DRAFT EPA/600/R-11/005A
DO NOT CITE OR QUOTE January 2013
External Review Draft
Update to
An Inventory of Sources and Environmental Releases of
Dioxin-Like Compounds in the United States for the Years
1987,1995, and 2000
NOTICE
THIS DOCUMENT IS AN EXTERNAL REVIEW DRAFT. It has not been formally released
by the U.S. Environmental Protection Agency and should not at this stage be construed to
represent Agency Policy. It is being circulated for comment on its technical accuracy and policy
implications.
National Center for Environmental Assessment
Office of Research and Development
U.S. Environmental Protection Agency
Washington, DC 20460
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DISCLAIMER
This document is distributed solely for the purpose of pre-dissemination peer review
under applicable information quality guidelines. It has not been formally disseminated by EPA.
It does not represent and should not be construed to represent any Agency determination or
policy. Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
ABSTRACT
The purpose of this document is to present an update and revision to the dioxin source
inventory published in 2006 (U.S. EPA, 2006), which is an inventory of sources and
environmental releases of dioxin-like compounds in the United States. The current document
presents updated estimates of environmental releases of dioxin-like compounds to the air, water,
land and products. The sources are grouped into five broad categories: combustion sources,
metals smelting/refining, chemical manufacturing, natural sources, and environmental reservoirs.
Estimates of annual releases to land, air, and water are presented for reference years 1987, 1995,
and 2000 (the years presented in the original report). The quantitative results are expressed in
terms of the toxicity equivalence (TEQ) of the mixture of polychlorinated dibenzo-p-dioxin
(CDD) and polychlorinated dibenzofuran (CDF) compounds present in environmental releases
using a procedure sanctioned by the World Health Organization (WHO) in 1998. This TEQ
procedure translates the complex mixture of CDDs and CDFs characteristic of environmental
releases into an equivalent toxicity concentration of 2,3,7,8-tetrachorodibenzo-p-dioxin (2,3,7,8-
TCDD), the most toxic member of this class of compounds. The total releases under the national
inventory for 1987 in g WHO9g TEQDF were 15,000 to air, 2,400 to land, 360 to water, and 36 to
products. For 1995, the releases in g WHO98 TEQDF were 3,400 to air, 2,500 to land, 30 to
water, and 47 to products. For 2000, the releases in g WHO9g TEQDF were 2,300 to air, 2,300 to
land, 28 to water, and 7 to products. While the overall decreasing trend in emissions seen in the
original report continues, the individual dioxin releases in this draft updated report are generally
higher than the values reported in 2006. This is largely due to the inclusion (in all three years) of
additional sources in the quantitative inventory that were not included in the 2006 report.
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS
LIST OF TABLES xv
LIST OF FIGURES xvii
LIST OF ABBREVIATIONS AND ACRONYMS xviii
PREFACE xxi
AUTHORS, CONTRIBUTORS, AND REVIEWERS xxii
EXECUTIVE SUMMARY xxiii
1. BACKGROUND, APPROACH, AND CONCLUSIONS 1-1
1.1. BACKGROUND 1-1
1.1.1. Dioxin-Like Compounds 1-1
1.1.2. Toxicity Equivalence Factors 1-2
1.1.3. Regulatory Summary 1-5
1.1.4. Information Sources 1-5
1.2. APPROACH 1-6
1.2.1. Reference Years 1-7
1.2.2. Release Types 1-7
1.2.3. Source Classes 1-8
1.2.4. Quantitative Method for Inventory of Sources 1-9
1.2.5. Uncertainties 1-12
1.3. SUMMARY AND CONCLUSIONS 1-15
1.3.1. Contemporary Formation Sources 1-16
1.3.2. Reservoir Sources 1-17
1.3.3. Time Trends 1-17
1.3.4. Sources Not Included in the Inventory 1-20
1.3.5. Congener Profiles of CDD/CDF Sources 1-20
1.3.6. Uncertainty Analysis 1-20
1.3.6.1. Air Releases 1-21
1.3.6.2. Land Releases 1-24
1.3.7. Relative Impact of Releases 1-24
2. MECHANISMS OF FORMATION OF DIOXIN-LIKE COMPOUNDS DURING
COMBUSTION OF ORGANIC MATERIALS 2-1
3. COMBUSTION SOURCES OF CDDs/CDFs: WASTE INCINERATION 3-1
3.1. MUNICIPAL WASTE COMBUSTION 3-1
3.1.1. Air Releases 3-1
3.1.2. Water Releases 3-2
3.1.3. Solid Residue Releases 3-2
3.1.4. Products 3-5
3.1.5. Release Summary 3-5
3.2. HAZARDOUS WASTE INCINERATION 3-6
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
3.2.1. Dedicated HWIs 3-7
3.2.1.1. Air Releases 3-7
3.2.1.2. Water Releases 3-8
3.2.1.3. Solid Residue Releases 3-8
3.2.1.4. Products—None 3-8
3.2.1.5. Release Summary 3-9
3.2.2. Industrial Boilers and Furnaces Burning Hazardous Waste 3-10
3.2.2.1. Air Releases 3-10
3.2.2.2. Water Releases 3-10
3.2.2.3. Solid Residue Releases 3-10
3.2.2.4. Products—None 3-10
3.2.2.5. Release Summary 3-10
3.2.3. Halogen Acid Furnaces Burning Hazardous Waste 3-12
3.2.3.1. Air Releases 3-12
3.2.3.2. Water Releases 3-12
3.2.3.3. Solid Residue Releases 3-12
3.2.3.4. Products—None 3-12
3.2.3.5. Release Summary 3-12
3.3. MEDICAL WASTE INCINERATION 3-13
3.3.1. Air Releases 3-13
3.3.2. Water Releases 3-14
3.3.3. Solid Residue Releases 3-14
3.3.4. Products—None 3-15
3.3.5. Release Summary 3-15
3.4. CREMATORIA 3-16
3.4.1. Human Crematoria 3-16
3.4.1.1. Air Releases 3-16
3.4.1.2. Water Releases 3-17
3.4.1.3. Solid Residue Releases 3-17
3.4.1.4. Products—None 3-17
3.4.1.5. Release Summary 3-17
3.4.2. Animal Crematoria 3-20
3.4.2.1. Air Releases 3-20
3.4.2.2. Water Releases—None 3-20
3.4.2.3. Solid Residue Releases 3-20
3.4.2.4. Products—None 3-21
3.4.2.5. Release Summary 3-21
3.5. SEWAGE SLUDGE INCINERATION 3-23
3.5.1. Air Releases 3-23
3.5.2. Water Releases 3-23
3.5.3. Solid Residue Releases 3-23
3.5.4. Products—None 3-24
3.5.5. Release Summary 3-25
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CONTENTS (continued)
3.6. TIRE COMBUSTION 3-26
3.6.1. Air Releases 3-26
3.6.2. Water Releases 3-26
3.6.3. Solid Residue Releases 3-26
3.6.4. Products—None 3-27
3.6.5. Release Summary 3-27
3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED
CHEMICAL PULP MILLS 3-28
3.8. BIOGAS COMBUSTION 3-29
4. COMBUSTION SOURCES OF CDDs/CDFs: POWER/ENERGY GENERATION 4-1
4.1. MOTOR VEHICLE FUEL COMBUSTION 4-1
4.1.1. Air Literature 4-1
4.1.2. Air Emission Factor 4-3
4.1.2.1. Leaded Gasoline 4-3
4.1.2.2. Unleaded Gasoline 4-4
4.1.2.3. Diesel Fuel 4-5
4.1.3. Air Activity Level 4-7
4.1.3.1. Gasoline 4-7
4.1.3.2. Diesel 4-8
4.1.4. Air Releases 4-8
4.1.5. Water Releases—None 4-8
4.1.6. Solid Residue Releases 4-8
4.1.7. Products—None 4-8
4.1.8. Release Summary 4-9
4.2. WOOD COMBUSTION 4-11
4.2.1. Residential Wood Combustion 4-11
4.2.1.1. Air Releases from Indoor Residential Wood Burners 4-12
4.2.1.2. Air Releases from Residential Outdoor Wood-Fired Boilers 4-13
4.2.1.3. Water Releases—None 4-14
4.2.1.4. Solid Residues from All Residential Wood Burning 4-15
4.2.1.5. Solid Residue Emission Factor 4-15
4.2.1.6. Solid Residue Activity Level 4-15
4.2.1.7. Solid Residue Releases 4-16
4.2.1.8. Release Summary 4-16
4.2.2. Industrial Wood Combustion 4-18
4.2.2.1. Air Releases 4-18
4.2.2.2. Water Literature—None 4-19
4.2.2.3. Solid Residue Releases 4-19
4.2.2.4. Release Summary 4-20
4.3. OIL COMBUSTION 4-22
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
4.3.1. Institutional/Commercial and Residential Oil Combustion 4-22
4.3.1.1. Air Releases 4-22
4.3.1.2. Water Releases—None 4-23
4.3.1.3. Solid Residue Releases—None 4-23
4.3.1.4. Products—None 4-23
4.3.1.5. Release Summary 4-23
4.3.2. Utility Sector and Industrial Oil Combustion 4-24
4.3.2.1. Air Literature 4-25
4.3.2.2. Air Emission Factor 4-25
4.3.2.3. Activity Level 4-25
4.3.2.4. Air Releases 4-26
4.3.2.5. Water Releases—None 4-26
4.3.2.6. Solid Residue Releases—None 4-26
4.3.2.7. Products—None 4-26
4.3.2.8. Release Summary 4-26
4.3.3. Waste Oil Combustion 4-27
4.3.3.1. Air Literature 4-28
4.3.3.2. Air Emission Factor 4-28
4.3.3.3. Activity Level 4-29
4.3.3.4. Air Releases 4-29
4.3.3.5. Water Releases - None 4-29
4.3.3.6. Solid Residue Releases - None 4-29
4.3.3.7. Products - None 4-29
4.3.3.8. Release Summary 4-29
4.4. COAL COMBUSTION 4-30
4.4.1. Coal-Fired Power Plants 4-30
4.4.1.1. Air Releases 4-31
4.4.1.2. Water Releases 4-32
4.4.1.3. Solid Residue Releases 4-32
4 A.I A. Product Literature—None 4-33
4.4.1.5. Release Summary 4-33
4.4.2. Coal-Fired Industrial Boilers 4-35
4.4.2.1. Air Releases 4-35
4.4.2.2. Water Literature 4-36
4.4.2.3. Solid Residue Releases 4-36
4.4.2.4. Release Summary 4-36
4.4.3. Residential Coal Combustion 4-37
4.4.3.1. Air Releases 4-37
4A3.2. Water Releases—None 4-38
4.4.3.3. Solid Residue Releases 4-38
4.4.3.4. Products—None 4-39
4.4.3.5. Release Summary 4-39
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
5. COMBUSTION SOURCES OF CDDs/CDFs: OTHER HIGH-TEMPERATURE
SOURCES 5-1
5.1. CEMENT KILNS 5-1
5.1.1. Air Releases 5-1
5.1.2. Water Releases 5-2
5.1.3. Solid Residue Releases 5-3
5.1.4. Products 5-4
5.1.5. Release Summary 5-4
5.2. LIGHTWEIGHT AGGREGATE KILNS 5-7
5.2.1. Air Releases 5-7
5.2.2. Water Releases—None 5-7
5.2.3. Solid Residue Releases—None 5-7
5.2.4. Product Literature—None 5-7
5.2.5. Release Summary 5-7
5.3. ASPHALT MIXING PLANTS 5-9
5.3.1. Air Releases 5-9
5.3.2. Water Releases 5-9
5.3.3. Solid Residue Releases 5-9
5.3.4. Products 5-10
5.3.5. Release Summary 5-10
5.4. PETROLEUM REFINING CATALYST REGENERATION PLANTS 5-11
5.4.1. Air Releases 5-11
5.4.2. Water Releases 5-12
5.4.3. Solid Residue Releases 5-12
5.4.4. Product Literature 5-12
5.4.5. Release Summary 5-12
5.5. CIGARETTE SMOKING 5-13
5.5.1. Air Releases 5-13
5.5.2. Water Releases—None 5-13
5.5.3. Solid Residue Releases 5-14
5.5.4. Products—None 5-14
5.5.5. Release Summary 5-14
5.6. PYROLYSIS OF BROMINATED FLAME RETARD ANTS 5-15
5.7. CARBON REACTIVATION FURNACES 5-15
5.7.1. Air Releases 5-15
5.7.2. Water Releases—None 5-16
5.7.3. Solid Residue Releases—None 5-16
5.7.4. Products 5-16
5.7.5. Release Summary 5-16
5.8. KRAFT BLACK LIQUOR RECOVERY BOILERS 5-17
5.8.1. Air Releases 5-17
5.8.2. Water Releases—None 5-17
5.8.3. Solid Residue Releases 5-18
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
5.8.4. Products 5-18
5.8.5. Release Summary 5-18
5.9. LIMEKILNS 5-19
5.9.1. Process Description 5-19
5.9.2. Regulations 5-20
5.9.3. Air Releases 5-20
5.9.4. Water Releases 5-21
5.9.5. Solid Residue Releases 5-21
5.9.6. Products 5-21
5.9.7. Release Summary 5-21
5.10. GLASS MANUFACTURING 5-22
5.11. OTHER IDENTIFIED SOURCES 5-24
6. COMBUSTION SOURCES OF CDDs/CDFs MINIMALLY CONTROLLED AND
UNCONTROLLED COMBUSTION SOURCES 6-1
6.1. COMBUSTION OF LANDFILL GAS 6-1
6.1.1. Air Releases 6-1
6.1.2. Water Releases 6-1
6.1.3. Solid Residue Releases—None 6-1
6.1.4. Products—None 6-1
6.1.5. Release Summary 6-1
6.2. ACCIDENTAL FIRES 6-3
6.2.1. Structural Fires 6-3
6.2.1.1. Air Releases 6-3
6.2.1.2. Water Releases 6-4
6.2.1.3. Solid Residue Releases 6-4
6.2.1.4. Products—None 6-4
6.2.1.5. Release Summary 6-4
6.2.2. Vehicle Fires 6-6
6.2.2.1. Air Releases 6-6
6.2.2.2. Water Releases 6-7
6.2.2.3. Solid Residue Releases 6-7
6.2.2.4. Products—None 6-8
6.2.2.5. Release Summary 6-8
6.3. LANDFILL FIRES 6-11
6.3.1. Air Releases 6-11
6.3.2. Water Releases—None 6-13
6.3.3. Solid Residue Releases—None 6-13
6.3.4. Products—None 6-13
6.3.5. Release Summary 6-13
6.4. FOREST AND BRUSH FIRES 6-14
6.4.1. Air Releases 6-14
6.4.2. Air Emission Factors 6-17
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CONTENTS (continued)
6.4.3. Air Activity Levels 6-18
6.4.4. Water Releases 6-19
6.4.5. Solid Residue Releases 6-19
6.4.6. Products—None 6-19
6.4.7. Release Summary 6-19
6.5. BACKYARD BARREL BURNING 6-21
6.5.1. Air Releases 6-21
6.5.2. Solid Residue Releases 6-23
6.5.3. Release Summary 6-24
6.6. RESIDENTIAL YARD WASTE BURNING 6-26
6.6.1. Air Releases 6-26
6.6.2. Water Releases—None 6-27
6.6.3. Solid Residue Releases 6-27
6.6.4. Products—None 6-27
6.6.5. Release Summary 6-27
6.7. LAND-CLEARING DEBRIS BURNING 6-28
6.7.1. Air Releases 6-28
6.7.2. Water Releases—None 6-29
6.7.3. Solid Residue Releases 6-29
6.7.4. Release Summary 6-29
6.8. UNCONTROLLED COMBUSTION OF POLYCHLORINATED
BIPHENYLS 6-31
6.9. VOLCANOES 6-32
6.10. FIREWORKS 6-32
6.11. OPEN BURNING AND OPEN DETONATION OF ENERGETIC
MATERIALS 6-32
6.12. UNDERGROUND COAL FIRES 6-33
6.13. AGRICULTURAL BURNING 6-33
6.13.1. Air Releases 6-33
6.13.2. Water Releases—None 6-34
6.13.3. Solid Residue Releases 6-35
6.13.4. Products—None 6-35
6.13.5. Release Summary 6-35
6.14. OPEN BURNING DEMOLITION/CONSTRUCTION WOOD 6-36
6.14.1. Air Releases 6-36
6.14.2. Water Releases—None 6-37
6.14.3. Solid Residue Releases 6-37
6.14.4. Release Summary 6-37
6.15. OIL SPILL BURNING 6-39
6.16. CANDLE BURNING 6-40
7. METAL SMELTING AND REFINING SOURCES OF CDD/CDFs 7-1
7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING 7-1
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CONTENTS (continued)
7.1.1. Primary Copper Smelting and Refining 7-1
7.1.1.1. Air Releases 7-1
7.1.1.2. Water Releases 7-1
7.1.1.3. Solid Residue Releases 7-1
7.1.1.4. Products 7-2
7.1.1.5. Release Summary 7-2
7.1.2. Primary Magnesium Smelting and Refining 7-3
7.1.2.1. Air Releases 7-3
7.1.2.2. Water Releases 7-4
7.1.2.3. Solid Residue Releases 7-4
7.1.2.4. Release Summary 7-4
7.1.3. Primary Nickel Smelting and Refining 7-6
7.1.3.1. Air Releases 7-6
7.1.3.2. Water Releases 7-6
7.1.3.3. Solid Residue Releases 7-6
7.1.3.4. Products 7-6
7.1.3.5. Release Summary 7-6
7.1.4. Primary Aluminum Smelting and Refining 7-7
7.1.5. Primary Titanium Smelting and Refining 7-7
7.1.5.1. Air Releases 7-8
7.1.5.2. Water Releases 7-8
7.1.5.3. Solid Residue Releases 7-8
7.1.5.4. Products 7-9
7.1.5.5. Release Summary 7-9
7.2. SECONDARY NONFERROUS METAL SMELTING AND REFINING 7-9
7.2.1. Secondary Aluminum Smelting and Refining 7-9
7.2.1.1. Air Releases 7-10
7.2.1.2. Water Releases 7-10
7.2.1.3. Solid Residue Releases 7-10
7.2.1.4. Products 7-10
7.2.1.5. Releases 7-10
7.2.2. Secondary Copper Smelting and Refining 7-11
7.2.2.1. Air Releases 7-12
7.2.2.2. Water Releases 7-12
7.2.2.3. Solid Residue Releases 7-12
7.2.2.4. Products 7-12
7.2.2.5. Releases 7-12
7.2.3. Secondary Lead Smelting 7-14
7.2.3.1. Air Releases 7-15
7.2.3.2. Water Releases 7-15
7.2.3.3. Solid Residue Releases 7-15
7.2.3.4. Products 7-15
7.2.3.5. Releases 7-15
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
7.2.4. Secondary Zinc Production 7-18
7.2.4.1. Air Releases 7-18
7.2.4.2. Water Releases 7-19
7.2.4.3. Solid Residue Releases 7-19
7.2.4.4. Products 7-19
7.2.4.5. Releases 7-19
7.3. PRIMARY FERROUS METAL SMELTING/REFINING 7-20
7.3.1. Sinter Production 7-20
7.3.1.1. Air Releases 7-20
7.3.1.2. Water Releases 7-21
7.3.1.3. Solid Residue Releases 7-21
7.3.1.4. Products 7-21
7.3.1.5. Releases 7-21
7.3.2. Coke Production 7-22
7.3.2.1. Air Releases 7-23
7.3.2.2. Water Releases 7-23
7.3.2.3. Solid Residue Releases 7-23
7.3.2.4. Products 7-23
7.3.2.5. Release Summary 7-24
7.4. SECONDARY FERROUS METAL SMELTING/REFINING 7-25
7.4.1. Air Releases 7-25
7.4.2. Water Releases 7-25
7.4.3. Solid Residue Releases 7-25
7.4.4. Products 7-25
7.4.5. Release Summary 7-25
7.5. FERROUS FOUNDRIES 7-27
7.5.1. Air Releases 7-27
7.5.2. Water Releases 7-27
7.5.3. Solid Residue Releases 7-27
7.5.4. Products 7-28
7.5.5. Release Summary 7-28
7.6. NONFERROUS METAL FOUNDRIES 7-29
7.6.1. Aluminum Foundries 7-29
7.6.2. Copper Foundries 7-31
7.7. SCRAP ELECTRIC WIRE RECOVERY 7-33
7.7.1. Air Releases 7-33
7.7.2. Water Releases 7-33
7.7.3. Solid Residue Releases 7-33
7.7.4. Products 7-33
7.7.5. Release Summary 7-34
7.8. DRUM AND BARREL RECLAMATION FURNACES 7-35
7.8.1. Air Releases 7-35
7.8.2. Water Releases 7-35
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
7.8.3. Solid Residue Releases 7-36
7.8.4. Products 7-36
7.8.5. Release Summary 7-36
8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 8-1
8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS 8-1
8.1.1. Air Releases 8-1
8.1.2. Water Releases 8-1
8.1.3. Solid Residue Releases 8-1
8.1.4. Products 8-2
8.1.5. Release Summary 8-2
8.2. STAND-ALONE CHLOR-ALKALI PLANTS 8-4
8.2.1. Process Description 8-5
8.2.2. Regulations 8-6
8.2.3. Literature 8-6
8.2.4. Releases 8-7
8.3. STAND ALONE VINYL CHLORIDE MANUFACTURING PLANTS 8-8
8.3.1. Process 8-9
8.3.2. Regulations 8-9
8.3.3. Literature 8-9
8.3.4. Releases 8-12
8.4. COMPLEX CHEMICAL PLANTS PRODUCING CHLORINE AND A VARIETY
OF CHLORINATED
ORGANICS 8-13
8.4.1. Chlorophenols 8-14
8.4.1.1. Process Description 8-14
8.4.1.2. Regulations for Chlorophenols 8-15
8.4.1.3. Products—Chlorophenols 8-17
8.4.1.4. Products—2,4 D 8-20
8.4.2. Chlorobenzenes 8-20
8.4.2.1. Process Description 8-20
8.4.2.2. Regulations for Chlorobenzenes 8-21
8.4.2.3. Products—Chlorobenzenes 8-22
8.4.3. Complex Plants 8-23
8.5. MUNICIPAL WASTEWATER TREATMENT PLANTS 8-26
8.5.1. Air Releases 8-27
8.5.2. Water Releases 8-27
8.5.3. Solid Residue Releases 8-27
8.5.4. Products 8-28
8.5.5. Releases 8-28
8.6. DRINKING WATER TREATMENT PLANTS 8-31
8.7. SOAPS AND DETERGENTS 8-31
8.8. TEXTILE MANUFACTURING AND DRY CLEANING 8-31
This document is a draft for review purposes only and does not constitute Agency policy.
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CONTENTS (continued)
8.9. DYES, PIGMENTS, AND PRINTING INKS 8-32
8.10. OTHER ALIPHATIC CHLORINE COMPOUNDS 8-32
8.11. RESIDENTIAL SEPTIC SYSTEMS 8-32
8.11.1. Process Description 8-33
8.11.2. Regulations 8-33
8.11.3. Emission Factor 8-33
8.11.4. Activity 8-34
8.11.5. Releases 8-34
9. NATURAL SOURCES OF CDDs/CDFs 9-1
9.1. BIOTRANSFORMATIONS 9-1
9.1.1. Biotransformation of Chlorophenols 9-1
9.1.2. Biotransformation of Higher CDDs/CDFs 9-2
9.1.3. Biotransformation of Animal Manure 9-2
9.2. PHOTOCHEMICAL TRANSFORMATIONS 9-3
9.2.1. Photolysis of PCP 9-4
9.2.2. Photolysis of Higher CDDs/CDFs 9-4
9.2.3. Photolysis in Water 9-4
9.2.4. Photolysis on Soil Surfaces 9-4
9.2.5. Photolysis on Vegetation 9-5
9.2.6. Photolysis in Air 9-5
9.3. CDDs/CDFs IN BALL CLAY 9-5
10. SOURCES OF DIOXIN-LIKE POLYCHLORINATED BIPHENYLS (PCBs) 10-1
10.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY 10-1
10.2. RELEASES FROM COMMERCIAL PCB PRODUCTS 10-2
10.2.1. Approved PCB Disposal/Destruction Methods 10-2
10.2.2. Releases of In-Service PCBs 10-2
10.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 10-4
10.4. COMBUSTION SOURCES 10-6
10.4.1. Municipal Waste Combustion 10-6
10.4.2. Industrial Wood Combustion 10-8
10.4.3. Medical Waste Incineration 10-9
10.4.4. Tire Combustion 10-10
10.4.5. Cigarette Smoking 10-11
10.4.6. Sewage Sludge Incineration 10-12
10.4.7. Backyard Barrel Burning 10-13
10.4.8. Petroleum Refining Catalyst Regeneration 10-15
10.4.9. Hazardous Waste Incineration 10-16
10.4.10. Power Plants 10-16
10.4.11. Forest Fires 10-17
10.5. METAL REFINING SOURCES 10-19
10.6. NATURAL SOURCES (originally Section 10.5) 10-23
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CONTENTS (continued)
10.6.1. Biotransformation of Other PCBs 10-23
10.6.2. Photochemical Transformation of Other PCBs 10-23
10.7. PAST USE OF COMMERCIAL PCBs (originally Section 10.6) 10-23
11. RESERVOIR SOURCES OF CDD/CDFs AND DIOXIN-LIKE PCBs 11-1
11.1. SOIL RESERVOIRS (originally Section 11.2.1) 11-2
11.1.1. Mechanisms Responsible for Releases from Surface Soils 11-4
11.1.2. Estimated Annual Releases from Soil to Water 11-4
11.1.2.1. Urban Runoff 11-4
11.1.2.2. Rural Soil Erosion 11-5
11.1.3. Estimated Annual Releases from Soil to Air 11-5
11.2. WATER RESERVOIRS (originally Section 11.2.2) 11-7
11.3. SEDIMENT RESERVOIRS (originally Section 11.2.3) 11-8
11.3.1. Mechanisms Responsible for Supply to and Releases from Sediment 11-8
11.3.2. Releases from Sediment to Water 11-8
11.4. BIOTA RESERVOIRS (originally Section 11.2.4) 11-8
11.4.1. Mechanisms Responsible for Supply to and Releases from Biota 11-9
11.4.2. Approaches for Measuring and Estimating Releases from Biota 11-9
11.5. PRODUCT RESERVOIRS 11-9
11.5.1. Bleached Chemical Wood Pulp 11-9
11.5.2. Chlorophenols 11-10
11.5.3. Vinyl Chloride Products 11-11
11.5.4. Chloranil 11-11
11.5.5. Polychlorinated Biphenyls (PCBs) 11-11
11.6. SUMMARY AND CONCLUSIONS (originally Section 11.3) 11-12
BIBLIOGRAPHY
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LIST OF TABLES
ES-1. Overview of changes to total quantities of TEQ emissions to air and land from the
2006 inventory xxiv
ES-2. Overview of total releases to air, land, water, and products in the updated inventory.. xxvii
ES-3. Changes in quantitative release estimates from 2006 Report to present Report xxxii
1-1. Nomenclature for dioxin-like compounds 1-25
1-2. TEF schemes for CDDs, CDFs, and PCBs 1-26
1-3. Municipal waste combustors 1-28
1-4. Hazardous waste combustors 1-29
1-5. Cement kilns not burning hazardous waste 1-30
1-6. Secondary aluminum smelters 1-30
1-7. Medical waste incinerators 1-31
1-8. Pulp and paper mills 1-31
1-9. Commercial/Industrial solid waste incinerators 1-31
1-10. Sewage sludge incinerators 1-32
1-11. Industrial, commercial, and institutional boilers and process heaters 1-32
1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 1-33
1-13. Summary of PCB releases for reference years 1987, 1995, and 2000 1-48
1-14. Summary of CDD/CDF reservoir releases 1-51
1-15. Summary of PCB reservoir releases 1-51
1-16. Ranking of top five sources by year and media release 1-52
1-17. Amounts of CDDs/CDFs contained in products in year manufactured 1-52
1-18. Trend analyses based on quantitative inventory 1-53
1-19. Uncertainty analysis for top nine air sources in 2000 1-54
3-1. Inventory of municipal waste combustors in 1987 3-31
3-2. Inventory of municipal waste combustors in 1995 3-39
3-3. Inventory of municipal waste combustors in 2000 3-49
3-4. TEQ emissions from medical waste incinerators for reference year 1987, 1995,
and 2000 3-57
5-1. CDD/CDF TEQ emission factors and emission estimates from Kraft lime kilns 5-25
6-1. CDD/CDF emission factors for forest fires 6-41
6-2. Comparison of Forest Fire Data 6-43
8-1. CDD/CDF concentrations in graphite electrode sludge from chlorine production 8-36
8-2. Releases of dioxin-like compounds in wastewater discharges from chlor-alkali
manufacturing facilities to surface water in 2000 8-37
8-3. Congener-specific and TEQ annual releases to air from a chlor-alkali facility
in 2000 8-38
8-4. Annual releases in 2000 from stand-alone chlor-alkali plants 8-39
8-5. Reported CDD/CDF concentrations in wastes from polyvinyl chloride
manufacture 8-40
8-6. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers 8-41
8-7. Annual releases in 2000 from stand-alone vinyl chloride plants 8-43
8-8. CDD/CDF concentrations in mono-through tetrachlorophenols 8-44
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LIST OF TABLES
8-9. Summary of specific dioxin-containing wastes that must comply with land
disposal restrictions 8-45
8-10. CDD/CDF concentrations (historical and current) in technical-grade
pentachlorophenol products 8-47
8-11. Historical CDD/CDF concentrations in pentachlorophenol-Na 8-49
8-12. CDD/CDF concentrations in chlorobenzenes 8-51
8-13. Annual releases in 2000 from complex plants producing chlorine and a variety
of chlorinated organics 8-52
8-14. CDD/CDF mean concentrations measured in the 2001 National Sewage Sludge
Survey 8-54
9-1. CDD and CDF concentrations in samples of animal manure in the
United Kingdom 9-7
10-1. Summary of PCB releases for reference years 1987, 1995, and 2000 10-24
10-2. PCB analysis for composite ash samples from barrel burning 10-27
11-1. Amounts of CDD/CDFs Landfilled 11-13
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LIST OF FIGURES
1-1. Process inputs and outputs 1-55
6-1. Congener profile for structure fires 6-44
6-2. Forest fire types in the United States 6-45
8-1. Congener profile for technical grade PCP 8-55
11-1. Fluxes among environmental reservoirs 11-14
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LIST OF ABBREVIATIONS AND ACRONYMS
APCD Air pollution control device
BDDs polybrominated dibenzo-p-dioxins
BDFs polybrominated dibenzofurans
Btu British thermal unit
CARB California Air Resources Board
CDD polychlorinated dibenzo-p-dioxin
CDF polychlorinated dibenzofuran
CFR Code of Federal Regulations
CKD cement kiln dust
DBF dibenzofuran
DCBz dichlorobenzene
DCI data call-in
DCP dichlorophenol
DL detection limit
dscm dry standard cubic meter
DSI dry sorbent injection
EDC ethylene dichloride
EIA Energy Information Administration
EPA U.S. Environmental Protection Agency
EPRI Electric Power Research Institute
ESP electrostatic precipitator
FF fabric filter
FIFRA Federal Insecticide, Fungicide, and Rodenticide Act
GAC granular activated carbon
GC/ECD gas chromatography/electron capture detector
GC/MS gas chromatography/mass spectrometry
HC1 hydrogen chloride
HCBz hexachlorobenzene
HDD halogenated dibenzo-p-dioxin
HDF halogenated dibenzofuran
HWI hazardous waste incinerator
HxCB hexachlorobiphenyl
IUPAC International Union of Pure and Applied Chemistry
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LOQ limit of quantitation
MB-WW mass burn waterwall
MCBz monochlorobenzene
MMT million metric tons
MSW municipal solid waste
MT metric ton (1000 kg)
MWI medical waste incinerator
NCASI National Council of the Paper Industry for Air and Stream Improvement
Nm3 standard cubic meter
NMOC nonmethane organic compound
OAQPS Office of Air Quality Planning and Standards
OH hydroxide ion
OPP Office of Pesticide Programs
ORD Office of Research and Development
OSW Office of Solid Waste
PCA Portland Cement Association
PCB polychlorinated biphenyl
PCP pentachlorophenol
PeCB pentachlorobiphenyl
PeCBz pentachlorobenzene
PM particulate matter
POTW publicly owned treatment works
ppb parts per billion
ppm parts per million
ppmv parts per million (volume basis)
ppt parts per trillion
PVC polyvinyl chloride
QA/QC quality assurance/quality control
RCRA Resource Conservation and Recovery Act
RDF refuse-derived fuel
SIC Standard Industrial Classification
SIP State Implementation Plan
TCBz trichlorobenzene
TCDD 2,3,7,8-tetrachlorobidenzo:p-dioxin
TCDF 2,3,.7,8-tetrachlorobidenzofuran
TeCB tetrachlorobiphenyl
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TeCP tetrachlorophenol
TEF toxicity equivalency factor
TEQ toxicity equivalence
TEQ/yr toxicity equivalents per year
TrCB trichlorobiphenyl
TrCP trichlorophenol
TRI Toxics Release Inventory
TSCA Toxic Substances Control Act
2,4-D 2,4-dichlorophenoxyacetic acid
2,4-DCP 2,4-dichlorophenol
2,4,5-T 2,4,5-trichlorophenoxy (phenoxy herbicides)
U.K. United Kingdom
USDA U.S. Department of Agriculture
VCM vinyl chloride monomer
WHO World Health Organization
WS wet scrubber
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PREFACE
In 2006, EPA released a Dioxin Inventory Report that provided a comprehensive inventory and
overview of sources and environmental releases of dioxin-like compounds in the United States
(U.S. EPA, 2006). The purpose of this current document is to present an update and revision to
the 2006 dioxin source inventory. This report includes some new data and also addresses
additional comments EPA received on the 2006 Dioxin Inventory Report after it was published.
This document was prepared by the National Center for Environmental Assessment, Office of
Research and Development of the U.S. Environmental Protection Agency.
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AUTHORS, CONTRIBUTORS, AND REVIEWERS
AUTHORS
John Schaum, National Center for Environmental Assessment, Office of Research and
Development, U.S. Environmental Protection Agency, Washington, DC.
David Cleverly, National Center for Environmental Assessment, Office of Research and
Development, U.S. Environmental Protection Agency, Washington, DC.
Matthew Lorber, National Center for Environmental Assessment, Office of Research and
Development, U.S. Environmental Protection Agency, Washington, DC.
CONTRIBUTORS
Dwain Winters, Office of Pollution Prevention and Toxics, U.S. Environmental Protection
Agency, Washington, DC
REVIEWERS
Linda Phillips, National Center for Environmental Assessment, Office of Research and
Development, U.S. Environmental Protection Agency, Washington, DC.
ACKNOWLEDGMENTS
This report is derived largely from the original version published in 2006. The contributions
from the numerous authors and reviewers of that report (see full list in U.S. EPA, 2006) are
gratefully acknowledged.
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EXECUTIVE SUMMARY
Synopsis
The purpose of this document is to present an update and revision to the dioxin source
inventory published in 2006 (U.S. EPA, 2006), which is an inventory of sources and
environmental releases of dioxin-like compounds in the United States for the years 1987, 1995,
and 2000. The current document presents updated estimates of environmental releases of dioxin-
like compounds to the air, water, land and products. These updates do not expand the scope of
the document beyond the three reference years covered in the original document: 1987, 1995,
and 2000.
The sources in this report are grouped into five broad categories: combustion sources,
metals smelting/refining, chemical manufacturing, natural sources, and environmental reservoirs.
The quantitative results are expressed in terms of the toxicity equivalence (TEQ) of the mixture
of polychlorinated dibenzo-p-dioxin (CDD) and polychlorinated dibenzofuran (CDF) compounds
present in environmental releases using a procedure sanctioned by the World Health
Organization (WHO) in 1998. This TEQ procedure translates the complex mixture of CDDs and
CDFs in the environmental releases into a single equivalent toxicity concentration (or mass) of
2,3,7,8-tetrachorodibenzo-p-dioxin (2,3,7,8-TCDD), the most toxic member of this class of
compounds.
The updated releases to land and air are presented in Table ES-1, alongside the results
from the 2006 report. The quantitative releases to water and products did not change.
While the overall decreasing trend in emissions seen in the original report continues, the
individual dioxin releases in this draft updated report are generally higher than the values
reported in 2006. This is largely due to the inclusion of additional sources in the quantitative
inventory that were not included in the 2006 report.
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Table ES-1. Overview of changes to total quantities of TEQ emissions to air and land
from the 2006 inventory
Description
2006 Report
Present Report
Air Releases (g WHO98 TEQ)
1987
1995
2000
13,500
3,200
1,300
15,000
3,400
2,300
Land Releases (g WHO98TEQ)
1987
1995
2000
130
150
82
2,400
2,500
2,300
For example, air releases are higher than listed in the 2006 report because the draft
updated report includes emissions from forest fires as well as adjustments to emission factors
used for municipal and medical waste incinerators. Forest fires were only reported as
preliminary in 2006, but new experimental data has resulted in more certainty in the
development of an emission factor for this source. Hence emissions were more accurately
quantified as compared to the preliminary estimate made in 2006 and reclassified for inclusion in
the quantitative inventory. The quantitative releases to land are markedly higher for all years
compared to the 2006 report, due almost entirely to including ash from backyard trash burning in
the current draft.
The current report still contains estimates for some sources that are considered
preliminary and not included in the quantitative inventory. Some of these sources are potentially
large and, if confirmed, could change the trend observations based on the currently quantified
sources, as happened with forest fires for this updated report.
Approach
Dioxin releases from a source can be in the form of products, air emissions, water
discharges, and solid residues. Solid residues can be used in products or disposed via landfills or
incinerators. Each source addressed in this document is evaluated in terms of all of these
outputs. However, not all of the outputs are considered to be environmental releases. Outputs
judged to have a reasonable likelihood for releases to the circulating environment include all air
emissions, water discharges, and landfarmed wastes. Outputs that are not generally considered
environmental releases include waste disposal at a lined landfill and intermediate products or
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internal waste streams. While it is recognized that some of the dioxins contained in products or
disposed in secure landfills may be released to the circulating environment at some time in the
future, they are less likely to be released to the circulating environment during the same year that
they entered into commerce or were landfilled. Consequently, these contained dioxins would not
initially be considered environmental releases. Ideally, releases derived from products and
landfill practices of past years would be included in the inventory for the reference year in which
the releases occur. Unfortunately, the current state of science does not support estimating when
and to what degree such releases may occur. For informational purposes, and when sufficient
information is available, this document provides estimates of the amounts of solid waste
disposed in landfills.
Sources can be categorized in terms of when releases occur: (1) contemporary
formation sources (sources that have essentially simultaneous formation and release) and (2)
reservoir sources (materials or places that contain previously formed CDDs/CDFs or dioxin-like
PCBs that are rereleased to the environment). The contemporary formation sources are
discussed in Chapters 3 through 10, and the reservoir sources are discussed in Chapter 11.
This document also classifies sources into five broad categories based mainly on their
formation process:
• Combustion. CDDs/CDFs are formed in most types of combustion. This document
addresses waste incineration, sources related to power/energy generation, a variety
high temperature sources (including cement kilns, asphalt plants, carbon reactivation
furnaces, and others) and minimally controlled or uncontrolled sources (including
landfill gas flares/fires, forest fires, backyard trash burning in barrels, and others).
• Metals Smelting/Refining. This category includes sources that are involved in
metals smelting, refining, and processing.
• Chemical Manufacturing. CDDs/CDFs can be formed as by-products in a variety
of chemical manufacturing operations. These include chlorine-bleached wood pulp,
chlorinated phenols (e.g., pentachlorophenol), PCBs, chlorobenzenes, phenoxy
herbicides (e.g., 2,4-D and 2,4,5-T), and chlorinated aliphatic compounds (e.g.,
ethylene dichloride, vinyl chloride, polyvinyl chloride).
• Biological, Photochemical, and Other Natural Processes. CDDs/CDFs can form
via biological processes such as the action of microorganisms on chlorinated phenolic
compounds and also during photolysis of highly chlorinated phenols.
• Reservoirs. Reservoirs are environmental compartments and materials that have the
capacity to store previously formed CDDs/CDFs or dioxin-like PCBs. These
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compounds are thus sequestered from the open and circulating environment.
Potential reservoirs include soils, sediments, and biota as well as some anthropogenic
materials, such as PCP-treated utility poles. Dioxin-like compounds in these
reservoirs have the potential for redistribution and circulation in the environment
through the physical processes such as leaching, volatilization, erosion,
sedimentation, and deposition. Whenever dioxins are released from their place of
storage back into the circulating environment, the reservoir is considered a source of
dioxin.
The approach used to estimate the emissions from most sources is based on an
emission factor which relates mass of dioxins released into the environment with some measure
of activity (e.g., kilograms of material processed per year, vehicle miles traveled per year, liters
of wastewater discharged per year). The emission factor representing a class of facilities is
developed by averaging the emission factors across the tested facilities in the class. This average
emission factor is then multiplied by the measure of activity for the class to get total releases.
In this update, a revised approach has been developed to characterize the confidence
ratings of the release estimates. The revised approach maintains the three major categories
previously used, i.e., (1) the quantitative inventory [which now includes the sum of the previous
confidence ratings that were subdivided into Class A, B, or C], (2) the preliminary release
estimates [previously assigned a rating of Class D], and the unquantifiable sources [previously
assigned a rating of Class E]. The major changes are the elimination of the Class A, B, or C
confidence distinctions in the quantitative inventory and the addition of the quantitative
uncertainty analysis of the quantitative inventory (presented in Section 1.3.6). The old Class A,
B, and C confidence ratings were eliminated because they were too subjective and difficult to
apply in a consistent fashion. Also, it was judged that confidence ratings for the individual
source classes were less essential because a new quantitative uncertainty analysis has been added
(see discussion below).
Key components of both the old and new schemes for classifying facilities are the criteria
for deciding whether a source belongs in the quantitative inventory or the preliminary class. This
update uses more specific guidance for making this decision. In order for a source to be included
in the quantitative inventory, it must (a) have emission tests for at least two units/source types
with sufficient documentation to directly derive emission factors, (b) the measured emission
factors must be reasonably consistent or have understandable differences, (c) the emission factor
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tests must represent units that are reasonably typical of the class and (d) the activity estimates
must be based on source-specific surveys.
The actual magnitude of releases from the preliminary sources could be significantly
lower or higher than estimated. Although EPA does not support including them in the
quantitative inventory at this time, some of these preliminary sources have the potential of being
major contributors of releases to the environment. Accordingly, they are important to identify
and could be used to help set priorities for future research and data collection. As the uncertainty
around these sources is reduced, they will be included in future inventory calculations.
Results
Eighty source categories were identified with the potential for dioxin emissions. An
overview of the total releases to air, land, water, and products is provided in Table ES-2. The
major conclusions regarding CDD/CDF releases from contemporary formation sources are
presented below:
• The total releases under the national quantitative inventory for 1987 in g WHOgg TEQDF
were 15,000 to air, 2,400 to land, 360 to water, and 36 to products.
• The total releases under the national quantitative inventory for 1995 in g WHOgg TEQop
were 3,400 to air, 2,400 to land, 30 to water, and 47 to products.
• The total releases under the national quantitative inventory for 2000 in g WHOgg TEQop
were 2,300 to air, 2,300 to land, 28 to water, and 7 to products.
Table ES-2. Overview of total releases to air, land, water, and products in the updated
inventory
Year
1987
1995
2000
Releases (g WHO98 TEQ)
Air
15,000
3,400
2,300
Land
2,400
2,400
2,300
Water
360
30
28
Products
36
47
7
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• The top three quantified air sources in 2000 were:
o forest fires (73 0 g WHO98 TEQDF),
o backyard barrel burning of refuse (600 g WHOgg TEQDF), and
o medical waste incinerators (400 g WHOgg TEQop).
• Sources with preliminary release estimates have the potential for large releases of dioxin-
like compounds. While not included in the current quantitative estimates listed above,
future inclusion of these sources could change current release estimates. The largest
preliminary sources in the current report are:
o accidental fires at landfills (1,300 g WHO98 TEQDF to air in 2000), and
o land clearing debris burning (85 g WHOgg TEQop to air in 2000).
• A total of 20 contemporary formation sources were identified as having unquantifiable
releases to one or more media. Information suggests these may be sources of dioxin-like
compounds, but it is insufficient to make a national estimate of releases.
• The chemical product with the largest amount of CDD/CDF is pentachlorophenol, but the
environmental releases associated with this product (primarily used to treat wood) could
not be estimated. Release estimates could only be made for 2,4-D, where it can be
assumed that the entire amount produced is released to the environment.
The environmental releases of dioxin-like PCBs have not been well characterized. PCBs
were not produced during the reference years, but are still present in capacitors, transformers,
building materials and other products in use today. No estimates could be made for releases
from these in-use products. Only one source (backyard barrel burning) was judged to have
adequate data to support quantitative air-release estimates for dioxin-like PCBs: 41, 43, and
34 g WHOgg TEQp for the years 1987, 1995, and 2000, respectively. Similarly, only two sources
(backyard barrel burning and municipal wastewater treatment) were judged to have adequate
data to support quantitative land release estimates for dioxin-like PCBs: 52, 78, and
20 g WHO9g TEQp for the years 1987, 1995, and 2000, respectively. Also, only preliminary
estimates could be made for 6 sources, and 10 sources were identified as being unquantifiable.
Although the information is limited, it suggests that, in terms of TEQs, PCB releases are much
lower than CDD/CDF releases.
Soil is likely to be the reservoir source with the greatest potential for release of
CDD/CDFs and PCBs to other environmental media, particularly to water. This is due to its
relatively large mass of stored CDD/CDFs and PCBs and the existence of demonstrated
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transport mechanisms for intermedia exchange, e.g., soil erosion to surface waters and particle
resuspension to air.
Discussion
Some observations about how releases have changed over the reference years can be
made for the quantified sources. It is important to understand, though, that these observations do
not include the sources classified as preliminary or unquantifiable. Some of the preliminary
sources are potentially very large and, if confirmed and included in future quantitative estimates,
could change the trend observations based on the currently quantified sources. With this caveat
in mind, the following trends were identified. In terms of total releases from all media, a 67%
reduction occurred from 1987 to 1995, a 23% reduction occurred from 1995 to 2000, and a 74%
reduction occurred from 1987 to 2000.
Significant amounts of the dioxin-like compounds produced annually in the United States
are not considered releases to the open and circulating environment and are not included in the
national inventory. Examples include dioxin-like compounds generated internal to a process but
destroyed before release and waste streams that are disposed of in approved landfills.
A number of contemporary formation sources were classified as preliminary or
unquantifiable and, therefore, were not included in the inventory. The largest contemporary
formation preliminary source is accidental fires at municipal solid waste landfills. This source
has the potential to significantly increase the release estimates for 2000 if preliminary estimates
are confirmed.
A series of analyses were used to assess the uncertainties of the quantitative inventory.
This analysis was limited to the air and land releases from the top sources (accounting for over
90% of the releases) in 2000. This first involved using a propagation of error approach, which
estimates the variance for the air emissions from each source and sums these to get the overall
variance in total emissions. Multiple factors contribute to the uncertainty in the emission
estimate for a class of facilities. These include sampling error which reflects the number of
facilities tested out of the total, the representativeness of the tests of long term conditions, and
measurement error from inaccuracies in the stack monitoring and chemical analysis. The
propagation of error approach used here assumes that the variability in the emissions from the
sampled facilities is an indication of the possible uncertainty in the emissions from the whole
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class of facilities. The analysis concludes that the total air releases from the top sources in 2000
sum to 2,100 g TEQ/year with a standard deviation of 1,300 g TEQ/year.
Secondly, a probabilistic analysis was conducted to evaluate the uncertainties in the air
releases. All emission factors were assumed to have log normal distributions with means and
standard deviations based on an arithmetic analysis of the data. A Monte Carlo analysis was
conducted using the Crystal Ball program. A total of 10,000 simulations were run, producing a
mean of 2,100 g TEQ and standard deviation of 1,100 g TEQ, which are very similar to the
results of the propagation-of-error approach described above. Percentiles were estimated as
1,100 g TEQ for 10%, 1,800 g TEQ for 50%, and 3,300 g TEQ for 90%. These percentiles can
be interpreted as the probability that the emissions will less than or equal to the specified
amount.
Finally, further analysis is offered on the uncertainties associated with the forest fire air
releases. These uncertainties are especially important to evaluate because they are the largest
source and have high uncertainty in the emission factor. Both chamber studies and field studies
have been used to measure these emissions. The field data suggest an emission factor of
0.95 ng TEQ/kg, and the chamber data suggest an emission factor of 7.5 ng TEQ/kg. If the
lower emission factor is used, the forest fires would have a release of 230 g TEQ, and the total
releases across the nine top sources in 2000 would be 1,600 g TEQ. Similarly, if the higher
emission factor is used, the forest fires would have a release of 1,800 g TEQ, and the total
releases across the nine top sources in 2000 would be 3,200 g TEQ.
The 2000 land releases were dominated by backyard barrel burning which had releases of
1,900 g WHOgg TEQ (88% of the total) and the uncertainty analysis for land releases was limited
to this one source. The releases from backyard barrel burning were based on a study by Lemieux
(1997). Ash samples from the experiments were combined, resulting in two composite samples,
one for recyclers (2,700 ng WHOgg TEQop /kg ash) and one for nonrecyclers
(620 ng WHOgg TEQop /kg ash). The final emission factor was based on the average of these
values (1,700 ng WHOgg TEQop /kg ash). The limited data do not allow statistical analyses such
as that done for the air releases. Instead a potential range of releases was estimated based on the
lower and upper emission factor estimates. The activity estimate for 2,000 was 1.2 MMT.
Combining this value with the lower emission factor yields a release estimate of
740 g WHOgg TEQ. Combining the activity with the higher emission factor yields a release
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estimate of 2,800 g WHOgg TEQ. Accordingly the potential range of releases is 740 to
2,800 g WHO98 TEQ. Relative to the average value (1,900 g WHO98 TEQ), the lower estimate
is 62% less and the upper estimate is 46% more.
Changes from 2006 Document
This discussion summarizes the changes from the 2006 report to the present report.
Quantitative release estimates of CDD/CDFs to air increased for all years. The changes reflect
the addition of new sources and adjustments to emission factors used for municipal and medical
waste incinerators. The largest new source was forest fires which was previously classified as
preliminary and not included in the quantitative inventory. Based on a number of new studies, it
was decided that sufficient data were now available to move this source into the quantitative
inventory. The forest fire releases in 2000 were about 4 times higher than 1987 and 1995 (due to
more fires) causing a particularly large percent increase in that year. Other new sources added to
the present document were secondary zinc smelters, glass manufacturers, lime kilns, agricultural
burning, outdoor wood combustors, aluminum foundries, copper foundries and septic systems.
Quantitative release estimates of CDD/CDFs to land also increased for all years. These
increases were due almost entirely to ash from backyard barrel burning which had not been
addressed in the 2006 report. The quantitative releases to water and products did not change.
The changes to the air and land releases are summarized in Table ES-3 below.
For dioxins, furans, and PCBs combined, the 2006 report indicated a 90% decrease in
quantitative releases from 1987 to 2000. The updated report now indicates a 74% decrease over
this time period. This reduction is due primarily to the addition of ash from backyard barrel
burning (which remained relatively constant over the years) and air releases from forest fires
(which had a particularly large release in 2000 as discussed above). The present document
emphasizes that some of the preliminary sources are potentially very large and, if confirmed,
could change the trend observations based on the currently quantified sources.
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Table ES-3. Changes in quantitative release estimates from 2006 Report to present Report
2006
Report
Present
Report
Primary Reason for Change
Air Releases (g WHO98 TEQ)
1987
1995
2000
13,500
3,200
1,300
15,000
3,400
2,300
Addition of forest fires, changes to municipal and
medical waste incinerators
Addition of forest fires, changes to municipal and
medical waste incinerators
Addition of forest fires, changes to municipal and
medical waste incinerators
Land Releases (g WHO9s TEQ)
1987
1995
2000
130
150
82
2,400
2,500
2,300
Addition of backyard barrel burners
Addition of backyard barrel burners
Addition of backyard barrel burners
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1 1. BACKGROUND, APPROACH, AND CONCLUSIONS
2
O
4 1.1. BACKGROUND
5 This report presents an update to the dioxin source inventory published in 2006 (U.S.
6 EPA, 2006). The update does not expand the scope of the document beyond the three reference
7 years covered in the original document: 1987, 1995, and 2000.
8 This document is organized in a parallel fashion to the 2006 document, i.e., both
9 documents use the same chapter/section sequence, although several additional sections have been
10 added for new sources. This first chapter of the document is a complete rewrite and should be
11 used as a replacement of Chapter 1 in the 2006 document. Chapter 2 on formation theory was
12 not updated because it is not critical for the inventory. All subsequent chapters have sections
13 organized by environmental media, i.e., releases to air, water, land, and products. Individual
14 sections do not repeat the material in the 2006 document. Instead, they summarize new literature
15 references and describe any changes in release estimates. At the end of each section, a table is
16 presented (in a shaded text box to facilitate their identification and location) that provides all
17 emission factors, activities, and release estimates. Most readers will only need to use this
18 updated document because it describes all changes from the 2006 document and provides the
19 bottom-line release estimates for all sources. Readers interested in further details about sources
20 (i.e., process descriptions, summaries of the older literature, information on congener profiles,
21 etc.) may find it helpful to consult the 2006 document.
22
23 1.1.1. Dioxin-Like Compounds
24 This document addresses specific compounds in the following chemical classes:
25 chlorinated dibenzo-/?-dioxins (CDDs), chlorinated dibenzofurans (CDFs), and polychlorinated
26 biphenyls (PCBs). The physical/chemical properties of these compounds vary according to the
27 degree and position of chlorine substitution. However, these compounds are generally
28 hydrophobic, persistent in the environment, resistant towards metabolism, and bioaccumulate in
29 the fatty tissues of animals and humans.
30 The CDDs include 75 individual compounds, CDFs include 135 individual compounds,
31 and PCBs include 209 individual compounds. These individual compounds are technically
32 referred to as congeners. 2,3,7,8-tetrachlorodibenzo-p-dioxin is the most widely studied (and
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1 historically considered to be the most toxic) chemical in this general class of compounds. A
2 relatively small subset of the CDDs, CDFs, and PCBs are considered to have dioxin-like toxicity.
3 These compounds have similar chemical structures and invoke a common battery of toxic
4 responses as 2,3,7,8-TCDD. Only 7 of the 75 CDD congeners and 10 of the 135 CDF congeners
5 are recognized to have dioxin-like toxicity; they are the ones with chlorine substitutions in, at a
6 minimum, the 2, 3, 7, and 8 positions. There are 209 PCB congeners; of which, only 12 are
7 recognized to have dioxin-like toxicity—those with four or more lateral chlorine atoms with one
8 or no substitution in the ortho position. These compounds are sometimes referred to as coplanar,
9 meaning that they can assume a flat configuration with rings aligned along the same plane.
10 Other halogenated compounds have been identified as having dioxin-like toxicity, such as
11 chlorinated naphthalenes, brominated dibenzo-p-dioxins and dibenzofurans, and similar
12 compounds with a mix of bromines and chlorines. However, as discussed below, these are not
13 addressed in this document.
14 The term "dioxins" has been used in several different ways in the literature. For
15 example, it has been used to refer to TCDD only, all CDDs and CDFs, or subsets of these
16 compounds. The present document uses "dioxins" to refer generally to the CDDs, CDFs, and
17 PCBs that have dioxin-like toxicity. (This can also be defined as the 17 CDDs/CDFs and 12
18 coplanar PCBs with toxicity equivalence factors [TEFs] greater than zero; this concept of
19 toxicity equivalence is discussed further in Section 1.1.2 below.) Similarly, the phrase "dioxin-
20 like compounds" is used in this document to refer to only those compounds with established TEF
21 values. As noted above, a number of other compounds have been suggested to have "dioxin-like
22 toxicity," but these are not addressed in this document.
23 This document focuses primarily on the 17 CDDs/CDFs, with a more limited discussion
24 of the 12 coplanar PCBs. This is because there are relatively little congener-specific data on
25 PCB releases.
26 Table 1-1 provides a complete listing of the chemical nomenclature used in this report.
27
28 1.1.2. Toxicity Equivalence Factors
29 CDDs, CDFs, and PCBs are commonly found as complex mixtures when detected in
30 environmental media, biological tissues, or releases from specific sources. Humans are likely to
31 be exposed to mixtures of these compounds that vary by source and pathway, complicating the
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1 assessment of human health risk assessment. To address this problem, the concept of a "toxicity
2 equivalence" (TEQ) has been developed.
3 TEFs compare the toxicity of each dioxin-like compound in the mixture to the
4 well-studied 2,3,7,8-TCDD, historically considered the most toxic member of the group. The
5 comparison procedure involves assigning individual TEFs to the 2,3,7,8-substituted CDD/CDF
6 congeners and dioxin-like PCBs. To accomplish this, scientists have reviewed the toxicological
7 databases and, with considerations of chemical structure, persistence, and resistance to
8 metabolism, have agreed to ascribe specific "order-of-magnitude" TEFs for each dioxin-like
9 congener relative to 2,3,7,8-TCDD, which is assigned a TEF of 1. The other congeners have
10 TEF values ranging from 1 to 0.00001.
11 To apply this concept, the TEF of each congener present in a mixture is multiplied by the
12 respective mass concentration, and the products are added to represent the 2,3,7,8-TCDD TEQ of
13 the mixture (eq 1-1).
14
15 TEQ = Ł Concentration, x TEF1 (1 -1)
z=l
16
17 A variety of TEF schemes have been developed since the 1980s. This can lead to
18 confusion when a TEQ value is presented without a clear designation of which TEF scheme was
19 used to calculate it. This document uses a nomenclature that distinguishes between the different
20 TEF schemes and identifies the congener groups included in specific TEQ calculations:
21
22 • I-TEQ refers to toxic equivalents derived using the international TEF scheme adopted by
23 EPA in 1989 (U.S. EPA, 1989).
24 • WHO94 TEQ refers to toxic equivalents derived using the 1994 World Health
25 Organization (WHO) extension of the I-TEF scheme, which includes 13 dioxin-like
26 PCBs (Ahlborg et al., 1994).
27 • WHOgg TEQ refers to toxic equivalents derived using the 1998 WHO update to the
28 previously established TEFs for dioxins, furans, and dioxin-like PCBs (Van den Berg
29 etal., 1998).
30 • WHO2005 TEQ refers to toxic equivalents derived using the 2005 WHO update to the
31 previously established TEFs for dioxins, furans, and dioxin-like PCBs (Van den Berg
32 et al., 2006).
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1
2 Table 1-2 shows all four of these TEF schemes.
3 The nomenclature also uses subscripts to indicate which family of compounds is included
4 in any specific TEQ calculation. Under this convention, a subscript D is used to designate
5 dioxins, a subscript F is used to designate furans, and a subscript P is used to designate PCBs.
6 As an example, WHOgg TEQDF would be used to describe a mixture for which only dioxin and
7 furan congeners were determined and where the TEQ was calculated using the WHOgg scheme.
8 If PCBs had also been determined, the nomenclature would be WHOgg TEQopp Note that in this
9 document I-TEQ sometimes appears without the D or F subscripts. This indicates that the TEQ
10 calculation includes both dioxins and furans.
11 This document uses the WHOgg TEF scheme as the primary basis for presenting TEQ
12 estimates. While the WHO2005 TEFs are more current, the previous version of this document
13 used the WHOgg TEFs. This document continues the use of the WHOgg TEFs to be consistent
14 with the 2006 document, allowing for easy comparison. A limited number of estimates were
15 generated using the newer TEF values, and it was seen that differences were inconsequential
16 (data not provi ded).
17 Throughout this document, environmental release estimates are presented in terms of
18 TEQs. This is consistent with previous versions of the inventory and is the common approach to
19 dioxin sources inventories worldwide (UNEP, 2005). Doing so facilitates comparisons across
20 sources. For the purposes of environmental fate modeling, however, it is important to use the
21 individual CDD/CDF and PCB congener values rather than TEQs. This is because the
22 physical/chemical properties of individual CDD/CDF congeners vary and, consequently, the
23 congeners will behave differently in the environment. For example, the relative mix of
24 congeners released from a stack cannot be assumed to remain constant during transport through
25 the atmosphere and deposition to various media. Further, the bioavailability of dioxin congeners
26 are different, so that bioaccumulation in the food chain up through humans results in different
27 relative proportions of dioxins compared to the profile of dioxins to which animals and humans
28 are exposed. Generally, human exposure to releases of dioxins from sources is a complex
29 phenomena encompassing proximity to source, congener-specific fate and transport
30 characteristics, and congener-specific bioavailability. For this reason, the amount of dioxins
31 being emitted from a specific source may not translate directly into human exposure.
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1 TEQ values are frequently based on some congeners that were not found above detection
2 limits (DLs). Undetected values are commonly referred to using the term "nondetect," or ND,
3 and that terminology is adopted here. EPA risk assessments typically address this issue by
4 assuming that NDs = 2DL. This document is not a risk assessment and uses a different
5 approach. Here, it is assumed that NDs = 0. This assumption allows a consistent approach to
6 this issue throughout the document. Because many studies did not provide DLs, the only
7 practical, consistent approach is to assume NDs = 0. Many assessments also present TEQ
8 estimates in two ways: first assuming NDs = 0 and then assuming NDs = 2 DL. Such
9 comparisons are useful for illustrating the impact of DLs on TEQ calculations. This approach
10 was used in some places in this document, but generally, it was not used for two reasons. First, it
11 was not possible in many instances due to lack of DL information. Second, many release
12 estimates are presented in terms of two TEF schemes and three reference years. Presenting all
13 values with two ways of treating DLs, would increase complexity enough to compromise the
14 readability of the document.
15
16 1.1.3. Regulatory Summary
17 Over the time frame represented by these inventories (1987-2000), EPA, states, and
18 industry have worked to develop regulations limiting dioxin emissions. Although not all of these
19 regulations are fully implemented yet, they have contributed to reductions in emissions from
20 certain source categories (see time trend discussion in Section 1.3.3). Tables 1-3 through 1-8
21 present a synopsis of the principal EPA emission standards for the control of dioxin releases.
22
23 1.1.4. Information Sources
24 The references used to support this report are based on an intensive literature review of
25 documents published in 2003 (or earlier) and selected documents published in 2004-2010. The
26 report also used information from databases maintained by EPA's Office of Air Quality Planning
27 and Standards and Office of Resource Conservation and Recovery (ORCR).
28 An important reference in this field is the Standardized Toolkit for Identification and
29 Quantification of Dioxin andFuran Releases issued by the United Nations Environment
30 Programme in 2005 (UNEP, 2005). This document was produced to help support
31 implementation of the Stockholm Convention on Persistent Organic Pollutants. This Toolkit
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1 provides a methodology to help countries just developing their inventories to estimate releases of
2 CDD/CDF and to lead them through the process of enhancing and refining these inventories. It
3 is intended to provide a consistent basis for assessing CDD/CDF releases over time and between
4 countries. This updated inventory frequently references the Toolkit and discusses the
5 recommended emission factors.
6 The EPA Toxics Release Inventory (TRI) began collecting data on PCBs in 1988 and on
7 CDDs/CDFs in 2000 (U.S. EPA, 2003b). The TRI reporting of dioxin sources provides
8 important information in the overall understanding of dioxin releases. These data were
9 considered in this report for the purposes of identifying possible sources and as supportive
10 evidence for where releases can occur, but they were not used for making quantitative release
11 estimates because of the following considerations:
12
13 • With respect to PCBs, for reporting years 1988-2000, the TRI data are reported as total
14 PCBs rather than on a congener-specific basis. Thus, it is unknown what portion of these
15 releases are dioxin-like PCBs, and TEQs cannot be calculated.
16 • With respect to CDDs/CDFs, for reporting year 2000, the TRI data are reported as the
17 sum of the 17 congeners with 2,3,7,8-chlorine-substituted compounds. Facilities had the
18 option to report an estimate of the congener distribution for total releases, though many
19 chose not to provide this information. Accordingly, much of the 2000 data could not be
20 used to make TEQ estimates.
21 • The TRI data are self-reported, and facilities are not required to take measurements to
22 support their emission estimates. Rather, they can be derived from emission factors or
23 other methods. Facilities are also not required to describe the approach used to make the
24 emission estimates. Consequently, it would be difficult to evaluate inconsistencies
25 between these estimates and those in this inventory.
26 • The TRI reports include SIC codes but lack further details describing the facilities in
27 terms of process, production, and pollution controls. Therefore, in many cases, it is not
28 clear where a reporting facility fits into the classification system used in this report.
29
30 1.2. APPROACH
31 This section describes the key components of the approach used to develop the dioxin
32 inventory. The discussion covers the selection of reference years, release types, how sources are
33 classified, quantitative methods used to develop release estimates, and confidence ratings.
34
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1 1.2.1. Reference Years
2 A central part of EPA's dioxin inventory is the organization of estimates of annual
3 releases of dioxin-like compounds into reference years 1987, 1995, and 2000. The selection and
4 use of three reference years provides a basis for comparing environmental releases over time.
5 The year 1987 was selected as the initial reference year because it was the earliest time
6 when it was feasible to assemble a reasonably comprehensive inventory. Prior to that time, very
7 little data existed on dioxin emissions from stacks or other release points. The first study
8 providing the type of data needed for a national inventory was the EPA National Dioxin Study
9 (U.S. EPA, 1987). The year 1987 also corresponds roughly with the time when significant
10 advances occurred in emissions measurement techniques and in the development of
11 high-resolution mass spectrometry and gas chromatography, which allowed analytical
12 laboratories to detect low levels of CDD and CDF congeners in environmental samples. Soon
13 after this time, a number of facilities began upgrades specifically intended to reduce CDD/CDF
14 emissions. Consequently, 1987 emissions are representative of levels that occurred before the
15 widespread installation of pollution control systems and pollution prevention techniques
16 specifically designed to reduce dioxin releases from man-made sources into the air, land, and
17 water.
18 EPA selected 1995 as the second reference year because it reflects the completion time of
19 the first set of regulatory activities specifically tailored to reduce dioxin releases from major
20 sources. By 1995, EPA had proposed or promulgated regulations limiting CDD/CDF emissions
21 from municipal waste combustors (MWCs), medical waste incinerators, and pulp and paper mill
22 facilities using bleached chlorine processes.
23 The year 2000 was chosen as the most current date that could be addressed when this
24 effort began in 2002. Also, it corresponds to a reasonable time interval since 1995 when one
25 could expect to see further changes occurring in releases as a result of continuing regulatory
26 activities, voluntary actions on the part of industry, and facility closures.
27
28 1.2.2. Release Types
29 A comprehensive assessment of potential dioxin releases from a source requires
30 consideration of all possible outputs. As diagrammed in Figure 1-1, the outputs of a process can
31 be in the form of products, air emissions, water discharges, and solid residues. Solid residues
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1 can be used in products, land disposed or incinerated. Each source addressed in this document is
2 evaluated in terms of all of these outputs. However, not all of the outputs are considered to be
3 environmental releases. Outputs judged to have a reasonable likelihood for release to the
4 circulating environment include all air emissions, water discharges, landfarmed wastes and
5 products which are directly released to the open environment such as some pesticides. Outputs
6 that are generally not considered an environmental release include waste disposal at lined
7 landfills, intermediate products or internal waste streams or products containing tightly bound
8 dioxins such as treated wood. Dioxins contained in some products or disposed in secure landfills
9 may be released to the circulating environment at some time in the future. They are less likely to
10 be released to the circulating environment during the same year that they enter into commerce or
11 are landfilled. Consequently, these contained dioxins would not initially be considered
12 environmental releases. Ideally, releases derived from such products and landfill practices of
13 past years would be included in the inventory for the reference year in which the releases occur.
14 Unfortunately, the current state of science does not support estimating when and to what degree
15 such releases may occur. However, for informational purposes, and when sufficient information
16 is available, this document provides estimates of the amount of dioxins contained in products or
17 disposed in landfills.
18
19 1.2.3. Source Classes
20 Sources can be categorized in terms of when releases occur: (1) contemporary formation
21 sources (sources that have essentially simultaneous formation and release) and (2) reservoir
22 sources (materials or places that contain previously formed CDDs/CDFs or dioxin-like PCBs that
23 are rereleased to the environment). The contemporary formation sources are discussed in
24 Chapters 3 through 10, and the reservoir sources are discussed in Chapter 11.
25 This document also classifies sources into five broad categories based mainly on their
26 formation process:
27
28 1. Combustion. CDDs/CDFs are formed in most types of combustion. These sources are
29 addressed in Chapters 3-6:
30 • Chapter 3 covers sources involved in waste incineration including municipal solid
31 waste (MSW), hazardous waste, medical waste, sewage sludge, and other types of
32 waste.
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1 • Chapter 4 covers sources related to power/energy generation including motor vehicles
2 and combustion of wood, oil, and coal.
3 • Chapter 5 covers a variety high temperature sources including cement kilns, asphalt
4 plants, carbon reactivation furnaces, and others.
5 • Chapter 6 covers minimally controlled or uncontrolled sources and includes landfill
6 gas flares/fires, forest fires, backyard trash burning in barrels, and others.
7 2. Metals Smelting/Refining. This category includes sources that are involved in metals
8 smelting, refining, and processing. They are addressed in Chapter 7.
9 3. Chemical Manufacturing. CDDs/CDFs can be formed as by-products in a variety of
10 chemical manufacturing operations. These are addressed in Chapter 8 and include
11 chlorine-bleached wood pulp, chlorinated phenols (e.g., pentachlorophenol), PCBs,
12 chlorobenzenes, phenoxy herbicides (e.g., 2,4-D and 2,4,5-T), and chlorinated aliphatic
13 compounds (e.g., ethylene dichloride, vinyl chloride, polyvinyl chloride).
14 4. Biological, Photochemical, and Other Natural Processes. CDDs/CDFs can form via
15 biological processes such as the action of microorganisms on chlorinated phenolic
16 compounds and also during photolysis of highly chlorinated phenols. These are
17 addressed in Chapter 9.
18 5. Reservoirs. Reservoirs are environmental compartments and materials that have the
19 capacity to store previously formed CDDs/CDFs or dioxin-like PCBs. These compounds
20 are thus sequestered from the open and circulating environment. Potential reservoirs
21 include soils, sediments, and biota as well as some anthropogenic materials, such as
22 PCP-treated utility poles. Dioxin-like compounds in these reservoirs have the potential
23 for redistribution and circulation in the environment through the physical processes such
24 as leaching, volatilization, erosion, sedimentation, and deposition. Whenever dioxins are
25 released from their place of storage back into the circulating environment, the reservoir is
26 considered a source of dioxin. Reservoirs are addressed in Chapter 11.
27
28 Note that Chapters 3-9, discussed above, address releases of only CDDs and CDFs.
29 Contemporary formation sources that releases dioxin-like PCBs are discussed in Chapter 10.
30 Reservoir sources that release CDDs, CDFs, or PCBs are covered in Chapter 11.
31
32 1.2.4. Quantitative Method for Inventory of Sources
33 Estimates of CDD/CDF releases to the air from individual facilities are derived from
34 stack testing, which provides the concentration of CDD/CDF in the flue gas. This is combined
35 with the flue gas flow rate and operating time to estimate annual releases as shown in
36 equation 1-2:
37
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_ C Fv CF H
TEQ 109 ng/g
2
3 where
4 ETEQ = annual TEQ emissions (g/year)
5 C = combustion flue gas TEQ concentration (ng/dscm) (20°C, 1 atm; adjusted to
6 7% O2)
7 Fv = volumetric flow rate of combustion flue gas (dscm/hour) (20°C, 1 atm; adjusted
8 to 7% O2)
9 CF = capacity factor; fraction of time that the facility operates
10 H = total hours in a year (8,760 hour/year)
11
12 A similar approach is used for estimating facility releases to other media. For example, releases
13 to water would involve multiplying the concentration of the CDD/CDF in the effluent by the
14 discharge rate. Ideally, national release estimates would be derived by testing every facility in a
15 source category, estimating their releases, and summing across facilities. This was feasible in
16 only a few situations such as wastewater releases from chlorine-bleached pulp and paper mills.
17 For all other source categories, EPA used a method to extrapolate from tested to untested sources
18 and derive national estimates of environmental releases. As explained below, this method is
19 based on the use of emission factors and activity levels.
20 The first step in this approach is to use emission monitoring data to derive an emission
21 factor (or series of emission factors) deemed to be representative of the source category (or
22 segments of a source category that differ in terms of configuration, fuel type, air pollution
23 control equipment, etc.). The emission factor relates mass of dioxins released into the
24 environment with some measure of activity (e.g., kilograms of material processed per year,
25 vehicle miles traveled per year, liters of wastewater discharged per year). For individual
26 facilities, it is calculated using the following equation (eq 1-3):
27
28 EF= (1-3)
29
30 where
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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
EF = emission factor (ng TEQ/kg)
ETEQ = annual TEQ emissions (g/year) (see eq 1-1)
A = annual activity rate (kg/year)
A similar approach is used for estimating emission factors for releases to other media.
For example, an emission factor for releases to water would involve dividing the annual TEQ
release rate via effluent discharges by the annual waste processing rate (or some other measure
of activity). The emission factor representing a class of facilities is developed by averaging the
emission factors across the tested facilities in the class. This average emission factor is then
multiplied by the measure of activity for the nontested facilities in the class (e.g., total kilograms
of material processed by these facilities annually). Finally, releases are summed for the tested
facilities and nontested facilities. In general, this procedure can be represented by the following
equations (eq 1-4 and 1-5):
n ft
"Total ~ / , ^Tested, i + / , ^Untested, i
otal ~ / , -^Tested, i ~*~ / ,
Untested ,i
(1-4)
(1-5)
where
Rlotal
Rlested, i
RlJntested, i
EFuntestedi
A,
annual releases from all facilities (g TEQ/year)
annual releases from all tested facilities in class i (g TEQ/year)
annual releases from all untested facilities in class i (g TEQ/year)
mean emission factor for untested facilities in class i (g TEQ/kg)
activity measure for untested facilities in class i (kg/year)
Note that even though this approach is presented using the term "emission factor," it is
intended to apply to releases to all media. The method was originally developed for evaluating
air emissions and is thus traditionally defined using this term. Also note that for most sources, a
small percentage of the facilities had been tested. In these cases, it was not worth the effort to
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1 estimate releases from tested and untested facilities separately as shown in equation 1-5. Instead,
2 the average emission factor was applied to the activity level for the whole class.
3 Some source categories are made up of facilities that vary widely in terms of design and
4 operating conditions. For these sources, as explained above, an attempt was made to create
5 subcategories that grouped facilities with common features and then to develop separate
6 emission factors for each subcategory. Implicit in this procedure is the assumption that facilities
7 with similar design and operating conditions should have similar CDD/CDF-release potential.
8 For most source categories, however, the specific combination of features that contributes most
9 to CDD/CDF or dioxin-like PCB releases is not well understood. Therefore, the procedure for
10 how to best subcategorize a source category was often problematic. For each subcategorized
11 source category in this document, a discussion is presented about the variability in design and
12 operating conditions, what was known about how these features contributed to CDD/CDF or
13 dioxin-like PCB releases, and the rationale for creating subcategories.
14 The emission factors developed for the inventory are intended to be used for estimating
15 total emissions for a source category rather than emissions from individual facilities. If applied
16 to individual facilities, the emission factor would likely overestimate releases from some
17 facilities and underestimate others. When it is applied to a class of facilities, these over- and
18 underestimates balance out to some extent. Thus, in using these emission factors, one can place
19 significantly greater confidence in an emission estimate for a class than in an estimate for any
20 individual facility. Given the limited amount of data available for deriving emission factors and
21 the limitations of our understanding about facility-specific conditions that determine formation
22 and control of dioxin-like compounds, the current state of knowledge cannot support the
23 development of emission factors that can be used to accurately estimate emissions on an
24 individual facility-specific basis.
25
26 1.2.5. Uncertainties
27 The quantitative inventory has multiple uncertainties, including the following:
28
29 • It is based on emissions testing that covers a small fraction of the facilities in most
30 classes.
31 • Facility testing is generally over short time periods during normal operating conditions.
32 The releases during start-up and shutdown may be different than normal operations. For
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1 conventional pollutants, releases are generally greater during these times, but dioxin
2 releases may occur at rates lower or higher than normal operations due to changes in
3 formation conditions. Recent efforts by EPA's Office of Air Quality Planning and
4 Standards are addressing emissions that occur during start-up and shutdown and may
5 allow these uncertainties to be addressed in the future.
