vvEPA
United States
Environmental Protection
Agency
Office of Research and
Development
Washington DC 20460
The Inventory of
Sources of Dioxin
in the United States
EPA/600/P-98/002Aa
April 1998
External Review Draft
Draft
(Do Not
Cite or
Quote)
Notice
This document is a preliminary draft. It has not been formally
released by EPA 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.
-------
-------
EPA/600/P-98/002Aa
> April 1998
DO NOT QUOTE OR CITE - External Review Draft
THE INVENTORY OF SOURCES OF
DIOXIN IN THE UNITED STATES
NOTICE
THIS DOCUMENT IS AN EXTERNAL REVIEW DRAFT. It has not been formally released by
the U.S. Environmental Protection Agency and should not at this stage be construed to
represent Agency policy. It is being circulated for comment on its technical accuracy and
policy implications. , ,
Exposure Analysis and Risk Characterization Group
National Center for Environmental Assessment '
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C.
-------
DRAFT-DO NOT QUOTE OR CITE
DISCLAIMER
This document is an external review 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.
-------
DRAFT-DO NOT QUOTE OR CITE
TABLE OF CONTENTS
List of Tables . . vjjj
List of Figures . . . x::
Acknowledgements . . . ....:........ xiv
1. INTRODUCTION ••:..../............:.......... 1-2
1.1. DESCRIPTION OF DIOXIN-LIKE COMPOUNDS '. . . ]'.'•'. '. ••';'''''''' 1 3
1.2 TOXICITY EQUIVALENCE FACTORS '. 1-4
2. OVERVIEW OF SOURCES 2-1
2.1. EMISSIONS INVENTORY METHODOLOGY ".'.'.'.'.'.'.'.'.'.'•" 2-1
2.2. GENERAL FINDINGS OF THE EMISSIONS INVENTORY •'•"•.•••;•••• ^ ?
2.3. GENERAL SOURCE OBSERVATIONS 2-10
3. COMBUSTION SOURCES OF CDD/CDF: .WASTE INCINERATION 3-1
3.1. MUNICIPAL SOLID WASTE INCINERATION 3-2
3-1-1- Descr'Ption of Municipal Solid Waste Incineration Technologies . 3-2
3.1.2, Characterization of MSWI Facilities in Reference Years 1995 and
1987 3-7
3.1.3. Estimation of CDD/CDF Emissions from MSWIs 3-8
3.1.4. Summary of CDD/CDF (TEQ) Emissions from MSWIs for 1995
and 1987 .....; . 3.^0
3.1.5 Congener Profiles of MSWI Facilities ; . 3.11
3.1.6 Estimated CDD/CDFs in MSWI Ash . .......... . 3-11
3.1.7 Current EPA Regulatory and Monitoring Activities . 3-12
3.2. HAZARDOUS WASTE INCINERATION ]'m\'m 3.13
3.2.1. Furnace Designs for Dedicated Hazardous Waste Incinerators 3-14
3.2.2. APCDs for Dedicated Hazardous Waste Incinerators ........ 3-16
3.2.3. Estimation of CDD/CDF Emission; Factors for Dedicated Hazardous
Waste Incinerators . . . 3-17
3.2.4.. Emission Estimates for Dedicated Hazardous Waste Incinerators 3-19
3.2.5. fndustrial Boilers and Furnaces Burning Hazardous Waste 3-21
3.3. MEDICAL WASTE INCINERATION m\ 3.22
3.3.1. Design Types,pf MWIs Operating in the United States . . ... . . 3-23
3.3.2. Characterization of MWIs for Reference Years 1995 and 1987 . 3-24
3.3.3. Estimation of CDD/CDF Emissions From MWIs . . 3 26
3,3.4. EPA/OAQPS Approach for Estimating CDD/CDF Emissions from
MWIs . . . ... 3_27
3.3.4.1. EPA/OAQPS Approach for Estimating Activity Level . 3-27
3.3.4.2. EPA/OAQPS Approach for Estimating CDD/CDF
Emission Factors 3-28
HI
-------
DRAFT-DO NOT QUOTE OR CITE
TABLE OF CONTENTS (continued)
3.3.4.3. EPA/OAQPS Approach for Estimating Nationwide
CDD/CDF TEQ Air Emissions 3-29
3.3.5. AHA Approach for Estimating CDD/CDF Emissions from MWIs . 3-30
3.3.6. EPA/ORD Approach for Estimating CDD/CDF Emissions from
MWIs 3-31
3.3.6.1. EPA/ORD Approach for Classifying MWIs and
Estimating Activity Levels ; 3.31
3.3.6.2. EPA/ORD Approach for Estimating CDD/CDF Emission
Factors „ 3-33
3.3.7. Summary of CDD/CDF Emissions From MWIs ..... 3.34
3.4. CREMATORIA 3.37
3.5. SEWAGE SLUDGE INCINERATION . 3-38
3.6. TIRE COMBUSTION .'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.' 3-40
3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED CHEMICAL
PULP MILLS . 3.42
3.8. BIOGAS COMBUSTION ............ 3-43
4. COMBUSTION SOURCES OF CDD/CDF: POWER/ENERGY GENERATION 4-1
4.1. MOTOR VEHICLE FUEL COMBUSTION 4.-]
4.1.1. Tailpipe Emission Studies 4.-)
4.1.2. Tunnel Emission Studies 4.5
4.1.3. National Emission Estimates 4.9
4.2. WOOD COMBUSTION '.'.'.'.'.'.'.'.'.'.'.'.'.'. 4-15
4.2.1. Residential Wood Combustion 4-16
4.2.2. Industrial Wood Combustion 4_19
4.3. OIL COMBUSTION '.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'. 4-23
4.3.1. Residential/Commercial Oil Combustion . . . 4-23
4.3.2. Utility Sector and Industrial Oil Combustion 4-24
4.4. COAL COMBUSTION '.'.'.'.'. 4-25
4.4.1. Utilities and Industrial Boilers 4_26
4.4.2.' Residential/Commercial Coal Combustion 4-28
5. COMBUSTION SOURCES OF CDD/CDF: OTHER HIGH TEMPERATURE
SOURCES g.., '
5.1. CEMENT KILNS . 5-1
5.1.1. Process Description of Portland Cement Kilns 5-1
5.1.2. Cement Kilns Burning Hazardous Waste 5.3
5.1.3. Air Pollution Control Devices Used on Cement Kilns . 5-4
5.1.4. CDD/CDF Emission Factors for Cement Kilns . . 5.4
5.1.5. National Estimates of CDD/CDF Emissions from Cement Kilns ... 5-7
5.1.6. Cement Kiln Dust 5.9
5.2. ASPHALT MIXING PLANTS ' 5 10
IV
-------
DRAFT-DO NOT QUOTE OR CITE '
TABLE OF CONTENTS (continued)
5.3. PETROLEUM REFINING CATALYST REGENERATION . ; '. 5-12
5.4, CIGARETTE SMOKING '....'.'. 5-15
5.5. PYROLYSIS OF BROMINATED FLAME RETARDANTS ......''. ]''. '. . . . . 5-18
5.6. CARBON REACTIVATION FURNACES ..... . 5-19
5.7. KRAFT BLACK LIQUOR RECOVERY BOILERS ... . . . ..... ..... . 5-22
5.8. OTHER IDENTIFIED SOURCES . . . . ............. .". ...... . 5-24
6. COMBUSTION SOURCES OF CDD/CDF: MINIMALLY CONTROLLED AND
UNCONTROLLED COMBUSTION SOURCES . 6-1
6.1. COMBUSTION OF LANDFILL GAS ! 6-1
6.2. ACCIDENTAL FIRES . . ... . ... .'.'.'.'.]''.'.'.'.'.'.', 6-2
6.2.1. Soot/Ash Studies 6-3
6.2.2. Fume/Smoke Studies . . . . . . . . .,. . 6-5
6.2.3. Data Evaluation . 6-6
6.3. LANDFILL FIRES . . . . ..........!/.'.. 6-8
6.4. FOREST AND BRUSH FIRES ''.'.'.'.'.''.'.'.'.'.'.''.'. . . ""." '6_10
6.5 BACKYARD TRASH BURNING .............. 6-14
6.6. UNCONTROLLED COMBUSTION OF POLYCHLORINATED BIPHENYLS
(PCBS) '....... 6-15
6,7. VOLCANOES .,',. .......... 6-16
7. METAL SMELTING AND REFINING SOURCES OF CDD/CDF . . . . 7-1
7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING .......... 7-1
7.2. SECONDARY NONFERROUS METAL SMELTING . . . . ......... 7-2
7.2.1. Secondary Aluminum Smelters . . . . * 7-2
7.2.2. Secondary Copper Smelters/Refiners . 7-5
7.2.3. Secondary Lead Smelters/Refiners 7-7
7.3. PRIMARY FERROUS METAL SMELTING/REFINING . . , . ........ 7-10
7.3.1 > Sinter Production . . 7-10
7.3.2 . Coke Production 712
7.3.3 Electric Arc Furnaces '." 7-13
7,4 FERROUS FOUNDRIES ...*.....].... '. '.'. 7-14
7.5. SCRAP ELECTRIC WIRE RECOVERY . .."...... . '.'. ...... 7-16
7.6. DRUM AND BARREL RECLAMATION FURNACES ......... . . . . . . ] . 7-18
8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES .......... 8-1
8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS ........!!!! 8-1
8.2. MANUFACTURE OF CHLORINE, CHLORINE DERIVATIVES, AND METAL
CHLORIDES .. 8-5
8.2.T. Manufacture of Chlorine . . . . .........'... 8-5
8,2.2. Manufacture of Chlorine Derivatives and Metal Chlorides . . . . . . 8-6
v
-------
DRAFT-DO NOT QUOTE OR CITE
TABLE OF CONTENTS (continiusd)
8.3. MANUFACTURE OF HALOGENATED ORGANIC CHEMICALS .... 8-7
8.3.1. Chlorophenols . .8-7
8.3.2. Chlorobenzenes g_1Q
8.3.3. Chlorobiphenyls 8-13
8.3.4. Polyvinyl Chloride 8-16
8.3.5. Other Aliphatic Chlorine Compounds 8-19
8.3.6. Dyes, Pigments, and Printing Inks ~. ...... 8-20
8.3.7. TSCA Dioxin/Furan Test Rule 8-22
8.3.8. Halogenated Pesticides and FIFRA Pesticides Data Call-In 8-23
8.4. OTHER CHEMICAL MANUFACTURING AND PROCESSING SOURCES . . 8-28
8.4.1. Municipal-Wastewater Treatment Plants 8-28
8.4.2. Drinking Water Treatment Plants 8-34
8.4.3. Soaps and Detergents 8-34
8.4.4. Textile Manufacturing and Dry Cleaning 8-36
9. BIOLOGICAL SOURCES OF CDD/CDF g.-,
9.1. BIOTRANSFORMATION OF CHLOROPHENOLS ... 9'-\
9.2. BIOTRANSFORMATION OF HIGHER CDD/CDFS . . . .' .' 9.4
10. PHOTOCHEMICAL SOURCES OF CDD/CDF 10 •,
10.1. PHOTOTRANSFORMATION OF CHLOROPHENOLS 101
10.2. PHOTOLYSIS OF HIGHER CDD/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 10-6:
10.2.4 Photolysis in Air 1Q-6
11. SOURCES OF DIOXIN-LIKE PCBs . -, -, -,
11.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY 111
11.2 RELEASES OF COMMERCIAL PCBs '.'.'.'.['. 11-3
11.2.1. Approved PCB Disposal/Destruction Methods 11-6
11.2.2. Accidental Releases of In-Service PCBs '.'.'.'.'.'. 11-8
11.2.3. Municipal Wastewater Treatment 11-11
11.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 11-13
11.4. COMBUSTION SOURCES !.'.'.'."' 11-13
11.4.1. Municipal Solid Waste Incineration .....' 11-13
11.4.2. Industrial Wood Combustion 11-15
11.4.3. Medical Waste Incineration 11-15
11.4.4. Tire Combustion 11-16
11.4.5. Cigarette Smoking 11-17
11.4.6. Sewage Sludge Incineration 11-18
VI
-------
DRAFT-DO NOT QUOTE OR CITE
TABLE OF CONTENTS (continued)
11.5. NATURAL SOURCES .. 11-18
11.5.1. Biotransformation of Other PCBs 11-18
11.5.2. Photochemical Transformation oi Other PCBs . . . 11-22
REFERENCES ...... . ... . .... R.-,
VII
-------
DRAFT-DO NOT QUOTE OR CITE
LIST OF TABLES
Table 1-1. Toxicity Equivalency Factors (TEF) for CDDs and CDFs 1-6
Table 1-2. Dioxin-Like PCBs ........ : 1-7
Table 1-3. Nomenclature, for Dioxin-Like Compounds 1-8
Table 2-1. Confidence Rating Scheme for U.S. Emission Estimates 2-12
Table 2-2. Dioxin-Like Compound Emission Inventory for the United States
(Reference Year 1995) ,,,2-13
Table 2-3. Dioxin-Like Compound Emission Inventory for the United States
(Reference Year 1987) 2-16
Table 2-4. CDD/CDF TEQ Emission Factors Used to Develop National Emission
Inventory Estimates of Releases to Air 2-22
Table 2-5. Order of Magnitude Estimates of CDD/CDF Air Emissions from Sources
Not Quantified in the National inventory (Reference Year 1995) ...... 2-24
Table 2-6. CDD/CDF. Air Emission Inventories for West Germany, Austria, The
Netherlands, Switzerland, Belgium, and the United Kingdom 2-25
Table 3-1. Inventory of MSWIs in 1995 by Technology, APCD, and Activity Level . 3-53
Table 3-2. Inventory of MSWIs in 1987 by Technology, APCD, and Annual Activity
Level 3.55
Table 3-3. Dioxin TEQ Emission Factors (ng TEQ per kg waste) for Municipal Solid
Waste Incineration 3.57
Table 3-4. Annual TEQ Emissions (g/yr) From MSWIs Operating in 1995 '.'. 3-59
Table 3-5. Annual TEQ Emissions to the Air From MSWIs Operating in 1987 3-60
Table 3-6. CDD/CDF Emission Factors for Hazardous Waste Incinerators and Boilers 3-62
Table 3-7. Summary of Annual Operating Hours for Each MWI Type 3-65
Table 3-8. OAQPS Approach: PM Emission Limits for MWIs and Corresponding
Residence Times in the Secondary Combustion Chamber 3-66
Table 3-9. OAQPS Approach: Estimated Nationwide CDD/CDF TEQ Emissions (g/yr)
for 1995 3_67
Table 3-10. AHA Approach: TEQ Emission Factors Calculated for Air Pollution
Control ... l 3-68
Table 3-11. AHA Assumptions of the Percent Distribution of Air Pollution Control
on MWIs Based on PM Emission Limits 3.59
Table 3-12. AHA Approach: Estimated Annual Nationwide CDD/CDF TEQ Emissions 3-70
Table 3-13. Comparison Between Predicted Residence Times and Residence Times
Confirmed by State Agencies from EPA/ORD Telephone Survey 3-71
Table 3-14. EPA/ORD Approach: Annual TEQ Emissions from Medical Waste
Incineration (MWI) for Reference Year 1995 3-72
Table 3-15. Summary of Annual TEQ Emissions from Medical Waste Incineration (MWI)
for Reference Year 1987 . . . ':...' 3.75
Table 3-16. Comparisons of Basic Assumptions Used in the EPA/ORD, the EPA/OAQPS,
and the AHA Approaches to Estimating Nationwide CDD/CDF TEQ '
Emissions from MWIs in 1995 3.75
VIII
-------
DRAFT-DO NOT QUOTE OR CITE
LIST OF TABLES (continued)
Table 3-17. GDD/CDF Air Emission Factors for a Crematorium .... . .... . 3.77
Table 3-18. CDD/CDF Emission Factors for Sewage Sludge Incinerators . 3.79
table 3-19. CDD/CDF Air Emission Factors for Tire Combustion . . . '. . . 3-81
Table 3-20. CDD/CDF Emission Factors for Combustion of Bleached-Kraft Mill Sludge
in Wood Residue Boilers • 3.33
Table 4-1. Descriptions and Results of Vehicle Emission Testing Studies for CDDs
and CDFs ...... 4 30
Table 4-2. Diesel-Fueled Automobile CDD/CDF Congener Emission Factors ".'.'.'.'. '. 4-31
Table 4-3. Diesel-Fueled Truck CDD/CDF Congener Emission Factors ........... 4-32
Table 4-4. Leaded Gasoline-Fueled Automobile CDD/CDF Congener Emission
Factors 4-33
Table 4-6. Unleaded Gasoline-Fueled (With Catalytic Converters) Automobile
CDD/CDF Congener Emission Factors 4.35
Table 4-7. European Tunnel Study Test Results "... '. ' ' 4.39
Table 4-8. Baltimore Harbor TunnelStudy: Estimated Emission Factors for Heavy-Dutv
(HD) Diesel Vehicles 4.40
Table 4-9. CDD/CDF Concentrations in Residential Chimney Soot from Wood Stoves
and Fireplaces 4-42
Table 4-10. CDD/CDF Concentrations in Residential Bottom Ash from Wood Stoves
and Fireplaces .... . , 4-43
Table 4-11. CDD/CDF Concentrations in Chimney Soot (Bavaria, Germany) . . . . . '. . 4.44
Table 4-12. CDD/CDF Emission Factors for Industrial Wood Combustors <...... 4.4-5
Table 4-13. Estimated CDD/CDF Emission Factors for Oil-Fired Residential Furnaces '. 4-47
Table 4-14. CDD/CDF Emission Factors for Oil-Fired Utility/Industrial Boilers ...... 4-49
Table 4-15. CDD/CDF Concentrations in Stack Emissions from U.S. Coal-Fired
Power Plants ' 4-51
Table 4-16. Characteristics of U.S. Coal-Fired Power Plants Tested by DOE ....... 4-52
Table 4-17. CDD/CDF Emission Factors for.Coal-Fired Utility/Industrial Power " ' : "••
Plants 4-53
Table 4.-18. CDD/CDF Emission Factors from Residential Coal Combwstors ...... 4-55
Table 5-1. CDD/CDF Emission Factors for Cement Kilns 5-26
Table 5-2. CDD Concentrations in Japanese Cigarettes, Smoke and Ash 5-29
Table 5-3. CDD/CDF Emissions in Cigarette Smoke . 5.31
Table 5-4. CDD/CDF Concentrations in Cigarette Tobacco. ................'. 5.33
Table 5-5. CDD/CDF Emission Factors for Black Liquor Recovery Boilers '. . . . . '; '. . 5.35
Table 5-6. Concentrations of CDD/CDF in Candle Materials and Emissions ...... 5-37
Table 6-1. CDD/CDF Emission Factors for a Landfill Flare ........ .-;. . . 6-18
Table 6-2. CDD/CDF in Dust Fall and Ashes from Volcanoes ............ . . . ; . 6-20
Table 7-1. CDD/CDF Emission Factors for Secondary Aluminum Smelters '.'.'.'.'.'.'.. 7-21
Table 7-2. CDD/CDF Emission Factors for a Secondary Copper Smelter ......... 7-23
Table 7-3. CDD/CDF Emission Factors for Secondary Lead Smelters ... .....] . [ 7-25
Table 7-4. Operating Parameters for U.S. Iron Ore Sinter Plants ....'. '. . . . 7-27
IX
-------
DRAFT-DO NOT QUOTE OR CITE
LIST OF TABLES (continued)
Table 7-5. CDD/CDF Emission Factors for a Ferrous Foundry 7-28
Table 7-6. CDD/CDF Emission Factors for a Scrap Wire Incinerator 7-30
Table 7-7. Geometric Mean CDD/CDF Concentrations in Fly Ash and Ash/Soil at
Meta| Recovery Sites 7-32
Table 7-8. CDD/CDF Emission Factors for a Drum and Barrel Reclamation Furnace . 7-33
Table 8-1. CDD/CDF Concentrations in Pulp and Paper Mill Bleached Pulp, Wastewater
Sludge, and Effluent (circa 1988} 8-40
Table 8-2. CDD/CDF Concentrations in Pulp and Paper Mill Bleached Pulp, Wastewater
Sludge, and Effluent (circa 1996' , 8-44
Table 8-3. Summary of Bleached Chemical Pulp and Paper Mill Discharges
of 2,3,7,8-TCDD and 2,3,7,8-TCDF ; 8-45
Table 8-4. CDD/CDF Concentrations in Graphite Electrode Sludge from Chlorine
Production 8-46
Table 8-5. CDD/CDF Concentrations in Metal Chlorides 8-47
Table 8-6. CDD/CDF Concentrations in Mono- through Tetra-Chlorophenols 8-48
Table 8-7. Historical CDD/CDF Concentrations in Historical and Current Technical
Pentachlorophenol Products 8-49
Table 8-8. Historical CDD/CDF Concentrations in Pentachlorophenol-Na ;'.'.'. 8-51
Table 8-9. Summary of Specific Dioxin-Containing Wastes That Must Comply with
Land Disposal Retrictions 8-52
Table 8-10. CDD/CDF Concentrations in Chlorobenzenes ...... 8-54
Table 8-11. Concentrations of CDD/CDF Congener Groups in Unused Commercial
PCB Mixtures 8.55
Table 8-12. 2,3,7,8-Substituted Congener Concentrations in Unused PCB Mixtures . 8-56
Table 8-13. Reported CDD/CDF Concentrations in Wastes from PVC Manufacture .. 8-57
Table 8-14. CDD/CDF Measurements in Products and Treated Wastewater from
U.S. PEDC/VCM/PVC Manufacturers 8-58
Table 8-15. CDD/CDF Concentrations in Dioxazine Dyes and Pigments (Canada) . . . 8-59
Table 8-16. CDD/CDF Concentrations in Printing Inks (Germany 8-60
Table 8-17. Chemicals Requiring TSCA Section 4 Testing Under the Dioxin/Furan Rule 8-61
Table 8-18. Congeners and Limits of Quantitation (LOQ) for Which Quantitation is
Required Under the Dioxin/Furan Test Ruleand Pesticide Data Call-l .... 8-62
Table 8-19. Precursor Chemicals Subject to Reporting Requirements Under TSCA
Section 8(a) . . . 8-63
Table 8-20. Results of Analytical Testing for Dioxins and Furans in the Chemicals
Tested To-Date 8-64
Table 8-21. CDDs and CDFs in Chloranil and Carbazole Violet Samples Analyzed
Pursuant to the EPA Dioxin/Furan Test Rule 8-65
Table 8-22. Status of First Pesticide Data-Call-in: Pesticides Suspected of Having t
the Potential to Become Contaminated with Dioxins if Synthesized under
Conditions Favoring Dioxin Formation 8-67
Table 8-23. Status of Second Pesticide Data-Call-in: Pesticides Suspected of Being
Contaminated with Dioxins 8-71
-------
- DRAFT-DO NOT QUOTE OR CITE
r - ' ,
LIST OF TABLES (continued}
Table 8-24. Summary of Results for CDDs and CDFs in Technical 2,4-D and 2,4-D
Ester Herbicides ............................... 8-74
Table 8-25. Summary of Analytical Data Submitted to EPA in Response to Pesticide
Data Call-Ins . ' 8 75
Table 8-26. CDD/CDF Concentrations in Samples of 2,4-D and Pesticide Formulations
Containing 2,4-D . . 8-77
Table 8-27. Mean CDD/CDF Measurements in Effluents from Nine U.S. POTWs . . / 8-78
Table 8-28. CDD/CDF Concentrations Measured in EPA's National Sewage Sludge
... 'Survey . ... . ... 8.79
Table 8-29. CDD/CDF Concentrations Measured in 99 Sludges Collected from ,75 '
U.S. POTWs During 1994 8-80
Table 8-30. Quantity of Sewage Sludge Disposed Annually by Primary, Secondary,
or Advanced Treatment POTWs and Potential Dioxin TEQ Releases ... 8-82
Table 8-31. CDD/CDF Concentrations in Swedish Liquid Soap, Tall Oil, and Tall Resin 8-83
Table 11 -1. Current Dioxin-Like PCB Emission Estimates for the United States
(Reference Year 1995) 1 -j_24
Table 11-2. Current Dioxin-Like PCB Emission Estimates for the United States "''...
(Reference Year 1987) "....• 11-25
Table 11 -3. Weight Percent Concentrations of Dioxin-like PCBs in Aroclors, Clophens,
and Kanechlors .".......-...!........ 'l 1-26
Table 11-4. Disposal Requirements for PCBs and PCB Items,.... 11-28
Table 11-5.( Off site Transfers of PCBs Reported in TRI (1988-1993) . . 11-29
Table 11-6. Releases of PCBs Reported in TRI (1988-1993) '....'.'.'.'.'.'.'. 11-30
Table 11-7. Aroclor Concentrations Measured in EPA's National Sewage Sludge
Survey il-31
Table 11-8. Dioxin-Like PCB Concentrations Measured in 99 Sludges Collected from
75 U.S. POTWs During 1994 11-32
Table 1J-9. Quantity of Sewage Sludge Disposed Annually by Primary, Secondary,
or Advanced Treatment POTWs and Potential Dioxin-Like PCB TEQ
Releases • 11.33
Table 11-10. PCB Congener Group Emission Factors for Industrial Wood Combustors 11-34
Table 11-11. PCB Congener Group Emission Factors for Medical Waste Incinerators
(MWIs) , .v... .... ... n-35
Table 11-12. PCB Congener Group Emission Factors for a Tire Combustor ........ 11-36
Table 11-13. Dioxin-Like PCB Concentrations in Cigarette Tobacco ........ . . . . ; 11-37
Table 11-14. Estimated Tropospheric Half-Lives of Dioxin-Like PCBs with Respect to
Gas-Phase Reaction with the OH Radical . . . . 11-38
XI
-------
DRAFT-DO NOT QUOTE OR CITE
LIST OF FIGURES
Figure 1-1. Chemical Structure of 2,3,7,8-TCDD and Related Compounds , . . 1-4
Figure 2-1. Estimated CDD/CDF TEQ Emissions to Air from Combustion Sources in
the United States (Reference Time Period: 1,995} 2-19
Figure 2-2. Estimated CDD/CDF TEQ Emissions to Air from Combustion Sources in
the United States (Reference Time Period: 1987) 2-20
Figure 2-3. Comparison of Central Tendency Estimates of Annual TEQ Emissions to
Air (grams/year) for Reference Years 1987 and 1995 2-21
Figdre 3-1. Typical Mass Burn Waterwafl Municipal Solid Waste Incinerator 3-45
Figure 3-2. Typical Mass Burn Rotary Kiln Combustor . 3-46
Figure 3-3. Typical Modular Excess:Air Combustor 3-47
Figure 3-4. Typical Modular Starved-Air Combustor with Transfer Rams 3-48
Figure 3-5. Typical Dedicated RDF-Fired Spreader Stoker Boiler .... 3.49
Figure 3-6. Fluidized-Bed RDF Incinerator 3.50
Figure 3-9. Congener and Congener Group Profiles for Air Emissions from a Mass-Burn
Waterwall MSWI, Equipped with a Dry Scrubber and Fabric Filter . . . . ; 3-61
Figure 3-10. Congener Profile for Air Emissions from Hazardous Waste Incinerators . . 3-63
Figure 3-11. Congener and Congerier Group Profiles for Air Emissions fromBoilers
and Industrial Fu 3-64
Figure 3-12. Congener and Congener Group Profiles for Air Emissions ........... 3-73
Figure 3-13. Congener and Congener Group Profiles for Air Emissions from Medical . . 3-74
Figure 3-14. Congener and Congener Group Profiles for Air Emissions from a
Crematorium 3-78
Figure 3-15. Congener and Congener Group Profiles for Air Emissions from Sewage
Sludge Incinerators , ._ 3.30
Figure 3-16. Congener and Congener Group Profiles for Air Emissions from a Tire
Combustor 3_82
Figure 3-17. Congener and Congener Group Profiles for Air Emissions from Bleached
Kraft Mill Combustors 3-84
Figure 4-1. Congener and Congener Group Profiles for Air Emissions from
Diesel-fueled Vehicles 4-36
Figure 4-2. Congener and Congener Group Profiles for Air Emissions from Leaded
Gas-fueled Vehicles 4-37
Figure 4-3. Congener and Congener Group Profiles for Air Emissions from Unleaded
Gas-fueled Vehicles .'. . . . 4-38
Figure 4-4. Tunnel Air Concentrations 4-41
Figure 4-5. Congener and Congener Group Profiles for Air Emissions from Industrial
Wood Combustors 4.45
Figure 4-6. Congener Group Profile for Air Emissions from Residential Oil-fueled
Furnaces 4-43
Figure 4-7. Congener and Congener Group Profiles for Air Emissions from Industrial
Oil-fueled Boilers 4-50
XII
-------
DRAFT-DO NOT QUOTE OR CITE
LIST OF FIGURES (continued)
Figure 4-8. Congener and Congener Group Profiles for Air Emissions from
, Industrial/Utility Coal-fueled Combustors 4-54
Figure 4-9. Congener Group Profile for Air Emissions from Residential Coal-fueled
Combustors .............. . . . 4-56
Figure 5-1. Congener Profile for Air Emissions from Cement Kilns Burning Hazardous
Waste ."....'.........: ....... 5-27
Figure 5-2. Congener and Congener Group Profiles for Air Emissions from Cement
Kilns Not Burning Hazardous Waste ; . . 5.28
Figure 5-3. CDD Profiles for Japanese Cigarettes, Smoke, and Ash 5-30
Figure 5-4. Congener Group Profiles for Mainstream and Sidestream Cigarette
Smoke Jf 5-32
Figure .5-5. Congener Group Profiles for Cigarette Tobacco from Various Countries . 5 34
Figure 5-6. Congener and Congener Group Profiles for Air Emissions from Kraft
Black Liquor Recovery Boilers . 5.35
Figure 6-1. Congener Profile for Landfill Flare Air Emissions . 6-19
Figure 7-1. Congener and Congener Group Profiles for Air Emissions from Secondary
Aluminum Smelters 7-22
Figure 7-2. Congener Group Profile for Air Emissions from a Secondary Copper
Smelter/Refiner 7-24
Figure 7-3. Congener and Congener Group Profiles for Air Emissions from Secondary
Lead Smelters/Refiners ...,;. 7-26
Figure 7-4. Congener and Congener Group Profiles for Air Emissions from a Ferrous
Foundry _, . , 7.29
Figure 7-5,. Congener Group Profile for Air Emissions from a Scrap Wire Incinerator . 7-31
Figure 7-6. Congener Group Profile for Air Emissions from a Drum Incinerator . . , . . 7-34
Figure 8-1. 104-Mill Study Full Congener Analysis Results for Pulp ... . . . 8-41
Figure 8-2. 104-Mill Study Full Congener Analysis Results for Sludge ..... . . . . . 8-42
Figure 8-3. 104-Mill Study Full Congener Analysis Results for Effluent , ........ . 8-43
Figure 8-4. Congener and Congener Group Profiles for Technical PCP 8-66
Figure 8-5. Congener Profile for 2,4-D (salts and esters) .......;........... 8-76
Figure 8-6. Congener Profiles for Sewage Sludge 8-81
XIII
-------
DRAFT-DO NOT QUOTE OR CITE
ACKNOWLEDGEMENTS
The National Center for Environmental Assessment (NCEA) within EPA's Office of
Research and Development was responsible for the preparation of this document. General
support was provided by Versar Inc. under EPA Contract Number 68-D5-0051. Dave
Cleverly of NCEA served as the EPA Work Assignment Manager (as well as contributing
author) providing overall direction and coordination of the production effort as well as
technical assistance and guidance.
XIV
-------
DRAFT-DO NOT QUOTE OR CITE
1. INTRODUCTION
In 1992, the U.S. Environmental Protection Agency's (EPA's) Office of Research and
Development (ORD) began an effort to reassess the exposure and health effects associated
with dioxin. As originally conceived and drafted, the .exposure portion of the Reassessment
did not include an emissions inventory component. ORD was concerned that there was
inadequate test data to construct an inventory and that the time and resources needed to
conduct an extensive testing program was outside the scope of the Reassessment. In
1992, special workshops were held to provide expert review and comment on early drafts
of both the exposure and health components of the Reassessment. Reviewers of these
early drafts strongly urged EPA to attempt an emissions inventory using the available data.
Responding to this suggestion, an inventory was developed and first published in
September 1994 as part of the overall draft Reassessment.
The draft Reassessment underwent reviews by both the public and EPA's Science
Advisory Board (SAB). The SAB supported the general approach used to produce the draft
inventory, but suggested several changes. Most notably, the SAB recommended that the
inventory be specific about the time:frame it represents: The SAB did not suggest that any
of the exposure chapters including the emissions inventory be resubmitted for SAB review.
In addition to SAB comments, EPA received a number of public comments regarding
the emission inventory. In response to all of these comments and the availability of
additional data, a number of changes have been made to the inventory since the 1994
draft. These changes have resulted in significant revisions to both the inventory structure
and actual emission estimates. Consequently, ORD has decided it would be prudent to
conduct an additional round of peer review of the revised inventory before incorporating it
jinto the final Reassessment. The purpose of this document is to provide to the peer
reviewers and interested members of the public, ORD's most recent estimates of dioxin
...-"•. . - . /
emissions for the years 1987 and 1995 along'with a detailed description of the analytical
process and rationale that support these estimates. The peer review of the dioxin emission
inventory will be conducted by an expert panel at a meeting to be held June 3-4, 1998, in
the Washington, D.C. area. EPA will use the comments of the peer review panel to help
guide final revisions to the inventory which will be published as a part of the final
Reassessment. .,'••• u
- .' • 1"1 : , . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
The inventory is supported by an extensive emissions data base. This data base is
available in conjunction with this report on a compact disk (CD). The data base includes all
emission test data and activity level data used to derive the inventory. Because of the
complexity of this data base, ORD elected to have it independently audited for the accuracy
of data inputs and calculations.
1.1. DESCRIPTION OF DIOXIN-LIKE COMPOUNDS
This document addresses compounds in the following chemical classes:
polychlorinated dibenzo-p-dioxins (PCDDs or CDDs), polychlorinated dibenzofurans (PCDFs
or CDFs), polybrominated dibenzodioxins (PBDDs or BDDs), polybrominated dibenzofurans
(PBDFs or BDFs}, and polychlorinated biphenyls (PCBs). The CDDs include 75 individual
compounds, and CDFs include 135 different compounds. These individual compounds are
technically referred to as congeners. Likewise, the BDDs include 75 different congeners,
and the BDFs include an additional 135 congeners. Only 7 of the 75 congeners of CDDs or
of BDDs are thought to have dioxin-like toxicity; these are ones with chlorine/bromine
substitutions in, at least, the 2, 3, 7, and 8 positions. Only 10 of the 135 possible
congeners of CDFs or of BDFs are thought to have dioxin-like toxicity; these also are ones
with substitutions in the 2, 3, 7, and 8 positions. While this suggests 34 individual CDDs,
CDFs, BDDs, or BDFs with dioxin-like toxicity, inclusion of the mixed chloro/bromo
congeners substantially increases the number of possible congeners with dioxin-like
activity. There are 209 PCB congeners. Only 13 of the 209 congeners are thought to
have dioxin-like toxicity; these are PCBs with four or more chlorines with just one or no
substitution in the ortho position. These compounds are sometimes referred to as coplanar,
meaning that they can assume a flat configuration with rings in the same plane. Similarly
configured polybrominated biphenyls are likely to have similar properties; however, the data
base on these compounds, with regard to dioxin-like activity, has been less extensively
evaluated. Mixed chlorinated and brominated congeners also exist, increasing the number
of compounds considered dioxin-like.
The physical/chemical properties of each congener vary according to the degree and
position of chlorine and/or bromine substitution. Very little is known about occurrence and
toxicity of the mixed (chlorinated and brominated) dioxin, furan, and biphenyl congeners.
The chlorinated and brominated dibenzodioxins and dibenzofurans are tricyclic aromatic
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE \
structurally. Certain PCBs (the so-called coplanar or mono-ortho coplanar congeners) are.
also structurally and conformationally similar. The most widely studied of these
compounds is 2,3,7,8-tetrachlorodibenzo-p-dioxm (TCDD).. This compound, often called
simply dioxin, represents the reference compound for this class of compounds. The
structure of 2,3,7,8-TCDD and several related compounds is shown in Figure 1-1.
Figure 1-1. Chemical Structure of 2,3,7,8-TCDD and Related Compounds
Cl
2,3,7,8-Tetrachlorodibenzo-p-dioxin
Cl
2,3,7,8-Tetrachlorodibenzofuran
ci
o .
1,2,3,7,8-Pentachlorodibenzo-p-dioxin
CK
2,3,4,7,8-Pentachlorodibenzofuran
ci
3,3',4,4',5,5'-Hexachlorobiphenyl
3,3',4,4',5-Pentachlorobiphenyl
1.2 TOXICITY EQUIVALENCE FACTORS
The dioxin-like compounds are often found in complex mixtures. For risk
assessment purposes, a toxicity equivalency procedure was developed to describe the
cumulative toxicity of these mixtures., This procedure involves assigning individual toxicity
equivalency factors (TEFs) to the 2,3,7,8 substituted CDD/CDF congeners. These TEF
values have been adopted by international convention (U.S. EPA, 1989). Subsequent to
the development of the TEFs for CDD/CDFs, TEFs were also developed for PCBs {Ahlborg
et al., 1994). TEFs are estimates of the toxicity of dioxin-like compounds relative to'the
toxicity of 2,3,7,8-TCDD, which is assigned a TEF of 1.0. All other congeners have lower
TEF values ranging from 0.5 to 0.00001,. Generally accepted TEF values for CDD/CDFs
and PCBs are shown in Table 1-1 and Table 1j2, respectively.
1-3
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
TEF values ranging from 0.5 to 0.00001. Generally accepted TEF values for CDD/CDFs
and PCBs are shown in Table 1-1 and Table 1-2, respectively.
Calculating the toxic equivalency (TEQ) of a mixture involves multiplying the
concentration of individual congeners by their respective TEF. The sum of the TEQ
concentrations for the individual congeners is the TEQ concentration for the mixture.
It should be recognized that revisions to the TEFs are periodically considered as new
scientific information becomes available. If revisions in the TEFs are adopted, then it would
be appropriate to adjust the TEQ release estimates calculated in the inventory. '
For purposes of this document, certain naming conventions have been adopted. All
quantities representing TEQs are labeled as TEQs. Unless specified otherwise, TEQ values
refer to CDD/CDFs and not other dioxin-like compounds. A complete list of abbreviations
and naming conventions are presented in Table 1-3. The phrase "dioxin-like compounds"
technically would include all the 2,3,7,8 substituted chlorinated and brominated dioxins and
furans, the 2,3,7,8 substituted chlorobromo dioxins and furans, and the coplanar PCBs. In
this document, however, because of the extremely limited data on the bromo and
chlorobromo compounds, this phrase refers only to the 2,3,7,8-substituted CDD/CDFs and
coplanar PCBs.
1 "4 April 1998
-------
DRAFTr-DO NOT QUOTE OR CITE
Table 1-1. Toxicity Equivalency Factors (TEF) for CDDs and CDFs
Compound
TEF
Mono-, Di-, and Tri-CDDs
2,3,7,8-TCDD
Other TCDDs
2,3,7,8-PeCDD
Other PeCDDs
2,3,7,8-HxCDD
Other HxCDDs
2,3,7,8-HpGDD
Other HpCDD
OCDD
0
1
0
0.5
0
0.1
0
0.01
0
0.001
Mono-, Di-, and Tri-CDFs
2,3,7,8-TCDF
Other TCDFs
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF y
Other PeCDFs
2,3,7,8-HxCDF
Other HxCDFs
2,3,7,8-HpCDF
Other HpCDFs
OCDF
0
0.1
0
0.05
0.5
0
0.1
0
0.01
0
0.001
Source: U.S. EPA (1989)
1-5
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 1 -2. Dioxin-Like PCBs
IUPAC No.
77
105
114
, 118
123
126
156
157
167
169
170
180
189
Compound
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',5I-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 -
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
Source: Ahlborg et al. (1994)
1-6
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 1-3. Nomenclature for Dioxin-Like Compounds
Term/Symbol
Congener
Congener
Group .
Isomer
Specific
Isomer
D
F
M
D ,
Tr
T
Pe
Hx
Hp
0
CDD
CDF
PCB
2378
Definition
f • • . • • -
Any one particular member of the same chemical family )e.g., there are 75 congeners of
chlorinated dibenzo-p-dioxins).
Group of structurally related chemicals that have the same degree of chlorination (e.g.,
there are eight congener groups .of CDDs, monochlorinated through octochlorinated).
Substances that belong to the same congener group (e.g., there are 22 isomers that
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)
Symborfor octa (i.e., eight halogen substitution)
Chlorinated dibenzo-p-didxins, halogens substituted in any position
Chlorinated dibenzofurans, halogens substituted in'any position
Polychlorinated biphenyls
Halogen substitutions in the 2,3,7,8 positions
Source: Adapted from U.S. EPA (1989)
1-7
April 1998
-------
-------
DRAFTS-DO NOT QUOTE OR CITE r
2. OVERVIEW OF SOURCES
This report summarizes information on the release of CDD/CDFs and dioxin-like PCBs
to the environment from known and suspected source categories. Where possible, national
estimates have been made of annual releases from source categories in the United States.
This collection of emission estimates is referred to' as the national inventory. The emission
factors and other information used to support development of this inventory are contained
in the comprehensive National Database of Sources of Environmental Releases of Dioxin-
Like Compounds in the United States. This is an electronic database using a spreadsheet
format developed by EPA specifically for this effort. The database addresses both
combustion and non-combustion source categories. For some source categories, emission
factors are developed according tp type of technology and type of pollution control systems.
employed. This electronic database has been published on a compact disk and is available
as a companion to this document.
This overview chapter explains the process used by EPA to derive these emission
estimates and also summarizes general findings and observations. The remainder of the
document discusses CDD/CDF and dioxin-like PCB emissions on a source category basis.
' - ^
2.1. EMISSIONS INVENTORY METHODOLOGY
In the United States, the major identified sources of environmental release have
been grouped into the following classes for the purposes of this report:
Combustion Sources: CDD/CDFs are formed in most combustion systems These can
include waste incineration (such as municipal solid waste, sewage sludge, medical
waste, and hazardous wastes), burning of various fuels (such as coal, wood, and
petroleum products), other high temperature sources (such as cement kilns),'and
poorly controlled combustion sources (such as building fires).
• , Metals Smelting and Refining Sources and Processing Sources: CDD/CDFs can be
formed during various types of primary and secondary metals operations including
iron ore sintering, steel production, and scrap metal recovery.
Chemical Manufacturing: CDD/CDFs can be former! ** hy-prr>H.,V^ frnm the
manufacture of chlorine bleached wood pulp, chlorinated phenols (e.g.,
pentachlorophenol - PCP), PCBs, phenoxy herbicides (e.g., 2,4,5-T), and chlorinated .
aliphatic compounds (e.g., ethylene dichlpride).
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
* Biological and Photochemical Processes: Recent studies have suggested that
CDD/CDFs can be formed under certain environmental conditions (e.g., composting)
from the action of microorganisms on chlorinated phenolic compounds. Similarly,
CDD/CDFs have been reported to be formed during photolysis of highly chlorinated
phenols.
• Reservoir Sources: Reservoirs are materials or places which contain previously
formed CDD/CDFs or dioxin-like PCBs and have the potential for redistribution and
circulation of these compounds into the environment. Potential reservoirs include
soils, sediments, vegetation, and PCP-treated wood. Recently, CDD/CDFs have
been discovered in ball day deposits. Although the origin of the CDD/CDFs in these
clays has not been confirmed, natural occurrence is a possibility.
For sources in each of the above classes (with the exception of Reservoir Sources),
emission estimates have been made in this report for air, land, water and products. Only
releases to the "circulating environment" were included in the inventory. The system
boundaries are further defined as follows:
• CDD/CDFs and dioxin-like PCBs in final products and waste discharges were
included whereas CDD/CDFs and dioxin-like PCBs in intermediate products or waste
streams were excluded. For example, the CDD/CDFs in a waste stream going to an
incinerator would not be included in the inventory but any CDD/CDFs in the stack
emissions would be included.
CDD/CDFs and dioxin-like PCBs in waste streams applied to land in the form of "land
farming" are included whereas those disposed in permitted landfills were excluded.
Properly designed and operated landfills are considered to achieve long term isolation
from the circulating environment. Land farming, however, involves the application
of wastes directly to land, clearly allowing for releases to the circulating
environment.
Commercial products which contain CDD/CDFs or dioxin-like PCBs and whose
subsequent use may result in releases to the environment were included in the
inventory. Examples include paper pulp, sewage sludge that is distributed/marketed
commercially, and certain pesticides.
The EPA's Science Advisory Board (SAB) reviewed an earlier draft of the national
r*
dioxin source emissions inventory and commented that the effort was comprehensive and
inclusive of most known sources (U.S. EPA, 1995f). However, the SAB emphasized that
source emissions are time-dependant, and recommended that emissions be associated with
a specific time reference. In consideration of these comments, EPA has developed in this
report emission estimates for two years: 1987 and 1995.
2-2
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
1987 was selected primarily because, prior to this time, little empirical data existed
for making source specific emission estimates. The first study providing the type of data
needed for a national inventory was EPA's National Dioxin Study (U.S. EPA, 1987a). The
year 1987 also corresponds roughly with the time that significant advances occurred in
emissions measurement techniques and in the development of high resolution mass
spectrometry and gas chromatography necessary for analytical laboratories to achieve low
level detection of CDD and CDF congeners in environmental samples. Soon after this time,
a number of facilities began upgrades specifically intended to reduce CDD/CDF emissions.
Consequently, 19871s also the latest time representative of the emissions occurring before
widespread installation of dioxin-specific emission controls.
1995 was selected as the latest time period that could practically be. addressed
consistent with the time table for producing the rest of the document. The data collected
in the companion document to this document on CDD/CDF and dioxin-like PCB levels in
environmental media and food were used to characterize conditions in the mid-1990's. So
the>missiqns data and media/food data in these two volumes are presented on a roughly
consistent basis.
A key element of the inventory is the method of extrapolation from tested facilities
to national estimates. Because only a few U.S. facilities in most source categories have
been tested for CDD/CDF emissions, an extrapolation was needed to estimate national
emissions for most source categories. Many of the national emission estimates were,
therefore, developed using a "top down" approach. The first step in this approach is to
derive from the available emission monitoring data an emission factor (or series of emission
factors) deemed to be representative of the source category (or segments of a source
category that differ in configuration, fuel type, air pollution control equipment, etc.) The
emission factor relates mass of CDD/CDFs or dioxin-like PCBs released into the environment
per some measure of activity (e.g., kilograms of material processed per year, vehicle miles
traveled per year, etc.). The emission factor was then multiplied by a national value for the
activity level basis of the emission factor (e.g., total kg of material processed in the United
States annually).
Although no categories had estimates developed from a true "bottom up" approach
(i.e., estimates developed using site-specific emissions and activity data for all individual
sources in a category and then summed to obtain a national total), existing facility-specific;
2-3 April Ig98
-------
DRAFT-DO NOT QUOTE OR CITE
emissions testing and activity level data for some source categories (e.g., municipal solid
waste incinerators) supported a semi- "bottom up" approach. In this approach, facility-
specific annual emissions were calculated for those facilities with adequate data. For the
untested facilities in the class, a subcategory (or class) emission factor was developed by
averaging the emission factors for the tested facilities in the class. This average emission
factor was then multiplied by the measure of activity for the non-tested facilities in the
class. Emissions were summed for the tested facilities and non-tested facilities. In
summary, this procedure can be represented by the following equations:
'-total = Z^i ^tested,! + 2-t ^untested,!
E total = 2~r ^tested,! + ^ \^'i * ^untested
Where: Etota, = annual emissions from all facilities (g TEQ/yr)
^tested,! = annual emissions from all tested facilities in class i (g TEQ/yr)
^untested,! = annual emissions from all untested facilities class i (g TEQ/yr)
Efj = mean emission factor for tested facilities in class i (g TEQ/kg)
AJ = activity measure for untested facilities class i (kg/yr)
Some source categories are made up of facilities that vary widely in terms of design
and operating conditions. For these sources, as explained above, an attempt was made to
create subcategories which grouped facilities with common features and then to develop
separate emission factors for each subcategory. Implicit in this procedure is the
assumption that facilities with similar design and operating conditions should have similar
CDD/CDF release potential. For most source categories, however, the specific combination
of features that contributes most to CDD/CDF or dioxin-like PCB release is not well
understood. Therefore, how to best subcategorize a source category was often
problematic. For each subcategorized source category in this report, a discussion is
presented about the variability in design and operating conditions, what is known about
how these features contribute to CDD/CDF or dioxin-like PCB release, and the rationale for
subcategorizing the category.
As discussed above, each source emission calculation required estimates of an
"emission factor" and the "activity level." For each emission source, the quantity and
2-4
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
quality of the available information for both terms varies considerably. Consequently, it is
important that emission estimates be accompanied by some indicator of the uncertainties
associated with their development. For this reason, a confidence rating scheme was
1 • I ,-
developed as an integral part .of the emission estimate in consideration of the following
factors:
• Emission Factor - The uncertainty in the emission factor estimate depends
primarily on how well the tested facilities represent the untested facilities. In
general, confidence in the emission factor increases with increases in the
number of tested facilities relative to the total number of facilities. Variability
in terms of physical design and operating conditions within a class or
subclass must also be considered. The more variability among facilities, the
less confidence that a test of any single facility is representative of that class
or subclass. The quality of the supporting documentation also affects
uncertainty; Whenever possible, original engineering test reports were used.
Peer reviewed reports from the open literature were also used for developing
some emission factors. In some cases, however, draft reports that had
undergone more limited review were used. In a few cases, unpublished
references were used (such as personal communication with experts) and are
clearly noted in the text.
• Activity Level - The uncertainty in the activity level estimate was judged
primarily on the basis of the extent of the underlying data. Estimates derived
from comprehensive surveys (including most facilities in a source category)
were assigned high confidence. As the number of facilities in the survey
relative to the total decreased, confidence also decreased. The "quality of the
supporting documentation also affects uncertainty. Peer reviewed reports
from the open literature (including government and trade association survey
data) were considered most reliable. In some cases, however, draft reports
that had undergone more limited review were used. In a few cases,
unpublished references were used (such as personal communication with
experts) and are clearly noted in the text.
The confidence rating scheme, presented in Table 2-1, provides criteria for assigning
a,"high," "medium," or "low" confidence rating for both the emission factor and activity
terms. The first rating applies to the "activity" term, and the second rating applies to the
"emission factor" term. In addition to the confidence rating,.the uncertainty in these
national release estimates is reflected by presenting, where possible, for each source
category, both a central or "best guess" value and a possible range from a lower to upper
estimate. These lower and upper estimates are riot intended to be absolute bounds, but
reasonable estimates of how much higher or lower the true value might be. Insufficient
2-5 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
data were available to statistically derive these ranges; therefore, a judgement-based
approach was developed. This approach uses the average or best guess estimate as the
central value of a range. The range was determined by treating the central value as a
geometric average of the end points of the range and determining those endpoints as
follows: ,
* Low confidence class: Upper end of range is 10 times higher than lower end.
* Medium confidence class: Upper end of range is 5 times higher than lower
end.
* High confidence class: Upper end of range is 2 times higher than lower end.
The overall confidence rating assigned to an emission estimate was the lower of the
confidence ratings assigned to the corresponding "activity" term and "emission factor"
term. It is emphasized that these ranges should be interpreted as judgements which are
symbolic of the relative uncertainty among sources, not statistical measures.
In some cases, sufficient information was available to make very preliminary
estimates of emissions of CDD/CDFs or dioxin-like PCBs, but the confidence in the activity
level estimates or emission factor estimates was so low that it was considered
inappropriate to include emission estimates in the inventory. These preliminary estimates
are discussed in the text and summarized in Table 2-6.
The emission factors developed for the emissions inventory are intended to be used
for estimating the total emissions for a source category rather than for individual facilities.
EPA has made uncertainty determinations for each of these emission factors based, in part,
on the assumption that by applying them to a group of facilities, the potential for
overestimating or underestimating individual facilities will to some extent be self
compensating. This means that in using these emission factors one can place significantly
greater confidence in an emission estimate for a class than can be placed on an emission
estimate of any individual facility. Given the limited amount of data available for deriving
emission factors, and the limitations of our understanding about facility-specific conditions
that determine formation and control of dioxin-like compounds, the current state of
knowledge cannot support the development of emission factors that can be used to
accurately estimate emissions on an individual facility-specific basis.
, 2"6- April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
2.2. GENERAL FINDINGS OF THE EMISSIONS INVENTORY
Nationwide emission estimates for the United States inventory are presented in
Tables 2-2 and 2-3 (emissions to air, water, land, and product) for the major known or
suspeced sources that could have releases of dioxin-like compounds to the environment.
The emission factors used to calculate these emission estimates were derived by setting
"not detected (ND)" values in test reports as zeros. Because detection limits were not
always reported in test reports, it was not possible to consistently develop emission factors
on, any other basis (e.g., values set at one-half the detection limit) for all source categories.
When detection limits were reported for all test reports for a given source category,
emission factors Were calculated and are presented in this report for both ND equals zero
and ND equals one-half the detection limit.
Table 2-2 presents estimated annual releases for the reference time period 1995.
Table 2-3 presents estimated annual releases for the reference time period 1987. Table 2-
4 lists the emission factors used to derive these emission estimates. For each source listed
in these tables, estimated emissions are presented where appropriate and where data are
adequate to .enable an estimate to be made. Figures 2-1 and 2-2 are charts that visually
display the range of emission estimates to air that are reported in Tables 2-2 and 2-3,
respectively. Figure 2-3 compares the ahnualmean TEQ emission estimates for the two
reference years. Table 2-5 presents order of magnitude estimates of CDD/CDF emissions
from suspected source categories not included in the inventory because uncertainty in the
emission factor and/or activity level was deemed too great.
Central estimates of re/eases of dioxin-like compounds to all environmental media
(except products) were approximately 3,OOO g. TEQ in 1995 and 11,900 g TEQ in 1987.
These estimates were generated by summing the emissions across all sources in the
inventory. Each of these estimates have an uncertainty range around them which is
derived from uncertainties in the estimates for individual sources (for 1987 the range is
5,000 to 29,100 g TEQ and for 1995 the range is 1,200 to 7,900 g TEQ).
The decrease in estimated emissions of dioxin-like compounds between 1987 and
1995 was due primarily to reductions in emissions from municipal and medical waste
incinerators. For both categories these emission reductions have occurred from a
combination of improved combustion and emission controls and from the closing of a
2"7 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
number of facilities. Regulations recently promulgated or under development should result
in some additional reduction in emissions from major combustion sources.
The environmental releases of dioxin-like compounds in the United States occur from
a wide variety of sources, but are dominated by releases to the air from combustion
sources. The current (i.e., 1995) inventory estimates that emissions from combustion
sources are more than an order of magnitude greater than emissions from all other
categories combined.
Insufficient data are available to comprehensively estimate point source releases of
dioxin-like compounds to water. Sound estimates of releases to water are only available
for chlorine bleached pulp and paper mills (356 g TEQ/yr for 1987 and 20 g TEQ/yr for
1995). Other releases to water bodies which cannot be quantified on the basis of existing
data include effluents from POTWs and most industrial/commercial sources.
Insufficient data are available to comprehensively estimate releases of dioxin-like
compounds to land. Contributions to land can occur in a variety of ways. One way is the
intentional disposal of materials containing dioxin-like compounds in properly managed
landfills where the potential for releases to the environment (i.e., groundwater or the
atmosphere) is assumed to be minimal. Sound estimates of such practices have only been
made for the disposal of municipal waste incinerator ash (1,800 g TEQ in 1995), sewage
sludge (194 g TEQ in 1995), and pulp and paper mill wastewater sludge (21 g TEQ in
1995). Other materials containing dioxin-like compounds which are typically landfilled
include dredge spoils and incinerator ash other than municipal waste incinerator ash. A
second way is land application of sewage sludge (207 g TEQ/yr in 1995) and pulp and
paper mill wastewater sludges (1.4 g TEQ/yr in 1995). In the past, a third way was the
improper land disposal of chemicals and waste products containing dioxin-like compounds.
The change over time in amounts of dioxin-like compounds being land disposed has
not been well characterized. Some of the emission controls installed in recent years have
reduced dioxin formation and others have removed more CDD/CDFs from air and water
emissions and transferred them to solid residues. It is unclear if the net effect of these
types of controls would lead to an increase or decrease in amount of CDD/CDFs in solid
residues.
• I
Data are available to estimate the amounts of CDD/CDFs and dioxin-like PCBs
contained in only a limited number of commercial products. No systematic survey has been
2-8
.April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
conducted to determine.levels of dipxin-like compounds in commercial products. The
available data does, however, allow estimates of the amounts of dioxin-like compounds in
bleached pulp (24 g TEQ/yr in 1995), POTW sludge used in fertilizers (7.0 g TEQ/yr in
1995), pentachlorophenol-treated wood (25,000 g TEQ/yr irr 1995), dioxazine dyes and
pigments «1 g TEQ/yr in 1995) and 2,4-D (18.4 g TEQ/yr in 1995).
