&EPA
United States
Environmental Protection
Agency
The Inventory of Sources
and Environmental Releases
of Dioxin-Like Compounds
in the United States: The
Year 2000 Update
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DRAFT EPA/600/P-03/002A
DO NOT CITE OR QUOTE March 2005
External Review Draft
The Inventory of Sources and Environmental Releases of
Dioxin-Like Compounds in the United States:
The Year 2000 Update
NOTICE
THIS DOCUMENT IS A PRELIMINARY 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
-------
DISCLAIMER
This document is a draft for review purposes only and does not constitute U.S.
Environmental Protection Agency policy. Mention of trade names or commercial products does
not constitute endorsement or recommendation for use.
ABSTRACT
The purpose of this report is to present a comprehensive inventory and overview of
sources and environmental releases of dioxin-like compounds in the United States. The major
identified sources of environmental releases of dioxin-like compounds are grouped into six broad
categories: combustion sources, metals smelting, refining and process sources, chemical
manufacturing sources, biological and photochemical processes sources, and environmental
reservoirs. Estimates of annual releases to land, air, and water are presented for each source
category and summarized for reference years 1987, 1995, and 2000. The quantitative results are
expressed in terms of the toxicity equivalent (TEQ) of the mixture of poly chlorinated
dibenzo-^-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-/>-dioxin (2,3,7,8-TCDD), the most toxic member of this class of
compounds. Using this WHO procedure, the annual releases of TEQDF-WHO98 to the U.S.
environment over the three reference years are 13,962 g in 1987, 3,280 g in 1995, and 1,529 g in
2000. This analysis indicates that between reference years 1987 and 2000, there was
approximately 89% reduction in the releases of dioxin-like compounds to the circulating
environment of the United States from all known sources combined. In 1987 and 1995, the
leading source of dioxin emissions to the U.S. environment was municipal waste combustion;
however, because of reductions in dioxin emissions from municipal waste combustors, it
dropped to the third ranked source in 2000. Burning of domestic refuse in backyard burn barrels
remained fairly constant over the years, but in 2000, it emerged as the largest source of dioxin
emissions.
Preferred Citation:
U.S. EPA (Environmental Protection Agency). (2005) The inventory of sources and environmental releases of
dioxin-like compounds in the United States: the year 2000 update. National Center for Environmental Assessment,
Washington, DC; EPA/600/P-03/002A. Available from: National Technical Information Service, Springfield, VA,
and online at http://epa.gov/ncea.
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CONTENTS
LIST OF TABLES xii
LIST OF FIGURES xxv
LIST OF ABBREVIATIONS AND ACRONYMS xxix
FOREWORD xxxiii
PREFACE xxxv
AUTHORS, CONTRIBUTORS, AND REVIEWERS xxxvi
EXECUTIVE SUMMARY xl
1. BACKGROUND, APPROACH, AND CONCLUSIONS 1-1
1.1. BACKGROUND 1-1
1.1.1. Reference Years 1-2
1.1.2. Regulatory Summary 1-3
1.1.3. Definition of Dioxin-Like Compounds 1-5
1.1.4. Toxicity Equivalency Factors (TEFs) 1-6
1.1.5. Information Sources 1-7
1.2. APPROACH 1-8
1.2.1. Source Classes 1-9
1.2.2. Quantitative Method for Inventory of Sources 1-11
1.2.3. Confidence Ratings 1-12
1.3. CONCLUSIONS 1-14
1.3.1. Total Environmental Releases 1-14
1.3.2. Time Trends 1-15
1.3.3. Sources Not Included in the Inventory 1-15
1.3.4. Formation Theory 1-16
1.3.5. Congener Profiles of CDD/CDF Sources 1-17
2. MECHANISMS OF FORMATION OF DIOXIN-LIKE COMPOUNDS DURING
COMBUSTION OF ORGANIC MATERIALS 2-1
2.1. MECHANISM 1 (PASS THROUGH): CDD/CDF CONTAMINATION IN
FUEL AS A SOURCE OF COMBUSTION STACK EMISSIONS 2-3
2.2. MECHANISM 2 (PRECURSOR): FORMATION OF CDDs/CDFs FROM
PRECURSOR COMPOUNDS 2-4
2.3. MECHANISM 3: DE NOVO SYNTHESIS OF CDDs/CDFs DURING
COMBUSTION OF ORGANIC MATERIALS 2-12
2.4. THE ROLE OF CHLORINE IN THE FORMATION OF CDDs/CDFs IN
COMBUSTION SYSTEMS 2-19
2.4.1. Review of Laboratory-Scale Studies 2-20
2.4.2. Review of Full-Scale Combustion Systems 2-26
2.5. POTENTIAL PREVENTION OF CDD/CDF FORMATION IN
COMBUSTION SYSTEMS 2-28
2.6. THEORY ON THE EMISSION OF PCBs 2-29
2.7. SUMMARY AND CONCLUSIONS 2-31
2.7.1. Mechanisms of Formation of Dioxin-Like Compounds 2-31
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CONTENTS (continued)
2.7.2. Role of Chlorine 2-33
2.7.3. General Conclusion 2-35
3. COMBUSTION SOURCES OF CDDs/CDFs: WASTE INCINERATION 3-1
3.1. MUNICIPAL WASTE COMBUSTION 3-2
3.1.1. Description of Municipal Waste Combustion Technologies 3-2
3.1.1.1. Furnace Types 3-2
3.1.1.2. Air Pollution Control Devices 3-5
3.1.1.3. Classification Scheme 3-7
3.1.2. Characterization of MWCs in Reference Years 2000, 1995,
and 1987 3-7
3.1.3. Estimation of CDD/CDF Emissions from MWCs 3-8
3.1.3.1. Estimating CDD/CDF Emissions from MWCs in
Reference Year 2000 3-8
3.1.3.2. Estimating CDD/CDF Emissions from MWCs in
Reference Years 1995 and 1987 3-9
3.1.4. Summary of CDD/CDF (TEQ) Emissions from MWCs for
2000, 1995, and 1987 3-11
3.1.5. Congener Profiles of Municipal Waste Combustion Facilities 3-12
3.1.6. Estimated CDDs/CDFs in MWC Ash 3-13
3.1.7. Recent EPA Regulatory Activities 3-16
3.2. HAZARDOUS WASTE INCINERATION 3-17
3.2.1. Furnace Designs for HWIs 3-18
3.2.2. APCDs for HWIs 3-19
3.2.3. Estimation of CDD/CDF Emission Factors for HWIs 3-21
3.2.4. Emission Estimates for HWIs 3-23
3.2.5. Recent EPA Regulatory Activities 3-25
3.2.6. Industrial Boilers and Furnaces Burning Hazardous Waste 3-25
3.2.7. Halogen Acid Furnaces Burning Hazardous Waste 3-27
3.2.8. Solid Waste from Hazardous Waste Combustion 3-28
3.3. MEDICAL WASTE INCINERATION 3-28
3.3.1. Design Types of MWIs Operating in the United States 3-28
3.3.2. Characterization of MWIs for Reference Years 1987, 1995,
and 2000 3-30
3.3.3. Estimation of CDD/CDF Emissions from MWIs 3-33
3.3.4. OAQPS Approach for Estimating CDD/CDF Emissions from
MWIs 3-34
3.3.4.1. OAQPS Approach for Estimating Activity Level 3-34
3.3.4.2. OAQPS Approach for Estimating CDD/CDF
Emission Factors 3-35
3.3.4.3. OAQPS Approach for Estimating Nationwide
CDD/CDF TEQ Air Emissions 3-36
3.3.5. AHA Approach for Estimating CDD/CDF Emissions from
MWIs 3-37
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CONTENTS (continued)
3.3.6. ORD Approach for Estimating CDD/CDF Emissions from
MWIs 3-38
3.3.6.1. ORD Approach for Classifying MWIs and
Estimating Activity Levels 3-38
3.3.6.2. ORD Approach for Estimating CDD/CDF
Emission Factors 3-40
3.3.7. Summary of CDD/CDF Emissions from MWIs 3-41
3.3.8. Recent EPA Regulatory Activities 3-43
3.4. CREMATORIA 3-44
3.4.1. Human Crematoria 3-44
3.4.1.1. Emissions Data 3-44
3.4.1.2. Activity Level Information 3-49
3.4.1.3. Emission Estimates 3-49
3.4.2. Animal Crematoria 3-49
3.4.2.1. Emissions Data 3-49
3.4.2.2. Activity Level Information 3-50
3.4.2.3. Emission Estimates 3-50
3.5. SEWAGE SLUDGE INCINERATION 3-50
3.5.1. Emission Estimates from Sewage Sludge Incinerators 3-51
3.5.2. Solid Waste from Sewage Sludge Incinerators 3-54
3.6. TIRE COMBUSTION 3-54
3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED
CHEMICAL PULP MILLS 3-56
3.8. BIOGAS COMBUSTION 3-57
4. COMBUSTION SOURCES OF CDDs/CDFs: POWER/ENERGY GENERATION ... 4-1
4.1. MOTOR VEHICLE FUEL COMBUSTION 4-1
4.1.1. Tailpipe Emission Studies 4-1
4.1.2. Tunnel Emission Studies 4-6
4.1.3. National Emission Estimates 4-9
4.1.3.1. Activity Information for On-Road Vehicles 4-9
4.1.3.2. Activity Information for Off-Road Uses 4-11
4.1.3.3. Emission Estimates 4-13
4.2. WOOD COMBUSTION 4-19
4.2.1. Flue Emissions From Wood Combustion (Residential) 4-20
4.2.1.1. Emissions Data 4-20
4.2.1.2. Activity Level Information 4-23
4.2.1.3. Emission Estimates 4-25
4.2.2. Stack Emissions From Wood Combustion (Industrial) 4-25
4.2.2.1. Emissions Data 4-25
4.2.2.2. Activity Level Information 4-28
4.2.2.3. Emission Estimates 4-29
4.2.3. Solid Waste from Wood Combustion (Residential and Industrial) 4-30
4.3. OIL COMBUSTION 4-35
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CONTENTS (continued)
4.3.1. Residential/Commercial Oil Combustion 4-36
4.3.2. Utility Sector and Industrial Oil Combustion 4-38
4.3.3. Used Oil Combustion 4-39
4.4. COAL COMBUSTION 4-39
4.4.1. Utilities and Industrial Boilers 4-40
4.4.2. Residential Coal Combustion 4-43
4.4.3. Solid Wastes from Coal Combustion 4-45
5. COMBUSTION SOURCES OF CDDs/CDFs: OTHER HIGH-TEMPERATURE
SOURCES 5-1
5.1. CEMENT KILNS 5-1
5.1.1. Process Description of Portland Cement Kilns 5-1
5.1.2. Cement Kilns That Burn Hazardous Waste 5-3
5.1.3. Air Pollution Control Devices 5-4
5.1.4. CDD/CDF Emissions Data 5-4
5.1.4.1. Emissions Data for 1989 Through 1996 5-5
5.1.4.2. Emissions Data for 1999 and 2000 5-7
5.1.4.3. Emission Factor Estimates for Cement Kilns Burning
Hazardous Waste 5-8
5.1.4.4. Emission Factor Estimates for Cement Kilns Burning
Nonhazardous Waste 5-9
5.1.4.5. Confidence Ratings of Emission Factor Estimates 5-9
5.1.5. Activity Level Information 5-10
5.1.6. National CDD/CDF Emission Estimates 5-10
5.1.6.1. Estimates for Reference Years 1987 and 1995 5-10
5.1.6.2. Estimates for Reference Year 2000 5-11
5.1.7. EPA Regulatory Activities 5-12
5.1.8. Solid Waste from Cement Manufacturing: Cement Kiln Dust 5-12
5.2. LIGHTWEIGHT AGGREGATE KILNS 5-15
5.3. ASPHALT MIXING PLANTS 5-16
5.4. PETROLEUM REFINING CATALYST REGENERATION 5-18
5.5. CIGARETTE SMOKING 5-23
5.6. PYROLYSIS OF BROMINATED FLAME RETARD ANTS 5-27
5.7. CARBON REACTIVATION FURNACES 5-27
5.8. KRAFT BLACK LIQUOR RECOVERY BOILERS 5-30
5.9. OTHER IDENTIFIED SOURCES 5-33
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. Emissions Data 6-1
6.1.2. Activity Level Information 6-1
6.1.2.1. 1987 and 1995 Activity Levels 6-2
6.1.2.2. 2000 Activity Level 6-2
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CONTENTS (continued)
6.1.3. Emission Estimates 6-3
6.2. ACCIDENTAL FIRES 6-3
6.2.1. Soot and Ash Studies 6-3
6.2.2. Fume and Smoke Studies 6-6
6.2.3. Data Evaluation 6-7
6.2.3.1. Structural Fires 6-7
6.2.3.2. Vehicle Fires 6-9
6.3. LANDFILL FIRES 6-10
6.3.1. Emissions Data 6-10
6.3.2. Activity Level Information and Emission Estimates 6-11
6.4. FOREST AND BRUSH FIRES 6-12
6.4.1. Emissions Data 6-12
6.4.2. Activity Level Information 6-16
6.4.2.1. Approach for Reference Year 2000 (Office of Air Quality
Planning and Standards [OAQPS]) 6-16
6.4.2.2. Approach for Reference Years 1987 and 1995 6-17
6.4.3. Emission Estimates 6-18
6.5. BACKYARD BARREL BURNING 6-18
6.5.1. Emissions Data 6-18
6.5.2. Activity Level Information 6-20
6.5.2.1. Summary of Barrel Burn Surveys 6-20
6.5.2.2. Estimates of Activity Level 6-22
6.5.2.3. Alternative Approach to Estimating Activity Level 6-24
6.5.3. Emission Estimates 6-24
6.5.4. Composition of Ash from Barrel Burning 6-25
6.6. RESIDENTIAL YARD WASTE BURNING 6-25
6.6.1. Emissions Data 6-25
6.6.2. Activity Level Information 6-26
6.6.3. Emission Estimate 6-27
6.7. LAND-CLEARING DEBRIS BURNING 6-27
6.7.1. Emissions Data 6-27
6.7.2. Activity Level Information 6-27
6.7.2.1. Residential Construction 6-28
6.7.2.2. Nonresidential Construction 6-28
6.7.2.3. Roadway Construction 6-28
6.7.2.4. Fuel Loading Factors 6-29
6.7.3. Emission Estimate 6-30
6.8. UNCONTROLLED COMBUSTION OF POLYCHLORINATED
BIPHENYLS 6-30
6.9. VOLCANOES 6-31
6.10. FIREWORKS 6-32
6.11. OPEN BURNING AND OPEN DETONATION OF ENERGETIC
MATERIALS 6-33
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CONTENTS (continued)
7. METAL SMELTING AND REFINING SOURCES OF CDDs/CDFs 7-1
7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING 7-1
7.1.1. Primary Copper Smelting and Refining 7-1
7.1.2. Primary Magnesium Smelting and Refining 7-3
7.1.3. Primary Nickel Smelting and Refining 7-5
7.1.4. Primary Aluminum Smelting and Refining 7-6
7.1.5. Primary Titanium Smelting and Refining 7-7
7.2. SECONDARY NONFERROUS METAL SMELTING 7-8
7.2.1. Secondary Aluminum Smelters 7-8
7.2.2. Secondary Copper Smelters 7-11
7.2.2.1. Emissions Data 7-12
7.2.2.2. Activity-Level Information 7-14
7.2.2.3. Emission Estimates 7-15
7.2.3. Secondary Lead Smelters 7-18
7.3. PRIMARY FERROUS METAL SMELTING/REFINING 7-20
7.3.1. Sinter Production 7-21
7.3.2. Coke Production 7-24
7.4. SECONDARY FERROUS METAL SMELTING/REFINING 7-25
7.5. FERROUS FOUNDRIES 7-27
7.6. SCRAP ELECTRIC WIRE RECOVERY 7-29
7.7. DRUM AND BARREL RECLAMATION FURNACES 7-31
7.8. SOLID WASTE FROM PRIMARY/SECONDARY IRON/STEEL MILLS/
FOUNDRIES 7-33
8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 8-1
8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS 8-1
8.1.1. Estimates of National Emissions in 1987 and 1995 8-4
8.1.2. Estimates of National Emissions in 2000 8-5
8.2. MANUFACTURE OF CHLORINE, CHLORINE DERIVATIVES, AND METAL
CHLORIDES 8-6
8.2.1. Manufacture of Chlorine 8-6
8.2.2. Manufacture of Chlorine Derivatives and Metal Chlorides 8-7
8.3. MANUFACTURE OF HALOGENATED ORGANIC CHEMICALS 8-7
8.3.1. Chlorophenols 8-8
8.3.1.1. Regulatory Actions for Chlorophenols 8-9
8.3.2. Chlorobenzenes 8-11
8.3.2.1. Regulatory Actions for Chlorobenzenes 8-12
8.3.3. Chlorobiphenyls 8-13
8.3.4. Polyvinyl Chloride 8-16
8.3.4.1. Wastewater 8-19
8.3.4.2. Wastewater Treatment Plant Solids 8-21
8.3.4.3. Stack Gas Emissions 8-23
8.3.4.4. Products 8-24
8.3.5. Other Aliphatic Chlorine Compounds 8-26
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CONTENTS (continued)
8.3.6. Dyes, Pigments, and Printing Inks 8-27
8.3.6.1. Dioxazine Dyes and Pigments 8-27
8.3.6.2. Phthalocyanine Dyes and Printing Inks 8-28
8.3.7. TSCA Dioxin/Furan Test Rule 8-29
8.3.8. Halogenated Pesticides and FIFRA Pesticides Data Call-In 8-30
8.4. OTHER CHEMICAL MANUFACTURING AND PROCESSING SOURCES . 8-40
8.4.1. Municipal Wastewater Treatment Plants 8-40
8.4.1.1. Sources 8-40
8.4.1.2. Releases to Water 8-42
8.4.1.3 Sewage Sludge Land Disposal 8-44
8.4.2. Drinking Water Treatment Plants 8-49
8.4.3. Soaps and Detergents 8-50
8.4.4. Textile Manufacturing and Dry Cleaning 8-52
9. BIOLOGICAL SOURCES OF CDDs/CDFs 9-1
9.1. BIOTRANSFORMATION OF CHLOROPHENOLS 9-1
9.2. BIOTRANSFORMATION OF HIGHER CDDs/CDFs 9-4
9.3. DIOXIN-LIKE COMPOUNDS IN ANIMAL MANURE 9-7
10. PHOTOCHEMICAL SOURCES OF CDDs/CDFs 10-1
10.1. PHOTOTRANSFORMATION OF CHLOROPHENOLS 10-1
10.2. PHOTOLYSIS OF HIGHER CDDs/CDFs 10-3
10.2.1. Photolysis in Water 10-3
10.2.2. Photolysis on Soil 10-4
10.2.3. Photolysis on Vegetation 10-5
10.2.4. Photolysis in Air 10-6
11. SOURCES OF DIOXIN-LIKE PCBs 11-1
11.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY 11-1
11.2. RELEASES OF COMMERCIAL PCBs 11-2
11.2.1. Approved PCB Disposal/Destruction Methods 11-6
11.2.1.1. Approved Incinerators/High-Efficiency Boilers 11-7
11.2.1.2. Approved Chemical Waste Landfills 11-7
11.2.1.3. Other Approved Disposal Methods 11-8
11.2.2. Emission Estimates 11-8
11.2.3. Accidental Releases of In-Service PCBs 11-9
11.2.3.1. Leaks and Spills 11-9
11.2.3.2. Accidental Fires 11-10
11.2.4. Municipal Wastewater Treatment 11-11
11.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 11-14
11.4. COMBUSTION SOURCES 11-14
11.4.1. Municipal Waste Combustors 11-14
11.4.2. Industrial Wood Combustion 11-15
11.4.3. Medical Waste Incineration 11-16
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CONTENTS (continued)
11.4.4. Tire Combustion 11-16
11.4.5. Cigarette Smoking 11-17
11.4.6. Sewage Sludge Incineration 11-18
11.4.7. Backyard Barrel Burning 11-19
11.4.8. Petroleum Refining Catalyst Regeneration 11-20
11.5. NATURAL SOURCES 11-20
11.5.1. Biotransformation of Other PCBs 11-21
11.5.2. Photochemical Transformation of Other PCBs 11-24
11.6. PAST USE OF COMMERCIAL PCBs 11-25
12. RESERVOIR SOURCES OF CDDs/CDFs AND DIOXIN-LIKE PCBs 12-1
12.1. POTENTIAL RESERVOIRS 12-1
12.2. CHARACTERIZATION OF RESERVOIR SOURCES 12-2
12.2.1. Soil 12-3
12.2.1.1. Potential Mass of Dioxin-Like Compounds Present 12-3
12.2.1.2. Mechanisms Responsible for Releases from Surface Soils .... 12-5
12.2.1.3. Estimated Annual Releases from Soil to Water 12-8
12.2.1.4. Estimated Annual Releases from Soil to Air 12-10
12.2.2. Water 12-12
12.2.2.1. Potential Mass of Dioxin-Like Compounds Present 12-12
12.2.2.2. Mechanisms Responsible for Supply to and Releases from
Water 12-13
12.2.3. Sediment 12-15
12.2.3.1. Potential Mass of Dioxin-Like Compounds Present 12-15
12.2.3.2. Mechanisms Responsible for Supply to and Releases from
Sediment 12-15
12.2.3.3. Releases from Sediment to Water 12-16
12.2.4. Biota 12-17
12.2.4.1. Potential Mass of Dioxin-Like Compounds Present 12-17
12.2.4.2. Mechanisms Responsible for Supply to and Releases from
Biota 12-18
12.2.4.3. Approaches for Measuring and Estimating Releases from
Biota 12-19
12.3. SUMMARY AND CONCLUSIONS 12-21
12.3.1. Reservoir Sources 12-21
12.3.2. Implications for Human Exposure 12-23
13. BALL CLAY 13-1
13.1. INTRODUCTION 13-1
13.2. CHARACTERISTICS OF MISSISSIPPI EMBAYMENT BALL CLAYS 13-1
13.3. LEVELS OF DIOXIN-LIKE COMPOUNDS IN BALL CLAY 13-2
13.4. EVIDENCE FOR BALL CLAY AS A NATURAL SOURCE 13-3
13.5. ENVIRONMENTAL RELEASES OF DIOXIN-LIKE COMPOUNDS FROM THE
MINING AND PROCESSING OF BALL CLAY 13-6
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CONTENTS (continued)
REFERENCES R-l
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LIST OF TABLES
Table 1-1.
Table 1-2.
Table 1-3.
Table 1-4.
Table 1-5.
Table 1-6.
Table 1-7.
Table 1-8.
Table 1-9.
Table 1-10.
Table 1-11.
Table 1-12.
Table 1-13.
Table 1-14.
Table 2-1.
Table 2-2.
The TEF scheme for I-TEQ
DF
. 1-19
The TEF scheme for dioxin-like PCBs, as determined by the World Health
Organization in 1994 1-20
The TEF scheme for TEQDFP-WHO98 1-21
Nomenclature for dioxin-like compounds 1-22
Known and suspected CDD/CDF sources 1-23
Inventory of contemporary releases (g TEQ/yr) of I-TEQDF from
known sources in the United States for references years 2000, 1995, and
1987 and preliminary release estimates for 2000 1-27
Inventory of contemporary releases (g TEQ/yr) of TEQDF-WHO98 from
known sources in the United States for reference years 2000, 1995, and
1987 and preliminary release estimates for 2000 1-32
Identification of products containing CDDs/CDFs (g I-TEQDF/yr) 1-37
Identification of products containing CDDs/CDFs (g TEQDF-WHO98/yr) ... 1-38
Confidence rating scheme for U.S. emission estimates 1-39
I-TEQDF emission factors used to develop national emission inventory
estimates of releases to air 1-40
TEQDF-WHO98 emission factors used to develop national emission inventory
estimates of releases to air 1-42
Releases (g TEQDF-WHO98) to the open environment from reservoir
sources
. 1-44
Sources in quantitative inventory ranked by releases to all media 1-45
Concentration of CDDs/CDFs on municipal incinerator fly ash at varying
temperatures 2-36
CDDs/CDFs formed from the thermolytic reaction of 690 mg benzene +
FeCl3 silica complex 2-37
Table 2-3. De novo formation of CDDs/CDFs after heating Mg-Al silicate, 4% charcoal,
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LIST OF TABLES (continued)
7% Cl, 1% CuCl2 • 2H2O at 300 °C 2-38
Table 3-1. Inventory of municipal waste combustors (MWCs) in 2000 by
technology, air pollution control device (APCD), size, and Annual
activity level (kg/yr) 3-59
Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 by
technology, air pollution control device (APCD), and annual
activity level (kg/yr) 3-61
Table 3-3. Inventory of municipal waste combustors (MWCs) in 1987 by
technology, air pollution control device (APCD), and annual
activity level (kg/yr) 3-63
Table 3-4. National average dioxin/furan congener concentrations for large
municipal waste combustors (ng/dscm @ 7% O2) 3-64
Table 3-5. National dioxin/furan TEQ emissions (g/yr) for large municipal
waste combustors 3-65
Table 3-6. CDD/CDF TEQ emission factors (ng TEQ/kg waste) for municipal
solid waste incineration 3-66
Table 3-7a. Annual I-TEQDF emissions from municipal waste combustors
(MWCs) operating in 1995 3-67
Table 3-7b. Annual TEQDF-WHO98 emissions from municipal waste combustors
(MWCs) operating in 1995 3-69
Table 3-8a. Annual I-TEQDF emissions to the air from municipal waste
combustors (MWCs) operating in 1987 3-71
Table 3-8b. Annual TEQDF-WHO98 emissions to the air from municipal waste
combustors (MWCs) operating in 1987 3-72
Table 3-9. Fly ash from a municipal incinerator (|_ig/kg) 3-73
Table 3-10. Comparison of the amount of TEQs generated annually in municipal
waste combustor ash 3-74
Table 3-11. Concentration of dioxin in fly ash samples from combustion of municipal
solid waste (ng/kg) 3-75
Table 3-12. Concentration of dioxin in fly ash samples from municipal solid waste 3-76
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LIST OF TABLES (continued)
Table 3-13. Dioxin and furan concentrations in municipal solid waste ash
5-77
Table 3-14a. CDD/CDF emission factors for hazardous waste incinerators and
boilers tested from 1993 to 1996 3-78
Table 3-14b. CDD/CDF emission factors for hazardous waste incinerators and
boilers tested in 2000 3-79
Table 3-15. CDD/CDF emission factors for halogen acid furnaces tested in 2000 3-80
Table 3-16. Estimated breakdown of facilities by air pollution control device (APCD) .. 3-81
Table 3-17. Summary of annual operating hours for each medical waste
incinerator (MWI) type 3-82
Table 3-18. EPA/Office of Air Quality Planning and Standards approach: estimated
nationwide I-TEQDF emissions for 1995 3-83
Table 3-19. EPA/Office of Air Quality Planning and Standards approach: particulate
matter emission limits for medical waste incinerator (MWI) types and
corresponding residence times in the secondary combustion chamber 3-84
Table 3-20. American Hospital Association approach: I-TEQDF emission factors
calculated for air pollution control device (APCD) 3-85
Table 3-21. American Hospital Association assumptions of the percent
distribution of air pollution control on medical waste incinerators
(MWIs) based on particulate matter (PM) emission limits 3-86
Table 3-22. American Hospital Association approach: estimated annual
nationwide I-TEQDF emissions 3-87
Table 3-23. Comparison between predicted residence times at medical waste
incinerators (MWIs) and residence times confirmed by state
agencies in the ORD telephone survey 3-88
Table 3-24. Summary of annual TEQ emissions from medical waste incinerators
(MWIs) for reference year 1987 (ORD approach) 3-89
Table 3-25. Office of Research and Development approach: TEQ emissions from
medical waste incinerators (MWIs) for reference year 1995 3-90
Table 3-26. Office of Research and Development approach: TEQ emissions from
medical waste incinerators (MWIs) for reference year 2000 3-91
03/04/05
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LIST OF TABLES (continued)
Table 3-27. Comparison of basic assumptions used in the ORD, OAQPS, and
AHA approaches to estimating nationwide CDD/CDF TEQ
emissions from medical waste incinerators (MWIs) for reference year
1995
Table 3-32.
Table 3-33.
Table 3-34.
Table 3-3 5.
Table 4-1.
Table 4-2.
Table 4-3.
Table 4-4.
Table 4-5.
Table 4-6.
3-92
Table 3-28.
Table 3-29.
Table 3-30.
Table 3 -31.
Congener-specific profile for Camellia Memorial Lawn Crematorium ....
Congener-specific profile for the Woodlawn Cemetery crematorium
Operational data for the Woodlawn Cemetery crematorium, scrubber inlet .
Congener-specific profile for the Camellia Memorial Lawn Crematorium
and the Woodlawn Cemetery crematorium
. 3-93
. 3-94
. 3-95
. 3-96
Congener-specific profile for the University of Georgia Veterinary
School
3-97
CDD/CDF emission factors for sewage sludge incinerators 3-98
CDD/CDF air emission factors for tire combustion 3-99
CDD/CDF emission factors for combustion of bleached-kraft mill
sludge in wood residue boilers 3-100
Descriptions and results of vehicle emission testing studies for CDDs and
CDFs 4-46
CDD/CDF congener emission factors for diesel-fueled automobiles (pg/L) . 4-48
CDD/CDF congener emission factors for diesel-fueled trucks (pg/L) 4-50
CDD/CDF congener emission factors for leaded gasoline-fueled automobiles
(pg/L) 4-52
CDD/CDF congener emission factors for unleaded gasoline-fueled
automobiles (without catalytic converters) (pg/L) 4-54
CDD/CDF congener emission factors for unleaded gasoline-fueled
automobiles (with catalytic converters) (pg/L) 4-56
Table 4-7. Total dioxin emission concentrations from heavy-duty diesel engines 4-58
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LIST OF TABLES (continued)
Table 4-8. Levels of 2,3,7,8-chlorine-substituted congeners and total CDDs/CDFs in
vehicle exhaust particles for gasoline engines and suspended particulate
matter (SPM) (pg/g) 4-59
Table 4-9. Levels of 2,3,7,8-chlorine-substituted congeners and total CDDs/CDFs in
vehicle exhaust particles for diesel engines (pg/g) 4-60
Table 4-10. European tunnel study test results (pg/m3) 4-61
Table 4-11. Baltimore Harbor tunnel study: estimated emission factors for heavy-duty
diesel vehicles (pg/km) 4-62
Table 4-12. Average CDD/CDF concentration in flue gas 4-64
Table 4-13. Results from Environment Canada residential wood stove analysis (pg TEQ/
kg wood) 4-65
Table 4-14. CDD/CDF mean emission factors for industrial wood combustors (ng/kg
wood) 4-66
Table 4-15. NCASI CDD/CDF TEQ concentrations and emissions for wood residue-fired
boilers 4-67
Table 4-16. CDD/CDF concentrations in residential chimney soot from wood
stoves and fireplaces (ng/kg) 4-68
Table 4-17. CDD/CDF concentrations in bottom ash from residential wood stoves and
fireplaces (ng/kg) 4-69
Table 4-18. CDD/CDF concentrations in chimney soot (Bavaria, Germany) 4-70
Table 4-19. Fly ash from wood-working industry (ng/kg) 4-71
Table 4-20. Electrostatic precipitator waste ash from wood-fired industrial boiler (ng/
kg) 4-72
Table 4-21. Estimated CDD/CDF emission factors for oil-fired residential furnaces .... 4-73
Table 4-22. CDD/CDF emission factors for oil-fired utility/industrial boilers (pg/L oil) . 4-74
Table 4-23. CDD/CDF concentrations in stack emissions from U.S. coal-fired power
plants (pg/Nm3) 4-75
Table 4-24. Characteristics of U.S. coal-fired power plants tested by the U.S.
03/04/05
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LIST OF TABLES (continued)
Department of Energy 4-76
Table 4-25. CDD/CDF emission factors for coal-fired utility/industrial power plants (ng/
kg coal) 4-77
Table 4-26. CDD/CDF emission factors for residential coal combustors (ng/kg coal) . . . 4-78
Table 4-27. Coal-fired utility solid wastes 4-79
Table 5-1. CDD/CDF emission factors for cement kilns burning hazardous waste for
reference years 1987 and 1995 5-35
Table 5-2. CDD/CDF emission factors for cement kilns burning hazardous waste for
reference year 2000 5-36
Table 5-3. CDD/CDF emission factors for cement kilns burning nonhazardous waste for
reference years 1987, 1995, and 2000 5-37
Table 5-4. National emission estimates for cement kilns for reference years 1987 and
1995 5-38
Table 5-5. National emission estimates for cement kilns for reference year 2000 5-38
Table 5-6. CDD/CDF concentrations in ash samples from cement kiln electrostatic
precipitator and lightweight aggregate (LWA) kiln fabric filter
(ng/kg) 5-39
Table 5-7. CDD/CDF estimates in cement kiln dust (CKD) for reference years
1987, 1995, and 2000 5-40
Table 5-8. Congener-specific profile for hot-mix asphalt plants 5-41
Table 5-9. CDD/CDF emission factors for petroleum catalytic reforming units 5-42
Table 5-10. CDD concentrations in Japanese cigarettes, smoke, and ash 5-43
Table 5-11. CDD/CDF emissions in cigarette smoke 5-44
Table 5-12. CDD/CDF concentrations in cigarette tobacco 5-45
Table 5-13. CDD/CDF mean emission factors (ng/kg feed) for black liquor recovery
boilers 5-46
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LIST OF TABLES (continued)
Table 5-14.
CDD/CDF TEQ emission factors and emission estimates from Kraft
recovery furnaces and Kraft lime kilns
Table 5-15. Concentrations of CDD/CDF in candle materials and emissions
Table 6-3.
Table 6-4.
Table 6-5.
Table 6-6.
Table 6-7.
Table 6-8.
Table 7-1.
Table 7-2.
Table 7-3.
Table 7-4.
Table 7-5.
Table 7-6.
Table 7-7.
Table 7-8.
. . . 5-47
.. . 5-47
Table 6-1. CDD/CDF emission factors for a landfill flare 6-34
Table 6-2. CDD/CDF emission factors for forest fires 6-35
Forest fire fuel loading factors 6-36
CDD/CDF air emission factors from barrel burning of household waste .... 6-37
CDD/CDF analysis for composite ash samples from barrel burning (ng/kg
of ash) 6-38
PCB analysis for composite ash samples from barrel burning (ng/kg of
ash)
6-39
CDDs/CDFs in dust fall and ashes from volcanoes 6-40
Residue of HpCDD/HpCDF and OCDD/OCDF in paper cartridges and
charges of selected pyrotechnic products (ng/kg) 6-40
CDD/CDF emission concentrations for primary copper smelters 7-34
CDD/CDF emissions data from primary and secondary copper and secondary
lead smelters 7-35
CDD/CDF emission factors for secondary aluminum smelters (ng/kg scrap
feed) 7-36
CDD/CDF emission factors for secondary copper smelters (ng/kg scrap
feed) 7-38
CDD/CDF emission estimates for Canadian coke oven facilities, blast
furnace facilities, and electric arc furnaces 7-39
CDD/CDF emission factors for secondary lead smelters 7-41
CDD/CDF emission factors for sinter plants (ng/kg sinter) 7-42
Operating parameters for U.S. iron ore sinter plants 7-43
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LIST OF TABLES (continued)
Table 7-9. CDD/CDF emission concentrations and rates for Canadian electric arc
furnaces 7-44
Table 7-10. CDD/CDF emission factors for a U.S. ferrous foundry 7-45
Table 7-11. Congener-specific profile for ferrous foundries 7-46
Table 7-12. CDD/CDF emission factors for a scrap wire incinerator 7-47
Table 7-13. CDD/CDF concentrations in fly ash and ash/soil at metal recovery sites .... 7-48
Table 7-14. CDD/CDF emission factors for a drum and barrel reclamation facility 7-49
Table 8-1. CDD/CDF concentrations in pulp and paper mill bleached pulp,
wastewater sludge, and effluent (circa 1988) 8-54
Table 8-2. CDD/CDF concentrations in pulp and paper mill bleached pulp,
wastewater sludge, and effluent (mid-1990s) 8-55
Table 8-3. Summary of bleached chemical pulp and paper mill discharges
of 2,3,7,8-TCDD and 2,3,7,8-TCDF (g/yr) 8-56
Table 8-4. CDD/CDF TEQ concentrations and emissions for the paper and pulp
industry by source 8-57
Table 8-5. CDD/CDF concentrations in graphite electrode sludge from chlorine
production (ug/kg) 8-58
Table 8-6. CDD/CDF concentrations in metal chlorides (ug/kg) 8-59
Table 8-7. CDD/CDF concentrations in mono- through tetrachlorophenols (mg/kg) . . . 8-60
Table 8-8. CDD/CDF concentrations (historical and current) in technical-grade
Pentachlorophenol (PCP) products (ug/kg) 8-61
Table 8-9. Historical CDD/CDF concentrations in pentachlorophenol-Na (PCP-Na)
(ug/kg) 8-63
Table 8-10. Summary of specific dioxin-containing wastes that must comply with
land disposal restrictions 8-64
Table 8-11. CDD/CDF concentrations in chlorobenzenes (ug/kg) 8-66
Table 8-12. Concentrations of CDD/CDF congener groups in unused commercial
03/04/05
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LIST OF TABLES (continued)
Polychlorinated biphenyl (PCB) mixtures 8-67
Table 8-13. 2,3,7,8-Substituted congener concentrations in unused polychlorinated
biphenyl (PCB) mixtures (ug/kg) 8-68
Table 8-14. Reported CDD/CDF concentrations in wastes from polyvinyl chloride
(PVC) manufacture (ug/kg) 8-69
Table 8-15. CDD/CDF measurements in treated wastewater and wastewater solids
from U.S. EDC/VCM/PVC manufacturers 8-70
Table 8-16. Emissions data for wastewater from PVC/EDC/VCM manufacturing
facilities
. 8-72
Table 8-17. Emissions data for wastewater from chlor-alkali production facilities 8-73
Table 8-18. Congener-specific Ian releases for PVC/EDC/VCM manufacturing
facilities 8-74
Table 8-19. Congener-specific air emissions for PVC/EDC/VCM manufacturing
facilities
. 8-75
Table 8-20. Congener-specific air emissions for chlor-alkali production facilities 8-76
Table 8-21. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC
manufacturers 8-77
Table 8-22. CDD/CDF concentrations in samples of dioxazine dyes and pigments
(ug/kg) (Canada) 8-79
Table 8-23. CDD/CDF concentrations in printing inks (ng/kg) (Germany) 8-81
Table 8-24. Chemicals requiring Toxic Substances Control Act Section 4 testing under the
dioxin/furan rule 8-82
Table 8-25. Congeners and limits of quantitation (LOQ) for which quantitation is
required under the dioxin/furan test rule and pesticide data call-in 8-83
Table 8-26. Precursor chemicals subject to reporting requirements under Toxic
Substances Control Act Section 8 8-84
Table 8-27. Results of analytical testing for dioxins and furans in the chemicals
tested to date under Section 4 of the dioxin/furan test rule
.. . 8-85
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LIST OF TABLES (continued)
Table 8-28. CDD/CDF concentrations in chloranil and carbazole violet samples
analyzed pursuant to the EPA dioxin/furan test rule (ug/kg) 8-86
Table 8-29. Status of first pesticide data call-in: pesticides suspected of having the
potential to become contaminated with dioxins if synthesized under
conditions favoring dioxin formation 8-87
Table 8-30. Status of second pesticide data call-in: pesticides suspected of being
contaminated with dioxins 8-92
Table 8-31. Summary of analytical data submitted to EPA in response to pesticide
data call-in(s) 8-95
Table 8-32. Summary of results for CDDs and CDFs in technical 2,4-D and 2,4-D
ester herbicides 8-96
Table 8-33. CDD/CDF concentrations in samples of 2,4-D and pesticide formulations
containing 2,4-D (ug/kg) 8-97
Table 8-34. Mean CDD/CDF measurements in effluents from nine U.S. publicly
owned treatment works (POTWs) 8-99
Table 8-35. Effluent concentrations of CDDs/CDFs from publicly owned treatment
works in Mississippi (pg/L) 8-100
Table 8-36. CDD/CDF concentrations measured in EPA's 1998/1999 National Sewage
Sludge Survey 8-101
Table 8-37. CDD/CDF concentrations measured in 99 sludges collected from U.S.
publicly owned treatment works (POTWs) during 1994 8-102
Table 8-38. Sewage sludge concentrations from publicly owned treatment works in
Mississippi (ng/kg dry matter) 8-103
Table 8-39. CDD/CDF concentrations measured in 1999 from a publicly owned treatment
works facility in Ohio 8-104
Table 8-40. CDD/CDF concentrations measured in the EPA 2001 National Sewage
Sludge Survey 8-105
Table 8-41. Quantity of sewage sludge disposed of annually for the reference year
1987 by primary, secondary, and advanced treatment publicly owned
treatment works and potential dioxin TEQ releases 8-106
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LIST OF TABLES (continued)
Table 8-42. Quantity of sewage sludge disposed of annually for the reference year
1995 by primary, secondary, or advanced treatment publicly owned
Treatment works and potential dioxin TEQ releases 8-107
Table 8-43. Quantity of sewage sludge disposed of annually for the reference year
2000 by primary, secondary, and advanced treatment publicly owned
treatment works and potential dioxin TEQ releases 8-108
Table 8-44. Biosolids disposal practices for reference year 2000 8-109
Table 8-45. CDD/CDF concentrations in Swedish liquid soap, tall oil, and tall
resin 8-110
Table 9-1. Estimated quantity of animal manure produced in the United States in
2000 9-9
Table 9-2. CDD and CDF concentrations (ng/kg dry weight) in samples of animal
manure in the United Kingdom 9-10
Table 11-1. Confidence rating classes for 2000 releases from all known and suspected
source categories of dioxin-like PCBs 11-28
Table 11-2. Inventory of contemporary releases of dioxin-like PCBs (g TEQP-
WHO98/yr) in the United States for 1987, 1995, and 2000 and preliminary
Release estimates of dioxin-like PCBs for 2000 (g TEQP-WHO98/yr) 11-29
Table 11-3. Weight percent concentrations of dioxin-like PCBs in aroclors, clophens,
and kanechlors 11-30
Table 11-4. Disposal requirements for PCBs andPCB items 11-34
Table 11-5. Off-site transfers of PCBs reported in the Toxics Release Inventory (TRI)
(1988-2000) 11-36
Table 11-6. Releases of PCBs reported in the Toxics Release Inventory (TRI) (1988-
2000) 11-37
Table 11-7. Aroclor concentrations measured in EPA's National Sewage Sludge
Survey 11-38
Table 11-8. Dioxin-like PCB concentrations measured in sludges collected from 74 U.S.
publicly owned treatment works (POTWs) during 1994 11-39
Table 11-9. Dioxin-like PCB concentrations in sewage sludge collected from a U.S.
03/04/05
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LIST OF TABLES (continued)
publicly owned treatment works during 1999 11-40
Table 11-10. Quantity of sewage sludge disposed of annually in 1989 by primary,
secondary, or advanced treatment publicly owned treatment works (POTWs)
and potential dioxin-like PCB TEQ releases 11-41
Table 11-11. Quantity of sewage sludge disposed of annually in 1995 by primary,
secondary, or advanced treatment publicly owned treatment works
(POTWs) and potential dioxin-like PCB TEQ releases 11-42
Table 11-12. Quantity of sewage sludge disposed of annually in 2000 by primary,
secondary, or advanced treatment publicly owned treatment works (POTWs)
and potential dioxin-like PCB TEQ releases 11-43
Table 11-13. PCB congener group emission factors for industrial wood combustors .... 11-44
Table 11-14. PCB congener group emission factors for medical waste incinerators
(MWIs) 11-45
Table 11-15. PCB congener group emission factors for a tire combustor 11-46
Table 11-16. Dioxin-like PCB concentrations in cigarette tobacco in brands from various
countries (pg/pack) 11-47
Table 11-17. Dioxin-like PCB concentrations in stack gas collected from a U.S. sewage
sludge incinerator 11-48
Table 11-18. Dioxin-like PCB emission factors from backyard barrel burning 11-49
Table 11-19. PCB congener group emission factors for a petroleum catalytic reforming
unit 11-50
Table 11-20. Estimated tropospheric half-lives of dioxin-like PCBs with respect to gas-
phase reaction with the OH radical 11-51
Table 11-21. Estimated PCB loads in the global environment as of 1985 11-52
Table 11-22. Estimated domestic sales of aroclors and releases of PCBs, 1957-1974
(metric tons) 11-53
Table 11-23. Estimated U.S. usage of PCBs by use category, 1930-1975 11-54
Table 11-24. Estimated direct releases of Aroclors to the U.S. environment, 1930-1974
(metric tons) 11-55
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LIST OF TABLES (continued)
Table 11-25. Estimated releases of dioxin-like PCB TEQs to the U.S. environment,
1930-1977 11-56
Table 12-1. Historical production, sales, and usage of 2,4-dichlorophenoxyacetic acid
(2,4-D) (metric tons) 12-25
Table 12-2. Historical production, sales, and usage of 2,4,5-trichlorophenoxyacetic acid
(2,4,5-T) (metric tons) 12-28
Table 12-3. CDD/CDF concentrations in recent sample of 2,4,5-trichlorophenoxyacetic
acid (2,4,5-T) 12-30
Table 12-4. PCB 138 fluxes predicted by Harner et al. (1995) 12-31
Table 12-5. Summary of flux calculations for total PCBs in Green Bay, 1989 12-32
Table 12-6. Comparison of estimated PCB concentrations with observed values 12-33
Table 13-1. Concentrations of CDDs determined in eight ball clay samples in the
United States 13-7
Table 13-2. Comparison of the mean CDD/CDF congener group distribution in ball
clay with the mean congener group distributions in urban and rural soils
in North America 13-8
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LIST OF FIGURES
Figure 1-1. Chemical structure of 2,3,7,8-TCDD and related compounds 1-49
Figure 1-2. Estimated CDD/CDF I-TEQ emissions to air from combustion sources in the
United States (reference year: 1987) 1-50
Figure 1-3. Estimated CDD/CDF I-TEQ emissions to air from combustion sources in the
United States (reference year: 1995) 1-51
Figure 1-4. Estimated CDD/CDF I-TEQ emissions to air from combustion sources in the
United States (reference year: 2000) 1-52
Figure 1-5. Comparison of estimates of annual I-TEQ emissions to air (g I-TEQ/yr) for
reference years 1987, 1995, and 2000 1-53
Figure 1-6. Estimated CDD/CDF WHO-TEQ emissions to air from combustion sources
in the United States (reference year: 1987) 1-54
Figure 1-7. Estimated CDD/CDF WHO-TEQ emissions to air from combustion sources
in the United States (reference year: 1995) 1-55
Figure 1-8. Estimated CDD/CDF WHO-TEQ emissions to air from combustion sources
in the United States (reference year: 2000) 1-56
Figure 1-9. Comparison of estimates of annual WHO-TEQ emissions to air (g WHO-
TEQ/yr) for reference years 1987, 1995, and 2000 1-57
Figure 1-10. The congener profiles (as fractional distributions to total CDD/CDF) of
anthropogenic sources of CDDs/CDFs in the United States 1-58
Figure 2-1. Typical CDD and CDF congener distribution in contemporary municipal solid
waste (MSW) 2-39
Figure 2-2. The de novo synthesis of CDDs/CDFs from heating carbon particulate at
300 °C at varying retention times 2-40
Figure 2-3. Temperature effects on CDD/CDF formation 2-41
Figure 3-1. Typical mass burn waterwall municipal solid waste incinerator 3-101
Figure 3-2. Typical mass burn rotary kiln combustor 3-102
Figure 3-3. Typical modular starved-air combustor with transfer rams 3-103
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LIST OF FIGURES (continued)
Figure 3-4. Typical modular excess-air combustor 3-104
Figure 3-5. Typical dedicated refuse-derived fuel-fired spreader stoker boiler 3-105
Figure 3-6. Fluidized-bed refuse-derived fuel incinerator 3-106
Figure 3-7. Municipal waste combustor design classes for 1987 3-107
Figure 3-8. Municipal waste combustor design classes for 1995 3-108
Figure 3-9. Municipal waste combustor design classes for 2000 3-109
Figure 3-10. Congener and congener group profiles for air emissions from a
mass-burn waterwall municipal waste combustor, equipped with a dry
scrubber and fabric filter 3-110
Figure 3-11. 2,3,7,8-TCDD frequency distribution (negative natural log
concentration) 3-111
Figure 3-12. 1,2,3,7,8-PeCDD frequency distribution (negative natural log
concentration) 3-112
Figure 3-13. Congener profile for air emissions from hazardous waste incinerators 3-113
Figure 3-14. Congener and congener group profiles for air emissions from boilers
and industrial furnaces burning hazardous waste 3-114
Figure 3-15. Congener and congener group profiles for air emissions from medical
waste incinerators without air pollution control devices 3-115
Figure 3-16. Congener and congener group profiles for air emissions from medical
waste incinerators equipped with a wet scrubber and fabric filter 3-116
Figure 3-17. Congener and congener group profiles for air emissions from the
crematoria at Camellia Memorial Lawn Crematorium and Woodlawn
Cemetery 3-117
Figure 3-18. Congener profile for air emissions from the University of Georgia animal
crematorium 3-118
Figure 3-19. Congener and congener group profiles for air emissions from sewage
sludge incinerators 3-119
Figure 3-20. Congener and congener group profiles for air emissions from a tire
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LIST OF FIGURES (continued)
Combustor 3-120
Figure 4-1. Congener and congener group profiles for air emissions from diesel-fueled
vehicles 4-80
Figure 4-2. Congener and congener group profiles for air emissions from leaded gas-
fueled vehicles 4-81
Figure 4-3. Congener and congener group profiles for air emissions from unleaded gas-
fueled vehicles 4-82
Figure 4-4. Tunnel air concentrations 4-83
Figure 4-5a. Congener and congener group profiles for air emissions from industrial
wood combustors 4-84
Figure 4-5b. Congener and congener group profiles for air emissions from bleached
Kraft mill bark combustors 4-85
Figure 4-6. Congener group profile for air emissions from residential oil-fueled
furnaces 4-86
Figure 4-7. Congener and congener group profiles for air emissions from industrial
Oil-fueled boilers 4-87
Figure 4-8. Congener and congener group profiles for air emissions from industrial/utility
coal-fueled combustors 4-88
Figure 4-9. Congener group profile for air emissions from residential coal-fueled
combustors 4-89
Figure 5-1. Congener profile for air emissions from cement kilns burning hazardous
waste for reference years 1987 and 1995 5-48
Figure 5-2. Congener profile for air emissions from cement kilns burning hazardous
waste for reference year 2000 5-49
Figure 5-3. Congener profile for air emissions from cement kilns burning nonhazardous
waste for reference years 1987, 1995, and 2000 5-50
Figure 5-4. Congener and congener group profiles for air emissions from petroleum
catalytic reforming units 5-51
Figure 5-5. CDD profiles for Japanese cigarettes, smoke, and ash 5-52
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LIST OF FIGURES (continued)
Figure 5-6. Congener group profiles for mainstream and sidestream cigarette smoke . . . 5-53
Figure 5-7. Congener group profiles for cigarette tobacco from various countries 5-54
Figure 5-8. Congener and congener group profiles for air emissions from Kraft black
liquor recovery boilers 5-55
Figure 6-1. Congener profile for landfill flare air emissions 6-41
Figure 6-2. Congener profile for forest fire simulation approach emissions 6-42
Figure 7-1. Congener and congener group profiles for air emissions from secondary
aluminum smelters 7-50
Figure 7-2a. Congener group profile for air emissions from a secondary copper smelter . . 7-51
Figure 7-2b. Congener and congener group profiles for a closed secondary copper
smelter 7-52
Figure 7-3. Congener and congener group profiles for air emissions from secondary
lead smelters 7-53
Figure 7-4. Congener profiles for air emissions from U.S. iron ore sinter plants 7-54
Figure 7-5. Congener group profile for air emissions from a scrap wire incinerator 7-55
Figure 7-6. Congener group profile for air emissions from a drum incinerator 7-56
Figure 8-1. 104 Mill Study full congener analysis results for pulp 8-111
Figure 8-2. 104 Mill Study full congener analysis results for sludge 8-112
Figure 8-3. 104 Mill Study full congener analysis results for effluent 8-113
Figure 8-4. Congener and congener group profiles for technical-grade PCP 8-114
Figure 8-5. Congener profile for 2,4-D (salts and esters) 8-115
Figure 8-6. Congener profiles for sewage sludge 8-116
Figure 12-1. Fluxes among reservoirs 12-34
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LIST OF ABBREVIATIONS AND ACRONYMS
AHA
AMSA
APCD
BDDs
BDFs
Btu
CaCl2
CARS
CBI
CDD
CDF
CFR
CSF
CKD
CO
CO2
CuCl
CuCl2
D
D
DBF
DCBz
DCI
DCP
DL
dscm
DSI
EDC
EIA
American Hospital Association
Association of Metropolitan Sewerage Agencies
Air pollution control device
Polybrominated dibenzo-p-dioxins
Polybrominated dibenzofurans
British thermal unit
Calcium chloride
California Air Resources Board
Confidential business information
Polychlorinated dibenzo-p-dioxin
Polychlorinated dibenzofuran
Code of Federal Regulations
Confidential Statement of Formula
Cement Kiln Dust
Carbon Monoxide
Carbon Dioxide
Copper (I) chloride
Copper (II) chloride
Symbol for Congener Class: Dibenzo-p-dioxin
Symbol for di (i.e., Two Halogen Substitution)
Dibenzofuran
Di chl orob enzene
Data Call-In
Dichlorophenol
Detection limit
Dry standard cubic meter
Dry sorbent injection
Ethyl ene di chloride
Energy Information Administration
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LIST OF ABBREVIATIONS AND ACRONYMS (continued)
EPA U.S. Environmental Protection Agency
EPRI Electric Power Research Institute
ESP Electrostatic precipitator
FF Fabric filter
FCEM Field Chemical Emissions Measurement
FeCl3 Ferric (iron) chloride
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
KC1 Potassium chloride
LOQ Limit of quantitation
MB-WW Mass burn waterwall
MCBz Monochlorobenzene
MgCl2 Magnesium chloride
MgO Magnesium oxide
MSW Municipal solid waste
MWI Medical waste incinerator
NaCl Sodium chloride
NaOCl Soldium hypochlorite
NCASI National Council of the Paper Industry for Air and Stream Improvement
MC12 Nickel chloride
NiO Nickel oxide
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Nm3
NMOC
OAQPS
02
OH
OPP
ORD
OSW
Pb
PCA
PCB
PCP
PCP-Na
PeCB
PeCBz
PM
POTW
ppb
ppm
ppmv
ppt
PVC
QA/QC
RCRA
RDF
SIC
SNUR
SO2
TCBz
TCDD
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LIST OF ABBREVIATIONS AND ACRONYMS (continued)
Standard cubic meter
Nonmethane organic compound
Office of Air Quality Planning and Standards
Molecular oxygen
Hydroxide ion
Office of Pesticide Programs
Office of Research and Development
Office of Solid Waste
Lead
Portland Cement Association
Polychlorinated biphenyl
Pentachl orophenol
Pentachlorophenate
Pentachl orobiphenyl
Pentachl orob enzene
Parti cul ate matter
Publicly owned treatment works
Parts Per Billion
Parts Per Million
Parts per million (volume basis)
Parts per trillion
Polyvinyl chloride
Quality Assurance/Quality Control
Resource Conservation and Recovery Act
Refuse-derived fuel
Standard Industrial Classification
Significant New Use Rule
Sulfur dioxide
Tri chl orob enzene
2,3,7,8-tetrachlorobidenzo-/>-dioxin
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LIST OF ABBREVIATIONS AND ACRONYMS (continued)
TCDF 2,3,.7,8-tetrachlorobidenzofuran
TeCB Tetrachlorobiphenyl
TeCP Tetrachlorophenol
TEF Toxicity equivalency factor
TEQ Toxicity equivalent
TEQ/yr Toxicity equivalents per year
TiCl4 Titanium tetrachloride
TrCB Trichlorobiphenyl
TrCP Trichlorophenol
TRI Toxics Release Inventory
TSCA Toxic Substances Control Act
2,4-D 2,4-Dichlorophenoxyacetic acid
2,4-DB 4-(2,4-Dichlorophenoxy) butyric acid
2,4-DCP 2,4-Dichlorophenol
2,4-DP 2-(2,4-Dichlorophenoxy) propionic acid
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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FOREWORD
The purpose of this report is to present an inventory of sources and environmental
releases of dioxin-like compounds in the United States. This inventory is associated with three
distinct reference years: 1987, 1995, and 2000. The presentation of information in this manner
permits the ranking of sources by magnitude of annual release and allows for the evaluation of
environmental trends over time.
The term "dioxin-like" includes congeners of poly chlorinated dibenzo-p-dioxins (CDDs),
polychlorinated dibenzofurans (CDFs) having chlorine atoms in the 2,3,7,8 positions on the
molecule, and certain coplanar-substituted polychlorinated biphenyls (PCBs). Dioxin-like refers
to the fact that these compounds have similar chemical structure and physical-chemical
properties and invoke a common battery of toxic response. Because of their hydrophobic nature
and resistance towards metabolism, these chemicals persist and bioaccumulate in fatty tissues of
animals and humans. Consequently, the principal route of chronic population exposure is
through the dietary consumption of animal fats, fish, shellfish, and dairy products. Dioxin-like
compounds are persistent in soils and sediments, with environmental half-lives ranging from
years to several decades. Understanding the sources and environmental releases of dioxin-like
compounds is fundamental to ultimately linking sources with population exposures. It is through
such understanding that actions can be taken to reduce human exposures.
This current inventory is an update of an external review draft report entitled, The
Inventory of Sources ofDioxin in the United States (EPA/600/P-98/002Aa), dated April 1998.
The 1998 draft inventory presented annual estimates of environmental releases for reference
years 1987 and 1995. A meeting of scientific and engineering experts was convened June 3-4,
1998, to review the scientific soundness of EPA's dioxin inventory. Overall, the reviewers found
the inventory report to be comprehensive and well documented and the "emission factor
approach" that was used to develop the inventory to be scientifically defensible. The review
committee recommended that EPA (a) take a less conservative approach for including data on
emissions of dioxin-like compounds from sources, especially data from foreign countries and
those found in the nonpeer-reviewed literature; (b) adopt a qualitative ranking system that clearly
indicates the relative amount of uncertainty behind the calculations of annual releases of
dioxin-like compounds; (c) present the inventory of sources and environmental releases specific
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to the reference years, because technologies and emissions of dioxin from sources changes over
time; and (d) present the dioxin inventory as a summary table of sources and estimated annual
releases, including quantifiable as well as poorly understood sources. The current inventory
reflects comments made by the review committee and also represents an update with the
inclusion of a third reference year, 2000.
This updated inventory of sources and environmental releases of dioxin-like compounds
concludes that, between 1987 and 2000, there was an approximately 89% reduction in the release
of dioxin-like compounds to the circulating environment of the United States from all known
sources combined. Annual emission estimates (TEQDF-WHO98) of releases of CDDs/CDFs to
air, water, and land from reasonably quantifiable sources are approximately 1,529 g in reference
year 2000; 3,280 g in reference year 1995; and 13,962 g in reference year 1987. In 1987 and
1995, the leading sources of dioxin emissions to the U.S. environment were municipal waste
combustors. The inventory also identifies bleached chlorine pulp and paper mills as a significant
source of dioxin to the aquatic environment in 1987 but a minor source in 1995 and 2000. The
inventory concludes that the major source of dioxin in 2000 was the uncontrolled burning of
refuse in backyard burn barrels in rural areas of the United States.
The reduction in environmental releases of dioxin-like compounds from 1987 to 2000 is
attributable to source-specific regulations, improvements in source technology, advancements in
the pollution control technologies specific to controlling dioxin discharges and releases, and the
voluntary actions of U.S. industries to reduce or prevent dioxin releases.
Peter W. Preuss, Ph.D.
Director
National Center for Environmental Assessment
Office of Research and Development
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PREFACE
This external review draft report presents an inventory of all known sources and
environmental releases of dioxin-like compounds in the United States associated with reference
years 1987, 1995, and 2000. This perspective allows for the observation of time trends of
releases of dioxin-like compounds to the open and circulating environment from industrial,
combustion, chemical, and ferrous and nonferrous metal smelting processes as they are
configured and operated in the United States. The assessment was prepared by the National
Center for Environmental Assessment, which is the health risk assessment program in the Office
of Research and Development.
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AUTHORS, CONTRIBUTORS, AND REVIEWERS
The National Center for Environmental Assessment (NCEA) was responsible for the
preparation of this document. Major portions of this report were prepared by Versar, Inc. under
EPA Contract No. 68-W-99-041. David Cleverly of NCEA served as the EPA Work Assignment
Manager, providing overall direction and coordination of the project, as well as an author of
several chapters.
Authors
David Cleverly, Environmental Scientist
National Center for Environmental Assessment (8623D)
Office of Research and Development
U.S. Environmental Protection Agency
Washington, DC 20460
Marit Espevik Randall
Versar, Incorporated
Springfield, VA
Charles Peck
Versar, Incorporated
Springfield, VA
Kelly McAloon
Versar, Incorporated
Springfield, VA
Ronald Lee
Versar, Incorporated
Springfield, VA
Greg Schweer,
Office of Pollution Prevention and Toxics,
Washington, DC.
Karie Traub Riley
Versar, Incorporated
Springfield, VA
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AUTHORS, CONTRIBUTORS, AND REVIEWERS (continued)
Contributors
Frank Behan, Office of Solid Waste, Office of Solid Waste and Emergency Response, U.S.
Environmental Protection Agency, Washington, DC.
Laurel Driver, Office of Air Quality Planning and Standards, Office of Air and Radiation, U.S.
Environmental Protection Agency, Research Triangle Park, NC.
Marietta Echeverria, National Center for Environmental Assessment, Office of Research and
Development, U.S. Environmental Protection Agency, Washington, DC.
Joseph Ferrario, Environmental Chemistry Laboratory, Office of Pesticide Programs, Office of
Prevention, Pesticides and Toxic Substances, U.S. Environmental Protection Agency, Stennis
Space Center, MS.
Roy Huntley,Office of Air Quality Planning and Standards, Office of Air and Radiation, U.S.
Environmental Protection Agency, Research Triangle Park, NC.
John Schaum, National Center for Environmental Assessment, Office of Research and
Development, U.S. Environmental Protection Agency, Washington, DC.
Walt Stevenson, Office of Air Quality Planning and Standards, Office of Air and Radiation, U.S.
Environmental Protection Agency, Research Triangle Park, NC.
Dwain Winters, Office of Pollution Prevention and Toxics, Office of Prevention, Pesticides and
Toxic Substances, U.S. Environmental Protection Agency, Washington, DC.
Reviewers
Internal EPA Review: Internal EPA review occurred from May 2 through June 5, 2003. The key
reviewers included the following individuals and offices:
Elmer Akin, USEPA REGION 4, Atlanta, GA.
Don Anderson, Office of Science and Technology, Office of Water, Washington, DC.
John D Bachmann, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Angela L. Bandemehr, Office of International Affaires, Washington, DC.
Frank Behan, Office of Solid Waste, Washington, DC.
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AUTHORS, CONTRIBUTORS, AND REVIEWERS (continued)
Tom Braverman, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Laurel Driver, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Dale Evarts, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Brian Gullett, National Risk Management Laboratory, Research Triangle Park, NC.
Bob Holloway, Office of Solid Waste, Washington, DC.
Roy Huntley, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Phil Lorang, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Ed Ohanian, Office of Water, Washington, DC.
Debbie Sisco, Office of Pesticide Programs, Washington, DC.
Alan Rubin, Office of Water, Washington, DC.
John Schaum, National Center for Environmental Assessment, Washington, DC.
Laurie Schuda, National Center for Environmental Assessment, Washington, DC.
Greg Schweer, Office of Pollution Prevention and Toxics, Washington, DC.
Joe Somers, Office of Transportation and Air Quality, Ann Arbor, MI.
Walt Stevenson, Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Dwain Winters, Office of Pollution Prevention and Toxics, Washington, DC.
Donn Viviani, Office of Policy, Economics and Innovation, Washington, DC.
External Peer Review: The April 1998 review draft of The Inventory of Sources ofDioxin in
the United States, (EPA/600/P-98/002Aa) was peer reviewed in a public meeting held in
Alexandria, Virginia, on June 3-4, 1998. Five reviewers participated in the meeting, to include:
Panel Chair
Valerie Thomas, Ph.D., Research Scientist, Center for Energy and Environmental Studies,
Princeton University.
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AUTHORS, CONTRIBUTORS, AND REVIEWERS (continued)
Panel Members
Patrick Dyke, President, PD Consulting, Oxford, United Kingdom.
Raouf Morcos, Manager, National Office of Pollution Prevention, Environment Canada
Quebec, Canada.
William Randall Seeker, Ph.D., Senior Vice President, Energy and Environmental Research,
Irvine, CA
Chun Yi Wu, Senior Engineer, Air Quality Division, Minnesota Pollution Control Agency
St. Paul, MN
ACKNOWLEDGMENT
The authors would like to acknowledge the efforts of Terri Konoza of NCEA who managed the
document production activities.
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EXECUTIVE SUMMARY
Background
The Inventory of Sources and Environmental Releases of Dioxin-Like Compounds in the
United States: The Year 2000 Update presents estimates of annual releases of dioxin-like
compounds specific to three reference years: 1987, 1995, and 2000. It is a detailed review and
description of all known sources and their associated activities that cause these compounds to be
released into the circulating environment, that is, to air, water, and land.
The primary purposes of the report are to:
1. Document and describe sources in the United States which release dioxin-like
compounds into the circulating environment.
2. Quantify annual releases to the environment of the United States from known
sources in a scientific and transparent manner.
3. Provide a reliable basis for time-trends analyses.
This is the second dioxin source inventory issued by the U.S. Environmental Protection
Agency (EPA). The first one was issued in draft form and covered the years 1987 and 1995
(U.S. EPA, 1998a). The current effort updates the earlier document and adds annual release
estimates for the year 2000. The Agency anticipates continuing to issue updates in future years.
Approach
Only sources judged to have a reasonable likelihood for releases to the "open and
circulating environment" were addressed in this document. The document discusses both
contemporary formation sources and reservoir sources. Reservoirs are materials or places that
contain previously formed CDDs/CDFs or dioxin-like PCBs that have the potential for
redistribution and circulation in the environment. Potential reservoirs include soils, sediments,
biota, water, and some anthropogenic materials. Reservoirs become sources when they release
compounds to the circulating environment. While reservoir sources are discussed in the
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document, they are not counted as part of the national inventory because they are not original
releases.
The emissions were computed on the basis of an emission factor and activity level. The
emission factor is the amount of dioxin emitted per unit of activity and is determined via
sampling and analyzing the environmental releases from the source. The activity level reflects
how much action is associated with a release and can take several forms such as kilograms of
material processed per year by an industrial facility, vehicle miles traveled per year by trucks and
automobiles, and liters of wastewater discharged into surface water from industrial sources.
These factors are multiplied to arrive at an estimate of total environmental releases for a given
year. The confidence in the accuracy of both the emission factor and activity level are rated as
low, medium, or high based on the quality and representativeness of the data. The overall
estimate of environmental release is also rated as low, medium, or high based on the lowest
rating assigned to either the emission factor or activity level. In some cases, the data were not
adequate to support even a low confidence rating. These cases were treated in two ways. If the
data were sufficient to make an approximate, but clearly nonrepresentative estimate of releases,
these were labeled as preliminary and not included in the national quantitative inventory. If the
limited data suggested that dioxin releases were possible from a source, but were not adequate to
support emission calculations, the source was labeled as unquantifiable. This approach resulted
in the following classification scheme:
Category A
Category B
Category C
Category D
Category E
High Confidence
Medium Confidence
Low Confidence
Preliminary
Unquantifiable
Included in the national quantitative
inventory
Not included in the national quantitative
inventory
Throughout this document, environmental release estimates are presented in terms of
toxic equivalents (TEQs). TEQs are derived from a toxicity weighting system that converts all
mixture components to a single value normalized to the toxicity of 2,3,7,8-TCDD (see Section
1.1.4 for details). This is done for convenience in presenting summary information and to
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facilitate comparisons across sources. For many situations, however, it is important to use the
individual CDD/CDF and PCB congener values rather than TEQs. The full congener-specific
release rates for most sources are given in an electronic database that will become available as a
companion to this document.
Results - Total Environmental Releases
Tables 1-6 and 1-7 in Chapter 1 show the emission estimates for all sources that could be
quantified, i.e., Categories A, B, C, and D. The Category D estimates are clearly labeled as
outside the national inventory. Category E sources are shown in Table 1-5.
For the year 2000, EPA makes the following conclusions:
• The total releases in the inventory (Categories A, B, and C) were 1,529 g TEQDF-
WHO98/yr. Releases to the air accounted for 92% of the total releases. The top three
sources were backyard barrel burning of refuse (32%), medical waste incinerators
(MWIs) (24%), and municipal waste combustors (MWCs) (5%).
The contemporary formation sources included Category D air releases totaling 6,777
g TEQDF-WHO98/yr. Forest fires accounted for 72% of the total releases.
• A total of 18 contemporary formation sources were identified as Category E.
• Releases from only two reservoir sources could be estimated for 2000: urban runoff
to surface water 142 g TEQDF-WHO98 and rural soil erosion to surface water 2,500 g
TEQDF-WHO98. Both of these estimates are preliminary (i.e., Category D). Releases
from the other reservoirs (air, sediment, water, and biota) could not be quantified
(i.e., Category E).
The following table summarizes the environmental releases of dioxin from all sources in
the inventory for years 2000, 1995, and 1987. It shows the sources in ranked order from highest
to lowest and also shows the percent contribution of each source to the total emissions. In 1987
and 1995, the leading source of dioxin emissions to the U.S. environment was municipal waste
combustion; however, because of reductions in dioxin emissions from MWCs, it dropped to the
third ranked source in 2000. Burning of domestic refuse in backyard burn barrels remained fairly
constant over the years, but in 2000, it emerged as the largest source of dioxin emissions.
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o
OJ
o
j^.
o
Top ten dioxin emitting sources for the years 2000,1995, and 1987
fe
H
o
H
O
O
&
O
Ranking of the year 2000 sources
Backyard barrel burning of refuse
Medical \^e/pathological incineration
Municipal \^aste combustion
Municipal \^astev\ater treatment sludge
Coal fired-utility boilers
Cement kilns (hazardous \^e burning)
Diesel heavy duty trucks
Primary Magnesium production
Industrial \rood combustion
Secondary aluminum smelting
Other
Total Environmental Releases
Year 2000
Grams
498.53
378.00
78.90
78.20
69.50
68.40
65.40
42.00
41.50
35.90
173.16
1529.49
Percent of
Total
32.59%
24.71%
5.16%
5.11%
4.54%
4.47%
4.28%
2.75%
2.71%
2.35%
11.32%
100.00%
Ranking of the year 1995 sources
Municipal \^e combustion
Backyard barrel burning of refuse
Medical waste/pathological incineration
Secondary copper smelters
Cement kilns (hazardous v\aste burning)
Municipal \^aste\^ater treatment sludge
Coal fired-utility boilers
Diesel heavy duty trucks
Secondary aluminum smelters
2,4-Dichlorophenoxy acetic acid
Other
Total Environmental Releases
Year 1995
Grams
1,250.00
628.00
488.00
271.00
156.10
116.10
60.10
33.30
29.10
28.90
219.33
3,279.93
Percent of
Total
38.11%
19.15%
14.88%
8.26%
4.76%
3.54%
1.83%
1.02%
0.89%
0.88%
6.69%
100.00%
Ranking of the year!987 sources
Municipal \^aste combustion
Medical \^aste/pathological incineration
Secondary copper smelters
Backyard barrel burning of refuse
Bleached chemical v\ood pulp and paper mills
Cement kilns (hazardous \^aste burning)
Municipal \^aste\^ater treatment sludge
Coal fired-utility boilers
Automobiles using leaded gasoline
2,4-Dichlorophenoxy acetic acid
Other
Total Environmental Releases
Year 1987
Grams
8,877.00
2,590.00
983.00
604.00
356.00
117.80
76.60
50.80
37.50
33.40
236.29
13,962.39
Percent of
Total
63.58%
18.55%
7.04%
4.33%
2.55%
0.84%
0.55%
0.36%
0.27%
0.24%
1.69%
100.00%
o
H
W
-------
Environmental releases of CDDs/CDFs in the United States occur from a wide variety of
sources but are dominated by releases to the air from combustion sources. The following pie
charts summarize the breakdown of CDD/CDF releases to air, water, and land for each of the
reference years.
Breakdown of Releases by Environmental Media
Year 2000 Year 1995
0.9% 4.6%
93.0%
94.5%
Year 1987
2.5% 0.9%
T
96.5%
EH Releases to Air
| Releases to Water
EH Releases to Land
Results - Time Trends
A significant reduction in total CDD/CDF environmental releases has occurred since
1987. EPA's best estimates of releases of CDDs/CDFs to air, water, and land (from reasonably
quantifiable sources) are approximately 1,529 g TEQDF-WHO98 in reference year 2000; 3,280 g
TEQDF-WHO98 in reference year 1995; and 13,962 g TEQDF-WHO98 in reference year 1987 (see
the following figure). From 1987 to 2000 there was approximately an 89% reduction in releases
to all media. Most of the reduction in dioxin releases (77%) occurred in the time period from
1987 to 1995.
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Year 1987
Year 199
Year 200'
Time-Trends of Environmental Releases of
Dioxin-like Compounds in the United States
3,000 6,000 9,000 12,000
TOTAL ENVIRONMENTAL RELEASES, WHO-TEQ gram/year
15,000
Reductions in environmental releases of dioxin-like compounds are attributed primarily
to reductions in air emissions from MWCs, MWIs, and cement kilns burning hazardous waste
and from wastewater discharged into surface waters from pulp and paper mills using chlorine.
These reductions have occurred from a combination of regulatory activities, improved emission
controls, voluntary actions on the part of industry, and the closing of a number of facilities. The
following table shows the reductions made among the largest sources.
Source category
Municipal waste
combustion
Medical waste
incineration
Cement kilns burning
hazardous waste
Bleached chemical
wood pulp and paper
mills
Media
release
Air
Air
Air
Surface
water
Reference
year 2000
(g TEQDF-
WH098)
78.9
378
68.4
1
Reference
year 1987
(gTEQDF-
WH098)
8877
2590
117.8
356
Percent
reduction in
environmental
releases
>99
85
42
>99
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Results - Sources Not Considered in the Inventory
Significant amounts of the dioxin-like compounds produced annually in the United States
are not considered releases to the open circulating environment and therefore, 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 Category D or E sources
and therefore, were not included in the inventory. The largest contemporary formation Category
D sources are forest fires, and accidental fires at municipal solid waste landfills. Taken together,
these sources have the potential to significantly increase the present inventory if preliminary
release estimates are confirmed.
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1 1. BACKGROUND, APPROACH, AND CONCLUSIONS
2 1.1. BACKGROUND
3 This report presents a comprehensive inventory of sources of releases of dioxin-like
4 compounds in the United States. It is a detailed review and description of all known sources and
5 their associated activities that cause these compounds to be released into the circulating
6 environment, that is, to air, water, and land.
7 The primary purposes of this report are to
8
9 • Document and describe sources in the United States of releases of dioxin-like
10 compounds into the circulating environment.
11
12 • Quantify annual releases to the environment of the United States from known sources
13 in a scientific and transparent manner.
14
15 • Provide a reliable basis for time-trends analyses, such as, observing changes in total
16 releases to the circulating environment with the passage of time. Time-trend analyses
17 provide a quantitative indication of the achievements made in reducing environmental
18 releases of dioxin-like compounds from known sources in the United States.
19
20 This is the second dioxin source inventory issued by the U.S. Environmental Protection
21 Agency (EPA). The first one was issued in draft form and covered the years 1987 and 1995
22 (U.S. EPA, 1998a). The current effort updates the earlier document and adds annual release
23 estimates for the year 2000. The Agency anticipates continuing to issue updates in future years.
24 The primary technical resource supporting the inventory of sources of dioxin-like
25 compounds is the U.S. Environmental Protection Agency's (EPA's) Database of Sources of
26 Environmental Releases of Dioxin-Like Compounds in the United States (U.S. EPA, 200 la).
27 This database includes congener-specific chlorinated dibenzo-p-dioxin (CDD) and chlorinated
28 dibenzofuran (CDF) emissions data extracted from original engineering test reports. After the
29 2000 update has been reviewed, an updated database will be made available to the public that
30 reflects the years 1987, 1995, and 2000.
31 The intended audience and users of the dioxin inventory include
32
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1 • Members of the general public who are interested in learning more about sources of
2 emissions of dioxin-like compounds to the U.S. environment and in obtaining peer-
3 reviewed estimates of releases.
4
5 • State and local regulatory agencies that are interested in obtaining reliable and peer-
6 reviewed information on sources and environmental releases of dioxin-like
7 compounds.
8
9 • EPA Regional and Program Offices that are responsible for evaluating the need for
10 regulating and/or preventing dioxin releases to the environment.
11
12 • Risk assessors in the private and public sectors who need reliable information on
13 sources and releases of dioxin-like compounds to improve quantitative risk
14 assessments of dioxin sources.
15
16 • Researchers who are interested in documented and time-specific dioxin source and
17 emissions data to be used in sequential time-trends analyses.
18
19 • Private and public stakeholder groups that are interested in obtaining reliable and
20 peer-reviewed information on dioxin sources and releases and in observing time
21 trends in environmental releases of dioxin-like compounds from specific source
22 categories.
23
24 1.1.1. Reference Years
25 A central part of EPA's Dioxin Inventory is the organization of estimates of annual
26 releases of dioxin-like compounds into reference years. The selection and use of three reference
27 years provides a basis for comparing environmental releases of dioxin-like compounds over time.
28 The year 1987 was selected as the initial reference year because it was the earliest time
29 when it was feasible to assemble a reasonably comprehensive inventory. Prior to that time, very
30 little data existed on dioxin emissions from stacks or other release points. The first study
31 providing the type of data needed for a national inventory was EPA's National Dioxin Study
32 (U.S. EPA, 1987a). The year 1987 also corresponds roughly with the time when significant
33 advances occurred in emissions measurement techniques and in the development of high-
34 resolution mass spectrometry and gas chromatography which allowed analytical laboratories to
35 detect low levels of chlorinated dibenzo-p-dioxin (CDD) and chlorinated dibenzofuran (CDF)
36 congeners in environmental samples. Soon after this time, a number of facilities began upgrades
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1 specifically intended to reduce CDD/CDF emissions. Consequently, 1987 emissions are
2 representative of levels of emissions that occurred before the widespread installation of dioxin-
3 specific emission controls.
4 EPA selected 1995 as the second reference year because it reflected the completion time
5 of the first set of regulatory activities specifically tailored to reduce dioxin releases from major
6 sources. By 1995, EPA had proposed or promulgated regulations limiting CDD/CDF emissions
7 from municipal waste combustors (MWCs), medical waste incinerators (MWIs), hazardous
8 waste incinerators, cement kilns burning hazardous waste, and pulp and paper mill facilities
9 using bleached chlorine processes.
10 The year 2000 was chosen as the most current date that could be addressed when this
11 effort began in 2002. Also, it corresponds to a reasonable time interval since 1995 when one
12 could expect to see further changes occurring in releases as a result of continuing regulatory
13 activities, voluntary actions on the part of industry, and facility closures.
14
15 1.1.2. Regulatory Summary
16 The following is a synopsis of EPA regulatory activities addressing releases of dioxin-like
17 compounds. As discussed in Section 1.3.2, these regulations (along with other factors)
18 contributed to the reductions in dioxin emissions observed over time.
19
20 Municipal Waste Combustors (MWCs^
21 In 1987, MWCs were the largest source of dioxin releases to the environment, amounting
22 to an estimated 64% of dioxin releases. In July 1987, as a result of these findings, EPA
23 announced plans to set regulatory standards for the control of dioxin and other pollutant
24 emissions to the air from MWCs. The Agency issued guidance to the states to ensure that best
25 available control technologies (BACT) were used on new facilities even before the development
26 of the upcoming regulations. BACT for dioxin control was identified as dry scrubbers (DSs)
27 combined with fabric filters (FFs) (52 FR 25399, July 7, 1987). EPA took the following
28 regulatory actions to reduce dioxin releases from MWCs:
29
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1 • December 20, 1989, EPA proposed dioxin standards for new MWCs and guidelines
2 for existing MWCs (54 FR 52251 and 54 FR 52209, respectively).
3
4 • November 15, 1990, Amendments to the Clean Air Act (CAA) were enacted and
5 Section 129 was added which specifies that revised standards and guidelines must be
6 developed for both large and small MWC plants and they must reflect more restrictive
7 performance levels. Section 129 includes a schedule for revising the 1991 standards
8 and guidelines.
9
10 • February 11, 1991, EPA promulgated final maximum achievable control technology
11 (MACT) dioxin standards and guidelines (56 FR 5488 and 56 FR 5514, respectively)
12 only on large MWCs (capacities above 250 tons per day).
13
14 • The Sierra Club, the Natural Resources Defense Council, and the Integrated Waste
15 Services Association filed complaints with the U.S. District Court for the Eastern
16 District of New York to require dioxin standards for small MWCs. The proposal
17 notice for the standards and guidelines was signed as scheduled and published on
18 September 20, 1994 (59 FR 48198 and 59 FR 48228, respectively).
19
20 • October 31, 1995, EPA issued final standards and guidelines on revised MACT
21 standards and guidelines to MWC units with aggregate plant capacity above 40 tons
22 per day.
23
24 Hazardous Waste Incinerators
25 * July 16, 1992, EPA issued proposed dioxin regulations (57 FR 31576) for
26 hazardous waste incinerators, hazardous waste burning cement kilns, and
27 hazardous waste burning lightweight aggregate kilns.
28
29 • May 18, 1993, EPA issued a Hazardous Waste Minimization and Combustion
30 Strategy. This required tighter permitting requirements for dioxin emissions
31 from Hazardous Waste Incinerators.
32 • September 30, 1999, EPA promulgated dioxin standards (under the CAA) for
33 hazardous waste incinerators, hazardous waste burning cement kilns, and
34 hazardous waste burning lightweight aggregate kilns.
35
36 Medical Waste Incinerators (MWIs)
37 • Feb 27, 1995, EPA proposed dioxin standards for
38 MWIs under the CAA (60 FR 10654).
39
40 • August 15, 2000, EPA promulgated dioxin emission standards (65 FR 49739).
41
42 Pulp and Paper Mills
43 • December 17, 1993, EPA proposed dioxin effluent standards under the CWA.
44
45 • April 15, 1998, EPA promulgated dioxin effluent standards under the CWA.
46
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1 1.1.3. Definition of Dioxin-Like Compounds
2 This inventory of sources and environmental releases addresses specific compounds in
3 the following chemical classes: polychlorinated dibenzo-p-dioxins (CDDs), polychlorinated
4 dibenzofurans (CDFs), and polychlorinated biphenyls (PCBs); it describes this subset of
5 chemicals as "dioxin like." Dioxin-like refers to the fact that these compounds have similar
6 chemical structures and physical-chemical properties, and they invoke a common battery of toxic
7 responses. Because of their hydrophobic nature and resistance towards metabolism, these
8 chemicals persist and bioaccumulate in the fatty tissues of animals and humans. The CDDs
9 include 75 individual compounds; CDFs include 135 compounds. These individual compounds
10 are technically referred to as congeners. Only 7 of the 75 congeners of CDDs, or of brominated
11 dibenzo-p-dioxins (BDDs), are thought to have dioxin-like toxicity; these are ones with chlorine
12 substitutions in—at a minimum—the 2, 3, 7, and 8 positions. Only 10 of the 135 possible
13 congeners of CDFs are thought to have dioxin-like toxicity; these also are ones with substitutions
14 in the 2, 3, 7, and 8 positions. This suggests that 17 individual CDDs/CDFs exhibit dioxin-like
15 toxicity.
16 There are 209 PCB congeners, of which only 13 are thought to have dioxin-like toxicity:
17 those with four or more lateral chlorine atoms with one or no substitution in the ortho position.
18 These compounds are sometimes referred to as coplanar, meaning that they can assume a flat
19 configuration with rings aligned along the same plane. The physical/chemical properties of each
20 congener vary according to the degree and position of chlorine substitution.
21 Generally speaking, this document focuses on the 17 CDDs/CDFs and a few of the
22 coplanar PCBs that are frequently encountered in source characterization or environmental
23 samples.
24 CDDs and CDFs are tricyclic aromatic compounds that have similar physical and
25 chemical properties. Certain PCBs (the so-called coplanar or mono-ortho coplanar congeners)
26 are also structurally and conformationally similar. The most widely studied of this general class
27 of compounds is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). TCDD, often called simply
28 "dioxin," represents the reference compound for this class of compounds. The structures of
29 TCDD and several related compounds are shown in Figure 1-1. Although sometimes confusing,
30 the term "dioxin" is often also used to refer to the complex mixtures of TCDD and related
31 compounds emitted from sources or found in the environment or in biological samples. It can
32 also be used to refer to the total TCDD "equivalents" found in a sample. This concept of toxicity
33 equivalency (TEQ) is discussed below.
34
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1 1.1.4. Toxicity Equivalency Factors (TEFs)
2 CDDs, CDFs, and PCBs are commonly found as complex mixtures when detected in
3 environmental media and biological tissues or when measured as environmental releases from
4 specific sources. Humans are likely to be exposed to mixtures of CDDs, CDFs, and dioxin-like
5 PCB congeners that vary by source and pathway, complicating the assessment of human health
6 risk assessment. In order to address this problem, the concept of TEQ has been considered and
7 discussed by the scientific community, and TEFs have been developed and introduced to
8 facilitate risk assessment of exposure to these chemical mixtures.
9 On the most basic level, TEFs compare the potential toxicity of each dioxin-like
10 compound in the mixture to the well-studied and well-understood toxicity of TCDD, the most
11 toxic member of the group. The comparison procedure involves assigning individual TEFs to the
12 2,3,7,8-substituted CDD/CDF congeners and "dioxin-like" PCBs. To accomplish this, scientists
13 have reviewed the toxicological databases along with considerations of chemical structure,
14 persistence, and resistance to metabolism and have agreed to ascribe specific "order of
15 magnitude" TEFs for each dioxin-like congener relative to TCDD, which is assigned a TEF of 1.
16 The other congeners have TEF values ranging from 1 to 0.00001.
17 Thus, these TEFs are the result of scientific judgment of a panel of experts using all of the
18 available data and are selected to account for uncertainties in the available data and to avoid
19 underestimating risk. In this sense, they can be described as "public health-conservative" values.
20 To apply this TEF concept, the TEF of each congener present in a mixture is multiplied by the
21 respective mass concentration, and the products are summed to represent the 2,3,7,8-TCDD TEQ
22 of the mixture (eq 1-1).
23
24 TEQ a ^i-n(Congener, x TEF) + (Congener} x TEF) + (Congenern x TEFJ (1-1)
25
26 The TEF values for CDDs and CDFs were originally adopted by international convention
27 (U.S. EPA, 1989a). These values were further reviewed and/or revised, and TEFs were also
28 developed for PCBs (Ahlborg et al., 1994; van den Berg et al., 1998). A problem arises in that
29 past and present quantitative exposure and risk assessments may not have clearly identified
30 which of three TEF schemes was used to estimate the TEQ. This document uses a new uniform
31 TEQ nomenclature that clearly distinguishes between the different TEF schemes and identifies
32 the congener groups included in specific TEQ calculations. The nomenclature uses the following
33 abbreviations to designate which TEF scheme was used in the TEQ calculation:
34
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1 • I-TEQ refers to the international TEF scheme adopted by EPA in 1989 (U.S. EPA,
2 1989a). See Table 1-1.
3
4 • TEQ-WHO94 refers to the 1994 World Health Organization (WHO) extension of the
5 I-TEF scheme to include 13 dioxin-like PCBs (Ahlborg et al., 1994). See Table 1-2.
6
7 • TEQ-WHO98 refers to the 1998 WHO update to the previously established TEFs for
8 dioxins, furans, and dioxin-like PCBs (van den Berg et al., 1998). See Table 1-3.
9
10 The nomenclature also uses subscripts to indicate which family of compounds is included
11 in any specific TEQ calculation. Under this convention, the subscript D is used to designate
12 dioxins, the subscript F to designate furans, and the subscript P to designate PCBs. As an
13 example, "TEQDF-WHO98" would be used to describe a mixture for which only dioxin and furan
14 congeners were determined and where the TEQ was calculated using the WHO98 scheme. If
15 PCBs had also been determined, the nomenclature would be "TEQDFP-WHO98." Note that the
16 designations TEQDF-WHO94 and I-TEQDF are interchangeable, as the TEFs for dioxins and furans
17 are the same in each scheme. Note also that in this document I-TEQ sometimes appears without
18 the D and F subscripts. This indicates that the TEQ calculation includes both dioxins and furans.
19 A complete listing of the nomenclature used in this report is depicted in Table 1-4. This
20 document emphasizes the WHO98 TEF scheme as the preferred scheme to be used to assign TEQ
21 to complex environmental mixtures.
22 Throughout this document, environmental release estimates are presented in terms of
23 TEQs. This is done for convenience in presenting summary information and to facilitate
24 comparisons across sources. For purposes of environmental fate modeling, however, it is
25 important to use the individual CDD/CDF and PCB congener values rather than TEQs. This is
26 because the physical/chemical properties of individual CDD/CDF congeners vary and,
27 consequently, the congeners will behave differently in the environment. For example, the
28 relative mix of congeners released from a stack cannot be assumed to remain constant during
29 transport through the atmosphere and deposition to various media. The full congener-specific
30 release rates for most sources are given in an electronic database that will become available as a
31 companion to this document.
32
33 1.1.5. Information Sources
34 In general, the literature used to prepare this report includes documents published in 2003
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1 or earlier. Some 2004 documents are cited, primarily in Chapter 2 on Formation Theory, but a
2 thorough literature review has not been extended past 2003.
3 EPA's Toxic Release Inventory (TRI) began collecting data on PCBs in 1988 and on
4 CDD/CDFs in 2000 (U.S. EPA, 2003c). These data have been considered in this report for
5 purposes of identifying possible sources but were not used for making quantitative release
6 estimates because of the following:
7
8 • With respect to PCBs, the TRI data are reported as total PCBs and not on a congener-
9 specific basis. Thus, it is unknown what portion of these releases are dioxin-like
10 PCBs and, therefore, TEQs cannot be calculated. In this present format, the PCB TRI
11 data is not readily usable within the structure of this dioxin inventory.
12
13 • With respect to CDDs/CDFs, the reporting format under TRI is the sum quantity of
14 the 17 toxic CDDs and CDFs that are emitted in a given year (i.e., the sum of the
15 2,3,7,8-chlorine substituted compounds). Neither the releases of the individual
16 CDD/CDF congeners nor the TEQS must be reported, therefore, the dioxin TRI data
17 is not readily usable within the structure of this dioxin inventory.
18
19 • The accuracy of the TRI data are unknown because they are self-reported and are not
20 required to be based on measurements.
21
22 • The TRI reports lack specific details and descriptions of the reporting industries.
23 This information is needed for the dioxin inventory, because the calculation of source-
24 specific emission factors (representative of industrial source categories) strongly
25 depends on closely matching facilities in terms of similarity of process, production,
26 and pollution control.
27
28 • The TRI reporting format does not include information on the strengths/weaknesses
29 of the data, and therefore, it would be difficult to evaluate these data in terms of the
30 confidence rating scheme developed for this inventory.
31
32
33 1.2. APPROACH
34 Only sources judged to have a reasonable likelihood for releases to the "circulating
35 environment" were addressed in this document. Examples of the circulating environment system
36 boundary are
37
38 • CDDs/CDFs and dioxin-like PCBs in air emissions and wastewater discharges are
39 included, whereas CDDs/CDFs and dioxin-like PCBs in intermediate products or
40 internal wastestreams are not included. For example, the CDDs/CDFs in a
41 wastestream going to an on-site incinerator are not addressed in this document, but
42 any CDDs/CDFs in the stack emissions from the incinerator are included.
43
44 • CDDs/CDFs and dioxin-like PCBs in wastestreams applied to land in the form of
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1 "land fanning" are included, whereas those disposed of in permitted landfills were
2 excluded. Properly designed and operated landfills are considered to achieve long-
3 term isolation from the circulating environment. Land farming, however, involves the
4 application of wastes directly to land, clearly allowing for releases to the circulating
5 environment.
6
7 1.2.1. Source Classes
8 In the United States, the major identified sources of environmental releases of dioxin-like
9 compounds have been grouped into five broad categories:
10
11 Combustion. CDDs/CDFs are formed in most combustion systems, which can include waste
12 incineration (such as municipal solid waste, sewage sludge, medical waste, and hazardous
13 wastes), the burning of various fuels (such as coal, wood, and petroleum products), other high-
14 temperature sources (such as cement kilns), and poorly or uncontrolled combustion sources (such
15 as forest fires, building fires, and open burning of wastes).
16
17 Metals smelting, refining, and processing. CDDs/CDFs can be formed during various types of
18 primary and secondary metals operations, including iron ore sintering, steel production, and scrap
19 metal recovery.
20
21 Chemical manufacturing. CDDs/CDFs can be formed as by-products from the manufacture of
22 chlorine-bleached wood pulp, chlorinated phenols (e.g., pentachlorophenol [PCP]), PCBs,
23 phenoxy herbicides (e.g., 2,4,5-T), and chlorinated aliphatic compounds (e.g., ethylene
24 dichloride).
25
26 Biological and photochemical processes. Recent studies suggest that CDDs/CDFs can be
27 formed under certain environmental conditions (e.g., composting) from the action of
28 microorganisms on chlorinated phenolic compounds. Similarly, CDDs/CDFs have been reported
29 to be formed during photolysis of highly chlorinated phenols.
30
31 Reservoirs. Reservoirs are materials or places that contain previously formed CDDs/CDFs or
32 dioxin-like PCBs, which have the potential for redistribution and circulation in the environment.
33 Potential reservoirs include soils, sediments, biota, water, and some anthropogenic materials.
34 Reservoirs become sources when they have releases to the circulating environment.
35 Sources can also be divided in terms of when releases occur: (1) contemporary formation
36 sources (sources that have essentially simultaneous formation and release) and (2) reservoir
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1 sources (materials or places that contain previously formed CDDs/CDFs or dioxin-like PCBs that
2 are re-released to the environment). The contemporary formation sources are discussed in
3 Chapters 2 through 11 and the reservoir sources are discussed in Chapter 12. The presence of
4 CDDs/CDFs in ball clay is discussed in Chapter 13. Table 1-5 provides a comprehensive list of
5 all known or suspected sources of CDDs/CDFs in the United States. The checkmarks indicate
6 how each source was classified in terms of the following six categories:
7
8 1. Contemporary formation sources with reasonably well-quantified releases (see
9 Section 1.4.2). These sources are listed in Table 1-5 and release estimates are shown
10 in Tables 1-6 and 1-7.
11
12 2. Contemporary formation sources with preliminary release estimates. These sources
13 are listed in Table 1-5 and release estimates for 2000 are shown in Tables 1-6 and 1-7.
14
15 3. Contemporary formation sources without quantified release estimates. These sources
16 are listed in Table 1-5.
17
18 4. Reservoir sources with reasonably well-quantified releases. These sources would
19 have been listed in Table 1-5 and release estimates would have been shown in Table
20 1-13, but none have yet been identified.
21
22 5. Reservoir sources with preliminary release estimates. These sources are listed in
23 Table 1-5 and release estimates are shown in Table 1-13.
24
25 6. Reservoir sources without quantified releases. These sources are listed in Table 1-5.
26
27 Only contemporary formation sources (numbers 1-3 above) are considered for inclusion
28 in the national inventory. Reservoir sources are not considered because they are not original
29 releases, but rather the recirculation of past releases.
30 This document includes discussions on products that contain dioxin-like compounds.
31 Some of these products, such as 2,4-D, are considered to be sources because they are clearly used
32 in ways that result in environmental releases. These products have been classified into one of the
33 above six groups. Other products containing dioxin-like compounds, such as vinyl chloride
34 products, do not appear to have environmental releases and are not considered sources. For all
35 CDD/CDF-containing products, this document summarizes the available information about
36 contamination levels and, where possible, makes estimates of the total amount of CDDs/CDFs
37 produced annually in these products. Estimates of the CDD/CDF TEQ amounts in products are
38 summarized in Tables 1-8 and 1-9.
39
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1 1.2.2. Quantitative Method for Inventory of Sources
2 Some source types have a high percentage of facilities with measured CDD/CDF releases
3 such as municipal waste combustion, hazardous waste incineration, cement kilns that burn
4 hazardous waste, effluent from chlorine-bleached pulp and paper mills, and sewage sludge
5 (biosolids) that are applied to farm lands and grazing lands. Other source categories, have
6 relatively few tested facilities. In these cases, EPA relies on the use of emission factors to
7 estimate CDD/CDF releases from the untested facilities. This provides a method of
8 extrapolation from tested facilities to national estimates of environmental releases. Many of the
9 national emission estimates, therefore, have been developed using this "top-down" approach.
10 The first step in this approach is to derive from the available emissions monitoring data
11 an emission factor (or series of emission factors) deemed to be representative of the source
12 category (or segments of a source category that differ in configuration, fuel type, air pollution
13 control equipment, etc.). The emission factor relates mass of CDDs/CDFs or dioxin-like PCBs
14 released into the environment with some measure of activity (e.g., kilograms of material
15 processed per year, vehicle miles traveled per year, etc.). It was developed by averaging the
16 emission factors for the tested facilities in the class. This average emission factor was then
17 multiplied by the measure of activity for the nontested facilities in the class (e.g., total kilograms
18 of material processed by these facilities annually). Finally, emissions were summed for the
19 tested facilities and nontested facilities. In summary, this procedure can be represented by the
20 following equations:
21
22 ^total~ Li^1 tested, I L,^1 untested, I (1~2)
23
24 ^total ~LJ^tested, I L,(^i*-"-i)untested (1~3)
25
26 where:
27 Etotal = annual emissions from all facilities (g TEQ/yr)
28 Etested j = annual emissions from all tested facilities in class I (g TEQ/yr)
29 E,,,^,^! = annual emissions from all untested facilities in class I (g TEQ/yr)
30 EF; = mean emission factor for tested facilities in class I (g TEQ/kg)
31 Aj = activity measure for untested facilities in class I (kg/yr)
32
33 Figures 1-2 through 1-4 and 1-6 through 1-8 depict the various source categories along
34 with their emission factors, activity levels, and annual emissions for the reference years 1987,
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1 1995, and 2000 in I-TEQ and WHO-TEQ units. Figures 1-5 and 1-9 depict comparisons of the
2 estimated I-TEQ and WHO-TEQ air emissions for the reference years 1987, 1995, and 2000.
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 emission
6 factors for each subcategory. Implicit in this procedure is the assumption that facilities with
7 similar design and operating conditions should have similar CDD/CDF release potential. For
8 most source categories, however, the specific combination of features that contributes most to
9 CDD/CDF or dioxin-like PCB release is not well understood. Therefore, how to best
10 subcategorize a source category was often problematic. For each subcategorized source category
11 in this document, a discussion is presented about the variability in design and operating
12 conditions, what is known about how these features contribute to CDD/CDF or dioxin-like PCB
13 release, and the rationale for subcategorizing the category.
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. EPA has
16 made uncertainty determinations for each of these emission factors based, in part, on the
17 assumption that by applying them to a group of facilities, the potential for overestimating or
18 underestimating individual facilities will, to some extent, be self-compensating. This means that
19 in using these emission factors one can place significantly greater confidence in an emission
20 estimate for a class than in an estimate for any individual facility. Given the limited amount of
21 data available for deriving emission factors and the limitations of our understanding about
22 facility-specific conditions that determine formation and control of dioxin-like compounds, the
23 current state of knowledge cannot support the development of emission factors that can be used
24 to accurately estimate emissions on an individual facility-specific basis. The emission factors
25 developed for each of the categories discussed in this national emissions inventory are listed in
26 Tables 1-11 and 1-12.
27
28 1.2.3. Confidence Ratings
29 As discussed above, each source emission calculation required estimates of an "emission
30 factor" and an "activity level." For each emission source, the quantity and quality of the
31 available information for both terms vary considerably. Consequently, it is important that
32 emission estimates be accompanied by some indicator of the uncertainties associated with their
33 development. For this reason, a qualitative confidence rating scheme was developed as an
34 integral part of the emission estimate in consideration of the following factors:
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1 • Emission factor. The uncertainty in the emission factor estimate depends primarily on
2 how well the tested facilities represent the untested facilities. In general, confidence
3 in the emission factor increases with increases in the number of tested facilities
4 relative to the total number of facilities. Variability in terms of physical design and
5 operating conditions within a class or subclass must also be considered. The more
6 variability among facilities, the less confidence that a test of any single facility is
7 representative of that class or subclass. The quality of the supporting documentation
8 also affects uncertainly. Whenever possible, original engineering test reports were
9 used. Peer-reviewed reports from the open literature were also used for developing
10 some emission factors. In some cases, however, draft reports that had undergone
11 more limited review were also used. In a few cases, unpublished references (such as
12 personal communication with experts) were used and are clearly noted in the text.
13
14 • Activity level. The uncertainty in the activity level estimate was judged primarily on
15 the basis of the extent of the underlying data. Estimates derived from comprehensive
16 surveys (including most facilities in a source category) were assigned high
17 confidence. As the number of facilities in the survey relative to the total decreased,
18 confidence also decreased. The quality of the supporting documentation also affects
19 uncertainty. Peer-reviewed reports from the open literature (including government
20 and trade association survey data) were considered most reliable. However, as with
21 the emission factor estimates, draft reports that had undergone more limited review
22 were used in some cases, and in a few cases, unpublished references, such as personal
23 communication with experts, were used. These are clearly noted in the text.
24
25 The confidence rating scheme in Table 1-10, presents the qualitative criteria used to
26 assign a high, medium, or low confidence rating to the emission factor and activity level terms
27 for those source categories for which emission estimates can be reliably quantified. The overall
28 "confidence rating" assigned to an emission estimate was determined by the confidence ratings
29 assigned to the corresponding "activity level" term and "emission factor" term. If the lowest
30 rating assigned to either the activity level or the emission factor term is "high," then the category
31 rating assigned to the emission estimate is high (also referred to as "A"). If the lowest rating
32 assigned to either the activity level or the emission factor term is "medium," then the category
33 rating assigned to the emission estimate is medium (also referred to as "B"). If the lowest rating
34 assigned to either the activity level or the emission factor term is "low," then the category rating
35 assigned to the emission estimate is low (also referred to as "C"). It is emphasized that this
36 confidence rating scheme should not be interpreted as a statistical measure, but rather as
37 subjective judgment of the relative uncertainty among sources.
38 For many source categories, either emission factor information or activity level
39 information was inadequate to support development of reliable quantitative release estimates for
40 one or more media. For some of these source categories, sufficient information was available to
41 make preliminary estimates of emissions of CDDs/CDFs or dioxin-like PCBs; however, the
42 confidence in the activity level estimates or emission factor estimates was so low that they cannot
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1 be included in the sum of quantified emissions from sources with confidence ratings of A, B, and
2 C. These preliminary estimates were given an overall confidence class rating of D (Tables 1-6
3 and 1-7 show preliminary release estimates for the year 2000 only). As preliminary estimates of
4 source magnitude, they can be used to help prioritize future research and data collection. The
5 actual magnitude of emissions from these sources could be significantly lower or higher than
6 these preliminary estimates. Although EPA has chosen not to include them in the more
7 thoroughly characterized emissions of the national inventory, some of these poorly characterized
8 sources have the potential of being major contributors of releases to the environment. It is
9 important to present these estimates because they may help determine priorities for future data
10 collection efforts. As the uncertainty around these sources is reduced, they will be included in
11 future inventory calculations.
12 For other sources, some information exists that suggests that they may release dioxin-like
13 compounds; however, the available data were judged to be insufficient for developing any
14 quantitative emission estimate. These source categories were assigned a confidence category
15 rating of "E" and also were not included in the national inventory (see listings in Table 1-5 under
16 the "Not quantifiable" column).
17
18 1.3. CONCLUSIONS
19 1.3.1. Total Environmental Releases
20 Nationwide emission estimates of I-TEQDF and TEQDF-WHO98 for the United States are
21 presented in Tables 1-6 and 1-7, respectively. For the year 2000, EPA makes the following
22 conclusions:
23
24 • The total releases in the inventory (Categories A, B, and C) were 1,529 g TEQDF-
25 WHO98/yr. These were dominated by releases to the air (92%). Most of the air
26 releases were from combustion sources. The top three sources were backyard barrel
27 burning of refuse (32%), MWIs (24%), and MWCs (5%).
28
29 • The contemporary formation sources included Category D air releases totaling 6,777
30 g TEQDF-WHO98/yr. These were dominated by forest fires (72%) .
31
32 • A total of 18 contemporary formation sources were identified as Category E.
33
34 • Releases from only two reservoir sources could be estimated for 2000: urban runoff to
35 surface water 142 g TEQDF - WHO98 and rural soil erosion to surface water 2,500 g
36 TEQDF-WHO98. Both of these estimates are preliminary (i.e., category D). Releases
37 from the other reservoirs (air, sediment, water, and biota) could not be quantified (i.e.,
38 Category E).
39
03/04/05 1-14 DRAFT-DO NOT CITE OR QUOTE
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1 1.3.2. Time Trends
2 A significant reduction in total CDD/CDF environmental releases has occurred since
3 1987. EPA's best estimates of releases of CDDs/CDFs to air, water, and land from reasonably
4 quantifiable sources (Categories A, B, and C) are approximately 1,529 g TEQDF-WHO98 in
5 reference year 2000; 3,280 g in reference year 1995; and 13,962 g in reference year 1987. From
6 1987 to 2000 there was approximately an 89% reduction in releases to all media. Most of the
7 reduction in dioxin releases (77%) occurred in the time period from 1987 to 1995.
8 In 1987 and 1995, municipal waste combustion was the leading source of dioxin
9 emissions to the U.S. environment, however, because of reductions in dioxin emissions from
10 MWCs, it dropped to the third ranked source in 2000. Burning of domestic refuse in backyard
11 burn barrels remained fairly constant over the years, but in 2000, it emerged as the largest source
12 of dioxin emissions. A complete listing of all sources in the inventory ranked in order of releases
13 is provided in Table 1-14.
14 Reductions in environmental releases of dioxin-like compounds are attributed primarily
15 to reductions in air emissions from MWCs, MWIs, cement kilns burning hazardous waste, and
16 wastewater discharged into surface waters from pulp and paper mills using chlorine. These
17 reductions have occurred from a combination of regulatory activities (see Section 1.1.2),
18 improved emission controls, voluntary actions on the part of industry, and the closing of a
19 number of facilities.
20
21 1.3.3. Sources Not Included in the Inventory
22 Significant amounts of the dioxin-like compounds produced annually in the United States
23 are not considered releases to the open circulating environment and are not included in the
24 national inventory. Examples include dioxin-like compounds generated internal to a process but
25 destroyed before release, and waste streams that are disposed of in approved landfills.
26 The only product judged to have the potential for environmental release, and therefore,
27 considered for the inventory, was 2,4-D. Release estimates are provided for 1987 and 1995.
28 Since 1995, the chemical manufacturers of 2,4-D have been undertaking voluntary actions to
29 significantly reduce the dioxin-content of the product. No information is available on the extent
30 of these reductions and therefore, no release estimate could be made for 2000. Regarding other
31 products, data are presented on the amounts of CDDs/CDFs contained in the following: bleached
32 pulp, ethylene dichloride/vinyl chloride, pentachlorophenol-treated wood, and dioxazine dyes
33 and pigments. None of these, however, were considered to have release potential and were not
34 included in the inventory.
03/04/05 1-15 DRAFT-DO NOT CITE OR QUOTE
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1 A number of contemporary formation sources were classified as D or E and therefore,
2 were not included in the inventory. The largest contemporary formation Category D sources are
3 forest fires, and accidental fires at municipal solid waste landfills. Taken together, these sources
4 have the potential to significantly increase the present inventory if preliminary release estimates
5 are confirmed.
6 The possibility remains that truly undiscovered sources exist. Many of the sources that
7 are well accepted today were discovered only in the past 20 years. For example, CDDs/CDFs in
8 stack emissions from MWCs were not detected until the late 1970s; CDDs/CDFs in the
9 wastewater effluent from bleached pulp and paper mills were found unexpectedly in the mid-
10 1980s; iron ore was not recognized as a source until the early 1990s.
11
12 1.3.4. Formation Theory
13 Current theory proposes that CDDs/CDFs are formed within the cool-down region of
14 combustion processes, either de novo or from dioxin precursors. De novo synthesis involves
15 solid phase reactions with carbon, chlorine, and oxygen, on combustion generated particles
16 promoted by copper chloride as a catalyst. A less efficient, but plausible, formation process is
17 the gas phase formation from precursors catalyzed by the presence of a transition metal such as
18 copper chloride. The temperatures ideal for de novo dioxin formation are from 200 to 400° C.
19 Reducing temperatures to below 200° C, especially at the air pollution control device, will
20 minimize dioxin formation and releases from combustion sources. Chlorine sources present in
21 feeds are necessary for dioxin formation. Experiments suggest that chlorine content of 1% in the
22 feed/fuel is the threshold for a direct relationship to dioxin formation from combustion sources,
23 i.e., C12 > 1% is strongly correlated to the amount of dioxin formed, but C12 < 1% is not.
24 However, in well designed, controlled, and operated full-scale combustion systems there doesn't
25 appear to be a direct relationship with the amount of chlorine present in the waste or the amount
26 of dioxin emissions from the stack.
27 Controversy exists regarding PVC'srole in the formation of CDDs/CDFs during
28 municipal waste combustion. Experimental evidence suggests that PVC combustion generates
29 hydrogen chloride gas (HC1) and dioxin precursors such as chlorobenzenes and chlorophenols,
30 both of which may contribute to dioxin formation. HC1 is a progenitor of chlorine radicals that
31 then participate in the dioxin formation chemistry. Precursors are foundation molecules to dioxin
32 formation. If PVC was the only source of chlorine and dioxin precursors during the combustion
33 of MSW, then the removal of PVC may reduce the amount of dioxin formed and emitted.
34 However, the complex mixture of materials comprising MSW provides sufficient chlorine for de
03/04/05 1-16 DRAFT-DO NOT CITE OR QUOTE
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1 novo synthesis, and dioxin precursors are formed as products of the incomplete combustion of
2 the waste constituents. Therefore, the elimination of PVC from the waste prior to combustion
3 doesn't necessarily eliminate the formation and emissions of CDDs/CDFs from municipal waste
4 combustion.
5 Current information strongly suggests that releases of CDDs/CDFs to the U. S.
6 environment occur principally from anthropogenic activities. However, scientific studies have
7 identified the possibility of natural formation of some CDDs/CDFs (e.g., ball clay).
8
9 1.3.5. Congener Profiles of CDD/CDF Sources
10 This document presents congener profiles for a number of sources as shown in Figure 1-
11 10. These profiles show the relative amounts of CDD/CDF congeners in the environmental
12 releases. They can be useful for (1) identifying source contributions to near-field air
13 measurements of CDDs/CDFs, (2) comparing sources, and (3) providing insights on the
14 formation of CDDs/CDFs in the releases. There are numerous procedures for deriving a
15 congener profile, and there is no single agreed-upon convention (Cleverly et al., 1997; Lorber et
16 al., 1996; Hagenmaier et al., 1994).
17 In this document, congener profiles were developed primarily by calculating the ratio of
18 specific 2,3,7,8-substituted CDDs/CDFs in the emission or product to the total (C14 - C18)
19 CDDs/CDFs. With respect to combustion sources, the profiles were derived by dividing the
20 congener-specific emission factors by the total (C14 - C18) CDD/CDF emission factor for each
21 tested facility and then averaging the congener profiles developed for all tested facilities within
22 the combustor type. For chemical processes and commercial chemicals, CDD/CDF profiles were
23 typically generated by dividing average congener concentrations (ppt) in the chemical by the total
24 CDDs/CDFs present. Profiles for selected source categories are presented in Figure 1-10.
25 On the basis of inspection and comparisons of the average CDD/CDF congener profiles
26 across combustion and noncombustion sources, the following observations were made (Cleverly
27 et al., 1997) (these generalizations are derived from this data set, and their application beyond
28 these data is uncertain):
29
30 • It appears that combustion sources emit all 2,3,7,8-substituted CDDs/CDFs, although
31 in varying percentages of total CDDs/CDFs.
32
33 • In combustion source emissions, 2,3,7,8-TCDD is usually 0.1 to 1% of total
34 CDDs/CDFs. The exception is stack emissions from industrial oil-fired boilers,
35 where the available, but limited, data indicate that 2,3,7,8-TCDD constitutes an
36 average of 7% of total CDD/CDF emissions.
37
03/04/05 1-17 DRAFT-DO NOT CITE OR QUOTE
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1 • It cannot be concluded that octa-CDD (OCDD) is the dominant congener for all
2 combustion-generated emissions of CDDs/CDFs. OCDD dominates total emissions
3 from mass-burn MWCs that have DSs and FFs for dioxin control, industrial oil-fired
4 boilers, industrial wood-fired boilers, unleaded gasoline combustion, diesel fuel
5 combustion in trucks, and sewage sludge incinerators. The dominant congeners for
6 other combustion sources are 1,2,3,4,6,7,8-HpCDF in emissions from mass-burn
7 MWCs equipped with hot-sided electrostatic precipitators (ESPs), hazardous waste
8 incineration, and secondary aluminum smelters and 2,4-D salts and esters; OCDF in
9 emissions from medical waste incineration and industrial/utility coal-fired boilers;
10 2,3,4,7,8-PeCDF in cement kilns burning hazardous waste; and 2,3,7,8-TCDF in
11 cement kilns not burning hazardous waste.
12
13 • Evidence for a shift in the congener patterns potentially caused by the application of
14 different air pollution control systems within a combustion source type can be seen in
15 the case of mass-burn MWCs. For mass-burn MWCs equipped with hot-sided ESPs,
16 the most prevalent CDD/CDF congeners are 1,2,3,4,6,7,8-HpCDF; OCDD;
17 !,2,3,4,6,7,8-HpCDD/l,2,3,4,7,8-HxCDF; 2,3,4,6,7,8-HxCDF/octa-CDF (OCDF);
18 1,2,3,6,7,8-HxCDF. The most prevalent congeners emitted from MWCs equipped
19 with DS/FF are OCDD; 1,2,3,4,6,7,8-HpCDD; 1,2,3,4,6,7,8-HpCDF; OCDF; and
20 2,3,7,8-TCDF/l,2,3,4,7,8-HxCDD; 2,3,4,6,7,8-HxCDF.
21
22 • There is evidence of marked differences in the distribution of CDD/CDF congeners
23 between cement kilns burning and not burning hazardous waste. When not burning
24 hazardous waste as supplemental fuel, the dominant congeners appear to be 2,3,7,8-
25 TCDF; OCDD; 1,2,3,4,6,7,8-HpCDD, and OCDF. When burning hazardous waste,
26 the dominant congeners are 2,3,7,8-PeCDF; 2,3,7,8-TCDF; 1,2,3,4,7,8-HxCDF; and
27 1,2,3,4,6,7,8-HpCDD. When burning hazardous waste, OCDD and OCDF are minor
28 constituents of stack emissions.
29
30 • The congener profile of 2,4-D salts and esters seems to mimic a combustion source
31 profile in the number of congeners represented and in the minimal amount of 2,3,7,8-
32 TCDD relative to all 2,3,7,8-substituted congeners. A major difference is the
33 prevalence of 1,2,3,7,8-PeCDD in 2,4-D (14%), which is not seen in any other
34 combustion or noncombustion sources presented here.
35
36 • There are similarities in the congener profiles of PCP, diesel truck emissions,
37 unleaded gasoline vehicle emissions, and emissions from industrial wood combustors.
38 In these sources, OCDD dominates total emissions, but the relative ratio of
39 1,2,3,4,6,7,8-HpCDD to OCDD is also quite similar.
40
41 • The congener profiles for diesel truck exhaust and air measurements from a tunnel
42 study of diesel traffic are quite similar.
03/04/05 1-18 DRAFT-DO NOT CITE OR QUOTE
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Table 1-1. The TEF scheme for I-TEQ
DF
Dioxin congeners
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
TEF
1
0.5
0.1
0.1
0.1
0.01
0.001
Furan congeners
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
TEF
0.1
0.05
0.5
0.1
0.1
0.1
0.1
0.01
0.01
0.001
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Table 1-2. The TEF scheme for dioxin-like PCBs, as determined by the
World Health Organization in 1994
Chemical structure
3,3',4,4'-TeCB
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',4,4',5,5'-HxCB
3,3',4,4',5,5'-HxCB
3,3',4,4',5,5'-HxCB
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
IUPAC number
PCB-77
PCB-105
PCB-114
PCB-118
PCB-123
PCB-126
PCB-156
PCB-157
PCB-167
PCB-169
PCB-170
PCB-180
PCB-189
TEF
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
03/04/05
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Table 1-3. The TEF scheme for TEQDFP-WHO98
Dioxin congeners
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
TEF
1
1
0.1
0.1
0.1
0.01
0.0001
Furan congeners
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
TEF
0.1
0.05
0.5
0.1
0.1
0.1
0.1
0.01
0.01
0.0001
Chemical structure
3,3',4,4'-TeCB
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
IUPAC number
PCB-77
PCB-81
PCB-105
PCB-114
PCB-118
PCB-123
PCB-126
PCB-156
PCB-157
PCB-167
PCB-169
PCB-189
TEF
0.0001
0.0001
0.0001
0.0005
0.0001
0.0001
0.1
0.0005
0.0005
0.00001
0.01
0.0001
03/04/05
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Table 1-4. Nomenclature for dioxin-like compounds
Term/
symbol
Congener
Congener
group
Isomer
Specific
isomer
D
F
M
D
Tr
T
Pe
Hx
Hp
O
CDD
CDF
PCB
2,3,7,8
Definition
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 8 congener groups of CDDs, monochlorinated
through octochlorinated).
Substances that belong to the same congener group (e.g., 22 isomers constitute
the congener group of TCDDs).
Denoted by unique chemical notation (e.g., 2,4,8, 9-tetrachlorodibenzofuran is
referred to as 2,4,8,9-TCDF).
Symbol for congener class: dibenzo-p-dioxin
Symbol for congener class: dibenzofuran
Symbol for mono (i.e., one halogen substitution)
Symbol for di (i.e., two halogen substitution)
Symbol for tri (i.e., three halogen substitution)
Symbol for tetra (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)
Chlorinated dibenzo-p-dioxin, halogens substituted in any position
Chlorinated dibenzofuran, halogens substituted in any position
Polychlorinated biphenyl
Halogen substitutions in the 2,3,7,8 positions
Source: Adapted from U.S. EPA (1989).
03/04/05
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Table 1-5. Known and suspected sources of CDDs/CDFs
Emission source category
Contemporary formation sources
Quantifiable
Categories
A,B&C
Preliminary
estimate
Category D
Not
quantifiable
Category E
Reservoir sources
Quantifiable
Categories
A,B&C
Preliminary
estimate
Category D
Not
quantifiable
Category E
I. COMBUSTION SOURCES
Waste incineration
Municipal waste combustion
Hazardous waste incineration
Boilers/industrial furnaces
Medical waste/pathological incineration
Crematoria
Sewage sludge incineration
Tire combustion
Pulp and paper mill sludge incinerators
Biogas combustion
Power/energy generation
Vehicle fuel combustion - leaded*
- unleaded
- diesel
Wood combustion - residential
- industrial
Coal combustion - residential
- industrial/utility
Oil combustion - residential
- industrial/utility
£
/
£
£
7
,
/
/
/
/
/
/
/
/
/
to
-------
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o
j^.
o
Table 1-5. Known and suspected CDD/CDF sources (continued)
Emission source category
Other high-temperature sources
Cement kilns (hazardous waste burning)
Cement kilns (nonhazardous waste burning)
Asphalt mixing plants
Petroleum refining catalyst regeneration
Cigarette combustion
Carbon reactivation furnaces
Kraft recovery boilers
Manufacture of ball clay products
Glass Manufacturing
Lime Kilns
Rubber Manufacturing
Minimally controlled or uncontrolled combustion
Combustion of landfill gas in flares
Landfill fires
Accidental fires (structural)
Accidental fires (vehicles)
Forest, brush, and straw fires
Backyard barrel burning
Uncontrolled combustion of PCBs
Burning of candles
Contemporary formation sources
Quantifiable
Categories
A,B&C
\
/
Preliminary
estimate
Category D
'
\
Not
quantifiable
Category E
£
Reservoir sources
Quantifiable
Categories
A,B&C
Preliminary
estimate
Category D
Not
quantifiable
Category E
II. METAL SMELTING/REFINING
Ferrous metal smelting/refining
Sintering plants
Coke production
Electric arc furnaces
Ferrous foundries
'
/
to
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
j^.
o
Table 1-5. Known and suspected CDD/CDF sources (continued)
Emission source category
Nonferrous metal smelting/refining
Primary aluminum
Primary copper
Primary magnesium
Primary nickel
Secondary aluminum
Secondary copper
Secondary lead
Scrap electric wire recovery
Drum and barrel reclamation
Contemporary formation sources
Quantifiable
Categories
A,B&C
/
/
Preliminary
estimate
Category D
'
Not
quantifiable
Category E
'
/
Reservoir sources
Quantifiable
Categories
A,B&C
Preliminary
estimate
Category D
Not
quantifiable
Category E
III. CHEMICAL MANUFACTURING (releases to the environment)
Bleached chemical wood pulp and paper mills
Mono- to tetrachlorophenols
Pentachlorophenol
Chlorobenzenes
Chlorobiphenyls (leaks/spills)
Ethylene dichloride/vinyl chloride
Dioxazine dyes and pigments
2,4-Dichlorophenoxy acetic acid
Municipal wastewater treatment
Tall oil-based liquid soaps
IV. BIOLOGICAL AND PHOTOCHEMICAL
PROCESSES
V. RESERVOIR SOURCES
'
\
'
'
to
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
j^.
o
Table 1-5. Known and suspected CDD/CDF sources (continued)
Emission source category
Land
Air
Water
Sediments
Anthropogenic structures
PCP-treated wood
Contemporary formation sources
Quantifiable
Categories
A,B&C
Preliminary
estimate
Category D
Not
quantifiable
Category E
Reservoir sources
Quantifiable
Categories
A,B&C
Preliminary
estimate
Category D
/
Not
quantifiable
Category E
/
/
/
/
aLeaded fuel production and the manufacture of motor vehicle engines requiring leaded fuel for highway use have been prohibited in the United States.
(See Section 4.1 for details.)
to
-------
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o
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o
Table 1-6. Inventory of contemporary releases (g TEQ/yr) of I-TEQDF from known sources in the United States for
reference years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D)
Emission source category
Confidence rating"
2000 Inventory
A
B
2000
Preliminary
C II D
1995 Inventory
A
B
C
1987 Inventory
A
B
C
RELEASES TO AIR
WASTE INCINERATION
Municipal waste combustion
Hazardous waste incineration
Boilers/industrial furnaces
Halogen acid furnaces
Medical waste/pathological
incineration
Crematoria - human
- animal
Sewage sludge incineration
Tire combustion
Pulp and paper mill sludge
incineratorsb
Biogas combustion
78.9
3.18
9.4
1.82
0.3
378
0.26
0.51
0.01
0.22
1,100
5.7
14
0.38
461
0.2
0.11
7,915
5
5.8
0.77
2,440
0.14
0.11
POWER/ENERGY GENERATION
Vehicle fuel combustion
- leaded gasoline0
- unleaded gasoline on-road
- unleaded gasoline off-road
- diesel on-road
- diesel off-road
- equipment
- railroad
- commercial marine vessel
Wood combustion
- residential
6.7
0.35
61.7
21
6.4
4
11.3
1.3
4.4
31.5
11
6.6
4.5
15.7
31.9
3.3
26.3
8.8
5.5
3.6
22
to
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 1-6. Inventory of contemporary releases (g TEQ/yr) of I-TEQDF from known sources in the United States for
reference years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D)
(continued)
Emission source category
- industrial
Coal combustion
- utility boilers
- residential11
- commercial/industrial
Oil combustion
- industrial/utility (residual oil)
- industrial/utility (distillate oil)
- institutional/commercial heating
(residual oil)
- institutional/commercial heating
(distillate oil)
- residential (distillate oil)
Confidence rating"
2000 Inventory
A
B
70.4
2000
Preliminary
C II D
39.4
1.47
6.3
0.56
2.53
3.59
2.7
35.4
1995 Inventory
A
B
60.9
C
24.9
9.3
6.4
0.73
2.7
3.93
1987 Inventory
A
B
51.4
C
25.2
15.5
7.2
1.34
3.24
4.22
OTHER HIGH-TEMPERATURE SOURCES
Cement kilns (hazardous waste
burning)
Lightweight aggregate kilns
burning hazardous waste
Cement kilns (nonhazardous waste
burning)
Asphalt mixing plants
Petroleum refining catalyst
regeneration
Cigarette combustion
Carbon reactivation furnaces
Kraft recovery boilers
0.75e
63.3
1.79
16.6
2.09
0.4
0.08
0.55
2.3
145.3
2.4
15.9
2.14
0.8
0.08
2
109.6
3.3
12.3
7
2.11
1
0.06
to
oo
o
o
2
O
H
O
HH
H
W
O
-------
o
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o
4^
o
Table 1-6. Inventory of contemporary releases (g TEQ/yr) of I-TEQDF from known sources in the United States for
reference years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D)
(continued)
Emission source category
Confidence rating"
2000 Inventory
A
B
2000
Preliminary
C II D
1995 Inventory
A
B
C
1987 Inventory
A
B
C
MINIMALLY CONTROLLED OR UNCONTROLLED COMBUSTION1
Combustion of landfill gas
Landfill fires
Accidental fires - structural
Accidental fires - vehicles
Forest and brush fires'1
Backyard barrel burning1
Residential yard waste burning^
Land clearing debris burning
472.6
22
1,1268
16
23.8
4,538
9.5
528
595
573
METALLURGICAL PROCESSES
Ferrous metal smelting/refining
- sintering plants
- coke production
- electric arc furnaces
- foundries
Nonferrous metal smelting/refining
- primary copper
- secondary aluminum
- secondary copper
- secondary lead
- primary magnesium
Drum and barrel reclamation
24.4
42
0.29
2.35
33.8
0.85
0.58
6.03
59.3
13.9
25.1
<0.5
1.63
27.4
266
0.08
<0.5
1.22
29.3
15.3
966
0.08
CHEMICAL MANUFACTURE/PROCESSING SOURCES
Ethylene dichloride/vinyl chloride
Akalies/chlorine manufacturing
5.51
0.08
11.2
to
VO
o
O
2
O
H
O
HH
H
W
O
-------
o
OJ
o
j^.
o
Table 1-6. Inventory of contemporary releases (g TEQ/yr) of I-TEQDF from known sources in the United States for
reference years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D)
(continued)
Emission source category
TOTAL RELEASES TO AIR"
Confidence rating"
2000 Inventory
A
B
C
1,375.54
2000
Preliminary
D
6381.4
1995 Inventory
A
B
C
2,861.08
1987 Inventory
A
B
C
12,291.95
RELEASES TO WATER
CHEMICAL MANUFACTURE/PROCESSING SOURCES
Bleached chemical wood pulp and
paper mills
POTW (municipal) wastewater
Ethylene dichloride/vinyl chloride
Akalies/chlorine manufacturing
TOTAL RELEASES TO WATER"
1.02
23.8
1.85
26.67
15.7
15.7
28
0.043
28.04
356
356
RELEASES TO LAND
CHEMICAL MANUFACTURING/PROCESSING SOURCES
Bleached chemical wood pulp and
paper mill sludge
Ethlyene dichloride/vinyl chloride
Municipal wastewater treatment
sludge
Commercially marketed sewage
sludge
2,4-Dichlorophenoxy acetic acid
TOTAL RELEASES TO LAND"
OVERALL RELEASES TO OPEN
AND CIRCULATING
ENVIRONMENT
0.08
78.2
1.9
1.45
81.63
1,483.84
(SUM OF COLUMS A, B, C)
6,397.0
2
156.5
4
18.4
0.73
181.63
3,070.75
(SUM OF COLUMS A, B, C)
14.1
103
3.5
21.3
141.9
12,788.85
(SUM OF COLUMS A, B, C)
O
O
2
O
H
O
HH
I
O
C
o
H
W
-------
o
OJ
o
j^.
o
Table 1-6. Inventory of contemporary releases (g TEQ/yr) of I-TEQDF from known sources in the United States for
reference years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D)
(continued)
The most reliable estimates of environmental releases are those sources in
categories A, B, and C.
Included in estimate for Wood combustion - industrial.
°Leaded fuel production and the manufacture of motor vehicle engines
requiring leaded fuel for highway use have been prohibited in the
United States. (See Section 4.1 for details.)
Includes combustion of bituminous/subbituminous coal and anthracite coal.
This estimate is based on a TEQDF-WHO98 emissions estimate.
This refers to conventional pollutant control, not dioxin emissions control.
Very few of the sources listed in this inventory control specifically for
CDD/CDF emissions.
gCongener-specific emissions data were not available; the Nordic TEQ
estimate was used as a surrogate for the I-TEQDF emissions estimate.
Includes forest wildfires and prescribed burning for forest management.
This term refers to the burning of residential waste in barrels.
includes burning of brush and leaves.
Total reflects only the total of the estimates made in this report.
A = Characterization of the source category judged to be adequate for
quantitative estimation with high confidence in the emission factor and
high confidence in activity level.
B = Characterization of the source category judged to be adequate for
quantitative estimation with medium confidence in the emission factor
and at least medium confidence in activity level.
C = Characterization of the source category judged to be adequate for
quantitative estimation with low confidence in either the emission
factor and/or the activity level.
D = Preliminary indication of the potential magnitude of I-TEQDF emissions
from "Unqualified" (Category D) sources; based on extremely limited
data, judged to be clearly nonrepresentative.
POTW = Publicly owned treatment works
-------
o
OJ
o
4^
o
Table 1-7. Inventory of contemporary releases (g TEQ/yr) of TEQDF-WHO98 from known sources in the United States
for reference years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D)
Emission source category
Confidence rating"
2000 Inventory
A
B
2000
Preliminary
C II D
1995 Inventory
A
B
C
1987 Inventory
A
B
C
RELEASES TO AIR
WASTE INCINERATION
Municipal waste combustion
Hazardous waste incineration
Boilers/industrial furnaces
Halogen acid furnaces
Medical waste/pathological
incineration
Crematoria - human
- animal
Sewage sludge incineration
Tire combustion
Pulp and paper mill sludge
incinerators0
Biogas combustion
78.9"
3.2
9.6
1.82
0.31
378
0.27
0.51
0.01
0.22
1,250
5.8
14.2
0.39
488
0.21
0.11
8,877
5
5.8
0.78
2,590
0.14
0.11
POWER/ENERGY GENERATION
Vehicle fuel combustion
- leaded gasoline11
- unleaded gasoline on-road
- unleaded gasoline off-road
- diesel on-road
- diesel off-road
- equipment
- railroad
- commercial marine vessel
Wood combustion
- residential
- industrial
7
0.36
65.4
22
6.8
4.3
11.3"
41.5
1.6
4.7
33.3
12
7
4.8
15.7"
26.2
37.5
3.6
27.8
9.4
5.8
3.8
22"
26.5
to
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 1-7. Inventory of contemporary releases (g TEQ/yr) of TEQDF-WHO98 from known sources in the United States for reference
years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D) (continued)
Emission source category
Coal combustion
- utility boilers
- residential'
- commercial/industrial
Oil combustion
- industrial/utility (residual oil)
- industrial/utility (distillate oil)
- institutional/commercial heating
(residual oil)
- institutional/commercial heating
(distillate oil)
- residential (distillate oil)
Confidence rating"
2000 Inventory
A
B
69.5
2000
Preliminary
C II D
1.69
7.25
0.65
2.92
4.54
2.7"
35.4"
1995 Inventory
A
B
60.1
C
10.7
7.3
0.84
3.11
4.98
1987 Inventory
A
B
50.8
C
17.8
8.3
1.54
3.73
5.35
OTHER HIGH-TEMPERATURE SOURCES
Cement kilns (hazardous waste
burning)
Lightweight aggregate kilns
burning hazardous waste
Cement kilns (nonhazardous waste
burning)
Asphalt mixing plants
Petroleum refining catalyst
Regeneration
Cigarette combustion
Carbon reactivation furnaces
Kraft recovery boilers
0.75
68.4
1.86
17.2
2.19
0.4
0.08"
0.55"
2.3
156.1
2.4"
16.6
2.24
0.8
0.08"
2
117.8
3.3"
12.7
2.21
1
0.06"
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 1-7. Inventory of contemporary releases (g TEQ/yr) of TEQDF-WHO98 from known sources in the United States for reference
years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D) (continued)
Emission source category
Confidence rating"
2000 Inventory
A
B
2000
Preliminary
C II D
1995 Inventory
A
B
C
1987 Inventory
A
B
C
MINIMALLY CONTROLLED OR UNCONTROLLED COMBUSTION1
Combustion of landfill gas
Landfill fires
Accidental fires - structural
- vehicles
Forest and brush fires'1
Backyard barrel burning1
Residential yard waste burning^
Land clearing debris burning
498.53
22"
1,1268
16"
23.8"
4,880
10.2
568
628
604
METALLURGICAL PROCESSES
Ferrous metal smelting/refining
- sintering plants
- coke production
- electric arc furnaces
- foundries
Nonferrous metal smelting/refining
- primary copper
- secondary aluminum
- secondary copper
- secondary lead
- primary magnesium
Drum and barrel reclamation
27.6
42"
0.29"
2.48
35.9
0.86
0.61
6.03"
59.3"
13.9"
28
<0.5b
1.72
29.1
271
0.08
<0.5b
1.29
32.7
16.3
983
0.08
CHEMICAL MANUFACTURE/PROCESSING SOURCES
Ethylene dichloride/vinyl chloride
Akalies/chlorine manufacturing
Bleached chemical wood pulp and
paper mills
5.46"
0.08"
11.2"
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 1-7. Inventory of contemporary releases (g TEQ/yr) of TEQDF-WHO98 from known sources in the United States for reference
years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D) (continued)
Emission source category
TOTAL RELEASES TO AIRk
Confidence rating"
2000 Inventory
A
B
C
1,422.51
2000
Preliminary
D
6,764.11
1995 Inventory
A
B
C
3,101.16
1987 Inventory
A
B
C
13,479.69
RELEASES TO WATER
CHEMICAL MANUFACTURE/PROCESSING SOURCES
Bleached chemical wood pulp and
paper mills
POTW (municipal) wastewater
Ethylene dichloride/vinyl chloride
Akalies/chlorine manufacturing
TOTAL RELEASES TO WATER"
1.02
22.6"
1.82"
25.44
13
13
28
0.043"
28.04
356
356
RELEASES TO LAND
CHEMICAL MANUFACTURING/PROCESSING SOURCES
Bleached chemical wood pulp and
paper mill sludge
Ethlyene dichloride/vinyl chloride
Municipal wastewater treatment
sludge
Commercially marketed sewage
sludge
2,4-Dichlorophenoxy acetic acid
TOTAL RELEASES TO LAND1
OVERALL RELEASES TO OPEN
AND CIRCULATING
ENVIRONMENT
0.08
78.2
1.9
1.36
81.54
1,529.49
(SUM OF COLUMS A, B, C)
6777.1
2
116.1
3
28.9
0.73"
150.73
3,279.93
(SUM OF COLUMS A, B, C)
14.1
76.6
2.6
33.4
126.7
13,962.39
(SUM OF COLUMS A, B, C)
o
o
2
o
H
O
HH
H
W
O
C
o
H
W
The most reliable estimates of environmental releases are those sources in
categories A, B, and C.
bThis estimate is based on a TEQDF-WHO98 emissions estimate.
Included in estimate for Wood combustion - industrial.
dLeaded fuel production and the manufacture of motor vehicle engines
requiring leaded fuel for highway use have been prohibited in the
United States. (See Section 4.1 for details.)
Includes combustion of bituminous/subbituminous coal and anthracite coal.
-------
O
O
2
O
H
O
HH
H
W
Table 1-7. Inventory of contemporary releases (g TEQ/yr) of TEQDF-WHO98 from known sources in the United States for reference
years 2000,1995, and 1987 (Columns A, B & C) and preliminary release estimates for 2000 (Column D) (continued)
fThis refers to conventional pollutant control, not dioxin emissions control.
Very few of the sources listed in this inventory control specifically for
CDD/CDF emissions.
gCongener-specific emissions data were not available; the Nordic TEQ
estimate was used as a surrogate for the I-TEQDF emissions estimate.
Includes forest wildfires and prescribed burning for forest management.
This term refers to the burning of residential waste in barrels.
includes burning of brush and leaves.
kTotal reflects only the total of the estimates made in this report.
A = Characterization of the source category judged to be adequate for
quantitative estimation with high confidence in the emission factor
and high confidence in activity level.
B = Characterization of the source category judged to be adequate for
quantitative estimation with medium confidence in the emission factor
and at least medium confidence in activity level.
C = Characterization of the source category judged to be adequate for
quantitative estimation with low confidence in either the emission
factor and/or the activity level.
D = Preliminary indication of the potential magnitude of I-TEQDF emissions
from "Unqualified" (Category D) sources; based on extremely limited
data, judged to be clearly nonrepresentative.
POTW = Publicly owned treatment works
O
-------
Table 1-8. Identification of products containing CDDs/CDFs (g I-TEQDF/yr)
Product
Bleached chemical wood pulp
Ethylene dichloride/vinyl chloride
Chloaranil
Pentachlorophenol
2,4 -Dichlorophenoxy acetic acid
TOTAL AMOUNT IN PRODUCTS
2000
0.58
0.02
1.16
7,325
NA
7,327
1995
40
0.02
50.6
8,400
18.4
8,509
1987
505
NA
NA
36,000
21.3
36,526
NA = Information not available
Only 2,4-D is considered an environmental release.
03/04/05
1-37
DRAFT—DO NOT CITE OR QUOTE
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Table 1-9. Identification of products containing CDDs/CDFs (g TEQDF-
WH098/yr)
Product
Bleached chemical wood pulp
Ethylene dichloride/vinyl chloride
Chloranil
Pentachlorophenol
2,4 -Dichlorophenoxy acetic acid
TOTAL AMOUNT IN PRODUCTS
2000
0.58
0.02
1.16
4,395
NA
4,397
1995
40
0.02
64
4,800
28.9
4,933
1987
505
NA
NA
20,000
33.4
20,538
NA = Information not available
Only 2,4-D is considered an environmental release.
03/04/05
1-38
DRAFT—DO NOT CITE OR QUOTE
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Table 1-10. Confidence rating scheme for U.S. emission estimates
Confidence rating
Activity level estimate
Emission factor estimate
Categories/media for which releases can be reasonably quantified
High
Medium
Low
Derived from comprehensive survey
Based on estimates of average plant
activity level and number of plants or
limited survey
Based on data judged possibly
nonrepresentative
Derived from comprehensive survey
Derived from testing at a limited but
reasonable number of facilities believed
to be representative of source category
Derived from testing at only a few,
possibly nonrepresentative facilities or
from similar source categories
Categories/media for which releases cannot be reasonably quantified
Preliminary estimate
Not quantified
Based on extremely limited data,
judged to be clearly nonrepresentative
No data available
Based on extremely limited data, judged
to be clearly nonrepresentative
( 1 ) Argument based on theory but no
data, or
(2) Data available indicating formation
but not in a form that allows
developing an emission factor
03/04/05
1-39
DRAFT—DO NOT CITE OR QUOTE
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o
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o
4^
o
Table 1-11. I-TEQDF emission factors used to develop national emission inventory estimates of releases to air
Emission source category
I-TEQDF emission factor
2000
1995
1987
Emission factor units
WASTE INCINERATION
Municipal waste combustion
Hazardous waste incineration
Boilers/industrial furnaces
Halogen acid furnaces
Medical waste/pathological incineration
Crematoria - human
- animal
Sewage sludge incineration
Tire combustion
Pulp and paper mill sludge incinerators15
2.82
2.12
1.21
0.803
630a
410
0.11
6.65
0.282
38.2a
3.83
0.64
598a
17,000
6.94
0.282
573a
3.83
0.64
l,706a
17,000
6.94
0.282
ng TEQ/kg waste combusted
ng TEQ/kg waste combusted
ng TEQ/kg waste combusted
ng TEQ/kg waste feed
ng TEQ/kg waste combusted
ng TEQ/body
ng TEQ/kg animal
ng TEQ/kg dry sludge combusted
ng TEQ/kg tires combusted
POWER/ENERGY GENERATION
Vehicle fuel combustion - leaded0
- unleaded
- diesel
Wood combustion - residential
- industrial
Coal combustion - utility
Oil combustion - industrial/utility
NA
1.5
172
0.5
0.56-13.2d
0.079
0.2
45
1.5
172
2
0.56-13.2d
0.079
0.2
45
1.5
172
2
0.56-13.2d
0.079
0.2
pg TEQ/km driven
pg TEQ/km driven
pg TEQ/km driven
ng TEQ/kg wood combusted
ng TEQ/kg wood combusted
ng TEQ/kg coal combusted
ng TEQ/L oil combusted
OTHER HIGH-TEMPERATURE SOURCES
Cement kilns burning hazardous waste
Lightweight aggregate kilns
Cement kilns not burning hazardous waste
Petroleum refining catalyst regeneration
Cigarette combustion
Carbon reactivation furnaces
Kraft recovery boilers
1.04-28.586
2.06
0.27
1.52
0.00043-0.0029
1.2
0.029
1.04-28.586
0.27
1.52
0.00043-0.0029
1.2
0.029
1.04-28.586
0.27
1.52
0.00043-0.0029
1.2
0.029
ng TEQ/kg clinker produced
ng TEQ/ kg waste feed
ng TEQ/kg clinker produced
ng TEQ/barrel reformer feed
ng TEQ/cigarette
ng TEQ/kg of reactivated carbon
ng TEQ/kg solids combusted
MINIMALLY CONTROLLED OR UNCONTROLLED COMBUSTION
Backyard barrel burningf
72.8
72.8
72.8
ng TEQ/kg waste combusted
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 1-11. I-TEQDF emission factors used to develop national emission inventory estimates of releases to air
(continued)
Emission source category
I-TEQDF emission factor
2000
1995
1987
Emission factor units
METALLURGICAL PROCESSES
Ferrous metal smelting/refining - sintering plants
Nonferrous metal smelting/refining
- primary copper
- secondary aluminum smelting
- secondary copper smelting8
- secondary lead smelters
Drum and barrel reclamation
0.55-4.14
<0.31
21.1
0.05-8.31
16.5
0.55-4.14
O.31
21.1
0.05-8.31
16.5
0.55-4.14
O.31
21.1
0.05-8.31
16.5
ng TEQ/kg sinter
ng TEQ/kg copper produced
ng TEQ/kg scrap feed
ng TEQ/kg scrap consumed
ng TEQ/kg lead produced
ng TEQ/drum
CHEMICAL MANUFACTURING/PROCESSING SOURCES
Ethylene dichloride/vinyl chloride
0.95a
ng TEQ/kg EDC produced
O
O
2
O
H
O
HH
H
W
"Different emission factors were derived for various subcategories within this industry; the value listed is a weighted average.
Included in total for Wood combustion - industrial.
°Leaded fuel production and the manufacture of motor vehicle engines requiring leaded fuel for highway use have been prohibited in the United States.
(See Section 4.1 for details.)
dEmission factor of 0.56 ng I-TEQDF/kg used for nonsalt-laden wood; emission factor of 13.2 ng I-TEQDF/kg used for salt-laden wood.
eEmission factor of 1.04 ng I-TEQDF/kg used for kilns with air pollution control device inlet temperatures less than 232 °C; emission factor of 28.58 ng
I-TEQDF/kg used for kilns with APCD inlet temperatures greater than 232 °C.
Includes the burning of brush and leaf residential yard waste.
facility-specific emission factors were used ranging from 3.6 to 16,600 ng I-TEQDF/kg scrap consumed.
O
-------
o
OJ
o
4^
o
Table 1-12. TEQDF-WHO98 emission factors used to develop national emission inventory estimates of releases
to air
Emission source category
TEQDF-WHO98 emission factor
2000
1995
1987
Emission factor units
WASTE INCINERATION
Municipal waste combustion
Hazardous waste incineration
Boilers/industrial furnaces
Halogen acid furnaces
Medical waste/pathological incineration
Crematoria - humanb
- animal
Sewage sludge incineration
Tire combustion
Pulp and paper mill sludge incinerators0
2.82
2.13
1.21
0.836
630a
434
0.12
6.74
0.281
43. 4a
3.88
0.65
633a
17,000
7.04
0.281
644a
3.88
0.65
l,811a
17,000
7.04
0.281
ng TEQ/kg waste combusted
ng TEQ/kg waste combusted
ng TEQ/kg waste combusted
ng TEQ/kg waste feed
ng TEQ/kg waste combusted
ng TEQ/body
ng TEQ/kg animal
ng TEQ/kg dry sludge combusted
ng TEQ/kg tires combusted
POWER/ENERGY GENERATION
Vehicle fuel combustion - leadedd
- unleaded
- diesel
Wood combustion - residential
- industrial6
Coal combustion - utility
Oil combustion - industrial/utility
NA
1.6
182
2b
0.6-13.2
0.78
0.23
53
1.6
182
2b
0.6-13.2
0.078
0.23
53
1.6
182
2b
0.6-13.2
0.078
0.23
pg TEQ/km driven
pg TEQ/km driven
pg TEQ/km driven
ng TEQ/kg wood combusted
ng TEQ/kg wood combusted
ng TEQ/kg coal combusted
ng TEQ/L oil combusted
OTHER HIGH-TEMPERATURE SOURCES
Cement kilns burning hazardous waste
Lightweight aggregate kilns
Cement kilns not burning hazardous waste
Petroleum refining catalyst regeneration
Cigarette combustion
Carbon reactivation furnaces
Kraft recovery boilers
l.ll-30.7f
1.99
0.26
1.59
0.00044-0.003
1.2b
0.028
l.ll-30.7f
0.26
1.59
0.00044-0.003
1.2b
0.028
l.ll-30.7f
0.26
1.59
0.00044-0.003
1.2b
0.028
ng TEQ/kg clinker produced
ng TEQ/ kg waste feed
ng TEQ/kg clinker produced
ng TEQ/barrel reformer feed
ng TEQ/cigarette
ng TEQ/kg of reactivated carbon
ng TEQ/kg solids combusted
to
o
o
2
o
H
O
HH
H
W
O
O
-------
o
o
o
OO
Table 1-12. TEQDF-WHO98 emission factors used to develop national emission inventory estimates of releases
to air (continued)
Emission source category
TEQDF-WHO98 emission factor
2000
1995
1987
Emission factor units
MINIMALLY CONTROLLED OR UNCONTROLLED COMBUSTION
Backyard barrel burning8
76. 8b
76.8b
76.8b
ng TEQ/kg waste combusted
METALLURGICAL PROCESSES
Ferrous metal smelting/refining - sintering plants
Nonferrous metal smelting/refining
- primary copperb
- secondary aluminum smelting
- secondary copper smelting11
- secondary lead smelters
Drum and barrel reclamation
0.62-4.61
0.31
22.4
0.05-8.81
17.5
0.62-4.61
0.31
22.4
0.05-8.81
17.5
0.62-4.61
0.31
22.4
0.05-8.81
17.5
ng TEQ/kg sinter
ng TEQ/kg copper produced
ng TEQ/kg scrap feed
ng TEQ/kg scrap consumed
ng TEQ/kg lead produced
ng TEQ/drum
CHEMICAL MANUFACTURING/PROCESSING SOURCES
Ethylene dichloride/vinyl chloride
0.95a'b
ng TEQ/kg EDC produced
O
O
2
O
H
O
HH
H
W
different emission factors were derived for various subcategories within this industry; the value listed is a weighted average.
bCongener-specific data were not available; the TEQDF emission factor was used as a surrogate for the TEQDF-WHO98 emission factor.
Included in total for Wood combustion - industrial.
dLeaded fuel production and the manufacture of motor vehicle engines requiring leaded fuel for highway use have been prohibited in the United States.
(See Section 4.1 for details).
eEmission factor of 0.6 ng I-TEQDF/kg used for non-salt-laden wood; emission factor of 13.2 ng I-TEQDF/kg used for salt-laden wood.
Emission factor of 1.11 ng I-TEQDF/kg used for kilns with air pollution control device inlet temperatures less than 232 °C; emission factor of 28.58 ng
I-TEQDF/kg used for kilns with APCD inlet temperatures greater than 232 °C.
gThis term refers to the burning of residential waste in barrels.
hFacility-specific emission factors were used ranging from 3.6 to 16,600 ng TEQDF-WHO98/kg scrap consumed.
O
-------
Table 1-13. Releases (g TEQDF-WHO98) to the open environment from reservoir sources
Urban runoff to surface
water
Rural soil erosion to
surface water
Reference year
2000
142 (D)
2,500 (D)
Reference year
1995
133 (D)
2,600 (D)
Reference year
1987
124 (D)
2,900 (D)
Letter in parenthesis shows the confidence rating for these releases.
03/04/05
1 -44 DRAFT—DO NOT CITE OR QUOTE
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Table 1-14. Sources in quantitative inventory ranked by releases to all media
Ranking of the year 2000 sources
Backyard barrel burning of refuse (Air)
Medical waste/pathological incineration (Air)
Municipal waste combustion (Air)
Municipal wastewater treatment sludge
(Land)
Coal fired-utility boilers (Air)
Cement kilns (hazardous waste burning)
(Air)
Diesel heavy duty trucks (Air)
Primary Magnesium production (Air)
Industrial wood combustion (Air)
Secondary aluminum smelting (Air)
Ethylene dichloride/vinyl chloride production
(Water + Land + Air)
Sintering plants (Air)
Diesel off road equipment (Air)
Yr 2000
(grams)
498.53
378
78.9
78.2
69.5
68.4
65.4
42
41.5
35.9
29.42
27.6
22
Percent
of Total
32.59%
24.71%
5.16%
5.11%
4.54%
4.47%
4.28%
2.75%
2.71%
2.35%
1.92%
1.80%
1.44%
Ranking of the year 1995 sources
Municipal waste combustion (Air)
Backyard barrel burning of refuse
(Air)
Medical waste/pathological incineration
(Air)
Secondary copper smelters (Air)
Cement kilns (hazardous waste burning)
(Air)
Municipal wastewater treatment sludge
(Land)
Coal fired-utility boilers (Air)
Diesel heavy duty trucks (Air)
Bleached chemical wood pulp and paper
mills (Water + Land)
Secondary aluminum smelting (Air)
2,4-Dichlorophenoxy acetic acid (Land)
Sintering plants (Air)
Industrial wood combustion (Air)
Yr 1995
(grams)
1250
628
488
271
156.1
116.1
60.1
33.3
30
29.1
28.9
28
26.2
Percent
of Total
38.11%
19.15%
14.88%
8.26%
4.76%
3.54%
1.83%
1.02%
0.91%
0.89%
0.88%
0.85%
0.80%
Ranking of the year 1987 sources
Municipal waste combustion (Air)
Medical waste/pathological
incineration (Air)
Secondary copper smelters (Air)
Backyard barrel burning of refuse
(Air)
Bleached chemical wood pulp and
paper mills (Water + Land)
Cement kilns (hazardous waste
burning) (Air)
Municipal wastewater treatment
sludge (Land)
Coal fired-utility boilers (Air)
Automobiles using leaded gasoline
(Air)
2,4-Dichlorophenoxy acetic acid
(Land)
Sintering plants (Air)
Diesel heavy duty trucks (Air)
Industrial wood combustion (Air)
Yr 1987
(grams)
8877
2590
983
604
370.1
117.8
76.6
50.8
37.5
33.4
32.7
27.8
26.5
Percent
of Total
63.58%
18.55%
7.04%
4.33%
2.65%
0.84%
0.55%
0.36%
0.27%
0.24%
0.23%
0.20%
0.19%
-------
Table 1-14. Sources in quantitative inventory ranked by releases to all media (continued)
Ranking of the year 2000 sources
Cement kilns (nonhazardous waste burning)
(Air)
Residential wood combustion (Air)
Sewage sludge incineration (Air)
Industrial/utility oil combustion (distillate oil)
(Air)
Automobiles using unleaded gasoline (Air)
Diesel railroad locomotives (Air)
Residential heating (distillate oil) (Air)
Diesel commercial marine vessel (Air)
Hazardous waste incineration (Air)
Institutional/commercial heating (distillate
oil) (Air)
Secondary lead smelting (Air)
Petroleum Refining Catalyst Regeneration
(Air)
Commercially marketed sewage sludge
(Land)
Yr 2000
(grams)
17.2
11.3
9.6
7.25
7
6.8
4.54
4.3
3.2
2.92
2.48
2.19
1.9
Percent
of Total
1.12%
0.74%
0.63%
0.47%
0.46%
0.44%
0.30%
0.28%
0.21%
0.19%
0.16%
0.14%
0.12%
Ranking of the year 1995 sources
Cement kilns (nonhazardous waste
burning) (Air)
Residential wood combustion (Air)
Sewage sludge incineration (Air)
Diesel off road equipment (Air)
Ethylene dichloride/vinyl chloride
production (Water + Land + Air)
Industrial/utility oil combustion
(residual oil) (Air)
Industrial/utility oil combustion
(distillate oil) (Air)
Diesel railroad locomotives (Air)
Hazardous waste incineration (Air)
Residential heating (distillate oil) (Air)
Diesel commercial marine vessel (Air)
Automobiles using unleaded gasoline
(Air)
Institutional/commercial heating
(distillate oil) (Air)
Yr 1995
(grams)
16.6
15.7
14.2
12
11.97
10.7
7.3
7
5.8
4.98
4.8
4.7
3.11
Percent
of Total
0.51%
0.48%
0.43%
0.37%
0.36%
.33%
0.22%
0.21%
0.18%
0.15%
0.15%
0.14%
0.09%
Ranking of the year 1987 sources
Residential wood combustion (Air)
Industrial/utility oil combustion
(residual oil) (Air)
Secondary aluminum smelting (Air)
Cement kilns (nonhazardous waste
burning) (Air)
Diesel off road equipment (Air)
Industrial/utility oil combustion
(distillate oil) (Air)
Diesel railroad locomotives (Air)
Sewage sludge incineration (Air)
Residential heating (distillate oil)
(Air)
Hazardous waste incineration (Air)
Diesel commercial marine vessel
(Air)
Institutional/commercial heating
(distillate oil (Air)
Automobiles using unleaded
gasoline (Air)
Yr 1987
(grams)
22
17.8
16.3
12.7
9.4
8.3
5.8
5.8
5.35
5
3.8
3.73
3.6
Percent
of Total
0.16%
0.13%
0.12%
0.09%
0.07%
0.06%
0.04%
0.04%
0.04%
0.04%
0.03%
0.03%
0.03%
-------
Table 1-14. Sources in quantitative inventory ranked by releases to all media (continued)
Ranking of the year 2000 sources
Akalies/chlorine manufacturing (Water +
Air)
Lightweight aggregate kilns burning
hazardous waste (Air)
Boilers/industrial furnaces (Air)
Industrial/utility oil combustion (residual oil)
(Air)
Bleached chemical wood pulp and paper
mills (Water + Land)
Secondary copper smelting (Air)
Kraft recovery boilers (Air)
Institutional/commercial heating (residual oil)
(Air)
Drum and barrel reclamation (Air)
Tire incineration (Air)
Cigarette combustion (Air)
Unleaded gasoline off-road equipment (Air)
Halogen acid furnaces (Air)
Primary copper smelting (Air)
Crematoria - human (Air)
Automobiles using leaded gasoline (Air)
Yr 2000
(grams)
1.9
1.86
1.82
1.69
1.1
0.86
0.75
0.65
0.61
0.51
0.4
0.36
0.31
0.29
0.27
0
Percent
of Total
0.12%
0.12%
0.12%
0.11%
0.07%
0.06%
0.05%
0.04%
0.04%
0.03%
0.03%
0.02%
0.02%
0.02%
0.02%
0.00%
Ranking of the year 1995 sources
Commercially marketed sewage sludge
(Land)
Lightweight aggregate kilns burning
hazardous waste (Air)
Kraft recovery boilers (Air)
Petroleum Refining Catalyst
Regeneration (Air)
Secondary lead smelting (Air)
Automobiles using leaded gasoline (Air)
Industrial/utility oil combustion
(residual oil) (Air)
Cigarette combustion (Air)
Primary copper smelting (Air)
Boilers/industrial furnaces (Air)
Crematoria - human (Air)
Tire incineration (Air)
Drum and barrel reclamation (Air)
Carbon reactivation furnaces (Air)
Yr 1995
(grams)
3
2.4
2.3
2 24
1.72
1.6
0.84
0.8
0.5
0.39
0.21
0.11
0.08
0.08
Percent
of Total
0.09%
0.07%
0.07%
0.07%
0.05%
0.05%
0.03%
0.02%
0.02%
0.01%
0.01%
0.003%
0.002%
0.002%
Ranking of the year 1987 sources
Lightweight aggregate kilns
burning hazardous waste (Air)
Commercially marketed sewage
sludge (Land)
Petroleum Refining Catalyst
Regeneration (Air)
Kraft recovery boilers (Air)
Industrial/utility oil combustion
(residual oil) (Air)
Secondary lead smelting (Air)
Cigarette combustion (Air)
Boilers/industrial furnaces (Air)
Primary copper smelting (Air)
Crematoria - human (Air)
Tire incineration (Air)
Drum and barrel reclamation (Air)
Carbon reactivation furnaces (Air)
Yr 1987
(grams)
3.3
2.6
2.21
9
1.54
1.29
1
0.78
0.5
0.14
0.11
0.08
0.06
Percent
of Total
0.02%
0.02%
0.02%
0.01%
0.01%
0.01%
0.01%
0.01%
0.004%
0.001%
0.001%
0.001%
0.000%
-------
o
OJ
o
4^
o
Table 1-14. Sources in quantitative inventory ranked by releases to all media (continued)
Ranking of the year 2000 sources
TOTAL
Yr 2000
(grams)
1529.49
Percent
of Total
100%
Ranking of the year 1995 sources
Yr 1995
(grams)
3279.93
Percent
of Total
100%
Ranking of the year 1987 sources
Yr 1987
(grams)
13962.39
Percent
of Total
100%
oo
O
H
O
HH
H
W
O
c
o
-------
2,3,7,8-Tetrachlorodibenzo-p-dioxin
ci
1,2,3,7,8-Pentachlorodibenzo-p-dioxin
CI
S.S'^'.S.S'-Hexachlorobiphenyl
ci
2,3,7,8-Tetrachlorodibenzofuran
ci
2,3,4,7,8-Pentachlorodibenzofuran
ci
3,3',4,4',5-Pentachlorobiphenyl
Figure 1-1. Chemical structure of 2,3,7,8-TCDD and related compounds.
03/04/05
1 -49 DRAFT—DO NOT CITE OR QUOTE
-------
Emission Source
(tested / total units)
Municipal Waste Combustion (19 /113)
Medical Waste Incineration (8 / 5000)
Secondary Copper Smelting (2 / 4)
Backyard Barrel Burning (6 /)
Cement Kilns Burning Haz Waste (10 / ?)
Utility / Industrial Coal Combustion (11 / >1000)
On-road Leaded Gas Fuel Combustion (? / ?)
Iron Ore Sinter Plants (2 / ?)
On-road Diesel Fuel Combustion (NA)
Industrial Wood Burning (9 / ?)
Residential Wood Burning (7 / 25000000)
Off-road Diesel Fuel Combustion (NA)
Utility / Industrial Residual Oil Combustion (? / ?)
Secondary Aluminum Smelting (6 / 67)
Cement Kilns Not Burning Haz Waste (15/7)
Utility / Industrial Distillate Oil Combustion (>2 / ?)
Sewage Sludge Incineration (13 /199)
Hazardous Waste Incineration (17 /171-227)
On-road Unleaded Gas Fuel Combustion (? / ?)
Manufacture of EDC/VC (? / ?)
Best Estimate of
I-TEQ Emission Factor
(ng/kgorng/L)
Total Annual "Activity"
(thousand metric tons/yr or
million L/yr)
Annual I-TEQ Emission
(g l-TEQ/yr)
The figures include sources with annual I-TEQ emission estimates greater than 5 g l-TEQ/yr in
one or both of the Reference Years 1987 or 1995. Derivation of the emission factors
and annual "Activity" estimates (e.g., kg of waste incinerated) are presented in the following
chapters of this report. The difference in bar shading indicates the degree of confidence in the
estimate. The set of numbers following the source categories indicates the number of
facilities/sites for which emission test data are available versus the number of facilities/sites
in the category. A question mark (?) indicates that the precise number of facilities/sites
could not be estimated.
Legend
Figure 1-2. Estimated CDD/CDF I-TEQ emissions to air from combustion
sources in the United States (reference year: 1987).
Note: Municipal solid waste incineration is currently referred to as municipal waste
combustion.
03/04/05
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DRAFT—DO NOT CITE OR QUOTE
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Emission Source
(tested /total units)
Municipal Waste Combustion (39 /130)
Medical Waste Incineration (20 / 2400)
Secondary Copper Smelting (2 / 3)
Backyard Barrel Burning (6 /)
Cement Kilns Burning Haz Waste (10 / 34)
Utility/Industrial Coal Combustion (11 />1000)
On-road Leaded Gas Fuel Combustion (? / ?)
Iron Ore Sinter Plants (21 11)
On-road Diesel Fuel Combustion (NA)
Industrial Wood Burning (9 / ?)
Residential Wood Burning (7 / 25000000)
Off-road Diesel Fuel Combustion (NA)
Utility /Industrial Residual Oil Combustion (? / ?)
Secondary Aluminum Smelting (6 / 76)
Cement Kilns Not Burning Haz Waste (15 /178)
Utility /Industrial Distillate Oil Combustion (>2 / ?)
Sewage Sludge Incineration (13 / 257)
Hazardous Waste Incineration (17 /162)
On-road Unleaded Gas Fuel Combustion (? / ?)
Manufacture of EDC/VC (? / ?)
Best Estimate of
I-TEQ Emission Factor
(ng/kg or ng/L)
Total Annual "Activity"
(thousand metric tons/yr or
million L/yr)
Annual I-TEQ Emission
(g l-TEQ/yr)
The figures include sources with annual I-TEQ emission estimates greater than 5 g l-TEQ/yr in
one or both of the Reference Years 1987 or 1995. Derivation of the emission factors
and annual "Activity" estimates (e.g., kg of waste incinerated) are presented in the following
chapters of this report. The difference in bar shading indicates the degree of confidence in the
estimate. The set of numbers following the source categories indicates the number of
facilities/sites for which emission test data are available versus the number of facilities/sites
in the category. A question mark (?) indicates that the precise number of facilities/sites
could not be estimated.
Figure 1-3. Estimated CDD/CDF I-TEQ emissions to air from combustion
sources in the United States (reference year: 1995).
Note: Municipal solid waste incineration is currently referred to as municipal
waste combustion.
03/04/05
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DRAFT—DO NOT CITE OR QUOTE
-------
Emission Source
(tested/total units)
Municipal Waste Combustion (195 / 251)
Medical Waste Incineration (22 / ?)
Secondary Copper Smelting (1 / 2)
Backyard Barrel Burning (6 / ?)
Cement Kilns Burning Haz Waste (10 /17)
Utility / Industrial Coal Combustion (11 / >1000)
On-road Leaded Gas Fuel Combustion (0 / 0)
Iron Ore Sinter Plants (2/11)
On-road Diesel Fuel Combustion (NA)
Industrial Wood Burning (9 / ?)
Residential Wood Burning (19 / 25000000)
Off-road Diesel Fuel Combustion (NA)
Utility/ Industrial Residual Oil Combustion (?/ ?)
Secondary Aluminum Smelting (6 / ?)
Cement Kilns Not Burning Haz Waste (15 / ?)
Utility / Industrial Distillate Oil Combustion (>2 / ?)
Sewage Sludge Incineration (14 / ?)
Hazardous Waste Incineration (22 /132)
On-road Unleaded Gas Fuel Combustion (?/ ?)
Manufacture of EDC/VC (8 /12)
Best Estimate of
I-TEQ Emission Factor
(ng/kg or ng/L)
Total Annual "Activity"
(thousand metric tons/yr or
million L/yr)
Annual I-TEQ Emission
(g l-TEQ/yr)
The figures include sources with annual I-TEQ emission estimates greater than 5 g l-TEQ/yr in
one or both of the Reference Years 1987 or 1995. Derivation of the emission factors
and annual "Activity" estimates (e.g., kg of waste incinerated) are presented in the following
chapters of this report. The difference in bar shading indicates the degree of confidence in the
estimate. The set of numbers following the source categories indicates the number of
facilities/sites for which emission test data are available versus the number of facilities/sites
in the category. A question mark (?) indicates that the precise number of facilities/sites
could not be estimated.
Legend
Figure 1-4. Estimated CDD/CDF I-TEQ emissions to air from combustion
sources in the United States (reference year: 2000).
03/04/05
1-52
DRAFT—DO NOT CITE OR QUOTE
-------
Municipal Waste Combustion
Backyard Barrel Burning
Medical Waste Incineration
Secondary Copper Smelting
Cement Kilns Burning Haz Waste
Residential Wood Burning
UtilityJIndustrial Coal Combustion
On-Road Diesel Fuel Combustion
Secondary Aluminum Smelting
Industrial Wood Burning
Iron Ore Sinter Plants
Cement Kilns Mot Burning Haz Waste
Sewage Sludge Incineration
Manufacture of EDCA'C
Utility/Industrial Oil Combustion
Crematoria (human)
Hazardous Waste Incineration
On-Road Unleaded Gas Fuel Combustion
On-Road Leaded Gas Fuel Combustion
0.1
10
100
1000
10000
11987 D1995 D2000
Figure 1-5. Comparison of estimates of annual I-TEQ emissions to air
(g I-TEQ/yr) for reference years 1987,1995, and 2000.
03/04/05
1-53
DRAFT—DO NOT CITE OR QUOTE
-------
Emission Source
(tested /total units)
Municipal Waste Combustion (19/113)
Medical Waste Incineration (8 / 5000)
Secondary Copper Smelting (2 / 4)
Backyard Barrel Burning (NA)
Cement Kilns Burning Haz Waste (10 / ?)
Utility/Industrial Coal Combustion (11 />1000)
On-road Leaded Gas Fuel Combustion (? / ?)
Iron Ore Sinter Plants (2 / ?)
On-road Diesel Fuel Combustion (NA)
Industrial Wood Burning (9 / ?)
Residential Wood Burning (7 / 25000000)
Off-road Diesel Fuel Combustion (NA)
Utility / Industrial Residual Oil Combustion (? / ?)
Secondary Aluminum Smelting (6 / 67)
Cement Kilns Not Burning Haz Waste (15 / ?)
Utility / Industrial Distillate Oil Combustion (>2 / ?)
Sewage Sludge Incineration (13 /199)
Hazardous Waste Incineration (17 /171-227)
On-road Unleaded Gas Fuel Combustion (? /?)
Manufacture of EDC/VC (? / ?)
Best Estimate of
WHO-TEQ Emission Factor
(ng/kg or ng/L)
Total Annual "Activity"
(thousand metric tons/yr or
million L/yr)
Annual WHO-TEQ Emission
(g WHO-TEQ/yr)
The figures include sources with annual WHO-TEQ emission estimates greater than 5 g WHO-TEQ/yr in
one or both of the Reference Years 1987 or 1995. Derivation of the emission factors
and annual "Activity estimates (e.g., kg of waste incinerated) are presented in the following
chapters of this report. The difference in bar shading indicates the degree of confidence in the
estimate. The set of numbers following the source categories indicates the number of
facilities/sites for which emission test data are available versus the number of facilities/sites
in the category. A question mark (?) indicates that the precise number of facilities/sites
could not be estimated.
Figure 1-6. Estimated CDD/CDF WHO-TEQ emissions to air from
combustion sources in the United States (reference year: 1987).
Note: Municipal solid waste incineration is currently referred to as municipal
waste combustion.
03/04/05
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DRAFT—DO NOT CITE OR QUOTE
-------
Emission Source
(tested / total units)
Municipal Waste Combustion (39 /130)
Medical Waste Incineration (20 / 2400)
Secondary Copper Smelting (2 / 3)
Backyard Barrel Burning (6 /)
Cement Kilns Burning Haz Waste (10/34)
Utility/Industrial Coal Combustion (11 />1000)
On-road Leaded Gas Fuel Combustion (? / ?)
Iron Ore Sinter Plants (2/11)
On-road Diesel Fuel Combustion (NA)
Industrial Wood Burning (9 / ?)
Residential Wood Burning (7 / 25000000)
Off-road Diesel Fuel Combustion (NA)
Utility/ Industrial Residual Oil Combustion (? / ?)
Secondary Aluminum Smelting (6 / 76)
Cement Kilns Not Burning Haz Waste (15 /178)
Utility/Industrial Distillate Oil Combustion (>2/?)
Sewage Sludge Incineration (13 / 257)
Hazardous Waste Incineration (17 /162)
On-road Unleaded Gas Fuel Combustion (? / ?)
Manufacture of EDC/VC (? / ?)
Best Estimate of Total Annual "Activity"
WHO-TEQ Emission Factor (thousand metric tons/yr or
(ng/kg or ng/L)
million L/yr)
Annual WHO-TEQ Emission
(g WHO-TEQ/yr)
The figures include sources with annual WHO-TEQ emission estimates greater than 5 g WHO-TEQ/yr in
one or both of the Reference Years 1987 or 1995. Derivation of the emission factors
and annual "Activity" estimates (e.g., kg of waste incinerated) are presented in the following
chapters of this report. The difference in bar shading indicates the degree of confidence in the
estimate. The set of numbers following the source categories indicates the number of
facilities/sites for which emission test data are available versus the number of facilities/sites
in the category. A question mark (?) indicates that the precise number of facilities/sites
could not be estimated.
Figure 1-7. Estimated CDD/CDF WHO-TEQ emissions to air from
combustion sources in the United States (reference year: 1995).
03/04/05
1-55
DRAFT—DO NOT CITE OR QUOTE
-------
Emission Source
(tested /total units)
Municipal Waste Combustion (195 / 251)
Medical Waste Incineration (22 / ?)
Secondary Copper Smelting (1 / 2)
Backyard Barrel Burning (6 / ?)
Cement Kilns Burning Haz Waste (10 /17)
Utility/ Industrial Coal Combustion (11 /> 1,000)
On-Road Leaded Gas Fuel Combustion (0 / 0)
Iron Ore Sinter Plants (2/11)
On-road Diesel Fuel Combustion (NA)
Industrial Wood Burning (9 / ?)
Residential Wood Burning (19 / 25000000)
Off-road Diesel Fuel Combustion (NA)
Utility / Industrial Residual Oil Combustion (? / ?)
Secondary Aluminum Smelting (6 / ?)
Cement Kilns Not Burning Haz Waste (15 / ?)
Utility / Industrial Distillate Oil Combustion (>2 / ?)
Sewage Sludge Incineration (14 / ?)
Hazardous Waste Incineration (22 /132)
On-road Unleaded Gas Fuel Combustion (? / ?)
Manufacture of EDC/VC (8 /12)
Best Estimate of
WHO-TEQ Emission Factor
(ng/kg or ng/L)
Total Annual-Activity"
(thousand metric tons/yr or
million L/yr)
Annual WHO-TEQ Emission
(g WHO-TEQ/yr)
5 S 8 8
888
The figures include sources with annual WHO-TEQ emission estimates greater than 5 g WHO-TEQ/yr in one
or both of reference years 1995 and 1987. Derivations of emission factors and annual "activity" estimates
(e.g., kg of waste incinerated) are presented in this report. The difference in bar shading indicates the
degree of confidence in the estimate. The set of numbers following the source categories indicates the
number of facilities/sites for which emission test data are available versus the number of facilities/sites in the
category. A question mark (?) indicates that the precise number of facilities/sites could not be estimated.
Legend
Low Confidence
Medium Confidem
High Confidence
Figure 1-8. Estimated CDD/CDF WHO-TEQ emissions to air from
combustion sources in the United States (reference year: 2000).
03/04/05
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DRAFT—DO NOT CITE OR QUOTE
-------
Municipal Waste Combustion
Backyard Barrel Burning
Medical Waste Incineration
Secondary Copper Smelting
Cement Kilns Burning Haz Waste
Residential Wood Burning
Utility/Industrial Coal Combustion
On-Road Diesel Fuel Combustion
Secondary Aluminum Smelting
Industrial Wood Burning
Iron Ore Sinter Plants
Cement Kilns Not Burning Hai Waste
Sewage Sludge Incineration
Manufacture of EDC/VC
Utility/Industrial Oil Combustion
Crematoria (human)
Hazardous Waste Incineration
On-Road Unleaded Gas Fuel Combustion
On-Road Leaded Gas Fuel Combustion
0.1
10
100
1000
10000
• 1987 D1995 D2000
Figure 1-9. Comparison of estimates of annual WHO-TEQ emissions to air (g
WHO-TEQ/yr) for reference years 1987,1995, and 2000.
03/04/05
1-57
DRAFT—DO NOT CITE OR QUOTE
-------
Municipal Waste Combustor with Hot ESP
1,
_
fs///s/s/s
1.
i.l
Municipal Waste Combustor with DS/FF
••ill I
4* 4* if 4* -
**
4* 4* if
* *
4*
Medical/hospital Waste Incinerators
Hazardous Waste Incinerators
1. i
..ill.l
I
I
-Illllll I
I
Figure 1-10. The Congener Profiles (as percent distributions to the
sum of CDD + CDF) of Anthropogenic Sources of Chlorinated
Dibenzo-p-Dioxins and Chlorinated Dibenzofurans in the United
States.
03/04/05
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DRAFT—DO NOT CITE OR QUOTE
-------
.4* .4*
Backyard Refuse Barrel Burning
I
4* "?* 4* 4* -v*"
Portland Cement Kilns
1
Industrial Wood Waste Combustion
I .
Portland Cement Kilns Burning Hazardous Waste
^
Ttt
Figure 1-10. The Congener Profiles (as percent distributions to the sum of CDD +
CDF) of Anthropogenic Sources of Chlorinated Dibenzo-p-Dioxins and Chlorinated
Dibenzofurans in the United States (continued).
03/04/05
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DRAFT— DO NOT CITE OR QUOTE
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Coal-fired Electrical Generating Facilities
Oil-fired Electrical Generating Facilities
25%
20%
15%
10%
70%
60%
50%
• •I
Petroleum Refineries
:
_ _ m _ _ •
^v* /* •/* •/* •/ •//'
-------
Secondary Aluminum Smelters
5%n
5%-
4%-
4%-
3%-
3%-
2%-
2%-
1%-
1%-
0%
....Illllllll
Secondary Lead Smelters
777TT
i
0.04%
0.03%
0.02%
0.01%
Secondary Copper Smelters
I
t
Iron Foundries
.1 . I
A* A* jlfb ^J?
Figure 1-10. The Congener Profiles (as percent distributions to the sum of CDD +
CDF) of Anthropogenic Sources of Chlorinated Dibenzo-p-Dioxins and Chlorinated
Dibenzofurans in the United States (continued).
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Automobiles Burning Leaded Gasoline
t
45%
40%
35%
30%
25%
20%
15%
10%
•< *
Diesel Truck Exhaust
d
Automobiles Burning UnLeaded Gasoline
V &
<\v _N"
1
id
Crematoria
A A
nK aV
I
I
. . • 1 1
J_
y/////////x/////
Figure 1-10. The Congener Profiles (as percent distributions to the sum of CDD +
CDF) of Anthropogenic Sources of Chlorinated Dibenzo-p-Dioxins and Chlorinated
Dibenzofurans in the United States (continued).
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Forest Fires
70%
60%
50%
40%
30%
20%
10%
0%
i
Figure 1-10. The Congener Profiles (as percent distributions to the sum of CDD +
CDF) of Anthropogenic Sources of Chlorinated Dibenzo-p-Dioxins and Chlorinated
Dibenzofurans in the United States (continued).
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1 2. MECHANISMS OF FORMATION OF DIOXIN-LIKE COMPOUNDS
2 DURING COMBUSTION OF ORGANIC MATERIALS
3
4 More than a decade of combustion research has contributed to a general understanding of
5 the central molecular mechanisms that form CDDs/CDFs emitted from combustion sources.
6 Current understanding of the conditions necessary to form CDDs/CDFs were primarily derived
7 from studies of full-scale municipal waste combustors (MWCs), augmented with observations
8 involving the experimental combustion of synthetic fuels and feeds within the laboratory.
9 However, the formation mechanisms elucidated by these studies are generally relevant to most
10 combustion systems in which organic material is burned with chlorine.
11 Intensive studies have examined MWCs from the perspective of identifying the specific
12 formation mechanism(s) that occurs within the system. This knowledge may lead to methods
13 that prevent the formation of CDDs/CDFs and their release into the environment. Although
14 much has been learned from such studies, a method that completely prevents CDDs/CDFs from
15 forming during the combustion of certain organic materials in the presence of a source of
16 chlorine and oxygen is still unknown. The wide variability of organic materials incinerated and
17 thermally processed by a wide range of combustion technologies that have variable temperatures,
18 residence times, and oxygen requirements adds to this complex problem. However, central
19 chemical events that participate in the formation of CDDs/CDFs can be identified by evaluating
20 emission test results from MWCs in combination with laboratory experiments.
21 CDD/CDF emissions from combustion sources can potentially be explained by three
22 principal mechanisms that should not be regarded as being mutually exclusive. In the first
23 mechanism (referred to as "pass through"), CDDs/CDFs are present as contaminants in the
24 combusted organic material; they pass through the furnace and are emitted unaltered. This
25 mechanism is discussed in Section 2.1. In the second mechanism (referred to as "precursor"),
26 CDDs/CDFs ultimately form from the thermal breakdown and molecular rearrangement of
27 precursor ring compounds, which are defined as chlorinated aromatic hydrocarbons that have a
28 structural resemblance to the CDD/CDF molecules. Ringed precursors that emanate from the
29 combustion zone are a result of the incomplete oxidation of the constituents of the feed (i.e.,
30 products of incomplete combustion). The precursor mechanism is discussed in Section 2.2. The
31 third mechanism (referred to as "de novo synthesis") is similar to the precursor mechanism and is
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1 described in Section 2.3. De novo synthesis describes a pathway of CDD/CDF formation from
2 heterogeneous reactions on fly ash (particulate matter [PM]) involving carbon, oxygen, hydrogen,
3 chlorine, and a transition metal catalyst. With these reactions, intermediate compounds that have
4 an aromatic ring structure are formed.
5 Studies in this area suggest that aliphatic compounds, which arise as products of
6 incomplete combustion, may play a critical role in initially forming simple ring molecules, which
7 later evolve into complex aromatic precursors. CDDs/CDFs are then formed from the
8 intermediate compounds. In both the second and the third mechanism, formation occurs outside
9 the furnace, in the so-called post-combustion zone. Particulate-bound carbon is suggested as the
10 primary reagent in the de novo synthesis pathway.
11 Section 2.4 presents an overview of studies that have investigated the role that chlorine
12 plays in forming CDDs/CDFs. Although chlorine is an essential component for the formation of
13 CDDs/CDFs in combustion systems, the empirical evidence indicates that for commercial-scale
14 incinerators, chlorine levels in feed are not the dominant controlling factor for rates of CDD/CDF
15 stack emissions. There are complexities related to the combustion process itself, and some types
16 of air pollution control equipment tend to mask any direct association. Therefore, the chlorine
17 content of fuel and feeds to a combustion source is not a good indicator of levels of CDDs/CDFs
18 emitted from the stack of that source.
19 Section 2.5 discusses the generation and formation of coplanar PCBs. The presence of
20 coplanar PCBs in stack emissions from combustors is an area in need of further research.
21 Evidence to date suggests that PCB emissions are mostly attributable to PCB contamination in
22 waste feeds and that emissions are related to the first mechanism described above. However,
23 newly published research has also indicated that it is possible that PCBs form in much the same
24 way as described in the second and third mechanisms identified in the formation of CDDs/CDFs
25 within the post-combustion zone.
26 Section 2.7 provides a closing summary of the three principal formation mechanisms and
27 the role of chlorine. From the discussions in this chapter, it should be evident that no clear
28 distinction exists between the precursor and the de novo synthesis mechanisms of CDD/CDF
29 formation. Both formation pathways depend on the evolution of precursors within combustion
30 gases, the interaction of reactive fly ashes, a generally oxidative environment, the presence of a
31 transition metal catalyst, the presence of gaseous chlorine, and a favorable range of temperature.
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1 The temperature of the combustion gases (i.e., flue gases) is perhaps the single most important
2 factor in forming dioxin-like compounds. Temperatures between 200 and 450 °C are most
3 conducive to the formation of CDDs/CDFs, with maximum formation occurring at around
4 350 °C. If the temperature falls outside this range, the amount of CDDs/CDFs formed is
5 minimized.
6
7 2.1. MECHANISM 1 (PASS THROUGH): CDD/CDF CONTAMINATION IN FUEL AS
8 A SOURCE OF COMBUSTION STACK EMISSIONS
9 The first mechanism involved in stack emissions of CDDs/CDFs is the incomplete
10 destruction of CDD/CDF contaminants present in the fuel or feeds delivered to the combustion
11 chamber. Not all of these molecules are destroyed by the combustion system, thus allowing trace
12 amounts to be emitted from the stack. Most work in this area has involved the study of
13 incineration of municipal solid waste (MSW), where CDDs/CDFs were analytically measured in
14 the raw refuse fed into the incinerator. CDDs/CDFs are ubiquitous in the environment (air,
15 water, and soil) and in foods and paper; therefore, they clearly are present in municipal waste
16 (Tosine et al., 1983; Ozvacic, 1985; Clement et al., 1988; Federal Register, 1991a; Abad et al.,
17 2002).
18 Abad et al. (2002) have provided contemporary measurements of CDDs/CDFs in raw
19 MSW. Twenty-two samples were collected and analyzed for CDDs/CDFs over a one year period
20 from September 1998 through September 1999. The congeners that dominated the total mass of
21 CDDs/CDFs were the OCDD and 1,2,3,4,7,8,9-HpCDD. Figure 2-1 displays the mean CDD and
22 CDF congener distribution from this study. Abad et al. (2002) found that the I-TEQ
23 concentration in the MSW was highly variable and ranged from 1.55 to 45.16 ng I-TEQ/kg
24 MSW.
25 A number of studies have provided evidence that most of the CDDs/CDFs present in the
26 MSW are destroyed during combustion (Abad et al., 2002; Clement et al., 1988; Commoner et
27 al., 1984, 1985, 1987; Hay et al., 1986; Environment Canada, 1985). These studies have
28 involved a mass balance of the input versus output of CDDs/CDFs at two operational MWCs.
29 The mass of CDDs/CDFs outside the incinerator furnace was found to be much greater than the
30 mass of CDDs/CDFs in the raw MSW fed into the incinerator, and the profiles of the
31 distributions of CDD/CDF congeners were strikingly different. Primarily, the more highly
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1 chlorinated congeners were detected as contaminants in the waste, whereas the total array of
2 tetra- to octa-CDDs/CDFs could be detected in the stack gases. Moreover, the ratio of the total
3 concentration of CDDs in the MSW in relation to the total CDF concentration was greater than 1,
4 whereas in typical incinerator stack emissions, this ratio is less than 1 (meaning more
5 dibenzofurans are emitted than dioxins). Such evidence gives the conclusion that CDDs/CDFs
6 are being synthesized after the contaminated feed has been combusted (Abad et al., 2002).
7 Moreover, it is expected that the conditions of thermal stress imposed by high temperatures
8 reached in typical combustion would destroy and reduce the CDDs/CDFs present as
9 contaminants in the waste feed to levels that are 0.0001 to 10% of the initial concentration,
10 depending on the performance of the combustion source and the level of combustion efficiency.
11 Stehl et al. (1973) demonstrated that the moderate temperature of 800 °C enhances the
12 decomposition of CDDs at a rate of about 99.95% but lower temperatures result in a higher
13 survival rate.
14 Theoretical modeling has shown that unimolecular destruction of CDDs/CDFs at 99.99%
15 can occur at the following temperatures and retention times within the combustion zone: 977 °C
16 with a retention time of 1 sec, 1,000 °C at a retention time of 0.5 sec, 1,227 °C at a retention time
17 of 4 msec, and 1,727 °C at a retention time of 5 |_isec (Schaub and Tsang, 1983). Thus,
18 CDDs/CDFs would have to be in concentrations of parts per million in the feed in the combustor
19 to be found in the parts-per-billion or parts-per-trillion level in the stack gas emissions (Shaub and
20 Tsang, 1983). However, it cannot be ruled out that CDDs/CDFs in the waste or fuel may
21 contribute (up to some percentage) to the overall concentration leaving the stack. The only other
22 possible explanation for CDD/CDF emissions from high-temperature combustion of organic
23 material is formation outside and downstream of the furnace.
24 The above studies point to formation mechanisms other than simple pass through of
25 noncombusted feed contamination. These formation mechanisms are discussed and reviewed in
26 the following sections.
27
28 2.2. MECHANISM 2 (PRECURSOR): FORMATION OF CDDs/CDFs FROM
29 PRECURSOR COMPOUNDS
30 The second mechanism involves the formation of CDDs/CDFs from aromatic precursor
31 compounds in the presence of a chlorine donor. This mechanism has been elucidated by
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1 laboratory experiments involving the combustion of known precursors in quartz ampules under
2 starved-air conditions and in experiments that investigated the role of combustion fly ash in
3 promoting the formation of CDDs/CDFs from precursor compounds. The general reaction in this
4 formation pathway is an interaction between an aromatic precursor compound and chlorine
5 promoted by a transition metal catalyst on a reactive fly ash surface (Stanmore, 2004; Dickson and
6 Karasek, 1987; Liberti and Brocco, 1982). Examples of well-studied precursor compounds
7 include chorobenzenes, chlorophenols, phenol, and benzene (Esposito et al., 1980). Gaseous
8 hydrogen chloride (HC1), free chorine (C12), and chlorine radicals (C1-) are the chlorinating agents
9 within the combustion gases. CDD/CDF formation results from heterogeneous gas-phase
10 reactions involving chlorinated precursor compounds and a source of chlorine. Chlorophenol and
11 chlorobenzene compounds are measured in flue gases from MWCs (Dickson and Karasek, 1987).
12 Precursors are carried from the furnace to the flue duct as products of incomplete combustion.
13 These compounds can adsorb on the surface of combustion fly ash or entrain in the gas phase
14 within the flue gases. Thus, there are two formation pathways from precursor compounds:
15 heterogeneous solid-phase reactions and homogeneous gas-phase reactions. In the post-
16 combustion region outside the furnace, heterogeneous reactions on the surface of reactive fly ash
17 can ensue to form CDDs/CDFs from the precursor compounds. This occurs at the cool down
18 temperatures of 200 to 400 °C. The heterogeneous gas-phase reactions occur from the breakdown
19 and molecular rearrangement of precursor compounds followed by condensation and chlorination
20 at the higher temperatures of 500 to 800 °C. Both reaction pathways are catalyzed by copper
21 chloride (CuCl2) or another transition metal.
22 Laboratory experiments involving the controlled combustion of precursor compounds have
23 caused the breakdown of the precursor reagent and the subsequent appearance of CDDs/CDFs as
24 products of the reaction. For example, Jansson et al. (1977) produced CDDs through the pyrolysis
25 of wood chips treated with tri-, tetra-, and pentachlorophenol (PCP) in a bench-scale furnace
26 operated at 500 to 600 °C. Stehl and Lamparski (1977) combusted grass and paper treated with
27 the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in a bench-scale furnace at 600 to 800
28 °C and generated ppmv levels of TCDD. Ahling and Lindskog (1982) reported CDD formation
29 during the combustion of tri- and tetrachlorophenol formulations at temperatures of 500 to 600
30 °C. Decreases in oxygen during combustion generally increased the CDD yield.
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1 Ahling and Lindskog (1982) noted that adding copper salts to the tetrachlorophenol
2 formulation significantly enhanced the yield of CDDs. This may have been an early indication of
3 copper's role in catalyzing the condensation of chlorophenol to dioxin. Combustion of PCP
4 resulted in low yields of CDDs. However, when PCP was burned with an insufficient supply of
5 oxygen in the presence of copper, the investigators noted the formation of tetra- through
6 octachlorinated congeners. Buser (1979) generated CDDs/CDFs on the order of 0.001 to 0.08%
7 (by weight) by heating tri-, tetra-, and pentachlorobenzenes at 620 °C in quartz ampules in the
8 presence of oxygen. It was noted that chlorophenols formed as combustion byproducts; Buser
9 (1979) speculated that these chlorophenols were acting as reaction intermediates in the formation
10 of CDDs/CDFs.
11 The second condition postulated to regulate the synthesis of CDDs/CDFs from the
12 aromatic precursor compound is the adsorption and interaction with the reactive surface of
13 combustion-generated fly ash (PM) entrained in the combustion plasma and the presence of a
14 transition metal catalyst ( Stanmore, 2004; Dickson et al., 1992; Bruce et al., 1991; Cleverly et al.,
15 1991; Gullet et al., 1990a; Commoner et al., 1987; Dickson and Karasek, 1987; Vogg et al.,
16 1987). These are heterogeneous solid-phase reactions that occur at temperatures below 450 °C.
17 The molecular precursor leaves the gas phase and condenses onto the fly ash particle. This
18 condition, which places greater emphasis on heterogeneous surface reactions and less emphasis on
19 homogeneous gas-phase reactions, was first postulated by Shaub and Tsang (1983) using thermal-
20 kinetic models based on the temperature of the heat of formation, adsorption, and desorption.
21 Shaub and Tsang modeled CDD production from chlorophenols and concluded that solid-phase
22 formation of CDDs/CDFs was of greater importance than gas-phase formation within an
23 incineration system. The temperature of the combustion gases is a critical factor in the formation
24 of CDDs/CDFs from aromatic precursor compounds (Weber and Hagenmaier, 1999; Fangmark et
25 al., 1994; Vogg et al., 1987, 1992; Oberg et al.,1989). Vogg et al. (1987) found that formation
26 probably occurs outside and downstream from the combustion zone of a furnace in regions where
27 the temperature of the combustion offgases has cooled within a range of 200 to 450 °C.
28 After carefully removing organic contaminants from MWC fly ash, Vogg et al. (1987)
29 added known concentrations of isotopically labeled CDDs/CDFs to the matrix. The MWC fly ash
30 was then heated for 2 hr in a laboratory furnace at varying temperatures. The treated fly ash was
31 exposed to temperatures increasing in 50 °C increments within a temperature range of 150 to 500
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1 °C. Table 2-1 summarizes these data. Because the relative concentration of CDDs/CDFs
2 increased while exposed to varying temperatures, it was concluded that the temperature of the
3 combustion gas is crucial to promoting the formation of CDDs/CDFs on the surface of fly ash.
4 Within a temperature range of 200 to 450 °C, the concentration of CDDs/CDFs increases to some
5 maxima; outside this range, the concentration diminishes.
6 The region of cooler gas temperature is often referred to as the "post-combustion zone."
7 The heat loss may be inherent to the conduction and transfer through the combustion gas metal
8 ducting system or related to adsorbing/exchanging heat to water in boiler tubes. This region
9 extends from near the exit of the furnace to the point of release of the combustion gases at stack
10 tip.
11 Fangmark et al. (1994) found that CDDs/CDFs exhibit a similar dependence at a
12 temperature range of 260 to 430 °C, with maximum formation occurring around 340 °C. Using a
13 pilot-scale combustor, Behrooz and Altwicker (1996) found that the formation of CDDs/CDFs
14 from the precursor 1,2-dichlorobenzene rapidly occurred within the post-combustion region in a
15 temperature range of 390 to 400 °C, with residence times of only 4 to 5 sec. On the other hand,
16 CDD/CDF formation from 1,2-dichlorophenol seemed to require higher temperatures.
17 Oberg et al. (1989) examined the role of temperature in the formation kinetics using a full-
18 scale hazardous waste incinerator (HWI) operating in Sweden. The investigators observed that
19 maximum CDD/CDF formation transpired in the boiler used to extract heat for cogeneration of
20 energy. In this study, significant increases in total concentration of I-TEQDF occurred between 280
21 and 400 °C, and concentrations declined at temperatures above 400 °C. Weber and Hagenmaier
22 (1999) showed that in gas-phase reactions, chlorophenols react in the presence of oxygen at
23 temperatures above 340 °C to form CDDs/CDFs. Phenoxyradicals were formed, which in turn
24 caused the formation of CDDs. Polychlorinated dihydroxybiphenyls were identified as reaction
25 intermediates in the gas-phase dimerization of chlorophenols, and these intermediates could form
26 CDFs.
27 Konduri and Altwicker (1994) proposed that rate-limiting factors were the nature and the
28 concentrations of the precursors, the reactivity and availability of the fly ash surface, and the
29 residence time in the post-combustion zone. Dickson and Karasek (1987) investigated fly ash
30 reactivity with 13C6-chlorophenol compounds. Several samples of fly ash from MWCs, copper
31 smelters, and a variety of combustion fuels were heated at 300 °C in quartz tubes under conditions
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1 known to catalyze the conversion of chlorophenols to CDDs/CDFs. The MSW fly ashes included
2 a sample from a poorly operated mass burn refractory incinerator and a sample from a well-
3 operated fluidized-bed combustor. The MWC fly ashes proved to be the most active catalytic
4 medium, despite similarities with respect to specific surface area and average pore diameters. The
5 fly ash from the refractory MWC generated about seven times more mass of dioxin-like
6 compounds than the fluidized-bed MWC. In the MSW fly ashes, all CDD/CDF congener groups
7 were formed from labeled chlorophenols; however, only trace amounts of heptachloro- and
8 octachlorodioxin were formed with the copper smelter/refiner. X-ray photoelectron spectroscopy
9 revealed the presence of chlorine adsorbed to the surface of the MWC fly ash but an absence of
10 chlorine sorbed to the copper smelter fly ash.