6 • Testing has sometimes found individual facilities within a class with unusually low or
7 high dioxin releases for unknown reasons.
8 • It does not include the emissions from a number of suspected sources that lack sufficient
9 data to make reliable estimates (defined below as preliminary or unquantifiable sources).
10 Because many types of sources release dioxins, it is likely that some have been missed
11 completely.
12
13 All of these factors introduce uncertainty into the release estimates. While most of these
14 uncertainties are impossible to characterize, some can be evaluated as discussed below.
15 The original inventory report (U.S. EPA, 2006) used a qualitative scheme to assess
16 uncertainty. This scheme assigned qualitative confidence ratings to the emission factors, activity
17 levels, and release estimates. The five confidence ratings (Class A, B, C, D, or E) were defined
18 as follows:
19
20 • Classes A, B, and C—Class A indicates high confidence, Class B indicates medium
21 confidence, and Class C indicates low confidence. These three classes make up the
22 quantitative inventory.
23 • Class D—For many source categories, very limited release data were available and
24 judged to be inadequate to support development of reliable quantitative release estimates
25 for one or more media. For some of these source categories, sufficient information was
26 available, however, to make preliminary estimates of releases. These preliminary
27 estimates were assigned to Class D.
28 • Class E—For other sources, no dioxin release data were available, but either formation
29 theory or similarity to other sources with measured releases suggested that releases may
30 occur. These sources were identified to the extent possible, but no release estimates
31 could be made. They were assigned to Class E.
32
33 The overall confidence rating assigned to an emissions estimate was determined by the lowest
34 rating assigned to either the emission factor or activity level.
35 In this update, a revised approach has been developed to characterize the confidence
36 ratings of the release estimates. The revised approach maintains the three major categories
37 previously used, i.e., (1) the quantitative inventory [which now includes the sum of the previous
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1 confidence ratings that were subdivided into Class A, B, or C], (2) the preliminary release
2 estimates [previously assigned a rating of Class D], and the unquantifiable sources [previously
3 assigned a rating of Class E]. The major changes are the elimination of the Class A, B, or C
4 confidence distinctions in the quantitative inventory and the addition of the quantitative
5 uncertainty analysis of the quantitative inventory (presented in Section 1.3.6). The old Class A,
6 B, and C confidence ratings were eliminated because they were too subjective and difficult to
7 apply in a consistent fashion. Also, it was judged that confidence ratings for the individual
8 source classes were less essential because a new quantitative uncertainty analysis has been
9 added. It was determined that the more important issue was the uncertainty in the total national
10 release estimate. Accordingly, the new quantitative approach focuses on this issue.
11 Key components of both the old and new scheme for assessing uncertainty are the criteria
12 for deciding whether a source belongs in the quantitative inventory or preliminary class. This
13 update uses more specific guidance for making this decision. In order for a source to be included
14 in the quantitative inventory, it must (a) have emission tests for at least two units/source types
15 with sufficient documentation to directly derive emission factors, (b) the measured emission
16 factors must be reasonably consistent or have understandable differences, (c) the emission factor
17 tests must represent units that are reasonably typical of the class and (d) the activity estimates
18 must be based on source-specific surveys.
19 The actual magnitude of releases from the preliminary sources could be significantly
20 lower or higher than estimated. Although EPA has chosen not to include them in the quantitative
21 inventory, it must be emphasized that some of the preliminary sources have the potential of being
22 major contributors of releases to the environment. Accordingly, they are important to identify
23 and can be used to help set priorities for future research and data collection. As the uncertainty
24 around these sources is reduced, they will be included in future inventory calculations.
25 The data used in this document come from hundreds of studies which reported values
26 using a wide range of significant figures. In the present report, the decision about how many
27 significant figures to use began with the general policy to report previously published data in the
28 same manner as in the original publication and to report calculated values with a number of
29 significant figures no more than the input with the least number of significant figures. This
30 document reports all emission factors and releases in TEQs. TEQs are derived from toxicity
31 equivalency factors that are presented with only one significant figure. Although this suggests
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1 that all TEQ estimates should be presented with only one significant figure, they are commonly
2 reported to 2 or more significant figures in the literature. Limiting the number of significant
3 figures to 1 for the larger release estimates introduces large rounding adjustments. Therefore, it
4 was decided to present the release estimates to 2 significant figures when they equal or exceed 10
5 g TEQ/year. Releases less than 10 g TEQ/year were limited to only 1 significant figure.
6 Releases less than 0.1 g TEQ/year were presented as <0.1 to reflect the additional uncertainty in
7 such small estimates and because they have negligible contributions to the total releases.
8 Similarly the emission factors were reported to 2 significant figures for values that equal or
9 exceed 0.1 ng TEQ/kg and to 1 significant figure for values less than 0.1 ng TEQ/kg. Activity
10 estimates are typically very large numbers and are generally known with more certainty than the
11 emission factors. Therefore, it was decided to report activities to 3 or fewer significant figures.
12
13 1.3. SUMMARY AND CONCLUSIONS
14 Table 1-12 lists all of the quantitative and preliminary CDD/CDF release estimates
15 developed in this document. It also identifies all of the unquantifiable sources. Where feasible,
16 the table presents release estimates to air, water, land, and products for each reference year. As
17 discussed earlier, the preliminary release estimates are not part of the official inventory, but they
18 are included in this table to provide a complete picture of what is known and unknown about
19 potential CDD/CDF releases.
20 Table 1-13 lists all of the quantitative and preliminary PCB release estimates and
21 unquantifiable PCB sources. It is organized in the same manner as Table 1-12. Both Tables
22 1-12 and 1-13 include only contemporary formation sources, i.e., those which form CDD/CDFs
23 during the same time frame as when the releases occur. Releases can also occur from reservoirs,
24 which are defined as materials or places that contain previously released CDD/CDFs or dioxin-
25 like PCBs and have the potential for redistributing these compounds into the environment.
26 Tables 1-14 (CDD/CDFs) and 1-15 (PCBs) present releases for reservoirs. Releases from
27 reservoirs are not considered to be part of the official inventory because they are not original
28 releases but rather the recirculation of past releases.
29
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1 1.3.1. Contemporary Formation Sources
2 Eighty source categories were identified with the potential for dioxin emissions. The
3 major conclusions regarding CDD/CDF releases from contemporary formation sources are
4 presented below:
5
6 • The total releases under the national quantitative inventory for 1987 in g WHOgg TEQDF
7 were 15,000 to air, 2,400 to land, 360 to water, and 36 to products.
8 • The total releases under the national quantitative inventory for 1995 in g WHOgg TEQop
9 were 3,400 to air, 2,400 to land, 30 to water, and 47 to products.
10 • The total releases under the national quantitative inventory for 2000 in g WHOgg TEQop
11 were 2,300 to air, 2,300 to land, 28 to water, and 7 to products.
12 • Table 1-16 presents a ranking of the top five sources based on the magnitude of
13 environmental release by year and media. The top three air sources in 2000 were forest
14 fires (730 g WHO98 TEQDF), backyard barrel burning of refuse (600 g WHO98 TEQDF),
15 and medical waste incinerators (400 g WHOgg TEQop).
16 • Preliminary sources have the potential for large releases of dioxin-like compounds. The
17 largest preliminary sources are accidental fires at landfills (1,300 g WHOgg TEQop to air
18 in 2000) and land clearing debris burning (85 g TEQop to air in 2000).
19 • A total of 20 contemporary formation sources were identified as having unquantifiable
20 releases to one or more media. Information suggests these may be sources of dioxin-like
21 compounds, but it is insufficient to make a national estimate of releases.
22 • Table 1-17 lists the amounts of CDD/CDF found in several chemical products. The
23 largest amounts are found in pentachlorophenol, but the environmental releases
24 associated with this product (primarily used to treat wood) could not be estimated.
25 Release estimates could only be made for 2,4-D, where it can be assumed that the entire
26 amount produced is released to the environment.
27
28 The environmental releases of dioxin-like PCBs have not been well characterized. PCBs
29 were not produced during the reference years, but are still present in capacitors, transformers,
30 building materials and other products in use today. No estimates could be made for releases
31 from these in-use products. As shown in Table 1-13, only one source (backyard barrel burning)
32 was judged to have adequate data to support quantitative air-release estimates of 41, 43, and
33 34 g WHO9g TEQp for the years 1987, 1995, and 2000, respectively. Similarly, only two sources
34 (backyard barrel burning and municipal wastewater treatment) were judged to have adequate
35 data to support quantitative land release estimates of 52, 78, and 20 g WHOgg TEQp for the years
36 1987, 1995, and 2000, respectively. Also, preliminary estimates could be made for 6 sources,
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1 and 10 sources were identified as being unquantifiable. Although the information is limited, it
2 suggests that, in terms of TEQs, PCB releases are much lower than CDD/CDF releases.
3
4 1.3.2. Reservoir Sources
5 Soil is likely to be the reservoir source with the greatest potential for release of
6 CDD/CDFs and PCBs to other environmental media, particularly to water. This is due to its
7 relatively large mass of stored CDD/CDFs and PCBs and the existence of demonstrated
8 transport mechanisms for intermedia exchange, e.g., soil erosion to surface waters and particle
9 resuspension to air.
10 The preliminary estimates of CDD/CDF TEQs in soil runoff to waterways (Table 1-14)
11 are more than 100 times greater than known industrial point-source releases to water. It is
12 unclear how much of the soil erosion and runoff represents recently deposited CDD/CDFs from
13 primary sources or longer-term accumulation. Much of the eroded soil comes from tilled
14 agricultural lands, which would include a mix of CDD/CDFs from various deposition times.
15 Five possible product reservoirs were identified: bleached chemical wood pulp,
16 pentachlorophenol, vinyl chloride, chloranil, and PCBs. No estimates could be made for the
17 total mass of CDD/CDFs contained in these reservoirs or their releases.
18
19 1.3.3. Time Trends
20 Some observations about how releases have changed over the reference years can be
21 made for the quantified sources. It is important to understand, though, that these observations do
22 not include the sources classified as preliminary or unquantifiable. Some of the preliminary
23 sources are potentially very large and, if confirmed, could change the trend observations based
24 on the currently quantified sources. With this caveat in mind, the following trends were
25 identified.
26 Table 1-18 shows the total releases in 1987, 1995, and 2000 and the percent changes
27 from 1987 to 1995, 1995 to 2000, and 1987 to 2000. A few sources were included in some
28 reference years and not others due to lack of information. Removal of these sources from the
29 yearly totals only had a large effect on the water release estimates. Thus, the water totals
30 presented in Table 1-18 reflect this adjustment (discussed further below).
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1 In terms of total releases from all media, a 67% reduction occurred from 1987 to 1995, a
2 23% reduction occurred from 1995 to 2000, and a 74% reduction occurred from 1987 to 2000.
3 Further insight can be gained from examining trends occurring in each medium:
4
5 • Air—The reductions in total air releases were 85% from 1987 to 2000. Three sources
6 accounted for over 100% of the reduction: municipal waste incinerators (74%), medical
7 waste incinerators (18%), and secondary copper smelters (8%). These reductions were
8 offset by increases in releases from forest fires, which increased by a factor of 4 from
9 1987 to 2000: 180 g WHO98 TEQ in 1987 to 730 g WHO98 TEQ in 2000. Table 1-16
10 shows that the nonindustrial sources have moved to the top of the rankings.
11 • Land—Very little change occurred in land releases over the reference years (4%
12 reduction in 1987 to 2000). Land release estimates could only be made for
13 seven sources, and these were dominated by structural fires and backyard barrel burning.
14 • Water—Only one source—bleached pulp and paper mills—had water release estimates
15 for each of the reference years. Thus, the trend analysis is limited to this source. The
16 reductions from 1987 to 2000 were almost 100% (360 to 1 g WHO98 TEQ).
17 • Product—The reductions in product releases were 81% from 1987 to 2000. Release
18 estimates could only be made for two products: 2,4-D and land-applied municipal
19 wastewater treatment sludge. Assuming that dioxins have been eliminated from 2,4-D by
20 2000 (data are lacking to confirm this), this reduction is virtually 100%. Releases from
21 sludge actually increased from 1987 to 2000, although the amounts were low (i.e.,
22 7 gWHO98 TEQ in 2000).
23
24 One way to assess the validity of these trends is to consider the uncertainties associated with
25 the release estimates. As discussed in Section 1.3.6 a propagation of error analysis was used to
26 derive the standard deviation for the air release estimate for the year 2000 based on the top 9
27 sources (releases = 2,100 g WHO98 TEQ with SD = 1,300). A similar analysis of the 1987 data
28 suggests that the air releases (14,000 g WHO98 TEQ) have an SD of 3,000. This means that the
29 1987 releases minus two SDs still exceeds the 2000 releases plus two SDs. As a point of
30 comparison, for normal distributions, 95% of the probability falls within two SDs of the mean.
31 Although the distribution of possible releases is likely skewed, the large difference between the
32 total releases and their associated SDs suggest that little overlap occurs between the possible
33 range of estimates for the 1987 and 2000 releases. Thus the results of this analysis strongly
34 support the observation of a downward trend.
35
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1 Finally further evidence of future downward trends in dioxin emissions to the air can be
2 based on recent rulemaking and data collection efforts conducted by EPA's Office of Air Quality
3 Planning and Standards. The Clean Air Act requires that regulation support efforts include
4 estimates of current nationwide baseline emissions and future reductions that will occur after full
5 implementation of the regulations. The list below shows these estimates for regulation support
6 activities that have occurred after 2000:
7 • Sewage sludge incineration - Baseline estimates for 2010 were 0.4 g WHO2oos TEQ/yr
8 with future reductions of 0 g WHO2005 TEQ/yr (ERG, 201 la). This compares to the
9 estimates presented here of 10 g WHOgg TEQ/yr for the year 2000.
10 • Medical waste incineration - Baseline estimates for 2008 were 0.83 g WHO2005 TEQ/yr
11 with future reductions of 0.66 g WHO2005 TEQ/yr (Holloway, 2009). This compares to
12 the estimates presented here of 400 g WHO98 TEQ/yr for the year 2000.
13 • Secondary copper smelting - US EPA concluded that no dioxin emissions occurred from
14 secondary copper smelting plants in 2006 because all had been shut down (Federal
15 Register, 2006). This compares to the estimates presented here of 0.9 g WHOgg TEQ/yr
16 for the year 2000.
17 • Industrial, Commercial, Institutional Boilers and Process Heaters - Baseline estimates for
18 2008 were 37 g WHO2oo5 TEQ/yr with future reductions of 23 g WHO2oo5 TEQ/yr
19 (Singleton and Gibson, 2011). This source category does not match exactly with the
20 source definitions used here. It includes industrial oil burning boilers (7 g WHOgg
21 TEQ/yr for the year 2000) and industrial coal burning boilers (41 g WHO98 TEQ/yr for
22 the year 2000)
23 • Commercial/Industrial solid waste incineration - Baseline estimates for 2010 were 165 g
24 total CDD/Fs with future reductions of 115 g total CDD/Fs (ERG, 201 Ib). Unfortunately
25 as of press time for the present document, no TEQ conversions were available for these
26 estimates, making comparisons difficult. Also this source category does not match
27 exactly with the source definitions used here.
28
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1 1.3.4. Sources Not Included in the Inventory
2 Significant amounts of the dioxin-like compounds produced annually in the United States
3 are not considered releases to the open and circulating environment and are not included in the
4 national inventory. Examples include dioxin-like compounds generated internal to a process but
5 destroyed before release and waste streams that are disposed of in approved landfills.
6 A number of contemporary formation sources were classified as preliminary or
7 unquantifiable and, therefore, were not included in the inventory. The largest contemporary
8 formation preliminary source is accidental fires at MSW landfills. This source has the potential
9 to significantly increase the release estimates for 2000 if preliminary estimates are confirmed.
10 The possibility remains that truly undiscovered sources exist. Many of the sources that
11 are well accepted today were discovered only in the recent past. For example, CDDs/CDFs in
12 stack emissions from MWCs were not detected until the late 1970s; CDDs/CDFs in the
13 wastewater effluent from bleached pulp and paper mills were found unexpectedly in the
14 mid-1980s; iron ore was not recognized as a source until the early 1990s.
15
16 1.3.5. Congener Profiles of CDD/CDF Sources
17 The 2006 document presented congener profiles for a number of sources, showing the
18 relative amounts of CDD/CDF congeners in environmental releases. While these profiles can be
19 useful for identifying sources, they are not essential to the inventory itself. Therefore, they were
20 not updated in the present document.
21
22 1.3.6. Uncertainty Analysis
23 The purpose of this section is to present a quantitative analysis of the uncertainty in the
24 total release estimates. Given the wide scope of this document (over 80 source categories,
25 three reference years and four release media), a number of steps were taken to simplify this
26 analysis. First, it was limited to the 2000 releases because these are the most current. Second, it
27 was limited to the air and land releases. The releases to the other media are so much smaller,
28 they will have negligible impact on the overall uncertainty (air—2,300 g WHOgg TEQ, land—
29 2,200 g WHOgg TEQ, water—28 g WHO98 TEQ and product—7 g WHO98-TEQ). Finally, the
30 number of source categories included in the analyses was limited to the largest ones, with
31 cumulative contributions of about 90% of the total releases.
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1
2 1.3.6.1. Air Releases
3 The uncertainty was first evaluated using a propagation of error approach. This involves
4 estimating the variance for the emissions from each source and summing these to get the overall
5 variance in total emissions. Multiple factors contribute to the uncertainty in the emission
6 estimate for a class of facilities. These include sampling error which reflects the number of
7 facilities tested out of the total, the representativeness of the tests of long term conditions and
8 measurement error from inaccuracies in the stack monitoring and chemical analysis. The
9 propagation of error approach used here assumes that the variability in the emissions from the
10 sampled facilities is an indication of the possible uncertainty in the emissions from the whole
1 1 class of facilities. While some of the variability is due to differences in the design and operation
12 of the facilities, some also results from the various sources of uncertainty. It is impossible to
13 know how much of the variability can be attributed to design/operation versus uncertainty, so
14 this approach interprets all of the variability as an indication of the possible uncertainty. While
15 this may imply an overestimate of the uncertainty, this is offset to some degree by the limitations
16 of the database, such as the small n's for many classes, lack of testing during start-up and
17 shutdown, use of short term testing to represent long term conditions, etc.
18 The total releases (Rtotai) are calculated by summing the releases across the 9 largest air
19 sources (Ri) which account for over 90% of the total:
20
21 ^=X (1-6)
2=1
22
23 The emissions from each source are computed as the product of the emission factor and activity:
24
25 RTotal=fJEFixAi (1-7)
z=l
26
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1 where
2 Riotai = Total Releases (g TEQ/year)
3 EF; = Emission factor for source i (ng TEQ/kg)
4 A; = Activity for source i (kg/year)
5
6 The emission factor is calculated on the basis of emission measurements that involve some error.
7 Sampling error results from the fact, in general, only a small subset of the total facilities in each
8 source class was tested. Measurement error is associated with stack sampling procedures and
9 has been estimated to be +/- 30% for dioxins (U.S. EPA, 1990b). Lanier and Hendrix (2001)
10 assessed the accuracy of Test Method 23 for stack measurements of PCDD and PCDFs. For
11 determination of total PCDD/PCDF mass, the analysis found that RSD varied between about 6.3%
12 and 20% for stack concentrations in the range of 2 to 27 ng/dscm. Although activity estimates also
13 have uncertainty, it is assumed here that this is negligible compared to the uncertainty in the
14 emission factor. The amount of error in estimating the releases from each source is assumed to
15 be independent of each other. The variance in releases from each source is estimated using the
16 variance of the emission factor data and treating the activity as a constant:
17
9
18 variance in Rj.otal = ^_variance in EFi xAt2 (1-8)
z=l
19
20 Generally, the variance estimates for the emission factors were derived using the standard
r\
21 equation, i.e. E(x - 0) /(n-1). However, in a few cases, some special considerations were
22 necessary:
23
24 • The emission factor data for forest fires consisted of a series of chamber tests and field
25 tests. Given the fundamental differences in the data from these two types of tests, it was
26 not considered appropriate to combine them. Instead, the emission factor was estimated
27 for each data set and averaged to get the best overall estimate:
28
29 EF = 0.5(EFfield+EFMer) (1-9)
30
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1 variance inEF = 0.5 2( variance inEFfield+ variance inEFchamber} (1-10)
2
3 • In 2000, stack tests were available for all operating municipal waste incinerators and
4 cement kilns burning hazardous waste. The total emissions for these two classes were
5 estimated by summing the individual emissions from each facility. Thus, an
6 emission-factor approach based on a subset of the facilities was not necessary. Because
7 all facilities were tested, in theory, there is no sampling error. However, it is recognized
8 that factors other than sampling error can contribute to the error in these estimates.
9 Therefore, the variance for these sources were estimated and included in the propagation
10 of error calculation.
11
12 Table 1-19 summarizes the results of this analysis. The analysis concludes that the total
13 emissions sum to 2,100 g TEQ/year with a standard deviation of 1,300 g TEQ/year.
14 Frey and Zhao (2004) demonstrated that probabilistic methods can be used to evaluate
15 uncertainties in emission inventories for benzene, formaldehyde, chromium, and arsenic.
16 Accordingly, a probabilistic approach was also explored here as discussed below.
17 Probabilistic methods for evaluating uncertainty require developing distributions for the
18 input variables. Frey and Zhao (2004) fit their emission factor data to parametric distributions
19 using maximum likelihood estimation. This is a complex procedure and difficult to apply
20 accurately to the emission factor data sets with low n values. Instead, all emission factors were
21 assumed to have log normal distributions with means and standard deviations based on an
22 arithmetic analysis of the data. Log normal distributions have been found to apply to many types
23 of environmental data including emission factors (Frey and Zhao, 2004). A Monte Carlo
24 analysis was conducted using the Crystal Ball program. A total of 10,000 simulations were run,
25 producing a mean of 2,100 g TEQ and standard deviation of 1,100 g TEQ, which are very similar
26 to the results of the propagation-of-error approach described above. Percentiles were estimated
27 as 1,100 g TEQ for 10%, 1,800 g TEQ for 50%, and 3,300 g TEQ for 90%. These percentiles
28 can be interpreted as the probability that the emissions will less than or equal to the specified
29 amount.
30 Finally, further analysis is offered on the uncertainties associated with the forest fires.
31 These uncertainties are especially important to evaluate because they are the largest source and
32 have high uncertainty in the emission factor. As stated above, both chamber studies and field
33 studies have been used to measure these emissions. The field data suggest an emission factor of
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1 0.95 ng TEQ/kg, and the chamber data suggest an emission factor of 7.5 ng TEQ/kg. If the
2 lower emission factor is used, the forest fires would have a release of 230 g TEQ, and the total
3 releases across the 9 top sources would be 1,600 g TEQ. Similarly, if the higher emission factor
4 is used, the forest fires would have a release of 1,800 TEQ, and the total releases across the
5 nine top sources would be 3,200 g TEQ.
6
7 1.3.6.2. Land Releases
8 The 2000 land releases were dominated by backyard barrel burning which had releases of
9 1,900 g WHO98 TEQ (88% of the total) and the uncertainty analysis was limited to this
10 one source. The releases from backyard barrel burning were based on a study by Lemieux
11 (1997). Ash samples from the experiments were combined, resulting in two composite samples,
12 one for recyclers (2,700 ng WHOgg TEQDF /kg ash) and one for nonrecyclers
13 (620 ng WHOgg TEQDF /kg ash). The final emission factor was based on the average of these
14 values (1,700 ng WHOgg TEQop /kg ash). The limited data do not allow a statistical analysis
15 such as done for the air releases. Instead a potential range of releases was estimated based on the
16 lower and upper emission factor estimates. The activity estimate for 2,000 was 1.2 MMT.
17 Combining this value with the lower emission factor yields a release estimate of
18 740 g WHOgg TEQ. Combining the activity with the higher emission factor yields a release
19 estimate of 2,800 g WHOgg TEQ. Accordingly the potential range of releases is 740 to
20 2,800 g WHO9g TEQ. Relative to the average value (1,900 g WHO9g TEQ), the lower estimate
21 is 62% less and the upper estimate is 46% more.
22
23 1.3.7. Relative Impact of Releases
24 When comparing national release estimates across sources, it should not be assumed that
25 the magnitude of dioxin-like compound emissions is proportional to their impact on human
26 health. Human exposure to dioxins occurs primarily via the diet. Therefore, factors such as the
27 proximity of sources to food production areas and their location relative to wind direction may
28 cause disproportionate impacts from emissions.
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Table 1-1. Nomenclature for dioxin-like compounds
Term/symbol
CDD
CDF
PCB
M
D
Tr
T
Pe
Hx
Hp
O
2,3,7,8
Congener
Congener group
Isomer
Specific isomer
Definition
Chlorinated dibenzo-/?-dioxin, halogens substituted in any position
Chlorinated dibenzofuran, halogens substituted in any position
Polychlorinated biphenyl
Symbol for mono (i.e., one halogen substitution)
Symbol for di (i.e., two halogen substitution)
Symbol fortri (i.e., three halogen substitution)
Symbol fortetra (i.e., four halogen substitution)
Symbol for penta (i.e., five halogen substitution)
Symbol for hexa (i.e., six halogen substitution)
Symbol for hepta (i.e., seven halogen substitution)
Symbol for octa (i.e., eight halogen substitution)
Halogen substitutions in the 2,3,7,8-positions
Any one particular member of the same chemical family (e.g., there are
75 congeners of CDDs)
Group of structurally related chemicals that have the same degree of chlorination
(e.g., there are eight congener groups of CDDs, MCDD through OCDD)
Substances that belong to the same congener group (e.g., 22 isomers constitute
congener group of TCDDs)
the
Isomers denoted by unique chemical notation (e.g., 2,4,8, 9-tetrachlorodibenzoruran
is referred to as 2,4,8,9-TCDF)
MCDD = monochlorinated.
OCDD = octachlorinated.
Source: Adapted from U.S. EPA (1989).
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-25 DRAFT: DO NOT CITE OR QUOTE
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Table 1-2 TEF schemes for CDDs, CDFs, and PCBs
Compound
Chlorinated dibenzo-p-dioxins
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
Chlorinated dibenzofurans
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,6,7,8,9-HpCDF
OCDF
I-TEFs
1
0.5
0.1
0.1
0.1
0.01
0.0001
0.1
0.05
0.5
0.1
0.1
0.1
0.1
0.01
0.01
0.0001
WHO94
WH098
1
1
0.1
0.1
0.1
0.01
0.0001
0.1
0.05
0.5
0.1
0.1
0.1
0.1
0.01
0.01
0.0001
WH02005
1
1
0.1
0.1
0.1
0.01
0.0003
0.1
0.03
0.3
0.1
0.1
0.1
0.1
0.01
0.01
0.0003
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-26 DRAFT: DO NOT CITE OR QUOTE
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Table 1-2. TEF schemes for CDDs, CDFs, and PCBs (continued)
Compound
Polychlorinated Biphenyls
3,3',4,4'-TCB (PCB-77)
3,4,4',5-TCB (PCB-81)
2,3,3',4,4'-PeCB (PCB-105)
2,3,4,4',5-PeCB(PCB-114)
2,3',4,4',5-PeCB(PCB-118)
2',3,4,4',5-PeCB (PCB-123)
3,3',4,4',5-PeCB (PCB-126)
2,3,3',4,4',5-HxCB (PCB-156)
2,3',4,4',5,5'-HxCB (PCB-157)
\ /
2,3',4,4',5,5'-HxCB (PCB-167)
3,3',4,4',5,5'-HxCB (PCB-169)
2,2',3,3',4,4',5-HpCB (PCB-170)
2,2',3,4,4',5,5'-HpCB (PCB-180)
2,3,3',4,4' 5,5'-HpCB (PCB-189)
I-TEFs
WHO94
0.0005
0.0001
0.0005
0.0001
0.0001
0.1
0.0005
0.0005
0.00001
0.01
0.0001
0.00001
0.0001
WHO98
0.0001
0.0001
0.0001
0.0005
0.0001
0.0001
0.1
0.0005
0.0005
0.00001
0.01
0.0001
WH02005
0.0001
0.0003
0.00003
0.00003
0.00003
0.00003
0.1
0.00003
0.00003
0.00003
0.03
0.00003
OCDF = octachlorodibenzofuran.
OCDD = octachlorinated.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-27 DRAFT: DO NOT CITE OR QUOTE
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Table 1-3. Municipal waste combustors"
Category15
New, large
Existing, large
With electrostatic precipitators as the APCD
With dry scrubber/fabric filters as the APCD
New, small
Existing, small
With electrostatic precipitators as the APCD
With dry scrubber/fabric filters as the APCD
Stack emission limitc
(ng total CDD/CDF/dscm)
13
60
30
13
60
30
Effective date
September 20, 1994d
June 19, 1996e
When SIPs are
approvedf
June 6, 200 1s
When SIPs are
approved11
aAir emission standards promulgated on December 19, 1995.
bLarge = aggregate capacity >225 tons/day; small = aggregate capacity <225 tons/day.
°ng total CDD/CDF/dscm = nanograms total C14-C18 CDDs plus CDFs per dry standard cubic meter of stack gas
volume, corrected to 7% O2.
dBegan construction on this date.
eModified or upgraded on this date.
fWhen SIPs have been approved by EPA (approximately 3 years from the final rule, or 1998).
8For facilities constructed on or before this date.
hWhen SIPs have been approved by EPA (approximately 3 years from the final rule, or 2003).
APCD = air pollution control device.
SIP = State Implementation Plan.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-28 DRAFT: DO NOT CITE OR QUOTE
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Table 1-4. Hazardous waste combustors3
Source category
Incinerators burning
hazardous waste
Cement kilns burning
hazardous waste
Lightweight aggregate
kilns burning hazardous
waste
Solid fuel boilers
burning hazardous waste
Liquid fuel boilers
burning hazardous waste
Hydrochloric acid
production furnaces
burning hazardous waste
Standards for new sources
For an incinerator with dry
APCD and/or waste heat boiler:
0.11 ng I-TEQ/dscm
For all other incinerators:
0.20 ng I-TEQ/dscm
0.20 ng I-TEQ/dscm, or
0.40 ng I-TEQ/dscm when PM
control device operated >400°F
0.20 ng I-TEQ/dscm, or rapid
quench of combustion gas to
below 400°F at kiln exit
Either CO of 100 ppmv or HC
of 10 ppmv
For a LFB with dry APCD:
0.40 ng I-TEQ/dscm.
For all other LFBs:
Either CO of 100 ppmv or HC
of 10 ppmv
Either CO of 100 ppmv or HC
of 10 ppmv
Standards for existing sources
For an incinerator with dry APCD
and/or waste heat boiler:
0.20 ng I-TEQ/dscm, or
0.40 ng I-TEQ/dscm when PM
control device operated >400°F
For all other incinerators:
0.40 ng I-TEQ/dscm
0.20 ng I-TEQ/dscm, or
0.40 ng I-TEQ/dscm when PM
control device operated >400°F
0.20 ng I-TEQ/dscm, or rapid
quench of combustion gas to
below 400°F at kiln exit
Either CO of 100 ppmv or HC of
10 ppmv
For a LFB with dry APCD:
0.40 ng I-TEQ/dscm.
For all other LFBs:
Either CO of 100 ppmv or HC of
10 ppmv
Either CO of 100 ppmv or HC of
10 ppmv
aAir emission standards promulgated October 12, 2005.
bng I-TEQ/dscm = nanogram I-TEQ per dry standard cubic meter of stack gas volume corrected to 7% O2.
APCD = Air pollution control device (dry = dry scrubber or fabric filter).
2 CO = carbon monoxide continuously monitored.
3 HC = Total hydrocarbons continuously monitored.
4 LFB = Liquid fuel boiler.
PM = Paniculate matter.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-29 DRAFT: DO NOT CITE OR QUOTE
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Table 1-5 Cement kilns not burning hazardous waste"
Existing cement kilnsb
New cement kilnsb
0.20 ng I-TEQ/dscm and temperature control
<400EF at the APCD inlet
0.40 ng I-TEQ/dscm when PM control device
operated >400EF
0.20 ng I-TEQ/dscm and temperature control
<400EF at the APCD inlet
0.40 ng I-TEQ/dscm when PM control device
operated >400EF
aAir emission standards promulgated on June 14, 1999.
bng I-TEQ/dscm = nanograms I-TEQ per dry standard cubic meter of stack gas volume corrected to 7% O2
APCD = Air pollution control device.
PM = Paniculate matter.
Table 1-6. Secondary aluminum smelters"
Process
Sweat furnace
Thermal chip dryer
Scrap dryer/delacquering kiln/decoating kiln
Scrap dryer/delacquering kiln/decoating kiln
equipped with an afterburner
Emission standard
0.8 ng I-TEQ/dscm stack gas corrected to 7% O2
2.50 ug I-TEQ per MT of scrap charged to the dryer
0.25 g I-TEQ per MT of scrap charged to the kiln
5.0 g I-TEQ per MT of scrap charged to the kiln
aAir emission standards promulgated on March 23, 2000.
MT = metric ton.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-30 DRAFT: DO NOT CITE OR QUOTE
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Table 1-7. Medical waste incinerators"
Category
Large
Medium
Small
Small rural
Existing (ng
WHO20o5TEQ/dscm)
0.054
0.020
0.013
2.1
New (ng
WHO20o5TEQ/dscm)
0.035
0.014
0.013
"Federal Register, 2009.
Table 1-8 Pulp and paper mills"
Pollutant
Tetrachlorodibenzo-p-dioxin
Tetrachlorodibenzofuran
Maximum 1-day wastewater discharge
<5 parts per quadrillion
31.9 picograms per liter
"Effluent limitation guidelines promulgated on April 15, 1998.
Table 1-9. Commercial/Industrial solid waste incinerators"
Category
Incinerators
Energy Recovery Units -
solids
Energy Recovery Units -
liquid/gas
Waste Burning Kilns
Small, remote Incinerators
Existing (ng
WHOioosTEQ/dscm)
0.13
0.059
0.32
0.0070
57
New (ng
WHOioosTEQ/dscm)
0.13
0.011
0.002
0.0030
31
"Federal Register, 201 la.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-31 DRAFT: DO NOT CITE OR QUOTE
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Table 1-10. Sewage sludge incinerators3
Category
Multiple Hearth
Fluidized Bed
Existing (ng
WHO2oo5TEQ/dscm)
0.32
0.10
New (ng
WHO2oo5TEQ/dscm)
0.0022
0.0044
"FederalRegister, 20lib.
Table 1-11. Industrial, commercial, and institutional boilers and process heaters"
Category
Coal Stoker
Coal Fluidized Bed
Pulverized Coal
Biomass Stoker/other
Biomass Fluidized Bed
Biomass Dutch
Oven/Suspension Burner
Biomass Fuel Cells
Biomass Suspension/Grate
Liquid
Gas 2 (Other Process Gases)
Non-continental liquid
Existing (ng
WHOioosTEQ/dscm)
0.003
0.002
0.004
0.005
0.02
0.2
4
0.2
4
0.08
4
New (ng
WHOioosTEQ/dscm)
0.003
0.002
0.003
0.005
0.02
0.2
0.003
0.2
0.002
0.08
0.002
"FederalRegister, 20lie.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 1-32 DRAFT: DO NOT CITE OR QUOTE
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Table 1-12 Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
to
OJ
Source
Air releases
Q. Inv.
Prelim.
NQ.
Land releases
Q. Inv.
Prelim.
NQ.
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ.
WASTE INCINERATION
Municipal solid waste
incinerators
1987
1995
2000
Hazardous waste
incinerators
1987
1995
2000
Industrial boilers burning
haz. waste
1987
1995
2000
Halogen acid furnaces
burning haz. waste
1987
1995
2000
9,500
1,200
77
5
6
3
0.8
0.4
0.7
0.3
0.3
0.3
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
H »
O^
HH^S
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Medical waste incinerators
1987
1995
2000
Human crematoria
1987
1995
2000
Animal crematoria
1987
1995
2000
Sewage sludge incinerators
1987
1995
2000
Tire combustion
1987
1995
2000
Biogas combustion
1987
1995
2000
Air releases
Q. Inv.
2,700
510
400
0.2
0.2
0.3
6
14
10
Prelim.
3
4
4
0.1
0.1
0.5
0.2a
0.2a
0.2a
NQ
Land releases
Q. Inv.
Prelim.
O.la
O.la
O.la
NQ
Water releases
Q. Inv.
Prelim.
NQ.
X
X
X
X
X
X
X
X
X
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
§
i
a,
§•
a
o_
I
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
O
c
o
H
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-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
POWER/ENERGY GENERATION
Leaded gasoline, on-road
1987
Leaded gasoline, off-road
1987
Unleaded gasoline,
on-road
1987
1995
2000
Unleaded gasoline,
off road
1987
1995
2000
Diesel, on-road
1987
1995
2000
Diesel, off-road
1987
1995
2000
50
5
6
7
51
55
64
3
0.2
0.3
0.4
19
20
23
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Indoor residential wood
burners
1987
1995
2000
Outdoor wood-fired
boilers
2000
Industrial wood
combustion
1987
1995
2000
Commercial and
residential oil combustion
1987
1995
2000
Utility sector and
industrial oil combustion
1987
1995
2000
Air releases
Q. Inv.
36
19
15
78
78
82
6
6
7
19
14
15
Prelim.
9
NQ
Land releases
Q. Inv.
21
11
9
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Waste oil combustion
1987
1995
2000
Industrial coal-fired
utilities
1987
1995
2000
Industrial coal -fired boilers
1987
1995
2000
Residential coal
combustion
1987
1995
2000
Air releases
Q. Inv.
51
60
70
48
46
41
10
5
3
Prelim.
0.6
0.7
0.7
NQ
Land releases
Q. Inv.
17
18
22
Prelim.
0.1
0.1
<0.1
NQ
Water releases
Q. Inv.
Prelim.
NQ.
X
X
X
Product releases
Q. Inv.
Prelim.
NQ
OTHER HIGH TEMPERATURE SOURCES
Cement kilns burning
hazardous waste
1987
1995
2000
120
160
19
4a
4a
3a
X
X
X
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Cement kilns not burning
hazardous waste
1987
1995
2000
Lightweight aggregate
kilns
1987
1995
2000
Asphalt mixing plants
1987
1995
2000
Petroleum refining catalyst
regeneration plants
1987
1995
2000
Cigarette smoking
1987
1995
2000
Air releases
Q. Inv.
13
17
17
3a
2a
2
5a
5a
5a
2
2
2
1
0.8
0.7
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
0.1
0.1
0.1
NQ
Water releases
Q. Inv.
Prelim.
NQ.
X
X
X
X
X
X
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
00 §
i
a,
§•
a
o
O 3
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Carbon reactivation
furnaces
1987
1995
2000
Kraft black liquor recovery
boilers
1987
1995
2000
Lime kilns
2000
Glass manufacturing
1987
1995
2000
Automobile shredders and
thermal APCDs at plating
and painting facilities
1987
1995
2000
Air releases
Q. Inv.
0.1
0.1
0.1
2
2
0.9
0.1
0.4a
0.4a
0.4a
Prelim.
NQ
X
X
X
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
MINIMALLY CONTROLLED OR UNCONTROLLED COMBUSTION
Combustion of landfill gas
1987
1995
2000
Structural fires
1987
1995
2000
Vehicle fires — cars and
other vehicles
1987
1995
2000
Landfill fires
1987
1995
2000
Forest and brush fires
1987
1995
2000
Backyard burning
1987
1995
2000
180
170
730
610
630
600
2a
T
22a
24
18
16
39a
29a
24a
1,300
1,300
1,300
260
200
180
lla
7a
6a
2,000
2,000
2,000
18a
17a
73a
X
X
X
X
X
X
X
X
X
§•
rs
I
I
o
0 §
i
a,
§•
a
o
§
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Residential yard burning
1987
1995
2000
Land clearing debris
burning
1987
1995
2000
Open burning of
demolition/construction
wood
1987
1995
2000
Fireworks, underground
coal fires, open burning of
energetic materials, PCBs,
candles, oil spills
1987
1995
2000
Sugar cane burning
1987
1995
2000
Air releases
Q. Inv.
4
5
5
Prelim.
83
79
85
22
22
22
28
31
35
NQ
X
X
X
Land releases
Q. Inv.
Prelim.
0.1
0.1
0.1
8
8
9
240
240
240
1
2
2
NQ
X
X
X
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
o
a
i
a,
§•
a
o_
I
O 3
0|
2 ^
o^
H »
O^
HH^S
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
METALLURGICAL PROCESSES
Primary copper smelting
and refining
1987
1995
2000
Primary magnesium
smelting and refining
1987
1995
2000
Primary nickel smelting
and refining
1987
1995
2000
Primary titanium smelting
and refining
1987
1995
2000
Secondary aluminum
smelting
1987
1995
2000
0.3a
0.5a
0.5a
13
13
8
11
20
8
X
X
X
X
X
X
X
X
X
X
X
X
X
X
§•
rs
I
I
o
i
a,
§•
a
o
§
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
S«
&
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Secondary zinc production
1987
1995
2000
Secondary copper smelting
1987
1995
2000
Secondary lead smelting
1987
1995
2000
Sinter production
1987
1995
2000
Coke production
1987
1995
2000
Secondary ferrous metal
smelting/refining
1987
1995
2000
Air releases
Q. Inv.
4a
T
T
990
270
0.9
1
2
2
33
28
24
10a
9a
8a
37
46
59
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
O
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to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Ferrous foundries
1987
1995
2000
Aluminum foundries
1987
1995
2000
Copper foundries
1987
1995
2000
Scrap electric wire
recovery
1987
1995
2000
Drum and barrel
reclamation furnaces
1987
1995
2000
Air releases
Q. Inv.
13
19
16
<0.1a
<0.1a
<0.1a
0.6
0.6
0.6
Prelim.
0.3a
0.3a
0.3a
NQ
X
X
X
Land releases
Q. Inv.
Prelim.
NQ
X
X
X
X
X
X
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
•§
: §
i
a,
§•
a
o_
I
o s
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ.
Product releases
Q. Inv.
Prelim.
NQ
CHEMICAL MANUFACTURING/PROCESSING SOURCES
Bleached chemical pulp
and paper mills
1987
1995
2000
Stand-alone chlor-alkali
plants
1987
1995
2000
Stand-alone vinyl chloride
plants
1987
1995
2000
Complex chemical plants
producing chlorine and a
variety of chlorinated
orgamcs
1987
1995
2000
<0.1a
<0.1a
0.6a
5
14
2
0.2
1
360
28
1
2a
2a
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
Municipal wastewater
treatment plants
1987
1995
2000
Residential septic systems
1987
1995
2000
Manufacturing of soaps,
detergents, textiles, dyes,
pigments, and inks
1987
1995
2000
All natural processes and
sources, including ball
clay, biotransformation,
etc.
1987
1995
2000
Air releases
Q. Inv.
Prelim.
NQ
X
X
X
X
X
X
Land releases
Q. Inv.
62
120
50
Prelim.
0.2
0.2
0.3
NQ
X
X
X
Water releases
Q. Inv.
Prelim.
13
12
15
NQ.
X
X
X
Product releases
Q. Inv.
3
18
7
Prelim.
NQ
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
H S.
O
c
o
H
W
-------
to
OJ
Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO9s TEQDr/year)
(continued)
Source
TOTALS
1987
1995
2000
Air releases
Q. Inv.
15,000
3,400
2,300
Prelim.
1,500
1,500
1,500
NQ
Land releases
Q. Inv.
2,400
2,400
2,300
Prelim.
270
270
330
NQ
Water releases
Q. Inv.
360
30
28
Prelim.
13
12
15
NQ.
Product releases
Q. Inv.
36
47
7
Prelim.
NQ
§•
rs
I
aResults provided in I-TEQ.
TO x = Releases are possible during this year, but the data are insufficient to develop estimates.
| Q. Inv. = Quantitative Inventory.
KT-J Prelim. = Preliminary.
J NQ = Not quantified.
g APCD = air pollution control device.
8 Blanks = No evidence that releases occur.
o
a
i
a,
I
a
o
o s
o|
^ ^
o^
H »
o^
HH^S
H S.
O
c
o
H
W
-------
Table 1-13 Summary of PCB releases for reference years 1987,1995, and 2000 (g WHO98 TEQp/year)
to
OJ
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ
Product releases
Q. Inv.
Prelim.
NQ
RELEASES FROM COMMERCIAL PCB PRODUCTS
PCB incineration
Accidental fires, leaks,
and spills
X
X
X
X
X
CHEMICAL MANUFACTURING AND PROCESSING SOURCES
Municipal wastewater
treatment
1987
1995
2000
51
78
19
2
12
3
COMBUSTION SOURCES
Municipal waste
combustors
1987
1995
2000
Industrial wood
combustion
Medical waste
incineration
1987
1995
2000
Tire combustion
7
15
15
97
18
14
X
X
§•
rs
I
I
o
•
00 §
i
a,
§•
a
o
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
O
c
o
H
W
-------
Table 1-13. Summary ofPCB releases for reference years 1987,1995, and 2000 (g WHO98 TEQp/year) (continued)
to
OJ
Source
Cigarette smoking
1987
1995
2000
Sewage sludge
incineration
1987
1995
2000
Backyard barrel burning
1987
1995
2000
Petroleum refining
catalyst regeneration
Hazardous waste
incineration
Power plants
Forest fires
1987
1995
2000
Air releases
Q. Inv.
41
43
34
Prelim.
0.1
0.1
0.4
1
0.7
12
11
49
NQ
X
X
X
Land releases
Q. Inv.
1
1
0.8
Prelim.
NQ
X
Water releases
Q. Inv.
Prelim.
NQ
Product releases
Q. Inv.
Prelim.
NQ
§•
rs
I
I
o
§
i
a,
§•
a
o
O 3
H S.
O
c
o
H
W
-------
Table 1-13. Summary ofPCB releases for reference years 1987,1995, and 2000 (g WHO98 TEQp/year) (continued)
to
OJ
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ
Product releases
Q. Inv.
Prelim.
NQ
METAL REFINING
Iron ore sintering
1987
1995
2000
Copper smelting
Aluminum smelting
TOTAL
1987
1995
2000
41
43
34
4
3
3
120
48
82
X
X
52
79
20
2
12
3
§•
rs
I
I
o
0 §
i
a,
§•
a
o
O 3
0|
^ ^
o^
H »
O^
HH^S
H S.
x = Releases are possible during this year, but the data are insufficient to develop estimates.
Q. Inv. = Quantitative Inventory.
Prelim. = Preliminary.
NQ = Not quantified.
Blanks = No evidence that releases occur.
O
c
o
H
W
-------
Table 1-14. Summary of CDD/CDF reservoir releases (g WHO9s TEQDr)
Source
Soil reservoirs
1987
1995
2000
Water, sediment,
biota reservoirs
1987
1995
2000
Product reservoirs
1987
1995
2000
Air releases
Q. Inv.
Prelim.
NQ
X
X
X
X
X
X
X
X
X
Land releases
Q. Inv.
Prelim.
NQ
X
X
X
X
X
X
Water releases
Q. Inv.
Prelim.
5,000a
4,600a
4,300a
NQ
X
X
X
X
X
X
Includes both urban and rural waters.
x = Releases are possible during this year, but the data are insufficient to develop estimates.
Q. Inv. = Quantitative Inventory.
Prelim. = Preliminary.
NQ = Not quantified.
Table 1-15 Summary of PCB reservoir releases (g WHO98 TEQP)
Source
Soil reservoirs
1987
1995
2000
Water, sediment,
biota reservoirs
1987
1995
2000
Product reservoirs
1987
1995
2000
Air releases
Q. Inv.
Prelim.
NQ
X
X
X
X
X
X
X
X
X
Land releases
Q. Inv.
Prelim.
NQ
X
X
X
X
X
X
Water releases
Q. Inv.
Prelim.
200a
180a
170a
NQ
X
X
X
X
X
X
Includes rural waters only.
x = Releases are possible during this year, but the data are insufficient to develop estimates.
Q. Inv. = Quantitative Inventory.
Prelim. = Preliminary.
NQ = Not quantified.
This document is a draft for review purposes only and does not constitute Agency policy.
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Table 1-16. Ranking of top five sources by year and media release
Air
Land
Water
1987 releases (g TEQ)
Municipal waste — 9,500
Medical waste — 2,700
2° copper— 990
Backyard barrel — 610
Forest— 180
Backyard barrel— 2,000
Structure fires — 260
Municipal waste
treatment — 62
Residential wood — 21
Coal utilities — 17
Paper mills — 360
1995 releases (g TEQ)
Municipal waste incineration — 1,200
Backyard barrel — 630
Medical waste incineration — 510
2° copper— 270
Forest— 170
Backyard barrel— 2, 100
Structure fires— 200
Municipal waste treatment — 120
Coal utilities— 18
Residential wood — 1 1
Paper mills — 28
Chlor-alkali plants — 2
2000 releases (g TEQ)
Forest— 730
Backyard barrel — 600
Medical waste incineration — 400
Industrial wood — 82
Municipal waste incineration — 77
Backyard barrel— 2,000
Structure fires — 180
Municipal waste treatment — 50
Coal utilities— 22
Residential wood — 9
Chlorinated organics — 25
Chlor-alkali plants— 2
Paper mills — 1
Table 1-17 Amounts of CDDs/CDFs (g WHO9s TEQDr/year) contained in
products in year manufactured
Product
Bleached chemical wood pulp
Ethylene dichloride/vinyl chloride
Chloranif
Pentachlorophenol
2,4 -Dichlorophenoxy acetic acid (2,4-D)a
TOTAL
1987
500
NA
64b
20,000
33
21,000
1995
40
0.02
0.4b
4,800
29
4,900
2000
0.6
0.02
1.2b
4,200
NA
4,200
aOnly 2,4-D is considered to be an environmental release.
bUnits are I-TEQ.
NA = not available.
This document is a draft for review purposes only and does not constitute Agency policy.
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Table 1-18. Trend analyses based on quantitative inventory"
Air
Land
Water3
Product
Total
Releases (g WHO98 TEQ)
1987
15,000
2,400
360
36
18,000
1995
3,400
2,500
28
47
6,000
2000
2,300
2,300
1
7
4,600
Percent change
1987 to 1995
-77
+4
-92
+31
-67
1995 to 2000
-32
-8
-96
-85
-23
1987 to 2000
-85
-4
-100
-81
-74
aThese trends are based on the quantitative inventory only, i.e., they do not include the sources classified as
preliminary or unquantifiable. Some of the preliminary sources are potentially very large and if confirmed
could significantly change the trend observations.
bWater releases are based on bleached pulp and paper plants only because this is only source covered in all
three reference years.
This document is a draft for review purposes only and does not constitute Agency policy.
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Table 1-19. Uncertainty analysis for top nine air sources in 2000
Forest fires
Backyard barrel burning
Medical waste
Uncontrolled
Controlled
Municipal waste
combustion
Coal fired utility boilers
Industrial wood
Salt laden
Nonsalt laden
Diesel on-road vehicles
Cement kilns
Burning haz waste
Not burning haz waste
Industrial coal-fired
boilers
Total releases
Activity (kg)
Total
2.44 x 1011
7.79 x 109
1.98 x 108
4.03 x 108
8.94 x 1011
8.0 x 108
1.16 x 1011
1.19 x 10lla
6.37 x 1010
5.92 x 1010
Emission factor
(ngWHO98-TEQ/kg)
mean
3
77
1,900
51
0.078
15
0.6
540b
0.27
0.7
n
13
5
7
13
105
11
5
9
7
22
13
15
SD
4.7
53
1,600
81
0.2
11
0.6
240b
0.9
1.3
Releases
(gWH098-TEQ)
Total
730
600
380
20
77
70
12
70
64
19
17
41
2,100
SD
1,100
410
320
33
27
130
8.9
66
29
7
55
78
1,300
aUnits are L.
bUnits are pg WHO98-TEQ/L.
This document is a draft for review purposes only and does not constitute Agency policy.
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Process Inputs and Outputs
Air Emissions
Inputs
Process
—S Product
—\ Water Discharges
Solid Residues
Landfill
Incinerator
By-Product
Open
Land
Disposal
Figure 1-1. Process inputs and outputs.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 2. MECHANISMS OF FORMATION OF DIOXIN-LIKE COMPOUNDS DURING
2 COMBUSTION OF ORGANIC MATERIALS
3
4
5 This chapter has not been updated because it is not critical to the inventory and may be
6 best presented elsewhere. Accordingly, any future updates to this chapter will be pursued
7 independently from the inventory.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3. COMBUSTION SOURCES OF CDDS/CDFS: WASTE INCINERATION
2
3
4 3.1. MUNICIPAL WASTE COMBUSTION
5 3.1.1. Air Releases
6 More information was available for the municipal waste incinerators than any other
7 source, allowing a detailed approach for estimating the total emissions. Stack test data were
8 available for 11 of 111 facilities in 1987, 27 of 125 facilities in the 1995, and 78 of 105 facilities
9 in 2000. These data were used to develop emission factors for over 20 design classes based on
10 the combination of furnace type and air pollution controls. Additionally, a complete list of all
11 facilities operating in the reference years and their activity levels were available. Releases from
12 the tested facilities were derived directly from the stack tests, and the releases from the untested
13 facilities were derived by assigning it an emission factor and multiplying by the activity. Finally,
14 the total releases for each reference year were estimated by summing the releases from each
15 facility operating in that year.
16 This approach is a modification of the approach used in the 2006 report. Emission
17 factors were changed for a few design classes to make them more consistent, and new tables
18 were developed for each reference year that list each facility and its emission factor, activity
19 level, and emission rate (see Tables 3-1, 3-2, and 3-3). This led to some minor changes in total
20 emissions.
21 The releases for the year 2000 were also estimated using the UNEP (2005) emission
22 factors:
23
24 • Low technology, no APCD—35,000 ng I-TEQ/kg
25 • Controlled, minimal APCD—350 ng I-TEQ/kg
26 • Controlled, good APCD—30 ng I-TEQ/kg
27 • High technology, sophisticated APCD—0.5 ng I-TEQ/kg
28
29 The emission factor for controlled facilities with good APCDs (30 ng I-TEQ/kg) was
30 applied to all small incinerators (defined as those with operating capacities less than 250 tons/day
31 and totaling 2.6 million tons in 2000), and the emission factor for high technology facilities with
32 sophisticated APCDs (0.5 ng I-TEQ/kg) was applied to all large facilities (defined as those with
This document is a draft for review purposes only and does not constitute Agency policy.
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1 operating capacities greater than 250 tons/day and totaling 27 million tons in 2000). This
2 approach yields a release estimate of 92 g I-TEQ/year, which is comparable to the
3 69 g I-TEQop/year estimate reported here based on adding emissions of each facility.
4
5 3.1.2. Water Releases
6 Some municipal waste combustors use wet scrubbers to treat emissions. Water
7 discharges may be associated with such devices. Some of these facilities have water treatment
8 systems that reduce particulate levels (and associated dioxins) prior to discharge. No
9 information was found to estimate the magnitude of CDD/CDF releases from these devices.
10 Accordingly, releases are possible, but estimates could not be made (Not quantifiable).
11
12 3.1.3. Solid Residue Releases
13 In the United States, all municipal waste combustor ash (except the portion used in
14 products—see discussion below) is disposed in permitted landfills. As defined in this inventory,
15 landfilled material does not represent a release to the open environment and is not included in the
16 source inventory. However, for informational purposes and when sufficient information is
17 available, this document provides estimates of the amounts of ash landfilled. The discussion
18 below presents estimates of the amount of dioxin in municipal waste ash sent to landfills.
19 Municipal waste combustors create solid residues in the form of fly ash, which is
20 collected from the stack by APCDs, and bottom ash, which is discharged directly from the
21 combustor. As discussed in EPA (2006), a variety of studies have measured dioxin levels in
22 municipal waste combustor ash from the United States. Only two of these provided congener
23 data allowing TEQ calculations:
24
25 • Ashes from five state-of-the-art municipal waste combustor facilities located in different
26 regions of the United States were analyzed for all 2,3,7,8-substituted CDDs/CDFs. The
27 TEQ levels in the ash (fly ash mixed with bottom ash) ranged from 106 to
28 466 ng I-TEQDF/kg, with a mean value of 258 ng I-TEQDF/kg CDFs (U.S. EPA, 1990a).
29 • Washington State Department of Ecology (1998) reported CDD/CDF congener data for
30 ash and other solid residuals from three municipal incinerators (Fort Lewis, Bellingham
31 [municipal plus medical wastes], and Spokane). The data were compiled and evaluated
32 to determine a total I-TEQ concentration and loading. The results showed fly ash ranging
33 from 0.51 to 4.98 ug I-TEQ/kg, bottom ash ranging from 0.00 to 0.2 ug I-TEQ/kg, and
34 mixed ash ranging from 0.038 to 0.163 ug I-TEQ/kg.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 EPA (2006) also summarized municipal waste combustor ash information from a variety of
2 studies conducted in other countries, with two reporting TEQ calculations:
O
4 • Kobylecki et al. (2001) analyzed the reduction of dioxins in fly ash by pelletizing the ash
5 and reburning the pellets in a laboratory-scale bubbling fluidized-bed furnace. Fly ash
6 for the test input material was collected from a fly ash filter vessel during 4 days of
7 municipal waste combustor operation. The total TEQ value derived by Kobylecki was
8 862 ng I-TEQDF/kg of fly ash.
9 • Sakai et al. (2001) analyzed the levels of dioxins and PCBs in fly ash and bottom ash
10 from a newly constructed municipal waste combustor in Japan. TEQ values derived from
11 the data give a total of 423 ng I-TEQDF/kg for fly ash and 10.5 ng I-TEQDF/kg for bottom
12 ash for dioxins and 31.6 ng I-TEQop/kg for fly ash and 0.85 ng I-TEQop/kg for bottom
13 ash for PCBs.
14
15 UNEP (2005) provided emission factors for fly ash ranging from 15 to 500 ug I-TEQ/MT of
16 municipal solid waste burned and emission factors for bottom ash ranging from 1.5 to
17 75 ug I-TEQ/MT of municipal solid waste burned. For municipal waste combustors with
18 controlled combustion and good APCD (this class would be typical of many of the U.S.
19 facilities), the recommended values were 200 ug I-TEQ/MT of municipal solid waste burned for
20 fly ash and 7 ug I-TEQ/MT of municipal solid waste burned for bottom ash.
21 Given the very limited data on TEQ levels in ash from U.S. facilities, it was decided to
22 use the UNEP (2005) default recommendations as follows: the UNEP recommendations for
23 municipal waste combustors with controlled combustion and minimal APCDs
24 (200 ug I-TEQ/MT of municipal solid waste burned for fly ash and 7 ug I-TEQ/MT of municipal
25 solid waste burned for bottom ash) were assumed to apply to 1987. Extensive improvements in
26 APCDs (including reductions in the use of hot-sided electrostatic precipitators ESPs) occurred
27 from 1987 to 1990. So reductions would also be expected in the dioxin content of the ash. Thus,
28 the UNEP recommendations for municipal waste combustors with controlled combustion and
29 good APCDs (15 ug I-TEQ/MT of municipal solid waste burned for fly ash and
30 1.5 ug I-TEQ/MT of municipal solid waste burned for bottom ash) were assumed to apply to
31 1995 and 2000. These assumptions are summarized below:
32 • 1987—200 ng I-TEQ/kg of municipal solid waste burned for fly ash and 7 ng I-TEQ/kg
33 of municipal solid waste burned for bottom ash
This document is a draft for review purposes only and does not constitute Agency policy.
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1 • 1995—15 ng I-TEQ/kg of municipal solid waste burned for fly ash and 1.5 ng I-TEQ/kg
2 of municipal solid waste burned for bottom ash
3 • 2000—15 ng I-TEQ/kg of municipal solid waste burned for fly ash and 1.5 ng I-TEQ/kg
4 of municipal solid waste burned for bottom ash
5
6 Multiplying the emission factors by the total municipal waste activity levels, yielded the
7 following estimates of amount of dioxin in landfilled ash:
8
9 • 1987—2,800 gl-TEQ
10 • 1995—490 gl-TEQ
11 • 2000—490 g I-TEQ
12
13 As indicated earlier, in the United States, all municipal waste combustor ash (except the portion
14 used in products—see discussion below) is disposed in permitted landfills and, therefore, not
15 included in the source inventory.
16 The amount of ash generated by municipal waste incineration is not directly used in the
17 procedure described above to estimate the amount of dioxin in landfilled ash. However, this
18 may be of interest and is estimated here for informational purposes only. An estimated 7 MMT
19 of total ash (bottom ash plus fly ash) were generated by municipal waste combustors in 1992
20 (telephone conversation between J. Loundsberry, EPA Office of Solid Waste, and L. Brown,
21 Versar, Inc., February 24, 1993). EPA indicated that 2 to 5 MMT of total ash were produced
22 annually in the late 1980s from municipal waste combustors, with fly ash comprising 5 to 15%
23 of the total (U.S. EPA, 1991). UNEP (2005) indicates that the amount of fly ash generated per
24 ton of municipal solid waste is typically 1-2%, and the amount of bottom ash generated per ton
25 of municipal solid waste is approximately 10-20%. The amounts of ash generated were
26 calculated using the midpoints of these ranges:
27
28 • 1987—The total municipal solid waste burned was estimated as 13.7 billion kg (this
29 implies that 0.2 billion kg of fly ash and 2.1 billion kg of bottom ash were generated).
30 • 1995—The total municipal solid waste burned was estimated as 29.8 billion kg (this
31 implies that 0.4 billion kg of fly ash and 4.5 billion kg of bottom ash were generated).
This document is a draft for review purposes only and does not constitute Agency policy.
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1 • 2000—The total municipal solid waste burned was estimated as 29.4 billion kg (this
2 implies that 0.4 billion kg of fly ash and 4.4 billion kg of bottom ash were generated).
3
4 3.1.4. Products
5 The primary purpose of municipal waste combustors is waste disposal rather than the
6 manufacture of products. However, some municipal waste combustor ash has been used in
7 road-building materials (UNEP, 2005). The concentration of CDD/CDFs in these products
8 would be a fraction of the level found in the original residues. For example, if the product
9 contained 1% municipal waste combustor residues, the CDD/CDF concentration would be 1% of
10 the level found in the original residue. No information could be found on the residue content of
11 these products. Similarly, no information could be found on the quantity of ash going into such
12 products. It is possible that the ash is tightly bound to the construction materials, reducing the
13 chance of release to the open environment. However, no data could be found on this issue.
14 Accordingly, releases are probably small, but estimates could not be made (Not quantifiable).
15
16 3.1.5. Release Summary
17 The inventory decision criteria and release estimates to all media are summarized below.
Inventory Decision Criteria for Municipal
Waste Incinerators
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
E ^mission factor tests represent units that are typical of the
ass.
ctivity estimates based on source-specific surveys.
onclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
This document is a draft for review purposes only and does not constitute Agency policy.
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Municipal Waste Incinerators
Air Releases
Emission Factors
• 1987—Table 3-1.
• 1995—Table 3-2.
• 2000—Table 3-3.
Activity Levels
• 1987—Table 3-1 (overall total is 13.7 billion kg of waste).
• 1995—Table 3-2 (overall total is 29.8 billion kg of waste).
• 2000—Table 3-3 (overall total is 29.4 billion kg of waste).
Releases
• 1987—Table 3-1. Total releases were 9,500 g WHO98 TEQDF/yr (8,500 g I-TEQDF/yr).
• 1995—Table 3-2. Total releases were 1,200 g WHO98 TEQDF/yr (1,100 g I-TEQDF/yr).
• 2000—Table 3-3. Total releases were 77 g WHO98 TEQDF/yr (69 g I-TEQDF/yr).
Water Releases
Water releases are possible, but data are insufficient to make quantitative estimates (Not
quantifiable).
Solid Residue Releases
All municipal waste combustor ash (except the portion used in products—see below) is disposed
in permitted landfills. As defined in this inventory, landfilled material does not represent a
elease to the open environment and is not included in the source inventory.
Products
Jroduct releases are possible, but data are insufficient to make quantitative estimates (Not
quantifiable).
1 3.2. HAZARDOUS WASTE INCINERATION
2 Hazardous wastes are burned in a variety of situations and are covered in a number of
3 different sections in this report.
4
5 • Hazardous waste is burned in facilities dedicated to burning this type of waste. Most of
6 these dedicated facilities are located on site at chemical manufacturing facilities and burn
7 only the waste associated with their on-site industrial operations. Hazardous waste is also
8 burned at dedicated facilities located off site. These facilities accept waste from multiple
9 sources. On- and off-site dedicated hazardous waste burning facilities are addressed in
10 Section 3.2.1.
11 • Hazardous waste is also burned in industrial boilers and furnaces that are permitted to
12 burn the waste as supplemental fuel. These facilities have significantly different furnace
13 designs and operations than those of dedicated hazardous waste incinerators (HWIs).
14 They are discussed in Section 3.2.2.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 • Hazardous waste is also burned in halogen acid furnaces (HAFs), in which halogen acids
2 (such as HC1) may be produced from halogenated secondary materials. These facilities
3 are discussed in Section 3.2.3.
4 • A number of cement kilns and lightweight aggregate kilns are also permitted to burn
5 hazardous waste as auxiliary fuel. These are discussed separately in Section 5.1.
6 • Mobile HWIs are typically used for site cleanup at Superfund sites. These units can be
7 transported from one location to another and operate for a limited duration at any given
8 location. Due to a lack of information about these facilities, they are not included in this
9 inventory.
10
11 3.2.1. Dedicated HWIs
12 3.2.1.1. Air Releases
13 No changes were made in the air-release estimates reported in U.S. EPA (2006). Where
14 feasible, this document subdivides the combustors in each source category into design classes
15 judged to have similar potential for CDD/CDF emissions. However, this would not have been
16 useful for dedicated HWIs because information was lacking about the amount of waste burned in
17 each of the design classes. Additionally, all HWI designs achieve excellent combustion
18 efficiency using high temperatures and long residence times, suggesting that little difference in
19 emission factors would be observed among the design classes. Minor changes in design and
20 operating procedures would be expected in 2000 due to the stricter emission limits that became
21 effective at that time. Therefore, the strategy used to develop emission factors for HWIs was to
22 assume that the emission tests conducted prior to 2000 represented facilities in operation during
23 the reference years 1987 and 1995 and the emission tests conducted in 2000 represented the
24 facilities operating in 2000.
25 The emission factors were developed using stack test data from a database compiled by
26 the EPA Office of Solid Waste (OSW). This database summarizes the results of stack testing for
27 CDDs/CDFs at a number of HWIs between 1993 and 2000 (U.S. EPA, 2002b). For the purposes
28 of estimating emissions in 1995, an emission factor was developed using data from 17 HWIs
29 tested between 1993 and 1996. For the purposes of estimating emissions in 2000, an emission
30 factor was developed using data from 10 HWIs tested in 2000 (a total of 22 HWIs were tested in
31 2000, but flue gas flow rates were available for only 10 of these incinerators). For the purposes
32 of estimating emissions in 1987, the emission factor derived for 1995 was assumed to apply to
This document is a draft for review purposes only and does not constitute Agency policy.
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1 1987. The 1987 activity estimate is from Dempsey and Oppelt (1993), and the 1995/2000
2 estimate is based on Federal Register (1996).
3 The emission factors assumed here were in the range of 2-4 ng I-TEQ/kg, which falls in
4 between the values recommended by UNEP (2005) for the top two performing classes:
5
6 • Low technology, no APCD—35,000 ng I-TEQ/kg
7 • Controlled, minimal APCD—350 ng I-TEQ/kg
8 • Controlled, good APCD— 10 ng I-TEQ/kg
9 • High technology, sophisticated APCD—0.75 ng I-TEQ/kg
10
11 3.2.1.2. Water Releases
12 Many HWIs use wet scrubber systems, which can have water discharges. However, no
13 information was found to support release estimates (Not quantifiable).
14
15 3.2.1.3. Solid Residue Releases
16 EPA (1987) contains limited data on ash generated from hazardous waste incineration.
17 The study indicates that the mean concentrations of CDDs and CDFs from an HWI with an
18 afterburner were 538 ug/kg and 2,853 ug/kg, respectively (Table 3-8 in U.S. EPA, 1987).
19 Specific data for congeners and for ash quantities were not provided. Accordingly, quantitative
20 estimates cannot be made about amounts of CDD/CDFs in solid residues from dedicated HWIs.
21 In the United States, all HWI ash is disposed in permitted landfills. As defined in this inventory,
22 landfilled material does not represent a true release to the open environment and is not included
23 in the source inventory.
24
25 3.2.1.4. Products—None
26
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3.2.1.5. Release Summary
2 The inventory decision criteria and releases are summarized below:
Inventory Decision Criteria for Dedicated HWIs
Air Water Solids Products
mission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission
'actors.
Vleasured emission factors consistent or have Yes
understandable differences.
mission factor tests represent units that are typical of the Yes
;lass.
activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
Dedicated HWIs
Air Releases
Emission Factors
• 1987—3.9 ng WHO98 TEQDF/kg (3.8 ng I-TEQDF/kg) of waste feed.
• 1995—3.9 ng WHO98 TEQDF/kg (3.8 ng I-TEQDF/kg) of waste feed.
• 2000—2.1 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg) of waste feed.
Activity Levels
• 1987—1.3 billion kg.
• 1995—1.5 billion kg.
• 2000—1.5 billion kg.
Releases
• 1987—5 g (WHO98 TEQDF or I-TEQDF).
• 1995—6 g WHO98 TEQDF (5.7 g I-TEQDF).
• 2000-3 g WH098 TEQDF (3 g I-TEQDF).
Water Releases
}ossible, but data are insufficient to make quantitative estimates (Not quantifiable).
Solid Residue Releases
Ash is landfilled, so it is not considered an environmental release.
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3.2.2. Industrial Boilers and Furnaces Burning Hazardous Waste
2 3.2.2.1. Air Releases
3 The emission factors for industrial boilers and furnaces burning hazardous waste were
4 derived from test data for three facilities presented in the OSW database. Minor changes in
5 design and operating procedures would be expected in 2000 due to the stricter emission limits
6 that became effective at that time. Therefore, the strategy used to develop emission factors for
7 these facilities was to assume that the emission tests conducted prior to 2000 represented
8 facilities in operation during the reference years 1987 and 1995 and the emission tests conducted
9 in 2000 represented the facilities operating in 2000. The activity level used in US EPA, 2006
10 (derived from survey data in Dempsey and Oppelt, 1993 and other OSW data) for 2000 was
11 changed from 1.5 to 0.6 billion kg based on the assumption that no change occurred from 1995.
12 As a result, minor changes were also made in the air-release estimate for reference year 2000.
13 3.2.2.2. Water Releases
14 Some industrial boilers use wet scrubber systems, which can have water discharges.
15 However, no information was found to support release estimates (Not quantifiable).
16
17 3.2.2.3. Solid Residue Releases
18 Because these facilities are typically burning liquid waste, little ash would be generated.
19
20 3.2.2.4. Products—None
21
22 3.2.2.5. Release Summary
23 The releases are summarized below:
24
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Industrial Boilers and Furnaces Burning Hazardous Waste
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
Industrial Boilers and Furnaces Burning Hazardous Waste
Air Releases
Emission Factors
• 1987—0.65 ng WHO98 TEQDF/kg (0.64 ng I-TEQDF/kg) of waste feed.
• 1995—0.65 ng WHO98 TEQDF/kg (0.64 ng I-TEQDF/kg) of waste feed.
• 2000—1.2 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of waste feed.
Activity Levels
• 1987—1.2 billion kg.
• 1995—0.6 billion kg.
• 2000—0.6 billion kg.
Releases
• 1987—0.8 g WHOgg TEQoF (0.8 g I-TEQDF).
• 1995—0.4 g WHOgg TEQoF (0.4 g I-TEQDF).
• 2000—0.7 g WHO98 TEQDF (0.7 g I-TEQDF).
Water Releases
}ossible, but data are insufficient to make quantitative estimates (Not quantifiable).
Solid Residue Releases
Jone.
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3.2.3. Halogen Acid Furnaces Burning Hazardous Waste
2 3.2.3.1. Air Releases
3 No changes were made to the air-release estimates. The emission factors for halogen
4 acid furnaces (HAFs) burning hazardous waste were derived from the same OSW database used
5 for dedicated HWIs. For the purposes of estimating emissions in 2000, an emission factor was
6 developed using data from two HAFs tested in 2000. For the purposes of estimating emissions
7 in 1987 and 1995, the emission factor derived for 2000 was assumed to apply to the earlier years.
8 The activity estimate was based on survey data provided by OSW for 2000 and assumed to be
9 also representative of the earlier years.
10
11 3.2.3.2. Water Releases
12 No information was found to support release estimates.
13
14 3.2.3.3. Solid Residue Releases
15 Because these facilities are typically burning liquid waste, no ash would be generated.
16
17 3.2.3.4. Products—None
18
19 3.2.3.5. Release Summary
20 The inventory decision criteria and releases are summarized below:
Inventory Decision Criteria for Halogen Acid Furnaces Burning Hazardous Waste
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
This document is a draft for review purposes only and does not constitute Agency policy.
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Halogen Acid Furnaces Burning Hazardous Waste
Air Releases
Emission Factors
• 1987—0.84 ng WHO98 TEQDF/kg (0.80 ng I-TEQDF/kg) of waste feed.
• 1995—0.84 ng WHO98 TEQDF/kg (0.80 ng I-TEQDF/kg) of waste feed.
• 2000—0.84 ng WHO98 TEQDF/kg (0.80 ng I-TEQDF/kg) of waste feed.
Activity Levels
• 1987—376 million kg.
• 1995—376 million kg.
• 2000—376 million kg.
Releases
• 1987—0.3 g WHO98 TEQDF (0.3 g I-TEQDF).
• 1995—0.3 g WHO98 TEQDF (0.3 g I-TEQDF).
• 2000—0.3 g WHO98 TEQpp (0.3 g I-TEQDF).
Water Releases
*ossible, but data are insufficient to make quantitative estimates (Not quantifiable).
Solid Residue Releases
None.
Products
None.
1 3.3. MEDICAL WASTE INCINERATION
2 3.3.1. Air Releases
3 Changes were made to the emission factors. The U.S. EPA, 2006 report divided the
4 uncontrolled class into two subclasses and the controlled class into three subclasses. Some of
5 these classes had very few tested facilities, and the range of emission factors overlapped between
6 subclasses. Thus, it was decided to combine these classes into one emission factor for
7 uncontrolled facilities (1,870 ng WHO98 TEQ/kg, 1,760 ng I-TEQ/kg) based on testing at
8 seven facilities and one for controlled facilities (51 ng WHO98 TEQ/kg, 50 ng I-TEQ/kg) based
9 on testing at 12 facilities. For comparison purposes, the UNEP (2005) emission factor
10 recommendations are provided below:
11 • Uncontrolled, batch, no APCD—40,000 ng I-TEQ/kg
12 • Controlled, batch, minimal APCD—3,000 ng I-TEQ/kg
13 • Controlled, batch, good APCD—525 ng I-TEQ/kg
14 • Controlled, continuous, excellent APCD—1 ng I-TEQ/kg
15
This document is a draft for review purposes only and does not constitute Agency policy.
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1 Activity estimates are based on survey data summarized in U.S. EPA, 2006. Table 3-4
2 shows the activities and release estimates for each year. These changes resulted in small
3 increases in total releases compared to the original values reported in U.S. EPA, 2006.
4
5 3.3.2. Water Releases
6 Some medical waste incinerators use wet scrubber systems, which can have water
7 discharges. However, no information was found to support release estimates (Not quantifiable).
8
9 3.3.3. Solid Residue Releases
10 In the United States, all ash from medical waste incinerators is disposed in permitted
11 landfills. As defined in this inventory, landfilled material does not represent a true release to the
12 open environment and is not included in the source inventory. However, for informational
13 purposes, the discussion below presents estimates of the amount of dioxin in landfilled ash.
14 Fiedler et al. (2002) tested a hospital waste incinerator in Thailand. The furnace had a
15 static grate and was equipped with a secondary combustion chamber and two afterburners. The
16 flue gases passed over an alkaline water bath before being discharged through a flue stack.
17 Overall, the plant appeared poorly designed and poorly maintained. Bottom ash concentrations
18 of 1,390 and 1,980 ng -TEQ/kg were found. The authors suggest the high results were due to the
19 poor combustion conditions in the primary chamber and the practice of leaving the bottom ashes
20 overnight in the chamber to slowly cool down.
21 As indicated above, emission testing data could be located for only one facility. The poor
22 condition of this facility suggests it is not representative of U.S. facilities. UNEP (2005)
23 suggests emission factors ranging from 150 to 920 ng I-TEQ/kg of waste burned (for combined
24 bottom ash and fly ash) for controlled facilities. The average of this range is assumed for all
25 reference years: 530 ng I-TEQop/kg of waste. These UNEP recommendations are not linked to
26 specific references and appear to represent the professional judgment and consensus among the
27 authors. It is unknown how representative this emission factor is of U.S. facilities. Accordingly,
28 it is regarded as preliminary.
