPT-2016-0724.
DecaBDE is one congener in a class of chemicals known as polybrominated diphenyl ethers
(PBDEs). PBDEs are a class of substances that contain an identical base structure but differ in
the number of attached (1-10) bromine atoms. Commercial PBDEs are only used as flame
retardants. PBDE flame retardants perform well in many products, preserving the durability and
performance of the material while providing flame retardancy at a reasonable cost. These
characteristics have resulted in their widespread use in hundreds of consumer products,
including many plastics and textiles (upholstery). Flame retardants, in general, are incorporated
into products in one of two ways. They are either chemically bound to the product matrix as
"reactive" mixtures, or they are dissolved in the polymer materials as "additives." PBDEs are
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additive flame retardants. Additive flame retardants are relatively unattached to the polymer
matrix and may readily migrate from products to the surrounding environment during
manufacture, normal use, and disposal (Verslycke et al.. 2005). End of use for products
containing PBDEs include disposal in landfills as well as recycling (USGS. 2006) or incineration
(Verslycke et al.. 2005).
DecaBDE specifically has a variety of uses as an additive flame retardant in plastic enclosures
for televisions, computers, audio and video equipment, textiles and upholstered articles, wire
and cables for communications and electronics, and other applications (U.S. EPA. 2017b). The
primary use of DecaBDE is in high-impact polystyrene-based products and in the manufacture
of textiles and plastics. The three major product categories in which DecaBDE has been used as
a flame retardant are: textiles, electronic equipment, and building and construction materials
(U.S. EPA. 2017b). DecaBDE is also used as a flame retardant for multiple applications in the
aerospace and automotive industries, including replacement parts for cars and aircraft (EPA-
HQ-QPPT-2016-0724)(U.S. EPA. 2017b).
The uses of DecaBDE that are considered within the scope of the exposure and use assessment
during various life cycle stages (i.e., manufacturing, processing, use (industrial, commercial and
consumer), distribution and disposal) are depicted in Table 4-1 and the life cycle diagram
(Figure 4-1). The information is grouped according to Chemical Data Reporting (CDR) processing
codes and internationally harmonized functional, product and article use categories from the
Organisation for Economic Co-operation and Development (OECD) in combination with other
data sources (e.g., published literature and consultation with stakeholders), to provide an
overview of the uses.
Use categories are drawn from CDR definitions laid out in Instructions for Reporting for the
2016 CDR (U.S. EPA, 2016c). "Commercial use" means the use of a chemical or a mixture
containing a chemical (including as part of an article) in a commercial enterprise providing
saleable goods or services. "Consumer use" means the use of a chemical or a mixture
containing a chemical (including as part of an article, such as furniture or clothing) when sold to
or made available to consumers for their use.
Table 4-1. Use Categories and Subcategories for DecaBDE
Life Cycle Stage
Category3
Subcategory13
References
Manufacture
Domestic manufacture
Domestic manufacture
U.S. EPA (2016a)
Import
Import
U.S. EPA (2016a)
Processing
Processing -
incorporation into
formulation, mixture,
or reaction
Flame retardant in:
Plastic product manufacturing
Textile, and apparel
manufacturing
U.S. EPA (2016a)
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Life Cycle Stage
Category3
Subcategory13
References
Processing-
Incorporation into
Article
Flame retardant in:
High impact polystyrene (HIP) -
based products
Textiles
Electronic plastic casings
Rubber (wire casings)
Building and construction
materials
Multiple automotive and
aerospace components including
adhesives, plastics, and fabrics
U.S. EPA (2017b); EPA-
HQ-OPPT-2016-0724
Recycling
Flame retardant in:
Recycled plastic pallets
EPA-HQ-OPPT-2016-
0724
Commercial/Consumer
Uses (includes
imported articles)
Articles - Plastic articles
(hard and soft,
including HIP based
products)
Flame retardant in:
Plastic electronic casings
Toys intended for children's use
U.S. EPA (2017b); EPA-
HQ-OPPT-2016-0724
Articles - Fabrics,
textiles, and apparel
Flame retardant in:
Furniture and furnishings
Curtains
Construction and building
materials
U.S. EPA (2017b)
Articles-Complex
articles
Flame retardant in:
Vehicles (automotive and
aerospace - includes replacement
parts)
U.S. EPA (2017b);
EPA-HQ-OPPT-2016-
0724
Distribution in
commerce
Distribution
Distribution in commerce
U.S. EPA (2017b)
Disposal
Air Releases
Fugitive air emissions
U.S. EPA (2017f)
Point source air emissions
Water Releases
Surface water discharge
U.S. EPA (2017f)
Land releases
Solid wastes
U.S. EPA (2017f)
Off-Site Releases
Transfers off-site
U.S. EPA (2017f)
Recycling
Recycled plastics articles containing
DecaBDE not intended for use as a
flame retardant (toy's intended for
children's use, electronic casings,
HIPs)c
EPA-HQ-OPPT-2016-
0724
aThese categories of use appear in the Life Cycle Diagram, reflect CDR and OECD codes, and broadly represent the uses of
decabromodiphenyl ether in commercial and/or consumer settings.
These subcategories reflect more specific uses of decabromodiphenyl ether based on stakeholder outreach, and comments
received on EPA's Preliminary Information on Manufacturing, Processing, Distribution, Use, and Disposal published in August
2017.
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CEPA plans to analyze the use of DecaBDE in recycled plastic pallets, as the flame retardant properties of DecaBDE are still
utilized for this particular use. EPA does not expect to consider recycled articles, where those articles do not have intended
flame retardant applications.
Descriptions of the commercial or consumer use categories identified from the 2017 OECD
Harmonized Use Codes are summarized below (OECD. 2017b):
The "Plastic articles" category encompasses consumer products made of both hard and soft
plastics, which includes DecaBDE as a flame retardant, including furniture & furnishings, foam in
furniture or mattresses, computer casings, and toys intended for children's products (such as
play structures).
The "Fabrics, textiles, and apparel articles" category encompasses construction and building
materials, furniture and furnishings, curtains, and other articles with routine direct contact
during normal use.
The "Complex articles" category encompasses road vehicles and other vehicles for passengers
and goods such as cars, trucks, and airplanes, and machinery, mechanical appliances, electrical
and electronic articles such as computers and drills. It also encompasses replacement parts for
both the automotive and aerospace industries.
4.3. Characterization of Expected Environmental Partitioning
If released to air, based on its vapor pressure (3 x 10"8 mm Hg) and Henry's law constant
(4.5 x 10"8 atm m3/mole), DecaBDE will generally partition into water rather than the air.
Further, DecaBDE will tend to partition to soil and airborne particulates rather than air due to
its vapor pressure and octanol-air partition coefficient (log Koa = 16). DecaBDE adsorbed to
particulates in the air can be removed from the atmosphere via wet or dry deposition, but the
presence of the compound at remote sites globally indicates that particulate-bound DecaBDE
can undergo long-range transport in the atmosphere.
If released to water, DecaBDE in surface water is expected to partition to sediments and
suspended particulates, based on its octanol-water partition coefficient (log Kow = 9.97) and
organic carbon partition coefficient (log Koc = 6.5). Due to its vapor pressure and Henry's law
constant, DecaBDE is not likely to partition from water into air.
In wastewater treatment, DecaBDE is likely to sorb to biosolids due to its log Koc and water
solubility (0.02 mg/L) and is unlikely to volatilize to the air due to its Henry's law constant. Due
to its log Koc, most DecaBDE in wastewater is expected to be removed by adsorption to
biosolids, which may later be landfilled, land-applied, or incinerated. Release of free DecaBDE in
effluent water is expected to be limited, although DecaBDE adsorbed to small particles may be
present in effluent.
If released to soil, due to its Henry's law constant, vapor pressure, and log Koc, DecaBDE is not
expected to volatilize from moist or dry soil. Further, DecaBDE is not likely to be mobile in
groundwater, soil pore water, or the aqueous phase in other subsurface environments based
Page 24 of 190
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on its log Koc and water solubility, although DecaBDE sorbed to colloids or other particles may
be transported in subsurface environments.
If released to landfill, based on its water solubility and log Koc, migration of DecaBDE from
landfills into leachate is expected to be limited and slow. Volatilization of DecaBDE from solid
waste is not likely due to its vapor pressure.
DecaBDE also may partition to the tissues of organisms that live in water, soil, and sediment via
dermal or gill exposure and ingestion. Exposure to water column organisms is also possible via
resuspension of the chemical from the sediment to water either sorbed to particulates or part
of the dissolved phase. The above characterization is meant to describe the primary behavior or
movement of the chemical through a generic environment, not the complete exclusion of the
chemical from a given media (e.g., water) or elimination of the possibility for more complex
behavior in a particular location.
If released to the indoor environment, volatilization of DecaBDE from consumer products or
articles, contaminated water, or other aqueous solutions is not likely due to its vapor pressure
and Henry's law constant. Any potential emission to air would likely quickly partition to
suspended dust. Due to its log Koa and vapor pressure, DecaBDE is more likely emitted from
solid articles through direct transfer to dust or abrasion, partitioning to dust and other
particulates. The relationship between the initial concentration of DecaBDE in articles, emission
of DecaBDE into indoor environments through various mechanisms and resulting indoor-dust
levels, and the final concentration of DecaBDE in articles prior to disposal is not well
characterized even though there is supporting data for some aspects of these processes for
certain consumer articles.
4.4. Overview of Lifecycle and Potential Sources of Exposure
4.4.1. Background and Brief Description of Lifecycle
Flame retardants are incorporated into products in one of two manners. They are either
chemically bound to the product matrix as "reactive" mixtures, or they are dissolved in the
polymer materials as "additives." DecaBDE is an additive flame retardant. Additive flame
retardants are not chemically bound and are relatively unattached to the polymer matrix.
Therefore, they have the potential of migrating from products to the surrounding environment
during manufacture, normal use, and disposal (U.S. EPA. 2017b).
DecaBDE's primary use is in high impact polystyrene-based products that are used in plastics,
specifically in plastic enclosures for televisions, computers, audio and video equipment, and
mobile phones. It is also used in textiles and upholstered articles (including carpets, upholstery
fabric, back coatings, cushions, mattresses, and tents), wire and cables for communications and
electronics, and other miscellaneous applications (U.S. EPA. 2017b; BSEF. 2007).
Page 25 of 190
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MFQ/IMPORT PROCESSING COMMERCIAL, CONSUMER USES* RELEASES and WASTE DISPOSAL
Manufacture
(including Import)
(<25,000 lbs a)
Imported Articles'1
| Manufacture
aChemical Data Reporting (CDR) data for 2015; U.S. manufacturers and importers agreed to voluntarily phase out domestic
manufacture and import of the chemical no later than December 31, 2013. Preliminary data for the 2016 CDR indicates the
total in 2015 is less than 25,000 lbs. The total volume of DecaBDE manufactured (including imported) in the United States was
16,696,951 lbs in 2012, between 1,000,000 and 10,000,000 lbs in 2013, between 100,000 and 500,000 lbs in 2014, and less than
25,000 lbs in 2015. Actual production volume for years 2013 through 2015 is claimed as confidential business information.
bAn unknown but significant quantity of DecaBDE is expected to be imported in articles.
Figure 4-1. Lifecycle Diagram for DecaBDE
4.4.2. Manufacturing
The commercial production of DecaBDE involves bromination of diphenyl oxide to varying
degrees. The degree of bromination is controlled either through stoichiometry or through
control of reaction kinetics. The product is dried following reaction and separation steps to
form a solid powder {ATSDR, 2004,1004954}. DecaBDE is not expected to be manufactured or
handled as a liquid during these operations. Therefore, the most likely sources of releases and
occupational exposures are associated with fugitive dust. These include air releases from
transfer and packaging operations (fugitive dust to ambient air as well as dust that is collected
and channeled through a dedicated point as a stack release) and solid waste from floor
sweepings, disposal of used transfer containers containing residual DecaBDE, and liquid waste
from equipment cleaning. Fugitive vapor air releases are not expected due to the low vapor
pressure. Releases to land are possible when floor sweepings and other solid waste are
collected and disposed in landfills. Similarly, the collection and disposal of liquid equipment
cleaning solutions has the potential of generating liquid waste containing DecaBDE (aqueous
waste to surface waters and sent to publicly owned treatment works, and organic waste
collected and sent for other disposal or waste treatment such as incineration). Historical and
recent TRI data confirm primary releases are to air, followed by landfill and water {U.S. EPA,
2016, 3479565}(TRI 2016). Occupational exposures from inhalation and dermal exposure to
Incorporated into
Formulation, Mixture, or
Reaction Products
(Flame retardant in: plastic
product manufacturing;
textiles, apparel, and leather
manufacturing)
Incorporation into Article
Components
(Flame retardant in: HIP based
products; textiles; electronic
plastic casings; rubber (wire
casings); building and
construction materials; multiple
automotive and aerospace
components including
adhesives, plastics, and fabrics)
Recycling
Recycled plastics containing
deca BDE not intended for
use as flame retardant (e.g.
plastic pallets, children's
products)
Articles - Fabrics, textiles, and
apparel
(Flame retardant in: furniture and
furnishings; curtains; construction and
building materials; other articles)
Articles - Plastic articles (hard and
soft, including HIP based products)
(Flame retardant in: plastic electronic
casings)
Articles - Complex articles
(Flame retardant in automotive and
aerospace vehicles - including replacement
parts)
| ^ Processing
~
Emissions to Air
Wastewater
Liquid Wastes
Solid Wastes
Decabromodiphenyl
Ether (DecaBDE)
*Past/Legacy Uses Include: plastic pellets
Page 26 of 190
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dust are expected during transfer and packaging operations and from fugitive dust emissions
from process operations. However, exposure to liquids is not anticipated.
Table 4-2. CDR Production Volumes 2010-2015
CDR Reporting
Year
2010
2011
2012
2013
2014
2015
Production
Volume (lb)
51,008,002
18,110,827
10,000,000-
50,000,000
1,000,000-
10,000,000
100,000-
500,000
<25,000
4.4.3. Imported Articles
The 2016 CDR data indicate that DecaBDE is manufactured (including import) in quantities less
than 25,000 lbs (U.S. EPA. 2017b). However, significant quantities are also imported as a
component of articles, including: plastics in televisions, computers, audio and video equipment;
textiles and upholstered articles such as carpets, upholstery fabric, cushions, mattresses, and
tents; wire and cables for communications and electronics; and other miscellaneous
applications (EPA-HQ-QPPT-2016-0724). The quantity of DecaBDE in these articles is unknown;
however, it may be substantial. Potential releases from these articles may occur when DecaBDE
migrates from the articles during use, disposal, and waste management. Occupational dermal
exposures are expected to be minimal, but possible from handling and repackaging articles.
Inhalation and dermal exposures are possible during recycling operations (e.g. recycling of
plastics) (EPA-HQ-QPPT-2016-0724).
4.4.4. Processing: Incorporated into Formulation, Mixture, or Reaction
Products and Incorporation into Article Components
DecaBDE is combined with other ingredients (e.g., monomers) and then molded, extruded,
formed into final products, or applied to a finished article, where curing may occur (ACC. 2002).
Releases to air, land, and water are expected from DecaBDE and DecaBDE flame retardant
formulations (solids and liquids) as well as from off-spec products containing the additive flame
retardant. Air releases (fugitive dust and dust collected and channeled to a stack) are expected
from transfer operations. Releases to land may occur during disposal of transfer containers
containing residual material, collection and disposal of floor sweepings, and disposal of off-spec
product. Equipment and general area cleaning with aqueous cleaning materials may result in
releases to water. Current and historical TRI data indicate the primary releases are to air,
followed by landfill and water (U.S. EPA. 2016d). Occupational exposures from inhalation and
dermal exposure of dust is expected during transfer and packaging operations and from fugitive
dust emissions from process operations. Dermal exposure to liquids is possible from incidental
contact of liquid flame retardant formulations containing DecaBDE during transfer, loading, and
mixing operations. Occupational exposures are most likely to occur when the bags of flame
retardant are emptied into a hopper prior to mixing. Once formulated, DecaBDE is encased in
the polymer matrix and worker exposure is unlikely (ACC. 2002).
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4.4.5. Processing: Recycling
DecaBDE is present in plastic that may be recycled and subsequently reused (EPA-HQ-OPPT-
2016-0724). Environmental releases from recycling facilities are expected from discarded
material that cannot be recycled and reclaimed and is disposed in landfills. Releases to air and
water are not expected. Limited occupational exposure to workers at recycling facilities is
possible from dermal contact during handling of plastic material that is received and introduced
into recycling operations, and from inhalation exposure to dust from grinding and shredding
operations.
4.4.6. Industrial/Commercial Use: Fabrics, Textiles and Apparel
(textile manufacturing)
DecaBDE is combined with other ingredients and incorporated into the back coating of various
textiles via roll or dip coating processes. Releases are expected from disposal of transfer
containers associated with DecaBDE formulations, waste from equipment and area cleaning,
disposal of off-spec product, and bath dumps. Historical TRI data indicate most releases are
associated with disposal to landfills, smaller quantities to air, and minimal releases to water. No
releases to air or water from textile facilities reporting to TRI have occurred since 2013 (U.S.
EPA. 2016d). Inhalation exposures may occur due to: fugitive dust generated from unloading
and transfer of the solid flame retardant into mixing vessels; mist generated from the squeezing
of the immersed fabric with rollers; from the roll coating application during back coating; and,
after the coating operations are complete, during fabric cutting. Dermal exposures to solid and
liquid DecaBDE mixtures in fabric finishing may occur from unloading operations, mixing
finishing baths, equipment cleaning, and unintentional spilling (ERG. 2004).
4.4.7. Industrial/Commercial Use: Incorporation into Plastic Articles
(wire and cable coatings)
DecaBDE is combined with other ingredients and then molded, extruded, formed into final
products, or applied to wire or cable (ACC. 2002). Releases are expected from transfer
operations, disposal of transfer containers, waste from equipment and area cleaning, and
disposal of off-spec product. Historical TRI data indicate most releases are associated with
disposal to landfills, smaller quantities to air, and minimal or no releases to water (U.S. EPA.
2016d). Inhalation exposure from fugitive dust that is generated from unloading and transfer of
the flame retardant into mixing vessels may occur. Dermal exposure is most likely during
formulation when the bags of flame retardant are emptied into a hopper prior to mixing. Once
formulated, DecaBDE is encased in the cured coating and the potential for worker exposure is
minimal.
4.4.8. Industrial/Commercial Use Articles - Complex articles
Article components containing DecaBDE such as fabrics and plastic parts are incorporated into
finished products such as automobiles and aircraft. Releases to land are expected from disposal
of off-spec products that contain DecaBDE. Releases to air and water are not expected.
Page 28 of 190
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Occupational exposure from dermal contact with article components during installation is
possible. Inhalation exposure is not expected.
4.4.9. Consumer Articles
Articles treated with DecaBDE are used in the home, in business settings, and in the
transportation sector. DecaBDE has also been found in children's products such as plastic play
structures, and toys (EPA-HQ-QPPT-2016-0724). DecaBDE is also found in plastics used as
components in electrical appliances and equipment such as stereos, computers, televisions,
circuit boards, casings, and cable insulation. Other specified uses in the transportation and
construction sector are in the fabrics of automobiles, aircrafts, and in wood used as building
materials (U.S. EPA. 2017b). DecaBDE's primary use is in high impact polystyrene-based
products that are used in plastics, specifically in plastic enclosures for televisions, computers,
and audio and video equipment. It is also used in textiles and upholstered articles (including
carpets, upholstery fabric, curtains, cushions, mattresses, and tents), wire and cables for
communications and electronics, and other miscellaneous applications (EPA-HQ-QPPT-2016-
0724)(U.S. EPA. 2017b). The end-of-life disposal and waste handling options for products
containing DecaBDE include disposal in landfills, recycling (USGS. 2006) and incineration (BSEF.
2007; Janssen. 2005).
4.4.10. Qualitative Trends Over Time for Releases and Occupational
Exposures
DecaBDE was historically used as the flame retardant of choice in many commercial and
consumer products including a wide variety of plastics, textiles, and other uses. Releases to all
media and corresponding occupational exposures associated with manufacturing, processing,
and use were significant. However, due to potential human health and environmental risks, the
principle domestic manufacturers and importers of commercially-available DecaBDE agreed to
voluntarily phase out domestic manufacture and import of the chemical no later than
December 31, 2013. This resulted in a steady decrease in domestic production volume from
millions of pounds per year to less than 25,000 pounds in 2015 (U.S. EPA. 2017b) and (U.S. EPA.
2016a).
TRI data show a corresponding decrease in releases that are reported in each industry sector
using DecaBDE. The number of manufacturing facilities, textile manufacturing facilities, wire
and cable manufacturing facilities, and other facilities reporting TRI releases has decreased
from several dozen to only one manufacturer and 23 other facilities. The total yearly releases to
all media and quantities managed as waste have seen a similar decline from millions to
thousands of pounds (U.S. EPA. 2016d).
4.5. Environmental Monitoring
Hundreds of studies show that DecaDBE has been detected in a wide variety of media.
Table 4-3 summarizes the monitoring data for DecaBDE identified in the peer-reviewed
literature across all media considered. Also included in the count are available monitoring
Page 29 of 190
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database sources. Only studies or databases that reported measurements of the chemical of
interest above the limit of detection were extracted and included in the "# of studies" count.
The frequency of detection is provided as a measure, across all samples in all extracted studies,
of the frequency that the chemical was measured above the limit of detection. Note, the
frequency of detection is reported only for peer-reviewed sources, unless the only data sources
available were database sources.
The patterns in Table 4-3 are generally consistent with the fate summary and physical-chemical
properties in that DecaBDE was detected at relatively higher concentrations in indoor dust, soil,
sediment, and sludge/biosolids. DecaBDE was detected at relatively lower concentrations in
indoor air, ambient air, and surface water. Detection in ambient air reflects releases to air,
which is an important environmental pathway to surface water and sediment. In addition,
DecaBDE was reported in influent/effluent and landfill leachate, reflecting releases to water
and land.
Table 4-3. Summary of DecaBDE Monitoring Data from the Peer-Reviewed Literature
Media
Presence
No. of Datasets
Frequency of Detection3
Indoor dust
Yes
75
96%
Indoor air
Yes
16
94%
Ambient air
Yes
34
94%
Surface/Ground water
Yes
11
100%
Drinking water
No
0
n/a
Soil
Yes
40
100%
Sediment
Yes
65
94%
Biosolids
Yes
19
98%
Wastewater (influent, effluent)
Yes
10
88%
Landfill leachate
Yes
2
97%
Vegetation/Diet
Yes
9
90%
Other
Yes
3
(varies by media)
frequency of detection for peer reviewed studies only
The following chart provides the number of studies reporting DecaBDE monitoring data over
time. For this chart, the year the study is published rather than the sampling timeframe is used
as a proxy, though for most studies, samples were collected a few years prior to publication.
Note, EPA recognizes that the sampling dates, rather than the publication date, would be a
better reflection of temporal trends.
Page 30 of 190
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1980 1905 1990 IMS 2000 2005 2010 2015
Figure 4-2. Frequency of peer-reviewed publications identified that contained DecaBDE
monitoring data.
All environmental monitoring data that passed EPA's evaluation criteria are presented
graphically in the plots below. In short, EPA evaluated sampling methods, analytical
approaches, quality assurance procedures, spatial and temporal representativeness, and clarity
in reporting. These plots help visualize the data and are organized by study year and
microenvironment, when reported. Note, some studies are discussed in 4.7, 4.9, and 4.11 as
these studies integrate information on monitoring data and supplemental contextualizing
information on uses, sources, and trends.
Page 31 of 190
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4.5.1. Indoor Dust
_j commercial
ฆ residential
Shen et al. 2017
Harrad et al. 2016
Cristale et al. 2016
Sun et al. 2016
Tao et al. 2016
Shen et al. 2015
Li et al. 2015
Toms et al. 2015
Besis et al. 2014
Hassan and Shoeib 2014
Abafe and Martincigh 2014
Ali et al. 2014
Cequier et al. 2014
Cao et al. 2013
Batterman etal. 2010
Wu et al. 2010
Huang etal. 2010
Muenhor et al. 2010
Harrad et al. 2008
Norrgran Engdahl et al. 2017
Dodson etal. 2017
Al-Omran and Harrad 2017
Cowell et al. 2017
Korczetal. 2016
Meng et al. 2016
Kuang et al. 2016
Coelho et al. 2016
Harrad et al. 2016
Ali etal. 2016
Venier et al. 2016
10A-6
10M
0.01 1 100
Concentration (ng/g)
10M
10A6
Figure 4-3. Concentration of DecaBDE (ng/g) in indoor dust for commercial (2008 to 2017) and
residential (2016 and 2017) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within.
Page 32 of 190
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Cristale et al. 2016
Sun et al. 2016
Tao et al. 2016
Zhu et al. 2015
Zheng et al. 2015
Canbaz et al. 2015
Kefeni et al. 2014
Hassan and Shoeib 2014
Schreder and La Guardia 2014
Krol et al. 2014
Abafe and Martincigh 2014
Ward et al. 2014
Jiang et al. 2014
Cequier et al. 2014
Bennett et al. 2014
Shiet al. 2014
Chao et al. 2014
Johnson et al. 2013
Tue et al. 2013
Lee et al. 2013
Tang et al. 2013
Bjorklund et al. 2012
Aliet al. 2012
Niet al. 2012
Dodson et al. 2012
Vorkamp et al. 2011
Dirtu and Covaci 2010
Cunha et al. 2010
Huang et al. 2010
Imm et al. 2009
10A-6
10M
0.01 1 100
Concentration (ng/g)
10A4
10*6
Figure 4-4. Concentration of DecaBDE (ng/g) in indoor dust for residential locations (2009 to
2016). For each year, the range of values reported is presented by the entire length of the
bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within.
Page 33 of 190
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| residential
ฆ vehicle
Harrad et al. 2008
Allen et al. 2008
Allen et al. 2008
Wu et al. 2007
Besis et al. 2017
Gevao et al. 2016
Abafe and Martincigh 2016
Harrad et al. 2016
Ali et al. 2016
Olukunle et al. 2015
Hassan and Shoeib 2014
Harrad and Abdallah 2011
Cunha et al. 2010
Lagalante et al. 2009
Harrad et al. 2008
0.001
0.1
10 1000
Concentration (ng/g)
10A5
10A7
Figure 4-5. Concentration of DecaBDE (ng/g) in indoor dust for residential locations (2007 and
2008) and vehicles (2008 to 2017). For each year, the range of values reported is presented by
the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within.
The above figures for indoor dust contain data for the following: (Al-Omran and Harrad. 2017;
Besis et al.. 2017a; Cowell et al.. 2017; Dodson et al.. 2017; Norrgran Engdahl et al.. 2017; Shen
et al.. 2017; Abafe and Martincigh. 2016; Ali et al.. 2016; Coelho et al.. 2016; Cristale et al..
2016; Gevao et al.. 2016; Harrad et al.. 2016; Korcz et al.. 2016; Kuang et al.. 2016; Meng et al..
2016b; Sun et al.. 2016; Tao et al.. 2016; Venier et al.. 2016; Canbaz et al.. 2015; Li et al.. 2015c;
Olukunle et al.. 2015; Shen et al.. 2015; Toms et al.. 2015; Zheng et al.. 2015a; Zhu et al.. 2015;
Abafe and Martincigh. 2014; Ali et al.. 2014; Bennett et al.. 2014; Besis et al.. 2014; Cequier et
al.. 2014; Chao et al.. 2014; Hassan and Shoeib. 2014; Jiang et al.. 2014; Kefeni et al.. 2014; Krol
et al.. 2014; Schrederand La Guardia. 2014; Shi et al.. 2014; Ward et al.. 2014; Cao et al.. 2013;
Johnson et al.. 2013; Lee et al.. 2013; Tang et al.. 2013; Tue et al.. 2013; Ali et al.. 2012b;
Bjorklund et al.. 2012; Dodson et al.. 2012; Ni et al.. 2012; Harrad and Abdallah. 2011; Vorkamp
et al.. 2011; Batterman et al.. 2010; Cunha et al.. 2010; Dirtu and Covaci. 2010; Huang et al..
2010; Muenhor et al.. 2010; Wu et al.. 2010b; Imm et al.. 2009; Lagalante et al.. 2009; Allen et
al.. 2008a. b; Harrad et al.. 2008; Wu et al.. 2007)
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4.5.2. Indoor Air
commercial
ฆ residential
vehicle
| modeled
Sun et al. 2016
Tao et al. 2016
Cequier et al. 2014
Bjorklund et al. 2012
Ding et al. 2016
Venier et al. 2016
Sun et al. 2016
Tao et al. 2016
Cequier et al. 2014
Bjorklund et al. 2012
Konoplev et al. 2012
Vorkamp et al. 2011
Allen et al. 2013
Abdallah and Harrad 2010
Mandalakis et al. 2008
Cousins et al. 2014
10A-6 10A-4 0.01
100 10A4
Concentration (ng/m3]
Figure 4-6. Concentration of DecaBDE (ng/m3) in indoor air for commercial locations (2012 to
2016), residential locations (2011 to 2016), vehicles (2008 to 2013), and modeled data (2014).
For each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (Ding et al.. 2016; Sun et al.. 2016; Tao et al.. 2016;
Venier et al.. 2016; Cequier et al.. 2014; Cousins et al.. 2014; Allen et al.. 2013; Bjorklund et al..
2012; Konoplev et al.. 2012; Vorkamp et al.. 2011; Abdallah and Harrad. 2010; Mandalakis et
al.. 2008)
Page 35 of 190
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4.5.3. Ambient Air
| background
i near facility
ฆ particulate
Besis et al. 2017
Ding et al. 2016
Li et al. 2016
Li et al. 2016
Liu et al. 2016
Zhang et al. 2013
Konoplev et al. 2012
Niet al. 2012
Wang et al. 2012
Moeller et al. 2012
Yu et al. 2011
Chen et al. 2011
Moller et al. 2011
Zhang et al. 2009
Wilford et al. 2008
Cetin and Odabasi 2008
Cetin and Odabasi 2007
Cetin and Odabasi 2007
ter Schure et al. 2004
Strandberg et al. 2001
Luo et al. 2014
Heam et al. 2012
Chen et al. 2011
Qiu et al. 2010
Han et al. 2009
Shi et al. 2009
Cetin and Odabasi 2008
Cetin and Odabasi 2007
Besis et al. 2017
Li et al. 2016
10A-5
10M
0.001 0.01 0.1
Concentration (ng/m3)
10
100
Figure 4-7. Concentration of DecaBDE (ng/m3) in ambient air for background locations (2001
to 2017), near facility locations (2007 to 2014), and particulate data (2016 and 2017). For each
year, the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark color
within.