11 CDD congener groups have been postulated to form from the labeled PCP precursors by
12 (1) first forming octachlorodioxin by the condensation of two PCP molecules, and (2) forming
13 other less-chlorinated dioxins through dechlorination of the more highly chlorinated isomers.
14 These steps seemed to proceed by an increased reactivity of the chemisorbed precursor molecule
15 caused by the removal of one or more hydrogen or chlorine atoms along the ring structure
16 (Dickson and Karasek, 1987), an observation consistent with the kinetic model of Shaub and
17 Tsang (1983).
18 In related experiments, Dickson and Karasek (1987) more specifically reported on forming
19 CDDs/CDFs from condensation reactions of chlorophenols on the surface of MWC fly ash heated
20 in a bench-scale furnace. Their experiment was designed to mimic conditions of MSW
21 incineration, to identify the step-wise chemical reactions involved in converting a precursor
22 compound into dioxin, and to determine whether MWC fly ash could promote these reactions.
23 MWC fly ash was obtained from facilities in Canada and Japan. The fly ash was rinsed with
24 solvent to remove any organic constituents prior to initiating the experiment. Twenty grams of fly
25 ash were introduced into a bench-scale furnace (consisting of a simple flow-tube combustion
26 apparatus) and heated at 340 °C overnight to desorb any remaining organic compounds from the
27 matrix. 13C12-labeled PCP and two trichlorophenol isotopes (13C12-2,3,5-trichlorophenol and
28 3,4,5-trichlorophenol) were added to the surface of the clean fly ash matrix and placed in the oven
29 for 1 hr at 300 °C. Pure inert nitrogen gas (flow rate of 10 mL/min) was passed through the flow
30 tube and a constant temperature was maintained.
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1 Tetra- through octa-CDDs were formed from the labeled PCP experiment; more than 100
2 |_ig/g of total CDDs were produced. The congener pattern was similar to that found in MWC
3 emissions. The 2,3,5-trichlorophenol experiment primarily produced HxCDDs and very small
4 amounts of tetra- and octa-CDDs. The 3,4,5-trichlorophenol experiment mainly produced OCDD
5 and 1,2,3,4,6,7,8-HpCDD.
6 Dickson and Karasek (1987) proposed that CDDs on fly ash surfaces may result from
7 chlorophenol undergoing molecular rearrangement or isomerization as a result of dechlorination,
8 dehydrogenation, and transchlorination before condensation occurs. These reactions were
9 proposed as controlling the types and amounts of CDDs that are ultimately formed. Born et al.
10 (1993) conducted experiments on the oxidation of chlorophenols with fly ash in a quartz tube
11 reactor heated to about 300 °C. The MWC fly ash mediated the oxidation of chlorophenols to
12 produce carbon dioxide (CO2) and carbon monoxide (CO) as major products and poly chlorinated
13 benzenes, monobenzofurans, and nonhalogenated dibenzo-/>-dioxins as trace species. Formation
14 of these trace aromatic species occurred after residence times of only 7 to 8 sec, which was
15 consistent with the later experimental result of Behrooz and Altwicker (1995), which showed the
16 potential for rapid formation from a precursor.
17 Milligan and Altwicker (1996) fitted experimental flow-tube reactor data to classical
18 catalytic reaction models to empirically explain the interaction of 2,3,4,6-tetrachlorophenol (as a
19 model precursor) with reactive MWC fly ash during MSW incineration. The precursor was found
20 to be highly adsorptive on the surface of fly ash, with a first-order dependence on gas-phase
21 precursor concentration to CDD formation. The investigators concluded that chlorophenol's
22 dependence on gas-phase concentration to form CDDs on fly ash reflects the highly heterogeneous
23 nature of the fly ash surface. Moreover, the estimated 6 x 1018 adsorption sites per gram of fly ash
24 suggested the presence of highly energetic sites, which may be important in the surface-catalyzed
25 reactions forming CDDs. An interesting observation by Milligan and Altwicker (1996) was that
26 precursor molecules appeared to compete with oxygen molecules for the reactive sites; therefore,
27 chlorophenols are expected to adsorb less readily to the fly ash surface in the presence of oxygen.
28 Experimental evidence suggests that condensation to CDD of chlorophenol compounds
29 via isomerization and the "Smiles" rearrangement on reactive MWC fly ash surfaces is a proven
30 pathway for the formation of dioxins from a precursor compound (Addink and Olie, 1995).
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1 However, no detailed mechanisms have been presented for CDD/CDF formation from other
2 precursors such as chlorobenzenes under conditions simulating incineration.
3 A condition in the synthesis of CDDs/CDFs from aromatic precursor compounds is that
4 the presence of a transition metal catalyst promotes the chemical reaction on the surface of fly ash.
5 Copper chloride (CuCl2) is a strong catalyst for promoting surface reactions on particulate matter
6 to convert aromatic precursor compounds to CDDs/CDFs (Vogg et al., 1987). CuCl2 promotes
7 ring condensation reactions (of the chlorophenols) on fly ash to form CDDs/CDFs (Addink and
8 Olie, 1995) via the Ullman reaction (Born et al., 1993). In the Ullman reaction, copper catalyzes
9 the formation of diphenyl ethers by the reaction of halogenated benzenes with alkali metal
10 phenolates (Born et al., 1993), with copper participating in a nucleophilic aromatic substitution
11 reaction. Thus, Born et al. (1993) proposed a similar mechanism in catalyzing the formation of
12 dioxin-like compounds. Using the Ullman reaction as a model, the authors proposed that the
13 copper-catalyzed condensation of two ortho-substituted chlorophenol molecules form chlorine-
14 free dibenzo-p-dioxins.
15 Vogg et al. (1987) proposed an oxidation reaction pathway, giving rise to the formation of
16 CDDs/CDFs in the post-furnace regions of the incinerator in the following order: (1) HC1 is
17 thermolytically derived as a product of the combustion of heterogeneous fuels containing
18 abundant chlorinated organic chemicals and chlorides; (2) oxidation of HC1, with CuCl2 as a
19 catalyst, yields free gaseous chlorine via the Deacon reaction; (3) phenolic compounds (present
20 from combustion of lignin in the waste or other sources) entrained in the combustion plasma are
21 substituted on the ring structure by contact with the free chlorine; and (4) a chlorinated precursor
22 to dioxin (e.g., chlorophenol) is further oxidized (with CuCl2 as a catalyst) to yield CDDs/CDFs
23 and chlorine.
24 Gullett et al. (1990a, b, 199la, b, 1992) studied the formation mechanisms through
25 extensive combustion research at EPA and verified the observations of Vogg et al. (1987). It was
26 proven that CDDs/CDFs could ultimately be produced from low-temperature (i.e., 350 °C)
27 reactions between dichloride (C12) and a phenolic precursor combining to form a chlorinated
28 precursor, followed by oxidation of the chlorinated precursors (catalyzed by a copper catalyst such
29 as CuCl2), as shown below.
30 1. The initial step in dioxin formation is the formation of chlorine from HC1 in the
31 presence of oxygen (the Deacon process) as follows (Bruce et al., 1991; Vogg et al., 1987):
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2 Heat
3 2HC1 + Vi O2 > H2O + C12
4
5 2. Phenolic compounds adsorbed on the surface of fly ash are chlorinated to form the
6 dioxin precursor, and the dioxin is formed as a product from the breakdown and molecular
7 rearrangement of the precursor. The reaction is promoted by CuCl2 acting as a catalyst (Vogg et
8 al., 1987; Dickson and Karasek, 1987; Gullett et al., 1992):
9
10 (a) phenol + C12 > chlorophenol (dioxin precursor)
11
12 CuCl2
13 (b) 2-chlorophenol + V2 O2 > dioxin + C12
14
15 Eklund et al. (1986) observed the high-temperature formation of a large variety of
16 chlorinated toxic compounds, including CDDs/CDFs, from precursors during a simple experiment
17 in which phenol was oxidized with HC1 at 550 °C. One milligram of phenol was placed in a
18 quartz tube reactor with an aqueous solution (10 |_iL) of HC1 and heated at a temperature of 550
19 °C for 5 min. Trichlorobenzene, dichlorophenol, dichlorobenzofuran, tetrachlorobenzene,
20 trichlorophenol, and tetrachlorophenol were identified as major products formed. Monochloro-
21 benzene, chlorophenol, dichlorobenzene, tetrachloropropene, pentachloropropene,
22 trichlorobenzofuran, tetrachlorodibenzofuran, trichlorodibenzo-p-dioxin, tetrachlorodibenzo-/?-
23 dioxin, hexachlorodibenzo-p-dioxin, hexachlorodibenzofuran, pentachlorobenzene,
24 pentachlorobiphenyl, and pentachlorodihydroxycylohexane were observed as minor products.
25 Trace species formed included monochlorodibenzofuran, pentachlorodibenzofuran,
26 pentachlorodibenzo-p-dioxin, octachlorodibenzofuran, and octachlorodibenzo-p-dioxin.
27 Eklund et al. (1986) hypothesized that chlorinated organic compounds can be produced
28 from phenols, acids, and any chlorine source in the hot post-combustion region (just beyond the
29 exit to the furnace). The reaction was seen as very sensitive to HC1 concentration. No chlorinated
30 compounds could be detected when HC1 concentrations were <10"3 mol.
31 Nestrick et al. (1987) reported that the thermolytic reaction between benzene (an
32 unsubstituted precursor) and iron (III) chloride on a silicate surface yielded CDDs/CDFs at
33 temperatures >150 °C. The experimental protocol introduced 100 to 700 mg benzene and 13C6-
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1 benzene into a macroreactor system consisting of a benzene volatilization chamber connected to a
2 glass tube furnace. The investigators noted the relevance of this experiment to generalizations
3 about combustion processes because benzene is the usual combustion byproduct of organic fuels.
4 Inert nitrogen gas carried the benzene vapor to the furnace area. The exit from the glass tubing to
5 the furnace was plugged with glass wool, and silica gel was introduced from the entrance end to
6 give a bed depth of 7 cm to which ferric trichloride (FeCl3) was added to form an FeCl3/silica
7 reagent. The thermolytic reaction took place in a temperature range of 150 to 400 °C at a
8 residence time of 20 min. Although di- through octa-CDDs/CDFs were formed by this reaction at
9 all temperatures studied, the percent yields were extremely small. Table 2-2 summarizes these
10 data.
11
12 2.3. MECHANISMS: DENOVO SYNTHESIS OF CDDs/CDFs DURING
13 COMBUSTION OF ORGANIC MATERIALS
14 The third mechanism, de novo synthesis, promotes CDD/CDF formation in combustion
15 processes from the oxidation of carbon particulate catalyzed by a transition metal in the presence
16 of chlorine. As in the precursor mechanism (mechanism 2), synthesis is believed to occur in
17 regions outside of the furnace zone of the combustion process, where the combustion gases have
18 cooled to a range of temperatures considered favorable to formation chemistry. A key component
19 to de novo synthesis is the production of intermediate compounds (either halogenated or
20 nonhalogenated) that are precursors to CDD/CDF formation. Research in this area has produced
21 CDDs/CDFs directly by heating carbonaceous fly ash in the presence of a transition metal catalyst
22 without the apparent generation of reactive intermediates. Thus, the specific steps involved in the
23 de novo process have not been fully and succinctly delineated. However, laboratory
24 experimentation has proven that MWC fly ash itself is a reactive substrate, and the matrix can
25 actually catalyze the de novo formation chemistry. Typically, fly ash is composed of an alumina-
26 silicate construct, with 5 to 10% concentrations of silicon, chlorine (as inorganic chlorides),
27 sulfur, and potassium (NATO, 1988). Twenty percent of the weight of fly ash particles is carbon,
28 and the particles have specific surface areas in the range of 200 to 400 m2/kg (NATO, 1988).
29 The de novo synthesis essentially is the oxidative breakdown of macromolecular carbon
30 structures, and CDDs/CDFs are formed partially from the aromatic carbon-oxygen functional
31 groups embedded in the carbon skeleton (Huang et al., 1999). The distinguishing feature of the de
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1 novo synthesis over the precursor synthesis is the oxidation of carbon in particulate at the start of
2 the process to yield precursor compounds. In mechanism 2, the precursor compound is the
3 starting molecule of the condensation reactions forming CDDs/CDFs (Dickson et al., 1992). By
4 this distinction, however, one could argue that mechanism 3 is really an augmentation of
5 mechanism 2 because the production of CDDs/CDFs may still require the formation of a
6 CDD/CDF precursor as an intermediate species. Nevertheless, a distinction is presented here to
7 describe additional pathways suggested for the thermal formation of these compounds.
8 To delineate the de novo synthesis of CDDs/CDFs, Stieglitz et al. (1989a) conducted
9 experiments that involved heating particulate carbon containing adsorbed mixtures of magnesium-
10 aluminum (Mg-Al) silicate in the presence of CuCl2 (as a catalyst to the reaction). The authors
11 described heating mixtures of Mg-Al silicate with activated charcoal (4% by weight), chloride as
12 potassium chloride (7% by weight), and CuCl2 (1% in water) in a quartz flow tube reactor at 300
13 °C. The retention time was varied at 15 min, 30 min, and 1, 2, and 4 hr to obtain differences in
14 the amounts of CDDs/CDFs that could be formed. The results are summarized in Table 2-3. In
15 addition to the CDDs/CDFs formed as primary products of the de novo synthesis, the investigators
16 observed precursors formed at the varying retention times during the experiment. In particular,
17 similar yields of tri- through hexachlorobenzenes, tri- through heptachloronaphthalenes, and tetra-
18 through heptachlorobiphenyls were quantified; this was seen as highly suggestive of the role these
19 compounds may play as intermediates in the continued formation of CDDs/CDFs.
20 Stieglitz et al. (1989a) made the following observations:
21
22 • The de novo synthesis of CDDs/CDFs via the oxidation of carbonaceous particulate
23 matter occurred at a temperature of 300 °C. Additionally, the experiment yielded
24 parts-per-billion to parts-per-million concentrations of chlorinated benzenes,
25 chlorinated biphenyls, and chlorinated naphthalenes through a similar mechanism.
26 When potassium bromide was substituted for potassium chloride as a source of
27 halogen for the organic compounds in the reaction, polybrominated dibenzo-p-dioxins
28 and dibenzofurans formed as reaction products.
29
30 • The transition metal compound CuCl2 catalyzed the de novo synthesis of CDDs/CDFs
31 on the surface of particulate carbon in the presence of oxygen, yielding CO2 and
32 chlorinated/brominated aromatic compounds.
33
34 • Particulate carbon, which is characteristic of combustion processes, may act as the
35 source for the direct formation of CDDs/CDFs, as well as other chlorinated organics.
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1
2 More recently, Stieglitz et al. (1991) investigated the role that particulate carbon plays in
3 the de novo formation of CDDs/CDFs from fly ash containing appreciable quantities of organic
4 chlorine. The investigators found that the fly ash contained 900 ng/g of bound organic chlorine.
5 Only 1% of the organic chlorine was extractable. Heating the fly ash at 300 to 400 °C for several
6 hours caused the carbon to oxidize, leading to a reduction in the total organic chlorine in the
7 matrix and a corresponding increase in the total extractable organic chlorine (5% extractable total
8 organic chlorine at 300 °C and 25 to 30% at 400 °C). From this, the authors concluded that the
9 oxidation and degradation of carbon in fly ash are the sources of the formation of CDDs/CDFs;
10 therefore, they are essential in the de novo synthesis of these compounds.
11 Addink et al. (1991) conducted a series of experiments to observe the de novo synthesis of
12 CDDs/CDFs in a carbon fly ash system. In this experiment, 4 g of carbon-free MWC fly ash were
13 combined with 0.1 g of activated carbon and placed into a glass tube between two glass wool
14 plugs. The glass tube was then placed into a furnace at specific temperatures ranging from 200 to
15 400 °C. This protocol was repeated for a series of retention times and temperatures. The
16 investigators observed that CDD/CDF formation was optimized at 300 °C and at the furnace
17 retention times of 4 to 6 hr. Figure 2-2 displays the relationship between retention time,
18 temperature, and CDD/CDF production from the heating of carbon parti culate.
19 Addink et al. (1991) also investigated the relationship between furnace temperature and
20 CDD/CDF production from the heating of carbonaceous fly ash. Figure 2-3 displays this
21 relationship. In general, the concentration began to increase at 250 °C and crested at 350 °C, with
22 a sharp decrease in concentration above 350 °C. The authors also noted a relationship between
23 temperature and the CDD/CDF congener profile: at 300 to 350 °C, the less chlorinated tetra- and
24 penta-CDD/CDF congeners increased in concentration, whereas hexa-, hepta-, and octa-
25 CDD/CDF congeners either remained the same or decreased in concentration. The congener
26 profile of the original MWC fly ash (not subject to de novo experimentation) was investigated
27 with respect to changes caused by either temperature or residence time in the furnace. No
28 significant changes occurred, leading the authors to propose an interesting hypothesis for further
29 testing: after formation of CDDs/CDFs occurs on the surface of fly ash, the congener profile
30 remains fixed and insensitive to changes in temperature or residence time, indicating that some
31 form of equilibrium is reached in the formation kinetics.
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1 Gullett et al. (1994) used a pilot-scale combustor to study the effect of varying combustion
2 gas composition, temperature, residence time, quench rate, and sorbent (Ca[OH]2) injection on
3 CDD/CDF formation. The fly ash loading was simulated by injecting fly ash collected from a
4 full-scale MWC. Sampling and analysis indicated that CDDs/CDFs formed on the injected fly ash
5 at levels representative of those observed at full-scale MWCs. A statistical analysis of the results
6 showed that, although the effect of combustor operating parameters on CDD/CDF formation is
7 interactive and very complicated, substantial reduction in CDD/CDF formation can be realized
8 with high-temperature sorbent injection to reduce HC1 or C12 concentrations, control of excess air
9 (also affects the ratio of CDDs to CDFs formed), and increased quench rate.
10 Milligan and Altwicker (1995) found that increases in the carbon gasification rate caused
11 increases in the amounts of CDDs/CDFs formed and gave further evidence linking the oxidation
12 of carbon to the formation of CDDs/CDFs. Neither the gas-phase CO2 or CO (products of carbon
13 oxidation) act as precursors to chlorobenzenes or CDDs/CDFs from reactions with carbon
14 particulate (Milligan and Altwicker, 1995). Activated carbon, with its high surface area and
15 excellent adsorptive characteristics, also has the highest gasification rate of all residual carbon
16 (Addink and Olie, 1995).
17 Experimental evidence suggests the following factors for the de novo synthesis of
18 CDDs/CDFs from carbon: (a) carbon consisting of imperfect and degenerated layers of graphite,
19 (b) the presence of oxygen, (c) the presence of chlorine, (d) catylization of the reactions by CuCl2
20 or some other transition metal, and (e) temperatures in the range of 200 to 350 °C (Huang and
21 Buekens, 1995). The oxidation of carbon in fly ash is apparently inhibited at temperatures below
22 200 °C, thus indicating the lower temperature limit for the thermal inertization ofde novo
23 synthesis (Lasagni et al., 2000).
24 Lasagni et al. (2000) determined that at a temperature of 250 °C, the primary product of
25 the gasification of carbon in fly ash is CO2, but in a temperature range of 250 to 325 °C, organic
26 compounds are formed as products of the oxidation of the carbon. Addink and Olie (1995) raised
27 the possibility that the molecular backbone of CDDs/CDFs may be present in carbon. If this is the
28 case, the generation of dioxins and furans from the oxidation of carbon would not require the
29 formation of intermediate aromatic ring structures. More work is needed to confirm these
30 possibilities.
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1 The de novo synthesis of CDDs/CDFs also involves the possibility that aromatic
2 precursors are formed within the post-combustion zone in the following manner: (1) fuel
3 molecules are broken down into smaller molecular species (e.g., Cl and C2 molecules) during
4 primary combustion, and (2) these simple molecules recombine in the post-combustion zone to
5 form larger-molecular aromatic species (i.e., chlorobenzenes and chlorophenols) (Altwicker et al.,
6 1993). Thus, small molecular products that evolve in the hot zone of the furnace as a
7 consequence of incomplete fuel or feed material combustion may be important foundation
8 molecules to the subsequent formation of precursor compounds in the cooler, post-combustion
9 region.
10 Eklund et al. (1988) reported formation of a wide range of chlorinated organic compounds,
11 including CDDs, CDFs, and PCBs, from the oxidation of methane with HC1 at temperatures of
12 400 to 950 °C in a quartz flow tube reactor. No active catalysts or reactive fly ashes were added
13 to the combustion system. From these experimental results, the authors hypothesized that
14 chlorocarbons, including CDDs/CDFs, are formed at high temperatures via a series of reversible
15 reactions starting with chloromethyl radicals. The chloromethyl radicals can be formed from the
16 reaction of methyl radicals and HC1 in a sooting flame. Methane is chlorinated by HC1 in the
17 presence of oxygen at high temperatures, forming chlorinated methanes, which react with methyl
18 radicals at higher temperatures (e.g., 800 °C) to form aromatic compounds. In an oxidative
19 atmosphere, chlorinated phenols are formed, but alkanes and alkenes are the primary products.
20 The chlorinated phenols then act as precursors for the subsequent formation of CDDs/CDFs.
21 Aliphatic compounds are common products of incomplete combustion, and they may be
22 critical to the formation of simple ring structures in the post-combustion zone (Weber et al., 1999;
23 Sidhu, 1999; Froese and Hutzinger, 1996a, b; Jarmohamed and Mulder, 1994). The aromatic
24 precursor compounds may be formed in a potentially rich reaction environment of aliphatic
25 compounds, reactive fly ash particles, HC1, and oxygen. Sidhu (1999) noted that combustion of
26 acetylene on carbon (a common combustion effluent) in the presence of gaseous HC1 and CuCl2
27 (as a catalyst) at 300 °C led to the formation of intermediate precursors and, subsequently,
28 CDDs/CDFs.
29 Propene oxidized at 350 to 550 °C when in contact with reactive MWC fly ash in a flow
30 tube reactor formed a wide range of chlorinated aromatic compounds when the resulting
31 combustion gases were mixed with HC1 (Jarmohamed and Mulder, 1994). Although the
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1 conversion was low (1 to 3%), the oxidation of propene on fly ash in the presence of HC1 can
2 yield chlorinated benzenes and monobenzofurans. Incorporating an oxygen atom into the
3 monobenzofuran structure then leads to the formation of monodibenzofuran. The HC1 contributes
4 chlorine to the aromatic ring through the Deacon reaction, and cyclization on the fly ash surface
5 can yield cyclohexadienyl-substituted benzenes, which in turn can be further oxidized into CDFs.
6 Froese and Hutzinger (1996a) investigated the heterogeneous combustion reactions of the
7 nonchlorinated C2 aliphatics. Acetylene, as a model aliphatic compound, was allowed to react
8 with precleaned MWC fly ash in a tube flow reactor at approximately 600 °C. Metal oxides
9 (SiO2, Fe2O3, and CuO)—rather than the metal chlorides used in other precursor
10 experiments—were added separately as catalysts. The reactants were put into contact with HC1
11 vapor, which was introduced at a constant flow rate. The acetylene flow was set at 1.1 mL/min
12 and constantly fell to near 0.9 mL/min over 30 min. Regulated air flow maintained homeostatic
13 oxidation conditions.
14 Chorobenzenes and chlorophenols were formed, with isomer patterns generally resembling
15 isomer patterns of chlorobenzene and chlorophenol emissions from MWCs. CuO was seen as
16 catalyzing condensation and chlorination reactions under heterogeneous conditions to form the
17 chlorinated CDD/CDF precursor compounds. Other more volatile compounds formed were short-
18 chain aliphatic products, such as chloromethane, dichloromethane, and chloro- and
19 dichloroacetylene. Chlorobenzene congeners were not the major products formed; perchlorinated
20 aliphatic compounds dominated as gas-phase reaction products.
21 Froese and Hutzinger (1997) noted that perchlorinated aliphatic compounds (e.g.,
22 hexachloropropene, hexachloro-1,3-butadiene, and hexachlorocyclopentadiene) are important
23 intermediates in aromatic ring formation; they concluded that the catalytic reaction of C2 aliphatic
24 compounds at 600 °C dramatically contributes to the formation of chlorinated and nonchlorinated
25 aromatic compounds during combustion. Thus, aliphatic compounds can form CDD/CDF
26 precursor compounds. Variable temperature effects were observed in the formation of
27 CDDs/CDFs in the same reactions. Maximal OCDD formation occurred at 400 °C, and the tetra-
28 hepta homologue groups were maximally formed at 600 °C. For CDFs, production of more
29 highly chlorinated homologues occurred at 400 °C, and the formation of tetrachlorodibenzofurans
30 occurred at 500 °C. Froese and Hutzinger (1996a) noted a 100-fold increase in
31 tetrachlorodibenzofuran formation at 500 °C when compared with formation at 400 °C. An
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1 explanation for this increase is that the higher temperature maximized the formation of the
2 CDD/CDF precursor (chlorophenol) from the aliphatic starting compound.
3 Froese and Hutzinger (1996b) produced poly chlorinated benzene and phenol compounds at
4 a temperature range of 300 to 600 °C. This was caused by the heterogeneous combustion
5 reactions of ethylene and ethane over fly ash in the presence of HC1, oxygen, and a metal catalyst.
6 No chlorobenzene congener precursors were formed from ethylene and ethane at 300 °C;
7 however, the formation rate increased with temperature until a maximum production was
8 achieved at 600 °C. No definitive temperature dependence was observed for the formation of
9 chlorophenols from the aliphatic starting compounds. However, at 500 °C, 2,4,6-trichlorophenol
10 dominated the reaction products; at 300 °C, PCP was initially produced.
11 Froese and Hutzinger (1996b) also investigated the effects of elemental catalysts on
12 potentiating the heterogeneous combustion reactions by measuring the amount of chlorobenzene
13 and chlorophenol product formed from the reactions of ethylene/HCl over each catalyst at
14 600 °C. The reaction with SiO2 did not have a catalytic effect. A12O3 catalytic action showed
15 high intensity for the dichlorobenzene isomers and decreasing intensity for the higher chlorinated
16 isomers. Comparison of the amount of di chlorobenzene product formed indicated that an equal
17 quantity was produced with either A12O3 or fly ash; however, A12O3 formed four to five times
18 more product than did the CuO catalyst. For tri- to hexachlorobenzene congeners, MWC fly ash
19 reactions produced 5 to 10 times more product than did the metal catalysts. However, the
20 presence of the CuO catalyst in these reactions produced a chlorobenzene congener pattern
21 comparable to the fly ash reactions. With regard to chlorophenol production, A12O3 also produced
22 a unique dichlorophenol pattern, suggesting that A12O3 has a unique catalytic effect in the high-
23 temperature reactions of C2 aliphatic compounds.
24 Reactions with CuO produced additional products, including chlorinated methyl
25 compounds, chlorinated C2 aliphatics, and perchlorinated C3-C5 alkyl compounds. The authors
26 noted that these perchlorinated alkyl groups, formed by reacting ethylene and ethane over fly ash
27 in the presence of the CuO catalyst, are key intermediate compounds to the formation of first
28 aromatic rings in typical combustion systems. This emphasizes the importance of copper's
29 catalytic effects in a combustion fly ash system. A12O3 catalyzed reactions produced
30 nonchlorinated naphthalene and alkylbiphenyl compounds. Furthermore, the organic chlorine in
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1 aliphatic compounds may also act as a direct source of chlorine for the formation of CDDs/CDFs
2 in a carbon fly ash system (Weber et al., 1999).
3 In an earlier experiment using a similar flow tube apparatus, Froese and Hutzinger (1994)
4 formed chlorinated benzenes and phenols in fly ash catalyzed reactions with trichloroethylene at
5 temperatures of 400 to 500 °C. In this case, metal oxides (CuO, FeO3, and A12O3) were used as
6 catalysts, but no HC1 was added for oxychlorination of product compounds. Under combustion
7 conditions, temperature-dependent formation of chlorinated aromatics occurred from the
8 trichloroethylene starting compound. Reaction with fly ash at 600 °C formed hexachlorobenzene
9 in concentrations that were about 1,000 times greater than at 400 and 500 °C, with similar results
10 for chlorophenols. The authors hypothesized that key aromatic precursors for CDDs/CDFs are
11 formed in the higher-temperature region of a post-combustion zone (about 600 °C) and are then
12 carried to the cooler post-combustion region (about 300 °C), where the precursors form
13 CDDs/CDFs.
14
15 2.4. THE ROLE OF CHLORINE IN THE FORMATION OF CDDs/CDFs IN
16 COMBUSTION SYSTEMS
17 The formation of CDDs/CDFs in the post-combustion region of combustion systems via
18 either the precursor or de novo synthesis mechanisms requires the availability of a source of
19 chlorine (Luijk et al., 1994; Addink et al., 1995; Stanmore, 2004; Wikstrom et al., 2004 ).
20 Chlorine concentration in this region is related somehow to the chlorine content of combustion
21 fuels and feed materials in incineration/combustion systems because there can be no other source.
22 The main question regarding the role of chlorine in forming CDDs/CDFs is whether or not a
23 positive and direct correlation exists between the amount of chlorine in feeds and the amount of
24 CDDs/CDFs formed and emitted from the stack of a combustion system. If a direct relationship
25 appears to exist, then reductions in the chlorine content of fuels/feeds prior to combustion should
26 result in a corresponding reduction in the concentrations of CDDs/CDFs formed after combustion.
27 If the oxychlorination reactions require a number of steps, then the relationship between chlorine
28 in uncombusted fuels and CDDs/CDFs formed after combustion may not be linear, although it
29 may still be dependent in some nonlinear association. The main question can best be addressed by
30 examining both formation mechanisms revealed in laboratory-scale combustion experiments and
31 correlations between chlorine inputs with CDD/CDF outputs in commercial-scale combustors.
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1 2.4.1. Review of Laboratory-Scale Studies
2 A wide body of experimental evidence has elucidated the direct and indirect associations
3 between chlorine in feeds and fuels and the potential formation of CDDs/CDFs during
4 combustion. The de novo synthesis of CDDs/CDFs requires two basic reactions: the transfer of
5 chlorine to residual carbon particulate with subsequent formation of carbon-chlorine bonds and
6 the oxidation of this macromolecular complex to yield CO2 and volatile and semivolatile organic
7 compounds as side products (Weber et al., 1999). Transition metal compounds, such as CuCl2,
8 catalyze these reactions. Gaseous HC1, C12, and chlorine radicals are the most abundant sources of
9 chlorine available for participating in the formation of CDDs/CDFs and are initially formed as a
10 combustion by-product from the inorganic and organic chlorine contained in the fuel (Wikstrom et
11 al., 2003; Rigo, 1998; Addink et al., 1995; Rigo et al., 1995; Halonen et al., 1994; Luijk et al.,
12 1994; Altwicker et al., 1993; Wagner and Green, 1993; Dickson et al., 1992; Bruce et al., 1991;
13 Gullet et al., 1990b; Commoner et al., 1987; Vogg et al., 1987).
14 MSW contains approximately 0.45 to 0.90% (w/w) chlorine (Domalski et al., 1986). The
15 most predominant chlorine species formed from MSW combustion is gaseous HC1, which average
16 between 400 and 600 ppm in the combustion gas (Wikstrom et al., 2003; U.S. EPA, 1987a).
17 Chlorine is initially released from the chlorine in the MSW and is rapidly transformed to HC1 by
18 the abstraction of hydrogen from reacting with hydrocarbons present in the fuel (Wikstrom et al.,
19 2003). HC1 may oxidize to yield free chlorine gas by the Deacon process, and the free chlorine
20 directly chlorinates a CDD/CDF precursor along the aromatic ring structure. Further oxidation of
21 the chlorinated precursor in the presence of a transition metal catalyst (of which CuCl2 was found
22 to be the most active) yields CDDs/CDFs (Altwicker et al., 1993). Increasing the yield of chlorine
23 in vapor phase from HC1 oxidation generally increases the rate of CDD/CDF formation.
24 Formation kinetics are most favored at temperatures ranging from 200 to 450 °C. However HC1
25 is considered a weak chlorinating agent because of the tenacity of the hydrogen to carbon bond of
26 aromatic compounds(Wikstrom et al., 2003).
27 Chlorine production from gaseous HC1 can be reduced either by limiting initial HC1
28 concentration or by shortening the residence time in the Deacon process temperature (Bruce et al.,
29 1991; Gullett et al., 1990b; Commoner et al., 1987). Bruce et al. (1991) observed a general
30 increase in CDD/CDF formation with increases in the vapor-phase concentration of chlorine.
31 Bruce et al. (1991) verified a dependence of the formation of CDDs/CDFs in the post-combustion
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1 zone on the concentration and availability of gaseous chlorine. This finding is in agreement with
2 a simple experiment by Eklund et al. (1986) in which unsubstituted phenol was mixed with HC1 at
3 550 °C in a quartz tube reactor. A wide range of toxic chlorinated hydrocarbons was formed,
4 including CDDs/CDFs. Eklund et al. (1988) also found a dependence of the amounts of
5 chlorinated phenol product formed from the nonchlorinated starting material on the increased
6 amount of HC1 introduced into the reaction. Under the conditions of this experiment, no
7 chlorinated compounds were formed at an HC1 concentration of less than 10"3 mol, and maximum
8 chlorophenol concentration occurred at around 108 mol.
9 Born et al. (1993) also observed that increasing levels of HC1 gave rise to increasing rates
10 of oxychlorination of precursors, with increasing chances for the post-combustion formation of
11 CDDs/CDFs. However, Addink et al. (1995) observed that an HC1 atmosphere and/or chlorine
12 produced approximately equal quantities of CDDs/CDFs during the de novo synthesis from
13 oxidation of particulate carbon. Such results suggest that chlorine production via the Deacon
14 process reaction in the de novo synthesis may not be the only chlorination pathway and may
15 indicate that the HC1 molecule can be a direct chlorinating agent. In addition, some chlorine is
16 expected to be formed from the oxidation of metal chlorides (e.g., CuCl2), but Cl2formation from
17 the Deacon process is greater because of the continuous supply of HC1 delivered from the
18 combustion chamber (Bruce et al., 1991). In this case, a first-order dependence of HC1 to Cl2is
19 observed.
20 More recently, however, Wikstrom et al. (2003) have reported on the importance of
21 chlorine species on the de novo formation of CDDs/CDFs. HC1 can react with oxidizing radicals
22 (e.g., hydroxyl radical or OH) to produce chlorine radicals (C1-). Cl- are highly reactive and can
23 replace hydrogen atoms with chlorine atoms in the H-C bond of the aromatic structure. Thus, HC1
24 is most likely an indirect chlorinating agent via the formation of chlorine radicals.
25 Experimentally, about 18% of the total chlorine content in fuels can be thermally
26 converted to chlorine radicals in the post-combustion zone (Procaccini et al., 2003). Although
27 HC1 is the primary chlorine-containing product formed from the combustion of chlorine rich fuels,
28 HC1 may not be the major chlorinating agent in the formation of chloro-organics in the cooled
29 down region of the combustor. The experiments of Procaccini et al. (2003) indicate that the major
30 role of HC1 in the formation of chloro-organic compounds at cooler temperatures may be that of a
31 chemical progenitor of chlorine radicals. HC1 reacts with the oxidizing radicals OH and O
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1 abundantly present in combustion off-gases to reform C1-. Chlorine radicals readily abstract
2 hydrogen atoms from the H-C bond of aromatic compounds formed as combustion by-products of
3 organic fuels. By this means, unsubstituted aromatic compounds, e.g., benzene, undergo oxy-
4 chlorination reactions with the Cl- to form chlorobenzenes and chlorophenols. These products are
5 well defined precursor compounds for the synthesis of CDDs/CDFs.
6 Wagner and Green (1993) investigated the correlation of chlorine content in feed to stack
7 emissions of chlorinated organic compounds in a pilot-scale incinerator using HC1 flue gas
8 measurements as a surrogate for fuel-bound organic chlorine. In addition to MSW as a fuel,
9 variable amounts of polyvinyl chloride (PVC) resin were added during 6 of 18 stack test runs.
10 The resulting data were regressed to determine the coefficient of correlation between HC1
11 measurements and total chlorobenzene compound emission measurements. In nearly all of the
12 different regression analyses performed, the relationship between HC1 emissions and emissions of
13 chlorinated organic compounds was positive and well defined. In addition, the investigators
14 found a direct dependence of HC1 emission levels on the level of PVC in the waste, with generally
15 increasing amounts of HC1 formed as increasing amounts of PVC were added. From these
16 experiments, they concluded that decreased levels of organically bound chlorine in the waste
17 incinerated led to decreased levels of chlorinated organic compounds in stack emissions.
18 Kanters and Louw (1994) investigated a possible relationship between chlorine content in
19 waste feed and chlorophenol emissions in a bench-scale thermal reactor. MSW incineration with
20 a higher content of chlorine in the feed caused higher emissions of chlorophenols via the de novo
21 synthesis pathway. The investigators lowered the chlorine content of the prototype MWC by
22 replacing chlorine-containing fractions with cellulose. They observed appreciable decreases in the
23 amounts of chlorophenol formed from combustion and concluded that reductions in the chlorine
24 content of waste feeds or elimination of PVC prior to municipal waste combustion should result
25 in a corresponding reduction in chlorophenol and CDD/CDF emissions.
26 In a similar experiment, Wikstrom et al. (1996) investigated the influence of chlorine in
27 feed materials in the formation of CDDs/CDFs and benzenes in a laboratory-scale fluidized bed
28 reactor. Seven artificial fuels (composed of 34% paper, 30% wheat flour, 14% saw dust, 7%
29 polyethylene, and 2% metals), to which varying amounts of organic chlorine and inorganic
30 chlorine (CaCl2 • 6H2O) were added, were combusted. The chlorine content of these fuels varied
31 from 0.12 to 2%. All combustion was performed with a high degree of combustion efficiency
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1 (99.999%) to avoid the formation of polyvinylidene chloride and naphthalenes as products of
2 incomplete combustion of pure PVC. With the combustion conditions held constant, only the
3 chlorine content of the fuel was varied. Flue gases were sampled for CDDs/CDFs and
4 chlorobenzenes.
5 In these experiments, concentrations of PCB isomers were approximately 1,000-fold
6 higher than CDDs/CDFs (expressed as concentration of I-TEQDF). Moreover, a correlation was
7 found between I-TEQDF and PCB levels in the flue gases and the chlorine content of the fuel. A
8 fivefold increase in both I-TEQDF and PCB concentrations was observed in the flue gases from
9 combustion of fuels containing 0.5 and 1.7% total chlorine. Furthermore, no differences were
10 observed in the amount of chlorinated product produced or when the source of chlorine in the fuel
11 was organic or inorganic. No correlation was observed between total CDD/CDF and PCB
12 formation and total chlorine in the feed when chlorine levels in feed were or lower (0.5%). The
13 highest amounts of CDDs/CDFs and PCBs were formed from the fuel with the highest total
14 chlorine content (1.7%).
15 Under the conditions of this experiment, Wikstrom et al. (1996) observed that a chlorine
16 fuel content of 1% was a threshold for forming excess CDDs/CDFs and PCBs during combustion.
17 The authors noted that MSW in Sweden contained about 0.7% chlorine, of which approximately
18 40% was organic chlorine. They concluded that MSW was below the observed threshold value of
19 1% chlorine content associated with a general increase in CDD/CDF and PCB formation in the
20 post-combustion region. They also stated that their study did not support the hypothesis that
21 elimination of only PVC from waste prior to combustion will cause a significant reduction in
22 CDD/CDF emissions if the combustion process is well controlled (high combustion efficiency).
23 Wang et al. (2003) verified the existence of a theoretical chlorine-in-fuel threshold when they
24 demonstrated de novo synthesis combusting fuels with 0.8 to 1.1% chlorine.
25 A primary by-product of PVC combustion is HC1. Paciorek et al. (1974) thermally
26 degraded pure PVC resin at 400 °C and produced 550 mg/g HC1 vapor as a primary thermolysis
27 product, which was observed as being 94% of the theoretical amount, based on the percent weight
28 of chlorine on the molecule. Ahling et al. (1978) concluded that HC1 can act as a chlorine donor
29 to ultimately yield chlorinated aromatic hydrocarbons from the thermolytic degradation of pure
30 PVC and that these yields are a function of transit time, percent oxygen, and temperature. They
31 observed data from 11 separate experiments conducted with temperatures ranging from 570 to
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1 1,130 °C. These data indicated that significant quantities of various isomers of dichloro-,
2 trichloro-, tetrachloro-, and hexachlorobenzenes could be produced. Choudhry and Hutzinger
3 (1983) proposed that the radical species Cl- and H- generated in the incineration process may
4 attack the chlorinated benzenes and abstract hydrogen atoms to produce orthochlorine-substituted
5 chlorophenol radicals. These intermediate radical species then react with molecular oxygen to
6 yield ortho-substituted chlorophenols. As a final step, the ortho-substituted chlorophenols act as
7 ideal precursors to yield CDDs/CDFs with heat and oxygen. The chlorine in aliphatic compounds
8 has been observed as both yielding high amounts of HC1 during combustion and acting as a direct
9 chlorine source for the de novo synthesis of CDDs/CDFs (Weber et al., 1999).
10 In addition to HC1 as a by-product of PVC combustion, Kim et al. (2004) determined that
11 the combustion of pure PVC yielded appreciable amounts of PAHs, PCBs, chlorobenzenes, and
12 chlorophenols. They suggested that the gas-phase production of PCBs and chlorobenzenes
13 contributed to the gas-phase formation of CDDs/CDFs through the precursor mechanism.
14 Chlorophenols, however, contributed to the de novo formation. Kim et al. (2004) reported that the
15 de novo synthesis of CDDs/CDFs from chlorophenols was approximately 100 times greater than
16 formation from PCB and chlorobenzene precursors.
17 Takeo et al. (2002) found a clear correlation between dioxin formation and the chlorine
18 content of mixed plastics combusted in a laboratory scale incinerator. PVC, polyethylene (PE),
19 polystyrene (PS), and polyethylene terephthalate (PET) and their various mixtures were burned at
20 temperatures greater than 600 °C. Average CO concentrations in the exhaust gases were varied
21 from 2 to 880 ppm as a general indication of the quality of the fire in the combustion chamber.
22 When incinerated, each type of plastic formed CDDs/CDFs in the exhaust gases. Of the total
23 CDDs formed, hexa-CDD and tetra-CDD formed in the greatest amounts when PE was
24 combusted. Mono-CDF was the most abundant CDF formed from PE combustion. Mono-ortho
25 coplanar PCBs were preferentially formed over nonortho-PCBs. The combustion of PS caused
26 tetra-CDD to be formed in the greatest abundance of all possible CDDs whereas tetra-CDF was
27 the most abundant dibenzofuran. Mono-ortho PCBs formed more than nonortho coplanar PCBs
28 when PS was combusted. The combustion of PET mostly formed mono-CDD and mono-CDF
29 among the CDDs/CDFs formed. When PVC was combusted with the conditions of high
30 temperature and low CO (good combustion), a total of 53.5 ng/g of total CDD was formed, with
31 the hexa-CDD predominating. In addition, good combustion conditions formed a total of 771
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1 ng/g of CDFs, with C12 and C13 CDF congeners dominating. When PVC was combusted with the
2 conditions of low temperature and high CO (poor combustion), the total CDDs and CDFs formed
3 increased significantly to 429 ng/g and 8,492 ng/g, respectively. Tri-CDD and di-CDF dominated
4 the congener distributions suggesting that poor combustion of PVC tends to form high levels of
5 lower chlorinated CDDs/CDFs. The investigators observed that maintaining good combustion
6 tended to minimize the formation of CDDs/CDFs from the combustion of chlorinated plastics.
7 Shibata et al. (2003) reported on forming CDDs/CDFs from the combustion of PVC in
8 quartz ampules. Synthesis of CDDs/CDFs proceeded de novo in a temperature range of 200 to
9 400 °C and catalyzed by copper oxide (CuO). Maximum formation occurred at 300 °C. Hepa-
10 and Octa-CDD were the dominant CDDs observed in the flue gases whereas tetra-, penta-and
11 hexa-CDFs dominated the CDFs. The ratio of CDFs to CDDs from PVC combustion was greater
12 than 1, which is typical of MSW combustion (Shabata et al., 2003).
13 Addink and Altwicker (1999) reported on the role of the inorganic chloride ion in the
14 formation of CDDs/CDFs using the labeled compound Na37Cl. The inorganic chloride ion forms
15 carbon-chlorine bonds on soot particles during combustion. The chlorine in the soot can be
16 directly inserted into a CDD/CDF molecule during formation or it can exchange with the chloride
17 ions in the transitional metal catalyst, which promotes CDD/CDF formation. Thus, the inorganic
18 chlorine ion participates as a chlorine donor to CDD/CDF formation.
19 De Fre and Rymen (1989) reported on the formation of CDDs/CDFs from hydrocarbon
20 combustion in a domestic gas/oil burner in the presence of 15 and 300 ppm concentrations of HC1.
21 More than 100 chlorinated organic compounds were detected in the flue gases whenever HC1 was
22 injected into the system. The investigators observed formation of CDDs and CDFs in all
23 experiments where HC1 was injected in a hydrocarbon flame. In this case, CDFs were always
24 more abundant than CDDs. It was concluded that the relationship between the HC1 concentration
25 and the emitted concentration of CDDs/CDFs under fixed combustion conditions appeared to be
26 exponential for a wide range of temperatures (240 to 900 °C).
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1 2.4.2. Review of Full-Scale Combustion Systems
2 The review of experimental data clearly indicates an association between chlorine content
3 of feed/fuels and the potential synthesis of CDDs/CDFs. Paradoxically, the review of full-scale
4 operating incineration processes does not yield such unequivocal results, indicating that complex
5 kinetic events make strong associations difficult in full-scale systems. The following is a review
6 of studies of the association between chlorine in feeds and stack releases of CDDs/CDFs in full-
7 scale incineration systems.
8 In the stack testing of a variety of industrial stationary combustion sources during the
9 National Dioxin Study in 1987, EPA made a series of qualitative observations about the
10 relationship between total chlorine present in the fuel/waste and the magnitude of emissions of
11 CDDs/CDFs from the stack of the tested full-scale combustion facilities (U.S. EPA, 1987a). In
12 general, combustion units with the highest CDD emission concentrations had greater quantities of
13 chlorine in the fuel; conversely, sites with the lowest CDD emission concentrations contained
14 only trace quantities of chlorine in the feed. The typical chlorine content of various combustion
15 fuels was reported by Lustenhouwer et al. (1980) as coal, 1,300 |_ig/g; MSW, 2,500 |_ig/g; leaded
16 gasoline, 300 to 1,600 |_ig/g; and unleaded gasoline, 1 to 6 pg/g.
17 Thomas and Spiro (1995) also analyzed the relationship between CDD/CDF emissions
18 from combustion and the chlorine content of feed materials. Thomas and Spiro (1996) plotted
19 average CDD/CDF emission factors for a variety of combustion processes (black liquor boilers,
20 unleaded gasoline combustion, leaded gasoline combustion, wire incineration, cigarette
21 combustion, sewage sludge incineration, MWC, PCP-treated wood combustion, hazardous waste
22 incineration, and hospital waste incineration) against the average chlorine concentration of the
23 combusted material. The plot showed that average CDD/CDF emissions of combustion source
24 categories tend to increase with the average chlorine content of the combusted fuel. This analysis
25 indicated that combustion sources with relatively high combustion efficiency and adequate air
26 pollution controls tended to have emissions two orders of magnitude lower than those of poorly
27 operated sources. This suggests that the magnitude of CDD/CDF emissions is strongly dependent
28 on chlorine concentration in fuels in the context of the more poorly controlled and operated
29 combustion sources, and the association becomes less apparent in the well controlled facilities
30 operating with good combustion practices. The slope of the log-log plot was between 1 and 2 for
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1 the poorly controlled and operational facilities indicating that the relationship between chlorine
2 content and CDD/CDF emissions was more than proportional.
3 Costner (1998) reported finding a positive correlation between chlorine content of feed
4 material and CDD/CDF emissions at a full-scale hospital waste incinerator. Costner concluded
5 that emissions at this facility were dependent on chlorine input at a concentration as low as
6 0.031% and that there was no evidence of a threshold in the relationship between chlorine in feed
7 and CDD/CDF emissions.
8 Rigo et al. (1995) summarized the results of a study commissioned by the American
9 Society of Mechanical Engineers (ASME, 1995). The study was a statistical evaluation of the
10 relationship between HC1 concentration in flue gases and various combustion systems (i.e.,
11 MWCs, hospital waste incinerators, HWIs, biomass combustors, laboratory combustors, and
12 bench-scale combustors) to stack emissions of total CDDs/CDFs. In this study, HC1 was used as a
13 surrogate for total chlorine content in the fuel. The data analysis was sufficient for 92 facilities in
14 the database that showed both HC1 and CDD/CDF emissions. Of the 92 facilities, 72 did not
15 show a statistically significant relationship between chlorine input and CDD/CDF output in
16 emissions streams, 2 showed increasing CDD/CDF concentrations with increasing chlorine, and 8
17 showed decreasing CDD/CDF concentrations with increasing chlorine. AMSE (1995) reports the
18 following conclusion:
19
20 The failure to find simultaneous increases in most cases and finding inverse
21 relationships in a few indicates that any effect chlorine has on CDD/CDF emissions
22 is smaller than the variability of other causative factors. Whatever effect chlorine
23 has on CDD/CDF emissions in commercial-scale systems is masked by the effect
24 of APCS (air pollution control systems) temperature, ash chemistry, combustion
25 conditions, measurement imprecision, and localized flow stratification.
26
27 Liberson and Belanger (1995) reported the results of an analysis of the formation and
28 emission of CDDs/CDFs as a function of total chlorine in combustion feed materials at a rotary
29 kiln HWI. The data were generated from multiple test series conducted over a 13-month period at
30 the HWI while operating a carbon injection system specifically designed to control and reduce
31 CDD/CDF stack emissions. The chlorine feed rates ranged from 0 to 3,300 Ib/hr, and the
32 CDD/CDF emission rates ranged from 0.7 to 39 ng/dscm. The authors noted that multiple series
33 of CDD/CDF control systems were used on this HWI (i.e., a high temperature secondary
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1 combustion chamber, a spray dryer-evaporative quench that further cools the combustion gases,
2 activated carbon injection to adsorb semivolatile organics, and a cool-side electrostatic
3 precipitator followed by an acid gas scrubber to collect HC1 and C12). From analyses of the data,
4 the authors concluded that no correlation exists between CDD/CDF emissions and chlorine feed
5 in a modern MWC using carbon injection for CDD/CDF control.
6 More recently, Wang et al. (2003) investigated the association between chlorine content of
7 waste feeds and CDD/CDF emissions from full-scale combustion systems. Previously, Wikstrom
8 et al. (1996) had discerned a chlorine content in feeds of 1% as being a threshold concentration to
9 the formation of CDDs/CDFs, i.e., association with the magnitude of CDDs/CDFs formed
10 occurred only when chlorine content in the feed was > 1%. Wang et al (2003) confirmed the
11 apparent existence of a chlorine threshold to the emissions of total CDDs/CDFs after statistically
12 reviewing input of chlorine in feed versus output of CDDs/CDFs in emissions at two tested
13 medical incinerators and two tested MWCs. Additionally, the authors examined second-hand data
14 from 13 other dioxin sources obtained from the literature and found that the formation of CDFs
15 was greater than the formation of CDDs when the chlorine content of the waste feed exceeded the
16 threshold. However, when the chlorine content was below the approximate 1% threshold, the
17 formation of CDDs was greater than the formation of CDFs. The authors proposed that chlorine
18 content below the threshold formed chlorinated precursors to CDDs rather than forming the
19 dibenzofuran molecule. Chlorine content above the threshold contributed to deterioration of
20 combustion conditions causing the formation of PAHs, which, in turn, contributed to the
21 formation of CDFs.
22
23 2.5. POTENTIAL PREVENTION OF CDD/CDF FORMATION IN COMBUSTION
24 SYSTEMS
25 Given what is currently understood about oxychlorination reactions in the synthesis of
26 CDDs/CDFs, researchers have identified certain interventions that could be taken to reduce or
27 impede formation in combustion systems. Rayhunathan and Gullett (1996) demonstrated in a
28 pilot-scale incinerator that sulfur compounds can combine with the metal catalyst necessary to
29 stimulate the Deacon reaction of HC1 and oxygen to yield C12, thereby neutralizing the catalyzing
30 agent and reducing the formation of CDDs/CDFs. The Deacon reaction, which forms free
31 chlorine in the combustion plasma, is seen as occurring only in the presence of a catalyst. Thus,
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1 the sulfur dioxide (SO2) molecule (formed when sulfur in the fuel combines with oxygen) can
2 inhibit the catalytic activity of the fly ash by either combining with a metal-based Deacon catalyst
3 in the fly ash or depleting the C12 formed. The authors observed that the principal action of sulfur
4 in inhibiting the formation of CDDs/CDFs in combustion systems is through SO2 depletion of C12,
5 as follows:
6
7 C12 + SO2 + H2O « 2HC1 + SO2
8
9 The relevance of this finding is that the co-combustion of MSW with coal (that contains
10 sulfur) should lead to dramatic reductions in the amount of CDDs/CDFs formed and emitted, and
11 it may explain why, in the United States, coal combustion at power plants results in CDD/CDF
12 emission rates more than a magnitude lower than those at MWCs.
13 Naikwadi and Karasek (1989) investigated the addition of calcium oxide (CaO) and
14 triethylamine (TEA) to the flue gases of a combustion system as an inhibitor of the catalytic
15 activity of fly ash. They placed 500 |_ig 13C-labeled PCP (a dioxin precursor) in a combustion flow
16 tube and allowed it to react with organic-extracted MWC fly ash at 300 °C under an air stream.
17 Under these conditions, CDDs/CDFs were formed at concentrations ranging from 1,660 to 2,200
18 ng per 100 |_ig 13C-PCP. The experimental method was then modified by mixing reactive MWC
19 fly ash with either CaO or TEA. The results showed that the amount of CDDs/CDFs formed
20 could be reduced by an order of magnitude from the reaction of PCP with fly ash and the addition
21 of TEA as an inhibitor. When CaO was mixed with fly ash, the amount of CDDs/CDFs formed
22 decreased more than 20-fold.
23
24 2.6. THEORY ON THE EMISSION OF PCBs
25 Air emissions of PCBs from MSW incineration is less well studied. Probably the
26 formation mechanisms that apply to CDDs/CDFs would also apply to PCBs. Mechanism 1 (pass
27 through) is implicit in the Toxic Substances Control Act rule, which requires 99.9999%
28 destruction in HWIs. When this occurs, 0.0001% of the initial amount of PCBs fed into the FIWI
29 may be emitted from the stack. This may indicate that some small fraction of the PCBs present in
30 the fuel fed into an incineration process may result in PCB emissions from the stack of the
31 process.
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1 PCBs have been measured as contaminants in raw refuse prior to incineration in an MWC
2 (Choudhry and Hutzinger, 1983; Federal Register, 199la). Using this information, it is possible
3 to test mechanism 1 for CDD/CDF emissions: that the PCB contamination present in the fuel is
4 mainly responsible for emissions from the stack. The mass balance of total PCBs, beginning with
5 measurement in the raw refuse and ending with measurement at the stack of an RDF MWC
6 (Federal Register, 199la), can be used to calculate the destruction rated efficiency (DRE) of
7 incineration of the PCB-contaminated MSW. Using results from test number 11 at the RDF
8 facility (Federal Register, 199 la), a computation of DRE can be made using the following
9 equation (Brunner, 1984):
10
11
12 DRE=WJ-WO x 100% (2-1)
13 Wj
14
15 where:
16 Wj = mass rate of contaminant fed into the incinerator system
17
18 W0 = mass rate of contaminant exiting the incinerator system
19
20 In test 11, 811 ng total PCBs/g refuse were measured in the MSW fed into the incineration
21 system, and 9.52 ng/g were measured at the inlet to the pollution control device (i.e., outside the
22 furnace region but preceding emission control). From these measurements, a DRE of 98.8% can
23 be calculated. Therefore, it appears that PCB contamination in the raw MSW fed into this
24 particular incinerator may have accounted for the PCB emissions from the stack of the MWC.
25 PCBs can be thermolytically converted into CDFs (Choudhry and Hutzinger, 1983;
26 U.S. EPA, 1984). This process occurs at temperatures somewhat lower than those typically
27 measured inside the firebox of an MWC. Laboratory experiments conducted by EPA indicate that
28 the optimum conditions for CDF formation from PCBs are near a temperature of 675 °C in the
29 presence of 8% oxygen and a residence time of 0.8 sec (U.S. EPA, 1984). This resulted in a 3 to
30 4% efficiency of conversion of PCBs into CDFs. Because 1 to 2% of the PCBs present in the raw
31 refuse may survive the thermal stress imposed in the combustion zone of the incinerator (Federal
32 Register, 1991a), it is reasonable to presume that PCBs in the MSW may contribute to the total
33 mass of CDF emissions released from the stack of the incinerator.
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1 Although it appears that contamination of waste feed with PCBs may be an important
2 factor in detecting PCBs in stack emissions from combustion processes, recent research has
3 indicated that these compounds may also be formed in the post-combustion zone, either from de
4 novo synthesis or from precursor compounds. Zheng et al. (1999) observed the formation of
5 PCBs in the post-combustion zone from the pyrolysis of chlorobenzenes using a laboratory-scale
6 furnace. The investigators observed that PCBs were optimally formed from less-chlorinated
7 chlorobenzenes (e.g., 1,3-dichlorobenzene) catalyzed by CuCl2. In this experiment, maximum
8 PCB production occurred at a temperature of 350 °C. Wikstrom et al. (1998) reported secondary
9 formation of PCBs in the post-combustion zone similar to the de novo synthesis of CDDs/CDFs,
10 albeit PCBs were formed in only small amounts relative to CDDs/CDFs.
11 Fangmark and coworkers (1994) postulated that formation of PCBs and CDDs/CDFs in
12 the post-combustion zone may occur through the same mechanisms. On the other hand,
13 Blumenstock et al. (1998) produced results in a pilot-scale furnace that were inconsistent with the
14 de novo formation of CDDs/CDFs in the post-combustion zone (i.e., PCBs seemed to be
15 optimally formed at high temperatures in oxygen-deficient atmospheres). Shin and Chang (1999)
16 noted a positive correlation between PCB concentrations on MSW incineration fly ash and fly ash
17 concentrations of CDDs/CDFs, suggesting that high PCB levels in fly ash may be a contributory
18 cause of the post-combustion formation of CDDs/CDFs (i.e., PCBs are precursors to
19 CDDs/CDFs). Nito et al. (1997) noted the formation of CDFs and CDDs from the pyrolysis of
20 PCBs in a fluidized bed system, indicating that PCBs in feeds may account for CDFs formed in
21 MSW incineration. More combustion-related research needs to be conducted to firmly establish
22 whether or not PCB contamination in feeds or post-combustion formation (or both) may explain
23 the presence of PCBs in combustion flue gases.
24
25 2.7. SUMMARY AND CONCLUSIONS
26 2.7.1. Mechanisms of Formation of Dioxin-Like Compounds
27 There are three primary mechanisms for CDD/CDF emissions from combustion sources.
28 Mechanism 1 (pass through). This mechanism involves CDDs/CDFs contained in the feed
29 passing through the combustor intact and being subsequently released into the environment. For
30 most systems, this is not thought to be a major contributor to CDD/CDF emissions for three
31 reasons. First, for commercial systems with good combustion controls, the temperatures and
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1 residence times should result in the destruction of most CDDs/CDFs in the feed. Second, mass
2 balance studies of a number of combustion systems show that more CDDs/CDFs can be detected
3 in the cool down region downstream of the furnace than in the feed. Third, the CDD/CDF
4 congener profile in the feed differs from the congener profile in the stack emissions.
5 Consequently, synthesis appears to be a more important mechanism than pass through. The
6 concentration of CDDs/CDFs in the flue gases of any particular combustion system will
7 ultimately be derived as a result of the balance between reactions leading to formation and
8 reactions leading to destruction of these compounds.
9 Mechanism 2 (precursor). This mechanism involves the formation of CDDs/CDFs from
10 the thermal breakdown and molecular rearrangement of aromatic precursors either originating in
11 the feed or forming as a product of incomplete combustion. Actual synthesis of CDDs/CDFs
12 occurs in the post-combustor environment. Gaseous benzene is the most abundant aromatic
13 compound associated with products of incomplete combustion of waste. Benzene reacts with
14 chlorine radicals within the combustion gas plasma causing aromatic H abstraction and the
15 subsequent formation of chlorobenzenes and chlorophenols. Homogeneous gas-phase formation
16 of CDDs/CDFs occurs from these precursor compounds at temperatures >500 °C, catalyzed by the
17 presence of copper compounds. In addition, the CDDs/CDFs can form from gas-phase
18 precursors as heterogeneous, catalytic reactions with reactive fly ash surfaces. This reaction has
19 been observed to be catalyzed by the presence of a transition metal sorbed to the fly ash. The
20 most potent catalyst is CuCl2. Relatively low temperatures in the range of 200 to 450 °C has been
21 identified as a necessary condition for these heterogeneous reactions to occur, with either lower or
22 higher temperatures inhibiting the process. Because these reactions involve homogeneous gas-
23 phase and heterogeneous solid-phase chemistry, the rate of emissions is less dependent on reactant
24 concentration than on conditions that are favorable to formation, such as temperature, retention
25 time, source and species of chlorine, and the presence of a catalyst.
26 Mechanism 3 (de novo synthesis). This mechanism involves the heterogeneous solid-
27 phase formation of CDDs/CDFs in the post-combustion environment on the surface of fly ash.
28 Such heterogeneous chemistry occurs in two ways: (1) Directly from the oxidation of carbon
29 within the fly ash and subsequent reactions with organic and inorganic chlorine, and (2) The
30 oxidative breakdown of macromolecular carbon structures (e.g., graphite), and oxychlorination
31 reactions of aromatic precursors (such as chlorobenzenes and chlorophenols) on fly ash surfaces
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1 leading to CDD/CDF formation. In either case, formation kinetics is most favored at temperatures
2 in the range of 200 to 450 °C and is promoted by the catalytic properties of either the fly ash or
3 the presence of a transition metal compound. Mechanisms 2 and 3 can occur simultaneously,
4 share a number of common reaction pathways, and occur in the same physical environment, and
5 they are controlled by many of the same physical conditions. In well-designed and well-operated
6 combustion systems, the precursor species needed for mechanism 2 are reduced; consequently de
1 novo synthesis can become the dominant pathway for formation. In systems with incomplete
8 combustion, it is difficult to sort out the relative contribution of these two mechanisms to total
9 emissions. Both mechanisms, however, can be curtailed if steps are taken to minimize the
10 physical conditions needed to support formation (i.e., time, temperature, and reactive surface).
11 The combustion formation chemistry of PCBs is less well studied than that of
12 CDDs/CDFs, but it is reasonable to assume that these same three mechanisms would apply. For
13 waste incineration, PCBs can exist in significantly higher concentrations in the feed than do
14 CDDs/CDFs. Consequently, mechanism 1 may play a more prominent role in the origin of PCB
15 emissions than CDD/CDF emissions.
16
17 2.7.2. Role of Chlorine
18 From the various analyses on the role and relationship of chlorine to CDD/CDF formation
19 and emissions, the following observations and conclusions are made.
20 1. Although chlorine is an essential component in the formation of CDDs/CDFs in
21 combustion systems, the empirical evidence indicates that, for commercial-scale incinerators,
22 chlorine levels in feed are not the dominant controlling factor for the amount of CDDs/CDFs
23 released in stack emissions. Important factors that can affect the rate of CDD/CDF formation
24 include overall combustion efficiency, post-combustion flue gas temperatures and residence
25 times, and the types and designs of air pollution control devices employed on combustion
26 systems. Data from bench-, pilot-, and commercial-scale combustors indicate that CDD/CDF
27 formation can occur by three principal mechanisms. Some of these data, primarily from bench-
28 and pilot-scale combustors, have shown direct correlation between chlorine content in fuels and
29 rates of CDD/CDF formation. Other data, primarily from commercial-scale combustors, show a
30 weaker relationship between the presence of chlorine in feed and fuels and rates of CDD/CDF
31 released from the stacks of combustion systems. The conclusion that the amount of chlorine in
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1 feed is not a strong determinant of the magnitude of CDD/CDF stack emissions applies to the
2 overall population of commercial-scale combustors. For any individual commercial-scale
3 combustor, circumstances may exist in which changes in chlorine content in feed could affect
4 CDD/CDF emissions. For uncontrolled combustion, such as open burning of household waste,
5 chlorine content of wastes may play a more significant role in levels of CDD/CDF emissions than
6 the one observed in commercial-scale combustors.
7 2. Both organic and inorganic forms of chlorine in combustion fuels yields abundant
8 gaseous HC1 in the post-combustion region. It has been shown that chlorine radicals are the most
9 potent chlorinating agent in the formation of chloro-organic compounds from combustion. HC1
10 may be the dominant chemical progenitor of chlorine radicals participating in oxychlorination
11 reactions to CDD/CDF synthesis. Formation of chlorine radicals from HC1 occurs in the cool
12 down zone via the oxidation of HC1 in the presence of a transition metal catalyst (the Deacon
13 reaction). Although the preponderance of scientific evidence suggests that this is an important
14 pathway for producing chlorinated compounds in emissions, it is still unclear whether HC1 can
15 also directly chlorinate aromatics or whether it must first be oxidized to yield free chlorine.
16 3. Laboratory-scale experiments have examined correlations between chlorine content of
17 feeds and total CDDs/CDFs formed in combustion systems. These experiments suggested that for
18 feeds containing <1% chlorine, the amount of CDDs/CDFs formed is independent of the chlorine
19 content of the feed. For feeds with a chlorine content >1%, a direct correlation is observed. The
20 existence of an apparent threshold to the chlorine content of waste has been verified in full-scale
21 combustion systems. It has not been determined, however, whether these relationships are
22 relevant to poorly controlled combustion of wastes and biomass such as backyard barrel burning,
23 landfill fires, and agricultural burning.
24 4. The combustion of PVC can contribute to the formation of CDDs/CDFs in two ways.
25 Firstly, gaseous HC1 is a primary product formed from the combustion of PVC. We have seen
26 that HC1 is a major contributor of chlorine radicals necessary for the formation of CDDs/CDFs.
27 Thus, PVC indirectly contributes to dioxin synthesis. Secondly, the combustion of PVC directly
28 forms benzene which is followed by oxychlorination reactions that further form chlorinated
29 benzenes and chlorinated phenols; these compounds then act as precursors to CDD/CDF
30 formation.
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1 5. The most critical factors associated with minimizing CDD/CDF formation in
2 combustion systems are (a) Achieving nearly complete combustion of the feed through the
3 application of good combustion practice (i.e., time, temperature, and turbulence), and (b) Assuring
4 that combustion gases are quenched to below the temperature range for heterogeneous solid-phase
5 formation chemistry in the post-combustion region of the system, i.e. reduce the temperature to
6 below 200 °C.
7
8 2.7.3. General Conclusion
9 Although the formation chemistry of CDDs/CDFs is more complicated and less
10 understood than the relatively simple constructs described in this review, the current weight of
11 evidence suggests that the formation mechanisms outlined above describe the principal pathways
12 of most CDDs/CDFs formed and emitted from combustion sources.
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Table 2-1. Concentration of CDDs/CDFs on municipal incinerator fly ash at
varying temperatures
Congener
CDD
Tetra
Penta
Hexa
Hepta
Octa
CDF
Tetra
Penta
Hexa
Hepta
Octa
CDD/CDF concentration on fly ash (ng/g)
Temperature
200 °C
15
40
65
100
90
122
129
61
48
12
250 °C
26
110
217
208
147
560
367
236
195
74
300 °C
188
517
1,029
1,103
483
1,379
1,256
944
689
171
350 °C
220
590
550
430
200
1,185
1,010
680
428
72
400 °C
50
135
110
60
15
530
687
260
112
12
Source: Adapted from Vogg et al. (1987).
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Table 2-2. CDDs/CDFs formed from the thermolytic reaction of 690 mg benzene +
FeCl3 silica complex
Congener
DiCDD
TriCDD
TCDD
PeCDD
HxCDD
HpCDD
OCDD
Total CDDs
DiCDF
TriCDF
TCDF
PeCDF
HxCDF
HpCDF
OCDF
Total CDFs
Mass produced (ng)
4.9
54
130
220
170
98
20
696.9
990
7,800
12,000
20,000
33,000
40,000
74,000
187,000
Number of mols produced
0.019
0.019
0.4
0.62
0.44
0.23
0.04
1.94
4.2
29
39
59
88
98
167
484.2
Percent yielda
4.3 e-7
4.3 e-6
9.0 e-6
1.4 e-5
9.9 e-6
5.2 e-6
9.0 e-7
4.4 e-5
9.5 e-5
6.6 e-4
8.8e-4
1.3 e-3
2.0 e-3
1.1 e-3
3. 8 e-3
1.1 e-2
percent yield = (number of mols of CDD or CDF/mols benzene) x 100.
Source: Nestricketal. (1987).
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Table 2-3. De novo formation of CDDs/CDFs after heating Mg-Al silicate, 4%
charcoal, 7% Cl, 1% CuCl2 in H2O at 300 °C
Congener
TCDD
PeCDD
HxCDD
HpCDD
OCDD
Total CDDs
TCDF
PeCDF
HxCDF
HpCDF
OCDF
Total CDFs
Concentration of CDD/CDF (ng/g)
Reaction time (hr)
0.25
2
110
730
1,700
800
3,342
240
1,360
2,500
3,000
1,260
8,360
0.5
4
120
780
1,840
1,000
3,744
280
1,670
3,350
3,600
1,450
10,350
1
14
250
1,600
3,500
2,000
7,364
670
3,720
6,240
5,500
1,840
17,970
2
30
490
2,200
4,100
2,250
9,070
1,170
5,550
8,900
6,700
1,840
24,160
4
100
820
3,800
6,300
6,000
17,020
1,960
8,300
14,000
9,800
4,330
38,390
Source: Stieglitzetal. (1989a).
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350
300
O) 200
100
50
Figure 2-1. Typical CDD and CDF congener distribution in
contemporary municipal solid waste (MSW).
Source: Adapted from Abad et al. (2002).
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1000
Total CDDs
Total CDFs
Retention time (hr)
Figure 2-2. The de novo synthesis of CDDs/CDFs from heating carbon particulate at
300 °C at varying retention times.
Source: Addink et al. (1991).
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1000
800-
600-
M
O
400-
200-
1 00
200 300
Temperature (°C)
400
Total CDD
Total CDF
500
Figure 2-3. Temperature effects on CDD/CDF formation.
Source: Addink et al. (1991).
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1 3. COMBUSTION SOURCES OF CDDs/CDFs: WASTE INCINERATION
2
3 Incineration is the destruction of solid, liquid, or gaseous wastes through the application
4 of heat within a controlled combustion system. The purposes of incineration are to reduce the
5 volume of waste that needs land disposal and to reduce the toxicity of the waste. In keeping with
6 this definition, incinerator systems can be classified by the types of wastes incinerated:
7 municipal solid waste (MSW) incineration (commonly referred to as municipal waste
8 combustion), medical and pathological waste incineration, hazardous waste incineration, sewage
9 sludge incineration, tire incineration, and biogas flaring. Each of these types of incineration is
10 discussed in this chapter. The purpose of this chapter is to characterize and describe waste
11 incineration technologies in the United States and to derive estimates of annual releases of CDDs
12 and CDFs into the atmosphere from waste incineration facilities for reference years 1987, 1995,
13 and 2000.
14 As noted in Chapter 2, combustion research has developed three theories on the
15 mechanisms involved in the emission of CDDs and CDFs from combustion systems: (1)
16 CDDs/CDFs can be introduced into the combustor with the feed and pass through the system
17 unchanged (pass through), (2) CDDs/CDFs can be formed during combustion (precursor), and/or
18 (3) CDDs/CDFs can be formed via chemical reactions in the post-combustion portion of the
19 system (de novo synthesis). The total CDD/CDF emissions are likely to be the net result of all
20 three mechanisms; however, the relative importance of each mechanism is often uncertain.
21 To the extent practical with the available data, the combustors in each source category
22 were divided into classes according to similarity of emission factors. This classification effort
23 attempted to reflect the emission mechanisms described above. The emission mechanisms
24 suggest that the aspects of combustor design and operation that could affect CDD/CDF emissions
25 are furnace design, composition of the waste feed, temperature in the post-combustion zone of
26 the system, and the type of air pollution control device (APCD) used to remove contaminants
27 from the flue gases. Therefore, incineration systems that are similar in terms of these factors
28 should have similar CDD/CDF emissions. Accordingly, this chapter proposes classification
29 schemes that divide combustors into a variety of design classes based on these factors. Design
30 class, as used here, refers to the combination of furnace type and accompanying APCD.
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1 3.1. MUNICIPAL WASTE COMBUSTION
2 As noted above, emissions can be related to several factors, including furnace design,
3 composition of the waste feed, temperature in the post-combustion zone of the system, and type
4 of APCD used to remove contaminants from the flue gases. This section proposes a
5 classification scheme that divides municipal waste combustors (MWCs) into a variety of design
6 classes on the basis of those factors. Because different APCDs are operated at different
7 temperatures, operating temperature is used to define some design classes. To account for the
8 influence of the waste feed, the proposed classification system distinguishes between refused-
9 derived fuel (RDF) and normal MSW. This section begins with a description of the MWC
10 technology and then proposes the design classification scheme. Using this scheme, the municipal
11 waste combustion industry is characterized for the reference years 1987, 1995, and 2000.
12 Finally, the procedures for estimating emissions are explained and the results summarized.
13
14 3.1.1. Description of Municipal Waste Combustion Technologies
15 For the purposes of this report, municipal waste combustion furnace types are divided
16 into three major categories: mass burn, modular, and RDF. Mass burn and RDF technologies
17 dominate the large MWC category and modular technology dominate the small MWC category.
18 Each of these furnace types is described below, followed by a description of the APCDs used
19 with the system.
20
21 3.1.1.1. Furnace Types
22 Mass burn. This furnace type was so named because it burned MSW as received (i.e.,
23 no preprocessing of the waste was conducted other than removal of items too large to go through
24 the feed system). Today, a number of other furnace types also burn unprocessed waste, as
25 described below. Mass burn furnaces are distinguished from the other types because they burn
26 the waste in a single stationary chamber. In a typical mass burn facility, MSW is placed on a
27 grate that moves through the combustor. The 1995 inventory indicated that the combustion
28 capacities of mass burn facilities range from 90 to 2,700 metric tons of MSW per day. Three
29 subcategories of mass burn technologies are described below.
30
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1 • Mass burn refractory-walled systems represent an older class of MWCs (generally
2 built in the late 1970s to early 1980s) that were designed only to reduce the volume of
3 waste disposed of by 70 to 90%. These facilities usually lack boilers to recover the
4 combustion heat for energy purposes. In the mass burn refractory-walled design, the
5 MSW is delivered to the combustion chamber by a traveling grate or a ram feeding
6 system. Combustion air in excess of stoichiometric amounts (i.e., more oxygen is
7 supplied than is needed for complete combustion) is supplied both below and above
8 the grate. As of 2000, few mass burn refractory-walled MWCs remain; almost all
9 have closed or been dismantled.
10
11 • Mass burn waterwall (MB-WW) facilities represent enhanced combustion efficiency,
12 as compared with mass burn refractory-walled incinerators. Although it achieves
13 similar volume reductions, the MB-WW incinerator design provides a more efficient
14 delivery of combustion air, resulting in higher sustained temperatures. Figure 3-1 is a
15 schematic of a typical MB-WW MWC. The term "waterwall" refers to a series of
16 steel tubes that run vertically along the walls of the furnace and contain water. Heat
17 from combustion produces steam, which is then used to drive an electrical turbine
18 generator or for other industrial needs. This transfer of energy is called energy
19 recovery. MB-WW incinerators are the dominant form of incinerator found at large
20 municipal waste combustion facilities.
21
22 • Mass burn rotary kilns use a water-cooled rotary combustor that consists of a rotating
23 combustion barrel configuration mounted at a 15- to 20-degree angle of decline. The
24 refuse is charged at the top of the rotating kiln by a hydraulic ram (Donnelly, 1992).
25 Preheated combustion air is delivered to the kiln through various portals. The slow
26 rotation of the kiln (10 to 20 rotations/hr) causes the MSW to tumble, thereby
27 exposing more surface area for complete burnout of the waste. These systems are
28 also equipped with boilers for energy recovery. Figure 3-2 is a schematic of a typical
29 rotary kiln combustor.
30
31 Modular. This is a second general type of municipal waste combustion furnace used in
32 the United States. As with the mass burn type, modular incinerators burn waste without
33 preprocessing. Modular MWCs consist of two vertically mounted combustion chambers (a
34 primary and secondary chamber). In the 1995 inventory, the combustion capacity of modular
35 combustors ranged from 4 to 270 metric tons per day, that is, they are predominately small
36 MWCs. The two major types of modular systems, excess air and starved air, are described
37 below.
38
39 • The modular excess-air system consists of a primary and a secondary combustion
40 chamber, both of which operate with air levels in excess of stoichiometric
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1 requirements (i.e., 100 to 250% excess air). Figure 3-3 illustrates a typical modular
2 excess-air MWC.
3
4 • In the starved (or controlled) air type of modular system, air is supplied to the primary
5 chamber at substoichiometric levels. The products of incomplete combustion entrain
6 in the combustion gases that are formed in the primary combustion chamber and then
7 pass into a secondary combustion chamber. Excess air is added to the secondary
8 chamber, and combustion is completed by elevated temperatures sustained with
9 auxiliary fuel (usually natural gas). The high, uniform temperature of the secondary
10 chamber, combined with the turbulent mixing of the combustion gases, results in low
11 levels of PM and organic contaminants being formed and emitted. Therefore, many
12 existing modular units lack post-combustion APCDs. Figure 3-4 is a schematic view
13 of a modular starved-air MWC.
14
15 Refuse-Derived Fuel (RDF). The third major type of MWC furnace technology is
16 designed to combust RDF; this technology is generally used at very large MWC facilities. RDF
17 is a general term that describes MSW from which relatively noncombustible items are removed,
18 thereby enhancing the combustibility of the waste. RDF is commonly prepared by shredding,
19 sorting, and separating out metals to create a dense MSW fuel in a pelletized form having a
20 uniform size. Three types of RDF systems are described below.
21
22 • The dedicated RDF system burns RDF exclusively. Figure 3-5 shows a typical
23 dedicated RDF furnace using a spreader-stoker boiler. Pelletized RDF is fed into the
24 combustor through a feed chute using air-swept distributors; this allows a portion of
25 the feed to burn in suspension and the remainder to burn out after falling on a
26 horizontal traveling grate. The traveling grate moves from the rear to the front of the
27 furnace, and distributor settings are adjusted so that most of the waste lands on the
28 rear two-thirds of the grate. This allows more time to complete combustion on the
29 grate. Underfire and overfire air are introduced to enhance combustion, and these
30 incinerators typically operate at 80 to 100% excess air. Waterwall tubes, a
31 superheater, and an economizer are used to recover heat for production of steam or
32 electricity. The 1995 inventory indicated that dedicated RDF facilities range from 227
33 to 2,720 metric tons per day total combustion capacity.
34
35 • CofiredRDFs burn either RDF or normal MSW, along with another fuel.
36
37 • The fluidized-bed RDF burns the waste in a turbulent and semisuspended bed of sand.
38 The MSW may be fed into the incinerator either as unprocessed waste or as a form of
39 RDF. The RDF may be injected into or above the bed through ports in the combustor
40 wall. The sand bed is suspended during combustion by introducing underfire air at a
41 high velocity, hence the term "fluidized." Overfire air at 100% of stoichiometric
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1 requirements is injected above the sand suspension. Waste-fired fluidized-bed RDFs
2 typically operate at 30 to 100% excess air levels and at bed temperatures around 815
3 °C. Atypical fluidized-bed RDF is represented in Figure 3-6. The technology has
4 two basic designs: (1) a bubbling-bed incineration unit and (2) a circulating-bed
5 incineration unit. The 1995 inventory indicated that fluidized-bed MWCs have
6 capacities ranging from 184 to 920 metric tons per day. These systems are usually
7 equipped with boilers to produce steam.
9 3.1.1.2. Air Pollution Control Devices
10 MWCs are commonly equipped with one or more post-combustion APCDs to remove
11 various pollutants prior to release from the stack, such as PM, heavy metals, acid gases, and
12 organic contaminants (U.S. EPA, 1992d). Types of APCDs include
13
14 • Electrostatic precipitator
15 • Fabric filter
16 • Spray dry scrubbing system
17 • Dry sorbent injection
18 • Wet scrubber
19
20 Electrostatic precipitator (ESP). The ESP is generally used to collect and control PM
21 that evolves during MSW combustion by introducing a strong electrical field in the flue gas
22 stream; this in turn charges the particles entrained in the combustion gases (Donnelly, 1992).
23 Large collection plates receive an opposite charge to attract and collect the particles. CDD/CDF
24 formation can occur within the ESP at temperatures in the range of 150 °C to about 350 °C. As
25 temperatures at the inlet to the ESP increase from 150 to 300 °C, CDD/CDF concentrations have
26 been observed to increase by approximately a factor of 2 for each 30 °C increase in temperature
27 (U.S. EPA, 1994f). As the temperature increases beyond 300 °C, formation rates decline.
28 Although ESPs in this temperature range efficiently remove most particulates and the
29 associated CDDs/CDFs, the CDD/CDF formation that occurs can result in a net increase in
30 CDD/CDF emissions. This temperature-related formation of CDDs/CDFs within the ESP can be
31 applied, for purposes of this report, to distinguish cold-sided ESPs, which operate at or below
32 230 °C, from hot-sided ESPs, which operate at an inlet temperature greater than 230 °C. Most
33 ESPs have been replaced with better-performing and lower-cost fabric filter technology.
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1 Fabric filter (FF). FFs are also PM control devices that remove dioxins associated with
2 particles and any vapors that adsorb to the particles. The filters are usually 6- to 8-inch-diameter
3 bags, 30 feet long, made from woven fiberglass material, and arranged in series. An induction
4 fan forces the combustion gases through the tightly woven fabric. The porosity of the fabric
5 allows the bags to act as filter media and retain a broad range of particle sizes (down to less than
6 1 jam in diameter). The FF is sensitive to acid gas; therefore, it is usually operated in
7 combination with spray dryer adsorption of acid gases.
8 Spray dry scrubbing system (SDSS). Spray dry scrubbing, also called spray dryer
9 adsorption, involves the removal of both acid gas and PM from the post-combustion gases. By
10 themselves, the units probably have little effect on dioxin emissions. In a typical SDSS, hot
11 combustion gases enter a scrubber reactor vessel. An atomized hydrated lime slurry (water plus
12 lime) is injected into the reactor at a controlled velocity (Donnelly, 1992). The slurry rapidly
13 mixes with the combustion gases within the reactor. The water in the slurry quickly evaporates,
14 and the heat of evaporation causes the combustion gas temperature to rapidly decrease. The
15 neutralizing capacity of hydrated lime reduces the acid gas constituents of the combustion gas
16 (e.g., HC1 and SO2) by greater than 70%. A dry product consisting of PM and hydrated lime
17 settles to the bottom of the reactor vessel.
18 SDSS technology is used in combination with ESPs or FFs. SDSSs reduce ESP inlet
19 temperatures to make a cold-sided ESP. In addition to acid gas, particulate, and metals control,
20 SDSSs with FFs or ESPs achieve greater than 90% dioxin control (U.S. EPA, 1992d), and they
21 typically achieve greater than 90% SO2 and HC1 control.
22 Dry sorbent injection (DSI). DSI is used to reduce acid gas emissions. By themselves,
23 these units probably have little effect on dioxin emissions. In this system, dry hydrated lime or
24 soda ash is injected directly into the combustion chamber or into the flue duct of the hot post-
25 combustion gases. In either case, the reagent reacts with and neutralizes the acid gas constituents
26 (Donnelly, 1992).
27 Wet scrubber (WS). WS devices are designed for acid gas removal and are more
28 common to MWC facilities in Europe than in the United States. They should help reduce
29 emissions of dioxin in both vapor and particle forms. The devices consist of two-stage
30 scrubbers. The first stage removes HC1, and the second stage removes SO2 (Donnelly, 1992).
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1 Water is used to remove HC1 and caustic or hydrated lime is added to remove SO2 from the
2 combustion gases.
3 Other types of APCDs. In addition to the APCDs described above, some less common
4 types are also used in some MWCs. An example is activated carbon injection (CI) technology.
5 Activated carbon is injected into the flue gas prior to the gas reaching SDSSs with FFs (or ESP).
6 Dioxin (and mercury) are absorbed onto the activated carbon, which is then captured by the FFs
7 or ESP. CI technology improves dioxin control technologies by an additional 75% and is
8 commonly referred to as flue gas polishing. Many APCDs have been retrofitted to include CI,
9 including more than 120 large MWCs.
10
11 3.1.1.3. Classification Scheme
12 Based on the array of municipal waste combustion technologies described above, a
13 classification system for deriving CDD/CDF emission estimates was developed. Assuming that
14 facilities with common design and operating characteristics have a similar potential for
15 CDD/CDF emission, the MWCs operating in 1987 and 1995 were divided into categories
16 according to the eight furnace types and seven APCDs described above. This resulted in 17
17 design classes in 1987 and 40 design classes in 1995. Because fewer types of APCDs were used
18 in 1987 than in 1995, fewer design classes are needed for estimating emissions. The MWCs
19 operating in 2000 were divided into three furnace types and 12 APCDs, resulting in 36 design
20 classes. Design classes for all three reference years are summarized in Figures 3-7 through 3-9.
21
22 3.1.2. Characterization of MWCs in Reference Years 2000,1995, and 1987
23 Table 3-1 lists, by design/APCD type, the number of facilities and activity level (kg
24 MSW incinerated /yr) for MWCs in reference year 2000. Similar inventories are provided for
25 reference years 1995 and 1987 in Tables 3-2 and 3-3. This information was derived from five
26 reports: U.S. EPA, 1987b; SAIC, 1994; Taylor and Zannes, 1996; Solid Waste Technologies,
27 1994; and Huckaby, 2003. In general, the information was collected via telephone interviews
28 with the plant operators.
29 Using Tables 3-1, 3-2, and 3-3, a number of comparisons can be made between the
30 reference years:
31
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1 • The number of facilities stayed about the same (113 in 1987, 130 in 1995, and 104
2 facilities in 2000), but the amount of MSW incinerated more than doubled from 1987
3 to 1995 (13.8 billion kg in 1987 and 28.8 billion kg in 1995) and remained constant
4 from 1995 to 2000 (27.7 billion kg in 2000).
5
6 • The dominant furnace technology shifted from modular in 1987 (57 units and 1.4
7 billion kg) to MB-WW facilities in 1995 (57 units and 17 billion kg) and 2000 (142
8 units and 19 billion kg).
9
10 • The dominant APCD technology shifted from hot-sided ESPs in 1987 (54 units and
11 11 billion kg) to FFs in 1995 (55 units and 16 billion kg) and spray dryer with FF, CI,
12 and selective noncatalytic reduction (88 large MSW units) and ESPs (28 small
13 MWCs)in2000.
14
15 • The use of hot-sided ESPs dropped from 54 facilities in 1987 (11 billion kg) to 16
16 facilities in 1995 (2.2 billion kg).
17
18 • The number of uncontrolled facilities dropped from 38 in 1987 (0.6 billion kg) to 10
19 in 1995 (0.2 billion kg) and 8 in 2000 (0.1 billion kg).
20
21 3.1.3. Estimation of CDD/CDF Emissions from MWCs
22 Compared with other CDD/CDF source categories, MWCs have been more extensively
23 evaluated for CDD/CDF emissions. In 2000, due to new regulations, EPA's Office of Air
24 Quality Planning and Standards (OAQPS) obtained emission test reports for all large MWCs.
25
26 3.1.3.1. Estimating CDD/CDF Emissions from MWCs in Reference Year 2000
27 OAQPS has obtained dioxin test reports for all 167 large MWCs following emission
28 control retrofits and used these data to calculate emissions for large MWCs for reference year
29 2000. Test reports for small MWCs will not be obtained until retrofits are completed in 2005.
30 Emissions for small MWCs for 2000 were estimated on the basis of emission factors. Using the
31 test reports, concentrations and emissions were calculated for each of the 17 named dioxin/furan
32 congeners and the remainder of the congener groups (homologues), making up total dioxin/furan
33 emissions (for 27 congeners/groups) for each of the 167 MWC units (Huckaby, 2003). The
34 calculations were based on the individual congener/group concentrations for the MWC, the flue
35 gas flow rate and MWC steam generation rate during the test, and the annual steam generation at
36 the MWC. Table 3-4 presents congener concentration with three different detection limit (DL)
37 assumptions: (1) a value of zero for concentrations below the DL, (2) a value of one-half the DL
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1 for concentrations below the DL, and (3) a value of the DL for concentrations below the DL.
2 Table 3-5 lists the national dioxin/furan TEQ emissions for large MWCs.
3
4 3.1.3.2. Estimating CDD/CDF Emissions from MWCs in Reference Years 1995 and 1987
5 Within the context of this report, adequate emission testing for CDDs/CDFs was
6 available for 1 1 of the 113 facilities in the 1987 inventory and 27 of the 130 facilities in the 1995
7 inventory. Nationwide CDD/CDF air emissions from MWCs for reference years 1987 and 1995
8 were estimated using the three-step process described below.
9 Step 1. Estimation of emissions from all stack-tested facilities. The EPA stack testing
1 0 method (EPA Method 23) produces a measurement of CDDs/CDFs in units of mass
1 1 concentration of CDD/CDF (nanograms per dry standard cubic meter of combustion gas
12 [ng/dscm]) at standard temperature and pressure (20 °C and 1 atmosphere [atm]) and adjusted to
13 a measurement of 7% oxygen in the flue gas (U.S. EPA, 1995b). This concentration is assumed
14 to represent conditions at the point of release from the stack into the air. Equation 3-1 was used
15 to derive annual emission estimates for each tested facility:
16
17 ETEQ= C*V
18 W9ng/g (3-1)
19
20 where:
21 E^Q = annual TEQ emissions (g/yr)
22 C = combustion flue gas TEQ concentration (ng/dscm) (20 °C, 1 atm; adjusted to 7% O2)
23 V = volumetric flow rate of combustion flue gas (dscm/hr) (20 °C, 1 atm; adjusted to
24 7% O2)
25 CF = capacity factor, fraction of time that the MWC operates (0.85)
26 H = total hours in a year (8,760 hr)
27
28 After calculating annual emissions for each tested facility, the emissions were summed
29 across all tested facilities for each reference year. (Many of the emission tests do not correspond
30 exactly to these two years. In these cases, the equipment conditions present at the time of the test
3 1 were compared with those during the reference year to determine their applicability.)
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1 Step 2. Estimation of emissions from all nonstack-tested facilities. This step involves
2 multiplying the emission factor and annual activity level for each MWC design class and then
3 summing across classes. The activity levels for reference years 1995 and 1987 are summarized
4 in Tables 3-2 and 3-3, respectively. The emission factors were derived by averaging the emission
5 factors across each tested facility in a design class. The emission factor for each facility was
6 calculated using the following equation:
7
8 EFMWC= CxFv
9 /„ (3-2)
10 where:
1 1 EFMWC = emission factor, average ng TEQ/kg of waste burned
12 C = TEQ or CDD/CDF concentration in flue gases (ng TEQ/dscm) (20 °C,
13 1 atm; adjusted to 7% O2)
14 Fv = volumetric flue gas flow rate (dscm/hr) (20 °C, 1 atm; adjusted to 7% O2)
15 Iw = average waste incineration rate (kg/hr)
16
17 Example: An MB-WW MWC equipped with a cold-sided ESP.
18 Given:
19 C = 10 ng TEQ/dscm (20 °C, 1 atm; adjusted to 7% O2)
20 Fv = 40,000 dscm/hr (20 °C, 1 atm; adjusted to 7% O2)
21 Iw= 10,000 kg MSW/hr
22
23 EF MB-WW = 10«g x 4Q,QQQdscm x hr
24 dscm hr 1 0,000 kg
25
26 = 40 ng TEQ
27 kg MSW burned
28
29 EPA was not able to obtain engineering test reports of CDD/CDF emissions for a number
30 of design classes. In these cases, the above procedure could not be used to derive emission
3 1 factors. Instead, the emission factors of the tested design class that was judged most similar in
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1 terms of dioxin control was assumed to apply to the untested class. The following logic was used
2 to make this decision:
3
4 1. The tested APCDs for the furnace type of the untested class were reviewed to see
5 whether any operated at a similar temperature.
6
7 2. If any operated at similar temperatures, the one with the most similar technology was
8 assumed to apply.
9
10 3. If none operated at a similar temperature, then the most similar furnace type with the
11 same control device was assumed to apply.
12
13 Table 3-6 lists all design categories with no tested facilities and shows the class with tested
14 facilities that was judged to be most similar.
15 The emission factors for each design class are the same for both reference years because
16 the emission factor is determined only by the design and operating conditions and is independent
17 of the year of the test.
18 Step 3. Sum emissions from tested and untested facilities. This step involves
19 summing emissions from all tested and untested facilities. This process is shown in Tables 3-7a
20 and 3-7b and 3-8a and 3-8b for the reference years 1995 and 1987, respectively. The tables are
21 organized by design class and show the emission estimates for the tested and untested facilities
22 separately. The calculation of emissions from untested facilities is broken out to show the
23 activity level and emission factor for each design class.
24
25 3.1.4. Summary of CDD/CDF (TEQ) Emissions from MWCs for 2000,1995, and 1987
26 The activity level estimates (i.e., the amount of MSW that is annually combusted by the
27 various municipal waste combustion technologies) are given a high confidence rating for 1987
28 (13.8 billion kg of waste), 1995 (28.8 billion kg of waste), and 2000 (27.7 billion kg of waste).
29 For all three years, independent sources conducted comprehensive surveys of activity levels for
30 virtually all facilities (U.S. EPA, 1987b; Solid Waste Technologies, 1994; SAIC, 1994; Taylor
31 and Zannes, 1996; Huckaby, 2003).
32 The emission factor estimates are given a high confidence rating for 2000 and a medium
33 confidence rating for both 1995 and 1987. All facilities were tested in 2000, whereas a moderate
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1 fraction of the facilities were tested in 1995 and 1987: 27 of 130 facilities (21%) in 1995 and 11
2 of 113 facilities in 1987 (10%). The tested facilities represented 27 and 21% of the total activity
3 level of operating MWCs in 1995 and 1987, respectively. These tests represent most of the
4 design categories identified in this report. The emission factors were developed from emission
5 tests that followed standard EPA protocols, used strict QA/QC procedures, and were well
6 documented in engineering reports. Because all tests were conducted under normal operating
7 conditions, some uncertainty exists about the magnitude of emissions that may occur during
8 other conditions (e.g., upset conditions, start up, and shut down).
9 These confidence ratings produce an overall high confidence rating in the annual
10 emission estimates of 78.9 g I-TEQDF in 2000 (13.7 g TEQDF-WHO98 [15.3 g I-TEQDF] for large
11 MWC units and 63.6 g I-TEQDF for small MWC units). A medium confidence rating is assigned
12 to the annual emission estimates of 1,250 g TEQDF-WHO98 (1,100 g I-TEQDF) in 1995 and 8,877
13 g TEQDF-WH098 (7,915 g I-TEQDF) in 1987.
14
15 3.1.5. Congener Profiles of Municipal Waste Combustion Facilities
16 The air emissions from MWCs contain a mixture of CDD and CDF congeners. These
17 mixtures can be translated into what are called "congener profiles," which represent the
18 distribution of total CDDs and total CDFs present in the mixture. A congener profile may serve
19 as a signature of the types of CDDs/CDFs associated with a particular MWC technology and
20 APCD. Figure 3-10 is a congener profile of an MB-WW MWC equipped with an SDSS and FF
21 (the most common type of MWC and APCD design in use today). This congener profile
22 indicates that OCDD dominates CDD/CDF emissions and that every toxic CDD/CDF congener
23 is detected in the emissions. Figures 3-11 and 3-12 present 2,3,7,8-TCDD frequency distribution
24 and 1,2,3,7,8-PeCDD frequency distribution, respectively. According to Huckaby (2003), the
25 distribution of these two congeners varies little from MWC to MWC. Although these two
26 congeners represent less than 1% of total dioxin/furan emissions, they contribute approximately
27 13 to 23% of the I-TEQDF emissions, depending on which TEF system is used.
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1 3.1.6. Estimated CDDs/CDFs in MWC Ash
2 Ash from MWCs is required to be disposed of in permitted landfills from which releases
3 to the general environment are controlled. For background purposes, however, some information
4 is presented below about the quantities of CDDs/CDFs in ash from MWCs.
5 An estimated 7 million metric tons of total ash (bottom ash plus fly ash) were generated
6 by MWCs in 1992 (telephone conversation between J. Loundsberry, U.S. EPA Office of Solid
7 Waste, and L. Brown, Versar, Inc., February 24, 1993). EPA indicated that 2 to 5 million metric
8 tons of total ash were produced annually in the late 1980s from MWCs, with fly ash comprising
9 5 to 15% of the total (U.S. EPA, 1991b).
10 EPA reported the results of analyses of MWC ash samples for CDDs/CDFs (U.S. EPA,
11 1990c). Ashes from five state-of-the-art facilities located in different regions of the United States
12 were analyzed for all 2,3,7,8-substituted CDDs/CDFs. The TEQ levels in the ash (fly ash mixed
13 with bottom ash) ranged from 106 to 466 ng I-TEQDF/kg, with a mean value of 258 ng I-
14 TEQDF/kg. CDD/CDF levels are generally much higher in fly ash than in bottom ash. For
15 example, Fiedler and Hutzinger (1992) reported levels of 13,000 ng I-TEQDF/kg in fly ash.
16 In another study (Washington State Department of Ecology, 1998), CDD/CDF congener
17 data were reported for ash and other solid residuals from three municipal incinerators (Fort
18 Lewis, Bellingham [municipal plus medical wastes], and Spokane). The data were compiled and
19 evaluated to determine a total I-TEQ concentration and loading. Nondetect values were included
20 as either zero or one-half the DL or at the DL. The results were as follows, assuming that
21 nondetect values were at zero concentration:
22
23 Location Type of Residual I-TEQ (|ag/kg) I-TEQ (mg/day)
24 Ft. Lewis Bottom ash 0 0
25 Fly ash 4.98 0.76
26 Bellingham Mixed ash
27 (average of three tests) 0.038 1.14
28 Spokane Mixed ash 0.163 38
29 Fly ash 0.51 24.3
30 Bottom ash 0.0001 0.02
31
32
33 In Shane et al. (1990), ash from five municipal incinerators was analyzed for a number of
34 constituents, including CDDs (but not CDFs) and PCBs. For dioxins, three of the incinerators
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1 were at nondetectable levels (DL of 1 |ig/kg). The other two incinerators had detectable levels of
2 five CDD congener groups (no analyses were reported for individual congeners), and the
3 averages for the two units were 26, 59, 53, 25, and 12 |_ig/kg for TCDD, PeCDD, HxCDD,
4 HpCDD, and OCDD, respectively. These levels were much higher that those reported by EPA
5 (U.S. EPA, 1990c).
6 For PCBs, the five sets of ashes were analyzed for 10 congener groups. All groups were
7 detected for one of the incinerators. However, the other four incinerators contained little or no
8 octa, nona, or deca congeners. The average PCB concentration (all congener groups) for the five
9 incinerators was 216 pg/kg, with a range of 99 to 322 pg/kg.
10 No generation rates of the ashes were given (Shane, 1990), therefore, the measured
11 concentrations cannot be readily converted to quantities of CDDs or PCBs. The ashes from each
12 of the five incinerators were disposed of in multiple fashions. For two of the incinerators, the ash
13 was sent to metal recovery and also landfilled. For a third, the fly ash was sold. For a fourth, the
14 ashes were only landfilled. For the fifth, the ashes were used in road building and also landfilled.
15 For those incinerators with more than one ash disposition, no breakdown was given of how much
16 went to each location. Fifteen other incinerators were discussed in Shane (1990). Thirteen of
17 them disposed of their ash exclusively in landfills, and the other two partially disposed of their
18 ash in landfills.
19 Table 7 in Clement et al. (1988) presents 13 data sets for CDD/CDF congener groups for
20 municipal incinerator ash. The average data for each congener group and the ranges of each
21 group are given in Table 3-9. No data were presented for individual congeners or for ash
22 quantities.
23 Ash from three incinerators (one in North America, one in Europe, and one in Japan) had
24 mean CDD concentrations of 363, 588, and 2.6 pg/kg, respectively (Table 3-3 in U.S. EPA,
25 1987a). The values ranged from less than 0.5 to 3.537 pg/kg. For CDFs, the respective mean
26 concentrations for the first two incinerators were 923 and 288 pg/kg. Data for the third
27 incinerator were not reported. The CDF range for the two incinerators was from less than 0.5 to
28 1,770 j-ig/kg. No data were given for individual congeners or for quantities of ashes.
29 In Table 1 in Lahl et al. (1991), data are presented for concentrations of total CDDs and
30 total CDFs in the ash from an ESP from a municipal incinerator. Total CDDs were 140.46 |_ig/kg
31 in the summer samples and 86 |_ig/kg in the winter samples. Total CDFs were 54.97 |_ig/kg in the
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1 summer samples and 73.85 |_ig/kg in the winter samples. No data were given for individual
2 congeners, nor was there information about the quantity of precipitator ash generated. It was
3 assumed that the data were not for TEQs.
4 A wire reclamation incinerator was reported to have 0.41 |_ig/kg of CDDs and 11.6 |_ig/kg
5 of CDFs in fly ash from its stack emissions (Table 3-11 in U.S. EPA, 1987a). For the same
6 incinerator, the furnace ash concentrations were reported as 0.58 pg/kg CDDs and 0.73 pg/kg
7 CDFs. Again, no data were given for individual congeners or for quantities of the ashes.
8 Data from the aforementioned sources are compiled in Table 3-10 of this document for
9 comparison purposes. Annual TEQ amounts were estimated by multiplying the mean TEQ total
10 ash concentration by the estimated amount of MWC ash generated annually (approximately 7
11 million metric tons in 1995 and 5 million metric tons in 1987). Where possible, ash quantities
12 were broken down into fly ash or bottom ash. Fly ash was assumed to be 10% of the total ash
13 and bottom ash was assumed to be 90% of the total ash.
14 Imagawa et al. (2001) analyzed samples collected from eight Japanese MSW incinerators
15 to determine dioxin levels in the fly ash (Table 3-11). Specific congener data were not available,
16 so TEQ calculations could not be performed.
17 Kobylecki et al. (2001) analyzed the reduction of dioxins in fly ash by pelletizing the ash
18 and reburning the pellets in a laboratory-scale bubbling fluidized-bed furnace. Fly ash for the
19 test input material was collected from a fly ash filter vessel during 4 days of MWC operation.
20 The concentrations of the dioxin collected and composited congeners are shown in Table 3-12.
21 The total TEQ value derived by Kobylecki was 862 ng I-TEQDF/kg of fly ash.
22 Sakai et al. (2001) analyzed the levels of dioxins and PCBs in fly ash and bottom ash
23 from a newly constructed MWC in Japan (Table 3-13). TEQ values derived from the data give a
24 total of 423 ng I-TEQDF/kg for fly ash and 10.5 ng I-TEQDF/kg for bottom ash for dioxins and
25 31.6 ng I-TEQDF/kg for fly ash and 0.85 ng I-TEQDF/kg for bottom ash for PCBs.
26 Each of the five facilities sampled by EPA had companion ash disposal facilities
27 equipped with leachate collection systems or some means of collecting leachate samples (U.S.
28 EPA, 1990c). Leachate samples were collected and analyzed for each of these systems.
29 Detectable levels were found in the leachate at only one facility (3 ng I-TEQDF/L); the only
30 detectable congeners were HpCDDs, OCDD, and HpCDFs.
31
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1 3.1.7. Recent EPA Regulatory Activities
2 As part of the 1990 Clean Air Act mandates, EPA promulgated CDD/CDF emission
3 standards for all existing and new MWC units at facilities with aggregate combustion capacities
4 greater than 35 metric tons per day (Federal Register, 1995e). These standards, established under
5 Section 129 of the Clean Air Act, required facilities to use "maximum achievable control
6 technology" (MACT) at MWC units and emission control retrofit for large MWC units (units
7 with capacities greater than 225 metric tons per day) by December 2000. In response to a court
8 remand, the regulations were subsequently amended to remove small MWC units (units with
9 capacities ranging from 35 to 225 metric tons per day) (Federal Register, 1995e). The specific
10 emission standards for large MWCs (expressed as ng/dscm of total CDD/CDF, based on standard
11 dry gas corrected to 7% oxygen) are a function of the size, APCD configuration, and age of the
12 facility, as listed below.
13
14 1995 Emission standards for large MWCs
15 (ng total CDD/CDF/dscnO Facility age, size, and APCD
16 60 Existing; >225 metric tons/day; ESP-
17 based APCD
18 30 Existing; >225 metric tons/day; non-
19 ESP-based APCD
20 13 New; >225 metric tons/day
21
22 EPA reestablished emission standards for small MWCs (MWC units between 35 and 225
23 tons/day combustion capacity) in December 2000. These standards contain two different dioxin
24 emission limits: one for small MWCs at plants with an aggregate capacity greater than 250
25 tons/day (Class I MWCs) and another for small MWCs at plants with an aggregate capacity less
26 than 250 tons/day (Class II MWCs). The limit for the Class I MWCs is the same as the 1995
27 limits for large MWCs. The limit for the smaller Class II MWCs is 125 ng/dscm. These small
28 MWCs are on schedule to comply with the standards by December 2005. Small MWC emissions
29 were estimated to be 63 g/yr I-TEQ in 2000 and should be less than 2 g/yr in 2005 when all
30 control retrofits are completed (U.S. EPA, 2003e).
31
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1 3.2. HAZARDOUS WASTE INCINERATION
2 Hazardous waste incineration is the controlled pyrolysis and/or oxidation of potentially
3 dangerous liquid, gaseous, and solid waste. It is one technology used to manage hazardous waste
4 under RCRA and the Comprehensive Environmental Response, Compensation, and Liability Act
5 (CERCLA, or Superfund) programs.
6 Hazardous wastes are burned in a variety of situations and are covered in a number of
7 different sections in this report.
8
9 • Much hazardous waste is burned in facilities dedicated to burning this type of waste.
10 Most of these dedicated facilities are located on-site at chemical manufacturing
11 facilities and burn only the waste associated with their on-site industrial operations.
12 Hazardous waste is also burned at dedicated facilities located off-site. These facilities
13 accept waste from multiple sources. On- and off-site hazardous waste burning
14 facilities are addressed in Sections 3.2.1 to 3.2.4.
15
16 • Hazardous waste is also burned in industrial boilers and furnaces that are permitted to
17 burn the waste as supplemental fuel. These facilities have significantly different
18 furnace designs and operations than those of dedicated hazardous waste incinerators
19 (HWIs). They are discussed in Section 3.2.6.
20
21 • Hazardous waste is also burned in halogen acid furnaces (HAFs), in which halogen
22 acids (such as HC1) may be produced from halogenated secondary materials. These
23 facilities are discussed in Section 3.2.7.
24
25 • A number of cement kilns and lightweight aggregate kilns are also permitted to burn
26 hazardous waste as auxiliary fuel. These are discussed separately in Section 5.1.
27
28 • Mobile HWIs are typically used for site cleanup at Superfund sites. These units can
29 be transported from one location to another and operate for a limited duration at any
30 given location. Because these facilities are transitory, they are not included in this
31 inventory at this time.
32
33 The following subsections review the types of hazardous waste incineration technologies
34 commonly in use in the United States and present the CDD/CDF emission estimates from all
35 facilities operating in 1987, 1995, and 2000.
36
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1 3.2.1. Furnace Designs for HWIs
2 The four principal furnace designs employed for the combustion of hazardous waste in
3 the United States are rotary kiln, liquid injection, fixed-hearth, and fluidized-bed (Dempsey and
4 Oppelt, 1993). The majority of commercial operations use rotary kiln incinerators. On-site
5 (noncommercial) hazardous waste incineration technologies use an equal mix of rotary kiln and
6 liquid injection furnaces, along with some fixed-hearth and fluidized-bed operations (U.S. EPA,
7 1996h). These HWI technologies are discussed below.
8 Rotary kiln. Rotary kiln incinerators consist of a rotary kiln coupled with a high-
9 temperature afterburner. Because rotary kilns are excess air units designed to combust hazardous
10 waste in any physical form (i.e., liquid, semisolid, or solid), they are the most common type of
11 HWI used by commercial off-site operators. The rotary kiln is a horizontal cylinder lined with
12 refractory material. Rotation of the cylinder on a slight slope provides for gravitational transport
13 of the hazardous waste through the kiln (Buonicore, 1992a). The tumbling action of the rotating
14 kiln causes mixing and exposure of the waste to the heat of combustion, thereby enhancing
15 burnout.
16 Solid and semi-solid wastes are loaded into the top of the kiln by an auger or rotating
17 screw. Fluid and pumpable sludges and wastes are typically introduced into the kiln through a
18 water-cooled tube. Liquid hazardous waste is fed directly into the kiln through a burner nozzle.
19 Auxiliary fuel (natural gas or oil) is burned in the kiln chamber at startup to reach elevated
20 temperatures. The typical heating value of hazardous waste (8,000 British thermal units
21 [Btu]/kg) is sufficient to sustain combustion without auxiliary fuel (U.S. EPA, 1996h). The
22 combustion gases emanating from the kiln are passed through a high-temperature afterburner
23 chamber to more completely destroy organic pollutants entrained in the flue gases. Rotary kilns
24 can be designed to operate at temperatures as high as 2,580 °C, but more commonly operate at
25 about 1,100 °C.
26 Liquid injection. Liquid injection incinerators are designed to burn liquid hazardous
27 waste. These wastes must be sufficiently fluid to pass through an atomizer for injection as
28 droplets into the combustion chamber. The incinerator consists of a refractory-lined steel
29 cylinder mounted in either a horizontal or a vertical alignment. The combustion chamber is
30 equipped with one or more waste burners. Because of the rather large surface area of the
31 atomized droplets of liquid hazardous waste, the droplets quickly vaporize. The moisture
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1 evaporates, leaving a highly combustible mix of waste fumes and combustion air (U.S. EPA,
2 1996h). Secondary air is added to the combustion chamber to complete the oxidation of the
3 fume and air mixture.
4 Fixed-hearth. Fixed-hearth incinerators are starved-air or pyrolytic incinerators. Waste
5 is ram-fed into the primary chamber and incinerated at about 50 to 80% of stoichiometric
6 requirements. The resulting smoke and pyrolytic combustion products are then passed through a
7 secondary combustion chamber where relatively high temperatures are maintained by the
8 combustion of auxiliary fuel. Oxygen is introduced into the secondary chamber to promote
9 complete thermal oxidation of the organic molecules entrained in the gases. Other types of
10 hearths include roller hearths and rotary hearths. Roller hearths use a conveyor system to move
11 waste from the kiln entrance to the exit. In rotary hearths, waste enters and exits through the
12 same gate, and the hearth rotates inside a circular tunnel kiln.
13 Fluidized-bed. The fluidized-bed incinerator is similar in design to the incinerators used
14 in MSW incineration (see Section 3.1). In fluidized-bed HWIs, a layer of sand is placed on the
15 bottom of the combustion chamber. The bed is preheated by underfire auxiliary fuel at startup.
16 The hot gases channel through the sand at relatively high velocity, and the turbulent mixing of
17 combustion gases and combustion air causes the sand to become suspended (Buonicore, 1992a)
18 and take on the appearance of a fluid medium; hence the term "fluidized-bed" combustor. The
19 incinerator is operated at temperatures below the melting point of the bed material (typical
20 temperatures are within a range of 650 to 940 °C). A constraint on the types of waste burned is
21 that the solid waste particles must be capable of being suspended within a furnace. When the
22 liquid or solid waste is combusted in the fluid medium, the exothermic reaction causes heat to be
23 released into the upper portion of the combustion chamber. The upper portion typically has
24 much larger volume than the lower portion, and temperatures can reach 1,000 °C (Buonicore,
25 1992a). This high temperature is sufficient to combust volatilized pollutants emanating from the
26 combustion bed.
27
28 3.2.2. APCDs for HWIs
29 Most HWIs use APCDs to remove undesirable components from the flue gases that
30 evolve during the combustion of the hazardous waste. These unwanted pollutants include
31 suspended ash particles (PM), acid gases, metals, and organic pollutants. The APCD controls
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1 collect these pollutants and reduce the amount discharged from the incinerator stack to the
2 atmosphere. The levels and types of these combustion byproducts are highly site-specific,
3 depending on factors such as waste composition and incinerator system design and operating
4 parameters (e.g., temperature and exhaust gas velocity). The APCD typically comprises a series
5 of different devices that work together to clean the combustion exhaust flue gas. Unit operations
6 usually include exhaust gas cooling followed by PM and acid gas control.
7 Exhaust gas cooling may be achieved using a waste heat boiler or heat exchanger, by
8 mixing with cool ambient air, or by injecting a water spray into the exhaust gas. A variety of
9 types of APCDs are used to remove PM and acid gases. Such devices include WSs (such as
10 venturi, packed bed, and ionizing systems), ESPs, and FFs (sometimes used in combination with
11 dry acid gas scrubbing). In general, the control systems can be grouped into the following three
12 categories: wet, dry, and hybrid wet/dry systems. The controls for acid gases (either dry or wet
13 systems) cause temperatures to be reduced preceding the control device. This impedes the
14 formation of CDDs/CDFs in the post-combustion area of the typical FIWI. It is not unusual for
15 stack concentrations of CDDs/CDFs at a particular HWI to be in the range of 1 to 100 ng/dscm
16 (Helble, 1993), which is low when compared with those of other waste incineration systems.
17 However, the range of total CDD/CDF flue gas concentrations measured in the stack emissions
18 of HWIs during trial burns across the class of HWI facilities spans four orders of magnitude,
19 ranging from 0.1 to 1,600 ng/dscm (Helble).
20 The three categories of APCD systems are described below:
21
22 • Wet system. A WS is used for both particulate and acid gas control. Typically, a
23 venturi scrubber and a packed-bed scrubber are used in a back-to-back arrangement.
24 Ionizing WSs, wet ESPs, and innovative venturi-type scrubbers may be used for more
25 efficient particulate control. WSs generate a wet effluent liquid wastestream
26 (scrubber blowdown). They are relatively inefficient at fine particulate control when
27 compared with dry control techniques and have equipment corrosion concerns.
28 However, WSs provide efficient control of acid gases and have lower operating
29 temperatures (compared with dry systems), which may help control the emissions of
30 volatile metals and organic pollutants.
31
32 • Dry system. In SDSSs, an FF or ESP is used for particulate control, frequently in
33 combination with dry scrubbing for acid gas control. Compared with WSs, SDSSs
34 are inefficient in controlling acid gases.
35
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1 • Hybrid system. In hybrid systems, a dry technique (ESP or FF) is used for
2 particulate control, followed by a wet technique (WS) for acid gas control. Hybrid
3 systems have the advantages of both wet and dry systems (lower operating
4 temperature for capture of volatile metals, efficient collection of fine particulates,
5 efficient capture of acid gases) while avoiding many of the disadvantages. In some
6 hybrid systems, known as "zero discharge systems," the WS liquid is used in the dry
7 scrubbing operation, thus minimizing the amount of liquid byproduct waste.
9 Facilities that do not use any APCDs fall under a separate and unique category. These are
10 primarily liquid waste injection facilities, which burn wastes with low ash and low chlorine
11 content; therefore, they are low emitters of PM and acid gases.
12
13 3.2.3. Estimation of CDD/CDF Emission Factors for HWIs
14 To estimate emission factors, EPA's Office of Research and Development (ORD)
15 generally subdivides the combustors in each source category into design classes judged to have
16 similar potential for CDD/CDF emissions. However, as explained below, dedicated HWIs have
17 not b een sub divi ded.
18 Total CDD/CDF emissions are likely the net result of all three of the mechanisms
19 described above (pass through, precursor, and de novo synthesis); however, the relative
20 importance of each mechanism can vary among source categories. In the case of HWIs, the third
21 mechanism (post-combustion formation) is likely to dominate, because HWIs are typically
22 operated at high temperatures and with long residence times, and most have sophisticated real-
23 time monitoring and controls to manage the combustion process. Therefore, any CDDs/CDFs
24 present in the feed or formed during combustion are likely to be destroyed before exiting the
25 combustion chamber. Consequently, for purposes of generating emission factors, it was decided
26 not to subdivide this class on the basis of furnace type.
27 Emissions resulting from the post-combustion formation of CDDs/CDFs in HWIs can be
28 minimized using a variety of technologies:
29
30 • Rapid Flue Gas Quenching. The use of wet and dry scrubbing devices to remove
31 acid gases usually results in the rapid reduction of flue gas temperatures at the inlet to
32 the APCD. If the temperature is reduced below 200 °C, the low-temperature catalytic
33 formation of CDDs/CDFs is substantially retarded.
34
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1 • Use of PM APCDs. PM control devices can effectively capture condensed and
2 adsorbed CDDs/CDFs that are associated with the entrained PM (in particular, those
3 adsorbed on unburned carbon-containing particulates).
4
5 • Use of Activated Carbon. Activated CI is used at some HWIs to collect (sorb)
6 CDDs/CDFs from the flue gas. This may be achieved using carbon beds or by
7 injecting carbon and collecting it in a downstream PM APCD.
9 All of these approaches appear very effective in controlling dioxin emissions at dedicated
10 HWIs; emissions data are insufficient to generalize about any minor differences. Consequently,
11 for purposes of generating emission factors, ORD decided not to subdivide this class on the basis
12 of APCD type.
13 EPA's Office of Solid Waste (OSW) compiled a database summarizing the results of
14 stack testing for CDDs/CDFs at a number of HWIs between 1993 and 2000 (U.S. EPA, 2002b).
15 The CDD/CDF emission factors for HWIs in 1995 are based on data from 17 HWIs tested
16 between 1993 and 1996; emissions of HWIs in 2000 are based on data from 22 HWIs tested in
17 2000. The furnace types and numbers at the 22 HWI facilities tested in 2000 were 11 rotary kiln
18 incinerators, 6 liquid injection incinerators, 2 rotary hearth units, 1 fluidized-bed incinerator, and
19 1 roller hearth.
20 Rather than classifying the dedicated HWI designs to derive an emission factor, ORD
21 decided to derive the emission factor as an average across all tested facilities. First, an average
22 emission factor was calculated using eq 3-3.
23
24 EFHm= CxFv
25 /„ (3-3)
26
27 where:
28 EFHWI = emission factor (average ng TEQ per kg of waste burned)
29 C = TEQ or CDD/CDF concentration in flue gases (ng TEQ/dscm) (20 °C,
30 1 atm; adjusted to 7% O2)
31 Fv = volumetric flue gas flow rate (dscm/hr) (20 °C, 1 atm; adjusted to 7% O2)
32 Iw = average waste incineration rate (kg/hr)
33
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1 Although 22 HWIs were tested in 2000, the OSW database contained values for flue gas
2 flow rates for 12 of these incinerators. Therefore, only 12 HWIs could be used to develop an
3 emission factor. After developing an average emission factor for each HWI, the overall average
4 congener-specific emission factor was derived using eq 3-4.
5
6 ^W^W;7 = (EFHWIi + EFHWI2 + EFHWI3 + + EFHM]7) /N (3-4)
1
8 where:
9 EFavgHWI = average emission factor for the tested HWIs (ng/kg)
10 N = number of tested facilities
11
12 Tables 3-14a and 3-14b present the average emission factors developed for specific
13 congeners, total CDDs and total CDFs, and TEQs for the HWIs tested from 1993 to 1996 and in
14 2000, respectively. The average congener emission profile for the 17 HWIs tested from 1993
15 through 1996 are presented in Figure 3-13. The average emission factor for the 17 HWIs was
16 3.88 ng TEQDF-WHO98/kg (3.83 ng I-TEQDF/kg) of waste feed (assuming nondetect values are
17 zero). The average emission factor for the 22 HWIs tested in 2000 was 2.13 ng TEQDF-
18 WHO98/kg (2.12 ng I-TEQDF/kg) of waste feed (assuming nondetect values are zero). The
19 emission factor developed for reference year 1995 was used as a surrogate for reference year
20 1987.
21
22 3.2.4. Emission Estimates for HWIs
23 Although emissions data were available for 10% of HWIs operating in 1995 and 17% of
24 the HWIs operating in 2000 in the United States (i.e., 22 of the 132 HWIs operating in 2000 have
25 been tested), the emission factor estimates are assigned a medium confidence rating because of
26 uncertainties resulting from the following:
27
28 • Variability of the waste feeds. The physical and chemical composition of the waste
29 can vary from facility to facility and even within a facility. Consequently, CDD/CDF
30 emissions measured for one feed may not be representative of those of other feeds.
31
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1 • Trial burns. Much of the CDD/CDF emissions data were collected during trial
2 burns, which are required as part of the RCRA permitting process and are used to
3 establish the destruction rate efficiency of principal hazardous organic constituents in
4 the waste. During trial burns, a prototype waste is burned that is intended to
5 maximize the difficulty in achieving good combustion. For example, chlorine,
6 metals, and organics may be added to the waste. The FIWI may also be operated
7 outside normal operating conditions. The temperature of both the furnace and the
8 APCD may vary by a wide margin (high and low temperatures), and the waste feed
9 system may be increased to maximum design load. Accordingly, it is uncertain how
10 representative the CDD/CDF emissions measured during the trial burn will be of
1 1 emissions during normal operating conditions.
12
13 Dempsey and Oppelt (1993) estimated that up to 1.3 million metric tons of hazardous
14 waste were combusted in HWIs during 1987. A confidence rating of medium is assigned to this
15 estimate. EPA estimated that 1.5 million metric tons of hazardous waste were combusted in
16 HWIs each year in the early 1990s (Federal Register, 1996b). The activity level estimate for
17 1995 is assigned a high confidence rating because it is based on a review by EPA of the various
18 studies and surveys conducted in the 1990s to assess the quantity and types of hazardous wastes
19 being managed by various treatment, storage, and disposal facilities. Because of a lack of data
20 regarding the amount of waste burned in 2000, the 1995 estimate (1.5 million metric tons) was
21 also used for determining TEQ emissions for 2000.
22 The annual TEQ emissions for reference years 1987, 1995, and 2000 were estimated
23 using eq 3-5.
24
25 -t^HWI ~ ^ HWl X •"-HWI (?'-*)
26 where:
27 EJJWJ = annual emissions from all HWIs, tested and nontested (g TEQ/yr)
28 EFHWI = mean emission factor for HWIs (ng TEQ/kg of waste burned)
29 AHWI = annual activity level of all operating HWIs (million metric tons/yr)
30
3 1 Applying the average TEQ emission factor for dedicated HWIs (3.88 ng TEQDF-
32 WHO98/kg waste [3.83 ng I-TEQDF/kg waste]) to these production estimates yields estimated
33 emissions of 5 g TEQ (TEQDF-WHO98 or I-TEQDF) in 1987 and 5.8 g TEQDF-WHO98 (5.7 g I-
34 TEQDF) in 1995. For 2000, applying the average TEQ emission factors for dedicated HWIs (2.13
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1 ng TEQDF-WHO98/kg waste [2.12 ng I-TEQDF/kg waste]) to a production estimate of 1.5 million
2 metric tons yields estimated emissions of 3.2 g TEQDF-WHO98 (3.18 g I-TEQDF). Medium
3 confidence rating is assigned to these estimates because the emission factor was given a medium
4 confidence rating.
5
6 3.2.5. Recent EPA Regulatory Activities
7 The EPA regulated CDD/CDF emissions from HWIs (Federal Register, 1999b, 2004).
8 The regulations are specific to the I-TEQ concentration in the combustion gases leaving the
9 stack. Existing FIWIs equipped with waste heat boilers and dry scrubbers (as air pollution
10 control devices) cannot emit more than 0.28 ng I-TEQ/dscm. All other existing HWIs are limited
11 to 0.4 ng I-TEQ/dscm of stack gas. Regulatory requirements are more strict for newly built
12 HWIs. Newly built HWIs equipped with waste heat boilers and dry scrubbers (as air pollution
13 control devices) cannot emit more than 0.11 ng I-TEQ/dscm. All other newly built HWIs are
14 limited to 0.2 ng I-TEQ/dscm of stack gas.
15
16 3.2.6. Industrial Boilers and Furnaces Burning Hazardous Waste
17 In 1991, EPA established rules that allow the combustion of some liquid hazardous waste
18 in industrial boilers and furnaces (Federal Register, 1991c). These facilities typically burn oil or
19 coal for the primary purpose of generating electricity. Liquid hazardous waste can only be
20 burned as supplemental (auxiliary) fuel, and the rule limits use to no more than 5% of the
21 primary fuels. These facilities typically use an atomizer to inject the waste as droplets into the
22 combustion chamber. They are equipped with particulate and acid gas emission controls and in
23 general are sophisticated, well-controlled facilities that achieve good combustion.
24 The national OSW database contains congener-specific emission concentrations for two
25 boilers burning liquid hazardous waste as supplemental fuel tested from 1993 to 1996. The
26 average congener and congener group emission profiles for the industrial boiler data set are
27 presented in Figure 3-14. The database also contains congener-specific emission concentrations
28 for four boilers tested in 2000. Of the boilers tested in 2000, sufficient data to calculate average
29 TEQ emissions were available for only one boiler. The average congener and TEQ emission
30 factors are presented in Tables 3-14a and 3-14b. The limited set of emissions data prevented
31 subdividing this class to derive an emission factor. The equation used to derive the emission
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1 factor is the same as eq 3-4. The TEQ emission factors for the industrial boiler are 0.65 ng
2 TEQDF-WHO98/kg (0.64 ng I-TEQDF/kg) of waste feed for 1993 to 1996 and 1.212 ng TEQDF-
3 WHO98/kg (1.214 ng I-TEQDF/kg) of waste feed for 2000. These emission factors are assigned a
4 low confidence rating because they reflect testing at only 2 of 136 hazardous waste boilers and
5 furnaces operating from 1993 to 1996 and only 1 of the 114 hazardous waste boilers and furnaces
6 operating in 2000.
7 Dempsey and Oppelt (1993) estimated that approximately 1.2 billion kg of hazardous
8 waste were combusted in industrial boilers/furnaces in 1987. EPA estimated that in each year in
9 the early 1990s approximately 0.6 billion kg of hazardous waste were combusted in industrial
10 boilers/furnaces (Federal Register, 1996b). It is possible that cement kilns and light-weight
11 aggregate kilns burning hazardous waste were included in the estimate by Dempsey and Oppelt
12 for 1987; the estimate for 1995 does not appear to include these hazardous waste-burning kilns.
13 A confidence rating of low is assigned to the estimated activity level for 1987, which was largely
14 based on a review of state permits (Dempsey and Oppelt, 1993). The activity level estimate for
15 1995 is assigned a medium confidence rating because it was based on a review by EPA of the
16 various studies and surveys conducted in the 1990s to assess the quantity and types of hazardous
17 wastes being managed by various treatment, storage, and disposal facilities. Because of a lack of
18 data regarding the amount of waste burned in 2000, the 1995 estimate (1.5 million metric tons)
19 was used as a surrogate for 2000.
20 Equation 3-5, which was used to calculate annual TEQ emissions for dedicated HWIs,
21 was also used to calculate annual TEQ emissions for industrial boilers/furnaces. Multiplying the
22 average TEQ emission factors by the total estimated kg of liquid hazardous waste burned in
23 1987, 1995, and 2000 yields annual emissions in g-TEQ/yr. From this procedure, the emissions
24 from all industrial boilers/furnaces burning hazardous waste as supplemental fuel are estimated
25 as 0.78 g TEQDF-WHO98 (0.77 g I-TEQDF) in 1987, 0.39 g TEQDF-WHO98 (0.38 g I-TEQDF) in
26 1995, and 1.82 g TEQ (TEQDF-WHO98 or I-TEQDF) in 2000. Because of the low confidence
27 rating for the emission factor, the overall confidence rating is low for the emission estimates for
28 all three reference years.
29
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1 3.2.7. Halogen Acid Furnaces Burning Hazardous Waste
2 Hazardous waste can be used in the production of halogen acids using an HAF.
3 According to EPA rules, products that qualify as "hazardous waste," as defined in 40 CFR 261.2,
4 must be regulated as such, even if the products are used in the production of halogen acids using
5 an HAF (Federal Register, 1991b).
6 The national OSW database contains congener-specific emission concentrations for two
7 HAFs burning liquid hazardous waste as supplemental fuel tested in 2000. Data from these two
8 facilities were used to calculate an emission factor for HAFs. The average congener and TEQ
9 emission factors are presented in Table 3-15. The equation used to derive the emission factor is
10 the same as eq 3-4 above. The average TEQ emission factor for HAFs is 0.836 ng TEQDF-
11 WHO98/kg (0.803 ng I-TEQDF/kg) of waste feed for reference year 2000. This emission factor is
12 assigned a low confidence rating because it reflects testing at only 12.5% of all HAFs operating
13 in 2000 (2 out of 16).
14 The amount of hazardous waste combusted using HAFs in 2000 was conservatively
15 estimated to be 375,600 metric tons. This estimate is based on data provided by OSW that
16 described activity levels for each individual HAF in 2000. Activity data were available for 14 of
17 the 16 facilities. By assuming that plants operate continuously throughout the year, that they are
18 always running at 80% of maximum capacity, and that the activity levels represent the maximum
19 capacity, a conservative estimate for the annual quantity burned per HAF was derived (23,480
20 kg/yr). This quantity, multiplied by the total universe of 16 facilities, yields the final estimate of
21 375,600 metric tons. This was assigned a low confidence rating because the data was possibly
22 nonrepresentative.
23 Equation 3-5, which was used to calculate annual TEQ emissions for dedicated HWIs,
24 was also used to calculate annual TEQ emissions for HAFs. Multiplying the average TEQ
25 emission factors by the total estimated kg of liquid hazardous waste burned in 2000 yields annual
26 emissions in g I-TEQDF. From this procedure, the emissions from all industrial boilers/furnaces
27 burning hazardous waste as supplemental fuel are estimated as 0.31 g TEQDF-WHO98 (0.3 g I-
28 TEQDF). Because of the low confidence rating for the emission factor, the overall confidence
29 rating is low for the emission estimates.
30
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1 3.2.8. Solid Waste from Hazardous Waste Combustion
2 U.S. EPA (1987a) contains limited data on ash generated from hazardous waste
3 incineration. EPA indicated that 538 |_ig/kg and 2,853 |_ig/kg were the mean concentrations of
4 CDDs and CDFs, respectively, from a hazardous waste incinerator with an afterburner (Table 3-8
5 in U.S. EPA, 1987a). Specific data for congeners and for ash quantities were not provided.
6
7 3.3. MEDICAL WASTE INCINERATION
8 Medical waste incineration is the controlled burning of solid wastes generated primarily
9 by hospitals, veterinary facilities, and medical research facilities. EPA defines medical waste as
10 any solid waste generated in the treatment, diagnosis, or immunization of humans or animals or
11 research pertaining thereto or in the production or testing of biologicals (Federal Register,
12 1997b). The primary purposes of medical waste incineration are to reduce the volume and mass
13 of waste in need of land disposal and to sterilize the infectious materials. The following
14 subsections review the basic types of medical waste incinerator (MWI) designs used to incinerate
15 medical waste and the distribution of APCDs used on MWIs and summarize the derivation of
16 dioxin TEQ emission factors for MWIs and the national dioxin TEQ emission estimates for
17 reference years 1987, 1995, and 2000.
18
19 3.3.1. Design Types of MWIs Operating in the United States
20 For purposes of this document, EPA has classified MWIs into three broad technology
21 categories: modular furnaces using controlled air, modular furnaces using excess air, and rotary
22 kilns. Of the MWIs in use today, the vast majority are believed to be modular furnaces using
23 controlled air. EPA has estimated that 97% are modular furnaces using controlled air, 2% are
24 modular furnaces using excess air, and 1% are rotary kiln combustors (U.S. EPA, 1997b).
25 Modular furnaces using controlled air. Modular furnaces have two separate
26 combustion chambers mounted in series (one on top of the other). The lower chamber is where
27 the primary combustion of the medical waste occurs. Medical waste is ram-fed into the primary
28 chamber, and underfire air is delivered beneath the incinerator hearth to sustain good burning of
29 the waste. The primary combustion chamber is operated at below stoichiometric levels, hence
30 the terms "controlled air" or "starved air." With sub stoichiometric conditions, combustion
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1 occurs at relatively low temperatures (760 to 985 °C). Under the conditions of low oxygen and
2 low temperatures, partial pyrolysis of the waste occurs and volatile compounds are released.
3 The combustion gases pass into a second chamber. Auxiliary fuel (such as natural gas) is
4 burned to sustain elevated temperatures (985 to 1,095 °C) in this secondary chamber. The net
5 effect of exposing the combustion gases to an elevated temperature is more complete destruction
6 of the organic contaminants entrained in the combustion gases emanating from the primary
7 combustion chamber. Combustion air at 100 to 300% in excess of stoichiometric requirements is
8 usually added to the secondary chamber. Gases exiting the secondary chamber are directed to an
9 incinerator stack (U.S. EPA, 1991d, 1997b; Buonicore, 1992b). Because of its low cost and
10 good combustion performance, this design has been the most popular choice for MWIs and has
11 accounted for more than 95% of systems installed over the past two decades (U.S. EPA, 1990d,
12 1991d; Buonicore, 1992b).
13 Modular furnaces using excess air. These systems use the same modular furnace
14 configuration as described above for the controlled-air systems. The difference is that the
15 primary combustion chamber is operated at air levels of 100 to 300% in excess of stoichiometric
16 requirements, hence the name "excess air." A secondary chamber is located on top of the
17 primary unit. Auxiliary fuel is added to sustain high temperatures in an excess-air environment.
18 Excess-air MWIs typically have smaller capacity than do controlled-air units, and they are
19 usually batch-fed operations. This means that the medical waste is ram-fed into the unit and
20 allowed to burn completely before another batch of medical waste is added to the primary
21 combustion chamber. Figure 3-4 shows a schematic of a typical modular furnace using excess
22 air.
23 Rotary kiln. In terms of design and operational features, the rotary kiln technology used
24 in medical waste incineration is similar to that employed in both municipal and hazardous waste
25 incineration (see description in Section 3.1). Because of their relatively high capital and
26 operating costs, few rotary kiln incinerators are in operation for medical waste treatment (U.S.
27 EPA, 1990d, 199Id; Buonicore, 1992b).
28 MWIs can be operated in three modes: batch, intermittent, and continuous. Batch
29 incinerators burn a single load of waste, typically only once per day. Waste is loaded, and ashes
30 are removed manually. Intermittent incinerators, which are loaded continuously and frequently
31 with small waste batches, operate less than 24 hr/day, usually on a shift basis. Either manual or
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1 automated charging systems can be used, but the incinerator must be shut down for ash removal.
2 Continuous incinerators are operated 24 hr/day and use automatic charging systems to charge
3 waste into the unit in small, frequent batches. All continuous incinerators operate using a
4 mechanism to automatically remove the ash from the incinerator (U.S. EPA, 1990d, 1991d).
5
6 3.3.2. Characterization of MWIs for Reference Years 1987,1995, and 2000
7 Medical waste incineration remains a poorly characterized industry in the United States in
8 terms of knowing the exact number of facilities in operation over time, the types of APCDs
9 installed on these units, and the aggregate volume and weight of medical waste that is combusted
10 in any given year (U.S. EPA, 1997b). The primary reason for this lack of information is that
11 permits were not generally required for the control of pollutant stack emissions from MWIs until
12 the early 1990s, when state regulatory agencies began setting limits on emissions of PM and
13 other contaminants (Federal Register, 1997b). Prior to that, only opacity was controlled.
14 The information available to characterize MWIs from 1987 and 1995 comes from
15 national telephone surveys, stack emission permits, and data gathered by EPA during public
16 hearings (Federal Register, 1997b). For 2000, information was also provided by a memorandum
17 on emissions from MWIs (Strong and Hanks, 1999) and a limited telephone survey conducted by
18 Versar, Inc. (McAloon, 2003). Strong and Hanks provided information on MWIs in the United
19 States, including the APCD being used by each facility.
20 In 2003, Versar used the Strong and Hanks memorandum to identify six states as having a
21 large number of medical waste facilities operating in 1999. A telephone survey was conducted
22 with the state agencies in each of these six states to obtain the number of MWIs that were
23 operating in 2000. Versar was able to obtain an updated list from four of the six states, which are
24 listed below, along with the dates they were contacted, the number of MWIs operating in 1999,
25 the updated number of MWIs for that state in 2000, and the percent of facilities closed over this
26 time period for each state.
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1 No. of MWIs Percent of facilities
2 State Date contacted 1999 2000 closed from 1999 to 2000
3 Illinois Jan. 16,2003 97 13 86.6
4
5 Louisiana Jan. 16,2003 92 24 73.91
6
7 Maryland Dec. 2,2002 36 30 16.67
8
9 Michigan Nov. 26,2002 228 45 80.26
10
11 The geometric mean of the closure percentages for the four states was determined to be
12 54.09 and the arithmetic mean was 64.36. Maryland had the lowest closure percent from 1999 to
13 2000; however, through discussions with representatives of Maryland state agencies, it was
14 determined that close to 70% of the facilities operating in 1999 would be shut down as of 2003.
15 It was therefore assumed that the average closure percent of 64.36 was a fairly good estimate for
16 all states. This average was applied to the total number of facilities operating in 1999 from the
17 Strong and Hanks (1999) memorandum to estimate the number of facilities operating in 2000.
18 The information obtained from these sources suggests the following:
19
20 • The number of MWIs in operation for each reference year was approximately 5,000 in
21 1987 (U.S. EPA, 1987d), 2,375 in 1995 (Federal Register, 1997b), and 1,065 in 2000
22 (Strong and Hanks, 1999; McAloon, 2003).
23
24 • The amount of medical waste combusted annually in the United States was
25 approximately 1.43 billion kg in 1987 (U.S. EPA, 1987d) and 0.77 billion kg in 1995
26 (Federal Register, 1997b).
27
28 These estimates indicate that between 1987 and 1995 the total number of operating MWIs
29 and the total amount of waste combusted decreased by more than 50%. From 1995 to 2000, the
30 total number of operating MWIs decreased by approximately 55%. A variety of factors probably
31 contributed to the reduction in the number of operating facilities, including federal and state
32 regulations and air pollution requirements. In 1997, EPA adopted emission guidelines for
33 existing MWIs (incinerators constructed on or before June 20, 1996) and new source
34 performance standards for new MWIs (incinerators constructed after June 20, 1996). The Clean
35 Air Act requires that states implement the emission guidelines according to a state plan and that
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1 they submit the state plan to EPA within 1 year of EPA's promulgation of the guidelines (i.e., by
2 September 15, 1998). The compliance schedule, however, allows up to three years from EPA
3 approval of the state plan for MWIs to comply, provided the plan includes enforceable
4 increments of progress. All MWIs were required to be in compliance within three years of
5 approval of their state plan or by September 15, 2002, whichever was earlier.
6 Compliance is stated to be either completion of retrofit of air pollution controls or
7 shutdown of the facility. As a result, many facilities have closed down and hospitals have
8 switched to less expensive medical waste treatment technologies such as autoclaving (Federal
9 Register, 1997b). Autoclaving, or steam sterilization, is one of the most common waste
10 management practices used today. This process involves placing bags of infectious waste into a
11 sealed chamber, sometimes pressurized, and then heating it by direct contact with steam to
12 sterilize the waste.
13 The actual controls used on MWIs on a facility-by-facility basis in 1987 are unknown,
14 and EPA generally assumes that MWIs were mostly uncontrolled (U.S. EPA, 1987d). However,
15 the modular design does cause some destruction of organic pollutants within the secondary
16 combustion chamber. Residence time within the secondary chamber is key to inducing the
17 thermal destruction of the organic compounds. Residence time is the time that the organic
18 compounds entrained within the flue gases are exposed to elevated temperatures in the secondary
19 chamber. EPA has demonstrated with full-scale MWIs that increasing residence time from 1/4
20 sec to 2 sec in the secondary chamber can reduce organic pollutant emissions, including
21 CDDs/CDFs, by up to 90% (Federal Register, 1997b). In this regard, residence time can be
22 viewed as a method of air pollution control.
23 EPA estimates that about two-thirds of the medical waste burned in MWIs in 1995 went
24 to facilities that had some method of air pollution control (Federal Register, 1997b). The types
25 of APCDs installed and the methods used on MWIs include DSI, FFs, ESPs, WSs, and FFs
26 combined with packed-bed scrubbers (composed of granular activated carbon). Some organic
27 constituents in the flue gases can be adsorbed by the packed bed. Within the uncontrolled class
28 of MWIs, about 12% of the waste was combusted in facilities with design capacities of less than
29 200 Ib/hr, with the majority of waste burned at facilities with capacities greater than 200 Ib/hr. In
30 controlled facilities, an estimated 70% of the aggregate activity level is associated with facilities
31 equipped with either WSs, FFs, or ESPs; 29.9% is associated with facilities that use DSI
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1 combined with FFs; and less than 1% is associated with facilities that have an FF/packed-bed
2 APCD (AHA, 1995; Federal Register, 1997b).
3 Strong and Hanks (1999) provided information on the types of APCDs used by facilities
4 operating in 1999. Ten types were included in the memorandum, which included residence time
5 as a type of control technology. The 10 types were 1/4-sec combustion, 1-sec combustion, 2-sec
6 combustion, low-efficiency WS, moderate-efficiency WS, high-efficiency WS, dry lime inject-
7 FF, dry lime inject-FF with CI, WS/dry lime inject-FF, and spray dryer FF with CI. Table 3-16
8 provides an estimated breakdown of these APCDs.
9
10 3.3.3. Estimation of CDD/CDF Emissions from MWIs
11 Emission tests reported for 22 MWIs (about 3% of the existing facilities operating in
12 2000) were collected for use in this document; emission levels of dioxin-like compounds at most
13 facilities are unmeasured. Because so few facilities have been evaluated, the estimation of
14 annual air emissions of CDDs/CDFs from MWIs is quite dependent on extrapolations,
15 engineering judgment, and assumptions. In addition, the information about the activity levels of
16 these facilities is also quite limited. These data limitations have lead to a variety of approaches
17 for estimating CDD/CDF emissions from MWIs:
18
19 1. OAQPS approach (Federal Register, 1997b). EPA's OAQPS used this
20 approach in support of the promulgation of final air emission standards for
21 hospital/medical/infectious waste incinerators.
22
23 2 American Hospital Association (AHA) approach (AHA, 1995) The AHA
24 proposed an approach in its comments on drafts of this document and on the proposed
25 MWI emissions regulations.
26
27 3. ORD approach. In the preparation of this document, EPA's ORD developed a
28 third approach.
29
30 Given the limitations of existing information, both the OAQPS and the AHA approaches
31 are reasonable methods for calculating annual releases of CDDs/CDFs from MWIs. Both
32 methods relied heavily on a series of assumptions to account for missing information. In
33 developing a third approach, ORD built upon the other two approaches by using the most logical
34 features of each. Because of the uncertainties about the existing data, it is currently not known
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1 which approach gives the most accurate estimate of CDD/CDF air emissions from all MWIs
2 nationwide. The three approaches yield different air emission estimates, but the estimates all
3 agree within a factor of 4.
4
5 3.3.4. OAQPS Approach for Estimating CDD/CDF Emissions from MWIs
6 As stated in Section 3.3.2, EPA promulgated final standards of performance for new and
7 existing MWIs under the Clean Air Act Amendments on September 15, 1997 (Federal Register,
8 1997b). CDD/CDF stack emission limits for existing MWIs were established as follows: 125
9 ng/dscm of total CDD/CDF (at 7%t oxygen, 1 atm), equivalent to 2.3 ng/dscm TEQ. In order to
10 evaluate emissions reductions that will be achieved by the standard, OAQPS estimated, as a
11 baseline for comparison, nationwide annual CDD/CDF emissions from all MWIs operating in
12 1995.
13
14 3.3.4.1. OAQPS Approach for Estimating Activity Level
15 As a starting point for deriving national estimates, OAQPS constructed an inventory of
16 the numbers and types of MWIs believed to be operating in 1995. The inventory was based on
17 an inventory of 2,233 MWIs prepared by the AHA (AHA, 1995), supplemented with additional
18 information compiled by EPA. This created a listing of 2,375 MWIs in the United States. The
19 following assumptions were then used to derive activity level estimates:
20
21 1. The analysis divided MWIs into three design types on the basis of mode of daily
22 operation: batch, intermittent, or continuous. This was done using the information
23 from the inventory on design-rated annual incineration capacity of each facility. The
24 smaller capacity units were assumed to be batch operations, and the others
25 were classified as either intermittent or continuous, assuming a ratio of 3 to 1.
26
27 2. The activity level of each facility was estimated by multiplying the design-rated
28 annual incineration capacity of the MWI (kg/hr) by the hours of operation (hr/yr).
29 The annual hours of operation were determined by assuming a capacity factor
30 (defined as the fraction of time that a unit operates over the year) for each design type
31 of MWI (Randall, 1995). Table 3-17 is a summary of the OAQPS estimated annual
32 operating hours for each MWI design type.
33
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1 3.3.4.2. OA QPS Approach for Estimating CDD/CDF Emission Factors
2 On the basis of information obtained from the AHA and state regulatory agencies, one-
3 third of the population of MWIs operating in 1995 was estimated to have had no APCD (i.e.,
4 they were uncontrolled), and two-thirds had some type of APCD. CDD/CDF TEQ emission
5 factors were then developed for uncontrolled and controlled MWIs as shown below.
6 Estimating TEQ emission factors for uncontrolled facilities. The uncontrolled
7 category of facilities was subdivided by residence time of the secondary combustion chamber.
8 On the basis of tests at three MWIs, OAQPS concluded that stack emissions of CDDs/CDFs
9 from uncontrolled facilities were dependent on the residence time (i.e., the amount of time the
10 compounds are exposed to elevated temperatures within the secondary combustion chamber)
11 (Strong, 1996). The tests demonstrated that when the residence time in the secondary chamber
12 was short (<1 sec), the stack emissions of CDDs/CDFs would increase; conversely, the longer
13 the residence time (>1 sec), the greater the decrease in CDD/CDF emissions. The emissions
14 testing at these MWIs provided the basis for the derivation of I-TEQDF emission factors for
15 residence times of 1/4 sec, 1 sec, and 2 sec. Table 3-18 summarizes the emission factors
16 developed for each MWI type as a function of residence time.
17 The OAQPS inventory of MWIs in 1995 did not provide residence times for each facility.
18 OAQPS overcame this data gap by assuming that residence time in the secondary combustion
19 chamber corresponded approximately with the PM stack emission limits established in state air
20 permits. This approach assumed that the more stringent PM emission limits would require
21 longer residence times in the secondary chamber in order to further oxidize carbonaceous soot
22 particles and reduce PM emissions. Table 3-19 lists the assumed residence times in the
23 secondary chamber corresponding to various state PM emission limits. State implementation
24 plans (SIPs) were reviewed to determine the PM emission limits for incinerators, and from this
25 review both a residence time and an I-TEQDF emission factor were assigned to each uncontrolled
26 MWI on the inventory.
27 Estimating TEQ emission factors for controlled MWIs. Two-thirds of the MWI
28 population were assumed to have some form of APCD. As discussed in Section 3.3.2, APCDs
29 typically used by MWIs consist of one or more of the following: WS, SDSS, and FF combined
30 with a packed bed. The OAQPS approach also included the addition of activated carbon to the
31 flue gases as a means of emissions control (i.e., SDSSs combined with CI). TEQ emission
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1 factors were developed for these control systems on the basis of incinerator emissions testing
2 data gathered in support of the regulations (U.S. EPA, 1997b). Because the inventory did not list
3 the APCDs for all MWIs, state requirements for PM control were used to make assumptions
4 about the type of APCD installed on each facility in the inventory. These assumptions are
5 summarized in Table 3-19.
6
7 3.3.4.3. OAQPS Approach for Estimating Nationwide CDD/CDF TEQ Air Emissions
8
9 Annual TEQ emissions for each MWI facility were calculated as a function of the design
10 capacity of the incinerator, the annual waste charging hours, the capacity factor, and the TEQ
11 emission factor as shown in eq 3-6.
12
13 EMm = (C*H*C1)*FTEQ (3-6)
14 where:
15 EMWJ = annual MWI CDD/F TEQ stack emissions (g/yr)
16 C = MWI design capacity (kg/hr)
17 H = annual medical waste charging hours (hr/yr)
18 Cj = capacity factor (unitless)
19 F^Q = CDD/CDF TEQ emission factor (g TEQ/kg)
20
21 The annual TEQ air emission of all MWIs operating in 1995 is the sum of the annual emissions
22 of each individual MWI. The following equation is applied to estimate annual TEQ emissions
23 from all MWIs.
24
25 EMM (nationwide) = (EmMM] + EmMWl2 + EmMWl3 + + EmMWl23j5) (3 -7)
26
27 where:
28 EMWJ (nationwide) = nationwide MWI TEQ emissions (g/yr)
29
30 Table 3-18 summarizes estimated I-TEQDF emissions for 1995 using the OAQPS approach.
31
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1 3.3.5. AHA Approach for Estimating CDD/CDF Emissions from MWIs
2 In 1995, the AHA responded to EPA's request for public comment on the 1994 draft
3 public release of this document. As part of its comments (AHA, 1995), the AHA attached an
4 analysis of CDD/CDF emissions from MWIs prepared by Doucet (1995) for the AHA. Doucet
5 estimated the total number of MWIs operating in 1995, the distribution of APCDs, CDD/CDF
6 TEQ emission factors, and nationwide TEQ emissions. The following is a brief discussion of the
7 AHA inventory and the Doucet analysis.
8 From a national telephone survey of member hospitals conducted between September and
9 November 1994, the AHA developed what is generally considered to be the first attempt to
10 systematically inventory MWIs in the United States. Approximately 6% of the hospitals with
11 MWIs were contacted (AHA, 1997). The AHA survey showed that, as of December 1994, 2,233
12 facilities were in operation. Doucet (1995) subdivided the AHA MWI inventory into two
13 uncontrolled categories on the basis of combustor design-rated capacity and two controlled
14 categories on the basis of APCD equipment. Doucet then developed CDD/CDF emission factors
15 for each MWI category. Test reports of 19 MWIs were collected and evaluated. Average
16 CDD/CDF TEQ flue gas concentrations (ng/dscm at 7% oxygen) were derived by combining
17 tests from several MWIs in each capacity range category and APCD. The average TEQ flue gas
18 concentrations were then converted to average TEQ emission factors, which were in units of Ib
19 TEQ/106 Ib of medical waste incinerated (equation for conversion not given). Table 3-20 lists
20 the I-TEQDF emission factors calculated by Doucet for each level of assumed APCDs on MWIs.
21 As in the OAQPS approach (Section 3.3.4), the distribution of the APCD categories was
22 derived by assuming that state PM limits would indicate the APCD on any individual MWI
23 (Doucet, 1995). Table 3-21 displays the AHA assumptions of air pollution control used on
24 MWIs on the basis of PM emission limits.
25 With the activity levels, the percent distribution of levels of controls, and the CDD/CDF
26 TEQ emission factors having been calculated with existing data, the final step of the AHA
27 approach was the estimation of annual I-TEQDF emissions (g/yr) from MWIs nationwide.
28 Although no equation was given, it is presumed that the emissions were estimated by multiplying
29 the activity level for each MWI size and APCD category by the associated I-TEQDF emission
30 factor. The sum of these calculations for each designated class yields the estimated annual I-
31 TEQDF emissions for all MWIs nationwide. Doucet (1995) indicated that these computations
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1 were appropriate for I-TEQDF emissions in 1995. Table 3-22 summarizes the nationwide annual
2 I-TEQDF emissions from MWIs using the AHA approach.
3
4 3.3.6. ORD Approach for Estimating CDD/CDF Emissions from MWIs
5 Because of the limitations of the emissions data and activity levels, the ORD approach
6 used many of the logical assumptions developed in the OAQPS and AHA approaches. The
7 discussion below describes the rationale for how these decisions were made and presents the
8 resulting emission estimates.
9
10 3.3.6.1. ORD Approach for Classifying MWIs and Estimating Activity Levels
11 As with the OAQPS and AHA approaches, the ORD approach divided the MWIs into
12 controlled and uncontrolled classes. The rationale for further dividing these two classes is
13 discussed below.
14 Uncontrolled MWIs. For purposes of assigning CDD/CDF emission factors and activity
15 levels to the uncontrolled class of MWIs, the OAQPS approach divided this class on the basis of
16 residence time within the secondary combustion chamber. This approach has theoretical appeal,
17 because it is logical to expect more complete combustion of CDDs/CDFs with longer residence
18 times at high temperatures. Unfortunately, the residence times on a facility-by-facility basis are
19 not known, making it difficult to assign emission factors and activity levels on this basis. As
20 discussed earlier, the OAQPS approach assumed that residence time would strongly correlate
21 with state PM stack emission requirements (i.e., the more stringent the PM requirements, the
22 longer the residence time required to meet the standard).
23 This PM method for estimating residence time resulted in the following distribution of
24 residence times: 6% of the waste incinerated at MWIs with 1/4-sec residence time, 26% of the
25 waste incinerated at MWIs with 1-sec residence time, and 68% of the waste incinerated at MWIs
26 with 2-sec residence time. Thus, about two-thirds of the activity level within the uncontrolled
27 class was assumed in the OAQPS approach to be associated with facilities with the longest
28 residence time and the lowest CDD/CDF emission factor.
29 The AHA approach subcategorized the uncontrolled class on the basis of design-rated
30 capacity. There is also theoretical support for this approach. Smaller-capacity operations (<200
31 Ib/hr) are likely to have higher emissions because they are more likely to be operating in a batch
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1 mode. The batch mode results in infrequent operation with more start up and shut down cycles.
2 Thus, the batch-operated MWI usually spends more time outside of the ideal range of operating
3 conditions. In support of this approach, the AHA presented limited empirical evidence indicating
4 that CDD/CDF emission factors calculated from emission test reports for the low-capacity units
5 were about a factor of 2 higher than the emission factors for the high-capacity units (>200 Ib/hr)
6 (Doucet, 1995).
7 Thus, both the OAQPS and the AHA approaches have a sound theoretical basis but lack
8 strong supporting data. In order to decide which of the two approaches to use, ORD first tested
9 the assumption that there is a strong relationship between state PM requirements and residence
10 time. ORD conducted a limited telephone survey of regulatory agencies in four states where a
11 large number of MWI facilities were in operation: Michigan, Massachusetts, New Jersey, and
12 Virginia (O'Rourke, 1996). The results of the limited survey, summarized in Table 3-23, did not
13 verify the existence of a strong relationship between PM emission limits and residence time in
14 the secondary chamber at MWIs.
15 Next, the available emission testing data for low- and high-capacity units were evaluated
16 to determine whether, as posited in the AHA approach, smaller-capacity units have greater
17 emission factors than do larger-capacity units. This evaluation indicated a distinct difference in
18 the emission factors between the two capacity categories, although the difference in the set of
19 data evaluated was not as great as the difference observed in the data set evaluated in the AHA
20 approach. The ORD approach, therefore, adopted the subcategorization scheme used in the AHA
21 approach.
22 Controlled MWIs. Both the OAQPS approach and the AHA approach subcategorized
23 the controlled MWIs on the basis of APCD equipment. However, the two approaches differed in
24 the subcategories developed. The AHA approach divided the controlled class into two groups:
25 facilities equipped with WSs (alone, with an ESP, or with an FF) and facilities equipped with
26 DSI and an FF (Doucet, 1995). The OAQPS approach divided the controlled class into three
27 groups: facilities equipped with WSs, facilities equipped with SDSSs (with or without CI), and
28 facilities equipped with FFs and packed bed scrubbers. This third category comprises a few
29 facilities located primarily in the northeastern United States (O'Rourke, 1996). The ORD
30 approach adopted the two subcategories of the AHA approach and the third subcategory of the
31 OAQPS approach.
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1 For 1987, the ORD approach assumed that every MWI was uncontrolled. An EPA study
2 of MWIs conducted at that time indicated that MWIs operating in 1987 did not need controls
3 because they were not subject to state or federal limits on either PM or organic pollutant
4 emissions (U.S. EPA, 1987d). The activity level estimates were derived from data presented in
5 that 1987 study. This approach resulted in the following activity level assumptions for 1987: (a)
6 15% of the activity level (0.22 billion kg) was incinerated annually by MWIs with capacities less
7 than or equal to 200 Ib/hr, and (b) 85% of the activity level (1.21 billion kg) was incinerated
8 annually by facilities with capacities greater than 200 Ib/hr (see Table 3-24). For 1995, ORD
9 used the activity levels for each facility as reported in the OAQPS inventory; the activity levels
10 were then summed across facilities for each APCD subclass (see Table 3-25).
11 In 1997, the amount of waste combusted by MWIs was estimated to be
12 0.8 million tons/yr (0.7 billion kg/yr) (National Research Council, 2000). This number
13 represents a 9% decrease from 1995. If we assume that this decrease occurred every 2 years from
14 1997 to 2000, the estimated amount of waste combusted by MWIs for 2000 would be 0.6 billion
15 kg/yr. This is a conservative estimate, considering the large number of facilities that have shut
16 down or switched to less expensive medical waste treatment technologies. For 2000 activity
17 level estimates, the same distributions among APCD classes were assumed as for 1995. These
18 activity level estimates are presented in Table 3-26. For all years, these activity levels were
19 assigned a rating of low confidence because the data were judged to be possibly
20 nonrepresentative.
21
22 3.3.6.2. ORD Approach for Estimating CDD/CDF Emission Factors
23 ORD collected the engineering reports of 24 tested MWIs to calculate 1987 and 1995
24 emission estimates. After reviewing these test reports, ORD determined that 20 met the criteria
25 for acceptability (see Section 3.1.3). In some cases, CDD/CDF congener-specific data were not
26 reported or values were missing. In other cases, the protocols used in the laboratory analysis
27 were not described; therefore, no determination of the adequacy of the laboratory methods could
28 be made. For 2000, two additional test reports from facilities operating in that year were
29 obtained and were included with the previously obtained test reports in order to calculate updated
30 emission estimates. Each test report was included in its respective MWI subclass according to its
31 APCD and was also included in the overall emission estimate.
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1 The EPA stack testing method (EPA Method 23) produces a measurement of
2 CDDs/CDFs in units of mass concentration (ng/dscm) at standard temperature and pressure and 1
3 atm and adjusted to a measurement of 7% oxygen in the flue gas (U.S. EPA, 1995b). This
4 concentration is assumed to represent conditions at the point of release from the stack into the air
5 and to be representative of routine emissions. The emission factors were derived by averaging
6 the emission factors across each tested facility in a design class. The emission factor for each
7 tested MWI was calculated using the following equation:
8
9 EFMM = CxFv
10 4 (3-8)
11
12 where:
13 EFMWI = emission factor per MWI (average ng TEQ per kg medical waste burned)
14 C = average TEQ concentration in flue gases of tested MWIs (ng TEQ/dscm)
15 (20 °C, 1 atm; adjusted to 7% O2)
16 Fv = average volumetric flue gas flow rate (dscm/hr) (20 °C, 1 atm; adjusted
17 to7%O2)
18 Iw = average medical waste incineration rate of the tested MWI (kg/hr)
19
20 The emission factor estimate for each design class for 1995 and the number of stack tests
21 used to derive the estimate are shown in Table 3-25. Table 3-26 provides the updated emission
22 factor estimates for 2000. Figures 3-15 and 3-16 present congener and congener group profiles
23 for air emissions from MWIs lacking APCDs and for MWIs equipped with a WS/FF APCD
24 system, respectively.
25
26 3.3.7. Summary of CDD/CDF Emissions from MWIs
27 Because the stack emissions from so few facilities have been tested relative to the number
28 of facilities in this industry and because several tested facilities are no longer in operation or
29 installed new APCD after testing, the ORD approach did not calculate nationwide CDD/CDF
30 emissions by calculating emissions from the tested facilities and adding those to calculated
3 1 emissions for the nontested facilities. Rather, the ORD approach (as well as the OAQPS and
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1 AHA approaches) multiplied the emission factor and activity level developed for each design
2 class and then summed the calculated emissions for all classes. Tables 3-24, 3-25, and 3-26
3 summarize the resulting national TEQ air emissions for reference years 1987, 1995, and 2000,
4 respectively. These tables also indicate the activity level and the TEQ emission factor used in
5 estimating annual TEQ emissions.
6 In estimating annual TEQ emissions for each reference year, a low confidence rating was
7 assigned to the estimate of the activity level. The primary reason for the low confidence rating is
8 that very limited information is available on a facility-level basis for characterizing MWIs in
9 terms of the frequency and duration of operation, the actual waste volume handled, and the level
10 of pollution control. The 1987 inventory of facilities was based on very limited information.
11 Although the 1995 OAQPS inventory was more comprehensive than the 1987 inventory, it was
12 still based on a fairly limited survey of operating facilities (approximately 6%). The 2000
13 inventory included only two additional facilities and estimated an activity level based on a 1997
14 value and the distribution among APCDs from the 1995 estimates.
15 The emission factor estimates were given a low confidence rating because the reports of
16 only 20 tested MWI facilities could be used to derive emission factors representing the 2,375
17 facilities operating in 1995 (i.e., less than 1% of the estimated number of operating facilities) and
18 only two additional test reports were obtained for 2000. Even fewer tested facilities could be
19 used to represent the larger number of facilities operating in 1987 (8 tested facilities were used to
20 represent 5,000 facilities). The limited emission tests available cover all design categories used
21 here to develop emission factors. However, because of the large number of facilities in each of
22 these classes, it is very uncertain whether the few tested facilities in each class capture the true
23 variability in emissions.
24 Table 3-26 shows the year 2000 emissions estimate as being 378 g TEQDF-WHO98. The
25 TEQ emissions are estimated to have been 488 g TEQDF-WHO98 (461 g I-TEQDF) in 1995 (Table
26 3-25) and 2,590 g TEQDF-WHO98 (2,440 g I-TEQDF) in 1987 (Table 3-24). Since the activity
27 level and emission factors had low confidence ratings, the emission estimates for all years were
28 assigned a low confidence rating.
29 As explained above, the ORD approach to estimating national CDD/CDF TEQ emissions
30 is a "hybridization" of the OAQPS and AHA approaches. Table 3-27 compares the main features
31 of each of the three approaches. The 1995 TEQ emissions estimated here (461 g I-TEQDF/yr) are
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1 about 3.5 times higher than those of OAQPS and AHA (141 and 138 g I-TEQDF/yr, respectively).
2 Most of this difference is due to differences in the emission estimates for the uncontrolled
3 facilities (ORD: 432 g I-TEQDF/yr; OAQPS: 136 g I-TEQDF/yr; AHA: 120 g I-TEQDF/yr). An
4 explication of the differences in how these groups estimated emissions from the uncontrolled
5 facilities is presented below:
6
7 • Differences between the ORD and AHA approaches. The ORD approach adopted
8 the classification scheme of the AHA approach for the uncontrolled class and
9 assumed similar activity levels. Thus, the difference in emission estimates is
10 primarily due to differences in the emission factors used. Both groups used similar
11 emission factors for facilities with design capacities less than or equal to 200 Ib/hr,
12 but the emission factor for MWIs greater than 200 Ib/hr used in the ORD approach
13 was higher than the one used in the AHA approach by a factor of 3. The factors differ
14 because the two approaches used different sets of emission tests to derive their
15 emission factors.
16
17 • Differences between the ORD and OAQPS approaches. Because the two
18 approaches sub categorized the uncontrolled facilities into different classes, the
19 activity levels and emission factors cannot be directly compared. Considering the
20 class as a whole, however, both approaches used essentially identical activity levels.
21 The OAQPS approach assigned 68% of the total activity to the class with the lowest
22 emission factor (i.e., those with greater than 2-sec residence time). The emission
23 factor for this class, 74 ng I-TEQDF/kg, is considerably lower than either emission
24 factor used in the ORD approach (1,680 and 1,860 ng I-TEQDF/kg).
25
26 Given the uncertain database available for making these estimates, it is difficult to know
27 which of the three estimation approaches yields the most accurate annual TEQ estimate.
28 However, despite the differences in methodologies and assumptions used, the three approaches
29 yielded annual TEQ estimates that are not fundamentally different; the estimates differ from each
30 other by a factor of 4 or less. Because the ORD approach was the last of the three to be
31 developed, it had the benefit of being able to use the most logical and supportable features of the
32 previously developed OAQPS and AHA approaches.
33
34 3.3.8. Recent EPA Regulatory Activities
35 In September 1997, the EPA promulgated final regulations under the Clean Air Act
36 Amendments limiting CDD/CDF stack emissions from MWIs (Federal Register, 1997b). These
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1 emission limits are specific to the sum of CDD and CDF emissions (the sum of tetra through
2 octa CDDs and CDFs). For either new or existing MWIs that were operational before or after
3 June 20, 1996, EPA limits the total CDD/CDF concentration in the stack gases to 2.3 ng/dscm.
4 This would require the application of wet scrubbers, dry sorbent injection of activated carbon
5 combined with fabric filters and/or spray dryers and fabric filters. EPA expects that many
6 facilities which currently operate onsite incinerators will switch to less expensive methods of
7 treatment and disposal of medical and infectious waste when faced with the compliance costs
8 associated with the emission standards for MWIs. EPA projects that, following full compliance
9 with these standards, annual emissions from MWIs will be 5 to 7 g I-TEQDF/yr.
10
11 3.4. CREMATORIA
12 3.4.1. Human Crematoria
13 3.4.1.1 Emissions Data
14 Bremmer et al. (1994) measured CDD/CDF emissions at two crematoria in the
15 Netherlands. The first, a "cold"-type furnace with direct, uncooled emissions, was calculated to
16 yield 2,400 ng I-TEQDF per body. In the cold-type furnaces, the coffin is placed inside at a
17 temperature of about 300 °C. The temperature of the chamber is then increased to 800 to 900 °C
18 using a burner and kept there for 2 to 2.5 hr. The second furnace, a "warm" type in which flue
19 gases are cooled to 220 °C prior to discharge, was calculated to yield 4,900 ng I-TEQDF per body.
20 In the warm-type furnace, the coffin is placed in a chamber preheated to 800 °C or higher for 1.2
21 to 1.5 hr. The chamber exhausts from both furnace types were incinerated in an afterburner at a
22 temperature of about 850 °C. The higher emission rate for the warm-type furnace was attributed
23 by the authors to the formation of CDDs/CDFs during the intentional cooling of the flue gases to
24 220 °C.
25 Jager et al. (1992) (as reported in Bremmer et al., 1994) measured an emission rate of
26 28,000 ng I-TEQDF per body for a crematorium in Berlin, Germany. No operating process
27 information was provided by Bremmer et al. for the facility.
28 Mitchell and Loader (1993) reported even higher emission factors for two crematoria in
29 the United Kingdom. The first facility tested was manually operated and had primary and
30 secondary combustion chambers preheated to 650 °C and a residence time of 1 sec in the
31 secondary combustion chamber. The second tested facility was computer controlled and had
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1 primary and secondary combustion chambers heated to 850 °C and a residence time of 2 sec in
2 the secondary combustion chamber. The measured stack gas TEQ concentrations ranged from 42
3 to 71.3 ng I-TEQDF/m3 (at 11% oxygen) at the first facility and from 25.4 to 45.5 ng I-TEQDF/m3
4 (at 11% oxygen) at the second facility. Emission factors based on these test results and gas
5 generation rates reported by Bremmer et al. (1994) were calculated to range from 70,000 to
6 80,000 ng I-TEQup/body (HMIP, 1995).
7 Takeda et al. (1998) measured CDD/CDF emissions at 10 crematoria in Japan. Although
8 there are more than 1,600 crematoria in Japan, the 10 tested facilities handle 4% of the
9 cremations carried out in Japan annually. A wide range of CDD/CDF emissions were observed.
10 When nondetect values were treated as zero, the emission factor range was 42 to 62,000 ng I-
11 TEQDF/body (mean of 9,200 ng I-TEQDF/body). When nondetect values were treated as one-half
12 the DL, the range was 450 to 63,000 ng I-TEQDF/body (mean of 11,000 ng I-TEQDF/body).
13 To obtain more data on CDD/CDF emissions from crematoria in Japan, Takeda et al.
14 (2001) measured CDD/CDF emissions at 17 additional crematoria. In that study, all the
15 crematoria except one had secondary combustion chambers. Additionally, one crematorium had
16 a secondary combustion chamber but did not use it. One to four main chambers were connected
17 to the secondary chambers, and the temperature of the main chambers ranged from
18 approximately 650 to 1,150 °C. In most cases, only one body was cremated at time. However,
19 between two and four bodies were cremated at four sampling events. A coffin and any
20 accompanying materials were combusted along with the body. Emission factors ranged from 120
21 to 24,000 ng I-TEQDF/body. In general, as the average temperature in the main combustion
22 chamber increased, CDD/CDF emissions decreased. However, the crematorium that had a
23 secondary combustion chamber but did not use it had both high temperatures in the main
24 combustion chamber and high CDD/CDF emissions. Additionally, with the rise of the average
25 temperature in the secondary combustion chamber of the eight crematoria without dust
26 collectors, CDD/CDF emissions decreased. For crematoria with dust collectors, the relationship
27 between the average temperature in the secondary combustion chamber and CDD/CDF emissions
28 was not clear.
29 EPA obtained test data from two crematoria for humans operating in the United States,
30 one at Camellia Memorial Lawn in California (CARB, 1990c) and one at Woodlawn Cemetery in
31 New York (U.S. EPA, 1999f). Additionally, EPA obtained test data from one crematorium for
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1 animals operating in the United States: University of Georgia Veterinary School (U.S. EPA,
2 2000e); however, it is not appropriate to use the emission factors from this facility to characterize
3 emissions associated with human cremation.
4 Testing at the Camellia Memorial Lawn crematorium, which is classified as a warm-type
5 facility using the criteria of Bremmer et al. (1994), was conducted in 1990 (CARB, 1990c). The
6 combusted material at this facility consisted of the body, as well as 4 pounds of cardboard, up to
7 6 pounds of wood, and an unquantified amount of unspecified plastic wrapping. The three
8 emission tests conducted at this facility, which operates using an afterburner, yielded an average
9 emission factor of 543 ng TEQDF-WHO98/body (501 ng I-TEQDF/body). Table 3-28 presents the
10 congener-specific emission factors for this facility.
11 Testing at Woodlawn Cemetery, which has a crematorium with a primary combustion
12 chamber, a secondary combustion chamber, and a scrubber APCD, was conducted in 1995. Tests
13 were run at three secondary combustion chamber temperatures: 675, 870, and 980 °C (U.S. EPA,
14 1999f). The combusted material consisted of the body, as well as a 10- to 100-pound casket
15 constructed of fiberboard, particle board, or wood and various body wrappings and articles such
16 as a plastic sheet, a cloth sheet, or clothes. For this facility, average emission factors of 325 and
17 961 ng TEQDF-WHO98/body cremated (310 and 780 ng I-TEQDF/body cremated) were calculated,
18 based on emissions collected at the scrubber inlet and outlet, respectively. The congener-specific
19 emission factors for this facility are shown in Table 3-29.
20 In 1995, 1,155 crematoria were reported to be operating in the United States; this number
21 had decreased to approximately 1,060 by 2000. To determine whether the emissions data
22 collected at the Woodlawn Cemetery facility are representative of a typical crematorium
23 operating in the United States, representatives from the Cremation Association of North America
24 (CANA) were contacted to identify the typical operating conditions at U.S. crematoria.
25 According to the CANA representatives, all crematoria operating in the United States have
26 primary and secondary combustion chambers. Additionally, crematoria with operating
27 conditions that indicate the presence of an afterburner are considered to contain secondary
28 combustion chambers. The primary and secondary combustion chambers at U.S. crematoria
29 typically operate at between 675 and 870 °C, but many operate at 980 °C, as required by their
30 respective states.
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1 Only one or two facilities in the United States incorporate the use of an APCD, such as a
2 scrubber. Therefore, the inlet dioxin emission factors rather than the outlet dioxin emission
3 factors at the Woodlawn crematorium would be representative of a typical crematorium operating
4 in the United States (telephone conversation between Allen Krobath, CANA, and K. Riley,
5 Versar, Inc., February 12, 2003, and telephone conversation between Dale Walter, Mathews
6 Cremation, and K. Riley, Versar Inc., February 13, 2003).
7 In the previous inventory, an average emission factor of 17,000 ng I-TEQDF/body
8 (assuming nondetect values are zero) was developed, based on emission factors measured for 16
9 of the tested facilities, including the one at Camellia Memorial Lawn (CARB, 1990c), the 10
10 Japanese facilities (Takeda et al., 1998), the two Dutch facilities (Bremmer et al., 1994), the one
11 German facility (Jager et al., 1992), and the two British facilities (Mitchell and Loader, 1993).
12 The more recent data provided by Takeda et al. (2001) for the 17 Japanese facilities support the
13 emission factor of 17,000 ng I-TEQDF/body. However, an average emission factor developed
14 using the data reported for the two U.S. crematoria (i.e., the outlet values for the Camellia
15 Memorial Lawn facility and the inlet values for the Woodlawn Cemetery facility) is 434 ng
16 TEQDF-WHO98/body (410 I-TEQDF/body cremated), assuming nondetect values are zero. These
17 values are two orders of magnitude less than the overall average calculated above. An
18 examination of the differences in U.S. and foreign operating practices may provide a rationale for
19 the large discrepancies.
20 Bremmer et al. (1994) reported an emission factor of 2,400 ng I-TEQDF/body for a Dutch
21 facility with a cold-type furnace and an emission factor of 4,900 ng I-TEQDF/body for another
22 Dutch facility with a warm-type furnace where flue gases were cooled to 220 °C. Neither of the
23 U.S. facilities are considered to have cold-type furnaces. Additionally, the flue gases at the
24 Camellia Memorial Lawn crematorium were not cooled prior to exiting the furnace. At the
25 Woodlawn Cemetery facility, the flue gases were cooled from 681 to 860 °C prior to entering the
26 scrubber to 271 to 354 °C by the time they exited the scrubber and the furnace. The emissions
27 were higher at the scrubber outlet than at the inlet (961 vs. 325 ng TEQDF-WHO98/body [780 vs.
28 319 I-TEF/body]); however, the emissions were not on the same magnitude as reported by
29 Bremmer for the warm-type facility (4,900 ng I-TEQDF/body). The Jager et al. (1992) report did
30 not include operating process information; therefore the German facility could not be compared
31 with the U.S. facilities. Additionally, the emission values derived from the Mitchell and Loader
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1 (1993) emission concentrations were calculated using gas generation rates from the Bremmer et
2 al. report and, as such, may not be indicative of crematoria in the United States.
3 In the Takeda et al. (1998, 2001) reports, the burn time for the cremations varied from 47
4 to 117 min. The average burn time in the U.S. studies was 120 min. This shorter burn time may
5 not be optimal for dioxin reduction, resulting in higher dioxin emissions. Also, the secondary
6 combustion chamber temperatures ranged from 250 to 950 °C in the Takeda studies, again
7 resulting in higher emission rates. In fact, in Takeda et al. (2001) two of the three runs that had
8 the highest TEQ concentrations per body came from a crematorium that did not use a secondary
9 combustion chamber. Of the 31 crematoria sampled in Takeda et al. (2001), 26 had lower than
10 5,000 ng I-TEQDF/body.
11 Because the Woodlawn facility is unique in that it incorporates an APCD, the sample data
12 for the air stream entering the scrubber versus the stream exiting the scrubber should be analyzed.
13 A comparison of the dioxin concentrations of these air streams shows a significant increase in
14 dioxin concentrations in the stream exiting the scrubber. This increase can be attributed to the
15 decrease in temperature that occurred in the scrubber. Upon exiting the scrubber, the flue gas
16 temperatures were in the range of 271 to 354 °C, compared with temperatures of between 681
17 and 860 °C at the scrubber inlet. As discussed in Section 2, these exit flue gas temperatures lie in
18 the optimum temperature range for dioxin formation; therefore, an increase in dioxin
19 concentrations would be expected.
20 An analysis of scrubber inlet dioxin data indicates that the average dioxin concentrations
21 increased with temperature (189, 445, and 503 ng TEQDF-WHO98/body at 681, 772, and 860 °C,
22 respectively). Because the operating temperatures are outside the temperature range for the
23 formation of dioxin (200 to 400 °C), dioxin concentrations should decrease as temperatures
24 increase. Further analysis of the data shows that as temperatures at the scrubber inlet increased,
25 so did concentrations of PM, HC1, and lead (Table 3-30). The data also indicate that oxygen
26 levels decreased as the temperature increased (U.S. EPA, 1999). Given these data, one could
27 speculate that as the temperature increased, incomplete combustion conditions arose, leading to
28 an increase in dioxin formation.
29 Using data from U.S. crematoria, EPA recommends an average emission factor of 434 ng
30 TEQDF-WHO98/body (410 ng I-TEQDF/body). This is derived from the scrubber inlet dioxin
31 concentrations from the Woodlawn Cemetery study and the results from the Camellia Memorial
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1 Lawn study. These average congener-specific emission are presented in Table 3-31, and the
2 CDD/CDF congener and congener group emission profiles are presented in Figure 3-17.
3 Because the emission factor was derived using emissions data from only 2 of 1,060 crematoria,
4 the average emission factor is assigned a low confidence rating.
5
6 3.4.1.2. Activity Level Information
1 A total of 323,371 cremations were performed in reference year 1987; 488,224 in 1995;
8 and 629,362 in 2000. A high confidence rating is assigned to these activity level estimates
9 because they are based on comprehensive data provided by CANA (CANA, 2002; Springer,
10 1997).
11
12 3.4.1.3. Emission Estimates
13 Combining the average emission rate of 434 ng WHO-TEQ98/body (410 ng I-
14 TEQDF/body) with the number of cremations in 1987, 1995, and 2000 (323,371; 488,224; and
15 629,362, respectively) yields an estimated annual release of 0.14 g TEQDF-WHO98 (0.14 g I-
16 TEQDF) in 1987, 0.21 g TEQDF-WHO98 (0.2 g I-TEQDF) in 1995, and 0.27 g TEQDF-WHO98 (0.26
17 g I-TEQDF) in 2000. An overall confidence rating of low was assigned to the emissions, since the
18 emission factor had a low rating.
19
20 3.4.2. Animal Crematoria
21 3.4.2.1. Emissions Data
22 Only one study that measured CDD/CDF emissions from animal cremation could be
23 located. In 1999, CDD/CDF emissions were measured from a newly installed animal
24 incineration unit located at the University of Georgia Veterinary School (U.S. EPA, 2000e). The
25 incineration unit, which consists of a primary and a secondary combustion chamber, is used to
26 dispose of animals (mostly cows and horses) used in experimentation. Emissions are
27 uncontrolled, with the exception of an NFPA spark screen located at the stack outlet. Based on
28 four test runs, the average TEQ emission factor was 0.12 TEQDF-WHO98/kg (0.11 ng I-TEQDF/kg)
29 of animal cremated. The average emission factors for these test runs are provided in Table 3-32
30 and a congener-specific profile based on these data is provided as Figure 3-18.
31
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1 3.4.2.2. Activity Level Information
2 As part of the 2000 National Emissions Inventory, OAQPS calculated a national animal
3 cremation activity level estimate of 81.9 million kg/yr for reference year 2000. This estimate was
4 scaled from the 1999 activity level estimate by applying the ratio of the 2000 national human
5 population (281,421,906) to the 1999 national human population (249,440,000). The 1999
6 national activity level was based on 1990 data provided by the OAQPS Emission Standards
7 Division. The 1999 and 2000 activity level estimates assume that animal mortality and
8 cremation rates are constant and that the animal population is directly proportional to human
9 population.
10
11 3.4.2.3. Emission Estimates
12 Applying the TEQ emission factor of 0.12 ng TEQDF-WHO98/kg (0.11 ng I-TEQDF/kg) of
13 animal combusted to the activity level estimated by OAQPS (81.9 million kg/yr) yields estimated
14 annual emissions of 0.0098 g TEQDF-WHO98 (0.009 g I-TEQDF) in 2000. This estimate does not
15 include events such as the mass burning of animals affected by mad cow disease. These
16 estimates are based on extremely limited data and should be regarded as preliminary indications
17 of possible emissions from this source; further testing is needed to confirm the true magnitude of
18 the emissions.
19
20 3.5. SEWAGE SLUDGE INCINERATION
21 The three principal combustion technologies used to incinerate sewage sludge in the
22 United States are the multiple-hearth incineration, fluidized-bed incineration, and electric furnace
23 incineration (Brunner, 1992; U.S. EPA, 1995b). All of these technologies are "excess-air"
24 processes (i.e., they combust sewage sludge with oxygen in excess of theoretical requirements).
25 Approximately 80% of operating sludge incinerators are multiple-hearth design, about 20% are
26 fluidized-bed incinerators, and fewer than 1% are electric incinerators. Other types of furnaces
27 not widely used in the United States are single-hearth cyclones, rotary kilns, and high-pressure
28 wet-air oxidation units (U.S. EPA, 1997b; Maw, 1998).
29 Multiple-hearth incinerators. These types of furnaces consist of refractory hearths
30 arranged vertically in series, one on top of the other. Dried sludge cake is fed to the top hearth of
31 the furnace. The sludge is mechanically moved from one hearth to another through the length of
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1 the furnace. Moisture is evaporated from the sludge cake in the upper hearths. The center
2 hearths are the burning zone, where gas temperatures reach 871 °C. The bottom hearths are the
3 burn-out zone, where the sludge solids become ash. A waste-heat boiler is usually included in
4 the burning zone, where steam is produced to provide supplemental energy at the sewage
5 treatment plant. Air pollution control measures typically include a venturi scrubber, an
6 impingement tray scrubber, or a combination of both. Wet cyclones and dry cyclones are also
7 used (U.S. EPA, 1995b).
8 Fluidized-bed incinerators. A fluidized-bed incinerator is a cylindrical refractory-lined
9 shell with a steel plate structure that supports a sand bed near the bottom of the furnace (Brunner,
10 1992). Air is introduced through openings in the bed plate supporting the sand. This causes the
11 sand bed to undulate in a turbulent air flow; hence, the sand appears to have a fluid motion when
12 observed through furnace portals. Sludge cake is added to the furnace at a position just above
13 this fluid motion of the sand bed. The fluid motion promotes mixing in the combustion zone.
14 Sludge ash exits the furnace with the combustion gases; therefore, air pollution control systems
15 typically consist of high-energy venturi scrubbers or venturi/impingement tray combinations
16 (U.S. EPA, 1995b).
17 Electric furnaces. Also called infrared furnaces, these consist of a long rectangular
18 refractory-lined chamber. A belt conveyer system moves the sludge cake through the length of
19 the furnace. To promote combustion of the sludge, supplemental heat is added by electric
20 infrared heating elements located just above the traveling belt within the furnace. Electric power
21 is required to initiate and sustain combustion. Emissions are usually controlled with a venturi
22 scrubber or some other WS (Brunner, 1992; U.S. EPA, 1995b).
23
24 3.5.1. Emission Estimates from Sewage Sludge Incinerators
25 EPA measured CDD/CDF emissions at three multiple-hearth incinerators as part of Tier 4
26 of the National Dioxin Survey (U.S. EPA, 1987a). During the pretest surveys, two of the
27 facilities were judged to have "average" potential and one facility was judged to have "high"
28 potential for CDD/CDF emissions with respect to other sewage sludge incinerators. The results
29 of these tests include congener group concentrations in stack gas but lack measurement results
30 for specific congeners other than 2,3,7,8-TCDD and 2,3,7,8-TCDF. The results show a wide
31 variability in the emission factors at these three facilities; total CDD/CDF emission factors
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1 ranged from 90 to 3,400 ng/kg (average of 1,266 ng/kg). Total TEQ emissions could not be
2 determined for these facilities because of the lack of congener-specific data.
3 In 1990, EPA measured CDD/CDF emissions (including all 17 toxic congeners) at
4 another multiple-hearth incinerator and also at a fluidized-bed incinerator (U.S. EPA, 1990f).
5 Assuming nondetects are zero, the total CDD/CDF emission factors for these two facilities were
6 79 and 846 ng/kg, and the total average TEQ emission factors were 3.6 and 43.2 ng TEQDF-
7 WHO98/kg (2.4 and 43.3 ng I-TEQDF/kg) of dry sludge. In 1995, the Association of Metropolitan
8 Sewerage Agencies (AMSA) submitted to EPA the results of stack tests conducted at an
9 additional 13 sewage sludge incinerators (Green et al., 1995). Two of these data sets were
10 considered not usable by EPA because either DLs or feed rates and stack flow rates were not
11 provided. As with the EPA-tested facilities (U.S. EPA, 1987a, 1990f), wide variability was
12 observed in the emission factors for the 11 AMSA facilities. Assuming nondetects are zero, total
13 CDD/CDF emission factors ranged from 0 to 1,392 ng/kg (average of 217 ng/kg), and total
14 average TEQ emission factors ranged from 0 to 16 ng TEQDF-WHO98/kg (average, 3.47 ng) (3.46
15 ng I-TEQDF/kg) of dry sludge.
16 In 1999, stack tests were conducted at a multiple hearth-incinerator equipped with a
17 venturi scrubber and a three-tray impingement conditioning tower (U.S. EPA, 2000f). Four test
18 runs were conducted; however, the first test run was aborted, and the CDD/CDF results from the
19 fourth test run were determined to be statistical outliers (p<0.05). The back-half emission
20 concentrations for test run 4 were 50 to 60% lower than those for test runs 2 and 3. Overall, total
21 CDD/CDF emissions measured during test run 4 were 48 ng/kg, whereas total CDD/CDF
22 emissions measured during test runs 2 and 3 were 120 and 116 ng/kg, respectively. It could not
23 be determined whether the lower concentrations associated with test run 4 were due to analyte
24 loss or whether they represented an accurate reflection of a change in incinerator emission
25 releases.
26 The average TEQ emission factor, excluding test run 4, was 3.28 ng TEQDF-WHO98/kg
27 (3.23 ng I-TEQDF/kg). The average TEQ emission factor based on the data for the 11 AMSA
28 facilities (Green et al., 1995) and the three facilities reported by EPA (U.S. EPA, 2000f, 1990f) is
29 6.74 ng TEQDF-WHO98/kg (6.65 ng I-TEQDF/kg) of dry sludge, assuming nondetect values are
30 zero. Figure 3-19 presents the average congener and congener group profiles based on these
31 data. Additionally, Table 3-33 presents the average congener and congener-specific group
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1 emission factors and the average TEQ emission factors for these facilities. Table 3-33 also
2 presents 2,3,7,8-TCDD, 2,3,7,8-TCDF, and congener-specific group emission factors for the
3 three facilities reported by EPA (1987a).
4 Other countries have reported similar results. Bremmer et al. (1994) reported an emission
5 rate of 5 ng I-TEQDF/kg for a fluidized-bed sewage sludge incinerator in the Netherlands that was
6 equipped with a cyclone and a WS. Cains and Dyke (1994) measured CDD/CDF emissions at
7 two sewage sludge incinerators in the United Kingdom. The emission rate at an incinerator
8 equipped with an ESP and a WS ranged from 2.75 to 28 ng I-TEQDF/kg. The emission rate
9 measured at a facility equipped with only an ESP was 43 ng I-TEQDF/kg.
10 In 1988, approximately 199 sewage sludge incineration facilities combusted about 0.865
11 million metric tons of dry sewage sludge (Federal Register, 1993b). In 1995, approximately 257
12 sewage sludge incinerators (some of which were backup or alternate incinerators) combusted
13 about 2.11 million dry metric tons of sewage sludge (Maw, 1998). Using trends in wastewater
14 flow rates from the 1988 National Sewage Sludge Survey and from the 1984 to 1996 Needs
15 Surveys, EPA estimated that in 2000 approximately 6.4 million metric tons of dry sewage sludge
16 would be generated (U.S. EPA, 1999e). Of this amount, EPA projected that 22% (1.42 million
17 metric tons) would be incinerated.
18 According to EPA, sewage sludge generation will increase to 6.9 million dry tons in 2005
19 and 7.4 million dry tons in 2010; however, the percentage of sewage sludge incinerated will
20 decrease slightly, to 20% in 2005 and 19% in 2010. EPA estimates that approximately 1.38
21 million metric tons of dry sewage sludge will be incinerated in 2005 and 1.41 million metric tons
22 will be incinerated in 2010. EPA believes that incineration as a disposal method for sewage
23 sludge will decrease as a result of increasing costs and public concerns about the environmental
24 and health impacts associated with incineration.
25 A medium confidence rating is assigned to the average TEQ emission factor because it
26 was derived from stack testing at 14 U.S. sewage sludge incinerators. The 1988 activity level
27 estimate (used as a surrogate for the 1987 activity level) and the 2000 activity level estimate are
28 assigned a high confidence rating because they are based on extensive EPA surveys to support
29 rule-making activities. The 1995 activity level estimate is assigned a medium confidence rating
30 because assumptions were made for numerous facilities concerning hours of operation, operating
31 capacity, and design capacity.
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1 Using the above estimated amounts of sewage sludge incinerated per year and the average
2 TEQ emission factor of 6.74 ng TEQDF-WHO98/kg (6.65 ng I-TEQDF/kg), the estimate of TEQ
3 emissions to air is 5.8 g TEQDF-WHO98 (5.8 g I-TEQDF) in 1987, 14.2 g TEQDF-WHO98 (14 g I-
4 TEQDF) in 1995, and 9.6 g TEQDF-WHO98/kg (9.4 g I-TEQDF/kg) in 2000. Since the emission
5 factor had a medium confidence rating, the overall emission estimates were assigned a medium
6 confidence rating for all years.
7
8 3.5.2. Solid Waste from Sewage Sludge Incinerators
9 In Table 5-16 of U.S. EPA (1987a), data are presented indicating that 2,3,7,8-TCDD was
10 not detected in the bottom ash or scrubber water filtrate from three sewage sludge incinerators.
11 However, total CDDs for the three incinerators and the filtrate were nondetected, 20 ng/kg, 10
12 ng/kg, and 0.3 ng/kg, respectively. For total CDFs, the respective values were nondetected, 70
13 ng/kg, 50 ng/kg, and 4 ng/kg. No data were given for any congeners (other than 2,3,7,8-TCDD)
14 nor were there any data on the quantities of ash or filtrate.
15
16 3.6. TIRE COMBUSTION
17 Most discarded tires are combusted in dedicated tire incinerators or cement kilns. Some
18 are combusted as auxiliary fuel in industrial boilers and in pulp and paper mill combustion
19 facilities. Additionally, tires may be unintentionally burned in an uncontrolled fashion at
20 landfills (open burning). This section addresses the total TEQ emissions that may result from the
21 combustion of tires in dedicated tire incinerators, industrial boilers, and pulp and paper mill
22 combustion facilities, but excludes cement kilns (addressed in Section 5.1). The open burning of
23 tires is not discussed in this report due to the lack of information.
24 Emissions of CDDs/CDFs from the incineration of discarded automobile tires were
25 measured from one dedicated tire incinerator tested by the California Air Resources Board
26 (CARB, 199 la). The facility consists of two excess air furnaces equipped with steam boilers to
27 recover the energy from the heat of combustion. Whole tires were fed to the incineration units at
28 rates ranging from 2,800 to 5,700 kg/hr during the three test days. The facility was equipped
29 with a DS and an FF for the control of emissions prior to exiting the stack. Table 3-34 presents
30 the congener-specific emission factors for this facility. Figure 3-20 presents CDD/CDF congener
31 and congener group profiles based on these TEQ emission factors. From these data, the average
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1 emission factor is estimated to be 0.281 ng TEQDF-WHO98/kg (0.282 ng I-TEQDF/kg) of tires
2 incinerated (when all nondetect values are treated as zero). This emission factor is used to
3 estimate annual TEQ releases from the tire combustion source category for the years 1987, 1995,
4 and 2000. EPA assigned a low confidence rating to the estimated TEQ emission factor because it
5 is possible that it is not representative of TEQ emissions from all tire combustion facilities. It is
6 also possible that this emission factor is an underestimation of emissions from this source
7 category, because it was derived from the emissions of a facility equipped with very advanced air
8 pollution control technology specific for the control of dioxin emissions. These devices (DS/FF)
9 are capable of greater than 95% reduction and control of dioxin-like compounds prior to
10 discharge from the stack into the air. Because other facilities may not be equipped with similar
11 air pollution control systems, the TEQ emissions could be higher than the estimates developed
12 above. For example, Cains and Dyke (1994) reported much higher emission rates for two tire
13 incinerators in the United Kingdom that were equipped with only simple grit arresters. These
14 emissions produced emission factors of 188 and 228 ng I-TEQDF/kg of tires combusted.
15 EPA estimated that approximately 500 million kg of tires were combusted in 1990
16 (U.S. EPA, 1992a). Of this total, 23% (115 million kg) were combusted in cement kilns, and it is
17 assumed that the remaining 385 million kg were combusted in dedicated tire combustion
18 facilities, industrial boilers, and pulp and paper mill combustion facilities. This activity level
19 was adopted for the years 1987 and 1995 and is assigned a medium confidence rating.
20 The Rubber Manufacturers Association (2002) reported that 281 million scrap tires,
21 weighing approximately 5.68 million metric tons, were generated in the United States in 2001.