The mixture of ODD and CDF congeners in the emission from a source category (i.e.,
the "congener profile ") may serve as a source-specific signature for that category:
Although uncertainties exist, these congener profiles may assist researchers in:
(1) identification of specific combustion source contributions to near field air measurements
of CDD/CDFs; (2) comparing sources in terms of discerning differences in the types and
amplitude of CDD/CDF congeners emitted; and (3) providing insights on formation of CDDs
and CDFs in various sources and chemicals.
The procedures and results of the U.S. inventory are consistent with the published
national inventories for several European countries. Table 2-6 presents CDD/CDF TEQ
/" • ' '
source-specific air emission estimates reported for West Germany (Fiedler and Hutzinger,
1992); Austria (Riss and Aichinger, 1993); The Netherlands (Koning et al., 1993; Bremmer
et al., 1994); Switzerland (Scnatowitz et al., 1993); Belgium (Wevers and DeFre, 1995);
and the United Kingdom (Douben et al., 1995; UK Department of the Environment, 1995).
The emission estimates for West Germany, Switzerland, the United Kingdom, and The
Netherlands suggest that municipal waste incinerators and metal smelters/refiners are the
largest sources of air emissions. In Austria, domestic combustion of wood is believed to be
the largest source followed by emissions from the metallurgical industry. Although an
emissions inventory for Sweden has not yet been published, Rappe (1992a) and Lexen et
al. (1993) have identified emissions from ferrous and nonferrous metals smelting/refining
facilities as potentially the largest current source in Sweden. It should be noted that these
emission inventories are expected to change over time due to changing industrial practices,
facility closures and .upgrades, and regulatory actions.
Some investigators have argued that national inventories such as this one may be
underestimating emissions due to the possibility of unknown sources. This claim has been
supported with mass balance analyses suggesting that deposition exceeds emissions
(Rappe et al., 1991; Harrad et al. 1992b; Brzuzy and Hites, 1995). The uncertainty,
however, in both emissions and deposition estimates in the United States prevent the use
2-9
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
of this approach for reliably evaluating this issue. A variety of other factors do indicate,
however, that the inventory could underestimate CDD/CDF emissions:
• A number of sources were not included in the inventory even though limited
evidence exists (primarily from studies performed in Europe) indicating that these
sources can emit CDD/CDFs. These sources include various components of the
metals industries such as iron ore sintering and foundries. Table 2-6 presents rough
estimates of what U.S. national emissions could be if the emission factors reported
in these other studies are representative of emission factors for U.S. facilities.
• The possibility remains that truly unknown sources exist. Many of the sources
which are well accepted today were only discovered in the past 10 years. For
example, CDD/CDFs were found unexpectedly in the wastewater effluent from
bleached pulp and paper mills in the mid 1980s. Ore sintering is now listed as one
of the leading sources of CDD/CDF emissions in Germany, but was first reported in
the early 1990s.
• Another potentially important source which is not represented in'the inventory is ,
reservoirs. In this context, reservoirs are places such as soils, sediments, vegetation
or other media which contain dioxin-like compounds originally formed some time in
the past and have the potential for current emissions. The dioxin-like compounds in
these "reservoirs" can be re-released to the environment by processes such as
volatilization and particle resuspension. Such releases may (or may not) add
significantly to the mass of dioxin-like compounds circulating in the environment and
potentially contributing to human exposure. Two of the largest potential reservoirs
are soils and pentachlorophehol (PCP) treated wood. PCP contains low levels of
CDD/CDFs and wood which has been treated with this pesticide represents a large
reservoir of CDD/CDFs. CDD/CDFs may be released from the PCP-treated wood to
the air by volatilization or to surrounding soils by leaching. Although hypothesized
to occur, no reliable measurements have been made. Similarly, no empirical evidence
exists on the possible magnitude of reservoir emissions from soil to air.
2.3. GENERAL SOURCE OBSERVATIONS
Current emissions of CDD/CDFs to the U.S. environment result principally from
anthropogenic activities. Three lines of evidence support this finding:
• Studies of sediment corings in lakes in the United States show a consistent pattern
of change in CDD/CDF concentration in the sediments over time. The time period
when increases are observed in CDD/CDF levels in sediments coincides with the
time period when general industrial activity began increasing rapidly. CDD/CDF
concentrations in sediments began to increase around the 1930s, and continued to
, increase until the 1960s and 1970s. Decreases appear to have occurred only during
the most recent time periods (i.e., 1970s and 1980s). These trend observations are
consistent among the dated sediment cores collected from over 20 freshwater and
marine water bodies in various locations throughout the United States and Europe.
2-10 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Levels of CDD/CDF in sediments from these lakes are considered to be a reasonable
indicator of the rate of environmental deposition. The period of increase generally
matches the time when a variety of industrial activities began rising and the period
of decline appears to correspond with growth in pollution abatement. Some of
these abatements may be linked with dioxih emissions (i.e., elimination of open
burning, paniculate controls on combustors, phase out of leaded gasoline, and bans
or restrictions on PCBs, 2,4,5-T, and PCP.
No large natural sources of CDD/CDF have been identified. EPA's current estimate
of emissions from all sources of CDD/CDFs suggests that forest fires are a minor
source of emissions compared to anthropogenic combustion activity. To date, no
studies have demonstrated formation of CDD/CDFs by volcanoes. Recently
CDD/CDFs have been discovered in ball clay deposits in western MS, KY and TN.
Although the origin of the dioxins in these clays may be natural, it has not been
confirmed. .
1 >- . ** , *
CDD/CDF levels in human tissues from the general population in industrialized
countries are higher than levels observed in less-industrialized countries. Human
populations in Europe and North America have significantly higher mean tissue levels
(e.g., blood, adipose tissues and breast milk) than human populations in developing
countries of Asia and South East Asia {Schecter, 1994). In addition, tissues taken
from preserved, 140 to 400 year old human remains show almost the complete
absence of CDD/CDFs, well below levels found in tissues of modern people (Tonq et
al., 1990).
No clear evidence exists showing that the emissions of CDD/CDFs from known
sources correlate proportionally with general population exposures. Although the emissions
inventory shows the relative contribution of various sources to total emissions, it cannot be
assumed that these sources make the same relative contributions to human exposure. It is
quite possible that the major sources of CDD/CDF in food may not be those sources .that
represent the largest fractions of total emissions in the United States. The geographic
locations of sources relative to the areas from which much of the beef, pork, milk, and fish
is produced are important to consider. That is, the agricultural areas which produce much
of our food may not necessarily be located near or down wind of the major sources of
CDD/CDFs.
2"1.1 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 2-1. Confidence Rating Scheme for U.S. Emission Estimates
Confidence
Rating
Activity Level Estimate
Emission Factor Estimate
High
Derived from comprehensive
survey
Derived from comprehensive survey
Medium
Based on estimates of average
plant activity level and number of
plants or limited survey
Derived from testing at a limited but
reasonable number of few facilities
belieyed to be representative.of
source category
Low
Based on expert judgement or
unpublished estimates
Derived from testing at only a few,
possibly non-representative facilities
or from similar source categories or
foreign surveys where differences
in industry practices may be likely
2-12
April 1998
-------
-------
TJ
Q>
"•P
O
IO
O)
O)
0)
0)
(D
CC
W S
f-H -t-
P"-I (v
U co
p^ ~o
f\
§
5
1
o
1
i
)
<
2
<
<
<
Z
ssj
X
u
o
5
d
10
o
|| Cigarette combustion
<
*
<
z
<
z
<
<
z
u
z
o
Ul
z
o
z
Carbon reactivation furnaces
<
•
*
*
*
«^
X
o
in
CO
CN
o
*~
Kraft recovery boilers
^
<
2
2
<
<
<
<
2
*
*
*
*
1 Minimally Controlled or Uncontrolled
Combustion
Combustion of landfill gas in flares
<
«
z
<
<
<
Z
*
*
*
*
CO
01
£
T3
s
<
<
*
*
*
*
*
Accidental fires (structural)
<
<
<
*
*
*
*
*
i*
«
II Accidental fires (vehicles)
^
<
<
<
<
z
<
z
— '
§
CD
§
ev
to
(D
•o
v>
0)
(0
s
1
CD
1
«
0)
I
<
. ,
<
<
<
<
^
<
z
*
*
*
*
II Backyard trash burning
<
,
<
*
*
*
*
*
Uncontrolled combustion of PCBs
« Metallurgical Processes
Ferrous metaf smelting/refining
<
«
<
*
*
*
*
*
*
*
*
1 - Sintering plants
z
^
<
II - Secondary aluminum smelting j
z
<
<
^
•
*
*
r
o
r*>
^?
in
f*
- Secondary copper smelting \
z
^
<
<
*
#
*
*
*
'5
5
in
to
pi
CO
(O
o
o
I
"5
«
•D
(0
_Q)
ro
•D
§
O)
OL
<
-------
fc
O
O
.w
S
t3
CD
C
o
in
0)
CT>
(D
CD
CD
O
CD
CD
CC
09
CD
CO
T3
CD
o>
CX -
I I
.0
Q
CD
H
PH
c
o
< 'to
•K .2
E
LU
T3
O
Q.
O
O
CD
C
'x
o
b
CN
I
CN
_CD
£}
<•
: T
! ^
> c
• •-
5
. i
o
CM
*
q
i
CD
CM
10
• O)
CO
CO
*
*
*
*
03
1 Chemical Manuf./Processing Sources
Bleached chemical wood pulp and pap
mills'
>. c
3 2
S 2
c:
u
• 2
CD
UJ
. Z
CD
LU
" Z
CD
ill
Z
1
CD
UJ
CD
Z
CD
u.
i
CD
UJ
Z
••
C3
UJ
1
Mono- to tetrachloropfienols
=
1 J
'- u
c»
) C
c
ir
CN
J
!
CD
Ul
Z
CD
UJ
CD
Ul
Z
1
CD
Z
CD
•a
i
'O
UJ
Z
O
UJ
0
UJ
, "5
c
(U
JZ
Q
0
_O
U
CD
•
>
> c
f u
> i
' <'
t 1
' 2
c:
u.
-2
i
CD
u.
CD
Ul
Z
CD
UJ
•'
CD
UJ
CD
Ul
Z
CD
UJ
,
O
UJ
Z
CD
UJ
CD
UJ
Z
Chlorobenzenes
<
2
J <
^
Z
i
;
CD
UJ
Z
O
u.
Z
CD
UJ
z
1
CO
UJ
$
,
CD
til
CD
UJ
CD
u.
Chlorobiphenyls (leaks/spills)
\ f
*
*
;
a
O
u.
UJ
*
* "
- *
*
*
*
*
Ethylene dichloride/vinyl chloride
V
•
_T-
T"
CC
-tr
c
T-
c
!
CD
111
2
O
UJ
Z
CD
ill
Z
i
CD
UJ
Z
CD
UJ
2
CD
Ul
Z
,
'
CD
= 'ill
CD
UJ
CD
UJ
2
Dioxazine dyes and pigments
I I
c
• ?
"^
a
. r-
C
f
»-
i
CD
u.
CD
u.
CD
UJ
!
CD
* U]
CD
UJ
CD
UJ
2
,
' '
CD
Ul
Z
CD
Ul
Z
CD
•111
2,4-Dichlorophenoxy acetic acid
E a
: 3
> u
^ T-
r-
P.
c
,<*
I
in
CO
S
CM
0
CM
Z
2
z
z
^
z
2
2
Z
Non-incinerated municipal sludge
> .
*
•
*
CD
u
2
CD
-UJ
CD
UJ
' .!
CD
. u
CD
•111
2
CD
Ul
2
(
'
S
CD
HI
Z
CD
--- UJ
§
<0
03
CO
CO
XI
• _L
*o
H
. <
<
2
<
2
2
*•
.,
*
*
*
*
*
'•
^
2
2
2
§
Biological Formation
c <
! Z
<
' "2.
<
2
*
*
*
*
*
*
*
*
*
«
*
Photochemical Formation
: <
c <
: z
2
z
*
*
*
*
*
*
*
*
*
1 * .
•
• Reservoir Sources
Emissions from chlorophenol-treated w
ni •• '" *
••*
p-
^
IT
r-
o
o
in
CM
CO
PS
1-
co
00
o
CM
CM
CO
CM
•8
S
i
in
r-.
cs?
CD
CM
o
TOTAL0
1
CO
£
£- «
CO C
-§ 8 .
w ' C
O 0)
• s- -o
^ , . C
Tj- . Q) O
i ' s o'
-§ S ' § S J_: '
" to a ra w in
- ^ 1 S'E1^
T- Q) O m
«<• 3 o .1 § ' fi
C
_ .5 O 03 V 03
o ' -D " £ £ £
~ v os t: •& -°
O .*^ XI Q C 0)
03 ^ .~ i^« to ^
a> £ E g nia
& c " 1 i>g
03 o >-.E;;:
' = =03 n) 03 -^
' .0 to o *o !=
0 ' (D 'c C E S
| I i s fe *
*- ' •"- ' "S • "c *" S
C 03 2 O W C
o "> S o S w
» = E 03 .2 o
c »° to r— > £;
i 'II gif
•g S «„• g 2 .9 |-
C *• 0 (D T3 w S
f -a 1 2 III
ra "§ C 1 ^ "o ~ '
f 1 1 11 2*
™ ~ fe _ c m c
- - S £ S 1- .E o "
03 '5 ,= > g D,
.£ 03 « := 5 >• C
T3 "" C C ° <° 'Q
§ c g g . E c
03 o> fe T3 ra .«
S E E o § u.- 8 ' g
>. "» ^ ^ ' g " y S g
1 III |s8s s
-" S^S §="03 -r
o - 2 S E ^°S- S
-!• filill!|-.|
c , OT *g . aj Q o ^ o
ro SE£-o.2?pro;§
(U •— ,^ *-" U i. *Jj (/J _C~
CR = Confidence rating. First letter is
H = High Confidence,
M = Medium Confidence,
L = Low Confidence.
Leaded fuel production in the United S
TOTAL reflects only the total of the es
It is not known what fraction, if any, o
Included within total for Wood Combus
Includes releases of dioxin-like PCBs -ar
Some evidence exists suggesting that
* Evidence exists suggesting that this ca
estimates and/or activity level estimate
A = Not applicable.
EG = Expected to be negligible (i.e., less t
co
o>
o>
Q.
•<
'to
I
CN
-------
00
O)
ra
0)
o
c
CO
£
DC
I/)
CD
4-»
to
£
c
r>
CD
o *-
s I
o
LU
•a
I
jn:
'3
CN
CD
II II
. <
< <
Z Z
CO
g 2
CO
I
n
1
,_ in
co O
d
Waste Incineration
Municipal waste incin
ard
tion
tion
Power/Energy Gen
Vehicle fuel com
<
<
CO
en
-
a.
o
CO
CN
So
g pl
-------
u
•p
0)
o
oo
O)
CD
CD
0}
O
_C
o>
cc
tn
£
03
+-*
O
w
•H
O «t>
D £
c
13
S
8
>«
|-
CJ
03
1
0>
D
3
O
n
i
S
J
2
<
.
<
z
<
<
z
<
z
:_,
X
CO
o
m
0
1 Cigarette combustion
z
<
«
<
^
<
'Z
<
<
^
<
<
z
<
<
UJ
Z
C3
Z
C5
UJ
Carbon reactivation furnaces
<
^
<
*
*
*
' *
5
X
to
•*
o
CM
cn
d
| Kraft recovery boilers
2
<
^
<
^
^
< *
*
*
*
* '
*
1 Minimally Controlled or Uncontrolled
Combustion
Combustion of landfill gas in flares
2
<
2
<
<
'Z
<
<
z
<
z
*
*
*
*
Landfill fires
2
<
^
<
- •
*
*
* '
*
* '
*
| Accidental fires (structural)
2
<
2
<
«
*
*
*
*
*
*
*
II Accidental fires (vehicles)
2
. <
2
- <
<
z
<
z
<
z
<
z
— J
CO
CO
lO
CO
CO
in
1
1
£
CO
•o
§
.a
In"
o
O
U-
;
<
z
<
.<
-Z
<
Z
' <
z
<
z
*
*
»
' *
1 Backyard trash burning
|
<
z
<;
*
*
* '
*
*
*
II Uncontrolled combustion of PCBs
' •-
» Metallurgical Processes
Ferrous metal smelting/refining
J
<
2
^
*
*
*
*
»
*
*
*
*
*
II - Sintering plants
i
<
2
^
*
*
*
*
*
*
• *
*
•*
t *
I uojjonpoad a)|oo - II
2
<£
Z
<
*..
' *
* '
*
*
*
*
*
*
* '
II - Electric arc furnaces
;
O)
o
CO
II - Secondary aluminum smelting I
<
<
z
<
*
*
, *
*
»
*
*
*
i
o
o>
Q.
<
CN
-------
1
o
,0
FT
oo
o>
to
CD
CD
O
O
I
ro
w
•o
5
CD
JC
CD
O
8
1
1
Q.
O
O
o
X
o
CO
IN
^J
XI
£
S .
o
*?
Ul
\r~
H
&
\
i
"Q
B
«
,
C
"
'
3
M
0
t
"
C
1
a:
U
s
."
•5
1
u
is
-1
5:
U
s
3
I
1
3
&
u
S
3
*2
O
fe
I
S
1
Q
9
3
c 3
) 3
i ?
! !
IT
)
S
n
X
0
IN
^f
O
|
s
in
CO
tn
CO
CM
in
CM
*
*
1 Chemical Manuf./Processlng Sources
Bleached chemical wood pulp and paper
mills
t
o
o
i
ID
ill
CD
z
CD
u
CD
u
Z
!
CD
z
a
z
o
UJ
z
1-
Mono- to tetrachlorophenols
CD
CD
1
a
o
z
CD
L
U
U
1
CD
Z
CD
Z
u.
z
Pentachlorophenol
o
tD
i
CD
«
z
a
CD
u
Z
i
CD
Z
CD
Z
cs
UJ
Z
|| Chlorobenzenes
z
CD
CD
1
CD
CD
z
1
CD
U
!
CD
Z
CD
Z
O
U.
Chlorobiphenyls (leaks/spills)
CD
CD
1
O
Ul
*
•
*
*
*
Ethylene dichloride/vinyl chloride
°
CD
CD
L
CD
z
S
CD
u
:
CD
Z
CD
Z
CD
UJ
Z
w
C:
o
ra
'5.
•o
c
(O
VI
to
•a
co
c
•H
CO
X
o
b
"
CD
CD
I
CD
z
CD
u
CD
u
1
CD
Z
CD
Z
CD
u.
2,4-Dichlorophenoxy acetic acid
•*
=
in
i-.
o
o
CM
2
z
<
Z
<
Z
<
z
<
z
<
z
<
|| Non-incinerated sludge
«
*
CD
CD
L
2
z
CD
li
"Z.
CD
Ul
Z
!
O
CD
Z
CD
UJ
Z
| Tall oil-based liquid soaps
2
z
•
9
*
*
*
*
<
Z
<
z
<
II Biological Formation i
z
z
*
*
*
*
*
*
*
*
Photochemical Formation
<
2
="
*
*
*
*
*
*
*
*
*
II Reservoir Sources
[I Emissions from chlorophenol-treated wood
||
r~
in
en
10
r-
CD
in
CO
m
•*
0)
in
CM
to
CN
O
P>
*""
•*
O
in
CO
in
m
CN
in
CN
o
CM
CO
CN
•*
r-
CO
CO
<*
1 TOTAL0 |
i rating assigned to "emission factor." (See Section 2.1 and Table 2-1 for details):
S
a
•o
o
8
CO
fr
ictivity level" est
to
o
T3
0}
C
.2*
*«
O)
re
CR = Confidence rating. First letter is
H = High Confidence,
g leaded fuel for highway use have been prohibited in the United States. (See Section 4.1 for detail
c
'5
cr
V
tn
.c
c
0)
£
Ic
servoir'* source. The estimated emissions may be solely the result of combustion.
re
tn
i
vt
o
Q.
£
tn
to
cture of motor vt
report.
iions from forest
M = Medium Confidence,
L = Low Confidence.
ll
i-e
•^ ra
ra a?
« ro
ra ™
Leaded fuel production in the United St
TOTAL reflects only the total of the est
tn
'E
0)
Q)
ra
to
01
.c
It is not known what fraction, if any, ol
re
•c
1
c
_g
Included within total for Wood Combus
B estimates are H/M. The confidence ratings for the CDD/CDF estimates are H/H.
insufficient data are available for making a quantitative or qualitative emission estimate.
nates of emissions for reference year 1995 have been made (see Table 2-5), but the confidence in
in the inventory.
o
o.
c
'x
_o
T3
1
O
Dnfidence ratings
u
CD
^
i-
u_
0
y
Q
O
•o
Includes releases of dioxin-like PCBs an
1
1
c
0
i
rce of CDD/CDF
o
tn
ra
w
en
V
ro
u
tn
Ic
Some evidence exists suggesting that tl
(t_
1
CD
C
E
1
a.
c
o
CDD/CDF emissi
'o
03
U
D
0
tn
ra
tn
•>,
o
0)
03
Evidence exists suggesting that this cai
Q.
<
00
CN
< LLJ
-------
o
-H
•-P
,W
in
§"§
5-1 O
4-1 -H
0)
-o S
00
M (U
-H 0)
c3 ILJ
05!
a~
w
U
4J
-H
cs
CD
«.s
•H
fa
CO. I
c,| -1-L
>_• t/\ . i 4 ^ .* h.
"E 2
o .§
l--oH
•.§ §3
iS
O)
Q.
<
3 CD
I
is?
O5
T—
CN
Ililfll
. 1.0-0
-) lOOX
LOOO'O
LOOOO-O
ti
Ii
.i
ii-
•- « s -c •»
«^? o °
•^ c Q- en
C 0) 35 fP CO
o> o to »- -m
o o c o> co ^i
>-o 1-i >1"
• c ' £
g <» 1 I ~
•8 g S1 .g
f£§Si
•^ v-ii CD -a
H §•-J £ 1
«S cJ5'8
9> I— O T3 »-
= D> » S °
.D)^ .2 C
-------
R
O
•H
4J
CO
S °° -K-
82 §
^ §1
^ 0 F-oF
•H ft §§S
Q
O
-d
ro
S
°
™
^
5l
3?!~
55
,2|
s «
Is
0) -—,
£J.2
O §
C S
o o
f
4
TJ
CD
O)
8
o
o
o
3r
II"
111
Dll
OOOOOOL r- Tl 01
000001. 0> (0 S "5 OT ^.
CD S B ,
ooooi
oo0l
oj _
£ g jj o
5
I •§ 2 * i i
I
l"O
li'Ii15
c'- ~ *
ll
.2 >- .£ •= g > <»
E ... CO ^ CD ^»
CD CD r" «^ ^!£ t-*
ooooi. d) o In •— n -Q •»
w P <2 T3 H m os
0001
001
<»•
* c »:
Sal.
rc
• § q>- o « i
too'o •£• i_ 'S a: J3 *" co
— "Ill II|
loooo'o co Q) <" p M_ .2 .2
i
| 5
! 5 M I |
C r~ -^ ^ ' O
•~" .— Q O-^ CO
co t »J2 .£
-------
ex
w
in
§•
S § .i
0 ^ ' 1 '
• s I
(U ^
_j ro.
§ fO
"jj ^
w a,
u
u ^
i • vl/
M i_i
a> m
T3 i^_i
*« cS '
O 0)
iw ~C
o w
M (rt
O l.
w S)
-H - ^^.
•
. i \ . -
.
,
O, , . So>o«S^o)c™— —, c c-' • c !« • ra ' „ • c
S'-d | -I | s '8 § .i | i1 8 .i g .9 i 5 5 -E S .2
O "^ » 1 1 - N = = 1 1 5 " 1 I I i § 1 1 1
°
O
0
o
o
0
o
,_
o
r \ ~CO"oS«I,'S^pOQrorn-Q^c:.E:tr
-------
DRAFT-DO NOT QUOTE OR CITE
' Table 2-4. CDD/CDF TEQ Emission Factors Used to Develop National
Emission Inventory Estimates of Releases to Air
II Emission Source
I Waste Incineration
jf Municipal waste incineration
|j Hazardous waste incineration
|| Boilers/industrial furnaces
|| Medical waste/pathological incineration
[J Crematoria
|| Sewage sludge incineration
|| I ire combustion
I Pulp and paper mill sludge incinerators
j bioQas combustion
1 Power/Energy Generation
I Vehicle fuel combustion - leaded13
j - unleaded
1 - diesel
r— — — — . —
j wood combustion - residential
I - industrial
[ Coal combustion - residential
- industrial/utility
Oil combustion . residential
- industrial/utility
Other High Temperature Sources
Cement kilns burning hazardous waste
uement kilns not burning hazardous waste
Asphalt mixing plants
Petro. refining catalyst regeneration
Cigarette combustion
Carbon reactivation furnaces
Kraft recovery boilers *
Minimally Controlled or Uncontrolled Combustion
Combustion of landfill gas in flares
Landfill fires
Accidental fires (structural)
Accidental fires (vehicle)
Forest, brush, and straw fires
Backyard trash burning
Uncontrolled combustion of PCBs
TEQ-
Emission
Factor
a
3.8
0.64
a
500
6.94
0.282
b
* *
45.7
1.7
172
2
0.82
* *
0.087
* *
0.2
24.34
0.29
* *
*
0.00043
to
0.0029
NEC
0.028
* #
* *
*
* *
2
* #
*
-T '
Emission Factor Units
ng TEQ/kg waste combusted \
ng TEQ/kg waste combusted
\
ng TEQ/body . ~1
ng TEQ/kg dry sludge combusted
ng TEQ/kg tires combusted
pg TEQ/km driven
pg TEQ/km driven
pg TEQ/km driven
ng TEQ/kg wood combusted 1
ng TEQ/kg wood combusted ||
ng TEQ/kg coal combusted
ng TEQ/L combusted
ng/kg clinker produced ||
ng/kg clinker produced
pg TEQ/cigarette
ng TEQ/kg solids combusted
__
ng TEQ/kg biomass combusted II
II
1
2-22
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 2-4. CDD/CDF TEQ Emission Factors Used to Develop National
Emission Inventory Estimates of Releases to Air (continued)
Emission Source
Metallurgical Processes
Ferrous metal smelting/refining
- Sintering plants
- Coke production
- Electric arc furnaces
- Ferrous foundries
Nonferrous metal smelting/refining
- Secondary aluminum smelting
- Secondary copper smelting
- Secondary lead smelters • •;
i
Scrap electric wire recovery
Drum and barrel reclamation
Chemical Manuf ./Processing Sources
Bleached chemical wood pulp and paper mills
Mono- to tetrachlorophenols
Pentachlorophenpl
Chlorobenzenes
Chlorobiphenyls (leaks/spills)
Ethylene dichloride/vinyl chloride
Dioxazine dyes and pigments ,
2,4-Dichloropherioxy acetic acid
Non-incinerated sludge
Tall oil-based liquid soaps
Biological Formation
Photochemical Formation
Reservoir Sources .
Emissions from chlorophenol-treated wood
TEQ
Emission
Factor
* *
* #
* *
* *
13.1
779
0.051 to
8.31
*
49.4
• , ' *
NEC
NEG
NEG
NEG
*
NEG
NEG
NA
NEG
NA -
#
*
Emission Factor Units
• • •— •
. —
-
...
ng/kg scrap feed
ng/kg scrap consumed
ng/kg lead produced
— •• .
ng TEQ/drum
•
_
"
(L
'
-
'
•
—
-
—
"' ' '
a Different emission factors were derived for various subcategories within this industry.
b Included within total for Wobd Combustion - Industrial. ,
Some evidence exists suggesting that this category is a source of CDD/CDF emissions. However, insufficient data
are available for making a quantitative or qualitative emission estimate.
** Evidence exists suggesting that this category is a source of CDD/CDF emissions. Preliminary estimates of emissions foe
reference year 1995 have been made (see Table 2-5), but the confidence in the emission factor estimates and/or activity
level estimates are so low that the estimates are too uncertain to include in the inventory.
NA = Not applicable. - . .
NEG = Expected to be negligible!(i.e., less than 1 ;gram per year) or non-existent.
2-23
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 2-5. Order of Magnitude Estimates of CDD/CDF Air Emissions from
Sources Not Quantified in the National Inventory3
(Reference Year 1995)
Estimated Emission to Air
(g TEQ./yr)
Potential Emission Source
1 -
Accidental Vehicle Fires
Asphalt Mixing Plants
Backyard Trash Burning
Biogas Combustion
Coke Production
Combustion of Landfill Gas in Flares
Electric Arc Furnaces
Ferrous Metal Foundries
Landfill fires
Residential/Commercial Coal Combustion
Residential/Commercial Oil Combustion
Iron Ore Sintering
Although some evidence exists that the following categories are sources of CDD/CDF emissions
to air, the available data are insufficient for making even order of magnitude emission estimates:
petroleum refining catalyst regeneration, uncontrolled combustion of PCBs, scrap electric wire
burners, bleached wood pulp and paper mills, manufacturers of ethylene dichloride/vinyl chloride,
accidental structural fires, photochemical formation, and chlorophenol-treated wood.
2-24
April 1998
-------
E
o
en
^
•o
'c
05
~O
CD
E"
"5
CO
•o
_co
QJ
N
'I
w
CO
TJ
C
.CO
'j^
o
•M
TJ^P 'S 1
m *- *O -S
1 t*s
2 2 -J
' » li
^ o .2 c
'E "§>"> i^
3- c CD H
5 2 -S
J^
*•= " 1
E CO <
.2 -0 C
^5 o> t""
CQ O> o
^Z- "~
•o —
>.
3
X
,
-
c
"c 'in ^1
•§ S (§1 • "o
^ O M^l
•I|s
w —
•5. ,„ -
H-* 05
a .1
^ .<2 -0 C
•£ en o)
2 —
"to
•a - 1 >
< oo a
0) —
O £
25 eg 1 CD .« T?
§ 1
H >
fc £
S .8
a . 8 ..
'E
01
~
^^
Table 2-6. CDD/CDF
~ ^ S^r
S g -° a
^ Jj O> f"~
o 2 s
Emission Source
===±=
c
Tf C
C
to
0)
I 5
S |
m to >
| § 8
*H to £
o = S
Q< ^i
==±=L:
CO
: c • c
C c
C ' c
C c
C £ c
c c
c ' c
M
Sludge incinerators
hemical Manuf./Processing Snnrrn:
All manuf./processing sources
Chlorine manufacture
Manuf. haloa. oraanic chemical.s
o
o co
° . "7 ^ "
- 0 CM T-
2 • *- CM
* CN
CM o
O 10 03 00 S
' .C ' I i . •
CM o in co '
T- (o • «- *~
0, . ' * . "
o . c S d S £
o - 8 . °> p
o
c • 1° ^ « ••
c , v '
- ' p ^
05
_ G CO ^" CM
W
'. •
, * 00
, c • ... • ,
- » CN
011 ID -
C , ' 10
•* "> A
10 . 0
C '
0
- to
10 !r
Manuf. halog. inorganic chemical
'aste Incineration
Municipal waste incineration
Hazardous waste incineration
Medical waste/pathological incine
Crematoria
g
=!==!=!=J=L
-5
5 CO - rs. ' . '
, ^ 10 05
r^ ^ ' • c c
C5 -CO
K - ts
X 0 d c c
O Q CO
co
^" c c
co ,
CO CO CO
°. • °. 03 • = c
O P CM
"> 10
? ^ c c '
CO
" .•* en .
,.: CM oo
T— ^ '
O ^ ' m. -
d p »-
• -
—
0
Sewage sludge incineration
Tire combustion
Combustion of landfill gas
stallurqical Processes
Ferrous metal smelting/refining
- Sintering plants
- Coke production
- Secondary ferrous smeltin
S
' I — * — ' *
10
c ' ^
o
oi
10
10
c o
c
CM '1O
«— . »— '
CO
.10
r>
0
CO
1
co
CO
Nonferrous metal smelting/refininc
Scrap electric wire recovery
Drum and barrel reclamation
00
05
05
in
CN
I
Csl
-------
I
T>
O)
c
1
CO
•5
CQ
o
i CO
(P
.S? *
£ .1
o
c
CO
1_
CD
O
I
I
o
'55
to
's
UJ
u.
Q
O
Q
Q
U
CD*
.(0
1^ 3-
2 £ -a C
Use
22-
0> 2?-=
1 o -a C
D 52s
*"e 1 -^
.2 .0 a
o> in HI
•5 CO H
co co c
ii 8 •&
"g •" u
£* co ^~
•g en as
w —
o —
« w —
•a w fe
e o <
£ Jo""
H r:~
I'S co C
l/j CO U.
< co a
CO ~
ro ~ ~
Ji|l
Emission Source
IO
*—
CM
q
d
,_
d
ower/Enerav Generation
Ou
Vehicle fuel combustion - all fuel
in
C
CN
o
CN
A
- leaded
co
(
o
CO
c
o
CO
d
A
•D
- unleade
(r
C
CO
CM
CO
A
"a
V
— ^
co
V
.2-
~
- industrial/u'
co
in
o
o>
CM
a
o
p
in
d
V
u
3
0
"ro
c
o
V)
3
O
O
6
CM
C
V
CO
GO
CM
A
- residential
E
~co
o>
V
£
•^
- industrial/ui
co
c
co
o
^
c
ct
0
CM
ther High Temperature Sources
Cement kilns
O
co
co
d
I
J
Q.
?
X
'E
.c
Q.
CO
c
c
c
c
c
c
c
Petro. refining catalyst regeneration
CM
o
d
A
Cigarette combustion
CO
a
CM
Accidental fires
c
c
c
c
c
c
c
Uncontrolled combustion of PCBs
CO
o
c
c
Carbon reactivation furnaces
c
c
c
c
c
c
c
s
c
_l
CM
0
c
o
c>
c
o
rj;
CO
CO
Lime production
o
d
tn
CM
c
d
Ceramics and alass manufacture
CO
O)
Q.
<
CO
CN
CN
-------
O
TJ
05
5
"c
^>
OJ
_c
. c
o
'co
03
'E
LU
TJ
05
.C
4-*
0
_C3
•g^E 'i 1
•~ "° 5 u
3 C?O5 H
2O5 c
*"• *—
03 -12 -
•a E S 5
•li£g
D C 03 H
5 *** 5
~~
*•-¥?
E to <
3 XI C
3)10 LU
Oj O3 ^^~
CD O3 _g
C "« >
•g-Stf
8 o "•;
4-i o> H
> 05 as
> .— «w
t/5 —
O —
CO 03 •— •
11 1 £
o> (o xi a
H »•.- £
.c 03 1-
t? 0*3 a
CO _. - _
2 ~
'co —
"^tn XI >
•= 03 a
» 00 LU
< 00 0)
• O3 —
*" "5 ~
8 I -° o
CD 2 —
CD
o
r • i
to
c
.2
' CO
.2
LU
LC
«-
.
0
c\
*
00
m
CO
CO
lurces
straw fii
5 ra-
"3 3
atural/Aqric
Forest, br
z
>
. c
1
c
c
c
c
c
iC
c
ormatio
Biological
: c
c
c
c
c
c
c
.0
to
1
CO
u
'p
Photochel
00
0
in
CM
o
o
5
•a
ra
0)
^
"o
lorpphen
£
u
0 I
eservoir Soi
Emissions
oc
8
CO
o
O3
LO
0
O
^J1
O
CO
. in
O5
LO
CO
O
o
CM
O
O
00
*ST
o
«
o
co
CM
O3
CO
O
H
to
a.-
o
c
o
'»
U)
o
s
E
3
'E
1
o>
c
co
O3
o>
•o
c
CO
3
•a
LU
"S
o
CN
tN
_£
J3
1=
^4
01 >.
.'•&«.'I
"S CM §
S.^ ™ 1
si-ji
ts'|I«
o 8 S~
| S-ll
11• 1 1
» ° IS'
§ -o •« ^
i "-s S
= _- o o
O CO U Q.
? 8 ,- s •
CO
. c
1
s
CO
&
if 55
a>
>
J3
-?
CO
-10
s
CN S, 1
O -i CO
°> CT -n —
- ro ^ jo
~- 0> m 05
CO — — ro
D) ^ 00 ^
c ep O5
'3 c?£ T5
5I^S
•§<•"£•
10 -D t» g
>- £ o> O
JJ ^ .E tS
•a ee E • S
9J .« o o
u. o: ii to
CO
3 ' -
J3
•E
o —
U LO
— O5
O 05
CD »
O
I"
2
O
&
CO
c _;
— LO
CO O)
>-m
CO ^
.CO ^
to c
!i
51
. >
•o
2
o
_c -
4^
o .
c c
CO .2
•S s
O 3
S"§
CD i.
•»- a.
| «.
8.8
1?
'•o § =
— °63
0-0*0
§ s «/5.
T3 CD = «
O .^ CO »
O •— CD to
S CO Q. T-,
- ri^l
5rll
Q) »*- QJ
lf^~
5-15 xj co
« f ' 3 S '
to
— o> i .t co
?; m > P
i c 5
10 CD
5£
% u
11
^~ aj
*ff
P|
LO LU
O5 „_
O5 O
^•K S b-
. s co o>
5- CD
c '5 2
,- -2 'S i
* » S S
5 J "5-°
O) p H- "D
f I °-g
s ° si
•S 11 S
a | 3 ,.
•3 i oS
! -5 p
CO
® CO
s g-
XQ
O i^
Q rs
to ^
•- =
*- to
CO CD
3 T3
•g =
E o
CO
-I I § i» §
co to co to o co
co ^) o T3 Q) ».
3 3
O O
to to
ro 43
o o
O £
».£ a r.
£ E E I
2 S S o)
i .J= vt 0)
c c c to
.0000
'w '53 'SS CD
co co co u
"E 1 E 3
Q) 03 Q) O.
s--s
(D
(ft
CO
CD
O)
a.
<
CN
-------
-------
DRAFT-DO NOT QUOTE OR CITE
3. COMBUSTION SOURCES OF CDD/CDF: WASTE INCINERATION
Incineration is the destruction of solid, liquid, or gaseous wastes through the
application of heat within a controlled combustion system. The purposes of incineration
are to reduce the volume of waste that needs land disposal and to reduce the toxicity of
the waste, making it more sterile. In keeping with this definition, incinerator systems can
be classified by the types of wastes incinerated: municipal solid waste incineration;
medical and pathological waste incineration; hazardous waste incineration; sewage sludge
incineration; tire Incineration; and biogas flaring. Each of these types of incinerators are
discussed in this chapter. The purposes of this chapter are to: characterize and describe
waste incineration technologies in the United States and to derive estimates of annual
releases of CDDs and CDFs into the atmosphere from these facilities for reference years
1987 and 1995.
Combustion research has developed three theories on the mechanisms involved in
the emission of CDDs and CDFs from combustion systems: (1) CDD/CDFs can be
introduced into the combustor with the feed and pass through the system unchanged,
(2) CDD/CDFs can be formed during combustion, or (3) CDD/CDFs can be formed via
chemical reactions in the post-combustion portion of the system. The total CDD/CDF
emissions are likely to be the net result of all three mechanisms; however, their relative
importance is often uncertain. To the extent practical with the available data, the
combustors in each source category were divided into classes judged to have similar
emission factors. This classification effort attempted to reflect the emission mechanisms
described above. The emission mechanisms suggest that the aspects of combustor design
and operation that could affect CDD/CDF emissions are furnace design, composition of the
waste feed, temperature in the post-combustion zone of the system, and type of air
pollution control device (APCD) used to remove contaminants from the flue gases.
Therefore, incineration systems that are similar in terms of these factors should have similar
CDD/CDF emissions. Accordingly, this chapter proposes classification schemes that divide
combustors into a variety of design classes based on these factors. Design class/as used
here, refers to the combination of furnace type and accompanying APCD.
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
3,1. MUNICIPAL SOLID WASTE INCINERATION
As discussed previously, CDD/CDF emission theory suggests that CDD/CDF
emissions can be related to several factors, including furnace design, composition of the
waste feed, temperature in the post-combustion zone of the system, and type of APCD
used to remove contaminants from the flue gases. Accordingly, this chapter proposes a
classification scheme that divides municipal solid waste incinerators (MSWIs) into a variety
of design classes based on those factors. Some APCDs are operated at different
temperatures; therefore, operating temperature is used to define some design classes.
Because the theory also suggests that feed can influence CDD/CDF emissions, the
proposed furnace classification system distinguishes refused-derived fuel from normal
municipal solid waste (MSW). This section begins with a description of the MSWI
technology and then proposes the design classification scheme. Using this scheme, the
MSWI industry is characterized for the reference years 1987 and 1995. Finally, the
procedures for estimating emissions are explained, and results summarized.
3.1.1. Description of Municipal Solid Waste Incineration Technologies
For purposes of this report, MSWI furnace types are divided into three major
categories: mass burn, modular, and refuse-derived fuel. Each of these furnace types is
described below, followed with a description of the APCDs used with these systems.
Furnace Types
Mass Burn: Historically, this furnace type derived its name because it burned MSW
as received (i.e., no preprocessing of the waste was conducted other than removal of items
too large to go through the feed system). Today, a number of other furnace types also
burn unprocessed waste (as described below). Mass burn furnaces are distinguished from
these others because they burn the waste in a single stationary chamber. In a typical mass
burn facility, MSW is placed on a grate that moves through the combustor. The 1995
inventory indicates that the combustion capacity of facilities ranges from 90 to 2,700
metric tons of MSW per day. Three subcategories of mass burn (MB) technologies are
described below:
Mass burn refractory-walled (MB-REF) systems represent an older class of MSWIs
(generally built in the late 1970s to early 1980s) that were designed only to reduce
the volume of waste in need of disposal by 70 to 90 percent. These facilities
3-2
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
* - t \
usually lacked boilers to recover the combustion heat for energy purposes. In the
MB-REF design, the MSW is delivered to the combustion chamber by a traveling
grate and/or a ram feeding system. Combustion air in excess of stoichiometric
amounts (i.e., more oxygen is supplied than needed for complete combustion) is
supplied both below and above the grate.
Mass burn waterwall (MB-WW) facilities represent enhanced combustion efficiency
as compared with MB-REF incinerators. Although it achieves similar volume
reductions, the MB-WW incinerator design provides a more efficient delivery of
combustion air, resulting in sustained higher temperatures. Figure 3-1 is a schematic
of a typical MB-WW MSWI. The term 'waterwall ' refers to a series of steel tubes
running vertically along the walls of the furnace. The tubes contain water, which '
when heated by combustion, transfer energy from the heat of combustion to the
water. The water reaches boiling temperature, and steam is produced. The steam
is then used to drive an electrical turbine generator or for other industrial needs.
This transfer of energy is termed 'energy recovery.'
Mass burn rotary kiln combustors (MB-RC) use a water-cooled rotary .combustor
which consists of a rotating combustion barrel configuration mounted at a 15-20°
angle of decline. The refuse is charged at the top of the rotating kiln by a hydraulic
ram (Donnelly, 1992K Preheated combustion air is delivered to the kiln through
various portals. The slow rotation of the kiln (i.e., 10 to 20 rotations/hour) causes
the MSW to tumble, thereby exposing more surface area for complete burnout of
the MSW. These systems are also equipped with boilers for energy recovery.
Figure 3-2 is a schematic of a typical MB-RC MSWI.
Modular incinerator: This is the second general type of MSWI furnace used in the
United States. As with the mass burn type, modular incinerators burn waste without
preprocessing. Modular MSWIs consist of two vertically mounted combustion chambers
(i.e., a primary and secondary chamber). In the 1995 inventory, modular combustors'
combustion capacity ranged from 4 to 270 metric tons/day. The two major types of
modular systems, "excess air" and "starved air," are,described below.
The modular excess-air system consists of a primary and secondary combustion
chamber, both of which operate with air levels in excess of stoichiometric
requirements (i.e., 100 to 250 percent excess air). Figure 3-3 illustrates a typical
modular excess-air MSWI.
Starved (or controlled) air. is a newer type of modular system, which is easier and
less expensive to operate than the excess-air systems. In these systems, air is
supplied to the primary chamber at sub-stoichiometric levels. The products of ,
incomplete combustion entrain in the combustion gases that are formed in the
primary combustion chamber, then pass into a secondary combustion chamber.
Excess air is added to the secondary chamber, and combustion is completed by
elevated temperatures sustained with auxiliary fuel (usually natural gas). The high.
3"3 - " -< April 1998'
-------
DRAFT-DO NOT QUOTE OR CITE
and uniform temperature of the secondary chamber, combined with the turbulent
mixing of the combustion gases, results in low-levels of particulate matter ancl
organic contaminants being formed and emitted. Therefore, many existing modular
units lack post-combustion air pollution control devices. Figure 3-4 is a schematic
view of a modular starved-air MSWI.
Refuse-Derived Fuel (RDF): The third major type of MSWI furnace technology is
designed to combust refuse-derived fuel (RDF). RDF is a general term that describes MSW
from which relatively noncombustible items are removed, thereby enhancing the
combustibility of the MSW. RDF is commonly prepared by shredding, sorting, and
separating out metals to create a dense MSW fuel in a pelletizecl form, having a uniform
size. Three types of RDF systems are described below.
" ''
• The dedicated RDF system burns RDF exclusively. Figure 3-5 shows a typical
dedicated RDF using a spreader-stoker boiler. Pelletized RDF is fed into the
combustor through a feed chute, using air-swept distributors; this allows a portion
of the feed to burn in suspension and the remainder to burn out after falling on a
horizontal traveling grate. The traveling grate moves from the rear to the front of
the furnace, and distributor settings are adjusted so that most of the waste lands on
the rear two-thirds of the grate. This allows more time to complete combustion on
the grate. Underfire and overfire air are introduced to enhance combustion, and
these incinerators typically operate at 80 to 100 percent excess air. Waterwall
tubes, a superheater, and an economizer are used to recover heat for production of
steam and/or electricity. The 1995 inventory indicates that dedicated RDF facilities
range in total combustion capacity from 227 to 2,720 metric tons/day,
• Cofired RDFs burn both RDF and normal MSW.
The fluidized-bed RDF (FB-RDF) burns the waste in a turbulent and semi-suspended
bed of sand. The MSW may be fed into the incinerator either as unprocessed waste
or as a form 'of RDF. The RDF may be injected into or above the bed through ports
in the combustor wall. The sand bed Is suspended during combustion by introducing
underfire air at a high velocity, hence the term "fluidized." Overfire air at 100
percent stoichiometric requirements is injected above the sand suspension. Waste-
fired FB-RDFs typically operate at 30 to 100 percent excess air levels and at bed
temperatures around 815°C (1,500°F). A typical FB-RDF is presented as Figure 3-6.
Technology has two basic design concepts: (1) a bubbling-bed incineration unit and
(2) a circulating-bed incineration unit. The 1995 inventory indicates that fluidized-
bed MSWls have capacities ranging from 184 to 920 metric tons/day. These
systems are usually equipped with boilers to produce steam.
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Air Pollution Control Devices (APCDs)
MSWIs are commonly equipped with one or more post-combustion APCDs to
remove various pollutants prior to release from the stack (e.g., particulate matter, heavy
metals, acid gases, and/or organic contaminants) (U.S. EPA, 1992d). These APCDs
include: :J .
Electrostatic precipitator (ESP),
Fabric filter (FF), ,
• Dry scrubber (DS),
Dry sorbent injection (DSI), and
Wet scrubber (WS) ( .
i
Electrostatic Precipitator: The ESP is generally used to collect and control
particulate matter that evolves during MSW combustion, by introducing a strong electrical
field in the flue gas stream; this, in turn, charges the particles entrained in the combustion
gases (Donnelly, 1992). Large collection plates receive an opposite charge to attract and
collect the particles. CDD/CDF formation can occur within the ESP at temperatures in the
range of 150 to about 350°C. As temperatures at the inlet to the ESP increase from
1 50 to 300°C, CDD/CDF concentrations have been observed to increase by approximately
a factor of two for each 30°C increase in temperature (U.S. EPA, 1994f). As temperature
increases beyond 300°C, formation rates decline. Although ESPs in this temperature range
efficiently remove most particulates and the associated CDD/CDFs, the formation that
occurs can result in a net increase in CDD/CDF emissions. This temperature, related
formation of CDD/CDF within the ESP can be applied to distinguish hot-side ESPs from
cold-side ESPS. For purposes of this report, ESPs are classified as follows:
• A cold-side ESP operates at or below 230°C.
••"'* A hot-side ESP operates at an inlet temperature greater than 230°C.
Fabric Filters (FF): FFs are also particulate matter control devices, which remove
dioxins associated with particles and any vapors that adsorb to the particles. Six- to 8-inch
diameter bags, made from woven fiberglass material, are usually arranged 'in series. An
induction fan forces the combustion gases through the tightly woven fabric. The porosity
of the fabric allows the bags |o act as filter media and retain a broad range of particles
3-5 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
sizes {i.e., down to less than 1 micrometer in diameter). The FF is sensitive to acid gas;
therefore, it is usually operated in combination with spray dryer adsorption of acid gases.
Dry Scrubbers (PS): DSs, also called spray dryer adsorption, involve both the
removal of acid gas and paniculate matter from the post-combustion gases. By
• , ,/
themselves, these units probably have little effect on dioxin emissions. In a typical DS
system, hot combustion gases enter a scrubber reactor vessel. An atomized hydrated lime
slurry (water plus lime) is injected into the reactor at a controlled velocity (Donnelly, 1992).
The hydrated lime slurry rapidly mixes with the combustion gases within the reactor. The
water in the hydrated lime slurry quickly evaporates, and the heat of evaporation causes
the combustion gas temperature to rapidly decrease. The neutralizing capacity of hydrated
lime reduces the combustion gas content of acid gas constituents (e.g., hydrogen chloride
gas, and sulfur dioxide gas) by greater than 70 percent. A dry product, consisting of
particulate matter and hydrated lime, settles to the bottom of the reactor vessel. DS
technology is used in combination with ESPs. The DS reduces ESP inlet temperatures to
make a cold-side ESP. DS/FFs have achieved greater than 95 percent reduction and control
of CDD/CDFs in MSWI emissions (U.S. EPA, 1 992d).
Dry Sorbent Injection (DSI): DSI is used to reduce acid gas emissions. By themselves,
these units probably have little effect on dioxin emissions. DSI involves the injection of dry
hydrated lime or soda ash either directly into the combustion chamber or into the flue duct
of the hot post-combustion gases. In either case, the reagent reacts with and neutralizes
the acid gas constituents (Donnelly, 1992).
Wet Scrubber (WS): WS devices are designed for acid gas removal, and are more
common to MSWIs in Europe'than in the United States. They should help reduce emissions
of dioxin in both vapor and particle forms. WS devices consist of two-stage scrubbers. The
first stage removes HCI, and the second stage removes SO2 (Donnelly, 1992). Water is
used to remove the HCI, and caustic or hydrated lime is added to remove SO2 from the
combustion gases.
In addition to the APCDs described above, some less common types are also used in
some MSWIs. An example is the Electro Granular Bed (EGB), which consists of a packed
bed of activated carbon. An electric field is passed through the packed bed; particles
entrained in the flue gases are given a negative charge, and the packed bed is given a
positive charge. EGB systems function much like an ESP. Particulate matter is collected
within the bed; therefore, they will remove dioxins associated with collected particles and
3-6 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
any vapors that adsorb to the particles. Only one facility in the United States currently
employs the EGB system, a fluidized bed-RDF MSWI.
Classification Scheme .
Based on the array of MSWI technologies described above, a classification system
for deriving CDD/CDF emission estimates was developed. As discussed earlier, it is
assumed that facilities with common design and, operating characteristics have a similar
, potential for CDD/CDF emissions. The MSWIs operating in 1987 and 1995 were divided
according to the eight furnace types and seven APCDs described above. This resulted in
17 design classes in 1987 and 40 design classes in 1995. Because fewer types of APCDs
were used in 1987 than in 1995, fewer design classes are needed for estimating emissions.
This taxonomy is summarized in Figures 3-7 and 3-8. ,
3.1.2. Characterization of MSWI Facilities in Reference Years 1995 and 1987
Table 3-1 lists by design/APCD type, the number of facilities and activity level (kg
MSW incinerated per year) for MSWIs in the reference year 1995. A similar inventory is
provided for reference year 1987 in Table 3-2. This information was derived from four
reports: U.S. EPA (1987b), Sytems Applications International (1995), Taylor and Zannes
(1996), and Solid Waste Technologies (1994). In general, these studies collected the
information via telephone interviews with the plant operators.
Using Tables 3-1 and 3-2, a number of comparisons can be made between the two
reference years:
' " )
The number of facilities stayed about the same (113 in 1987 and 130 in 1995), but
the amount of MSW incinerated more than doubled (13.Bullion kg in 1987 and
28.8-billion kg in 1995). '
The dominant furnace technology shifted from,modular in 1987 (57 units and 1.4-
billion kg) to mass burn waterwall facilities in 1995 (57 units and 17-billion kg).
• The dominant APCD technology shifted from hot-sided ESPs in 1987 (54 units and
11-billion kg) to fabric filters in 1995 (55 units and 16-billion kg)'.
The use of hot-sided ESPs dropped from 54 facilities in 1987 (11 -billion kg) to 16
facilities in 1995 (2.2-billion kg).
The number of uncontrolled facilities dropped from 38 in 1987 (0.6-billion kg) to 10
facilities in 1995 (0.2-billion kg). ,
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
3.1.3. Estimation of CDD/CDF Emissions from MSWIs
Compared to other CDD/CDF source categories, MSWIs have been more extensively
evaluated for CDD/CDF emissions. Within the context of this report, adequate emission
testing for CDD/CDFs were available for 11 of the 113 facilities in the 1987 inventory and
27 of the 130 facilities in the 1995 inventory. Nationwide CDD/CDF air emissions from
MSWIs were estimated using a three-step process as described below.
Step 1. Estimation of emissions from all stack tested facilities. The EPA stack testing
method (EPA Method 23) produces a measurement of CDD/CDF in units of mass
concentration of CDD/CDF (i.e., nanograms per dry standard cubic meter of combustion gas
[ng/dscm]) at standard temperature and pressure (20°C and one atmosphere), and adjusted
to a measurement of 7 percent oxygen in the flue gas (U.S. EPA, 1995b). This
concentration is assumed to represent conditions at the point of release from the stack into
the air. Equation 3-1 below was used to derive annual emission estimates for each tested
facility:
E = CxVx CFx H
TEQ 109 nglg
>,
Where:
— Annual TEQ emission (g /yr)
C = Combustion flue gas TEQ concentration (ng/dscm) (20°C, 1 atm;
adjusted to 7% O2)
V = Volumetric flow rate of combustion flue gas (dscm/hour) (20°C, 1
atm; adjusted to 7% O2)
CF = Capacity factor, fraction of time that the MSWI operates (i.e., 0.85)
H = Total hours in a year (8,760 hr/yr)
After calculating annual emissions for each tested facility, the emissions were summed
across all tested facilities for each reference year. [Note: many of the emission tests do
, i" , ' " •• , ' '
not correspond exactly to these 2 years. In these cases, the equipment conditions present
at the time of the test were compared to those during the reference year to determine their
applicability.]
Step 2. Estimation of emissions from all non-tested facilities. This step involves
multiplying the emission factor and annual activity level for each MSWI design class and
3~8 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
then summing across classes. The activity levels for reference years 1995 and 1 987 are
summarized in Tables 3-1 and 3-2, respectively.'The emission factors were derived by
averaging the emission factors across each tested facility in a design class. The emission
factor for each facility was calculated using the following equation:
EF - C X F*
, ,rmswi--• —~ (Eqn. 3-2)
Where:
£Fmsw> = Emission factor, average ng TEQ per kg of waste burned
c '= TEQ or CDD/CDF concentration in flue gases (ng TEQ/dscm) (20°C, 1
atm; adjusted to 7% O2)
Fv • ~ • Volumetric flue gas flow rate (dscm/hr) (20°C, 1 atm; adjusted to 7%
lw = Average waste incineration rate (kg/hr)
Example: A mass burn waterwall MSWI equipped with cold-sided ESP.
Given:
C _= 10 ng TEQ/dscm (20°C, 1 atm; adjusted to 7% O2)
Fv =• 40,000 dscm/hr (20°C, 1 atm; adjusted to 7% O2)
lw = 10,000 kg MSW/hr "
= 10 ng 40,000 dscm hr
EF = 40/zg TEQ
• MBWW ~, ,,CTI/—r ~
. . -kg • MSW burned
EPA was not able to obtain engineering test reports of CDD/CDF emissions for a
number of design classes. In these cases, the above procedure could not be used to derive
emission factors. Instead, the emission factors of the tested design class that was judged
most similar in terms of dioxin control was assumed to apply to the untested class. The
following logic was used to make this decision:
3-9
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
1. The tested APCDs for the furnace type of the untested class were reviewed to see if
any operated at a similar temperature.
2. If any operated at similar temperatures, the one with most similar technology was
assumed to apply.
3, If none operated at a similar temperature, then the most similar furnace type with
same control device was assumed to apply.
Table 3-3 lists all design categories with no tested facilities and shows the class with
tested facilities that was judged most similar.
It should be understood that the emission factors for each design class are the same
for both reference years. This is because the emission factor is determined only by the
design and operating conditions and is independent of the year of the test.
Step 3. Sum emissions from tested and untested facilities. This step simply involves
summing emissions from all tested and untested facilities. This process is shown in Tables
3-4 and 3-5 for the reference years 1995 and 1987, respectively. The tables are organized
by design class and show separately the emission estimates for the tested and .untested
facilities. The calculation of emissions from untested facilities is broken out to show the
activity level and emission factor for each design class.