Page 36 of 190
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Li et al. 2014
Cousins etal. 2014 |
Buser et al. 2007 I
Zhang et al. 2017 I
| particulate
modeled
10A-5 10A-4 0.001 0.01 0.1
Concentration (ng/m3)
10
100
Figure 4-8. Concentration of DecaBDE (ng/m3) in ambient air for particulate data (2014) and
modeled data (2014 to 2017). For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within.
The above figures for ambient air contain data for the following: (Besis et al.. 2017b; Zhang et
al.. 2017: Ding etal.. 2016: Li etal.. 2016d: Li etal.. 2016c: Liuetal.. 2016: Li etal.. 2015b:
Cousins et al.. 2014: Luo et al.. 2014: Zhang et al.. 2013: Hearn et al.. 2012: Konoplev et al..
2012: Moeller et al.. 2012: Ni et al.. 2012: Wang et al.. 2012a: Chen et al.. 2011a: Moller et al..
2011: Yu etal.. 2011b: Qiu et al.. 2010: Han et al.. 2009: Shi et al.. 2009: Zhang etal.. 2009:
Cetin and Odabasi. 2008: Wilford et al.. 2008: Buser et al.. 2007: Cetin and Odabasi. 2007a. b;
ter Schure et al.. 2004: Strandberg et al.. 2001)
4.5.4. Surface Water
Cetin et al. 2016
Kirchgeorg et al. 2016
Zhang et al. 2015
He et al. 2012
Zhang et al. 2009
Zarnadze and Rodenburg 2008
Cetin and Odabasi 2007
ter Schure et al. 2004
Wang et al. 2013
Wu et al. 2008
Zhang et al. 2017 I
0.01
0.1
| background
| near facility
modeled
10
100
Concentration (ng/L)
Figure 4-9. Concentration of DecaBDE (ng/L) in surface water for background locations (2004
to 2016), near facility locations (2008 and 2013), and modeled data (2017). For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Zhang et al.. 2017: Cetin et al.. 2016: Kirchgeorg et
al.. 2016: Zhang et al.. 2015a: Wang et al.. 2013: He et al.. 2012: Zhang et al.. 2009: Wu et al..
2008: Zarnadze and Rodenburg. 2008: Cetin and Odabasi. 2007a: ter Schure et al.. 2004)
Page 37 of 190
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4.5.5. Drinking Water
Of the studies searched, EPA did not identify any studies that reported extractable DecaBDE
data in drinking water. DecaBDE is expected to adsorb to suspended particulates, based on its
octanol-water partition coefficient (log Kow = 9.97) and organic carbon partition coefficient (log
Koc = 6.5). As a result, DecaBDE is not expected to be present in drinking water.
4.5.6. Soil
| background
| near facility
Vadav et al. 2017
McGrath et al. 2016
Wei et al. 2016
Wu et al. 2015
Sun etal. 2015
Zhang et al. 2015
Liu et al. 2014
Chen etal. 2012
Jiang et al. 2012
Ni et al. 2012
llyas et ai. 2011
Meng et al. 2011
Qin et al. 2011
Yuet al. 2011
Duan etal. 2010
Jiang et al. 2010
Huang et al. 2010
Li et al. 2009
Sun et al. 2009
Zou et al. 2007
Li et al. 2016
McGrath et al. 2016
Deng et al. 2016
Xu et al. 2015
Zhang et al. 2015
Jiang et al. 2014
Cetin 2014
Tang et al. 2014
Zhang et al. 2014
Wang et al. 2014
10A-4
0.01
1 100
Concentration (ng/g)
10A4
10*6
Figure 4-10. Concentration of DecaBDE (ng/g) in soil for background (2007 to 2017) and near
facility (2014 to 2016) locations. For each year, the range of values reported is presented by
the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within.
Page 38 of 190
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Tue et al. 2013
llyas et al. 2011
Zhang et al. 2011
Qin et al. 2011
Gao et al. 2011
Shi et al. 2009
Luo et al. 2009
Li et al. 2008
Yang et al. 2008
Malcolm Pirnie Inc 1979
10M
0.01
1 100
Concentration (ng/g)
10A4
10*6
Figure 4-11. Concentration of DecaBDE (ng/g) in soil for near facility locations from 1979 to
2013. For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
The above figures for soil contain data for the following: (Yadav et al.. 2017; Deng et al.. 2016; Li
et al.. 2016b; McGrath et al.. 2016; Wei et al.. 2016; Sun et al.. 2015; Wu et al.. 2015; Xu et al..
2015a; Zhang et al.. 2015b; Zhang et al.. 2015a; Cetin. 2014; Jiang et al.. 2014; Liu et al.. 2014a;
Tang et al.. 2014a; Wang et al.. 2014; Zhang et al.. 2014b; Tue et al.. 2013; Chen et al.. 2012a;
Jiang et al.. 2012; Ni et al.. 2012; Gao et al.. 2011; llyas et al.. 2011a; Meng et al.. 2011; Qin et
al.. 2011; Yu et al.. 2011a; Zhang et al.. 2011b; Duan et al.. 2010; Huang et al.. 2010; Jiang et al..
2010; Li et al.. 2009; Luo et al.. 2009; Shi et al.. 2009; Sun et al.. 2009; Li et al.. 2008; Yang et al..
2008; Zou et al.. 2007; Malcolm Pirnie Inc. 1979)
Page 39 of 190
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4.5.7. Sediment
Wu et ai. 2017
Yinetal. 2017
Du et al. 2017
Wu et al. 2017
Wang et al. 2017
Su et al. 2017
Goto et al. 2017
Zhen et ai. 2016
Wang et al. 2016
Wang et al. 2016
Piazza et al. 2016
Ruczyriska et al. 2016
Mathieu and Mccall 2016
Crane and Hennes 2016
Cheng et al. 2015
Wang et al. 2015
Liu et al. 2015
Wang etal. 2015
Kukudka etal. 2015
Su et al. 2015
Lee et al. 2015
Wang et al. 2015
Zhang et al. 2015
Ma et al. 2014
Zhang etal. 2014
Zhao etal. 2013
Richman et al. 2013
Wu et al. 2013
Baron et al. 2013
Sun et al. 2013
10A-4
0.01
1 100
Concentration (ng/g)
10M
10*6
Figure 4-12. Concentration of DecaBDE (ng/g) in sediment for background locations from
2013 to 2017. For each year, the range of values reported is presented by the entire length of
the bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within.
Page 40 of 190
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ฆ background
-j near facility
He etal. 2012
La Guardia et al. 2012
Wang et al. 2012
Dodder et al. 2012
Li etal. 2012
Liu et al. 2012
Wuetal. 2012
llyas et al. 2011
Grant et al. 2011
Jiang et al. 2011
Pan et al. 2011
Dosis et al. 2011
Roosens et al. 2010
Vane et al. 2010
Ricklund et al. 2010
Wang et al. 2009
Moon et al. 2007
Xiang et al. 2007
Labandeira et al. 2007
Sudaryanto 2007
Qiu et al. 2007
Li et al. 2006
Breivik et al. 2006
Aghadadashi and Mehdinia 2016
Peverly et al. 2015
Zhang et al. 2015
Sun et al. 2013
La Guardia et al. 2012
Huetal. 2010
Guerra et al. 2010
10M
0.01
1 100
Concentration (ng/g)
10A4
10*6
Figure 4-13. Concentration of DecaBDE (ng/g) in sediment for background (2006 to 2012) and
near facility (2010 to 2016) locations. For each year, the range of values reported is presented
by the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within.
Page 41 of 190
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near facility
Ramu et al. 2010
Shi et al. 2009
Wang et al. 2007
Moon et al. 2007
Moon and Choi 2007
10A-4 0.01 1 100 10A4 10*6
Concentration (ng/g)
Figure 4-14. Concentration of DecaBDE (ng/g) in sediment for near facility locations from
2007 to 2010. For each year, the range of values reported is presented by the entire length of
the bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within.
The above figures for sediment contain data for the following: (Du et al.. 2017; Goto et al..
2017: Su et al.. 2017: Wangetal.. 2017: Wu et al.. 2017c: Wu et al.. 2017a: Yin etal.. 2017:
Aghadadashi and Mehdinia. 2016: Crane and Hennes. 2016: Mathieu and Mccall. 2016: Piazza
et al.. 2016: Ruczyriska et al.. 2016: Wang et al.. 2016a: Wang et al.. 2016b: Zhen et al.. 2016:
Cheng et al.. 2015: Kukucka et al.. 2015: Lee et al.. 2015: Liu et al.. 2015: Peverly et al.. 2015: Su
et al.. 2015b: Wang et al.. 2015a: Wang et al.. 2015c: Wang et al.. 2015b: Zhang et al.. 2015b:
Zhang et al.. 2015a: Ma et al.. 2014: Zhang et al.. 2014c: Baron et al.. 2013: Richman et al..
2013: Sun etal.. 2013: Wu et al.. 2013: Zhaoetal.. 2013a: Dodder etal.. 2012: Heetal.. 2012:
La Guardia et al.. 2012: Li et al.. 2012: Liu et al.. 2012a: Wang et al.. 2012b: Wu et al.. 2012:
Dosis et al.. 2011: Grant et al.. 2011: llyas et al.. 2011b: Jiang et al.. 2011: Pan et al.. 2011:
Guerra et al.. 2010: Hu et al.. 2010: Ramu et al.. 2010: Ricklund et al.. 2010: Roosens et al..
2010b: Vane et al.. 2010: Shi et al.. 2009: Wang et al.. 2009: Labandeira et al.. 2007: Moon et
al.. 2007a: Moon et al.. 2007b: Moon and Choi. 2007: Qiu et al.. 2007: Sudaryanto. 2007: Wang
et al.. 2007a: Xiang et al.. 2007: Breivik et al.. 2006: Li et al.. 2006b)
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4.5.8. Sludge/Biosolids
Wu et al.
Li et al.
Man et al.
Stiborova et al.
Guerra et al.
Deng et al.
Lee et al.
Lee et al.
Gorga et al.
Ilyas et al.
Daso et al.
Davis et al.
Mascolo et al.
Andrade et al.
Sanchez-Brunete et al.
Shi et al.
Ricklund et al.
Wang et al.
North
2017
2016
2015
2015
2015
2015
2014
2014
2013
2013
2012
2012
2010
2010
2009
2009
2009
2007
2004
0.01
0.1
10 100
Concentration (ng/g)
10A3
10A4
Figure 4-15. Concentration of DecaBDE (ng/g) in sludge/biosolids for near facility locations
from 2004 to 2017. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within.
This figure contains data for the following: (Wu et al.. 2017b; Li et al.. 2016a; Deng et al.. 2015;
Guerra et al.. 2015; Man et al.. 2015; Stiborova et al.. 2015; Lee et al.. 2014a; Lee et al.. 2014b;
Gorga et al.. 2013; Ilyas et al.. 2013; Daso et al.. 2012; Davis et al.. 2012; Andrade et al.. 2010;
Mascolo et al.. 2010; Ricklund et al.. 2009; Sanchez-Brunete et al.. 2009; Shi et al.. 2009; Wang
etal.. 2007b; North. 2004)
Page 43 of 190
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4.5.9. Influent/Effluent
Li et al. 2016
Deng et al. 2016
Deng et al. 2015
Man et al. 2015
Schreder and La Guardia 2014
Wang et al. 2013
Daso et al. 2012
Hope et al. 2012
Ricklund et al. 2009
North 2004
0.01 0.1 1 10 100 1000 10A4 10A5
Concentration (ng/L)
Figure 4-16. Concentration of DecaBDE (ng/L) in influent/effluent for near facility locations
from 2004 to 2016. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within.
This figure contains data for the following: (Deng et al.. 2016; Li et al.. 2016a; Deng et al.. 2015;
Man et al.. 2015; Schreder and La Guardia. 2014; Wang et al.. 2013; Daso et al.. 2012; Hope et
al.. 2012; Ricklund etal.. 2009; North. 2004)
4.5.10. Landfill Leachate
Kwan etal. 2013
near facility
Daso et al. 2013
0.1 1 10 100 1000 10A4 10A5
Concentration (ng/L)
Figure 4-17. Concentration of DecaBDE (ng/L) in landfill leachate for near facility locations in
2013. For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (Daso et al.. 2013; Kwan et al.. 2013)
Page 44 of 190
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4.5.11. Vegetation/Diet
Norrgran Engdahl et al. 2017
Shi et al. 2017
Shi et al. 2014
Chen et al. 2012
Yuet al. 2011
Mariussen et al. 2008
Wang et al. 2014
Tian et al. 2012
Yang et al. 2008
0.01
ฆ background
near facility
10 100
Concentration (ng/g)
1000
10A4
Figure 4-18. Concentration of DecaBDE (ng/g) in vegetation/diet for background (2008 to
2017) and near facility (2008 to 2014) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Norrgran Engdahl et al.. 2017; Shi et al.. 2017; Shi et
al.. 2014; Wang et al.. 2014; Chen et al.. 2012c; Tian et al.. 2012; Yu et al.. 2011a; Mariussen et
al.. 2008; Yang etal.. 2008)
4.5.12. Other
Three studies were identified that reported DecaBDE concentrations in incinerator waste and in
seawater.
4.5.12.1. Incinerator Waste
near facility
McGrath et al. 2016
1
10
100
Concentration (ng/g)
Figure 4-19. Concentration of DecaBDE (ng/g) in incinerator waste for near facility locations in
2016. The range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (McGrath et al.. 2016)
4.5.12.2. Seawater
Moeller et al. 2012
Oros et al. 2005
10A-4
0.001
0.01
Concentration (ng/L)
0.1
Figure 4-20. Concentration of DecaBDE (ng/L) in seawater for background locations in 2005
and 2012. The range of values reported is presented by the entire length of the bar.
Page 45 of 190
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This figure contains data for the following: (Moeller et al.. 2012; Pros et al.. 2005)
4.6. Biomonitoring
Many studies show that DecaBDE has been detected in a wide variety of matrices. Table 4-4
summarizes the biomonitoring data for DecaBDE identified in the peer-reviewed literature
across all matrices considered. Also included in the count are available monitoring database
sources. Only studies or databases that reported measurements of the chemical of interest
above the limit of detection were extracted and included in the "# of studies" count. The
frequency of detection is provided as a measure, across all samples in all extracted studies, of
the frequency that the chemical was measured above the limit of detection. Note, the
frequency of detection is reported only for peer-reviewed sources, unless the only data sources
available were database sources.
DecaBDE was detected in all matrices, which is generally consistent with the fate summary and
physical-chemical properties. Dietary exposure through the food-chain and trophic transfer
may contribute to presence in biological matrices.
Table 4-4. Summary of DecaBDE Biomonitoring Data from the Peer-Reviewed Literature and
Monitoring Databases
Matrix
Presence
No. of Datasets
Frequency of Detection
Human blood (serum)
Yes
30
66%
Human (other)
Yes
36
87%
Fish
Yes
20
91%
Birds
Yes
18
84%
Terrestrial invertebrates
Yes
2
86%
Aquatic invertebrates
Yes
10
90%
Terrestrial mammals
Yes
11
79%
Aquatic mammals
Yes
1
100%
Other
Yes
2
100%
The following chart provides the number of studies that have reported DecaBDE biomonitoring
data over time. For this chart, the year the study is published rather than the sampling
timeframe is used as a proxy, though for most studies, samples were collected a few years prior
to publication. Note, EPA recognizes that the sampling dates, rather than the publication date,
would be a better reflection of temporal trends.
Page 46 of 190
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Figure 4-21. Frequency of peer-reviewed publications identified that contained DecaBDE
biomonitoring data.
All biomonitoring data that passed EPA's evaluation criteria are presented graphically in the
plots below. These plots help visualize the data and are organized by study year and
microenvironment, when reported. Note, some studies are discussed in Sections 4.7 and 4.11
as they pulled together information on monitoring data alongside supplemental contextualizing
information on uses, sources, and trends.
Page 47 of 190
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4.6.1. Human blood (serum)
Thomsen et al. 2008
Bjermo et al. 2017
Abou-Elwafa Abdallah et al. 2017
Meng et al. 2016
Zhao et al. 2016
Zhou et al. 2014
Vorkamp et al. 2014
Yang et al. 2013
Chen et al. 2013
Zhao et al. 2013
Kim et al. 2012
Liu et al. 2012
Zhang et al. 2011
Wu et al. 2010
Antignac et al. 2009
Jin et al. 2009
Ren et al. 2009
Kawashiro et al. 2008
Gomara et al. 2007
Yang et al. 2013
Eguchi et al. 2012
Ren et al. 2009
Weiss et al. 2006
Li et al. 2017
Zheng et al. 2014
Zhu et al. 2009
Jakobsson et al. 2002
CTD-Canada 2018
CTD-United States 2018
0.001
ฆ general
ฆ high-end
occupational
MMDB
0.01
0.1
1 10 100
Concentration (ng/g)
1000
10A4
10A5
Figure 4-22. Concentration of DecaBDE (ng/g) in human blood (serum) for consumer (2008),
general (2007 to 2017), high-end (2006 to 2013), and occupational (2002 to 2017)
populations, as well as monitoring database results fMDI. 2002). For each year/database, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Abou-Elwafa Abdallah et al.. 2017; Bjermo et al..
2017; Li et al.. 2017; Meng et al.. 2016a; Zhao et al.. 2016b; Vorkamp et al.. 2014; Zheng et al..
2014; Zhou et al.. 2014; Chen et al.. 2013; Yang et al.. 2013; Zhao et al.. 2013b; Eguchi et al..
2012; Kim et al.. 2012; Liu et al.. 2012b; Zhang et al.. 2011a; Wu et al.. 2010a; Antignac et al..
Page 48 of 190
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2009; Jin et al.. 2009; Ren et al.. 2009; Zhu et al.. 2009; Kawashiro et al.. 2008; Thomsen et al..
2008; Gomara et al.. 2007; Weiss et al.. 2006; Jakobsson et al.. 2002).(MDI. 2002)
general
Vorkamp et al. 2014
10
100
1000
Concentration (ng/L)
Figure 4-23. Concentration of DecaBDE (ng/L) in human blood (serum) for the general
population in 2014. The range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (Vorkamp et al.. 2014)
Page 49 of 190
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4.6.2. Human (other)
| General
| high-end
occupational
Antignac et al.
Leonetti et al.
Yang et al.
Xu et al.
Abdallah and Harrad
Krol et al.
Zhou et al.
Malarvannan et al.
Zhao et al.
Tang et al.
Gascon et al.
Liu et al.
Gomara et al.
Eggesbo et al.
Sun et al.
Koh et al.
Frederiksen et al.
Antignac et al.
Jin et al.
Polder et al.
Sudaryanto et al.
Gomara et al.
She et al.
Kumsue et al.
Wu et al.
Xu et al.
Ma et al.
Malarvannan et al.
Zheng et al.
Ma et al.
2016
2016
2016
2015
2014
2014
2014
2013
2013
2013
2012
2012
2011
2011
2010
2010
2009
2009
2009
2008
2008
2007
2007
2007
2007
2015
2011
2009
2014
2012
0.001
0.01
0.1 1
Concentration (ng/g)
10
100
1000
Figure 4-24. Concentration of DecaBDE (ng/g) in human (other) for general (2007 to 2016),
high-end (2009 to 2015), and occupational (2012 to 2014) populations. For each
year/database, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
Page 50 of 190
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Ma et al. 2011
CTD-Faroe Islands 2018
CTD-Spain 2018
CTD-United States 2018
| occupational
MMDB
ฆ
0.001 0.01 0.1 1 10 100 1000
Concentration (ng/g)
Figure 4-25. Concentration of DecaBDE (ng/g) in human (other) for occupational populations
in 2011, as well as monitoring database results. For each year/database, the range of values
reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within.
The above figures for human (other) contain data for the following: (Antignac et al.. 2016;
Leonetti et al.. 2016; Yang et al.. 2016b; Xu et al.. 2015b; Abdallah and Harrad. 2014; Krol et al..
2014; Zheng et al.. 2014; Zhou et al.. 2014; Malarvannan et al.. 2013; Tang et al.. 2013; Zhao et
al.. 2013b; Gascon et al.. 2012; Liu et al.. 2012b; Eggesbp et al.. 2011; Gomara et al.. 2011; Ma
et al.. 2011; Koh et al.. 2010; Sun et al.. 2010; Antignac et al.. 2009; Frederiksen et al.. 2009; Jin
et al.. 2009; Malarvannan et al.. 2009; Polder et al.. 2008; Sudaryanto et al.. 2008; Gomara et
al.. 2007; Kumsue etal.. 2007; She etal.. 2007; Wu etal.. 2007).2 (Ma etal.. 2012; Ma et al..
2011; MDI. 2002)
4.6.2.1. Dermal Wipes
Cowell et al. 2017
general
0.2
0.22
0.24 0.26
Concentration (ng/cm2)
0.28
0.3
Figure 4-26. Concentration of DecaBDE (ng/cm2) in dermal wipes for the general population in
2017. The minimum and maximum of reported central tendency estimates are shown.
This figure contains data for the following: (Cowell et al.. 2017)
CTD 2018
MMDB
10 100 1000
Concentration (ng/wipe)
Figure 4-27. Concentration of DecaBDE (ng/wipe) in dermal wipes from a monitoring
database (CTD). The range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (MDI. 2002)
Page 51 of 190
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4.6.3. Aquatic invertebrates
Dosis et al. 2016
Pizzini et al. 2015
Poma et al. 2014
Koenig et al. 2013
Richman et al. 2013
La Guardia et al. 2012
Fu et al. 2011
Wang et al. 2009
Miyake et al. 2008
Moon et al. 2007
0.01
0.1
10 100
Concentration (ng/g)
1000
10A4
10A5
Figure 4-28. Concentration of DecaBDE (ng/g) in aquatic invertebrates for background
locations from 2007 to 2016. For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within.
This figure contains data for the following: (Dosis et al.. 2016; Pizzini et al.. 2015; Poma et al..
2014; Koenig et al.. 2013; Richman et al.. 2013; La Guardia et al.. 2012; Fu et al.. 2011; Wang et
al.. 2009; Miyake et al.. 2008; Moon et al.. 2007b)
Page 52 of 190
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4.6.4. Fish
Gandhi et al.
Koenig et al.
He et al.
Chen et al.
Mo et al.
Zhang et al.
Kuo et al.
Roosens et al.
Roots et al.
Shaw et al.
Shi et al.
Wu et al.
Guo et al.
Miyake et al.
Bogdal et al.
Guo et al.
Meng et al.
Munschy et al.
Bureau et al.
Johnson et al.
2017
2013
2012
2012
2012
2011
2010
2010
2010
2009
2009
2008
2008
2008
2007
2007
2007
2007
2006
2006
0.01
0.1
10 100
Concentration (ng/g)
1000
10M
10A5
Figure 4-29. Concentration of DecaBDE (ng/g) in fish for background locations from 2006 to
2017. For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (Gandhi et al.. 2017; Koenig et al.. 2013; Chen et al..
2012c; He et al.. 2012; Mo et al.. 2012; Zhang et al.. 2011b; Kuo et al.. 2010; Roosens et al..
2010b; Roots et al.. 2010; Shaw et al.. 2009; Shi et al.. 2009; Guo et al.. 2008; Miyake et al..
2008; Wu et al.. 2008; Bogdal et al.. 2007; Guo et al.. 2007; Meng et al.. 2007; Munschy et al..
2007; Burreau et al.. 2006; Johnson et al.. 2006)
Page 53 of 190
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4.6.5. Aquatic mammals
Shaw et al. 2009
m
background
1
1.2
1.4
Concentration (ng/g)
1.6
1.8
2
Figure 4-30. Concentration of DecaBDE (ng/g) in aquatic mammals for background locations
in 2009. The minimum and maximum of reported central tendency estimates are shown.
This figure contains data for the following: (Shaw et al.. 2009)
4.6.6. Terrestrial invertebrates
background
Yuet al. 2011
10A-6
10A-5
10M
0.001
0.01 0.1 1
10
100
1000
Concentration (ng/g)
Figure 4-31. Concentration of DecaBDE (ng/g) in terrestrial invertebrates for background
locations in 2011 and 2017. For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within.
This figure contains data for the following: (Yin et al.. 2017: Yu et al.. 2011a)
Page 54 of 190
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4.6.7. Birds
ฆ background
Fernie et al. 2017
Polder and Ju 2017
Zhao et al. 2016
Su et al. 2015
Tang et al. 2015
Gentes et al. 2015
Spears and Isanhart 2014
Chen et al. 2012
Chen et al. 2012
Mo et al. 2012
Sormo et al. 2011
Munoz-Arnanz et al. 2011
Yuet al. 2011
Sagerup et al. 2009
Johansson et al. 2009
Park et al. 2009
Shi et al. 2009
Bustnes et al. 2007
0.001 0.01 0.1
10 100 1000 10A4
Concentration (ng/g)
Figure 4-32. Concentration of DecaBDE (ng/g) in birds for background locations from 2007 to
2017. For each year, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (Fernie et al.. 2017; Polder et al.. 2017; Zhao et al..
2016a; Gentes et al.. 2015; Su et al.. 2015a; Tang et al.. 2015; Spears and Isanhart. 2014; Chen
et al.. 2012b; Chen et al.. 2012c; Mo et al.. 2012; Munoz-Arnanz et al.. 2011; Sprmo et al.. 2011;
Yu et al.. 2011a; Johansson et al.. 2009; Park et al.. 2009; Sagerup et al.. 2009; Shi et al.. 2009;
Bustnes et al.. 2007)
Page 55 of 190
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4.6.8. Terrestrial mammals
Norrgran Engdahl et al. 2017
Zhao et al. 2016
Guo et al. 2012
Shaw et al. 2012
Chen et al. 2012
Yuet al. 2011
Kunisue et al. 2008
Mariussen et al. 2008
Isobe et al. 2007
Voorspoels et al. 2006
Sormo et al. 2006
0.01
0.1
10 100
Concentration (ng/g)
1000
10A4
10A5
Figure 4-33. Concentration of DecaBDE (ng/g) in terrestrial mammals for background
locations from 2006 to 2017. For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within.
This figure contains data for the following: (Norrgran Engdahl et al.. 2017; Zhao et al.. 2016a;
Chen et al.. 2012c; Guo et al.. 2012; Shaw et al.. 2012; Yu et al.. 2011a; Kunisue et al.. 2008;
Mariussen et al.. 2008; Isobe et al.. 2007; Sprmo et al.. 2006; Voorspoels et al.. 2006)
4.6.9. Other
Two studies were identified that reported concentrations of DecaBDE in amphibians.
4.6.9.1. Amphibians
background
Zhao et al. 2016
0.01 0.1
1
10
Concentration (ng/g)
Figure 4-34. Concentration of DecaBDE (ng/g) in amphibians for background locations in 2011
and 2016. For each year, the range of values reported is presented by the entire length of the
bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within.
This figure contains data for the following: (Zhao et al.. 2016a; Liu et al.. 2011)
4.7. Trends in Monitoring Data
Several studies reported temporal trends for DecaBDE in the following media:
Indoor Dust
Page 56 of 190
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Ambient Air
Soils
Sediments
Biosolids
Humans
Aquatic Invertebrates
Fish
Birds
Those studies are summarized below.
4.7.1. Indoor Dust
Two studies reported DecaBDE levels in dust from 2004 to 2010 (Whitehead et al., 2013) and
(Yu et al., 2012). The difference between the studies appears to be greater than any trends that
are seen with time.
3000
2500
"3 2000
c
o
1500
500
ป 2214275
2007
Year
2189119
Ms
Figure 4-35. Concentration of DecaBDE (ng/g) in indoor dust from 2004 to 2010.
4.7.2. Ambient Air
One study (Strandberg et al., 2001) reported DecaBDE levels in ambient air across 4 locations
and 3 years. Again, no strong temporal trends were observed.
Page 57 of 190
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0.0004
0.00035
0.0003
0.00025
a 0.0002
0.00015
0.0001
0.00005
1998
Eagle Harbor ฆ Sturgeon Point ฆ Sleeping Bear dunes w Chicago
Figure 4-36. Concentration of DecaBDE (ng/m3) in ambient air from 1997 to 1999.
4.7.3. Soils
One study measured DecaBDE in soils (Yu et a\., 2012). Over the short, 2 year, time period of
observation, levels did appear to be increasing.
400
350
300
250
I
c
_o
200
150
ro
c
0)
u
c
s
100
50
0
2008
Year
2009
Figure 4-37. Concentration of DecaBDE (ng/g) in soils from 2008 to 2009.
Page 58 of 190
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4.7.4. Sediments
Two studies reported DecaBDE concentrations in sediments from 1974 to 2005 Kohler et al.
(2008) and Chen et al. (2007). Within the second study, data were provided for three core
samples. A general increasing trend was observed.
1 1
1
. J , 1 1 1
i i i i i i i f i i i i i i i i i i i f i i i
i
O)
ฆ9 .$> .$> $ ^ ^ ^ ^
Year
ฆ 1927729 ฆ 459965 - Core 1 ฆ 459965 - Core 2 >S 459965 - Core 3
Figure 4-38. Concentration of DecaBDE (ng/g dry weight) in sediments from 1974 to 2005.
This is corroborated by Figure 1 in Yang et al. (Yang et al.. 2016a) that presents DecaBDE
monitoring data from lake sediment cores collected throughout the United Kingdom from 1955
through 2010. DecaBDE concentrations increased steadily from 1955 to 1990, followed by a
greater rate of increase between 1990 and 2010. In addition to levels increasing with time,
DecaBDE levels were also higher in more urban lake sediments.
Increasing DecaBDE levels with time was also seen in Figures 7 and 2 of Mathieu and Mccall
(2016) and Li et al. (2006a). respectively, for lake sediment cores collected throughout
Washington state and the Great Lakes. Specifically, Mathieu and Mccall (2016) showed a sharp
increase in DecaBDE levels from the 1990s through 2010 for sediment cores from three lakes. In
Li et al. (2006a). total DecaBDE annual load to the sediment of all the Great Lakes showed a
steady increase from 1980 to 2005.
4.7.5. Biosolids
No studies were identified that could be extracted temporally. However, Figure 3 from Andrade
et al. (2015) presents time trends of DecaBDE in biosolids collected in waste water treatment
plants from the U.S. Over the time period of 2005 to 2011, levels in biosolids appear relatively
stable.