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1 The amounts of dioxin in landfilled ash were estimated by multiplying the emission
2 factor by the activity level:
3
4 • 1987—760 gl-TEQoF
5 • 1995—410 gl-TEQoF
6 • 2000—320 g I-TEQoF
7
8 Because the ash is landfilled, it is not considered a release to the open environment and is not
9 included in the source inventory.
10 The total amount of landfilled ash is not directly used in the calculation above. However,
11 it may be of interest and is provided below for information purposes only. The estimates were
12 generated by assuming that the combined fly and bottom equals 20% of the waste feed (UNEP,
13 2005). This yields the following estimates:
14 • 1987—0.28 billion kg
15 • 1995—0.15 billion kg
16 • 2000—0.12 billion kg
17
18 3.3.4. Products—None
19
20 3.3.5. Release Summary
21 The inventory decision criteria and releases to all media are summarized below:
Inventory Decision Criteria for Medical
Waste Incinerators
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Enmission factor tests represent units that are typical of the
ass.
ctivity estimates based on source-specific surveys.
onclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
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Medical Waste Incinerators
Air Releases
Emission Factors
• 1987—Table 3-4.
• 1995—Table 3-4.
• 2000—Table 3-4.
Activity Levels
• 1987—Table 3-4.
• 1995—Table 3-4.
• 2000—Table 3-4.
Releases
• 1987—2,700 g WHO98 TEQDF/yr (2,600 g I-TEQDF/yr).
• 1995—510 g WHO98 TEQDF/yr (490 g I-TEQDF/yr).
• 2000—400 g WHO98 TEQDF/yr (3 80 g I-TEQDF/yr).
Water Releases
*ossible, but data are insufficient to make quantitative estimates (Not quantifiable).
Solid Residue Releases
The ash is landfilled so it is not considered an environmental release.
Products
None.
1 3.4. CREMATORIA
2 3.4.1. Human Crematoria
3 3.4.1.1. Air Releases
4 No changes were made to the air-release estimates. The emission factor was derived on
5 the basis of testing at two U.S. facilities and assumed to apply to all reference years. It
6 corresponds to the low end of the range recommended by UNEP (2005):
7 400 ng I-TEQ/cremation for facilities with optimal control, 10,000 ng I-TEQ/cremation for
8 facilities with medium control, and 90,000 ng I-TEQ/cremation for facilities with no control.
9 Activity information was derived from CANA (2006).
10
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3.4.1.2. Water Releases
2 These facilities do not use wet scrubbers, and there are no other identifiable water
3 releases associated with their operation.
4
5 3.4.1.3. Solid Residue Releases
6 No information was found on the disposition of cremation ash. It is assumed here that all
7 of it is eventually released to the open environment.
8 UNEP (2005) recommends an ash emission factor of 2,500 ng I-TEQ/cremation for
9 facilities with medium or optimal control. The CDD/CDF concentrations in the bottom ashes
10 collected from a two-chamber crematory in Thailand were 44 and 48 ng I-TEQ/kg of bottom ash
11 (UNEP, 2005; Fiedler et al., 2002). Based on the average of these tests, a concentration of
12 46 ng I-TEQ/kg of bottom ash is assumed for each reference year. This facility appears to have a
13 similar design to U.S. facilities. However, the emission factor was assigned a preliminary rating
14 because it is based on testing at only one facility.
15 The total bottom ash generated was estimated by multiplying the number of bodies
16 cremated per year (CANA, 2006), 5.5% ash content (Forbes et al., 1953), and 70 kg (average
17 adult body weight). This yields the following estimates:
18
19 • 1987—1.24 million kg
20 • 1995—1.88 million kg
21 • 2000—2.42 million kg
22
23 The solid residue releases were estimated by multiplying the ash concentration by the ash
24 activity level.
25 3.4.1.4. Products—None
26
27 3.4.1.5. Release Summary
28 The inventory decision criteria and releases are summarized below. The ash is typically
29 disposed in landfills and therefore not considered an environmental release.
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Inventory Decision Criteria for Human Crematoria
Air Water Solids Products
Emission tests for at least two units/source types with Yes No
mfficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have Yes Yes
understandable differences.
mission factor tests represent units that are typical of the Yes Yes
;lass.
activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
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Human Crematoria
Air Releases
Emission Factors
• 1987—450 ng WHO98 TEQDF/body cremated (430 ng I-TEQDF/body cremated).
• 1995—450 ng WHO98 TEQDF/body cremated (430 ng I-TEQDF/body cremated).
• 2000—450 ng WHO98 TEQDF/body cremated (430 ng I-TEQDF/body cremated).
Activity Levels
• 1987—A total of 323,371 cremations were performed.
• 1995—A total of 488,224 cremations were performed.
• 2000—A total of 629,362 cremations were performed.
Releases
• 1987—0.2 g WHO98 TEQDF (0.1 g I-TEQDF).
• 1995-0.2 g WH098 TEQDF (0.2 g I-TEQDF).
• 2000—0.3 g WHO98 TEQDF (0.3 g I-TEQDF).
Water Releases
None.
Solid Residue Releases
Emission Factors
• 1987—46 ng I-TEQ/kg of ash (Preliminary).
• 1995—46 ng I-TEQ/kg of ash (Preliminary).
• 2000—46 ng I-TEQ/kg of ash (Preliminary).
Activity Levels
• 1987—1.24 million kg ash.
• 1995—1.88 million kg ash.
• 2000—2.42 million kg ash.
Releases
• 1987—0.1 g I-TEQDF (Preliminary).
• 1995—0.1 g I-TEQDF (Preliminary).
• 2000—0.1 g I-TEQDF (Preliminary).
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3.4.2. Animal Crematoria
2 3.4.2.1. Air Releases
3 Minor changes were made in how these air releases were estimated. For destruction of
4 animal carcasses, UNEP (2005) recommends emission factors of 5 ng I-TEQ/kg for state-of-the-
5 art facilities, 50 ng I-TEQ/kg for updated facilities, and 500 ng I-TEQ/kg for uncontrolled
6 facilities. As described in EPA, 2006, only one U.S. facility emission test could be located. This
7 facility had very low emissions and may not be representative of most facilities. The mid-range
8 value recommend by UNEP was judged to more likely represent typical U. S. facilities.
9 Therefore, this emission factor was assumed to apply to each of the reference years:
10 50 ng I-TEQop/kg of animal cremated. Based on the limited test data and questions about its
11 representativeness, this emission factor is considered a preliminary estimate.
12 As part of the 2000 inventory, OAQPS (U.S. EPA, 2002b) calculated a national animal
13 cremation activity level estimate of 81.9 million kg/year for reference year 2000. Assuming that
14 the fraction of the population owning pets and the fraction of pets cremated stay reasonably
15 constant, this value can be extrapolated to the other reference years by assuming that animal
16 cremation rates are proportional to the human population. The following U.S. population
17 estimates were used in this exercise: 1987—242 billion, 1995—263 billion, and
18 2000—291 billion. The data for each reference year are presented below:
19
20 • 1987—68 million kg/year.
21 • 1995—74 million kg/year
22 • 2000—81.9 million kg/year
23
24 3.4.2.2. Water Releases—None
25
26 3.4.2.3. Solid Residue Releases
27 All ash from these facilities is assumed to be disposed in permitted landfills. As defined
28 in this inventory, landfilled material does not represent a true release to the open environment
29 and is not included in the source inventory. However, for informational purposes, the discussion
30 below presents estimates of the amount of dioxin in landfilled ash.
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1 As indicated above, emission testing data could be located for only one facility. No
2 bottom ash testing was reported for this facility. It has a similar design to the human cremation
3 facility in Thailand where testing found 44 and 48 ng I-TEQ/kg of bottom ash (UNEP, 2005;
4 Fiedler et al., 2002). Based on the average of these tests, an bottom ash concentration of
5 46 ng I-TEQ/kg is assumed for all reference years. It is completely unknown how representative
6 this facility is of U.S. facilities. Accordingly, it must be regarded as preliminary.
7 The total bottom ash generated was estimated by multiplying the mass of animals
8 cremated per year (see above) and 5.5% ash content (value for humans from Forbes et al., 1953).
9 This yields the following estimates:
10
11 • 1987—3.7 million kg
12 • 1995—4.1 million kg
13 • 2000—4.5 million kg
14
15 These estimates are considered preliminary because they are derived from Class D-rated
16 estimates for mass of animals cremated.
17 The amounts of dioxin in landfilled ash were estimated by multiplying the bottom ash
18 concentration by the ash activity level:
19
20 • 1987—0.17 g I-TEQDF (Preliminary)
21 • 1995—0.19 gl-TEQoF (Preliminary)
22 • 2000—0.21 gl-TEQoF (Preliminary)
23
24 The ash from these facilities is assumed to be landfilled and, therefore, is not considered a
25 release to the open environment.
26
27 3.4.2.4. Products—None
28
29 3.4.2.5. Release Summary
30 The inventory decision criteria and releases are summarized below:
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Animal Crematoria
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
No
Yes
No
Yes
P
Animal Crematoria
Air Releases
Emission Factors
• 1987—50 ng I-TEQop/kg of animal cremated (Preliminary).
• 1995—50 ng I-TEQop/kg of animal cremated (Preliminary).
• 2000—50 ng I-TEQpp/kg of animal cremated (Preliminary).
Activity Levels
• 1987—68 million kg/yr.
• 1995—74 million kg/yr.
• 2000—81.9 million kg/yr.
Releases
• 1987—3 g I-TEQDF (Preliminary).
• 1995—4 g I-TEQDF (Preliminary).
• 2000—4 g I-TEQDF (Preliminary).
Water Releases
None.
Solid Residue Releases
This ash is landfilled and, therefore, is not considered an environmental release.
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 3.5. SEWAGE SLUDGE INCINERATION
2 3.5.1. Air Releases
3 No changes were made to the air-release estimates. The emission factor of 6.7 ng
4 WHOgg TEQDF/kg was derived from testing at 14 U.S. facilities and applied to all three reference
5 years. UNEP (2005) recommends emission factors of 0.4 ng I-TEQ/kg for state-of-art facilities
6 and 4 ng I-TEQ/kg for updated facilities with controls. The emission factor used here is similar
7 to the UNEP recommendation for updated facilities with controls. The activity estimates were
8 derived from survey data summarized in EPA, 2006.
9
10 3.5.2. Water Releases
11 Because some sewage sludge incinerators use wet scrubber systems, it is possible that
12 water discharges occur. However, wastewater from wet scrubbers is often treated and then
13 reintroduced to the wastewater treatment plant, so that no water discharges occur directly from
14 the incinerator (in these cases, the CDD/CDFs in the effluent would likely end up in the sewage
15 sludge). As discussed below, some limited information is available on dioxin levels in scrubber
16 water. No information is available on quantities of scrubber effluent from U.S. facilities or what
17 portion is recycled back to the wastewater treatment operation. Therefore, releases are possible,
18 but no quantitative estimates could be made (Not quantifiable).
19 In Table 5-16 of EPA (1987), data are presented indicating that 2,3,7,8-TCDD was not
20 detected in scrubber water filtrate from three sewage sludge incinerators. However, total CDDs
21 for the three incinerators averaged 0.3 ng/kg, and total CDFs averaged 4 ng/kg. No data were
22 given for any congeners (other than 2,3,7,8-TCDD), nor were there any data on the quantities of
23 filtrate.
24 The European inventory (EU, 1999) reports concentrations between 1.2 and
25 6.5 pg I-TEQ/L in scrubber effluents from sewage sludge incinerators.
26
27 3.5.3. Solid Residue Releases
28 All ash from these facilities is assumed to be disposed in permitted landfills. As defined
29 in this inventory, landfilled material does not represent a true release to the open environment
30 and is not included in the source inventory. However, for informational purposes, the discussion
31 below presents estimates of the amount of dioxin in landfilled ash.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-23 DRAFT: DO NOT CITE OR QUOTE
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1 Testing of multiple hearth furnaces in the United Kingdom (Dyke et al., 1997) showed
2 CDD/CDF in the grate ash at concentrations of 39 ng TEQ/kg and 470 ng TEQ/kg in fly ash
3 from the ESP. Rates of ash production were 430 kg/ton of grate ash and 13 kg/ton of ESP ash
4 for the multiple hearth plant. Levels in ash (all the ash was collected in the ESP) from fluidized
5 bed combustion were much lower (<1 ng TEQ/kg); 373 kg of ESP ash were produced per ton of
6 sludge combusted in the fluidized bed.
7 In Table 5-16 of EPA (1987), data are presented indicating that 2,3,7,8-TCDD was not
8 detected in the bottom ash from three sewage sludge incinerators. However, total CDDs for the
9 three incinerators were nondetects, 20 ng/kg, and 10 ng/kg. For total CDFs, the values were
10 nondetects, 70 ng/kg, and 50 ng/kg. No data were given for any congeners (other than
11 2,3,7,8-TCDD), nor were there any data on the quantities of ash.
12 UNEP (2005) recommends default residue emission factors of 0.5 ng I-TEQ/kg of
13 sewage sludge for updated and modern furnaces. This was adopted for all reference years. This
14 is considered a preliminary (Class D) estimate because there were no U.S. data and very limited
15 European data to support it.
16 No data on ash generation rates were found. Rather, the activity was based on the annual
17 amount of sewage sludge incinerated—see the discussion above.
18 The amounts of dioxin in landfilled ash were estimated by multiplying the emission
19 factor by the activity level:
20
21 • 1987—0.43 gl-TEQoF (Preliminary)
22 • 1995—1.0 gI-TEQDF (Preliminary)
23 • 2000—0.71 gI-TEQDF (Preliminary)
24
25 The ash from these facilities is assumed to be landfilled and, therefore, is not considered a
26 release to the open environment.
27
28 3.5.4. Products—None
29
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-24 DRAFT: DO NOT CITE OR QUOTE
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1 3.5.5. Release Summary
2 The inventory decision criteria and releases to all media are summarized below:
Inventory Decision Criteria for Sewage
Sludge Incinerators
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
Sewage Sludge Incinerators
Air Releases
Emission Factors
• 1987—6.7 ng WHO98 TEQDF/kg (6.6 ng I-TEQDF/kg).
• 1995—6.7 ng WHO98 TEQDF/kg (6.6 ng I-TEQDF/kg).
• 2000—6.7 ng WHO98 TEQDF/kg (6.6 ng I-TEQDF/kg).
Activity Levels
• 1987—0.865 billion kg of dry sewage sludge.
• 1995—2.11 billion kg of dry sewage sludge.
• 2000—1.42 billion kg of dry sewage sludge.
Releases
• 1987—6 g WHOgg TEQDF (6 g I-TEQDF).
• 1995—14 g WHOgg TEQDF (14 g I-TEQDF).
• 2000— 10 g WHO98 TEQpp (9 g I-TEQDF).
Water Releases
}ossible but quantitative releases could not be made (Not quantifiable).
Solid Residue Releases
The ash from these facilities is assumed to be landfilled and, therefore, is not considered a
release to the open environment.
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-25 DRAFT: DO NOT CITE OR QUOTE
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1 3.6. TIRE COMBUSTION
2 This section covers releases from dedicated tire incinerators. Tires are also burned in
3 cement kilns, which are covered in Section 5.1. Some are combusted as auxiliary fuel in
4 industrial boilers and in pulp and paper mill combustion facilities, but the amount of tires going
5 to these types of facilities is assumed to be negligible (note that emissions from industrial boilers
6 are covered in Sections 3.2 and 4.3, and emissions from pulp and paper mills are covered in
7 Sections 3.7 and 8.1). Additionally, tires may be unintentionally burned in an uncontrolled
8 fashion at landfills (open burning). The open burning of tires is not discussed in this report due
9 to the lack of information, and, thus, is an unquantifiable source.
10
11 3.6.1. Air Releases
12 No changes were made to the air-release estimates. The emission factor of 0.28 ng
13 WHOgg TEQop/kg was derived from testing at one facility that was equipped with a dry scrubber
14 and fabric filter (CARB, 1991). Because other facilities may be equipped with less sophisticated
15 air pollution control systems, the TEQ emissions could be higher. For example, Cains and Dyke
16 (1994) reported much higher emission rates for two tire incinerators in the United Kingdom that
17 were equipped with only simple grit arresters. Because the emission factor is based on testing at
18 only one facility and it is inconsistent with other data, the release estimate is considered
19 preliminary. The activity estimates were derived from survey data from EPA, (1992b) and
20 Rubber Manufacturers Association (RMA) (2002).
21
22 3.6.2. Water Releases
23 Some tire combustion facilities may have wet scrubbers indicating that water releases are
24 possible. No information could be found on CDD/CDF levels in effluent or amounts of effluent
25 discharged from these facilities. Therefore, releases are possible but could not be quantified (Not
26 quantifiable).
27
28 3.6.3. Solid Residue Releases
29 Both bottom ash and fly ash can be created from tire combustion. No information could
30 be found on CDD/CDF levels in ash or amounts of ash associated with these facilities. Any ash
31 would be landfilled, and therefore, would not be considered an environmental release.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-26 DRAFT: DO NOT CITE OR QUOTE
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1
2 3.6.4. Products—None
3
4 3.6.5. Release Summary
5 The inventory decision criteria and releases are summarized below:
Inventory Decision Criteria for Tire Combustion
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
No
No
No
Yes
P
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-27 DRAFT: DO NOT CITE OR QUOTE
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Tire Combustion
Air Releases
Emission Factors
• 1987—0.28 ng WHO98 TEQDF/kg (0.28 ng I-TEQDF/kg) (Preliminary).
• 1995—0.28 ng WHO98 TEQDF/kg (0.28 ng I-TEQDF/kg) (Preliminary).
• 2000—0.28 ng WHO98 TEQDF/kg (0.28 ng I-TEQDF/kg) (Preliminary).
Activity Levels
• 1987—0.385 billion kg.
• 1995—0.385 billion kg.
• 2000—1.8 billion kg.
Releases
• 1987—0.1 g WHO98 TEQDF/yr (0.1 g I-TEQDF/yr) (Preliminary).
• 1995—0.1 g WHO98 TEQDF/yr (0.1 g I-TEQDF/yr) (Preliminary).
• 2000—0.5 g WHO98 TEQDF/yr (0.5 g I-TEQDF/yr) (Preliminary).
Water Releases
}ossible but quantitative releases could not be made (Not quantifiable).
Solid Residue Releases
Ash generated at these facilities is landfilled and, therefore, not considered an environmental
release.
Products
None.
1 3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED CHEMICAL
2 PULP MILLS
3 Approximately 20.5% of the wastewater sludges generated at bleached chemical pulp
4 mills are dewatered and burned in bark boilers at the mills (NCASI, 1995). These sludges can
5 contain CDDs/CDFs and elevated levels of chloride (NCASI, 1995). However, the sludges
6 generally make up less than 10% of the total feed to the boilers. Most of the feed is composed of
7 wood residues. On this basis, it is believed that the dioxin emission estimates derived in
8 Section 4.2.2 for industrial wood-burning facilities include emissions from boilers burning
9 wastewater sludges generated at bleached chemical pulp mills.
10
11
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-28 DRAFT: DO NOT CITE OR QUOTE
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1 3.8. BIOGAS COMBUSTION
2 No changes were made to the release estimates. The emission factor was derived from
3 testing at one facility in Germany and was considered preliminary. The activity was derived
4 from data on the amount of sewage sludge generated and assumptions about how much gas is
5 generated from the sludge. No other water, solid residue, or product releases occur from this
6 source. The inventory decision criteria and releases are summarized below:
Inventory Decision Criteria for Biogas Combustion
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Air
No
Yes
Yes
Yes
P
Water
Solids
Products
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-29 DRAFT: DO NOT CITE OR QUOTE
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Biogas Combustion
Air Releases
Emission Factors
• 1987—0.46 ng I-TEQoF/Nm3 of digester gas combusted (Preliminary).
• 1995—0.46 ng I-TEQoF/Nm3 of digester gas combusted (Preliminary).
• 2000—0.46 ng I-TEQpF/Nm3 of digester gas combusted (Preliminary).
Activity Levels
• 1987—467-million Nm3 (Preliminary).
• 1995—467-million Nm3 (Preliminary).
• 2000—467-million Nm3 (Preliminary).
Releases
• 1987—0.2 g I-TEQDF/yr (Preliminary).
• 1995—0.2 g I-TEQDF/yr (Preliminary).
• 2000—0.2 g I-TEQDF/yr (Preliminary).
Water Releases
None.
Solid Residue Releases
None.
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
1/7/2013 3-30 DRAFT: DO NOT CITE OR QUOTE
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Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987
to
OJ
Design" class
APCDb
MBWW
H-ESP
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Facility
name
Pinellas Co.
St. Petersburg
Tampa
Chicago
North Andover
Saugus
Baltimore (RESCO)
Wilmington
Glen Cove
Westchester Co.
Tulsa
Harrisburg
Philadelphia E.
Philadelphia NW
Nashville Thermal
Hampton WTE
Harrisonburg
Norfolk
City
located
Pinellas Co.
St. Petersburg
Tampa
Chicago
North Andover
Saugus
Baltimore
Wilmington
Glen Cove
Peekskill
Tulsa
Harrisburg
Philadelphia
Philadelphia
Nashville
Hampton
Harrisonburg
Norfolk NAS
State
FL
FL
FL
IL
MA
MA
MD
NC
NY
NY
OK
PA
PA
PA
TN
VA
VA
VA
H-ESP subtotals
Activity level0
(kg/y)
5.63E+08
3.24E+08
2.82E+08
4.51E+08
4.22E+08
4.22E+08
6.34E+08
5.63E+07
7.04E+07
6.34E+08
2.11E+08
2.03E+08
2.11E+08
2.11E+08
3.16E+08
5.63E+07
2.82E+07
1.01E+08
5.20E-H)9
I-TEQ EFd
(ng/kg)
478
478
478
478
WHO TEQ
EFe (ng/kg)
535
535
535
535
Actual tested stack emissions
478
478
478
478
535
535
535
535
Actual tested stack emissions
478
535
Actual tested stack emissions
Actual tested stack emissions
478
478
535
535
Actual tested stack emissions
478
535
Actual tested stack emissions
Annual air emissions
(g/y)
I-TEQoF
269
155
135
216
200
202
303
27
34
44
101
147
100
101
151
27
13
222
2,450
WH098
TEQoF
301
173
151
241
224
226
339
30
38
47
113
167
112
113
169
30
15
251
2,740
§•
rs
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§!
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31
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-------
to
OJ
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
Design" class
APCDb
MBWW
DS/FF
19
Facility
name
Marion Co.
City
located
Brooks
State
OR
DS/FF subtotals
Totals For Mass Burn Waterwall
MB/REF
H-ESP
20
21
22
23
24
25
26
27
28
29
30
31
Stamford I
Stamford II
Washington
Baltimore (Pulaski)
Clinton
Brooklyn (Henry
St.)
Brooklyn (SW)
Belts Avenue
Euclid
Ogden
Portsmouth
Waukesha
Stamford
Stamford
Washington
Baltimore
Clinton Township
Brooklyn
Brooklyn
Queens
Euclid
Layton
Portsmouth
Waukesha
CT
CT
DC
MD
MI
NY
NY
NY
OH
UT
VA
WI
H-ESP subtotals
MB/REF
WS
32
33
34
New Canaan
Louisville
Shreveport
New Canaan
Louisville
Shreveport
CT
KY
LA
Activity level0
(kg/y)
1.55E+08
1.55E+08
5.35E+09
5.63E+07
1.01E+08
2.82E+08
3.38E+08
1.69E+08
2.82E+08
2.11E+08
2.82E+08
5.63E+07
1.27E+08
4.51E+07
4.93E-K)7
2.00E+09
3.04E+07
2.82E+08
5.63E+07
I-TEQ EFd
(ng/kg)
0.67
WHO TEQ
EFe (ng/kg)
0.72
473
473
473
554
554
554
Actual tested stack emissions
473
473
473
473
473
473
473
473
554
554
554
554
554
554
554
554
236
236
236
254
254
254
Annual air emissions
(sly)
I-TEQoF
0.1
0.1
2,450
27
48
133
160
80
133
100
133
27
60
21
23
945
7
66
13
WH098
TEQoF
0.1
0.1
2,740
31
56
156
179
94
156
117
156
31
70
25
27
1,100
8
72
14
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31
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-------
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
to
OJ
Design" class
APCDb
MB/REF
WS (continued)
35
36
37
38
Facility
name
Fall River
S.E. Oakland Co.
Huntington
Sheboygan
City
located
Fall River
Auburn Hills
Huntington
Sheboygan
State
MA
MI
NY
WI
WS subtotals
MB/REF
DS/FF
39
Framingham
Framingham
MA
DS/FF subtotals
Totals For Mass Burn Refractory
MOD/SA
H-ESP
40
41
42
43
44
45
46
47
48
49
50
Sitka
Tuscaloosa
Purham
Red Wing
Savage
Pascagoula
Oswego Co.
Oneida Co.
Hampton
Cleburne
Barron Co.
Sitka
Tuscaloosa
Purham
Red Wing
Savage
Moss Point
Fulton
Rome
Hampton
Clebume
Almena
AK
AL
MN
MN
MN
MS
NY
NY
SC
TX
WI
H-ESP subtotals
Activity level0
(kg/y)
1.69E+08
1.69E+08
1.27E+08
6.76E+07
9.01E-H)8
1.41E+08
1.41E-HJ8
3.04E-H)9
7.04E+06
8.45E+07
2.25E+07
2.03E+07
1.69E+07
4.22E+07
5.63E-K)7
5.63E+07
7.60E+07
3.24E+07
2.25E+07
4.37E+08
I-TEQ EFd
(ng/kg)
236
236
236
236
WHO TEQ
EFe (ng/kg)
254
254
254
254
0.67
0.72
79
79
79
85.7
85.7
85.7
Actual tested stack emissions
79
79
79
85.7
85.7
85.7
Actual tested stack emissions
79
79
79
85.7
85.7
85.7
Annual air emissions
(sly)
I-TEQoF
40
40
30
16
212
0.1
0.1
1,160
0.6
6.7
1.8
0.1
1.3
o o
J.J
4.5
4.5
6.0
2.6
1.8
33
WH098
TEQoF
43
43
32
17
229
0.1
0.1
1,330
0.6
7.2
1.9
0.1
1.5
3.6
4.8
4.8
6.5
2.8
1.9
36
§•
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31
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-------
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
to
OJ
Design" class
APCDb
MOD/SA
UNC
MOD/SA
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
Facility
name
Batesville
Blytheville
Hope
Hot Springs
North Little Rock
Osceola
Stuttgart
Cassia Co.
Simpson Co.
Harpswell
Fort Leonard Wood
Livingston
Wrightsville
Auburn
Candia
Canterbury
Durham
Groveton
Litchfield
Meredith
Nottingham
City
located
Batesville
Blytheville
Hope
Hot Springs
North Little Rock
Osceola
Stuttgart
Burley
Simpson Co.
Harpswell
Fort Leonard Wood
Park Co.
Wrightsville
Auburn
Candia
Canterbury
Durham
Groveton
Litchfield
Meredith
Nottingham
State
AR
AR
AR
AR
AR
AR
AR
ID
KY
ME
MO
MT
NC
NH
NH
NH
NH
NH
NH
NH
NH
Activity level0
(kg/y)
1.41E+07
1.97E+07
1.07E+07
2.82E+07
2.82E+07
1.41E+07
1.69E+07
1.41E+07
2.17E+07
3.94E+06
2.11E+07
2.11E+07
1.41E+07
1.41E+06
4.22E+06
2.82E+06
3.04E+07
6.76E+06
6.20E-K)6
8.73E-K)6
2.25E+06
I-TEQ EFd
(ng/kg)
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
WHO TEQ
EFe (ng/kg)
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
17
Annual air emissions
(sly)
I-TEQoF
0.2
0.3
0.2
0.5
0.5
0.2
0.3
0.2
0.3
0.1
0.3
0.3
0.2
0.1
0.1
0.1
0.5
0.1
0.1
0.1
<0.1
WH098
TEQoF
0.2
0.3
0.2
0.5
0.5
0.2
0.3
0.2
0.4
0.1
0.4
0.4
0.2
0.1
0.1
0.1
0.5
0.1
0.1
0.2
O.I
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i
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31
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-------
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
to
OJ
Design" class
APCDb
UNC (continued)
72
73
74
75
76
77
78
79
80
81
82
83
84
85
Facility
name
Pittsfield
Wilton
Wolfeboro
Cattaraugus Co.
Skaneateless
Miami
Johnsonville
Dyersburg
Carthage City
Center
Gatesville
Newport News
Salem
Bellingham
City
located
Pittsfield
Wilton
Wolfeboro
Cuba
Skaneateless
Miami
Johnsonville
Dyersburg
Carthage City
Center
Gatesville
Newport News
Salem
Bellingham
State
NH
NH
NH
NY
NY
OK
SC
TN
TX
TX
TX
VA
VA
WA
UNC subtotals
MOD/SA
WS
86
87
88
89
Collegeville
Lewisburg
Palestine
Waxahachie
Collegeville
Lewisburg
Palestine
Waxahachie
MN
TN
TX
TX
WS subtotals
MOD/SA
90
Windham
Windham
CT
Activity level0
(kg/y)
1.35E+07
8.45E+06
4.51E+06
3.15E+07
3.66E+06
3.04E+07
1.41E+07
2.82E+07
1.01E+07
1.01E+07
5.63E+06
9.86E+06
2.82E+07
2.82E+07
5.17E+08
1.41E+07
1.69E+07
7.89E+06
1.41E+07
5.30E+07
3.04E+07
I-TEQ EFd
(ng/kg)
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
WHO TEQ
EFe (ng/kg)
17
17
17
17
17
17
17
17
17
17
17
17
17
17
16.2
16.2
16.2
16.2
17
17
17
17
16.2
17
Annual air emissions
(sly)
I-TEQoF
0.2
0.1
0.1
0.5
0.1
0.5
0.2
0.5
0.2
0.2
0.1
0.2
0.5
0.5
8.5
0.2
0.3
0.1
0.2
0.8
0.5
WH098
TEQoF
0.2
0.1
0.1
0.5
0.1
0.5
0.2
0.5
0.2
0.2
0.1
0.2
0.5
0.5
8.9
0.2
0.3
0.1
0.2
0.8
0.5
§•
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I
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§
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§!
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31
^
HH ^3
H S.
MŁ
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&
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c
O
H
W
-------
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
to
OJ
Design" class
APCDb
FF
91
92
Facility
name
Auburn
Portsmouth
City
located
Auburn
Portsmouth
State
ME
NH
FF subtotals
Totals For Modular-Starved Air
MOD/EA
UNC
93
94
Mayport
Bellingham
Mayport NAS
Bellingham
FL
WA
UNC subtotals
MOD/EA
WS
95
East Chicago
East Chicago
IN
WS subtotals
MOD/EA
EGB
96
Pittsfield
Pittsfield
MA
EGB subtotals
Totals For Modular Excess Air
RDF/Co
H-ESP
97
98
Lakeland
Ames
Lakeland
Ames
FL
IA
H-ESP subtotals
Totals For Refuse Derived Fuel Cofired With Coal
RDF/Ded
H-ESP
99
100
101
102
103
104
Dade Co.
Honolulu
Haverhill
Albany
Niagara Falls
Akron
Miami
Honolulu
Lawrence
Albany
Niagara
Akron
FL
HI
MA
NY
NY
OH
Activity level0
(kg/y)
5.63E+07
5.63E+07
1.43E-HJ8
1.15E-KJ9
1.35E+07
2.82E+07
4.17E407
1.27E+08
1.27E+08
6.76E+07
6.76E+07
2.36E+08
8.45E+07
5.63E+07
1.41E-HJ8
1.41E-HJ8
8.45E+08
1.69E+08
3.66E+08
1.69E+08
6.20E+08
2.82E+08
I-TEQ EFd
(ng/kg)
16.2
16.2
WHO TEQ
EFe (ng/kg)
17
17
16.2
16.2
17
17
16.2
17
0.67
0.72
231
231
231
231
1,490
1,490
1,680
1,680
Actual tested stack emissions
1,490
1,490
1,490
1,680
1,680
1,680
Annual air emissions
(sly)
1-TEQop
0.9
0.9
2.3
44
0.2
0.5
0.7
2.1
2.1
0.1
0.1
2.8
20
13
33
33
1,260
252
546
252
924
420
WH098
TEQoF
1.0
1.0
2.5
48
0.2
0.5
0.7
2.2
2.2
0.1
0.1
2.9
20
13
33
33
1,420
284
615
284
1,040
473
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H S.
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&
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-------
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
to
OJ
Design" class
APCDb
105
Facility
name
Columbus
City
located
Columbus
State
OH
H-ESP subtotals
RDF/Ded
WS
106
107
Duluth
St. Louis
Duluth
St. Louis
MN
MO
WS subtotals
Totals for refuse-derived fuel — dedicated
MB/RK
H-ESP
108
109
110
N. Dayton
S. Dayton
Gallatin
Dayton
Dayton
Gallatin
OH
OH
TN
H-ESP subtotals
MB/RK
FF
111
Galax
Galax
VA
FF subtotals
Totals for mass burn rotary kiln
TOTALS FOR ALL MWCs operating in 1987
Activity level0
(kg/y)
5.63E+08
3.01E-H)9
1.13E+08
2.25E+08
3.38E-KJ8
3.49E+09
1.69E+08
1.69E+08
5.63E+07
3.94E+08
1.58E+07
1.58E+07
4.10E+08
1.37E+10
I-TEQ EFd
(ng/kg)
WHO TEQ
EFe (ng/kg)
Actual tested stack emissions
236
236
254
254
478
478
478
535
535
535
47
93.1
Annual air emissions
(g/y)
1-TEQop
840
4,490
27
53
80
4570
81
81
27
189
0.7
0.7
190
8450
WH098
TEQoF
946
5,060
29
53
82
5140
90
90
30
210
1.5
1.5
212
9510
§•
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31
H S.
MŁ
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-------
to
Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued)
aMWC Design class: FB/RDF = Fluidized-bed refuse-derived fuel; MB/WW = Mass burn waterwall; MB/RK = Mass burn rotary kiln; MB/REF = Mass burn
refractory walled; MOD/EA = Modular excess air; RDF/Ded = Dedicated refuse-derived fuel; RDF/co = Refuse-derived fuel cofired with coal (slash indicates
devices used in conjunction).
5: bAPCD = air pollution control device. This includes DS/FF (dry scrubber with fabric filters); H-ESP (hot-sided electrostatic precipitator); EGB (electrified
a, gravel bed); WS (wet scrubber); FF (fabric filter); UNC = uncontrolled or no APCD.
g ° Activity Level is the annual amount (kg) of municipal solid waste or refuse derived fuel expected to be combusted by the MWC. It is estimated by multiplying
I the annual design capacity of the furnace by 85%. The figure of 85% represents the assumption that the MWC will experience downtime during the year for
51 maintenance and repairs.
Ł' dThe I-TEQDF Emission Factor (EF) expressed in units of ng TEQ/kg combusted.
s^ eThe WHO98 TEQDF Emission Factor (EF) expressed in units of ng TEQ/kg combusted.
s
00 §
i
a,
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31
H S.
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&
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-------
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995
to
OJ
Design" class
APCDb
MB/WW
DS/FF
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Facility
name
Huntsville RRF
Long Beach RRF
Commerce RRF
Modesto RRF
Bridgeport RESCO
Convanta SECONN
Bristol RRF
Mid-Conn RRF
Pasco Co.
Broward Co. S
B reward Co. N
Lake Co. RRF
Savannah RRF
Indianapolis RRF
Saugus RESCO
Kent Co. RRF
Jackson Co.
New Hanover
Gloucester Co.
Warren Energy RRF
City
located
Huntsville
Long Beach
Commerce
Crows Landing
Bridgeport
Preston
Bristol
Hartford
Hudson
Fort Lauderdale
Fort Lauderdale
Okahumpka
Savannah
Indianapolis
Saugus
Grand Rapids
Jackson
Wilmington
Westville
Oxford
Township
State
AL
CA
CA
CA
CT
CT
CT
CT
FL
FL
FL
FL
GA
IN
MA
MI
MI
NC
NJ
NJ
Activity
level0
(kg/y)
1.94E+08
3.89E+08
1.07E+08
2.25E+08
6.34E+08
1.69E+08
1.83E+08
5.63E+08
2.96E+08
6.34E+08
6.34E+08
1.49E+08
1.41E+08
6.65E+08
4.22E+08
1.76E+08
5.63E+07
7.01E+07
1.62E+08
1.13E+08
I-TEQ EFd
(ng/kg)
0.67
0.67
WHO TEQ EFe
(ng/kg)
0.72
0.72
Actual tested stack emissions
Actual tested stack emissions
0.67
0.67
0.67
0.67
0.67
0.67
0.67
0.67
0.67
0.72
0.72
0.72
0.72
0.72
0.72
0.72
0.72
0.72
Actual tested stack emissions
Actual tested stack emissions
0.67
0.67
0.67
0.67
0.67
0.72
0.72
0.72
0.72
0.72
Annual air emissions
(sly)
I-TEQoF
0.1
0.3
0.1
0.1
0.4
0.1
0.1
0.4
0.2
0.4
0.4
0.1
0.1
0.7
0.3
0.1
0.1
0.1
0.1
0.1
WH098
TEQoF
0.1
0.3
0.1
0.2
0.5
0.1
0.1
0.4
0.2
0.5
0.5
0.1
0.1
0.7
0.3
0.1
0.1
0.1
0.1
0.1
§•
rs
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31
^
HH ^3
H S.
MŁ
O '
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c
O
H
W
-------
to
OJ
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
Design" class
APCDb
MB/WW
DS/FF
(continued)
21
22
23
24
25
26
27
28
29
Facility
name
Onondaga Co.
Babylon RRF
Hempstead
Marion Co.
Montgomery Co.
Lancaster Co.
1-95 Energy RRF
Spokane Regional
Skagit Co. RRF
City
located
Onondaga
Babylon
Westbury
Brooks
Conshohocken
Bainbridge
Lorton
Spokane
Mount Vernon
State
NY
NY
NY
OR
PA
PA
VA
WA
WA
DS/FF subtotals
MB/WW
C-ESP
30
31
32
33
34
35
36
37
Pinellas Co.
Hillsborough Co.
McKay Bay
Southernmost RRF
Olmstead RRF
Westchester RESCO
Walter B. Hall RRF
Nashville Thermal
St. Petersburg
Tampa
Tampa
Key West
Rochester
Peekskill
Tulsa
Nashville
FL
FL
FL
FL
MN
NY
OK
TN
C-ESP subtotals
Activity
level0
(kg/y)
2.79E+08
2.11E+08
7.06E+08
1.55E+08
3.38E+08
3.38E+08
8.45E+08
2.25E+08
5.01E+07
9.13E+09
8.45E+08
3.38E+08
2.82E+08
4.22E+07
5.63E+07
6.34E+08
3.17E+08
2.96E+08
2.81E+09
I-TEQ EFd
(ng/kg)
0.67
WHO TEQ EFe
(ng/kg)
0.72
Actual tested stack emissions
Actual tested stack emissions
Actual tested stack emissions
0.67
0.67
0.72
0.72
Actual tested stack emissions
0.67
0.67
0.72
0.72
Actual tested stack emissions
6.1
6.1
6.1
6.1
6.1
6.1
6.1
6.54
6.54
6.54
6.54
6.54
6.54
6.54
Annual air emissions
(sly)
I-TEQoF
0.2
0.3
0.1
0.1
0.2
0.2
0.9
0.2
O.I
6.3
5.2
2.1
1.7
0.3
0.3
3.9
1.9
1.8
17
WHO98
TEQoF
0.2
0.3
0.1
0.1
0.2
0.2
1.0
0.2
O.I
6.8
5.5
2.2
1.8
0.3
0.4
4.1
2.1
1.9
18
§•
rs
I
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§!
*&
31
^
HH ^3
H S.
w^-
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&
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c
O
H
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-------
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
MB/WW
DS/C-ESP
38
39
40
41
42
43
44
45
Facility
name
Millbury
Greater Portland
Covanta Haverhill
New Hanover
Essex Co. RRF
CamdenRRF
Adirondack RRF
Charleston RRF
City
located
Millbury
Portland
Haverhill
Wilmington
Newark
Camden
Hudson Falls
Charleston
State
MA
ME
MA
NC
NJ
NJ
NY
SC
DS/C-ESP subtotals
MB/WW
DSI/FF
46
47
SES Claremont RRF
Concord
Claremont
Concord
NH
NH
DSI/FF subtotals
MB/WW
DS/CI/FF
48
49
50
Hennepin Energy
Union Co. RRF
Wheelabrator Falls
Minneapolis
Rahway
Falls Creek
MN
NJ
PA
DS/CI/FF subtotals
MB/WW
H-ESP
51
52
53
54
University City RRF
Long Beach RRF
Harrisburg WTE
NASA RRF
Charlotte
Long Beach
Harrisburg
Hampton
NC
NY
PA
VA
Activity
level0
(kg/y)
4.22E+08
1.41E+08
4.65E+08
5.63E+07
6.41E+08
2.96E+08
1.22E+08
1.69E+08
2.73E+09
5.63E+07
1.41E+08
1.97E+08
3.38E+08
4.06E+08
4.22E+08
1.17E+09
6.62E+07
5.63E+07
2.03E+08
5.63E+07
I-TEQ EFd
(ng/kg)
6.1
WHO TEQ EFe
(ng/kg)
6.54
Actual tested stack emissions
6.1
6.1
6.1
6.54
6.54
6.54
Actual tested stack emissions
6.1
6.54
Actual tested stack emissions
Actual tested stack emissions
1.9
2.07
1.5
1.5
1.61
1.61
Actual tested stack emissions
478
478
535
535
Actual tested stack emissions
Actual tested stack emissions
Annual air emissions
(sly)
I-TEQoF
2.6
1.4
2.8
0.3
3.9
0.7
0.7
1.0
13
0.2
0.3
0.5
0.5
0.6
0.6
1.7
32
27
147
27
WHO98
TEQoF
2.8
1.5
3.0
0.4
4.2
0.8
0.8
1.1
15
0.2
0.3
0.5
0.5
0.7
0.7
1.9
35
30
167
30
§•
rs
I
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s
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>!
§!
*&
31
^
HH ^3
H S.
w^-
O '
&
O
c
O
H
W
-------
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
MB/WW
H-ESP
(continued)
55
56
Facility
name
Harrisonburg RRF
Baltimore (RESCO)
City
located
Harrisonburg
Baltimore
State
VA
MD
H-ESP subtotals
MB/WW
DSI/H-ESP
57
North Andover
North Andover
MA
DSI/H-ESP subtotals
MB/WW
DSI/CI/H-ESP
58
Alexandria RRF
Alexandria
VA
DSI/CI/H-ESP subtotals
Totals for mass burn waterwall
MB/REF
WS
59
60
New Canaan MWC
Fall River
New Canaan
Fall River
CT
MA
Subtotals for MB/REF WS
MB/REF
DS/C-ESP
61
Pulaski
Baltimore
MD
DS/C-ESP subtotals
MB/REF
C-ESP
62
Clinton
Clinton
MI
C-ESP subtotals
MB/REF
DS/FF
63
64
Mid Maine Waste
Huntington
Auburn
Huntington
ME
NY
DS/FF subtotals
Activity
level0
(kg/y)
2.82E+07
6.34E+08
1.04E-H)9
4.22E+08
4.22E+08
2.75E+08
2.75E-KJ8
1.74E+10
3.52E+07
1.69E+08
2.04E+08
4.22E+08
4.22E+08
1.69E+08
1.69E+08
5.63E+07
2.11E+08
2.67E+08
I-TEQ EFd
(ng/kg)
WHO TEQ EFe
(ng/kg)
Actual tested stack emissions
Actual tested stack emissions
Actual tested stack emissions
Actual tested stack emissions
236
236
254
254
Actual tested stack emissions
Actual tested stack emissions
0.67
0.67
0.72
0.72
Annual air emissions
(sly)
I-TEQoF
5.8
9.9
249
3.3
3.3
2.1
2.1
293
8.3
40
48
22
22
40
40
<0.1
0.1
0.1
WHO98
TEQoF
5.9
11
279
3.5
3.5
2.3
2.3
327
9.0
43
52
22
22
43
43
0.1
0.2
0.2
§•
rs
I
'TS
s
i
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§•
31
H S.
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&
O
c
O
H
W
-------
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
MB/REF
DSI/FF
65
Facility
name
Davis Co.
City
located
Layton
State
UT
DSI/FF subtotals
Totals for mass burn refractory
MB/RK
C-ESP
66
67
Montenay Bay
Sumner Co.
Panama City
Gallatin
FL
TN
MB/RK C-ESP subtotals
MB/RK
DSI/C-ESP
68
Dayton RRF
Dayton
OH
DSI/C-ESP subtotals
MB/RK
DSI/FF
69
70
Dutchess Co.
MacArthur WTE
Poughkeepsie
Ronkonkoma
NY
NY
DSI/FF subtotals
MB/RK
DS/FF
71
72
Delaware Co.
York Co.
Chester
York
PA
PA
DS/FF subtotals
Totals for mass burn rotary kiln
RDF/ded
C-ESP
73
74
75
76
Dade Co. RRF
Niagara Falls RDF
Central Wayne Co.
Ramsey-WA
Miami
Niagara Falls
Dearborn
Red Wing
FL
NY
MI
MN
Activity
level0
(kg/y)
1.13E+08
1.13E-KJ8
1.18E-KJ9
1.44E+08
5.63E+07
2.00E+08
5.07E+08
5.07E+08
1.13E+08
1.46E+08
2.59E+08
7.57E+08
3.79E+08
1.14E+09
2.10E+09
8.45E+08
6.20E+08
1.41E+08
2.03E+08
I-TEQ EFd
(ng/kg)
1.91
WHO TEQ EFe
(ng/kg)
2.07
47
47
47
93.1
93.1
93.1
Actual tested stack emissions
47
0.62
93.1
0.68
Actual tested stack emissions
231
253
Actual tested stack emissions
Actual tested stack emissions
231
253
Annual air emissions
(sly)
1-TEQop
0.2
0.2
110
6.8
2.7
9.5
24
24
5.3
6.7
12
0.5
0.2
0.7
46
199
143
33
47
WHO98
TEQoF
0.2
0.2
117
13
5.2
18
47
47
10
14
24
0.5
0.3
0.8
90
214
157
36
51
§•
rs
I
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s
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>!
§!
*&
31
^^
HH ^3
H S.
w^-
O '
&
O
c
O
H
W
-------
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
Facility
name
City
located
State
RDF/ded C-ESP subtotals
RDF/ded
DS/C-ESP
77
78
79
80
West Palm Beach
SEMASS RRF
Western L Superior
Honolulu RRF
Palm Beach
Rochester
Duluth
Honolulu
FL
MA
MN
HI
DS/C-ESP subtotals
RDF/ded
DS/FF
81
82
83
84
85
86
87
SEMASS RRF
Maine Energy RRF
Penobscot Energy
Greater Detroit RRF
Wilmarth Plant
Norfolk Navy Yard
Mid-Connecticut
Rochester
Biddeford
Orrington
Detroit
Mankato
Norfolk
Hartford
MA
ME
ME
MI
MN
VA
CT
DS/FF subtotals
RDF/ded
DSI/FF
88
Elk River RRF
Elk River
MN
DSI/FF subtotals
RDF/ded
DSI/H-ESP
89
Haverhill Lawrence
Lawrence
MA
DSI/H-ESP subtotals
RDF/ded
H-ESP
90
Kodak MWC
Rochester
NY
H-ESP subtotals
Activity
level0
(kg/y)
1.81E-KJ9
5.63E+08
5.07E+08
7.32E+07
6.08E+08
1.75E-KJ9
7.60E+08
1.69E+08
1.97E+08
6.20E+08
2.03E+08
5.63E+08
5.63E+08
3.07E+09
4.22E+08
4.22E+08
2.00E+08
2.00E+08
4.22E+07
4.22E+07
I-TEQ EFd
(ng/kg)
0.53
0.53
0.53
0.53
WHO TEQ EFe
(ng/kg)
0.56
0.56
0.56
0.56
0.24
0.26
Actual tested stack emissions
Actual tested stack emissions
Actual tested stack emissions
47
0.24
93.1
0.26
Actual tested stack emissions
47
93.1
285
316
1,490
1,680
Annual air emissions
(sly)
I-TEQoF
422
0.3
0.3
0.1
0.3
0.9
0.2
0.1
<0.1
0.1
0.1
0.1
0.1
0.7
20
20
57
57
63
63
WHO98
TEQoF
458
0.3
0.3
0.1
0.3
0.9
0.2
0.1
O.I
0.2
0.1
0.1
0.1
0.8
39
39
63
63
71
71
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Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
Facility
name
City
located
State
Totals for dedicated refuse derived fuel
MOD/SA
UNC
91
92
93
94
95
96
97
98
99
Batesville MWC
Stuttgart MWC
OsceolaMWC
Miami Airport
NIEHS MWC
Livingston/Park Co.
Miami MWC
Coos Bay MWC
Pentagon MWC
Batesville
Stuttgart
Osceola
Miami
Durham
Park Co.
Miami
Coquille
Arlington
AR
AR
AR
FL
NC
MT
OH
OR
VA
UNC subtotals
MOD/SA
H-ESP
100
101
102
103
Juneau MWC
Harford Co.
City of Clebume
Barren Co.
Juneau
Aberdeen
Clebume
Almena
AK
MD
TX
WI
H-ESP subtotals
MOD/SA
C-ESP
104
105
106
107
PerhamMWC
Polk Co. MWC
Oswego Co.
Westmoreland
Perham
Fosston
Fulton
Greensburg
MN
MN
NY
PA
C-ESP subtotals
Activity
level0
(kg/y)
7.30E-H)9
2.82E+07
1.77E+07
1.41E+07
1.69E+07
1.13E+07
2.03E+07
2.96E+07
3.52E+07
1.41E+07
1.87E+08
1.97E+07
1.01E+08
3.24E+07
2.82E+07
1.81E-KJ8
3.21E+07
2.25E+07
5.63E+07
1.41E+07
1.25E-KJ8
I-TEQ EFd
(ng/kg)
WHO TEQ EFe
(ng/kg)
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
16.2
17
17
17
17
17
17
17
17
17
79
79
79
79
85.7
85.7
85.7
85.7
16.2
16.2
16.2
16.2
17
17
17
17
Annual air emissions
(sly)
I-TEQoF
564
0.5
0.3
0.2
0.3
0.2
0.3
0.5
0.6
0.2
3.1
1.6
8.0
2.6
2.2
14
0.5
0.4
0.9
0.2
2.0
WHO98
TEQoF
633
0.5
0.3
0.2
0.3
0.2
0.3
0.5
0.6
0.2
3.1
1.7
8.7
2.8
2.4
16
0.6
0.4
1.0
0.2
2.2
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31
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-------
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
MOD/SA
DS/DSI/C-ESP
108
Facility
name
Chamber Medical
City
located
Hampton
State
SC
DS/DSI/C-ESP subtotals
MOD/SA
DSI/FF
109
St. Croix WTE
New Richmond
WI
DSI/FF subtotals
MOD/SA
WS
110
111
112
Fergus Falls
Center MWC
Panola Co.
Fergus Falls
Center
Carthage
MN
TX
TX
WS subtotals
MOD/SA
WS/FF
113
Recomp Bellingham
Bellingham
WA
WS/FF subtotals
Totals for modular-starved air
MOD/EA
UNC
114
Mayport NAS
Mayport
FL
UNC subtotals
MOD/EA
H-ESP
115
Richards Asphalt Co.
Savage
MN
H-ESP subtotals
MOD/EA
DSI/H-ESP
116
Sitka MWC
Sitka
AK
DSI/H-ESP subtotals
MOD/EA
C-ESP
117
118
Pope-Douglas SW
Red Wing
Alexandria
Red Wing
MN
MN
Activity
level0
(kg/y)
7.60E+07
7.60E-KJ7
2.87E+07
2.87E-HJ7
2.65E+07
1.13E+07
1.13E+07
4.90E+07
2.82E+07
2.82E+07
6.46E+08
1.41E+07
1.41E+07
1.97E+07
1.97E+07
1.41E+07
1.41E+07
2.03E+07
2.03E+07
I-TEQ EFd
(ng/kg)
16.2
WHO TEQ EFe
(ng/kg)
17
0.02
0.03
16.2
16.2
16.2
17
17
17
16.2
17
16.2
17
Actual tested stack emissions
118
119
Actual tested stack emissions
Actual tested stack emissions
Annual air emissions
(sly)
I-TEQoF
1.2
1.2
0.1
<0.1
0.4
0.2
0.2
0.8
0.5
0.5
22
0.2
0.2
2.3
2.3
1.7
1.7
0.3
0.1
WHO98
TEQoF
1.3
1.3
0.1
<0.1
0.5
0.2
0.2
0.9
0.5
0.5
24
0.2
0.2
2.4
2.4
1.7
1.7
0.3
0.1
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Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued)
to
OJ
Design" class
APCDb
119
Facility
name
Pascagoula RRF
City
located
Moss Point
State
MS
C-ESP subtotals
MOD/EA
DS/FF
120
WallingfordRRF
Wallingford
CT
DS/FF subtotals
MOD/EA
DSI/FF
121
Springfield RRF
Agawam
MA
DSI/FF subtotals
MOD/EA
WS/C-ESP
122
Pittsfield RRF
Pittsfield
MA
WS/C-ESP subtotals
Totals for modular excess air
FB/RDF
DS/FF
123
Fayetteville RRF
Fayetteville
NC
DS/FF subtotals
FB/RDF
DSI/FF
124
lacoma RRF
Tacoma
WA
DSI/FF subtotals
FB/RDF
DSI/EGB
125
LaCrosse Co.
La Crosse
WI
DSI/EGB subtotals
Totals for fluidized bed/refuse-derived fuel
Totals for all MWCs operating in 1995
Activity
level0
(kg/y)
4.22E+07
8.28E-K)?
1.18E+08
1.18E-KJ8
1.01E+08
1.01E-H)8
6.76E+07
6.76E+07
4.17E+08
1.69E+08
1.69E+08
8.45E+07
8.45E-K)7
1.13E+08
1.13E-HJ8
3.66E+08
2.98E+10
I-TEQ EFd
(ng/kg)
16.2
WHO TEQ EFe
(ng/kg)
17
16.2
17
16.2
17
Actual tested stack emissions
0.67
0.72
0.67
0.72
Actual tested stack emissions
Annual air emissions
(sly)
1-TEQop
0.7
1.1
1.9
1.9
1.6
1.6
1.1
1.1
10
0.1
0.1
0.1
0.1
0.1
0.1
0.3
1050
WHO98
TEQoF
0.7
1.1
2.0
2.0
1.7
1.7
1.2
1.2
10
0.1
0.1
0.1
0.1
0.1
0.1
0.3
1200
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aMWC Design class: FB/RDF = Fluidized-bed refuse-derived fuel; MB/WW = Mass burn waterwall; MB/RK = Mass burn rotary kiln; MB/REF = Mass burn
refractory walled; MOD/EA = Modular excess air; RDF/Ded = Dedicated refuse-derived fuel; RDF/co = Refuse-derived fuel cofired with coal (slash indicates
devices used in conjunction).
-------
; bAPCD = air pollution control device. This includes DS/FF (dry scrubber with fabric filters); H-ESP (hot-sided electrostatic precipitator); EGB (electrified
| gravel bed); WS (wet scrubber); FF (fabric filter); UNC = uncontrolled or no APCD.
0 Activity Level is the annual amount (kg) of municipal solid waste or refuse derived fuel expected to be combusted by the MWC. It is estimated by multiplying
the annual design capacity of the furnace by 85%. The figure of 85% represents the assumption that the MWC will experience downtime during the year for
maintenance and repairs.
5^ dThe I-TEQDF Emission Factor (EF) expressed in units of ng TEQ/kg combusted.
I? eThe WHO98 TEQDF Emission Factor (EF) expressed in units of ng TEQ/kg combusted.
o
1
I
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I
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-
00 §
i
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§
31
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Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000
to
OJ
Design" Class
APCDb
MB/WW
DS/FF/CI/SNCR
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Facility Name
Huntsville
Stanislaus
Bristol RRF
Wheelabrator Lisbon Inc.
Hillsborough Co. RRF
McKay Bay REF
Lake Co. RRF
Lee Co. RRF
Pasco Co. RRF
Pinellas Co. RRF
Savannah RRF
Indianapolis RRF
Haverhill RRF
Wheelabrator North Andover
Wheelabrator Saugus
Montgomery Co. RRF
Kent Co. WTE Facility
Central Wayne Energy
Covanta Hennepin
New Hanover Co. WTE
Wheelabrator Concord
City Located
Madison
Stanislaus
Hartford
New London
Hillsborough
Hillsborough
Lake
Lee
Pasco
Pinellas
Chatham
Marion
Essex
Essex
Essex
Montgomery
Kent
Wayne
Hennepin
New Hanover
Merrimack
State
AL
CA
CT
CT
FL
FL
FL
FL
FL
FL
GA
IN
MA
MA
MA
MD
MI
MI
MN
NC
NH
Activity
Level0
(kg/y)
1.77E+08
2.61E+08
1.86E+08
1.79E+08
3.58E+08
1.80E+08
1.66E-K)8
3.95E-K)8
3.10E+08
8.91E-K)8
1.21E-K)8
6.54E-K)8
5.68E-K)8
3.83E+08
4.32E+08
5.20E+08
1.80E+08
6.18E+07
3.65E+08
1.27E+08
1.84E+08
Emission Factor (ng
TEQ/kg)
I-TEQoF
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
WH098
TEQoF
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Annual Air Emissions
(sly)
I-TEQoF
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
O.I
0.1
O.I
0.1
0.1
0.1
0.1
0.3
0.02
0.1
0.1
O.I
O.I
WHO98
TEQoF
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
O.I
0.2
O.I
0.1
0.1
0.1
0.1
0.3
0.02
0.1
0.1
O.I
O.I
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31
^
HH ^3
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to
OJ
Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued)
Design" Class
APCDb
MB/WW
DS/FF/CI/SNCR
(continued)
MB/WW
DS/FF/SNCR
MBAVW
DS/FF/CI
MBAVW
DS/FF
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
Facility Name
Gloucester Co.
Union Co. RRF
Niagara Falls
Onondaga Co. RRF
Babylon RRF
Huntington RRF
Wheelabrator Westchester
Walter B. Hall RRF (Tulsa)
Marion Co. WTE
Lancaster Co.
Wheelabrator Falls RRF
Montenay Montgomery
Nashville Thermal Transfer Corp.
Alexandria/ Arlington RRF
1-95 Energy RRF
Spokane Regional Facility
City Located
Gloucester
Union
Niagara
Onondaga
Suffolk
Suffolk
Westchester
Tulsa
Marion
Bainbridge
Bucks
Montgomery
Davidson
Alexandria
Fairfax
Spokane
State
NJ
NJ
NY
NY
NY
NY
NY
OK
OR
PA
PA
PA
TN
VA
VA
WA
DS/FF/CI/SNCR subtotals
Long Beach SERRF
Wheelabrator South Broward
Wheelabrator North Broward
Hempstead
Los Angeles
Ft. Lauderdale
Broward
Nassau
CA
FL
FL
NY
DS/FF/SNCR subtotals
Wheelabrator Bridgeport, L.P.
Southeastern Connecticut RRF
Warren Energy RF
Fairfield
New London
Warren
CT
CT
NJ
DS/FF/CI subtotals
Jackson Co. RRF
New Hanover Co.
SES Claremont
Jackson
New Hanover
Sullivan
MI
NC
NH
DS/FF subtotals
Activity
Level0
(kg/y)
1.81E+08
5.09E+08
7.14E-K)8
3.35E-K)8
2.20E-K)8
3.16E-K)8
6.50E-K)8
3.39E-K)8
1.84E-K)8
3.81E-K)8
5.25E-K)8
4.03E-K)8
2.25E+08
3.32E+08
1.09E+09
2.85E+08
1.34E+10
5.74E+08
7.56E+08
7.76E+08
8.87E+08
2.99E+09
7.08E+08
7.08E+08
1.25E+08
1.25E+08
6.27E+07
6.27E+07
6.27E+07
1.88E+08
Emission Factor (ng
TEQ/kg)
I-TEQoF
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
0.67
0.67
0.67
WHO98
TEQoF
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
0.72
0.72
0.72
Annual Air Emissions
(s/y)
I-TEQoF
<0.1
<0.1
0.4
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
0.1
<0.1
0.5
<0.1
0.1
<0.1
<0.1
2.3
0.1
0.2
0.1
0.5
WHO98
TEQoF
O.I
O.I
0.4
O.I
O.I
O.I
0.1
O.I
O.I
0.1
O.I
0.6
O.I
0.1
O.I
O.I
2.5
0.1
0.2
0.1
0.5
0.9 0.9
0.1
0.1
<0.1
0.2
<0.1
<0.1
0.1
<0.1
0.1
0.1
O.I
0.2
0.1
0.1
0.1
0.3
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31
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to
Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued)
Design" Class
APCDb
MB/WW
DS/ESP/CI/SNCR
MB/WW
DS/ESP/CI
MB/WW
C-ESP
MB/WW
H-ESP
MB/WW
UNC
48
49
50
51
52
53
54
55
56
57
58
59
60
Facility Name
McKay Bay REF
Wheelabrator Millbury
Wheelabrator Baltimore
Greater Portland Region RRF
CamdenRRF
Essex Co. RRF
City Located
Hillsborough
Worcester
Independent
City
Cumberland
Camden
Essex
State
FL
MA
MD
ME
NJ
NJ
DS/ESP/CI/SNCR subtotals
Adirondack RRF
Foster Wheeler Charleston RRF
Washington
Charleston
NY
SC
DS/ESP/CI subtotals
Southernmost WTE
Olmstead WTE Facility
NASA
Monroe
Olmstead
Hampton City
FL
MN
VA
C-ESP subtotals
Harrisburg WTE | Dauphin
PA
H-ESP subtotals
Harrisonburg | Harrisonburg
VA
UNC subtotals
Totals for all MB/WW
MB/REF
DSI/H-ESP
MB/REF
DS/FF
61
62
Davis/Wasatch
Davis
UT
DSI/H-ESP subtotals
Mid Maine Waste Action Corp.
Androscoggin
ME
DS/FF subtotals
Totals for all MB/REF
MB/RK
DS/FF
MB/RK
DS/FF/CI/SNCR
MB/RK
DSI/FF
63
64
65
66
American Ref-Fuel of Delaware Valley | Delaware
DS/FF subtotals
York Co. | York
PA
PA
DS/FF/CI/SNCR subtotals
Dutchess Co. RRF
MacArthur WTE
Dutchess
Suffolk
NY
NY
Activity
Level0
(kg/y)
1.80E-K)8
4.64E+08
7.15E+08
1.73E-K)8
2.77E+08
9.85E-K)8
2.79E+09
1.62E+08
2.11E+08
3.74E+08
3.74E+08
6.27E+07
6.27E+07
4.99E+08
1.54E+08
1.54E+08
3.14E+07
3.14E+07
2.05E+10
1.25E+08
1.25E+08
6.27E+07
6.27E+07
1.88E+08
1.11E+09
1.11E+09
3.97E+08
3.97E+08
1.25E+08
1.52E+08
Emission Factor (ng
TEQ/kg)
I-TEQoF
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
6.1
6.1
6.1
Tested
1.9
Tested
0.67
Tested
Tested
Tested
Tested
WHO98
TEQoF
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
6.54
6.54
6.54
Tested
2.07
Tested
0.72
Tested
Tested
Tested
Tested
Annual Air Emissions
(s/y)
I-TEQoF
<0.1
0.1
0.4
0.2
0.4
0.2
1.3
1.0
0.3
1.3
2.3
0.4
0.4
3.1
21
21
0.1
0.1
30
2.7
2.7
<0.1
<0.1
2.7
0.5
0.5
0.1
0.1
<0.1
<0.1
WHO98
TEQoF
<0.1
0.1
0.4
0.2
0.4
0.2
1.3
1.0
0.3
1.3
2.4
0.4
0.4
3.2
23
23
0.1
0.1
33
2.9
2.9
0.1
0.1
3.0
0.5
0.5
0.1
0.1
0.1
<0.1
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to
Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued)
Design" Class
APCDb
MB/RK
FF
MB/RK
H-ESP
MB/RK
C-ESP
67
68
69
Facility Name City Located
State
DSI/FF subtotals
Galax City SW |Grayson
VA
FF subtotals
Bay Resource Management Center | Bay
FL
H-ESP subtotals
Sumner Co. |Sumner
TN
C-ESP subtotals
Totals for all MB/RK
MOD/EA
DS/FF
MOD/EA
DSI/FF
MOD/EA
WS/C-ESP
MOD/EA
C-ESP
MOD/EA
H-ESP
70
71
72
73
74
75
Wallingford RRF |New Haven
CT
DS/FF subtotals
Springfield RRF |Hampden
MA
DSI/FF subtotals
Pittsfield RRF [Berkshire
MA
WS/C-ESP subtotals
Pope-Douglas Waste Douglas
Red Wing Solid Waste Boiler Facility Goodhue
MN
MN
C-ESP subtotals
Pascagoula |Jackson
MS
H-ESP subtotals
Totals for all MOD/EA
MOD/SA
C-ESP
MOD/SA
DSI/C-ESP
MOD/SA
DSI/H-ESP
MOD/SA
DS/FF/CI
76
77
78
79
80
81
82
Juneau RRF Juneau Borough
Perham Renewable RF Otter Tail
Polk Co. Polk
Barron Co. Barren
AK
MN
MN
WI
C-ESP subtotals
City of Cleburne | Johnson
TX
DSI/C-ESP subtotals
Harford Co. WTE Fac. | Harford
MD
DSI/H-ESP subtotals
Oswego Co. WTE | Oswego
NY
DS/FF/CI subtotals
Activity
Level0
(kg/y)
2.78E+08
1.76E+07
1.76E+07
1.54E-K)8
1.54E+08
6.27E+07
6.27E+07
2.02E+09
1.32E+08
1.32E+08
1.13E+08
1.13E+08
1.13E+08
1.13E+08
2.26E+07
2.26E+07
4.52E+07
4.70E+07
4.70E+07
4.50E+08
2.20E+07
3.57E+07
2.51E+07
3.14E+07
1.14E+08
3.57E+07
3.57E+07
1.13E+08
1.13E+08
6.27E+07
6.27E+07
Emission Factor (ng
TEQ/kg)
I-TEQoF
Tested
Tested
47
Tested
0.025
16.2
16.2
16.2
118
16.2
16.2
16.2
16.2
16.2
Tested
Tested
WHO98
TEQoF
Tested
Tested
93.1
Tested
0.024
17
17
17
119
17
17
17
17
17
Tested
Tested
Annual Air Emissions
(s/y)
I-TEQoF
<0.1
0.2
0.2
8.1
8.1
3.0
3.0
12
0.1
0.1
<0.1
<0.1
1.8
1.8
0.4
0.4
0.8
5.6
5.6
8.3
0.4
0.6
0.4
0.5
1.9
0.6
0.6
5.4
5.4
0.1
0.1
WHO98
TEQoF
0.1
0.3
0.3
8.9
8.9
5.9
5.9
16
0.1
0.1
<0.1
<0.1
1.9
1.9
0.4
0.4
0.8
5.6
5.6
8.4
0.4
0.6
0.4
0.5
1.9
0.6
0.6
6.0
6.0
0.1
0.1
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Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued)
Design" Class
APCDb
MOD/SA
DSI/FF
MOD/SA
MOD/SA
WS
MOD/SA
UNC
83
84
85
86
87
88
89
90
Facility Name
Coos Bay Incinerator
City Located
Coos
State
OR
DSI/FF subtotals
Arlington -Pentagon
Arlington
VA
MOD/SA subtotals
Fergus Falls
Panola Co. WTE
Center RRF
Otter Tail
Panola
Shelby
MN
TX
TX
WS subtotals
Miami Airport
Livingston/Park Co.
Miami RRF
Dade
Park
Ottawa
FL
MT
OK
UNC subtotals
Totals for all MOD/SA
RDF/Ded
DS/FF/SNCR
RDF/Ded
DS/FF/CI/SNCR
RDF/Ded
DS/FF
RDF/Ded
DSI/FF
RDF/Ded
91
92
93
94
95
96
97
98
99
100
101
Mid-Connecticut RRF
SEMASS RRF
Maine Energy Recovery
Wilmarth Plant
Hartford
Plymouth
York
Blue Earth
CT
MA
ME
MN
DS/FF/SNCR subtotals
Dade Co. RRF | Dade
FL
DS/FF/CI/SNCR subtotals
Penobscot Energy Recovery
Greater Detroit RRF
Great River Energy
SPSA Waste to Energy
Penobscot
Wayne
Sherburne
Portsmouth
ME
MI
MN
VA
DS/FF subtotals
Red Wing Plant | Goodhue
MN
DSI/FF subtotals
LaCrosse Co. | LaCrosse
WI
Activity
Level0
(kg/y)
4.70E+07
4.70E+07
3.14E+07
3.14E+07
2.95E-K)7
1.25E+07
1.25E+07
5.46E+07
1.88E+07
2.26E+07
3.29E+07
7.43E+07
5.33E+08
7.50E+08
3.65E+08
2.47E+08
2.03E+08
1.57E+09
6.68E+08
6.68E+08
2.20E+08
6.93E+08
2.85E+08
4.89E+08
1.69E+09
1.82E+08
1.82E+08
4.44E+07
Emission Factor (ng
TEQ/kg)
I-TEQoF
Tested
16.2
16.2
16.2
16.2
16.2
16.2
16.2
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
WHO98
TEQoF
Tested
17
17
17
17
17
17
17
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Tested
Annual Air Emissions
(s/y)
I-TEQoF
<0.1
<0.1
0.5
0.5
0.5
0.2
0.2
0.9
0.3
0.4
0.5
1.2
10
0.1
0.1
<0.1
0.1
0.2
1.3
1.3
<0.1
0.5
0.1
0.5
1.1
0.1
0.1
0.7
WHO98
TEQoF
<0.1
<0.1
0.5
0.5
0.5
0.2
0.2
0.9
0.3
0.4
0.6
1.3
11
0.1
0.1
O.I
0.1
0.2
1.4
1.4
O.I
0.5
0.1
0.5
1.1
0.1
0.1
0.7
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Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued)
Design" Class
APCDb
DSI/FF/WSp/SNCR
RDF/Ded
C-ESP
RDF/Ded
DS/ESP
RDF/Ded
DS/ESP/FF/CI
102
103
104
Facility Name
City Located
State
DSI/FF/WSp/SNCR subtotals
Central Wayne Co.
Wayne
MI
C-ESP subtotals
Honolulu RRF | Honolulu
HI
DS/ESP subtotals
SEMASS RRF | Plymouth
MA
DS/ESP/FF/CI subtotals
Totals for all RDF/Ded
FB/RDF
DSI/FF
105
Tacoma
Pierce
WA
DSI/FF subtotals
Totals for all FB/RDF
Totals for all MWCs operating in year 2000
Activity
Level0
(kg/y)
4.44E+07
1.56E-K)8
1.56E+08
5.15E-K)8
5.15E+08
7.41E+08
7.41E+08
5.56E+09
9.41E-K)?
9.41E+07
9.41E+07
2.94E+10
Emission Factor (ng
TEQ/kg)
I-TEQoF
Tested
Tested
Tested
0.67
WHO98
TEQoF
Tested
Tested
Tested
0.72
Annual Air Emissions
(s/y)
I-TEQoF
0.7
0.1
0.1
2.0
2.0
0.1
0.1
5.6
0.1
0.1
0.1
69
WHO98
TEQoF
0.7
0.1
0.1
2.2
2.2
0.10
0.10
5.9
0.1
0.1
0.1
77
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aMWC Design class: FB/RDF = Fluidized-bed refuse-derived fuel; MB/WW = Mass burn waterwall; MB/RK = Mass burn rotary kiln; MB/REF = Mass burn
refractory walled; MOD/EA = Modular excess air; RDF/Ded = Dedicated refuse-derived fuel.
bAPCD = air pollution control device. DS/FF/CI/SNCR (dry scrubber followed by fabric filter with carbon injection and nitrogen oxide control); DS/FF/SNCR
(dry scrubber followed by fabric filter with nitrogen oxide control); DS/FF/CI (dry scrubber followed by fabric filter with carbon injection); DS/FF (dry
scrubber followed by fabric filter); DSI/FF (duct sorbent injection followed by fabric filter); DSI/FF/WSp/SNCR (duct sorbent injection followed by fabric filter
with water spray and nitrogen oxide control); DS/ESP/CI/SNCR (dry scrubber followed by electrostatic precipitator with carbon injection and nitrogen oxide
control); DS/ESP/CI (dry scrubber followed by electrostatic precipitator with carbon injection); C-ESP (cold-sided electrostatic precipitator); H-ESP (hot-sided
electrostatic precipitator); DSI/C-ESP (duct sorbent injection followed by cold-sided electrostatic precipitator); DSI/H-ESP (duct sorbent injection followed by
hot-sided electrostatic precipitator); WS (wet scrubber); WS/C-ESP (wet scrubber followed by cold-sided electrostatic precipitator); UNC (uncontrolled).
0 Activity Level is the annual amount (kg) of municipal solid waste or refuse derived fuel expected to be combusted by the MWC. It is estimated by multiplying
the annual design capacity of the furnace by 85%. The figure of 85% represents the assumption that the MWC will experience downtime during the year for
maintenance and repairs.
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Table 3-4. TEQ air emissions from medical waste incinerators (MWIs) for
reference year 1987,1995, and 2000
MWI class
No. of tested
facilities/total
I-TEQDF
emission
factor
(ng/kg)
WHO98
TEQDF
emission
factor
(ng/kg)
Activity level
(kg/yr)
Annual
I-TEQDF
emissions
(g/yr)
Annual
WHO98
TEQDF
emissions
(g/yr)
1987
Uncontrolled
Controlled
TOTAL
7/5,000
0
1,800
1,900
1.43E+09
0
1.43E+09
2,600
0
2,600
2,700
0
2,700
1995
Uncontrolled
Controlled
TOTAL
7/1,770
12/605
1,800
50
1,900
51
2.54E+08
5.17E+08
7.71E+08
460
26
490
480
26
510
2000
Uncontrolled
Controlled
TOTAL
7/975
12/333
1,800
50
1,900
51
1.98E+08
4.03E+08
6.01E+08
360
20
380
380
20
400
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1 4. COMBUSTION SOURCES OF CDDS/CDFS: POWER/ENERGY GENERATION
2
O
4 4.1. MOTOR VEHICLE FUEL COMBUSTION
5 This section covers on-road and off-road vehicles. The activity estimates were changed
6 so that all are on a per-liter basis rather than a per-km driven basis, resulting in small changes in
7 the air-release estimates. Other changes include addition of new literature studies, clarifications
8 about derivations of emission factors, and discussions about the uncertainties associated with the
9 estimates for off-road vehicles. Separate release estimates for 2-stroke engines (also referred to
10 as 2-cycle engines) were considered, but insufficient information was available on both emission
11 factors and activities to do this. The activity estimates are based on total fuel sold and include
12 fuels used in all types of engines. Thus, 2-stroke engines are represented, and the uncertainties
13 associated with their emissions are discussed. The confidence ratings for releases from all off-
14 road vehicles were changed to preliminary due to lack of emissions test data. There were
15 insufficient data to make an emission estimate for waste motor oil; see Section 4.3 for
16 information on combustion of waste motor oil.
17
18 4.1.1. Air Literature
19 A number of additional studies on dioxin emissions from diesel engines were found as
20 summarized below.
21 Gullett and Ryan (2002) characterized CDD/CDF emissions from two heavy duty diesel
22 trucks under highway driving conditions and while idling: a 1989 Ford with a turbocharged
23 Cummins engine and mechanical fuel controls and a 1990 Kenworth with a T800 engine
24 equipped with the first generation of electronic fuel controls. The Ford trailer was loaded at
25 16,900 kg, and the Kenworth trailer at 8,400 kg. The Kenworth was tested using both a high
26 mileage and the same engine in rebuilt, or "low mileage" condition. The average emission
27 factors reported for each vehicle and driving condition are presented below:
28
29 • Ford/highway: 385 pg WHO98 TEQ/L
30 • Kenworth/highway (old engine): 58 pg WHO98 TEQ/L
31 • Kenworth/highway (rebuilt engine): 24 pg WHO98 TEQ/L
32 • Kenworth/idle: 6 pg WHO98 TEQ/L
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1 Tests were also performed using a low-sulfur fuel, which was representative of U.S. diesel fuels
2 in 2000.