22 Approximately 115 million of these scrap tires were combusted as tire-derived fuel, or roughly
23 2.32 million metric tons (2.32 billion kg) of tires. Subtracting the 23% of the tires burned in
24 cement kilns yields a total of 1.8 billion kg of tires estimated to have been combusted in facilities
25 other than cement kilns in 2001. This figure is used to represent the activity level for tire
26 combustion in the year 2000. This activity level is assigned a medium confidence rating.
27 Annual emissions for the reference years is estimated by multiplying the activity level
28 times the TEQ emission factor. The TEQ emission factor of 0.281 ng TEQDF-WHO98/kg (0.282
29 ng I-TEQDF/kg) of tires combusted was used to estimate annual emissions for all years.
30 Multiplying the emission factor by the activity level (385 million kg of tires) yields an estimate
31 of 0.11 g TEQDF-WHO98/yr (0.11 g I-TEQDF/yr) emitted to the air in 1987 and 1995. Using the
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1 same emission factor multiplied by the estimated activity level of 1.8 billion kg tires combusted
2 in 2000 gives an estimate of 0.51 g TEQDF-WHO98/yr (0.51 g I-TEQDF/yr). The estimated TEQ
3 emissions to air from tire combustion for the years 1987, 1995, and 2000 are given a low
4 confidence rating because of the low confidence rating of the emission factor.
5
6 3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED CHEMICAL PULP
7 MILLS
8 Approximately 20.5% of the wastewater sludges generated at bleached chemical pulp
9 mills are dewatered and burned in bark boilers at the mills. These sludges can contain
10 CDDs/CDFs and elevated levels of chloride. However, the level of heat input from sludge in the
11 mixed feed to bark boilers rarely exceeds 10% (NCASI, 1995).
12 NCASI (1995) provided congener-specific test results for four wood residue/sludge
13 boilers tested between 1987 and 1993. Sludge comprised 6 to 10% of the solids in the feed. The
14 average congener-specific emission factors derived from the stack test results obtained from
15 these facilities are presented in Table 3-35. The average TEQ emission factor derived from the
16 test results is 0.062 ng I-TEQDF-WHO98 (0.061 ng I-TEQDF/kg) of feed (i.e., sludge and wood
17 residue), assuming nondetect values are zero. The range in facility-specific emission factors was
18 wide (0.0004 to 0.118 ng I-TEQDF/kg, assuming nondetect values are zero).
19 NCASI (1995) also presented stack emission test results for five other bark boilers.
20 These boilers combusted only bark during the tests even though the boilers normally fire bark in
21 combination with sludge and coal. These boilers are discussed in Section 4.2.2 as industrial
22 facilities burning wood scrap/residues. The average TEQ emission factor for these facilities was
23 0.4 ng I-TEQDF/kg of feed. The emissions test data presented in NCASI (1995), and discussed
24 above, indicate that the CDD/CDF emission factors for bark/sludge combustors are similar to the
25 emission factor developed in Section 4.2.2 for industrial facilities burning only wood
26 residues/scrap. Based on the fact that wood residues comprise a far greater fraction of the feed to
27 these bark/sludge burners than does sludge, the national TEQ emission estimates derived in
28 Section 4.2.2 of this report for industrial wood-burning facilities are assumed to include
29 emissions from these bark/sludge combustion units.
30
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1 3.8. BIOGAS COMBUSTION
2 Using a specially developed sampling apparatus, Schreiner et al. (1992) measured the
3 CDD/CDF content of a flare combusting exhaust gases from an anaerobic sewage sludge digestor
4 in Germany. The nozzle of the apparatus was moved through three cross-sections of the flame
5 and cooling zone. The CDD/CDF content was 1.4 pg I-TEQDF/ standard cubic meter (Nm3) at the
6 bottom of the flare, 3.3. pg I-TEQDF/Nm3 at the top of the flare, and 13.1 pg I-TEQDF/Nm3 in the
7 middle of the flare. Congener-specific results were not reported. Using the theoretical ratio of
8 flare gas volume to digestor gas volume combusted, 78.6:1, and the average CDD/CDF content
9 of the three measurements, 5.9 pg I-TEQDF/Nm3, yields an emission rate of 0.46 ng I-TEQDF/Nm3
10 of digestor gas combusted.
11 During 1996, publicly owned treatment works (POTWs) in the United States treated
12 approximately 122 billion L of wastewater daily (U.S. EPA, 1997c). Although reliable data are
13 not readily available on the amount of sewage sludge generated by POTWs that is subjected to
14 stabilization by anaerobic digestion, a reasonable approximation is 25% of the total sludge
15 generated (i.e., the sludge generated from treatment of about 30 trillion L per day of wastewater).
16 An estimated 196 kg of sludge solids are generated for every million L of wastewater subjected
17 to primary and secondary treatment (Water Pollution Control Federation, 1990). Thus,
18 multiplying 30 billion L/day (25% of 122 billion L) by 196 kg/million L and 365 days/yr yields
19 an annual estimate of 2 million metric tons of sludge solids that may be anaerobically digested in
20 POTWs annually.
21 The volume of sludge digestor gas combusted in flares annually can be estimated using
22 operation parameters for a "typical" anaerobic digestor system as described in Water Pollution
23 Control Federation (1990). Multiplying the annual amount of sludge solids of 2 million metric
24 tons by the following parameters and appropriate conversion factors yields an annual flared
25 digestor gas volume of 467-million Nm3:
26
27 • Fraction of total solids that are volatile solids = 75%;
28 • Reduction of volatile solids during digestion = 50%;
29 • Specific gas production = 0.94 m3/kg volatile solids reduced; and
30 • Fraction of produced gas that is flared = 66%.
31
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1 Because there are no direct measurements of CDD/CDF emissions from U.S. anaerobic
2 sludge digestor flares and because of uncertainties about the activity level for biogas combustion,
3 no national emission estimate has been developed for inclusion in the national inventory.
4 However, a preliminary estimate of the potential annual TEQ emissions from this source can be
5 obtained by multiplying the emission factor of 0.46 ng I-TEQDF/Nm3 of digestor gas flared by the
6 estimated volume of gas flared annually in the United States, 467 million Nm3. This calculation
7 yields an annual potential release in 2000 of 0.22 g. This estimate should be regarded as a
8 preliminary indication of possible emissions from this source category; further testing is needed
9 to confirm the true magnitude of these emissions.
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o
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o
Table 3-1. Inventory of municipal waste combustors (MWCs) in 2000 by technology, air pollution control
device (APCD), sizea, and annual activity level (kg/yr)
APCD"
DSI/FFC
DSI/ESP
DSI/FF/
H2O/SNCR
ESP
FF
WS
WS/ESP
SDd/FF/CI/
SNCR
SD/ESP
SD/ESP/CI
SD/ESP/
CI/SNCR
SD/ESP/
FFVCI
SD/FF
SD/FFe/
SNCR
SD/FF/CI
SD/FF/
CI/SNCR
MWC type
MB/RC
Size
(N)
S(4)
S(4)
L(6)
L(3)
Activity
level
2.52e+08
1.96e+08
l.Ole+09
3.6e+08
MB
Size
(N)
S(2)
Activity
level
5.69e+07
MB/WW/RC
Size
(N)
S(l)
Activity
level
1.59e+07
MB/REF
Size
(N)
S(2)
Activity
level
1.14e+08
MB/WW
Size
(N)
S(2)
S(8)
L(6)
L(4)
L(15)
S(4)
S(2)
L(5)
L(81)
Activity
level
5.69e+08
2.96e+08
8.17e+08
3.39e+08
2.54e+09
1.14e+08
1.14e+08
8.63e+08
1.13e+10
MOD/EA
Size
(N)
S(3)
S(3)
S(3)
S(3)
Activity
level
1.03e+08
8.37e+07
1.03e+08
1.20e+08
Size
(N)
S
S
S
S
S
S
Activity
level
4.27e+07
1.35e+08
1.04e+08
2.85e+07
4.95e+07
5.69e+07
FB/RDF
Size
(N)
S(2)
Activity
level
8.45e+07
RDF
Size
(N)
L(2)
L(2)
S(2)
L(4)
L(2)
L(12)
L(l)
L(4)
Activity
level
1.65e+08
4.03e+07
1.42e+08
9.78e+08
6.72e+08
1.53e+09
3.31e+08
6.06e+08
TOTAL
Size
(N)
S(14)
L(2)
S(9)
L(2)
S(28)
S(3)
S(4)
L(6)
L(4)
L(4)
L(15)
L(2)
S(9)
L(18)
L(l)
S(6)
L(5)
L(88)
Activity
level
5.40e+08
1.65e+08
2.49e+08
4.03e+07
8.22e+08
4.44e+07
4.95e+07
8.17e+08
9.78e+08
3.39e+08
2.54e+09
6.72e+08
2.90e+08
2.54e+09
3.31e+08
1.71e+08
8.63e+08
1.23e+10
O
O
2
O
H
O
HH
H
W
O
c
o
H
W
-------
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Table 3-1. Inventory of municipal waste combustors (MWCs) in 2000 by technology, air pollution control
device (APCD), sizea, and annual activity level (kg/yr) (continued)
APCD"
SD/FF/
SNCR
Unc
TOTAL
MWC type
MB/RC
Size
(N)
L(9)
Activity
level
1.37e+09
MB
Size
(N)
Activity
level
MB/WW/RC
Size
(N)
Activity
level
MB/REF
Size
(N)
Activity
level
MB/WW
Size
(N)
L(13)
S(2)
L(124)
Activity
level
2.72e+09
2.85e+07
1.86e+10
MOD/EA
Size
(N)
Activity
level
Size
(N)
S
Activity
level
6.75e+07
FB/RDF
Size
(N)
Activity
level
RDF
Size
(N)
L(7)
L(34)
Activity
level
1.09e+09
5.41e+09
TOTAL
Size
(N)
L(20)
S(8)
L(167)
Activity
level
3.8e+09
9.6e+07
2.54e+10
oo
o
Tor size, S = small; L = large.
bSlash(es) indicates devices used in conjunction.
°Also equipped with flue gas cooling (138 to 143 °C).
dAlso equipped with furnace dry sorbent injection system.
eAlso equipped with compact hybrid paniculate collector system.
APCD:
CI = Carbon injection
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
H2O = Water scrubber
SD = Spray dryer
SNCR = Selective noncatalytic reduction
Unc = Uncontrolled
WS = Wet scrubber
MWC type:
FB/RDF = Fluidized-bed refuse-derived fuel
MB = Mass burn
MB/RC = Mass burn rotary kiln
MB/REF = Mass burn refractory walled
MB/WW/RC = Mass burn waterwalled/refractory walled
MOD/EA = Modular excess air
RDF = Refuse-derived fuel
-------
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Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 by technology, air pollution control device
(APCD), and annual activity level (kg/yr)
APCD"
Unc
H-ESP
C-ESP
DSI/H-ESP
DS/FF
DS/CI/FF
DS/FF/C-ESP
WS/FF
WS/C-ESP
DS/C-ESP
DS/DSI/C-ESP
DSI/CI/H-ESP
DSI/C-ESP
DSI/FF
DSI/EGB
ws
TOTAL
MWC type
MB/RC
N
2
2
6
9
12
Activity
level
2.00e+08
1.14e+090
5.07e+08
2.59e+08
2.10e+09
MB/REF
N
1
2
1
1
2
7
Activity level
1.69e+08
2.68e+08
4.22e+08
1.13e+08
2.04e+08
1.18e+09
MB/WW
N
6
8
1
28
3
8
1
2
57
Activity level
1.04e+09
2.81e+09
4.22e+08
8.57e+09
1.17e+09
2.31e+09
2.75e+08
1.97e+08
1.68e+10
FB/RDF
N
1
1
1
3
Activity level
1.69e+08
8.45e+07
1.13e+08
3.66e+08
RDF/ded
N
1
4
1
7
1
4
1
19
Activity level
4.22e+07
1.81e+09
2.00e+08
2.51e+09
5.63e+08
1.75e+09
4.22e+08
7.30e+09
MOD/SA
N
9
4
4
1
1
1
3
23
Activity level
1.87e+08
1.82e+08
1.25e+08
2.82e+07
7.60e+07
3.42e+07
4.90e+07
6.80e+07
MOD/EA
N
1
1
3
1
1
1
1
9
Activity level
1.41e+07
1.97e+07
8.28e+07
1.41e+07
1.18e+08
6.76e+07
1.01 e+08
4.18e+08
TOTAL
N
10
12
22
3
41
3
1
1
1
13
1
1
6
9
1
5
130
Activity
level
2.01e+08
1.29e+09
5.19e+09
6.37e+08
1.28e+10
1.17e+09
5.63e+08
2.82e+07
6.76e+07
4.49e+09
7.60e+07
2.75e+08
5.07e+08
1.21e+09
1.13e+08
2.53e+08
2.88e+10
O
o
2
o
H
O
HH
H
W
aSlash(es) indicates devices used in conjunction.
O
c
o
H
W
-------
S Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 by technology, air pollution control device
2 (APCD), and annual activity level (kg/yr) (continued)
o
APCD:
C-ESP = Cold-sided electrostatic precipitator
CI = Carbon injection
DS = Dry scrubber
DSI = Dry sorbent injection
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
SD = Spray dryer
Unc = Uncontrolled
WS = Wet scrubber
MWC type:
FB/RDF = Fluidized-bed refuse-derived fuel
MB/RC = Mass burn rotary kiln
oo MB/REF = Mass burn refractory walled
ON MB/WW = Mass burn waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
RDF/ded = Refuse-derived fuel/dedicated
-------
o
OJ
o
4^
o
Table 3-3. Inventory of municipal waste combustors (MWCs) in 1987 by technology, air pollution control
device (APCD), and annual activity level (kg/yr)
APCD"
Unc
H-ESP
DS/FF
FF
EGB
WS
TOTAL
MWC type
MB/RC
N
3
1
4
Activity
level
3.94e+08
1.58e+07
4.10e+08
MB/REF
N
12
1
7
20
Activity
level
2.00e+09
1.41e+07
9.01e+08
3.04e+09
MB/WW
N
19
1
20
Activity
level
5.20e+09
1.55e+08
5.35e+09
RDF/ded
N
7
2
9
Activity
level
3.01e+09
3.38e+08
3.35e+09
RDF/coflred
N
3
3
Activity
level
2.53e+08
2.53e+08
MOD/SA
N
36
2
3
4
53
Activity
level
5.73e+08
1.17e+08
1.43e+08
5.30e+07
1.15e+09
MOD/EA
N
2
1
1
4
Activity
level
4.17e+07
6.76e+07
1.27e+08
2.36e+08
TOTAL
N
38
54
2
4
1
14
113
Activity
level
6.15e+08
1.12e+10
2.96e+08
1.59e+08
6.76e+07
1.425e+09
1.38e+10
aSlash indicates devices used in conjunction.
APCD:
DS = Dry scrubber
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
Unc = Uncontrolled
WS = Wet scrubber
O
O
2
O
H
O
HH
H
W
O
c
o
H
W
MWC type:
MB/RC = Mass burn rotary kiln
MB/REF = Mass burn refractory walled
MB/WW = Mass burn waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
RDF/cofired = Refuse-derive fuel/cofired
RDF/ded = Refuse-derived fuel/dedicated
-------
Table 3-4. National average dioxin/furan congener concentrations for
large municipal waste combustors (ng/dscm @ 7%O2)
Congener
TrCDD
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
Other TCDD
Other PeCDD
Other HxCDD
Other HpCDD
TrCDF
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
Other TCDF
Other PeCDF
Other HxCDF
Other HpCDF
TOTAL
Nondetect set to zero3
0.0305
0.0054
0.0159
0.016
0.0371
0.0318
0.2185
0.3452
0.2319
0.3232
0.4936
0.2198
0.037
0.0721
0.0503
0.0687
0.0824
0.0587
0.0131
0.0656
0.1555
0.0237
0.0904
1.0805
0.7466
0.3256
0.0787
4.7851
Nondetect set to
Vz detection limit3
0.0305
0.0058
0.0163
0.0162
0.0364
0.0319
0.2187
0.3452
0.2389
0.3336
0.5016
0.2198
0.037
0.0723
0.051
0.0687
0.0825
0.0593
0.0134
0.0663
0.1572
0.024
0.0922
1.0828
0.7584
0.3287
0.0787
4.8337
Nondetect set to
detection limit3
0.0305
0.0061
0.0167
0.0164
0.0374
0.032
0.2187
0.3452
0.2459
0.344
0.5096
0.2198
0.037
0.0725
0.0516
0.0688
0.0825
0.0599
0.0137
0.0669
0.1589
0.0242
0.0939
1.085
0.7702
0.3318
0.0787
4.8836
aValues incorporating use of the detection limit when the laboratory report indicated "not detected" for individual
CDD/CDF congeners.
Source: Huckaby (2003).
03/04/05
3-64
DRAFT—DO NOT CITE OR QUOTE
-------
Table 3-5. National dioxin/furan TEQ emissions (g/yr) for large municipal
waste combustors
Basis
TEQ (1989
NATO)a
TEQ(1997WHO)b
Total mass basis
Nondetect set to zero
15.3
13.7
665
Nondetect set to 1A
detection limit
15.4
13.8
671
Nondetect set to
detection limit
15.5
14
678
aTEQ (1989 NATO) = I-TEQDF
bTEQ (1997 WHO) = TEQDF-WHO9
Source: Huckaby (2003).
03/04/05
3-65
DRAFT—DO NOT CITE OR QUOTE
-------
o
OJ
o
4^
o
Table 3-6. CDD/CDF TEQ emission factors (ng TEQ/kg waste) for municipal solid waste incineration
Incinerator
design
MOD/SA
MOD/EA
FB/RDF
Air pollution
control device
(APCD)a
C-ESP
DS/DSI/C-ESP
DSI/FF
FF
H-ESP
UNC
WS
WS/FF
C-ESP
DS/FF
DSI/FF
DSI/H-ESP
EGB
H-ESP
Unc
WS
WS/C-ESP
DS/FF
DSI/EGB
DSI/FF
Average I-
TEQDF
emission
factor
16.2
16.2
0.025
16.2
79
0.025
16.2
16.2
16.2
16.2
0.025
118
0.025
118
0.025
16.2
16.2
0.63
0.63
0.63
Average
TEQDF-
WH098
emission
factor
17
17
0.024
17
85.7
0.024
17
17
17
17
0.024
119
0.024
119
0.024
17
17
0.72
0.72
0.72
Basis and rationale
Based on MOD/EA; C-ESP, similar furnace (modular design) and same APCD
Based on MOD/EA; C-ESP, similar furnace (modular design) and similar emission control
Based on direct tests
Based on MOD/EA; C-ESP, similar furnace (modular design) and similar emission control
Based on direct tests
Based on MOD/SA; DSI/FF, same furnace and most similar expected emissions
Based on MOD/EA; C-ESP, similar furnace (modular design) and similar APCD temperature
Based on MOD/EA; C-ESP, similar furnace (modular design) and similar APCD temperature
Based on direct tests
Based on MOD/EA; C-ESP, same furnace and similar temperature in APCD; may overestimate emissions
Based on MOD/SA; DSI/FF, similar (modular design) furnace and same APCD
Based on MOD/EA; H-ESP, same furnace and similar emissions
Based on MOD/SA; DSI/FF, same furnace and most similar expected emissions
Based on direct tests
Based on MOD/SA; DSI/FF, same furnace and most similar expected emissions
Based on MOD/EA; C-ESP, same furnace and similar APCD temperature
Based on MOD/EA; C-ESP, same furnace and similar APCD
Based on MB/WW; DS/FF similar furnace and same APCD
Based on MB/WW; DS/FF similar furnace; may underestimate emissions
Based on MB/WW; DS/FF similar furnace; may underestimate emissions
Oi
Oi
"Slash indicates devices used in conjunction.
APCD:
C-ESP = Cold-sided electrostatic precipitator
DS = Dry scrubber
DSI = Dry sorbent injection
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
Unc = Uncontrolled
WS = Wet scrubber
Incinerator design:
FB/RDF = Fluidized-bed refuse-derived fuel
MB/WW = Mass bum waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
-------
Table 3-7a. Annual I-TEQDF emissions from municipal waste combustors
(MWCs) operating in 1995
MWC type
MB/WW
MB/REF
MB/RC
RDF/ded
MOD/SA
Air pollution
control device
(APCD)a
C-ESP
DS/C-ESP
DS/CI/FF
DS/FF
DSI/CI/H-ESP
DSI/FF
DSI/H-ESP
H-ESP
Subtotal
C-ESP
DS/C-ESP
DS/FF
DSI/FF
WS
Subtotal
C-ESP
DS/FF
DSI/C-ESP
DSI/FF
Subtotal
C-ESP
DS/C-ESP
DS/FF
DSI/FF
DSI/H-ESP
H-ESP
DS/FF/C-ESP
Subtotal
C-ESP
DSI/FF
H-ESP
Unc
WS
WS/FF
DS/DSI/C-
ESP
Subtotal
I-TEQDF
emissions from
tested facilities
(gTEQ/yr)
0
170
39.8
21.6
0
0
0
61.4
0
5.54
32.5
33
0
8.01
Average
I-TEQDF
emission factor
(ng/kg)
6.1
6.1
1.5
0.63
7.74
473
0.63
1.91
236
470.646475
231
0.53
0.24
231
231
1492
0.24
16.2
79
0.025
16.2
16.2
16.2
Activity
level
nontested
facilities
(kg/yr)
2.81e+09
1.88e+09
7.44e+08
5.98e+09
0
0
4.22e+08
1.79e+08
0
0
2.68e+08
1.13e+08
2.04e+08
2.00e+08
7.57e+08
5.07e+08
1.46e+08
1.67e+09
1.14e+09
1.58e+09
4.22e+08
2.00e+08
4.22e+07
5.63e+08
1.25e+08
0
8.03e+07
1.87e+08
4.90e+07
2.82e+07
7.60e+07
I-TEQDF
emissions
from
nontested
facilities
(g TEQ/yr)
17.1
121
0
0
0.168
0.216
48.1
48.5
9.4
40.6
385
593
2
10.8
Total
I-TEQDF
emissions
from all
facilities
(gTEQ/yr)
17.1
291
39.8
21.6
0.168
0.216
48.1
110
9.4
46.1
418
626
2
18.8
03/04/05
3-67
DRAFT—DO NOT CITE OR QUOTE
-------
Table 3-7a. Annual I-TEQDF emissions from municipal waste combustors
(MWCs) operating in 1995 (continued)
MWC type
MOD/EA
FB/RDF
TOTAL
Air pollution
control device
(APCD)a
C-ESP
DS/FF
DSI/FF
DSI/H-ESP
H-ESP
Unc
WS/C-ESP
Subtotal
DS/FF
DSI/EGB
DSI/FF
Subtotal
I-TEQDF
emissions from
tested facilities
(gTEQ/yr)
0.0643
2.39
0
0
280
Average
I-TEQDF
emission factor
(ng/kg)
16.2
16.2
0.025
118
b
0.025
16.2
0.63
Activity
level
nontested
facilities
(kg/yr)
6.25e+07
1.18e+08
l.Ole+08
1.41e+07
0
1.41e+07
6.76e+07
1.69e+08
1.13e+08
8.45e+07
I-TEQDF
emissions
from
nontested
facilities
(g TEQ/yr)
1
5.64
0.106
0.231
820
Total
I-TEQDF
emissions
from all
facilities
(gTEQ/yr)
1.07
8.03
0.106
0.0709
0.0532
0.231
1,100
aSlash indicates devices used in conjunction.
Value could not be calculated.
APCD:
C-ESP = Cold-sided electrostatic precipitator
CI = Carbon injection
DS = Dry scrubber
DSI = Dry sorbent injection
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
Unc = Uncontrolled
WS = Wet scrubber
MWC type:
FB/RDF = Fluidized-bed refuse-derived fuel
MB/RC = Mass burn rotary kiln
MB/REF = Mass burn refractory walled
MB/WW = Mass burn waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
RDF/ded = Refuse-derived fuel/dedicated
03/04/05
3-68
DRAFT—DO NOT CITE OR QUOTE
-------
Table 3-7b. Annual TEQDF-WHO98 emissions from municipal waste
combustors (MWCs) operating in 1995
MWC type
MB/WW
MB/REF
MB/RC
RDF/ded
MOD/SA
Air pollution
control device
(APCD)a
C-ESP
DS/C-ESP
DS/CI/FF
DS/FF
DSI/CI/H-ESP
DSI/FF
DSI/H-ESP
H-ESP
Subtotal
C-ESP
DS/C-ESP
DS/FF
DSI/FF
WS
Subtotal
C-ESP
DS/FF
DSI/C-ESP
DSI/FF
Subtotal
C-ESP
DS/C-ESP
DS/FF
DSI/FF
DSI/H-ESP
H-ESP
DS/FF/C-ESP
Subtotal
C-ESP
DSI/FF
H-ESP
Unc
WS
WS/FF
DS/DSI/C-ESP
Subtotal
TEQDF-
WH098
emissions
from
tested
facilities
(g
TEQ/yr)
0
2.24
0.68
2.1
2.26
0.3
0
183
191
43
22.5
0
0
0
65.4
0
0.265
0
10.5
10.8
35.6
0.34
0.1
0
0
0
0
36.1
0
0.0008
8.69
0
0
0
0
8.69
Average
TEQDF-
WHO98
emission
factor
(ng/kg)
6.54
6.54
1.61
0.72
—
-
8.22
535
_
—
0.72
2.07
254
93.1
0.68
93.1
93.1
253
0.56
0.26
253
253
1679
253
17
-
85.7
0.024
17
17
17
Activity level
nontested
facilities
(kg/yr)
2.81e+09
1.88e+09
7.44e+08
5.98e+09
0
0
4.22e+08
1.79e+08
0
0
2.68e+08
1.13e+08
2.04e+08
2.00e+08
7.57e+08
5.07e+08
1.46e+08
1.67e+09
1.14e+09
1.58e+09
4.22e+08
2.00e+08
4.22e+07
5.63e+08
1.25e+08
0
8.03e+07
1.87e+08
4.90e+07
2.82e+07
7.60e+07
TEQDF-
WH098
emissions
from
nontested
facilities
(g TEQ/yr)
18.4
12.3
1.2
4.04
0
0
3.47
94.7
134
0
0
0.181
0.234
51.9
52.3
18.6
0.53
47.2
13.6
80
422
0.638
0.405
107
50.6
70.9
0.144
651
2.12
0
6.88
0.005
0.832
0.478
1.29
11.6
Total
TEQDF-
WHO98
emissions
from all
facilities
(g TEQ/yr)
18.4
14.54
1.88
6.14
2.26
0.3
3.47
278
325
43
22.5
0.181
0.234
51.9
117.8
18.6
0.8
47.2
24.1
90.8
458
0.98
0.5
107
50.6
70.9
0.144
687
2.12
0.0008
15.57
0.005
0.832
0.478
1.29
20.3
03/04/05
3-69
DRAFT—DO NOT CITE OR QUOTE
-------
Table 3-7b. Annual TEQDF-WHO98 emissions from municipal waste
combustors (MWCs) operating in 1995 (continued)
MWC type
MOD/EA
FB/RDF
TOTAL
Air pollution
control device
(APCD)a
C-ESP
DS/FF
DSI/FF
DSI/H-ESP
H-ESP
Unc
WS/C-ESP
Subtotal
DS/FF
DSI/EGB
DSI/FF
Subtotal
TEQDF-
WHO98
emissions
from
tested
facilities
(g
TEQ/yr)
0.068
0
0
0
2.35
0
0
2.42
0
0
0
0
315
Average
TEQDF-
WH098
emission
factor
(ng/kg)
17
17
0.024
119
-
0.024
17
0.72
0.72
0.72
Activity level
nontested
facilities
(kg/yr)
6.25e+07
1.18e+08
l.Ole+08
1.41e+07
0
1.41e+07
6.76e+07
1.69e+08
1.13e+08
8.45e+07
935
TEQDF-
WHO98
emissions
from
nontested
facilities
(g TEQ/yr)
1.06
2.01
0.002
1.68
0
0.003
1.15
5.9
0.114
0.076
0.057
0.247
Total
TEQDF-
WH098
emissions
from all
facilities
(g TEQ/yr)
1.13
2.01
0.002
1.68
2.35
0.003
1.15
8.32
0.114
0.076
0.057
0.247
1,250
aSlash indicates devices used in conjunction.
APCD:
C-ESP = Cold-sided electrostatic precipitator
CI = Carbon injection
DS = Dry scrubber
DSI = Dry sorbent injection
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
Unc = Uncontrolled
WS = Wet scrubber
MWC type:
FB/RDF = Fluidized-bed refuse-derived fuel
MB/RC = Mass burn rotary kiln
MB/REF = Mass burn refractory walled
MB/WW = Mass burn waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
RDF/ded = Refuse-derived fuel/dedicated
03/04/05
3-70
DRAFT—DO NOT CITE OR QUOTE
-------
Table 3-8a. Annual I-TEQDF emissions to the air from municipal waste
combustors (MWCs) operating in 1987
MWC type
MB/WW
MB/REF
MB/RC
RDF/ded
RDF/cofired
MOD/SA
MOD/EA
TOTAL
Air
pollution
control
device
(APCD)a
DS/FF
H-ESP
Subtotal
DS/FF
H-ESP
WS
Subtotal
FF
H-ESP
Subtotal
H-ESP
WS
Subtotal
H-ESP
FF
H-ESP
Unc
WS
Subtotal
EGB
Unc
WS
Subtotal
I-TEQDF
emissions
from tested
facilities
(g TEQ/yr)
0.0373
433
433
0
0
0
0
0
48.2
48.2
840
0
840
0
0
0.0643
0
0
0.0643
0
0
0
0
1,320
Average
I-TEQDF
emission
factor
(ng/kg)
473
0.63
473
236
47.0
285
1492
231
231
16.2
79.0
0.025
16.2
0.025
0.025
16.2
Activity
level
nontested
facilities
(kg/yr)
3.3e+09
1.41e+08
2.00e+09
9.01e+08
1.58e+07
2.25e+08
2.45e+09
3.38e+08
2.53e+08
1.43e+08
3.61e+08
5.73e+08
5.30e+07
6.76e+07
4.17e+07
1.27e+08
I-TEQDF
emissions from
nontested
facilities
(g TEQ/yr)
0
1,550
1,550
0.0887
944
212
1160
0.741
64.2
65
3,660
78.1
3,730
58.6
2.29
28.5
0.0142
0.848
31.6
0.0017
0.0010
2.03
2.03
6,590
Total I-TEQDF
emissions from
all facilities
(g TEQ/yr)
0.0373
1,980
1,980
0.0887
944
212
1,160
0.741
112
113
4,500
78.1
4,570
58.6
2.29
28.5
0.0142
0.848
31.7
0.0017
0.001
2.03
2.03
7,915
aSlash indicates devices used in conjunction.
APCD:
DS = Dry scrubber
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
Unc = Uncontrolled
WS = Wet scrubber
MWC type:
MB/RC = Mass burn rotary kiln
MB/REF = Mass burn refractory walled
MB/WW = Mass burn waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
RDF/cofired = Refuse-derived fuel/cofired
RDF/ded = Refuse-derived fuel/dedicated
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Table 3-8b. Annual TEQDF-WHO98 emissions to the air from municipal
waste combustors (MWCs) operating in 1987
MWC type
MB/WW
MB/REF
MB/RC
RDF/ded
RDF/cofired
MOD/SA
MOD/EA
TOTAL
Air
pollution
control
device
(APCD)a
DS/FF
H-ESP
Subtotal
DS/FF
H-ESP
WS
Subtotal
FF
H-ESP
Subtotal
H-ESP
WS
Subtotal
H-ESP
FF
H-ESP
Unc
WS
Subtotal
EGB
Unc
WS
Subtotal
TEQDF-
WHO98
emissions
from tested
facilities
(g TEQ/yr)
0.039
485
485
0
0
0
0
0
53.4
53.4
946
0
946
0
0
0.068
0
0
0.068
0
0
0
0
1,485
Average
TEQDF-
WH098
emission
factor
(ng/kg)
-
535
0.72
535
254
93.1
316
1,679
253
253
17
85.7
0.024
17
0.024
0.024
17
Activity
level
nontested
facilities
(kg/yr)
0
3.27e+09
1.41e+08
2.00e+09
9.01e+08
1.58e+07
2.25e+08
2.45e+09
3.38e+08
2.53e+08
1.43e+08
3.61e+08
5.73e+08
5.30e+07
6.76e+07
4.17e+07
1.27e+08
TEQDF-
WH098
emissions
from
nontested
facilities
(g TEQ/yr)
0
1,732
1,732
0.095
1,058
229
1,287
1.47
71.2
72.7
4,114
85.5
4,200
64.1
2.43
30.9
0.014
0.898
34.2
0.0016
0.001
2.15
2.15
7,392
Total TEQDF-
WH098
emissions from
all facilities
(g TEQ/yr)
0.039
2,218
2,218
0.095
1,058
229
1,287
1.47
124.6
126.1
5,060
85.5
5,146
64.1
2.43
31
0.014
0.898
34.3
0.0016
0.001
2.15
2.15
8,877
aSlash indicates devices used in conjunction.
APCD:
DS = Dry scrubber
EGB = Electro gravel bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator
Unc = Uncontrolled
WS = Wet scrubber
MWC type:
MB/RC = Mass burn rotary kiln
MB/REF = Mass burn refractory walled
MB/WW = Mass burn waterwalled
MOD/EA = Modular excess air
MOD/SA = Modular starved air
RDF/cofired = Refuse-derived fuel/cofired
RDF/ded = Refuse-derived fuel/dedicated
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Table 3-9. Fly ash from a municipal incinerator (jig/kg)
Congener group
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TOTAL CDDs
TCDF
PeCDF
HxCDF
HpCDF
OCDF
TOTAL CDFs
Average concentration
3.7
6.4
9.1
2.3
1.5
23
12
17
14
2.9
1.2
47
Concentration range
1.6-12
2-25
1.5-42
0.5-9.2
0.2-6
6.2-94
5.1-36
8.3-40
3.9-40
0.8-9.2
ND-2.1
22-110
Source: Clement etal. (1988).
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Table 3-10. Comparison of the amount of TEQs generated annually in
municipal waste combustor ash
Data source
U.S. EPA, 1990c
Washington State
Department of Ecology
(1998)
Ft. Lewis
Bellingham
Spokane
Shane etal. (1990)
Clement et al. (1988)
U.S. EPA. (1987a)
North America
Europe
Japan
Wire reclamation
Lahl etal. (1991)
Type of
ash
Mixed
Bottom
Fly
Mixed
Mixed
Fly
Bottom
Fly
Fly
Fly
Fly
Fly
Fly
Bottom
Mixed
Mean total
CDD/CDF
concentrati
on
(ng/kg)
12383
0
71,280
1,884
1,414
10,320
100
175,000
70,000
1,286,000
876,000
2,600
12,010
1,310
177,640
Mean I-
TEQDF
(ng/kg)
258
0
4,980
38
163
510
0.1
-
-
-
-
-
-
-
Annual TEQ
amount
1995 value3
(gl-
TEQDF/yr)
1806
0
3,486
266
1,141
357
1
-
-
-
-
-
-
-
Annual TEQ
amount
1987 value3
(gl-
TEQDF/yr)
1290
0
2,490
190
815
255
0.05
-
-
-
-
-
-
-
aln calculating the annual TEQ amounts, fly ash and bottom ash were considered to be 10% and
90% of the total ash, respectively.
- = Value could not be calculated
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Table 3-11. Concentration of dioxin in fly ash samples from combustion of
municipal solid waste (ng/kg)
Congener
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
Stoker incinerators
B
5,000
20,000
45,000
70,000
125,000
25,000
50,000
65,000
75,000
40,000
c
200,000
340,000
440,000
340,000
110,000
210,000
410,000
400,000
230,000
20,000
D
80,000
200,000
250,000
230,000
160,000
330,000
320,000
300,000
200,000
40,000
E
75,000
105,000
90,000
37,000
15,000
50,000
45,000
22,000
10,000
1,000
Fluidized-bed incinerators
F
6,000
10,000
12,000
8,000
7,000
13,000
14,000
21,000
17,000
10,000
I
10,000
28,000
41,000
40,000
25,000
18,000
32,000
34,000
33,000
13,000
J
10,000
37,000
100,000
200,000
187,000
50,000
125,000
210,000
225,000
150,000
L
5,000
10,000
30,000
40,000
50,000
70,000
120,000
200,000
270,000
120,000
Source: Imagawa et al. (2000) (numbers estimated from Figure 2 of report).
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Table 3-12. Concentration of dioxin in fly ash samples from municipal solid
waste
Congener
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
TOTAL
Concentration (ng/kg)
8,000
9,000
40,000
10,800
8,000
8,000
10,000
9,500
8,500
8,000
119,800
TEQ (ng/kg)
15
45
100
50
1
10
300
300
40
1
862
Source: Kobylecki et al. (2001) (values estimated from values in Figure 4 of "Before
Incineration").
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Table 3-13. Dioxin and furan concentrations in municipal solid waste ash
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
TOTAL
Concentrations (ng/kg)
Fly ash
19
78
92
210
130
1,300
2,800
150
290
320
310
310
21
400
1,100
110
320
8,250
Bottom ash
1.6
3.1
2.6
5.6
3.6
33
110
4.8
5.3
5.9
4.4
4.9
0.36
6.7
23
1.6
9.3
226
I-TEQs (ng/kg)
Fly ash
19
39
9.2
21
13
13
2.8
15
14.5
160
31
31
2.1
40
11
1.1
0.32
423
Bottom ash
1.6
1.65
0.26
0.56
0.36
0.33
0.11
0.48
0.265
2.95
0.44
0.49
0.036
0.67
0.23
0.016
0.0093
10.5
Source: Sakaietal. (2001).
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Table 3-14a. CDD/CDF emission factors for hazardous waste incinerators
and boilers tested from 1993 to 1996
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 I-TEQDF
Total TEQnF-WHO9S
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Incinerator average mean
emission factor (17 facilities)
(ng/kg feed)
Nondetect set to
1A detection limit
0.44
0.18
0.22
0.32
0.49
1.77
4.13
2.96
2.36
2.56
9.71
3.95
0.31
2.7
16.87
1.74
13.79
4.22
4.29
NR
NR
NR
NR
4.13
NR
NR
NR
NR
13.78
153
Nondetect
set to zero
0.14
0.14
0.18
0.28
0.48
1.74
3.74
2.69
2.33
2.51
9.71
3.95
0.29
2.7
16.68
1.71
13.46
3.83
3.88
NR
NR
NR
NR
3.74
NR
NR
NR
NR
13.46
153
Hot-sided ESP boilers mean
emission factor (2 facilities)
(ng/kg feed)
Nondetect set to
1A detection limit
0.1
0.11
0.15
0.2
0.22
1.17
5.24
0.81
0.38
0.52
0.83
0.37
0.08
0.56
1.04
0.18
0.7
0.78
0.83
0.77
1.15
1.67
2.34
5.24
5.47
5.51
4.04
1.94
0.7
28.83
Nondetect
set to zero
0
0.04
0.08
0.18
0.2
1.17
5.24
0.81
0.38
0.52
0.83
0.37
0.02
0.56
0.93
0.16
0.7
0.64
0.65
0.77
0.77
1.62
2.34
5.24
5.47
5.51
4.04
1.94
0.7
28.39
ESP = Electrostatic precipitator
NR = Not reported
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Table 3-14b. CDD/CDF emission factors for hazardous waste incinerators
and boilers tested in 2000
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 I-TEQDF
Total TEQnF-WHO9S
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Incinerator average mean
emission factor (12 facilities)
(ng/kg feed)3
Nondetect set to
1A detection limit
0.0615
0.6141
0.2347
0.5408
0.3037
2.729
5.211
0.6931
0.9406
0.88
4.085
3.031
2.667
1.218
28.74
5.056
36.27
2.54
2.809
NR
NR
NR
NR
5.211
NR
NR
NR
NR
36.27
195.7
Nondetect
set to zero
0.036
0.0907
0.1395
0.4351
0.2178
2.699
5.17
0.6399
0.8375
0.735
4.045
3.001
2.637
1.121
28.71
5.021
36.23
2.119
2.127
NR
NR
NR
NR
5.17
NR
NR
NR
NR
36.23
194.1
Hot-sided ESP boilers mean
emission factor (1 facility)
(ng/kg feed)3
Nondetect set to
1A detection limit
0.0346
0.0488
0.1149
0.1715
0.3361
1.406
1.554
0.9531
0.4599
0.8836
3.611
0.69
0.038
1.3272
4.6345
0.1895
0.7841
1.313
1.335
NR
NR
NR
NR
1.554
NR
NR
NR
NR
0.7841
17.24
Nondetect
set to zero
0
0
0.0789
0.1228
0.231
1.4055
1.5541
0.9531
0.3862
0.8836
3.6108
0.561
0
1.3272
4.6345
0.1257
0.7841
1.214
1.212
NR
NR
NR
NR
1.554
NR
NR
NR
NR
0.7841
16.66
"Values incorporating use of the detection limit when the laboratory report indicated "not
detected" for individual CDD/CDF congeners.
NR = Not reported
Source: U.S. EPA(2002b).
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Table 3-15. CDD/CDF emission factors for halogen acid furnaces tested in
2000
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 I-TEQDF
Total TEQnF-WHO9S
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Incinerator average mean emission factor (12 facilities)
(ng/kg feed)
Nondetect set to
1A detection limit
0.0274
0.1164
0.0979
0.1663
0.1686
0.9868
1.4944
0.3821
0.5830
0.5689
1.1244
0.7172
0.4412
0.2685
3.4914
1.0429
25.015
0.8176
0.8519
NR
NR
NR
NR
1.4944
NR
NR
NR
NR
25.015
62.4773
Nondetect set to zero
0.0208
0.112
0.0913
0.1594
0.1293
0.9868
1.4944
0.3821
0.583
0.5689
1.1244
0.7172
0.4412
0.2685
3.4914
1.0429
25.015
0.8034
0.8356
NR
NR
NR
NR
1.4944
NR
NR
NR
NR
25.015
62.4607
NR = Not reported
Source: U.S. EPA (2002b).
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Table 3-16. Estimated breakdown of facilities by air pollution control device
(APCD)
APCD
1/4-sec combustion
1-sec combustion
2-sec combustion
Low-efficiency wet scrubber
Moderate-efficiency wet scrubber
High-efficiency wet scrubber
Dry lime inject fabric filter
Dry lime inject fabric filter with carbon injection
Wet scrubber/dry lime inject fabric filter
Spray dryer fabric filter with carbon injection
Number of
facilities
229
259
455
208
75
16
44
7
14
1
Percent of
total
17.5
19.8
34.8
15.9
5.7
1.2
3.4
0.5
1.1
0.1
Source: Strong and Hanks (1999).
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Table 3-17. Summary of annual operating hours for each medical waste
incinerator (MWI) type
MWI
Continuous
commercial
Continuous
onsite
Intermittent
Batch
Capacity range
(Ib/hr)
>1,000
501-1,000
>1,000
<500
Case by case
Annual
charging hours
(hr/yr)
7,776
1,826
2,174
1,250
Case by case
Maximum annual
charging hours
(hr/yr)
8,760
5,475
4,380
Capacity
factor
0.89
0.33
0.40
0.29
Case by case
Source: U.S. EPA (1990e).
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Table 3-18. Office of Air Quality Planning and Standards approach:
estimated nationwide I-TEQDF emissions for 1995
Medical waste
incinerator type
Batch
Continuous
Continuous/
intermittent
Intermittent
Batch
Continuous
Continuous/
intermittent
Intermittent
Continuous
Continuous/
intermittent
Intermittent
Continuous
Continuous/
intermittent
Intermittent
TOTAL
Residence time
(sec) or air
pollution control
device
0.25
1
2
0.25
1
2
0.25
1
2
0.25
1
2
CDD/CDF
emission
factor
(ng/kg)
193,997
44,500
3,650
193,997
44,500
3,650
193,997
44,500
3,650
193,997
44,500
3,650
I-TEQDF
emission
factor
(ng/kg)
3,960
909
74
3,960
909
74
3,960
909
74
3,960
909
74
Subtotal: uncontrolled
Wet scrubber
Wet scrubber
Wet scrubber
Wet scrubber
426
426
426
426
10
10
10
10
Subtotal: controlled w/wet scrubber
Dry scrubber, no
carbon
Dry scrubber, no
carbon
Dry scrubber, no
carbon
Dry scrubber, with
carbon
Dry scrubber, with
carbon
365
365
365
70
70
7
7
7
2
2
Subtotal: controlled w/dry scrubber
Fabric filter/ packed
bed
33,400
681
Activity
level
(kg/yr)
5.95e+06
4.20e+05
2.14e+05
1.20e+06
5.10e+06
3.01e+07
4.54e+06
5.10e+06
9.79e+07
4.18e+06
5.57e+07
4.31e+07
2.54e+08
2.42e+04
1.88e+08
1.22e+08
6.04e+07
3.70e+08
9.94e+07
7.86e+06
2.07e+07
1.43e+07
3.70e+06
1.46e+08
6.99e+05
7.71e+08
CDD/CDF
emissions
(g/yr)
1.15e+03
1.87e+01
7.81e-01
2.33e+02
2.27e+02
1.10e+02
8.81e+02
2.27e+02
3.57e+02
8.11e+02
2.48e+03
1.57e+02
6.66e+03
1.03e-02
S.Ole+01
5.20e+01
2.57e+01
1.58e+02
3.63e+01
2.87e+00
7.56e+00
l.OOe+00
2.59e-01
4.80e+01
2.34e+01
6.88e+03
I-TEQDF
emissions
(g/yr)
2.36e+01
3.82e-01
1.58e-02
4.75e+00
4.64e+00
2.23e+00
1. 80e+01
4.64e+00
7.24e+00
1.666+01
5.06e+01
3.19e+00
1.36e+02
2.42e-04
1.88e+00
1.22e+00
6.04e-01
3.70e+00
6.96e-01
5.50e-02
1.45e-01
2.86e-02
7.40e-03
9.32e-01
4.76e-01
1.41e+02
NA = Not applicable
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Table 3-19. Office of Air Quality Planning and Standards approach:
particulate matter emission limits for medical waste incinerator (MWI) types
and corresponding residence times in the secondary combustion chamber
MWI type
Intermittent and
continuous
Batch
Particulate matter
emission limit
(gr/dscf)
>0.3
0.16 to < 0.3
0.1 to<0.16
>0.079
0.042 to <0.079
0.026 to <0.042
Residence time in
secondary chamber
(sec)
0.25
1
2
0.25
1
2
I-TEQDF emission
factor
(kg I-TEQDF/kg
waste)
3.96e-9
9.09e-10
7.44e-ll
3.96e-9
9.09e-10
7.44e-ll
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Table 3-20. American Hospital Association approach: I-TEQDF emission
factors calculated for air pollution control device (APCD)
APCD3
Uncontrolled
MWIs up to 200 Ib/hr
MWIs >200 Ib/hr
WS/FF/ESP
DSI/FF
I-TEQDF emission factor
(lb/106lb of waste)
1.53e-03
5.51e-04
4.49e-05
6.95e-05
Number of medical waste
incinerators (MWIs)
test reports usedb
413
11
8
aSlash(es) indicates devices used in conjunction.
bThe same MWI may have been used more than once in deriving emission factors.
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
WS = Wet scrubber
Source: Doucet (1995).
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Table 3-21. American Hospital Association assumptions of the percent
distribution of air pollution control on medical waste incinerators (MWIs)
based on particulate matter (PM) emission limits
PM emission limitsa
(gr/dscf)
>0.10
0.08to<0.10
0.03 to <0. 08
<0.03
Percent MWIs
uncontrolled15
50
25
0
0
Percent MWIs with
WSs/ FFs/ESPs
50
75
98
30
Percent MWIs
with DSI/FF
0
0
2
70
aPM emission limits at the stack.
bNo air pollution control device installed on the MWI.
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
WS = Wet scrubber
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Table 3-22. American Hospital Association approach: estimated annual
nationwide I-TEQDF emissions
Air pollution
control
device
(APCD)a
Uncontrolled
WS/FF/ESP
DI/FF
TOTAL
Medical waste
incinerator15
(Ib/hr)
<200
>200
I-TEQDF
emission factor0
(g/kg waste)
1.54e-06
5.51e-07
Subtotal uncontrolled
>200
>200
4.49e-08
6.95e-08
Subtotal controlled
Medical waste
incineratord
(kg/yr)
2.28e+07
1.54e+08
1.77e+08
3.51e+08
2.60e+07
3.77e+08
5.54+08
Annual I-TEQDF
emissions
(g/yr)
3.51e+01
8.48e+01
1.20e+02
15.8e+01
1.81
1.76e+01
1.38e+02
aSlash(es) indicates devices used in conjunction.
bDesign capacity of the primary combustion chamber.
cDerived from tested facilities.
dAnnual amount of medical waste incinerated by each APCD class.
APCD:
DI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
MWI = Medical waste incinerator
WS = Wet scrubbers
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Table 3-23. Comparison between predicted residence times at medical waste
incinerators (MWIs) and residence times confirmed by state agencies in the
Office of Research and Development telephone survey
State
Michigan
Massachusetts
Virginia
New Jersey
Residence
time
categories
(sec)
1/4
1
2
1/4
1
2
1/4
1
2
1/4
1
2
Percentage of uncontrolled
MWIs predicted by
particulate matter method
(no. of MWIs)
2 (6/280)
2 (5/280)
96 (269/280)
6 (6/94)
0 (0/94)
94 (88/94)
1 1 (6/56)
0 (0/50)
89 (50/56)
0 (0/53)
0 (0/53)
100 (53/53)
Percentage of uncontrolled
MWIs confirmed by state
agency (no. of MWIs)
96 (269/280)
3 (9/280)
1 (1/280)
Unknown
Unknown
4 (2/50)
4.5 (1/22)
91 (20/22)
4.5 (1/22)
Unknown
Unknown
Unknown
Source: O'Rourke (1996).
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o
OJ
o
4^
o
Table 3-24. Summary of annual TEQ emissions from medical waste incinerators (MWIs) for reference year
1987 (ORD approach)
MWI class3
<200 Ib/hr
>200 Ib/hr
TOTAL
No. of tested
facilities
3
5
8
Activity
level
(kg/yr)
2.19e+08
1.21e+09
1.43e+09
Total CDD/
CDF
emission
factor"
(g/kg)
9.25e-05
6.05e-05
I-TEQDF
emission
factor
(g/kg)
1.86e-06
1.68e-06
TEQDF-
WHO98
emission
factor
(g/kg)
1.98e-06
1.78e-06
Annual
CDD/
CDF
emissions
(g/yr)
2.02e+04
7.32e+04
9.34e+04
Annual
I-TEQDF
emissions
(g/yr)
4.08e+02
2.03+03
2.44+03
Annual
TEQDF-
WHO98
emissions
(g/yr)
4.34e+02
2.14e+03
2.59e+03
oo
VO
o
o
2
O
H
O
HH
H
W
"Categorization scheme of the American Hospital Association approach (Doucet, 1995).
O
c
o
H
W
-------
o
OJ
o
4^
o
Table 3-25. Office of Research and Development approach: TEQ emissions from medical waste incinerators
(MWIs) for reference year 1995
MWI class
(air
pollution
control
device
[APCD])
Uncontrolled
Controlled
TOTAL
MWI
subclass
(capacity
or
APCD3)
<200 Ib/hr
>200 Ib/hr
WS/FF/
ESP
DSI/FF
FF/PBS
No. of
tested
facilities
3
5
9
2
1
Total
CDD/
CDF
emission
factor
(ng/kg)
9.25e+04
6.05e+04
4.67e+04
2.85e+02
l.lle+05
I-TEQDF
emission
factor
(ng/kg)
1.86e+03
1.80e+03
7.22e+01
6.78
1.35e+03
TEQDF-
WHO98
emission
factor
(ng/kg)
1.98e+03
1.78e+03
7.43e+01
6.86
1.49e+03
Activity
level
(kg/yr)
3.06e+07
2.23e+08
3.71e+08
1.46e+08
6.99e+05
7.71e+08
Annual
CDD/
CDF
emissions
(g/yr)
2.83e+03
1.35e+04
1.73e+03
4.16e+01
7.76e+01
1.82e+04
Annual
I-TEQDF
emissions
(g/yr)
5.71e+01
3.75e+02
2.68e+01
9.90e-01
9.44e-01
4.61e+02
Annual
TEQDF-
WHO98
emissions
(g/yr)
6.06e+01
3.98e+02
2.76e+01
l.OOe+00
1.04e+00
4.88e+02
VO
o
O
O
2
O
H
O
HH
H
W
aSlash(es) indicates devices used in conjunction.
APCD:
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
PBS = Packed-bed scrubber
WS = Wet scrubber
O
c
o
H
W
-------
o
OJ
o
4^
o
Table 3-26. Office of Research and Development approach: TEQ emissions from medical waste incinerators
(MWIs) for reference year 2000
MWI class
(air pollution
control
device
[APCD])
Uncontrolled
Controlled
TOTAL
MWI subclass
(capacity or
APCD3)
<200 Ib/hr
>200 Ib/hr
WS/FF/
ESP
DSI/FF
FF/PBS
No. of
tested
facilities
O
5
10
3
1
Total
CDD/CDF
emission factor
(ng/kg)
9.25e+04
6.05e+04
4.55e+03
2.67e+02
l.lle+05
3.77e+04
TEQDF-WH098
emission factor
(ng/kg)
1.98e+03
1.78+03
6.63e+01
4.61
1.49e+03
7.57e+02
Activity
level
(kg/yr)
2.40e+07
1.74e+08
2.88e+08
1.14e+08
5.40e+05
6.00e+08
Annual
CDD/CDF
emissions
(g/yr)
2.22e+03
1.05e+04
1.31e+03
3.04e+01
5.99e+01
1.28e+04
Annual
TEQDF-
WHO98
emissions
(g/yr)
4.75e+01
3.10e+02
1.91e+01
5.26e-01
8.05e-01
3.78e+02
O
O
2
o
H
O
HH
H
W
aSlash(es) indicates devices used in conjunction.
APCD:
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
PBS = Packed-bed scrubber
WS = Wet scrubber
O
c
o
H
W
-------
Table 3-27. Comparison of basic assumptions used in the ORD, OAQPS, and
AHA approaches to estimating nationwide CDD/CDF TEQ emissions from
medical waste incinerators (MWIs) for reference year 1995
Assumption
Number of MWIs
Estimated activity level
Percent of activity level at
uncontrolled MWIs
Percent of activity level at
controlled MWIs
Subclassification of
uncontrolled class
Assumed distribution of
uncontrolled class
Air pollution control
devices (APCDs) assumed
for controlled class
Assumed distribution of
controls
Emission factor approach
used
No. of tested MWIs used to
develop emission factors
Uncontrolled I-TEQDF
emission factors (ng/kg)
Controlled I-TEQDF
emission factors (ng/kg)f
ORD approach
2,375
7.71e+08kg/yr
33
67
Same as AHA
assumption
Same as AHA
assumption
WS/FF/ESP
DSI/FF
FF/PBS
Yes/analogous to
AHA method
Yes
Uncontrolled: 8
Controlled: 11
1,865 = <200 Ib/hr
1,680 = >200 Ib/hr
WS/FF/ESP: 72.2
DSI/FF: 6.8
FF/PBS: 1350
OAQPS approach
2,375
7.71e+08kg/yr
33
67
By residence times in
secondary chamber
By residence times of 0.25, 1,
and 2 sec by state PM
emission limits
WS
DS no carbon
DS carbon
FF/PBS
Yes/analogous to AHA
method
Yes
Uncontrolled: 10
Controlled: 23
3,960 = 0.25 sec RTa
909 = 1 sec RTb
74 = 2 sec RTC
WS: 10
DS no carbon: 7
DS with carbon: 2
FF/PBS: 681
AHA approach
2,233
5.54e+08 kg/yr
32
68
By design capacity
By estimated annual hrs
of operation of <200 Ib/hr
and >200 Ib/hr design
capacity
WS/FF/ESP
DSI/FF
Yes/based on survey and
state PM emission limits
Yes
Uncontrolled: 13
Controlled: 12
1,540 = <200 Ib/hr4
55 1=>200 Ib/hr6
WS/FF/ESP: 44.9
DSI/FF: 69.5
a0.25 seconds residence time in the secondary chamber.
bl second residence time in the secondary chamber.
°2 seconds residence time in the secondary chamber.
dDesign capacities less than or equal to 200 Ib/hr.
Ttesign capacities greater than 200 Ib/hr.
Emission factors as reported in Tables 3-9, 3-12, and 3-14.
AHA = American Hospital Association
OAQPS = Office of Air Quality Planning and Standards
ORD = Office of Research and Development
PM = Paniculate matter
RT = Residence time
APCD:
DS = Dry scrubber
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
PBS = Packed-bed scrubber
WS = Wet scrubber
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Table 3-28. Congener-specific profile for Camellia Memorial Lawn
Crematorium
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility emission factor
Assuming nondetect
set to zero
(ng/body)
28.9
89.6
108
157
197
1,484
2,331
206
108
339
374
338
657
135
1,689
104
624
4,396
4,574
501
543
554
860
2,224
3,180
2,331
4,335
2,563
4,306
2,030
624
23,007
Assuming nondetect set to
1A detection limit
(ng/body)
28.9
89.6
108
157
197
1,484
2,331
206
117
349
374
338
657
135
1,813
112
624
4,396
4,725
508
550
554
860
2,224
3,180
2,331
4,335
2,563
4,306
2,154
624
23,131
Source: CARS (1990c).
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Table 3-29. Congener-specific profile for the Woodlawn Cemetery
crematorium
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
Total I-TEQDF
Total TEQDF-WHO98
Mean emission factor,
scrubber inlet (ng/body)
Nondetect set
to zero
11
31
74
115
83
724
1,120
106
116
285
263
278
146
466
962
165
435
319
325
Nondetect set to
1A detection limit
12
44
74
115
83
724
1,120
106
116
285
264
278
146
466
963
165
435
329
341
Mean emission factor,
scrubber outlet (ng/body)
Nondetect
set to zero
39
168
239
565
524
1,253
10,698
256
150
409
252
253
139
429
872
142
3,499
780
961
Nondetect set to 1A
detection limit
45
364
258
603
553
1,302
1,154
279
170
463
280
282
148
474
948
148
363
780
961
Source: U.S. EPA (1999f).
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Table 3-30. Operational data for the Woodlawn Cemetery crematorium,
scrubber inlet
Parameter
Particulate matter (gr/dscf @ 7% O2)
Hydrochloric acid (Ib/hr)
Lead (g/hr)
Oxygen (%)
Mean value
675 °C
0.015
0.053
0.1
9.9
870 °C
0.033
0.14
0.32
8.6
980 °C
0.068
0.26
0.59
7.5
Source: U.S. EPA (1999f).
03/04/05
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Table 3-31. Congener-specific profile for the Camellia Memorial Lawn
Crematorium and the Woodlawn Cemetery crematorium
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 I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility emission factor (ng/body)
Nondetect set to zero
20
67
91
136
140
1,104
1,721
156
112
312
319
308
401
300
1,326
135
530
410
434
467
838
1,923
2,384
1,721
3,586
2,441
3,575
1,897
530
19,362
Nondetect set to 1A detection limit
20
60
91
136
140
1,104
1,721
156
117
317
319
308
401
300
1,387
138
530
329
341
467
838
1,923
2,384
1,721
3,586
2,441
3,575
1,958
530
19,424
Source: CARS (1990c); U.S. EPA (1999f).
03/04/05
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Table 3-32. Congener-specific profile for the University of Georgia
Veterinary School
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 CDD/CDF
Total I-TEQDF
Total TEQDF-WHO98
Mean facility emission factor (ng/kg of animal)
Nondetect set to zero
7.51e-03
2.13e-02
4.46e-03
8.86e-03
7.17e-03
5.03e-03
l.Ole-03
1.79e-02
6.70e-03
1.41e-01
2.93e-02
1.85e-02
7.44e-02
2.35e-02
4.20e-03
3.16e-03
2.00e-04
0.37
0.11
0.12
Nondetect set to 1A detection limit
7.51e-03
2.13e-02
4.46e-03
8.86e-03
7.17e-03
5.03e-03
l.Ole-03
1.79e-02
6.70e-03
1.41e-01
2.93e-02
1.85e-02
7.44e-02
2.35e-02
4.20e-03
3.16e-03
2.00e-04
0.37
0.11
0.12
Source: U.S. EPA(2000e).
03/04/05
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Table 3-33. CDD/CDF emission factors for sewage sludge incinerators
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 TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total I-TEQDF
Total TEQDF-WHO98
Total CDD/CDF
Mean emission factor (ng/kg)
for U.S. EPA (1987a)
(3 facilities)
Nondetect
set to zero
0.39
NR
NR
NR
NR
NR
46.2
179
NR
NR
NR
NR
NR
NR
NR
NR
109
37.6
2.66
16.6
53.9
46.2
528
253
75.4
144
109
NR
NR
1,266
Nondetect set to
1A detection
limit
0.44
NR
NR
NR
NR
NR
46.2
179
NR
NR
NR
NR
NR
NR
NR
NR
109
37.7
2.81
16.9
54
46.2
528
253
75.9
144
109
NR
NR
1,268
Mean emission factor (ng/kg) for
Green et al. (1995) (11 facilities)
U.S. EPA (1990f) (2 facilities)
U.S. EPA (1999) (1 facility)
Nondetect set
to zero
0.16
0.22
0.04
0.12
0.29
2.46
12.78
25.41
1.92
6.47
2.11
0.77
0.03
1.22
1.46
0.17
1.17
35.8
1.11
1.74
4.39
12.78
123.85
59.94
12.69
2.63
1.17
6.65
6.74
256
Nondetect set to
1A detection limit
0.26
0.3
0.11
0.17
0.35
2.59
13.16
25.41
1.92
6.47
2.11
0.77
0.03
1.22
1.46
0.17
1.17
37.81
1.63
2.25
5.03
13.16
124.1
60.16
13.5
3.12
1.55
6.87
7.01
262
NR = Not reported
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Table 3-34. CDD/CDF air emission factors for tire combustion
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 TEQnF-WHO9S
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility emission factor (ng/kg)
Assuming nondetect set to zero
0.149
0.006
0.018
0.055
0.036
0.379
4.156
0.319
0.114
0.086
0.103
0.059
0.036
0.1
0
0.027
0.756
4.799
1.6
0.282
0.281
0.153
0.032
0.391
0.695
4.156
1.204
0.737
0.71
0.119
0.802
8.999
Assuming nondetect set to
1A detection limit
0.149
0.026
0.023
0.062
0.048
0.379
4.156
0.319
0.118
0.091
0.111
0.09
0.068
0.148
0.166
0.095
0.756
4.843
1.962
0.311
0.318
0.153
0.032
0.391
0.695
4.156
1.204
0.737
0.71
0.186
0.802
9.067
Source: CARS (1991a).
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Table 3-35. CDD/CDF emission factors for combustion of bleached-kraft
mill sludge in wood residue boilers
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 TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total I-TEQDF
Total TEQDF-WHO98
Total CDD/CDF
Mean emission factors
(ng/kg feed)
Nondetect set to zero
0.005
0.005
0.012
0.05
0.035
0.301
1.189
0.104
0.022
0.019
0.069
0.043
0.036
0.004
0.274
0.081
0.187
0.101
0.03
0.599
0.956
1.189
0.56
0.469
0.748
1.102
0.187
0.061
0.062
5.941
Nondetect set to
1A detection limit
0.013
0.012
0.022
0.056
0.043
0.302
1.192
0.107
0.029
0.027
0.071
0.046
0.041
0.012
0.275
0.083
0.188
0.108
0.109
0.6
0.958
1.192
0.56
0.47
0.748
1.102
0.188
0.082
0.087
6.037
Source: NCASI(1995).
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Riddling
Secondary Conveyor
Fan
Vibrating
Conveyor
Belt Total
Conveyor Ash
Discharge
Figure 3-1. Typical mass burn waterwall municipal solid waste incinerator.
Source: U.S. EPA (1997b).
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Figure 3-2. Typical mass burn rotary kiln combustor.
Source: U.S. EPA (1997b).
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To Stacker
Waste Heat Boiler
Primary
Gas Burner
Feed
Chute
Waste Tipping Floor
Secondary
Chamber
NV
Primary Chamber
Charge
Hopper
Transfer Rams
/
Ash
Quench
Primary Air
Secondary
Gas Burner
Figure 3-3. Typical modular starved-air combustor with transfer rams.
Source: U.S. EPA (1997b).
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Figure 3-4. Typical modular excess-air combustor.
Source: U.S. EPA (1997b).
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Superheater
Figure 3-5. Typical dedicated refuse-derived fuel-fired spreader stoker
boiler.
Source: U.S. EPA (1997b).
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Thermocouple
Sludge
Inlet
Fluid izing
Air Inlet
Exhaust and Ash
Freeboard
Pressure Tap
Sight
/> Glass
Burner
Tuyeres
Fuel Gun
Pressure Tap
Startup
Preheat
Burner
for Hot
Windbox
Figure 3-6. Fluidized-bed refuse-derived fuel incinerator.
Source: U.S. EPA (1997b).
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Muncipal Solid Waste
Incinerator Design
Classes for 1987
Rotary Kiln
Combustor
-
H-ESP
FF
Figure 3-7. Municipal waste combustor design classes for 1987.
DS/FF = Dry scrubber combined with a fabric filter
EGB = Electrogranular activated carbon bed
FF = Fabric filter
H-ESP = Hot-sided electrostatic precipitator (temperature at control device is greater than 230 °C)
WS = Wet scrubber
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Muncipal Solid Waste
Incinerator Design
Classes for 1995
Figure 3-8. Municipal waste combustor design classes for 1995.
C-ESP = Cold-sided electrostatic precipitator (temperature at control device is below less than 230 °C)
DS/CI/FF = Dry scrubber with carbon injection and fabric filter
DS/FF = Dry scrubber combined with a fabric filter
DSI/FF = Dry sorbent injection coupled with a fabric filter
EGB = Electrogranular activated carbon bed
H-ESP = Hot-sided electrostatic precipitator (temperature at control device is greater than 230 °C)
WS = Wet scrubber
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Municipal Solid Waste Incinerator Design Classes for 2000
1
I I
1 1 1
Mass Burn
Modular, Excess air M Modular, Starved air
1
Waterwall
I
H
-| SD/FF/CI
1 bu/hh -1 SD/FF
-| SD/FF/CI/SNCR
"I Ubl""h L-| WS/FSP
-| SD/FF/SNCR
-| SD/ESP/CI
-| SD/FF/SNCR
-| SD°/FF/CI/SNCR
-| SD/FF
-| DSI/FF
-| ESP
H FF
L-| SD/FF/CI/SNCR
-| DSI/ESP
-| DSI/FF
-| ESP
H
-| SD/FF/CI
L| ws
M Refuse-Derived Fuel
-| DSI/FF1
-| SD/ESP
-| SD/FF
-| SD/FF/CI/SNCR
-| DSI/FF/hhO/SNCR
-| SD/ESP/FF/CI
-| SD/FF/SNCR
-| SD/FF/SNCR
L-| ESP
Figure 3-9. Municipal waste combustor design classes for 2000.
aAlso equipped with furnace dry sorbent injection system
bAlso equipped with flue gas cooling (280-290 °F)
°Also equipped with compact hybrid paniculate collector system
CI = Carbon injection
DSI = Dry sorbent injection
ESP = Electrostatic precipitator
FF = Fabric filter
H2O = Water scrubber
SD = Spray dryer
SNCR = Selective noncatalytic reduction
WS = Wet scrubber
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.02 0.04 0.06 0.08 0.1
0.12
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.08 0.1 0.15 0.2 0.25
Figure 3-10. Congener and congener group profiles for air emissions from
a mass burn waterwall municipal waste combustor equipped with a dry
scrubber and fabric filter.
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o
OJ
o
4^
o
fe
H
O
O
o
H
O
HH
H
W
ND = 0 ND = 1/2 detection limit ND = full detection limit
Arithmetic average (ng/dscm @ 7%O2) 0.00545 0.00578 0.0061
Arithmetic standard deviation 0.01542 0.01535 0.0153
o
o
30
25
20
15
10
n
0-.5 .5-1 1-1.5 1.5-2 2-2.5 2.5-3 3-3.5 3.5^ 4^.5 4.5-5 5-5.5 5.5-6 6-6.5 6.5-7 7-7.5 7.5-8 8-8.5 8.5-9 9-9.5 9.5-10
Bin
DND = 0
• ND = 1/2 detection limit
n ND = full detection limit
Figure 3-11. 2,3,7,8-TCDD frequency distribution (negative natural log concentration).
O
c
o
H
W
-------
o
OJ
o
4^
o
fe
H
O
O
o
H
O
HH
H
W
35
30
25
•£ 20
3
O 15
10
5
0
ND = 0 ND = 1/2 detection limit ND = full detection limit
Arithmetic average (ng/dscm @ 7%O2) 0.01589 0.0163 0.01669
Arithmetic standard deviation 0.03375 0.03364 0.0336
0-.5 .5-1 1-1.5 1.5-2 2-2.5 2.5-3 3-3.5 3.5-4 4-4.5 4.5-5 5-5.5 5.5-6 6-6.5 6.5-7 7-7.5 7.5-8 8-8.5 8.5-9 9-9.5 9.5-10
Bin
• ND = 0
• ND = 1/2 detection limit
n ND = full detection limit
Figure 3-12. 1,2,3,7,8-PeCDD frequency distribution (negative natural log concentration).
O
c
o
H
W
-------
Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15
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
Figure 3-13. Congener profile for air emissions from hazardous waste
incinerators.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2
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-OCD:
Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25
Figure 3-14. Congener and congener group profiles for air emissions from
boilers and industrial furnaces burning hazardous waste.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
2,3,Z,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-FeCDF
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,Z,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
Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25
Nondetects set equal to zero.
Figure 3-15. Congener and congener group profiles for air emissions from
medical waste incinerators without air pollution control devices.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
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-OCDl
Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2
Figure 3-16. Congener and congener group profiles for air emissions from
medical waste incinerators equipped with a wet scrubber and fabric filter.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
4D 2378
6D 123478
6D 123789
5F 12378
6F 123478
6F 123789
T1234678
8F
Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2
Figure 3-17. Congener and congener group profiles for air emissions from
the crematoria at Camellia Memorial Lawn Crematorium and Woodlawn
Cemetery.
Source: CARS (1990c); U.S. EPA (1999f).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Figure 3-18. Congener profile for air emissions from the University of
Georgia animal crematorium.
Source: U.S. EPA (2000e).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25 0.3
4D2378
5D 12378
6D 123478
6D 123678
6D 123789
7D 1234678
8D 12346789
4F2378
5F 12378
5F 23478
6F 123478
6F 123678
6F 123789
6F 234678
7F 1234678
7F 1234789
8F 12346789
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.1 0.2 0.3 0.4
4D Total
5D Total
6D Total
7D Total
8D 12346789
4F Total
5F Total
6F Total
7F Total
8F 12346789
Figure 3-19. Congener and congener group profiles for air emissions from
sewage sludge incinerators.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.1 0.2 0.3 0.4 0.5
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-EpCDD
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
Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.1 0.2 0.3 0.4 0.5
Figure 3-20. Congener and congener group profiles for air emissions from a
tire combustor.
Source: CARD (199la); nondetects set equal to zero.
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1 4. COMBUSTION SOURCES OF CDDs/CDFs: POWER/ENERGY GENERATION
2
3 4.1. MOTOR VEHICLE FUEL COMBUSTION
4 Ballschmiter et al. (1986) reported detecting CDDs/CDFs in used motor oil, thus
5 providing some of the first evidence that CDDs/CDFs might be emitted by the combustion
6 processes in gasoline- and diesel-fueled engines. Incomplete combustion and the presence of a
7 chlorine source in the form of additives (such as dichloroethane or pentachlorophenate) in the oil
8 or the fuel were speculated to lead to the formation of CDDs/CDFs. The congener patterns found
9 in the used oil samples were characterized by Ballschmiter et al. as being similar to the patterns
10 found in fly ash and stack emissions from municipal waste incinerators.
11 Since 1986, several studies have been conducted to measure or estimate CDD/CDF
12 concentrations in emissions from vehicles. Although there is no standard approved protocol for
13 measuring CDDs/CDFs in vehicle exhaust, some researchers have developed and implemented
14 several measurement approaches for collecting and analyzing tailpipe emissions. Other
15 researchers have estimated vehicle exhaust emissions of CDDs/CDFs indirectly from studies of
16 tunnel air. The results of these two types of studies are summarized in Sections 4.1.1 and 4.1.2.
17 Estimates of national annual CDD/CDF TEQ emissions from on-road and off-road motor
18 vehicles fueled with leaded gasoline, unleaded gasoline, and diesel fuel based on the results of
19 those studies are presented in Section 4.1.3. It should be noted, however, that relatively few tests
20 on emissions from diesel and unleaded gasoline-fueled vehicles are available, considering the
21 variety and number of such vehicles currently in operation and the range of operational,
22 technical, and environmental conditions in which they are operated. As a result, the emission
23 factors developed in this report for on-road and off-road motor vehicles are quite uncertain.
24
25 4.1.1. Tailpipe Emission Studies
26 Marklund et al. (1987) provided the first direct evidence of the presence of CDDs/CDFs
27 in car emissions from tailpipe measurements on Swedish cars. Approximately 20 to 220 pg I-
28 TEQDF from tetra- and penta-CDDs/CDFs were reported per kilometer driven for four cars
29 running on leaded gasoline. For this study, an unleaded gasoline was used, with tetramethyl lead
30 (0.15 g/L, or 0.57 g/gal) and dichloroethane (0.1 g/L as a scavenger) added. The fuel used may
31 not have accurately represented commercial fuels at that time, which typically contained a
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1 mixture of chlorinated and brominated scavengers (Marklund et al., 1990). Also, the lead
2 content of the fuel used (0.15 g lead/L), although the normal lead content for Swedish fuels at the
3 time, was higher than the lead content of leaded gasoline in the United States during the late
4 1980s (lowered to 0.1 g lead/gal, or 0.026 g lead/L effective January 1, 1986). Marklund et al.
5 (1987) reported a striking similarity between the TCDF and PeCDF congener profiles in the car
6 exhausts and those found in emissions from municipal waste incinerators. For two cars running
7 on unleaded gasoline, CDD/CDF emissions were below the detection limit (DL), which
8 corresponded to approximately 13 pg I-TEQDF/km driven.
9 Table 4-1 presents a summary of the results of Marklund et al. (1987) and subsequent
10 studies, which are discussed below. Tables 4-2 and 4-3 present the results of tailpipe emission
11 studies reported for diesel-fueled trucks and cars, respectively. The results of studies of leaded
12 gasoline-fueled cars are shown in Table 4-4 and those for unleaded gasoline-fueled cars in Tables
13 4-5 and 4-6. Figures 4-1, 4-2, and 4-3 present congener and congener group profiles for
14 emissions from diesel-fueled vehicles, leaded gasoline-fueled vehicles, and unleaded gasoline-
15 fueled vehicles, respectively.
16 Virtually no testing of vehicle emissions for CDDs/CDFs in the United States has been
17 reported. In 1987, the California Air Resources Board (CARB) produced a draft report on the
18 testing of the exhausts of four gasoline-fueled cars and three diesel-fueled vehicles (one truck,
19 one bus, and one car) (CARB, 1987a). However, CARB indicated to EPA that the draft report
20 should not be cited or quoted to support general conclusions about CDDs/CDFs in motor vehicle
21 exhausts because of the small sample size of the study and because the use of low-resolution
22 rather than high-resolution mass spectrometry in the study resulted in high DLs and inadequate
23 selectivity in the presence of interferences (Lew, 1993).
24 CARB stated that the results of a single sample from the heavy-duty diesel truck could be
25 reported, because congeners from most of the homologue groups were present in the sample at
26 levels that could be detected by the analytical method and there were no identified interferences
27 in this sample. This test was conducted under steady-state conditions (50 km/hr) for 6 hr with an
28 engine with a fuel economy of 5.5 km/L. The TEQ emission factor of this one sample was
29 equivalent to 7,190 pg TEQDF-WHO98/L (7,290 pg I-TEQDF/L) of fuel burned. Assuming a fuel
30 economy of 5.5 km/L yields an emission factor of 1,307 pg TEQDF-WHO98/km (1,325 pg I-
31 TEQDF/km). Assuming that nondetect values are zero yields TEQ emission factors of 3,280 pg
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1 TEQDF-WHO98/L (3,720 pg I-TEQDF/L) of fuel burned and 596 pg TEQDF-WHO98/km (676 pg I-
2 TEQDF/km) driven (Lew, 1996).
3 Haglund et al. (1988) sampled exhaust gases from three different vehicles (one car fueled
4 with leaded gasoline and one with unleaded gasoline and a heavy-duty diesel truck) for the
5 presence of brominated dibenzo-^-dioxins (BDDs) and brominated dibenzofurans (BDFs). The
6 authors concluded that the dibromoethane scavenger added to the tested gasoline probably acted
7 as a halogen source. TBDF emissions were measured as 23,000 pg/km in the car with leaded
8 gasoline and 240 pg/km in the car with unleaded gasoline. TBDD and PeBDF emissions were
9 measured as 3,200 and 980 pg/km, respectively, in the car with leaded gasoline. All BDDs/BDFs
10 were below DLs in the diesel truck emissions.
11 Bingham et al. (1989) analyzed the exhausts of four cars using leaded gasoline (uniformly
12 having the following lead and organics content: 0.45 g/L tetramethyl lead, 0.22 g/L
13 dichloroethane, and 0.2 g/L dibromoethane) and the exhaust of one car using unleaded gasoline.
14 Analytical results and DLs were reported for only 5 of the 17 toxic CDD/CDF congeners. TEQ
15 emission rates for the cars using leaded fuel, based on detected congeners only, ranged from 1 to
16 39 pg I-TEQDF/km. CDDs/CDFs were not detected in the exhaust from the vehicle using
17 unleaded fuel; the total TEQ emission rate for this car, based on one-half the DLs for the five
18 reported congeners, was 20 pg I-TEQDF/km.
19 Marklund et al. (1990) tested Swedish cars fueled with commercial fuels, measuring
20 CDD/CDF emissions before and after the muffler. Both new and old vehicles were tested. The
21 tests were done on three cars using unleaded gasoline and two cars using leaded gasoline (0.15 g
22 Pb/L with dichloroethane and dibromoethane scavengers). CDDs/CDFs were not detected in the
23 fuels at a DL of 2 pg I-TEQDF/L but were detected at a level of 1,200 pg I-TEQDF/L in the new
24 semisynthetic engine lube oil used in the engines. The test driving cycle used (31.7 km/hr as a
25 mean speed, 91.2 km/hr as a maximum speed, and 17.9% of time spent idling) yielded fuel
26 economies ranging from approximately 9 to 10 km/L (22 to 24 miles/gal) in the various cars.
27 The reported ranges of emission factors were
28
29 • Leaded gas, before muffler: 2.4 to 6.3 pg I-TEQDF/km (21 to 60 pg I-TEQDF/L of fuel
30 consumed)
31
32 • Leaded gas, in tailpipe: 1.1 to 2.6 pg I-TEQDF/km (10 to 23 pg I-TEQDF/L)
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1 • Unleaded gas, catalyst-equipped, measured in tailpipe: 0.36 pg I-TEQDF/km (3.5 pg
2 I-TEQDF/L)
3
4 • Unleaded gas, before muffler: 0.36 to 0.39 pg I-TEQDF/km (3.5 pg I-TEQDF/L)
5
6 The TEQ levels in exhaust gases from older cars using leaded gasoline were up to six
7 times greater when measured before the muffler than when measured after the muffler. No
8 muffler-related difference was observed in new cars running on leaded gasoline or in old or new
9 cars running on unleaded gasoline.
10 Marklund et al. (1990) also analyzed the emissions of a heavy-duty diesel-fueled truck for
11 CDDs/CDFs. None were detected; however, the authors pointed out that the test fuel was a
12 reference fuel and may not have been representative of commercial diesel fuel. Also, due to
13 analytical problems, a much higher DL (about 100 pg I-TEQDF/L) was realized in this diesel fuel
14 test than in the gasoline tests conducted (5 pg I-TEQDF/L). Further uncertainty was introduced
15 because the diesel emission samples were collected only before the muffler.
16 Hagenmaier et al. (1990) ran a set of tests using conditions comparable to the FTP-73 test
17 cycle on gasoline- and diesel-fueled engines for light-duty vehicles in Germany. The following
18 average TEQ emission rates per liter of fuel consumed were reported:
19
20 • Leaded fuel: 1,287 pg TEQDF-WHO98/L (1,080 pg I-TEQDF/L)
21
22 • Unleaded fuel (catalyst-equipped): 7.9 pg TEQDF-WHO98/L (7.2 pg I-TEQDF/L)
23
24 • Unleaded fuel (not catalyst-equipped): 60.2 pg TEQDF-WHO98/L (50.9 pg I-TEQDF/L)
25
26 • Diesel fuel: 24.8 pg TEQDF-WHO98/L (20.8 pg I-TEQDF/L)
27
28 In 1991, Schwind et al. (1991) published the major findings of a German study of
29 emissions of halogenated dibenzo-p-dioxins and dibenzofurans from internal combustion engines
30 running on commercial fuels. The full report was published in 1992 (Hutzinger et al., 1992).
31 The study was conducted by the universities of Stuttgart, Tubingen, and Bayreuth for the Federal
32 Ministry for Research and Technology, the Research Association for Internal Combustion
33 Engines, and the German Association for the Petroleum Industry and Coal Chemistry. Tests
34 were conducted using engine test benches and rolling test benches under representative operating
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1 conditions. Tests were performed on leaded gasoline engines, unleaded gasoline engines, diesel
2 car engines, and diesel truck engines.
3 The reported range of CDD/CDF emission rates across the test conditions in units of pg I-
4 TEQ/L of fuel consumed are presented below. Tables 4-2 through 4-6 show the results from
5 tests that were not conducted under normal operating conditions with commercial fuels and for
6 which congener-specific emission results were presented in Hutzinger et al. (1992).
7
8 • Leaded fuel: 72 to 1,417 pg TEQDF-WHO98/L (52 to 1,184 pg I-TEQDF/L)
9
10 • Unleaded fuel (not catalyst-equipped): 102 to 181 pg TEQDF-WHO98/L (96 to 177 pg
11 I-TEQDF/L)
12
13 • Unleaded fuel (catalyst-equipped): 9.6 to 28 pg TEQDF-WHO98/L (10 to 26 pg I-
14 TEQDF/L)
15
16 • Diesel fuel (cars): 12 to 140 pg TEQDF-WHO98/L (10 to 130 pg I-TEQDF/L)
17
18 • Diesel fuel (trucks): 79 to 82 pg TEQDF-WHO98/L (70 to 81 pg I-TEQDF/L
19
20 Although no specific details on the methodology used were provided, Hagenmaier (1994)
21 reported that analyses of emissions of a diesel-fueled bus run either on steady-state or on the
22 "Berlin cycle" showed no CDDs/CDFs present at a DL of 1 pg/L of fuel consumed for individual
23 congeners.
24 Gullett and Ryan (1997) reported the results of the first program to sample diesel engine
25 emissions for CDDs/CDFs during actual highway and city driving. The exhaust emissions from
26 a 1991 Freightliner diesel tractor with a 10.3 L, six-cylinder Caterpillar engine—representative of
27 the first generation of computerized fuel-controlled vehicles manufactured in the United
28 States—were sampled during both highway and city routes. The average emission factor for the
29 three highway tests conducted (15.1 pg I-TEQDF/km; range, 11.7 to 18.7 pg I-TEQDF/km;
30 standard deviation, 3.5 pg I-TEQDF/km) was a factor of 3 below the average of the two city
31 driving tests (49.9 pg I-TEQDF/kg; range, 3 to 96.8 pg I-TEQDF/km). DLs were considered to be
32 zero in the calculation of these emission factors. The average of all five tests was 29 pg
33 I-TEQDF/km with a standard deviation of 38.3 pg I-TEQDF/km. This standard deviation reflects
34 the 30-fold variation in the two city driving route tests.
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1 Geueke et al. (1999) analyzed dioxin emissions from heavy-duty vehicle diesel engines in
2 Germany. Table 4-7 depicts the results of the analysis. I-TEQ values ranged from 2 to 18 pg I-
3 TEQ/m3, including one value so high that it could not be reproduced. Miyabara et al. (1999)
4 analyzed CDDs/CDFs found in vehicle exhaust particles from a gasoline engine and a diesel
5 engine in Japan. Table 4-8 presents the data from three tests conducted on the exhaust particles
6 deposited on the tailpipe of the gasoline engine. TEQ values ranged from 3.46 to 5.33 pg I-
7 TEQ/g of exhaust particles. Suspended PM was also collected from an electrostatic precipitator
8 (ESP) connected to a highway tunnel. The I-TEQ for the suspended PM was 242 pg I-TEQ/g,
9 two orders of magnitude higher than the I-TEQ for exhaust particles deposited on the tailpipes.
10 Table 4-9 depicts the data from three tests conducted on the exhaust particles deposited on the
11 tailpipe of the diesel engine. TEQ values ranged from 7.13 to 14 pg I-TEQ/g of soot.
12
13 4.1.2. Tunnel Emission Studies
14 Several European studies and one U.S. study evaluated CDD/CDF emissions from
15 vehicles by measuring the presence of CDDs/CDFs in tunnel air. This approach has the
16 advantage of allowing the random sampling of large numbers of cars with a range of ages and
17 maintenance levels. The disadvantage of this approach is that it relies on indirect measurements
18 (rather than tailpipe measurements), which may introduce bias and make interpretation of the
19 findings difficult. Concerns have been raised that the tunnel monitors are detecting resuspended
20 particulates that have accumulated over time, leading to overestimates of emissions. Also, the
21 driving patterns encountered in these tunnel studies are more or less steady-state driving
22 conditions, which may produce emission levels different from those of the transient driving cycle
23 and cold engine starts that are typical of urban driving conditions. These studies are summarized
24 below in chronological order.
25 Rappe et al. (1988) reported the CDD/CDF content of two air samples (60 m3 per sample)
26 collected from a tunnel in Hamburg, Germany, in January 1986 to be 0.44 and 0.59 pg TEQDF-
27 WHO98/m3 (0.42 and 0.58 pg I-TEQDF/m3). Each sample was collected over a period of about
28 60 hr. The tunnel handled 65,000 vehicles per day, of which 17% were classified as "heavy
29 traffic." The congener-specific results of the two samples are presented in Table 4-10. Ambient
30 air measured in September 1986 at a nearby highway in Hamburg was reported to contain
31 CDD/CDF levels two to six times lower than those measured in the tunnel.
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1 Larssen et al. (1990) and Oehme et al. (1991) reported the results of a tunnel study in
2 Oslo, Norway, performed during April-May of 1988. Oehme et al. estimated total vehicle
3 emissions by measuring CDD/CDF concentrations in tunnel inlet and outlet air of both the uphill
4 and downhill lanes. Emission rates for light-duty and heavy-duty vehicle classes in the uphill
5 and downhill lanes were estimated by counting the number of light-duty and heavy-duty vehicles
6 passing through the tunnel on workdays and a weekend and assuming a linear relationship
7 between the percentage of the light- or heavy-duty traffic and the overall emission rate. Thus, the
8 linear relationship for each emission rate was based on only two points (i.e., the weekday and
9 weekend measurements).
10 The emission rates estimated in this study, in units of Nordic TEQ, are as follows:
11
12 • Light-duty vehicles using gasoline (approximately 70 to 75% using leaded gas):
13 uphill = 520 pg TEQ/km; downhill = 38 pg TEQ/km; mean = 280 pg TEQ/km
14
15 • Heavy-duty diesel trucks: uphill = 9,500 pg TEQ/km; downhill = 720 pg TEQ/km;
16 mean = 5,100 pg TEQ/km
17
18 The mean values are the averages of the emission rates corresponding to the two
19 operating modes: vehicles moving uphill on a 3.5% incline at an average speed of 37 miles per
20 hour (mph) and vehicles moving downhill on a 3.5% decline at an average speed of 42 mph.
21 Although Oehme et al. reported results in units of Nordic TEQ, the results in I-TEQDF should be
22 nearly identical (only about 3 to 6% higher), because the only difference between the two TEQ
23 schemes is the TEF assigned to 1,2,3,7,8-PeCDF (0.1 in Nordic TEQ and 0.05 in I-TEQDF), a
24 minor component of the toxic CDDs/CDFs measured in the tunnel air. Table 4-10 presents the
25 congener-specific differences in concentrations between the tunnel inlet and outlet
26 concentrations.
27 Wevers et al. (1992) measured the CDD/CDF content of air samples taken during the
28 winter of 1991 inside a tunnel in Antwerp, Belgium. During the same period, background
29 concentrations were determined outside the tunnel. Two to four samples were collected from
30 each location with two devices: a standard high-volume sampler with a glass fiber filter and a
31 modified two-phase high-volume sampler equipped with a glass fiber filter and a polyurethane
32 foam (PUF) plug. The I-TEQDF concentration in the air sampled with the filter with PUF device
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1 was 74 to 78% of the value obtained with the high-volume sampler. However, the results
2 obtained from both sets of devices indicated that the tunnel air had a CDD/CDF TEQ
3 concentration about twice as high as that of the outside air (filter with PUF: 80.3 fg I-TEQDF/m3
4 for tunnel air vs. 35 fg I-TEQDF/m3 for outside air; filter only: 100 fg I-TEQDF/m3 for tunnel air
5 vs. 58 fg I-TEQDF/m3 for outside air). The authors presented the congener-specific results for
6 only one tunnel air measurement; these results are presented in Table 4-10.
7 During October-November 1995, Gertler et al. (1996, 1998) conducted a study at the Fort
8 McHenry Tunnel in Baltimore, Maryland. Their stated objective was to measure CDD/CDF
9 emission factors from in-use vehicles operating in the United States, with particular emphasis on
10 heavy-duty vehicles. The air volume entering and leaving the tunnel bore that is used by most of
11 the heavy-duty vehicles (i.e., approximately 25% of the vehicles using the bore are heavy-duty)
12 was measured, and the air was sampled for CDDs/CDFs during seven 12-hr sampling periods.
13 Three of the samples were collected during daytime (6 a.m. to 6 p.m.) and four samples were
14 collected during the night (6 p.m. to 6 a.m.). The air volume and concentration measurements
15 were combined with information on vehicle counts (obtained from videotapes) and tunnel length
16 to determine average emission factors.
17 A total of 33,000 heavy-duty vehicles passed through the tunnel during the seven sample
18 runs (21.2 to 28.8% of all vehicles). The emission factors, calculated on the assumption that all
19 CDDs/CDFs emitted in the tunnel were from heavy-duty vehicles, are presented in Table 4-11.
20 The average TEQ emission factor was reported to be 182 pg TEQDF-WHO98/mile (172 pg I-
21 TEQDF/km). The major uncertainties identified by the study authors were tunnel air volume
22 measurement, sampler flow volume control, and analytical measurement of CDDs/CDFs.
23 EPA's Office of Transportation and Air Quality (OTAQ) reviewed the Gertler et al.
24 (1996) study (Lorang, 1996) and found it to be technologically well done; no major criticisms or
25 comments on the test methodology or protocol were offered, nor did OTAQ find any reason to
26 doubt the validity of the emission factor determined by the study. OTAQ noted that the
27 particulate emission rate for heavy-duty vehicles measured in the study (0.32 g/mile) was lower
28 than the general particulate emission rate used by EPA (about 1 g/mile) and, thus, may
29 underestimate CDD/CDF emissions under different driving conditions. OTAQ cautioned that the
30 reported emission factor should be regarded only as a conservative estimate of the mean emission
31 factor for the interstate trucking fleet under the driving conditions of the tunnel (i.e., speeds on
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1 the order of 50 mph, with those of the entering traffic slightly higher and those of the exiting
2 traffic slightly lower).
3 Figure 4-4 graphically presents the results of the studies by Rappe et al. (1988), Oehme et
4 al. (1991), Wevers et al. (1992), and Gertler et al. (1996, 1998). The figure compares the
5 congener profiles (i.e., congener concentrations or emission factors normalized to total
6 concentration or emission factor of 2,3,7,8-substituted CDDs and CDFs) reported in the four
7 studies. The dominant congeners in the Rappe et al., Wevers et al., and Gertler et al. studies are
8 OCDD; 1,2,3,4,6,7,8-HpCDD; OCDF; and 1,2,3,4,6,7,8-HpCDF. With the exception of OCDD,
9 these congeners are also major congeners reported by Oehme et al. The Oehme et al. study also
10 differs from the other tunnel studies in that the total of 2,3,7,8-substituted CDFs dominates the
11 total of 2,3,7,8-substituted CDDs (by a factor of 2), whereas the other three observed just the
12 opposite.
13
14 4.1.3. National Emission Estimates
15 Estimates of national CDD/CDF TEQ emissions for reference years 1987 and 1995 are
16 presented in this section only for on-road vehicles using gasoline or diesel fuel. For reference
17 year 2000, the Office of Air Quality Planning and Standards (OAQPS) developed national
18 CDD/CDF TEQ emission estimates for on-highway gasoline and diesel vehicles, off-highway
19 gasoline and diesel equipment, diesel railroad equipment, and diesel commercial marine vessels.
20
21 4.1.3.1. Activity Information for On-Road Vehicles
22 Reference year 2000 activity information for on-highway gasoline and diesel vehicles was
23 estimated by OAQPS as county-level vehicle miles traveled (VMT). The estimates include
24 calculations by month, road type, and vehicle type. To develop the VMT, OAQPS relied on the
25 data supplied by the Federal Highway Administration (FHWA).
26 For on-highway gasoline-driven vehicles, OAQPS calculated a national activity level of
27 4,071 billion km for 2000. The activity level for each vehicle type was:
28
29 Vehicle Type Billion km
30 • Light-duty vehicles: 2,574.95
31 • Light-duty trucks 1: 1,004.23
32 • Light-duty trucks 2: 342.79
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1 • Heavy-duty vehicles: 131.97
2 • Motorcycles: 17.70
3
4 For on-highway diesel-fueled vehicles, OAQPS estimated a national activity level of 359
5 billion km for 2000. The activity level for each vehicle type was:
6
7 Vehicle Type Billion km
8 • Light-duty vehicles: 6.44
9 • Light-duty trucks 1: 6.44
10 • 2B-heavy diesel Vehicles: 33.80
11 • Light heavy-duty vehicles: 25.75
12 • Medium heavy-duty vehicles: 59.55
13 • Heavy heavy-duty vehicles: 217.26
14 • Buses heavy-duty vehicles: 9.66
15
16 For reference year 1995, FHWA reported that 1,448 billion total vehicle miles (2,330
17 billion km) were driven by automobiles and motorcycles in the United States. Trucks accounted
18 for 1,271 billion km (790 billion VMT), and buses accounted for 10 billion km (6.4 billion
19 VMT) (U.S. DOC, 1997). In 1992, diesel-fueled trucks accounted for 14.4% of total truck
20 vehicle km driven; gasoline-fueled trucks accounted for the remaining 85.6% (U.S. DOC,
21 1995b). Applying this factor of 14.4% to the 1995 truck estimate of 1,271 billion km results in
22 an estimate of 183 billion km driven by diesel-fueled trucks in 1995.
23 All other vehicle kilometers driven (VKD) (2,947 billion km) are assumed to be by
24 gasoline-fueled vehicles (nondiesel trucks, all automobiles, all buses, and all motorcycles);
25 although a fraction of buses and automobiles use diesel fuel, the exact numbers are not known. It
26 is further assumed that all of these kilometers were driven by unleaded gasoline-fueled vehicles,
27 because in 1992 only 1.4% of the gasoline supply was leaded fuel (EIA, 1993). Use of leaded
28 fuel should have declined further by 1995, because its use in motor vehicles for highway use in
29 the United States was prohibited as of December 31, 1995 (Federal Register, 1985a).
30 For reference year 1987, an estimated 3,092 billion km were driven in the United States,
31 of which trucks accounted for 887 billion km (U.S. DOC, 1995a). In 1987, diesel-fueled trucks
32 accounted for 17.2% of total truck kilometers driven (U.S. DOC, 1995b). Applying this factor of
33 17.2% to the 1987 truck kilometer estimate of 887 billion results in an estimate of 153 billion km
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1 driven by diesel-fueled trucks. All other VKD (2,939 billion) are assumed to have been by
2 gasoline-fueled vehicles. Leaded gasoline accounted for 24.1% of the gasoline supply in 1987
3 (EIA, 1993); thus, 708 billion km are estimated to have been driven by leaded gasoline-fueled
4 vehicles. The remaining 2,231 billion km are estimated to have been driven by unleaded
5 gasoline-fueled vehicles. These mileage estimates are given a high confidence rating because
6 they are based on U.S. Census Bureau transportation studies.
7
8 4.1.3.2. Activity Information for Off-Road Uses
9 Although on-road vehicles are the largest users of gasoline and diesel fuel, certain sectors
10 of the economy account for significant amounts of farm, railroad, marine vessel, and other
11 off-highway uses. Reference year 2000 activity information for off-highway gasoline and diesel
12 equipment was estimated by OAQPs from NONROAD model runs prepared for the National
13 Emissions Inventory. For off-highway gasoline-driven equipment, OAQPS calculated a national
14 activity level of 23,091.01 million liters for 2000. The activity level for each equipment type is:
15
16 Vehicle Type Million Liters
17 • Recreational equipment, 2-stroke engines: 2,032.77
18 • Construction and mining equipment, 2-stroke engines: 102.21
19 • Industrial equipment, 2-stroke engines: 1.14
20 • Lawn and garden equipment, 2-stroke engines: 1,192.40
21 • Agricultural equipment, 2-stroke engines: 3.40
22 • Commercial equipment, 2-stroke engines: 79.49
23 • Logging equipment, 2-stroke engines: 26.50
24 • Recreational equipment, 4-stroke engines: 1,782.93
25 • Construction and mining equipment, 4-stroke engines: 473.18
26 • Industrial equipment, 4-stroke engines: 579.16
27 • Lawn and garden equipment, 4-stroke engines: 8,100.78
28 • Agricultural equipment, 4-stroke engines: 306.62
29 • Commercial equipment, 4-stroke engines: 3,255.45
30 • Logging equipment, 4-stroke engines: 37.85
31 • Airport ground support equipment, 4-stroke engines: 7.57
32 • Industrial equipment, 4-stroke engines, other oil field equipment: 124.92
33 • Pleasure craft, 2-stroke: 3,607.50
34 • Pleasure craft, 4-stroke: 1,374.10
35 • Railroad, 4-stroke: 3.79
36
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1 For off-highway diesel-driven vehicles, diesel railroad equipment, and diesel commercial
2 marine vessels, OAQPS calculated national activity levels of 40,125.37, 12,491.86, and 7,684.39
3 million liters, respectively, for reference year 2000. For diesel commercial marine vessels, the
4 national activity level comprises port emissions (5,905.24 million liters) and underway emissions
5 (1,968.41 million liters). The activity level for each type of diesel railroad equipment is:
6
7 Diesel Locomotive Type Million Liters
8 • Class I locomotives: 10,561.30
9 • Class II/III locomotives: 700.30
10 • Passenger trains: 230.91
11 • Commuter trains: 215.77
12 • Yard locomotives: 794.94
13
14 The following paragraphs define each of the off-road fuel uses listed at the beginning of
15 this section and present distillate fuel sales (in liters) in each sector for reference years 1987 and
16 1995 (EIA, 1992, 1997a). For these sectors, the majority of "distillate fuel" sales are diesel fuels;
17 a small fraction are fuel oils. The activity level information for reference years 1987 and 1995
18 are provided for informational purposes only, as emission estimates for these years could not be
19 calculated due to the lack of emission factors.
20 Farm use includes sales for use in tractors, irrigation pumps, and other agricultural
21 machinery, as well as fuel used for crop drying, smudge pot fuel, and space heating of buildings.
22 Sales were 11,352.45 million liters in 1987 and 13,158.1 liters in 1995.
23 Railroad use includes sales to railroads for any use, including diesel fuel for locomotives
24 and fuel used for heating buildings operated by railroads. Sales were 10,788.42 liters in 1987
25 and 12,980.18 liters in 1995.
26 Marine vessels includes sales for the fueling of commercial or private boats, such as
27 pleasure craft, fishing boats, tug boats, and oceangoing vessels, including vessels operated by oil
28 companies. Excluded are sales to the U.S. Armed Forces. Sales were 7,059.79 liters in 1987 and
29 8,854.08 liters in 1995.
30 Off-highway use includes sales for use in (a) construction equipment, including
31 earthmoving equipment, cranes, stationary generators, air compressors, etc., and (b) sales for
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1 nonconstruction off-highway uses such as logging. Sales were 5,905.24 liters in 1987 and
2 8,225.7 liters in 1995.
3
4 4.1.3.3 Emission Estimates
5 Using the results of the studies discussed in Section 4.1.1, separate national annual
6 emission estimates are developed below for vehicles burning leaded gasoline, unleaded gasoline,
7 and diesel fuel.
8 Leaded gasoline. The literature indicates that CDD/CDF emissions occur from full
9 combustion in vehicles using leaded gasoline and that considerable variation occurs depending,
10 at least in part, on the types of scavengers used. Marklund et al. (1987) reported emissions
11 ranging from 20 to 220 pg I-TEQDF/km from four cars fueled with a reference unleaded fuel to
12 which lead (0.5 g/leaded gal) and a chlorinated scavenger were added. Marklund et al. (1990)
13 reported much lower emissions in the exhaust of cars using a commercial leaded fuel (0.5 g/L)
14 containing both dichloroethane and dibromoethane as scavengers (1.1 to 6.3 pg I-TEQDF/km).
15 The difference in the emission measurements in the 1987 and 1990 studies was attributed to the
16 different mix of scavengers used in the two studies, which may have resulted in preferential
17 formation of mixed chlorinated and brominated dioxins and furans.
18 Hagenmaier et al. (1990) reported TEQ emissions of 1,080 pg I-TEQDF/L of fuel
19 (approximately 129 pg TEQDF-WHO98/km [108 pg I-TEQDF/km]) from a car fueled with a
20 commercial leaded fuel (lead content not reported). Bingham et al. (1989) reported emissions
21 ranging from 1 to 39 pg I-TEQDF/km from four cars using gasoline with a lead content of 1.7 g/L
22 in New Zealand. The German study reported by Schwind et al. (1991) and Hutzinger et al.
23 (1992) measured emissions of 52 to 1,184 pg I-TEQDF/L (approximately 7.2 to 142 pg TEQDF-
24 WHO98/km [5.2 to 118 pg I-TEQDF/km]) for cars under various simulated driving conditions.
25 The tunnel study by Oehme et al. (1991) estimated that emissions from cars running primarily on
26 leaded gasoline (70 to 75% of the cars) ranged from 38 to 520 pg Nordic TEQ/km.
27 The average emission factor (see Table 4-4) is 532 pg TEQDF-WHO98/L (450 pg I-
28 TEQDF/L), as reported for the tailpipe emission studies performed using commercial leaded fuel
29 (Marklund et al., 1990; Hagenmaier et al., 1990; Schwind et al., 1991), which presented
30 analytical results for all 17 toxic CDD/CDF congeners. Assuming an average fuel economy of
31 10 km/L, this emission factor is approximately 53 pg TEQDF-WHO98/km (45 pg I-TEQDF/km). A
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1 low confidence rating is assigned to this emission factor because it is based on European fuels
2 and emission control technologies, which may have differed from U.S. leaded-fuel and engine
3 technologies, and because the factor is based on tests with only nine cars.
4 Combining the average emission factor developed above (53 pg TEQDF-WHO98/km [45
5 pg I-TEQDF/km], assuming nondetect values are zero) with the estimate for kilometers driven by
6 leaded gasoline-fueled vehicles in 1987 (708 billion km) suggests that 37.5 g TEQDF-WHO98
7 (31.9 g I-TEQDF) were emitted from vehicles using leaded fuels in 1987. Although some on-road
8 vehicles used leaded fuel in 1995, further use of leaded fuel in motor vehicles for highway use in
9 the United States was prohibited as of December 31, 1995 (Federal Register, 1985a). In 1992,
10 the last year for which data are available on consumption of leaded gasoline by on-road vehicles,
11 only 1.4% of the gasoline supply was leaded gasoline (EIA, 1993). A conservative assumption
12 that 1% of the total VKD in 1995 (29.5 billion km of a total of 2,947 billion km) was leaded
13 gasoline-fueled vehicles, in conjunction with the emission factor of 53 pg TEQDF-WHO98/km (45
14 pg I-TEQDF/km), yields an annual emission of 1.6 g TEQDF-WHO98 (1.3 g I-TEQDF) in 1995.
15 These emission estimates are assigned a low confidence rating on the basis of the low rating for
16 the emission factor.
17 Unleaded gasoline. The literature documenting results of European studies indicates that
18 CDD/CDF emissions from vehicles burning unleaded fuels are lower than emissions from
19 vehicles burning leaded gas with chlorinated scavengers. It also appears, based on the limited
20 data available, that catalyst-equipped cars have lower emission factors than do noncatalyst-
21 equipped cars. Marklund et al. (1987) did not detect CDDs/CDFs in emissions from two
22 catalyst-equipped cars running on unleaded gasoline at a DL of 13 pg I-TEQDF/km. Marklund et
23 al. (1990) reported emission factors of 0.36 and 0.39 pg I-TEQDF/km for two noncatalyst-
24 equipped cars and an emission factor of 0.36 pg I-TEQDF/km for one catalyst-equipped car.
25 Hagenmaier et al. (1990) reported an emission factor of 5.1 pg I-TEQDF/km for one noncatalyst-
26 equipped car and 0.7 pg I-TEQDF/km for one catalyst-equipped car. Schwind et al. (1991) and
27 Hutzinger et al. (1992) reported emission factors of 9.6 to 17.7 pg I-TEQDF/km for several
28 noncatalyst-equipped cars tested under various conditions; the reported emission factor range for
29 catalyst-equipped cars was 1 to 2.6 pg I-TEQDF/km.
30 All automobiles running on unleaded gasoline in the United States are equipped with
31 catalysts. The average emission factor reported for the tailpipe emission studies performed on
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1 catalyst-equipped cars (Hagenmaier et al. 1990; Schwind et al., 1991; Hutzinger et al., 1992) is
2 15.6 pg TEQDF-WHO98/L (14.9 pg I-TEQDF/L) (see Table 4-6). A low confidence rating is
3 assigned to this emission factor because the European fuels and emission control technology used
4 may have differed from U.S. fuels and technology and also because the emission factor range is
5 based on tests with only three catalyst-equipped cars.
6 OAQPS calculated emissions for reference year 2000 for dioxins and furans from
7 gasoline-fueled vehicles using the final version of the MOBILE6 model. On-road emissions
8 were calculated by converting the emission factor of 15.6 pg TEQDF-WHO98/L (14.9 pg I-
9 TEQDF/L) to a milligram per mile basis using a conversion factor of 3.78e-09 and assuming a
10 fuel economy of 21.5 miles/gal. The new emission factor was then multiplied by the
11 corresponding county-level VMT in miles per year. The off-highway gasoline equipment
12 emission estimates for reference year 2000 were developed by multiplying the mean emission
13 factor of 15.6 pg TEQDF-WHO98/L (14.9 pg I-TEQDF/L) by 2000 activity estimates developed
14 from NONROAD model runs prepared for the National Emissions Inventory. The activity
15 estimates represent county-level gasoline consumption in gallons. The emission factor was
16 converted from pg/L to mg/gallon by multiplying by a conversion factor of 3.78e-09. The use of
17 these methodologies resulted in national estimates for reference year 2000 of 7 g TEQDF-WHO98
18 (6.7 g I-TEQDF) for on-highway gasoline vehicles and 0.36 g TEQDF-WHO98 (0.35 g I-TEQDF) for
19 off-highway gasoline equipment.
20 Applying the same emission factors from Gertler et al. (1996, 1998) and assuming an
21 average fuel economy of 10 km/L yields an emission factor of 1.6 pg TEQDF-WHO98/km (1.5 pg
22 I-TEQDF/km). Applying this emission factor to the estimate derived for VKD in 1995 by all
23 gasoline-fueled vehicles (2,947 billion km) suggests that 4.7 g TEQDF-WHO98 (4.4 g I-TEQDF)
24 were emitted from vehicles using unleaded fuels in 1995. Applying the same emission factors to
25 the estimate derived above for VKD in 1987 by unleaded gasoline-fueled vehicles (2,231 billion
26 km) suggests that 3.6 g TEQDF-WHO98 (3.3 g I-TEQDF) may have been emitted in 1987. The
27 emission estimates for all reference years were assigned a low confidence rating on the basis of
28 the low rating given to the emission factor.
29 Diesel fuel. Limited data are available upon which to base an evaluation of the extent of
30 CDD/CDF emissions resulting from diesel fuel combustion, and these data address only
31 emissions from on-road vehicles; no emissions data are available for off-road diesel uses
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1 (construction vehicles, farm vehicles, and stationary equipment). Two U.S. tailpipe studies have
2 been reported: CARS (1987a) and Gullett and Ryan (1997). CARS reported a relatively high
3 emission factor of 676 pg I-TEQDF/km (nondetect values assumed to be zero) for one heavy-duty
4 truck with a fuel economy of 5.5 km/L at 50 km/hr. Gullett and Ryan reported a range of
5 emission factors for one diesel truck tested on six highway or city driving routes of 3 to 96.8 pg
6 I-TEQDF/km (mean of 29 pg I-TEQDF/km).
7 The results of several tailpipe studies conducted in Europe have also been published.
8 Marklund et al. (1990) reported no emissions at a detection limit of 100 pg I-TEQDF/L (or 18 pg
9 I-TEQDF/km, assuming a fuel economy of 5.5 km/L) for one tested truck. Schwind et al. (1991)
10 and Hutzinger et al. (1992) reported emission factors of 32 to 81 pg I-TEQDF/L (or 6 to 15 pg I-
11 TEQDF/km, assuming a fuel economy of 5.5 km/L) for a truck engine run under various simulated
12 driving conditions. Hagenmaier (1994) reported no emissions from a bus at a detection limit of 1
13 pg/L of fuel consumed for individual congeners. For diesel-fueled cars, Hagenmaier et al. (1990)
14 reported an emission factor of 24 pg I-TEQDF/L (or approximately 2.4 pg I-TEQDF/km) for one
15 tested car. Schwind et al. and Hutzinger et al. reported emission factors of 5 to 13 pg I-
16 TEQDF/km for a car engine run under various simulated driving conditions.
17 The tunnel study by Oehme et al. (1991) generated an estimated mean emission factor of
18 5,100 pg TEQ/km and a range of 720 to 9,500 pg TEQ/km (in units of Nordic TEQ) for diesel-
19 fueled trucks. Insufficient information was provided in Oehme et al. to enable an exact
20 calculation of emissions in units of I-TEQDF or TEQDF-WHO98. However, based on the
21 information that was provided, the mean emission factor in units of TEQ is approximately 5,250
22 to 5,400 pg I-TEQDF/km. These indirectly estimated emission factors are considerably larger than
23 those reported in engine studies by Marklund et al. (1990), Schwind et al. (1991), and Hutzinger
24 et al. (1992); the CARB (1987a) diesel truck emission factor falls at the low end of the range.
25 Although aggregate samples representing several thousand heavy-duty diesel vehicles
26 were collected in Oehme et al. (1991), several characteristics of the study introduce considerable
27 uncertainty with regard to the use of the study's results as a basis for estimating emissions in the
28 United States: (a) heavy-duty vehicles represented only 3 to 19% of total vehicle traffic in the
29 tunnel; (b) the majority of the light-duty vehicles were fueled with leaded gasoline, the
30 combustion of which, as noted in Table 4-4, can release considerable amounts of CDD/CDFs;
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1 and (c) technology differences likely existed between the 1988 Norwegian and the 1987 and
2 1995 U.S. vehicle fleets.
3 The tunnel study conducted in Baltimore, Maryland, by Gertler et al. (1996, 1998) shares
4 the disadvantages of all tunnel studies relative to studies that directly measured CDDs and CDFs
5 in tailpipe emissions. Specifically, tunnel studies rely on indirect measurements (rather than
6 tailpipe measurements), which may introduce bias, and the emission factors calculated from
7 these studies reflect driving conditions of only the vehicle fleet using the tunnel and not
8 necessarily of the overall vehicle fleet under other driving conditions.
9 However, the Gertler et al. study does have strengths that are lacking in the Oehme et al.
10 (1991) tunnel study, and it has advantages over the two U.S. diesel truck tailpipe studies,
11 including: (a) the study was conducted in the United States (fairly recently) and thus reflects
12 current U.S. fuels and technology, (b) virtually no vehicle using the tunnel used leaded gasoline,
13 (c) the tunnel walls and streets were cleaned 1 week prior to the start of sampling and, in
14 addition, the study analyzed road dust and determined that resuspended road dust contributed
15 only about 4% of the estimated emission factors, (d) heavy-duty vehicles comprised, on average,
16 a relatively large percentage (25.7%) of vehicles using the tunnel, and (e) a large number of
17 heavy-duty vehicles—approximately 33,000—passed through the tunnel during the sampling
18 period, which generates confidence that the emission factor is representative of interstate trucks.
19 Considering the strengths and weaknesses of the available emission factor data from the
20 tailpipe and tunnel studies, the mean TEQ emission factor reported by Gertler et al. (1996,
21 1998)—182 pg TEQDF-WHO98/km (172 pg I-TEQDF/km)—is assumed to represent the best
22 current estimate of the average emission factor for on-road diesel-fueled trucks. This emission
23 factor is assigned a low confidence rating because it may not be representative of emission rates
24 for the entire fleet of diesel-fueled trucks under the wide array of driving conditions encountered
25 on the road.
26 For reference year 2000, OAQPS developed national CDD/CDF TEQ emission estimates
27 for on-highway diesel vehicles, off-highway diesel equipment, diesel railroad equipment, and
28 diesel commercial marine vessels. For on-highway diesel vehicles, OAQPS combined the
29 calculated mean emission factors from Gertler et al. (1996, 1998) with the OAQPS estimate for
30 vehicle miles driven. The pg/km emission factors were first converted to a mg/mile basis using a
31 conversion factor of 1.61e-09. OAQPS estimated national emissions of 65.4 g TEQDF-WHO98
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1 (61.7 g I-TEQDF) from on-highway diesel-fueled vehicles for reference year 2000. For all years
2 the emissions from diesel vehicles were assigned a low confidence rating because the emission
3 factors were assigned a low confidence rating.
4 For off-highway diesel equipment, OTAQ developed the NONROAD emissions model
5 to estimate emissions from nonroad (off-road) equipment types. However, the NONROAD
6 model does not contain emission factors for calculating CDD/CDF emissions. To calculate 2000
7 emissions, OAQPS estimated fuel consumption, as reported by the May 2002 "Lockdown C"
8 draft version of NONROAD, and multiplied this estimate by an average fuel efficiency of
9 7 miles/gal and the emission factor from Gertler et al. (1996, 1998). The NONROAD model
10 does not contain activity estimates for commercial marine vessels and railroad equipment.
11 OAQPS developed estimates for county-level diesel consumption, in gallons, for diesel
12 commercial marine vessels and diesel railroad equipment, and multiplied these estimates by an
13 average fuel efficiency of 7 miles/gal and the emission factor from Gertler et al. (1996, 1998).
14 The results from using these methodologies suggest that 22 g TEQDF-WHO98 (21 g of I-TEQDF),
15 4.3 g TEQDF-WHO98 (4 g of I-TEQDF), and 6.8 g TEQDF-WHO98 (6.4 g of I-TEQDF) were emitted
16 from off-highway diesel equipment, diesel commercial marine vessels, and diesel railroad
17 equipment, respectively, in reference year 2000.
18 The use of the same emission factors from Gertler et al. (1996, 1998) and an assumption
19 of an average fuel economy of 10 km/L results in an emission factor of 1.6 pg TEQDF-WHO98/km
20 (1.5 pg I-TEQDF/km). Applying this factor to the estimate for VKD in 1995 in the United States
21 by diesel-fueled trucks (183 billion km) suggests that 33.3 g TEQDF-WHO98 (31.5 g of I-TEQDF)
22 were emitted from diesel-fueled trucks in 1995. Combining the same emission factors with the
23 estimate derived above for VKD in 1987 by diesel-fueled trucks (153 billion km) suggests that
24 27.8 g TEQDF-WHO98 (26.3 g of I-TEQDF) were emitted from diesel-fueled trucks in 1987.
25 For 1987 and 1995 off-road diesel emissions, EPA used the emission factor from Gertler
26 et al. (1996, 1998) and multiplied it by an average fuel efficiency of 2.98 km/L (U.S. EPA,
27 2003d) and a conversion factor of 1.61E-09 g-km/pg-mile to obtain emission factors of 0.51 ng I-
28 TEQDF/L and 0.54 ng TEQDF-WHO98/L. These emission factors are assigned a low confidence
29 rating because they possibly are nonrepresentative of the source. Multiplying these emission
30 factors by the 1987 activity factors for off-highway equipment (17,278.61 million liters), marine
31 vessels (7,068.35 million liters), and railroad use (10,801.5 million liters), EPA estimates the
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1 following emissions for 1987: 8.8 g of I-TEQDF (9.4 g TEQDF-WHO98) for off-highway
2 equipment; 3.6 g of I-TEQDF (3.8 g TEQDF-WHO98) for marine vessels; and 5.5 g of I-TEQDF (5.8
3 g TEQDF-WHO98) for railroad use. Similarly, using the 1995 activity factors for off-highway
4 equipment (21,409.71 million liters), marine vessels (8,864.81 million liters), and railroad use
5 (12,995.91 million liters), EPA estimates the following emissions for 1995: 11 g of I-TEQDF (12
6 g TEQDF-WHO98) for off-highway equipment; 4.5 g of I-TEQDF (4.8 g TEQDF-WHO98) for marine
7 vessels; and 6.6 g of I-TEQDF (7 g TEQDF-WHO98) for railroad use. These emission estimates are
8 given a low confidence rating because the emission factor may possibly be nonrepresentative of
9 the source.
10
11 4.2. WOOD COMBUSTION
12 For the reference year 1987, wood energy consumption is estimated to have been 2,437
13 trillion British thermal units (Btu), or 3.2% of total primary energy consumed in the United
14 States. In 1995, wood fuel (including black liquor solids) provided about 2.6% (2,350 trillion
15 Btu) of the total primary energy consumed (EIA, 1997b). Wood energy consumption in 2000 is
16 estimated to have been 2,473 trillion Btu, or 2.5% of the total primary energy consumed (EIA,
17 2003a). The industrial sector is the largest consumer of wood fuel, accounting for 65% of total
18 wood fuel consumption in 1987, 72% in 1995, and 80% in 2000. The residential sector
19 accounted for 35% of total wood fuel consumption in 1987, 25% in 1995, and 18% in 2000. The
20 commercial sector accounted for approximately 2% of total wood fuel consumption in all three
21 reference years (EIA, 2003a).
22 These energy consumption estimates appear to include the energy value of black liquor
23 solids, which are combusted in recovery boilers by wood pulp mills. In 1987, 1995, and 2000,
24 the energy values of combusted black liquor solids were 950, 1,078, and 998 trillion Btu,
25 respectively (American Paper Institute, 1992; American Forest and Paper Association, 1997;
26 Gillespie, 2002). Subtracting the estimates of black liquor energy values from the 1987, 1995,
27 and 2000 national totals for wood fuel yields 1,487, 1,272, and 1,475 trillion Btu, respectively.
28 Assuming that 1 kg of oven-dried wood (2.15 kg of green wood) provides approximately 19,000
29 Btu (EIA, 1994), an estimated 78.3, 66.9, and 77.6 million metric tons of oven-dried wood
30 equivalents were burned for energy purposes in 1987, 1995, and 2000, respectively. Of these
31 totals, an estimated 44.8, 31.4, and 23 million metric tons were consumed by the residential
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1 sector in 1987, 1995, and 2000, respectively. An estimated 33.2, 32.6, and 51.5 million metric
2 tons were consumed by the industrial sector in 1987, 1995, and 2000, respectively.
3 The following subsections discuss the results of relevant emission studies for the
4 residential and industrial sectors and present annual TEQ emission estimates for reference years
5 1987, 1995, and 2000.
6
7 4.2.1. Flue Emissions From Wood Combustion (Residential)
8 Several studies have provided direct measurement of CDDs/CDFs in flue gas emissions
9 from wood-burning stoves and fireplaces (Schatowitz et al., 1993; Vikelsoe et al., 1993;
10 Bremmer et al., 1994; Broker et al., 1992; Launhardt and Thoma, 2000; Environment Canada,
11 2000). The findings of each of these studies are summarized below.
12
13 4.2.1.1. Emissions Data
14 Schatowitz et al. (1993) measured the CDD/CDF content of flue gas emissions from
15 several types of wood burners used in Switzerland: a household stove (6 kW), automatic chip
16 furnaces (110 to 1,800 kW), and a wood stick boiler (35 kW). The emissions from combustion
17 of a variety of wood fuels were measured (natural beech wood, natural wood chips, uncoated
18 chipboard chips, waste wood chips from building demolition, and household paper and plastic
19 waste). The results from the testing of the household stove are most relevant for assessing
20 releases from residential combustion. The household stove was tested with the stove door both
21 open and closed. The open-door stove can be assumed to be representative of fireplaces because
22 both have an uncontrolled draft. Although the congener and congener group analytical results
23 were not reported, the following emission factors (dry weight for wood, wet weight for
24 household waste) and emission rates (corrected to 13% oxygen) for the household stoves and
25 furnaces were reported.
26
27 Stoves
28
29 • Open-door burn of beech wood sticks: 0.77 ng I-TEQDF/kg
30 (0.064 ng I-TEQDF/Nm3)
31
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1 • Closed-door burn of beech wood sticks: 1.25 ng I-TEQDF/kg
2 (0.104ng I-TEQDF/Nm3)
3
4 • Closed-door burn of household waste: 3,230 ng I-TEQDF/kg
5 (114.4ngI-TEQDF/Nm3)
6
7 Furnaces
8
9 • Natural wood chips: 0.79 to 2.57 ng I-TEQDF/kg
10
11 • Chipboard chips (uncoated): 0.29 to 0.91 ng I-TEQDF/kg
12
13 • Waste wood chips from building demolition: 26 to 173.3 ng I-TEQDF/kg
14
15 Vikelsoe et al. (1993) studied emissions of CDD/CDF congener groups from residential
16 wood stoves in Denmark. The wood fuels used in the experiments were seasoned birch, beech,
17 and spruce, equilibrated to 18% absolute moisture. Four different types of stoves (including one
18 experimental stove) were evaluated under both normal and optimal operating conditions (i.e.,
19 well-controlled, with carbon monoxide emissions as low as possible). Total CDD/CDF
20 emissions varied widely for the 24 different fuel/stove type/operating condition combinations.
21 Emissions from spruce were about twice as high as those from birch and beech. Surprisingly, the
22 optimal operating condition led to significantly higher CDD/CDF emissions for two stove types
23 but not for the other stoves. The predominant congener group for all experiments was TCDF.
24 The weighted average emission factor and flue gas concentration for wood stoves (considering
25 wood and stove types) were reported to be 1.9 and 0.18 ng Nordic TEQ/Nm3, respectively.
26 Because Vickelsoe et al. did not measure congener levels, the reported emission factor and
27 emission rate were estimated by assuming the same congener distribution in each congener group
28 that had been found for municipal waste incinerators.
29 Bremmer et al. (1994) reported results of testing performed with a cast-iron wood-
30 burning stove with a combustion chamber lined with fire refractory clay. Measurements were
31 conducted at three loads (maximum, average, and minimum) using clean wood as fuel. The
32 emission factors ranged from 1 to 3.3 ng I-TEQDF/kg (average of about 2.2 ng I-TEQDF/kg).
33 Bremmer et al. also reported results of testing conducted with a fireplace of a type that is
34 common in the Netherlands. Measured emission factors from the burning of clean wood ranged
35 from 13 to 28.5 ng I-TEQDF/kg (average of about 20 ng I-TEQDF/kg). The authors noted that the
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1 measured emission factors for fireplaces were considerably higher than those reported by others
2 (see Broker et al., 1992, below) and assigned "great uncertainty" to the emission factors.
3 Broker et al. (1992) reported results of a series of three tests with a wood stove and a
4 fireplace. The average, minimum, and maximum emission factors measured for the wood stove
5 tests ranged from 0.53 to 0.94 ng I-TEQDF/kg. The geometric mean of the two average values
6 was 0.71 ng I-TEQDF/kg. The average of the minimum and maximum emission factors measured
7 for the fireplace tests ranged from 0.2 to 1.06 ng I-TEQDF/kg. The geometric mean of these two
8 average values is 0.46 ng I-TEQDF/kg.
9 Launhardt and Thoma (2000) conducted an investigation on organic pollutants from a
10 domestic heating system using various solid biofuels. Tests were conducted using a multifuel
11 furnace designed for domestic applications. Table 4-12 shows the average dioxin concentration
12 in the flue gas for the four fuels used: spruce wood, wheat straw, hay, and triticale. The
13 concentrations in the flue gas range from 52 to 891 pg TEQ/m3.
14 Environment Canada (2000) conducted a study on the release of dioxins and furans into
15 the atmosphere by residential wood combustors. The study analyzed two wood stoves believed
16 to be representative of stoves used in Canada: a conventional wood stove that was popular in the
17 early 1980s and an advanced combustion, noncatalytic, EPA-certified wood stove. Each stove
18 was tested using hard maple and black spruce wood. Results from the study ranged from 0.222
19 to 0.952 ng I-TEQ/kg wood (see Table 4-13). Because these tests took place in North America
20 using indigenous wood and they included the analysis of an EPA-certified wood stove, the mean
21 value of the Environment Canada study (0.5 ng I-TEQ/kg wood) will be used to determine the
22 national emission estimate for residential burning of clean wood in fireplaces and stoves. This
23 emission factor is assigned a low confidence rating because it is judged to be nonrepresentative
24 of all residential wood combustion (e.g., home fireplaces).
25 Several studies have reported that combustion of treated or manufactured wood in stoves
26 and fireplaces can result in significantly higher CDD/CDF emission factors. A few researchers
27 (e.g., Vikelsoe et al., 1993) have reported high CDD/CDF emission rates when
28 pentachlorophenol (PCP)-contaminated wood is combusted in residential wood stoves and
29 furnaces. The European Inventory (Quab and Fermann, 1997) used the results of these studies to
30 derive best estimates of CDD/CDF emission factors for combustion of "slightly contaminated
31 wood (excluding PCP)" and "PCP-contaminated wood" to be 50 and 500 ng I-TEQDF/kg,
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1 respectively. Although it is likely that there is some residential combustion of these types of
2 wood in the United States, there are no corresponding activity level data upon which to base a
3 national annual estimate of emissions.
4
5 4.2.1.2. Activity Level Information
6 In 1987, 22.5 million households in the United States burned wood (EIA, 1991). Wood
7 was used as the primary heating fuel in 5 million of those households and as a secondary source
8 for aesthetic purposes (i.e., in fireplaces) in 17.4 million (EIA, 1991, 1997b). Lower numbers
9 were reported for 1995: wood was reported to be used as the primary fuel in only 3.53 million
10 households (EIA, 1997b). More rural low-income households consumed wood as a primary
11 heating fuel than did other sectors of the population. The majority of these households used
12 wood-burning stoves as the primary heating appliance. Although fireplaces were the most
13 common type of wood-burning equipment in the residential sector, only 7% of fireplace users
14 reported using fireplaces for heating an entire home (EIA, 1991, 1994).
15 In 1987, residential wood consumption was 852 trillion Btu (44.8 million metric tons),
16 or 35% of total U.S. consumption (EIA, 1997b). Residential wood consumption in 1995 was 596
17 trillion Btu (31.4 million metric tons), or 25% of total U.S. wood energy consumption (EIA,
18 1997b). The Energy Information Administration (EIA) estimated that 433 trillion Btu (23
19 million metric tons) of wood were consumed in residences in 2000 (EIA, 2003b). These
20 production estimates are given high confidence ratings because they are based on recent
21 government survey data.
22 OAQPS developed emission estimates for residential wood combustion from the results
23 of a study by EPA's Emission Factor and Inventory Group (U.S. EPA, 2001d). The activity data
24 for residential wood combustion were based on the type of combustion unit. Activity data for
25 wood stoves and fireplaces with inserts were estimated on the basis of total amount of wood
26 consumed in a year. OAQPS used 1997 national activity data to extrapolate an estimate for 1999
27 by applying a growth rate factor based on wood energy consumption data from EIA. Activity
28 data for fireplaces were estimated on the basis of number of homes in the U. S. with usable
29 fireplaces, as reported by the U.S. Census Bureau.
30 OAQPS assumed that the extent of wood consumption in residential combustion units is
31 directly related to ambient temperature (with more wood consumption in colder climates).
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1 Historical climate data were used to assign each U.S. county to one of five climate zones, as
2 defined by the National Climatic Data Center. Each climate zone was then assigned a percentage
3 of total national wood consumption on the basis of information contained in the EIA's
4 Residential Energy Consumption database.
5 The consumption in each climate zone was then allocated to individual counties in that
6 zone. Each county was designated as urban or rural to reflect unit location preferences reported
7 in the 1999 American Housing Survey, which estimated that 68% of fireplaces are found in urban
8 areas, compared with 32% in rural areas. An estimated 69% of wood stoves are found in rural
9 areas, compared with 31% in urban areas. Fireplaces with inserts were evenly split between
10 urban and rural areas. In each zone, the total urban and rural county wood consumption was
11 summed and an adjustment was made within the zone for each county's consumption if the urban
12 and rural totals did not match the expected percentage. These steps resulted in final cordwood
13 consumption by county, which was converted to tons of wood consumed using a conversion
14 factor of one cord of wood equaling 1.163 tons.
15 Wood consumption estimates for stoves and fireplaces with inserts were further
16 categorized to account for the different designs of units that exist in the marketplace. Different
17 designs of stoves and inserts have been found to have different levels of emissions. According to
18 data received from the Hearth Products Association, the three primary types of units currently in
19 use are noncertified (92% of the stoves manufactured), certified noncatalytic (5.7%), and
20 certified catalytic (2.3%). These proportions were applied to the national, state, and county
21 cordwood consumption estimates prior to the application of emission factors.
22 Activity level estimates in million metric tons per year for each wood combustion
23 category are:
24
25 • Fireplaces: 2.79 million metric tons/yr
26 • Fireplaces with inserts, certified catalytic: 0.92 million metric tons/yr
27 • Fireplaces with inserts, certified noncatalytic: 0.47 million metric tons/yr
28 • Fireplaces with inserts, noncertified: 7.64 million metric tons/yr
29 • Noncatalytic wood stoves: 0.26 million metric tons/yr
30 • Catalytic wood stoves: 0.64 million metric tons/yr
31 • Conventional wood stoves: 10.60 million metric tons/yr
32
33
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1 4.2.1.3. Emission Estimates
2 The emission factor used to determine national emission estimates (0.5 ng I-TEQ/kg
3 wood) was obtained from Environment Canada (2000) because it was the most comprehensive
4 and recent study.
5 Combining the best estimate of the emission factor (0.5 ng I-TEQDF/kg wood) with the
6 mass of wood consumed in residences in 1987, 1995, and 2000 yields annual TEQ air emissions
7 from this source of approximately 22, 15.7, and 11.3 g I-TEQDF, respectively. These estimates
8 are given a low confidence rating for all years because the emission factor was judged to be of
9 low confidence.
10
11 4.2.2. Stack Emissions From Wood Combustion (Industrial)
12 4.2.2.1. Emissions Data
13 Congener-specific measurements of CDDs/CDFs in stack emissions from industrial
14 wood-burning furnaces were measured by CARB at four facilities in 1988 (CARB, 1990b, e, f,
15 g). Measurements of CDD/CDF congener groups and 2,3,7,8-TCDD and 2,3,7,8-TCDF were
16 reported for one facility by EPA (U.S. EPA, 1987a). The National Council of the Paper Industry
17 for Air and Stream Improvement (NCASI) presented congener-specific emission factors for five
18 boilers tested during burns of bark and wood residue (NCASI, 1995). The average congener-
19 specific emission factors derived from the four CARB and five NCASI studies are presented in
20 Table 4-14. Average congener and congener group profiles are presented in Figure 4-5a for the
21 four CARB studies and in Figure 4-5b for the five NCASI studies.
22 CARB (1990b) measured CDDs/CDFs in the emissions from a quad-cell wood-fired
23 boiler used to generate electricity. The fuel consisted of coarse wood waste and sawdust from
24 nonindustrial logging operations. The exhaust gases passed through a multicyclone before
25 entering the stack. From this study, the average TEQ emission factor for total CDDs/CDFs was
26 calculated to be 0.64 ng I-TEQDF/kg of wood burned.
27 In the second study (CARB, 1990e), CDDs/CDFs in the emissions from two spreader-
28 stoker wood-fired boilers operated in parallel by an electric utility for generating electricity were
29 measured. The exhaust gas stream from each boiler was passed through a dedicated ESP, after
30 which the gas streams were combined and emitted to the atmosphere through a common stack.
31 Stack tests were conducted when the facility burned fuels allowed by existing permits and when
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1 it burned a mixture of permitted fuel supplemented by urban wood waste at a ratio of 7:3. From
2 this study, the average TEQ emission factor for total CDDs/CDFs was calculated to be 0.82 ng I-
3 TEQDF/kg of wood burned.
4 In the third study (CARS, 1990f), CDDs/CDFs in the emissions from twin fluidized-bed
5 combustors designed to burn wood chips for the generation of electricity were measured. The air
6 pollution control device (APCD) system consisted of ammonia injection for controlling nitrogen
7 oxides and a multicyclone and ESP for controlling PM. During testing, the facility burned wood
8 wastes and agricultural wastes allowed by existing permits. From this study, the average TEQ
9 emission factor for total CDDs/CDFs was calculated to be 1.32 ng I-TEQDF/kg of wood burned.
10 In the fourth study (CARB, 1990g), CDDs/CDFs in the emissions from a quad-cell wood-
11 fired boiler were measured. During testing, the fuel consisted of wood chips and bark. The flue
12 gases passed through a multicyclone and an ESP before entering the stack. From this study, the
13 average TEQ emission factor for total CDDs/CDFs was calculated to be 0.5 ng I-TEQDF/kg of
14 wood burned.
15 NCASI (1995) presented stack emission test results for five boilers burning bark or wood
16 residues. One of these facilities, equipped with a multicyclone, normally burned bark in
17 combination with sludge and coal. Another facility, equipped with an ESP, normally fired
18 pulverized coal. The other three facilities were spreader-stokers equipped with multicyclones or
19 ESPs. Although stack gas flow rates were obtained during these tests, accurate measurements of
20 the amounts of bark and wood fired were not made and had to be estimated from steam
21 production rates. The average TEQ emission factor for these facilities was 0.46 ng TEQDF-
22 WHO98/kg (0.4 ng I-TEQDF/kg of feed).
23 The mean of the emission factors derived from the four CARB studies and five NCASI
24 studies—0.6 ng TEQDF-WHO98/kg wood (0.56 ng I-TEQDF/kg wood), assuming nondetect values
25 are zero—is used in this document as most representative of industrial wood combustion. This
26 emission factor was assigned a medium confidence rating. However, these mean emission
27 factors may not be appropriate for the combustion of waste wood containing elevated chlorine
28 content. NCASI (1995) concluded that CDD/CDF emissions from facilities burning salt-laden
29 wood residue may be considerably higher than those from facilities burning salt-free wood.
30 Similarly, Umweltbundesamt (1996) reported the results of stack gas testing at
31 approximately 30 facilities of varying design types burning various types of wood fuel. He noted
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1 that CDD/CDF emissions were elevated when the combustion conditions were poor, as
2 evidenced by elevated carbon monoxide emissions and/or when the fuel contained elevated
3 chlorine levels. Umweltbundesamt attributed the correlation between elevated CDD/CDF
4 emissions and elevated chlorine content of the fuel to the fire-retardant effects of chlorine, which
5 may have inhibited complete combustion. The chlorine content of untreated wood and of bark
6 were reported as 0.001 to 0.01% by weight and 0.01 to 0.02% by weight, respectively.
7 Chipboard can contain up to 0.2% chlorine by weight because of binding agents used to
8 manufacture the chipboard. Preservative-treated wood and PVC-coated wood were reported to
9 contain chlorine contents as high as 1.2 and 0.3% by weight, respectively.
10 The facility tested by EPA in 1987 (U.S. EPA, 1987a) was located at a lumber products
11 plant that manufactures overlay panels and other lumber wood products. Nearly all the wood fed
12 to the lumber plant had been stored in sea water adjacent to the facility and therefore had a
13 significant concentration of inorganic chloride. The wood-fired boiler tested was a three-cell
14 dutch oven equipped with a waste heat boiler. The feed wood was a mixture of bark, hogged
15 wood, and green and dry planer shavings. The exhaust gases from the boiler passed through a
16 cyclone and fabric filter prior to discharge from the stack. From this study, an average emission
17 factor for total CDDs/CDFs of 1,020 ng/kg of wood burned (with a range of 552 to 1,410 ng/kg)
18 was reported for the three collected samples. An average TEQ emission factor of 17.1 ng
19 I-TEQDF/kg of wood burned (with a range of 7.34 to 22.8 ng/kg) was estimated by EPA using
20 measured congener group concentrations and concentrations of 2,3,7,8-TCDD and 2,3,7,8-
21 TCDF. Similar emission factors were reported by Luthe et al. (1998) from testing conducted
22 during the 1990s at four Canadian coastal, salt-laden wood-fueled boilers—1.4, 2.6, 17.4, and
23 27.6 ng I-TEQDF/kg of wood combusted.
24 The overall average of the five tested facilities in Canada and the United States is 13.2 ng
25 I-TEQDF/kg of wood combusted. The confidence rating assigned to this emission factor is low
26 because it is based on reporting of limited congener data at one U.S. facility and testing at four
27 non-U.S. sources and because the fraction of salt-laden wood combusted across facilities is likely
28 to have been highly variable.
29 For the reference year 2000, NC AST provided congener-specific estimates of CDD/CDF
30 releases from the pulp and paper industry, including emissions from wood residue-fired boilers
31 (Gillespie, 2002). The emission factors were taken from the "NCASI Handbook of Chemical
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1 Specific Information for SARA (Superfund Amendments and Reauthorization Act) Section 313
2 Form R Reporting." The factors provided in the handbook were compiled from valid test data
3 supplied to NCASI by a variety of sources, including NCASI member companies that had
4 performed the tests in response to a regulatory program. Data from 11 bark and wood residue-
5 fired boilers used by the forest products industry were used to calculate an emissions estimate.
6 Concentrations of emissions from the wood residue-fired boilers were 0.018 |_ig TEQDF-
7 WHO98/ton of wood (see Table 4-15).
8
9 4.2.2.2. Activity Level Information
10 In 1987, 33.2 million metric tons of wood were burned for fuel in industrial furnaces. In
11 1995, industrial wood consumption totaled 32.6 million metric tons. EIA (2003a) estimated that
12 industrial wood consumption totaled 1988 trillion Btu (104.6 million metric tons) in 2000. This
13 total becomes 51.5 million metric tons with the removal of kraft black liquor combustion. The
14 majority of wood fuel consumed in the industrial sector consists of wood waste (chips, bark,
15 sawdust, and hogged fuel). Consumption in the industrial sector is dominated by two industries:
16 paper and allied products and lumber and wood products (EIA, 1994). These activity level
17 estimates are assigned a high confidence rating because they are based on recent government
18 survey data.
19 Activity level data on combustion of salt-laden wood are not normally collected, even
20 though the associated emission factor is greater than the factor associated with nonsalt-laden
21 wood. Nonetheless, attempts have been made to estimate this activity level. NCASI combined
22 the results from a 1995 survey of combustion units in the pulp and paper industry with an ad hoc
23 telephone survey of mills in the Pacific Northwest (Oregon and Washington) to produce a
24 conservative estimate—254,000 metric tons (0.8% of the estimated 32.6 million metric tons of
25 industrial wood consumed that year)—of the amount of salt-laden wood burned at U.S. pulp and
26 paper mills in 1995. NCASI suspected that a similar fraction of industrial wood combusted in
27 1987 by pulp and paper mills was salt-laden (Gillespie, 1998).
28 For purposes of the NCASI survey, salt-laden wood was defined as wood that had been
29 transported, stored, or otherwise exposed to saltwater prior to being processed as fuel. None of
30 the three responding mills in Oregon reported the use of salt-laden wood. Eight of the 13
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1 responding mills in Washington reported some combustion of salt-laden wood. The estimated
2 percentage of salt-laden wood to total wood consumption in the Washington mills was 17%.
3 As noted above, the majority of industrial wood combustion (97%) occurs in two
4 industries: the paper and allied products industry and the lumber and wood products industry.
5 The relative amounts of wood combusted by each of these two industries were the same in 1990
6 and 1992, the only years for which these statistics are readily available (EIA, 1991, 1994).
7 Therefore, it can be assumed that the percentage of total wood combusted nationally by the
8 lumber and wood products industry that is salt-laden is the same percentage as for the paper and
9 allied products industry, 0.8%. Therefore, the total percentage of wood combusted by industry
10 that is salt-laden is 1.6%. For the reference years 1987, 1995, and 2000, this equates to 0.5, 0.5,
11 and 0.8 million metric tons, respectively. These activity level estimates are assigned a low
12 confidence rating because they are possibly nonrepresentative of the activity levels for the source
13 category combusting salt-laden wood.
14
15 4.2.2.3. Emission Estimates
16 Applying the average TEQ emission factor from the four CARB and five NCASI studies
17 (0.6 ng TEQDF-WHO98/kg wood [0.56 ng I-TEQDF/kg wood]) to the estimated quantities of
18 nonsalt-laden wood burned by industrial facilities in 1987 (33.2 million metric tons), 1995 (32.6
19 million metric tons), and 2000 (51.5 million metric tons) yields estimated TEQ emissions to air
20 of 19.9 g TEQDF-WHO98 (18.6 g I-TEQDF) in 1987, 19.6 g TEQDF-WHO98 (18.3 g I-TEQDF) in
21 1995, and 30.9 g TEQDF-WHO98 (28.8 g I-TEQ) in 2000.
22 Applying the average TEQ emission factor from the five studies on boilers combusting
23 salt-laden wood (13.2 ng I-TEQDF/kg wood) to the estimated quantities of salt-laden wood burned
24 by industrial facilities in 1987 (0.5 million metric tons), 1995 (0.5 million metric tons), and 2000
25 (0.8 million metric tons) yields estimated TEQ emissions to air of 6.6 g I-TEQDF in both 1987
26 and 1995 and 10.6 g I-TEQDF in 2000.
27 Total emissions for 1987, 1995, and 2000 are estimated to have been 26.5, 26.2, and 41.5
28 g TEQDF-WHO98 (25.2, 24.9, and 39.4 g I-TEQDF), respectively. Of the 2000 estimate, NCASI
29 estimates that 0.74 g TEQDF-WHO98/yr of dioxins were emitted from pulp and paper wood-fired
30 boilers (Gillespie, 2002). As noted above, the total emissions are based on tests conducted at
31 nine facilities in two industries that account for 97% of total industrial wood fuel combustion.
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1 The remaining 3% of industrial combustion and the combustion of wood by the commercial
2 sector (for which no reliable activity level estimates are available) may not be well represented
3 by the emission factors used above, particularly if poorly controlled combustors or treated wood
4 (e.g., treated with PCP or plastics) are burned. The emission estimates for 1987, 1995, and 2000
5 are given a low confidence level because the activity level estimates were assigned a low
6 confidence rating .
7
8 4.2.3. Solid Waste from Wood Combustion (Residential and Industrial)
9 The measurement of CDDs/CDFs in chimney soot and bottom ash from wood-burning
10 stoves and fireplaces has been reported by several researchers (Bumb et al., 1980; Nestrick and
11 Lamparski, 1982, 1983; Clement et al., 1985b; Bacher et al., 1992; Van Oostam and Ward, 1995;
12 and Dumler-Gradl et al., 1995a).
13 Bumb et al. (1980) detected TCDDs (nondetects to 0.4 i-ig/kg), HxCDDs (0.2 to 3 pg/kg),
14 HpCDDs (0.7 to 16 pg/kg), and OCDD (0.9 to 25 pg/kg) in residues from the wall of a home
15 fireplace and from the firebrick of another home fireplace; for lack of a suitable analytical
16 method, analysis was not performed for PeCDDs. Neither of the fireplaces sampled by Bumb et
17 al.(1980)had burned pre servati ve-treated wood.
18 Nestrick and Lamparski (1982, 1983) expanded the research of Bumb et al. by conducting
19 a survey of CDD concentrations in chimney soot from residential wood-burning units in three
20 rural areas of the United States. Samples were collected from the base of six chimneys in each of
21 the three study areas. Samples were not collected from units where any type of treated or
22 manufactured wood had been burned. For lack of a suitable analytical method, analysis was not
23 performed for PeCDDs. The results of this survey are summarized in Table 4-16. There was
24 wide variation in the results across soot samples, with standard deviations for congeners and
25 congener groups often equal to or exceeding the mean value; however, CDDs in each congener
26 group were detected in the soot from almost all sampled units. The authors concluded that the
27 results did not appear to present any easily discernible patterns with respect to geographic region,
28 furnace operational parameters, or wood fuel type. They attributed the wide variability observed
29 to differences in design of the units, which affected the sampling point or the conditions at the
30 sampling point, and possible contamination of the fuel wood.
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1 Clement et al. (1985b) analyzed chimney soot and bottom ash from residential wood
2 stoves and fireplaces in Canada. The CDD/CDF congener concentrations are presented in Table
3 4-16 (soot) and Table 4-17 (bottom ash). CDD/CDF congeners were detected in all samples
4 analyzed, although the relative amounts of the different congener groups varied considerably and
5 inconsistently between wood-burning unit types and between ash and soot samples from the
6 same unit. Clement et al. (1985b) also presents total CDD/CDF concentration data for bottom
7 ashes from outside open-air burning of wood. No analyses were reported for individual
8 congeners. The results for the congener groups are presented below. The quantities of ashes
9 produced by the outside open-air burning test were not presented; hence it is not possible to
10 readily determine the quantities of CDDs/CDFs disposed of.
11
12 Congener group Concentration (|ag/kg)
13 TCDDs 0.8
14 PeCDDs 4.2
15 HxCDDs 7.2
16 HpCDDs 11
17 OCDD 10
18 TCDFs 2.2
19 PeCDFs 7.6
20 HxCDFs 8.2
21 HpCDFs 11
22 OCDF 1.7
23
24 Bacher et al. (1992) characterized the full spectrum (mono through octa substitution) of
25 CDD/CDF and BDD/BDF congeners in the soot from an old farmhouse in southern Germany.
26 The chimney carried smoke from an oven that had used untreated wood at the rate of about
27 5 m3/yr for more than 10 yr. The sample was taken during the annual cleaning by a chimney
28 sweep. The only BDF detected was mono-BDF (230 ng/kg). No BDDs, BCDDs, or BCDFs
29 were detected at a DL of 20 ng/kg. The results for the tetra- through octa-CDDs/-CDFs are
30 presented in Table 4-16. The results indicate that CDFs dominated the CDDs in each congener
31 group except octa. Also, the less-chlorinated congener groups dominated the more highly
32 chlorinated congener groups for both the CDDs and the CDFs. The TEQ content of the chimney
33 soot was 755 ng TEQDF-WHO98/kg (720 ng I-TEQDF/kg), of which less than 30% was due to
34 CDDs.
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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
29
30
31
32
Van Oostdam and Ward (1995) analyzed soot from two wood stoves in British Columbia,
Canada. The average TEQ concentration was 246 ng TEQDF-WHO98/kg (211 ng I-TEQDF/kg).
The congener-specific results are presented in Table 4-16. The soot from a wood stove burning
salt-laden wood in a coastal area was found to have an I-TEQDF content of 7,706 ng I-TEQDF/kg,
or 20 to 90 times greater than the concentrations found in the soot from the other two tested
stoves.
Dumler-Gradl et al. (1995a) analyzed chimney soot samples collected by chimney sweeps
from 188 residences in Bavaria. The summary results of the survey, the largest published survey
of its kind to date, are presented in Table 4-18. As in Nestrick and Lamparski (1982, 1983) and
Clement et al. (1985b), CDDs/CDFs were detected in all samples; however, there was wide
variability in total TEQ concentrations within and across unit type/fuel type combinations.
The Washington State Department of Ecology (1998) reported CDD/CDF congener data
for ash from hog fuel boilers at three paper mills. The data were compiled and evaluated to
determine total I-TEQ concentrations and loading. Nondetect values were included as zero, one-
half the DL, or at the DL. The results, assuming nondetect values are at zero, are shown below.
Location
Daishowa America,
Port Angeles
Ft. James
Rayonier
Type of residual
Mixed ash
Fly ash
Filter ash
Vacuum Filter and grate
Filter ash
Fly ash
I-TEQDF (ng/kg)
0.31
35.4
12,640
1,150
2,299
225
I-TEQDF (mg/day)
0.012
0.544
68.9
6.27
12.5
1.23
Pohlandt and Marutzky (1994) presented CDD/CDF concentration data for various ashes
("bottom," "furnace," "boiler," and "fly") from 12 wood-burning boilers. The fly ash samples
from two wood-working industry boilers appeared to have the greatest concentrations of
CDDs/CDFs. Table 4-19 lists the average congener concentration for the two boilers. Three
boiler bottom ash samples contained detectable amounts of only total HpCDDs/HpCDFs and
OCDD/OCDF. All the other boiler samples were from boilers that burned copper/chrome/boron-
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1 impregnated woods. These samples had total TEQs (assumed to be I-TEQs) ranging from 0.07
2 to 89 ppt, the highest being the fly ash samples (52 and 89 ppt). The quantities produced by the
3 boilers that were tested were not reported; hence it is not possible to readily determine the
4 quantities of CDDs/CDFs disposed of.
5 Carpenter (2001) reported the results of analyses of two ash samples from wood-burning
6 facilities in New Hampshire. Both samples were from the burning of clean (i.e., untreated) wood
7 chips, sawdust, and bark. The first sample was a combination of fly ash and bottom ash. The
8 second sample was only fly ash, but it was a combination of fly ash from two wood-burning
9 boilers. For the first sample, none of the 2,3,7,8-substituted congeners were detected at DLs that
10 ranged from 0.98 ng/kg for 2,3,7,8-TCDD and 2,3,7,8-TCDF to 9.8 ng/kg for OCDD and OCDF.
11 (All other congeners had a DL of 4.9 ng/kg.) For the second sample, all but two congeners were
12 below DLs (which ranged from 0.379 to 0.831 ng/kg). The two congeners that exceeded DLs
13 were OCDD at 1.261 ng/kg, and 1,2,3,4,6,7,8-HpCDF at 1.022 ng/kg. For this sample, assuming
14 that the nondetected congeners were not present, I-TEQDF concentration is 0.011 ng/kg. The
15 quantities of the ash produced were not reported.
16 In a CARB report of emissions from a wood waste-fired incinerator (CARB, 1990b), data
17 are given for CDDs and CDFs for four ash samples. The concentrations of 2,3,7,8-substituted
18 CDD/CDF congeners for each of those four tests were all below the method detection limits
19 (MDLs) except for OCDD, which was detected in three samples at concentrations of 14, 18, and
20 32 ng/kg, and 2,3,7,8-TCDF, which was detected in one sample at a concentration of 2.2 ng/kg.
21 The MDLs for each CDD and CDF congener ranged from 0.63 ppt (for 2,3,7,8-TCDD) to 9.5 ppt
22 (for HpCDF congeners). Total CDD and CDF values are given for each of the four samples.
23 However, those values assume that nondetected congeners are at the MDL level. Consequently,
24 the total CDD and total CDF values are biased high. The average of the four total CDD values is
25 28.8 ng/kg (with a range of 20.3 to 44 ng/kg). The average of the four total CDF values is 21.9
26 ng/kg (with a range of 16 to 26.9 ng/kg).
27 In CARB (1990e), data are presented for CDDs/CDFs for several samples of ESP waste
28 ash from a wood-fired boiler. The report provides sample results for 2 weeks of sampling
29 conducted at the facility. During the first week, the boiler burned fuels that were allowed by the
30 facility permit; during the second week, the boiler burned a mixture containing 70% permitted
31 fuel and 30% urban wood wastes. For the six samples collected over the 3 days of the first week,
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1 many of the concentrations of CDD/CDF congeners in the ESP ash were below the DLs. The
2 reported CDD concentrations in ESP waste ash ranged from 24 to 264 ng/kg, and the CDF
3 concentrations ranged from 12 to 151 ng/kg. However, those values assume that nondetected
4 congeners were present at the detection level. One sample did not have any nondetect values for
5 CDDs. The total CDD concentration for this sample was 264 ng/kg, or about 11.4 ng/kg TEQDF-
6 WHO98 (8.3 ng/kg I-TEQDF). The TEQDF-WHO98 and I-TEQDF CDF concentrations for this
7 sample are both less than 1.5 ng/kg. These values are less than 1 ng/kg for the other five
8 samples. All of the samples had some nondetects for the CDF analysis.
9 Six samples were also collected over 3 days during the second week of sampling, when
10 the 70/30 permitted/urban wood waste mix was burned. For the samples from the second week,
11 the CDD concentrations in ESP waste ash ranged from 1,365 to 3,190 ng/kg, and the CDF
12 concentrations ranged from 2,866 to 11,282 ng/kg. CARB (1990e) assumed that nondetected
13 congeners were present at the detection level; however, this is a reasonable estimate for this data
14 set because there was only one nondetect value. Table 4-20 presents the average congener
15 concentrations for these samples. The report did not present quantities of ESP ashes produced by
16 the boiler; therefore, it is not possible to readily determine the quantities of CDDs/CDFs
17 disposed.
18 Appendix II of Luthe et al. (1998) shows TEQ concentrations (assumed to be I-TEQDF) in
19 ashes collected from APCDs from "salt-laden" wood steam boilers. The I-TEQDF content of
20 ashes from three of the primary multiclone hoppers varied significantly, 0.0978, 0.186, and 9.375
21 pg/kg. Two samples of ash were taken from the secondary multiclone hoppers. The secondary
22 multiclone removes dust from the primary multiclone emissions; therefore, the ash is finer than
23 primary dust. The I-TEQDF values for the ash were 1.073 and 20.879 pg/kg. The I-TEQDF values
24 for two samples taken from the ESP that collects dust from the secondary multiclone emissions,
25 which therefore is finer than multiclone dust, are 3.926 and 8.044 pg/kg. No data are given for
26 individual congeners. In fact, because the reference discusses only "dioxins," it is unclear
27 whether the TEQ data are for CDDs or for CDDs plus CDFs. Quantities of collected ash were
28 not given.
29 Table II of a report by Luthe et al. (1996) presents data for the "TEQs [assumed to be I-
30 TEQs] on particulates from a secondary collection device for boilers at four paper mills burning
31 salt-laden wood. Eight data points are given (two for each mill), the average of which is 3.6
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1 l-ig/kg. The range of values is 1.3 to 8 pg/kg. As in Luthe et al. (1998), no data are given for
2 individual congeners. It is also unclear whether the TEQ data are for CDDs or for CDDs plus
3 CDFs. Quantities of collected ash are not given.
4 Table 5-16 of the National Dioxin Survey (U.S. EPA, 1987a) contains data indicating that
5 the bottom ash from wood combustion from one source (it is not indicated whether it was a
6 boiler) contained 140 ng/kg of 2,3,7,8-TCDD, 138,200 ng/kg of CDDs, and 7,400 ng/kg of
7 CDFs. For a second wood combustion source, the ash contained no detectable 2,3,7,8-TCDD,
8 but it did contain about 125 ng/kg of CDDs and nondetectable levels of CDFs. The fabric filter
9 dust from the second source contained 100 ng/kg of 2,3,7,8-TCDD, 1,143,600 ng/kg of CDDs,
10 and 315,600 ng/kg of CDFs. Specific data for congeners and for ash/dust quantities are not
11 given.
12 NCASI also provided information on emissions from wood residue boiler ash for
13 reference year 2000 (Gillespie, 2002). As with the boiler emissions, emission factors for the
14 boiler ash were taken from the "NCASI Handbook of Chemical Specific Information for SARA
15 Section 313 Form R Reporting." Total TEQ concentrations were estimated to be 13.2 ng/kg.
16 Because 72% of the total ash produced is landfilled, emission estimates were 2.21 g TEQDF-
17 WHO98/yr for ash landfilled and 0.62 g/yr for ash not landfilled (see Table 4-15). It is not known
18 at this time whether the amount of dioxin in nonlandfilled ash results in an environmental
19 release. Therefore, this value was not included in the inventory.
20
21 4.3. OIL COMBUSTION
22 The two major categories of fuel oils that are burned by combustion sources are distillate
23 oils and residual oils. These oils are further distinguished by grade: numbers 1 and 2 are
24 distillate oils, 5 and 6 are residual oils, and 4 is either distillate oil or a mixture of distillate and
25 residual oils. Number 6 fuel oil is sometimes referred to as Bunker C. Distillate oils are more
26 volatile and less viscous than residual oils. They have negligible nitrogen and ash content and
27 usually contain less than 0.3% sulfur (by weight). Distillate oils are used mainly in domestic and
28 small commercial applications. The heavier residual oils (5 and 6), being more viscous and less
29 volatile than distillate oils, must be heated for ease of handling and to facilitate proper
30 atomization. Because residual oils are produced from the residue after the lighter fractions
31 (gasoline, kerosene, and distillate oils) are removed from the crude oil, they may contain
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1 significant quantities of ash, nitrogen, and sulfur. Residual oils are used mainly in utility,
2 industrial, and large commercial applications (U.S. EPA, 1995b).
3
4 4.3.1. Residential/Commercial Oil Combustion
5 No testing data could be located for the CDD/CDF content of air emissions from
6 residential/commercial oil-fired combustion units in the United States. However, EPA (U.S.
7 EPA, 1997b) estimated CDD/CDF congener group and TEQ emission factors using average
8 CDD/CDF concentrations reported for soot samples from 21 distillate fuel oil-fired furnaces used
9 for central heating in Canada and a particulate emission factor for distillate fuel oil combustors
10 (300 mg/L of oil) obtained from AP-42 (U.S. EPA, 1995b). The TEQ emission factor estimate
11 was derived using the calculated emission factors for 2,3,7,8-TCDD; 2,3,7,8-TCDF; and the 10
12 congener groups. These emission factors are assigned a low confidence rating because they were
13 developed from soot samples and may not be representative of the source category. These
14 emission factors are presented in Table 4-21, and the congener group profile is presented in
15 Figure 4-6.
16 Because the representativeness of the emission factor of 1987 emissions is uncertain, no
17 national emission estimate is proposed at this time. For reference year 1995, a preliminary
18 estimate of potential national TEQ emissions from this source category was made using the
19 emission factor presented in Table 4-21 (190 pg TEQDF-WHO98/L [150 pg I-TEQDF/L] of oil
20 combusted). Distillate fuel oil sales to the residential/commercial sector totaled 39.7 billion L in
21 1995 (EIA, 1997a). Applying the emission factors from U.S. EPA (1997b) to this fuel oil sales
22 estimate results in estimated emissions of 7.5 g TEQDF-WHO98 (6 g I-TEQDF) in 1995.
23 For reference year 1987, assuming a barrel of oil contains 158.99 liters, distillate fuel oil
24 sales to the residential and commercial sector totaled 28.1 billion liters (177 million barrels) and
25 16.2 billion liters (102 million barrels), respectively (EIA, 1999). Likewise, residual oil sales to
26 the commercial sector in 1987 totaled 6.7 billion liters (42 million barrels) (EIA, 1999). Using
27 the emission factor presented in Table 4-21 (150 pg I-TEQDF/L of oil combusted and 190 pg
28 TEQDF-WHO98/L of oil combusted), EPA estimates that 4.22 g I-TEQDF or 5.35 g TEQDF-WHO98
29 were emitted in 1987 for the residential sector for home heating with distillate oil. For the
30 institutional/commercial sector, EPA estimates TEQ emissions of 1.34 g I-TEQDF (1.54 g TEQDF-
31 WHO98) for residual oil and 3.24 g I-TEQDF (3.73 g TEQDF-WHO98) for distillate oil for the year
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1 1987, using an emission factor of 200 pg I-TEQDF/L of oil combusted (230 pg TEQDF-WHO98/L
2 of oil combusted) (see Section 4.3.2). Because the representativeness of the emission factor for
3 1987 emissions is uncertain, EPA has given this estimate a low confidence rating.
4 For reference year 1995, a low confidence estimate of potential national TEQ emissions
5 from this source category was made using the same emission factors used for the 1987 estimates.
6 Distillate fuel oil sales to the residential and commercial sector totaled 26.2 and 13.5 billion
7 liters, respectively, in 1996 (EIA, 1997a). Applying the respective emission factors to these fuel
8 oil sales estimates results in estimated emissions of 3.93 g I-TEQDF (4.98 g TEQDF-WHO98) for
9 the residential sector and 2.7 g I-TEQDF (3.11 g TEQDF-WHO98) for the institutional/commercial
10 sector in 1995. Residual oil sales to the commercial sector in 1995 totaled 3.7 billion liters (23
11 million barrels) (EIA, 1999). Applying the emission factor of 200 pg I-TEQDF/L of oil
12 combusted (230 pg TEQDF-WHO98/L of oil combusted) (see Section 4.3.2) yields TEQ emissions
13 of 0.73 g I-TEQDF (0.84 g TEQDF-WHO98) for residual oil in 1995.
14 For reference year 2000, OAQPS developed national emission estimates for residual oil
15 and distillate oil consumed in institutional/commercial heating and distillate oil consumed in
16 residential heating. OAQPS used state-level 2000 activity data (EIA, 2003b), which were
17 allocated to counties by the 1999 county-to-state proportion of employment for numerous SIC
18 codes, as identified by the U.S. Census Bureau for 2000. OAQPS estimated that 2.82 billion L of
19 residual oil and 12.7 billion L of distillate oil were consumed in institutional/commercial heating
20 in 2000. Applying the emission factor of 230 pg TEQDF-WHO98/L (200 pg I-TEQDF/L) of oil
21 combusted (see Section 4.3.2) yields TEQ emissions of 0.65 g TEQDF-WHO98 (0.56 g I-TEQDF)
22 for residual oil and 2.92 g TEQDF-WHO98 (2.53 g I-TEQDF) for distillate oil for 2000. OAQPS
23 estimated that 23.9 billion L of distillate oil were consumed for residential heating in 2000.
24 Using the emission factors discussed above (U.S. EPA, 1997b), OAQPS estimated emissions of
25 4.54 g TEQDF-WHO98 (3.59 g I-TEQDF) from distillate oil used for residential heating in 2000.
26 These emission estimates for all years are given a low confidence rating because the emission
27 factor was given a low confidence rating.
28
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1 4.3.2. Utility Sector and Industrial Oil Combustion
2 Preliminary CDD/CDF emission factors were reported (U.S. EPA, 1997b) for oil-fired
3 utility boilers using the results of boiler tests conducted over several years. The data are a
4 composite of various furnace configurations and APCD systems. Table 4-22 lists the median
5 emission factors presented by EPA. The congener and congener group profiles based on these
6 data are presented in Figure 4-7. The median I-TEQDF emission factor was reported to be 366 pg
7 TEQDF-WHO98/L (314 pg I-TEQDF/L) of oil burned.
8 In 1993, the Electric Power Research Institute (EPRI) sponsored a project to gather
9 information of consistent quality on power plant emissions. The Field Chemical Emissions
10 Measurement (FCEM) project included testing of two cold-sided, ESP-equipped, oil-fired power
11 plants for CDD/CDF emissions (EPRI, 1994). The averages of the congener and congener group
12 emission factors reported for these two facilities are presented in Table 4-22. The average TEQ
13 emission factor is 93.6 pg TEQDF-WHO98/L (83.1 pg I-TEQDF/L) of oil burned when nondetect
14 values are treated as zero.
15 The TEQ emission factors reported by EPRI (1994) are less than the median TEQ
16 emission factor reported by EPA by a factor of 3 to 4 (U.S. EPA, 1997b). For purposes of this
17 assessment, the EPA median and EPRI mean emission factors were averaged for an emission
18 factor of 230 pg TEQDF-WHO98/L (200 pg I-TEQDF/L). Although the estimated emission factors
19 are assumed to be the current best estimates for utility/industrial oil burning, they are assigned a
20 low confidence rating.
21 Residual fuel oil sales totaled 77.3 billion L in 1987 and 46.6 billion L in 1995 (EIA,
22 1992, 1997a). Vessel bunkering was the largest consumer (48% of sales), followed by electric
23 utilities and the industrial sector. A high confidence rating is assigned to these production
24 estimates. Application of the TEQ emission factor of 230 pg TEQDF-WHO98/L (200 pg I-
25 TEQDF/L) to these residual fuel oil sales results in estimated TEQ emissions of 17.8 g TEQDF-
26 WHO98 (15.5 g I-TEQDF) for 1987 and 10.7 g TEQDF-WHO98 (9.3 g I-TEQDF) for 1995.
27 For reference year 2000, OAQPS developed national emission estimates for residual and
28 distillate oil consumption for the industrial sector. OAQPS used state-level 2000 activity data
29 (EIA, 2003b), which were allocated to counties by the 1999 county-to-state proportion of
30 employment for numerous SIC codes, as identified by the U.S. Census Bureau for 2000. OAQPS
31 estimated that 7.33 billion L of residual oil and 31.5 billion L of distillate oil were consumed in
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1 the industrial sector in 2000. OAQPS combined these national activity levels with the emission
2 factor of 230 pg TEQDF-WHO98/L (200 pg I-TEQDF/L) to estimate 2000 TEQ emissions of 1.69 g
3 TEQDF-WHO98 (1.47 g I-TEQDF) from residual oil consumption and 7.25 g TEQDF-WHO98 (6.3 g
4 I-TEQDF) from distillate oil combustion. Emission estimates for all reference years were assigned
5 a low confidence rating on the basis of the low rating for the emission factor.
6
7 4.3.3. Used Oil Combustion
8 The emission factors derived by EPA (U.S. EPA, 1997b) and EPRI (1994) were based on
9 combustion of virgin oil by utility boilers. Significantly greater emission factors have been
10 reported by Bremmer et al. (1994) for combustion of used oil by smaller combustion units in the
11 Netherlands. Flue gases from a garage stove consisting of an atomizer fueled by spent
12 lubricating oil from diesel engines (35 mg ClVkg) were reported to contain 0.1 ng I-TEQDF/Nm3
13 (2,000 pg I-TEQDF/kg) of oil burned. The flue gases from a hot water boiler consisting of a
14 rotary cup burner fueled with the organic phase of rinse water from oil tanks (340 mg ClVkg)
15 contained 0.2 ng I-TEQDF/Nm3 (4,800 pg I-TEQDF/kg) of oil burned. The flue gases from a steam
16 boiler consisting of a rotary cup burner fueled by processed spent oil (240 mg ClVkg) contained
17 0.3 ng I-TEQDF/Nm3 (6,000 pg I-TEQDF/kg) of oil burned. The emission factor for a ferry
18 burning heavy fuel oil containing 11 ng/kg organic chlorine was 3,200 to 6,500 pg I-TEQDF/kg of
19 oil burned.
20 From these data, Bremmer et al. (1994) derived an average emission factor for
21 combustion of used oil of 4,000 pg I-TEQDF/kg of oil burned. Bremmer et al. also reported
22 measuring CDD/CDF emissions from a river barge and a container ship fueled with gas oil (less
23 than 2 ng/kg of organic chlorine). The exhaust gases contained from 0.002 to 0.2 ng I-
24 TEQDF/Nm3. From these data, Bremmer et al. derived an average emission factor for inland oil-
25 fueled vessels of 1,000 pg I-TEQDF/kg oil burned. The applicability of these emission factors to
26 used oil combustors in the United States is uncertain. Therefore, estimates of potential emissions
27 from used oil combustion in the United States are not being developed at this time.
28
29 4.4. COAL COMBUSTION
30 During 2000, coal consumption accounted for approximately 18.9% of the energy
31 consumed in the United States from all sources (EIA, 2003). Of the 980 million metric tons of
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1 coal consumed in 2000, 891 million metric tons (90.9%) were consumed by electric utilities,
2 including independent power producers; 85.4 million metric tons (8.7%) were consumed by the
3 industrial sector, including 26.2 million metric tons consumed by coke plants; and 3.7 million
4 metric tons (0.4%) were consumed by residential and commercial sources (EIA, 2003). In 1995,
5 coal consumption (872 million metric tons of coal) accounted for approximately 22% of the
6 energy consumed from all sources in the United States (U.S. DOC, 1997). Of this total, 88.4%
7 (771 million metric tons) were consumed by electric utilities; 11% (96 million metric tons) were
8 consumed by the industrial sector, including consumption of 30 million metric tons by coke
9 plants; and 0.6% (5.3 million metric tons) were consumed by residential and commercial sources
10 (EIA, 1997b). Comparable figures for 1987 for total coal consumption of 759 million metric
11 tons are as follows: consumption by electric utilities, 651 million metric tons; consumption by
12 coke plants, 33.5 million metric tons; consumption by other industries, 68.2 million metric tons;
13 and consumption by the residential and commercial sectors, 6.3 million metric tons (EIA, 1995c).
14 These production estimates are assigned a high confidence rating because they are based on
15 detailed studies specific to the United States.
16 The following two subsections discuss the results of relevant emission studies for the
17 utility/industrial and residential sectors, respectively, and present annual TEQ emission estimates
18 for reference years 1987, 1995, and 2000.
19
20 4.4.1. Utilities and Industrial Boilers
21 Few studies have been performed to measure CDD/CDF concentrations in emissions
22 from coal-fired plants. Those studies did not have the congener specificity or DLs necessary to
23 fully characterize this potential source (U.S. EPA, 1987a; NATO, 1988; Wienecke et al., 1992).
24 The results of more recent testing of coal-fired utility and industrial boilers in the Netherlands
25 (Bremmer et al., 1994), the United Kingdom (Cains and Dyke, 1994; CRE, 1994), Germany
26 (Umweltbundesamt, 1996), and the United States (Riggs et al., 1995; EPRI, 1994) have achieved
27 lower DLs.
28 Bremmer et al. (1994) reported the results of emission measurements at two coal-fired
29 facilities in the Netherlands. The emission factor reported for a pulverized coal electric power
30 plant equipped with an ESP and a wet scrubber for sulfur removal was 0.35 ng I-TEQDF/kg of
31 coal combusted (0.02 ng I-TEQDF/Nm3 at 11% oxygen). The emission factor reported for a grass-
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1 drying chain grate stoker equipped with a cyclone APCD was 1.6 ng I-TEQDF/kg of coal fired
2 (0.16 ng I-TEQDF/Nm3 at 11% oxygen).
3 Cains and Dyke (1994) reported an emission factor of 102 to 109 ng I-TEQDF/kg of coal
4 at a small-scale facility in the United Kingdom that was equipped with an APCD consisting of
5 only a grit arrester. CRE (1994) reported results of testing at 13 commercial and industrial coal-
6 fired boilers in the United Kingdom, with TEQ emission factors ranging from 0.04 to 4.8 ng I-
7 TEQDF/kg coal combusted (mean value of 0.6 ng I-TEQDF/kg). CRE also reported testing results
8 for one coal-fired power plant, 0.06 ng I-TEQDF/kg of coal combusted. Umweltbundesamt
9 (1996) reported that the I-TEQDF content of stack gases from 16 coal-burning facilities in
10 Germany ranged from 0.0001 to 0.04 ng I-TEQDF/m3; however, the data provided in that report
11 did not enable emission factors to be calculated.
12 In 1993, the U.S. Department of Energy (DOE) sponsored a project to assess emissions of
13 hazardous air pollutants at coal-fired power plants. As part of the project, CDD/CDF stack
14 emissions were measured at seven U.S. coal-fired power plants. The preliminary results of the
15 project, concentrations in stack emissions, were reported by Riggs et al. (1995) and are
16 summarized in Table 4-23. The levels reported for individual 2,3,7,8-substituted congeners were
17 typically very low (less than or equal to 0.033 ng/Nm3) or not detected. In general, CDF levels
18 were higher than CDD levels. OCDF and 2,3,7,8-TCDF were the most frequently detected
19 congeners (at four of the seven plants). Table 4-24 presents characteristics of the fuel used and
20 the APCD employed at each plant. Riggs et al. (1995) could not attribute variations in emissions
21 between plants to any specific fuel or operational characteristic.
22 As mentioned in Section 4.3.2, EPRI sponsored the FCEM project to gather information
23 of consistent quality on power plant emissions. Testing for CDD/CDF emissions was performed
24 on four coal-fired power plants equipped with cold-sided ESPs. Two plants burned bituminous
25 coal and two burned sub-bituminous coal. The results of the testing were integrated into the final
26 results of the DOE project discussed above (Riggs et al., 1995) and published in 1994 (EPRI,
27 1994). The average congener and congener group emission factors derived from this 11-facility
28 data set, as reported in EPRI (1994), are presented in Table 4-25. Congener and congener group
29 profiles for the data set are presented in Figure 4-8. The average emission factor, assuming
30 nondetect values are zero, is 0.078 ng TEQDF-WHO98/kg (0.079 ng I-TEQDF/kg) of coal
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1 combusted. A medium confidence rating is assigned to the emission factors derived from the
2 DOE and EPRI studies because they were based on recent testing at U.S. power plants.
3 Because the EPRI and DOE data characterized emissions from units with only cold-sided
4 ESPs, there has been uncertainty regarding the applicability of the emission factors derived from
5 these data to units with hot-sided ESPs. In July 1999, EPA conducted testing of stack emissions
6 at a coal-fired utility equipped with a hot-sided ESP. The preliminary results of this testing
7 indicated that the TEQ emission factor for hot-sided ESPs is of the same order of magnitude as
8 the average TEQ emission factors derived above.
9 Applying the TEQ emission factor of 0.078 ng TEQDF-WHO98/kg (0.079 ng I-TEQDF/kg)
10 of coal combusted to the consumption totals of 651, 771, and 891 million metric tons of coal
11 consumed by U.S. utility sectors in 1987, 1995, and 2000, respectively, yields estimated annual
12 emissions by the utility sector of 50.89 g TEQDF-WHO98 (51.4 g I-TEQDF) in 1987, 60.1 g TEQDF-
13 WHO98 (60.9 g I-TEQDF) in 1995, and 69.5 g TEQDF-WHO98 (70.4 g I-TEQDF) in 2000. These
14 emission estimates are assigned a medium confidence rating because the emission factor for this
15 category was judged to be medium.
16 No testing results could be located for CDD/CDF content in air emissions from
17 commercial and industrial coal-fired combustion units in the United States. It is uncertain
18 whether the data collected in the European studies (Bremmer et al., 1994; CRE, 1994) accurately
19 represent U.S. sources, but the data suggest that emission factors for commercial/industrial
20 sources might be higher than those reported for U.S. coal-fired utilities. Therefore, no national
21 emission estimate has been derived for this category. However, preliminary estimates of
22 potential national TEQ emissions from this source category can be derived for 1987, 1995, and
23 2000 using the total coal consumption for each of those reference years, excluding consumption
24 by coke plants, and the average emission factor, 0.6 ng I-TEQDF/kg coal combusted. Applying
25 the emission factor to the estimated combustion for 1987, 1995, and 2000 (68.2, 66, and 59.14
26 million metric tons, respectively) yields 40.9 g I-TEQDF/kg for 1987, 39.6 g I-TEQDF/kg for 1995,
27 and 35.4 g I-TEQDF/kg of coal combusted for 2000. These estimates should be regarded as
28 preliminary indications of possible emissions from commercial/industrial coal-fired boilers;
29 further testing is needed to confirm the true magnitude of these emissions.
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1 4.4.2. Residential Coal Combustion
2 In the residential sector, coal is usually combusted in underfeed or hand-stoked furnaces.
3 Other coal-fired heating units include hand-fed room heaters, metal stoves, and metal and
4 masonry fireplaces. Stoker-fed units are the most common design for warm-air furnaces and for
5 boilers used for steam or hot water production. Most coal combusted in these units is either
6 bituminous or anthracite. These units operate at relatively low temperatures and do not
7 efficiently combust the coal. Coal generally contains small quantities of chlorine; therefore, the
8 potential for CDD/CDF formation exists. Typically, coal-fired residential furnaces are not
9 equipped with PM or gaseous pollutant control devices that may limit emissions of any
10 CDDs/CDFs formed (U.S. EPA, 1997b). No testing results for CDD/CDF content in air
11 emissions from residential/commercial coal-fired combustion units in the United States could be
12 located; however, several relevant studies have been performed in European countries.
13 Thub et al. (1995) measured flue gas concentrations of CDDs/CDFs from a household
14 heating system in Germany fired with either salt lignite coal (total chlorine content of 2,000 ppm)
15 or normal lignite coal (total chlorine content of 300 ppm). CDDs/CDFs were detected in the flue
16 gases generated by combustion of both fuel types (see Table 4-26). The congener profiles and
17 patterns were similar for both fuel types, with OCDD the dominant congener and TCDF the
18 dominant congener group. However, the emissions were higher by a factor of 8 for the "salt"
19 coal (0.109 ng I-TEQDF/m3, or 2.74 ng I-TEQDF/kg) than for the "normal" coal (0.015 ng I-
20 TEQDF/m3, or 0.34 ng I-TEQDF/kg).
21 Using the results of testing performed by the Coal Research Establishment in the United
22 Kingdom, Eduljee and Dyke (1996) estimated emission factors for residential coal combustion
23 units of 2.1 ng I-TEQDF/kg for anthracite coal and 5.7 to 9.3 ng I-TEQDF/kg (midpoint of 7.5 ng
24 I-TEQDF/kg) for bituminous coal.
25 CDD/CDF emission factors were estimated (U.S. EPA, 1997b) for coal-fired residential
26 furnaces using average particulate CDD/CDF concentrations from chimney soot samples
27 collected from seven coal ovens and PM emission factors obtained from AP-42 that are specific
28 to anthracite and bituminous coal combustion (U.S. EPA, 1995b). The TEQ emission factors
29 estimated (60 and 98.5 ng I-TEQDF/kg of anthracite and bituminous coal, respectively) were
30 derived using the calculated emission factors for 2,3,7,8-TCDD, 2,3,7,8-TCDF, and the 10
31 congener groups (U.S. EPA, 1997b). EPA stated that the estimated factors should be considered
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1 representative of maximum emission factors because soot may not be representative of the PM
2 actually emitted to the atmosphere. These emission factors are presented in Table 4-26; congener
3 group profiles are presented in Figure 4-9.
4 Although the congener group profiles of the measurements by Thub et al. (1995) and the
5 estimates by EPA (U.S. EPA, 1997b) are similar, the TEQ emission factors of the two studies
6 differ by factors of 175 to 289. The emission factors used by Eduljee and Dyke (1996) to
7 estimate national annual TEQ emissions from residential coal combustion in the United
8 Kingdom fall in between the other two sets of estimates but are still about one to two orders of
9 magnitude greater than the estimated emission factor for industrial and utility coal combustors
10 (see Section 4.4.1).
11 For 1987 and 1995, preliminary estimates of potential national TEQs were derived using
12 the emission factors of Eduljee and Dyke (1996). U.S. EPA (1997b) reported that 72.5% of the
13 coal consumed by the residential sector in 1990 was bituminous and 27.5% was anthracite.
14 Assuming that these relative proportions reflect the actual usage in 1987 and 1995, then
15 application of the emission factors from Eduljee and Dyke (2.1 ng I-TEQDF/kg of anthracite coal
16 and 7.5 ng I-TEQDF of bituminous coal) to the consumption values of 6.3 and 5.3 million metric
17 tons in 1987 and 1995, respectively, (U.S. DOC, 1997) results in an estimated TEQ emission of
18 37.9 and 32.0 g I-TEQDF in 1987 and 1995, respectively. These estimates should be regarded as
19 preliminary indications of possible emissions from this source category because the emission
20 factor is judged to be clearly nonrepresentative of the sources. Further testing is needed to
21 confirm the true magnitude of these emissions.
22 For 2000, OAQPS developed national emission estimates for coal combustion for
23 residential heating. The activity level for residential coal combustion was taken from state-level
24 2000 activity data (EIA, 2003b). Because EIA no longer disaggregates coal consumption into
25 anthracite versus bituminous/lignite, OAQPS estimated each state's coal consumption using the
26 state's 1999 proportion of anthracite versus bituminous/lignite to total coal consumption.
27 Emissions were allocated to the county level as a proportion of state population in states that
28 consume anthracite coal and bituminous and lignite coal for residential heating. OAQPS
29 estimated that in 2000, 67,400 metric tons of anthracite coal and 343,000 metric tons of
30 bituminous and lignite coal were consumed for residential heating. Applying the TEQ emission
31 factors of 2.1 ng I-TEQDF/kg of anthracite coal combusted and 7.5 ng I-TEQDF/kg of bituminous
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1 coal combusted (Eduljee and Dyke, 1996) to these production factors yields preliminary
2 estimates of annual emissions of 0.14 g I-TEQDF of anthracite coal and 2.6 g I-TEQDF of
3 bituminous/sub-bituminous coal in 2000.
4
5 4.4.3. Solid Wastes from Coal Combustion
6 A limited amount of CDD/CDF concentration data have been developed for utility
7 industry solid wastes (U.S. EPA, 1999b), and these data are for wastes that are comanaged (i.e.,
8 combinations of fly ash, bottom ash, boiler slag, and flue gas desulfurization wastes). A total of
9 15 samples were taken from 11 disposal sites. The average concentration for each of the CDD
10 and CDF congeners is presented in the second column of Table 4-27. It should be noted that
11 most of the concentration values shown in Table 4-27 represent limits of detection.
12 Consequently, the values overestimate actual concentrations.
13 EPA (U.S. EPA, 1999c, Section 3.3) indicates that approximately 63 million tons
14 (assumed to be short tons, i.e., 2,000 pounds) of large-volume utility coal combustion solid
15 wastes were produced in 1995. Of this amount, about 67% was landfilled and the balance was
16 disposed of in surface impoundments. The concentration data presented in Table 4-27 are for
17 only the 53 million tons that were comanaged (about 84% of the total wastes). For purposes of
18 this analysis it is assumed that the CDD/CDF concentrations in the comanaged wastes are the
19 same as for the entire waste quantity. Combining the concentration data with the 63 million tons
20 of total waste yields the total quantities of each congener disposed of in 1995. These data are
21 presented in the fourth column of Table 4-27. As indicated in Section 4.4 of this document, total
22 consumption of coal for electric utility boilers in 1987 was 98.4% of 1995 consumption.
23 Consequently, the quantities of CDDs/CDFs disposed of in 1987 is assumed to be 98.4% of the
24 1995 values. These values are presented in column 3 of Table 4-27. The 1995 congener
25 quantities are converted into I-TEQDF and TEQDF-WHO98 values in columns 5 and 6. Because
26 this does not constitute an environmental release, the values are not included in the inventory.
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o
OJ
o
4^
o
Table 4-1. Descriptions and results of vehicle emission testing studies for CDDs and CDFs
Study
CARB (1987a); Lew
(1996)
Marklundetal. (1987)
Binghametal. (1989)
Marklundetal. (1990)
Hagenmaier et al.
(1990)
Oehmeetal. (1991)
(tunnel study)
Schwindetal. (1991)
Hutzinger et al. (1992)
Country
United States
Sweden
New Zealand
Sweden
Germany
Norway
Germany
Fuel type
Diesel (truck)
Unleaded
Leaded
Unleaded
Leaded
Unleaded
Leaded
Unleaded
Leaded
Diesel (truck)
Unleaded
Unleaded
Leaded
Diesel (car)
—
Leaded
Unleaded
Unleaded
Diesel (car)
Diesel (truck)
Scavenger3
No
No
Yes
No
Yes
No
Yes
No
Yes
No
No
No
Yes
No
—
Yes
No
No
No
No
Catalyst
equipped
NR
Yes
No
NR
NR
No
No
Yes
No
NR
No
Yes
No
NR
—
No
No
Yes
No
No
Number
of test
vehicles
1
2
4
1
4
2
2
1
2
1
1
1
1
1
e
1
1
1
1
1
TEQ emission
factor"
(pg/km driven)
676-1325°
[597-1307]
Not detected (< 13)
Approx. 20-220
Not detected (<20)
1-39
0.36-0.39
2.4-6.3
0.36
l.l-2.6d
Not detected (<18)c
5.1C[6.0]
0.7C [0.8]
108C [129]
2.1C[2.5]
520f
38f
Avg = 280
9500f
720f
Avg = 5 100
5.2-1 18C [7.2-142]
9.6-17.7c [10.2-18.1]
1-2.6C [1-2.8]
1-13C [1.2-14]
13-15C [14-15]
Driving cycle; sampling location
6-hr dynamometer test at 50 km/hr
A10 (2 cycles); muffler exhaust
A10 (2 cycles); muffler exhaust
A10 (3 or 4 cycles); muffler exhaust
A10 (3 or 4 cycles); muffler exhaust
FTP-73 test cycle; before muffler
FTP-73 test cycle; before muffler
FTP-73 test cycle; in tailpipe
FTP-73 test cycle; in tailpipe
U.S. federal mode 13 cycle; before muffler
Comparable to FTP-73 test cycle; in tailpipe
Comparable to FTP-73 test cycle; in tailpipe
Comparable to FTP-73 test cycle; in tailpipe
Comparable to FTP-73 test cycle; in tailpipe
Cars moving uphill (3.5% incline) at
60 km/hr
Cars moving downhill (3.5% decline) at
70 km/hr
Car average
Trucks moving uphill (3.5% incline) at
60 km/hr
Trucks moving downhill (3.5% decline) at
70 km/hr
Truck average
Various test conditions (loads and speeds)
Various test conditions (loads and speeds)
Various test conditions (loads and speeds)
Various test conditions (loads and speeds)
Various test conditions (loads and speeds)
O
O
2
O
H
O
HH
H
W
O
V
O
-------
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o
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o
Table 4-1. Descriptions and results of vehicle emission testing studies for CDDs and CDFs (continued)
Study
Gertleretal. (1996,
1998) (tunnel study)
Gullett and Ryan
(1997)
Country
United States
United States
Fuel type
Diesel (truck)
Diesel (truck)
Scavenger3
-
No
Catalyst
equipped
-
-
Number
of test
vehicles
g
1
TEQ emission
factor"
(pg/km driven)
Mean = 172
Mean = 29
Driving cycle; sampling location
Mean of seven 12-hr samples
Mean of five sample routes
aExcept in Marklund et al. (1987), dichloroethane and dibromoethane were used as scavengers.
bValues listed are in units of I-TEQDF. Values in brackets are in units of TEQDF-WHO98.
°Results reported were in units of pg TEQ/L of fuel. For purposes of this table, the fuel economy factor used by Marklund et al. (1990), 10 km/L (24
miles/gal), was used to convert the emission rates into units of pg TEQ/km driven for the cars. For the diesel-fueled truck, the fuel economy factor reported in
CARB (1987a) for a 1984 heavy-duty diesel truck, 5.5 km/L (13.2 miles/gal), was used.
dTable reflects the range of summary results reported in Marklund et al. (1990); however, the congener-specific results for the single run reported indicate an
emission rate of about 7.3 pg I-TEQDF/km.
Tests were conducted over portions of 4 days, with traffic rates of 8000-14,000 vehicles/day. Heavy-duty vehicles (defined as vehicles over 7 m in length)
ranged from 4 to 15% of total.
'Emission factors are reported in units of pg Nordic TEQ/km driven; the values in units of I-TEQDF/km are expected to be about 3 to 6% higher.
BTests were conducted over 5 days, with heavy-duty vehicle rates of 1800-8700 vehicles per 12-hr sampling event. Heavy-duty vehicles accounted for 21
to 28% of all vehicles.
NR = Not reported
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Table 4-2. CDD/CDF congener emission factors for diesel-fueled automobiles (pg/L)
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 (nondetect set to 0)
Total I-TEQDF (nondetect set to !/2 DL)
Total TEQDF-WHO98 (nondetect set to 0)
Total TEQDF-WHO98 (nondetect set to !/2 DL)
Automobile tailpipe emission study results
63 km/hra
7.9
9
ND(5.1)
ND(5.1)
ND(5.1)
44.1
440
20.5
ND(5.1)
7.1
6.5
6.7
ND(5.1)
ND(5.1)
40.7
8.5
94.4
501
184.4
20.8
22.2C
24.8
26.2
Idling
(test no. 25)"
13.1
6.3
21.4
36
28
107
635
79
171
58.7
121
75
17.1
52
159
11.9
214
846.8
958.7
100.7
100.7
103.1
103.1
57km/hr
(test no. 24)"
2.4
4.1
1
1.4
2
22.9
525
18.1
1.8
3.4
4.1
o
J
0.8
ND (0.4)
18.9
7.1
101
558.8
158.2
10.4
10.4
11.9
1.9
57km/hr
(full load)
(test no. 28)"
22
23
7.8
21
10
166
560
236
111
85
68
55
4.7
31
214
7.8
305
809.8
1117.5
129.6
129.6
140.4
140.4
Mean emission factors
Assuming
nondetect set
to zero
11.4
10.6
7.6
14.6
10
85
540
88.4
71
38.6
49.9
34.9
5.7
20.8
108.2
8.8
178.6
679.1
604.7
65.4
70
Assuming
nondetect set to
¥2 detection
limit (DL)
11.4
10.6
8.2
15.2
10.6
85
540
88.4
71.6
38.6
49.9
34.9
6.3
21.4
108.2
8.8
178.6
681
606.7
65.7
70.4
oo
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o
Table 4-2. CDD/CDF congener emission factors for diesel-fueled automobiles (pg/L) (continued)
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 (nondetect set to 0)
Total CDD/CDF (nondetect set to !/2 DL)
Automobile tailpipe emission study results
63 km/hra
37.4
19.7
23.6
88.5
440.5
76.7
39.3
25.6
80.6
94.4
926.3
926.3
Idling
(test no. 25)"
317
214
256
187
635
436
821
556
321
214
3,957
3,957
57km/hr
(test no. 24)"
31
22
20
77
525
58
36
26
72
101
968
968
57km/hr
(full load)
(test no. 28)"
394
228
164
356
560
3,093
1,205
472
241
305
7,018
7,018
Mean emission factors
Assuming
nondetect set
to zero
195
121
116
177
540
916
525
270
179
179
3,217
Assuming
nondetect set to
¥2 detection
limit (DL)
195
121
116
177
540
916
525
270
179
179
3,217
VO
aSource: Hagenmaieretal. (1990).
bSource: Schwind et al. (1991); Hutzinger et al. (1992).
°AnI-TEQDF emission factor of 23. 6 pg/L is reported in Hagenmaier et al. (1990); however, anI-TEQDF emission factor of 22.2 pg/L is calculated, based on
reported congener levels.
ND = Not detected; value in parenthesis is the detection limit
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Table 4-3. CDD/CDF congener emission factors for diesel-fueled trucks (pg/L)
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 (nondetect set to 0)
Total I-TEQDF (nondetect set to 1A DL)
Total TEQDF-WHO98 (nondetect set to 0)
Total TEQDF-WHO98 (nondetect set to 1A DL)
Truck tailpipe study results
50 km/hr
(test no. 40)a
25
5
14
28
14
119
1355
87
45
18
56
84
4.7
63
375
40
397
1,560
1,170
81
81
82
82
90 km/hr
(full load)
(test no. 42)a
16
18
5.7
6
6
74
353
53
34
51
29
31
5.1
23
71
5.4
104
478.7
406.5
70
70
79
79
50 km/hr "
ND (560)
ND (1,340)
ND (2,160)
ND (1,770)
ND (2,640)
116,000
344,400
ND (605)
ND (4,750)
ND (5,190)
ND (8,210)
ND (6,480)
13,400
ND (7,780)
73,460
ND(1 1,700)
140,400
460,400
227,300
3,720
7,290
3,280
7,190
Mean emission factors
Assuming
nondetect set to
zero
13.7
7.7
6.6
11.3
6.7
38,731
115,369
46.7
26.3
23
28.3
38.3
4,469
28.7
24,636
15.1
46,981
154,146
76,292
1,290
1,150
Assuming
nondetect set to Vz
detection limit (DL)
107
231
367
307
446
38,731
115,369
148
819
887
1,397
1,119
4,469
1,325
24,636
1,960
46,981
155,558
83,739
2,480
2,450
J^.
o
-------
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o
Table 4-3. CDD/CDF congener emission factors for diesel-fueled trucks (pg/L) (continued)
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 (nondetect set to 0)
Total CDD/CDF (nondetect set to !/2 DL)
Truck tailpipe study results
50 km/hr
(test no. 40)a
200
32
130
200
1,355
763
230
524
509
397
4,340
4,340
90 km/hr
(full load)
(test no. 42)a
208
117
67
155
353
694
736
268
76
104
2,778
2,778
50 km/hr "
ND (3,760)
ND (3,020)
ND (45,300)
203,300
344,000
25,000
47,900
169,200
150,700
140,300
1,080,500
1,104,700
Mean emission factors
Assuming
nondetect set to
zero
136
49.7
65.7
67,892
115,252
8,831
16,294
56,670
50,414
46,932
362,538
Assuming
nondetect set to Vz
detection limit (DL)
762
553
7,620
67,892
115,252
8,831
16,294
56,670
50,414
46,932
370,596
"Source: Schwind et al. (1991); Hutzinger et al. (1992).
bSource: Lew (1993, 1996).
ND = Not detected; value in parenthesis is the detection limit
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Table 4-4. CDD/CDF congener emission factors for leaded gasoline-fueled automobiles (pg/L)
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
,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-CDD
Total 2,3,7,8-CDF
Total I-TEQDF ( nondetect set to 0)
Total I-TEQDF (nondetect set to
!/2 DL)
Total TEQDF-WHO98 (nondetect
set to 0)
Total TEQDF-WHO98 (nondetect
set to !/2DL)
Automotive tailpipe emission study results
FTP cycle3
ND (14.4)
ND(36)
ND(54)
ND(54)
ND(54)
ND(54)
ND(90)
432
21.6
43.2
ND(54)
ND(54)
ND(54)
ND(54)
ND(54)
ND(54)
ND(90)
ND
496.8
65.9
102
65.9
111
63 km/hr"
128
425
188
207
188
503
498
1,542
1,081
447
856
856
ND(76)
273
4,051
ND(76)
230
2,137
9,336
1,075
1,080
1,287
1,291
Idling
(test no.