3.1.4. Summary of CDD/CDF (TEQ) Emissions from MSWIs for 1995 and 1987
The activity level estimates (i.e., the amount of MSW that is annually combusted by
the various MSWI technologies) are given a "high" confidence rating for both 1987 and
1995. For both years, comprehensive surveys of activity levels were conducted by
independent sources on virtually all facilities (U.S. EPA, 1987b; Systems Application
International, 1995; Taylor and Zannes, 1996; Solid Waste Technologies, 1994).
The emission factor estimates are given a "medium" confidence rating for both
1987 and 1995. A moderate fraction of the facilities were tested in both years: 11 of 113
facilities in 1987 (10 percent), and 27 of 130 facilities (21 percent) in 1995. Moreover, the
tested facilities represent 21 and 27 percent of the total activity level of operating MSWIs
in 1987 and 1995, respectively. These tests represent most of the design categories
3-10
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
identified in this report. The emission factors were developed from emission tests that
followed standard EPA protocols, used strict QA/QC procedures, and were well
documented in engineering reports. Because all tests were conducted under normal
operating conditions/some uncertainty exists about the magnitude of emissions that may
occur during other times (i.e., upset conditions, start-up and shut-down).
These confidence ratings produce an overall "medium" confidence rating. Using the
procedures established for this report for a "medium" confidence rating, the best estimate
of the annual emissions is assumed to be the geometric average of a range that varies by a
factor of five between the low and high ends. For 1987, the central estimate of the^annual
emissions is 7,915-g TEQ/yr, and the range is calculated to.be 3,540- to 17,698-g TEQ/yr.
For 1995, the central estimate of annual emissions is 1,100-g TEQ/yr, and the range is
calculated to be 492-to 2,460-g TEQ/yr.
3.1.5 Congener Profiles of MSWI Facilities
The TEQ air emissions from MSWIs are actually a mixture of CDD and CDF
congeners. These mixtures can be translated into what are termed 'congener profiles,'
which represent the distribution of total CDDs and CDFs present in the mixture. A
congener profile may serve as a signature of the types of CDDs and CDFs associated with
particular MSWI technology and APCD. Figure 3-9 is a congener profile of a mass-burn
waterwall MSWI equipped with a dry scrubber and fabric filter (i.e., the most common type
of MSWI and APCD design in use today). In general, the congener profile suggests that
OCDD dominates total CDD/CDF emissions. In addition, every toxic CDD/CDF congener is
detected in the emissions.
3.1.6 Estimated CDD/CDFs in MSWI Ash
Ash from MSWIs is required to be disposed in permitted landfills. Based on
protocols of this report, ash from MSWIs are, therefore, not considered environmental
releases of CDD/CDFs and are not included in the inventory. For background purposes,
however, some information is presented below about the quantities of CDD/CDFs in ash
from MSWIs.
An estimated 7-million metric tons of total ash (bottom ash plus fly ash) were
generated by MSWIs in 1992 (telephone conversation between J. Loundsberry, U.S. EPA
Office of Solid Waste, and L. Brown, Versar Inc., on February 24, 1993). U.S. EPA
3'11 '.,.': April 1998 '
-------
DRAFT-DO NOT QUOTE OR CITE
(1991b) indicated that 2- to 5-million metric tons of total ash were produced annually in the
late 1980s from MSWIs, with fly ash comprising 5 to 15 percent of the total. U.S. EPA
(1990c) reported the results of analyses of MSWI ash samples for CDDs and CDFs. Ashes
from five state-of-the-art facilities located in different regions of the United States were
analyzed for all 2,3,7,8-substituted CDDs and CDFs. The TEQ levels in the ash (fly ash
mixed with bottom ash) ranged from 106 to 466 ng/kg, with a mean value of 258 ng/kg.
CDD/CDF levels in fly ash are generally much higher than in bottom ash. For example,
Fiedler and Hutzinger (1992) reported levels of 13,000-ng TEQ/kg in fly ash. Multiplying
the mean TEQ total ash concentration by the estimated amount of MSWI ash generated
annually (approximately 7-million metric tons in 1995 and 5-million metric tons in 1987)
yields an estimated annual TEQ in MSWI ash of 1,800-g TEQ/yr in 1995 and 1,300-g
TEQ/yrin 1987.
Each of the five facilities sampled in U.S. EPA (1990c) had companion ash disposal
facilities equipped with leachate collection systems or some means of collecting leachate
samples. Leachate samples were collected and analyzed for each of these systems.
Detectable levels were only found in the leachate at one facility (TEQ = 3 ng/L); the only
detectable congeners were HpCDDs, OCDD, and HpCDFs.
3.1.7 Current EPA Regulatory and Monitoring Activities
On December 19, 1995, EPA promulgated CDD/CDF emission standards for all
existing and new MSWI units with aggregate capacities to combust greater than 35 metric
tons per day (Federal Register, 1995e). The specific emission standards (expressed as
ng/dscm of total CDD/CDF - based on standard dry gas corrected to 7 percent oxygen) are
a function of the size, APCD configuration, and age of the facility as listed below:
1995 Emission standard
(ng total CDD/CDF/dscm) Facility age, size, and APCD
60 • Existing; > 225 metric tons/day; ESP-
based APCD
30 • Existing; > 225 metric tons/day; non-
ESP-,based APCD
125 • Existing; > 35 to ^225 metric
tons/day
13 • New; > 35 metric tons/day
3"12 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
States have up to 3 years from promulgation of the Federal standards to submit
revised State Implementation Plans to EPA for approval. Once approved, States have the
primary responsibility to implement the new standards. This could occur as early as the
year 2000. As this date approaches, EPA's Office of air Quality Planning and Standards
(OAQPS) estimates that the current estimate of national emissions of CDD/CDFs from
existing MSWIs will decline from current levels. OAQPS estimates full compliance by all
MSWIs with the 1995 standards will result in an annual emission of about 24-g TEQ/yr
(U.S. EPA, 1996d).
3.2. HAZARDOUS WASTE INCINERATION
Hazardous waste inpineration (HWI) is the controlled pyrolysis and/or oxidation of
potentially dangerous liquid, gaseous and solid waste. HWI is one technqlogy used to
manage hazardous waste under RCRA and CERCLA (Superfund) programs. As described
below, hazardous wastes are burned in a variety of situations and are covered in a number
. - /
of different sections in this report.
Much of the hazardous waste is burned in facilities dedicated to burning waste.
Most of these dedicated facilities are located "onsite" at chemical manufacturing
facilities and only burn waste associated with their on-site industrial operations.
Hazardous waste is also burned at dedicated facilities located "offsite" from
manufacturing facilities and accept waste from multiple sources. These fixed
location facilities dedicated to burning hazardous waste at both on- and off-site
locations are addressed in Sections 3.2.1 to 3.2.4.
Hazardous waste is also burned in industrial boilers and furnaces that are permitted
to burn the waste as supplemental fuel. These facilities have significantly different
, furnace designs and operations than dedicated HWIs; therefore, they are discussed
in Section 3.2.5. '
A number of cement kilns are also permitted to burn hazardous waste as auxiliary
fuel; these are discussed separately in Section 5.1.
Mobile HWIs are typically used for site cleanup at Superfund sites and operate for a
limited duration at any given location. These units are 'mobile' in the sense that
they can be transported from one location to another. Due to the transitory nature
of these facilities, they are not included in this inventory.
3-13
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
The following subsections review the types of HWI technologies commonly in use in
the United States, and present the derivation of emissions estimates of CDD/CDFs from all
facilities operating in 1995 and 1987.
3.2.1. Furnace Designs for Dedicated Hazardous Waste Incinerators
The four principal furnace designs employed for the combustion of hazardous waste
in the United States are: liquid injection, rotary kiln, fixed hearth, and fluidized-bed
incinerators (Dempsey and Oppelt, 1993). The majority of commercial operations are of
the rotary kiln incinerator type. On-site (noncommercial) HWI technologies are an equal mix
of rotary kiln and liquid injection facilities, with a few additional fixed hearths and fluidized
bed operations {U.S. EPA, 1996h). Each of these MWI technologies is discussed below:
Rotary Kiln HWI: Rotary kiln incinerators consist of a rotating kiln, coupled with a
high temperature afterburner. Because these are excess air units designed to combust
hazardous waste in any physical form (i.e., liquid, semi-solid, or solid), rotary kilns are the
most common type of hazardous waste incinerator used by commercial "off-site"
operators. The rotary kiln is a horizontal cylinder lined with refractory material.. Rotation'of
the cylinder on a slight slope provides for gravitational transport of the hazardous waste
through the kiln (Buonicore, 1992a). The tumbling action of the rotating kiln causes mixing
and exposure of the waste to the heat of combustion, thereby enhancing burnout. Solid
and semi-solid wastes are loaded into the top of the kiln by an auger or rotating screw.
Fluid and pumpable sludges and wastes are typically introduced into the kiln through a
water-cooled tube. Liquid hazardous waste is fed directly into the kiln through a burner
nozzle. Auxiliary fuel (natural gas or oil) is burned in the kiln chamber at start-up to reach
elevated temperatures. The typical heating value of hazardous waste (i.e., 8,000 Btu/kg) is
sufficient to sustain combustion without auxiliary fuel (U.S. EPA, 1996h). The combustion
gases emanating from the kiln are passed through a high temperature afterburner chamber
to more completely destroy organic pollutants entrained in the flue gases. Rotary kilns can
be designed to operate at temperatures as high as 2,580°C, but more commonly operate at
about 1,100°C.
Liquid Injection HWI: Liquid injection incinerators (Llls) are designed to burn liquid
hazardous waste. These wastes must be sufficiently fluid to pass through an atomizer for
3"14 , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
injection as droplets into the combustion chamber. The Llls consist of a refractory-lined
steel cylinder mounted either in a horizontal or vertical alignment. The combustion
chamber is equipped with one or more waste burners. Because of the rather large surface
area of the atomized droplets of liquid hazardous waste, the droplets quickly vaporize. The
moisture evaporates, leaving a highly combustible mix of waste fumes and combustion air
(U.S. EPA, 1 99ph). Secondary air is added to the combustion chamber to complete the
oxidation of the fume/air mixture.
Fixed Hearth HWh Fixed hearths, the third principal hazardous waste incineration
technology, are starved air or pyrolytic incinerators, which are two-stage combustion units.
Waste is ram-fed into the primary chamber and incinerated below stoichiometric
requirements (i.e., at about 50 to 80 percent of stoichiometric air requirements). The
resulting smoke and pyrolytic combustion products are then passed though a secondary
combustion chamber where relatively high temperatures are maintained by the combustion
of auxiliary fuel. Oxygen is introduced into the secondary chamber to promote complete
thermal oxidation of the organic molecules entrained in the gases.
Fluidized-bed HWI: The fourth hazardous waste incineration technology is the
fluidized-bed incinerator, which is similar in design to that used in MSW incineration. (See
Section 3.1 .) In this configuration, a layer of sand is placed on the bottom of the
combustion chamber. The bed is preheated by underfire auxiliary fuel at startup. During
combustion of auxiliary fuel at start-up, the hot gases are channeled through the sand at
relatively high velocity, and the turbulent mixing of combustion gases and combustion air
causes the sand to become suspended (Buonicore, 1992a). This takes on the appearance
of a fluid medium, hence the incinerator is termed a 'fluidized bed' combustor The
incinerator is operated below the melting point temperature of the bed material. Typical
temperatures of the fluid medium are within the range of 650 to 940°C. A constraint on
the types of waste burned is that the solid waste particles must be capable of being
suspended within the furnace. When the liquid or solid waste is combusted in the fluid
medium, the exothermic reaction causes heat to be released into the upper portion of the
combustion chamber. The upper portion is typically much larger in volume than the lower
portion, and temperatures can reach 1,000°C {Buonicore, 1992a). This high temperature is
sufficient to combust volatilized pollutants emanating from the combustion bed.
i| 1998
-------
DRAFT-DO NOT QUOTE OR CITE
3.2.2. APCDs for Dedicated Hazardous Waste Incinerators
Most HWIs use APCDs to remove undesirable components from the flue gases that
evolved during the combustion of the hazardous waste. These unwanted pollutants include
suspended ash particles ("particulate matter" or PM), acid gases, metal, and organic
pollutants. The APCD controls or collects these pollutants and reduces their discharge from
the incinerator stack to the atmosphere. Levels and kinds of these combustion byproducts
are highly site-specific, depending on factors such as waste composition and incinerator
system design and operating parameters (e.g., temperature and exhaust gas velocity). The
,/ i * / • „ i i •
APCD is typically comprised of a series of different devices that work together to clean
the exhaust combustion flue gas. Unit operations usually include exhaust gas cooling,
followed by particulate matter and acid gas control.
Exhaust gas cooling may be achieved using a waste heat boiler or heat exchanger,
mixing with cool ambient air, or injection of a water spray into the exhaust gas. A variety
of different types of APCDs are employed for the removal of particulate matter and acid
gases. Such devices include: wet scrubbers (such as venturi,, packed bed, and ionizing
systems), electrostatic precipitators, and fabric filters (sometimes used in combination with
dry acid gas scrubbing). In general, the control systems can be grouped into the following
three categories: "wet," "dry," and "hybrid wet/dry" systems. The controls for acid gases
(either dry or wet systems) cause temperatures to be reduced preceding the control device.
This impedes the extent of formation of CDDs and CDFs in the post-combustion area of the
typical HWI. It is not unusual for stack concentrations of CDD/CDFs at a particular HWI to
be in the range of 1- to 100-ng CDD/CDF/dscm (Helble, 1993), which is low in comparison
to other waste incineration systems. The range of total CDD/CDF flue gas concentrations
measured in the stack emissions of HWIs during trial burns across the class of HWI
facilities, however, has spanned four orders of magnitude (ranging from 0.1 to 1,600
ng/dscm) (Helble, 1993). The APCD systems are described below:
• Wet Systems: A wet scrubber is used for both particulate and acid gas control.
Typically, a venturi scrubber and packed-bed scrubber are used in a back-to-back
arrangement. Ionizing wet scrubbers, wet electrostatic precipitators, and innovative
venturi-type scrubbers may be used for more efficient particulate control. Wet
scrubbers generate a wet effluent liquid wastestream (scrubber blowdpwn), are
relatively inefficient at fine particulate control compared to dry control techniques,
3-16 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
and have equipment corrosion concerns. However, wet scrubbers do provide
efficient control of acid gases and have lower operating temperatures (compared
; with dry systems), which may help control the emissions of volatile metals and
organic pollutants.
• Dry Systems: In dry systems, a fabric filter or electrostatic precipitator (ESP) is used
for particulate control. A fabric filter or ESP is frequently used in combination with
dry scrubbing for acid gas control. Dry scrubbing systems, in comparison with wet
scrubbing systems, are inefficient in controlling acid gases.
• Hybrid Systems: In hybrid systems, a dry technique (ESP or fabric filter) is used for
particulate control, followed by a wet technique (wet scrubber) for acid gas control.
Hybrid systems have the advantages of both wet and dry systems (lower operating
temperature for capture of volatile metals, efficient collection of fine particulate,
efficient capture of acid gases), while avoiding many of the individual
disadvantages. In some hybrid systems, known as "zero discharge systems," the
wet scrubber liquid is used in the dry scrubbing operation, thus minimizing the
s amount of liquid byproduct waste.
* Uncontrolled HWIs: Facilities that do not use any air pollution control devices fall
under a separate and unique category. These are primarily liquid waste injection
facilities, which burn low ash and chlorine content wastes; therefore, they are low
emitters of PM and acid gases. ,
3.2.3. Estimation of CDD/CDF Emission Factors for Dedicated Hazardous Waste
Incinerators
i .-": ' ,
For purposes of estimating emission factors, this document considers subdividing
the combustors in each source category into design classes judged to have similar potential
for CDD/CDF emissions. As explained below, it was decided not to subdivide dedicated
HWIs. ,-.'•'•
Combustion research has identified three mechanisms involved in the emission of
CDD/CDFs from combustion systems: (IKCDD/CDFs can be introduced into the combustor
with the feed and pass through the system not completely burned/destroyed; (2) CDD/CDFs
can be formed by chemical reactions inside the combustion chamber; and (3) GDD/CDFs
can be formed by chemical reactions outside the combustion chamber. The total CDD/CDF
emissions are likely to be the net result of all three mechanisms; however, the relative
i^, . . •. • • .'.,••
3'17 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
importance of the mechanisms can vary among source categories. In the case of HWIs, the
third mechanism (i.e., post-combustion formation) is likely to dominate, because HWIs are
typically operated at high temperatures and long residence times, and most have
sophsiticated real-time monitoring and controls to manage the combustion process.
Therefore, any CDD/CDFs present in the feed or formed during combustion are likely to be
destroyed before exiting the combustion chamber. Consequently, for purposes of
generating emission factors, it was decided not to subdivide this class on the basis of
furnace type.
Emissions resulting from the post-combustion formation in HWIs can be minimized
through a variety of technologies:
* Rapid Flue Gas Quenching: The use of wet and dry scrubbing devices to remove
acid gases usually results in the rapid reduction of flue gas temperatures at the inlet
to the PM APCD. If temperature is reduced below 200°C, the low-temperature
catalytic formation of CDD/CDFs is substantially retarded.
* Use of Particulate Matter (Pm) Air Pollution Control Devices: PM control devices can
effectively capture condensed and adsorbed CDD/CDFs that are associated with the
entrained particulate matter (in particular, that which is adsorbed on unburned
carbon containing particulates).
* Use of Activated Carbon: Activated carbon injection is used at some HWIs to
collect (sorb) CDD/CDFs from the flue gas. This may be achieved using carbon beds
or by injecting carbon and collecting it in a downstream PM APCD.
All of these approaches appear very effective in controlling dioxin emissions at
dedicated HWIs, and insufficient emissions data are available to generalize about any minor
differences. Consequently, for purposes of generating emission factors, it was decided not
to subdivide this class on the basis of APCD type.
EPA compiled a data base summarizing the results of stack testing for CDDs and
CDFs at 17 HWIs (U.S. EPA, 1996c). Most facilities were tested between 1993 and
1996. For purposes of this report, CDD/CDF emission factors were estimated based on
the results of the emission tests contained in this data base. The breakdown of furnace
types of tested HWI facilities is as follows: 10 rotary kiln incinerators, 4 liquid injection
incinerators, 1 fluidized-bed incinerator, and 2 fixed-bed.
3'18 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
As stated earlier, EPA/ORD decided not to subclassify the dedicated HWI designs for
purposes of deriving an emission factor (EF). Instead, the EF was derived as an average
.across all 17 tested facilties. First, an average emission factor was calculated for each of
17 HWIs with Equation 3-3.
' EF - C X ^
*rhWi ~ j—r (Eqn. 3-3)
'•'
Where:
EFhwi = Emission factor(average ng TEQ per kg of waste burned).
C TEQ or CDD/CDF concentration in flue gases (ng TEQ/dscm) (20°C, 1
atm; adjusted to 7% O2j.
,F-V = Volumetric flue gas flow rate (dscm/hr) (20°C, 1 atm; adjusted to 7%
02^' • -•••/.•
lw = Average waste incineration rate (kg/hr).
After developing average emission factors for each HWI, the overall average congener-
specific emission factor was derived for all 17 tested HWIs using Equation 3-4.
(Eqn. 3-4)
Where:
EFHWI = Average emission factor of 18 tested MWIs ng/kg
Table 3-6 presents the average emission factors developed for specific congeners, total
CDDs/CDFs, and TEQs for operating HWIs. The average congener emission profiles for the
17 HWIs are presented in Figure 3-10. The average TEQ emission factor for the 17 tested
HWIs is 3.8-ng TEQ/kg of waste feed (assuming not detected values are zero).
3.2.4. Emission Estimates for Dedicated Hazardous Waste Incinerators
Although emissions data on a relatively high number of dedicated HWIs were
available (i.e., 17 of 162 have been tested), the emission factor estimate is assigned a
"medium" confidence rating due to uncertainties resulting from:
Extreme heterogeneity of the waste feeds. The physical and chemical composition
of the waste can vary from facility to facility and even within a facility.
3"19 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Consequently, CDD/CDF emissions measured for one feed may not be representative
of other feeds.
• Trial burns. Much of the CDD/CDF emissions data were collected during trial burns,
which are required as part of the RCRA permitting process and are used to establish
Destruction Rated Efficiency of principal hazardous organic constituents in the
waste. During trial burns, a prototype waste is burned, which is intended to
maximize the difficulty in achieving good combustion. For example, chlorine,
metals, and organics may be added to the waste. The HWI may also be operated
outside normal operating conditions. The temperature of both the furnace and the
APCD may vary by a wide margin {high and low temperatures), and the waste feed
system may be increased to maximum design load. Accordingly, it is uncertain how
representative the CDD/CDF emissions measured during the trial burn will be of
emissions during normal operating conditions.
Dempsey and Oppelt (1993) estimated that up to 1.3-rnillion metric tons of
hazardous waste were combusted in dedicated HWIs during 1987. The best estimate of
,; ' „.,!', ' •»• '
the amount of hazardous waste combusted in 1995 is 1.5-million metric tons (Federal
Register, 1996b). The activity level estimate for 1995 is assigned a "high" confidence
rating, because it is based on a thorough review of the various studies and surveys
conducted in the 1990s to assess the quantity and types of hazardous wastes being
managed by various treatment, storage, and disposal facilities. A confidence rating of
"medium" is assigned to the activity level estimate for 1987.
• '. ,»:
The annual TEQ emissions for the reference years 1995 and 1987 were estimated
using Equation 3-5.
(Eqn. 3-5)
Where:
EHW, = Annual emissions from all HWIs, tested and non-tested (g TEQ/yr)
= Mean emission factor for HWIs (ng TEQ/kg of waste burned)
= Annual activity level of all operating HWIs (million metric tons/yr)
Applying the average emission factor for dedicated HWIs (3.8-ng TEQ/kg waste) to
these production estimates yields estimated emissions of 5.7-g TEQ in 1 995 and 5.0-g TEQ
in 1987 for HWIs. The "medium" confidence rating assigned to the emission factor,
combined with the high confidence rating for the 1995 activity level and medium
3-20 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
confidence rating for the 1 987 activity level, yields an overall medium confidence rating for
both years. Accordingly, the estimated range of annual emissions is assumed to vary by a
factor of five between the low and high ends of the range. For 1 995, the range of TEQ
emissions is estimated to be 2.6- to 12.8-g TEQ/yr, For 1987, the range of TEQ emissions
is estimated to be 2. 2- to 11. 2-g TEQ/yr.
EPA/OSW has also developed estimates of the CDD/GDF emissions from dedicated
HWIs as part of the development of the Hazardous Waste Incineration Rule (U.S. EPA,
1997d). Like ORD, OSW also decided not to subdivide the dedicated HWIs on the basis of,
design. Instead of an emission factor approach, OSW used an imputation method to
estimate emissions at untested facilites. This procedure involved randomly selecting
measured CDD/CDF flue gas concentrations (ng/dscm) from the pool of tested HWI
facilities and assigning them to the untested facilites. With this procedure, all non-tested
HWIs have an equal chance of being assigned any flue gas concentration from the pool of
measured values. The flue gas concentrations were combined with flue gas flow rates for
each facility to estimate the emission rate. A key difference in these approaches is that
ORD uses waste feed rate directly in the calculation of emissions and the OSW approach is
independent of waste feed rate. Both procedures are reasonable ways to deal with the
broad range of uncertainties and both yield similar emission estimates. ORD has not
identified any inherent advantage of one approach over the other and elected to use the
emission factor approach primarily because it is consistent with the methods used in this
document to characterize CDD/CDF emissions from all other source categories.
3.2.5. Industrial Boilers and Furnaces Burning Hazardous Waste
In 1 991 , EPA established rules that allow the combustion of some liquid hazardous
waste in industrial boilers and furnaces (Federal Register, 1991c). These facilities typically
burn oil or coal for the primary purpose of generating electricity. Liquid hazardous waste
can only be burned as supplemental (auxiliary) fuel, and usage is limited by the rule to no
more than 5 percent of the primary fuels. These facilities typically use an atomizer to inject
the waste as droplets into the combustion chamber and are equipped with particulate and ;
acid gas emission controls. In general, they are sophisticated, well controlled facilities,
which achieve good combustion. <
The national data base contains congeneMspecific emission concentrations for two
tested boilers burning liquid hazardous waste as supplemental fuel. The average congener
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
'"' . ' • ii , , ,
and congener group emission profiles for the industrial boiler data set are presented In
Figure 3-11. The average congener and TEQ emission factors are presented in Table 3-6.
The limited set of emissions data prevented subdividing this class for the purpose of
deriving an emission factor. The equation used to derive the emission factor is the same as
Equation 3-4 above. The average TEQ emission factor for the two industrial boilers is 0.64-
ng TEQ/kg of waste feed. This emission factor is assigned a "low" confidence rating,
because it reflects testing at only 2 of the 136 hazardous waste boilers/furnaces.
Dempsey and Oppelt (1993) estimated that approximately 1.2-billion kg of
hazardous waste were combusted in industrial boilers/furnaces in 1987. EPA estimates
that in 1995 approximately 0.6-billion kg of hazardous waste were combusted in industrial
boilers/furnaces (Federal Register, 1996b). The activity level estimate for 1995 is assigned
a "high" confidence rating, because it is based on a thorough review of the various studies
and surveys conducted in the 1990s to assess the quantity and types of hazardous wastes
being managed by various treatment, storage, and disposal facilities (Federal Register,
1996b). A confidence rating of "medium" is assigned to the estimated activity level for
1987. The 1987 estimate was largely based on a review of State permits (Dempsey and
Oppelt, 1993).
Equation 3-5, used to calculate annual TEQ emissions for dedicated HWIs. was also
used to calculate annual TEQ emissions for industrial boilers/furnaces. Multiplying the
average TEQ emission factor of 0.64-ng TEQ/kg of waste feed by the total estimated kg of
liquid hazardous waste burned in 1995 and 1987 yields the annual emissions in g TEQ/yr.
From this procedure, the emissions from all industrial boilers/furnaces burning hazardous
Waste as supplemental fuel are estimated as 0.38-g TEQ/yr in 1995 and 0.77-g TEQ/yr in
1987. Because of th.e low confidence .rating for the emission factor, the overall confidence
rating is low for both the 1987 and 1995 emission estimates. Accordingly, it is assumed
that the uncertainty range around the best estimate varies by a factor of 10 between the
low and high ends of the range. Thus, the uncertainty ranges are 0.12- to 1.2-g TEQ/yr for
1995 and 0.24- to 2.4-g TEQ/yr for 1987.
3,3. MEDICAL WASTE INCINERATION
Medical waste incineration (MWI) is the controlled burning of solid wastes generated
primarily by hospitals, veterinary, and medical research facilities. The U.S. EPA defines
medical waste as any solid waste generated in the treatment, diagnosis, or immunization of
3"22 , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
humans or animals, or research pertaining thereto, or in the production or testing of
biologicals (Federal Register, 1997b). The primary purposes of MWI are to reduce the
volume and mass of waste in need of land disposal, and to sterilize the infectious materials.
The following subsections review the basic types of MWI designs used to incinerate
medical waste, review the distribution of APCDs used on MWIs, summarize the derivation
• of dioxin TEQ emission factors for MWIs, and summarize the national dioxin TEQ emission
estimates for reference years 1995 and 1987.
3.3.1. Design Types of MWIs Operating in the United States
For purposes of this document, EPA has classified MWIs into three broad technology
categories: modular furnaces using controlled-air, modular furnaces using excess-air, and
rotary kilns. Of the MWIs in use today, the vast majority are believed to be modular
furnaces using controlled-air. EPA has estimated that 97 percent are modular furnaces
using controlled-air, 2 percent are modular furnaces using excess air, and 1 percent are
rotary kiln combustors (U.S. EPA, 1997b).
Modutar Furnaces Using ControHed-air: Modular furnaces have two separate
combustion chambers mounted in series (one on top of the other). The lower chamber is
-where the primary combustion of the medical waste occurs. Medical waste is ram-fed into
the primary chamber, and underfire air is delivered beneath the incinerator hearth to sustain
good burning of the waste. The primary combustion chamber is operated at below
stoichiometric levels, hence the terms "controlled" or "starved-air." With sub-
stoichiometric conditions, combustion occurs at relatively low temperatures (i.e., 760 tp
985°C). Under the conditions of low oxygen-and low temperatures, partial pyrolysis of the
waste occurs, and volatile compounds are released. The combustion gases pass into a
second chamber. Auxiliary fuel (such as natural gas) is burned to sustain elevated
temperatures (i.e., 985 to 1,095°C) in this secondary chamber. The net effect of exposing
the combustion gases to an elevated temperature is more complete destruction the organic
contaminants entrained in the combustion gases emanating from the primary combustion
chamber. Combustion air at 100 to 300 percent in excess of stoichiometric requirement is
usually added to the secondary chamber. Gases exiting the secondary chamber are
directed to an incinerator stack (U.S. EPA, 1997b; U.S. EPA, 1991d; Buonicore, 1992b).
Figure 3-12 displays a schematic of a typical modular furnace using controlled-air. Because
of their low cost and good combustion performance, this design has been the most popular
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
choice for MWIs and has accounted for more than 95 percent of systems installed over the
past two decades (U.S.'EPA, 1990d; U.S. EPA, 1991d; Buonicore, 1992b).
Modular Furnaces Using Excess-air: These systems use the same modular furnace
configuration as described above for the controlled air systems. The difference is that the
primary combustion chamber is operated at air levels of 100 percent to 300 percent in
excess of stoichiometric requirements. Hence the name 7excess-air." A secondary
chamber is located on top of the primary unit. Auxiliary fuel is added to sustain high
temperatures in an excess-air environment. Excess-air MWIs are typically smaller in
capacity than controlled-air units and are usually batch-fed operations. This means that the
medical waste is ram-fed into the unit and allowed to burn completely before another batch
of medical waste is added to the primary combustion chamber.
Rotary Kiln MWI: This technology is similar in terms of design and operational
features to the rotary kiln technology employed in both municipal and hazardous waste
incineration. (See description in Section 3.1.) Because of their relatively high capital and
operating costs, few rotary kiln incinerators are in operation for medical waste treatment
(U.S. EPA, 1990d; U.S. EPA, 1991 d; Buonicore, 1992b).
MWIs can be operated in three modes: batch, intermittent, and continuous. Batch
incinerators burn a single load of waste, typically only once per day. Waste is loaded, and
ashes, are removed manually. Intermittent incinerators, loaded continuously and frequently
with small waste batches, operate less than 24 hours per day, usually on a shift-type basis.
Either manual or automated charging systems can be used, but the incinerator must be shut
down for ash removal. Continuous incinerators are operated 24 hours per day and use
automatic charging systems to charge waste into the unit in small, frequent batches. All
continuous incinerators operate using a mechanism to automatically remove the ash from
the incinerator (U.S. EPA, 1990d; U.S. EPA, 1991d).
3.3.2. Characterization of MWIs for Reference Years 1995 and 1987
MWI remains a poorly characterized industry in the United States in terms of
knowing the exact number of facilities operational over time, the types of APCDs installed
on these units, and the aggregate volume and weight of medical waste that is combusted
in any given year (U.S. EPA, 1997b). The primary reason for this is that permits were not
generally required for the control of pollutant stack emissions from MWIs until the early
1990s when State regulatory agencies began setting limits on emissions of particulate
3-24 Aprj| -I998
-------
DRAFT-DO NOT QUOTE OR CITE
matter and other contaminants (Federal Register, 1997b). Prior to that timeframe, only
opacity was controlled.
The information available to characterize MWIs comes from national telephone
surveys, stack emission permits, and data gathered by EPA during public hearings (Federal
Register, 1997b). This information suggests the following:
The number of MWIs in operation was approximately 5,000 in 1987 (U.S. EPA,
1987) and 2,375 in 1995 (Federal Register, 1997b).
• The amount of medical waste combusted annually in the United States was
approximately 1.43-billion kg in 1987 (U.S. EPA, 1987d) and 0.77-billion kg in 1995
(Federal Register, 1997b).
These estimates indicate that, between 1987 and 1995, the total number of operating
MWIs and the total amount of waste combusted decreased by more than 50 percent.
Certain activities caused this to occur, including more stringent air pollution control
requirements by State regulatory agencies and the development of less expensive medical
waste treatment technologies, such as autoclaving (Federal Register, 1997b). Because
many MWIs have small waste charging capacity (i.e., about 50 metric tons per day), the
installation of even elementary APCDs proved not to be cost effective. Thus, a large
number of facilities elected to close rather than retrofit. .
The actual controls used on MWIs on a facility-by-facility basis in 1987 are
unknown, and EPA generally assumes that MWIs were mostly uncontrolled (U.S.
EPA,1987d). However, the modular design does cause some destruction of organic
pollutants within the secondary combustion chamber. Residence time within the secondary
chamber is key to inducing the thermal destruction of the organic compounds. Residence
time is the time that the organic compounds entrained within the flue gases are exposed to
elevated temperatures in the secondary chamber. EPA has demonstrated with full-scale
MWIs that increasing residence time from 1/4 second to 2 seconds in the secondary
chamber can reduce organic pollutant emissions, including CDD/CDFs, by up to 90 percent
(Federal Register, 1 997b). In this regard, residence time can be viewed as a method of air
pollution control.
EPA estimates that about two-thirds of medical waste burned in MWIs in 1995 went
to facilities equipped with some method of air pollution control (FederalRegister, 1997b).
The types of APCDs installed and the methods used on MWIs include: dry sorbent injection.
3'25 • Ajfjril 1998
-------
DRAFT-DO NOT QUOTE OR CITE
fabric filters, electrostatic precipitators (ESPs), wet scrubbers, and fabric filters combined
with packed-bed scrubbers (composed of granular activated carbon). Some organic
constituents in the flue gases can be adsorbed by the packed bed. Within the uncontrolled
class of MWIs, about 12 percent of the waste were combusted in facilities with design
capacities of <200 Ibs/hr, with the majority of waste burned facilities >200 Ib/hr. The
estimated breakdown of controlled facilities is: 70 percent of the aggregate activity level
are associated with facilities equipped with either wet scrubbers, fabric filters, or ESPs;
29.9 percent are associated with facilities utilizing dry sorbent injection, combined with
fabric filters, and less than 1 percent is associated with facilities having the fabric
filter/packed-bed APCD (AHA, 1995; Federal Register, 1997b).
3.3.3. Estimation of CDD/CDF Emissions From MWIs
Only 1 percent of existing facilities (i.e., 24 MWIs) has been stack sampled for
CDD/CDFs. Consequently, most facilities have unmeasured emission levels of dioxin-like
il " H ' ' ' ' '! "I" • "' ' ' • , • '
compounds. Because so few have been evaluated, the estimation of annual air emissions
of CDD/CDFs from MWIs is quite dependent on extrapolations, engineering judgement, and
the use of assumptions. In addition, the information about the activity levels of these
facilities is also quite limited. With these data limitations, two approaches have been used
in the past to estimate CDD/CDF emissions from MWIs, and a third is proposed here.
These three approaches are as follows:
1- EPA/OAQPS Approach: EPA's Office of Air Quality Planning and
Standards used this approach in support of the promulgation of final
air emission standards for hospital/medical/infectious waste
incinerators (Federal Register, 1997b).,
2. AHA Approach: The American Hospital Association proposed an approach in
its comments on 'drafts of this document and on the proposed MWI emissions
regulations (AHA, 1995).
3. EPA/ORD Approach: In preparation of this document, EPA's Office of
Research and Development (ORD) has developed a third approach.
Given the limitations with existing information, both the EPA/OAQPS and AHA approaches
are reasonable methods for calculating annual releases of CDD/CDFs from MWIs. Both
methods relied heavily on a series of assumptions to account for missing information. In
developing a third approach, EPA/ORD built upon the other two approaches by utilizing the
3-26 . April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
most logical features of each. Because of the uncertainties with existing data, it is
currently hot known which approach gives the most accurate estimate of CDD/CDF air
emissions from all MWIs, nationwide. The three approaches yield different air emission
estimates, but the estimates all agree within a factor of four. As discussed below, the
EPA/ORD approach used the strengths of the other two approaches, and represents"some
improvement in estimating CDD/CDF emissions.
3.3.4. EPA/OAQPS Approach for Estimating CDD/CDF Emissions from MWIs
On September 15, 1997, EPA promulgated final standards of performance for new
and existing MWIs under the Clean Air Act Amendments (Federal Register, 1997b).
CDD/CDF stack emission limits for existing MWIs were established as follows: 125
ng/dscm of total CDD/CDF (at 7 percent O2, 1 atm), equivalent to 2.3 ng/dscm TEQ. In
order to evaluate emissions reductions that wil| be achieved by the standard, OAQPS
estimated, as a baseline for comparison, nationwide annual CDD/CDF emissions from all
MWIs operating in 1995.
3.3.4.1. EPA/OAQPS Approach for Estimating Activity Level
As a starting point for deriving the national estimates, OAQPS constructed an
inventory of the numbers and types of MWIs believed to be operating in 1995. The
inventory was based on ah inventory of 2,233 MWIs prepared by the American Hospital
Association (AHA, 1995), supplemented with additional information compiled by EPA. This
created a listing of 2,375 MWjs in the United States. Next a series of assumptions were
used to derive activity level estimates, as follows:
. - . j i ." . •• • . • • ' • •-.••.
1. The analysis divided MWIs into three design types based on the mode of
daily operation: batch, intermittent, and continuous. This was done using the
information from the inventory on design-rated annual incineration capacity of
each facility. The smaller capacity units were assumed to be batch
operations, and the others were classified as either intermittent or
continuous, assuming a ratio of three to one.
2. The activity level of each facility was estimated by multiplying the design-
rated annual incineration capacity of the MWI (kg/hr) by the hours of
- operation (hr/yr). The annual hours of operation were determined by
assuming a capacity factor (defined as the fraction of time that a unit
operates over the year) for each design type of MWI (Randall, 1 995). Table
3'27 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
1 ' ''•,
3-7 is a summary of the OAQPS estimated annual operating hours per IMWI
design type.
3.3.4.2. EPA/OAdPS Approach for Estimating CDD/CDF Emission Factors
Based on information obtained from AHA and State regulatory agencies, one-third of
the population of MWIs operating in 1995 was etimated to have had no APCDs (i.e., were
uncontrolled), and two-thirds had some type of APCD. CDD/CDF TEQ emission factors
were then developed for uncontrolled and controlled MWIs. The procedure was as follows:
Estimating TEQ Emission Factors for Uncontrolled Facilities: The uncontrolled
category of facilities was subdivided by residence time of the secondary combustion
chamber. Based on tests at three MWIs, OAQPS concluded that stack emissions of
CDD/CDFs from uncontrolled facilities were dependent on the residence time (i.e., the
duration of time the compounds are exposed to elevated temperatures within the secondary
combustion champer) (Strong, 1996). The tests demonstrated that when the residence
N|" , ' ; ,i • .,,
time in the secondary chamber was short (i.e., < 1 sec), the stack emissions of
CDDC/CDFs would increase; conversely, the longer the residence time (i.e., > 1 sec),, the
CDD/CDF emissions decrease. The emissions testing at these MWIs provided the basis for
the derivation of CDD/CDF TEQ emission factors for residence times of 1/4-sec, 1-sec and
2-sec. Table 3-8 is a summary of the emission factors developed for each MWI type as a
function of residence time. ;
The OAQPS inventory of MWIs in 1995 did not provide residence times for each
facility. OAQPS overcame this data gap by assuming that residence time in the secondary
combustion chamber approximately corresponds with the particulate matter (PM) stack
emission limits established in State air permits. This approach assumed that the more
stringent PM emission limits would require longer residence times in the secondary chamber
in order to further oxidize carbonaceous soot particles and reduce PM emissions. Table 3-8
lists the assumed residence times in the secondary chamber corresponding to various State
PM emission limits. State Implementation Plans (SIPs) were reviewed to determine the PM
emission limits for incinerators, and from this review, both a residence time and a TEQ
I , ' * ' ' ' ', '!'',"' "I ,':
emission factor were assigned to each uncontrolled MWI on the.inventory.
, ' , ' ' ;, ' ',' i1'!1 i|h • ' • ' - • '
Estimating TEQ Emission Factors for Controlled MWIs: Two-thirds of the MWI
population were assumed to have some form of APCD. AS previously discussed, APCDs
typically used by MWIs consist of one or more of the following: wet scrubber, dry scrubber,
3-28
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
and fabric filter combined with a packed bed. The EPA/OAQPS approach also included the
addition of activated carbon to the flue gases as a means of emissions control (i.e., dry
scrubbers combined with carbon injection). TEQ emission factors were developed for these
control systems based on incinerator emissions testing data gathered in support of the
regulations (U.S. EPA, 1997b). Because the inventory did not list the APCDs for all MWIs,
State requirements for PM control were used to make assumptions about the type of APCD
s -,"'*•'',,
installed on each facility in the inventory. These assumptions are summarized in Table 3-9.
3.3.4.3. EPA/OAQPS Approach for Estimating Nationwide CDD/CDF TEQ Air
Emissions
Annual TEQ emissions for each MWI facility were calculated as a function of the
design capacity of the incinerator, the annual waste charging hours, the capacity factor,
and the TEQ emission faptor as shown in Equation 3-6. - • -
Emnwi = (CxHx Cj ) x F.
TEQ (Eqn. 3-6)
Where-.
Emmwi = Annual MWI CDD/F TEQ stack emissions (g/yr)
C =, MWI design capacity (kg/hr)
H = Annual medical waste charging hours (hr/yr)
CT - Capacity factor (unitless)
FTEQ = CDD/CDF TEQ emission factor (g TEQ/kg)
The annual TEQ air emission of all MWIs operating in 1995 is the sum of the annual
emissions of each of the individual MWIs. The following equation is applied to estimate
annualTEQ emissions from all MWIs. ' - -
Emmm,m > (Eqn. 3-7)
Where:
Emmwi(nationw'de) = Nationwide MWI TEQ emissions (g/yr)
3-29. April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-9 is a summary of annual CDD/CDF TEQ emissions for 1995 estimated using the
EPA/OAQPS Approach.
3.3.5. AHA Approach for Estimating CDD/CDF Emissions from MWIs
In 1995, the American Hospital Association (AHA) submitted written comments to
EPA in response to EPA's request for public comment of the 1994 draft public release of
this document (AHA, 1995). As part of these comments, the AHA attached an analysis of
CDD/CDF emissions from MWIs prepared by Doucet (1995) for the AHA. Doucet (1995)
estimated the total number of MWIs operating in 1995, the distribution of APCDs,
CDD/CDF TEQ emission factors, and tfoe nationwide TEQ emissions. The following is a
brief discussion of the AHA inventory and the Doucet (1995) analysis.
From a natipnal telephone survey of member hospitals conducted between
September and November 1994, the AHA developed what is generally considered as the
first attempt to systematically inventory MWIs in the United States. Approximately 6
percent of the hospitals with MWIs were contacted (AHA, 1997). The AHA survey showed
that, as of December, 1994, 2,233 facilities were in operation. Doucet (1995) subdivided
the AHA MWI inventory into two uncontrolled categories on the basis of combustor design-
rated capacity and two controlled categories on the basis of APCD equipment. Doucet
(1995) then developed CDD/CDF emission factors for each category of MWIs. Test reports
of 19 MWIs were collected and evaluated. Average CDD/CDF TEQ flue gas concentrations
(i.e., ng/dscm @7 percent O2) were derived by combining tests from several MWIs in each
capacity range category and APCD. The average TEQ flue gas concentrations were then
converted to average TEQ emission factors, which were in units of Ib TEQ/106 Ibs of
medical waste incinerated (equation for conversion not given). Table 3-10 is a summary of
TEQ emission factors calculated by Doucet (1995) for each level of assumed APCDs on
MWIs.
Similar to the EPA/OAQPS Approach (Section 3.3.4), the distribution of the APCD
categories was derived by assuming that State paniculate emission (PM) limits would
indicate the APCD on any individual MWI (Doucet, 1995). Table 3-11 displays the AHA
assumptions of air pollution control (APC) utilized on MWIs based upon PM emission limits.
With the activity levels, the percent distribution of levels of controls, and the
CDD/CDF TEQ emission factors having been calculated with existing data, the final step of
the AHA Approach was the estimation of annual TEQ emissions (g/yr) from MWIs,
3-30 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
nationwide, Although no equation is given, it is presumed that the emissions were
estimated by multiplying the activity level for each MWI size and APCD category by the
associated TEQ emission factor. The sum of these calculations for each designated class
yields the estimated annual TEQ emissions for all MWIs, nationwide. Doucet (1995)
indicates that these computations are appropriate for TEQ emissions in 1995. Table 3-12
summarizes the nationwide annual TEQ emissions from MWIs using the AHA Approach.
3.3.6. EPA/ORD Approach for Estimating CDD/CDF Emissions from MWIs
Because of limitations in emissions data and on activity levels, the EPA/ORD
approach used many of the logical assumptions developed in the EPA/OAQPS and AHA
approaches. The discussion below describes the rationale for how these decisions were
made, and presents the resulting emission estimates.
3.3.6.1. EPA/ORD Approach for Classifying MWIs and Estimating Activity Levels
As with the EPA/OAQPS and AHA approaches, the EPA/ORD approach divided the
MWIs into controlled and uncontrolled classes. The decisions about further dividing these
two classes are described below:
Uncontrolled MWIs: For purposes of assigning CDD/CDF emission factors and
activity levels to the uncontrolled class of MWIs, the EPA/OAQPS approach divided this
class on the basis of residence time within the secondary combustion chamber. This
approach has theoretical appeal, because it is logical to expect more complete combustion
of CDD/CDFs with longer residence times at high temperatures. Unfortunately/the
residence times on a facility-by-facility basis are not known, making it difficult to assign
emission factors and activity levels on this basis. As discussed earlier, the EPA/OAQPS
approach assumed that residence time would strongly correlate with State PM stack
emission requirements (i.e., the more stringent the PM requirements, the longer the
residence time required to meet the standard). This PM method for estimating residence
time resulted in the following distribution of residence times: 6 percent of the waste
incinerated at MWIs with 1/4-sec residence time; 26 percent of the waste incinerated at
MWIs with 1-sec residence time; and 68 percent of the waste incinerated at MWIs with 2-
sec residence time. Thus, about two-thirds of the activity level within the uncontrolled
class were assumed in the EPA/OAQPS approach to be associated with facilities with the
longest residence time and the lowest CDD/CDF emission factor.
3-31 Aprii 1998
-------
DRAFT-DO NOT QUOTE OR CITE
The AHA approach subcategorized the uncontrolled class on the basis of design-
rated capacity. There is also theoretical support for this approach. Smaller capacity
operations (i.e., <200 Ib/hr) are likely to have higher emissions, because they are more
likely to be operating in a batch mode. The batch mode results in infrequent operation with
more start-up and shut-down cycles. Thus, the batch-operated MWI usually spends more
time outside of the ideal range of operating conditions. In support of this approach, the
AHA presented limited empirical evidence indicating that CDD/CDF emission factors
calculated from emission test reports for the low capacity units were about a factor of two
higher than the emission factors for the high capacity units (Doucet, 1995).
Thus, both the EPA/OAQPS and AHA approaches have a sound theoretical basis but
lack strong supporting data. In order to decide which of the two approaches to use, ORD
first tested the assumption that there is a strong relationship between State PM
requirements and residence time. ORD conducted a limited telephone survey of regulatory
agencies in four States where a large number of MWI facilities were in operation: Michigan,
Massachusetts, New Jersey, and Virginia (O'Rourke, 1996). The results of the limited
survey, summarized in Table 3-13, did not verify the existence of a strong dependent
relationship between PM emission limits and residence time in the secondary chamber at
MWIs.
Next, the available emission testing data for small and high capacity units (i.e., less
than and greater than 200 Ib/hr) were evaluated to determine if, as posited in the AHA
approach, smaller capacity units have greater emission factors than large capacity units.
This evaluation indicated a distinct difference in the emission factors between the two
capacity categories, although the difference in the set of data evaluated was not as great
as the difference observed in the data set evaluated in the AHA approach. The EPA/ORD
approach, therefore, adopted the subcategorization scheme used in the AHA approach.
Controlled MWIs: Both the EPA/OAQPS approach and the AHA approach
subcategorized the controlled MWIs on the basis of APCD equipment. However, the two
approaches differed in the subcategories developed. The AHA approach divided the
controlled class into two groups: facilities equipped with wet scrubbers (alone, with an
ESP, or with a fabric filter), and facilities equipped with dry sorbent injector and a fabric
filter (Doucet, 1995). The EPA/OAQPS approach divided the controlled class into three
groups: facilities equipped with wet scrubbers, facilities equipped with dry scrubbers (with
or without carbon injection), and facilities equipped with fabric filters and packed bed
3'32 . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
scrubbers. This third category is comprised of a few facilities primarily located in the
Northeast United States (O'Rourke, 1996). The EPA/ORD approach adopted the two
subcategories of the AHA approach and the third subcategory of the EPA/OAQPS
approach. For 1995, ORD used the activity levels for each facility as determined by the
EPA/OAQPS inventory; the activity levels were then summed across facilities for each
APCD subclass.,
For 1987, the EPA/ORD approach assumed that every MWI was uncontrolled on the
basis of a EPA study of MWI incineration conducted at that time (U.S. EPA, 1987d). This
study indicates that MWIs operating in 1987 did not need controls, because they were not
subject to State or Federal limits on either PM or organic pollutant emissions. The activity
level estimates were derived from additional EPA studies (U.S. EPA, 1987d). this approach
resulted in the following activity level assumptions for 1987: (3) 15 percent of the activity
level (i.e., 0.2-billion kg medical waste) were incinerated/yr by MWIs with capacities less
than or equal to 200 Ib/hr, and (b) 85 percent of the activity level (i.e., 1-billion kg/yr) were
incinerated by facilities with capacities greater than 200 Ib/hr.
3.3.6.2. EPA/ORD Approach for Estimating CDD/CDF Emission Factors
EPA/ORD collected the engineering reports of 24 tested MWIs. After reviewing
these test reports, 19 met the criteria for acceptability. (See Section 3.1.3 for further
details on the criteria.) In some cases, CDD/CDF congener-specific data were not reported,
ori values were missing. In other cases, the protocols used in the laboratory analysis were
not described; therefore, no determination of the adequacy of the laboratory methods could
be made. .
The EPA stack testing method (EPA Method 23) produces a measurement of
CDD/CDFs in units of mass concentration (i.e., nanograms per dry standard cubic meter of "
combustion gas (ng/dscm)) at standard temperature and pressure and one atmosphere and
adjusted to a measurement of 7 percent oxygen in the flue gas (U.S. EPA, 1995b). This
concentration is assumed to represent conditions at the point of release from the stack into
the air, and to be representative of routine emissions. The emission factors were derived
by averaging the emission factors across each tested facility in a design class. The emission
factor for each tested MWIs was calculated using the following equation:
3-33
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
C x Fv
EFmwi = J (Eqri. 3-8)
W . '
Where:
EFmwi - Emission Factor per MWI (average ng TEQ per kg of medical
waste burned).
C = Average TEQ concentration in flue gases of tested MWIs (ng
TEQ/dscm) (20°C, 1 atm; adjusted to 7% O2).
Fv = Average volumetric flue gas flow rate (dscm/hr) (20°C, 1 atm;
adjusted to 7% O2).
lw = Average medical waste incineration rate of the tested MWI
(kg/hr). '
The emission faqtor estimate for each design class and the nurriber of stack tests used to
derive it are shown in Table 3-14. Figures 3-12 and 3-13 present congener and congener
group profiles for air emissions from MWIs lacking APCDs and for MWIs equipped with a
wet scrubber/baghouse/fabric filter APCD system, respectively. -
3.3.7. Summary of CDD/CDF Emissions From MWIs
Because the stack emissions from so few facilities have been tested (i.e., 19 test
reports) relative to the number of facilities in this industry (i.e., 2,375 facilities in 1995 and
5,000 facilities in 1987) and because several tested facilities are no longer in operation or
have installed new APCD after testing, the EPA/ORD approach did not calculate nationwide
< , i •.....• . , . -
CDD/CDF emissions by calculating emissions from the tested facilities and adding those to
calculated emissions for the non-tested facilities. Rather, the EPA/ORD approach (as well
as the EPA/OAQPS and AHA approaches) calculated nationwide CDD/CDF emissions by
multiplying the emission factor and activity level developed for each design class and then
summing the calculated emissions for all classes. Tables 3-14 and 3-15 summarize the
resulting national TEQ air emissions for the reference years 1995 and 1987, respectively.
In addition, the Tables indicate the activity level and the TEQ emission factor used in
estimating annual TEQ emissions!
In estimating annual TEQ emissions in both reference years, a "low" confidence
rating was assigned to the estimate of the activity level. The primary reason for the low
confidence rating is that very limited information is available on a facility level basis for
characterizing MWIs in terms of the frequency and duration of operation, the actual waste
3-34
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
volume handled, and the level of pollution control. The 1987 inventory of facilities was
based on very limited information. Although the 1995 EPA/OAQPS inventory was more
comprehensive than the 1987 inventory, it was still based on a fairly limited survey of
operating facilities (i.e., approximately 6 percent).
The emission factor estimates were given a "low" confidence rating, because only
the reports of 1.9 tested MWI facilities could be used to derive emissions factors
representing the 2,375 facilities operating in 1995 (i.e., less than 1 percent of estimated
number of operating facilities). Even fewer tested facilities could be used to represent the
larger number of facilities operating in 1987 (i.e., 8 tested facilities were used to represent
5,000 facilities). The limited emission tests available do cover all design categories used
here to develop emission factors. However, because of the large number of facilities in
each of these classes, it is very uncertain whether the few tested facilities in each class
capture the true variability in emissions. .
• Reference Year 1995: Based on the low confidence ratings for both the activity
level and the emission factor, the estimated range of potential annual TEQ emissions
from MWIs in 1995 is assumed to vary by a factor of 10 (between the low and high
ends of the range). From Table 3-14, the central estimate of TEQ emissions in 1995
is estimated to be 477 g/yr, with a range of 1 51 to 1,510 g TEQ/yr.
• Reference Year. 1987: Based on the low confidence ratings for both the activity level
and the emission factor, the estimated range of potential annual TEQ emissions from
MWIs in 1987 is assumed to vary by a factor of 10 (between the low and high ends
of the range). From Table 3-15, the central estimate of TEQ emissions in 19S7 is
estimated to be 2;470 g/yr, with a range of 781 - to ,7,810-g TEQ/yr.
As explained above, the EPA/ORD approach to estimating national CDD/CDF TEQ
emissions is a 'hybridization' of the EPA/OAQPS and AHA approaches. Table 3-16
compares the main features of each of the three approaches. The 1995 TEQ emissions
estimated here (477-g TEQ/yr) are about 3.5 times higher than those of QAQPS and AHA
(141- and 138-g TEQ/y, respectively). Most of this difference is due to differences in the
• , ' ' '
emission estimates for the uncontrolled facilities (ORD% - 436-g TEQ/yr, OAQPS - 136-g
3-35
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
TEQ/yr, AHA - 120-g TEQ/yr). An analysis of the differences in how these groups
estimated emissions from the uncontrolled facilities are presented below:
• Differences between the EPA/ORD and AHA Approaches: The ORD approach
adopted the classification scheme of the AHA approach for the uncontrolled class
and assumed similar activity levels. Thus, the difference in emission estimates is
primarily due to differences in the emission factors used. Both groups use similar
emission factors for facilities with design capacities less than or equal to 200 Ibs/h,
but the emission factor for MWIs > 200 Ibs/hr used in the EPA/ORD approach was
higher than that used in the AHA approach by a factor of three. This results from
the fact that the two approaches used different sets of emission tests to derive their
emission factors.
• Differences between the EPA/ORD and EPA/OAQPS Approaches: Because the two
approaches subcategorized the uncontrolled facilities into different classes, the
activity levels and emission factors cannot be directly compared. Considering the
class as a whole, however, both approaches used essentially identical activity levels.
The EPA/OAQPS approach assigned 68 percent of the total activity to the class with
the lowest emission factor (i.e., those with >2-sec residence time). The emission
factor for this class, 74-ng TEQ/kg, is considerably lower than either emission factor
a'1 ' ' i . • ' '
used in the EPA/ORD approach (1,700- and 1,860-ng TEQ/kg).
11 , „ • '" ; - , ( " • \ i
Given the uncertain data base available for making these estimates, it is difficult to
know which of these three estimation approaches yields the most accurate annual TEQ
estimate. However, despite the differences in methodologies and assumptions used, the
three approaches yield annual TEQ estimates that are not fundamentally different; the
estimates differ from each other by a factor of four or less. Because the EPA/ORD
approach was the last of the three to be developed, it has the benefit of being able to
utilize the most logical and supportable features of the previously developed EPA/OAQPS
and AHA approaches.
Regardless of the approach taken to estimate what the CDD/CDF emissions from
2,375 MWIs were in 1995, the National Emission Standards promulgated by EPA in
September 1997 (Federal Register, 1997b) require substantial reductions of CDD/CDF air
3"36 April 1998
-------
DRAFTS-DO NOT QUOTE OR CITE
emissions from MWIs. As a result of these standards, MWI emissions will be thoroughly
assessed for purposes of compliance with the CDD/CDF standard. Compliance testing will
allow the development of a more comprehensive emissions data base and more accurate
characterization of this industry.