3 Kim et al. (2003) conducted a study in Korea that measured CDD/CDF emissions from a
4 light duty diesel engine under various loadings. The average CDD/CDFs concentrations per unit
5 of exhaust gas with 25, 50, and 75% load rate are 14.5, 6.9, and 6.4 pg TEQ/Nm3, respectively.
6 According to the authors, these values, respectively, convert to 2.0, 0.6, and 0.5 pg TEQ/L fuel.
7 Norbeck et al. (1998) measured CDD/CDF emissions from a 6-cylinder, 310-hp diesel
8 engine over the heavy-duty transient test cycle. Emission testing was conducted at the Los
9 Angeles County Metropolitan Transportation Authority emission test facility. Dioxin sampling
10 was conducted for the pre-1993 and reformulated fuels. Although PCDDs and PCDFs were
11 detected, the most toxic isomers, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, and 2,3,4,7,8-PeCDF were
12 not detected in either the pre-1993 or reformulated fuel. TEQ profiles were incomplete due to
13 the low levels of CDD and PCDF detected in the emission samples.
14 Mayer et al (2003) reports on the use of fine-pored hot gas traps with filtration
15 efficiencies exceeding 99% of the solid particles in the diesel exhaust gas. Catalyzed particle
16 traps also achieve greater than 99% reduction in emissions of semi-volatile hydrocarbons (Laroo
17 et al., 2011, CRC, 2009). This technology is used by original equipment manufacturers on new
18 diesel exhaust systems and has been used to retrofit on-road and off-road engines in the U.S.
19 Mayer et al testing with fuel borne catalysts indicate that in these situations, the large effective
20 area of the filter, and the engine exhaust gas components in conjunction with the fuel borne
21 catalysts can promote undesirable chemical reactions that release toxic secondary emissions.
22 Dioxins and furans were found not to form in most trap systems but fuel-borne additives
23 containing copper with extremely high fuel chlorine levels (up to 110 ppm), caused emissions to
24 increase by four orders of magnitude. Copper fuel additives are not registered for use in the U.S. in
25 on-road engines.
26 Laroo et al. (2011), Liu et al. (2011) and Hovemann et al. (2010) compared emissions of
27 dioxins and furans using various catalyzed aftertreatment systems, including diesel oxidation
28 catalysts, catalyzed diesel paniculate filters, and copper and iron zeolite selective catalytic
29 reduction (SCR) systems that are currently used in on-road diesel trucks in the U.S. These
30 studies report no increase in dioxin or furan emissions when using catalyzed aftertreatment
This document is a draft for review purposes only and does not constitute Agency policy.
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1 systems and fuel chlorine levels that were representative and one order of magnitude higher than
2 what is currently in ultra low sulfur pump diesel fuel.
3 UNEP (2005) presents emission factors for a variety of engine types and fuels. These
4 were originally presented in units of jig I-TEQ/MT and are converted to pg I-TEQ/L below
5 (assumes diesel fuel has a density of 0.85 kg/L and gasoline has a density of
6 0.75 kg/L—Hazardous Substances Database,
7 http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen7HSDB.htm):
8
9 • Leaded gasoline, 4-stroke engine—1,600 pg I-TEQ/L
10 • Leaded gasoline, 2-stroke engine—2,600 pg I-TEQ/L
11 • Unleaded gasoline, 4-stroke engine without catalyst—75 pg I-TEQ/L
12 • Unleaded gasoline, 4-stroke engine with catalyst—0
13 • Unleaded gasoline, 2-stroke engine without catalyst—1,900 pg I-TEQ/L
14 • Diesel engines—85 pg I-TEQ/L
15
16 4.1.2. Air Emission Factor
17 In the original document, some of the emission factors were presented on a per-km driven
18 basis and some on a per-liter of fuel basis. The present document changes all vehicle emission
19 factors to a per-liter basis. Separate emission factors were developed for vehicles burning leaded
20 gasoline, unleaded gasoline, and diesel fuel.
21
22 4.1.2.1. Leaded Gasoline
23 The literature indicates that CDD/CDF emissions occur from vehicles using leaded
24 gasoline, and that considerable variation occurs depending, at least in part, on the types of
25 additives used in the fuel or motor oil (Ballschmiter et al., 1986; Marklund et al., 1990).
26 The average emission factor, as reported for the tailpipe emission studies performed
27 using commercial leaded fuel (see Table 4-4 in U.S. EPA, 2006), was 532 pg WHO9g TEQDF/L
28 (450 pg I-TEQoF/L), (Marklund et al., 1990; Hagenmaier et al., 1990; Schwind et al., 1991).
29 This emission factor was applied to 1987 but was not needed for the other years due to the
30 phaseout of leaded gasoline.
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1 For application to off-road engines, this emission factor is considered preliminary
2 because it is based on automobile testing and it is uncertain how well it applies to off-road
3 engines (see discussion below).
4
5 4.1.2.2. Unleaded Gasoline
6 The literature documenting results of European studies indicates that CDD/CDF
7 emissions from vehicles burning unleaded fuels are lower than emissions from vehicles burning
8 leaded gas with chlorinated scavengers. It also appears, based on the limited data available, that
9 catalyst-equipped cars have lower emission factors than do noncatalyst-equipped cars (Marklund
10 et al., 1987; Marklund et al., 1990; Hagenmaier et al., 1990; Schwind et al., 1991). All
11 automobiles running on unleaded gasoline in the United States are equipped with catalysts
12 (commonly known as "catalytic converters"). The average emission factor reported for the
13 tailpipe emission studies performed on catalyst-equipped cars (Hagenmaier et al., 1990; Schwind
14 et al., 1991; Hutzinger et al., 1992) was calculated as 15.6 pg WHO9g TEQDF/L
15 (14.9 pg I-TEQop/L) This emission factor was assumed to apply to each reference year.
16 For application to off-road engines, this emission factor is considered preliminary
17 because it is based on automobile testing, and it is uncertain how well it applies to off-road
18 engines. Off-road engines can have very different designs. For example, few, if any, off-road
19 gasoline engines have the mechanisms for fuel efficiency and emission control that on-road
20 engines have, such as feedback control systems that monitor and correct the air-to-fuel ratio for
21 combustion; either oxidation or three-way catalysts or exhaust gas recirculation systems (EGR);
22 or overhead valves. Two-stroke engines are much more commonly used in off-road applications
23 than on-road vehicles. The compression ratios for these engines are generally significantly less
24 than those of four-stroke engines (U.S. EPA, 2002c). As a result, emissions of traditional
25 pollutants from two-stroke engines are higher than from four-stroke engines. For example, EPA
26 estimates emissions of PM from two-stroke, off-road motorcycles to be more than 20 times that
27 of four-stroke motorcycles (U.S. EPA, 2002a). Although dioxin emissions do not always
28 correspond to emissions of conventional pollutants, it is possible that two-stroke off-road engines
29 have higher dioxin emissions. This belief is strongly reflected in the UNEP (2005) emission
30 factor recommendations of 1,900 pg I-TEQ/L for unleaded gasoline in two-stroke engines
31 without catalysts versus zero for unleaded gasoline in four-stroke engines with catalyst. The
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1 UNEP (2005) recommendations for two-stroke engines were not adopted here due to the lack of
2 supporting references.
3
4 4.1.2.3. Diesel Fuel
5 Data available upon which to base an evaluation of the extent of CDD/CDF emissions
6 resulting from diesel fuel combustion are discussed in this section. These data address only
7 emissions from on-road vehicles; no emissions data are available for off-road diesel uses
8 (construction vehicles, farm vehicles, and stationary equipment).
9 Laroo et al. (2011) reported emission factors for a 2008 model year diesel engine of 1.89
10 pg I-TEQ/L without aftertreatment under steady-state operation; 1.28 pg I-TEQ/L for an engine
11 with copper zeolite urea SCR, diesel oxidation catalyst, and catalyzed paniculate filter
12 aftertreatment under transient operation; and 0.21 pg I-TEQ/L for an engine equipped with a
13 diesel oxidation catalyst and catalyzed paniculate filter under transient operation. Liu et al.
14 (2011) reported emission factors for a 2010 model year diesel engine of 0.31 pgWHO 1998
15 TEQ/hp-hr without aftertreatment; 0.12 pg WHO 1998 TEQ/hp-hr for an engine with copper
16 zeolite urea SCR, diesel oxidation catalyst, and catalyzed particulate filter aftertreatment and
17 0.13 pg WHO 1998 TEQ/hp-hr for an engine equipped with a diesel oxidation catalyst and
18 catalyzed parti culate filter under steady-state operation. Hovemann et al. (2010) reported
19 emissions factors of 0.11 pg/m3 for steady-state operation and 0.10 pg/m3 for transient operation
20 of a diesel engine with aftertreatment including a diesel oxidation catalyst, copper zeolite SCR
21 and urea. The Health Effects Institute (2009) reported a range of emissions from 0.13 - 1.4 pg I-
22 TEQ/L for three diesel engines equipped with catalyzed particulate filters.
23 Although aggregate samples representing several thousand heavy-duty diesel vehicles
24 were collected in Oehme et al. (1991), several characteristics of the study introduce considerable
25 uncertainty with regard to the use of the study's results as a basis for estimating emissions in the
26 United States: (a) heavy-duty vehicles represented only 3 to 19% of total vehicle traffic in the
27 tunnel; (b) the majority of the light-duty vehicles were fueled with leaded gasoline, which can
28 lead to increased releases of CDD/CDFs; and (c) technology differences likely existed between
29 the 1988 Norwegian and the 1987 and 1995 U.S. vehicle fleets.
30 The tunnel study conducted in Baltimore, MD, by Gertler et al. (1996, 1998) shares the
31 disadvantages of all tunnel studies relative to those that directly measured CDDs and CDFs in
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1 tailpipe emissions. Specifically, tunnel studies rely on indirect measurements (rather than
2 tailpipe measurements), which may introduce bias, and the emission factors calculated from
3 these studies reflect the mix of vehicles using the tunnel—and not necessarily the overall vehicle
4 fleet. Also, they reflect the driving conditions of the tunnel (surface slope, speed, braking, etc.),
5 which may not be representative of usual driving conditions.
6 However, the Gertler et al. (1996, 1998) study does have strengths that are lacking in the
7 Oehme et al. (1991) tunnel study, and it has advantages over the two U.S. diesel truck tailpipe
8 studies, including: (a) the study was conducted during the reference year time frame (1995) in
9 the United States and, thus, reflects U.S. fuels and technology of that time period, (b) virtually no
10 vehicle using the tunnel was fueled with leaded gasoline, (c) the tunnel walls and streets were
11 cleaned one week prior to the start of sampling and, in addition, the study analyzed road dust and
12 determined that resuspended road dust contributed only about 4% of the estimated emission
13 factors, (d) the heavy-duty vehicles comprised, on average, a relatively large proportion (25.7%)
14 of vehicles using the tunnel, and (e) a large number of heavy-duty vehicles—approximately
15 33,000—passed through the tunnel during the sampling period, which generates confidence that
16 the emission factor is representative of interstate trucks. It should be noted, though, that the
17 study was most representative of heavy duty trucks because these were the primary type of
18 vehicle using the tunnel. For other diesel vehicles (e.g., light duty trucks, automobiles, buses),
19 the study is less representative, and uncertainty is greater.
20 Considering the strengths and weaknesses of the available emission factor data from the
21 tailpipe and tunnel studies, the mean TEQ emission factor reported by Gertler et al. (1996,
22 1998)—182 pg WHO98 TEQDF/km (172 pg I-TEQDF/km)—is assumed to represent the best
23 current estimate of the average emission factor for on-road diesel-fueled vehicles. This emission
24 factor was converted to a per-liter basis assuming a fuel efficiency of 2.98 km/L (U.S. EPA,
25 2003a). This yields an emission factor of 540 pg WHO98 TEQDF/L (510 pg I-TEQDF/L), which
26 was assumed to apply to all reference years for both on-road and off-road vehicles. It is likely
27 that the fleet average emission factor has decreased over the reference years (due to
28 improvements in engine/emission designs), but insufficient information was available to account
29 for this. For application to off-road vehicles, the factor is considered preliminary because it is
30 based on truck testing, and it is uncertain how well it applies to other types of diesel vehicles
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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
such as heavy duty vehicles used in construction, tractors, off-road military vehicles, ships, and
locomotives.
4.1.3. Air Activity Level
The activity estimates for internal combustion engines were derived on the basis of fuel
consumed as reported by the Energy Information Administration (EIA, 2008a).
4.1.3.1. Gasoline
EIA (2008a) provides data on the total "motor gasoline product supplied," which
represents all gasoline consumed in the United States. These data were reported as barrels per
year and are converted here to liters by multiplying by 42 gal/barrel and 3.78 L/gal. For 1987, it
is assumed that 24% of the gasoline was leaded (1.00 x lo11 L) and the remainder unleaded
(3.18 x 1011 L) (EIA, 1993). For years 1995 and 2000, it is assumed that leaded gasoline was
produced in negligible amounts. The total amount of unleaded gasoline consumed in 1995 was
4.00 x 1011 L, and the total amount consumed in 2000 was 4.93 x 1011 L. EIA does not provide
data that allow the gasoline uses to be divided between on road and off road. However,
U.S. EPA (2006) provided estimates for the year 2000 suggesting that 5% of the gasoline was
used for off-road engines (kilometers driven on road were converted to liters, assuming an
average fuel efficiency of 10 km/L). This percentage was assumed to apply to all reference
years, resulting in the following estimates:
1987
1995
2000
Leaded (L)
Total
1.00 x 1011
0
0
On-road
9.5 x 1010
0
0
Off-road
0.5 x 1010
0
0
Unleaded (L)
Total
3.18 x 1011
4.00 x 1011
4.93 x 1011
On-road
3.03 x 1011
3.80x 1011
4.68 x 1011
Off-road
0.15 x 1011
0.20 x 1011
0.25 x 1011
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1 4.1.3.2. Diesel
2 EIA provides data on "distillate fuel oil product supplied," which represents all distillate
3 fuel consumed in the United States. Distillate fuel includes diesel and other fuels used primarily
4 for space heating. The diesel portion of the distillate fuel was determined using EIA data on
5 "sales of distillate fuel oil by end use." For 2001, these data suggest the following:
6
7 • Diesel fuel used on road is 55% of the total.
8 • Diesel fuel used off road (includes off-highway, farm, railroad, vessels, and military
9 categories) is 20% of the total.
10 • Other uses of distillate fuels (includes residential, commercial, industrial, and electric
11 power categories) make up 25% of the total.
12
13 It is assumed that these percentages for 2001 apply to all reference years. Applying these to the
14 "distillate fuel oil product supplied," yields:
15
16 • 1987—9.48 x 1010 L on road, 3.45 x 1010 L off road
17 • 1995—1.02 x 1011 L on road, 3.71 x 1010 L off road
18 • 2000—1.19 x 1011 L on road, 4.32 x 1010 L off road
19
20 4.1.4. Air Releases
21 Air-release estimates were made by multiplying the emission factors with the activity
22 estimates. Separate release estimates were made for leaded gasoline, unleaded gasoline, diesel
23 off road, and diesel on road.
24
25 4.1.5. Water Releases—None
26
27 4.1.6. Solid Residue Releases
28 Solid residue releases could result from disposal/recycling of mufflers or catalytic
29 converters. No information could be found on the possible CDD/CDF content of these materials.
30
31 4.1.7. Products—None
32
This document is a draft for review purposes only and does not constitute Agency policy.
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1 4.1.8. Release Summary
2 The inventory decision criteria and release estimates to all media are summarized below:
Inventory Decision Criteria for Motor Vehicle
Combustion — On-road
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
4
5
Inventory Decision Criteria for Motor Vehicle
Combustion — Off-road
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
No
No
Yes
P
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Motor Vehicle Combustion
Air Releases
Emission Factors
Leaded Gasoline
• 1987—530 pg WHO98 TEQDF/L (450 pg I-TEQDF/L) (Preliminary for off-road).
Unleaded Gasoline
• 1987—16 pg WHO98 TEQDF/L (15 pg I-TEQDF/L) (Preliminary for off-road).
• 1995—16 pg WHO9g TEQDF/L (15 pg I-TEQDF/L) (Preliminary for off-road).
• 2000—16 pg WHO98 TEQoF/L (15 pg I-TEQDF/L) (Preliminary for off-road).
Diesel
• 1987—540 pg WHO98 TEQDF/L (510 pg I-TEQDF/L) (Preliminary for off-road).
• 1995—540 pg WHO98 TEQDF/L (510 pg I-TEQDF/L) (Preliminary for off-road).
• 2000—540 pg WHO98 TEQDF/L (510 pg I-TEQDF/L) (Preliminary for off-road).
Activity Levels
Leaded Gasoline, On-road
• 1987—9.5 x l010L/yr.
Leaded Gasoline, Off-road
• 1987—0.5 x l010L/yr.
Unleaded Gasoline, On-road
• 1987—3.03 x !OnL/yr.
• 1995—3.80 x !OnL/yr.
• 2000—4.68 x 1011 L/yr.
Unleaded Gasoline, Off-road
• 1987—3.18 x 1011 L/yr.
• 1995—4.00 x 1011 L/yr.
• 2000—4.93 x 1011 L/yr.
Diesel, On-road
• 1987—0.15 x 1010 L/yr.
• 1995—0.20 x 1011 L/yr.
• 2000—0.25 x 1011 L/yr.
Diesel, Off-road
• 1987—3.45 x 1010 L/yr.
• 1995—3.71 x 1010 L/yr.
• 2000—4.32 x 1Q10 L/yr.
This document is a draft for review purposes only and does not constitute Agency policy.
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Motor Vehicle Combustion (continued)
Releases
Leaded Gasoline, On— road
• 1987—50 g WHO98 TEQDp (43
Leaded Gasoline, Off— road
• 1 987—3 g WHO98 TEQDF (2 g
Unleaded Gasoline, On-road
• 1 987—5 g WHO98 TEQDF (5 g
• 1 995—6 g WHO98 TEQoF (6 g
• 2000—7 g WHO98 TEQoF (7 g
Unleaded Gasoline, Off-road
• 1987—0.2 g WHO98 TEQoF (0.
• 1995—0.3 g WHO98 TEQoF (0.
• 2000—0.4 g WHO98 TEQDF (0.
Diesel, On-road
• 1 987—5 1 g WHO98 TEQDF (48
• 1995—55 g WHO98 TEQDF (52
• 2000—64 g WHO98 TEQDF (6 1
Diesel, Off-road
• 1987—19 g WHO98 TEQoF (18
• 1995—20 g WHO98 TEQoF (19
• 2000—23 g WHO98 TEQoF (22
g I-TEQDF)
I-TEQop) (Preliminary).
i-TEQDF).
i-TEQDF).
I-TEQDF).
2 g I-TEQDF) (Preliminary).
3 g I-TEQop) (Preliminary).
4 g I-TEQDF) (Preliminary).
g I-TEQDF).
g I-TEQDF).
g I-TEQDF).
g I-TEQop) (Preliminary).
g I-TEQop) (Preliminary).
g I-TEQop) (Preliminary).
Water Releases
No information was found suggesting that water releases from internal combustion engines
would contain CDDs and CDFs.
Solid Residue Releases
No information was found suggesting that solid residue releases from internal combustion
engines would contain CDDs and CDFs.
Products
None.
1
2
3 4.2. WOOD COMBUSTION
4 4.2.1. Residential Wood Combustion
5 Several new literature studies were added, but no changes were made to the estimates of air
6 releases from traditional residential wood-burning fireplaces and stoves. New sections were
7 developed on the air releases from outdoor wood-fired boilers and on solid residues from all
8 forms of residential wood burning.
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1 This section focuses on residential burning of natural untreated wood. It should be noted
2 though, that treated wood may be burned at some residences with the potential for increased
3 CDD/CDF emissions. Wevers et al. (2003) measured CDD/CDF emissions from domestic
4 wood-burning appliances and reported emission factors of 22.4 ng I-TEQ/kg for burning
5 untreated wood and 1,702 ng I-TEQ/kg for burning treated wood. Tame et al. (2003) measured
6 CDD/CDF levels in ash from wood combustion in a cone calorimeter. Ash from burning
7 untreated pine had an average of 0.050 ng I-TEQ/kg ash. For the CCA (chromated copper
8 arsenate) treated pine, burnt under identical conditions, a significant increase was observed, with
9 an average of 35 ng I-TEQ/kg. Tame et al. (2007) reviewed the literature on the role of
10 preservatives in the formation of dioxin in the combustion of wood. They conclude that current
11 and emerging wood preservatives significantly increase dioxin formation during combustion in
12 domestic stoves and in fires. Not all investigators, however, have observed these increases.
13 Wasson et al. (2005) conducted chamber tests to measure CDD/CDF emissions from burning
14 CCA treated wood. Emission factors ranged from 1.4 to 2.3 ng WHOgg TEQ/kg, which are
15 similar to those for untreated wood.
16
17 4.2.1.1. Air Releases from Indoor Residential Wood Burners
18 A study conducted in Australia by Gras et al. (2002) measured dioxin emissions from a
19 variety of wood-burning appliances and wood types. The average values for various wood types
20 were 7.5 ng WHOgg TEQ/kg for eucalyptus, 19 ng WHOgg TEQ/kg for manufactured wood, and
21 < 1 ng WHOgg TEQ/kg for softwoods.
22 Gullett et al. (2003) measured dioxin emissions from residential fireplace and woodstove
23 appliances burning fuels available from the San Francisco Bay area. Common California natural
24 firewoods and manufactured artificial logs were tested under operating conditions intended to
25 reflect domestic use patterns in the Bay area, which are primarily episodic burning for aesthetic
26 reasons. Average CDD/CDF emissions factors ranged from 0.25 to 1.4 ng WHOgg TEQ/kg of
27 wood burned for natural wood fuels and 2.4 ng WHOgg TEQ/kg for artificial logs.
28 Pfeiffer et al. (2000) measured CDD/CDF emissions from wood fired household
29 appliances used in Germany. Emission factors ranged from 0.141 to 0.785 ng I-TEQ/kg.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 Wevers et al. (2003) measured CDD/CDF emissions from domestic wood burning
2 appliances used in Belgium. The average emission factor was 22.4 ng I-TEQ/kg for burning
3 untreated wood.
4 UNEP (2005) recommended an emission factor of 100 jig I-TEQ/TJ (TJ = terajoule or
5 1012 joule) for virgin biomass-fired stoves. Assuming that wood combustion produces
6 12-15 MJ/kg where MJ = megajoule or 106 joule (UNEP, 2005), this converts to 1.2 to
7 1.5 ng I-TEQ/kg of wood burned.
8 The emission factor selected for indoor residential wood burning was based on
9 Environment Canada (2000) because these tests took place in North America using indigenous
10 wood, and they included the analysis of an EPA-certified wood stove. The mean value of the
11 Environment Canada study (0.5 ng I-TEQ/kg wood or ng WHOgg TEQ/kg wood) was applied to
12 all reference years.
13 Activity estimates were derived from EIA (2008b), which reports energy production from
14 residential wood burning in BTUs. These were converted to mass of wood burned by dividing
15 these values by 14,080 BTU/kg (average heat value of seasoned wood at 20% moisture—ORNL,
16 2008). This yields estimates of 71 MMT in 1987, 37 MMT in 1995 and 30 MMT in 2000.
17
18 4.2.1.2. Air Releases from Residential Outdoor Wood-Fired Boilers
19 Outdoor wood-fired boilers (OWBs) are wood-fired furnaces used for heating, typically
20 in residential settings. They are located some distance from the house, usually in an insulated
21 shed. Each OWE houses an oversized firebox surrounded by a water jacket. Water is circulated
22 through the jacket and piped underground to deliver hot water for space heating and domestic
23 use. OWBs are designed to burn large amounts of wood over extended periods of time;
Q Q 9
24 fireboxes range in size from 20 ft to 150 ft and can heat buildings up to 20,000 ft . They can
25 produce from 115,000 BTU/hour up to 3.2 million BTU/hour, although most residential
26 installations are less than 1 million BTU/hour (NESCAUM, 2006).
27 Because OWBs operate in a cyclic fashion, they can produce large amounts of smoke.
28 When an OWE is in the "off cycle and does not need to generate heat, the air damper closes to
29 cut off the air supply. This creates an oxygen-starved environment in which the fire smolders,
30 creating smoke and creosote that condenses on the internal steel surfaces. When heat needs to be
31 produced, the air damper opens and natural draft forces air into the firebox, pushing the smoke
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1 and air pollutants out the stack. Measured emissions peak when the unit has received a fresh
2 load of fuel and the wood has not yet reached a charcoal stage. In the field test conducted by
3 NESCAUM, the unit's internal stack temperature never reached levels that would have resulted
4 in complete combustion. In comparing emissions of particulate matter (PM) from various
5 sources, it was noted that one OWE can emit as much PM as four heavy duty diesel trucks.
6 Generally, OWBs do not use catalytic or noncatalytic emission control devices commonly
7 employed by other residential combustion devices (NESCAUM, 2006).
8 OWBs have not been tested for CDD/CDF emissions. Their cyclic air flow and low
9 operating temperatures (see discussion above), suggests that their emissions may be best
10 represented by a value near the upper end of measurements for natural wood burned in wood
11 stoves. Accordingly, an emission factor of 20 ng WHOgg TEQop/kg wood (based on Wevers
12 et al., 2003) is used to represent OWBs. This emission factor is assigned a preliminary
13 confidence rating because it is not based on testing of actual OWBs.
14 EPA estimates that there were more than 100,000 OWBs in use in the United States in
15 2007; NESCAUM estimates that more than 155,000 units have been sold since 1990 (U.S. EPA,
16 2007a). An average household in the Northeast (where many of these units are used) consumes
17 63.1 million BTU per year for space heating (EIA, 2001). Multiplying this value by the
18 100,000 OWBs in use suggests they produced a total of 6.3 trillion BTU in 2007. Dividing this
19 value by 14,080 BTU per kilogram (the average heat value of seasoned wood at 20% moisture
20 [ORNL, 2008]) yields a total wood consumption of 448,000 MTs in 2007, and this is assumed to
21 apply to 2000. Because it is not known how many units were in operation in 1987 and 1995, the
22 activity level could not be estimated for these years.
23 This procedure assumes that all OWBs supply 100% of a home's space heating needs,
24 which may lead to an overestimate of wood consumed. The assumption that the 2007 activity
25 value applies to 2000 also leads to an overestimate. However, the assumption that only seasoned
26 wood is burned, when in fact unseasoned wood may also be used, would underestimate the
27 amount of wood consumed. It is unclear to what extent these uncertainties offset each other.
28
29 4.2.1.3. Water Releases—None
30
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1 4.2.1.4. Solid Residues from All Residential Wood Burning
2 EPA (2006) summarizes studies measuring CDDs/CDFs in chimney soot from wood-
3 burning stoves and fireplaces by several researchers (Bumb et al., 1980; Nestrick and Lamparski,
4 1982, 1983; Clement et al., 1985; Bacher et al., 1992; Van Oostam and Ward, 1995; Dumler-
5 Gradl et al., 1995). The CDD/CDF levels ranged from 80 to 350 ng WHO98 TEQ/kg.
6 Wunderli et al. (1996) measured CDD/CDF levels in ash of wood-burning facilities in
7 Switzerland. The facilities were characterized as small-to-medium sized, but they were not
8 described in detail. Some of them had air pollution controls and may have been more
9 sophisticated than most residential wood stoves. The mean level for natural wood burning was
10 2.5 ng I-TEQ/kg of fly ash (n = 6) and 5.3 ng I-TEQ/kg of bottom ash (n = 8). UNEP (2005)
11 used this reference to support their recommendation of 10 ng I-TEQ/kg of ash residue from
12 biomass-fired stoves.
13
14 4.2.1.5. Solid Residue Emission Factor
15 The CDD/CDF levels in soot are likely to be higher than bottom ash from wood burning,
16 so the soot based studies noted above were not used to select an emission factor. Instead, the
17 UNEP (2005) recommendation of 10 ng I-TEQ/kg of ash residue (based on Wunderli et al.,
18 [1996] data for wood-burning bottom ash) was selected as the best for residential wood burning.
19 The congener profile for bottom ash from natural wood burning reported by Wunderli et al.
20 (1996) indicated that the WHO98 TEQs were only about 4% greater than the I-TEQs. On this
21 basis, the UNEP recommendation can also be expressed as 10 ng WHOgg TEQ/kg of ash residue.
22
23 4.2.1.6. Solid Residue Activity Level
24 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to
25 8% ash (Ragland et. al, 1991). A mid-range value of 3% is assumed here for all wood burned.
26 Multiplying this percentage by the amount of wood consumed (as reported above) yields the ash
27 production amounts for each reference year: 2.13 MMT in 1987, 1.11 MMT in 1995, and
28 0.9 MMT in 2000.
29
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1 4.2.1.7. Solid Residue Releases
2 Solid residue releases were estimated by multiplying the ash emission factor by the ash
3 activity level. These release estimates include both indoor and outdoor sources of residential
4 wood combustion. Some ash from residential wood combustion is disposed with household
5 garbage that is sent to municipal landfills. This portion of the ash would not be considered a
6 release to the open environment. The remainder is land disposed in a manner that is assumed to
7 be releasable to the environment. One study reported that approximately 80% of all ash is land
8 applied in the Northeast United States, less than 10% is land applied in the Southeast (University
9 of Georgia, 2002). Because the portion going to a landfill is probably small, it is assumed here
10 that all of the ash releases can be considered an environmental release.
11
12 4.2.1.8. Release Summary
13 The inventory decision criteria and release estimates to all media are summarized below:
14
Inventory Decision Criteria for Indoor Residential Wood Burners
Air Water Solids Products
Emission tests for at least two units/source types with Yes Yes
lUfficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes Yes
ifferences.
Emission factor tests represent units that are typical of the Yes Yes
;lass.
activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary). Q Q_
15
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Residential Wood Combustion
Air Releases
Emission Factor
Indoor Residential Wood Burners
• 1987—0.5 ng WHO98 TEQDF/kg (I-TEQDF/kg) of wood.
• 1995—0.5 ng WHO98 TEQDF/kg (I-TEQDF/kg) of wood.
• 2000—0.5 ng WHO98 TEQDF/kg (I-TEQDF/kg) of wood.
Outdoor Wood-Fired Boilers
• 1987—20 ng WHO98 TEQDF/kg of wood (Preliminary).
• 1995—20 ng WHO98 TEQDF/kg of wood (Preliminary).
• 2000—20 ng WHO98 TEQDF/kg of wood (Preliminary).
Activity Level
Indoor Residential Wood Burners
• 1987—71 MMT.
• 1995—37 MMT.
• 2000—30 MMT.
Outdoor Wood-Fired Boilers
• 1987—Not Available.
• 1995—Not Available.
• 2000—0.448 MMT (Preliminary).
Releases
Indoor Residential Wood Burners
• 1987—36 g (WHO98 TEQDF or I-TEQDF).
• 1995—19g(WHO98TEQDForI-TEQDF).
• 2000—15 g (WHO98 TEQDF or I-TEQDF).
Outdoor Wood-Fired Boilers
• 1987—Not Available
• 1995—Not Available
• 2000—9 g WHO98 TEQDF (Preliminary).
Water Releases
None.
This document is a draft for review purposes only and does not constitute Agency policy.
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Residential Wood Combustion (continued)
Solid Residue Releases
Emission Factors
• 1987—10 ng WHO98 TEQDF/kg (I-TEQDF/kg) of ash.
• 1995—10 ng WHO98 TEQDF/kg (I-TEQDF/kg) of ash.
• 2000—10 ng WHO98 TEQDF/kg (I-TEQDF/kg) of ash.
Activity Levels
• 1987—2.13 MMT of ash.
• 1995—1.11 MMT of ash.
• 2000—0.9 MMT of ash.
Releases
• 1987—21 g (WHO98 TEQDF or I-TEQDF).
• 1995—11 g (WHO98 TEQDF or I-TEQDF).
• 2000—9 g (WHO98 TEQDF or I-TEQDF).
Products
None.
1
2
3 4.2.2. Industrial Wood Combustion
4 4.2.2.1. Air Releases
5 No changes were made to the emission factor estimates for industrial burning of salt and
6 nonsalt laden wood. However, an additional study is discussed below which shows that
7 combustion temperature and wood condition can have a large impact on emission factors.
8 Yasuhara et al. (2003) measured CDD/CDF emissions from a wood burning incinerator
9 in Japan. With combustion temperature of about 600EC, the following emission factors
10 (ng WHO98 TEQ/kg) were measured: pine—167, cedar—164, seawater impregnated pine—392,
11 seawater impregnated cedar bark—559 and seawater impregnated cedar without bark—828.
12 Much lower emission factors were measured when the combustion temperature was increased to
13 800EC: pine—2.3, beech—3.5, chlordane impregnated waste wood—40 and pentachlorophenol
14 impregnated waste wood—44.
15 For nonsalt laden wood, the mean of the emission factors derived from the four CARB
16 studies and five NCASI studies (assuming nondetect values were zero) is
17 0.6 ng WHO98 TEQDF/kg wood (0.56 ng I-TEQDF/kg wood) and is used in this document as the
18 most representative of industrial wood combustion for all reference years.
19 NCASI (1995) concluded that CDD/CDF emissions from facilities burning salt-laden
20 wood residue may be considerably higher than those from facilities burning salt-free wood. The
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1 overall average of the five tested facilities in Canada (Luthe et al., 1998) and the United States
2 (U.S. EPA, 1987), 13.2 ng I-TEQop/kg of wood, was applied to all three reference years. Based
3 on the congener profile reported by Luthe et al. (1998), this converts to 15.3 ng WHO9g TEQ/kg.
4 Similarly, no change was made to the activity estimate for salt laden wood. However, the
5 activity estimate for nonsalt laden wood was changed for all years to reflect more recent data in
6 EIA (2008c). Values are reported in the release summary below.
7
8 4.2.2.2. Water Literature—None
9
10 4.2.2.3. Solid Residue Releases
11 As indicated in U.S. EPA (2006), the ash concentrations from the NCASI Handbook
12 (13.2 ng WHOgg TEQop/kg) appears to fall within the range of values reported in the various
13 studies and a reasonable value for mixed bottom and fly ash. Oeheme and Muller (1995)
14 measured CDD/CDF levels in ash from wood-fired boilers in Switzerland. The levels in bottom
15 ash were on the order of 1 ng I-TEQ/kg when natural wood was incinerated. However, in filter
16 ash the levels were about two orders of magnitude higher. Burning of waste wood from house
17 demolition and construction resulted in concentrations in the range of 1-10 ng I-TEQ/kg.
18 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to
19 8% ash (Ragland et al, 1991). A mid-range value of 3% is assumed here for all wood burned.
20 Multiplying this percentage by the amount of wood consumed (as reported in the release
21 summary below) yields the ash production amounts for each reference year: 3.48 MMT in 1987,
22 3.51 MMT in 1995, and 3.48 MMT in 2000.
23 All ash from industrial wood combustion is assumed to be disposed in a secure landfill
24 and is, therefore, not considered an environmental release. However, the amounts of dioxin in
25 landfilled ash from industrial wood burning can be estimated by multiplying the ash
26 concentration and ash amounts presented above. This yields the following estimates:
27
28 • 1987—46 g WHO9g TEQDF/kg
29 • 1995—46 g WHO9g TEQoF/kg
30 • 2000—46 g WHO9g TEQoF/kg
31
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1 4.2.2.4. Release Summary
2 The inventory decision criteria and release estimates to all media are summarized below:
4
Inventory Decision Criteria for Industrial Wood Combustion
Air Water Solids Products
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
differences.
mission factor tests represent units that are typical of the Yes
class.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q_
5
6
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Industrial Wood Combustion
Air Releases
Emission Factor
Nonsalt-Laden Wood
• 1987—0.6 ng WHO98 TEQDF/kg (0.56 ng I-TEQDF/kg) of wood.
• 1995—0.6 ng WHO98 TEQDF/kg (0.56 ng I-TEQDF/kg) of wood.
• 2000—0.6 ng WHO98 TEQDF/kg (0.56 ng I-TEQDF/kg) of wood.
Salt-Laden Wood
• 1987—15 ng WHO98 TEQ/kg (13 ng I-TEQDF/kg) of wood.
• 1995—15 ng WHO98 TEQ/kg (13 ng I-TEQDF/kg) of wood.
• 2000—15 ng WHO98 TEQ/kg (13 ng I-TEQDF/kg) of wood.
Activity Level
Nonsalt-Laden Wood
• 1987—116 MMT.
• 1995—117 MMT.
• 2000—116 MMT.
Salt-Laden Wood
• 1987—0.5 MMT.
• 1995—0.5 MMT.
• 2000—0.8 MMT.
Releases
Nonsalt-Laden Wood
• 1987—70 g WH098 TEQDF (65 g I-TEQDF).
• 1995—70 g WHO98 TEQoF (65 g I-TEQDF).
• 2000—70 g WHO98 TEQoF (65 g I-TEQDF).
Salt-Laden Wood
• 1987—8 g WHO98 TEQoF (7 g I-TEQDF).
• 1995—8 g WHO98 TEQoF (7 g I-TEQDF).
• 2000—12 g WHO98 TEQDF (10 g I-TEQDF).
Total Industrial Releases
• 1987—78 g WHO98 TEQDF (72 g I-TEQDF).
• 1995—78 g WH098 TEQDF (72 g I-TEQDF).
• 2000—82 g WHO98 TEQDF (75 g I-TEQDF).
Water Releases
None.
Solid Residue Releases
All ash is assumed to be landfilled and, therefore, is not considered to be an environmental
release.
1
2
3
4
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Industrial Wood Combustion (continued)
Products
None.
1
2
3 4.3. OIL COMBUSTION
4 Section 4.1 covered combustion of gasoline and diesel fuels in engines. This section
5 addresses the combustion of other types of distillate oil products and residual fuel oils. These
6 products are burned primarily in furnaces or boilers in both residential/institutional settings and
7 in large industrial facilities. Distillate fuel oils are distilled from crude oil. Residual oils are
8 what remain of the crude oil after gasoline, and the distillate fuel oils are extracted through
9 distillation. Residual and distillate oils are further distinguished by grade: Numbers 1 and 2 are
10 distillate oils. No. 1 is similar to kerosene and is the fraction that boils off right after gasoline.
11 No. 2 is the diesel that trucks and some cars run on, leading to the name "road diesel"; this
12 category is addressed in Section 4.1.
13 Fuel Grades 5 and 6 are residual oils and sometimes referred to as "heavy fuel oils."
14 Number 6 fuel oil is sometimes referred to as Bunker C. Fuel Grade 4 is either distillate oil or a
15 mixture of distillate and residual oils. Distillate oils are more volatile and less viscous than
16 residual oils, which have negligible nitrogen and ash content, and usually contain less than
17 0.3% sulfur (by weight). Distillate oils are used mainly in domestic and small commercial
18 applications. The heavier residual oils (Grades 5 and 6), being more viscous and less volatile
19 than distillate oils, must be heated for ease of handling and to facilitate proper atomization.
20 Because residual oils are produced from the residue after the lighter fractions are removed from
21 the crude oil, they may contain significant quantities of ash, nitrogen, and sulfur.
22
23 4.3.1. Institutional/Commercial and Residential Oil Combustion
24 4.3.1.1. Air Releases
25 No changes were made to the emission factors. No testing for CDD/CDF emissions from
26 commercial or residential oil-fired combustion units in the United States could be located.
27 However, EPA (1997a) estimated CDD/CDF congener group and TEQ emission factors using
28 average CDD/CDF concentrations reported for soot samples from 21 distillate fuel oil-fired
29 furnaces used for central heating in Canada and a PM emission factor for distillate fuel oil
30 combustors (300 mg/L oil) obtained from AP-42 (U.S. EPA, 1995a). The TEQ emission factor
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1 estimate—0.19 ng WHOgg TEQop/L of oil (0.15 ng I-TEQop/L of oil)—was derived using the
2 calculated emission factors for 2,3,7,8-TCDD, 2,3,7,8-TCDF, and the 10 congener groups.
3 These results are near the upper end of the range from Pfeiffer et al. (2000) who measured
4 CDD/CDF emissions from oil fired household appliances used in Germany. Emission factors
5 were in the range of 0.025 to 0.135 ng I-TEQ/kg.
6 Minor updates were made to the activity estimates. EIA (2008a) data were used to derive
7 the activity levels. EIA supplied yearly data on total distillate fuel oil and total residual fuel oil
8 supplied in the United States. EIA also provided a breakdown of fuel oil sales by sector for the
9 years back to 2001. The sector percentages for 2001 were assumed to apply to each of the
10 reference years. These percentages were multiplied by the totals (also used conversion factors of
11 42 gal/barrel and 3.79 L/gal) to estimate the amount of distillate fuel oil consumed in the
12 residential and commercial sectors. On this basis, the following estimates were made for each
13 reference year: 1987—29.4 billion L, 1995—31.7 billion L, and 2000—36.9 billion L.
14
15 4.3.1.2. Water Releases—None
16
17 4.3.1.3. Solid Residue Releases—None
18
19 4.3.1.4. Products—None
20
21 4.3.1.5. Release Summary
22 The inventory decision criteria and release estimates are summarized below:
23
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Inventory Decision Criteria for Institutional/Commercial and Residential Oil Combustion
Air Water Solids Products
Emission tests for at least two units/source types with sufficient
documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
1
2
Institutional/Commercial and Residential Oil Combustion
Air Releases
Emission Factors
• 1987—190 pg WHO98 TEQDF/L (150 pg I-TEQDF/L) of oil combusted.
• 1995—190 pg WHO98 TEQDF/L (150 pg I-TEQDF/L) of oil combusted.
• 2000—190 pg WHO98 TEQDF/L (150 pg I-TEQDF/L) of oil combusted.
Activity Levels
• 1987—29.4 billion L.
• 1995—31.7 billion L.
• 2000—36.9 billion L.
Releases
• 1987—6 g WH098 TEQDF (4 g I-TEQDF).
• 1995—6 g WHO98 TEQoF (5 g I-TEQDF).
• 2000—7 g WHO98 TEQoF (6 g I-TEQDF).
Water Releases
These facilities do not have wastewater releases.
Solid Residue Releases
These facilities do not have solid releases.
Products
None.
4
5 4.3.2. Utility Sector and Industrial Oil Combustion
6 Minor changes were made to the activity estimates as explained below.
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1 4.3.2.1. Air Literature
2 In 1993, the Electric Power Research Institute (EPRI) sponsored a project to gather
3 information of consistent quality on power plant emissions. The Field Chemical Emissions
4 Measurement (FCEM) project included testing of two cold-sided, ESP-equipped, oil-fired power
5 plants for CDD/CDF emissions. EPA (1997a) reports on testing at oil fired utility boilers for a
6 variety of furnace configurations and APCDs.
7 Some boilers use low-NOx burners, which reduce flame turbulence, delay fuel/air
8 mixing, and establish fuel-rich zones within the boiler during initial combustion. The longer,
9 less intense flames that result from the altered combustion lower flame temperatures and reduce
10 thermal NOx formation (Colburn, 1996), Because low-NOx burners reduce temperatures and,
11 thus, the completeness of combustion the potential exists for increased CDD/CDF formation.
12 However, this has not yet been evaluated via stack testing.
13
14 4.3.2.2. Air Emission Factor
15 EPA (2006) based the emission factor on the average of the EPRI (1994) and EPA
16 (1997a) studies. The emission factor—230 pg WHOgg TEQop/L oil combusted
17 (200 pg I-TEQop/L oil combusted)—was applied to all three reference years.
18
19 4.3.2.3. Activity Level
20 Updated EIA data were used to derive the activity levels. EIA supplied yearly data on
21 total distillate fuel oil and total residual fuel oil supplied in the United States. EIA also provided
22 a breakdown of fuel oil sales by sector for the years back to 2001. The sector percentages for
23 2001 were assumed to apply to each of the reference years. Multiplying these percentages by the
24 totals yields the following estimates for each reference year (also used conversion factors of
25 42 gal/barrel and 3.79 L/gal):
26
27 Distillate Fuel Oil—Industrial and Electric Power Use
28
29 • 1987—10.4 billion L
30 • 1995—11.2 billion L
31 • 2000—13.0 billion L
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1 Residual Fuel Oil—Total
2
3 • 1987—73.4 billion L
4 • 1995—49.5 billion L
5 • 2000—53.0 billion L
6
7 4.3.2.4. Air Releases
8 The air releases were estimated by multiplying the emission factor and activity estimates.
9
10 4.3.2.5. Water Releases—None
11
12 4.3.2.6. Solid Residue Releases—None
13
14 4.3.2.7. Products—None
15
16 4.3.2.8. Release Summary
17 The inventory decision criteria and release estimates are summarized below:
18 |
Inventory Decision Criteria for Utility Sector and Industrial Oil Combustion
Air Water Solids Products
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
differences.
mission factor tests represent units that are typical of the Yes
class.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q_
19
20
21
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Utility Sector and Industrial Oil Combustion
Air Releases
Emission Factors
• 1987—230 pg WHO98 TEQDF/L (200 pg I-TEQDF/L) of oil combusted.
• 1995—230 pg WHO98 TEQDF/L (200 pg I-TEQDF/L) of oil combusted.
• 2000—230 pg WHO98 TEQDF/L (200 pg I-TEQDF/L) of oil combusted.
Activity Level
• 1987—83.8 billion L.
• 1995—60.7 billion L.
• 2000—66.0 billion L.
Releases
• 1987—19 g WH098 TEQDF (17 g I-TEQDF).
• 1995—14 g WHO98 TEQDF (12 g I-TEQDF).
• 2000—15 g WHO98 TEQDF (13 g I-TEQDF).
Water Releases
These facilities do not have wastewater releases.
Solid Residue Releases
These facilities do not have solid releases.
Products
These facilities do not have products.
1
2
3 4.3.3. Waste Oil Combustion
4 Waste oil includes used crankcase oils from automobiles and trucks, used industrial
5 lubricating oils (such as metal working oils), and other used industrial oils (such as heat transfer
6 fluids). When discarded, these oils become waste oils due to a breakdown of physical properties
7 and contamination by the materials they come in contact with. The different types of waste oils
8 may be burned as mixtures or as single fuels where supplies allow. Waste, or used, oil can be
9 burned in a variety of combustion systems including industrial boilers; commercial/institutional
10 boilers; space heaters; asphalt plants; cement and lime kilns; other types of dryers and calciners;
11 and steel-production blast furnaces (U.S. EPA, 1998c). USDOE (2006) reports the following
12 breakout for 2006 in billions of gallons:
13
14 Asphalt Plants - 0.286
15 Space Heaters -0.113
16 Industrial Boilers -0.093
17 Utility Boilers -0.080
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1 Steel Mills -0.080
2 Cement Kilns -0.033
3 Others - 0.095 (includes: marine boilers, pulp & paper mills, commercial boilers)
4
5 Total - 0.780
6
7 CDD/F emissions from all of these facility types except space heaters were covered in other parts
8 of this document. So this section will address only releases from space heaters.
9
10 4.3.3.1. Air Literature
11
12 Bremmer et al. (1994) measured the CDD/CDF emissions from the combustion of used
13 oil by small combustion units in the Netherlands. Flue gases from a garage stove consisting of
14 an atomizer fueled by spent lubricating oil from diesel engines (35 mg ClVkg) were reported to
15 contain 0.1 ng I-TEQoF/Nm3 (2 ng I-TEQop/kg) oil burned. The flue gases from a hot water
16 boiler consisting of a rotary cup burner fueled with the organic phase of rinse water from oil
17 tanks (340 mg ClVkg) contained 0.2 ng I-TEQDF/Nm3 (4.8 ng I-TEQDF/kg) oil burned. The flue
18 gases from a steam boiler consisting of a rotary cup burner fueled by processed spent oil (240 mg
19 ClVkg) contained 0.3 ng I-TEQDF/Nm3 (6 ng I-TEQop/kg) oil burned. The emission factor for a
20 ferry burning heavy fuel oil containing 11 ng/kg organic chlorine was 3.2 to 6.5 ng I-TEQop/kg
21 oil burned. From these data, Bremmer et al. (1994) derived an average emission factor for
22 combustion of used oil of 4 ng I-TEQop/kg oil burned.
23 Measured data from the burning of recycled waste oils are available from Austria, where
24 emissions from a small incinerator gave a concentration of 0.02 ng TEQ/Nm3 (at 11% 02)
25 equivalent to an emission factor of 0.37 ng TEQ/kg of waste oil burned (LUA, 1997).
26
27
28 4.3.3.2. Air Emission Factor
29
30 The emission factor measured by Bremmer et al. (1994) for small combustion units was
31 selected as most relevant to space heaters, i.e. 2 ng I-TEQop/kg. Based on the limited data from
32 only one study and uncertainty about how the units tested by Bremmer et al. compare to space
33 heaters in the U.S., this is considered to be a preliminary estimate.
34
35
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1 4.3.3.3. Activity Level
2
3 The total amount of waste oil burned in 1983 was 0.59 billion gallons (USEPA, 1993).
4 Comparing this estimate with the 2006 estimate (described above) and assuming linear growth,
5 implies that used oil combustion has increased at a rate of about 1.4% per year. The 2006 data
6 indicates that 14.5 % of the total waste burned was in space heaters. Assuming this percentage
7 remains constant and using the annual growth rate, allows estimates of the amount of oil burned
8 in space heaters for each of the reference years (converted to kg based on 3.78 L/gal and density
9 of0.88kg/L):
10
11 1987-0.30 billion kg
12 1995-0.33 billion kg
13 2000-0.35 billion kg
14
15 Based on the lack of survey data specific to the reference years and facility types, these estimates
16 are considered preliminary.
17
18
19 4.3.3.4. Air Releases
20
21 The air releases were estimated by multiplying the emission factor and activity estimates.
22
23 4.3.3.5. Water Releases - None
24
25 4.3.3.6. Solid Residue Releases-None.
26
27 4.3.3.7. Products-None.
28
29 4.3.3.8. Release Summary
30
31 The inventory decision criteria and release estimates are summarized below:
32
33
Inventory Decision Criteria for Waste Oil Combustion
Air Water Solids Product
Emission tests for at least two units/source types with No
sufficient documentation to directly derive emission factors
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Inventory Decision Criteria for Waste Oil Combustion
Measured emission factors consistent or have Yes
understandable differences
Emission factor tests represent units that are typical of the No
class
Activity estimates based on source-specific surveys No
Conclusion (Q = Quantitative, P = Preliminary)
1
2
Emission Factors
• 1987 - 2 ng I-TEQop/kg oil combusted (Preliminary)
• 1995 - 2 ng I-TEQop/kg oil combusted (Preliminary)
• 2000 - 2 ng I-TEQpp/kg oil combusted (Preliminary)
Waste Oil Combustion
Air Releases
Activity Levels
• 1987-0.30 billion kg (Preliminary)
• 1995 - 0.33 billion kg (Preliminary)
• 2000-0.35 billion kg (Preliminary)
Releases
• 1987-0.60 g I-TEQDF (Preliminary)
• 1995 - 0.66 g I-TEQDF (Preliminary)
• 2000 - 0.70 g I-TEQpF (Preliminary)
Water Releases
These facilities do not have wastewater releases.
Solid Residue Releases
These facilities do not have solid releases.
Products
These facilities do not have products.
4
5
6
7 4.4. COAL COMBUSTION
8 4.4.1. Coal-Fired Power Plants
9 No changes were made to the air emission factors or activity estimates, but additional
10 background information is provided. Minor changes were made to the activity estimates for
11 solid residues resulting in minor changes in residue amounts.
12
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1 4.4.1.1. Air Releases
2 UNEP (2005) reports that Dutch data from large coal-fired power plants gave an
3 emission factor of 0.35 ug I-TEQ/MT; German data were between 0.004 and 0.2 ug I-TEQ/MT ,
4 and U.K. data had a median value of 0.14 ug I-TEQ/MT (range: 0.06-0.32 ug I-TEQ/MT).
5 As discussed in EPA (2006), EPRI and DOE data were used to derive an emission factor
6 of 0.078 ng WHO9g TEQDF/kg of coal combusted (0.079 ng I-TEQDF/kg). This is an average
7 over 11 U.S. facilities, but it is on the low end of the range reported in UNEP (2005) for
8 European facilities. Thus, there is some concern that this emission factor may be an
9 underestimate. One reason why it may be low is because all of the tested facilities had
10 cold-sided ESPs and experience in other industries suggested that higher emissions were likely
11 from facilities with hot-sided ESPs. In recognition of this concern, EPA/Department of Energy
12 (DOE) conducted testing of stack emissions in 1999 at the coal-fired Presque Island electric
13 utility boiler in Wisconsin, which was equipped with a hot-sided ESP. The testing showed no
14 increases in dioxin concentrations from the flue gas inlet to the outlet of a hot-sided ESP
15 (personal communication from Thomas Feeley, National Energy Technical Laboratory,
16 U.S. Department of Energy, Pittsburgh, PA to David Cleverly, National Center for
17 Environmental Assessment, U.S. Environmental Protection Agency, Washington, DC on
18 December 17, 2008). Accordingly, it is assumed that the TEQ emission factor for coal fired
19 utilities with hot-sided ESPs is of the same order of magnitude as the average TEQ emission
20 factors derived above.
21 In the year 2000, 10 facilities with an SIC code for electric services reported dioxin
22 releases under the EPA TRI program (U.S. EPA, 2008). The sum of the air releases across these
23 facilities was 63.2 g, which EPA estimates is equal to 8.9 g WHOgg TEQop No releases to other
24 media were reported. Also, in the year 2000, two facilities with an SIC code for electric and
25 other services combined reported dioxin releases under EPA's TRI program (U.S. EPA, 2008).
26 The sum of the air releases across these facilities was 457 g, which EPA estimates is equal to
27 22.2 g WHOgg TEQop. No releases to other media were reported. As explained in Chapter 1, the
28 TRI data are not used to make quantitative estimates in this document but rather as supportive
29 evidence that releases do occur.
30 The activity estimates were derived from EIA (1999b).
31
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1 4.4.1.2. Water Releases
2 No data on CDD/CDF levels in water releases from these facilities were found. Because
3 CDD/CDFs are found in the air emissions from these facilities, it is possible they could also be
4 found in scrubber waters. Thus, water releases of CDD/CDFs from these facilities are
5 considered possible but unquantifiable.
6
7 4.4.1.3. Solid Residue Releases
8 Dyke et al. (1997) provided data on residues from industrial coal combustion in the
9 United Kingdom: Concentrations in fly ash were 0.23-8.7 ng TEQ/kg ash, and grate ash were
10 0.02-13.5 ng TEQ/kg. UNEP (2005) used these data to derive an average value of
11 4 ng I-TEQ/kg. A limited amount of CDD/CDF concentration data have been developed for ash
12 from coal combustion facilities in the United States (U.S. EPA, 1999c), and these data are for
13 wastes that are comanaged (i.e., combinations of fly ash, bottom ash, boiler slag, and flue gas
14 desulfurization wastes). A total of 15 samples were taken from 11 disposal sites. The total mean
15 concentration was 0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg).
16 The total mean concentration from EPA (1999c) was selected as the only U.S. data
17 available and within the range reported for the United Kingdom. This value of
18 0.73 ng WHOg TEQop/kg (0.62 ng I-TEQop/kg) was assumed to apply to all reference years.
19 The American Coal Ash Association (ACAA—http://www.acaa-usa.org/) releases annual
20 production and use estimates for coal ash. Production estimates for the reference years are as
21 follows:
22
23 • 1987—75.4 MMT
24 • 1995—83.6 MMT
25 • 2000—98.2 MMT
26 According to ACAA, between 25 and 30% of industrial coal ash was recycled in a variety
27 of ways including use in cement, grout, road base materials, manufactured aggregate, fill
28 material, snow/ice control, and agriculture. These amounts were estimated as 30% of the total
29 ash:
30
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1 • 1987—22.6 MMT
2 • 1995—25.1 MMT
3 • 2000—29.5 MMT
4
5 The potential for environmental releases from these uses is unknown, but it is assumed here that
6 all of the CDD/CDF in the recycled ash represent an environmental release (release estimates are
7 shown in the summary below). The emission factor presented above is based on recent testing at
8 11 disposal sites, but it is uncertain how much actual release occurs from these products.
9 The ash that was not recycled was disposed of in landfills, and these residues are not
10 considered environmental releases. These amounts were multiplied by the ash emission factor
11 (presented above) to get the amount landfilled (on a TEQ basis):
12
13 • 1987—38.5 g WHO98 TEQDF (32.7 g I-TEQDF)
14 • 1995—42.7 g WHO98 TEQDF (36.3 g I-TEQDF)
15 • 2000—50.2 g WHO98 TEQDF (42.6 g I-TEQDF)
16
17 4.4.1.4. Product Literature—None
18
19 4.4.1.5. Release Summary
20 The inventory decision criteria and release estimates for all media are summarized below:
21
22
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Inventory Decision Criteria for Industrial Coal-Fired
Utilities
Air Water Solids Products
Emission tests for at least two units/source types with sufficient Yes
documentation to directly derive emission factors.
Measured emission factors consistent or have understandable Yes
differences.
Emission factor tests represent units that are typical of the class. Yes
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
Yes
Yes
Yes
Yes
Q
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Industrial Coal-Fired Utilities
Air Releases
Emission Factor
• 1987—0.078 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg).
• 1995—0.078 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg).
• 2000—0.078 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg).
Activity Levels
• 1987—651 MMT.
• 1995—771 MMT.
• 2000—894 MMT.
Releases
• 1987—51 g WHO98 TEQDF (51 g I-TEQDF).
• 1995—60 g WHO98 TEQDF (61 g I-TEQDF).
• 2000—70 g WHO98 TEQDF (71 g I-TEQDF).
Water Releases
because some evidence exists that wastewater from these facilities may contain CDDs and
'DFs, they are classified as possible but unquantifiable (Not quantifiable) sources.
Solid Residue Releases
Emission Factor
• 1987—0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) of ash.
• 1995—0.73 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg) of ash.
• 2000—0.73 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg) of ash.
Activity Levels
• 1987—22.6 MMT ash.
• 1995—25.1 MMT ash.
• 2000—29.5 MMT ash.
Releases
• 1987—17 g WHO98 TEQoF (14 g I-TEQDF).
• 1995—18 g WHO98 TEQoF (16 g I-TEQDF).
• 2000—22 g WHO98 TEQDF (18 g I-TEQDF).
1
2
3 4.4.2. Coal-Fired Industrial Boilers
4 4.4.2.1. Air Releases
5 No changes were made to the air emission factors, but they were upgraded from a
6 confidence rating of preliminary to quantifiable. This was because they were based on a
7 reasonably large study (n = 15) from the U.K. (CRE, 1994) and the likelihood that the
8 technologies were similar to U.S. facilities. The activity estimates were updated using EIA
9 (2006), which indicated that the amount of coal burned in industrial utilities was 68.2 MMT in
10 1987, 66.3 MMT in 1995, and 59.2 MMT in 2000.
11
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1 4.4.2.2. Water Literature
2 No data on CDD/CDF levels in water releases from these facilities were found. Because
3 CDD/CDFs are found in the air emissions from these facilities, it is possible they could also be
4 found in scrubber waters. Thus, water releases of CDD/CDFs from these facilities are
5 considered possible but unquantifiable.
6
7 4.4.2.3. Solid Residue Releases
8 No data on the CDD/CDF content of ash from industrial boilers were found; however,
9 this should be similar to the values presented in Section 4.4.1 for coal-fired utilities. Also, the
10 activity estimates presented for coal-fired utilities include ash from all coal combustion used to
11 generate electricity. Thus, they should represent most of the industrial utility boilers. So it is
12 assumed that the solid residue releases presented for the utilities include the releases from
13 industrial boilers (see Section 4.4.1).
14
15 4.4.2 A. Release Summary
16 The inventory decision criteria and release estimates for all media are summarized below:
17
Inventory Decision Criteria for Industrial Coal-Fired Boilers
Air Water Solids Products
Emission tests for at least two units/source types with sufficient Yes
documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
ifferences.
Emission factor tests represent units that are typical of the Yes
;lass.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
18
19
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Industrial Coal-Fired Boilers
Air Releases
Emission Factors
• 1987—0.7 ng WHO98 TEQDF/kg (0.6 ng I-TEQDF/kg)of coal combusted.
• 1995—0.7 ng WHO98 TEQDF/kg (0.6 ng I-TEQDF/kg) of coal combusted.
• 2000—0.7 ng WHO98 TEQDF/kg (0.6 ng I-TEQDF/kg) of coal combusted.
Activity Levels
• 1987—68.2 MMT.
• 1995—66.3 MMT.
• 2000—59.2 MMT.
Releases
leases
• 1987—48 g WHO98 TEQDF (41 g I-TEQDF).
• 1995—46 g WHO98 TEQDF (40 g I-TEQDF).
• 2000—41 g WHO98 TEQpp (36 g I-TEQDF).
Water ]
Water Releases
ecause some evidence exists that wastewater from these facilities may contain CDDs and
CDFs, they are classified as possible but unquantifiable sources.
Solid Residue Releases
These releases are included in the estimates for coal-fired utilities presented in Section 4.4.1.
Products
No information was found suggesting that products from these facilities would contain CDDs
and CDFs.
2
3
4 4.4.3. Residential Coal Combustion
5 4.4.3.1. Air Releases
6 No changes were made to the air emission factor, but it was upgraded from preliminary to
7 quantitative. Also a new study was found as summarized below.
8 Paradiz et al. (2008) measured CDD/F emissions from a coal fired domestic stove. The
9 study was conducted in Italy using a high chlorine content coal. Testing with a non-insulated
10 chimney yielded an emission factor of 1326 I-TEQ jig/ton of coal burned. Testing with an
11 insulated chimney yielded an emission factor of 126 I-TEQ jig/ton of coal burned. A
12 pronounced effect of the temperature profile in the chimney on PCDD/F emissions was
13 identified, suggesting formation in the chimney.
14
15 As discussed in the original document, the emission factor was based on an analysis by
16 Eduljee and Dyke (1996) on data from the Coal Research Establishment in the United Kingdom
17 (2.1 ng I-TEQop/kg for anthracite coal and 5.7 to 9.3 ng I-TEQop/kg [midpoint,
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1 7.5 ng I-TEQop/kg] for bituminous coal). Wevers et al. (2003) measured CDD/CDF emissions
2 from various types of household appliances used in Belgium. The average emission factor for
3 anthracite coal burners was 77.1 ng I-TEQ/kg. UNEP (2005) reports that European studies
4 generally show a range of 1.6 to 50 ng TEQ/kg for typical coal and emission factors as high as
5 660 ng I-TEQ/kg for high chlorine coals. Ultimately UNEP (2005) recommends 3 ng I-TEQ/kg
6 for domestic burning with typical coals. Based on the similarity of the emission factor data
7 summarized by UNEP for typical coals and estimates by Eduljee and Dyke (1996), the emission
8 factor was upgraded from preliminary to quantitative. The congener data for emissions from
9 normal lignite (Thub et al., 1995), indicate that the WHOgg TEQs were less than 9% higher than
10 the I-TEQs. Based on this small difference, the I-TEQ emission factor was assumed to be
11 essentially equivalent when expressed as WHOgg TEQs.
12 The activity estimates were updated using EIA (2006), which indicated that the amount
13 of coal burned at residences was 1.6 MMT in 1987, 0.8 MMT in 1995, and 0.5 MMT in 2000.
14 EPA (1997a) reported that 72.5% of the coal consumed by the residential sector in 1990 was
15 bituminous and 27.5% was anthracite. These factors were assumed to apply to all reference
16 years.
17
18 4.4.3.2. Water Releases—None
19
20 4.4.3.3. Solid Residue Releases
21 The solid residues from coal-fired utility boilers are likely to be similar to the solid
22 residues from residential units. On this basis, the same emission factor is assumed to apply, i.e.,
23 0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg). UNEP (2005) suggests a "first estimate"
24 emission factor for residues from coal fired stoves of 5,000 ng I-TEQ/kg. This is based on
25 measurements in soot, which may not be representative of bottom ash. A preliminary confidence
26 rating is assigned to this emission factor because it is based on testing from different facilities.
27 The total amount of ash generated by these facilities is assumed to be 10% of the total
28 coal used. On this basis, the solid residues are estimated to be 0.16 MMT in 1987, 0.08 MMT in
29 1995, and 0.05 MMT in 2000. Some of this ash is likely to be disposed along with household
30 trash and taken to a municipal landfill. This portion would not be considered an environmental
31 release. Others may dispose of it on their property in a manner that is open to the environment.
This document is a draft for review purposes only and does not constitute Agency policy.
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1
2 4.4.3.4. Products—None
O
4 4.4.3.5. Release Summary
5 The inventory decision criteria and release estimates for all media are summarized below:
Inventory Decision Criteria for Residential Coal Combustion
Emission tests for at least two units/source types with sufficient
documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Air
Yes
Yes
Yes
Yes
Q
Water Solids Products
No
No
Yes
P
This document is a draft for review purposes only and does not constitute Agency policy.
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Residential Coal Combustion
Air Releases
Emission Factors
Anthracite
• 1987—2.1 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg).
• 1995—2.1 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg).
• 2000—2.1 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg).
Bituminous
• 1987—7.5 ng WHO98 TEQDF/kg (7.5 ng I-TEQDF/kg).
• 1995—7.5 ng WHO98 TEQDF/kg (7.5 ng I-TEQDF/kg).
• 2000—7.5 ng WHO98 TEQDF/kg (7.5 ng I-TEQDF/kg).
ai7«klc
Activity Levels"
• 1987—1.6 MMT.
• 1995—0.8 MMT.
•_ 2000—0.5 MMT.
Releases
1987—10 g WHO98 TEQDF or I-TEQDF.
1995—5 g WHO98 TEQDF or I-TEQDF.
2000—3 g WHO98 TEQDF or I-TEQDF.
Water R<'
Water Releases
These facilities do not have wastewater releases.
Solid Residue Releases
Emission Factors
• 1987—0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) (Preliminary).
• 1995—0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) (Preliminary).
• 2000—0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) (Preliminary).
Activity Levels
• 1987—0.16 MMT.
• 1995—0.08 MMT.
• 2000—0.05 MMT.
Releases
• 1987—0.1 g WHO98 TEQDF (0.1 g I-TEQDF) (Preliminary).
• 1995—0.1 g WHO98 TEQoF (0.1 g I-TEQDp) (Preliminary).
• 2000— <0.1 g WHO98 TEQDF (<0.1 g I-TEQp) (Preliminary).
Products
These facilities do not have products.
2 aNote: 72.5% of the coal burned is bituminous, and 27.5% is anthracite.
3 bNote: An unknown portion of this is landfilled and, therefore, is not considered a release to the open environment.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5. COMBUSTION SOURCES OF CDDS/CDFS: OTHER
2 HIGH-TEMPERATURE SOURCES
O
4
5 5.1. CEMENT KILNS
6 5.1.1. Air Releases
7 No changes were made to the air-release estimates from cement kilns. However,
8 additional background information is provided below.
9 The present report uses higher emission factors for cement kilns burning hazardous waste
10 in 1987 and 1995 than kilns not burning hazardous waste (emission factors were not needed in
11 2000 for hazardous waste burners because virtually all facilities had been tested). As discussed
12 below, these higher emissions were more likely due to APCD temperatures than the hazardous
13 waste.
14 World Business Council for Sustainable Development (2006) evaluated 2,200 CDD/CDF
15 measurements made at cement kilns from the late 1970s until recently. This report concluded
16 that coprocessing of alternative fuels and raw materials, fed to the main burner, kiln inlet or the
17 precalciner does not influence or change the emissions of persistent organic pollutants (POPs).
18 EPA (1999) also concluded that hazardous waste burning at cement kilns is not likely to affect
19 emissions of dioxins/furans. Rather, these reports conclude that reducing the temperature at the
20 inlet of the air pollution control device is one factor shown to have a significant impact on
21 limiting dioxin formation and emissions at all types of cement kilns, independent of waste
22 feeding. Lower APCD temperatures are believed to prevent the postcombustion catalytic
23 formation of CDD/CDFs. This is supported by emissions testing at a Portland cement kiln which
24 showed that CDDs/CDFs were almost entirely absent at the inlet to a hot-sided ESP, but
25 measurements taken at the exit showed conclusively that dioxins were formed within the
26 hot-sided ESP (U.S. EPA, 1997b). After 1995, a number of cement kilns added exhaust
27 gas-quenching units upstream of the APCD to reduce the inlet APCD temperature, thereby
28 reducing CDD/CDF stack concentrations.
29 UNEP (2005) also concluded that APCD temperature is the key factor affecting
30 CDD/CDF emissions and recommended emission factors on this basis:
31
This document is a draft for review purposes only and does not constitute Agency policy.
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1 • ESP temperature <200°C—0.05 ng I-TEQ/kg of clinker
2 • ESP temperature 200-300°C—0.6 ng I-TEQ/kg of clinker
3 • ESP temperature >300°C—5 ng I-TEQ/kg of clinker
4
5 In the year 2000, nine facilities with an SIC code for "cement, hydraulic" reported dioxin
6 releases under the EPA TRI program (U.S. EPA, 2008). The total air releases across these
7 facilities was 201 g, which EPA estimates is equal to 36 g WHOgg TEQop No releases to other
8 media were reported. As explained in Chapter 1, the TRI data are not used to make quantitative
9 estimates in this document, but, rather, the data are offered as supportive evidence that releases
10 do occur.
11 For kilns burning hazardous waste, the emission factors were derived using test report
12 data from 1989-1996 (U.S. EPA, 1996a). These data provided APCD inlet temperature data for
13 88 test runs at 14 cement kilns and allowed development of emission factors for kilns with
14 APCD inlet temperatures greater than 232°C and for kilns with APCD inlet temperatures less
15 than 232°C. These were used in 1987 and 1995. In 2000, almost all of the facilities had been
16 tested, and it was unnecessary to use an emission-factor/activity-level approach to derive release
17 estimates (U.S. EPA, 2002a).
18 For the kilns not burning hazardous waste, insufficient information was available to
19 derive temperature-specific emission factors, and the same emission factor was assumed to apply
20 to all facilities. This was derived from data in Bell (1999) and EPA (1996b) on a total of
21 16 facilities. The lack of temperature data for the kilns not burning hazardous waste introduces
22 uncertainty into the emission-factor assumption and may be an underestimate if the testing did
23 not include facilities with high-temperature control devices.
24 The activity data for clinker production were derived from information provided by U.S.
25 DOC (1996) and Portland Cement Association (2001). All emission factors, activities, and
26 release estimates are shown in the release summary below.
27
28 5.1.2. Water Releases
29 It is possible that the effluent from the APCD systems at these facilities contains CDDs
30 and CDFs because they have been measured in the stack gases. No information was found on
31 the levels in the effluent, so this is considered a possible but unquantifiable source.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.1.3. Solid Residue Releases
2 No changes were made to the solid residue release estimates from cement kilns.
3 However, additional background information is provided below.
4 Cement kiln dust (CKD) is the solid residual material collected by the APCD system of a
5 cement kiln. Gross CKD (or as-generated CKD) is either recycled back into the kiln system or
6 removed from the system for disposal (becoming net CKD or as-managed CKD). Most of the
7 net CKD is disposed in secure landfills, but some is used for a variety of beneficial purposes
8 such as municipal waste daily cover material, municipal waste landfill final cover material, soil
9 stabilization for roadways or other structures, waste neutralization/stabilization/solidification
10 (e.g., food wastes, hazardous wastes, etc.), and agricultural soil amendment. It is assumed that
11 CDD/CDF releases could occur during the beneficial uses but not from the landfilled portions.
12 As discussed in EPA, 2006 data on the amounts of CKD used for beneficial purposes was
13 provided by the Portland Cement Association and split between kilns burning and not burning
14 hazardous waste based on the relative amounts of clinker produced.
15 A wide range of CDD/PCDF concentrations in the CKD has been measured. A range
16 from 0.001 to 30 ng TEQ/kg has been reported for U.K. kilns (Dyke et al., 1997), and
17 1-40 ng TEQ/kg were summarized for German tests (SCEP, 1994). As discussed in EPA
18 (2006), for kilns burning hazardous waste, the CKD concentration is assumed to be
19 35 ng I-TEQ/kg (n = 5), and for the kilns not burning hazardous waste, the CKD concentration is
20 assumed to be 0.003 ng I-TEQ/kg (n = 6). These emission factors were applied to all reference
21 years. They are considered preliminary because of the inconsistency in measured values and
22 lack of understanding for the differences. The dioxin concentrations in CKD were also used to
23 estimate the amounts of CDD/CDFs in landfilled CKD, as shown below:
24
1987
1995
2000
Kilns burning hazardous waste
CKD activity
(million kg)
426
505
365
Landfilled
(gl-TEQ)
14.9
17.7
12.8
Kilns not burning hazardous waste
CKD activity
(million kg)
2,230
2,642
1,858
Landfilled
(gl-TEQ)
0.007
0.008
0.006
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.1.4. Products
2 Clinker is the primary product of cement kilns and is ultimately used to make Portland
3 cement. EPA (1993a) described the results of sampling and analysis of clinker conducted in
4 1992 and 1993. Clinker samples were collected from five cement kilns burning nonhazardous
5 waste and six kilns burning hazardous waste. CDDs/CDFs were not detected in any of the
6 samples. Some of the CKD is beneficially reused as discussed above. Releases associated with
7 beneficial uses of CKD are covered under the solid residue section.
8
9 5.1.5. Release Summary
10 The inventory decision criteria and releases to all media are summarized below:
11
Inventory Decision Criteria for
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Cement Kilns
Air Water
Yes
Yes
Yes
Yes
Q
Solids Products
Yes
No
Yes
Yes
P
12
13
This document is a draft for review purposes only and does not constitute Agency policy.
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Cement Kilns Not Burning Hazardous Waste
Air Releases
Emission Factor
• 1987—0.27 ng WHO98 TEQDF/kg (0.26 ng I-TEQ/kg) of clinker produced.
• 1995—0.27 ng WHO98 TEQDF/kg (0.26 ng I-TEQ/kg) of clinker produced.
• 2000—0.27 ng WHO98 TEQDF/kg (0.26 ng I-TEQ/kg) of clinker produced.
Activity Levels
• 1987—47.2 billion kg of clinker.
• 1995—61.3 billion kg of clinker.
• 2000—63.7 billion kg of clinker.
Releases
• 1987—13 g WHO98 TEQDF/yr (12 g I-TEQDF/yr).
• 1995—17 g WHO98 TEQDF/yr (16 g I-TEQDF/yr).
• 2000—17 g WHO98 TEQDF/yr (17 g I-TEQDF/yr).
Water Releases
It is possible that the effluent from the APCD systems at these facilities contains CDDs and
CDFs because they have been measured in the stack gases. No information was found on levels
in the effluent, so this considered a possible but unquantifiable source.
Solid Residue Releases
Emission Factor
• 1987—0.003 ng I-TEQ/kg (Preliminary).
• 1995—0.003 ng I-TEQ/kg (Preliminary).
• 2000—0.003 ng I-TEQ/kg (Preliminary).
Activity Levels
• 1987—632 million kg.
• 1995—547 million kg.
• 2000—480 million kg.
Releases for Beneficial Uses
• 1987—<0.1 g I-TEQ (Preliminary).
• 1995—<0.1 g I-TEQ (Preliminary).
• 2000—<0.1 g I-TEQ (Preliminary).
Products
No information was found suggesting that clinker contained measureable levels of CDDs and
CDFs. Beneficial uses of CKD are covered under solid residues.
1
2
3
This document is a draft for review purposes only and does not constitute Agency policy.
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Cement Kilns Burning Hazardous Waste
Air Releases
Emission Factors
• 1987—APCD > 232°C: 31 ng WHO98 TEQDF/kg (29 ng I-TEQ/kg) of clinker produced.
APCD < 232°C: 1.1 ng WHO98 TEQDF/kg (1.0 ng I-TEQ/kg) of clinker produced.
• 1995—APCD > 232°C: 31 ng WHO98 TEQDF/kg (29 ng I-TEQ/kg) of clinker produced.
APCD < 232°C: 1.1 ng WHO98 TEQDF/kg (1.0 ng I-TEQ/kg) of clinker produced.
• 2000—EFs not needed because all individual facilities were tested.
Activity Levels
• 1987—APCD > 232°C: 3.8 billion kg of clinker.
APCD < 232°C: 1 billion kg of clinker.
• 1995—APCD > 232°C: 5.04 billion kg of clinker.
APCD < 232°C: 1.26 billion kg of clinker.
• 2000—Activity estimates not needed because all individual facilities were tested.
Releases
• 1987—APCD > 232°C: 120 g WHO98 TEQDF/yr (110 g I-TEQDF/yr).
APCD < 232°C: 1 g WHO98 TEQDF/yr (1 g I-TEQDF/yr).
• 1995—APCD > 232°C: 160 g WHO98 TEQDF/yr (150 g I-TEQDF/yr).