12)c
NR
43
17
32
NR
119
380
NR
49
26
33
22
NR
NR
170
NR
1115
>591
>1,415
>52
>52
>72
>72
Full load
(test no.
13)c
60
106
15
35
NR
136
513
678
367
156
70
60
NR
25
NR
NR
NR
>865
> 1,356
>300
>300
>352
>352
64 km/hr
(test no.
14)c
141
468
206
228
206
554
549
1,697
1,190
492
942
942
NR
301
4,460
NR
253
2,352
> 10,277
> 1,184
> 1,184
> 1,417
> 1,417
Rated
power
(test no.
15)c
NR
40
16
30
NR
111
1,166
78
45
24
31
20
NR
NR
158
NR
447
> 1,363
>803
>56
>56
>75
>75
FTP cycle
(test no.
22C)
5
73
41
62
35
518
1,581
214
218
225
381
375
85
1,033
2,301
109
1,128
2,315
6,069
419
419
454
454
Mean emission factors
Assuming
nondetect
set to
zero
67
165
69
85
107
277
670
774
425
202
330
325
28
326
1,857
36
529
1,440
4,832
>450
>532
Assuming
nondetect
set to 1A
detection
limit (DL)
68
168
73
89
114
281
676
774
425
202
334
329
50
332
1,861
58
536
1,469
4,900
>456
>539
J^.
to
o
o
2
o
H
O
HH
H
W
O
O
-------
o
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o
4^
o
Table 4-4. CDD/CDF congener emission factors for leaded gasoline-fueled automobiles (pg/L) (continued)
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 (nondetect set
toO)
Total CDD/CDF (nondetect set to
!/2 DL)
Automotive tailpipe emission study results
FTP cycle3
5,220
ND (360)
ND (540)
ND(90)
ND(90)
15,300
2,430
ND (540)
ND (270)
ND(90)
22,950
23,940
63 km/hr"
4,555
3,338
1,868
1,164
498
50,743
11,591
6,308
5,642
230
85,937
85,937
Idling
(test no.
12)c
517
658
354
194
380
2,167
452
192
170
1,115
6,199
6,199
Full load
(test no.
13)c
8,134
2,161
623
297
513
20,513
3,608
477
NR
NR
>36,326
>36,326
64 km/hr
(test no.
14)c
5,012
3,675
2,056
1,281
549
55,857
12,757
6,947
6,210
253
94,597
94,597
Rated
power
(test no.
15)c
4,558
6,389
1,973
2,374
1,166
29,353
10,580
12,553
4,767
447
74,160
74,160
FTP cycle
(test no.
22C)
921
359
996
988
1,581
4,290
3,165
3,132
2,920
1,128
19,480
19,480
Mean emission factors
Assuming
nondetect
set to
zero
4,131
2,369
1,124
900
670
25,460
6,369
4,230
3,285
529
> 49,066
Assuming
nondetect
set to 1A
detection
limit (DL)
4,131
2,394
1,163
906
676
25,460
6,369
4,268
3,307
536
>49,212
aSource: Marklund et al. (1990); values in the table were calculated from the reported units of pg/km to pg/L using a fuel economy of 9 km/L for leaded gas as
reported in Marklund et al. (1990).
bSource: Hagenmaier et al. (1990).
cSource: Schwind et al. (1991); Hutzinger et al. (1992).
NR = Not reported
ND = Not detected; value in parenthesis is the reported detection limit
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Table 4-5. CDD/CDF congener emission factors for unleaded gasoline-fueled automobiles (without catalytic
converters) (pg/L)
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 (nondetect set to 0)
Total I-TEQDF (nondetect set to
!/2 DL)
Total TEQDF-WHO98 (nondetect set
toO)
Total TEQDF-WHO98 (nondetect set
to !/2 DL)
Automotive tailpipe emission study results
FTP cycle3
ND(5)
ND(3)
ND(40)
ND(40)
ND(40)
ND(40)
ND(50)
64
ND(7)
ND(7)
ND(40)
ND(40)
ND(40)
ND(40)
ND(40)
ND(40)
ND(70)
ND
64
6.4
26.2
6.4
26.9
63 km/hrb
2.6
19.1
16.6
17.1
17.6
40.4
176
44
44.5
20.7
41.9
21.2
37.8
54.3
27.9
16.6
119
289.4
427.9
50.9
50.9
60.2
60.2
FTP cycle
(test no.
21)c
24
14
24
84
15
192
868
70
40
30
68
62
47
55
278
ND(1)
374
1,221
1,024
96.4
96.4
102
102
64 km/hr
(test no.
17)c
44
31
26
28
29
66
280
71
72
34
68
34
61
88
45
27
194
504
694
122
122
138
138
64 km/hr
(test no.
20)c
7
11
25
42
23
121
685
77
69
184
88
35
ND(1)
42
22
24
288
914
829
144
144
148
148
64 km/hr
(test no.
31/2)c
8.9
14.1
16.3
60.1
17.1
197.8
2,634
295.2
161.8
135.2
129.1
113.2
36.9
82.1
418
54.5
991
2,948
2,417
177
177
181
181
Mean emission factors
Assuming
nondetect
set to zero
14.4
14.9
18
38.5
17
103
774
104
64.6
67.3
65.8
44.2
30.5
53.6
132
20.4
328
979
910.4
99.5
106
Assuming
nondetect
set to 1A
detection
limit (DL)
14.8
15.1
21.3
41.9
20.3
106
778
104
65.1
67.9
69.2
47.6
33.9
56.9
135
23.8
334
998
936
103
109
o
o
2
o
H
O
HH
H
W
O
V
O
-------
o
OJ
o
4^
o
Table 4-5. CDD/CDF congener emission factors for unleaded gasoline-fueled automobiles (without catalytic
converters) (pg/L) (continued)
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 (nondetect set to 0)
Total CDD/CDF (nondetect set to
!/2DL
Automotive tailpipe emission study results
FTP cycle3
13
ND(3)
ND(40)
ND(10)
ND(5)
170
ND(7)
ND(40)
ND(20)
ND(7)
183
249
63 km/hr"
435
481
305
93
176
569
931
378
476
119
3,963
3,963
FTP cycle
(test no.
21)c
429
837
484
392
868
718
531
165
278
374
5,076
5,076
64 km/hr
(test no.
17)c
706
784
496
147
280
923
1,513
615
773
194
6,431
6,431
64 km/hr
(test no.
20)c
500
542
563
225
685
478
437
258
445
288
4,421
4,421
64 km/hr
(test no.
31/2)c
304
170
114
301
2,634
6,379
1,969
1,226
1,088
991
15,176
15,176
Mean emission factors
Assuming
nondetect
set to zero
398
469
327
193
774
1,540
897
440
510
328
5,875
Assuming
nondetect
set to 1A
detection
limit (DL)
398
469
330
194
774
1,540
897
444
512
328
5,886
aSource: Marklund et al. (1990); the pg/L values in the table were calculated from the reported units of pg/km assuming a fuel economy of 10 km/L for
unleaded gas.
bSource: Hagenmaieret al. (1990).
cSource: Schwind et al. (1991); Hutzinger et al. (1992).
ND = Not detected; value in parenthesis is the reported detection limit
-------
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Table 4-6. CDD/CDF congener emission factors for unleaded gasoline-fueled automobiles (with catalytic
converters) (pg/L)
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 (nondetect set to 0)
Total I-TEQDF (nondetect set to Vi DL)
Total TEQDF-WHO98 (nondetect set to 0)
Total TEQDF-WHO98 (nondetect set to Vi DL)
Automotive tailpipe emission study test results
63 km/hra
1.6
1.6
2.4
3.5
3.1
15.3
170
4.3
3.3
2.4
4.8
6.3
0.2
4.6
16.3
ND (0.2)
27.9
197.5
70.1
7.2
7.2
7.8
7.8
64 km/hr
(test no. 29)"
3
2.6
5.3
6
6
27.8
275
10.6
8.7
7.2
10.6
9.1
ND (3.8)
18.1
54.3
ND (3.8)
38
325.7
156.6
16
16.2
17.1
17.3
64 km/hr
(test no. 30)"
ND (7.9)
ND (7.9)
ND (7.9)
6.4
ND (7.9)
78.1
427
12.7
5.1
6.2
4.5
3.9
2.1
8.2
154.2
7.9
106
511.5
310.8
10.1
16.8
9.6
18.3
64 km/hr
(test no. 18)"
14
4
1
2
2
14
197
35
13
6
5
7
5
ND(1)
51
1
140
234
263
26.3
26.4
28
28.1
Mean emission factors
Assuming
nondetect
set to zero
4.7
2.1
2.2
4.5
2.8
33.8
267
15.7
7.5
5.5
6.2
6.6
1.8
7.7
69
2.2
78
317
200
14.9
15.6
Assuming
nondetect set
to Vz detection
limit (DL)
5.6
3
3.2
4.5
3.8
33.8
267
15.7
7.5
5.5
6.2
6.6
2.3
7.9
69
2.7
78
321
201
16.6
17.9
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Table 4-6. CDD/CDF congener emission factors for unleaded gasoline-fueled automobiles (with catalytic
converters) (pg/L) (continued)
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 (nondetect set to 0)
Total CDD/CDF (nondetect set to !/2 DL)
Automotive tailpipe emission study test results
63 km/hra
28.6
25.5
26.3
38.7
170
52.6
53.4
33.3
27.1
27.9
483.4
483.4
64km/hr
(test no. 29)"
51
51
56
50
275
152
122
71
62
38
928
928
64 km/hr
(test no. 30)"
13
ND(15)
36
163
427
79
29
60
174
106
1,095
1,087
64 km/hr
(test no. 18)"
82
101
50
25
197
332
84
39
83
140
1,133
1,133
Mean emission factors
Assuming
nondetect
set to zero
43.7
44.4
42.1
69.2
267.3
153.9
72.1
50.8
86.5
78
910
Assuming
nondetect set
to Vz detection
limit (DL)
43.7
46.3
42.1
69.2
267.3
153.9
72.1
50.8
86.5
78
945
aSource: Hagenmaieretal. (1990).
bSource: Schwind et al. (1991); Hutzinger et al. (1992).
ND = Not detected; value in parenthesis is the reported detection limit
-------
Table 4-7. Total dioxin emission concentrations from heavy-duty diesel
engines
Sample
Stationary engine 1 (SI)
Stationary engine 2 (S2)
Stationary engine 3 (S3)
Stationary engine 4 (S4)
Stationary engine 5 (S5)
Truck engine 1 (VI)
Truck engine 2 (V2)
Truck engine 3 (V3)
Concentration in exhaust"
(pgl-TEQ/m3)
6.1
61b
18C
6.9
6.6
9.7
2.1
2
Sample volume (m3)
32.89
10.35
10.73
10.06
10.06
10.03
10.07
9.99
"Detection limit for sampling: 4.1 pg/m3 for stationary samples, 4.5 pg/m3 for truck samples.
bAnalysis could not be confirmed.
°High analytical detection limit (11 pg/m3).
Source: Geueke et al. (1999).
03/04/05
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Table 4-8. Levels of 2,3,7,8-chlorine-substituted congeners and total
CDDs/CDFs in vehicle exhaust particles for gasoline engines and suspended
particulate matter (SPM) (pg/g)
Congener
2,3,7,8-TCDD
Other TCDD
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
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
Other HxCDF
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
OCDD
OCDF
Total CDD/CDF
I-TEQ
Sample 1
<4.4
6.21
3.98
36.8
<7.6
<7.6
5.58
2.87
24.4
4.3
<3.8
<3.8
4.14
6.85
4.94
<1.9
<1.9
47.2
<8.2
<8.2
<1.9
<1.9
<1.9
8.76
4.78
161
3.73
Gasoline
Sample 2
<2.1
19
5.17
68.8
<3.6
11.5
6.46
5.24
53.9
<1.8
2.66
<1.8
20.5
3.95
4.48
<0.9
4.94
23.7
11.4
11.3
12.7
1.06
8.36
13.8
5.09
294
5.33
Sample 3
<1.2
7.41
3.53
41.9
<2.1
4.25
3.07
3.66
38.3
0.86
1.36
0.63
10.5
2.26
2.35
<0.5
1.99
15.2
7.64
9
7.41
0.5
4.88
17
3.03
187
3.46
SPM
<5.2
4,580
108
2,830
40.8
1,240
184
107
29,700
42.3
96.7
71
1,100
243
231
38.6
387
1,600
1,700
1,360
1,330
143
778
3,650
1450
26,000
242
Source: Miyabaraetal. (1999).
03/04/05
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Table 4-9. Levels of 2,3,7,8-chlorine-substituted congeners and total
CDDs/CDFs in vehicle exhaust particles for diesel engines (pg/g)
Congener
2,3,7,8-TCDD
Other TCDD
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
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
Other HxCDF
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
OCDD
OCDF
Total CDD/CDF
I-TEQ
Sample 1
2.81
267
5.71
84.2
10.5
165
3.17
1.11
27.3
3.39
4.59
2.14
40.9
1.29
<1.2
<1.2
<1.2
3.7
8.78
10.1
<1
<1
<1
<2.8
<4.4
642
10.6
Diesel
Sample 2
<14.4
117
15.9
335
<28.8
73.5
16.6
<11.5
211
<17.3
<17.3
<17.3
28.1
15.9
31.3
<10.1
<10.1
182
<36
<36
<8.6
<8.6
<8.6
<23
<36
1030
7.13
Sample 3
<2
86.9
7.5
313
8.15
83.6
15.1
9.52
243
4.01
4.6
<1.5
26.9
9.03
8.22
0.86
9.58
79
1.24
<1
4.69
<1
6.28
<0.5
4.25
925
14
Source: Miyabaraetal. (1999).
03/04/05
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Table 4-10. European tunnel study test results (pg/m3)
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-CDD
Total 2,3,7,8-CDF
Total I-TEQDF (nondetect set to 0)
Total I-TEQDF (nondetect set to l/i DL)
Total TEQDF-WHO98 (nondetect set to 0)
Total TEQDF-WHO98 (nondetect set to
!/2 DL)
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF (nondetect set to 0)
Total CDD/CDF (nondetect set to 1A DL)
Tunnel air
Germany3
ND (0.01)
0.31
0.37
1.19
0.44
1.9
6.3
0.17
0.4
0.19
0.26
0.16
ND (0.04)
0.12
1.2
ND(0.16)
ND(1.3)
10.51
2.5
0.58
0.59
0.73
0.74
0.23
2.5
7.8
3.4
6.3
3.5
3.6
2.
1.9
ND(1.3)
31.2
31.9
Tunnel air
Germany3
0.06
0.28
ND(0.17)
0.66
ND(0.17)
2
6.4
0.72
0.36
NR
0.13
0.15
ND (0.05)
ND (0.05)
0.98
ND(0.17)
ND(1)
9.40
2.34
0.42
0.44
0.55
0.58
0.22
1.3
2.7
3.4
6.4
6.2
4.1
1.1
1.2
ND(1)
26.6
27.1
Tunnel
air
Belgium"
0.002
0.025
0.025
0.042
0.03
0.468
2.19
0.013
0.143
0.039
0.073
0.093
0.143
0.004
0.499
0.074
0.25
2.782
1.33
0.096
0.096
0.106
0.106
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Tunnel air
Norway
(workdays)0'11
0.02
0.18
0.06
0.29
0.25
1.41
0.1
0.58
0.83
0.78
0.79
0.62
0.04
0.74
1.78
0.22
1.62
2.31
7.98
0.91
0.91
1
1
0.26
1.78
1.32
1.31
0.1
13.20
10.17
6.42
2.62
1.62
38.8
38.8
Tunnel air
Norway
(weekend)0'11
0.02
0.04
0.03
0.03
0.06
0.16
0.5
0.07
0.75
0.58
0.34
0.31
0.03
0.13
0.93
0.14
2.54
0.84
5.82
0.48
0.48
0.49
0.49
0.16
0.41
0.12
0.23
0.5
1.7
7.91
2.08
1.41
2.54
17.06
17.06
"Source: Rappe et al. (1988).
bSource: Wevers et al. (1992).
"Source: Oehme et al. (1991).
dListed values are the differences between the concentrations at the inlet and outlet of the northbound tunnel lanes.
DL = Detection limit
ND = Not detected; value in parenthesis is the detection limit
NR = Not reported
03/04/05
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Table 4-11. Baltimore Harbor tunnel study: estimated emission factors for heavy-duty diesel vehicles (pg/km)a
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Run-specific emission factors
Run 2
24.5
40.2
18.2
37.5
53.6
0
0
0
0
24.5
15.4
0.3
27.7
15.2
12.6
0
0
174
95.7
73.8
93.8
245
110
677
0
0
0
124
136
0
0
1,291
Run 3
61.6
20.6
25.2
28.2
56.5
401
3,361
94.3
48.9
75.7
139
75.1
14.8
82.5
280
58.5
239
3,954
1,108
175
182
0
21.9
0
802
3,361
901
119
319
223
239
5,987
Run5
0
15.4
46.5
64.3
91.6
729
3,382
67.6
72.6
131
204
73.7
75.6
152
445
60.8
401
4,328
1,684
170
175
140
83.3
753
1,498
3,382
1,314
1,152
852
814
401
10,390
Run 6
21.2
5.6
8.3
19.6
48.4
111
1,120
152.8
23.6
46.6
93.8
51
0
55.7
154
31.1
175
4,328
1,684
170
175
165
35.6
54.5
142
1,120
656
78.4
67.6
144
175
2,638
Run 8
37.8
38.4
64.5
153
280
2,438
9,730
155.8
53.3
85
124
61.3
20.6
93
313
25
416
1,335
784
96
97
311
174
2,009
5,696
9,730
2,416
1,055
444
513
416
22,766
Run 9
40.1
0
0
71.1
126
963
5,829
73.4
0
63.9
164
54.4
37.2
86.8
354
2.3
534
7,028
1,371
153
147
109
0
1,666
1,933
5,829
1,007
282
719
354
534
12,434
Run 10
54.9
83
123
186
370
2,080
7,620
61.7
43.3
108
166
95.5
63.5
111
308
34.9
370
10,515
1,362
303
337
97.3
165
2,971
4,377
7,620
687
626
619
637
370
18,168
Mean
f*in i ssirtn
CiiiiaMUii
factors
34.3
29
40.8
80
147
960
4,435
86.5
34.5
76.4
129
58.8
34.2
85.2
267
30.4
305
5,725
1,107
172
182
152
84.2
1,162
2,064
4,435
997
491
451
384
305
10,525
J^.
to
o
o
2
o
H
O
HH
H
W
O
V
O
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Table 4-11. Baltimore Harbor tunnel study: estimated emission factors for heavy-duty diesel vehicles (pg/km)a
(continued)
Congener/congener group
Heavy-duty vehicles as % of total
vehicles
Run-specific emission factors
Run 2
21.2
Run 3
22
Run5
22.6
Run 6
34
Run 8
28.8
Run 9
24.2
Run 10
27.4
Mean
emission
factors
25.7
O
O
2
o
H
O
HH
H
W
O
aListed values are based on the difference between the calculated chemical mass entering the tunnel and the mass exiting the tunnel. All calculated negative
emission factors were set equal to zero. All CDD/CDF emissions were assumed to result from heavy-duty diesel-fueled vehicles.
Source: Gertleretal. (1996, 1998).
O
-------
Table 4-12. Average CDD/CDF concentration in flue gas
Fuel
Spruce wood
Wheat straw
Hay (set-aside land)
Triticale (whole crop)
Concentration (pg TEQ/m3)
52
656
891
52
Number of trials
7
5
4
5
Source: Launhardt and Thoma (2000).
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Table 4-13. Results from Environment Canada residential wood stove analysis (pg TEQ/kg wood)
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
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
TOTAL
Average (ng/kg wood)
U.S. EPA-certified
Maple
Run 1
212
108
21
21
21
2
1
129
22
243
22
15
17
10
2
2
0
846
Run 2
214
138
16
16
16
2
0
134
24
371
31
18
17
10
1
1
0
1,012
Run 3
256
117
17
17
17
2
0
127
23
350
23
20
14
11
2
1
0
998
0.952
Spruce
Run 1
82
41
10
10
10
1
0
95
12
186
12
8
8
8
1
1
0
486
Run 2
110
66
18
18
18
2
0
47
13
149
13
13
13
13
2
2
0
496
Run 3
91
57
14
14
14
2
0
55
17
302
23
15
10
10
2
2
0
628
0.537
Conventional
Maple
Run 1
68
34
8
8
8
1
0
28
6
85
27
10
7
4
2
1
0
298
Run 2
75
56
13
13
13
1
1
38
4
78
11
8
8
8
2
1
1
331
Run 3
56
47
9
9
9
2
1
36
4
66
10
6
6
6
1
1
0
269
0.299
Spruce
Run 1
63
27
7
7
7
1
0
27
5
54
16
4
4
4
1
0
0
228
Run 2
70
39
7
7
7
2
1
16
2
17
7
7
7
7
1
1
0
198
Run 3
66
41
10
10
10
1
0
18
5
33
18
8
8
8
1
1
0
240
0.222
O
O
2
o
H
O
HH
H
W
O
Source: Environment Canada (2000).
O
-------
o
OJ
o
4^
o
Table 4-14. CDD/CDF mean emission factors for industrial wood combustors (ng/kg wood)
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 TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total I-TEQDF
Total TEQDF-WH098
Total CDD/CDF
Four facilities tested by CARB
Nondetect set to
zero
0.007
0.044
0.042
0.086
0.079
0.902
6.026
0.673
0.79
0.741
0.761
0.941
0.343
0.45
2.508
0.26
1.587
0.151
1.039
1.748
2.936
6.026
4.275
9.75
7.428
3.747
1.588
0.82
0.84
38.69
Nondetect set to
Vz detection limit
0.016
0.054
0.055
0.096
0.132
0.905
6.026
0.673
0.79
0.741
0.768
0.941
0.35
0.491
2.749
0.344
1.59
0.154
1.039
1.748
2.936
6.026
4.275
9.75
7.428
3.988
1.59
0.85
0.87
38.93
Five facilities tested by NCASI
Nondetect
set to zero
0.066
0.11
0.179
0.191
0.522
0.635
1.317
0.707
0.145
0.159
0.108
0.071
0.064
0.015
0.072
0.017
0.049
1.628
1.958
1.792
1.12
1.317
4.532
1.548
0.536
0.111
0.049
0.4
0.46
14.593
Nondetect set to ¥2
detection limit
0.068
0.112
0.183
0.193
0.524
0.637
1.317
0.719
0.149
0.164
0.111
0.073
0.067
0.017
0.074
0.02
0.06
1.629
1.98
1.796
1.132
1.317
4.552
1.549
0.543
0.116
0.06
0.41
0.46
14.674
Nine facilities tested by
CARB and NCASI
Nondetect set
to zero
0.04
0.079
0.115
0.138
0.321
0.745
3.329
0.684
0.406
0.389
0.375
0.418
0.178
0.192
1.062
0.113
0.674
0.969
1.521
1.663
1.821
3.329
4.353
4.93
3.316
1.58
0.674
0.56
0.6
24.155
Nondetect set to
Vz detection limit
0.046
0.084
0.123
0.143
0.342
0.748
0.329
0.69
0.409
0.392
0.379
0.419
0.183
0.209
1.155
0.152
0.681
0.97
1.533
1.665
1.823
0.329
4.364
4.93
3.32
1.674
0.681
0.58
0.62
24.294
Oi
Oi
O
O
2
O
H
O
HH
H
W
O
V
O
CARB = California Air Resources Board
NCASI = National Council for Air and Stream Improvement
Sources: CARB (1990b, e, f, g); NCASI (1995).
-------
Table 4-15. NCASI CDD/CDF TEQ concentrations and emissions for wood
residue-fired boilers
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
Wood-fired boiler emissions
TEQ
concentrations
(median us/ton)
0
0
0
4.00e-04
5.00e-04
1.05e-03
5.69e-04
4.40e-03
7.50e-04
5.00e-03
9.00e-04
7.00e-04
2.10e-03
9.00e-04
2.80e-04
1.10e-04
2.10e-05
1.77e-02
Emissions
(ns/yr)
0
0
0
1.68e+07
2.10e+07
4.41e+07
2.39e+07
1.85e+08
3.15e+07
2.10e+08
3.78e+07
2.94e+07
8.82e+07
3.78e+07
1.18e+07
4.62e+06
8.82e+05
7.43e+08
Wood-fired boiler ash not landfilled
(72% of total ash landfilled)
TEQ
concentrations
(ns/ks)
1.84e+00
1.73e+00
3.25e-01
4.28e-01
2.60e-01
4.01e-01
1.90e-02
4.20e+00
3.35e-01
3.23e+00
2.21e-01
1.606-01
5.40e-02
3.80e-02
4.10e-03
1.30e-03
5.40e-04
1.326+01
Emissions (ng/yr)
3.06e+08
2.88e+08
5.41e+07
7.12e+07
4.33e+07
6.71e+07
3.96e+06
7.06e+08
5.56e+07
5.37e+08
3.68e+07
2.66e+07
8.98e+06
6.32e+06
6.82e+05
2.16e+05
1.64e+05
6.19e+08
(ash not landfilled)
2.21e+09
(ash landfilled)
NCASI = National Council for Air and Stream Improvement
Source: Gillespie (2002).
03/04/05
4-67
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Table 4-16. CDD/CDF concentrations in residential chimney soot from
wood stoves and fireplaces (ng/kg)
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-TEQnf
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
U.S. east
region3
66
NR
250e
250e
208
1,143
2,033
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
3,450
NR
>125
>123
1,987
NR
2,183
2,104
2,033
NR
NR
NR
NR
NR
8,307
U.S. west
region3
13.3
NR
522e
522e
282
1,653
2,227
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
4,175
NR
>112
>110
269
NR
4,273
3,243
2,227
NR
NR
NR
NR
NR
10,012
U.S.
central
region3
66
NR
l,831e
l,831e
1,450
6,160
13,761
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
21,437
NR
>479
>467
1,511
NR
14,243
12,603
13,761
NR
NR
NR
NR
NR
42,118
German
farmhouse1"
150
70
35
60
30
90
90
930
560
590
330
400
70
200
490
40
70
525
3,680
720
755
3,900
880
600
200
90
13,400
6,100
3,200
720
70
29,160
Canadian
wood
stovec
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
ND(10)
ND(10)
ND(50)
100
200
ND(10)
ND(10)
ND(50)
ND(50)
ND(50)
300
Canadian
fireplace0
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
ND(10)
500
1,700
500
400
300
1,400
1,700
400
100
7,000
Canadian
wood
stove"
ND(12)
70
ND(10)
625
281
948
530
235
58
68
51
57
8
24
97
20
41
2,454
659
211
246
11
608
3,450
1,550
530
1,010
948
482
154
41
8,784
^Source: Nestrick and Lamparski (1982, 1983); mean values listed, six samples collected in each region.
bSource: Bacher et al. (1992).
C8ource: Clement etal. (1985b).
dSource: Van Oostdam and Ward (1995); mean of two samples, nondetect values assumed to be zero.
eAnalytical method could not distinguish between congeners; listed value is the sum of both congeners.
NR = Not reported
ND = Not detected; value in parenthesis is the reported detection limit
03/04/05
4-68 DRAFT—DO NOT CITE OR QUOTE
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Table 4-17. CDD/CDF concentrations in bottom ash from residential wood
stoves and fireplaces (ng/kg)
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 TEQ
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Canadian
wood stove ash
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
ND(10)
ND(10)
ND(50)
300
2,600
9,100
2,200
1,000
700
ND(50)
15,900
Canadian wood
stove ash
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
100
3,000
10,000
1,200
900
400
4,600
9,300
1,000
100
30,600
Canadian
wood stove ash
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
100
200
700
500
100
100
200
500
300
ND(50)
2,700
Canadian
fireplace ash
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
ND(10)
ND(10)
300
2,000
3,100
ND(10)
ND(10)
100
400
100
6,000
NR = Not reported.
ND = Not detected; value in parenthesis is the reported detection limit
Source: Clement et al. (1985b).
03/04/05
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Table 4-18. CDD/CDF concentrations in chimney soot (Bavaria, Germany)
Unit type
Oven
Tiled stove
Heating system
Oven
Tiled stove
Oven
Fuel type
Wood
Wood
Wood
Wood/coal
Wood/coal
Wood, wood/coal,
waste
Number of
samples
33
39
9
27
5
5
CDD/CDF concentrations in soot
(ngI-TEQDF/kg)
Minimum
10.4
4
16.9
77.3
53.1
116.3
Mean
2,015
3,453
1,438
2,772
549
6,587
Maximum
15,849
42,048
20,450
10,065
4,911
10,652
Source: Dumler-Gradl et al. (1995a).
03/04/05
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DRAFT—DO NOT CITE OR QUOTE
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Table 4-19. Fly ash from wood-working industry (ng/kg)
Congener/congener group
2,3,7,8-TCDD
Total TCDD
1,2,3,7,8-PeCDD
Total PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Total HxCDD
1,2,3,4,6,7,8-HpCDD
Total HpCDD
Total OCCD
TOTAL TCDD TEQ
2,3,7,8-TCDF
Total TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Total PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,6,7,8-HxCDF
Total HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Total HpCDF
Total OCDF
TOTAL CDF TEQ
Average
concentration
<15
1,730
100
1,250
130
150
140
750
280
470
300
130
1,300
100
120
790
40
40
<10
150
320
<10
570
60
I-TEQDF
<15
50
13
15
14
3
-
0.3
95-110
13
5
60
4
4
<1
3
<0.1
-
0.06
89-90
TEQDF-WH098
<15
100
13
15
14
3
-
0.03
145-160
13
5
60
4
4
<1
O
<0.1
-
0.006
89-90
Source: Pohlandt and Marutzky (1994).
03/04/05
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Table 4-20. Electrostatic precipitator waste ash from wood-fired industrial
boiler (ng/kg)
Congener/congener group
2,3,7,8-TCDD
Total TCDD
1,2,3,7,8-PeCDD
Total PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Total HxCDD
1,2,3,4,6,7,8-HpCDD
Total HpCDD
Total OCDD
TOTAL CDD
2,3,7,8-TCDF
Total TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Total PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Total HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Total HpCDF
Total OCDF
TOTAL CDF
TOTAL DIOXINS/FURANS
Average
concentration
17.85
239
30.67
226.83
20.33
26.33
23.33
300
325
706.67
786.67
2,439.17
285
2,713.33
154.5
641.67
2,666.67
244.83
179.67
296.67
7.28
1,520
147.67
21.33
248.33
48.33
7,196.67
I-TEQDF
17.85
15.33
2.03
2.63
2.33
-
3.25
-
0.79
44.22
28.5
7.73
320.83
24.48
17.97
29.67
0.73
-
1.48
0.21
0.05
431.64
475.64
TEQDF-WH098
17.85
30.67
2.03
2.63
2.33
-
3.25
-
0.08
58.85
28.5
7.73
320.83
24.48
17.97
29.67
0.73
-
1.48
0.21
0
431.6
490.44
Source: CARB (1990e, Table 30).
03/04/05
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Table 4-21. Estimated CDD/CDF emission factors for oil-fired residential
furnaces
Congener/
congener group
2,3,7,8-TCDD
Total PeCDD
Total HxCDD
Total HpCDD
OCDD
2,3,7,8-TCDF
Total PeCDF
Total HxCDF
Total HpCDF
OCDF
TOTAL
Mean
facility
emission
factor
(pg/L oil)
56
82
66
63
66
53
420
170
73
30
WHO-
TEF
1
1
0.1
0.01
0.0001
0.1
0.05
0.1
0.01
0.0001
Emission
factor (pg
TEQDF-
WHO98/L
oil)
56
82
7
1
0
5
21
17
1
0
190
I-TEF
1
0.5
0.1
0.01
0.001
0.1
0.05
0.1
0.01
0.001
Emission
factor (pg
I-TEQDF/L
oil)
56
41
7
1
0
5
21
17
1
0
149
Source: U.S. EPA (1997b).
03/04/05
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Table 4-22. CDD/CDF emission factors for oil-fired utility/industrial
boilers (pg/L oil)
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
U.S. EPA (1997b)
median
emission factora'b
117
104
215
97
149
359
413
83
77
86
109
68
104
86
169
179
179
1,453
1,141
314
366
102
104
145
359
413
90
131
172
27
179
1,722
EPRI (1994) mean emission factor3'0
Non detect set to
zero
0
24.7
63.3
65.8
79.7
477
2,055
0
64.1
49.3
76.5
35.4
0
23.8
164
0
0
2,766
414
83.1
93.6
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
3,179
Nondetect set to Vz
detection limit
26.6
43.1
108
79.3
102
546
2,141
35.7
73.9
59.6
94.9
45.2
37.7
42.2
218
137
139
3,047
883
147
167
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
3,931
a Assumes a density for residual fuel oil of 0.87 kg/L.
bNumber of facilities not reported.
"Based on two cold-side power plants equipped with electrostatic precipitators.
NR = Not reported
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o
OJ
o
4^
o
Table 4-23. CDD/CDF concentrations in stack emissions from U.S. coal-fired power plants (pg/Nm3)
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-CDD
Total 2,3,7,8-CDF
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Plant 1
ND (3.5)
ND (0.56)
ND (0.56)
ND (0.44)
ND (0.56)
ND (1.7)
ND(12)
ND (1.7)
ND(1)
2.4
3.3
1.1
ND (0.44)
ND(2)
2
ND (0.63)
5.6
0
14
1.8
ND(1)
1.3
3.4
ND(12)
ND (5.2)
5.4
7.6
4.3
5.6
29
Plant 2
ND(3.5)
ND (4.8)
ND (5.7)
5
4.9
29
32
8.1
ND (5.7)
ND(19)
16
ND(5)
11
ND (4.2)
29
ND(6.1)
33
71
97
12
4.4
18
45
32
29
33
39
34
33
279
Plant 3
1
ND(1.8)
ND (3.6)
ND(1.8)
ND(1.8)
ND(1.8)
ND(14)
7.8
7.2
6.6
8.4
2.9
ND(1.8)
3
6
ND (3.6)
2.4
1
44.3
12
6
2.7
ND (2.4)
ND(14)
78
61
29
9
2.4
200.1
Plant 4
ND(2)
ND(10)
ND(10)
ND(10)
ND(10)
ND(10)
ND(20)
ND(2)
ND(10)
ND(10)
ND(10)
ND(10)
ND(10)
ND(10)
ND(10)
ND(10)
ND(20)
0
0
NR
ND(10)
ND(10)
ND(10)
ND(20)
ND(2)
ND(10)
ND(10)
ND(10)
ND(20)
0
Plant 5
ND (3.3)
ND (4.7)
ND (15.4)
ND (9.9)
ND(12.1)
ND (26.4)
ND(131)
ND (3.3)
ND (3.2)
ND (3.2)
ND (16.4)
ND (5.8)
ND (8.8)
ND (16.4)
ND(23)
ND (15.4)
ND(131)
0
0
6.7
ND (4.7)
ND (26.3)
ND (26.4)
ND(131)
ND (3.3)
ND (6.6)
ND (16.4)
ND (29.5)
ND(131)
6.7
Plant 6
ND (2.6)
ND (3.2)
ND (2.7)
ND (4.2)
ND (4.3)
4.3
20
13
ND (5.7)
ND (4.8)
ND(5.1)
ND(4)
ND (6.9)
ND (2.5)
ND(30)
ND(5)
ND(19)
24.3
13
ND (2.6)
ND (3.2)
ND(4)
ND(14)
20
88
14
ND(5)
ND(20)
ND(19)
122
Plant 7
ND (1.7)
ND(1.8)
ND(2)
ND (1.4)
ND (1.2)
2.4
21.6
0.7
ND(l.l)
ND (1.4)
ND(1.8)
ND(1.3)
ND(1.5)
ND(2)
ND (2.2)
ND(2.1)
11.4
24
12.1
ND(55)
ND(32)
ND(24)
ND(8.1)
21.6
ND(37)
o
J
ND(27)
2.9
11.4
38.9
o
o
2
o
H
O
HH
H
W
O
V
O
ND = Not detected; value in parenthesis is the detection limit
NR = Not reported; suspected contamination problem
Source: Riggs et al. (1995).
-------
Table 4-24. Characteristics of U.S. coal-fired power plants tested by the U.S.
Department of Energy
Plant no.
1
2
3
4
5
6
7
Coal type
Bituminous
Bituminous
Sub-bituminous
Sub-bituminous
Bituminous
Lignite
Bituminous
Coal chlorine
content (mg/kg)
800
1,400
300
390
1,400
400
1,000
Temperature (°C)a
ESP
160
130
-
-
130
170
150
FF
-
-
150
70
-
-
-
FGD
-
-
-
130
120
170
-
Stack
160
130
150
75
40
110
150
Temperature at pollution control device and stack.
ESP = Electrostatic precipitator
FF = Fabric filter
FGD = Flue gas desulfurization system
Source: Riggs et al. (1995).
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Table 4-25. CDD/CDF emission factors for coal-fired utility/industrial
power plants (ng/kg coal)a
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 I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean emission factor
Nondetect set to zero
0.005
0
0
0.004
0.004
0.216
0.513
0.109
0.007
0.074
0.098
0.014
0.013
0.043
0.354
0.087
0.158
0.079
0.078
0.051
0.014
0.03
0.063
0.513
0.154
0.18
0.104
0.064
0.158
1.331
Nondetect set to 1A
detection limit
0.018
0.016
0.034
0.028
0.035
0.241
0.644
0.117
0.021
0.084
0.12
0.03
0.038
0.06
0.385
0.112
0.281
0.124
0.131
0.052
0.015
0.03
0.074
0.644
0.158
0.18
0.104
0.064
0.281
1.602
aEleven-facility data set.
Source: EPRI (1994).
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Table 4-26. CDD/CDF emission factors for residential coal combustors
(ng/kg coal)
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 2,3,7,8-CDDc
Total 2,3,7,8-CDFc
Total I-TEQDFC
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
"Salt"
lignite"
0.58
0.73
0.63
0.6
0.4
3.24
16.19
2.49
2.24
2.09
0.38
1.86
0.07
1.01
2.59
0.25
0.63
22.37
13.6
2.74
14.23
14.15
11.14
7.06
16.19
80.34
29.21
12.72
3.87
0.63
189.5
"Normal"
lignitea
0.06
0.08
0.06
0.09
0.06
0.59
2.42
0.5
0.43
0.31
0.13
0.36
0.02
0.12
0.95
0.06
0.3
3.38
3.2
0.34
9
2.22
1.81
0.82
2.42
20.33
8.98
3.78
1.27
0.3
50.9
Anthraciteb
1.6
NR
NR
NR
NR
NR
77
42
NR
NR
NR
NR
NR
NR
NR
NR
4.2
NR
NR
60
61.6
31
60
57
77
412
340
130
32
4.2
1,205
Bituminous11
2.4
NR
NR
NR
NR
NR
120
63
NR
NR
NR
NR
NR
NR
NR
NR
6.3
NR
NR
98.5
92.4
46
90
86
120
613
550
190
47
6.3
1,841
aSource: Thub et al. (1995); listed results represent means of three flue gas samples.
bSource: U.S. EPA (1997b); based on average paniculate CDD/CDF concentrations from chimney soot samples
collected from seven coal ovens and paniculate emission factors for anthracite and bituminous coal combustion.
°Values as reported in sources.
NR = Not reported
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Table 4-27. Coal-fired utility solid wastes
Congener
2,3,7,8-TCDDd
l,2,3,7,8-PeCDDd
l,2,3,4,7,8-HxCDDd
l,2,3,6,7,8-HxCDDd
1,2,3,7,8,9-HxCDD6
l,2,3,4,6,7,8-HpCDDf
OCDDg
2,3,7,8-TCDFh
l,2,3,7,8-PeCDFd
2,3,4,7,8-PeCDFd
l,2,3,4,7,8-HxCDFe
l,2,3,6,7,8-HxCDFd
2,3,4,6,7,8-HxCDFd
l,2,3,7,8,9-HxCDFd
1,2,3,4,6,7,8-HpCDF6
l,2,3,4,7,8,9-HpCDFd
OCDF1
Mean
concentration3
(ng/kg)
0.17
0.25
0.35
0.28
0.3
0.59
10.54
0.19
0.17
0.17
0.25
0.18
0.28
0.24
0.29
0.35
0.59
Grams per
year
disposed of
in solid
waste" 1987
10
14
20
16
17
33
593
11
10
10
14
10
16
14
16
20
33
Grams per
year
disposed of
in solid waste0
1995
10
14
20
16
17
34
603
11
10
10
14
10
16
14
17
20
34
TOTAL
I-TEQDF
/yr (g) 1995
9.72
7.15
2
1.6
1.72
0.34
0.6
1.09
0.49
4.86
1.43
1.03
1.6
1.37
0.17
0.2
0.03
35.41
TEQDF-
WH098/yr
(g) 1995
9.72
14.3
2
1.6
1.72
0.34
0.6
1.09
0.49
4.86
1.43
1.03
1.6
1.37
0.17
0.2
0.01
41.98
Source: U.S. EPA (1999b, Table 2-9).
bAssumes that solid waste quantity for 1987 is 98.4% of 1995 quantity, based on total utility coal use in those years
(see Section 4.4).
"Based on EPRI estimate of 63 million tons/yr of large-volume utility coal combustion solid wastes. See Section
3.3 of U.S. EPA (1999c). Assumes all waste characteristics are same as for comanaged wastes.
dAll 17 analyses were nondetects.
eSixteen of the 17 analyses were nondetects.
Eleven of the 17 analyses were nondetects.
Tive of the 17 analyses were nondetects.
fourteen of the 17 analyses were nondetects.
'Fifteen of the 17 analyses were nondetects.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25 0.3
0.35
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25 0.3
0.35
I Cars I I Trucks
Note: Based on profiles calculated from emission factors (ND = !4 DL) from Tables 4-2 and 4-3.
Figure 4-1. Congener and congener group profiles for air emissions from
diesel-fueled vehicles.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.01 0.02 0.03 0.04
0.05
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3 0.4 0.5
Note: Based on profiles calculated from emission factors (ND = !4 DL) from Table 4-4.
Figure 4-2. Congener and congener group profiles for air emissions from
leaded gas-fueled vehicles.
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.05 0.1 0.1S 0.2 0.25 0.3
0.35
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25 0.3
0.35
Note: Profiles are for catalytic converter equipped vehicles; based on data from Table 4-6.
Figure 4-3. Congener and congener group profiles for air emissions from
unleaded gas-fueled vehicles.
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§0.6
§0.5
•a
•5
^0.4
8
8
SO-3
I
§0.2
S
I0-1
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
• Norway (Row l)a ^H Germany (Row 2)b ^H Germany (Row 3)b
I Belgium (Row 4)c ^1 Baltimore, USA (Row 5)d
Note: Congener numbers refer to the congeners in order as listed in Table 4-7.
Figure 4-4. Tunnel air concentrations.
"Source: Oehme(1991).
bSource: Rappe et al. (1988).
"Source: Wevers et al. (1992).
dSource: Gertleretal. (1996, 1998).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.05 0.1
0.15
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
Ratio (mean congener group emission factor/total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25
0.3
Nondetects set equal to zero.
Figure 4-5a. Congener and congener group profiles for air emissions from
industrial wood combustors.
Sources: CARB (1990b, e, f, g).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3
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
Ratio (congener emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3
Nondetects set equal to zero.
Figure 4-5b. Congener and congener group profiles for air emissions from
bleached Kraft mill bark combustors.
Source: NCASI (1995).
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Ratio (congener group emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3
0.4
Figure 4-6. Congener group profile for air emissions from residential
oil-fueled furnaces.
Source: U.S. EPA (1995c).
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Ratio Factor (congener emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2
0.25
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0.05 0.1 0.15 0.2
0.25
Figure 4-7. Congener and congener group profiles for air emissions from
industrial oil-fueled boilers.
Source: U.S. EPA (1995c; 1997b).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
0.09
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.05 0.1 0.15 0.2 0.25 0.3
0.35
Nondetects set equal to zero.
Figure 4-8. Congener and congener group profiles for air emissions from
industrial/utility coal-fueled combustors.
Source: EPRI(1994).
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Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.1 0.2 0.3
0.4
I Anthracite
I I Bituminous
Figure 4-9. Congener group profile for air emissions from residential
coal-fueled combustors.
Source: U.S. EPA (1997b).
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1 5. COMBUSTION SOURCES OF CDDs/CDFs: OTHER
2 HIGH-TEMPERATURE SOURCES
3
4 5.1. CEMENT KILNS
5 This section addresses CDD/CDF emissions from Portland cement kilns. These facilities
6 use high temperatures to convert mineral feedstocks into Portland cement and other types of
7 construction materials. For purposes of this analysis, cement kilns are subdivided into two
8 categories: those that burn hazardous waste and those that do not. Additionally, for the 1987 and
9 1995 estimates, the hazardous waste-burning cement kiln category was further divided into kilns
10 with inlet air pollution control device (APCD) temperatures above 232 °C and below 232 °C.
11 The following subsections describe cement kiln technology, the derivation of TEQ emission
12 factors for cement kilns that burn hazardous waste as supplemental fuel and those that do not,
13 and the derivation of annual TEQ air emissions (g/yr) for reference years 1987, 1995, and 2000.
14
15 5.1.1. Process Description of Portland Cement Kilns
16 In the United States, the primary cement product is Portland cement. Portland cement is
17 a fine, gray powder consisting of a mixture of four basic materials: lime, silica, alumina, and iron
18 compounds. Cement production involves heating (pyroprocessing) the raw materials to a very
19 high temperature in a rotary (rotating) kiln to induce chemical reactions that produce a fused
20 material called clinker. The cement clinker is then ground into a fine powder and mixed with
21 gypsum to form the Portland cement.
22 The cement kiln is a large, steel, rotating cylindrical furnace lined with refractory
23 material. The kiln is aligned on a slight angle, usually a slope of 3 to 6 degrees, which allows the
24 materials to pass through the kiln by gravity. The kiln rotates at about 50 to 70 revs/hr, and the
25 rotation induces mixing and the downward movement of mixed materials. The upper end of the
26 kiln, known as the cold end, is generally where the raw materials, or meal, are fed into the kiln.
27 Midpoint injection is practiced at some facilities. The lower end of the kiln, known as the hot
28 end, is where the combustion of primary fuels (usually coal and petroleum coke) occurs,
29 producing a high temperature. The cement kiln operates using countercurrents: hot combustion
30 gases are convected up through the kiln while the raw materials pass down toward the lower end.
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1 As the meal moves through the cement kiln and is heated by hot combustion gases, water is
2 vaporized and pyroprocessing of materials occurs.
3 The cement kiln consists of three thermal zones to produce cement clinker. Zone 1 is at
4 the upper end of the kiln where the raw meal is added. Temperatures in this zone typically range
5 from ambient up to 600 °C. In this area of the kiln, moisture is evaporated from the raw meal.
6 Zone 2 is known as the calcining zone. Calcining occurs when the hot gases from the
7 combustion of primary fuels dissociate calcium dioxide from the limestone and form calcium
8 oxide. In this zone, temperatures range from 600 to 900 °C. Zone 3, the burning or sintering
9 zone, is the lowest and hottest region of the kiln. Here, temperatures in excess of 1,500 °C
10 induce the calcium oxide to react with silicates, iron, and aluminum in the raw materials to form
11 the cement clinker. The formation of clinker actually occurs close to the combustion of primary
12 fuel. The chemical reactions that occur in zone 3 are referred to as pyroprocessing.
13 The cement clinker, which leaves the kiln at the hot end, is a gray, glass-hard material
14 consisting of dicalcium silicate, tricalcium silicate, calcium aluminate, and tetracalcium
15 aluminoferrite. At this point, the temperature of the clinker is about 1,100 °C. The hot clinker is
16 then dumped onto a moving grate, where it cools as it passes under a series of cool-air blowers.
17 After it is cooled to ambient temperature, the clinker is ground into a fine powder and mixed with
18 gypsum to produce the Portland cement product.
19 Cement kilns can be either wet process or dry process. In the wet process, the raw
20 materials are ground and mixed with water to form a slurry, which is fed into the kiln through a
21 pump. This is an older process. A greater amount of heat energy is needed in the wet process
22 kiln than in other types of kilns. These kilns consume about 5 to 7 trillion Btu per ton of clinker
23 product to evaporate the additional water. In the dry process, a preheater is used to dry the raw
24 meal before it enters the kiln. A typical preheater consists of a vertical tower containing a series
25 of cyclone-type vessels. Raw meal is added at the top of the tower and hot exhaust gases from
26 the kiln operation preheat the meal, thus lowering the fuel consumption of the kiln. Dry kilns are
27 now the most popular type of cement kiln.
28 Portland cement clinker production in the United States is estimated to have been 52
29 billion kg in 1987 (U.S. DOC, 1996), 67.6 billion kg in 1995 (U.S. DOC, 1996), and 75.2 billion
30 kg in 2000 (PCA, 2001, 2003a). The 2000 estimate is based on the assumption that of the annual
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1 maximum clinker capacity reported for that reference year (PCA, 2001), only 90% was actually
2 produced (PCA, 2003a).
3
4 5.1.2. Cement Kilns That Burn Hazardous Waste
5 The high temperatures achieved in cement kilns make the kilns an attractive technology
6 for combusting hazardous waste as supplemental fuel. Sustaining the relatively high combustion
7 temperatures that are needed to form cement clinker (1,100 to 1,500 °C) requires the burning of a
8 fuel with a high energy output. Therefore, coal or petroleum coke is typically used as the primary
9 fuel source. Because much of the cost of operating the cement kiln at high temperatures is
10 associated with the consumption of fossil fuels, some cement kiln operators burn hazardous
11 liquid and solid waste as supplemental fuel. In 2000, approximately 60% of all facilities burned
12 hazardous waste as the primary fuel to offset the amount of coal/coke purchased and burned by
13 the kiln (PCA, 2001). Organic hazardous waste may have a heating value similar to that of coal
14 (9,000 to 12,000 Btu/lb for coal). The kiln operator may charge the waste generator a disposal
15 fee to combust the hazardous waste; this fee also offsets the cost of kiln operation. The high-
16 energy and ignitable wastes include diverse substances, such as waste oils, spent organic
17 solvents, sludges from the paint and coatings industry, waste paints and coatings from auto and
18 truck assembly plants, and sludges from the petroleum refining industry (Greer et al., 1992).
19 The conditions in the cement kiln mimic conditions of hazardous waste incineration. For
20 example, the gas residence time in the burning zone is typically 3 sec at temperatures in excess of
21 1,500 °C (Greer et al., 1992). The method of introducing liquid and solid hazardous waste into
22 the kiln is a key factor in the complete consumption of the waste during the combustion of the
23 primary fuel. Liquid hazardous waste is either injected separately or blended with the primary
24 fuel (coal). Solid waste is mixed and burned along with the primary fuel.
25 Trial burns have consistently shown that destruction and removal efficiencies of 99.99 to
26 99.9999% can be achieved for very stable organic wastes using cement kilns (Greer et al., 1992).
27 Hazardous waste was combusted at 34 of the 212 kilns operating in 1995 (Federal Register,
28 1996b) and at 33 of the 201 kilns operating in 2000 (e-mail correspondence between M. Benoit,
29 Cement Kiln Recycling Coalition, and K. Riley, Versar, Inc., dated February 24, 2003; PCA,
30 2001). Other types of supplemental fuel used by these facilities include natural gas, fuel oil,
31 automobile tires, used motor oil, sawdust, and scrap wood chips.
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1 5.1.3. Air Pollution Control Devices
2 The pyroprocessing of raw meal in a cement kiln also produces fine particulates, referred
3 to as cement kiln dust (CKD). CKD is collected and controlled with fabric filters (FFs),
4 electrostatic precipitators (ESPs), or both. Acid gases such as SO2 can be formed during
5 pyroprocessing of the sulfur-laden minerals and fuels, but the minerals have high alkalinity,
6 which partially neutralizes SO2 gases. Most APCDs used at cement kilns in 1987 and 1995 were
7 considered to be hot-sided control devices. A hot-sided control device is one that operates at kiln
8 exhaust gas temperatures above 232 °C (some EPA rules use different definitions for hot-sided
9 control devices for different industries). Most APCDs currently used at cement kilns are cold-
10 sided devices (i.e., they operate at kiln exhaust gas temperatures below 232 °C.
11 Reducing the temperature at the inlet of the APCD is one factor that has been shown to
12 have a significant impact on limiting dioxin formation and emissions at cement kilns (U.S. EPA,
13 1997d). Emissions testing at a Portland cement kiln showed that CDDs/CDFs were almost
14 entirely absent at the inlet to a hot-sided ESP, but measurements taken at the exit showed
15 conclusively that dioxins were formed within the hot-sided ESP (U.S. EPA, 1997d). Reducing
16 the kiln exhaust gas temperature in the APCD to below 232 °C has been shown to substantially
17 limit CDD/CDF formation. Lower temperatures are believed to prevent the post-combustion
18 catalytic formation of CDDs/CDFs. Consequently, a number of cement kilns have added exhaust
19 gas-quenching units upstream of the APCD to reduce the inlet APCD temperature, thereby
20 reducing CDD/CDF stack concentrations. A quenching unit usually consists of a water spray
21 system within the flue duct.
22
23 5.1.4. CDD/CDF Emissions Data
24 The general strategy used in this document for deriving emission factors is to divide each
25 source category on the basis of design and operation. However, because cement kilns are
26 relatively uniform in terms of kiln design, raw feed material, operating temperatures, and
27 APCDs, they have been categorized, as noted above, only on the basis of whether or not
28 hazardous waste is burned as a supplementary fuel.
29 CDD/CDF emissions data from tests conducted between 1989 and 1996 were obtained
30 for 16 cement kilns burning hazardous waste and 15 cement kilns burning nonhazardous waste
31 (U.S. EPA, 1996c). More recent CDD/CDF emissions data were also obtained from tests
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1 conducted in 2000 at 3 cement kilns burning hazardous waste (U.S. EPA, 2002b) and from tests
2 conducted in June and July of 1999 at one facility burning nonhazardous waste (Bell, 1999). The
3 majority of stack emissions data from cement kilns burning hazardous waste were derived during
4 trial burns and may overestimate the CDD/CDF emissions that most kilns achieve during normal
5 operations. Stack emissions data from kilns burning nonhazardous waste were derived from
6 testing during normal operations.
7
8 5.1.4.1. Emissions Data for 1989 Through 1996 (U.S. EPA, 1996c)
9 The average TEQ emission factors based on the data reported by EPA in 1996 (U.S. EPA,
10 1996c) are 0.000941 to 232 ng TEQDF-WHO98/kg (average of 22.48 ng TEQDF-WHO98/kg [20.91
11 ng I-TEQDF/kg]) clinker produced for cement kilns burning hazardous waste and 0.000012 to
12 2.76 ng TEQDF-WHO98/kg (average of 0.29 ng TEQDF-WHO98/kg [0.27 ng I-TEQDF/kg]) clinker
13 produced for cement kilns burning nonhazardous waste.
14 These data show that the average emission factor for kilns burning hazardous waste is
15 about 90 times greater than that for kilns burning nonhazardous waste. However, it should be
16 noted that the average emission factor for kilns burning hazardous waste was derived from "near
17 worst case" testing of hazardous waste-burning kilns. As discussed in Section 5.1.8, a
18 comparison of CDD/CDF concentrations in CKD samples shows a similar relationship (i.e., the
19 CDD/CDF TEQ concentration of the CKD from kilns burning hazardous waste was about 100
20 times higher than that of the dust from kilns burning nonhazardous waste). Although the average
21 emission factors for the two groups of kilns differ substantially, the emission factors for
22 individual kilns in the two groups overlap. Therefore, other aspects of the design and operation
23 of the kilns—in particular, the temperature of the APCD equipment (as discussed in Section
24 5.1.3)—are likely affecting CDD/CDF emissions.
25 Previous attempts to understand these differences using parametric testing of cement
26 kilns yielded mixed results. EPA conducted a limited comparison (U.S. EPA, 1997d) of
27 CDD/CDF TEQ stack gas concentrations (ng TEQ/dscm) between cement kilns burning
28 hazardous wastes and those not burning hazardous wastes. Those comparisons were made at 14
29 cement kilns. With the exception of the fuel being burned, operating conditions (e.g., APCD
30 temperature) were the same or similar for each set of comparisons. Baseline conditions used coal
31 as the only primary fuel. The results of these comparisons found:
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1 • seven kilns in which the baseline (i.e., no combustion of hazardous waste) CDD/CDF
2 TEQ stack gas concentrations were about the same as those for the burning of
3 hazardous wastes,
4
5 • two kilns in which the baseline CDD/CDF I-TEQDF stack gas concentrations were
6 about double those for the burning of hazardous wastes, and
7
8 • five kilns in which the hazardous waste CDD/CDF I-TEQDF stack gas concentrations
9 were substantially greater (3- to 29-fold greater) than those for the baseline operating
10 conditions.
11
12 Subsequently, ORD conducted analyses of the available emissions data to evaluate, on a
13 congener-specific basis, whether there were significant differences in emission factors between
14 (a) kilns burning hazardous waste and those burning nonhazardous waste, (b) kilns with APCD
15 inlet temperatures greater than 232 °C and those with temperatures less than 232 °C, (c)
16 hazardous waste-burning and nonhazardous waste-burning facilities with APCD inlet
17 temperatures greater than 232 °C, (d) hazardous waste-burning and nonhazardous waste-burning
18 facilities with APCD inlet temperatures less than 232 °C, (e) hazardous waste-burning facilities
19 with APCD inlet temperatures less than and greater than 232 °C, and (f) nonhazardous waste-
20 burning facilities with APCD inlet temperatures less than and greater than 232 °C. The results of
21 all analyses showed significant differences in the sample mean values (p<0.05).
22 Given the strong empirical evidence that real differences exist, ORD decided to address
23 the kilns burning hazardous waste separately from those burning nonhazardous waste to develop
24 a CDD/CDF emissions inventory and to subdivide the hazardous waste-burning category into
25 subcategories by APCD inlet temperature (i.e., less than 232 °C and greater than 232 °C). APCD
26 inlet temperature data were available for 88 test runs at 14 cement kilns. The number of test runs
27 conducted at individual kilns ranged from 1 to 26. Each test run was treated as an individual
28 facility and each was classified according to APCD inlet temperature and whether or not
29 hazardous waste was burned. The emission factor for each cement kiln test run was calculated
30 using eq 5-1.
31
32 EFCK = CxFv (5-1)
33 Id
34
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1 where:
2 EFCK = Cement kiln emission factor (burning or not burning hazardous waste)
3 (ng TEQ/kg of clinker produced)
4
5 C = TEQ or CDD/CDF concentration in kiln exhaust gases (ng TEQ/dscm)
6 (20 °C, 1 atm; adjusted to 7% O2)
7
8 Fv = Volumetric kiln exhaust gas flow rate (dscm/hr) (20 °C, 1 atm; adjusted to 7% O2)
9
10 Icl = Average cement kiln clinker production rate (kg/hr)
11
12 After developing the emission factor for each cement kiln test run, the overall average congener-
13 specific emission factor was derived for all test runs in each subcategory using eq 5-2.
14
EF-,. + EFni^ + EF-.. + ........ + EF
_ Ofv1 _ ol^2
avgCK ~
15 where:
16 EFavgCK = Average emission factor of tested cement kilns burning hazardous
17 waste as supplemental fuel and with APCD inlet temperatures
18 either greater than or less than 232 °C (ng TEQ/kg clinker)
19
20 N = Number of cement kiln test runs
21
22 TEQ emission values for hazardous waste-burning cement kilns with APCD inlet temperatures
23 greater than 232 °C and less than 232 °C are 30.7 and 1.11 ng TEQDF-WHO98/kg clinker
24 produced, respectively.
25
26 5.1.4.2. Emissions Data for 1999 and 2000 (U.S. EPA, 2002b; Bell, 1999)
27 The results of a test conducted in 1999 for a cement kiln burning nonhazardous waste
28 (Bell, 1999) showed average TEQDF-WHO98 and I-TEQ emission factors of 0.14 ng/kg clinker
29 produced. This value is within the range of emission factor values developed using the 1989
30 through 1996 data (U.S. EPA, 1996c).
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1 The results of three tests conducted in 2000 for cement kilns burning hazardous waste
2 showed average TEQ emission factors ranging from 0.08 to 6.1 ng TEQDF-WHO98/kg (0.07 to 5.4
3 I-TEQ/kg) clinker produced. The average TEQ emission factor for these three facilities is 2.2 ng
4 TEQDF-WHO98/kg (2 I-TEQ/kg) clinker produced. The results obtained from these three
5 facilities fall within the range of results obtained from the 1989 to 1996 data (U.S. EPA, 1996c);
6 however, two of the facilities (Holnam plant in Holly Hill, South Carolina, and Giant plant in
7 Bath, Pennsylvania) had results that fell toward the low end of the data range.
8 Because of the limited availability of new emissions data, EPA investigated whether
9 cement kilns burning hazardous waste had changed their operating practices, in particular,
10 whether APCDs were still operating above 232 °C. The emissions data from the three facilities
11 tested in 2000 indicated APCD temperatures between 246 and 260 °C. However, according to
12 representatives from a number of hazardous waste-burning cement kilns, at least 85% of the kilns
13 operating in 2000 operated with inlet APCD temperatures below 232 °C. For the 1987 and 1995
14 national emission estimates, it was assumed that 20% of the facilities operated with APCD inlet
15 temperatures below 232 °C and 80% operated above 232 °C. Of the test runs conducted between
16 1989 and 1996 at temperatures above 232 °C, the majority of the inlet APCD temperatures were
17 below 316 °C. The individual emission factors for the kilns with APCD inlet temperatures
18 below 316 °C were all less than 7 ng TEQDF-WHO98/kg clinker produced. The kiln with the
19 highest inlet APCD temperature (385 °C) had the highest TEQ emission factor (150 ng TEQDF-
20 WHO98/kg clinker produced). This kiln, however, stopped burning hazardous waste before 2000.
21
22 5.1.4.3. Emission Factor Estimates for Cement Kilns Burning Hazardous Waste
23 For reference years 1987 and 1995, EPA estimated the TEQ emission factor by
24 subdividing the emissions data reported in 1996 (U.S. EPA, 1996c; i.e., 1989 through 1996 data)
25 by inlet APCD temperature above and below 232 °C. For cement kilns operating at temperatures
26 above 232 °C, the TEQ emission factor is 30.7 ng TEQDF-WHO98/kg clinker produced, and for
27 cement kilns operating at temperatures below 232 °C, the TEQ emission factor is 1.11 ng TEQDF-
28 WHO98/kg clinker produced. These emission factors are presented in Table 5-1 and the average
29 congener profile is presented in Figure 5-1.
30 Because a vast majority of the facilities had reduced their APCD inlet temperature to
31 below 232 °C in 2000 and because only a few new test reports applicable to reference year 2000
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1 were available, EPA removed the 232 °C divider and combined the emission factor results (U.S.
2 EPA, 1996c; i.e., 1989 through 1996 data) for facilities that were still operating in 2000 with the
3 newer data reported (U.S. EPA, 2002b). Therefore, emission tests from five facilities (U.S. EPA,
4 1996c) were not used to estimate the 2000 emission factor because the facilities no longer burned
5 hazardous waste in 2000. Using this approach, a conservative TEQ emission estimate of 5.95 ng
6 TEQDF-WHO98/kg (5.49 ng I-TEQ/kg) clinker produced was developed for reference year 2000.
7 The congener-specific emission factors are presented in Table 5-2 and the average congener and
8 congener group profiles are presented in Figure 5-2.
9
10 5.1.4.4. Emission Factor Estimates for Cement Kilns Burning Nonhazardous Waste
11 Because only one test report applicable to reference year 2000 was located for a cement
12 kiln burning nonhazardous waste (Bell, 1999), and the results from the tests were similar to the
13 results reported by EPA in 1996 (U.S. EPA, 1996c; i.e. 1989 through 1996 data), EPA combined
14 the results from the two data sets to obtain a TEQ emission factor estimate of 0.27 ng TEQDF-
15 WHO98/kg (0.26 ng I-TEQ/kg) clinker produced for reference years 1987, 1995, and 2000. The
16 congener-specific emission factors are presented in Table 5-3 and the average congener and
17 congener group profiles are presented in Figure 5-3.
18
19 5.1.4.5. Confidence Ratings of Emission Factor Estimates
20 The TEQ emission factors are given a low confidence rating for all subcategories and all
21 years. The emission factor for nonhazardous waste-burning kilns was given a low rating because
22 test data were available for only 16 facilities. The tested facilities may not be representative of
23 routine CDD/CDF emissions from all kilns burning nonhazardous waste. Although a higher
24 percentage of the kilns burning hazardous waste (with reported APCD temperature data) had
25 been tested, greater uncertainty exists about whether the emissions are representative of normal
26 operations because the tests used trial burn procedures and because a greater majority of the
27 operating facilities had reduced their APCD temperatures to below 232 °C. Accordingly, a low
28 confidence rating was also assigned to the estimated emission factors for kilns burning hazardous
29 waste.
30
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1 5.1.5. Activity Level Information
2 In 1987, approximately 52 billion kg of cement clinker were produced in the United
3 States (U.S. DOC, 1996). In 1995, approximately 67.6 billion kg of clinker were produced in the
4 United States (U.S. DOC, 1996), and of this amount, Health (1995) reported that 61.3 billion kg
5 were produced by cement kilns burning nonhazardous waste; therefore, approximately 6.3 billion
6 kg were produced by cement kilns burning hazardous waste. Based on the fact that 9.3% of the
7 clinker produced in 1995 was from cement kilns burning hazardous waste, it is assumed that
8 approximately 4.8 billion kg of the clinker produced in 1987 were from cement kilns burning
9 hazardous waste.
10 In 2000, cement kilns produced approximately 75.2 billion kg of clinker. This amount is
11 based on the assumption that cement kilns operated at 90% of the maximum annual clinker
12 capacity of 83.6 billion kg (PCA, 2003a). Based on the annual clinker capacities of individual
13 cement kilns, approximately 11.5 billion kg of clinker (15%) were produced by cement kilns
14 burning hazardous waste and approximately 63.7 billion kg of clinker (85%) were produced by
15 cement kilns burning nonhazardous waste (PCA, 2001). The activity level estimates for 1995
16 and 2000 are given a high confidence rating because they are based on comprehensive survey
17 data, but the rating for 1987 is medium because of uncertainty concerning the proportion
18 produced by hazardous waste-burning kilns (U.S. EPA, 1996c).
19
20 5.1.6. National CDD/CDF Emission Estimates
21 5.1.6.1. Estimates for Reference Years 1987 and 1995
22 National estimates of CDD/CDF air emissions (g TEQ/yr) from all Portland cement kilns
23 for reference years 1987 and 1995 were made by multiplying the average TEQ emission factors
24 by an estimate of the annual activity level (cement clinker produced) for each of the three
25 subcategories (hazardous waste-burning kilns with APCD inlet temperatures greater than 232 °C
26 and less than 232 °C and kilns burning nonhazardous waste). Of the 10 hazardous waste-burning
27 kilns with APCD temperature data, 8 facilities (80%) had APCD inlet temperatures greater than
28 232 °C and 2 facilities (20%) had APCD inlet temperatures less than 232 °C. If the percentages
29 of hazardous waste-burning kilns with input temperatures less than and greater than 232 °C
30 represent the actual distribution of activity level in the industry, then these percentages, coupled
31 with the TEQ emission factors presented in Table 5-1 and Table 5-3 (hazardous waste cement
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1 kilns and nonhazardous waste cement kilns, respectively) and the activity levels established in
2 Section 5.1.5 can be used to calculate the annual national TEQ emission estimates shown in
3 Table 5-4.
4 Overall, 131 g TEQDF-WHO98 (122 g I-TEQDF) were produced by cement kilns in 1987.
5 Of this amount, 116.7 g TEQDF-WHO98 (108.6 g I-TEQDF) were produced by hazardous waste-
6 burning cement kilns with inlet APCD temperatures greater than 232 °C, 1.1 g TEQDF-WHO98
7 (1 g I-TEQDF) were produced by cement kilns burning hazardous waste with inlet APCD
8 temperatures less than 232 °C, and 12.7 g TEQDF-WHO98 (12.3 g I-TEQDF) were produced by
9 cement kilns burning nonhazardous waste. In 1995, a total of 173 g TEQDF-WHO98 (161 g I-
10 TEQDF) were produced by cement kilns. Of this amount, 154.7 g TEQDF-WHO98 (144 g I-TEQDF)
11 were produced by hazardous waste-burning cement kilns with inlet APCD temperatures greater
12 than 232 °C, 1.4 g TEQDF-WHO98 (1.3 g I-TEQDF) were produced by cement kilns burning
13 hazardous waste with inlet APCD temperatures less than 232 °C, and 16.6 g TEQDF-WHO98 (15.9
14 g I-TEQDF) were produced by cement kilns burning nonhazardous waste.
15 The overall rating for these emission estimates is low because the emission factors had a
16 low confidence rating.
17
18 5.1.6.2. Estimates for Reference Year 2000
19 National estimates of CDD/CDF air emissions (g TEQ/yr) from all Portland cement kilns
20 for reference year 2000 were made by multiplying the average TEQ emission factors by an
21 estimate of the annual activity level (cement clinker produced) for each the two categories
22 (hazardous waste and nonhazardous waste). The TEQ emission factors presented in Table 5-2
23 and Table 5-3 (hazardous waste-burning and nonhazardous waste-burning cement kilns,
24 respectively) and the activity levels established in Section 5.1.5 were used to calculate the annual
25 national TEQ emission estimates shown in Table 5-5. Overall, 85.6 g TEQDF-WHO98 (79.9 g I-
26 TEQDF) were produced by cement kilns in 2000. Of this amount, 68.4 g TEQDF-WHO98 (63.3 g I-
27 TEQDF) were produced by hazardous waste-burning cement kilns and 17.2 g TEQDF-WHO98 (16.6
28 g I-TEQDF) were produced by cement kilns burning nonhazardous waste. This estimated amount
29 produced by cement kilns not burning hazardous waste is on the same order of magnitude as the
30 44 g TEQDF-WHO98 predicted in the National Emission Standards for Hazardous Air Pollutants
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1 for the Portland Cement Manufacturing Industry, promulgated on June 14, 1999 (Federal
2 Register, 1999a).
3 All of these emission estimates have an overall confidence rating of low because the
4 emission factors had a low confidence rating.
5
6 5.1.7. EPA Regulatory Activities
7 Under the authority of the Clean Air Act, EPA promulgated national emission standards
8 for new and existing cement kilns burning nonhazardous waste in May 1999 (Federal Register,
9 1999a, 2004). The regulations are specific to the I-TEQ concentration in the combustion gases
10 leaving the stack. Existing and new cement kilns either combusting or not combusting hazardous
11 waste as auxiliary fuel cannot emit more than 0.2 ng I-TEQ/dscm. In addition, the temperature of
12 the combustion gases measured at the inlet to the air pollution control device cannot exceed 232
13 °C. The rule requires owners or operators of facilities to test for CDDs/CDFs every 21/2 years.
14 The Office of Air Quality Planning and Standards (OAQPS) expects this rule to reduce I-TEQDF
15 emissions from existing and new facilities by 36% over the next few years (Federal Register,
16 1999a, 2004).
17 In July 1999, under the j oint authority of the Clean Air Act and the Resource
18 Conservation and Recovery Act (RCRA), EPA promulgated national emission standards for
19 combustion facilities (including cement kilns) burning hazardous waste (Federal Register,
20 1999b).
21
22 5.1.8. Solid Waste from Cement Manufacturing: Cement Kiln Dust
23 EPA characterized CKD (the solid residual material generated during the manufacturing
24 of cement) in a report to Congress (U.S. EPA, 1993g) that was based in part on a 1991 survey of
25 cement manufacturers conducted by the Portland Cement Association (PCA). Survey responses
26 were received from 64% of the active cement kilns in the United States. On the basis of the
27 survey responses, EPA estimated that in 1990 the U.S. cement industry generated about 12.9
28 million metric tons of gross CKD and 4.6 million metric tons of net CKD, of which 4.2 million
29 metric tons were land-disposed. The material collected by the APCD system is called gross CKD
30 (or as-generated CKD); it is either recycled back into the kiln system or removed from the system
31 for disposal (becoming net CKD or as-managed CKD). As discussed below, low levels of dioxin
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1 have been measured in CKD. This material is disposed of in permitted landfills and therefore is
2 not considered to be an environmental release. On this basis, it is not included in the inventory
3 of dioxin releases presented in this report. However, for informational purposes only, this
4 section develops estimates of the amount of dioxin in CKD for the reference years 1987, 1995,
5 and 2000.
6 The PC A recently provided current estimates of the amount of CKD removed from the
7 manufacturing process for beneficial reuse and long-term management units (i.e., landfill
8 disposal) in 1990, 1995, and 2000. Possible beneficial reuses include municipal waste daily
9 cover material, municipal waste landfill final cover material, soil stabilization for roadways or
10 other structures, waste neutralization/stabilization/solidification (food wastes, hazardous wastes,
11 etc.), and agricultural soil amendment. The PCA estimated that the amount of CKD beneficially
12 reused on or off site was 752 million kg in 1990, 652 million kg in 1995, and 575 million kg in
13 2000. The amount of CKD disposed of annually in landfills was estimated to be 2.7 billion kg in
14 1990, 3.1 billion kg in 1995, and 2.2 billion kg in 2000.
15 In its report to Congress, EPA also included the results of sampling and analysis of CKD
16 and clinker conducted in 1992 and 1993 (U.S. EPA, 1993g). The purposes of the sampling and
17 analysis efforts were to (a) characterize the CDD/CDF content of clinker and CKD, (b) determine
18 the relationship, if any, between the CDD/CDF content of CKD and the use of hazardous waste
19 as fuel, and (c) determine the relationship, if any, between the CDD/CDF content of CKD and
20 the use of wet-process and dry-process cement kilns.
21 Clinker samples were collected from five cement kilns burning nonhazardous waste and
22 six kilns burning hazardous waste. CDDs/CDFs were not detected in any of the samples. Tetra-
23 through octa-chlorinated CDDs/CDFs were detected in the gross CKD samples obtained from 10
24 of the 11 kilns and in the net CKD samples obtained from 8 of the 11 kilns. The CDD/CDF
25 content for gross CKD ranged from 0.008 to 247 ng I-TEQDF/kg and from 0.045 to 195 ng I-
26 TEQDF/kg for net CKD. Analyses for seven PCB congeners were also conducted, but no
27 congeners were detected in any clinker or CKD sample.
28 Mean CDD/CDF concentrations in net CKD generated by the kilns burning hazardous
29 waste were higher (35 ng I-TEQDF/kg) than in net CKD generated by the facilities burning
30 nonhazardous waste (0.003 ng I-TEQDF/kg). These calculations of mean values treated nondetect
31 values as zero. If the nondetects had been excluded from the calculation of the means, the mean
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1 for net CKD from kilns burning hazardous waste would increase by a factor of 1.2 and the mean
2 for net CKD from kilns burning nonhazardous waste would increase by a factor of 1.7. One
3 sampled kiln had a net CKD TEQ concentration more than two orders of magnitude greater than
4 the TEQ levels found in samples from any other kiln. If this kiln were considered atypical of the
5 industry (U.S. EPA, 1993g) and were not included in the calculation, then the mean net CKD
6 concentration for hazardous waste-burning kilns would decrease to 2.9 ng I-TEQDF/kg.
7 CDD/CDF congener data for CKD from Holnam, Inc., Seattle, Washington, were
8 presented in a report by the Washington State Department of Ecology (1998). The data were
9 compiled and evaluated to determine total I-TEQ concentrations and loadings. Nondetect values
10 were included as either zero, one-half of the detection limit (DL), or at the DL. The results of
11 three separate tests were as follows, assuming that nondetect values were zero:
12
13
14
15
16
17
18 EPA provided data for ashes from an ESP connected to a cement kiln and an FF
19 connected to a lightweight aggregate (LWA) kiln (U.S. EPA, 1999d). The average congener
20 concentrations for the ash samples are listed in Table 5-6. The average concentrations for the
21 cement kiln were determined from two different waste streams, each with five sample burns.
22 The average concentrations for the LWA kiln were determined using one waste stream with three
23 sample burns.
24 The amount of CDDs/CDFs associated with CKD was calculated for informational
25 purposes only. National estimates were divided among cement kilns burning hazardous waste
26 and those burning nonhazardous waste for both CKD that was beneficially reused and CKD that
27 was sent landfills. The activity levels used in the estimates were those provided by the PCA
28 (2003b). The 1990 activity levels provided by PCA were used for reference year 1987. The
29 CDD/CDF concentrations in CKD used in the estimates were 35 ng I-TEQDF/kg for cement kilns
Date
05/15/96
10/21/97
10/21/97
Location
Not stated
HLMNbin
HLMN final
I-TEQ
(ng/kg)
0.038
0.67
0.95
I-TEQ
(mg/day)
0.0038
0.0674
0.0948
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1 burning hazardous waste (which includes the high value discussed above) and 0.003 ng I-
2 TEQDF/kg for cement kilns burning nonhazardous waste.
3 As shown in Table 5-7, by combining the appropriate activity levels and CDD/CDF
4 concentrations, national estimates of CDDs/CDFs in CKD were developed for reference years
5 1987, 1995, and 2000. For cement kilns burning hazardous waste, approximately 4.2 g I-TEQDF
6 in 1987, 3.6 g I-TEQDF in 1995, and 3.3 g I-TEQDF in 2000 were produced from CKD that was
7 beneficially reused, and approximately 14.9 g I-TEQDF in 1987, 17.7 g I-TEQDF in 1995, and 12.8
8 g I-TEQDF in 2000 were produced from CKD that was disposed of in a landfill. For cement kilns
9 burning nonhazardous waste, approximately 0.0019 g I-TEQDF in 1987, 0.0016 g I-TEQDF in
10 1995, and 0.0014 g I-TEQDF in 2000 were produced from CKD that was beneficially reused and
11 approximately 0.0067 g I-TEQDF in 1987, 0.0079 g I-TEQDF in 1995, and 0.0056 g I-TEQDF in
12 2000 were produced from CKD that was disposed of in a landfill.
13 EPA is currently developing CKD storage and disposal requirements. In 1999, a
14 proposed rule for the standards for the management of CKD was developed by EPA (Federal
15 Register, 1999b). Under the rule, CKD would remain a nonhazardous waste, provided that
16 proposed management standards are met, which would protect groundwater and control releases
17 of fugitive dust. Additionally, the rule proposes concentration limits on various pollutants in
18 CKD used for agricultural purposes (Federal Register, 1999d).
19
20 5.2. LIGHTWEIGHT AGGREGATE KILNS
21 LWA kilns heat raw materials such as clay, shale, or slate to expand the particles to form
22 lightweight materials for use in concrete products. In 1995, only 5 of the more than 36 LWA
23 kilns in the United States were burning hazardous waste; in 2000, 9 LWA kilns were burning
24 hazardous waste. LWA kilns are estimated to have emitted 3.3 g I-TEQDF to air in 1990 (Federal
25 Register, 1998b) and 2.4 g I-TEQDF in 1997 (Federal Register, 1999b); these estimates are used
26 in this report for reference years 1987 and 1995, respectively.
27 The CDD/CDF emission factors for 2000 are based on the data for five LWA kilns tested
28 in 2000 (U.S. EPA, 2002b). They were calculated using the process described in Section 3.2.3.
29 The average emission factor for the LWA kilns was 1.986 ng TEQDF-WHO98/kg (2.063 ng I-
30 TEQDF/kg) of waste feed, assuming nondetect values of zero. These were assigned a low
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1 confidence rating because the emission factor may not be representative of emissions from the
2 source category.
3 The amount of hazardous waste combusted using LWA kilns in 2000 was conservatively
4 estimated to be 903,000 metric tons, based on estimated activity levels derived for each halogen
5 acid furnace (HAF) in 2000. Data were available for all of the nine facilities operating in 2000.
6 A conservative estimate for the average annual quantity burned per HAF (100,280 metric tons/yr)
7 was derived by assuming that plants operate continuously throughout the year, and are always
8 running at 80% of capacity. This quantity, multiplied by the total universe of nine facilities,
9 yields the final estimate. Because the activity level was not derived from a survey but was
10 estimated, it is given a low confidence rating.
11 Equation 3-5, used to calculate annual TEQ emissions for dedicated hazardous waste
12 incinerators, was also used to calculate annual TEQ emissions for LWA kilns. Multiplying the
13 average TEQ emission factors by the total estimated amount of liquid hazardous waste burned in
14 2000 yields an annual emissions estimate. From this procedure, the emissions from all LWA
15 kilns burning hazardous waste as supplemental fuel are estimated as 1.86 g TEQDF-WHO98 (1.79
16 g I-TEQDF) for 2000. Because of the low confidence rating for the emission factor, the overall
17 confidence rating for the emission estimates is low.
18
19 5.3. ASPHALT MIXING PLANTS
20 Asphalt consists of an aggregate of gravel, sand, and filler mixed with liquid asphalt
21 cement or bitumen. Filler typically consists of limestone, mineral stone powder, and sometimes
22 ash from power plants and municipal waste combustors. The exact composition of an asphalt
23 formulation depends on how it will be used. The aggregate typically constitutes more than 92%
24 by weight of the total asphalt mixture. The components of the aggregate are dried, heated to a
25 temperature ranging from 135 to 163 °C, and then mixed and coated with the bitumen at an
26 asphalt mixing installation. "Old" asphalt (i.e., asphalt from dismantled bridges and roads) can
27 be heated and disaggregated to its original components and reused in the manufacture of new
28 asphalt (U.S. EPA, 1996i). "Hot mix" asphalt paving materials can be manufactured by (a) batch
29 mix plants, (b) continuous mix plants, (c) parallel-flow drum mix plants, and (d) counterflow
30 drum mix plants (U.S. EPA, 1998c).
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1 Bremmer et al. (1994) reported the CDD/CDF emissions factor for an asphalt mixing
2 plant in the Netherlands as 47 ng I-TEQDF per metric ton of produced asphalt. No congener-
3 specific emission factors were reported. The mixing plant heated old asphalt to about 150 °C in
4 an individual recycling drum with kiln exhaust gases that were mixed with ambient air and
5 heated to a temperature of 300 to 400 °C. Parallel to this recycling drum was the main drum,
6 which dried and heated the aggregate (sand and gravel/granite chippings) to a temperature of
7 about 220 °C. The kiln exhaust gases leaving the recycling drum were led along the main burner
8 of the main drum for incineration. The old asphalt, the minerals from the main drum, and new
9 bitumen from a hot storage tank (about 180 °C) were mixed in a mixer to form new asphalt.
10 Natural gas fueled the plant during the sample collection period, and 46% of the feed was old
11 asphalt. The plant's APCD system consisted of cyclones and an FF.
12 Umweltbundesamt (1996) reported lower emission factors for three tested facilities in
13 Germany that were also equipped with FFs. These three facilities were fueled by oil or butane
14 gas and used old asphalt at rates ranging from 30 to 60% of the feed. The emission factors
15 calculated from the stack gas concentrations, gas flow rates, and hourly throughputs for these
16 three facilities were 0.2, 3.5, and 3.8 ng I-TEQDF/metric ton of asphalt produced.
17 OAQPS directed Midwest Research Institute to conduct emissions testing at asphalt
18 concrete production plants in 1997 (U.S. EPA, 2001b). The institute performed emissions tests
19 on the inlet and outlet of FFs that control emissions from the counterflow rotary dryer process
20 used at the asphalt plant in Clayton, North Carolina, and from the parallel-flow rotary dryer
21 process used at the asphalt plant in Gary, North Carolina. In both processes, virgin aggregate of
22 various sizes was fed to the drum by cold-feed controls in proportions dictated by the final mix
23 specifications. Aggregate was delivered at the opposite end of the burner in the counter-flow
24 continuous drum mix process and at the same end as the burner in the parallel-flow continuous
25 drum mix process.
26 The Clayton facility used an FF for particulate matter (PM) control, and the Gary facility
27 used a knockout box as the primary control and an FF as a secondary control. The average
28 asphalt production rates at the Clayton facility were 171, 276, 240, and 185 tons/hr for the four
29 test runs and 201, 199, and 163 tons/hr for the three test runs at the Gary facility. Mix
30 temperatures for both facilities ranged from 148 to 155 °C. Emission profiles from both facilities
31 indicated low releases of dioxin into the air. The average emission factor developed for the
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1 seven test runs was 0.0011 ng TEQDF-WHO98/kg processed (see Table 5-8 for congener-specific
2 TEQs).
3 Approximately 25 million metric tons of asphalt bitumen were produced in the United
4 States in 1992. An identical quantity was produced in 1990 (U.S. DOC, 1995a). Bitumen
5 constitutes approximately 5% by weight of finished paving asphalt (Bremmer et al., 1994). Thus,
6 an estimated 500 million metric tons of paving asphalt are produced in the United States
7 annually. Approximately 500 million tons of hot mix asphalt paving materials were produced at
8 the estimated 3,600 active asphalt plants in the United States in 1996 (U.S. EPA, 1998c). This
9 activity level was adopted for 1987, 1995, and 2000 with a high confidence level. The activity
10 level is given a high rating because it is based on a comprehensive survey.
11 For reference years 1987 and 1995, a preliminary estimate of the potential magnitude of
12 annual TEQ emissions for U.S. production of asphalt can be obtained by averaging the emission
13 factors for the four facilities reported by Bremmer et al. (1994) and Umweltbundesamt (1996).
14 Applying this average emission factor (14 ng I-TEQDF/metric ton of asphalt produced) to the
15 activity level of 500 million metric tons of paving asphalt produced annually yields an annual
16 emission of 7 g I-TEQDF/yr (congener-specific results were not reported in either report;
17 therefore, TEQDF-WHO98 estimates could not be calculated). The preliminary estimates for 1987
18 and 1995 have been revised in this report to use the emission factor developed from two U.S.
19 facilities (i.e., 1.1 ng TEQDF-WHO98/metric ton of asphalt produced). This changes the emission
20 estimates for these years to 0.55 g TEQDF-WHO98/yr. Since activity levels have remained
21 constant, this emission estimate also applies to the year 2000. These emission estimates are still
22 considered to be preliminary, since the emission factor is based on testing at only 2 of 3,600 total
23 facilities.
24
25 5.4. PETROLEUM REFINING CATALYST REGENERATION
26 Regeneration of spent catalyst from the reforming process at petroleum refineries is a
27 potential source of CDDs/CDFs, according to limited testing conducted in the United States
28 (Amendola and Barna, 1989; Kirby, 1994), Canada (Maniff and Lewis, 1988; Thompson et al.,
29 1990), and the Netherlands (Bremmer et al., 1994). This section summarizes the catalyst
30 regeneration process, relevant studies performed to date, and the status of EPA regulatory
31 investigations of this source.
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1 Catalytic reforming is the process used to produce high-octane reformates from lower-
2 octane reformates for blending of high-octane gasolines and aviation fuels. The reforming
3 process occurs at high temperature and pressure and requires the use of a platinum or
4 platinum/rhenium catalyst. During the reforming process, a complex mixture of aromatic
5 compounds, known as coke, is formed and deposited onto the catalyst. As coke deposits onto the
6 catalyst, its activity is decreased. The high cost of the catalyst necessitates its regeneration.
7 Catalyst regeneration is achieved by removing the coke deposits via burning at temperatures of
8 399 to 454 °C and then reactivating the catalyst at elevated temperatures (454 to 538 °C) using
9 chlorine or chlorinated compounds (e.g., methylene chloride, 1,1,1-trichloroethane, and ethylene
10 dichloride; most refineries use chlorine of perchloroethylene). Burning of the coke produces kiln
11 exhaust gases that can contain CDDs and CDFs along with other combustion products. Because
12 kiln exhaust gases, if not vented directly to the atmosphere, may be scrubbed with caustic or
13 water, internal effluents may become contaminated with CDDs/CDFs (Kirby, 1994; SAIC,
14 1994).
15 Three basic catalyst regeneration processes are used: semi-regenerative, cyclic, and
16 continuous. During the semi-regenerative process, the entire catalytic reformer is taken offline.
17 In the cyclic process, one of two (or more) reforming reactors is taken off line for catalyst
18 regeneration; the remaining reactor(s) remains on line so that reforming operations continue. In
19 the continuous process, aged catalyst is continuously removed from one or more on-line stacked
20 or side-by-side reactors, regenerated in an external regenerator, and then returned to the system;
21 the reforming system, consequently, never shuts down (SAIC, 1994).
22 In 1988, the Canadian Ministry of the Environment detected concentrations of CDDs in
23 an internal waste stream of spent caustic at a petroleum refinery that ranged from 1.8 to 22.2
24 |_ig/L and CDFs ranging from 4.4 to 27.6 |_ig/L (Maniff and Lewis, 1988). The highest
25 concentration of 2,3,7,8-TCDD was 0.0054 |_ig/L. CDDs were also observed in the refinery's
26 biological sludge at a maximum concentration of 74.5 pg/kg, and CDFs were observed at a
27 maximum concentration of 125 pg/kg. The concentration of CDDs/CDFs in the final combined
28 refinery plant effluent was below the DLs.
29 Amendola and Barna (1989) reported detecting trace levels of hexa- to octa-CDDs and
30 CDFs in untreated wastewaters (up to 2.9 pg I-TEQDF/L) and wastewater sludges (0.26 to 2.4 ng
31 I-TEQDF/kg) at a refinery in Ohio. The levels of detected total CDDs/CDFs in the wastewater
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1 and sludge were much lower (<3 ng/L and <1 i-ig/kg, respectively) than the levels reported by
2 Maniff and Lewis (1988). No CDDs/CDFs were detected in the final treated effluent (less than
3 0.2 ng I-TEQDF/L). The data collected in the study were acknowledged to be too limited to
4 enable identifying the source(s) of the CDDs/CDFs within the refinery. The study authors also
5 presented in an appendix to their report the results of analyses of wastewater from the catalyst
6 regeneration processes at two other U.S. refineries. In both cases, untreated wastewaters
7 contained CDDs/CDFs at levels ranging from high pg/L to low ng/L (results were reported for
8 congener group totals, not specific congeners). However, CDDs/CDFs were not detected in the
9 only treated effluent sample collected at one refinery.
10 Thompson et al. (1990) reported total CDD and CDF concentrations of 8.9 ng/m3 and 210
11 ng/m3, respectively, in stack gas samples from a Canadian petroleum refinery's reforming
12 operation. They also observed CDDs/CDFs in the pg/L to ng/L range in the internal washwater
13 from a scrubber of a periodic/cyclic regenerator.
14 Beard et al. (1993) conducted a series of benchtop experiments to investigate the
15 mechanism(s) of CDD/CDF formation in the catalytic reforming process. A possible pathway
16 for the formation of CDFs was found, but the results could not explain the formation of CDDs.
17 Analyses of the kiln exhaust gas from burning coked catalysts revealed the presence of
18 unchlorinated dibenzofuran in quantities up to 220 pg/kg of catalyst. Chlorination experiments
19 indicated that dibenzofuran and possibly biphenyl and similar hydrocarbons act as CDF
20 precursors and can become chlorinated in the catalyst regeneration process. Corrosion products
21 on the steel piping of the process plant seem to be the most likely chlorinating agent.
22 In May 1994, EPA's Office of Water conducted a sampling and analytical study of
23 catalyst regeneration wastewater for CDDs/CDFs at three petroleum refining plants (Kirby,
24 1994). The study objectives were to determine the analytical method best suited for determining
25 CDDs/CDFs in refinery wastewater and to screen and characterize wastewater discharges from
26 several types of reforming operations for CDDs/CDFs. The report for this study (Kirby, 1994)
27 also presented results submitted voluntarily to EPA by two other facilities. The sampled internal
28 untreated wastewaters and spent caustics were found to contain a wide range of CDD/CDF
29 concentrations, 0.1 pg I-TEQDF/L to 57.2 ng I-TEQDF/L. The study results also showed that 90%
30 of the TEQ was contained in the wastewater treatment sludges generated during the treatment of
31 wastewater and caustic from the regeneration process.
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1 In 1995, EPA issued a notice of its proposed intent to not designate spent reformer
2 catalysts as a listed hazardous waste under RCRA (Federal Register, 1995b). The final rule was
3 issued in August 1998 (Federal Register, 1998a). The Agency's assessment of current
4 management practices associated with recycling of reforming catalyst found no significant risks
5 to human health or the environment. The Agency estimated that 94% of the approximately 3,600
6 metric tons of spent reformer catalyst sent off site by refineries are currently recycled for their
7 precious metal content. However, EPA made no determination of the "listability" of spent
8 caustic residuals formed during regeneration of spent reforming catalyst. The Agency did
9 identify the potential air releases from the combustion of the reforming catalyst prior to
10 reclamation as being possibly of concern. The Agency requested comments on (a) opportunities
11 for removing dioxin prior to discharge of scrubber water into the wastewater treatment system,
12 (b) opportunities to segregate this wastestream, and (c) potential health risks associated with
13 insertion of dioxin-contaminated media back into the refinery process (such as the coker). In this
14 proposed rulemaking, EPA also noted the possibility of dioxin releases to air during regeneration
15 operations.
16 As part of its regulatory investigation under RCRA, EPA's Office of Solid Waste
17 commissioned a study to analyze and discuss existing data and information concerning
18 CDD/CDF formation in the treatment of catalytic reformer wastes. This report (SAIC, 1994)
19 also identified potential process modifications that may prevent the formation of CDDs/CDFs.
20 The report's authors concluded that, although the available data indicate that CDDs/CDFs can be
21 generated during the catalyst regeneration process, the available data indicate that CDD/CDF
22 concentrations in treated wastewater and in solid waste are minimal. Releases to air could result
23 from vented kiln exhaust gases at some facilities. In addition, the CDDs/CDFs formed could
24 possibly be reintroduced into other refining operations (e.g., the coker) and resulting products.
25 In 1998, emissions from the caustic scrubber used to treat gases from the external
26 regeneration unit of a refinery in California were tested (CARB, 1999). This facility uses a
27 continuous regeneration process. The reactor is not taken offline during regeneration; rather,
28 small amounts of catalyst are continuously withdrawn from the reactor and are regenerated. The
29 emissions from the regeneration unit are neutralized by a caustic scrubber before being vented to
30 the atmosphere. The catalyst recirculation rate during the three tests ranged from 733 to 1,000
31 Ib/hr.
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1 All 2,3,7,8-substituted CDDs/CDFs were detected in each of the three samples collected.
2 The average emission factors in units of ng/barrel of reformer feed are presented in Table 5-9.
3 The congener profile is presented in Figure 5-4. The samples showed a wide range in
4 concentrations of the CDD/CDF congeners (up to fivefold difference); however, the congener
5 profile was consistent in all samples. The concentrations of the individual furan congener groups
6 were always higher than the concentrations of the corresponding dioxin congener group. The
7 average TEQDF-WHO98 emission factor for these three tests is 3.18 ng TEQ/barrel and the
8 average I-TEQDF is 3.04 ng TEQ/barrel.
9 In 1991, stack testing was performed on the exhaust from one of the three semi-
10 regenerative catalytic reforming units of a refinery in California (Radian Corporation, 1991). A
11 caustic solution is introduced to the exhaust to neutralize HC1 emissions from the catalyst beds
12 prior to release to the atmosphere. The tested unit was considered to be representative of the
13 other units. Each unit is periodically (approximately once per year) taken off line so the catalyst
14 beds can be regenerated. The tested unit has a feed capacity of 7,000 barrels per day.
15 Approximately 59,500 pounds of catalyst were regenerated during the tested regeneration cycle,
16 which lasted for 62 hr.
17 The average emission factors for this facility (in units of ng/barrel of reformer feed) are
18 presented in Table 5-9 and the congener profile is presented in Figure 5-4. The majority of the
19 2,3,7,8-substituted CDD congeners were not detected during testing. In contrast, the majority of
20 the 2,3,7,8-substituted CDF congeners were detected. The average TEQDF-WHO98 emission
21 factor (assuming nondetect values are zero) is 1.04e-03 ng TEQ/barrel and the average I-TEQDF
22 emission factor is l.Ole-03 ng TEQ/barrel. These values are three orders of magnitude less than
23 the emission factor reported in CARB (1999). The calculation of these emission factors involved
24 several assumptions: the unit is regenerated once per year, the unit operates at capacity (7,000
25 barrels/day), and the facility operates 362 days per year.
26 The average of the two facility emission factors, 1.59 ng TEQDF-WHO98/barrel (1.52 ng I-
27 TEQDF/barrel) of reformer feed, is assumed to apply to all reference years (1987, 1995, and 2000)
28 and is assigned a low confidence rating. Only one continuous and only one semiregenerative unit
29 in the United States have been tested. Combined, these two facilities represent less than 1% of
30 the catalytic reforming capacity in U.S. petroleum refineries in 1987 (3.805 million barrels per
31 day), 1995 (3.867 million barrels per day), and 2000 (3.770 million barrels per day) (EIA,
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1 2002a). The average emission factor developed above assumes that emissions are proportional to
2 reforming capacity; however, they may be more related to the amount of coke burned, the APCD
3 equipment present, or other process parameters.
4 The national daily average catalytic reforming capacities in the United States were 3.805,
5 3.867, and 3.770 million barrels per day for 1987, 1995, and 2000, respectively (EIA, 2002a).
6 These were assigned a high confidence rating because they are based on comprehensive surveys
7 of industry. If it is conservatively assumed that all units operated at full capacity in 1987, 1995,
8 and 2000, then applying the average emission factors of TEQ/barrel yields annual emissions of
9 2.21 g TEQDF-WH098 (2.11 g I-TEQDF) in 1987, 2.24 g TEQDF-WHO98 (2.14 g I-TEQDF) in 1995,
10 and 2.19 g TEQDF-WHO98 (2.09 g I-TEQDF) in 2000. These emissions have a low confidence
11 rating because they are based on an emission factor with a low confidence rating.
12
13 5.5. CIGARETTE SMOKING
14 Bumb et al. (1980) were the first to report that cigarette smoking is a source of CDD
15 emissions. Subsequent studies by Muto and Takizawa (1989), Ball et al. (1990), and Lofroth and
16 Zebiihr (1992) also reported the presence of CDDs as well as CDFs in cigarette smoke. A study
17 by Matsueda et al. (1994) reported the CDD/CDF content of the tobacco from 20 brands of
18 cigarettes from seven countries. Although a wide range in the concentrations of total
19 CDDs/CDFs and total TEQs were reported in these studies, similar congener profiles and
20 patterns were reported. The findings of each of these studies are described in this section.
21 No studies published to date have demonstrated a mass balance, and it is not known
22 whether the CDDs/CDFs measured in cigarette smoke are the result of formation during tobacco
23 combustion, volatilization of CDDs/CDFs present in the unburned tobacco, or a combination of
24 these two source mechanisms. The combustion processes operating during cigarette smoking are
25 complex and could be used to justify both source mechanisms. As reported by Guerin et al.
26 (1992), during a puff, gas-phase temperatures reach 850 °C at the core of the firecone, and solid-
27 phase temperatures reach 800 °C at the core and 900 °C or greater at the char line. Thus,
28 temperatures are sufficient to cause at least some destruction of CDDs/CDFs initially present in
29 the tobacco. Both solid- and gas-phase temperatures rapidly decline to 200 to 400 °C within 2
30 mm of the char line.
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1 Formation of CDDs/CDFs has been reported in combustion studies with other media in
2 this temperature range of 200 to 900 °C. However, it is known that a process likened by Guerin
3 et al. (1992) to steam distillation takes place in the region behind the char line because of high,
4 localized concentrations of water and temperatures of 200 to 400 °C. At least 1,200 tobacco
5 constituents (e.g., nicotine, n-paraffin, some terpenes) are transferred intact from the tobacco into
6 the smoke stream by distillation in this region, and it is plausible that CDDs/CDFs present in the
7 unburned tobacco would be subject to similar distillation.
8 Bumb et al. (1980), using low-resolution mass spectrometry, analyzed the CDD content
9 of mainstream smoke from the burning of a U.S. brand of unfiltered cigarette. A package of 20
10 cigarettes was combusted in each of two experiments. Approximately 20 to 30 puffs of 2 to 3 sec
11 duration were collected from each cigarette on a silica column. Hexa-, hepta-, and octa-CDDs
12 were detected at levels of 0.004 to 0.008, 0.009, and 0.02 to 0.05 ng/g, respectively.
13 Muto and Takizawa (1989) employed a continuous smoking apparatus to measure CDD
14 congener concentrations in the mainstream smoke generated from the combustion of one kind of
15 filtered cigarette (brand not reported). The apparatus pulled air at a constant continuous rate
16 (rather than a pulsed rate) through a burning cigarette and collected the smoke on a series of traps
17 (glass fiber filter, polyurethane foam, and XAD-II resin). The CDD content of the smoke, as well
18 as the CDD content of the unburned cigarette and the ash from the burned cigarettes, were also
19 analyzed using low-resolution mass spectrometry. The results are presented in Table 5-10, and
20 the congener group profiles are presented in Figure 5-5. Table 5-11 and Figure 5-6 present the
21 mainstream smoke results on a mass-per-cigarette basis to enable comparison with the results of
22 other studies.
23 The major CDD congener group found was HpCDD, which accounted for 84% of total
24 CDDs found in the cigarette, 94% of total CDDs found in smoke, and 99% of total CDDs found
25 in the ash. The 2,3,7,8-HpCDDs also accounted for the majority of the measured TEQ in the
26 cigarettes and smoke; however, none were measured in the ash. Although no PeCDDs were
27 detected in the cigarette, PeCDDs were detected at low levels in the smoke, indicating probable
28 formation during combustion. On the basis of the similarities in the congener group profiles for
29 the three media, the study authors concluded that most of the CDDs found in the cigarette smoke
30 result from volatilization of CDDs/CDFs present in the unburned cigarette rather than being
31 formed during combustion.
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1 Ball et al. (1990) measured the CDD/CDF content of mainstream smoke for the 10 best-
2 selling German cigarette brands. The international test approach (1 puff/min; puff flow rate of
3 35 mL/2 sec) was employed with an apparatus that smoked 20 cigarettes at a time in three
4 successive batches and had a large collection device. The average TEQ content (on both an I-
5 TEQDF and a TEQDF-WHO98 basis) in mainstream smoke for the 10 brands tested, normalized to
6 a mass-per-cigarette basis, was 0.09 pg/cigarette (i.e., 16.5 times less than the value reported by
7 Muto and Takizawa, 1989, for a Japanese cigarette brand). However, the congener group
8 profiles were similar to those reported by Muto and Takizawa, with HpCDD and OCDD the
9 dominant congener groups found.
10 Lofroth and Zebiihr (1992) measured the CDD/CDF content of mainstream and
11 sidestream smoke from one common Swedish cigarette brand. The cigarette brand was labeled
12 as giving 17 mg carbon monoxide, 21 mg tar, and 1.6 mg nicotine. The international test
13 approach was used, and the smoke was collected on glass fiber filters followed by two
14 polyurethane plugs. The analytical results for mainstream and sidestream smoke are presented in
15 Table 5-11. The TEQ content in mainstream smoke, normalized to a mass-per-cigarette basis,
16 was 0.96 pg TEQDF-WHO98/cigarette (0.9 pg I-TEQDF/cigarette) (i.e., about two times less than
17 the value reported by Muto and Takizawa, 1989, and 10 times greater than the average value
18 reported by Ball et al., 1990). As in the Muto and Takizawa and Ball et al. studies, the dominant
19 congener groups were HpCDDs and OCDD; however, HpCDFs were also relatively high in
20 comparison with the other congener group totals. The sidestream smoke contained 2.08 pg
21 TEQDF-WHO98/cigarette (1.96 pg I-TEQDF/cigarette), or twice that of mainstream smoke.
22 Using high-resolution mass spectrometry, Matsueda et al. (1994) analyzed the CDD/CDF
23 content of tobacco from 20 brands of commercially available cigarettes collected in 1992 from
24 Japan, the United States, Taiwan, China, the United Kingdom, Germany, and Denmark. Table 5-
25 12 presents the study results. The total CDD/CDF content ranged from 109 to 1,136 pg/pack and
26 total TEQDF-WHO98 content ranged from 1.9 to 14 pg/pack (1.4 to 12.6 pg/pack on an I-TEQDF
27 basis). The Chinese cigarette brand contained significantly lower CDDs/CDFs and TEQs than
28 any other brand of cigarette. Figure 5-7 depicts the congener group profiles for the average
29 results for each country. A high degree of similarity is seen in the CDF congener group profiles
30 of the tested cigarette brands. The Japanese and Taiwanese cigarettes show CDD congener group
31 profiles different from the other countries' cigarettes.
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1 Brown et al. (2002) estimated that 440 billion cigarettes were consumed in the United
2 States in 2000. In 1995, approximately 487 billion cigarettes were consumed in the United States
3 and by U.S. overseas armed forces personnel. In 1987, approximately 575 billion cigarettes were
4 consumed. According to the Tobacco Institute (1995), per capita U.S. cigarette consumption,
5 based on total U.S. population aged 16 and over, was a record high of 4,345 in 1963, declining to
6 2,415 in 1995 and 1,563 in 2000 (USDA, 1997; U.S. Census Bureau, 2000). The activity level
7 estimates by Brown et al. (2002) were adopted and a high confidence rating is assigned because
8 they are based on known consumption rates.
9 The available emission factor data presented above provide the basis for two methods of
10 estimating the amount of TEQs that may have been released to the air in the United States in
11 2000, 1995, and in 1987 from the combustion of cigarettes. The confidence rating assigned to
12 the emission factor is low because of the very limited amount of testing performed to date. First,
13 an annual emission estimate for 2000 of 0.19 g TEQ (on a TEQDF-WHO98 or I-TEQDF basis) is
14 obtained if it is assumed that (a) the average TEQ content of seven brands of U.S. cigarettes
15 reported by Matsueda et al. (1994)—8.8 pg TEQDF-WHO98/pack (8.6 pg I-TEQDF/pack)—is
16 representative of cigarettes smoked in the United States, (b) CDDs/CDFs are not formed and the
17 congener profile reported by Matsueda et al. (1994) is not altered during combustion of
18 cigarettes, and (c) all CDDs/CDFs contributing to the TEQ are released from the tobacco during
19 smoking.
20 The second method of estimating is based on the assumption that the TEQ emission rates
21 for a common Swedish brand of cigarette reported by Lofroth and Zebiihr (1992) for mainstream
22 smoke (0.96 pg TEQDF-WHO98/cigarette [0.9 pg I-TEQDF/cigarette]) and sidestream smoke (2.08
23 pg TEQDF-WHO98/cigarette [1.96 pg I-TEQDF/cigarette]) are representative of the emission rates
24 for U.S. cigarettes. For 2000, the two methods yield estimates of 0.13 g TEQDF-WHO98 and 0.67
25 g TEQDF-WHO98 (0.63 g I-TEQDF). For 1995, the two methods yield estimates of 0.21 g (on a
26 TEQDF-WHO98 or I-TEQDF basis) and 1.48 g TEQDF-WHO98 (1.41 g I-TEQDF). For 1987, the two
27 methods yield estimates of 0.25 g TEQ (on a TEQDF-WHO98 or I-TEQDF basis) and 1.75 g
28 TEQDF-WH098 (1.67 g I-TEQDF).
29 For purposes of this report, the best estimates of annual emissions are assumed to be the
30 average of the annual emissions estimated by the two methods for 2000, 1995, and 1987 (0.4 g,
31 0.8 g, and 1 g TEQDF-WHO98 or I-TEQDF, respectively). These emissions were assigned a low
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1 confidence rating because the emission factor had a low confidence rating. Although these
2 emission quantities are relatively small when compared to the emission quantities estimated for
3 various industrial combustion source categories, they are significant because humans are directly
4 exposed to cigarette smoke.
5
6 5.6. PYROLYSIS OF BROMINATED FLAME RETARD ANTS
7 The pyrolysis and photolysis of brominated phenolic derivatives and polybrominated
8 biphenyl ethers used as flame retardants in plastics (especially those used in electronic devices),
9 textiles, and paints can generate considerable amounts of polybrominated dibenzo-^-dioxins
10 (BDDs) and dibenzofurans (BDFs) (Watanabe and Tatsukawa, 1987; Thoma and Hutzinger,
11 1989; Luijk et al., 1992). Watanabe and Tatsukawa (1987) observed the formation of BDFs from
12 the photolysis of decabromobiphenyl ether. Approximately 20% of the decabromobiphenyl ether
13 was converted to BDFs in samples that were irradiated with ultraviolet light for 16 hr.
14 Thoma and Hutzinger (1989) observed the formation of BDFs during combustion
15 experiments with polybutylene-terephthalate polymers containing 9 to 11% decabromodiphenyl
16 ether. Maximum formation of BDFs occurred at 400 to 600 °C, with a BDF yield of 16%.
17 Although the authors did not provide specific quantitative results for similar experiments
18 conducted with octabromodiphenyl ether and l,2-bis(tri-bromophenoxy)ethane, they did report
19 that BDDs and BDFs were formed.
20 Luijk et al. (1992) studied the formation of BDDs/BDFs during the compounding and
21 extrusion of decabromodiphenyl ether into high-impact polystyrene polymer at 275 °C. HpBDF
22 and OBDF were formed during repeated extrusion cycles, and the yield of BDFs increased as a
23 function of the number of extrusion cycles. HpBDF increased from 1.5 to 9 ppm (in the polymer
24 matrix), and OBDF increased from 4.5 to 45 ppm after four extrusion cycles.
25 Insufficient data are available at this time from which to derive annual BDD/BDF
26 emission estimates for this source.
27
28 5.7. CARBON REACTIVATION FURNACES
29 Granular activated carbon (GAC) is an adsorbent that is widely used to remove organic
30 pollutants from wastewater and to treat finished drinking water at water treatment plants.
31 Activated carbon is manufactured from the pyrolytic treatment of nut shells and coal (Buonicore,
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1 1992a). The properties of GAC make it ideal for adsorbing and controlling vaporous organic and
2 inorganic chemicals entrained in combustion plasmas as well as soluble organic contaminants in
3 industrial effluents and drinking water. The high ratio of surface area to particle weight
4 (600:1,600 m2/g), combined with the extremely small pore diameter of the particles (15 to 25
5 angstroms), increases the adsorption characteristics (Buonicore, 1992a). GAC eventually
6 becomes saturated, and the adsorption properties significantly degrade. When saturation occurs,
7 GAC usually must be replaced and discarded, which significantly increases the costs of pollution
8 control.
9 The introduction of carbon reactivation furnace technology in the mid-1980s created a
10 method involving the thermal treatment of used GAC to thermolytically desorb the synthetic
11 compounds and restore the adsorption properties for reuse (Lykins et al., 1987). Large-scale
12 regeneration operations, such as those used in industrial water treatment operations, typically use
13 multiple-hearth furnaces. For smaller-scale operations, such as those used in municipal water
14 treatment operations, fluidized-bed and infrared furnaces are used. Emissions are typically
15 controlled by afterburners followed by water scrubbers (U.S. EPA, 1997b).
16 The used GAC can contain compounds that are precursors to the formation of
17 CDDs/CDFs during the thermal treatment process. EPA measured precursor compounds in spent
18 GAC that was used as a feed material to a carbon reactivation furnace tested during the National
19 Dioxin Study (U.S. EPA, 1987a). The total chlorobenzene content of the GAC ranged from 150
20 to 6,630 ppb. Trichlorobenzene was the most prevalent species present, with smaller quantities
21 of di- and tetra-chlorobenzenes detected. Total halogenated organics were measured to be about
22 ISOppm.
23 EPA has stack-tested two GAC reactivation furnaces for the emission of dioxin (U.S.
24 EPA, 1987a; Lykins et al., 1987). One facility was an industrial carbon reactivation plant, and
25 the second facility was used to restore GAC at a municipal drinking water plant. EPA (U.S.
26 EPA, 1997b) reported results of other testing performed at a county water facility in California
27 during 1990.
28 The industrial carbon reactivation plant processed 36,000 kg/day of spent GAC used in
29 the treatment of industrial wastewater effluents. This facility was chosen for testing because it
30 was considered to be representative of other facilities in the source category (U.S. EPA, 1987a).
31 Spent carbon was reactivated in a multiple-hearth furnace, cooled in a water quench, and shipped
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1 back to primary chemical manufacturing facilities for reuse. The furnace was fired by natural gas
2 and consisted of seven hearths arranged vertically in series. The hearth temperatures ranged from
3 480 to 1,000 °C. Air pollutant emissions were controlled by an afterburner, a sodium spray
4 cooler, and an FF. Temperatures in the afterburner were about 930 °C. The estimated I-TEQDF
5 emission factor (treating nondetect values as zero) was 0.76 ng TEQDF-WHO98/kg (0.64 ng
6 I-TEQDF/kg) carbon processed. The emission factor for total CDDs/CDFs was 58.6 ng/kg.
7 Because analyses were performed only for 2,3,7,8-TCDD; 2,3,7,8-TCDF; OCDD; and OCDF
8 and the congener groups, equivalent concentrations were assumed for all toxic and nontoxic
9 congeners in each of the penta-, hexa-, and hepta-congener groups.
10 The second GAC reactivation facility tested by EPA consisted of a fluidized-bed furnace
11 located at a municipal drinking water treatment plant (Lykins et al., 1987). The furnace was
12 divided into three sections: a combustion chamber, a reactivation section, and a dryer section.
13 The combustion section was fired by natural gas and consisted of a stoichiometrically balanced
14 stream of fuel and oxygen. Combustion temperatures were about 1,038 °C. Gases from the
15 reactivation and combustion section were directed through an acid gas scrubber and high-
16 temperature afterburner prior to discharge from a stack. Although measurable concentrations of
17 dioxin-like compounds were detected in the stack emissions, measurements of the individual
18 CDD/CDF congeners were not performed; therefore, it was not possible to derive TEQ emission
19 factors for this facility. With the afterburner operating, no CDD congeners below HpCDD were
20 detected in the stack emissions. Concentrations of HpCDDs and OCDD ranged from 0.001 to
21 0.05 ppt/volume basis (ppt/v) and 0.006 to 0.28 ppt/v, respectively. All CDF congener groups
22 were detected in the stack emissions even with the afterburner operating. Total CDFs emitted
23 from the stack averaged 0.023 ppt/v.
24 EPA (U.S. EPA, 1997b) reported a TEQ emission factor of 1.73 ng I-TEQDF/kg of carbon
25 processed for the reactivation unit at a county water facility in California in 1990. The emission
26 factor for total CDDs/CDFs was reported to be 47 ng/kg (i.e., similar to the total CDD/CDF
27 emission factor of 58.6 ng/kg at the industrial GAC facility). Because congener-specific results
28 were not reported, it was not possible to calculate the TEQDF-WHO98 emission factor. The report
29 also did not provide the configuration and type of furnace tested; however, it did state that the
30 emissions from the furnace were controlled by an afterburner and a scrubber.
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1 The industrial GAC reaction furnace test data indicate that an average of 0.64 ng
2 I-TEQDF/kg of GAC may be released. The I-TEQDF emission rate for the reactivation unit at the
3 county water treatment facility was 1.73 ng I-TEQDF/kg carbon. Low confidence ratings are
4 given to these emission factors because only two GAC reactivation furnaces were stack-tested
5 and not all congeners were analyzed at the industrial GAC facility.
6 The mass of GAC that is reactivated annually in carbon reactivation furnaces is not
7 known. However, a rough estimate, to which a low confidence rating is assigned, is the mass of
8 virgin GAC shipped each year by GAC manufacturers. According to the U.S. Department of
9 Commerce (1990c), 48,000 metric tons of GAC were shipped in 1987. EPA reported that in
10 1990, water and wastewater treatment operations consumed 65,000 metric tons of GAC (U.S.
11 EPA, 1995c, 1997b). The 1990 activity level is used in this document as a surrogate for the 1995
12 and 2000 activity levels.
13 Applying the average TEQ emission factor of 1.2 ng (TEQDF-WHO98 or I-TEQDF) per kg
14 of reactivated carbon for the two tested facilities to the estimates of potential GAC reactivation
15 volumes, yields annual release estimates of 0.06 g (TEQDF-WHO98 or I-TEQDF) in 1987 and
16 0.08 g (TEQDF-WHO98 or I-TEQDF) in 1995 and 2000 (assuming that the activity level for 1990 is
17 representative of the 1995 and 2000 activity levels). These emission estimates are assigned a low
18 confidence rating because both the activity and emission factor estimates had low confidence
19 ratings.
20
21 5.8. KRAFT BLACK LIQUOR RECOVERY BOILERS
22 Kraft black liquor recovery boilers are associated with the production of pulp in the
23 making of paper using the Kraft process. In this process, wood chips are cooked in large vertical
24 vessels called digesters at elevated temperatures and pressures in an aqueous solution of sodium
25 hydroxide and sodium sulfide. Wood is broken down into two phases: a soluble phase
26 containing primarily lignin and an insoluble phase containing the pulp. The spent liquor (called
27 black liquor) from the digester contains sodium sulfate and sodium sulfide, which the industry
28 recovers for reuse in the Kraft process.
29 In the recovery of black liquor chemicals, weak black liquor is first concentrated in
30 multiple-effect evaporators to about 65% solids. The concentrated black liquor also contains 0.5
31 to 4% chlorides by weight, which are recovered through combustion. The concentrated black
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1 liquor is sprayed into a Kraft black liquor recovery furnace equipped with a heat recovery boiler.
2 The bulk of the inorganic molten smelt that forms in the bottom of the furnace contains sodium
3 carbonate and sodium sulfide in a ratio of about 3:1. The combustion gas is usually passed
4 through an ESP that collects PM prior to being vented out the stack. The PM can be processed to
5 further recover and recycle sodium sulfate (Someshwar and Pinkerton, 1992).
6 In 1987, EPA stack-tested three Kraft black liquor recovery boilers for the emission of
7 dioxin in conjunction with the National Dioxin Study (U.S. EPA, 1987a). The three sites tested
8 by EPA were judged to be typical of Kraft black liquor recovery boilers at that time. During
9 pretest surveys, two facilities were judged to have average potential and one was judged to have
10 high potential for CDD/CDF emissions, based on the amount of chlorine found in the feed to
11 these units. Dry-bottom ESPs controlled emissions from two of the boilers; a wet-bottom ESP
12 controlled emissions from the third. The results of these tests include congener group
13 concentrations but lack measurement results for specific congeners other than 2,3,7,8-TCDD and
14 2,3,7,8-TCDF.
15 NCASI (1995) provided congener-specific emission test results for six additional boilers
16 tested during 1990 to 1993. Three boilers were of the direct contact type, and three were
17 noncontact type. All were equipped with ESPs. The average congener and congener group
18 emission factors are presented in Table 5-13 for the three facilities reported by EPA (U.S. EPA,
19 1987a) and the six facilities reported by NCASI (1995). Figure 5-8 presents the average
20 congener and congener group profiles based on the test results presented by NCASI (1995).
21 The average TEQ emission factor, based on the data for the six NCASI facilities with
22 complete congener data, is 0.028 ng TEQDF-WHO98/kg (0.029 ng I-TEQDF/kg) of black liquor
23 solids, assuming nondetect values are zero, and 0.078 ng TEQDF-WHO98/kg (0.068 ng I-
24 TEQDF/kg), assuming nondetect values are present at one-half the DL. This value is assumed to
25 apply to all three reference years (1987, 1995, and 2000). The results for the three facilities
26 reported by EPA were not used in the derivation of the TEQ emission factor because congener-
27 specific measurements for most 2,3,7,8-substituted congeners were not made in the study (U.S.
28 EPA, 1987a). A medium confidence rating is assigned to those emission factors because they
29 were derived from the stack-testing of six Kraft black liquor recovery boilers that were judged to
30 be fairly representative of technologies used at Kraft pulp mills in the United States.
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1 A 1995 survey of the industry indicated that 215 black liquor recovery boilers were in
2 operation at U.S. pulp and paper mills. All but one of these boilers used ESPs for control of
3 particulate emissions; the one unique facility used dual scrubbers. In addition, ESPs were
4 reported to have been the predominant means of particulate control at recovery boilers for the
5 past 20 years (Gillespie, 1998).
6 The amounts of black liquor solids burned in Kraft black liquor recovery boilers in the
7 United States during 1987 and 1995 were 69.8 million metric tons and 80.8 million metric tons,
8 respectively (American Paper Institute, 1992; American Forest and Paper Association, 1997).
9 These activity level estimates are assigned a high confidence rating because they are based on
10 comprehensive industry survey data. Combining the emission factors derived above with the
11 activity level estimates for 1987 and 1995 yields estimated annual emissions from this source of
12 approximately 2 g (TEQDF-WHO98 or I-TEQDF) in 1987 and 2.3 g (TEQDF-WHO98 or I-TEQDF) in
13 1995. These emission estimates were assigned a medium confidence rating because the emission
14 factor had a medium confidence rating.
15 For 2000, NCASI provided estimates of activity levels for Kraft recovery furnaces and
16 Kraft lime kilns and CDD/CDF releases, including emissions from 11 Kraft recovery furnaces
17 and four Kraft lime kilns (Gillespie, 2002). The activity levels were reported to be 90.7 million
18 metric tons for Kraft recovery furnaces and 13 million metric tons for Kraft lime kilns. These
19 activity level estimates are assigned a high confidence rating because they are based on
20 comprehensive industry survey data. Emission factors were taken from the NCASI Handbook of
21 Chemical Specific Information for SARA Section 313 Form R Reporting. The factors provided
22 in this handbook were compiled from valid test data supplied to NCASI by a variety of sources,
23 including NCASI member companies who had performed the tests in response to a regulatory
24 program. They were assigned a high confidence rating because they are based on a
25 comprehensive survey of stack emissions. Congener-specific CDD/CDF TEQ emission factors
26 were provided for both source categories (Table 5-14). Using the congener-specific emission
27 factors and the activity levels provided above, NCASI estimated CDD/CDF TEQDF-WHO98
28 emissions for each congener (Table 5-14) and reported total emissions as 0.75 g TEQDF-
29 WHO98/yr and 6.9e-5 g TEQDF-WHO98/yr for Kraft recovery furnaces and Kraft lime kilns,
30 respectively. This 2000 emission estimate was rated as high confidence because both the
31 emission factor and activity level were rated as high confidence.
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1 5.9. OTHER IDENTIFIED SOURCES
2 Several manufacturing processes are identified as potential sources of CDD/CDF
3 formation because the processes use chlorine-containing components or involve application of
4 high temperatures. However, no testing of emissions from these processes has been performed in
5 the United States, and only minimal emission rate information has been reported for these
6 processes in other countries. Therefore, these sources are rated as Category E sources, meaning
7 their emissions cannot be quantified.
8 Burning of candles. Schwind et al. (1995) analyzed the wicks and waxes of uncolored
9 candles as well as the fumes of burning candles for CDDs/CDFs, total chlorophenol, and total
10 chlorobenzene content. The results, presented in Table 5-15, show that beeswax contained the
11 highest levels of CDDs/CDFs and total chlorophenols. In contrast, the concentration of total
12 chlorobenzenes in stearin wax was higher than that in paraffin or beeswax by a factor of 2 to 3.
13 The concentrations of the three analyte groups were significantly lower in the wicks than in the
14 waxes. Emissions of CDDs/CDFs from all three types of candles were very low during burning.
15 In fact, comparison of the emission factor with the original CDD/CDF concentrations in the wax
16 indicates a net destruction of the CDDs/CDFs originally present in the wax. Information on the
17 activity level is lacking, therefore, no estimate of environmental release can be made at this time.
18 Glass manufacturing. Annual emissions of less than 1 g I-TEQDF/yr have been
19 estimated for glass manufacturing facilities in the Netherlands (Bremmer et al., 1994) and the
20 United Kingdom (Douben et al., 1995). Glass is manufactured by heating a mixture of sand and,
21 depending on the type of glass, lime, sodium carbonate, dolomite, clay, or feldspar to a
22 temperature of 1,400 to 1,650 °C. In addition, various coloring and clarifying agents may be
23 added. Chlorine enters the process as a contaminant (NaCl) in sodium carbonate (Bremmer et al.
24 1994). However, the emission factors used by Bremmer et al. (1994) and Douben et al. (1995)
25 were not reported. Umweltbundesamt (1996) reported relatively low emission factors
26 (approximately 0.002 and 0.007 ng I-TEQDF/kg) for two glass manufacturing facilities in
27 Germany.
28 Lime kilns. Annual emissions from lime kilns in Belgium and the United Kingdom have
29 been reported by Wevers and De Fre (1995) and Douben et al. (1995), respectively. However,
30 the emission factors used to generate those estimates were not provided. Umweltbundesamt
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1 (1996) reported low emissions (0.016 to 0.028 ng I-TEQDF/kg) during tests at two lime kilns in
2 Germany.
3 Ceramics and rubber manufacturers. Douben et al. (1995) estimated annual emissions
4 from ceramic manufacturers and rubber manufacturers in the United Kingdom. Lexen et al.
5 (1993) had previously detected high concentrations of CDDs/CDFs in emissions from a ceramic
6 manufacturer in Sweden that occasionally glazed ceramics by volatilization of sodium chloride in
7 a coal-fired oven. Lexen et al. (1993) also detected high pg/L levels of I-TEQDF in the scrubber
8 water from the vulcanization process at a Swedish rubber manufacturer.
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Table 5-1. CDD/CDF emission factors for cement kilns burning hazardous
waste for reference years 1987 and 1995
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 I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Kilns burning hazardous waste mean emission factor
(nondetect values set equal to zero)
(ng/kg clinker produced)
APCD inlet temperature
>232 °C
3.38
4.28
4.85
6.93
9.55
27.05
18.61
36.26
13.36
23.48
22.24
8.46
0.96
13.33
7.73
2.16
2.51
28.58
30.7
406.76
608.65
845.99
192.99
18.61
295.72
127.99
50.75
8.36
2.51
2,558.33
APCD inlet temperature
<232 °C
0.02
0.13
0.29
0.42
0.4
3.16
1.08
3.24
0.23
0.65
0.55
0.27
0.06
0.52
0.34
0.16
0.37
1.04
1.11
1.78
0.89
0.69
0.42
1.08
11.52
3.83
1.88
0.47
0.37
22.92
APCD = Air pollution control device
Source: U.S. EPA (1996c).
03/04/05
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Table 5-2. CDD/CDF emission factors for cement kilns burning hazardous
waste for reference year 2000
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 I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean emission factor
(ng/kg clinker produced)
Nondetect set to zero
0.1
1.05
1.35
3.14
3.41
15.8
4.86
12.12
2.03
4.08
3.22
1.38
0.28
2.61
1.22
0.37
0.36
5.49
5.95
161.5
217.62
330.66
62.87
4.86
103.57
43.22
18.72
1.29
0.36
864.55
Nondetect set to 1A detection
limit
0.11
0.55
0.69
1.18
1.3
6.14
2.57
3.03
1.06
2.29
1.35
0.69
0.23
1.23
0.54
0.22
0.23
2.87
3.13
40.75
37.68
83.76
7.26
2.57
18.34
6.15
4.13
1.03
0.23
347.91
Source: U.S. EPA (1996c); U.S. EPA (2002b).
03/04/05
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Table 5-3. CDD/CDF emission factors for cement kilns burning nonhazardous
waste for reference years 1987,1995, and 2000a
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 I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean emission factor
(ng/kg clinker produced)
Nondetect set to zero
0.01
0.03
0.03
0.04
0.04
0.39
0.64
0.73
0.1
0.22
0.17
0.05
0.01
0.08
0.13
0
0.22
0.26
0.27
1.89
1.92
5.51
0.78
0.64
7.72
2.06
0.56
0.23
0.22
21.53
Nondetect set to 1A detection
limit
0.02
0.04
0.04
0.05
0.06
0.39
0.64
0.73
0.11
0.23
0.18
0.06
0.02
0.08
0.14
0.02
0.24
0.27
0.3
1.89
1.92
5.51
0.78
0.64
7.72
2.06
0.56
0.23
0.24
21.55
The same CDD/CDF emission factor was assumed for all three years.
Source: U.S. EPA (1996c); Bell (1999).
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Table 5-4. National emission estimates for cement kilns for reference years
1987 and 1995
Category
TEQ emission factor
(ng/kg clinker)
I-TEQDF
TEQDF-
WHO98
Activity
level
(billion kg
clinker/yr)
Annual TEQ emission
(g/yr)
I-TEQDF
TEQDF-
WHO98
Reference year 1987
Hazardous waste >232 °C
Hazardous waste <232 °C
Nonhazardous waste
28.58
1.04
0.26
30.7
1.11
0.27
TOTAL
3.8
1
47.2
52
108.6
1
12.3
122
116.7
1.1
12.7
131
Reference year 1995
Hazardous waste >232 °C
Hazardous waste <232 °C
Nonhazardous waste
28.58
1.04
0.26
30.7
1.11
0.27
TOTAL
5.04
1.26
61.3
67.6
144
1.3
15.9
161
154.7
1.4
16.6
173
Table 5-5. National emission estimates for cement kilns for reference
year 2000
Category
Hazardous waste
Nonhazardous waste
TEQ CCD/CDF
concentrations
(ng/kg clinker)
I-TEQDF
5.49
0.26
TEQDF-
WHO98
5.95
0.27
TOTAL
Activity
level
(billion kg
clinker/yr)
11.5
63.7
75.2
Annual TEQ emission
(g/yr)
I-TEQDF
63.3
16.6
79.9
TEQDF-
WHO98
68.4
17.2
85.6
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Table 5-6. CDD/CDF concentrations in ash samples from cement kiln
electrostatic precipitator and lightweight aggregate (LWA) kiln fabric filter
(ng/kg)
Congener
2,3,7,8-TCDD
Total TCDD
1,2,3,7,8-PeCDD
Total PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Total HxCDD
12,2,3,4,6,7,8-HpCDD
Total HpCDD
OCDD
Cement
kiln
Avg.
cone.
0.429
36.1
0.886
54.9
1.03
2.36
2.47
173
17.7
55.2
21
LWA
kiln
Avg.
cone.
3.97
333
17.3
467
15.4
35.6
56.6
500
133
300
133
Total TCDD TEQs
2,3,7,8-TCDF
Total TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Total 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
Total HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Total HpCDF
OCDF
4.65
18.1
1.04
2.59
31.8
2.13
0.869
0.523
2.14
9.26
1.84
0.739
3.06
1.43
833
4630
100
267
2930
267
100
7.8
133
1230
167
22.6
2670
39.2
Total TCDF TEQs
Cement kiln
I-TEQ
0.429
0.443
0.103
0.236
0.247
0.177
0.021
1.66
0.465
0.0518
1.3
0.213
0.0869
0.0523
0.214
0.0184
0.00739
0.00143
2.41
WHO-
TEQ
0.429
0.886
0.103
0.236
0.247
0.177
0.0021
2.08
0.465
0.0518
1.3
0.213
0.869
0.0523
0.214
0.0184
0.00739
0.000143
2.4
LWA kiln
I-TEQ
3.97
8.65
1.54
3.56
5.66
1.33
0.133
2.48
83.3
5
133
26.7
10
0.780
13.3
1.67
0.226
0.0392
274
WHO-TEQ
3.97
17.3
1.54
3.56
5.66
1.33
0.133
33.4
83.3
5
133
26.7
10
0.780
13.3
1.67
0.226
0.00392
274
03/04/05
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Table 5-7. CDD/CDF estimates in cement kiln dust (CKD) for reference
years 1987,1995, and 2000
Category
CDD/CDF
concentration
(ngl-
TEQDF/kg of
CKD)
CKD beneficially reused on
or off site
Activity level
(million kg
tons
CKD/yr)
Annual TEQ
CDD/CDF
concentration
(g/yr)
CKD sent to a landfill for
disposal
Activity
level
(million kg
tons
CKD/yr)
Annual TEQ
CDD/CDF
concentration
(g/yr)
Reference year 1987
HW kilns
NHW kilns
35
0.003
120
632
4.2
0.0019
426
2,230
14.9
0.0067
Reference year 1995
HW kilns
NHW kilns
35
0.003
104
547
3.6
0.0016
505
2,642
17.7
0.0079
Reference year 2000
HW kilns
NHW kilns
35
0.003
94
480
3.3
0.0014
365
1,858
12.8
0.0056
HW = Hazardous waste
NHW = Nonhazardous waste
03/04/05
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Table 5-8. Congener-specific profile for hot-mix asphalt plants
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
Total TEQDF-WHO98
Mean emission factor (2 facilities)
(ng/kg combusted)
Nondetect set to zero
1.62e-05
2.70e-05
4.30e-06
2.95e-05
2.09e-05
1.23e-05
5.81e-07
4.32e-04
9.07e-05
1.21e-04
9.64e-05
2.95e-05
1.73e-04
4.83e-05
1.58e-05
6.91e-06
1.19e-07
1.12e-03
Nondetect set to 1A detection limit
6.27e-04
4.12e-04
8.61e-05
1.06e-04
9.99e-05
2.71e-05
4.76e-06
4.88e-04
1.08e-04
4.10e-04
1.62e-04
8.12e-05
2.14e-04
1.10e-04
2.71e-05
2.17e-05
3.13e-06
2.99e-03
Source: U.S. EPA (2001b).
03/04/05
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Table 5-9. CDD/CDF emission factors for petroleum catalytic reforming units
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
,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-CDD
Total 2,3,7,8-CDF
Total I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Semiregenerative unit
(ng/barrel)a
Nondetect set
to zero
ND
5.69e-05
4.22e-05
ND
ND
7.02e-04
2.55e-03
2.32e-04
4.68e-04
1.09e-03
1.06e-03
1.07e-03
ND
1.24e-03
2.94e-03
8.32e-04
l.Ole-03
3.35e-03
9.94e-03
l.Ole-03
1.04e-03
ND
3.56e-04
1.28e-03
1.39e-03
2.55e-03
2.70e-03
5.12e-03
7.85e-03
4.88e-03
l.Ole-03
2.71e-02
Nondetect set to
1A detection limit
2.35e-05
9.58e-05
8.09e-05
5.52e-05
5.10e-05
7.02e-04
2.55e-03
2.32e-04
4.68e-04
1.09e-03
1.06e-03
1.07e-03
6.82e-05
1.24e-03
9 Q4.P-03
Z-.^T-C \J J
8.32e-04
l.Ole-03
3.56e-03
l.OOe-02
1.08e-03
1.12e-03
2.35e-05
3.56e-04
1.28e-03
1.39e-03
2.55e-03
2.70e-03
5.12e-03
7.85e-03
4.88e-03
l.Ole-03
2.72e-02
Continuous regeneration unit
(ng/barrel)a
Nondetect set
to zero
1.61e-02
2.87e-01
3.47e-01
8.45e-01
5.56e-01
3.02e+00
1.71e+00
6.10e-01
1.72e+00
2.33e+00
4.70e+00
3.58e+00
4.34e-01
3.10e+00
1.59e+01
1.45e+00
3.75e+00
6.77e+00
3.76e+01
3.04e+00
3.18e+00
6.84e+00
5.61e+00
8.18e+00
6.58e+00
1.71e+00
4.68e+01
3.30e+01
2.96e+01
2.11e+01
3.75e+00
1.63e+02
Nondetect set to
1A detection limit
1.61e-02
2.87e-01
3.47e-01
8.45e-01
5.56e-01
3.02e+00
1.71e+00
6.10e-01
1.72e+00
2.33e+00
4.70e+00
3.58e+00
4.34e-01
3.10e+00
1.59e+01
1.45e+00
3.75e+00
6.77e+00
3.76e+01
3.04e+00
3.18e+00
6.84e+00
5.61e+00
8.18e+00
6.58e+00
1.71e+00
4.68e+01
3.30e+01
2.96e+01
2.11e+01
3.75e+00
1.63e+02
aOne barrel assumed to be equivalent to 139 kg.
ND = Not detected
Sources: Radian Corporation (1991); CARB (1999).
03/04/05
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Table 5-10. CDD concentrations in Japanese cigarettes, smoke, and ash
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Cigarette
(Pg/g)
ND (0.5)
ND (0.5)
2.01a
a
a
1343
257
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
1602.01
NR
13.9
13.7
44.9
ND (0.5)
13.41
1629
257
NR
NR
NR
NR
NR
1944
Concentrations
Mainstream smoke
(ng/m3)
ND (0.22)
0.43
2.15a
a
a
783
240
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
1025.58
NR
8.5
8.3
68
1.51
7.51
4939
240
NR
NR
NR
NR
NR
5256
Ash
(Pg/g)
ND (0.5)
ND (0.5)
0.56a
a
a
ND (0.5)
ND (0.5)
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
0.56
NR
0.06
0.06
4.63
ND (0.5)
5.01
3211
ND (0.5)
NR
NR
NR
NR
NR
3221
"Value reported only for total 2,3,7,8-substituted HxCDDs.
ND = Not detected; value in parenthesis is the detection limit
NR = Not reported
Source: Muto and Takizawa (1989).
03/04/05
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Table 5-11. CDD/CDF emissions in cigarette smoke
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Concentrations normalized to a per cigarette basis (pg/cig)
Muto and
Takizawa (1989)
(1 Japanese brand)
(mainstream
smoke)
ND (0.04)
0.075
0.376
b
b
137
42
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
179.45
NR
1.49
1.49
11.9
0.264
1.31
864
42
NR
NR
NR
NR
NR
919.47
Ball et al. (1990)
(avg. of 10 German
brands)
(mainstream
smoke)
ND (0.03)
ND (0.03)
0.06
0.05
0.04
1.3
3.4
0.19
0.13
0.04
ND (0.03)
0.03
0.03
0.05
0.16
0.03
0.11
4.85
0.77
0.09
0.09
0.51
0.14
0.53
2.9
3.4
1.41
0.83
0.35
0.27
0.11
10.45
Lofroth and
Zebiihr (1992)
(1 Swedish brand)
(mainstream
smoke)
0.028
0.15
0.1
0.34
0.25
6.05
22.1
1.2C
0.34C
0.34
1.3C
0.48
0.14
0.21
10
2.6
3.2
29.02
19.81
0.9
0.96
0.61
1.07
2.52
12.3
22.1
4.5
3.23
5.3
19.8
3.2
74.63
Lofroth and
Zebiihr (1992)
(1 Swedish brand)
(sidestream smoke)
0.07
0.32
0.19
0.6
0.55
12.2
38.8
2.1C
0.8C
0.6
3.8C
1.2
0.39
0.5
23.5
5
10.7
52.7
48.6
1.96
2.08
0.67
2.14
5.2
21.3
38.8
5.75
6.35
12.9
47.8
10.7
151.6
Emissions calculated assuming 0.0035 m3 of smoke are inhaled per 20 cigarettes smoked (Muto and Takizawa,
1992).
bMuto and Takizawa (1989) reported a value only for total 2,3,7,8-HxCDDs (0.38 pg/cig).
"Concentrations listed include the contribution of a coeluting non-2,3,7,8-substituted congener.
ND = Not detected; value in parenthesis is the detection limit
NR = Not reported
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Table 5-12. CDD/CDF concentrations in cigarette tobacco
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Concentrations in brands from various countries (pg/pack)
U.S.
(avg. of 7
brands)
1.2
1.6
6.9
a
a
52.7
589.3
18.2
8.7
b
8.1
C
c
C
17.6
d
24.6
651.7
77.2
8.6
8.8
47.1
27.6
40.6
108.7
589.3
183.8
57.7
29.1
27.3
24.6
1,135.8
Japan
(avg. of 6
brands)
0.5
1.4
4.8
a
a
17.8
244
4.8
5.3
b
8.1
C
C
c
11.1
d
10.5
268.5
39.8
4.6
5.1
296.3
33.6
29.2
40
244
102.1
45.9
26.4
16.6
10.5
844.6
United
Kingdom
(avg. of 3
brands)
1.7
3.1
6.1
a
a
23.9
189.5
15.6
21.2
b
17
C
C
c
13.6
d
8.3
224.3
75.7
12.6
14
85.1
62.9
49.2
47.7
189.5
348.9
134.5
51.3
19
8.3
996.4
Taiwan
(1 brand)
1
3.3
12.2
a
a
26.4
272.7
11
16
b
12.9
C
C
c
13.2
d
13.9
315.6
67
9.3
10.7
329
150.5
99.4
62
272.7
372.1
149.1
45.8
18.5
13.9
1513
China
(1 brand)
ND
1.1
1.1
a
a
2.2
28.2
1.2
1.5
b
2.2
C
C
c
1.5
d
0.5
32.6
6.9
1.4
1.9
9.7
5.2
5.4
3.8
28.2
35.4
11.2
7.8
1.7
0.5
108.9
Denmark
(1 brand)
0.5
0.8
6.2
a
a
53.3
354.3
2.2
4.3
b
4.3
C
C
c
7
d
10.5
415.1
28.3
3.8
3.9
17
9.8
26.7
93.1
354.3
97.8
35.5
18.1
11.1
10.5
673.9
Germany
(1 brand)
1.1
3.3
5.7
a
a
32.7
288.6
7.9
14.4
b
13.2
C
C
c
12.9
d
13.9
331.4
62.3
9.1
10.5
49.5
40.8
40.6
60.2
288.6
233.4
97.5
40.8
21.2
13.9
886.5
"Value reported only for total 2,3,7,8-substituted HxCDDs.
Value reported only for total 2,3,7,8-substituted PeCDFs.
"Value reported only for total 2,3,7,8-substituted HxCDFs.
dValue reported only for total 2,3,7,8-substituted HpCDFs.
Source: Matsueda et al. (1994).
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Table 5-13. CDD/CDF mean emission factors (ng/kg feed) for black liquor
recovery boilers
Congener
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
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 TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total I-TEQDF
Total TEQDF-WHO98
Total CDD/CDF
U.S. EPA (1987)
(3 facilities)
Nondetect set to
zero
0
NR
NR
NR
NR
NR
4.24
0.04
NR
NR
NR
NR
NR
NR
NR
NR
0.35
0.21
0.27
0.8
2.05
4.24
0.95
0.64
1.16
1.05
0.35
0.10a
0.10a
11.71
Nondetect set to Vz
detection limit
0.04
NR
NR
NR
NR
NR
4.24
0.06
NR
NR
NR
NR
NR
NR
NR
NR
0.35
0.36
0.35
1.02
2.05
4.24
1
0.77
1.2
1.05
0.35
0.15a
0.16a
12.17
NCASI (1995)
(6 facilities)
Nondetect set to
zero
0
0
0.001
0.003
0.006
0.108
1.033
0.04
0.03
0.033
0.007
0.012
0.005
0.01
0.024
0
0.113
0.106
0.013
0.104
0.252
1.033
1.27
0.37
0.102
0.024
0.113
0.029
0.028
3.386
Nondetect set to Vz
detection limit
0.016
0.016
0.018
0.015
0.019
0.135
1.054
0.049
0.036
0.037
0.022
0.021
0.016
0.021
0.035
0.014
0.13
0.123
0.059
0.122
0.279
1.054
1.275
0.376
0.109
0.038
0.13
0.065
0.072
3.566
"Estimate based on the measured data for 2,3,7,8-TCDD; 2,3,7,8-TCDF; OCDD; and OCDF and congener group
emissions (i.e., for the penta-, hexa-, and hepta-CDD and CDFs, it was assumed that the measured emission factor
within a congener group was the sum of equal emission factors for all congeners in that group, including non-
2,3,7,8-substituted congeners).
NR = Not reported
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Table 5-14. CDD/CDF TEQ emission factors and emission estimates from
Kraft recovery furnaces and 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
Kraft recovery furnaces
TEQDF-WH098
(ng/lb BLS)
O.OOe+00
O.OOe+00
O.OOe+00
2.00e-04
5.00e-04
4.90e-04
1.42e-04
5.00e-04
l.OOe-04
1.50e-03
4.00e-04
2.00e-04
O.OOe+00
4.00e-04
6.00e-05
O.OOe+00
2.60e-05
Emissions
(ng/yr)
O.OOe+00
O.OOe+00
O.OOe+00
3.33e+07
8.31e+07
8.15e+07
2.36e+07
8.31e+07
1.66e+07
2.49e+08
6.65e+07
3.33e+07
O.OOe+00
6.65e+07
9.98e+06
O.OOe+00
4.32e+06
Kraft lime kilns
TEQDF-WH098
(ng/lb CaO)
O.OOe+00
O.OOe+00
O.OOe+00
l.OOe-04
O.OOe+00
2.80e-04
2.56e-04
8.00e-04
l.OOe-04
O.OOe+00
9.00e-04
2.00e-04
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
Emissions
(ng/yr)
O.OOe+00
O.OOe+00
O.OOe+00
2.60e+03
O.OOe+00
7.27e+03
6.65e+03
2.08e+04
2.60e+03
O.OOe+00
2.34e+04
5.20e+03
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
BLS = Black liquor solids
CaO = Calcium oxide
Table 5-15. Concentrations of CDD/CDF in candle materials and emissions
Wax
material
Paraffin
Stearin
Beeswax
Paraffin
Stearin
Beeswax
Candle
component
Wax
Wax
Wax
Wick
Wick
Wick
Concentration
CDD/CDF
(ngI-TEQDF/kg)
0.59
1.62
10.99
0.18
0.12
0.08
Total
chlorophenols
(M-g/kg)
14.8
32.3
256
1.23
0.94
0.74
Total
chlorobenzenes
(M.g/kg)
130
330
120
0.67
0.34
0.35
Emission factor
CDD/CDF
(ngI-TEQDF/kg
burnt wax)
0.015
0.027
0.004
NR
NR
NR
Source: Schwindetal. (1995).
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Ratio (congener emission factor/total CDD/CDF emission factor)
Oa 0.005 0.01 0.015
0.02
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
aNondetect set equal to zero.
Figure 5-1. Congener profile for air emissions from cement kilns burning
hazardous waste for reference years 1987 and 1995.
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Ratio (congener emission factor / 2378-CDD/CDF emission factor)
0.020
0.030
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.1 0.2 0.3 0.4 0.5
Figure 5-2. Congener profile for air emissions from cement kilns burning
hazardous waste for reference year 2000.
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Ratio (congener emission factor/2378-CDD/CDF emission factor)
0.050
0.100
0.150
0.200
0.250
0.300
Ratio (congener group emission factor/total CDD/CDF emission
factor)
0.050
0.100
0.150
0.200
0.250
0.300
0.350
Figure 5-3. Congener profile for air emissions from cement kilns burning
nonhazardous waste for reference years 1987,1995, and 2000.
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Ratio (mean congener emission factor/total CDD/CDF emission factor)
Oa 0.02 0.04 0.06 0.08 0.1 0.12
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HiCDD
1,2,3.6,7,8-HiCDD
1.2,3.7,8.9-HiCDD
1.2.3.4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OODD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HzCDF
1,2,3,6,7,8-HzCDF
1.2,3,7,8,9-HzCDF
2,3,4,6,7,8-HiCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpODF
1,2,3,4,6,7,8,9-OCDF
ooooooooq
xxxxxxxxxxxx
Ratio (mean congener emission factor/total CDD/CDF emission factor)
Oa 0.05 0.1 0.15 0.2 0.25 0.3 0.35
HpCDD
• Continents Reformer
' Nondetect set equal to zero.
Semi-regenerative Reformer
Figure 5-4. Congener and congener group profiles for air emissions from
petroleum catalytic reforming units.
Source: CARB (1999); Radian (1991).
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1.1
1.0
§0.9
o
8 0.8
O
lo.7
g
8
53 0.4
g
If 0.3
o
0.2
0.1
0
TCDD PeCDD
^B Cigarettes (row 1)
^H Ash (row 3)
HxCDD HpCDD OCDD
^B Mainstream Smoke (row 2)
Figure 5-5. CDD profiles for Japanese cigarettes, smoke, and ash.
Source: Matsueda et al. (1994).
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1
§0.9
u
g 0.8
§0.7
g-0.5
0.4
0.3
0.2
0.1
0
TCDD PeCDD HxCDD HpCDD OCDD TCDF PeCDF HxCDF HpCDF OCDF
^H Japanese Mainstream (row 1) ^H German Mainstream (row 2)
^H Swedish Mainstream (row 3) ^H Swedish Sidestream (row 4)
Figure 5-6. Congener group profiles for mainstream and sidestream
cigarette smoke
Source: Matsueda et al. (1994).
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0.6
0.5
I
80.4
I
§ 0.3
I
S3 0.2
0.1
/A
/A
TCDD PeCDD HxCDD HpCDD OCDD TCDF PeCDF HxCDF HpCDF OCDF
I China (column 1) I I Denmark (column 2) I Japan (column 3)
I I Germany (column 4) I United Kingdom (column S) I I United States (column 6)
Figure 5-7. Congener group profiles for cigarette tobacco from various
countries.
Source: Matsuedaetal. (1994).
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Ratio (congener emission factor / total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25 0.3 0.35
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDI
1,2,3,6,7,8-HxCDI
1,2,3,7,8,9-HxCDI
1,2,3,4,6,7,8-HpCDI
1,2,3,4,6,7,8,9-OCDI
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDI
1,2,3,6,7,8-HxCDI
1,2,3,7,8,9-HxCDI
2,3,4,6,7,8-HxCDI
1,2,3,4,6,7,8-HpCDl
1,2,3,4,7,8,9-HpCDl
1,2,3,4,6,7,8,9-OCDI
aNondetect set equal to zero.
oa
Ratio (mean congener group emission factor / total CDD/CDF emission factor)
0.1 0.2 0.3 0.4
Figure 5-8. Congener and congener group profiles for air emissions from
Kraft black liquor recovery boilers.
Source: NCASI (1995).
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1 6. COMBUSTION SOURCES OF CDDs/CDFs: MINIMALLY CONTROLLED
2 AND UNCONTROLLED COMBUSTION SOURCES1
3
4 6.1. COMBUSTION OF LANDFILL GAS
5 6.1.1. Emissions Data
6 Although no data could be located on levels in untreated landfill gas, several studies have
7 reported detecting CDDs/CDFs in the emissions resulting from the combustion of landfill gas.
8 Only one study of CDD/CDF emissions from a landfill flare has been reported for a U.S. landfill
9 (CARS, 1990d). The TEQDF-WHO98 and I-TEQDF emission factor calculated from the results of
10 this study is approximately 2.4 ng TEQ/m3 of landfill gas combusted. The congener-specific
11 results of this study are presented in Table 6-1. Figure 6-1 presents the CDD/CDF congener
12 emission profile based on these emission factors. Bremmer et al. (1994) reported a lower
13 emission factor, 0.4 ng I-TEQDF/m3, from the incineration of untreated landfill gas in a flare at a
14 facility located in the Netherlands. No congener-specific emission factors were provided. The
15 average TEQ emission factor for the CARB (1990d) and Bremmer et al. (1994) studies is 1.4 ng
16 I-TEQDF/m3 of landfill gas combusted.
17 Umweltbundesamt (1996) reported even lower TEQ emission factors for landfill gas
18 burned in engines or boiler mufflers rather than in a flare. The reported results for 30 engines
19 and mufflers tested in Germany ranged from 0.001 to 0.28 ng I-TEQDF/m3, with most values
20 below 0.1 ng I-TEQDF/m3. However, Bremmer et al. (1994) also reported an emission factor of
21 0.5 ng I-TEQDF/m3 from a landfill gas-fired engine in the Netherlands.
22
23 6.1.2. Activity Level Information
24 In 1996 EPA promulgated emission standards and guidelines to control emissions of
25 landfill gas from existing and future landfills under the Clean Air Act (Federal Register, 1996a).
26 Those regulations require the largest landfills in the United States (on the basis of design
27 capacity) to periodically measure and determine their annual emissions of landfill gas. Landfills
is chapter discusses combustion sources of CDDs/CDFs that have some (in the case
of combustion of landfill gas) or no post-combustion pollution control equipment for
conventional pollutant emissions.
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1 that emit more than 50 metric tons of nonmethane organic compounds (NMOC) annually must
2 collect landfill gas and reduce its NMOC content by 98% weight through use of a control device.
3
4 6.1.2.1. 1987 and 1995 Activity Levels
5 EPA estimated that when the regulations were implemented, the controls would reduce
6 annual NMOC emissions from existing landfills by 77,600 metric tons. The cost analysis
7 supporting this rulemaking based control device costs on open flares, because flares are
8 applicable to all the regulated facilities. Assuming that the mass reduction would be achieved by
9 use of flares, the corresponding volume of landfill gas burned would be approximately 14 billion
10 m3/yr. The calculation was based on an assumed default NMOC concentration in landfill gas of
11 1,532 ppmv and a conversion factor of 3.545 mg/m3 of NMOC per 1 ppmv of NMOC (Federal
12 Register, 1993d). Of the approximately 312 landfills that were affected by the promulgation of
13 the emission standards and guidelines in 1996, EPA estimated that more than 100 had some form
14 of collection or control system, or both, in place in 1991 (Federal Register, 1991b). Thus, a
15 rough approximation of the volume of landfill gas combusted was 4.7 billion m3/yr (or 33% of
16 the future expected 14 billion m3/yr reduction). This estimate is similar to the 2 to 4 billion m3 of
17 landfill gas estimated by the Energy Information Administration (EIA, 1994) as collected and
18 consumed for energy recovery purposes in 1992. EIA (1992) estimated that between 0.9 and 1.8
19 billion m3 of landfill gas was collected and burned in 1990 for energy recovery purposes. As
20 there were no specific data available for the year 1987, EPA assumed that the mean of this range,
21 1.35 billion m3, would serve as an approximate estimate of the volume of landfill gas combusted
22 in 1987.
23
24 6.1.2.2. 2000 Activity Level
25 According to the EPA 2001 Inventory of Greenhouse Gas Emissions, approximately 7.7
26 billion m3 of landfill gas were combusted in 2000 through 477 landfill flares (average of 16.5
27 million m3 landfill gas per flare). In the United States, there are currently more than 1,000
28 landfill flares (U.S. EPA, 2003b). Assuming that the landfill gas combustion through the 477
29 landfill flares inventoried is representative of the landfill gas combustion through the more than
30 1,000 flares in the United States, approximately 16 billion m3 of landfill gas was combusted in
31 the United States through flares in 2000.
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1 6.1.3. Emission Estimates
2 The limited emission factor data that are available were judged inadequate for developing
3 national emission estimates that could be included in the national inventory. However, a
4 preliminary estimate of the potential annual TEQ releases from landfills can be obtained using
5 the estimated volume of combusted gas and the available emission factors. Combining the
6 estimates of landfill gas volume that is combusted (1.35 billion m3 in 1987, 4.7 billion m3 in
7 1995, and 16 billion m3 in 2000) with the emission factor of 1.4 ng I-TEQDF/m3 of flare-
8 combusted gas yields annual emission estimates of 1.9, 6.6, and 22 g I-TEQDF/m3 for 1987, 1995,
9 and 2000, respectively. These estimates should be regarded as preliminary indications of
10 possible emissions from this source; further testing is needed to confirm the true magnitude of
11 those emissions.
12
13 6.2. ACCIDENTAL FIRES
14 Accidental fires in buildings and vehicles are uncontrolled combustion processes that,
15 because of poor combustion conditions, typically result in relatively high emissions of
16 incomplete combustion products (Bremmer et al., 1994), which can include CDDs and CDFs.
17 Polyvinyl chloride (PVC) building materials and furnishings, chloroparaffm-containing textiles
18 and paints, and other chlorinated organic compound-containing materials appear to be the
19 primary sources of the chlorine (Retard, 1993). Although the results of several studies have
20 demonstrated the presence of CDD/CDF concentrations in soot deposits and residual ash from
21 such fires, few direct measurements of CDDs/CDFs in the fumes or smoke of fires have been
22 reported. The results of some of those studies are described below, and an evaluation of the
23 available data follows.
24
25 6.2.1. Soot and Ash Studies
26 Christmann et al. (1989b) analyzed the soot formed during combustion and pyrolysis of
27 pure PVC and PVC cable sheathings in simple laboratory experiments designed to mimic the
28 conditions of fires. For the combustion experiments, 2 g of a PVC sample were incinerated with
29 a laboratory gas burner. The combustion products were collected on the inner walls of a cooled
30 gas funnel placed above the sample. For the pyrolysis experiments, about 50 mg of the sample
31 were placed in a quartz tube and heated to about 950 °C for 10 min in either an air atmosphere or
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1 a nitrogen atmosphere. The combustion experiments yielded CDD/CDF concentrations in soot
2 of 110 pg I-TEQDF/kg for a low-molecular-weight PVC, 450 |_ig I-TEQDF/kg for a high-
3 molecular-weight PVC, and 270 |_ig I-TEQDF/kg for PVC cable. The pyrolysis experiments in the
4 air atmosphere yielded lower CDD/CDF concentrations in soot: 24.4 |_ig I-TEQDF/kg for a low-
5 molecular-weight PVC, 18.7 pg I-TEQDF/kg for a high-molecular-weight PVC, and up to 41 |_ig I-
6 TEQDF/kg for PVC cable.
7 In general, more CDFs than CDDs were formed. The less-chlorinated CDF congeners
8 were dominant in the combustion experiments; however, the HpCDF and OCDF congeners were
9 dominant in the pyrolysis experiments. No CDDs/CDFs were detected in pyrolysis experiments
10 under a nitrogen atmosphere. Also, no CDDs/CDFs were detected when chlorine-free
11 polyethylene samples were subjected to the same combustion and pyrolysis conditions.
12 Deutsch and Goldfarb (1988) reported finding CDD/CDF concentrations ranging from
13 0.04 to 6.6 |ag/kg in soot samples collected after a 1986 fire in a State University of New York
14 lecture hall. The fire consumed or melted plastic furnishings, cleaning products containing
15 chlorine, wood, and paper.
16 Funcke et al. (1988; as reported in Bremmer et al., 1994, and Retard, 1993) analyzed 200
17 ash and soot samples from sites of accidental fires in which PVC was involved. CDDs/CDFs
18 were detected in more than 90% of the samples at concentrations in the ng I-TEQDF/kg to |_ig I-
19 TEQDF/kg range. Fires involving the combustion of materials containing relatively large amounts
20 of PVC and other chlorinated organic substances resulted in the highest levels of CDDs/CDFs,
21 with concentrations ranging from 0.2 to 110 pg I-TEQDF/kg of residue.
22 Thiesen et al. (1989) analyzed residues from surfaces of PVC-containing materials that
23 were partially burned during accidental fires at sites in Germany that manufactured or stored
24 plastics. CDD/CDF concentrations in residues were reported as 0.5 |_ig I-TEQDF/kg for soft PVC,
25 4.6 pg I-TEQDF/kg for PVC fibers, and 28.3 |ag I-TEQDF/kg for a hard PVC. The ratio of total
26 CDFs to total CDDs in the three samples ranged from 4:1 to 7:1. The dominant 2,3,7,8-
27 substituted CDF and CDD congeners in all three samples were 1,2,3,4,6,7,8-HpCDF and
28 1,2,3,4,6,7,8-HpCDD.
29 In an accidental fire at a Swedish carpet factory in 1987, 200 metric tons of PVC and 500
30 metric tons of PVC-containing carpet were burned. Marklund et al. (1989) analyzed snow
31 samples up to 1,500 m downwind from the fire site and found CDD/CDF concentrations in the
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1 top 2 cm ranging from 0.32 |_ig I-TEQDF/m2 at 10 m of the site to 0.01 |_ig I-TEQDF/m2 at 1,500 m.
2 Because of an atmospheric inversion and very light wind at the time of the fire, the smoke from
3 the fire remained close to the ground. The soot deposited onto the snow was thus assumed to be
4 representative of the soot generated and released from the fire. Wipe samples of soot from
5 interior posts of the plant that were 5 and 20 m from the fire contained EADON TEQ
6 concentrations of 0.18 and 0.05 pg/m2, respectively. On the basis of these deposition
7 measurements, the investigators estimated total CDD/CDF emissions from the fire to be less than
8 3 mg I-TEQDF.
9 Carroll (1996) estimated a soot-associated CDD/CDF emission factor (i.e., not including
10 volatile emissions) of 28 to 138 ng I-TEQDF/kg of PVC burned for the Swedish carpet factory fire
11 using the following assumptions: (a) the PVC carpet backing was one-half the weight of the
12 carpet, (b) the carpet backing contained 30% by weight PVC resin, and (c) 20 to 100% of the
13 PVC and PVC carpet backing present in the warehouse actually burned. Using the results of
14 wipe samples collected at downwind distances of up to 6,300 m, Carroll (1996) also estimated a
15 similar soot-associated emission factor (48 to 240 ng I-TEQDF/kg of PVC burned) for a fire at a
16 plastics recycling facility in Lengerich, Germany.
17 Fiedler et al. (1993) presented a case study of CDD/CDF contamination and associated
18 remedial actions taken at a kindergarten in Germany following a fire that destroyed parts of the
19 roof, windows, and furnishings. Soot collected from the building contained CDDs/CDFs at a
20 concentration of 45 |_ig I-TEQDF/kg (15 pg I-TEQDF/m2). The study authors attributed the
21 CDDs/CDFs detected to the combustion of plastic and wooden toys, floors, and furnishings;
22 however, no information was provided on the quantities of those materials.
23 Fiedler and Lindert (1998) presented results of soot sampling following a serious fire at
24 the airport in Diisseldorf, Germany. Polystyrene sheets and PVC-coated cables were involved in
25 the fire, together with PCB-containing condensers (bulbs). Surface wipe samples contained up to
26 0.33 |ag I-TEQDF/m2. Concentrations in soot ranged from 7 to 130 |_ig I-TEQDF/kg.
27 Concentrations of polybrominated dibenzo-p-dioxins and dibenzofurans were detected in soot at
28 concentrations as high as 0.9 mg/kg soot.
29 Wichmann et al. (1993, 1995) measured the CDD/CDF content of ash and debris and
30 deposited surface residues that resulted from experimental test burns of two cars (a 1974 Ford
31 Taurus [old car] and a 1988 Renault Espace [new car]), one subway car, and one railway coach in
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1 a tunnel in Germany. On the basis of measurements obtained from sampled ash and debris and
2 from soot collectors placed at regular intervals up to 420 m downwind of the burn site, the total
3 amounts of CDDs/CDFs in the ash/debris and tunnel surface residues from each vehicle burn
4 experiment were estimated as follows: 1974 model car—0.044 mg I-TEQDF; 1988 model
5 car—0.052 mg I-TEQDF; subway car—2.6 mg I-TEQDF; and railway coach—10.3 mg I-TEQDF.
6 For each vehicle burn experiment, the mass of TEQ in tunnel surface residue exceeded the mass
7 in ash and debris; 73 to 89% were accounted for by the tunnel surface residues and 11 to 27% by
8 ash and debris. The average CDD/CDF content of the ash and debris from each experimental
9 burn was as follows: new car—0.14 \ig I-TEQDF/kg; old car—0.3 |_ig I-TEQDF/kg; subway
10 car—3.1 |_ig I-TEQDF/kg; and railway coach—5.1 |_ig I-TEQDF/kg.
11
12 6.2.2. Fume and Smoke Studies
13 Merk et al. (1995) collected fume and smoke generated during the burning of 400 kg of
14 wood and 40 kg of PVC in a building (4,500 m3 volume) over a 45-min period. The sampling
15 device consisted of dual glass fiber filters to collect particles greater than 0.5 pm followed by a
16 polyurethane foam filter to collect vapor phase CDDs/CDFs. The particulate phase and gas
17 phase showed the same congener pattern: decreasing concentration with increasing degree of
18 chlorination, thus indicating no preferential sorption of more highly chlorinated congeners to
19 smoke particulates. However, the CDDs/CDFs found in the gas phase (about 5 ng I-TEQDF/m3)
20 accounted for more than 90% of the detected CDDs/CDFs. The authors also reported that the
21 soot deposited from this fire onto aim2 aluminum sheet resulted in surface contamination of
22 0.05 pg I-TEQDF/m2.
23 Although it was stated in Merk et al. (1995) that the building was "closed," subsequent
24 communication with one of the coauthors (Schramm, 1998) clarified that a "gas cleaning" system
25 was in operation. Because a ventilation system was in operation, there was likely some loss of
26 vapor-phase CDDs/CDFs from the hall. Therefore, the deposits (from particulate deposition and
27 vapor-phase condensation) on the test aluminum plate may not have reflected total CDD/CDF
28 formation during the fire.
29 Dyke and Coleman (1995) reported a fourfold increase in CDD/CDF TEQ concentrations
30 in the ambient air during "bonfire night" in Oxford, England. Bonfire night (November 5) is an
31 annual event during which it is customary to set off fireworks and have bonfires to commemorate
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1 a failed plot to overthrow the king in 1605. Air concentrations before and after bonfire night
2 ranged from 0.15 to 0.17 pg I-TEQDF/m3. The air concentration during bonfire night was 0.65 pg
3 I-TEQDF/m3. The dominant congeners in all samples were the hepta- and octa-CDDs. The study
4 was not designed to collect data that would enable calculation of an emission rate or to
5 differentiate the relative importance of the various materials combusted. However, the results do
6 indicate that open burning of materials likely to be combusted in accidental fires (with the
7 exception of fireworks) results in the release of CDDs and CDFs.
8
9 6.2.3. Data Evaluation
10 6.2.3.1. Structural Fires
11 6.2.3.1.1. Emissions data. Only limited emissions data for structural fires were located. Most
12 of the studies obtained involved situations (field and laboratory) where relatively high loadings
13 of PVC or plastics were combusted. The effects of different mixes of combusted materials,
14 oxygen supplies, building configurations, durations of burn, and so forth that were likely to be
15 found in accidental fires cannot be accounted for by the factors that can be derived from these
16 studies. Also, most of the studies addressed only soot or ash residues and did not address
17 potential volatile emissions of CDDs/CDFs which, according to Merk et al. (1995), may
18 represent 90% of the CDDs/CDFs generated during the burning of PVC.
19 Two reports (Carroll, 1996; Thomas and Spiro, 1995) attempted to quantify CDD/CDF
20 emissions from U.S. structural fires, and Lorenz et al. (1996) estimated emissions from structural
21 fires in Germany. Carroll (1996) estimated the total CDD/CDF content of soot and ash generated
22 from the 358,000 residential fires reported in the United States for 1993 (U.S. DOC, 1995a).
23 Detailed estimates were developed of the PVC content of typical homes, including plumbing,
24 wiring, siding and windows, wallpaper, blinds and shades, and upholstery. Statistical data on fire
25 loss (i.e., dollar value) was used to provide the typical loss per recorded fire (9.5% of value),
26 which was assumed to also represent the typical percentage of PVC burned. Extrapolating to all
27 358,000 one- to two-family unit fires yielded an annual mass of 2,470 metric tons of PVC
28 burned.
29 Carroll then developed TEQ emission factors from the results of Thiesen et al. (1989) and
30 Marklund et al. (1989). The estimated CDD/CDF content ranged from 0.47 to 22.8 g I-TEQDF ,
31 with 0.07 to 8.6 g I-TEQDF in soot and 0.4 to 14.2 g I-TEQDF in ash. A soot emission factor (i.e.,
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1 grams of soot produced per gram of PVC combusted) was derived from the investigator's
2 assumptions regarding the surface area of the soot collection funnel used by Christmann et al.
3 (1989a) and the soot deposition rate on that funnel. These I-TEQDF emission factors were then
4 applied to the estimated 2,470 metric tons of PVC burned annually in one- to two-family unit
5 residential fires to obtain estimates of the annual mass of TEQ that would be found in the soot
6 and ash of residential fires (0.48 to 22.8 g I-TEQDF/yr). The average emission per fire is thus 1.3
7 to 64 pg I-TEQDF.
8 Thomas and Spiro (1995) estimated that 20 g I-TEQDF may be released annually to air
9 from structural fires. This estimate assumes an emission factor of 4 ng I-TEQDF/kg of material
10 combusted (i.e., the emission rate for "poorly" controlled wood combustion), a material
11 combustion factor of 6,800 kg per fire, and 688,000 structural fires per year. The average
12 emission per fire is thus 29 |_ig I-TEQDF.
13 Lorenz et al. (1996) estimated annual generation of CDDs/CDFs in Germany using data
14 on the number of residential and industrial/commercial structural fires coupled with data on
15 CDD/CDF content in soot and ash residues remaining after fires. The potential annual I-TEQDF
16 generation was estimated to be 78 to 212 g.
17 Using the emissions data estimated by Carroll (1996) and Thomas and Spiro (1995)
18 provides an average emission factor of 32 |_ig I-TEQ/fire.
19
20 6.2.3.1.2. Activity level information. In 1987, there were approximately 2,330,000 fires in the
21 Unites States, of which approximately 745,600 (32%) were structural fires (FEMA, 1999). In
22 1995, approximately 574,000 structural fires were reported in the United States. Of these,
23 426,000 were reported for residential structures, including 320,000 in one- to two-family units,
24 94,000 in apartments, and 12,000 in other residential settings. The types of structures for the
25 remaining 148,000 fires were public assembly, 15,000; educational, 9,000; institutional, 9,000;
26 stores, and offices 29,000; special structures, 29,000; storage, 39,000; and industry, utility, and
27 defense 18,000. The latter two categories may be underreported, as some incidents were not
28 recorded because they were handled by private fire brigades or fixed suppression systems (U.S.
29 DOC, 1997). For 2000, the National Fire Data Center estimated that approximately 1,708,000
30 fires occurred in the United States, of which approximately 512,400 (30%) were structural fires
31 (FEMA, 2001).
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1 6.2.3.1.3. Emission estimates. The limited data available on structural fires were judged
2 inadequate for developing national emission estimates. This conclusion was also reached for
3 national emission inventories developed for the Netherlands (Bremmer et al., 1994) and the
4 United Kingdom (U.K. Environment Agency, 1995). However, preliminary estimates can be
5 calculated by combining the average emission factor of 32 |_ig I-TEQ/fire and the number of
6 structural fires in the Unites States (745,600 in 1987; 426,000 in 1995; and 512,400 in 2000).
7 This yields an annual release of 24 g I-TEQDF in 1987, 14 g I-TEQDF in 1995, and 16 g I-TEQDF
8 in 2000. Confidence in these estimated emissions is very low because of the numerous
9 assumptions employed in their derivation. If the conclusion of Merk et al. (1995) is assumed to
10 be correct, that 90% of the CDDs/CDFs formed in fires are in the gaseous phase rather than
11 particulate phase (particles greater than 0.5 [am diameter), and it is also assumed that the
12 estimates of Carroll (1996) and Thomas and Spiro (1995) do not totally account for volatile
13 emissions, then the total CDD/CDF emissions estimated by Carroll and Thomas and Spiro may
14 be underestimates. Further testing is needed to confirm the true magnitude of these releases.
15
16 6.2.3.2. Vehicle Fires
17 As with structural fires, the limited data available on vehicle fires were judged inadequate
18 for developing national emission estimates that could be included in the national inventory.
19 However, a preliminary estimate of the range of potential CDD/CDF emissions that may result
20 from vehicle fires can be calculated using the results reported by Wichmann et al. (1993, 1995)
21 for controlled vehicle fires in a tunnel (0.044 mg I-TEQDF for an old car to 2.6 mg I-TEQDF for a
22 subway car). Although Wichmann et al. did not measure volatile CDDs/CDFs (which were
23 reported by Merk et al., 1995, to account for the majority of CDDs/CDFs formed during a fire),
24 the study was conducted in a tunnel, and it is likely that a significant fraction of the volatile
25 CDDs/CDFs sorbed to tunnel and collector surfaces and were thus measured as surface residues.
26 The number of vehicle fires reported in the United States was approximately 561,530 in
27 1987 (FEMA, 1997), 406,000 in 1995 (U.S. DOC, 1997), and 341,600 in 2000 (FEMA, 2001).
28 If it is assumed that 99% of those fires involved cars and trucks (i.e., the approximate percentage
29 of all U.S. motor vehicles that are in-service cars and trucks; U.S. DOC, 1995a) and that the
30 applicable emission rate is 0.044 mg I-TEQDF per incident, then the annual TEQ formation is
31 24.4 g I-TEQDF for 1987, 17.7 g I-TEQDF for 1995, and 14.9 g I-TEQDF for 2000. The emission
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1 factor of 2.6 mg I-TEQDF/fire is assumed to be applicable to the remaining 1% of vehicle fires,
2 thus yielding an emission of 14.6 g I-TEQDF/yr for 1987, 10.6 g I-TEQDF/yr for 1995, and 8.9 g I-
3 TEQDF/yr for 2000. The total TEQ annual emissions for 1987, 1995, and 2000 are roughly
4 estimated to be 39, 28.3, and 23.8 g I-TEQDF/yr, respectively. These estimates should be
5 regarded as preliminary indications of possible emissions from this source category; further
6 testing is needed to confirm the true magnitude of these emissions.
7
8 6.3. LANDFILL FIRES
9 6.3.1. Emissions Data
10 In the late 1980s, two serious fires occurred in landfills near Stockholm, Sweden. The
11 first fire was in a large pile of refuse-derived fuel. Using measurements of chlorobenzenes in the
12 air emissions, it was estimated that 50 to 100 kg of chlorobenzenes were released. CDD/CDF
13 emissions were estimated to be several tens of grams, on the assumption that the ratio of
14 CDDs/CDFs to chlorobenzenes in landfill fire emissions is similar to the ratio observed in stack
15 gases of MWCs. To measure releases in connection with the second fire, which occurred at a
16 large conventional landfill, birch leaves were collected from trees close to the fire and at
17 distances up to 2 km downwind of the fire, as well as from nearby areas not affected by smoke
18 from the fire. The discharge of CDDs/CDFs necessary to cause the concentrations measured on
19 the leaves was estimated to be several tens of grams (Persson and Bergstrom, 1991).
20 In response to these incidents, Persson and Bergstrom (1991) also measured CDD/CDF
21 emissions from experimental fires designed to simulate surface landfill fires and deep landfill
22 fires. The experiments used 9-month-old domestic waste. The tests showed no significant
23 difference in CDD/CDF content of the fire gas produced by the simulated surface and deep fires.
24 The average CDD/CDF emission rate was reported to be 1 pg Nordic TEQ/kg of waste burned.
25 Persson and Bergstrom (1991) and Bergstrom and Bjorner (1992) estimated annual
26 CDD/CDF Nordic TEQ emissions in Sweden from landfill fires to be 35 g. The estimate was
27 based on the emission rate of 1 pg Nordic TEQ/kg waste burned, an assumed average density of
28 landfill waste of 700 kg/m3, an assumed waste burn of 150 m3 for each surface landfill fire (167
29 fires in Sweden per year), and an assumed waste burn of 500 m3 for each deep landfill fire (50
30 fires in Sweden per year). The estimates of waste burn mass for each type of fire were the
31 average values obtained from a survey of 62 surface fires and 25 deep fires. The estimated
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1 number of fires per year was based on the results of a survey of all Swedish municipalities for
2 fires reported during 1988 and 1989. In 1991, Sweden had an estimated 400 municipal landfills
3 (Persson and Bergstrom, 1991).
4 Ruokojarvi et al. (1995) measured ambient air concentrations of CDDs/CDFs in the
5 vicinity of real and experimental landfill fires in Finland. The most abundant toxic congeners
6 were the hepta- and octa-CDDs and the penta-, hepta-, and octa-CDFs. The highest contributions
7 to the measured TEQ were made by 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF. In Finland, annual
8 CDD/CDF emissions from landfill fires are estimated to be 50 to 70 g Nordic TEQ (Aittola,
9 1993, as reported by Ruokojarvi et al., 1995).
10
11 6.3.2. Activity Level Information and Emission Estimates
12 Although no U.S. monitoring studies are available, an emission factor similar to the
13 Swedish emission factor would be expected in the United States, because the contents of the
14 municipal waste in the United States and Sweden are expected to be similar. Because no data
15 could be located on characterization of landfill fires in the United States (i.e., number, type, mass
16 of waste involved), the limited data available were judged inadequate for developing national
17 emission estimates that could be included in the national inventory. However, a preliminary
18 estimate of the potential magnitude of TEQ emissions associated with landfill fires in the United
19 States can be obtained by assuming a direct correlation of emissions to population size for the
20 United States and Sweden or by assuming a direct correlation between emissions and the number
21 of landfills in each country.
22 Both the United States and Sweden are industrialized countries. Although the per capita
23 waste generation rate in the United States is nearly 1.5 times that of Sweden, the composition of
24 municipal waste and the fraction of municipal waste disposed of in landfills in the two countries
25 are nearly identical (U.S. EPA, 1996b). The population of Sweden was 8,825,417 in 1995 (U.S.
26 DOC, 1995a) and 8,873,052 in 2000 (U.S. DOC, 2002). Based on these population estimates
27 and the estimated annual Nordic TEQ emission factor of 35 g, the per capita landfill
28 fire-associated Nordic TEQ emission factor is 4 |_ig TEQ per person per year for both 1995 and
29 2000. Because congener-specific results were not provided in Persson and Bergstrom (1991) and
30 Bergstrom and Bjorner (1992), it was not possible to derive emission factors in units of TEQDF-
31 WHO98 or I-TEQDF. Applying this factor to the U.S. population of 263,814,000 in 1995 (U.S.
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1 DOC, 1995a) and 281,421,906 in 2000 (U.S. DOC, 2003a) results in an estimated annual
2 emission of 1,050 g TEQ for 1995 and 1,126 g TEQ for 2000. These estimates should be
3 regarded as preliminary indications of possible emissions from this source category; further
4 testing is needed to confirm the true magnitude of these emissions.
5
6 6.4. FOREST AND BRUSH FIRES
7 6.4.1. Emissions Data
8 Because CDDs/CDFs have been detected both in the soot from residential wood burning
9 (Bumb et al., 1980; Nestrick and Lamparski, 1982, 1983; Bacher et al., 1992) and in the flue
10 gases from residential wood burning (Schatowitz et al., 1993; Vickelsoe et al., 1993; Launhardt
11 and Thoma, 2000; Environment Canada, 2000), it is reasonable to assume that wood burned in
12 forest and brush fires may also be a source of CDDs/CDFs (Section 4.2 contains details on these
13 studies).
14 Only one study (Tashiro et al., 1990) could be found that reported direct measurements of
15 CDDs/CDFs in the emissions from forest fires. This study reported detection of total
16 CDDs/CDFs in air at levels ranging from about 15 to 400 pg/m3. The samples were collected
17 from fixed collectors located 10m above the ground and from aircraft flying through the smoke.
18 Background samples collected before and after the tests indicated negligible levels in the
19 atmosphere. These results were presented in a preliminary report; however, no firm conclusions
20 were drawn about whether forest fires are a CDD/CDF source. The final report on this study,
21 Clement and Tashiro (1991), showed total CDD/CDF levels in the smoke of about 20 pg/m3.
22 The authors concluded that CDDs/CDFs are emitted during forest fires but recognized that some
23 portion of these emissions could represent resuspension from residues deposited on leaves rather
24 than newly formed CDDs/CDFs.
25 Although not designed to directly assess whether CDDs/CDFs are formed during brush
26 fires, Buckland et al. (1994) measured CDD/CDF levels in soil samples from both burnt and
27 unburnt areas in national parks in New Zealand 6 weeks after large-scale brush fires. Four
28 surface soil cores (2 cm depth) were collected and composited from each of three burnt and three
29 unburnt areas. Survey results indicated that brush fires did not have a major impact on the
30 CDD/CDF levels in soil. The I-TEQDF contents in soil sample composites of the three unburnt
31 areas were 3, 8.7, and 10 ng/kg. The I-TEQDF contents in the soil sample composites of three
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1 burnt areas were 2.2, 3.1, and 36.8 ng/kg. Total CDD/CDF contents ranged from 1,050 to 7,700
2 ng/kg in the unburnt area soil samples and from 1,310 to 27,800 ng/kg in the burnt area soil
3 samples. OCDD accounted for 94 to 97% of the total CDD/CDF content in all samples.
4 Similarly, a survey of controlled straw-field burning in the United Kingdom (Walsh et al.,
5 1994) indicated that the straw burning did not increase the CDD/CDF burden in the soil;
6 however, a change in congener distribution was observed. Soils from three fields were sampled
7 immediately before and after burning, along with ash from the fire. The mean I-TEQDF
8 concentrations in the preburn soil, postburn soil, and ash were 1.79, 1.72, and 1.81 ng/kg,
9 respectively. Concentrations of 2,3,7,8-TCDF were lower in the postburn soils than in the
10 preburn soils. Conversely, the concentrations of OCDD were higher in the postburn soils,
11 indicating possible formation of OCDD during the combustion process.
12 Van Oostdam and Ward (1995) reported finding no detectable levels of 2,3,7,8-
13 substituted CDDs/CDFs in three soil samples and four ash samples following a forest fire in
14 British Columbia. The DLs on a congener-specific basis (unweighted for TEQ) ranged from 1 to
15 2 ng/kg. Nondetect values were also reported for ashes at a slash and burn site; the soil contained
16 about 0.05 ng I-TEQDF/kg, whereas background soil contained about 0.02 ng I-TEQDF/kg.
17 The concentrations presented by Clement and Tashiro (1991) cannot accurately be
18 converted to an emission factor because the corresponding rates of combustion gas production
19 and wood consumption are not known. As a result, four alternative approaches were considered
20 to develop an emission factor.
21 Soot-based approach. This approach assumes that the levels of CDDs/CDFs in chimney
22 soot are representative of the CDDs/CDFs in emissions. The CDD/CDF emission factor is
23 calculated as the product of the CDD/CDF concentration in soot and the total paniculate
24 emission factor. This calculation involves first assuming that the CDD/CDF levels measured in
25 chimney soot (720 ng I-TEQDF/kg) by Bacher et al. (1992) are representative of the CDD/CDF
26 concentrations of particles emitted during forest fires. Second, the total particulate generation
27 factor must be estimated. Using primarily data for head fires, Ward et al. (1976) estimated the
28 national average particulate emission factor for wildfires as 150 Ib/ton biomass dry weight.
29 Ward et al. (1993) estimated the national average particulate emission factor for prescribed
30 burning as 50 Ib/ton biomass dry weight. Combining the total particulate generation rates with
31 the I-TEQDF level in soot results in emission factor estimates of 54 ng of I-TEQDF and 18 ng of I-
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1 TEQDF/kg of biomass burned in wildfires and prescribed burns, respectively. These estimated
2 factors are likely to be overestimates because the levels of CDDs/CDFs measured in chimney
3 soot by Bacher et al. (1992) may represent the accumulation and enrichment of CDDs/CDFs
4 measured in chimney soot over time, leading to much higher assumed levels than what is actually
5 on emitted particles.
6 Carbon monoxide (CO) approach. CO is a general indicator of the efficiency of
7 combustion, and the emission factors of many emission products can be correlated with the CO
8 emission factor. Data from Schatowitz et al. (1993) for emissions during natural wood burning
9 in open stoves suggest an emission factor of 10 |_ig I-TEQDF/kg of CO. Combining this factor
10 with the CO emission factor during forest fires (roughly 0.1 kg CO/kg of biomass, Ward et al.,
11 1993) yields an emission factor of 1,000 ng I-TEQDF/kg biomass. This factor is higher than the
12 soot-based factor discussed above, which is itself considered to be an overestimate. In addition,
13 although the formation kinetics of CDDs/CDFs during combustion are not well understood,
14 CDD/CDF emissions have not been shown to correlate well with CO emissions from other
15 combustion sources.
16 Wood stove approach. This approach assumes that the emission factor for residential
17 wood burning (using natural wood and open door, i.e., uncontrolled draft) applies to forest fires.
18 As discussed in Section 4.2.1, this approach suggests an emission factor of about 0.5 ng I-
19 TEQ/kg wood combusted. This value appears more reasonable than the factors suggested by the
20 soot and CO approaches because it is based on direct measurement of CDDs/CDFs from
21 combustion of wood rather than on indirect techniques. However, forest fire conditions differ
22 significantly from combustion conditions in wood stoves. For example, forest fire combustion
23 does not occur in an enclosed chamber, and the biomass consumed in forest fires is usually green
24 and includes underbrush, leaves, and grass.
25 Forest fire simulation approach. This approach quantifies CDD/CDF emissions
26 through the combustion of forest biomass in a controlled-burn facility. Using this approach,
27 Gullet and Touati (2003) estimated CDD/CDF emissions through the testing of three biomass
28 samples collected from the Oregon coast near Seal Rock and from four biomass samples
29 collected from the North Carolina Piedmont region, approximately 200 km from the Atlantic
30 coast. The samples generally consisted of equal portions of live shoots (needles cut from tree
31 branches) and needle litter gathered from the forest floor. The Oregon samples were composed
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1 of pine needles (Pinus contorta and Pinus monticold) and hemlock needles (Tyuga heterophylla);
2 the North Carolina samples were composed entirely of lobolly pine (Pinus taeda). The
3 combustion of these seven samples, piled approximately 10 cm high, took place on top of an
4 open, flat combustion platform. CDD/CDF emissions were measured using a Graseby PS-1
5 sampler and EPA's ambient TO-9 method.
6 As shown in Table 6-2, the overall average total TEQ emission factor for the seven
7 samples was 20 ng TEQDF-WHO98/kg (18.6 ng I-TEQDF), assuming nondetects were zero.
8 Separately, the average total TEQ emission factors for the three Oregon samples and the four
9 North Carolina samples were 15 ng and 25 ng TEQDF-WHO98/kg, respectively. Even though the
10 average TEQ emission factors for the Oregon and North Carolina runs were similar, CDF
11 congeners were dominant in the Oregon samples, whereas CDD congeners were dominant in the
12 North Carolina samples. Figure 6-2 shows the congener profile for the Oregon and North
13 Carolina samples combined.
14 To test an alternative CDD/CDF sampling method, CDD/CDF emissions from one of the
15 Oregon samples were also measured using a "Nomad" (a prototype portable sampler designed for
16 mobile, in-field sampling). The results from both sampling methods showed very similar
17 CDD/CDF TEQ values, total values, and ratio values. An additional Oregon sample was also
18 combusted to test influences of fuel configuration on emissions. In this experiment, the biomass
19 was placed in a metal barrel with air holes cut into the bottom. The results of this test run
20 showed the highest total TEQ emission value calculated in this study (47 ng TEQDF-WHO98/kg).
21 However, this value is similar to the next highest total TEQ value (46 ng TEQDF-WHO98/kg).
22 Because the waxy cuticle layer on pine needles has been demonstrated to absorb
23 lipophilic compounds from the atmosphere, Gullet and Touati (2003) also extracted a raw, as-
24 received Oregon biomass sample to determine whether the observed emissions were due to
25 simple vaporization of existing CDDs/CDFs or the formation of new CDDs/CDFs in the
26 combustion process. The CDD/CDF concentration in the extracted Oregon biomass sample
27 measured 1.3 ng TEQDF-WHO98/kg, which is approximately 20 times lower than the Oregon
28 CDD/CDF emission concentrations (average of 25 ng TEQDF-WHO98/kg and range of 14 to 46 ng
29 TEQDF-WHO98/kg). The CDD/CDF isomer patterns were similar between the extracted biomass
30 samples and the emission samples. Therefore, this preliminary evidence suggests CDD/CDF
31 emissions are not due solely to vaporization o f cuticle-bound CDDs/CDFs but are formed anew
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1 during forest fires. Additionally, the new CDDs/CDFs formed may be adsorbed to the waxy
2 cuticle layer in such a manner that the isomer pattern reflects the ambient CDD/CDF
3 concentrations.
4 Many factors may affect forest fire CDD/CDF emissions, such as the type of fire (crown
5 vs. understory and duff), types of species combusted, and location of the fire (near-coastal vs.
6 inland). Additionally, combustion conditions such as wind speed and fuel moisture content may
7 also result in variation of emissions. Therefore, these variables yield uncertainties in the
8 calculation of a representative emission factor through forest fire simulations. However, the
9 emission factor of 20 ng TEQDF-WHO98/kg (18.6 ng I-TEQDF) calculated through this approach
10 appears to be more reasonable than the factors suggested by the soot, CO, and wood stove
11 approaches, as the forest fire simulation approach directly measures CDD/CDF emissions from
12 forest biomass combusted in an open pile. Additionally, the forest biomass samples consisted of
13 both live shoots and needle litter of representative species from two distinct locations.
14
15 6.4.2. Activity Level Information
16 6.4.2.1. Approach for Reference Year 2000 (Office of Air Quality Planning and Standards
17 fOAQPSJ)
18 As part of the 2000 National Emissions Inventory, OAQPS developed activity levels of
19 wildfires and prescribed burning on a county-level basis for reference year 2000. The number of
20 acres burned by wildfires and prescribed burning was obtained from the U.S. Forest Service
21 (USFS) and four U.S. Department of Interior agencies: Bureau of Land Management, National
22 Park Service, U.S. Fish and Wildlife Service, and Bureau of Indian Affairs (BIA). USFS
23 provided data for federal, state, and private lands. All data were provided on a state level except
24 for the BIA wildfire data and the USFS prescribed burning data, which were provided on a
25 regional level.
26 Prior to allocating the forest fire activity to the county level, the BIA and USFS regional
27 data were first allocated to the state level. The BIA data were allocated to the state level, using
28 the number of acres of tribal land in each state. The USFS data were allocated using factors
29 developed from landcover data in the Biogenic Emissions Landcover Database (BELD2) within
30 EPA's Biogenic Emissions Inventory System; however, the BELD2 data for California were
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1 replaced with data from the 1996 National Toxics Inventory because USFS's Region 5 contains
2 both Hawaii and California.
3 For each of the forest fire categories, the activity from all the agencies were then totaled
4 by state and allocated to the county level using state-to-county landcover factors developed from
5 BELD2. These BELD2 factors were based on the acreage of rural forest, brush, and grass in each
6 county. This procedure was used for all states except Alaska and Hawaii, for which BELD2 does
7 not contain landcover data. For Alaska and Hawaii, state-to-county factors were derived from
8 data contained in the allocation factor file used for the 1996 National Emissions Inventory.
9 Using this approach, OAQPS estimated that approximately 8,357,958 acres were burned by
10 wildfires in 2000 and approximately 1,261,607 acres were burned by prescribed fires in 2000.
11 To obtain the amount of biomass consumed by wildfires and prescribed burning, the acres
12 of forest burned were combined with region-specific fuel loading factors, as shown in Table 6-3.
13 Nationally, approximately 228 million tons of biomass were consumed by wildfires and 15.8
14 million metric tons of biomass were consumed by prescribed burning in 2000.
15
16 6.4.2.2. Approach for Reference Years 1987 and 1995
17 According to the Council on Environmental Quality's 25th Annual Report (CEQ, 1997),
18 5 million acres of forest were lost to wildfires in 1987 and 7 million acres were lost in 1995.
19 Estimates of the acreage consumed annually during prescribed burns are not readily available for
20 reference years 1995 and 1997. An estimated 5.1 million acres of biomass were burned in 1989
21 during prescribed burns (Ward et al., 1993). This value of 5.1 million acres is assumed to be an
22 appropriate value to use for reference years 1987 and 1995.
23 To obtain the amount of biomass consumed by wildfires and prescribed burning, the acres
24 of forest burned were combined with biomass consumption rates of 9.43 metric tons per acre in
25 areas consumed by wildfires (Ward et al., 1976) and 7.44 metric tons per acre in areas consumed
26 in prescribed burns. For reference years 1987 and 1995, approximately 38 million tons were
27 consumed by prescribed burns. For wildfires, approximately 47 million metric tons of biomass
28 were consumed in 1987 and approximately 66 million metric tons of biomass were consumed in
29 1995.
30
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1 6.4.3. Emission Estimates
2 Combining the emission factor developed using the forest fire simulation approach (20 ng
3 TEQDF-WHO98/kg biomass [18.6 ng I-TEQDF/kg biomass]) with the amount of biomass
4 consumed annually in wildfires and prescribed fires (total of 85 million metric tons in 1987, 104
5 million metric tons in 1995, and 244 million metric tons in 2000) yields annual emission
6 estimates of 1,700 g TEQDF-WHO98 (1,581 g I-TEQDF) for 1987; 2,080 g TEQDF-WHO98 (1,934 g
7 I-TEQDF) for 1995; and 4,880 g TEQDF-WHO98 (4,538 g I-TEQDF) for 2000. For wildfires
8 specifically, annual reference year emission estimates are 940 g TEQDF-WHO98 (874.2 g I-
9 TEQDF) for 1987; 1,320 g TEQDF-WHO98 (1,228 g I-TEQDF) for 1995; and 4,560 g TEQDF-
10 WHO98 (4,241 g I-TEQDF) for 2000. For prescribed fires specifically, annual emission estimates
11 are 760 g TEQDF-WHO98 (706.8 g I-TEQDF) for reference years 1987 and 1995 and 320 g TEQDF-
12 WHO98 (297 g I-TEQDF) for reference year 2000. These estimates should be regarded as
13 preliminary indications of possible emissions from this source; further testing is needed to
14 confirm the true magnitude of emissions. The activity level for both forest fires and biomass
15 combustion is given a low confidence rating because these values were estimated and may not be
16 representative. The emission factor is highly variable and dependent on type of biomass burned,
17 therefore, it is judged to be clearly nonrepresentative.
18
19 6.5. BACKYARD BARREL BURNING
20 6.5.1. Emissions Data
21 In many rural and nonurban areas of the United States, residences may dispose of
22 household refuse through the practice of open backyard burning. This practice usually consists
23 of combustion of the refuse in a 208-L capacity steel drum. Holes are punched near the bottom
24 of the drum to allow combustion air to enter. Ignition is achieved with the use of a petroleum
25 fuel, e.g., kerosene. The low combustion temperatures and oxygen-starved conditions associated
26 with the burning of household refuse in "burn barrels" results in poor and uncontrolled
27 combustion conditions. Under such conditions, products of incomplete combustion are formed
28 and visible smoke is emitted into the air.
29 The practice of the open burning of refuse in burn barrels causes CDDs and CDFs to be
30 formed and released as toxic air contaminants. In 1997, EPA's Control Technology Center, in
31 cooperation with the New York State Department of Health and Department of Environmental
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1 Conservation, conducted an initial study that examined, characterized, and quantified emissions
2 from simulated open burnings of household waste materials in barrels (Lemieux, 1997). The
3 representative waste was prepared on the basis of the typical percentages of various waste
4 materials disposed of by New York State residents; hazardous wastes (chemicals, paints, oils,
5 etc.) were not included in the test waste. A variety of compounds, including CDDs/CDFs, were
6 measured in the emissions from two simulated open burnings of this "baseline" waste.