3.4. CREMATORIA
Bremmer et al'. (1994) categorized crematoria into two basic operating types: a
"cold" type and a "warm" type. In the "cold" type furnaces, the coffin is placed inside at a
temperature of about 300°C. Using a burner, the temperature of the chamber is increased
to 800-900°C and kept at that temperature for 2 to 2.5 hours. In the "warm" type
furnace, the coffin is placed in a chamber preheated to 800°C or higher for 1.2 to 1.5
hours. The chamber exhausts from both furnace types are incinerated in an after burner at
a temperature of about 850°C. Flue gases are then discharged to the atmosphere either:
(a) directly without cooling; (b) after mixing with ambient air using an air blast to a
temperature of about 20Q-350°C; or (c) after mixing with ambient air as in "b," followed by
further cooling to about 150°C in an air cooler and passage through a fabric filter.
Bremmer et al. (1994) measured CDD/CDF emissions at two crematoria in The
Netherlands. The first, a cold-type furnace with direct uncooled emissions/was calculated
to yield 2.4-^g TEQ per body. The second furnace, a warm type with cooling of flue gases
to 220°C prior to discharge, was calculated to yield 4.9-//g TEQ per body. The higher-
emission rate for the warm-type furnace was attributed by Bremmer et al. (1994) to the
formation of CDD/CDF during the intentional cooling of the flue gases to 220°C.
Jager et al. (1992) (as reported in Bremmer et al., 1994) measured an emission rate
of 28-^9 TEQ per body for a crematorium in Berlin, Germany. No operating process
information was provided by Bremmer et al. (1994) for the facility.
In the United States, CDD/CDF emissions were measured at one crematorium
(GARB, 1990c) classified as a warm-type facility using the criteria of Bremmer et al.
(1994). The combusted material at this facility was comprised of the body, as well as 4
pounds of cardboard, up to 6 pounds of wood, and ,an unquantified amount of unspecified
plastic wrapping. The three emission tests conducted at this facility yielded an average
emission factor, of 0.5-^g TEQ/body. Although this emission factor is very similar to the
emission factors reported by Bremmer et ai. (1994), a "low" confidence rating is assigned
to the factor, because it represents testing at only one U.S. facility. Table 3-17 presents
3-37
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
the congener-specific emission factors for this facility. Figure 3-14 presents CDD/CDF
congener and congener group emission profiles based on these emission factors.
In 1995, 1,155 crematories were reported in the United States (Springer, 1997).
However, there are no readily available data on the number of "cold" versus "warm"
crematoria furnaces. In 1995, 21.1 percent of the deceased bodies were cremated (i.e.,
488,224 cremations), and 15.2 percent of the deceased were cremated in 1987 (i.e.,
323,371 cremations) (Springer, 1997). Cremations are projected to increase to 25 percent
in the year 2000 and 37 percent in the year 2010 (Springer, 1997). A high confidence
rating is assigned to these activity level estimates, because they are based on recent data
provided by the Crematoria Association of North America.
Combining the emission rate of 0.5-yug TEQ/body with the number of cremations in
1995 (488,224) yields an estimated annual release of 0,24-g TEQ per year. Based on the
low confidence rating assigned to the emission factor of 0.5-^g TEQ/body, the estimated
range of potential emissions is assumed to vary by a factor of 10 between the low and high
ends of the range. Assuming that the best estimate of annual emissions (0.24-g TEQ/yr) is
the geometric mean of this range, then the range is calculated to be 0.07- to 0.75-g
TEQ/yr. Combining the emission rate of 0.5-^g TEQ/body with the number of cremations in
1987 (323,371) yields an estimated release of 0.16-g (range 0.05- to 0.51-g TEQ/yr).
3.5. SEWAGE SLUDGE INCINERATION
;' '' i " ' ' • , • , ,-.,,„' • ' . ,
The three principal combustion technologies used to incinerate sewage sludge in the
United States are the multiple-hearth incinerator, fluidized-bed incinerator, and the electric
furnace (Brunner, 1992; U.S. EPA, 1995b). All of these technologies are "excess-air"
processes (i.e., they "combust sewage sludge with oxygen in excess of theoretical
requirements). Over 80 percent of operating sludge incinerators are multiple-hearth design.
About 15 percent are fluidized-bed incinerators, and 3 percent are electric incinerators.
Other types of technologies not widely used in the United States are single-hearth
cyclones, rotary kilns, and high-pressure wet-air oxidation (U.S. EPA, 1997b).
Multiple-hearth Incinerator: This consists of refractory hearths arranged vertically in
series, one on top of the other. Dried sludge cake is fed to the top hearth of the furnace.
The sludge is mechanically moved from one hearth to another through the length of the
furnace. Moisture is evaporated from the sludge cake in the upper hearths of the furnace.
The center hearths are the burning zone, where gas temperatures reach 871 °C. The
3-38
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
bottom hearths are the burn-out zone, where the sludge solids become ash. A waste-heat
boiler is usually included in the burning zone, where steam is produced to provide
supplemental energy at the sewage treatment plant. Air pollution control measures
typically include a venturi scrubber, an impingement tray scrubber, or a combination of
both. Wet cyclones and dry cyclones are also used (U.S. EPA, 1995b).
" ' •
Fluidized-bed Incinerator: This is a cylindrical refractory-lined shell with a steel plate
structure that supports a sand bed near the bottom of the furnace (Brunner, 1992). Air is
introduced through openings in the bed plate supporting the sand. This causes the sand
bed to undulate in a turbulent air flow; hence, the sand appears to have a .fluid motion
when observed through furnace portals. Sludge cake is added to the furnace at a position
just above this fluid motion of the sand bed. The fluid motion promotes mixing in the
combustion zone. Sludge ash exits the furnace with the combustion gases; therefore, air
pollution control systems typically consist of high-energy venturi scrubbers. Air pollution
control measures typically include a venturi scrubber or venturi/impingement tray
combinations (U.S. EPA, 1995b).
Electric Furnaces: Also called infrared furnaces, these consist of a long rectangular
refractory-lined chamber. A belt conveyer system moves the sludge cake through the
length of the furnace. To promote combustion of the sludge, supplemental heat is added
by electric infrared heating elements within the furnace that are located just above the
traveling belt. Electric power is required to initiate and sustain combustion. Emissions are
usually controlled with a venturi scrubber or some other wet scrubber (Brunner, 1992; U.S.
EPA, 1995b).
EPA measured CDD/CDF emissions at two multiple-hearth incinerators and one
fluidized-bed incinerator as part of Tier 4 of the National Dioxin Survey (U.S. EPA, 1987a).
The results of these tests include congener group concentrations in stack gas, but lack
measurement results for specific congeners other than 2,3,7,8-TCDD and 2,3,7,8-TCDF. In
1 995, the Association of Metropolitan Sewerage Agencies (AMSA) submitted to EPA the
results of stack tests conducted at an additional 15 sewage sludge incinerators (Green et
alv, 1995). Two of these data sets were considered not useable by EPA, because either
detection limits or feed rates and stack flow were not provided. The average congener and
congener group emission factors are presented in Table 3-18 for the three facilities from
U.S. EPA (1987a) and the 13 AMSA facilities from .Green ef al. (1995). A wide variability
was observed in the emission factors for the tested facilities. The total CDD/CDF emission
3-39
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
factor for the three U.S. EPA (1987a) facilities ranged from 90 to 3,400 ng/kg. For the 13
facilities reported in Green et al. (1995), a similarly large variability in emission factors was
observed. Figure 3-15 presents the average congener and congener group profiles based
on these data.
The average TEQ emission factor based on the data for the 13 AMSA facilities is
6,94-ng TEQ/kg of dry sludge combusted, assuming nondetected values are 0 and 7.19-ng
TEQ/kg of dry sludge, assuming nondetected values are present at one-half the detection
limit. Other countries have reported similar results. Bremmer et al. (1994) reported an
emission rate of 5-ng TEQ/kg for a fluidized-bed sewage sludge incinerator, equipped with a
cyclone and wet scrubber, in The Netherlands. Cains and Dyke (1994) measured CDD/CDF
emissions at two sewage sludge incinerators in the United Kingdom. The emission rate at
an incinerator equipped with an electrostatic precipitator and wet scrubber ranged from
2.75-ng TEQ/kg to 28.0-ng TEQ/kg. The emission rate measured at a facility equipped
with only an electrostatic precipitator was 43.0-ng TEQ/kg.
In 1992, approximately 199 sewage sludge incineration facilities combusted about
0.865-million metric tons of dry sewage sludge (Federal Register, 1993b). No comparable
data are available for the 1987 and 1995 reference time periods. For purposes of this
report, it is assumed that 0.865-million metric tons of dry sewage sludge were incinerated
during the two time periods. Given this mass of sewage sludge incinerated/yr, the estimate
of TEQ emissions to air is 6.0-g TEQ per year, using the average AMSA TEQ emission
factor of 6.94-ng TEQ/kg.
in . " « ; - , ' „ „ , ,
A "medium" confidence rating is assigned to the average TEQ emission factor for
the AMSA facilities (6.94-ng TEQ/kg), because it was derived from stack testing at 13
sewage sludge incinerators. The activity level estimate is assigned a "high" confidence
rating, because it is based on an extensive EPA survey to support rulemaking activities.
Based on these confidence ratings, the estimated range of potential annual emissions is
assumed to vary by a factor of five between the low and high ends of the range. Assuming
that the estimate of annual emissions (6.0-g TEQ/yr) is the geometric mean of this range,
then the range is calculated to be 2.7- to 13.4-g TEQ/yr.
3.6. TIRE COMBUSTION
Emissions of dioxin-like compounds from the incineration of automobile tires were
measured from a tire incinerator stack tested by the State of California Air Resources Board
3"40 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
(CARB, 1991 a). The facility consists of two excess air furnaces equipped with steam
boilers to recovery the energy from the heat of combustion. Discarded whole tires were
fed to the incineration units at rates ranging from 2,800 to 5,700 kg/hr during the 3 test
days. The furnaces are equipped to burn natural gas as auxiliary fuel. The steam produced
from the boilers is used to drive electrical turbine generators that produce 14.4 megawatts
of electricity. The facility is equipped with a dry acid gas scrubber and fabric filter for the
control of emissions prior to exiting the stack.
Emission factors for CDD/CDF and TEQ in units of ng/kg of tires combusted were
derived ,as average values from the one facility stack tested in California (CARB, 1991 a)'.
Table 3-19 presents the congener-specific emission factors for this facility. Figure 3-16
presents CDD/CDF congener and congener group profiles based on these emission factors.
From these data, the average emission factor is estimated to be 0.282-ng TEQ/kg of tires
incinerated when all not detected values are treated as zero. Cains and Dyke (1994)
reported much higher emission rates for two tire incinerators equipped only with simple grit
arresters in the United Kingdom, 188- and 228-ng TEQ/kg of combusted tire.
EPA estimated that approximately 0.50 million metric tons of tires were incinerated
in 1990 in the United States (U.S. EPA, 1992a). This activity level estimate is given a
"medium" confidence rating, because it is based on both published data and professional
judgement. The use of scrap tires'as a fuel was reported to have increased significgntly
during the late 1980s; however, no quantitative estimates were provided in U.S. EPA
(1992a) for this period. In 1990, 10.7 percent of the 242-million scrap tires generated
were burned for fuel. This percentage is expected to continue to increase (U.S. EPA,
1992a). Of the tires burned for energy recovery purposes, approximately 46 percent were
utilized by pulp and paper facilities, 23 percent were utilized by cement kilns, and 19
percent were utilized by one tire-to-energy facility (U.S. EPA, 1995c).
If it is assumed that 500-million kilograms of discarded tires are incinerated annually
in the United States, then, using the emission factors derived from staqk data from the one
tested facility, an average of 0.14 grams of TEQ per year are estimated to be emitted to
,, the air. It must be noted that these may be underestimates of emissions from this source
category, because the one facility tested in California is equipped with a dry scrubber
combined with a fabric filter for air pollution control. These devices are capable of greater
than 95 percent reduction and control of dioxin-like compounds prior to discharge from the
stack. It is hot know to what extent other tire incineration facilities operating in the U.S.
3-41
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
are similarly controlled. If such facilities are not so equipped, then the uncontrolled
emission of CDD/CDF and TEQ could be much greater than the estimates developed above.
1 ,' ' ' • ' '" ' ', . ' ' H' '
Therefore, the estimated emission factor of dioxin from tire incineration is given a "low"
confidence rating. Based on these confidence ratings, the estimated range of potential
annual emissions is assumed to vary by a factor of 10 between the low and.high, ends of
the range. Assuming that the best estimate of annual emissions (0.14-g TEQ/yr) is the
geometric mean of this range, then the range is calculated to be 0.04- to 0.45-g TEQ/yr.
3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED CHEMICAL PULP MILLS
Approximately 20.5 percent of the wastewater sludges generated at bleached
chemical pulp mills are dewatered and burned in the facilities' bark burners. These sludges
can contain CDD/CDFs and fairly significant levels of chloride. However, the level of heat
input from sludge in the mixed feed rarely exceeds 10 percent in most bark boilers (NCASI,
1995).
NCASI (1995) provided congener-specific test results for four wood residue/sludge
boilers tested between 1987 to 1993. The congener-specific emission factors derived from
the stack test results obtained frpm one of these facilities (a spreader stoker equipped with
an ESP) are presented in Table 3-20. During testing, the sludge feed rate averaged 3,,2
tons per hour, and the feed rate for wood residue averaged 30.3 tons per hour. The
average TEQ emission factors derived from the test results are O.OQ1 ng/kg of feed (i,,e.,
sludge and wood residue), assuming nondetected values are 0 and 0.005 ng/kg of feed,
assuming nondetected values are present at one-half the detection limit. The average TEQ
concentration in the stack gas reported for this facility by NCASI (1995) was 1.4E-04
ng/dscsm (at 12 percent CO2). The results of testing of stack emissions at the other three
boilers burning sludge, wood residue, and coal were reported by NCASI (1995) to have
significantly higher (i.e., factors of 41 to 207 times greater) average TEQ concentrations in
the stack gases. However, reliable emission factors for these facilities could not be
derived, because stack gas flow rates and sludge feed rates were not available.
NCASI (1995) also presented stack emission test results for five other bark boilers,
at least one of which normally fires bark in combination with sludge and coal. Although
stack gas flow rates were obtained during these tests, accurate measurements of the
amounts of bark/wood fired were not measured and thus had to be estimated by NCASI
(1995). The average congener and congener group emission factors derived from the test
3-42
April 1998
-------
' ; . '• DRAFT-DO NOT QUOTE OR CITE
results at these facilities are also presented in Table 3-20. Figure 3-17 presents the
congener and congener group profiles based on these data. The average TEQ emission
factor for these facilities is 0.4 ng/kg of feed or 80 to 400 times greater than the emission
factor derived for the sole facility burning sludge and wood for which complete test results
and operating parameters are available. This average TEQ emission factor is very similar to
the average emission factor for industrial wood combustion derived in Section 4.2.2 of this
report from testing by the California Air Resources Board of four industrial wood
combustors (0.82 ng/kg of feed). /
The available emissions test results for combustion of bleached Kraft mill
wastewater sludge are not adequate to enable derivation of CDD/CDF emission factors
specific to these bark/sludge combustors. However, the emissions test data presented in
NCASI (1995), and discussed above, indicate that the CDD/CDF emission factors for
bark/sludge combustors are similar to the emission factor developed in Section 4.2.2 for
industrial facilities burning only wood residues/scrap. Thus, based on this conclusion about
the applicability of the industrial wood combustor emission factor, and the fact that wood
residues comprise a far greater fraction of the feed to these burners than does sludge, the
national TEQ emission estimates derived in Seption 4.2.2 of this report for industrial wood
burning facilities are assumed to include emissions from these bark/sludge combustion
units.
3.8. BIOGAS COMBUSTION ,
Schreiner et al. (1992) measured the CDD/CDF content of a flare combusting
exhaust gases from an anaerobic sewage sludge digester in Germany: The CDD/CDF
content at the bottom of the flare was 1.4-pg TEQ/Nm3, 3.3. pg TEQ/Nm3 at the top of the
flare, and 13.1 pg TEQ/Nm3 in the middle of the flare. Congener-specific results were not
reported. Using the theoretical ratio of flare gas volume to digester gas volume combusted,
78.6:1, and the average CDD/CDF content of the three measurements, 5.9-pg TEQ/Nm3,
an emission rate of 0.46-ng TEQ/Nm3 of digester gas combusted is yielded.
During 1996, POTWs in the United States treated approximately 122-billion liters of
wastewater daily (U.S. EPA, 1997c). Although reliable data are not readily available,on the
amount of sewage sludge generated by POTWs that is subjected to stabilization by
anaerobic digestion, a reasonable approximation is 25 percent of the total sludge generated
(i.e., the sludge generated from treatment'of about^O-trillion liters per day of wastewater).
3~43 . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
An estimated 196 kg of sludge solids are generated for every million liters of wastewater
subjected to primary and secondary treatment (Water Pollution Control Federation, 1990).
Thus, multiplying 30-billion liters per day (i.e., 25 percent of 122-billion liters) by 196
kg/million liters and 365 days/yr yields an annual estimate of 2-million metric tons of sludge
solids that may be anaerobically digested in POTWs annually.
The volume of sludge digestor gas combusted in flares annually can be estimated
using operation parameters for a "typical" anaerobic digestor system as described in Water
Pollution Control Federation (1990). Multiplying the annual amount of sludge solids of 2-
million metric tons by the following parameters and appropriate conversion factors yields an
annual flared digestor gas volume of 467-million Nm3:
'ii ; • , " ' .
• Fraction of total solids that are volatile solids = 75 percent;
• Reduction of volatile solids during digestion = 50 percent;
• Specific gas production = 0.94 m3/kg volatile solids reduced; and
• Fraction of produced gas that is flared = 66 percent.
Because there are no direct measurements of CDD/CDF emissions from U.S.
anerobic sludge digestor flares and because of uncertainties about the activity level for
biogas combustion, no national emission estimate has been developed for inclusion in the
national inventory. However, a preliminary order of magnitude estimate of the potential
annual TEQ emissions from this source can be obtained by multiplying the emission factor
of 0.46-ng TEQ/Nm3 of digestor gas flared by the estimated volume of gas flared annually
in the United States, 467-million Nm3. This calculation yields an annual potential release of
0.22 grams, which, when rounded to the nearest order of magnitude to emphasize the
uncertainty in this estimate, results in a value of 0.1-g TEQ/yr. This estimate should be
regarded as a preliminary indication of possible emissions from this source category; further
'•.'.'.•• . - • •
testing is needed to confirm the true magnitude of these emissions.
3-44
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Figure 3-1. Typical Mass Burn Waterwall Municipal Solid Waste Incinerator
Source: U.S. EPA (1997b)
3^45
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Figure 3-2. Typical Mass Burn Rotary Kiln Combustor
* i ,,...' •«, ,/ • •
Source: U.S: EPA (199?b)
3-46
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Figure 3-3. Typical Modular Excess-Air Combustor
Source: U.S. EPA (1997b)
3-47
ApriU-998
-------
DRAFT-DO NOT QUOTE OR CITE
ToStackcr
Waste Ha BAr
Riray
fed
Qute
///////////// J
Secondary
Ssxndary
Charter
TTT
o o o
o o o
o o o
JM>
^—
Rimy Charter
RreDoor
TrEnsferftrtB
Seooncby
GBsBirer
fet\
Qjercti
Poroyfir
Figure 3-4. Typical Modular Starved-Air Combustor with Transfer Rams
Source: U.S. EPA (1997b)
3-48
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
apaheeter
Safe
Figure 3-5. Typical Dedicated RDF-Fired Spreader Stoker Boiler
Source: U.S. EPA (1997b)
3-49
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Thermocouple
Sludge
Inlet
Fluidlzing
Air Inlet
Exhaust and Ash
Pressure Tap
Sight
Glass
Burner
Tuyeres
m
i
— i
KeTractory
Arch
i
J
IWindbox
•— S
1
tel
i
— i
Fuel Gun
Pressure Tap
Startup
Preheat
Burner
for Hot
Windbox
Figure 3-6. Fluidized-Bed RDF Incinerator
Source: U.S. EPA (1997b)
3-50
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Watemall
-
Refractory
Walled
DS/FF
HrESP
-
WS
DS&F
H-ESP
Muncipal Solid Waste
Incinerator Design
Classes for 1987
I — •- • — L- , :
MM* Bum
- \
Refute-Derived Fuel
i
I
Modultr
Key: DS/FF = Dry Scrubber combined with a Fabric Filter
H-ESP = Hot-side Electrostatic Precipitator (Temperature at control device is >230°C)
WS = Wet Scrubber
UNO = Uncontrolled (no APCD)
EGB = Electro Granular Activated Carbon Bed
FF = Fabric Filter
Figure 3-7. MSWI Design Classes for 1987
3-51
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Muncipal Solid Waste
Incinerator Design
Classes for 1995
Watttwt*
-
DS/FF
OStfF
DS1CVFF
DSC-ESP
DSm-ESP
DSIKVH-ESP
C-ESP
H-ESP
I
Mil} Bum
I
I
Retractor/
Walled
-
WS
C-ESP
DSFF
DSlfFF
I
Rotary Kin
Combustor
|
C-ESP
DSI/C-ESP
DSI/FF
DS/FF
Refuse-Derived Fuel
1
I
Dedicated
Stoker-boiler
F
DS/FF
DSI/FF
DS/C-ESP
DSI/H-ESP
C-ESP
H-ESP
DSfcF/C-ESP
I
luldized-bed
DS/FF
DSI/FF
DSI/EGB
Starv&d-air
Modular
Uncontrolled
. C-ESP
H-ESP
WS
WS/FF
DSI/FF
DS/DSI/C-ESP
1
Excess-air
Uncontrolled
C-ESP •
WS/C-ESP
DS/FF
DSI/FF
DSI/H-ESP
H-ESP
Key: DS/FF = Dry Scrubber combined with a Fabric Filter
DSI/FF = Dry Sorbent Injection coupled with a Fabric Filter
DS/CI/FF = Dry Scrubber -Carbon Injection-Fabric Filter
C-ESP - Cold-side Electrostatic Precipitator (Temperature at control device is below =;2300C)
H-ESP - Hot-side Electrostatic Precipitator (Temperature at control device is
WS = Wet Scrubber
UNC = Uncontrolled (no APCD)
EGB = Electro Granular Activated Carbon Bed
Figure 3-8. MSWI Design Classes for 1995
3-52
April 1998
-------
H
O
cx
H
O
o
Q
ti
UH
>
—I
>*
•D
CD
Q"
U
a.
CO
_o
o
o
0)
XI
in.
ro
H
U*"™* Wrf
05
OS
O
0)
to
£ «
2
JQ
CD
„ *»1| CM
' - "1 "
*• ^J
Si
,1,
|!
«B|
5 w
tn /j
~f 3 £
J
0.
f
*ll
d
- It
tn
a
>UI
i
, to
a
i-. s,
UJ
"33
o
o
II
'I
5
.
p
'
CM
CD
P
p
P .
P
P
P
P
CM
P
CM
P
P
No.
Facilities
I 2.10E+09JI
P
p
80+369'Z
5.07E+08
P
p
p
p
p
p
p
1.14E+09
P
g
4-
UJ
o
q
CM
O
o
CD
15
o J
m
S
>
CM
O
-
O
o
o
-
o
o
0
0
CM
• o
-
0
0
•1
ll
1.18E+09J
g
UJ
s
CM
O
1.13E+08
o
o
o
4.22E+08
p
o
o
o
2.68E+08
0
1.69E+08
o .
o
If
fc
£T
CD
I"
o
o
CM
0
-
o
CO
O
O
0
CO,
s *
-
CO
to
O
No.
Facilities
If"
o
0
1.97E+08
O
2.75E+08
0
2.31E+09
o
o
o
.8
+
UJ
8.57E+09
4.22E+08
2.81E + 09
1.04E+09
o
If
m
•o
-
-'
^°
o
o
o
o
o
o
o
-
o
0
0
0
No.
Facilities
S
Ul
to
to
CO
o
1.13E+08
8.45E + 07
o
o \
o
o
o
o
0
0
1.69E + 08
o
o
o
o
; _r
u.
Q
tr
m
,
O
o
-
o
O ,
O
-
p
o
p
-
*-,
•t
-
p
il
f II n
p
o
4.22E+08
o
p
. p
1.75E+0*
p
p
5.63E+08
p
2.51E+09
g
+
CM
1.81E+09
4"22E+07
P
If
RDF/Ded
CO
o
•-
p
•p
-
p
p
-
p
p -
. p
p
.«
"
OJ
i-
6.80E+08
4.90E+07
O
3.24E+07J
o
0
7.60E+07
o
o
2.82E+07
o
o
o
o
1.25E + 08
1.82E.+08
1.87E+08
|f
g<
I"
p
p
-
p
p
p
p
--
p
p
p
- ]
CO
-
S
4.18E + 08
p
p
1.01E + 08
p
p
.p
p
6.76E+07
p
P
P ,
80 + 381H
1.41E+07
8.28E+07
1.97E+07
1.41E+07
J-
> -QJ
IJJ
S
s Ml
• |j i
in
-'
tn
to
CO
'- '
-
-
CO
5.
CO
CM .
CM
CM
O
S
4
(5
o
2.53E+08 I
8.
+
UJ
CO
1.21E+09 |
5.07E+08
2;75E+08 |
7.60E+07 |
4.49E+09
6.76E+07 |
2.82E+07 |
5.63E+08
1.17E+09,
1.28E + 10 |
6.37E+08 |
5.19E+09 |
1.29E+09 |
2.01 E +08 |
JE "3
S
-5
00
G>
o.
<
00
IA
CO
-------
u- S
e>
s c c
o •£ **
S o .2.
.2. . £
C fc- 4J
CO
CD
3
•S
o
0 » II
II 11. m
u. i O
ti; O li£
to Si 55
Q Q a
CO
o>
O)
Q.
<
- S
S 2
4-r Q.
S 8 fe
s —
CD r5 _ > CD
CD XI
— I— _o
o 2 CD 3
ir o o
t co
2 » 2
O "il 2 t II m
O O C/3 n CD
13 I O Q t UJ
in
oo
-------
ID
o
<
"55
.c
<
TJ
CQ
Q"
O
D_
• <
>^
D)
_O
O
JZ
O
.2
^D
r>-
oo
ro
B.
MH
U
g
B *
O ^2
Z3- ^
a w
H ^
% °
O
•Q
o
CO
_0)
J2
1 4
,-
&•
'to
'
o
cc.
CD
0
CM
^
O
O
"-
OJ
o
No. of
Facilities
CD
o
LU
0
CO
CO
o
+
LU
O
CO
o
o
^
o
LU
^t
'-
CO
o
~r
LU
O
q
oi
'
°
i_
ll
LU
DC
m
o
o
o
0
~ ,
CO
o
No. of
Facilities
CO
O
LU
LD
CO
.LD
O
0
0
00
O
LU
LD
LD
*-
O
-(-
LU
0
.04
LD
O
l_
•I ~*
J$. w
< _J
"^ '' ' '
^
CD
j
CO
CM ,
O
o
0
!>.
0
No. of
Facilities -
to
CO
0
LU
LD
CO
CO
00
o
LU
CO
CO
CO
o
o
o
8
-}- >
LU
t~
O
CO
o
^•5.
^1
< J
CD
0
T3
OJ
Q
LL
Q
tr .
CO
o
o
o
o
CO
o
No. of
Facilities
CO
o
LU
CO
LD
CM '
O
0
-
\
o
o
00
o
-f_
LU
CO
LO
CM
O
- -
If
T3 • . ' -
.^
O
0
LL.
Q
CC
00
o>
O)
Q.
<
LO
10
CO
-------
CO
LO
"fr
_ -
O
.<
1
ro u.
Q "-
f\ II il
< "
>^ II 1
CT> (I I]
fcj 51 co
u ° OB
w II II '
w .0 II
fc? oo 1 to
O en j LU
2, c II o
L, CO 1 CM
O ~- 1 —
25 w |j ||
b H o
9 1- =>|
5 1 ^
3 > u il
Q £ 0> I
. CM || 1^1
Sll to 11 ?H
1 •=: « o
-2 I I ^ ro
If II
a>
o
"T*
LU
LO
*~
r-
o
4-
LU
O
CO
LO
O
00
o
+
LU
CO
xl
^
O
00
0
LU
r**»
^
*~
00
o
-f
LU
CO
to'
k_
>.^>
;l -5
*^ >
1
1
II *r
1 ^
11 o
O
II ^
•*
^
T—
O
.
o
0
CM
No. of
Facilities
00
o
•(-
LU
CO
CO
CM'
00
o
_}.
LU
CM
^
o
LU
CO
r**
CO
o
0
o
^
o
LU
5
_>•
.•e"-*!
LU
Q
0
^
CO
^
*-
T—
"*
CN
^.
LO
CO
CO
"5
d co
15 S
O CD
1— LL.
o
-f-
LU
00
CO
*-
O)
o
_l_
LU
CM
^
o
+
LU
CO
r^»
CD
00
0
oS
LO
^
00
o
LU
CD
0)
CM
o
LU
CM
T-
^
00
o
LU
LO
CO
>.
'•i-3 -^
< ^
'
*
^ ,
o
to
'5. iS
'5 ±!
fl) II
tt o
£ ^
S LL
*5 -5 • TJ ,_
« f m g
LU V — >.
T3 -. ^3 f «-
= 2 = ^111
£: »$5f e
g ° ^.iZ 2 ° £
C M Q •— qj S ^
r> II "m ^ ^ "^
2 S ! i g 2» S'
1) -X. C\ uL \^ ^ S
-
"S ^
== "a
03 Tn
§ "° .** O
QJ i_ (^
c >.= . " fe CO ? "O
£T 2 4= 3 _ CD CO
5 'S 5 "S « £ cS
O rr > DC •— <" O
CC .— *t rr* ^
C; C "a O CO LU
3 m m IS LL JS CD
CD ,. O Q 3 "5
„ [g | =5 DC •§ -g
<§ 5 5 Q II 2 2
^ II II "O II II
|| II " O "
0 LU ^ * 'S W m
CC CC ^ -£J Q Q
CO CO CO f~\ f~\ CD'O
^ «cr ^ "r; '"-| «^ ^r
S ^ ^ DC CC S S
oo
o>
a>
a.
<
CD
LO
CO
-------
c
o
CD
"5
C
CO
CD
O
CO
"co
a.
"o
"c
3
o
M—
S^
CD
frj
rj
H- (
O
^
^^
S
O.
P'
|
O
9
i
03
Q.
;a
LU
. |—
03
c_
CO
o
•*-»
o
CO
LL
• • c
o
"OT
OT
E
LU
a
LU
X
o
G
CO
CO
_03 ,
LQ
CD
03
: CO
' . O
CO
DC
"O
• • ' . -C
CO
OT
OT
a j»
LU ^£
1- 03
c c
03.2 T
CO OT 0
o5 -52 2
> E co
< LU U.
.2
"4->
3
"o O 03
£ '£ .2
c >
.- ;.o. 03
< U a
."5
"o
u.
— o
to i!
Q- CO
'O 03 m H.
= » I "s
3 .JO. o 03
2 5 = a
03
3
03 "ti
iH -CO
5 03
CD O-
03 E
0- 03
f= *^
•2 o
f~\ CL.
8 < •
Q_ • *-
< , ^5
fe • • .i
•~ OT
'55 . g
•i-1 C
OT C
O -n
E . c
_ CO
C 03
CD 0
s 1
CD 3
C - H-
^ CD
' C
M
CD "5
E m
£ a:
« CO ,.
Ou i
co x
LU ^
U ^
CO
Q OT OT OT OT OT Q OT
-•. OT co to- co OT .. co
>03CDQ303CD>CD
>OC3ot3'o>U
SS.TJ.'O' 73 =0 T> 2 =0
CCCCCCCC
oooooooo
~O ~O ~O ~O ~O "O ~O "a
03 CD 03' 03 03 03 03 03
OTOTOTOTOTOTOTOT
COCOCOCOCOCDCOCD
CQCaCQCacacamCa
n ^ r- it-
*~™ *~ LO CD r^ 03 r^» .^
CDCOr1- OI^»— l">>«^-
Q.
co
LU n '
LU LJ_ =E ^ LU
H'cowcocococoH1
o Q Q Q a a a x
n — •
3 g
03 >
k.
W 03
OT +-1 '
CD CO
55
03
•H
CO
Q R Q 03
o y o a.
°- 2? °- E
< < < 5
| 1 1 Q
C. n* L_- f
CD s *T (0
CD ^ CD g
nn "« r^ *•
E .§ E §
OT w OT 3
nil
•* **
•.ii •« tf
LL. H- 0- "
u- ti: co Q;
co co H1 co
£3 « Q Q I LU
« OT .».».» CJ
UC3 > ^ > DC
i ii i
•5 ^5 2 2 2 S
c c. c c c c
o p o o o o
T3 "O "O "O T3 -Q
CD 03 03 03 CD > CD
OT OT OT OT OT OT
CO CO CD 'CO CO CO
DO 03 03 03 03 03
r- CO r- "
M LO O »— Tf CN
Q.
CO
O O LL tt CO
H1 co co co H' J2
O Q Q Q X 5
c >.
3 O
0 CO '
0 *™
!E DC .
- -
2 S • '8
c c c
0 0 0
0 0 0
c c c
.2 .2 .°
OT 'OT 'OT
OT OT OT
'E "E- .'E
CD CD CD
JO CD CD *
I E 1'.
CO CO CO
•a -o -a
c c .c
CD. CO CD
03 03 03
O 0 O
CO CD , CO
C C , C
V- i— k.
H— M— H-
tD CD CD
E E E
CO CD CO
OT OT CO
^ ^ «.
LL. LL. LL
LL LL LL
CO to Jo co CO to
a OT a to a to1
.^ CD .^ CD 03
^ 0 Of 0 Of 0
n £ 03 £ 03 £
c c c c 'c c
o o o o o o
TJ T3 T3 T3 ~O ~O
03 03 03 03 03 03
OT OT OT OT to OT
CD CO CO .CD CD CO
03 O3 DO 03 03 03
1
CD
•* ^
^ • ^^ 1^^ ^^ 00
^ O ^J- ^d- >* CN
a.
co
LU
O_ LL f') H- CL
0 LL !=J it CO
*V CO CO CO u. ^
O Q Q Q.LL X
C c
3 5
OT CO
0 *""
S DC
03
^
"o "o -P
i: 4= E
C C 03
O O Q
O^ O c
c c c
0 O +-
Q 'w "co Q
0 -^ -!2 0
Q_ c c Q
< CD CD <
u. i- ^- L_
CO CO CO C
III 1
"OT OT "OT "to
TJ -o -a -a
c c c c
i CO CD CD C
03 03 03 03
0 O O O
CO CD CO Cl
C C C C
1_ I- >_ 1_
333 3
M— M— *^- H—
03 03 CD 03
E E-E , E
CO CD CD CC
OT W .CO CO
•* ^ •. *.
U- Q- Q- D.
LL CO CO CO
r^ LU LU LU
\JJ I ' 1 = 1
OT OT CO Q O O W U
OT 03 OT. • - • - ' - tO • -
CDCDCD^^^CD^
^^^999^9
«-•'»- i- Q Q Q £ C
•o TS TD oc DC o: .Ha DC
cccccccc
oooooooo
0)0303030303030;
OT OT OT OT OT OT OT K
COCOCOCDCDCOCDCC
CQ CQ CQ CQ CQ 03 CQ CO
CN ^ ^ °
NOO.OCM
-------
T3
a>
c
I
I
'o
CO
a.
'5
'E
3
CD
CO
C
to
DC
•o
c
CO
.52
to
CO
CO
O "ff
LJJ sS
1- ra
0 g£
2 $ 2
> 'E to
< UJ U_
c
.0
3
"o s 8
D- +; •—
— O CD
< O Q
"o
to ,_
• — o
CO +J
f?, CO
« 2 ® &
i S ~ «
3 ro o to
2 5 J= 0
CD CD
— — 33
O 0 4jj 4jj
C C CD CD
O O Q. Q.
oo E E
C C CD CD
O O CO +-• +J
Q 1 1 .i 8 8
o "E 'E So °- °-
< ® ® i ^ "f
Q) CD CO 0 CO CO
|1 I 0 1 1
to 'to co o to to
"O "CJ "U3 ~ T3 T3
c c c S- c c
CD CO CD « CO CO
"E ~c "c jg "B "B
"53 "53 '53 '5 "53 '53
CD Q) CD CD CD
73 73 73 CO "O TO
CO CO CO to CO CO
33 3 §33
*O *U "O C "U "U
o o o _ o o
JEJE E c j=E
CD CD ID m CD CD
oo o 500
CO CO CO m CO CO
c c c c c: c
33 3 ^ 3 3
**~ **~ **~* Vf_ **"~ **~~
J§ CO CO 05 CO CO
1 1 1 * 1 E
'(/>*(/> w "55 *eo
co to co ==; co co
UJ UJ UJ ^ UJ UJ
66+2642066
.» .-to .^ to ... ... ...
^r ^r ^ ^f ^ <£ ^r ^
ujuj ^uj ^couiui
•6-a "-a "T-JTJTJ
oo£o£ooo
2275^75^22
cccccccc
oooooooo
T3TJ73737373737D
CDCDCDCDCDCDCDCD
cocococococococo
cocococococococo
CQ CQ CQ CQ CQ CO CO CQ
r-. r-.
CM CM
-^0-t^Ot-r-
Q.
CO
HI
1
o
D. W U- Q. U-
co Q ^ co o =;:
UJyjyjUJ^tOCO
oaau_x=>55
k.
"co
CO "O
D >
o fo
2 GO
-(— •
CO
E '
CO
CD
CD
>
O
>-
CO to CO
E Q § §
1 t * .__ .«
O co co
Q Q_ co co
^ < I I CD
^* C ~^
C CO CD 0 £
— co -g £ £
£ 73 CD CD £•
3 C CO Q. O. E
•«± CO c X X CD
2 a, o 0 0 +-
0 O 'co J- >- Q Q
Q. CD .tO .CO JS Q (J
E E 'E 'p 'E D_ D_
S £$% I < <
m C — 'w to — —
E -i5 '£ | | E E
"53 0 to *- ^ 'to "co
73 ^ -0 ^ "g T3 -0
co _ _ to co co
o -5 ® S S o Q>
I III III
^3 i_ —^ M— *^- -3 ^
"~ JS "^ 0 0 "£ "^
to "53^ g g g g g
UJ CO "J CO CO UJ UJ
to .^ .> ., .^ to .^ .^ .^
^ . >
_ CO CC
1 E E
CO i i
000
O 0 0
CO CO CC
c c c
L_ h_ k_
333
v^_ 14— kf_
CD CO CC
I 1 1
'to 'tO 'c/5
1 1 1 1 1 1
UL LL. LL
CO CO CO
Q Q Q
• >. • ». • •
> > ^>
555
CQ CO CO
222
c c c
000
73 73 73
000
CO CO CO
CO CO CC
CO CQ CO
CO CO CO
CD CD CD
odd
CO
„ O u_
LL. itt ||
U- UJ LL
CO CO CO
Q Q Q
73
0
^
0
N
12 u_
3 Q
LL CC
2 o
CO ~
CO JO
> to
> 4-
to co
CO 4->
II
^ 0
v- C
0 J5
^E
a o
UJ O
ll
CO 3
1. L
OJ O
O co
CO ^~
"Z. Q
u.
«
H—
O
't-
J2
CO
CD
£L
0
Q.
3
O
o
c
o
"4-1
0
.0_
'c
c
0
JD
o
CO
M—
O
CO
4—
CO
73
C
CO
c
o
o
0
JET
c
0
.Q
CO
O
JZ
4->
?
73
0
Q.
3
O
o
0
JD
3
O
CO
t—
Q
II
O
o
o
CM
CM
O
0
_CO
0
O
0
73
"5
c
0
o
CO
£
3
to
L_
0
Q.
E
0>
4-(
•*—
B
CO
4-<
"o.
"o
£
Q.
0
*4->
CD
4-J
CO
E
s
0
"53
73
0
73
"to
73
O
0
II
0
o
o
CM
CM
0
O
CO
to
0
_o
0
"5
4-*
o
o
to
0
k_
3
4-*
CO
0
Q.
E
0
i2>
I—
o
ecipitat
k_
a.
o
'•t-i
CD
ctrost
0
0
73
0
'53
4-*
o
I
II
0
.a
3
o
to
0
II
Q
O
a.
o
c
73
"ci
C
O
O
II
00
O)
O)
Q.
<
CO
up
00
73
0
J3
C
O
ja
CD
o
73
0
4-t
CD
'-P
O
CD
k.
.2
"3
c
CO
g 9>
O
CD
UJ
Q
II LL
c Q Q Q O
CD
LU
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-4 Annual TEQ Emissions (g/yr) From MSWIs Operating in 1995
Municipal Solid Waste
Incinerator Design
Mass Burn Rotary Kiln
RDF Dedicated
!
'
Fluidized-bed RDF
Air Pollution
Control
Device
C-ESP
DS/C-ESP
DS/CI/FF
DS/FF
DSI/CI/H-ESP
DSI/FF ,
DSI/H-ESP
H-ESP
C-ESP
DS/C-ESP
DS/FF
DSI/FF
ws
C-ESP
DS/FF
DSI/C-ESP
DSI/FF
C-ESP
DS/C-ESP
DS/FF
DSI/FF
DSI/H-ESP
H-ESP
DS/FF/C-ESP
C-ESP
DSI/FF
H-ESP
UNC
WS
WS/FF
DS/DSI/C-
ESP
C-ESP
DS/FF
0SI/FF
DSI/H-ESP
H-ESP
UNC
WS/C-ESP
DS/FF
DSl/EGB
DSI/FF
Emissions
From Tested
Facilities
(gTEQ/yr)
0
2.09
0.635
2.01
2.12
0.279
0
163
170
39.8
21.6
0
0
- 0
61.4
0
0.245
0
5.29
5.54
32.5
0.321
0.0975
0
0
0
0
33
0
,0.000801
8.01
0
0
0
0
8.01
0.0643
0
0
0
2.32
0
0
2.39
0
0
0
0
280
Average TEQ
Emission
Factor
(ng/kg)
6.1
6.1
1.5
0.63
7.74
473
.-
0.63
1.91
236
47
0.646
47
47
231
0.527
0.24
231
231
1490
0.24
16
79
0.0247
16
16
16
16
. 16
0.0247
118
0.0247
16
0.63
0.63
0.63
.Activity Level
s* Non-Tested
Facilities
(kg/yr)
2.81e+09
1.88e + 09
7.44e + 08
5.98e + 09
o
0
4.22e + 08
1.79e + 08
0
0
2.68e + 08
1.136 + 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
6.25e + 07
1.18e + 08
1.01e4-08
1.41e + 07
0
1.41e + 07
6.76e+07
1.69e + 08
1.13e + 08
8.45e + 07
Emissions From
Non-Tested
Facilities
(g TEQ/yr)
17.1
11.4
1.12
3.77
0
3.27
84.5
121
0
0
J 0.168
0.216
48.1
48.5
9.4
0.489
23.8
6.85
40.6
385
0.603
0.379
97.6
46.2
63
0.135
593
2
0
6.34
0.00463
0.785
0.451
1.22
10.8
1
1.9
0.00251
1.66
0,
0.000348
, 1 .08
5.64
0.106
0.0709
0.0532
0.231
Total
Emissions
From All
Facilities
(g TEQ/yr)
17.1
13.5
1 75
5.77
0.279
3.27
247
291
39.8
21 6
0.168
0.21 6
48.1
110
9.4
0.734
23.8
12.1
46.1
418
0.924
0.477
97.6
46.2
63
0.135
626
.0.000801
14.4
0.00463
0.785
0.451
1.22
18.8
1 07
1 9
0.00251
1.66
2 32
0.000348
1.08
8.03
0.106
0.0709
0.0532
0.231
Key: DS/FF = Dry Scrubber combined with a Fabric Filter
DSI/FF = Dry Sorbent Injection coupled with a Fabric Filter " .
DS/CI/FF = Dry Scrubber -Carbon Injection-Fabric Filter
C-ESP = Cold-side Electrostatic Precipitator (Temperature at control device is below =;2300C)
H-ESP = Hot-side Electrostatic Precipitator (Temperature at control device is >230°C)
WS = Wet Scrubber
UNC = Uncontrolled (no APCD)
EGB = Electro Granular Activated Carbon Bed
ng/kg = nanogram per kilogram
kg/yr = kilograms per year , '
3-59
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-5. Annual TEQ Emissions to the Air From MSWIs Operating in 1987
Incinerator Design
Mass Burn Waterwall
Mass Burn Refractory
Mass Burn Rotary Kiln
RDF Dedicated
RDF Cofired
Modular Starved-air
Pollution
Control
Device
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
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
Average TEQ
Emission
Factor
(ng/kg)
473
0.63
473
236
47
285
1490
231
231
16
79
0.0247
16
0.0247
0.0247
16
Activity Level
Non-Tested
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
Emissions From
Non-Tested
Facilities
(g TEQ/yr)
0
1550
1550
0.0887
944
212
1,160
0.741
64.2
65
. 3660
78.1
3730
58.6
2.29
28.5
0.0142
0.848
31.6
0.00167
0.00103
2.03
2.03
Total Emissions
From All
Facilities
(g TEQ/yr)
0.0373
1980
1980
0.0887
944
212
1,160
0.741
112
113
4500
78.1
4570
58.6
2.29
28.5
0.0142
0.848
31.7
0.001 67
0.00103
2.03
2.03
Key: DS/FF = Dry Scrubber combined with a Fabric Filter'
DSI/FF - Dry Sorbent Injection coupled with a Fabric Filter
DS/CI/FF = Dry Scrubber -Carbon Injection-Fabric Filter
C-ESP = Cold-side Electrostatic Prepipitator (Temperature at control device is below d230°C)
H-ESP = Hot-side Electrostatic Precipitator (Temperature at control device is *230°C)
WS - Wet Scrubber
UNC = Uncontrolled (no APCD)
EGB *= Electro Granular Activated Carbon Bed
ng/kg = nanogram per kilogram
kg/yr ~ kilograms per year '
3-60
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
0.02
(congener emission factor / total CDD/CDF emission factor)
0.04
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
0.12
Ratio (congener group emission factor / total CDD/CDF emission factor)
°-05 0.1 0.15
Figure 3-9. Congener and Congener Group Profiles for Air Emissions from a Mass-Burn
Waterwall MSWI, Equipped with a Dry Scrubber and Fabric Filter
3-61
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-6. CDD/CDF Emission Factors for Hazardous Waste Incinerators and Boilers
I Congener/Congener Group
|| 2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1 1,2,3.4,7,8-HxCDD
1 1,2,3,6,7.8-HxCDD
1,2,3,7,8,9-HxCDD
| 1,2,3,4,6,7,8-HpCDD
I OCDD
I 2,3,7,8-TCDF
I 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 '
I Total TEQ (nondetects = 0)
Total TEQ (nondetects =1/2 DL)
I Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF {nondetects = 0)
Total CDD/CDF (nondetects = 1/2 DL)
Incinerator Average
Mean emission factor
(17 facilities)
ing/kg feed)
Nondetects
Set to 1/2
Det. Limit
0.44
0.18
0.22
0.32
0.49
1.77
4.13
2.96
2.36
2.56
9.71
3.96
0.31
2.70
16.87
1.74
13.78
4 22
137.36
=• L
Nondetects
Set to
Zero
0.14
0.14
0.18
0.28
0.48
1.75
3.74
2.69
2.33
2.51 .
9.71
3.95
0.29
2.70
16.68
1.71
13.46
3.83
137.36
- — .
Hot-Side ESP Boilers I
Mean emission factor |
(2 facilities)
(ng/kq feed) li
Nondetects
Set to 1/2
Det. Limit
0.10
0.11
0.15
0.20
0.22
1.17
5.24
0.81
0.38
0.52
0.83
0.37
0.08
0.56
1.04
0.18
0.70
0.78
0.77
1.15
1.67
2.34
5.24
5.47
. 5.50
4.04
1 94
0.70
28.83
Nondetects
Set to
Zero
0.00
0.04
0.08
0.18
0.20
1 17
5.24
0.81
0.38
0152
0,83
0.37
0.02
0.56
0.93
0.16
0.70
0.64
0.77
0.77
1.62
2.34
5:24
5.47
5.51
4.04
1 CIA
0.70
28.83
ng/kg - nanograms per kilogram
Source: U.S. EPA <1996c).
3-62
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
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 3-10. Congener Profile for Air Emissions from Hazardous Waste Incinerators
3"63 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor /total CZ3D/CDF emission factor)
°-OS 0.1 0.1S
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-HxCJDD
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-P*CDF
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-axCDF
1,2.3,4,6,7.8-HpCDF
1,2,3,4,7.8.9-HpCDF
1.2.3.4,6,7,8.9-dCDF
O.2
Ratio (congener group emission factor / total CDD/CDF emission factor)
0-05 0.1 0.15 0.2
0.2S
Figure 3-11. Congener and Congener Group Profiles for Air Emissions from
Boilers and Industrial Furnaces Burning Hazardous Waste
3-64
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-7. Summary of Annual Operating Hours for Each MWI Type
" t -/
MWIType
Continuous
commercial
Continuous
onsite
Intermittent
Batch
Capacity Ranges <
«b/hr} -
> 1,000
501 - 1,000
> 1,000
^ 500
Case by case
Annual charging t
hours
• ' (hr/yrf ^
7,776
1,826
2,174
1 ,250
Case by case
i Maximum annual
charging hours
8,760
5,475
4,380
Capacity
0.89
0.33
0.40
0.29
Ib/hr = pounds per hour
hr/yr = hours per year
3-65
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-8. OAQPS Approach: PM Emission Limits for MWIs and Corresponding
Residence Times in the Secondary Combustion Chamber
MWIType
Intermittent and
Continuous
Batch
PM Emission Limit8
(gr/dscf }
2:0.3
0.16 to < 0.30
0.10 to <;0.16
;> 0.079
0.042 to < 0.079
0.026 to < 0.042
Residence Time in
2° Chamber
(seconds) ;:
0.25
1.0
2.0
0.25
1.0
2.0
TEQ Emission
Factor:*
(kg TEQ/kg waste)
3.96 e-9
9.09 e-10
7.44 e-1 1
3.96 e-9
9.09 e-10
gr/dscf = grains per dry standard cubic foot at standard temperature and pressure.
3-66
April 1998
-------
DRAFTS-DO NOT QUOTE OR CITE
Table 3-9. OAQPS Approach: Estimated Nationwide CDD/CDF TEQ Emissions (g/yr) for 1995
[;MWI ; -
^ * 'Type M~V '
_1^ * • <-•
Batch
Continuous
Continuous/
Intermittent
Intermittent
•Subtotal: , „
Uncontrolled - -*
Batch
Continuous
Intermittent
Subtotal: Controlled X
'W/Wet Scrubber
Continuous
Continuous
on-site/ Intermittent
Continuous
Continuous
on-site/ Intermittent
Subtotal: Controlled
w/Dry Scrubber
Intermittent
Total MWI v
Residence^
' ,- Tirne or - '"
'> '/APCD**7-
0.25 sec
1.00 sec
2.00 sec
0.25 sec
1 .00 sec
2.00 sec
0.25 sec
1 .00 sec
2.00 sec
0.25 sec
1 .00 sec
2.00 sec
v cV "*
''*'*•&-
Wet Scrubber
Wet Scrubber
Wet Scrubber
\ - s
Dry Scrubber
no carbon
Dry Scrubber
with no
carbon
Dry Scrubber
with Carbon
Dry Scrubber
with Carbon
-f *" s
Fabric Filter/
Packed Bed
s
, CDD/CDF
<~/rfo £F,iA f
1.94e + 05
4.45e + 04
3.65e + 03
1.94e + 05
4'.45e + 04
3.65e + 03
1.94e + 05
4.45e + 04
3.65e + 03
1.94e + 05
4.45e + 04
3.65e + 03
\
'< f »
4.26e + 02
4.26e + 02
4.26e + 02
H *? "%
3.65e + 02
3.56e + 02
7.00e + 01
7.00e + 01
!i~
3.34e + 04
^TEQ,'
'EF;/
3.966 + 03
9.09e + 02
7.40e + 01
3.96e + 03
9.09e + 02
7.40e + 01
3.96e + 03
9.09e + 02
7.40e + 01
3.96e + 03
9.09e + 02
7.40e + 01
i o
* „ „ ^ ' *
/
10
10
10
^ \ -,
7
7
2
2
"> 4s ^ #
ft ^ / /
3^1
6.81e + 02
•
*" ^Activity
~ Level * *
5.95e + 06
4.20e + 05
2.14e + 05
1.20e + 06
5.10e + 06
3.01e + 07
4.54e+06
4.24e + 07
9.79e + 07
4.18e + 06
1.83e + 07
NA '
2»53e-M)8
i^» « '
2.42e + 04
1.88e + 08
6.04e + 07
3.7le+08
'I
9.94e + 07
7.86e + 06
1.43e + 07
3.706 + 06
i:46e+j08'
7 v. '•
6.99e + 05
CDD/CDF^
s Emissions
1.15e + 03
1.876 + 01
7.82e-01
2.34e + 02
2.27e + 02
1.10e + 02
8.80e + 02
1.88e + 03
3.57e + 02
8.11e + 02
8.12e + 02
NA
>6.65e+O3
1 .OOe-02
8.01e + 01
2.58e + 01
1.58e+02
3.63e + 01
2.87
1.00
2.61e-01
4.80e+01
N ^
2.34e + 01
- TEQ
"" Emissions ^
2.35e + 01
3,82e-01
1.60e-02
4777
4.64
2.24
1,80e + 0,1
3.85e + 01
7.29
1. 656 + 01
1.66e + 01
NA
1.36e+02
2.00e-04
1 .90
6.11e-01
3.74 >
^
7.39e-01
5.80e-02
2.40e-02
6.00e-03
9.82e-O1 ' :
> „
4.76e-01
NA = Not applicable
ng/kg = nanograms per kilogram
kg/yr = kilograms per year
g/yr = grams per year
3-67
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-10. AHA Approach: TEQ Emission Factors Calculated for Air Pollution Control
ARC Category
Uncontrolled
MWIs up to 200 Ib/hr
MWIs > 200 Ib/hr
Wet scrubber/BHF/ESPb
Dry sorbent injection/Fabric Filter
TEQ Emission-Factor
(lb/1.06'lbs waste)
1.53e-03
5.51e-04
4.49e-05
6.95e-05
Number of MWI Test
Reports Used'8
4
13
11
8
The same MW| may have been used more than once in deriving emission factors.
Wet scrubbers-bag house filters-electrostatic precipitators. Bag house is also called Fabric
Filter. '
Source: Doucet (1995).
3-68
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-11. AHA Assumptions of the Percent Distribution of Air Pollution
Control on MWIs Based on PM Emission Limits
* ~y * > ^
* '/''*• f * ^~ **
, ~ PM Emission Limits8 -
V, *•' "(gr/dSCf) ""?
2 : 0.10
0.08 to < 0.10
0.03 to < 0.08
< 0.03
, ,- Percent MWIs.:
~ + sUncohtroIIedb^"~f
'50%
25%
0%
0%
Percent-MWIs with Wet ,
!> ,-. ^Scrubbers/ -"
' " - "-rBHRs/ESPs6*'''" -
50%
75%
98%
30% ...
^ ^<-y
^Percent ,.,
0%
0%
2%
70%
Paniculate matter (PM) emission limits at the stack, grains per dry standard cubic foot
(gr/dscf).
Uncontrolled means there is no air pollution control device installed on the MWI.
c Scrubbers/BHFs/EDPs means wet scrubbers-bag house filters-electrostatic precipitators.
DI/FF means dry sorbent injection combined with fabric filters.
3-69
April! 998
-------
DRAFT-DO NOT QUOTE OR CITE
1 , Ih" " , *'»' ' , " , . i
Table 3-12. AHA Approach: Estimated Annual Nationwide CDD/CDF TEQ Emissions
APCD8
Uncontrolled
Subtotal:
Uncontrolled
WS/BHF/ESP
DI/FF
Subtotal: Controlled
Total
MWI Capacity6
(Ib/hr)
<; 200
> 200
>200
>200
/
CDD/CDF TEQ
Emission Factor0
(g/kg waste)
1.54e-06
5.51 e-07
4.49 e-08
6.95 e-08
MWI Activity
. Leveld
(kg/yr)
2.28e + 07
1.54e + 08
1.77e+08
3.51 e + 08
2.60 e + 07
3.77e+08>v
.
"5,54 •e4-08;^':^'-:
Annual TEQ
Emissions
(g/yr)
3.51e + 01
8.48e + 01
1.20e+02
1.58e + 01
1.81
1.76&+01
1:38e+b2-^r't
APCD = Air Pollution Control Device assumed by AHA. Uncontrolled means there is no air
pollution control device installed op the MWI. WS/BHF/ESP = Wet scrubber-bag house
filter-electrostatic precipitator. DI/FF = Dry sorbent injection-fabric filter.
MWI capacity is the design capacity of the primary combustion chamber.
c TEQ Emission Factor derived from tested facilities.