APCD < 232°C: 1 g WHO98 TEQDF/yr (1 g I-TEQDF/yr).
• 2000—19 g WHO98 TEQDF/yr (17 g I-TEQDF/yr).
Water Releases
~.t is possible that the effluent from the APCD systems at these facilities contain CDDs and CDFs
because they have been measured in the stack gases. No information was found on levels in the
ffluent, so this considered a possible but unquantifiable source.
Solid Residue Releases
Emission Factor
• 1987—35 ng I-TEQDF/kg (Preliminary).
• 1995—35 ng I-TEQDF/kg (Preliminary).
• 2000—35 ng I-TEQDF/kg (Preliminary).
Activity Level for Beneficial Uses
• 1987—120 million kg.
• 1995—104 million kg.
• 2000—94 million kg.
This document is a draft for review purposes only and does not constitute Agency policy.
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Cement Kilns Burning Hazardous Waste (continued)
Releases for Beneficial Uses
• 1987—4 g I-TEQ (Preliminary).
• 1995—4 g I-TEQ (Preliminary).
• 2000—3 g I-TEQ (Preliminary).
Products
No information was found suggesting that clinker contained measureable
CDFs. Beneficial uses of CKD are covered under solid residues.
levels of CDDs and
1
2
3 5.2. LIGHTWEIGHT AGGREGATE KILNS
4 5.2.1. Air Releases
5 No changes were made to the air-release estimates, but some clarifications are provided.
6 Lightweight aggregate (LWA) kilns burning hazardous waste are estimated to have emitted
7 3.3 g I-TEQoF to air in 1990 (Federal Register, 1998) and 2.4 g I-TEQDF in 1997 (Federal
8 Register, 1999); these estimates are used in this report for reference years 1987 and 1995,
9 respectively. The emission factor estimate for 2000 is 1.99 ng WHOgg TEQop/kg
10 (2.06 ng I-TEQoF/kg) based on testing at 5 kilns (U.S. EPA, 2002a). As discussed in EPA, 2006,
11 activity data were available on all 9 facilities operating in 2000 from EPA's Office of Solid
12 Waste. This information was combined with assumptions about annual feed rates and operating
13 time percentage to get total activity estimates. EPA (2006) mislabeled the activity estimates as
14 applying to halogen acid furnaces rather than light weight aggregate kilns.
15
16 5.2.2. Water Releases—None
17
18 5.2.3. Solid Residue Releases—None
19
20 5.2.4. Product Literature—None
21
22 5.2.5. Release Summary
23 The inventory decision criteria and releases to all media are summarized below:
24
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Lightweight Aggregate Kilns
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
1
2
Lightweight Aggregate Kilns
Air Releases
Emission Factors
• 1987—not needed.
• 1995—not needed.
• 2000—2.0 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg) of waste feed.
Activity Levels
• 1987—not needed.
• 1995—not needed.
• 2000—903,000 MT.
Releases
• 1987—3gI-TEQDF.
• 1995—2gI-TEQDF.
• 2000—2 g WHO98 TEQDF (2 g I-TEQDF).
Water Releases
No information was found suggesting that water releases from these facilities would contain
CDDs and CDFs.
Solid Residue Releases
No information was found suggesting that solid residues from these facilities would contain
CDDs and CDFs.
Products
No information was found suggesting that products from these facilities would contain CDDs
and CDFs.
3
4
5
6
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.3. ASPHALT MIXING PLANTS
2 5.3.1. Air Releases
3 Changes were made to the air emission factor, and the releases estimated for 2000 were
4 also assumed to apply to the reference years 1987 and 1995.
5 The original report estimated the emission factor on the basis of tests at two U.S.
6 facilities. The original report also included information on testing at one facility in the
7 Netherlands: 0.047 ng I-TEQ/kg (Bremmer et al., 1994) and three facilities in Germany: 0.0002,
8 0.0035, and 0.0038 ng I-TEQ/kg (Umweltbundesamt, 1996). Because the European facilities are
9 likely similar to those in the United States, the y were averaged in with the U.S. facilities to
10 derive an emission factor of 0.0095 ng I-TEQ/kg, and this was applied to all reference years.
11 This factor falls within the range recommended by UNEP (2005) for asphalt mixing plants:
12 0.0.007 to 0.07 ng I-TEQ/kg. The confidence rating was upgraded from preliminary to
13 quantifiable based on the additional testing used to support it and similarity to UNEP, 2005.
14 The original report provided an activity estimate of 500 million tons for 2000 based on
15 1996 survey data. Because this industry is fairly stable in terms of growth and the activity data
16 are near the midpoint of the reference year range, it is reasonable to assume it applies to all
17 reference years. Asphalt can be produced at both fixed and mobile facilities. It is unclear if this
18 activity estimate includes both types of plants or only those at fixed locations. The National
19 Cooperative Highway Research Program Web site and other related sites were searched, but no
20 relevant information was found.
21
22 5.3.2. Water Releases
23 No information was found suggesting that water releases from these facilities would
24 contain CDDs and CDFs.
25
26 5.3.3. Solid Residue Releases
27 UNEP (2005) indicates that flue gas cleaning residues are likely to have CDD/CDFs and
28 suggests an emission factor of 0.06 ng I-TEQ/kg. No information was available on the quantity
29 of this material generated. Also, it is likely that these residues would be landfilled and, therefore,
30 not considered a release.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.3.4. Products
2 No information was found suggesting that products from these facilities would contain
3 CDDs and CDFs.
4
5 5.3.5. Release Summary
6 The inventory decision criteria and releases are summarized below:
7
Inventory Decision Criteria for Asphalt Mixing Plants
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
This document is a draft for review purposes only and does not constitute Agency policy.
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Asphalt Mixing Plants
Air Releases
Emission Factors
• 1987—0.009 ng I-TEQ/kg of asphalt produced.
• 1995—0.009 ng I-TEQ/kg of asphalt produced.
• 2000—0.009 ng I-TEQ/kg of asphalt produced.
Activity Levels
• 1987— 500 MMT.
• 1995— 500 MMT.
• 2000—500 MMT.
Releases
• 1987— 5gI-TEQ.
• 1995— 5gI-TEQ.
• 2000—5 g I-TEQ.
Water Releases
No information was found suggesting that water releases from
CDDs and CDFs.
these facilities would contain
Solid Residue Releases
Any solid residues from these facilities would be landfilled and not considered an environmental
release.
Products
No information was found suggesting that products from these
and CDFs.
facilities would contain CDDs
1
2
3 5.4. PETROLEUM-REFINING CATALYST REGENERATION PLANTS
4 5.4.1. Air Releases
5 No changes were made to the air-release estimates. The average of the emission factors
6 for two California facilities (1.59 ng WHOgg TEQoF/barrel (1.52 ng 1-TEQop/barrel) of reformer
7 feed) is assumed to apply to all reference years. The activity estimates were derived from EIA,
8 2002.
9 In the year 2000, one facility with an SIC code for petroleum bulk stations and terminals
10 reported dioxin releases under EPA's TRI program (U.S. EPA, 2008). The total air releases for
11 this facility was 102.8 g, which EPA estimates is equal to 3 g WHOgg TEQDF. No releases to
12 other media were reported. As explained in Chapter 1, the TRI data are not used to make
13 quantitative estimates in this document, but, rather, the data are offered as supportive evidence
14 that releases do occur.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.4.2. Water Releases
2 As discussed in EPA (2006), CDD/CDFs have been detected in wastewaters from these
3 facilities. However, insufficient information is available on the levels and quantities of these
4 wastes to generate release estimates. On this basis, they are considered possible but
5 unquantifiable sources.
6
7 5.4.3. Solid Residue Releases
8 As discussed in EPA (2006), CDD/CDFs have been detected in solid residues from these
9 facilities. However, insufficient information is available on the levels and quantities of these
10 wastes to estimate the amounts. However, these residues would be landfilled and, therefore, not
11 considered an environmental release.
12
13 5.4.4. Product Literature
14 No information was found suggesting that products from these facilities would contain
15 CDDsandCDFs.
16
17 5.4.5. Release Summary
18 The inventory decision criteria and releases are summarized below:
Inventory Decision Criteria for Petroleum-Refining Catalyst Regeneration
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
pie class.
Uctivity estimates based on source-specific surveys.
[Conclusion (Q = Quantitative, P = Preliminary).
Air Water Solids
Yes
Yes
Yes
Yes
Q
Plants
Products
19
20
This document is a draft for review purposes only and does not constitute Agency policy.
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Petroleum-Refining Catalyst Regeneration Plants
Air Releases
Emission Factors
• 1987—1.6 ng WHO98 TEQDF/barrel (1.5 ng I-TEQDF/barrel) of reformer feed.
• 1995—1.6 ng WHO98 TEQDF/barrel (1.5 ng I-TEQDF/barrel) of reformer feed.
• 2000—1.6 ng WHO98 TEQDF/barrel (1.5 ng I-TEQDF/barrel) of reformer feed.
Activity Levels
• 1987—1,390 million barrels.
• 1995—1,410 million barrels.
• 2000—1,380 million barrels.
Releases
• 1987—2 g WHO98 TEQDF (2 g I-TEQDF).
• 1995-2 g WH098 TEQDF (2 g I-TEQDF).
• 2000—2 g WHO98 TEQDF (2 g I-TEQDF).
Water Releases
CDD/CDFs have been detected in wastewaters from these facilities. However, insufficient
information is available on the levels and quantities of these wastes to generate release estimates.
On this basis, they are considered possible but unquantifiable sources.
Solid Residue Releases
Any solid residues from these facilities would be landfilled and not considered an environmental
release.
Products
No information was found suggesting that products from these facilities would contain CDDs
and CDFs.
10
11
12
13
14
15
1
2
3 5.5. CIGARETTE SMOKING
4 5.5.1. Air Releases
5 No changes were made to the air-release estimates. The air emission factor was derived
6 using data from Matsueda et al. (1994) and Lofroth and Zebiihr (1992). The activity estimates
7 were based on Brown (2002).
5.5.2. Water Releases—None
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.5.3. Solid Residue Releases
2 No information was found suggesting that ash from cigarette smoking would contain
3 CDDs and CDFs.
4
5 5.5.4. Products—None
6
7 5.5.5. Release Summary
8 The inventory decision criteria and releases are summarized below. Although these
9 emission estimates are relatively small compared to many other sources, they have increased
10 importance because humans are directly exposed to cigarette smoke.
11
Inventory Decision Criteria for Cigarette Smoking
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
12
13
This document is a draft for review purposes only and does not constitute Agency policy.
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Cigarette Smoking
Air Releases
Emission Factors
• 1987—1.7 pg WHO98 TEQDF/cigarette (1.6 pg I-TEQDF/cigarette).
• 1995—1.7 pg WHO9g TEQDF/cigarette (1.6 pg I-TEQDF/cigarette).
• 2000—1.7 pg WHOgg TEQpF/cigarette (1.6 pg I-TEQDF/cigarette).
Activity Levels
• 1987—575 billion cigarettes.
• 1995—487 billion cigarettes.
• 2000—440 billion cigarettes.
Releases
• 1987—1 g WHO98 TEQDF (0.9 g I-TEQDF).
• 1995—0.8 g WHO98 TEQDF (0.8 g I-TEQDF).
• 2000—0.7 g WHO98 TEQDF (0.7 g I-TEQDF).
Water Releases
None.
Solid Residue Releases
No information was found suggesting that ash from cigarette smoking would contain CDDs and
CDFs.
Products
Not applicable.
2
3 5.6. PYROLYSIS OF BROMINATED FLAME RETARD ANTS
4 The primary purpose of this report is to provide emission estimates for chlorinated
5 dibenzo-p-dioxins and dibenzofurans. However, the brominated dibenzo-p-dioxins (BDDs) and
6 dibenzofurans (BDFs) may also have dioxin-like toxicity. To date, though, no TEQs have been
7 established for these compounds. Because these compounds are related to the CDDs and CDFs,
8 some information on their emissions from facilities that pyrolyze brominated flame retardants is
9 included in EPA (2006).
10
11 5.7. CARBON REACTIVATION FURNACES
12 5.7.1. Air Releases
13 No changes were made to the air-release estimates. The emission factor was derived
14 from two GAC reactivation furnaces stack-tested by EPA (U.S. EPA, 1987; Lykins et al., 1987).
15
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1 One test was conducted at a multiple hearth facility which is typical of large scale operations and
2 the second test was conducted at a fluidized bed facility which is more typical of smaller
3 operations. The activity was estimated on the basis of the mass of virgin GAC shipped each year
4 by GAC manufacturers according to the U.S. Department of Commerce (U.S. DOC, 1990).
5
6 5.7.2. Water Releases—None
7
8 5.7.3. Solid Residue Releases—None
9
10 5.7.4. Products
11 No information was found suggesting that products from these facilities would contain
12 CDDs and CDFs.
13
14 5.7.5. Release Summary
15 The inventory decision criteria and releases are summarized below:
16
Inventory Decision Criteria for Carbon
Reactivation Furnaces
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
17
18
This document is a draft for review purposes only and does not constitute Agency policy.
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Carbon Reactivation Furnaces
Air Releases
Emission Factors
• 1987— 1.2 ng (WHO98 TEQDF or I-TEQDF) per kg of reactivated carbon.
• 1995—1.2 ng (WHO9g TEQDF or I-TEQDp) per kg of reactivated carbon.
• 2000— 1.2 ng (WHOgg TEQDF or I-TEQDF) per kg of reactivated carbon.
Activity Levels
• 1987—48,000 MT.
• 1995—65,000 MT.
• 2000—65,000 MT.
Releases
• 1987—0.1 g (WHO98 TEQDF or I-TEQDF).
• 1995—0.1 g (WHO98 TEQDF or I-TEQDF).
• 2000—0.1 g (WHO98 TEQDF or I-TEQDF).
Water Releases
No water releases are produced.
Solid Residue Releases
No solid residues are produced.
Products
No information was found suggesting that products from these facilities would contain CDDs
and CDFs.
2
3 5.8. KRAFT BLACK LIQUOR RECOVERY BOILERS
4 5.8.1. Air Releases
5 No changes were made to the air-release estimates. The emission factor for 1987 and
6 1995 was based on the data for the six NCASI facilities (NCASI, 1995). For 2000, the emission
7 factor was based on "NCASI Handbook of Chemical Specific Information for SARA
8 Section 313 Form R Reporting." Activity estimates were derived from information provided by
9 American Paper Institute (API, 1992), American Forest and Paper Association (AF&PA,1997),
10 and NCASI (2002).
11
12 5.8.2. Water Releases—None
13
14
15
16
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.8.3. Solid Residue Releases
2 Fly ash is typically collected in ESPs at these facilities. Because CDD/CDFs have been
3 detected in the stack gases, they are likely to be also contained in the fly ash, but no
4 measurements have been reported. Any solid residues are likely to be landfilled and, therefore,
5 are not considered an environmental release.
6
7 5.8.4. Products
8 No information was found suggesting that products from these facilities would contain
9 CDDs and CDFs.
10
11 5.8.5. Release Summary
12 The inventory decision criteria and releases are summarized below:
13
Inventory Decision Criteria for Kraft Black
Liquor Recovery Boilers
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
14
15
This document is a draft for review purposes only and does not constitute Agency policy.
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Kraft Black Liquor Recovery Boilers
Air Releases
Emission Factors
• 1987—0.03 ng WHO98 TEQDF/kg (0.03 ng I-TEQDF/kg) of black liquor solids.
• 1995—0.03 ng WHO98 TEQDF/kg (0.03 ng I-TEQDF/kg) of black liquor solids.
• 2000—0.010 ng WHO98 TEQDF/kg of black liquor solids.
Activity Levels
• 1987—69.8 MMT.
• 1995—80.8 MMT.
• 2000—90.7 MMT for Kraft recovery furnaces.
Releases
• 1987—2 g (WHO98 TEQDF or I-TEQDF).
• 1995—2 g (WHO98 TEQDF or I-TEQDF).
• 2000—0.9 g WHO98 TEQDF/yr.
Water Releases
No water releases are produced.
Solid Residue Releases
Any solid residues from these facilities would be landfilled and not considered an environmental
release.
Products
No information was found suggesting that products from these facilities would contain CDDs
and CDFs.
2
3 5.9. LIMEKILNS
4 This is a new section covering lime kilns used in the pulp and paper industry as well as
5 other industries.
6
7 5.9.1. Process Description
8 Lime making consists of burning of calcium and/or magnesium carbonate at a
9 temperature between 900 and 1,500°C. The burned lime is either delivered to the end user in the
10 form of quicklime or reacted with water in a hydrating plant to produce hydrated lime or slaked
11 lime. Different fuels—solid, liquid, or gaseous—are used in lime burning. Most of the kilns are
12 either shaft or rotary design and have countercurrent flow of solids and gases. Fluidized bed
13 kilns and rotary hearths may also be found (UNEP, 2005).
14
15
This document is a draft for review purposes only and does not constitute Agency policy.
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1 5.9.2. Regulations
2 None specific to dioxins.
3
4 5.9.3. Air Releases
5 Annual emissions from lime kilns in Belgium and the United Kingdom have been
6 reported by Wevers and De Fre (1995) and Douben et al. (1995), respectively. However, the
7 emission factors used to generate those estimates were not provided. Umweltbundesamt (1996)
8 reported emission factors of 0.016 to 0.028 ng I-TEQop/kg during tests at two lime kilns in
9 Germany.
10 UNEP (2005) reports that data from Europe on seven kilns, of which four were rotary
11 kilns and three were shaft kilns, showed CDD/PCDF concentrations below 0.1 ng TEQ/Nm3.
12 Measurements at two annular shaft kilns in Germany were all below 0.05 ng I-TEQ/Nm3.
13 High concentrations of CDD/PCDF have been measured at three kilns, two rotary kilns,
14 and one shaft kiln, in Sweden. The measurements made between 1989 and 1993 gave
15 concentrations between 4.1 and 42 ng N-TEQ/Nm3. All measurements of high CDD/PCDF
16 concentrations have been explained by the raw material, fuel content, or less-than-optimum
17 burning conditions, underlining the importance of controlling the kiln inputs and maintaining a
18 stable kiln operation (IPPC, 2001).
19 UNEP (2005) recommends two emission factors. For no dust controls or poor fuel,
20 10 ug I-TEQ/MT of CaO are recommended, and for kilns with good dust controls,
21 0.07 ug I-TEQ/MT of CaO are recommended.
22 In the year 2000, one facility with an SIC code for lime reported dioxin releases under the
23 EPA TRI program (U.S. EPA, 2008). The total air releases for this facility was 0.73 g, which
24 EPA estimates is equal to 0.15 g WHOgg TEQop The total land releases for this facility was
25 2.8 g, which EPA estimates is equal to 0.6 g WHOgg TEQop. No releases to other media were
26 reported. As explained in Chapter 1, the TRI data are not used to make quantitative estimates in
27 this document but rather as supportive evidence that releases do occur.
28 For 2000, the emission factor of 0.0058 ng WHO98 TEQDF/kg of CaO was used on the
29 basis of "NCASI Handbook of Chemical Specific Information for SARA Section 313 Form R
30 Reporting." The factors provided in this handbook were compiled from test data supplied to
31 NCASI by a variety of sources, including NCASI member companies who had performed the
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1 tests in response to a regulatory program. Congener-specific CDD/CDF TEQ emission factors
2 were provided (see Table 5-1).
3 For 2000, NCASI provided estimates of activity levels for Kraft lime kilns (Gillespie,
4 2002). The activity levels were reported to be 13 MMT. Insufficient information was available
5 to make release estimates for the other reference years.
6
7 5.9.4. Water Releases
8 No information was found suggesting that any water releases from these facilities would
9 contain CDDs and CDFs.
10
11 5.9.5. Solid Residue Releases
12 Any solid residues from these facilities would be landfilled and are not considered an
13 environmental release.
14
15 5.9.6. Products
16 No information was found suggesting that products from these facilities would contain
17 CDDs and CDFs.
18
19 5.9.7. Release Summary
20 The inventory decision criteria and releases are summarized below:
21
22
Inventory Decision Criteria
for Lime Kilns
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
he class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
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Lime Kilns
Air Releases
Emission Factors
• 1987—NA.
• 1995—NA.
• 2000—0.006 ng WHO98 TEQDF/kg of CaO.
Activity Levels
• 1987—NA.
• 1995—NA.
• 2000—13 MMT.
Releases
• 1987—NA.
• 1995—NA.
• 2000—0.1 g WHO98 TEQDF/yr.
Water Releases
No information was found suggesting that any water releases from these facilities would contain
CDDs and CDFs.
Solid Residue Releases
Any solid residues from these facilities would be landfilled and are not considered an
environmental release.
Products
No information was found suggesting that products from these facilities would contain CDDs
and CDFs.
1
2
3 5.10. GLASS MANUFACTURING
4 This is a new section.
5 UNEP (2005) provides an emission factor for glass manufacturing operations using dust
6 abatement of 0.015 ng I-TEQ/kg of product. This factor was based on testing at three facilities
7 in Germany. It was assumed to apply to all reference years. The amount of glass produced in
8 the United States during 1999 was 18 MMT (DOE, 2002). Data were not found for the earlier
9 years, and this value was assumed to apply to all of the reference years.
10 No information was found on CDD/CDF levels in the solid waste generated from glass
11 manufacturing. However, these residues would be landfilled and, therefore, are not considered
12 to be an environmental release.
13 The inventory decision criteria and releases are summarized below:
14
15
16
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Glass
Manufacturing
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
1
2
Glass Manufacturing
Air Releases
Emission Factors
• 1987—0.02 ng I-TEQDF/kg of metal feed.
• 1995—0.02 ng I-TEQDF/kg of metal feed.
• 2000—0.02 ng I-TEQDF/kg of metal feed.
Activity Levels
• 1987—18MMT.
• 1995—18MMT.
• 2000—18MMT.
Releases
• 1987—0.4 gI-TEQDF.
• 1995—0.4 gl-TEQoF.
• 2000—0.4 g 1-TEQpp.
Water Releases
None.
Solid Residue Releases
None.
Products
None.
4
5
6
7
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1 5.11. OTHER IDENTIFIED SOURCES
2 A number of additional operations may be sources of CDD/CDF formation because the
3 processes use chlorine-containing components or involve application of high temperatures.
4 These include ceramics/rubber production facilities and plating/painting facilities which use
5 thermal air-pollution control devices. Additionally automobile shredding was identified as a
6 potential source of CDD/CDF releases. However, no testing of emissions from these processes
7 has been performed in the United States, and only minimal emission rate information has been
8 reported for these processes in other countries. Therefore, emissions from these sources are
9 possible but cannot be quantified.
10
Miscellaneous Sources
Possible Air Releases
Ceramics and rubber manufacturers (Not quantifiable).
Thermal air pollution control devices used at plating facilities and painting operations (Not
quantifiable).
Automobile shredders (Not quantifiable).
Possible Water Releases
Ceramics and rubber manufacturers (Not quantifiable).
11
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1
2
3
Table 5-1. CDD/CDF TEQ emission factors and emission estimates from
Kraft lime kilns
Congener
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Total
WH098 TEQDF
(ng/lb CaO)
0.00 x 10°
0.00 x 10°
0.00 x 10°
l.OOx 10~4
0.00 x 10°
2.80 x 1Q~4
2.56 x 1Q~4
8.00 x 1Q~4
l.OOx KT4
0.00 x 10°
9.00 x 1Q~4
2.00 x 1Q~4
0.00 x 10°
0.00 x 10°
0.00 x 10°
0.00 x 10°
0.00 x 10°
2.64 x 1Q~3
WH098 TEQDF
(ng/kg CaO)
0.00 x 10°
0.00 x 10°
0.00 x 10°
2.20 x 1Q~4
0.00 x 10°
6.16x 1Q~4
5.63 x 1Q~4
1.76x 1Q~3
2.20 x 1Q~4
0.00 x 10°
1.98 x 1Q~3
4.40 x 1Q~4
0.00 x 10°
0.00 x 10°
0.00 x 10°
0.00 x 10°
0.00 x 10°
5.80 x 1Q~3
4
5
CaO = Calcium oxide.
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1 6. COMBUSTION SOURCES OF CDDs/CDFs MINIMALLY CONTROLLED AND
2 UNCONTROLLED COMBUSTION SOURCES
3
4
5 6.1. COMBUSTION OF LANDFILL GAS
6 6.1.1. Air Releases
7 No changes were made to the air-release estimates. The emission factor was derived by
8 averaging test results for one landfill flare in California (CARB, 1990) and one in the
9 Netherlands (Bremmer et al., 1994). This value was assumed to apply to all reference years:
10 1.4 ng I-TEQoF/m3. The emission factors for the two facilities differed by a factor of six. UNEP
11 (2005) used studies from Germany and the U.K. to derive an emission factor of 8 ug I-TEQ/TJ of
12 gas burned. Assuming that the landfill gas has a heating value of 16 MJ/m3 (half that of natural
13 gas), this converts to 0.13 ng I-TEQ/m3. Based on the limited data and inconsistency in emission
14 factors this was considered preliminary. As described in the 2006 document, survey data and
15 assumptions were used to derive activity estimates.
16
17 6.1.2. Water Releases
18 No wet scrubbers are used for these facilities, so no releases to surface waters should
19 occur.
20
21 6.1.3. Solid Residue Releases—None
22
23 6.1.4. Products—None
24
25 6.1.5. Release Summary
26 The inventory decision criteria and releases to all media are summarized below:
27
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Inventory Decision Criteria for Landfill Gas
Air Water Solids Products
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission
factors.
leasured emission factors consistent or have No
understandable differences.
Emission factor tests represent units that are typical of the Yes
;lass.
Activity estimates based on source-specific surveys. Yes
1
Conclusion (Q = Quantitative, P = Preliminary).
Combustion of Landfill Gas
Air Releases
Emission Factors
1987—1.4 ng I-TEQDF/m3 (Preliminary).
1995—1.4 ng I-TEQDF/m3 (Preliminary).
2000—1.4 ng I-TEQDF/m3 (Preliminary).
Activity Levels
• 1987—1.35 billion m3.
• 1995—4.7 billion m3.
• 2000—16 billion m3.
Releases
• 1987—2 g I-TEQoF (Preliminary).
• 1995—7 g I-TEQoF (Preliminary).
• 2000—22 g I-TEQpF (Preliminary).
Water Releases
None.
Solid Residue Releases
None.
Products
None.
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1 6.2. ACCIDENTAL FIRES
2 6.2.1. Structural Fires
3 6.2.1.1. Air Releases
4 No changes were made to the air-release estimates, but additional background
5 information is provided below.
6 The most recent evidence of the release of CDD/CDFs from combustion of structures
7 was from the collapse of the World Trade Center Towers. Pleil and Lorber (2007) examined
8 dioxin congener concentrations and profiles from several fires including the fires that burned at
9 Ground Zero after the collapse of the Towers for upwards of 200 days, the Binghamton office
10 fire that occurred in the early 1980s starting from a transformer fire in the basement of the office
11 building, and an office fire from a building in Philadelphia. The air concentrations that resulted
12 from World Trade Center fires exceeded 100 pg WHOgg TEQoF/m3 for several ambient air
13 measurements within 500 m of the fires. The Binghamton office fire was dominated by the
14 combustion of PCBs in the transformers. The Philadelphia office fire was typical of urban
15 building structures. Pleil and Lorber (2007) looked at profiles of CDD/CDFs in impacted air,
16 dust, and soot, and compared these profiles with background profiles. While their analysis did
17 not allow for generation of an emission factor, it did produce a congener profile (see Figure 6-1).
18 The presence of manufactured boards and treated lumber in structures is expected to
19 increase dioxin emissions relative to the combustion of untreated natural wood. As discussed in
20 Section 4.2, Tame et al. (2007) reviewed the literature on the role of preservatives in the
21 formation of dioxin in the combustion of wood. They conclude that current and emerging wood
22 preservatives significantly increase dioxin formation during combustion in domestic stoves and
23 in fires. Also Bhargava et al. (2002) conducted calorimeter testing and derived emission factors
24 of 20.5 ng WHO9g TEQ/kg for chip boards andl5.4 ng WHO9g TEQ/kg for medium density
25 fiberboard (MDF) compared to nondetect to 2.5 ng WHOgg TEQ/kg for natural woods.
26 The original report (U.S. EPA, 2006) recommends an emission factor of 32 ug I-TEQ/fire
27 based on averaging data from Carroll (1996) and Thomas and Spiro (1995). These were based
28 on soot measurements or other indirect methods and were assigned a preliminary confidence
29 rating. This emission factor can be converted to a mass basis by dividing by a default
30 fuel-loading factor for structural fires of 1.15 tons/fire (ERG, 2001), yielding 28 ng I-TEQ/kg.
31 This is much less than the emission factor of 400 ng I-TEQ/kg recommended by UNEP (2005).
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1 No changes were made to the activity estimates which were derived from survey data in FEMA
2 (1997, 2001) and are presented in the release summary below.
3
4 6.2.1.2. Water Releases
5 It is possible that dioxin-contaminated particles could be entrained in water used to fight
6 fires or rainwater that falls on the site. This water could run off the site and eventually get into
7 surface waters. No quantitative release estimates could be made.
8
9 6.2.1.3. Solid Residue Releases
10 Solid residue releases are possible because CDDs and CDFs have been measured in solid
11 residues remaining after structural fires. EPA (2006) summarized six field studies with residue
12 concentrations ranging from 0.03 to 130 ug I-TEQDF/kg. This wide data range is understandable
13 considering that the amount/types of treated wood and household products found in structures is
14 likely to be highly variable. The geometric mean of 2 ug 1-TEQop/kg of residue was selected as
15 a central value. This was converted to an emission factor by assuming that 15% of the fuel is
16 converted to ash (this is based on the assumption that structural fires will generate ash at a
17 similar rate as observed for bottom ash in municipal waste combustion, which is reported by
18 UNEP [2005] to be typically 10-20%). This yields an emission factor of 300 ng I-TEQDF/kg of
19 material burned, which was assumed to apply to all reference years. Based on an analysis of the
20 congener data reported by Christmann et al. (1989b) for soot from a building fire, this emission
21 factor will be the same when converted to WHOgg TEQs. This value is similar to the UNEP,
22 2005 recommendation of 400 ng I-TEQop/kg of material burned.
23 The activity estimates used to calculate residue releases for structural fires were
24 computed by multiplying the number of fires by the default fuel-loading factor for structural fires
25 of 1.15 tons/fire (ERG, 2001).
26
27 6.2.1.4. Products—None
28
29 6.2.1.5. Release Summary
30 The inventory decision criteria and releases to all media are summarized below.
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1 The air-release estimates presented here are similar to those reached for national emission
2 inventories developed for the Netherlands (Bremmer et al., 1994) and the United Kingdom (U.K.
3 Department of the Environment, 1995).
4
Inventory Decision Criteria for
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
he class.
Activity estimates based on source-specific surveys.
onclusion (Q = Quantitative, P = Preliminary).
5
6
Structural Fires
Air Water
No
Yes
Yes
P
Solids Products
Yes
Yes
Yes
Yes
Q
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Structural Fires
Air Releases
Emission Factors
• 1987—32 ug I-TEQDF/fire (Preliminary).
• 1995—32 ug 1-TEQoF/fire (Preliminary).
• 2000—32 ug I-TEQpF/fire (Preliminary).
Activity Levels
• 1987—746,000 fires.
• 1995—574,000 fires.
• 2000—512,000 fires.
Releases
• 1987—24 g I-TEQDF (Preliminary).
• 1995—18 g I-TEQDF (Preliminary).
• 2000—16 g I-TEQDF (Preliminary).
Water Releases
*ossible but unquantifiable releases.
Solid Residue Releases
Emission Factors
• 1987—300 ng (WHO98 or I-TEQDF/kg) of material burned.
• 1995—300 ng (WHO98 or I-TEQDF/kg) of material burned.
• 2000—300 ng (WHO98 or I-TEQDF/kg) of material burned.
Activity Levels
• 1987—860,000 tons.
• 1995—660,000 tons.
• 2000—589,000 tons.
Releases
es
1987—260 g (WHO98 or I-TEQDF).
1995—200 g (WHO98 or I-TEQDF).
2000—180 g (WHO98 or I-TEQDF).
Products
None.
1
2
3 6.2.2. Vehicle Fires
4 6.2.2.1. Air Releases
5 No changes were made to the air-release estimates. Wichmann et al. (1993, 1995)
6 measured CDD/CDF emissions from controlled vehicle fires in a tunnel (two cars, one subway
7
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1 car, and one railway car). This study suggests an emission factor of 0.044 mg I-TEQop for cars
2 and trucks and 2.6 mg I-TEQoF/fire for other vehicles. These values were assumed for all
3 reference years. They are uncertain because Wichmann et al. (1993, 1995) based their estimates
4 on surface deposits. This procedure may not have fully accounted for volatile CDDs/CDFs,
5 which were reported by Merk et al. (1995) to account for the majority of CDDs/CDFs formed
6 during a fire. Given the indirect method of measuring emissions, they are considered
7 preliminary estimates. UNEP (2005) derived an emission factor of 0.094 mg I-TEQoF/incident.
8 This was also based on Wichmann et al. (1995) and represents an average across all vehicle
9 types.
10 The activity estimates were based on the number of vehicle fires reported in the United
11 States: approximately 561,530 in 1987 (FEMA, 1997), 406,000 in 1995 (U.S. DOC, 1997), and
12 341,600 in 2000 (FEMA, 2001). Also, the assumption was made that 99% of those fires
13 involved cars and trucks (the approximate percentage of all U.S. motor vehicles that are
14 in-service cars and trucks; U.S. DOC, 1995).
15
16 6.2.2.2. Water Releases
17 It is possible that dioxin-contaminated particles could be entrained in water used to fight
18 fires or rainwater that falls on the site. This water could run off the site and eventually get into
19 surface waters. No quantitative release estimates could be made. Therefore, this is a possible
20 but unquantifiable source.
21
22 6.2.2.3. Solid Residue Releases
23 The original document (US EPA, 2006) did not address solid residue releases. Solid
24 residue releases are possible because CDDs and CDFs have been measured in solid residues
25 remaining after vehicle fires. Wichmann et al. (1995) measured an average of
26 0.01 mg I-TEQoF/fire for cars and trucks and 0.8 mg I-TEQoF/fire for other vehicles. These
27 values were adopted here for all reference years using the same data; UNEP (2005) derived a
28 solid residues emission factor of 0.018 mg I-TEQoF/incident for all vehicles. These emission
29 factors were combined with the same activity data reported above to estimate releases.
30
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1 6.2.2.4. Products—None
2
3 6.2.2.5. Release Summary
4 The inventory decision criteria and releases to all media are summarized below:
5
Inventory Decision Criteria for Vehicle Fires
Air Water Solids Products
Emission tests for at least two units/source types with No Yes
sufficient documentation to directly derive emission
factors.
leasured emission factors consistent or have Yes
understandable differences.
Emission factor tests represent units that are typical of the Yes Yes
;lass.
Activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary).
6
7
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Vehicle Fires
Air Releases
Emission Factors
Cars and Trucks
• 1987—0.044 mg I-TEQDF/incident (Preliminary).
• 1995—0.044 mg I-TEQDF/incident (Preliminary).
• 2000—0.044 mg I-TEQDF/incident (Preliminary).
Other Vehicles
• 1987—2.6 mg I-TEQoF/incident (Preliminary).
• 1995—2.6 mg I-TEQDF/incident (Preliminary).
• 2000—2.6 mg I-TEQDF/incident (Preliminary).
Activity Levels
Cars and Trucks
• 1987—556,000 vehicle fires.
• 1995—402,000 vehicle fires.
• 2000—338,000 vehicle fires.
Other Vehicles
• 1987—5,600 vehicle fires.
• 1995—4,060 vehicle fires.
• 2000—3,400 vehicle fires.
Releases
Cars and Trucks
• 1987—24 g I-TEQDF (Preliminary).
• 1995—18 g I-TEQDF (Preliminary).
• 2000—15 g I-TEQDF (Preliminary).
Other Vehicles
• 1987—15 g I-TEQoF (Preliminary).
• 1995—11 g I-TEQoF (Preliminary).
• 2000—9 g I-TEQDF (Preliminary).
All Vehicles
• 1987—39 g I-TEQoF (Preliminary).
• 1995—29 g I-TEQoF (Preliminary).
• 2000—24 g I-TEQpF (Preliminary).
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Vehicle Fires (continued)
Water Releases
*ossible but unquantifiable releases.
Solid Residue Releases
Emission Factors
Cars and Trucks
• 1987—0.01 mg I-TEQDF/incident.
• 1995—0.01 mg I-TEQDF/incident.
• 2000—0.01 mg I-TEQDF/incident.
Other Vehicles
• 1987—0.8 mg I-TEQDF/incident.
• 1995—0.8 mg I-TEQoF/incident.
• 2000—0.8 mg I-TEQDF/incident.
Activity Levels
Cars and Trucks
• 1987—556,000 vehicle fires.
• 1995—402,000 vehicle fires.
• 2000—338,000 vehicle fires.
Other Vehicles
• 1987—5,600 vehicle fires.
• 1995—4,060 vehicle fires.
• 2000—3,400 vehicle fires.
Releases
Cars and Trucks
• 1987—6gI-TEQDF.
• 1995—4gI-TEQDF.
• 2000—3 g I-TEQDF.
Other Vehicles
• 1987—5gI-TEQDF.
• 1995—3gI-TEQDF.
• 2000—3 g I-TEQDF.
All Vehicles
• 1987—11 gl-TEQoF.
• 1995—7gI-TEQDF.
• 2000—6 g I-TEQpF.
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1 6.3. LANDFILL FIRES
2 6.3.1. Air Releases
3 The original report derived a preliminary release estimate from landfill fires using a per
4 capita release factor of 4 ug I-TEQ per person developed from Swedish data. This factor was
5 estimated by dividing the national release estimate for Sweden by the population. This per capita
6 approach assumes that landfill fires increase over the reference years in proportion to the
7 population. However, improved regulations and increases in methane recovery systems at
8 landfills are likely to have reduced landfill fire frequency/magnitude over this time frame.
9 Accordingly, a new approach is suggested below that does not show a downward trend.
10 Collet and Fiani (2006) reported on the measurement of PAH, PCB, and CDD/CDF
11 emission from simulated forest and landfill fires. For the landfill simulations, samples were
12 collected from two landfills located in southwest France. They collected samples from what they
13 characterized as the superficial part of the landfill ground, only the first 15 cm. These samples
14 included municipal wastes and nonhazardous industrial wastes containing various plastics, wood,
15 rubber, rags, and so on. The combustion chamber had an air flow of 1,800 nm3/hour,
16 corresponding to 22.5 volume changes per hour, to simulate open burning conditions. Emissions
17 were sampled near the chamber exit and prior to the scrubber. They conducted two landfill fire
18 simulations, and the emission factors for CDD/CDFs, in ng I-TEQ/kg, were 242 and
19 233 ng I-TEQ/kg. Collet and Fiani also provided emission factors for 12 dioxin-like PCBs, in
20 ng I-TEQ/kg, and they were 9.9 and 16.6 ng I-TEQ/kg. Their landfill samples were collected
21 over a surface area of 2 m2, allowing generation of emission factors on an area basis. The
22 emission factors for CDD/CDFs, in ng I-TEQ/m2, were 1380 and 1321, and for the
23 12 dioxin-like PCBs, also in ng I-TEQ/m2, were 56.3 and 94.2.
24 Persson and Bergstrom (1991) conducted experiments simulating surface and deep fires
25 and estimated an emission factor of 1000 ng Nordic TEQ/kg of material burned for landfill fires.
26 This value (assumed equal to 1000 ng I-TEQ/kg) was also adopted by UNEP (2005). This factor
27 is about four times higher than the factor developed by Collet and Fiani (2006). The midpoint of
28 this range, or 600 ng I-TEQ/kg, was adopted here for each reference year. Neither Persson and
29 Bergstrom (1991) nor Collet and Fiani (2006) reported individual congener data that would have
30 allowed converting this I-TEQ estimate to a WHOgg TEQ estimate. However, Ruokojarvi et al.
31 (1995) reported congener profiles for air concentrations measured during a landfill fire in
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1 Finland. This profile suggest that the WHOgg TEQs would be about 20% greater than the
2 I-TEQs. On this basis, the emission factor of 600 ng I-TEQ/kg was converted to
3 700 ng WHOgg TEQ/kg. The kinds of wastes and combustion conditions occurring in landfill
4 fires are likely to be highly variable. It is very uncertain how well these are represented in the
5 limited experiments used to derive the emission factors. Therefore, this emission factor was
6 assigned a preliminary confidence rating.
7 Blomqvist et al. (2007) used an emission factor range of 40 to 900 ng TEQ/kg for landfill
8 fires in the Swedish inventory. This was based on two studies conducted in Sweden, one
9 described as a "model study on household waste" and the other as one that "quantified emissions
10 from real waste dump fires."
11 In order to use the per kg emission factors reported above, it is necessary to estimate the
12 amount of waste burned in landfill fires. Persson and Bergstrom (1991) assumed that 100,000 kg
13 of material are burned in each surface fire and 350,000 kg are burned in deep fires. The
14 midpoint of this range (225,000 kg) was multiplied by the number of landfill fires occurring in
15 the United States. The U.S. Fire Administration (USFA, 2001) reports that an average of
16 8,300 landfill fires occur each year (where landfills are defined broadly to include public or
17 private areas where waste is buried; this includes municipal solid waste landfills and general
18 refuse disposal areas and dumps in open ground). This suggests that a total of 1.9 MMT of
19 material/year are burned in landfill fires in the United States. No information was found on how
20 the number of landfill fires has changed over the reference years, and this amount (1.9 MMT)
21 was assumed to apply to each of the years. As discussed above, the actual trend is probably
22 downward because improved regulations and increases in methane recovery systems at landfills
23 are likely to have reduced landfill fire frequency/magnitude over this time frame. Considering
24 the lack of data to accurately reflect this trend and the uncertainty in the assumptions about the
25 amount of waste burned per fire, these activity estimates are considered preliminary
26 (Preliminary).
27 As shown below, this approach suggests a total release of 1,100 g I-TEQ. Another way
28 to estimate landfill fire releases is by using a per fire emission factor. Personn and Bergstrom
29 (1991) estimated that 35 g Nordic TEQ were released from landfills fires in Sweden. This
30 estimate assumed that 217 fires occurred per year (167 surface fires and 50 deep fires). This
31 implies an average release of 0.16 g Nordic TEQ/fire. Multiplying this by the number of fires
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1 occurring in the United States (8,300/year as reported by the USFA, 2001) suggests a total
2 release of 1,300 g Nordic TEQ. This value is similar to the original one using a per capita
3 approach, which gave estimates of about 1,000 g I-TEQ/year (assuming minor differences
4 between Nordic TEQs and I-TEQs). Although these alternative approaches suggest similar
5 releases, the release estimate is still considered preliminary due to the uncertainties in both the
6 emission factor and activity estimates.
7
8 6.3.2. Water Releases—None
9
10 6.3.3. Solid Residue Releases—None
11
12 6.3.4. Products—None
13
14 6.3.5. Release Summary
15 The inventory decision criteria and releases to all media are summarized below:
16
Inventory Decision Criteria for Landfill Fires
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
No
Yes
No
P
17
18
19
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Landfill Fires
Air Releases
Emission Factors
• 1987—700 ng WHO98 TEQ/kg (600 ng I-TEQ/kg) of material burned (Preliminary).
• 1995—700 ng WHO98 TEQ/kg (600 ng I-TEQ/kg) of material burned (Preliminary).
• 2000—700 ng WHO98 TEQ/kg (600 ng I-TEQ/kg) of material burned (Preliminary).
Activity Levels
• 1987—1.9 MMT (Preliminary).
• 1995—1.9 MMT (Preliminary).
• 2000—1.9 MMT (Preliminary).
Releases
• 1987—1,300 g WHO98 TEQDF (1,100 g I-TEQDF) (Preliminary).
• 1995—1,300 g WHO98 TEQDF (1,100 g I-TEQDp) (Preliminary).
• 2000—1,300 g WHO98 TEQpp (1,100 g I-TEQDF) (Preliminary).
Water Releases
None.
Solid Residue Releases
None.
Products
None.
3 6.4. FOREST AND BRUSH FIRES
4 6.4.1. Air Releases
5 As described below, a number of additional studies have been identified, allowing
6 updates to the air-release estimates from forest fires.
7 Ikeguchi and Tanaka (1999) simulated the open burning of several waste types using a
8 large furnace with open doors. The flue gas was sampled immediately downstream of the
9 furnace. One test was conducted with tree and leaf materials. A total of 162.7 kg of this material
10 were burned in a batch mode lasting 33 minutes. The emission factor was estimated as
11 4.7 I-TEQ/kg of waste. UNEP (2005) used this study to support their recommended emission
12 factor of 5 ng TEQ/kg of biomass burned for forest fires.
13 Gonczi et al. (2005) measured dioxin emissions from burning various types of domestic
14 wastes under a variety of conditions. One test involved the open burning of garden waste, which
15 was composed of approximately one half wood branches and one half leaves and grass. A
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1 sampling hood was mounted 0.5 m above the fire to collect the emissions. This test yielded an
2 emission factor of 27 ng TEQ/kg.
3 Blomqvist et al. (2007) used an emission factor of 2 ng TEQ/kg for forest fires in the
4 Swedish inventory. This was based on work by Bhargava et al. (2002) who measured dioxin
5 emissions from the combustion of different wood materials in a cone calorimeter.
6 Collet and Fiani (2006) studied the emissions of PAHs, PCBs, and CDD/CDF emissions
7 from simulated forest and landfill fires in France. They collected samples from two forests in the
8 southeast and southwest of France during August, 2003. The samples consisted of litters,
9 mosses, heathers, brackens, conifer needles, pine cones, shrubs, barks, pine, and oak branches.
10 The 80 m3 combustion chamber had an air flow of 1,800 m3/hour, corresponding to 22.5 volume
11 changes per hour, to simulate open burning conditions. Emissions were sampled near the
12 chamber exit prior to the scrubber and measured in accordance with existing European standards
13 (EN 1948-1-2-3 for CDD/CDFs and PCBs). For the five simulated forest fire tests, they
14 estimated these emission factors for CDD/CDFs, in ng I-TEQ/kg: 10.4, 1.02, 25.9, 12.1, and 3.3,
15 for an average of 10.5 ng I-TEQ/kg. Collet and Fiani also provide emission factors for
16 12 dioxin-like PCBs, in ng I-TEQ/kg: 0.48, 0.35, 2.34, 0.74, and 0.23, for an average of
17 0.8 ng I-TEQ/kg. Based on these results they provide a "first estimate" of emissions from forest
18 fires in France of 28.8 g I-TEQ/year.
19 Using a controlled-burn facility, Gullett and Touati (2003) estimated CDD/CDF
20 emissions through the testing of three biomass samples collected from the Oregon coast near
21 Seal Rock and from four biomass samples collected from the North Carolina Piedmont region,
22 approximately 200 km from the Atlantic coast. The samples generally consisted of equal
23 portions of live shoots (needles cut from tree branches) and needle litter gathered from the forest
24 floor. The Oregon samples were composed of pine needles (Pinus contorta and Pinus
25 monticold) and hemlock needles (Tyuga heterophylla); the North Carolina samples were
26 composed entirely of lobolly pine (Pinus taedd). The combustion of these seven samples, piled
27 approximately 10 cm high, took place on top of an open, flat combustion platform. The average
28 total TEQ emission factors for the three Oregon samples and the four North Carolina samples
29 were 15 ng and 25 ng WHOgg TEQDF/kg, respectively. Because the waxy cuticle layer on pine
30 needles has been demonstrated to absorb lipophilic compounds from the atmosphere, Gullett and
31 Touati (2003) also extracted a raw, as-received Oregon biomass sample to determine whether the
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1 observed emissions were due to simple vaporization of existing CDDs/CDFs or the formation of
2 new CDDs/CDFs in the combustion process. The CDD/CDF concentration in the sample
3 measured 1.3 ng WHOgg TEQop/kg, which is approximately 20 times lower than the Oregon
4 CDD/CDF emission factor. The CDD/CDF isomer patterns of the extracted biomass samples
5 and the emission samples were similar. Therefore, this preliminary evidence suggests CDD/CDF
6 emissions are not due solely to vaporization of cuticle-bound CDDs/CDFs but are primarily a
7 result of new formation during forest fires.
8 Gullett et al. (2008) present emission factor data for several types of forest and grass
9 fires. The study used the same burn chamber as described above for Gullett and Touati (2003).
10 Burn tests (n = 27) on forest biomass from five sources gave emission factors ranging from 0.3
11 to 26.3 ng TEQ/kg of carbon burned with an average of 5.8 ng TEQ/kg of carbon burned (the
12 TEQs were reported to be essentially the same whether presented as I-TEQs or WHOgs) The
13 authors indicate that forest biomass contains approximately 50% carbon. Thus, the reported
14 emission factors can be converted to a whole biomass basis by multiplying by 0.5. The study
15 also found that the total CDD/CDF in the emissions exceeded the amounts in the raw biomass by
16 a factor of four, confirming that formation was occurring during the combustion process.
17 Meyer et al. (2004, 2007) conducted a series of chamber and field tests in Australia to
18 characterize dioxin emission from a variety of fire types. Five chamber tests were conducted
19 with forest leaf litter (eucalyptus, box, and ironbark) and producing a mean emission factor of
20 0.37 ng WHOgg TEQop/kg of fuel. A total of 18 forest fire field tests were conducted using
21 portable high volume air samplers. The field monitors also measured CC>2, which was related to
22 combusted biomass and used to calculate emission factors. The field test results are summarized
23 below:
24
25 • Ten prescribed burns in Queensland (coastal forest), Victoria (eucalyptus), and Western
26 Australia (jarrah forest) with a mean emission factor of 0.5 ng WHOgg TEQop/kg of fuel.
27 • Three fires in tropical savannas with a mean emission factor of 1.1 ng WHOgg TEQDF/kg
28 of fuel.
29 • Two wildfires in Victoria (mixed eucalyptus) with a mean emission factor of
30 0.7 ng WHO9g TEQDF/kg of fuel.
31 • Three woodland fires with a mean emission factor of 1.5 ng WHOgg TEQop/kg of fuel.
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1 6.4.2. Air Emission Factors
2 Several lines of evidence indicate that forest fires release dioxins to the environment.
3 Sediment core studies have shown that dioxins were found at measurable levels prior to the
4 industrial revolution (Smith et al., 1992, 1993). The most likely source for these residues is
5 natural fires. Gullett et al. (2003, 2008) used chamber tests to show that more dioxins are
6 emitted than contained in the biomass being burned. Finally, multiple chamber studies and
7 one large field study (summarized above) have now measured dioxins in forest fire emissions.
8 Thus, it is reasonably well established that dioxin emissions occur from forest fires.
9 The chamber studies have shown a wide range of results (means across tests vary from
10 0.37 to 25 ng TEQ/kg) suggesting that emissions are highly variable across fuel types and fire
11 conditions. The Australian field measurements suggest emission factors near the low end of the
12 chamber results. Meyer et al. (2004) believe that the chamber tests have overestimated dioxin
13 emissions due to longer residence time in the formation temperatures than occurs in the field.
14 They also support their belief that forest fires have low dioxin emissions on the basis of ambient
15 air monitoring in southern Victoria during the large forest fires in northeast Victoria in January
16 2003. The monitor showed clear impacts of the plume during the fire based on sharp increases in
17 particulate and potassium salts (biomass tracer) but no increases in dioxins.
18 As summarized in Table 6-1, a total of 6 chamber studies have been conducted with a
19 variety of wood types and a cumulative n of 46. Also, as summarized in Table 6-1, one large
20 field study was conducted in Australia involving various types of forests with an n of 18. The
21 w-weighted average for the field tests is 0.8 ng TEQDF/kg and for the chamber tests is
22 5.9 ng TEQop/kg. As discussed below, both types of tests have uncertainties, and the midpoint
23 of this range (3 ng TEQop/kg) was selected as a reasonable assumption for a central value
24 emission factor and applied to all three reference years.
25 The confidence in this emission factor depends on how representative the test data are of
26 the types of wood and fires that occur in North America:
27
28 • Wood types—Over 20 different types of forests exist in the United States (see Figure 6-2)
29 with a variety of wood types, biomass density, moisture content, height, etc. The
30 chamber tests did not represent all wood types found in North America but did include
31 some common types such as pine and oak. All of the field tests were conducted in
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1 Australia; some included pines, but others were primarily eucalyptus and jarrah trees,
2 which are uncommon in the United States.
3 • Fire types—A number of different types of fires can occur such as ground fires, which
4 burn the humus layer of the forest floor but do not burn appreciably above the surface;
5 surface fires, which burn forest undergrowth and surface litter; and crown fires, which
6 advance through the tops of trees or shrubs. It is not uncommon for two or three of the
7 types to occur simultaneously. The ground level monitors cannot directly sample the
8 high smoke plume generated near the tops of trees during a crown fire. Some of the
9 smoke generated during a crown fire is present at ground level, but it is uncertain how
10 representative this smoke is of the main plume. Ground/surface fires create a smoke
11 plume, which starts near ground level, and the monitors are much more likely to collect
12 samples, which are representative of these emissions. Similarly, the chamber tests cannot
13 mimic the intensity and scale of crown fires but may be representative of the conditions
14 associated with the smaller ground/surface fires.
15
16 In summary, the forest fire data appear to represent some but not all of the wood types
17 and fire types that occur in North America. The large database of emission tests suggest a wide
18 range of emission factors, but this is reasonable considering that they cover a wide variety of
19 wood types, fire types and burn conditions. The wide range of results increases the confidence
20 that the full range of emission factors have been characterized and that the midpoint of the range
21 provides a reasonable central point estimate. On this basis, the emission factor has been
22 upgraded from preliminary to quantifiable.
23
24 6.4.3. Air Activity Levels
25 EPA (2006) derived forest fire activity estimates using data on acres burned per year and
26 estimates of the amount of biomass per acre. New data for acres burned were found at a
27 database managed by the National Interagency Fire Center (MFC) (www.nifc.gov/fire). These
28 new data are compared to the previously used data in Table 6-2. The data are generally
29 comparable except for the wildfire data for 1987 and 1995 where the MFC data are less than half
30 the previously used values. These two estimates were changed to reflect these new data. The
31 amount of biomass burned per acre was assumed to be 9.43 MT/acre for wildfires and
32 7.44 MT/acre for prescribed burns (Ward et al., 1976). The total forest fire activities were
33 estimated as 61 MMT in 1987, 55 MMT in 1995 and 243.8 MMT in 2000. A review of the
34 NFIC historical data on wildfires from 1960 to 2008 suggests that the acres burned in 2000 were
35 above average and the acres burned in 1987 and 1995 were below average.
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1 6.4.4. Water Releases
2 It is possible that dioxin-contaminated particles could be entrained in water used to fight
3 fires or rainwater that falls on the site. This water could run off the site and eventually get into
4 surface waters. No quantitative release estimates could be made. Therefore, this is a possible
5 but unquantifiable source.
6
7 6.4.5. Solid Residue Releases
8 Buckland et al. (1994) collected soil samples in a national park near Sydney, Australia.
9 Some were collected in areas where large brush fires had occurred 6 weeks earlier and others in
10 areas where no fires had occurred. The sampling depth was 2 cm. The dioxin content of
11 samples from burnt areas ranged from 2.2 to 36.8 pg I-TEQ/g, and the samples from unburnt
12 areas ranged from 3.0 to 10.0 pg I-TEQ/g. They concluded that the fires had not had a major
13 impact on the soil levels.
14 No other direct measures of CDD/CDF content of forest fire ash were found. Wunderli
15 et al. (1996) determined an average of 10 ng I-TEQ/kg of ash generated for clean wood burned in
16 stoves. This value is similar to the levels measured by Buckland et al. (1994) in surface soils
17 after fires and is assumed here for forest fires. UNEP (2005) recommended 4 ng I-TEQ/kg of
18 material burned (this was derived from an estimate of 200 ng I-TEQ/kg of ash and assumption of
19 2% ash). This emission factor is assigned a preliminary confidence rating because direct
20 measurements were available from only one area/fire type and it is unclear if it is representative
21 of other areas.
22 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to
23 8% ash (Ragland et al., 1991). A midrange value of 3% is assumed here for all wood burned.
24 Multiplying this value by the activity factors discussed above for biomass burned in fires yields
25 the following: 1.8 MMT in 1987, 1.7 MMT in 1995, and 7.3 MMT in 2000.
26
27 6.4.6. Products—None
28
29 6.4.7. Release Summary
30 The inventory decision criteria and releases to all media are summarized below:
31
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Inventory Decision Criteria for Forest and
2
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
he class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Air
Yes
Yes
Yes
Yes
Q
Brush Fires
Water Solids Products
Yes
Yes
No
Yes
P
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Forest and Brush Fires
Air Releases
Emission Factors
• 1987—3 ng WHO98 TEQDF/kg.
• 1995—3 ng WHO98 TEQDF/kg.
• 2000—3 ng WHO98 TEQDF/kg.
Activity Levels
• 1987—61 MMT.
• 1995—55 MMT.
• 2000—243.8 MMT.
Releases
es
1987—180 g WHO98 TEQDF.
1995—170 g WHO98 TEQoF.
2000—730 g WHO98 TEQDF.
Water Releases
None.
Solid Residue Releases
Emission Factors
• 1987—10 ng I-TEQDF/kg ash (Preliminary).
• 1995—10 ng I-TEQDF/kg ash (Preliminary).
• 2000—10 ng I-TEQDF/kg ash (Preliminary).
Activity Levels
• 1987—1.8 MMT ash.
• 1995—1.7 MMT ash.
• 2000—7.3 MMT ash.
Releases
• 1987—18 g I-TEQoF (Preliminary).
• 1995—17 g I-TEQoF (Preliminary).
• 2000—73 g I-TEQDF (Preliminary).
Products
None.
1
2
3 6.5. BACKYARD BARREL BURNING
4 6.5.1. Air Releases
5 Additional studies are presented below, and changes were made to the 2000 activity
6 estimate and resulting release estimate.
7
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1 Hirai et al (2003) estimated total CDD/F emission factors from soil measurements at
2 open burning sites. Soil concentrations in India of 52 pg TEQ/g implied an emission factor over
3 500 pg TEQ/g of waste. Soil concentrations in Cambodia of 400 pg TEQ/g implied an emission
4 factor over 4000 pg TEQ/g of waste.
5 Wevers et al. (2004) measured dioxin emissions from the combustion of garden waste in
6 barrels and in open fires, and the incineration of household waste in an empty oil drum. Each set
7 of experiments was composed of eight individual experiments over 4 hours. Air samples were
8 taken in the plume with a medium volume sampler equipped with a quartz filter and a
9 polyurethane plug. Emission factors in the order of magnitude of 4.5 ng TEQ/kg combusted
10 garden waste and 35 ng TEQ/kg burned municipal waste were determined.
11 Hedman et al. (2005) measured the emissions of CDD/CDFs and PCBs from
12 uncontrolled domestic combustion of waste. The waste fuels used were garden waste, paper,
13 paper and plastic packaging, refuse-derived fuel (RDF), PVC, and electronic scrap. Samples
14 were collected from the emissions drawn through a conical fume hood placed directly over the
15 barrel. Combustions including PVC and electronic scrap emitted several orders of magnitude
16 more dioxins than the other waste fuels. Emissions from the other fuels had considerable
17 variations, but the levels were difficult to relate to waste composition. Emission factors of
18 CDD/CDF and PCB from the backyard burning ranged from 2.2 to 13,000 ng (WHO TEQ)/kg.
19 The levels found in ash usually were less than 5% of the total. For assessment of total emissions
20 of dioxins and PCB from backyard burning of low and moderately contaminated wastes, an
21 emission factor range of 4-72 ng WHO TEQ/kg is suggested.
22 Gonczi et al. (2005) tested emissions from burning domestic wastes in barrels (19 tests)
23 and open fires (2 tests). Gas collected above these fires allowed for estimation of emission
24 factors for CDD/CDFs and dioxin-like PCBs for barrel burn and open fire conditions. The
25 material burned consisted of various mixtures of garden wastes, straw, paper, several forms of
26 plastic, waste motor oil, RDF, and computer scrap. A barrel burn with a mix of garden waste
27 and polyvinyl chloride (PVC) waste had the highest emission factor of
28 96,000 ng WHOgg TEQop/kg burned. The other emission tests ranged from 2.2 to
29 890 ng WHO98 TEQP/kg burned.
30 The emission factor selected in the original report was 76.8 ng WHOgg TEQDF/kg
31 (72.8 ng I-TEQoF/kg) based on studies by Gullett et al. (1999, 2000) and Lemieux et al. (2000).
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1 This falls within the range found by Gonczi et al. (2005), about twice the level found by Weveres
2 et al. (2004) and near the upper end of the range recommended by Hedman et al. (2005).
3 Accordingly, the original emission factor still appears to be a reasonable central estimate, and no
4 changes were made.
5 The original report (US EPA, 2006) presented data from six surveys on the prevalence of
6 backyard trash burning. This data was combined with trash generation rates and Census data on
7 rural populations to derive national estimates of the amount of trash burned in backyards for each
8 of the reference years. The original report also described an alternative activity estimate for
9 2000 developed by OAQPS. The alternative method used similar factors applied on a county by
10 county basis and made adjustments for amount of waste recycled and influence of open burning
11 bans. The present report considered the OAQPS method more accurate and adopted it for the
12 year 2000. This resulted in a 16% increase in activity and a corresponding increase in releases in
13 2000. No changes were made to the release estimates for 1987 and 1995. All activity estimates
14 are presented in the release summary below.
15
16 6.5.2. Solid Residue Releases
17 Minh et al. (2003) measured CDDs and CDFs in soils from open burning dump sites for
18 municipal waste in the Philippines, Cambodia, India, and Vietnam. Average levels across sites
19 ranged from 2 to 520 pg WHOgg TEQ/g. The levels were higher than those in agricultural and
20 urban areas distant from the dump sites.
21 Lemieux (1997) collected ash samples from open barrel burning and analyzed them for
22 CDDs/CDFs. Ash samples from the experiments were combined, resulting in two composite
23 samples, one for recyclers, and one for nonrecyclers. The average of the recycler and
24 nonrecycler values were averaged and assumed to apply to all three reference years: 1,670 ng
25 WHOgg TEQDF/kg (1,640 ng I-TEQDF/kg) of ash.
26 The generation rate of ash from backyard barrel burning is assumed to match that of
27 municipal waste incineration, which has a central estimate of 15% for bottom ash as discussed in
28 Section 3.1. Applying this to the total amount burned (as discussed above) yields these activity
29 levels for each reference year: 1.2 MMT in 1987, 1.2 MMT in 1990, and 1.2 MMT in 2000.
30 The solid residue releases were estimated by multiplying the emission factor and activity
31 level for each reference year (results shown in summary chart below). It is possible that some of
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1 the ash from barrel burning is taken to municipal waste landfills, but most is probably not.
2 Therefore, all of these releases are assumed to occur to the open environment.
3
4 6.5.3. Release Summary
5 The inventory decision criteria and releases to all media are summarized below:
6
Inventory Decision Criteria for Backyard Barrel Burning
Air Water Solids Products
Emission tests for at least two units/source types with Yes Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have Yes Yes
understandable differences.
mission factor tests represent units that are typical of the Yes Yes
class.
Activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary). Q Q
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Backyard Barrel Burning
Air Releases
Emission Factors
• 1987—77 ng WHO98 TEQDF/kg (73 ng I-TEQDF/kg).
• 1995—77 ng WHO98 TEQDF/kg (73 ng I-TEQDF/kg).
• 2000—77 ng WHO98 TEQDF/kg (73 ng I-TEQDF/kg).
Activity Levels
• 1987—7.87 MMT.
• 1995—8.18 MMT.
• 2000—7.79 MMT.
Releases
es
1987—610 g WHO98 TEQDF (570 g I-TEQDF).
1995—630 g WHO98 TEQDF (600 g I-TEQDF).
2000—600 g WHO98 TEQDF (570 g I-TEQDF).
Water Relea;
None
Solid Residue Releases
Emission Factors
• 1987—1,700 ng WHO98 TEQDF/kg (1,600 ng I-TEQDF/kg) of ash.
• 1995—1,700 ng WHO98 TEQDF/kg (1,600 ng I-TEQDF/kg) of ash.
• 2000—1,700 ng WHO98 TEQDF/kg (1,600 ng I-TEQDF/kg) of ash.
Activity Levels
• 1987—1.2 MMT.
• 1995—1.2 MMT.
• 2000—1.2 MMT.
Releases
es
1987—2,000 g WHO98 TEQDF (1,900 g I-TEQDF).
1995—2,000 g WHO98 TEQDF (2,000 g I-TEQDF).
2000—2,000 g WHO98 TEQDF (1,900 g I-TEQDF).
Products
None.
1
2
3
4
5
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1 6.6. RESIDENTIAL YARD WASTE BURNING
2 Additional studies are presented below, and changes were made to the release estimates.
O
4 6.6.1. Air Releases
5 Ikeguchi and Tanaka (1999) simulated the open burning of several waste types using a
6 large furnace with open doors. The flue gas was sampled immediately downstream of the
7 furnace. One test was conducted with tree and leaf materials. A total of 162.7 kg of this material
8 were burned in a batch mode lasting 33 minutes. The emission factor was estimated as
9 4.7 I-TEQ/kg of waste.
10 Gonczi et al. (2005) measured dioxin emissions from burning various types of domestic
11 wastes under a variety of conditions. One test involved the open burning of garden waste, which
12 was composed of approximately one half wood branches and one half leaves and grass. A
13 sampling hood was mounted 0.5 m above the fire to collect the emissions. This test yielded an
14 emission factor of 27 ng TEQ/kg.
15 Wevers et al. (2004) measured dioxin emissions from the combustion of garden waste in
16 barrels and in open fires, and the incineration of household waste in an empty oil drum. Each set
17 of experiments was composed of eight individual experiments over 4 hours. Air samples were
18 taken in the plume with a medium volume sampler equipped with a quartz filter and a
19 polyurethane plug. For garden waste, an emission factors of 4.5 ng TEQ/kg of waste was
20 determined.
21 Hedman et al. (2005) measured the emissions of CDD/CDFs and PCBs from
22 uncontrolled burning of various forms of household waste. Samples were collected from the
23 emissions drawn through a conical fume hood placed directly over the barrel. For burns with
24 garden waste (n = 3), CDD/CDF emission factors ranged from 12 to 100 ng WHO9g TEQ/kg of
25 material burned with a median value of 20 ng WHOgg TEQ/kg of material burned.
26 The studies summarized above had central values ranging from about 4 to
27 27 ng WHO98 TEQ/kg of material burned. A midrange value of 10 ng WHO98 TEQ/kg of
28 material burned was selected as an overall central estimate.
29 As described in the original report, OAQPS estimated that 255,000 MT of leaf and
30 255,000 MT of brush (total of 510,000 MT of yard waste) were burned in 2000. Estimates for
31 1987 and 1995 were derived by assuming that the activities would be proportional to the total
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1 U.S. population for these years. This approach yields the following activity levels for each
2 reference year: 441,000 MT in 1987, 485,000 MT in 1995, and 510,000 MT in 2000.
3
4 6.6.2. Water Releases—None
5
6 6.6.3. Solid Residue Releases
7 Hedman et al. (2005) measured an ash emission factor of 0.02 ng WHOgg TEQ/kg of
8 waste burned for barrel burning of garden waste. It is assigned a preliminary confidence rating
9 because it is based on only one waste sample.
10
11 6.6.4. Products—None
12
13 6.6.5. Release Summary
14 The inventory decision criteria and releases to all media are summarized below:
15
16
17
18
Inventory Decision Criteria for Residential Yard Waste
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Air Water
Yes
Yes
Yes
Yes
Q
Burning
Solids Products
No
Yes
Yes
P
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Residential Yard Waste Burning
Air Releases
Emission Factors
• 1987— 10 ng WHO98 TEQDF/kg.
• 1995—10 ng WHO98 TEQDF/kg.
• 2000— 10 ng WHO98 TEQDF/kg.
Activity Levels
• 1987—441,000 MT.
• 1995—485,000 MT.
• 2000—510,000 MT.
Releases
• 1987—4 g WHO98 TEQDF.
• 1995—5 g WHO98 TEQDF.
• 2000—5 g WHO98 TEQpF.
Water Releases
None.
Solid Residue Releases
Emission Factors
• 1987—0.02 ng WHO98 TEQDF/kg of material burned (Preliminary).
• 1995—0.02 ng WHO98 TEQDF/kg of material burned (Preliminary).
• 2000—0.02 ng WHO98 TEQDF/kg of material burned (Preliminary).
Activity Levels
• 1987—441,000 MT.
• 1995—485,000 MT.
• 2000—510,000 MT.
Releases
• 1987—<0. Ig WHO98 TEQDF (Preliminary).
• 1995—<0.1 g WHO98 TEQoF (Preliminary).
• 2000—<0.1 g WHO98 TEQDF (Preliminary).
Products
None.
2
3
4 6.7. LAND-CLEARING DEBRIS BURNING
5 6.7.1. Air Releases
6 The emission factor was changed to correspond to the new forest fire emission factor. No
7 direct measurements of CDD/CDF emissions from the burning of land-clearing debris have been
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1 performed, so the average emission factor of 3 ng WHOgg TEQop/kg, which was used for forest
2 fires is also used for burning of land-clearing debris. This factor was assumed to apply to all
3 three reference years. A preliminary confidence rating was assigned to the emission factor
4 estimate because it was derived from forest fire testing and may not be representative of
5 land-clearing debris burning.
6 No changes were made to the activity level estimates. As described in EPA (2006), these
7 were provided by OAQPS and involved multiplying estimates of acres cleared during residential,
8 nonresidential, and roadway construction by the fuel-loading factors.
9
10 6.7.2. Water Releases—None
11
12 6.7.3. Solid Residue Releases
13 Wunderli et al. (1996) determined an average of 10 ng I-TEQ/kg of ash generated for
14 clean wood. This value is recommended by UNEP (2005) for virgin biomass fired stoves and is
15 adopted here for ash from land-clearing debris burning. It is assigned a preliminary confidence
16 rating because ash from land-clearing debris burning may be different from stove ash.
17 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to
18 8% ash (Ragland et al., 1991). A midrange value of 3% is assumed here for all debris burned.
19 Multiplying this value by the activity factors discussed above for land clearing debris fires yields
20 the following: 831,000 MT in 1987, 792,000 MT in 1995, and 852,000 MT in 2000.
21
22 6.7.4. Release Summary
23 The inventory decision criteria and releases to all media are summarized below:
24
25
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Inventory Decision Criteria for Land-Clearing Debris Burning
Air Water Solids Products
Emission tests for at least two units/source types with No No
mfficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
No No
mission factor tests represent units that are typical of the
lass.
activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary).
1
2
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Land-Clearing Debris Burning
Air Releases
Emission Factors
• 1987—3 ng WHO98 TEQDF/kg (Preliminary).
• 1995—3 ng WHO9g TEQDF/kg (Preliminary).
• 2000—3 ng WHO98 TEQDF/kg (Preliminary).
Activity Levels
• 1987—27.7 MMT.
• 1995—26.4 MMT.
• 2000—28.4 MMT.
Releases
• 1987—83 g WHO98 TEQDF (Preliminary).
• 1995—79 g WHO98 TEQDF (Preliminary).
• 2000—85 g WHO98 TEQDF (Preliminary).
Water Releases
None.
Solid Residue Releases
Emission Factors
• 1987— 10 ng I-TEQoF/kg of ash (Preliminary).
• 1995—10 ng I-TEQoF/kg of ash (Preliminary).
• 2000— 10 ng I-TEQpF/kg of ash (Preliminary).
Activity Levels
• 1987—0.831 MMT ash.
• 1995—0.792 MMT ash.
• 2000—0.852 MMT ash.
Releases
• 1987—8 g WHO98 TEQDF (Preliminary).
• 1995—8 g WHO98 TEQDF (Preliminary).
• 2000—9 g WHO98 TEQpF (Preliminary).
Products
None.
1
2
3 6.8. UNCONTROLLED COMBUSTION OF POLYCHLORINATED BIPHENYLS
4 No new studies were found on this topic, and no changes were made to the release
5 estimate. The use of PCBs in new transformers in the United States is banned, and their use in
6
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1 existing transformers and capacitors is being phased out under regulations promulgated under the
2 Toxic Substances Control Act.
3 Because of the accidental nature of these incidents, the variation in duration and intensity
4 of elevated temperatures, the variation in CDD/CDF content of residues, and the uncertainty
5 regarding the amount of PCBs still in service in electrical equipment, EPA judged the available
6 data inadequate for developing any quantifiable emission estimates. Therefore, they are
7 considered unquantifiable for air and solid residue releases. Information on this source is also
8 presented in Chapter 11.
Uncontrolled Combustion of PCBs
CDDs and CDFs have been detected in soot from PCB fires, but the available information is
insufficient to make quantitative release estimates. Therefore, it is considered an unquantifiable
source for air and solid residue releases.
9 6.9. VOLCANOES
10 No evidence exists that this source can release CDDs/CDFs and, therefore, it is not even
11 considered unquantifiable.
12 6.10. FIREWORKS
13 No new studies were found on this topic, and no changes were made to the release
14 estimate. Evidence exists that fireworks can release CDDs/CDFs to the air and solid residues,
15 but insufficient information exists to make a quantitative estimate. Therefore, it is considered
16 unquantifiable for air and solid residue releases.
17
Fireworks
CDDs and CDFs have been detected in fireworks ash and in air after using fireworks, but the
available information is insufficient to make quantitative release estimates. Therefore, it is
considered an unquantifiable source for air and solid residue releases.
18 6.11. OPEN BURNING AND OPEN DETONATION OF ENERGETIC MATERIALS
19 No evidence exists that this source can release CDDs/CDFs, and, therefore, it is not even
20 considered unquantifiable.
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1 6.12. UNDERGROUND COAL FIRES
2 Underground coal fires are a possible source of CDD/CDFs to the air because CDD/CDF
3 releases have been measured from other forms of coal burning. However, no emissions data or
4 activity information were found specifically for this source, so no quantitative release estimate
5 could be made (Not quantifiable).
6
Underground Coal Fires
The available information is insufficient to make quantitative release estimates (Not
quantifiable).
7
8 6.13. AGRICULTURAL BURNING
9 This source category was not included in the original report. Agricultural fields are
10 sometimes burned prior to harvesting to facilitate crop collection and sometimes after harvesting
11 to clear the fields and control weeds. In the United States, it is believed that this practice is most
12 prevalent for sugar cane, and it is the only crop addressed in this section.
13
14 6.13.1. Air Releases
15 Gullett et al. (2006) measured dioxin emission from simulated sugarcane field burns.
16 Sugarcane leaves from Hawaii and Florida were burned in a manner simulating the natural
17 physical dimensions and biomass density found during the practice of preharvest field burning.
18 Eight composite burn tests consisting of 3-33 kg of biomass were conducted, some with
19 replicate samplers. Emission factor calculations using sampled concentration and measured
20 mass loss compared well to rigorous carbon balance methods commonly used in field sampling.
21 The two sources of sugarcane had distinctive emission levels, as did tests on separate seasonal
22 gatherings of the Florida sugarcane. The average emission factor for two tests of Hawaii
23 sugarcane was 114 ng TEQ/kg of biomass and for two gatherings of Florida sugarcane was
24 11 ng TEQ/kg biomass and 2 ng TEQ/kg biomass (these values were originally reported on a
25 carbon basis and were converted to a total biomass basis by multiplying by 45%).
26 Meyer et al. (2004) conducted a series of chamber and field tests in Australia to
27 characterize dioxin emissions from a variety of fire types including agricultural fires. The mean
28 emission factors from the chamber tests are listed below:
29
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1 • Straw— 17 ng WHO98 TEQDF/kg of fuel.
2 • Sorghum—3 5 ng WHO9g TEQDF/kg of fuel.
3 • Sugar cane—5 ng WHOgg TEQDF/kg of fuel.
4
5 Additionally, two field tests were conducted during sugar cane burning. These tests used
6 portable high volume air samplers. The field monitors also measured CC>2, which was related to
7 combusted biomass and used to calculate emission factors. The emission factor was
8 1.2 ng WHO98 TEQDF/kg of fuel.
9 UNEP (2005) recommended an emission factor for agricultural residue burning of
10 30 ng I-TEQ/kg of material burned (in fields where pesticides or other contaminants are present)
11 and 0.5 ng I-TEQ/kg of material burned (in fields where pesticides or other contaminants are not
12 present).
13 In summary, sugar cane chamber tests have produced a very wide range of emission
14 factors from 2 to 114 ng TEQ/kg. The limited field testing yielded an emission factor of
15 1 ng TEQ/kg. Accordingly, there is considerable uncertainty about what value is most
16 representative of U.S. conditions. For the purposes of a preliminary estimate, a value of
17 10 ng TEQ/kg (rounded geometric mean of range) was selected.