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4.7.6. Humans
One longitudinal study was identified (Darnerud et al.. 2015). which reported human blood
concentrations of DecaBDE from 1996 through 2010. Levels appear relatively stable, with a
possible peak in the early 2000's.
1.8
1.6
;v;>v:v
ft*#;
Year
Figure 4-39. Concentration of DecaBDE (ng/m3) in human blood from 1996 to 2010.
4.7.7. Aquatic Invertebrates
One monitoring database (USGS) provided three years of data for DecaBDE concentrations in
aquatic invertebrates from 2004 through 2006. No apparent trend was observed, with central
tendency concentrations decreasing and then increasing through the 3-year period. The same
lack of trend was observed for the minimum and maximum concentrations.
USGS-Tissue
0.01 0.1
Concentration (ng/g)
10
Figure 4-40. Concentration of DecaBDE (ng/g) in aquatic invertebrates from 2004 to 2006. For
each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
color within (dark blue).
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4.7.8. Fish
Figure 1 from de Boer et al. (2004) reported DecaBDE levels in Lake Ontario lake trout from
1979 through 2004. While levels appeared relatively stable until the late 1990's, a large
increase was seen in 2004.
The large increase between 2000 and 2005 was corroborated by results from one monitoring
database (USGS) which showed a similar increase after 2000 and a maximum DecaBDE
concentration in 2004. DecaBDE levels in fish were stable between 2005 and 2007 with a
decrease in 2010 and 2012.
USGS-Tissue 2000
USGS-Tissue 2001
USGS-Tissue 2002
USGS-Tissue 2003
USGS-Tissue 2004
USGS-Tissue 2005
USGS-Tissue 2006
USGS-Tissue 2007
USGS-Tissue 2010
USGS-Tissue 2012
Figure 4-41. Concentration of DecaBDE (ng/g) in fish from 2000 to 2012. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate color within (dark
blue).
4.7.9. Birds
Two studies were identified that measured levels in 4 types of bird eggs over 30 years (Baron et
al.. 2015; Johansson et al.. 2011). Dramatic increases in concentrations were seen from the
beginning of study (1974) through the early 2000's, when levels appeared to peak.
USGS-Tissue
Concentration (ng/g)
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3500
3000
2500
2000
1500
> 1000
s
j
I
1
I
:
: :
$
250
200
150
100
50
c t- (ฆ f
* *> *
9 -9 -9
^ ^ JV
$ $ $
Year
$S 1927644 - Peregrine falcon ฆ 3336454 - White stork ฆ 3336454 - Black kite O 3336454 - Greater flamingo
Figure 4-42. Concentration of DecaBDE (ng/g Iw) in bird eggs from 1974 to 2014.
This is corroborated by Figure 1 from Ismail et al. (2009) who studied DecaBDE levels in
peregrine falcon eggs in the United Kingdom. Levels appeared to increase from 1980 until the
late 1990's and then begin to decrease,
4.8. Modeled Intake and Dose Data
Eleven studies that modeled DecaBDE dose were identified: (Ali et al., 2016; Civan and Kara,
2016; Gou et al.., 2016b; Gou et al., 2016a; Polder et al,, 2016; Li et a I,. 2015a; Chao et. al., 2014;
Asante et al,. 2011; Trudel et al.. 2011; Roosens et al.. 2010a; Chen et al.. 2009). On average,
estimated doses were below 5 ng/kg/day. The highest estimated average daily dose resulted
from ingestion, followed by inhalation. Dermal exposure had a negligible contribution to
estimated doses.
Page 62 of 190
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Figure 4-43. Estimated average daily dose (ng/kg/day) of DecaBDE for inhalation (blue),
ingestion (orange), dermal (grey), and total (gold) exposure. Data are presented for infants,
toddlers, children, and adults. If available, information on the age range, exposure media,
and location of exposure are provided in the x axis description. The study year and HERO ID
(diagonal text below the year) are also provided.
In addition to modeled doses, 14 studies were identified that estimated intake of DecaBDE (Anh
et al., 2017; Han et al,, 2016; Harrad et al.. 2016; Tao et al,. 2016; Sahlstrom et al.. 2015; Jiang
et a!.. 2014; Liu et al.. 2014b; de Wit et al.. 2012; Chen et al.. 2011b; D'Hollander et al.. 2010; Jin
et ai.. 2010; U.S. EPA. 2010; Covaci et al.. 2009; Roosens et al.. 2009). Similar to modeled doses,
inhalation and ingestion exposures resulted in the highest estimates, with one toddler
inhalation estimate (Jiang et al., 2014) exceptionally high at over 4,000 ng/day. The Vietnamese
receptor group (Anh et al., 2017) showed higher ingestion estimates than other receptor
groups from the UK, U.S., China, Belgium, and Sweden.
Page 63 of 190
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5000
4000
3000
2000
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ฆ Inhalation ฆ Ingestion B Dermal ฆ Total
Figure 4-44. Estimated average intake (ng/day) of DecaBDE for inhalation (blue), ingestion
(orange), dermal (grey), and total (gold) exposure. Data are presented for infants, toddlers,
children, and adults. If available, information on the age range, exposure media, season, and
location of exposure are provided in the x axis description. The study year and HERO ID
(diagonal text below the year) are also provided.
4.9. Overview of Existing Exposure Assessments
Multiple DecaBDE assessments have been conducted, including by EPA, other U.S. and
international government agencies, and industry groups, and have been identified as
authoritative sources.
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EPA's Exposure Assessment of Polybrominated Diphenyl Ethers (PBDEs) (U.S. EPA. 2010), which
included DecaBDE, describes the PDBE exposure potential for adults, children, and infants
considering the following pathways: house dust ingestion, house dust dermal contact,
inhalation, breastmilk ingestion, milk ingestion, dairy ingestion, egg ingestion, beef ingestion,
pork ingestion, poultry ingestion, other meat ingestion, freshwater/marine fin fish ingestion,
and freshwater/marine shellfish ingestion. Adult and child exposures were dominated by dust
ingestion and dermal contact with dust, while infant exposures were dominated by breastmilk
ingestion. The next highest adult exposure pathways included milk ingestion, dairy ingestion,
and inhalation of indoor air (Table 4-5). U.S. EPA (2010) estimated a total adult intake for
DecaBDE of 1.4 x 102 ng/day, but reported only total PBDE intakes for children and infants;
DecaBDE intakes were not reported. The assessment identified household consumer products
as the main source of PBDEs in house dust.
Table 4-5. Total Adult Intake Estimates of DecaBDE (U.S. EPA. 2010). Sorted Highest to Lowest
Exposure Pathway
Estimate in ng/day
House dust ingestion
1.0 x 102
House dust dermal contact
2.5 x 101
Dairy ingestion
6.3 x 10ฐ
Milk ingestion
3.0 x 10ฐ
Inhalation
1.5 x 10ฐ
Egg ingestion
5.7 x 10"1
Pork ingestion
2.5 x 10"1
Other meats
1.9 x 10"1
Beef ingestion
1.5 x 10"1
Poultry ingestion
1.4 x 10"1
Fresh/marine finfish
9.0 x 10"2
Water ingestion
6.0 x 10"2
In its 2010 exposure assessment, EPA discussed the American Chemistry Council's Brominated
Flame Retardant Industry Panel's assessment of DecaBDE developed for the Voluntary
Children's Chemical Evaluation Program (VCCEP). The VCCEP assessment estimated DecaBDE
exposures for infants breastfed by a mother who worked in a DecaBDE formulation site, infants
breastfed by a mother who is involved in the disassembling of electronic monitors, children
mouthing DecaBDE-containing plastic electronic products, children inhaling DecaBDE
particulates released from plastic electronic products, and children exposed to DecaBDE in the
general environment [e.g., soil and dust, diet, ambient air, and water (Hays and Pyatt. 2006)1.
See Table 4-6 for the estimated intakes calculated for the pathways addressed in the VCCEP
assessment. The highest estimated exposure scenario in this assessment was the upper
estimated aggregate estimated exposure for a breast-fed infant of a mother involved in the
formulation of DecaBDE. The aggregate exposure for this scenario included the intake for
ingestion of breast milk combined with ingestion from consumer electronic products, ingestion
from mouthing fabric, and general exposures. EPA reviewed the VCCEP DecaBDE assessment in
2005 and expressed concern about dust ingestion by children via hand-to-mouth activity (U.S.
EPA. 2005b).
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Table 4-6. Intakes of DecaBDE by Children Estimated by Hays and Pyatt (2006)
Age (years) or
Lifestage
Exposu re
Pathway Specific
Mid-Range Estimate
(ng/kg/day)
Upper Estimate
(ng/kg/day)
0 to 2
Ingesting breast milk from a
mother who is involved in the
formulation of DecaBDE
(bagging operation)
1.9 x 104 (birth to 3
months)
3.4 x 105 (birth to 2 years)
0 to 2
Ingesting breast milk from a
mother who is involved in the
disassembling of electronics
3.3 x 10ฐ (birth to 3
months)
2.5 x 101 (birth to 2 years)
0 to 2
Mouthing DecaBDE-containing
plastic electronic products
4.3 x 10ฐ
2.5 x 102
0 to 2
Inhaling DecaBDE particulates
released from plastic electronic
products
3.1 x 10"1
6.3 x 10"1
Children of all ages
Exposed to DecaBDE via the
general environment (e.g., soil
and dust, diet, ambient air, and
water)
1.2 x 103
3.9 x 105
Aggregate
Infant
Intakes for ingestion of breast
milk from a mother who is
involved in the formulation of
DecaBDE, plus ingestion from
consumer electronic products,
ingestion from mouthing fabric,
and general exposures
4.6 x 104
7.6 x 105
Infant
Intakes for ingestion of breast
milk from a mother who is
involved in disassembling
DecaBDE-containing products,
plus ingestion from consumer
electronic products, ingestion
from mouthing fabric, and
general exposures
2.7 x 104
4.1 x 105
Child
Intake from general exposures
1.2 x 103
3.9 x 105
Hays and Pyatt, in the VCCEP assessment (Hays and Pyatt. 2006). included estimates of
occupational exposures for breast-feeding women. For the scenario involving disassembling
electronic monitors, they used serum levels from a study of Swedish workers; the upper level
for the analysis was 9.9 ng/g serum lipid and median level was 4.8 ng/g serum lipid (Sjodin et
al.. 1999). They used the air-serum level ratio from this study and (Sjodin et al.. 2001) to
estimate serum levels for the formulation scenario. This scenario, which was thought to be the
highest occupational exposure, was for a woman engaged in bagging DecaBDE during
manufacture or in emptying bags of DecaBDE into hoppers for formulators and compounders.
Hays and Pyatt (2006) selected as the upper air concentration level the American Industrial
Hygiene Association Workplace Environmental Exposure Level (WEEL) of 5 mg/m3 and a mid-
range estimate of 1 mg/m3 based on a European Union study that concluded that the majority
of workplace air levels were below 1 mg/m3 (ECB. 2007).
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Health Canada (2012) evaluated infant, child, and adult DecaBDE exposures via inhalation of
ambient air, inhalation of indoor air, ingestion of drinking water, ingestion of food and
beverages, ingestion of dust, infant ingestion of breastmilk, and children's oral exposure from
mouthing of hard plastic toys. Infants and children had the highest total intakes among the age
groups. Health Canada (2012) concluded that the predominant sources of exposure are breast
milk for breast-fed infants, mouthing of hard plastic toys for children ages 0.5 to 4 years of age,
and ingestion of indoor dust and food for all other age groups.
Table 4-7. Estimated Exposure of the General Population to DecaBDE from Health Canada
Assessment (Health Canada. 2012)
Age Group
Estimated Total Intake
(ng/kg/bw per day)
0 to 0.5 years (breast milk fed)
5 x 101 to 1.9 x 102
0 to 0.5 years (formula fed)
4.1 x 101
0 to 0.5 years (not formula fed)
7.9 x 101
0.5 to 4 years
8.9 x 101
5 to 11 years
3.6 x 101
12 to 19 years
1.3 x 101
20 to 59 years
9.3 x 10ฐ
60+ years
7.9 x 10ฐ
The National Academy of Sciences (NRC. 2000) developed "conservative" estimates of exposure
to flame retardants, including DecaBDE, for comparison with a reference toxicity dose
considering the following exposure pathways: adult dermal contact with DecaBDE on fabric,
adult inhalation of DecaBDE particles from eroded upholstery, adult inhalation of DecaBDE
vapor, and 1-year-old child oral exposure from repeated sucking on upholstery fabric treated
with DecaBDE. In this assessment, NAS estimated two adult dermal absorbed doses using
different assumptions regarding the absorption of DecaBDE. The first estimate of dermal-
absorbed dose assumed immediate absorption of DecaBDE (9.8 x 105 ng/kg-day), i.e., that the
skin and clothing of the person sitting on the treated fabric would offer no barrier to movement
of a non-ionic substance and there would be adequate water present (e.g., sweat) to dissolve
the nonionic substance and transfer to the skin and into the body of the person. This estimate
assumes that all of the substance that dissolves is immediately absorbed by the body. NAS
calculated an alternative iteration of dermal exposure, which had the same assumptions as the
first estimate, with the exception of the assumption of 100% immediate absorption, which was
replaced with an estimate of the rate at which the substance could penetrate the skin and
assuming the substance dissolved up to is solubility limit in water. The second dermal exposure
estimate resulted in a considerably lower dose (1.33 x 10"3 ng/kg-day). NAS' estimate of particle
time-averaged inhalation exposure concentration for a person was higher (4.8 x 102 ng/m3)
compared to its vapor inhalation estimate (3.8 x 102 ng/m3). NAS also estimated a dose for
children mouthing fabric back-coated with DecaBDE to be 2.6 x 104 ng/kg-day. They calculated
this dose based on the following exposure parameters: area density of the substance (i.e., the
mass per unit surface area), area of the fabric sucked on each occasion, fractional rate (per unit
time) of substance extraction by saliva, fraction of time a child sucks the treated fabric, and the
average body weight of a 1-year-old child. This assessment did not report total intakes.
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The European Chemicals Agency (ECHA) in its proposal for a restriction of DecaBDE (ECHA,
2014) concluded that the indoor environment is an important exposure pathway for
consumers. This ECHA assessment stated that the main routes of human exposure to DecaBDE
include exposure from food consumption, inhalation of particulate-bound DecaBDE in indoor
and outdoor air, and through skin uptake. Children aged 1 to 3 years were identified as the age
group with the highest exposures, and breastfed infants were also anticipated to be highly
exposed on a body weight basis. The assessment said that fetuses are exposed to DecaBDE
through transport across the placental barrier. That said, occupational exposures were found to
be significantly higher than consumer exposures.
The United Nations Environment Programme (UNEP) Persistent Organic Pollutants Review
Committee's risk profile of DecaBDE (UNEP. 2014) cited U.S. EPA's exposure assessment (U.S.
EPA. 2010) to support their conclusion that ingestion and dermal contact with dust, inhalation
of indoor air, and breastmilk are the dominant exposure pathways. It also noted food as a
lesser but still important pathway based on the Health Canada (2012) analysis that identified
food and dust as the main sources of exposure in adults.
4.10. Representative Exposure Scenarios
DecaBDE was produced and released at higher levels in the past, but continues to be released
under current conditions of use. Across the lifecycle, while releases from manufacturing and
processing may be declining over time, releases associated with use, disposal, and recycling are
likely to increase over time until the stock of available materials with DecaBDE is depleted. This
depletion may take several years because of how long articles are typically used before being
disposed and/or recycled. Historical and recent TRI data confirm primary releases are to air,
followed by landfill and water. When released to air, DecaBDE is likely to partition to
particulates where it can be deposited to nearby waterbodies and catchments. A large number
of monitoring studies frequently report DecaBDE in sediment.
Experimental product testing studies suggest that DecaBDE can be emitted from articles during
use through abrasion and direct transfer to dust on surfaces (Rauert and Harrad. 2015; Rauert
et al.. 2014a; Kemmlein et al.. 2006). There are a wide range of studies that have reported
DecaBDE in dust (see Section 4.5.1). Only a subset of dust-monitoring studies considers
potential indoor sources, which could contribute to levels reported in dust. However, some
studies note associations between emission rates from articles and increased levels in dust
(Liagkouridis et al.. 2016; Rauert et al.. 2014b).
Human exposure to DecaBDE has been documented. Several biomonitoring studies have
reported levels in serum and breast milk (see Sections 4.6.1 and 4.6.2). Only a subset of these
studies considers source attribution and includes exposure assessments. Those that do suggest
that indoor dust and dietary exposures are primary exposure pathways. Based on its physical-
chemical properties, ingestion is likely the primary exposure route. Inhalation would likely be
comprised of particles which could be swallowed, and dermal absorption is likely low.
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Exposure to ecological receptors has been documented. Several biomonitoring studies have
reported levels in tissues of fish, birds, and invertebrates (see Section 4.6.3 through Section
4.6.9). Only a subset of these studies considers source attribution and includes exposure
assessments. Those that do suggest that environmental and biological levels can be higher near
point sources. However, DecaBDE has also been detected in remote areas far away from point
sources indicating potential for long-range transport.
Representative Exposure Scenarios:
Ecological: Recycled electronics containing DecaBDE results in releases to air, which deposit to
nearby waterbodies and catchments, leading to increased concentrations in sediment and
uptake into organisms who ingest or reside within sediment.
Ecological: Direct releases to water and indirect releases to water (deposition from air) from
industrial processing facilities is treated at a local wastewater treatment plant. Sludge
containing elevated concentrations of DecaBDE is then land-applied where exposure to
terrestrial organisms can occur.
Consumer: Residential homes contain several electronic and textile articles with DecaBDE.
These articles can emit DecaBDE into indoor air and indoor dust through direct transfer,
abrasion, and diffusion. Indoor dust is ingested by children and leads to increased internal dose
of DecaBDE.
General Population: Air releases and deposition to soil from industrial facilities and land
application of sludge to soil result in uptake to vegetation and other edible terrestrial food
sources. Individuals who consume these dietary sources may have increased internal dose of
DecaBDE.
General Population: Direct releases to water and indirect releases to water (deposition from
air) from industrial facilities lead to elevated uptake and concentrations in edible fish species.
Individuals who consume these fish (recreational fishers) may have increased internal dose of
DecaBDE.
Occupational and General Population: Workers who are in direct contact with DecaBDE during
industrial operations breathe occupational air with elevated concentrations of DecaBDE. These
particulates are primarily ingested after inhalation leading to elevated internal dose. Workers
in this scenario who are breast-feeding may have elevated concentrations of DecaBDE in
breast-milk which can be transferred to infants during breast-feeding.
Occupational: Manufacturing of DecaBDE results in particulates that are transferred to
workplace air during transfer and packaging operations. Workers at the remaining
manufacturing facility can inhale these particulates and the particles can settle on exposed skin.
Both inhalation and dermal exposures are possible.
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Occupational: Processing of DecaBDE into plastic articles results in particulates that are
transferred to workplace air when bags of solid (powder or granular) flame retardant are
emptied into hoppers during process operations. Workers at plastic processing facilities can
inhale these particulates and the particles can settle on exposed skin. Workers can also be
exposed to liquid flame retardant formulations when small quantities of the liquid are spilled
during transfer operations. Inhalation and dermal exposures are possible from solid DecaBDE
formulations and dermal exposure is possible from liquid flame retardant formulations.
Occupational: Processing of DecaBDE into formulation, mixture, or reaction products and
subsequent incorporation into article components results in particulates that are transferred to
workplace air when bags of solid (powder or granular) flame retardant are emptied into
hoppers during process operations. Workers can inhale these particulates and the particles can
settle on exposed skin. Workers can also be exposed to liquid flame retardant formulations
when small quantities of the liquid are spilled during transfer operations. Inhalation and dermal
exposures are possible from solid DecaBDE formulations and dermal exposure is possible from
liquid flame retardant formulations.
Occupational: Recycling of plastic articles containing DecaBDE results in particulates that are
transferred to workplace air during grinding and shredding operations. Workers at recycling
facilities can inhale these particulates and the particles can settle on exposed skin. Both
inhalation and dermal exposures are possible.
Occupational: Processing of DecaBDE into textiles results in mist generated from squeezing
immersed fabric with rollers and from roll coating applications and results in particulates
generated from transfer of solid DecaBDE flame retardant formulations into mixing vessels.
Workers at these textile processing facilities can inhale these mists and particulates and
droplets or particulates can settle on exposed skin. Both inhalation and dermal exposure are
possible.
4.11. Summary of Review Articles
Many review articles for DecaBDE were identified, including several conducted in the past 2-3
years. One of the most recent reviews was a 2017 ATSDR toxicological review of PBDEs (ATSDR.
2017). ATSDR reported concentrations of DecaBDE in ambient air (<1.0 x 10"4-0.9 ng/m3),
airplane air (
-------
4.11.1. Dust
Bramwell et al. (2016) conducted a systematic review of studies published between 2007 and
2015 on human exposure to PBDEs in dust and diet and internal dose. DecaBDE was not
measured in any of the studies on dietary exposure to PBDEs, but DecaBDE was the
predominant congener found in dust in almost of all the studies. The median dust
concentration of DecaBDE in the studies ranged from 106-2,574 ng/g dry weight, with a
maximum concentration of 310,000 ng/g dry weight. Serum measurements were sparse but
ranged from below detect to 11 ng/g. However, none of the studies reported significant
associations between DecaBDE in dust and internal dose. The authors stated that this may be
due to recent advances in the ability of laboratories to more accurately measure DecaBDE,
because DecaBDE adsorbs to a much greater extent than other PBDEs increasing the difficulty
of quantification.
Coelho et al. (2014) also reviewed available published literature describing PBDE concentrations
in indoor dust from different regions of the world and different locations from 2003 to 2013.
Data from houses close to e-waste centers (high exposure) and airplanes (occasional exposure)
were excluded as the authors aim was to describe normal exposure. The highest levels of
DecaBDE were reported in car interiors (190,000 ng/g) and in the trunks of cars (2,700 ng/g) in
the U.K. Also in the U.K., the highest median level of DecaBDE in house dust was observed at
10,000 ng/g. In general, median concentrations of 1,000 ng/g were observed. The authors also
reviewed literature that matched indoor dust and human biological samples (ie serum, hair,
breast milk, cord blood) which demonstrated that indoor dust is an important exposure
pathway.
These findings are higher than those reported by Akortia et al. (2016) who report median
concentrations of DecaBDE of 141-180 ng/g dry weight in dust, but similar to ATSDR (2017) who
report dust levels up to 29,000 ng/g.
These findings are generally consistent with the monitoring data presented in Section 7.1.
4.11.2. Soil
McGrath et al. (2017) reviewed soil contamination data on PBDEs presented in English language
peer-reviewed scientific literature published up until May 2017. PBDEs have been ubiquitously
detected in soils across the world with DecaBDE as the most prevalent congener in all land-use
categories, with concentrations ranging from 0.11-8,060 ng/g dry weight. Industrial
contamination via production of PBDEs or PBDE-containing products was identified as having
the strongest potential to contaminate surrounding soils, followed by disposal via landfill,
dumping, incineration and recycling of Deca-BDE containing products. Electronic waste appears
to be one of the greatest contributors to contamination in regions where the practice is
widespread. High levels of contamination have been indicated in China and other parts of Asia
and Africa where informal methods such as burning or acid-stripping of electrical components
may enhance release of PBDEs. PBDEs have also been determined in almost all background soils
assessed including remote areas of Antarctica and northern polar regions.
Page 71 of 190
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Akortia et al. (2016) reports relatively lower levels with median measurements ranging from
10.8-28.6 ng/g dry weight in soil to 1,430 ng/g dry weight in soil.
In general, central tendency soil measurements ranged from 100 to 1,000 ng/g in the
monitoring data presented in Section 4.5.
4.11.3. Surface Water and Sediments
Iqbal et al. (2017) reviewed available published literature describing DecaBDE levels in
freshwater environments. Levels in riverine water are increasing, from below detection in the
1970's and 1980's to 2 to 200 ng/L in North American and European rivers in the 2000's. A
recent study found levels of DecaBDE in two rivers in France ranging from 2.1-295 ng/L.
DecaBDE is expected to be found bound to sediments, rather than in freshwater. Sediments
concentrations worldwide vary greatly from below the limit of detection to 100's of ng/g. This is
supported by the ATSDR findings of sediment concentrations from < 0.51-16,000 ng/g (ATSDR.
2017). DecaBDE was detected in aquatic sediments in a European river at 84 ng/g dry weight. A
study in this river reported that DecaBDE represented almost 80% of the total BDEs in surface
sediment samples. Temporally, DecaBDE concentrations have been steadily increasing in all
media across the period studied. Temporally, higher levels were detected across all media near
manufacturing sites and urban areas, but levels were also measured in remote and Arctic
environments.
Lee and Kim (2015) reviewed the available literature on the occurrence of PBDEs in the marine
environment and found concentrations ranging from 0.005-7,340 ng/g dry weight, much lower
than the levels measured in fresh waters. The authors also noted low levels of DecaBDE in
biota, and attribute this to its low potential to bioaccumulate versus to sorb to sediments.
Akortia et al. (2016) reports relatively lower levels with median sediment levels of 0.819-27,419
ng/g dry weight in fish levels of 0.01-8.2 ng/g lipid weight.
4.11.4. Human Biomonitoring
Tang and Zhai (2017) reviewed the published literature describing PBDE levels in placentas,
cord blood, and breast milk from 1996 to 2016. They reported median concentrations of
DecaBDE of up to: 45.6 ng/g lipid weight in breast milk, 27.11 ng/g lipid weight in cord blood,
and 3.3 ng/g lipid weight in placentas in countries in North America, Asia, Europe, Oceania and
Africa. The highest levels of PBDEs in human biological samples were detected at e-waste
recycling sites in South China, East China and South Korea. This is supported by reviews aimed
primarily at understanding impacts at e-waste facilities, including Sepulveda et al. (2010). The
authors also examined temporal trends and determined DecaBDE levels reached a peak in 2006
worldwide.
These findings are higher than those reported by other studies, including Akortia et al. (2016)
who report median concentrations of DecaBDE of 0.06 ng/g lipid weight in breast milk and 0.90
ng/g lipid weight in human serum and ATSDR (2017) who report levels in human blood (<0.1-
4.8 ng/g lipid weight) and breast milk (0.25-8.24 ng/g lipid weight).
Page 72 of 190
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4.11.5. Dose
Malliari and Kalantzi (2017) reviewed children's non-dietary exposure to brominated flame
retardants in indoor environments by searching peer-reviewed literature published between
2002 and 2017. They identified spatial variability, with higher DecaBDE exposure via indoor dust
in the U.S. and Europe (highest median concentration of 190,000 ng/g), and lower exposure in
the Middle East, Australia, and Africa (highest median concentration of 1,540 ng/g). In Asia,
exposure was highest near e-waste recycling areas (highest median concentration of 22,500
ng/g). By combining air and dust concentrations with accepted media intake rates, the authors
report that dust ingestion was the dominant exposure pathway for PBDEs, followed by
inhalation of indoor air. The authors reported mean daily intakes for ingestion from dust
exposure for DecaBDE: these ranged from 0.092 ng/kg bw/day in Turkey to 610 ng/kg bw/day
in the U.K. in homes, and from 0.0069 ng/kg bw/day in the U.S. to 28 ng/kg/ bw/day in the U.K.
in early childhood facilities and schools. The authors also cite studies showing dermal contact
and mouthing of toys also contribute to total exposure, however, at a lower rate than dust
ingestion.
These estimates generally align with those of U.S. EPA (2010) and Health Canada (2012) who
estimate daily intake from dust ingestion at 10 ng/day and 10-90 ng/kg/day.
5. Hexachlorobutadiene (HCBD)
5.1. Chemistry and Physical-Chemical Properties
Chemical Name
Hexachlorobutadiene
CAS RN
87-68-3
Synonyms
HCBD; Hexachloro-1,3-butadiene; 1,3-Butadiene, hexachloro-; 1,3-Butadiene,
1,1,2,3,4,4-hexachloro-; l,l,2,3,4,4-Hexachloro-l,3-butadiene; 1,3-
Hexachlorobutadiene; Perchlorobutadiene; Perchloro-1, 3-butadine;
Perchlorobutadiene; 1,3-butadiene, hexachloro-; Hexachlorobuta-l,3-diene
Molecular Formula
C4CI6
Structure
CI CI
CI CI
Source: (UNEP. 2012: HSDB. 2005)
MW
260.76
Density (g/cm3)
1.556 at 25ฐC (Havnes et al., 2014)
Molar Volume (cm3/mol)
168 [Calculated based on the molar mass and density]
Log Kow
4.78 (Hansch et al.. 1995)
Log Koa
5.2 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Log Koc
4.1 [Kow method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Vapor Pressure (mm Hg)
0.22 (Daubert and Danner. 1989)
Henry's Law (atm-m3/mol)
0.01 at 20ฐC (Warner et al.. 1987)
Water Solubility (mg/L)
3.2 (Baneriee et al.. 1980)
Water Solubility (mol/L)
1.2 x 10"5 [Calculated based on water solubility and molecular weight]
Page 73 of 190
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5.2. Uses
Since the publication of the Use Document in August 2017 for HCBD, EPA received 11 public
comments and communicated with several companies, industry groups, chemical users, and
other stakeholders to aid in identifying and verifying conditions of use of HCBD (U.S. EPA.
2017c). These interactions and comments further informed EPA's understanding of the uses for
HCBD. The information and input received from the public comments and stakeholder
engagement has been incorporated into this document to the extent appropriate. Non-
confidential public comments and stakeholder meeting summaries can be found in EPA's
docket at EPA-HQ-QPPT-2016-0738.
HCBD is primarily generated as a by-product of the manufacture of chlorinated hydrocarbons,
particularly perchloroethylene, trichloroethylene, and carbon tetrachloride, but it can also be
produced during magnesium manufacturing via electrolysis (POPRC. 2013; U.S. EPA. 2003).
According to recent reports to the UN Environmental Programme, HCBD does not appear to be
intentionally manufactured in Europe, Japan, Canada, or the United States. Intentional
production in Europe ceased as early as the late 1970s; in various other parts of the world,
production of HCBD has been restricted or banned in subsequent years; however, the chemical
continues to be manufactured as a byproduct of chemical manufacturing (Working Group of
the Basel Convention. 2016).