Activity Level is the annual amount of medical waste incinerated by each APCD class. '
Ib/hr = pounds per hour
g/kg = grams per kilogram
kg/yr = kilograms per year
g/yr «= grams per year
3-70
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-13. 'Comparison Between Predicted Residence Times and Residence
Times Confirmed by State Agencies from EPA/ORD Telephone Survey
"- T State '%. x
- ;.-***/ \1
Michigan
Massachusetts
Virginia
New Jersey
x,Resldence?Time
^ Categories*^
\ ""
1/4 second
1 .0 second
2.0 seconds
1 /4 second
1 .0 second
2.0 seconds
1 /4 second
1 .0 second
2.0 seconds
1 /4 second
1 .0 second
2.0 seconds
Percentage of ~,
#-. Uncontrolled .JMWIs
Predicted by PM Method
2% (6/280 MWIs)
2% (5/280)
96% (269/280)
6% (6/94 MWIs)
0% (0/94)
94% (88/94)
1 1 % (6/56)
0 % (0/50)
89% (50/56)
0% (0/53 MWIs)
0% (0/53)
100% (53/53)
Percentage of .Uncontrolled
MWls 'Confirmed by State
96% (269/280 MWIs)
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).
3-71
April 1998
-------
in
o>
o>
CO
CD
ffi
CD
CC
a
CO
•i
£
ICO It
c II
0
Il~
n E "5
< a "~
UJ
CO
c O '55 .>•
,• UJ ,
•
-"*,*
I'll
g B
0
05
r*
in"
CO
0
CD
CO
CO
CM'
-
!*•
0
CD
CO
q
CO
CO
•* "°TJ +
IE «J o
|fp
§ p a -sl 9
•s i- o S +
E s g a
111 £0
•»- -o S
o ffl -2
o §1
1 *~~ i£
CO
CO Jr
_JO O
CD
in
CM
en
CO
.
ry j|« || ~~
5 co "* 1 O
> O O
CM
O
CD
05
r*«
CO
Tf
0
05
•.
«-
00
0
0>
f-^
CO
o
05
CM
co
o
+
0>
in
CO
*
00
CD ^
11
CO C5
as S o-
> CD CO
> U. UJ
o
0)
o
O)
O5
0
05
CO
T—
•*
00
0
05
CO
•^
T~
"^
CM
o
4-
05
in
00
CM
CM
= 05
15 ^
>. to &
± "r-* (0
Q i U-
o
05
o
in
O5
o
05
CO
rv
in
0
05
O)
O)
CO*
co
o
05
in
CO
in
O
-f-
05
T—
I?
~ m !s
L. 0)
„ TJ J3
2 «-§
ja o =:
CO CD U
u- a. co
•o
_CD
"5
U.
o
0
1
CM
0)
^ 1
fv
^'
0
05
CM
o
CM
00
0
05
(V
r>*
To
o
[^
CO
oo
c»
Q.
<
CM
r-^
co
ntrol Devices
0
O
.0
3
"o
Q_
II
Q
U
a.
•^
E
CO
k_
D5
_O
•^
05
a.
CO
E
E
ro
o
CO
c
II
O3
C
k.
CO
a>
05
a.
CO
E
CD
L_
TO
_O
12
II
,_
.>
"CD
CD
•*"
CD
D.
CO
CD
CD
II
>.
CO
3
O
CD
a.
CO
•a
3
O
a.
u
u
^
£
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (mean congener emission factor / total CDD/CDF emission factor)
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-rixCDF
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)
°-OS 0.1 o.lS m
0.2
0.25
Figure 3-12. Congener .and Congener Group Profiles for Air Emissions
from Medical Waste Incinerators without APCD
3-73
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
0.01 0.02 0.03 0.04 O.OS 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-fffCDD
1.2,3,4,6.7.8,9-OCDD
2,3.7.8-TCDF
:'\T.\ 1,
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-fixCDF
1,2,3.4.6,7,8-HpCDF
1,2.3.4.7,8.9-Hi)CDF
1,2,3,4.6,7,8,9-OCDF
Ratio (congener group emission factor / total CDD/CDF emission factor)
°-os 0.1 0.15
0.2
Nondetects set equal to zero.
Figure 3-13. Congener and Congener Group Profiles for Air Emissions from Medical
Waste Incinerators Equipped with a Wet Scrubber, Baghouse, and Fabric Filter
3-74
April 1998
-------
r^
00
0)
CD
CD
>-
CD
O
C
CD
1 il
-£
CD
DC
, O
• M—
§
|
s
CD
C
'o
_c
CD
CO
CD
1
CD
0
w "§
o" |
o ^
S §
o 'i
s s
HCJ
III
O H
* CD
o i
£j c
H ^'
LL ^
S |
Q 1
3
C/J
LO
r_
1
CD
15
CD
o,. "/?
S
^ i,U *•» •&•
•"!•=::
Sj *W> to
O £ ^
§"",£"&
•*£ ***^ ^
^c ^
A V "
W
t?r~^ '
"'CJ /*» _§^*"-^
^iy §^*m^
vT "S "*^ ^
^•^^ ^.^j ^ ^^f»
J*""" ?"/.**•
^ * ^ ^
** >,
?>
fe i
S O ^L *-**
"|*5 &^
c 'S
j ~ - '
+* ~o> f
IS ~
*^^
j
^ ^
__
1j «"" J
(~ S
*ft ^ * *
° CO
,o u.
z ^
^ ^ ^ *
/
"w "/ '
^
>~
" ^
'»
'CN
o
CD
00
q
^f
^^
0
CD
CN
q
CN .
CO
0
CD
CO
00
»
LO
O
1
CD
in
CN
O)
00
0
CD
O)
CN
CO
.C
o
o
CN
VI
CO
0
CD
CO
q
CN
^^
o
CD
CO
l<
CO
9
CD'
O
•
^~
LO
9
CN
O
CO
O)
O
CD
t —
CN
LO
IS
o
o
,CNI
A
J
O
CD
rh
CN
^-
O
CD
CO
CO
03
O)
O
CD
CO
00
-
• CD
o
, ,
LO
O)
05
X
^JJ
0
: I '-
^
• 'CD
O
Q..
0-
I
CD
-*-»
'o
CD
E
CD
• O
CO
c
CD'
.£
&_ '
O
O) vl c
CD .CD C '
«-• CD CD '
• CD i«. *—
O O3 . ^
fc- X »s o
fl} rt\ ^^ CD 2s
/ | A2 £*
_ , 03 i_ CD
8 ' E §. « tt
• co CD "•- Q- eo
1 I ill
1— OJ oj O-
" II II II
u |j u
-$• °* w £
ra ^1 O3 C3) -0
00
05
cn
0.
.<
LO
t>»
t
CO
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-16. Comparisons of Basic Assumptions Used in the EPA/ORD, the EPA/OAQPS, and the
AHA Approaches to Estimating Nationwide CDD/CDF TEQ Emissions from MWIs in 1995
I Assumptions
Reference Year
Number of MWIs
Estimated Activity
Level
Percent of Activity
Level at Uncontrolled
MWIs
Percent of Activity
Level at Controlled
MWIs
Subcfassification of
Uncontrolled Class
Assumed Distribution
of Uncontrolled Class
APCDs Assumed for
Controlled Class
I Assumed Distribution
of Controls
Emission Factor
I Approach Used
I No. of Tested MWIs
Used to Develop
Emission Factors
Uncontrolled TEQ
Emission Factors
(ng/kg)
Controlled TEQ
Emission Factors
(ng/kg)
EPA/ORD Approach
1995
2,375
7.71 e + 08 kg/yr
33%
67%
Same as AHA
assumption
Same as AHA
assumption
WS/FF/ESP
DI/FF
FF/Packed Bed Scrub
Yes/ Analogous to
AHA method.
Yes
Uncontrolled: 8
Controlled: 1 1
1,865 = s200 Ib/hr
1,701 = >200lb/hr
f/ WS/FF/ESP: 72
g/ DSI/FF: 7
h/FF/PBS: 1,352
1995
2,375
7.71 e + 08 kg/yr
33%
67%
By residence times (RT) in
secondary chamber
By RT of 0.25, 1 .0 and 2.0
sec by State PM emission
limits
WS
DS-no Carbon
DS-Carbon
FF/Packed Bed Scrub
Yes/ Analogous to AHA
method
Yes
Uncontrolled: 10
Controlled: 23
a/ 3,960 = 0.25 s RT
b/ 909 = 1 .0 s RT
c/ 200 Ib/hr 74 =2.0sRT
/WS: 10
/ DS no carbon: 7
k/ DS with carbon: 2
/FF/PBS: 681
1995
2,233
5. 54 e + 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
DI/FF
Yes/ Based on survey
and State PM
emission limits
Yes
Uncontrolled: 13
Controlled: 12
d/ 1,540 =s200 Ib/hr
e/ 551= > 200 Ib/hr
ml WS/FF/ESP: 44.9
n/ DSI/FF: 69.5
WS - Wet Scrubber; FF = Fabric Filter; ESP = Electrostatic Precipitator; DSI = Dry Sorbent Injection; DS
Dry Scrubber; no carbon = without the addition of activated carbon; with carbon = with the addition of
activated carbon; PBS = Packed Bed Scrubber.
a 0.25 seconds residence time (RT) in the secondary chamber.
b 1.0 seconds residence time (RT) in the secondary chamber.
c 2.0 seconds residence time (RT) in the secondary chamber.
d design capacities less than or equal to 200 Ibs/hr.
e design capacities greater than 200 Ibs/hr.
Ib/hr « pounds per hour
kg/yr « kilograms per year
3-76
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-17. CDD/CDF Air Emission Factors for a 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
t,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDD
Total 2,3,7,8-GDF
Total TEQ
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
TotalTCDF
Total PeCDF
Total HxCDF
Total HpCDF :
Total OCDF
Total CDD/CDF
=====!^======================s=========l
Mean Facility Emission Factor
Assuming
ND = zero
(ng/body)-
28.9
89.6
, 1 08
157
197
1,484
2,331
206
108
339
374
338
657
135
1,689
104
624
4,396-
4,574
501
554
860
2,224
3,180
2,331
4,335
2,563
4,306
2,030
624
23,007
Assuming
ND = 1/2 det limit
(ng/body)
28.9
89.6
108
157
197
1 484
t f^TU^T
2,331
206
117
349
374
338
657
135
1,813 '
112
624
r ,
4,396
4,725
508
554
860
2,224
3,180
2,331
4,335
2,563
4,306
2,154
624 II
23,131 I
ng/body = nanograms per body
Source: CARB (1990c)
3-77
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
0.02 p.04 0.06 0.08 0.1
0.12
2,3,7,8-TCDD
1.2.3,7,S-PcCI>r>
1.2,3.4,7.S-HxCDD
1, 2.3,6,7. 8-HxCDE>
1.2,3.7.8,9-HxCDD
1,2,3.4.6,7,8-HpCbD
1.2.3.4,6,7,8,9-OCpD
2,3,7,8-TCDF
l,2,3.7,S-PeCDF
2.3,4,7,8-PcCDF
1,2,3.4.7,8-HjcCDF
1^^.6.7.8-HxCDF
2^,4,6.7,8-HxCDF
1 ,2,3,4.6.7.S-HpCbF
1 ^,3 .4.7,8,9-HpCDF
Ratio (congener group emission factor / total CDD/CDF emission factor)
°-05 0.1 0.15
0.2
Source: CARB (1990c); nondetects set equal to zero.
Figure 3-14. Congener and Congener Group Profiles for
Air Emissions from a Crematorium
3-78
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-18. 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
11,2,3,7,8,9-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
I Total HxCDF
Total HpCDF
Total OCDF
Total TEQ
Total CDD/CDF
1
U.S. EPA (1987a) - 3 facilities
Mean Emission Factor (ng/kq)
Nondetects
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 .
1,266
Nondetects
Set to
1/2 Det. 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
54.0
46.2
528
253
75.9
144
109
NR
. 1,268
=s==:====================
Green et al. (1995) - 13 facilities
Mean Emission Factor (nq/kq)
Nondetects
Set to
Zero
0.12
0.23
0.03
0.10
0.29
2.55
13.60
26.60
1.98
6.84
".' 2.17
0.79
0.03
1.26
~ 1 .46
0.17
1.22
35.80
6 82
1 .74
4.39
13.60
123.85
59.94
12.69
2.63
1 .22
6.94
257
======!=
Nondetects
Set to
1/2 Det. Limit
O"2"?
O ?9
O 1 1
O 1fi
O ^R
2 70
14.00
26.63
2 OR
6QQ
2 24
O 8^
0.08
1 4R
1 64
0.27
*1.62
37.81 ,
• 1 RQ
2.25
5.03
14.00
124.10
60.16
13.50
^19 I
1.62
7.19
263
=======£
ng/kg = nanograms per kilogram
NR = not reported
Sources: U.S. EPA (1987a); Green et al. (1995)
3-79
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25
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-PcCDF
1,2,3,4.7,8-HxCDF
1^,3,6,7,8-HxCiDF
1^,3,7.8,9-HxCDF
2^.4,6,7.8-HxCDF
1^,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
Figure 3-15. Congener and Congener Group Profiles for
Air Emissions from Sewage Sludge Incinerators
3-80
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 3-19. CDD/CDF Air Emission Factors for Tire Combustion
II
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 ,
Mean Facility Emission Factor
Assuming
ND = zero
(ng/kg) ,
0.149
» 0.006
6.018
0.055
0.036
0.379
4.156
0.319.
0.114
0.086
0.103
0.059
0.036
0.100
0.000
0.027
0.756
4.799
1.600
0.282
0.153
0.032
0.391
0.695
4.156
1.204
0.737
0.710
0.119
0.756
8.953
Assuming
ND = 1/2 det limit
(ng/kg)
0.149
0.026
0,023
0.062
0.048
0.379
4.156
0.319
0.118
0.091
0.111
0.090
0.068S
0.148
0.166
0.095
0.756
4.843
1.962
0.310
0.153
0.0,32
0.391
0.695
4.156
1 .204
0.737
0.710
0.186 .
0.756
ng/kg = nanograms per kilogram
ND = not detected
Source: CARB (1991 a)
3-81
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
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-HxCpD
1,2,3 ,7.8.9-HxCDD
1.2,3,4.6,7,S-Hp
-------
DRAFT-DO NOT QUOTE OR CITE
fable 3-20. CDD/CDF Emission Factors for Combustion of Bleached-Kraft
Mill Sludge in Wood Residue Boilers
Congener
12,3,7,8-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-HxCOF
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 TEQ
Total CDD/CDF
'
- =^==^=r=:=
Sludge and Wood - 1 facility
Mean Emission Factors
(ng/kg feed)
; Nondetects
Set to
Zero
0
0
0
0
0
0
0.025
0.005
0
0
0
0
0
0
0
0
0
0
0
0
0
0.025
0.094
0
0 ;
-0
0
0.001
0.119
, Nondetects
Set to
1/2 Det. Limit
0.001
0.001
0.001
0.001
0.001
0.003
0.025
0.005
0.003
0.003
0.001
0.001.
0.001
0.001
0.001
0.000
0.001
0.002
0.001
0.002
0.003
0.025
0.094
0.003
0.001
0.001
0.001'
0.005
< 0.134
=^5=«— — — — — —
1 ' "^
Wood Residue Only - 5 facilities
Mean Emission Factors
Nondetects
Set to
Zero
0.066
.0.110
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
1.120
1.317
4.532
1.548
0.536
0.111
0.049
0.401
14.593
Nondetects I
Set to
1/2 Det Limit I
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
0.020
0.060
1.629
1.980
1.796
1.132
1.317
4.552
1.549
0.543
0.116
0.060
0 409
14.674
ng/kg = nanograms per kilogram
Source: NCASI (1995)
3-83
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
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-PtCDD
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)
O.I O.2 O.3
O.4
Figure 3-17. Congener and Congener Group Profiles
for Air Emissions from Bleached Kraft Mill Combustors
3-84
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
*
4. COMBUSTION SOURCES OF CDD/CDF: POWER/ENERGY GENERATION
4.1. MOTOR VEHICLE FUEL COMBUSTION
Ballschmiter et'al. (1986) reported detecting CDD/CDFs in used motor oil and thus
provided some of the first evidence that CDD/CDFs might be emitted by the combustion
processes in gasoline- and diesel-fueled engines. Incomplete combustion and the presence
of a chlorine source in the form of additives in the oil or the fuel (such as dichloroethane or
pentachlorophenate) were speculated to lead to the formation of CDDs and CDFs. The
^ " ' ' "" -'
congener patterns found in the used oil samples were characterized by Ballschmiter et al.
(1986) as similar to the patterns found in fly ash and stack emissions from municipal waste
incinerators.
Since 1986, several studies have been conducted to measure or estimate CDD/CDF
concentrations in emissions from vehicles. Although there is no standard approved
protocol for measuring CDD/CDFs in vehicle exhausts, researchers have developed and
implemented several measurement approaches for collecting and analyzing vehicle
exhausts. Other researchers have estimated vehicle exhaust emissions of CDD/CDFs
indirectly from studies of tunnel air. The results of these two types of studies are
summarized in chronological order in the following Section 4.1.1 and Section 4.1.2.
Estimates of national annual CDD/CDF TEQ emissions from on-road motor vehicles fueled
with leaded gasoline, unleaded gasoline, and diesel fuel are presented in Section 4.1.3
based on the results of these studies. National emission estimates have not been
generated for off-road vehicles (i.e., construction and farm vehicles) or stationary sources
using these fuel types because of lack of emission factor data.
4.1.1. Tailpipe Emission Studies
Marklund et al. (1987) provided the first direct evidence of the presence of CDDs
and CDFs in car emissions based on tailpipe measurements on Swedish cars.
Approximately 20 to 220 pg of TEQ from tetra- and penta-CDD/CDFs were reported per
kilometer driven for four cars running on leaded gasoline. For this study, an unleaded
gasoline was used to which was added tetramethyl lead (0.1 5 grams of lead per liter [g/L]
or 0.57 grams per gallon) and dichloroethane (0.1 g/L as a scavenger). The fuel used may
not accurately represent commercial fuels, which typically contain a mixture of chlorinated
. , . 4-1 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
and brominated scavengers (Marklund et al., 1990). Also, the lead content of the fuel used
(0.15 g lead/L), although the normal lead content for Swedish fuels at the time (Marklund
et al., 1990), was higher than the lead content of leaded gasoline in the United States
during the late 1980s (lowered to 0.10 g lead/gallon or 0.026 g lead/L effective January 1,
1986). Marklund et al. (1987) reported a striking similarity in the TCDF and PeCDF
congener profiles in the car exhausts and those found in emissions from municipal waste
incinerators. For two cars running on unleaded gasoline, CDD/CDF emissions, were below
the detection limit, which corresponded to approximately 13 pg of TEQ per kilometer
driven.
Table 4-1 presents a summary description of the results of the Marklund et al.
(1987) study and subsequent studies (presented in chronological order) discussed below.
Tables 4-2 and 4-3 present the results of tailpipe emission studies reported for diesel-fueled
cars and trucks, respectively, table 4-4 presents the results of studies using leaded
gasoline-fueled cars, and Tables 4-5 and 4^6 present results of studies with cars fueled by
unleaded gasoline. Figures 4-1, 4-2, and 4-3 present congener and congener group profiles
from diesel-fueled vehicles, leaded gasoline-fueled vehicles, and unleaded gasoline-fueled
vehicles, respectively.
Virtually no testing of vehicle emissions in the United States for CDD/CDFs has been
reported. In 1987, the California Air Resources Board (CARB) produced a draft report on
the testing of the exhausts of four gasoline-powered cars and three diesel fuel-powered
vehicles (one truck, one bus, and one car) (CARB, 1987a). However, CARB indicated to
EPA that the draft report should not be cited or quoted to support general conclusions
about CDD/CDFs in motor vehicle exhausts because of the small sample size of the study
and because the use of low rather than high resolution mass spectrometry in the study
resulted in high detection limits and inadequate selectivity in the presence of interferences
(Lew, 1993). CARB did state that the results of a single sample from the heavy-duty diesel
truck could be reported, because congeners from most of the homologue groups were
present in the sample at levels that could be detected by the analytical method and there
were no identified interferences in this sample. This test was conducted under steady
state conditions (50 km/hrj for 6 hours with an engine with a fuel economy of 5.5 km/L.
The TEQ emission factor of this one sample was equivalent to 7,290 pg/L of fuel burned (br
1,300 pg/km driven) if nondetected values are treated as one-half the detection limit.
4-2 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Treating nondetected values as zeros yields a TEQ concentration equivalent to 3,720 pg/L
of fuel burned (or 663 pg/km driven) (Lew, 1996).
," -^ ' '
Haglund et al. (1988) sampled exhaust gases from three different vehicles (two cars
fueled with leaded and unleaded gasoline, respectively, and a heavy-duty diesel truck) for
the presence of brominated dibenzb-p-dioxins (BDD) and brominated dibenzofurans (BDF).
The authors concluded that the dibromoethane scavenger added to the tested gasoline
probably acted as a halogen source. TBDF emissions measured 23,000 pg/km in the car
with leaded gasoline and 240 pg/km in the car with unleaded gasoline. TBDD and PeBDF
emissions measured 3,200 and 980 pg/km, respectively, in the car with leaded gasoline.
All BDD/Fs were below detection limits in the diesel truck emissions.
Bingham et al. (1989) also analyzed 2,3,7,8-substituted CDD/CDFs in automobile
exhausts. Four cars using leaded gasoline (0.45 g/JL tetramethyllead, 0.22 g/L
dichloroethane, and 0.2 g/L dibromoethane) were tested, and one car using unleaded
gasoline was tested. Only HpCDD and OCDD were detected in the exhaust from the
vehicle using unleaded fuel. The total TEQ emission rate for this car, based on these
detected congeners, was 1 pg/km; the detection limit for the other 2,3,7,8-substituted
CDD/CDFs was a combined 28 pg TEQ/km. 2,3,7,8-TCDF was detected in the exhaust of
two of four cars using leaded fuel. OCDD was detected in the exhaust from three of the
cars, and PeCDF and HpCDD were each detected in the exhaust from one car. TEQ
emission rates for the cars using leaded fuel, based on detected congeners only, were 5 to
39 pg/km.
Marklund et al. (1990) tested cars fueled with commercial fuels, measuring
CDD/CDF emissions before and/or after the muffler of Swedish vehicles (including new and
old vehicles). Three cars were tested using unleaded gasoline, and two cars were tested
with leaded gasoline (0.15 g Pb/L and dichloroethane and dibromoethane scavengers).
CDD/CDFs were not detected in the fuels at a detection limit of 2 pg TEQ/L, but were
detected at a level of 1,200 pg TEQ/L in the new semi-synthetic engine lube oil used in the
engines. The test driving cycle employed (i.e., 31.7 km/hr as a mean speed; 91.2 km/hr as
a maximum speed; and 17.9 percent of time spent idling) yielded a fuel economy of
approximately 9 to 10 km/L or 22 to 24 miles/gallon, Marklund et al. (1990) reported the
"following emission results in units of pg TEQ/L of fuel consumed and also in units of pg
TEQ/km driven during the test: .
4-3
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
• Leaded gas/before muffler: 2.4 to 6.3 pg TEQ/km (or 21 to 60 pg TEQ/L of fuel
consumed); _.
• Leaded gas/in tailpipe: 1.1 to 2.6 pg TEQ/km (or 10 to 23 pg TEQ/L);
• Unleaded gas/catalyst-equipped/in tailpipe: 0.36 pg TEQ/km (or 3.5 pg TEQ/L);
and
• Unleaded gas/before muffler: 0.36 to 0.39 pg TEQ/km (or 3.5 pg TEQ/L).
The TEQ levels in exhaust gases from older cars using leaded gasoline were up to six times
greater when measured before the muffler than after the muffler. No muffler-related
difference in new cars running on leaded gasoline or in old or new cars running on unleaded
„ "i " '! ' • ''• ' '„,''"',
gasoline was observed.
Marklund et al. (1990) also analyzed the emissions from a heavy-duty diesel-fueled
truck for CDD/CDFs. None were detected; however, the authors pointed out that the test
"V " : ". ", ;' '•' • •••'' '"' ' : ; : ,'• ;.•; •
fuel was a reference fuel and may not be representative of commercial diesel fuel. Also,
due to analytical problems, a much higher detection limit (about 100 pg TEQ/L) was
employed in the diesel fuel test than in the gasoline tests (5 pg TEQ/L). Further uncertainty
was introduced by the fact that diesel emission samples were only collected prior to the
muffler.
Hagenmaier et al. (1990) ran a set of tests using conditions comparable to the FTP-
73 test cycle on gasoline- and diesel-fueled engines for light duty vehicles in Germany. The
following average TEQ emission rates per liter of fuel consumed were reported:
* ', , : - • , ' ' ' . ' .
• Leaded fuel: 1,083 pg TEQ/L;
'' " '!'' * ,.'',' L,, ' '
• Unleaded fuel (catalyst-equipped): 7 pg TEQ/L;
• Unleaded fuel (not catalyst-equipped): 51 pg TEQ/L; and
ii! ' ' ..,,''"'• ', i
• Diesel fuel: 24 pg TEQ/L.
The major findings of a German study of emissions of halogenated dibenzodioxins
and dibenzofurans from internal combustion engines running on commercial fuels were
published in 1991 (Schwind et al., 1991), and the full detailed report was published in
1992 (Hutzinger et al., 1992). The study was conducted by the Universities of Stuttgart,
Tubingen, and Bayreuth for the Federal Ministry for Research and Technology, the Research
4-4 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Association for Internal Combustion Engines, and the German Association for the Petroleum
Industry and Coal Chemistry. Tests were conducted using engine test benches and rolling
test benches under representative operating conditions. Tests were performed on leaded
gasoline engines, unleaded gasoline engines, diesel car engines, and diesel truck engines.
The reported range of GDD/CDF emission rates across the test conditions in units of pg
TEQ per liter of fuel consumed are presented below. The results from those tests
conducted under normal operating conditions with commercial fuels and for which
congener-specific emission results were presented in Hutzinger et al. (1992) are listed in
Tables 4-2 through 4-6.
•_ Leaded fuel: 52 to 1,184 pg TEQ/L;
• Unleaded fuel (not catalyst-equipped): 57 to 177 pg TEQ/L;
• Unleaded fuel (catalyst-equipped): 15 to 26 pg TEQ/L;
• Diesel fuel (cars): 10 to 130 pg TEQ/L; and
• Diesel fuel (trucks): 70 to 81 pg TEQ/L. '..'.'
Although no specific details on the methodology used were provided, Hagenmaier
(1994) reported that analyses of emissions of a diesel-fueled bus run either on steady state
or on the "Berlin cycle" showed no CDD/CDF present at a detection limit of 1 pg/L of fuel
consumed for individual congeners.
Gullett and Ryan (1997) recently reported the results of the first program to sample
diesel engine emissions for CDD/CDFs during actual highway and city driving. The exhaust
emissions from a 1991 Freightliner diesel tractor with a 10.3 L, 6-cylinder Caterpillar
i ' ;
engine, representative of the first generation of computerized fuel controlled vehicles
manufactured in the United States', were sampled during both highway and city driving
routes. The average emission factor'for the three highway tests conducted (15.1 pg
TEQ/km; range 11.7-18.7 pg TEQ/km; standard deviation of 3.5 pg TEQ/km) was a factor
of three below the average of the two city driving tests (49.9 pg TEQ/kg; range 3.0-96.8
pg TEQ/km). Detection limits were considered as zeros in the calculation of these emission
factors. The average of all five tests was 29.0 pg TEQ/km with a standard deviation of
38.3 pg TEQ/km; this standard deviation reflects the 30-fold variation in the two city
driving route tests.
: - . 4^5 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Hi " , '
4.1.2. Tunnel Emission Studies
Several European studies and one recent U.S. study evaluated CDD/CDF emissions
from vehicles by measuring the presence of CDD/CDFs in tunnel air. This approach has the
advantage that it allows random sampling of large numbers of cars, including a range of
ages and maintenance levels. The disadvantage of this approach is that it relies on indirect
measurements (rather than tailpipe measurements), which may introduce unknown
uncertainties and make interpretation of the findings difficult. Concerns have been raised
that the tunnel monitors are detecting resuspended particulates that have accumulated over
time, leading to overestimates of emissions. Also, the driving patterns encountered in
these tunnel studies are more or less steady state driving conditions rather than the
transient driving cycle and cold engine starts that are typical of urban driving conditions and
that may affect emission levels. Each of these studies is summarized below in
chronological order.
Rappe et at. (1988) reported the CDD/CDF content of two air samples (60 m3 per
sample) collected from a tunnel in Hamburg, Germany, during January of 1986 to be 0.42
and 0.58 pg TEQ/m3. Each sample was cojlected for a period of about 60 hours. Rappe et
at. (1988) reported that the tunnel handles 65,000 vehicles per day of which 17 percent
were class'ified as "heavy traffic." The congener-specific results of the two samples are
presented in Table 4-7. Rappe et al. (1988) concluded that the results clearly show that
' traffic (with leaded gasoline and halogenated additives) is a source of CDD/CDFs in ambient
air. Measurement of ambient air conducted in September of 1986 at a "nearby highway in
Hamburg was reported to contain CDD/CDF levels two to six times lower than those
measured in the tunnel;
Larssen et al. (1990) and Oehme et al. (1991) reported the results of a tunnel study
in Olso, Norway, performed during April/May of 1988. Oehme et al. (1991) estimated total
vehicle emissions by measuring CDD/CDF concentrations in tunnel inlet and outlet air of
both the uphill and downhill lanes. Emission rates for light-duty and heavy-duty vehicle
1 • .,i,ii< • ., , i , • . i ,' i, • • • .,, i ,,,,,,,',, •: • ,1',, •, , • i
classes in the uphill and downhill lanes were estimated by counting the number of light-
duty vs. heavy-duty vehicles passing through the tunnel on workdays and a weekend and
assuming a linear relationship between the percentage of the light- or heavy-duty traffic
and the overall emission rate. Thus, the linear relationship for each emission rate was
4-6 - April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
i • ,
based on only two points (i.e., the weekday and weekend measurements). The emission
rates, in units of Nordic TEQ, estimated in this study are:
• Light-duty vehicles using gasoline (approximately 70-75 percent using leaded
gas): uphill = 520 pg TEQ/km; downhill = 38 pg TEQ/km; mean = 280 pg
TEQ/km; and
• Heavy-duty diesel trucks: uphill - 9,500 pg TEQ/km; downhill = 720 pg
TEQ/km; mean = 5,100 pg TEQ/km.
The mean values are the averages of the emission rates corresponding to the two operating
modes: vehicles moving uphill on a 3.5 percent incline at an average speed of 37 miles per
hour and vehicles moving downhill on a 3.5 percent decline at an average speed of 42
miles per hour. Although Oehme et al. (1991) reported results in units of Nordic TEQs
rather than l-TEQs,,the results in I:TEQ should be nearly identical (i.e., about 3 to 6 percent
higher), because the only difference between the two TEQ schemes is the toxic
equivalency factor assigned to 1,2,3,7,8-PeCDF (0.1 in Nordic and 0.05 in I-TEQ), a minor
component of the toxic CDD/CDFs measured in the tunnel air. Table 4-7 presents the
congener-specific differences in concentrations between the tunnel inlet and outlet
concentrations. .
Wevers et al. (1992) measured the CDD/CDF content of air samples taken during
the winter of 1991 inside a tunnel in Antwerp, Belgium. During the same period,
background concentrations were determined outside the tunnel. Two to four samples were
collected from each location with two devices: a standard high volume sampler with a
glass fiber filter and a modified two-phase high volume sampler equipped with a glass fiber
filter and a polyurethane foam plug (PUF). The TEQ concentration in the air sampled with
the filter/PUF device was 74 to 78 percent of the value obtained with only the high volume
sampler only device. However, the results obtained from both sets of devices indicated
that the tunnel air had a dioxin TEQ concentration about twice as high as the outside air
(filter/PUF: 80.3 fg TEQ/m3 for tunnel air vs. 35 fg TEQ/m3 for outside air; filter only: 100 ,
fg TEQ/m3 for tunnel air vs. 58 fg TEQ/m3 for outside air). Wevers et al. (1992) presented J
the congener-specific results for only one tunnel air measurement; these results are
presented in Table 4-7 From these data, Bremmer et al. (1994) calculated an emission
factor of 65 pg TEQ/km driven for all road traffic collectively.
, 4-7 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
During October/November 1995, Gertler et al. (1996; 1998) conducted a study at
the Fort McHenry Tunnel in Baltimore, Maryland, with the stated objective of measuring
CDD/CDF emission factors from in-use vehicles operating in the United States, with
particular emphasis on heavy-duty vehicles. The air volume entering and leaving the tunnel
bore that services most of the heavy-duty vehicles (i.e., approximately 25 percent of the
vehicles using the bore are heavy-duty) was measured, and the air was sampled for
ii ' ' ' • !
CDD/CDFs during 7 sampling periods of 12-hour duration. Three of the samples were
collected during daytime (i.e., 6 am to 6 pm) and four samples were collected during the
night (i.e., 6 pm to 6 am). The air volume and concentration measurements were combined
with information on vehicle counts (obtained from videotapes) and tunnel length to
determine average emission factors. A total of 33,000 heavy-duty vehicles passed through
the tunnel during the seven sample runs. Heavy-duty vehicles accounted for 21.2 to 28.8
percent of all vehicles passing through the tunnel for the seven sample runs. The emission
factors calculated, assuming that all CDD/CDF emitted in the tunnel were from heavy-duty
Vehicles, are presented in Table 4-8. The average TEQ emission factor was reported to be
172 pg TEQ/km. The major uncertainties in the study were tunnel air volume
measurement, sampler flow volume control, and analytical measurement of CDD/CDF
(Gertler etal., 1996; 1998).
EPA's Office of Mobile Sources (QMS) has reviewed the Gertler et al, (1996) study
(Lorang, 1996). Overall, QMS found the study to be technologically well done, with no
major criticisms or comments on the test methodology or protocol. QMS found no reason
to doubt the validity of the emission factor determined by the study. OMS did note that
the particulate emission rate for heavy-duty vehicles measured in the study {0.32 g/mile) is
lower than the general particulate emission rate used by EPA (i.e., about 1" g/mile) and,
thus, may underestimate CDD/CDF emissions under different driving conditions. OMS
cautioned that the reported emission factor should be regarded only as a conservative
estimate of the mean emission factor for the interstate trucking fleet under the driving
conditions of the tunnel (i.e., speeds on the order of 50 miles/hour with the entering traffic
slightly higher and the exiting traffic slightly lower.
Figure 4-4 graphically presents the results of the studies by Rappe et al. (1988),
Oehme et al. (1991), Wevers et al. (1992), and Gertler et al. (1996). The figure compares
the congener profiles (i.e., congener concentrations or emission factors normalized to total
4-8 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
concentration or emission factor of 2,3,7,8-substituted CDDs and CDFs) reported in the
four studies. The dominant congeners in the Rappe et al. (1988), Wevers et al. (1992),
and Gertleret al. (1996) studies are OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF, and
1,2,3,4,6,7,8-HpCDF.'With the exception of OCDD, these congeners are also major
congeners reported by Oehme et al. (1991). The Oehme et al. (1991) study also differs
from the "other two studies jn that the total of 2,3,7,8-substituted CDFs dominates total
2,3,7,8-substituted CDDs (by a factor of 2), whereas just the opposite is observed in Rappe
et al. (1988), Wevers et al. (1992), and Gertler et al. (1996).
4.1.3. National Emission Estimates
Estimates of national CDD/CDF TEQ emissions are' presented in this section only for
on-road vehicles utilizing gasoline or diesel fuel. Because emission factors are lacking for
off-road uses (i.e., construction vehicles, farm vehicles, and stationary industrial
equipment), no emission estimates could be developed at this time.
Activity information: The U.S. Federal Highway Administration, as reported in U.S.
Department of Commerce (DOC) (1997), reports that 1,586-billion total vehicle miles
(2,552 billion km) were driven in the United States during 1994 by automobiles and
motorcycles. Because 1994 is the last year for which data are available, these data are
used as a surrogate for 1995 activity levels. Trucks accounted for 840-billion vehicle miles
(1,351-billion km), and buses accounted for 6.4-billion vehicle miles (10-billion km)
(U.S. DOC, 1997). In 1992, diesel-fueled trucks accounted for 14.4 percent of total truck
vehicle km driven; gasoline-fueled trucks accounted for the remaining 85.6 percent (U.S.
DOC, 1995b). Applying this factor (i.e., 14.4 percent) to the 1994 truck km estimate (i.e.,
1,351-billion km) indicates that an estimated 195-billion km were driven by diesel-fueled
trucks in 1994. It is assumed that all other vehicle km driven (3,718-bilIion km) were those
of gasoline-powered vehicles. It is further assumed that all of these km were driven by
unleaded gasoline-powered vehicles because in 1992, only 1.4 percent of the gasoline
supply were leaded fuel (EIA, 1993); usage should have further declined by 1995, because
use of leaded fuel in motor vehicles for highway use in the United States was prohibited as
of December 31, 1995 (Federal Register, 1985a).
'" ' •'•
4-9 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
i ••,''" ' • ' '
Similar information for 1987 is as follows. An estimated 3,092-billion km were
driven in the United States of which trucks accounted for 687-billion km (U.S. DOC,
1995a). In 1987, diesel-fueled trucks accounted for 17.2 percent of total truck km driven
{U.S. DOC, 1995b). Applying this factor (i.e., 17.2 percent) to the 1987 truck km estimate
(i.e., 887-billion km) indicates that an estimated 153-billion km were driven by diesel-fueled
trucks. It is assumed that all other vehicle km driven (2,939-billion km) were those of
gasoline-powered vehicles. Leaded gasoline accounted for 24.1 percent of the gasoline
supply in 1987 (EIA, 1993). Thus, it can be estimated that 708-billion km (i.e., 24.1
percent of 2,939-billion km) were driven by leaded gasoline-fueled vehicles. The remaining
2,231-billion km are estimated to have been driven by unleaded gasoline-fueled vehicles.
These mileage estimates are given a "high" confidence rating on the basis that they are
based on recent U.S. Bureau of the Census transportation studies.
Emission Estimates: Using the results of the studies discussed in Section 4,.1.1,
I, •!; • ', . ' -,,',' . , •'",•, i J.: ..,':,• ! '
separate annual national emission estimates are developed below for vehicles burning
leaded gasoline, unleaded gasoline, and diesel fuel. Estimates are provided for the years
1987 and 1995. The emission estimates for reference year 1995 are based on activity
data (i.e., kilometers driven) for calendar year 1994.
-,' , " , •" ' " , '• ,' ; . : . •'••, . '• ,..-..
Leaded Gasoline: Literature indicates that CDD/CDF emissions do occur from
vehicles using leaded gasoline and that considerable variation occurs depending, at least in
part, on the types of scavengers used. Marklund et al. (1987) reported emissions ranging
from 20 to 220 pg TEQ/km from four cars fueled with a reference unleaded fuel to which
lead (0.5 gplg) and a chlorinated scavenger were added. Marklund et al. (1990) reported
much lower emissions in the exhaust of cars (1.1 to 6.3 pg TEQ/km) using a commercial
leaded fuel (0.57 gplg) containing both dichloroethane and dibromoethane as scavengers.
Marklund et al. (1990) attributed the difference in the emission measurements of the 1987
and 1990 studies to the different mix of scavengers used in the two studies, which may
have resulted in preferential formation of mixed chlorinated and brominated dioxins and
furans. Hagenmaier et al. (1990) reported TEQ emissions of 1,083 pg/L of fuel (or
approximately 108 pg TEQ/km) from a car fueled with a commercial leaded fuel (lead
content not reported). Bingham et al. (1989) reported emissions from four cars using
I
4-10 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
' i ' " J
gasoline with a lead content of 1.7 gplg in New Zealand to range from 5 to 39 pg TEQ/km.
The German study reported by Schwind et al. (1991) and Hutzinger et al. (1992) measured
emissions of 52 to 1,184 pg TEQ/L (or approximately 5.2 to 118 pg TEQ/km) for cars
under various simulated driving conditions. The tunnel study by Oehme et al. (1991)
estimated that emissions from cars running primarily on leaded gasoline (i.e., 70 to 75
percent of the cars) ranged from 3.8 to 520 pg Nordic TEQ/km.
As shown in Table 4-4, the average emission factor reported for the tailpipe
emission studies performed using commercial leaded fuel (i.e., Marklund et al., 1990;
Hagenmaier et al., 1990; and Schwind et al., 1991) is 457 pg TEQ/L (or 45.7 pg/km
assuming an average fuel economy of 10 km/L). A "low" confidence rating is assigned to
this factor because it is based on European fuels and emission control technologies, which
may have differed from U.S. leaded-fuels and engine technology, and also because the
factor is based is based on tests with only nine cars.
Combining the average emission factor developed above (45.7 pg TEQ/km) with the
estimate for km driven by leaded fuel-powered vehicles in 1987 (708-billion km) suggests
that 32.4 g TEQ/yr were emitted from vehicles using leaded fuels in 1987. Based on the
low confidence rating assigned to the emission factor estimate, the estimated range of
potential emissions is assumed to have varied by a factor of 10 between the low and high
ends of the range. Assuming that the mean estimate of emissions in 1987 (32.4 g TEQ/yr)
is the geometric mean of the actual range, then the range is calculated to be 10.2 to 102 g
TEQ/yr. Although there likely was minor use of unleaded fuel in 1995, further use of
leaded fuel in motor vehicles for highway use in the United States was prohibited as of
December 31, 1995 (Federal Register, 1985a).
Unleaded Gasoline: The literature documenting results of European studies indicates
that CDD/CDF emissions are less from vehicles burning unleaded fuels than are the
emissions from vehicles burning leaded gas with chlorinated scavengers. It also'appears,
based on the limited data available, that catalyst-equipped cars have lower emission factors
than noncatalyst-equipped cars. Marklund et al. (1987) did not detect CDD/CDF in
emissions from two catalyst-equipped cars running on unleaded gasoline at a detection limit
of 13 pg TEQ/km. Marklund et al. (1990) reported emission factors of 0.36 and 0.39 pg
TEQ/km for two noncatalyst-equipped cars and an emission factor of 0.36 pg TEQ/km for
4-11
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
one catalyst-equipped car. Hagenmaier et al. (1990) reported an emission factor of 5.1 pg
TEQ/km for one noncatalyst-equipped car and 0.7 pg TEQ/km for one catalyst-equipped
car. Schwind et al. (1991) and Hutzinger et al. (1992) reported emission factors of 5.7 to
17.7 pg TEQ/km for several noncatalyst-equipped cars tested under various conditions; the
reported emission factor range for catalyst-equipped cars was 1.5 to 2.6 pg TEQ/knn.
All automobiles running on unleaded gasoline in the United States are equipped with
catalysts. As shown in Table 4-6, the average emission factor reported for the tailpipe
emission studies performed on catalyst-equipped cars (i.e., Hagenmaier et al. 1990;
Schwind et al., 1991; and Hutzinger et al., 1992) is 17 pg TEQ/L (or 1.7 pg TEQ/km
assuming an average fuel economy of 10 km/L). A "low" confidence rating is assigned to
,,1 '.. , •"' ' , ' " '' ' "' h ' ' i ' n • j •
this emission factor because the European fuels and emission control technology used may
differ from current U.S. fuels and technology and also because the emission factor range is
based on tests with;only three catalyst-equipped cars.
Combining the calculated mean emission factor of 1.7 pg TEQ/km with the estimate
derived above for vehicle km driven in 1995 by unleaded gasoline-powered vehicles (3,718
billion km) suggests that 6.3 g of TEQ were emitted from vehicles using unleaded fuels in
1995. Based on the low confidence rating for the emission factor, the estimated range of
potential annual emissions is assumed to vary by a factor of 10 between the low and high
ends of the range. Assuming that the mean estimate of annual emissions (6.3 g TEQ/yr) is
the geometric mean of the actual range, the range is calculated to be 2.0 to 20 g TEQ/yr.
Applying the same emission factor (1.7 pg/km) to the estimate derived above for
Vehicle km driven in 1987 by unleaded gasoline-powered vehicles (2,231 -billion km),
• ' 'ft, ' , '"'"' '• ' '.',''' ; :' , '..' ', ; ••'' . , l"';"' '•'''.';'
Suggests that 3.8 g of TEQ may have emitted in 1987. Assuming that this estimate is the
' ".;':" • •' •. , ,. " '"'•:• !V '' *., '.' ' ' • . I
geometric mean of the actual range yields a range of 1.2 to 12 g TEQ/yr.
""' ' ; ' \ '•:: •
Diesel Fuel: Few data are available upon which to base an evaluation of the extent
of CDD/CDF emissions resulting from diesel fuel combustion. The limited data available
address emissions only from on-road vehicles; no emissions data are available for off-road
diesel uses (i.e., construction vehicles, farm vehicles, arid stationary equipment). Two U.S.
tailpipe studies are available: CARB (1987a) and Gullett and Ryan (1997). CARB (1987a)
reported a relatively high emission factor of 663 pg TEQ/km (not detected values assumed
to be zero) for one tested heavy-duty truck with a fuel economy at 50 km/hr of 5.5 km/L.
4-12 . April 1998
-------
DRAFT—DO NOT QUOTE OR CITE
: . \ . , .
Gullett and Ryan (1997) reported a range of emission, factors for one diesel truck tested on
six highway or city driving routes, 3.0 to 96.8 pg TEQ/km (mean of 29.0 pg TEQ/km).
The results of several tailpipe studies conducted in Europe have also been published.
Marklund et al. (1990) reported no emissions at a detection limit of 100 pg TEQ/L (or 18 pg
TEQ/km assuming a fuel economy of 5.5 km/L) for one tested truck. Schwind et al. (1991)
and Hutzinger et al. (1992) reported emission factors of 32 to 81 pg TEQ/L (or 6 to 15 pg
TEQ/km assuming a fuel economy of 5.5 km/L) for a truck engine run under various
simulated driving conditions. Hagenmaier (1994) reported no emissions from a bus at a
detection limit of 1 pg/L of fuel consumed for individual congeners. For diesel-fueled cars,
Hagenmaier et al. (1990) reported an emission factor of 24 pg TEQ/L (or approximately 2.4
pg TEQ/km) for one tested car. Schwind et al. (1991) and Hutzinger et al. (1992) reported
emission factors of 5 to 13 pg TEQ/km for a car engine run under various simulated driving
conditions. .. " " .
The tunnel study by Oehme et al. (1991) generated an estimated mean emission
factor of 5,100 pg TEQ/km and a range of 720 to 9,500 pg TEQ/km (in units of Nordic
TEQ) for diesel-fueled trucks. Insufficient information was provided in Oehme et al. (1991)
to enable an exact calculation of emission in units of I-TEQ. However, based on the
information that was provided, the mean emission factor in units of I-TEQ is approximately
5,250 to 5,400 pg l-TEQ/km. These indirectly estimated emission factors are considerably
larger than those reported from engine studies by Marklund et al. (1990), Schwind et al.
(1991), and Hutzinger et .a I. (1992); the CARB (1987a) diesel truck emission factor falls at
the low end of the range. Although aggregate samples were collected in this study
representing several thousand heavy duty diesel vehicles, several characteristics of this
study introduce considerable uncertainty with regard to using the study's results as a basis
for estimating emissions in the United States. These factors include: (1) heavy-duty
vehicles comprised only 3 to 19 percent of total vehicle traffic in the tunnel; (2) the
majority of the light-duty vehicles were fueled with leaded gasoline the combustion of
which, as noted above in Table 4-4, can release considerable amounts of CDD/CDFs; and
(3) technology differences likely existed between the 1988 Norwegian and the 1987 and
1995 U.S. vehicle fleets.
The recent tunnel study conducted in Baltimore, Maryland, by Gertler et al. (1996;
1998) has the same disadvantages shared by all tunnel studies relative to tailpipe studies.
4-13 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Specifically, tunnel studies rely on indirect measurements (rather than tailpipe
measurements), which may introduce unknown uncertainties, and the emission factors
calculated from these studies reflect driving conditions by the vehicle fleet using the tunnel
and not necessarily the overall vehicle fleet under other driving conditions. However, the
Gertler et al. (1996; 1998) study does have strengths lacking in the Oehme et al. (1991)
tunnel study. Also, the Gertler et al. (1996; 1998) study has benefits over the two U.S.
diesel truck taipipe studies. These include: (1) the study is a recent study conducted in
the United St.ates and thus reflects current U.S. fuels and technology; (2) virtually no
vehicle using the tunnel used leaded gasoline; (3) the tunnel walls and streets were cleaned
1 week prior to the start of sampling and, in addition, the study analyzed road dust and
determined that resuspended road dust contributed only about 4 percent of the estimated
emission factors; (4) heavy-duty vehicles comprised, on average, a relatively large
percentage (25.7 percent) of vehicles using the tunnel; and (5) a large number of heavy-
duty vehicles, approximately 33,000, passed through the tunnel during the sampling period,
which generates confidence that the emission factor is representative of interstate trucks.
In consideration of the strengths and weaknesses of the available emission factor
data from the tailpipe and tunnel studies, the mean TEQ emission factor reported by Gertler
et al. (1996; 1998), 172 pg TEQ/km, is assumed to represent the best current estimate of
the average emission factor for on-road diesel-fueled trucks. Because it may not be
. i , , , . : . 11
representative of emission rates for the entire fleet of diesel-fueled trucks under the wide
array of driving conditions encountered on the road, this emission factor is assigned a
"low" confidence rating.
Combining the calculated mean emission factor from Gertler et al. (1996; 1998)
with the above estimate for vehicle kms driven in 1995 in the United States by diesel-
fueled trucks (195-billion km) suggests that 33.5 g of TEQ were emitted from trucks using
diesel fuel in 1995. Based on the "low" confidence rating assigned to this emission factor,
the estimated range of potential annual emissions is assumed to vary by a factor of 10
between the low and high ends of the range. Assuming that the mean estimate of annual
emissions (33.5 g TEQ/yr) is the geometric mean of the actual range, then the range is
calculated to be 10.6 to 106 g TEQ/yr.
Combining the same emission factor (172 pg TEQ/km) to the estimate derived above
for vehicle km driven in 1987 by diesel-fueled trucks (153-billion km) suggests that: 26.3 g
4-14 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
of TEQ were emitted from diesel-fueled trucks in 1987; the range is calculated (8.3 to 83.2
g TEQ/yr).
4.2. WOOD COMBUSTION
In 1995, wood fuel provided about 2.6 percent (or 2,350-trillion Btu) of the total
primary energy consumed in the United States (EIA, 19975). During 1987, wood energy
consumption is estimated to have been 2,437-trillion Btu, or 3.2 percent of, total primary
energy consumed (EIA, 1997b). The industrial sector is the largest consumer of wood fuel,
accounting for almost 72 percent of total wood fuel consumption in 1995 and 65 percent
in 1987. The residential sector accounted for 25 percent of consumption in 1995 and 35
percent in 1987. The electric utility sector accounted for less than 1 percent of total
consumption in both years. There are no accurate sources to provide reliable estimates of
commercial wood energy use; consumption is thought to be between 20- and 40-trillion
Btu, or 2 to 4 percent of total wood consumption (EIA, 1994; EIA, 1997b).
These energy consumption estimates, however, appear to include the energy value
of black liquor solids. Which are combusted in recovery boilers by wood pulp mills. In 1,987
and 1995, the energy value of combusted black liquor solids were 950-trillion Btu and
1,078-trillion Btu, respectively (American Paper Institute, 1992; American Forest & Paper
Association, 1997). Subtracting these black liquor energy value estimates from the
national totals for wood fuel yields 1,487-trillion Btu in 1987 and 1,272-trillion Btu in
1995. Assuming that 1 kg of oven-dried wood (i.e., 2.15 kg of green wood) provides
approximately 19,000 Btu (EIA, 1994), then an estimated 66.9-million and 78.3-million
metric tons of oven-dried wood equivalents were burned for energy purposes in 1995 and
1987, respectively. Of these totals, an estimated 31.4-million metric tons and 44.8-million
metric tons were consumed by the residential sector in 1995 and 1987, respectively. An
estimated 35.5-million metric tons and 33.5-million metric tons were consumed by the
industrial sector in 1995 and 1987, respectively.
The following two subsections discuss the results of relevant emission studies for
the residential and industrial sectors and present annual emission estimates. -
4-15 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
4.2.1. Residential Wood Combustion
! i '' ' ' I . i|. , _ . i
The measurement of CDDs and CDFs jn chimney soot and bottom ash from wood-
burning stoves and fireplaces has been reported by several researchers (Bumb et al., 1980;
Nestrick and Lamparski, 1982 and 1983; Clement et al., 1985b; Bacher et al., 1992; Van
Oostam and Wprd, 1995; and Dumler-Gradl et al., 1995a). Two studies have provided
direct measurement of CDD/CDFs in flue gas emissions from wood stoves (Schatowitz et
al., 1993; Vikelsoe et al., 1993). The findings of each of these studies are summarized in
the following paragraphs.
Bumb et al. (1980) detected TCDDs (ND-0.4 /^g/kg), HxCDDs (0.2-3 ,ug/kg),
HpCDDs (0.7-16 /zg/kg), and OCDD (0.9-25 /ug/kg) in residues from the wall of one home
fireplace and from the firebrick of another home fireplace; for lack of a suitable analytical
method, analysis was not performed for PeCDDs. Neither of the fireplaces sampled by
Bumb et al. (1980) had burned preservative-treated wood.
Nestrick and Lamparski (1982; 1983) expanded the research of Bumb et al. (1980)
by conducting a survey of CDD concentrations in chimney soot from residential wood-
burning units in three different rural areas of the United States. Samples were collected
from the base of six chimneys in each of the three study areas. Results of a pilot study at
one residential chimney site had determined that this location provided the highest CDD
concentrations in soot. Samples were not collected from units where any type of treated
or manufactured wood had been burned. For lack of a suitable analytical method, analysis
was not performed for PeCDDs. The results of this,survey are summarized in Table 4-9.
There was wide variation in the results across soot samples with standard deviations for
congeners and congener groups often equal to or exceeding the mean value; however,
CDDs in each congener group were detected in the soot from almost all sampled units.
Nestrick and Lamparski (1982; 1983) concluded that the-results do not appear to present
any easily discernible patterns with respect to geographic region, furnace operational •
parameters, or wood fuel type. Nestrick and Lamparski (1982; 1983) attribute the wide
variability observed to differences in design of the different units, which affected the
sampling point and/or the conditions at the sampling point, and/or possible contamination
of the fuel wood.
Clement et al. (1985b) analyzed chimney soot and bottom ash from residential
' • f ' • . , • ' .' ' . .,•,•> ;. . '
woodstoves and fireplaces in Canada. The CDD/CDF congener concentrations are
4-16 April 1998
-------
DRAFT-DO NOT QUOTE OR GITE
presented in Table 4-9v (soot) arid Table 4-10 (bottom ash). CDD/CDF congeners were
detected in all samples analyzed, although the relative amounts of the different congener
groups varied considerably and inconsistently within the type of wood burning unit and
between ash and soot samples from the same unit.
Bacher et al. (1992) characterized the full spectrum (i.e., mono- through octa-
substitution) of chlorinated and brominated dibehzo-p-dioxin and dibenzofuran congeners in
the soot from an old farmhouse in southern Germany. The chimney carries smoke from an
oven that had used untreated wood at the rate of about 5 m3 per year for more than 10
* . , • ,
years, the sample was taken during the annual cleaning by a chimney sweep. The only
BDF detected was mono-BDF (230 ng/kg). No BDDs, BCDDs, or BCDFs were detected at a
detection limit of 20 ng/kg. The results for the tetra- through octa- CDDs and CDFs are
presented in Table 4-9. The results indicate that CDFs dominate the CDDs in each
congener group except octa. Also, the lower chlorinated congener groups dominate the
>
higher chlorinated congener groups for both the CDDs and CDFs. The TEQ content of the
chimney soot was 720 ng/kg of which less than 30 percent was due to CDDs.
Van Oostdam and Ward' (1995) analyzed soot from two wood stoves in British
Columbia, Canada, and found TEQ concentrations of 86 and 335 ng TEQ/kg. The
congener-specific results are presented in Table 4-9. The soot from a wood stove burning
salt-laden wood in a coastal area was found to have a TEQ content of 7,706 ng TEQ/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 4-11. As was observed by
Nestrick and Lamparski (1982; 1983) and Clement et al. (1985b), CDD/CDFs were
detected in all samples; however, there was wide variability in total TEQ concentrations
within and across unit type/fuel type combinations.
Schatowitz et al. (1993) measured the CDD/CDF content of flue gas emissions from
several types of wood burners used in Switzerland: a household stove (6 kW), automatic
chip furnaces (110 to 1,800 kW), and a wood stick boiler (35 kW). The emissions from
combustion of a variety of wood fuels were measured (natural beech wood, natural wood
chips, uncoated chipboard chips, waste wood chips from building demolition, and
• 4-17 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
household paper and plastic waste). The results from the testing o.f the household stove
are most relevant for assessing releases from residential combustion. The household stove
was tested with the stove door both open and closed. The open door stove can be
assumed to be representative of fireplaces because both have an uncontrolled draft.