7 Combustion studies were subsequently performed by EPA to provide additional baseline
8 waste tests and to provide an initial indication of the impact of limited variation in waste
9 composition and combustion conditions on CDD/CDF emissions from a simulated domestic
10 backyard barrel burn of 6.8 kg of unshredded household waste (Gullet et al., 1999, 2000a, b;
11 Lemieux et al., 2000; Lemieux, 2000). The results of seven baseline open burning waste tests
12 were reported in these EPA studies. These tests exhibited variation in the emissions of
13 CDDs/CDFs, with a one- to two-order of magnitude spread between the lowest and highest
14 values for individual congeners, congener groups, total CDDs/CDFs, and TEQ values. The
15 average TEQ emission factor for the seven baseline tests was 72.8 ng I-TEQDF/kg of waste
16 burned (setting nondetect values equal to zero) and 73.7 ng I-TEQDF/kg of waste burned (setting
17 nondetect values equal to one-half the DL). The corresponding TEQDF-WHO98 values were 76.8
18 and 77.7 ng/kg. Table 6-4 presents the average congener and congener group results for these
19 tests.
20 In addition to the baseline tests, the combustion experiments included testing at three
21 different PVC levels: 0, 1, and 7.5% by weight PVC. The average emissions were 14, 201, and
22 4,916 ng I-TEQDF/kg of waste burned, respectively. Two tests using waste impregnated with
23 inorganic chloride (CaCl2) at a concentration of 7.5% by weight (and no PVC) averaged 734 ng I-
24 TEQDF/kg. Qualitative comparisons suggest that the tests conducted with higher chlorine, via
25 PVC or CaCl2, resulted in substantial increases in TEQ emissions.
26 Other variations in baseline waste composition included conducting one test with
27 compressed waste, one test with a double load of waste, and one test in which some of the waste
28 paper was wetted to simulate high-moisture burns. These tests resulted in a higher mean TEQ
29 emission factor (534 ng I-TEQDF/kg) than that of the baseline runs.
30 Several waste combustion variables were evaluated, such as average temperatures at
31 prescribed barrel heights; length of time temperatures (favorable temperature ranges) for
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1 CDD/CDF formation; and measurement of CO, CO2, O2, paniculate matter, and HC1. Statistical
2 analyses of the results indicated that CO emissions and temperature measured in the uppermost
3 portion of the barrel were the best predictors of TEQ variation. However, the wide variability in
4 test results (from less than 10 to more than 6,000 ng I-TEQDF/kg) also indicates that a high degree
5 of CDD/CDF emission variation can be expected due to factors that are not wholly related to
6 waste composition or burning practice, such as waste orientation. A mean emission factor of the
7 baseline tests (without PVC added) was developed from the data. This mean emission factor was
8 78.6 mg TEQDF-WHO/kg, and was used to estimate releases from barrel burning. The emission
9 factor is given a low confidence rating because it is possibly nonrepresentative of barrel burning
10 emissions.
11
12 6.5.2. Activity Level Information
13 The amount of refuse that is combusted annually in the United States in residential
14 backyard burn barrels is largely unknown. Although no national statistics are available, a limited
15 number of telephone surveys have attempted to measure the prevalence of backyard barrel
16 burning in a few geographical areas. This limited number of surveys, combined with census data
17 enumerating the rural and nonurban population of the United States, is used in this report to
18 estimate annual activity level in terms of the quantity of refuse combusted in burn barrels per
19 reference year. The following is a summary of this estimation procedure.
20
21 6.5.2.1. Summary of Barrel Burn Surveys
22 A total of seven surveys of the prevalence of backyard combustion of domestic refuse in
23 burn barrels were identified in the literature. For the most part, these surveys were an attempt to
24 estimate the barrel burning activity in a specific state, county, or region in support of regulatory
25 determinations on barrel burning. In general, the results of the surveys showed a prevalence of
26 barrel burning within the rural population to range from 12 to 40%. The mean of all surveys
27 combined was 28%. The following is a review of the surveys.
28 The Two Rivers Region Council of Public Officials (TRRCPO) and Patrick Engineering
29 conducted a telephone survey in the early 1990s of residents in five central Illinois counties.
30 They found that about 40% of the residents in a typical rural Illinois county burn household
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1 waste. The survey also indicated that, on average, those households that burn waste dispose of
2 approximately 63% of their household waste by burning it in barrels (TRRCPO, 1994).
3 Similar results were obtained in a survey conducted by Zenith Research Group, Inc.,
4 (2000) for the Western Lake Superior Sanitary District of Minnesota. This survey of 760
5 residents of selected portions of northwestern Wisconsin and northeastern Minnesota addressed,
6 in part, the use of burn barrels or other devices to burn household garbage or other materials.
7 Among all survey respondents, 27.5% admitted they currently use burn barrels or other devices to
8 burn household garbage or other materials.
9 Environics Research Group conducted a household garbage disposal and burning survey
10 of 1,516 residents of Ontario, Canada. All respondents resided in detached single-family homes
11 (Environics Research Group, 2001). Approximately 24% of all respondents reported burning
12 their household refuse in burn barrels.
13 E.H. Pechan and Associates conducted a residential municipal solid waste survey for the
14 Mid-Atlantic/Northeast Visibility Union (MANE-VU) states and tribes (Pechan, 2002). The
15 MANE-VU entities include: Connecticut, Delaware, the District of Columbia, Maine, Maryland,
16 Massachusetts, New Hampshire, New Jersey, New York, Pennsylvania, the Penobscot Indian
17 Nation, Rhode Island, the St. Regis Mohawk Tribe, and Vermont. Household waste burning
18 surveys were conducted by telephone for 72 residents in rural, suburban, and urban jurisdictions,
19 as classified by the 1990 census. The residents were asked to estimate the number of households
20 in their jurisdiction that burned household waste or trash. In general, the survey estimated that
21 11.9% of the rural population burned refuse in backyard burn barrels.
22 The State of California Air Resources Board (CARB) undertook a study of the prevalence
23 of backyard refuse burning in rural areas of 21 air management districts in California (CARB,
24 2002). From this study, CARB estimated that approximately 18% of the rural population in
25 California combusted their household refuse in backyard burn barrels.
26 In 1993, the St. Lawrence County Planning Office in Canton, New York, conducted a
27 survey of open burning of domestic refuse (St. Lawrence County, 1993). From the survey, it was
28 concluded that 48.2% of 9,926 households in rural areas of the County burned household refuse
29 in burn barrels.
30 In 1997, the State of Maine Department of Conservation Forestry Bureau surveyed rural
31 town fire wardens and state fire rangers regarding the prevalence of backyard burning of
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1 household waste. It was revealed through the survey that each day approximately 19,147 kg
2 domestic refuse was being combusted state-wide in approximately 8,510 burn barrels. In relation
3 to the total population, it was noted that 1 burn barrel existed for every 144 people.
4
5 6.5.2.2. Estimates of Activity Level
6 The following chart summarizes the steps taken in estimating total quantity of household
7 refuse combusted in backyard burn barrels in the years 1987, 1995, and 2000.
8
9 Steps taken in estimating total quantity of household refuse (kg/yr)
10 combusted in burn barrels
11
12 Reference year Reference year Reference year
13 SteP Assumption 2000 1995 1987
14 1. U.S. population 281,400,000 260,600,000 242,300,000
15 2. Population in rural and 59,000,000 52,700,000 50,700,000
nonurban areas of the
U.S.
16 3. Percent nonurban 28% 40% 40%
population burning
17 4. Adjusted population 16,726,500 21,080,000 20,280,000
burning MSW in
barrels
18 5. Per capita MSW 616 616 616
generation rate, kg/yr
19 6. Percent of MSW 63% 63% 63%
generated is burned at
homes
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1 7. Adjusted per capita 388 388 388
MSW burned, kg/yr
2 8. Total refuse generated 6,491,220,120 8,180,726,400 7,870,262,400
by rural, nonurban
population burning
MSW, kg/yr
3
4 Steps 1 and 2: The U.S. Census Bureau Statistical Abstract of the United States was used to
5 determine population size.
6 Step 3: The assumption of the percent of rural population combusting refuse in burn barrels was
7 derived from surveys as follows:
8 a. Reference year 2000 used the overall mean prevalence rate from 6 surveys (CARB,
9 2002; Zenith Research Group, 2003; Environics, 2001: Pechan and Associates, 2004; St
10 Lawrence County, 1993; and TRRCPO, 1994). This produced a mean prevalence of
11 28%. This overall mean percentage should reflect the impact of state bans and/or
12 restrictions on the practice of open burning of refuse.
13 b. Reference years 1995 and 1987 used the survey of TRRCPO (1994). This produced a
14 prevalence of 40%. This mean percentage should reflect the fact that the practice of open
15 burning of refuse was not banned or restricted by the maj ority of the states.
16 Step 4: The above mean prevalence rates were used to calculate the number of people residing in
17 rural areas assumed to have burned household refuse in burn barrels in each reference year
18 (assumption in step 2 multiplied by the percentage in step 3).
19 Step 5: The annual per capita household refuse generation rate is from the Municipal Solid Waste
20 Fact Book (2000). The figure of 616 kg/person/year is the result of subtracting out weight of
21 yard waste from the per capita generation rate.
22 Step 6: The assumption that 63% of municipal solid waste (MSW) generated in rural areas is
23 burned in backyard burn barrels and is derived from a survey conducted in rural counties of
24 Illinois (TRRCPO, 1994).
25 These activity levels are adopted and assigned a confidence rating of low because they are
26 derived from limited surveys that are possibly nonrepresentative of the national activity level.
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1 6.5.2.3. Alternative Approach to Estimating Activity Level
2 Actual amounts of refuse combusted in burn barrels in the United States is unknown and
3 must be estimated. The EPA Office of Air Quality Planning and Standards (OAQPS) developed
4 activity levels of residential MSW combusted in backyard barrels for reference year 2000. The
5 activity levels were determined by first estimating the amount of waste generated for each county
6 in the United States. The amount of waste generated was estimated by using a national average
7 per capita waste generation factor, which is 1.5 kg/person/day. This value was calculated using
8 population data from the 2000 Census and 2000 waste generation data (U.S. EPA, 2002d). To
9 better reflect the actual amount of household residential waste subject to being burned,
10 noncombustibles (glass and metals) and yard waste were excluded. This factor was then applied
11 to the portion of the county's total population that is considered rural, since open burning is
12 generally not practiced in urban areas. Using data from TRRCPO (1994), it was estimated that
13 for rural populations, 25 to 32% of generated MSW is burned. A median value of 28% was
14 assumed for the nation, and this correction factor was applied to the total amount of waste
15 generated. Controls (or burning bans) were accounted for by assuming that no burning takes
16 place in counties where the urban population is at least 80% of the total population (i.e., urban
17 plus rural). Zero emissions from open burning were attributed to these counties.
18 This technique produced an estimated annual activity level of 7.79 billion kg of
19 residential household waste combusted in burn barrels in the year 2000. This estimate is
20 approximately 16.5% greater than the estimate used in this report.
21
22 6.5.3. Emission Estimates
23 CDD/CDF emissions from burn barrels for reference years 1987, 1995, and 2000 were
24 calculated by multiplying the estimated annual total weight of household refuse combusted in
25 burn barrels (see Section 6.5.2.2, Estimates of activity level) by the dioxin emission factor. The
26 emission factor was 76.8 ng TEQDF-WHO98/kg (72.8 ng I-TEQDF/kg) of waste burned.
27 Annual nationwide TEQ emissions for 1987, 1995, and 2000 were calculated using
28 eq6-l.
29
30 ErEQ = EFrEQxAL (6-1)
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1 Where:
2 E^Q = Annual TEQDF emissions, g/yr
3 EFTEQ = TEQDF emission factor, 76.8 ng TEQDF-WHO98/kg of waste burned
4 AL Annual activity level: 7,870,262,400 kg in 1987; 8,180,726,400 kg in 1995; and
5 6,491,220,120 kg in 2000.
6
7 Using this equation, the estimated nationwide TEQDF emissions were
8
9 Reference year 1987: 604 g TEQDF-WHO98 (573 g I-TEQDF)
10 Reference year 1995: 628 g TEQDF-WHO98 (595 g I-TEQDF)
11 Reference year 2000: 498.53 g TEQDF-WHO98 (472.56 g I-TEQDF)
12
13 A low confidence rating is given to both the emission factor and the estimate of activity
14 level, therefore, the confidence rating is low for the estimate of TEQ emissions from backyard
15 barrel burning of refuse.
16
17 6.5.4. Composition of Ash from Barrel Burning
18 Ash samples were collected from open barrel burning (Lemieux, 1997) and analyzed for
19 CDDs/CDFs and PCBs. Ash samples from the experiments were combined, resulting in two
20 composite samples, one for recyclers and one for nonrecyclers. The results for PCBs depict only
21 the data for specific PCB congeners. The remaining PCB data reported in Lemieux (1997) could
22 not be related to a particular congener. The results are presented in Tables 6-5 and 6-6.
23
24 6.6. RESIDENTIAL YARD WASTE BURNING
25 6.6.1. Emissions Data
26 It is reasonable to assume that residential yard waste burning may be a source of
27 CDDs/CDFs, as they have been detected in forest and brush fires. No direct measurements of
28 CDD/CDF emissions from residential yard waste burning have been performed; however, Gullet
29 and Touati (2003) measured an average CDD/CDF emission factor of 20 ng TEQDF-WHO98/kg
30 during forest fire simulations where biomass samples from Oregon and North Carolina were
31 burned on an open platform (see Section 6.4). Therefore, the emission factor of 20 ng TEQDF-
32 WHO98/kg developed by Gullet (2003) will be used for residential yard waste burning.
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1 6.6.2. Activity Level Information
2 Pechan (2002) estimated that approximately 233 Ib of yard waste per household per year
3 (based on a four-person household) were burned in 2000. This is similar to the estimate of 106
4 to 319 Ib yard waste per household per year (based on a four-person household) that Pechan
5 calculated using the results of its household yard waste burning survey. The telephone survey
6 was completed by 181 rural, suburban, and urban jurisdictions of the MANE-VU entities. The
7 results indicated that approximately 28% of the population in rural areas burn household yard
8 waste and that households typically conduct two to three burns per year. Additionally, as
9 indicated by information provided by three respondents, 1 to 3 cubic yards of yard waste is
10 typically burned at a time.
11 As part of the 2000 National Emissions Inventory, OAQPS determined on a county-level
12 basis the amount of yard waste burned in 2000. The activity level estimates were based on the
13 assumption that yard waste was generated at a rate of 0.54 Ib/person/day in 2000, which in turn
14 was derived using population data for 2000 and the assumption that 27.7 million tons of yard
15 waste were generated in 2000 (U.S. EPA, 2002d). Of the total amount of yard waste generated,
16 the composition was assumed to be 25% leaves, 25% brush, and 50% grass by weight (U.S. EPA,
17 200la). Because open burning of grass clippings is not typically practiced by homeowners, only
18 50% of the yard waste generated was assumed to be burnable. Additionally, OAQPS assumed
19 that burning primarily occurs in rural areas (i.e., the per capita yard waste generation factor was
20 applied to only the rural population in each county) and that only 28% of the total yard waste
21 generated is actually burned (see Section 6.5).
22 The amount of yard waste assumed to be generated in each county was then adjusted for
23 variation in vegetation using BELD2. For counties with 10 to 50% forested land, the amount of
24 yard waste generated was reduced to 50% and for counties with less than 10% forested land, to
25 zero (i.e., no yard waste was generated). Adjustments for variation in vegetation were not made
26 to counties where the percentage of forested acres was greater than or equal to 50%. Before
27 calculating the percentage of forested acres per county, the acreage of agricultural lands was
28 subtracted from the acreage of forested lands to better account for the native vegetation that
29 would likely be occurring in the residential yards of farming states. Controls (or burning bans)
30 were accounted for by assuming that no burning takes place in counties where the urban
31 population exceeded 80% of the total population (i.e., urban plus rural). Using this method,
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1 OAQPS estimated that 255,000 metric tons of leaf and 255,000 metric tons of brush (total of
2 510,000 metric tons of yard waste) were burned in 2000.
3
4 6.6.3. Emission Estimate
5 Using the emission factor of 20 ng TEQDF-WHO98/kg (18.6 ng I-TEQDF/kg) and the
6 activity level of 510,000 metric tons yard waste burned in 2000, CDD/CDF emissions from open
7 burning of yard waste were 10.2 g TEQDF-WHO98 (9.5 g I-TEQDF) in 2000. Assuming 772 and
8 754 million kg of yard waste were burned in 1987 and 1995, respectively, then 15.4 g TEQDF-
9 WHO98 (14.4 g I-TEQDF) and 15.19 g TEQDF-WHO98 (14 g I-TEQDF) were emitted in 1987 and
10 1995, respectively. These should be regarded as preliminary estimates of possible emissions
11 from this source; further testing is needed to confirm the true magnitude of emissions. This is
12 because both the emission factor and activity levels are judged to be clearly nonrepresentative of
13 the source category.
14
15 6.7. LAND-CLEARING DEBRIS BURNING
16 6.7.1. Emissions Data
17 Land clearing is the clearing of land for the construction of new buildings (residential and
18 nonresidential) and highways. During the clearing process trees, shrubs, and brush are often torn
19 out, collected in piles, and burned. As with residential yard waste burning, it is assumed that the
20 burning of land-clearing debris may generate CDDs/CDFs because emissions have been detected
21 from forest and brush fires. No direct measurements of CDD/CDF emissions from the burning
22 of land-clearing debris have been performed, so the average emission factor of 20 ng TEQDF-
23 WHO98/kg, which was used for both forest fires and residential yard waste burning, is also used
24 for burning of land clearing debris (see Sections 6.4 and 6.6).
25
26 6.7.2. Activity Level Information
27 Activity levels associated with land clearing debris were calculated by OAQPS on a
28 county-level basis using the number of acres disturbed through residential, nonresidential, and
29 roadway construction.
30
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1 6.7.2.1. Residential Construction
2 In 2000, approximately 330,551 acres were disturbed by residential construction. This
3 number is based on county-level housing permit data and regional housing start data obtained
4 from the Census Bureau for single-family units, two-family units, and apartments. The county
5 permit data were first adjusted to equal regional housing-start data, and then the number of
6 buildings in each housing category was estimated. The total number of acres disturbed by
7 residential construction was then determined by applying the following conversion factors to the
8 housing-start data for each category:
9
10 Unit type Acres per building
11 Single-family unit 1/4
12 Two-family unit 1/3
13 Apartment 1/2
14
15 6.7.2.2. Nonresidential Construction
16 In 2000, approximately 336,224 acres were disturbed by nonresidential construction.
17 This number is based on the national value of construction put in place, as reported by the
18 Census Bureau. The national value was allocated to counties using construction employment
19 data from the Bureau of Labor Statistics and Dun & Bradstreet. A conversion factor of 1.6 acres
20 disturbed per $100,000 spent was applied to the county-level estimates of the value of
21 construction put in place to obtain the acres disturbed by nonresidential construction per county.
22 The conversion factor was developed using the Price and Cost Indices for Construction by
23 adjusting the 1992 value of 2 acres per $100,000 for 2000.
24
25 6.7.2.3. Roadway Construction
26 In 2000, approximately 190,367 acres were disturbed by roadway construction. This
27 number is based on 1999 Federal Highway Administration state expenditure data for capital
28 outlay within the following six road classifications: interstate (urban and rural), other arterial
29 (urban and rural), and collectors (urban and rural). The expenditure data were converted to miles
30 of road constructed based on data from the North Carolina Department of Transportation
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1 (NCDOT). According to NCDOT, approximately $4 million per mile is spent for freeway and
2 interstate projects, and approximately $1.9 million per mile is spent for arterial and collector
3 projects. The number of miles was then converted to acres disturbed using the following
4 conversion factors for each road classification category:
5
6 Road type Acres per mile
7 Interstate, urban 15.2
8 Interstate, rural 15.2
9 Other arterial, urban 15.2
10 Other arterial, rural 12.7
11 Collectors, urban 9.8
12 Collectors, rural 7.9
13
14 For 1995, state expenditure for capital outlay was assumed to be 74% of the total funding.
15 This percentage was derived using 2000 data (U.S. DOT, 2002). For 1987, 74% of the total
16 capital outlay of the average of 1985 and 1989 was used (capital outlays for 1985 and 1989 are
17 reported in U.S. DOT, 2002). Therefore, approximately 83,110 and 123,140 acres were
18 disturbed as the result of roadway construction in 1987 and 1995, respectively.
19
20 6.7.2.4. Fuel Loading Factors
21 To obtain the amount of biomass consumed by the burning of land-clearing debris, the
22 total acreage of land disturbed in each county by residential, nonresidential, and roadway
23 construction was distributed according to vegetation type (hardwood, softwood, and grass) and
24 then combined with vegetation-specific fuel loading factors. The percentage of vegetation type
25 within each county was determined using BELD2. The average loading factors used for each
26 fuel type is as follows:
27
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1 Fuel Fuel loading factor (tons/acre)
2 Hardwood 99
3 Softwood 57
4 Grass 4.5
5
6 Using this method, OAQPS estimated that 28.4 million metric tons of biomass were
7 burned through land clearing activities in 2000. EPA developed a national average biomass
8 loading factor of 33 metric tons burned per acre in 2000. Using this loading factor combined
9 with total acreage disturbed, EPA estimates that approximately 27.7 and 26.4 million metric tons
10 of biomass were burned by land clearing in 1987 and 1995, respectively.
11
12 6.7.3. Emission Estimate
13 Using the emission factor of 20 ng TEQDF-WHO98/kg (18.6 ng I-TEQDF/kg) and the
14 activity level estimates in Section 6.7.2.4, CDD/CDF emissions from land clearing burning were
15 568 g TEQDF-WHO98 (528 g I-TEQDF) in 2000, 528 g TEQDF-WHO98 (491 g I-TEQDF) in 1995,
16 and 553 g TEQDF-WHO98 (515 g I-TEQDF) in 1987. These should be regarded as preliminary
17 estimates of possible emissions from this source because the emission factor is clearly
18 nonrepresentative; further testing is needed to confirm the true magnitude of emissions.
19
20 6.8. UNCONTROLLED COMBUSTION OF POLYCHLORINATED BIPHENYLS
21 The accidental combustion of PCB-containing electrical equipment or intentional
22 combustion of PCBs in incinerators and boilers not approved for PCB burning (40 CFR 761)
23 may produce CDDs/CDFs. At elevated temperatures, such as in transformer fires, PCBs can
24 undergo reactions to form CDFs and other by-products. More than 30 accidental fires and
25 explosions involving PCB transformers and capacitors in the United States and Scandinavia that
26 involved the combustion of PCBs and the generation of CDDs/CDFs have been documented
27 (Hutzinger and Fiedler, 1991b; O'Keefe and Smith, 1989; Williams et al., 1985). For example,
28 analyses of soot samples from a Binghamton, New York, office building fire detected 20 |_ig/g of
29 total CDDs (0.6 to 2.8 |_ig/g of 2,3,7,8-TCDD) and 765 to 2,160 |_ig/g of total CDFs (12 to 270
30 |_ig/g of 2,3,7,8-TCDF). At that site, the fire involved the combustion of a mixture containing
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1 PCBs (65%) and chlorobenzene (35%). Laboratory analyses of soot samples from a PCB
2 transformer fire that occurred in Reims, France, indicated total CDD and CDF levels in the range
3 of 4 to 58,000 ng/g and 45 to 81,000 ng/g, respectively.
4 Using a bench-scale thermal destruction system, Erickson et al. (1984) determined the
5 optimum conditions for CDF formation to be 675 °C, an excess oxygen concentration of 8%, and
6 a residence time of 0.8 sec or longer. Combusting mineral oil and silicone oil containing 5, 50,
7 and 500 ppm of Aroclor 1254 at these conditions for 0.8 sec yielded PCB to CDF conversion
8 efficiencies as high as 4%. Up to 3% conversion efficiency was observed when an askarel (70%
9 Aroclor 1260) was combusted under the same conditions.
10 The use of PCBs in new transformers in the United States is banned, and their use in
11 existing transformers and capacitors is being phased out under regulations promulgated under the
12 Toxic Substances Control Act.
13 Because of the accidental nature of these incidents, the variation in duration and intensity
14 of elevated temperatures, the variation in CDD/CDF content of residues, and uncertainty
15 regarding the amount of PCBs still in service in electrical equipment, EPA judged the available
16 data inadequate for developing any quantifiable emission estimates. However, Thomas and
17 Spiro (1995) conservatively estimated that about 15 g of TEQ may be generated annually from
18 fires in commercial and residential buildings each year. This estimate is based on the following
19 assumptions: (a) the I-TEQDF emission rate is 20 pg/kg of PCB burned, (b) 74,000 metric tons of
20 PCB are still in use in various electrical equipment, and (c) 1% of the in-use PCBs are burned
21 during the course of structural fires annually.
22
23 6.9. VOLCANOES
24 To date, no studies demonstrating the formation of CDDs/CDFs by volcanoes have been
25 published. Given the available information from the studies discussed below, volcanoes do not
26 appear to be sources of CDD/CDF release to the environment.
27 Gribble (1994) summarized some of the existing information on the formation of
28 chlorinated compounds by natural sources, including volcanoes. Gribble reported that several
29 studies had demonstrated the presence of chlorofluorocarbons and simple halogenated aliphatic
30 compounds (one and two carbon chain length) in volcanic gases. In addition, several chlorinated
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1 monoaromatic compounds as well as three PeCB congeners were reported as having been
2 detected in the ash from the 1980 eruption of Mount St. Helens. Gribble hypothesized that the
3 formation of these PCB compounds was the result of rapid, incomplete, high-temperature
4 combustion of chloride-containing plant material in the eruption zone. However, he presented no
5 information indicating formation of CDDs/CDFs by volcanoes.
6 Lamparski et al. (1990) analyzed groundfall ash samples collected at various distances
7 and locations from Mount St. Helens following the eruption in 1980. The findings of this study
8 indicate that volcanic paniculate emissions were free of detectable PCBs and nearly free of
9 detectable CDDs (0.8 ng/kg HpCDD detected) upon exiting the volcano and remained so
10 throughout their period of deposition in the blast zone. However, upon transport through the
11 atmosphere, measurable and increasing levels of CDDs and PCBs were detected in deposited ash
12 as it passed from rural to urban environments. The authors hypothesized that CDDs and PCBs in
13 the atmosphere became associated with the volcanic ash particulates through gas-phase sorption
14 or particulate agglomeration.
15 Takizawa et al. (1994) investigated the CDD/CDF content of volcanic dust fall from two
16 active volcanoes in Japan (Mt. Fugendake and Sakurajima). The study was not designed to
17 determine whether the CDDs/CDFs observed were formed by the volcanoes or were scavenged
18 from the atmosphere by the falling dust and ash. The dust fall was collected for 1-month periods
19 during July and October 1992; two samples of the volcanic ash were collected in 1992. The
20 results of the sample analyses for 2,3,7,8-substituted CDDs and CDFs, presented in Table 6-7,
21 show that no 2,3,7,8-substituted congeners with less than seven chlorines were detected;
22 however, the authors reported that non-2,3,7,8-substituted congeners in the less-chlorinated
23 congener groups were detected.
24
25 6.10. FIREWORKS
26 In order to produce various effects and illuminations, modern fireworks contain not only
27 black powder but also substances such as chlorine-based oxidizers, flame-coloring copper salts,
28 and pulverized polyvinylchloride, which are known to be involved in dioxin-forming processes.
29 During deflagration of pyrotechnics, core temperatures reach as high as 2,500 °C, which would
30 most likely inhibit the formation of organic pollutants. However, CDDs/CDFs may be generated
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1 in the areas adjacent to the combustion zone, where temperatures are lower and dwell times are
2 longer. Therefore, CDDs/CDFs may be generated during the cooling period of the deflagration
3 products because the temperatures of the smoke and ash are within the possible temperature
4 range of dioxin formation (Fleischer et al., 1999).
5 During a celebration in Oxford, England, that was accompanied by fireworks and
6 bonfires, Dyke and Coleman (1995) reported a fourfold increase in CDD/CDF TEQ
7 concentrations in the ambient air (see Section 6.2.2). Air concentrations before and after the
8 celebration ranged from 0.15 to 0.17 pg I-TEQDF/m3. The air concentration during the
9 celebration was 0.65 pg I-TEQDF/m3. Fleischer et al. (1999) conducted an experiment to measure
10 the air emissions resulting specifically from the following seven types of fireworks: firecracker,
11 cone fountain, jumping jack, whistler, sparkling rocket, roman candle, and four-color fountain.
12 The paper cartridges and charges were separated from each firework and deflagrated separately in
13 a steel chamber. CDD/CDF concentrations were measured both in air samples and in paper and
14 ash samples. The results indicated that dioxins were not present in significant quantities in the
15 air samples collected. Therefore, Fleisher et al. suspected that the increased background
16 concentration of CDDs/CDFs detected by Dyke and Coleman (1995) was due mainly to the
17 bonfires and not the fireworks. However, concentrations of HpCDD and OCDD/F were present
18 in the paper and ash collected after the fireworks were detonated at concentrations ranging from
19 less than the DL (10 ng/kg) to 1,200 ng/kg. Table 6-8 depicts the results of Fleischer's tests.
20 Given the lack of information on the potential for CDD/CDF emissions from fireworks, the
21 emissions cannot be quantified.
22
23 6.11. OPEN BURNING AND OPEN DETONATION OF ENERGETIC MATERIALS
24 Open burning and open detonation (OB/OD) practices are routinely used to destroy
25 surplus or unserviceable energetic materials. Mitchell and Suggs (1998) conducted a study to
26 determine emission factors from OB/OD in which air samples were collected for CDD/CDF
27 analysis during four burns and after three detonations. The results of the study indicated that
28 emission levels of CDDs/CDFs as a result of disposal of energetic materials by OB/OD were
29 nondetectable.
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Table 6-1. CDD/CDF emission factors for a landfill flare
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility emission factor"
(ng/m3 gas combusted)
0.018
0.092
0.074
0.074
0.259
0.755
4.414
14.074
0.385
1.136
1.455
0.422
0.11
0.681
1.215
0.073
0.639
5.686
20.192
2.392
2.433
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
aAssumes heat content of 1.86e+07 J/m3 for landfill gas (Federal Register, 1996a).
NR = Not reported
Source: CARB (1990d).
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Table 6-2. CDD/CDF emission factors for forest fires
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 CDD/CDF
Total TEQDF-WHO98
Total I-TEQDF
Mean emission factor (ng/kg)
Nondetect set to zero
1.15
3.83
5.68
10.70
17.34
166.27
663.67
6.98
6.34
10.09
16.72
7.14
1.11
9.81
25.39
3.06
10.27
965.54
19.90
18.59
Nondetect set to 1A detection
limit
1.28
3.83
5.68
10.70
17.34
166.27
663.67
6.98
6.35
10.11
16.74
7.16
1.20
9.85
25.39
3.12
10.32
965.95
20.07
18.77
Source: Gullet (2003).
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Table 6-3. Forest fire fuel loading factors
Region
Alaska
California
Intermountain
North Central
Northern
Pacific Northwest
Rocky Mountain
Southern
Southwestern
Fuel loading factors (tons per acre)
Wildfires
6
18
8
11
60
60
30
9
10
Prescribed burning
12.6
14.2
6.3
8.7
47.3
47.3
23.7
7.1
7.9
Source: U.S. EPA (2002e).
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Table 6-4. CDD/CDF air emission factors from barrel burning of household waste
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
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Average air emission factors"
(ng/kg waste burned)
Nondetect set to 1A detection limit
3.4
8.2
6.6
9.9
19.1
39.8
49.7
45.6
37.2
65.2
113.8
38.5
61.9
O
128.6
14.6
37.5
136.6
545.8
73.7
77.7
413
281
221
105
43
1,880
1,021
492
169
32
4,657
Nondetect set to zero
2.7
8.1
6.4
9.7
19
39.8
49.7
45.6
37.2
65.2
113.8
38.5
61.9
2.5
124.4
15
36.4
135.4
540.4
72.8
76.8
413
281
221
105
43
1,880
1,021
492
169
30
4,655
aListed values are the arithmetic averages of seven tests for the congeners and the averages of five tests for the
congener groups.
Sources: Lemieux (2000), Gullett et al. (1999, 2000a, 2000b).
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Table 6-5. CDD/CDF analysis for composite ash samples from barrel
burning (ng/kg of ash)
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
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD
Total CDF
Total CDD/CDF
Average
concentration in
composite ash sample
Avid
recycler
31
230
270
420
300
4,000
9,600
830
1,000
2,500
2,300
2,100
2,900
810
12,000
1,400
8,200
2,500
4,100
5,600
7,600
9,600
25,000
21,000
19,000
17,000
8,200
14,851
34,040
48,891
Non-
recycler
9
53
44
74
56
630
690
220
270
690
480
490
670
150
2,100
170
560
490
740
1,300
1,300
690
8,200
6,600
4,600
2,900
560
1,556
5,800
7,356
I-TEQDF
Avid
recycler
31
115
27
42
30
40
9.6
83
50
1,250
230
210
290
81
120
14
8.2
-
-
-
-
-
-
-
-
-
-
-
-
-
Non-
recycler
9
26.5
4.4
7.4
5.6
6.3
0.69
22
13.5
345
48
49
67
15
21
1.7
0.56
-
-
-
-
-
-
-
-
-
-
-
-
-
TEQDF-WH098
Avid
recycler
31
230
27
42
30
40
0.96
83
50
1,250
230
210
290
81
120
14
0.82
-
-
-
-
-
-
-
-
-
-
-
-
-
Non-
recycler
9
53
4.4
7.4
5.6
6.3
0.069
22
13.5
345
48
67
15
21
1.7
0.056
-
-
-
-
-
-
-
-
-
-
-
-
-
Source: Lemieux (1997).
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Table 6-6. PCB analysis for composite ash samples from barrel burning
(ng/kg of ash)
Compound
2-Chlorobiphenyl
2,3'-Dichlorobiphenyl
2,2',6-Trichlorobiphenyl
2,2',5-Trichlorobiphenyl
2,3',5-Trichlorobiphenyl
2,3',4-Trichlorobiphenyl
2,4',5-Trichlorobiphenyl
2,4,4'-Trichlorobiphenyl
2,2',4,6'-Tetrachlorobiphenyl
2,2',3,6'-Tetrachlorobiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2,2',3,5'-Tetrachlorobiphenyl
2,2',4,4',5-Pentachlorobiphenyl
2,2',3,3',5-Pentachlorobiphenyl
2,2',3,4,5,5'-Hexachlorobiphenyl
Avid recycler
<2,500
3,700
<500
32,000
800
<500
1,500
<500
<500
5,300
3,100
2,600
3,400
400
1,200
Nonrecycler
4,900
4,700
5,600
6,300
800
700
900
500
1,500
1,300
1,800
1,200
1,300
<500
<500
Source: Lemieux (1997).
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Table 6-7. CDDs/CDFs in dust fall and ashes from volcanoes
2,3,7,8-substituted
congener group
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
Dust fall (mg/km2/month)a
July 1992
<0.5
<0.5
<0.5
9.2
14
<0.5
<0.5
<0.5
1.9
4.2
Oct. 1992
<0.5
<0.5
<0.5
5.2
11
<0.5
<0.5
<0.5
2.8
1.8
Volcanic ash (ng/kg)b
Ash no. 1
<0.1
<0.1
<0.1
2.5
1.7
<0.1
<0.1
<0.1
1.2
<0.5
Ash no. 2
<0.1
<0.1
<0.1
1.8
2.2
<0.1
<0.1
<0.1
1.2
<0.5
aDust fall measured from the active volcano Fugendake.
Volcanic ash measured from the active volcano Sakurajima.
Source: Takizawaetal. (1994).
Table 6-8. Residue of HpCDD/HpCDF and OCDD/OCDF in paper
cartridges and charges of selected pyrotechnic products (ng/kg)
Product
Firecracker
Cone fountain
Jumping Jack
Whistler
Sparkling rocket
Roman candle
Four-color fountain
Paper Cartridges
HpCDD
16
111
<10
22
30
<10
<10
OCDD
322
384
33
353
129
426
18
OCDF
79
22
24
121
12
39
<10
Charge
HpCDD
<10
<10
<10
<10
<10
<10
<10
OCDD
535
<10
28
35
13
<10
<10
OCDF
26
<10
<10
1200
<10
22
<10
Source: Fleischer etal. (1999).
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Ratio (congener emission factor/total 2378-CDD/CDF emission factor)
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
0.1
0.2
0.3
0.4
0.5
0.6
Figure 6-1. Congener profile for landfill flare air emissions.
Source: CARB (1990d).
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Ratio (congener emission factor / 2378-CDOCDFemission factor)
0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800
4D2378
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-HxCDF
1,2,3,4,7,8-PeCDF
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
Figure 6-2. Congener profile for forest fire simulation approach emissions.
Source: Gullet and Touati (2003).
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1 7. METAL SMELTING AND REFINING SOURCES OF CDDs/CDFs
2
3 7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING
4 Little information has been published on the potential for the formation and
5 environmental release of CDDs/CDFs from primary nonferrous metal manufacturing facilities.
6 Oehme et al. (1989) reported the presence of CDDs/CDFs in the wastewater of a magnesium
7 refining facility and in the receiving water sediments downstream of a nickel refining facility in
8 Norway. The information from this study is insufficient for evaluating CDD/CDF emissions, if
9 any, from the smelting/refining of magnesium and nickel in the United States. The potential for
10 formation and release of CDDs/CDFs by primary copper smelters in the United States has been
11 reported by Environmental Risk Sciences (1995) to be negligible. Lexen et al. (1993) reported
12 finding few or no CDDs/CDFs in solid wastes from a primary aluminum smelter. Bramley
13 (1998) indicated that the smelting/refining of titanium may be a source of CDDs/CDFs. The
14 findings of these studies are discussed in the following subsections.
15
16 7.1.1. Primary Copper Smelting and Refining
17 Environmental Risk Sciences (1995) prepared an analysis for the National Mining
18 Association on the potential for CDD/CDF emissions from the primary copper smelting industry.
19 The analysis included reviewing the process chemistry and technology of primary copper
20 smelting, identifying operating conditions, and comparing process stream compositions from
21 seven of the eight U.S. primary copper smelters that are members of the National Mining
22 Association. The analysis also included stack testing for CDDs/CDFs at two facilities. The stack
23 testing involved the principal off-gas streams for copper smelters: main stack, plant tail gas
24 stack, and vent fume exhaust (Secor International Inc., 1995a, b). The two facilities that were
25 tested (Phelps Dodge Mining Co. in Playas, New Mexico, and Cyprus Miami Mining Co. in
26 Claypool, Arizona) were selected as representative of the other facilities in the industry because
27 of their similarity to the other facilities in terms of process chemistry, process stream
28 composition, and process stream temperatures. CDDs/CDFs were not detected in the air
29 emissions from either facility.
30 The results of the assessment of the process chemistry and technology, the operating
31 conditions, and process stream compositions indicate that although there is some potential for
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1 CDD/CDF formation in this industry, several factors lessen the probability, including the
2 following: (a) most of the energy used to melt copper is derived from oxidation of copper sulfide
3 ore minerals (CuFeS2) rather than carbon (fossil fuels), (b) low concentrations of organic carbon
4 and chloride are present in raw materials and reagents, (c) high concentrations of SO2 are present
5 in process gases (6 to 40% by volume), (d) high temperatures are maintained in the furnaces and
6 converters (1,100 to 1,500 °C), and (e) copper (II) chloride is apparently absent in process
7 emissions.
8 In 2001, emission measurements for various persistent, bioaccumulative, and toxic
9 substances, including CDDs/CDFs, were collected in Canada as a voluntary initiative under the
10 Great Lakes Binational Toxics Strategy (Cianciarelli, 200la). One of the facilities tested was the
11 Falconbridge Kidd Metallurgical plant in Timmins, Ontario, a copper smelting plant. Emission
12 summaries are provided in Table 7-1 as TEQ concentrations corrected for 11% oxygen for the
13 average of three runs. The total concentrations for each run were 3.8, 1.7, and 0.7 pg TEQ/m3,
14 respectively. Annual CDD/CDF emission rates were estimated to be 0.002 g I-TEQ/yr.
15 In 2002, Environment Canada began developing a generic dioxin/furan emissions testing
16 protocol for use by the base metals smelting sector (Charles E. Napier Company, Ltd., 2002).
17 Several base metals smelting and refining complexes were identified, and a summary of readily
18 available published information on dioxin/furan emissions from the base metals smelter
19 processes was compiled. A summary of this information is provided in Table 7-2. Four facilities
20 were identified as primary copper smelters and had CDD/CDF emission concentrations ranging
21 from less than 1 to 559 pg I-TEQ/dscm.
22 In 1995, eight primary smelters were in operation in the United States, one of which
23 closed at the end of the year (Edelstein, 1995). Total refinery production was 1.60 million metric
24 tons in 1995, including 0.36 million metric tons from scrap material (Edelstein, 1995), and 1.13
25 million metric tons in 1987 (USGS, 1997c). In 2000, four primary smelters of copper were in
26 operation in the United States, producing 1.61 million metric tons of copper (USGS, 2002).
27 The results of this assessment were developed using the stack test data from the two
28 tested facilities in the United States. Conservatively assuming that all nondetect values were
29 present at one-half the detection limit, Environmental Risk Sciences (1995) calculated the annual
30 TEQ emission to air to be less than 0.5 g I-TEQDF in 1995 for the seven facilities (out of a total of
31 eight) belonging to the National Mining Association. Assuming that 1987 feed and processing
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1 materials were similar, 1987 releases can be estimated at less than 0.5 g I-TEQDF as well.
2 Because the number of facilities was reduced in 2000, the national emission estimate is reduced
3 proportionally to 0.29 g I-TEQ. The activity level estimates are assigned a high confidence
4 rating and the emission factor estimates a medium rating; therefore, the emission estimates are
5 assigned a medium confidence rating. The activity levels are based on comprehensive surveys.
6 The emission factors are reasonably representative of emissions from the source category.
7
8 7.1.2. Primary Magnesium Smelting and Refining
9 Oehme et al. (1989) reported that the production of magnesium can lead to the formation
10 of CDDs and CDFs. They estimated that 500 g of I-TEQDF were released to the environment in
11 wastewater and 6 g I-TEQDF were released to air annually from a magnesium production facility
12 in Norway; CDFs predominated, with a CDF-to-CDD concentration ratio of 10:1. At the time of
13 sampling, the magnesium production process involved formation of magnesium oxide (MgO)
14 from calcinated dolomite followed by a step in which magnesium chloride (MgCl2) was produced
15 by heating MgO/coke pellets in a shaft furnace in a pure chlorine atmosphere to about 700 to 800
16 °C. The MgCl2 was then electrolyzed to form metallic magnesium and chloride. The chloride
17 excess from the MgCl2 process and the chloride formed during electrolysis were collected by
18 water scrubbers and directly discharged to the environment. The discharged wastewater
19 contained 200 to 500 ppm of suspended PM. All but trace quantities of the hexa through octa
20 congeners were associated with the particulates; up to 10% of the tetra and penta congeners were
21 present in the water phase.
22 A study by the firm operating the facility (Musdalslien et al., 1998) indicated that
23 installation of a water treatment system had reduced annual emissions to water to less than 1 g
24 Nordic TEQ, and emissions to air had been reduced to less than 2 g Nordic TEQ. This study also
25 presented results demonstrating that the carbon-reducing agent used in the MgCl2 production step
26 and the operating conditions of the shaft furnace greatly affected the formation of CDDs/CDFs.
27 Gases from the furnace were measured nine times over sampling periods of 6 to 8 hr. The
28 calculated emission factor to air (i.e., before any air pollution control device [APCD] controls)
29 ranged from 468 to 3,860 ng Nordic TEQ per kg of MgCl2 produced. The APCD controls
30 consisted of three water scrubbers, a wet electrostatic precipitator (ESP), and an incinerator.
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1 From 1950 to 2000, the United States was the world's largest producer of metallic
2 magnesium (Kramer, 1995). In 1995, three magnesium production facilities were operating in
3 the United States. As in the Norwegian plant, an electrolytic process (electrolysis of MgCl2) was
4 used at the plants in Texas (capacity of 65,000 metric tons/yr) and Utah (capacity of 40,000
5 metric tons/yr) to recover metallic magnesium from MgCl2. However, these two facilities
6 reportedly used seawater and lake brines as the source of magnesium, and the procedures to
7 obtain and purify MgCl2 did not involve chlorinating furnaces and carbonized pellets (Lockwood
8 et al., 1981). A thermic process was used to recover magnesium from dolomite at the facility in
9 Washington (capacity of 40,000 metric tons/yr) (Kramer, 1995). In thermic processes, MgO, a
10 component of calcinated dolomite, is reacted with a metal such as silicon (usually alloyed with
11 iron) to produce metallic magnesium. In 2000, the Magnesium Corporation of America facility
12 near Rowley, Utah, was the only operational magnesium smelting facility in the United States.
13 Monitoring of wastewater discharges from U.S. magnesium production facilities for
14 CDD/CDF content has not been reported. Wastewater discharges of CDDs/CDFs reported for
15 the Norwegian facility (Oehme et al., 1989), discussed in the previous paragraphs, are not
16 adequate to support development of wastewater emission factors for U.S. facilities because of
17 possible differences in the processes used to manufacture MgCl2 and pollution control
18 equipment.
19 Monitoring of air emissions for CDD/CDF content has been reported for the Magnesium
20 Corporation of America facility near Rowley, Utah (Western Environmental Services and
21 Testing, Inc., 2000). The average emission rates (for three tests) reported for the melt reactor
22 stack and the cathode stack were 0.31 mg I-TEQDF/hr and 0.16 mg I-TEQDF/hr, respectively.
23 Emissions data were judged inadequate for developing national emission estimates for
24 1987 that could be included in the national inventory. The confidence in the degree to which the
25 one tested facility represents the emissions from the other two U.S. facilities is low. However, an
26 estimate of the potential TEQ annual emissions for 1995 from U.S. primary magnesium
27 production facilities can be made by assuming that the average total emission factor for the Utah
28 facility measured in May 2000 (0.47 mg I-TEQDF/hr ) is representative of the other two facilities
29 for magnesium production. Specifically, if it is assumed that this facility operated for 24 hr/day
30 for 365 days in 1995, then the annual release in 1995 would have been 4.1 g I-TEQDF. If it is
31 further assumed that this facility operated at 98% of its rated capacity of 40,000 metric tons/yr,
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1 then the production-based emission factor would be 105 ng I-TEQDF/kg of magnesium produced.
2 Applying this emission factor to 98% of the industry's production capacity in 1995 (142,000
3 metric tons) yields a preliminary annual emission estimate of 14.6 g I-TEQDF in 1995.
4 In 2000, the Magnesium Corporation of America facility near Rowley, Utah, was the only
5 operational magnesium smelting facility. Production of primary magnesium at this facility was
6 400,000 metric tons in 2000. Using the emission factor of 105 ng I-TEQDF/kg of magnesium
7 produced, the national estimate for dioxin releases in 2000 due to primary magnesium smelting is
8 42 g I-TEQ/yr. The emission factor has a high confidence rating because it was developed using
9 data from this facility; therefore, the emission estimate is assigned a high confidence level.
10
11 7.1.3. Primary Nickel Smelting and Refining
12 Oehme et al. (1989) reported that certain primary nickel refining processes generate
13 CDDs and CDFs, primarily CDFs. Although the current low-temperature process used at the
14 Norwegian facility is estimated to result in releases to water of only 1 g I-TEQDF/yr, a high-
15 temperature (800 °C) process to convert nickel chloride to nickel oxide that had been used for
16 17 yr at the facility is believed to have resulted in significant releases in earlier years, based on
17 the ppb levels of CDFs detected in aquatic sediments downstream of the facility.
18 According to Kuck (1995), the only nickel mining and smelting complex in the United
19 States (located in Oregon) had a capacity of 16,000 metric tons/yr. The facility had been on
20 standby since August 1993 and had no production in 1994. The facility restarted operations in
21 April 1995 and produced 8,290 metric tons of nickel that year. In 1998, the smelter closed
22 because of low nickel prices (USGS, 2002).
23 Monitoring of discharges for CDD/CDF content at this one U.S. facility has not been
24 reported. Emissions of CDDs/CDFs were reported for a Norwegian facility in the late 1980s, as
25 discussed above. The emissions information contained in the Norwegian study (Oehme et al.,
26 1989) is not adequate to support development of emission factors for the U.S. facility for 1987
27 and 1995. Because the facility closed in 1998, emission estimates for 2000 for primary nickel
28 smelting are zero.
29
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1 7.1.4. Primary Aluminum Smelting and Refining
2 No sampling of air emissions for the presence of CDDs/CDFs has been reported for this
3 industry. Lexen et al. (1993) reported that samples of filter powder and sludge from a lagoon at
4 the only primary aluminum production plant in Sweden showed no or little CDDs/CDFs.
5 Because the primary smelting process does not use chlorine, there is widespread belief that
6 dioxin emissions from primary aluminum smelting facilities do not exist; therefore, no sampling
7 has been done.
8 In the primary aluminum smelting process, bauxite ore, a hydrated oxide of aluminum
9 consisting of 30 to 56% alumina (A12O3), is refined into alumina by the Bayer process. The
10 alumina is then shipped to a primary aluminum smelter for electrolytic reduction to aluminum.
11 Electrolytic reduction of alumina occurs in shallow rectangular cells, or pots, which are steel
12 shells lined with carbon. Carbon electrodes (petroleum coke mixed with a pitch binder)
13 extending into the pot serve as the anodes and the carbon lining serves as the cathode. Three
14 types of pots are used: prebaked anode cell, horizontal stud Soderberg anode cell, and vertical
15 stud Soderberg anode cell. Most of the aluminum produced in the United States is produced
16 using the prebaked cells. Molten cryolite (Na3AlF6) functions as both the electrolyte and the
17 solvent for the aluminum. Aluminum is deposited on the cathode as molten metal (U.S. EPA,
18 1998a).
19 Prior to casting, the molten aluminum may be batch treated in reverberatory furnaces
20 (such as those used in secondary aluminum smelting) to remove oxides, gaseous impurities, and
21 active metals such as sodium and magnesium. One process consists of adding a flux of chloride
22 and fluoride salts and then bubbling chlorine gas through the molten mixture (U.S. EPA, 1998a).
23 U.S. production of primary aluminum was 3.343 million metric tons in 1987 and 3.375
24 million metric tons in 1995. In 1995, 13 companies operated 22 primary aluminum reduction
25 plants (USGS, 1997d, e). In 2000, 12 companies operated 23 primary aluminum reduction plants
26 and primary aluminum smelters produced 3.7 million metric tons of aluminum (USGS, 2002).
27 Because emission factors have not been developed for this sector, there are no emission estimates
28 for this category.
29
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1 7.1.5. Primary Titanium Smelting and Refining
2 It has been suggested that carbochlorination processes used in this industry may be a
3 source of CDDs/CDFs (Bramley,1998; ERG, 1998). As discussed below, CDDs/CDFs have
4 been measured in titanium dioxide production sludges. A brief summary of the processes used in
5 this industry is presented in the following paragraphs.
6 In primary titanium smelting, titanium oxide ores and concentrates are chlorinated in
7 fluidized-bed reactors in the presence of coke at 925 to 1,010 °C to form titanium tetrachloride
8 (TiCl4). The TiCl4 is separated from other chlorides by double distillation. The TiCl4 is then
9 either oxidized at 985 °C to form pigment-grade titanium dioxide or reduced using sodium or
10 magnesium to form titanium sponge (i.e., metallic titanium) (Knittel, 1983). Titanium ingot is
11 produced by melting titanium sponge or scrap or a combination of both using electron beam,
12 plasma, and vacuum arc methods. Scrap currently supplies about 50% of ingot feedstock
13 (Gambogi, 1996).
14 Titanium sponge is produced at two facilities in the United States, one in Albany, Oregon,
15 and the other in Henderson, Nevada. In 1995, the U.S. production volume of titanium sponge
16 was withheld to avoid disclosing proprietary data; domestic sponge capacity was 29,500 metric
17 tons/yr. In 1987, U.S. production of titanium sponge was 17,849 metric tons. More than 90% of
18 titanium dioxide is produced using the process described above. Titanium dioxide pigment is
19 used in paints, plastics, and paper products. In 1995, titanium dioxide was produced at nine
20 facilities in the United States. Production volumes in 1987 and 1995 were 821,000 and 1.8
21 million metric tons, respectively (Gambogi, 1996; USGS, 1997f). In 2000, four companies at
22 eight facilities in seven states produced 1.44 million metric tons of titanium dioxide (USGS,
23 2002). Titanium dioxide production creates a sludge waste, and CDDs/CDFs have been
24 measured in these sludges (U.S. EA, 2001f). For the most part, these sludges have been disposed
25 of in either on-site or off-site RCRA Subtitle D solid waste disposal facilities. However, given
26 the potential for leaching of the heavy metals from the sludge in the Subtitle D landfill, EPA has
27 listed this waste as hazardous waste under Subtitle C. These sludges are now considered a
28 hazardous waste under RCRA and must be disposed of in permitted landfills (U.S. EPA, 2001f).
29 Therefore, they are not considered to cause environmental releases per the definition in this
30 document and are not included in the inventory.
31
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1 7.2. SECONDARY NONFERROUS METAL SMELTING
2 Secondary smelters primarily engage in the recovery of nonferrous metals and alloys from
3 new and used scrap and dross. The principal metals of this industry, both in terms of volume and
4 value of product shipments, are aluminum, copper, lead, zinc, and precious metals (U.S. DOC,
5 1990a). Scrap metal and metal wastes may contain organic impurities such as plastics, paints,
6 and solvents. Secondary smelting and refining processes for some metals (e.g., aluminum,
7 copper, and magnesium) use chemicals such as sodium chloride, potassium chloride, and other
8 salts. The combustion of these impurities and chlorine salts in the presence of various types of
9 metal during reclamation processes can result in the formation of CDDs/CDFs, as evidenced by
10 their detection in the stack emissions of secondary aluminum, copper, and lead smelters (Aittola
11 et al., 1992; U.S. EPA, 1987a, 1997b).
12
13 7.2.1. Secondary Aluminum Smelters
14 Secondary aluminum smelters reclaim aluminum from scrap using two processes:
15 precleaning and smelting. Both processes may produce CDD/CDF emissions.
16 Precleaning processes involve sorting and cleaning scrap to prepare it for smelting. Cleaning
17 processes that may produce CDD/CDF emissions use heat to separate aluminum from
18 contaminants and other metals. These techniques are "roasting" and "sweating." Roasting uses
19 rotary dryers with a temperature high enough to vaporize organic contaminants but not high
20 enough to melt aluminum. An example of roasting is the delacquering and processing of used
21 beverage cans. Sweating involves heating aluminum-containing scrap metal to a temperature
22 above the melting point of aluminum but below the melting temperature of other metals such as
23 iron and brass. The melted aluminum trickles down and accumulates in the bottom of the sweat
24 furnace and is periodically removed (U.S. EPA, 1997b).
25 After precleaning, the treated aluminum scrap is smelted and refined. This usually takes
26 place in a reverberatory furnace. Once smelted, flux is added to remove impurities. The melt is
27 demagged to reduce the magnesium content of the molten aluminum by adding chlorine gas. The
28 molten aluminum is then transferred to a holding furnace and alloyed to final specifications (U.S.
29 EPA, 1997b).
30 CDD/CDF emissions to air have been measured at six U.S. secondary aluminum
31 operations. Four facilities were tested in 1995 and two facilities were tested in 1992. Three of
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1 the four 1995 tests were conducted by EPA in conjunction with the Aluminum Association to
2 identify emission rates from facilities with potentially maximum-achievable-control-technology -
3 grade operations and APCD equipment. The fourth test was performed by EPA (U.S. EPA,
4 1995h). Results from two facilities tested by the California Air Resources Board (CARB) in
5 1992 were presented in two confidential reports.
6 The first facility tested in 1995 was a top-charge melt furnace (Advanced Technology
7 Systems, Inc., 1995). During testing, the charge material to the furnace was specially formulated
8 to contain no oil, paint, coatings, rubber, or plastics (other than incidental amounts). The
9 CDD/CDF emissions from such a clean charge, 0.27 ng TEQDF-WHO98/kg (0.26 ng I-TEQDF/kg)
10 charge material, would be expected to represent the low end of the normal industry range.
11 The second facility operated a sweat furnace to preclean the scrap and a reverberatory
12 furnace to smelt the precleaned aluminum (U.S. EPA, 1995h). Stack emissions were controlled
13 by an afterburner operated at 788 °C. The TEQ emission factor for this facility was 3.37 ng
14 TEQDF-WHO98/kg (3.22 ng I-TEQDF/kg) aluminum produced.
15 The third facility employed a crusher/roasting dryer as a precleaning step followed by a
16 reverberatory furnace (Galson Corporation, 1995). The emissions from the two units were
17 vented separately. The exhaust from the crusher/dryer was treated with an afterburner and a
18 fabric filter (FF). The exhaust from the furnace passed through an FF with lime injection. Both
19 stack exhausts were tested, and the combined TEQ emission factor was 13.55 ng TEQDF-
20 WHO98/kg (12.95 ng I-TEQDF/kg) aluminum produced. Because the activity level of the facility
21 at the time of sampling was treated as confidential business information, the calculated emission
22 factor was based on the reported typical production rates of the two operations: 26,000 Ib/hr for
23 the crusher/dryer and 6,700 Ib/hr for the furnace.
24 The fourth facility operated a scrap roasting dryer followed by a sidewell reverberatory
25 furnace (Envisage Environmental Inc., 1995). The emissions from the two units were vented
26 separately. Exhaust from the dryer passed through an afterburner and a lime-coated FF. The
27 exhaust from the furnace passed through a lime-coated FF. Both stack exhausts were tested, and
28 the combined TEQ emission factor was 37.94 ng TEQDF-WHO98/kg (36.03 ng I-TEQDF/kg) of
29 charge material. Problems with the scrap dryer were discovered after the testing was completed.
30 Also, operating conditions during testing were reported to represent more worst-case than typical
31 operations.
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1 The two facilities tested by CARB in 1992, which were reported in two confidential
2 reports (CARB, 1992a, b, as reported in U.S. EPA, 1997b) had TEQ emission factors of
3 consumed 55.68 and 23.44 ng TEQDF-WHO98/kg (52.21 and 21.67 ng I-TEQDF/kg) of scrap
4 aluminum. One facility was equipped with a venturi scrubber; the other was assumed to be
5 uncontrolled (U.S. EPA, 1997b).
6 The congener and congener group emission factors derived from these stack tests are
7 presented in Table 7-3. The average congener and congener group profiles are presented in
8 Figure 7-1. The average of the TEQ emission factors measured at the six tested facilities
9 (including the facility at which a specially formatted clean charge was used) is 22.4 ng TEQDF-
10 WHO98/kg (21.1 ng I-TEQDF/kg) of scrap feed. (Although the emission factors at two of the
11 facilities tested in 1995 are based on the output rather than the input rate, the two rates are
12 assumed, for purposes of this report, to be roughly equivalent.) Although the 1992 and 1995
13 testing was conducted at U.S. facilities, a low confidence rating is assigned to the average
14 emission factor because it is based on the results of testing at only six facilities, several of which
15 may have more effective APCDs than the other facilities in the industry.
16 For comparison purposes, the European Commission uses 22 ng I-TEQDF/kg scrap
17 aluminum as the typical emission factor for the European Dioxin Inventory (Quab and Fermann,
18 1997). Umweltbundesamt (1996) reported stack testing results for 25 aluminum smelters and
19 foundries in Germany. This study provided sufficient data to enable calculation of TEQ emission
20 factors for 11 of the tested facilities. The calculated emission factors ranged from 0.01 to 167 ng
21 I-TEQDF/kg of scrap feed. Three facilities had emission factors exceeding 100 ng I-TEQDF/kg,
22 and two facilities had emission factors of less than 1 ng I-TEQDF/kg. The mean emission factor
23 for the 11 facilities was 42 ng I-TEQDF/kg.
24 Approximately 727,000 metric tons of scrap aluminum were consumed by 67 secondary
25 aluminum smelters in 1987 (U.S. DOC, 1995c). In 1995, consumption of scrap aluminum by the
26 76 facilities that compose the secondary aluminum smelting industry had nearly doubled to 1.3
27 million metric tons (USGS, 1997a; The Aluminum Association, 1997). In 2000, secondary
28 aluminum smelters consumed 1.6 million metric tons of scrap aluminum (USGS, 2002). A high
29 confidence rating is assigned to these production estimates because they are based on government
30 survey data. Applying the I-TEQDF emission factor of 21.1 ng TEQ/kg of scrap feed to these
31 consumption values yields estimated annual emissions of 15.3 g I-TEQDF in 1987, 27.4 g I-TEQDF
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1 in 1995, and 33.8 g I-TEQDF in 2000. Applying the TEQDF-WHO98 emission factor of 22.4 ng
2 TEQ/kg to the consumption values yields estimated annual emissions of 16.3 g TEQDF-WHO98 in
3 1987, 29.1 g TEQDF-WHO98 in 1995, and 35.9 g TEQDF-WHO98 in 2000. These emission
4 estimates are assigned a low confidence rating because the rating given to the emission factor
5 was low.
6 It should be noted that a significant amount of scrap aluminum is also consumed by other
7 segments of the aluminum industry. However, this scrap is generally from metal manufacturing
8 processes, including metal and alloy production (e.g., borings, turnings, and dross), rather than
9 old scrap that results from recycling of consumer products (e.g., cans, radiators, auto shredders).
10 In 1995, integrated aluminum companies consumed 1.4 million metric tons of scrap aluminum
11 and independent mill fabricators consumed 0.68 million metric tons (USGS, 1997a).
12
13 7.2.2. Secondary Copper Smelters
14 Secondary copper smelting is part of the scrap copper, brass, and bronze reprocessing
15 industry. Brass is an alloy of copper and zinc; bronze is an alloy of copper and tin. Facilities in
16 this industry fall into three general classifications: secondary smelting, ingot making, and
17 remelting. Similar processing equipment may be used at all three types of facilities, so the
18 distinguishing features are not immediately apparent (U.S. EPA, 1994g).
19 The feature that distinguishes secondary smelters from ingot makers and remelters is the
20 extent to which pyrometallurgical purification is performed. A typical charge at a secondary
21 smelter may contain from 30 to 98% copper. The secondary smelter upgrades the material by
22 reducing the quantity of impurities and alloying materials, thereby increasing the relative
23 concentration of copper. This degree of purification and separation of the alloy constituents does
24 not occur at ingot makers and remelters. Feed material to a secondary copper smelter is a
25 mixture of copper-bearing scrap such as tubing, valves, motors, windings, wire, radiators,
26 turnings, mill scrap, printed circuit boards, telephone switching gear, and ammunition casings.
27 Nonscrap items like blast furnace slags and drosses from ingot makers or remelters may represent
28 a portion of the charge. The secondary smelter operator uses a variety of processes to separate
29 the alloy constituents. Some purify the scrap in the reductive atmosphere of a blast furnace and
30 then purify the charge in the oxidizing atmosphere of a converter. Other secondary smelters
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1 perform all purification by oxidation in top-blown rotary converters or in reverberatory furnaces
2 (U.S. EPA, 1994g).
3 The ingot makers blend and melt scrap copper, brass, and bronze of various compositions
4 to produce a specification brass or bronze ingot. When necessary, the ingot makers add ingots of
5 other metals (e.g., zinc or tin) to adjust the metallurgy of the final product. The feed materials for
6 ingot makers contain relatively high amounts of copper. Examples of feed materials include
7 copper tubing, valves, brass and bronze castings, ammunition shell casings, and automobile
8 radiators. "Fire-refined" anode copper or cathode copper may also be charged. Items such as
9 motors, telephone switchboard scrap, circuit board scrap, and purchased slags are not used by
10 ingot makers. The reductive step (melting in a reducing atmosphere, as in a blast furnace) that
11 some secondary smelters employ is not used by ingot makers. Ingot makers do, however, use
12 some of the other types of furnaces used by secondary smelters, including direct-fired converters,
13 reverberatory furnaces, and electric induction furnaces (U.S. EPA, 1994g).
14 Remelting facilities do not conduct substantial purification of the incoming feeds. These
15 facilities typically melt the charge and then cast or extrude a product. The feeds to a remelter are
16 generally alloy material of approximately the desired composition of the product (U.S. EPA,
17 1994g).
18
19 7.2.2.1. Emissions Data
20 Stack emissions of CDDs/CDFs from a secondary copper smelter were measured by EPA
21 during 1984 and 1985 as part of the National Dioxin Tier 4 Study (U.S. EPA, 1987a). The
22 facility chosen for testing was estimated to have a high potential for CDD/CDF emissions
23 because of the abundance of chlorinated plastics in the feed. This facility ceased operations in
24 1986. The facility was chosen for testing by EPA because the process technology and air
25 pollution control equipment in place were considered typical for the source category. Copper and
26 iron-bearing scrap were fed in batches to a cupola blast furnace, which produced a mixture of
27 slag and black copper. Approximately 4 to 5 tons of metal-bearing scrap were fed to the furnace
28 per charge, with materials typically being charged 10 to 12 times per hour. Coke fueled the
29 furnace and represented approximately 14% (by weight) of the total feed. During the stack tests,
30 the feed consisted of electronic telephone scrap and other plastic scrap, brass and copper shot,
31 iron-bearing copper scrap, precious metals, copper-bearing residues, refinery by-products,
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1 converter furnace slag, anode furnace slag, and metallic floor-cleaning material. The telephone
2 scrap made up 22% (by weight) of the feed and was the only scrap component that contained
3 plastic materials. Oxygen-enriched combustion air for combustion of the coke was blown
4 through tuyeres (nozzles) at the bottom of the furnace. At the top of the blast furnace were four
5 natural gas-fired afterburners to aid in completing combustion of the exhaust gases. Fabric
6 filters (FFs) controlled particulate emissions, and the flue gas was then discharged into a
7 common stack. The estimated emission factors derived for this site are presented in Table 7-4.
8 The emission factors are based on the total weight of scrap fed to the furnace. Based on the
9 measured congener and congener group emission factors, the TEQ emission factor is 779 ng I-
10 TEQDF/kg (810 ng TEQDF.WHO98/kg) of scrap metal smelted. Figure 7-2a presents the congener
11 group profile based on these emission factors.
12 In 1992, stack testing of the blast furnace emissions of a secondary smelter located in
13 Philadelphia, Pennsylvania (Franklin Smelting and Refining Co.), was conducted by Applied
14 Geotechnical & Environmental Services Corporation (AGES, 1992). Similar to the facility
15 tested by EPA in 1984-1985, this facility processed low-purity copper-bearing scrap, telephone
16 switch gear, and slags, as well as higher copper content materials (U.S. EPA, 1994g). The
17 facility used a blast (cupola-type) furnace coupled with a pair of rotary converters to produce
18 blister copper. The blast furnace used coke as both the fuel and the agent to maintain a reducing
19 atmosphere. The black copper-slag mixture from the blast furnace was charged to the rotary
20 converters for further refining with the aid of oxygen, sand, and oak logs (AGES, 1992; U.S.
21 EPA, 1994g). The APCD equipment installed on the blast furnace included an afterburner,
22 cooling tower, and baghouse. During testing, the afterburner was reported to be operating
23 erratically and was particularly low during one of the two sampling episodes. Stack gas flow was
24 also low during both sampling episodes because one or more baghouse compartments were
25 inoperable (AGES, 1992). The estimated emission factors derived for this site from the AGES
26 results are presented in Table 7-4. The emission factors are based on the total weight of scrap fed
27 to the blast furnace. The TEQ emission factor was 16,618 ng I-TEQDF/kg (16,917 ng TEQDF-
28 WHO98/kg) of scrap. Figure 7-2b presents the congener and congener group profiles based on
29 these emission factors.
30 In 1991, stack testing of the rotary furnace stack emissions of a secondary smelter
31 (Chemetco, Inc.) located in Alton, Illinois, was conducted by Sverdrup Corp. (1991). The
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1 Chemetco facility used four tap-down rotary (i.e., oxidizing) furnaces. Furnace processed gas
2 emissions were controlled by a primary quencher and a venturi scrubber. The feed was relatively
3 high-purity copper scrap containing minimal, if any, plastics. The same manufacturing process
4 and APCD equipment were in place in 1987 and 1995 (U.S. EPA, 1994g). Because this facility
5 operated under oxidizing rather than reducing conditions and processed relatively high-purity
6 scrap, the potential for CDD/CDF formation and release was expected to be dramatically
7 different from that of the two tested facilities reported above. The estimated emission factors
8 derived for this site from the results of Sverdrup Corp. (1991) are presented in Table 7-4. The
9 emission factors are based on the total weight of scrap feed going to the furnace. The TEQ
10 emission factor was 3.60 ng I-TEQDF/kg (3.66 ng TEQDF-WHO98/kg) of scrap.
11 Only limited data on emissions from secondary copper smelters are reported in the
12 European Dioxin Inventory (LUA, 1997). TEQ emission factors reported for German shaft
13 furnaces/converters and reverberatory furnaces range from 5.6 to 110 ng I-TEQDF/kg and from
14 0.005 to 1.56 ng I-TEQDF/kg, respectively. Emission factors reported for two smelter and casting
15 furnaces in Sweden in which relatively clean scrap is used as input are 0.024 and 0.04 ng I-
16 TEQDF/kg. A smelter in Austria is reported to have a TEQ emission factor of 4 ng I-TEQDF/kg.
17 The minimum, typical, and maximum default emission factors selected in LUA are 5, 50, and
18 400 ng I-TEQDF/kg, respectively.
19 In the 2002 Environment Canada report on CDD/CDF emissions from the base metals
20 smelting sector (Charles E. Napier Company, Ltd., 2002), three secondary copper smelters were
21 identified (see Table 7-2). CDD/CDF emission concentrations were reported as ranging from
22 less than 100 to less than 500 pg I-TEQ/dscm.
23
24 7.2.2.2. Activity-Level Information
25 In 1987, four secondary copper smelters were in operation: Franklin Smelting and Refining Co.
26 (Philadelphia, Pennsylvania), Chemetco, Inc. (Alton, Illinois), Southwire Co. (Carrollton,
27 Georgia), and a facility located in Gaston, South Carolina, that was owned by American
28 Telephone and Telegraph (AT&T) until 1990 when it was purchased by Southwire Co. In 1987,
29 estimated smelter capacities were 13,600 metric tons for the Franklin facility, 120,000 metric
30 tons for the Chemetco facility, 48,000 metric tons for the Southwire facility, and 85,000 metric
31 tons for the AT&T facility (Edelstein, 1999). In 1995, only three of these four facilities were in
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1 operation. The Southwire facility in Gaston (previously owned by AT&T) was closed in January
2 1995. The Franklin facility subsequently ceased operations in August 1997. Estimated smelter
3 capacities in 1995 were 16,000 metric tons for the Franklin facility, 135,000 metric tons for the
4 Chemetco facility, and 92,000 metric tons for the Southwire facility (Edelstein, 1999). In May
5 2000, the Southwire Co. closed its facility and ceased operations (Edelstein, 2000). In November
6 2001, Chemetco closed its facility and ceased operations (Edelstein, 2001). According to
7 Edelstein (2001), smelters and refineries consumed 255,000 metric tons of purchased copper-
8 based scrap in 2000 and 196,000 metric tons in 2001. Assuming Chemetco was the sole smelter
9 facility in 2001, and that Chemetco operated for 10 of 12 months in 2001, Chemetco's estimated
10 annual consumption of copper-based scrap would be 235,000 metric tons per year. Assuming
11 Chemetco's annual consumption rate did not change from 2000 to 2001, the estimated
12 consumption of copper-based scrap for the Southwire Co. in 2000 would have been 20,000
13 metric tons.
14
15 7.2.2.3. Emission Estimates
16 Although little research has been done to define the CDD/CDF formation mechanisms in
17 secondary copper smelting operations, two general observations have been made (Buekens et al.,
18 1997). The presence of chlorinated plastics in copper scraps used as feed for smelters is believed
19 to increase the CDD/CDF formation. Second, the reducing or pyrolytic conditions in blast
20 furnaces can lead to high CDD/CDF concentrations in the furnace process gases. As noted in
21 Section 7.2.2.1, two of the U.S. facilities that have been tested (i.e., U.S. EPA, 1987a; AGES,
22 1992) had the following characteristics: both processed low-purity scrap containing significant
23 quantities of plastics and both used blast furnaces. The APCD equipment at both facilities
24 consisted of an afterburner, a cooling tower (Franklin facility only), and an FF (U.S. EPA,
25 1994g). The other tested U.S. facility used oxidizing rather than reducing conditions and
26 processed relatively high-purity scrap (Sverdrup, 1991).
27 Annual TEQ emissions for 1987, 1995, and 2000 were derived as the sum of the TEQ
28 emissions for each secondary copper facility in operation during the reference years. The
29 following discussion summarizes the procedure used to estimate annual TEQ air emissions.
30 The Franklin Smelting facility operated in 1987 and 1995 but not in 2000. The TEQ
31 emission factor measured at this facility in 1992 is assumed to be representative of the TEQ
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1 emission factor in 1987 and 1995. Combining this emission factor (16,618 ng I-TEQDF/kg
2 [16,917 ng TEQDF-WHO98/kg] of scrap feed) with the estimated smelter capacities (data are not
3 available on the amount of scrap processed) for this facility in 1987 (13,600,000 kg) and 1995
4 (16,000,000 kg) yields TEQ emission estimates of 226 g I-TEQDF (230 g TEQDF-WHO98) in 1987
5 and 266 g I-TEQDF (271 g TEQDF-WHO98) in 1995. This facility ceased operations in 1997.
6 The Chemetco facility operated in 1987, 1995, and 2000. Similarly, for purposes of this
7 report, the TEQ emission factor for the Chemetco facility is considered to be representative of the
8 TEQ emission factor for this facility for 1987, 1995, and 2000. Combining this emission factor
9 (3.60 ng I-TEQDF/kg [3.66 ng TEQDF-WHO98/kg] of scrap feed) with the estimated smelter
10 capacities of 120,000,000 kg in 1987 and 135,000,000 kg in 1995 yields TEQ estimates of 0.43 g
11 I-TEQDF (0.44 g TEQDF-WHO98) in 1987 and 0.49 g I-TEQDF (0.49 g TEQDF-WHO98) in 1995.
12 Combining the same emission factor with the scrap consumption for this facility in 2000
13 (235,000,000 kg) yields a TEQ estimate of 0.85 g I-TEQDF (0.86 g TEQDF-WHO98) for 2000.
14 The facility in Gaston, South Carolina, was in operation during 1987 but ceased
15 operations in 1995. Prior to 1990, when this facility was owned by AT&T, the plant processed a
16 great deal of high-plastics-content scrap (such as whole telephones). This scrap was fed to a
17 pyrolysis unit prior to entering the blast furnace. In addition to a blast furnace, the facility also
18 had an oxidizing reverberatory furnace for processing higher purity scrap. The facility had
19 separate FFs for the blast furnace, the converters, and the reverberatory furnace (U.S. EPA,
20 1994g). Because this facility processed low-purity, high-plastics-content scrap in 1987, and
21 presumably processed much of this in the reducing atmosphere of a pyrolysis unit and blast
22 furnace, the average of the TEQ emission factors for the Tier 4 (U.S. EPA, 1987a) and Franklin
23 facilities (8,700 ng I-TEQDF/kg [8,860 ng TEQDF-WHO98/kg]) was used to estimate potential
24 emissions in 1987 of 740 g I-TEQDF (753 g TEQDF-WHO98) (assuming an activity level of
25 85,000,000 kg). This activity level is the estimated capacity of the facility; data were not
26 available on the amount of scrap processed.
27 The Southwire facility had both a blast furnace and a reverberatory furnace. In 1992,
28 approximately 50% of incoming scrap was processed in each furnace (U.S. EPA, 1994g). Unlike
29 the two tested facilities and the Gaston facility, the Southwire facility stopped processing plastic-
30 coated scrap in the 1970s. In addition, this facility had a more complex APCD system, which
31 may have reduced the formation and release of CDDs/CDFs. The blast furnace processed gases
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1 passed through an afterburner (871°C), U-tube coolers, and an evaporative spray system before
2 entering the FF at a temperature of 107 to 191°C. For these reasons, EPA has determined that
3 the existing emissions data for secondary smelters cannot reliably be used to generate a
4 quantitative estimate of potential emissions during 1987, 1995, or 2000 for this facility.
5 Total secondary copper smelter emissions for 1987 are the sum of the Franklin smelting
6 facility emissions (271 g TEQDF-WHO98 or 266 g I-TEQDF), the Chemetco smelter facility (0.44 g
7 TEQDF-WHO98 or 0.43 g I-TEQDF ) and the Gaston, South Carolina, facility (753 g TEQDF-
8 WHO98 or 740 g I-TEQDF). Total secondary copper smelter emissions for 1987 are 983.44 g
9 TEQDF-WH098 (966.43 g I-TEQDF).
10 Total secondary copper smelter emissions for 1995 are the sum of the Franklin smelting
11 facility emissions (271 g TEQDF-WHO98 266 g I-TEQ DF) and the Chemetco smelter facility (0.49
12 g TEQDF-WHO98 or 0.49 g TEQDF-WHO98 ). Total secondary copper smelter emissions for 1995
13 are 271.49 g TEQDF-WHO98 (266.49 I-TEQDF).
14 The Chemetco smelter provides the TEQ emissions estimate for the year 2000. Total
15 secondary copper smelter emissions for 2000 are 0.86 g TEQDF-WHO98 (0.85 g I-TEQDF).
16 A high confidence rating is assigned to the production and consumption estimates because they
17 are based on government survey data. A low confidence rating is assigned to the TEQ emission
18 estimates because they are based on limited measurements made at three smelters, one of which
19 was not in operation in 1987 or 1995.
20 It should be noted that a significant amount of scrap copper is consumed by other
21 segments of the copper industry. In 1995 and 2000, brass mills and wire-rod mills consumed
22 886,000 and 1,070,000 metric tons of copper-based scrap, respectively; foundries and
23 miscellaneous manufacturers consumed 71,500 and 96,200 metric tons, respectively (USGS,
24 1997a; Edelstein, 2001). As noted above, however, these facilities generally do not conduct any
25 significant purification of the scrap. Rather, the scrap consumed is already of alloy quality, and
26 processes employed typically involve only melting, casting, and extruding. Thus, the potential
27 for formation of CDDs/CDFs is expected to be much less than the potential during secondary
28 smelting operations.
29
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1 7.2.3. Secondary Lead Smelters
2 The secondary lead smelting industry produces elemental lead through the chemical
3 reduction of lead compounds in a high-temperature furnace (1,200 to 1,260 °C). Smelting is
4 performed in reverberatory, blast, rotary, or electric furnaces. Blast and reverberatory furnaces
5 are the most common types of smelting furnaces used by the 23 facilities that make up the
6 current secondary lead smelting industry in the United States. Of the 45 furnaces at these 23
7 facilities, 15 are reverberatory furnaces, 24 are blast furnaces, 5 are rotary furnaces, and 1 is an
8 electric furnace. The electric furnace and 11 of the 24 blast furnaces are co-located with
9 reverberatory furnaces, and most share a common exhaust and emissions control system (U.S.
10 EPA, 1994h).
11 Furnace charge materials consist of lead-bearing raw materials, lead-bearing slag and
12 drosses, fluxing agents (blast and rotary furnaces only), and coke. Scrap motor vehicle lead-acid
13 batteries represent about 90% of the lead-bearing raw materials at a typical lead smelter. Fluxing
14 agents consist of iron, silica sand, and limestone or soda ash. Coke is used as fuel in blast
15 furnaces and as a reducing agent in reverberatory and rotary furnaces. Organic emissions from
16 co-located blast and reverberatory furnaces are more similar to the emissions of a reverberatory
17 furnace than to those of a blast furnace (U.S. EPA, 1994h).
18 In 1987, the lead smelting industry consisted of 24 facilities producing 0.72 million
19 metric tons of lead (U.S. EPA, 1994h). In 1995, there were 23 companies producing 0.97 million
20 metric tons (USGS, 1997a), and in 2000 there were 27 secondary lead smelters in operation in
21 the United States producing 1.02 million metric tons (USGS, 2002). In 1995, the total annual
22 production capacity of the 23 companies that made up the U.S. lead smelting industry was 1.36
23 million metric tons. Blast furnaces not co-located with reverberatory furnaces accounted for 21%
24 of capacity (or 0.28 million metric tons). Reverberatory furnaces and blast and electric furnaces
25 co-located with reverberatory furnaces accounted for 74% of capacity (or 1.01 million metric
26 tons). Rotary furnaces accounted for the remaining 5% of capacity (or 0.07 million metric tons)
27 (U.S. EPA, 1994h).
28 Actual production volume statistics by furnace type were not available. However, if it is
29 assumed that the total actual production volume of the industry reflects the production capacity
30 breakdown by furnace type, then the estimated actual production volumes of blast furnaces (not
31 co-located), reverberatory and co-located blast/electric and reverberatory furnaces, and rotary
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1 furnaces were 0.15, 0.53, and 0.04 million metric tons, respectively, in 1987; 0.2, 0.72, and 0.05
2 million metric tons, respectively, in 1995; and 0.29, 1, and 0.07 million metric tons, respectively,
3 in 2000.
4 A report commissioned by Environment Canada (Charles E. Napier Company, Ltd.,
5 2000) reviewed published literature and other information on the dioxin/furan formation
6 mechanisms; dioxin/furan emissions; emission control technology, including cost; and
7 dioxin/furan published emission standards pertinent to steel production processes of plants in
8 Canada. The report included four facilities identified as primary lead smelters (see Table 7-5).
9 CDD/CDF emission concentrations were reported to range from less than 100 to less than 1,000
10 pg I-TEQ/dscm.
11 CDD/CDF emission factors were estimated for lead smelters using the results of emission
12 tests performed by EPA at three smelters (a blast furnace [U.S. EPA, 1995e], a co-located
13 blast/reverberatory furnace [U.S. EPA, 1992e], and a rotary kiln furnace [U.S. EPA, 1995d]).
14 The air pollution control systems at the three tested facilities consisted of both FFs and scrubbers.
15 Congener-specific measurements were made at both APCD exit points at each facility. Table 7-6
16 presents the congener and congener group emission factors for the FF and the scrubber for each
17 site. Figure 7-3 presents the corresponding profiles for the FF emissions from the tested blast
18 furnace and reverberatory furnace. For the facilities in operation in 1995, all 23 smelters
19 employed FFs, with only 9 employing scrubber technology. Facilities with scrubbers accounted
20 for 14% of the blast furnace (not co-located) production capacity, 52% of the reverberatory and
21 co-located furnace production capacity, and 57% of the rotary furnace production capacity. TEQ
22 emission factors (ng TEQ/kg lead produced when nondetect values are set equal to zero) from the
23 reported data for each of the three furnace configurations, presented as a range reflecting the
24 presence or absence of a scrubber, are:
25
26 • Blast furnace: 0.64 to 8.81 ng TEQDF-WHO98/kg (0.63 to 8.31 ng I-TEQDF/kg)
27
28 • Reverberatory/co-located furnace: 0.05 to 0.42 ng TEQDF-WHO98/kg (0.05 to 0.41 ng
29 I-TEQDF/kg)
30
31 • Rotary furnace: 0.24 to 0.66 ng TEQDF-WHO98/kg (0.24 to 0.66 ng I-TEQDF/kg)
32
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1
2
3
4
5
6
7
8
9
10
11
12
13
If these ranges of emission rates are assumed to be representative of those at nontested
facilities with the same basic furnace configuration, with and without scrubbers, then combining
these emission rates with the estimated production volumes derived above and the percentage of
each configuration type that have scrubbers yields the following estimated air emissions in g I-
TEQDF for 1987, 1995, and 2000:
A medium confidence rating is assigned to the emission factors because stack test data
were available for 3 of the 27 smelters operating in the United States (of which only 16 were in
operation as of December 1993), and the stack test data used represent the three major furnace
configurations. The activity level estimate has been assigned a medium confidence rating
because, although it is based on a U.S. Department of Commerce estimate of total U.S.
production, no production data were available on a furnace type or furnace configuration basis.
Therefore, a medium confidence rating is assigned to the emission estimates.
Configuration
Blast furnaces w/scrubbers
Blast furnaces w/o scrubbers
Reverberatory furnaces
w/scrubbers
Reverberatory furnaces w/o
scrubbers
Rotary furnaces w/scrubbers
Rotary furnaces w/o scrubbers
TOTAL
Estimated annual TEQ emissions (g TEQ)a
Ref. year 1987
TEQDF-
WH098
0.013
1.136
0.014
0.106
0.015
0.004
1.288
I-TEQDF
0.013
1.072
0.014
0.104
0.015
0.004
1.223
Ref. year 1995
TEQDF-
WH098
0.018
1.515
0.019
0.145
0.019
0.005
1.721
I-TEQDF
0.018
1.429
0.019
0.142
0.019
0.005
1.632
Ref. year 2000
TEQDF-
WH098
0.026
2.197
0.026
0.202
0.026
0.007
2.484
I-TEQDF
0.026
2.073
0.026
0.197
0.026
0.007
2.354
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Calculated using emission factors based on nondetect values set equal to zero.
7.3. PRIMARY FERROUS METAL SMELTING/REFINING
Iron is manufactured from its ores (magnetic pyrites, magnetite, hematite, and carbonates
of iron) in a blast furnace, and the iron obtained from this process is further refined in steel plants
to make steel. The primary production of iron and steel involves two operations identified by
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1 European researchers as potential emission sources of CDDs/CDFs: iron ore sinter production
2 and coke production. Each of these potential sources is discussed in the following subsections.
3
4 7.3.1. Sinter Production
5 At some iron manufacturing facilities, iron ores and waste iron-bearing materials undergo
6 sintering to convert the materials to usable feed for the blast furnace. In the sintering process,
7 iron ore fines and waste materials are mixed with coke fines and the mixture is placed on a grate
8 that is then heated to a temperature of 1,000 to 1,400 °C. The heat generated during combustion
9 sinters the small particles. Iron-bearing dusts and slags from processes in the steel plant are the
10 types of iron-bearing waste materials used as a feed mix for the sinter plant (Knepper, 1981;
11 Capes, 1983; U.S. EPA, 1995b).
12 Several European investigators have reported that iron ore sinter plants are major sources
13 of airborne emissions of CDDs/CDFs (Rappe, 1992b; Lexen et al., 1993; Lahl, 1993, 1994).
14 Lahl reported that the practice of recycling dusts and scraps from other processes in the steel
15 plant for use in the sintering plant introduces traces of chlorine and organic compounds that
16 generate the CDDs/CDFs found in these plants.
17 Organic compounds that are potential precursors to CDD/CDF formation come primarily
18 from oil, which is found in mill scale, as well as some blast furnace sludges that are used as part
19 of the sinter feed mixture. Most U.S. plants limit the amount of oil because it increases
20 emissions of volatile organic compounds and may create a fire hazard. In addition, plants with
21 FFs must limit the oil content because the oil tends to blind the FFs. Typical oil content of the
22 feed at U.S. sinter plants ranges from 0.1 to 0.75% (Calcagni et al., 1998).
23 Sinter plants in Sweden have been reported to emit up to 3 ng I-TEQDF/Nm3 stack gas, or
24 2 to 4 g I-TEQDF/yr (Rappe, 1992b; Lexen et al., 1993). Bremmer et al. (1994) reported the
25 results of stack testing at three iron ore sintering plants in the Netherlands. One facility equipped
26 with wet scrubbers (WSs) had an emission factor of 1.8 ng I-TEQDF/dscm (at 11% oxygen). The
27 other two facilities, both equipped with cyclones, had emission factors of 6.3 and 9.6 ng I-
28 TEQDF/dscm (at 7% oxygen). Lahl (1993, 1994) reported stack emissions for sintering plants in
29 Germany (after passage through mechanical filters and electrostatic precipitators) ranging from 3
30 to 10 ng I-TEQDF/Nm3. A compilation of emission measurements by the German Federal
31 Environmental Agency indicated stack emission concentrations ranging from 1.2 to 60.6 ng I-
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1 TEQDF/m3 (at 7% oxygen); the majority of emissions in 1996 were around 3 ng I-TEQDF/m3
2 (Umweltbundesamt, 1996).
3 The report commissioned by Environment Canada in 2000 to review steel production
4 processes in Canadian plants (Charles E. Napier Company, Ltd., 2000) included information on
5 emissions from iron sintering. For iron sintering, the CDD/CDF emissions from one facility, the
6 Stelco Hilton Works sinter plant, were assumed to be representative of the 1998 sinter
7 production. The average emission rate was 19.9 ng I-TEQ/day. Applying a production rate of
8 1,143 metric tons/day yields a mass emission factor of 17.4 ng I-TEQ/kg of sinter.
9 EPA conducted tests at two of the nine U.S. sinter plants operating in 1997 in order to
10 quantify emissions of CDDs/CDFs (Calcagni et al., 1998). In choosing representative plants for
11 testing, EPA considered a variety of issues, including the types and quantities of feed materials,
12 the types of emission controls, and the oil content of the sinter feed. EPA decided to test a plant
13 with an FF and a plant with a venturi (or wet) scrubber. FFs and WSs are the principal APCDs
14 used to control emissions from the sinter plant windbox. Four plants used an FF and five plants
15 used a WS. The types of feed materials and oil content at the two selected plants were
16 determined to be representative of other plants in the industry. Sampling was performed over 3
17 days (4 hr/day) at each plant.
18 The average CDD/CDF TEQ concentrations measured in the stack emissions were 0.19
19 ng I-TEQDF/Nm3 and 0.81 ng I-TEQDF/Nm3 for the WS and the FF, respectively. The
20 corresponding TEQ emission factors are 0.62 ng TEQDF-WHO98/kg (0.55 ng I-TEQDF/kg) sinter
21 and 4.61 ng TEQDF-WHO98/kg (4.14 ng I-TEQDF/kg) sinter, respectively, for WSs and FFs.
22 These emission factors are assigned a high rating because they are based on EPA testing at two
23 facilities considered by EPA to be representative of both current and 1995 standard industry
24 practices.
25 Congener-specific emission factors for these two facilities are presented in Table 7-7.
26 Figure 7-4 presents the congener profiles for these facilities. Although concentrations were
27 higher from the FF than from the scrubber, both concentrations were low relative to what had
28 been reported from testing at German, Dutch, Swedish, and Canadian sinter plants. These
29 differences may be due to differences between the operation or APCDs of U.S. sinter plants and
30 the tested European plants.
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1 Most of the U.S. integrated iron and steel plants, including those with sinter plants, have
2 eliminated the purchase and use of chlorinated organics in their facilities. Their rolling mill oils
3 (lubricants and hydraulic fluids) do not contain chlorinated compounds. In addition, routine
4 analysis of waste materials going to the sinter plant have not detected any chlorinated solvents.
5 Finally, none of the U.S. plants use an ESP to control emissions from the sinter windbox
6 (Calcagnietal., 1998).
7 In 1996 (data were not readily available for 1995), 11 sintering plants were operating in
8 the United States, with a total annual production capacity of about 17.6 million metric tons
9 (Metal Producing, 1996). Since the 1980s, the size of this industry has decreased dramatically.
10 In 1982, 33 facilities were in operation, with a combined total capacity of 48.3 million metric
11 tons (U.S. EPA, 1982b). The nine U.S. sinter plants operating in 1995 had a combined capacity
12 of 15.6 million metric tons (Calcagni et al., 1998). In 1987, sinter consumption by iron and steel
13 plants was 14.5 million metric tons (AISI, 1990); in 1995, consumption was 12.4 million metric
14 tons (Fenton, 1996), or approximately 70% of production capacity, assuming that production
15 capacity in 1995 was the same as in 1996. These activity level estimates are assigned a
16 confidence rating of medium.
17 As shown in Table 7-8, 59% of 1998 sinter production capacity was at facilities with WSs
18 and 41% was at facilities with FFs. If it is assumed that these proportions of APCD-to-
19 production capacity existed in 1995 and that actual production in 1995 was equal to sinter
20 consumption at iron and steel plants (12.4 million metric tons), then estimated TEQ emissions
21 from WS-equipped facilities were 4.5 g TEQDF-WHO98 (4 g I-TEQDF) and emissions from FF-
22 equipped facilities were 23.4 g TEQDF-WHO98 (21 g I-TEQDF), for a total of 27.9 g TEQDF-
23 WHO98 (25.1 g I-TEQDF). These emission estimates are assigned an overall medium confidence
24 rating on the basis of the medium rating for the activity level estimates.
25 If these same assumptions are applied to the 1987 sinter consumption rate of 14.5 million
26 metric tons, then estimated TEQ emissions from WS-equipped facilities were 5.3 g TEQDF-
27 WHO98 (4.7 g I-TEQDF) and emissions from FF-equipped facilities were 27.4 g TEQDF-WHO98
28 (24.6 g I-TEQDF), for a total of 32.7 g TEQDF-WHO98 (29.3 g I-TEQDF). These emission
29 estimates are less certain than the estimates for 1995 because of uncertainties concerning actual
30 APCDs in place in 1987 and the content of waste feed (i.e., oil content and presence of
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1 chlorinated organics in the oil) at that time. Consequently, a low confidence rating is assigned to
2 the emission factor and the emission estimate.
3 In 2000, a total of 10,600 million metric tons of sinter were consumed in blast furnaces
4 (Fenton, 2001). This activity level has a high confidence rating because it is based on a
5 comprehensive survey. Assuming the same proportions for facilities with wet scrubbers and
6 facilities with fabric filters as was done for 1995 and 1987, then estimated TEQ emissions from
7 wet scrubber-equipped facilities were 3.9 g TEQDF-WHO98 (3.4 g I-TEQDF) and emissions from
8 fabric filter-equipped facilities were 23.7 g TEQDF-WHO98 (21.3 g I-TEQDF), for a total of 27.6
9 TEQDF-WHO98 (24.4 g I-TEQDF) for the year 2000. This emission estimate is assigned a high
10 confidence rating based on the high ratings given to the activity level and emission factor for
11 reference year 2000.
12
13 7.3.2. Coke Production
14 Coke is the principal fuel used in the manufacture of iron and steel. It is the solid
15 carbonaceous material produced by the destructive distillation of coal in high-temperature ovens.
16 No testing of CDD/CDF emissions from U.S. coke facilities has been reported. However, at a
17 facility in the Netherlands, Bremmer et al. (1994) measured a CDD/CDF emission rate to air
18 during the water quenching of hot coke of 0.23 ng I-TEQDF/kg of coal consumed. Bremmer et al.
19 estimated minimal CDD/CDF air emissions (0.002 ng I-TEQDF/kg of coal) for flue gases
20 generated during the charging and emptying of the coke ovens.
21 The report commissioned by Environment Canada in 2000 to review steel production
22 processes in Canadian plants (Charles E. Napier Company, Ltd., 2000) also provided information
23 on emissions from coke ovens. For coke making and coke ovens, emissions were estimated on
24 the basis of plant capacity and estimated production and were reported as 0.3 ng I-TEQ/kg coke
25 produced (see Table 7-5).
26 Although no testing of CDD/CDF emissions from U.S. coke plants has been reported
27 upon which to base an estimate of national emissions, a preliminary estimate of potential TEQ
28 annual emissions from U.S. coke plants can be made by combining the estimated consumption
29 values of 33.5 million metric tons in 1987, 29.9 million metric tons in 1995, and 26.2 million
30 metric tons in 2000 (EIA, 2002), with the emission factor reported by Bremmer et al. (1994) for a
31 Dutch coke plant (0.23 ng I-TEQDF/kg of coal consumed). These calculations yield annual
03/04/05 7-24 DRAFT—DO NOT CITE OR QUOTE
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1 emissions of 7.7, 6.9, and 6.03 g I-TEQDF for 1987, 1995, and 2000, respectively. These
2 estimates should be regarded as preliminary indications of possible emissions from this source
3 category; further testing is needed to confirm the true magnitude of these emissions.
4
5 7.4. SECONDARY FERROUS METAL SMELTING/REFINING
6 Electric arc furnaces in Europe have been reported to be sources of CDD/CDF emissions;
7 no testing has been reported at U.S. facilities. Electric arc furnaces are used to produce carbon
8 and steel alloys, primarily from scrap material, using a batch process. The input material is
9 typically 100% scrap. Scrap, alloying agents, and fluxing materials are loaded into the
10 cylindrical, refractory-lined furnace, and then carbon electrodes are lowered into the mix. The
11 current of the opposite polarity electrodes generates heat through the scrap. Processing time of a
12 batch ranges from about 1.5 to 5 hr to produce carbon steel and from 5 to 10 hr to produce alloy
13 steel (U.S. EPA, 1995b).
14 The melting of scrap ferrous material contaminated with metalworking fluids and plastics
15 that contain chlorine provides the conditions conducive to formation of CDDs/CDFs. Tysklind
16 et al. (1989) studied the formation and release of CDDs/CDFs at a pilot 10-ton electric furnace in
17 Sweden. Scrap ferrous metal feedstocks containing varying amounts of chlorinated compounds
18 (PVC plastics, cutting oils, or calcium chloride) were charged into the furnace under different
19 operating conditions (continuous feed, batch feed into the open furnace, or batch feed through the
20 furnace lid). During continuous charging operations, the highest emissions, 1.5 ng Nordic
21 TEQ/dry Nm3 (after an FF), were observed with a feedstock consisting of scrap metal with PVC
22 plastics (1.3 g chlorine/kg feedstock). This emission rate equates to 7.7 ng Nordic TEQ/kg of
23 feedstock.
24 The highest emissions during batch charging also occurred when the scrap metal with
25 PVC plastic was combusted (0.3 ng Nordic TEQ/dry Nm3 or 1.7 ng Nordic TEQ/kg of
26 feedstock). Much lower emissions (0.1 ng Nordic TEQ/dry Nm3 or 0.6 ng Nordic TEQ/kg of
27 feedstock) were observed when scrap metal with cutting oils that contained chlorinated additives
28 (0.4 g chlorine/kg feedstock) was melted. Although these cutting oil-related emissions were not
29 significantly different from the emissions observed from the melting of no-chlorine scrap metal,
30 relatively high levels of CDDs/CDFs (110 ng Nordic TEQ/dry Nm3) were detected in flue gases
31 prior to the FF.
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1 The congener profiles of raw flue gas samples (prior to the APCD) showed that CDFs
2 rather than CDDs were predominant in all three feedstock types. The congener profile from the
3 test burn with PVC-containing feedstock showed a higher chlorinated congener content than was
4 observed with the other feedstocks.
5 Eduljee and Dyke (1996) used a range of 0.7 to 10 ng I-TEQDF/kg of scrap feed to
6 estimate national emissions for the United Kingdom. This range was assumed to be
7 representative of no-chlorine and high-chlorine operations. However, the study authors provided
8 little information on the supporting emission test studies (i.e., tested facility operational
9 materials, feed rates, congener-specific emission rates).
10 Umweltbundesamt (1996) reported stack testing results for a variety of electric arc
11 furnaces in Germany. Sufficient data were provided in the report to enable calculation of TEQ
12 emission factors for six of the tested facilities. Two facilities had emission factors exceeding 1
13 ng I-TEQDF/kg of scrap processed, and two facilities had emission factors less than 0.1 ng I-
14 TEQDF/kg of scrap. The mean emission factor was 1.15 ng I-TEQDF/kg of scrap. The TEQ
15 concentrations in the stack gases at these facilities (corrected to 7% oxygen) ranged from less
16 than 0.1 to 1.3 ng I-TEQDF/m3.
17 The report commissioned by Environment Canada in 2000 to review steel production
18 processes at Canadian plants (Charles E. Napier Company, Ltd., 2000) included information on
19 emissions from iron sintering and provided information on emissions from electric arc furnaces,
20 which were estimated on the basis of plant capacity and estimated production. An average
21 emission factor of 2.1 ng I-TEQDF/kg steel produced was developed (see Table 7-5).
22 In March 2000, Environment Canada reported on source testing for the determination of
23 CDD/CDF emissions from a facility in Ontario (Cianciarelli, 2000). Sampling was conducted on
24 the exhaust stack of the electric arc furnace of Dofasco Inc., and both concentrations and
25 emission rates were provided (see Table 7-9). Total CDD/CDF concentrations were reported to
26 be 51.15 pg TEQ/m3, and the total emission rate was reported to be 0.47 ng TEQ/kg steel
27 produced. In August 2000, the Emissions Research and Measurement Division of Environment
28 Canada conducted source testing to determine CDDs/CDFs from the electric arc furnace of
29 another facility, Gerdau Courtice Steel Inc. (Cianciarelli, 200la). These results (presented in
30 Table 7-9) are being used to support the Canadian dioxin/furan inventory for electric arc
03/04/05 7-26 DRAFT—DO NOT CITE OR QUOTE
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1 furnaces. The total CDD/CDF concentrations were reported to be 125.5 pg TEQ/m3, and the
2 total emission rate was reported to be 1.1 ng TEQ/kg steel produced.
3 In 1987, electric arc furnaces accounted for 38.1% of U.S. steel production, or 30.8
4 billion kg of raw steel produced (Peters, 1988). In 1995, electric arc furnaces accounted for
5 40.4% of U.S. steel production, or 38.4 of the total 95.2 million metric tons of raw steel produced
6 (Fenton, 1996). In 2000, electric arc furnaces accounted for 46.2% of U.S. steel production, or
7 49 of the 106 million metric tons of raw steel produced (USGS, 2002).
8 No testing of CDD/CDF emissions from U.S. electric arc furnaces on which to base an
9 estimate of national emissions has been reported. A preliminary estimate of potential TEQ
10 annual emissions from U.S. electric arc furnaces can be made by combining the production
11 estimate of steel and an average emission factor of 1.21 ng I-TEQDF/kg steel derived from the
12 data reported in Umweltbundesamt (1996) and the three Environment Canada reports (Charles E.
13 Napier Company, Ltd., 2000; Cianciarelli, 2000, 2001a). This calculation yields an annual
14 emission estimate of 37.3 g I-TEQDF in 1987, 46.5 g I-TEQDF in 1995, and 59.3 g I-TEQDF in
15 2000. These estimates should be regarded as preliminary indications of possible emissions from
16 this source category; further testing is needed to confirm the true magnitude of these emissions.
17
18 7.5. FERROUS FOUNDRIES
19 Ferrous foundries produce high-strength iron and steel castings used in industrial
20 machinery, pipes, and heavy transportation equipment. Iron and steel castings are solid solutions
21 of iron, carbon, and various alloying materials. Castings are produced by injecting or pouring
22 molten metal into cavities of a mold made of sand, metal, or ceramic material. Metallic raw
23 materials are pig iron, iron and steel scrap, foundry returns, and metal turnings (U.S. EPA,
24 1995b, 1997b).
25 The melting process takes place primarily in cupola (or blast) furnaces and to a lesser
26 extent in electric arc furnaces. About 70% of all iron castings are produced using cupolas,
27 although steel foundries rely almost exclusively on electric arc furnaces or induction furnaces for
28 melting. The cupola is typically a vertical, cylindrical steel shell with either a refractory-lined or
29 a water-cooled inner wall. Charges are loaded at the top of the unit; the iron is melted as it flows
30 down the cupola, and is removed at the bottom. Electric induction furnaces are batch-type
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1 furnaces in which the charge is melted by a fluctuating electromagnetic charge produced by
2 electrical coils surrounding the unit (U.S. EPA, 1995b, 1997b).
3 Iron and steel foundries, particularly those using electric arc furnaces, are highly
4 dependent on iron and steel scrap. Of the estimated 72 million metric tons of iron and steel scrap
5 consumed by the iron and steel industry in 1995, 25% (or 18 million metric tons) were used by
6 ferrous foundries. The other 75% were used by primary ferrous metal smelters (principally those
7 using electric arc furnaces) (USGS, 1997b). In 2000, 20% (12.4 million metric tons) were used
8 by ferrous foundries; the remaining 80% were used by primary ferrous smelters (USGS, 2000).
9 In 2000, there were approximately 1,100 ferrous foundries in the United States producing
10 1.3 million metric tons of steel castings and 10 metric tons of iron castings. Thus, foundries face
11 the same potential for CDD/CDF emissions as do electric arc furnaces because of their use of
12 scrap that contains chlorinated solvents, plastics, and cutting oils (see Section 7.4) The potential
13 for formation and release of CDDs/CDFs during the casting process is not known.
14 In 1993, emissions testing was conducted at a U.S. ferrous foundry (CARB, 1993a, as
15 reported in U.S. EPA, 1997b). The tested facility consisted of a batch-operated, coke-fired
16 cupola furnace charged with pig iron, scrap iron, scrap steel, coke, and limestone. Emission
17 control devices operating during the testing were an oil-fired afterburner and an FF. The
18 congener and congener group emission factors derived from the testing are presented in Table 7-
19 10. The calculated TEQ emission factor for this set of tests is 0.42 ng TEQDF-WHO98 (0.37 ng I-
20 TEQDF/kg) of metal charged to the furnace.
21 Umweltbundesamt (1996) reported stack testing results for a variety of ferrous foundries
22 in Germany. Sufficient data were provided to enable calculation of TEQ emission factors for
23 eight of the tested facilities. Three facilities had emission factors exceeding 1 ng I-TEQDF/kg of
24 metal charge, and four facilities had emission factors less than 0.1 ng I-TEQDF/kg of metal
25 charge. The emission factors span more than four orders of magnitude. The mean emission
26 factor was 1.26 ng I-TEQDF/kg of metal feed.
27 In 1997, EPA conducted testing for emissions of dioxins at two ferrous foundries (U.S.
28 EPA, 1999a, b). One study was conducted on the cupola's WS, the second study was performed
29 on the cupola's FF. A summary of the results is presented in Table 7-11. The emission factor
30 developed from these tests is 2.05 ng I-TEQ/kg of metal processed.
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1 Because of the wide range of emissions for the tested German foundries reported in
2 Umweltbundesamt (1996), the confidence in the degree to which the three tested U.S. facilities
3 represent the mean emission factor for the approximately 1,100 U.S. foundries is considered very
4 low. Therefore, the limited data available were judged inadequate for developing national
5 emission estimates that could be included in the national inventory. However, a preliminary
6 estimate of potential TEQ annual emissions from U.S. ferrous foundries can be made by
7 combining the mean emission factor (1.23 ng I-TEQDF/kg of metal feed) derived from the data
8 reported in Umweltbundesamt (1996), CARS (1993), and U.S. EPA (1997) with an estimated
9 activity level for U.S. foundries.
10 In 1987, U.S. shipments from ferrous foundries were 9.19 million metric tons, of which
11 about 90% were iron castings and 10% were steel castings (Houck, 1991). In 1995, U.S.
12 shipments from the approximately 1,000 U.S. ferrous foundries were 13.9 million metric tons, of
13 which about 90% were iron castings and 10% were steel castings (Fenton, 1996). In 2000, U.S.
14 shipments from the approximate 1,100 U.S. ferrous foundries were 11.3 million metric tons, of
15 which about 89% were iron castings and 11% were steel castings (USGS, 2001). Using the mean
16 emission factors and these activity levels yield annual emission estimates of 11.3 g I-TEQDF, 17.1
17 g I-TEQDF, and 13.9 g I-TEQDF for 1987, 1995, and 2000, respectively. These estimates should
18 be regarded as preliminary indications of possible emissions from this source category; further
19 testing is needed to confirm the true magnitude of these emissions.
20
21 7.6. SCRAP ELECTRIC WIRE RECOVERY
22 The objective of wire recovery is to reclaim the metal (copper, lead, silver, and gold) in
23 the electric wire by removing the insulating material. The recovery facility then sells the
24 reclaimed metal to a secondary metal smelter. Wire insulation commonly consists of a variety of
25 plastics, asphalt-impregnated fabrics, or burlap. Chlorinated organics are used to preserve the
26 cable casing in below-ground cables. The combustion of chlorinated organic compounds in the
27 cable insulation, catalyzed by the presence of wire metals such as copper and iron, can lead to the
28 formation of CDDs and CDFs (Van Wijnen et al., 1992).
29 Although, in the past, scrap electric wire was commonly recovered using thermal
30 processing to burn off the insulating material, current recovery operations typically no longer
31 involve thermal treatment, according to industry and trade association representatives. Instead,
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1 scrap electric wire is mechanically chopped into fine particles. The insulating material is then
2 removed by mixing, followed by settling of the heavier metal (telephone conversations between
3 T. Leighton, Versar, Inc., and R. Garino, Institute of Scrap Recycling Industries, March 2, 1993,
4 and T. Leighton and J. Sullivan, Triple F. Dynamics, March 8, 1993).
5 EPA measured dioxin-like compounds emitted to the air from a scrap wire reclamation
6 incinerator during its 1986 National Dioxin Study of combustion sources (U.S. EPA, 1987a).
7 EPA determined that the tested facility was typical of this industrial source category at that time.
8 Insulated wire and other metal-bearing scrap material were fed to the incinerator on a steel pallet.
9 The incinerator operated in a batch mode, with the combustion cycles for each batch of scrap
10 feed lasting between 1 and 3 hr. Natural gas was used to incinerate the material. Although most
11 of the wire had a tar-based insulation, PVC-coated wire was also fed to the incinerator.
12 Temperatures during combustion in the primary chamber furnace were about 570 °C. The tested
13 facility was equipped with a high-temperature, natural gas-fired afterburner (980 to 1090 °C).
14 Emission factors estimated for this facility are presented in Table 7-12. The estimated TEQ
15 emission factor (based only on 2,3,7,8-TCDD, 2,3,7,8-TCDF, OCDD, and OCDF) is 15.8 ng
16 TEQDF-WHO98 (16.9 ng I-TEQDF/kg) of scrap feed. Figure 7-5 presents a congener group profile
17 based on these emission factors.
18 Bremmer et al. (1994) reported emission factors for three facilities in the Netherlands that
19 subsequently ceased operations. Emission rates at a facility burning underground cables and
20 cables containing PVC ranged from 3.7 ng I-TEQDF/kg to 14 ng I-TEQDF/kg. The emission rates
21 at a second facility ranged from 21 ng I-TEQDF/kg of scrap (when burning copper core coated
22 with greasy paper) to 2,280 ng I-TEQDF/kg of scrap (when burning lead cable). The third facility,
23 which burned motors, was reported to have an emission rate of 3,300 ng I-TEQDF/kg of scrap.
24 On the basis of these measurements, Bremmer et al. used emission rates of 40 ng I-TEQDF/kg of
25 scrap and 3,300 ng I-TEQDF/kg of scrap for estimating national emissions in the Netherlands for
26 facilities burning wires and cables and those burning motors.
27 Although limited emission testing has been conducted at one U.S. facility, the activity
28 level for this industry sector in reference years 1987, 1995, and 2000 is unknown; therefore, an
29 estimate of national emissions cannot be made. It is uncertain how many facilities in the United
30 States still combust scrap wire. Trade association and industry representatives state that U.S.
31 scrap wire recovery facilities now burn only minimal quantities of scrap wire. However, an
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1 inventory of CDD/CDF sources in the San Francisco Bay area noted that two facilities thermally
2 treated electric motors to recover electrical windings (BAAQMD, 1996).
3 In addition to releases from regulated recovery facilities, CDD/CDF releases from small-
4 scale burning of wire at unregulated facilities and open air sites have occurred; however, the
5 current magnitude of small-scale, unregulated burning of scrap wire in the United States is not
6 known. Harnly et al. (1995) analyzed soil/ash mixtures from three closed metal recovery
7 facilities and from three closed sites using open burning for copper recovery near a California
8 desert town. The geometric means of the total CDD/CDF concentrations at the facility sites and
9 the open burning sites were 86,000 and 48,500 ng/kg, respectively. The geometric mean TEQ
10 concentrations were 2,900 and 1,300 ng I-TEQDF/kg, respectively. A significantly higher
11 geometric mean concentration (19,000 ng I-TEQDF/kg) was found in fly ash located at two of the
12 facility sites.
13 The congener-specific and congener group results from this study are presented in Table
14 7-13. The results show that the four dominant congeners in the soil samples at both the facility
15 and the open burning sites were OCDF, 1,2,3,4,6,7,8-HpCDF, 1,2,3,4,7,8-HxCDF, and 2,3,7,8-
16 TCDF. A slightly different profile was observed in the fly ash samples, with 1,2,3,7,8-PeCDF
17 and 1,2,3,4,7,8,9-HpCDF replacing OCDD and 2,3,7,8-TCDF as the dominant congeners.
18 Van Wijnen et al. (1992) reported similar results for soil samples collected from
19 unpermitted incineration sites of former scrap wire and cars in the Netherlands. Total CDD/CDF
20 concentrations in the soil ranged from 60 to 98,000 ng/kg, with 9 of the 15 soil samples having
21 levels above 1,000 ng/kg. Chen et al. (1986) reported finding high levels of CDDs/CDFs in
22 residues from open air burning of wire in Taiwan, and Huang et al. (1992) reported elevated
23 levels in soil near wire scrap recovery operations in Japan. Bremmer et al. (1994) estimated an
24 emission rate to air of 500 ng I-TEQDF/kg of scrap for illegal, unregulated burning of cables in the
25 Netherlands.
26
27 7.7. DRUM AND BARREL RECLAMATION FURNACES
28 Hutzinger and Fiedler (1991b) reported detecting CDDs/CDFs in stack gas emissions
29 from drum and barrel reclamation facilities at levels ranging from 5 to 27 ng/m3. EPA measured
30 dioxin-like compounds in the stack gas emissions of a drum and barrel reclamation furnace as
31 part of the National Dioxin Study (U.S. EPA, 1987a).
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1 Drum and barrel reclamation facilities operate a burning furnace to thermally clean used
2 55-gallon steel drums of residues and coatings. The drums processed at these facilities come
3 from a variety of sources in the petroleum and chemical industries. The thermally cleaned drums
4 are then repaired, repainted, relined, and sold for reuse. The drum-burning process subjects the
5 used drums to an elevated temperature in a tunnel furnace fired by auxiliary fuel for a sufficient
6 time so that the paint, interior linings, and previous contents are burned or disintegrated. Used
7 drums are loaded onto a conveyor that moves at a fixed speed. As the drums pass through the
8 preheat and ignition zone of the furnace, residual contents of the drums drain into the furnace ash
9 trough. A drag conveyor moves these sludges and ashes to a collection pit. The drums are air-
10 cooled as they exit the furnace. Exhaust gases from the burning furnace are typically drawn
11 through a breeching fan to a high-temperature afterburner.
12 The afterburner at the facility tested by EPA operated at an average of 827 °C during
13 testing and achieved a 95% reduction in CDD/CDF emissions (U.S. EPA, 1987a). Emission
14 factors estimated for this facility are presented in Table 7-14. On the basis of the measured
15 congener and congener group emissions, the average TEQ emission factor is estimated to be 17.5
16 ng TEQDF-WHO98/drum (16.5 ng I-TEQDF/drum). The congener group profile is presented in
17 Figure 7-6.
18 Approximately 2.8 to 6.4 million 55-gallon drums are reclaimed by incineration annually
19 in the United States (telephone conversation between C. D. Ruiz, Versar, Inc., and P. Rankin,
20 Association of Container Reconditioners, December 21, 1992). This estimate is based on the
21 assumption that 23 to 26 incinerators are in operation; each incinerator, on average, handles 500
22 to 1,000 drums/day; and, on average, each incinerator operates 5 days/wk, with 14 days
23 downtime/yr for maintenance activities. The weights of 55-gallon drums vary considerably;
24 however, on average, a drum weighs 38 Ib (or 17 kg); therefore, an estimated 48 to 109 million
25 kg of drums are incinerated annually. For 1987 and 1995, EPA assumed that 4.6 million drums
26 were burned each year (i.e., the midpoint of the range); applying the emission factors developed
27 above, the estimated annual emission of TEQ is 0.08 g TEQDF-WHO98 (0.08 g I-TEQDF).
28 In 1997, the Reusable Industrial Packaging Association esimated that approximately 35
29 million 55-gallon barrels were reclaimed in 1997 (RIPA, 1997). Assuming the number of drums
30 treated in 1997 has remained constant through 2000, the estimate for 2000 would be 0.61 g
31 TEQDF-WH098(0.58gI-TEQDF).
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1 A low confidence rating is assigned to the activity level estimates for all reference years
2 because they are based on expert judgment rather than a published reference. A low confidence
3 rating is also assigned to the emission factor, because it was developed from stack tests
4 conducted at just one U.S. drum and barrel furnace and thus may not represent average emissions
5 from current operations in the United States. Based on these ratings, the emission estimates are
6 assigned a low confidence rating.
7
8 7.8. SOLID WASTE FROM PRIMARY/SECONDARY IRON/STEEL
9 MILLS/FOUNDRIES
10 Table 17 in Quab and Fermann (1997) contains summary data on the typical annual
11 quantities and ranges of TEQ (Norwegian-TEQ [NTEQ] and I-TEQ) from various solid residuals
12 from the metallurgical industries in Europe, but support information and specific congeners were
13 not discussed. The summary data for annual TEQ generation are presented below (in grams) for
14 informational purposes only and are not included in the inventory of dioxin releases presented in
15 this report, because they are disposed of in permanent landfills and are not considered an
16 environmental release.
17
18 • Grey iron foundries, FF dust and scrubber sludge: 0.817 NTEQ
19 • Steel mill coke oven door leakage dust: 0.31 NTEQ
20 • Steel mill coke oven door leakage dust: 0.04 I-TEQ
21 • Pig iron tapping slag: 0.041 NTEQ
22 • Basic oxygen furnace scrubber sludge: 1.53 NTEQ (range, 0.3-7.81)
23 • Electric furnace FF dust: 3.1 I-TEQ (range of 0.4-2.4)
24 • Electric furnace slag or FF dust: 19.2 NTEQ
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Table 7-1. CDD/CDF emission concentrations for primary copper smelters
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
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
TOTAL
Emission concentrations
(pg TEQ/m3 @ 11% oxygen)
Run 1
0
0
0
0.1
0.1
0.1
0
0.7
0.1
2.2
0
0.1
0.3
0
0.1
0
0
3.8
Run 2
0
0
0
0
0
0.1
0
0.2
0
0.9
0.2
0.1
0.2
0
0.1
0
0
1.7
Run3
0
0.1
0
0
0
0
0
0.1
0
0
0.1
0
0.1
0
0
0
0
0.7
Source: Cianciarelli (200la).
03/04/05
7-34
DRAFT—DO NOT CITE OR QUOTE
-------
Table 7-2. CDD/CDF emissions data from primary and secondary copper
and secondary lead smelters
Company, location
Process units
Emission control
technology
CDD/CDF emission
concentration
(pg I-TEQ/dscm)
Primary copper smelters
Norddeutsche Affmerie,
Germany
Falconbridge, Sudbury,
Ontario (nickel and copper)
Noranda, Home smelter,
Noranda, Quebec
Noranda, Gaspe smelter,
Murdockville, Quebec
Outokumpu flash smelting
furnace
Peirce-Smith converter
Roasting
Electric smelting
Peirce-Smith converters
Noranda reactor
Noranda continuous
converter
Reverberatory furnace
Peirce-Smith converter
Waste heat boiler, ESP
ESP
Cyclone/ESP
ESP
ESP
<20
559
<1
82
Secondary copper smelters
Norddeutsche Affmerie,
Germany
Huttenwerke Kayser,
Germany
Mansfelder Kupfer und
Messing, Germany
Unknown company,
Germany
Unknown company,
Germany
Unknown company,
Germany
Unknown company,
Germany
Peirce-Smith converter
Blast furnace
Peirce-Smith converters
Reverberatory anode furnace
Hearth furnace (for tin/lead)
Blast furnace
Shaft furnace
Rotary furnace
Rotary furnace
Rotary furnace
FF
Post-combustion, waste
heat boiler, FF
FF
Waste heat boiler, FF
FF
Post-combustion, waste
heat boiler, cooler, FF, FF
with lime/coke injection
Post-combustion, dry
quench with secondary
off-gas, FF
FF
Gas cooling, FF
Gas cooling, FF, activated
carbonized lignite
adsorbent boxes
<500
<500
<100
<500
<100
<100-1,000
<100
<100
ESP = Electrostatic precipitator
FF = Fabric filter
Source: Charles E. Napier Company, Ltd. (2002).
03/04/05
7-35
DRAFT—DO NOT CITE OR QUOTE
-------
o
OJ
o
4^
o
Table 7-3. CDD/CDF emission factors for secondary aluminum smelters (ng/kg scrap feed)
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 I-TEQDFf
Total TEQDF-WHO98f
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility
emission factor3
ND (0.01)
0.02
0.05
0.13
0.15
0.51
0.42
0.44
0.06
0.17
0.32
0.11
0.02
0.3
0.07
0.03
0.3
0.26
0.27
NR
NR
NR
NR
0.42
NR
NR
NR
NR
0.3
NR
Mean facility
emission factorb
0.13
0.39
0.24
0.86
1.26
7.67
14.97
0.74
1.51
2.44
2.44
2.69
1.02
3.82
11.39
5.5
30.4
3.22
3.37
3.30
4.91
11.45
14.71
14.97
29.67
28.73
32.23
39.44
30.4
209.81
Mean facility
emission factor0
0.51
1.19
1.35
1.52
2.51
2.6
1.01
14.2
10.47
11.06
21.84
7.1
0.47
7.09
14.61
1.21
3.15
12.95
13.55
46.03
28.07
35.51
6.01
1.01
161.8
222.75
115.32
39.94
3.15
659.6
Mean facility
emission factor*1
2.17
3.84
2.88
5.39
7.22
18.01
NR
47.12
20.01
29.6
52.32
16.31
1.2
22.96
35.29
5.17
18.77
36.03
37.94
NR
NR
NR
NR
NR
NR
NR
NR
NR
18.77
NR
Mean facility
emission factor6
1.97
7.1
4.26
5.3
5.3
28.9
33.2
23.2
33.8
48
46.1
46.1
22
39
122
27.1
60.5
52.21
55.68
47.8
64
78
58.5
33.2
620
585
515
247
60.5
2309
Mean facility
emission factor"
0.845
3.64
2.82
4.12
2.02
19.3
24.3
4.84
1.18
23.3
17.6
16.9
1.35
16
42.6
6.2
29.5
21.67
23.44
0.845
3.64
8.95
19.3
24.3
4.84
35.1
52
48.8
29.5
227
o
o
o
H
O
HH
H
W
O
O
O
H
W
aSource: Advanced Technology Systems, Inc. (1995).
bSource: U.S. EPA (1995h).
-------
oj Table 7-3. CDD/CDF emission factors for secondary aluminum smelters (ng/kg scrap feed) (continued)
o
o °Source: Galson Corporation (1995).
dSource: Envisage Environmental, Inc. (1995).
Source: CARB (1992a, 1992b), as reported in U.S. EPA (1997b).
fTEQ calculations assume nondetect values are zero.
NR = Not reported
ND = Not detected (value in parenthesis is the detection limit)
O
o
2
o
H
O
HH
H
W
O
V
O
-------
Table 7-4. CDD/CDF emission factors for secondary copper smelters (ng/kg
scrap feed)
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 I-TEQDFe
Total TEQDF-WHO98e
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean EPA Tier 4
emission factora'b
127
NR
NR
NR
NR
NR
1,350
2,720
NR
NR
NR
NR
NR
NR
NR
NR
2,520
779f
810f
736
970
1,260
2,080
1,350
13,720
8,640
4,240
3,420
2,520
38,890
Franklin smelting
facility mean
emission factor0
227
846
1,476
1,746
2,132
17,065
55,668
4,457
9,455
5,773
70,742
20,524
5,362
12,082
37,251
7,570
82,192
16,618
16,917
14,503
30,248
55,765
38,994
55,668
108,546
71,136
164,834
66,253
82,192
688,139
Chemetco smelting
facility mean
emission factor*1
ND (0.05)
0.21
0.39
0.70
1.26
8.95
22.45
2.11
1.47
2.63
7.30
2.15
4.06
0.27
11.48
2.74
21.61
3.6
3.66
3.05
5.19
9.62
16.71
22.45
46.42
27.99
27.96
23.38
21.61
204.33
aNo nondetect values were reported for 2,3,7,8-TCDD, 2,3,7,8-TCDF, or any congener group in the three test runs.
bSource: U.S. EPA (1987a).
cSource: AGES (1992).
dSource: Sverdrup Corp. (1991).
eTEQ calculations assume nondetect values are zero.
•Estimated using the measured data for 2,3,7,8-TCDD, 2,3,7,8-TCDF, OCDD, and OCDF and congener group
emissions (i.e., for the penta-, hexa-, and hepta-CDDs and CDFs, it was assumed that the measured emission
factor within a congener group was the sum of equal emission factors for all congeners in that group, including
non-2,3,7,8-substituted congeners).
NR = Not reported
ND = Not detected (value in parenthesis is the detection limit)
03/04/05
7-38
DRAFT—DO NOT CITE OR QUOTE
-------
Table 7-5. CDD/CDF emission estimates for Canadian coke oven facilities,
blast furnace facilities, and electric arc furnaces
Comp any/facility
Location
Plant
capacity
(net
tonnes/yr)
Estimated
production
(net tonnes)
Estimated
CDD/CDF
emissions
(gl-TEQ)
Estimated
CDD/CDF
emission
factor
(ngl-
TEQ/kg)
Coke oven facilities
Algoma Steel Inc.
Dofasco Inc.
Stelco Inc. Lake Erie
Steel
Stelco Inc., Hilton
Works
Sault Ste. Marie,
Ontario
Hamilton, Ontario
Nanticoke, Ontario
Hamilton, Ontario
TOTAL
1,021,000
1,656,000
563,000
1,035,000
4,275,000
979,000
1,588,000
540,000
993,000
4,100,000
0.29
0.48
0.16
0.3
1.23
0.296
0.302
0.296
0.302
Blast furnace facilities
Algoma Steel Inc
Dofasco Inc.
Stelco Inc. Lake Erie
Steel
Stelco Inc., Hilton
Works
Sault Ste. Marie,
Ontario
Hamilton, Ontario
Nanticoke, Ontario
Hamilton, Ontario
TOTAL
2,270,000
2,725,000
1,680,000
2,720,000
9,395,000
2,177,000
2,613,000
1,611,000
2,608,000
9,009,000
0.01
0.01
O.01
O.01
O.I
NA
NA
NA
NA
Electric arc furnaces
AltaSteel Ltd.
Atlas Specialty Steels
Atlas Stainless Steels
Co-Steel Lasco
Dofasco Inc.
Gerdau MRM Steel
Inc.
Gerdan MRM Steel
Inc.
IPSCO Inc.
Ispat Sidbec Inc.
Ivanco Rolling Mills
Inc.
Slater Steels, Hamilton
Specialty Bar Div.
Stelco-McMaster Ltee
Edmonton, Alberta
Welland, Ontario
Tracy, Quebec
Whitby, Ontario
Hamilton, Ontario
Cambridge, Ontario
Selkirk, Manitoba
Regina,
Saskatchewan
Contrecoeur, Quebec
L' Original, Ontario
Hamilton, Ontario
Contrecoeur, Quebec
295,000
218,000
118,000
907,000
1,225,000
290,000
281,000
907,000
1,633,000
408,000
363,000
499,000
256,000
189,000
103,000
788,000
1,065,000
252000
244,000
788,000
1,419,000
355,000
315,000
434,000
0.67
0.49
0.27
0.79
0.5
0.66
0.63
1.13
3.69
0.92
0.82
1.13
2.62
2.59
2.62
1
0.469
2.62
2.58
1.43
2.6
2.59
2.6
2.6
03/04/05
7-39
DRAFT—DO NOT CITE OR QUOTE
-------
Table 7-5. CDD/CDF emission estimates for Canadian coke oven facilities,
blast furnace facilities, and electric arc furnaces (continued)
Comp any/facility
Sydney Corp.
Location
Sydney, Nova Scotia
TOTAL
Plant
capacity
(net
tonnes/yr)
454,000
7,598,000
Estimated
production
(net tonnes)
395,000
6,603,000
Estimated
CDD/CDF
emissions
(gl-TEQ)
0.4
12.1
Estimated
CDD/CDF
emission
factor
(ngl-
TEQ/kg)
1.01
Source: Charles E. Napier Company, Ltd. (2000).
03/04/05
7-40
DRAFT—DO NOT CITE OR QUOTE
-------
Table 7-6. CDD/CDF emission factors for secondary lead smelters"
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
(nondetect set to zero)
Total TEQDF-WHO98
(nondetect set to zero)
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
(nondetect set to 0)
Total CDD/CDF
(nondetect set to l/i
detection limit)
Blast furnaceb
(ng/kg lead produced)
Before
scrubber
2.11
0.99
0.43
0.99
1.55
2.06
1.4
8.73
3.88
6.65
5.83
1.67
0.11
2.06
2.34
0.63
1.39
9.52
33.28
8.31
8.81
74.33
39.29
20.05
4.2
1.39
145.71
69.59
19.73
4.74
1.39
380.43
380.44
After
scrubber
0.25
0.03
0
0.03
0.03
0.08
0.39
0.93
0.43
0.36
0.37
0.11
0
0.11
0.19
0.06
0.18
0.82
2.74
0.63
0.64
7.39
1.73
0.81
9.72
0.18
17.34
3.45
1.02
0.11
0.18
41.92
42.27
Blast/reverb0
(ng/kg lead produced)
Before
scrubber
0
0
0
0
0
0.1
0.57
1.46
0.24
0.31
0.63
0.19
0
0.15
0.48
0
0.29
0.68
3.75
0.41
0.42
0.97
0.15
0.14
0.09
0.57
8.21
3.07
1.14
0.72
0.29
15.36
15.36
After
scrubber
0
0
0
0
0
0.06
0.55
0.49
0.02
0
0
0
0
0
0
0
0
0.61
0.51
0.05
0.05
1.58
0.16
0.02
0.09
0.55
4.71
0.36
0.19
0.01
0.00
7.66
7.74
Rotary kiln"
(ng/kg lead produced)
Before
scrubber
0.1
0.01
0
0
0
0
0.24
0.4
0.14
0.14
0.11
0.02
0.04
0
0.03
0
0
0.35
0.88
0.24
0.24
3.4
0.29
0.1
0.01
0.24
10.82
1.69
0.15
0.05
0
16.76
16.8
After
scrubber
0.24
0
0
0
0
0.22
2.41
1.2
0.4
0.46
0.27
0.1
0.13
0
0.13
0
0
2.87
2.68
0.66
0.66
7.9
0.27
0.23
0.29
2.41
28.57
5.04
0.73
0.14
0
45.57
45.62
aExcept where noted, emission factors were calculated assuming nondetect values are zero.
bSource: U.S. EPA (1995e).
cSource: U.S. EPA (1992e).
dSource: U.S. EPA (1995d).
03/04/05
7-41
DRAFT—DO NOT CITE OR QUOTE
-------
Table 7-7. CDD/CDF emission factors for sinter plants (ng/kg sinter)
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDFa
Wet scrubber
Nondetect set to
zero
0.049
0.138
0.03
0.612
0.288
0.696
0.496
0.602
0.343
0.349
0.421
0.164
0.011
0.142
0.247
0.036
0.103
2.309
2.418
0.55
0.62
NR
NR
NR
NR
0.496
NR
NR
NR
NR
0.103
4.73
Nondetect set to Vz
detection limit
0.049
0.138
0.03
0.612
0.288
0.696
0.496
0.602
0.343
0.349
0.421
0.164
0.014
0.142
0.247
0.036
0.103
2.309
2.421
0.55
0.62
NR
NR
NR
NR
0.496
NR
NR
NR
NR
0.103
4.73
Fabric filter
Nondetect set
to zero
0.406
0.937
0.135
1.469
0.609
0.698
0.695
10.232
3.518
3.228
1.382
0.495
0.029
0.285
0.316
0
0.05
4.949
19.535
4.14
4.61
NR
NR
NR
NR
0.695
NR
NR
NR
NR
0.05
24.48
Nondetect set to Vz
detection limit
0.406
0.937
0.135
1.469
0.609
0.698
0.695
10.232
3.518
3.228
1.382
0.495
0.057
0.285
0.316
0.115
0.192
4.949
19.82
4.14
4.61
NR
NR
NR
NR
0.695
NR
NR
NR
NR
0.192
24.77
aThe listed values for total CDD/CDF include only the 17 toxic congeners.
Source: Calcagnietal. (1998).
03/04/05
7-42
DRAFT—DO NOT CITE OR QUOTE
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Table 7-8. Operating parameters for U.S. iron ore sinter plants
Company
AK Steel
AK Steel"
Bethlehem Steel
Bethlehem Steel
Geneva Steel
Inland Steel
LTV Steel
U.S. Steel
Weirton Steel3
Wheeling-Pittsburgh Steel
WCI Steel
Location
Middletown, OH
Ashland, KY
Burns Harbor, IN
Sparrows Point, MD
Provo, UT
East Chicago, IN
East Chicago, IN
Gary, IN
Weirton, WV
East Steubenville, WV
Warren, OH
TOTAL
1998 capacity
(1000 metric
ton/yr)
907
816a
2,676
3,856
816
1,089
1,270
3,992
l,179a
519
477
17,597b
Current air
pollution control
device
Wet scrubber
NA
Wet scrubber
Wet scrubber
Fabric filter
Fabric filter
Wet scrubber
Fabric filter
NA
Wet scrubber
Fabric filter
aNot in operation during
bWhen the Ashland, KY,
tons.
NA = Not available
1998 (Calcagni et al., 1998).
and Weirton, WV, facilities are excluded,
total 1998 capacity was 15,600,000 metric
Sources: Metal Producing (1991, 1996); Calcagni et al. (1998).
03/04/05
7-43
DRAFT—DO NOT CITE OR QUOTE
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Table 7-9. CDD/CDF emission concentrations and rates for Canadian
electric arc furnaces
Congener
Mean facility concentration
(pgTEQ/m3)
Runl
Run 2
Run 3
Avg.
Mean facility emission rate
(ng TEQ/tonne steel)
Runl
Run 2
Run 3
Avg.
Dofasco Inc.
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
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
TOTAL
0
1.96
0
0
0.25
0.11
0.04
9.96
0.48
5.88
1.12
0.51
0
0
0.11
0
0.01
20.43
1.99
4.09
0
0.33
0
0
0.01
37.11
1.23
14.9
2.23
0.81
0.52
0
0.05
0
0
63.26
0
6.44
0
1.13
0.63
0.05
0
29.45
1.6
22.98
3.86
2.02
1.43
0
0.16
0
0
69.76
0.66
4.16
0
0.49
0.29
0.05
0.02
25.51
1.1
14.59
2.4
1.11
0.65
0
0.11
0
0
51.15
0
20.5
0
0
2.7
1.2
0.4
104.2
5
61.6
11.7
5.3
0
0
1.1
0
0.1
213.8
17.2
35.3
0
2.8
0
0
0
320.9
10.6
128.8
19.3
7
4.5
0
0.4
0
0
547.1
0
60.5
0
10.6
5.9
0.5
0
276.5
15
215.7
36.3
19
13.4
0
1.5
0
0
654.9
5.7
38.8
0
4.5
2.9
0.6
0.1
233.9
10.2
135.4
22.4
10.4
6
0
1
0
0
471.9
Gerdau Courtice Steel Inc.
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
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
TOTAL
6.3
8.3
0.6
1
0.8
0.2
0
65
5.5
95.5
12.5
6.9
5.8
0.5
0.7
0.1
0
209.7
2.7
4.7
0.4
0.7
0.5
0.1
0
29.4
2.9
46.2
7.9
4.6
4.3
0.5
0.5
0.1
0
105.5
2.6
3.1
0.2
0.4
0.3
0.1
0
18
1.7
26
4.3
2.4
1.7
0.2
0.2
0
0
61.3
3.9
5.4
0.4
0.7
0.5
0.1
0
37.5
3.4
55.9
8.2
4.6
3.9
0.4
0.5
0.1
0
125.5
57
75
5
9
8
1
0
588
50
864
113
62
52
5
6
1
0
1896
21
37
3
6
4
1
0
232
23
364
63
36
34
4
4
1
0
832
22
27
2
o
J
3
1
0
154
15
222
37
20
14
2
2
0
0
524
33.3
46.3
3.3
6
5
1
0
324.7
29.3
483.3
71
39.3
o o o
55.5
3.7
4
0.7
0
1084
Source: Cianciarelli (2000).
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Table 7-10. CDD/CDF emission factors for a U.S. ferrous foundry
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 (for reported congeners)
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF (not including OCDD)
Mean facility emission factor
(ng/kg scrap feed)
0.033
0.086
NR
0.051
NR
0.093
NR
0.52
0.305
0.35
0.19
0.17
NR
0.101
0.193
NR
0.059
0.262
1.888
0.372
0.415
3.96
1.76
0.55
0.19
NR
25.8
850
1.74
0.24
0.06
884.3
NR = Not reported
Source: CARB (1993a), as reported in U.S. EPA (1997b).
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Table 7-11. Congener-specific profile for ferrous foundries
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
Total I-TEQ
Mean emission factor (2 facilities)
(ngl-TEQ/kg)
Nondetect set to zero
0.11
0.15
0.012
0.023
0.028
0.0033
0.16
0.084
1.08
0.21
0.1
0.0079
0.075
0.0082
0.0014
0.00009
0.00007
2.05
Nondetect set to 1A detection limit
0.11
0.15
0.012
0.023
0.028
0.0033
0.16
0.084
1.08
0.21
0.1
0.0079
0.075
0.0082
0.0014
0.00009
0.00007
2.05
Sources: U.S. EPA (1999a, 1999b).
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Table 7-12. CDD/CDF emission factors for a scrap wire incinerator
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility emission factor" (ng/kg scrap feed)
0.374
NR
NR
NR
NR
NR
1,000
2.67
NR
NR
NR
NR
NR
NR
NR
NR
807
NR
NR
16.9b
15.8
1,000
4.42
13.7
71.1
347
107
97.4
203
623
807
3,273
aNo nondetect values were reported for 2,3,7,8-TCDD, 2,3,7,8-TCDF, or any congener group in the three test runs.
Estimated on the basis of the measured data for 2,3,7,8-TCDD, 2,3,7,8-TCDF, OCDD, and OCDF and congener
group emissions (i.e., for the penta-, hexa-, and hepta-CDDs and CDFs, it was assumed that the measured
emission factor within a congener group was the sum of equal emission factors for all congeners in that group,
including non-2,3,7,8-substituted congeners).
NR = Not reported
Source: U.S. EPA (1987a).
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Table 7-13. CDD/CDF concentrations in fly ash and ash/soil at metal
recovery sites
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 TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total I-TEQDF
Total CDD/CDF
Metal recovery facilities
Fly ash (2 sites)
Geometric
mean
(Hg/kg)
a
400
1,200
2,300
1,700
12,000
18,000
15,000
35,000
10,000
46,000
12,000
5,000
5,000
71,000
25,000
100,000
a
2,000
4,000
24,000
18,000
23,000
110,000
88,000
110,000
100,000
19,000
510,000
Relative
percent of
total
CDD/CDF
0.1
0.2
0.5
0.3
2.4
3.5
2.9
6.9
2
9
2.4
1
1
13.9
4.9
19.6
a
0.4
0.8
4.7
3.5
4.5
21.6
17.3
21.6
19.6
Ash/soil (3 sites)
Geometric
mean
(Hg/kg)
a
0.24
0.25
0.49
1.3
2.6
7.2
6.4
2.9
1.4
5.9
1.8
0.92
1.6
12
3
14
a
1.4
2.7
4.1
7.2
14
12
12
17
14
2.9
85
Relative
percent of
total
CDD/CDF
0.3
0.3
0.6
1.5
3.1
8.5
7.5
3.4
1.6
6.9
2.1
1.1
1.9
14.1
3.5
16.5
a
1.6
3.2
4.8
8.5
16.5
14.1
14.1
20
16.5
Open burn sites
Ash/soil (3 sites)
Geometric
mean
(Hg/kg)
a
0.24
0.13
0.33
0.39
1.2
3.4
1.7
0.58
0.66
2.7
0.76
0.66
0.49
4.3
0.71
6.6
a
2.8
0.98
2
3.4
5.6
7
7.6
7.4
6.6
1.3
48.5
Relative
percent of
total
CDD/CDF
0.5
0.3
0.7
0.8
2.5
7
3.5
1.2
1.4
5.6
1.6
1.4
1
8.9
1.5
13.6
a
5.8
2
4.1
7
11.5
14.4
15.7
15.3
13.6
aAnalytical method used had low sensitivity for TCDDs; results were not reported.
Source: Harnly et al. (1995).
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Table 7-14. CDD/CDF emission factors for a drum and barrel reclamation
facility
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-CDD
Total 2,3,7,8-CDF
Total I-TEQDF
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Mean facility emission factor" (ng/drum)
2.09
NR
NR
NR
NR
NR
37.5
36.5
NR
NR
NR
NR
NR
NR
NR
NR
22.4
NR
NR
16.5b
17.5
50.29
29.2
32.2
53.4
37.5
623
253
122
82.2
22.4
1,303
aNo nondetect values were reported for 2,3,7,8-TCDD, 2,3,7,8-TCDF, or any congener group in the three test runs.
'Estimated on the basis of the measured data for 2,3,7,8-TCDD, 2,3,7,8-TCDF, OCDD, and OCDF and congener
group emissions (i.e., for the penta-, hexa-, and hepta-CDDs and CDFs, it was assumed that the measured
emission factor within a congener group was the sum of equal emission factors for all congeners in that group,
including non-2,3,7,8-substituted congeners).
NR = Not reported
Source: U.S. EPA (1987a).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.01 0.02 0.03 0.04 0.05 0.06 0.07
0.08
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
2,3,4,8,7,8-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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0.05 0.1 0.15 0.2
0.25
Figure 7-1. Congener and congener group profiles for air emissions from
secondary aluminum smelters.
Sources: U.S. EPA (1995h); Galson Corporation (1995).
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Ratio (congener group emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3
0.4
Figure 7-2a. Congener group profile for air emissions from a secondary
copper smelter.
Source: U.S. EPA (1987c).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.02 0.04 0.06 0.08 0.1 0.12
0.14
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25
Figure 7-2b. Congener and congener group profiles for a closed secondary
copper smelter.
Source: AGES (1992).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
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
Ratio (congener group emission factor/total CDD/CDF emission factor)
0 0.1 0.2 0.3 0.4 0.5
0.6
I Blast furnace
J Reverb/co-located furnace
Figure 7-3. Congener and congener group profiles for air emissions from
secondary lead smelters. Profiles are for emissions from fabric filters; nondetect
values set equal to zero.
Sources: U.S. EPA (1992e, 1995d, e).
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Ratio (congener emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3 0.4
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
I Wet scrubber
Figure 7-4. Congener profiles for air emissions from U.S. iron ore sinter
plants.
Source: Calcagnietal. (1998).
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Ratio (congener group emission factor/total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25 0.3
0.35
Figure 7-5. Congener group profile for air emissions from a scrap wire
incinerator.
Source: U.S. EPA (1987a).
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Ratio (congener group emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3 0.4 0.5
0.6
Figure 7-6. Congener group profile for air emissions from a drum
incinerator.
Source: U.S. EPA (1987a).
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1 8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES
2
3 8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS
4 In March 1988, EPA and the U.S. pulp and paper industry jointly released the results of a
5 screening study that provided the first comprehensive data on the formation and discharge of
6 CDDs/CDFs from pulp and paper mills (U.S. EPA, 1988d). This early screening study of five
7 bleached kraft mills (the Five Mill Study) confirmed that the pulp bleaching process was
8 primarily responsible for the formation of CDDs/CDFs. The study results showed that 2,3,7,8-
9 TCDD was present in seven of nine bleached pulps, five of five wastewater treatment sludges,
10 and three of five treated wastewater effluents. The study results also indicated that 2,3,7,8-
11 TCDD and 2,3,7,8-TCDF were the principal CDDs/CDFs formed.
12 To provide EPA with more complete data on the release of these compounds by the U.S.
13 industry, EPA and the U.S. pulp and paper industry jointly conducted a survey during 1988 of
14 104 pulp and paper mills in the United States to measure levels of 2,3,7,8-TCDD and 2,3,7,8-
15 TCDF in effluent, sludge, and pulp. That study, commonly called the 104 Mill Study, was
16 managed by the National Council of the Paper Industry for Air and Stream Improvement, Inc.
17 (NCASI), with oversight by EPA, and included all mills where chemically produced wood pulps
18 were bleached with chlorine or chlorine derivatives. The final study report (U.S. EPA, 1990a)
19 was released in July 1990.
20 An initial phase of the 104 Mill Study involved the analysis of bleached pulp (10
21 samples), wastewater sludge (9 samples), and wastewater effluent (9 samples) from eight kraft
22 mills and one sulfite mill for all 2,3,7,8-substituted CDDs/CDFs. These analyses were
23 conducted to test the conclusion drawn in the Five Mill Study that 2,3,7,8-TCDD and 2,3,7,8-
24 TCDF were the principal CDDs/CDFs found in pulp, wastewater sludge, and wastewater effluent
25 on a TEQ basis. Although at the time of the study there were no reference analytical methods for
26 many of the 2,3,7,8-substituted CDDs/CDFs, the data obtained were considered valid by EPA for
27 the purposes intended because of the identification and quantification criteria used, duplicate
28 sample results, and limited matrix spike experiments. Table 8-1 presents a summary of the
29 results obtained in terms of the median concentrations and the range of concentrations observed
30 for each matrix (pulp, sludge, and effluent). Figures 8-1 through 8-3 present congener profiles
31 for each matrix (normalized to total CDD/CDF and total I-TEQDp) using the median reported
32 concentrations.
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1 After examination of the raw, mill-specific data, EPA (U.S. EPA, 1990a) concluded that
2 the congener profiles were fairly consistent across matrices within mills and that 2,3,7,8-TCDD
3 and 2,3,7,8-TCDF accounted for the majority of TEQ in the samples. Using the median
4 concentrations and treating nondetect values as either zero or one-half the detection limit (DL),
5 EPA concluded that 2,3,7,8-TCDF accounted for 95.4 to 99.5% of the total TEQDF-WHO98 (95.8
6 to 99% of the total I-TEQDF) in pulp, 94.1 to 96.5% of the TEQDF-WHO98 (94.1 to 95.8% of the
7 I-TEQDF) in sludge, and 81.7 to 96.4% of the TEQDF-WHO98 (81.1 to 91.7% of the I-TEQDF) in
8 effluent.
9 NCASI reported on a similar full-congener analysis study for samples collected from
10 eight mills during the mid-1990s (Gillespie, 1997). The results of these analyses are presented in
11 Table 8-2. The frequency of detection of 2,3,7,8-TCDD and 2,3,7,8-TCDF was significantly
12 lower than in the 1988 study; therefore, deriving meaningful summary statistics concerning the
13 relative importance of 2,3,7,8-TCDD and 2,3,7,8-TCDF to the total TEQ is difficult. With all
14 nondetect values assumed to be zero, 2,3,7,8-TCDD and 2,3,7,8-TCDF accounted for 97% of the
15 total effluent TEQDF-WHO98 (91% of the I-TEQDF), 53% of the total sludge TEQDF-WHO98
16 (46% of the I-TEQDF), and 87% of the total pulp TEQDF-WHO98 (87% of the I-TEQDF). Because
17 of the high frequency of nondetects when all nondetect values are one-half the DL, 2,3,7,8-
18 TCDD and 2,3,7,8-TCDF accounted for only 13% of the total effluent I-TEQDF, 13% of the total
19 sludge I-TEQDF, and 28% of the total pulp I-TEQDF.
20 In 1992, the pulp and paper industry conducted its own NCAST-coordinated survey of
21 2,3,7,8-TCDD and 2,3,7,8-TCDF emissions (NCASI, 1993). Ninety-four mills participated in
22 the study, and NCASI assumed that the remaining 10 (of 104) operated at the same levels as
23 measured in the 1988 104 Mill Study. All nondetect values were counted as one-half the DL. If
24 a DL was not reported, it was assumed to be 10 pg/L for effluent and 1 ng/kg for sludge or
25 bleached pulp. The data used in the report were provided by individual pulp and paper
26 companies that had been requested by NCASI to generate the data using the same protocols used
27 in the 104 Mill Study.
28 In 1993, as part of its efforts to develop revised effluent guidelines and standards for the
29 pulp, paper, and paperboard industry, EPA published the development document for the
30 guidelines and standards being proposed for this industry (U.S. EPA, 1993d). The development
31 document presented estimates of the 2,3,7,8-TCDD and 2,3,7,8-TCDF annual discharges in
32 wastewater from the mills in this industry as of January 1, 1993. To estimate these discharges,
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1 EPA used the most recent information about each mill from four databases (104 Mill Study, EPA
2 short-term monitoring studies at 13 mills, EPA long-term monitoring studies at eight mills, and
3 industry self-monitoring data submitted to EPA). The 104 Mill Study data were used for only
4 those mills that did not report making any process changes subsequent to the 104 Mill Study and
5 did not submit any more recent effluent monitoring data.
6 Gillespie (1994) and Gillespie (1995) reported the results of 1993 and 1994 updates,
7 respectively, to the 1992 NCASI survey. As in the 1992 survey, companies were requested to
8 follow the same protocols for generating data used in the 104 Mill Study. Gillespie (1994, 1995)
9 reported that fewer than 10% of mills had 2,3,7,8-TCDD and 2,3,7,8-TCDF concentrations in
10 effluent above the nominal DLs of 10 pg/L and 100 pg/L, respectively. EPA obtained similar
11 results in its short- and long-term sampling for 18 mills; 2,3,7,8-TCDD was detected at four
12 mills, and 2,3,7,8-TCDF was detected at nine mills (U.S. EPA, 1993d).
13 Gillespie (1994) reported that wastewater sludges at most mills (90%) contained less than
14 31 ng/kg of 2,3,7,8-TCDD and less than 100 ng/kg of 2,3,7,8-TCDF. Gillespie (1995) reported
15 that 90% of the mills had 2,3,7,8-TCDD and 2,3,7,8-TCDF concentrations in sludge of less than
16 17 ng/kg and 76 ng/kg, respectively, in 1994. U.S. EPA (1993d) reported similar results but
17 found detectable levels of 2,3,7,8-TCDD and 2,3,7,8-TCDF in sludges from 64% and 85%,
18 respectively, of the facilities sampled.
19 In Gillespie (1994), nearly 90% of the bleached pulps contained less than 2 ng/kg of
20 2,3,7,8-TCDD and less than 160 ng/kg of 2,3,7,8-TCDF. Gillespie (1995) reported that 90% of
21 the bleached pulps contained 1.5 ng/ng or less of 2,3,7,8-TCDD and 5.9 ng/kg or less of 2,3,7,8-
22 TCDF. The final levels in white paper products would correspond to levels in bleached pulp, so
23 bleached paper products would also be expected to contain less than 2 ng/kg of 2,3,7,8-TCDD.
24 On April 15, 1998, EPA promulgated effluent limitations guidelines and standards for
25 certain segments of the pulp, paper, and paperboard industry (Federal Register, 1998c). The
26 industry segments covered by this rulemaking (i.e., the bleached paper-grade kraft and soda
27 subcategory and the paper-grade sulfite subcategory) are those segments responsible for more
28 than 90% of the bleached chemical pulp production in the United States. For this rule, EPA
29 updated the estimates of baseline loadings made in 1993 for the proposed rule by using more
30 recent data collected by EPA, NCASI (including the 1994 NCASI survey), and individual
31 facilities (U.S. EPA, 1997f). These revised estimates are presented in the last column in Table 8-
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1 3. EPA projects that, after full compliance with these rules, annual TEQ discharges will be
2 reduced to 5 g in effluent and 7 g in sludge.
3
4 8.1.1. Estimates of National Emissions in 1987 and 1995
5 The U.S. annual discharges of 2,3,7,8-TCDD and 2,3,7,8-TCDF are summarized in Table
6 8-3 for each of the six surveys discussed above. EPA release estimates for 1988 (U.S. EPA,
7 1990a) and for 1995 (U.S. EPA, 1997f) are believed to best represent emissions in reference
8 years 1987 and!995, respectively. During the period between EPA's 104 Mill Study and
9 issuance of the development document (U.S. EPA, 1993d), the U.S. pulp and paper industry
10 reduced releases of CDDs/CDFs, primarily by instituting numerous process changes to reduce
11 the formation of CDDs/CDFs during the production of chemically bleached wood pulp. Details
12 on the process changes implemented are provided in U.S. EPA (1993d) and Gillespie (1995).
13 Much of the reduction between 1988 and 1995 can be attributed to process changes for pollution
14 prevention.
15 The confidence ratings for these release estimates are judged to be high because direct
16 measurements were made at virtually all facilities, indicating a high level of confidence in both
17 the production and the emission factor estimates. The best estimates of annual emissions in 1987
18 (i.e., the 1988 estimates presented in Table 8-3) are 356 g TEQ/yr for effluent and 343 g TEQ/yr
19 for sludge. The best estimates of annual emissions in 1995 (i.e., the 1995 estimates presented in
20 Table 8-3) are 28 g TEQ/yr for effluent and 50 g TEQ/yr for sludge. The CDD/CDF content in
21 bleached chemical wood pulp as a product is estimated to be approximately 505 g TEQ and 40 g
22 TEQ in 1987 and 1995, respectively. Although EPA provided an estimate of contaminant levels
23 of CDDs/CDFs in wood pulp, it is currently not known if the dioxin contamination in the product
24 actually resulted in a release to the open and circulating environment.
25 In 1990, the majority (75.5%) of the wastewater sludge generated by these facilities was
26 placed in landfills or in surface impoundments, with the remainder incinerated (20.5%), applied
27 to land directly or as compost (4.1%), or distributed as a commercial product (less than 1%)
28 (U.S. EPA, 1993e). Data on the disposition of wastewater sludges are available only for years
29 1988 through 1995. On the basis of these data, the best estimate of TEQ applied to land (i.e., not
30 incinerated or landfilled) is 14.1 g TEQ (4.1% of 343 g) for 1987 and 2 g (4.1% of 50 g) for
31 1995. These emission estimates are assigned a high level of confidence on the basis of the high
32 confidence ratings given to both the activity level and emission factor estimates.
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1
2 8.1.2. Estimates of National Emissions in 2000
3 In 2000, NC AST provided estimates of congener-specific CDD/CDF releases from the
4 pulp and paper industry in effluent, wastewater residuals, and pulp (Gillespie, 2002). Emission
5 factors were taken from the "NCASI Handbook of Chemical Specific Information for SARA
6 (Superfund Amendments and Reauthorization Act) Section 313 Form R Reporting." Emission
7 factors were compiled from valid test data supplied to NCASI by a variety of sources, including
8 member companies that had performed the tests in response to a regulatory program. The mass
9 throughput parameter of total pulp production (31.9 million metric tons/yr) was provided by the
10 American Forest and Paper Association and included data from 12 elemental chlorine-free mills.
11 The effluent flow from chemical pulp mills with aerated stabilization basins (1509 million
12 gal/day) and with activated sludge treatment (660 million gal/day) was taken from the NCASI
13 database and included data from five aerated stabilization basin mills and three activated sludge
14 treatment mills. The primary waste treatment residuals from pulp mills (0.974 million dry metric
15 tons/yr) and the combined, secondary, and dredged waste treatment residuals from pulp mills
16 (1.37 million dry metric tons/yr) were also taken from the NCASI database and included data
17 from five mills for the primary residuals and data from three mills for the secondary residuals
18 (Gillespie, 2002).
19 Table 8-4 provides a breakdown of TEQoF-WHOgg concentrations and emissions by
20 congener. Total TEQDF-WHO98 concentrations were reported to be 0.49 pg/L, 1.72 ng/kg, and
21 0.02 pg/g for effluent, sludge, and pulp, respectively. CDD/CDF emission estimates were
22 reported as 1.02 g TEQDF.WHO98/yr, 1.93 g TEQDF.WHO98/yr, and 0.582 g TEQDF.WHO98/yr
23 for effluent, sludge, and pulp, respectively.
24 Fifty-one percent of the sludge generated was sent to landfills or lagoons. It is uncertain
25 how much of the remaining 49% of the sludge was applied to land. However, a conservative
26 estimate can be developed by applying the 4.1% used to develop the 1987 and 1995 estimates.
27 In this case, 0.08 g TEQoF-WHOgg/yr of sludge is estimated to have been applied to land in 2000.
28 These estimates are assigned a high confidence rating because they are based on recent industry
29 survey data; however, EPA is working with NCASI to develop a QA/QC protocol to monitor the
30 data being collected.
31
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1 8.2. MANUFACTURE OF CHLORINE, CHLORINE DERIVATIVES, AND METAL
2 CHLORIDES
3 Testing of CDD/CDF emissions to air, land, or water from U.S. manufacturers of
4 chlorine, chlorine derivatives, and metal chlorides on which to base estimates of national
5 emissions has not been reported. Sampling of graphite electrode sludges from European chlorine
6 manufacturers indicates high levels of CDFs. Limited sampling of chlorine derivatives and
7 metal chlorides in Europe indicates low-level contamination in some products.
8
9 8.2.1. Manufacture of Chlorine
10 Chlorine gas is produced by electrolysis of brine electrolytic cells. Until the late 1970s,
11 the primary type of electrolytic process used in the chloralkali industry to produce chlorine
12 consisted of the use of mercury cells containing graphite electrodes. As shown in Table 8-5,
13 high levels of CDFs have been found in several samples of graphite electrode sludge from
14 facilities in Europe. The CDFs predominate in these sludges, and the 2,3,7,8-substituted
15 congeners account for a large fraction of the respective congener totals (Rappe et al., 1990b,
16 1991; Rappe, 1993; Strandell et al., 1994). During the 1980s, titanium metal anodes were
17 developed to replace graphite electrodes (U.S. EPA, 1982a; Curlin and Bommaraju, 1991).
18 Currently, no U.S. facility is believed to use graphite electrodes in the production of chlorine gas
19 (telephone conversation between L. Phillips, Versar, Inc., and T. Fielding, U.S. EPA, Office of
20 Water, February 1993).
21 Although the origin of the CDFs in graphite electrode sludge is uncertain, chlorination of
22 the cyclic aromatic hydrocarbons (such as dibenzofuran) present in the coal tar used as a binding
23 agent in the graphite electrodes has been proposed as the primary source (Strandell et al., 1994).
24 For this reason, sludges produced using metal electrodes were not expected to contain CDFs.
25 However, results of an analysis of metal electrode sludge from a facility in Sweden, analyzed as
26 part of the Swedish Dioxin Survey, showed that the sludge contained high levels of CDFs
27 (similar to those of the graphite sludge) and primarily nondetectable levels of CDDs (Strandell et
28 al., 1994). The sludge showed the same type of CDF congener pattern reported by Rappe et al.
29 (1991) and Rappe (1993). Strandell et al. (1994) suggested that chlorination of polyaromatic
30 hydrocarbons present in the rubber linings of the electrolytic cell may have formed the CDFs
31 found in the one sample analyzed.
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1 Although EPA does not regulate CDDs/CDFs specifically, it issued restrictions under the
2 Resource Conservation and Recovery Act (RCRA) on the land disposal of wastewater and
3 sludges generated by chlorine manufacturers that use the mercury cell process and the diaphragm
4 process (with graphite electrodes) (waste codes K071, K073, and K106) (40 CFR 268).
5
6 8.2.2. Manufacture of Chlorine Derivatives and Metal Chlorides
7 The limited sampling of chlorine-derivative products indicates that they contain very low,
8 if any, concentrations of CDDs/CDFs. Rappe et al. (1990c) analyzed a sample of chlorine bleach
9 consisting of 4.4% sodium hypochlorite. Most of the 2,3,7,8-substituted CDD/CDF congeners
10 were below the limits of detection (0.3 to 7 pg/L for all congeners except OCDD and OCDF,
11 which were 12 and 20 pg/L, respectively). No 2,3,7,8-substituted CDDs were detected. Tetra-,
12 penta-, and hexa-CDFs were detected at levels of 13 pg/L or lower. The TEQ content of the
13 sample was 4.9 pg I-TEQDp/L. Hutzinger and Fiedler (1991a) reported finding no CDDs/CDFs
14 at a detection limit of 4 ng/kg in chlorine gas or in samples of 10% sodium hypochlorite, 13%
15 sodium hypochlorite, and 31 to 33% hydrochloric acid at a detection limit of 1 |ig/kg.
16 Hutzinger and Fiedler (199la) reported the results of analyses of samples of ferric
17 chloride (FeCls), aluminum trichloride (Aids), CuCb, CuCl, silicon tetrachloride (SiCU), and
18 titanium tetrachloride (TiCl4) for their content of HpCDF, OCDF, HpCDD, and OCDD. The
19 sample of FeCl3 contained HpCDF and OCDF in the low |ig/kg range, but no HpCDD or OCDD
20 was detected at a DL of 0.02 |ig/kg. One of the two samples of AlCls analyzed also contained a
21 low (|ig/kg) concentration of OCDF. The samples of CuCb and CuCl contained concentrations
22 of HpCDF, OCDF, and OCDD of less than 1 |ig/kg. The results are presented in Table 8-6.
23
24 8.3. MANUFACTURE OF HALOGENATED ORGANIC CHEMICALS
25 Several chemical production processes generate CDDs/CDFs (Versar, 1985; Hutzinger
26 and Fiedler, 199la). CDDs/CDFs can be formed during the manufacture of chlorophenols,
27 chlorobenzenes, and chlorobiphenyls (Versar, 1985; Ree et al., 1988). Consequently, disposal of
28 industrial wastes from manufacturing facilities producing these compounds may result in the
29 release of CDDs/CDFs to the environment. Also, the products themselves may contain these
30 compounds, and their use or consumption may result in additional releases to the environment.
31 CDD/CDF congener distribution patterns indicative of noncombustion sources have been
32 observed in sediments in southwest Germany and the Netherlands. According to Ree et al.
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1 (1988), the congener patterns found suggest that wastes from the production of chlorinated
2 organic compounds may be important historical sources of CDD/CDF contamination in these
3 regions. The production and use of many of the chlorophenols, chlorophenoxy herbicides, and
4 PCB products are now banned or strictly regulated in most countries. However, these products
5 may have been a source of the environmental contamination that occurred prior to the 1970s and
6 may continue to be a source of environmental releases under certain limited use and disposal
7 conditions (Rappe, 1992a).
8
9 8.3.1. Chlorophenols
10 Chlorophenols have been widely used for a variety of pesticidal applications. The more-
11 highly chlorinated phenols (tetra- and pentachlorophenol [PCP]) and their sodium salts have
12 been used primarily for wood preservation. The less-chlorinated phenols have been used
13 primarily as chemical intermediates in the manufacture of other pesticides. For example, 2,4-
14 dichlorophenol is used to produce the herbicides 2,4-dichlorophenoxyacetic acid (2,4-D), 4-(2,4-
15 dichlorophenoxy)butanoic acid (2,4-DB), 2-(2,4-dichlorophenoxy)-propanoic acid (2,4-DP),
16 Nitrophen, Genite, and Zytron, and 2,4,5-trichlorophenol was used to produce hexachlorophene,
17 2,4,5-T, Silvex, Erbon, Ronnel, and Gardona (Gilman et al., 1988; Hutzinger and Fiedler,
18 1991a). (Sections 8.3.7 and 8.3.8 contain information on EPA actions to control CDD/CDF
19 contamination of pesticides, including PCP and its salts, and to obtain additional data on
20 CDD/CDF contamination of pesticides.)
21 The two major commercial methods used to produce chlorophenols are (1) electrophilic
22 chlorination of molten phenol by chlorine gas in the presence of catalytic amounts of a metal
23 chloride and organic chlorination promoters and stabilizers, and (2) alkaline hydrolysis of
24 chlorobenzenes under heat and pressure using aqueous methanolic sodium hydroxide. Other
25 manufacturing methods include conversion of diazonium salts of various chlorinated anilines and
26 chlorination of phenolsulfonic acids and benzenesulfonic acids, followed by the removal of the
27 sulfonic acid group (Gilman et al., 1988; Hutzinger and Fiedler, 1991a).
28 Because of the manufacturing processes employed, commercial chlorophenol products
29 can contain appreciable amounts of impurities (Gilman et al., 1988). During the direct
30 chlorination of phenol, CDDs/CDFs can form either by the condensation of tri-, tetra-, and
31 pentachlorophenols or by the condensation of chlorophenols with hexachlorocyclohexadienone
32 (which forms from excessive chlorination of phenol). During alkaline hydrolysis of
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1 chlorobenzenes, CDDs/CDFs can form through chlorophenate condensation (Ree et al., 1988;
2 Oilman et al., 1988; Hutzinger and Fiedler, 1991a).
3 The limited information on CDD/CDF concentrations in chlorophenols published in the
4 1970s and early 1980s was compiled by Versar (1985) and Hutzinger and Fiedler (199la). The
5 results of several major studies cited by these reviewers (Firestone et al., 1972; Rappe et al.,
6 1978a, 1978b) are presented in Table 8-7. Typically, CDDs/CDFs were not detected in
7 monochlorophenols and dichlorophenols (DCP) but were reported in trichlorophenols (TrCP)
8 and tetrachlorophenols (TeCP). More recent results of testing of 2,4-dichlorophenol (2,4-DCP),
9 performed in response to the Toxic Substances Control Act (TSCA) dioxin/furan test rule,
10 showed no detectable concentrations of 2,3,7,8-substituted tetra- through hepta-CDD/CDFs.
11 Other than a study by Hagenmaier (1986) that reported finding 2,3,7,8-TCDD at a
12 concentration of 0.3 |ig/kg in a sample of 2,3,4,5-tetrachlorophenol, no more recent data on
13 concentrations of CDDs and CDFs could be found in the literature for the mono- through tetra-
14 chlorophenols. Tables 8-8 and 8-9 present summaries of several studies that reported CDD/CDF
15 concentrations in PCP and in PCP-Na products, respectively. Many of these studies do not
16 report congener-specific concentrations, and many are based on products obtained from non-U.S.
17 sources.
18
19 8.3.1.1. Regulatory Actions for Chlorophenols
20 Section 8.3.8 of this report describes regulatory actions taken by EPA to control the
21 manufacture and use of chlorophenol-based pesticides. In the mid-1980s, EPA's Office of Solid
22 Waste (OSW) promulgated, under RCRA, land disposal restrictions on wastes (wastewaters and
23 nonwastewaters) resulting from the manufacture of chlorophenols (40 CFR 268). Table 8-10
24 lists all wastes in which CDDs/CDFs are specifically regulated by EPA as hazardous
25 constituents, including chlorophenol wastes (waste codes F020 and F021). The regulations
26 prohibit the land disposal of these wastes until they are treated to a level below the routinely
27 achievable DLs in the waste extract listed in Table 8-10 for each of the following congener
28 groups: TCDDs, PeCDDs, HxCDDs, TCDFs, PeCDFs, and HxCDFs. Wastes from PCP-based
29 wood-preserving operations (waste codes K001 and F032) are also regulated as hazardous wastes
30 under RCRA (40 CFR 261).
31 EPA's Office of Water promulgated effluent limitations for facilities that manufacture
32 chlorinated phenols and discharge treated wastewater (40 CFR 414.70). These effluent
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1 limitations do not specifically regulate CDDs or CDFs. The effluent limitations for the
2 individually regulated chlorinated phenols are less than or equal to 39 jig/L for facilities that use
3 biological end-of-pipe treatment.
4 DCPs and TrCPs are subject to reporting under the dioxin/furan test rule, which is
5 discussed in Section 8.3.7 of this report. Since the effective date of that rule (June 5, 1987), only
6 the 2,4-DCP isomer has been commercially produced in (or imported to) the United States, and
7 as noted in Table 8-7, no CDDs/CDFs were detected in the product. Testing is required for the
8 other DCPs and TrCPs, if manufacture or importation resumes. Similarly, TeCPs were subject to
9 reporting under the Dioxin/Furan Pesticide Data Call-In (DCI) (discussed in Section 8.3.8 of this
10 report). Since issuance of the DCI, the registrants of TeCP-containing pesticide products have
11 elected to no longer support the registration of their products in the United States.
12 In January 1987, EPA entered into a settlement agreement with PCP manufacturers that
13 set limits, effective in February 1989, on the allowed uses of PCP and its salts and the maximum
14 allowable concentrations of 2,3,7,8-TCDD and HxCDDs. Section 8.3.8 discusses the 1987 PCP
15 settlement agreement and includes estimates of current releases of CDDs/CDFs associated with
16 use of PCP in the United States. Section 12.3.1 provides an estimate of the amount of
17 CDDs/CDFs that may have entered the environment or that are contained within treated wood
18 products as a result of prior use of PCP and PCP-Na.
19 Since the late 1980s, U.S. commercial production of chlorophenols has been limited to
20 2,4-dichlorophenol (2,4-DCP) and PCP. As noted above, disposal of wastes generated during
21 the manufacture of chlorophenols is strictly regulated, and thus releases to the environment are
22 expected to be negligible. With regard to releases associated with the use of 2,4-DCP, no
23 CDDs/CDFs have been detected in 2,4-DCP. Releases associated with the use of PCP are
24 presented in Sections 8.3.8 and 12.3.1.
25
26 8.3.2. Chlorobenzenes
27 Chlorobenzenes have been produced in the United States since 1909. U.S. production
28 operations were developed primarily to provide chemical raw materials for the production of
29 phenol, aniline, and various pesticides based on the higher chlorinated benzenes. Because of
30 (incremental) changes in the processes used to manufacture phenol and aniline and the phaseout
31 of highly chlorinated pesticides such as DDT and hexachlorobenzene, U.S. production of
32 Chlorobenzenes in 1988 had decreased to 50% of the peak production level, in 1969.
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1 Chlorobenzenes can be produced via three methods: (1) electrophilic substitution of
2 benzene (in liquid or vapor phase) with chlorine gas in the presence of a metal salt catalyst, (2)
3 oxidative chlorination of benzene with HC1 at 150 to 300 °C in the presence of a metal salt
4 catalyst, and (3) dehydrohalogenation of hexachlorocyclohexane wastes at 200 to 240 °C with a
5 carbon catalyst to produce trichlorobenzene, which can be further chlorinated to produce more-
6 highly chlorinated benzenes (Ree et al., 1988; Hutzinger and Fiedler, 1991a; Bryant, 1993).
7 All chlorobenzenes currently manufactured in the United States are produced by the
8 electrophilic substitution process using liquid-phase benzene (i.e., temperature is at or below
9 80 °C). Ferric chloride is the most common catalyst employed. Although this method can be
10 used to produce mono- through hexachlorobenzene, the extent of chlorination is controlled to
11 yield primarily monochlorobenzene (MCBz) and dichlorobenzene (DCBz). The finished product
12 is a mixture of chlorobenzenes, and refined products must be obtained by distillation and
13 crystallization (Bryant, 1993).
14 CDDs/CDFs can be produced inadvertently during the manufacture of chlorobenzenes by
15 nucleophilic substitution and pyrolysis mechanisms (Ree et al., 1988). The criteria required for
16 production of CDDs/CDFs via nucleophilic substitution are (1) oxygen as a nuclear substituent
17 (i.e., presence of chlorophenols) and (2) production or purification of the substance under
18 alkaline conditions. Formation via pyrolysis requires reaction temperatures above 150 °C (Ree
19 et al., 1988; Hutzinger and Fiedler, 1991a). The liquid-phase electrophilic substitution process
20 currently used in the United States does not meet either of these criteria. Although Ree et al. and
21 Hutzinger and Fiedler state that the criteria for formation of CDDs/CDFs via nucleophilic
22 substitution may be present in the catalyst neutralization and purification/distillation steps of the
23 manufacturing process, Opatick (1995) states that the chlorobenzene reaction product in U.S.
24 processes remains mildly acidic throughout these steps.
25 Table 8-11 summarizes the very limited published information on CDD/CDF
26 contamination of chlorobenzene products. The presence of CDDs/CDFs has been reported in
27 TCBz, PeCBz, and HCBz. No CDDs/CDFs have been reported in MCBz or DCBz. Conflicting
28 data exist concerning the presence of CDDs/CDFs in TCBz. One study (Villanueva et al., 1974)
29 detected no CDDs/CDFs in one sample of 1,2,4-TCBz at a DL of 0.1 |ig/kg. Hutzinger and
30 Fiedler (1991a) reported unpublished results of Dr. Hans Hagenmaier showing CDD/CDF
31 congener group concentrations ranging from 0.02 to 0.074 |ig/kg in a sample of mixed TCBz.
32 Because the TCBz examined by Hagenmaier contained about 2% hexachlorocyclohexane, it is
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1 reasonable to assume that the TCBz was produced by dehydrohalogenation of
2 hexachlorocyclohexane (a manufacturing process not currently used in the United States).
3
4 8.3.2.1. Regulatory Actions for Chlorobenzenes
5 EPA determined, as part of the Federal Insecticide, Fungicide, and Rodenticide Act
6 (FIFRA) DCI (discussed in Section 8.3.8), that the 1,4-DCBz manufacturing processes used in
7 the United States are not likely to form CDDs/CDFs. MCBz, DCBz, and TCBz are listed as
8 potential precursor chemicals under the TSCA dioxin/furan test rule and are subject to reporting
9 (see Section 8.3.7). In addition, EPA issued a Significant New Use Rule (SNUR) under Section
10 5(a)(2) of TSCA on December 1, 1993 (effective January 14, 1994) for PeCBz and 1,2,4,5-
11 TeCBz (Federal Register, 1993c). This rule requires persons to submit a notice to EPA at least
12 90 days before manufacturing, importing, or processing either of these compounds in amounts of
13 10,000 pounds or greater per year per facility for any use. All registrations of pesticide products
14 containing HCBz were cancelled in the mid-1980s (Carpenter et al., 1986).
15 OSW promulgated land disposal restrictions on wastes (i.e., wastewaters and
16 nonwastewaters) resulting from the manufacture of chlorobenzenes (40 CFR 268). Table 8-10
17 lists all solid wastes for which EPA specifically regulates CDDs and CDFs, including
18 chlorobenzene wastes, as hazardous constituents. The regulations prohibit the land disposal of
19 these wastes until they are treated to a level below the routinely achievable DLs in the waste
20 extract listed in Table 8-10 for each of the following congener groups: TCDDs, PeCDDs,
21 HxCDDs, TCDFs, PeCDFs, and HxCDFs.
22 EPA's Office of Water promulgated effluent limitations for facilities that manufacture
23 chlorinated benzenes and discharge treated wastewater (40 CFR 414.70). These effluent
24 limitations do not specifically address CDDs and CDFs. The following chlorinated benzenes are
25 regulated: chlorobenzene; 1,2-dichlorobenzene; 1,3-dichlorobenzene; 1,4-dichlorobenzene;
26 1,2,4-trichlorobenzene; and hexachlorobenzene. The effluent limitations for the individual
27 regulated chlorinated benzenes are less than or equal to 77 jig/L for facilities that use biological
28 end-of-pipe treatment and less than or equal to 196 jig/L for facilities that do not use biological
29 end-of-pipe treatment.
30 Since at least 1993, U.S. commercial production of chlorobenzenes has been limited to
31 MCBz, 1,2-dichlorobenzene (1,2-DCBz), 1,4-di chlorobenzene (1,4-DCBz), and, to a much lesser
32 extent, 1,2,4-trichlorobenzene (1,2,4-TCBz). As noted above, CDD/CDF formation is not
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1 expected under the normal operating conditions of the processes currently used in the United
2 States to produce these four chemicals. No tetra-, penta-, or hexachlorinated benzenes are now
3 intentionally produced or used in the United States (Bryant, 1993). Thus, releases of
4 CDDs/CDFs from the manufacture of chlorobenzenes in 1995 were estimated to be negligible.
5 Because the information available on CDD/CDF content of MCBz to PeCBz is very limited and
6 is based primarily on unpublished European data, and because information on the chlorobenzene
7 manufacturing processes in place during 1987 is not readily available, no emission estimates can
8 be made for 1987.
9
10 8.3.3. Chlorobiphenyls
11 PCBs are manufactured by the direct batch chlorination of molten biphenyl in the
12 presence of a catalyst, followed by separation and purification of the desired chlorinated
13 biphenyl fractions. During the manufacture of PCBs, the inadvertent production of CDFs also
14 occurs. This section addresses potential releases of CDDs/CDFs associated with leaks and spills
15 of PCBs. CDFs have been shown to form when PCB-containing transformers and capacitors
16 undergo malfunctions or are subjected to fires that result in accidental combustion of the
17 dielectric fluid. This combustion source of PCB-associated CDFs is discussed in Section 6.6.
18 Section 11.2 addresses releases of dioxin-like PCBs.
19 PCB production is believed to have occurred in 10 countries. The total amount of PCBs
20 produced worldwide since 1929 (i.e., the first year of known production) is estimated to total 1.5
21 billion kg. Initially, PCBs were primarily used as dielectric fluids in transformers. After World
22 War II, PCBs found steadily increasing use as dielectric fluids in capacitors, as heat-conducting
23 fluids in heat exchangers, and as heat-resistant hydraulic fluids in mining equipment and vacuum
24 pumps. PCBs also were used in a variety of "open" applications (i.e., uses from which PCBs
25 cannot be recollected) including plasticizers, carbonless copy paper, lubricants, inks, laminating
26 agents, impregnating agents, paints, adhesives, waxes, additives in cement and plaster, casting
27 agents, dedusting agents, sealing liquids, fire retardants, immersion oils, and pesticides (DeVoogt
28 and Brinkman, 1989).
29 PCBs were manufactured in the United States from 1929 until 1977. U.S. production
30 peaked in 1970, with a volume of 38.56 million kg. Monsanto Corporation, the major U.S.
31 producer, voluntarily restricted the use of PCBs in 1971, and annual production fell to 18.14
32 million kg in 1974. Monsanto Corporation ceased PCB manufacture in mid-1977 and shipped
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1 the last inventory in October 1977. Regulations issued by EPA beginning in 1977, principally
2 under TSCA (40 CFR 761), strictly limited the production, import, use, and disposal of PCBs.
3 (See Section 4.1 for details on TSCA regulations.) The estimated cumulative production and
4 consumption volumes of PCBs in the United States from 1930 to 1975 were 635.03 million kg
5 produced; 1.36 million kg imported (primarily from Japan, Italy, and France); 568.35 million kg
6 sold in the United States; and 68.04 million kg exported (ATSDR, 1993; DeVoogt and
7 Brinkman, 1989).
8 Monsanto Corporation marketed technical-grade mixtures of PCBs primarily under the
9 trade name Aroclor. The Aroclors are identified by a four-digit numbering code in which the last
10 two digits indicate the chlorine content by weight percent. The exception to this coding scheme
11 is Aroclor 1016, which contains only mono- through hexachlorinated congeners with an average
12 chlorine content of 41%. The following list shows the percentages of total Aroclor production,
13 by (Aroclor mixture) during 1957 to 1977, as reported by Brown (1994).
14
15 1957-1977
16 U.S. Production
17 Aroclor (°A
18
19
20
21
22
23
24
25
26
27
28 The trade names of the major commercial technical-grade mixtures of PCBs
29 manufactured in other countries included Clophen (Germany), Fenclor and Apirolio (Italy),
30 Kanechlor (Japan), Phenoclor and Pyralene (France), Sovtel (USSR), Delor and Delorene
31 (Czechoslovakia), and Orophene (German Democratic Republic) (DeVoogt and Brinkman,
32 1989). Some of the mixtures marketed under these trade names were similar in terms of chlorine
33 content (by weight percent and average number of chlorines per molecule) to various Aroclors,
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1221
1016
1232
1242
1248
1254
1260
1262
1268
0.96
12.88
0.24
51.76
6.76
15.73
10.61
0.83
0.33
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1 as shown below. Mixtures that are comparable in terms of chlorine content were marketed under
2 several trade names, as shown below.
3
4 Aroclor Clophen Pyralene Phenoclor Fenclor Kanechlor
5 1232 2000 200
6 1242 A-30 3000 DP-3 42 300
7 1248 A-40 DP-4 400
8 1254 A-50 DP-5 54 500
9 1260 A-60 DP-6 64 600
10
11
12 During the commercial production of PCBs, thermal oxidative cyclization under alkaline
13 conditions resulted in the inadvertent production of CDFs in most of the commercial PCB
14 mixtures (Brown et al., 1988; ATSDR, 1993). Bowes et al. (1975a) first reported detection of
15 CDFs in Aroclor products; samples of unused Aroclors manufactured in 1969 and 1970 were
16 found to have CDF (i.e., TCDF through HxCDF) concentrations ranging from 0.8 to 2 mg/kg.
17 Bowes et al. (1975b) employed congener-specific analytical methodology and detected 2,3,7,8-
18 TCDF and 2,3,4,7,8-PeCDF at concentrations ranging from 0.11 to 0.33 mg/kg and 0.12 to 0.83
19 mg/kg, respectively, in unused samples of Aroclor 1254 and Aroclor 1260. The presence of
20 CDDs in commercial PCB mixtures, although at much lower concentrations than those of the
21 CDFs, was reported by Hagenmaier (1987) and Malisch (1994). Table 8-12 presents the CDF
22 and CDD congener group concentrations reported by Bowes et al. (1975a) and those reported in
23 subsequent years for unused PCBs by Erickson (1986), ATSDR (1993), Hagenmaier (1987), and
24 Malisch (1994).
25 Several researchers reported concentrations of specific CDD/CDF congeners in
26 commercial PCB mixtures (Bowes et al., 1975b; Brown et al., 1988; Hagenmaier, 1987; Malisch,
27 1994). Table 8-13 presents the results of these four studies. Only the Hagenmaier (1987) and
28 Malisch (1994) studies, however, reported the concentrations of all 2,3,7,8-substituted CDDs and
29 CDFs. It is evident from the table that major variations are found in the levels of 2,3,7,8-TCDF
30 and 2,3,4,7,8-PeCDF in the Clophen mixtures reported by Hagenmaier (1987) and Malisch
31 (1994) and the corresponding levels in the Aroclor mixtures reported by Bowes et al. (1975b)
32 and Brown et al. (1988).
33 Brown et al. (1988) compared the levels of 2,3,7,8-TCDF; 2,3,4,7,8-PeCDF; and
34 1,2,3,7,8,9-HxCDF in used samples (i.e., samples from previously used capacitors and
35 transformers) and unused samples of Aroclors 1016, 1242, 1254, and 1260. The concentration
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1 ranges reported for the used and unused Aroclors were similar, leading Brown et al. (1988) to
2 conclude that CDFs are not formed during the normal use of PCBs in electrical equipment.
3 Amounts of CDD/CDF TEQ emissions that may have been released to the environment
4 during 1987, 1995, and 2000 from spills and leaks of in-service PCBs cannot be accurately
5 estimated because reliable data regarding leaked and spilled PCBs are not available.
6
7 8.3.4. Polyvinyl Chloride
8 PVC resins are produced when free radical initiators are used to induce the
9 polymerization of vinyl chloride monomer (VCM). With the exception of one plant that uses a
10 process involving the catalytic reaction of acetylene and HC1 to manufacture VCM directly,
11 VCM is typically produced by the thermal dehydrochlorination (commonly known as cracking)
12 of ethylene dichloride (EDC). The cracking of EDC requires elevated pressure (20 to 30
13 atmospheres) and temperature (450 to 650 °C) and yields VCM and HC1 at about a 1:1 molar
14 ratio. EDC is produced by two different methods: (1) direct chlorination of ethylene with
15 chlorine in the presence of a catalyst at a temperature of 50 to 60 °C and pressure of 4 to 5
16 atmospheres, and (2) oxychlorination, which involves reaction of ethylene with HC1 and oxygen
17 in the presence of a catalyst at temperatures generally less than 325 °C. The primary source of
18 HC1 for the oxy chlorination process is the HC1 produced from the cracking of EDC to form
19 VCM. All VCM plants, with the exception of the one facility noted above, are integrated with
20 EDC production facilities (Vinyl Institute, 1998).
21 Although it has generally been recognized that CDDs/CDFs are formed during the
22 manufacture of EDC, VCM, and PVC, manufacturers and environmental public interest groups
23 have disagreed as to the quantity of CDDs/CDFs that are formed and released to the environment
24 in wastes and possibly in PVC products. Although EPA regulates emissions from EDC/VCM
25 production facilities under the Clean Water Act (40 CFR 61), the Clean Air Act (40 CFR 414),
26 and RCRA (40 CFR 268, waste codes F024, KOI9, and K020), CDDs/CDFs are not specifically
27 regulated pollutants; as a consequence, monitoring data for CDDs/CDFs in emissions are
28 generally lacking.
29 In 1993, Greenpeace International issued a report on CDD/CDF emissions associated
30 with the production of EDC/VCM (Greenpeace, 1993). Greenpeace estimated that 5 to 10 g I-
31 TEQDF are released to the environment (air, water, and ground combined) annually for every
32 100,000 metric tons of VCM produced. This emission factor was based on data gathered by
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1 Greenpeace on four European plants. The Vinyl Institute responded with a critique of the
2 Greenpeace report (ChemRisk, 1993). Miller (1993) summarized the differing views of the two
3 parties. According to Miller, European PVC manufacturers claimed the emission factor was 0.01
4 to 0.5 g I-TEQoF/100,000 metric tons of VCM, but although Greenpeace and ChemRisk used
5 basically the same monitoring information to develop their emission factors, Greenpeace
6 adjusted the emission factor to account for unquantified fugitive emissions and waste products
7 that contain unspecified amounts of CDDs/CDFs.
8 In 1995, Greenpeace issued another report (Stringer et al., 1995) reiterating the
9 organization's concern that the generation and emission of CDDs/CDFs may be significant and
10 urging that further work be initiated to quantify and prevent emissions. Stringer et al. (1995)
11 presented the results of analyses of three samples of chlorinated wastes obtained from U.S.
12 EDC/VCM manufacturing facilities. The three wastes were characterized according to EPA
13 hazardous waste classification numbers as an F024 waste (waste from the production of short-
14 chain aliphatics by free radical catalyzed processes), a KOI9 waste (heavy ends from the
15 distillation of ethylene from EDC production), and a probable K020 waste (heavy ends from
16 distillation of VC in VCM manufacture). Table 8-14 presents the analytical results reported by
17 Stringer et al. (1995). This study acknowledged that because EDC/VCM production
18 technologies and waste treatment and disposal practices are very site-specific, the limited
19 information available on CDD/CDF generation and emissions made it difficult to quantify
20 amounts of CDDs/CDFs generated and emitted.
21 In response to the lack of definitive studies, and at the recommendation of EPA, U.S.
22 PVC manufacturers initiated an extensive monitoring program, the Dioxin Characterization
23 Program, to evaluate the extent of any CDD/CDF releases to air, water, and land, as well as any
24 product contamination. Manufacturers performed emission and product testing at various
25 facilities that were representative of various manufacturing and process control technologies. In
26 1998, the Vinyl Institute completed studies of CDD/CDF releases in wastewater, wastewater
27 treatment plant solids, and stack gases, as well as studies of CDD/CDF content of products (i.e.,
28 PVC resins and EDC sold as products) (Vinyl Institute, 1998).
29 After the completion of the studies, the Vinyl Institute created an external advisory group
30 to advise the institute on the conduct of the Dioxin Characterization Program and to provide an
31 independent review of the program results. In its final evaluation report, the advisory group
32 judged the industry's coverage to be fairly comprehensive in terms of the number of facilities
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1 and waste streams sampled. The number of samples of PVC product, stack emissions,
2 wastewaters, and wastewater sludges obtained from the different types of manufacturing
3 facilities was deemed by the advisory group to provide a sufficient database to evaluate annual
4 industry releases. The advisory group concluded that the process established by the Vinyl
5 Institute to ensure that data collected as part of its Dioxin Characterization Program were
6 representative of normal process operations was a good one. After auditing the Vinyl Institute's
7 estimates of annual releases, the advisory group concluded that the data were properly validated
8 and that the results were extrapolated to annual industry release estimates in a creditable
9 scientific manner.
10 EPA reviewed the Vinyl Institute (1998) studies and concurred with the conclusions of
11 the external advisory group. EPA assigned a high confidence rating to the activity level
12 estimates and a medium confidence rating to the emission factor estimates developed by the
13 Vinyl Institute.
14 In September 2002, the Chlorine Chemistry Council (CCC) met to review dioxin release
15 estimates for 2000 for various EDC/VCM manufacturing facilities. Several companies provided
16 stack gas emissions and wastewater emissions data, as well as a discussion of how they
17 generated the release and transfer estimates reported in the TRI for 2000. In March 2004, the
18 CCC met again to discuss the results, to date, of the Chlorine Chemistry Council CDD/CDF Data
19 Validation Study for PVC/EDC/VCM and chlor-alkali facilities. The study's goal was to
20 provide facility-specific water, air, and land release estimates for the years 2000 and 2002. As of
21 the date of this report, data validation studies were provided for 16 of 20 facilities in the CCC
22 that were considered chlor-alkali production facilities and PVC/EDC/VCM manufacturing
23 plants.
24
25 8.3.4.1. Wastewater
26 The Vinyl Institute (1998) presented results for treated wastewater samples collected
27 during April and May of 1995 at six sites that manufactured only PVC, at three sites that
28 manufactured EDC and VCM, and at one site that manufactured EDC, VCM, and PVC. In terms
29 of production, the six PVC-only sites represent approximately 15% of the total estimated 1995
30 U.S. and Canadian PVC production. Together, the three EDC/VCM sites and the one
31 EDC/VCM/PVC site represent 27% of the total estimated 1995 U. S. EDC production. Samples
32 taken from PVC-only sites were taken from sites that manufactured suspension PVC resin as
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1 well as those that manufactured dispersion PVC resin. Samples for the other four sites were
2 taken from sites that used direct and oxychlorination processes, fixed and fluidized beds, and
3 low- and high-temperature direct chlorination. The wastewater samples from one of the
4 EDC/VCM sites, one of the PVC-only sites, and the EDC/VCM/PVC site were taken from
5 effluents derived from process areas not limited to EDC/VCM, EDC/VCM/PVC, or PVC
6 manufacturing.
7 The results of the sampling are presented in Table 8-15. In all samples, the method
8 detection limit (MDL) for all congeners except OCDD and OCDF was 10 pg/L or less. The
9 MDL for OCDD and OCDF was 50 pg/L or less. CDDs/CDFs were detected in two of the six
10 samples from PVC-only sites (0.52 and 2 pg I-TEQop/L, assuming nondetect values are equal to
11 zero [ND = 0]). The overall mean TEQ concentrations were 0.88 pg I-TEQDF/L (assuming ND =
12 0) and 4.7 pg I-TEQDF/L (assuming ND = 1/2 MDL). CDDs/CDFs were detected in all four of
13 the samples from EDC/VCM/PVC sites. The overall mean TEQ concentrations were 0.42 pg I-
14 TEQoF/L (assuming ND = 0) and 4.4 pg I-TEQDF/L (assuming ND = 1/2 MDL).
15 Using these sample results, the Vinyl Institute developed I-TEQDF emission factors for
16 the two site categories: PVC-only and EDC/VCM/PVC manufacturing facilities. First,
17 individual site release rates were estimated using the treated wastewater effluent flow rate
18 recorded by the site during sampling, assuming that the site continuously released CDDs/CDFs
19 at its calculated total I-TEQop, 24 hr/day, 360 day/yr, at the recorded water effluent rate. The
20 total releases from each site category (PVC-only or EDC/VCM/PVC facilities) were then
21 estimated by averaging the individual release rates per 1000 metric ton of PVC or EDC using the
22 estimated 1995 PVC and EDC production statistics for the sampled sites. These values were
23 then scaled up to estimate total U.S. releases in treated wastewater from the site categories. It is
24 not possible using the data presented in the Vinyl Institute study to calculate emission factors for
25 TEQoF-WHOgg. However, because 1,2,3,7,8-PeCDD was not detected in any wastewater
26 sample, the TEQoF-WHOgg emission factors would be lower than the I-TEQop emission factors.
27 The mean emission factors derived from the sample results for the PVC-only facilities are
28 2.3 |ig I-TEQDF/1,000 metric tons of PVC (ND = 0) and 29 |ig I-TEQDF/1,000 metric tons of
29 PVC (ND = 1/2 MDL). The mean emission factors for the EDC/VCM/PVC facilities are 2.9 |ig
30 I-TEQoF/1,000 metric tons (ND = 0) and 15 |ig I-TEQDF/1,000 metric tons of EDC (ND = 1/2
31 MDL).
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1 The Vinyl Institute (1998) combined these emission factors with 1995 industry
2 production statistics (5,212 metric tons of PVC and 11,115 metric tons of EDC) to yield release
3 estimates of 0.011 g I-TEQDF (ND = 0) and 0.15 g I-TEQDF (ND = 1/2 DL) from PVC-only
4 manufacturing sites and 0.032 g I-TEQDF (ND = 0) and 0.17 g I-TEQDF (ND = 1/2 DL) from
5 EDC/VCM and EDC/VCM/PVC facilities for a total I-TEQDF release to water in 1995 of 0.043 g
6 (ND = 0) and 0.32 g (ND = 1/2 DL).
7 Data validation studies of the CCC provided water release estimates for 16 facilities that
8 were considered chlor-alkali production facilities and PVC/EDC/VCM manufacturing plants
9 (CCC, 2004). Half of these facilities were not involved with the production of PVC/EDC/VCM.
10 Tables 8-16 and 8-17 depict the congener-specific data associated with the water releases from
11 the PVC/EDC/VCM manufacturing plants and the chlor-alkali production facilities, respectively.
12 For the reference year 2000, water releases for PVC/EDC/VCM manufacturing facilities were
13 23.8 g I-TEQop (22.6 g TEQoF-WHOgg), while water releases for chlor-alkali plants were 1.85 g
14 I-TEQoF (1.82 g TEQDF-WHO98). More than 99% of the water releases from PVC/EDC/VCM
15 plants occurred at three facilities. More than 98% of the water releases from chlor-alkali plants
16 occurred at three facilities, with one facility accounting for over 58% of the water releases.
17 These emission estimates are assigned a medium confidence rating on the basis of the medium
18 rating given to the emission factor estimates.