18 Gullett et al. (2006) derived activity estimates for sugar cane burning in the United States
19 using the following factors: the sugar cane field area for Hawaii, Texas, Louisiana, and Florida; a
20 biomass production rate of 20 dry tons/ha; and the assumption that 50% of the sugar cane crop
21 was burned with 90% combustion efficiency. This approach suggests that about 3.5 MMT of
22 sugar cane were burned. The data were from the 2001-2003 time frame and are assumed here to
23 apply to 2000. USDA (2009) indicates that sugar cane production increased by about 10% from
24 1995 to 2000, and a similar amount is assumed for 1987 to 1995. On this basis, the amount of
25 sugar cane burned in 1987 was 2.8 MMT, and the amount in 1995 was 3.1 MMT. Considering
26 the multiple assumptions required for this estimate, it is assigned a preliminary confidence
27 rating.
28
29 6.13.2. Water Releases—None
30
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1 6.13.3. Solid Residue Releases
2 Gullett et al. (2006) measured the dioxin content of ash from several samples with a
3 range of 0.004 to 1.22 ng WHO98 TEQ/kg of initial carbon of the biomass. Meyer et al. (2004)
4 measured the dioxin content of sugar cane ash as 1 ng WHOgg TEQ/kg of carbon. An emission
5 factor of 1 ng WHOgg TEQ/kg of carbon was selected as a central value within the range
6 observed by Gullett et al. (2006). It was converted to 0.5 ng TEQ/kg of biomass burned
7 assuming 45% carbon in the biomass. UNEP (2005) recommends a higher land emission factor
8 for agricultural residue burning of 10 ng I-TEQ/kg of material burned, but the basis was not
9 clear. Based on the limited testing showing widely ranging results, it was assigned a preliminary
10 confidence rating.
11
12 6.13.4. Products—None
13
14 6.13.5. Release Summary
15 The inventory decision criteria and releases to all media are summarized below:
16
Inventory Decision Criteria for
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Vleasured emission factors consistent or have
understandable differences.
Sugar Cane Burning
Air Water
Yes
No
Yes
Solids Products
Yes
No
Yes
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
P
Yes
P
17
18
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1
2
Sugar Cane Burning
Air Releases
Emission Factors
• 1987—10 ng WHO98 TEQDF/kg of biomass (Preliminary).
• 1995—10 ng WHO98 TEQDF/kg of biomass (Preliminary).
• 2000—10 ng WHOgg TEQDF/kg of biomass (Preliminary).
Activity Levels
• 1987—2.8 MMT (Preliminary).
• 1995—3.1 MMT (Preliminary).
2000—3.5 MMT (Preliminary).
Releases
eleases
• 1987—28 g WHO98 TEQDF (Preliminary).
• 1995—31 g WHO98 TEQDF (Preliminary).
• 2000—35 g WHO98 TEQDF (Preliminary).
VI7~i T>
Water Releases
None.
. Solid Residue Releases
Emission Factors
• 1987—0.5 ng WHO98 TEQDF/kg of biomass (Preliminary).
• 1995—0.5 ng WHO98 TEQDF/kg of biomass (Preliminary).
• 2000—0.5 ng WHO98 TEQDF/kg of biomass (Preliminary).
Activity Levels
• 1987—2.8 MMT (Preliminary).
• 1995—3.1 MMT (Preliminary).
• 2000—3.5 MMT (Preliminary).
Releases
• 1987—1 g WHO98 TEQDF (Preliminary).
• 1995—2 g WHO98 TEQDF (Preliminary).
• 2000—2 g WHO98 TEQpF (Preliminary).
Products
None.
3
4
5 6.14. OPEN BURNING DEMOLITION/CONSTRUCTION WOOD
6 6.14.1. Air Releases
7 This is a new section. No direct measurements of CDD/CDF emissions from the open
8 burning of demolition/construction wood were found. However, this activity involves similar
9
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1 material as burned in structural fires. As discussed in Section 6.2.1, the presence of
2 manufactured boards and treated lumber in structures is expected to increase dioxin emissions
3 relative to the combustion of untreated natural wood. Section 6.2.1 derived a structural fire
4 emission factor of 32 ug I-TEQ/fire by averaging data from Carroll (1996) and Thomas and
5 Spiro (1995) and converting to a mass basis by dividing by a default fuel-loading factor for
6 structural fires of 1.15 tons/fire (ERG, 2001), yielding 28 ng I-TEQ/kg. This factor was assumed
7 to apply to the open burning of demolition/construction wood for all three reference years. A
8 preliminary confidence rating was assigned to the emission factor estimate because it was
9 derived from structural fire estimates that were considered preliminary.
10 U.S. DOE (2000) reports that 8 MMT of wood construction and demolition debris were
11 generated in 1995. The majority of this waste was legally disposed via landfill or incineration.
12 However, an unknown portion is open burned at construction sites. For the purposes of a
13 preliminary estimate, it is assumed that 10% of the total, or 0.8 MMT, is open burned during all
14 three reference years.
15
16 6.14.2. Water Releases—None
17
18 6.14.3. Solid Residue Releases
19 As discussed in Section 6.2, an ash emission factor of 300 ng WHOgg TEQDF/kg of
20 material burned was developed for structural fires and is adopted here for ash from open burning
21 of construction/demolition wood. A preliminary confidence rating was assigned to the emission
22 factor estimate because it was derived from structural fire estimates.
23 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to
24 8% ash (Ragland et al., 1991). A midrange value of 3% is assumed here for all wood burned.
25 Multiplying this value by the activity factors discussed above for open burning of
26 construction/demolition wood yields the following: 0.024 MMT in all reference years. These are
27 given a preliminary confidence rating because they are derived from emission factors with
28 preliminary confidence ratings.
29
30 6.14.4. Release Summary
31 The inventory decision criteria and releases to all media are summarized below:
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Open Burning Demolition/Construction Wood
Air Water Solids Products
Emission tests for at least two units/source types with No No
mfficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
No No
mission factor tests represent units that are typical of the
lass.
activity estimates based on source-specific surveys. No No
Conclusion (Q = Quantitative, P = Preliminary).
1
2
This document is a draft for review purposes only and does not constitute Agency policy.
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Open Burning Demolition/Construction Wood
Air Releases
Emission Factors
• 1987—28 ng WHO98 TEQDF/kg (Preliminary).
• 1995—28 ng WHO98 TEQDF/kg (Preliminary).
• 2000—28 ng WHO98 TEQDF/kg (Preliminary).
Activity Levels
• 1987—0.8 MMT (Preliminary).
• 1995—0.8 MMT (Preliminary).
• 2000—0.8 MMT (Preliminary).
Releases
• 1987—22 g WHO98 TEQDF (Preliminary).
• 1995—22 g WHO98 TEQDF (Preliminary).
• 2000—22 g WHO98 TEQDF (Preliminary).
Water Releases
None.
Solid Residue Releases
Emission Factors
• 1987—300 ng WHO98 TEQDF/kg (Preliminary).
• 1995—300 ng WHO98 TEQDF/kg (Preliminary).
• 2000—300 ng WHO98 TEQDF/kg (Preliminary).
Activity Levels
• 1987—0.024 MMT (Preliminary).
• 1995—0.024 MMT (Preliminary).
• 2000—0.024 MMT (Preliminary).
Releases
• 1987—7 g WHO98 TEQDF (Preliminary).
• 1995—7 g WHO98 TEQDF (Preliminary).
• 2000—7 g WHO98 TEQpF (Preliminary).
Products
None.
1
2
3 6.15. OIL SPILL BURNING
4 Aurell and Gullett (2010) measured dioxin emissions during in situ burning of oil spilled
5 into the Gulf of Mexico over the time period of July 13-16, 2010. They derived an emission
6 factor of 1.7 ng TEQ/kg of oil burned assuming that congeners below detection limits equal zero.
7
This document is a draft for review purposes only and does not constitute Agency policy.
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1 If congeners below detection limits were set to their full detection limit, the emission factor was
2 estimated to be 3.0 ng TEQ/kg. However, no activity information was found specifically for in
3 situ oil burning during the reference years, so no quantitative release estimate could be made
4 (Not quantifiable).
5
Oil Spill Burning
The available information is insufficient to make quantitative release estimates (Not
quantifiable).
6
7
8 6.16. CANDLE BURNING
9 Candle burning is a possible source of CDD/CDFs to the air because CDD/CDF releases
10 have been measured from other types of fires. However, no emissions data or activity
11 information were found specifically for this source, so no quantitative release estimate could be
12 made (Not quantifiable).
13
Candle Burning
The available information is insufficient to make quantitative release estimates (Not
quantifiable).
14
15
This document is a draft for review purposes only and does not constitute Agency policy.
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Table 6-1. CDD/CDF emission factors (ng/kg) for forest fires
to
OJ
Biomass description
and location
Tree from Central North
Carolina
Pile— Central North
Carolina
Supplement — Central
North Carolina
Supplement — Western
North Carolina
Supplement — Oregon
Shrub — California
Shrub — Florida
Central North Carolina
Oregon
Tree and leaves from Japan
Wood, leaves, and grass
from Sweden
Wood type
Loblolly pine
Loblolly pine
Loblolly pine
White pine
Hemlock/Pine
Titi, pine straw,
gallberry
Maritime chaparral
White pine
Hemlock/Pine
Unspecified
Unspecified
Test device
Chamber
Chamber
Chamber
Chamber
Chamber
Chamber
Chamber
Chamber
Chamber
Chamber
Hood over fire
on plate
n
1
10
2
2
2
2
2
4
O
1
1
ng TEQor/kg of biomass
Mean (Range)
0.86a
0.615a
0.93a
1.225a
1.64a
8.36a
2.62a
25 (14-47)
15 (1-56)
4.7
27
Reference
Gullett et al. (2008)
Gullett et al. (2008)
Gullett et al. (2008)
Gullett et al. (2008)
Gullett et al. (2008)
Gullett et al. (2008)
Gullett et al. (2008)
Gullett and Touati
(2003)
Gullett and Touati
(2003)
Ikeguchi and Tanaka
(1999)
Gonczi et al. (2005)
§•
rs
I
§
i
a,
Tl rs
H §
>!
SI
*&
31
^^
HH ^3
H S.
w^-
O '
&
O
c
O
H
W
-------
to
OJ
Table 6-1. CDD/CDF emission factors (ng/kg) for forest fires (continued)
Biomass description
and location
Litters, mosses, heathers,
brackens, conifer needles,
pine cones, shrubs, barks,
and branches from France
Forest leaf litter from
three locations in Australia
Prescribed forest fires in
Queensland, Victoria, and
Western Australia
Tropical
savanna — Australia
Wildfires in Victoria
Woodlands in Australia
Wood type
Pine and oak
Eucalyptus, box,
ironback
Eucalyptus
Unspecified
Eucalyptus
Unspecified
Test device
Chamber
Chamber
Field
Field
Field
Field
n
5
5
10
3
2
O
ng TEQor/kg of biomass
Mean (Range)
10 (1-26)
0.37 (0.09-0.79)
0.5 (0.07-1. 4)a
1.1 (0.2-2.8)a
0.7 (0.6-0.8)a
1.5(0.9-2.5)a
Reference
Collet and Fiani
(2006)
Meyer et al. (2004)
Meyer et al. (2004,
2007)
Meyer et al. (2004,
2007)
Meyer et al. (2004,
2007)
Meyer et al. (2004,
2007)
§•
rs
I
to
§
i
a,
°t
'Tl rs
§!
*&
31
aOriginally reported as ng TEQ/kg of carbon and converted to ng TEQ/kg of biomass by multiplying by 0.5.
H S.
w^-
O '
&
O
c
O
H
W
-------
1
2
Table 6-2. Comparison of Forest Fire Data (million acres burned/year)
Fire type and year
Wildfires— 1987
Wildfires— 1995
Wildfires— 2000
Prescribed Fires — 1987
Prescribed Fires — 1995
Prescribed Fires— 2000
CEQ, 1997
5
7
5.1
5.1
U.S. EPA, 2002d
8.36
1.26
NIFC, 2009
2.45
1.84
7.39
NA
NA
1.19
4
5
NA= Not Available.
This document is a draft for review purposes only and does not constitute Agency policy.
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Congener Ratio
1
2
2,3,7,8-TCDD
1,2,3,7,8-PCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HpCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
0.1
0.2
0.3
Source: Pleil and Lorber (2007)
Figure 6-1. Congener profile for structure fires.
This document is a draft for review purposes only and does not constitute Agency policy.
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to
OJ
I
§
o
S§
H §
>!
O S
-
H S.
W K-
i
O
a
o
H
W
Common Forest Types on Non-Federal Land, 1992
MwlD: 27B2.
prupvr ulu IM ulflUM L en
1MB map Dlnur w
far 'UEDfcSOfTL' to knartr
Figure 6-2. Forest fire types in the United States.
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1 7. METAL SMELTING AND REFINING SOURCES OF CDD/CDFS
2
O
4 This chapter addresses dioxin releases associated with primary and secondary metal
5 processing. Primary processes involve the extraction of the base metal from mineral ores.
6 Secondary processes extract the base metal from recycled or waste materials.
7
8 7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING
9 7.1.1. Primary Copper Smelting and Refining
10 Minor changes were made to the air-release estimates.
11
12 7.1.1.1. Air Releases
13 The emission factor was derived from testing at two facilities by Environmental Risk
14 Sciences, Inc. (1995), who used stack testing results to calculate the annual TEQ emission to air
15 to be less than 0.5 g I-TEQop in 1995 for the seven facilities (out of a total of eight) belonging to
16 the National Mining Association. Using the activity level presented below of 1.60 MMT for
17 1995, the emission factor is calculated to be 0.31 ng I-TEQop/kg of copper. This emission factor
18 was applied to all three reference years.
19 In 1987, copper refineries produced 1.13 MMT of copper (USGS, 1997a). In 1995,
20 eight primary copper smelters were in operation in the United States; one of which closed at the
21 end of that year (Edelstein, 1995). Total refinery production was 1.60 MMT in 1995, including
22 0.36 MMT from scrap material (Edelstein, 1995). In 2000, four primary smelters of copper were
23 in operation in the United States, producing 1.61 MMT of copper (USGS, 2002a).
24
25 7.1.1.2. Water Releases
26 No information was found on water releases from these facilities.
27
28 7.1.1.3. Solid Residue Releases
29 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
30 ash and possibly other solid residues at these facilities because they have been found in the air
This document is a draft for review purposes only and does not constitute Agency policy.
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1 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
2 environmental release.
3
4 7.1.1.4. Products
5 No information was found indicating that CDD/CDFs were present in products from
6 these facilities.
7
8 7.1.1.5. Release Summary
9 The inventory decision criteria and releases to all media are summarized below:
10
11
Inventory Decision Criteria for Primary Copper Smelting and
Air Water
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
differences.
Emission factor tests represent units that are typical of the Yes
class.
Activity estimates based on source-specific surveys. Yes
Refining
Solids Products
Conclusion (Q = Quantitative, P = Preliminary). Q
12
This document is a draft for review purposes only and does not constitute Agency policy.
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Primary Copper Smelting and Refining
Air Releases
Emission Factors
• 1987—0.31 ng I-TEQDF/kg of copper.
• 1995—0.31 ng I-TEQDF/kg of copper.
• 2000—0.31 ng I-TEQpp/kg of copper.
Activity Levels
• 1987—1.13 MMT of copper.
• 1995—1.60 MMT of copper.
• 2000—1.61 MMT of copper.
Releases
• 1987—0.3 gl-TEQ.
• 1995—0.5 gl-TEQ.
• 2000—0.5 gl-TEQ.
Water Releases
None.
Solid Residue Releases
None.
Products
None.
1
2
3 7.1.2. Primary Magnesium Smelting and Refining
4 7.1.2.1. Air Releases
5 No change was made to the emission factor, but minor changes were made to the activity
6 estimates and resulting release estimates. The emission factor was derived from stack testing at a
7 Utah facility (Western Environmental Services and Testing, Inc., 2000). This was originally
8 reported as 105 ng I-TEQ/kg of magnesium produced and is converted here to
9 94 ng WHOgg TEQ/kg of magnesium produced based on congener data presented in Western
10 Environmental Services and Testing, Inc., 2000. Even though the testing occurred at only
11 one facility, the estimated releases for the year 2000 are included in the quantitative inventory.
12 This is because the Utah facility was the only one operating in the United States in 2000.
13 Additional facilities were operating in 1987 and 1995 and it is uncertain how well the testing at
14 the Utah facility represented the others. Therefore, the release estimates for 1987 and 1995 were
15
This document is a draft for review purposes only and does not constitute Agency policy.
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1 considered preliminary. The activity estimates were derived from production data from the
2 U.S. Geological Society (USGS, 2002).
3 Under the EPA TRI program for 2000, this facility reported air releases of
4 623 g CDD/CDFs (3.3 g WHOgg TEQop) and on-site surface impoundments of
5 1,661 g CDD/CDFs (8.3 g WHO98 TEQDF) (U.S. EPA, 2008). No releases to other media were
6 reported. As explained in Chapter 1, the accuracy of the TRI data is unknown, and, therefore,
7 they are not used to make quantitative estimates in this document but rather as supportive
8 evidence that releases do occur.
9
10 7.1.2.2. Water Releases
11 Monitoring of wastewater discharges from U.S. magnesium production facilities for
12 CDD/CDF content has not been reported. Wastewater discharges of CDDs/CDFs reported for
13 the Norwegian facility (Oehme et al., 1989) are not adequate to support development of
14 wastewater emission factors for U.S. facilities because of possible differences in the processes
15 used to manufacture MgCb and pollution control equipment. Therefore, water releases are
16 possible but could not be quantified.
17
18 7.1.2.3. Solid Residue Releases
19 CDD/CDFs have been reported in waste sludge generated during magnesium production.
20 EPA (2008) reports that in the year 2001, Magnesium Corporation of America (Rowley, UT)
21 released 2,289 g total CDD/CDF (10 g WHO9g TEQDF, or 12 g I-TEQop) to on-site surface
22 impoundments. The potential for environmental release is unknown (Not quantifiable).
23
24 7.1.2.4. Release Summary
25 The inventory decision criteria and releases to all media are summarized below:
26
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Primary Magnesium Smelting and Refining
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
No
Yes
Yes
P/Qa
1
2 "Preliminary for 1987 and 1995, Quantitative for 2000 because testing occurred at only facility operating in 2000.
3
4
Primary Magnesium Smelting and Refining
Air Releases
Emission Factors
• 1987—94 ng WHO98 TEQDF/kg (110 ng I-TEQDF/kg). (Preliminary)
• 1995—94 ng WHO98 TEQDF/kg (110 ng I-TEQDF/kg). (Preliminary)
• 2000—94 ng WHO98 TEQDF/kg (110 ng I-TEQDF/kg).
Activity Levels
• 1987—0.142 MMT.
• 1995—0.142 MMT.
• 2000—0.083 MMT.
Releases
leases
• 1987—13 g WHOgg TEQoF (16 g I-TEQDp). (Preliminary)
• 1995—13 g WHOgg TEQoF (16 g I-TEQDF). (Preliminary)
• 2000—8 g WHO98 TEQDF (9 g I-TEQDF).
Water Releases
leleases are possible but could not be quantified.
Solid Residue Releases
leleases are possible but could not be quantified.
Products
Jone.
5
6
This document is a draft for review purposes only and does not constitute Agency policy.
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2 7.1.3. Primary Nickel Smelting and Refining
3 No changes were made in the release estimates from these facilities.
4
5 7.1.3.1. Air Releases
6 The emissions information contained in the Norwegian study (Oehme et al., 1989) is not
7 adequate to support development of emission factors for the U.S. facility for 1987 and 1995.
8 Since the only U.S. facility closed in 1998, emissions for 2000 are zero.
9
10 7.1.3.2. Water Releases
11 EPA (2006) reports that one study (Oehme et al., 1989) measured CDD/CDFs in
12 wastewater releases from a nickel production plant in Norway. The information is not adequate
13 to support development of emission factors for the United States. Thus, releases are possible but
14 could not be quantified in 1987 and 1995. Since the only U.S. facility closed in 1998, emissions
15 for 2000 are zero.
16
17 7.1.3.3. Solid Residue Releases
18 No information was found indicating that CDD/CDFs were present in solid residues from
19 these facilities.
20
21 7.1.3.4. Products
22 No information was found indicating that CDD/CDFs were present in products from
23 these facilities.
24
25 7.1.3.5. Release Summary
26 The release estimates are summarized below:
27
This document is a draft for review purposes only and does not constitute Agency policy.
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Primary Nickel Smelting and Refining
Air Releases
Releases are possible but
could not be quantified in 1987 and
1995 and were zero in 2000.
Water Releases
Releases are possible but
could not be quantified in 1987 and
1995 and were zero in 2000.
Solid Residue Releases
Mone.
Products
Mone.
2
3 7.1.4. Primary Aluminum Smelting and Refining
4 No changes were made to the release estimates for these facilities, but additional
5 background information is provided below.
6 The use of hexachloroethane during aluminum production has been identified as a cause
7 for dioxin emissions (UNEP, 2005). The production of hexachloroethane ceased in the
8 United States in the 1970s, so it is not likely to have been used for this purpose during the
9 reference years (ATSDR, 1997). UNEP (2005) did not determine emission factors for primary
10 aluminum production.
11 Kucherenko et al. (2001) measured CDD/CDFs emissions from a primary aluminum
12 plant in Krasnoyarsk, Russia. The air release emission factor was estimated as 11 ng I-TEQ/kg,
13 and the water release emission factor was estimated as 0.141 ng I-TEQ/L. It is unknown how
14 similar this plant is to those in the United States.
15 In summary, insufficient information is available to estimate if CDD/CDF releases occur
16 from these facilities in the United States.
17
18 7.1.5. Primary Titanium Smelting and Refining
19 No changes were made to the release estimates from these facilities, but additional
20 background information is provided below.
21 In the year 2000, nine facilities with an SIC code for inorganic pigments reported dioxin
22 releases under EPA's TRI program. The air and water releases summed across these facilities
23
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1 were less than 1 g WHO98 TEQDF. A total of 240 g WHO98 TEQDF were disposed in landfills
2 (U.S. EPA, 2008). No releases to other media were reported. As explained in Chapter 1, the
3 accuracy of the TRI data is unknown, and therefore, they are not used to make quantitative
4 estimates in this document but rather as supportive evidence that releases do occur.
5
6 7.1.5.1. Air Releases
1 Based on the TRI data reported above, air releases are possible but could not be
8 quantified.
9
10 7.1.5.2. Water Releases
11 Based on the TRI data reported above, water releases are possible but could not be
12 quantified.
13
14 7.1.5.3. Solid Residue Releases
15 Titanium dioxide production creates a variety of sludge wastes, which can contain
16 CDDs/CDFs. As discussed above, the TRI data suggest that inorganic pigment facilities
17 disposed a total of 240 g WHO98 TEQDF in landfills in 2000 (U.S. EPA, 2008).
18 EPA (2001) reports the following measurements in wastes generated in conjunction with
19 chlorinators:
20
21 • Millennium Baltimore, chloride solids/waste acid: 812 ng WHOgg TEQDF/L.
22 • Millennium Baltimore, filter press solids: 2,615 ng WHOgg TEQDF/kg.
23 • DuPont Edge Moor, iron rich: 58.7 ng WHO9g TEQDF/kg.
24 • DuPont New Johnsonville, wastewater treatment solids: 402 ng WHOgg TEQop/kg.
25
26 EPA (2001) reports that the production of wastewater treatment sludges from comingled chloride
27 and sulfate process wastewaters at the Millennium Plant was 93,121 MT/year. Combining this
28 production rate with an assumed 1,000 ng WHOgg TEQop/kg suggests that about
29 90 g WHOgg TEQDF/year may be associated with these sludges at this plant.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 For the most part, these sludges have been disposed of in either on-site or off-site RCRA
2 Subtitle D solid waste disposal facilities. However, given the potential for leaching of the heavy
3 metals from the sludge in the Subtitle D landfill, EPA has listed this waste as hazardous waste
4 under Subtitle C. These sludges are now considered a hazardous waste under RCRA and must
5 be disposed of in permitted landfills (U.S. EPA, 2001). These amounts are not considered to
6 cause environmental releases under the definition in this document.
7
8 7.1.5.4. Products
9 No information was found indicating that CDD/CDFs were present in products from
10 these facilities.
11
12 7.1.5.5. Release Summary
13 The release estimates are summarized below:
14
Primary Titanium Smelting and Refining
Air Releases
Not quantifiable.
Water Releases
Not quantifiable.
Solid Residue Releases
None.
Products
None.
15
16
17 7.2. SECONDARY NONFERROUS METAL SMELTING AND REFINING
18 7.2.1. Secondary Aluminum Smelting and Refining
19 No changes were made in the release estimates from these facilities, but some additional
20 background information is provided below.
21
This document is a draft for review purposes only and does not constitute Agency policy.
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1 7.2.1.1. Air Releases
2 The emission factors were derived from testing at seven facilities (CARB, 1992a, b; U.S.
3 EPA, 1995c). Activity data were based on survey information from USGS (2002a).
4 In the year 2000, 29 facilities with an SIC code for secondary smelting and refining of
5 nonferrous metals reported dioxin releases under the EPA TRI program (U.S. EPA, 2008). Most
6 of these facilities appeared to be aluminum producers. The sum of the air releases across these
7 facilities was 1,022 g, which EPA estimates is equal to 13.8 g WHOgg TEQop No releases to
8 other media were reported. As explained in Chapter 1, the TRI data are not used to make
9 quantitative estimates in this document but rather as supportive evidence that releases do occur.
10
11 7.2.1.2. Water Releases
12 No information was found indicating that CDD/CDFs were present in water releases from
13 these facilities.
14
15 7.2.1.3. Solid Residue Releases
16 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
17 ash and possibly other solid residues at these facilities because they have been found in the air
18 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
19 environmental release.
20
21 7.2.1.4. Products
22 No information was found indicating that CDD/CDFs were present in products from
23 these facilities.
24
25 7.2.1.5. Releases
26 The inventory decision criteria and releases to all media are summarized below:
27
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Secondary Aluminum Smelting and Refining
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
1
2
Secondary Aluminum Smelting and Refining
Air Releases
Emission Factors
• 1987—15 ng WHOgg TEQDF/kg (14 ng I-TEQDF/kg).
• 1995—15 ng WHOgg TEQDF/kg (14 ng I-TEQDF/kg).
• 2000—5.2 ng WHO98 TEQDF/kg (4.9 ng I-TEQDF/kg).
Activity Levels
• 1987—0.7 MMT.
• 1995—1.3 MMT.
• 2000—1.6 MMT.
Releases
• 1987—11 g WHOgg TEQDF(10 g I-TEQDF).
• 1995—20 g WHOgg TEQDF(18 g I-TEQDF).
• 2000—8 g WH098 TEQDF(8 g I-TEQDF).
Water Releases
None.
Solid Residue Releases
None.
Products
None.
4
5 7.2.2. Secondary Copper Smelting and Refining
6 No changes were made in the release estimates from these facilities.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 7.2.2.1. Air Releases
2 Only three facilities were active during the reference years. The emission factors were
3 derived from stack testing at these plants as described in US EPA (2006). The release summary
4 below shows the emission factor and activity estimates (based on data for each plant) in each
5 reference year.
6
7 7.2.2.2. Water Releases
8 No information was found indicating that CDD/CDFs were present in water releases from
9 these facilities.
10
11 7.2.2.3. Solid Residue Releases
12 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
13 ash and possibly other solid residues at these facilities because they have been found in the air
14 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
15 environmental release.
16
17 7.2.2.4. Products
18 No information was found indicating that CDD/CDFs were present in products from
19 these facilities.
20
21 7.2.2.5. Releases
22 The inventory decision criteria and releases to all media are summarized below:
23
This document is a draft for review purposes only and does not constitute Agency policy.
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1
2
Inventory Decision Criteria for Secondary Copper Smelting and Refining
Air Water Solids Products
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
VIeasured emission factors consistent or have understandable Yes
differences.
mission factor tests represent units that are typical of the Yes
class.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
This document is a draft for review purposes only and does not constitute Agency policy.
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Secondary Copper Smelting and Refining
Air Releases
Emission Factors
Franklin
• 1987—17,000 ng WHO98 TEQDF/kg (17,000 ng I-TEQDF/kg).
• 1995—17.000 ng WHO98 TEQDF/kg (17,000 ng I-TEQDF/kg).
Chemetco
• 1987—3.7 ng WHO98 TEQDF/kg (3.6 ng I-TEQDF/kg).
• 1995—3.7 ng WHO98 TEQDF/kg (3.6 ng I-TEQDF/kg).
• 2000—3.7 ng WHO98 TEQDF/kg (3.66 ng I-TEQDF/kg).
Gaston
• 1987—8,900 ng WHO98 TEQDF/kg (8,700 ng I-TEQDF/kg).
Activity Levels
Franklin
• 1987—13,600,000 kg.
• 1995—16,000,000 kg.
Chemetco
• 1987—120,000,000 kg.
• 1995—135,000,000 kg.
• 2000—235,000,000 kg.
Gaston
• 1987—85,000,000 kg.
Releases
• 1987—990 g WHO98 TEQDF (970 g I-TEQDF).
• 1995—270 g WHO98 TEQDF (270 g I-TEQDF).
• 2000—0.9 g WHO98 TEQDF (0.8 g I-TEQDF).
Water Releases
None.
Solid Residue Releases
None.
Products
None.
1
2
3 7.2.3. Secondary Lead Smelting
4 No changes were made in the release estimates from these facilities.
This document is a draft for review purposes only and does not constitute Agency policy.
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1
2 7.2.3.1. Air Releases
3 Three types of furnaces are used in secondary lead smelting. CDD/CDF emission factors
4 were estimated for secondary lead smelters using the results of emission tests performed by EPA
5 at three smelters (a blast furnace [U.S. EPA, 1995b], a colocated blast/reverberatory furnace
6 [U.S. EPA, 1992a], and a rotary kiln furnace [U.S. EPA, 1995c]). Activity estimates were
7 derived from USGS survey data. The release summary below shows the emission factor and
8 activity for each furnace type in each reference year.
9
10 7.2.3.2. Water Releases
11 No information was found indicating that CDD/CDFs were present in water releases from
12 these facilities.
13
14 7.2.3.3. Solid Residue Releases
15 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
16 ash and possibly other solid residues at these facilities because they have been found in the air
17 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
18 environmental release.
19
20 7.2.3.4. Products
21 No information was found indicating that CDD/CDFs were present in products from
22 these facilities.
23
24 7.2.3.5. Releases
25 The inventory decision criteria and releases to all media are summarized below:
26
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Secondary Lead Smelting
Air Water Solids Products
Emission tests for at least two units/source types with Yes
lUfficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable Yes
differences.
mission factor tests represent units that are typical of the Yes
class.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
This document is a draft for review purposes only and does not constitute Agency policy.
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Secondary Lead Smelting
Air Releases
Emission Factors
Blastfurnaces without scrubber
• 1987, 1995, 2000— 8.8 ng WHO98 TEQDF/kg (8.3 ng I-TEQDF/kg).
Blastfurnaces with scrubber
• 1987, 1995, 2000—0.64 ng WHO98 TEQDF/kg (0.63 ng I-TEQDF/kg).
Reverberatory and colocatedfurnaces without scrubber
• 1987, 1995, 2000—0.42 ng WHO98 TEQDF/kg (0.41 ng I-TEQDF/kg).
Reverberatory and colocated furnaces with scrubber
• 1987, 1995, 2000—0.05 ng WHO98 TEQDF/kg (0.05 ng I-TEQDF/kg).).
Rotary furnaces without scrubber
• 1987, 1995, 2000—0.66 ng WHO98 TEQDF/kg (0.66 ng I-TEQDF/kg).
Rotary furnaces with scrubber
• 1987, 1995, 2000—0.24 ng WHO98 TEQDF/kg (0.24 ng I-TEQDF/kg).
Activity Levels
Blastfurnaces (14% with and 86% without scrubbers)
• 1987—0.15 MMT.
• 1995—0.2 MMT.
• 2000—0.29 MMT.
Reverberatory and colocated furnaces (52% with and 48% without scrubbers)
• 1987—0.53 MMT.
• 1995—0.72 MMT.
• 2000—1 MMT.
Rotary furnaces (57% with and 43% without scrubbers)
• 1987—0.04 MMT.
• 1995—0.05 MMT.
• 2000—0.07 MMT.
Releases
• 1987—1 g WHO98 TEQoF (1 g I-TEQDF).
• 1995— 2 g WH098 TEQDF (2 g I-TEQDF).
• 2000—2 g WH098 TEQDF (2 g I-TEQDF).
Water Releases
None.
Solid Residue Releases
None.
Products
None.
This document is a draft for review purposes only and does not constitute Agency policy.
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2
3 7.2.4. Secondary Zinc Production
4 This is a new section.
5 More than one-fourth of the total zinc (Zn) consumed in 2002 by domestic industries was
6 secondary Zn. About 87% of recycled zinc was derived from new scrap, generated mainly in
7 galvanizing and die casting plants and brass mills. The remaining 13% was obtained from brass
8 products, flue dust, old die casts, and old rolled Zn articles. Recycled Zn was used by 2 primary
9 smelters and 13 large and medium (more than 1,000 tons/year) sized secondary smelters
10 principally for production of zinc chemicals, mainly oxide, and Zn metal, including alloys
11 (USGS, 2002b).
12 Clean new scrap, mainly brass, rolled zinc clippings, and rejected die castings, usually
13 requires only remelting. In the case of mixed nonferrous shredded metal scrap, zinc is separated
14 from other materials by hand or magnetic separation. Most of the zinc recovered from dust
15 produced during remelting of galvanized steel scrap, is recovered in rotary kilns by using the
16 Waelz process (USGS, 2009a).
17
18 7.2.4.1. Air Releases
19 UNEP (2005) proposed several zinc related emission factors based on testing at facilities
20 in Germany and Japan:
21
22 • Kilns with no APCs—1,000 ngl-TEQ/kg of zinc
23 • Hot briquetting/rotary furnaces with basic dust controls—100 ng I-TEQ/kg of zinc
24 • Furnaces with comprehensive pollution controls—5 ng I-TEQ/kg of zinc
25 • Zinc melting—0.3 ng I-TEQ/kg of zinc
26
27 The European Dioxin Inventory (Quass et al., 2001) suggests an emission factor of
28 50 ng I-TEQ/kg of zinc with a range of 5 to 500 ng I-TEQ/kg for secondary zinc production.
29 The central value of 50 ng I-TEQ/kg of zinc was selected for all reference years.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 The secondary slab zinc production in the United States was 82,500 MT in 1987,
2 131,000 MT in 1995 and 135,000 MT in 2000 (USGS, 2009b).
3
4 7.2.4.2. Water Releases
5 No information was found indicating that CDD/CDFs were present in water releases from
6 these facilities.
7
8 7.2.4.3. Solid Residue Releases
9 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
10 ash and possibly other solid residues at these facilities because they have been found in the air
11 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
12 environmental release.
13
14 7.2.4.4. Products
15 No information was found indicating that CDD/CDFs were present in products from
16 these facilities.
17
18 7.2.4.5. Releases
19 The inventory decision criteria and releases to all media are summarized below:
20
Inventory Decision Criteria for Secondary
Zinc Production
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
21
22
This document is a draft for review purposes only and does not constitute Agency policy.
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Secondary Zinc Production
Air Releases
Emission Factor
• 1987—50ngI-TEQ/kgofzinc.
• 1995—50ngI-TEQ/kgofzinc.
• 2000—50 ng I-TEQ/kg of zinc.
Activity Levels
• 1987—82,500 MT.
• 1995—131,000 MT.
• 2000—135,000 MT.
Releases
• 1987—4gI-TEQ.
• 1995—7gI-TEQ.
• 2000—7 g I-TEQ.
Water Releases
None.
Solid Residue Releases
None.
Products
None.
1
2
3 7.3. PRIMARY FERROUS METAL SMELTING/REFINING
4 7.3.1. Sinter Production
5 No changes were made to the release estimates except the air releases in 2000, which
6 decreased slightly due to computational corrections.
7
8 7.3.1.1. Air Releases
9 Two types of APCDs are used in sinter production: wet scrubbers and fabric filters. The
10 emission factors for facilities with these two types of APCDs were derived from testing at
11 two U.S. sintering plants operating in 1997 (Calcagni et al., 1998). Activity estimates were
12 derived from several sources: Calcagni et al. (1998), AISI (1990), and Fenton (1996). The
13 release summary below shows the emission factor and activity for each APCD type in each
14 reference year.
15
16
17
This document is a draft for review purposes only and does not constitute Agency policy.
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1 7.3.1.2. Water Releases
2 No information was found indicating that CDD/CDFs were present in water releases from
3 these facilities.
4
5 7.3.1.3. Solid Residue Releases
6 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
7 ash and possibly other solid residues at these facilities because they have been found in the air
8 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
9 environmental release.
10
11 7.3.1.4. Products
12 No information was found indicating that CDD/CDFs were present in products from
13 these facilities.
14
15 7.3.1.5. Releases
16 The inventory decision criteria and releases to all media are summarized below:
17
Inventory Decision Criteria for Sinter Production
Air Water Solids Products
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
ifferences.
Emission factor tests represent units that are typical of the Yes
;lass.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary). Q
18
19
This document is a draft for review purposes only and does not constitute Agency policy.
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Sinter Production
Air Releases
Emission Factors
Wet scrubber
tscrubber
• 1987—0.62 ng WHO98 TEQDF/kg (0.55 ng I-TEQDF/kg) of sinter.
• 1995—0.62 ng WHO98 TEQDF/kg (0.55 ng I-TEQDF/kg) of sinter.
• 2000—0.62 ng WHO98 TEQDF/kg (0.55 ng I-TEQDF/kg) sinter.
Fabric filter
I nn^i
1987—4.6 ng WHO98 TEQDF/kg (4.1 ng I-TEQDF/kg) of sinter.
1995—4.6 ng WHO98 TEQDF/kg (4.1 ng I-TEQDF/kg) of sinter.
2000—4.6 ng WHO98 TEQDF/kg (4.1 ng I-TEQDF/kg) of sinter.
p\7Alea
Activity Levels"
• 1987—14.5 MMT.
• 1995—12.4 MMT.
• 2000—10.6 MMT.
Releases
es
1987—33 g WHO98 TEQDF (30 g I-TEQDF).
1995—28 g WH098 TEQDF(25 g I-TEQDF).
2000—24 g WHO98 TEQpF (21 g I-TEQDF).
Water Rel»
Water Releases
None.
Solid Residue Releases
None.
Products
None.
2 aFifty-nine percent of sinter production was at facilities with wet scrubbers and 41% was at facilities with fabric
3 filters.
4
5
6 7.3.2. Coke Production
7 Minor changes were made to the air emission factor and resulting air-release estimates.
8 The confidence rating was upgraded from preliminary to quantifiable for the air releases due to
9 addition of facility tests used to estimate the emission factor.
10
This document is a draft for review purposes only and does not constitute Agency policy.
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1 7.3.2.1. Air Releases
2 US EPA (2006) used the emission factor of 0.23 ng I-TEQop/kg of coal consumed
3 estimated by Bremmer, et al. (1994). Another study measured dioxin emissions at four Canadian
4 facilities (Charles E. Napier Company, Ltd., 2000). The present study averages the emission
5 factor across the facilities tested in both studies to derive an emission factor of
6 0.29 ng I-TEQop/kg of coal consumed. This emission factor was applied to all three reference
7 years. Coke production estimates were obtained from EIA (2002). The confidence rating was
8 upgraded from preliminary to quantitative because the emission factor was derived from two
9 studies involving 5 facilities.
10 In the year 2000, four facilities with an SIC code for steel works, blast furnaces
11 (including coke ovens), and rolling mills reported dioxin releases under the EPA TRI program
12 (U.S. EPA, 2008). The sum of the air releases across these facilities was 31.8 g, which EPA
13 estimates is equal to 4.1 g WHOgg TEQDF. No releases to other media were reported. As
14 explained in Chapter 1, the TRI data are not used to make quantitative estimates in this document
15 but rather as supportive evidence that releases do occur.
16
17 7.3.2.2. Water Releases
18 Although water is used in quench towers to cool hot coke, it is recycled, and the
19 evaporate is replenished. Therefore no water releases occur.
20
21 7.3.2.3. Solid Residue Releases
22 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
23 ash and possibly other solid residues at these facilities because they have been found in the air
24 emissions. These residues are disposed in landfills and, therefore, are not considered to be an
25 environmental release.
26
27 7.3.2.4. Products
28 No information was found indicating that CDD/CDFs were present in products from
29 these facilities.
30
This document is a draft for review purposes only and does not constitute Agency policy.
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1 7.3.2.5. Release Summary
2 The inventory decision criteria and releases to all media are summarized below:
Inventory Decision Criteria for Coke Production
Air Water Solids Products
mission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
differences.
mission factor tests represent units that are typical of the Yes
;lass.
activity estimates based on source-specific surveys.
Yes
Conclusion (Q = Quantitative, P = Preliminary).
Q
Coke Production
Air Releases
Emission Factors
• 1987—0.29 ng I-TEQDF/kg of coal.
• 1995—0.29 ng I-TEQDF/kg of coal.
• 2000—0.29 ng I-TEQDF/kg of coal.
Activity Levels
• 1987—33.5 MMT.
• 1995—29.9 MMT.
• 2000—26.2 MMT.
Releases
1987—lOgl-TEQoF.
1995—9gI-TEQDF.
2000—8 g I-TEQDF.
Water Releases
None.
Solid Residue Releases
None.
Products
None.
5
6
This document is a draft for review purposes only and does not constitute Agency policy.
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2
3 7.4. SECONDARY FERROUS METAL SMELTING/REFINING
4 No changes were made in the release estimates from these facilities.
5 7.4.1. Air Releases
6 No changes were made in the air-release estimates, but the confidence rating was
7 upgraded from preliminary to quantifiable. This was based on the support for the emission factor
8 from testing at 6 facilities in Germany and 13 facilities in Canada. The emission factor was
9 derived by averaging the data reported in Umweltbundesamt (1996) and the three Environment
10 Canada reports (Charles E. Napier Company, Ltd., 2000; Cianciarelli, 2000, 2001). Based on the
11 congener data reported by Cianciarelli, 2000, the I-TEQs are approximately equivalent to the
12 WHOgg TEQs. The activity estimates were derived from steel-production data from USGS
13 (2002a).
14
15 7.4.2. Water Releases
16 No information was found indicating that CDD/CDFs were present in water releases from
17 these facilities.
18
19 7.4.3. Solid Residue Releases
20 Although no measurement data were found, CDD/CDFs are likely to be present in the fly
21 ash and possibly other solid residues at these facilities because they have been found in the air
22 emissions. These residues are disposed in landfills and, therefore, are not considered an
23 environmental release.
24
25 7.4.4. Products
26 No information was found indicating that CDD/CDFs were present in products from
27 these facilities.
28
29 7.4.5. Release Summary
30 The inventory decision criteria and releases to all media are summarized below:
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Secondary Ferrous
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Metal
Air
Yes
Yes
Yes
Yes
Q
Smelting/Refining
Water Solids Products
1
2
3
Secondary Ferrous Metal Smelting/Refining
Air Releases
Emission Factors
• 1987—1 .2 ng (WHO98 or I-TEQDF/kg) of steel.
• 1995—1 .2 ng (WHO98 or I-TEQDF/kg) of steel.
• 2000—1 .2 ng (WHO98 or I-TEQDF/kg) of steel.
Activity Levels
• 1987— 30.8 MMT.
• 1995— 38.4 MMT.
• 2000—49.0 MMT.
Releases
• 1987— 37 g (WHO98 or I-TEQop).
• 1 995—46 g (WHO98 or I-TEQDF).
• 2000—59 g (WHO98 or I-TEQDF).
Water Releases
None.
Solid
Residue Releases
None.
Products
None.
4
5
6
7
This document is a draft for review purposes only and does not constitute Agency policy.
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1 7.5. FERROUS FOUNDRIES
2 No changes were made to the release estimates for these facilities, but some additional
3 background information is provided below.
4
5 7.5.1. Air Releases
6 The emission factor for the ferrous foundries was estimated by combining the mean
7 emission factor derived from the data reported in Umweltbundesamt (1996), CARB (1993), and
8 EPA (1997a), yielding a value of 1.23 ng I-TEQop/kg of metal feed. This was converted to
9 1.37 ng WHOgg TEQop/kg based on the congener profile reported in EPA, 1997a. The emission
10 data represent a total of 10 facilities and generated emission factors ranging over 4 orders of
11 magnitude. Based on the inconsistency of these results for reasons that are not clear, the release
12 estimates are considered preliminary. The activity estimates were derived from survey data from
13 USGS (2001).
14 In the year 2000, five facilities with an SIC code for gray and ductile iron foundries
15 reported dioxin releases under the EPA TRI program (U.S. EPA, 2008). The sum of the air
16 releases across these facilities was 117 g, which EPA estimates is equal to 21.5 g WHOgg TEQop.
17 No releases to other media were reported. As explained in Chapter 1, the TRI data are not used
18 to make quantitative estimates in this document but rather as supportive evidence that releases do
19 occur.
20
21 7.5.2. Water Releases
22 Liquid pollution makes up a small portion of the total waste stream from foundries
23 (Freeman, 1995). Water is used in foundries to cool metal and other work pieces and in the wet
24 scrubber air emission system. No information was found on CDD/CDF levels in these
25 wastewaters.
26
27 7.5.3. Solid Residue Releases
28 Solid waste makes up a large portion of the pollution from foundries. One-quarter to
29 one ton of solid waste per one ton of castings is expected (Shah, 1995). The waste comes from
This document is a draft for review purposes only and does not constitute Agency policy.
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1 sand, slag, emissions control dust, and spent refractories. Molding and core sand make up
2 66-88% of the total waste from ferrous foundries (U.S. EPA, 1992b).
3 Slag waste is often very complex chemically and contains a variety of contaminants from
4 the scrap metals. Common components include metal oxides, melted refractories, sand, and coke
5 ash (if coke is used). Fluxes may also be added to help remove the slag from the furnace. Slag
6 may be hazardous if it contains lead, cadmium, or chromium from steel or nonferrous metals
7 melting. Iron foundry slag may be highly reactive if calcium carbide is used to desulfurize the
8 iron. No information was found on CDD/CDF levels in these solid wastes. However, they are
9 typically landfilled and thus not considered a release to environment.
10
11 7.5.4. Products
12 No information was found indicating that CDD/CDFs were present in products from
13 these facilities.
14
15 7.5.5. Release Summary
16 The inventory decision criteria and releases to all media are summarized below:
17
Inventory Decision Criteria for Ferrous Foundries
Air Water Solids Products
Emission tests for at least two units/source types with Yes
lUfficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable No
ifferences.
Emission factor tests represent units that are typical of the Yes
;lass.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
18
19
This document is a draft for review purposes only and does not constitute Agency policy.
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Ferrous Foundries
Air Releases
Emission Factors
• 1987—1.4 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of metal feed. (Preliminary)
• 1995—1.4 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of metal feed. (Preliminary)
• 2000—1.4 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of metal feed. (Preliminary)
Activity Levels
• 1987—9.19 MMT.
• 1995—13.9 MMT.
• 2000—11.3 MMT.
Releases
• 1987—13 g WHO98 TEQDF (11 g I-TEQDF). (Preliminary)
• 1995—19 g WHO98 TEQDF (17 g I-TEQDF). (Preliminary)
• 2000—16 g WHO98 TEQDF (14 g I-TEQDF). (Preliminary)
Water Releases
None.
Solid Residue Releases
None.
Products
None.
1
2
3 7.6. NONFERROUS METAL FOUNDRIES
4 This is a new section.
5
6 7.6.1. Aluminum Foundries
7 No CDD/CDF emissions data were found for aluminum foundries. However, UNEP
8 (2005) provides a range of emission factors for various types of aluminum processing. For the
9 purposes of a preliminary estimate, a midrange value of 3.5 ng I-TEQ/kg was assumed to apply
10 to all reference years. This corresponds to well-controlled facilities with fabric filters and lime
11 injection.
12 The activity estimate for aluminum foundries in 2000 was found to be 95,600 MT based
13 on the USGS Minerals Yearbook (USGS, 2000). The earlier years were estimated by assuming
14
This document is a draft for review purposes only and does not constitute Agency policy.
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1 that foundry production was a constant ratio with total consumption: 82,500 MT in 1995 and
2 72,000 MT in 1987.
3 Foundries typically have solid waste associated with residues from the casting process.
4 No information was found on CDD/CDF levels in these materials. However, these residues
5 would be landfilled and, therefore, are not considered an environmental release.
6 The inventory decision criteria and releases to all media are summarized below:
7
Inventory Decision Criteria for Aluminum Foundries
Air Water Solids Products
mission tests for at least two units/source types with No
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable
ifferences.
Emission factor tests represent units that are typical of the No
;lass.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
This document is a draft for review purposes only and does not constitute Agency policy.
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Aluminum Foundries
Air Releases
Emission Factors
• 1987—3.5 ng I-TEQDF/kg of metal feed (Preliminary).
• 1995—3.5 ng I-TEQDF/kg of metal feed (Preliminary).
• 2000—3.5 ng I-TEQDF/kg of metal feed (Preliminary).
Activity Levels
• 1987—72,000 MT.
• 1995—82,500 MT.
• 2000—95,600 MT.
Releases
• 1987—0.3 g I-TEQDF (Preliminary).
• 1995—0.3 g I-TEQDF (Preliminary).
• 2000—0.3 g I-TEQDF (Preliminary).
Water Releases
None.
Solid Residue Releases
None.
Products
None
1
2
3 7.6.2. Copper Foundries
4 UNEP (2005) provides an emission factor for copper casting operations of
5 0.03 ng I-TEQ/kg of copper based on emissions testing at foundries in Germany. This was
6 assumed to apply to all reference years.
7 The activity estimate for copper foundries in 2000 was found to be 26,000 MT based on
8 the USGS Minerals Yearbook (USGS, 2000). The earlier years were estimated by assuming that
9 foundry production was a constant ratio with total consumption: 21,000 MT in 1995 and
10 18,500 MT in 1987.
11 Foundries typically have solid waste associated with residues from the casting process.
12 No information was found on CDD/CDF levels in these materials. However, these residues
13 would be landfilled and, therefore, are not considered to be an environmental release.
14 The inventory decision criteria and releases to all media are summarized below:
15
16
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Aluminum Foundries
Air Water Solids Products
Emission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
VIeasured emission factors consistent or have understandable Yes
ifferences.
Emission factor tests represent units that are typical of the Yes
;lass.
Activity estimates based on source-specific surveys.
Yes
Conclusion (Q = Quantitative, P = Preliminary).
Q
2
3
Copper Foundries
Air Releases
Emission Factors
• 1987—0.03 ng I-TEQDF/kg of metal feed.
• 1995—0.03 ng I-TEQDF/kg of metal feed.
• 2000—0.03 ng I-TEQDF/kg of metal feed.
Activity Levels
• 1987—72,000 MT.
• 1995—82,500 MT.
• 2000—95,600 MT.
Releases
• 1987—<0.1gI-TEQDF.
• 1995—<0.1gI-TEQDF.
• 2000—<0.1 g 1-TEQoF-
Water Releases
None.
Solid Residue Releases
None.
Products
None.
4
5
6
7
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2 7.7. SCRAP ELECTRIC WIRE RECOVERY
3 No changes were made in the release estimates for these facilities. It is unknown how
4 many facilities in the United States conducted scrap wire recovery operations over the reference
5 years, so no activity estimates could be made, and therefore, no release estimates could be made
6 as well.
7
8 7.7.1. Air Releases
9 As reported in EPA (2006), CDDs/CDFs have been measured in the emissions from these
10 facilities. The emission factor from EPA (1987) of 15.8 ng WHO98 TEQDF (16.9 ng I-TEQDF/kg)
11 of scrap feed was applied to all reference years. This factor is considered preliminary because it
12 is based on testing at only one facility. Lacking activity information on these facilities; however,
13 no estimates of air releases can be made.
14
15 7.7.2. Water Releases
16 No information was found indicating that these facilities have water effluents.
17
18 7.7.3. Solid Residue Releases
19 Ash is produced as a byproduct when scrap wire is combusted. Harnly et al. (1995)
20 analyzed soil/ash mixtures from three closed metal recovery facilities and from three closed sites
21 using open burning for copper recovery near a California desert town. The geometric means of
22 the total CDD/CDF concentrations at the facility sites and the open burning sites were 86,000
23 and 48,500 ng/kg, respectively. The geometric mean TEQ concentrations were 2,900 and
24 1,300 ng I-TEQop/kg, respectively. A significantly higher geometric mean concentration
25 (19,000 ng I-TEQop/kg) was found in fly ash located at two of the facility sites. Lacking activity
26 information on these facilities, no estimates of releases from solid residues can be made. The
27 portion of the ash that is disposed in landfills would not be considered an environmental release.
28
29 7.7.4. Products
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1 No information was found indicating that CDD/CDFs were present in products from
2 these facilities.
3 7.7.5. Release Summary
4 The inventory decision criteria and releases to all media are summarized below.
5
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Scrap Electric Wire Recovery
Air Releases
Releases are possible but
cannot be
quantified (Not quantifiable).
Water Releases
Mone.
Solid Residue Releases
Releases are possible but
cannot be
quantified (Not quantifiable).
Products
Mone.
2
3 7.8. DRUM AND BARREL RECLAMATION FURNACES
4 Changes were made to the activity estimates and resulting air-release estimates from
5 these facilities.
6
7 7.8.1. Air Releases
8 The emission factor estimate (17.5 ng WHOgg TEQDF/drum) was based on testing at a
9 reclamation facility equipped with an afterburner (U.S. EPA, 1987). The testing at this facility
10 indicated that the afterburner achieved a 95% reduction in CDD/CDF emissions. It is possible
11 that some of these facilities do not have afterburners and using this emission factor may
12 underestimate their emissions by 20 times. Based on this uncertainty and data from only one
13 facility, this emission factor is considered preliminary. EPA (2006) reports that 35 million
14 drums were reclaimed in 1997 based on RIPA (1997), and this was assumed for the activity level
15 in 2000. EPA (2006) assumed an activity level of 4.6 million drums in 1987 and 1995 based on
16 a personal communication. These activity assumptions imply a large change in barrel
17 reclamation activity over a short time period, which seems unlikely. Because the RIPA (1997) is
18 a stronger reference, the activity assumptions for 1987 and 1995 were changed to 35 million
19 barrels as well. However, survey data were lacking for all years and these activity estimates are
20 considered preliminary.
21
22 7.8.2. Water Releases
23
24
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1 No information was found indicating that CDD/CDFs were present in water releases from
2 these facilities.
O
4 7.8.3. Solid Residue Releases
5 Sludges and ashes are stored in collection pits at these facilities. No information was
6 found indicating that CDD/CDFs were present in solid residues from these facilities. However,
7 it is reasonable to assume that CDD/CDFs are present in these ashes because they have been
8 found in the ash from other types of combustion. Lacking measurement information, no
9 estimates of releases from solid residues can be made (Not quantifiable). The portion of the
10 solid waste that is disposed in landfills would not be considered an environmental release.
11
12 7.8.4. Products
13 No information was found indicating that CDD/CDFs were present in products from
14 these facilities.
15
16 7.8.5. Release Summary
17 The inventory decision criteria and releases to all media are summarized below:
18
Inventory Decision Criteria for Drum and Barrel Reclamation Furnaces
Air Water Solids Products
mission tests for at least two units/source types with No
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable
ifferences.
Emission factor tests represent units that are typical of the Yes
;lass.
Activity estimates based on source-specific surveys. No
Conclusion (Q = Quantitative, P = Preliminary). P
19
20
21
22
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1
2
Drum and Barrel Reclamation Furnaces
Air Releases
Emission Factors
• 1987—17.5 ng WHO98 TEQDF/drum (16.5 ng I-TEQDF/drum) (Preliminary).
• 1995—17.5 ng WHO98 TEQDF/drum (16.5 ng I-TEQDF/drum) (Preliminary).
• 2000— 17.5 ng WHO98 TEQDF/drum (16.5 ng I-TEQDF/drum) (Preliminary).
Activity Levels
• 1987—35 million drums burned.
• 1995—35 million drums burned.
• 2000—35 million drums burned.
Releases
• 1987—0.6 g WHO98 TEQDF (0.6 g I-TEQDF) (Preliminary).
• 1995—0.6 g WHO98 TEQDF (0.6 g I-TEQDF) (Preliminary).
• 2000—0.6 g WHO98 TEQDF (0.6 g I-TEQDF) (Preliminary).
Water Releases
Solid Residue Releases
leleases are possible but cannot be quantified.
Products
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1 8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES
2
3
4 8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS
5 No changes were made to the release estimates for these facilities; however, some
6 additional discussion is provided below to clarify how the estimates were derived.
7
8 8.1.1. Air Releases
9 Air releases from incineration of sludges are covered in Section 3.7.
10
11 8.1.2. Water Releases
12 For 1987 and 1995, an emission-factor approach was not needed because release
13 estimates were available for virtually all facilities. These data came from six industry-wide
14 surveys as described in EPA (2006).
15 An emission-factor approach was used to estimate releases in 2000 because a
16 comprehensive plant survey was not done for this year. The emission factor and activity
17 estimates were provided by NCASI (Gillespie, 2002) based on data from multiple facilities.
18
19 8.1.3. Solid Residue Releases
20 As described in EPA (2006), the amounts of CDD/CDFs in solid residues came from the
21 comprehensive industry surveys in 1987 and 1995. In 1990, the majority (75.5%) of the
22 wastewater sludge generated by these facilities was placed in landfills or in surface
23 impoundments, with the remainder incinerated (20.5%), applied to land or used as compost
24 (4.1%), or distributed as a commercial product (less than 1%) (U.S. EPA, 1993b). Data on the
25 disposition of wastewater sludges are available only for years 1988 through 1995. On the basis
26 of these data, the best estimate of the amount applied to land (i.e., not incinerated or landfilled) is
27 14.1 g WHO98 or I-TEQ (4.1% of 343 g) for 1987 and 2 g 1 g WHO98 or I-TEQ (4.1% of 50 g)
28 for 1995.
29 For 2000, the primary waste treatment residuals from pulp mills
30 (0.974 million dry MT/year) and the combined, secondary, and dredged waste treatment
31 residuals from pulp mills (1.37 million dry MT/year) were derived from the NCASI database
32 (Gillespie, 2002) on multiple facilities. This yields a total sludge production of
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1 2.34 million dry MT. Fifty-one percent of the sludge generated in 2000 was sent to landfills or
2 lagoons (Gillepsie, 2002). It is uncertain how much of the remaining 49% of the sludge was
3 applied to land. However, a conservative estimate can be developed by applying the 4.1% used
4 to develop the 1987 and 1995 estimates. This implies that 1.19 MMT was landfilled and
5 0.096 MMT were land applied.
6 The CDD/CDFs in sludges that are land applied are assumed to represent environmental
7 releases. These amounts are shown in the release summary below. The CDD/CDFs in sludges
8 that are landfilled are not considered to be environmental releases, and these amounts are listed
9 below:
10
11 • 1987—260 g WHOgg or I-TEQ/year
12 • 1995—38 g WHOgg or I-TEQ/year
13 • 2000—2 g WHOgg or I-TEQ/year
14
15 8.1.4. Products
16 The surveys discussed above provide information on the amounts of CDD/CDFs found in
17 wood pulp: 500 g WHO98 or I-TEQ in 1987, 40 g WHO98 or I-TEQ in 1995, and 0.6 g WHO98 or
18 I-TEQ in 2000. It is unknown if environmental releases occur from paper products made from
19 the pulp. The CDD/CDFs in wood pulp products can be considered to be a reservoir as
20 discussed further in Chapter 11.
21
22 8.1.5. Release Summary
23 The inventory decision criteria and releases to all media are summarized below:
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Inventory Decision Criteria for Bleached Chemical Wood Pulp and Paper Mills
Air Water Solids Products
Emission tests for at least two units/source types with Yes Yes
mfficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have Yes Yes
understandable differences.
mission factor tests represent units that are typical of the Yes Yes
;lass.
activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary). Q Q_
1
2
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Bleached Chemical Wood Pulp and Paper Mills
Air Releases
Air releases from incineration of sludges are covered in Section 3.7.
Water Releases
Emission Factor
• 2000—0.49 pg (WHO98 or I-TEQ/L) of wastewater.
Activity Level
• 2000—2.87 trillion L.
Releases
• 1987—360 g (WHO98 or I-TEQ).
• 1995—28 g (WHO98 or I-TEQ).
• 2000—1 g (WHO98 or I-TEQ).
Solid Residue Releases
Emission Factor
• 2000—1.8 ng (WHO98 or I-TEQ/kg) of sludge.
Activity Level
Land Applied
• 2000—0.096 million dry MT.
Releases
Land Applied
• 1987—14 g(WHO98 or I-TEQ).
• 1995—2 g (WHO98 or I-TEQ).
• 2000—0.2 g (WHO98 or I-TEQ).
Products
Releases
• 1987—Not quantifiable.
• 1995—Not quantifiable.
• 2000—Not quantifiable.
1
2
3 8.2. STAND-ALONE CHLOR-ALKALI PLANTS
4 In the original report, Section 8.2 covered the manufacture of chlorine, chlorine
5 derivatives, and metal chlorides, and Section 8.3 covered the manufacture of halogenated organic
6 chemicals. These two sections have been reorganized into the following three sections:
7
8 8.2—Stand-Alone Chlor-Alkali Plants
9
10
11
12
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1 8.3—Stand-Alone Vinyl Chloride Manufacturing Plants
2 8.4—Complex Chemical Plants Producing Chlorine and a Variety of Chlorinated Organics
3
4 Because the changes to these sections are extensive, they are presented here in their entirety.
5 Although the reorganization is extensive, only minor changes were made to the release estimates.
6 This section covers plants that produce only chlorine, sodium hydroxide (NaOH), and
7 related caustic chemicals (also known as chlor-alkali plants). These chemicals are also produced
8 at complex plants that produce a variety of chlorinated organic compounds. The CDD/CDF
9 releases associated with chlor-alkali production at these complex plants are covered in
10 Section 8.4.
11
12 8.2.1. Process Description
13 Chlorine gas is produced by electrolysis of brine in electrolytic cells. Three processes are
14 in use: the diaphragm-cell process, the membrane-cell process, and the mercury-cell process. In
15 the diaphragm-cell process, a porous diaphragm divides the electrolytic cell, which contains
16 brine, into an anode compartment and a cathode compartment. When an electric current passes
17 through the brine, the chlorine ions and sodium ions from the salt move to the electrodes.
18 Chlorine gas is produced at the anode, and sodium ions at the cathode react with the water,
19 forming caustic soda. In the membrane-cell process, the compartments are separated by a
20 membrane rather than a diaphragm. Brine is pumped into the anode compartment, and only
21 sodium ions pass into the cathode compartment, which contains pure water. Thus, the caustic
22 soda produced has very little salt contamination. In the mercury-cell process, mercury, which
23 flows along the bottom of the electrolytic cell, serves as the cathode. When an electric current
24 passes through the brine, chlorine is produced at the anode, and sodium dissolves in the mercury,
25 forming an amalgam of sodium and mercury (Chorine Institute, 2010).
26 Until the late 1970s, the primary type of electrolytic process used in the chlor-alkali
27 industry to produce chlorine consisted of the use of mercury cells containing graphite electrodes.
28 During the 1980s, titanium metal anodes were developed to replace graphite electrodes
29 (U.S. EPA, 1982; Curlin and Bommaraju, 1991). Currently, no U.S. facility is believed to use
30 graphite electrodes in the production of chlorine gas (telephone conversation between L. Phillips,
31 Versar, Inc., and T. Fielding, U.S. EPA, Office of Water, February 1993).
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1 8.2.2. Regulations
2 Although EPA does not regulate CDDs/CDFs specifically, it issued restrictions under
3 RCRA on the land disposal of wastewater and sludges generated by chlorine manufacturers that
4 use the mercury-cell process and the diaphragm-cell process (with graphite electrodes) (waste
5 codes K071, K073, and K106) (40 CFR 268).
6
7 8.2.3. Literature
8 As shown in Table 8-1, high levels of CDFs have been found in several samples of
9 graphite electrode sludge from facilities in Europe. The CDFs predominate in these sludges, and
10 the 2,3,7,8-substituted congeners account for a large fraction of the respective congener totals
11 (Rappe et al., 1990, 1991; Rappe, 1993; Strandell et al., 1994). Although the origin of the CDFs
12 in graphite electrode sludge is uncertain, chlorination of the cyclic aromatic hydrocarbons (such
13 as dibenzofuran) present in the coal tar used as a binding agent in the graphite electrodes has
14 been proposed as the primary source (Strandell et al., 1994). For this reason, sludges produced
15 using metal electrodes were not expected to contain CDFs. However, results of an analysis of
16 metal electrode sludge from a facility in Sweden, analyzed as part of the Swedish Dioxin Survey,
17 showed that the sludge contained high levels of CDFs (similar to those of the graphite sludge)
18 and primarily nondetectable levels of CDDs (Strandell et al., 1994). The sludge showed the
19 same type of CDF congener pattern reported by Rappe et al. (1991) and Rappe (1993). Strandell
20 et al. suggested that chlorination of polyaromatic hydrocarbons present in the rubber linings of
21 the electrolytic cell may have produced the CDFs found in the one sample analyzed.
22 The Chlorine Chemistry Council (CCC), a trade association representing manufacturers
23 that produce and/or use chlorine, sampled a variety of waste streams at seven stand-alone
24 chlor-alkali facilities in the United States (CCC, 2004). Note that one of these plants (Occidental
25 in Deer Park, TX) also produced vinyl chloride monomer (VCM), but the processes and
26 associated waste streams are adequately separated such that it can be treated as a stand-alone
27 facility. This information is also summarized in Dyke and Amendola (2007). This study
28 measured CDD/CDF releases to water from all seven facilities as summarized in Table 8-2. Air
29 releases were only detected at one facility (see Table 8-3). Dyke and Amendola (2007)
30 summarized the amount of CDD/CDF in all waste streams and provided a confidence rating for
31
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1 each value (see Table 8-4). Table 8-4 shows the amount of CDD/CDFs that are sent to off-site
2 incinerators, landfills, and deep-well injection facilities. The releases from incineration are
3 included in the estimates presented for hazardous waste incinerators (see Section 3.2). The
4 amounts sent to secure landfills and deep-well injection facilities are not considered to be
5 environmental releases.
6 Dyke and Amendola (2007) present release estimates for both the years 2000 and 2002.
7 The 2002 values are not reproduced here but are generally lower or similar to the 2000 values.
8 In the year 2000, five facilities with an SIC code for alkalies and chlorine reported dioxin
9 releases under the EPA TRI program (U.S. EPA, 2008). The sum of the air releases across these
10 facilities was 204 g, which EPA estimates is equal to 3.3 g WHOgg TEQop The sum of the
11 water releases across these facilities was 1,416 g, which EPA estimates is equal to
12 24.8 g WHOgg TEQop. No releases to other media were reported. As explained in Chapter 1, the
13 TRI data are not used to make quantitative estimates in this document but rather as supportive
14 evidence that releases do occur.
15
16 8.2.4. Releases
17 The information presented in Dyke and Amendola (2007) was selected as the best basis
18 for estimating CDD/CDF releases from these facilities. The seven stand-alone chlor-alkali plants
19 covered in this study are believed to represent most of the stand-alone chlor-alkali production in
20 the United States. Therefore, it was unnecessary to develop emission factors to estimate releases
21 from untested facilities. The Dyke and Amendola release estimates are specific to the year 2000.
22 No release data were found for earlier years. Because the chemical production rates and
23 technologies used at these facilities were probably similar in 1995 and 2000, the 2000 results are
24 assumed to apply to 1995. However, significant changes may have occurred since 1987, so no
25 release estimates could be made for 1987. The releases to all media are presented in Table 8-4
26 and summarized below.
27 The solid residues from these plants are disposed in secure landfills or by deep-well
28 injection and, therefore, are not considered an environmental release. The amounts are
29 summarized below:
30 • 1987—Not Available
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1 • 1995—2.7 gl-TEQ
2 • 2000—2.7 g I-TEQ
O
4 The inventory decision criteria and releases to all media are summarized below:
5
Inventory Decision Criteria for Stand-Alone Chlor-Alkali Plants
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Air
Yes
Yes
Yes
Yes
Q
Water Solids Products
Yes
Yes
Yes
Yes
Q
6
7
Stand-Alone Chlor-Alkali Plants
Air Releases
• 1987— Not available.
• 1995— 0.03 g I-TEQ.
• 2000—0.03 g I-TEQ.
Water Releases
• 1987— Not available.
• 1995— 2 g I-TEQ.
• 2000—2 g I-TEQ.
Solid Residue Releases
None. The solid residues from these plants are disposed in secure landfills or by
injection and, therefore, are not considered an environmental release.
deep-well
Products
No information was found suggesting that CDD/CDFs are found in the products
facilities.
from these
9
10 8.3. STAND-ALONE VINYL CHLORIDE MANUFACTURING PLANTS
11
12
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1 As explained at the beginning of Section 8.2, this is a new section based on the
2 reorganization of Sections 8.2 and 8.3 in the original report. This section covers plants that
3 produce only polyvinyl chloride (PVC) and PVC intermediates such as ethylene dichloride
4 (EDC) and VCM. These chemicals are also produced at complex plants that produce a variety of
5 chlorinated organic compounds. The CDD/CDF releases associated with vinyl chloride
6 production at these complex plants are covered in Section 8.4.
7
8 8.3.1. Process
9 PVC resins are produced from the polymerization of VCM. VCM is typically produced
10 by the thermal dehydrochlorination (commonly known as cracking) of EDC. The cracking of
11 EDC requires elevated pressure (20 to 30 atm) and temperature (450 to 650EC) and yields VCM
12 and HC1 at about a 1:1 molar ratio. EDC is produced by two different methods: (1) direct
13 chlorination of ethylene with chlorine in the presence of a catalyst at a temperature of 50 to
14 60EC and pressure of 4 to 5 atm; and (2) oxychlorination, which involves reaction of ethylene
15 with HC1 and oxygen in the presence of a catalyst at temperatures generally less than 325EC.
16 The primary source of HC1 for the oxychlorination process is the HC1 produced from the
17 cracking of EDC to form VCM. Most VCM manufacturing facilities are integrated with EDC
18 production facilities (The Vinyl Institute, 1998).
19
20 8.3.2. Regulations
21 Although EPA regulates emissions from EDC/VCM production facilities under the Clean
22 Water Act (40 CFR 61), the Clean Air Act (40 CFR 414), and RCRA (40 CFR 268, waste codes
23 F024, KOI9, and K020), CDDs/CDFs are not specifically regulated pollutants.
24
25 8.3.3. Literature
26 Although it has been generally recognized that CDDs/CDFs can be formed during the
27 manufacture of EDC, VCM, and PVC, manufacturers and environmental public interest groups
28 have disagreed as to the quantity of CDDs/CDFs that are formed and released to the environment
29 in wastes and possibly in PVC products. Greenpeace International initially determined that
30 CDDs and CDFs can be formed during the manufacture of PVC. In 1993, it issued a report on
31 CDD/CDF emissions associated with the production of EDC/VCM (Greenpeace, 1993).
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1 Greenpeace estimated that 5 to 10 g I-TEQop were released to the environment (air, water, and
2 ground combined) annually for every 100,000 MT of VCM produced. This emission factor was
3 based on data gathered by Greenpeace on four European plants. The Vinyl Institute responded
4 with a critique of the Greenpeace report (ChemRisk, 1993). Miller (1993) summarized the
5 differing views of the two parties. According to Miller, European PVC manufacturers claimed
6 the emission factor was 0.01 to 0.5 g I-TEQDF/100,000 MT of VCM, and although Greenpeace
7 and ChemRisk used basically the same monitoring information to develop their emission factors,
8 Greenpeace adjusted the emission factor to account for unquantified fugitive emissions and
9 waste products that contain unspecified amounts of CDDs/CDFs.
10 In 1995, Greenpeace issued a second report (Stringer et al., 1995) reiterating the
11 organization's concern that the generation and the emission of CDDs/CDFs may be significant
12 and urging that further work be initiated to quantify and prevent emissions. Stringer et al. (1995)
13 presented the results of analyses of three samples of chlorinated wastes obtained from
14 U.S. EDC/VCM manufacturing facilities. The three samples were characterized according to
15 EPA hazardous waste classification numbers as an F024 waste (waste from the production of
16 short-chain aliphatics by free radical-catalyzed processes), a KOI9 waste (heavy ends from the
17 distillation of ethylene from EDC production), and a probable K020 waste (heavy ends from
18 distillation of vinyl chloride in VCM manufacturing). Table 8-5 presents the analytical results
19 reported by Stringer et al. (1995). This study acknowledged that because EDC/VCM production
20 technologies and waste treatment and disposal practices are very site-specific, the limited
21 information available on CDD/CDF generation and emissions made it difficult to quantify
22 amounts of CDDs/CDFs generated and emitted.
23 In response to the lack of definitive studies, and at the recommendation of the EPA,
24 U.S. PVC manufacturers began an extensive monitoring program—the Dioxin Characterization
25 Program (DCP). The objective of the DCP was to evaluate the extent and magnitude of potential
26 CDD/CDF releases to air, water, and land, as well as the potential for PVC product
27 contamination. Manufacturers performed emissions and product testing at several facilities that
28 were representative of various manufacturing and process control technologies. In 1998, The
29 Vinyl Institute completed studies of CDD/CDF releases in wastewater, wastewater treatment
30 plant solids, and stack gases, as well as studies of the CDD/CDF content of products (PVC resins
31 and EDC sold as products) (The Vinyl Institute, 1998). This study presented results for
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1 22 samples from 14 of the 24 U.S. and Canadian facilities manufacturing suspension and mass
2 PVC resins (13 pipe resins, 3 bottle resins, and 6 packaging resins). The results for U.S.
3 manufacturers are summarized in Table 8-6. The 14 sampled sites represented approximately
4 74% of estimated 1995 U.S. and Canadian suspension and mass PVC resin production.
5 CDDs/CDFs were detected in only one sample (0.043 ng I-TEQDF/kg, assuming nondetects
6 equal to zero). The overall mean TEQ concentrations were 0.002 ng I-TEQDF/kg (assuming
7 nondetects equal to zero) and 0.7 ng I-TEQop/kg (assuming nondetects equal to one-half the
8 DL). The DLs were 2 ng/kg or less for all congeners in all samples except for OCDD and
9 OCDF, which had DLs of 6 ng/kg or less.
10 The same study also presented results for six samples from four of the seven U.S.
11 facilities manufacturing dispersion PVC resins. CDDs/CDFs were detected in five of the
12 samples. The results are summarized in Table 8-6. In terms of production, the four sampled
13 sites represent approximately 61% of estimated 1995 U.S. dispersion PVC resin production. The
14 results ranged from not detected to 0.008 ng I-TEQDF/kg (overall mean = 0.001 ng I-TEQDF/kg,
15 assuming nondetects equal to zero, and 0.4 ng I-TEQop/kg, assuming nondetects equal to
16 one-half the DL). The DLs were 2 ng/kg or less for all congeners in all samples except for
17 OCDD and OCDF, which had DLs of 4 ng/kg or less.
18 Results were also presented for five samples from 5 of the 15 U.S. facilities
19 manufacturing EDC. The results are summarized in Table 8-6. In terms of production, the
20 five sampled sites represented approximately 71% of the estimated EDC produced in the United
21 States in 1995. CDDs/CDFs were detected in only one sample (0.03 ng I-TEQDF/kg). The
22 overall mean TEQ concentrations were 0.006 ng I-TEQDF/kg (nondetects equal to zero) and
23 0.21 ng I-TEQop/kg (nondetects equal to one-half the DL). The DLs for all congeners were
24 1 ng/kg or less.
25 EPA (2006) used concentration and production data to estimate that vinyl chloride
26 contained 0.02 g I-TEQ in 1995 and 0.02 g I-TEQ in 2000. It is unknown if releases occurred
27 from these products.
28 The Chlorine Chemistry Council (CCC), a trade association representing manufacturers
29 that produce and/or use chlorine, also sponsored studies to measure CDD/CDF releases from the
30 production of chlorine and chlorinated organics. The information from The Vinyl Institute and
31 CCC studies was summarized in a recent article by Dyke and Amendola (2007). This article
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1 identifies two facilities as stand-alone vinyl chloride plants. Dyke and Amendola (2007)
2 summarized the releases of CDD/CDF to all media for the year 2000 and provided a confidence
3 rating for each value analogous to one used in this report (see Table 8-7). Dyke and Amendola
4 (2007) presented release estimates for both the years 2000 and 2002. The 2002 values are not
5 reproduced here but are generally lower or similar to the 2000 values.