Although the congener/congener group analytical results were not reported, the following
emission factors (dry weight for wood; wet weight for household waste) and emission rates
{corrected to 13 volume% oxygen) for the household stove were reported by Schatowitz et
al. (1993):
• Open door burn of beech wood sticks: 0.77 ng TEQ/kg (0.064 ng TEQ/Nm3);
• Closed door burn of beech wood sticks: 1.25 ng TEQ/kg ' (0.104 ng TEQ/Nm3);
and
• Closed door burn of household waste: 3,230 ng TEQ/kg (114.4 ng TEQ/Nm3).
Vikelsoe et al. (1993) studied emissions of CDD/CDF congener groups from
residential wood stoves in Denmark. The wood fuels used in the experiments were
seasoned birch, beech, and spruce, equilibrated to 18 percent absolute moisture. Four
different types of stoves (including one experimental stove) were evaluated under both
normal and optimal (i.e., well controlled with CO emission as low as possible) operating
conditions. Widely varying total CDD/CDF emissions were found for the 24 different
fuel/stove type/operating condition combinations. The emissions from spruce were about
twice as high as the emissions from birch and beech. Surprisingly, the "optimal" operating
•i! ,':,'',„ « ' v "„, ' ' ' '. ' ii ' , ' • ,."''" '!' ' i •'
condition led to significantly higher CDD/CDF emissions for two stove types, but not for the
other stoves. The predominant congener group for all experiments was TCDF. The
weighted average (considering wood and stove types) emission rate and emission factor for
wood stoves were reported to be 1.9 ng Nordic-TEQ/kg and 0.18 ng Nordic-TEQ/Nrn3,
respectively. Because Vickelsoe et al. (1993) did not measure congener levels, the
reported emission factor and emission rate were estimated by assuming the same congener
distribution in each congener group that had been found for municipal waste incinerators.
Based on the results reported by Schatowitz et al. (1993) and Vickelsoe et al.
., i , ' ".,;" '':''; t - / . , "i , :' •/ , ••'.' '.','• .'' ' ;' ' ''. ""'', , " " . ' ',
(1993), 2 ng TEQ/kg appear to be a reasonable average emission factor for residential
: ': l! • • f ' , '•'• ':.' :":''• , • *' '•.','.. ' i ' '
wood burning. A "low" confidence rating was assigned to this estimate on the basis that it
4-18 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
is derived from only two direct measurement studies. Although the studies were
conducted in Europe, residential wood burning practices are probably sufficiently similar to
apply to the United States.
In 1987, 22.5-million households in the United States burned wood (EIA, 1991). Of
these households, wood was used in 1987 as the primary heating fuel in 5-million
households and as a secondary source for aesthetic purposes (i.e., fireplaces) in 17.4-
miilion households (EIA, 1991; EIA, 1997b). Lower numbers were reported fpr 1995;
wood was reported to be used as the primary fuel in 3.53-million households (EIA, 1997b).
More rural low-income households consume wood as a primary heating fuel than do other
sectors of the population. The majority of these households use wood-burning stoves as
the primary heating appliance. Although fireplaces are the most common type of wood-
burning equipment in the residential sector, only 7 percent of fireplace users report use of
fireplaces for heating an entire home (EIA, 1991; EIA, 1994).
Residential wood consumption in 1995 was 596-trillion Btu (31.4-million metric
tons), or 25 percent of total U.S. wood energy consumption (EIA, T997b). In 1987,
residential wood consumption was 852-trillion Btu (44.8-million metric tons), or 35 percent
of total U.S. consumption (EIA, 1997b). These production estimates are given "high"
confidence ratings because they are based on recent government survey data.
Combining the best estimate of the emission factor (2 ng TEQ/kg wood) wjth the
mass of wood consumed,by residences in the years 1995 and 1987 indicates that the
annual TEQ air emissions from this source were approximately 62.8 grams in 199.5 and
89.6 grams in 1987. Based on the "low" confidence rating assigned to the emission
\
factor, the estimated range of potential annual emissions is assumed to vary by a factor of
10 between the low and high ends of the range. Assuming that the best estimate of
annual emissions in 1995 (62.8 g TEQ/yr) is the geometric mean of this range, then the
range is calculated to be 19.8 to 198 g TEQ/yr. For 1987, the range is calculated to be
28.3 to 283 g TEQ/yr.
( ' *
4.2.2. Industrial Wood Combustion
Congener-specific measurements of CDD/CDFs in stack emissions from industrial '
wood-burning furnaces were measured by the California Air Resources Board at four
facilities in 1988 (CARB, 1990b; CARB, 1990e; CARB, 1990f; CARB, 1990g).
'4-19 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
•••'',. .it . «'•''., • . ' ,i
Measurements of CDD/CDF congener groups and 2,3,7,8-TCDD and 2,3,7,8-TGDF were
reported for one facility by EPA (U.S. EPA, 1987a). the National Council of the Paper
Industry for Air and Stream Improvement (NCASI) (1995) presented congener-specific
emission factors for five boilers tested during burns of bark/wood residue. The average
congener emission factors derived from the four CARS studies are presented in Table 4-12.
Congener and congener group profiles are presented in Figure 4-5.
In GARB (1990b), CDD/CDFs were measured in the emissions from a quad-cell
wood-fired boiler used to generate electricity. The fuel consisted of coarse wood waste
and sawdust from nonindustrial logging operations. The exhaust gas passed through a
multicyclone before entering the stack. From this study, average emission factors for total
CDD/CDF and total TEQ are calculated to be 48.1 and 0.64 ng/kg of wood burned,
respectively.
In CARB (1990e), CDD/CDFs were measured in the emissions from two spreader
stoker wood-fired boilers operated in parallel by an electric utility for generating electricity.
The exhaust gas stream from each boiler is passed through a dedicated ESP after which the
gas streams are combined and emitted to the atmosphere through a common stack. Stack
tests were conducted both when the facility burned fuels allowed by existing permits and
when the facility burned a mixture of permitted fuel supplemented by urban wood waste at
a ratio of 70:30. From this study, average emission factors for total CDD/CDF and total
TEQ are calculated to be 29.2 and 0.82 ng/kg of wood burned, respectively.
In CARB (1990f), CDD/CDFs were measured in the emissions from a twin fluidized
bed combustors designed to burn wood chips for the generation of electricity. The air
pollution control device (APCD) system consisted of ammonia injection for controlling
nitrogen oxides, and a multiclone and electrostatic precipitator for controlling paniculate
matter. During testing, the facility burned wood wastes and agricultural wastes allowed by
existing permits. From this study, average emission factors for total CDD/CDF and total
1 ' ' '',.'' ' ' ' ' • I • •
TEQ are calculated to be 47.9 and 1.32 ng/kg of wood burned, respectively.
In CARB (1990g), CDD/CDFs were measured in the emissions from a quad-cell
wood-fired boiler. During testing, the fuel consisted of wood chips and bark. The flue
gases passed through a multicyclone and an ESP before entering the stack. From this
study, average emission factors for total CDD/CDF and total TEQ are calculated to be 27.4
and 0.50 ng/kg of wood burned, respectively.
4-20 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
The facility tested by EPA was located at a lumber products plant that manufactures
overlay panels and other lumber wood products. The wood-fired boiler tested was a three-
cell dutch oven equipped with a waste heat boiler. The feed wood was a mixture of bark,
hogged wood, and green and dry planar shavings. Nearly all the wood fed to the lumber
plant had been stored in sea water adjacent to the facility and, therefore, had a significant >
concentration of inorganic chloride. The exhausted gases from the boiler passed through a
cyclone and fabric filter prior to discharge from the stack. From this study, an average
emission factor for total CDD/CDF of 1,020 ng/kg of wood burned (range: 552 to 1,410
ng/kg) was reported. An average emission factor for TEQ of 17.1 ng/kg of wood burned
(range: 7.34 to 22.8 ng/kg) was estimated by EPA using measured congener group
concentrations and concentrations of 2,3,7,8-TCDD and 2,3,7,8-TCDF. These emission
factors from the burning of salt wood are significantly higher than those measured in the
four CARB studies. This finding was consistent with the conclusion of NCASI (1995) that
CDD/CDF emissions from facilities burning salt-laden wood residue may be considerably
higher than from those burning salt-free wood.
NCASI (1995) presented stack emission test results for five boilers burning bark or
wood residues. One of these facilities, equipped with a multicyclone, normally burns bark
in combination with sludge and coal. One other facility, equipped with an ESP, normally
; '
fires pulverized coal. The other three facilities were spreader stokers equipped with
multicyclones or ESPs. Although stack gas flow rates were obtained during these tests,
accurate measurements of the amounts of bark/wood fired were riot made and had to be
estimated .by~ NCASI (1995) from steam production rates. The average TEQ emission factor
for these facilities was 0.4 ng/kg of feed.
The mean of the emission factors derived from the four CARB studies, 0.82 ng
TEQ/kg wood (assuming nondetected values are zero), is used in this report as most
representative of industrial wood combustion. The results of the EPA study were not used
in the derivation of this mean emission factor because congener-specific measurements for
most 2,3,7,8-substituted congeners were not made. Because congener-specific test data
were available for these four facilities and because the mean TEQ emission factor derived
-. f ..-,', ,
from these test data is very similar to that estimated by NCASI (1995) for five wood-fired
.. boilers, this emission factor was assigned a "medium" confidence rating.
4-21 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
It should be noted, however, that this emission factor (0.82 ng TEQ/kg wood) may
not be an appropriate emission factor to apply to the combustion of waste wood containing
elevated chlorine content. Umweltbundesamt (1996) reported the results of stack gas
testing at approximately 30 facilities of varying design type as well as type of wood fuel
combusted. Elevated CDD/CDF emissions were observed when the combustion conditions
were poor, as evidenced by elevated carbon monoxide emissions, and/or when the fuel
contained elevated chlorine levels. Umweltbundesamt (1996) attributed the correlation
i ' ' . • •• •,' , . • '. ;
between elevated CDD/CDF emissions and elevated chlorine content of the fuel to the fire
i' ,''•''' '" ; ,'; . V . • V • |;I '' ' •' !
retardant effects of chlorine, which may have inhibited complete combustion. The chlorine
content of untreated wood and bark were reported to range from 0.001 to 0.01 percent by
weight and 0.01 to 0.02 percent by weight, respectively. Chipboard can contain up to 0.2
percent chlorine by weight because of binding agents used to manufacture the chipboard.
Preservative-treated wood and PVC-coated wood were reported to contain chlorine
contents as high as 1.2 and 0.3 percent by weight, respectively.
"'' , '. ' ' • ''"' ' : • .''' '•'.••'.' , ',
As discussed in Section 4.2, industrial wood consumption in 1995 totaled 35.5-
million metric tons. The majority of wood fuel consumed in the industrial sector consists of
wood waste (i.e., chips, bark, sawdust, and hogged fuel). Consumption in the industrial
sector is dominated by two industries: the "Paper and Allied Products" industry - SIC 26
and the "Lumber and Wood Products" industry - SIC 24 (EIA, 1994). A similar amount,
33.5-million metric tons, was burned for fuel in industrial furnaces in 1987 (EIA, 1994).
These activity level estimates are assigned a "high" confidence rating because they are
based on recent government survey data.
Applying the average TEQ emission factor from the four CARB studies (0.82 ng
TEQ/kg wood) to the estimated quantities of wood burned by industrial facilities in 1995
and 1987 yields estimated TEQ emissions to air of 29.1 g TEQ in 1995 and 27.5 g TEQ in
1987. Based on the "medium" confidence rating given to the TEQ emission factor, the
estimated range of potential annual emissions is assumed to vary by a factor of five
between the low and high ends of the range. Assuming that the estimates of annual
emissions to air for these 2 years are the geometric means of the respective ranges, then
the ranges are calculated to be 13.0 to 65.0 g TEQ in 1995 and 12.3 to 61.5 g TEQ in
1987.
4-22 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
4.3. OIL COMBUSTION
Two major categories of fuel oil are burned by combustion sources: distillate oils
and residual oils. These oils are further distinguished by grade numbers, with Nos. 1 and 2
being distillate oils; Nos. 5 and 6 being residual oils; and No. 4 either distillate oil or a
mixture of distillate and residual oils. No. 6 fuel oil is sometimes referred to as Bunker C.
Distillate oils are more volatile and less viscous than residual oils. They have negligible
nitrogen and ash contents and usually contain less than 0-3 percent sulfur (by weight).
Distillate oils are used mainly in domestic and small commercial applications. Being more
viscous and less volatile than distillate oils, the heavier residual oils (Nos. 5 and 6) must be
heated for ease of handling and to facilitate proper atomization. Because residual oils are
produced from the residue remaining after the lighter fractions (gasoline, kerosene, and
distillate oils) are removed from the crude oil, they contain significant quantities of ash,
nitrogen, and sulfur. Residual oils are used mainly in utility, industrial, and large commercial
application (U.S. EPA, 1995b).
4.3.1. Residential/Commercial Oil Combustion
No testing of the CDD/CDF content of air emissions from residential/commercial oil-
fired combustion units in the United States could be located. However, U.S. EPA (1997b)
has estimated CDD/CDF congener group and TEQ emission factors based on average
CDD/CDF concentrations reported for soot samples from 21 distillate fuel oil-fired furnaces
used for central heating in Canada, and a paniculate emission factor for distillate fuel oil
combustprs (300 mg/L of oil) obtained from AP-42 (U.S. EPA, 1995b). The TEQ emission
factor estimate in U.S. EPA (1997b) was derived using the calculated emission factors for
2,3,7,8-TCDD, 2,3,7,8-TCDF, and the 10 congener groups. These emission factors are
presented in Table 4-13/and the congener group profile is presented in Figure 4-6.
Because there are no direct measurements of CDD/CDF emissions in stack gases
from U.S. residential oil-fired combustors and because of uncertainties associated with
using chimney soot data to estimate stack emissions, no national emission estimates for
this category are proposed at this time. However,,a preliminary order of magnitude
estimate of national TEQ emissions from this source category can be derived using the
emission factor presented in Table 4-13 (150 pg TEQ/L of oil combusted). Distillate fuel oil
sales to the residential/commercial sector totaled 39.7 billion liters in 1995 (EIA, 1997a).
4-23 _.' April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Application of the TEQ emission factor of 150 pg TEQ/L to this fuel oil sales estimate
results in estimated TEQ emissions of 6.0 g TEQ in 1995, which, when rounded to the
nearest order of rnagnitude to emphasize the uncertainty in this estimate, results in a value
of 10 g TEQ/yr. This estimate should be regarded as a preliminary indication of possible
emissions from this source category; further testing is needed to confirm the true
magnitude of the emissions.
4.3.2. Utility Sector and Industrial Oil Combustion
Preliminary CDD/CDF emission factors for oil-fired utility boilers developed from
boiler tests conducted over the past several years are reported in U.S. EPA (1995c). The
data are a composite of various furnace configurations and APCD systems. Table 4-14 lists
the median emission factors presented in U.S. EPA (1995c; 1997b). The congener and
congener group profiles based on these data are presented in Figure 4-7. The median TEQ
emission factor was reported to be 314 pg/L of oil burned.
In 1993, the Electric Power Research Institute (EPRI) sponsored a project to gather
information of consistent quality on power plant emissions. This project, the Field
Chemical Emissions Measurement (FCEM) project, included testing of two cold side ESP-
equipped oil-fired power plants for CDD/CDF emissions (EPRI, 1994). The averages of the
congener and congener group emission factors reported for these two facilities are also
presented in Table 4-14. The average TEQ emission factor is 95.5 pg/L of oil burned when
nondetected values are treated as zero (170 pg/L when nondetected values are treated as
one-half the detection limit).
The TEQ emission factor reported in EPRI (1994) is a factor of three less than the
median TEQ emission factor reported in U.S. EPA (1 995c; 1997b). For purposes of this
assessment, an emission factor of 200 pg/L (i.e., the average of 95.5 and 314 pg/L) is
assumed to be current best estimate of the average TEQ emission factor for
utility/industrial oil burning. This estimate is assigned a "low" confidence rating.
TEQ emission factors an order of magnitude larger were reported by Bremmer et al.
(1994), based on measurements of CDD/CDF emission from three stationary used oil
combustion units and from a ferry fired with a blend of used and virgin oil. Flue gases from
a garage stove consisting of an atomizer fueled by spent lubricating oil from diesel engines
•' ',V - •' "' '. ; • '• '' " '', .V- - "" ' *' " '
(35 mg ClVkg) were reported to contain 0.1 ng TEQ/Nnrr (or 2 ng TEQ/kg of oil burned).
4-24 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
The flue gases from a hot water boiler consisting of a rotary cup burner fueled with the
organic phase of rinse water from oil tanks (340 mg Cl'/kg) contained 0.2 ng TEQ/Nm3 (or
'4.8 ng TEQ/kg of oil burned). The flue gases from a steam boiler consisting of a rotary cup
burner fueled by processed spent oil (240 mg ClVkg) contained 0.3 ng TEQ/Nm3 (or 6.0 ng
TEQ/kg of oil burned). The emission rate from the ferry (heavy fuel oil containing 11 ng/kg
organic chlorine) was 3.2 to 6.5 ng TEQ/kg of oil burned. From these data, Bremmer et al.
(1994) derived an average emission factor for combustion of used oil of 4 ng TEQ/kg of oil
burned.
Bremmer et al. (1994) also reported measuring CDD/CDF emissions from a river
barge and a container ship fueled with gas oil (less than 2 ng/kg of organic chlorine). The
exhaust gases contained from 0.002 to 0.2 ng TEQ/Nm3. From these data, Bremmer et al.
(1994) derived an average emission factor for inland oil-fueled vessels of T ng; TEQ/kg oil
burned. .
Residual fuel oil sales totaled 46.6-billion liters in 1995 and 77.3 billion liters in
1987 (EIA, 1992; 1997a). Vessel bunkering was the largest consumer (48 percent of
sales) followed by electric utilities and the industrial sector. A "high" confidence rating is
assigned to these production estimates. Application of the TEQ emission factor of 200
pg/L to these residual fuel oil sales results in estimated TEQ emissions of 9.3 g TEQ in
1995 and 15.5 g TEQ in 1987. Based on the "low" confidence rating assigned to the
ejnission factors, the estimated range of potential emissions is assumed to vary by a factor
of 10 between the low and high ends of the range. Assuming that the estimate of TEQ
emissions in 1995 (i.e., 9.3 g TEQ) is the geometric mean of the range, then the range is
calculated to be 2.9 to 29 g TEQ/yr. For the year 1987, the range is calculated to be 4.9
to 49 g TEQ/yr.
4.4. COAL COMBUSTION
During 1995, coal consumption accounted for approximately 22 percent of the
energy consumed from all sources in the United States (U.S. DOC, 1997). In 1995, 872-
million metric tons of coal were consumed in the United States. Of this total, 88.4 percent
(or 771-million metric tons) were consumed by electric utilities, 1 T.O percent (or 96-million
metric tons) were consumed by the industrial sector (including consumption of 30 million
metric tons by coke plants), and 0.6 percent (or 5.3-million metric tons) were consumed by
4-25 ; . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
residential and commercial sources (EIA, 1997b). Comparable figures for 1987 are: total
consumption, 759-million metric tons; consumption by electric utilities, 651-million metric
tons; consumption by coke plants, 33.5-million metric tons; consumption by other
industries, 68.2-million metric tons; and consumption by the residential and commercial
sectors, 6.3-million metric tons (EIA, 1995c). These production estimates are assigned a
"high" confidence rating because they are based on detailed studies specific to the United
States.
The following two subsections discuss the results of relevant emission studies for
the utility/industrial and residential sectors and present annual emission estimates.
4.4.1. Utilities and Industrial Boilers
Until recently, few studies had been performed to measure CDD/CDF concentrations
in emissions from coal-fired plants, and several of these studies did not have the congener
specificity and/or detection limits necessary to fully characterize this potential source (U.S.
EPA, 1987a; NATO, 1988; Wienecke et al., 1992). Recently, the results of testing of coal-
fired utility and industrial boilers have been reported for facilities in The Netherlands, the
United Kingdom, and the United States.
Bremmer et al. (1994) reported the results of emission measurements at two coal-
fired facilities in The Netherlands. The emissjon rate from a pulverized coal electric power
plant equipped with an ESP and a wet scrubber for sulfur removal was reported as 0.02 ng
TEQ/Nm3 (at 11 percent O2) (or 0.35 ng TEQ/kg of coal fired). The emission rate for a
grass drying chain grate stoker equipped with a cyclone APCD was reported to be 0.16 ng
TEQ/Nm3 (at 11 percent O2) (or 1.6 ng TEQ/kg of coal fired). Cains and Dyke (1994)
recently reported an emission rate of 102 to 109 ng TEQ/kg of coal at a small-scale facility
in the United Kingdom that was equipped with an APCD consisting only of a grit arrester.
Umweltbundesamt (1996) reported that the TEQ content of stack gases from 16 coal-
burning facilities in Germany ranged from 0.0001 to 0.04 ng TEQ/m3; the data provided in
this report did not enable emission factors to be calculated.
The U.S. Department of Energy sponsored a project in 1993 to assess emissions of
hazardous air pollutants at coal-fired power plants. As part of this project, CDD/CDF stack
emissions were measured at seven U.S. coal-fired power plants. The preliminary results of
this project (i.e., concentrations in stack emissions) were reported by Riggs et al. (1995)
1 jr | f , , , , • , ,
4-26 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
• - ' '. y • " - - ' •
and are summarized in Table 4-15. The levels reported for individual 2,3,7/8-substituted
congeners were typically not detected or very low (i.e., ^0.033 ng/Nm3). In general, CDF
levels were higher than CDD levels. OCDF and 2,3,7,8-TCDF were the most frequently
detected congenersl'(i.e., at four of the seven plants). Table 4-16 presents characteristics
of the fuel used and APCD employed at each plant. Variation in emissions between plants
! ~ •
could riot be attributed by Riggs et al. (1995) to any specific fuel or operational
characteristic.
During the early 1990s, EPRI also sponsored a project to gather information of
consistent quality on power plant emissions. This project, the Field Chemical Emissions
Measurement (FCEM) project,.included testing of four cold-side ESP-equipped coal-fired
power plants for CDD/CDF emissions. Two plants burned bituminous coal and two burned
subbituminous coal. The final results of the DOE project discussed above were integrated
with the results of the EPRI testing and published in 1994 (EPRI, 1994). The average
congener and congener group emission factors derived from this 11 facility data set, as
reported in EPRI (1994), are presented in Table 4-17. Congener and congener group
profiles for the data set are presented in Figure 4-8. The average TEQ emission factor,
assuming nondetected values are zero, is 0.087 ng/kg of coal combusted. The average
TEQ emission rate, assuming nondetected values are one-half the detection limit, is 0.136
ng/kg of coal combusted. A "medium" confidence rating is assigned to these emission
factors because they are based on recent testing at U.S. facilties.
As stated above, consumption of coal by the U.S. utility and industrial sectors
(excluding consumption at coke plants) was 837-million metric tons in 1995 and 719-
million metric tons in 1987. Applying the TEQ emission factor of 0.087 ng TEQ/kg of coal'
combusted to these production factors yields estimated annual emissions of 72.8 g TEQ in
1995 and 62.6 g TEQ in 1987.
Based on the "medium" confidence rating assigned to the estimated TEQ emission
factor, the estimated range of potential emissions is assumed to vary by a factor of five
between the low and high ends of the range; Assuming that the estimated emissions
(assuming nondetected values are zero) of 72.8 g TEQ in 1995 and 62.6 g TEQ in 1987
are the geometric means of these ranges for these years, then the ranges are calculated to
be 32.6 to 163 g TEQ in 1995 and 28 to 140 g TEQ in 1987.
4-27 •- • " ' April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
4.4.2. Residential/Commercial Coal Combustion
Coal is usually combusted in underfeed or hand-stoked furnaces in the residential
sector. Other coal-fired heating units include hand-fed room heaters, metal stoves, and
metal and masonry fireplaces. Stoker-fed units are the most common design for warm-air
furnaces and for boilers used for steam or hot water production. Most coal combusted in
these units are either bituminous or anthracite. These units operate at relatively low
temperatures and do not efficiently combust the coal. Coal generally contains small
quantities of chlorine and CDD/CDF; therefore, the potential for CDD/CDF formation exists.
Typically, coal-fired residential furnaces are not equipped with particulate matter or gaseous
pollutant control devices that may limit emissions of any CDD/CDFs formed (U.S. EPA,
I997b). No testing of the CDD/CDF content of air emissions from residential/commercial
coal-fired combustion units in the United States could be located. However, several
relevant studies have been performed in European countries.
Thub et al. (1995} measured flue gas concentrations of CDD/CDF from a household
heating system in Germany, fired either with "salt" lignite coal (i.e., total chlorine content
of 2,000 ppm) or "normal" lignite coal (i.e., total chlorine content of 306 ppm). CDD/CDFs
were detected in the flue gases generated by combustion of both fuel types. (See
Table 4-18.) The congener profiles and patterns were similar for both fuel types, with
OCDD the dominant congener and TCDF the dominant congener group. However, the
emissions were higher for the "salt" coal (0.109 ng TEQ/m3 or 2.74 ng TEQ/kg of coal) by
a factor of eight than for the "normal" coal (0.015 ng TEQ/m3 or 0.34 ng TEQ/kg of coal).
1 ' ' i, ' ' • "j! ,; ' • : ' '
Eduljee and Dyke (1996) used the results of testing performed by the Coal Research
Establishment in the United Kingdom to estimate emission factors for residential coal
combustion units as follows:
• Anthracite coal: 2.1 ng TEQ/kg of coal; and
• Bituminous coal: 5.7 to 9.3 ng TEQ/kg of coal (midpoint of 7.5 ng TEQ/kg).
ni i ; • _,. ,, „ ,• .. '" ,.i'i ii ,'„'.,';
CDD/CDF emission factors for coal-fired residential furnaces were estimated in U.S.
EPA (1997b) based on average particulate CDD/CDF concentrations from chimney soot
I1 i ' , . '•': ''•'.' ','.'. ' ;•!": ' i J. ' , •
samples collected from seven coal ovens, and particulate matter emission factors specific
to anthracite and bituminous coal combustion obtained from AP-42 (U.S. EPA, 1995b).
The TEQ emission factors estimated in U.S. EPA (1997b) (i.e., 68.0 and 98.5 ng TEQ/kg of
anthracite and bituminous coal, respectively) were derived using the calculated emission
4-28 April 1998
-------
DRAFT.-DO NOT QUOTE OR CITE
factors for 2,3,7,8-TCDD 2,3,7,8-TCDF, and the 10 congener groups. U.S. EPA (1997b)
stated that the estimated factors should be considered to represent maximum emission
factors, because soot may not be .representative of the paniculate matter actually emitted
to the atmosphere. These emission factors are presented in Table 4-18, and congener
group profiles are presented in Figure 4-9.
Although the congener group profiles of the Thub et al. (1995) measurements and
the U.S. EPA (1997b) estimates are similar, the TEQ emission factors differ by factors of
175 to 289 between the two studies. The emission factors used by Eduljee and Dyke
(1996) to estimate national annual emissions of GDD/CDF TEQs from residential coal
combustion in the United Kingdom fall in between those other two sets of estimates but
are still about one to two orders of magnitude greater than the estimated emissions factor
from industrial/utility coal combustors.
Because there are no direct measurements of CDD/CDF emissions from U.S.
residential coal-fired combustors and because of uncertainties regarding the comparability
of U.S. and German and British coal and combustion units, no national emission estimate
for this category is proposed at this time. However, a preliminary order of magnitude
estimate of national TEQ emissions from this source category can be derived using the
emission factors of Eduljee and Dyke (1996). As noted above, 5.3 million metric tons of
coal were consumed by the residential/commercial sector in 1995 (U.S. DOC, 1997). U.S.
EPA (i 997b) reports that 72.5 percent pf the coal consumed by the residential sector in
-j •
1990 were bituminous and 27.5 percent were anthracite. Assuming that these relative
proportions reflect the actual usage in 1995, then application of the emission factors from
Eduljee and Dyke (1996) (i.e., 2.1 ng TEQ/kg of anthracite coal and 7.5 ng TEQ/kg of
bituminous coal) to the consumption value of, 5.3-million metric tons results in an estimated
TEQ emission of 32.0 g TEQ in 1995, which,, when rounded to the nearest order of
magnitude to emphasize the uncertainty in this estimate, results jn.a value of 10 g TEQ/yr.
This estimate should be regarded as a preliminary indication of possible emissions from this
source category; further testing is needed to confirm the true magnitude of these
emissions. ,
4-29 ' April 1998
-------
§
to
3
I
^
"o
I
ll
i£ °D
c I
.2 Q
.H UJ
u3 CD
w „ M
S 8-5
z"o ;>
#~» "O
££
1!
1
i
"3
£
£•
c
i
>.
TJ
CO
.c
I
in
to
to
CD
CD
imomet
TJ
(6
8
CO
CO
03
OC
z
o
3?
o
1
.2
O
C/J
is
CO
TJ
S
S
-1
"ra
co
o>
co a
cc ro
< 2
O ~
4-* 4->
X X
CD CD
C C
"en "to"
jp ^CD
>• >
0 U
O 0
CO
V 0
— (N
3 o
0 CM
S •
11
•s s-
C CO
W Q
>z
31
5-8
CO TJ
-ps
c
"8
CO
00
en
—
"ro
4-»
CD
TJ
C
3
.*:
ra
to to
3 3
.c .c
x x
"5 "5
E E
CD ffl
5-S
0 0
£2 £2
o o
ro
CO
<- 10
cc oc
z z
31
•S-o
•8-8
CD C!
"c ^
TJ
C
CO
s
IM
§
Z
ro
00
en
^
E
CO
O)
c
bo
CD
5=
i
s
E E o. 0.0
CD a> J3-.9- g.
CD CD ^ ^ fO
.Q .a .£ .E »-
CD" CD CD" CD •§
u o o o o
to to M tj S
4- 4- 4- 4- -0
CO CO CO CO ,£
.0
CO
V
TJ
CD
ro Q
CO co cp
?• CO : z z
3|3|3
s
•a TJ o
0) ts ID ~a 3
~D CD "O Q) fa
CO "O (0 "O — -
Q) (O CD CO —
Z) ""* O ""* CD
Q
C
•g
CO
o
ro
ro
—
"ra
CD
TJ
_3
a. a. Q. a.
'o. "5. "a. "a.
_c c _c c
"o "o "o "o
o o u o
to to to co
CD CD CD CD
+- *- 4^ 4J
CO CO CO CO
CL a. a. a.
S S S S
Q) CD O
ra
CD
o
ro
ro
CO
S
CD
ra
E
c
CD
ra
.c
C !^ "^
"^- S r^
I £ o %
S ra t • "c5
4-- "CD !° ^
ro c ^o
ID g ~ TJ
c «? ~ ">
si ||
•— ^ a. o
g T3 OS OS
a co | -|
"11 11
o o c c
£ £ co to
CO 03 U O
CO CD k. w
O O 1- l-
o
o 2
00 ^
CM IO
•o " ^ -o "
O -o CO S O CO
CM CO > » CM >
in co m a r~- a
-
(
1
'
1
>.
|
o
p
2
-5;
ra-o
E c
J= C
CD 3
o a
to w en en to
TJ TJ TJ TJ TJ
CD CD CD CD CD
a. a. a. a. a.
CO CO CO to CO
TJ TJ TJ TJ TJ
C C C C C
ra co ra ra co
to w en en en
TJ TJ TJ TJ TJ
O O O O O
CD CD O CD CD
to to to to co
C C C C C
.2 .2 .2 .2 .2
TJ TJ TJ TJ TJ
o o o o o
u o o o o
"to 1o to to "en
CD CD CD CD CD
en w to to en
o o o o o
._ ._ ._ ._ .=
ra ra ra ra en
CM f-- 10 ei jjj
IO tO T- ID i-
0 0 g 0 0
|3iiS
TJ TJ m '
TJ CD CD S 3
CD TD T3 ^— ^
TJ ra ro _ —
CO CD CD CD -
=> = 5g
c
ro
CD
CD
— CM
§1
— ~
"ro ™
TJ
"ra "5
CD en
CD
e
O Si
}le routes
F
ra
to
CD
0
C
ra
CD
O
ro
CM
c
a
CD
E
,
0
Z
<
;
"CD
CO
CD
b
CO
CO
•o
(
•^
ro
c
i
oc
.
c;
CM
CO
CD ^
§ E
8 io
O ID
I I
CO -s;
— m
ra cc
II
1§
>• fD
TJ O
CD 4-*
to g
O >•
% E
I i
•». o
Is
i-s
8-2
OT CD CD
CD "5 €
CO 3 ,
CD CD °
> r- 3
ra *< t
S „•£
o, -7; »
S
TJ
s=. f S
§| g-S
CD "• .
> tt> "5) t-
«S-gf
CO O £ C
_CD -O 3 CD
•a S S S
>lll
f!!i
.2 O CD "o
to o *
CD oj 00
CO
£ CD CD
4- •* .>
o. — =:
CD C) TJ
O iii _
>z
v
° ii
CD Q. O
C ,~UJ
ra "5 I-
4^ (0 O)
E 3 "o
g C eo
Ij S = "g
1 3 S S-
ra TJ .£ 3
0 3 to JS
2 ° t; 5
j. Q. ra
I £ = 'S
" CO O o)
ill!
Q OC o E
O. TJ
fcS
§ g.
TJ S
3 CD
eo
t &
E "°
3 10
en ,_
H- CD
O >
m O
& to
to •;=
CD E
8 sfi
*P CD +j
! Q) > Q
1 w > -^
_CD en
J3 --
en n
CD "
i- i-
-------
w
H
U
B-
S
a
s
z
o
Q
f\
£
u
CO
U-
.0
CO
'E
HI
^
0>
g
0)
o
u
u_
O
O
O
O
O
CD
2
o
2
3
CD
(D
£
CD
CO
CD
5 .
CM
•4
o
CD
1-
co
2
o
co
u.
c
o
"co
u>
1
c
(0
CD
tfl
42
^5
CO
n> ;
D?
.>.
•c
3
CO
c
_o
CO
CO
E
HI
CD
Q.
'a.
'co
—
A
O
O
3
"^
.
I
c
4J
1 E
fffi_
'E"°^I
3 CM O3
(0^ Q.
CO —
< II
O
Z
0
C Q>
£' — N_J
,, "S,
3 1 O>
« O.
JOQ —
» 350: —
in Q> ^
it
in
co^S--;
_c d^^
"^ 4-1 *Y- ^
wE£ —
CD
+J
^< —
^•sl
00 QC "™*
co —
5
;
D
»
5 Q.
=?0
e<5
5
3)
5
^ CO CM CN CO O O
r-cDcoindiriS
r-T T— T— CO :
"S-COCDCDOOO
^of^yogS
CMCOOO»-OCOO
CN CM |^; CM r- CD CO
<* »- o •* o en in
CM *t T- t- CM CM LO
«- co «* co oo f^ in
«uT »A " CO t^ CO CO
Cv ^8 ^~ ^_ en
O5 ^^ ^~ ^~ ^~ ^~ ^^
r~ cri in in in *a- 2
' ' ^*
000
o
QOOQ
9oOO-r
LJ XXX
f~\ CO i i i *•
1— obr>-" rococo
oor^Ttcor^tf
I^ CO CO CO CO CO ^r
CO" CM CM CM CM CM Q
CM~'-'-«-'-'-O
^•COCOCflOM^cNOOCO
30 ^v co ^^ co ^^ c^ r^
*"" ,*^
^•OCOOOI^OOCNOOCO
oo'-coro^tinoooeooo
DO f^ co ^f co (^i co r^
' ^~ T~~
co<-inoomS<--frcoin
cor-cocoin^rco^^tD
^-OO^I''— OOO^COT— T—
oo^-co'tcodooor>;o
- O
^£
o> T- r» T- in r- cs o> o> •*
1
in ^ •>- in t~. P P r> in •*
Oinr^cocotninoeo'*
CM— •«* co
O -OQ
Z ZZ ,
i
.-
U-U-
U-U-U-U-gg
fjQ-Q-OOOOCOOOr^OO
h- oooor^r^oor^cor^
oo i^.r* •* CD r~ eo •* •<*
t> co" 't co" co" co" *t co co ^
co" CM co" eg CM CM co" CM CM Q
CM «- CM" »- «- 1- CM" »- 1- O
or- r-
T-CO in
oo o co
coco
-r^
ro^-in
r-oco
coco
oq in coco
C35 P- O) O)
O»-CMCM
1 *~
00 CN^-^-
00 OOOO
in «—
CO OOOO
OOO)'-'-
o^j-oojg
OOOCM^j
inr-
,-t
c
—
ct
1-
OO II II
tv)Co"CJ ^
CMCNI— 1—
CO CO' CO Ct
o o o c
nt-cor^oo>
t— T- *— T- lf>'C3>^lf> CN T- T-
in^cor-ocD,noo>o>
22l^^incnSeM^^
^ootcoocoincM-in
ncMT-coinocM^KNco
coi-
r-cMOP-moocococMi-
CO'CM CMP— cNiincocMr— o
in .«-
CO CM CM t- CD »* 00 in CO CM
•"ti^coinmp-cococo'*
p-encoooocoojino1*
•*
QOO_ U.U-U-
C_J CD X Q.C— ) f) Q\ x CiC,
o o o o o o o o t5 e
r>
CM
co"
rs.
N
co"
oooo
§°-
oooo
CO CO
CO CD
in in
coco
co'co
coco
coco
CMCN
roqy
•*
E
a
— T3
£CM
CO^~
II II
oo
ZZ
LLLL
OO
CJO
*— \ f
LJ I—
QQ
OU
CO CC
o c
H-l-
"'•
"55
^
CD
C
CD
O)
O
u
1
o
a.
0)
0
ID
CO
CO
XI'
•n
0
4-*
co
3
0 ,
CO
• o
.£2
o
CM
CM
.CM
**—
0
"p ^
1= l~
.2 i-"
*4_i CD
S g ?J
M 5 CO
•So 2
CO -C —
f < CO
0) . ^
CO CD ®
1°= S5
CD C 0)
£^ -1
• S e 5
co 0 0 X
Q. Q. CO .-
c £ co p
•~ (o — en
§ - - 2
75 =5, ro -
>- STO
"S ® 03 tt
g CO .'co ®
8 ^ ' E "?
- 4-* M- ^ ,C
® o § >
"° rt 05 5
4_i ^^ m "7?
is ^^
^» • *
<• _,-• •«
M ^
Q " -£-55
, z * tr cc-
-------
g
u
g
B
O
S
I
I
10
o
1
u.
8
I
UU
O
§
o
JX
a
2
(Z
•a
o
e
3
UL
"s>
&
Q
t
CO
tj-
3
n
2
H-
1
U*
C.
•§
,!2
UJ
i
S
"5
w
m
§.
"O
D
W
(D
0.
_CX
"5
H
J*
u
2
[ ,
f_>
r
i
C
E
£ T3 • —
M «- _&
^ 8
Q
Z
1 "3
lo-S
*•""
j_i^
u. — *^
^** nj . *^ ^7
j£ i-go
O p ^Q OC "—
£
^*.
£ § —
* — • • *t ^J
^1^1
10 S —
5
J
£
>•
3 §•
=- 0
IS
u
D>
C
o
J
r- ro
O CO CD O ^ f^ -
T- CM CO CO Tj- oo IB
" «-
« CD
**; r» co *? r» £; co
^ P*» CO ^~ CO «C" U>
^- ^ oo ,_
~ O O O O n o
CO m 2 K S ° °
Z Z Z Z Z *~ W
2 2 £ «o r»
1- co r^ p^ co to"
CO P^ *& CO P^ ^"
r** co co co co co y
co CM" CM CM" CM CM tj
CO Q *—
COOJP^cnS-CDCMgcDg
CM ^~
1 CD *—
p»coococo2P~coi-co
CDCDCOOOCO^'CO^.lD^l
|||||8l|||
zzzzz^z^^
ScoKcMCoiritNP^SS
coi§2Sco^S^°^
U. U-
U- U- U. U- Q Q
U-OOxXXXcOoS
f\Q_Q_COGOCT)COP*CO
1— OOOOP~P~COP~(OP»
co p~p~^cb"p-"co^f^-~
P^CO^l'COCOCO'Ci'COCOyr
COCMCO'CMCMCMCOCMCMCJ
CMT-CM"«-»-r-CM"«-«-O
«p2 <2
ss ^
OD
^s°
^~C!CM
2 p* *~
o 6
o o o o
^CO CM CU
(D CM COpC
rj- CM
r» ID
CO CD O O
p» O f~ '•*
Tj- •*
o o
CD P<- ^. ^
io_ T- oo ro
^ ^J*
4^
1
s
o ^
fl> ^
Q u. N *~
O O II II
co co -z. z
""22
CM CM 1- 1—
ix ?M ," r"
0000
H h- 1- I-
ssi||s||||
CO ,_ «— in ID "5T
CM S ,_ •* 0 •* CM
to CO ID °° 2" » t "1 "*- °l
(D ^ ^ r- lt> U> *t
o o °"
PpjcoooSSooo
- - 10 ". R o co N. •*; ".
§§§"""
o t [^ S S ro co S J° o
to
o^coo^ScocMOcn
CN «~ CN ^ r^ CN
D Q Q _ u_ u- U-
QQQQ^U-QQQLI_
8'~'tx
•S 2
QJ — *
5 -5
- !
O 0)
« Oj
1 "5
0> 3
ra ^
Q. _^
C *~
CO
Q) CO — >
3 ^™ CD
•5 — co
> _: co
(D «—
•a *- •-
(u a> co
1 18
S 'i —
•° 1 5
| £2
z
II < CO
Q tii *si
Z DC CC
CO
O)
a>
~
Q.
CM
CO
-------
2
1
Ill
o
O
Q
Q
O
o
S
Emission Factors |
i
•
•a
-I
.. c
•J
UJ
&
'5.
'<5
H--
Automotivf
Assuming
NO = 1/2 del limit
(pg/U
rag
C Q) j^
•g N _,
3».S
S§~
JSSU
o .O-j
£IP
u_ ^
5 Eo
o^O-j
•0 C>5 g
! tri-
ll
'. i_^
fo'c=r
-* '= "S g
tfl«s
-.41 '.'
CO
17? 3
S c"5 g
£SE-
«
CN
E-d°3
I||I
I « n
:«SB
to~ •
. « < -r
g- . =d
• "S O>
tfi*
u-
ngener/Cohgener Group
O
SCO CO CO Tt «- - co
in in
— ~ CO
S 0 co o = ^ co
^ ^ «— co *z ,_ «—
T- 00 CD CO CO 't O)
*± co o CN o in •*
•«- <*• CM CM CM in in
O co in to E CD co
CO O «- CO z CO ^
»- »- in
i3£Bi£l
oo in oo r^ oo co oo
CN CM CO O 00 O 05
»-«*»- CM «- in >*
2 *
r~T co co co co co 5
co CM" CM" CM CM" CM cj
CN~T-"v-'—'t-'.-'O
•* in CM «* ro o CM T- oo CD
r^cMOcocNincocoinco
r»»tcMcoco coco in
^•incMOinoocoi^cocn
r^CMOCOCVJCMCMUJCOCM
r* «t CM co co co oo in
Tfroom.-minco«-cooo
«-T-CMOOI^OOCOOOCM
tMCMCMCOCO OCOT-T-
- .«- CM *-
ooinr»-^o£EooEi^
r^Tj-eMcocMZ^inZ^j.
: " . -. "
t^ O CN CM CM £ *- O E CO
coo)O>Tt^j-zocozin
•co«-Ttcno> co^- CN
»*.«—'. <*
oor«cooo!EinE£E£
PvCDUJt>-CO^-CMzzz
co eo r7
£ ro co co CN S 5 g 5 2
Z^I-CMCOCNZZ£:Z,-
CN>-r~cococo"coT-co"o
^•oo'sfininr^i^.int^-co
inO'S-oooo — CNO — CM
^-~W Q rf.Ol
2 . Z .
co^^ininininininro
CM *f
z z z zz z z
U. U-.
UL U.U. U. Q°
--8888JS
S'9 §$*:?$ IS; .
f\Q-Q_OOOOO>OOr^CO
1— oooor»rvcor~cor-
oor»^-^'coi^eo^-'*
r-" co »t co" co co ^f ,co co t
eOCMCOCN"cM"cMCOCN"cN"cj
CM"«-CM"«-r-r-CN">— t-O
cn o r-
co o . in
t o> ; ^
^•* ! A,
l
O CM O
^c co in
t 00 T*-
r-"^-" Al
in ro 01 cn
r- CO «- «-
co o •* •<*
CM CD
CO CO CO CO
co o in in
•«*.«•* <«
T- Al
Al
CN 1^. ^t ^t
ID r^ CO OD
CO CN «- »-
CM O »- >-
*" Al AJ
AJ
in co o o
co in o O
00 CO CO CO
AJ 1" Al Al
Al .
»- in CM CM
cn «- in in
">•*««
Al 1—
. Al
r^ CD in co
co co r- oo
«- CO O O
CM cn «- «-
0 S roCM
Z?S2
V
. 1
•£
°s
s^
g fe 1 «
9000
00 00 Z Z
KrC--
co co S C3
CM CM H- J—
^i2.^i2
^-^j-cococoocnoot^co
cocncoor-cocoeooco
«-co«-o>co^tcocMcoin
Tf CM «-" in CD >* co
CM
^cn^ooocnoincn
COCOCMOr^COCDCOOOCM
^COr-O>CD^tCOCMCNin
•* cMr^ in co «t co •
CM
«-cncooo»-oincMOco
cMincnoooocDcococMCM
cncoo)coincM»-i-oj»-
T- ^f CO CO CM «-
ooo)co^i-cocoocor»i^
inooi^t^cDinoointO'*
incocnco«-coininp»'*
'tCD«-CM«-O3OCM^-
CM t- «-
cMincOt-ror^t^p^Oco
«-r^mootinin^t»-in
OcoocMinoor>a>cM.cM
to co CN T- incNcoco
in r-
eo"
CM
r~coit<*Or^cMCMOin
«- in in cn co co in cn r^ "-
in co co «- co «- •* T- «- «-
CM ^
incooo^toocot-ooeMO
incocococn^'cno'i'co
incooO'-ttr^incococN
•*««-«- O"— coin
• in »-
oooooooooo
CMCD^t-cncooco«*r»cn
-Ilii^giS
Q D .Q _ n_ U- U-
QQQQgtl.QQQU-
oV^a.8o0^ ^8
££££o£i££xo
oooooooooo
CM
CM
cn
^~
AJ
co
CO
o
CJ)
<*
Al
O 0
59
OJO)
0 O
CO CO
•* Ti-
i> r»
r» t^
o> cn
in in
co a>
CO CO
CM CM
CO CO
CO CO
cn a>
in in
00 00
in ^*
cn cn
CM co"
CM CM
2
S
IS
N «-
II II
Q a
z z
U- U_
Q Q
o o
o o
S S
00
o
cn
cn
•a
c
.C -
O
Q.
a>
cn
*-
o
o
I
no
"S
a
a.
3
=£
2
O
a.
o
£ E
1 I
•o
I
o
a.
.E
"« =
- 2 - i
11
1?
t o
!!,«•*
n u <^"
QC O , *Q) *O *Q)
22 CC £T CE
-------
CD
£
.1
o
5
1
1
c
in
4
1=
mission Factors
g
Results
ips Emission Study
Automotive Tailp
4-*
:=
c?s
•s-o rr
§ £2~S
S-s
< X
0
e <5
•| N_,
g« g
!i~
CM
f^s
;sss
03 ta —
S
|?«?=
5 e-s g
S|E
. P
fo'^3
•2 e>S g
SI~~
t^Oa
5" o . =:
£ e"S g
fcSEs
Cs
_
JCQ ,—
•si
SSEa
O
JH —
s-2^
t££
ngener/Congener Group
8
CO *- CO O) CO 03 00
™SS8°£
*t O) O 10 O CO rj-
•* •* od 06 r«: ° £;
»— T- <— CO t—
cn T- co «- «- oo Tj-
cd •* o C3 r-^ r-^ <2
r- CM
1^ r- IT) CM CO «- 10
^ CN Tt- CM M 00
«— CD
<* T- CO CO O) CO O
^f CO W CM CM IO CO
rj- Tt »!• ^ IO CM CO
CM i— CM CO r- O) to i^ r^ o J^
^r s? o o o o c
E.£J^3¥3io
9 5 Q Q Q a a
^^••z.-z.-z.-z.'z.
Q
a a a P.
_ o a Q y •
° oo o 5-
D X X X -V
Q OlX loo
O Q) t * * •>
£j a. co co cn r~
1- 00 t^l^OO CO
co rC ^f CD t~^ •*
r^ co co co co co g
CO CM CM CM CM CM" O
CM'r-'^-'^^r-'O
^•<-cncMCDcna>mco^-
Oior^oir^cocD^^co
cococO'l-coincM*'
•4-COCOCOCMU>— cMcnT-Oin*-
io»-irirococdcNodiTj-ooir>PcMCMTtoo
>-COOOOOCO — TtCMCMCO
r- Q CM
z
»-CM'*00'*T-COU>f~'*
t^r-cococococo'*cMcn
^
ooococMr^iocoP^
r~n-co«oCM«-
•^M^OOOOOOC
co ^••^•"t^t-'t'd-i^
Q Q
ZHQQQQQQD
-z.-z.-z.-z.-z.-z.-z.
LL. U.
u-ii. u-u. ° Q
--S8881S
Qfixxxx-r-V
ft^^^T^^00-?5.
gOLQ-OOOOCJOOt^OO
h-coobr^r^corCcDK
cotCt^^-«or»cb"'*^f
r^co'^cococo'fcoco^
COCM~COCMCM"cMCOCM(N~c_
CM'-CM»-'-'-CM'-«-O
CO CO CO
o> o> «-
o a> in
^Sg
00 t^ 1^ t^
cn •* T- «-
CM CM
T)- cn >* Tt
«- CM TJ- M-
cn co T- «-
Tj- ^f CM CM
o cn CM CM
IO CO «- *-
>-•*•*•*
5|5 SB
Tt en o> cn
cri t^ d o
CO CM ID U>
CM •*
9^-t^
H CO cog
]
i
^. 1
ScM
o ~—
Qu. N^
Q a n
CO CO z ;
r» r-~ ~ ~
pjm O O
CM CM 1- 1-
000
1- H H H
cocno^t^or^^tcMco
o^tco*— r^if>co^u5co
oocnr^co'toi^oooo
co^co<-r~iooo'tioco
SO't'-'tcncococo*-
co«-»-coa>cocncMOcn
CM CO «- i- «-
ocMcoioiooor^oomoo
o^cDCMoor^coiO'ti'CO
IDinmcMCD^J-^t'CM'tCM
CDThcor-OcocotocOTi
ococn^'CocM'-T-r^cn
r-r^^'-cMcniocDt^'-
cnr^'tcMcocO'-iocO'*
escococnmr-cMco
U)^-u>cocDcn<-cococn
Tf^tCO »-lDOCO't'-
cocooomor^oot*-
, •*»-— I^— >*CM —
Q Q «- O Q
ziiz ziiz
a.g§8g^S£fe
Ow x aOo« x O-CJ
HCifxTOHClXIO
(UC3(OR]tD(OtO(D(D
OOOOOOOOO
1— h-'t— 1— 1— 1— 1— 1— I— H
co
00
in
n
00
ID
CO CD
n in
M CM
* •*
•*•*
r> co
*.*.
ccfcd
co co
p~ r~
o o
in in
CO CO
cn co
CO CO
CO CD
00 «*
. 2
S
IS
N *-
II II
Q Q
Z Z
LL LL
O Q
O O
Q O
0 0
"m "col
i8 1°
1
O)
T3
0)
•
o
c
o
c
o
•a
tJ
s
O
a.
±i
C
3
O
Q.
tt)
I
_eg
D
CM
co
cn
n
a.
£
*J
C
2 x co
< cii 6
"u "S "S
CE' EC CC
-------
CO
o
+-*
o
s.
o-
'co
co
CD
c
CD
a>
o
o
u.
o
o
o
o
o
e
/
UJ
H
rt
^r
04.
O
w
H
0
P-
0
g:
Z
0^
Q
!
H
PL,
^5-
^^
^\
f-
. >
o
o
o
S-
CO
O
.c
4-«
5
"CD
3
U.
CD
_C
"o
ro
CD
TJ
CD
T3
CO
CD
CD
4
.a
co
£
0
o
l^
_o
"to
to
1
UJ
c
g
&
1
to
CO
CD
1—
•o
C
O
'8
E
LU
CD,
O.
J2.
"5
CD
1
O
3
M
1
O> 4-t '
C CO _
E ^
• 3 eN o
« ;r D.
to T^ —
< 11 .'.
Q
-Z
1-1, O
~i i-
c ^^
•|^2
if_
1 0^5
•^ C.TT O)
4-" (?! °-
to 8~'~:
. ^"w> - _ .'
cJ
=£co co — •
1 6*=^
to to— ~
£
*—
£cN£_
1 d •==!
•* £j| ™
to| —
£ ~
~r- "*T
•*- "3>
CD Q.
COOC —
co —
'
Q.
3
s
CD
C
i CD
O>
c
o
O
S
c
CD
O)
f-
O
o
eo o CN in oo oo ix
in co co ^* co co «,j
CO
\
ix T- CN in oo oo r-
•* CM CN <* CN CO S
co^
Th "* T- CM CM »*' f-
«- »- en
en en en en
C£E£C£«:!^S
Z Z Z Z
^
O CD co o O oo in
co oj in CD co ix J^
CN
CD co »* in «- co o
»- T- CN co co in ^
^—
•
0
o o o
gooo-S-
CJ X X X "V
fj Q_ 00 CO O) P**
H- ob r^" rx ce> CD
r** to-co co co co Q
co* csT oT oT csT . to in CM to co en o r^ o
«- ., • eo 1^
,
rxiriincNeoooixocNO
»- *~ to rx
co T- — in •*
O «-
Z
T>.»-cMincn«-eNeNeneD
t- in *~
tor^cMcO'— oo""— cooooo
oodix'oencoed^tco00
T- T- — t- in —
0 0
Z Z
COCO<*OOCOCMCOCOCMcn
'i'CocM'i'eDO'i'eoorx
i CM
0
Z
LL. LL.
LL. LL. LL. LL. a Q
y_ ,j_ Q Q Q O ^^
°t£c£ciobcici'^i»'
h—oocor^i^cor^op^
co r^ ^^'*"sj* CD r^ CD ^f ^^
I^ CO ^J" CO CO CO ^^ CO CO Jt
COCMCOCMCMCNCOCNCMQ
^^ IX
CM O " *-
eocM
rx o in
«- o »-
CO CM
^ co CD eo
COCO CM CN
CM CN
in coo tx
^ 2
in co
|x CD CD CD
irieo *~ *~
CM in
CO T-
•-
in «- CM CM.
rx 'o r^ fx
en ix
«—
E
4-*
CD
— -o
2cN
s ^~
0 0 II II
OO 00 2 Z
ix p^ "•" ' "
n n ^ ^
CM CM" t- i—
o o o o
H-h-l-l-
ix eo <- CM eo en ^ oo in o
co eo CM en ix co CM o eo oo
CN «~
rx Tj- «- CM co en T- co in o
coTtcNtnixcocMoeoco
CM «—
oooincMencoooeooO't
«- T- CO «-
ro in eb co ix en en o-* to
«-T-COeOCN|xcNCOIxO
Q
Z
»-t-eooincNCM«-cMoo
CM «- T-
eomcorxoeo^i-coT-en
odincoo6|v"cMcocoix|x
CNCMCMCO^minCOCMCM
QOOQ LLLULL^
OQOO^OQOO^
I-Q!XXOI-I£IXO
oooooooooo
1- 1- H 1- t- 1- 1- 1- 1- 1-
m
en
O
en
coco
coco
* *
in ix
en co
9.9.
'-"'-
00 00
CM CM
en en
^ «*
CO CO
00 CO
E™
~"
CD
aj •—
N »—
II II
00
zz
LL LL
QQ
00
O O
00
0 0
^^
a
a
a
IT.
CC
c
o
CD
-a
•g
O CM
a. en
CD en
CD -—
^ "5
.22 ~
CO
CD
CO
CD
.C-
CD
D)
C
C £
£ — =
sol
a. en ..
en ^""
IZ en
. en
CD
CO >0 —
CD
T3
£. 5
I, < CO
Q "CD "CD
Z DC cc
-------
DRAFT-DO NOT QUOTE OR CITE
2,3.7,B-TCD1>
1,2,3.7.8-plcDD
l,2,3.4,7.8-Hx:CDD
1.2,3.O.7.8-HaeCDE>
1.2.3.7.8. 8-HxCDD
l.2.3.4.B.7.8-HpGE>r>
1. 2.3.4. B.7.8.D-OCDD
2.3,7,8-TapF
1.2,3.7.8-P«CDF
2,3.4. 7.8-P-CDF
1.2.3.4.7.8-HxCDF
X.2.3.0.7.»-rixCDF
2.3.4,B.7.B-HxGE>F
1.2.3.4.8.7.8-HpCDF
1.2.3.4,7.B.O-HpCDF
1.2.3.-4.O.7.B.O-OCDF
Ratio Ccono«n«r
O.O5 O.I
n {actor / total ODD/CDF* •mission factor)'
O.15 O.2 O.2S O.3
0.35
Ratio (congener group emission factor / total CDD/CDF emission factor)
0.05 0.1 0.15 0.2 0.25 0.3
0.35
I Cars li:...v •:.:.! Trucks
N»u »«u4 u pr.nl4j ulenUud from raUjion Oeton (ND - 1/2 DL) from T>blu 4-2 ud 4-3.