19
20 8.3.4.2. Wastewater Treatment Plant Solids
21 The Vinyl Institute (1998) presented results for 14 samples collected in 1996 from nine
22 EDC/VCM/PVC manufacturing sites. Samples were collected from 4 of the 5 U.S. sites that
23 manufactured EDC, VCM, and PVC; 3 of the 7 U.S. sites that manufactured EDC and VCM but
24 not PVC; and 2 of the 21 sites that manufactured PVC but not EDC or VCM. On the basis of
25 1995 production data, the two PVC-only sites manufactured approximately 4.7% of the total
26 estimated U.S. and Canadian PVC resin produced. The sampled EDC/VCM and
27 EDC/VCM/PVC sites manufactured 56% of the total estimated 1995 U.S. EDC produced.
28 Samples from the PVC-only sites were taken from sites that manufactured suspension PVC resin
29 as well as sites that manufactured dispersion PVC resin. Samples taken from the EDC/VCM and
30 EDC/VCM/PVC sites were taken from sites that used direct and oxychlorination processes, fixed
31 and fluidized EDC reactor beds, low- and high-temperature direct chlorination, and air, oxygen,
32 and mixed air-oxygen feeds.
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1 On the basis of the sample results, the Vinyl Institute determined that the results for
2 facilities using different EDC reactor bed technologies (fluidized bed vs. fixed bed) appeared to
3 differ significantly; therefore, they developed annual I-TEQDF emission estimates for three
4 categories: PVC-only, EDC/VCM/PVC fixed-bed, and EDC/VCM/PVC fluidized-bed facilities.
5 Nine U.S. sites use fixed-bed technology and six use fluidized-bed technology. Four of each
6 type of facility were sampled by the Vinyl Institute. It is not possible, using the data presented in
7 the Vinyl Institute (1998), to calculate emission factors for TEQDF-WHO98. Because 1,2,3,7,8-
8 PeCDD was detected in only 3 of 10 samples but OCDD and OCDF were detected in all
9 samples, it is likely that the TEQoF-WHOgg emission factors would not be significantly different
10 from the I-TEQop emission factors.
11 Results of the sampling are presented in Table 8-15. The MDLs for all congeners were
12 less than 150 ng/kg and usually less than 10 ng/kg. CDDs/CDFs were detected in all samples.
13 The ranges of TEQ concentrations (dry-weight basis) for the two PVC-only facilities were 1.1 to
14 2.6 ng I-TEQoF/kg (ND = 0) and 2.8 to 4.4 ng I-TEQDF/kg (ND = 1/2 MDL). On an emission-
15 factor basis, the ranges were 1.7 to 46 jig I-TEQDF/1,000 metric tons of PVC produced (ND = 0)
16 and 4.3 to 78 |ig I-TEQDF/1,000 metric ton of PVC produced (ND = 1/2 DL). The range of TEQ
17 concentrations for the samples from the EDC/VCM or EDC/VCM/PVC sites were 88 to 6,850
18 ng I-TEQoF/kg (ND = 0) and 93 to 6,850 ng I-TEQDF/kg (ND = 1/2 DL). On an emission-factor
19 basis, the ranges were 28 to 4,000 |ig I-TEQDF/1,000 metric tons of EDC (ND = 0) and 29 to
20 4,000 |ig I-TEQDF/1,000 metric tons of EDC (ND = 1/2 DL).
21 The annual amounts of I-TEQDp generated in 1995 in each of the three facility categories
22 were estimated by the Vinyl Institute as follows. First, total annual contributions at each
23 sampled site were estimated by multiplying the I-TEQDp from the sample by the annual
24 production of wastewater solids at that site. These annual site contributions of I-TEQDF were
25 then summed for each of the three facility types and multiplied by the ratio of each category's
26 total annual production of PVC or EDC to the sum of the annual production of the sampled sites
27 in that category.
28 The Vinyl Institute (1998) combined these emission factors with 1995 industry
29 production statistics to yield estimated amounts of I-TEQDp in wastewater treatment plant solids.
30 For PVC-only facilities, estimated amounts are 0.069 g I-TEQDF/yr (ND = 0) and 0.12 g
31 I-TEQop/yr (ND = 1/2 DL), assuming an annual PVC production of 5,212,000 metric tons. For
32 EDC/VCM/PVC fixed-bed facilities, the estimated amounts of TEQ are 1 g I-TEQDF/yr (ND = 0
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1 or ND = 1/2 DL), assuming an EDC annual production volume of 5,400,000 metric tons. For
2 EDC/VCM/PVC fluidized-bed facilities, the estimated amount of TEQ is 11 g I-TEQDF/yr (ND =
3 0 or ND = 1/2 DL), assuming EDC annual production volume of 5,600,000 metric tons. Thus,
4 total amounts of TEQ in wastewater treatment plant solids are estimated to have been 12.1 g I-
5 TEQoF in 1995 (ND = 0 or ND = 1/2 DL).
6 According to the Vinyl Institute survey data, member companies dispose of wastewater
7 solids by three methods: (1) RCRA hazardous waste landfilling (approximately 1% of industry
8 total solids), (2) landfarming (approximately 6%), and (3) secure on-site landfilling (93%).
9 Solids disposed of by methods 1 and 3 are assumed to be well controlled to prevent release into
10 the general environment, whereas solids disposed of by landfarming are not as well controlled
11 and could be released to the environment. Therefore, an estimated 0.73 g I-TEQDF (6% of 12.1 g
12 I-TEQop) can be considered as potentially released to the environment in 1995.
13 From the data validation studies presented in March 2004, only one facility (the Georgia
14 Gulf facility in Plaquemine, LA) reported releases resulting from land farming activities in 2000
15 (CCC, 2004). The congener-specific profile is presented in Table 8-18. Releases to land from
16 PVC/EDC/VCM facilities in 2000 were 1.36 g TEQDF-WHO98 (1.45 g I-TEQDF).
17 These emission estimates are assigned a medium confidence rating on the basis of the
18 medium rating given to the emission factor estimates.
19
20 8.3.4.3. Stack Gas Emissions
21 By grouping similarities of design and service, the Vinyl Institute (1998) subcategorized
22 thermal destruction units at EDC/VCM and/or PVC manufacturing units into three categories:
23 type A—vent gas incinerators at PVC-only resin plants, type B—vent gas thermal oxidizers at
24 EDC/VCM plants, and type C—liquid-only and liquid/vent gas thermal oxidizers at EDC/VCM
25 plants. Using an industry-wide survey, the Vinyl Institute identified 22 type A units at 11
26 facilities, 23 type B units at 10 facilities, and 17 type C units at 10 facilities. The Vinyl Institute
27 gathered test data from 5 of the 22 type A units (3 facilities representing 7% of total U.S. and
28 Canadian EDC/VCM/PVC production in 1995), 14 of the 23 type B units (8 facilities), and 13 of
29 the 17 type C units (7 facilities). The sampled type B and C units represent 70% of total U.S.
30 and Canadian EDC/VCM/PVC production in 1995.
31 Annual I-TEQop emission estimates were generated by the Vinyl Institute by combining
32 estimated emissions from tested units (i.e., based on measured stack gas results and plant-
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1 specific activity data) with an estimate of emissions from untested units. The emissions from the
2 untested units were estimated by multiplying the average emission factor for the tested units in
3 the category (the most likely estimate) or by multiplying the average emission factor of the tested
4 units with the highest emissions in each class (the upper-bound estimate) by the activity level for
5 the untested units. It is not possible using the data presented in the Vinyl Institute report to
6 calculate emission factors for TEQap-WHOgg.
7 The Vinyl Institute estimates of most likely and upper-bound emissions during 1995 for
8 these three categories are as follows:
9
Most likely emission Upper-bound emission
Category estimate (g I-TEQDF/yr) estimate (g I-TEQDF/yr)
PVC-only incinerators 0.0014 0.0019
EDC/VCM liquid and liquid/vents 3.7 7.2
EDC/VCM vents for VCM only 6.9 21.6
10
11 The Vinyl Institute (1998) also estimated emissions that may result from incineration of
12 EDC/VCM/PVC wastes processed by off-site, third-party processing. Using the emission factors
13 for liquid and liquid/vents developed in its study, the institute estimated that potential emissions
14 to air from this source category would be 0.65 g I-TEQop/yr (most-likely estimate) and 2.3 g I-
15 TEQop/yr (upper-bound estimate). Combining these third-party release estimates with those
16 developed above yields a 1995 estimate of 11.2 g I-TEQop/yr.
17 Data validation studies of the CCC indicate that eight P VC/EDC/VCM manufacturing
18 facilities released 5.51 g I-TEQDp (5.46 g TEQoF-WHOgg) to air, while two chlor-alkali
19 production plants reported releases to air of 0.08 g TEQDF-WHO98 in 2000 (CCC, 2004). More
20 than 85% of the air releases from PVC/EDC/VCM manufacturing facilities occurred at two
21 facilities. Congener-specific profiles of the release estimates are provided in Tables 8-19 and 8-
22 20. These emission estimates for 1995 and 2000 are assigned a medium confidence rating on the
23 basis of the medium rating given to the emission factor estimates.
24
25 8.3.4.4. Products
26 The Vinyl Institute (1998) presented results for 22 samples from 14 of the 24 U.S. and
27 Canadian facilities manufacturing suspension and mass PVC resins (13 pipe resins, 3 bottle
28 resins, and 6 packaging resins). The results are summarized in Table 8-19. The 14 sampled sites
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1 represent approximately 74% of estimated 1995 U.S. and Canadian suspension and mass PVC
2 resin production. CDDs/CDFs were detected in only one sample (0.043 ng I-TEQop/kg,
3 assuming ND = 0). The overall mean TEQ concentrations were 0.002 ng I-TEQDF/kg (ND = 0)
4 and 0.7 ng I-TEQDF/kg (ND = 1/2 MDL). The MDLs were 2 ng/kg or less for all congeners in
5 all samples except for OCDD and OCDF, which had MDLs of 6 ng/kg or less.
6 The same study also presented results for six samples from four of the seven U.S.
7 facilities manufacturing dispersion PVC resins. CDDs/CDFs were detected in five of the
8 samples. The results are summarized in Table 8-21. In terms of production, the four sampled
9 sites represent approximately 61% of estimated 1995 U.S. dispersion PVC resin production. The
10 results ranged from not detected to 0.008 ng I-TEQop/kg (overall mean = 0.001 ng I-TEQop/kg,
11 assuming ND = 0, and 0.4 ng I-TEQDF/kg, assuming ND = 1/2 MDL). The MDLs were 2 ng/kg
12 or less for all congeners in all samples except OCDD and OCDF, which had MDLs of 4 ng/kg or
13 less.
14 Results were also presented for five samples from 5 of the 15 U.S. facilities
15 manufacturing EDC. The results are summarized in Table 8-21. In terms of production, the five
16 sampled sites represent approximately 71% of total U.S. estimated 1995 EDC produced.
17 CDDs/CDFs were detected in only one sample (0.03 ng I-TEQop/kg). The overall mean TEQ
18 concentrations were 0.006 ng I-TEQDF/kg (ND = 0) and 0.21 ng I-TEQDF/kg (ND = 1/2 MDL).
19 The MDLs for all congeners were 1 ng/kg or less.
20 Using 1995 U.S. production data, 4.846 million metric tons of suspension and mass PVC,
21 0.367 million metric tons of dispersion PVC resins, and 1.362 million metric tons of EDC were
22 produced. Based on the average TEQ concentration observed, the Vinyl Institute estimated that
23 the total I-TEQDp contents of suspension/mass PVC resins, dispersion PVC resins, and EDC was
24 0.01 g, 0.004 g, and 0.008 g, respectively (ND = 0), and 3.39 g, 0.15 g, and 0.29 g, respectively
25 (ND = 1/2 MDL). Therefore, total I-TEQDF present in PVC in 1995 was estimated to be between
26 0.02 g (ND = 0) and 3.83 g (ND = 1/2 MDL). It is not possible using the data presented in the
27 Vinyl Institute report to calculate emission factors for TEQoF-WHOgg. However, because
28 neither 1,2,3,7,8-PeCDD nor OCDD was detected in any sample, the TEQDF-WHO98 emission
29 factors would be very similar to the I-TEQDp emission factors.
30 In 2000, approximately 6.55 million metric tons of PVC and 9.91 million metric tons of
31 EDC were produced in North America (C&EN, 2002). In 1995, approximately 5.58 million
32 metric tons of PVC and 7.83 million metric tons of EDC were produced in North America
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1 (C&EN, 2002). Of this total, approximately 94% of PVC production and approximately 17% of
2 EDC production occurred in the United States and were sold as products. The breakdown of
3 PVC manufacturing was as follows: 87 % of PVC produced was for suspension and mass PVC
4 products and 7 % was for dispersion PVC resins. Assuming these percentages remained the
5 same for 2000, it is estimated that approximately 5.69 million metric tons of suspension and
6 mass PVC and 0.43 million metric tons of dispersion PVC resins were produced, and 1.72
7 million metric tons of EDC were produced. Applying the same average TEQ observed in the
8 Vinyl Institute samples from 1998, EPA estimated the total I-TEQop contents of suspension/mass
9 PVC resins, dispersion PVC resins, and EDC produced in 2000 to be 0.01 g, 0.0004 g, and 0.01
10 g, respectively (ND = 0) and 3.99 g, 0.17 g, and 0.36 g, respectively (ND = 1/2 MDL).
11 Therefore, total I-TEQDF present in PVC in 2000 was estimated to be between 0.02 g (ND = 0)
12 and 4.52 g (ND = 1/2 MDL).
13
14 8.3.5. Other Aliphatic Chlorine Compounds
15 Aliphatic chlorine compounds are used as monomers in the production of plastics, as
16 solvents and cleaning agents, and as precursors for chemical synthesis (Hutzinger and
17 Fiedler, 199la). These compounds are produced in large quantities. In 1992, 14.6 million metric
18 tons of halogenated hydrocarbons were produced (U.S. International Trade Commission, 1946-
19 1994). The production of 1,2-dichloroethane and vinyl chloride accounted for 82% of this total
20 production. Highly chlorinated CDDs/CDFs (hexa- to octachlorinated congeners) have been
21 found in nanograde-quality samples of 1,2-dichloroethane (55 ng/kg of OCDF in one of five
22 samples), tetrachloroethene (47 ng/kg of OCDD in one of four samples), epichlorohydrin (88
23 ng/kg of CDDs and 33 ng/kg of CDFs in one of three samples), and hexachlorobutadiene (360 to
24 425 ng/kg of OCDF in two samples) obtained in Germany from the company Promochem
25 (Hutzinger and Fiedler, 199la; Heindl and Hutzinger, 1987). No CDDs/CDFs were detected in
26 two samples of allyl chloride, three samples of 1,1,1-trichloroethane, and four samples of
27 trichloroethylene (DL ranged from 5 to 20 ng/kg) (Heindl and Hutzinger, 1987). Because no
28 more recent or additional data could be found in the literature to confirm these values for
29 products manufactured or used in the United States, no national estimates of CDD/CDF
30 emissions are made for the inventory.
31 EPA's Office of Water promulgated effluent limitations for facilities that manufacture
32 chlorinated aliphatic chlorine compounds and discharge treated wastewater (40 CFR 414.70).
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1 These effluent limitations do not specifically address CDDs or CDFs. The following chlorinated
2 aliphatic compounds are regulated: 68 jig/L for 1,2-dichloroethane and 22 jig/L for
3 tetrachloroethylene. Similarly, OSW promulgated restrictions on land disposal of wastes
4 generated during the manufacture of many chlorinated aliphatics (40 CFR 268); however, these
5 restrictions do not specifically regulate CDDs/CDFs.
6
7 8.3.6. Dyes, Pigments, and Printing Inks
8 Several researchers analyzed various dyes, pigments, and printing inks obtained in
9 Canada and Germany for the presence of CDDs/CDFs (Williams et al., 1992; Hutzinger and
10 Fiedler, 1991a; Santl et al., 1994). The following subsections discuss the findings of those
11 studies.
12
13 8.3.6.1. Dioxazine Dyes and Pigments
14 Williams et al. (1992) analyzed the CDD/CDF content in dioxazine dyes and pigments
15 available in Canada. As shown in Table 8-20, OCDD and OCDF concentrations in the ng/kg
16 range and HpCDD, HxCDD, and PeCDD concentrations in the |ig/kg range were found in Direct
17 Blue 106 dye (three samples), Direct Blue 108 dye (one sample), and Violet 23 pigments (six
18 samples) (Williams et al., 1992). These dioxazine pigments are derived from chloranil, which
19 has been found to contain high levels of CDDs/CDFs and has been suggested as the source of
20 contamination among these dyes (Christmann et al., 1989a; Williams et al., 1992; U.S. EPA,
21 1992b). In May 1990, EPA received test results showing that chloranil was heavily
22 contaminated with dioxins; levels as high as 2,903 jig TEQoF-WHOgg/kg (3,065 jig I-TEQDp/kg)
23 were measured in samples from four importers (mean value of 1,388 jig TEQop-WHCWkg
24 [1,754 |ig I-TEQDF/kg]) (U.S. EPA, 1992b; Remmers et al., 1992). (See Section 8.3.7 for
25 analytical results.)
26 In the early 1990s, EPA learned that I-TEQop levels in chloranil could be reduced by
27 more than two orders of magnitude (to less than 20 |ig/kg) through manufacturing feedstock and
28 process changes. EPA's Office of Pollution Prevention and Toxics subsequently began efforts to
29 complete an industry-wide switch from the use of contaminated chloranil to low-dioxin
30 chloranil. Although chloranil is not manufactured in the United States, significant quantities are
31 imported. As of May 1992, EPA had negotiated agreements with all chloranil importers and
32 domestic dye/pigment manufacturers known to EPA that used chloranil in their products to
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1 switch to low-dioxin chloranil. In May 1993, when U.S. stocks of chloranil with high levels of
2 CDDs/CDFs had been depleted, EPA proposed a SNUR under Section 5 of TSCA that would
3 require industry to notify EPA at least 90 days prior to the manufacture, import, or processing,
4 for any use, of chloranil containing CDDs/CDFs at a concentration greater than 20 jig I-
5 TEQDF/kg (Federal Register, 1993a; U.S. EPA, 1993c).
6 In 1983, approximately 36,500 kg of chloranil were imported (U.S. ITC, 1984). The U.S.
7 International Trade Commission has not published quantitative import data for chloranil since
8 1984. If it is assumed that this import volume reflects actual usage of chloranil in the United
9 States during 1987 and that the CDD/CDF contamination level was 1,388 |ig TEQDF-WHO98/kg
10 (1,754 jig I-TEQop/kg), then the maximum release into the environment via processing wastes
11 and finished products was 50.6 g TEQDF-WHO98 (64 g I-TEQDF). If it is assumed that the import
12 volume in 1995 was also 36,500 kg but that the imported chloranil contained 10 jig I-TEQDp/kg
13 on average, then the total potential annual TEQ release associated with chloranil in 1995 was
14 50.6 g TEQDF-WH098 (64 g I-TEQDF).
15 In 1986, EPA promulgated the Inventory Update Rule (IUR) that requires the partial
16 updating of the Toxic Substances Control Act (TSCA) Chemical Inventory database. Every four
17 years, chemical manufacturers and importers of chemicals listed on the TSCA inventory that
18 produce at one plant site or import at production volume levels of 10,000 or more pounds must
19 report the range of chemical production or import. According to information entered in the
20 TSCA database, 10,000 to 500,000 pounds (4,540 to 227,000 kg) of chloranil were imported in
21 1994 and 2000 (http://www.epa.gov/opptintr/iur/iur02/search03.htm). Assuming the imported
22 chloranil contained the same concentration of dioxin as the 1995 estimate above (10 //g I-
23 TEQDF/kg), the total potential annual TEQ release associated with chloranil in 2000 was 0.05 to
24 2.27 g I-TEQDF-WHO98 (mean of 1.16 g I-TEQDF).
25
26 8.3.6.2. Phthalocyanine Dyes and Printing Inks
27 Hutzinger and Fiedler (199la) found CDDs/CDFs (tetra-, penta-, and hexachlorinated
28 congeners) in the |ig/kg range in a sample of a Ni-phthalocyanine dye. No CDDs/CDFs were
29 detected (DL of 0.1 to 0.5 |ig/kg) in two samples of Cu-phthalocyanine dyes and in one Co-
30 phthalocyanine dye (Hutzinger and Fiedler, 1991a).
31 Santl et al. (1994) reported the results of analyses of four printing inks obtained from a
32 supplier in Germany. Two of the inks are used for rotogravure printing and two are used for
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1 offset printing. The results of the analyses are presented in Table 8-21. The
2 content of the inks ranged from 17.7 to 87.2 ng/kg (15 to 88.6 ng/kg on an I-TEQop basis).
3 Primarily non-2,3,7,8-substituted congeners were found. The identities of the dyes and pigments
4 in these inks were not reported.
5 Although EPA provided an estimate of potential environmental release based on limited
6 information of contaminant levels of CDDs/CDFs in the product, the estimate is still too
7 uncertain to include in the quantitative inventory of sources. It is currently not known if the
8 dioxin contamination in the product actually results in a release to the open and circulating
9 environment.
10
11 8.3.7. TSCA Dioxin/Furan Test Rule
12 Citing evidence that halogenated dioxins and furans may be formed as by-products
13 during chemical manufacturing processes (Versar, 1985), EPA issued a rule under Section 4 of
14 TSCA that requires chemical manufacturers and importers to test for the presence of
15 CDDs/CDFs and BDDs/BDFs in certain commercial organic chemicals (Federal Register,
16 1987c). The rule listed 12 manufactured or imported chemicals that required testing and 20
17 chemicals not currently manufactured or imported that would require testing if manufacture or
18 importation resumed. These chemicals are listed in Table 8-24. The specific dioxin and furan
19 congeners that require quantitation and the target limits of quantitation (LOQs) that are specified
20 in the rule are listed in Table 8-25. Under Section 8(a) of TSCA, the final rule also required that
21 chemical manufacturers submit data on manufacturing processes and reaction conditions for
22 chemicals produced using any of the 28 precursor chemicals listed in Table 8-26. The rule stated
23 that subsequent to this data-gathering effort, testing may be proposed for additional chemicals if
24 any of the manufacturing conditions used favored the production of dioxins and furans.
25 Twenty-three sampling and analytical protocols and test data for 10 of the 12 chemicals
26 that required testing were submitted to EPA (U.S. EPA, 2003f). Manufacture or import of two
27 substances (tetrabromobisphenol-A-bis-2,3-dibromopropylether and tetrabromobisphenol-A-
28 diacrylate) have stopped since the test rule was promulgated. (All data and reports in the EPA
29 TSCA docket are available for public review and inspection at EPA Headquarters in
30 Washington, DC.)
31 Table 8-27 presents the results of analytical testing for CDDs/CDFs for the chemicals
32 that have data available in the TSCA docket. Five of these 10 chemicals contained CDDs/CDFs.
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1 Positive results were obtained for 2,3,5,6-tetrachloro-2,5-cyclohexadiene-l,4-dione (chloranil),
2 pentabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenyloxide, and 1,2-
3 Bis(tribromophenoxy)-ethane. Table 8-28 presents the quantitative analytical results for four
4 submitted chloranil samples, as well as the results of an EPA analysis of a sample of carbazole
5 violet, which is manufactured from chloranil.
6 Although testing conducted under this test rule for 2,4,6-tribromophenol indicated no
7 halogenated dioxins or furans above the LOQs, Thoma and Hutzinger (1989) reported detecting
8 BDDs and BDFs in a technical-grade sample of this substance. Total TBDD, TBDF, and PeBDF
9 were found at 84 |ig/kg, 12 |ig/kg, and 1 |ig/kg, respectively. No hexa-, hepta-, or octa-BDFs
10 were detected. Thoma and Hutzinger (1989) also analyzed analytical-grade samples of two other
11 brominated flame retardants, pentabromophenol and tetrabromophthalic anhydride; no BDDs or
12 BDFs were detected (DLs not reported).
13
14 8.3.8. Halogenated Pesticides and FIFRA Pesticides Data Call-In
15 In the late 1970s and early 1980s, attention began to focus on pesticides as potential
16 sources of CDDs/CDFs in the environment. Up to that time, CDD/CDF levels were not
17 regulated in end-use pesticide products. However, some of the active ingredients in pesticides,
18 particularly chlorinated phenols and their derivatives, were known or suspected to be
19 contaminated with CDDs/CDFs. During the 1980s and 1990s, EPA took several actions to
20 investigate and control CDD/CDF contamination of pesticides.
21 Actions to regulate 2,4,5-T and Silvex. In 1983, EPA cancelled the sale of Silvex and
22 2,4,5-T for all uses (Federal Register, 1987e). Earlier, in 1979, EPA had ordered emergency
23 suspension of the forestry, rights-of-way, and pasture uses of 2,4,5-T. Emergency suspensions of
24 the forestry, rights-of-way, pasture, home and garden, commercial/ornamental turf, and aquatic
25 weed control/ditch bank uses of Silvex were also ordered (Federal Register, 1979; Plimmer,
26 1980). The home and garden, commercial/ornamental turf, and aquatic weed control/ditch bank
27 uses of 2,4,5-T had been suspended in 1970.
28 Actions to regulate PCP. In 1984, EPA issued a notice of intent to cancel registrations
29 of pesticide products containing PCP (including its salts) for all wood preservative uses (Federal
30 Register, 1984). This notice specified modifications to the terms and conditions of product
31 registrations that were required in order to avoid cancellation of the products. In response to this
32 notice, several trade associations and registrants requested administrative hearings to challenge
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1 EPA's determinations. After carefully considering the comments and alternatives suggested
2 during the preheating stage of the administrative proceedings, EPA concluded that certain
3 changes to the 1984 notice were appropriate. These changes, finalized in 1986 (Federal Register,
4 1986), included the following: (a) all wood preservative uses of PCP and its salts were classified
5 as "restricted use" only by certified applicators, (b) specific worker protection measures were
6 required, (c) limits were placed on the HxCDD content of PCP, and (d) label restrictions for
7 home and farm uses of PCP prohibited its application indoors and to wood intended for interior
8 use (with a few exceptions) as well as its application in a manner that might result in direct
9 exposure of domestic animals or livestock or in the contamination of food, feed, or drinking and
10 irrigation water.
11 EPA subsequently amended its Notice on the wood preservative uses to establish reliable
12 and enforceable methods for implementing certified limits for HxCDD and 2,3,7,8-TCDD in
13 registered wood preservative pesticide products (Federal Register, 1987a). Levels of 2,3,7,8-
14 TCDD were not allowed to exceed 1 ppb in any product, and after February 2, 1989, any
15 manufacturing-use PCP released for shipment could not contain HxCDD levels that exceeded an
16 average of 2 ppm over a monthly release or a batch level of 4 ppm (a gradually phased-in
17 requirement). On January 21, 1987, EPA prohibited the registration of PCP and its salts for most
18 nonwood uses (Federal Register, 1987b). EPA deferred action on several uses (uses in
19 pulp/paper mills, oil wells, and cooling towers) pending receipt of additional exposure, use, and
20 ecological effects data. On January 8, 1993, EPA issued a press advisory stating that its special
21 review of these deferred nonwood uses was being terminated because all of these uses had been
22 either voluntarily cancelled by the registrants or cancelled by EPA for failure of the registrants to
23 pay the required annual maintenance fees (U.S. EPA, 1993f).
24 PCP was one of the most widely used biocides in the United States prior to the regulatory
25 actions to cancel and restrict certain of its wood and nonwood preservative uses. PCP was
26 registered for use as a herbicide, defoliant, mossicide, and mushroom house biocide. It also
27 found use as a biocide in pulp-paper mills, oil wells, and cooling towers. These latter three uses
28 were terminated on or before 1993 (U.S. EPA, 1993f). However, the major use (greater than
29 80% of consumption) of PCP was and continues to be wood preservation.
30 The production of PCP for wood preserving began on an experimental basis in the 1930s.
31 In 1947, nearly 3,200 metric tons of PCP were reported to have been used in the United States by
32 the commercial wood preserving industry. Use in this industry steadily increased through the
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1 mid-1970s (American Wood Preservers Institute, 1977). Although domestic consumption
2 volumes are not available for all years, it is estimated, on the basis of historical
3 production/export data for PCP reported in Mannsville (1983), that 90 to 95% of production
4 volume has typically been consumed domestically rather than exported. A reasonable estimate
5 of average annual domestic PCP consumption during the period 1970 to 1995 is about 400,000
6 metric tons. This estimate assumes an average annual consumption rate of 20,000 metric tons/yr
7 during the 1970s, 15,000 metric tons/yr during the 1980s, and 10,000 metric tons/yr during the
8 1990s.
9 Table 8-8 presents a compilation of published data on the CDD/CDF content of
10 technical-grade PCP. The only samples that have been analyzed for all dioxin-like CDDs/CDFs
11 were manufactured in the mid to late 1980s. Figure 8-4 presents these data in graphical form. It
12 is evident from the figures that the predominant congener groups are OCDD, OCDF, HpCDF,
13 and HpCDD, and the dominant 2,3,7,8-substituted congeners are OCDD, 1,2,3,4,6,7,8-HpCDD,
14 and OCDF. Waddell et al. (1995) tested analytical-grade PCP (from Aldrich Chemical Co.) for
15 CDD/CDF content and found the same congener profile; however, the CDD/CDF levels were
16 three to four orders of magnitude lower. Table 8-9 presents a similar compilation of published
17 data on the CDD/CDF content of PCP-Na. The table shows the same patterns of dominant
18 congeners and congener groups reported for PCP.
19 Samples of technical PCP manufactured during the mid to late 1980s contained about 1.7
20 mg TEQDF-WHO98/kg (3 mg I-TEQ/kg), based on the data presented in Table 8-8. No published
21 reports could be located that present the results of any congener-specific analyses of PCP
22 manufactured since the late 1980s. However, monthly measurements of CDD/CDF congener
23 group concentrations in technical PCP manufactured for use in the United States have been
24 reported to EPA from 1987 to the present (KMG-Bernuth, 1997; Pentachlorophenol Task Force,
25 1997; U.S. EPA, 1999a). The average congener group concentrations reported to EPA for the
26 years 1988 (i.e., one year after EPA regulations were imposed limiting HxCDD and 2,3,7,8-
27 TCDD concentrations in PCP) to 1999 are presented in Table 8-8. In general, the average
28 congener group concentrations during the period 1988 to 1999 are lower by factors of 2 to 4 than
29 those observed in the mid to late 1980s' full congener analysis samples. If it is assumed that the
30 toxic CDD/CDF congeners have also been reduced by similar factors, then the TEQ content of
31 PCP manufactured since 1988 is about 0.6 mg TEQDF-WHO98/kg (1 mg I-TEQ/kg).
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1 An estimated 12,000 metric tons of PCP were used for wood preservation in the United
2 States in 1987 (WHO, 1991). An estimated 8,400 metric tons were used in 1994 (American
3 Wood Preservers Institute, 1995); for purposes of this report, it is assumed that an identical
4 amount was used in 1995. In 1999, approximately 7,710 metric tons of PCP were produced
5 annually in the United States (Council of Great Lakes Industries, 1999); for purposes of this
6 report, it is assumed that an identical amount was produced in 2000. Assuming that 95% of the
7 production volume was consumed domestically (Mannsville, 1983), and that all of the PCP
8 produced in 2000 was used for wood preservation, approximately 7,325 metric tons of PCP was
9 used in the United States for wood preservation. Combining these activity level estimates with
10 the TEQ concentration estimates presented above indicates that 20,000 ug TEQoF-WHOgg
11 (36,000 ug I-TEQDF ), 4,800 ug TEQDF-WHO98 (8,400 ug I-TEQDF ), and 4,175 ug TEQDF-
12 WHC-98 (7,325 ug I-TEQDF ) were incorporated into PCP-treated wood products in 1987, 1995,
13 and 2000, respectively. These amounts in PCP products are not considered an environmental
14 release and therefore are not included in the inventory. As discussed below, there is some
15 evidence that releases could occur, but no consistent estimation approach could be found.
16 Although the estimates of the mass of TEQ in treated wood are fairly certain, no studies
17 are available that provide measured CDD/CDF release rate data from which a reliable estimate
18 can be made of the amount of CDDs/CDFs that have or will volatilize or leach from treated
19 wood. Several recent field studies, discussed in the following paragraphs, demonstrate that
20 CDDs/CDFs do apparently leach into soil from PCP-treated wood, but the studies do not provide
21 release rate data. No studies were located that provide any measured CDD/CDF volatilization
22 rates from PCP-treated wood. Although CDDs/CDFs have very low vapor pressures, they are
23 not bound to, nor do they react with, the wood in any way that would preclude volatilization.
24 Several studies, discussed below, have attempted to estimate potential CDD/CDF volatilization
25 releases using conservative assumptions or modeling approaches, but these estimates span many
26 orders of magnitude.
27 Gurprasad et al. (1995) analyzed three PCP-treated utility poles and their surrounding
28 surface soils for penta- through octa-CDD content. All three poles showed significant levels of
29 HxCDD (0.29 to 0.47 mg/kg), HpCDD (4.69 to 6.63 mg/kg), and OCDD (27.9 to 42.1 mg/kg),
30 but no PeCDD. Surface soils collected 2 cm from the poles also had detectable levels of
31 HxCDD, HpCDD, and OCDD; however, no consistent pattern was found between the CDD
32 concentrations in the poles and those in the adjacent soils. The soil concentrations did, however,
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1 show the same relative congener group pattern observed in the wood. CDD concentrations in
2 soils obtained 20 cm from the poles were an order of magnitude less than those measured at 2
3 cm. Soils 26 m from the poles showed nondetect values or values close to the DL of 0.01 to 0.02
4 mg/kg.
5 In a study of the leaching of PCP from 31 utility poles, the Electric Power Research
6 Institute (EPRI, 1995) found similar patterns of PCP distribution in soils surrounding poles as
7 those found by Gurprasad et al. (1995) for CDDs. PCP concentrations decreased by as much as
8 two orders of magnitude between 7.5 cm from the poles and 20 cm from the poles, with an
9 average decrease of slightly more than one order of magnitude over this distance. EPRI (1995)
10 also found no obvious trend between PCP concentration in the wood (eight poles analyzed) and
11 the age of the poles (4 to 11 years) or the PCP concentration in the surface soil. On the basis of
12 their results and those of EPRI (1995), Gurprasad et al. concluded that CDDs probably leach
13 from PCP-treated utility poles with the PCP/oil carrier and travel in the soil in a similar manner.
14 Wan (1995) and Wan and Van Oostdam (1995) measured CDD/CDF concentrations in
15 waters and sediments from ditches surrounding utility poles and railroad ties and demonstrated
16 that chlorophenol-treated wood could serve as a source of CDD/CDFs to the aquatic
17 environment. Ten samples were collected at each of six utility pole sites and five railroad tie
18 sites 1 to 2 days after major rainfall events and then were composited into one sample per site
19 prior to analyses. Total CDDs (mean value of 76.7 mg/kg) and total CDFs (mean value of 18.7
20 mg/kg) detected in chlorophenol/creosote-treated utility poles were about 6 to 8 times greater,
21 respectively, than the CDD and CDF concentrations detected in chlorophenol/creosote-treated
22 railroad ties. Total CDDs found in water from railway ditches without utility poles (i.e., only
23 treated railroad ties were present) were approximately 20 times higher than the background level
24 found in farm ditch water. Total CDDs in railway ditches with utility poles were 4,300 times
25 higher than the background levels. Water from railway ditches without utility poles contained
26 total CDF levels 13 times higher than background levels, whereas water in ditches adjacent to
27 poles were 8,500 times higher than background levels. Total CDDs in ditch sediments adjacent
28 to, and 4 m downstream of, utility poles were about 5,900 and 2,200 times higher, respectively,
29 than background levels; total CDFs for the same sites were about 8,100 and 1,700 times higher,
30 respectively, than background levels. Total CDDs found in ditch sediments of railway and ditch
31 sediments adjacent to utility poles were about 5 and 700 times higher, respectively, than
32 background levels; while total CDFs were about 9 and 1,800 times higher, respectively, than
33 background levels. Both CDDs and CDFs were found in utility ditch sediments 4 m downstream
34 of treated power poles, but at levels of 200 and 400 times, respectively, lower than those found
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1 adjacent to poles, indicating that they were transported from point sources of contamination. The
2 corresponding values for CDFs were 5,400 and 8,000 times, respectively, higher in
3 concentration.
4 Bremmer et al. (1994) estimated an annual release of 15 to 125 g of I-TEQop from PCP-
5 treated wood in the Netherlands. The lower estimate was based on three basic assumptions:
6 (1) the half-life of PCP in treated wood is 15 years (according to industry sources), (2) the half-
7 life of CDDs/CDFs in treated wood is 10 times that of PCP (i.e., 150 years) because of the lower
8 vapor pressures of CDDs/CDFs relative to PCP, and (3) the typical CDD/CDF concentration in
9 PCP has been 3000 |ig/kg. The higher estimate was based on an assumed half-life of PCP in
10 wood of 15 years and the results of an indoor air study by Papke et al. (1989) conducted at
11 several kindergartens where PCP-treated wood had been used. Although Papke et al. found no
12 clear correlation between indoor air concentrations of CDD/CDF and PCP across the range of
13 CDD/CDF concentrations observed in the 20-plus samples (2.6 to 427 pg CDD/CDF/m3), there
14 did appear to be a positive correlation at the sites with more elevated CDD/CDF concentrations.
15 Bremmer et al. (1994) reported that the average ratio of PCP to I-TEQ DF air concentrations at
16 these elevated sites to be 1:5 x 10"6 (or about the same ratio as the concentration of I-TEQ DF in
17 technical PCP). The results of the Papke et al. (1989) study imply that CDDs/CDFs may be
18 released from PCP-treated wood at the same rate as PCP rather than at a rate 10 times slower.
19 Rappe (1995) used the emission factor approach developed by Bremmer et al. (1994) and
20 an assumed U.S. usage volume of PCP over the past 50 years (0.5 million metric tons) to
21 estimate that as much as 10.5 kg of I-TEQDp could volatilize from PCP-treated wood in the
22 United States annually. Eitzer and Kites (1987) derived a dramatically different estimate of
23 CDD/CDF volatilization from PCP-treated wood in the United States: 3 kg/yr of total
24 CDD/CDF (or 66 g of I-TEQDF per year, assuming an I-TEQDF content in PCP of 3 mg/kg).
25 Eitzer and Kites based their estimate on an assumption that 0.1% of the PCP produced annually
26 enters the atmosphere and that the CDD/CDF contaminants present in the PCP (assumed to be
27 130 mg/kg) are released to the atmosphere at the same rate as the PCP (i.e., 0.1%). The basis for
28 the first assumption by Eitzer and Kites is not clear because EPA, which was cited as the source
29 of the 0.1% emission factor (U.S. EPA, 1980), does not appear to address volatilization of PCP
30 from in-service treated wood. The report does, however, estimate that most PCP in treated wood
31 leaches relatively rapidly from the wood, presumably to land, within a period of 12 years.
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1 Eduljee and Dyke (1996) and Douben et al. (1995) estimated that 0.8 g of I-TEQDF is
2 released to the air annually from PCP-treated wood in the United Kingdom. This estimate was
3 based on the assumed emission of 0.1% of the CDD/CDF present in PCP-treated wood during
4 the first year of the service life of the wood that was assumed by Eitzer and Kites (1987). No
5 emission was assumed for subsequent years of use of the treated wood.
6 The California Air Resources Board (Chinkin et al., 1987) generated estimates of
7 CDD/CDF volatilization releases at wood treatment facilities from bundles of treated wood that
8 remain on site for 1 month prior to shipment. An "adapted" version of a model developed by
9 McCord (1981) was used for estimating volatile releases from a constantly filling lagoon. The
10 model is primarily driven by chemical-specific vapor pressures and air diffusivity coefficients.
11 Chinkin et al. did not provide all model input parameter values used to generate the emission
12 estimates. However, running the model with typical dimensions for treated poles yields an I-
13 TEQop emission rate on the order of 6E-12 g/yr-pole, an extremely low number (170 billion
14 poles would together emit 1 g TEQ/yr).
15 Actions to identify other pesticides containing CDDs/CDFs. In addition to cancelling
16 some pesticide registrations and establishing product standards, EPA's Office of Pesticide
17 Programs (OPP) issued two DCIs in 1987. Pesticide manufacturers are required to register their
18 products with EPA in order to market them commercially in the United States. Through the
19 registration process, mandated by FIFRA, EPA can require that the manufacturer of each active
20 ingredient generate a wide variety of scientific data through several mechanisms. The most
21 common process is the five-phase reregi strati on process, with which the manufacturers (i.e.,
22 registrants) of older pesticide products must comply. In most registration activities, registrants
23 must generate data under a series of strict testing guidelines, 40 CFR 158—Pesticide Assessment
24 Guidelines (U.S. EPA, 1988b). EPA can also require additional data from registrants, when
25 necessary, through various mechanisms, including the DCI process.
26 The purpose of the first DCI, dated June and October 1987, "Data Call-In Notice for
27 Product Chemistry Relating to Potential Formation of Halogenated Dibenzo-p-dioxin or
28 Dibenzofuran Contaminants in Certain Active Ingredients," was to identify, using an analysis of
29 raw materials and process chemistry, those pesticides that might contain halogenated dibenzo-p-
30 dioxin (HDD) and halogenated dibenzofuran (HDF) contaminants. The 93 pesticides (76
31 pesticide active ingredients) to which the DCI applied, along with their corresponding
32 Shaughnessey and Chemical Abstract code numbers, are presented in Table 8-29. (The
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1 Shaughnessey code is an internal EPA tracking system. It is of interest because chemicals with
2 similar code numbers are similar in chemical nature [e.g., salts, esters, and acid forms of 2,4-D].)
3 All registrants supporting registrations for these chemicals were subject to the
4 requirements of the DCI unless their product qualified for a Generic Data Exemption (i.e., a
5 registrant exclusively used a FIFRA-registered pesticide produces] as the source[s] of the active
6 ingredient[s] identified in Table 8-29 in formulating their produces]). Registrants whose
7 products did not meet the Generic Data Exemption were required to submit the types of data
8 listed below to enable EPA to assess the potential for formation of tetra- through hepta-HDD or
9 FIDF contaminants during manufacture. Registrants, however, had the option to voluntarily
10 cancel their product or "reformulate to remove an active ingredient" to avoid having to comply
11 with the DCI.
12
13 • Product identity and disclosure of ingredients. EPA required submittal of a
14 Confidential Statement of Formula (CSF), based on the requirements specified in 40
15 CFR 158.108 and 40 CFR 158.120, Subdivision D: Product Chemistry. Registrants
16 who had previously submitted still-current CSFs were not required to resubmit this
17 information.
18
19 • Description of beginning materials and manufacturing process. Under the
20 requirements mandated by 40 CFR 158.120, Subdivision D, EPA required submittal
21 of a manufacturing process description for each step of the manufacturing process,
22 including specification of the range of acceptable conditions of temperature, pressure,
23 or pH at each step.
24
25 • Discussion of the formation of impurities. Under the requirements mandated by 40
26 CFR 158.120, Subdivision D, EPA required submittal of a detailed discussion and
27 assessment of the possible formation of HDDs and HDFs.
28
29 The second DCI, dated June and October 1987, "Data Call-In for Analytical Chemistry
30 Data on Polyhalogenated Dibenzo-p-Dioxins/Dibenzofurans (HDDs and HDFs)," was issued for
31 68 pesticides (16 pesticide active ingredients) suspected to be contaminated by CDDs/CDFs (see
32 Table 8-28). All registrants supporting registrations for these pesticides were subject to the
33 requirements of this DCI unless the product qualified for various exemptions or waivers.
34 Pesticides covered by the second DCI were strongly suspected by EPA to contain detectable
35 levels of CDDs/CDFs.
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1 Under the second DCI, registrants whose products did not qualify for an exemption or
2 waiver were required to generate and submit the following types of data in addition to the data
3 requirements of the first DCI:
4
5 • Quantitative method for measuring CDDs or CDFs. Registrants were required to
6 develop an analytical method for measuring the HDD/HDF content of their products.
7 The DCI established a regimen for defining the precision of the analytical method.
8 Target LOQs were established in the DCI for specific CDD/CDF congeners (see
9 Table 8-23).
10
11 • Certification of limits of CDDs or CDFs. Registrants were required to submit a
12 "Certification of Limits" in accordance with 40 CFR 158.110 and 40 CFR 158.120,
13 Subdivision D. Analytical results were required that met the guidelines described
14 above.
15
16 Registrants could select one of two options to comply with the second DCI. The first
17 option was to submit relevant existing data, develop new data, or share the cost to develop new
18 data with other registrants. The second option was to alleviate the DCI requirements through
19 several exemption processes, including a Generic Data Exemption, voluntary cancellation,
20 reformulation to remove the active ingredient of concern, an assertion that the data requirements
21 did not apply, or the application or award of a low-volume, minor-use waiver.
22 The data contained in CSFs, as well as any other data generated under 40 CFR 158.120,
23 Subdivision D, are typically considered confidential business information (CBI) under the
24 guidelines prescribed in FIFRA because they usually contain information regarding proprietary
25 manufacturing processes. In general, all analytical results submitted to EPA in response to both
26 DCIs are considered CBI and cannot be released by EPA into the public domain. Summaries
27 based on the trends identified in that data, as well as data made public by EPA, are summarized
28 below.
29 The two DCIs included 161 pesticides. Of these, 92 are no longer supported by
30 registrants. Following evaluation of the process chemistry submissions required under the DCIs,
31 OPP determined that formation of CDDs/CDFs was not likely during the manufacture of 43 of
32 the remaining 69 pesticides; thus, analysis of samples of these 43 pesticides was not required by
33 OPP. Evaluation of process chemistry data is ongoing at OPP for an additional 7 pesticides.
34 Tables 8-29 and 8-30 indicate which pesticides are no longer supported, those for which OPP
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1 determined that CDD/CDF formation is unlikely, and those for which process chemistry data or
2 analytical testing results are under review (U.S. EPA, 1995f).
3 OPP required that analysis of production samples be performed on the remaining 19
4 pesticides (see Table 8-31). The status of the analytical data generation/evaluation to date is
5 summarized as follows: (a) no detection of CDDs/CDFs above the LOQs in registrant
6 submissions for 13 active ingredients, (b) detection of CDDs/CDFs above the LOQs for 2,4-D
7 acid (two submissions) and 2,4-D 2-ethyl hexyl acetate (one submission), and (c) ongoing data
8 generation or evaluation for four pesticides.
9 Table 8-32 presents a summary of results obtained by EPA for CDDs/CDFs in eight
10 technical 2,4-D herbicides; these data were extracted from program files in OPP. Because some
11 of these files contained CBI, the data in this table were reviewed by OPP staff to ensure that no
12 CBI was being disclosed (Funk, 1996). Figure 8-5 presents a congener profile for 2,4-D based
13 on the average congener concentrations reported in Table 8-33.
14 Schecter et al. (1997) reported the results of analyses of samples of 2,4-D manufactured
15 in Europe, Russia, and the United States (see Table 8-33). The total TEQ concentrations
16 measured in the European and Russian samples were similar to those measured in the EPA DCI
17 samples; however, the levels reported by Schecter et al. for U.S. samples were significantly
18 lower. Similarly, Masunaga et al. (2001) reported the analyses of two agrochemical formulations
19 containing 2,4-D manufactured in Japan (Table 8-31). The total TEQ concentration measured in
20 one of the samples was similar to what Schecter et al. (1997) reported for the U.S. samples; no
21 TEQ was detected in the other sample.
22 As discussed in Section 12.2.1, an estimated 28,100 metric tons of 2,4-D were used in the
23 United States in 2000, making it one of the top 10 pesticides in terms of quantity used (EPA
24 proprietary data). The pesticide 2,4-D is the only product judged to have the potential for
25 environmental release through its agricultural use. However, no estimate of environmental
26 release can be made for the year 2000. Since 1995, the chemical manufacturers of 2,4-D have
27 been undertaking voluntary actions to significantly reduce the dioxin content of the product. No
28 information is available on the level of dioxin contamination, if any, that may have been present
29 in 2,4-D in the year 2000. An estimated 26,300 and 30,400 metric tons were used during 1995
30 and 1987, respectively (U.S. EPA, 1997e, 1988c). On the basis of the average CDD/CDF
31 congener concentrations in 2,4-D presented in Table 8-33 (not including OCDD and OCDF), the
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1 corresponding TEQoF-WHOgg concentration is 1.1 |ig/kg (0.7 jig I-TEQop/kg). Combining this
2 TEQ concentration with the activity level estimates for 1995 and 1987 indicates that
3 28.9 g TEQDF-WHO98 (18.4 g I-TEQDF) were released in 1995 and 33.4 g TEQDF-WHO98 (21.3
4 g I-TEQop) in 1987. The release estimates for 1987 and 1995 are assigned a high confidence
5 rating, indicating high confidence in both the production and the emission factor estimates.
6 Because no estimate can be made for 2000, it is rated as Category E.
7
8 8.4. OTHER CHEMICAL MANUFACTURING AND PROCESSING SOURCES
9 8.4.1. Municipal Wastewater Treatment Plants
10 8.4.1.1. Sources
11 CDDs/CDFs have been measured in nearly all sewage sludges tested, although the
12 concentrations and, to some extent, the congener profiles and patterns differ widely. Potential
13 sources of the CDDs/CDFs include microbial formation (discussed in Chapter 9), runoff to
14 sewers from lands or urban surfaces contaminated by product uses or deposition of previous
15 emissions to air (discussed in Section 12.2.1), household wastewater, industrial wastewater,
16 chlorination operations within the wastewater treatment facility, or a combination of all the
17 above (Rappe, 1992a; Rappe et al., 1994; Horstmann et al., 1992; Sewart et al., 1995; Cramer et
18 al., 1995; Horstmann and McLachlan, 1995).
19 The major source(s) for a given publicly owned treatment works (POTW) is likely to be
20 site specific, particularly in industrialized areas. For example, Rieger and Ballschmiter (1992)
21 traced the origin of CDDs/CDFs found in municipal sewage sludge in Ulm, Germany, to metal
22 manufacturing and urban sources. The characteristics of both sources were similar and
23 suggested generation via thermal processing. However, in a series of recent studies, Horstmann
24 et al. (1992, 1993a, b) and Horstmann and McLachlan (1994a, b, 1995) demonstrated that
25 wastewater generated by laundering and bathing could be the major source at many, if not all,
26 POTWs that serve primarily residential populations. Although runoff from streets during
27 precipitation events, particularly from streets with high traffic density, was reported by these
28 researchers as contributing measurably, the total contribution of TEQ from household
29 wastewater was eight times greater than that from surface runoff at the study city.
30 Horstmann et al. (1992) provided initial evidence that household wastewater could be a
31 significant source. Horstmann et al. (1993a) measured CDD/CDF levels in the effluent from
32 four different loads of laundry from two different domestic washing machines. The
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1 concentrations of total CDDs/CDFs in the four samples ranged from 3,900 to 7,100 pg/L and
2 were very similar in congener profile, with OCDD being the dominant congener, followed by the
3 hepta- and hexa-CDDs. Because of the similar concentrations and congener profiles found, the
4 authors concluded that the presence of CDDs/CDFs in washing machine wastewater is
5 widespread. A simple mass balance performed using the results (Horstmann and McLachlan,
6 1994a) showed that the CDDs/CDFs found in the four washing machine wastewater samples
7 could account for 27 to 94% of the total CDDs/CDFs measured in the sludge of the local
8 wastewater treatment plant.
9 Horstmann et al. (1993a) performed additional experiments that showed that detergents,
10 commonly used bleaching agents, and the washing cycle process itself were not responsible for
11 the observed CDDs/CDFs. To determine whether the textile fabric or fabric finishing processes
12 could account for the observed CDDs/CDFs, Horstmann et al. (1993b), Horstmann and
13 McLachlan (1994a, b), and Klasmeier and McLachlan (1995) analyzed the CDDs/CDFs content
14 of raw cotton cloth, white synthetic materials, and more than 100 new textile finished products.
15 Low concentrations were found in most products (less than 50 ng/kg of total CDDs/CDFs), but a
16 small percentage contained high concentrations, up to 290 |ig/kg of total CDDs/CDFs. On the
17 basis of the concentrations and patterns found, the authors concluded that neither unfinished new
18 fabrics nor common cotton finishing processes could explain the CDD/CDF levels found in
19 wastewater; rather, the use of CDD-/CDF-containing textile dyes and pigments and the use in
20 some developing countries of PCP to treat unfinished cotton appeared to be the sources of the
21 detected CDDs/CDFs.
22 Horstmann and McLachlan (1994a, b, 1995) reported the results of additional
23 experiments showing that the small percentage of clothing items with high CDD/CDF levels
24 could be responsible for the quantity of CDDs/CDFs observed in household wastewater and
25 sewage sludge. They demonstrated that the CDDs/CDFs can be gradually removed from the
26 fabric during washing; they can be transferred to the skin, subsequently transferred back to other
27 textiles, and then washed out, or they can be transferred to other textiles during washing and then
28 removed during subsequent washing.
29
30 8.4.1.2. Releases to Water
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1 8.4.1.2.1. Emissions data. The presence of CDDs/CDFs in sewage sludge suggests that
2 CDDs/CDFs may also be present in the wastewater effluent discharges of POTWs; however, few
3 studies reporting the results of effluent analyses for CDDs/CDFs have been published.
4 Rappe et al. (1989a) tested the effluent from two Swedish POTWs for all 2,3,7,8-
5 substituted CDD/CDF congeners. OCDD was detected in the effluents from both facilities at
6 concentrations ranging from 14 to 39 pg/L. Rappe et al. detected 1,2,3,4,6,7,8-HpCDD and
7 1,2,3,4,6,7,8-HpCDF in the effluent of one facility at concentrations of 2.8 and 2 pg/L,
8 respectively. No 2,3,7,8-substituted tetra-, penta-, and hexa-CDDs or CDFs were detected (DLs
9 of 0.2 to 20 pg/L).
10 Ho and Clement (1990) reported the results of sampling during the late 1980s of 37
11 POTWs in Ontario, Canada, for each of the five CDD/CDF congener groups with four to eight
12 chlorines. The sampled facilities included 27 secondary treatment facilities, seven primary
13 treatment facilities, one tertiary plant, and two lagoons. The facilities accounted for about 73%
14 of the sewage discharged by POTWs in Ontario. No CDDs/CDFs were detected (DL in low
15 ng/L range) in the effluents from the lagoons and the tertiary treatment facility. Only OCDD and
16 TCDF were detected in the effluents from the primary treatment facilities (two and one effluent
17 samples, respectively). HpCDD, OCDD, TCDF, and OCDF were detected in the effluents from
18 the secondary treatment facilities (detected in four or fewer samples at levels ranging from 0.1 to
19 11 ng/L).
20 Gobran et al. (1995) analyzed the raw sewage and final effluent of an Ontario, Canada,
21 wastewater treatment plant for CDD/CDF congeners over a 5-day period. Although HpCDD,
22 OCDD, HpCDF, and OCDF were detected in the raw sewage (12 to 2,300 pg/L), no
23 CDDs/CDFs were detected in the final effluent at congener-specific DLs ranging from 3 to 20
24 pg/L.
25 The California Regional Water Quality Control Board (CRWQCB, 1996) reported the
26 results of effluent testing at nine POTWs in the San Francisco area. A total of 30 samples were
27 collected between 1992 and 1995 and 1 to 6 samples were analyzed for each POTW. As
28 summarized in Table 8-32, the overall mean TEQ concentration is 0.27 pg TEQoF-WHOgg/L
29 (0.29 pg I-TEQoF/L). With the exception of OCDD, most 2,3,7,8-substituted CDD/CDF
30 congeners were seldom detected.
31 Rappe et al. (1998) analyzed effluent samples from 17 POTWs in Mississippi, 10 of
32 which receive input from industrial facilities. Treatment processes at the facilities include the
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1 use of one or more of the following: lagoons, activated sludge, aerated digestion, wetlands,
2 oxidative ditch, and trickling filter. Additionally, 12 of the facilities use chlorine gas in the
3 treatment process. The wastewater flows at the facilities range from 0.11 to 39.75 million liters
4 per day; however, wastewater flow rates were not known for two facilities. Table 8-33 presents
5 the concentrations of dioxins measured in the effluent samples for each facility and total TEQ
6 emission factors. Concentrations were only congener-specific for 2,3,7,8-TCDD; 2,3,7,8-TCDF;
7 1,2,3,7,8-PeCDD; 2,3,4,7,8-PeCDF; OCDD; and OCDF. Also provided were concentrations for
8 total HxCDD and total HpCDD. The total TEQ concentrations reported by Rappe et al.
9 (assuming ND = 1/2 DL) ranged from 0.274 to 3.84 pg I-TEQDF/L (average of 0.86 pg/I-
10 TEQop/L) Because concentrations for all congeners were not provided, emission factors could
11 not be calculated in TEQDF-WHO98.
12 The CRWQCB (1996) data were collected to provide representative effluent
13 concentrations for the San Francisco area. These data cannot be considered to be representative
14 of CDD/CDF effluent concentrations at the 16,000-plus POTWs nationwide. Therefore, the data
15 can be used only to generate a preliminary estimate of the potential mass of CDD/CDF TEQ that
16 may be released annually by U.S. POTWs.
17
18 8.4.1.2.2. Activity level information. Based on the results of the 1996 and 2000 Clean Water
19 Needs Surveys, estimates show that approximately 122 billion liters and 148 billion liters of
20 wastewater were treated daily by POTWs in the United States in 1996 and 2000, respectively
21 (U.S. EPA, 1997c, 2004).
22 Wastewater treatment data were not available for the year 1987, however, an estimate
23 was developed using the population of the United States as a surrogate. In 2000, the population
24 of the United States was approximately 281 million people. Using the estimate of water treated
25 daily by POTWs in 2000, approximately 527 L/person of wastewater were treated daily by
26 POTWs. In 1990, the population of the United States was approximately 249 million people.
27 Assuming the population did not change drastically between 1987 and 1990, and assuming that
28 the daily domestic wastewater treatment per person remained constant between 1987 and 2000,
29 EPA estimates that approximately 131 billion liters of wastewater were treated daily at POTWs
30 in 1987.
31
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1 8.4.1.2.3. Emission Estimates. By multiplying the amount of wastewater treated by 365 days/yr
2 and by the "overall mean" TEQ concentrations reported by CRWQCB (i.e., 0.27 pg TEQop-
3 WHO98/L and 0.29 pg I-TEQDF/L), yields annual TEQ release estimates of 12.9 g TEQDF-
4 WHO98 (13.9 g of I-TEQDF), 12 g TEQDF-WHO98 (13 g of I-TEQDF), and 14.6 g TEQDF-WHO98
5 (15.7 g I-TEQop) for 1987, 1995, and 2000, respectively. These estimates should be regarded as
6 preliminary indications of possible emissions from this source.
7
8 8.4.1.3. Sewage Sludge Land Disposal
9 Sewage sludge is the solid, semi-solid, or liquid residue generated during the treatment of
10 wastewater. During wastewater treatment, nutrients, pathogens, inorganic compounds (metals
11 and trace elements), and organic compounds (CDDs/CDFs, PCBs, and surfactants) from the
12 incoming wastewater are partitioned to the resulting sewage sludge (National Research Council,
13 2002). The sludge is either disposed of through methods such as incineration or landfill/surface
14 disposal or beneficially used through methods such as land application.
15 Sewage sludge that is applied to land is referred to as biosolids. In order to be applied to
16 the land, the biosolids must be treated to meet land application regulatory requirements (Federal
17 Register, 1993b). With respect to land application, biosolids are often used for crop production,
18 gardening, forestry, turf growth, and landscaping. Some other uses include strip mine and gravel
19 pit reclamation and wetland restoration. Land application of biosolids is beneficial because it
20 improves the physical and chemical properties of the soil needed for plant growth, it reduces the
21 need for other disposal methods, and it reduces or eliminates the need for commercial fertilizers.
22 Commercial fertilizers often have higher nutrient contents than do biosolids; therefore, the
23 application of biosolids to land in lieu of commercial fertilizers may reduce the impacts of high
24 levels of excess nutrients entering the environment (U.S. EPA, 1999e).
25
26 8.4.1.3.1. Emissions data. EPA conducted the National Sewage Sludge Survey in 1988 and
27 1989 to obtain national data on sewage sludge quality and management. As part of this survey,
28 EPA analyzed sludges from 174 POTWs that employed at least secondary wastewater treatment
29 for more than 400 analytes, including CDDs/CDFs. Although sludges from only 16% of the
30 POTWs had detectable levels of 2,3,7,8-TCDD, all sludges had detectable levels of at least one
31 CDD/CDF congener (U.S. EPA, 1996a). I-TEQDF concentrations as high as 1,820 ng/kg dry
32 weight were measured. The congener-specific results of the survey are presented in Table 8-36.
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1 If all nondetect values found in the study are assumed to be zero, then the mean and median I-
2 TEQop concentrations of the sludges from the 174 POTWs are 50 and 11.2 ng/kg (dry-weight
3 basis), respectively. If the nondetect values are set equal to the DL, then the mean and median I-
4 TEQop concentrations are 86 and 50.4 ng/kg, respectively (U.S. EPA, 1996a; Rubin and White,
5 1992).
6 Green et al. (1995) and Cramer et al. (1995) reported the results of analyses of 99
7 samples of sewage sludge collected from wastewater treatment plants across the United States
8 during the summer of 1994 as part of the 1994/1995 Association of Metropolitan Sewerage
9 Agencies (AMSA) survey. These data are summarized in Table 8-37. To calculate average
10 results in units of TEQ, Green et al. averaged the results from all samples collected from the
11 same facility to ensure that the results were not biased toward the concentrations found at
12 facilities from which more than one sample was collected. Also, eight samples were excluded
13 from the calculation of the overall TEQ averages because it was unclear as to whether they were
14 duplicate samples from other POTWs. POTW average TEQ concentrations were calculated for
15 74 POTWs. If all nondetect values are assumed to be zero, then the overall study mean and
16 median I-TEQop concentrations are 47.7 and 33.4 ng I-TEQop/kg (dry weight basis), respectively
17 (standard deviation of 44.7 ng I-TEQop/kg). The corresponding mean and median TEQop-
18 WHOgg concentrations are 36.3 and 25.5 ng/kg, respectively (standard deviation, 38.6).
19 The mean and median results reported by Green et al. (1995) and Cramer et al. (1995) are
20 very similar in terms of total TEQ to those reported by EPA for samples collected five years
21 earlier (U.S. EPA, 1996a; Rubin and White, 1992). The predominant congeners in both data sets
22 are the octa- and hepta-CDDs and CDFs. Although not present at high concentrations, 2,3,7,8-
23 TCDF was commonly detected.
24 In addition to effluents, Rappe et al. (1998) also analyzed the levels of CDDs and CDFs
25 in municipal sewage sludge from the 17 POTWs in Mississippi. Table 8-38 presents the
26 concentrations of dioxins measured in the sewage sludge samples and total TEQ emission factors
27 reported by Rappe et al. Concentrations were only congener specific for 2,3,7,8-TCDD; 2,3,7,8-
28 TCDF; 1,2,3,7,8-PeCDD; 2,3,4,7,8-PeCDF; OCDD; and OCDF. Also provided were
29 concentrations for total HxCDD and total HpCDD. The TEQ emission factors (assuming ND =
30 1/2 DL) reported by Rappe et al. ranged from 2.26 to 1,270 ng I-TEQDp/kg. The predominant
31 congeners in all samples were the octa- and hepta-CDDs. The sludge with the highest
32 concentrations of octa- and hepta-CDDs was from the Picayune POTW, which receives
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1 industrial inputs, including effluents from wood treatment facilities that likely contain PCP. In
2 general, the sludge with the lowest TEQ values were from the facilities that do not receive
3 effluent from industrial facilities. Additionally, the samples with the two lowest TEQ values
4 were from facilities that do not use free chlorine as a disinfectant.
5 In 1999, sewage sludge samples from a POTW in Ohio were collected and analyzed for
6 CDDs/CDFs (U.S. EPA, 2000f). The facility, which accepts both domestic and industrial
7 wastewater, employs secondary wastewater technology. Assuming nondetects are zero, the
8 mean TEQ emission factor is 21.9 ng TEQoF-WHOgg/kg (dry-weight basis). These results are
9 presented in Table 8-39.
10 In 2000 and 2001, AMSA conducted another survey of dioxin-like compounds in sewage
11 sludge (Alvarado et al., 2001). A total of 200 sewage sludge samples were collected from 171
12 POTWs located in 31 states. Assuming nondetects are zero, TEQ emission factors range from
13 0.08 to 3,578.61 ng TEQoF-WHOgg/kg. The mean and median TEQ emission factors are 34.5
14 and 11.79 ng TEQDF-WHO98/kg, respectively.
15 EPA conducted another National Sewage Sludge Survey to characterize the dioxin and
16 dioxin-like equivalence levels in biosolids produced by 6857 POTWs operating in the United
17 States in 2001 (U.S. EPA, 2002a). Samples were collected from 94 POTWs using secondary or
18 higher treatment practices. All facilities had been sampled previously as part of the 1988/1989
19 National Sewage Sludge Survey. The overall mean and median TEQoF-WHOgg concentrations
20 were 75 and 15 ng/kg, respectively. However, when the data were weighted using the daily
21 influent wastewater flow rates (i.e., the number of facilities with wastewater flow rate
22 >100 Mg/day, >10 but < 100 Mg/day, >1 but < 10 Mg/day, and < 1 Mg/day), the overall mean and
23 median TEQDF-WHO98 concentrations were 21.7 and 15.5 ng/kg, respectively. These data are
24 summarized in Table 8-40.
25 The CDD/CDF concentrations and congener group patterns observed in the U.S. surveys
26 are similar to those reported for sewage sludges in several other Western countries. Stuart et al.
27 (1993) reported mean CDD/CDF concentrations of 23.3 ng I-TEQDF/kg (dry weight) for three
28 sludges from rural areas, 42.3 ng I-TEQDF/kg for six sludges from light industry/domestic areas,
29 and 52.8 ng I-TEQDp/kg for six sludges from industrial/domestic areas collected during 1991-
30 1992 in England and Wales. Naf et al. (1990) reported concentrations ranging from 31 to 40 ng
31 I-TEQop/kg (dry weight) in primary and digested sludges collected from the POTW in
32 Stockholm, Sweden, during 1989. Gobran et al. (1995) reported an average concentration of
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1 15.7 ng 1-TEQop/kg in anaerobically digested sludges from an industrial/domestic POTW in
2 Ontario, Canada. In all three studies, the congener group concentrations increased with
3 increasing degrees of chlorination, with OCDD the dominant congener. Figure 8-6 presents
4 congener profiles, using the mean concentrations reported by Green et al. (1995).
5 Because the mean I-TEQDF concentration values reported in the 1988/1989 sewage
6 sludge survey (U.S. EPA, 1996a) and the 1995 survey (Green et al., 1995; Cramer et al., 1995)
7 were very similar, the estimated amounts of TEQs that may have been present in sewage sludge
8 and released to the environment in 1987 and 1995 were assumed to be the same. These values
9 were estimated using the average (49 ng 1-TEQop/kg) of the mean I-TEQop concentration values
10 (ND = DLs) reported by U.S. EPA (1996a) (50 ng I-TEQDF/kg) and by Green et al. (1995) and
11 Cramer et al. (1995) (36.3 ng TEQDF-WHO98/kg [47.7 ng I-TEQDF/kg]). Therefore, the overall
12 average mean emission factor for the reference years 1987 and 1995 is 36.3 ng TEQop-
13 WHCWkg (48.9 ng I-TEQDF/kg). The emission factor of 21.7 ng TEQDF-WHO98/kg, as
14 calculated from the 2001 survey, appears to be the most reasonable TEQ emission factor
15 estimate for reference year 2000 because this estimate is nationally weighted on the basis of
16 wastewater flow rates of POTWs operating in the United States in 2001.
17
18 8.4.1.3.2. Activity level information. According to the results of its 1988/1989 National
19 Sewage Sludge Survey, EPA estimated that approximately 5.4 million dry metric tons of sewage
20 sludge were generated in 1989 (Federal Register, 1993b). EPA also used the results of the 1984
21 to 1996 Clean Water Needs Surveys to estimate that 6.3 million dry metric tons of sewage sludge
22 were generated in 1998. Because estimates for reference years 1987 and 1995 are not available,
23 the 1989 and 1998 activity level estimates are used for 1987 and 1995, respectively. Tables 8-41
24 and 8-42 list the volumes, by use and disposal practices, of sludge disposed of annually for
25 reference years 1987 and 1995.
26 U.S. EPA (1999) estimated that 6.6 million dry metric tons of sewage sludge would be
27 generated in 2000. Table 8-43 lists the volumes, by use and disposal practices, of sludge
28 disposed of annually for reference year 2000. Similarly, the National Research Council (NRC)
29 (NRC, 2002) analyzed the amount of biosolids being applied to land in 2002. Citing 2001 data
30 (unpublished) from the Wisconsin Department of National Resources, NRC estimated that
31 approximately 8,650 of the 16,000 POTWs operating in the United States generated sewage
32 sludge requiring use or disposal. Using data from 37 states, an estimated 5,900 of these sewage
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1 sludge generators either land applied or publicly distributed more than 3.4 million dry tons of
2 biosolids annually. The volume of biosolids, by use and disposal practices, is presented in Table
3 8-44. The volume of biosolids and their distribution among the various categories estimated by
4 the NRC are very close to those estimated by the EPA.
5
6 8.4.1.3.3. Emission estimates. The annual potential releases of CDDs/CDFs are determined by
7 multiplying the mean total TEQ concentrations by the sludge volumes generated. The results for
8 reference years 1987, 1995, and 2000 are reported in Table 8-41, 8-42, and 8-43, respectively.
9 For reference year 1987, the total annual potential release from nonincinerated sludges was 151 g
10 TEQDF-WHO98. Of this amount, 2.6 g TEQDF-WHO98 (3.5 g I-TEQDF ) entered commerce as a
11 product for distribution and marketing and 76.6 g TEQDF-WHO98 (103 g I-TEQDF ) was applied
12 to land. The remaining 71.8 g TEQDF-WHO98 did not result in an environmental release because
13 it was sent to RCRA Subtitle D landfills or disposal sites. For reference year 1995, the total
14 annual potential release from nonincinerated sludges was 178 g TEQDF-WHO98. Of this amount,
15 3 g TEQDF-WHO98 (4 g I-TEQDF) entered commerce as a product for distribution and
16 marketing, and 116.1 g TEQoF-WHOgg (156.5 g I-TEQop) was applied to land. The remaining
17 58.9 g TEQoF-WHOgg did not result in an environmental release because it was sent to RCRA
18 Subtitle D landfills or disposal sites. For the year 2000, the total annual release of
19 nonincinerated sludges was 111 g TEQDF-WHO98. Of this amount, 1.9 g TEQDF-WHO98 (1.9 g
20 I-TEQDF) entered commerce as a product for distribution and marketing, and 78.2 g TEQDF-
21 WHO98 (78.2 g I-TEQDF) was applied to land. The remaining 30.9 g TEQDF-WHO98 did not
22 result in an environmental release because it was sent to RCRA Subtitle D landfills or disposal
23 sites.
24 These release estimates are assigned a high confidence rating for both the production and
25 emission factor estimates. The high rating was based on the judgment that the 174 facilities
26 tested as part of the 1988/1989 National Sewage Sludge Survey by EPA (U.S. EPA, 1996a), the
27 74 facilities tested as part of the 1994/1995 AMSA Survey (Green et al., 1995 and Cramer et al.,
28 1995), and the 94 facilities tested as part of the 2001 National Sewage Sludge Survey (EPA
29 2002) were reasonably representative of the variability in POTW technologies and sewage
30 characteristics nationwide.
31
32 8.4.2. Drinking Water Treatment Plants
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1 There is no strong evidence that chlorination of water for drinking purposes results in the
2 formation of CDDs/CDFs. Few surveys of CDD/CDF content in finished drinking water have
3 been conducted. Those that have been published have only rarely reported the presence of any
4 CDDs/CDFs, even at low pg/L DLs, and in those cases, CDDs/CDFs were also present in the
5 untreated water.
6 Rappe et al. (1989b) reported the formation of tetra- through octa-CDFs when tap water
7 and double-distilled water were chlorinated using chlorine gas. The CDF levels found in the
8 single samples of tap water and double-distilled water were 35 and 7 pg I-TEQop/L, respectively.
9 No CDDs were detected at DLs ranging from 1 to 5 pg/L. However, the water samples were
10 chlorinated at a dosage rate of 300 mg/L, which is considerably higher (by one to two orders of
11 magnitude) than the range of dosage rates typically used to disinfect drinking water. The authors
12 hypothesized that the CDFs or their precursors were present in chlorine gas.
13 Rappe et al. (1990a) analyzed a 1,500 L sample of drinking water from a municipal
14 drinking water treatment plant in Sweden. Although the untreated water was not analyzed, a
15 sludge sample from the same facility was analyzed. The large sample volume enabled DLs on
16 the order of 0.001 pg/L. The TEQ content of the water and sludge was 0.0029 pg I-TEQop/L and
17 1.4 ng/kg, respectively. The congener patterns of the drinking water and sludge sample were
18 very similar, suggesting that the CDDs/CDFs detected in the finished water were present in the
19 untreated water.
20
21 8.4.3. Soaps and Detergents
22 As discussed in Section 8.4.1, CDDs/CDFs were detected in nearly all sewage sludges
23 tested, whether the sludges were obtained from industrialized areas or from rural areas. Because
24 of the ubiquitous presence of CDDs/CDFs in sewage sludge, several studies have been
25 conducted to determine their source(s). A logical category of products to test, because of their
26 widespread use, is detergents, particularly those that contain or release chlorine during use (i.e.,
27 hypochlorite-containing and dichloroisocyanuric acid-containing detergents). The results of
28 studies conducted to date, summarized below, indicate that CDDs/CDFs are not formed during
29 use of chlorine-free detergents, chlorine-containing or chlorine-releasing detergents, or chlorine
30 bleach during household bleaching operations.
31 Sweden's Office of Nature Conservancy (1991) reported that the results of a preliminary
32 study conducted at one household indicated that CDDs/CDFs may be formed during use of
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1 dichloroisocyanurate-containing dishwasher detergents. A more extensive main study with
2 multiple runs was then conducted using standardized food, dishes, cutlery, and other household
3 items. Testing of laundry washing and fabric bleaching and actual testing of the CDD/CDF
4 content of detergents was also performed. The study examined (1) hypochlorite- and
5 dichloroisocyanurate-containing dishwasher detergents, (2) sodium hypochlorite-based bleach
6 (4.4% NaOCl) in various combinations with and without laundry detergent, and (3) sodium
7 hypochlorite-based bleach, used at a high enough concentration to effect bleaching of a pair of
8 imported blue j eans.
9 CDDs/CDFs were not detected in either the chlorine-free detergent or the detergent with
10 hypochlorite; 0.6 pg TEQ/g were detected in the detergent containing dichloroisocyanurate. The
11 results of all dishwasher and laundry washing machine tests showed very low levels of
12 CDDs/CDFs, often nondetected values. There was no significant difference between the controls
13 and the test samples; in fact, the control samples had a higher TEQ content than did some of the
14 test samples. The drainwater from the dishwasher tests contained <1 to <3 pg I-TEQDp/L (the
15 water-only control sample contained <2.8 pg I-TEQDF/L). The CDD/CDF content of the laundry
16 drainwater samples ranged from <1.1 to <4.6 pg I-TEQop/L (the water-only control sample
17 contained <4.4 pg I-TEQDF/L).
18 Thus, under the study's test conditions, CDDs/CDFs were not formed during
19 dishwashing or laundry washing or during bleaching with hypochlorite-containing bleach. No
20 definitive reason could be found for the difference in results between the preliminary study and
21 the main study for dishwashing with dichloroisocyanurate-containing detergents. The authors of
22 the study suggested that differences in the foods used and the prewashing procedures employed
23 in the two studies were the likely causes of the variation in the results.
24 Rappe et al. (1990c) analyzed a sample of a Swedish commercial soft soap, a sample of
25 tall oil, and a sample of tall resin for CDD/CDF content. Tall oil and tall resin, by-products of
26 the pulping industry, are the starting materials for the production of soft, liquid soap. Crude tall
27 oil, collected after the Kraft pulping process, is distilled under reduced pressure at temperatures
28 of up to 280 to 290 °C, yielding tall oil and tall resin. The measured TEQ content of the liquid
29 soap was found to be 0.647 ng TEQDF-WHO98/L (0.447 ng I-TEQDF/L). PeCDDs were the
30 dominant congener group, followed by HpCDDs, HxCDDs, PeCDFs, and OCDD, with some
31 tetra-CDFs and CDDs also present. The TEQ contents of the tall oil (12 ng TEQDF-WHO98/kg
32 [9.4 ng I-TEQDF/kg]) and tall resin (196 ng TEQDF-WHO98/kg [200 ng I-TEFDF/kg]) were
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1 significantly higher than the level found in the liquid soap. The tall oil contained primarily tetra-
2 and penta-CDDs and CDFs, whereas the tall resin contained primarily HpCDDs, HxCDDs, and
3 OCDD. The investigators compared the congener patterns of the three samples and noted that
4 although the absolute values for the tetra- and penta-CDDs and CDFs differed among the tall oil,
5 tall resin, and liquid soap samples, the same congeners were present. The congener patterns for
6 the more-highly chlorinated congeners were very similar. Table 8-44 presents the results of the
7 study.
8 In 1987, 118 million L of liquid household soaps were shipped in the United States (U.S.
9 DOC, 1990b); shipment quantity data are not available in the 1992 U.S. Economic Census (U.S.
10 DOC, 1996). Because only one sample of liquid soap has been analyzed for CDD/CDF content
11 (Rappe et al., 1990c), no estimate of environmental release can be made.
12
13 8.4.4. Textile Manufacturing and Dry Cleaning
14 As discussed in Section 8.4.1, CDDs/CDFs have been detected in almost all sewage
15 sludges tested, whether they were obtained from industrialized areas or rural areas. To determine
16 whether textile fabric or fabric finishing processes could account for the observed CDDs/CDFs,
17 several studies were conducted in Germany. These studies, summarized in the following
18 paragraphs, indicate that some finished textile products do contain detectable levels of
19 CDDs/CDFs and that they can be released from the textile during laundering or dry cleaning;
20 however, textile finishing processes are typically not sources of CDD/CDF formation. Rather,
21 the use of CDD/CDF-containing dyes and pigments and the use in some countries of PCP to treat
22 unfinished cotton appear to be the sources of the detected CDDs/CDFs.
23 Horstmann et al. (1993b) analyzed the CDD/CDF content of eight different raw
24 (unfinished) cotton cloths containing fiber from different countries and five different white
25 synthetic materials (acetate, viscose, bleached polyester, polyamide, and polyacrylic). The
26 maximum concentrations found in the textile fabrics were 30 ng/kg in the cotton products and 45
27 ng/kg in the synthetic materials. Also, a cotton finishing scheme was developed that subjected
28 one of the cotton materials to a series of 16 typical cotton finishing processes; one sample was
29 analyzed following each step. The fabric finishing processes showing the greatest effect on
30 CDD/CDF concentration were the application of an indanthrene dye and the "wash and wear"
31 finishing process, which together resulted in a CDD/CDF concentration of about 100 ng/kg. On
32 the basis of the concentrations found, the authors concluded that neither unfinished new fabrics
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1 nor common cotton finishing processes could explain the CDD/CDF levels found in laundry
2 wastewater.
3 Fuchs et al. (1990) reported that the dry-cleaning solvent redistillation residues collected
4 from 12 commercial and industrial dry-cleaning operations contained considerable amounts of
5 CDDs/CDFs. The reported I-TEQop content ranged from 131 to 2,834 ng/kg, with the dominant
6 congeners being OCDD and HpCDD. Towara et al. (1992) demonstrated that neither the use of
7 chlorine-free solvents nor variation of the dry-cleaning process parameters lowered the
8 CDD/CDF content of the residues.
9 Umlauf et al. (1993) conducted a study to characterize the mass balance of CDDs/CDFs
10 in the dry-cleaning process. The soiled clothes (containing 16 pg total CDDs/CDFs per kg)
11 accounted for 99.996% of the CDD/CDF input. Input of CDDs/CDFs from indoor air containing
12 0.194 pg/m3 accounted for the remainder (0.004%). The dry-cleaning process removed 82.435%
13 of the CDDs/CDFs in the soiled clothing. Most of the input CDDs/CDFs (82.264%) were found
14 in the solvent distillation residues. Air emissions (at 0.041 pg/m3) accounted for 0.0008% of the
15 total input, which was less than the input from indoor air. The fluff (at a concentration of
16 36 ng/kg) accounted for 0.1697%, and water effluent (at a concentration of 0.07 pg/L) accounted
17 for 0.0000054%.
18 Horstmann and McLachlan (1994a, b, 1995) analyzed 35 new textile samples (primarily
19 cotton products) obtained in Germany for CDDs/CDFs. Low levels were found in most cases
20 (total CDD/CDF less than 50 ng/kg). The dominant congeners were OCDD and HpCDD.
21 However, several colored T-shirts from a number of clothing producers had extremely high
22 levels, with concentrations up to 290,000 ng/kg. Because the concentrations in identical T-shirts
23 purchased at the same store varied by up to a factor of 20, the authors concluded that the source
24 of CDDs/CDFs was not a textile finishing process, because a process source would have resulted
25 in a more consistent level of contamination. Klasmeier and McLachlan (1995) subsequently
26 analyzed 68 new textile products obtained in Germany for OCDD and OCDF. Most samples had
27 nondetectable levels (42 samples <60 ng/kg). Only four samples had levels exceeding 500
28 ng/kg.
29 Horstmann and McLachlan (1994a, b) reported finding two different congener group
30 patterns in the more contaminated of the 35 textile products. One pattern agreed with the
31 congener pattern for PCP reported by Hagenmaier and Brunner (1987), whereas the other pattern
32 was similar to that reported by Remmers et al. (1992) for chloranil-based dyes. The authors
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1 hypothesized that the use of PCP to preserve cotton, particularly when it is randomly strewn on
2 bales of cotton as a preservative during sea transport, was the likely source of the high levels
3 occasionally observed. Although the use of PCP for nonwood uses was prohibited in the United
4 States in 1987 (see Section 8.3.8), PCP is still used in developing countries, especially to
5 preserve cotton during sea transport (Horstmann and McLachlan, 1994a).
6 Horstmann and McLachlan (1994a, b) conducted additional experiments that
7 demonstrated that the small percentage of clothing items with high CDD/CDF levels could be
8 responsible for the quantity of CDDs/CDFs observed in household wastewater (see Section
9 8.4.1.1).
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Table 8-1. CDD/CDF concentrations in pulp and paper mill bleached pulp, wastewater sludge, and wastewater
effluent (circa 1988)
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'b
Total 2,3,7,8-CDFa'b
Total I-TEQDF
(nondetect = 0)b
Total I-TEQDF
(nondetect = !/2 DL)b
Total TEQDF-WHO98
(nondetect = 0)b
Total TEQDF-WH098
(nondetect = !/2 DL)b
Total CDD/CDF"
Median
(ng/kg)
6.4
ND(0.3)
ND(0.4)
ND(0.5)
ND(0.5)
3.3
46
18
ND(0.7)
ND(0.2)
ND(0.3)
ND(0.3)
ND(0.3)
ND(0.3)
ND(0.6)
ND(0.6)
2.2
55.7
18
8.28
8.56
8.24
8.59
120
Bleached pulp
Range
(ng/kg)
0.4 to 124
ND(0.1)tol.4
ND(0.2) to 0.4
ND(0.2)tol.6
ND(0.2)to0.5
2.3 to 8.4
28 to 81
1.4 to 716
ND(0.1)to3.9
ND(0.1)to4.7
ND(0.2) to ND(0.6)
ND(0.1)toND(0.4)
ND(0.1)toND(0.4)
ND(0.2) to ND(0.4)
ND(0.1)to0.8
ND(0.1)toND(2.1)
ND(2.8)to4.3
No. of
detects
(10 samples)
10
2
1
2
1
10
10
10
4
3
0
0
0
0
3
0
8
89.47
91.7
i
Median
(ng/kg)
63
ND(2.5)
ND(3.1)
ND(3.2)
ND(3.9)
37
698
233
6.2
4.7
ND(2.5)
ND(1.4)
ND(1.7)
ND(1.7)
6.6
ND(1.6)
22
798
272.5
90.12
91.72
1,695
Wastewater sludge
Range
(ng/kg)
ND(6.3)tol80
ND(1.4)to28
ND(1.5)to40
ND(1.7)to95
ND(1.7)to80
18 to 490
263 to 1,780
13 to 1150
ND(1.2)to22
ND(0.9) to 38
ND(0.9)to31
ND(0.9) to 33
ND(0.9) to ND(4)
ND(0.9) to 34
ND(3.6)to70
ND(1.2)tolO
ND(54) to 168
No. of
detects
(9 samples)
8
1
1
1
1
9
9
9
6
6
2
1
0
1
7
1
8
Median
(Pg/L)
42
ND(9.6)
ND(12)
ND(12)
ND(12)
170
3,000
120
ND(7.2)
ND(6.3)
ND(8.4)
ND(7.1)
ND(6.2)
ND(8.2)
ND(23)
ND(22)
190
3,212
310
58.89
66.57
56.02
66.09
4,013
Wastewater effluent
Range
(Pg/L)
ND(ll)to98
ND(2.8)toND(25)
ND(6.6)toND(12)
ND(6.6) to ND(24)
ND(6.6) to ND(23)
77 to 270
1,000 to 4,600
12 to 840
ND(2.2) to 36
ND(2.2) to 33
ND(4.8)toND(15)
ND(4.8)toND(15)
ND(2.5)toND(15)
ND(4.8)toND(15)
ND(13)to44
ND(6.4)toND(41)
ND(180)to230
No. of
detects
(9 samples)
8
0
0
0
0
9
9
9
2
2
0
0
0
0
3
0
8
oo
"Calculated assuming nondetect values were zero.
bSum of median values.
DL = Detection limit
ND = Not detected (value in parenthesis is the detection limit)
Source: U.S. EPA (1990a).
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Table 8-2. CDD/CDF concentrations in pulp and paper mill bleached pulp, wastewater sludge, and wastewater
effluent (mid-1990s)
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-CDF"
Total I-TEQDF
(nondetect = 0)"
Total I-TEQDF
(nondetect = !/2 DL)a
Total TEQDF-WHO98
(nondetect = O)1
Total TEQDF-WH098
(nondetect = !/2 DL)a
Bleached pulp
Mean
nondetect
= 0
(ng/kg)
0.3
0
0
0
0
0
2.4
10.3
0
0.4
0
0
0
0
0
0
0
2.7
10.7
1.53
6.4
1.5
7.6
Median
(ng/kg)
ND(1)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(10)
ND(1)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(10)
Range
(ng/kg)
ND(l)to5
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(10)tol5
ND(l)to 170
ND(3) to ND(7)
ND(3) to 7
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(3) to ND(7)
ND(6)toND(14)
No. of
detects/
samples
1/18
0/18
0/18
0/18
0/18
0/18
3/16
7/18
0/18
1/18
0/18
0/18
0/18
0/18
0/18
0/18
0/18
Wastewater sludge
Mean
nondetect
= 0
(ng/kg)
0.8
0
0.5
2.3
1.6
41.4
445
6.2
0
0.5
0
0
0
0.5
1.2
0
0
492
8.4
3
12.9
2.6
15.2
Median
(ng/kg)
ND(1)
ND(5)
ND(5)
ND(5)
ND(5)
7
150
3
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(5)
ND(10)
Range
(ng/kg)
ND(l)to4
ND(4) to ND(52)
ND(4) to 7
ND(4)to 18
ND(4) to 14
ND(4) to 330
21 to 2,900
ND(l)to31
ND(4) to ND(52)
ND(4) to 7
ND(4) to ND(52)
ND(4) to ND(52)
ND(4) to ND(52)
ND(4) to 6
ND(4) to 10
ND(4) to ND(52)
ND(9)toND(100)
No. of
detects/
samples
4/12
0/12
1/13
2/13
2/13
9/13
10/10
9/12
0/13
1/13
0/13
0/13
0/13
1/13
2/13
0/13
0/13
Wastewater effluent
Mean
nondetect
= 0
(Pg/L)
1.2
0
0
0
0
3.2
99
2.3
103
2.3
1.5
53.6
1.4
66.5
Median
(ng/kg)
ND(ll)
ND(53)
ND(53)
ND(53)
ND(53)
ND(53)
ND(llO)
ND(ll)
ND(53)
ND(53)
ND(53)
ND(53)
ND(53)
ND(53)
ND(53)
ND(53)
ND(106)
Range
(Pg/L)
ND(10)to21
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to 58
ND(100)to370
ND(10)to23
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(50) to ND(55)
ND(104)to
ND(llO)
No. of
detects/
samples
1/18
0/18
0/18
0/18
0/18
1/18
6/14
2/18
0/18
0/18
0/18
0/18
0/18
0/18
0/18
0/18
0/18
oo
* Sum of mean values.
DL = Detection limit
ND = Not detected (value in parenthesis is the detection limit)
Source: Gillespie (1997).
-------
Table 8-3. Summary of bleached chemical pulp and paper mill discharges of
2,3,7,8-TCDD and 2,3,7,8-TCDF (g/yr)
Matrix
Effluent
Sludge6
Pulp
Congener
2,3,7,8-TCDD
2,3,7,8-TCDF
TEQ
2,3,7,8-TCDD
2,3,7,8-TCDF
TEQ
2,3,7,8-TCDD
2,3,7,8-TCDF
TEQ
U.S. EPA
1988a
201
1,550
356
210
1,320
343
262
2,430
505
NCASI
1992"
22
99
32
33
118
45
24
124
36
U.S. EPA
1993C
71
341
105
177
149
NCASI
1993"
19
76
27
24
114
35
22
106
33
NCASI
1994"
14.6
49
19.5
18.9
95.2
28.4
16.2
78.8
24.1
U.S. EPA
1995"
16
120
28
50
40
The total discharge rate of congener or TEQ (based only on 2,3,7,8-TCDD and 2,3,7,8-TCDF
concentrations) was summed across all 104 mills. Data from 104 Mill Study (U.S. EPA, 1990a).
bThe total discharge rate of congener or TEQ (based only on 2,3,7,8-TCDD and 2,3,7,8-TCDF
concentrations) was summed across all 104 mills. The daily discharge rates reported in NCASI (1993) and
Gillespie (1994, 1995) were multiplied by a factor of 350 days/yr to obtain estimates of annual discharge
rates. 1992 NCASI survey (NCASI, 1993), 1993 update (Gillespie, 1994), and 1994 update (Gillespie,
1995).
The discharges in effluent and sludge were estimated in U.S. EPA (1993d, 19971) for January 1, 1993. The
TEQ discharge in pulp was estimated by multiplying the 1988 discharge estimate by the ratio of the 1988
and!993 effluent discharge estimates (i.e., the estimate of the reduction in 1988 discharges achieved by
pollution prevention measures taken by the industry between 1988 and 1993).
The discharges in effluent and sludge were estimated in U.S. EPA (1997f) for mid-1995. The TEQ
discharge in pulp was estimated by multiplying the 1988 discharge estimate by the ratio of the 1988
and!995 effluent discharge estimates (i.e., the estimate of the reduction in 1988 discharges achieved by
pollution prevention measures taken by industry between 1988 and 1995).
eApproximately 20.5% of the sludge generated in 1990 was incinerated. The remaining 79.5% was
predominantly landfilled (56.5%) or placed in surface impoundments (18.1%); 4.1% was land-applied
directly or as compost, and 0.3% was distributed or marketed (U.S. EPA, 1993e).
~ = No information given
03/04/05
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Table 8-4. CDD/CDF TEQ concentrations and emissions for the paper and
pulp industry by source
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
Effluent
TEQ
conc.a
(pg/L)
0
O.OOe+00
O.OOe+00
1.30e-01
9.00e-02
7.00e-02
7.37e-02
l.OOe-01
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
1.90e-02
5.00e-03
2.00e-03
4.90e-01
TEQ
emission
s (ng/yr)
O.OOe+00
O.OOe+00
O.OOe+00
2.71e+08
1.88e+08
1.46e+08
1.54e+08
2.08e+08
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
3.96e+07
1.04e+07
4.17e+06
1.02e+09
Waste treatment
residuals not lagooned
or landfilled (sludge)
(49% not landfilled)
TEQ
conc.a
(ng/kg)
4.00e-01
5.00e-02
l.OOe-02
S.OOe-02
9.00e-02
1.82e-01
2.80e-01
4.00e-01
l.OOe-02
l.OOe-01
4.00e-02
l.OOe-02
5.00e-02
O.OOe+00
1.70e-02
O.OOe+00
3.70e-03
1.72
Residuals total
Residuals not landfilled
TEQ
emissions
(ng/yr)
4.63e+08
6.24e+07
1.25e+07
8.53e+07
9.05e+07
1.97e+08
2.81e+08
4.66e+08
1.25e+07
1.25e+08
4.63e+07
1.25e+07
5.15e+07
O.OOe+00
1.83e+07
O.OOe+00
3.93e+06
1.93e+09
9.44e+08
Pulp
TEQ
conc.a
(Pg/g
pulp)
l.OOe-02
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
3.00e-03
3.04e-03
l.OOe-03
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
2.00e-03
O.OOe+00
l.OOe-03
O.OOe+00
6.00e-05
2.01e-02
TEQ
emissions
(ng/yr)
2.90e+08
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
8.69e+07
8.80e+07
2.90e+07
O.OOe+00
O.OOe+00
O.OOe+00
O.OOe+00
5.79e+07
O.OOe+00
2.90e+07
O.OOe+00
1.74e+06
5.82e+08
aTEQ concentrations are in TEQDF-WHO9!
Source: Gillespie (2002).
03/04/05
8-57
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Table 8-5. CDD/CDF concentrations in graphite electrode sludge from chlorine
production (jig/kg)
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 TEQnF-WHO9Sa
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).
03/04/05
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Table 8-6. CDD/CDF concentrations in metal chlorides (jig/kg)
Congener group
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
FeCl3
—
—
—
ND
ND
—
—
—
12
42
AlCl3a
—
—
—
ND
ND
—
—
—
ND
ND
AlCl3a
—
—
—
ND
0.1
—
—
—
ND
34
CuCl2
—
—
—
0.03
0.6
—
—
—
0.1
0.5
CuCl
—
—
—
ND
0.03
—
—
—
0.08
0.2
TiCl4
—
—
—
ND
ND
—
—
—
ND
ND
SiCl4
—
—
—
ND
ND
—
—
—
ND
ND
aAlC!3 was tested twice.
ND = Not detected; detection limit of 0.02
~ = No information given
Source: Hutzinger and Fiedler (1991a).
03/04/05
8-59
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o
OJ
o
4^
o
Table 8-7. CDD/CDF concentrations in mono- through tetrachlorophenols (mg/kg)
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)a
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
(Nasalt)b'c
<0.02
O.03
<0.03
<0.1
<0.1
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
(Nasalt)b'c
0.7
5.2
9.5
5.6
0.7
0.5
10
70
70
10
-
oo
o
aSource: Firestone et al. (1972); because of poor recoveries, authors stated that actual CDD/CDF levels may have been considerably higher than those
reported.
bSource: Rappe et al. (1978a); common Scandinavian commercial chlorophenols.
°Source: Rappe et al. (1978b); common Scandinavian commercial chlorophenols.
ND = Not detected (value in parenthesis is the detection limit, if reported)
+ = Detected but not quantified
~ = No information given
-------
o
OJ
o
4^
o
Table 8-8. CDD/CDF concentrations (historical and current) in technical-grade pentachlorophenol (PCP)
products (jig/kg)
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-TEQDF'
Total TEQoF-WHCV
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
655,800
1978"
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
130,000
—
-
-
-
-
-
-
-
-
900
4,000
32,000
120,000
130,000
1,280,000
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
-
1,970
1,304
ND (10)
ND (10)
4,500
135,000
610,000
ND (10)
-
-
62,000
130,000
941,500
1985
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
1.688e+20
ND
ND
4,694
283,000
1,475,000
6
10
1,982
125,000
222,000
2,111,692
1986
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
1.038e+20
ND
ND
2,925
134,000
930,000
ND
3
1,407
146,000
233,000
1,447,335
1987'
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
1,085,000
19878
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
1,270,000
1985-88"
ND (0.05)
ND(1)
8
600
13
89,000
2,723,000
ND (0.5)
ND(1)
ND(1)
67
2
ND(1)
ND(1)
22,000
3,400
237,000
2.813e+20
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
—
-
> 1,270
>127
ND(10)
ND(10)
8,900
130,000
1,100,000
ND(10)
ND(10)
14,000
36,000
170,000
1,459,000
1988-99'
—
-
-
-
—
—
-
—
-
-
—
—
-
-
-
-
-
—
-
-
-
ND(1)
ND(10)
1,440
55,560
-
ND(10)
ND(10)
3,070
36,530
-
-
1988-991
ND (0.5)
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
—
-
-
-
ND
3
1,490
48,430
191,700
48
520
13,650
76,090
136,310
468,240
Un-
known11
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
-
-
-
-
-
-
-
-
-
-
-
oo
"Source: Buser and Bosshardt (1976); mean of 10 samples of "high" CDD/CDF-content PCP received from Swiss commercial sources in 1973.
bSource: Rappe et al. (1978b); sample of U.S. origin, "presumably prepared by alkaline hydrolysis of hexachlorobenzene."
'Source: U.S. Department of Health and Human Services (1989); composite of technical-grade materials produced in 1979 by Monsanto Industrial Chemical Co. (St. Louis,
MO), Reichhold Chemicals, Inc. (White Plains, NY), and Vulcan Materials Co. (Birmingham, AL).
dSource: Cull et al. (1984); mean of four "recent" production batches from each of two manufacturers of technical PCP using three different analytical methods; ANOVA
showed no statistically significant difference in CDD/CDF concentrations between the eight samples (samples obtained in the United Kingdom).
"Source: Pentachlorophenol Task Force (1997); samples of "penta" manufactured in 1985, 1986, and 1988.
'Source: Hagenmaier and Brunner( 1987); sample of WitophenP (Dynamit Nobel - Lot no. 7777) (obtained in Germany).
8Source: Hagenmaier and Brunner (1987); sample of PCP produced by Rhone Poulenc (obtained in Germany).
hSource: Harrad et al. (1991); PCP-based herbicide formulation from NY State Dept. Environmental Conservation.
'Source: Pentachlorophenol Task Force (1997); average of monthly batch samples for the period January 1987 to August 1996.
-------
oo
to
Table 8-8. CDD/CDF concentrations (historical and current) in technical pentachlorophenol (PCP) products
(continued)
^Source: KMG-Bermuth, Inc. (1997); average of monthly batch samples for the period February 1987 to December 1996 (excluding the following months, for which data
were not available: February 1993, January 1992, December 1991, September 1991, December 1988, and September 1988).
kSource: Schecter et al. (1 997); sample found stored in a barn in Vermont.
'Calculated assuming nondetects were zero.
kSource: Schecter et al. (1 997); sample found stored in a barn in Vermont.
'Calculated assuming nondetects were zero.
ND = Not detected (value in parenthesis is the detection limit)
— = No information given
-------
Table 8-9. Historical CDD/CDF concentrations in pentachlorophenol-Na
(PCP-Na) (jig/kg)
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-CDDh
Total 2,3,7,8-CDFh
Total I-TEQDFh
Total TEQDF-WHO98h
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF11
1969a
--
3,600
—
--
--
17,000
9,600
3,600
--
1973b
--
--
—
--
--
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
53,063
38,795
452
406
27
213
3,900
18,500
41,600
82
137
3,000
13,200
37,200
117,859
1987
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
35,289
4,499
79.5
58.5
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
1,059,253
126,492
3,374
2,566
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
43,841
1,201
1,096
1.9
140
14,000
100,000
81,000
1,200
6,400
49,000
91,000
36,000
378,742
"Source: 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 "low" CDD/CDF-content PCP-Na received from
Swiss commercial sources.
'Source: Buser and Bosshardt (1976); sample of "high" CDD/CDF-content PCP-Na received from a Swiss
commercial source.
dSource: Hagenmaier and Brunner (1987); sample of Dowicide-G purchased from Fluka; sample obtained in
Germany.
'Source: Hagenmaier and Brunner (1987); sample of PreventolPN (Bayer AG); sample obtained in Germany.
'Source: 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.
03/04/05
8-63
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Table 8-10. Summary of specific dioxin-containing wastes that must comply
with land disposal restrictions'1
EPA
hazardous
waste
number
Waste description
Land disposal
restriction effective
date
Regulated
waste
constituent
F020
Wastes (except wastewater 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 wastewater 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 wastewater 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 wastewater 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 wastewater 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
03/04/05
8-64
DRAFT-DO NOT CITE OR QUOTE
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Table 8-10. Summary of specific dioxin-containing wastes that must comply
with land disposal restrictions'1 (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. F020-F023, 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
of2,4-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
Tor wastewater, the treatment standard for all regulated waste constituents except PeCDFs is 0.063 ng/L; the
standard for PeCDFs is 0.035 ng/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.
03/04/05
8-65
DRAFT-DO NOT CITE OR QUOTE
-------
o
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o
Table 8-11. CDD/CDF concentrations in chlorobenzenes (|ig/kg)
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)
~
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)
~
1,2,4-TrCBz
("pure")"
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)
~
Mixed
TrCBz
(47%)a
0.027
0.14
0.259
0.253
0.081
0.736
0.272
0.091
0.03
0.016
1.904
1,2,4,5-TeC
Bz
(99%)a
ND (0.02)
0.2
0.5
0.8
0.4
0.03
0.2
0.8
1.5
2.1
~
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
~
HCBz
(97%)a
ND (20)
ND (20)
ND (20)
470
6,700
ND (20)
ND (20)
ND (20)
455
2,830
~
HCBzb
~
~
~
~
50-212,000
~
~
~
~
350-58,300
~
oo
Oi
Oi
aSource: Hutzinger and Fiedler (1991a); 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
O
O
2
O
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 8-12. Concentrations of CDD/CDF congener groups in unused commercial polychlorinated biphenyl (PCB)
mixtures (mg/kg)
PCB mixture
Aroclor 1016
Aroclor 1242
Aroclor 1242
Aroclor 1242
Clophen A-30
Clophen A-30
Aroclor 1248
Clophen A-40
Kanechlor 400
Aroclor 1254
Aroclor 1254
Aroclor 1254
Aroclor 1254
Clophen A-50
Aroclor 1260
Aroclor 1260
Aroclor 1260
Aroclor 1260
Clophen A-60
Clophen A-60
Clophen A-60
Phenoclor
DP-6
Clophen T-64
Prodelec 3010
Year of
manufacture
1972
—
—
—
1969
—
1969
1970
—
—
-
1969
—
—
-
—
-
CDF congener group concentrations
TCDF
ND
0.07
2.3
0.25
6.377
0.713
0.5
1.289
0.1
0.2
0.02
0.05
5.402
0.3
0.1
0.8
0.2
15.786
16.34
1.4
0.7
0.3
1.08
PeCDF
ND
0.03
2.2
0.7
2.402
0.137
1.2
0.771
0.2
0.4
0.2
0.1
2.154
1
0.4
0.9
0.3
11.655
21.164
5
10
1.73
0.35
HxCDF
ND
0.003
ND
0.81
0.805
0.005
0.3
0.144
1.4
0.9
0.6
0.02
2.214
1.1
0.5
0.5
0.3
4.456
7.63
2.2
2.9
2.45
0.07
HpCDF
—
—
—
0.108
0.001
0.02
—
—
—
0.479
1.35
—
—
—
1.517
2.522
0.82
-
OCDF
—
—
—
0.016
ND
0.011
—
—
—
0.069
—
—
—
0.639
1.024
—
-
Total
CDF
ND
0.15
4.5
1.9
9.708
0.855
22.2352
1.7
1.5
0.8
0.2
10.318
3.8
1
2.2
0.8
34.052
48.681
8.6
13.6
5.4
2
CDD congener group concentrations
TCDD
—
—
—
0.0007
ND
ND
—
—
—
ND
—
—
—
0.0004
ND
—
-
PeCDD
—
—
—
ND
ND
ND
—
—
—
ND
—
—
—
0.002
ND
—
-
HxCDD
—
—
—
0.001
ND
ND
—
—
—
ND
—
—
—
0.002
ND
—
-
HpCDD
—
—
—
0.006
0.005
0.012
—
—
—
0.011
—
—
—
0.003
0.014
—
-
OCDD
—
—
—
0.031
0.025
0.03
—
—
—
0.027
—
—
—
0.015
0.032
—
-
Total
CDD
—
—
—
0.039
0.03
0.042
—
—
—
0.038
—
—
—
0.022
0.046
—
-
Source
a
b,c
b,c
b
e
d
b
d
b,c
a
a
b,c
b
d
b,c
a
b, c
a
e
d
a
a
b
b
oo
"Source: Bowes et al. (1975a).
"Source: Erickson (1986).
cSource: ATSDR(1993).
dSource: Hagenmaier (1987).
'Source: Malisch( 1994).
ND = Not detected
— = No information given
-------
o
OJ
o
4^
o
Table 8-13. 2,3,7,8-Substituted congener concentrations in unused polychlorinated biphenyl (PCB) mixtures (|ig/kg)
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 TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDFe
Total I-TEQDFe
Total TEQoF-WHO,/
Congener concentrations in Clophens
A-30"
ND
ND
ND
0.8
ND
5.6
31.1
1,032.6
135.8
509.2
301.4
65.3
ND
50.6
43.7
22.5
15.7
0.7
ND
1.2
5.6
31.1
6,376.6
2,402.4
804.8
108.3
15.7
9,746.4
407.2
407.2
A-30"
ND
ND
ND
ND
ND
2.4
24.7
36.9
14.9
13.1
1.9
0.8
ND
0.1
0.6
ND
ND
ND
ND
ND
5.4
24.7
713
136.5
5.1
0.8
ND
885.5
11.3
11.3
A-40"
ND
ND
ND
ND
ND
4.4
30.3
250.2
52.7
171.3
48.4
19.6
0.7
6.8
7
2.8
11.4
ND
ND
ND
11.6
30.3
1,289.4
770.8
143.6
19.5
11.4
2,276.61
A-50"
ND
ND
ND
ND
ND
5.3
26.9
1,005.7
155.2
407.5
647.5
227.5
8.3
62.5
205.5
72.2
69.2
ND
ND
ND
11
26.9
5,402.3
2,153.7
2,213.8
478.8
69.2
10,355.7
409.6
409.5
A-60"
ND
0.1
0.2
ND
ND
2.5
14.9
2,287.7
465.2
1,921.9
1,604.2
157.6
42.8
369.5
480.6
321.7
639.2
0.4
9
1.8
3
14.9
15,785.7
11,654.6
4,455.8
1,517
639.2
34,074.4
1,439.2
1,439
A-60"
ND
ND
ND
ND
ND
6.8
32.3
3,077.2
1,750.8
2,917.0
2,324.1
351.3
19
4,08.3
1,126.1
304
1,024.3
ND
ND
ND
13.5
32.3
16,340
21,164
7,630.2
2,522.3
1,024.3
48,726.5
2,179
2,178
Congener concentrations in Aroclors
1016C
..
-
-
-
-
-
-
0.1
-
1.75
-
-
0.08
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1242C
..
—
—
—
—
-
-
40.1
—
40.8
—
—
0.26
—
-
-
-
..
—
—
-
-
..
-
-
-
-
..
-
-
1248"
..
-
-
-
-
-
-
330
-
830
-
-
-
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1254C
..
-
-
-
-
-
-
28
-
110
-
-
28.8
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1254C
..
-
-
-
-
-
-
20.9
-
179
-
-
28.7
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1254C
..
—
—
—
—
-
-
55.8
—
105
—
—
19.4
—
-
-
-
..
—
—
-
-
..
—
—
-
-
..
-
-
1254"
..
-
-
-
-
-
-
110
-
120
-
-
-
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1260C
..
-
-
-
-
-
-
63.5
-
135
-
-
5.1
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1260C
..
-
-
-
-
-
-
6.88
-
58.2
-
-
9.7
-
-
-
-
..
-
-
-
-
..
-
-
-
-
..
-
-
1260C
..
—
—
—
—
-
-
29
—
112
—
—
10.7
—
-
-
-
..
—
—
-
-
..
—
—
-
-
..
-
-
oo
ON
oo
"Source: Malisch (1994).
"•Source: Hagenmaier (1987).
'Source: Brown et al. (1988).
•"Source: Bowes (1975b).
'Calculated assuming nondetect values were zero.
ND = Not detected
- = No information given
-------
Table 8-14. Reported CDD/CDF concentrations in wastes from poly vinyl
chloride (PVC) manufacture (jig/kg)
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 TEQnF-WHO9S
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
O
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).
03/04/05
8-69
DRAFT-DO NOT CITE OR QUOTE
-------
o
OJ
o
4^
o
Table 8-15. CDD/CDF measurements in treated wastewater and wastewater solids from U.S. EDC/VCM/PVC
manufacturers
Congener/congener groups
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-TEQDF (nondetect = 0)
Mean I-TEQDF (nondetect = 1A
DL)
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Treated wastewater
PVC-only facilities
No.
detects/
samples
0/6
0/6
0/6
0/6
0/6
2/6
1/6
0/6
0/6
0/6
1/6
1/6
0/6
1/6
1/6
1/6
2/6
0/6
0/6
0/6
2/6
1/6
0/6
0/6
1/6
1/6
2/6
Concentration
range3
(ng/L)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.42
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
ND
ND
26
260
ND
ND
ND
5.8
3.8
ND
6.1
26
6.2
33
4.4
ND
ND
ND
48
260
ND
ND
30
49
33
EDC/VCM/PVC facilities
No.
detects/
samples
0/4
0/4
0/4
0/4
0/4
1/4
1/4
0/4
0/4
0/4
0/4
0/4
0/4
1/4
3/4
2/4
4/4
0/4
0/4
0/4
1/4
1/4
0/4
0/4
1/4
3/4
4/4
Concentration
range3
(ng/L)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.88
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
ND
ND
14
130
ND
ND
ND
ND
ND
ND
6.5
78
20
900
4.7
ND
ND
ND
22
130
ND
ND
14
140
900
Wastewater solids
EDC/VCM/PVC facilities
No.
detects/
samples
4/8
3/8
4/8
7/8
6/8
8/8
8/8
8/8
8/8
8/8
8/8
8/8
8/8
7/8
8/8
7/8
8/8
6/8
5/8
7/8
8/8
8/8
8/8
8/8
8/8
8/8
8/8
Concentration
rangeb'c
(ng
Min.
ND
ND
ND
ND
ND
74
390
18
36
50
180
74
78
ND
570
ND
1,800
1,680
ND
ND
ND
74
390
210
380
750
880
1,800
/kg)
Max.
109
320
455
520
645
3,230
9,700
460
1,500
1,750
7,550
3,650
2,800
425
20,600
12,000
4,200,000
1,680
730
1,630
3,915
5,300
9,700
9,800
18,000
31,000
39,400
4,200,000
PVC-only facilities
No.
detects/
samples
1/2
0/2
1/2
1/2
1/2
2/2
2/2
0/2
0/2
0/2
1/2
1/2
1/2
0/2
1/2
1/2
2/2
1/2
1/2
1/2
2/2
2/2
1/2
1/2
2/2
2/2
2/2
Concentration
rangeb>c
(ng/kg)
Min.
ND
ND
ND
ND
ND
28
200
ND
ND
ND
ND
ND
ND
ND
9.7
ND
39
1.9
ND
ND
ND
58
200
ND
ND
1.5
11
39
Max.
2
ND
3.2
2.3
2.4
35
640
ND
ND
ND
3.6
2.4
3.8
ND
12
2
43
3.6
6.3
3.3
14
64
640
4.8
4
11
18
43
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"Method detection limits for individual samples were less than 10 pg/L for all congeners and congener groups except OCDD and OCDF, which had MDLs less than 50 pg/L.
bDry-weight basis.
'Methods detection limits for all congeners were less than 150 ng/kg and usually were less than 10 ng/kg.
-------
S Table 8-15. CDD/CDF measurements in treated wastewater and wastewater solids from U.S. EDC/VCM/PVC
2 manufacturers (continued)
o
Source: Vinyl Institute (1998).
EDC = Ethylene dichloride
VCM = Vinyl chloride monomer
PVC = Polyvinyl chloride
DL = Detection limit
ND = Not detected
oo
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HH
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-------
Table 8-16. Emissions data for wastewater from PVC/EDC/VCM manufacturing facilities
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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-TEQDF
Total TEQDF-WHO98
Annual Release to Water (g/yr)
Dow Chemical
Freeport, TX
O.OOE+00
O.OOE+00
5.64E-01
O.OOE+00
3.52E-01
1.98E+01
1.23E+02
2.77E+00
3.71E+00
1.67E+00
2.76E+01
O.OOE+00
O.OOE+00
6.08E+00
1.31E+02
1.93E+01
3.31E+02
6.91E+00
6.50E+00
Dow Chemical
Plaquemine, LA
6.45E-02
1.19E-01
8.70E-01
O.OOE+00
5.34E-01
2.90E+01
6.29E+02
4.78E+00
3.77E+00
2.01E+00
2.22E+01
O.OOE+00
1.08E+00
3.82E+00
1.64E+02
1.18E+01
3.81E+02
7.71E+00
6.86E+00
Georgia Gulf
Plaquemine, LA
6.90E-04
3.55E-03
3.98E-03
4.46E-03
5.00E-03
3.43E-02
1.18E-01
7.61E-03
6.57E-03
2.11E-02
2.00E-02
1.41E-02
9.34E-03
7.89E-03
1.11E-01
2.41E-02
4.05E-01
2.28E-02
2.41E-02
Occidental
Convent, AL
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
3.26E-04
1.49E-01
2.85E-04
6.00E-04
1.03E-04
1.72E-02
1.89E-04
O.OOE+00
O.OOE+00
2.51E-04
O.OOE+00
3.55E-02
2.04E-03
1.87E-03
Occidental
Deer Park, TX
O.OOE+00
O.OOE+00
2.20E-03
2.64E-03
2.45E-03
7.67E-02
1.19E+00
5.08E-05
2.35E-03
3.68E-03
3.71E-02
2.77E-02
2.89E-02
1.44E-02
6.90E-01
2.61E-01
5.85E+00
3.08E-02
2.45E-02
Occidental
Ingleside, TX
1.79E-02
9.25E-02
8.38E-02
8.55E-02
7.70E-02
9.50E-02
1.84E-01
1.60E-02
8.91E-02
8.89E-02
8.83E-02
1.03E-01
9.80E-02
9.68E-02
l.OOE-01
9.70E-02
1.85E-01
1.81E-01
2.27E-01
Occidental
LaPorte, TX
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
5.18E-02
O.OOE+00
O.OOE+00
O.OOE+00
4.21E-02
O.OOE+00
O.OOE+00
O.OOE+00
1.18E-01
3.18E-02
6.72E-01
6.43E-03
5.78E-03
PPG Industries
Lake Charles, LA
O.OOE+00
2.37E-03
5.28E-03
6.27E-03
4.60E-03
4.03E-01
2.97E+00
6.47E+00
1.43E+01
1.08E+01
1.23E+01
3.96E+00
3.23E+00
1.57E+00
4.41E+00
2.64E+00
1.21E+01
8.98E+00
8.97E+00
oo
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Table 8-17. Emissions data for wastewater from chlor-alkali production facilities
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-TEQDF
Total TEQDF-WHO98
Annual Release to Water (g/yr)
Dow Chemical
Midland, TX
O.OOE+00
O.OOE+00
1.72E-02
O.OOE+00
O.OOE+00
5.44E-01
3.63E+00
1.55E-02
O.OOE+00
8.64E-03
5.90E-02
O.OOE+00
O.OOE+00
3.96E-02
8.81E-01
1.45E-02
1.25E+00
3.67E-02
3.23E-02
Occidental
Battleground, TX
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
4.83E-01
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
4.83E-04
4.83E-05
Occidental
Deer Park, TX
2.40E-02
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
7.79E-01
2.15E+01
6.31E-01
1.20E+00
2.07E-01
2.11E+00
3.80E-01
2.03E-03
O.OOE+00
5.91E-01
5.66E-03
4.88E+00
5.40E-01
5.16E-01
Occidental
Delaware City, DE
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
4.09E-03
1.02E-03
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
2.31E-03
O.OOE+00
O.OOE+00
1.30E-04
1.26E-04
Occidental
Hahnville, LA
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
1.33E-02
9.74E-02
1.93E-01
8.97E-01
8.51E-01
2.96E+00
1.18E+00
6.31E-01
6.00E-01
4.47E+00
6.89E-01
1.75E+00
1.08E+00
1.08E+00
Occidental
Mobile, AL
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
1.15E-03
2.88E-04
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
6.49E-04
O.OOE+00
O.OOE+00
3.64E-05
3.54E-05
Occidental
Muscle Shoals, AL
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+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
8.64E-08
PPG Industries
Natrium, WV
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
O.OOE+00
2.21E-01
3.13E+00
6.38E-02
6.23E-02
3.29E-01
1.11E-01
O.OOE+00
O.OOE+00
O.OOE+00
1.54E-01
O.OOE+00
6.60E-01
1.93E-01
1.89E-01
oo
o
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2
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H
O
Source: Chlorine Chemistry Council CDD/CDF Data Validation Project (2004).
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-------
Table 8-18. Congener-Specific land releases for PVC/EDC/VCM manufacturing facilities
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-TEQDF
Total TEQDF-WHO98
Annual Release to Land (g/yr)
Georgia Gulf
Plaquemine, LA
4.19E-03
3.91E-02
1.23E-01
1.22E-01
7.77E-02
1.71E+00
8.64E+00
7.65E-02
3.54E-01
3.70E-01
2.69E+00
2.11E+00
1.54E+00
5.95E-01
2.81E+01
6.54E+00
1.18E+02
1.45E+00
1.36E+00
Source: Chlorine Chemistry Council CDD/CDF Data Validation Project (2004).
03/04/05
8-74
DRAFT-DO NOT CITE OR QUOTE
-------
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Table 8-19. Congener-specific air emissions for PVC/EDC/VCM manufacturing facilities
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-TEQDF
Total TEQDF-WHO98
Annual Release to Air (g/yr)
Dow Chemical
Freeport, TX
1.42E-02
1.98E-01
1.01E+00
O.OOE+00
3.86E-01
3.73E+00
9.46E+00
1.26E+00
1.80E+00
1.28E+00
1.20E+01
O.OOE+00
3.43E-01
2.50E+00
3.23E+01
5.34E+00
6.69E+01
3.08E+00
3.11E+00
Dow Chemical
Plaquemine, LA
6.11E-05
4.98E-03
2.80E-02
O.OOE+00
1.18E-02
1.02E-01
2.65E-01
2.63E-02
3.84E-02
3.15E-02
3.96E-01
O.OOE+00
4.77E-03
4.80E-02
1.47E+00
9.81E-02
3.21E+00
9.19E-02
9.12E-02
Georgia Gulf
Plaquemine, LA
1.64E-03
2.68E-03
2.83E-03
2.34E-03
1.26E-03
1.64E-02
1.24E-01
9.20E-02
7.21E-02
3.46E-02
1.71E-01
7.09E-02
4.17E-02
1.33E-02
3.17E-01
3.43E-02
1.01E+00
6.82E-02
6.85E-02
Occidental
Convent, AL
4.53E-03
1.03E-02
3.79E-03
9.96E-03
4.84E-03
5.68E-03
4.74E-03
1.52E-02
1.74E-02
9.22E-03
1.44E-02
8.52E-03
3.15E-03
1.33E-03
1.96E-02
2.36E-03
1.53E-02
2.16E-02
2.67E-02
Occidental
Deer Park, TX
O.OOE+00
9.76E-03
4.72E-02
3.27E-02
5.64E-02
1.37E+00
1.35E+01
5.71E-02
1.21E-01
1.42E-01
1.38E+00
5.82E-01
5.55E-01
5.56E-02
1.19E+01
2.32E+00
5.28E+01
5.81E-01
5.26E-01
Occidental
Ingleside, TX
5.96E-03
3.38E-02
1.07E-01
1.22E-01
8.99E-02
1.58E+00
9.51E+00
4.38E-02
3.54E-01
3.71E-01
3.58E+00
3.38E+00
7.73E-01
1.94E+00
2.57E+01
5.13E+00
4.69E+01
1.61E+00
1.58E+00
Occidental
LaPorte, TX
O.OOE+00
6.81E-03
9.37E-03
1.65E-02
9.83E-03
1.51E-01
4.75E-01
7.78E-03
2.42E-02
2.53E-02
4.13E-02
3.62E-02
8.02E-03
4.09E-02
2.49E-01
2.31E-02
2.31E-01
3.92E-02
4.19E-02
PPG Industries
Lake Charles, LA
2.28E-04
2.20E-04
1.89E-03
7.61E-04
4.50E-04
6.09E-03
3.95E-02
1.29E-02
1.28E-02
8.71E-03
4.81E-02
2.50E-02
9.68E-03
8.79E-03
2.77E-01
4.12E-02
7.50E-01
2.01E-02
1.95E-02
oo
o
H
O
Source: Chlorine Chemistry Council CDD/CDF Data Validation Project (2004).
O
&
O
c
o
H
W
-------
Table 8-20. Congener-specific air emissions for chlor-alkali production facilities
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-TEQDF
Total TEQnF-WHO9S
Annual Rele
Dow Chemical
Midland, TX
2.65E-02
3.86E-03
8.05E-03
O.OOE+00
3.32E-03
2.03E-02
8.63E-02
2.28E-02
9.10E-03
7.63E-03
6.61E-02
O.OOE+00
1.82E-03
9.03E-03
1.48E-01
2.78E-02
2.25E-01
4.61E-02
4.77E-02
ase to Air (g/yr)
PPG Industries
Natrium, WV
2.81E-03
O.OOE+00
O.OOE+00
2.01E-03
2.01E-03
8.67E-02
2.08E-01
4.38E-02
3.21E-03
3.01E-02
4.42E-02
6.42E-03
6.02E-03
2.17E-02
1.42E-01
3.89E-02
6.38E-02
3.36E-02
3.33E-02
Source: Chlorine Chemistry Council CDD/CDF Data Validation Project (2004).
03/04/05
8-76
DRAFT-DO NOT CITE OR QUOTE
-------
o
OJ
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o
Table 8-21. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers
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-TEQDF (nondetect = 0)
Mean I-TEQDF (nondetect = Vi DL)
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/
samples3
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
0/22
0/22
0/22
1/22
0/22
0/22
0/22
1/22
0/22
0/22
Range" (ng/kg)
Min.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.002
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
ND
ND
0.64
ND
ND
ND
ND
ND
ND
ND
0.37
ND
ND
ND
0.7
ND
ND
ND
0.64
ND
ND
ND
0.37
ND
ND
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
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
ND
ND
ND
ND
ND
ND
ND
0.001
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
ND
ND
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.38
0.4
0.24
0.32
0.97
1.3
ND
ND
0.3
ND
ND
0.38
EDC sold as product"
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
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
ND
ND
ND
ND
ND
ND
ND
0.001
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Max.
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.1
0.4
11
0.21
ND
ND
ND
ND
ND
ND
ND
ND
2.02
11
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o
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2
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H
O
HH
H
W
O
aTwo of these 22 samples were duplicate samples from two sites. The results were averaged and treated as one sample for each site.
bMethod detection limits (MDLs) for individual samples were less than 2 ng/kg for all congeners and congener groups except OCDD and OCDF, which had
MDLs less than 6 ng/kg.
-------
^ °MDLs for individual samples were less than 2 ng/kg for all congeners and congener groups except OCDD and OCDF, which had MDLs less than 4 ng/kg.
<~f> d"Sales" EDC is defined as EDC sold commercially for non-VCM uses or exported from the United States.
eMDLs were less than 1 ng/kg for all congeners in all samples.
DL = Detection limit
ND = Not detected
Source: Vinyl Institute (1998).
oo
-------
Table 8-22. CDD/CDF concentrations in samples of dioxazine dyes and pigments (^ig/kg) (Canada)
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
l,2,3,6,7,8-HxCDFa
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-TEQDFb
Total TEQDF-WHO98b
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF b
Blue 106
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
31
41,953
ND (0.3)
ND (0.3)
ND (0.3)
12
—
ND (0.3)
50
-
12,463
41,984
12,525
56.4
7.45
ND (0.3)
ND (0.3)
ND (0.3)
34
41,953
ND (0.3)
ND (0.3)
12
71
12,463
54,533
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
6
28,523
ND (0.3)
ND (0.3)
ND (0.3)
2
—
ND (0.3)
10
-
1,447
28,529
1,459
30.3
3.4
ND (0.3)
ND (0.3)
ND (0.3)
8
28,523
0.3
ND (0.3)
2
32
1,447
30,012
ND (0.3)
ND (0.3)
-
ND (0.3)
ND (0.3)
9
18,066
ND (0.3)
ND (0.3)
ND (0.3)
2
—
ND (0.3)
14
-
1,006
18,075
1,022
19.5
2.3
ND (0.3)
ND (0.3)
ND (0.3)
12
18,066
ND (0.3)
ND (0.3)
2
26
1,006
19,112
Blue 108
ND (0.3)
ND (0.3)
-
ND (0.3)
ND (0.3)
ND (0.3)
23
ND (0.3)
ND (0.3)
ND (0.3)
ND (0.3)
—
ND (0.3)
9
-
11
23
20
0.1
0.1
ND (0.3)
ND (0.3)
1
ND (0.3)
23
ND (0.3)
ND (0.3)
ND (0.3)
12
11
47
Violet 23
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
9
7,180
ND (0.3)
0.5
ND (0.3)
76
—
ND (0.3)
13
-
941
7,189
1,031
16.0
8.7
ND (0.3)
ND (0.3)
21
30
7,180
ND (0.3)
0.5
76
26
941
8,275
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
1
806
ND (0.3)
ND (0.3)
ND (0.3)
4
—
ND (0.3)
10
-
125
807
139
1.4
0.6
ND (0.3)
ND (0.3)
2
5
806
ND (0.3)
ND (0.3)
5
14
125
957
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
16
11,022
ND (0.3)
ND (0.3)
ND (0.3)
39
—
ND (0.3)
11
-
3,749
11,038
3,799
18.9
5.6
ND (0.3)
ND (0.3)
7
36
11,022
ND (0.3)
ND (0.3)
39
29
3,749
14,882
ND (0.3)
ND (0.3)
-
ND (0.3)
ND (0.3)
10
7,929
ND (0.3)
ND (0.3)
ND (0.3)
31
—
ND (0.3)
4
-
1,556
7,939
1,591
12.7
4.2
ND (0.3)
ND (0.3)
ND (0.3)
11
7,929
ND (0.3)
ND (0.3)
31
13
1,556
9,540
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
2
1,627
ND (0.3)
ND (0.3)
ND (0.3)
9
—
ND (0.3)
1
-
147
1,629
157
2.7
1.1
ND (0.3)
ND (0.3)
ND (0.3)
2
1,627
0.4
ND (0.3)
9
2
147
1,787
ND (0.3)
ND (0.3)
~
ND (0.3)
ND (0.3)
4
1,420
ND (0.3)
ND (0.3)
ND (0.3)
7
—
ND (0.3)
12
-
425
1,424
444
2.7
1
ND (0.3)
ND (0.3)
1
6
1,420
ND (0.3)
ND (0.3)
7
21
425
1,880
oo
VO
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o
2
O
H
O
HH
H
W
O
"Results listed for 1,2,3,4,7,8-HxCDF include concentrations for 1,2,3,6,7,8-HxCDF.
bCalculations assume nondetected values are equal to zero.
-------
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oo
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o
O
O
2
O
H
O
HH
H
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O
Table 8-22. CDD/CDF concentrations in samples of dioxazine dyes and pigments (^ig/kg) (Canada) (continued)
O
^ ND = Not detected (value in parenthesis is the detection limit)
~ = Not reported
Source: Williams et al. (1992).
-------
Table 8-23. CDD/CDF concentrations in printing inks (ng/kg) (Germany)
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 a
Total TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Rotogravure
(2-color)
ND(1)
8
19
325
155
2,770
5,810
2.5
ND(2)
ND(2)
4
ND(3)
ND(3)
ND(3)
40
ND(4)
129
9,087
175.5
88.6
87.2
4
58
2,679
5,630
5,810
5.5
13
29
64
129
14,422
Rotogravure
(4-color)
ND(1.5)
ND(4)
ND(5)
310
105
1,630
2,350
14
ND(4)
ND(4)
7
ND(5)
ND(5)
ND(5)
14
ND(7)
ND(10)
4,395
35
62.4
60.3
ND(2)
145
2,485
3,460
2,350
28
ND(4)
45
14
ND(10)
8,527
Offset
(4-color)
ND(2)
15
16
82
42
540
890
7
ND(4)
ND(4)
27
ND(5)
ND(5)
ND(5)
315
11
960
1,585
1,320
35.4
41.2
77
35
660
1,100
890
90
340
95
566
960
4,813
Offset
(4-color)
ND(2)
6
11
21
14
240
230
7
ND(3)
ND(3)
35
ND(5)
ND(5)
ND(5)
42
ND(6)
165
522
249
15
18
38
25
246
445
230
35
110
94
63
165
1,451
""Calculations assume nondetect values were zero.
ND = Not detected (value in parenthesis is the detection limit)
~ = Not reported
Source: Santletal. (1994).
03/04/05
8-81
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Table 8-24. Chemicals requiring Toxic Substances Control Act Section 4 testing under the
dioxin/furan rule
Currently manufactured or imported as of June 5,1987
CAS No. Chemical name
79-94-7 Tetrabromobisphenol-A
118-75-2 2,3,5,6-Tetrachloro-2,5-cyclohexadiene-l,4-dione
118-79-6 2,4,6-Tribromophenol
120-83-2 2,4-Dichlorophenol
1163-19-5 Decabromodiphenyloxide
4162-45-2 Tetrabromobisphenol-A-bisethoxylate
21850-44-2 Tetrabromobisphenol-A-bis-2,3-dibromopropylethera
25327-89-3 Allyl ether of tetrabromobisphenol-A
32534-81-9 Pentabromodiphenyloxide
32536-52-0 Octabromodiphenyloxide
37853-59-1 l,2-Bis(tribromophenoxy)-ethane
55205-38-4 Tetrabromobisphenol-A-diacrylatea
Not currently manufactured or imported as of June 5,1987b
CAS No. Chemical name
79-95-8 Tetrachlorobisphenol-A
87-10-5 3,4',5-Tribromosalicylanide
87-65-0 2,6-Dichlorophenol
95-77-2 3,4-Dichlorophenol
95-95-4 2,4,5-Trichlorophenol
99-28-5 2,6-Dibromo-4-nitrophenol
120-36-5 2[2,4-(Dichlorophenoxy)]-propanoic acid
320-72-9 3,5-Dichlorosalicyclic acid
488-47-1 Tetrabromocatechol
576-24-9 2,3-Dichlorophenol
583-78-8 2,5-Dichlorophenol
608-71-9 Pentabromophenol
615-58-7 2,4-Dibromophenol
933-75-5 2,3,6-Trichlorophenol
1940-42-7 4-Bromo-2,5-dichlorophenol
2577-72-2 3,5-Dibromosalicylanide
3772-94-9 Pentachlorophenyl laurate
37853-61-5 Bismethylether of tetrabromobisphenol-A
Alkylamine tetrachlorophenate
- Tetrabromobisphenol-B
aNo longer manufactured in or imported into the United States (Cash, 1993).
bAs of August 5, 1995, neither manufacture nor importation of any of these chemicals had resumed in the United
States (Holderman, 1995).
03/04/05 8-82 DRAFT-DO NOT CITE OR QUOTE
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Table 8-25. Congeners and limits of quantitation (LOQ) for which
quantitation is required under the dioxin/furan test rule and pesticide Data
Call-in
Chlorinated dioxins
and furans
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
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
Brominated dioxins
and furans
2,3,7,8-TBDD
1,2,3,7,8-PeBDD
1,2,3,4,7,8-HxBDD
1,2,3,6,7,8-HxBDD
1,2,3,7,8,9-HxBDD
1,2,3,4,6,7,8-HpBDD
2,3,7,8-TBDF
1,2,3,7,8-PeBDF
2,3,4,7,8-PeBDF
1,2,3,4,7,8-HxBDF
1,2,3,6,7,8-HxBDF
1,2,3,7,8,9-HxBDF
2,3,4,6,7,8-HxBDF
1,2,3,4,6,7,8-HpBDF
1,2,3,4,7,8,9-HpBDF
LOQ
(US/kg)
0.1
0.5
2.5
2.5
2.5
100
1
5
5
25
25
25
25
1,000
1,000
03/04/05
8-83
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Table 8-26. Precursor chemicals subject to reporting requirements under
Toxic Substances Control Act Section 8(a)a
CAS No.
Chemical Name
85-22-3
87-61-6
87-84-3
89-61-2
89-64-5
89-69-0
92-04-6
97-74-6
94-81-5
95-50-1
95-56-7
95-57-8
95-88-5
95-94-3
95-50-7
99-30-9
99-54-7
106-46-7
108-70-3
108-86-1
108-90-7
117-18-0
120-82-1
348-51-6
350-30-1
615-67-8
626-39-1
827-94-1
Pentabromoethylbenzene
1,2,3-Trichlorobenzene
l,2,3,4,5-Pentabromo-6-chlorocyclohexane
1,4-Dichloro-2-nitrobenzene
4-Chloro-2-nitrophenol
2,4,5-Trichloronitrobenzene
2-Chloro-4-phenylphenol
4-Chloro-o-toloxy acetic acid
4-(2-Methyl-4-chlorophenoxy) butyric acid
o-Di chl orob enzene
o-Bromophenol
o-Chlorophenol
4-Chlororesorcinol
1,2,4,5-Tetrachlorobenzene
5-Chloro-2,4-dimethoxy aniline
2,6-Dichloro-4-nitroaniline
1,2-Dichloro-4-nitrobenzene
p-Dichlorobenzene
1,3,5-Trichlorobenzene
Bromobenzene
Chl orob enzene
l,2,4,5-Tetrachloro-3-nitrobenzene
1,2,4-Trichlorobenzene
o-Chl orofluorob enzene
3-Chloro-4-fluoronitrobenzene
Chlorohydroquinone
1,3,5-Tribromobenzene
2,6-Dibromo-4-nitroaniline
aDibromobenzene (CAS No. 106-37-6) was identified in the preamble to 52 FR 21412 as one of 29 precursor
chemicals; however, it was inadvertently omitted from the regulatory text. Because the regulatory text identified
only 28 chemicals, 28 chemicals appear in 40 CFR 766.38 and in this table.
03/04/05
8-84
DRAFT-DO NOT CITE OR QUOTE
-------
Table 8-27. Results of analytical testing for dioxins and furans in the
chemicals tested to date under Section 4 of the dioxin/furan test rule
CAS
number
79-94-7
118-75-2
118-79-6
120-83-2
1163-19-5
25327-89-3
32536-52-0
378-53-59-1
32534-81-9
4162-45-2
Chemical name
Tetrabromobisphenol-A
2,3,5,6-Tetrachloro-2,5-
cyclohexadiene-
1,4-dione (chloranil)
2,4,6-Tribromophenol
2,4-Dichlorophenol
Decabromodiphenyl
oxide
Allyl ether of
tetrabromobisphenol-A
Octabromodiphenyl
oxide
l,2-Bis(tribromo-
phenoxy)-ethane
Pentabromodiphenyl
oxide
Tetrabromobisphenol-A-
bisethoxylate
No. of
chemical
companies
that
submitted
data
3
6
1
1
3
1
3
1
3
1
No. of
positiv
e
studies
0
5
0
0
o
5
0
o
3
i
3
0
Congeners detected
(detection range in Hg/kg)
a
See Table 8-26
a
a
2,3,7,8-PeBDD(ND-0.1)
l,2,3,4,7,8/l,2,3,6,7,8-HxBDD(ND-0.5)
1,2,3,7,8,9-HxBDD (ND-0.76)
1,2,3,7,8-PeBDF (ND-0.7)
l,2,3,4,7,8/l,2,3,6,7,8-HxBDF(ND-0.8)
1,2,3,4,6,7,8-HpBDF (17-186)
a
2,3,7,8-TBDD (ND-0.71)
l,2,3,7,8-PeBDD(ND-0.1)
2,3,7,8-TBDF (ND-12.6)
1,2,3,7,8-PeBDF (ND-6.3)
2,3,4,7,8-PeBDF (ND-83.1)
l,2,3,4,7,8/l,2,3,6,7,8-HxBDF(ND-67.8)
1,2,3,7,8,9-HxBDF (ND-56.0)
1,2,3,4,6,7,8-HpBDF (ND-330)
2,3,7,8-TBDF (ND-0.04)
l,2,3,4,7,8/l,2,3,6,7,8-HxBDF(ND-0.03)
1,2,3,4,6,7,8-HpBDF (ND-0.33)
1,2,3,7,8-PeBDD (ND-5.9)
l,2,3,4,7,8/l,2,3,6,7,8-HxBDD(ND-6.8)
l,2,3,4,7,8/l,2,3,6,7,8-HxBDD(ND-6.8)
1,2,3,7,8,9-HxBDD (ND-0.02)
2,3,7,8-TBDF(ND-3.1)
1,2,3,7,8-PeBDF (0.7-10.2)
2,3,4,7,8-PeBDF (0.1-2.9)
1,2,3,4,7,8/1,2,3,6,7,8-HxBDF (15.6-61.2)
1,2,3,4,6,7,8-HpBDF (0.7-3.0)
a
aNo 2,3,7,8-substituted dioxins and furans detected above the test rule target limits of quantitation (see
Table 8-18).
Source: Holderman and Cramer (1995).
03/04/05
8-85
DRAFT-DO NOT CITE OR QUOTE
-------
Table 8-28. CDD/CDF concentrations in chloranil and carbazole violet
samples analyzed pursuant to the EPA dioxin/furan test rule (jig/kg)
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-TEQDFa
Total TEQDF-WHO98a
Chloranil
Importer
1
ND(1)
ND(2)
ND(3)
ND(3)
ND(1)
110
240,000
ND(1)
ND(1)
ND(1)
35
ND(5)
6
ND(5)
33
ND(15)
18,000
263
31
Importer
2
ND(1)
ND(2)
ND(10)
75
48
8,200
180,000
ND(2)
ND(1)
ND(1)
ND (860)
ND (860)
ND (680)
ND (680)
240,000
ND(IOO)
200,000
2,874
2,532
Importer
3
ND(2)
ND(5)
ND(5)
ND(5)
ND(5)
390
760,000
ND(1)
ND(3)
ND(3)
ND(4)
ND(4)
ND(4)
ND(4)
36
ND(15)
50,000
814
85
Importer
4
ND(2)
ND(6)
ND(3)
6
9
2,300
71,000
ND(2)
ND(5)
ND(5)
5,600
ND (600)
ND (600)
ND (600)
230,000
ND (400)
110,000
3,065
2,903
Carbazole
violet
ND (0.8)
ND (0.5)
ND(1.2)
ND(1.2)
ND(1.2)
28
1,600
ND(1.6)
ND (0.9)
ND (0.9)
ND(20)
ND(20)
ND(20)
ND(20)
15,000
ND(20)
59,000
211
156
Calculated assuming nondetect values are zero.
ND = Not detected (value in parenthesis is the minimum detection limit)
Source: Remmersetal. (1992).
03/04/05
8-86
DRAFT-DO NOT CITE OR QUOTE
-------
o
OJ
o
4^
o
Table 8-29. Status of first pesticide data call-in: pesticides suspected of having the potential to become
contaminated with dioxins if synthesized under conditions favoring dioxin formation
Shaughnessey
code
000014
008706
009105
012001
012101
019201
019202
019401
025501
027401
28201
028601
029201
29601
029902
029906
030602
031301
031503
031516
031563
034502
035502
Pesticide [active ingredient]
Dichlorodifluoromethane
O-(4-Bromo-2,5-dichlorophenyl) O,O-dimethyl phosphorothioate
Dimethylamine 2,3,5-triiodobenzoate
Neburon
Crufomate
MCPB, 4-butyric acid [4-(2-Methyl-4-chlorophenoxy)butyric acid]
MCPB, Na salt [Sodium 4-(2-methyl-4-chlorophenoxy)butyrate]
4-Chlorophenoxyacetic acid
Chloroxuron
Dichlobenil
Propanil [3 ',4'-Dichloropropionanilide]
Dichlofenthion [O-(2,4-Dichlorophenyl) O,O-diethyl phosphorothioate)]
DDT [Dichloro diphenyl trichloroethane]
Dichlone [2,3-dichloro-l,4-naphthoquinone]
Ammonium chloramben [3-amino-2,5-dichlorobenzoic acid]
Sodium chloramben [3-amino-2,5-dichlorobenzoic acid]
Sodium 2-(2,4-dichlorophenoxy)ethyl sulfate
DCNA [2,6-Dichloro-4-nitroaniline]
Potassium 2-(2-methyl-4-chlorophenoxy)propionate
MCCP, DBA Salt [Diethanolamine 2-(2-methyl-4-chlorophenoxy)propionate]
MCPP, IOE [Isooctyl 2-(2-methyl-4-chlorophenoxy)propionate]
Dicapthon [O-(2-chloro-4-nitrophenyl) O,O-dimethyl phosphorothioate]
Monuron trichloroacetate [3 -(4-chlorophenyl)- 1 , 1 -dimethylurea trichloroacetate]
CAS
number
75-71-8
2104-96-3
17601-49-9
555-37-3
299-86-5
94-81-5
6062-26-6
122-88-3
1982-47-4
1194-65-6
709-98-8
97-17-6
50-29-3
117-80-6
1076-46-6
1954-81-0
136-78-7
99-30-9
1929-86-8
1432-14-0
28473-03-2
2463-84-5
140-41-0
Support
withdrawn
Yes
Yes
Yes
Yes
Yes
No
No
No
Yes
No
No
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
No
Yes
Yes
Testing
required
~
~
~
~
~
Yes
No
Yes
~
Yes
No
~
-
~
-
~
-
Yes
~
~
No
~
~
oo
oo
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 8-29. Status of first pesticide data call-in: pesticides suspected of having the potential to become contaminated
with dioxins if synthesized under conditions favoring dioxin formation (continued)
Shaughnessey
code
35505
35506
35901
53501
55001
55005
55201
57501
58102
58301
58802
59401
61501
62201
62202
62203
62204
62206
62207
62208
62209
62210
Pesticide [active ingredient]
Diuron [3 -(3 ,4-dichlorophenyl)- 1 , 1 -dimethylurea]
Linuron [3 -(3 ,4-dichlorophenyl)- 1-methoxy- 1 -methylurea]
Metobromuron [3 -(p-bromopheny 1)- 1 -methoxy- 1 -methylurea]
Methyl parathion [O,O-Dimethyl O-p-nitrophenyl phosphorothioate]
Dichlorophene [Sodium 2,2'-methylenebis(4-chlorophenate)]
Dichlorophene, sodium salt [Sodium 2,2'-methylenebis(4-chlorophenate)]
1 ,2,4,5-Tetrachloro-3 -nitrobenzene
Ethyl parathion [O,O-diethyl O-p-nitrophenyl phosphorothioate]
Carbophenothion [S-(((p-chlorophenyl)thio)methyl) O,O-diethyl phosphorodithioate]
Ronnel [O,O-dimethyl O-(2,4,5-trichlorophenyl) phosphorothioate]
Mitin FF [Sodium 5-chloro-2-(4-chloro-2-(3-(3,4-dichlorophenyl)ureido)phenoxy)
benzenesulfonate]
Orthodichlorobenzene
Paradichlorobenzene
Chlorophene [2-Benzyl-4-chlorophenol]
Potassium 2-benzyl-4-chlorophenate
Sodium 2-benzyl-4-chlorophenate
2-Chlorophenol
2-Chloro-4-phenylphenol
Potassium 2-chloro-4-phenylphenate
4-Chloro-2-phenylphenol
4-Chloro-2-phenylphenol, potassium salt
6-Chloro-2-phenylphenol
CAS
number
330-54-1
330-55-2
3060-89-7
298-00-0
97-23-4
10254-48-5
117-18-0
56-38-2
786-19-6
229-84-3
3567-25-7
95-50-1
106-46-7
120-32-1
35471-49-9
3184-65-4
95-57-8
92-04-6
18128-16-0
Not
available
53404-21-0
85-97-2
Support
withdrawn
No
No
Yes
No
Yes
Yes
Yes
No
Yes
Yes
No
Yes
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Testing
required
No
No
~
No
~
~
~
No
~
~
No
~
No
No
In review
In review
~
~
~
~
~
~
oo
oo
oo
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 8-29. Status of first pesticide data call-in: pesticides suspected of having the potential to become contaminated
with dioxins if synthesized under conditions favoring dioxin formation (continued)
Shaughnessey
code
62211
62212
62213
62214
62215
64202
64208
64209
64214
64218
67707
69105
69144
77401
77406
78780
79202
79301
80403
Pesticide [active ingredient]
6-Chloro-2-phenylphenol, potassium salt
4-Chloro-2-phenylphenol, sodium salt
6-Chloro-2-phenylphenol, sodium salt
4 and 6-Chloro-2-phenylphenol, diethanolamine salt
2-Chloro-4-phenylphenol, sodium salt
4-Chloro-2-cyclopentylphenol
Fentichlor [2,2'-Thiobis(4-chloro-6-methylphenol)]
Fentichlor [2,2'-Thiobis(4-chlorophenol)]
4-Chloro-2-cyclopentylphenol, potassium salt of
4-Chloro-2-cyclopentylphenol, sodium salt
Chlorophacinone
ADBAC [Alkyl* dimethyl benzyl ammonium chloride *(50% C14, 40% C12, 10%
C16)]
ADBAC [Alkyl* dimethyl 3,4-dichlorobenzyl ammonium chloride *(61% C12, 23%
C14, 11%C16, 5% CIS)]
Niclosamide [2-Aminoethanol salt of 2',5-dichloro-4'-nitrosalicylanilide]
5-Chlorosalicylanilide
2-Methyl-4-isothiazolin-3 -one
Tetradifon [4-chlorophenyl 2,4,5-trichlorophenyl sulfone]
Chloranil [tetrachloro-p-benzoquinone]
6-Chlorothymol
CAS
number
18128-17-1
10605-10-4
10605-11-5
53537-63-6
31366-97-9
13347-42-7
4418-66-0
97-24-5
35471-38-6
53404-20-9
3691-35-8
68424-85-1
Not
available
1420-04-8
4638-48-6
Not
available
116-29-0
118-75-2
89-68-9
Support
withdrawn
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Testing
required
~
~
~
~
~
~
~
~
~
-
No
No
No
No
~
~
-
~
~
oo
oo
VO
o
o
2
o
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 8-29. Status of first pesticide data call-in: pesticides suspected of having the potential to become contaminated
with dioxins if synthesized under conditions favoring dioxin formation (continued)
Shaughnessey
code
80811
81901
82602
84101
84901
86801
97003
100601
101001
101101
104301
106001
108201
109001
109301
109302
109801
109901
Pesticide [active ingredient]
Anilazine [2,4-Dichloro-6-(o-chloroanilino)-s-triazine]
Chlorothalonil [tetrachloroisophthalonitrile]
Sodium 2,3 ,6-Trichlorophenylacetate
Chlorfenvinphos
O-(2-Chloro-l-(2,5-dichlorophenyl)vinyl) O,O-diethyl phosphorothioate
PCMX [4-Chloro-3,5-xylenol]
Piperalin [3-(2-Methylpiperidino)propyl 3,4-dichlorobenzoate]
Fenamiphos
p-Chlorophenyl diiodomethyl sulfone
Metribuzin
Bifenox [methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate]
Methazole [2-(3 ,4-dichlorophenyl)-4-methyl- 1 ,2,4-oxadiazolidine-3 ,5-dione]
Diflubenzuron [N-(((4-chlorophenyl)amino)carbonyl)-2,6-difluorobenzamide]
Oxadiazon [2-tert-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)- delta 2 -1,3,4-
oxadiazoline-5 -one]
Fenvalerate
Fluvalinate [N-2-Chloro-4-trifluoromethyl)phenyl-DL-valine (+-)-cyano(3 -phenoxy-
phenyl)methyl ester]
Iprodione [3-(3 ,5-Dichlorophenyl)-N-( 1 -methylethyl)-2,4-dioxo- 1 -
imidazolidinecarboxamide (9CA)]
Triadimefon
[ 1 -(4-Chlorophenoxy)-3 ,3-dimethyl- 1 -( 1H- 1 ,2,4-triazol-l -yl)-2-butanone]
CAS
number
101-05-3
1897-45-6
2439-00-1
470-90-6
1757-18-2
88-04-0
3478-94-2
Not
available
20018-12-6
21087-64-9
42576-02-3
20354-26-1
35367-38-5
19666-30-9
51630-58-1
69409-94-5
36734-19-7
43121-43-3
Support
withdrawn
Yes
No
Yes
Yes
Yes
No
No
No
Yes
No
Yes
Yes
No
No
No
No
No
No
Testing
required
~
Yes
~
~
~
No
No
No
~
No
-
~
Yes
Yes
In review
No
No
No
oo
VO
o
O
O
2
O
H
O
HH
H
W
O
-------
o
OJ
o
4^
o
Table 8-29. Status of first pesticide data call-in: pesticides suspected of having the potential to become contaminated
with dioxins if synthesized under conditions favoring dioxin formation (continued)
Shaughnessey
code
110902
111401
111601
111901
112802
113201
119001
123901
125601
128838
206600
Pesticide [active ingredient]
Diclofop - methyl [methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propanoate]
Profenofos [O-(4-Bromo-2-chlorophenyl)-O-ethyl S-propyl phosphorothioate]
Oxyfluorfen [2-chloro-l-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene]
Imazalil [l-(2-(2,4-Dichlorophenyl)-2-(2-propenyloxy)ethyl)-lH-imidazole]
Bromothalin [N-Methyl-2,4-dinitro-n-(2,4,6-tribromophenyl)-6-
(trifuloromethyl)benzenamine]
Vinclozolin [3-(3,5-Dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (9CA)]
Fenridazon [Potassium l-(p-chlorophenyl)-l,4-dihydro-6-methyl-4-oxo- pyridazine-
3-carboxylate]
Tridiphane [2-(3,5-Dichlorophenyl)-2-(2,2,2-trichloroethyl) oxirane]
Paclobutrazol
Linalool
Fenarimol [a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidinemethanol]
CAS
number
51338-27-3
41198-08-7
42874-03-3
35554-44-0
63333-35-7
50471-44-8
83588-43-6
58138-08-2
76738-62-0
78-70-6
60168-88-9
Support
withdrawn
No
No
No
No
No
No
No
No
No
No
No
Testing
required
Yes
In review
In review
No
No
No
In review
No
No
In review
No
oo
O
O
2
O
H
O
HH
H
W
- = No information given
O
-------
o
OJ
o
j^.
o
Table 8-30. Status of second pesticide data call-in: pesticides suspected of being contaminated with dioxins
Shaughnessey
code
29801
29802
29803
30001
30002
30003
30004
30005
30010
30011
30013
30014
30016
30017
30019
30020
30021
30023
30024
30025
30028
30029
30030
30033
Pesticide [active ingredient]
Dicamba [3,6-dichloro-o-anisic acid]
Dicamba dimethylamine [3,6-dichloro-o-anisic acid]
Diethanolamine dicamba [3, 6-dichloro-2 -anisic acid]
2,4-Dichlorophenoxyacetic acid
Lithium 2,4-dichlorophenoxyacetate
Potassium 2,4-dichlorophenoxyacetate
Sodium 2,4-dichlorophenoxyacetate
Ammonium 2,4-dichlorophenoxyacetate
Alkanol* amine 2,4-dichlorophenoxyacetate *(salts of the ethanol and
ispropanol series)
Alkyl* amine 2,4-dichlorophenoxyacetate *(100% C12)
Alkyl* amine 2,4-dichlorophenoxyacetate *(100% C14)
Alkyl* amine 2,4-dichlorophenoxyacetate *(as in fatty acids of tall oil)
Diethanolamine 2,4-dichlorophenoxyacetate
Diethylamine 2,4-dichlorophenoxyacetate
Dimethylamine 2,4-dichlorophenoxyacetate
N,N-Dimethyloleylamine 2,4-dichlorophenoxyacetate
Ethanolamine 2,4-dichlorophenoxyacetate
Heptylamine 2,4-dichlorophenoxyacetate
Isopropanolamine 2,4-dichlorophenoxyacetate
Isopropylamine 2,4-dichlorophenoxyacetate
Morpholine 2,4-dichlorophenoxyacetate
N-Oleyl-l,3-propylenediamine 2,4-dichlorophenoxyacetate
Octylamine 2,4-dichlorophenoxyacetate
Triethanolamine 2,4-dichlorophenoxyacetate
CAS
number
1918-00-9
2300-66-5
25059-78-3
94-75-7
3766-27-6
14214-89-2
2702-72-9
2307-55-3
Not available
2212-54-6
28685-18-9
Not available
5742-19-8
20940-37-8
2008-39-1
53535-36-7
3599.58-4
37102-63-9
6365-72-6
5742-17-6
6365-73-7
2212-59-1
2212-53-5
2569-01-9
Support
withdrawn
No
No
Yes
No
No
Yes
No
Yes
Yes
Yes
Yes
Yes
No
Yes
No
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Testing
required
Yes
Yes
-
Yes
No
~
No
~
~
~
~
~
No
~
No
~
~
~
~
No
~
~
~
~
oo
VO
to
o
o
2
O
H
O
HH
H
W
O
-------
o
OJ
o
j^.
o
Table 8-30. Status of second pesticide data call-in: pesticides suspected of being contaminated with dioxins
(continued)
Shaughnessey
code
30034
30035
30039
30052
30053
30055
30056
30062
30063
30064
30065
30066
30072
30801
30804
30819
30853
30856
30863
31401
31419
31453
31463
31501
Pesticide [active ingredient]
Triethylamine 2,4-dichlorophenoxyacetate
Triisopropanolamine 2,4-dichlorophenoxyacetate
N,N-Dimethyl oleyl-linoleyl amine 2,4-dichlorophenoxyacetate
Butoxyethoxypropyl 2,4-dichlorophenoxyacetate
Butoxy ethyl 2,4-dichlorophenoxyacetate
Butoxypropyl 2,4-dichlorophenoxyacetate
Butyl 2,4-dichlorophenoxyacetate
Isobutyl 2,4-dichlorophenoxyacetate
Isooctyl(2-ethylhexyl) 2,4-dichlorophenoxyacetate
Isooctyl(2-ethyl-4-methylpentyl) 2,4-dichlorophenoxyacetate
Isooctyl(2-octyl) 2,4-dichlorophenoxyacetate
Isopropyl 2,4-dichlorophenoxyacetate
Propylene glycol butyl ether 2,4-dichlorophenoxyacetate
4-(2,4-Dichlorophenoxy)butyric acid
Sodium 4-(2,4-dichlorophenoxy)butyrate
Dimethylamine 4-(2,4-dichlorophenoxy)butyrate
Butoxy ethanol4-(2,4-dichlorophenoxy)butyrate
Butyl 4-(2,4-dichlorophenoxy)buty rate
Isooctyl4-(2,4-dichlorophenoxy)butyrate
2-(2,4-Dichlorophenoxy)propionicacid
Dimethylamine 2-(2,4-dichlorophenoxy)propionate
Butoxy ethyl 2-(2,4-dichlorophenoxy)propionate
Isooctyl2-(2,4-dichlorophenoxy)propionate
MCPP acid [2-(2-Methyl-4-chlorophenoxy)propionic acid]
CAS
number
2646-78-8
32341-80-3
55256-32-1
1928-57-0
1929-73-3
1928-45-6
94-80-4
1713-15-1
1928-43-4
25168-26-7
1917-97-1
94-11-1
1320-18-9
94-82-6
10433-59-7
2758-42-1
32357-46-3
6753-24-8
1320-15-6
120-36-5
53404-32-3
53404-31-2
28631-35-8
7085-19-0
Support
withdrawn
No
No
Yes
Yes
No
Yes
Yes
Yes
No
Yes
Yes
No
Yes
No
No
No
Yes
Yes
Yes
No
No
No
No
No
Testing
required
No
No
~
~
No
~
~
~
Yes
~
~
No
-
Yes
No
No
~
~
~
Yes
No
No
No
Yes
oo
I
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2
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Table 8-30. Status of second pesticide data call-in: pesticides suspected of being contaminated with dioxins
(continued)
Shaughnessey
code
31519
35301
44901
44902
44904
54901
63004
63005
63006
63007
64203
64212
64219
64220
64501
78701
79401
82501
83701
104101
Pesticide [active ingredient]
MCPP, DMA [Dimethylamine 2-(2-methyl-4-chlorophenoxy)propionate]
Bromoxynil [3,5-dibromo-4-hydroxybenzonitrile]
Hexachlorophene [2,2'-Methylenebis(3,4,6-trichlorophenol)]
Hexachlorophene, Na salt [Monosodium
2,2'-methylenebis(3,4,6-trichlorophenate)]
Hexachlorophene, K salt [Potassium
2,2'-methylenebis(3,4,6-trichlorophenate)]
Irgasan [5-Chloro-2-(2,4-dichlorophenoxy)phenol]
Tetrachlorophenols
Tetrachlorophenols, sodium salt
Tetrachlorophenols, alkyl* amine salt*(as in fatty acids of coconut oil)
Tetrachlorophenols, potassium salt
Bithionolate sodium [Disodium 2,2'-thiobis(4,6-dichlorophenate)]
Phenachlor [2,4,6-Trichlorophenol]
Potassium 2,4,6-trichlorophenate
2,4,6-Trichlorophenol, sodium salt
Phenothiazine
Dacthal-DCPA [Dimethyl tetrachloroterephthalate]
Endosulfan [hexachlorohexahydromethano-2,4,3 -benzodioxathiepin-3 -oxide]
Silvex [2-(2,4,5-trichlorophenoxy)propionic acid]
Tetrachlorvinphos [2-Chloro-l-(2,4,5-trichlorophenyl)vinyl dimethyl
phosphate]
Edolan [Sodium l,4',5'-trichloro-2'-(2,4,5-trichlorophenoxy)
methanesulfonanilide]
CAS
number
32351-70-5
1689-84-5
70-30-4
5736-15-2
67923-62-0
3380-34-5
25167-83-3
25567-55-9
Not available
53535-27-6
6385-58-6
88-06-2
2591-21-1
3784-03-0
92-84-2
1861-32-1
115-29-7
93-72-1
961-11-5
69462-14-2
Support
withdrawn
No
No
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
Yes
No
Yes
Testing
required
No
Yes
~
~
~
Yes
~
~
~
~
~
~
~
~
~
Yes
No
-
Yes
~
oo
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Table 8-31. Summary of analytical data submitted to EPA in response to pesticide data call-in(s)
Shaughnessey
code
019201
019401
027401
029801
029802
030001
030063
030801
031301
031401
031501
035301
054901
078701
081901
083701
108201
109001
110902
Pesticide
Common name
MCPB, 4-butyric acid
4-CPA
Dichlobenil
Dicamba
Dicamba, dimethylamine
2,4-D
2,4-D, 2EH
2,4-DB
DCNA
2,4-DP
Mecoprop (MCPP)
Bromoxynil
Irgasan
Dacthal (DCPA)
Chlorothalonil
Tetrachlorvinphos
Diflubenzuron
Oxadiazon
Dichlofop-methyl
Chemical name
4-(2-methyl-4-chlorophenoxy)butyric acid
4-Chlorophenoxyacetic acid
2,6-Dichlorobenzonitrile
3,6-Dichloro-o-anisic acid
3,6-Dichloro-o-anisic acid, dimethylamine salt
2,4-Dichlorophenoxy acetic acid
Isooctyl(2-ethylhexyl)2,4-dichlorophenoxy acetate
4-(2,4-Dichlorophenoxy)butyric acid
2,6-Dichloro-4-nitroaniline
2-(2,4-Dichlorophenoxy)propionic acid
2-(2-methyl-4-chlorophenoxy)propionic acid
3,5-Dibromo-4-hydroxybenzonitrile
5-Chloro-2-(2,4-dichlorophenoxy)phenol
Dimethyl tetrachloroterephthalate
Tetrachloroisophthalonitrile
2-Chloro-l-(2,4,5-trichlorophenyl)vinyl dimethyl phosphate
N-(((4-chlorophenyl)amino)carbonyl)-2,6-difluorobenzamide
2-Tert-butyl-4(2,4-dichloro-5-isopropoxyphenyl)-delta2-l,3,4-oxadiazoline-5-one
Methyl-2-(4-(2,4-dichlorophenoxy)phenoxy)propanoate
Number of
positive
submissions" to
date
0
0
0
0
0
2
1
0
Pending
0
0
0
0
Pending
Pending
0
0
Pending
0
oo
OD
o
o
2
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H
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""'Positive" is defined as the detection of any congener at a concentration equal to or exceeding the limits of quantitation listed in Table 8-23.
Sources: U.S. EPA (1995a); personal communication from S. Funk, U.S. EPA, to D. Cleverly, U.S. EPA, March 27, 1996.
-------
Table 8-32. Summary of results for CDDs and CDFs in technical 2,4-D and
2,4-D ester herbicides
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
EPA
LOQa
(Hi/kg)
0.1
0.5
2.5
2.5
2.5
100
-
1
5
5
25
25
25
25
1,000
1,000
-
Total
no. of
technicals
8
8
8
8
8
8
-
8
8
7
8
8
8
8
8
8
-
Number of
technicals
greater than
LOQ
2
3
0
0
0
0
-
0
0
0
0
0
0
0
0
0
-
Observed
maximum
cone.
(Hi/kg)
0.13
2.6
0.81
0.77
0.68
1.5
-
0.27
0.62
0.73
1.6
1.2
1.4
1.1
8.3
1.2
-
TOTAL0
I-TEQDF
TEQnF-WHOQS
Average
conc.b
(Hi/kg)
0.06
0.78
0.31
0.39
0.24
0.21
-
0.07
0.38
0.07
0.36
0.11
0.16
0.14
2.17
0.18
-
5.6
0.7
1.1
aLOQ required by EPA in the data call-in.
bAverage of the mean results for multiple analyses of four technical 2,4-D and/or 2,4-D ester products for which
detectable CDD/CDF congener concentrations less than the LOQs were quantified; nondetect values were
assumed to be zero.
Total equals the sum of the individual congener averages.
LOQ = Limit of quantitation
~ = Analyses not performed
Source: U.S. EPA Office of Pesticide Program file.
03/04/05
8-96
DRAFT-DO NOT CITE OR QUOTE
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Table 8-33. CDD/CDF concentrations in samples of 2,4-D and pesticide formulations containing 2,4-D (|j,g/kg)
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
l,2,3,7,8-/l,2,3,4,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-/1,2,3,4,7,9
-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
(nondetect = 0)
Total 2,3,7,8-CDF
(nondetect = 0)
Total I-TEQop
(nondetect = 0)b
Total TEQoF-WHO,,,
(nondetect = 0)b
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
Acbar
Super
(Gaza
City")
ND(O.l)
0.1
ND(O.l)
ND(O.l)
ND(O.l)
0.1
0.1
0.3
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
ND(O.l)
0.1
ND(O.l)
0.2
0.3
0.6
0.082
0.134
—
-
-
-
-
—
—
-
-
-
__
Amco
Super
(Gaza
City")
ND(O.l)
ND(O.l)
ND(O.l)
0.2
ND(O.l)
1.2
2.6
ND(O.l)
0.2
ND(O.l)
0.1
ND(O.l)
ND(O.l)
ND(O.l)
0.8
ND(O.l)
3.8
4
4.9
0.066
0.061
—
-
-
-
-
—
—
-
-
-
__
(Bethlehem)
ND(O.l)
1.2
ND(O.l)
0.6
0.4
0.3
0.1
ND(O.l)
0.7
0.1
0.4
0.1
ND(O.l)
0.1
0.1
ND(O.l)
0.4
2.6
1.9
0.85
1.449
—
-
-
-
-
—
—
-
-
-
__
Chimprom
(Russia)
ND (0.02)
0.03
0.02
0.05
ND (0.02)
0.23
0.85
ND(O.l)
1.2
0.06
0.08
0.11
ND (0.02)
0.05
0.24
0.02
0.46
1.18
2 22
0.142
0.156
—
-
-
-
-
-
-
-
-
-
__
Dragon
Lawn
Weed
Killer
ND (0.001)
0.0014
ND (0.001)
0.0024
0.001
0.0017
0.0063
0.0036
0.001
0.0011
0.0013
ND (0.001)
ND (0.001)
0.0011
0.0016
ND (0.001)
0.0039
0.0128
0.0136
0.0023
0.003
—
-
-
-
-
-
-
-
-
-
__
KGRO
(U.S.)
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
0.0144
0.1628
0.0009
—
-
-
-
-
-
-
-
-
-
__
Pro Care
Premium
(U.S.)
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
--
0.0143
0.4253
0.0012
—
-
-
-
-
-
-
-
-
-
__
Ortho
Weed-B-
Gone
(U.S.)
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
0.0091
0.1095
0.0014
—
-
-
-
-
-
-
-
-
-
__
Sigma Co.
(U.S.)
—
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
0.127
3.0507
0.0013
—
-
-
-
-
-
-
-
-
-
__
American
Brand
Chemical
Co. (U.S.)
—
-
-
-
-
-
--
—
-
-
-
-
-
-
-
-
--
0.0278
0.0822
0.0019
—
-
-
-
-
—
—
-
-
-
__
Ishihara
Sangyo
Kaisha,
Ltd.
(Japan)
0.0021
0.011
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND(O.Ol)
ND (0.002)
0.0038
ND (0.002)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND(O.OIO)
-
-
0.0078
0.013
0.041
0.018
0.008
ND (0.005)
ND(O.Ol)
2.7
0.89
0.019
0.006
ND(O.Ol)
3.7
Nissan
Chemical
Industries,
Ltd.
(Japan)
ND (0.002)
ND (0.002)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND(O.Ol)
ND (0.002)
ND (0.002)
ND (0.002)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND (0.005)
ND(O.Ol)
-
-
ND
ND
ND (0.002)
ND (0.002)
ND (0.005)
ND (0.005)
ND(O.Ol)
0.0093
ND (0.002)
ND (0.005)
ND (0.005)
ND(O.Ol)
0.0093
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'"2,4-D manufactured in Europe and packaged in Palestine
bCalculated assuming nondetect values are zero.
ND = not detected (value in parenthesis is the detection limit)
-------
S Table 8-33. CDD/CDF concentrations in samples of 2,4-D and pesticide formulations containing 2,4-D (|j,g/kg)
2 (continued)
o
~ = No information given
Sources: Schecter et al. (1997); Maunaga et al. (2001).
oo
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2
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Table 8-34. Mean CDD/CDF measurements in effluents from nine U.S.
publicly owned treatment works (POTWs)
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 TEQDF-WHO98
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
No. of
detections/
samples
0/30
0/30
0/30
0/30
0/30
3/30
13/30
1/27
1/30
1/30
1/30
1/30
1/30
1/30
2/30
0/30
1/30
—
4/27
0/27
1/30
3/30
13/30
2/30
1/30
1/30
2/30
1/30
Range of
DLs
(Pg/L)
0.31-8.8
0.45-15
0.43-9.8
0.81-10
0.42-9.7
0.75-18
6.2-57
0.74-4.4
0.64-9.4
0.61-14
0.25-6.8
0.23-6.8
0.57-10
0.25-7.9
0.36-6.9
0.19-11
0.86-28
—
1.2-8.8
0.62-200
0.84-11
0.75-18
6.2-57
0.39-6.8
0.64-25
0.93-17
0.36-19
0.86-28
Total CDD/CDF
Range of detected
concentrations
(POTW mean basis)
(pg/L)
Minimum
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Maximum
ND
ND
ND
ND
ND
5
99.75
1.3
2
2.8
2.4
1.5
2
ND
4.6
ND
3.2
99.75
16.6
2.42
2.33
9.7
ND
1.7
8.4
99.75
25
20
13
4.6
3.2
99.75
Overall mean
concentrations3
Nondetect
set to 0
(Pg/L)
0
0
0
0
0
1.06
29.51
0.14
0.22
0.31
0.27
0.17
0.22
0
0.68
0
0.36
30.57
2.37
0.29
0.27
1.23
0
0.19
1.83
29.51
6.61
2.22
1.44
0.68
0.36
42
Nondetect
set to 1A DL
(Pg/L)
0.98
1.32
1.38
1.42
1.31
3.61
37.95
0.98
1.58
1.68
1.22
0.97
1.72
0.93
1.83
1.18
3.4
47.98
15.49
3.66
4.28
2.61
6.27
1.93
4.77
37.95
7.7
4.72
3.43
2.41
3.4
71.96
aThe overall means are the means of the individual POTW mean concentrations rather than the means of the
individual sample concentrations.
DL = Detection limit
ND = Not detected
~ = No information given
Source: CRWQCB (1996).
03/04/05
8-99
DRAFT-DO NOT CITE OR QUOTE
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Table 8-35. Effluent concentrations of CDDs/CDFs from publicly owned treatment works in Mississippi (pg/L)
Facility
Waynesboro
Meridian
Pascagoula
W. Biloxi
Gulfport
Laurel
Brookhaven
Natchez
Picayune
Picayune3
Waveland
Corinth
New Augusta
Beaumont
Leaksville
McLain
Hattiesburg S
Hattiesburg N
Average (nondetect = 0)
2,3,7,8-
TCDD
ND(0.17)
0.18
ND(0.13)
0.18
0.16
ND(0.18)
ND(0.18)
ND(0.16)
ND (0.22)
ND(0.13)
ND(0.18)
ND(0.15)
ND(O.l)
ND(O.l)
ND(0.12)
ND (0.06)
ND(0.16)
ND(0.19)
0.17
2,3,7,8-
TCDF
0.18
0.12
0.15
0.24
0.24
0.15
0.54
0.41
0.56
0.54
17
0.17
1.3
0.14
0.72
ND (0.05)
ND (0.24)
0.18
1.42
1,2,3,7,8-
PeCDD
ND (0.2)
ND(0.16)
ND(0.15)
ND(0.15)
ND(0.15)
ND (0.23)
0.45
0.6
ND (0.27)
ND(0.12)
0.22
ND(0.16)
0.28
ND(0.13)
0.25
ND(O.IO)
ND (0.24)
ND (0.26)
0.36
2,3,4,7,8-
PeCDF
ND(O.l)
ND (0.09)
0.11
0.082
0.094
ND(0.12)
0.16
0.34
ND(0.14)
ND (0.07)
0.66
ND (0.09)
0.085
0.088
0.15
ND (0.06)
ND(O.ll)
ND(0.13)
0.2
Total
HxCDD
ND
1.3
ND
ND
ND
ND
0.85
2.5
6.5
6
ND
0.77
21
0.64
8.9
2.5
1.2
0.96
4.43
Total
HpCDD
3.5
7.6
0.82
0.9
2.3
2.9
3.2
2.4
38
30
3
2.7
120
2.4
46
14
4.5
9.1
16.3
OCDD
13
58
3.6
4
9.9
38
28
9.1
120
53
14
18
2500
11
780
200
59
73
221.76
OCDF
1.8
1.8
0.46
ND (0.34)
0.78
ND (0.48)
1.7
1.8
2
106
0.9
1.1
0.66
3.2
0.77
2.9
8.99
Total
I-TEQ
0.316
0.445
0.264
0.378
0.371
0.334
0.796
1.03
0.715
0.397
2.4
0.276
3.84
0.274
1.6
0.377
0.32
0.457
0.81
oo
o
o
O
O
2
O
H
O
O
V
O
c
o
aBlind double.
ND = Not detected (value in parenthesis is the detection limit)
Source: Rappe et al. (1998).
-------
Table 8-36. CDD/CDF concentrations measured in EPA's 1998/1999
National Sewage Sludge Survey
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
Percent
detected
16
18
25
49
39
98
100
65
22
26
43
35
16
27
71
26
80
Total I-TEQDF
Total 2,3,7,8-CDD/CDF
Maximum
concentration
detected
(ng/kg)
116
736
737
737
737
52,500
905,000
337
736
736
1,500
737
1,260
737
7,100
842
69,500
1,820
—
Median concentration
(ng/kg)
Nondetect
set to
detection
limit
6.86
9.84
22.5
27.3
28
335
3,320
17
9.6
10.4
28
18
18
18
57
23
110
50.4
—
Nondetect
set to
zero
0
0
0
0
0
335
3,320
3.9
0
0
0
0
0
0
36
0
80
11.2
—
Mean concentration
(ng/kg)
Nondetect
set to
detection
limit
..
~
—
~
—
~
-
~
—
~
—
~
—
~
-
~
86a
—
Nondetect
set to
zero
..
~
—
~
—
~
-
~
—
~
—
~
—
~
-
~
50a
—
aValues presented by Rubin and White (1992) for 175 rather than 174 publicly owned treatment works.
~ = No information given
Source: U.S. EPA (1996a); for publicly owned treatment works with multiple samples, the pollutant
concentrations were averaged before the summary statistics presented in the table were calculated.
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o
OJ
o
4^
o
Table 8-37. CDD/CDF concentrations measured in 99 sludges collected from U.S. publicly owned treatment
works (POTWs) during 1994
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
Percent
detected
40
23
34
87
64
98
99
76
21
42
48
17
4
35
64
31
93
Average I-TEQDF (facility basis)b
Total 2,3,7,8-CDD/CDF
Maximum
concentration
detected
(ng/kg)
12.3
37.5
45.6
130
88.8
5,380
65,500
156
60.3
155
170
200
115
356
1,460
213
11,200
246
73,520
Average TEQDF-WHO98 (facility basis)b
Median concentration
(ng/kg)
Nondetect
set to
detection
limit
1.95
8.23
5.25
25.6
12.3
642
6,630
7.53
7.91
9.7
11.5
14
7.53
9.85
91.7
11.7
286
49.6
7,916
44.6
Nondetect
set to
zero
0
0
0
24.7
9.48
642
6,630
6.28
0
0
0
0
0
0
31.8
0
281
33.4
7,881
25.5
Mean concentration (ng/kg)
Nondetect
set to
detection limit3
2.72 (2.4)
10.9 (7.8)
11.1(8.13)
33.8 (27.6)
20.2 (17.7)
981 (977)
11,890(12,540)
12.8(19.6)
10.7(11.3)
15.7(19.8)
20.4 (25.3)
30.4 (53.6)
11.1(13.6)
21.8 (40.4)
223 (271)
27.1 (34.8)
786 (1,503)
64.5(50.1)
14,110(14,390)
57.2 (44.4)
Nondetect
set to
zero3
1.71 (2.86)
3.34 (7.43)
6.03 (10.2)
32.2 (28.8)
17(19.8)
981 (977)
11,890(12,540)
11.1(20.2)
3.53 (9.36)
10.5 (21.6)
14 (25.9)
5.13(21.9)
1.56(11.7)
13.6(41)
97.5 (207)
15 (33.4)
775 (1,506)
47.7 (44.7)
13,880 (14,200)
36.3 (38.6)
oo
o
to
aValue in parenthesis is the standard deviation.
bFor POTWs with multiple samples, the sample TEQ concentrations were averaged to POTW averages before calculation of the total TEQ mean and median
values presented in the table.
A total of 74 POTW average concentrations were used in the calculations. In addition, the following sample ID numbers were not included in the averaging
because, according to Green et al. (1995), it was not possible to determine whether they were duplicate or multiple samples from other POTWs: 87, 88, 89, 90,
91, 97, 98, and 106.
Source: Green et al. (1995); Cramer et al. (1995).
-------
o
OJ
o
4^
o
Table 8-38. Sewage sludge concentrations from publicly owned treatment works in Mississippi (ng/kg dry
matter)
Facility
Waynesboro
Meridian
Pascagoula
W. Biloxi
Gulfport
Laurel
Brookhaven
Natchez
Picayune
Picayune3
Waveland
Corinth
New Augusta
Beaumont
Leaksville
McLain
Hattiesburg S
Hattiesburg N
Average
(nondetect = 0)
2,3,7,8-
TCDD
2.1
ND (0.06)
2
0.84
1.9
0.17
2
ND (0.58)
5.3
4.1
1.6
0.3
ND(0.13)
0.17
ND (0.051)
0.076
1
ND (0.035)
1.2
2,3,7,8-
TCDF
2.9
2.1
3.6
2.4
9.1
0.3
2.5
8.3
69
66
2.6
1.8
0.17
0.67
0.14
0.17
1.1
1.7
9.7
1,2,3,7,8-
PeCDD
3.5
6.4
5.3
3.2
9.5
0.37
11
8.4
74
60
5.1
0.97
0.15
0.78
0.32
0.11
9.1
4
11
2,3,4,7,8-
PeCDF
1.4
2.8
3.5
1.3
3.4
0.25
2.5
ND(1.5)
24
17
1.9
0.93
0.094
0.37
0.11
0.031
2.2
2
3.4
Total
HxCDD
85
10
170
78
200
22
130
270
17,000
16,000
130
42
21
59
16
39
170
310
1,900
Total
HpCDD
920
100
970
280
1,100
160
1,400
1,100
250,000
210,000
580
230
140
470
92
140
1,3000
3,600
26,000
OCDD
7,400
7,400
4,300
1,800
7,700
2,700
9,300
6,800
480,000
420,000
3,500
3,300
1,400
1,900
560
2,600
4,400
27,000
55,000
OCDF
410
410
170
70
310
21
230
270
16,000
17,000
150
36
8.8
42
26
0.74
180
980
2,000
Total
I-TEQ
23.7
27.6
26.4
13.7
30.9
4.83
36.7
37.7
1,270
1,240
31.7
7.4
2.67
6.18
2.26
3.55
33
70.4
116 ±323
oo
o
oo
o
o
2
o
H
O
O
V
O
c
o
"Blind double.
ND = Not detected (value in parenthesis is the detection limit)
Source: Rappe et al. (1998).
-------
Table 8-39. CDD/CDF concentrations measured in 1999 from a publicly
owned treatment works facility in Ohio
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 TEQnF-WHOQ8
Median Concentration (ng/kg)
Nondetect set to
zero
ND
ND
2.67
21.33
30.33
298
2,963
26.67
4.33
10
21
5.33
ND
9
171
ND
364.67
21.87
Nondetect set to
1A detection limit
0.0018
0.0082
2.67
21.33
30.33
298
2,963
26.67
4.34
10
21
5.33
0.0033
9
171
0.01
364.67
21.88
Source: U.S. EPA (2000).
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Table 8-40. CDD/CDF concentrations measured in the EPA 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 TEQDF-WHO98
Mean concentration (ng/kg)
Nondetect set to
zero
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
21.7
Nondetect set to
1A detection limit
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
15.5
Source: U.S. EPA (2002a).
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Table 8-41. Quantity of sewage sludge disposed of annually for the reference
year 1987 by primary, secondary, and advanced treatment publicly owned
treatment works and potential dioxin TEQ releases
Use/disposal practice
Land application
Distribution and marketing
Surface disposal site/other
Sewage sludge landfill
Co-disposal landfills0
Sludge incinerators and
co-incinerators'1
Ocean disposal
TOTAL
Volume
disposed of
(thousands of
dry metric
tons/yr)
1,714
71
396
157
1,819
865
(336)f
5,357
Percent of
total volume
32b
1.3
7.4
2.9
33.9
16.1
(6.3)f
100
Potential dioxin release"
(gofTEQ/yr)
I-TEQnF
84
3.5
19.4
7.7
89.1
e
f
204
TEQDF-
WHO98
62.2
2.6
14.4
5.7
66
e
f
151
Totential dioxin TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume
generated (column 2) by the average of the mean I-TEQDF concentrations in sludge reported by Rubin and White
(1992) (i.e., 50 ng/kg dry weight) and Green et al. (1995) and Cramer et al. (1995) (47.7 ng/kg). The
calculations of TEQDF-WHO98 used the mean concentration of 36.3 ng TEQDF-WHO98/kg for the results reported
by Green et al. (1995) and Cramer et al. (1995).
Includes 21.9% applied to agricultural land, 2.8% applied as compost, 0.6% applied to forestry land, 3.1%
applied to "public contact" land, 1.2% applied to reclamation sites, and 2.4% applied in undefined settings.
GLandfills used for disposal of sewage sludge and solid waste residuals.
dCo-incinerators treat sewage sludge in combination with other combustible waste materials.
eSee Section 3.5 for estimates of CDD/CDF releases to air from sewage sludge incinerators.
fThe Ocean Dumping Ban Act of 1988 generally prohibited the dumping of sewage sludge into the ocean after
December 31, 1991. Ocean dumping of sewage sludge ended in June 1992 (Federal Register, 1993b). The
current method of disposal of the 336,000 metric tons of sewage sludge that were disposed of in the oceans in
1988 has not been determined.
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Table 8-42. Quantity of sewage sludge disposed of annually for the reference year 1995 by
primary, secondary, and advanced treatment publicly owned treatment works and
potential dioxin TEQ releases
Use/disposal practice
Land application13
Advanced treatment0
Other beneficial used
Surface disposal/landfill
Incineration
Other disposal method
TOTAL
Volume disposed
of (thousands of
dry metric
tons/yr)
2,500
700
500
1,100
1,400
100
6,300
Percent of
total volume
41
12
7
17
22
1
100
Potential dioxin release"
(g TEQ/yr)
I-TEQDF
122.3
34.2
24.5
53.8
e
4.9
240
TEQDF-
WHO98
90.7
25.4
18.2
39.9
e
3.6
178
Totential dioxin TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume
generated (column 2) by the average of the mean I-TEQDF concentrations in sludge reported by Rubin and White
(1992) (50 ng/kg dry weight) and Green et al. (1995) and Cramer et al. (1995) (47.7 ng/kg). The calculations of
TEQDF-WHO98 used the mean concentration of 36.3 ng TEQDF-WHO98/kg for the results reported by Green et al.
(1995) and Cramer et al. (1995).
bWithout further processing or stabilization, such as composting.
°Such as composting.
dEPA assumes that this category includes distribution and marketing (i.e., sale or give-away of sludge for use in
home gardens). Based on the 1988 National Sewage Sludge Survey and 1988 Needs Survey, approximately 1.3%
of the total volume of sewage disposed is distributed and marketed (Federal Register, 1993b). Therefore, it is
estimated that 3 g TEQDF-WHO98 (4 g I-TEQDF) were released through distribution and marketing in 1995.
eSee Section 3.5 for estimates of CDD/CDF releases to air from sewage sludge incinerators.
Sources: Federal Register (1990, 1993b).
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Table 8-43. Quantity of sewage sludge disposed of annually for reference
year 2000 by primary, secondary, and advanced treatment publicly owned
treatment works and potential dioxin TEQ releases
Use/disposal practice
Land application13
Advanced treatment0
Other beneficial used
Surface disposal/landfill
Incineration
Other disposal method
TOTAL
Volume disposed
of (thousands of
dry metric
tons/yr)
2,800
800
500
900
1,500
100
6,600
Percent of
total volume
43
12.5
7.5
14
22
1
100
Potential dioxin
release"
(g TEQ/yr)
TEQDF-WH098
60.8
17.4
10.9
19.5
e
2.17
111
a Potential dioxin TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume
generated (i.e., column 2) by the average of the mean TEQDF-WHO98 concentrations in sludge reported by U.S.
EPA (2002).
bWithout further processing or stabilization, such as composting.
°Such as composting.
dEPA assumes that this category includes distribution and marketing (sale or give-away of sludge for use in home
gardens). Based on the 1988 National Sewage Sludge Survey and 1988 Needs Survey, approximately 1.3% of
the total volume of sewage disposed is distributed and marketed (Federal Register, 1993b). Therefore, it is
estimated that 1.9 g TEQDF-WHO98 were released through distribution and marketing in 2000.
eSee Section 3.5 for estimates of CDD/CDF releases to air from sewage sludge incinerators.
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Table 8-44. Biosolids disposal practices for reference year 2000
Use/disposal practice
Land application
Surface disposal/landfill
Incineration
Other
TOTAL
Volume disposed of
(thousands of dry metric
tons/yr)
3,100
940
1,000
64
5,100
Percent of
total volume
61
18
20
1
100
Source: NRC (2002).
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Table 8-45. CDD/CDF concentrations in Swedish liquid soap, tall oil, and
tall resin
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
1,2,3,4,8-71,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3, 4,7, 8/9-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 TEQDF-WHO98a
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDFa
Liquid soap
(ng/L)
ND (0.009)
0.4
ND (0.02)
0.32
0.18
1.9
1
0.62
0.29
0.2
0.013
ND (0.004)
ND (0.004)
ND (0.004)
ND (0.005)
ND(O.Ol)
NA
3.8
1.123
0.447
0.647
0.12
15
3.4
3.6
1
1
1.3
0.15
ND(O.Ol)
NA
25.57
Tall oil
(ng/kg)
3.6
5.3
ND(2)
ND(2)
ND(2)
ND(1)
5.3
17
4.2
1.9
1.4
0.7
ND (0.7)
ND (0.5)
ND (0.8)
ND(2)
NA
14.2
25.2
9.4
12
31
380
3.3
ND(1)
5.3
26
41
4.9
ND(2)
NA
491.5
Tall resin
(ng/kg)
ND(1)
3.1
ND(4)
810
500
5,900
6,000
ND(2)
ND (0.4)
ND (0.5)
24
ND(1)
ND (0.7)
\ /
10
9.0
NA
13,213.1
43
200
196
ND(1)
25
6,800
11,000
6,000
ND(2)
ND (0.5)
56
19
NA
23,900
Calculations assume nondetect values are zero.
ND = Not detected (value in parenthesis is the detection limit)
NA = Not analyzed
~ = No information given
Source: Rappe et al. (1990c).
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Ratio (median congener cone. / total CDD/CDF cone.)
0.1 0.2 0.3 0.4
0.5
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HzCDD
1,2,3,7,8,9-HzCDD
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-HzCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HzCDF
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
Ratio (median congener TEQ conc./total TEQ cone.)
0.1 0.2 0.3 0.4 O.B 0.6 0.7
0.8
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
Nondetects set equal to l/i detection limit.
Figure 8-1. 104 Mill Study full congener analysis results for pulp.
Source: Median concentrations from U.S. EPA (1990a).
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Ratio (median congener cone. / total CDD/CDF cone.)
0.1 0.2 0.3 0.4
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
itaiio ^median congener icy conc./ioiai rev cone.;
0.1 0.2 0.3 0.4 0.5 0.6 0.7
0.8
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
Nondetects set equal to l/i detection limit.
Figure 8-2. 104 Mill Study full congener analysis results for sludge.
Source: Median concentrations from U.S. EPA (1990a).
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Ratio (median congener conc./total CDD/CDF cone.)
0.1 0.2 0.3 0.4 O.S 0.6 0.7
0.8
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
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
Ratio (median congener TEQ conc./total TEQ cone.)
0.1 0.2 0.3 0.4 0.5 0.6
0.7
Nondetects set equal to Vi detection limit.
Figure 8-3. 104 Mill Study full congener analysis results for effluent
Source: Median concentrations from U.S. EPA (1990a).
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Ratio (congener concentration / total CDD/CDF concentration)
0.1 0.2 0.3 0.4 0.5 0.6
0.7
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
Ratio (congener group concentration / total CDD/CDF concentration)
0.1 0.2 0.3 0.4 0.5 0.6
Nondetects set equal to zero.
Figure 8-4. Congener and congener group profiles for technical-grade PCP
(based on data reported in Table 8-7).
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Katio (mean congener cone. / mean total Z3'/B-UDU/UUf cone.)
0.1 0.2 0.3 0.4
0.5
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
Nondetect set equal to zero.
Figure 8-5. Congener profile for 2,4-D (salts and esters) (based on mean
concentrations reported in Table 8-26).
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Ratio (mean congener cone. / total 2378-CDD/CDF cone.)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.9
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
Nondetects set equal to l/i detection limit.
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
Katio (mean congener cone. / total 23/B-(JL)L>/uiJi- cone.)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0.9
Figure 8-6. Congener profiles for sewage sludge
Source: Green et al. (1995).
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1 9. BIOLOGICAL SOURCES OF CDDs/CDFs
2
3 Numerous laboratory and field research studies have demonstrated that biochemical
4 formation of CDDs/CDFs from chlorophenol precursors is possible. In addition, under certain
5 conditions, some CDDs/CDFs can be biodegraded to form less chlorinated (and possibly more
6 toxic) CDDs/CDFs. Both of these mechanisms are discussed in this chapter; however, the extent
7 to which CDDs/CDFs are formed by either mechanism in the environment is not known at
8 present.
9 The origin of the CDDs/CDFs that were recently discovered in ball clay deposits is not
10 yet determined, and natural occurrence is still considered a possibility. Chapter 13 discusses this
11 topic in detail.
12
13 9.1. BIOTRANSFORMATION OF CHLOROPHENOLS
14 Biochemical formation of CDDs/CDFs, particularly the more-highly chlorinated
15 congeners, from chlorophenol precursors is possible, as indicated in laboratory studies with
16 solutions of trichlorophenols and PCP in the presence of peroxidase enzymes and hydrogen
17 peroxide (Svenson et al., 1989; Oberg et al., 1990; Wagner et al., 1990; Oberg and Rappe, 1992;
18 Morimoto and Kenji, 1995) and with sewage sludge spiked with PCP (Oberg et al., 1992).
19 However, the extent to which CDDs/CDFs are formed in the environment via this mechanism
20 cannot be estimated at this time.
21 In 1991, Lahl et al. (1991) reported finding CDDs/CDFs in all 22 samples of the various
22 types of composts analyzed. The hepta- and octa-substituted CDDs and CDFs were typically the
23 dominant congener groups found. The I-TEQDF content of the composts ranged from 0.8 to 35.7
24 ng I-TEQDF/kg. The CDDs/CDFs found in compost may be primarily the result of atmospheric
25 deposition onto plants that are subsequently composted, but they may also be caused by uptake of
26 CDDs/CDFs from air by the active compost (Krauss et al., 1994). CDDs/CDFs are also
27 frequently detected in sewage sludges, and they may come primarily from the sources identified
28 in Section 8.4.1.
29 Peroxidases are common enzymes in nature. For example, the initial degradation of the
30 lignin polymer by white- and brown-rot fungi is peroxidase catalyzed (Wagner et al., 1990). The
31 conversion efficiency of chlorinated phenols to CDDs/CDFs that has been observed is low. In
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1 the solution studies, Oberg and Rappe (1992) reported a conversion efficiency of PCP to OCDD
2 of about 0.01%, Morimoto and Kenji (1995) reported a conversion efficiency of PCP to OCDD
3 of 0.8%, and Wagner et al. (1990) reported a conversion efficiency of trichlorophenol to HpCDD
4 of about 0.001%. Oberg et al. (1990) reported a conversion efficiency of trichlorophenols to
5 CDDs/CDFs of about 0.001%. In their sewage sludge study, Oberg et al. (1992) reported a
6 conversion efficiency of PCP to total CDDs of 0.0002 to 0.0004%.
7 Several researchers have conducted both laboratory and field studies in an attempt to
8 better understand the extent of and factors affecting the fate or formation of CDDs/CDFs in
9 composts and sewage sludges. The findings of several of these studies are discussed in the
10 following paragraphs. These findings are not always consistent because the congener profiles
11 and patterns detected—and the extent of CDD/CDF "formation," if any—may vary with compost
12 materials studied, differences in experimental or field composting design, and duration of the
13 studies.
14 Harrad et al. (1991) analyzed finished composts and active compost windrows from a
15 municipally operated yard waste composting facility in Long Island, New York. Concentrations
16 measured in 12 finished composts ranged from 14 to 41 ng I-TEQDF/kg (mean of 3 ng I-
17 TEQDF/kg). The concentrations in the five active compost samples (1 to 30 days in age) ranged
18 from 7.7 to 54 ng I-TEQDF/kg (mean of 21 ng I-TEQDF/kg). The authors observed that CDD/CDF
19 concentrations measured in two soil samples from the immediate vicinity of the composting
20 facility were significantly lower (1 and 1.3 ng I-TEQDF/kg) than the levels found in the composts,
21 suggesting that the source(s) of CDDs/CDFs in the composts was different than the source(s)
22 affecting local soils.
23 The authors also noted a strong similarity between the congener profiles observed in the
24 composts and the congener profile of a PCP formulation (i.e., predominance of 1,2,4,6,8,9-
25 HxCDF and 1,2,3,4,6,8,9-HpCDF in their respective congener groups), which indicated to them
26 that leaching of CDDs/CDFs from PCP-treated wood in the compost piles was the likely source
27 of the observed CDDs/CDFs. The levels of PCP in the 12 finished composts ranged from 7 to
28 190 pg/kg (mean of 33 |_ig/kg), and the PCP levels in the active compost samples ranged from 17
29 to 210 pg/kg (mean of 68 pg/kg). The PCP level in both soil samples was 1.5 pg/kg.
30 Goldfarb et al. (1992) and Malloy et al. (1993) reported the results of testing of composts
31 at three municipal yard waste composting facilities (5 to 91 ng I-TEQDF/kg, mean of 30 ng I-
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1 TEQDF/kg), two municipal solid waste composting facilities (19 to 96 ng I-TEQDF/kg, mean of 48
2 ng I-TEQDF/kg), and one municipal facility composting solid waste and dewatered sewage sludge
3 (37 to 87 ng I-TEQDF/kg, mean of 56 ng I-TEQDF/kg). All facilities were located in the United
4 States. Two general trends were observed for the three types of composts: a progressive increase
5 in analyte levels, with an increasing degree of chlorination for each compound type (CDDs,
6 CDFs, chlorophenols, and chlorobenzenes), and a progressive increase in concentration of each
7 congener or homologue group from yard waste to solid waste to solid waste/sewage sludge
8 composts. As noted above, the mean TEQ concentrations showed this same trend, which was
9 primarily due to increasing levels of 1,2,3,4,6,7,8-HpCDD and OCDD. The mean PCP
10 concentrations in the three compost types were 20 pg/kg (yard waste), 215 pg/kg (solid waste),
11 and 615 |_ig/kg (solid waste/sewage sludge).