Table 5-1. Use Categories and Subcategories for HCBD
Life Cycle Stage
Categorya
Subcategoryb
References
Manufacture
Domestic manufacture
Manufactured byproduct
U.S. EPA (2017c)
Processing
Specialty chemical
formulation and
packaging
Specialty chemical formulation
and packaging
U.S. EPA (2017c)
Recycling
Recycling
U.S. EPA (2016d)
Industrial, Commercial,
Consumer Uses
Clothing
Children's clothing
U.S. EPA (2017c)
Solvents
Solvents used as analytical
standards
U.S. EPA (2017c)
Waste fuel
Waste fuel for cement kilns
U.S. EPA (2017c)
Other
Manufacture of drywall or
carbon spheres
U.S. EPA (2017c)
Releases and Waste
Disposal
Emissions to air
Fugitive emissions
U.S. EPA (2016d)
Point source emissions
U.S. EPA (2016d)
Water Releases
Surface water discharge
U.S. EPA (2016d); EPA-HQ-
OPPT-2016-0738
Liquid Wastes
U.S. EPA (2016d)
Solid Waste
U.S. EPA (2016d)
aThese categories of conditions of use appear in the Life Cycle Diagram, broadly represent conditions of use of HCBD in
commercial and/or consumer settings.
Page 74 of 190
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bThese subcategories reflect more specific uses of HCBD based on stakeholder outreach, and comments received on EPA's
Preliminary Information on Manufacturing, Processing, Distribution, Use, and Disposal published in August 2017.
5.3. Characterization of Expected Environmental Partitioning
If released to air, with a vapor pressure of 0.22 mm Hg, HCBD is expected to exist solely as a
vapor in the ambient atmosphere.
If released to water, based on its log Kow (4.78) and log Koc (4.1), HCBD is likely to adsorb to
sediments and suspended particulates. Its Henry's law constant of 0.01 atm m3/mole and vapor
pressure of 0.22 mm Hg indicate HCBD may partition from water into air, although adsorption
to organic matter in sediments and suspended particles may inhibit volatilization, based on the
compound's log Koc-
In wastewater treatment plants, the majority of HCBD in wastewater is expected to be removed
through adsorption to sludge and volatilization to air based on its log Koc and Henry's law
constant, but some fraction of HCBD will likely remain in the wastewater treatment plant
effluent. Biosolids containing adsorbed HCBD may be landfilled, applied to soil, or incinerated.
Effluent is typically released to surface water, where HCBD may further partition to sediments
or suspended particles or volatilize to air.
If released to soil, HCBD may volatilize from moist or dry soil due to its Henry's law constant
and vapor pressure, but volatilization from soil may be limited by adsorption to organic matter
based on the log Koc of HCBD. Based on its log Koc and water solubility (3.2 mg/L), most HCBD in
soils and groundwater will adsorb to soil or particulate organic matter but free HCBD may be
somewhat mobile in soil pore water or groundwater in subsurface environments.
If released to landfill, HCBD is expected to migrate slowly into landfill leachate based on its log
Kow, and may volatilize from solid waste based on its vapor pressure.
HBCD also may partition to the tissues of organisms that live in water, soil and sediment via
dermal or gill exposure and ingestion. Exposure to water column organisms is also possible via
resuspension of the chemical from the sediment to water either sorbed to particulates or part
of the dissolved phase. The above characterization is meant to describe the primary behavior or
movement of the chemical through a generic environment, not the complete exclusion of the
chemical from a given media (e.g., water) or elimination of the possibility for more complex
behavior in a particular location.
If released to indoor environment, HCBD in consumer products or articles, contaminated water,
or other solutions is likely to volatilize based on its vapor pressure, Henry's law constant, and
log Koa- HCBD in indoor air is not likely to adsorb to dust or other particles due to its log Koa.
Based on its water solubility and log Koc, HCBD subjected to down-the-drain disposal is
expected to enter wastewater treatment or surface water either adsorbed to organic matter or
free in the water column.
Page 75 of 190
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5.4. Overview of Lifecycle and Potential Sources of Exposure
5.4.1. Background and Brief Description of Lifecycle
HCBD is an organic compound. It is a clear, colorless, oily liquid with a mild turpentine-like odor.
It does not naturally occur. HCBD is poorly soluble in water. When released to the environment,
it is expected to volatilize quickly. Further, its vapor pressure indicates that it will evaporate
from surfaces.
HCBD is manufactured as a by-product (U.S. EPA. 2017c). It is processed as a chemical
intermediate for products including plastic additives It is used as a waste fuel, as an analytical
standard, and as a component of consumer products and drywall. The primary end-of-life
disposal options for HCBD include combustion for energy recovery in cement kilns and
incineration on-site.
MFG/IMPORT
PROCESSING
INDUSTRIAL, COMMERCIAL, CONSUMER USES"
~
RELEASES and WASTE DISPOSAL
Manufacture
and Import6
Specialty Chemical
Formulation and
Packaging*
Waste Byproduct
Recyclingb
Prepared in Solvent as Analytical
Standards
Other Uses
e.g., drywall, potential reported use in
children's products
Waste Fuel for Cement Kilnsb
Emissions to Air
Liquid Wastes
Hexachlorobutadiene
~
~ Processing
m
Past/Legacy Uses Include: plastic and rubber additives,
protective coatings, graphite rods, pesticides/agricultural
fumigants, insecticides, algicide, herbicide, recovery system for
chlorine containing gases at chlorine plants
aNo data were submitted by manufacturers (including importers) under the CDR rule for the
2016 reporting period. HCBD is manufactured as an impurity or byproduct in the manufacture
of plastic additives. It is also available for purchase from distributors based in the United States,
Europe, and Asia and may be domestically manufactured in small quantities as a specialty
chemical below the IUR reporting threshold (U.S. EPA. 2017c).
bHCBD is produced as a waste byproduct during the manufacture of certain chemicals. Per 2016 TRI data, approximately 12
million pounds of HCBD was collected and managed on-site (300,000 pounds recycled and 11.7M pounds treated) during
manufacturing and processing operations; and 27,000 pounds were collected and transferred off site as a waste fuel by cement
kilns.
Figure 5-1. Lifecycle Diagram for HCBD
Page 76 of 190
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5.4.2. Manufacturing and Import
HCBD is primarily generated as a by-product of the manufacture of chlorinated hydrocarbons,
particularly perchloroethylene, trichloroethylene, and carbon tetrachloride, but it can also be
produced during magnesium manufacturing via electrolysis. According to recent reports to the
UN Environmental Programme, HCBD does not appear to be intentionally manufactured in
Europe, Japan, Canada, or the United States. Intentional production in Europe ceased as early
as the late 1970s; in various other parts of the world, production of HCBD has been restricted or
banned in subsequent years; however, the chemical continues to be manufactured as a
byproduct of chemical manufacturing.
Various methods for HCBD synthesis have been described in two patents. HCBD can be directly
synthesized through the chlorination of butadiene or butane or produced as a by-product of
chlorinated hydrocarbon manufacturing, including perchloroethylene, trichloroethylene, and
carbon tetrachloride. It appears that HCBD generated as a by-product during the synthesis of
other compounds of interest may be recovered or recycled for commercial purposes.
Occupational dermal exposures are possible from liquid residue during transfers in process
operations. Occupational inhalation exposure to fugitive vapors are possible.
5.4.3. Processing: Plastic Additive and Chemical Intermediate
HCBD may be processed as a plastic additive and as an intermediate for a variety of products.
Releases and occupational exposures associated with intermediates are expected from
unloading and loading operations and disposal of empty transfer containers. Releases and
exposures after completion of reactions is limited to potential contact with low concentrations
of unreacted HCBD from incomplete reactions. Specific release sources and exposure pathways
to all intermediate uses of HCBD may be similar to those observed from additives in plastic
compounding and finishing operations.
Releases of additives from plastic compounding and finishing operations are possible to water,
air, and land. Releases to water can occur from the release of cooling water from forming and
molding processes where water may have direct contact with plastics, and from equipment and
general area cleaning when aqueous cleaning solutions are used (U.S. EPA. 2014a). Land
releases are possible from the disposal of off-spec product and empty transfer containers. Air
releases are expected to be minimal but are possible from fugitive releases from transfer
operations. Occupational inhalation exposures from fugitive vapors and dermal exposure from
incidental contact with liquids may occur from unloading and transfer operations when the
HCBD is added to process equipment. Once incorporated into the plastic formulation, the
potential for worker exposure is not expected.
5.4.4. Industrial/Commercial Use: Solvent as an Analytical Standard
HCBD is available for purchase from distributors in the U.S., Europe, and Asia. Laboratories are
the only known direct U.S. consumers of high purity HCBD. Most distributors sell the product in
Page 77 of 190
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small quantities and specify its intended purpose as an analytical standard or reagent [ATSDR,
1995 as cited in the (U.S. EPA. 2017c)l.
Potential releases to all media are possible from use and disposal of unused experimental
reagents and laboratory equipment that may contain residual HCBD. However, releases directly
to the environment are expected to be minimal due to handling and disposal requirements at
laboratories. Similarly, inhalation and dermal exposure to laboratory personnel is possible from
the handling of laboratory reagents; however, it is expected to be reduced by from the use of
engineering controls such as fume hoods and personal protective equipment.
5.4.5. Industrial/Commercial Use: Waste Fuel
Waste containing HCBD is blended with conventional fuels and burned in cement kilns for
energy recovery (U.S. EPA. 2017c. 2016d). The destruction and removal efficiency of these kilns
and incinerators is expected to be significant but not complete, resulting in air releases from
incinerator flue gas and land releases from disposal of ash and slag. Minor water releases from
equipment cleaning are possible. Current and historical TRI data and 2017 Discharge
Monitoring Report data confirm the primary releases are to air, with minor releases to surface
water and land (U.S. EPA. 2017c. 2016d). Occupational exposures to HCBD at cement kilns and
related incinerator facilities are expected to be minimal.
5.4.6. Consumer Use: Consumer Products
Reports from manufacturers to the State of Washington's Department of Ecology under the
Children's Safe Product Act indicate that HCBD was detected in 5 of 88 consumer products
(WSDE. 2018a). In testing completed by the State of Washington, HCBD was not detected above
method reporting limits for 80 similar consumer products (WSDE. 2018b). Reports indicate that
HCBD was detected in jewelry, surface coatings of headwear, homogenous mixtures (likely
adhesive) in underwear, and surface coatings of dolls or soft toys (WSDE. 2018a). No function
was identified for four of the five products, while protective coating was identified as a function
for the headwear product. Manufacture of these products may lead to occupational exposures.
For example, occupational exposures in the textile manufacturing industry (inhalation and
dermal exposure to organic dust and chemicals) are expected during production and packaging
operations. Use of these products, if HCBD is present, may lead to consumer exposures
(inhalation and dermal exposure) when products are worn or used.
5.4.7. Qualitative Trends Over Time for Releases and Occupational
Exposures
According to the U.N., emissions of HCBD from domestic chlor-alkali plants dropped by 93%
from 1990 to 2005. Technological changes, more effective emission controls, and the end of
HCBD use as a solvent to scrub chlorine from exhaust gasses contributed to the decline. Euro
Chlor, a trade association representing the European Chlor-Alkali industry, stated that
historically HCBD was used in agriculture (e.g., seed dressing and fungicide) as well as in the
production of aluminum and graphite rods, but its use has "virtually ceased" in response to
concerns about how persistent, bioaccumulative, and toxic it might be (U.S. EPA. 2017c).
Page 78 of 190
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Data pertaining to occupational exposure have not been identified. However, TRI data confirm
the number of reporting facilities and the total domestic release quantities to all media have
remained relatively constant since 2000 (U.S. EPA. 2016d). These data show 14 facilities
submitted reports for HCBD in 2016. Of these, 9 facilities reported manufacture in the United
States, 0 reported import, 5 reported processing operations of some type, and 9 reported other
uses. Most waste was treated on site, with significant amounts being recycled. Historical TRI
data indicate that releases to air have remained the primary medium of release with minor
releases to land, and quantities have remained constant for many years. Releases to surface
water and quantities transferred to POTWs for wastewater treatment have decreased to
minimal levels over time such that total releases to water were less than one pound in 2016
(U.S. EPA. 2016d).
5.5. Environmental Monitoring
Dozens of studies show that HCBD has been detected in a wide variety of media. Table 5-2
summarizes the monitoring data for HCBD identified in the peer-reviewed literature across all
media found. Also included in the count are available monitoring database sources. Only
studies or databases that reported measurements of the chemical of interest above the limit of
detection were extracted and included in the "# of studies" count. The frequency of detection is
provided as a measure, across all samples in all extracted studies, of the frequency that the
chemical was measured above the limit of detection. Note, the frequency of detection is
reported only for peer-reviewed sources, unless the only data sources available were database
sources.
Generally consistent with the fate summary and physical-chemical properties of HCBD, higher
concentrations were reported in ambient air, surface water, soil, and sediment. Lower
concentrations were reported in drinking water, indoor air, and sludge/biosolids. HCBD was not
reported in indoor dust or landfill leachate. HCBD was reported in influent, effluent, and in
ambient air. This is consistent with release patterns that show primary releases to air, minor
releases to water, and no or limited indoor sources of HCBD. It is of particular note that the bulk
of monitoring studies are older and represent exposures when HCBD was used more broadly or
when past use as a byproduct in the chlor-alkali industry likely resulted in higher releases.
Table 5-2. Summary of HCBD Monitoring Data from the Peer-Reviewed Literature and
Monitoring Databases
Media
Presence
No. of Datasets
Frequency of Detection
Indoor dust
No
0
n/a
Indoor air
Yes
2
100%
Ambient air
Yes
5
100%
Surface/Ground water
Yes
45
83%
Drinking water
Yes
2
100%
Soil
Yes
8
75%
Sediment
Yes
38
88%
Biosolids
Yes
1
76%
Wastewater (influent, effluent)
No
1
n/a
Page 79 of 190
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Landfill leachate
No
0
n/a
Vegetation/Diet
Yes
1
60%
Other
Yes
1
n/a
The following chart provides the number of studies that have reported HCBD monitoring data
over time. For this chart, the year the study is published rather than the sampling timeframe is
used as a proxy, though for most studies, samples were collected a few years prior to
publication. Note, EPA recognizes that the sampling dates, rather than the publication date,
would be a better reflection of temporal trends.
tf>
0>
' 1
I
J
o-
1975
1 |
1900
llJ
1985 1990 1595
faL.t
2000 2005 2010 2015
Figure 5-2. Frequency of peer-reviewed publications identified that contained HCBD
monitoring data.
All environmental monitoring data that passed EPA's evaluation criteria are presented
graphically in the plots below. These plots help visualize the data and are organized by study
year and microenvironment, when reported. Note, some studies are discussed in Sections 5.7
and 5.11 as they integrate information on monitoring data alongside supplemental
contextualizing information on uses, sources, and trends.
5.5.1. Indoor Dust
EPA did not identify any studies with extractable HCBD data in indoor dust. There are not
expected to be indoor sources of HCBD (e.g. consumer products or building materials). HCBD
present in indoor air may be related to HCBD from outdoor air sources. HCBD in indoor air is
not likely to adsorb to dust or other particles due to its log Koa. As a result, HCBD is not
expected to be present in indoor dust.
Page 80 of 190
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5.5.2. Indoor Air
1 residenti
1
1 modeled
Crump et al. 2004
ATSDR 2005
I
100
1000
10A4
10A5
10A6
Concentration (ng/m3)
Figure 5-3. Concentration of HCBD (ng/m3) in indoor air for residential locations (2004) and
modeled data (2005). For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within.
This figure contains data for the following: (ATSDR. 2005b; Crump et al.. 2004)
5.5.3. Ambient Air
near facility
ฆ modeled
MMDB
ATSDR 2006 |
Pellizzari 1982
U.S. and EPA 1976 I
1979
0.01 0.1 1 10 100 1000 10A4 10A5 10A6
Concentration (ng/m3)
Figure 5-4. Concentration of HCBD (ng/m3) in ambient air for near facility locations (1976 to
2006), modeled data (1979), and from monitoring databases (EPA AMTIC). For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
This chart contains data for the following: (ATSDR. 2006: U.S. EPA. 1990: Pellizzari. 1982:
Pellizzari etal.. 1979: U.S. EPA. 1976)
Page 81 of 190
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5.5.4. Surface Water
| background
i near facility
MMDB
Fatta et al. 2007
BartHLetal. 1998
Gotz et al. 1998
Halfon and Poulton 1992
Gomez-Belinchon et al. 1991 I
Van De Meent et al. 1986
Oliver and Kaiser 1986
Fox et al. 1983
Burkhard et al. 1997
Botta et al. 1996
Chan 1993
Harris et al. 1984
IPCHEM-AT 1989-2013
IPCHEM-BA1989-2013
IPCHEM-BE 1989-2013
IPCHEM-CH 1989-2013
IPCHEM-CY 1989-2013
IPCHEM-CZ 1989-2013
IPCHEM-DE 1989-2013
IPCHEM-DK 1989-2013
IPCHEM-ES 1989-2013 I
IPCHEM-FI 1989-2013
IPCHEM-FR 1989-2013
IPCHEM-GB 1989-2013
IPCHEM-HR 1989-2013
IPCHEM-HS 1989-2013
IPCHEM-IE 1989-2013
IPCHEM-IS 1989-2013
IPCHEM-IT 1989-2013 I
IPCHEM-LT 1989-2013 |
10A-6
10A-4
0.01 1 100
Concentration (ng/L)
10A4
10*6
Figure 5-5. Concentration of HCBD (ng/L) in surface water for background locations (1983 to
2007), near facility locations (1984 to 1997), and from monitoring databases (IPCHEM). For
each year/database, the range of values reported is presented by the entire length of the bar.
The minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
Page 82 of 190
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IPCHEM-LU 1989
IPCHEM-LV 1989-
IPCHEM-MT 1989-
IPCHEM-NL 1989-
IPCHEM-NO 1989-
IPCHEM-PL 1989
IPCHEM-PT 1989-
IPCHEM-RO 1989-
IPCHEM-RS 1989
IPCHEM-SE 1989-
IPCHEM-SI 1989
IPCHEM-SK 1989-
USGS-GW 2000-
USGS-SW 2001-
USGS 2016-
2013
2013
2013
2013
2013
2013 H
2013
2013
2013
2013
2013
2013
2016 H
2015
2017
10A-6
0.01
1 100
Concentration (ng/L)
10*6
Figure 5-6. Concentration of HCBD (ng/L) in surface water from monitoring databases
(IPCHEM, USGS). For each database, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within.
The above figures for surface water contain data for the following: (EC. 2018; Fatta et al.. 2007;
Bart H L et al.. 1998; Gotz et al.. 1998; Burkhard et al.. 1997; Botta et al.. 1996; Chan. 1993;
Halfon and Poulton. 1992; Gomez-Belinchon et al.. 1991; USGS. 1991; Oliver and Kaiser. 1986;
van de Meent et al.. 1986; Harris et al.. 1984; Fox et al.. 1983)
5.5.5. Drinking Water
| background
ฆ Modelled
ATSDR 2013
Pellizzari et al. 1979 I
0.1
1
Concentration (ug/L)
10
Figure 5-7. Concentration of HCBD (ng/L) in drinking water for background locations (2013)
and modeled data (1979). For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within.
This figure contains data for the following: (ATSDR. 2013; Pellizzari et al.. 1979)
Page 83 of 190
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5.5.6. Soil
1 background
near facility
ฆฆ modeled
ฆฆฆ MMDB
Tang et al. 2014
ATSDR 2003
ฆ
Sun et al. 2017
Tang et al. 2016
ATSDR 2005
1
U.S. EPA 1976
Naylor and Loehr 1982
USGS-Soil 1990-2015
0.
31 0.1 1 10 100 1000 10A4 10A5 10A6
Concentration (ng/g)
Figure 5-8. Concentration of HCBD (ng/g) in soil for background locations (2003 and 2014),
near facility locations (1976 to 2017), modeled data (1982), and from monitoring databases
(USGS). For each year/database, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within.
This figure contains data for the following: (Sun et al.. 2017; Tang et al.. 2016; Tang et al..
2014b: ATSDR. 2005a. 2003: USGS. 1991: DOE. 1989: Navlorand Loehr. 1982: U.S. EPA. 1976)
Page 84 of 190
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5.5.7. Sediment
Richman and Milani 2010
Lee et al. 2005
Lee et al. 2000
Bart H L et al. 1998
Lee and Fang 1997
Norton 1996
Mudroch et al. 1992
Kaiser K et al. 1990
Oliver 1987
Oliver and Pugsley 1986
Fox et al. 1983
Durham and Oliver 1983
Serdar et al. 2000
Burkhard et al. 1997
Chan 1993
Malins et al. 1985
Koelmans etal. 1997
Kaiser K et al. 1990
Oliver and Kaiser 1986
Fox et al. 1983
ICES-Dome-Denmark 1985-2016
ICES-Dome-Germany 1985-2016
iES-Dome-The Netherlands 1985-2016
IPCHEM-BE 1985-2013
IPCHEM-DE 1985-2013
IPCHEM-DK 1985-2013
IPCHEM-ES 1985-2013
IPCHEM-FR 1985-2013
IPCHEM-HS 1985-2013
IPCHEM-IT 1985-2013
10A-6
| background
ฆJ near facility
| suspended
MMOB
10A-4
0.01 1 100
Concentration (ng/g)
10A4
10*6
Figure 5-9. Concentration of HCBD (ng/g) in sediment for background locations (1983 to 2010,
near facility locations (1985 to 2000), suspended sediments (1983 to 1997), and from
monitoring databases (ICES, IPCHEM). For each year/database, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within.
Page 85 of 190
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IPCHEM-LT 1985-2013
IPCHEM-LV 1985-2013
IPCHEM-MT 1985-2013
IPCHEM-NL 1985-2013
IPCHEM-SE 1985-2013
ฆฆ
ฆ
l
I
mmdb
USGS-Sediment 1987-2014
USGS 2016
EPA GLENDA 2003-2013
10A-6 10A-4 0.01 1 100 10A4 10^
Concentration (ng/g)
Figure 5-10. Concentration of HCBD (ng/g) in sediment from monitoring databases (IPCHEM,
USGS, EPA GLENDA). For each year/database, the range of values reported is presented by
the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within.
The above figures for sediment contain data for the following: (EC. 2018; U.S. EPA. 2018b;
Richman and Milani. 2010; Lee et al.. 2005. 2000; Serdar et al.. 2000; Bart H L et al.. 1998;
Burkhard et al.. 1997; C-L and M-D. 1997; Koelmans et al.. 1997; Norton. 1996; Chan. 1993;
Mudroch et al.. 1992; USGS. 1991; Kaiser K et al.. 1990; Oliver. 1987; Oliver and Pugsley. 1986;
Oliver and Kaiser. 1986; Malins et al.. 1985; Durham and Oliver. 1983; Fox et al.. 1983)
5.5.8. Sludge/Biosolids
Zhang et al. 2014
0.01 0.1 1
Concentration (ng/g)
Figure 5-11. Concentration of HCBD (ng/g) in sludge/biosolidsfor near facility locations in
2014. The range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark color
within.
This figure contains data for the following: (Zhang et al.. 2014a)
5.5.9. Influent/Effluent
EPA DMR 2007-2017
10 100 1000 10A4 10A5 10A6 10A7
Concentration (ng/L)
Figure 5-12. Concentration of HCBD (ng/L) in influent/effluent from monitoring databases
(EPA DMR). For each database, the range of values reported is presented by the entire length
of the bar. The minimum and maximum of reported central tendency estimates are shown as
a separate dark color within.
This figure contains data for the following: (U.S. EPA. 2007)
Page 86 of 190
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5.5.10. Landfill Leachate
Of the studies searched, we did not identify any studies with detectable levels of HCBD in
landfill leachate.
5.5.11. Vegetation/Diet
Pearson and Mcconnell 1975
0.001
0.1
Concentration (ng/g)
Figure 5-13. Concentration of HCBD (ng/g) in vegetation/diet for near facility locations in
1975. The range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (Pearson and Mcconnell. 1975)
5.5.12. Other
One study was identified that reported concentrations of HCBD in seawater.
5.5.12.1. Seawater
near facility
Pearson and Mcconnell 1975
0.1
1
10
100
Concentration (ng/L)
Figure 5-14. Concentration of HCBD (ng/L) in seawater for near facility locations in 1975. The
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Pearson and Mcconnell. 1975)
5.6. Biomonitoring
Dozens of studies show that HCBD has been detected in a wide variety of matrices. Table 5-3
summarizes the biomonitoring data for HCBD identified in the peer-reviewed literature across
all matrices. Also included in the count are available monitoring database sources. Only studies
or databases that reported measurements of the chemical of interest above the limit of
detection were extracted and included in the "# of studies" count. The frequency of detection is
provided as a measure, across all samples in all extracted studies, of the frequency that the
chemical was measured above the limit of detection. Note, the frequency of detection is
reported only for peer-reviewed sources, unless the only data sources available were database
sources.
Page 87 of 190
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Table 5-3. Summary of HCBD Biomonitoring Data from the Peer-Reviewed Literature and
Monitoring Databases
Matrix
Presence
No. of Datasets
Frequency of Detection
Human blood (serum)
No
0
n/a
Human (other)
No
0
n/a
Fish
Yes
25
48%
Birds
Yes
2
27%
Terrestrial invertebrates
Yes
3
78%
Aquatic invertebrates
Yes
17
37%
Terrestrial mammals
Yes
2
66%
Aquatic mammals
No
1
n/a
Other
No
0
n/a
The following chart provides the number of studies that reported HCBD biomonitoring data
over time. For this chart, the year the study is published rather than the sampling timeframe is
used as a proxy, though for most studies, samples were collected a few years prior to
publication. Note, EPA recognizes that the sampling dates, rather than the publication date,
would be a better reflection of temporal trends.
1975 1930 1985 1990 1995 2000 2005 2010 2015
Figure 5-15. Frequency of peer-reviewed publications identified that contained HCBD
biomonitoring data.
5.6.1. Human blood (serum)
EPA did not identify any studies with detectable levels of HCBD in human blood.
Page 88 of 190
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5.6.2. Aquatic invertebrates
ฆ background
MMDB
Vorkamp et al. 2004
Oliver 1984
Fox et al. 1983
IPCHEM-DE 2000-2013
ICES-Dome-Denmark 2000-2016
ICES-Dome-Germany 2000-2016
ICES-Dome-lreland 2000-2016
ICES-Dome-Lithuania 2000-2016
CES-Dome-The Netherlands 2000-2016
ICES-Dome-United Kingdom 2000-2016
IPCHEM-ES 2000-2013
IPCHEM-FR 2000-2013
IPCHEM-GB 2000-2013
IPCHEM-IT 2000-2013
IPCHEM-NL 2000-2013
IPCHEM-SI 2000-2013
USGS-Tissue 2002-2007
0.01 1
Concentration (ng/g)
Figure 5-16. Concentration of HCBD (ng/g) in aquatic invertebrates for background locations
(1983 to 2004) and from monitoring databases (IPCHEM, ICES, USGS). For each
year/database, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (EC. 2018; ICES. 2018; Vorkamp et al.. 2004; USGS.
1991: Oliver. 1984: Fox etal.. 1983)
Page 89 of 190
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5.6.3. Fish
ฆ background
MMDB
Lava et al. 2014
Jiirgens et al. 2013
Macgregor et al. 2010
Vorkamp et al. 2004
Bart H Let al. 1998
Kuehl et al. 1994
U.S. EPA 1992
De Boer 1989
Clark et al. 1984
Goldbach et al. 1976
Yip 1976
Pearson and Mcconnell 1975
ICES-Dome-Belgium 1999-2016
ICES-Dome-Denmark 1999-2016
ICES-Dome-Finland 1999-2016
ICES-Dome-Germany 1999-2016
ICES-Dome-lreland 1999-2016
ICES-Dome-Lithuania 1999-2016
CES-Dome-The Netherlands 1999-2016
IPCHEM-CY 1999-2013
IPCHEM-DK 1999-2013
IPCHEM-EE 1999-2013
IPCHEM-IE 1999-2013
IPCHEM-NL 1999-2013
USGS-Tissue-US - National 1999-2014
10A-4
0.001
0.01
0.1 1 10
Concentration (ng/g)
100
1000
10A4
Figure 5-17. Concentration of HCBD (ng/g) in fish for background locations (1975 to 2014) and
from monitoring databases (ICES, IPCHEM, USGS). For each year/database, the range of
values reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (EC. 2018; ICES. 2018; Lava et al.. 2014; Jurgens et
al.. 2013; Macgregor et al.. 2010; Vorkamp et al.. 2004; Bart H L et al.. 1998; Kuehl et al.. 1994;
U.S. EPA. 1992; USGS. 1991; De Boer. 1989; Clark et al.. 1984; Goldbach etal.. 1976; Yip. 1976;
Pearson and Mcconnell. 1975)
Page 90 of 190
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5.6.4. Aquatic mammals
ICES-Dome-Denmark 1999-2000
MMDB
0.
D1 0.1 1 10
Concentration (ng/g)
Figure 5-18. Concentration of HCBD (ng/g) in aquatic mammals from one monitoring
database (ICES). The range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (ICES. 2018)
5.6.5. Terrestrial invertebrates
Oliver 1987
Goldbach et al. 1976
Pearson and Mcconnell 1975
0.001
0.01
0.1
1
Concentration (ng/g)
10
100
1000
Figure 5-19. Concentration of HCBD (ng/g) in terrestrial invertebrates for background
locations from 1975 to 1987. For each year, the range of values reported is presented by the
entire length of the bar. The minimum and maximum of reported central tendency estimates
are shown as a separate dark color within.
This figure contains data for the following: (Oliver. 1987: Goldbach et al.. 1976: Pearson and
Mcconnell. 1975)
5.6.6. Birds
Vorkamp et al. 2004
Pearson and Mcconnell 1975
0.001
0.1
Concentration (ng/g)
Figure 5-20. Concentration of HCBD (ng/g) in birds for background locations in 1975 and 2004.
For each year, the range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (Vorkamp et al.. 2004: Pearson and Mcconnell. 1975)
Page 91 of 190
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5.6.7. Terrestrial mammals
Vorkamp et al. 2004
background
Pearson and Mcconnell 1975
0.001
0.01
0.1
1
10
Concentration (ng/g)
Figure 5-21. Concentration of HCBD (ng/g) in terrestrial mammals for background locations in
1975 and 2004. For each year, the range of values reported is presented by the entire length
of the bar.
This figure contains data for the following: (Vorkamp et al.. 2004; Pearson and Mcconnell. 1975)
5.7. Trends in Monitoring Data
Several studies reported temporal trends for HCBD in the following media:
Ambient Air
Soils
Sediments
Influent/Effluents
Aquatic Invertebrates
Fish
Aquatic Mammals
Those studies are summarized below.