Figure 4-1. Congener and Congener Group Profiles for Air Emissions from Diesel-fueled Vehicles
4-36
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
O.O1 O.O2 O.O3 O.O4 ,
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-HxCDE>
1,2,3,4,6,7,8-HpCDD
1.2.3,4,6.7.8,a-OCDp
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
J ,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)
O.I O.2 O.3 _ O.4 O.S
O.6.
i«d on pt»fil«M ••brauud from MBUatoB Awtan
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
O.O5 O.I O.1S 0.2 O.2S O.3
2.3,7.8-TCDD
1,2.3,7,8-PeCDD
1 .2,3.4.7. S-HxCDD
1 .2.3.6.7. S-HxCDD
1,2,3,7,8.9-HxCDD
1 ,2,3.4,6,7,8-apCDD
2,3,7.8-TCDF
1,2,3,7,8-PcCDF
2,3,4.7.8-PeCDF
1 ,2^.4,7,8-MxCDF
1 ,2,3.6.7,8-HxCDF
1,2^.7.8.9-HxCDF
2,3,4,«.7.8-MxCDF
1 ,2.3 ,4.6,7.8-HpCDF
J Jt.3,4.7,8,9-iipCDF
1^,3,4,6,7.8,9-OCDF
Ratio (congener group emission factor / total CDD/CDF emission factor)
0 O.OS 0.1 0.15 O.2 0.25
0.3
0.35
deaiUUOom Tabu,«.
Figure 4-3. Congener and Congener Group Profiles for Air Emissions from Unleaded Gas-fueled Vehicles
4-38
* A 998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-7. European Tunnel Study Test Results
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
Tunnel iAir
Germany
(Ref. A)
(pg/m3)
ND (0.01)
0.31
0.37
1.1,9
Q.44
1.9
6.3
6.17
0.40
0.19
0.26
0.16
ND (0.04)
0.12
1.2
ND(0.16)
ND(1.3)
. 10.51
2.50
0.58
0.23
2.5
7.8 ,
3.4
6.3
3.5
3.6
2.0
1.9 ,
ND(1.3)
31.2
Tunnel Air
Germany
(Ref . A)
(pg/m3)
0,06
0.28
ND(0.17)
0.66
ND(0.17)
2.0
6.4
0.72
0.36
NR
0.13
0.15
ND (0.05)
ND (0.05)
0.98
ND (0.17)
ND (1.0)
9.40
2.34
0.42
0.22
1.3
2.7
3.4
6.4
6.2
4.1
1.1
,1.2
ND(1.0)
26.6
Tunnel Air
Belgium
. (Ref.B)
(pg/mS)
0.002
0.025
0.025
0.042
0.030
0.468
2.190
0.013
0.143
0.039
0:073
0.093
0.143
0.004
0.499
0.074
0.250
2.782
1.330
0.096
NR
NR
NR
NR
/.MR
NR
NR
NR
NR
NR
NR
Tunnel Air
Norway
(workdays)3
1 (Ref/C)
(pg/m3)
0.02 '
0.18
0.06
0.29
0.25
1.41
0.10
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
0.26
1.78
1.32
1.31
0.10
13.20
10.17
6.42 ,
2.62
1.62
38.80
Tunnel Air
Norway
(weekend)3
(Ref. C)
(pg/m3)
0.02
0.04
0.03
,, 0.03
0.06
0.16
0.50
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
0.16
0.41
0.12 .
0.23
0.50
1 .70
7.91
,2.08
1.41
2.54
17.06
ND = Not detected; value Fn parentheses is the detection limit.
/ ' "~
Ref. A: Rappe et al. (1988)
Ref. B: Wevers et al. (1992)
Ref. C:Oehmeetal. (1991) "..-....'''
3 Listed values are the differences between the concentrations at the inlet and outlet of the northbound tunnel
lanes. , - ,
4-39
April 1998
-------
cJ
§ g
51
Ul
K
I
g
.—
42
1
to
c
D
CC
""§
ll
O
dl
11
£C
il
§1
cc
X "p
Hi
|-S
il
§s
cc
il
§1
cc
Run No. I
(pg/km)
o E
2«
il
CC
sr/Congener Group
c
CO
S
m o eo o r- o in
•* oi d 6 £ S 2
CO CM •* 00 ^ ro t
*T
O O CO (D O O O
_; _; CM oo r^ oo CM
S S *- •- m °, «°.
CM r^
»- o o «- to co en
0 0 0 r- _ ro 03
10
co •* in co o co o
55 S S *- N •* *-
CM en
CM ^ "
CO
(O CO CM CM ID v- T-
r- O 10 CO CD S m
ID CM CM CM 10 ' .
CO
IO CM CM 1C CD O O
«* o oo r~ co
CM >* T- CO IO
a
Q Q Q P.
-. Q Q Q y
° o o o •£•
_ D X X X -V
g S * =F =F «.
(j a. co oo o r^
f- co p» r^ oo eo
co r~ ^f to t~^ ^
rC co co co co co Q
CO CM CM CM CM CM o
CN «-" ^ «-' »-" «-" O
ioiOTj-o>oocMCMr^.Tj-in
(o-^co^od'tioSdS
cocpr^iocooo^co"
r»cooocomu5'-coo>o
«-'co°2">«^m1*m
COrJ-^^OJCD-^^CO"
^J-OO>'*'1-C>JCO^-CO^J-
codco2'*'s:«:'cocJ2
r« coiococo" "^
eocoo^J-cocoocooco
incoio^i'-dcOmidlZ
OOCDCOOOOOI^'*'-lO
CMCOCDCOT- lojfj'"^
iocMm ioco
T—
r~cn«-ooiooioc»
•*o6io'2'n'1*oicMa'cM
'*t^l~.«-00CNlOCN
O O 10 tt CO f« CM CD O O
»* in o r~ 10 CM
CM »- CM r- r-
LL U.
u. u. u. u. fj j Q
-S8888||
s§8^^$$55
QQ.D.COCOO)COr~00
^oooor^r-"cor^cor^
oo r-Tr-^'*cDr»o*f'*
i>TcoTfcoco"co^fcocot
COCM'cOCM'cM'cMCOCMCgo
CM»-CM«-T-«— CMr-T— O
ID f» CM
r-_ «-^ «-
It) r^
IO CM CO
t- CD O
IO CO CO
o <-"
co -.«- co
O CO «-
p^ «-
co r» 10
r- co CM
CM «-
10 •* CO
co r^
00 »t O
CO CD i-
'* T-^
^- 00 10
O> »- i-
co" ^
Tj- P~ 00
£ ID CO
ro r~
Q u.
o a
0 O
CO CO
p»" 1^ _,
co co g
CM CM 1—
co co n
S S S
1- H h-
CMCMCM'*lOt~-»-«-'*iOlO
t-3t'-O'*O)'CMI^COlO<*
T-^ ^ IO r-^ CM
•-^frcnioocoio^cococo
cot-ocoi^'tO'tiO'tr--
CM IO O> CM «- CM
CM
lOCOlOCMOlD^CO^tlOCO
"SS--.8S&--8
t- CM
OCOCOOOCM^CMCM^-r-O
t-Sf^"*COCT'-0000'*'t*'
r-" CO ^-" «-" O
pcnocM»-»-a>a>cocnr-
I"] COCOOT^COCMCMCn
CT ID'
10 o r» o o o »*• «o o o «-
CM t- CD *- «- CN
u.
oQD_ nU-U- c.'
QQDQ9u-QQQ"ry
On! X Q-OOin X Q.OQ
HQ-IIOl-ailXOO
COCDCDCDCOCDCOCOIDCDCI
o o o o o o o o o o e
l-H-l-l-l-l-l-l-h-l-l-
r^
IO
CM
*t
p^
CM
CM
• .«
Q-te
I >
(O
O)
O)
CD
•f
CO
I
u
E
CD O
C u
c c
D CD
~ £
CD CD
•5' °-
f I
s
S ti
s «
O
» *
*= C
"g '5
CO C
. CD
a> co
c
•3
CD
O)
C
•c
D.
i
•a
•5
•= CD D
O N T?
"co P >•
o _ >
CD CO ™
jz 3 x:
c "> E
CD ti O
* W "^
if!
(D > •-
g 2 B
t
CO += .2
J3 (0 tn
a, E?-!?
co
_
-------
DRAFT-DO NOT QUOTE OR CITE
1 0.7
ta
Q
O
Q 0.6
Q
O
I 0.5
0.4
a
o
o
g 0.3
&
a
•2
0.2
0.1
' 0
4 5 ,6 7 8 ,9 10 11 12 13 14 15 16 1-7
Congener Number
I Norway (Row 1)
Germany (Row 2)
Germany (Row 3)
• Belgium (Row 4) •• Baltimore, USA (Row 5)
Congener numbers refer to the congeners in order as listed in Table 4-7.
Figure 4-4. Tunnel Air Concentrations
4-41
April 1998'
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-9. CDD/CDF Concentrations in Residential Chimney Soot from Wood Stoves and Fireplaces
Congener/Congener
Group
2,3,7,8-TCDD
1,2,3,7.8-PaCDD
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
U.S. East
Region
(Ref. A)
(ng/kg)
66
NR
250*
250*
208
1,143
2,033
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
3,450
NR
126
1,987
NR
2,183
2,104
2,033
NR
NR
NR
NR
NR
8,307
U.S. West
Region
(Ref. A)
(ng/kg)
13.3
NR
522*
522*
282
1,653
2,227
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
4,175
NR
112
269
NR
4,273
3,243
2,227
NR
NR
NR
NR
NR
10,012
U.S. Central
Region
(Ref. A)
(ng/kg)
66
NR
1,831*
1,831*
1,450
6,160
13,761
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
21,437
NR
459
1,511
NR
14,243
12,603
13,761
NR
NR
NR
NR
NR
42,118
German
Farmhouse
1 (Ref. B)
(ng/kg)
150
70
35
60
30
90
90
930
560
590
330
400
70
200
490
40
70
525
3,680
720
3,900
880
600
200
90
13,400
6,100
3,200
720
70
29,160
Canadian
Wood Stove
(Ref. C)
(ng/kg)
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
Fireplace
(Ref. C)
(ng/kg)
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
(Ref. D)
(ng/kg)
ND (12)
70
ND (10)
625
281
948
530
235
58
68
51
57
8
24
97
20
41
2,454
659
211
11
608
3,450
1,550
530
1,010
948
482
154
41
8,783
NR « Not reported.
* x Analytical method could not distinguish between congeners; listed value is the sum of both congeners.
Ref. A: Nestrick and Lamparski (1982; 1983); mean values listed - six samples collected in each Region.
Ref. B.-Bacher et al. (1992)
Rof.C: Clement etal. (1985b) '
Ref. D: Van Oostdam and Ward (1995); mean of two samples - nondetected values assumed to be zero.
4-42
April A 998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-10. CDD/CDF Concentrations in Residential Bottom Ash from Wood Stoves and Fireplaces
Congener/Congener Group
2,3,7,8-TCDD
1^,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-HpGDD
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
(Ref. A)
(ng/kg)
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 (5.0)
300
2,600
9,100
2,200
1 ,000
700
ND (50)
15,900
.Canadian
Wood Stove
{Ref. A)
(ng/kg)
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
(Ref. A)
(ng/kg)
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
(Ref. A)
(ng/kg)
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.
Ref. A: Clement et al. (1985b)
4-43
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-11. 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
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-12. CDD/CDF Emission Factors for Industrial Wood Combustors
•
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 TEQ
Total CDD/CDF -
Four facilities tested by CARB
Mean Emission Factors {ng/kg wood)
Nondetects
Set to
Zero
0.007
0.044
0.042
0.086
0.079
0.902
6.026
0.673
0.790
0.741
0.761
0.941
0.343
0.450
2.508
0.260
1.587
0.151
1.039
1 .748
2.936
6.026
4.275
9.750
7.428
3.747
1.588
0.82
38.69
_ Nondetects
Set to
1/2 Det. Limit
0.016
0.054
0.055
0.096
0.132
0.905
6.026
0.672
0.79d
0.741
0.768
0.941
0.350
0.491
2.749
0.344
1.590
0.154
1.039
1.748
2.936
6.026
4.275
9.750
7.428
3.988 .
1 .590
0.85
38.93
Sources: CARB (1990b); CARB (1990e); CARB (1990f); CARB (1990g)
4-45
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CUD/CDF emission factor)
O.OS O.I
0.15
2,3,7,8-TCDI>
1.2,3.7,8-PeCDD
1.2,3.4.7,8-HxCDD
1.2,3,6,7.8-HxCr>E>
1,2,3,7,8,9-HxCDD
1.2.3,4.6,7,8-HpCDD
l,2,3,4,6.7,8,9-6cbD
2,3.7,8->T<::DF
1.2.3,7.8-PcCDF
2,3,4,7.8-PcCDF
1.2,3,4.7.8-HxCDF
„ il,!" " i
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
Ratio (mean congener group emission factor / total CDD/CDF emission factor)
O.OS 0.1 O.15 O.2 O.25
O.3
Figure 4-5. Congener and Congener Group Profiles for Air Emissions from Industrial Wood Combustors
4-46
AprU 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-13. Estimated CDD/CDF Emission Factors for Oil-Fired Residential Furnaces
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 <
. Mean Facility
Emission Factor
(pg/Loil)
56
NR
NR
NR -
NR
NR
66
53
NR
NR
NR
NR
NR
NR
NR
NR
30
NR
NR
150
139
82
66
63
66
663
420
170
73
30
1,772
Source: U.S. EPA (19,97b)
NR = Not reported.
4-47
April 1998
-------
0
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener group emission factor / total CDD/CDF emission factor)
0.1 0.2 0.3
0.4
Source: U-S, EPA (1995c)
Figure 4-6. Congener Group Profile for Air Emissions from Residential Oil-fueled Furnaces
4-48
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-14. CDD/CDF Emission Factors for Oil-Fired Utility/Industrial Boilers
J *
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
U.S. EPA,(1997b)
Median
Emission Factor
(pg/L oil)
117
104
215
97
149
359
413
83
77
86
109
68
104
86
169
179
179
1 ,453
1,141
314
102
104
145
359
413
90
131
172
27
179
1,722
EPRI (1994)
Mean Emission Factor
ND = zero
(pg/L oil)
0
24.7
63.3
65.8
79.7
477
2055
- 0
64.1
49.3
76.5
35.4
0
23.8
1 64
0
0
2,766
414
95.5
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
3,179
ND = 1/2 DL
(pg/L oil)
26.6
43.1
108
79.3
102
546
2141
35.7
73.9
59.6
94.9
45.2
37.7
42.2
218
137
139
3,047
883
170
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
3,931
Sources:
U.S. EPA (1997b) - number of facilities not reported.
EPRI (1994) - based on two cold side ESP-equipped power plants.
Note: Assumes a density for residual fuel oil of 0.87 kg/L.
4-49
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
X%.*tio Factor Ccongeoer emission factor / total GDD/GI>F emission
O O.OS 0.1 O.1S
2.3.-7.S-TCDr>
I.2,3.7.8-I>oCE>D
1.2.3.6.7.8-HXCDD
n i|
1.2.3.7.B.S>-Hx:CDr>
2.3.7.B-TCDP
1.2.3.7.»-PcCDF
2.3,4.7.m-PeCr>F
1 .2.3 .4.7.B-H3CCDF
1,2,3.6.7.8-HxCDF
1 ,2.3.7.S.S>-Hx:CDF
2.3,-«.
-------
CO
'•BL
CD
O
£
•a
E
LL
"CO
O
0
^>
E
S.
H—
CO
.2
^ ^ £
2 2 Q 2 Q Q 2
q o o o o o o
CM «- «- r-.,- r- CM
Q Q Q Q Q Q Q
CO CD CO 00 CO ^>
O *- CO *- T- T- - ^
*~ Q Q Q Q Q Q
2 2 2 2 2 2
to co R
J2 S. £ o CD o) CM
Q Q Q.IO ^ CM CO.
222
£2. d d d d — ~
2 2 2 2 2 Z Z
Q
Q Q Q R
-.000°,
g O O O £
Q 0 X X X 00
g 0_ CO CO CO r-~
j— • oo r"** P** co ^o
co r*** ^* co r** ^^
- - . - - - - Q
(*••» 00 CO CO CO CO ^
CO CN 0? CN 0? CN (j
tN'T- T-^ *- T- T- O
i ^
jv. r^ r^ ^ r^ r^ CM CM CM ^*
2 2 2222 22""
r>»ooT-ocj>u>oOo)
(», 10 ^t 10 •* CO CM " 10 lr'
^ Q Q Q Q Q Q Q Q g
CO CMiCM "* 00 00 ^ CO "^ ?
CO CO :CO ^_ IO 00 ^f ^J. T_ ^
qooooooooo
QQQQQQQQQQ
00 CD
oo CM co ^ ro »- o o co ^-
.^.«g..gN
P» 5J q « ^ . -
ooQQ'-Qt-T'cNT'co
22 22 2
'gg^w^.f .g -8^
ii^^^ii.^i..10-
U. U-
u. u. u- u. -C 1 Q •
Q Q Q Q U O
^ ^ 0 0 0 0 ^^
1— oooor-r~-.cor-.cor-.
co r— r— ^f co r— co ^^ *^
r-co-^i'Ciocooo-^i'Cocoy^
co" CM. co" CM" CM" CM co" CM" CM" (j
CM T- CM" T-_ T- T- CM" T- »- O
CM CM
co m
CM
o o
o o
CO
. *
PS
.»?
Q u.
.Q Q
U 0
CO CO
co" co"
CM CM
CD ID
o o
H H
uo CM rf *- r** r» , '
10 CO CM CO
CMCOrl:'T~Q00* H. (O ^ CD CO CO
. 2 . 22
Q Q Q _ .. M U_ LL
Q Q Q Q g U. Q Q Q "r
1-D.IXOHCLXXO
OOOOOOOOOO
l-l-f-HI-l-l-l-l-l-:
CO
00
CO
.CM
CM
T—
r«.
CD
o
o
CM
en
r-
CM
O)
CM
u.
Q
CJ
u
u
"CD
o
• +J
he detection lim
problem.
parentheses is t
3d contamination
C 4^
— o . — .
CD 03 IO
— to"05
"S "° "5
' " o t +s
£'§. 2
CD "^
"° • >- CO
S o be
CD
II II ££
Q cc §
2 2 CO
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-16. Characteristics of U.S. Coal-Fired Power Plants Tested by DOE
Plant
No.
1
2
3
4
5
6
7
Coal Type
Bituminous
Bituminous
Subbituminous
Subbituminous
Bituminous
Lignite
Bituminous
Coal
Chlorine
Content
(mg/kg)
800
1,400
300
390
1,400
400
r,ooo
Temperature (°C) at:
Pollution Control Device3
ESP
160
130
„
130
170
150
Bag
-_
™
150
70
.
—
FGD
—
—
130
120
170
—
Stack
160
130
150
75
40
110
150
8 ESP = Electrostatic precipitator. Bag = Baghouse, FGD = Flue gas desulfurization system.
Source: Riggs et al. (1995).
4-52
ApvU A 998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-17. CDD/CDF Emission Factors for Coal-Fired Utility/Industrial Power Plants
. .
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
Mean Emission Factor
ND = zero
(ng/kg coal)
0.007
0
0
0.005
0.005
0.216
0.517
0.109
0.008 ,
0.075
0.110
0.016
0.015
0.054
0.354
0.097
0.159
0.750
0.997
0.087
0.076
0.027
0.060
0.106
0.517
0.230
0.347
0.209
0.127
0.159
1.86
ND = 1/2 DL
(ng/kg coal)
0.020
0.018
0.038
0.031
0.039
0.241
, 0.648
0.117
0.025
0.085
• 0.136
0.031
0.043
0.075
0.385
0.126
' 0.281
1.035
1 .304 ,
0.136
0.078
0.029
0.060
0.120
0.648
0.250
0.223
0.209
0.133
0.281
2.03
Source: EPRI (1994) - 11 facility data set.
4-53
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
O.O1 O.OZ O.O3 O.O4 O.OS O.O6 O.O7 O.O8
O.O9
2,3.7.8-TCDD
1,2.3,7.8-PeCDD
1 ,2,3 ,4.7.8-fixCDr>
I ^,3,6,7,8-HxCDD
1.2.3.7,B,9-HxCr>D
1,2,3,4.6.7.8-HpCDD
I,2,3,4,6.7.8.£-OCt>l>
2,3.7.8-TCDF
1,2.3,7.8-PeCDF
2,3,4,7,8-PeCDF
1.2,3,4.7.8-HxCDF
145,3 ,6,7,8-HxCDF
2,3 ,4,6,7.«-HxCbF
1 ^^,4,6,7.8-HpCDF
1 .2,3.4,7.8.9-iHpCDF
Ratio (congener croup emission factor / total CDD/CDF emission factor) >
0.05 0.1 0.15 0.2 0.25 0.3
0.35
Figure 4-8. Congener and Congener Group Profiles for Air Emissions
from Industrial/Utility Coal-fueled Combustors
4-54
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 4-18. CDD/CDF Emission Factors from Residential Coal Combustors
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
i,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 '
"Salt" Lignite
Ref . A
(ng/kg coal)
0.58
0.73
0.63
0.60
0,40
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
13.60
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" Lignite
Ref. A
(ng/kg coal)
0.06
0.08
0.06
0.09
0.06
0.59
2.42
0.50
0.43
0.31
0.13
0.36
0.02
0.12
0.95
0.06
0.30
3.38
3.20
0.34
9.00
2.22
1.81
0.82
2.42
20.33
8.98 .
3.78
1.27
0.30
50.93
Anthracite
Ref. B
(ng/kg coal)
1.60
NR
, NR
NR
~NR
NR
77
42.0
NR
NR
NR
NR
NR
• NR
NR
NR
4.2
NR
NR
60.0
61.6
31
60
57
77
412
340
130
32
4.2
1,205
Bituminous
Ref. B
(ng/kg coal)
2.40
NR
NR
NR
NR
NR
120
63.0
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
Sources: Ref A: Thub et al. (1995); listed results represent means of three flue gas samples.
Ref B: U.S. EPA (1997b); based on average particufate CDD/CDF concentrations from chimney
soot samples collected from seven coal ovens and particulate emission factors for
anthracite and bituminous coal combustion.
NR = not reported.
4-55
April 1998.
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congenergroup emission factor/total CDD/CDF emission factor)
0.1 0.2 0.3
0.4
I Anthracite (U.S. EPA, 1997b)
Bituminous (U.S. EPA, 1997b)
Figure 4-9. Congener Group Profile for Air Emissions from Residential Coal-fueled Combustors
4-56
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
5. COMBUSTION SOURCES OF CDD/CDF: OTHER HIGH TEMPERATURE SOURCES
5.1. CEMENT KILNS
This section addresses CDD/CDF emissions from Portland cement kilns. These
facilities use high temperature to convert mineral feed stocks into Portland cement and
other types of construction materials. For purposes of this analysis, cement kilns have
been subdivided into two categories: those that burn hazardous waste and those that do
not. Lightweight aggregate kilns are not addressed in this report. The following sections
describe cement kiln technology, review the derivation of TEQ emission factors for cement
kilns that do burn and do not burn hazardous waste as supplemental fuel, and derive annual
TEQ air emissions (g/yr) for 1995 and 1987.
5.1.1. Process Description of Portland Cement Kilns
In the United States, the primary cement product is called Portland cement.
Portland cement is a fine, grayish powder consisting of a mixture of four basic materials:
lime, silica, alumina, and iron compounds. Cement production involves heating
(pyroprocessing) the raw materials to a very high temperature in a rotary (rotating) kiln to
induce chemical reactions that produce a fused material called clinker. The cement clinker
is further ground into a fine powder and mixed with gypsum to form the Portland cement.
The cement kiln is a large, rotating steel cylindrical furnace lined with refractory material.
The kiln is aligned on a slight angle, usually a slope of 3° - 6°. This allows for the materials
to pass through the kiln by gravity. The upper end of the kiln is known as the 'cold' end.
This is where the raw materials, or meal, is fed into the kiln. The lower end of the kiln is
known as the "hot" end. The hot end is where the combustion of primary fuels (usually
coal and petroleum coke) transpires to produce a high temperature. The cement kiln is
operated in a counter-current configuration. This means that the hot combustion gases are
conyected up through the kiln while the raw materials are passing down toward the lower
end. The kiln rotates about 50 to 70 revolutions per hour, and the rotation induces mixing
and the forward progress of mixed materials. As the meal moves through the cement kiln
and is heated by the hot combustion gases, water is vaporized and pyroprocessing of
materials occurs.
5-1 April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
«'. , • ,•'••. !••• -I. ' '' .'•''.. ; ' '
When operating, the cement kiln can be viewed as consisting of three temperature
zones necessary to produce cement clinker. Zone 1 is at the upper end of the kiln where
the raw meal is added. Temperatures in this zone typically range from ambient up to
600°C. In this area of the kiln, moisture is evaporated from the raw meal. The second -
thermal zone is known as the calcining zone. Calcining occurs when the hot combustion
gases from the combustion of primary fuels dissociates calcium carbonate from the
i , ' ' VI ' ,„
limestone to form calcium oxide. In this region of the kiln, temperatures are in a range of
600°C to 900°C. The third region of the kiln is known as the burning or sintering zone.
The burning zone is the hottest region of the kiln. Here temperatures in excess of 1,500°C
induce the calcium oxide tq react with silicates, iron and aluminum in the raw materials to
form cement clinker. The formation of clinker actually occurs near the lower end of the kiln
(close to the combustion of primary fuel) where temperatures are the hottest. The
chemical reactions that occur here are referred to as pyroprocessing.
The cement clinker that is formed and that leaves the kiln at the hot end is a gray-
, ' . j, i ' ,i ' '' "' ' ' " •' ''"; .«' ' ,!''' i
colored, glass-hard material comprised of dicalcium silicate, tricalcium silicate, calcium
aluminate, and tetracalcium aluminoferrite. At this point, the clinker has a temperature of
about 1,100°C. The hot clinker is then dumped onto a moving grate where it is cooled by
passing under a series of cool air blowers. Once cooled to ambient temperature, the clinker
is ground into a fine powder and mixed with gypsum to produce the Portland cement
product.
< • • \ • i . - ., , , •
Cement kilns can be either wet or dry processes; In the wet process, the raw
materials are ground and mixed with water to form a slurry. The meal-water slurry is fed
into the kiln through a pump. This is an older process. A greater amount of heat energy is
needed in the wet process than in other types of kilns. These kilns consume about 5 to 7
trillion BTUs per ton of clinker product to evaporate the additional water.
In the dry process, a pre-heater is used to pre-dry the raw meal. A typical pre-
heater consists of a vertical tower containing a series of cyclone-type vessels. Raw,meal is
added at the top of the tower, and hot kiln exhaust flue gases from the kiln operation are
used to preheat the meal prior to being loaded into the kiln. Pre-heating the meal has the
advantage of lowering fuel consumption of the kiln. Therefore, dry kilns are now the most
popular cement kiln type. EPA estimates that Portland cement clinker production in the
United States was 67.6-billion kg in 1995 and 52-billion kg in 1987 (U.S. DOC, 1996).
. 5-2 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
5.1.2. Cement Kilns Burning Hazardous Waste
The high temperatures achieved in cement kilns make cement kilns an attractive
technology for combusting hazardous waste as supplemental fuel. Sustaining the relatively
high combustion temperatures (1,100°C to 1,500°C) that are needed to form cement
clinker requires the burning of a fuel with a high energy output. Therefore, coal or
petroleum coke is typically used as the primary fuel source. Because most of the cost of
operating the cement kiln at high temperatures is associated with the consumption of fossil
fuels, some cement kiln operators have elected to burn hazardous liquid and solid waste as
supplemental fuel. Currently about 75 percent of the primary fuel is coal. Organic
hazardous waste may have a similar energy output as coal (9,000 to 12,000 Btu/lb for
coal). The strategy of combusting the waste as supplemental fuel is to off-set the amount
of coal/coke that is purchased and burned by the kiln. The operator may .charge a disposal
fee to the waste generator for the right to combust the hazardous waste at the kiln, which
also offsets the cost of kiln operation. Much of the high energy and ignitable wastes are
primarily comprised of such diverse substances as waste oils, spent organic solvents,
sludges from the paint and coatings industry, waste paints and coatings from the auto and
truck assembly plants, and sludges from the petroleum refining industry (Greer et al.,
1992).
The conditions inherent in the cement kiln mimic conditions of hazardous waste
incineration. For example, the gas residence time in the burning zone is typically three
seconds while at temperatures in excess of 1,500°C (Greer et al., 1992). In addition, trial
burns have consistently shown that 99.99 to 99.9999 percent destruction and removal
efficiencies for the very stable organic wastes can be achieved in cement kilns {Greer et al.,
1 992). Although the combustion of hazardous waste as supplemental or substitute fuel
does have apparent advantages, only 16 percent of the Portland cement kilns (34 of the
212 kilns) combusted hazardous waste in 1995 (Federal Register, 1996b). Other types of
supplemental fuel used by these facilities include automobile tires, used motor oil, and
sawdust, and scrap wood chips.
The method of introducing liquid and solid hazardous waste into the kiln is a key
factor to the complete consumption of the waste during the combustion of the primary
fuel. Liquid hazardous waste is either injected separately or blended with the primary fuel
(coal). Solid waste is mixed and burned along with the primary fuel.
• I
5-3 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
5.1.3. Air Pollution Control Devices Used on Cement Kilns
The pyroprocessing of raw meal in a cement kiln produces fine participates. This is
referred to as cement kiln dust. Cement kiln dust is collected and controlled with fabric
filters and/or electrostatic precipitators. Acid gases such as SO2 can be formed during
pyroprocessing of the sulfur-laden minerals, but the minerals have high alkalinity which
neutralizes SO2 gases. Most PM control devices used at cement kilns in 1995 and 1987
were considered to be hot-side control devices. A hot side control device is one that
operates at flue gas temperatures above 150°C (note that some EPA rules use different
definitions for hot side devices for different industries). This has been identified as the
critical temperature at or above which CDD/CDFs are formed.
' - , ' i!' ' i ' - ,,•',•' -.' ..' •' " ".",.'•' .
Reducing the flue gas temperature in the PM control device is one factor shown to
have a significant impact on limiting dioxin formation and emissions at cement kilns (U.S.
EPA, 1997d). Recent emissions testing at a Portland cement ki.ln showed that CDD/CDFs
were almost entirely absent at the inlet to a hot-sided ESP, but CDDs and CDFs were
measured at the exit to the ESP (U.S. EPA, 1997d). This conclusively showed that dioxins
were formed within the hot-side ESP. Reducing the flue gas temperature in the PM control
device to below 150°C has been shown to substantially limit CDD/CDF formation at
cement kilns. This is believed to be due to preventing the post-combustion catalytic
formation of CDD/CDFs. Consequently a number of cement kilns have added flue gas
quenching units upstream of the APCD to reduce the inlet APCD temperature, thereby
reducing CDD/CDF stack concentrations. A quench usually consists of a water spray
system within the flue duct. Thus, cement kilns tested after 1995 have substantially
reduced CDD/CDF emissions as compared to cement kilns used to derive emission
estimates in this report. ;
5.1.4. CDD/CDF Emission Factors for Cement Kilns
The source emissions data base contains test reports of CDD/CDF emissions from
12 cement kilns burning hazardous waste and 11 cement kilns not burning hazardous
waste (U.S. EPA,1996c) The majority of stack emissions data from cement kilns burning
hazardous waste were derived during trial burns, and may overestimate the CDD/CDF
emissions that most kilns achieve during normal operations. Stack emissions data from
kilns not burning hazardous waste were derived from testing during normal operations.
" ' 5-4 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
For purposes of deriving emission factors, the general strategy used in this
document is to consider subdividing each source category on the basis of design and
operation. However, cement kilns are relatively uniform in terms of kiln design, raw feed
material, temperatures of operation, and APCDs. Therefore, no subdivisions were made on
these bases. An important difference among kilns, however, is the whether or not
hazardous waste is burned as a supplementary fuel. The average TEQ emission factors are
24.34 ng TEQ per kg clinker produced and 0.29 ng TEQ kg clinker produced for cement
kilns burning and not burning hazardous waste, respectively. Accordingly, the average
emission factor for kilns burning hazardous waste is about 80 times greater than that for
kilns not burning hazardous waste. As discussed in Section 5.1.6 (Cement Kiln Dust), a
comparison of CDD/CDF concentrations in cement kiln dust samples from cement kilns
burning and not burning hazardous waste show a similar relationship (i.e., the cement kiln
dust from kilns burning hazardous waste had about 100 times higher CDD/CDF TEQ
concentration than dust from nonhazardous waste burning kilns).
It is possible that differences other than the use of hazardous waste are contributing
to the observed differences in emissions. Although the average emission factors for the
two groups of kilns differ substantially, the emission factors for individual kilns in the two
groups overlap. The five lowest emission factors for kilns burning hazardous waste span
the same range as the five highest emission factors for kilns not burning hazardous waste.
Accordingly, other aspects of the design and operation of the kilns may be affecting
CDD/CDF emissions. Possibilities include procedures for preheating the meal, type of
primary fuel, type of secondary fuel, and the characteristics of the raw meal. All tested
kilns were operating with hot-side ESPs during the stack tests.
Attempts to understand this issue through parametric testing of cement kilns have
yielded mixed results. EPA conducted a limited comparison of CDD/CDF TEQ stack gas
concentrations (ng TEQ/dscm) between cement kilns burning hazardous wastes and not
burning hazardous wastes (U.S. EPA, 1997d). These comparisons were made at 14
cement kilns. Operating conditions (e.g., APCD temperature), with the exception of the
fuel being burned, were the same or similar for each set of comparisons. Baseline
conditions used coal as the on|y primary fuel. The results of these comparisons showed:
5-5 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
• Seven kilns in which the baseline (i.e., no combustion of hazardous waste)
CDD/CDF TEQ stack gas concentrations were about the same as that for .the
burning of hazardous wastes;
• Two kilns in which the baseline CDD/CDF TEQ stack gas concentrations were
about double that for the burning of hazardous wastes; and
• Five kilns in which the hazardous waste CDD/CDF TEQ stack gas
concentrations were substantially greater (from 3 to 29 times greater) than
that for the baseline operating conditions.
Currently no satisfactory .explanation exists for the apparent differences in the
emission factors. Given the strong empirical evidence that real differences may exist,
EPA/ORD has decided to treat the kilns burning hazardous waste separately from those not
burning hazardous waste for the purposes of developing a CDD/CDF emissions inventory.
The average emission factor (EF) for each cement kiln was calculated using Equation
5-1. ' ' ; ' ' ' ^ ^ ^ ; _ .' '
C x Fv
EFck = • (Eq. 5-1)
•cl
Where: .'-.,.,
. , • ;, ' ,n i ' ' ' '" ' ' / , ' . , ,
EFck = Cement kiln emission factor (burning or not burning hazardous waste),
(ng TEQ per kg of clinker produced).
C = TEQ or CDD/CDF concentration in flue gases (ng TEQ/dscm) (20°C, 1
atm; adjusted to 7% O2).
Fv = Volumetric flue gas flow rate (dscm/hr) (20° C, 1 atm; adjusted to 7%
02).
lcl = Average cement kiln clinker production rate (kg/hr).
After developing average emission factors for each tested cement kiln, the overall average
<, y ' " • • .. • • .••',•' 'i • • ' - ' ' •: .1 • '
congener-specific emission factor was derived for all tested HWIs using Equation 5-2
below.
[EF + EFrfC + EFCK ......
L CK CK CK* _ _ (Eq. 5-2)
'N
5-6 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Where:
Average emission factor of tested cement kilns either
burning or not burning hazardous waste as
supplemental fuel (ng TEQ/kg clinker)
Number of cement kilns tested
The average emission factors representative of the cement kilns burning and not burning
hazardous waste are summarized in Table 5-1. Because the same test reports were used,
the emission factors are the same for both the 1995 and 1987 reference years. Congener
and congener group profiles for cement kilns burning hazardous waste are presented in
Figure 5-1 and for cement kilns not burning hazardous wastes in Figure 5-2.
5.1.5. National Estimates of CDD/CDF Emissions from Cement Kilns
National estimates of CDD/CDF air emissions (grams TEQ per year) from all Portland
cement kilns operating in 1995 and 1987 were made by multiplying the average TEQ
emission factor by the annual activity level (cement clinker produced) for cement kilns,
burning and not burning hazardous waste, respectively.
Nonhazardous waste burning cement kilns produced 61.3-billion kg of cement
clinker in 1995 (Heath,1995). Since a totalof 67.6-billion kg of cement clinker were
produced in the United States in 1995 (U.S. DOC, 1996), it follows that cement kilns
burning hazardous waste produced 6.3-billion kg of clinker (or 9.3 percent of the clinker
produced). Approximately 52-billion kg of cement clinker were produced in 1987 (U.S.
DOC, 1996). If it is assumed that 9.3 percent of this total clinker production was from
hazardous waste burning kilns, then about 4.8 billion kg of clinker were produced in
hazardous waste burning kilns in 1987. These activity level estimates are given a "high"
confidence rating, because they are based on recent survey data (U.S. EPA, 1996c).
The TEQ emission factors are given a "low" confidence rating for both cement kilns
burning and not burning hazardous waste. The TEQ EF for nonhazardous waste burning
kilns were given a low rating because only 11 out of 178 (6 percent^have been tested for
CDD/CDF emissions. These data may not be representative of routine CDD/CDF emissions
from all kilns not burning hazardous waste. Emission factors for the 11 tested kilns ranged
5-7 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
from not detected up to a maximum of 2.6 ng TEQ/kg clinker. Although a higher
• ^
percentage of the kilns burning hazardous waste had been tested (12 out of 34 or 35
percent of the kilns were tested in 1995) greater uncertainty exists about whether the
emissions are representative of normal operations due to trial burn procedures. Accordingly,
a low confidence rating was also assigned to the kilns burning hazardous waste.
The low confidence rating for the emission factors and high confidence rating 'for
the activity levels combine to produce an overall low confidence rating. Accordingly, the
estimated ranges of potential emissions are assumed to vary by a factor of 10 between the
low and high ends of the range:
1 '!( • ' - ' " '.-. : "i ••::. ." -. • , "<,'.;.
• 1995: For cement kilns not burning hazardous waste, the central estimate is
17.8 g TEQ/yr with a range of 5.6 g TEQ/yr to 56.3 g TEQ/yr. For cement
kilns burning hazardous waste, the central estimate is 153 g TEQ/yr with a
range of 48.4 g TEQ/yr to 484 g TEQ/yr.
• 1987: For cement kilns not burning hazardous waste, the central estimate is
13.7 g TEQ/yr with a range of 4.3 g,TEQ/yr to 43.3 g TEQ/yr. For cement
kilns burning hazardous waste, the central estimate is 117 g TEQ/yr with a
range of 37.0 g TEQ/yr to 370 g TEQ/yr. •
An alternative way to estimate CDD/CDF emissions would be to make no distinction
between kilns burning and not burning hazardous waste. If the test data are combined to
develop a single emission factor for all cement kilns, the average emission factor would
then be 12.84 ng TEQ/kg of clinker. Multiplying this average emission factor by the 67.6
billion kg of total cement clinker produced in 1995 would yield an emission estimate of 868
- "!•' ;; ,..•••,< :', .. ; :.', ; : ': . •• '' ,.<:,'';:•,;: ••• | , . '
g TEQ/yr. Applying the same procedure to the 52-billion kg of clinker produced in 1987
yields an emission estimate of 668 g TEQ/yr. The central estimates using this approach
exceed the upper estimates derived above using the approach of separating kilns burning
'"> ' '. ' " ; ' . ''•' '' ' ' '' . ' "i *', ' • '';'• ' '
and not burning hazardous waste.
On April 19, 1996, EPA proposed revised emission standards for cement kilns and
lightweight aggregate kilns burning hazardous waste (Federal Register, 1996b). These
< „ 1 " ' , ( • . .'., -, •'. • i,1,1,1 • r .: ' ,• I-' i
standards, including emission standards for CDD/CDF (0.20 ng tEQ/dscm at 7 percent O2),
were proposed under joint authority of the Clean Air Act (CAA) and the Resource
i _ i: ?" i ; • ' • •, . • '•.•,"> ' : ' .
»"!J ' " ' ' ", t ' ' ' „ '' ' "
III ' ' ' i ' ', "
5-8 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Conservation and Recovery Act (RCRA). The proposed standards reflect the performance
of Maximum Achievable Control Technologies (MACT) as specified by the CAA. These
standards should lead to lower CDD/CDF emissions than those estimated above for 1995.
' - - i ,
>5.1.6. Cement Kiln Dust
EPA characterized cement kiln dust (CKD) in a Report to Congress (U.S. EPA,
1993g). The report was based in part on a 1991 survey of cement manufacturers
conducted by the Portland Cement Association (PCA). Survey responses were received
from 64 percent of the active cement kilns in the United States. Based on the survey
responses, EPA estimated that in 1990 the U.S. cement industry generated about 12.9-
i - " i •
million metric tons of gross CKD and 4.6-million metric tons of "net CKD," of which 4.2-
million metric tons were land disposed. The material collected by the APCD system is
called "gross CKD" (or "as generated" CKD). The gross CKD is either recycled back into
the kiln system or is removed from the system for disposal (i.e., "net CKD" or "as
managed" CKD) (U.S. EPA, 1993g).
Also in support of the Report to Congress, EPA conducted sampling and analysis
during 1992 and 1993 of CKD and clinker. The purposes of the sampling andlanalysis
efforts were: (1) to characterize the CDD/CDF content of clinker and CKD ; (2) to determine
the relationship, if any, between the CDD/CDF content of CKD and the use of hazardous
waste as fuel; and (3) to determine the relationship, if any, between the CDD/CDF content
of CKD and the use of wet versus dry process cement kilns. Clinker samples were
collected from 9 kilns not burning hazardous waste and 11 kilns burning hazardous waste
(U.S. EPA, 1993g).
CDD/CDFs were not detected in any cement kiln clinker samples. Tetra- through
octa-chlorinated CDDs and CDFs were detected in the "gross CKD" samples obtained from
TO of the 11 kilns and in the "net CKD" samples obtained from 8 of the 11 kilns. The
CDD/CDF content of "gross CKD" ranged from 0.008 to 247 ng TEQ/kg and from 0.045 to
195 ng TEQ/kg for "net CKD." Analyses for seven PCB congeners were also conducted,
but no congeners were detected in any clinker or CKD sample. The mean CDD/CDF
concentrations in "net CKD" generated by the kilns burning hazardous waste are higher (35
ng TEQ/kg) than in "net CKD" generated by the facilities not burning hazardous waste
(3.0E-02 ng TEQ/kg). These calculations of mean values treated nondetected values as
5-9 April 1998
-------
DRAFT-Dp NOT QUOTE OR CITE
zero. If the nondetected values had been excluded from the calculation of the means, the
mean value for "net CKD" from kilns burning hazardous waste would increase by a factor
of 1.2, and the mean value for "net CKD" from kilns not burning hazardous waste would
increase by a factor of 1.7. One sampled kiln had a "net CKD" TEQ concentration more
than two orders of magnitude greater than the TEQ levels found in samples from any other
9 : I , f- ' . ,
kiln. If this kiln was considered atypical of the industry {U.S. EPA, 1993g) and was not
included in the calculation, then the mean "net CKD" concentration for hazardous waste
burning kilns decreases to 2.9 ng/kg.
AH CKD is normally disposed in engineered landfills and consequently not
categorized as an environmental release as defined in this emission inventory. The amount
of CDD/CDF associated with these materials is calculated for informational purposes. The
estimate of land:disposed CKD from the 1991 PCA Survey (4.2-million metric tons per year
Ibasis year is 19*90]) was divided among kilns burning hazardous waste (34 kilns) and those
,| • •••''. ', .•: •, "" .'•', , ;,•'. >' . '
that do not {1?| kilns) on the basis of the number of kilns in each category. The average
TEQ concentration in the net CKD from kilns burning hazardous waste (including the high
value discussed above) was 35 ng TEQ/kg. For kilns that do not have hazardous waste,
the average concentration in the "net CKD" was 3.6E-62. Multiplying these average
concentrations by the annual "net CKD" production yields estimates of 24-g TEQ/yr for
kilns burning hazardous waste and 0.1-g TEQ/yr for kilns not burning hazardous waste,
yielding a total of 24.1-g TEQ/yr for all kilns.
;;.!!: , - : " ' ' • •• , . ••• : •• '•. v:' ..!••• / •
5.2. ASPHALT MIXING PLANTS
Asphalt consists of an aggregate of gravel, sand, and filler mixed with liquid asphalt
cement or bitumen. Filler typically consists of limestone, mineral stone powder, and
1 '!: , u •>, , „ • • , • ,. , , : : , ; ,.-, J , • i. ,, , '
sometimes ash from power plants and municipal waste combustors. The exact
composition of an asphalt formulation depends on how it will be used. The components of
the aggregate are dried, heated, and mixed/coated with the bitumen at an asphalt mixing
installation. "Old" asphalt (i.e., asphalt from dismantled bridges and roads) can be
disaggregated to its original components through heating and reused in the manufacture of
new asphalt.
5-1 0 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
No data are available on CDD/CDF emissions, if any, from U.S. asphalt mixing
operations. However, limited data are available for facilities in The Netherlands and
Germany.
Bremmer et al. (1994) measured CDD/CJJF content in air emissions from an asphalt
mixing plant in The Netherlands to be 47-ng TEQ per metric ton of produced asphalt. No
congener-specific emission factors were reported by Bremmer et al. (1994). The tested
facility heated old asphalt in an individual recycling drum to about 150°C with flue gases
that were mixed with ambient air to a temperature of 300-400°C. Parallel to this recycling
drum, the "main drum" dried and heated the aggregate (sand and gravel/granite chippings)
to a temperature of about 220°C. The flue gases leaving the recycling drum are led along
the main burner of the main drum for incineration. The old asphalt, the minerals from the
main drum, and new bitumen from a hot storage tank (about 180°C) were mixed in a mixer
to form new asphalt. Natural gas fueled the tested facility during the sample collection
period and used old asphalt as 46 percent of the feed. The facility's APCD system
consisted of cyclones and a fabric filter.
Umweltbundesamt (1996) reported lower emission factors for three tested facilities
in Germany that were also equipped with fabric filters. These three facilities were fueled
by oil and/or butane gas and>used old asphalt at usage rates ranging from 30 to 60 percent
of the/feed. The emission factors calculated from the stack gas concentrations, gas flow
rates, and hourly thruputs for these three facilities were 0.2, 3.5, and 3.8 ng TEQ/metric
ton of asphalt produced.
Approximately 25-miIlion metric tons of asphalt bitumen were produced in the
United States in 1992. An identical quantity was produced in 1990 (U.S. DOC, 1995a).
Bitumen constitutes approximately 5 percent by weight of finished paving asphalt (Bremmer
et al., 1994). Thus/an estimated 500-million metric tons of paving asphalt are produced in
the United States annually.
Because there are no direct measurements of CDD/CDF emissions from U.S. asphalt
plants and because of uncertainties regarding the comparability of U.S. and Dutch asphalt
plant technologies and feed materials, no national emission estimate for this category is
proposed at this time. However, a preliminary order of magnitude estimate of the potential
annual TEQ emissions for U.S. production of asphalt can be obtained by averaging the '
emission factors for the four facilities reported by Bremmer et al. (1994) and
5-11 April 1998
-------
bRAFT-DO NOT QUOTE OR CITE
Umweltbundesarnt (1996). Applying this average emission factor (i.e., 14 ng TEQ/metric
ton of asphalt produced) to the activity level of 500-million metric tons of paving asphalt
produced annually yields an annual emission of 7 g TEQ/yr, which, when rounded to the
nearest order of magnitude to emphasize the uncertainty in this estimate, results in a value
"',':'" ' • ' , •" • ' ' ' ' ii ' '' '' ', ' '
of 10 g TEQ/yr. This estimate should be regarded as a preliminary indication of possible
emissions from this source category; further testing is needed to confirm the true
magnitude of these emissions.
5.3. PETROLEUM REFINING CATALYST REGENEfcATION
Regeneration of spent catalyst for use in the petroleum refinery reforming process is
a potential source of CDDs and CDFs based on limited testing conducted in the United
States (Amendola and Barna, 1989; Kirby, 1994), Canada (Maniff and Lewis, 1988;
Thompson et al., 1990), and The Netherlands (Bremmer et al., 1994). The available data
indicate that CDD/CDFs can be generated during the catalyst regeneration process.
However, the available data indicate that releases to water (i.e., treated wastewater) and in
solid waste are minimal. Releases to air could result from untreated vented flue gases at
some facilities, and the CDD/CDFs formed could possibly be reintroduced into other refining
operations (e.g., the coker) and resulting products. However, the available data are not
adequate to support even order of magnitude release estimates for air and product releases.
The following paragraphs summarize the catalyst regeneration process, relevant studies
performed to date, and the status of EPA regulatory investigations of this source.
s ' i;; . .•';.. • . :; ' .•••'-. .'•' ,';>''..',
Catalytic reforming is the process used to produce high octane reformates from
lower octane reformates for blending of high octane gasolines and aviation fuels. The
reforming process occurs at high temperature and pressure and requires the use of a
platinum or platinum/rhenium catalyst. During the reforming process, a complex mixture of
aromatic compounds, known as coke, is formed and deposited onto the catalyst. As coke
deposits onto the catalyst, its activity is decreased. The high cost of the catalyst
necessitates its regeneration. Catalyst regeneration is achieved by removing the coke
deposits via burning at temperatures of 750 to 8506F and then reactivating the catalyst at
elevated temperatures (850 to 1,000°F) using chlorine or chlorinated compounds (e.g.,
" methylene chloride, 1,1,1-trichloroethane, and ethylene dichloride). Burning of the coke
produces flue gases that can contain CDDs and CDFs along with other combustion
t ' ' ;!| ' ;i 'i '" ', ' • '
ii:, ' '..,,,•'''. • , ,
5-12 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
products. Because flue gases, if not vented directly to the atmosphere, may be scrubbed
with caustic or water, internal effluents may become contaminated with CDD/CDFs (Kirby,
1994; SAIC, 1994).
In 1988, the Canadian Ministry of the Environment detected concentrations of CDDs
in an internal wastestream of spent caustic in a petroleum refinery that ranged from 1.8 to
22.2 A*gL, and CDFs ranging from 4.4 to 27.6 //g/L (Maniff and Lewis, 1988). The highest
concentration of 2,3,7,8-TCDD w,as 0.0054 ^g/L. CDDs were also observed in the
refinery's biological sludge at a maximum concentration of 74.5 ^g/kg, and CDFs were
observed at a maximum concentration of 125 yug/kg. The concentration of CDD/CDFs in
the final combined refinery plant effluent was below the detection limits.
Amendola and Barna (1989) reported detecting trace levels of hexa- to octa-CDDs
and CDFs in untreated wastewaters (up to 2.9 pg TEQ/L) and Wastewater sludges (0.26 to
2.4 ng TEQ/kg) at a refinery in Ohio. The levels of detected total CDD/CDFs in the
wastewater and sludge were much lower «3 ng/L and < 1 /ug/kg, respectively) than the
levels reported by Maniff and Lewis (1988). No CDD/CDFs were detected in the final
treated effluent (i.e., less than 0.2 ng TEQ/L). The data collected in the study were
acknowledged to be too limited to enable identifying the source(s) of the CDD/CDFs within
the refinery. Amendola and Barna (1989) also present in ah appendix to their report the
results of analyses of wastewater from the reformer catalyst regeneration process units at
two other U.S. refineries. In both cases, untreated wastewaters contained CDDs and CDFs
at levels ranging from high pg/L to lo,w ng/L (results were reported for congener group
totals, not specific congeners). However, CDD/CDFs were not detected in the only treated
effluent sample collected at one refinery.
Thompson et al. (1990) reported total COD and CDF concentrations of 8.9 ng/m3
and 210 ng/m3, respectively, in stack gas samples from a Canadian petroleum refinery
reforming operation. Thompson et al. (1990) also observed CDDs and CDFs in the internal
wash water from a scrubber of a periodic/cyclic regenerator in the* pg/L to ng/L range.
Beard et al. (1993) conducted a series of benchtop experiments to investigate the
mechanism(s) of CDD/CDF formation in the catalytic reforming process. A possible
-; .- •
pathway for the formation of CDFs was found, but the results could not expjain the
formation of CDDs. Analyses of the flue gas from burning coked catalysts revealed the
presence of unchlorinated dibenzofuran (DBF) in quantities up to 220 /ug/kg of catalyst.
5-13 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Chlprination experiments indicated that dibenzofuran and possibly biphenyl and similar
hydrocarbons act as CDF precursors and can become chlorinated in the catalyst
regeneration process. Corrosion products on the steel piping of the process plant seem to
be the most likely chlorinating agent.
In May 1994, EPA's Office of Water conducted a sampling and analytical study of
catalytic reforming regeneration wastewater for CDD/CDFs at three petroleum refining
plants (Kirby, 1994). The study objectives were to determine the analytical method best
, ,,, „ ' , * ; " ' r ' , , ,'F i ' 1
suited for determining CDD/CDFs in refinery wastewater matrices and to
screen/characterize wastewater discharges from several types of reforming operations for
CDD/CDFs. The report for this study (Kirby, 1994) also presented results submitted
voluntarily to EPA by two other facilities. The sampled untreated wastewaters and spent
caustics were found to contain a wide range of CDD/CDF concentrations, 0.1 pg TEQ/L to
57.2 ng TEQ/L. The study results also showed that 90 percent of the TEQ is contained in
the wastewater treatment sludges generated during the treatment of wastewater and
caustic from the regeneration process.
EPA recently issued a notice of its proposed intent not to designate spent reformer
catalysts as a listed hazardous waste under RCRA (Federal Register, 1995b). The primary
oil/water/solids sludges at petroleum refineries are listed as hazardous wastes (K048,
K051, F037, and F038) (Federal Register, 1995b). The Agency's assessment of current
management practices associated with recycling reforming catalyst found no significant
risks to human health or the environment. The Agency estimated that 94 percent of the
approximately 3,600 metric tons of spent reformer catalyst generated annually are
currently recycled for their precious metal content. However, EPA made no determination
of the "listability" of spent caustic residuals formed during regeneration of spent reforming
catalysts. The Agency did identify potential air releases from the combustion of the
reforming catalyst prior to reclamation as possibly of concern. The Agency requested
comments on: (1) opportunities for removing dioxin prior to discharge of scrubber water
into the wastewater treatment system; (2) opportunities to segregate this wastestream;
and (3) potential health risk associated with insertion of dioxin-contaminated media back
into the refinery process (such as the coker). In this proposed rulemaking, EPA also noted
the possibility of dioxin releases to air during regeneration operations, but indicated that
EPA is scheduled to assess the need for development of MACT standards under the CAA
: 5-14 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
for petroleum refining refiner units in 1996. As part of its regulatory investigation under
,RCRA, EPA's OSW commissioned a study to analyze and discuss existing data and
information concerning CDD/CDF formation in the treatment of catalytic reformer wastes.
This report (SAIC, 1994) also identified potential process modifications that may prevent
the formation of CDD/CDFs.
5.4. CIGARETTE SMOKING
•• Bumb et al. (1980) were the first to report that cigarette smoking is a source of
CDD emissions. Subsequent studies by Muto and Takizawa (1989), Ball et al. (1990), and
Lofroth and Zebiihr (1992) also reported the presence of CDDs as well as CDFs in cigarette
smoke. A recent study by Matsueda et al. (1994) reported the CDD/CDF content of the
tobacco from 20 brands of cigarettes from seven countries. Although a wide range in the
concentrations of total CDD/CDFs and total TEQs were reported in these studies, similar
congener profiles and patterns were reported. The findings of each of these studies are
described in the following paragraphs.
No studies published to date have demonstrated a complete and thorough mass
balance, and it is not known whether the CDD/CDFs measured in cigarette smoke are the
result of formation during tobacco combustion, volatilization of CDD/CDFs present in the
unburned tobacco, or a combination of these two sources. The, combustion processes
operating during cigarette smoking are complex and could be used to justify both proposed
source mechanisms. As reported by Guerin et al. (1992), during a puff, gas phase
temperatures reach 850°C at the core of the firecone, and solid phase temperatures reach
800°C at the core and 900°C or greater at the char line. Thus, temperatures are sufficient
to cause at least some destruction of CDD/CDFs initially present in the tobacco. Both solid
and gas phase temperatures rapidly decline to 200 to 400°C within 2 mm of the char line.
Formation of CDD/CDFs has been reported in combustion studies with other media in this
temperature range of 200 to 900°C. However, it is known that a process likened by
Guerin et al. (1992) to steam distillation takes place in the region behind the char line
because of high localized concentrations of water and temperatures of 200 to 400°C. At
"least 1,200 tobacco constituents (e.g., nicotine, n-paraffin, some terpenes) are transferred
intact from the tobacco into the smoke stream by distillation in this area, and it is plausible
that CDD/CDFs present in the unburned tobacco would be subject to similar distillation.