12 Comparison of congener profiles by the authors indicated that the CDD/CDF residue in
13 PCP-treated wood in the compost feedstock was a major but not exclusive contributor of the
14 observed CDDs/CDFs. The authors postulated that biological formation of HxCDDs, HpCDDs,
15 and OCDD from chlorophenols (tri-, tetra-, and penta-) in the compost could be responsible for
16 the elevated levels of these congener groups relative to their presence in PCP.
17 Oberg et al. (1993) measured the extent of CDD/CDF formation in three conventional
18 garden composts; two were spiked with PCP and one was spiked with hexachlorobenzene. One
19 PCP-spiked compost was monitored for 55 days and the other for 286 days. A significant
20 increase in the concentrations of the higher chlorinated congeners, particularly the HpCDDs,
21 OCDD, and, to a lesser extent, OCDF, were observed. Similar results were reported for the
22 hexachlorobenzene-spiked compost, which was monitored for 49 days. Oberg et al. stated that
23 for a "typical" composting event, a two- to threefold increase in TEQ content corresponded with
24 an elevation of 0.2 to 0.5 ng I-TEQDF/kg dry weight.
25 Weber et al. (1995) subjected sewage sludges from two German communities to
26 anaerobic digestion in laboratory reactors for 60 days. The two sludges were spiked with 2,3,5-
27 trichlorophenol (10 to 25 mg/kg), a mixture of 2,3,5-trichlorophenol and dichlorophenols (2.5 to
28 25 mg/kg), or a mixture of di-, tri-, and tetrachlorobenzenes (4 to 40 mg/kg). The initial
29 CDD/CDF concentrations in the two sludges were 9 and 20 ng I-TEQDF/kg. In nearly all of the
30 digestion experiments, the addition of the precursors did not lead to any significant changes in
31 concentrations. The only exceptions were increased 2,3,7,8-TCDF concentrations in the mixed
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1 chlorophenol experiments and decreased 2,3,7,8-TCDF concentrations in the mixed
2 chlorobenzene experiments. However, the same increases or decreases for this congener were
3 also observed in the controls (i.e., no precursors added).
4 Researchers at the U.S. Department of Agriculture (USDA) (Fries et al., 1997) reported
5 that dairy cows that were fed PCP-treated wood excreted amounts of OCDD almost four times
6 greater than the amounts ingested. Feil and Tiernan (1997) reported that rats fed technical PCP
7 had liver concentrations of HxCDD, HpCDD, HpCDF, OCDD, and OCDF two to three orders of
8 magnitude higher than rats fed purified PCP. These results suggest the in vivo formation of
9 CDDs/CDFs from pre-dioxins (i.e., chlorinated phenoxy phenols present as contaminants in the
10 PCP). A follow-up USDA study (Huwe et al., 1998) investigated the metabolic conversion of a
11 pre-dioxin (monochloro-2-phenoxyphenol) to OCDD in a feeding study with rats. The results of
12 the study demonstrated the formation of OCDD from the pre-dioxin, although the conversion
13 was estimated to be less than 2%. Interestingly, the study noted that the presence of added
14 OCDD in the feed material increased the percentage of pre-dioxin conversion.
15 Wittsiepe et al. (1998) demonstrated that CDDs/CDFs can be formed through reaction of
16 chlorophenols with myeloperoxidase (a component of neutrophile granulocytes, a subgroup of
17 human leucocytes). The CDDs/CDFs formed showed different homologue patterns and
18 formation rates depending on the degree of chlorination of the chlorophenol substrate. The
19 formation rates ranged from 1 to 16 |_imol of CDD/CDF per mol of chlorophenol substrate.
20
21 9.2. BIOTRANSFORMATION OF HIGHER CDDs/CDFs
22 Results of several studies that examined the fate of a range of CDD/CDF congeners in
23 pure cultures, sediments, and sludges indicate that under certain conditions some CDD/CDF
24 congeners will undergo biodegradation to form less-chlorinated (and possibly more toxic)
25 CDDs/CDFs. However, the extent to which more toxic CDDs/CDFs are formed in the
26 environment via this mechanism cannot be estimated at this time. The following paragraphs
27 discuss studies that examined the products of biodegradation in sediments, compost, and sewage
28 sludge.
29 Several reports indicate that CDDs and CDFs may undergo microbial dechlorination in
30 anaerobic sediments. Adriaens and Grbic-Galic (1992; 1993) and Adriaens et al. (1995) reported
31 the results of a series of microcosm studies using Hudson River sediment (contaminated with
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1 Aroclor 1242) and aquifer material (contaminated with CDDs) from Pensacola, Florida. Both
2 types of substrates were spiked with several CDDs (1,2,3,4,6,7,8-HpCDD; 1,2,3,4,7,8-HxCDD;
3 and l,2,4,6,8,9-/l,2,4,6,7,9-HxCDD) and CDFs (1,2,3,4,6,7,8-HpCDF and 1,2,4,6,8-PeCDF) and
4 monitored over a 16-month period at an incubation temperature of 30 °C. The Hudson River
5 sediment was spiked with 144 pg/kg of each congener, and the Pensacola aquifer material was
6 spiked with 63 |_ig/kg of each congener.
7 All of the congeners, with the exception of 1,2,3,4,6,7,8-HpCDF, showed a slow decrease
8 in concentration over time, which was attributed to biologically mediated reductive
9 dechlorination, with net disappearance rates ranging from 0.0031 wk"1 to 0.0175 wk"1 (i.e., half-
10 lives of approximately 1 to 4 yr). However, Adriaens et al. (1995) concluded that actual half-
11 lives may be orders of magnitude higher. The experiment with 1,2,3,4,6,7,8-HpCDD yielded
12 formation of two HxCDDs (1,2,3,4,7,8- and 1,2,3,6,7,8-). Thus, removal of the peri-substituted
13 (1,4,6,9) chlorines was favored, with enrichment of 2,3,7,8-substituted congeners. No less-
14 chlorinated congeners were identified from incubation with the other tested congeners. 1,2,4,6,8-
15 PeCDF was also examined in dichlorophenol-enriched cultures. After 6 months of incubation,
16 several TCDFs were identified, which also indicated that peri-dechlorination was the preferred
17 route of reduction.
18 Barkovskii and Adriaens (1995, 1996) reported that 2,3,7,8-TCDD (extracted from
19 Passaic River sediments) was susceptible to reductive dechlorination when incubated at 30 °C
20 under methanogenic conditions in a mixture of aliphatic and organic acids inoculated with
21 microorganisms obtained from Passaic River sediments. The initial concentration of 2,3,7,8-
22 TCDD (20 ± 4 |_ig/L) decreased by 30% to 14 ± 2 ng/L over a period of 7 months, with the
23 consecutive appearance and disappearance of tri-, di-, and mono-CDDs. Experiments were also
24 conducted by spiking the sediment with HxCDDs, HpCDDs, and OCDD. Up to 10% of the
25 spiked OCDD was converted to hepta-, hexa-, penta-, tetra-, tri-, di-, and mono-chlorinated
26 isomers, but the reaction stoichiometry was not determined. Two distinct pathways of
27 dechlorination were observed: the peri-dechlorination pathway of 2,3,7,8-substituted hepta- to
28 penta-CDDs, resulting in the production of 2,3,7,8-TCDD, and the peri-lateral dechlorination
29 pathway of non-2,3,7,8-substituted congeners.
30 Several studies have reported that CDDs/CDFs can be formed during composting
31 operations through biological action on chlorophenols present in the compost feed material. The
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1 results of studies that specify likely involvement of chlorophenols are described in Section 9.1.
2 Another possible formation mechanism was suggested by Vikelsoe et al. (1994), who reported
3 that more-highly chlorinated CDD/CDF congeners are formed when humic acid is reacted with a
4 peroxidase enzyme, hydrogen peroxide, and sodium chloride. It is expected that some organic
5 material in compost and sewage sludge has a humic-like structure. Several additional studies are
6 described below in which the potential involvement of chlorophenols could not be assessed
7 because chlorophenol concentrations in the composts were not reported.
8 Schafer et al. (1993) monitored the seasonal changes in the CDD/CDF content, as well as
9 the extent of CDD/CDF formation, in composts from a vegetable and garden waste composting
10 operation in Germany. Finished compost samples were collected and analyzed every 2 months
11 for 1 yr. An annual cycle was observed in TEQ concentrations, with peak concentrations in the
12 summer (approximately 8.5 ng I-TEQDF/kg) being 2.5 times higher than the lowest concentrations
13 observed in the winter (approximately 3.5 ng I-TEQDF/kg). No seasonal source was apparent that
14 could explain the observed differences in seasonal levels.
15 The CDD/CDF contents of the starting waste materials for two compost cycles (March
16 and September) were measured to monitor the extent of CDD/CDF formation during
17 composting. For the March cycle sample, most 2,3,7,8-substituted CDD/CDF congeners
18 decreased in concentration during composting. Four CDF congeners showed a slight increase in
19 concentration (less than 10%). For the September cycle sample, OCDD and HpCDD
20 concentrations increased 300% during composting. Less than 10% increases were observed for
21 HxCDDs and OCDF; all other 2,3,7,8-substituted CDD/CDF congeners showed decreases in
22 concentrations during composting.
23 Krauss et al. (1994) measured the extent of CDD/CDF formation during the composting
24 of household waste using a laboratory compost reactor. After 11 wk, the TEQ content of the
25 compost increased from 3 to 4.5 ng. The largest increases in mass content were observed for
26 HpCDD (primarily 1,2,3,4,6,7,8-HpCDD) and OCDD. TCDD, PeCDD, and HxCDD showed no
27 change in mass content. All CDF congener groups showed decreases in mass content; however,
28 the concentrations in both the starting and finished compost were close to the analytical detection
29 limits.
30 Oberg et al. (1994) reported the results of monitoring of two household waste composts
31 and two garden composts. The total CDD/CDF content of both household waste composts
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1 decreased over the 12-wk test period. Total CDD content and PCB content decreased, but total
2 CDF content increased, in contrast with the findings of Krauss et al. (1994). However, a small
3 increase in OCDD content in both composts was observed. The two garden composts were
4 monitored for a 60-wk period. Total CDD/CDF concentration increased, with the largest
5 increases observed for OCDD and HpCDDs. The less-chlorinated CDFs decreased in
6 concentration.
7 As a follow-up to a preliminary study (Hengstmann et al., 1990) that indicated CDD/CDF
8 concentrations may increase and congener profiles may change during anaerobic digestion of
9 sewage sludge, Weber et al. (1995) subjected sewage sludges from two German communities to
10 anaerobic digestion and aerobic digestion in laboratory reactors for 60 days and 20 days,
11 respectively. The initial average I-TEQDF concentrations in the raw sludges were 20 and 200 ng
12 I-TEQDF/kg. No significant increase or decrease in total CDD/CDF content or congener group
13 content was observed with either sludge. In contrast, a significant decrease in CDD/CDF content
14 was observed in the aerobic digestion experiments on both sludges. The greatest percentage
15 decreases in congener group concentrations (greater than 40%) were observed for TCDF,
16 PeCDF, HxCDF, TCDD, and PeCDD in the sludge initially containing 20 ng I-TEQDF/kg and for
17 TCDF, TCDD, HpCDD, and OCDD in the initially high-content sludge. The greatest percentage
18 decreases in congener concentrations (greater than 40%) were observed for non-2,3,7,8-
19 substituted congeners.
20 These data do not provide a basis for making a release estimate via biotransformation,
21 therefore biotransformation releases are classified as Category E (not quantifiable).
22
23 9.3. DIOXIN-LIKE COMPOUNDS IN ANIMAL MANURE
24 In 2000, approximately 9 billion individual livestock and poultry animals were raised on
25 commercial farms in the United States (U.S. Census Bureau, 200Ib). It is estimated that beef
26 animals, dairy cows, chickens, turkeys, and pigs, combined, produced in excess of 190 billion kg
27 (dry weight) of manure in 2000 (Table 9-1). Because livestock and poultry manure can provide
28 valuable organic material and nutrients for crop and pasture growth, most of the animal manure
29 generated at commercial farms and animal feed lots is applied to farmland as fertilizer. To the
30 extent dioxin-like compounds may contaminate animal manures, the practice of land-spreading
31 animal waste may result in releases of CDDs/CDFs to the open and circulating environment.
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1 Stevens and Jones (1993) published results of CDD and CDF detection in animal manure
2 applied to farmland in the United Kingdom. Manure from six milking dairy cows was sampled
3 at six farms in the northern United Kingdom. In addition, single samples of sheep, chicken, and
4 pig manure were collected from other farms in the region. The samples were shipped to a
5 laboratory for trace chemical analysis. Samples were analyzed using high-resolution gas
6 chromatography coupled with high-resolution mass spectrometry and a capillary column for the
7 identification of CDD/CDF congeners. Recoveries of the internal standard ranged from 51 to
8 94%, with a mean of 74% for CDD/CDF congeners. Table 9-2 summarizes the results of the
9 study. The pig and chicken manure contained approximately 0.2 ng WHO-TEQ/kg, and the cow
10 manure averaged 3.6 ng WHO-TEQ/kg in concentration.
11 This study provides extremely limited data on the possible levels and occurrences of
12 dioxin-like compounds in farm animal manure, and, therefore, these data are clearly not
13 representative of national releases of dioxin-like compounds from the land application of all farm
14 animal manure in the United States. Accordingly, EPA currently considers this source to be
15 unquantifiable (Category E) in terms of dioxin emissions.
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Table 9-1. Estimated quantity of animal manure produced in the United
States in 2000
Species
Swine
Layer
Broiler
Turkey
Beef
Dairy cow
Total
Numbers of
individuals on
farms in 2000"
6.73e+07
4.35e+08
8.26e+09
2.7e+08
9.73e+07
9.21e+06
Average
weight of
animal (lbs)b
135
4
2
15
800
1400
Total live
weight on
farms (Ibs)
9.09e+09
1.74e+09
1.65e+10
4.05e+09
7.78e+10
1.29e+10
Manure generation
rate factor
(dry weight Ib per
Ib live unit weight
per day)c
8.2e-03
1.6e-02
2.1e-02
1.2e-02
6.9e-03
le-02
Manure
generated
(Ib/yr dry
weight)
2.72e+10
1.02e+10
1.27e+ll
1.77e+10
1.96e+ll
4.71e+10
4.25e+ll
Manure
produced
(kg dry weight)
1.23e+10
4.61e+09
5.74e+10
8.04e+09
8.89e+10
2.13e+10
1.936+11
"Source: U.S. Census Bureau (200Ib).
bSource: U.S. EPA (2001e).
°Source: Stevens and Jones (2003).
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Table 9-2. CDD and CDF concentrations (ng/kg dry weight) in samples of
animal manure in the United Kingdom
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 CDD/CDF
WHO-TEQ
Cows (n = 6)
(mean)
0.17
0.46
2.4
4.5
2.6
120
460
0.3
0.3
0.28
0.6
0.51
1.9
0.4
7.6
12
35
920
3.6
Sheep (n = 1)
0.11
0.41
0.9
0.86
0.56
9.4
53
.2
.1
.2
.4
.1
0.15
1.4
5.2
0.56
5
700
2.1
Pig(n = l)
0.01
0.07
0.26
0.1
0.07
0.8
11
0.03
0.04
0.06
0.05
0.06
0.04
0.06
0.48
0.04
0.73
26
0.19
Chicken
(n=l)
0.01
0.04
0.03
0.09
0.12
1.4
14
0.03
0.09
0.12
0.15
0.07
0.05
0.14
0.37
0.09
0.8
33
0.2
Source: Stevens and Jones (1993).
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1 10. PHOTOCHEMICAL SOURCES OF CDDs/CDFs
2
3 10.1. PHOTOTRANSFORMATION OF CHLOROPHENOLS
4 Several researchers have demonstrated that CDDs/CDFs can be formed via photolysis of
5 PCP under laboratory conditions. These studies are described below. However, the extent to
6 which CDDs/CDFs are formed in the environment via this mechanism cannot be estimated at
7 this time.
8 Lamparski et al. (1980) conducted laboratory studies to determine the effect of simulated
9 summer sunlight on the formation of OCDD, HpCDDs, and HxCDDs in wood that was pressure-
10 treated in the laboratory with PCP. In the first set of experiments, wood veneers (southern pine)
11 treated with purified PCP or with Dowicide EC-7, using methylene chloride as the PCP carrier,
12 were exposed to light for 70 days. The PCP concentration in the treated wood was 5% by
13 weight, which approximates the concentration in the outer layer of PCP-treated wood utility
14 poles. Photolytic condensation of PCP to form OCDD was observed, with the OCDD
15 concentration increasing by a maximum factor of 3,000 for the purified PCP and by a factor of 20
16 for EC-7 at about day 20 before leveling off. HpCDD and HxCDD were also formed, apparently
17 by photolytic degradation of OCDD rather than by condensation of PCP and tetrachlorophenols.
18 The HxCDD concentration increased by a factor of 760 for the purified PCP and by a factor of 50
19 for EC-7 over the 70-day exposure period. The predominant HpCDD congener formed was
20 1,2,3,4,6,7,8-HpCDD as a result of an apparently preferential loss of chlorine at the peri position
21 (i.e., positions 1, 4, 6, and 9).
22 In a second set of experiments conducted by Lamparski et al. (1980), a hydrocarbon oil
23 (P-9 oil) was used as the carrier to treat the wood. The increases observed in the OCDD,
24 HpCDD, and HxCDD were reported to be much lower relative to the increases observed in the
25 first set of experiments, which used methylene chloride as the carrier. Results were reported only
26 for OCDD. The OCDD concentration increased by a maximum factor of 1.5 for both EC-7 and
27 technical PCP and by a factor of 88 for purified PCP. The authors concluded that the oil either
28 reduced condensation of PCP to OCDD or accelerated degradation to other species by providing
29 a hydrocarbon trap for free-radical species.
30 Vollmuth et al. (1994) studied the effect of irradiating laboratory water and landfill
31 seepage water that contained PCP under conditions simulating those used to purify water with
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1 ultraviolet (UV) radiation (5-hr exposure to 254 nm radiation from low-pressure mercury lamps).
2 Before irradiation, the three solutions tested contained approximately 1 mg/L of PCP or PCP-Na,
3 but the CDD/CDF content of one solution varied dramatically from those of the other two (1.5
4 vs. 2,066 and 2,071 pg I-TEQDF/L). Irradiation resulted in nearly total destruction of PCP
5 (greater than 99% loss) in all three experiments. An overall net increase in I-TEQDF-content was
6 observed in the initially low I-TEQDF-content water, but a net decrease was observed for the two
7 initially high I-TEQDF-content waters.
8 Irradiation of laboratory water containing purified PCP showed an increase in I-TEQDF
9 concentration from 1.5 pg/L to 214.5 pg/L. The increase was due entirely to the formation of
10 1,2,3,4,6,7,8-HpCDD, OCDD, and 1,2,3,4,6,7,8-HpCDF. Formation of non-2,3,7,8-substituted
11 HpCDDs and HpCDFs was also observed. The ratios of the concentrations of these non-2,3,7,8-
12 congeners to the concentrations of the 2,3,7,8-congeners were 0.6 for HpCDDs and 5 for
13 HpCDFs. The HpCDD and HpCDF congeners formed indicated that the operative mechanism
14 was photoinduced dechlorination of OCDD at a peri position and dechlorination of OCDF at
15 only the 1- and 9-peri positions.
16 Irradiation of water containing technical PCP-Na (Dowicide-G) resulted in a net loss in I-
17 TEQDF content, from 2,065.5 pg/L to 112.7 pg/L. The only 2,3,7,8-substituted congener showing
18 an increased concentration was 1,2,3,6,7,8-HxCDD. The other congeners originally present in
19 the technical PCP-Na showed reductions of 80.6 to 100%.
20 The I-TEQDF content of seepage water from a landfill (2,071 pg I-TEQDF/L) was reduced
21 by a factor of 2 to 1,088 pg I-TEQDF/L. However, several 2,3,7,8-substituted congeners did
22 increase in concentration (1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, 1,2,3,4,6,7,8-HpCDF, and
23 OCDF).
24 Waddell et al. (1995) also studied the effect of irradiating distilled laboratory water
25 containing PCP under conditions simulating those used to purify water with UV radiation. The
26 results obtained were similar to those of Vollmuth et al. (1994). Analytical-grade PCP at a
27 concentration of 10 mg/L was exposed for 12 min to 200 to 300 nm radiation from a medium-
28 pressure mercury lamp. All CDD/CDF congener groups increased in concentration over the
29 12-min exposure period, with the greatest increases observed for OCDD (75-fold increase) and
30 HpCDDs (34-fold increase). The I-TEQDF content of the solution increased from 4.2 pg I-
31 TEQDF/L to 137 pg I-TEQDF/L over the 12-min period. The dominant congeners formed, in terms
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1 of both concentration and contribution to I-TEQDF, were 1,2,3,4,6,7,8-HpCDD, OCDD, and
2 1,2,3,7,8,9-HxCDD.
3
4 10.2. PHOTOLYSIS OF HIGHER CDDs/CDFs
5 Photolysis appears to be one of the few environmentally significant degradation
6 mechanisms for CDDs/CDFs in water, air, and soil. Although, in most studies, good mass
7 balances were not obtained and the photolytic pathways for CDDs/CDFs were not fully
8 identified, a major photolysis pathway appears to be photodechlorination, resulting in formation
9 of less-chlorinated CDDs/CDFs. A preferential loss of chlorines from the peri positions (1, 4, 6,
10 and 9) rather than from the lateral positions (2, 3, 7, and 8) was reported for some congener
11 groups when irradiated as dry films and sorbed to soil and in gas-phase CDDs/CDFs (Choudhry
12 and Webster, 1989; Kieatiwong et al., 1990; Sivils et al., 1994, 1995; Tysklind et al., 1992).
13 Several researchers reported that carbon-oxygen cleavage and other mechanisms may be
14 similarly or more important pathways for CDDs/CDFs containing four or fewer chlorines.
15 Because of the difficulties inherent in controlling experimental variables for nonvolatile
16 and highly lipophilic compounds such as CDDs/CDFs, few photolysis studies have been
17 performed on natural waters, soils, atmospheric particulates, and atmospheric gases to examine
18 the rates and products of photolysis under environmentally relevant conditions. Thus, it is not
19 possible at this time to quantitatively estimate the mass of various CDD/CDF congeners formed
20 in the environment annually via photolytic mechanisms. Sections 10.2.1 through 10.2.4
21 summarize the key findings of recent environmentally significant studies for the water, soil, and
22 air media.
23
24 10.2.1. Photolysis in Water
25 Numerous studies have demonstrated that CDDs/CDFs will undergo photodechlorination
26 following first-order kinetics in organic solution, with preferential loss of chlorine from the
27 lateral positions. Photolysis is slow in pure water, but it increases dramatically when solvents
28 serving as hydrogen donors such as hexane, benzene, methanol, acetonitrile, hexadecane, ethyl
29 oleate, dioxane, and isooctane are present. However, only a few studies have examined the
30 photolysis of CDDs/CDFs using natural waters and sunlight.
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1 Choudhry and Webster (1989) experimentally determined the sunlight photolysis half-life
2 of 1,3,6,8-TCDD in pond water to be 3.5 days (more than 10 times greater than the half-life
3 predicted by laboratory experiments using a water/acetonitrile solution). The authors attributed
4 this significant difference in photolysis rates to the light screening/quenching effects of dissolved
5 organic matter.
6 Friesen et al. (1990) examined the photolytic behavior of 1,2,3,4,7-PeCDD and
7 1,2,3,4,6,7,8-HpCDD in water:acetonitrile (2:3, v/v) and in pond water under sunlight at 50
8 degrees north latitude. The observed half-lives of these two compounds in the water :acetonitrile
9 solution were 12 and 37 days, respectively, but were much shorter in pond water, 0.94 and 2.5
10 days, respectively. Similarly, Friesen et al. (1993) studied the photodegradation of 2,3,7,8-TCDF
11 and 2,3,4,7,8-PeCDF by sunlight using water:acetonitrile (2:3, v/v) and lake water. The observed
12 half-lives were 6.5 and 46 days, respectively, in the water:acetonitrile solution and 1.2 and 0.19
13 days, respectively, in lake water. The significant differences between the natural water and
14 water:acetonitrile solution results were attributed to indirect or sensitized photolysis due to the
15 presence of naturally occurring components in the lake and pond water.
16 Dung and O'Keefe (1992), in an investigation of aqueous photolysis of 2,3,7,8-TCDF and
17 1,2,7,8-TCDF, reported findings similar to those of Friesen et al. (1993). The photolysis rates of
18 the two TCDF congeners observed in river and lake water (half-lives of about 4 to 6 hr) were
19 double those observed in pure water (half-lives of about 8 to 11 hr). The authors attributed the
20 difference in rates to the presence of natural organics in the river and lake water that may act as
21 sensitizers.
22
23 10.2.2. Photolysis on Soil
24 Photolysis of CDDs/CDFs on soil has not been well characterized. According to the data
25 generated to date, however, photolysis is an operative degradation process only in the near-
26 surface soil where UV light penetrates (the top few millimeters or less of soil), and
27 dechlorination of peri-substituted chlorines appears to occur preferentially.
28 Miller et al. (1989) studied the CDD degradation products resulting from irradiation of
29 13C-labeled OCDD on two soil types using sunlamps. Approximately 38 to 42% of the OCDD
30 was degraded by day 5 of the experiment; no significant further loss of OCDD was observed over
31 the following 10 days. Although the authors determined that photodechlorination was not the
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1 dominant photolysis pathway, it was observed in both soils; approximately 10 to 30% of the less-
2 chlorinated congeners were produced from the immediate more-highly chlorinated congeners.
3 The HpCDD and HxCDD congeners observed as degradation products were present in
4 proportions similar to the number of congeners in each congener group. However, the
5 investigators observed greater yields of 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD than would be
6 expected on the basis of the number of potential TCDD and PeCDD congeners. One-fifth to
7 one-third of the total yield of PeCDDs was 1,2,3,7,8-PeCDD, and one-half of the total yield of
8 TCDDs was 2,3,7,8-TCDD.
9 Kieatiwong et al. (1990) performed experiments similar to those of Miller et al. (1989)
10 using natural sunlight rather than sunlamps for irradiation of 13C-labeled OCDD on soils.
11 Photodechlorination was estimated to account for approximately 10% of the loss of OCDD.
12 One-third to one-half of the total yield of PeCDDs was 1,2,3,7,8-PeCDD, and one-half of the
13 total yield of TCDDs was 2,3,7,8-TCDD. These findings, along with those of Miller et al.
14 (1989), indicate that the 2,3,7,8-substituted TCDD and PeCDD congeners were either
15 preferentially formed or were photochemically less reactive than the other congeners that were
16 formed.
17 Tysklind et al. (1992) studied the sunlight photolysis of OCDD on soil and reported
18 results similar to those of Miller et al. (1989) and Kieatiwong et al. (1990). Photodechlorination
19 was observed with production of HpCDDs, HxCDDs, PeCDDs, and TCDDs over the 16-day
20 irradiation period. Photodechlorination at the peri-substituted positions was the preferred
21 photodechlorination mechanism; the proportions of 2,3,7,8-substituted congeners present in the
22 soils after 16 days for each congener group were as follows: HxCDD, 65%; PeCDD, 40%; and
23 TCDD, 75%. Tysklind et al. (1992) also studied the sunlight photolysis of OCDF on soil.
24 Photodechlorination was observed; however, unlike the case with OCDD, photodechlorination of
25 the lateral-substituted positions was found to be the dominant photodechlorination mechanism,
26 resulting in a relative decreasing proportion of 2,3,7,8-substituted congeners during the
27 irradiation period. 2,3,7,8-TCDF was not observed in any of the irradiated samples.
28
29 10.2.3. Photolysis on Vegetation
30 Photolysis of CDDs/CDFs sorbed on the surface of vegetation has not been well
31 characterized, and the findings to date are somewhat contradictory. McCrady and Maggard
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1 (1993) reported that 2,3,7,8-TCDD sorbed on the surface of reed canary grass (Phalaris
2 arundinaceaL.) undergoes photolytic degradation with a half-life of 44 hr in natural sunlight. In
3 contrast, Welsch-Pausch et al. (1995) found little difference in the CDD/CDF congener patterns
4 between grass (Lolium multifloruni) grown on an outdoor plot and grass grown in a greenhouse
5 (i.e., UV light transmission blocked).
6 In an attempt to clarify this contradiction, Welsch-Pausch and McLachlan (1995) studied
7 the photodegradation of CDDs/CDFs on pasture grass (Arrhenatherion elatioris) during two
8 growing cycles (summer and autumn) using two greenhouses. One greenhouse was constructed
9 of glass that blocks UV transmission, and the other was constructed of plexiglass (4 mm) with a
10 UV light transmission of greater than 50% in the 280 to 320 nm range. In both the summer and
11 autumn exposure periods, the concentrations of CDDs/CDFs (on a congener-group basis) were
12 similar in the grass exposed to UV light and the grass that was not exposed. The authors
13 concluded that if photodegradation was occurring, it was a relatively insignificant factor in the
14 accumulation of CDDs/CDFs in pasture grass.
15
16 10.2.4. Photolysis in Air
17 Photolysis of CDDs/CDFs in the atmosphere has not been well characterized. On the
18 basis of data generated to date, however, photolysis appears to be a significant mechanism for
19 degradation (principally, dechlorination of the peri-substituted chlorines) of those CDDs/CDFs
20 present in the atmosphere in the gas phase. For airborne CDDs/CDFs sorbed to particulates,
21 photolysis appears to proceed very slowly, if at all. Because of the low volatility of CDDs/CDFs,
22 few studies have been attempted to measure actual rates of photodegradation of gas-phase
23 CDD/CDF, and only recently have studies examined the relative importance of photolysis to
24 particulate-bound CDDs/CDFs.
25 Sivils et al. (1994, 1995) studied the gas-phase photolysis of several CDDs (2,3,7-
26 TrCDD; 2,3,7,8-TCDD; 1,2,3,4-TCDD; 1,2,3,7,8-PeCDD, and 1,2,4,7,8-PeCDD) by irradiating
27 the effluent from a gas chromatograph with broadband radiation in the UV/visible region for
28 periods of up to 20 min. The irradiated sample was then introduced into a second gas
29 chromatograph to measure the extent of dechlorination. The results showed that degradation
30 followed first-order kinetics and that an inverse relationship existed between the degree of
31 chlorination and the rate of disappearance. Although the lack of photoproducts prevented an
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1 independent confirmation of the preferential loss mechanism, the results indicate that laterally
2 substituted congeners (chlorines at the 2, 3, 7, and 8 positions) degrade at a slower rate than do
3 the peri-substituted congeners (chlorines at the 1, 4, 6, and 9 positions). Although Sivils et al.
4 (1994) did not present the rate constants, the degradation rate for 2,3,7,8-TCDD (30% loss in
5 20 min) was reported to be slower than the rates for all other tested CDDs. Also, 1,2,4,7,8-
6 PeCDD (with two perichlorines) degraded significantly faster than did 1,2,3,7,8-PeCDD (with
7 only one perichlorine).
8 Mill et al. (1987) studied the photolysis of 2,3,7,8-TCDD sorbed onto small-diameter fly
9 ash particulates suspended in air. The results indicated that fly ash confers photostability on
10 2,3,7,8-TCDD. Little (8%) to no loss was observed on the two fly ash samples after 40 hr of
11 illumination. Tysklind and Rappe (1991) and Koester and Kites (1992) reported similar results
12 of photolysis studies with fly ash. Tysklind and Rappe (1991) subjected fly ash from two
13 German incinerators to various simulated environmental conditions. The fraction of
14 photolytically degradable CDD/CDF after 288 hr of exposure was in the range of 20 to 40% of
15 the extractable CDD/CDF. However, a 10 to 20% reduction was also observed in the darkened
16 control samples. With the exception of HpCDD and HpCDF, the concentration of all other
17 congener groups either increased or stayed the same during the exposure period from hour 144 to
18 hour 288.
19 Koester and Kites (1992) studied the photodegradation of CDDs/CDFs naturally adsorbed
20 to fly ash collected from five electrostatic precipitators. They observed no significant
21 degradation in 11 photodegradation experiments performed on the ash for periods ranging from 2
22 to 6 days. The authors concluded that (a) the absence of photodegradation was not due to the
23 absence of a hydrogen-donor organic substance; (b) other molecules on the ash, as determined by
24 a photolysis experiment with an ash extract, inhibited photodegradation, either by absorbing light
25 and dissipating energy or by quenching the excited states of the CDDs/CDFs; and (c) the surface
26 of the ash itself may have hindered photolysis by shielding the CDDs/CDFs from light.
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1 11. SOURCES OF DIOXIN-LIKE PCBs
2
3 The purpose of this chapter is twofold: (1) to identify sources that release dioxin-like
4 polychlorinated biphenyl (PCB) congeners into the environment and (2) to derive national
5 estimates for releases from these sources in the United States. PCBs have been found in all
6 media and in all parts of the world. PCBs were produced in relatively large quantities for use in
7 commercial products such as dielectrics, hydraulic fluids, plastics, and paints. They are no
8 longer commercially produced in the United States, but they continue to be released to the
9 environment through the use and disposal of these products. PCBs may also be inadvertently
10 produced as by-products during the manufacture of certain organic chemicals and also as
11 products of the incomplete combustion of some waste materials.
12
13 11.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY
14 Table 11-1 provides a compilation of known or suspected dioxin-like PCB-emitting
15 source categories in the United States for which emission measurements of dioxin-like PCB
16 congeners, Aroclors, or PCB congener groups have been reported in government, industry, and
17 trade association reports; conference proceedings and journal articles; and comments submitted
18 to EPA on previous versions of this document. The intent of Table 11-1 is to clearly identify
19 those source categories and media (air, water, land, and products) for which the available data are
20 adequate for reliably quantifying emissions of dioxin-like PCBs and those for which the data are
21 inadequate.
22 Nationwide emission estimates for the United States inventory are presented in
23 Table 11-2 (emissions to air, water, land, and product) for those source categories for which
24 estimates can be reliably quantified (the category has been assigned a confidence rating of A, B,
25 or C) (see Section 1.4.2 for details on confidence ratings). Table 11-2 also lists, in the far right
26 column, preliminary estimates of the potential magnitude of emissions from "unquantified"
27 sources (i.e., sources assigned a confidence rating of D) in reference year 1995. Because of large
28 uncertainties for these Category "D" estimates, they are not included in the quantitative
29 inventory.
30 Releases to the environment of "old" dioxin-like PCBs (dioxin-like PCBs manufactured
31 prior to the production ban) can occur from ongoing use and disposal practices. Prior to
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1 regulations enacted beginning in the late 1970s that limited the manufacture/use/disposal of
2 PCBs, significant quantities were released to the environment in association with (a) the
3 manufacture of PCBs, (b) the manufacture of products containing PCBs, and (c) the use and
4 disposal of products containing PCBs as well as materials that may have been contaminated with
5 trace levels of PCBs from prior PCB use or disposal. Following the ban on PCB production,
6 releases from these first two categories ceased. The third type of releases, those associated with
7 product use and disposal, will continue in at least four ways:
8
9 1. Disposal of products containing greater than 2 pounds of PCBs (e.g., dielectric fluids
10 in transformers and large capacitors), which is controlled by disposal regulations that
11 have minimized environmental releases;
12
13 2. Disposal of products containing small quantities of PCBs (e.g., small capacitors,
14 fluorescent lighting fixtures) or trace quantities of PCBs (e.g., wastepapers), which is
15 subject to disposal as municipal solid waste but which may result in some release to
16 the general environment;
17
18 3. Leaks and spills of still-in-service PCBs; and
19
20 4. Illegal disposal of PCBs.
21
22 No significant release of newly formed dioxin-like PCBs is occurring in the United
23 States. Unlike CDDs/CDFs, PCBs were intentionally manufactured in the United States in large
24 quantities from 1929 until production was banned in 1977. Although it has been demonstrated
25 that small quantities of dioxin-like PCBs can be produced during waste combustion, no strong
26 evidence exists that they are produced in significant quantities as by-products during combustion
27 or chemical processes. The widespread occurrence of dioxin-like PCBs in the U.S. environment
28 most likely reflects past releases associated with PCB production, use, and disposal. Further
29 support for this finding is based on observations of reductions since the 1980s in PCB
30 concentrations in Great Lakes sediment and in other areas.
31
32 11.2. RELEASES OF COMMERCIAL PCBs
33 PCBs were commercially manufactured by the direct batch chlorination of molten
34 biphenyl with anhydrous chlorine in the presence of a catalyst, followed by separation and
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1 purification of the desired chlorinated biphenyl fractions. The degree of chlorination was
2 controlled by the chlorine contact time in the reactor. Commercial PCB production is believed to
3 have been confined to 10 countries. Total PCBs produced worldwide since 1929 (the first year
4 of known production) has been estimated at 1.5 million metric tons.
5 Initially, PCBs were used primarily as dielectric fluids in transformers. After World War
6 II, PCBs found steadily increasing use as dielectric fluids in capacitors, as heat-conducting fluids
7 in heat exchangers, and as heat-resistant hydraulic fluids in mining equipment and vacuum
8 pumps. PCBs also were used in a variety of "open" applications (i.e, uses from which PCBs
9 cannot be recollected), including plasticizers, carbonless copy paper, lubricants, inks, laminating
10 agents, impregnating agents, paints, adhesives, waxes, additives in cement and plaster, casting
11 agents, dedusting agents, sealing liquids, fire retardants, immersion oils, and pesticides (DeVoogt
12 and Brinkman, 1989).
13 U.S. production peaked in 1970, with a volume of 39,000 metric tons. In 1971,
14 Monsanto Corporation, the major U.S. producer, voluntarily restricted the sale of PCBs for all
15 applications, with the exception of "closed electrical systems." Annual production fell to 18,000
16 metric tons in 1974. Monsanto ceased PCB manufacture in mid-1977 and shipped the last
17 inventory in October of that year. Regulations issued by EPA beginning in 1977, principally
18 under Toxic Substances Control Act (40 CFR 761), have strictly limited the production, import,
19 use, and disposal of PCBs. The estimated cumulative production and consumption volumes of
20 PCBs in the United States from 1930 to 1975 are 635,000 metric tons produced, 1,400 metric
21 tons imported (primarily from Japan, Italy, and France), 568,000 metric tons sold in the United
22 States, and 68,000 metric tons exported (Versar, Inc., 1976). The reliability of these values is
23 +5% and -20% (Versar, Inc., 1976).
24 Monsanto Corporation marketed technical-grade mixtures of PCBs primarily under the
25 trade name Aroclor. The Aroclor mixtures are identified by a four-digit numbering code in
26 which the last two digits indicate the chlorine content by weight percent. The exception to this
27 coding scheme is Aroclor 1016, which contains only mono- through hexachlorinated congeners
28 with an average chlorine content of 41%. From 1957 until 1972, Monsanto also manufactured
29 several blends of PCBs and poly chlorinated terphenyls (PCTs) under the trade names Aroclor
30 2565 and Aroclor 4465: manufacture and sales volumes are not available for these blends. Listed
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1 below are the percentages of total Aroclor production during the years 1957 to 1977 by Aroclor
2 mixture, as reported by Brown (1994).
3
4 1957-1977
5 U.S. production
6 Aroclor (%)
7 1016 12.88
8 1221 0.96
9 1232 0.24
10 1242 51.76
11 1248 6.76
12 1254 15.73
13 1260 10.61
14 1262 0.83
15 1268 0.33
16
17 The trade names of the major commercial PCB technical-grade mixtures manufactured in
18 other countries included Clophen (Germany), Fenclor and Apirolio (Italy), Kanechlor (Japan),
19 Phenoclor and Pyralene (France), Sovtel (USSR), Del or and Delorene (Czechoslovakia), and
20 Orophene (German Democratic Republic) (DeVoogt and Brinkman, 1989). The mixtures
21 marketed under these trade names had similar chlorine content (by weight percent and average
22 number of chlorines per molecule) to those of various Aroclor mixtures. Listed below are
23 comparable mixtures in terms of chlorine content marketed under several trade names.
24
25 Aroclor Clophen Pyralene Phenoclor Fenclor Kanechlor
26 1232 2000 200
27 1242 A-30 3000 DP-3 42 300
28 1248 A-40 DP-4 400
29 1254 A-50 DP-5 54 500
30 1260 A-60 DP-6 64 600
31
32 Major advances in analytical separation and resolution techniques beginning in the 1970s
33 enabled various researchers to identify and quantify PCB congeners present in Aroclors,
34 Clophens, and Kanechlors (Jensen et al., 1974; Albro and Parker, 1979; Huckins et al., 1980;
35 Albro et al., 1981; Duinker and Hillebrand, 1983; Kannan et al., 1987; Tanabe et al., 1987;
36 Duinker et al., 1988; Schulz et al., 1989; Himberg and Sippola, 1990; Larsen et al., 1992; deBoer
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1 et al., 1993; Schwartz et al., 1993; Frame et al., 1996a, b; and Frame, 1997). Schulz et al. (1989)
2 were the first to identify and quantify all PCB congeners present in a series of Aroclors and
3 Clophens. Frame (1995) reported preliminary results of a nearly completed round robin study,
4 one goal of which was to determine the distribution of all PCB congeners above 0.05 weight
5 percent in various Aroclors (1221, 1016, 1242, 1260, and 1262) using 18 state-of-the-art gas
6 chromatography/mass spectrometry (GC/MS) or electron capture detector (GC/ECD) systems.
7 Table 11-3 presents mean summary statistics on the concentrations of the dioxin-like
8 PCBs in each mixture group (e.g., Aroclor 1248, Clophen A-40, and Kanechlor 400 are in one
9 mixture group) reported by these researchers. Table 11-3 also presents the mean TEQ
10 concentration of each congener in each mixture group as well as the total mean TEQ
11 concentration in the mixture group.
12 For each mixture group, the congeners detected were generally similar. There was,
13 however, wide variability in the concentrations reported by some researchers for some congeners.
14 Brown et al. (1995) compiled similar statistics using a somewhat different set of studies and
15 derived significantly lower mean concentrations of some congeners in several Aroclors. Frame
16 (1995) and Larsen (1995) attributed such differences either to potential limitations in the GC
17 columns used by various researchers to separate similar eluting congeners or to actual differences
18 in the congener concentrations in the Aroclor, Clophen, and Kanechlor lots analyzed by various
19 research groups.
20 The congener distributions also vary among the different mixtures. Therefore, the
21 calculated TEQs also vary. The congener distributions for various lots of Aroclor 1254, and the
22 corresponding TEQs, are presented in another study (Frame, 1999) in which the relative TEQs
23 for late production lots were reported to be much higher than those for the earlier production lots;
24 however, the late production lots were estimated to account for only about 1% of the total
25 production volume of Aroclor 1254. Therefore, the data for the later production lots were not
26 included in the average TEQ calculation for Aroclor 1254 in Table 11-3.
27 Because of the wide variability in the reported results, the uncertainty associated with the
28 mean concentrations reported in Table 11-3 is very large.
29 In the environment, PCBs also occur as mixtures of congeners, but their composition
30 differs from those of the commercial mixtures because after release to the environment, the
31 composition of PCB mixtures changes over time through partitioning, chemical transformation,
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1 and preferential bioaccumulation (U.S. EPA, 1996g). Dioxin-like PCB congeners differ by up to
2 one to two orders of magnitude in their water solubility, vapor pressure, Kow value, and Henry's
3 Law constant. Thus, although all the dioxin-like PCB congeners are poorly soluble in water and
4 have very low vapor pressures, they will volatilize and leach at different rates. Similarly, because
5 the congeners differ somewhat in their rates of biodegradation, bioaccumulation, and
6 photodegradation, the congener patterns found in environmental media and biota will vary from
7 those found in commercial mixtures.
8 Although environmental mixtures are often characterized in terms of Aroclors, this
9 characterization can be both imprecise and inappropriate. Qualitative and quantitative errors can
10 arise from judgements in comparing GC/MS peaks for a sample with the characteristic peak
11 patterns for different Aroclors, particularly for environmentally altered patterns (U.S. EPA,
12 1996g). For the same reason, it can be both imprecise and inappropriate to infer concentrations
13 of dioxin-like PCB congeners in an environmental sample on the basis of characterization of the
14 sample's Aroclor content and knowledge of the dioxin-like congener content in the commercial
15 Aroclor. Safe (1994) wrote, "Regulatory agencies and environmental scientists have recognized
16 that the composition of PCBs in most environmental extracts does not resemble the compositions
17 of the commercial product." Similarly, ATSDR (1993) stated, "It is important to recognize that
18 the PCBs to which people may be exposed are likely to be different from the original PCB source
19 because of changes in congener and impurity composition resulting from differential partitioning
20 and transformation in the environment and differential metabolism and retention."
21
22 11.2.1. Approved PCB Disposal/Destruction Methods
23 In 1978, EPA began regulating the disposal of PCBs and PCB-contaminated waste under
24 TSCA, PL 94-469. The disposal regulations, published in the Code of Federal Regulations, 40
25 CFR, Part 761, state that the preferred disposal method is incineration at 1,200 °C or higher. If
26 the waste contains material that cannot be destroyed by incineration, EPA clearance must be
27 obtained to dispose of the waste in a chemical waste landfill or by another approved manner.
28 The PCB disposal regulations describe disposal of three distinct types of PCB waste:
29 PCBs, PCB articles (items containing PCBs), and PCB containers. Within these categories,
30 further distinctions are made on the basis of the PCB concentration in the waste. The acceptable
31 disposal methods are based on the PCB concentrations in the specific waste to be destroyed. The
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1 acceptable disposal methods are Annex I incinerators, high-efficiency boilers, Annex II chemical
2 waste landfills, and other approved methods. The following paragraphs and Table 11-4 provide
3 brief descriptions of these disposal methods. More complete descriptions of the specific
4 methodologies are provided in 40 CFR, Part 761.
5
6 11.2.1.1. Approved Incinerators/High-Efficiency Boilers
1 PCB Annex I incinerators must meet the specific technical standards and criteria listed in
8 Annex I of EPA's PCB regulations. The minimum operating requirements for disposal of liquid
9 wastes are 2 sec at 1,200 °C with 3% excess oxygen (measured in the stack gas) or 1.5 sec at
10 1,600 °C with 2% excess oxygen (measured in the stack gas). Monitoring requirements,
11 approval conditions, and trial burn requirements are prescribed in Annex I. Commercial or
12 industrial incinerators intending to destroy liquid PCB wastes must demonstrate compliance with
13 the Annex I requirements through a comprehensive trial burn program. Annex I incinerators
14 operating at optimum performance level should destroy 99.997% of liquid PCB waste, with a
15 resulting maximum emission factor of 0.03 g/kg.
16 Criteria for Annex I incinerators were established for the destruction of liquid PCB
17 wastes; however, these incinerators also may be used for disposal of nonliquid PCB items (such
18 as capacitors), provided that a destruction and removal efficiency of 99.9999% and a maximum
19 emission factor of 0.001 g/kg are met.
20 High-efficiency boilers may be used to destroy PCBs and PCB-contaminated waste with
21 PCB concentrations not exceeding 500 ppm. Conventional industrial and utility boilers may be
22 designated as high-efficiency boilers if they are operated under the prescribed combustion
23 conditions defined in the PCB disposal regulations. The PCB regulations do not specify a
24 minimum PCB destruction efficiency for high-efficiency boilers; however, EPA-approved boilers
25 operated according to the regulations have reported destruction efficiencies in excess of 99.99%,
26 with a corresponding maximum emission factor of 0.1 g/kg (U.S. EPA, 1987c).
27
28 11.2.1.2. Approved Chemical Waste Landfills
29 Approved chemical waste landfills can be used for the disposal of some, but not all, PCB
30 wastes. PCB-contaminated materials acceptable for land disposal in an approved landfill include
31 PCB mixtures (e.g., certain PCB-contaminated soil/solid debris, PCB-contaminated dredged
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1 materials, and PCB-contaminated municipal sewage sludge), PCB articles that cannot feasibly be
2 incinerated (e.g., drained and flushed transformers), and drained PCB containers. Written
3 approval must be obtained from EPA in order to landfill PCB articles other than transformers.
4 PCB-contaminated materials not acceptable for land disposal in an approved landfill include
5 nonliquid PCB mixtures in the form of contaminated soil, rags, or other solid debris, and sealed
6 capacitors. Typically, PCBs disposed of in these landfills are placed in sealed containers, thereby
7 minimizing any PCB emissions.
8
9 11.2.1.3. Other Approved Disposal Methods
10 Other thermal and nonthermal destruction techniques may be approved by EPA Regional
11 Administrators if these processes can effect destruction of PCBs equivalent to that of incinerators
12 or boilers. After April 29, 1983, all other PCB disposal technologies (thermal and nonthermal)
13 used in more than one EPA Region had to be approved by EPA Headquarters. Examples of
14 thermal technologies approved for commercial-scale use or for research and development
15 projects include a pyrolysis process to treat contaminated soils, a fluid wall reactor, a cement
16 kiln, a diesel engine, a steam-stripping operation, an aluminum melting furnace, and a molten salt
17 process. Examples of approved nonthermal processes include chemical dechlorination processes,
18 physical/chemical extraction techniques, and biological reduction methods. The
19 physical/chemical techniques extract the PCBs from transformers or capacitors and concentrate
20 them for disposal; they do not destroy the PCBs.
21
22 11.2.2. Emission Estimates
23 Table 11-5 lists the amounts of PCBs reported in EPA's TRI as transferred off-site for
24 treatment, energy recovery, or disposal between 1988 and 2000. These quantities do not
25 necessarily represent entry of PCBs into the environment. If it is assumed that all transferred
26 PCBs are incinerated in high-efficiency boilers with a destruction and removal efficiency of
27 99.99%, then annual emissions of PCBs to air during 1988, 1995, and 2000 could have been as
28 high as 264 kg, 31 kg, and 15 kg, respectively. Because no stack testing data are available for
29 dioxin-like PCBs, it is not possible to estimate what fraction of these potential PCB releases
30 would have been the dioxin-like congeners.
31
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1 11.2.3. Accidental Releases of In-Service PCBs
2 After the 1977 ban on production of PCBs, releases of commercially produced PCBs to
3 the environment (aside from minimal releases occurring during approved disposal and/or
4 destruction) have been limited to accidental release of in-service PCBs (U.S. EPA, 1987c).
5 Accidental releases are the result of leaks or spills during failure/breakage of an existing piece of
6 PCB-containing equipment or of incomplete combustion during accidental fires involving PCB-
7 containing equipment. These two types of accidental releases are discussed in the following
8 subsections.
9
10 11.2.3.1. Leaks and Spills
11 PCBs that remain in active service at this time are those contained in "closed systems"
12 (i.e., those pieces of electrical equipment that completely enclose the PCBs and do not provide
13 direct atmospheric access of the PCBs during normal use). This equipment includes PCB
14 transformers, capacitors, voltage regulators, circuit breakers, and reclosures. With the exception
15 of PCB transformers and probably small PCB capacitors, the majority of the PCB-containing
16 electrical equipment in service during 1981 was owned by the electrical utility industry.
17 Approximately 70% of the estimated 140,000 PCB transformers in service in 1981 were owned
18 by nonutilities. No information was available on the relative distribution of small PCB
19 capacitors (Versar, Inc., 1988).
20 The number of each of these items owned by the utility industry, the quantity of PCBs
21 contained in each, and an estimate of the annual quantity of PCBs leaked and/or spilled were
22 investigated by the Edison Electric Institute and the Utility Solid Wastes Activity Group
23 (EEI/USWAG) for EPA in 1981. The findings of this investigation, which were reported in a
24 proposed modification to the PCB regulations (Federal Register, 1982a), indicated that more than
25 99% of the total quantity of PCBs contained in utility-owned electrical equipment in 1981
26 (73,700 metric tons) was in 40,000 PCB transformers (those containing >500 ppm of PCBs) and
27 large PCB capacitors (those containing >3 Ib of PCBs). An upper-bound estimate of the mass of
28 PCBs that leached or spilled from this equipment in 1981 was 177 metric tons. Approximately
29 95% of the estimated releases were the result of leaks from large PCB capacitors (Federal
30 Register, 1982a). Leaks/spills typically occur in transformers when the gasket joining the top to
31 the body corrodes, tears, or physically fails. PCBs can then leak past this failed section and
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1 potentially spill onto the surrounding ground. PCB capacitors typically fail by rupturing,
2 exposing the contained PCBs to the environment. Failure is caused by environmental and
3 weathering effects (e.g., lightning) or material failures (e.g., metal fatigue).
4 As of mid-1988, the total population of in-service PCB transformers and large PCB
5 capacitors was estimated to have decreased from 140,000 to 110,000 and from 3.3 million to 1.9
6 million, respectively (Versar, Inc., 1988). PCB transformers have normal operating lifetimes of
7 30 years and 40 years, respectively. The accelerated retirement rate over this 7-yr period was
8 attributed to EPA's PCB Electrical Use Rule (Federal Register, 1982b), which required the
9 removal of 950 food/feed industry transformers by 1985 and removal of 1.1 million unrestricted-
10 access large PCB capacitors by October 1988. In addition, EPA's PCB Transformer Fires Rule
11 (Federal Register, 1985b) required the removal by 1990 of 7,600 480-volt network transformers.
12 More recent inventories of PCB-containing electrical equipment are not available.
13 However, an Information Collection Request submitted by EPA to the Office of Management
14 and Budget for information on uses, locations, and conditions of PCB electrical equipment
15 estimated that there may be 150,000 owners of PCB-containing transformers used in industry,
16 utilities, government buildings, and private buildings (Federal Register, 1997a). It is expected,
17 and is demonstrated by the reported PCB transfers in the EPA's TRI (see Table 11-5), that many
18 owners of PCB electrical equipment have removed PCB-containing equipment to eliminate
19 potential liability.
20
21 11.2.3.2. Accidental Fires
22 The available information is not adequate to support an estimate of potential annual
23 releases of dioxin-like PCBs from accidental electrical equipment fires. For fires involving PCB
24 transformers or capacitors, the amount of PCBs released is dependent on the extensiveness of the
25 fire and the speed at which it is extinguished. A number of these fires are documented. A New
26 York fire involving 200 gallons of transformer fluid containing some 65% by weight PCBs
27 resulted in a release of up to 1,300 pounds of PCBs. A capacitor fire that burned uncontrolled for
28 2 hr in Sweden resulted in the destruction of 12 large utility capacitors containing an estimated
29 25 pounds each of PCBs, for a total potential release of 300 pounds. However, data are
30 incomplete on the exact amount of PCBs released as a result of these two fires.
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1 EPA has imposed reporting requirements to ensure that the National Response Center is
2 informed immediately of fires involving PCB transformers (40 CFR 761). The recordkeeping
3 requirements are used to document the use, location, and condition of PCB equipment.
4 Responses are mandatory but may be claimed by the submitter to be confidential information.
5 The annual number of PCB transformer fires is estimated at approximately 20 per year; the
6 number of PCB capacitor fires is unknown (U.S. EPA, 1987c). As these PCB-containing items
7 reach the end of their useful lives and are retired, their susceptibility to fires will be eliminated,
8 and the overall number of PCB transformer and capacitor fires will be reduced.
9
10 11.2.4. Municipal Wastewater Treatment
11 EPA conducted the National Sewage Sludge Survey in 1988 and 1989 to obtain national
12 data on sewage sludge quality and management. As part of this survey, EPA analyzed sludges
13 from 175 publicly owned treatment works (POTWs) that employed at least secondary wastewater
14 treatment for more than 400 analytes, including seven of the Aroclors. Sludges from 19% of the
15 POTWs had detectable levels of at least one of the following Aroclors: 1248, 1254, or 1260;
16 none of the other Aroclors were detected in any sample (detection limit was typically about 200
17 pg/kg dry weight) (U.S. EPA, 1996a). Analyses were not performed for dioxin-like PCB
18 congeners. The Aroclor-specific results of the survey are presented in Table 11-7.
19 Gutenmann et al. (1994) reported similar results in a survey of sludges from 16 large U.S.
20 cities for Aroclor 1260 content. At a detection limit of 250 |_ig/kg (dry weight), the investigators
21 detected Aroclor 1260 at only one facility (4,600 |ig/kg). These results indicate that PCBs are
22 not likely to be formed at POTWs, but rather are present because of disposal of PCB products or
23 recirculation of previously disposed PCB.
24 Although PCBs, measured as Aroclors, were not commonly detected in sewage sludge at
25 Pg/kg levels by U.S. EPA (1996a) and Gutenmann et al. (1994), the presence of dioxin-like PCB
26 congeners at lower concentrations may be more common. Green et al. (1995) and Cramer et al.
27 (1995) reported the results of analyses of 99 samples of sewage sludge for PCB congener
28 numbers 77, 81, 126, and 169. The sludge samples were collected from 74 wastewater treatment
29 plants across the United States during the summer of 1994. These data are summarized in Table
30 11-8. Results from all samples collected from the same facility were averaged by Green et al.
31 (1995) and Cramer et al. (1995) to ensure that results were not biased towards the concentrations
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1 found at facilities from which more than one sample was collected. If all nondetect values are
2 assumed to be zero, then the POTW mean TEQP-WHO94 and TEQP-WHO98 concentrations were
3 25.1 and 24.2 ng TEQ/kg (dry-weight basis), respectively. If the nondetect values are set equal to
4 the detection limits, then the POTW mean TEQP-WHO94 and TEQP-WHO98 concentrations were
5 25.2 and 24.3 ng TEQ/kg, respectively.
6 In 1999, sewage sludge samples from a POTW in Ohio were collected and analyzed for
7 PCBs (U.S. EPA, 2000f). The facility, which accepts both domestic and industrial wastewater,
8 employs secondary wastewater technology. Assuming nondects are zero, the mean TEQ
9 emission factor is 141 ng TEQP-WHO98/kg. These results are presented in Table 11-9.
10 In 2000 and 2001, the Association of Metropolitan Sewage Agencies conducted a survey
11 of dioxin-like PCB compounds in sewage sludge (Alvarado et al., 2001). A total of 200 sewage
12 sludge samples were collected from 171 POTWs located in 31 states. Assuming nondetects are
13 zero, the mean and median TEQ emission factors were reported as 8.3 and 3.37 ng TEQP-
14 WHO98/kg, respectively.
15 For 2001, EPA conducted another National Sewage Sludge Survey to characterize the
16 dioxin and dioxin-like equivalence levels in biosolids produced by the 6,857 POTWs operating
17 in the United States in 2001 (U.S. EPA, 2002a). Sewage sludge samples were collected from 94
18 POTWs that used secondary or higher treatment practices. All the facilities had been sampled as
19 part of the 1988/1989 National Sewage Sludge Survey. To determine the mean and median TEQ
20 emission estimates of the dioxin-like PCBs, EPA weighted the values on the basis of wastewater
21 flow rates of all POTWs in the United States (i.e., number of facilities with wastewater flow rate
22 >100 mg/day, >10 but < 100 mg/day, >1 but < 10 mg/day, and < 1 mg/day). The weighted mean
23 and median TEQP-WHO98 concentrations of the dioxin-like PCB congeners were 5.22 and 2.05
24 ng/kg, respectively.
25 According to the results of its 1988/1989 National Sewage Sludge Survey, EPA estimated
26 that approximately 5.4 million dry metric tons of sewage sludge were generated in 1989 (Federal
27 Register, 1993b). EPA also used the results of the 1984 to 1996 Clean Water Needs Surveys to
28 estimate that 6.3 million dry metric tons of sewage sludge were generated in 1998 and 6.6
29 million dry metric tons were generated in 2000 (U.S. EPA, 1999). Because estimates for 1987
30 and 1995 are not available, the 1989 and 1998 activity level estimates are used for reference
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1 years 1987 and 1995, respectively. Tables 11-10, 11-11, and 11-12 list the volume, by use and
2 disposal practices, of sludge disposed of annually for reference years 1989, 1995, and 2000.
3 These tables also list the estimated amount of dioxin-like PCB TEQs that may be present
4 in sewage sludge and potentially released to the environment. For reference years 1987 and
5 1995, these values were estimated using the POTW mean TEQP-WHO98 concentration calculated
6 from the results reported by Green et al. (1995) and Cramer et al. (1995). For reference year
7 2000, they were estimated using the POTW mean TEQP-WHO98 concentration reported by EPA
8 (U.S. EPA, 2002a) as part of the 2001 National Sewage Sludge Survey. Multiplying these TEQ
9 concentrations by the sludge volumes generated yields annual potential total releases of 101 g
10 TEQP-WHO98 (104.2 g TEQP-WHO94) in 1987, 118.5 g TEQP-WHO98 (123.1 g TEQP-WHO94) in
11 1995, and 26.6 g TEQP-WHO98 in 2000 for nonincinerated sludges.
12 Of the 101 g TEQP-WHO98 released in 1987, 1.7 g entered commerce as a product for
13 distribution and marketing, and the remainder was applied to land (41.5 g to land application and
14 9.6 g to surface disposal sites) or landfilled (48.2 g). Of the 118.5 g TEQP-WHO98 released in
15 1995, 60.5 g were applied to land without further processing or stabilization, 16.9 g underwent
16 advanced treatment such as composting, 26.6 g were disposed of on the surface or landfilled, and
17 the remainder was either used or disposed of in other ways. Of the 26.6 g TEQP-WHO98 released
18 in 2000, 14.6 g were applied to land without further processing or stabilization, 4.2 g underwent
19 advanced treatment such as composting, 4.7 g were disposed of on the surface or landfilled, and
20 the remainder was either used or disposed of in other ways. The PCBs in landfilled sludge were
21 not considered releases to the environment per the definition established in this document. The
22 other disposal practices were considered releases and were summed to get total land releases as
23 shown in Table 11-2.
24 The 1987 and 1995 release estimates are assigned a confidence rating of B, indicating
25 high confidence in the production estimate and medium confidence in the emission factor
26 estimates. The medium rating was based on the judgment that, although the 74 facilities tested
27 by Green et al. (1995) and Cramer et al. (1995) may be reasonably representative of the
28 variability in POTW technologies and sewage characteristics nationwide, the sample size was
29 still relatively small, and not all dioxin-like PCB congeners were monitored. The 2000 release
30 estimates are assigned a confidence rating of A, indicating high confidence in both the
31 production estimate and the emission factor estimates. High confidence was placed in the
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1 emission factors estimated because the emission factors were weighted on the basis of
2 wastewater flow rates of all POTWs in the United States.
3
4 11.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES
5 In the early 1980s, EPA investigated the extent of inadvertent generation of PCBs during
6 the manufacture of synthetic organic chemicals (Hammerstrom et al., 1985). For example,
7 phthalocyanine dyes and diarylide pigments were reported to contain PCBs in the mg/kg range.
8 EPA subsequently issued regulations under TSCA (40 CFR 761.3) that ban the distribution in
9 commerce of any products containing an annual average PCB concentration of 25 mg/kg (50
10 nig/kg maximum concentration at any time). In addition, EPA requires manufacturers with
11 processes that inadvertently generate PCBs and importers of products that contain inadvertently
12 generated PCBs to report to EPA any process or import for which the PCB concentration is
13 greater than 2 mg/kg for any resolvable PCB gas chromatographic peak.
14
15 11.4. COMBUSTION SOURCES
16 11.4.1. Municipal Waste Combustors
17 Municipal waste combustors (MWCs) have long been identified as potential PCB air
18 emission sources. Stack gas concentrations of PCBs for three MWCs were reported (U.S. EPA,
19 1987c); the average test results yielded an emission factor of 18 |_ig PCBs/kg refuse. Stack gas
20 emissions of PCBs from the three MWCs were quantified without determining the MWCs' PCB
21 destruction efficiency.
22 EPA also analyzed the PCB content of various consumer paper products (U.S. EPA,
23 1987c). The results indicated that paper products such as magazine covers and paper towels
24 contained up to 139 pg/kg of paper. These levels, which were reported in 1981, were attributed
25 to the repeated recycling of waste paper containing PCBs. For example, carbonless copy paper
26 manufactured prior to 1971 contained PCB levels as high as 7%. This copy paper then became a
27 component of waste paper, which was recycled. The PCBs were inevitably introduced into other
28 paper products, resulting in continued measurable levels in municipal refuse some four years
29 after the PCB manufacturing ban was imposed. RDF manufactured from these paper products
30 had PCB levels of 8,500 pg/kg, indicating that this fuel could be a source of atmospheric PCBs.
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1 Therefore, it was assumed that municipal refuse does contain detectable levels of PCBs and that
2 some of these PCBs may enter the atmosphere when the refuse is incinerated (U.S. EPA, 1987c).
3 Shane et al. (1990) analyzed fly ash from five MWCs for PCB congener group content.
4 Total PCB levels ranged from 99 to 322 |_ig/kg in the ash, with the tri-, tetra-, and penta-congener
5 groups occurring in the highest concentrations. The investigators also analyzed seven bottom ash
6 and eight bottom ash/fly ash mixtures for total PCB measured as Aroclor 1254. The detection
7 limit for this Aroclor analysis was 5 pg/kg. Aroclor 1254 was detected in two of the seven
8 bottom ash samples (26 and 8 pg/kg) and in five of the eight fly ash/bottom ash mixtures (range
9 of 6 to 33 i-ig/kg).
10 Sakai et al. (2001) analyzed the PCB levels in fly ash and bottom ash from a newly
11 constructed MWC in Japan. The I-TEQ values derived from the data give a total TEQ value of
12 31.6 ng/kg for fly ash and 0.85 ng/kg for bottom ash.
13 The development of more sensitive analytical methodologies has enabled researchers in
14 recent years to detect dioxin-like PCB congeners in the stack gases and fly ash from full-scale
15 and pilot-scale MWCs (Sakai et al., 1993a, b, 1994, 2001; Boers et al., 1993; Schoonenboom et
16 al., 1993). Similarly, the advances in analytical techniques have enabled researchers to determine
17 that dioxin-like PCBs can be formed during the oxidative solid combustion phase of incineration,
18 presumably due to dimerization of chlorobenzenes. Laboratory-scale studies have also
19 demonstrated that dioxin-like PCBs can be formed from heat treatment of fly ash in air
20 (Schoonenboom et al., 1993; Sakai et al., 1994); however, the available data are not adequate to
21 support development of a quantitative estimate of a dioxin-like PCB emission factor for this
22 source category.
23
24 11.4.2. Industrial Wood Combustion
25 Emissions of PCB congener groups (but not individual congeners) were measured during
26 stack testing at two industrial wood-burning facilities (CARB, 1990e, f). Table 11-13 presents
27 the average of the congener group (mono- through decachlorobiphenyl) emission factors for these
28 two facilities. No tetra- or more-highly chlorinated congeners (the congener groups containing
29 the dioxin-like PCBs) were detected at either facility at detection limits corresponding to
30 emission factors in the low range of ng/kg of wood combusted.
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1 In CARB (1990e), PCBs were measured in the emissions from two spreader stoker wood-
2 fired boilers operated in parallel by an electric utility for generating electricity. The exhaust gas
3 stream from each boiler was passed through a dedicated electrostatic precipitator (ESP), after
4 which the gas streams were combined and emitted to the atmosphere through a common stack.
5 Stack tests were conducted both when the facility burned fuels allowed by existing permits and
6 when the facility burned a mixture of permitted fuel supplemented by urban wood waste at a ratio
7 of70:30.
8 In CARB (1990f), PCBs were measured in the emissions from twin fluidized-bed
9 combustors designed to burn wood chips to generate electricity. The air pollution control device
10 (APCD) system consisted of ammonia injection for controlling nitrogen oxides and a multiclone
11 and an ESP for controlling PM. During testing, the facility burned wood wastes and agricultural
12 wastes allowed by existing permits.
13
14 11.4.3. Medical Waste Incineration
15 As discussed in Section 3.3, EPA has issued nationally applicable emission standards and
16 guidelines that address CDD/CDF emissions from medical waste incinerators (MWIs). Although
17 PCBs are not addressed in these regulations, the database of stack test results at MWIs compiled
18 for this rulemaking does contain limited data on PCB congener group emission factors. Data are
19 available for two MWIs lacking add-on APCD equipment and for two MWIs with add-on APCD
20 equipment in place. The average congener group emission factors derived from these test data
21 are presented in Table 11-14. Because data are available for only 4 of the estimated 1,065
22 facilities that make up this industry, and because these data do not provide congener-specific
23 emission factors, no national estimates of total PCB or dioxin-like PCB emissions are being
24 made at this time.
25
26 11.4.4. Tire Combustion
27 As discussed in Section 3.6, tires are burned in a variety of facilities including dedicated
28 tire burners, cement kilns, industrial boilers, and pulp and paper combustion facilities. Emissions
29 of PCB congener groups (but not individual congeners) were measured during stack testing of a
30 tire incinerator (CARB, 199 la). The facility consisted of two excess air furnaces equipped with
31 steam boilers to recover the energy from the heat of combustion. Discarded whole tires were fed
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1 to the incineration units at rates ranging from 2,800 to 5,700 kg/hr during the 3 testing days. The
2 furnaces were equipped to burn natural gas as auxiliary fuel. The steam produced from the
3 boilers drove electrical turbine generators that produced 14.4 megawatts of electricity. The
4 facility was equipped with a dry acid gas scrubber and a fabric filter for the control of emissions
5 prior to exiting the stack. Table 11-15 presents the congener group (mono- through
6 decachlorobiphenyl) emission factors for this facility. The emission factor for the total of the
7 tetra- through heptachlorinated congener groups was about 1.2 pg/kg of tire processed. Because
8 these data do not provide PCB congener-specific emission factors, no estimates of emissions of
9 dioxin-like PCBs can be made.
10
11 11.4.5. Cigarette Smoking
12 Using high-resolution mass spectrometry, Matsueda et al. (1994) analyzed tobacco from
13 20 brands of commercially available cigarettes collected in 1992 from Japan, the United States,
14 Taiwan, China, the United Kingdom, Germany, and Denmark for the PCB congeners 77, 126,
15 and 169. Table 11-16 presents the results of the study. However, no studies that examined the
16 tobacco smoke for the presence of these congeners have been reported. Thus, it is not known
17 whether the PCBs present in the tobacco are destroyed or volatilized during combustion or
18 whether PCBs are formed during combustion.
19 The combustion processes operating during cigarette smoking are complex and could be
20 used to support either of these potential mechanisms. As reported by Guerin et al. (1992), during
21 a puff, gas phase temperatures reach 850 °C at the core of the firecone, and solid phase
22 temperatures reach 800 °C at the core and 900 °C or greater at the char line. Thus, temperatures
23 are sufficient to cause at least some destruction of CDDs/CDFs initially present in the tobacco.
24 Both solid and gas phase temperatures rapidly decline to 200 to 400 °C within 2 mm of the char
25 line. Formation of dioxin-like PCBs has been reported in combustion studies with other media in
26 this temperature range (Sakai et al., 1994). However, it is known that a process likened by
27 Guerin et al. (1992) to steam distillation takes place in the region behind the char line because of
28 high localized concentrations of water and temperatures of 200 to 400 °C. At least 1,200 tobacco
29 constituents (e.g., nicotine, n-paraffin, some terpenes) are transferred intact from the tobacco into
30 the smoke stream by distillation in this area, and it is plausible that PCBs present in the unburned
31 tobacco would be subject to similar distillation.
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1 Brown et al. (2002) estimated that 440 billion cigarettes were consumed in the United
2 States in 2000. In 1995, approximately 487 billion cigarettes were consumed in the United States
3 and by U.S. Armed Forces personnel stationed overseas. In 1987, approximately 575 billion
4 cigarettes were consumed. According to the Tobacco Institute (1995), per capita U.S. cigarette
5 consumption, based on total U.S. population aged 16 years and over, was at a record high of
6 4,345 in 1963, declining to 2,415 in 1995, and 1,563 in 2000 (USDA, 1997; U.S. Census Bureau,
7 2000). The activity level estimates by Brown et al. (2002) were adopted here and assigned a high
8 confidence rating because they were based on well established rates of consumption.
9 A preliminary rough estimate of potential emissions of dioxin-like PCBs can be made
10 using the following assumptions: (a) the average TEQP-WHO98 content of seven brands of U.S.
11 cigarettes reported by Matsueda et al. (1994), 0.64 pg/pack (0.032 pg/cigarette), is representative
12 of cigarettes smoked in the United States; (b) dioxin-like PCBs are neither formed nor destroyed,
13 and the congener profile reported by Matsueda et al. (1994) is not altered during combustion of
14 cigarettes; and (c) all dioxin-like PCBs contributing to the TEQ are released from the tobacco
15 during smoking. On the basis of these assumptions, the calculated annual emissions would be
16 0.018 g TEQP-WHO98, 0.016 g TEQP-WHO98, and 0.014 g TEQP-WHO98 for reference years
17 1987, 1995, and 2000, respectively.
18
19 11.4.6. Sewage Sludge Incineration
20 EPA derived an emission factor of 5.4 |_ig of total PCBs per kg of dry sewage sludge
21 incinerated (U.S. EPA, 1996f). This emission factor was based on measurements conducted at
22 five multiple-hearth incinerators controlled with wet scrubbers. However, it is not known what
23 fraction of the emissions was dioxin-like PCBs.
24 In 1999, stack tests were conducted at a multiple-hearth incinerator in Ohio equipped
25 with a venturi scrubber and a three-tray impingement conditioning tower (U.S. EPA, 2000f).
26 Four test runs were conducted; however, the first test run was aborted, and the CDD/CDF results
27 from the fourth test run were determined to be statistical outliers (p<0.05). The back-half
28 emission concentrations for test run 4 were 50 to 60% lower than back-half emission
29 concentrations for test runs 2 and 3. Overall, total CDD/CDF emissions measured during test run
30 4 were 73.3 ng/kg, whereas those measured during test runs 2 and 3 were 215 and 173 ng/kg,
31 respectively. It could not be determined whether the lower concentrations associated with test
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1 run 4 were due to analyte loss or whether they represented an accurate reflection of a change in
2 incinerator emission releases. The average TEQ emission factor, excluding test run 4, was 0.51
3 ng TEQP-WHO98/kg (see Table 11-17). This emission factor was assigned a low confidence
4 rating because it is based on limited surveys that are judged to be possibly nonrepresentative.
5 In 1988, approximately 199 sewage sludge incineration facilities combusted about 0.865
6 million metric tons of dry sewage sludge (Federal Register, 1993b). In 1995, approximately 257
7 sewage sludge incinerators (some of which were backup or alternate incinerators) combusted
8 about 2.11 million dry metric tons of sewage sludge (Maw, 1998). Using trends in wastewater
9 flow rates from the 1988 National Sewage Sludge Survey and from the 1984 to 1996 Needs
10 Surveys, EPA estimated that in 2000 approximately 6.4 million metric tons of dry sewage sludge
11 would have been generated (U. S. EPA, 1999). Of this amount, EPA proj ected that 22% (1.42
12 million metric tons) would have been incinerated. These activity estimates were assigned a
13 confidence rating of medium because they were based on surveys judged to be representative of
14 sludge generation rates.
15 Using the above estimated amounts of sewage sludge incinerated per year and the average
16 TEQ emission factor of 0.51 ng TEQP-WHO98/kg, the estimated annual releases of total PCBs to
17 air were 0.44 g TEQP-WHO98 in 1987, 1.1 g TEQP-WHO98 in 1995, and 0.72 g TEQP-WHO98 in
18 2000. These emissions were assigned a low confidence rating because the emission factor was
19 given a low rating.
20
21 11.4.7. Backyard Barrel Burning
22 The low combustion temperatures and oxygen-starved conditions associated with
23 backyard barrel burning may result in incomplete combustion and increased pollutant emissions
24 (Lemieux, 1997). EPA's Control Technology Center, in cooperation with New York State's
25 departments of health and environmental conservation, conducted a study to examine,
26 characterize, and quantify emissions from the simulated open burning of household waste
27 materials in barrels (Lemieux, 1997). A representative waste to be burned was prepared on the
28 basis of the typical percentages of various waste materials disposed of by New York State
29 residents (i.e., nonavid recyclers); hazardous wastes such as chemicals, paints, and oils were not
30 included in the test waste. A variety of compounds, including dioxin-like PCBs, were measured
31 in the emissions from the simulated open burning. The measured TEQ emission factors for
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1 waste that had not been separated for recycling purposes were 1.02 * 10"2 \ig TEQP-WHO94/kg
2 and 5.26 x 10"3 |_ig TEQP-WHO98/kg of waste burned (see Table 11-18). These limited emissions
3 data were judged to be inadequate for estimating national emissions. The activity level for
4 backyard barrel burning is discussed in Section 6.5.
5
6 11.4.8. Petroleum Refining Catalyst Regeneration
7 As discussed in Section 5.3, regeneration of spent catalyst used in catalytic reforming to
8 produce high-octane reformates is a potential source of CDD/CDF air emissions. In 1998,
9 emissions from the caustic scrubber used to treat gases from the external catalyst regeneration
10 unit of a refinery in California were tested for CDDs/CDFs as well as PCB congener groups
11 (CARB, 1999). This facility uses a continuous regeneration process. The reactor is not taken off
12 line during regeneration; rather, small amounts of catalyst are continuously withdrawn from the
13 reactor and regenerated. The emissions from the regeneration unit are neutralized by a caustic
14 scrubber before being vented to the atmosphere. The catalyst recirculation rate during the three
15 tests ranged from 733 to 1,000 Ib/hr.
16 All PCB congener groups were detected in each of the three samples collected. The
17 average congener group emission factors in units of ng per barrel of reformer feed are presented
18 in Table 11-19. The total PCB emission factor was 118 ng/barrel. This emission factor assumes
19 that emissions are proportional to reforming capacity; emission factors may be more related to
20 the amount of coke burned, APCD equipment present, and/or other process parameters.
21 Because emissions, data are available for only one U.S. petroleum refinery (which
22 represents less than 1% of the catalytic reforming capacity at U.S. refineries), and because these
23 data do not provide congener-specific emission factors, no national estimates of total PCB or
24 dioxin-like PCB emissions are being made at this time.
25
26 11.5. NATURAL SOURCES
27 This section discusses biotransformation and photochemical transformation of other
28 PCBs. While there is some evidence that these processes occur, the data were considered
29 insufficient for developing release estimates.
30
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1 11.5.1. Biotransformation of Other PCBs
2 Studies show that under anaerobic conditions, biologically mediated reductive
3 dechlorination to less-chlorinated congeners, followed by slow anaerobic and/or aerobic
4 biodegradation, is a major pathway for destruction of PCBs in the environment. Research
5 reported to date and summarized below indicates that biodegradation should result in a net
6 decrease rather than a net increase in the environmental load of dioxin-like PCBs.
7 Laboratory studies (e.g., Bedard et al., 1986; Pardue et al., 1988; Larsson and
8 Lemkemeier, 1989; Hickey, 1995; Schreiner et al., 1995) have revealed that more than two dozen
9 strains of aerobic bacteria and fungi that are capable of degrading most PCB congeners with five
10 or fewer chlorines are widely distributed in the environment. Many of these organisms are of the
11 genus Pseudomonas or Alcaligenes. The maj or metabolic pathway involves addition of oxygen
12 at the 2,3-position by a dioxygenase enzyme, with subsequent dehydrogenation to the catechol
13 followed by ring cleavage. Several bacterial strains have been shown to possess a dioxygenase
14 enzyme that attacks the 3,4-position.
15 Only a few strains have demonstrated the ability to degrade hexa- and more chlorinated
16 PCBs. The rate of aerobic biodegradation decreases with increasing chlorination. The half-lives
17 for biodegradation of tetra-PCBs in fresh surface water and soil are 7 to 60+ days and 12 to 30
18 days, respectively. For penta- and more-highly chlorinated PCBs, the half-lives in fresh surface
19 water and soil are likely to exceed 1 year. PCBs with all or most chlorines on one ring and PCBs
20 with fewer than two chlorines in the ortho position tend to degrade more rapidly. For example,
21 Gan and Berthouex (1994) monitored over a 5-yr period the disappearance of PCB congeners
22 applied to soil with sewage sludge. Three of the tetra- and pentachlorinated dioxin-like PCBs
23 (IUPAC Nos. 77, 105, and 118) followed a first-order disappearance model, with half-lives
24 ranging from 43 to 69 months. A hexa-substituted congener (IUPAC No. 167) and a hepta-
25 substituted congener (IUPAC No. 180) showed no significant loss over the 5-yr period.
26 Prior to the early 1990s, little investigation focused on anaerobic microbial dechlorination
27 or degradation of PCBs, even though most PCBs, eventually accumulate in anaerobic sediments
28 (Abramowicz, 1990; Risatti, 1992). Environmental dechlorination of PCBs via losses of meta
29 and para chlorines has been reported in field studies for freshwater, estuarine, and marine
30 anaerobic sediments, including those from the Acushnet Estuary, the Hudson River, the
31 Sheboygan River, New Bedford Harbor, Escambia Bay, Waukegan Harbor, the Housatonic
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1 River, and Woods Pond (Brown et al., 1987; Rhee et al., 1989; Van Dort and Bedard, 1991;
2 Abramowicz, 1990; Bedard et al., 1995; Bedard and May, 1996). The altered PCB congener
3 distribution patterns found in these sediments (i.e., different patterns with increasing depth or
4 distance from known sources of PCBs) have been interpreted as evidence that bacteria may
5 dechlorinate PCBs in anaerobic sediment.
6 Reported results of laboratory studies confirm anaerobic degradation of PCBs. Chen et
7 al. (1988) found that "PCB-degrading" bacteria from the Hudson River could significantly
8 degrade the mono-, di-, and tri-PCB components of a 20 ppm Aroclor 1221 solution within 105
9 days. These congener groups make up 95 percent of Aroclor 1221. No degradation of more-
10 highly chlorinated congeners (present at 30 ppb or less) was observed, and a separate 40-day
11 experiment with tetra-PCB also showed no degradation.
12 Rhee et al. (1989) reported degradation of mono- to penta-substituted PCBs in
13 contaminated Hudson River sediments held under anaerobic conditions in the laboratory (N2
14 atmosphere) for 6 months at 25 °C. Amendment of the test samples with biphenyl resulted in
15 greater loss of PCBs. No significant decreases in the concentrations of the more highly
16 chlorinated congeners (more than five chlorines) were observed. No evidence of degradation
17 was observed in samples incubated in CO2/H2 atmospheres. Abramowicz (1990) hypothesized
18 that this result could be an indication that, in the absence of CO2, a selection is imposed favoring
19 organisms capable of degrading PCBs to obtain CO2 and/or low-molecular-weight metabolites as
20 electron receptors.
21 Risatti (1992) examined the degradation of PCBs at varying concentrations (10,000 ppm,
22 1,500 ppm, and 500 ppm) in the laboratory with "PCB-degrading" bacteria from Waukegan
23 Harbor. After 9 months of incubation at 22 °C, the 500 ppm and 1,500 ppm samples showed no
24 change in PCB congener distributions or concentrations, thus indicating a lack of degradation.
25 Significant degradation was observed in the 10,000 ppm sediment, with at least 20 congeners
26 ranging from TrCBs to PeCBs showing decreases.
27 Quensen et al. (1988) also demonstrated that microorganisms from PCB-contaminated
28 sediments (Hudson River) dechlorinated most tri- through hexa-PCBs in Aroclor 1242 under
29 anaerobic laboratory conditions. The Aroclor 1242 used to spike the sediment contained
30 predominantly tri- and tetra-PCBs (85 mol percent). Three concentrations of the Aroclor,
31 corresponding to 14, 140, and 700 ppm on a sediment dry-weight basis, were used.
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1 Dechlorination was most extensive at the 700 ppm test concentration: 53% of the total chlorine
2 was removed in 16 weeks, and the proportion of TeCBs through HxCBs decreased from 42 to
3 4%. Much less degradation was observed in the 140 ppm sediment, and no observable
4 degradation was found in the 14 ppm sediment. These results and those of Risatti (1992) suggest
5 that the organism(s) responsible for this dechlorination may require relatively high levels of
6 PCBs as a terminal electron acceptor to maintain a growing population.
7 Quensen et al. (1990) reported that dechlorination of 500 ppm spike concentrations of
8 Aroclor 1242, 1248, 1254, and 1260 by microorganisms from PCB-contaminated sediments in
9 the Hudson River and Silver Lake occurred primarily at the meta- and para- positions; ortho-
10 substituted mono- and di-PCBs increased in concentration. Significant decreases over the
11 incubation period (up to 50 weeks) were reported for dioxin-like PCBs 156, 167, 170, 180, and
12 189. Of the four dioxin-like TeCBs and PeCBs detected in the Aroclor spikes (IUPAC Nos. 77,
13 105, 114, and 118), all decreased significantly in concentration, with the possible exception of
14 PeCB 114 in the Aroclor 1260-spiked sediment.
15 Nies and Vogel (1990) reported similar results with Hudson River sediments incubated
16 anaerobically and enriched with acetone, methanol, or glucose. Approximately 300 ppm of
17 Aroclor 1242 (31 mol percent TeCBs, 7 mol percent PeCBs, and 1 mol percent HxCBs) were
18 added to the sediments prior to incubation for 22 weeks under an N2 atmosphere. Significant
19 dechlorination was observed, primarily at the meta- and para-positions on the more highly
20 chlorinated congeners (TeCBs, PeCBs, and HxCBs), resulting in the accumulation of less-
21 chlorinated, primarily ortho-substituted mono- through tri-substituted congeners. No significant
22 dechlorination was observed in the control samples (samples containing no added organic
23 chemical substrate and samples that were autoclaved).
24 Bedard and May (1996) also reported similar findings in the sediments of Woods Pond,
25 which was believed to be contaminated with Aroclor 1260. Significant decreases in the sediment
26 concentrations of PCBs 118, 156, 170, and 180 (relative to their concentrations in Aroclor 1260)
27 were observed. No increases or decreases were reported for the other dioxin-like PCBs.
28 Bedard et al. (1995) demonstrated that it is possible to stimulate substantial microbial
29 dechlorination of the highly chlorinated PCB mixture Aroclor 1260 in situ with a single addition
30 of 2,6-dibromobiphenyl. The investigators added 365 g of 2,6-dibromobiphenyl to 6-foot-
31 diameter submerged caissons containing 400 kg sediment (dry weight) and monitored the change
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1 in PCB congener concentrations for a period of 1 yr. At the end of the observation period, the
2 hexa- through monochlorinated PCBs decreased 74% in the top of the sediment and 69% in the
3 bottom. The average number of chlorines per molecule dropped 21%, from 5.83 to 4.61, with
4 the largest reduction observed in meta-chlorines (54% reduction) followed by para-chlorines
5 (6%). The dechlorination stimulated by 2,6-dibromobiphenyl selectively removed meta-
6 chlorines positioned next to other chlorines.
7 The findings of these latter studies are significant, because removal of meta- and para-
8 chlorines from the dioxin-like PCBs should reduce their toxicity and bioaccumulative potential
9 and also form less-chlorinated congeners that are more amenable to aerobic biodegradation.
10 Van Dort and Bedard (1991) reported the first experimental demonstration of biologically
11 mediated ortho-dechlorination of a PCB and stoichiometric conversion of that PCB congener
12 (2,3,5,6-TeCB) to less-chlorinated forms. In that study, 2,3,5,6-TeCB was incubated under
13 anaerobic conditions with unacclimated methanogenic pond sediment for 37 weeks, with
14 reported dechlorination to 2,5-DCB (21%); 2,6-DCB (63%); and 2,3,6-TrCB (16%).
15
16 11.5.2. Photochemical Transformation of Other PCBs
17 Photolysis and photo-oxidation may be major pathways for destruction of PCBs in the
18 environment. Research reported to date and summarized below indicates that ortho-substituted
19 chlorines are more susceptible to photolysis than are meta- and para-substituted congeners; thus,
20 photolytic formation of more toxic dioxin-like PCBs may occur. Oxidation by hydroxyl radicals,
21 however, apparently occurs preferentially at the meta- and para-positions, resulting in a net
22 decrease rather than a net increase in the environmental load of dioxin-like PCBs.
23 On the basis of the data available in 1983, Leifer et al. (1983) concluded that all PCBs,
24 especially the more highly chlorinated congeners and those that contain two or more chlorines in
25 the ortho position, photodechlorinate. In general, as the chlorine content increases, the photolysis
26 rate increases. More recently, Lepine et al. (1992) exposed dilute solutions (4 ppm) of Aroclor
27 1254 in cyclohexane to sunlight for 55 days in December and January. Congener-specific
28 analysis indicated that the amounts of many more-highly chlorinated congeners, particularly
29 mono-ortho-substituted congeners, decreased, whereas those of some less-chlorinated congeners
30 increased. The results for the dioxin-like PCBs indicated a 43.5% decrease in the amount of
31 PeCB 114, a 73.5% decrease in the amount of HxCB 156, and a 24.4% decrease in the amount of
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1 HxCB 157. However, TeCB 77 and PeCB 126 (the most toxic of the dioxin-like PCB
2 congeners), which were not detected in unirradiated Aroclor 1254, represented 2.5% and 0.43%,
3 respectively, of the irradiated mixture.
4 With regard to photo-oxidation, Atkinson (1987) and Leifer et al. (1983), using assumed
5 steady-state atmospheric OH concentrations and measured oxidation rate constants for biphenyl
6 and monochlorobiphenyl, estimated atmospheric decay rates and half-lives for gas-phase PCBs.
7 Atmospheric transformation was estimated to proceed most rapidly for those PCB congeners
8 containing either a small number of chlorines or those containing all or most of the chlorines on
9 one ring. Kwok et al. (1995) extended the work of Atkinson (1987) by measuring the OH radical
10 reaction rate constants for 2,2'-, 3,3'-, and 3,5-dichlorobiphenyl. These reaction rate constants,
11 when taken together with Atkinson's measurements for biphenyl and monochlorobiphenyl and
12 the estimation method described in Atkinson (1991), were used to generate more reliable
13 estimates of the gas-phase OH radical reaction rate constants for the dioxin-like PCBs. The
14 persistence of the PCB congeners increased with increasing degree of chlorination. Table 11-20
15 presents these estimated rate constants and the corresponding tropospheric lifetimes and half-
16 lives.
17 Sedlak and Andren (1991) demonstrated in laboratory studies that OH radicals generated
18 with Fenton's reagent rapidly oxidized PCBs (2-mono-PCB and the DiCBs through PeCBs
19 present in Aroclor 1242) in aqueous solutions. The results indicated that the reaction occurs via
20 addition of a hydroxyl group to one nonhalogenated site; reaction rates are inversely related to
21 the degree of chlorination of the biphenyl. The results also indicated that meta- and para-sites are
22 more reactive than ortho-sites due to stearic hindrance effects. On the basis of their kinetic
23 measurements and reported steady-state aqueous system OH concentrations or estimates of OH
24 radical production rates, the authors estimated environmental half-lives for dissolved PCBs
25 (mono-through octa-PCB) in fresh surface water and in cloud water to be 4 to 11 days and 0.1 to
26 10 days, respectively.
27
28 11.6. PAST USE OF COMMERCIAL PCBs
29 An estimated 1.5 million metric tons of PCBs were produced worldwide (DeVoogt and
30 Brinkman, 1989). Slightly more than one-third of these PCBs (568,000 metric tons) were used in
31 the United States (Versar, 1976). Although the focus of this section is on past uses of PCBs
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1 within the United States, it is necessary to note that the use and disposal of PCBs in many
2 countries, coupled with the persistent nature of PCBs, have resulted in their movement and
3 presence throughout the global environment. The ultimate sink of most PCBs released to the
4 environment is aquatic sediments. Currently, however, large quantities of PCBs are estimated to
5 be circulating between the air and water environments or are present in landfills and dumps,
6 some of which may offer the potential for re-release of PCBs into the air. Tanabe (1988)
7 presented a global mass balance for PCBs that indicated that as of 1985, 20% of the total PCBs
8 produced were present in seawater, whereas only 11% were present in sediments (see Table 11-
9 21). Nearly two-thirds of total global PCB production was estimated by Tanabe to still be in use
10 in electrical equipment or to be present in landfills and dumps.
11 As discussed in Section 11.2, an estimated 568,000 metric tons of PCBs were sold in the
12 United States from 1930 to 1975 (Versar, Inc., 1976). Table 11-22 presents annual estimates of
13 domestic sales by year for each Aroclor from 1957 to 1974. Estimates of PCB usage in the
14 United States by usage category from 1930 to 1975 are presented in Table 11-23. Prior to
15 voluntary restrictions by Monsanto Corporation in 1972 on sales for uses other than "closed
16 electrical systems," approximately 13% of the PCBs were used in "semi-closed applications,"
17 and 26% were used in "open-end applications." Most of the usage for semi-closed and open-end
18 applications occurred between 1960 and 1972 (Versar, Inc., 1976).
19 Table 11-24 presents estimates of the amounts of individual Aroclors that were directly
20 released to the environment (water, air, or soil) between 1930 and 1974. Because detailed usage
21 data were not available for the period 1930 to 1957, Versar, Inc. (1976) assumed that the usage
22 pattern for this period followed the average pattern for the period 1957 to 1959. The basic
23 assumption used by Versar, Inc., in deriving these estimates was that PCBs were released on the
24 order of 5% of those used in closed electrical systems, 60% of those used in semi closed
25 applications, and 25% of those used for plasticizers and that 90% of PCBs used for
26 miscellaneous industrial uses had escaped. The reliability of these release estimates was
27 assumed to be ±30%.
28 Versar, Inc. (1976) also estimated that 132,000 metric tons of PCBs were landfilled. This
29 total comprised 50,000 metric tons from capacitor and transformer production wastes, 36,000
30 metric tons from disposal of obsolete electrical equipment, and 46,000 metric tons from disposal
31 of material from open-end applications. An estimated additional 14,000 metric tons of PCBs,
03/04/05 11 -26 DRAFT—DO NOT CITE OR QUOTE
-------
1 although still "in service" in various semi-closed and open-end applications in 1976, were
2 ultimately destined for disposal in landfills.
3 An estimated 3,702 kg of TEQP-WHO98 were released directly to the U.S. environment
4 during the period 1930 to 1977 (see Table 11-25). These estimates are based on the Aroclor
5 release estimates presented in Table 11-22 and the mean TEQP-WHO98 concentrations in
6 Aroclors presented in Table 11-3.
03/04/05 11 -27 DRAFT—DO NOT CITE OR QUOTE
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Table 11-1. Confidence rating classes for 2000 releases from all known and
suspected source categories of dioxin-like PCBs
Source category
Approved PCB disposal
Accidental PCB releasees
Municipal wastewater treatment sludge
Municipal waste combustion
Industrial wood combustion
Medical waste incineration
Tire combustion
Cigarette combustion
Sewage sludge incineration
Backyard barrel burning
Petroleum refining catalyst regeneration
Air
E
E
E
E
E
E
D
C
D
E
Land
E
A
Water
E
A = Characterization of the Source Category judged to be Adequate for Quantitative Estimation with High Confidence in the
Emission Factor and High Confidence in Activity Level.
C = Characterization of the Source Category judged to be Adequate for Quantitative Estimation with Low Confidence in either
the Emission Factor and/or the Activity Level.
D = These are preliminary indications of the potential magnitude of emissions from "unquantified" sources in Reference Year
1995. These estimates were assigned a "confidence category" rating of D and are not included in the Inventory.
E = Not quantifiable.
Blank means not applicable or no data.
03/04/05
11-28
DRAFT—DO NOT CITE OR QUOTE
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Table 11-2. Inventory of contemporary releases of dioxin-like PCBs (g TEQp-WHO98/yr) in the United States for 1987,1995,
and 2000 and preliminary release estimates of dioxin-like PCBs for 2000 (g TEQp-WHO98/yr)
Emission Source Category
2000 Inventory
A
B
C
2000
Preliminary
D
1995 Inventory
A
B
C
1987 Inventory
A
B
C
Releases (g TEQ,-WHO9/yr) to Air
Cigarettes
Sewage sludge incineration
Backyard barrel burning
Petroleum refining catalyst regeneration
Total Quantified Releases to Airc
0.72
0.72
0.01
44.4
44.4
1.1
1.1
0.44
0.44
Releases (g TEQ,-WHO9/yr) to Land
Municipal Sludge
Nonincinerated sludge
Total Quantified Releases to Landc
18.8
18.8
77.4
77.4
51.1
51.1
Releases (g TEQ,-WHO ],/yr) to Products
Municipal Sludge Disposal
Nonincinerated sludge
Total Quantified Releases to Products1
0.5
0.5
2.0
2.0
1.7
1.7
to
VO
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Table 11-3. Weight percent concentrations of dioxin-like PCBs in aroclors, clophens, and kanechlors
Dioxin-like PCB congener
Aroclor 1016
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WHO98
Total TEQp-WHO94
Aroclor 1221
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WH098
Total TEQP-WH094
IUPAC
number
77
81
105
114
118
123
126
156
157
167
169
170
180
189
77
81
105
114
118
123
126
156
157
167
169
170
180
189
No. of
samples
analyzed
5
3
4
4
4
4
4
4
4
4
5
4
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
4
No. of
detections
0
0
1
0
1
0
0
0
0
0
0
0
0
0
4
1
3
0
4
0
0
0
0
0
0
0
0
0
Mean cone.
(nondetect set to
zero) (g/kg)
0
0
0.0375
0
0.0125
0
0
0
0
0
0
0
0
0
1.075
0.0875
0.3875
0
1.725
0
0
0
0
0
0
0
0
0
TEQP-WHO98 cone.
(nondetect set to
zero) (mg/kg)
0
0
0.00375
0
0.00125
0
0
0
0
0
0
0
0
0
0.005
0.005
0.1075
0.00875
0.03875
0
0.1725
0
0
0
0
0
0
0
0
0
0.328
0.749
Mean conc.a
(nondetect set to !4
detection limit)
(g/kg)
0
0
0.109
0
0.091
0
0
0
0
0
0
0
0
0
1.078
0.116
0.4
0
1.725
0
0
0
0
0
0
0
0
0
TEQP-WH098
conc.a (nondetect
set to Vi detection
limit) (mg/kg)
0
0
0.011
0
0.009
0
0
0
0
0
0
0
0
0
0.0200
0.0200
0.108
0.012
0.04
0
0.173
0
0
0
0
0
0
0
0
0
0.333
0.752
O
O
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O
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Table 11-3. Weight percent concentrations of dioxin-like PCBs in aroclors, clophens, and kanechlors (continued)
Dioxin-like PCB congener
Aroclor 1242, Clophen
A-30, and Kanechlor 300
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WH098
Total TEQP-WH094
Aroclor 1248, Clophen
A-40, and Kanechlor 400
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WHO98
Total TEQp-WH094
IUPAC
number
77
8
105
114
118
123
126
156
157
167
169
170
180
189
77
81
105
114
118
123
126
156
157
167
169
170
180
189
No. of
samples
analyzed
15
7
11
8
9
9
14
9
8
8
14
6
5
7
13
6
9
7
8
7
11
8
7
7
12
5
4
6
No. of
detections
15
6
11
5
9
7
8
8
2
2
2
2
2
0
13
4
8
6
8
7
6
8
3
3
3
4
4
1
Mean cone.
(nondetect set to
zero) (g/kg)
3.3
1.09
4.02
1.13
8.04
1.12
0.049
0.39
0.021
0.021
0.000013
0.19
0.16
0
4.36
1.76
10.12
3.39
20.98
1.48
0.11
1.13
0.19
0.16
0.01
0.96
1.24
0.0018
TEQP-WHO98 cone.
(nondetect set to
zero) (mg/kg)
0.33
0.11
0.4
0.57
0.8
0.11
4.94
0.2
0.011
0.00021
0.00013
0
0
0
7.47
8.70
0.44
0.18
1.01
1.69
2.1
0.15
10.55
0.56
0.09
0.0016
0.1006
0
0
0.0001833
16.87
18.55
Mean conc.a
(nondetect set to !4
detection limit)
(g/kg)
3.301
1.089
4.024
1.201
8.044
1.157
0.094
0.424
0.096
0.096
0.048
0.244
0.218
0
4.36
1.77
10.12
3.4
20.98
1.48
0.14
1.13
0.2
0.16
0.041
0.97
1.24
0.06
TEQP-WH098
conc.a (nondetect
set to 1A detection
limit) (mg/kg)
0.33
0.109
0.402
0.601
0.804
0.116
9.404
0.212
0.048
0.001
0.476
0
0
0
12.5
13.74
0.44
0.18
1.01
1.7
2.1
0.15
13.51
0.56
0.1
0.0016
0.41
0
0
0.006
20.16
21.83
O
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Table 11-3. Weight percent concentrations of dioxin-like PCBs in aroclors, clophens, and kanechlors (continued)
Dioxin-like PCB congener
Aroclor 1254, Clophen
A-50, and Kanechlor 500
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WH098
Total TEQP-WH094
Aroclor 1260, Clophen
A-60, and Kanechlor 600
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WH098
Total TEQP-WH094
IUPAC
number
77
81
105
114
118
123
126
156
157
167
169
170
180
189
77
81
105
114
118
123
126
156
157
167
169
170
180
189
No. of
samples
analyzed
15
6
12
9
11
8
14
10
9
10
14
8
7
7
15
6
11
9
11
8
14
11
8
10
14
8
7
8
No. of
detections
12
1
11
6
11
8
12
10
8
9
6
8
7
2
6
1
10
4
10
1
7
11
8
9
5
8
7
8
Mean cone.
(nondetect set to
zero) (g/kg)
0.8
7.85
35.83
12.17
81.65
4.59
0.99
11.08
1.91
2.74
0.08
5.06
5.79
0.045
125.94
126.04
0.13
0.08
1.59
0.71
9.51
0.0005
1.81
6.89
1.59
2.87
0.16
32.94
82.61
1.74
TEQP-WHO98 cone.
(nondetect set to
zero) (mg/kg)
0.0795
0.79
3.58
6.08
8.17
0.46
99.46
5.54
0.95
0.0274
0.8
0
0
0.0045429
0.01256
0.0075
0.16
0.35
0.95
0.00005
180.89
3.45
0.79
0.03
1.64
0
0
0.1739792
188.45
192.62
Mean conc.a
(nondetect set to !4
detection limit)
(g/kg)
0.83
7.86
35.83
12.23
81.65
4.59
1.02
11.08
1.93
2.74
0.12
5.06
5.79
0.13
0.17
0.1
1.59
0.77
9.51
0.08
1.84
6.89
1.59
2.87
0.19
32.94
82.61
1.74
TEQP-WH098
conc.a (nondetect
set to 1A detection
limit) (mg/kg)
0.08
0.79
3.58
6.11
8.17
0.46
101.7
5.54
0.97
0.03
1.23
0
0
0.013
128.67
128.78
0.017
0.01
0.16
0.39
0.95
0.008
183.82
3.45
0.79
0.03
1.92
0
0
0.17
191.71
195.89
to
o
o
*
o
H
O
HH
H
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O
&
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c
o
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8 Table 11-3. Weight percent concentrations of dioxin-like PCBs in aroclors, clophens, and kanechlors (continued)
o
-i^
o
Calculated for a congener only when at least one sample contained detectable levels of that congener.
Sources: Adapted from Schulz et al. (1989); Duinker and Hillebrand (1983; deBoer et al. (1993); Schwartz et al. (1993); Larsen, et al. (1992); Kannan et al.
(1987); Huckins et al. (1980); Albro and Parker (1979; Jensen et al. (1974); Albro et al. (1981); Duinker et al. (1988); Tanabe et al. (1987);
Himberg and Sippola (1990); Frame et al. (1996a); Frame et al. (1996b); Frame (1997).
-------
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o
Table 11-4. Disposal requirements for PCBs and PCB items
PCBs/items
PCBs
PCB articles
Waste characterization
Mineral oil dielectric fluids from
PCB transformers
Mineral oil dielectric fluids from
PCB-contaminated transformers
PCB liquid wastes other than
mineral oil dielectric fluid
Nonliquid PCB wastes (e.g.,
contaminated materials from spills)
Dredged materials and municipal
sewage treatment sludges containing
PCBs
Transformers
PCB capacitors'1
PCB hydraulic machines
Other PCB articles
Those analyzing >500 ppm PCB
Those analyzing 50-500 ppm
PCB
Those analyzing >500 ppm PCB
Those analyzing 50-500 ppm
PCB
PCB transformers
PCB contaminated transformers
Those containing >1,000 ppm
PCB
Those containing <1,000 ppm
PCB
Those containing PCB fluids
Those not containing PCB
fluids
Disposal requirements
Annex I incinerator3
Annex I incinerator
High-efficiency boiler (40 CFR 761. 10(a)(2)(iii))
Other approved incinerator15
Annex II chemical waste landfill0
Annex I incinerator
Annex I incinerator
High efficiency boiler (40 CFR 761.10(a)(2)(iii))
Other approved incinerator15
Annex II chemical waste landfill0
Annex I incinerator
Annex II chemical waste landfill
Annex I incinerator
Annex II chemical waste landfill
Other approved disposal method, 40 CFR 761.10(a)(5)(iii)
Annex I incinerator
Drained and rinsed transformers may be disposed of in
Annex II chemical waste landfill
Disposal of drained transformers is not regulated
Annex I incinerator
Drained and rinsed machines may be disposed of as
municipal solid waste or salvaged
Drained machines may be disposed of as municipal solid
waste or salvaged
Drained machines may be disposed of by Annex I or
Annex II
Annex I incinerator or Annex II chemical waste landfill
o
o
2
o
H
O
HH
H
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O
&
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o
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-------
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Table 11-4. Disposal requirements for PCBs and PCB items (continued)
PCBs/items
PCB containers
Waste characterization
Those used to contain only PCBs at
a concentration <500 ppm
Other PCB containers
Disposal requirements
As municipal solid waste provided any liquid PCBs are
drained prior to disposal
Annex I incinerator
Annex II, provided any liquid PCBs are drained prior to
disposal
Decontaminate per Annex IV
a Annex I incinerator defined in 40 CFR 761.40.
Requirements for other approved incinerators are defined in 40 CFR 761.10(e).
°Annex II chemical waste landfills are described in 40 CFR 761.41. Annex II disposal is permitted if the PCB waste contains less than 500 ppm PCB and is
not ignitable as per 40 CFR Part 761.41(b)(8)(iii).
dDisposal of containerized capacitors in Annex II landfills was permitted until March 1, 1981; thereafter, only Annex I incineration has been permitted.
Source: U.S. EPA (1987c).
O
o
2
o
H
O
HH
H
W
O
&
O
c
o
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Table 11-5. Off-site transfers of PCBs reported in the Toxics Release
Inventory (TRI) (1988-2000)
Year
2000
1999
1998
1997
1996
1995
1994
1993
1992
1991
1990
1989
1988
No. of TRI
forms filed
NA
NA
NA
NA
NA
NA
NA
16
20
26
NA
NA
122
Reported transfers (kg)
Transfers to
POTWs
102
0
0
a
0
0
0
120
0
0
0
0.5
113
Transfers for
treatment/disposal
150,888
434,666
386,903
471,319
160,802
308,347
466,948
463,385
766,638
402,535
1,181,961
2,002,237
2,642,133
Total transfers
150,990
434,666
386,903
471,319
160,802
308,347
466,948
463,505
766,638
402,535
1,181,961
2,002,237
2,642,246
Tacilities left that particular cell blank on the Form R submissions.
NA = Not available
POTWs = Publicly owned treatment works
Sources: U.S. EPA (1993h, 1995g, 1998b, 2003c).
03/04/05
11-36
DRAFT—DO NOT CITE OR QUOTE
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Table 11-6. Releases of PCBs reported in the Toxics Release Inventory (TRI) (1988-2000)
Year
2000
1999
1998
1997
1996
1995
1994
1993
1992
1991
1990
1989
1988
No. of TRI
forms filed
NA
NA
NA
NA
NA
NA
NA
16
20
26
NA
NA
122
Reported releases (kg)
Fugitive or
nonpoint air
emissions
158
0
0
0
2.3
0
0
0
0
0
2.3
0
2.7
Stack or point
air emissions
2,497
0
0
0
114
0
0
0
0
0
0
0
0
Surface
water
discharges
13
a
0
0
0
0
0
0
0
0
0
120
4.5
Underground
injection
0.5
a
a
a
0
0
0
0
0
0
0
0
0
On-site
releases to
land
648,128
60,854
3,081
4,179
0
0
120
0.5
0
32,372
453
341
Total
on-site
Releases
650,797
0
60,854
3,081
4,295
0
0
120
0.5
0
32,374
573
348
o
o
2
o
H
O
O
V
O
c
o
Tacilities left that particular cell blank on the Form R submissions.
NA = Not available
Sources: U.S. EPA (1993h, 1995g, 1998b, 2003c).
-------
Table 11-7. Aroclor concentrations measured in EPA's National Sewage
Sludge Survey"
Aroclor
1016
1221
1232
1242
1248
1254
1260
Any Aroclor (total)
Percent
detected
0
0
0
0
9
8
10
19
Maximum
concentration
(ng/kg)
—
—
5.2
9.35
4.01
14.7
Median concentration (ng/kg)
Nondetects set to
detection limit
—
—
0.209
0.209
0.209
1.49
Nondetects
set to zero
0
0
0
0
0
0
0
0
Tor POTWs with multiple samples, the pollutant concentrations were averaged before the summary statistics
presented in the table were calculated.
~ = No information given
Source: U.S. EPA (1996a).
03/04/05
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o
OJ
o
4^
o
Table 11-8. Dioxin-like PCB concentrations measured in sludges collected from 74 U.S. publicly owned
treatment works (POTWs) during 1994a b
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
IUPAC
number
77
81
105
114
118
123
126
156
157
167
169
170
180
189
Percent
detected
100
86
99
22
Maximum
concentration
(ng/kg)
22,900
1,250
3,020
1,470
Total TEQP-WHO94
Total TEQP-WHO98
Median concentration (ng/kg)
Nondetect set to
Vi detection
limit
783
27.3
91.6
8.5
9.5
9.3
Nondetect
set to zero
783
27
91.6
0
9.5
9.2
Mean concentration (ng/kg)
Nondetect set
to Vi detection
limit
2,243
65.2
237
32.5
25.2
24.3
Nondetect set
to zero
2,243
63.5
237
26.2
25.1
24.2
VO
o
O
2
O
H
O
O
V
O
c
o
Tor POTWs with multiple samples, the sample concentrations were averaged by Cramer et al. (1994) to POTW averages before calculation of the total TEQ
mean and median values presented in the table. The TEQP-WHO94 and TEQP-WHO98 values were calculated on a facility-level basis.
bBlank cells indicate that no measurements of these congeners were made.
Source: Green et al. (1995); Cramer et al. (1995).
-------
Table 11-9. Dioxin-like PCB concentrations in sewage sludge collected from
a U.S. publicly owned treatment works during 1999
Congener
3,3',4,4'-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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
IUPAC
number
77
105
114
123
118
126
156
157
167
169
170
180
189
Total TEQP-WHO98
Mean emission factor (ng/kg)
Nondetect set to 1A
detection limit
42,467
7,230
701
249
12,867
1,270
1,843
524
935
570
2,627
6,497
199
141
Nondetect set to zero
42,467
7,230
701
249
12,867
1,270
1,843
524
935
570
2,627
6,497
199
141
Source: U.S. EPA (2000f).
03/04/05
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Table 11-10. Quantity of sewage sludge disposed of annually in 1989 by
primary, secondary, or advanced treatment publicly owned treatment works
(POTWs) and potential dioxin-like PCB TEQ releases
Use/disposal practice
Land application
Distribution and marketing
Surface disposal site/other
Sewage sludge landfill
Co-disposal landfills0
Sludge incinerators and co-
incinerators'1
Ocean disposal5
TOTAL
Volume
disposed of
(thousands of
dry metric
tons/yr)
1,714
71
396
157
1,819
865
336
5,357
Percent
of
total
volume
32b
1.3
7.4
2.9
33.9
16.1
6.3
100
Potential TEQP-
WHO98 release3
(gofTEQ/yr)
41.5
1.7
9.6
4.2
44
e
0
101
Potential TEQP-
WHO94 release3
(gofTEQ/yr)
43
1.8
9.9
3.9
45.6
e
0
104.2
Totential TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume generated
(column 2) by the mean dioxin-like PCB TEQ concentration in 74 POTW sludges reported by Green et al. (1995)
and Cramer et al. (1995) (i.e., 24.2 ng TEQP-WHO98/kg and 25.1 ng TEQP-WHO94/kg).
Includes 21.9% applied to agricultural land, 2.8% applied as compost, 0.6% applied to forestry land, 3.1%
applied to "public contact" land, 1.2% applied to reclamation sites, and 2.4% applied in undefined settings.
GLandfills used for disposal of sewage sludge and solid waste residuals.
dCo-incinerators treat sewage sludge in combination with other combustible waste materials.
eSee Section 11.4.6 for a discussion of dioxin-like PCB releases to air from sewage sludge incinerators.
fThe Ocean Dumping Ban Act of 1988 generally prohibited the dumping of sewage sludge into the ocean after
December 31, 1991. Ocean dumping of sewage sludge ended in June 1992 (Federal Register, 1993b). The
current method of disposal of the 336,000 metric tons of sewage sludge that were disposed of in the oceans in
1988 has not been determined.
Sources: Federal Register (1990, 1993b); Green et al. (1995); Cramer et al. (1995).
03/04/05
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Table 11-11. Quantity of sewage sludge disposed of annually in 1995 by
primary, secondary, or advanced treatment publicly owned treatment works
(POTWs) and potential dioxin-like PCB TEQ releases
Use/disposal practice
Land application13
Advanced treatment0
Other beneficial used
Surface disposal/Landfill
Incineration
Other disposal method
TOTAL
Volume disposed
of (thousands of
dry metric tons/yr)
2,500
700
500
1,100
1,400
100
6,300
Percent of
total
volume
41
12
7
17
22
1
100
Potential dioxin release"
(gTEQ/yr)
TEQp-
WHO98
60.5
16.9
12.1
26.6
e
2.4
118.5
TEQp-
WHO94
62.8
17.6
12.6
27.6
e
2.5
123.1
Totential TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume generated
(column 2) by the mean dioxin-like PCB TEQ concentration in 74 POTW sludges reported by Green et al. (1995)
and Cramer et al. (1995) (i.e., 24.2 ng TEQP- WHO98/kg and 25.1 ng TEQP-WHO94/kg).
bWithout further processing or stabilization, such as composting.
°Such as composting.
dEPA assumed that this category includes distribution and marketing (i.e., sale or give-away of sludge for use in
home gardens). Based on the 1988 National Sewage Sludge Survey and 1988 Needs Survey, approximately 1.3%
of the total volume of sewage disposed was distributed and marketed (Federal Register, 1993b). Therefore, it is
estimated that 2 g (TEQP-WHO98 and TEQP-WHO94) were released through distribution and marketing in 1995.
eSee Section 3.5 for estimates of CDD/CDF releases to air from sewage sludge incinerators.
Sources: U.S. EPA (1999e); Green et al. (1995); Cramer et al. (1995).
03/04/05
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Table 11-12. Quantity of sewage sludge disposed of annually in 2000 by
primary, secondary, or advanced treatment publicly owned treatment works
(POTWs) and potential dioxin-like PCB TEQ releases
Use/disposal practice
Land application13
Advanced treatment0
Other beneficial used
Surface disposal/landfill
Incineration
Other disposal method
TOTAL
Volume disposed
of (thousands of
dry metric
tons/yr)
2,800
800
500
900
1,500
100
6,600
Percent of
total
volume
43
12.5
7.5
14
22
1
100
Potential
TEQDF-WHO98 release3
(g TEQ/yr)
14.6
4.2
2.6
4.7
e
0.5
26.6
Totential dioxin TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume
generated (column 2) by the average of the mean TEQDF-WHO98 concentrations in sludge reported by U.S. EPA
(2002) (i.e., 5.22 ng TEQDF-WHO98/kg).
bWithout further processing or stabilization, such as composting.
°Such as composting.
dEPA assumed that this category includes distribution and marketing (i.e., sale or give-away of sludge for use in
home gardens). Based on the 1988 National Sewage Sludge Survey and 1988 Needs Survey, approximately 1.3%
of the total volume of sewage disposed of was distributed and marketed (Federal Register, 1993b). Therefore, it
is estimated that 0.5 g TEQDF-WHO98 were released through distribution and marketing in 2000.
eSee Section 3.5 for estimates of CDD/CDF releases to air from sewage sludge incinerators.
Sources: U.S. EPA (1999e, 2002a).
03/04/05
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Table 11-13. PCB congener group emission factors for industrial wood
combustors"
Congener group
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Number of
detections
1
1
1
0
0
0
0
0
0
0
Maximum
concentration
detected
(ng/kg wood)
32.1
23
19.7
—
Mean concentration
(ng/kg)
Nondetect set
to detection
limit
39.4
50.9
42.3
22.7
17.6
17
17.9
15.8
25
36.3
Nondetect
set to zero
16
11.5
9.8
—
aTwo sites for each congener group.
~ = No information given
Source: CARB (1990e, 1990f).
03/04/05
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Table 11-14. PCB congener group emission factors for medical waste
incinerators (MWIs)a
Congener group
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Mean emission factor (ng/kg)
(2 MWIs without APCD)
Nondetects set to
detection limit
0.059
0.083
0.155
4.377
2.938
0.238
0.155
0.238
0.155
0.155
Nondetects
set to zero
0.059
0.083
0.155
4.377
2.938
0.238
0.155
0.238
0.155
0.155
Mean emission factor (ng/kg)
(2 MWIs with APCD)
Nondetects set to
detection limit
0.311
0.34
0.348
1.171
17.096
1.286
0.902
0.205
0.117
Nondetects
set to zero
0
0
0
0
9.996
1.078
0
0
0
aSee Section 3.3 for details on tested facilities.
APCD = Air pollution control device
~ = No information given
03/04/05
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Table 11-15. PCB congener group emission factors for a tire combustor"
Congener group
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Number
of
detections
0
1
1
0
2
1
1
0
0
0
Maximum
emission factor
(ng/kg)
34.8
29.5
2724
106.5
298.6
—
Mean emission factor
(ng/kg)
Nondetect set
to detection
limit
0.04
11.7
11.8
10
1092
55.9
107.7
20.9
17.7
41.9
Nondetect set
to zero
11.6
9.8
1092
35.5
99.5
—
Three samples for each congener group.
Source: CARB (1991a).
03/04/05
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o
oo
oo
o
Table 11-16. Dioxin-like PCB concentrations in cigarette tobacco in brands from various countries (pg/pack)a
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Total TEQP-WHO94
Total TEQP-WHO98
IUPAC
number
77
81
105
114
118
123
126
156
157
167
169
170
180
189
U.S.
(avg of 7
brands)
105.7
6.2
0.9
0.68
0.64
Japan
(avg of 6
brands)
70.2
7.8
0.9
0.82
0.8
United
Kingdom
(avg of 3
brands)
53
6.1
0.9
0.64
0.62
Taiwan
(1 brand)
133.9
14.5
2.4
1.54
1.49
China
(1 brand)
12.6
2.4
0.4
0.25
0.24
Denmark
(1 brand)
21.7
2.2
0.5
0.24
0.23
Germany
(1 brand)
39.3
7.3
1.6
0.76
0.75
o
o
2
o
H
O
O
V
O
c
o
aBlank cells indicate that no measurements of these congeners were made.
Source: Matsuedaetal. (1994).
-------
Table 11-17. Dioxin-like PCB concentrations in stack gas collected from a
U.S. sewage sludge incinerator
Congener
3,3',4,4'-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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
IUPAC
number
77
105
114
123
118
126
156
157
167
169
170
180
189
Total TEQP-WHO98
Mean emission factor (ng/kg)
Nondetect set to 1A
detection limit
92.37
18
2.56
0.82
38.65
4.51
4.25
1.41
2.55
3.61
7.19
17.79
0.6
0.51
Nondetect set to zero
92.37
18
2.56
0.82
38.65
4.51
4.25
1.41
2.55
3.61
7.19
17.79
0.6
0.51
Source: U.S. EPA (2000f).
03/04/05
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Table 11-18. Dioxin-like PCB emission factors from backyard 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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
IUPAC
number
77
81
105
114
118
123
126
156
157
167
169
170
180
189
Total TEQP-WHO94
Total TEQP-WHO98
Emission factors (jig/kg)
Testl
9.3
5.9
8.3
18.6
7.93e-03
4.21e-03
Test 2
15.2
4.9
14.3
28.7
1.24e-02
6.31e-03
Average
12.3
5.4
11.3
23.7
1.02e-02
5.26e-03
aBlank cells indicate that the congener was not detected in either of the two duplicate samples.
Source: Lemieux (1997).
03/04/05
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Table 11-19. PCB congener group emission factors for a petroleum catalytic
reforming unit"
Congener group
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Total PCBs
Mean
concentration
(ng/dscm)
(at 12% O2)
166
355
743
849
914
780
1,430
698
179
41.3
6,155
Mean
emission rate
(Ib/hr)
5.51e-08
1.17e-07
2.45e-07
2.81e-07
3.02e-07
2.57e-07
4.73e-07
2.32e-07
5.99e-08
1.39e-08
2.04e-06
Mean emission
factor
(lb/1000 bbl)
7.11e-09
1.52e-08
3.17e-08
3.62e-08
3.88e-08
3.30e-08
6.01e-08
2.95e-08
7.59e-09
1.76e-09
2.61e-07
Mean emission
factor
(ng/barrel)
3.23e+00
6.89e+00
1.44e+01
1.64e+01
1.76e+01
1. 50e+01
2.73e+01
1.34e+01
3.44e+00
7.98e-01
1.18e+02
Three samples and three detections for each congener group.
Source: CARB (1999).
03/04/05
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Table 11-20. Estimated tropospheric half-lives of dioxin-like PCBs with
respect to gas-phase reaction with the OH radical
Congener group
Tetrachlorobiphenyls
Pentachlorophenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Dioxin-like
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
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
Estimated
OH reaction
rate constant
(10 12 cm3/
molecule-sec)
0.583
0.71
0.299
0.383
0.299
0.482
0.395
0.183
0.214
0.214
0.266
0.099
0.099
0.125
Estimated
tropospheric
lifetime
(days)3
20
17
40
31
40
25
30
65
56
56
45
121
121
95
Estimated
tropospheric
half-life
(days)3
14
12
28
22
28
17
21
45
39
39
31
84
84
66
Calculated using a 24-hr, seasonal, annual, and global tropospheric average OH radical concentration of
9.7 x 105 molecule/cm3 (Prinnetal., 1995).
Source: Atkinson (1995) (based on Atkinson [1991]; Kwok et al. [1995]).
03/04/05
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Table 11-21. Estimated PCB loads in the global environment as of 1985
Environment
Terrestrial and coastal
Air
River and lake water
Seawater
Soil
Sediment
Biota
Total
Open ocean
Air
Seawater
Sediment
Biota
Total
Total load in environment
Degraded and incinerated
Land-stocked3
World production
PCB load
(metric tons)
500
3,500
2,400
2,400
130,000
4,300
143,100
790
230,000
110
270
231,170
374,000
43,000
783,000
l,200,000b
Percentage of
PCB load
0.13
0.94
0.64
0.64
35
1.1
39
0.21
61
0.03
0.07
61
100
Percentage of
world production
31
4
65
100
aStill in use in electrical equipment and other products, and deposited in landfills and dumps.
bThis value is from Tanabe (1988). DeVoogt and Brinkman (1989) estimated worldwide production to have been
1,500,000 metric tons.
Source: Tanabe (1988).
03/04/05
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o
OJ
o
4^
o
Table 11-22. Estimated domestic sales of aroclors and releases of PCBs, 1957-1974 (metric tons)
Year
1957
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
TOTAL
% of total
Estimated domestic sales
Aroclor
1016
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1,512
9,481
10,673
9,959
31,625
8.8
Aroclor
1221
10
7
115
47
43
64
164
270
167
239
200
62
230
670
1,005
78
16
26
3,412
0.9
Aroclor
1232
89
51
109
70
109
102
6
6
3
7
11
41
124
118
78
0
0
0
924
0.3
Aroclor
1242
8,265
4,737
6,168
8,254
8,993
9,368
8,396
10,692
14,303
17,943
19,529
20,345
20,634
22,039
9,970
330
2,812
2,815
195,596
54.2
Aroclor
1248
807
1,161
1,535
1,282
1,825
1,571
2,274
2,376
2,524
2,275
2,134
2,220
2,563
1,847
97
366
0
0
26,856
7.4
Aroclor
1254
2,023
3,035
3,064
2,761
2,855
2,869
2,681
2,849
3,509
3,191
3,037
4,033
4,455
5,634
2,114
1,585
3,618
2,805
56,120
15.6
Aroclor
1260
3,441
2,713
3,002
3,325
2,966
2,991
3,459
3,871
2,645
2,665
2,911
2,382
2,013
2,218
782
138
0
0
41,525
11.5
Aroclor
1262
14
83
163
148
164
196
188
202
253
348
381
327
323
464
0
0
0
0
3,255
0.9
Aroclor
1268
0
33
46
86
72
95
129
86
89
129
130
127
136
150
0
0
0
0
1,307
0.4
Total
PCB
releases
14,651
11,821
14,202
15,973
17,027
17,256
17,296
20,352
23,494
26,797
28,334
29,536
30,479
33,140
15,559
11,978
17,119
15,605
360,620
100
o
o
2
o
H
O
O
V
O
c
o
Source: Versar, Inc. (1976).
-------
Table 11-23. Estimated U.S. usage of PCBs by use category, 1930-1975
Use class
Closed electrical
systems
Semi-closed
applications
Open-end
applications
Use category
Capacitors
Transformers
Heat transfer
fluids
Hydraulics and
lubricants
Plasticizer uses
Carbonless copy
paper
Misc. industrial
Petroleum
additives
TOTAL
Amount used
(1000 metric
tons)
286
152
9
36
52
20
12
1
568
Percent of total
usage
50.3
26.8
1.6
6.3
9.2
3.5
2.1
<1
100
Reliability of
estimate (%)
±20
±20
±10
±10
±15
±5
±15
±50
Source: Versar, Inc. (1976).
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Table 11-24. Estimated direct releases of aroclors to the U.S. environment,
1930-19743 (metric tons)
Year
1930-56
1957
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
TOTAL
% of total
Estimated environmental releases
Aroclor
1016
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
76
474
534
498
1,582
2.1
Aroclor
1242
8,486
903
649
1,042
1,340
1,852
1,811
1,655
2,085
2,689
3,180
3,376
3,533
4,165
4,569
1,466
22
141
141
43,103
56.1
Aroclor
1248
2,447
319
483
724
556
792
659
935
980
1,025
876
814
853
993
697
51
0
0
0
13,205
17.2
Aroclor
1254
2,269
307
416
518
449
587
554
529
555
660
566
525
733
985
1,168
325
104
181
140
11,572
15
Aroclor
1260
1,614
423
355
507
540
611
571
682
755
497
472
504
433
452
474
121
9
0
0
9,019
11.7
Total PCB
releases
14,817
1,952
1,903
2,792
2,885
3,841
3,594
3,801
4,375
4,872
5,094
5,219
5,552
6,596
6,907
1,963
135
322
281
76,898
100
T)oes not include an additional 132,000 metric tons estimated to have been landfilled during this period.
Source: Versar, Inc. (1976).
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Table 11-25. Estimated releases of dioxin-like PCB TEQs to the U.S.
environment, 1930-1977
Aroclor
1016
1221
1232
1242
1248
1254
1260
1262
1268
Percent of
U.S. sales3
(1957-1974)
12.88
0.96
0.24
51.76
6.76
15.73
10.61
0.83
0.33
Estimated
PCB releases
(1930-1974)"
(metric tons)
1,582
43,103
13,205
11,572
9,019
Estimated
mean TEQP-
WHO98
concentration0
(mg/kg)
d
0.328
7.47
16.87
125.94
188.45
TOTAL
Estimated
total TEQp-
WHO98
released
(kg)
d
322
223
1,457
1,700
3,702
"Sales during the period 1957-1974 constituted 63% of all PCB sales during 1930-1977. Sales data for
individual Aroclors are not available for years prior to 1957; however, sales of Aroclors 1221, 1232, 1262, and
1268 were minor even prior to 1957.
bFrom Table 11-20.
Trom Table 11-3 (assumes nondetect values are zero).
dData are available for only a few samples of Aroclor 1016 where only two dioxin-like PCB congeners were
detected. The total TEQP-WHO98 released is less than 0.01 kg.
~ = Indicates that release estimates were not made because of relatively low usage amounts
Source: Versar, Inc. (1976).
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1 12. RESERVOIR SOURCES OF CDDs/CDFs AND DIOXIN-LIKE PCBs
2
3 National CDD/CDF source inventories have been conducted in several nations, including
4 the United Kingdom (U.K.), the Netherlands, Germany, Austria, and Sweden, to characterize
5 emissions from various source categories and estimate annual CDD/CDF emissions to air (and
6 sometimes other media). These inventories focused mainly on emissions from primary sources
7 (i.e., emissions from the site or process where the CDDs/CDFs are formed).
8 The authors of these inventories (Rappe, 1991; Harrad and Jones, 1992b; Bremmer et al.,
9 1994; Thomas and Spiro, 1995, 1996; Eduljee and Dyke, 1996; Jones and Alcock, 1996; Duarte-
10 Davidson et al., 1997) indicated that the annual estimates of releases to air provided in these
11 inventories may be underestimates of actual emissions for several reasons. First, on an empirical
12 basis, estimates of the amounts of CDDs/CDFs deposited annually from the atmosphere were
13 greater than the estimates of annual CDD/CDF emissions to the atmosphere. Second, because
14 the emission test data were limited, the inventories may underestimate releases from known
15 sources or may not identify all primary sources. Third, the investigators were not able to reliably
16 quantify emissions from potential reservoir (secondary) sources, including volatilization of
17 CDDs/CDFs from PCP-treated wood, volatilization from soil, and resuspension of soil particles.
18 Relatively little research of either a monitoring or a theoretical nature has been performed to
19 identify reservoir sources and to quantify the magnitude of current or potential future releases
20 from these sources.
21 This chapter presents background information on the major reservoir sources of
22 CDDs/CDFs and PCBs, including the potential magnitude (mass) of CDDs/CDFs and PCBs in
23 each reservoir, the chemical/physical mechanisms responsible for releases of these compounds,
24 and estimates of potential annual releases from each reservoir, if such estimates are feasible.
25 Annual releases from reservoir sources are not counted in the quantitative inventory of dioxin
26 sources because such releases are considered as recirculation of "old" and previously formed
27 dioxin.
28
29 12.1. POTENTIAL RESERVOIRS
30 Chapters 2 through 11 discuss both known and suspected sources of newly formed
31 dioxin-like compound releases to the environment in the United States. Once released into the
32 open environment, CDDs, CDFs, and PCBs partition to air, soils, water, sediments, and biota
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1 according to both the nature of the release and the contaminant's chemical and physical
2 properties.
3 For this analysis, reservoirs are defined as materials or places that contain previously
4 formed CDDs/CDFs or dioxin-like PCBs and have the potential for redistribution and circulation
5 of these compounds into the environment. Potential reservoirs include soils, sediments, biota,
6 water, and some anthropogenic materials. Reservoirs become sources when they release dioxin-
7 like compounds to the circulating environment over a defined time and space. Like other
8 sources, they would not include purely intermediate products or materials properly disposed in a
9 secure landfill. Reservoir sources are not included in the quantitative inventory of contemporary
10 sources because they do not involve original releases but rather the recirculation of past releases.
11 They can, however, contribute to human exposure and, therefore, are important to consider.
12 The rate of movement from one environmental medium to another is termed "flux," and
13 it refers to the direction and magnitude of flow and exchange over a reference time period and
14 space. Figure 12-1 presents a conceptual diagram of flux and exchange of dioxin-like
15 compounds to multiple environmental compartments, including the principal environmental
16 reservoirs—soil, water, air, sediment, and biota. This dynamic system consists of fluxes in and
17 out of the atmosphere as well as other exchanges between reservoirs and the atmosphere.
18 Movement between media can be induced by volatilization, wet and dry atmospheric particle
19 and vapor deposition, adsorption, erosion and runoff, resuspension of soils into air, and
20 resuspension of sediments into water.
21
22 12.2. CHARACTERIZATION OF RESERVOIR SOURCES
23 This section is organized according to reservoir type (soil, water, sediment, and biota),
24 with each subsection providing information in three parts: (1) the potential magnitude (mass) of
25 dioxin-like compounds in the reservoir, (2) the chemical/physical mechanisms responsible for
26 releases of these compounds, and (3) estimates of potential annual releases from the reservoir if
27 such estimates are feasible, given the available state of knowledge. Although, anthropogenic
28 structures (e.g., PCP-treated fenceposts, telephone poles) are potential reservoir sources, they are
29 not discussed here because they are covered in Chapter 8 (the most detailed discussion is on
30 PCP, Section 8.3.8).
31
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1 12.2.1. Soil
2 12.2.1.1. Potential Mass of Dioxin-Like Compounds Present
3 In estimating burdens for the U.K., Harrad and Jones (1992b) and Duarte-Davidson et al.
4 (1997) assumed that the majority of CDDs/CDFs in soil is present in the top 5 cm (except
5 possibly in cropland, where they may be present at greater depths due to plowing) and that the
6 soil density is 1,000 kg/m3. Coupling these assumptions with the rural and urban U.S. surface
7 areas and TEQ concentrations yields soil burden estimates of 1,350 kg TEQDF-WHO98 (1,530 kg
8 I-TEQDF) in rural soils and 220 kg TEQDF-WHO98 (250 kg I-TEQDF) in urban soils in the United
9 States.
10 Higher concentrations of CDDs/CDFs than those presented above for background urban
11 and rural soils may be present in soils underlain by municipal and industrial waste and in soils at
12 contaminated industrial sites. The lack of comprehensive data on CDD/CDF concentrations in
13 these soils, as well as the lack of data on the mass of these soils nationwide, precludes estimating
14 total national soil burdens for these soils at present. Higher concentrations may also be present
15 in the soils of areas that have been treated with pesticides contaminated with CDDs/CDFs.
16 Because of the lack of data, it is not possible to estimate current soil burdens of CDDs/CDFs
17 associated with past pesticide use; however, estimates can be made of the total mass of
18 CDD/CDF TEQs that have been applied to soil from past use of the pesticides 2,4-
19 dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T).
20 2,4-D and its salts and esters are widely used in agricultural and nonagricultural settings
21 in the United States as post-emergence herbicides for control of broadleaf weeds and brush.
22 Commercial production in the United States started in 1944 (Esposito et al., 1980) and 2,4-D has
23 been in large-scale, large-volume commercial use for many years (U.S. EPA, 1975). In terms of
24 annual volume, 2,4-D ranks among the top 10 pesticides used in the United States (U.S. EPA,
25 1994b, 1997e). Table 12-1 presents a compilation of domestic production, sales, and usage
26 volumes for 2,4-D and its salts and esters.
27 As described in Section 8.3.8, CDDs/CDFs were detected in several formulations of 2,4-
28 D and its derivatives during analyses performed to comply with EPA's 1987 Data Call-In (DCI)
29 for CDDs/CDFs. Although the analytical results of these tests indicated that CDDs/CDFs were
30 seldom above the regulatory limits of quantification (LOQ) established by EPA for the DCI,
31 several registrants detected and quantified CDDs/CDFs at lower LOQs. The results of these
32 tests are summarized in Table 8-25. The average TEQ in these tests was 1.1 jig TEQDF-
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1 WHO98/kg (0.7 |ig I-TEQDF/kg). Schecter et al. (1997) reported similar concentrations in 2,4-D
2 samples manufactured in Europe and Russia; lower levels were observed in U.S. products. The
3 results of Schecter et al. (1997) are presented in Table 8-27.
4 If it is assumed that the EPA DCI results are typical of CDD/CDF levels in 2,4-D
5 pesticides over the past 20 yr and that the average annual use of these pesticides in the United
6 States has been approximately 25,000 metric tons, then the estimated CDD/CDF TEQ released
7 to the environment from 2,4-D use during the period 1975 to 1995 was 550 g TEQDF-WHO98
8 (350gI-TEQDF).
9 2,4,5-T was used in the United States for a variety of herbicidal applications until the late
10 1970s to early 1980s. The major use of 2,4,5-T (about 41% of annual usage) was for control of
11 woody and herbaceous weed pests on rights-of-way. The other major herbicidal uses were
12 forestry (28% of usage), rangeland (20% of usage), and pasture (5% of usage). Uses of 2,4,5-T
13 for home or recreation areas and for lakes, ponds, and ditches were suspended by EPA in 1970;
14 rights-of-way, forestry, and pasture uses were suspended by EPA in 1979; and all uses were
15 canceled in 1983.
16 Table 12-2 presents a compilation of domestic production, sales, and usage volumes for
17 2,4,5-T and its salts and esters. As shown in Table 12-2, production and use of 2,4,5-T generally
18 increased each year following its introduction in the 1940s until the late 1960s. Production,
19 sales, and usage information for the 1970s are generally not available but are reported to have
20 steadily declined during that decade (Federal Register, 1979; Esposito et al., 1980).
21 Some information is available on the 2,3,7,8-TCDD content of 2,4,5-T, but little
22 information is available on the concentrations of the other 2,3,7,8-substituted CDD/CDFs that
23 may have been present. Plimmer (1980) reported that 2,3,7,8-TCDD concentrations as high as
24 70,000 jig/kg were detected in 2,4,5-T during the late 1950s. In a study of 42 samples of 2,4,5-T
25 manufactured before 1970, Woolson et al. (1972) found 500 to 10,000 |ig/kg of TCDDs in 7
26 samples, and another 13 samples contained 10,000 to 100,000 |ig/kg of TCDDs. HxCDDs were
27 found in 4 samples at levels between 500 and 10,000 |ig/kg and in 1 sample at a concentration
28 exceeding 10,000 |ig/kg but less than 100,000 i-ig/kg. The detection limit in the study was 500
29 jig/kg.
30 The average 2,3,7,8-TCDD concentration in 200 samples of Agent Orange, a defoliant
31 containing about a 50/50 mixture of the butyl esters of 2,4,5-T and 2,4-D that was used by the
32 U.S. Air Force in Vietnam, was 1,910 jig/kg (Kearney et al., 1973). Of the 200 samples, 64
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1 (32%) contained more than 500 jig/kg of 2,3,7,8-TCDD, with the highest concentration reported
2 to be 47,000 jig/kg. Storherr et al. (1971) reported detecting 2,3,7,8-TCDD at concentrations
3 ranging from 100 to 55,000 jig/kg in five samples of 2,4,5-T. Kearney et al. (1973) reported that
4 production samples of 2,4,5-T obtained from the three principal 2,4,5-T manufacturers in 1971
5 contained 2,3,7,8-TCDD at levels of <100 jig/kg, 100 jig/kg, and 2,300 jig/kg.
6 A 1975 survey of 10 lots of a commercial formulation containing 2,4,5-T showed 2,3,7,8-
7 TCDD concentrations ranging from 10 to 40 |ig/kg (Dow Chemical Co., undated). Analyses by
8 EPA of 16 technical-grade 2,4,5-T samples from five different manufacturers revealed 2,3,7,8-
9 TCDD contents ranging from <10 to 25 [ig/kg (Federal Register, 1979). Schecter et al. (1997)
10 reported the analytical results of one sample of 2,4,5-T purchased from Sigma Chemical Co.
11 (product number T-5785, lot number 16H3625). The results, presented in Table 12-3, indicate a
12 total TEQDF-WHO98 concentration of 3.26 jig/kg (2.88 jig I-TEQDF/kg).
13 Because of the wide variability (three orders of magnitude) in the limited available
14 information on the 2,3,7,8-TCDD content of 2,4,5-T (particularly the 2,4,5-T used in the 1950s)
15 and incomplete information on domestic usage, it is difficult to reliably estimate the amount of
16 2,3,7,8-TCDD that was released to the U.S. environment as a result of 2,4,5-T use. A very
17 uncertain estimate can be made using the following assumptions: (1) the average annual
18 consumptions during the 1950s, 1960s, and 1970s were 2,000, 4,000, and 1,500 metric tons/yr,
19 respectively; and (2) the average 2,3,7,8-TCDD concentrations in 2,4,5-T used over these three
20 decades were 10,000 jig/kg in the 1950s, 4,000 jig/kg in the 1960s, and 100 jig/kg in the 1970s.
21 Based on these assumptions, the very uncertain estimate of 2,3,7,8-TCDD input from 2,4,5-T use
22 over the period 1950 to 1979 is 36,000 g.
23 Another contributing source to the soil reservoir is CDD/CDF in sewage sludge applied
24 to land (i.e., surface disposal or land farming), estimated to have been 75 g TEQDF-WHO98 (103
25 g I-TEQDF) in 1995 (see Section 8.4.1 for details). If this same amount of TEQ had been applied
26 each year during the period 1975 to 1995, the total amount applied would have been 1,500 g
27 TEQDF-WH098 (2,000 g I-TEQDF).
28
29 12.2.1.2. Mechanisms Responsible for Releases from Surface Soils
30 Atmospheric deposition is believed to be the current primary source of dioxin-like
31 compounds in surface soil. CDDs/CDFs and PCBs are highly lipid soluble and have low
32 volatility, and they tend to partition to soil rather than into air or water. Once present in or on
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1 soils, physical/chemical and biological mechanisms (photolysis and biodegradation) can slowly
2 alter the composition and amount of compound present. Studies indicate that the dioxin-like
3 compounds (particularly the more highly chlorinated CDDs/CDFs) exhibit little downward
4 mobility after they are deposited in or on soil (Puri et al. 1989; Freeman and Schroy, 1985;
5 Orazio et al., 1992; Paustenbach et al., 1992). However, remobilization of the compounds to the
6 atmosphere is possible through volatilization and resuspension of soil particles.
7 Young (1983) conducted field studies on the persistence and movement of 2,3,7,8-TCDD
8 during 1973 to 1979 on a military test area that had been aerially sprayed with 73,000 kg of
9 2,4,5-T during 1962 to 1970. TCDD levels of 10 to 1,500 ng/kg were found in the top 15 cm of
10 soil 14 yr after the last application of herbicide at the site. Although actual data were not
11 available on the amount of 2,3,7,8-TCDD originally applied as a contaminant of the 2,4,5-T, best
12 estimates indicated that less than 1% of the applied 2,3,7,8-TCDD remained in the soil after
13 14 yr. Young suggested that photodegradation at the time of and immediately after aerial
14 application was responsible for most of the disappearance; however, once incorporated into the
15 soil, the data indicated a half-life of 10 to 12 yr. Similarly, Paustenbach et al. (1992) concluded
16 that the half-life of 2,3,7,8-TCDD in soils at the surface might be 9 to 15 yr and the half-life
17 below the surface could be 25 to 100 yr.
18 Ayris and Harrad (1997) studied the mechanisms affecting volatilization fluxes of several
19 PCB congeners (PCB numbers 28, 52, 101, 138, and 180) from soil and found positive
20 correlations between flux and soil temperature, soil moisture content, and soil PCB
21 concentration. For PCBs, secondary releases from soils (primarily via volatilization) are
22 believed to currently exceed primary emissions in the U.K. (Harner et al., 1995; Jones and
23 Alcock, 1996). Lee et al. (1998) quantified PCBs in air samples taken every 6 hr over a 7-day
24 period in the summer at a rural site in England and found a strong correlation between air
25 temperature and PCB congener concentrations. The concentrations followed a clear diurnal
26 cycle, thus providing some evidence that rapid, temperature-controlled soil-to-air exchange of
27 PCBs influences air concentrations and enables regional/global scale cycling of these
28 compounds.
29 CDDs/CDFs and PCBs sorbed to soil and urban dust particles can also be moved from
30 the terrestrial environment to the aquatic environment via stormwater runoff/erosion. Results of
31 recent research indicate that, for at least some water bodies, erosion/stormwater runoff is
32 currently the dominant mechanism for CDD/CDF input. Smith et al. (1995) analyzed CDD/CDF
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1 concentrations in sediment cores, air, precipitation, soil, and stormwater runoff in an effort to
2 determine the contributing sources of these compounds to the lower Hudson River. The mass
3 balance estimates developed from these data for 1990 to 1993 are stormwater runoff entering
4 tributaries (76% of total CDD/CDF input), anthropogenic wastes (19%), atmospheric deposition
5 (4%), and shoreline erosion (less than 1%). The authors projected the percent contribution of
6 these same sources for 1970 as anthropogenic wastes (70%), stormwater runoff into tributaries
7 (15%), atmospheric deposition (15%), and shoreline erosion (0.1%).
8 Lebeuf et al. (1996) analyzed sediment cores from different locations in the lower St.
9 Lawrence River Estuary and the Gulf of St. Lawrence. The congener group profiles found in the
10 samples indicate that the input of CDDs/CDFs is primarily from the atmosphere. Comparison of
11 the CDD/CDF concentrations in sediments collected from areas where sediment accumulation is
12 due primarily to fluvial transport with sediments from areas where sediment accumulation is due
13 primarily to direct atmospheric deposition onto the water indicates that the contribution of
14 CDDs/CDFs from direct atmospheric deposition represents less than 35% of the sediment
15 burden. Thus, the primary source of CDDs/CDFs is emissions to the atmosphere upwind of the
16 estuary that are deposited within the watershed and subsequently transported downstream by
17 fluvial waters.
18 Paustenbach et al. (1996) and Mathur et al. (1997) reported that stormwater runoff from
19 15 sites in the San Francisco area contained CDD/CDF TEQ at levels ranging from 0.01 to 65 pg
20 I-TEQDF/L; most samples contained less than 15 pg I-TEQDF/L. The sites differed widely in land
21 use; the highest levels measured were obtained from an urban but nonindustrialized area. A
22 distinct variability was noted in the results obtained at the same sampling location during
23 different rain events. The profiles of CDDs/CDFs in the urban stormwater samples were similar,
24 particularly in samples collected at the onset of rain events. Stowe (1996) reported similar
25 findings from analyses of sediments from three stormwater basins collecting runoff from a
26 military base, a city street, and parking lots.
27 Fisher et al. (1998) reported that urban runoff samples from eight sites (15 samples) in
28 the Santa Monica Bay watershed contained CDD/CDF TEQ at levels ranging from 0.7 to 53 pg
29 I-TEQDF/L (all but one sample were in the range of 0.7 to 10 pg I-TEQDF/L). The samples were
30 collected in 1988/1989 from continuously flowing storm drains during both dry and storm
31 periods. The mean concentration measured during storm events, 18 pg I-TEQDF/L, was higher
32 than concentration observed during dry periods, 1 pg I-TEQDF/L.
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1 12.2.1.3. Estimated Annual Releases from Soil to Water
2 Nonpoint sources of CDDs/CDFs to waterways include stormwater runoff from urban
3 areas and soil erosion in rural areas during storms. Approaches for estimating national loadings
4 to water for both of these sources are described below. The estimate derived below for the
5 potential annual national loading of CDDs/CDFs in urban runoff to waterways is uncertain, but it
6 suggests that the loading may be comparable to the contribution from known industrial point
7 sources (at least 20 g I-TEQDF in 1995). Similarly, the estimate derived below for the potential
8 annual national loading of CDDs/CDFs in rural eroded soils to waterways is uncertain, but it has
9 a stronger analytical base than does the urban runoff estimate. This loading estimate, however,
10 is significantly higher than the contribution from known industrial point sources.
11 Urban Runoff. Few data on CDD/CDF concentrations in urban runoff have been
12 reported. The most recent and largest data sets were reported in studies conducted in the San
13 Francisco Bay and Santa Monica Bay regions (Mathur et al., 1997; Fisher et al., 1998). These
14 studies found a wide range of CDD/CDF levels in samples of stormwater runoff from 23 sites,
15 varying from 0.01 to 83 pg I-TEQDF/L. The wide variability and limited geographic coverage of
16 these data preclude derivation of a national emission estimate at this time. However, by making
17 a number of assumptions, a preliminary estimate of the potential CDD/CDF magnitude from this
18 source can be made.
19 In order to estimate the amount of rainfall in urbanized areas of the conterminous United
20 States, a Geographic Information System (GIS) analysis was performed to determine the total
21 area of every U.S. Census urbanized area and the 30-yr annual average rainfall for each of those
22 areas and to calculate the product of the total areas of urbanized areas with the annual average
23 rainfall (Lockheed Martin Corp., 1998). This approach yields an estimate of 1.9 x 1014 L/yr. If
24 it is assumed that urban runoff in the United States averages 1 pg TEQDF-WHO98/L (1 pg I-
25 TEQDF/L) (i.e., approximately the midpoint of the range reported by Mathur et al., 1997, and
26 Fisher et al., 1998), this source could contribute a total of 190 g TEQDF-WHO98 or I-TEQDF/yr to
27 U.S. waterways. No data were available to make similar estimates for PCBs.
28 A similar analysis was conducted using historical precipitation data from the National
29 Oceanic and Atmospheric Administration (NOAA, 2004) and metropolitan/urban area statistics
30 from the 1990 and 2000 census. The 30-year annual average rainfall for each state was
31 calculated for 1987, 1995, and 2000. An approximation of the urban area for each state was
32 estimated by summing the acreage for each metropolitan area identified in the 1990 census.
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1 Assuming that the amount of land classified as urban did not change significantly from 1987 to
2 1990, the urban areas for each state in 1990 were assumed to be equal to those in 1987.
3 Similarly, an approximation for urban area for each state was estimated by summing the urban
4 area acreage available from the 2000 census. An approximation of the 1995 urban area for each
5 State was estimated by taking the average of the 1990 and 2000 estimates. Multiplying the 30-
6 year average rainfall by the urban area for each state and summing the results provides an
7 estimated amount of urban runoff for the conterminous United States. The urban runoff was
8 1.24 x 1014, 1.33 x 1014, and 1.42 x 1014 L/year for 1987, 1995, and 2000, respectively.
9 Applying the emission factors generated above, urban runoff contributed 124, 133, and 142 g I-
10 TEQDF or TEQDF-WHO98 to U.S. waterways in 1987, 1995, and 2000, respectively. These
11 numbers are in agreement with the estimate developed using Lockheed Martin (1998) data.
12 Rural Soil Erosion. Using acreage and erosion factors for cropland provided in the
13 2001 Annual National Resources Inventory (USDA, 2003), 1.36, 1.07, 0.96, and 0.91 billion
14 metric tons of soil and rill erosion were generated in 1987, 1992, 1997, and 2001, respectively.
15 Likewise, using acreage data for rangeland from USDA (2003) and a soil and rill erosion factor
16 of 4.2 tons/acre/year (USDA, 1995), approximately 1.55 billion metric tons of soil and rill
17 erosion were generated in 1987, 1992, 1997, and 2001. For purposes of estimating values for the
18 reference years 1995 and 2000, it is assumed that the 1995 erosion estimate will be the average
19 of soil and rill erosion estimates developed for 1992 and 1997, and that the 2001 numbers will
20 approximate those generated in 2000. The total amount of eroded soil entering waterways is
21 greater than this value, because this value does not include soil erosion from construction areas,
22 forests, and other non-crop and non-rangelands. The data summarized in the U.S. EPA, 2000b
23 report suggest that typical concentrations of CDDs/CDFs in soils in rural areas is about 2.8 ng
24 TEQDF-WHO98/kg. It is not known how well this estimate represents eroded soil from cropland
25 and rangeland. If these soils contain an average of 1 ng TEQDF/kg (i.e., a lower value than the
26 background value for all types of rural soil), they would contribute 2,900, 2,600, and 2,500 g
27 TEQDF-WHO98 to the Nation's waterways in 1987, 1995, and 2000, respectively. Given the
28 uncertainties in both the amount of eroded soil and dioxin levels, these estimates are considered
29 preliminary (i.e., category D). As with urban runoff, no data were available to make similar
30 estimates for PCBs.
31
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1 12.2.1.4. Estimated Annual Releases from Soil to Air
2 No quantitative estimates of the mass of dioxin-like compounds that may be released to
3 the atmosphere annually from U.S. soils have been published in the literature and none are
4 developed in this report. As noted above, the vapor flux of these compounds from soil to air is
5 dependent on the soil and air concentrations of dioxin-like compounds and the temperature,
6 moisture content, and organic carbon content of the soil. Most of these parameters are not
7 characterized well enough for the United States as a whole to enable a reliable estimate to be
8 made at present. Particle flux is dependent on many factors, including wind speed, vegetative
9 cover, activity level, particle size, soil type/conditions, moisture content, and particle density.
10 Through use of models and various assumptions, Kao and Venkataraman (1995) estimated the
11 fraction of ambient air CDD/CDF concentrations in the upper midwestern section of the United
12 States that may be the result of atmospheric re-entrainment of soil particles. Similarly, through
13 use of models and various assumptions, Jones and Alcock (1996) and Harner et al. (1995)
14 reached tentative conclusions about the relative importance of volatilization of dioxin-like
15 compounds from soils in the U.K.
16 Modeling re-entrainment of soil to the atmosphere was conducted by Kao and
17 Venkataraman (1995). Their model incorporated information on particle sizes, deposition
18 velocities, and concentrations of CDDs/CDFs in soils. Smaller particulates, with median
19 diameters ranging from about 0.01 |im to 0.3 |im, are primarily formed from combustion sources
20 when hot vapors condense and through accumulation of secondary reaction products on smaller
21 nuclei. Particles at the upper end of this size range will deposit to the ground in several days.
22 Large or coarse particles, having median diameters of about 8 |im, are generated from wind-
23 blown dust, sea spray, and mechanically generated particles. CDDs/CDFs absorbed onto
24 re-entrained soil would be included in this larger particle size. These larger particles have a
25 lifetime in the atmosphere from a few to many hours.
26 The fraction of ambient air concentration of CDDs/CDFs that results from soil
27 re-entrainment was established on the basis of the contribution of crustal sources to the ambient
28 aerosol. Data on typical crustal soil concentrations in air (15 to 50 i-ig/m3 for rural areas and 5 to
29 25 i-ig/m3 for urban areas) were combined with data on the average concentrations of
30 CDDs/CDFs in soils (73 ng/kg for rural, 2,075 ng/kg for urban, and 8,314 ng/kg for industrial
31 soils) published by Birmingham (1990) for Ontario, Canada, and several U.S. midwestern states.
32 This analysis estimated the concentrations of CDDs/CDFs in the ambient aerosol that originate
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1 from soils to be 1 x 10"3 to 4 x 10"3 pg/m3 in rural areas and 0.01 to 0.05 pg/m3 in urban areas.
2 These particulate dioxin concentrations were compared to average total particulate dioxin levels
3 of 1.36 pg/m3 in Eitzer and Kites (1989) to arrive at the conclusion that soil re-entrainment could
4 account for only 1 to 4% of the particulate dioxins in the atmosphere in urban areas and 0.1 to
5 0.3% of those in rural regions (Kao and Venkataraman, 1995).
6 This information on the size distribution of ambient aerosols and relative CDD/CDF
7 concentrations in different particle size fractions was integrated with particle size deposition
8 velocities to estimate the relative contribution to the total mass deposition flux for small and
9 large particle sizes. Even though re-entrained soil may constitute only a small fraction of the
10 atmospheric levels of CDDs/CDFs, the contribution of dioxins in re-entrained surface soil to the
11 total deposition flux could be significant because coarse particles dominate in dry deposition.
12 Soil re-entrainment could possibly account for as much as 70 to 90% of the total dry deposition
13 of CDDs/CDFs in urban areas and 20 to 40% in rural regions (Kao and Venkataraman, 1995).
14 Two approaches were used by Jones and Alcock (1996) to assess the potential
15 significance of CDD/CDF volatilization from soils: the fugacity quotient concept and a simple
16 equilibrium partitioning model. The fugacity quotient model compares fugacities of individual
17 CDD/CDF compounds in different environmental media to determine the tendency for these
18 compounds to accumulate in particular environmental compartments (McLachlan, 1996).
19 Fugacities for individual compounds, by media, were estimated by Jones and Alcock (1996) on
20 the basis of physical/chemical properties of the compounds as well as the concentrations in the
21 media. In this instance, fugacity quotients were calculated for air and soil by dividing each
22 compound's fugacity for air by that of soil. Quotients near 1 indicate equilibrium conditions
23 between media; values greater than 1 represent a tendency for flux (volatilization) from soil to
24 air, and values less than 1 indicate a net flux to the soil from the air. The equilibrium
25 partitioning model used by Jones and Alcock predicts the maximum (possible "worst case") flux
26 of CDDs/CDFs from soil to the atmosphere. Air phase-to-soil partition coefficients were
27 calculated using the ratios of soil and air fugacity capacities. Equilibrium air concentrations
28 were then calculated using typical U.K. soil concentrations for both urban and rural settings.
29 From the fugacity quotient model, Jones and Alcock (1996) concluded that the less-
30 chlorinated CDDs/CDFs may be close to soil-air equilibrium in the U.K., whereas for other
31 congeners, soil is a sink rather than a source to the atmosphere. The authors reported that the
32 equilibrium partitioning model predicted that 0.15 kg I-TEQ volatilizes annually from soil in the
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1 U.K. However, they discounted this estimate and concluded that soil volatilization is unlikely to
2 be a significant contributor to emissions. The likelihood that these estimates were high was
3 attributed to the fact that assumptions were made that the concentrations of CDDs/CDFs in air
4 were zero and the model does not consider the resistance of CDDs/CDFs to volatilize from soil.
5 Harner et al. (1995) developed a model to predict the long-term fate of PCBs in soils,
6 with emphasis on soil-to-air exchanges. Using data on levels of PCBs in air, soil, and vegetation
7 in the U.K., the investigators developed a mass balance model to simulate the fate of PCBs in
8 U.K. soils from 1935 to 1994. Specifically, monitoring data and physical/chemical property data
9 were compiled to calculate fugacities for PCB congeners 28, 52, 138, and 153. The model was
10 designed to provide an order-of-magnitude level of accuracy, due in part to the inherent
11 variability in the input data. The mass balance equations in the model included a bell-shaped
12 function for rates of emissions of PCBs, with the maximum emission rate occurring in 1967.
13 From these emissions rates, fluxes between air and soil over several decades were estimated.
14 Table 12-4 summarizes the calculated fluxes.
15 During the 1960s and 1970s, levels of total PCBs in U.K. soils reached average levels of
16 approximately 300 i-ig/kg as a result of atmospheric deposition. Because of restrictions on PCB
17 use during the last two decades, air concentrations have fallen, and the primary source to the
18 atmosphere is now believed to be volatilization from soils. The mass balance model estimated a
19 net flux of 700 kg/yr of total PCBs from soils to the atmosphere in 1994. However, this estimate
20 is presented with the caveat that the model tends to underestimate the rate of reduction of PCB
21 concentrations in recent years, which could be attributed to other mechanisms such as
22 biodegradation, photolysis, and other degradation processes.
23
24 12.2.2. Water
25 12.2.2.1. Potential Mass of Dioxin-Like Compounds Present
26 The surface area of inland waters (including the Great Lakes) in the United States is
27 about 359,000 km2 (U.S. DOC, 1995a). Assuming that the mean depth of inland water is 10 m
28 (Duarte-Davidson et al., 1997), the total inland water volume is approximately 3,600 billion m3.
29 No compilation of CDD/CDF measurements in inland surface waters is made for this report;
30 however, if it is assumed that the "typical" value used by Duarte-Davidson et al. (1997) for
31 rivers in the U.K., 38 pg I-TEQDF/m3, is representative of U.S. waters, then the burden is
32 calculated to be 137 g I-TEQDF.
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1 12.2.2.2. Mechanisms Responsible for Supply to and Releases from Water
2 As discussed in Section 12.2.1, dioxin-like compounds enter surface water from
3 atmospheric deposition, stormwater runoff erosion, and discharges of anthropogenic wastes.
4 Volatilization is the primary mechanism for release of dioxin-like compounds from the water
5 column to the atmosphere. Several studies have addressed the water-air exchange of dioxin-like
6 PCBs through volatilization in the Great Lakes (Achman et al., 1993; Hornbuckle et al., 1993;
7 Swackhamer and Armstrong, 1986; Baker and Eisenreich, 1990). No similar body of literature
8 has been developed to address volatilization of CDDs/CDFs from water.
9 Most studies that have addressed PCB water-air exchange have used the two-film model
10 developed by Whitman (1927) and made popular by Liss and Slater (1974). When assessing gas
11 exchange between air and water, the interface between the two phases can be considered as a
12 two-layer (film) system consisting of well-mixed gas and liquid films adjacent to the interface;
13 the rate of transfer is controlled by molecular diffusion through the stagnant boundary layer
14 (Achman et al., 1993). Liss and Slater (1974) applied the model to assess the flux of various
15 gases, specifically in the air-sea systems, and indicated the possibility of its use at any air-water
16 interface in the environment if the necessary data are available. Hornbuckle et al. (1993)
17 concluded that the two-film model is the best available tool for estimating regional and local flux
18 of PCBs from natural waters. The following paragraph, from Achman et al. (1993), succinctly
19 summarizes the model.
20 The basic equation used to describe the rate of transfer across the interface is
21
22 F = Kol(Cw-C*) (12-1)
23
24 where F is the flux (mol/m2-day), Cw (mol/m3) is the dissolved PCB concentration in the bulk
25 water, and C* (P/H, mol/m3) is the air concentration expressed as a water concentration in
26 equilibrium with the air. The variable P is the vapor-phase air concentration measured (mol/m3)
27 and converted to units of pressure using the ideal gas law; H is Henry's Law constant (atm-
28 m3/mol). The overall mass-transfer coefficient, Kol, has units of velocity (m/day). The
29 concentration gradient determines the direction of flux and drives the mass transfer, whereas Kol
30 is a kinetic parameter that quantifies the rate of transfer. The value of Kol is dependent on the
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1 physical and chemical properties of the compound as well as environmental conditions. The
2 reciprocal of Kol is the total resistance to transfer expressed on a gas (RT/Hka)- and liquid (l/kw)-
3 phase basis:
4
5 l/Kol = l/kw + RT/Hka (12-2)
6
7 where kw is the water-side mass transfer coefficient (m/day) and ka is the air-side mass transfer
8 coefficient (m/day). H is Henry's Law constant, R is the universal gas constant (8.2057 x 10"5
9 atm-m3/mol K), and T is the absolute temperature, K.
10 Achman et al. (1993) and Hornbuckle et al. (1993) calculated the volatilization rates of
11 PCBs from Green Bay on Lake Michigan on the basis of air and water samples simultaneously
12 collected over a 14-day period above and below the air-water interphase and analyzed for 85
13 PCB congeners. Air samples collected over nearby land were also analyzed for the 85 PCB
14 congeners. The direction and magnitude of flux for each congener were then calculated using
15 Henry's Law and meteorological and hydrological parameters in the "two-film" model (see eq
16 12-1).
17 The net total PCB transfer rate (i.e., the sum of all congener transfer rates) was found to
18 be from water to air (i.e., volatilization). However, during cool water temperature periods
19 (October), the direction of transfer reversed for many congeners. Calculated transfer rates to air
20 ranged from 15 to 300 ng/m2 per day at low wind speeds (1 to 3 m/sec) to 50 to 1,300 ng/m2 per
21 day at higher wind speeds (4 to 6 m/sec). On a congener basis, the less-chlorinated congeners
22 dominated total fluxes. The summary of flux calculations is presented in Table 12-5. The most
23 important factors influencing the magnitude of volatilization were the water concentration of
24 PCBs, wind speed, and water temperature. In addition, Achman et al. (1993) and Hornbuckle et
25 al. (1993) found that (1) atmospheric PCB concentrations were higher over contaminated water
26 than over nearby land, (2) atmospheric PCBs over water tended to increase with increasing
27 dissolved PCB concentrations, and (3) the congener distribution in the atmosphere correlated
28 linearly with the congener distributions in the adjacent water.
29 Achman et al. (1993) also summarized the PCB volatilization rates reported by other
30 researchers (Baker and Eisenreich, 1990; Swackhamer and Armstrong, 1986; Strachan and
31 Eisenreich, 1988; and Swackhamer et al., 1988) for Great Lakes water bodies. The results of
32 these other studies, presented below, also show net flux of PCBs from water to air.
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Total PCB
volatilization rate
1 Water Body (ng/m2-day) Reference
2 Lake Superior 141 Baker and Eisenreich (1990)
3 Lake Michigan 240 Strachan and Eisenreich (1988)
4 Lake Superior 63 Strachan and Eisenreich (1988)
5 SiskiwitLake 23 Swackhamer et al. (1988)
6 Lake Michigan 15 Swackhamer and Armstrong (1986)
7
8
9 12.2.3. Sediment
10 12.2.3.1. Potential Mass of Dioxin-Like Compounds Present
11 EPA conducted congener-specific measurements of CDDs/CDFs in the sediments from
12 11 U.S. lakes located in areas relatively unimpacted by nearby industrial activity. The mean
13 TEQ concentration in the uppermost sediment layers from these 11 lakes is 5.3 ng TEQDF-
14 WHO98/kg (5.3 ng I-TEQDF/kg) dry weight. For most of the lakes, the uppermost layer
15 represents about 10 yr worth of sedimentation. CDD/CDF concentrations in lakes impacted by
16 industrial activity may have higher concentrations. For example, Duarte-Davidson et al. (1997)
17 reported a TEQ concentration of 54 ng I-TEQDF/kg for urban sediments in the U.K.
18 As noted above, the surface area of inland waters in the United States is approximately
19 359,000 km2 (U.S. DOC, 1995a). In their calculations of sediment burdens in the U.K., Duarte-
20 Davidson et al. (1997) assumed that (1) the sediment surface area equals the water surface area,
21 (2) the majority of CDDs/CDFs are located in the top 5 cm of sediment, and (3) that sediment
22 density is 0.13 g dry weight/cm3. Applying these assumptions to the water surface area and
23 background TEQ concentration for U.S. sediments yields a burden of at least 120 kg TEQDF-
24 WHO98 (120 kg I-TEQDF).
25
26 12.2.3.2. Mechanisms Responsible for Supply to and Releases from Sediment
27 Because sediment is closely connected to the water column above it, evaluating the
28 potential for sediment to act as a reservoir of dioxin-like compounds is complex and likely to be
29 more difficult than studying dioxin-like compounds in a single medium, such as water or soil.
30 Volatilization and sedimentation are two mechanisms whereby persistent chemicals such as
31 CDDs/CDFs and PCBs are lost from water bodies/columns. Numerous authors (Swackhamer
32 and Armstrong, 1986; Muir et al., 1985; Ling et al., 1993) have noted that sediments are a likely
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1 sink for persistent hydrophobic organic compounds, because these compounds are likely to be
2 strongly bound to organic particles in the sediment.
3 For example, Muir et al. (1985) radiolabeled 2,3,7,8-TCDD and studied its dissipation
4 from sediments (collected from a farm pond and a lake) to the water column in laboratory
5 studies under static aerobic conditions at 10EC. After 675 days, more than 80% of the labeled
6 TCDD were still present in the pond sediment, and 87% were still present in the lake sediment.
7 Aeration had little effect on the dissipation rates.
8 The concept of fugacity is a useful way to estimate the behavior of dioxin-like
9 compounds in sediments. Fugacity (the tendency of a chemical to escape from a phase) is
10 expressed in units of pressure (pascals or Pa) and is the partial pressure exerted by the chemical
11 in each medium. Fugacity models estimate equilibrium concentrations in specific media at given
12 chemical concentrations in the environment. Clark et al. (1988) suggested evaluating
13 contaminant concentrations in multiple environmental media by comparing fugacity of adjoining
14 media (e.g., comparing sediment fugacity with water column fugacity to determine a chemical's
15 tendency to move from one to the other). The authors evaluated fugacities of certain
16 organochlorine compounds, including PCBs, in air, water, sediment, fish, and fish-eating birds
17 and their eggs. The authors presented PCBs fugacities developed from data collected in a study
18 of the Lake Ontario region. The fugacities of PCBs in various media can be ranked as
19 birds>fish>water>bottom sediment, indicating that PCBs and other similar chemicals are likely
20 to remain in bottom sediment and are less likely to re-enter the water column.
21
22 12.2.3.3. Releases from Sediment to Water
23 Given the lack of data, no quantitative estimates of annual releases can be made. Ling et
24 al. (1993) evaluated the fate of various chemicals, including PCBs, in Hamilton Harbour, located
25 in Ontario, Canada, using a modified version of the Quantitative Water Air Sediment Interaction
26 (QWASI) fugacity model. Among the processes evaluated were diffusion between air and water
27 and sediment and water; sediment deposition, resuspension, and burial; and sediment
28 transformation. Three primary compartments were studied: air, water, and bottom sediments.
29 The sediment was treated as a simple, well-mixed surface layer of active sediment and the buried
30 sediment underneath. Chemicals in the active sediment were assumed to be able to exchange
31 with the overlying water; chemicals in the buried sediment were assumed to be isolated from the
32 sediment-water exchange. Sediment was assumed to be homogenous rather than heterogenous.
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1 The epi- and hypolimnetic compartments of the water column were defined on the basis of a
2 thermocline, and the atmosphere was defined as a semi-infinite medium of constant, defined
3 composition.
4 Ling et al. estimated rates of PCB movement on the basis of 1987 loadings using two
5 models: one with and one without a thermocline. The results for the water-sediment transfer
6 using the model with a thermocline were -32 kg/yr entering the hypolimnion from the
7 epilimnion, -27 kg/yr entering the surface sediment from the hypolimnion, and -18 kg/yr
8 (>50%) going to burial. For sediment-to-water transfer, -7 kg/yr transferred to the hypolimnion
9 and then 12.5 kg/yr transferred to the epilimnion. Similar numbers were found in the single
10 water column model (the model without a thermocline).
11 Both the model with a thermocline and the model without a thermocline predicted
12 volatilization from the water to the atmosphere—1.6 kg/yr and 1.8 kg/yr, respectively.
13 However, the actual contribution of PCBs from sediment to air was not determined. A
14 comparison of estimated concentrations with observed values are presented in Table 12-6. For
15 PCBs, 68% were buried in the sediment, 20% were exported to Lake Ontario, 5.4% degraded in
16 the water and sediment, and 6% volatilized. The authors noted that these percentages are
17 uncertain. At the sediment-water exchange, more than 90% of each chemical was contained in
18 the sediment because of particle deposition and the high affinity of the chemical for sediment.
19 There was no indication that contaminants buried in the bottom sediments are transferred
20 through diffusion mechanisms back to the surface sediments; however, episodic release of these
21 chemicals from surface sediments can occur through mechanisms such as resuspension during
22 flooding or lake inversions and uptake/ingestion by benthic biota.
23
24 12.2.4. Biota
25 12.2.4.1. Potential Mass of Dioxin-Like Compounds Present
26 The mass of CDDs/CDFs in biota in the United States was not estimated as part of this
27 report. However, to place perspective on the potential magnitude of this reservoir, 82 g I-TEQDF
28 have been estimated to be present in biota in the U.K. (50 g in humans and 32 g in vegetation),
29 which is about three orders of magnitude less than the mass estimated to be present in U.K.
30 surface soils (Duarte-Davidson et al., 1997; Eduljee and Dyke, 1996). No data are available to
31 estimate the biota burden in the United States.
32
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1 12.2.4.2. Mechanisms Responsible for Supply to and Releases from Biota
2 Apparently, very little of the dioxin-like compounds contained in contaminated soil is
3 ultimately taken up by the vegetation growing in the soil. Kjeller et al. (1991) analyzed
4 concentrations of CDDs/CDFs in archived soil and grass samples collected from the mid-1840s
5 to 1989 at an English experimental station and found that only 0.006 to 0.02% of the soil burden
6 of CDDs/CDFs was taken up by the grass. In addition, scientists generally agree that, once taken
7 up by plant tissue, CDDs/CDFs are not translocated to other parts of the plant (e.g., fruits or
8 shoots) (Bacci and Gaggi, 1985; Hulster and Marschner, 1993, 1994; Nakamura et al., 1994).
9 Researchers have found that the concentration of dioxin-like compounds in a plant should
10 reach equilibrium with the vapor phase concentrations of dioxin-like compounds in the
11 surrounding air (Bacci et al., 1990a, b; Frank and Frank, 1989; Horstman and McLachlan, 1992;
12 McCrady and Maggard, 1993; McLachlan et al., 1995; Paterson et al., 1991; Simonich and Kites,
13 1994; Tolls and McLachlan, 1994; Welsch-Pausch et al., 1995). Horstman and McLachlan
14 (1992) stated that the leaf-air transfer of volatile compounds is a reversible process governed by
15 concentration gradients. If CDD/CDF concentrations are higher in the surrounding air than they
16 are in the air spaces within plant tissue, CDDs/CDFs should diffuse into the plant. Once
17 equilibrium is reached and CDD/CDF concentrations in the plant equal that of surrounding air,
18 no more CDDs/CDFs should be taken into the plant. When CDD/CDF concentrations in
19 surrounding air begin to decrease, CDDs/CDFs should diffuse (probably at a slow rate) out of
20 the plant tissue. Apparently, CDDs/CDFs are not bioconcentrated to a significant extent in the
21 lipid portion of the leaf cuticle (Gaggi et al., 1985). The CDDs/CDFs present in the leaf tissue
22 are predominantly released from the plant through leaf fall onto soil. Therefore, vegetation is
23 not likely to be a long-term reservoir of dioxin-like compounds.
24 Research suggests that dioxin-like compounds in animal tissue, unlike in vegetation,
25 seldom, if ever, reach equilibrium with vapor phase concentrations in the surrounding
26 atmosphere (or water column concentrations in the case of aquatic life). Rather, animals
27 exposed to dioxin-like compounds are known to bioaccumulate these compounds, primarily in
28 body fat (U.S. EPA, 1993a, j). Nonetheless, animals, unlike plants, can metabolize certain
29 chlorinated hydrocarbons after they enter the body (Carlberg et al., 1983). Dioxin-like
30 compounds can be released from an animal's body (at congener-specific rates) through
31 metabolic processes or through weight loss, breast-feeding, or sweating. McLachlan (1996)
32 reported the half-life for the clearance of 2,3,7,8-TCDD from humans to be 7 yr. As a result,
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1 animal life has a greater potential than does vegetation for being a long-term reservoir source of
2 CDDs/CDFs. The majority of the dioxin-like compounds released by animals in the form of
3 waste materials will be released to water or soil. Similarly, upon death, the dioxin-like
4 compounds remaining in the body will be deposited onto soil or aquatic sediments or will be
5 ingested by other animals.
6
7 12.2.4.3. Approaches for Measuring and Estimating Releases from Biota
8 Researchers have investigated the uptake and release of CDDs/CDFs by vegetation
9 through measurement of actual concentrations during uptake and release by vegetation grown in
10 closed systems (greenhouses). Bacci et al. (1992) conducted uptake and release studies of
11 1,2,3,4-TCDD by plant foliage in a closed system (specially constructed greenhouse).
12 Concentrations of TCDD vapor in the greenhouse air were maintained during the 370-hr uptake
13 phase at a mean concentration of 0.0062 ng/L (air concentration varied slightly from 0.005 to
14 0.0075 ng/L). To begin the release phase, the TCDD vapor source (amended sand) as well as the
15 greenhouse walls were removed, and release of CDDs/CDFs from the leaves was measured for
16 500 hr. The authors concluded that, during uptake, TCDD concentration in the leaves varied as a
17 function of time and was dependent on the concentration of vapor-phase TCDD in the
18 surrounding air. They estimated the release of TCDD from the vegetation to be relatively slow,
19 with a half-life of TCDD of 3,300 hr.
20 McCrady and Maggard (1993) conducted a mass balance study of uptake and release of
21 dioxin in grass foliage. The results indicated a half-life of dioxin in grass of 128 hr. These
22 researchers also noted that photodegradation of dioxins on the foliage appeared to be a
23 significant removal mechanism, in addition to volatilization. They calculated the
24 photodegradation half-life to be 44 hr.
25 Interpretation of uptake and release data over variable exposure times and contaminant
26 concentrations has led to the development of models describing air-to-vegetation equilibrium
27 and kinetics controlling the behavior of dioxin in vegetation. Some earlier fugacity modeling
28 attempts described the leaf of a plant as behaving as a single compartment. One-compartment
29 models were described by Bacci et al. (1990a, b), Trapp et al. (1990), and Schramm et al. (1987)
30 (as cited in Tolls and McLachlan, 1994). Researchers presenting most of the recently developed
31 models claim that the available data better support the concept of a leaf behaving as two
32 compartments (Riederer, 1990; Paterson et al., 1991; Horstman and McLachlan, 1992; McCrady
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1 and Maggard, 1993; Tolls and McLachlan, 1994; McLachlan et al., 1995). Input parameters
2 considered by most models include critical chemical characteristics of the contaminant,
3 characteristics of the plant, exposure times, and contaminant concentrations measured within the
4 plant. Riederer (1990) suggested treating a leaf as multiple compartments having different
5 accessibility to the atmosphere and different diffusion resistances.
6 Input parameters for the two-compartment model are octanol/water coefficients,
7 cuticle/water partition coefficients, aqueous solubility, and saturation vapor pressure of the
8 chemical of concern. Outputs of the model are prediction of equilibrium concentration in
9 different leaf tissues, estimates of air-to-vegetation bioconcentration equilibria, and
10 identification of leaf compartments in which compounds are likely to accumulate. Riederer
11 (1990) also presented an approach for using the model to semiquantitatively assess the potential
12 for revolatilization of dioxins from vegetation.
13 One advantage of the model presented by Riederer (1990) is that it considers critical
14 plant characteristics in the release of dioxins. A plant is an active organism, responding to
15 changes in its environment and acting accordingly to ensure its survival. Certain plant
16 characteristics, such as the action of stomata (specialized cells usually on the lower leaf surface
17 that open and close to control passage of vapors into and out of the leaf interior) and total leaf
18 volume, are important factors that effect the release rates of vapor phase contaminants from
19 vegetation.
20 Paterson et al. (1991) also presented a two-compartment model for release of dioxin-like
21 compounds from vegetation. This model describes a plant as being made up of compartments in
22 terms of their volume fractions of air, water, and nonpolar (lipid-soluble, or octanol-equivalent)
23 organic matter. Paterson et al. attempted to show that leaf-air equilibrium and kinetics can be
24 correlated with chemical properties of the contaminant and properties of the leaf. The authors
25 suggested that the clearance rate constant (&2) can be correlated with the bioconcentration factor.
26 This model does not consider critical plant characteristics, such as action of the stomata, and for
27 this reason it may be less reliable than models that do consider plant characteristics, such as the
28 model presented by Riederer (1990).
29 Horstman and McLachlan (1992) developed a fugacity model to describe release of
30 semivolatile organic compounds from the surface of a solid (spruce needles). Their approach
31 was slightly different in that their goal was instrument/method development, but their data
32 supported the behavior of a leaf as a two-compartment system.
03/04/05 12-20 DRAFT—DO NOT CITE OR QUOTE
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1 McCrady and Maggard (1993) also collected data supporting the importance of viewing a
2 leaf as a two-compartment system. They used a two-compartment model similar to the one
3 described by Paterson et al. (1991) that also does not consider critical plant characteristics and
4 thus may be less reliable than models that do (e.g., Reiderer, 1990).
5 Tolls and McLachlan (1994) exposed grass cultures for up to 240 hr to several
6 semivolatile organic compounds and then measured the release of contaminants from the grass.
7 They developed a two-compartment partitioning model based on the data they collected. The
8 model consisted of a small surface compartment (the leaf cuticle) and a large interior reservoir
9 (air spaces within the leaf). Their model assumes that the flux of a chemical is the product of the
10 fugacity difference (surface fugacity minus reservoir fugacity) and the conductance between the
11 leaf compartments.
12 In an attempt to validate this model, McLachlan et al. (1995) compared concentrations of
13 semivolatile organic compounds measured in grass grown under field conditions with
14 concentrations predicted by their previous laboratory work with a fugacity meter. The
15 concentrations measured in the grass cultures agreed with results predicted by the mathematical
16 model described by Tolls and McLachlan (1994).
17
18 12.3. SUMMARY AND CONCLUSIONS
19 As depicted in Figure 12-1 a set of complex relationships exists among reservoirs and
20 between reservoirs and contemporary formation sources. The significance of reservoirs for
21 human exposure is more dependent on their ability to affect the concentration of dioxin-like
22 compounds in other media than on their size or net release rate. This section first summarizes
23 and draws conclusions from the limited information available regarding the character and
24 magnitude of reservoir sources. This information is then used to discuss the implications of
25 reservoir sources to human exposure.
26
27 12.3.1. Reservoir Sources
28 Summary statements about soil reservoir sources:
29
30 • Soil is likely to be the reservoir source with the greatest potential for release of
31 CDDs/CDFs to other environmental media, particularly to water. This is due in part
32 to its relatively large mass of stored CDDs/CDFs, but more importantly, it is due to
03/04/05 12-21 DRAFT—DO NOT CITE OR QUOTE
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1 the existence of demonstrated transport mechanisms for intermedia exchange, for
2 example, soil erosion to surface waters and particle resuspension to air.
3
4 • The preliminary estimates of CDD/CDF runoff from urban areas to waterways is
5 comparable to known industrial point source releases, and runoff from agricultural
6 areas to surface waters is more than 100 times greater. It is unclear how much of the
7 soil erosion and runoff represents recently deposited CDDs/CDFs from primary
8 sources or longer-term accumulation. Much of the eroded soil comes from tilled
9 agricultural lands, which would include a mix of CDDs/CDFs from various
10 deposition times. The age of CDDs/CDFs in urban runoff is less clear.
11
12 • Based on the limited information currently available (i.e., primarily fugacity
13 modeling), volatilization of CDDs/CDFs from soils is not believed to significantly
14 alter ambient air concentrations. However, volatilization of PCBs from soil may be a
15 significant process.
16
17 • Based on the limited information currently available, resuspension of soil may
18 account for a small fraction (-4%) of CDD/CDF concentrations in air. This
19 resuspended soil may, however, constitute a more significant portion of dry
20 deposition.
21
22 Summary statements about water reservoir sources:
23
24 • It is unclear whether volatilization of CDDs/CDFs from water can significantly alter
25 air concentrations. For PCBs, however, the water-air exchange appears to be
26 significant and for some water bodies results in a net transfer from water to air.
27
28 • Water is the major media contributing CDDs/CDFs and PCBs to sediment. Note that
29 most of the CDDs/CDFs in sediments originally came from soils. For specific water
30 bodies, however, the CDDs/CDFs and PCBs in sediments may have been dominated
31 by local industrial discharges to water.
32
33 Summary statements about sediment reservoir sources:
34
35 • It is important to distinguish between surface and deep sediments. Surface sediments
36 are commonly resuspended and introduced back into the water; deep sediments
37 generally do not interact with the water column. Surface sediments can contribute
38 significantly to the CDD/CDF and PCB concentrations in water, whereas deep
39 sediments do not.
40
41 • There is little, if any, movement of dioxin-like compounds once they are buried in the
42 bottom sediments. Bottom sediments may be considered as sinks.
43
03/04/05 12-22 DRAFT—DO NOT CITE OR QUOTE
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1 Summary statements about biota reservoir sources:
2
3 • The mass of CDDs/CDFs in vegetation at any given time is likely to be small
4 compared to the mass in soil. Vegetation does play an important role in transferring
5 CDDs/CDFs from the air to the soil via the decay of plant biomass.
6
7 • Release by volatilization from vegetation has been studied and modeled using the
8 fugacity approach, and half-lives have been estimated. Based on these results,
9 volatilization is not believed to be a significant mechanism for release of
10 CDDs/CDFs and PCBs except possibly during forest/brush fires.
11
12 • The mass of CDDs/CDFs in animals at any given time is likely to be small compared
13 to the mass in soil. Similarly, releases are small and occur primarily by excretion and
14 decomposition of dead biomass.
15
16 12.3.2. Implications for Human Exposure
17 Although, the ability to make quantitative estimates of releases from reservoir sources is
18 limited at present, it is reasonable to conclude that the contribution of reservoir sources to human
19 exposure may be significant. Diet accounts for more than 95% of human exposure. Although
20 the size of the biota reservoir is small compared to the soil and sediment reservoirs, it is clearly
21 the key contributor to human exposure. The potential contribution of the other reservoirs to
22 human exposure is discussed below.
23 PCB reservoir releases. Because current sources of newly formed PCBs are most likely
24 negligible, human exposure to the dioxin-like PCBs is thought to be derived almost completely
25 from current releases of old PCBs stored in reservoir sources. Key pathways involve releases
26 from both soils and sediments to both aquatic and terrestrial food chains. One-third of general
27 population TEQDFP exposure is due to PCBs. Thus, at least one-third of the overall risk to the
28 general population from dioxin-like compounds comes from reservoir sources.
29 CDD/CDF releases from soil and sediments to water and exposure via the aquatic
30 pathway. The earlier discussion has shown that soils can have significant inputs to waterways
31 via soil erosion and runoff. Similarly, the sediment reservoir contributes significantly to
32 CDD/CDF concentrations in water. These releases appear to be greater than those from the
33 primary sources included in the inventory. Dioxins in waterways bioaccumulate in fish, and fish
34 consumption causes human exposure. Fish consumption makes up about one-third of the total
03/04/05 12-23 DRAFT—DO NOT CITE OR QUOTE
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1 general population CDD/CDF TEQ exposure. This suggests that a significant portion of the
2 CDD/CDF TEQ exposure could be due to releases from the soil and sediment reservoir.
3 CDD/CDF releases from soil to air and exposure via the terrestrial pathway.
4 Potentially, soil reservoirs could have vapor and particulate releases that deposit on plants and
5 enter the terrestrial food chain. The magnitude of this contribution, however, is unknown. EPA
6 plans future studies in agricultural areas that will compare modeled air concentrations from
7 primary sources to measured levels as a way to gain further insight to this issue.
03/04/05 12-24 DRAFT—DO NOT CITE OR QUOTE
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Table 12-1. Historical production, sales, and usage of 2,4-dichlorophenoxy-
acetic acid (2,4-D) (metric tons)a
Year
2000
1998/99
1996/97
1994/95
1993
1992
1991
1990
1989
1988
1987
1986
1985
1984
1983
1982
1981
1980
1979
1978
1977
1976
1975
1974
1973
1972
1971
1970
1969
2,4-D, acid
Production
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
5,859
6,164
5,763
—
—
—
—
—
—
24,948b
—
19,766
21,354
Sales
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
3,275
3,137
6,187
—
—
—
—
—
—
—
5,619
7,159
8,521
Domestic usage/
disappearance
(metric tons)
23,600-28,100°
23,600-28,100d
23,600-27,200e
21,800-26,300f
16,800-20,400g
16,800-20,400g
18,100-29,500h
18,100-29,500h
18,100-29,500'
23,600-30,400*
23,600-30,400k
-
-
-
-
-
-
-
-
-
-
17,418'
-
-
-
21,772'
15,700'
-
-
2,4-D, esters and salts
(as reported)1"
Production
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
8,618
—
—
7,702
8,762
8,987
11,313
11,874
8,958
12,552
10,913
16,134
6,558
13,400
10,192
—
—
25,854
Sales
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
12,150
0
0
8,234
8,400
8,002
11,147
13,453
9,256
10,196
7,813
13,414
5,991
13,698
10,899
18,654
19,920
20,891
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Table 12-1. Historical production, sales, and usage of 2,4-dichlorophenoxy-
acetic acid (2,4-D) (metric tons)a (continued)
Year
1968
1967
1966
1965
1964
1963
1962
1961
1960
1959
1958
1957
1956
1955
1954
1953
1952
1951
1950
1949
1948
1947
1946
1945
2,4-D, acid
Production
volume
(metric tons)
35,953
34,990
30,927
28,721
24,364
21,007
19,503
19,682
16,413
13,282
14,036
15,536
13,079
15,656
—
11,761
13,933
—
6,421
6,852
9,929
2,553
2,479
416
Sales
volume
(metric tons)
10,352
15,432
12,710
11,816
11,343
9,446
7,716
7,591
—
7,240
6,234
6,871
6,465
5,924
4,838
—
—
—
4,301
2,991
4,152
2,320
2,330
286
Domestic usage/
disappearance
(metric tons)
-
-
28,985m
22,906m
19,958m
15,059m
16,284m
14,107m
14,107m
15,468m
9,662m
-
-
-
-
-
-
-
-
-
-
-
-
-
2,4-D, esters and salts
(as reported)b
Production
volume
(metric tons)
42,690
37,988
32,895
28,740
24,660
20,178
16,831
16,683
15,436
12,438
11,295
12,392
9,635
13,390
10,268
10,733
11,358
—
5,274
5,829
2,458
1,468
515
—
Sales
volume
(metric tons)
30,164
29,300
25,075
21,454
18,263
16,333
13,075
12,533
13,661
7,070
5,649
7,125
7,294
8,121
6,886
8,855
9,637
—
3,219
3,211
1,598
1,108
81
—
aAll values from the U.S. International Trade Commission's (USITC) annual report series Synthetic Organic
Chemicals - United States Production and Sales unless footnoted otherwise (USITC, 1946-1994).
bNo data were reported for domestic usage/disappearance of 2,4-D esters and salts.
cSource: U.S. EPA (1991i).
dSource: U.S. EPA (2000e).
eSource: U.S. EPA proprietary data.
fSource: U.S. EPA (1997e).
BSource: U.S. EPA (1994b).
hSource: U.S. EPA (19921).
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Table 12-1. Historical production, sales, and usage of 2,4-dichlorophenoxy-
acetic acid (2,4-D) (metric tons)a (continued)
'Source: U.S. EPA (1991h).
JSource: U.S. EPA (1990e).
kSource: U.S. EPA (1988c).
'Source: U.S. EPA (1975).
mSource: USDA(1970).
— = Not reported to avoid disclosure of proprietary data
- = No information given
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Table 12-2. Historical production, sales, and usage of 2,4,5-trichlorophen-
oxyacetic acid (2,4,5-T) (metric tons)a
Year
1993
1992
1991
1990
1989
1988
1987
1986
1985
1984
1983
1982
1981
1980
1979
1978
1977
1976
1975
1974
1973
1972
1971
1970
1969
1968
1967
1966
1965
1964
2,4,5-T
Production
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
—
3,200-4,100d
—
—
—
—
—
—
—
—
—
2,268
7,951
6,601
7,026
5,262
5,186
Sales
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
1,329
757
2,312
—
1,691
Domestic usage/
disappearance
(metric tons)
-
-
-
-
-
-
-
-
-
-
-
900C
-
3,200e
4,100d
-
3,200e
900f
-
-
694g
3,200e
-
~7,000h'1
-7,000^
7,756h
3,266h
4,037h
2,4,5-T, esters and salts
(as reported)1"
Production
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
5,595
5,273
19,297
12,333
8,191
6,131
5,880
Sales
volume
(metric tons)
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
1,675
3,272
2,576
15,021
11,657
4,553
5,977
3,128
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Table 12-2. Historical production, sales, and usage of 2,4,5-trichlorophen-
oxyacetic acid (2,4,5-T) (metric tons)a (continued)
Year
1963
1962
1961
1960
1959
1958
1957
1956
1955
1954
1953
1952
1951
1950
1949
1948
1947
1946
1945
2,4,5-T
Production
volume
(metric tons)
4,123
3,796
3,134
2,874
2,516
1,668
2,419
2,345
1,327
1,223
2,395
1,583
—
852
—
—
—
—
—
Sales
volume
(metric tons)
1,928
1,021
1,196
—
1,039
692
—
816
662
639
—
—
—
297
—
—
—
—
—
Domestic usage/
disappearance
(metric tons)
3,266h
3,674h
2,449h
2,676h
2,495h
l,724h
-
-
l,300e
-
-
-
l,100e
-
-
-
-
-
-
2,4,5-T, esters and salts
(as reported)b
Production
volume
(metric tons)
4,543
4,765
3,536
3,594
3,644
2,372
3,098
3,196
1,720
1,761
2,443
1,423
—
—
—
—
—
—
—
Sales
volume
(metric tons)
2,585
2,543
2,372
1,891
1,843
1,151
1,337
1,473
1,077
615
1,817
569
—
—
—
—
—
—
—
aAll values from the U.S. International Trade Commission's (USITC) annual report series Synthetic Organic
Chemicals - United States Production and Sales unless footnoted otherwise (USITC, 1946-1994).
bNo data were reported for domestic usage/disappearance of 2,4-D esters and salts.
cSource: Esposito etal. (1980).
dSource: Federal Register (1979).
eSource: Thomas and Spiro (1995).
fSource: U.S. EPA (1977).
gSource: USDA (1971); reflects farm usage only.
hSource: USDA (1970); values include military shipments abroad.
'Source: Kearney et al. (1973) reports slightly lower domestic consumption for the years 1967 and 1968 than for
1966.
— = Not reported to avoid disclosure of proprietary data
~ = No information given
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Table 12-3. CDD/CDF concentrations in recent sample of 2,4,5-trichloro-
phenoxyacetic acid (2,4,5-T)
Congener/congener group
2,4,5-T sample
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
1.69
0.412
0.465
2.28
1.35
18.1
33.9
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
0.087
0.102
0.183
1.72
0.356
ND (0.012)
0.126
2.9
0.103
3.01
Total 2,3,7,8-CDDa
Total 2,3,7,8-CDFa
Total I-TEQDFa
Total TEQDF-WHO98a
58.2
8.59
2.88
3.26
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
a Calculated assuming nondetect values are zero.
ND = Not detected (value in parenthesis is the detection limit)
~ = No information given
Source: Schecter et al. (1997).
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Table 12-4. PCB 138 fluxes predicted by Earner et al. (1995)
Year
1950
1965
1975
1980
1994
Concentration
in air
(pg/m3)
4
280
49
6
Fugacity
in air
(Pascals x 10 9)
0.24
1.5
~
Fugacity
in soil
(Pascals x 10 »)
1.1
12
16
8.3
Concentration
in soil
(ng/g)
~
Net flux/direction
air -> soil (444 kg/yr)
air - soil (1000 kg/yr)
soil - air (820 kg/yr)
soil - air (700 kg/yr)
~ = No information given
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Table 12-5. Summary of flux calculations for total PCBs in Green Bay, 1989
Date
6-4
6-5
6-6
6-7
6-10
6-11
7-28
7-29
7-30
7-31
8-1
10-21
10-22
10-23
Site
18
18
10
10
4
10
18
21
14
10
4
14
10
4
Flux3
(ng/m2-day)
40
40
95
155
325
13
330
70
225
90
800
555
1,300
30
aNumbers indicate water-to-air transfer of total PCBs. They represent the sum of individual PCB congener fluxes
and are described as "daily" fluxes because they correspond to air samples collected over 5-10 hr and water
samples collected over ~1 hr.