5.7.1. Ambient Air
One monitoring database (EPA AMTIC) reported HCBD levels in ambient air from 1990 through
2014 (U.S. EPA. 1990). In general, HCBD concentrations spanned three orders of magnitude,
from 101 to 104 ng/m3, with no strong temporal trends observed. From 2004 to 2006, greater
variability was observed with a larger range of concentrations detected and/or higher
maximum concentrations.
Page 92 of 190
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EPAAMTIC 1990
EPAAMTIC 1991
EPAAMTIC 1992
EPAAMTIC 1993
EPAAMTIC 1994
EPAAMTIC 1995
EPAAMTIC 1996
EPAAMTIC 1997
EPAAMTIC 1998
EPAAMTIC 1999
EPAAMTIC 2000
EPAAMTIC 2001
EPAAMTIC 2002
EPAAMTIC 2003
EPAAMTIC 2004
EPAAMTIC 2005
EPAAMTIC 2006
EPAAMTIC 2007
EPAAMTIC 2008
EPAAMTIC 2009
EPAAMTIC 2010
EPAAMTIC 2011
EPAAMTIC 2012
EPAAMTIC 2013
EPAAMTIC 2014
0.1
100 1000
Concentration (ng/m3)
10A5
Figure 5-22. Concentration of HCBD (ng/m3) in ambient air from 1990 to 2014. For each row
of data, the entire length of the bar represents the range of values reported. The darker color
within the bar shows the minimum and maximum of reported central tendency estimates.
5.7.2. Soils
Eleven years of monitoring data were reported in the USGS database for HCBD concentrations
in soils. From 1990 to 2015, no strong temporal trends were observed, with concentrations
ranging over five orders of magnitude.
Page 93 of 190
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USGS-Soil 1990
USGS-Soil 1995
USGS-Soil 1997
USGS-Soil 1998
USGS-Soil 2003
USGS-Soil 2004
USGS-Soil 2008
USGS-Soil 2009
USGS-Soil 2011
USGS-Soil 2012
USGS-Soil 2015
Figure 5-23. Concentration of HCBD (ng/g) in soils from 1990 to 2015. For each year, the range
of values reported is presented by the entire length of the bar. The minimum and maximum
of reported central tendency estimates are shown as a separate color within (dark brown).
5.7.3. Sediments
Four monitoring databases (ICES, IPCHEM, USGS, EPA GLENDA) reported concentrations of
HCBD in sediments from 1985 through 2016 (EC. 2018: ICES. 2018: U.S. EPA. 2018b: USGS.
1991). Data presented in Figure 5-24 to Error! Reference source not found, were obtained by
filtering by media and desired date range. No strong temporal trends were observed when all
databases were considered together or when databases were individually considered. From
1985 through 2008, US sediments reported higher concentrations of HCBD than sediment
concentrations from The Netherlands, Germany, Belgium, France, Malta, Spain, and Denmark.
The latter group of seven countries are part of the European Union and subject to different
regulations than the US, which may contribute to the differences observed.
10
100 1000
Concentration (ng/g)
10A4
Page 94 of 190
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ICES-Dome - The Netherlands 1985
USGS-Sediment 1987
USGS-Sediment 1988
ICES-Dome Germany 1990
IPCHEM - Germany 1990
IPCHEM - The Netherlands 1990
USGS-Sediment 1990
ICES-Dome - Germany 1991
USGS-Sediment 1991
USGS-Sediment 1993
ICES-Dome - Germany 1994
IPCHEM - The Netherlands 1994
USGS-Sediment 1994
USGS-Sediment 1995
USGS-Sediment 1996
ICES-Dome - Germany 1997
IPCHEM - The Netherlands 1997
USGS-Sediment 1997
USGS-Sediment 1998
USGS-Sediment 1999
ICES-Dome - Germany 2000
IPCHEM - The Netherlands 2000
USGS-Sediment 2000
USGS-Sediment 2001
IPCHEM - Belgium 2002
USGS-Sediment 2002
EPA GLENDA 2003
IPCHEM - Belgium 2003
USGS-Sediment 2003
EPA GLENDA 2004
10M
| ICES-Dome - The Netherlands
USGS-Sediment
| ICES-Dome. Germany
| IPCHEM-Germany
IPCHEM - The Netherlands
IPCHEM - Belgium
EPA GLENDA
0.01
1 100
Concentration (ng/g)
10A4
10-6
Figure 5-24. Concentration of HCBD (ng/g) in sediments from 1985 to 2004. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
Page 95 of 190
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USGS-Sediment 2004
EPA GLENDA 2005
IPCHEM - Belgium 2005
IPCHEM - Malta 2005
USGS-Sediment 2005
EPA GLENDA 2006
ICES-Dome - Germany 2006
IPCHEM - France 2006
IPCHEM - Germany 2006
IPCHEM - Malta 2006
IPCHEM - Spain 2006
IPCHEM - The Netherlands 2006
USGS-Sediment 2006
EPA GLENDA 2007
ICES-Dome - Denmark 2007
IPCHEM - France 2007
IPCHEM - Unclear 2007
USGS-Sediment 2007
ICES-Dome - Denmark 2008
ICES-Dome - Germany 2008
IPCHEM - Denmark 2008
IPCHEM - France 2008
IPCHEM - Germany 2008
IPCHEM - Spain 2008
IPCHEM - Sweden 2008
IPCHEM - Unclear 2008
USGS-Sediment 2008
ICES-Dome - Denmark 2009
ICES-Dome - Germany 2009
IPCHEM - France 2009
10M
USGS-Sedlmcnt
| ICES-Dome - Germany
| IPCHEM - Germany
IPCHEM - the Netherlands
IPCHEM - Belgium
EPA GLENDA
IPCHEM ฆ Malta
| IPCHEM - France
IPCHEM - Spain
ICES-Dome - Denmark
IPCHEM - Unclear
| IPCHEM - Denmark
j IPCHEM - Sweden
0.01
1 100
Concentration (ng/g)
10M
10*6
Figure 5-25. Concentration of HCBD (ng/g) in sediments from 2004 to 2009. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate color within
(darker color).
Page 96 of 190
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IPCHEM - Spain 2009
IPCHEM - The Netherlands 2009
USGS-Sediment 2009
EPA GLENDA 2010
ICES-Dome - Denmark 2010
IPCHEM - Denmark 2010
IPCHEM-France2010
EPA GLENDA 2011
ICES-Dome - Denmark 2011
ICES-Dome - Germany 2011
IPCHEM - France 2011
IPCHEM-Italy 2011
IPCHEM - Latvia 2011
IPCHEM - Lithuania 2011
USGS-Sediment 2011
ICES-Dome - Germany 2012
IPCHEM - France 2012
IPCHEM - Germany 2012
IPCHEM-Italy 2012
IPCHEM - Lithuania 2012
IPCHEM-Spain 2012
USGS-Sediment 2012
ICES-Dome - Germany 2013
IPCHEM-France 2013
IPCHEM - Lithuania 2013
USGS-Sediment 2013
ICES-Dome - Germany 2014
USGS-Sediment 2014
USGS 2016
10M
USGS-Sediment
| ICES-Dome Germany
| IPCHEM - Germany
IPCHEM - The Neffiertands
EPA GLENDA
| IPCHEM ฆ France
IPCHEM - Spain
ICES-Dome - Denmark
| IPCHEM - Denmark
| IPCHEM ฆ Italy
IPCHEM - Latvia
IPCHEM - Lithuania
USGS
0.01
1 100
Concentration (ng/g)
10A4
10*6
Figure 5-26. Concentration of HCBD (ng/g) in sediments from 2009 to 2016. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
5.7.4. Influent/Effluents
One monitoring database (EPA DMR) reported HCBD levels in the influent/effluents of
wastewater from 2007 through 2017 (U.S. EPA. 2007). A decrease in concentration was
observed between 2007 and 2011, with levels steady between 2011 and 2017.
Page 97 of 190
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EPA DMR 2007 ฆ
EPA DMR 2008
EPA DMR 2009
EPA DMR 2010
EPA DMR 2011
EPA DMR 2012
EPA DMR 2013
EPA DMR 2014
EPA DMR 2015
EPA DMR 2016
EPA DMR 2017
10A-6 10A-4 0.01 1 100 10A4 10A6
Concentration (ng/L)
Figure 5-27. Concentration of HCBD (ng/g) in influent/effluents from 2007 through 2017. For
each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
5.7.5. Aquatic Invertebrates
Three monitoring databases (ICES, IPCHEM, USGS) reported concentrations of HCBD in aquatic
invertebrates from 2000 through 2016 (EC. 2018; ICES. 2018; USGS. 1991). Data presented in
Figure 5-28 and Figure 5-29 were obtained by filtering by media and desired date range. No
strong temporal trends were observed when all databases were considered together or when
databases were individually considered. Concentrations of HCBD in aquatic invertebrate were
all lower than 100 ng/L with the exception of the IPCHEM results reported in 2012 from
Slovenia, which had a median reported concentration of 15,000 ng/L.
Page 98 of 190
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ICES-Dome - Denmark
g IPCHEM - Denmark
ICES-Dome * United Kingdom
ฆ IPCHEM - UMtM) KlnBdom
IHBH USQ5-Tls*uc
IPCHEM - Spain
ฆ IPCHEM - France
g ICES-Dome - The Nelhertands
m IPCHEM ฆ The Neffierlands
mi ICES-Dome Germany
| ICES-Dome Ireland
g IPCHEM - Germany
[H ฆ IPCHEM - Ireland
BUS IPCHEM - Italy
ICES-Dome - Denmark 2000
I
IPCHEM - Denmark 2000
I
ICES-Dome - United Kingdom 2002
I
IPCHEM - United Kingdom 2002
I
USGS-Tissue 2002
ICES-Dome - United Kingdom 2003
IPCHEM - United Kingdom 2003
ฆ
ICES-Dome - United Kingdom 2004
I
IPCHEM - United Kingdom 2004
I
IPCHEM - Spain 2005
I
USGS-Tissue 2005
IPCHEM - Spain 2006
I
USGS-Tissue 2006
USGS-Tissue 2007
IPCHEM - France 2008
I
ICES-Dome - The Netherlands 2009
ฆฆ
IPCHEM - France 2009
I
IPCHEM - The Netherlands 2009
ICES-Dome - The Netherlands 2010
IPCHEM - France 2010
I
IPCHEM - The Netherlands 2010
ICES-Dome - Germany 2011
ฆ
ICES-Dome - Ireland 2011
ICES-Dome - The Netherlands 2011
I
ICES-Dome - United Kingdom 2011
I
IPCHEM - France 2011
I
IPCHEM - Germany 2011
hi
IPCHEM - Ireland 2011
IPCHEM-Italy 2011
IPCHEM - The Netherlands 2011
0.01
100 10*4
Concentration (ng/g)
Figure 5-28. Concentration of HCBD (ng/g) in aquatic invertebrates from 2000 through 2011.
For each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
Page 99 of 190
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IPCHEM - United Kingdom 2011
ICES-Dome - Germany 2012
ICES-Dome - Ireland 2012
ICES-Dome - The Netherlands 2012
ICES-Dome - United Kingdom 2012
IPCHEM - France 2012
IPCHEM - Ireland 2012
IPCHEM-Italy 2012
IPCHEM - Slovenia 2012
IPCHEM - The Netherlands 2012
IPCHEM - United Kingdom 2012
ICES-Dome - Germany 2013
ICES-Dome - Ireland 2013
ICES-Dome - Lithuania 2013
ICES-Dome - The Netherlands 2013
ICES-Dome - United Kingdom 2013
IPCHEM - Ireland 2013
IPCHEM - Lithuania 2013
IPCHEM - The Netherlands 2013
IPCHEM - United Kingdom 2013
ICES-Dome - Germany 2014
ICES-Dome - Ireland 2014
ICES-Dome - The Netherlands 2014
ICES-Dome - United Kingdom 2014
ICES-Dome - Belgium 2016
ICES-Dome - Germany 2016
ICES-Dome - The Netherlands 2016
ICES-Dome - United Kingdom 2016
| ICES-Dome - United Kingdom
IPCHEM - OmlMf Kingdom
IPCHEM ฆ Franc*
ICES-Dome - The Nelhcrtands
| IPCHEM-The
| ICES-Dome - ti
ICES-Dome - Ireland
^ IPCHEM Ireland
| IPCHEM ฆ Italy
IPCHEM ฆ Slovenia
ICES-Dome - Lithuania
IPCHEM - Lithuania
ICES-Dome - BctgKim
0.01
100
10*4
Concentration (ng/g)
Figure 5-29. Concentration of HCBD (ng/g) in aquatic invertebrates from 2011 through 2016.
For each year, the range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
5.7.6. Fish
Three monitoring databases (USGS, ICES, IPCHEM) reported concentrations of HCBD in fish
from 1999 through 2016 (EC. 2018; ICES, 2018; USGS. 1991). Data presented in Figure 5-30 and
Figure 5-31 were obtained by filtering by media and desired date range. When considering the
Page 100 of 190
-------
median reported concentrations, HCBD concentrations were stable in fish from the U.S. from
1999 to 2003, followed by a decrease from 2005 to 2007. No other strong temporal trends
were observed.
USGS-Tissue 1998
ICES-Dome - Denmark 1999
IPCHEM - Denmark 1999
USGS-Tissue 1999
ICES-Dome ฆ Denmark 2000
IPCHEM - Denmark 2000
USGS-Tissue 2000
USGS-Tissue 2001
USGS-Tissue 2002
USGS-Tissue 2003
USGS-Tissue 2004
USGS-Tissue 2005
USGS-Tissue 2006
USGS-Tissue 2007
ICES-Dome - The Netherlands 2009
IPCHEM - The Netherlands 2009
USGS-Tissue 2009
ICES-Dome - The Netherlands 2010
IPCHEM - Cyprus 2010
IPCHEM - The Netherlands 2010
USGS-Tissue 2010
ICES-Dome - The Netherlands 2011
IPCHEM - Estonia 2011
IPCHEM - The Netherlands 2011
USGS-Tissue 2011
ICES-Dome - Ireland 2012
ICES-Dome - The Netherlands 2012
IPCHEM - Cyprus 2012
IPCHEM - Estonia 2012
IPCHEM - Ireland 2012 I
mm
| USGS-Timuc
| ICES-Dome Denmark
| IPCHEM Denmark
ICES-Dome - The Netherlands
IPCHEM - The Netnerlanrts
IPC HEM - Cyprus
IPCHEM - Estonia
ICES-Dome - Ireland
ฆ IPCHEM ฆ Ireland
0.001
0.01
0.1 1
Concentration (ngig)
10
100
Figure 5-30. Concentration of HCBD (ng/g) in fish from 1998 through 2012. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
Page 101 of 190
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USGS-Tisaue
g ICES-Dome - The Nelheiland*
Iip~ IPGHEM ฆ The NeihertarHJs
ฆgi IPC MEM-Estonia
ICES-Qome - Germany
ฆ ICES-Dome - Belgium
ฆ ICES-Dome - Finland
^mi_J ICES-Dome - Lithuania
IPCHEM - The Netherlands 2012 |
USGS-Tissue 2012
ICES-Dome - Germany 2013
ICES-Dome - The Netherlands 2013
IPCHEM - Estonia 2013 |
IPCHEM - The Netherlands 2013 |
USGS-Tissue 2013
ICES-Dome - Germany 2014
ICES-Dome - The Netherlands 2014
USGS-Tissue 2014
ICES-Dome - Belgium 2016
ICES-Dome - Finland 2016
ICES-Dome - Lithuania 2016
ICES-Dome - The Netherlands 2016
0.001 0.01 0.1 1 10 100
Concentration (ngfg)
Figure 5-31. Concentration of HCBD (ng/g) in fish from 2012 through 2016. For each year, the
range of values reported is presented by the entire length of the bar. The minimum and
maximum of reported central tendency estimates are shown as a separate dark color within.
5.7.7. Aquatic Mammals
Two monitoring databases (ICES and IPCHEM) reported concentrations of HCBD in aquatic
mammals in Denmark for two years, 1999 and 2000 (EC. 2018; ICES. 2018). Results from both
databases showed an increase from 1999 to 2000.
ICES-Dome - Denmark
IPCHEM - Denmark
ICES-Dome - Denmark 2000
IPCHEM - Denmark 2000
0.01 0.1 1
Concentration (ng/g)
10
Figure 5-32. Concentration of HCBD (ng/g) in aquatic mammals in 1999 and 2000. For each
year, the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark color
within.
Page 102 of 190
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5.8. Modeled Intake and Dose Data
One study was identified that modeled dermal dose of HCBD (HHS, 2005). Adults were found to
have a slightly higher estimated dose than children ages 2-16 although all estimates were 0.04
ng/kg/day or lower.
0.05
0.04
ro
~a
~5d
go
ฃ
O
Q
ro
Q
oj
Of)
ra
>
<
0.03
0.02
0.01
HP
W>y
IP
hp up
HI
Child (2-6 yrs)
Child (7-16 yrs)
v Dermal
Adult
Figure 5-33. Estimated average daily dose (ng/kg/day) of HCBD for dermal exposure. Data are
presented for adults and two groups of children between 2-6 and 7-16 years of age.
5.9. Overview of Existing Exposure Assessments
EPA identified two risk assessments of HCBD. An assessment by Environment Canada and
Health Canada 'Canada. 2000). Priority Substances List Assessment Report:
Hexachlorobutadiene, stated that food and air appear to be the major routes of general
population exposure for HCBD. Sources of HCBD included releases during refuse combustion
and transboundary movement from foreign sources. This Canadian assessment estimated child
and adult exposures from air, drinking water, and food as well as the total intake from these
exposures; see Table 5-4. Data were insufficient to estimate intake from soil. The assessment
also identified a conservative environmental exposure value for pelagic organisms of 0.0027
Hg/L, which was the highest reported concentration of HCBD detected in the St. Clair River in
1994.
Page 103 of 190
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Table 5-4. Estimated Exposure of the General Population to HCBD (Environment Canada and
Health Canada (2000)
Age Group
Estimated Total Intake
(ng/kg/bw per day)
0 to 0.5 years
5.0 x 101 to 9.0 x 101
0.5 to 4 years
4.0 x 101 to 2.0 x 102
5 to 11 years
3.0 x 101 to 9.0 x 101
12 to 19 years
1 x 101 to 5 x 101
20 to 70 years
1 x 101 to 5 x 101
An assessment by Euro Chlor (2002) of risks to marine (North Sea) ecological receptors also
identified food as being a potentially significant source of HCBD. This assessment did not
provide unique concentrations or doses.
5.10. Representative Exposure Scenarios
HCBD is a highly regulated chemical. In tandem with increased regulation, releases of HCBD
have declined over time. This is likely due to many factors including improved control
technologies, increased use of processes that minimize waste, and required processing of waste
at hazardous waste facilities which have more stringent control technologies to reduce
emissions.
Human exposure to HCBD has limited documentation from one biomonitoring study.
Choudhary (1995) provide a review of HCBD exposure to humans and notes potential for
general population and occupational exposure at that time. The overall magnitude of exposures
has likely decreased due to lower releases and control technologies within facilities. However,
potential for human exposure remains. Based on its physical-chemical properties, inhalation is
likely the primary exposure route although ingestion and dermal exposure are possible.
Exposure to ecological receptors has been documented. Several biomonitoring studies have
reported levels in tissues of fish, birds, and invertebrates. Only a subset of these studies
considers source attribution and includes exposure assessments. Those that do suggest that
environmental and biological levels can be higher near point sources. In addition, the majority
of these monitoring studies is older and represents conditions when HCBD was likely released
to the environment in higher amounts. However, potential for ecological exposure remains as
some current releases still occur as documented through reporting to TRI, DMR, and AMTIC
databases.
Representative Exposure Scenarios:
Occupational: Byproduct generation of HCBD during manufacture of other chlorinated solvents
results in fugitive vapors during processing operations. Workers at these manufacturing
facilities can inhale these vapors. Both inhalation and dermal exposures are possible.
Occupational: Processing of HCBD into plastic articles results in fugitive vapors during unloading
and transfer operations when the formulations containing HCBD are added to process
Page 104 of 190
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equipment. Workers at these processing facilities can inhale these vapors. Both inhalation and
dermal exposures are possible.
Occupational: Industrial and commercial use of HCBD as a solvent in analytical standards results
in fugitive vapors. Laboratory workers may inhale these vapors and incidental contact with
exposed skin may occur from accidental spills during use of the standards. However, the use of
engineering controls such as fume hoods and personal protective equipment is expected to
reduce these exposures.
Occupational: Industrial and commercial use of waste derived fuel containing HCBD can result
in fugitive vapors during loading and unloading operations. Workers can inhale these vapors
and may be exposed due to accidental spills during transfer operations. However, these
exposures are expected to be minimized due to small concentrations of HCBD in the fuel and
when closed-system transfer operations are used.
Ecological: Releases to water from industrial operations during processing of HCBD into plastic
articles leads to elevated concentrations of HCBD in surface water and sediment, where
exposure to aquatic and terrestrial organisms can occur.
General Population: Releases of HBCD to air near industrial facilities from industrial and
commercial use as a waste fuel can lead to elevated concentrations of HCBD in ambient air,
where exposure to residents living near these facilities can occur.
5.11. Summary of Review Articles
Four review articles presented exposure and doses for HCBD. However, each of the review
articles was relatively dated, with publication dates ranging from 1975 to 2001.
Mumma and Lawless (1975) conducted a study between June 1973 and October 1974 to
identify possible sources and effects of a number of chemicals, including HCBD. At that time,
HCBD was only imported to the U.S., primarily as by-product, contaminant, or component of
waste materials from production of tetrachloride, perchloroethylene, and trichloroethylene.
Due to its lack of degradation, the authors recommended disposal via incineration.
The International Programme on Chemical Safety (IPCS. 1994) identified emissions from waste
and dispersive use as the main source of HCBD. Environmental transport occurs by
volatilization, adsorption to particulate matter, and subsequent deposition or sedimentation.
HCBD was predominantly found to be in sediment and biota. HCBD has been measured in urban
air below 0.5 |-ig/m3 and below 1 pg/m3 in remote areas. European freshwater concentrations
were recorded up to 2 |ag/L with mean levels below 100 ng/L. In the Great Lakes area of
Canada, much lower levels (around 1 ng/L) were measured; however, sediment levels were as
high as 120 M-g/kg dry weight. Older sediment layers from around 1960 contained higher
concentrations (up to 550 M-g/kg wet weight). Concentrations of HCBD in aquatic organisms,
birds, and mammals indicate bioaccumulation but not biomagnification. The concentrations of
HCBD in freshwater biota measured since 1980 generally do not exceed 100 M-g/kg fresh weight,
Page 105 of 190
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but in a polluted area can reach 120 mg/kg in the lipid offish. HCBD has also been detected in
human urine, blood, and tissues. One study reported occupational exposures of 1.6-12.2 mg/m3
and urine levels of up to 20 mg/L. Exposure of the general public mainly occurs indirectly via
ingestion of drinking water and food of high lipid content. Assuming a maximum concentration
of 2.5 |ag/L in contaminated drinking-water and 10 M-g/kg wet weight in contaminated fatty food
items (meat, fish, milk) and daily intakes of 2 L drinking-water, 0.3 kg meat, 0.2 kg fish and 0.5
kg milk, the authors noted a maximum total daily intake of 0.2 M-g/kg body weight can be
calculated for a 70-kg person.
Choudhary (1995) reported HCBD in 72 ambient air samples collected from urban and other
areas with expected high concentrations of HCBD at 3.6 ppt. HCBD was also detected in some
surface waters, but the incidence of detection was low (12 of 593 ambient water samples in the
EPA's STORET database). Additionally, HCBD was detected in some groundwater samples,
coastal waters of the Gulf of Mexico, and fish samples. In addition, it was detected in drinking
water at low levels and some foodstuffs in the UK and Germany, but not in the U.S. Exposures
to HCBD are also likely from occupationally related use of this compound where inhalation and
dermal contact are the most common routes of exposure.
Farrar (2001) described a study conducted by ICI (the chemical company) investigating the fate,
transport, and potential health implications resulting from the migration of HCBD in homes
near its sandstone quarries located on the bluff of the Mersey estuary close to Weston village in
England. As part of an extensive indoor monitoring program conducted by ICI, indoor air in a
small number of properties was shown to have HCBD levels greater than 0.6 ppb (24 hour time-
weighted average, the proposed toxicity benchmark), but the vast majority of properties in the
vicinity of the quarries were shown to be much lower.
More recently, Environment Canada and Health Canada (Canada. 2000), conducted an HCBD
exposure assessment and estimated daily intakes on the order of 101 to 102 ng/kg/day.
6. Phenol, Isopropylated, Phosphate (3:1)-PIP (3:1)
6.1. Chemistry and Physical-Chemical Properties
Chemical Name
Phenol, isopropylated, phosphate (3:1)
CASRN
2502-15-0
Synonyms
ITPP, PIP (3:1)
Molecular Formula
Page 106 of 190
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Structure
R"
ex
r"~0 s X)~*
Where R* = H or OH(CH3)2 and all three rings have at (east one -CH(CH3)2 group.
W
452.53
Density (g/cm3)
CAS 26967-76-0: 1.159 at 20ฐC (Kirk. 1982)
Molar Volume (cm3/mol)
390 [Calculated based on the molar mass and density]
Log Kow
9.07 [Estimated using EPISuite v4.11 (U.S. EPA. 2012)1
Log Koa
14 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Log Koc
5.7 [Kow method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Vapor Pressure (mm Hg)
2.1 x 10"8 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Henry's Law (atm-
m3/mole)
2.9 x 10"7 [Bond Method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Water Solubility (mg/L)
2.6 x 10"5 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Water Solubility (mol/L)
5.8 x 1011 [Calculated based on water solubility and molecular weight, estimated
using EPISuite v 4.11 (U.S. EPA. 2012)1
6.2. Uses
Since the publication of the Use Document in August 2017 for PIP (3:1), EPA received 15 public
comments on the Use Document and communicated with dozens of companies, industry
groups, chemical users, and other stakeholders to aid in identifying and verifying conditions of
use of PIP (3:1) (U.S. EPA. 2017e). These interactions and comments further informed EPA's
understanding of the uses for PIP (3:1). The information and input received from the public
comments and stakeholder engagement has been incorporated into this document to the
extent appropriate. Non-confidential public comments and stakeholder meeting summaries are
available in EPA's docket at EPA-HQ-QPPT-2016-0730.
As reported to the 2016 CDR, the types of processes using PIP (3:1) include incorporation into
articles, use as a chemical processing or manufacturing aid, and incorporation into a
formulation, mixture or reaction product. Because PIP (3:1) is a liquid, processing into lubricant
products and liquid flame retardants involves adding it into formulated mixtures.
PIP (3:1) is included in various formulations, where it may serve a functional purpose as a flame
retardant, plasticizer, anti-compressibility additive, anti-wear additive, or some combination of
these functions. PIP (3:1) is in hydraulic fluid, both in aviation and industrial machinery (EPA-
HQ-QPPT-2016-0730). In these hydraulic fluids, PIP (3:1) acts as a flame retardant and as an
anti-compressibility additive. It is also added to various lubricating oils, where it may act as a
flame retardant or an anti-compressibility additive. In some cases, such as lubricating oils used
in helicopter gear boxes and other circulating oils and grease for industrial equipment, its
functional purpose is as an anti-wear additive (EPA-HQ-QPPT-2016-0730).
Page 107 of 190
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PIP (3:1) is also added to various industrial products where it acts as both a plasticizer and
flame retardant. This includes epoxy coatings on the decks of shipping vessels, coatings for
pipes and insulation in construction, adhesives and sealants in insulation for pipes in chemical
plants and other manufacturing facilities (U.S. EPA. 2017e)(EPA-HQ-QPPT-2016-0730). PIP (3:1)
has been generally identified, by commenters and others, as a possible component in plastic
products and articles, including children's products, automotive, and aerospace products (U.S.
EPA. 2017e)(EPA-HQ-QPPT-2016-0730).
The uses of PIP (3:1) that are considered within the scope of the use and exposure assessment
during various life cycle stages (i.e. manufacturing, processing, use (industrial, commercial and
consumer), distribution and disposal) are depicted in Table 6-1 and the life cycle diagram
(Figure 6-1). The information is grouped according to Chemical Data Reporting (CDR) processing
codes and internationally harmonized functional, product and article use categories from the
Organisation for Economic Co-operation and Development (OECD) in combination with other
data sources (e.g., published literature and consultation with stakeholders), to provide an
overview of conditions of use.
Use categories are drawn from Instructions for Reporting for the 2016 CDR. "Industrial use"
means use at a site at which one or more chemicals or mixtures are manufactured (including
imported) or processed. "Commercial use" means the use of a chemical or a mixture containing
a chemical (including as part of an article) in a commercial enterprise providing saleable goods
or services. "Consumer use" means the use of a chemical or a mixture containing a chemical
(including as part of an article, such as furniture or clothing) when sold to or made available to
consumers for their use (U.S. EPA. 2016c).
Table 6-1. Use Categories and Subcategories for PIP (3:1)
Life Cycle Stage
Categorya
Subcategoryb
References
Manufacturing
Manufacturing
Domestic manufacturing
U.S. EPA (2016a)
Import
U.S. EPA (2016a)
Processing
Incorporated into
formulation, mixture, or
reaction product
Flame retardant in:
Plastic material and resin
manufacturing
Plastics product manufacturing
U.S. EPA (2016a); U.S. EPA
(2017e)
Aviation hydraulic fluid
U.S. EPA (2017e); EPA-HQ-
OPPT-2016-0730
Other industrial hydraulic fluid
U.S. EPA (2017e); EPA-HQ-
OPPT-2016-0730
Petroleum lubricating oils and
grease manufacturing
U.S. EPA (2016a); EPA-HQ-
OPPT-2016-0730
Paints and coatings manufacturing
- PIP 3:1 may act as a plasticizer,
flame retardant, or both
U.S. EPA (2016a); EPA-HQ-
OPPT-2016-0730
Adhesives and sealants
U.S. EPA (2017e); U.S. EPA
(2016a); EPA-HQ-OPPT-2016-
0730
Page 108 of 190
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Life Cycle Stage
Categorya
Subcategoryb
References
Processing,
incorporation into an
article
Flame retardant in
Adhesive manufacturing
Paint and coating
manufacturing
Plastic material resin
manufacturing
Transportation equipment
(PIP 3:1 may serve multiple
functional uses in these
sectors, including as a
plasticizer)
U.S. EPA (2016a); EPA-HQ-
OPPT-2016-0730
Petroleum lubricating oil and
grease manufacturing
U.S. EPA (2017e); U.S. EPA
(2016a); EPA-HQ-OPPT-2016-
0730
Synthetic rubber manufacturing
U.S. EPA (2016a)
Distribution in commerce
Distribution
Distribution in commerce
U.S. EPA (2017e); U.S. EPA
(2016a)
Industrial and commercial
use
Hydraulic fluid
Aviation hydraulic fluid used in
airplanes
U.S. EPA (2017e); U.S. EPA
(2016a); EPA-HQ-OPPT-2016-
0730
Hydraulic fluid for other industrial
functions such as mining
equipment
U.S. EPA (2017e); CDR2016,
EPA-HQ-OPPT-2016-0730
Lubricants and grease
Liquid lubricants and greases, for
example
- helicopter gear box oil
U.S. EPA (2017e); U.S. EPA
(2016a); EPA-HQ-OPPT-2016-
0730
Paints and coatings
Solvent based paint, water based
paint.