6
7 8.3.4. Releases
8 The information presented in Dyke and Amendola (2007) was selected as the best basis
9 for estimating CDD/CDF releases from these facilities. The two stand-alone vinyl chloride
10 plants covered in this study are believed to represent most of the stand-alone vinyl chloride
11 production in the United States. Therefore, it was not necessary to develop emission factors to
12 estimate releases from untested facilities. The Dyke and Amendola (2007) release estimates are
13 specific to the year 2000. Since the chemical production rates and technologies used at these
14 facilities have changed significantly since 1987, release estimates cannot be made for 1987 and
15 1995.
16 Table 8-7 shows the amount of CDD/CDFs that are sent to off-site incinerators and
17 landfills. The releases from incineration are included in the estimates presented for hazardous
18 waste incinerators (see Section 3.2). The amount sent to secure landfills (5.57 g I-TEQ in 2000)
19 is not considered to be an environmental release.
20 As discussed above, several studies have detected CDD/CDFs in PVC products.
21 However, no information is available on possible releases from these products, and therefore,
22 they are a potential but unquantifiable source (Not quantifiable).
23 The releases to all media from the stand-alone vinyl chloride plants are presented in
24 Table 8-7.
25 The inventory decision criteria and releases to all media are summarized below:
26
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Inventory Decision Criteria for Stand-Alone Vinyl
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Chloride
Air
Yes
Yes
Yes
Yes
Q
Manufacturing
Water Solids
Yes
Yes
Yes
Yes
Q
Plants
Products
1
2
Stand-Alone Vinyl Chloride Manufacturing Plants
Air Releases
• 1987—Not available.
• 1995—Not available.
• 2000—0.62 g I-TEQ.
Water Releases
• 1987—Not available.
• 1995—Not available.
• 2000—<0.1g I-TEQ.
Solid Residue Releases
None. The solid residues from these plants are disposed in secure landfills and, therefore, are
not considered to be an environmental release.
Products
Not quantifiable.
4
5 8.4. COMPLEX CHEMICAL PLANTS PRODUCING CHLORINE AND A VARIETY
6 OF CHLORINATED ORGANICS
7 As explained at the beginning of Section 8.2, this is a new section based on the
8 reorganization of Sections 8.2 and 8.3 in the original report. This section describes CDD/CDF
9 releases from facilities that produce combinations of chlorine and multiple chlorinated organic
10 chemicals. The plants that exclusively manufacture chlorine are covered in Section 8.2, and the
11 plants that exclusively produce vinyl chloride are covered in Section 8.3.
12
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1 The waste streams at these complex plants are typically combined, which prevents
2 derivation of chemical-specific release estimates. Instead, a facility-specific approach has been
3 used where the releases for each plant are estimated on the basis of the CDD/CDF levels and
4 total flow rates measured at the final release point.
5 These plants currently—or have in the past—produced a variety of chemicals that have
6 been associated with CDD/CDF releases. These include chlorine, vinyl chloride, chlorophenols,
7 chlorobenzenes, and chlorobiphenyls. Background information on the regulations, processes,
8 and products related to chlorine and vinyl chloride products were presented in Sections 8.2 and
9 8.3, respectively. Therefore, they are not repeated in this section. The production and use of
10 chlorophenols, chlorophenoxy herbicides, and PCB products are now banned or strictly regulated
11 in most countries. PCB production ceased prior to the first reference year, i.e., 1987. So
12 CDD/CDF releases associated with PCB production are not covered in this report (PCB releases
13 from nonproduction contemporary sources are covered in Chapter 10, and releases from
14 reservoirs are covered in Chapter 11).
15 Section 8.4 first presents separate discussions on chlorophenol and chlorobenzenes.
16 These discussions describe the manufacturing processes, regulations, and products for these
17 chemical groups. Then the section presents the release estimates occurring during production
18 activities at the complex plants.
19
20 8.4.1. Chlorophenols
21 8.4.1.1. Process Description
22 The two major commercial methods used to produce chlorophenols are (1) electrophilic
23 chlorination of molten phenol by chlorine gas in the presence of catalytic amounts of a metal
24 chloride and organic chlorination promoters and stabilizers, and (2) alkaline hydrolysis of
25 chlorobenzenes under heat and pressure using aqueous methanolic sodium hydroxide. Other
26 manufacturing methods include conversion of diazonium salts of various chlorinated anilines and
27 chlorination of phenolsulfonic acids and benzenesulfonic acids, followed by the removal of the
28 sulfonic acid group (Oilman et al., 1988; Hutzinger and Fiedler, 1991b).
29
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1 8.4.1.2. Regulations for Chlorophenols
2 In 1983, EPA cancelled the sale of Silvex and 2,4,5-T for all uses (Federal Register,
3 1987a). Earlier, in 1979, EPA had ordered emergency suspension of the forestry, rights-of-way,
4 and pasture uses of 2,4,5-T. Emergency suspensions of the forestry, rights-of-way, pasture,
5 home and garden, commercial/ornamental turf, and aquatic weed control/ditch bank uses of
6 Silvex were also ordered (Federal Register, 1979; Plimmer, 1980). The home and garden,
7 commercial/ornamental turf, and aquatic weed control/ditch bank uses of 2,4,5-T had been
8 suspended in 1970.
9 Pentachlorophenol (PCP) was one of the most widely used biocides in the United States
10 prior to the regulatory actions to cancel and restrict certain of its wood and nonwood preservative
11 uses. PCP was registered for use as a herbicide, defoliant, mossicide, and mushroom house
12 biocide. It also found use as a biocide in pulp-paper mills, oil wells, and cooling towers. These
13 latter three uses were terminated on or before 1993 (U.S. EPA, 1993b). However, the major use
14 (greater than 80% of consumption) of PCP was and continues to be wood preservation. An
15 overview of the history of the PCP pesticide rules is presented below.
16 In 1984, EPA issued a notice of intent to cancel registrations of pesticide products
17 containing PCP (including its salts) for all wood preservative uses (Federal Register, 1984). This
18 notice specified modifications to the terms and conditions of product registrations that were
19 required in order to avoid cancellation of the products. In response to this notice, several trade
20 associations and registrants requested administrative hearings to challenge EPA's
21 determinations. After considering the comments and alternatives suggested during the
22 preheating stage of the administrative proceedings, EPA concluded that certain changes to the
23 1984 notice were appropriate. These changes, finalized in 1986 (Federal Register, 1986),
24 included the following: (a) all wood preservative uses of PCP and its salts were classified as
25 "restricted use" only by certified applicators, (b) specific worker protection measures were
26 required, (c) limits were placed on the HxCDD content of PCP, and (d) label restrictions for
27 home and farm uses of PCP prohibited its application indoors and to wood intended for interior
28 use (with a few exceptions) as well as its application in a manner that might result in direct
29 exposure of domestic animals or livestock or in the contamination of food, feed, or drinking and
30 irrigation water.
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1 EPA subsequently amended its notice on the wood preservative uses to establish reliable
2 and enforceable methods for implementing certified limits for HxCDD and 2,3,7,8-TCDD in
3 registered wood preservative pesticide products (Federal Register, 1987b). Levels of
4 2,3,7,8-TCDD were not allowed to exceed 1 ppb in any product, and after February 2, 1989, any
5 manufacturing-use PCP released for shipment could not contain HxCDD levels that exceeded an
6 average of 2 ppm over a monthly release or a batch level of 4 ppm (a gradually phased-in
7 requirement). On January 21, 1987, EPA prohibited the registration of PCP and its salts for most
8 nonwood uses (Federal Register, 1987c). EPA deferred action on several uses (uses in
9 pulp/paper mills, oil wells, and cooling towers) pending receipt of additional exposure, use, and
10 ecological effects data. On January 8, 1993, EPA issued a press advisory stating that its special
11 review of these deferred nonwood uses was being terminated because all of these uses had been
12 either voluntarily cancelled by the registrants or cancelled by EPA for failure of the registrants to
13 pay the required annual maintenance fees (U.S. EPA, 1993b).
14 Di- and trichlorophenol manufacturers are subject to reporting under the Dioxin/Furan
15 Test Rule, which is discussed in Section 8.3.7 of the original report. Since the effective date of
16 that rule (June 5, 1987), only the 2,4-dichlorophenol isomer has been commercially produced in
17 (or imported to) the United States, and as noted in Table 8-8, no CDDs/CDFs were detected in
18 the product. Testing is required for the other di- and trichlorophenols if manufacture or
19 importation resumes. Similarly, tetrachlorophenols were subject to reporting under the
20 Dioxin/Furan Pesticide Data Call-In (discussed in Section 8.3.8 of the original report). Since
21 issuance of the Data Call-in, the registrants of tetrachlorophenol-containing pesticide products
22 have elected to no longer support the registration of their products in the United States.
23 In the mid-1980s, the EPA Office of Solid Waste (OSW) promulgated, under RCRA,
24 land disposal restrictions on wastes (wastewaters and nonwastewaters) resulting from the
25 manufacture of chlorophenols (40 CFR 268). Table 8-9 lists all wastes in which CDDs/CDFs are
26 specifically regulated by EPA as hazardous constituents, including chlorophenol wastes (waste
27 codes F020 and F021). The regulations prohibit the land disposal of these wastes until they are
28 treated to a level below the routinely achievable DLs for the EPA hazardous waste numbers
29 listed in Table 8-9 for each of the following congener groups: TCDDs, PeCDDs, HxCDDs,
30 TCDFs, PeCDFs, and HxCDFs. Wastes from PCP-based wood-preserving operations (waste
31 codes K001 and F032) are also regulated as hazardous wastes under RCRA (40 CFR 261).
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1 The EPA Office of Water promulgated effluent limitations for facilities that manufacture
2 chlorinated phenols and discharge treated wastewater (40 CFR 414.70). These effluent
3 limitations do not specifically regulate CDDs or CDFs. The effluent limitations for the
4 individually regulated chlorinated phenols are less than or equal to 39 ug/L for facilities that use
5 biological end-of-pipe treatment.
6
7 8.4.1.3. Products—Chlorophenols
8 Chlorophenols have been widely used for a variety of pesticidal applications. The
9 higher-chlorinated phenols (tetrachlorophenol and PCP) and their sodium salts have been used
10 primarily for wood preservation. The lower-chlorinated phenols have been used primarily as
11 chemical intermediates in the manufacture of other pesticides. For example, 2,4-dichlorophenol
12 is used to produce the herbicides 2,4-dichlorophenoxyacetic acid (2,4-D),
13 4-(2,4-dichlorophenoxy)butanoic acid (2,4-DB), 2-(2,4-dichlorophenoxy)-propanoic acid
14 (2,4-DP), Nitrophen, Genite, and Zytron, and 2,4,5-trichlorophenol was used to produce
15 hexachlorophene, 2,4,5-T, Silvex, Erbon, Ronnel, and Gardona (Gilman et al., 1988; Hutzinger
16 and Fiedler, 199Ib).
17 Because of the manufacturing processes employed, commercial chlorophenol products
18 can contain appreciable amounts of impurities (Gilman et al., 1988). During the direct
19 chlorination of phenol, CDDs/CDFs can form either by the condensation of tri-, tetra-, and
20 pentachlorophenols or by the condensation of Chlorophenols with hexachlorocyclohexadienone
21 (which forms from excessive chlorination of phenol). During alkaline hydrolysis of
22 chlorobenzenes, CDDs/CDFs can form through chlorophenate condensation (Ree et al., 1988;
23 Gilman et al., 1988; Hutzinger and Fiedler, 1991b)
24 The limited information on CDD/CDF concentrations in Chlorophenols published in the
25 1970s and early 1980s was compiled by Versar, Inc. (1985) and Hutzinger and Fiedler (1991b).
26 The results of several major studies cited by these reviewers (Firestone et al., 1972; Rappe and
27 Marklund, 1978; Rappe et al., 1978) are presented in Table 8-8. Typically, CDDs/CDFs were
28 not detected in mono- and diChlorophenols but were reported in tri- and tetrachlorophenols.
29 More recent results of testing of 2,4-dichlorophenol, performed in response to the Toxic
30 Substances Control Act (TSCA) dioxin/furan test rule, showed no detectable concentrations of
31 2,3,7,8-substituted tetra- through hepta-CDD/CDFs.
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1 Detailed information on 2,4,5-T production and 2,3,7,8-TCDD levels was presented in
2 Chapter 11 of the original report. Production of 2,4,5-T during the 1950s, 1960s, and 1970s was
3 estimated as 2,000, 4,000, and 1,500 MT/year, respectively. This was combined with estimates
4 of 2,3,7,8-TCDD levels in the product to estimate that the cumulative amount of 2,3,7,8-TCDD
5 in 2,4,5-T used over the period of 1950 to 1979 was 36,000 g. No product release estimates are
6 presented for the reference years because production ceased prior to 1987. After the chemical
7 was applied, it would have become incorporated into the soil reservoir. The potential amounts of
8 2,3,7,8-TCDD remaining in the soil reservoir and possible releases are discussed in Chapter 11.
9 The production of PCP for wood preserving began on an experimental basis in the 1930s.
10 In 1947, nearly 3,200 MT of PCP were reported to have been used in the United States by the
11 commercial wood preserving industry. Use in this industry steadily increased through the
12 mid-1970s (AWPI, 1977). Although domestic consumption volumes are not available for all
13 years, it is estimated, on the basis of historical production/export data for PCP reported in
14 Mannsville (1983), that 90 to 95% of production volume has typically been consumed
15 domestically rather than exported. A reasonable estimate of total domestic PCP consumption
16 during the period of 1970 to 1995 is about 400,000 MT. This estimate assumes an average
17 annual consumption rate of 20,000 MT/year during the 1970s, 15,000 MT/year during the 1980s,
18 and 10,000 MT/year during the 1990s.
19 Table 8-10 presents a compilation of published data on the CDD/CDF content of
20 technical-grade PCP. The only samples that have been analyzed for all dioxin-like CDDs/CDFs
21 were manufactured in the mid-to-late 1980s. Figure 8-1 presents these data in graphical form. It
22 shows that the predominant congener groups are OCDD, OCDF, and HpCDD, Waddell et al.
23 (1995) tested analytical-grade PCP (from Aldrich Chemical Co.) for CDD/CDF content and
24 found the same congener profile; however, the CDD/CDF levels were three to four orders of
25 magnitude lower. Table 8-11 presents a similar compilation of published data on the CDD/CDF
26 content of PCP-Na. The table shows the same patterns of dominant congeners and congener
27 groups reported for PCP
28 Samples of technical-grade PCP manufactured during the mid-to-late 1980s contained
29 about 1.7 mg WHO98 TEQDF/kg (3 mg I-TEQ/kg), based on the data presented in Table 8-10.
30 No published reports could be located that present the results of any congener-specific analyses
31 of PCP manufactured since the late 1980s. However, monthly measurements of CDD/CDF
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1 congener group concentrations in technical PCP manufactured for use in the United States have
2 been reported to EPA from 1987 to the present (letter dated March 5, 1997, from Thomas
3 Mitchell, KMG-Bernuth, to Matthew Lorber, U.S. EPA; letter dated February 7, 1997, from John
4 Wilkinson, Pentachlorophenol Task Force, to Matthew Lorber, U.S. EPA; U.S. EPA, 1999a).
5 The average congener group concentrations reported to EPA for the years 1988 (i.e., 1 year after
6 EPA regulations were imposed limiting HxCDD and 2,3,7,8-TCDD concentrations in PCP) to
7 1999 are presented in Table 8-10. In general, the average congener group concentrations during
8 the period of 1988 to 1999 are lower by a factor of 2 to 4 than the concentrations observed in the
9 mid-to-late 1980 (based on the full-congener analysis of samples). If it is assumed that the toxic
10 CDD/CDF congeners have also been reduced by a similar factor, then the TEQ content of PCP
11 manufactured since 1988 is about 0.6 mg WHO98 TEQDF/kg (1 mg I-TEQ/kg).
12 An estimated 12,000 MT of PCP were used for wood preservation in the United States in
13 1987 (WHO, 1991). An estimated 8,400 MT were used in 1994 (AWPI, 1995); for the purposes
14 of this report, it is assumed that an identical amount was used in 1995. In 1999, approximately
15 7,710 MT of PCP were produced annually in the United States (Council of Great Lakes
16 Industries, 1999); for the purposes of this report, it is assumed that an identical amount was
17 produced in 2000. Assuming that 95% of the production volume was consumed domestically
18 (Mannsville, 1983) and that all of the PCP produced in 2000 was used for wood preservation,
19 approximately 7,325 MT of PCP were used in the United States for wood preservation.
20 Combining these activity level estimates with the TEQ concentration estimates presented above
21 indicates that 20,000 g WHO98 TEQDF (36,000 g I-TEQDF), 4,800 g WHO98 TEQDF
22 (8,400 g I-TEQDF), and 4,200 g WHO98 TEQDF (7,300 g I-TEQDF) were incorporated into
23 PCP-treated wood products in 1987, 1995, and 2000, respectively. It is unknown how much of
24 the CDD/CDFs escape from the wood into the environment. Several field studies (Gurprasad et
25 al., 1995; EPRI, 1995; Wan, 1995; Wan and Van Oostdam, 1995) demonstrate that CDDs/CDFs
26 do apparently leach into soil from PCP-treated wood, but the studies do not provide release-rate
27 data. No studies were located that provide any measured CDD/CDF volatilization rates from
28 PCP-treated wood. Although CDDs/CDFs have very low vapor pressures, they are not bound to,
29 nor do they react with, the wood in any way that would preclude volatilization. Lorber et al.
30 (2002) compared the spatial distribution of CDD/CDF congeners in PCP-treated poles of
31 different ages. A trend for dioxins to concentrate in the outer portions of the pole over time
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1 suggests migration within the poles, and this migration may result in some environmental
2 release. However, this study could not quantify such releases. Several studies (Bremmer et al.
3 [1994], Rappe [1995], Eduljee and Dyke [1996] and Douben et al. [1995]) have attempted to
4 estimate potential CDD/CDF volatilization releases using conservative assumptions or modeling
5 approaches, but these estimates span many orders of magnitude. Therefore, no estimate could be
6 made as to what portion of the CDD/CDFs in products are released to the environment (Not
7 quantifiable). The cumulative amounts of CDD/CDFs in PCP-treated wood can also be
8 considered a potential reservoir source (see Chapter 11 for further discussion of this issue).
9
10 8.4.1.4. Products—2,4-D
11 Although 2,4-Dichlorophenoxyacetic acid (2,4-D) is not a true chlorophenol, it is
12 included in this section because it is produced from chlorophenols and, therefore, is closely
13 associated. The available information on 2,4-D production and CDD/CDF levels was
14 summarized in Chapter 11 of the original report. An estimated 28,100 MT of 2,4-D were used in
15 the United States in 2000, making it one of the top 10 pesticides in terms of quantity used (EPA
16 proprietary data). The pesticide 2,4-D is judged to have the potential for environmental release
17 through its agricultural use. Since 1995, the chemical manufacturers of 2,4-D have been
18 undertaking voluntary actions to significantly reduce the dioxin content of the product. No
19 information is available on the level of dioxin contamination, if any, that may have been present
20 in 2,4-D in 2000. An estimated 26,300 and 30,400 MT were used during 1995 and 1987,
21 respectively (U.S. EPA, 1997c, 1988). On the basis of the average CDD/CDF congener
22 concentrations in 2,4-D (not including OCDD and OCDF), the corresponding WHOgg TEQop
23 concentration is 1.1 |ig/kg (0.7 jig I-TEQop/kg). Combining this TEQ concentration with the
24 activity level estimates for 1995 and 1987 indicates that 28.9 g WHO98 TEQDF (18.4 g I-TEQDF)
25 were released in 1995 and 33.4 g WHO98 TEQDF (21.3 g I-TEQDF) was released in 1987. No
26 estimate can be made for 2000 because of the poor quality of existing information.
27
28 8.4.2. Chlorobenzenes
29 8.4.2.1. Process Description
30 Chlorobenzenes can be produced via three methods: (1) electrophilic substitution of
31 benzene (in liquid or vapor phase) with chlorine gas in the presence of a metal salt catalyst,
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1 (2) oxidative chlorination of benzene with HC1 at 150 to 300EC in the presence of a metal salt
2 catalyst, and (3) dehydrohalogenation of hexachlorocyclohexane wastes at 200 to 240EC with a
3 carbon catalyst to produce trichlorobenzene, which can be further chlorinated to produce
4 higher-chlorinated benzenes (Ree et al., 1988; Hutzinger and Fiedler, 1991b; Bryant, 1993).
5 All chlorobenzenes currently manufactured in the United States are produced by the
6 electrophilic substitution process using liquid-phase benzene (i.e., temperature is at or below
7 80EC). FeCb is the most common catalyst employed. Although this method can be used to
8 produce mono- through hexachlorobenzene, the extent of chlorination is controlled to yield
9 primarily monochlorobenzene and dichlorobenzene. The finished product is a mixture of
10 chlorobenzenes, and refined products must be obtained by distillation and crystallization (Bryant,
11 1993).
12
13 8.4.2.2. Regulations for Chlorobenzenes
14 EPA determined, as part of the Federal Insecticide, Fungicide, and Rodenticide Act
15 (FIFRA) Data Call-In, that the 1,4-dichlorobenzene manufacturing processes used in the United
16 States are not likely to form CDDs/CDFs. Mono-, di-, and trichlorobenzene are listed as
17 potential precursor chemicals under the TSCA dioxin/furan test rule and are subject to reporting.
18 In addition, EPA issued a Significant New Use Rule (SNUR) under Section 5(a)(2) of TSCA on
19 December 1, 1993 (effective January 14, 1994) for pentachlorobenzene and
20 1,2,4,5-tetrachlorobenzene (Federal Register, 1993). This rule requires that EPA be notified at
21 least 90 days before the manufacture, import, or processing of either of these compounds in
22 amounts of 10,000 pounds or greater per year per facility for any use. All registrations of
23 pesticide products containing hexachlorobenzene were cancelled in the mid-1980s (Carpenter
24 etal., 1986).
25 OSW promulgated land disposal restrictions on wastes (i.e., wastewaters and
26 nonwastewaters) resulting from the manufacture of chlorobenzenes (40 CFR 268). Table 8-9
27 lists all solid wastes for which EPA specifically regulates CDDs and CDFs, including
28 chlorobenzene wastes, as hazardous constituents. The regulations prohibit the land disposal of
29 these wastes until they are treated to a level below the routinely achievable DLs in the waste
30 extract listed in Table 8-9 for each of the following congener groups: TCDDs, PeCDDs,
31 HxCDDs, TCDFs, PeCDFs, and HxCDFs.
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1 The EPA Office of Water promulgated effluent limitations for facilities that manufacture
2 chlorinated benzenes and discharge treated wastewater (40 CFR 414.70). These effluent
3 limitations do not specifically address CDDs and CDFs. The following chlorinated benzenes are
4 regulated: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene,
5 1,2,4-trichlorobenzene, and hexachlorobenzene. The effluent limitations for the individual
6 regulated chlorinated benzenes are less than or equal to 77 ug/L for facilities that use biological
7 end-of-pipe treatment and less than or equal to 196 ug/L for facilities that do not use biological
8 end-of-pipe treatment.
9 Since at least 1993, U.S. commercial production of chlorobenzenes has been limited to
10 monochlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, and, to a much lesser extent,
11 1,2,4-tri chlorobenzene. As noted above, CDD/CDF formation is not expected under the normal
12 operating conditions of the processes currently used in the United States to produce these
13 four chemicals. No tetra-, penta-, or hexachlorinated benzenes are now intentionally produced or
14 used in the United States (Bryant, 1993). Thus, releases of CDDs/CDFs from the manufacture of
15 chlorobenzenes in 1995 were estimated to be negligible. Because the information available on
16 CDD/CDF content of mono-through pentachlorobenzene is very limited and is based primarily
17 on unpublished European data, and because information on the chlorobenzene manufacturing
18 processes in place during 1987 is not readily available, no emission estimates can be made for
19 1987.
20
21 8.4.2.3. Products—Chlorobenzenes
22 Chlorobenzenes have been produced in the United States since 1909. U.S. production
23 operations were developed primarily to provide chemical raw materials for the production of
24 phenol, aniline, and various pesticides based on the higher-chlorinated benzenes. Because of
25 (incremental) changes in the processes used to manufacture phenol and aniline and the phaseout
26 of highly chlorinated pesticides such as DDT and hexachlorobenzene, U.S. production of
27 chlorobenzenes in 1988 had decreased to 50% of the peak production level, in 1969.
28 CDDs/CDFs can be produced inadvertently during the manufacture of chlorobenzenes by
29 nucleophilic substitution and pyrolysis mechanisms (Ree et al., 1988). The criteria required for
30 production of CDDs/CDFs via nucleophilic substitution are oxygen as a nuclear substituent (i.e.,
31 presence of chlorophenols) and production or purification of the substance under alkaline
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1 conditions. Formation via pyrolysis requires reaction temperatures above 150°C (Ree et al.,
2 1988; Hutzinger and Fiedler, 1991b). The liquid-phase electrophilic substitution process
3 currently used in the United States does not meet either of these criteria. Although Ree et al.
4 (1988) and Hutzinger and Fiedler (1991b) state that the criteria for formation of CDDs/CDFs via
5 nucleophilic substitution may be present in the catalyst neutralization and purification/distillation
6 steps of the manufacturing process; Opatick (1995) states that the chlorobenzene reaction
7 product in U.S. processes remains mildly acidic throughout these steps.
8 Table 8-12 summarizes the very limited published information on CDD/CDF
9 contamination of chlorobenzene products. The presence of CDDs/CDFs has been reported in
10 tri-, penta-, and hexachlorobenzene. No CDDs/CDFs have been reported in mono- or
11 dichlorobenzene. Conflicting data exist concerning the presence of CDDs/CDFs in
12 tri chlorobenzene. One study (Villanueva et al., 1974) detected no CDDs/CDFs in one sample of
13 1,2,4-TCBz at a DL of 0.1 |ig/kg. Hutzinger and Fiedler (1991b) reported unpublished results of
14 a study by Dr. Hans Hagenmaier showing CDD/CDF congener group concentrations ranging
15 from 0.02 to 0.074 |ig/kg in a sample of mixed TCBz. Because the TCBz examined by
16 Hagenmaier contained about 2% hexachlorocyclohexane, it is reasonable to assume that it was
17 produced by dehydrohalogenation of hexachlorocyclohexane (a manufacturing process not
18 currently used in the United States).
19 In conclusion, although there is some evidence that CDD/CDFs may be present in
20 chlorobenzene products, insufficient information is available to make quantitative estimates.
21 Accordingly, they are considered to be unquantifiable.
22
23 8.4.3. Complex Plants
24 In the year 2000, two facilities with an SIC code for plastic materials, synthetic resins,
25 and nonvulcanizable elastomers reported dioxin releases under the EPA TRI program (U.S. EPA,
26 2008). The sum of the air releases across these facilities was 5.6 g, which EPA estimates is
27 equal to 0.5 gWHOgg TEQoF. No releases to other media were reported. As explained in
28 Chapter 1, the TRI data are not used to make quantitative estimates in this document but rather as
29 supportive evidence that releases do occur.
30 In the year 2000, four facilities with an SIC code for industrial organic chemicals not
31 classified elsewhere reported dioxin releases under the EPA TRI program (U.S. EPA, 2008).
This document is a draft for review purposes only and does not constitute Agency policy.
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1 The sum of the air releases across these facilities was 153 g, which EPA estimates is equal to
2 2.2 g WHOgg TEQop No releases to other media were reported. As explained in Chapter 1, the
3 TRI data are not used to make quantitative estimates in this document but rather as supportive
4 evidence that releases do occur.
5 The information presented in Dyke and Amendola (2007) was selected as the best basis
6 for estimating CDD/CDF releases from facilities that produce combinations of chlorine and
7 multiple chlorinated organic chemicals. The 10 complex chemical plants covered in this study
8 are believed to represent most facilities of this type in the United States. Therefore, it was
9 unnecessary to develop emission factors to estimate releases from untested facilities. Dyke and
10 Amendola reported their release estimates in I-TEQs, but stated that WHOgg values were usually
11 less than 20% different. Using the water congener profile, the WHOgg values were computed to
12 be only 4% higher that the I-TEQs. On this basis the I-TEQs were assumed to be equivalent to
13 the WHOgg TEQs for all releases. The Dyke and Amendola release estimates are specific to the
14 year 2000. Because the chemical production rates and technologies used at these facilities have
15 changed significantly, no release estimates could be made for 1987 and 1995.
16 Table 8-13 shows the amount of CDD/CDFs that are sent to off-site incinerators and
17 landfills. The releases from incineration are included in the estimates presented for hazardous
18 waste incinerators (see Section 3.2). The amounts sent to secure landfills (118 g I-TEQ in 2000)
19 are not considered to be environmental releases.
20 The releases to all media from the complex chemical plants are presented in Table 8-13.
21 The inventory decision criteria and releases to all media are summarized below:
22
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Complex Chemical Plants
Variety of Chlorinated Organics
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
VIeasured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Air
Yes
Yes
Yes
Yes
Q
Producing
Water
Yes
Yes
Yes
Yes
Q
Chlorine
Solids
Yes
Yes
Yes
Yes
Q
and a
Products
Yes
Yes
Yes
Yes
Q
1
2
This document is a draft for review purposes only and does not constitute Agency policy.
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Complex Chemical Plants Producing Chlorine and a Variety of Chlorinated Organics
Air Releases
• 1987—Not available.
• 1995—Not available.
• 2000—5 g (WHO98 or I-TEQ).
Water Releases
• 1987—Not available.
• 1995—Not available.
• 2000—25 g (WHO98 or I-TEQ).
Solid Residue Releases
Landfarmed
• 1987—Not available.
• 1995—Not available.
• 2000—1 g (WHO98 or I-TEQ).
Products
PVCs
• 1987—Not quantifiable.
• 1995—Not quantifiable.
• 2000—Not quantifiable.
Pentachlorophenols
• 1987—Not quantifiable.
• 1995—Not quantifiable.
• 2000—Not quantifiable.
2,4-Dichlorophenoxy acetic acid (2,4-D)
• 1987—33 g WH098 TEQDF (21 g I-TEQDF).
• 1995—29 g WHO98 TEQDF (18 g I-TEQDF).
• 2000—Not quantifiable.
Chlorobenzenes
• 1987—Not quantifiable.
• 1995—Not quantifiable.
• 2000—Not quantifiable.
1
2 8.5. MUNICIPAL WASTEWATER TREATMENT PLANTS
3 This section corresponds to Section 8.4.1 of the original report. Minor changes were
4 made to the solid residue and product release estimates.
5
6
This document is a draft for review purposes only and does not constitute Agency policy.
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1 8.5.1. Air Releases
2 Releases associated with sewage sludge incineration are covered in Section 3.5.
3
4 8.5.2. Water Releases
5 No changes were made to the emission factors, activities, or release estimates. The
6 CRWQCB data (memorandum dated March 21, 1996, from Lila Tang, California Regional
7 Water Quality Control Board, to David Cleverly, U.S. EPA) were the only U.S. data that
8 provided TEQ estimates for CDD/CDF levels in wastewaters from sewage treatment plants.
9 Accordingly, the concentration from this study (0.27 pg WHO9g TEQDF/L [0.29 pg I-TEQDF/L])
10 was assumed to apply to all reference years. However, these data were from plants in the San
11 Francisco area and cannot be considered to be representative of the 16,000-plus POTWs
12 nationwide. Therefore, the emission factor was considered preliminary. Activity estimates were
13 derived from EPA surveys as described in US EPA (2006) and are presented in the release
14 summary below.
15
16 8.5.3. Solid Residue Releases
17 The large U.S. studies (U.S. EPA, 1996b, 2002d; Green et al., 1995; Cramer et al., 1995)
18 were selected as the best basis for estimating emission factors. Because the mean I-TEQop
19 concentration values reported in the 1988/1989 sewage sludge survey (U.S. EPA, 1996b) and the
20 1995 survey (Green et al., 1995; Cramer et al., 1995) were very similar, the estimated amounts of
21 TEQs that may have been present in sewage sludge and released to the environment in 1987 and
22 1995 were assumed to be the same. These values were estimated using the average of the mean
23 concentration values (nondetects equal to DLs) reported by EPA (1996b) (50 ng I-TEQop/kg)
24 and by Green et al. (1995) and Cramer et al. (1995) (36.3 ng WHO98 TEQDF/kg
25 [47.7 ng I-TEQop/kg]). Therefore, the overall average mean emission factor for reference years
26 1987 and 1995 is 36.3 ng WHO98 TEQDF/kg (48.9 ng I-TEQDF/kg). The emission factor of
27 14 ng WHOgg TEQDF/kg (15 ng I-TEQDF/kg), as calculated from the 2001 survey (U.S. EPA,
28 2002d), appears to be the most reasonable TEQ emission factor estimate for reference year 2000
29 because this estimate is nationally weighted on the basis of wastewater flow rates of POTWs
30 operating in the United States in 2001 (see Table 8-14—note that the values in this table were
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1 recalculated, resulting in minor decreases compared to the original document, which presented
2 the data in Table 8-40).
3 No changes were made to the sludge activity results, which were presented in
4 three categories: land applied (includes advanced treatment since this refers to composting,
5 which is generally done in unlined containers), landfilled (includes sludge landfills, codisposal
6 landfills, and surface disposal), and product (includes distribution/marketing and beneficial use).
7 The summary table below presents the activities and releases for sludge, which is land applied or
8 used in products. These are assumed to result in environmental releases. The landfilled sludges
9 are not included in the summary because they are not considered to be environmental releases.
10 The activity estimates for the landfilled sludge were 2.37 million dry MT in 1987,
11 1.10 million dry MT in 1995, and 0.90 million dry MT in 2000. The CDD/CDF amounts in the
12 landfilled sludge were estimated as follows:
13
14 • 1987—86 g WHO TEQDF (120 g I-TEQDF/kg)
15 • 1995—40 g WHO TEQDF (54 g I-TEQDF/kg)
16 • 2000—13 g WHO TEQDF (14 g I-TEQDF/kg)
17
18 8.5.4. Products
19 The sewage sludge emission factors described above were also applied to the swage
20 sludge used as products. No changes were made to the activity estimates. All of these values
21 and the resulting release estimates are presented in the summary table below.
22
23 8.5.5. Releases
24 The inventory decision criteria and releases to all media are summarized below:
25
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Inventory Decision Criteria for Municipal Wastewater Treatment Plants
Air Water Solids Products
Emission tests for at least two units/source types with Yes Yes Yes
mfficient documentation to directly derive emission
'actors.
Measured emission factors consistent or have Yes Yes Yes
understandable differences.
mission factor tests represent units that are typical of the No Yes Yes
;lass.
activity estimates based on source-specific surveys. Yes Yes Yes
Conclusion (Q = Quantitative, P = Preliminary). P Q Q_
1
2
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Municipal Wastewater Treatment Plants
Air Releases
None.
Water Releases
Emission Factors
• 1987—0.27 pg WHO TEQDF/L (0.29 pg I-TEQDF/L) (Preliminary).
• 1995—0.27 pg WHO TEQDF/L (0.29 pg I-TEQDF/L) (Preliminary).
• 2000—0.27 pg WHO TEQDF/L (0.29 pg I-TEQDF/L) (Preliminary).
Activity Levels
• 1987—47.8 trillion L.
• 1995—44.5 trillion L.
• 2000—54.0 trillion L.
Releases
• 1987—13 g WHO TEQDF/yr (14 g I-TEQDF/yr) (Preliminary).
• 1995—12 g WHO TEQDF/yr (13 g I-TEQDF/yr) (Preliminary).
• 2000—15 g WHO TEQDF/yr (16 g I-TEQDF/yr) (Preliminary).
Solid Residue Releases
Emission Factors
• 1987—36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg).
• 1995—36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg).
• 2000—14 ng WHO TEQDF/kg (15 ng I-TEQDF/kg).
Activity Levels
Land Applied
• 1987—1.71 million dry MT/yr.
• 1995—3.20 million dry MT/yr.
• 2000—3.60 million dry MT/yr.
Releases
Land Applied
• 1987—62 g WHO TEQDF (84 g I-TEQDF/kg).
• 1995—120 g WHO TEQDF (160 g I-TEQDF/kg).
• 2000—50 g WHO TEQDF (54 g I-TEQDF/kg).
This document is a draft for review purposes only and does not constitute Agency policy.
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Municipal Wastewater Treatment Plants (continued)
Products
Emission Factors
• 1987—36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg).
• 1995—36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg).
• 2000—14 ng WHO TEQDF/kg (15 ng I-TEQDF/kg).
Activity Levels
• 1987—0.07 MMT.
• 1995—0.50 MMT.
• 2000—0.50 MMT.
Releases
• 1987—3 g WHO TEQDF (3 g I-TEQDF/kg).
• 1995—18 g WHO TEQDF (24 g I-TEQDF/kg).
• 2000—7 g WHO TEQDF (8 g I-TEQDF/kg).
1
2
3 8.6. DRINKING WATER TREATMENT PLANTS
4 This section corresponds to Section 8.4.2 in the original report. As discussed in the
5 original report, there is no evidence that releases of CDD/CDFs occur from drinking water
6 treatment plants. No changes were made to this conclusion.
7
8 8.7. SOAPS AND DETERGENTS
9 This section corresponds to Section 8.4.3 in the original report. As discussed in the
10 original report, there is some evidence that soaps and detergents may be a source of CDD/CDFs,
11 but the data were judged inadequate for making quantitative estimates.
12
Soaps and Detergents
Releases
Not quantifiable.
13
14
15 8.8. TEXTILE MANUFACTURING AND DRY CLEANING
16 This section corresponds to Section 8.4.4 in the original report. As discussed in the
17 original report, there is some evidence that textiles manufacturing and dry cleaning may be
18 sources of CDD/CDFs, but the data were judged inadequate for making quantitative estimates.
19
20
21
This document is a draft for review purposes only and does not constitute Agency policy.
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Textiles Manufacturing and Dry Cleaning
Releases
Not quantifiable.
1
2
3 8.9. DYES, PIGMENTS, AND PRINTING INKS
4 This section corresponds to Section 8.3.6 in the original report. As discussed in the
5 original report, very little chloranil has been produced in the United States since the 1980s, so
6 production releases during the reference years are probably negligible. EPA (2006) used
7 concentration and import data to estimate that chloranil imports contained 64 g I-TEQ in 1987,
8 0.4 g I-TEQ in 1995, and 1.2 g I-TEQ in 2000. It is unknown if releases occurred from these
9 products.
10
Chloranil Imports
Releases
Not quantifiable.
11
12
13 Similarly, some evidence exists that phthalocyanine dyes and printing inks may be a
14 source of CDD/CDFs, but the data were judged inadequate for making quantitative estimates.
15
Phthalocyanine Dyes and Printing Inks
Releases
Not quantifiable.
16
17
18 8.10. OTHER ALIPHATIC CHLORINE COMPOUNDS
19 This section corresponds to Section 8.3.5 in the original report. As discussed in the
20 original report, there is no strong evidence that CDD/CDFs are present in these compounds.
21
22 8.11. RESIDENTIAL SEPTIC SYSTEMS
23 This is a new section. Because CDD/CDFs have been measured in discharges from
24 municipal wastewater treatment systems, they may also be released from residential septic
25 systems. No information was found on measured CDD/CDF levels in the sewage entering these
26 systems. However, preliminary estimates can be made as discussed below.
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1 8.11.1. Process Description
2 Most residential septic systems consist of a septic tank and drainage field or dry well.
3 The household waste flows by gravity into the septic tank where biological digestion occurs and
4 solids settle out. The overflow goes into the drainage field or dry well where it slowly percolates
5 into the ground.
6
7 8.11.2. Regulations
8 None specific to dioxins.
9
10 8.11.3. Emission Factor
11 No measurements were found on the amount of CDD/CDF excreted by people. However
12 studies have been done with dairy cattle involving measurements of dioxins in their feed, milk,
13 feces, and urine under carefully controlled settings (Winters et al., 2000; Lorber et al., 2000;
14 McLachlan et al., 1990). These studies found that 50% to 100% of both TEQs and individual
15 congeners in the feed were recovered in the milk and feces. For purposes of a preliminary
16 estimate, it is assumed here that 100% of the dioxin TEQs ingested by people are excreted in the
17 feces. Clearly this is an overestimate particularly for lactating mothers. For the general
18 population, adult daily intakes are estimated to average 43 pg WHOgg TEQop for CDD/CDFs and
19 23 pg WHO98 TEQpcB for PCBs (U.S. EPA, 2004). It is assumed that 30 pg WHO98 TEQDF/day
20 represents a whole population average (children plus adults) for the CDD/CDFs. Assuming that
21 two thirds of an individual's excretion occurs at their residence, 20 pg WHOggTEQoF/day is
22 discharged to the septic system. It is also assumed that no TEQ degradation or formation occurs
23 in the septic system.
24 Septic systems are designed to trap the solid components of sewage in a septic tank. The
25 tank is periodically pumped, and the contents are discharged to a municipal wastewater treatment
26 system (these releases are covered in Section 8.5). Many of the smaller particles and oily
27 components will flow into the drainage field. The fraction CDD/CDFs released to the drainage
28 field will depend largely on the solids trapping efficiency of the system, which depends on
29 variables such as tank size, flow rates, and pumping frequency. For the purposes of a
30 preliminary estimate, this is assumed to be 50%. Thus, the overall emission factor is assumed to
31 be 10 pg WHOgg TEQop/day-person and would be applicable to all reference years. Considering
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1 the lack of direct feces measurements and multiple assumptions required for this estimate, it is
2 given a preliminary confidence rating.
3
4 8.11.4. Activity
5 Septic systems serve 25% of the U.S. population (U.S. EPA, 2005). The total U.S.
6 population is estimated to be 242 million in 1987, 263 million in 1995, and 300 million in 2000
7 (U.S. DOC, 2000). Multiplying by 25%, the activity for each reference year is 61 million in
8 1987, 66 million in 1995, and 75 million in 2000.
9
10 8.11.5. Releases
11 The releases from septic systems will occur via the liquid effluent that drains into the soil.
12 It is included with the solid residues because the release is to land.
13 The inventory decision criteria and releases to all media are summarized below:
14
Inventory Decision Criteria for Residential Septic Systems
Air Water Solids Products
mission tests for at least two units/source types with No
sufficient documentation to directly derive emission
'actors.
Vleasured emission factors consistent or have
understandable differences.
mission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
15
16
This document is a draft for review purposes only and does not constitute Agency policy.
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Residential Septic Systems
Air Releases
None.
Water Releases
None.
Solid Residue Releases
Emission Factors
• 1987—10 pg WHO9g TEQoF/day-person (Preliminary).
• 1995—10 pg WHO9g TEQoF/day-person (Preliminary).
• 2000—10 pg WHOgg TEQpF/day-person (Preliminary).
Activity Levels
• 1987—61 million people.
• 1995—66 million people.
• 2000—75 million people.
Releases
• 1987—0.2 g WHO98 TEQDF (Preliminary).
• 1995—0.2 g WHO9g TEQoF (Preliminary).
• 2000—0.3 g WHO98 TEQpF (Preliminary).
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Table 8-1. CDD/CDF concentrations (ug/kg) in graphite electrode sludge
from chlorine production
Congener/congener group
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDDa
Total 2,3,7,8-CDFa
Total I-TEQDFa
Total WHO98 TEQDFa
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDFa
Sludge 1
ND (0.006)
ND (0.007)
ND (0.018)
ND (0.012)
ND (0.016)
0.095
0.92
26
25
12
32
7
1.3
0.87
9.1
8.1
31
1.02
152.37
14.2
14.1
ND (0.006)
ND (0.070)
ND (0.046)
0.22
0.92
64
75
68
24
31
263.14
Sludge 2
ND (0.009)
ND (0.009)
ND (0.026)
ND (0.016)
ND (0.022)
0.21
2
56
55
25
71
16
2.8
1.9
19
19
76
2.21
341.7
30.5
30.4
ND (0.009)
ND (0.009)
ND (0.064)
0.48
2
150
240
140
53
76
661.48
Sludge 3
ND (0.009)
ND (0.009)
ND (0.029)
ND (0.019)
ND (0.025)
0.25
2.2
57
56
24
73
15
2.6
2
19
20
71
2.45
339.6
30.2
30.2
ND (0.009)
ND (0.009)
ND (0.074)
0.56
2.2
140
240
140
54
71
647.76
Sludge 4
ND
ND (0.033)
ND (0.49)
ND (0.053)
ND(1.2)
0.055
0.65
52
55
27
44
12
1.7
1.3
15
14
81
0.7
303
27.7
27.6
—
-
-
-
0.65
—
—
—
-
81
-
""Calculated assuming nondetect values were zero.
ND = Not detected (value in parenthesis is the reported detection limit).
~ = No information given.
Sources: Rappe et al. (1991); Rappe (1993).
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to
OJ
Table 8-2. Releases of dioxin-like compounds in wastewater discharges from chlor-alkali manufacturing
facilities to surface water in 2000
Congener
2,3,7,8 TCDD
1,2,3,7,8 PeCDD
1,2,3,4,7,8 HxCDD
1,2,3,6,7,8 HxCDD
1,2,3,7,8,9 HxCDD
1,2,3,4,6,7,8 HpCDD
OCDD
2,3,7,8 TCDF
1,2,3,7,8 PeCDF
2,3,4,7,8 PeCDF
1,2,3,4,7,8 HxCDF
1,2,3,6,7,8 HxCDF
1,2,3,7,8,9 HxCDF
2,3,4,6,7,8 HxCDF
1,2,3,4,6,7,8 HpCDF
1,2,3,4,7,8,9 HpCDF
OCDF
Total I-TEQ
Total WHO98 TEQDF
Occidental Chemical Corporation
Battleground,
TX
0.00
0.00
0.00
0.00
0.00
0.00
0.48
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
4.83e!04
4.83e!05
Deer Park, TX
0.02
0.00
0.00
0.00
0.00
0.08
21.50
0.63
1.20
0.21
2.11
0.38
2.03e!03
0.00
0.59
5.66e!03
4.88
0.53
0.51
Delaware City,
DE
0.00
0.00
0.00
0.00
0.00
0.00
4.09e!03
1.02e!03
0.00
0.00
0.00
0.00
0.00
0.00
2.31e!03
0.00
0.00
1.29e!04
1.26e!04
Hahnville,
LA
0.00
0.00
0.00
0.00
0.00
0.01
0.10
0.19
0.90
0.85
2.96
1.18
0.63
0.60
4.47
0.69
1.75
1.08
1.08
Mobile,
AL
0.00
0.00
0.00
0.00
0.00
0.00
1.15e!03
2.88e!04
0.00
0.00
0.00
0.00
0.00
0.00
6.49e!04
0.00
0.00
3.64e!05
3.54e!05
Muscle Shoals,
AL
0.00
0.00
0.00
0.00
0.00
0.00
1.13e!09
3.94e!08
1.33e!07
7.99e!08
1.85e!07
9.76e!08
2.29e!08
3.28e!08
1.32e!07
6.30e!08
1.34e!07
8.65e!08
8.63e!08
PPG Industries
Natrium,
WV
0.00
0.00
0.00
0.00
0.00
0.22
3.13
0.06
0.06
0.33
0.11
0.00
0.00
0.00
0.15
0.00
0.66
0.19
0.19
Total
0.02
0.00
0.00
0.00
0.00
0.31
25.22
0.89
2.16
1.39
5.18
1.56
0.63
0.60
5.22
0.69
7.29
1.80
1.59
§•
rs
I
'TS
s
§
i
a,
°t
§!
*&
31
^
HH ^3
H S.
MŁ
O '
&
O
c
O
H
W
Source: CCC (2004).
-------
Table 8-3. Congener-specific and TEQ annual releases to air (g/year) from a
chlor-alkali facility in 2000
Congener
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,7,8,9-HpCDD
OCDF
Total I-TEQoF
Total WHO9g TEQoF
PPG Industries
Natrium, WV
0.003
0.000
0.000
0.002
0.002
0.087
0.208
0.044
0.003
0.030
0.044
0.006
0.006
0.022
0.142
0.039
0.064
0.034
0.033
Source: Chlorine Chemistry Council (2004).
This document is a draft for review purposes only and does not constitute Agency policy
1/7/2013 8-38 DRAFT: DO NOT CITE OR QUOTE
-------
Table 8-4. Annual releases in 2000 from stand-alone chlor-alkali plants (g I-TEQ/year)
to
OJ
Plant/Location
Occidental — Mobile, AL
Confidence Rating
Occidental — Battleground,
TX
Confidence Rating
Occidental— Deer Park, TX
(CA)
Confidence Rating
Occidental — Delaware City,
DE
Confidence Rating
Occidental— Hahnville (Taft),
LA
Confidence Rating
Occidental — Muscle Shoals,
AL
Confidence Rating
PPG Industries — Natrium,
WV
Confidence Rating
Total
Chemicals
C12 (membrane-cell), caustic
potash, sodium silicate
C12 (diaphragm-cell), NaOH
C12 (mercury /diaphragm-
cell), NaOH
C12 (mercury-cell), NaOH,
caustic potash,
C12 (mercury /diaphragm-
cell), NaOH, sulfur
C12 (mercury -cell) and
caustic potash
C12 (mercury /diaphragm-cell
cell), NaOH
On-site
Air
0.034
R/H
0.03
Water
3.60 x 10~5
H/H
4.80x 10"
H/H
0.54
H/H
1.30x 10"
R/H
1.08
H/H
8.70 x 10"8
H/H
0.193
R/R
1.81
Landfill
0.0
Landfarm
0.0
Off-site transfers"
Landfill
0.83
H/H
0.38
R/H
0.81
H/H
0.2
H/H
0.38
H/H
0.085
H/H
2.69
Incineration
3.50 x 1Q-6
H/H
9.60 x 10~9
H/H
0.0
Well Inj
0.04
R/H
0.04
§•
rs
I
'TS
s
§
i
a,
§•
31
H S.
w^-
O '
&
O
c
O
H
W
"The off-site transfers represent the amount going to off-site facilities and not the amount released to the environment.
H = High.
R = Reasonable.
Source: Dyke and Amendola, 2007.
-------
Table 8-5. Reported CDD/CDF concentrations (ug/kg) in wastes from
polyvinyl chloride (PVC) manufacture
Congener/congener group
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDD
Total 2,3,7,8-CDF
Total I-TEQDF
Total WHO98 TEQoF
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
F024 waste
0.37
0.14
0.3
0.14
0.11
4.2
15
0.91
9.5
1.6
110
24
9.5
3.1
250
51
390
20.3
849.6
20
19.7
3.1
3.6
1.3
5
15
15
65
300
450
390
1,248
KOI 9 waste
260
890
260
330
620
920
1,060
680
975
1,050
10,100
9,760
21,800
930
13,400
1,340
43,500
4,340
103,535
5,928
6,333
1,230
3,540
3,950
1,270
1,060
20,600
45,300
63,700
16,600
43,500
200,750
K020 waste
0.06
0.05
0.08
0.06
0.07
0.89
3
0.44
1.8
0.58
11
2.4
1.3
0.89
38
6
650
4.21
712.4
3.2
2.6
1.9
1.7
a
1.7
3
6
11
27
58
650
760.3
aCongener group concentration reported in source is not consistent with reported congener concentrations.
Source: Stringer et al. (1995).
This document is a draft for review purposes only and does not constitute Agency policy
1/7/2013 8-40 DRAFT: DO NOT CITE OR QUOTE
-------
Table 8-6. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers
to
Congener/congener group
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Mean I-TEQop (nondetect = 0)
Mean I-TEQDF (nondetect = V2 DL)
Suspension and mass
PVC resins
No.
detects/
samples"
0/22
0/22
0/22
0/22
0/22
1/22
0/22
0/22
0/22
0/22
0/22
0/22
0/22
1/22
0/22
0/22
0/22
Range"5 (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.002
Max.
ND
ND
ND
ND
ND
0.64
ND
ND
ND
ND
ND
ND
ND
0.37
ND
ND
ND
0.7
Dispersion PVC resins
No. of
detects/
samples
0/6
0/6
0/6
0/6
0/6
1/6
0/6
0/6
0/6
0/6
0/6
0/6
0/6
0/6
0/6
0/6
2/6
Range0 (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.001
Max.
ND
ND
ND
ND
ND
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.38
0.4
EDC sold as product11
No. detects/
samples
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
1/5
1/5
1/5
Range6 (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.001
Max.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.1
0.4
11
0.21
§•
rs
I
'TS
s
i
a,
§•
a
o
31
H S.
O
c
o
H
W
-------
to
OJ
Table 8-6. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers (continued)
Congener/congener group
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Suspension and mass
PVC resins
No.
detects/
samples"
0/22
0/22
0/22
1/22
0/22
0/22
0/22
1/22
0/22
0/22
Range"5 (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
0.64
ND
ND
ND
0.37
ND
ND
Dispersion PVC resins
No. of
detects/
samples
1/6
1/6
5/6
1/6
0/6
0/6
1/6
0/6
0/6
2/6
Range0 (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
0.24
0.32
0.97
1.3
ND
ND
0.3
ND
ND
0.38
EDC sold as product11
No. detects/
samples
0/5
0/5
0/5
0/5
0/5
0/5
0/5
0/5
1/5
1/5
Range6 (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
ND
ND
ND
ND
ND
2.02
11
§•
rs
I
'TS
s
i
a,
§•
a
o
31
H S.
MŁ
O '
aTwo of these 22 samples were duplicate samples from two sites. The results were averaged and treated as one sample for each site.
bDetection limits (DLs) for individual samples were less than 2 ng/kg for all congeners and congener groups except OCDD and OCDF, which had DLs less than
6 ng/kg.
°DLs for individual samples were less than 2 ng/kg for all congeners and congener groups except OCDD and OCDF, which had DLs less than 4 ng/kg.
d"Sales" EDC is defined as EDC sold commercially for non-VCM uses or exported from the United States.
DLs were less than 1 ng/kg for all congeners in all samples.
DL = Detection limit.
EDC = Ethylene dichloride.
ND = Not detected.
PVC = Polyvinyl chloride.
VCM = Vinyl chloride monomer.
/O Source: The Vinyl Institute (1998).
O
H
W
-------
Table 8-7. Annual releases in 2000 from stand-alone vinyl chloride plants (g I-TEQ/year)
to
Plant/Location
Occidental — Deer Park, TX
Confidence Rating
Occidental — LaPorte, TX
Confidence Rating
Total
Chemicals
VCM
VCM
On-site
Air
0.581
H/H
0.039
H/H
0.62
Water
0.031
H/H
0.0064
H/H
0.04
Landfill
Landfarm
Off-site Transfers"
Landfill
0.474
H/H
5.1
H/H
5.57
Incineration
22.2
H/H
44.4
H/H
66.60
§•
rs
I
i
a.
\VJ
i|- aThe off-site transfers represent the amount going to off-site facilities and not the amount released to the environment.
^ H = High Confidence.
s
g Source: Dyke and Amendola, 2007.
*Tl O
H §
>!
O 5
O S.
t^i
OOQ
TO
H »
H §.
O^
O
O
H
W
-------
Table 8-8. CDD/CDF concentrations (mg/kg) in mono-through tetrachlorophenols
to
OJ
Congener/
congener
group
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
TOTAL
2-CPa
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
+
ND
ND
ND
ND
-
2,4-DCPa
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND
ND
ND
ND
ND
-
2,6-DCPa
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND
ND
ND
ND
ND
-
2,4,5-TrCP
(Na salt)"
ND (0.02) to 14
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND
ND
ND
ND
ND
-
2,4,5-TrCPa
ND (0.02) to 6.5
ND (0.02) to 1.5
ND (0.02)
ND (0.02)
ND (0.02)
ND
ND
ND
ND
ND
-
2,4,6-TrCPa
ND (0.02) to 49
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
+
+
+
ND
ND
-
2,4,6-TrCP
(Na salt)b
O.02
O.03
0.03
0.1
O.I
1.5
17.5
36
4.8
-
2,3,4,6-TeCPa
ND (0.02)
ND (0.02)
ND (0.02) to 15
ND (0.02) to 5.1
ND (0.02) to 0.17
+
+
+
+
+
-
2,3,4,6-TeCP
(Na salt)b
0.7
5.2
9.5
5.6
0.7
0.5
10
70
70
10
-
§•
rs
I
'TS
s
§
i
a,
§•
oo I aSource: Firestone et al. (1972); because of poor recoveries, the authors stated that actual CDD/CDF levels may have been considerably higher than those
reported.
bSources: Rappe and Marklund (1978); Rappe et al. (1978); common Scandinavian commercial chlorophenols.
ND = Not detected (value in parenthesis is the detection limit, if reported).
+ = Detected but not quantified.
~ = No information given.
31
H S.
w^-
O '
&
O
c
O
H
W
-------
Table 8-9. Summary of specific dioxin-containing wastes that must comply
with land disposal restrictions"
EPA
hazardous
waste number
Waste description
Land disposal
restriction effective
date
Regulated
waste
constituent
F020
Wastes (except waste water and spent carbon from
HC1 purification) from the production or
manufacturing use (as a reactant, chemical
intermediate, or component in a formulating
process) of tri- or tetrachlorophenol or of
intermediates used to produce their pesticide
derivatives. (This listing does not include wastes
from the production of hexachlorophene from
highly purified 2,4,5-trichlorophenol.)
November 8, 1988
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
F021
Wastes (except waste water and spent carbon from
HC1 purification) from the production or
manufacturing use (as a reactant, chemical
intermediate, or component in a formulating
process) of pentachlorophenol or of intermediates
used to produce its derivatives.
November 8, 1988
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
F022
Wastes (except waste water and spent carbon from
HC1 purification) from the manufacturing use (as
a reactant, chemical intermediate, or component in
a formulating process) of tetra-, penta-, or
hexachlorobenzenes under alkaline conditions.
November 8, 1988
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
F023
Wastes (except waste water and spent carbon from
HC1 purification) from the production of materials
on equipment previously used for the production
or manufacturing use (as a reactant, chemical
intermediate, or component in a formulating
process) of tri- and tetrachlorophenols. (This
listing does not include wastes from equipment
used only for the production or use of
hexachlorophene from highly purified
2,4,5-trichlorophenol.)
November 8, 1988
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
F026
Wastes (except waste water and spent carbon from
HC1 purification) from the production of materials
on equipment previously used for the
manufacturing use (as a reactant, chemical
intermediate, or component in a formulating
process) of tetra-, penta-, or hexachlorobenzene
under alkaline conditions.
November 8, 1988
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
This document is a draft for review purposes only and does not constitute Agency policy
1/7/2013 8-45 DRAFT: DO NOT CITE OR QUOTE
-------
Table 8-9. Summary of specific dioxin containing wastes that must comply
with land disposal restrictions" (continued)
EPA
hazardous
waste number
F027
F028
F039
K043
K099
Waste description
Discarded unused formulations containing tri-,
tetra-, or pentachlorophenol or discarded unused
formulations containing compounds derived from
these chlorophenols. (This listing does not
include formulations containing hexachlorophene
synthesized from prepurified 2,4,5-trichlorophenol
as the sole component.)
Residues resulting from the incineration or
thermal treatment of soil contaminated with EPA
Hazardous Wastes No. F020BF023, F026, and
F027.
Leachate (liquids that have percolated through
land-disposed wastes) resulting from the disposal
of more than one restricted waste classified as
hazardous under Subpart D of 40 CFR 268.
(Leachate resulting from the disposal of one or
more of the following EPA hazardous wastes and
no other hazardous wastes retains its EPA
hazardous waste number[s]: F020, F021, F022,
F026, F027, and/or F028.)
2,6-Dichlorophenol waste from the production of
2,4-D.
Untreated wastewater from the production of
2,4-D.
Land disposal
restriction effective
date
November 8, 1988
November 8, 1988
August 8, 1990
(wastewater)
May 8, 1992
(nonwastewater)
June 8, 1989
August 8, 1988
Regulated
waste
constituent
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
TCDDs
PeCDDs
HxCDDs
TCDFs
PeCDFs
HxCDFs
aFor wastewater, the treatment standard for all regulated waste constituents—except for PeCDFs—is 0.063 ng/L; the
standard for PeCDFs is 0.035 jig/L. For nonwastewater, the treatment standard for all regulated waste constituents
is 1 ng/kg. Treatment standards are based on incineration to 99.9999% destruction and removal efficiency.
Source: 40 CFR 268.
This document is a draft for review purposes only and does not constitute Agency policy
1/7/2013 8-46 DRAFT: DO NOT CITE OR QUOTE
-------
to
OJ
Table 8-10. CDD/CDF concentrations (historical and current) (ug/kg) in technical-grade pentachlorophenol
(PCP) products
Congener/
congener group
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDD1
Total 2,3,7,8-CDF1
Total I-TEQuF1
Total WHO98 TEQcF1
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF1
1973"
—
-
-
-
—
-
-
—
-
-
-
-
-
-
-
-
-
—
-
--
ND (20)
ND (30)
5,500
98,000
220,000
40
250
22,000
150,000
160,000
655,790
1978"
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
130,000
—
-
--
—
-
-
-
-
900
4,000
32,000
120,000
130,000
286,900
1979C
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
—
-
—
—
-
10,100
296,000
1,386,000
-
1,400
9,900
88,000
43,000
1,834,400
1984"
ND(10)
ND(10)
-
2,200
100
100,000
610,000
ND(10)
-
-
-
-
-
-
-
-
130,000
712,300
130,000
1,970
1,304
ND(10)
ND(10)
4,500
135,000
610,000
ND(10)
-
-
62,000
130,000
941,500
1985e
ND(0.05)
ND(1)
6
2,565
44
210,000
1,475,000
ND(0.5)
ND(1)
ND(1)
49
5
5
ND(1)
34,000
4,100
222,000
1,687,615
260,159
4,445
2,918
ND
ND
4,694
283,000
1,475,000
6
10
1,982
125,000
222,000
2,111,692
1986e
ND(0.05)
ND(1)
8
1,532
28
106,000
930,000
ND(0.5)
ND(1)
ND(1)
34
4
ND(1)
ND(1)
29,000
6,200
233,000
1,037,568
268,238
2,735
1,689
ND
ND
2,925
134,000
930,000
ND
3
1,407
146,000
233,000
1,447,335
1987f
ND(0.03)
1
ND(1)
831
28
78,000
733,000
ND(O.l)
0.5
1.5
125
ND(1)
32
ND(1)
11,280
637
118,000
811,860
130,076
1,853
1,088
1.9
6.5
1,700
154,000
733,000
0.8
141
4,300
74,000
118,000
1,085,150
1987g
ND(0.05)
2
ND(1)
1,480
53
99,900
790,000
ND(O.l)
0.2
0.9
163
ND(1)
146
ND(1)
19,940
980
137,000
891,435
158,230
2,321
1,488
0.4
15.2
3,300
198,000
790,000
0.4
343
13,900
127,000
137,000
1,269,559
1985B88"
ND(0.05)
ND(1)
8
600
13
89,000
2,723,000
ND(0.5)
ND(1)
ND(1)
67
9
ND(1)
ND(1)
22,000
3,400
237,000
2,812,621
262,469
4,173
1,509
ND
ND
912
117,000
2,723,000
ND
200
1,486
99,000
237,000
3,178,598
1991'
ND
ND
-
-
-
-
1,100,000
ND
ND
ND
-
-
-
-
-
-
170,000
1,100,000
170,000
31,270
>127
ND(10)
ND(10)
8,900
130,000
1,100,000
ND(10)
ND(10)
14,000
36,000
170,000
1,458,900
1988B996
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
—
-
—
ND(1)
ND(10)
1,440
55,560
-
ND(10)
ND(10)
3,070
36,530
-
960,000
1988B991
ND(0.5)
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
—
-
--
ND
3
1,490
48,430
191,700
48
520
13,650
76,090
136,310
468,241
Unknown11
ND(10)
ND(10)
ND(10)
860
20
36,400
296,810
ND(10)
ND(10)
ND(10)
200
ND (20)
ND (20)
ND (20)
2,000
140
19,940
334,090
22,280
810
525
—
-
-
-
-
-
-
-
-
-
--
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§
i
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^ Table 8-10. CDD/CDF concentrations (historical and current) (ug/kg) in technical-grade pentachlorophenol
to (PCP) products (continued)
aSource: Buser and Bosshardt (1976); mean of 10 samples of Ahigh@ CDD/CDF-content PCP received from Swiss commercial sources in 1973.
^ bSource: Rappe et al. (1978); sample of U.S. origin, Apresumably prepared by alkaline hydrolysis of hexachlorobenzene.@
^ °Source: NTP (1989); composite of technical-grade materials produced in 1979 by Monsanto Industrial Chemical Co. (St. Louis, MO), Reichhold Chemicals, Inc.
Ł (White Plains, NY), and Vulcan Materials Co. (Birmingham, AL).
| dSource: Cull et al. (1984); mean of four Arecent@ production batches from each of two manufacturers of technical PCP using three different analytical methods;
§ analysis of variance (ANOVA) showed no statistically significant difference in CDD/CDF concentrations between the eight samples (samples obtained in the
5' United Kingdom).
j? eSource: Letter dated February 7, 1997, from John Wilkinson, Pentachlorophenol Task Force, to Matthew Lorber, U.S. EPA; average of monthly batch samples
S for the period January 1987 to August 1996.
^ fSource: Hagenmaier and Brunner (1987); sample of Witophen P (Dynamit Nobel-Lot no. 7777) (obtained in Germany).
^ 8Source: Hagenmaier and Brunner (1987); sample of PCP produced by Rhone Poulenc (obtained in Germany).
5 hSource: Letter dated February 7, 1997, from John Wilkinson, Pentachlorophenol Task Force, to Matthew Lorber, U.S. EPA; samples of Apenta@ manufactured in
| 1985, 1986, and 1988.
^3 'Source: Harrad et al. (1991); PCP-based herbicide formulation from the New York State Department of Environmental Conservation.
^ JSource: Letter dated March 5, 1997, from Thomas Mitchell, KMG-Bernuth, to Matthew Lorber, U.S. EPA; average of monthly batch samples for the period
°° c§ February 1987 to December 1996 (excluding the following months, for which data were not available: February 1993, January 1992, December 1991, September
Ł S 1991, December 1988, and September 1988).
<$• kSource: Schecter et al. (1997); sample found stored in a barn in Vermont.
| 'Calculated assuming nondetects were zero.
^ ND = Not detected (value in parenthesis is the detection limit).
OS - = No information given.
c,
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Table 8-11. Historical CDD/CDF concentrations (ug/kg) in
pentachlorophenol-Na (PCP-Na)
Congener/congener
group
2,3,7,8-TCDD
,2,3,7,8-PeCDD
,2,3,4,7,8-HxCDD
,2,3,6,7,8-HxCDD
,2,3,7,8,9-HxCDD
,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
,2,3,4,7,8-HxCDF
,2,3,6,7,8-HxCDF
,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
,2,3,4,6,7,8-HpCDF
,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDDh
Total 2,3,7,8-CDFh
Total I-TEQDFh
Total WHO98 TEQDFh
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDFh
1969a
—
-
—
-
-
3,600
—
-
-
-
—
-
-
-
—
—
—
—
-
—
—
17,000
9,600
3,600
~
~
~
~
—
30,200
1973"
—
-
—
-
-
-
—
-
-
-
—
-
-
-
—
—
—
—
~
140
40
140
1,600
4,000
ND (20)
60
1,400
4,300
4,300
15,980
1973C
~
~
~
~
~
~
—
~
~
~
~
~
~
~
~
—
~
—
~
50
ND (30)
3,400
38,000
110,000
ND (20)
40
11,000
47,000
26,500
235,990
1987d
0.23
18.2
28.3
2,034
282
9,100
41,600
1.8
8.2
6.6
48
69
ND(1)
87
699
675
37,200
53,062.7
38,794.6
452
390
27
213
3,900
18,500
41,600
82
137
3,000
13,200
37,200
117,859
1987e
0.51
3.2
13.3
53
19
3,800
32,400
0.79
1.9
1.1
4.6
1.3
1.3
4.6
197
36
4,250
36,289
4,498.6
89.5
58.1
52
31
230
5,800
32,400
12
27
90
860
4,250
43,752
1992f
0.076
18.7
96
4,410
328
175,400
879,000
ND(1)
ND(4)
ND(4)
27.6
21.9
9.8
103
9,650
2,080
114,600
1,059,252.8
126,492.3
3,374
2,489
3.6
142.7
9,694
260,200
879,000
10.1
88.4
9,082.3
75,930
114,600
1,348,751
1980s8
ND(1.4)
28.3
ND(6.1)
4,050
ND(1.4)
33,800
81,000
149
319
324
ND (2.8)
225
480
ND (385)
6,190
154
36,000
118,878.3
43,841
1,201
1,110
1.9
140
14,000
100,000
81,000
1,200
6,400
49,000
91,000
36,000
378,742
aSource: Firestone et al. (1972); mean of two samples of PCP-Na obtained in the United States between 1967 and
1969.
bSource: Buser and Bosshardt (1976); mean of five samples of Alow@ CDD/CDF-content PCP-Na received from
Swiss commercial sources.
"Source: Buser and Bosshardt (1976); sample of Ahighg CDD/CDF-content PCP-Na received from a Swiss
commercial source.
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Table 8-11. Historical CDD/CDF concentrations (ug/kg) in pentachlorophenol
Na (PCP Na) (continued)
dSource: Hagenmaier and Brunner (1987); sample of Dowicide-G purchased from Fluka; sample obtained in
Germany.
eSource: Hagenmaier and Brunner (1987); sample of Preventol PN (Bayer AG); sample obtained in Germany.
fSource: Santl et al. (1994); 1992 sample of PCP-Na from Prolabo, France.
8Source: Palmer et al. (1988); sample of a PCP-Na formulation collected from a closed sawmill in California in the
late 1980s.
hCalculated assuming nondetect values were zero.
ND = Not detected (value in parenthesis is the detection limit).
~ = No information given.
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Table 8-12. CDD/CDF concentrations (ug/kg) in chlorobenzenes
to
OJ
Congener/
congener group
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
MCBza
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND
1,2-DCBz
(for
synthesis)3
0.3
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
ND (0.02)
0.5
ND (0.02)
ND (0.02)
ND (0.02)
0.8
1,2,4-TrCBz
(Apure@)b
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND
Mixed
TrCBz
(47%)a
0.027
0.14
0.259
0.253
0.081
0.736
0.272
0.091
0.03
0.016
1.9
1,2,4,5-TCBz
(99%)a
ND (0.02)
0.2
0.5
0.8
0.4
0.03
0.2
0.8
1.5
2.1
6.5
PeCBz
(98%)a
ND (0.02)
ND (0.02)
0.02
0.02
0.05
0.02
ND (0.02)
ND (0.02)
0.1
0.1
0.3
HCBz
(97%)a
ND (20)
ND (20)
ND
(20)470
6,700
ND (20)
ND (20)
ND (20)
455
2,830
10,455
HCBzb
~
~
~
~
50B212,000
—
~
—
—
350B58,300
400B270,300
§•
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"Source: Hutzinger and Fiedler (199 Ib); unpublished results of tests performed at the University of Bayreuth, Germany, and by Dr. H. Hagenmaier.
bSource: Villanueva et al. (1974); range of three samples of commercially available HCBz.
ND = Not detected (value in parenthesis is the detection limit, if reported).
~ = No information given.
31
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Table 8-13. Annual releases in 2000 from complex plants producing chlorine and a variety of chlorinated
organics (g I-TEQ/year)
Plant/Location
Dow Chemical — Midland MI
Confidence Rating
Dow Chemical — Plaquemine, LA
Confidence Rating
Dow Chemical — Freeport, TX
Confidence Rating
Company A, Plant Al
Confidence Rating
Occidental — Convent, LA
Confidence Rating
Occidental — Ingleside, TX
Confidence Rating
PPG Industries— Lake Charles, LA
Confidence Rating
Company B, Plant Bl
Confidence Rating
Occidental — Niagara Falls
Confidence Rating
Company B, Plant B2
Chemicals
Ag chemicals, polymers, others
Chlorine, EDC, others
Chlorine, EDC, VCM, solvents, others
Chlorine, EDC, VCM, others
Chlorine, NaOH, EDC
C12 (diaphragm-cell), NaOH, EDC, VCM
C12 (mercury-/diaphragm-cell), hydrogen,
NaOH, EDC, and VCM
C12, solvents, other chlorinated organics
C12, NaOH, organic chemicals
C12, EDC, solvents
On-site
Air
0.046
H/H
0.092
H/H
3.08
H/H
0.068
H/H
0.022
R/H
1.61
RH/H
0.02
H/H
0.037
R/H
3.80 x 10~3
H/H
8.38 x 10~3
Water
0.037
H/H
7.71
H/H
6.91
H/H
0.023
H/H
0.002
LR/H
0.018
H/H
8.98
H/H
1.07
R/H
1.40 x 10~3
H/H
3.72 x 1Q-1
Landfill
12.6
H/H
12.8
H/H
89.3
H/H
Landfarm
1.45
H/H
Off-site transfers"
Landfill
1.5
H/H
0.081
H/H
1.47
H/H
0.303
H/H
0.028
R/H
Incineration
2.18
H/H
12.1
R/H
8.66
H/H
0.208
210
R/H
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to
Table 8-13. Annual Releases in 2000 from complex plants producing chlorine and a variety of chlorinated organics
(g I-TEQ/year) (continued)
This document is a dra/
Plant/Location
Confidence Rating
Total
Chemicals
On-Site
Air
R/H
4.99
Water
R/H
25.12
Landfill
114.70
Landfarm
1.45
Off-site Transfers"
Landfill
3.38
Incineration
233.15
f H = High.
^ R = Reasonable.
~. L = Low.
3
s Source: Dyke and Amendola (2007).
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Table 8-14. CDD/CDF mean concentrations (ng/kg) measured in the 2001
National Sewage Sludge Survey
Congener
2,3,7,8-TCDD
1,2,3,7,8-PeCD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Average total WHO9g TEQDF
Average total I-TEQDF
Nondetect set to
1A detection limit
1.41
5.76
11.8
21.3
3.6
492
6,780
3.11
2.61
6.03
1.37
0.27
5.21
5.5
9.13
167
802
23
27
Nondetect set to
zero
1.1
4.57
7.49
15.1
2.22
273
2,730
2.3
1.5
2.8
1
0
2.6
3.36
2.8
88.2
279
14
15
Source: EPA (2002d).
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to
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1 9. NATURAL SOURCES OF CDDS/CDFS
2
3
4 Numerous laboratory and field research studies have demonstrated that biochemical and
5 photolytic formation of CDDs/CDFs from chlorophenol precursors is possible. In addition,
6 under certain conditions, some CDDs/CDFs can be biodegraded to form less-chlorinated (and
7 possibly more toxic) CDDs/CDFs. Both of these mechanisms are discussed in this chapter;
8 however, the extent to which CDDs/CDFs are formed by either mechanism in the environment is
9 unknown at present. The potential for releases of CDDs/CDFs from the application of animal
10 manure to farmland and the mining and use of ball clay are also discussed. Forest fires could be
11 considered a potential natural source, but it was decided that the discussion fit better in Chapter 6
12 on minimally and uncontrolled combustion sources. Similarly, volcanoes were discussed in
13 Chapter 6 where it indicates that no studies have demonstrated the formation of CDDs/CDFs by
14 volcanoes.
15
16 9.1. BIOTRANSFORMATIONS
17 9.1.1. Biotransformation of Chlorophenols
18 As discussed in the original report, the biochemical formation of CDDs/CDFs—
19 particularly the higher-chlorinated congeners—from chlorophenol precursors is possible, as
20 indicated in laboratory studies with solutions of trichlorophenols and PCP in the presence of
21 peroxidase enzymes and hydrogen peroxide. However, the extent to which CDDs/CDFs are
22 formed in the environment via this mechanism cannot be estimated at this time.
23 UNEP (2005) suggests the following emission factors for composted materials: garden
24 and kitchen wastes—15 ng I-TEQ/kg dry matter, and green materials from unimpacted
25 environments—5 ng I-TEQ/kg dry matter. The discussion indicates that some very high levels
26 (approximately 100 ng I-TEQ/kg dry matter) have been observed in compost as a result of
27 contaminated input.
28 Products from composting operations are typically land spread and have the potential to
29 be a land release. However, insufficient information is available on emission factors and
30 activities to make release estimates for composting or other potential sources involving
31 biotransformation of chlorophenol s (Not quantifiable).
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Biotransformation of Chlorophenols
Releases to Soil
Not quantifiable.
1 9.1.2. Biotransformation of Higher CDDs/CDFs
2 As discussed in the original report, results of several studies that examined the fate of a
3 range of CDD/CDF congeners in pure cultures, sediments, and sludges indicate that under
4 certain conditions, some CDD/CDF congeners will undergo biodegradation to form
5 lower-chlorinated (and possibly more toxic) CDDs/CDFs. However, the extent to which more
6 toxic CDDs/CDFs are formed in the environment via this mechanism cannot be estimated at this
7 time.