Source: Achmanetal. (1993).
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Table 12-6. Comparison of estimated PCB concentrations with observed
values
Variable
PCBs
Observed concentration
Sediment
Water
0.23-1.04 [ig/g
<20 |ig/m3
Estimated concentration from model without thermocline
Sediment
Water
Amount in sediment
Amount in water
Total mass
8.33
74.9 kg
2.33 kg
77.2kg
Estimated concentration from model with thermocline
Sediment
Hypolimnion
Epilimnion
Amount in sediment
Amount in hypolimnion
Amount in epilimnion
Total mass
0.527
8.48 |ig/m3
7.93 ng/m3
76.3 kg
1.28kg
1.02kg
78.6 kg
Source: Ling etal. (1993).
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SBIWC8S
Export
Food
^Sources
Figure 12-1. Fluxes among reservoirs.
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1 13. BALL CLAY
2
3 13.1. INTRODUCTION
4 The purpose of this chapter is to evaluate the potential for environmental releases of
5 dioxin-like compounds during the mining of ball clay and its subsequent uses. The presence of
6 dioxin-like compounds in ball clay was discovered in 1996 as a result of an investigation to
7 determine the sources of relatively high levels of dioxin found in two chicken fat samples during
8 a national survey of poultry. The survey was conducted jointly by the U.S. Department of
9 Agriculture (USDA), the U.S. Food and Drug Administration (FDA), and EPA to assess the
10 national prevalence and concentrations of CDDs, CDFs, and coplanar PCBs in poultry (Ferrario
11 etal., 1997).
12 The results of the investigation indicated that soybean meal added to chicken feed was the
13 source of dioxin contamination (Ferrario et al., 2000). Further investigation showed that the
14 CDD contamination came from the ball clay added to the soymeal as an anticaking agent. The
15 ball clay was added at approximately 0.3 to 0.5% of the soybean meal. Samples of raw ball clay
16 were subsequently taken at the mine of origin in Mississippi. Analysis of the samples showed
17 elevated levels of CDDs with a congener profile similar to the CDD profiles found in the
18 soymeal, chicken feed, and immature chickens.
19
20 13.2. CHARACTERISTICS OF MISSISSIPPI EMBAYMENT BALL CLAYS
21 The ball clays from the mine discussed above are part of a larger ball clay resource that
22 spans portions of western Kentucky, Tennessee, and Mississippi. These clays were deposited
23 along the shores of the Mississippi Embayment during the early to middle Eocene Epoch, which
24 occurred approximately 40 to 45 million years ago. The Mississippi Embayment ball clays are
25 secondary clays composed mainly of poorly defined crystalline kaolinite. Other minerals present
26 include illite, smectite, and chlorite. Quartz sand is the major nonclay mineral. These deposits
27 of ball clay occur in lenses surrounded by layers of sand, silt, and lignite. The clays can have a
28 gray appearance caused by the presence of finely divided carbonaceous particles. It is not
29 uncommon to find black carbonized imprints of fossil leaves and other plant debris in the clay
30 (Patterson and Murray, 1984).
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1 The plasticity of ball clay makes it an important natural resource for the ceramic industry.
2 The breakdown of the ceramic uses of ball clay is 33% for floor and wall tile, 24% for sanitary
3 ware, 11% for pottery, and 32% for other industrial and commercial uses (Virta, 2000). A minor
4 use of ball clay was as an anticaking agent in animal feeds, but this use has been banned by FDA
5 (Headrick et al., 1999). Total mining of ball clay in 1999 was 1.14 million metric tons (Virta,
6 2000).
7
8 13.3. LEVELS OF DIOXIN-LIKE COMPOUNDS IN BALL CLAY
9 The joint EPA/FDA and USD A investigation of ball clay as a source of dioxin
10 contamination in animal feeds resulted in sampling the clay at an operational mine in western
11 Mississippi. Eight samples of raw (unprocessed) ball clay were collected from an open mining
12 pit at a depth of about 10 to 15 m. Samples were prepared and analyzed by EPA using EPA
13 Method 1613 (Ferrario et al., 2000). The concentrations of the CDDs/CDFs present in the raw
14 ball clay samples from the one mine are shown in Table 13-1. The limits of detection:limits of
15 quantification for the CDDs/CDFs in the clay samples were 0.5:1 pg/g (ppt, dry weight) for the
16 tetras; 1:2 pg/g for the pentas, hexas, and heptas; and 5:10 pg/g for the octas. The mean
17 concentrations of all of the CDDs exceeded 100 ppt (dry weight).
18 OCDD was found at the highest concentration in all of the samples, followed by either
19 1,2,3,4,6,7,8-HpCDD or 1,2,3,7,8,9-HxCDD. The maximum OCDD concentration in the eight
20 samples was approximately 59,000 pg/g. The most toxic tetra- and penta-congeners were present
21 at unusually high concentrations in all of the samples, with average concentrations of 711 pg/g
22 and 508 pg/g for 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD, respectively. Although the ball clays
23 showed elevated levels of 2,3,7,8-substituted CDDs, they showed very low levels of 2,3,7,8-
24 substituted CDFs. In addition, there was a consistent ratio within the HxCDD congener
25 distribution across all samples (i.e., 1,2,3,7,8,9-HxCDD was present at higher concentrations
26 than the other 2,3,7,8-substituted HxCDD congeners). The average percent distribution among
27 the three individual 2,3,7,8-hexa congeners was 5:17:78. This congener pattern was observed in
28 all the raw ball clay samples analyzed.
29 The mean total TEQDF-WHO98 for the raw ball clay was determined to be 1,513 pg/g dry
30 weight; 2,3,7,8-TCDD accounted for 47% of the TEQDF-WHO98, followed by 1,2,3,7,8-PeCDD
31 at 34%. As expected, even though present at the highest concentration, OCDD contributed less
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1 than 1% percent of the total TEQDF-WHO98 due to its relatively small WHO-TEF. In
2 comparison, the typical range of background TEQDF-WHO98 concentrations in North American
3 urban and rural surface soils samples are 2 to 21 pg/g and 0.1 to 6 pg/g, respectively (U.S. EPA,
4 2000b). In soil samples, all 2,3,7,8-CDD/CDF congeners are detected, and 2,3,7,8-TCDD
5 represents less than 1% of total CDD/CDF present. The most prevalent congeners in soils are
6 OCDD followed by OCDF. Table 13-2 compares the mean CDD/CDF congener group
7 concentrations in ball clay with the mean congener group concentrations in rural and urban
8 background soils. This comparison indicates there are few similarities between the ball clay and
9 soils in the congener group distributions.
10
11 13.4. EVIDENCE FOR BALL CLAY AS A NATURAL SOURCE
12 Several lines of evidence suggest that dioxin-like compounds in ball clay are of natural
13 origin. The clay samples were obtained from undisturbed deposits. It is unknown how human
14 activity could have contaminated these deposits without disturbing them. The EPA laboratory in
15 Athens, Georgia, analyzed the Mississippi mine clays using a broad screen for anthropogenic
16 contaminants and no compounds were found outside of the normal range. All known
17 anthropogenic sources of dioxin have associated with them a wide variety of other contaminants.
18 The absence of elevated levels of other compounds is strong evidence that the dioxins found in
19 the clay are not the result of waste disposal.
20 The congener profiles of ball clay do not match those of known anthropogenic sources.
21 Cleverly et al. (1997) reported on the congener profiles that are typical of known anthropogenic
22 sources of dioxin-like compounds in the United States. These analyses were used as a basis for
23 comparison to the profile of the raw ball clay.
24 The congener pattern characteristic of waste combustion sources differs significantly
25 from the ball clay profile in several aspects. In combustion source emissions, all 2,3,7,8-
26 substituted CDD and CDF congeners are measured, and 2,3,7,8-TCDD is usually 0.1 to 1% of
27 total CDD/CDF mass emitted. In ball clay, 2,3,7,8-TCDD is approximately 5% of total mass of
28 dioxins present. As with the ball clay, the most prevalent 2,3,7,8-Cl-substituted CDD congeners
29 in most incinerator emissions are OCDD and 1,2,3,4,6,7,8-HpCDD; however, combustion
30 emissions contain appreciable amounts of CDFs, of which the 1,2,3,4,6,7,8-HpCDF, OCDF,
31 1,2,3,4,7,8-HxCDF, 2,3,7,8-TCDF and 2,3,4,6,7,8-HxCDF congeners dominate.
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1 The combustion of wood generates a congener profile not unlike that of waste incinerator
2 (i.e., the ratio of CDD:CDF is <1), and all laterally substituted congeners can be detected in
3 emissions. The combustion of tree bark produces a congener profile in which the CDD:CDF
4 ratio is >1, showing only minimal and barely detectable levels of CDFs in the smoke, the
5 exception being that 2,3,7,8-TCDF is present at approximately 2% of total mass. The dominant
6 congener in tree bark combustion emissions is OCDD (>30% total CDD/CDF mass), followed by
7 1,2,3,4,6,7,8-HpCDD and 1,2,3,7,8,9-HxCDD.
8 The congener profile of 2,4-D salts and esters seems to mimic a combustion source
9 profile in the number of congeners represented and in the minimal amount of 2,3,7,8-TCDD
10 relative to all 2,3,7,8-Cl substituted congeners. Nevertheless, unlike the combustion source
11 profile, the 1,2,3,7,8-PeCDD and the 1,2,3,4,6,7,8-HpCDF constitute major fractions of total
12 CDD/CDF contamination present in 2,4-D. The congener profile of technical-grade PCP is
13 clearly dominated by OCDD and 1,2,3,4,6,7,8-HpCDD; however, only trace amounts of 2,3,7,8-
14 TCDD are detected in PCP, and 1,2,3,4,6,7,8-HpCDF and OCDF constitute roughly 15% of
15 typical formulations.
16 Metal smelting and refining processes, such as secondary aluminum, copper, and lead
17 smelting, also have all the 2,3,7,8-Cl-substituted CDD/CDF congeners in stack emissions. In
18 secondary aluminum smelting, 2,3,7,8-TCDD is less than 0.1% of total CDDs/CDFs, whereas
19 PeCDF is nearly 25% of total emissions of dioxin-like compounds, and the CDD/CDF ratio is
20 <1. Secondary copper operations show a similar pattern of CDD/CDF emissions, but with five
21 compounds dominating emissions: 1,2,3,4,7,8-HxCDF; 1,2,3,6,7,8-HxCDF; 1,2,3,4,6,7,8-
22 HpCDF; OCDF; OCDD; and 1,2,3,4,6,7,8-HpCDD. In iron ore sintering, the dominant congener
23 in emissions of 2,3,7,8-Cl-substituted compounds is 2,3,7,8-TCDF.
24 A number of studies have shown that natural processes can produce chlorinated aromatic
25 compounds, including dioxin-like compounds. Gribble (1994) reviewed the biological
26 production of a wide variety of halogenated organic compounds in nature. The Mississippi salt
27 march grass "needlerush" (Juncus roemerianus) contains the aromatic compound 1,2,3,4-
28 tetrachlorobenzene, and the blue-green alga Anacystis marina naturally contains chlorophenol.
29 The soil fungus Penicillium sp. produces 2,4-dichlorophenol, and the common grasshopper is
30 known to secrete 2,5-dichlorophenol.
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1 Urhahn and Ballschmiter (1998) also provide a good review of the chemistry of the
2 biosynthesis of chlorinated organic compounds under natural conditions. It has been
3 hypothesized that CDDs, CDFs, and other chlorinated aromatic compounds can be naturally
4 formed from halogenated humic substances and halomethanes can be formed through
5 chloroperoxidase-mediated reactions in undisturbed peat bogs (Silk etal., 1997). A similar
6 chloroperoxidase-mediated biochemical formation of CDDs/CDFs from chlorophenols was
7 achieved under laboratory conditions by Oberg and Rappe (1992).
8 It has been observed that chlorophenols can be biosynthesized (Gribble, 1994; Silk et al.,
9 1997), and that chorophenols are readily adsorbed into peat-bentonite mixtures (Virarghavan and
10 Slough, 1999). Hoekstra et al. (1999) offered the hypothesis that 2,3,7,8-TCDD, 1,2,3,7,8-
11 PeCDD, and 1,2,3,7,8,9-HxCDD can be naturally formed in soils of coniferous forests from
12 chlorinated phenol. These same congeners are also the predominant congeners in the ball clay
13 from the Mississippi Embayment. Although none of these natural processes can be directly
14 connected with the presence of dioxin in ball clay, the existence of such mechanisms lends
15 plausibility to a hypothesis that they are of natural origin.
16 CDDs/CDFs have been found in other clays quite distant from Mississippi Embayment
17 ball clay deposits. No evidence of anthropogenic sources have been discovered in these areas
18 either. The presence of CDDs has been discovered in kaolinitic clay mined in Germany (Jobst
19 and Aldag, 2000). Because no anthropogenic source could be determined to explain the presence
20 and levels of CDDs in the ball clay, the authors speculated that they were the result of an
21 unknown geologic process. In addition, the German clay also has a congener profile similar to
22 that observed in the Mississippi ball clay, with an absence of CDFs at comparable concentrations
23 and the predominance of the 1,2,3,7,8,9-HxCDD among the toxic hexa-CDDs. The similarity in
24 the congener profiles in ball clay mined in the United States and Germany suggests a common
25 origin to the CDDs present in these clays (Ferrario et al., 2000).
26 In summary, no anthropogenic sources have been identified that explain the levels and
27 profiles of CDDs/CDFs present in the clay. On the other hand, no definitive scientific evidence
28 has been brought forward that identifies the principal chemical and physical mechanism involved
29 in the selective chemical synthesis of CDDs under the conditions inherent in the formation of
30 ball clays some 40 million years ago.
31
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1 13.5. ENVIRONMENTAL RELEASES OF DIOXIN-LIKE COMPOUNDS FROM THE
2 MINING AND PROCESSING OF BALL CLAY
3 In 1995, approximately 993 million kg of ball clay was mined in the United States (Virta,
4 2000). Multiplication of the mean TEQDF-WHO98 concentration in mined ball clay by the total
5 amount of ball clay mined in 1995 gives an estimate of 1,502 g TEQDF-WHO98 contained in all
6 the ball clay mined in 1995. It is unknown whether any of these CDDs are released to the
7 environment during the mining, initial refining, and product handling. As discussed above, most
8 ball clay is used to produce ceramics through a process of high-temperature vitrification. The
9 temperatures found in ceramic kilns are well above the levels needed for both volatilization and
10 destruction of CDDs. Despite these high temperatures, it is unclear whether some release occurs,
11 and no stack measurements have yet been made. Therefore, insufficient evidence is available to
12 make even a preliminary estimate of releases, and this activity is classified as a Category "E"
13 source.
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Table 13-1. Concentrations of CDDs determined in eight ball clay samples in
the United States
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
Concentration (pg/g, dry weight)
Mean
711
508
131
456
2,093
2,383
20,640
Median
617
492
134
421
1,880
2,073
4,099
Minimum
253
254
62
254
1,252
1,493
8,076
Maximum
1,259
924
193
752
3,683
3,346
58,766
Total TEQ
TEQDF-WH098
711
508
13
46
209
24
2
1,513
Source: Femioetal.(20l
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Table 13-2. Comparison of the mean CDD/CDF congener group distribution
in ball clay with the mean congener group distributions in urban and rural
soils in North America
Congener group
TCDD
TCDF
PeCDD
PeCDF
HxCDD
HxCDF
HpCDD
HpCDF
OCDD
OCDF
Total CDD/CDF
Mean concentration (pg/g, dry weight)
Raw ball clay
3,729
6
4,798
2
6,609
6
6,194
9
11,222
11
32,586
Urban background soil
36.1
23.5
18.1
40.8
31.7
23.5
194.4
46.4
2,596
40.2
3,067.1
Rural background soil
2.3
6.8
4.1
12.7
22.7
21.9
114.7
37.3
565.1
33.5
821.3
Sources: Adapted from U.S. EPA (2000a); Ferrario et al. (2000).
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REFERENCES
Abad, E; Adrados, A; Caixach, J; Rivera, J. (2002) Dioxin abatement strategies and mass balance at a municipal
waste management plant. Environ Sci Technol 36:92-99.
Abramowicz, D. (1990) Aerobic and anaerobic biodegradation of PCBs: A review. Critical Reviews in
Biotechnology. 10(3):241-251.
Achman, DA; Hornbuckle, KC; Eisenreich, SJ. (1993) Volatilization of polychlorinated biphenyls from Green Bay,
Lake Michigan. Environ Sci Technol 27(l):75-87.
Addink R; Altwicker, ER. (1999) Formation experiments of polychlorinated dibenzo-p-dioxins/dibenzofurans with
Na 37C1. Organohalogen Compounds 4:69-72.
Addink, R; Olie, K. (1995) Mechanisms of formation and destruction of polychlorinated dibenzo-p-dioxins and
dibenzofurans in heterogeneous systems. Environ Sci Technol 29:1425-1435.
Addink, R; Van Bavel, B; Visser, R; et al. (1990) Surface catalyzed formation of polychlorinated dibenzo-p-
dioxins/dibenzofurans during municipal waste incineration. Chemosphere 20(10-12): 1929-1934.
Addink, R; Drijver, DJ; Olie, K. (1991) Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans in the
carbon/fly ash system. Chemosphere 23(8-l):1205-1211.
Addink, R; Bakker, WCM; Olie, K. (1995) Influence of HC1 and C12 on the formation of polychlorinated dibenzo-p-
dioxins/dibenzofurans in a carbon/fly ash mixture. Environ Sci Technol 29:2055-2058.
Adriaens, P; Grbic-Galic, D. (1992) Effect of cocontaminants and concentration on the anaerobic biotransformation
of PCDD/F in methanogenic river sediments. Organohalogen Compounds 8:209-212.
Adriaens, P; Grbic-Galic, D. (1993) Reductive dechlorination of PCDD/F by anaerobic cultures and sediments.
Organohalogen Compounds 12:107-110.
Adriaens, P; Fu, Q; Grbic-Galic, D. (1995) Bioavailability and transformation of highly chlorinated dibenzo-p-
dioxins and dibenzofurans in anaerobic soils and sediments. Environ Sci Technol 29(9):2252-2260.
Advanced Technology Systems, Inc. (1995) Report on measurement of hazardous air pollutants from aluminum
melt furnace operations at Ravenswood Aluminum Corporation. Monroeville, PA: Advanced Technology Systems,
Inc.
AGES (Applied Geotechnical and Environmental Services Corp). (1992) Source sampling report - comprehensive
emissions testing; blast furnace. May/June 1992, Franklin Smelting and Refining Corp. Valley Forge, PA: AGES.
Report No. 42614.01-01.
AHA (American Hospital Association). (1995) Comments by the American Hospital Association in review of
Estimating Exposures to Dioxin-Like Compounds (EPA/600/688/005Ca-c; June 1994; External Review Draft).
Public Comment Number EXP-48-A1, received January 17, 1995.
AHA (American Hospital Association). (1997) Letter dated January 20, 1997, from V. James McLarney, Associate
Vice President, American Hospital Association (AHA), Chicago, IL, to Mr. John Schaum, National Center for
Environmental Assessment, U.S. Environmental Protection Agency, Washington, D.C. (with attachments).
Ahlborg, VG; Becking, GC; Birnbaum, LS; et al. (1994) Toxic equivalency factors for dioxin-like PCBs.
Chemosphere 28(6): 1049-1067.
03/04/05 R-l DRAFT-DONOTCITEORQUOTE
-------
Ahling, B; Lindskog, A. (1982) Emission of chlorinated organic substances from combustion. In: Hutzinger, O.;
Safe, S., eds, Chlorinated dioxins and related compounds, impact on the environment. New York, NY: Pergamon
Press.
Ahling, B; Bjorseth, A; Lunde, G. (1978) Formation of chlorinated hydrocarbons during combustion of polyvinyl
chloride. Chemosphere 7:799-806.
AISI (American Iron and Steel Institute). (1990) Annual statistical report -1989. Washington, DC: American Iron
and Steel Institute.
AISI (American Iron and Steel Institute). (1995) Annual statistical report -1994. Washington, DC: American Iron
and Steel Institute.
Aittola, JP. (1993) Environmental emissions from landfill fires, preliminary investigation. Viatek Topiola Og,
Espoo, Finland.
Aittola, J; Paasivirta, J; Vattulainen, A. (1992) Measurements of organochloro compounds at a metal reclamation
plant. Organohalogen Compounds 9:9-12.
Albro, PW; Parker, CE. (1979) Comparison of the compositions of Aroclor 1242 and Aroclor 1016. Journal of
Chromatography 169:161-166.
Albro, PW; Corbett, JT; Schroeder, JL. (1981) Quantitative characterization of poly chlorinated biphenyl mixtures
(Aroclors® 1248, 1254, and 1260) by gas chromatography using capillary columns. Journal of Chromatography
205:103-111.
Altwicker, ER; Milligan, MS. (1993) Formation of dioxins: Competing rates between chemically similar precursors
and de novo reactions. Chemosphere 27 (1-3):301-307.
Altwicker, ER, Konduri, R; Lin C; Milligan, MS. (1993) Formation of precursors to chlorinated dioxin/furans under
heterogeneous conditions. Combust Sci Tech. 88:349-368.
Alvarado, MJ; Armstrong, BS;Crouch, E. (2001) The AMSA 2000/2001 survey of dioxin-like compounds in
biosolids: statistical analysis. Cambridge, MA: Cambridge Environmental Inc., dated October 30, 2001.
Amendola, GA; Barna, DR. (1989) USEPA petroleum refinery dioxin screening survey: BP Oil-Lima, Ohio
Refinery. Westlake, OH: U.S. Environmental Protection Agency, Region 5, Environmental Sciences Division.
American Forest and Paper Association (1997) Paper, paperboard, and wood pulp statistics: data through 1996.
Washington, DC: American Forest and Paper Association.
American Paper Institute (1992) Statistics of paper, paperboard, and wood pulp: data through 1991. New York,
NY: American Paper Institute.
American Society of Mechanical Engineers (ASME). (1995) The relationship between chlorine in waste streams and
dioxin emissions from waste combustor stacks. ASME, 45 East 4th Street, NY, NY. Report number CRTD-Vol. 36.
American Wood Preservers Institute. (1977) Pentachlorophenol~a wood preservative. McLean, VA: American
Wood Preservers Institute. March 1, 1977.
American Wood Preservers Institute (1995) 1994 Wood preserving industry production statistical report. McLean,
VA: American Wood Preservers Institute.
Atkinson, R. (1987) Estimation of OH radical reaction rate constants and atmospheric lifetimes for
polychlorobiphenyls, dibenzo-p-dioxins, and dibenzofurans. Environ. Sci. Technol. 21:305-307.
03/04/05 R-2 DRAFT-DONOTCITEORQUOTE
-------
Atkinson, R. (1991) Atmospheric lifetimes of dibenzo-p-dioxins and dibenzofurans. The Science of the Total
Environment 104:17-33.
Atkinson, R. (1995) Personal communication with Greg Schweer (Versar, Inc.): estimated congener-specific gas
phase reaction rate constants of OH radical with PCBs, PCDDs, PCDFs.
ATSDR (Agency for Toxic Substances and Disease Registry) (1993) Toxicological profile for selected PCBs
(Aroclor-1260, -1254, -1248, -1242, -1232, -1221, and -1016). Atlanta, GA: Public Health Service, ATSDR. NTIS
Publication No. PB93-182517.
Ayris, S; Harrad, S. (1997) Factors affecting the volatilization of PCBs from soil. Organohalogen Compounds
33:250-254.
BAAQMD (Bay Area Air Quality Management District). (1996) Air emissions of dioxins in the Bay area. San
Francisco, CA: Bay Area Air Quality Management District. March 27, 1996.
Bacci, E; Gaggi, C. (1985). Polychlorinated biphenyls in plant foliage: translocation or volatilization from
contaminated soils? Bulletin of Environmental Contamination and Toxicology 35:673-681.
Bacci, E; Calamari, D; Gaggi, C; et al. (1990a) Bioconcentration of organic chemical vapors in plant leaves:
experiments measurements and correlation. Environ Sci Technol 24(6):885-889.
Bacci, E; Calamari, D; Gaggi, C; et al. (1990b) Bioconcentration of organic chemical vapors in plant leaves: the
azalea model. Chemosphere 21(4-5):525-535.
Bacci, E; Cerejeira, MJ; Gaggi, C; et al. (1992) Chlorinated dioxins: volatilization from soils and bioconcentration in
plant leaves. Bulletin of Environmental Contamination and Toxicology 48:401-408.
Bacher, R; Swerev, M; Ballschmiter, K. (1992) Profile and pattern of monochloro- through
octachlorodibenzodioxins and -dibenzofurans in chimney deposits from wood burning. Environ. Sci. Technol.
26(8):1649-1655.
Baker, JE; Eisenreich, SJ. (1990) Concentrations and fluxes of poly cyclic aromatic hydrocarbons and
polychlorinated biphenyls across the air-water interface of Lake Superior. Environ Sci Technol 24(3):342-352.
Ball, M; Papke, O; Lis, A. (1990) Polychloridibenzodioxine und polychlordibenzofurane in cigaretterauch. Beitrage
zur Tabakforschung International 14(6):393-402.
Ballschmiter, K; Buchert, H; Niemczyk, R; et al. (1986) Automobile exhausts versus municipal waste incineration as
sources of the polychloro-dibenzodioxins (PCDD) and -furans (PCDF) found in the environment. Chemosphere
15(7):901-915.
Barkovskii, AL; Adriaens, P. (1995) Reductive dechlorination of tetrachloro-dibenzo-p-dioxin partitioned from
Passaic River sediments in an autochthonous microbial community. Organohalogen Compounds 24:17-21.
Barkovskii, AL; Adriaens, P. (1996) Microbial dechlorination of historically present and freshly spiked chlorinated
dioxins and diversity of dioxin-dechlorinating populations. Applied and Environmental Microbiology 62(12):4556-
4562.
Battelle. (1999) Source characterization for sewage sludge incinerator emissions. Volume I. Draft test report.
Research Triangle Park, NC: U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards.
EPA Contract No. 68-D-99-009, Work Assignment 1-05.
Beard, A; Krishnat, PN; Karasek, FW. (1993) Formation of polychlorinated dibenzofurans by chlorination and de
novo reactions with FeCl3 in petroleum refining processes. Environ. Sci. Technol. 27(8): 1505-1511.
03/04/05 R-3 DRAFT-DONOTCITEORQUOTE
-------
Bedard, DL; May, RJ. (1996) Characterization of the poly chlorinated biphenyls in the sediments of Woods Pond:
evidence for microbial dechlorination of Aroclor 1260 in situ. Environ Sci Technol 30(l):237-245.
Bedard, DL; Unterman, R; Bopp, LH; et al. (1986) Rapid assay for screening and characterizing microorganisms for
the ability to degrade polychlorinated biphenyls. Applied and Environmental Microbiology 51(4):761-768.
Bedard, DL; Smullen, LA; DeWeerd, KA; et al. (1995) Chemical activation of microbially-mediated PCB
dechlorination: a field study. Organohalogen Compounds 24:23-28.
Behrooz, GS; Altwicker, ER. (1995) Formation of polychlorinated dioxins, furans, benzenes and phenols in the post-
combustion region of a heterogeneous combustor: Effect of bed material and post-combustion temperature. Environ
Sci Technol 29:1156-1162.
Behrooz, GS; Altwicker, ER. (1996) Rapid formation of polychlorinated dioxins/furans during the heterogeneous
combustion of 1,2-dichlorobenzene and 2,4-dichlorophenol. Chemosphere 32 (1): 133-144.
Bell, A. (1999) AB2588 emissions testing at California Portland Cement Company's Colton Plant; Coal Firing and
Coal with Tires Firing. Prepared by Delta Air Quality Services, Incorporated for California Portland Cement
Company. September 1999.
Berenyi, EB (1993) A decade of municipal waste combustion in the United States: prospects and problems. In:
Municipal waste combustion, proceedings of an international specialty conference of the Air and Waste Management
Association. Williamsburg, Va; March 1993. pp. 51-66.
Berenyi, EB; Gould, RN (1993) Municipal waste combustion in 1993. Waste Age 24:51-56.
Bergstrom, J; Bjorner, B. (1992) Dioxiner ock brander vid ovfallsuplag. Mamo, Miljokonsulterna i Studsvik AB.
Stiftelsen reforsk. FoU nr 68. 94 p. (English summary).
Bingham, AG; Edmunds, CJ; Graham, BW; et al. (1989) Determination of PCDDs and PCDFs in car exhaust.
Chemosphere 19(l-6):669-673.
Birmingham, B. (1990) Analysis of PCDD and PCDF patterns in soil samples: use in the estimation of the risk of
exposure. Chemosphere 20(7-9):807-814.
Blumenstock, M; Zimmermann, R; Schraumm, L-W; et al. (1998) Presence of polychlorinated dibenzo-p-dioxins
(PCDD), dibenzofurans (PCDFs), biphenyls (PCB), chlorinated benzenes (PCBz) and polycyclic aromatic
hydrocarbons (PAH) under various combustion conditions in a post combustion chamber. Organohalogen
Compounds 36:59-63.
Boers, JP; de Leer, EWB; Gramberg, L; et al. (1993) Levels of coplanar PCBs in flue gases of high temperature
processes and their occurrence in environmental samples. Organohalogen Compounds 11:233-236.
Born, JGP; Mulder, P; Louw, R. (1993) Fly ash mediated reactions of phenol and monochlorophenols:
Oxychlorination, deep oxidation, and condensation. Environ. Sci. Technol. 27: 1849-1863.
Boschi, G; Cocheo, V; Giannandrea, G; et al. (1992) Hospital and municipal solid waste incinerators: Correlation
between PVC present in waste feed and emitted organic micropollutants. Organohalogen Compounds 9:37-38.
Bowes, GW; Mulvihill, MJ; Simoneit, BRT; et al. (1975a) Identification of chlorinated dibenzofurans in American
polychlorinated biphenyls. Nature 256:305-307.
Bowes, GW; Mulvihill, MJ; DeCamp, MR; Kende, AS. (1975b) Gas chromatographic characteristics of authentic
chlorinated dibenzofurans; identification of two isomers in American and Japanese polychlorinated biphenyls. J
Agric Food Chem 23(6): 1222-1223.
03/04/05 R-4 DRAFT-DONOTCITEORQUOTE
-------
Bramley, MJ. (1998) Dioxin and hexachlorobenzene releases from magnesium production in North America: lessons
from Noranda's project in Asbestos, Quebec. Greenpeace Canada.
Bremmer, HJ; Troost, LM; Kuipers, G; et al. (1994) Emissions of dioxins in The Netherlands. National Institute of
Public Health and Environmental Protection (RIVM) and Netherlands Organization for Applied Scientific Research
(TNO). Report No. 770501018.
Broker, G; Geueke, KJ; Hiester, E; et al. (1992) Emission polychloierter dibenzo-p-dioxins und -furane aus
hausbrand-feuerungen. Essen, Germany: Landesanstalt Ftir Immissionsschutz Nordhein-Westfalen. ISSN 0720-
8499.
Brown, JF. (1994) Determination of PCB metabolic, excretion, and accumulation rates for use as indicators of
biological response and relative risk. Environ. Sci. Technol. 28(13):2295-2305.
Brown, A. (2002) 2002 North Carolina flue-cured tobacco production guide.
Brown, JF; Bedard, DL; Brennan, MJ; et al. (1987) Fob/chlorinated biphenyl dechlorination in aquatic sediments.
Science 236:709-712.
Brown, JF; Carnahan, JC; Dorn, SB; et al. (1988) Levels of bioactive PCDF congeners in PCB dielectric fluids from
capacitors and transformers. Chemosphere 17(9): 1697-1702.
Brown, JF; Frame, GM; Olson, DR; et al. (1995) The sources of the coplanar PCBs. Organohalogen Compounds
26:427-430.
Bruce, KR; Beach, LO; Gullet, RK. (1991) The role of gas-phase C12 in the formation of PCDD/PCDF during waste
combustion. Waste Management 11:97-102.
Brunner, CR. (1984) Incineration systems, selection and design. New York, NY: Van Nostrand Reinhold Co.
Brunner, CR. (1992) Sewage sludge. In: Buonicore, A.J., Davis, W.T., eds., Air pollution engineering manual. Air
and Waste Management Association. New York, NY: Van Nostrand Reinhold. pp. 296-311.
Bruzy, LP; Hites, RA. (1995) Estimating the atmospheric deposition of poly chlorinated dibenzo-p-dioxins and
dibenzofurans from soil. Environ. Sci. Technol. 29:2090-2098.
Bryant, JG. (1993) Chlorinated benzenes. In: Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Vol.6.
pp. 87-100.
Buckland, SJ; Dye, EA, Leathern, SV; et al. (1994) The levels of PCDDs and PCDFs in soil samples collected from
conservation areas following brush fires. Organohalogen Compounds 20:85-89.
Buekens, A; Stieglitz, L; Huang, H; et al. (1997) Preliminary investigation of formation mechanism of chlorinated
dioxins and furans in industrial and metallurgical processes. Organohalogen Compounds 31:516-520.
Bumb, RR; Crummett, WB; Cutie, SS; et al. (1980) Trace chemistries of fire: a source of chlorinated dioxins.
Science 210(4468):385-390.
Buonicore, AJ. (1992a) Control of gaseous pollutants. In: Buonicore, A.J., Davis, W.T., eds., Air pollution
engineering manual. Air and Waste Management Association. New York, NY: Van Nostrand Reinhold.
Buonicore, AJ. (1992b) Medical waste incineration. In: Buonicore, A.J., Davis, W.T., eds., Air pollution
engineering manual, Air and Waste Management Association. New York, NY: Van Nostrand Reinhold.
03/04/05 R-5 DRAFT-DONOTCITEORQUOTE
-------
Burton, BK; Kiser, JVL. (1993) Status and directions of the U.S. municipal waste combustion industry. In:
Municipal waste combustion, proceedings of an international specialty conference of the Air and Waste Management
Association. Williamsburg, Va.; March 1993. pp. 3-11.
Buser, HR. (1979) Formation of poly chlorinated dibenzofurans (PCDFs), and dibenzo-p-dioxins (PCDDs) from the
pyrolysis of chlorobenzenes. Chemosphere 8:415-424.
Buser, HR; Bosshardt, HP. (1976) Determination of poly chlorinated dibenzo-p-dioxins and dibenzofurans in
commercial pentachlorophenols by combined gas chromatography-mass spectrometry. Journal of the AOAC
59(3):562-569.
Cains, PW; Dyke, P. (1994) Emissions of chlorinated dibenzodioxins and dibenzofurans from waste combustion
plants in the UK. Organohalogen Compounds 20:271-276.
Calamari, D; Bacci, E; Focardi, S; etal. (1991) Role of plant biomass in the global environmental partitioning of
chlorinated hydrocarbons. Environ Sci Technol 25(8): 1489-95.
Calcagni, J; Ciolek, M; Mulrine, P. (1998) Dioxin emissions from U.S. sinter plants. Abstract. Research Triangle
Park, NC: U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards.
California Regional Water Quality Control Board (CRWQCB). (1996) Memorandum to David Cleverly (U.S.
Environmental Protection Agency) from Lila Tang (California Regional Water Quality Control Board).
Cement Kiln Recycling Coalition. (2003) Email correspondence between M. Benoit, Cement Kiln Recycling
Coalition, andK. Riley, Versar, Inc., on February 24, 2003.
CANA (Cremation Association of North America). (2002) Confirmed 2000 Statistics: 2000-2025.
http://www.cremationassociation.org/docs/WebOOConfirmed.pdf
CANA. (2003) Telephone conversation between Allen Krobath, CANA, andK. Riley, Versar, Inc., on February 12,
2003.
Capes, CE. (1983) Size enlargement. In: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. 21:77-105.
New York, NY: John Wiley and Sons.
CARD (California Air Resources Board). (1987a) Determination of PCDD and PCDF emissions from motor
vehicles. Draft report. October 1987. Test Report No. C-86-029.
CARD (California Air Resources Board). (1990a) ARE evaluation test conducted on a hospital waste incinerator at
Los Angeles Co. - USC Medical Center Los Angeles, California. Engineering Evaluation Branch, Monitoring and
Laboratory Division. Test Report C-87-122.
CARD. (1990b) Evaluation on a woodwaste fired incinerator at Koppers Company, Oroville,California. Test Report
No. C-88-065. Engineering Evaluation Branch, Monitoring and Laboratory Division. May 29, 1990.
CARD. (1990c) Evaluation test on two propane fired crematories at Camellia Memorial Lawn Cemetery. Test
Report No. C-90-004. Engineering Evaluation Branch, Monitoring and Laboratory Division. Preliminary Draft.
CARD. (1990d) Compliance testing for non-criteria pollutants at a landfill flare. Confidential Report No. ERC-2.
Engineering Evaluation Branch, Monitoring and Laboratory Division. [As reported in U.S. EPA, 1997b.]
CARD. (1990e) Evaluation test on a wood waste fired incinerator at Pacific Oroville Power Inc. Test Report No. C-
88-050. Engineering Evaluation Branch, Monitoring and Laboratory Division. May 29, 1990.
03/04/05 U DRAFT-DONOTCITEORQUOTE
-------
CARD. (1990f) Evaluation test on twin fluidized bed wood waste fueled combustors located in Cental California.
Test Report No. C-87-042. Engineering Evaluation Branch, Monitoring and Laboratory Division. February 7, 1990.
CARD. (1990g) Evaluation test on a wood waste fired incinerator at Louisiana Pacific Hardboard Plant, Oroville,
CA. Test Report No. C-88-066. Engineering Evaluation Branch, Monitoring and Laboratory Division. [As reported
inNCASI, 1995.]
CARD. (1991a) Emissions test of the Modesto Energy Project tires-to-energy facility. Project No. C-87-072.
Engineering Evaluation Branch, Monitoring and Laboratory Division. May 24, 1991.
CARD. (1991b) Evaluation test of a hospital refuse fired incinerator at American Environmental Management
Corporation. Engineering Evaluation Branch, Monitoring and Laboratory Division. Test Report No. C-89-001.
CARD. (1992a) Dioxin/furan estimates from a secondary aluminum facility. Confidential Report No. ERC-9.
Engineering Evaluation Branch, Monitoring and Laboratory Division. [As reported in U.S EPA, 1997b.]
CARD. (1992b) Emission measurements on delacquering system. Confidential Report No. ERC-32. Engineering
Evaluation Branch, Monitoring and Laboratory Division. [As reported in U.S EPA, 1997b.]
CARD. (1993a) Emissions measurement of toxic compounds from a cupola baghouse at a steel foundry.
Confidential Report No. ERC-61. Engineering Evaluation Branch, Monitoring and Laboratory Division. [As
reported in U.S. EPA, 1997b.]
CARD. (1999) Determination of emissions from the No. 3 reformer as Tosco Refining Company San Francisco Area
Refinery at Avon. Project No. C-96-0396. Engineering and Laboratory Branch, Monitoring and Laboratory
Division.
CARD. (2002) Staff report: Initial statement of reasons for the proposed airborne toxic control measure to reduce
emissions of toxic air contaminants from outdoor residential waste burning. State of California Air Resource Board
Sacramento, CA. January 4.
Carlberg, GE; Ofstad, EB; Drangsholt, H. (1983) Atmospheric deposition of organic micropollutants in Norway
studied by means of moss and lichen analysis. Chemosphere 12(3):341-356.
Carpenter, A. (2001) Telefax from Andrew Carpenter, Resource Management, Inc. to Stephen Schwartz, Versar, Inc.
January 23, 2001.
Carpenter, C; Schweer, G; Stinnett, G; et al. (1986) Exposure assessment for hexachlorobenzene. Washington, DC:
U.S. Environmental Protection Agency, Office of Toxic Substances. EPA 560/5-86-019.
Carroll, WF. (1996) Is PVC in house fires the great unknown source of dioxin? Fire and Materials 20:161-166.
Cash, G. (1993) Document on dioxin/furan data call-ins [memorandum to John Schaum, U.S. EPA, Office of
Research and Development]. Washington, D.C.: U.S. Environmental Protection Agency, Office of Pollution
Prevention and Toxics. May 4, 1993.
CCC (Chlorine Chemistry Council). (2004) CDD/CDF data validation studies. CDD/CDF release estimates for
occidental chemical corporation. Convent, LA; Deer Park (VCM Plant), TX; Ingleside, TX; LaPorte, TX; Mobile,
AL. March 2003.
Cement Kiln Recycling Coalition. (2003) Email correspondence between M. Benoit, Cement Kiln Recycling
Coalition, andK. Riley, Versar, Inc., on February 24, 2003.
CEQ (Council on Environmental Quality). (1997) Environmental Quality 1990. 25th Annual Report. Washington,
DC: Council on Environmental Quality. Executive Office of the President of the United States.
03/04/05 R-7 DRAFT-DONOTCITEORQUOTE
-------
ChemRisk. (1993) Critique of dioxin factories. Prepared for: The Vinyl Institute, September 1993.
Chen, YR; Chen, CJ; Lee, CC; Chuong, CY. (1986) Reproductive effects of emissions from waste electrical products
combustion. Presented at: Dioxin '86, 6th International Symposium on Chlorinated Dioxins and Related
Compounds; Fukuoka, Japan.
Chen, M; Hong, CS; Bush, B; Rhee, GY. (1988) Anaerobic biodegradation of polychlorinated biphenyls by bacteria
from Hudson River sediments. Ecotoxicol. and Environ. Safety 16:95-105.
Chinkin, LR; Weir, BR; Latimer, DA. (1987) Inventory of chlorophenol use in the forest products industry and
investigation of related emissions of chlorinated dibenzodioxins and dibenzofurans. Sacramento, CA: California Air
Resources Board. Contract No. A5-125-32.
Chlorine Chemistry Council. (2002) Information provided at meeting held in Washington,
DC, in September, 2002.
Choudhry, GG; Hutzinger, O. (1983) Mechanistic aspects of the thermal formation of halogenated organic
compounds including polychlorinated dibenzo-p-dioxins. New York, NY: Gordon and Breach.
Choudhry, GG; Webster, GRB. (1989) Environmental photochemistry of PCDDs. 2. Quantum yields of direct
phototransformation of 1,2,3,7-tetra-, 1,3,6,8-tetra-, 1,2,3,4,6,7,8-hepta-, and 1,2,3,4,6,7,8,9-octachlorodibenzo-p-
dioxin in aqueous acetonitrile and their sunlight half-lives. J Agric Food Chem 37:254-261.
Christmann, W; Kloppel, KD; Partscht, H; et al. (1989a) Tetrachlorobenzoquinones, a source of PCDD/PCDF.
Chemosphere 18(l-6):789-792.
Christmann, W; Kasiske, D; Kloppel, KD; et al. (1989b) Combustion of polyvinyl chloride - an important source for
the formation of PCDD/PCDF. Chemosphere 19(l-6):387-392.
Cianciarelli, D. (2000) "Measurement of PCDD/PCDF and hexachlorobenzene emissions from an electric arc
furnace shop, Dofasco Inc., Hamilton, Ontario." Report ERMD 99-08. Emissions Research Advancement Division,
Environment Canada.
Cianciarelli, D. (200 la) "Characterization of Organic Emissions from an Electric Arc Furnace, Gerdau Courtice
Steel Inc., Cambridge, Ontario," Report ERMD 2000-05. Emissions Research and Measurement Division,
Environmental Technology Advancement Directorate, Environment Canada.
Cianciarelli, D. (200 Ib) Characterization of emissions from the Kidd Metallurgical Copper Smelter Acid Plant,
Timmins, Ontario. Report ERMD 2001-07. Emissions Research and Measurement Division, Environmental
Technology Advancement Directorate, Environment Canada.
Charles E. Napier Company, Ltd. (2000) DRAFT - Background technical discussion paper on the release and control
of dioxins/furans from the steel sector. Prepared for Environment Canada, Minerals and Metals Division.
Charles E. Napier Company, Ltd. (2002) Final - Generic dioxin/furan emission testing protocol for the base metals
smelting sector. Prepared for Environment Canada.
Clark, T.; Clark, K; Paterson, S; et al. (1988) Wildlife monitoring, modeling, and fugacity. Environ Sci Technol
22(2): 120-127.
Clement, RE; Tashiro, C. (1991) Forest fires as a source of PCDD and PCDF. Presented at: Dioxin '91,11th
International Symposium on Chlorinated Dioxins and Related Compounds; Research Triangle Park, NC; September
1991.
03/04/05 R-8 DRAFT-DONOTCITEORQUOTE
-------
Clement, RE; Tosine, HM; Osborne, J; et al. (1985a) Levels of chlorinated organics in a municipal incinerator. In:
Keith, L.H.; Rappe, C.; Choudhary, G., eds., Chlorinated dioxins and dibenzofurans in the total environment II.
Boston, MA: Butterworth Publishers.
Clement, RE; Tosine, HM; Ali, B. (1985b) Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans in wood
burning stoves and fireplaces. Chemosphere 14:815-819.
Clement, RE; Tosine, HM; Osborne, J; et al. (1988) Gas chromatographic/mass spectrometric determination of
chlorinated dibenzo-p-dioxins and dibenzofurans in incinerator stack emissions and fly-ash: a 13-test study.
Biomedical and Environmental Mass Spectrometry 17:81-96.
Clement, RE; Boomer, D; Nalkwadi, KP; et al. (1990) Study of the relationship between trace elements and the
formation of chlorinated dioxin on flyash. In: Clement, R.E.; Kagel, R.O., eds, Emissions from combustion: origin,
measurement, control. Chelsea, MI: Lewis Publishers, Inc. pp. 57-64.
Cleverly, DH (1984) Chlorinated dibenzo-p-dioxins and furans in incineration of municipal solid waste.
Proceedings of workshop on energy from municipal waste research: A technical review of thermochemical systems,
February 22-24,1984, Kissimmee, FL. Argonne National lab, U.S. Department of Energy, pp. 295-319.
Cleverly, D; Schaum, J; Schweer, G; et al. (1997) The congener profiles of anthropogenic sources of chlorinated
dibenzo-p-dioxins and chlorinated dibenzofurans in the United states. Organohalogen Compounds 32:430-435.
Cleverly, DH; Morrison, RM; Riddle, BL; et al. (1991) Regulatory analysis of pollutant emissions, including
polychlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs), from municipal waste combustors. In:
Hattemer-Frey, H.A.; Travis,C., eds., Health effects of municipal waste incineration. Boca Raton, FL: CRC Press,
pp. 47-65.
Commoner, B. (1990) Making peace with the planet. New York, NY: Random House, Inc.
Commoner, B; McNamara, M; Shapiro, K; et al. (1984) Environmental and economic analysis of alternative
municipal solid waste disposal technologies, part II: The origins of chlorinated dioxins and dibenzofurans emitted by
incinerators that burn unseparated municipal solid waste, and an assessment of methods of controlling them. Center
for the Biology of Natural Systems, Queens College, CUNY, Flushing, New York. December 1, 1984.
Commoner, B; Webster, T, Shapiro, K; et al. (1985) The origins and methods of controlling polychlorinated
dibenzo-p-dioxin and dibenzofuran emissions from MSW incinerators. Presented at: 78th Annual Meeting of the Air
Pollution Control Assoc.; Detroit, MI; June 1985.
Commoner, B; Shapiro, K; Webster, T. (1987) The origin and health risks of PCDD and PCDF. Waste Management
and Research 5: 327-346.
Costner, PK. (1998) Correlation of chlorine input and PCDD/PCDF emissions at a full-scale hazardous waste
incinerator. Organohalogen Compounds 36:147-151.
Council of Great Lakes Industries. (1999) Octachlorostyrene and suggested industrial sources. A report to the Great
Lakes Binational Toxics Strategy OCS Workgroup.
Cramer, PH; Heiman, J; Horrigan, M; et al. (1995) Results of a national survey for polychlorinated dibenzo-p-
dioxins, dibenzofurans, and coplanar polychlorinated biphenyls in municipal biosolids. Organohalogen Compounds
24:305-308.
CRE. (1994) Emissions of environmental concern from coal utilisation. United Kingdom: Coal Research
Establishment. ECSC7220-EC/011. June 1994.
Crosby, DB. (1981) Environmental chemistry of pentachlorophenol. Pure & Appl. Chem. 53:1051-1080.
03/04/05 R-9 DRAFT-DONOTCITEORQUOTE
-------
Crummett, WB. (1982) Environmental chlorinated dioxins from combustion - the trace chemistries of fire
hypothesis. In: Hutzinger, O.; Frei, R.W.; Merian, E.; Pocchiari, F., eds. Chlorinated dioxins and related
compounds: impact on the environment. New York NY: Pergamon Press.
Cull, MR; Dobbs, AJ; Goudot, M; et al. (1984) Polychlorodibenzo-p-dioxins and dibenzofurans in technical
pentachlorophenol-results of a collaborative analytical exercise. Chemosphere 13(10): 1157-1165.
Curlin, LC; Bommaraju, TV. (1991) Alkali & chlorine products. In: Kirk-Othmer Encyclopedia of Chemical
Technology. 4th ed. pp. 938-1025.
deBoer, J. de; Stronck, CJN; Traag, WA; et al. (1993) Non-ortho and mono-ortho substituted chlorobiphenyls and
chlorinated dibenzo-p-dioxins, and dibenzofurans in marine and freshwater fish and shellfish from The Netherlands.
Chemosphere 26(10): 1832-1842.
De Fre, R; Rymen, R. (1989) PCDD and PCDF formation from hydrocarbon combustion in the presence of hydrogen
chloride. Chemosphere 19(l-9):331-336.
Dempsey, CR; Oppelt, ET. (1993) Incineration of hazardous waste: A critical review update. Air and Waste 43:25-
73.
Deutsch, DG; Goldfarb, TD. (1988) PCDD/PCDF contamination following a plastic fire in a university lecture hall
building. Chemosphere 17(12):2423-2431.
DeVoogt, P; Brinkman, UA. (1989) Production, properties and usage of poly chlorinated biphenyls. In: Halogenated
biphenyls, terphenyls, napthalenes, dibenzodioxins and related products. Kimbrough, R.; Jensen, A.A., Eds. New
York, NY: Elsevier Science Publishers.
Dickson, LC; Karasek, FW. (1987) Mechanism of formation of poly chlorinated dibenzo-p-dioxins produced on
municipal incinerator flyash from reactions of chlorinated phenols. J Chromatography 389:127-137.
Dickson, LC; Lenoir, D; Hutzinger, O. (1992) Quantitative comparison of de novo and precursor formation of
polychlorinated dibenzo-p-dioxins under simulated municipal solid waste incinerator post combustion conditions.
Environ Sci Technol 26:1822-1828.
Domalski, ES; Churney, KL; Ledford, AE; et al. (1986) Monitoring the fate of chlorine from MSW sampling
through combustion. Part 1: Analysis of the waste stream for chlorine. Chemosphere 15(9-12): 1339-1354.
Donnelly, JR. (1992) Waste incineration sources: refuse. In: Buonicore, A.J.; Davis, W.T., eds, Air pollution
engineering manual. Air and Waste Management Association. New York, NY: Van Nostrand Reinhold. pp. 263-
275.
Douben, PET; Eduljee, GH; Dyke, P. (1995) A review of potential PCDD and PCDF emission sources in the UK.
Organohalogen Compounds 24:131-136.
Doucet, LG. (1995) Reassessment of dioxin emissions from MWIs. In: Comments submitted by the American
Hospital Association to the U.S. Environmental Protection Agency on EPA's Reassessment Document for 2,3,7,8-
TCDD and Related Compounds. January 13, 1995.
Dow Chemical Co. (unknown) A closer look at the pesticide question for those who want the facts.
Duarte-Davidson, R; Sewart, A; Alcock, RE; et al. (1997) Exploring the balance between sources, deposition and the
environmental burden of PCDD/Fs in the U.K. terrestrial environment: an aid to identifying uncertainties and
research needs. Environ Sci Technol 31(1): 1-11.
03/04/05 R-10 DRAFT-DONOTCITEORQUOTE
-------
Duinker, JC; Hillebrand, MTJ. (1983) Characterization of PCB components in Clophen formulations by capillary
GC-MS and GC-ECD techniques. Environ Sci Technol 17(8):449-456.
Duinker, JC; Schulz, DE; Petrick, G. (1988) Multidimensional gas chromatography with electron capture detection
for the determination of toxic congeners of polychlorinated biphenyl mixtures. Analytical Chemistry 60:478-482.
Dumler-Gradl, R; Thoma, H; Vierle, O. (1995a) Research program on dioxin/furan concentration in chimney soot
from house heating systems in the Bavarian area. Organohalogen Compounds 24:115-118.
Dumler-Gradl, R; Tartler, D; Thoma, H; et al. (1995b) Detection of polybrominated diphenylethers (PBDE),
dibenzofurans (PBDF) and dibenzodioxins (PBDD) in scrap of electronics and recycled products. Organohalogen
Compounds 24:101-104.
Dung, M; O'Keefe, PW. (1992) Comparative rates of photolysis of polychlorinated dibenzofurans in organic solvents
and in aqueous solutions. Organohalogen Compounds 8:233-236.
Dyke, P; Coleman, P. (1995) Dioxins in ambient air, Bonfire Night 1994. Organohalogen Compounds 24:213-216.
Eastern Research Group, Inc. (1998) Report of the meeting to peer review the Inventory of Sources of Dioxininthe
United States. Washington, DC: U.S. Environmental Protection Agency, Office of Research and Development.
EPA Contract No. 68-D5-0028, Work Assignment No. 98-05.
Edelstein, DL (1995) Minerals yearbook - copper. Reston, VA: U.S. Geological Survey, Geologic Division.
Edelstein, DL. (1999) Personal communication between D. Edelstein (U.S. Geological Survey) and G. Schweer
(Versar, Inc.), August 17, 1999.
Eduljee, GH; Dyke, P. (1996) An updated inventory of potential PCDD and PCDF emission sources in the UK. The
Science of the Total Environment 177:303-321.
EER (Energy and Environmental Research Corp.). (1993) Engineering analysis and technical support to control
metal and organic emissions from combustion of hazardous waste in incinerators and BIFs. Washington, DC: Office
of Solid Waste. EPA Contract No. 68-CO-0094, Work Assignment No. 2-6.
EIA (Energy Information Administration). (1991) Estimates of U.S. biofuels consumption in 1990. Washington,
DC: U.S. Department of Energy, Office of Coal, Nuclear, Electric and Alternate Fuels. DOE/EIA-0548(90).
EIA. (1992) Fuel oil and kerosene sales 1991. Washington, DC: U.S. Department of Energy, Office of Oil and Gas.
DOE/EIA-0535(91).
EIA. (1993) Petroleum supply annual 1992, volume 1. Washington, DC: U.S. Deprtment of Energy, Office of Oil
and Gas. DOE/EIA-0340(92)/1.
EIA. (1994) Estimates of U.S. biomass energy consumption 1992. Washington, DC: U.S. Department of Energy,
Office of Coal, Nuclear, Electric, and Alternative Fuels. DOE/EIA-0548(92).
EIA. (1995a) Fuel oil and kerosene sales 1994. Washington, DC: U.S. Department of Energy, Office of Oil and
Gas. DOE/EIA-0535(94).
EIA. (1995b) Monthly energy review - October 1995. Washington, DC: U.S. Department of Energy, Office of
Energy Markets and End Use. DOE/EIA-0035(95/10).
EIA. (1995c) Annual energy review 1994. Washington, DC: U.S. Department of Energy, Office of Energy Markets
and End Use. DOE/EIA-0884(94).
EIA. (1997a) Fuel oil and kerosene sales 1996. Washington, DC: U.S. Department of Energy, Office of Oil and
Gas. DOE/EIA-0535(96).
03/04/05 R-ll DRAFT-DONOTCITEORQUOTE
-------
EIA. (1997b) Annual energy review 1996. Washington, DC: U.S. Department of Energy, Office of Energy Markets
and End Use. DOE/EIA-0384(96).
EIA. (1997c) Petroleum supply annual 1996, Volume 1. Washington, DC: U.S. Department of Energy, Office of
Oil and Gas. DOE/EIA-0340(96/1).
EIA. (1999) State energy data report 1996, consumption estimates. Washington, DC: U.S. Department of Energy,
Office of Energy Markets and End Use. DOE/EIA-0214(96).
EIA. (2001) Petroleum supply annual 2001, Volume 1. Washington, DC: U.S. Department of Energy, Office of Oil
and Gas. DOE/EIA-0340(01)/1.
EIA. (2002a) Annual energy review 2000. www.eia.doe.gov
EIA. (2002b) Quarterly Coal Report, www.eia.doe.gov
EIA. (2003a) Monthly Energy Review, Energy Consumption by Sector for the Year 2000.
www.eia.doe.gov/mer/consump.html. Last modified: January, 2003.
EIA. (2003b) 2000 State Energy Data. Washington, D.C. March 2003. (Internet Address:
http ://www. eia. doe .gov/emeu/states/sep_fuel/html/pdf/fuel_all.pdf).
Eitzer, BD; Hites, RA. (1987) Reply to comment on "Airborne dioxins and dibenzofurans: sources and fate."
Environ Sci Technol 21:924.
Eitzer, BD; Hites, RA. (1989) Dioxins and furans in the ambient atmosphere: A baseline study. Chemosphere 18(1-
6):593-598.
Eklund, G; Pedersen, JR; Stromberg, B. (1986) Phenol and HC1 at 550°C yield a large variety of chlorinated toxic
compounds. Nature 320: 155-156. March 13.
Eklund, G; Pedersen, JR; Stromberg, B. (1988) Methane, hydrogen chloride and oxygen form a wide range of
chlorinated organic species in the temperature range 400°C-959°C. Chemosphere 17 (3): 575-586.
Environics Research Group. (2001) Household garbage disposal and bBurning - Ontario survey. Prepared for
Environment Canada.
Environment Canada. (1985) The national incineration testing and evaluation program: Two-stage combustion
(Prince Edward Island). Environment Canada, Ottawa, Ontario, Canada. Report EPS 3/UP/l. September 1985.
Environment Canada. (2000) Characterization of organic compounds from selected residential wood stoves and
fuels. Environment Canada, Emissions Research and Measurement Division, Ottawa, Canada, Report ERMD 2000-
01. December 2001.
Environmental Risk Sciences, Inc. (1995) An analysis of the potential for dioxin emissions in the primary copper
smelting industry. Prepared for the National Mining Association.
Envisage Environmental, Inc. (1995) Test result summary for development of MACT standards. Testing location:
Wabash Alloys. Richfield, OH: Envisage Environmental Inc.
EPRI (Electric Power Research Institute). (1994) Electric utility trace substances synthesis report. Palo Alto, CA:
EPRI. EPRITR-104614.
EPRI. (1995) Pentachlorophenol (PCP) in soils adjacent to in-service utility poles in New York State. Palo Alto,
CA: EPRI. EPRI TR-104893.
03/04/05 R-12 DRAFT-DONOTCITEORQUOTE
-------
Erickson, M. (1986) Analytical chemistry of PCBs. Boston, MA, Butterworth Publishers.
Erickson, MD; Cole, CJ; Flora, JD; et al. (1984) Thermal degradation products from dielectric fluids. Washington,
D.C.: U.S. Environmental protection Agency, Office of Toxic Substances. EPA-560/5-84-009.
Esposito, MP; Tiernan, TO; Drydent, FE. (1980) Dioxins. Prepared for the U.S. Environmental Protection Agency,
Cincinnati, OH. November, 1980. EPA-600/2-80-197.
Fangmark, I; Stomberg, G; Berge, N; et al. (1994) Influence of postcombustion temperature profiles on the
formation of PCDDs, PCDFs, PCBzs, and PCBs in a pilot incinerator. Environ Sci Technol 28:624-629.
Federal Emergency Management Agency (FEMA). (1997) Fire in the United States. Washington, DC, United
States Fire Administration. FA-173/August 1997.
FEMA. (2001) The national fire problem. Washington, DC, United States Fire Administration. Source:
http://www.usfa.fema.gov/nfdc/national.htm
Federal Register. (1979) Decision and emergency order suspending registrations for certain uses of 2,4,5-T and
Silvex. FR (March 15) 44:15874-15920.
Federal Register. (1982a) Fob/chlorinated biphenyls (PCBs) use in electrical equipment. FR (April 22) 47:17426.
Federal Register. (1982b) Poly chlorinated biphenyls (PCBs) manufacturing, processing, distribution in commerce
and use prohibitions; use in electrical equipment. FR (August 25) 47:37342.
Federal Register. (1982c) FR (October 29) 47:49322.
Federal Register. (1984) Pentachlorophenol, and inorganic arsenicals; intent to cancel registrations of pesticide
products containing creosote, pentachlorophenol (including its salts) and the inorganic arsenicals; determination
concluding the rebuttal presumption against registration of the wood preservative uses of pesticide products;
availability of position document. FR(July 13)49:28666-28689.
Federal Register. (1985a) Regulation of fuels and fuel additives; Gasoline lead content: final rule and supplemental
notice of proposed rulemaking. FR (March 7) 50:9386-9408.
Federal Register. (1985b) Fob/chlorinated biphenyls in electrical transformers. FR (July 17) 50:29170.
Federal Register. (1986) Creosote, pentachlorophenol, and inorganic arsenicals; amendment of notice of intent to
cancel registrations. FR (January 10) 51:1334-1348.
Federal Register. (1987a) Pentachlorophenol; amendment of notice of intent to cancel registrations. F.R. (January 2)
52:140-148.
Federal Register. (1987b) Final determination and intent to cancel and deny applications for registrations of pesticide
products containing pentachlorophenol (including but not limited to its salts and esters) for non-wood uses. FR
(January 21) 52:2282-2293.
Federal Register. (1987c) Polyhalogenated dibenzo-p-dioxins/dibenzofurans; testing and reporting requirements;
final rule. FR (June 5) 52:21412-21452.
Federal Register. (1987d) Appendix A to part 60 (Amended). FR (December 16) 52:47853-47856.
Federal Register. (1990) National sewage sludge survey: availability of information and data, and anticipated
impacts on proposed regulation. FR (November 9) 55:47210-47283.
03/04/05 R-13 DRAFT-DONOTCITEORQUOTE
-------
Federal Register. (1991a) Standards of performance for new stationary sources and final guidelines for municipal
waste combustors. FR (February 11) 56:5488-5527.
Federal Register. (1991b) Standards of performance for new stationary sources and guidelines for control of existing
sources: municipal solid waste landfills: proposed rule and guideline. FR (May 30) 56:24468.
Federal Register. (1991c) FR (February 21) 56:7134.
Federal Register. (1993a) 2,3,5,6-Tetrachloro-2,5-cyclohexadiene-l,4-dione; proposed significant new use of a
chemical substance. FR (May 12) 58:27980-27986.
Federal Register. (1993b) Standards for the use or disposal of sewage sludge; final rules. FR (February 19) 58:9248-
9404.
Federal Register. (1993c) Chemicals; toxic chemical release reporting; community right-to-know; significant new
use rule. FR (December 1) 58:63500-63518.
Federal Register. (1993d) Standards of performance for new stationary sources and guidelines for control of existing
sources: Municipal solid waste landfills: notice of availability. FR (June 21) 58:33790-33792.
Federal Register. (1995a) Proposed standards of performance for new stationary sources and emission guidelines for
existing sources: medical waste incinerators. FR (February 27) 60:10654-010691.
Federal Register. (1995b) Hazardous waste management system; identification and listing of hazardous waste:
petroleum refining process wastes; land disposal restrictions for newly identified wastes; and CERCLA hazardous
substance designation and reportable quantities. FR (November 20) 60:57747-57800.
Federal Register. (1995c) National emission standards for hazardous air pollutants from secondary lead smelting:
final rule. FR (June 23) 60:32587-32601.
Federal Register. (1995d) National emission standards for hazardous air pollutants (NESHAP); secondary lead
smelters; PVC in feedstock: proposed rule; amendments. FR (April 19) 60:19556.
Federal Register. (1995e) Standards of performance for new stationary sources and emission guidelines for existing
sources: municipal waste combustors, final rule. FR (December 19) 60:65387-65436.
Federal Register. (1996a) Standards of performance for new stationary sources and guidelines for control of existing
sources: municipal solid waste landfills: final rule and guideline. FR (March 12) 61:9905-9944.
Federal Register. (1996b) Revised standards for hazardous waste combustors: proposed rule. FR (April 19) 61:
17357-17536.
Federal Register. (1997a) Toxic chemicals; PCBs; submission of IRC No. 1000 to OMB; information collection
activities. FR (January 21) 62:3035-3036.
Federal Register. (1997b) Standards of performance for new stationary sources and emission guidelines for existing
sources: hospital/medical/infectious waste incinerators; final rule. FR (September 15) 62:48347-48391.
Federal Register. (1998a) Hazardous waste management system; identification and listing of hazardous waste;
petroleum refining process wastes; land disposal restrictions for newly identified wastes; and CERCLA hazardous
substance designation and reportable quantities. F.R. (August 8) 63:42110-42189.
Federal Register. (1998b) Source category listing for Section 112(d)(2) rulemaking pursuant to Section 112(c)(6)
requirements. FR (April 10) 63:17838-17855.
03/04/05 R-14 DRAFT-DONOTCITEORQUOTE
-------
Federal Register. (1998c) National emission standards for hazardous air pollutants for source category: pulp and
paper production; effluent limitations guidelines, pretreatment standards, and new source performance standards:
pulp, paper, andpaperboard category. FR (April 15) 63:18504-18751.
Federal Register. (1999a) National emission standards for hazardous air pollutants for source categories; Portland
Cement manufacturing industry. FR (June 14) 64:31897-31962.
Federal Register. (1999b) NESHAPS: Final standards for hazardous air pollutants for hazardous waste combustors.
FR (September 30) 64:52828-53077.
Federal Register. (1999c) Emission guidelines for existing stationary sources: small municipal waste combustion
units; proposed rule. New source performance standards for new small municipal waste combustion units. FR
(August 30) 64:47233-47307.
Federal Register. (1999d) Standards for the Management of Cement Kiln Dust; Proposed Rule. FR (August 20)
64:161.
Federal Register. (2004) National emission standards for hazardous air pollutants: proposed standards for hazardous
air pollutants for Hazardous Waste Combustors (Phase 1 Final replacement standards and Phase II): Proposed rule.
FR (April 201) 69:21998-21385.
Feil, VJ; Tiernan, T. (1997) Pentachlorophenol as a source of dioxins and furans. Organohalogen Compounds
33:353-354.
Fenton, M. (1996) Minerals yearbook - iron and steel. Washington, DC: U.S. Department of the Interior, U.S.
Geological Survey.
Fenton, M. (2001) Minerals yearbook - iron and steel. Washington, DC: U.S. Department of the Interior, U.S.
Geological Survey.
Ferrario, J; Byrne, C. (2000) Polychlorinated dibenzo-p-dioxins in the environment from ceramics and pottery
produced from ball clay. Presented at the 20th International Symposium on Halogenated Environemntal Organic
Pollutants and POPs, Monterey, California, August 13-17, 2000.
Ferrario, J; Byrne, C; Lorber, M; et al. (1997) A statistical survey of dioxin-like compounds in United States poultry
fat. Organohalogen Compounds, 32:245-251.
Ferrario, J; Byrne, C; Cleverly, D. (2000) 2,3,7,8-Dibenzo-p-dioxins in mined clay products from the United States:
evidence for possible natural formation. Environ. Sci. and Technol, 34:4524-4532.
Fiedler, H. (1993) Formation and sources of PCDD/PCDF. Organohalogen Compounds 11:221-228.
Fiedler, H; Hutzinger, O. (1992) Sources and sinks of dioxins: Germany. Chemosphere,25:1487-1491.
Fiedler, H; Lindert, M. (1998) Dtisseldorf Airport fire 1996: results and comparison with accidental fires.
Organohalogen Compounds 36:69-72.
Fiedler, H; Hutzinger, O; Hosseinpour, J. (1993) Analyses and remedial actions following an accidental fire in a
kindergarten. Organohalogen Compounds 14:19-22.
Firestone, D; Ress, J; Brown, NL; et al. (1972) Determination of polychlorodibenzo-p-dioxins and related
compounds in commercial chlorophenols. J Assoc Off Anal Chem 55(l):85-92.
Fisher, TS; Hayward, DG; Stephens, RD; Stenstrom, MK. (1998) Polychlorinated di-benzo-dioxins and di-benzo-
furans in Los Angeles urban runoff. Submitted for publication.
03/04/05 R-15 DRAFT-DONOTCITEORQUOTE
-------
Fleischer, O; Wichmann, H; Lorenz, W. (1999) Release of poly chlorinated dibenzo-p-dioxins and dibenzofurans by
setting off fireworks. Chemosphere 39:925-932.
Frame, GM. (1995) A comprehensive, multicenter study of PCB elution on capillary GC columns. Pittcon '95. New
Orleans, LA; March 8, 1995; Paper 717.
Frame, GM. (1997) A collaborative study of 209 PCB congeners and 6 aroclors on 20 different HRGC columns.
Fresenius Journal of Analytical Chemistry. 357(6):714-722.
Frame, GM. (1999) Improved Procedure for Single DB-XLB Column GC MS-SIM Quantitation of PCB Congener
Distributions and Characterization of Two Different Preparations Sold as "Aroclor 1254" J High Resol Chromatogr
22(10):533-540.
Frame, GM; Cochran, JW; Bowadt, SS. (1996a) Complete PCB congener distributions for 17 aroclor mixtures
determined by 3 HRGC systems optimized for comprehensive, quantitative, congener-specific analysis. J High
Resol Chromatogr 19(12):657-668.
Frame, GM; Wagner, RE; Carnahan, JC; et al. (1996b) Comprehensive, quantitative, congener-specific analyses of
eight aroclors and complete PCB congener assignments on DB-1 capillary GC columns. Chemosphere 33(4):603-
623.
Frank, H; Frank, W. (1989) Uptake of airborne tetrachloroethane by spruce needles. Environ Sci Technol
23(3):365-367.
Freeman, RA; Schroy, J.M. (1985) Environmental mobility of dioxins. Aquatic Toxicology and Hazard
Assessment: Eighth Symposium, ASTM STP 891, R.C. Banner and DJ. Hansen, Eds. American Society for Testing
and Materials, Philadelphia, PA. pp. 422-439.
Fries, GF; Dawson, TE; Paustenbach, DJ; et al. (1997) Biosynthesis of hepta- and octa-chlorodioxins in cattle and
evidence for lack of involvement by rumen microorganisms. Organohalogen Compounds 33:296-301.
Friesen, JK; Muir, DCG; Webster, GRB. (1990) Evidence of sensitized photolysis of polychlorinated dibenzo-p-
dioxins in natural waters under sunlight conditions. Environ Sci Technol 24(11): 1739-1744.
Friesen, KJ; Loewen, MD; Foga, MM. (1993) Environmental aquatic photodegradation of chlorinated dibenzofurans
and their photoproducts. Organohalogen Compounds 12:135-137.
Froese, KL; Hutzinger, O. (1994) The formation of chlorinated benzenes and phenols in fly ash catalysed reactions
oftrichloroethylene. Chemosphere 28 (11):1977-1987.
Froese, KL; Hutzinger, O. (1996a) Polychlorinated benzene and polychlorinated phenol in heterogeneous
combustion reactions of ethylene and ethane. Environ Sci Technol 30:1009-1013.
Froese, KL; Hutzinger, O. (1996b) Polychlorinated benzene, phenol, dibenzo-p-dioxin, and dibenzofuran in
heterogeneous combustion reactions of acetylene. Environ Sci Technol 30: 998-1008.
Froese, K; Hutzinger, O. (1997) Mechanisms of formation of polychlorinated benzenes and phenols from
heterogeneous reactions of Cs aliphatics. Environ Sci Technol 31:542-547.
Fuchs, R; Towara, J; Hutzinger, O. (1990) PCDD/F in the dry-cleaning process. Organohalogen Compounds 3:441-
444.
Funcke, W; Theisen, J; Balfanz, E; Konig, J. (1988) Polychlorierte Dibenzofurane (PCDF) und polychlorierte
Dibenzo(p)dioxine (PCDD) in Ruckstanden und emissionen eines Brandes in Anwesenheit von PBC-haltigen
materialien. Staub-ReinhaltungderLuft48. 393-396.
03/04/05 R-16 DRAFT-DONOTCITEORQUOTE
-------
Funk, S. (1996) Memorandum from S. Funk (EPA/OPP/HED) to Wm. Hazel (EPA/OPP/HED). Washington, DC:
U.S. Environmental Protection Agency, Office of Pesticide Programs. May 28, 1996.
Gaggi, C; Bacci, E; Calamari, D; et al. (1985) Chlorinated hydrocarbons in plant foliage: An indication of the
tropospheric contamination level. Chemosphere 14(11-12): 1673-1686.
Galson Corporation. (1995) Source test report: Source emission testing at Roth Brothers Smelting Corporation.
East Syracuse, NY: Galson Corporation.
Gambogi, J. (1996) Minerals yearbook - titanium. Reston, VA: U.S. Geological Survey, Geologic Division.
Gan, DR; Berthouex, PM. (1994) Disappearance and crop uptake of PCBs from sludge-amended farmland. Water
Environment Research 66(l):54-69.
Gertler, AW; Sagebiel, JC; Dippel, WA; et al. (1996) A study to quantify on-road emissions of dioxins and furans
from mobile sources: phase 2. Reno, NV: Desert Research Institute.
Gertler, A; Sagebiel, J; Dippel, W; et al. (1998) Measurement of dioxin and furan emissions factors from heavy duty
diesel vehicles. J of the Air and Waste Mgmt Assoc 48:276-278.
Geueke, K; Gessner, A; Quass, U; et al. (1999) PCDD/F emissions from heavy duty vehicle diesel engines.
Chemosphere 38:2791-2806.
Gillespie, WJ. (1994) A summary of data reflective of U.S. pulp and paper industry progress in reducing the
TCDD/TCDF content of effluents, pulps and wastewater treatment sludges. Organohalogen Compounds 20:255-
260.
Gillespie, WJ. (1995) Progress in reducing the TCDD/TCDF content of effluents, pulps and wastewater treatment
sludges from the manufacturing of bleached chemical pulp. Research Triangle Part, NC: National Council of the
Paper Industry for Air and Stream Improvement, Inc.
Gillespie, WJ. (1997) Letter to G. Schweer (Versar, Inc.) dated February 10, 1997. Research Triangle Park, NC:
National Council of the Paper Industry for Air and Stream Improvement, Inc.
Gillespie, WJ. (1998) Letter to G. Schweer (Versar, Inc.) dated October 8, 1998. Research Triangle Park, NC:
National Council of the Paper Industry for Air and Stream Improvement, Inc.
Gillespie, W. (2002) Letter to C. Peck (Versar, Inc.) Dated August 5, 2002. "Estimated PCDD/F releases from the
pulp and paper industry" Research Triangle Park, NC: National Council of the Paper Industry for Air and Stream
Improvement, Inc.
Oilman, AP; Douglas, VM; Newhook, RC; et al. (1988) Chlorophenols and their impurities: a health hazard
evaluation. Health and Welfare Canada. Document No. H46-2/88-110E.
Gobran, T; Khurana, V; MacPherson, K; et al. (1995) PCDD/PCDF levels in raw sewage, final effluent, sludge, and
ash samples from an Ontario wastewater treatment plant. Organohalogen Compounds 24:75-80.
Goldfarb, TD; Malloy, TA; Surico, M. (1992) PCDDs, PCDFs, PCBs, chlorophenols (CPs) and chlorobenzenes
(CBzs) in samples from various types of composting facilities in the United States. Organohalogen Compounds
8:253-256.
Green, LC; Lester, RL; Armstrong, SR. (1995) Comments on Estimating Exposures to Dioxin-Like Compounds:
Review Draft. Cambridge, MA: Cambridge Environmental Inc. Dated January 12, 1995, and May 11, 1995.
03/04/05 R-17 DRAFT-DONOTCITEORQUOTE
-------
Greenpeace. (1993) Dioxin factories: a study of the creation and discharge of dioxins and other organochlorines
from the production of PVC. Amsterdam, The Netherlands: Greenpeace International.
Greer, WL; Johnson, MD; Raught, EC; Steuch, HE; Trusty, CB. (1992) Portland cement. In: Buonicore, A.J.;
Davis, W.T.; eds. Air pollution engineering manual, Air and Waste Management Association. New York, NY: Van
Nostrand Reinhold.
Gribble, GW. (1994) The natural production of chlorinated compounds. Environ. Sci. Technol. 28(7):310A-319A.
Guerin, MR; Jenkins, RA; Tomkins, BA. (1992) The chemistry of environmental tobacco smoke: composition and
measurement. Chelsea, MI: Lewis Publishers.
Gullett, BK; Lemieux, PM. (1994) Role of combustion and sorbent parameters in prevention of poly chlorinated
dibenzo-p-dioxin and polychlorinated dibenzofuran formation during waste combustion. Environ Sci Technol
28(1):107-118.
Gullett, BK; Ryan, JV. (1997) On-road sampling of diesel engine emissions of polychlorinated dibenzo-p-dioxin and
polychlorinated dibenzofuran. Organohalogen Compounds 32:451-456.
Gullett, B; Touati, A. (2003) PCDD/F emissions from forest fire simulations. Atmospheric Environment 37:803-
813.
Gullett, BK; Bruce, KR; Beach, LO. (1990a) Formation of chlorinated organics during solid waste combustion.
Waste Management and Research 8:203-214.
Gullett, BK; Bruce, KR; Beach, LO. (1990b) The effect of metal catalysts on the formation of polychlorinated
dibenzo-p-dioxin and polychlorinated dibenzofuran precursors. Chemosphere 20: 1945-1952.
Gullett, BK; Bruce, KR; Beach, LO. (1991a) The effect of sulfur compounds on the formation mechanism of PCDD
and PCDF in municipal waste combustors.U.S. EPA, Research Triangle Park,NC; Acurex Corp., Research Triangle
Park,NC. In: Conference papers from the second international conference on municipal waste combustion, April 15-
19, 1991, Tampa, FL. Air and Waste Management Association, Pittsburgh, PA. pp.16-34.
Gullett, BK; Bruce, KR; Beach, LO; et al. (1991b) Mechanistic steps in the production of PCDD and PCDF during
waste combustion. Presented at: Dioxin '91,11th International Symposium on Chlorinated Dioxins and Related
Compounds; Research Triangle Park, NC; September 1991.
Gullett, B; Bruce, K; Beach, L. (1992) Mechanistic steps in the production of PCDD and PCDF during waste
combustion. Chemosphere 25(7-10): 1387-1392.
Gullett, BK; Lemieux, PM; Lutes, CC; et al. (1999) PCDD/F emissions from uncontrolled, domestic waste burning.
Organohalogen Compounds 41:27-30.
Gullett, BK; Lemieux, PM; Winterrowd, CK; et al. (2000a) PCDD/F emissions from uncontrolled, domestic waste
burning. Organohalogen Compounds 46:193-196.
Gullett, BK; Lemieux, PM; Lutes, CC; et al. (2000b) Emissions of PCDD/F from uncontrolled, domestic waste
burning. Chemosphere (in press).
Gurprasad, N; Constable, M; Haidar, N; et al. (1995) Polychlorinated dibenzo-p-dioxins (PCDDs) leaching from
pentachlorophenol-treated utility poles. Organohalogen Compounds 24:501-504.
Gutenmann, WH; Rutzke, M; Kuntz, HT; et al. (1994) Elements and polychlorinated biphenyls in sewage sludges of
large cities in the United States. Chemosphere 28(4):725-728.
03/04/05 R-18 DRAFT-DONOTCITEORQUOTE
-------
Hagenmaier, H. (1986) Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in commercial chlorophenols and
related products. Fresenius Z Anal Chem. 325:603-606.
Hagenmaier, H. (1987) Belastung der umwelt mit dioxinen. Institut fur Organische Chemie der Universitat
Tubingen.
Hagenmaier, H. (1994) Contributions of diesel-powered vehicles and wood burning to overall PCDD/PCDF
emissions. Organohalogen Compounds 20:267-270.
Hagenmaier, H; Brunner, H. (1987) Isomer-specific analysis of pentachlorophenol and sodium pentachlorophenate
for2,3,7,8-substitutedPCDD andPCDF at sub-ppb levels. Chemosphere 16:1759-1764.
Hagenmaier, H; Kraft, M; Jager, W; et al. (1986) Comparison of various sampling methods for PCDDs and PCDFs
in stack gas. Chemosphere 15:1187-1192.
Hagenmaier, H; Dawidowsky, V; Weber, UB; et al. (1990) Emission of polyhalogenated dibenzodioxins and
dibenzofurans from combustion-engines. Organohalogen Compounds 2:329-334.
Hagenmaier, H; Lindig, C; She, J. (1994) Correlation of environmental occurrence of polychlorinated dibenzo-p-
dioxins and dibenzofurans with possible sources. Chemosphere 29(9-11):2163-2174.
Haghunathan, K; Gullett, BK. (1996) Role of sulfur in reducing PCDD and PCDF formation. Environ Sci Technol
30: 1827-1834.
Haglund, P; Egeback, K-E; Jansson, B. (1988) Analysis of PBDD/F in vehicle exhaust. Presented at: Dioxin '88, 8th
International Symposium on Chlorinated Dioxins and Related Compounds; Umea, Sweden; August 1988.
Halonen, L; Tarhanen, J; Ollikainen, S; et al. (1994) The effect of inorganic and organic chlorine on formation of
highly chlorinated organic compounds during incineration: Laboratory pilot study. Chemosphere 28 (12): 2129-
2138.
Hammerstrom, K; Schweer, G; Adkins, L; et al. (1985) Exposure assessment for polychlorinated biphenyls (PCBs):
incidental production, recycling, and selected authorized uses. Washington, DC: U.S. Environmental Protection
Agency, Office of Toxic Substances. EPA Contract No. 68-01-6271, Task No. 21.
Harner, T; Mackay, D; Jones, KC. (1995) Model of the long-term exchange of PCBs between soil and the
atmosphere in the southern U.K. Environ Sci Technol 29(5): 1200-1209.
Harnly, M; Stephens, R; McLaughlin, C; et al. (1995) Polychlorinated dibenzo-p-dioxin and dibenzofuran
contamination at metal recovery facilities, open burn sites, and a railroad car incineration facility. Environ Sci
Technol 29(3):677-684.
Harrad, SJ; Malloy, TA; Khan, MA; et al. (1991) Levels and sources of PCDDs, PCDFs, chlorophenols (CPs) and
chlorobenzenes (CBzs) in composts from a municipal yard waste composting facility. Chemosphere 23(2): 181-191.
Harrad, SJ; Sewart, AP; Jones, KC. (1992a) PCDD/CDFs in the British environment: sinks, sources and temporal
trends. Organohalogen Compounds 9:89-92.
Harrad, SJ; Jones, KC. (1992b) A source inventory and budget for chlorinated dioxins and furans in the United
Kingdom environment. The Science of the Total Environment 126:89-107.
Hay, DJ; Finkelstein, A; Klicius, R. (1986) The national incineration testing and evaluation program: An assessment
of two-stage incineration and pilot scale emission control. Paper presented to U.S. EPA Science Advisory Board,
Washington, DC. Environment Canada, Ottawa, Ontario, Canada. June 1986.
03/04/05 R-19 DRAFT-DONOTCITEORQUOTE
-------
Headrick, M; Hollinger, K; Lovell, R; et al. (1999) PBBs, PCBs, and dioxins in food animals, their public health
implications. Chemical Food Borne Hazards and Their Control, 15:109-131.
Heath, E. (1995) Memorandum from Elizabeth Heath of Research Triangle Institute, to Joseph Wood of Emission
Standards Division, OAQPS, EPA, August 23, 1995. "Assignment of Existing Cement Kilns to Model Kilns by
Type of Process."
Heindl, A; Hutzinger, O. (1987) Search for industrial sources of PCDD/PCDF. III. Short-chain chlorinated
hydrocarbons. Chemosphere 16(8/9): 1949-1957.
Helble, JJ. (1993) Analysis of dioxin emissions from the incineration of hazardous waste. Washington, DC: U.S.
Environmental Protection Agency, Office of Solid Waste, Permits and State Programs Division.
Hengstmann, R; Hamann, R; Weber, H; et al. (1990) Impact of sewage sludge and sewer slimes by poly chlorinated
dibenzo-p-dioxins and polychlorinated dibenzofurans. Organohalogen Compounds 4:407-412.
Hickey, WJ. (1995) Enhancing PCB biodegradatin in soil with chlorobenzoate-degrading inoculants.
Organohalogen Compounds 24:29-32.
Himberg, K; Sippola, E. (1990) Multidimensional gas chromatography - mass spectrometry as a method for the
determination of coplanar PCB congeners. Organohalogen Compounds 4:183-186.
Kites, RA. (1991) Atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans.
Prepared for the U.S. Environmental Protection Agency, Methods Research Branch, Atmospheric Research and
Exposure Assessment Laboratory, Office of Research and Development, Research Triangle Park, NC. EPA/600/3-
91/002.
HMIP. (1995) A review of dioxin emissions in the UK. Her Majesty's Inspectorate of Pollution.
HMIP/CPR2/41/1/38.
Ho, AKW; Clement, RE. (1990) Chlorinated dioxins/furans in sewage and sludge of municipal water pollution
control plants. Chemosphere 20(10-12):1549-1552.
Hoekstra, EJ; De Leer, WB; Brinkman, UT. (1999) Natural formation of chlorinated phenols, dibenzo-p-dioxins, and
dibenzofurans in soil of a Douglas Fir forest. Environ. Sci. and Technol. 33:2543-2549.
Holderman, TS. (1995) Dioxin levels from D/F test rule data submittals. Memorandum from T.S. Holderman
(EPA/OPPT/CMD) to A. Adenuga (Versar, Inc.). Dated Aug. 2, 1995.
Holderman, TS; Cramer, PH. (1995) Updated results of polyhalogenated dibenzo-p-dioxin/dibenzofuran testing and
reporting under the Toxic Substances Control Act (TSCA). Organohalogen Compounds 24:137-140.
Horstmann, M; McLachlan, MS. (1994a) Textiles as a source of polychlorinated dibenzo-p-dioxins and
dibenzofurans (PCDD/CDF) in human skin and sewage sludge. Environ Sci and Pollut Res 1(1): 15-20.
Horstmann, M; McLachlan, MS. (1994b) Polychlorinated dibenzo-p-dioxins and dibenzofurans in textiles and their
transfer to human skin, sewage sludge and other matrices. Organohalogen Compounds 20:251-254.
Horstmann, M; McLachlan, MS. (1995) Concentrations of polychlorinated dibenzo-p-dioxins (PCDD) and
dibenzofurans (PCDF) in urban runoff and household wastewaters. Chemosphere 31(3):2887-2896.
Hornbuckle, KC; Achman, DR; Eisnreich, SJ. (1993) Over-water and over-land, polychlorinated biphenyls in Green
Bay, Lake Michigan. Environ Sci Technol 27(l):87-97.
Horstmann, M; McLachlan, MS. (1992) Initial development of a solid-phase fugacity meter for semivolatile organic
compounds. Environ Sci Technol 26(8): 1643-1649.
03/04/05 R-20 DRAFT-DO NOT CITE OR QUOTE
-------
Horstmann, M; McLachlan, M; Reissinger, M. (1992) Investigation of the origin of PCDD/CDF in municipal
sewage. Organohalogen Compounds 9:97-100.
Horstmann, M; McLachlan, M; Reissinger, M. (1993a) Further investigations of the sources of PCDD/CDF in
municipal sewage sludge. Organohalogen Compounds 11:293-296.
Horstmann, M; McLachlan, M; Reissinger, M; et al. (1993b) An investigation of PCDD/CDF formation during
textile production and finishing. Organohalogen Compounds 11:417-420.
Hryhorczuk, OD; Withrow, WA; Hesse, CS; et al. (1981) A wire reclamation incinerator as a source of
environmental contamination with TCDDs and TCDFs. Archives of Environmental Health 36(5):228-234.
Huang, H; Buekens, A. (1995) On the mechanisms of dioxin formation in combustion processes. Chemosphere 31
(9):4099-4117.
Huang, CW; Miyata, H; Lu, J; et al. (1992) Levels of PCBs, PCDDs and PCDFs in soil samples from incineration
sites for metal reclamation in Taiwan. Chemosphere 24(11): 1669-1676.
Huang, H; Biesemans, M, Buekens, A. (1999) Characterization of the nature of de novo synthesis by 13C NMR.
Organohalogen Compounds 41:105-108.
Huckins, JN; Stalling, DL; Petty, JD. (1980) Carbon-foam chromatographic separation of non-o-o'-chlorine
substituted PCBs from Aroclor mixtures. J. Assoc. Off. Anal. Chem. 63(4):750-755.
Huckaby. (2003) Memorandum from Jason Huckaby, ERG, to Walt Stevenson, U.S., Environmental Protection
Agency. Dioxin/Furan Congener Emissions from Large Municipal Waste Combustion (MWC) Units at MACT
Compliance (year 2000). March 27, 2003.
Htilster, A; Marschner, H. (1993) Soil-plant transfer of CDD/PCDF to vegetables of the cucumber family
(Cucurbitaceae). Environ Sci Technol 28(6): 1110-1115.
Htilster, A; Marschner, H. (1994) The influence of root exudates on the uptake of CDD/PCDF by plants.
Organohalogen Compounds 20:31-34.
Hutzinger, O; Fiedler, H. (199 la) Formation of dioxins and related compounds in industrial processes. In:
Bretthauer, E.W.; Kraus, H.W.; di Domenico, A., eds. Dioxin perspectives. A pilot study on international
information exchange on dioxins and related compounds. New York, NY: Plenum Press.
Hutzinger, O; Fiedler, H. (1991b) Formation of dioxins and related compounds from combustion and incineration
processes. In: Bretthauer, E.W.; Kraus, H.W.; di Domenico, A., eds. Dioxin perspectives. A pilot study on
international information exchange on dioxins and related compounds. New York, NY: Plenum Press.
Hutzinger, O; Fiedler, H. (1992) From source to exposure: some open questions. Organohalogen Compounds 9:1-4.
Hutzinger, O; Essers, U; Hagenmaier, H. (1992) Untersuchungen zur emission halogenierter dibenzodioxine und
dibenzofurane aus verbrennungsmortoren beim betrieb mit handelsublichen betriebsstoffen. Universities of
Bayreuth, Stuttgart and Tubingen, Germany. GSF-Forschungszentrum, Munich, Germany, ISSN 0937-9932.
Huwe, JK; Feil, VJ; Tiernan, TO. (1998) In vivo formation of octachlorodibenzo-p-dioxin from a predioxin.
Organohalogen Compounds 36:93-95.
Imagawa, T; Lee, C. (2001) Correlation of poly chlorinated naphthalenes with polychlorinated dibenzofurans formed
from waste incineration. Chemosphere. 44:1151-1520.
03/04/05 R-21 DRAFT-DONOTCITEORQUOTE
-------
Jager, J; Wilken, M; Zeschmar-Lahl, B. (1992) Dioxin und furan emissionen in Berlin eine hochrechnung. Staub-
Reinhaltung der Luft. 52:99-106.
Jansson, B; Sundstrom, G; Ahling, B. (1977) Formation of poly chlorinated dibenzo-p-dioxins during combustion of
chlorophenol formulations. Science in the Total Environment 10: 209-217.
Jarmohamed, W; Mulder, P. (1994) Oxychlorination and combustion of propene on fly-ash formation of chlorinated
benzenes, dibenzodioxins and mono- and dibenzofurans. Chemosphere 29 (9-11): 1911-1917.
Jensen, S; Sundstrom, G; Frescati, L. (1974) Structures and levels of most chlorobiphenyls in two technical PCB
products and in human adipose tissue. Ambio 3(2):70-76.
Jobst, H; Aldag, R. Umweltchem. Okotox. 2000, 1, 2-4.
Jones, KC; Alcock, RE. (1996) Dioxin inputs to the environment: A review of temporal trend data and proposals for
a monitoring programme to detect past and future change in the U.K. Department of Environment report.
Jury, WA; Spencer, WF; Farmer, WJ. (1983) Behavior assessment model for trace organics in soil: model
description. J Environ Qua! 12:558-564.
Kannan, N; Tanabe, S; Wakimoto, T; et al. (1987) Coplanar polychlorinated biphenyls in Aroclor and Kanechlor
mixtures. J Assoc Off Anal Chem 70(3):451-454.
Kanters, J; Louw, R. (1994) Chlorine input and output in combustion of municipal solid waste in a lab-scale mini-
reactor system. Chemosphere 29 (9-11): 1919-1925.
Kao, AS; Venkataraman, C. (1995) Estimating the contribution of reentrainment to the atmospheric deposition of
dioxin. Chemosphere 31(10):4317-4331.
Karasek, FW; Dickson, LC. (1987) Model studies of polychlorinated dibenzo-p-dioxin formation during municipal
refuse incineration. Science 237: 754-756. August 14.
Katami, T; Yasuhara, A; Okuda, T; Shibamoto, T. (2002) Formation of PCDDs, PCDFs, and coplanar PCBs from
polyvinylchloride during combustion in an incinerator. Environ Sci Technol 36:1320-1324.
Kearney, PC; Woolson, EA; Isensee, AR; et al. (1973) Tetrachlorodibenzodioxin in the environment: sources, fate,
and decontamination. Environmental Health Perspectives. 5:273-277.
Kieatiwong, S; Nguyen, LV; Hebert, VR; et al. (1990) Photolysis of chlorinated dioxins in organic solvents and on
soils. Environ Sci Technol 24(10): 1575-1580.
Kim, K-S; Hong, K-H; Ko, Y-H (2004) Emission characteristics of PCDD/Fs, PCBs, chlorobenzenes,
chlorophenols, and PAHs from polyvinylchloride bomustion at various temperatures. J Air Waste Manage Assoc
54:555-562.
Kirby, R. (1994) Petroleum refining industry - presence of dioxins and furans in wastewater generated by reforming
operations. Washington, DC: U.S. Environmental Protection Agency, Office of Water, Engineering and Analysis
Division. May 1994.
Kirsbaum, IZ; Domburg, GE; Sergeyeva, VN. (1972) Extension of application range of gas chromatography to
analysis of lignin pyrolysis products. Latv. PSR Zinat. Akad. Vestis, Khim. Ser, pp 700-707. Cited in:
Choudhry,G.G.; Hutzinger, O. (1983). Mechanistic aspects of the thermal formation of halogenated organic
compounds including polychlorinated dibenzo-p-dioxins. New York, NY: Gordon and Breach.
03/04/05 R-22 DRAFT-DO NOT CITE OR QUOTE
-------
Kjeller, L; Jones, KC; Johnston, AE; et al. (1991) Increases in the polychlorinated dibenzo-p-dioxin and -furan
content of soils and vegetation since the 1840s Environ. Sci. Technol. 25(9): 1619-1627.
Klasmeier, J; McLachlan, MS. (1995) A screening method for detection of OCDD/F in textiles. Organohalogen
Compounds 23:131-134.
KMG-Bernuth, Inc. (1997) Letter from Thomas H. Mitchell (KMG-Bernuth) to Matthew Lorber (U.S.
EPA/ORD/NCEA). March 5, 1997. Houston, TX: KMG-Bernuth, Inc.
Knepper, WA. (1981) Iron. In: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. 13:735-753. New York,
NY: John Wiley and Sons.
Knittel, D. (1983) Titanium and titanium alloys. In: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed.
23:98-130. New York, NY: John Wiley and Sons.
Kobylecki, R; Ohira, K; Ito, I; et al. (2001) Dioxin and fly ash free incineration by ash pelletization and reburning.
Environmental Science and Technology. 35:4313-4319.
Koester, CJ; Hites, RA. (1992) Photodegradation of polychlorinated dioxins and dibenzofurans adsorbed to fly ash.
Environ. Sci. Technol. 26(3):502-507.
Konduri, R; Altwicker, E. (1994) The effect of the electric field on the formation of PCDD in electrostatic
precipitators. Hazardous Waste & Hazardous Materials 11 (1): 145-156.
Koning, J; Sein, AA; Troost, LM; et al. (1993) Sources of dioxin emissions in the Netherlands. Organohalogen
Compounds 14:315-318.
Kramer, D.A. (1995) Minerals yearbook - magnesium. Reston, VA: U.S. Geological Survey, Geologic Division.
Krauss, T; Krauss, P; Hagenmaier, H. (1994) Formation of PCDD/PCDF during composting? Chemosphere
28(1):155-158.
Kuck, PH. (1995) Minerals yearbook - nickel. Reston, VA: U.S. Geological Survey, Geologic Division.
Kutz, FW; Barnes, DG; Bretthauer, EW; et al. (1990) The International Toxicity Equivalency Factor (I-TEF) method
for estimating risks associated with exposures to complex mixtures of dioxins and related compounds. Toxicological
and Environmental Chemistry 26:99-109.
Kwok, ESC; Atkinson, R; Arey, J. (1995) Rate constants for the gas-phase reactions of the OH radical with
dichlorobiphenyls, 1-chlorodibenzo-p-dioxin, 1,2-dimethoxybenzene, and diphenyl ether: estimation of OH radical
reaction rate constants for PCBs, PCDDs, and PCDFs. Environ Sci Technol 29(6): 1591-1598.
Lahl, U. (1993) Sintering plants of steel industry - the most important thermical PCDD/CDF source in industrialized
regions. Organohalogen Compounds 11:311-314.
Lahl, U. (1994) Sintering plants of steel industry - PCDD/F emission status and perspectives. Chemosphere 29(9-
11):1939-1945.
Lahl, U; Wilken, M; Zeschmar-Lahl, B; Jager, J. (1991) PCDD/PCDF balance of different municipal waste
management methods. Chemosphere 23(8-10): 1481-1489.
Lamparski, LL; Stehl, RH; Johnson, RL. (1980) Photolysis of pentachlorophenol-treated wood. Chlorinated
dibenzo-p-dioxin formation. Environ Sci Technol 14(2): 196-200.
03/04/05 R-23 DRAFT-DO NOT CITE OR QUOTE
-------
Lamparski, LL; Nestrick, TJ; Cutie, SS. (1990) The impact on the environment of airborne paniculate matter from
the eruption of Mount Saint Helens in May 1980. In: Clement, R.; Kogel, R., eds, Emissions from combustion
processes: origin, measurement, control. Chelsea, MI: Lewis Publishers.
Lane, JC. (1980) Gasoline and other motor fuels. In: Kirk-Othmer Encyclopedia of Chemical Technology. 3rded.
Vol. 11, pp. 652-695.
Larsen, B; Bewadt, S; Facchetti, S. (1992) Separation of toxic congeners fromPCB mixtures on two series coupled
narrow-bore columns (50 m SIL-8 and 25 m HT-5). International Journal of Environmental Analytical Chemistry
(47): 147-166.
Larsen, BR. (1995) HRGC separation of PCB congeners. J. HighResol. Chromatogr. 18:141-151.
Larsson, P; Lemkemeier, K. (1989) Microbial mineralization of chlorinated phenols and biphenyls in sediment-water
systems from humic and clear-water lake. Water Research 23(9): 1081-1085.
Larssen, S; Brevick, EM; Oehme, M. (1990) Emission factors of PCDD and PCDF for road vehicles obtained by a
tunnel experiment. Organohalogen Compounds 1:453-456.
Lasagni, M; Collina, E; Tettamanti, M; et al. (2000) Kinetics of MSWI fly ash thermal degradation. 1. Empirical rate
equation for native carbon gasification. Environ Sci Technol 34:130-136.
Launhardt, T; Thoma, H. (2000) Investigation on organic pollutants from a domestic heating system using various
solid biofuels. Chemosphere 40:1149-1157.
Lebeuf, M; Gobeil, C; Brochu, C; et al. (1996) Direct atmospheric deposition versus fluvial inputs of PCDD/Fs to
the sediments of the Lower St. Lawrence Estuary. Organohalogen Compounds 28:20-24.
Lee, RG; Hung, H; Mackay, D; et al. (1998) Measurement and modeling of the diurnal cycling of atmospheric PCBs
and PAHs. Environ Sci Technol 32(14):2172-2179.
Leifer, A; Brink, RH; Thorn, GC; et al. (1983) Environmental transport and transformation of poly chlorinated
biphenyls. Washington, D.C.: U.S. Environmental Protection Agency, Office of Toxic Substances. EPA-560/5-83-
025.
Lemieux, PM. (1997) Evaluation of emissions from the open burning of household waste in barrels. Research
Triangle Park, NC: U.S. Environmental Protection Agency, National Risk Management Research Laboratory. EPA-
600/R-97-134a.
Lemieux, P. (2000) Barrel burn experiment results. E-mail from P. Lemieux (EPA/ORD) to D. Cleverly
(EPA/ORD) dated September 7, 2000.
Lemieux, PM; Gullett, BK; Lutes, CC; et al. (2000) Parameters influencing emissions of PCDDs/Fs from open
burning of household waste in barrels. Presented at: AWMA/Environment Canada Specialty Conference "Recent
Advances in the Science and Management of Air Toxics," April 10-12, 2000, Banff, Alberta, Canada.
Lepine, F; Milot, S; Vincent, N. (1992) Formation of toxic PCB congeners and PCB-solvent adducts in a sunlight
irradiated cyclohexane solution of Aroclor 1254. Bull Environ Contam Toxicol 48:152-156.
Lew, G. (1993) Letter to John Schaum concerning CARB (1987) draft report on CDD/CDFs in vehicle exhausts.
Sacramento, CA: California Air Resources Board, Monitoring and Laboratory Division. Available for inspection at:
U.S. Environmental Protection Agency, Office of Research and Development, National Center for Environmental
Assessment, Washington, D.C.
Lew, G. (1996) Letter to G. Schweer (Versar, Inc.) dated January 11, 1996. Sacramento, CA: State of California
Air Resources Board, Engineering and Laboratory Branch. Available for inspection at: U.S. Environmental
03/04/05 R-24 DRAFT-DO NOT CITE OR QUOTE
-------
Protection Agency, Office of Research and Development, National Center for Environmental Assessment,
Washington, D.C.
Lexen, K; De Wit, C; Jansson, B; et al. (1993) Polychlorinated dibenzo-p-dioxin and dibenzofuran levels and
patterns in samples from different Swedish industries analyzed within the Swedish dioxin survey. Chemosphere
27(1-3): 163-170.
Liberson, GL; Belanger, WD. (1995) An analysis of dioxin production as a function of chlorine feed. In: Solid
Waste Management: Thermal Treatment & Waste-to-Energy Technologies, Kilgroe, J., ed. Proceedings of an
interantional specialty conference sponsored by the Air and Waste Management Association, Washington, D.C.
April 18-21, 1995, pp. 425-432.
Liberti, A; Brocco, D. (1982) Formation of polychlorodibenzodioxins and polychlorodibenzofurans in urban
incinerator emissions. In: Hutzinger, O.; Frei, R.W.; Merian, E.; Pocchiari, F., eds., Chlorinated dioxins and
related compounds. New York, NY: Pergamon Press.
Liberti, A; Goretti, G; Russo, MV. (1983) PCDD and PCDF formation in the combustion of vegetable wastes.
Chemosphere 12(4/5):661-663.
Ling, H; Diamond, M; Mackay, D. (1993) Application of the QWASI fugacity/aquivalence model to assessing
sources and fate of contaminants in Hamilton Harbour. Journal of Great Lakes Research 19 (3): 582-602.
Liss, PS.; Slater, PG. (1974) Flux of gases across the air-sea interface. Nature 247:181-184.
Lockheed Martin Corp. (1998) Urbanized areas rainfall. EPA Contract No. 68-C5-0091.
Lockwood, LF; Ansel, G; Haddad, PO. (1981) Magnesium and magnesium alloys. In: Kirk-Othmer Encyclopedia of
Chemical Technology. 3rded. 14:570-615. New York, NY: John Wiley and Sons.
Lofroth, G; Zebtihr, Y. (1992) Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDFs) in
mainstream and sidestream cigarette smoke. Bull. Environ. Contam. Toxicol. 48:789-794.
Lorang, PA. (1996) Comments on the API document: A study to quantify on-road emissions of dioxins and furans
from mobile sources: phase 2. Ann Arbor, MI: U.S. Environmental Protection Agency, National Vehicle and Fuel
Emissions Laboratory. Memorandum dated December 1996.
Lorber, M; Braverman, C; Gehring, P; et al. (1996) Soil and air monitoring in the vicinity of a municipal solid waste
incinerator. Part I: soil monitoring. Oreganohalogen Compounds 28:255-261.
Lorenz, W; Wichmann, H; Bahadir, M. (1996) Balancing of the release of poly chlorinated dibenzo-p-dioxins and
dibenzofurans in fire accidents~a contribution to the discussion. Reinhaltung der Luft. 56:49-53.
LUA (Landesumweltamt Nordrhein-Westfalen). (1997) Identification of relevant industrial sources of dioxins and
furans in Europe. MaterialienNo. 43. Essen, Germany: North Rhine-Westphalia State Environment Agency. ISSN
0947-5206.
Luijk, R; Covers, HA; Neilssen, L. (1992) Formation of polybrominated dibenzofurans during extrusion of high
impact polystyrene/decabromodiphenyl ether/antimony (III) oxide. Environ. Sci. Technol. 26(11):2191-2198.
Luijk, R; Akkerman, DM; Slot, P; et al. (1994) Mechanism of formation of polychlorinated dibenzo-p-dioxins and
dibenzofurans in the catalyzed combustion of carbon. Environ Sci Technol 28: 312-321.
Lustenhouwer, JA; Olie, K; Hutzinger, O. (1980) Chlorinated dibenzo-p-dioxins and related compounds in
incinerator effluents. A review of measurements and mechanisms of formation. Chemosphere 9:501-522.
03/04/05 R-25 DRAFT-DO NOT CITE OR QUOTE
-------
Luthe, C; Karidio, I; Uloth, V. (1996) Controlling dioxins emissions in coastal power boilers: a status report. Pulp
and Paper Canada. 97(9):76-82.
Luthe, C; Karidio, I; Uloth, V. (1998) Dioxins formation in salt-laden power boilers: a mass balance. Chemosphere
36(2):231-249.
Lykins, BW; Clark, R; Cleverly, DH. (1987) Polychlorinated dioxin and furan discharge during carbon reactivation.
Journal of Environmental Engineering 114(2): 330-316.
Mahle, NH; Whitting, LF. (1980) The formation of chlorodibenzo-p-dioxins by air oxidation and chlorination of
bituminous coal. Chemosphere 9:693-699.
Malisch, R. (1994) Determination of PCDD/PCDF inPCB products and milk samples; correlation between PCB-
and PCDD/PCDF-contamination of milk samples. Organohalogen Compounds 20:209-214.
Malloy, TA; Goldfarb, TD; Surico, MTJ. (1993) PCDDs, PCDFs, PCBs, chlorophenols (CPs) and chlorobenzenes
(CBzs) in samples from various types of composting facilities in the United States. Chemosphere 27(l-3):325-334.
Maniff, K; Lewis, M. (1988) MISA monitoring discovers dioxins and furans in wastewater stream of petroleum
refinery. Ministry of the Environment Communique. December 5, 1988.
Mannsville. (1983) Mannsville chemical products synopsis. Cortland, NY: Mannsville Chemical Products Corp.
December 1983.
Marklund, S; Kjeller, LO; Hasson, M; et al. (1986) Determination of PCDDs and PCDFs in incineration samples and
pyrolytic products. In: Rappe, C.; Choudhary, G.; Keith, L.H., eds. Chlorinated dioxins and dibenzofurans in
perspective. Lewis Publishers Inc., Michigan, pp. 79-94.
Marklund, S; Rappe, C; Tysklind, M; et al. (1987) Identification of poly chlorinated dibenzofurans and dioxins in
exhausts from cars run on leaded gasoine. Chemosphere 16(l):29-36.
Marklund, S; Andersson, R; Tysklind, M; et al. (1989) Emissions of PCDDs and PCDFs from a PVC-fire in
Holmsund, Sweden. Chemosphere 18(1-6): 1031-1038.
Marklund, S; Andersson, R; Tysklind, M; et al. (1990) Emissions of PCDDs and PCDFs in gasoline and diesel
fueled cars. Chemosphere 20(5):553-561.
Mathur, DB; Stephenson, MJ; Wenning, RJ; et al. (1997) PCDD/PCDFs in storm water outfalls adjacent to urban
areas and petroleum refineries in San Francisco Bay, California, USA. Organohalogen Compounds 32:1-5.
Matsueda, T; Kurokawa, Y; Nakamura, M; et al. (1994) Concentrations of PCDDs, PCDFs and coplanarPCBs in
cigarettes from various countries. Organohalogen Compounds 20:331-334.
Matthews Cremation. (2003) Telephone conversation between Dale Walter, Mathews Cremation, and K. Riley,
Versar, Inc., on February 13, 2003.
Mattila, H; Virtanen, T; Vartiainen, T; et al. (1992) Emissions from combustion of waste plastic material in fixed
bed boiler. Organohalogen Compounds 9:147-150.
Maw, K. (1998) E-mail to G. Schweer (Versar, Inc.) dated July 13, 1998. Research Triangle Park, NC: Pacific
Environmental Services.
McAloon, K. Versar, Inc., Jan. 20, 2003. Memorandum "2000 Medical Waste Incinerator (MWI) Update for
Sources and Environmental Releases of Dioxin-like Compounds in the United States: Year 2000 Update" Available
for inspection at: Versar, Inc., Springfield, Virginia.
03/04/05 R-26 DRAFT-DO NOT CITE OR QUOTE
-------
McCord, AT. (1981) A study of the emission rate of volatile compounds from lagoons.
Presented at the National Conference of Management of Uncontrolled Hazardous Waste Sites.
McCormack, WB; Moore, R; Sandy, CA. (1981) Organolead compounds. In: Kirk-Othmer Encyclopedia of
Chemical Technology. 3rded. Vol. 14, pp. 180-195.
McCrady, JK; Maggard, SP. (1993) Uptake and photodegradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin sorbed to
grass foliage. Environ Sci Technol 27:343-350.
McLachlan, M. (1996) Bioaccumulation of hydrophobic chemicals in agricultural food chains. Environ Sci Technol
30:252-259.
McLachlan, MS; Welsch-Pausch, K; Tolls, J. (1995) Field validation of a model of the uptake of gaseous SOC in
Lolium multiflorum (rye grass). Environ Sci Technol 29(8): 1998-2004.
Merk, M; Schramm, KW; Lenoir, D; et al. (1995) Determination of the PCDD/F concentration in the fumes from a
PVCfire. Organohalogen Compounds 23:491-494.
Metal Producing. (1991) Sinter plant roundup. 33 Metal Producing. May 1991. p. 24.
Metal Producing. (1996) Census of the North American steel industry. 33 Metal Producing. March 1996. pp. 39-
52.
Micklewright, JT. (1994) Wood preservation statistics, 1993. A report to the wood preserving industry in the United
States.
Midwest Research Institute (MRI). (1996) Updated medical waste incinerator data base. Memorandum from B.
Strong/B. Hardee (MRI) to R. Copeland (U.S. Environmental Protection Agency, BSD Combustion Group). EPA
Contract No. 68-D1-0115.
Mill, T; Rossi, M; McMillen, D; et al. (1987) Photolysis of tetrachlorodioxin and PCBs under atmospheric
conditions. Internal report prepared by SRI International for U.S. Environmental Protection Agency, Office of
Health and Environmental Assessment, Washington, D.C.
Miller, A. (1993) Dioxin emissions from EDC/VCM plants. Environ. Sci. Technol. 27:1014-1015.
Miller, GC; Hebert, VR; Miille, MJ; et al. (1989) Photolysis of octachlorodibenzo-p-dioxin on soils: production of
2,3,7,8-TCDD. Chemosphere 18:1265-1274.
Milligan, MS; Altwicker, ER. (1995) Mechanistic aspects of the de novo synthesis of poly chlorinated dibenzo-p-
dioxins and furans in fly ash from experiments using isotopically labeled reagents. Environ. Sci. Technol. 29: 1353-
1358.
Milligan, MS; Altwicker, ER. (1996) Chlorophenol reactions on fly ash. Equilibrium surface coverage and global
kinetics. Environ Sci Technol 30: 230-236.
Mitchell, D; Loader, A. (1993) Investigation of pollutant emissions from crematoria. United Kingdom. Warren
Spring Laboratory. Report No. LR908(PA).
Mitchell, W; Suggs, J. (1998) Emission factors for the disposal of energetic materials by open burning and open
detonation (OB/OD). USEPA.
Miyabara, Y; Hashimoto, S; Sagai, M; et al. (1999) PCDDs and PCDFs in vehicle exhaust particles in Japan.
Chemosphere 39:143-150.
Moche, W; Thanner, G. (1998) PCDD/F emissions from coal combustion in small residential plants. Organohalogen
Compounds 36:329-332.
03/04/05 R-27 DRAFT-DO NOT CITE OR QUOTE
-------
Morimoto, K; Kenji, T. (1995) Effect of humic substances on the enzymatic formation of OCDD from PCP.
Organohalogen Compounds 23:387-392.
Muir, CG; Yarechewski, AL.; Corbet, RL; et al. (1985) Laboratory and field studies on the fate of 1,3,6,8 -
tetrachlorodibenzo-p-dioxin in soil and sediments. J Agric Food Chem 33:518-523.
Musdalslien, VI; Nokleby, PH; Wallevik, O. (1998) Formation of dioxins from carbonaceous materials in production
of anhydrous magnesium chloride. Organohalogen Compounds 36:81-84.
Muto, H; Takizawa, Y. (1989) Dioxins in cigarette smoke. Archives of Environmental Health 44(3): 171-174.
Muto, H; Takizawa, Y. (1992) Potential health risk via inhalation/ingestion exposure to poly chlorinated dibenzo-p-
dioxins and dibenzofurans. Bull. Environ. Contam. Toxicol. 49:701-707.
Naf, C; Broman, D; Ishaq, R; et al. (1990) PCDDs and PCDFs in water, sludge and air samples from various levels
in a waste water treatment plant with respect to composition changes and total flux. Chemosphere 20(10-12): 1503-
1510.
Naikwadi, KP; Karasek, FW. (1989) Prevention of PCDD formation in MSW incinerators by inhibition of catalytic
activity of fly ash produced. Chemosphere 19 (1-6): 299-304.
Nakamura, M; Matsueda, T; Kurokawa, Y; et al. (1994) Levels and profiles of CDDs and PCDFs in soils and plants.
Organohalogen Compounds 20:103-106.
Nash, RG; Beall, ML, Jr. (1980) Distribution of silvex, 2,4-D, and TCDD applied to turf in chambers and field plots.
Journal of Agricultural and Food Chemistry 28:614-623.
National Research Council. (2000) Waste Incineration and Public Health. Committee on Health Effects of Waste
Incineration, Board of Environmental Studies and Toxicology, Commission on Life Sciences. National Academy
Press, Washington DC.
National Research Council (2002). Biosolids Applied to Land. Advancing Standards and Practices. Committee on
Toxicants and Pathogens in Biosolids Applied to Land, Board on Environmental Studies and Toxicology, Division
on Earth and Life Sciences. The National Academies Press Inc, Washington, DC.
NATO (North Atlantic Treaty Organization). (1988) Pilot study on international information
exchange on dioxins and related compounds: Emissions of dioxins and related compounds from combustion and
incineration sources. North Atlantic Treaty Organization, Committee on the Challenges of Modern Society. Report
#172. August 1988.
NCASI (National Council of the Paper Industry for Air and Stream Improvement). (1993) Summary of data
reflective of pulp and paper industry progress in reducing the TCDD/TCDF content of effluents, pulps and
wastewater treatment sludges. New York, NY. NCASI. June 1993.
NCASI. (1995) NCASI summary of PCDD/F emission from wood residue and black liquor combustion. Attachment
2 to comments submitted on January 13, 1995, to EPA's Office of Health and Environmental Assessment concerning
the draft document entitled "Estimating Exposure to Dioxin-Like Compounds."
Nestrick, TJ; Lamparski, LL. (1982) Isomer-specific determination of chlorinated dioxins for assessment of
formation and potential environmental emission from wood combustion. Anal Chem 54(13):2292-2299.
Nestrick, TJ; Lamparski, LL. (1983) Assessment of chlorinated dibenzo-p-dioxin formation and potential emission to
the environment from wood combustion. Chemosphere 12(4/5):617-626.
03/04/05 R-28 DRAFT-DO NOT CITE OR QUOTE
-------
Nestrick, TJ; Lamparski, LL, Crummett, WB. (1987) Thermolytic surface-reaction of benzene and iron (III) chloride
to form chlorinated dibenzo-p-dioxins and dibenzofurnas. Chemosphere 16(4):777-790.
Nies, L; Vogel, TM. (1990) Effects of organic substrates on dechlorination of Aroclor 1242 in anaerobic sediments.
Applied and Environmental Microbiology 56(9):2612-2617.
Nito, SN; Akimoto, Y; Imagawa,T; et al. (1997) Comparative study on formations of polychlorinated dibenzo-p-
dioxin, chlorinated dibenzofuran and related compounds by pyrolysis of some precursors on unused sand for
fluidized bed incinerator and long term used sand. Chemosphere 35:1717-1727.
Oberg, LG; Rappe, C. (1992) Biochemical formation of PCDD/Fs from chlorophenols. Chemosphere 25(l-2):49-
52.
Oberg, T; Warman, K; Berstrom, J. (1989) Production of chlorinated aromatics in the post-combustion zone and
boiler. Chemosphere 19(l-6):317-322.
Oberg, LG; Glas, B; Swanson, SE; et al. (1990) Peroxidase-catalyzed oxidation of chlorophenols to polychlorinated
dibenzo-p-dioxins and dibenzofurans. Arch. Environ. Contam. Toxicol. 19:930-938.
Oberg, LG; Andersson, R; Rappe, C. (1992) De novo formation of hepta- and octachlorodibenzo-p-dioxins from
pentachlorophenol in municipal sewage sludge. Organohalogen Compounds 9:351-354.
Oberg, LG; Wagman, N; Andersson, R; et al. (1993) De novo formation of PCDD/Fs in compost and sewage sludge
- a status report. Organohalogen Compounds 11:297-302.
Oberg, LG, Wagman, N; Koch, M; et al. (1994) Polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho
PCBs in household organic-waste compost and mature garden waste compost. Organohalogen Compounds 20:245-
250.
Oehme, M; Mano, S; Bjerke, B. (1989) Formation of polychlorinated dibenzofurans and dibenzo-p-dioxins by
production processes for magnesium and refined nickel. Chemosphere 18(7-8): 1379-1389.
Oehme, M; Larssen,S; Brevik, EM. (1991) Emission factors of PCDD/CDF for road vehicles obtained by atunnel
experiment. Chemosphere 23:1699-1708.
O'Keefe, PW; Smith, RM. (1989) PCB capacitor/transformer accidents. In: Kimbrough, R.D.; Jensen, A.A., eds.
Halogenated biphenyls, terphenyls, napthalenes, dibenzodioxins and related products. New York, NY: Elsevier
Science Publishers.
Olie, K; Berg, MVD; Hutzinger, O. (1983) Formation and fate of PCDD and PCDF from combustion processes.
Chemosphere 12(4/5):627-636.
Opatick, RE. (1995) Chlorobenzene Producers Association comments onEPA's external review draft of Estimating
Exposure to Dioxin-Like Compounds. Chlorobenzene Producers Association. January 10, 1995.
Orazio, CE; Kapila, S; Puri, RK; et al. (1992) Persistence of chlorinated dioxins and furans in the soil environment.
Chemosphere 25(7-10): 1469-1474.
O'Rourke, K. (1996) Memorandum to David Cleverly dated December 16, 1996, concerning MWI phone survey
summary. Available for inspection at: U.S. Environmental Protection Agency, Office of Research and
Development, National Center for Environmental Assessment, Washington, DC.
Ozvacic, V. (1985) A review of stack sampling methodology for PCDDs/PCDFs. Chemosphere 15(9-12): 1173-1178.
03/04/05 R-29 DRAFT-DO NOT CITE OR QUOTE
-------
Paciorek, KL; Kratzer, RH; Kaufman, J; et al. (1974) Oxidative thermal decomposition of poly (vinyl chloride)
compositions. J Appl Polym Sci 18:3723-3729.
Palmer, F H; Sapudar, RA; Heath, JA; et al. (1988) Chlorinated dibenzo-p-dioxin and dibenzofuran contamination in
California from chlorophenol wood preservative use. California State Water Resources Control Board. Report No.
88-5WQ.
Papke, O; Ball, M; Lis, ZA; et al. (1989) PCDD and PCDF in indoor air in kindergartens in Northern W. Germany.
Chemosphere 18:617-626.
Pardue, JH; Delaune, RD; Patrick, WH. (1988) Effect of sediment pH and oxidation-reduction potential on PCB
mineralization. Water, Air and Soil Pollution 37:439-447.
Patterson, SH; Murray, HH. (1984) Kaolin, refractory clay, ball clay, and halloysite in North America, Hawaii, and
the Caribbean region. U.S. Geological Survey. Professional Paper No. 1306.
Paterson, S; Mackay, D; Bacci, E; et al. (1991) Correlation of the equilibrium and kinetics of leaf-air exchange of
hydrophobic organic chemicals. Environ Sci Technol 25(5):866-871.
Paustenbach, D; Wenning, PJ; Lau, V; et al. (1992) Recent developments on the hazards posed by 2,3,7,8-TCDD in
soil: implications for setting risk-based cleanup levels at residential and industrial sites. Journal of Toxicology and
Environmental Health 36:103-149.
Paustenbach, DJ; Wenning, PJ; Mathur, D; et al. (1996) PCDD/PCDFs in urban stormwater discharged to San
Francisco Bay, California, USA. Organohalogen Compounds 28:111-116.
Pechan and Associates, Inc. (2002) Draft Technical Mamorandum No. 1: Survey Results for Open Burning Activity
and Rule Effectiveness in the MANE-VU Region. Prepared for Mid-Atlantic Regional Air Management
Association.
Pechan and Associates. (2004) Final technical memorandum numbers 1A: Survey results for open burning activity
and rule effectiveness in the MANE-VU Region, and 2: Activity data and emission estimates for residential open
burning in the MANE-VU Region. December 20.
Pentachlorophenol Task Force (1997) Letter from John Wilkinson (Pentachlorophenol Task Force) to Matthew
Lorber(U.S. EPA/ORD/NCEA). February 7, 1997. Washington, DC: Pentachlorophenol Task Force.
Persson, PE; Bergstrom, J. (1991) Emission of chlorinated dioxins from landfill fires. Proceedings Sardinia 91:
Third International Landfill Symposium, pp. 1635-1641.
Peters, JA. (1983) Evaluation of hazardous waste incineration in cement kilns at San Juan Cement Company.
Prepared for Incineration Research Branch, Industrial Research Laboratory, U.S. Environmental Protection Agency,
Cincinnati, OH.
Peters, A. (1988) Minerals yearbook - iron and steel. Reston, VA: U.S. Geological Survey, Geologic Division.
Pitea, D; Lasagni, M; Bonati, L; et al. (1989a) The combustion of municipal solid wastes and PCDD and PCDF
emissions. Part 1. PCDD and PCDF inMSW. Chemosphere 18(7-8): 1457-1464.
Pitea, D; Lasagni, M; Bonati, L; et al. (1989b) The combustion of municipal solid wastes and PCDD and PCDF
emissions. Part 2. PCDD and PCDF in stack gases. Chemosphere 18(7-8): 1465-1474.
Plimmer, JR. (1980) Herbicides. In: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. 12, pp. 297-
351.
03/04/05 R-30 DRAFT-DO NOT CITE OR QUOTE
-------
Pohlandt, K; Marutzky, R. (1994) Concentration and distribution of poly chlorinated dibenzo-p-dioxins (PCDD) and
polychlorinated dibenzofurans (PCDF) in wood ash. Chemosphere 28(7): 1311-1314.
Portland Cement Association. (2001) U.S. and Canadian Portland Cement Industry: Plant Information Summary.
Skokie, Illinois.
Portland Cement Association. (2003a) E-mail correspondence between G. Hawkins, Portland Cement Association,
and K. Riley, Versar, Inc., on January 31, 2003.
Portland Cement Association. (2003b) E-mail correspondence between Garth Hawkins, Portland Cement
Association and Karie Riley, Versar, Inc., on March 18, 2003.
Prinn, RG; Weiss, RF; Miller, BR; et al. (1995) 269:187.
Procaccini, C; Bozzelle, JW; Longwell, JP; Sarafim, AF; et al. (2003) Formation of chlorinated aromatics by
reactions of Cl*, C12 and Hcl with benzene in the cool-down zone of a combuster. Environ Sci Technol 37:1684-
1689.
Puri, RK; Clevenger, TE; Kapila, S; et al. (1989) Studies of parameters affecting translocation of tetrachlorodibenzo-
p-dioxin in soil. Chemosphere 18(1-6): 1291-1296.
Quab, U; Fermann, M. (1997) Identification of relevant industrial sources of dioxins and furans in Europe. North
Rhine-Westphalia State Environment Agency. Report No. 43.
Quab, U; Fermann, MW; Broker, G. (1998) Steps towards a European dioxin emission inventory. Organohalogen
Compounds 36:7-10.
Quensen, JF; Tiedje, JM; Boyd, SA. (1988) Reductive dechlorination of polychlorinated biphenyls by anaerobic
microorganisms from sediment. Science 242:752-754.
Quensen, JF; Boyd, SA; Tiedje, JM. (1990) Dechlorination of four commercial polychlorinated biphenyl mixtures
(Aroclors) by anaerobic microorganisms from sediments. Appl Environ Microbiol 56(l):2360-2369.
Radian Corporation. (1991) Results of dioxin testing on the catalytic reformer unit #1 exhaust Texas Refinery;
Bakersfield, California. Radian Corp.: Sacramento, CA. August 8, 1991.
Radian Corporation. (1994) Memorandum from R. Harrison, C. Blackley to W. Stevenson, U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards, Research Triangle Park, N.C. Radian Corp.,
Research Triangle Park, N.C. February 16, 1994.
Raghunathan, K; Gullett, BK (1996) Role of sulfur in reducing PCDD and PCDF formation. Environ Sci Technol:
30(6): 1827-1834.
Randall, D. (1995) Memorandum dated April 8, 1995, from David Randall and Brian Hardee, Midwest Research
Institute, Gary, North Carolina, to Richard Copland, Combustion Group, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina. Subject: Emission
factors for medical waste incinerators (MWIs), EPA Contract No. 68-01-0115; EPA Docket Number A-91-61; IV B
042.
Rappe, C. (1991) Sources of human exposure to CDDs and PCDFs. In: Biological Basis for Risk Assessment of
Dioxin and Related Compounds, Banbury Report No. 35, M. Gallo, R. Scheuplein, and K. van der Heiden (Eds),
Plainview, NY: Cold Spring Harbor Laboratory Press.
Rappe, C. (1992a) Sources of PCDDs and PCDFs. Introduction. Reactions, levels, patterns, profiles and trends.
Chemosphere 25(l-2):41-44.
03/04/05 R-31 DRAFT-DONOTCITEORQUOTE
-------
Rappe, C. (1992b) Sources of exposure, environmental levels and exposure assessment of PCDDs and PCDFs.
Organohalogen Compounds 9:5-8.
Rappe, C. (1993) Sources of exposure, environmental concentrations and exposure assessment of PCDDs and
PCDFs. Chemosphere 27(1-3):211-225.
Rappe, C. (1995) Comments on the USEPA draft document. In: Comments submitted to EPA by the Integrated
Waste Services Association on EPA's Estimating Exposure to Dioxin-Like Compounds. Washington, DC: Integrated
Waste Services Association. January 13, 1995.
Rappe, C; Marklund, S; Buser, HR; et al. (1978a) Formation of polychlorinated dibenzo-p-dioxins (PCDDs) and
dibenzofurans (PCDFs) by burning or heating chlorophenates. Chemosphere 3:269-281.
Rappe, C; Gara, A; Buser, HR. (1978b) Identification of polychlorinated dibenzofurans (PCDFs) in commercial
chlorophenol formulations. Chemosphere 12:981-991.
Rappe, C; Andersson, R; Berggvist, PA; et al. (1987) Overview of the environmental fate of chlorinated dioxins and
dibenzofurans. Sources, levels and isomeric pattern in various matrices. Chemosphere 16(8-9):1603-1618.
Rappe, C; Kjeller, LO; Bruckmann, P; et al. (1988) Identification and quantification of PCDD/CDFs in urban air.
Chemosphere 17(1):3-20.
Rappe, C; Kjeller, LO; Andersson, R. (1989a) Analyses of PCDDs and PCDFs in sludge and water samples.
Chemosphere 19(1-6): 13-20.
Rappe, C; Swanson, S; Gals, B; et al. (1989b) Formation of PCDDs and PCDFs by the chlorination of water.
Chemosphere 19(12): 1875-1880.
Rappe, C; Kjeller, LO; Kulp, SE. (1990a) Sampling and analysis of PCDDs and PCDFs in surface water and
drinking water at 0.001 ppq levels. Organohalogen Compounds 2:207-210.
Rappe, C; Glas, B; Kjeller, LO; et al. (1990b) Levels of PCDDs and PCDFs in products and effluent from the
Swedish pulp and paper industry and chloralkali process. Chemosphere 20(10-12): 1701-1706.
Rappe, C; Andersson, R; Lundstrom, K; et al. (1990c) Levels of polychlorinated dioxins and dibenzofurans in
commercial detergents and related products. Chemosphere 21(l-2):43-50.
Rappe, C; Kjeller, L; Kulp, S; et al. (1991) Levels, profile and pattern of PCDDs and PCDFs in samples related to
the production and use of chlorine. Chemosphere 23(11-12): 1629-1636.
Rappe, C; Andersson, R; Karlaganis, G; et al. (1994) PCDDs and PCDFs in samples of sewage sludge from various
areas in Switzerland. Organohalogen Compounds 20:79-84.
Rappe, C; Anderson, R; Bonner, M; et al. (1998) PCDDs and PCDFs in municipal sewage sludge and effluent from
POTW in the State of Mississippi, USA. Chemosphere 36:315-328.
Ree, KC; Evers, EHG; Van Der Berg, M. (1988) Mechanism of formation of polychlorinated dibenzo(p)dioxins
(PCDDs) and polychlorinated dibenzofurans (PCDFs) from potential industrial sources, lexicological and
Environmental Chemistry 17:171-195.
Remmers, J; Dupuy, A; McDaniel, D; et al. (1992) Polychlorinated dibenzo-p-dioxin and dibenzofuran
contamination in chloranil and carbazole violet. Chemosphere 25(7-10): 1505-1508.
Reusable Industrial Packaging Association. (1997) 1997 Statistics as found on the Reusable Industrial Packaging
Association (RIPA) webpage (http://www.reusablepackaging.org/Stats.html)
03/04/05 R-32 DRAFT-DO NOT CITE OR QUOTE
-------
Rhee, GY; Bush, B; Brown, MP; et al. (1989) Anaerobic biodegradation of polychlorinated biphenyls in Hudson
River sediments and dredged sediments in clay encapsulation. Water Research 23(8):957-964.
Riederer, M. (1990) Estimating partitioning and transport of organic chemicals in the foliage/atmosphere system:
discussion of a fugacity-based model. Environ Sci Technol 24(6):829-837.
Rieger, R; Ballschmiter, K. (1992) Search for sources of CLxDD/CLxDF in sewage sludge of mixed
industrial/domestic origin. Organohalogen Compounds 9:203-206.
Riggs, KB; Brown, TD; Schrock, ME. (1995) PCDD/PCDF emissions from coal-fired power plants. Organohalogen
Compounds 24:51-54.
Rigo, H.G. (1998) Dioxin and chlorine: New evidence of no material relationship in a commercial scale system.
Organohalogen Compounds 36:261-264.
Rigo, GH; Chandler, JA; Larder, SW. (1995) The relationship between chlorine and dioxin emissions from waste
combustors. In: Solid Waste Management: Thermal Treatment & Waste-to-Energy Technologies, Kilgroe, I, ed.
Proceedings of an international specialty conference sponsored by the Air and Waste Management Association,
Washington, D.C. April 18-21, 1995. ASME/CRTD-Volume 36.
Risatti, JB. (1992) Rates of microbial dechlorination of polychlorinated biphenyls (PCBs) in anaerobic sediments
from Waukegan Harbor. Champaign, IL: The Illinois Hazardous Waste Research and Information Center. HWRIC
RR-061.
Riss, A; Aichinger, H. (1993) Reduction of dioxin emissions and regulatory measures in Austria. Organohalogen
Compounds 14:341-344.
Robbins, JA; Edgington, DN. (1973) Geochim Cosmochim Acta 39, p.285. As cited in: Czuczwa, J.M; Kites, R.A.
(1985). Historical record of polychlorinated dioxins and furans in Lake Huron sediments. In: Keith, L.H.; Rappe.
C.; Choudhary, G, eds. Chlorinated dioxins and dibenzofurans in the total environment II. Boston, MA: Butterworth
Publishers.
Retard, W. (1993) Fires. In: Current views on the impact of dioxins and furans on human health and the
environment. Washington, DC: Toxicology Forum, Inc.
Rubber Manufacturers Association. (2002) http://www.rma.org/scrap_tires/scrap_tire_markets/
Rubin, A; White, C. (1992) Computer printout from National Sewage Sludge Survey Data
Base. U.S. Environmental Protection Agency, Office of Science and Technology, Health and Ecological Criteria
Division, Sludge Risk Assessment Branch. December 21, 1992.
Ruokojarvi, P; Ettala, M; Rahkonen, P; et al. (1995) Polychlorinated dibenzo-p-dioxins and -furans (PCDDs and
PCDFs) in municipal waste landfill fires. Chemosphere 30(9): 1697-1708.
Safe, S. (1992) Development, validation and limitations of toxic equivalency factors. Chemosphere 25(l-2):61-64.
Safe, S. (1994) Polychlorinated biphenyls (PCBs): environmental impact, biochemical and toxic responses, and
implications for risk assessment. Crit Rev Toxicol 21(1):51-88.
Safe, S. (1995) Human dietary intake of aryl hydrocarbon (Ah) receptor agonists: mass balance estimates of
exodioxins and endodioxins and implications for health assessment. Organohalogen Compounds 26:7-13.
SAIC (Science Applications International Corporation). (1994) Identification of sources of dioxin in catalytic
reformers and potential mitigation. Cincinnati, OH: U.S. Environmental Protection Agency, Risk Reduction
Engineering Laboratory. EPA Contract No. 68-CO-0044.
03/04/05 R-33 DRAFT-DO NOT CITE OR QUOTE
-------
Sakai, S; Hiraoka, M; Takeda, N; et al. (1993a) CoplanarPCBs and PCDD/PCDFs in municipal waste incineration.
Chemosphere 27(l-3):233-240.
Sakai, S; Hiraoka, M; Takeda, N; et al. (1993b) On emission and formation of non-ortho CBs and mono-ortho CBs
in municipal waste incineration. Organohalogen Compounds 11:245-248.
Sakai, S; Hiraoka, M; Takeda, N; et al. (1994) Behavior of coplanar PCBs in oxidative condition of municipal waste
incineration. Organohalogen Compounds 20:309-313.
Sakai, S; Hayakawa, K; Takatsuki, H; et al. (2001) Dioxin-like PCBs released from waste incineration and their
deposition flux. Environmental Science and Technology 35:3601-3607.
Santl, H; Gruber, L; Stohrer, E. (1994) Some new sources of poly chlorinated dibenzodioxins (PCDDs) and
dibenzofurans (PCDFs) in waste papers and recycled pulps. Chemosphere 29(9-11): 1995-2003.
Schafer, K; McLachlan, MS; Reissinger, M; et al. (1993) An investigation of PCDD/F in a composting operation.
Organohalogen Compounds 11:425-428.
Schatowitz, B; Brandt, G; Gather, F; et al. (1993) Dioxin emissions from wood combustion. Organohalogen
Compounds 11:307-310.
Schaub, WM; Tsang, W. (1983) Physical and chemical properties of dioxins in relation to their disposal. In: Tucker,
R.E.; Young, A.L., Gray, A.P., eds. Human and Environmental Risks of Chlorinated Dioxins and Related
Compounds. New York, NY: Plenum Press.
Schecter, A; Papke, O; Isaac, J; et al. (1997) 2,3,7,8 Chlorine substituted dioxin and dibenzofuran congeners in 2,4-
D, 2,4,5-T and pentachlorophenol. Organohalogen Compounds 32:51-55.
Schecter, AJ; Michalek, JE; May, J; et al. (1998) Dioxin and dibenzofuran congeners in 2,4-dichlorophenoxyacetic
acid, 2,4,5-trichlorophenoxyacetic acid, and Agent Orange. Organohalogen Compounds 36:285-288.
Schmitt, R. (1993) Comments on pesticide data call-in [memorandum to John Schaum, U.S. Environmental
Protection Agency, Office of Research and Development]. Washington, D.C.: U.S. Environmental Protection
Agency, Office of Pesticide Programs. April 27, 1993.
Schoonenboom, MH; Tromp, PC; Olie, K. (1993) The formation of coplanar PCBs, PCDDs and PCDFs in a fly-ash
model system. Organohalogen Compounds 11:277-280.
Schoonenboom, MH; Olie, K. (1995) Formation of PCDDs and PCDFs from anthracene and chloroanthracene in a
model fly ash system. Environ Sci Technol 29:2005-2009.
Schramm, KW. (1998) Personal communication between Dr. Karl-Werner Schrammand Greg Schweer, Versar, Inc.
September 29, 1998.
Schramm, K; Reischl, A; Hutzinger, O. (1987) Chemosphere 16:2653-2663.
Schreiner, M; Reifenhauser, W; Vierle, O. (1992) Measurements of the emission concentrations of PCDD/PCDF in a
digester-torch of a municipal sewage plant. Organohalogen Compunds 9:255-257.
Schreiner, G; Schimmel, H; Ballschmiter, K. (1995) Influence of the substitution pattern on the microbial
degradation of mono- to tetrachlorinated dibenzofurans and dibenzodioxins. Organohalogen Compounds 24:43-46.
Schulz, DE; Petrick, G; Duinker, JC. (1989) Complete characterization of poly chlorinated biphenyl congeners in
commerical Aroclor and Clophen mixtures by multidimensional gas chromatography-electron capture detection.
Environ Sci Technol 23:852-859.
03/04/05 R-34 DRAFT-DO NOT CITE OR QUOTE
-------
Schwartz, TR; Tillitt, DE; Feltz, KP; et al. (1993) Determination of mono- and non~o-o'-chlorine substituted
polychlorinated biphenyls in Aroclors and environmental samples. Chemosphere 26(8): 1443-1460.
Schwind, K-H; Thoma, H; Hutzinger, O; et al. (1991) Emission halogenierter dibenzodioxine (PXDD) und
dibenzofurane (PXDF) aus verbrennungsmotoren. UWSF-Z. Umweltchem. Oekotox. 3, 291-298. [English
translation]
Schwind, KH; Hosseinpour, J; Fiedler, H; et al. (1995) Human exposure to consumer products: analysis of
chlorinated organic compounds in candles and their exhaust fumes. Organohalogen Compounds 26:113-116.
Secor International, Inc. (1995a) Emission measurement results for furans and dioxins from the main stack at the
Phelps Dodge-Hidalgo Smelter, Playos, New Mexico. Prepared for the Phelps Dodge Mining Company.
Secor International, Inc. (1995b) Furans and dioxins emission measurement results for Cyprus Miami Mining
Corporation. Prepared for the Cypress Amax Minerals Company.
Sedlak, DL; Andren, AW. (1991) Aqueous-phase oxidation of polychlorinated biphenyls by hydroxyl radicals.
Environ Sci Technol 25(8):1419-1427.
Sewart, A; Harrad, SJ; McLachlan, MS; et al. (1995) PCDD/Fs and non-o-PCBs in digested U.K. sewage sludges.
Chemosphere 30(l):51-67.
Shane, BS; Henry, CB; Hotchkiss, JH; et al. (1990) Organic toxicants and mutagens in ashes from eighteen
municipal refuse incinerators. Arch Environ Contam Toxicol 19:665-673.
Shaub, WM; Tsang, W. (1983) Dioxin formation in incinerators. Environ. Sci. Technol. 17: 721-730.
Shibata, E; Yamamoto, S; Kasai, E; Nakamura, E. (2003) Formation behavior of PCDD/Fs in PVC pyrolysis with
copper oxide. Chemosphere 50:1235-1242.
Shin, K-J; Chang, Y-S. (1999) Characterization of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, and
heavy metals in fly ash produced from Korean municipal solid waste incinerators. Chemosphere 38:2655-2666.
Sidhu, S. (1999) Role of aliphatic precursors in the formation mechanism of PCDD/F, PCB/ and PCN.
Organohalogen Compounds 41:59-62.
Silk, PJ; Lonergan, GC; Arsenault, TL; et al. (1997) Evidence of natural organochlorine formation in peat bogs.
Chemosphere 35:2865-2880.
Simonich, SL; Kites, RA. (1994) Vegetation-atmosphere partitioning of poly cyclic aromatic hydrocarbons. Environ
Sci Technol 28(5):939-943.
Sivils, LD; Kapila, S; Yan, Q; et al. (1994) Studies on gas-phase phototransformation of polychlorinated dibenzo-p-
dioxins. Organohalogen Compounds 19:349-353.
Sivils, LD; Kapila, S; Yan, Q; et al. (1995) Studies on vapor phase phototransformation of polychlorinated dibenzo-
p-dioxins (PCDDs): effect of environmental parameters. Organohalogen Compounds 24:167-172.
Smith, RM; O'Keefe P; Briggs, R; et al. (1992) Measurement of PCDFs and PCDDs in air samples and lake
sediments at several locations in upstate New York. Chemosphere 25(l-2):95-98.
Smith, RM; O'Keefe, PW; Hilker, D; et al. (1995) Direct and indirect contribution of atmospheric PCDDs and
PCDFs to Hudson River National Estuarine Research Reserve sediment cores. Organohalogen Compounds 24:141-
145.
03/04/05 R-35 DRAFT-DO NOT CITE OR QUOTE
-------
Solid Waste Technologies. (1994) A comprehensive status report onMSW waste-to-energy facilities, incinerators
refuse-derived-fuel, and tire processing facilities throughout North America. Kansas City, MO: HCI Publications.
84pp.
Someshwar, AV; Pinkerton, JE. (1992) Wood processing industry. In: Buonicore, A.J., Davis, W.T., eds., Air
pollution engineering manual. Air and Waste Management Association. New York, NY: Van Nostrand Reinhold. pp.
835-847.
Southerland, JH; Kuykendal, WB; Lamasan, WH; et al. (1987) Assessment of combustion sources as emitters of
chlorinated dioxin compounds: A report on the results of tier 4 of the National Dioxin Strategy. Chemosphere
16(8/9):2161-2168.
Springer, JM. (1997) Personal communication with A. Paintal, Versar, Inc. Cremation Association of North
America. January 7, 1998.
St. Lawrence County. (1993) Legal open burning and on-premises burial of solid waste in St. Lawrence County, NY:
The environmental impacts. St. Lawrence County Planning Office, Canton, NY. February 5.
Stanmore, BR. (2004) The formation of dioxins in combustion systems. Combustion and Flame 136:398-427.
Stehl, RH; Lamparski, LL. (1977) Combustion of several 2,4,5-trichlorophenoxy compounds: formation of 2,3,7,8-
tetrachlorodibenzo-p-dioxin. Science 197:1008-1009.
Stehl, RH; Papenfuss, RR; Bredeweg, RA; et al. (1973) The stability of pentachlorophenol and chlorinated dioxins
to sunlight, heat, and combustion. In: E.H. Blair ed., Chlorodioxins - origin and fate. Washington, DC: American
Chemical Society.
Stevens, JL; Jones, KC. (2003) Quantification of PCDD/F concentrations in animal manure and comparison of the
effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/F.
Chemosphere 50:1183-1191.
Stieglitz, L; Zwick, G; Beck, J; et al. (1989a) Carbonaceous particles in fly ash~a source for the de novo synthesis of
organochlorocompounds. Chemosphere 19(l-6):283-290.
Stieglitz, L; Zwick, G; Beck, J; et al. (1989b) On the de-novo synthesis of PCDD/PCDF on fly ash of municipal
waste incinerators. Chemosphere 18:1219-1226.
Stieglitz, L; Vogg, H; Zwick, G; et al. (1991) On formation conditions of organohalogen compounds from paniculate
carbon of fly ash. Chemosphere 23(8-10): 1255-1264.
Storherr, RW; Watts, RR; Gardner, AM; et al. (1971) Steam distillation technique forthe analysis of 2,3,7,8-
tetrachlorodibenzo-p-dioxin in technical 2,4,5-T. Journal of the AOAC 54(1):218-219.
Stowe, RA. (1996) A needle in a haystack. Environmental Protection. August 1996. pp. 22-25.
Strachan, WMJ; Eisenreich, SJ. (1988) Mass balancing of toxic chemicals in the Great Lakes: the role of
atmospheric deposition. Windsor, Ontario: International Joint Commission.
Strandell, ME; Lexen, KM; deWit, CA; et al. (1994) The Swedish Dioxin Survey: Summary of results from
PCDD/F and coplanar PCB analyses in source-related samples. Organohalogen Compounds 20:363-366.
Stringer, RL; Costner, P; Johnston, PA. (1995) PVC manufacture as a source of PCCD/Fs. Organohalogen
Compounds 24:119-123.
03/04/05 R-36 DRAFT-DO NOT CITE OR QUOTE
-------
Strong, B. (1996) Memorandum dated January 31, 1996, from Brian Strong and Brian Hardee, Midwest Research
Institute, Gary, North Carolina, to Richard Copland, Combustion Group, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina. Subject: Updated
medical waste incinerator data base, EPA Contract No. 68-01-0115; EPA Docket Number A-91-61; IV B 022.
Strong, B; Hanks, K. MRI, Feb. 22, 1999. Memorandum "Emissions Inventory for Hospital, Medical, Infectious
Waste Incinerators Covered by the Proposed Section 1 l(d)/129 Federal Plan" EPA Docket number A-98-24, item
II-B-1.
Stuart, B; Carter, D; Hoodless, RA. (1993) Report on the examination of sewage sludges for polychlorinated
dibenzo-p-dioxins and polychlorinated dibenzofurans. London, England: Laboratory of the Government Chemist.
Suter-Hofmann, M; Schlatter, CH. (1986) Toxicity of paniculate emissions from a municipal incinerator: critique of
the concept of TCDD-equivalents. Chemosphere 15:1733-1743.
Svenson, A; Kjeller, LO; Rappe, C. (1989) Enzyme-mediated formation of 2,3,7,8-tetrasubstituted chlorinated
dibenzodioxins and dibenzofurans. Environ Sci Technol 23(7):900-902.
Sverdrup Corp. (1991) Chemetco, Inc., compliance testing, final report. St. Louis, MO: Sverdrup Corp. April 19,
1991.
Swackhamer, DL; Armstrong, DE. (1986) Estimation of the atmospheric and nonatmospheric contributions and
losses of polychlorinated biphenyls for Lake Michigan on the basis of sediment records of remote lakes. Environ Sci
Technol 20 (9): 879-883.
Swackhamer, DL; McVeety, BD; Kites, RA. (1988) Deposition and evaporation of polychlorobiphenyl congeners to
and from Siskiwit Lake, Isle Royale, Lake Superior. Environ Sci Technol 22(6):664-672.
Sweden's Office of Nature Conservancy. (1991) Organochlorine compounds from dishwashing detergents and
bleach? Sweden Office of Nature Conservancy Report No. 4009.
Systems Application International. (1995) MSWI database of all existing facilities in the U.S. Prepared in Sept.
1995 for U.S. Environmental Protection Agency, Office of Policy Analysis.
Takeda, N; Takaoka, M; Fujiwara, T; et al. (1998) Research on PCDDs/DFs emissions from crematories in Japan.
Organohalogen Compounds 36:167-170.
Takeda, N; Takaoka, M; Fujiwara, T; et al. (2001) Measures to prevent emissions of PCDDs/DFs and coplanar
PCBs from crematories in Japan. Chemosphere 43:763-771.
Takizawa, Y; Asada, S; Muto, H. (1994) Dioxins in dust fall and volcanic ash from the active volcanos Fugendake
and Sakurajima. Organohalogen Compounds 20:359-362.
Tanabe, S. (1988) PCB problems in the future: foresight from current knowledge. Environ Pollut 50:5-28.
Tanabe, S; Kannan, N; Wakimoto, T; et al. (1987) Method for the determination of three toxic non-orthochlorine
substituted coplanar PCBs in environmental samples at part-per-trillion levels. Intern J Environ Anal Chem 29:199-
213.
Tashiro, C; Clement, RE; Stocks, BJ; et al. (1990) Preliminary report: dioxins and furans in prescribed burns.
Chemosphere 20:1533-1536.
Taylor, A; Zannes, M. (1996) The 1996 IWSA municipal waste combustion directory of United States facilities.
Integrated Waste Services Association. 16 pps.
03/04/05 R-37 DRAFT-DO NOT CITE OR QUOTE
-------
The Aluminum Association. (1997) U.S. aluminum industry plant directory, November 1997. Washington, DC: The
Aluminum Association.
The Tobacco Institute. (1995) Tobacco industry profile 1995. Washington, DC: The Tobacco Institute.
The Vinyl Institute. (1998) Dioxin characterization program. Phase I Report. Morristown, NJ: The Vinyl Institute.
August 10, 1998.
Thiesen, J; Funcke, W; Balfanz, E; et al. (1989) Determination of PCDFs and PCDDs in fire accidents and
laboratory combustion tests involving PVC-containing materials. Chemosphere 19(l-6):423-428.
Thoma, H; Hutzinger, O. (1989) Content and formation of toxic products in flame retardants. Presented at:
Workshop on Brominated Aromatic Flame Retardants. Slokloster, Sweden; October 24-26, 1989.
Thomas, VM; Spiro, TG. (1995) An estimation of dioxin emissions in the United States. Toxicological and
Environmental Chemistry 50:1-37.
Thomas, VM; Spiro, TG. (1996) The U.S. dioxin inventory: are there missing sources. Environ Sci Technol
30(2):82A-85A.
Thompson, TS; Clement, RE; Thornton, N; et al. (1990) Formation and emission of PCDDs/PCDFs in the petroleum
refining industry. Chemosphere 20(10-12): 1525-1532.
Thub, U; Popp, P; Ehrlich, C; et al. (1995) Domestic lignite combustion as source of polychlorodibenzodioxins and
furans (PCDD/F). Chemosphere 31(2):2591-2604.
Tiernan, TO; Wagel, DJ; Garrett, JH; et al. (1995) Determination of PCDD/PCDF in polyvinyl chloride (PVC) and
in related manufacturing process samples. Organohalogen Compounds 23:65-68.
Tolls, J; McLachlan, MS. (1994) Partitioning of semivolatile organic compounds between air and Lolium
multiflorum (Welsh rye grass). Environ Sci Technol 28(1): 159-166.
Tong, HY; Gross, ML; Schecter, A; etal. (1990) Sources of dioxins in the environment: second stage study of
PCDD/Fs in ancient human tissue and environmental samples. Chemosphere 20(7-9):987-992.
Tosine, H; Clement, R; Osvacic, V; et al. (1983) Levels of chlorinated organics in a municipal incinerator. Presented
before the Division of Environmental Chemistry, American Chemical Society 186th National Meeting, September, 1,
1983.
Towara, J; Hiller, B; Hutzinger, O; et al. (1992) PCDD/F in distillation residues from dry cleaning machines.
Chemosphere 25:1509.
Trapp, S; Matthies, M; Scheunert, I.; et al. (1990) Environ Sci Technol 24:1246-1252.
TRRCPO (Two Rivers Region Council of Public Officials and Patrick Engineering, Inc.) (1994) Emission
characteristics of burn barrels. Prepared for U.S. Environmental Protection Agency, Region V.
Tysklind, M; Rappe, C. (1991) Photolytic transformation of poly chlorinated dioxins and dibenzofurans in fly ash.
Chemosphere 23(8-10): 1365-1375.
Tysklind, M; Soderstrom; Rappe, C; et al. (1989) PCDD and PCDF emissions from scrap metal melting processes at
a steel mill. Chemosphere 19(1-6):705-710.
Tysklind, M; Carey, AE; Rappe, C; et al. (1992) Photolysis of OCDF and OCDD on soil. Organohalogen
Compounds 8:293-296.
03/04/05 R-38 DRAFT-DO NOT CITE OR QUOTE
-------
Umlauf, G; Horstmann, M; Klein, P; et al. (1993) Mass balance of PCDD/F in a dry cleaning machine.
Organohalogen Compounds 11:413-416.
Umweltbundesamt. (1996) Determination of requirements to limit emissions of dioxins and furans. Report from the
Working Group of the Subcommittee Air/Technology of the Federal Government/Federal States Immission Control
Committee. Berlin, Germany.
United Kingdom, Department of the Environment. (1995). United Kingdom Comments on "Estimating Exposure to
Dioxin-Like Compounds". January, 1995.
Urhahn, T; Ballschmiter, K. (1998) Chemistry of the biosynthesis of halogenated methanes: Cl-Organohalogens as
pre-industrial chemical stressors in the environment. Chemosphere 37:1017-1032.
U.S. Census Bureau. (2000) Census 2000.
U.S. Census Bureau. (200la) County Business Patterns 1999, CBP-99-1, Washington, DC. June 2001.
U.S. Census Bureau (200 Ib) Statistical abstract of the United States: 2001.
USDA (U.S. Department of Agriculture). (1970) Restricting the use of phenoxy herbicides - costs to farmers.
Washington, DC: Economic Research Service and Agricultural Research Service. Agricultural Economic Report
No. 194.
USDA. (1971) Farmer's use of pesticides in 1971 and quantities. Washington, DC: Economics Research Service.
Agricultural Economic Report No. 252.
USDA. (1977) The pesticide review - 1975. Washington, DC: Agricultural Stabilization and Conservation Service.
USDA. (1980) The biologic and economic assessment of pentachlorophenol, inorganic arsenicals, and creosote.
Washington, DC: U.S. Department of Agriculture. Technical Bulletin No. 1658-1.
USDA. (1995) Graphic highlights of natural resource trends in the United States between 1982 and 1992.
Washington, DC: U.S. Department of Agriculture, Natural Resources Conservation Service, National Resources
Inventory.
USDA. (1996) Major land uses: 1945-1992. Washington, DC: U.S. Department of Agriculture, Economic
Research Service.
USDA. (1997) Tobacco leaf and products statistics and analysis. Washington, DC: U.S. Department of Agriculture,
Economic Research Service.
U.S. DHHS (Department of Health and Human Services). (1989) Toxicology and carcinogenesis studies of two
pentachlorophenol technical-grade mixtures in B6C3F1 mice (feed studies). Research Triangle Park, NC: U.S.
Department of Health and Human Services, National Toxicology Program. NIH Publication No. 89-2804.
U.S. Department of Transportation (USDOT) (2002) 2002 Status of the Nation's Highways, Bridges, and Transit:
Conditions and Performance Report to Congress. Washington, DC: USDOT, Federal Highway Administration,
Federal Transit Administration
U.S. DOC (U.S. Department of Commerce). (1990a) 1987 Census of manufactures. Smelting and refining of
nonferrous metals and alloys. Washington, DC: Bureau of the Census. Report No. 33C-18.
03/04/05 R-39 DRAFT-DO NOT CITE OR QUOTE
-------
U.S. DOC. (1990b) 1987 Census of manufacturers. Soap, cleaners, and toilet goods. Washington, DC: Bureau of
the Census. Report No. MC-87-I-28D.
U.S. DOC. (1990c) 1987 Census of manufactures. Industrial inorganic chemicals. Washington, DC: Bureau of the
Census. Report No. MC87-I-28A.
U.S. DOC (1995a) Statistical abstract of the United States, 1995. 118th ed.
U.S. DOC (1995b) 1992 Census of transportation. Truck inventory and use survey. Washington, DC: Bureau of the
Census. Report No. TC92-T-52.
U.S. DOC (1995c) 1992 Census of manufactures. Smelting and refining of nonferrous metals and alloys.
Washington, DC: Bureau of the Census. Report No. MC92-I-33C.
U.S. DOC (1995d) 1992 Census of manufactures. Blast furnaces, steel works, and rolling and finishing mills.
Washington, DC: Bureau of the Census. Report No. MC92-I-33A.
U.S. DOC (1996) 1992 Economic census report series - disc 1G. Washington, DC: Bureau of the Census. CD-
EC92-1G.
U.S. DOC (1997) Statistical abstract of the United States, 1997. 117th edition. Washington, DC: Bureau of the
Census.
U.S. DOC (2002) International Data Base. Bureau of the Census. Source: http://blue.census.gov/cgi-bin/ipc/idbagg
U.S. DOC (2003a) Census 2000 Summary File 1 (SF 1) 100-Percent Data. Bureau of the Census. Available online
at http://factfinder.census.gov/servlet/DTTable?_ts=64261331968.
U.S. DOC (2003b) Census 2000 Summary File 3 (SF 3) Sample Data. Bureau of the Census. Available online at
http://factfmder.census.gov/servlet/DTTable?_ts=65970407015.
U.S. DOT (Department of Transportation) (2002) 2002 Status of the Nation's Highways, Bridges, and Transit:
Conditions and Performance Report to Congress. Washington, DC: USDOT, Federal Highway Administration,
Federal Transit Administration.
U.S. Environmental Protection Agency; Environment Canada. (1991) The environmental characterization of RDF
combustion technology. Mid-Connecticut facility, Hartford,CT. Test program and results, volume II., June 1991.
U.S. EPA (Environmental Protection Agency). (1975) Production, distribution, use and environmental impact
potential of selected pesticides. Washington, DC: Office of Pesticide Programs and Office of Water and Hazardous
Materials.
U.S. EPA. (1977) Pesticide usage survey of agricultural, governmental, and industrial sectors in the United States,
1974. Washington, DC: Office of Pesticide Programs. EPA-540/9-78-007.
U.S. EPA. (1979) Polychlorinated biphenyls (PCBs) in manufacturing, processing, distribution in commerce, and use
prohibition: Final rule. Federal Register 44:31514-31568.
U.S. EPA. (1980) Materials balance for chlorophenols. Level I-preliminary. Washington, DC: Office of Toxic
Substances. EPA-560/13-80-004.
U.S. EPA. (1982a) Development document for effluent limitations guidelines and standards for the inorganic
chemicals manufacturing point source category. Washington, DC: Office of Water Regulations and Standards. EPA
440/1-82/007.
03/04/05 R-40 DRAFT-DO NOT CITE OR QUOTE
-------
U.S. EPA. (1982b) Development document for effluent limitations guidelines and standards for the iron and steel
manufacturing point source category. Volume II. Washington, DC: Office of Water. EPA-440/1-82/024.
U.S. EPA. (1984) Thermal degradation products from dielectric fluids. Washington, DC: Office of Toxic
Substances. EPA-560/5-84-009.
U.S. EPA. (1987a) National dioxin study Tier 4 - combustion sources. Engineering analysis report. Research
Triangle Park, NC: Office of Air Quality Planning and Standards. EPA-450/4-84-014h.
U.S. EPA. (1987b) Municipal waste combustion study. Characterization of the municipal waste combustion
industry. Washington, DC: Office of Air and Radiation. EPA/530-SW-87-021b.
U.S. EPA. (1987c) Locating and estimating air emissions from sources of poly chlorinated biphenyls (PCB).
Research Triangle Park, NC: Office of Air Quality Planning and Standards, EPA-450/4-84-007n.
U.S. EPA. (1987d) Hospital waste combustion study: Data gathering phase. Research Triangle Park, NC: Office of
Air Quality Planning and Standards. EPA-450/3-88-017.
U.S. EPA. (1987e) Interim procedures for estimating risks associated with exposures to mixtures of chlorinated
dibenzo-p-dioxins and dibenzofurans (CDDs and CDFs). EPA/625/3-87/012.
U.S. EPA. (1988a) Estimating exposure to 2,3,7,8-TCDD. Washington, DC: Office of Health and Environmental
Assessment. EPA/600/6-88/005A.
U.S. EPA. (1988b) Pesticide assessment guidelines, subdivision D - product chemistry. Series 61-4, addendum 1 on
data reporting. Washington, DC: Office of Pesticide Programs. NTIS No. PB88-191705.
U.S. EPA. (1988c) Pesticide industry sales and usage: 1987 market estimates. Washington, DC: Office of Pesticide
Programs.
U.S. EPA. (1988d) U.S. EPA cooperative dioxin screening study. Washington, DC: Office of Water Regulations
and Standards. EPA-440/1-88-025.
U.S. EPA. (1989a) Interim procedures for estimating risks associated with exposures to mixtures of chlorinated
dibenzo-p-dioxins and -dibenzofurans (CDDs and CDFs) and 1989 update. Washington, DC: Risk Assessment
Forum. EPA/625/3-89/016.
U.S. EPA. (1989b) Review of draft documents: a cancer risk-specific dose estimate for 2,3,7,8-TCDD. Washington,
DC. EPA Science Advisory Board Ad Hoc Dioxin Panel./625/3-89/016.
U.S. EPA. (1990a) Summary report on USEPA/Industry Cooperative Dioxin Study. "The 104 Mill Study."
Washington, DC: Office of Water Regulations and Standards. July 1990.
U.S. EPA. (1990b) Medical waste incineration emission test report. AMI Central Carolina Hospital, Sanford, North
Carolina. Volume I. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMB Report No.
90-MWI-5.
U.S. EPA. (1990c) Characterization of municipal waste combustion ash, ash extracts, and leachates. Washington,
DC: Office of Solid Waste and Emergency Response. EPA 530-SW-90-029A.
U.S. EPA. (1990d) Operation and maintenance of hospital medical waste incinerators. Research Triangle Park, NC:
Office of Air Quality Planning and Standards. EPA/625/6-89/024.
U.S. EPA. (1990e) Pesticides industry sales and usage: 1988 market estimates. Washington, DC: Office of
Pesticides and Toxic Substances.
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U.S. EPA. (1990f) Emissions of metals, chromium and nickel species, and organics from municipal wastewater
sludge incinerators. Cincinnati, OH: Office of Research and Development, Risk Reduction Engineering Laboratory.
EPA Contract No. 68-CO-0027, Work Assignment No. 0-5.
U.S. EPA. (1991a) Regulatory determination-landfills and surface impoundments receiving pulp and paper mill
sludge. Washington, DC: Office of Solid Waste and Emergency Response. EPA/530-SW-91-077.
U.S. EPA. (1991b) Methodology for assessing environmental releases of and exposure to municipal solid waste
combustor residuals. Washington, DC: Office of Research and Development. EPA/600/8-91/031.
U.S. EPA. (1991c) Medical waste incineration emission test report: Jordan Hospital, Plymouth, Massachusetts.
Volume 1. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMB Report 90-MWI-6.
U.S. EPA. (1991d) Medical and institutional waste incineration: regulations, management, technology, emissions,
and operations. Cincinnati, OH: Center for Environmental Research Information. EPA/625/4-91/030.
U.S. EPA. (1991e) Medical waste incineration emission test report. Morristown Memorial Hospital, Morristown,
New Jersey. Volume I. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMB Report
No. 91-MWI-8.
U.S. EPA. (1991f) Medical waste incineration emission test report. Borgess Medical Center, Kalamazoo, Michigan.
Volume!. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMB Report 91-MWI-9.
U.S. EPA. (1991g) Medical waste incineration emission test report: Cape Fear Memorial Hospital, Wilmington, NC;
Volume I-III. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMB Report 90-MWI-
05.
U.S. EPA. (1991h) Pesticides industry sales and usage: 1989 market estimates. Washington, DC: Office of
Pesticides and Toxic Substances.
U.S. EPA. (1991i) Workshop report on toxicity equivalency factors for polychlorinated biphenyls congeners.
EPA/625/3-91/020.
U.S. EPA. (1992a) Markets for scrap tires. Washington, DC: Office of Solid Waste and Emergency Response.
EPA/530-SW-90-074A.
U.S. EPA (1992b) Industry agrees to switch to low-dioxin chloranil from contaminated chloranil. Chemicals in
Progress Bulletin 12(2):23.
U.S. EPA. (1992c) 1990 National census of pulp, paper, and paperboard manufacturing facilities. Response to 308
questionnaire. Part A: Technical Information. Washington, DC: Office of Water.
U.S. EPA. (1992d) Economic impact and preliminary regulatory impact analysis for proposed MACT-based
emission standards and guidelines for municipal waste combustors. Research Triangle Park, NC: Office of Air
Quality Planning and Standards. EPA-450/3-91-029.
U.S. EPA. (1992e) Secondary lead smelter emission test report, East Penn Manufacturing, Lyon Station,
Pennsylvania. Research Triangle Park, NC: Office of Air Quality Planning and Standards, Emission Measurement
Branch. EMB Report No. 92-SLS-3.
U.S. EPA. (1992f) Pesticides industry sales and usage: 1990 and 1991 market estimates. Washington, DC: Office
of Prevention, Pesticides and Toxic Substances. 733-K-92-001.
U.S. EPA. (1993a) Interim report on data and methods for assessment of 2,3,7,8~tetrachlorodibenzo-p-dioxin risks
to aquatic life and associated wildlife. Washington, DC: Office of Research and Development. EPA/600/R-93/055.
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U.S. EPA. (1993b) States support efforts on forming voluntary agreement on pulp and paper mill sludge. Chemicals
in Progress Bulletin 14(3):20.
U.S. EPA. (1993c) EPA publishes proposed rule for chloranil. Chemicals in Progress Bulletin 14(2):26.
U.S. EPA. (1993d) Development document for proposed effluent limitations guidelines and standards for the pulp,
paper and paperboard point source category. Washington, DC: Office of Water. EPA-821-R-93-019.
U.S. EPA. (1993e) Economic analysis of impacts of integrated air/water regulations for the pulp and paper industry
on disposal of wastewater sludge. Washington, DC: Office of Pollution Prevention and Toxics, Regulatory Impacts
Branch.
U.S. EPA. (1993f) Press advisory: EPA terminates special review of non-wood pesticide uses of pentachlorophenol.
Washington, DC: Office of Pesticide Programs. January 8, 1993.
U.S. EPA. (1993g) Report to Congress on cement kiln dust. Washington, DC: Office of Solid Waste. December
1993.
U.S. EPA. (1993h) 1991 Toxics release inventory - public data release. Washington, DC: Office of Pollution
Prevention and Toxics. EPA-745-R-93-003.
U.S. EPA. (19931) 1992 Needs survey report to Congress. Washington, DC: Office of Water. EPA-832-R-93-002.
U.S. EPA. (1993J) Wildlife exposure factors, Vol. I. Washington, DC: Office of Health and Environmental
Assessment, Office of Research and Development. EPA/600/R-93/187a.
U.S. EPA. (1994a) Health assessment for 2,3,7,8-TCDD and related compounds. Public Review Draft.
EPA/600/EP-92/001.
U.S. EPA. (1994b) Pesticide industry sales and usage: 1992 and 1993 market estimates. Washington, DC: Office
of Prevention, Pesticides and Toxic Substances. EPA 733-K-94-001.
U.S. EPA. (1994c) Medical waste incinerators background information for proposed standards and guidelines:
Industry profile report for new and existing facilities. Research Triangle Park, NC: Office of Air Quality Planning
and Standards. EPA-453/R-94-042a.
U.S. EPA. (1994d) Medical waste incinerators-background information for proposed standards and guidelines:
Environmental impacts report for new and existing facilities. Research Triangle Park, NC: Office of Air Quality
Planning and Standards. EPA-453/R-94-046a.
U.S. EPA. (1994e) Universe of hazardous waste combustion facilities. Washington, DC: Office of Solid Waste and
Emergency Response. EPA-530-F-94-030.
U.S. EPA. (19941) Combustion emissions technical resource document (CETRED). Washington, DC: Office of
Solid Waste and Emergency Response. Draft Report. EPA/530-R-94-014.
U.S. EPA. (1994g) Preliminary source assessment for the secondary copper smelting industry. Draft report.
Research Triangle Park, NC: Office of Air Quality Planning and Standards. EPA Contract No. 68-D1-118, Work
Assignment Nos. 25, 40, and 46.
U.S. EPA. (1994h) Secondary lead smelting industry: background information document for proposed standards.
Final report. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EPA-450/R-94-024.
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U.S. EPA. (1995a) An SAB report: A second look at dioxin. Review of the Office of Research and Development's
reassessment of dioxin and dioxin-like compounds by the Dioxin Reassessment Review Committee. Science
Advisory Board (1400) September 1995. EPA-SAB-EC-95-021.
U.S. EPA. (1995b) Compilation of air pollutant emission factors. 5th edition. Research Triangle Park, NC: Office
of Air Quality Planning and Standards.
U.S. EPA. (1995c) Locating and estimating air emissions from sources of dioxins and furans. Draft final report.
Research Triangle Park, NC: Office of Air Quality Planning and Standards. Contract No. 68-D2-0160.
U.S. EPA. (1995d) Final emission test report, HAP emission testing on selected sources at a secondary lead smelter,
Tejas Resources, Inc., Terrell, Texas. Research Triangle Park, NC: Office of Air Quality Planning and Standards,
Emission Measurement Branch. EMB Report No. 93-SLS-l.
U.S. EPA. (1995e) Final emission test report, HAP emission testing on selected sources at a secondary lead smelter,
Schuylkill Metals Corporation, Forest City, Missouri. Research Triangle Park, NC: Office of Air Quality Planning
and Standards, Emission Measurement Branch. EMB Report No. 93-SLS-2.
U.S. EPA. (1995f) SRRD's dioxin/furan status report. Washington, DC: Office of Pesticide Programs, Special
Review and Reregistration Division. September 12, 1995.
U.S. EPA. (1995g) 1993 Toxics release inventory - public data release. Washington, DC: Office of Pollution
Prevention and Toxics. EPA-745-R-95-010.
U.S. EPA. (1995h) Secondary aluminum plant emission test report: Rochester Aluminum Smelting Corporation.
Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMC Report 95-SAL-01.
U.S. EPA. (19951) Draft technical support document for HWC MACT standards. Volume II: HWC emissions
database, Appendix A. Washington, DC: Office of Solid Waste and Emergency Response.
U.S. EPA. (1996a) Percentile estimates used to develop the list of pollutants for round two of the Part 503
Regulation. Washington, DC: Office of Science and Technology. EPA Contract No. 68-C4-0046.
U.S. EPA. (1996b) Municipal solid waste factbook, version 3.0. Washington, DC: Office of Solid Waste.
U.S. EPA. (1996c) EPA OSW hazardous waste combustion data base. Washington, DC: U.S. EPA, Office of Solid
Waste.
U.S. EPA. (1996d) National dioxin emission estimates from municipal waste combustors. Research Triangle Park,
NC: U.S. EPA, Office of Air Quality Planning and Standards. June 1996.
U.S. EPA. (1996e) National dioxin emissions from medical waste incinerators. Research Triangle Park, NC: Office
of Air Quality Planning and Standards. Docket #A-91-61, Item IV-A-007.
U.S. EPA. (19961) Emissions inventory of Section 112(c)(6) pollutants: polycyclic organic matter (POM), 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD)/2,3,7,8-tetrachlorodibenzofuran (TCDF), polychlorinated biphenyl compounds
(PCBs), hexachlorobenzene, mercury, and alkylated lead. Research Triangle Park, NC: Office of Air Quality
Planning and Standards. September 1996.
U.S. EPA. (1996g) PCBs: Cancer dose-response assessment and application to environmental mixtures.
Washington, D.C.: Office of Research and Development. EPA/600/P-96/001.
U.S. EPA. (1996h) Draft technical support document for hazardous waste combustor MACT standards. Volume I:
Description of source categories. Washington, DC: Office of Solid Waste and Emergency Response. February
1996.
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U.S. EPA. (19961) EIIP. Volume II: Chapter 3 - Preferred and alternative methods for estimating air emissions from
hot-mix asphalt plants. Research Triangle Park, NC: U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards.
U.S. EPA. (1996J) List of Municipal Solid Waste Landfills. Washington, DC: Office of Solid Waste, Municipal and
Industrial Solid Waste Division.
U.S. EPA. (1997a) Chapter 8. Dose-response modeling for 2,3,7,8-TCDD. January 1997 Workshop Review Draft.
EPA/600/P-92/001C8.
U.S. EPA. (1997b) Locating and estimating air emissions from sources of dioxins and furans. Research Triangle
Park, NC: Office of Air Quality Planning and Standards. DCN No. 95-298-130-54-01.
U.S. EPA. (1997c) 1996 Clean Water Needs Survey Report to Congress. Washington, DC: Office of Water.
U.S. EPA. (1997d) Draft technical support document for hazardous waste combustors MACT standards (NODA).
Volume I: MACT evaluations based on revised database. Washington, DC: Office of Solid Waste and Emergency
Response. April 1997.
U.S. EPA. (1997e) Pesticide industry sales and usage: 1994 and 1995 market estimates. Washington, DC: Office
of Prevention, Pesticides and Toxic Substances. EPA-733-R-97-002.
U.S. EPA. (1997f) Supplemental technical development document for effluent limitations guidelines and standards
for the pulp, paper, and paperboard category. Washington, DC: Office of Water. EPA-82 l-R-97-011.
U.S. EPA. (1998a) Inventory of sources of dioxin in the United States. National Center for Environmental
Assessment, Office of Research and Development. Workshop Review Draft. EPA/600/P-98/002Aa.
U.S. EPA. (1998b) 1996 Toxics release inventory-public data release. Washington, DC: Office of Pollution
Prevention and Toxics. EPA 745-R-98-005.
U.S. EPA. (1998c) AP-42: Compilation of air pollutant emissions factors. Volume I: stationary point and area
sources. Supplement D to the 5th edition. Research Triangle Park, NC: U.S. EPA, Office of Air Quality Planning
and Standards.
U.S. EPA. (1998d) Municipal Solid Waste Landfills, Volume 2: Summary of the Requirements for Section lll(d)
State Plans for Implementing the Municipal Solid Waste Landfill Emission Guidelines. Research Triangle Park, NC:
Office of Air Quality Planning and Standards. EPA-456/R-98-009.
U.S. EPA. (1999a) Monthly reporting of CDD/CDF content in technical pentachlorophenol manufactured by KMG-
Bermuth, Inc. and Vulcan Chemicals, 1987 to 1999. Washington, DC: Office of Pesticide Programs.
U.S. EPA. (1999b) Technical background document for the Report to Congress on remaining wastes from fossil fuel
combustion: waste characterization. Washington, DC: Office of Solid Waste and Emergency Response.
U.S. EPA. (1999c) Technical background document for the Report to Congress on remaining wastes from fuel
combustion: industry statistics and waste management practices. Washington, DC: Office of Solid Waste and
Emergency Response.
U.S. EPA. (1999d) EPA OSWER hazardous waste combustor emissions data base. Washington, DC: Office of Solid
Waste and Emergency Response.
U.S. EPA. (1999e) Biosolids Generation, Use, and Disposal in the United States. Office of Solid Waste and
Emergency Response. EPA530
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U.S. EPA. (1999f) Emission Test Evaluation of a Crematory at Woodlawn Cemetary in the Bronx, NY. Office of
Air Quality Planning and Standards. EPA-454/R-99-049
U.S. EPA. (1999g) Final Report - Volume I of II, Iron and Steel Foundries Manual Emissions Testing Cupola Wet
Scrubber General Motors Corp. Saginaw, Michigan. Office of Air Quality Planning and Standards. EPA-454/R-99-
025A.
U.S. EPA. (1999h) Final Report - Volume I of II, Iron and Steel Foundries Manual Emissions Testing of Cupola
Baghouse at Waupaca Foundry in Tell City, Indiana. Office of Air Quality Planning and Standards. EPA-454/R-99-
017A.
U.S. EPA. (2000a) E-mail from John Bachmann (EPA/OAQPS) to Dwain Winters (EPA/OPPT). Revised MWI,
MWC dioxin estimates. May 1, 2000.
U.S. EPA. (2000b) Exposure and human health reassessment of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and
related compounds. Part 1: Estimating exposure to dioxin-like compounds. Washington, DC: National Center for
Environmental Assessment, Office of Research and Development. EPA/600/P-00/001B(b-d).
U.S. EPA. (2000c) Exposure and human health reassessment of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and
related compounds. Part 2: Health assessment for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and related
compounds. Washington, DC: National Center for Environmental Assessment, Office of Research and
Development. EPA/600/P-00/001Be.
U.S. EPA. (2000d) Exposure and human health reassessment of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and
related compounds. Part 3: Dioxin: Integrated summary and risk characterization for 2,3,7,8-tetrachlorodibenzo-p-
dioxin (TCDD) and related compounds. Washington, DC: National Center for Environmental Assessment, Office of
Research and Development. EPA/600/P-00/001Bf.
U.S. EPA. (2000e) Emission Test Evaluation of a Pathological Waste Incinerator at the University of Georgia.
Research Triangle Park, NC: Office of Air Quality Planning and Standards. EPA-456/R-00-004.
U.S. EPA. (2000f) Source Characterization for Sewage Sludge Incinerators. Washington, DC: Office of Air Quality
Planning and Standards. EPA-454/R-00-038a
U.S. EPA. (2001a) Municipal Solid Waste in The United States: 1999 Facts and Figures. Office of Solid Waste and
Emergency Response. EPA530-R-01-014
U.S. EPA. (200 Ib) Hot Mix Asphalt Plants Emission Assessment Report. Office of Air Quality Planning and
Services. Research Triangle Park, NC. EPA-454/C-01-002.
U.S. EPA. (2001c) Exposure and Human Health Reassessment of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin (TCDD) and
Related Compounds. Part I: Estimating Exposure to Dioxin-Like Compounds. Volume 1: Sources of Dioxin-Like
Compounds in the United States. Office of Research and Development. Washington, DC. EPA/600/P-00/001Cb.
U.S. EPA. (2001d) Documentation Report for National and County-level Emission Estimates for Residential Wood
Combustion. Prepared for EFIG by Eastern Research Group, Inc. July 3, 2001.
U.S. EPA (2001e) Environmental assessment of proposed revisions to the national pollutant discharge elimination
system regulation and the effluent guidelines for concentrated animal feeding operations. Office of Water
Regulations and Standards, Washington DC; EPA-821-B-01-001, January.
U.S. EPA (20011) Final titanium dioxide listing background document for the inorganic chemical listing
determination. Office of Solid Waste. Washington, DC.
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U.S. EPA. (2002a) Statistical Support Document for the Development of Round 2 Biosolids Use or Disposal
Regulations. Office of Science and Technology. EPA-822-R-02-034.
U.S. EPA. (2002b) Hazardous Waste MACT Database. Office of Solid Waste.
http://www.epa.gov/epaoswer/hazwaste/combust/ph2nodal/page2-3.htm#Words Accessed February 25, 2003.
U.S. EPA. (2002c) Landman, Larry C. Draft: Updating Fuel Economy Estimates in MOBILE6.3. Document
Number M6.GHG.001. EPA420-P-02-005. http://www.epa.gov/otaq/models/mobile6/p02005.doc
U.S. EPA. (2002d) Municipal Solid Waste in The United States: 2000 Facts and Figures. Office of Solid Waste and
Emergency Response. EPA530-R-02-001
U.S. EPA. (2002e) Documentation for Version 2 of the 1999 NEI for Criteria Air Pollutants, Area Sources. Research
Triangle Park, NC: Office of Air Quality Planning and Standards, Emission Factor and Inventory Group. November,
2002.
U.S. EPA. (2003a) Telephone conversation between C. Gross, U.S. EPA Office of Water, and K. Riley, Versar, Inc.,
on February 26, 2003.
U.S. EPA. (2003b) E-mail from B. Guzzone, U.S. EPA Landfill Methane Outreach Program, to K. Riley, Versar,
Inc., on February 28 and March 7, 2003.
U.S. EPA. (2003c) EPA TRI Explorer (Ver 4.01). Office of Environmental Information. Available online at
http ://www. epa. gov/triexplorer.
U.S. EPA. (2003d) Documentation of Emission Estimation Methods for Year 2000 and 2001 Mobile andNonpoint
Source Dioxin Inventories, Prepared for U.S. EPA, Office of Air Quality Planning and Standards, Prepared by E.H.
Pechan & Associates, Inc. May, 2003
U.S. EPA. (2003e) Correspondence from U.S. EPA, Office of Air Quality Planning and Standards to D. Cleverly,
U.S. EPA, Office of Research and Development, dated June 5, 2003.
U.S. EPA. (2003f) Chemical Information Collection and Data Development (Testing) web site,
http://www.epa.gov/opptintr/chemtest/polvha.pdf.
U.S. EPA. (2004) Clean water needs survey 2000, discharge report. Office of Water, Office of Wastewater
Management, Washington, DC. Available online at http://cfpub.epa.gov/cwns/rpt dischargel OO.cfm.
USGS (U.S. Geological Survey). (1997a) Minerals yearbook: recycling - nonferrous metals chapter. Reston, VA:
U.S Geological Survey, Geologic Division.
USGS. (1997b) Mineral commodity survey - iron and steel scrap. Washington, DC: U.S. Department of the Interior,
U.S. Geological Survey.
USGS. (1997c) Statistical compendium: copper. Washington, DC: U.S. Department of the Interior, U.S. Geological
Survey.
USGS. (1997d) Statistical compendium - aluminum. Reston, VA: U.S. Geological Survey, Geologic Division.
USGS. (1997e) Mineral commodities summary - aluminum. Reston, VA: U.S. Geological Survey, Geologic
Division.
USGS. (19971) Statistical compendium - titanium. Reston, VA: U.S. Geological Survey, Geologic Division.
USGS. (2002) Mineral Commodity Summaries for 2000. Reston, VA: U.S. Geological Survey, Geologic Division.
03/04/05 R-47 DRAFT-DO NOT CITE OR QUOTE
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U.S. International Trade Commission (1946 through 1994) Synthetic organic chemicals - United States production
and sales. Washington, DC: U.S. International Trade Commission.
U.S. International Trade Commission (1984) Imports of benzenoid chemicals and products 1983; investigation no.
332-135. Washington, DC: U.S. International Trade Commission. USITC Publication No. 1548.
Van den Berg, M; Birnbaum, L; Bosveld, ATC; et al. (1998) Toxic equivalency factors (TEFs) for PCBs, PCDDs,
PCDFs for humans and wildlife. Environmental Health Perspectives 106:775-792.
VanDort, H.M; Bedard, DL. (1991) Reductive ortho and meta dechlorination of a polychlorinated biphenyl
congener by anaerobic microorganisms. Appl Environ Microbiol 57:1576-1578.
Van Oostdam, JC; Ward, JEH. (1995) Dioxins and furans in the British Columbia environment. Victoria, British
Columbia: BC Environment, Environmental Protection Department.
Van Wijnen, JH; Liem, AKD; Olie, K; et al. (1992) Soil contamination with PCDDs and PCDFs of small (illegal)
scrap wire and scrap car incineration sites. Chemosphere 24(2): 127-134.
Vermont Air Pollution Control Division. (1996) Source emission test at Safety Medical Systems, Colchester, VT.
Waterbury, VT: State of Vermont, Agency of Natural Resources, Air Pollution Control Division.
Versar, Inc. (1976) PCBs in the United States: industrial use and environmental distribution. Washington, DC:
U.S. Environmental Protection Agency, Office of Toxic Substances. EPA Contract No. 68-01-3259, Task I.
Versar, Inc. (1985) List of chemicals contaminated or precursors to contamination with incidentally generated
polychlorinated and polybrominated dibenzodioxins and dibenzofurans. EPA Contract No. 68-02-3968, Task No.
48.
Versar, Inc. (1988) PCB exposure assessment of scrap/salvage facilities. Washington, DC: U.S. Environmental
Protection Agency, Office of Toxic Substances. EPA Contract No. 68-02-4254. Task No. 136.
Vikelsoe, J; Madsen, H; Hansen, K. (1993) Emission of dioxins from Danish wood-stoves. Organohalogen
Compounds 11:405-408.
Vickelsoe, J; Lassen, P; Johansen, E; et al. (1994) Formation of PCDD/PCDFs via an enzymatically mediated
chlorination of humic acids. Organohalogen Compounds 20:351-354.
Villanueva, EC; Jennings, RW; Burse, VW; et al. (1974) Evidence of chlorodibenzo-p-dioxin and
chlorodibenzofuran in hexachlorobenzene. J Agr Food Chem 22(5):916-917.
Viraraghavan, T; Slough, K. (1999) Sorption of pentachlorophenol on peat-bentonite mixtures. Chemosphere
39:1487-1496.
Virta, R L. (2000) Clays. U.S. Geological Survey, Mineral Commodity Summaries. February 2000. Available on
the USGS Internet site: http://www.usgs.gov/.
Vogg, H; Metzger, M; Steiglitz, L. (1987) Recent findings on the formation and decomposition of PCDD/PCDF in
municipal solid waste incineration. Waste Management and Research 5(3):285-294.
Vogg, H; Nunsinger, H, Merz, A; et al. (1992) Influencing the production of dioxin/furan in solid waste incineration
plants by measures affecting the combustion as well as the flue gas cleaning systems. Chemosphere 25(1-2): 149-152.
Vollmuth, S; Zajc, A; Niessner, R. (1994) Formation of polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans during the photolysis of pentachlorophenol-containing water. Environ Sci Technol 28(6): 1145-1149.
03/04/05 R-48 DRAFT-DO NOT CITE OR QUOTE
-------
Waddell, DS; Boneck-Ociesa, H; Gobran, T; etal. (1995) PCDD/PCDF formation by UV photolysis of
pentachlorophenol with and without the addition of hydrogen peroxide. Organohalogen Compounds 23:407-412.
Wagner, JC; Green, AES. (1993) Correlation of chlorinated organic compound emissions from incineration with
chlorinated organic input. Chemosphere 26 (11):2039-2054.
Wagner, HC; Schramm, KW; Hutzinger, O. (1990) Biogenic polychlorinated dioxin and furan from trichlorophenol.
Organohalogen Compounds 3:453-456.
Walsh, PJJ; Brimblecombe, P; Creaser, CS; et al. (1994) Biomass burning and polychlorinated dibenzo-p-dioxins &
furans in soil. Organohalogen Compounds (20):283-287.
Wan, MT. (1995) Treated wood as a source of dioxin/furan releases. Organohalogen Compounds 24:109-114.
Wan, MT; Van Oostdam, J. (1995) Utility and railway rights-of-way contaminants: dioxins and furans. J Environ
Qua! 24:257-265.
Wang, LC; Lee, WJ; Lee, WS; Chang-Chien, GP; et al. (2003) Effect of chlorine content in feeding wastes of
incineration on the emission of poly chlorinated dibenzo-p-dioxins/dibenzofurans. The Science of the Total
Environment 302:185-198.
Ward, DE; McMahon, CK; Johansen, RW. (1976) An update on paniculate emissions from forest fires. Presented at:
69th Annual Meeting of the Air Pollution Control Association. Portland, OR. June 27-July 1, 1976.
Ward, DE; Peterson, J; Hao, W.M. (1993) An inventory of paniculate matter and air toxic emissions from prescribed
fires in the USA for 1989. Presented at: 86th Annual Meeting & Exhibition, Air & Waste Management Association;
Denver, Colorado; June 1993.
Washington State Department of Ecology. (1998) Washington State dioxin source assessment. Publication No. 98-
320.
Watanabe, I; Tatsukawa, R. (1987) Formation of brominated dibenzofurans from the photolysis
of flame retardant decabromobiphenyl ether in hexane solution by UV and sun light. Bull. Environ. Contam.
Toxicol. 39:953-959.
Water Pollution Control Federation. (1990) Operation of municipal wastewater treatment plants. Manual of Practice
No. 11. Alexandria, VA: Water Pollution Control Federation.
Weber, H; Disse, G; Hamann, R; et al. (1995) Influence of the aerobic and anaerobic digestion on the levels of
chlorinated dibenzofurans and dibenzodioxins in sewage sludge. Organohalogen Compounds 24:81-85.
Weber, P; Altwicker, E; Dinjus, E; et al. (1999) The role of aliphatic organic chlorine in the formation of
PCDD/PCDF on fly ash in comparison to inorganic chlorine. Organohalogen Compounds 41:11-14.
Weber, R; Hagenmaier, H. (1999) Mechanism of formation of polychlorinated dibenzo-p-dioxins and dibenzofurans
from chlorophenols in gas phase reactions. Chemosphere 38:529-549.
Welsch-Pausch, K; McLachlan, MS. (1995) Photodegradation of PCDD/Fs on pasture grass. Organohalogen
Compounds 24:509-512.
Welsch-Pausch, K; McLachlan, MS; Umlauf, G. (1995) Determination of the principal pathways of polychlorinated
dibenzo-p-dioxins and dibenzofurans to Lolium multiflorum (Welsh Ray Grass). Environ Sci Technol 29:1090-
1098.
03/04/05 R-49 DRAFT-DO NOT CITE OR QUOTE
-------
Wenning, RJ; Harris, MA; Paustenbach, DJ; et al. (1992) Potential sources of 1,2,8,9-tetrachlorodibenzo-p-dioxin in
the aquatic environment. Ecotoxicology and Environmental Safety 23:133-146.
Western Environmental Services and Testing, Inc. (2000) Magnesium Corporation of America,Rowley, Utah.
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Melt reactor and cathode stacks. May 2000.
File Number 00-1043.
Wevers, M; De Fre, R. (1995) Estimated evolution of dioxin emissions in Belgium from 1988 to 1995.
Organohalogen Compounds 24:105-108.
Wevers, M; De Fre, R; Rymen, T. (1992) Dioxins and dibenzofurans in tunnel air. Volume 9 (Sources of Exposure)
of Extended Abstracts. Organohalogen Compounds 9:321-324.
Whitman, WG. (1927) The two-film theory of gas absorption. Chemical and Metallurgical Engineering 29(4): 146-
148.
WHO (World Health Organization). (1991) IARC monographs on the evaluation of carcinogenic risks to humans:
occupational exposures in insecticide application, and some pesticides. Geneva, Switzerland: World Health
Organization, International Agency for Research on Cancer.
Wichmann, H; Zelinski, V; Scholz-Bottcher, B; et al. (1993) Sampling strategy to investigate the distribution
behavior of low volatile pollutants like "dioxins" during vehicle fires in traffic tunnels. Chemosphere 26(6): 1159-
1166.
Wichmann, H; Lorenz, W; Bahadir, M. (1995) Release of PCDD/F and PAH during vehicle fires in traffic tunnels.
Chemosphere 31(2): 275 5-2766.
Wienecke, J; Kruse, H; Wassermann, O. (1992) Organic compounds in the flue gas from a power station with
circulatory fluid bed combustion of coal. Chemosphere 25(12): 1889-1895.
Wikstrom, E; Lofvenius, G; Rappe, C; et al. (1996) Influence of level and form of chlorine on the formation of
chlorinated dioxins, dibenzofurans, and benzenes during combustion of an artificial fuel in a laboratory reactor.
Environ Sci Technol 30:1637-1644.
Wikstrom, E; Persson, A; Marklund, S. (1998) Secondary formation of PCDDs, PCDFs, PCBs, PCBzs, PHPhs and
PAHs during MSW combustion. Organohalogen Compounds 36:65-68.
Wikstrom, E; Ryan, S; Touati, A; Telfer; M; et al. (2003) Importance of chlorine speciation on de Novo formation of
polychlorinated dibenzo-p-dioxins and polychlorinated dibanzofurans. Environ Sci Technol 37:1108-1113.
Wilken, M; Cornelsen, B; Zeschmar-Lahl, B; et al. (1992) Distribution of PCDD/PCDF and other organochlorine
compounds in different municipal solid waste fractions. Chemosphere 25:1517-1523.
Williams, CH; Prescott, CL; Stewart, PB; et al. (1985) Formation of polychlorinated dibenzofurans and other
potentially toxic chlorinated pyrolysis products inPCB fires. In: Keith, L.H.; Rappe, C.; Choudhary, G., eds.,
Chlorinated dioxins and dibenzofurans in the total environment II. Boston, MA: Butterworth Publishers.
Williams, DT; LeBel, GL; Benoit, FM. (1992) Polychlorodibenzodioxins and polychlorodibenzofurans in dioxazine
dyes and pigments. Chemosphere 24(2): 169-180.
Wittsiepe, J; Kullmann, Y; Schrey, P; et al. (1998) Myeloperoxidase - catalyzed formation of PCDD/F from
chlorophenols. Organohalogen Compounds 36:351-356.
Woolson, EA; Thomas, RF; Ensor, PDJ. (1972) Survey of polychlorodibenzo-p-dioxin content in selected pesticides.
J Agr Food Chem 20(2):351-354.
03/04/05 R-50 DRAFT-DO NOT CITE OR QUOTE
-------
Wunsch, P; Leichsenring, S; Schramm, K; et al. (1994) Temperature dependence of PCDD/F-formation in boiler
ash. Chemosphere 29(6): 1235-1243.
Yamamoto, T; Fukushima, M. (1992) Modeling study on contribution of combustion source complex to PCDD/CDF
levels in urban air. Organohalogen Compounds 9:343-346.
Younes, M. (1998) WHO toxic equivalency factors (TEFs) for dioxin-like compounds for humans and wildlife.
Summary of WHO meeting held in Stockholm, Sweden on June 15-18. World Health Organization, International
Programme on Chemical Safety.
Young, AL. (1983) Long-term studies on the persistence and movement of TCDD in a natural ecosystem. In:
Human and environmental risks of chlorinated dibenzodioxins and related compounds. Tucker, R.E.; Young, A.L.;
Gray, A.P., Eds. Plenum Press.
Zenith Research Group. (2000) Summary report on burn barrels. Prepared for the Western Lake Superior Sanitary
District, Minnesota. January 18.
Zenith Research Group. (2001) A survey of residents of Northeast Minnesota & Northwest Wisconsin. Prepared for
the Western Lake Superior Sanitation District, Duluth, MN.
Zheng, M-H; Liu, P-Y; Xu, X-B. (1999) Mechanism of formation of poly chlorinated biphenyls from the pyrolysis of
chlorobenzenes. Organohalogen Compounds 41:15-18.
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