PIP (3-1) may be incorporated into
paints and coatings as a flame
retardant and plasticizer
U.S. EPA (2017e); U.S. EPA
(2016a); EPA-HQ-OPPT-2016-
0730
Adhesives and sealants
Single component adhesive such
as
-Vimasco industrial insulation
adhesive
- fasttack sealant spray
U.S. EPA (2017e); U.S. EPA
(2016a)
Consumer Use
Complex articles
Road vehicles for passengers and
goods
U.S. EPA (2017e); EPA-HQ-
OPPT-2016-0730
Other machinery, mechanical
appliances, electronic/electronic
articles
EPA-HQ-OPPT-2016-0730
Plastic articles (hard and
soft)
Furniture & furnishings, including
furniture coverings
U.S. EPA (2017e); EPA-HQ-
OPPT-2016-0730
Toys intended for children's use
(and child dedicated articles)
U.S. EPA (2017e); EPA-HQ-
OPPT-2016-0730
Other
Insulation products not covered
elsewhere
U.S. EPA (2017e); EPA-HQ-
OPPT-2016-0730
Disposal
Recycling
Incineration of lubricating oils
containing PIP (3:1) for base oil
recovery
EPA-HQ-OPPT-2016-0730
Page 109 of 190
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aThese categories of conditions of use appear in the Life Cycle Diagram, reflect CDR codes and OECD codes, and broadly
represent conditions of use of PIP (3:l)ether in industrial and/or commercial settings.
bThese subcategories reflect more specific uses of phenol, isopropylated, phosphate (3:1) ether based on stakeholder outreach,
and comments received on EPA's Preliminary Information on Manufacturing, Processing, Distribution, Use, and Disposal
published in August 2017.
Descriptions of the industrial, commercial, or consumer use categories identified from the 2017
OECD Harmonized Use Codes are summarized below (OECD. 2017b).
The "hydraulic fluid" category encompasses chemical substances, typically liquid, used for
transmitting pressure and Extreme pressure (EP)-additives; and to transfer power in hydraulic
machinery. This includes phosphate ester based hydraulic fluids for aircraft and other
machinery.
The "lubricants and greases" category encompasses chemical substances used to reduce
friction, heat generation and wear between solid surfaces. PIP (3:1) is in some lubricants and
greases in small quantities as an anti-wear additive.
The "paints and coatings" category encompasses chemical substances used to paint or coat
substrates. Phenol isopropylated phosphate is present in coatings in the insulation industry and
marine industry as a plasticizer and flame retardant, and may be found in industrial coatings
more widely. This includes paints that have been formulated with water or solvent as the main
vehicle.
The "adhesives and sealants" category encompasses chemical substances used to fasten other
materials together or prevent the passage of liquid or gas. PIP (3:1) is found as a flame
retardant and plasticizer in adhesives and sealants in the insulation industry. This includes
products that are single component adhesives and one component caulks which are premixed
in their final product formulations.
The "complex articles" category encompasses road vehicles for passengers and goods such as
cars and trucks, and machinery, mechanical appliances, electrical and electronic articles such as
computers and drills.
The "plastic articles" category encompasses consumer products made of both hard and soft
plastics, which include PIP (3:1) as a flame retardant or plasticizer, including toys intended for
children's use, and furniture and furnishings, including furniture coverings such as computer
casing and foam in furniture or mattresses.
The "other" category encompasses consumer articles not covered elsewhere, which contain PIP
(3:1) as a flame retardant.
6.3. Characterization of Expected Environmental Partitioning
If released to air, the Henry's law constant (2.9 x 10"7 atm m3/mole) and log Koa (14) of PIP (3:1)
indicate it is likely to partition from the air into water and soil or airborne particles,
Page 110 of 190
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respectively. Particulate-bound PIP (3:1) may be removed from the atmosphere via wet or dry
deposition.
If released to water, its log Kow (9.07) and log Koc (5.7), indicate PIP (3:1) released to surface
water will adsorb to sediments and particulates suspended in the water column. PIP (3:1) is not
likely to volatilize from surface water due to its Henry's law constant.
Due to its log Kow and log Koc, PIP (3:1) in wastewater is likely to be removed via adsorption to
biosolids, which may then be landfilled, land-applied, or incinerated. PIP (3:1) is not expected to
be removed from wastewater by volatilization due to its Henry's law constant. Although release
of free PIP (3:1) with wastewater treatment plant effluent is expected to be limited, some PIP
(3:1) may be adsorbed to small particles present in effluent.
If released to soil, PIP (3:1) is not expected to volatilize from moist or dry soils due to its Henry's
law constant and vapor pressure (2.1 x 10~8 mm Hg). Based on its log Koc and water solubility
(2.6 x 10"5 mg/L), PIP (3:1) is likely to adsorb to soil and particulate organic matter. Free PIP
(3:1) is not expected to be mobile in soil pore water or groundwater, but may be absorbed to
colloids and other small particles which are mobile in subsurface environments.
If released to landfill, PIP (3:1) is expected to undergo limited, slow migration from solid waste
into landfill leachate due to its log Koc and water solubility. Based on its vapor pressure and log
Koa, PIP (3:1) is not likely to volatilize from solid waste.
PIP (3:1) also may partition to the tissues of organisms that live in water, soil, and sediment via
dermal or gill exposure and ingestion. Exposure to water column organisms is also possible via
resuspension of the chemical from the sediment to water either sorbed to particulates or part
of the dissolved phase. The above characterization is meant to describe the primary behavior or
movement of the chemical through a generic environment, not the complete exclusion of the
chemical from a given media (e.g., water) or elimination of the possibility for more complex
behavior in a particular location.
If released to the indoor environment, based on its vapor pressure and Henry's law constant,
PIP (3:1) is not likely to volatilize from consumer products or articles, contaminated water, or
other solutions. Any phenol, isopropylated, phosphate (3:1) that is emitted to indoor air is
expected to partition to organic matter including dust due to its log Koa. PIP (3:1) is most likely
to be emitted from consumer products via abrasion or direct partitioning to dust and other
particulates.
PIP (3:1) that is disposed down the drain with wastewater is expected to be associated with
organic matter in the wastewater based on its log Koc, and concentrations of free PIP (3:1) in
the water column will be limited.
Page 111 of 190
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6.4. Overview of Lifecycle and Potential Sources of Exposure
6.4.1. Background and Brief Description of Lifecycle
PIP (3:1) belongs to the group of triaryl phosphates and is a type of organophosphate ester. It is
a mixture of as many as 50 unspecified isomers. PIP (3:1) is primarily incorporated into flexible
polyurethane foam, plasticizers, and lubricants as a flame retardant. It is used as a component
in consumer products such as furniture and furnishings. It is also used in a variety of industrial
or commercial liquids such as hydraulic fluid, greases, paints, coatings, and adhesives. The end-
of-life disposal options for products containing PIP (3:1) include disposal in landfills, recycling,
and incineration (EPA-HQ-OPPT-2016-0730).
MFG/IMPORT
PROCESSING
INDUSTRIAL, COMMERCIAL, CONSUMER USES*
RELEASES and WASTE DISPOSAL
Manufacture
and Import
(6.0 million lbs a)
~
Incorporated into
Formulation, Mixture,
or Reaction Products
As a flame retardant,
lubricant additive, flexible
polyurethane foam, and
plasticizer
Incorporated into
Articles
As a flame retardant and
lubricant additive
Repackaging
Recycling
^ Processing
Hydraulic Fluid
e.g., aviation hydraulic fluid and other industrial
machinery
Lubricants and Greases
e.g., liquid lubricants and greases
Paints and Coatings
e.g., solvent based paint and water based paint
Adhesives and Sealants
e.g. single component laminating adhesives
Complex Articles
e.g., road vehicles, other machinery and
electronic articles
Plastic Articles (hard and soft)
e.g., furniture & furnishings, children's products
Other
e.g., insulation products not covered elsewhere
~
Emissions to Air
Liquid Wastes
Solid Wastes
Phenol,
isopropylated,
phosphate (3:1)
(PIP (3:1))
*Past/Legacy Uses Include: Solvent in photographic printing and
processing, asbestos abatement and other construction products
aCDR data for 2015.
Figure 6-1. Lifecycle Diagram for PIP (3:1)
6.4.2. Manufacturing
Triaryl phosphates are manufactured from phosphorous oxychloride and phenol. The
manufacturing process is carried out in closed reactors and the hydrogen chloride gas
generated during the reaction absorbed in water. One manufacturer indicated the process has
three stages of reaction followed by a distillation stage. From distillation, PIP (3:1) can be
recycled back to the first reactor as needed. The product is sent through a batch washing step
to remove small contaminants. Dehydration and filtration steps then remove water and any
further solids to make a clear product. The final product is transferred to temporary storage
until use or sale. This process occurs in continuous, closed operations except during the batch
Page 112 of 190
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washing step, which is performed under vacuum. Hydration and filtration is also a closed
system.
Generally, there is no waste produced in the manufacture of the chemical with almost 100
percent of the material recycled back into the reactors. However, fugitive air releases from
various process steps, water releases from separation and drying steps as well as equipment
and area cleaning, and land releases from disposal of spent filters are expected (EPA-HQ-OPPT-
2016-0730). Inhalation exposures from fugitive emissions during the reaction, drying, and
transfer operations may occur. Incidental dermal exposure from product sampling and transfer
operations may also occur (EPA-HQ-QPPT-2016-0730).
Table 6-2. Production Volume of Phenol, Isopropylated, Phosphate (3:1)
CDR Reporting
Year
2010
2011
2012
2013
2014
2015
Production
Volume (lb)
12,362,683
14,932,040
3,191,017
2,968,861
5,632,272
5,951,318
6.4.3. Processing: Incorporation into Formulation, Mixture, or Reaction
Products
PIP (3:1) is used as a formulation component and incorporated into mixtures for a variety of
products including plastic resins, hydraulic fluids, lubricating oils and grease, and adhesives and
sealants. Releases to air, water, and land are expected from the associated unit operations. The
primary sources of release include container residue, process equipment cleaning, and off-spec
products (OECD. 2009). Although PIP (3:1) has a low vapor pressure, fugitive air emissions may
occur from unloading, transfer into process equipment, and packaging of the final product.
Releases to water may result from equipment and general area cleaning with aqueous cleaning
materials. Land releases may occur from disposal of empty transport containers and off-spec
product. Inhalation exposure to fugitive vapors is expected to be minimal due to the low vapor
pressure, but inhalation exposure to plastic resins containing PIP (3:1) may occur during
unloading, transfer, and processing. Dermal exposure is possible from incidental contact during
unloading and transfer operations and from product packaging (OECD. 2009).
6.4.4. Processing: Incorporation into Articles
PIP (3:1) is an additive flame retardant that is used in a variety of articles including plastic
resins, foam, and synthetic rubber. Flame retardants in general are incorporated into products
in one of two manners. They are either chemically bound to the product matrix as "reactive"
mixtures, or they are dissolved in the polymer materials as "additives." Additive flame
retardants are not chemically bound and are relatively unattached to the polymer matrix.
Therefore, they have the potential of migrating from products to the surrounding environment
during manufacture, normal use, and disposal (Verslycke et al.. 2005).
Flexible polyurethane foam is manufactured in "slabstock" or "molded" forms. The slabstock
manufacturing process generates continuous slabs of foam or buns which are cut to shape for
the finished product. Typically, buns cure for 24 hours before fabrication or shipping and off
Page 113 of 190
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gassing may occur. Fugitive and stack (or point) air releases of PIP (3:1) may occur from gasses
generated from this and other processes. Releases to land are expected from disposal of waste
foam generated from cutting operations, floor sweepings, and disposal of empty transport
containers. Releases to water are possible from equipment and general area cleaning
operations. Inhalation exposure to volatile emissions from curing and unloading operations may
occur. Inhalation and dermal exposure to particulates may also occur during the cutting and
finishing steps that can generate fugitive dust. Molded foam is produced when the
polymerization occurs in a closed mold resembling the shape of the final product. Similar
releases and occupational exposures are expected (U.S. EPA. 2005a).
Releases of additives from rubber manufacturing are possible to water, air, and land. Water
releases are expected to be most prevalent. Sources include processed wastewater from
cooling or heating medium and vulcanization, where water has direct contact with the rubber
mixture. Releases to water can also occur from equipment and general area cleaning with
aqueous cleaning solutions (OECD. 2004). Land releases are possible from the disposal of off-
spec product and empty transfer containers. Air releases are expected to be minimal; however,
fugitive air releases are possible. Occupational inhalation exposure to fugitive vapors is
possible, and incidental dermal exposure is expected during unloading and transfer operations
when the PIP (3:1) is added to process equipment. Once incorporated into the rubber
formulation and reacted, worker exposure is not expected (OECD. 2004).
6.4.5. Industrial Use: Hydraulic Fluid / Lubricants and Greases
Organophosphate esters are among the most widely used classes of synthetic compounds in
hydraulic fluids, in part because they impart better fire resistance than mineral oils and are
better lubricants than water. PIP (3:1) is used in aviation and industrial machinery hydraulic
fluid EPA-HQ-QPPT-2016-0730. In these hydraulic fluids, PIP (3:1) acts as a flame retardant and
as an anti-compressibility additive. After the useful life of the hydraulic oils, the used oil is
recovered for reuse or incinerated. PIP (3:1) is also added to various lubricating oils, where
again it may act as a flame retardant or an anti-compressibility additive. In some cases, such as
lubricating oils used in helicopter gear boxes and other circulating oils and grease for industrial
equipment, its functional purpose is as an anti-wear additive (Akin Gump; Shell).
PIP (3:l)is added to formulations during the manufacture of hydraulic fluids, lubricants, and
greases in batch blending processes and incorporated into equipment for use (e.g., aircraft and
automotive) (EPA-HQ-QPPT-2016-0730). Fugitive air releases of PIP (3:1) are expected to be
minimal due to its low vapor pressure. Water and land releases are not expected from waste
hydraulic fluids and greases because used fluids and grease are typically collected for reuse or
incineration (EPA-HQ-QPPT-2016-0730). Dermal exposure to PIP (3:1) (full hand immersion,
splashing, or spraying) is expected from handling hydraulic fluids, lubricants and greases.
Inhalation exposure to fugitive vapors is expected to be minimal, but possible; inhalation
exposure to mist is possible if the fluid is spray-applied. Transportation workers aside from
those who regularly handle these fluids can also be exposed to hydraulic fluid vapor; for
example, airline crews exposed to hydraulic or engine oil smoke or fumes (Austrian Federal
Ministry of Agriculture. 2013).
Page 114 of 190
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6.4.6. Industrial/Commercial Use: Paints and Coatings / Adhesives and
Sealants
PIP (3:1) is added to coatings, adhesives, and sealants for a variety of industrial uses. This
includes epoxy coatings on the decks of shipping vessels, coatings for pipes and insulation in
construction, and adhesives and sealants in pipe insulation in chemical plants and other
manufacturing facilities (Akzo Nobel; Vimasco). Potential application methods of these coatings
to industrial substrates may include roll, dip, and spray processes. The quantity of releases and
level of occupational exposures varies with each process; however, each presents possible
releases to all media (air, water, land) and exposure to all routes (inhalation to vapors or mists
and dermal exposure to liquids). Release sources include: fugitive air emissions of vapors from
transfer operations and the application process, and overspray if spray application is used;
water releases from equipment cleaning with aqueous cleaning solutions and waste from bath
dumps; and land releases from empty transfer containers and substrate trimming or other
finishing processes. Inhalation exposure to fugitive vapors from transfer operations, equipment
cleaning, and application processes may occur. Inhalation exposure to mists is expected if a
spray or roll coating application process is used. Each of these processes is also expected to
result in dermal exposure (OECD. 2009).
6.4.7. Consumer Use: Complex Articles / Plastic Articles / Other
PIP (3:1) has been generally identified by commenters and others as a possible component in
plastic products and articles, including children's, automotive, and aerospace products (EPA-
HQ-QPPT-2016-0730).
6.4.8. Qualitative Trends Over Time for Releases for Releases and
Occupational Exposures
PIP (3:1) is not reported to the Toxics Release Inventory and no release data over time were
identified. However, the production and use of PIP (3:1) may have increased since the flame
retardant pentabromodiphenylether was banned and phased out of production in 2013. Since
that time, a prominent flame retardant formulation with PIP (3:1) as a component began to be
used in increasing quantities in upholstered furniture, infant products, and other items, such
that it became one of the most commonly detected flame retardants in the U.S. (NTP. 2013).
Releases to various media of this flame retardant may have increased proportionally with an
increase in production and use volume. Conversely, some products identified in August 2017,
including intumescent firestop and asbestos abatement products, are no longer in commerce,
or no longer include PIP (3:1) in their formulations (EPA-HQ-QPPT-2016-0730).
6.5. Environmental Monitoring
PIP (3:1) was detected in relatively few environmental monitoring studies. A supplemental
search for PIP (3:1) was conducted to determine if any studies co-reported information on aryl
phosphate chemicals. A few studies reported PIP (3:1) itself in environmental media. The
chemical most reported in environmental media from the supplemental search is Triphenyl
Page 115 of 190
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Phosphate (TPP). TPP and PIP (3:1) can be found in the same mixture, formulation, or article.
Instead, Table 6-3 provides a summary of the monitoring data for PIP (3:1) and TPP identified in
the peer-reviewed literature across all media considered. Also included in the count are
available monitoring database sources. Only studies or databases that reported measurements
of the chemical of interest above the limit of detection were extracted and included in the "# of
studies" count. The frequency of detection is provided as a measure, across all samples in all
extracted studies, of the frequency that the chemical was measured above the limit of
detection. Note, the frequency of detection is reported only for peer-reviewed sources, unless
the only data sources available were database sources.
This is generally consistent with the fate summary and reported physical-chemical properties in
that PIP (3:1) was detected in indoor dust, soil, ambient air, and sediment in higher
concentrations and was not reported in other media. However, reported uses indicate higher
likelihood of release to water and no detections in water were found.
Table 6-3. Summary of PIP (3:1) and TPP Monitoring Data from the Peer-Reviewed Literature
Media
Presence
No. of Datasets
Frequency of Detection
Indoor dust
Yes
29
95%
Indoor air
Yes
9
62%
Ambient air
Yes
2
87%
Surface/Ground water
No
0
n/a
Drinking water
No
0
n/a
Soil
Yes
2
38%
Sediment
Yes
3
66%
Biosolids
No
0
n/a
Wastewater (influent, effluent)
No
0
n/a
Landfill leachate
No
0
n/a
Vegetation/Diet
No
0
n/a
Other
No
0
n/a
The following chart provides the number of studies that have reported PIP (3:1) monitoring
data over time. For this chart, the year the study is published rather than the sampling
timeframe is used as a proxy, though for most studies, samples were collected a few years prior
to publication. Note, EPA recognizes that the sampling dates, rather than the publication date,
would be a better reflection of temporal trends.
Page 116 of 190
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Figure 6-2. Frequency of peer-reviewed publications identified that contained PIP (3:1) and
TPP monitoring data.
All environmental monitoring data that passed EPA's evaluation criteria are presented
graphically in the plots below. These plots help visualize the data and are organized by study
year and microenvironment, when reported. Note, some studies are discussed in Sections 6.7
and 6.11 as they pulled together information on monitoring data alongside supplemental
contextualizing information on uses, sources, and trends.
Page 117 of 190
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6.5.1. Indoor Dust
ฆ commercial
ฆ residential
Muenhor et al. 2018
Persson et al. 2018
Larsson et al. 2018
Zheng et al. 2017
Bjomsdotter et al. 2017
Xu et al. 2016
He et al. 2015
Ali et al. 2012
Muenhor et al. 2018
Zheng et al. 2017
Sugeng et al. 2017
Bjomsdotter et al. 2017
Coelho et al. 2016
Ballesteros-Gomez et al. 2016
Zheng et al. 2015
He et al. 2015
Araki et al. 2014
Fromme et al. 2014
Cequier et al. 2014
Brandsma et al. 2014
Kim et al. 2013
Ali et al. 2012
Ali et al. 2012
Bergh et al. 2011
Kanazawa et al. 2010
Meeker and Stapleton 2010
Stapleton et al. 2009
Bjomsdotter et al. 2017
Brandsma et al. 2014
0.1
100 1000 10A4
Concentration (ng/g)
10A7
Figure 6-3. Concentration of PIP (3:1) and TPP (ng/g) in indoor dust for commercial locations
2012 to 2018), residential locations (2009 to 2018), and vehicles (2014 and 2017). For each
year, the range of values reported is presented by the entire length of the bar. The minimum
and maximum of reported central tendency estimates are shown as a separate dark color
within.
This figure contains data for the following: (Larsson et al.. 2018; Muenhor et al.. 2018; Persson
et al.. 2018; Bjomsdotter et al.. 2017; Sugeng et al.. 2017; Zheng et al.. 2017; Ballesteros-Gomez
et al.. 2016; Coelho et al.. 2016; Xu et al.. 2016; He et al.. 2015; Zheng et al.. 2015a; Araki et al..
2014; Brandsma et al.. 2014; Cequier et al.. 2014; Kim et al.. 2013; Ali et al.. 2012b; Ali et al..
2012a; Bergh et al.. 2011; Kanazawa et al.. 2010; Meeker and Stapleton. 2010; Stapleton et al..
2009)
Page 118 of 190
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6.5.2. Indoor Air
ฆ commercial
Persson et al. 2018
Xu et al. 2016
Saito et al. 2007
Fromme et al. 2014 |
Cequier et al. 2014
Bergh et al. 2011
Kanazawa et al. 2010
Saito et al. 2007
Otake et al. 2004
10A-6
10A-5 10A-4 0.001 0.01 0.1
Concentration (ng/m3)
10
100
Figure 6-4. Concentration of PIP (3:1) and TPP (ng/m3) in indoor air for commercial (2007 to
2018) and residential (2004 to 2014) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Persson et al.. 2018; Xu et al.. 2016; Cequier et al..
2014; Fromme et al.. 2014; Bergh et al.. 2011; Kanazawa et al.. 2010; Saito et al.. 2007; Otake et
al.. 2004)
6.5.3. Ambient Air
background
| occupational
Xu et al. 2016
0.001
0.01
0.1
1 10
Concentration (ng/m3)
Figure 6-5. Concentration of PIP (3:1) and TPP (ng/m3) in ambient air for background (2014)
and occupational (2016) locations. For each year, the range of values reported is presented by
the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within.
This figure contains data for the following: (Xu et al.. 2016; Salamova et al.. 2014)
6.5.4. Soil
Matsukami et al. 2015
David and Seiber 1999
1
10
100
Concentration (ng/g)
1000
10A4
Figure 6-6. Concentration of PIP (3:1) and TPP (ng/g) in soil for near facility (1999 and 2015)
locations. For each year, the range of values reported is presented by the entire length of the
Page 119 of 190
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bar. The minimum and maximum of reported central tendency estimates are shown as a
separate dark color within.
This figure contains data for the following: (Matsukami et al.. 2015; David and Seiber. 1999)
6.5.5. Sediment
| commercial
^ฆnea
r facility
Muenhor et al. 2018
| residential
Matsukami et al. 2015
^HSHE^pSH
Muenhor et al. 2018
I
0.1
1 10 100
1000
Concentration (ng/g)
Figure 6-7. Concentration of PIP (3:1) and TPP (ng/g) in sediment for commercial (2018), near
facility (2015), and residential (2018) locations. For each year, the range of values reported is
presented by the entire length of the bar. The minimum and maximum of reported central
tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Muenhor et al.. 2018: Matsukami et al.. 2015)
6.5.6. Other
EPA did not identify any studies with extractable PIP (3:1) nor TPP data in surface water,
drinking water, wastewater treatment plants influent or effluent, or landfill leachate. PIP (3:1) is
not expected to be present in these media due to the following:
For surface water, PIP (3:1) is expected to adsorb to sediments and particulates
suspended in the water column based on its log Kow (9.07) and log Koc (5.7).
For drinking water, PIP (3:1) is expected to adsorb to suspended particulates based on
its log Kow (9.07) and log Koc (5.7).
For wastewater treatment plants influent or effluent, due to its log Kow and log Koc, PIP
(3:1) in wastewater is likely to be removed via adsorption to biosolids, which may then
be landfilled, land-applied, or incinerated.
For landfill leachate, PIP (3:1) is expected to undergo limited, slow migration from solid
waste into landfill leachate due to its log Koc and water solubility.
Of the studies searched, EPA did not identify any studies with detectable levels of PIP (3:1) nor
TPP in sludge/biosolids or vegetation/diet.
6.6. Biomonitoring
A small number of studies show PIP (3:1) detected in any biological matrix. No monitoring data
were identified for PIP (3:1). Instead, Table 6-4 summarizes the biomonitoring data for TPP
identified in the peer reviewed literature across all matrices considered. Also included in the
count are available monitoring database sources. Only studies or databases that reported
Page 120 of 190
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measurements of the chemical of interest above the limit of detection were extracted and
included in the "# of studies" count. The frequency of detection is provided as a measure,
across all samples in all extracted studies, of the frequency that the chemical was measured
above the limit of detection. Note, the frequency of detection is reported only for peer-
reviewed sources, unless the only data sources available were database sources.
PIP (3:1) was detected in matrices where it was expected due to physical-chemical properties;
however, for many matrices, PIP (3:1) data has not been collected.
Table 6-4. Summary of TPP, a Surrogate for PIP (3:1), Biomonitoring Data from the Peer-
Reviewed Literature
Matrix
Presence
No. of Datasets
Frequency of Detection
Human blood (serum)
Yes
1
100%
Human (other)
Yes
5
85%
Fish
No
0
n/a
Birds
Yes
1
84%
Terrestrial invertebrates
No
0
n/a
Aquatic invertebrates
No
0
n/a
Terrestrial mammals
Yes
1
100%
Aquatic mammals
No
0
n/a
Other
No
0
n/a
The following chart provides the number of studies that reported TPP biomonitoring data over
time. For this chart, the year the study is published rather than the sampling timeframe is used
as a proxy, though for most studies, samples were collected a few years prior to publication.
Note, EPA recognizes that the sampling dates, rather than the publication date, would be a
better reflection of temporal trends.
J
TJ tL
3
to
o
S
jCt
e,
^1
z
2014
2015
2016
2017
2018
Figure 6-8. Frequency of peer-reviewed publications identified that contained TPP, a
surrogate for PIP (3:1), biomonitoring data.
Page 121 of 190
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6.6.1. Human blood (serum)
Hennquez-Hernandez et al. 2017
general
10
12
14
Concentration (ng/g)
16
18
20
Figure 6-9. Concentration of TPP (ng/g), a surrogate for PIP (3:1), in human blood (serum) for
the general population in 2017. The minimum and maximum of reported central tendency
estimates are shown.
This figure contains data for the following: (Hennquez-Hernandez et al.. 2017)
6.6.2. Human (other)
general
Fromme et al. 2014
10
100
1000 10A4
Concentration (ng/L)
10A5
10A6
Figure 6-10. Concentration of TPP (ng/L), a surrogate for PIP (3:1), in human (other) for the
general population in 2014 and 2015. For each year, the range of values reported is presented
by the entire length of the bar. The minimum and maximum of reported central tendency
estimates are shown as a separate dark color within.
This figure contains data for the following: (Cequier et al.. 2015: Fromme et al.. 2014)
6.6.2.1. Dermal Wipes
general
| occupational
Larsson et al. 2018
Sugeng et al. 2017
Xu et al. 2016
\
0.001 0.01 0.1
10 100 1000
Concentration (ng/wipe)
Figure 6-11. Concentration of TPP (ng/wipe), a surrogate for PIP (3:1), in dermal wipes for the
general (2017 and 2018) and occupational (2016) populations. For each year, the range of
values reported is presented by the entire length of the bar. The minimum and maximum of
reported central tendency estimates are shown as a separate dark color within.
This figure contains data for the following: (Larsson et al.. 2018: Sugeng et al.. 2017: Xu et al..
2016)
Page 122 of 190
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6.6.3. Birds
Zheng et al. 2015
0.1 022 0.34 0.46 0.58 0.7
Concentration (ng/g)
Figure 6-12. Concentration of TPP (ng/g), a surrogate for PIP (3:1), in birds for background
locations in 2015. The range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (Zheng et al.. 2015b)
6.6.4. Terrestrial mammals
Hennquez-Hernandez et al. 2017
general
20
22
24
Concentration (ng/g)
26
28
30
Figure 6-13. Concentration of TPP (ng/g), a surrogate for PIP (3:1), in terrestrial mammals for
background locations in 2017. The minimum and maximum of reported central tendency
estimates are shown.
This figure contains data for the following: (Hennquez-Hernandez et al.. 2017)
6.6.5. Other
EPA did not identify any studies with detectable levels of PIP (3:1) nor TPP in aquatic
invertebrates, fish, aquatic mammals, or terrestrial invertebrates.
6.7. Trends in Monitoring Data
EPA did not identify any studies that reported trends for PIP (3:1) nor closely-related chemicals.
Of the monitoring databases searched, no monitoring data was available for PIP (3:1).
6.8. Modeled Intake and Dose Data
Five studies modeled the average daily dose for TPP, a closely-related chemical to PIP (3:1)
(Larsson et al.. 2018: Muenhor et al.. 2018: Zheng et al.. 2017: Coelho et al.. 2016: He et al..
2015). Estimated doses were generally less than 2 ng/kg/day, with a few exceptions seen. For
He et al. (2015). the average daily dose calculated using the average concentration in dust is
presented in the figure below. The error bars represent the daily dose corresponding to
maximum concentrations in dust samples.