8 Therefore, these releases are not quantifiable.
Biotransformation of Higher CDDs/CDFs
Releases to Soil
Not quantifiable.
9 9.1.3. Biotransformation of Animal Manure
10 Because livestock and poultry manure can provide valuable organic material and
11 nutrients for crop and pasture growth, most of the animal manure generated at commercial farms
12 and animal feed lots is applied to farmland as fertilizer. To the extent dioxin-like compounds
13 may contaminate animal manures, the practice of land-spreading animal waste may result in
14 releases of CDDs/CDFs to the open and circulating environment.
15 Mass balance studies have shown that no new formation of dioxins and furans appears to
16 occur within a cow (Winters et al., 2000; Lorber et al., 2000; McLachlan et al., 1990). These
17 studies have involved measuring the dioxins present in the feeds provided to dairy cows and then
18 measuring the dioxins in the cow milk, feces, and urine in carefully controlled settings. Studies
19 by EPA (Winters et al., 2000; Lorber et al., 2000) involved four cows, sampled three times
20 between July and November of 1997. Preliminary testing on urine showed nondetects as
21 expected, so this matrix was not included in further testing. The tests were designed to represent
22 typical conditions (feed types, dairy cow housing, etc.) in the United States with regard to the
23 production of milk. The feed and feces concentrations ranged from 0.13 to
This document is a draft for review purposes only and does not constitute Agency policy.
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1 0.30 ng WHOgg TEQop/kg dry weight basis, and milk concentrations ranged from 0.53 to
2 0.96 ng WHOgg TEQop/kg lipid basis. The feces concentrations in these lactating cows were
3 about one order of magnitude lower than that measured by Stevens and Jones (2003) in the
4 United Kingdom (U.K.) (see Table 9-1). A mass balance was determined by dividing the mass
5 of CDD/CDFs present in feces and milk by the mass in the feed and then multiplying by 100% (a
6 finding of 100% suggests that the dioxins excreted in milk and feces equals that in the feed; a
7 finding greater than 100% suggests formation). These matrices were sampled once the cows
8 were well into lactation, so an assumption of steady state was reasonable. The mass balance of
9 both TEQs and individual congeners ranged from about 50 to 100%, suggesting no internal
10 formation of CDD/CDFs by the cows. The average mass balance over 17 congeners was 73%.
11 McLachlan et al. (1990) conducted a similar experiment with one cow in a background setting
12 and also found mass balances between 50 and 100%, with an average of 75% over all
13 17 CDD/CDF congeners.
14 As discussed in the original report, reasonably good data are available on the generation
15 rates of livestock manure. However, limited data are available on CDD/CDF levels in livestock
16 manure. Further, mass balance studies on lactating cows suggest that no new formation of
17 CDD/CDFs are occurring. Thus, while the land application of farm animal manure is a potential
18 land release, it is concluded that insufficient data are available to quantify these releases, and
19 because of the mass balance studies, these may be better characterized as a redistribution rather
20 than a new formation. Accordingly, EPA currently considers this source to be unquantifiable in
21 terms of dioxin emissions.
Biotransformation of Animal Manure
Releases to Soil
Not quantifiable.
22
23 9.2. PHOTOCHEMICAL TRANSFORMATIONS
24 A number of researchers have demonstrated that CDD/CDFs can be formed via various
25 types of photochemical transformations.
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1 9.2.1. Photolysis of PCP
2 As discussed in the original report, several studies have demonstrated that photolysis of
3 PCP may lead to the formation of CDD/CDFs; however, the information is considered
4 inadequate to estimate releases of CDD/CDFs to the environment.
Photolysis of PCP
Releases to Wood or Air
Not quantifiable.
5 9.2.2. Photolysis of Higher CDDs/CDFs
6 As discussed in the original report, a number of studies have demonstrated that photolysis
7 of higher CDD/CDFs may lead to the formation of CDD/CDFs; however, the information is
8 considered inadequate to estimate releases of CDD/CDFs to the environment.
Photolysis of Higher CDDs/CDFs
Releases to Air, Water, or Soil
Not quantifiable.
9 9.2.3. Photolysis in Water
10 As discussed in the original report, a number of studies have demonstrated that photolysis
11 in water may lead to the formation of CDD/CDFs; however, the information is considered
12 inadequate to estimate releases of CDD/CDFs to the environment.
Photolysis in Water
Releases to Water
Not quantifiable.
13 9.2.4. Photolysis on Soil Surfaces
14 As discussed in the original report, studies have demonstrated that photolysis on soil
15 surfaces may lead to the formation of CDD/CDFs; however, the information is considered
16 inadequate to estimate releases of CDD/CDFs to the environment.
Photolysis on Soil
Releases to Soil
Not quantifiable.
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1 9.2.5. Photolysis on Vegetation
2 As discussed in the original report, studies have demonstrated that photolysis on
3 vegetation may lead to the formation of CDD/CDFs; however, the information is considered
4 inadequate to estimate releases of CDD/CDFs to the environment.
Photolysis on Vegetation
Releases to Biota
Not quantifiable.
5 9.2.6. Photolysis in Air
6 As discussed in the original report, studies have demonstrated that photolysis in air may
7 lead to the formation of CDD/CDFs; however, the information is considered inadequate to
8 estimate releases of CDD/CDFs to the environment.
Photolysis in Air
Releases to Air
Not quantifiable.
9 9.3. CDDS/CDFS IN BALL CLAY
10 As discussed in the original report, studies have demonstrated that CDD/CDFs are found
11 naturally in ball clay. Releases from ball clay may occur when it is disturbed during mining and
12 subsequent processing. Accordingly, such releases have both a natural and an anthropogenic
13 aspect to them. Multiplication of the mean WHOgg TEQop concentration in mined ball clay by
14 the total amount of ball clay mined in 1995 gives an estimate of 1,502 g WHOgg TEQop
15 (U.S. EPA, 2006). It is unknown how much of these CDD/CDFs contained in mined ball clay
16 are released to the environment during the mining, initial refining, and product handling. Most
17 ball clay is used to produce ceramic products where releases may occur from processes such as
18 drying or high-temperature vitrification. The temperatures found in ceramic kilns vary but can
19 reach levels needed for both volatilization and destruction of CDD/CDFs. No stack
20 measurement data are available from these facilities, so there is insufficient evidence to make
21 even a preliminary estimate of releases.
This document is a draft for review purposes only and does not constitute Agency policy.
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Ball Clay
Releases to Air
Not quantifiable.
This document is a draft for review purposes only and does not constitute Agency policy.
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Table 9-1. CDD and CDF concentrations (ng/kg dry weight) in samples of animal manure in the United Kingdom
to
OJ
o
H
O
HH
H
W
O
&
O
c
o
H
W
§•
I
o
I
o
a
i
a,
§•
a
o
o g
O a
§
,CS
Congener
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
Total 2,3,7,8-CDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDF
Total CDD/CDF
WHO98 TEQ
Cowsa
(« = 6) (mean)
0.17
0.46
2.4
4.5
2.6
120
460
590.1
0.3
0.3
0.28
0.6
0.51
1.9
0.4
7.6
12
35
58.9
649
3.6
Cows"
(« = 10) (mean)
0.02
0.04
0.06
0.15
0.11
3.6
58
62.3
0.05
0.04
0.06
0.18
0.12
0.05
0.16
1.8
0.17
2.4
5.0
67.4
0.2
Sheep"
(» = 1)
0.11
0.41
0.9
0.86
0.56
9.4
53
65.2
1.2
1.1
1.2
1.4
1.1
0.15
1.4
5.2
0.56
5
18.3
83.5
2.1
Piga
(« = 1)
0.01
0.07
0.26
0.1
0.07
0.8
11
12.3
0.03
0.04
0.06
0.05
0.06
0.04
0.06
0.48
0.04
0.73
1.6
13.9
0.2
Chicken"
(« = 1)
0.01
0.04
0.03
0.09
0.12
1.4
14
15.7
0.03
0.09
0.12
0.15
0.07
0.05
0.14
0.37
0.09
0.8
1.9
17.6
0.2
Sources: "Stevens and Jones (2003); Personal communication, M. Lorber (2008), who provided the raw data for the study summarized in Lorber et al. (2000).
The data reflect four cows sampled three times; n = 10 instead of 12 because two cows in one sampling date were exposed to feed purposefully contaminated
with PCP-treated wood shavings.
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1 10. SOURCES OF DIOXIN-LIKE POLYCHLORINATED BIPHENYLS (PCBS)
2
3
4 This chapter estimates releases of dioxin-like PCB congeners to the environment. PCB
5 releases from media reservoirs (i.e., soil, sediment, and water) are covered in Chapter 11. This
6 chapter covers other PCB sources, primarily conventional point sources. These sources are
7 assumed to have contemporary formation releases. This is uncertain, though, because some
8 portion of these releases may be passed through from inputs to outputs rather than new
9 formation. Both Chapters 10 and 11 contain information on releases associated with PCB
10 products.
11
12 10.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY
13 The primary changes to this chapter include the addition of several new source
14 categories, addition of background information to a number of the other sources, and minor
15 changes to the release estimates. Additionally, the release summary table (see Table 10-1) has
16 been reformatted to match the new one used for CDD/CDFs.
17 Relatively few sources have well-characterized releases of dioxin-like PCBs. As shown
18 in Table 10-1,2 sources had quantitative release estimates, 6 sources had preliminary release
19 estimates and 9 sources were identified as being unquantifiable. Although the information is
20 limited, it suggests that, in terms of TEQs, PCB releases are much lower than CDD/CDF
21 releases.
22 Two potential source categories that could not be addressed are contaminated PCB sites
23 and wastes with less than 50-ppm PCB (which are not regulated under TSCA). No information
24 was found that would allow evaluation of releases from these sources.
25 The original report concluded that it is likely that no significant releases of newly formed
26 dioxin-like PCBs are occurring in the United States. This is based on three arguments. First,
27 although the data are limited, the inventory presented here suggests that new releases are low in
28 comparison to the amounts currently present in the environment. As shown in Table 10-1, the
29 total quantitative release estimates for 2000 sum to only about 30 g WHOgg TEQP/year to air and
30 20 g WHOgg TEQp/year to land. As discussed in Chapter 11, the surface soils in the United
31 States are estimated to contain about 95 kg of PCB TEQs. Also, the release estimates may
32 overestimate new releases because some portion may be passed through from inputs to outputs
This document is a draft for review purposes only and does not constitute Agency policy.
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1 rather than new formation. Second, the new releases appear low compared to past releases
2 associated with PCB production, use, and disposal. As discussed in Section 10.7, an estimated
3 3,702 kg of WHOgg TEQp were released directly to the U.S. environment between 1930 and
4 1977. Third, North American sediment studies have shown decreasing PCB levels since the
5 1980s (Lebeuf et al., 1995; Cleverly et al., 1996), indicating that releases of newly formed PCBs
6 are not large enough to prevent this decline. Accordingly, the original statement is still believed
7 to likely be true, but it is acknowledged to be uncertain because releases could be estimated for
8 only a few sources.
9
10 10.2. RELEASES FROM COMMERCIAL PCB PRODUCTS
11 10.2.1. Approved PCB Disposal/Destruction Methods
12 As discussed in the original report, landfilling and incineration can be used as disposal
13 methods for PCBs. It is assumed that the amounts landfilled would not represent an
14 environmental release. The incineration facilities achieve a high combustion efficiency, but
15 some releases are possible. The original report summarizes TRI information on total PCB
16 releases to air, surface water, and land. Insufficient information was available to convert these
17 releases to TEQ estimates.
18
19
PCB Incineration
Releases
Not quantifiable.
20
21
22 10.2.2. Releases of In-Service PCBs
23 As discussed in the original report, insufficient information is available to make
24 quantitative release estimates occurring from in-service PCBs. No changes were made to this
25 conclusion, but some additional background information on accidental fires is provided below.
26 Also, this section was expanded to include nonaccidental releases of in-service PCBs.
27 A variety of PCB products can remain in use for long time periods, such as paint, caulk,
28 transformers, and capacitors. Releases from these products can occur via vaporization or leaks
29 or during disposal operations. As discussed in the original report (see Section 10.6),
30 approximately 568,000 MT of PCBs were used in the United States between 1930 and 1975. An
This document is a draft for review purposes only and does not constitute Agency policy.
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1 estimated 50.3% were used in capacitors, and 26.8% were used in transformers. Assuming that
2 these products contained an average of 8 mg WHOgg TEQp/kg (average concentration for
3 Aroclor 1242, which accounted for over 50% of total sales—see Section 10.6 of original report),
4 then a total of 3,500 kg of WHOgg TEQp were used in capacitors and transformers. It is
5 unknown how much of this material is still in use today or what amount of releases may be
6 occurring. Note that these products can be considered reservoirs because the releases can occur
7 after their initial use, so they are also discussed in Chapter 11.
8 A report by the Environment Agency in the United Kingdom assessed the importance of
9 releases of PCBs from various sources (Dyke, 2002). This report concluded that leaks from
10 capacitors and transformers are likely to be the largest source of PCB releases occurring
11 currently, although this is expected to decline as these devices are taken out of service and
12 disposed. Leaks from electrical equipment were estimated to account for 80% of the total PCB
13 releases occurring in the United Kingdom in 1998 (Dyke, 2002).
14 A number of PCB transformer fires have occurred in the United States, leading to PCB
15 contamination of the interiors of office buildings (Michaud et al., 1994). Soot can be produced
16 in large amounts, consisting of particles that may contain PCB concentrations up to
17 5,000-8,000 mg/kg of soot (Michaud et al., 1994). The following are several examples of PCB
18 fires in office buildings.
19 In the case of a transformer fire in the basement of the New York State office building in
20 Binghamton, NY, the circulation of PCB-contaminated soot particles resulted in an average
21 interior surface concentration of 162 mg/m2 (expressed as the equivalent Aroclor 1254
22 concentration) (Erickson, 1997). Additionally, the soot samples from the Binghamton PCB fire
23 contained about 20 mg/g and 700 mg/g of total CDDs and total PCDFs, respectively (Erickson,
24 1997). In 1985, a PCB transformer fire occurred in the basement transformer vault in the main
25 building of the New Mexico State Highway Department Office Building (CDC, 1985). Interior
26 air concentrations of PCBs in the transformer vault were found to average about 48 ug/m3.
27 Surface wipes on horizontal surfaces had PCB concentrations ranging from 4,700 to
28 30 million ug/m2. Other notable U.S. transformer fires include the office building at
29 1 Marke Plaza in San Francisco in 1983, the Saniford Street office building in Boston in 1981,
30 and the Page Belcher building in Tulsa (Michaud et al., 1994). In these fires, indoor air PCB
31 concentrations ranged from 140 to 1,500 ug/m3; interior surfaces to the buildings ranged from
This document is a draft for review purposes only and does not constitute Agency policy.
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9 Q
1 20-90 ug/m total PCBs. TCDF concentrations ranged from 4-30 pg/m in the indoor office air
/^
2 and from 200-700 ng/m to interior surfaces.
Releases of In-Service PCBs
Releases
Not quantifiable.
5
6
7 10.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES
8 The original report discussed Municipal Wastewater Treatment under Section 10.2. In
9 this update, it has been moved to this section because these facilities are not associated with
10 commercial PCB products and do conduct a type of chemical processing. Minor changes were
11 made to the release estimates as summarized below.
12 For reference years 1987 and 1995, the concentration of dioxin-like PCBs that may be
13 present in sewage sludge was estimated as 24.3 ng WHOgg TEQP/kg. This is based on the 1994
14 survey of 74 plants as reported by Green et al. (1995) and Cramer et al. (1995). For reference
15 year 2000, the concentration of dioxin-like PCBs that may be present in sewage sludge was
16 estimated as 5.22 ng WHO9g TEQP/kg. This is based on the 2001 survey of 94 plants (U.S. EPA,
17 2002d). The activity estimates were based on the 1988/1989 National Sewage Sludge Survey
18 and the results of the 1984 to 1996 Clean Water Needs Surveys (U.S. EPA, 1999b). All
19 beneficial uses were assumed to have the potential for release to the environment, resulting in
20 increases in the product release estimates compared to the original report.
21 As discussed in EPA (2006), there is no clear evidence that other types of chemical
22 manufacturing and processing facilities release dioxin-like PCBs.
23 The inventory decision criteria and releases to all media are summarized below:
24
25
26
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Municipal Wastewater
Treatment
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
VIeasured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
Yes
Yes
Yes
Q
1
2
Municipal Wastewater Treatment
Soil Releases
Emission Factors
• 1987—24 ng WHO98 TEQP/kg of sludge.
• 1995—24 ng WHO98 TEQP/kg of sludge.
• 2000—5.2 ng WHO98 TEQP/kg of sludge.
Activity Levels
• 1987—2.1 MMT of sludge.
• 1995—3.2 MMT of sludge.
• 2000—3.6 MMT of sludge.
Releases
• 1987—51 g WHOgg TEQp.
• 1995—78 g WHOgg TEQP.
• 2000— 19 g WHO98 TEQp.
Product Releases
Emission Factors
• 1987—24 ng WHO98 TEQP/kg of sludge.
• 1995—24 ng WHO98 TEQP/kg of sludge.
• 2000—5.2 ng WHO98 TEQP/kg of sludge.
Activity Levels
• 1987—0.07 MMT of sludge.
• 1995—0.5 MMT of sludge.
• 2000—0.5 MMT of sludge.
Releases
• 1987—2 g WHOgg TEQp.
• 1995—12 g WHOgg TEQp.
• 2000—3 g WHO98 TEQp.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 10.4. COMBUSTION SOURCES
2 10.4.1. Municipal Waste Combustion
3 The 2006 report concluded that insufficient information was available to develop
4 quantitative release estimates from municipal waste incinerators. A number of additional studies
5 are presented below that allow making preliminary estimates.
6 Dyke (2002) provides a review of PCB emission factors for municipal waste incinerators.
7 These vary from 0.000027 to 14 ng TEQp/kg. Dyke et al. (2003) provide a similar literature
8 survey of 1990's data on incinerator emissions and fly ash concentrations of concurrently
9 measured dioxin-like PCBs and CDD/CDF TEQ. Their literature summary supports the
10 observation that WHOgg TEQp emission concentrations from MWCs are an order of magnitude
11 and more lower than WHOgg TEQDF. They also provide some PCB emission factors from these
12 references, showing a fairly wide range from as low as 0.0085 to as high as
13 25.6 ug WHOgg TEQp/MT. Finally, they provide results of their own testing on two MWCs with
14 different levels of pollution control. For one MWC, three of four tests were nondetect for all
15 14 PCBs measured and the other test showed some positive concentrations. For the second
16 MWC, two tests had positive measurements for PCB-114, PCB-118, PCB-123, and PCB-180.
17 The range of reported WHOgg TEQp emission concentrations was between 0 (assuming ND = 0)
18 and 0.016 ng WHO98 TEQP/Nm3 (assuming ND = QL).
19 Sakai et al. (1999) found that the input of coplanar PCBs into the municipal solid waste
20 incineration facilities in Kyoto City (Japan) was 0.13-0.29 mg-TEQ per ton waste, the total
21 output of coplanar PCBs (the sum released from emission gas, fly ash, and bottom ash) was 4.9
22 mg TEQ per ton waste. The PCB emission factor for gas releases was reported to be 1.2 jig
23 TEQ/ton of waste burned. They reported PCB concentrations in fly ash of 0.053 ng TEQ/g and in
24 bottom ash as 0.000023 ng TEQ/g.
25 CDD/CDFs and dioxin-like PCBs were measured in the emissions from an MWC in
26 Madrid, Spain, which was equipped with a high level of pollution control (Abad et al., 2006).
27 Over 16 samples, CDD/CDF emissions averaged 0.047 ng I-TEQ/Nm3, and dioxin-like PCBs
28 added an average of 0.0015 ng I-TEQ/Nm3, with most of this dioxin-like PCB contribution from
29 PCB-126.
30 Eight incinerators, including two commercial MWCs, were sampled for CDD/CDFs,
31 PCBs, and HCB in a study conducted in Japan (Kim et al., 2004a). The average concentration
This document is a draft for review purposes only and does not constitute Agency policy.
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1 over all eight incinerators was 0.281 ng WHO98 TEQDF/Nm3 for CDD/CDFs and
2 0.023 ng WHO98 TEQp/Nm3 for PCBs, suggesting a factor of difference of 10 on average. The
3 disparity from one of the two MWC incinerators was 0.069 ng WHO98 TEQoF/Nm3 for
4 CDD/CDF and 0.009 ng WHO98 TEQP/Nm3 for PCBs. Emissions were much lower for the other
5 MWC, with reported TEQ concentrations uninformative at 0.000 ng WHO98 TEQoFP/Nm3.
6 Francois et al. (2005) provide side-by-side measurements of CDD/CDFs and dioxin-like
7 PCBs, which contradict the observations provided by Dyke et al. (2003). Francois et al. (2005)
8 reports on testing at 15 incinerators including three MWCs in Belgium. The dioxin-like PCBs
9 often dominated the overall TEQ emissions. For example, the average shares of the dioxin-like
10 PCBs to total TEQ were 22, 34, and 97% for the three MWCs. The stack concentrations of
11 dioxin-like PCBs were 0.0008, 0.045, and 0.0034 ng WHO98 TEQP/Nm3, compared to
12 corresponding CDD/CDF concentrations of 0.0014, 0.0014, and 0.012 ng WHO98 TEQDF/Nm3.
13 Based on these concentrations and other plant characteristics, annual dioxin-like PCB emissions
14 were quantified in all of these plants at 0.4, 7.0, and 1.2 mg WHO98 TEQP/year.
15 Kim et al. (2005) measured 209 congeners in stack emissions from nine facilities in
16 Japan, including three MWCs. They did not measure CDD/CDFs, but their measured
17 concentrations can be compared with other studies identified above. They detected PCBs at all
18 facilities, with total PCBs ranging from 10-700 ng/Nm3 and coplanar PCBs in the range of
19 1-25 ng/Nm3 (0.008-0.324 ng WHO98 TEQP/Nm3). On a class basis, the average from the
20 MWCs was the highest at 0.136 ng WHO98 TEQP/Nm3.
21 The PCB emission factor for municipal waste incinerators was assumed to equal the
22 geometric mean of the range reported by Dyke et al., 2003 (0.0085 to
23 25.6 ug WHO98 TEQP/MT) which is 0.5 ng WHO98 TEQP/kg. This emission factor is considered
24 preliminary due to the inconsistency in the results. The activity data are presented in Chapter 3.
25 PCBs are also likely to be present in the ash, but these would be landfilled and not considered an
26 environmental release. The inventory decision criteria and releases to all media are summarized
27 below:
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Municipal Waste Combustion
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
No
Yes
Yes
P
1
2
Municipal Waste Combustion
Air Releases
Emission Factors
• 1987—0.5 ng WHO98 TEQP/kg (Preliminary).
• 1995—0.5 ng WHO98 TEQP/kg (Preliminary).
• 2000—0.5 ng WHO98 TEQP/kg (Preliminary).
Activity Levels
• 1987—13.
• 1995—29.
• 2000—29.
Releases
• 1987—7 g
• 1995—15
• 2000—15
7 billion kg.
8 billion kg.
4 billion kg.
WHO9g TEQp (Preliminary).
g WHO98 TEQp (Preliminary).
g WHO98 TEQp (Preliminary).
4
5 10.4.2. Industrial Wood Combustion
6 As discussed in EPA (2006), evidence exists that PCBs can be released from industrial
7 wood combustion, but the information is insufficient to make quantitative release estimates. No
8 changes were made to this conclusion.
9
Industrial Wood Combustion
Releases
Not quantifiable.
10
This document is a draft for review purposes only and does not constitute Agency policy.
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1 10.4.3. Medical Waste Incineration
2 EPA (2006) concluded that insufficient evidence existed to derive emission factors for
3 PCB releases from medical waste combustion. As discussed below, additional studies were
4 found that allowed making preliminary release estimates.
5 Dyke et al. (2003) surveyed the literature for studies providing measurements of
6 dioxin-like PCBs along with CDD/CDFs from power stations and waste incineration processes.
7 They identified a study published in 1996 (Ehrlich et al., 1996) in which the PCB emission
8 concentration from a medical waste incineration was 0.035 ng WHOgg TEQp/Nm3, while it was
9 0.97 ng WHOgg TEQoF/Nm3 for CDD/CDFs. They also conducted their own measurements on a
10 medical waste incinerator in the United Kingdom. They quantified concentrations of PCB-118,
11 PCB-123, PCB-170, and PCB-180—but not the other 14 congeners. Assuming ND = 0, one of
12 two runs had a concentration of 0.00007 ng WHOgg TEQp/Nm3, while the other had a
13 concentration of 0.022 WHOgg TEQp/Nm3 at ND = 0. In contrast, the same two runs had
14 CDD/CDF concentrations at ND = 0 at 0.07 and 0.05 ng WHO9g TEQDF/Nm3.
15 The data reported by Dyke et al. (2003) suggest that PCB TEQ emissions are 1 to 25% of
16 the dioxin emissions. The Ehrlich et al. (1996) data suggest that the PCB TEQ emissions are 4%
17 of the dioxin emissions. The Ehrlich et al. (1996) value was selected as a central estimate and
18 multiplied by the average CDD/CDF emission factor for each reference year (total CDD/CDF
19 emissions divided by the total activity as reported in Chapter 3). This procedure gave the
20 emission factors shown below. These emission factors are considered preliminary because the
21 studies provided insufficient information to directly derive them. The activity data are presented
22 in Chapter 3. PCBs are also likely to be present in the ash, but these would be landfilled and not
23 considered an environmental release. The inventory decision criteria and releases to all media
24 are summarized below:
This document is a draft for review purposes only and does not constitute Agency policy.
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1
2
Inventory Decision Criteria for Medical Waste Incineration
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
Emission factor tests represent units that are typical of the
class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
No
Yes
Yes
P
Medical Waste Incineration
Air Releases
Emission Factors
• 1987—68 ng WHO98 TEQP/kg (Preliminary).
• 1995—24 ng WHO9g TEQP/kg (Preliminary).
• 2000—24 ng WHO98 TEQP/kg (Preliminary).
Activity Levels
• 1987—1.43 billion kg.
• 1995—0.77 billion kg.
• 2000—0.6 billion kg.
Releases
• 1987—97 g WHOgg TEQP (Preliminary).
• 1995—18 g WHOgg TEQp (Preliminary).
• 2000—14 g WHO98 TEQp (Preliminary).
3
4
5 10.4.4. Tire Combustion
6 As discussed in EPA (2006), evidence exists that PCBs can be released from tire
7 combustion, but the information is insufficient to make quantitative release estimates. No
8 changes were made to this conclusion.
9
Tire Combustion
Releases
Not quantifiable.
10
This document is a draft for review purposes only and does not constitute Agency policy.
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1 10.4.5. Cigarette Smoking
2 As discussed in the original report, PCB releases can occur during cigarette
3 smoking. No changes were made to these estimates as summarized below.
4 A preliminary estimate of potential emissions of dioxin-like PCBs can be made using the
5 following assumptions: (a) the average WHOgg TEQP content of seven brands of U.S. cigarettes
6 reported by Matsueda et al. (1994), 0.64 pg/pack (0.032 pg/cigarette), is representative of
7 cigarettes smoked in the United States; (b) dioxin-like PCBs are neither formed nor destroyed,
8 and the congener profile reported by Matsueda et al. (1994) is not altered during combustion of
9 cigarettes; and (c) all dioxin-like PCBs contributing to the TEQ are released from the tobacco
10 during smoking. This emission factor is considered preliminary because of the multiple
11 assumptions required in its derivation. Cigarette consumption is discussed in Section 5.5.
12 The inventory decision criteria and releases to all media are summarized below:
13
14
Inventory Decision Criteria for Cigarette Smoking
Air Water Solids Products
mission tests for at least two units/source types with No
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable
differences.
mission factor tests represent units that are typical of the
;lass.
activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
This document is a draft for review purposes only and does not constitute Agency policy.
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Cigarette Smoking
Air Releases
Emission Factors
• 1987—0.03 pg WHO9g TEQP/cigarette (Preliminary).
• 1995—0.03 pg WHO98 TEQP/cigarette (Preliminary).
• 2000—0.03 pg WHO98 TEQp/cigarette (Preliminary).
Activity Levels
• 1987—575 billion cigarettes.
• 1995—487 billion cigarettes.
• 2000—440 billion cigarettes.
Releases
• 1987—<0.1 g WHO9g TEQp (Preliminary).
• 1995—<0.1 g WHO98 TEQp (Preliminary).
• 2000—<0.1 g WHO98 TEQp (Preliminary).
1
2
3 10.4.6. Sewage Sludge Incineration
4 As discussed in the original report, PCB releases can occur from sewage sludge
5 incineration. No changes were made to these estimates as summarized below. Additional
6 information was found regarding a stack test for a sewage sludge incinerator in the United
7 Kingdom (Dyke et al., 2003). This was not used in the emission factor derivation because all
8 dioxin-like PCB congeners were below the detection limits of about 0.12 ng/Nm3 for each
9 congener.
10 The emission factor was based on measurements conducted at a multiple-hearth
11 incinerator in Ohio equipped with a venturi scrubber and a three-tray impingement conditioning
12 tower (U.S. EPA, 2000b). This emission factor was considered preliminary because it is based
13 on testing at only one facility. Sewage sludge activity data are presented in Chapter 8.
14 The inventory decision criteria and releases to all media are summarized below:
This document is a draft for review purposes only and does not constitute Agency policy.
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Inventory Decision Criteria for Sewage Sludge Incineration
Air Water Solids Products
Emission tests for at least two units/source types with No
lUfficient documentation to directly derive emission factors.
Measured emission factors consistent or have understandable
differences.
mission factor tests represent units that are typical of the
;lass.
activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
1
2
Sewage Sludge Incineration
Air Releases
Emission Factors
• 1987—0.51 ng WHO98 TEQP/kg of sludge (Preliminary).
• 1995—0.51 ng WHO98 TEQP/kg of sludge (Preliminary).
• 2000—0.51 ng WHO98 TEQP/kg of sludge (Preliminary).
Activity Levels
• 1987—0.865 MMT.
• 1995—2.11 MMT.
• 2000—1.42 MMT.
Releases
• 1987—0.4 g WHO98 TEQp (Preliminary).
• 1995—1 g WHO9g TEQp (Preliminary).
• 2000—0.7 g WHO98 TEQp (Preliminary).
4
5 10.4.7. Backyard Barrel Burning
6 The original report concluded that insufficient information was available to make
7 quantitative PCB release estimates for backyard barrel burning. New information is provided
8 below, which allowed making both air and land release estimates for this source category.
9 Gonczi et al. (2005) tested emissions from burning domestic wastes in barrels (19 tests)
10 and open fires (2 tests). Gas collected above these fires allowed for estimation of emission
11 factors. The material burned consisted of various mixtures of garden wastes, straw, paper,
12 several forms of plastic, tires, waste motor oil, RDF, and computer scrap. A barrel burn with a
13
This document is a draft for review purposes only and does not constitute Agency policy.
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1 mix of garden waste and polyvinyl chloride (PVC) waste had the highest emission factor of
2 190 ng PCB TEQ/kg burned. The other tests ranged from 0.3 to 3.2 ng WHO98 TEQP/kg burned.
3 The dioxin-like PCBs generally made up much less than 10% of the total TEQ emissions.
4 As reported in EPA (2006), Lemieux (1997) also measured PCB emissions from tests
5 simulating backyard barrel burning. The average emission factor across two tests was
6 5.26 ng WHOgg TEQP/kg waste burned. This emission factor was selected as the most
7 representative of typical domestic waste.
8 Lemieux (1997) also collected ash samples from open barrel burning and analyzed for
9 PCBs. Ash samples from the experiments were combined, resulting in two composite
10 samples—one for recyclers and one for nonrecyclers (see Table 10-2). The overall average was
11 0.8 ng WHC-98 TEQp/kg of ash.
12 The activity levels for backyard barrel burning (total waste burned and ash generated)
13 were presented in Section 6.5.2.
14 The inventory decision criteria and releases to all media are summarized below:
15
16
Inventory Decision Criteria for Backyard Barrel Burning
Air Water Solids Products
Emission tests for at least two units/source types with Yes Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes Yes
ifferences.
Emission factor tests represent units that are typical of the Yes Yes
;lass.
activity estimates based on source-specific surveys. Yes Yes
Conclusion (Q = Quantitative, P = Preliminary). Q Q
This document is a draft for review purposes only and does not constitute Agency policy.
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Backyard Barrel Burning
Air Releases
Emission Factors
• 1987—5.3 ng WHO98 TEQP/kg of waste burned.
• 1995—5.3 ng WHO98 TEQP/kg of waste burned.
• 2000—5.3 ng WHO98 TEQP/kg of waste burned.
Activity Levels
• 1987—7.87 MMT.
• 1995—8.18 MMT.
• 2000—6.49 MMT.
Releases
• 1987—41 g WHO98 TEQp.
• 1995—43 g WHO98 TEQP.
• 2000—34 g WHO98 TEQp.
Solid Residue Releases
Emission Factors
• 1987—0.8 ng WHO98 TEQP/kg of ash.
• 1995—0.8 ng WHO98 TEQP/kg of ash.
• 2000—0.8 ng WHO98 TEQP/kg of ash burned.
Activity Levels
• 1987—1.2 MMT.
• 1995—1.2 MMT.
• 2000—0.97 MMT.
Releases
• 1987—1 gWHO98 TEQp.
• 1995—1 gWHO98 TEQp.
• 2000—0.8 g WHO98 TEQp.
1
2
3 10.4.8. Petroleum Refining Catalyst Regeneration
4 As discussed in EPA (2006), evidence exists that PCBs can be released from petroleum
5 refining catalyst regeneration, but the information is insufficient to make quantitative release
6 estimates. No changes were made to this conclusion.
7
Petroleum Refining Catalyst Regeneration
Air Releases
Not quantifiable.
This document is a draft for review purposes only and does not constitute Agency policy.
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1 10.4.9. Hazardous Waste Incineration
2 This is a completely new section on hazardous waste incineration.
3 Two studies were identified from outside of the United States that measured emissions of
4 dioxin-like PCBs along with dioxins and furans from hazardous waste incinerators. One of the
5 studies was consistent with studies on municipal solid waste incinerators, which showed
6 CDD/CDF TEQ emissions to be an order of magnitude and more higher than PCB emissions.
7 Kim et al. (2005) measured 209 congeners in stack emissions from nine facilities, which
8 included two industrial waste incinerators and a "specific industrial waste incinerator." The
9 emission concentrations of the dioxin-like PCBs in the industrial waste incinerators were
10 0.136 for the "specific" incinerator and 0.025 ng WHO98 TEQP/Nm3 for the average of the
11 two industrial waste incinerators. These were characterized as being equal to 2.9 and 1.3% of
12 the emission concentrations of WHOgg TEQDF. On the other hand, Francois et al. (2005)
13 measured dioxins, furans, and coplanar PCBs from 15 facilities including one HWI. The
14 concentration of the PCBs was 0.0051 ng WHOgg TEQp/Nm3, which was almost three times
15 higher than the measurement of CDD/CDFs, at 0.0019 ng WHO9g TEQP/Nm3. The annual
16 emission of dioxin-like PCBs from this facility was estimated at 1.5 mg WHOgg TEQp/year.
17 Given the inconsistent results from these two studies, it is unclear how to make emission
18 estimates on even a preliminary basis.
19 Therefore, the available data were judged inadequate to support development of a
20 quantitative estimate of a dioxin-like PCB emission factor for this source category.
21
22
Hazardous Waste Incineration
Releases
Not quantifiable.
23
24
25 10.4.10. Power Plants
26 This is a completely new section.
27 Emissions from power plants were estimated to account for 2% of the total PCB releases
28 occurring in the United Kingdom in 1998 (Dyke, 2002).
29 Brodsky et al. (2003) reported on measurements from six combustion sources in Russia,
30 including two power plants. Numerous individual congener concentrations in the stack gas
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1 emissions were provided including some dioxin-like PCBs, although no TEQ estimates were
2 provided and no congener-specific emission factors were provided. Concentrations were
3 provided for PCB-105, PCB-118, PCB-123, PCB-156, PCB-157, PCB-170, andPCB-180. The
4 TEQ concentration in the power plant for these congeners was 0.02 ng WHOgg TEQp/Nm3.
5 Francois et al. (2005) reported on testing at 15 incinerators including one coal-fired
6 power plant. They measured emissions of CDD/CDF and PCB as
7 0.0003 ng WHOgg TEQDF/Nm3 and 0.0009 ng WHO9g TEQP/Nm3, respectively. Extrapolating to
8 annual emissions, they estimated an emission of 1.17 mg WHOgg TEQp/year. Dyke et al. (2003)
9 reported on emission measurements from a coal-fired power station in the United Kingdom.
10 They found nondetects for all dioxin-like PCBs tested, except a positive for PCB-180 in one of
11 two tests.
12 The available data were judged inadequate to support development of a quantitative
13 estimate of a dioxin-like PCB emission factor for this source category.
14
15
Power Plants
Releases
Not quantifiable.
16
17
18 10.4.11. Forest Fires
19 This is a completely new section.
20 Collet and Fianni (2006) conducted five forest fire test burns in a chamber of about
21 80 m3. The samples were collected from forests in two regions of southern France and the tests
22 were conducted by the French Agency for Environment and Energy Management. Blank
23 samples were also taken to ensure that the chamber did not introduce contaminants to the burns.
24 Emission concentrations were determined for the 17 CDD/CDFs and 12 dioxin-like PCBs.
25 Generally, PCBs explained about 6% of the total TEQ emissions, except for one forest fire burn,
26 where emissions overall were close to blanks and PCBs contributed 26% in this case. The
27 emission factors for CDD/CDFs ranged from 1.0 ng I-TEQop/kg burned (the low for the test
28 close to the blank) to 26 ng I-TEQop/kg. The TEF scheme used to characterize PCB emissions
29 was not clear but assumed here to be WHOgg. This implies that the PCB emission factor ranged
30 from 0.06 to 1.6 WHO98 TEQP.
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1 For the purposes of deriving a preliminary estimate, it is assumed that the PCB TEQ
2 emission factor is 6% of the one for CDD/CDFs (based on the results from Collet and Fianni
3 [2006]). As discussed in Chapter 6, the forest fire emission factor is 3 ng WHOgg TEQop/kg.
4 This is adjusted to 0.2 ng WHOgg TEQp/kg for PCBs. This emission factor is considered
5 preliminary because it is uncertain how well the limited testing represents all fire/wood types.
6 The activity levels for forest fires are presented in Chapter 6. PCBs are also likely to be present
7 in the ash, but insufficient information was available to make quantifiable estimates.
8 The inventory decision criteria and releases to all media are summarized below:
9
10
Inventory Decision Criteria for Forest Fires
Air Water Solids Products
mission tests for at least two units/source types with Yes
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable Yes
ifferences.
Emission factor tests represent units that are typical of the No
;lass.
activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
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Forest Fires
Air Releases
Emission Factors
• 1987—0.2 ng WHO98 TEQP/kg (Preliminary).
• 1995—0.2 ng WHO98 TEQP/kg (Preliminary).
• 2000—0.2 ng WHO98 TEQP/kg (Preliminary).
Activity Levels
• 1987—61 MMT.
• 1995—55 MMT.
• 2000—243.8 MMT.
Releases
• 1987—12 g WHO98 TEQp (Preliminary).
• 1995—11 g WHO98 TEQp (Preliminary).
• 2000—49 g WHO98 TEQp (Preliminary).
Solid Residue Releases
Not quantifiable.
1
2
3 10.5. METAL REFINING SOURCES
4 This is a completely new section.
5 Kim et al. (2004) measured all 209 PCB congeners in stack emissions from
6 nine facilities, including a sintering furnace in a ferrous metal foundry and two smelting furnaces
7 in nonferrous metal foundries in Japan. All nine facilities emitted PCBs, with total PCBs
8 ranging from 10-700 ng/Nm3 and coplanar PCBs in the range of 1-25 ng/Nm3
9 (0.008-0.324 ng WHO98 TEQP/Nm3). The three metal facilities had these results: aluminum
10 smelting furnace—0.020 ng WHO98 TEQp/Nm3; copper smelting
11 furnace—0.026 ng WHO98 TEQP/Nm3; and sintering furnace—0.018 ng WHO98 TEQP/Nm3. In
12 terms of a relationship to CDD/CDFs, Kim et al. (2004) developed a ratio of the TEQ
13 concentration of dioxin-like PCBs to that of CDD/CDFs and found the narrow range of 0.032 to
14 0.050, suggesting that the TEQ concentration of dioxin-like PCBs was over an order of
15 magnitude lower than that of CDD/CDFs.
16 Stack gas emissions of dioxin-like PCBs were measured along with CDD/CDFs from
17 three iron ore sintering plants in the United Kingdom between 2002 and 2003 (Aries et al.,
18 2006). The dioxin-like PCBs found at the highest concentrations were PCB-118 at 6-9 ng/Nm3,
19 followed by 105 at 2-4 ng/Nm3, and 77 at 2-3 ng/Nm3, with others detected at below 2 ng/Nm3.
20 On a TEQ basis, including CDD/CDFs and dioxin-like PCBs (the authors calculated CDD/CDF
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1 using I-TEFs while dioxin-like PCB TEQ was calculated using WHOgg TEFs), the PCBs
2 contributed less than 10% of the total TEQ concentration, which averaged between 0.6 and
3 1.6 ng total TEQ/Nm3. The mass emissions of total TEQ from the three plants, calculated based
4 on emission concentrations in conjunction with mass loadings, totaled 8.7, 9.2, and
5 10.9 g TEQ/year over the three plants.
6 Kim et al. (2004a) reported on the testing of eight incinerators including two sintering
7 furnaces and four smelting furnaces for CDD/CDFs, PCBs, and HCB. The average over all
8 eight incinerators, on a WHO9g TEQ basis, was 0.281 ng/Nm3 for CDD/CDFs and 0.023 ng/Nm3
9 for PCBs, suggesting a factor of 10 difference on average. The aluminum nonferrous metal
10 smelter showed a PCB TEQ concentration at 0.016 ng WHOgg TEQp/Nm3, which was only
11 one-half that of CDD/CDF TEQ, not the order of magnitude suggested by averaging all
12 eight facilities. The copper smelter had the same TEQ concentration for both PCBs and
13 CDD/CDFs: 0.002 ng WHO98 TEQP/Nm3. The most informative tests, perhaps, were the
14 two iron ferrous metal smelters, where CDD/CDF overwhelmed PCB emissions. The CDD/CDF
15 emission concentrations were 1.492 and 0.926 ng WHOgg TEQoF/Nm3, while the PCB emission
16 concentrations were 0.112 and 0.067 ng WHOgg TEQp/Nm3, respectively.
17 Brodsky et al. (2003) reported on measurements from six combustion sources in Russia,
18 including a nonferrous metallurgy plant, a cement plant, an aluminum plant in the calcination
19 furnace, and an aluminum plant in the entry into the electrostatic filter. Numerous individual
20 congener concentrations in the stack gas emissions were provided including some dioxin-like
21 PCBs, although no TEQ estimates were provided and no congener-specific emission factors were
22 provided. Concentrations were provided forPCB-105, PCB-118, PCB-123, PCB-156, PCB-157,
23 PCB-170, and PCB-180. The TEQ concentration in these four facilities ranged from 0.001 to
24 0.006 ng WHO9g TEQP/Nm3. Brodsky et al. (2003) provided a total concentration (sum of all
25 congeners) and an emission factor of total PCBs in ug/MT.
26 Fisher et al. (2004) reported on tests for an experimental sinter box apparatus, which is
27 essentially a small pilot plant. A raw mix of typical iron ore feed—including iron ore fines,
28 fluxes, fuel in the form of coke, and some recycled materials—was combined with five different
29 amounts of potassium chloride to test the effect of chloride on CDD/CDF and dioxin-like PCB
30 emissions. A correlation was found for both CDD/CDF and dioxin-like PCB emissions with
31 chloride content. At a chloride concentration in the entire feed of 250 mg/kg and less, which
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1 encompassed a baseline run and a run at 250 mg/kg chloride, CDD/CDF emissions were fairly
2 steady, suggesting chloride did not affect emissions at concentrations in this range, but at higher
3 concentrations with up to about 800 mg/kg chloride added, the effect was second order. For
4 PCBs, the effect was more linear—a linear rise in PCB emissions was noted with increasing
5 chloride content. PCDF concentrations dominated CDD/CDF, and on a TEQ basis, CDD/CDF
6 dominated over PCBs. Specifically, the ratio of PCB to CDD/CDF TEQ concentrations was in
7 the range of 0.07 for the five tests. On a TEQ basis, PCB-126 contributed 90-95% of total PCB
8 TEQ, but PCB-105 and PCB-118 contributed the most on a straight concentration basis. The
9 authors concluded that at typical chloride concentrations of 50-100 mg/kg in the industry, the
10 total CDD/CDF/PCB concentrations are expected to be below 1.5 ng TEQ/Nm3.
11 Francois et al. (2004) measured emissions at 15 facilities, including two metal smelters
12 and an iron ore sintering plant. For most facilities, their sampling indicated that the TEQ
13 emissions of dioxin-like PCBs nearly matched that of dioxins. With the iron ore sintering plant,
14 however, the dioxin-like PCBs were an order of magnitude less than dioxins:
15 0.058 ng WHOgg TEQP/Nm3 versus 0.65 ng WHO9g TEQDF/Nm3. For the aluminum and copper
16 smelters, PCB emissions were a factor of 2 (at 0.046 ng WHO9g TEQP/Nm3) and a factor of 4 (at
17 0.017 ng WHOgg TEQp/Nm3) less than dioxin TEQ, respectively. They calculated total annual
18 TEQ emissions for these plants and estimated dioxin-like PCB emissions to be 2.3 and
19 18.8 mg WHOgg TEQp/year for the aluminum and copper smelters, respectively, and to be much
20 higher at 474 mg WHOgg TEQp/year for the iron ore sintering plant.
21 As described above, several studies outside of the United States have measured
22 dioxin-like PCBs along with CDD/CDFs from a variety of metal processing facilities including
23 ferrous and nonferrous smelters, iron ore sintering facilities, and other combustion units within
24 the metal refining industry. These studies did not report emission factors but the concentration
25 data consistently suggest that emissions from iron ore sintering plants are about an order of
26 magnitude or more lower than CDD/CDFs, on a TEQ basis. Accordingly, for the purposes of a
27 preliminary estimate, the PCB emission factor is assumed to be 10% of the CDD/CDF emission
28 factor. The activity levels (from Chapter 7) and release estimates are shown below. The studies
29 also indicate that PCB emissions are occurring from copper and aluminum smelting operations,
30
This document is a draft for review purposes only and does not constitute Agency policy.
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1 but the results are not consistent and not easily converted to TEQ emission factors. Thus,
2 quantitative estimates could not be made for these facilities.
3 The inventory decision criteria and releases to all media are summarized below:
4
Inventory Decision Criteria for Iron Ore Sinter Production
Air Water Solids Products
Emission tests for at least two units/source types with No
sufficient documentation to directly derive emission factors.
Vleasured emission factors consistent or have understandable
ifferences.
Emission factor tests represent units that are typical of the
;lass.
activity estimates based on source-specific surveys. Yes
Conclusion (Q = Quantitative, P = Preliminary).
5
6
Iron Ore Sinter Production
Air Releases
Emission Factors
Wet Scrubber
• 1987—0.06 ng WHO98 TEQP/kg of sinter (Preliminary).
• 1995—0.06 ng WHO98 TEQP/kg of sinter (Preliminary).
• 2000—0.06 ng WHO98 TEQP/kg of sinter (Preliminary).
Fabric Filter
• 1987—0.5 ng WHO9g TEQP/kg of sinter (Preliminary).
• 1995—0.5 ng WHO98 TEQP/kg of sinter (Preliminary).
• 2000—0.5 ng WHO98 TEQP/kg of sinter (Preliminary).
Activity Levels"
• 1987—14.5 MMT.
• 1995—12.4 MMT.
• 2000—10.6 MMT.
Releases
• 1987—4 g WHO98 TEQP (Preliminary).
• 1995—3 g WHO98 TEQP (Preliminary).
• 2000—3 g WHO98 TEQP (Preliminary).
7
8 aFifty-nine percent of sinter production was at facilities with wet scrubbers, and 41% was at facilities with fabric
9 filters.
10
11
12
This document is a draft for review purposes only and does not constitute Agency policy.
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Copper and Aluminum Smelting
Air Releases
Not quantifiable.
4 10.6. NATURAL SOURCES (ORIGINALLY SECTION 10.5)
5 As discussed in EPA (2006), there is no clear evidence that releases of dioxin-like PCBs
6 occur from natural sources. No changes were made to this conclusion.
7
8 10.6.1. Biotransformation of Other PCBs
9 As discussed in the original report, studies have shown that under anaerobic conditions,
10 biologically mediated reductive dechlorination to lower-chlorinated congeners, followed by slow
11 anaerobic and/or aerobic biodegradation, is a major pathway for destruction of PCBs in the
12 environment. This research indicates that biodegradation should result in a net decrease rather
13 than a net increase in the environmental load of dioxin-like PCBs.
14
15 10.6.2. Photochemical Transformation of Other PCBs
16 Photolysis and photo-oxidation may be major pathways for destruction of PCBs in the
17 environment. Research reported to date and summarized in the original report indicates that
18 ortho-substituted chlorines are more susceptible to photolysis than are meta- and para-substituted
19 congeners; thus, photolytic formation of more toxic dioxin-like PCBs may occur. Oxidation by
20 hydroxyl radicals, however, apparently occurs preferentially at the meta and para positions,
21 resulting in a net decrease rather than a net increase in the environmental load of dioxin-like
22 PCBs.
23
24 10.7. PAST USE OF COMMERCIAL PCBS (ORIGINALLY SECTION 10.6)
25 This section provides background information about the amount of PCBs used in the past
26 and does not discuss release estimates for the reference years. No changes were made to this
27 section. As discussed in the original report, an estimated 568,000 MT of PCBs were sold in the
28 United States between 1930 and 1975. The environmental releases associated with production,
29 use, and disposal during this time period were estimated as 3,702 kg WHOgg TEQp.
30
This document is a draft for review purposes only and does not constitute Agency policy.
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Table 10-1. Summary of PCB releases for reference years 1987,1995, and 2000 (g WHO98 TEQP/year)
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ
Product releases
Q. Inv.
Prelim.
NQ
Releases from commercial PCB products
PCB incineration
Releases from in-service
PCBs
X
X
X
X
X
Chemical manufacturing and processing sources
Municipal wastewater
treatment
1987
1995
2000
51
78
19
2
12
3
Combustion sources
Municipal waste
combustors
1987
1995
2000
Industrial wood
combustion
Medical waste
incineration
1987
1995
2000
Tire combustion
7
15
15
97
18
14
X
X
§•
rs
s
3
TO
a
I
I
a,
§•
I
-------
to
Table W 1. Summary of PCB releases for reference years 1987,1995, and 2000 (g WHO98 TEQP/year)
(continued)
Source
Cigarette smoking
1987
1995
2000
Sewage sludge
incineration
1987
1995
2000
Backyard barrel
burning
1987
1995
2000
Petroleum-refining
catalyst regeneration
Hazardous waste
incineration
Power plants
Forest fires
1987
1995
2000
Air releases
Q. Inv.
41
43
34
Prelim.
<01
<0.1
<0.1
0.4
1
0.7
12
11
49
NQ
X
X
X
Land releases
Q. Inv.
1
1
0.8
Prelim.
NQ
X
Water releases
Q. Inv.
Prelim.
NQ
Product releases
Q. Inv.
Prelim.
NQ
§•
C5
S
3
TO
a
I
to
fe
H
O
O
o
H
O
HH
H
W
O
O
O
H
W
I
a,
§•
OQ
TO
I
-------
to
OJ
Table W 1. Summary of PCB releases for reference years 1987,1995, and 2000 (g WHO98 TEQP/year)
(continued)
Source
Air releases
Q. Inv.
Prelim.
NQ
Land releases
Q. Inv.
Prelim.
NQ
Water releases
Q. Inv.
Prelim.
NQ
Product releases
Q. Inv.
Prelim.
NQ
Metal refining
Iron ore sintering
1987
1995
2000
Copper smelting
Aluminum smelting
Total
1987
1995
2000
41
43
34
4
3
3
120
48
82
X
X
52
79
20
2
12
3
§•
rs
s
3
TO
a
I
to
I
a,
§•
o
3-
TO*
OQ
I
fe
H
O
O
o
H
O
HH
H
W
O
O
O
H
W
x = Releases are possible during this year, but the data are insufficient to develop estimates.
Q. Inv. = Quantitative Inventory.
Prelim. = Preliminary.
NQ = Not quantified.
-------
1
2
Table 10-2. PCB analysis for composite ash samples from barrel burning
Congener
3,3',4,4'-TCB
3,4,4',5-TCB
2,3,3',4,4'-PeCB
2,3,4,4',5-PeCB
2,3',4,4',5-PeCB
2',3,4,4',5-PeCB
3,3',4,4',5-PeCB
2,3,3',4,4',5-HxCB
2,3,3',4,4',5'-HxCB
2,3',4,4',5,5'-HxCB
3,3',4,4',5,5'-HxCB
2,3,3',4,4',5,5'-HpCB
Total WHO98 TEQp
IUPAC
number
77
81
105
114
118
123
126
156
157
167
169
189
Emission factors (ug/kg)
Recycler
1.2
3.4
0.7
0.6
0.0009
Nonrecycler
1
3.5
<0.5
<0.5
0.0006
Average
1.1
3.5
0.5
0.4
0.0008
3
4
5
6
7
Averages and TEQs calculated assuming half the values for entries shown as less than.
IUPAC = International Union of Pure and Applied Chemistry.
Source: Lemieux (1997).
This document is a draft for review purposes only and does not constitute Agency policy.
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1 11. RESERVOIR SOURCES OF CDD/CDFS AND DIOXIN-LIKE PCBS
2
3
4 This introduction has been expanded to more clearly define reservoirs. Chapters 2
5 through 10 of this document discuss sources with the potential for initial releases of dioxin-like
6 compounds to the environment in the United States. This chapter addresses releases from
7 reservoirs that are defined as materials or places that contain previously released CDD/CDFs or
8 dioxin-like PCBs and have the potential for redistributing these compounds into the environment.
9 Potential reservoirs include soils, sediments, biota, water, and some products. Products that
10 contain CDD/CDFs can be considered reservoirs when they have the potential for releases after
11 their initial use. The atmosphere could be considered a reservoir but is excluded here because it
12 is the primary medium for transporting and distributing CDDs and CDFs over large geographical
13 areas. Thus, it is considered a temporary holding place rather than a long-term reservoir.
14 Although water is also an important transport medium, the residence times can be long, and,
15 therefore, it is appropriately considered a reservoir.
16 The definition of reservoirs as used in this document also excludes CDD/CDFs contained
17 in natural ball clay deposits. The CDD/CDFs contained in ball clay were formed by geochemical
18 processes that are thought to have occurred millions of years ago. Any release from ball clay
19 would be an initial release to the contemporary environment, and, therefore, ball clay is not
20 considered to be a reservoir. Potential ball clay releases are covered in Chapter 9 on Natural
21 Sources.
22 Soils in some locations could have elevated CDD/CDF levels due to past activities such
23 as pesticide use, spills, illegal disposal, or fires. These areas would be considered part of the soil
24 reservoir and would have the potential for greater release rates than normal soils with background
25 CDD/CDF levels. The soil-release estimates presented in this document do not include releases
26 from these "hot spots" due to lack of appropriate information. However, they could be important
27 events on a local scale and should be considered where feasible.
28 Dioxin-like compounds are sequestered by a reservoir only until physical processes
29 cause these contaminants to become released into the open environment over a defined time and
30 space. When this occurs, reservoirs become sources of dioxin-like compounds in the circulating
31 environment. Figure 11-1 presents a conceptual diagram of flux and exchange of dioxin-like
32 compounds to multiple environmental compartments such as soils, water, air, sediments, and
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1 biota. This dynamic system consists of fluxes in and out of the atmosphere as well as other
2 exchanges between reservoirs and the atmosphere (recall that the atmosphere is not defined here
3 as an environmental reservoir, rather as a transport medium for dioxin-like compounds).
4 Movement of dioxin-like compounds between media can be induced by the physical processes of
5 volatilization, wet and dry atmospheric particle and vapor deposition, adsorption, erosion and
6 runoff, resuspension of soils into air, and resuspension of sediments into water.
7 This chapter describes the major reservoir sources of CDD/CDFs and PCBs, including, to
8 the extent feasible, estimates of the potential mass of CDD/CDFs and PCBs in each reservoir, the
9 chemical/physical mechanisms responsible for releases of these compounds, and estimates of
10 potential annual releases from each reservoir.
11
12 11.1. SOIL RESERVOIRS (ORIGINALLY SECTION 11.2.1)
13 This section provides revised estimates of the amounts of CDD/CDFs in soil reservoirs.
14 Harrad and Jones (1992) and Duarte-Davidson et al. (1997) estimated the CDD/CDF
15 content of soils in the United Kingdom by multiplying the soil surface area by the contamination
16 depth, soil density, and CDD/CDF concentration in the soil. A similar approach was used here
17 to estimate the amount CDD/CDFs in surface soils of the United States. The following inputs
18 were used in these calculations:
19
20 • Surface soils were divided into rural and urban areas to reflect differences in the
21 CDD/CDF levels. Urban areas were assumed to have an average concentration of
22 10 pg WHO TEQDF/g, and rural soils, 2 pg WHO TEQDF/g (U.S. EPA, 2007b).
9
23 • The urban land area in the United States is 1.82 million km based on Census Bureau
24 statistics for metropolitan areas (USD A, 2002). The portion of urban areas covered by
25 impervious surfaces (rather than soil) varies widely. For the purposes of a preliminary
26 estimate, it was assumed that an average of 50% of the metropolitan land area had soil
27 coverage. The land area of nonmetropolitan areas in the United States is
28 7.28 million km2 (USDA, 2002).
29 • The soil density was assumed to be 2.6 g/cm3 (Brady, 1984).
30 • The contamination depth was assumed to be 10 cm (U.S. EPA, 2007b).
31
32 Based on these assumptions, the amount of CDD/CDFs in U.S. surface soils was estimated as
33 2,370 kg WHO TEQDF in urban soils and 3,790 kg WHO TEQDF in rural soils, for a total of
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1 6,150 kg WHO TEQDF. EPA (2007b) found that average PCB TEQs were about 4% of average
2 total D/F/P TEQs in rural soils. Assuming this percentage applies to urban areas as well, this
3 would imply that the soil reservoir contains about 95 kg WHO TEQp. These calculations are not
4 definitive and only indicate approximate amounts of dioxins that may be contained in U. S.
5 surface soils.
6 Soils in some locations could have elevated CDD/CDF levels (or "hot spots") due to
7 uncontrolled activities such as spills, illegal disposal, or fires. Elevated soil levels could also
8 occur in areas where 2,4-D and 2,4,5-T were used and areas with land-applied sludges/ash.
9 These areas would be considered part of the soil reservoir and would have the potential for
10 greater release rates than normal soils with background CDD/CDF levels. The amounts in
11 landfills could also be considered part of the soil reservoir, although the potential for release is
12 much less. No estimates could be made for the additional CDD/CDF soil burdens due to the
13 uncontrolled activities, but estimates were made for the other activities as discussed below.
14 Estimates can be made for the total mass of CDD/CDF TEQs that have been applied to
15 soil from past use of the pesticides 2,4-dichlorophenoxyacetic acid (2,4-D) and
16 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). As discussed in Chapter 11 of the original report,
17 the total amounts of CDD/CDF released to the environment are as follows:
18
19 • From 2,4-D use during the period of 1975 to 1995, the total release was estimated as
20 0.55 kg WHO98 TEQDF (0.35 kg I-TEQDF).
21 • From 2,4,5-T use over the period of 1950 to 1979, the total release was estimated as
22 36kgof2,3,7,8-TCDD.
23
24 The amounts of CDD/CDFs in landfills can also be considered a soil reservoir with the
25 potential for releases in the future. The earlier chapters provided estimates of the amounts of
26 CDD/CDFs landfilled for many sources. As shown in Table 11-1, the total amounts landfilled
27 were estimated as 3,750 g TEQ in 1987, 1,050 g TEQ in 1995, and 1,310 g TEQ in 2000. If it is
28 assumed that most landfills operate for 30 years and the average annual input equals the average
29 over the reference years (2,040 g TEQ), then the cumulative sum would be 61,000 g TEQ. This
30 should be regarded as a preliminary estimate because it is based on numerous assumptions and
31 limited data.
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1 A variety of waste types containing CDD/CDFs are land applied such as sewage sludge,
2 wood pulp sludge, residential wood burning ash, and beneficial uses of cement kiln clinker.
3 These sources also contribute to the soil reservoir. As shown in Table 1-9, these sum to
4 2,400 g TEQ in 1987, 2,500 g TEQ in 1995, and 2,300 g TEQ in 2000. If it is assumed that
5 operations persist for 30 years and the average annual input equals the average over the reference
6 years (2,400 g TEQ), then the cumulative sum would be 72,000 g TEQ. This should be regarded
7 as a preliminary estimate because it is based on numerous assumptions and limited data.
8 In summary, the total mass of CDD/CDF that is contained in the soil reservoir is
9 approximately 6,150 kg WHOgg TEQ with perhaps an additional 170 kg TEQ from past
10 additions (landfills - 61 kg TEQ, pesticide use - 37 kg TEQ and land-applied sludges/ash - 72 kg
11 TEQ). As discussed below, various forms of degradation/removal can occur in soil, which
12 would reduce these contributions from the past, making it uncertain how much of these remain in
13 the soil reservoir today.
14
15 11.1.1. Mechanisms Responsible for Releases from Surface Soils
16 As discussed in the original report, a number of studies have demonstrated that soil
17 releases can occur via erosion, degradation, volatilization, and particle resuspension.
18 11.1.2. Estimated Annual Releases from Soil to Water
19 Nonpoint sources of CDD/CDFs to waterways include stormwater runoff from urban
20 areas and soil erosion in rural areas during storms. Approaches for estimating national loadings
21 to water for both of these sources are described below.
22
23 11.1.2.1. Urban Runoff
24 No changes were made in this update. As discussed in the original report, a wide range
25 of CDD/CDF concentrations were measured in urban runoff at 23 sites in California (Mathur
26 et al., 1997; Fisher et al., 1999). The midpoint of the 4 order of magnitude range was selected.
27 Based on the wide range of results and uncertainty about the representativeness of the samples,
28 this factor is considered preliminary. The run-off volume was calculated based on rainfall data
29 and urban area data. All factors and release estimates are presented in the release summary
30 below.
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1
2 11.1.2.2. Rural Soil Erosion
3 The original report also presented estimates for CDD/CDF releases from rural soils. No
4 changes were made to the activity estimates, but updates were made to the emission factors as
5 discussed below.
6 The data summarized in EPA (2007b) suggest that the typical concentration of
7 CDD/CDFs in soils in rural areas is about 1.7 ng WHOgg TEQop/kg based on samples from
8 27 locations. Similarly, EPA (2007b) suggests that the typical concentration of PCBs in soils in
9 rural areas is about 0.07 ng WHOgg TEQp/kg. These values were assumed to apply to all
10 three reference years. It is not known how well these estimates represent eroded soil from
11 cropland and rangeland and were given a preliminary confidence rating. Multiplying the
12 emission factor and activities, yields CDD/CDF release estimates of 4,900, 4,400 and
13 4,200 g WHOgg TEQDF for 1987, 1995, and 2000, respectively. Similarly, the PCB release
14 estimates were calculated as 200, 180, and 170 g WHO9g TEQP for 1987, 1995, and 2000,
15 respectively. These release estimates have preliminary confidence ratings because the emission
16 factor has a preliminary rating.
17
18 11.1.3. Estimated Annual Releases from Soil to Air
19 As discussed in the original report, a number of investigators have studied releases from
20 soil to air, but no quantitative estimates of the mass of dioxin-like compounds that may be
21 released to the atmosphere annually from U.S. soils have been published in the literature and
22 none were developed for this report. Particulate dioxin concentrations were compared with
23 average total particulate dioxin levels to arrive at the conclusion that soil reentrainment could
24 account for only 1 to 4% of the particulate dioxins in the atmosphere in urban areas and 0.1 to
25 0.3% of those in rural regions (Kao and Venkataraman, 1995).
26 The inventory decision criteria and releases to all media are summarized below:
27
28
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Inventory Decision Criteria for Soil Reservoirs
Air Water Solids Products
Emission tests for at least two units/source types with
sufficient documentation to directly derive emission
factors.
Measured emission factors consistent or have
understandable differences.
Emission factor tests represent units that are typical of
the class.
Activity estimates based on source-specific surveys.
Conclusion (Q = Quantitative, P = Preliminary).
Yes
No
No
Yes
P
1
2
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Soil Reservoirs
Releases to Air
Not quantifiable.
Releases to Urban Water
Emission Factors
• 1987—1 pg WHO9g TEQoF/L (1 pg I-TEQDF/L) (Preliminary).
• 1995—1 pg WHO98 TEQoF/L (1 pg I-TEQDF/L) (Preliminary).
• 2000—1 pg WHO9g TEQoF/L (1 pg I-TEQDF/L) (Preliminary).
Activity Levels
• 1987—1.24 x lQ14L/yr.
• 1995—1.33 x lQ14L/yr.
• 2000—1.42 x lQ14L/yr.
Releases
• 1987—120 g (WHO98 TEQDF or I-TEQDF) (Preliminary).
• 1995—130 g (WHO98 TEQoF or I-TEQDp) (Preliminary).
• 2000—140 g (WHO98 TEQoF or I-TEQDp) (Preliminary).
Release to Rural Water
Emission Factors
• 1987—1.7 ng WHO98 TEQDF/kg (Preliminary) and
0.07 ng WHO98 TEQp/kg (Preliminary).
• 1995—1.7 ng WHO98 TEQDF/kg (Preliminary) and
0.07 ng WHO98 TEQp/kg (Preliminary).
• 2000—1.7 ng WHO98 TEQDF/kg (Preliminary) and
0.07 ng WHO98 TEQp/kg (Preliminary).
Activity Levels
• 1987—2.91 billion MT of soil.
• 1995—2.62 billion MT of soil.
• 2000—2.46 billion MT of soil.
Releases
• 1987—4,900 g WHO98 TEQDF (Preliminary) and 200 g WHO98 TEQP (Preliminary).
• 1995—4,500 g WHO98 TEQDF (Preliminary) and 180 g WHO98 TEQP (Preliminary).
• 2000—4,200 g WHO98 TEQDF (Preliminary) and 170 g WHO98 TEQP (Preliminary).
1
2
3 11.2. WATER RESERVOIRS (ORIGINALLY SECTION 11.2.2)
4 As discussed in the original report, water reservoirs have the potential for releases to air
5 or sediment, but no quantifiable estimates could be made.
6
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Water Reservoirs
Releases to Air
Not quantifiable.
Releases to Sediment
Not quantifiable.
2
3
4 11.3. SEDIMENT RESERVOIRS (ORIGINALLY SECTION 11.2.3)
5 The original report used assumptions about the water surface area, sediment depth, and
6 background TEQ concentration for U.S. sediments to estimate that at least
7 120 kg WHOgg TEQop (120 kg I-TEQop) are present in the sediment reservoir.
8
9 11.3.1. Mechanisms Responsible for Supply to and Releases from Sediment
10 The original report identified atmospheric deposition of CDDs and CDFs as an important
11 mechanism for CDD/CDFs to enter sediments and those sediments are a likely sink for these
12 compounds because they are strongly bound to organic particles in the sediment.
13
14 11.3.2. Releases from Sediment to Water
15 As discussed in the original report, studies have attempted to evaluate the transfers from
16 sediment to water to air, but the information needed to estimate this release nationally is lacking.
17 For this reason, no quantitative estimates can be made for annual releases from sediment
18 reservoirs to water.
19
Sediment Reservoirs
Releases to Water
Not quantifiable.
20
21
22 11.4. BIOTA RESERVOIRS (ORIGINALLY SECTION 11.2.4)
23 CDD/CDFs are found in all types of biota including vegetative matter and animal tissues.
24 No studies were found that estimated the mass of CDD/CDFs in biota in the United States.
25
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1 11.4.1. Mechanisms Responsible for Supply to and Releases from Biota
2 The original report identified vapor absorption and desorption as an important
3 mechanism for plants and ingestion/bioaccumulation as an important mechanism for animals.
4
5 11.4.2. Approaches for Measuring and Estimating Releases from Biota
6 The original report describes a number of studies that evaluate the CDD/CDF releases
7 from biota to soil and air, but insufficient information is available to make quantitative estimates
8 for national releases.
9
Biota Reservoirs
Releases to Air
Not quantifiable.
Releases to Soil
Not quantifiable.
10
11
12 11.5. PRODUCT RESERVOIRS
13 This is a new section. As discussed in Chapter 8, a number of chemical products contain
14 CDD/CDFs. Some of these can be considered reservoirs because they have the potential for
15 CDD/CDF releases after their initial use. Others are used in a manner such that any releases
16 would occur during their initial use, and therefore, they are not considered a reservoir for future
17 releases. For example, 2,4-D is a pesticide that is applied to foliage and would have an
18 immediate release to biota and soil. Although it may persist in the environment after application,
19 it would become part of the biota or soil reservoir rather than a separate product reservoir.
20 Similarly, chlorobenzenes are used as pesticides or chemical intermediates for pesticides and,
21 therefore, are not considered product reservoirs. The products that may represent potential
22 reservoirs are discussed below.
23
24 11.5.1. Bleached Chemical Wood Pulp
25 The primary discussion of potential dioxin releases from the bleached chemical wood
26 pulp and paper industry is presented in Section 8.1. Many products made from bleached
27 chemical wood pulp remain in use long after their production and, therefore, represent a potential
28 reservoir. The limited data available on the dioxin concentrations in these products indicate
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1 decreasing levels over time, but the data are insufficient to make a reliable estimate of the
2 cumulative amounts. As reported in Section 8.1, wood pulp is estimated to have contained
3 500 g WHO98 TEQ in 1987, 40 g WHO98 TEQ in 1995, and 0.6 g WHO98 TEQ in 2000. The
4 total reservoir of CDD/CDFs in these products would be the cumulative amount of these
5 products remaining in use minus any degradation or releases that have occurred. Insufficient
6 information is available to estimate the size of the total reservoir or the possible releases.
7
8 11.5.2. Chlorophenols
9 The primary discussion of potential dioxin releases from chlorophenol production is
10 presented in Section 8.4. The lower-chlorinated phenols have been used primarily as chemical
11 intermediates in the manufacture of other pesticides. Pesticides are typically used the same year
12 as they are produced and, therefore, are not a reservoir for future releases. The
13 higher-chlorinated phenols (tetrachlorophenol and PCP) and their sodium salts have been used
14 primarily for wood preservation. Wood products treated with these chemicals have long service
15 lives and represent a potential reservoir. As discussed in Chapter 8, an estimate of average
16 annual domestic PCP consumption during the period of 1970 to 1995 is about 400,000 MT. As
17 reported in Section 8.4, PCP is estimated to have contained 20,000 g WHO98 TEQ in 1987,
18 4,800 g WHO TEQ in 1995, and 4,200 g WHO98 TEQ in 2000. The limited data available on the
19 dioxin concentrations in these products indicate decreasing levels over time, but the data are
20 insufficient to make a reliable estimate of the cumulative amounts. It is unknown how much of
21 the CDD/CDFs degrade in situ or escapes from the wood into the environment. Several recent
22 field studies, as discussed in Chapter 8, demonstrate that CDD/CDFs do apparently leach into
23 soil from PCP-treated wood, but the studies do not provide release-rate data. No studies were
24 located that provide any measured CDD/CDF volatilization rates from PCP-treated wood.
25 Although CDD/CDFs have very low vapor pressures, they are not bound to, nor do they react
26 with, the wood in any way that would preclude volatilization. Several studies (see Chapter 8)
27 have attempted to estimate potential CDD/CDF volatilization releases using conservative
28 assumptions or modeling approaches, but these estimates span many orders of magnitude.
29 Insufficient information is available to estimate the size of the total reservoir or the possible
30 releases.
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1 11.5.3. Vinyl Chloride Products
2 The primary discussion of potential dioxin releases from vinyl chloride production is
3 presented in Section 8.3. Many vinyl chloride products remain in use long after their production
4 and, therefore, represent a potential reservoir. Limited data are available on the dioxin
5 concentrations in these products, but the data are insufficient to make a reliable estimate of the
6 cumulative amounts. As discussed in Section 8.3, concentration and production data can be used
7 to estimate that vinyl chloride contained 0.02 g I-TEQ in 1995 and 0.02 g I-TEQ in 2000. The
8 total reservoir of CDD/CDFs in these products would be the cumulative amount of these
9 products remaining in use minus any degradation or releases that have occurred. Insufficient
10 information is available to estimate the size of the total reservoir or the possible releases.
11
12 11.5.4. Chloranil
13 The primary discussion of potential dioxin releases from chloranil production is
14 presented in Section 8.9. Chloranil is used to make dyes and pigments. These products may
15 remain in use long after their production and, therefore, represent a potential reservoir. As
16 discussed in Section 8.9, chloranil imports contained 64 g I-TEQ in 1987, 0.4 g I-TEQ in 1995,
17 and 1.2 g I-TEQ in 2000. The total reservoir of CDD/CDFs in these products would be the
18 cumulative amount of these products remaining in use minus any degradation or releases that
19 have occurred. Insufficient information is available to estimate the size of the total reservoir or
20 the possible releases.
21
22 11.5.5. Polychlorinated Biphenyls (PCBs)
23 As discussed in Chapter 10 (the primary chapter on PCBs), production of PCBs ceased in
24 the 1970s. However, they were used in a variety of products that can remain in use for long time
25 periods, such as transformers and capacitors. The portion of these products that are still in use
26 today represents potential reservoirs because releases can occur via leaks or during disposal
27 operations. As discussed in the original report (see Section 10.6), approximately 568,000 MT of
28 PCBs were used in the United States between 1930 and 1975. An estimated 50.3% were used in
29 capacitors, and 26.8% were used in transformers. Assuming that these products contained an
30 average of 8 mg WHOgg TEQp/kg (average concentration for Aroclor 1242, which accounted for
31 over 50% of total sales—see Section 10.6 of original report), then a total of 3,500 kg of
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1 WHOgg TEQp were used in capacitors and transformers. It is unknown how much of this
2 material is still in use or what amount of releases may be occurring.
3 In summary, five possible product reservoirs were identified: bleached chemical wood
4 pulp, pentachlorophenol, vinyl chloride, chloranil, and PCBs. No estimates could be made for
5 the cumulative mass of CDD/CDFs contained in these reservoirs or their releases.
6
Product Reservoirs
Releases to Air
Bleached Chemical Wood Pulp (Not quantifiable).
Pentachlorophenol (Not quantifiable).
Vinylchloride (Not quantifiable).
Chloranil (Not quantifiable).
PCBs (Not quantifiable).
Releases to Soil
Bleached Chemical Wood Pulp (Not quantifiable).
Pentachlorophenol (Not quantifiable).
Vinylchloride (Not quantifiable).
Chloranil (Not quantifiable).
PCBs (Not quantifiable).
7
8
9 11.6. SUMMARY AND CONCLUSIONS (ORIGINALLY SECTION 11.3)
10 The original report presented a series of conclusions about the relative importance of
11 reservoir sources and their implications to human exposure. Because this version of the
12 document contains only slight revisions to reservoir source estimates, the same general
13 observations made in the previous version still apply. In addition, reservoir sources are all still
14 considered "preliminary", and thus not part of the quantitative inventory.
15
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Table 11-1. Amounts of CDD/CDFs Landfilled (g WHO98 TEQ/year)
Source
Municipal waste incinerators
Medical waste incinerators
Animal crematoria
Sewage sludge
Industrial wood
Industrial coal-fired utilities
Cement kilns
Magnesium smelting and refining
Titanium smelting and refining
Chlor-akali plants
Vinyl chloride plants
Complex organic chemical plants
Municipal wastewater treatment sludge
Total
1987
2800
760
0.2
0.4
46
39
15
86
3,750
1995
490
410
0.2
1
46
43
18
40
1,050
2000
490
320
0.2
0.7
46
50
13
10a
240a
3
6
118
13
1,310
"Based on TRI data (U.S. EPA, 2008).
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Sources
.Sources
Fluxes Among Dioxin Reservoiis
Figure 11-1. Fluxes among environmental reservoirs.
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