Page 123 of 190
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30
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Figure 6-14. Estimated average daily dose (ng/kg/day) of TPP, a closely related chemical to
PIP (3:1), for inhalation (blue), ingestion (orange), dermal (grey), and total (gold) exposure.
Data are presented for infants, toddlers, children, and adults. If available, information on the
age range and location of exposure are provided in the x axis description. The study year and
HERO ID (diagonal text below the year) are also provided. Error bars represent the average
daily dose estimated using maximum concentrations in dust samples.
In addition to modeled doses, one study estimated intake of TPP, a closely related chemical to
PIP (3:1) (Bjornsdotter et al.. 2017). An additional scenario described as a worst case scenario
was not plotted in the figure below. The worst case scenario assumed high dust ingestion and
maximum concentration in dust and resulted in estimated doses of 157, 428, 191, and 3100
ng/day for workers, drivers, non-workers, and stay-at-home toddlers, respectively.
Page 124 of 190
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40
30
>
to
"D
ฆ"a 20
c
01
2A
n
ฆt-j
c
10
0 wst&mm
Worker Driver Non-worker Stay-at-home toddler
ฆ Total
Figure 6-15. Estimated average intake (ng/day) of TPP, a closely related chemical to PIP (3:1),
for total exposure. Data are presented for workers, drivers, non-workers, and stay-at-home
toddlers.
6.9. Overview of Existing Exposure Assessments
A human health arid environmental risk evaluation of PIP (3:1) was sponsored by the
Environment Agency of the United Kingdom and Wales (and referred to as isopropylated
triphenyl phosphate) (European Environment Agency, 20091 This assessment calculated
predicted concentrations in air, soil, drinking water, food (fish, root crops, leaf crops, meat, and
milk) and reported total daily human intake from regional sources and 22 production or
application scenarios. These scenarios were based on OECD emission scenario methods for
plastic additives (i.e., polyvinyl chlorine additive), lubricants, and scenarios developed under the
UK Existing Substances Regulation for other substances with similar uses, e.g., thermoplastics
and polyurethane, textile coating, pigment dispersions, paints, and adhesives. The scenarios
predicted to have the highest total daily intakes were two polyvinyl chloride-related
scenarioscompounding and combined compounding and conversion (1.1 x 105 and 1.2 x 10s
ng/kg bw/day, respectively) and textile/fabric coatingcombined compounding and
application of coating (1.0 x 105 ng/kg bw/day). This assessment predicted total intake from
regional sources to be much lower than these industrial scenarios (3.0 x 102 ng/kg bw/day).
Page 125 of 190
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6.10. Representative Exposure Scenarios
PIP (3:1) has a wide variety of uses with potential for release and exposure. However, there is
limited data for PIP (3:1) itself to document these exposures. Human exposure to PIP (3:1) has
limited documentation from one completed assessment, and read-across monitoring data from
TPP and other aryl phosphates. Based on its physical-chemical properties, ingestion is likely the
primary exposure route. Inhalation would likely be comprised of particles which could be
swallowed, and dermal absorption is likely low. There is also limited documentation for
exposure to ecological receptors from one completed assessment, and read-across monitoring
data from TPP and other aryl phosphates.
Representative Exposure Scenarios:
Occupational: Manufacturing of PIP (3:1) results in fugitive emissions from reaction, drying, and
transfer operations. Workers can inhale these emissions and incidental dermal contact during
unloading and transfer operations can occur. Inhalation and dermal exposure to workers in
manufacturing facilities is possible.
Occupational: Processing of PIP (3:1) into articles such as plastic resins, foam, and synthetic
rubber results in generation of fugitive vapors from liquid formulations containing PIP (3:1) and
from curing steps. Fugitive dust from cutting and finishing operations can also be generated.
Workers can inhale these vapors and dusts, and particles can settle on exposed skin. Workers
can also be exposed to liquid formulations when small quantities of the liquid are spilled during
transfer operations. Both inhalation and dermal exposures are possible.
Occupational: Processing of PIP (3:1) into hydraulic fluids, lubricating oils, and grease results in
incidental dermal contact during unloading and transfer operations. Dermal exposure to
workers in these processing facilities is possible.
Occupational: Use of PIP (3:1) in hydraulic fluids, lubricating oils, and grease results in full hand
immersion, splashing, or spraying during handling. Dermal exposure to workers who use these
products is possible. Inhalation and dermal exposure to mist from spray application of these
products is also possible.
Occupational: Use of PIP (3:1) in industrial coatings. Application methods that include spray or
roll coating result in generation of mist. Inhalation of mists for workers in these facilities
performing these tasks is possible. Dermal exposure is also possible.
Ecological: Fugitive releases from manufacturing result in releases to air, which deposit to
nearby waterbodies and catchments, leading to increased concentrations in sediment and soil
and potential uptake into organisms who ingest or reside within sediment and soil.
General Population: As reported in the UK assessment, releases to air and water from
processing and use facilities leads to presence in air, soil, drinking water, and dietary sources
which contribute to intake to the general population.
Page 126 of 190
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Consumer: Residential homes may contain several articles with PIP (3:1). These articles can
emit PIP (3:1) into indoor air and indoor dust through direct transfer, abrasion, and diffusion.
Indoor air is inhaled and indoor dust is ingested by children and may lead to increased internal
dose of PIP (3:1).
6.11. Summary of Review Articles
No review articles were identified that presented exposure estimates or doses for PIP (3:1)
other than the authoritative sources presented in Section 6.9. For PIP (3:1), the United Kingdom
Environmental Agency conducted a human health and environmental risk assessment for PIP
(3:1) and predicted occupational exposures on the order of 0.1 mg/kg/day and general
population exposures on the order of 3 x 10~4 mg/kg/day driven by consumption of
contaminated fish (European Environment Agency. 2009).
From Section 6.6, human biomonitoring studies report TPP serum levels in the range of 2 ng/g.
7. 2, 4, 6-Tris(tert-butyl) Phenol (2, 4, 6-TTBP)
7.1. Chemistry and Physical-Chemical Properties
Chemical Name
2,4,6-Tris(-tert-butyl)phenol
CASRN
732-26-3
Synonyms
2,4,6 TTBP, 2,4,6-TRIS, 2,4,6-tritert-butylphenol; 2,4,6-Tri(tert-butyl)phenol; Phenol, 2,4,6-
tris(l,l-dimethylethyl); 2,4,6-Tris(tert-butyl)phenol; 2,4,6-Tri(Tert-Butyl)Phenol; 2,4,6-Tri-t-
butylphenol; 2,4,6-Tri-tert-butylphenol; 2,4,6-Tris(l,l-dimethylethyl)phenol; Phenol, 2,4,6-tri-
tert-butyl-; Polyolefin alkyl
Molecular
Formula
C18H30O
Structure
CH;
H'C\/
chs
\)
CH* / Wh,
HO
HjC \
CH;
MW
262.43
Density (g/cm3)
0.864 at 27ฐC (Havnes et al.. 2014)
Molar Volume
(cm3/mol)
304 [Calculated based on the molar mass and density]
Log Kow
6.06 (Chemicals Inspection and Testing Institute. 1992)
Log Koa
9.5 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Log Koc
4.4 [Kow method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Vapor Pressure
(mm Hg)
6.6 x 10"4 [Extrapolated from (Lilev. 1984)1
Page 127 of 190
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Henry's Law
(atm-m3/mole)
6.5xl0"6 [Calculated based on VP/WS. estimated using EPISuite v4.11 (U.S. EPA. 2012)1
Water Solubility
(mg/L)
35 (Chemicals Inspection and Testing Institute. 1992)
Water Solubility
(mol/L)c
1.3 x 10"4 [Calculated based on water solubility and molecular weight]
7.2. Uses
Use of 2,4,6 TTBP is prohibited by engineering standards of some large businesses in the U.S.
For example, Toyota's North America construction site management handbook prohibits 2,4,6
TTBP due to its ban in Japan (Toyota Motor Engineering & Manufacturing. 2007). GE's Design
Requirements for Regulated Materials and Chemicals lists 2,4,6-Tris(-tert-butyl)phenol as
prohibited from use in parts, products, or other chemical substances (General Electric
Company. 1995). In addition, IBM's Engineering Specification 46G3772 environmental
requirements prohibits lubricants containing the chemical (IBM. 2018).
Since the publication of the Use Document in August 2017 for 2,4,6 Tris(tert-butyl)phenol, EPA
received 12 public comments and communicated with several companies, industry groups,
chemical users, and other stakeholders to aid in identifying and verifying conditions of use of
2,4,6 TTBP (U.S. EPA. 2017a). These interactions and comments further informed EPA's
understanding of the uses for 2,4,6 TTBP. The information and input received from the public
comments and stakeholder engagement has been incorporated into this document to the
extent appropriate. Non-confidential public comments and stakeholder meeting summaries can
be found in EPA's docket at EPA-HQ-QPPT-2016-0734.
The primary use of 2,4,6 TTBP in the U.S. is as an intermediate and reactant in chemical
processing (U.S. EPA. 2014b). It is also used as a component of both industrial and commercial
fuel additives and lubricant additives. 2,4,6 TTBP is found in a variety of end-use products as an
antioxidant in the automotive sector including fuel and lubricant additives (U.S. EPA. 2014b).
However, it has also been identified for possible use industrially as a reactant in the production
of other organic chemicals, plastics, and resins (U.S. EPA. 2014b).
The EU's OSPAR Commission identified five potential uses of 2,4,6 TTBP in Europe: a chemical
intermediate in the production of antioxidants used in rubber and plastic; a lubricating agent in
the transportation sector; a by-product in production of 4-tert-butylphenol, an additive for
gasoline and fuel oil distillate; and use in the offshore sector (OSPAR. 2006). The OSPAR
commission also indicated that 2,4,6 TTBP is listed as an impurity in 2,6 di-tert-butylphenol at
concentration of 0.003%. However, the only use reported by industry in the EU was as a
chemical intermediate used in the production of antioxidants used in rubber and plastic; the
other potential uses were not confirmed (OSPAR. 2006). The chemical's only use in Canada is as
a fuel additive (Environment Canada and Health Canada. 2008). but it has also been used as a
lubricant additive in Canada in the past, as well as in the Netherlands (SKF. 2017; Environment
Canada and Health Canada. 2008)). Industrial use of 2,4,6 TTBP is prohibited in Japan under the
Chemical Substances Control Law (NICNAS. 2017).
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Use of 2,4,6 TTBP is prohibited by engineering standards of some large businesses in the US. For
example, Toyota's North America construction site management handbook prohibits 2,4,6 TTBP
due to its ban in Japan (Toyota Motor Engineering & Manufacturing. 2007). GE's Design
Requirements for Regulated Materials and Chemicals lists 2,4,6 TTBP as prohibited from use in
parts, products, or other chemical substances (General Electric Company. 1995). In addition,
IBM's Engineering Specification 46G3772 environmental requirements prohibit lubricants
containing the chemical (IBM. 2018).
In the 2012 Chemical Data Reporting, 2,4,6 TTBP was reported to be used industrially as an
intermediate and reactant for processing in plastics and resin manufacturing and other organic
chemical manufacturing, and as a fuel additive in petroleum and coal products manufacturing
(U.S. EPA. 2014b). 2,4,6 TTBP also had reported uses in the fuels and related products category.
The chemical is an ingredient in automobile fuel injector cleaners, as well as in lubricant
additives and fuel additives (as an antioxidant) in gasoline and jet fuel.
A variety of commercial fuel additives were also found to contain 2,4,6 TTBP, all at levels below
3 percent by weight (U.S. EPA. 2017a). Champion Brands' Fuel Stabilizer is marketed for use in
2-cycle, 4-cycle, gas, and diesel engine fuel systems to deter development of residue during
periods of non-use (Champion Brands. 2014). Cyclo Industries' Fuel Stabilizer is similarly
marketed for 2- and 4-cycle engines to prevent gum and varnish build-up (Cyclo Industries.
2018). Champion Brands' Engine Oil Additive (also sold as Engine Oil Treatment and Engine
Protectant Oil Treatment) is marketed for engine wear protection in cars or light trucks during
extreme cold or heat to maintain engine performance (Champion Brands. 2014).
At least two fuel injector cleaners sold in the US also contain 2,4,6 TTBP. The fuel injectors in a
vehicle supply a fixed amount of gasoline to the engine (Ryan. 2011). Over time, components of
fuel may oxidize and form residue that builds up on fuel injectors, negatively impacting engine
performance and fuel efficiency (Cole. 2011). Products for fuel injector cleaning that contain
2,4,6 TTBP include Arctic Cat's Fuel Injector Cleaner (also sold as Fuel Injector and Carburetor
Cleaner), which is recommended for use in stored sleds, Rislone's Fuel Injector Cleaner, which is
recommended as an all-around fuel additive for gasoline and diesel engines, and Hy-Per Lube
Corporation's Total Fuel System Cleaner, which is recommended for use in all cars, trucks, and
marine engines (Arctic Cat. 2018; Hy-per Lube. 2018; Rislone. 2018).
A 2008 Environment Canada Screening Assessment of 2,4,6 TTBP identified that the substance
is not naturally produced in the environment, has historically been used as a lubricant additive,
and currently used in Canada as a fuel, oil, and gasoline additive (U.S. EPA. 2017a). Although
use as a fuel additive is the only known use for 2,4,6 TTBP in Canada, several additional use
pattern codes and corresponding applications were noted in the 2001 and 2007 survey,
including: feedstock fuels, chemical intermediates, pesticides, fertilizers, salt for deicing,
solvents, cutting fluids, aerosol propellants, hydraulic fluids, lubricants and additives,
cleaning/washing agents and additives, plant protection products, agricultural products,
explosives, antioxidants, corrosion inhibitors, tarnish inhibitors, scavengers, and anti-scaling
agents (U.S. EPA. 2017a).
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The categories of use that are considered within the scope of the use and exposure assessment
during various life cycle stages including manufacturing, processing, use (industrial, commercial
and consumer), distribution and disposal are depicted in Table 7-1 and the life cycle diagram
(Figure 7-1). The information is grouped according to Chemical Data Reporting (CDR) processing
codes and internationally harmonized functional, product and article use categories from the
Organization for Economic Co-operation and Development (OECD) in combination with other
data sources (e.g., published literature and consultation with stakeholders), to provide an
overview of the uses.
Use categories are drawn from Instructions for Reporting for the 2016 CDR. "Industrial use"
means use at a site at which one or more chemical substances or mixtures are manufactured
(including imported) or processed. "Commercial use" means the use of a chemical or a mixture
containing a chemical (including as part of an article) in a commercial enterprise providing
saleable goods or services. "Consumer use" means the use of a chemical or a mixture
containing a chemical (including as part of an article, such as furniture or clothing) when sold to
or made available to consumers for their use (U.S. EPA. 2016c).
Table 7-1. Use Categories and Subcategories for 2,4,6 TTBP
Life Cycle Stage
Categorya
Subcategoryb
References
Manufacture
Domestic manufacture
Domestic manufacture
(U.S. EPA. 2016a); U.S. EPA
(2017a); EPA-HQ-OPPT-
2016-0734
Processing
Processing -
reactant/chemical
intermediate
Intermediate
(U.S. EPA. 2016a); U.S. EPA
(2017a); EPA-HQ-OPPT-
2016-0734
Processing -
incorporation into
formulation, mixture or
reaction product
Fuels and fuel additives/Antioxidant
U.S. EPA (2016a); U.S. EPA
(2017a); EPA-HQ-OPPT-
2016-0734
Repackaging
Fuels and fuel additives/Antioxidant
U.S. EPA (2017a); EPA-HQ-
OPPT-2016-0734
Industrial,
Commercial,
Consumer Uses
Fuels and related
products
Fuel additive/fuel injector
cleaner/Antioxidant
U.S. EPA (2017a); EPA-HQ-
OPPT-2016-0734
Maintenance,
manufacture, and repair
of motor
vehicles/machinery
Wholesale and retail trade and
repair of motor vehicles
U.S. EPA (2017a)
Lubricating
agent/additive in the
transportation sector
Liquid lubricants and grease
[additive/antioxidant]
U.S. EPA (2017a)
Other uses
Fuel oil
EPA-HQ-OPPT-2016-0734
Emissions to air
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Life Cycle Stage
Categorya
Subcategoryb
References
Releases and
Waste Disposal
Wastewater
Liquid wastes
Solid wastes
aThese categories appear in the Life Cycle Diagram and broadly represent the uses of 2,4,6 TTBP in commercial and/or
consumer settings.
These subcategories reflect CDR and OECD codes and more specific uses of 2,4,6 TTBP based on stakeholder outreach, and
comments received on EPA's Preliminary Information on Manufacturing, Processing, Distribution, Use, and Disposal published
in August 2017.
Descriptions of the commercial or consumer use subcategories identified from the 2017 OECD
Harmonized Use Codes are summarized below (OECD. 2017b):
The "antioxidant" functional use category includes chemical substances that retard oxidation,
rancidity, deterioration, and gum formation. Used to maintain the quality, integrity, and safety
of finished products by inhibiting the oxidative degradation of the ingredients in the
formulation.
The "fuel additives" product use subcategory covers products added to fuels to improve
properties such as stability, corrosion, oxygenation, and octane rating.
The "Liquid lubricants and greases" product use subcategory is defined as liquids that reduce
friction, heat generation and wear between surfaces.
7.3. Characterization of Expected Environmental Partitioning
If released to air, the vapor pressure and Henry's law constant of 2, 4, 6 TTBP indicate that
some fraction of 2, 4, 6 TTBP will partition out of the air to water, airborne particulates, or soil,
while some remains in the vapor phase. Particulate-bound 2, 4, 6 TTBP may be removed from
the air through dry or wet deposition.
If released to water, 2, 4, 6 TTBP is expected to adsorb to suspended and settled sediments. It
would be expected to accumulate in sediments via partitioning and settling, but also undergo
transport downstream in both the aqueous phase and as part of suspended solids based on its
partitioning parameters and water solubility. Volatilization to the air may occur based on its
Henry's law constant, but would likely be negligible in most environments due to adsorption to
sediments.
Releases to waste water treatment plants should result in significant partitioning to biosolids
along with some release of particulate bound 2, 4, 6 TTBP to surface water due to release of
particulates in the effluent. The portion of the chemical bound to biosolids could then be either
landfilled or applied to soil.
If released to soil, 2,4,6-Tris(tert-butyl) phenol is unlikely to undergo volatilization from dry soil
based on its organic carbon partitioning and volatility. In moist soil, its Henry's law constant
Page 131 of 190
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indicates that volatilization from the aqueous phase in soils may occur but will be limited by
adsorption to soil organic matter. 2,4,6-Tris(tert-butyl) phenol will largely be associated with
soil organic matter due to its log Koc but may have some mobility in soil due to its relatively high
water solubility.
If released to landfill, 2,4,6-Tris(tert-butyl) phenol should migrate slowly into leachate and will
only migrate slowly to other environments. Volatilization is likely to be small based on its
partitioning parameters.
2,4,6-Tris(tert-butyl) phenol also may partition to the tissues of organisms that live in water, soil
and sediment via dermal or gill exposure and ingestion. Exposure to water column organisms is
also possible via resuspension of the chemical from the sediment to water either sorbed to
particulates or part of the dissolved phase. The above characterization is meant to describe the
primary behavior or movement of the chemical through a generic environment, not the
complete exclusion of the chemical from a given media (e.g., water) or elimination of the
possibility for more complex behavior in a particular location.
If released to the indoor environment, 2,4,6-Tris(tert-butyl) phenol will tend to partition to
particulates and dust in the indoor environment based on its affinity for organic carbon relative
to air. If the chemical enters the home via tap water, volatilization will not be a significant
removal process in most cases. If released down the drain, it is likely it would arrive at nearby
wastewater treatment plants due to relative mobility in water due to high water solubility and
low Koc-
7.4. Overview of Lifecycle and Potential Sources of Exposure
7.4.1. Background and Brief Description of Lifecycle.
2,4,6 TTBP is domestically manufactured at one known U.S. facility and is not imported by any
facilities above the CDR reporting threshold. It is a yellow solid that dissolves in many organic
solvents, but not in aqueous or alcoholic alkaline solutions (Environment Canada and Health
Canada. 2008). 2,4,6 TTBP is primarily used as a site-limited intermediate that is destroyed in
the production of other chemicals that are used as fuel additives. The majority of the remaining
production volume is formulated and sold to customers who also use it as a fuel additive
(containing unreacted 2,4,6 TTBP). A secondary use is in various formulations used in motor
vehicle maintenance operations. Minor uses include: as a laboratory agent (analytical
standard); as lubricating grease, cleaning/washing agents and additives for automobile
servicing. Other miscellaneous uses include a component of fuel oil (U.S. EPA. 2017a).
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MFG/IMPORT
INDUSTRIAL, COMMERCIAL, CONSUMER USES
RELEASES and WASTE DISPOSAL
Manufacture
(10M-50M lbs)4
Reactant/Chemical
Intermediate
(9.4M-47M lbs)'
Incorporation Into
Formulation, Mixture, or
Reaction Product
e.g. fuels and fuel
additives
(0.6M-3M lbs)3
Repackaging
Fuels and Related Products
e.g., fuel injector cleaner, fuel additive
Maintenance, Manufacture, and
Repair of Motor
Vehicles/Machinery
e.g., wholesale and retail trade and
repair of motor vehicles
Lubricating Agent/Additive in
the Transportation Sector
e.g.. lubricating grease,
cleaning/washing agents and additives,
latex manufacture
Other Uses
e.g., fuel oil, RAO038 analytical
Emissions to Air
Liquid Wastes
Solid Wastes
2, 4, 6-Tris (tert-butyl)
phenol (2, 4, 6-TTBP)
~
~ Processing
I I uses
aFor the 2016 CDR, one company reported the manufacture and/or import of 2, 4, 6-TTBP in the U.S. above the reporting
threshold. The production volume of was claimed as confidential business information. The CDR production was also CBI in
2012. PubChem and EPA have reported historical production ranges (e.g., in 2006 production ranged between 10 and 50 million
pounds). 94% of the production volume is reported to be used as a reactant/intermediate, destroyed in the manufacture of
other chemicals. The remaining portion of the production volume is incorporated into formulations or mixtures.
Figure 7-1. Lifecycle Diagram for 2,4, 6 TTBP
7.4.2. Manufacturing and Processing as a Reactant/Chemical
Intermediate
2,4,6 TTBP is manufactured as a solid powder at ambient temperature (Environment Canada
and Health Canada. 2008) that is transferred to temporary storage vessels for use as a site-
limited intermediate for the manufacture of other products (U.S. EPA. 2017a). Releases to air,
water, and land are possible from the associated unit operations and transfer and on-site
storage steps prior to the chemical being consumed in reaction. The primary sources of release
include fugitive dust emissions, disposal and release of transfer-container cleaning solutions
and disposal of empty containers, process equipment cleaning, and off-spec product. Fugitive
and stack air (dust) emissions are expected from transfer of 2,4,6 TTBP into temporary storage
and subsequent unloading and transfer into process equipment for final production of the final
product. Release to water may result from equipment and general area cleaning with if
aqueous cleaning materials are used. However, due to the low water solubility, cleaning with
organic solvents is more likely and would be expected to be collected for incineration. Land
releases may occur from disposal of empty storage containers and floor sweepings. Inhalation
exposure to fugitive dust may occur during unloading, transfer, and processing steps. Dermal
exposure is possible from contact during unloading and transfer operations.
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7.4.3. Processing: Incorporation into Formulation, Mixture, or Reaction
Products
2,4,6 TTBP is manufactured as a solid powder (Environment Canada and Health Canada. 2008)
and formulated into products such as fuels and fuel additives at the U.S. manufacturing facility
for sale to domestic customers (U.S. EPA. 2017a). Releases to air, land, and water are expected
from 2,4,6 TTBP and 2,4,6 TTBP formulations (solids and liquids). Air releases (fugitive dust and
dust collected and channeled to a stack) are expected from transfer operations. Releases to
land may occur during disposal of transfer containers containing residual material, collection
and disposal of floor sweepings, and disposal of off-spec product. Equipment and general area
cleaning with liquid cleaning materials may result in releases to water, although waste cleaning
solutions from cleaning with organic solvents are more likely to be collected for incineration.
Occupational exposures from inhalation of fugitive dust and dermal exposure to dust may occur
during transfer and packaging operations and from fugitive dust emissions from process
operations. Dermal exposure to liquids is possible from incidental contact of liquid 2,4,6 TTBP
formulations during transfer, loading, and mixing operations (OECD. 2017a).
7.4.4. Industrial, Commercial, and Consumer Use: Fuel and Related
Products (fuel additives)
Fuel additive formulations containing 2,4,6 TTBP in solution may be shipped to end users in a
variety of container types. Fugitive air releases of 2,4,6 TTBP are expected to be minimal due to
the low vapor pressure, but are possible from unloading and transfer operations. It is expected
that the majority of 2,4,6 TTBP is destroyed (burned) as the fuel is consumed/used. Land
releases may occur from disposal of empty transport containers and waste absorbents used to
clean regular spills and leaks from loading operations. Waste from equipment cleaning with
organic cleaning solutions is anticipated to be collected for incineration. Water releases are
possible from equipment and general area cleaning with aqueous cleaning solutions. Dermal
exposure to 2,4,6 TTBP may occur from transfer and fuel loading operations. Inhalation
exposure to fugitive air releases are expected to be minimal due to the low vapor pressure, but
are possible.
7.4.5. Industrial, Commercial, and Consumer Use: Motor Vehicle
Repair, Lubricating Agents and Additives in the Transportation Sector
(lubricating grease, cleaning/washing agents and other additives)
Automobile lubricants, greases, and other additives containing 2,4,6 TTBP are expected to be
shipped to end users as liquids in a variety of packaging container types. Fugitive air releases of
2,4,6 TTBP are expected to be minimal due to the low vapor pressure and they are expected to
be in liquid formulation. Water releases are not expected from waste lubricants because waste
material is usually incinerated (OECD. 2017a). However, land releases may occur from disposal
of empty transport containers and other waste that is not incinerated (OECD. 2017a;
Environment Canada and Health Canada. 2008). Dermal exposure to 2,4,6 TTBP (full hand
immersion, splashing, or spraying) is expected from handling lubricants. Inhalation exposure to
Page 134 of 190
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fugitive vapors is not likely, but is possible; however, inhalation exposure to mist may occur if
spray application processes are used (OECD. 2017a).
7.4.6. Industrial/Commercial Use: Other Uses (e.g., laboratory
research)
Small quantities of 2,4,6 TTBP are used in laboratories as an analytical standard. Potential
releases to all media are possible from use and disposal of unused experimental reagents and
laboratory equipment that may contain residual 2,4,6 TTBP. However, releases directly to the
environment are expected to be minimal due to handling and disposal requirements in
laboratory settings. Similarly, inhalation and dermal exposure to laboratory personnel is
possible from the handling of laboratory reagents; however, it is expected to be minimal due to
the use of engineering controls such as fume hoods and personal protective equipment.
7.4.7. Qualitative Trends Over Time for Releases for Releases and
Occupational Exposures
2,4,6 TTBP is not reported to the Toxics Release Inventory and no release data over time were
identified.
7.5. Environmental Monitoring
2,4,6 TTBP was detected in relatively few environmental monitoring studies. A supplemental
search was conducted for 2,4,6 TTBP to determine if any studies co-reported information on
aromatic phenol chemicals. The chemical most reported in environmental media from the
supplemental search is Butyl Hydroxytoluene (BHT) BHT. BHT and 2,4,6 TTBP are structurally
similar, have similar physical-chemical properties, but different uses. BHT is an antioxidant and
food additive, whereas the uses of 2,4,6 TTBP are narrower. It may be possible that BHT could
degrade to 2,4,6 TTBP in the environment. Table 7-2 provides a summary of the monitoring
data for 2,4,6 TTBP and BHT identified in the peer-reviewed literature across all media
considered. Also included in the count are available monitoring database sources. Only studies
or databases that reported measurements of the chemical of interest above the limit of
detection were extracted and included in the "# of studies" count. The frequency of detection is
provided as a measure, across all samples in all extracted studies, of the frequency that the
chemical was measured above the limit of detection. Note, the frequency of detection is
reported only for peer-reviewed sources, unless the only data sources available were database
sources.
This is generally consistent with the fate summary and reported physical-chemical properties
for in that 2,4,6 TTBP was detected in surface water, influent/effluent, air, and dust. It is also
notable that releases are primarily expected to air and water.
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Table 7-2. Summary of 2,4,6 TTBP and BHT Monitoring Data from Peer-Reviewed Literature
Media
Presence
No. of Datasets
Frequency of Detection
Indoor dust
Yes
1
100%
Indoor air
Yes
1
100%
Ambient air
Yes
1
3%
Surface/Ground water
Yes
2
97%
Drinking water
No
0
n/a
Soil
No
0
n/a
Sediment
Yes
3
4%
Biosolids
No
0
n/a
Wastewater (influent, effluent)
Yes
1
17%
Landfill leachate
No
0
n/a
Vegetation/Diet
No
0
n/a
Other
No
0
n/a
The following chart provides the number of studies that reported 2,4,6 TTBP monitoring data
over time. For this chart, the year the study is published rather than the sampling timeframe is
used as a proxy, though for most studies, samples were collected a few years prior to
publication. Note, EPA recognizes that the sampling dates, rather than the publication date,
would be a better reflection of temporal trends.
Figure 7-2. Frequency of peer-reviewed publications identified that contained 2,4,6 TTBP
monitoring data.
All environmental monitoring data that passed EPA's evaluation criteria are presented
graphically in the plots below. These plots help visualize the data and are organized by study
year and microenvironment, when reported. Note, some studies are discussed in Sections 7.7
Page 136 of 190
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and 7.11 as they pulled together information on monitoring data alongside supplemental
contextualizing information on uses, sources, and trends.
7.5.1. Indoor Dust
Liu et al. 2017
10 100 1000 10A4
Concentration (ng/g)
Figure 7-3. Concentration of 2,4,6 TTBP and BHT (ng/g) in indoor dust for residential locations
in 2017. The range of values reported is presented by the entire length of the bar. The
minimum and maximum of reported central tendency estimates are shown as a separate
dark color within.
This figure contains data for the following: (Liu et al.. 2017)
7.5.2. Indoor Air
Concentration (ng/m3)
Figure 7-4. Concentration of 2,4,6 TTBP and BHT (ng/m3) in indoor air for commercial
locations in 1989. The minimum and maximum of reported central tendency estimates are
shown.
This figure contains data for the following: (Kosaka et al.. 1989)
7.5.3. Ambient Air
Japanese Ministry of Environment 2010 |
10A-6 10A-5 10A-4 0.001 0.01 0.1 1 10 100
Concentration (ng/m3)
Figure 7-5. Concentration of 2,4,6 TTBP and BHT (ng/m3) in ambient air for background
locations in 2010. The range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (Japanese Ministry of Environment. 2010)
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7.5.4. Surface Water
ฆ background
Calderon-Preciado et al. 2011
10 100
1000
10A4
10A5
Concentration (ng/L)
Figure 7-6. Concentration of 2,4,6 TTBP and BHT (ng/L) in surface water for background
locations in 1999 and 2011. For each year, the range of values reported is presented by the
entire length of the bar.
This figure contains data for the following: (Calderon-Preciado et al.. 2011; Davi and Gnudi.
1999)
7.5.5. Sediment
background
Japanese Ministry of Environment 2005
Japanese Ministry of Environment 2004
ฆ
10A-6
10A-5
10A-4
0.001 0.01 0.1
Concentration (ng/g)
10
100
Figure 7-7. Concentration of 2,4,6 TTBP and BHT (ng/g) in sediment for background locations
from 2004 to 2010. For each year, the range of values reported is presented by the entire
length of the bar.
This figure contains data for the following: (Japanese Ministry of Environment. 2010. 2005.
2004)
7.5.6. Influent/Effluent
USGS 2012
100
140
180
Concentration (ng/L)
220
260
300
Figure 7-8. Concentration of 2,4,6 TTBP and BHT (ng/L) in influent/effluent for near facility
locations in 2012. The range of values reported is presented by the entire length of the bar.
This figure contains data for the following: (USGS. 2012)
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7.5.7. Other
EPA did not identify any studies with extractable 2,4,6 TTBP nor BHT data in drinking water or
landfill leachate. 2,4,6 TTBP is not expected to be present in these media due to the following:
For drinking water, 2,4,6 TTBP is expected to adsorb to suspended and settled
sediments.
For landfill leachate, 2,4,6 TTBP should migrate slowly into leachate.
EPA did not identify any studies with detectable levels of 2,4,6 TTBP nor BHT in soil,
sludge/biosolids, or vegetation/diet.
7.6. Biomonitoring
2,4,6 TTBP has a handful of reports of biomonitoring data. There are only a small handful of
studies that show 2,4,6 TTBP detected in any biological matrix. A supplemental search was also
performed on BHT, a surrogate for 2,4,6 TTBP; however no studies were identified with
extractable biomonitoring data. Table 7-3 provides a summary of the biomonitoring data for
2,4,6 TTBP identified in the peer reviewed literature across all matrices considered. Also
included in the count are available monitoring database sources. Only studies or databases that
reported measurements of the chemical of interest above the limit of detection were extracted
and included in the "# of studies" count. The frequency of detection is provided as a measure,
across all samples in all extracted studies, of the frequency that the chemical was measured
above the limit of detection. Note, the frequency of detection is reported only for peer-
reviewed sources, unless the only data sources available were database sources.
This is generally consistent with the fate summary in that 2,4,6 TTBP was detected in matrices
where it was expected due to physical-chemical properties; however, for many matrices, 2,4,6
TTBP data have not been collected.
Table 7-3. Summary of 2,4,6 TTBP Biomonitoring Data from the Peer-Reviewed Literature and
Monitoring Databases
Matrix
Presence
No. of Datasets
Frequency of Detection
Human blood (serum)
No
0
n/a
Human (other)
No
0
n/a
Fish
Yes
1
n/a
Birds
No
0
n/a
Terrestrial invertebrates
No
0
n/a
Aquatic invertebrates
No
0
n/a
Terrestrial mammals
No
0
n/a
Aquatic mammals
No
0
n/a
Other
No
0
n/a
The following chart provides the number of studies that reported 2,4,6 TTBP biomonitoring
data over time. For this chart, the year the study is published rather than the sampling
timeframe is used as a proxy, though for most studies, samples were collected a few years prior
Page 139 of 190
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to publication. Note, EPA recognizes that the sampling dates, rather than the publication date,
would be a better reflection of temporal trends.
7.6.1. Fish
USGS-Tissue 1999-2003
MMDB
100
120
140
Concentration (ng/g)
160
180
200
Figure 7-9. Concentration of 2,4,6-tris(tert-butyl) phenol (ng/g) in fish from one monitoring
database (USGS). The minimum and maximum of reported central tendency estimates are
shown.
This figure contains data for the following HERO IDs: (USGS. 1991)
7.6.2. Other
EPA did not identify any studies with detectable levels of 2,4,6 TTBP in human blood (serum),
human (other), aquatic invertebrates, aquatic mammals, terrestrial invertebrates, birds, or
terrestrial mammals.
7.7. Trends in Monitoring Data
EPA identified one study (Davi and Gnudi. 1999) that reported trends for 2,4,6 TTBP in surface
water. No studies were identified that reported trends for closely-related chemicals. Only one
monitoring database (USGS) reported data for concentrations of 2,4,6 TTBP in fish (USGS.
1991).
7.7.1. Surface Water
One study reported in surface water from 1994 to 1996 (Davi and Gnudi. 1999). A steady
decrease in 2,4,6, TTBP was observed with time.
Page 140 of 190
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Ll
1994 1995 1996
Year
Figure 7-10. Concentration of 2,4,6 TTBP (ng/L) in surface water from 1994 to 1996.
7.7.2. Fish
One monitoring database (USGS) reported 2,4,6 TTBP concentrations in fish from 1999 through
2003 and showed no change in concentration during that period (USGS. 1991).
USGS-Tissue 1998 |
USGS-Tlssim
USGS-Tissue 1999 ฆ
USGS-Tissue 2000 |
USGS-Tissue 2001 ฆ
USGS-Tissue 2002 |
USGS-Tissue 2003 ฆ
100
200
300 400
Concentration (ng/g)
SOO
600 700 800 900 1000
Figure 7-11. Concentration of 2,4,6 TTBP (ng/g) in fish from 1998 through 2003. Only central
tendencies (dark blue) were reported.
7.8. Modeled Intake and Dose Data
One study (Liu et al.. 2017) was identified that modeled the average daily dose for the sum of
seven synthetic phenolic antioxidant analogues and was used as a surrogate for 2,4,6 TTBP.
Urban environments resulted in higher dose estimates than rural environments, and children
also had higher dose estimates than adults.
6000
5000
00
4000
c
o
to
ฃ 3000
u
c
O
U
2000
1000
Page 141 of 190
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. . T .
Adult, rural
Figure 7-12. Estimated average daily dose (ng/kg/day) of the sum of seven synthetic phenolic
antioxidant analogues, which are used as a surrogate for 2,4,6 TTBP, for total exposure. Data
are presented for children and adults, separated by urban and rural regions.
7.9. Overview of Existing Exposure Assessments
Environment Canada and Health Canada (2008 prepared a screening assessment of 2,4,6 TTBP
for ecological concerns related to persistence, bioaccumulation, and toxicity criteria. It stated
that 2,4,6 TTBP is expected to adsorb strongly to soil and sediment, partition to lipids, and
persist in water, soil, and sediments, and potentially biomagnify in food chains. The assessment
also noted that the known use of 2,4,6 TTBP in Canada is as a fuel additive based on a 2007
survey, and most of the 2,4,6 TTBP is destroyed during combustion of the fuel. The European
Union (European Chemicals Agency (ECHA), 2008) assessed risks of p-tert-butylphenol and
stated that formation of 2,4,6 TTBP during the production of p-tert-butylphenol was
theoretically possible but the material is not detected in the final product (detection limit of 2
PPm).
The Australian Government Department of Health (NICNAS, 2013) also evaluated persistence,
bioaccumulation, and toxicity of 2,4,6 TTBP. It similarly concluded that the chemical would be
expected to be combusted in the fuels to which it was added. This assessment expected that
2,4,6 TTBP releases to water would partition mainly to sediment, and releases to sewage
treatment would partition to biosolids, which might be applied to agriculture soils.
Page 142 of 190
12
_ 10
>-
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QjD 8
'cS
aj 6
in
o
Q
= 4
'ro
O
CD
w) 2
ro
k_
<
X
Child, urban
Child, rural Adult, urban
Total
-------
No reported estimated exposure intake or dose estimates were presented in the authoritative
sources for 2,4,6 TTBP.
7.10. Representative Exposure Scenarios
2,4,6 TTBP has a narrow set of uses. Each of these uses has potential for release and exposure.
However, there is limited monitoring data for 2,4,6 TTBP itself to document these exposures.
Based on its physical-chemical properties, ingestion is likely the primary exposure route.
Inhalation would likely be comprised of particles which could be swallowed, and dermal
absorption is likely low.
Occupational: Manufacturing of 2,4,6 TTBP as a solid powder results in particulates that are
transferred to workplace air during transfer and packaging operations. Workers at
manufacturing facilities can inhale these particulates and the particles can settle on exposed
skin. Both inhalation and dermal exposures are possible.
Occupational: 2,4,6 TTBP that is manufactured as a solid powder and subsequently formulated
into products such as fuels and fuel additives results in particulates in workplace air during
transfer operations. Inhalation and dermal exposures to workers from particulates in facilities
formulating 2,4,6 TTBP are possible.
Occupational: Use of 2,4,6 TTBP in fuel additives may result in dermal exposure from incidental
contact during transfer and fuel loading operations.
Occupational: Use of 2,4,6 TTBP in lubricants results in full hand immersion, splashing, or
spraying during handling. Dermal exposure to workers who use these products is possible.
Inhalation and dermal exposure to mist from spray application of these products is also
possible.
Occupational: Industrial and commercial use of 2,4,6 TTBP as an analytical standard may result
in generation of particulates in workplace air. Laboratory workers may inhale these particulates
and incidental contact with exposed skin may occur from accidental spills during use of the
standards. However, the use of engineering controls such as fume hoods and personal
protective equipment is expected to reduce these exposures.
General Population: Manufacturing of 2,4,6 TTBP results in fugitive air releases of particulates
which may lead to elevated air concentrations for residents living near these facilities.
Ecological: Cleaning of equipment during use of industrial, commercial, and consumer use of
fuels leads to releases to water and elevated concentrations in surface water where aquatic
organisms may be exposed.
Consumer: Use of 2,4,6 TTBP in lubricants results in full hand immersion, splashing, or spraying
during handling. Dermal exposure to consumers who use these products is possible. Inhalation
and dermal exposure to mist from spray application of these products is also possible.
Page 143 of 190
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7.11. Summary of Review Articles
No review articles were identified that presented exposure estimates or doses for 2,4,6 TTBP,
other than the authoritative sources presented in Section 7.9. For 2,4,6 TTBP, Environment
Canada and Health Canada conducted an ecological screening assessment in 2008, and
determined the potential for 2,4,6 TTBP contamination of soils and sediments after incomplete
combustion as a fuel additive, but reported that 2,4,6 TTBP was not measured above 2 ppm in
fuel additives. Minimal exposure data were reported in 2008 for this assessment.
8. Pentachlorothiophenol (PCTP)
8.1. Chemistry and Physical-Chemical Properties
Chemical Name
Pentachlorothiophenol
CASRN
133-49-3
Synonyms
PCTP; Benzenethiol, 2,3,4,5,6-pentachloro-; Benzenethiol, pentachloro-; Benzenethiol,
pentachloro-; Pentachlorobenzenethiol; Pentachloro-benzenethiol; Pentachlorothiophenol;
Pentachlorothio-phenol 1; Pentachlorthiofenol; Pentachlorobenzenethiol
Molecular Formula
CsHCIsO
Structure
SH
ฐyS^j
Source: (NLM. 2018)
MW
282.40
Density (g/cm3)
1.745 (Estimated by ACD/Labs in Chemistry Dashboard, 2017)
Molar Volume
(cm3/mol)
162 [Calculated based on the molar mass and density]
Log Kow
5.91 [Estimated using EPISuite v4.11 (U.S. EPA. 2012)1
Log Koa
8.2 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Log Koc
4.3 [Kow method, estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Vapor Pressure
(mm Hg)
5.1 x 10"6 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Henry's Law (atm-
m3/mole)
1.5 x 10"4 [Group Method, estimated using EPISuite v4.11 (U.S. EPA. 2012)1
Water Solubility
(mg/L)
0.0048 [Estimated using EPISuite v 4.11 (U.S. EPA. 2012)1
Water Solubility
(mol/L)
1.7 x 10"8 [Calculated based on water solubility and molecular weight, estimated using
EPISuite v 4.11 (U.S. EPA. 2012)1
8.2. Uses
Since the publication of the Use Document in August 2017 for PCTP, EPA received 9 public
comments and communicated with several companies, industry groups, chemical users, and
Page 144 of 190
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other stakeholders to aid in identifying and verifying conditions of use of PCTP (U.S. EPA.
2017d). These interactions and comments further informed EPA's understanding of the uses for
PCTP. The information and input received from the public comments and stakeholder
engagement has been incorporated into this document to the extent appropriate. Non-
confidential public comments and stakeholder meeting summaries can be found in EPA's
docket at EPA-HQ-OPPT-2016-0739.
PCTP is obtained from hexachlorobenzene (a fungicide not used in the U.S. since 1984) (by
treatment with sodium sulfide and sulfur in methanol, or with sodium hydrogensulfide (U.S.
EPA. 2017d). Additionally, PCTP may be obtained with a "reaction of hydrogen sulfide with
pentachlorophenol in the presence of an acidic catalyst, e.g., aluminum chloride or boron
trifluoride" (U.S. EPA. 2017d).
No company has reported manufacture and/or import of PCTP (PCTP) in the U.S. above the
reporting threshold of the Chemical Data Reporting (CDR) Rule for 2016 (U.S. EPA. 2016c). Only
one company reported manufacture and/or import of PCTP in the U.S. in 2012 (U.S. EPA.
2017d).
Historically, PCTP (or its zinc salt) was used as the preferred peptizer for natural rubber.
However the National Institutes of Health (NIH) reports that PCTP is banned in most parts of
the world because it forms several teratogenic decomposition products (HSDB. 2015).
According to Ullmann's Encyclopedia of Industrial Chemistry, PCTP has been replaced by 2,2'-
dibenzamidodiphenyldisulfide (DBD), which reacts similarly, but is less toxic (HSDB. 2015).
PCTP is primarily used in the rubber manufacturing industry. According to Ullmann's
Encyclopedia of Industrial Chemistry, PCTP is used as a mastication agent in the rubber industry
and more specifically, a peptizing agent for natural rubber viscosity reduction in the early stages
of rubber manufacturing (HSDB. 2015). Mastication and peptization are processing stages
during which the viscosity of rubber is reduced to a level facilitating further processing
(Struktol. 2018). It is possible to reduce the viscosity of natural and synthetic rubbers through
solely mechanical efforts, but peptizers allow this process to be less sensitive to varying time
and temperature, which improves the uniformity between batches (HSDB. 2015).
Although PCTP is reportedly largely replaced by 2,2'-dibenzamidodiphenyldisulfide (DBD) as the
preferred peptizing agent for natural rubber, the predominant use of PCTP remains as a
peptizer (HSDB. 2015). PCTP is primarily used in the peptization process of natural rubber.
There is little data, however, on the types of end-use products that contain PCTP. A search of
several product data bases including EPA's Chemical and Product Categories (CPCat) database,
the National Library of Medicine's Household Products Database, and the Consumer Product
Information Data Base (CPID), returned no product Safety Data Sheets (SDS). A Google search of
PCTP returned no SDS' containing that chemical. A search of the website of the chemical
processor, Struktol, returned five general technical data sheets for rubber peptizers, however
none of them mention specific chemicals.
Page 145 of 190
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The Swedish Chemicals Agency KEMI Commodity Guide suggests that PCTP may be found in
butadiene rubber, isoprene rubber, natural rubber, and other rubber materials (U.S. EPA.
2017d). It is possible that imported products containing these materials could contain PCTP.
However, a letter to EPA from the Rubber Manufacturers Association, dated Feb. 22, 2017,
indicates that its members "do not currently use ... PCTP to manufacture tires produced in the
U.S. or imported into the U.S." (EPA-HQ-QPPT-2016-0739).
Material
Content in Material,%
Butadiene rubber (BR)
15-20
Isoprene rubber (IR)
15-20
Natural rubber (NR)
15-20
Other rubber materials
15-20
Source: (Keml. 2007)
Research has shown PCTP to be a breakdown product of pentachloronitrobenzene, a fungicide,
and hexachlorobenzene (HCB), a fungicide that has not been used in the U.S. since 1984 (U.S.
EPA. 2017d). HCB is listed as POP under the Stockholm Convention (UNEP. 2008). However, no
program that monitors PCTP across various media has been identified.
Table 8-1. Use Categories and Subcategories for PCTP
Life Cycle Stage
Category3
Subcategory13
References
Manufacture
Manufacture
Manufacture
U.S. EPA (2017d)
Processing
Incorporation into rubber
Cross-linking agent used in
rubber manufacturing
U.S. EPA (2017d)
Industrial, Commercial,
Consumer Uses
Incorporation into articles
Golf ball manufacturing
U.S. EPA (2017d)
Other uses
Laboratory research
U.S. EPA (2017d)
Releases and Waste
Disposal
Emissions to air
Wastewater
Liquid wastes
Solid wastes
aThese categories of conditions of use appear in the Life Cycle Diagram, broadly represent conditions of use of PCTP in
commercial and/or consumer settings.
These subcategories reflect more specific uses of PCTP based on stakeholder outreach, and comments received on EPA's
Preliminary Information on Manufacturing, Processing, Distribution, Use, and Disposal published in August 2017.
8.3. Characterization of Expected Environmental Partitioning
If released to air, PCTP in the atmosphere is expected to remain in part in the vapor phase,
while some fraction will partition from air into water due to its Henry's law constant (1.5 x 10~4
atm m3/mole), or from air into soil and airborne particulates due to its vapor pressure (5.1 x 10"
6 mm Hg) and log Koa (8.2). Particulate-bound PCTP may be removed from the atmosphere
through wet or dry deposition.
If released to water, based on its log Kow (5.91) and log Koc (4.3), PCTP in surface water is
expected to adsorb to sediments and particulates suspended in the water column. PCTP may
Page 146 of 190
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volatilize from water due to its Henry's law constant, although volatilization is expected to be
limited by adsorption to particulates.
PCTP is likely to be removed from wastewater in treatment plants via adsorption to biosolids,
which may then be landfilled, applied to soil, or incinerated, based on its log Koc and log Kow.
Volatilization of PCTP from wastewater is expected to be limited due to its Henry's law
constant. Release of free PCTP with wastewater treatment plant effluent is expected to be
limited, although PCTP adsorbed to small particles may be released with effluent.
If released to soil, due to its log Koc and water solubility (4.8 x 10"3 mg/L), PCTP released to soil
is expected to adsorb to organic matter. PCTP is not likely to volatilize from dry soil based on its
vapor pressure. Based on its Henry's law constant, PCTP may volatilize from moist soil, but
volatilization will be limited by adsorption to soil organic matter. Mobility of PCTP in soil pore
water and groundwater is expected to be limited due to its log Koc and water solubility,
although PCTP may adsorb to colloids or other small particulates which are mobile in
subsurface environments.
If released to landfill, migration of PCTP to landfill leachate is expected to be slow and limited
due to its log Koc and water solubility, although PCTP bound to small particulates may migrate
into landfill leachate more rapidly. PCTP is not likely to volatilize from solid waste due to its
vapor pressure and log Koa.
PCTP also may partition to the tissues of organisms that live in water, soil and sediment via
dermal or gill exposure and ingestion. Exposure to water column organisms is also possible via
resuspension of the chemical from the sediment to water either sorbed to particulates or part
of the dissolved phase. The above characterization is meant to describe the primary behavior or
movement of the chemical through a generic environment, not the complete exclusion of the
chemical from a given media (e.g., water) or elimination of the possibility for more complex
behavior in a particular location.
If released to the indoor environment, based on its log Koa, vapor pressure, and Henry's law
constant, PCTP is not likely to volatilize from consumer products or articles, contaminated
water, or other solutions. PCTP is more likely to be emitted from consumer products via
abrasion or direct partitioning to dust. If it is present in the indoor air, PCTP is likely to deposit
in dust or other organic matter due to its log Koa.
PCTP released down-the-drain to wastewater is expected to adsorb to organic matter in the
wastewater due to its log Koc and log Kow-
8.4. Overview of Lifecycle and Potential Sources of Exposure
8.4.1. Background and Brief Description of Lifecycle
No U.S. companies currently domestically manufacture or import PCTP above the CDR reporting
threshold. However, two domestic uses of PCTP have been identified. In the primary use, PCTP
Page 147 of 190
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is processed as a cross-linking agent and used in the commercial manufacture of golf balls. It is
also used in small quantities in laboratory research (U.S. EPA. 2017d. 2016e).
MFG/IMPORT
Manufacture
and Import
(Mass CBIa)
PROCESSING
Cross-linking Agent for
Rubber Manufacturing
(peptizer)
Repackaging
INDUSTRIAL, COMMERCIAL, CONSUMER USES*
~
Golf Equipment Manufacturing
e.g., golf balls
Other Uses
e.g., laboratories research
RELEASES and WASTE DISPOSAL
Emissions to Air
Liquid Wastes
Pentachlorothiophenol
(PCTP)
~
Processing
~
'Past/Legacy Uses Include: Rubber
Product Manufacturing in tires
aNo company has reported manufacture and/or import of pentachlorothiophenol (PCTP) in the U.S. above the reporting
threshold of the CDR Rule for 2016. Only one company reported manufacture and/or import of PCTP in the U.S. in 2012. The
production volume of PCTP was claimed as confidential business information (CBI).
bPCTP is mentioned in over 2,100 patents.
*A letter to EPA from the Rubber Manufacturers Association, dated Feb. 22, 2017, indicates that its members "do not currently
use PCTP to manufacture tires produced in the U.S. or imported into the U.S."
Figure 8-1. Lifecycle Diagram for PCTP
8.4.2. Manufacturing and Import
Small quantities of PCTP, a dry powder, may be domestically manufactured and imported (U.S.
EPA. 2017d). It can be manufactured by treatment of hexachlorobenzene (a fungicide not used
in the U.S. since 1984) with sodium sulfide and sulfur in methanol, or with sodium
hydrogensulfide. Additionally, PCTP may be created with a "reaction of hydrogen sulfide with
pentachlorophenol in the presence of an acidic catalyst, e.g., aluminum chloride or boron
trifluoride" (U.S. EPA. 2017d).
Because the product is a dry powder, the most likely sources of releases and occupational
exposures from manufacturing processes are associated with fugitive dust. These include air
releases from transfer and packaging operations (fugitive dust to ambient air as well as dust
that is collected and channeled through a dedicated point as a stack release) and solid waste
from floor sweepings, disposal of used transfer containers containing residual PCTP, and liquid
waste from equipment cleaning. Fugitive vapor air releases are not expected due to the low
vapor pressure. Releases to land are possible when floor sweepings and other solid waste are
Page 148 of 190
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collected and disposed in landfills. Similarly, the collection and disposal of liquid equipment
cleaning solutions has the potential of generating liquid waste containing PCTP (aqueous waste
to surface waters and sent to publicly owned treatment works, and organic waste collected and
sent for other disposal or waste treatment such as incineration). Occupational exposures from
inhalation of fugitive dust and dermal exposure to dust from transfer and packaging operations
and from fugitive dust emissions from process operations is possible. However, dermal
exposure to liquids is not anticipated. Similarly, inhalation exposure to fugitive vapors is not
expected due to PCTP's low vapor pressure.
8.4.3. Processing: Cross-linking Agent for Rubber Manufacturing
PCTP is used as an additive in the rubber manufacturing industry, specifically as a peptizer to
make rubber more pliable (U.S. EPA. 2017d). Although releases of PCTP after cross-linking
occurs are expected to be minimal, releases of additives such as cross-linking agents from
rubber manufacturing are possible to water, air, and land (predominantly prior to reaction
processes are complete). Water releases are expected to be most prevalent. Sources include
process wastewater from cooling or heating medium and vulcanization, where water has direct
contact with the rubber mixture. Releases to water can also occur from equipment and general
area cleaning (OECD. 2004). Land releases are possible from the disposal of off-spec product
and empty transfer containers. Air releases are expected to be minimal due to the low vapor
pressure of PCTP. Occupational inhalation and dermal exposure to dust is possible from
unloading and transfer operations when the PCTP mixture is added to process equipment. Once
incorporated into the rubber formulation, the potential for worker exposure is not expected.
8.4.4. Industrial/Commercial Use: Golf Equipment Manufacturing (golf
balls)
PCTP is used as an additive in the manufacture of golf balls (EPA-HQ-QPPT-2016-0739).
Releases to all media are possible. Land releases may occur from the disposal of off-spec
product and empty transfer containers. Water releases may occur from process wastewater or
from equipment and general area cleaning with aqueous cleaning solutions. Air releases are
expected to be minimal due to the low vapor pressure of PCTP. Occupational inhalation and
dermal exposure to dust may occur from unloading and transfer operations when the PCTP
mixture is added to process equipment. Once incorporated into the product, the potential for
worker exposure is not expected.
8.4.5. Industrial/Commercial Use: Other Uses (e.g. laboratory
research)
Small quantities of PCTP are used as a laboratory reagent. Potential releases to all media are
possible from use and disposal of unused experimental reagents and laboratory equipment that
may contain residual PCTP. However, releases directly to the environment are expected to be
minimal due to handling and disposal requirements at laboratories. Similarly, inhalation and
dermal exposure to laboratory personnel is possible from the handling of laboratory reagents;
Page 149 of 190
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however, it is expected to be minimized by the use of engineering controls such as fume hoods
and personal protective equipment.
8.5. Environmental Monitoring
No studies were identified that reported extractable PCTP data in environmental media.
Therefore, no summary charts or graphs are presented here.
8.6. Biomonitoring
Very few detections of PCTP in biomonitoring matrices are reported. This is potentially caused
by a lack of monitoring data for PCTP, rather than an absence of PCTP in biomonitoring media.
Table 8-2 summarizes the biomonitoring data for PCTP identified in the peer-reviewed
literature across all matrices considered. Also included in the count are available monitoring
database sources. Only studies or databases that reported measurements of the chemical of
interest above the limit of detection were extracted and included in the "# of studies" count.
The frequency of detection is provided as a measure, across all samples in all extracted studies,
of the frequency that the chemical was measured above the limit of detection. Note, the
frequency of detection is reported only for peer-reviewed sources, unless the only data sources
available were database sources.
Table 8-2. Summary of PCTP Biomonitoring Data from the Peer-Reviewed Literature
Matrix
Presence
No. of Datasets
Frequency of Detection
Human blood (serum)
No
0
n/a
Human (other)
Yes
2
100%
Fish
No
0
n/a
Birds
No
0
n/a
Terrestrial invertebrates
No
0
n/a
Aquatic invertebrates
No
0
n/a
Terrestrial mammals
No
0
n/a
Aquatic mammals
No
0
n/a
Other
No
0
n/a
The following chart provides the number of studies that reported PCTP biomonitoring data over
time. For this chart, the year the study is published rather than the sampling timeframe is used
as a proxy, though for most studies, samples were collected a few years prior to publication.
Note, EPA recognizes that the sampling dates, rather than the publication date, would be a
better reflection of temporal trends.
Page 150 of 190
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2.0"
1-5"
t1 |
0.0
1992 1993 1994 1995 1996 1997 1998 1999 2000
Figure 8-2. Frequency of peer-reviewed publications identified that contained PCTP
biomonitoring data.
8.6.1. Human (other)
general
high-end
To-Figueras et al. 1992
ฆฆฆฆฆฆฆ
To-Figueras et al. 2000
10 100 1000 10A4
Concentration (ng/L)
Figure 8-3. Concentration of PCTP (ng/L) in human (other) for the general (1992) and high-end
(2000) populations. For each year, the range of values reported is presented by the entire
length of the bar. The minimum and maximum of reported central tendency estimates are
shown as a separate dark color within.
This chart contains data for the following: (To-Figueras et al.. 2000; To-Figueras et al.. 1992)
8.6.2. Other
Of the studies searched, EPA did not identify any studies with detectable levels of PCTP in
human blood (serum), aquatic invertebrates, fish, aquatic mammals, terrestrial invertebrates,
birds, or terrestrial mammals.
8.7. Trends in Monitoring Data
Of the studies searched, EPA did not identify any studies that reported trends for PCTP nor
closely-related chemicals. Of the monitoring databases searched, no monitoring data was
available for PCTP.
8.8. Modeled Intake and Dose Data
Of the studies searched, EPA did not identify any studies that reported modeled dose or intake
data for PCTP.
Page 151 of 190
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8.9. Overview of Existing Exposure Assessments
EPA did not identify existing assessments of PCTP.
8.10. Representative Exposure Scenarios
PCTP has narrowly defined uses. Each of these uses has some potential for release and
exposure. However, there is limited monitoring data for PCTP to document these exposures.
Based on its physical-chemical properties, ingestion is likely the primary exposure route.
Inhalation would likely be comprised of particles which could be swallowed, and dermal
absorption is likely low.
Occupational: Manufacture of PCTP as a dry powder results in particulates in workplace air
during transfer and packaging operations. Inhalation and dermal exposures to workers in these
manufacturing facilities are possible.
Occupational: Processing of PCTP into rubber results in particulates in workplace air during
unloading and transfer operations when PCTP mixture is added to processing equipment.
Inhalation and dermal exposures to workers in these processing facilities are possible.
Occupational: Use of PCTP in the manufacture of golf balls results in particulates in workplace
air during unloading and transfer operations. Inhalation and dermal exposures to workers in
these facilities are possible
Occupational: Industrial and commercial use of PCTP as laboratory reagent may result in
generation of particulates in workplace air. Laboratory workers may inhale these particulates
and incidental contact with exposed skin may occur from accidental spills during use of the
reagent. However, the use of engineering controls such as fume hoods and personal protective
equipment is expected to reduce these exposures.
General Population: Rubber manufacturing is expected to result in water releases which could
result in bioaccumulation to fish and subsequent ingestion by recreational fisherman.
Ecological: Rubber manufacturing and golf equipment manufacture are expected to result in
releases to water which could result in exposures to aquatic organisms.
8.11. Summary of Review Articles
No review articles were identified that presented exposure estimates or doses for PCTP
Serum data are not available for PCTP and minimal exposure data are available.
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