'5-15 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
1 , ' ' ||I:|1 ' '< ' i :
Bumb et al. (1980), using low resolution mass spectrometry, analyzed the CDD
content of mainstream smoke from the burning of a U.S. brand of unfiltered cigarette. A
package of 20 cigarettes was combusted in each of two experiments. Approximately 20 to
30 puffs of 2 to 3 seconds duration were collected from each cigarette on a silica column.
Hexa-, hepta-, and octa-CDD were detected at levels of 6.004-0.008, 0.009, and 0.02-
0.05 ng/g, respectively.
Muto and Takizawa (1989) employed a continuous smoking apparatusjo measure
t
CDD congener concentrations in the mainstream smoke generated from the combustion of
one kind of filtered cigarette (brand not reported). The apparatus pulled air at a constant
continuous rate (rather that a pulsed rate) through a burning cigarette and collected the
smoke on a series of traps (glass fiber filter, polyurethane foam, and XAD-II resin). The
CDD content of the smoke, as well as the CDD content of the unburned cigarette and the
ash from the burned cigarettes, were also analyzed using low-resolution mass
spectrometry. The results for all three media are presented in Table 5-2, and the congener
group profiles for the three media are presented in Figure 5-3. Table 5-3 and Figure 5-4
present the mainstream smoke results on a mass per cigarette basis to enable comparison
with the results pf other studies. The major CDD congener group found was HpCDD,
which accounted for 84 percent of total CDDs found in the cigarette, 94 percent of total
CDDs found in smoke, and 99 percent of total CDDs found in the ash. The 2,3,7,8-
HpCDDs also accounted for the majority of the measured TEQ in the cigarettes and smoke;
however, none were measured in the ash. Although no PeCDDs were detected in the
cigarette, PeCDDs were detected at low levels in the smoke, indicating probable formation
during combustion. Based on the similarities in the congener group profiles for the three
media, Muto and Takizawa (1989) concluded that most of the CDDs found in the cigarette
smoke appear to be the result of volatilization of CDD/CDFs present in the unburned
cigarette rather than resulting from formation during combustion.
Ball et al. (1990) measured the CDD/CDF content of mainstream smoke for the 10
best-selling German cigarette brands. The international test approach (i.e., 1 puff/min; puff
' • '" •: :-f! ' ' ' '.'', ' ••" ':"' ' ''.' •''"• ' (•'•''<'''• ' ' «:'"•,;! ':'/:; ;' ' : ii«:^'.! ; ' ••'',.
flow rate of 35 mL/2 sec) was employed with an apparatus that smoked 20 cigarettes at a
time in three successive batches with a large collection device. The average TEQ content
in mainstream smoke for the 10 brands tested, normalized to a mass per cigarette basis,
was 0.09 pg/cigarette (i.e., 16.5 times less than the value reported by Muto and Takizawa
5-16 April 1998
-------
• DRAFT-DO NOT QUOTE OR CITE
(1989) for a Japanese cigarette brand). However, the congener group profiles were similar
to those reported by Muto and Takizawa (1989) with HpCDD and OCDD the dominant
congener groups found.
Lofroth and Zebiihr (1992) measured the CDD/CDF content of mainstream and
sidestream smoke from one common Swedish cigarette brand. The cigarette brand was
labeled as giving 17 mg carbon monoxide, 21 mg tar, and 1.6 mg nicotine. The
international test approach (i.e., 1 puff/min; puff flow rate of 35 mL/2 sec) was utilized,
and the smoke was collected on glass fiber filters followed by two polyurethane plugs. The
analytical results for mainstream and sidestream smoke are presented in Table 5-3. The
TEQ content in mainstream smoke> normalized to a mass per cigarette basis, was 0.90
pg/cigarette (i.e., about 2 times less than the value reported by Muto and Takizawa (1989)
and 10 times greater than the average value reported by Ball et al. 1990).. As was reported
by Muto and Takizawa (1989) and^in Ball et al. (1990) study, the dominant congener
groups were HpCDDs and OCDD; however, HpCDFs were also relatively high compared to
the other congener group totals. The sidestream smoke contained about 2-pg TEQ per
^
cigarette or twice that of mainstream smoke.
Using high-resolution mass spectrometry, Matsueda et al. (1994) analyzed the
CDD/CDF content of tobacco from 20 brands of commercially available cigarettes collected
in 1992 from Japan, United States, Taiwan, China, United Kingdom, Germany, and
Denmark. Table 5-4 presents the study results. The total CDD/CDF content and total TEQ
content ranged from 109 to 1,136 pg/pack and from 1.4 to 12.6 pg/pack, respectively.
The Chinese cigarette brand contained significantly less CDD/CDFs and TEQs than any
other brand of cigarette. Figure 5-5 depicts the congener group profiles for the average
results for each country. A high degree of similarity is shown in the CDF congener group
profiles between the tested cigarette brands. The Japanese and Taiwanese cigarettes
show CDD congener group profiles different from the other countries' pigarettes.
In 1995, approximately 487-billion cigarettes were consumed in the United States
and by U.S. overseas armed forces personnel. In 1987, approximately 575-billion
cigarettes were consumed. Per-capita U.S. cigarette consumption, based on total U.S.
population aged 16 and over, declined to 2,41 5 in 1995; the record high was 4,345 in
1963 (The Tobacco Institute, 1995; USDA, 1997). These activity level estimates are
assigned a "high" confidence rating.
5-17 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
The available emission factor data presented above enable estimates of the amount
of TEQs that may have been released to the air in 1994 from the combustion of cigarettes
estimated by two methods. The confidence rating assigned to the emission factor is "low"
based on the very limited amount of testing performed to date. First, an annual emission
estimate for 1995 of 0.21-g TEQ is obtained if it is assumed that: (1) the average TEQ
content of seven brands of U.S. cigarettes reported by Matsueda et al. (1994), 8.60
pg/pack (or 0.43 pg/cigarette) are representative of cigarettes smoked in the United States;
(2) CDD/CDFs are not formed, and the congener profile reported by Matsueda et al. (1994)
IS not altered during combustion of cigarettes; and (3) all CDD/CDFs contributing to the
TEQ are released from the tobacco during smoking. The second method is to assume that
the TEQ emission rates for a common Swedish brand of cigarette reported by Lofroth and
Zebuhr (1992) for mainstream smoke (0.90 pg/cigarette) and sidestream smoke (2.0
pg/cigarette) are representative of the emission rates for U.S. cigarettes. This second
method yields an annual emission estimate of 1.41 g TEQ. For 1987, the two methods
yield estimates of 0.25 g TEQ and 1.67 g TEQ.
Because of the "low" confidence rating assigned to the emission factor, the
estimated range of potential air emissions is assumed to vary by a factor of 10 between the
. . - ,p> . .
low and high ends of the range. Assuming that the average of the annual emissions
estimated by the two methods for 1995 (i.e., 0.8 g TEQ) and 1987 (i.e., 1.0 g TEQ) are
the geometric means of the ranges for these years, the ranges are calculated to be 0.25 to
2.5 g TEQ for 1994 and 0.31 to 3.1 g TEQ for 1987. Although these emission quantities
are relatively small when compared to the emission quantities estimated for various
industrial combustion source categories, these emissions assume significance because
humans are directly exposed to cigarette smoke.
5.5. PYROLYSIS OF BROMINATED FLAME RETARDANT8
! The pyrolysis and photolysis of brominated phenolic derivatives and polybroiminated
' • .. :l> "" , i ''•:.'', " " V •'• " f '. ;• .:• V .'•,•••
biphenyl ethers used as flame retardants in plastics (especially those used in electronic
devices), textiles, and paints can generate considerable amounts of polybrominated
dibenzo-p-dioxins (BDDs) and dibenzofurans (BDFs) (Watanabe and Tatsukawa, 1987;
Thoma and Hutzinger, 1989; Luijk et al., 1992). Watanabe and Tatsukawa (1987)
observed the formation of BDFs from the photolysis of decabromobiphenyl ether.
) ' • '• '' , :'
5-18 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Approximately 20 percent of the decabromobiphenyl ether were converted to BDFs in
samples that were irradiated with ultraviolet light for 16 hours. ,
Thoma and Hutzinger (1989) observed the formation of BDFs during combustion
experiments with polybutylene-terephthalate polymers containing 9 to 11 percent
decabromodiphenyl ether. Maximum formation of BDFs occurred at 400 to 600°C, with a
BDF yield of 16 percent. Although Thoma and Hutzinger (1989} did not provide specific
quantitative results for similar experiments conducted with octabromodiphenyl ether and
1,2-bis(tri-bromophenoxy)ethane, they did report that BDDs and BDFs were formed.
Luijk et al.(1992) studied the formation of BDD/BDFs during the compounding/
extrusion of decabromodiphenyl ether into high-impact polystyrene polymer at 275°C.
HpBDF and OBDF were formed during repeated extrusion cycles, and the yield of BDFs
increased as a.function of the number of extrusion cycles. HpBDF increased from 1.5 to
9 ppm (in the polymer matrix), and OBDF increased from 4.5 to 45 ppm after four extrusion
cycles.
Insufficient data are available at this time upon which to derive annual BDD/BDF
emission estimates from this source.
5.6. CARBON REACTIVATION FURNACES
Granular activated carbon (GAC) is an adsorbent that is widely used to remove
organic pollutants from wastewater and in the treatment of finished drinking water at water
treatment plants. Activated carbon is manufactured from the heat treatment of nut shells
and coal under pyrolytic conditions (Buonicore, 1992a). The properties of GAG make it -
ideal for adsorbing and controlling, vaporous organic and inorganic chemicals entrained in
combustion plasmas, as well as soluble organic, contaminants in industrial effluents and
drinking water. The high ratio of surface area to particle weight (e.g., 600 - 1600 m2/g),
combined with the extremely small pore diameter of the particles (e.g., 15-25 Angstroms)
increases the adsorption characteristics (Buonicore, 1992a). GAC will eventually become
saturated, and the adsorption properties will significantly degrade. When saturation occurs,
GAC usually must be replaced and discarded, which significantly increases the costs of
pollution control. The introduction of carbon reactivation furnace technology in the rnid-
1980s created a method involving the thermal treatment of used GAC to thermolytically
desorb the synthetic compounds and restore,the adsorption properties for reuse (Lykins et
5-19 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
a)., 1987). Large-scale regeneration operations, such as those used in industrial water
^ ' . i.
treatment operations, typically utilize multiple-hearth furnaces. For smaller-scale
operations, such as those used in municipal water treatment operations, fluidized-bed and
infrared furnaces are used. Emissions are typically controlled by afterburners followed by
water scrubbers {U.S. EPA, 1995c; 1997b).-
The used GAC can contain compounds that are precursors to the formation of
CDD/CDFs during the thermal treatment process. EPA measured precursor compounds in
spent GAC used as a feed material to a carbon reactivation furnace tested during the
National Dioxin Study (U.S. EPA, 1987a). The total chlprobenzene content of the GAC
ranged from 150 to 6,630 ppb. Trichlorobenzene was the most prevalent species present,
with smaller quantities of di- and tetra-chlorobenzenes detected, total halogenated
organics were measured to be about 150 ppm.
EPA has stack tested two GAC reactivation furnaces for the emission of dioxin (U.S.
EPA, 1987a; Lykins et al., 1987). One facility was an industrial carbon reactivation plant,
. • : " -, ' •'•;. ' ; • ," • ' ' , : ;•;' " ,: *. ...1 „ I • ' • . ; i , ' • .
and the second facility was used to restqre GAC at a municipal drinking water plant. U.S.
EPA (1995c; 1997b) reported results of testing performed at a county water facility in
California during 1990.
The industrial carbon regeneration plant processed 36,000 kg/day of spent GAC
used in the treatment of industrial wastewater effluents. Spent carbon was reactivated in
a multiple-hearth furnace, cooled in a water quench, and stored and shipped back to
primary chemical manufacturing facilities for reuse. The furnace fired natural gas, and
consisted of seven hearths arranged vertically in series. The hearth temperatures ranged
from 480 to 1,000°C. Air pollutant emissions were controlled by an afterburner, a sodium
spray cooler, and a fabric filter. Te.mperatures in the afterburner were about 930°C. From
I, ' 1, , ' ' , • | , • , „ ' • i' '• | .!.",•"' , , ' ,i
the results of this testing, a TEQ emission factor of 2.98 ng TEQ/kg carbon processed can
"' ' ' ,''t ' ", >'; " ' '.'. • ' ' * H.'.1 ' ' I,V' , "' ;. > : • ', '
be derived. The emission factor for total CDD/CDF was 58.6 ng/kg.
The second GAC reactivation facility tested by EPA consisted of a fluidized-bed
furnace located at a municipal drinking water treatment plant (Lykins et al., 1987). The
furnace was divided into three sections: a combustion chamber, a reactivation section, and
a dryer section. The combustion section was fired by natural gas, and consisted of a
sfoichiometrically balanced stream of fuel and oxygen. Combustion temperatures were
about 1,038°C. Off-gasses from the reactivation/combustion section were directed
,1, ' . " •'• ; ';:V" ' ' ';; -':
in"! L i ; ' i' » ' ' ' ,i ,iiij « ; "
5-20 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
through an acid gas scrubber and high-temperature afterburner prior to discharge from a
stack. Although measurable concentrations of dioxin-like compounds were detected in the
stack emissions, measurements of the individual CDD/CDF congeners were not performed;
therefore, it was not possible to derive TEQ emission factors for this facility. With the
afterburner operating, no CDD congeners below HpCDD were detected in the stack
emissions. Concentrations of HpCDDs and OCDD ranged from 0,001 to 0.05 ppt/v and
0.006 to 0.28 ppt/v, respectively. All CDF congener groups were detected in the stack
emissions even with the afterburner operating. Total CDFs emitted from the stack
averaged 0.023 ppt/v. . '. . : :
From the results of testing the regeneration unit at the county watervfacility reported
by U.S. EPA (1995c; 1997b), a TEQ emission factor of 1.73 ng TEQ/kg of carbon
processed can be derived. The emission factor for total CDD/tDF was 47 ng/kg. The
report did not provide the configuration and type, of furnace tested. However, the report
did state that the emissions from the furnace were controlled by an afterburner and a
scrubber. ,
The industrial GAC reaction furnace test data indicate that an average of 2.98 ng
TEQ per kg of GAG may be released to the air during an industrial operation. The TEQ
emission rate for the regeneration unit at the county water treatment facility was 1,73 ng
TEQ/kg carbon. "Low" confidence ratings are given to these emission factors, because
only one industrial GAC reactivation furnace in each category was stack tested.
The mass of GAC. that is reactivated annually in carbon reactivation furnaces is not
known. However, a rough estimate, to which a "low" confidence rating is assigned, is the
mass of virgin GAC shipped each year by GAC manufacturers. According to U.S. DOC
0 990c), 48,000 metric tons of GAC were shipped in 1987. Data for 1995 are not yet
available for GAC shipments from U.S. DOC (1996). However, U.S. EPA (1995c; 1997b)
reports water and wastewater treatment operations consumed 65,000 metric tons of GAC
in 1990. An estimated 50 percent of this volume Were used for industrial uses, and 50
percent were used for municipal uses. Industrial facilities potentially regenerated 24,000
metric tons and 32,500 metric tons of GAC in 1987 and 1990, respectively. In 1 987 and
1990 municipal facilities potentially regenerated 24,000 metric tons and 32,500 metric
tons, respectively.
5-21 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Applying the TEQ emission factor of 2.98 ng TEQ/kg of reactivated carbon to the
estimates of potential GAC reactivation volume by industrial facilities yields annual release
estimates of 0.072 g TEQ in 1987 and 0.097 g TEQ in 1990. Using the TEQ emission
factor of 1.73 ng/kg of reactivated carbon yields estimated annual emissions by municipal
facilities of 0.042 g TEQ in 1987 and 0.056 g TEQ in 1990. Based on the "low"
confidence ratings assigned to the activity level and emission factors, the estimated range
of potential annual emissions is assumed to vary by a factor of 10 between the low and
high ends of the range. Assuming that the total releases estimated for 1990 (i.e., 0.15 g
TEQ) and for 1987 (i.e., 0.11 g TEQ) are the geometric means of the ranges for those 2
years, the ranges are calculated to be 0.05 to 0.47 g TEQ in 1 990 and 0.03 to 0.34 g TEQ
in 1987.
'.' . • .: ' ' . . ' ' . ' . r • . , • ••
'. • ;•;;. •'.' .';:'<'.• • • '':i': •': '.'•..•• •'•''.? K • '
5.,7. KRAFT BLACK LIQUOR RECOVERY BOILERS
Kraft black liquor recovery boilers are associated with the production of pulp in
making of paper using the Kraft process. In this process, wood chips are cooked in large •
vertical vessels called digesters at elevated temperatures and pressures in an aqueous
solution of sodium hydroxide and sodium sulfide (Someshwar and Pinkerton, 1992). Wood
is broken down into two phases: a soluble phase containing primarily lignin, and an
insoluble phase containing the pulp. The spent liquor (called black liquor) from the digester
contains sodium sulfate and sodium sulfide that the industry finds beneficial in recovering
for reuse in the Kraft process. In the recovery of black liquor chemicals, weak black: liquor
is first concentrated in multiple-effect evaporators to about 65 percent solids. The
concentrated black liquor also contains 0.5 to 4 percent chlorides by weight (U.S. EPA,
1987a). Recovery of beneficial chemicals is accomplished through combustion in a Kraft
black liquor recovery furnace. The concentrated black liquor is sprayed into a furnace
equipped with a heat recovery boiler. The bulk of the inorganic molten smelt that forms in
the bottom of the furnace contains sodium carbonate and sodium sulfide in a ratio of about
3:1 (Someshwar and Pinkerton, 1992). The combustion gas is usually passed through an
electrostatic precipitator that collects paniculate matter prior to" being vented out the stack.
The particulate matter can be processed to further recover and recycle sodium sulfate.
In 1987, the U.S. EPA stack tested three Kraft black liquor recovery boilers for the
emission of dioxin in conjunction with the National Dioxin Study (U.S. EPA, 1987a). The
5-22 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
three sites tested by EPA were judged to be typical of Kraft black liquor recovery boilers at
that time. Dry bottom ESPs controlled emissions from two of the boilers; a wet bottom
ESP controlled emissions from the third. The results of these tests include congener group
concentrations but lack measurement results for specific congeners other than 2,3,7,8-
TCDD and 2,3,7,8-TCDF. NCASI (1995) provided congener-specific emission test results
for six additional boilers tested during the 1990 to 1993 time period. Three boilers were of
the direct contact type, and three were noncontact type. All were equipped with ESPs.
The average congener and congener group emission factors are presented in Table 5-5 for
the three facilities from U.S. EPA (1987a) and the six facilities from NCASI (1995). Figure
5-6 presents the average congener and congener group profiles based on the test results
presented in NCASI (1995).
The average TEQ emission factor based on the data for the six NCASI facilities with
complete congener data is 0.028 ng TEQ/kg of black liquor solids, assuming nondetected
values are zero and 0.068 ng TEQ/kg and are present at one-half the detection limit. The
results for the three .facilities reported in U.S. EPA (1987a) were not used in the derivation
of the TEQ emission factor, because congener-specific measurements for most 2,3,7,8-
substituted congeners were not made in the study. A "medium" confidence rating is
assigned to these emission factors, because the emission factors were derived from the
stack,testing of six Kraft black liquor recovery boilers that were judged to be fairly
representative of technologies used at Kraft pulp mills in the United States.
The amounts of black liquor solids burned in Kraft black liquor recovery boilers in the
United States during 1987 and 1995 were 69.8-million metric tons and 80.8-million metric
tons, respectively (American Paper Institute, 1992; American Forest & Paper Association,
1997). These activity level estimates are assigned a confidence rating of "high," because
they are based on recent industry survey data. Combining the emission factor of 0.028 ng
TEQ/kg of solids combusted with the activity level estimates of 69.8- and 80.8-mHlion
metric tons in 1987 and 1995, respectively, indicates that annual emissions from this
source were approximately 2.0 grams in 1 987 and 2.3 grams in 1995. Based on the
confidence ratings assigned to the emission factor and activity level estimates, the
estimated range of potential annual emissions is assumed to vary by a factor of five
between the low and high ends of the range. Assuming that the best estimate of annual
-TEQ emissions in 1987 (2.0 g TEQ/yr) is the geometric mean of this range, then the range
5-23 ' April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
IS calculated to be 0.9 to 4.5 g TEQ/yr. For 1995, the range is calculated to be 1.0 to 5.0
gTEQ/yr.
B.8. OTHER IDENTIFIED SOURCES
Several manufacturing processes are identified as potential sources of CDD/CDF
formation, because the processes use chlorine-containing components and/or involve
application of high temperatures. However, no testing of emissions from these processes
has been performed in the United States, and only minimal emission rate information has
been reported for these processes in other countries.
Burning of Candles - Schwind et al. (1995) analyzed the wicks and waxes of
uncolored candles, as well as the fumes of burning candles, for CDD/CDF, total
"" ,i!!' ' | : , ''''". ' '!' ' ' ' ' ' „ ''• ' '»[•,' ' '
chlorophenol, and total chlorobenzene content. The results are presented in Table 5-6. As
shown in Table 5-6, beeswax contained the highest levels of CDD/CDF and total
chlorophenols. In contrast, the concentration of total chlorobenzenes in stearin wax was a
factor of 2 to 3 times higher than in paraffin or beeswax. The concentrations of the three
analyte groups were significantly lower in the wicks than jn the waxes. Emissions of
CDD/CDF from all three types of candles were very low during burning. In fact, comparison
of the emission factor to the original CDD/CDF concentration in the wax indicates a net
destruction of the CDD/CDF originally presented in the wax.
' •''' '!'iii • ' ' • . ' • • j,1 " • • : :, ' , •
Information is not readily available on the volume of candles consumed annually in
the United States. However, the value of U.S. candle wholesale shipments in 199.2 was
"II' I" . , ' .• ' ' ' , » i !•,.,( , , | ,
nearly $360 million (U.S. DOC, 1996). Assuming that average wholesale cost per kg of
candle is $1, then the volume of candles shipped was 360-million kg. If it is further
assumed that 75 percent of the candle volume are actually burned and that the CDD/CDF
emissions rate is 0.015 ng/kg, then a rough "what if" estimate of the annual emission from
combustion of candles is 4 mg TEQ/yr.
Glass Manufacturing - Bremmer et al. (1994) and Douben et al. (1995) estimated
annual emissions of less that 1 gram TEQ/yr from glass manufacturing facilities in The
Netherlands and the United Kingdom, respectively. Glass is manufactured by heating to a
temperature of 1,400 to 1,650°C a mixture of sand and, depending on the type of glass,
1 , 'V ' " • '•'•'•"• ,,!'..•• . • . • ' • •!,' . • : ,?,:.;,.'.-:''
lime, sodium carbonate, dolomite, clay, or feldspar. In addition, various coloring and
clarifying agents may be added. Chlorine enters the process as a contaminant (i.e., NaCI)
5-24 , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
in sodium carbonate (Bremmer et al. 1994). However, the emission factors used by
Bremmer et al. (1994) and Douben et al. (1995) were not reported. Umweltbundesamt
(1996) reported relatively low emission factors (approximately 0.002 and 0.007 ng TEQ/kg)
for two glass manufacturing facilities in Germany.
Lime.Kilns - Annual emissions from lime kilns in Belgium and the United Kingdom
have been reported by Wevers and DeFre (1995) and Douben et al. (1995), respectively.
However, the emission factors used to generate these estimates were not provided.
Umweltbundesamt (1996) reported low emissions (0.016 to 0.028 ng TEQ/kg) during tests
at two lime kilns in Germany.'
Ceramics and Rubber Manufacturers - Similarly, Douben et al. (1995) estimated
annual emissions from ceramic manufacturers and rubber manufacturers in the United
Kingdom. Lexen et al. (1993) had previously detected high concentrations of CDD/CDF in
emissions from a ceramic manufacturer in Sweden, which occasionally glazed ceramics by
volatilization of sodium chloride in a coal-fired oven. Lexen et al. (1993) also detected high
'.•'.,•'• • ' • >
pg/L levels of TEQ in the scrubber ;water from the vulcanization process at a Swedish
rubber manufacturer.
5-25 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 5-1. CDD/CDF Emission Factors for Cement Kilns
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 TEQ (nondetects - 0)
Total TEQ {nondetects = 1/2 DU
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF (nondetects = 0)
Total CDD/CDF (nondetects = 1/2 DL)
Kilns Burning Hazardous Waste
Mean Emission Factor
(12 facilities)
(ng/kg clinker produced)
Nondetects
Set to 1/2
Det. Limit
1.22
3.68
3.90
4.54
6.37
14.58
4.35
18.17
10.96
27.38
16.97
7.22
1.46
10.52
6.68
1.44
1.02
24.45
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
* 1,443
Nondetects
Set to
Zero
1.21
3.67
3.89
4.54
6.36
14.58
4.34
18.17
10.87
27.26
16.84
7.18
1.43
10.45
6.68
1.42
1.00
24.34
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
21,443
Kilns Not Burning Hazardous Waste-
Mean Emission Factor
(11 facilities)
(ng/kg clinker produced)
Nondetects
Set to 1/2
Det. Limit
0.020
0.050
0.044
0.058
0.067
0.471
0.751
0.793
0.118
0.253
0.211
0.067
0.021
0.094
0.168
0.022
0.281
0.32
2.14
2.26
6.50
0.92
0.75
7.22
2.13
0.64
0.27
0.28
23.11
Nondetects
. Set to
Zero
0.013
0.038
0.031
0.045
0.053
0.466
0.751
0.792
0.108
0.243
0.202
0.058
0.007
0.089
0.159
0.006
0.255
0.29
2.14
2.26
6.50
0.92
0.75
7.22
2.13
0.64
0.26
0.26
23.08
NR « Not reported
Source: U.S. EPA (1996c)
5-26
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
,0 _ 0.005 0.07 6.015 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
Nondetects set equal to zero.
Figure 5-1. Congener Profile for Air Emissions from Cement Kilns Burning Hazardous Waste
5-27 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener group emission factor / total CDD/CDF emission factor)
0.05 0.1 0.15 . 0.2 0.25 0.3
0.35
Nondetects set equal to zero.
Ratio (congener emission factor / total CDD/CDF emission factor)
0.01 0.02 0.03
0.04
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
l,2.3.4.6.7,8-SipCDt>
1,2,3,4,6, 7,8.9-OCDD
2,3.7,8-CDF
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 5-2. Congener and Congener Group Profiles for Air Emissions
from Cement Kilns Not Burning Hazardous VVaste
5-28
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 5-2. 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-HxGDD
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
Cigarette .
(pg/g)
ND(0.5)
ND(0.5)
' 2.01
a
a
1,343
257
~
'
:
—
,
•
—
, ' —
i
1 ,602
.
13.88
44.9
ND{0.5)
13.41
1,629
257
-
.. "
—
- - •
1,944
Concentrations
Mainstream smoke
-------
DRAFT-DO NOT QUOTE OR CITE
'CDDconc,
1
8
1
1
o
u
/./
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
// '"'"- 'JV. Miiy Mn..i. i i\ frM"::::"i/! fJ"ii',~"'-j'.'!."f--^:
/ft i-~r-T,.. • V *j ..,....,
.^•••^^^Mir ^tgrflriT'''!!'-''!" f'Hm JXIHrKZHZWS:!:*:'®
^^————/) /t-tij ^. jfS,lSjS7 £Vi7*.:., •.:-,.>.',.ny
TCDJD PeCDD
^H Cigarettes (row 1)
^B Ash (row 3)
HxCDD HpCDD OCDD
HH Mainstream Smoke (row 2)
Figure 5-3. CDD Profiles for Japanese Cigarettes, Smoke, and Ash
5-30
April \ 998
-------
W
H
O
Q
Q
CD
O
CO
CD
S
co
CO
0
._
CO
.0
'35
LLJ
LL
O
O
O
0
O
co
in
CD
JD
CO
J—
• *.
.5?
^i>
•S:
'm
CD
ffl
CD
co
CO
b
i:
CO
o
4-»
•o
8
"5
£
S
z
* :i'
CO
.2
*3
s.
g'
o
c
o
"C
1 C
c
• Li
.£
^ <
. C
**- (
CC c
C
-
*-
.^
-
11
'"if
a:"® £
co»
T-2
=Sl
CO
IE
Oj= E
Sis
g w
,_'cB
"co
c_
31
-£
^
v
I"®
2.*
5 g
; E
3 CO
E*
> co
i te
J.«
] c
!"co
Q.
O
o
>-
CD
C
CD
CD
C
Q
O
l_
Q)
c
CD
CD
C
0
O
r>- CN CD o in CM oo
o co «- to in pj JJQ
00000"- co
S in o •* in in «-
QodddccicM
i .
coco
<-> C> CD IO Tj-
d d o o o m. t
00000*"°?
•Z.-Z.
^^
*$•'
OtO^
^.oqtoco.CN!coinc^ 9 Q
^dd^^ddcM m'«-
<3--d- OO^T-O
^dd^ddd®^"
co
"-•^-odooor-o^
OOOQOOOOOO
Z ;
,
: : i : j i : : : i
'
LULL
LLLLLLUL.QQ
O,Q Q Q ^^
o o x x x x • •
g^D*obobciobS-W-
H oo oo r*{ !•* oo r~"«o i>."
06 r-T rC <^ to" r-T to •* ^f
COCMCOCMCMCNCOCMCM(_)
tNr- CMi— T- »- CMr- T^ O
£«|0
in'*0'1
.
ooo
TOO),-;
mr^O)
oor> o
^-oo
p^ 1 ^f
^~ »-•
Ou.
OQ
OO
0000
coco"®
CMCMf—
co co co
ooo
£^«oo LO in 0)00^
d CM ^ CM co in to «- * »-
--
•<-r».cMcO"- coooo
d ^ CM T- CM * co in ^ °°
*~
*— ^co »— coinr»-r-
in r- m °J ^t'^j- oo co CM «—
d d d ^ °° t- d odd
. ' r
^
* /M fO
^ T3
o "i
CD C
"•§
5 u,
> 4-*
n
CO ^
i; »
s c
C -o
o -43
a. co^
£ ~
< CD
CJ
*: c
CD O
CC O
II
-------
DRAFT-DO NOT QUOTE OR CITE
1
I °-9
cS 0.8
3 0.7
o
§• 0.6
O
I °-5
ft*
0.4
"
0.2
a;
o
TCDD PeCDD HxCDD HpCDD OCDD TCDF PeCDF HxCDF HpCDF OCDF
HH Japanese Mainstream (row 1) HI German Mainstream (row 2)
Swedish Mainstream (row 3) ^H Swedish Sidestream (row 4)
Rgure 5-4. Congener Group Profiles for Mainstream and Sidestream Cigarette Smoke
5-32
April 1998
-------
B-
h—H
U
o<
O
w
-H
O
a
•E-H
g
O
Q
Q
U
U
ID
JD
o
°
5
£
ID
O)
o
c
in
c
o
iS
oncentr
u
LL.
0
r 5
**^_
O
,o
o
<*'
in
3
ID
v
O
CD
Q.
m
B
CO
.£
1
o
u
CO
0
~
ID
1
.§
CO
"O
IB
t_ •
JD
CO
C
O
'«
u:
•i«» '
Concen
>•=:
s
ID
CD
<3~
if =5
ID C
U
" , JtlL.
(0 1
p
•HV
CT
m i
"S-°
^~ T—
. •
£•*!
_ T
O c
¥i
w •*•
•a"?;
Il
c >
•• • .. '_!_ _
CO
T3
C
<0
a. co
CO
: —
"o)
°c £
~CQ f^1
. **-
C/J O
^ >
^
-
o
c
CD
CO
O \O.
P
»o
CO
CD
O
0
f
^^ ^^ ™^
T"1 CO ^^
* • • Co (o ^^t C
«y
O O CD 2? U
c*
i^"510^*
Ow^rocD^c^
-«CM ""cop;
^
^ ^T T
-coco "oo
*~CM
CM CD a, v^.%
*~ ^ to .2: oo
«" 10
0
\ o. oo oo co r** •
- oo r~ r^oo'co
oo p^ ^ co r^ ^4*
r^ co co co co co 5
co" CM" CM CM CM" CM" o
Oj "d; CM CO O
*~ *~ »— »—
£j^J3^ O0o9-Dc
^l^-0^ ° ° o^-a"
O O CO CN CO
— J2 "° Jjj ° ° Oco"°p;
*~ *~
s
f'.
: ' ' ' '
tO CM O CO m
1 .
'
^ "> °o JI 2
'
C^J js.' ,_ ffl CM C
^^f^COfqjJJo^-CN^-
*w\
o 00 r*» *— *; co 10 T- *— in
- d CN CO « TO CO " ^ °
coiriirico§5mJIf>''-c
co ""• * o ""; *"; Too in co
£J g oi CM' PJ'PJ ^ to 06 cr
^_COCO^^j^_^T-T—
~
•
<-cocNr>in.o?in.coofo
SSSSSlS^cd-
°? CO CM 0 9 T CO ^ CO LO
SJco'co'dSpjincocdd
?j CO CM ^ £] ° . ^- co to
*** ^*** ^ o oo oo ^ ^ ^* ^*
*• !D 3 ID 3
0) (0 CD CD CO
0 > > > >
| II ti II 11
00
o>
CO
a.
<
CO
CO
LO
-------
DRAFT-DO NOT QUOTE OR CITE
0.6 f-
g 0.5
8
fe.
.§ 0.4
8
8 0.3
&
I-
I 0.2
&
0.1
TCDD PeCDD HxCDD HpCDD OCDD TCDF PeCDF HxCDF HpCDF OCDF
1HH China (column 1)
\' LL Ji Germany (column 4)
Source: Matsueda etal. (1994)
Fi»-.9M Denmark (column 2)
HIIH United Kingdom (column 5)
\ Japan (column 3)
United States (column 6)
Figure 5-5. Congener Group Profiles for Cigarette Tobacco from Various Countries
5-34
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 5-5. CDD/CDF Emission Factors for Black Liquor Recovery 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 OGDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total TEQ
Total CDD/CDF
U.S. EPA (1987) - 3 Facilities
Mean Emission Factors
(ng/kg feed)
Nondetects
Set to
Zero
0
NR
NR
NR
NR
NR
4.24'
o.o4 ;
NR
NR
, NR ;'
NR
NR
NR
NR
NR '
0.35
• 0.21
0.27
0.80
2.05
4.24
0.95
0.64
1.16
1.05
0.35
NR
1 1 .71
Nondetects
Set to
1/2 Det. Limit
0.04
NR
NR
NR
NR
NR
4.24
0.06
:: NR
NR
NR
NR
NR
NR
NR
NR
0.35
0.36
0.13
1.02
2.05
4.24
1.00
0.77,
1.20
1.05
0^35
NR
12.17
NCASI 1(1995) - 6 Facilities
Mean Emission Factors
(ng/kg feed)
Nondetects
Set to
Zero
0
1 0
0.001
0.003
0.006
0.108
1 .033
0.040
0.030
0.033
0.007
0.012
0.005
0.010
0.024
0
0.040
0.106
0.013
0.104
0.252
1 .033
1 .270
0.370
0.102
0.024 -
0.040
0.028
3.314
Nondetects
Set to
1/2 Det. Limit
0.017
0.019
0.021
0.016
0.020
0.140
1.054
0.053
0.036
0.038
0.022
0.022
0.017
0.024
0.037
0.018
0.066
0.123
0.089
0.122
0.279
1.054
1.275
0.377
0.109
0.040
0.066
0.068
,3.535
Sources: U.S. EPA (T987a); NCASI (1995)
5-3.5
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
2,3,7,8-TCDD
l,2.3.7,8-Pe>6DD
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-Hp GDD
i.2,3.4,6,7,8.9-OCpD
2.3,7.8-TCpF
1.2.3,7,S-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-Hx6DF
2.3,4.6.7.B-HxCDF
1.2.3.4,6,7,8-HpCDF
l,2.3.4.7.8.S-Hf>CDF
Ratio (congener emission factor I total CDD/CDF emission factor)
0.05 0.1 0.1S 0.2 0.2S 0.3
0.35
Ratio (mean congener group emission factor / total CDD/CDF emission factor)
0.1 0.2 0.3 0.4
0.5
*: NCAS1 (JPffS};
*tt mqual to xiro.
Hgure 5-6. Congener and Congener Group Profiles for Air Emissions from Kraft Black Liquor Recovery Boilers
5-36
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 5-6. 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
CDD/CDF
(ng TEQ/kg)
0.59
1 .62
10.99
0.18
0.12
0.08
Concentration
ZChlorophenol
teg/kg)
14.8
32.3
256
1.23
0.94
0.74
ZChlorobenzenes
(/zg/kg)
130
330
120
0.67
0.34
0.35
Emission Factor
CDD/CDF
(ng TEQ/kg burnt wax)
0.015
0.027
0.004 .
. • '
Source: Schwind et al. (1995)
5-37
April 1998
-------
-------
DRAFT-DO NOT QUOTE OR CITE
6. COMBUSTION SOURCES OF CDD/CDF: MINIMALLY CONTROLLED
AND UNCONTROLLED COMBUSTION SOURCES
6.1. COMBUSTION OF LANDFILL GAS
The U.S. EPA recently promulgated emission standards/guidelines to control
emissions of landfill gas from existing and future landfills under the Glean Air Act (Federal
Register, 1996a). These regulations require the relatively largest landfills (i.e., largest on
the basis of design capacity) in the United States (approximately 312 landfills) to
periodically measure and determine their annual emission of landfill gas. Those landfills
that emit more than 50 metric tons of nonmethane organic compounds (NMOC) annually
must collect landfill gas and reduce the NMOC content by 98 weight percent through use
of a control device. EPA estimates that when implemented, these controls will reduce
NMOC annual emissions from existing landfills by 77,600 metric tons. The cost analysis
supporting this rulemaking based control device costs on open flares, because flares are
applicable to all the regulated facilities. Assuming that this mass reduction is achieved by
flares, the corresponding volume of landfill gas that will be burned is approximately
14-billion m3/yr (based on an assumed default NMOC concentration in landfill gas of 1,532
ppmv and a conversion factor of 3.545 mg/m3 of NMOC per 1 ppmv of NMOC [Federal
Register, 1993d]). EPA estimated that over 100 landfills had some form of collection
and/or control systems in place in 1991 (Federal Register, 1991b). Thus, a rough
approximation of the volume of landfill gas that is currently combusted is 4.7-biIlion m3/yr
(or 33 percent of future expected reductions). This estimate is similar to the 2.0- to
4.0-billion m3 of landfill gas that were estimated in EIA (1994) as collected and consumed
for energy recovery purposes in 1992. EIA (1992) estimated that between 0.9- and
1.8-billion m3 of landfill gas were collectedxand burned in 1990 for energy recovery
purposes.
Only one study of CDD/CDF emissions from a landfill flare was reported for a U.S.
landfill (GARB, 1990d). The TEQ emission factor calculated from the results of this study
is approximately 2.4 ng TEQ/m3 of landfill gas combusted. The congener-specific results of
this study are presented in Table 6-1. Figure 6-1 presents the CDD/CDF congener emission
profile based on these emission factors. Bremmer et al. (1994) reported a lower emission
factor, 0.4 ng TEQ/m3, from the incineration of untreated landfill gas in a flare at a facility
located in The Netherlands. No congener-specific emission factors were provided in
6-1 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Bremmer et si, (1994). The average TEQ emission factor for the GARB (1990d) and
Bremmer et al. (1994) studies is 1.4 ng TEQ/m3 of landfill gas combusted.
Umweltbundesamt (1996) reported even lower TEQ emission factors for landfill gas burned
in engines or boiler mufflers rather than in a flare. The reported results for 30 engines and
mufflers tested in Germany ranged from 6.001 to 0.28 ng f EQ/m3 with most values below
0.1 ng TEQ/m3. However, Bremmer et al. (1994) also reported an emission factor of 0.5
ng TEQ/m3 from a landfill-gas fired engine in The Netherlands.
The limited emission factor data available were thus judged inadequate for
developing national emission estimates that could be included in the national inventory.
However, a preliminary order of magnitude estimate of the annual TEQ release from this
source category can be obtained using the estimated volume of combusted gas and the
available emission factors. Combining the estimate of current landfill gas volume that is
combusted (4.7 billion m3/yr) with the emission factor of 1.4 ng TEQ/m3 of flare-
combusted gas yields an annual emission estimates of 6.6 g TEQ, which, when rounded to
,"'|L " • ' • ' »' r ',,'' '"• ! ' , " • , ,'•,','.' 1Ji'i , ' I i
the nearest order of magnitude to emphasize the uncertainty in this estimate, results in a
value of 10 g TEQ/yr. This estimate should be regarded as a preliminary indication of
possible emissions from this source category; further testing is needed to confirm the true
magnitude of these emissions.
'; • '• • ' " ' ' l"'1 ' '
6.2. ACCIDENTAL FIRES
Accidental fires occurring in buildings and vehicles are uncontrolled combustion
processes that typically result in relatively high emissions of incomplete combustion
. . . • ••:» i • :. , •. ,;• i' •' ' . ": !; ' ;"; •;]•..•
products because of poor combustion conditions (Bremmer et al., 1994). The incomplete
I |i ' .' i '• ', i -.', •, '.'.' '•'' ''.'"•,'. '• '!' . ' - :, ' '• ' ! '''i'(..'> '„ j '
combustion products can include CDDs and CDFs. Polyvinyl Chloride (PVC) building
, .'• Ill ' " '' ,' '__ • ! i', ,, '• I '. . •:' , '" . I ! , I ' ' ' I
materials and furnishings, chloroparaffin-containing textiles and paints, and other
''ij .' , :..'' i.. , •"."• '" : '• •',; .' ,' . : ' ", :'.:,' ' , i '*.',' ' ,
chlorinated organic compound-containing materials appear to be the primary sources of the
chlorine (Rotard, 1993). Although the results of several studies demonstrate the presence
of CDD/CDF concentrations in soot deposits and residual ashes from such fires, few direct
measurements of CDD/CDFs in the fumes/smoke of fires have been attempted. The results
of several of these studies are described below, followed by an evaluation of the available
data.
6-2 . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
6.2.1. Soot/Ash Studies
, Christmann et at. (1989b) analyzed the soot formed during combustion and pyrolysis
of pure PVC and PVC cable sheathings in simple laboratory experiments designed to mimic
the conditions of fires. For the combustion experiments, 2 grams of a PVC sample were
incinerated with a laboratory gas burner. The combustion products were collected on the
inner walls of a cooled gas funnel placed above the sample. For the pyrolysis experiments,
about 50 mg of the sample were placed in a quartz tutye and heated to about 950°C for 10
minutes in either an air atmosphere or a nitrogen atmosphere. The combustion experiments
yielded CDD/CDF concentrations in soot of 110 /^g TEQ/kg for a low molecular weight PVC,
450 /^g TEQ/kg for a high molecular weight PVC, and 270 //g TEQ/kg of PVC cable. The
pyrolysis experiments in the air atmosphere yielded lower CDD/CDF concentrations in soot:
24.4 IIQ TEQ/kg for a low molecular weight PVC, 18.7 //g TEQ/kg for a high molecular
weight PVC, and up to 41 //g TEQ/kg for PVC cable. In general, CDFs were predominantly
formed over CDDs. The lower chlorinated CDF congeners were dominant in the
combustion experiments; however, the HpCDF and OCDF congeners were dominant in the
pyrolysis experiments. No CDD/CDFs were detected in pyrolysis experiments under a
' "• .
nitrogen atmosphere. Also, no CDD/CDFs were detected when chlorine-free polyethylene
samples were subjected to the same combustion and pyrolysis conditions.
Deutsch and Goldfarb (1988) reported finding CDD/CDF concentrations ranging from
0.04 to 6.6 yug/kg in soot samples collected after a 1986 fire in a State University of New
York lecture hall. The fire consumed or melted plastic furnishings, cleaning products
containing chlorine, wood, and paper.
Funcke et al. (1988) (as reported in Bremmer et al., 1994 and Retard, 1993)
analyzed 200 ash and soot samples from sites of accidental fires in which PVC was . ,
involved. CDD/CDFs were detected in more than 90 percent of the samples at
concentrations in the ng TEQ/kg to //g TEQ/kg range. Fires involving the combustion of
materials containing relatively large amounts of PVC and other chlorinated organic
substances resulted in the highest levels of CDD/CDFs with CDD/CDF concentrations
ranging from 0.2 to 110 A*g TEQ/kg of residue.
Thiesen et al. (1989) analyzed residues from surfaces of PVC-containing materials
that were partially burned during accidental fires at sites in Germany that manufactured or
stored plastics. CDD/CDF concentrations in residues were reported as 0.5 /^g TEQ/kg for
i •' . "
6-3 , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
, i, ' , ' , ' ', lr "', '"','' V '' ' •' "• ' ' ' '
soft PVC, 4.6 /zg TEQ/kg for PVC fibers, and 28.3 /^g TEQ/kg for a hard PVC. The ratio of
total CDFs to total CDDs in the three samples ranged from 4 to 7. The dominant 2,3,7,8-
substituted CDF and CDD congeners in all three samples were 1,2,3,4,6,7,8-HpCDF and
1,2,3,4,6,7,8-HpCDD.
Following an accidental fire at a Swedish carpet factory in 1987, 200 metric tons of
PVC and 500 metric tons of PVC-containing carpet burned. Marklund et al. (1989)
analyzed snow samples within 1,500 meters downwind from the fire site and found
CDD/CDF concentrations in the top 2 cm ranging from 0.32 jug TEQ/m2 at 10 meters from
the site to 0.01 #g TEQ/m2 at 1,500 meters downwind of the site. Because of an
atmospheric inversion and very light wind at the time of the fire, the smoke from the fire
1 ' ' I • ;' ,' • . i . . . i , • • •• . .,i ' • I'
1 " ' '' '"'' :i ' ' '' • '' piii .''!,'
remained close to the ground. The soot deposited onto the snow was thus assumed to be
representative of the soot generated and released from the fire. Wipe samples of soot from
interior posts of the plant (5 and 20 meters from the fire) contained EADON TEQ
concentrations of 0.18 and 0.05 ^g/m2. On the basis of these deposition measurements,
Marklund et al. (1989) estimated the total CDD/CDF emission from the fire to be less than
3 mg TEQ.
Carroll (1996) estimated a soot-associated CDD/CDF emission factor (i.e., does not
include volatile emissions) of 28 to 138 ng TEQ/kg of PVC burned for this fire using the
following assumptions: (1) the PVC carpet backing was one-half the weight of the carpet;
(2) the carpet backing contained 30 percent by weight PVC resin; and (3) 20 to 100
percent of the PVC and PVC carpet backing present in the warehouse actually burned.
Carroll (1996) also estimated a similar soot-associated emission factor (48 to 240 ng
TEQ/kg of PVC burned) for a fire at a plastics recycling facility in Lengerich, Germany.
Carroll (1996) used the results of wipe samples collected at downwind distances of up to
6,300 meters from the fire to estimate the emission factor.
Fiedler et al. (1993) presented a case study of CDD/CDF contamination and
associated remedial actions taken at a kindergarten in Germany following a fire, which
destroyed parts of the roof, windows, and furnishings. Spot collected from the building
contained CDD/CDFs at a concentration of 45 yug TEQ/kg (or 15 //g TEQ/m2). Fiedler et al.
(1993) attributed the CDD/CDFs detected to the combustion of plastic and wooden toys,
' Mi! • ' ''? i"; ','' ' ' ,'', :' :'i;1 '' , "'' :'.'''1' V"' "''? " '• .' : '•••
floors, and furnishings; however, no information was provided on the quantities of these
materials that burned.
6-4 April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
Wichmann et al. (1993; 1995) measured the CDD/CDF content of ash/debris and
deposited surface residues that resulted from experimental test burns of two cars (a 1974
Ford Taurus and a 1988 Renault Espace), one subway car, and one railway coach in a
tunnel in Germany. Based on the measurements obtained from sampled ash/debris and
from soot collectors placed at regular spacing up to 420 meters downwind of the burn site,
the total amounts of CDD/CDF in the ash/debris and tunnel surface residues from each
vehicle burn experiment were estimated to be: 1974 model car - 0.044 mg TEQ; 1988
model car - 0.052 mg TEQ; subway car - 2.6 mg TEQ; and railway coach - 10.3 mg TEQ.
Of these total amounts of TEQ, 73 to 89 percent were accounted for by the tunnel surface
residues and 11 to 27 percent by ash/debris. The average CDD/CDF content of the
ash/debris from each experimental burn was as follows: new car - 0.14 /zg TEQ/kg; old car
-0.30 /j.g TEQ/kg; subway car - 3.1 //g TEQ/kg; and railway coach - 5.1 tig TEQ/kg.
6.2.2. Fume/Smoke Studies
Merk et a). (1995) collected fume/smoke generated during the burning of 400 kg of
wood and 40 kg of PVC in a closed building (4,500 m3 volume) over a 45-minute time
period. The sampling device .consisted of dual glass fiber filters to collect particles greater
than 0.5 jum, followed by a polyurethane foam filter to collect vapor phase CDD/CDFs. The
i
particulates and gas. phase showed the same congener pattern, decreasing concentration
with increasing degree of chlorination, thus indicating no preferential sorption of higher
chlorinated congeners to smoke particulates. However, the CDD/CDF found in the gas
phase (about 5 ng TEQ/m3) accounted for more than 90 percent of the detected
CDD/CDFs. Merk et al. (1995) also reported that the soot deposited from this fire resulted
in surface contamination of 0.050 //g TEQ/m2.
Dyke and Coleman (1995) reported a four-fold increase in CDD/CDF TEQ
concentrations in the ambient air during "bonfire" night in Oxford, England. Bonfire night
(November 5) is an annual event in England during which it is customary to set off
fireworks and have bonfires to commemorate a failed plot.to overthrow the king in 1605.
Air concentrations before and after bonfire night ranged from 0.15 to 0.17 pg TEQ/m3.
The air concentration during the bonfire night was 0.65 pg TEQ/m3. The dominant
congeners in all samples were the hepta- and octa- CDDs. The study was not designed to
collect data that would enable calculation of an emission rate nor to differentiate the
, 6-5 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
relative importance of the various materials combusted. However, the results do indicate
that open burning of materials likely to be combusted in accidental fires (with the exception
1 ,; « . . . . . . .
of fireworks) results in the release of CDDs and CDFs.
6.2.3. Data Evaluation
Structural Fires - The limited data avai|ab|e were judged inadequate for developing
national emission estimates that could be included in the national inventory. This
conclusion was also reached in national emission inventories developed for The Netherlands
(Bremmer et al., 1994) and the United Kingdom (UK Department of the Environment,
1995). Most cited studies involved situations (i.e., field and laboratory) where relatively
high loadings of PVC or plastics were combusted. The effects of different mixes of
combusted materials, oxygen supplies, building configurations, durations of burn, etc. likely
to be found in accidental fires cannot be accounted for by the factors that can be derived
from these studies. Also, most of these studies addressed only soot and/or ash residues
• "J "' .. ; - •'• '• '' ••'•.•". •' "".'';•'' .;•;,:•: ,•' i :"'- ?/" ' " ! ••' : • . . •• ' : •, '
and did not address potential volatile emissions of CDD/CDFs which, according to Merk et
a|. (1995), may represent 90 percent of the CDD/CDFs generated during burning of PVC.
" : ..•!•, ., \ .. :': ', i ;i '• ':;' :, M .- ' ;•,[••:;, ;<;"! ;: '„,! v • j • J ,
Two recent reports (Carroll, 1996; Thomas and Spiro, 1995) attempted to quantify
CDD/CDF emissions from U.S. structural fires, and Lorenz et al. (1996) estimated emissions
,; ' ':il; • . • ':'' V, .•!' . .,,•:: :.:•',,;; $• 'v-'f'-' .:••"•
from structural fires in the Federal Republic of Germany. The estimates derived in these
three studies are presented below, following a brief summary of the number of accidental
fires reported annually in the United States.
In 1995, approximately 574,000 structural fires were reported in the United States
(U.S. DOC, 1997). Of these, 426,000 were reported for residential structures, which
consist of 320,000 fires in 1 -2 family units, 94,000 fires in apartments, and 12,000 fires in
"I .."I . • • '. " , • . ! "" ." • . • .' i '. I •'• • I
"other" residential settings. The remaining 148,000 structural fires consist of 15,000 -
public assembly; 9,000 - educational; 9,000 - institutional; 29,000 - stores and offices;
29,000 - special structures; 39,000 - storage; and 18,000 - industry, utility, and defense.
' • ' i£i ' ' •', '' ; ' ' ' '•' ' , ' ' . I ''! ; •" I; ''";''" "" "r';M .'•'! '. ' [
The latter two categories may be under reported as some, incidents were handled by private
fire brigades or fixed suppression systems, which do not report (U.S. DOC, 1997).
Carroll (1996) estimated the total CDD/CDF content of soot and ash generated from
the 358,000 fires reported in U.S. DOC (I995a) for 1993 in 1-2 family unit residential
structural fires. The estimated soot/ash content ranged from 0.47 to 22.8 g TEQ with
6-6 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
0.07 to 8.6 g TEQ in soot and 0.4 to 14.2 g TEG. in ash. Carroll {1996} then developed
detailed estimates of the PVC content of typical homes (including plumbing, wiring, siding
and windows, wallpaper, blinds and shades, and upholstery), and, using statistical data on
fire loss (i.e., dollar value), the typical loss per recorded fire (9.5 percent) was assumed to
represent the typical percentage of PVC present that is burned. Extrapolating to all
358,000 1-2 family unit fires yielded an annual mass of PVC burned of 2,470 metric tons.
Carroll (1996) then developed TEQ emission factors from the results of Thiesen et al.
(1989) and Marklund et al. (1989) using a soot emission factor (i.e., grams of soot
produced per gram of PVC combusted) derived by Carroll (1996) based on assumptions
regarding the surface area of the soot collection funnel used by Marklund et al. (1989) and
the soot deposition rate on that funnel. These TEQ emission factors were then applied by
Carroll (1996) to the estimated 2,470 metric tons of PVC burned annually in 1-2 family unit
residential fires to obtain estimates of the annual mass of TEQ that would be found in the
soot and ash of residential fires (I.e.,.0.48 to 22.8 g TEQ/yr). If the conclusion of Merk et
al. (1995) that 90 percent of the' CDD/CDFs formed in fires are in the gaseous phase rather
than paniculate phase (i.e., greater than 0.5 //m diameter) is assumed, to be correct, then
the volatile CDD/CDF emissions corresponding to the range of soot/ash emissions estimated
by Carroll (1996) total 4.3 to 205 g TEQ/yr. There is very low confidence in these
estimated emissions because of the numerous assumptions employed in their derivation.
Thomas and Spiro (1995) estimated that 20 g of TEQ may be released annually to
air from structural fires. This estimate assumed an emission factor of 4 ng TEQ/kg.of
material combusted (i.e., the emission rate for "poorly controlled" wood combustion), an
assumed material combustion factor of 6,800 kg/fire, and 688,000 structural fires/yr.
Lorenz et al. (1996) estimated annual generation of CDD/CDF TEQs in the Federal
Republic of Germany using data on the number of residential and industrial/commercial
structural fires coupled with data on CDD/CDF content in soot and ash residues remaining
after fires. The potential annual TEQ generation was estimated to be 78 to 212 grams.
Vehicle Fires - The limited data available were judged inadequate for developing
national emission estimates that could be included in the national inventory. However, a
preliminary order of magnitude estimate of the range of potential CDD/CDF emissions that
may result from vehicle fires can be estimated using'the results reported by Wichmann, et
al. (1993; 1995) for controlled vehicle fires in a tunnel (0.044 mg TEQ for an old car to 2.6
6'7 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
mg TEQ for a subway car). Although Wichmann et al. (1993; 1995) did not measure
volatile CDD/CDFs (which were reported by Merk et al. (1995), to account for the majority
of CDD/CDFs formed during a fire), the study was conducted in a tunnel, and it is likely
that a significant fraction of the volatile CDD/CDFs sorbed to tunnel and collector surfaces
arid were thus pleasured as surface residues. In 1995, approximately 406,000 vehicle fires
were reported in the United States (U.S. DOC, 1997). If it is assumed that 99 percent of
the 406,000 reported vehicle fires in 1995 involved cars and trucks (i.e., approximate
percentage of in-service cars and trucks to .total of all motor vehicles, U.S. DOC (1995a)
• i. . ',;,* "' ;' , :, , "'-i, > •• ,i;' ,i." i'v .. •• : t V; '" •, ' i. ..;• • • .
and that the applicable emission rate is 0.044 mg/TEQ per incident, then the annual TEQ
formation is 17.7 g TEQ. The emission factor of 2.6 mg TEQ/fire is assumed to be
applicable to the remaining 1 percent of vehicle fires, thus yielding an emission of 10.6 g
TEQ/yr. The total TEQ annual emission is roughly estimated to be 28.3 g TEQ/yr, which,
.when rounded to the nearest order of magnitude to emphasize the uncertainty in this
estimate, results in a value of 10 g TEQ/yr. This estimate sould be regarded as a
,'lli1 • , , '...'I1 ,11" fill'l! ' . '! „ " '.i i I! •' ' '- ! '.III,;!'1 'M ', ' , "" I ' ' ' ,'"! '- , ' , ' i!" ! ' ', I '
preliminary indication of possible emissions from this source category; further testing is
f.l ". "• " .- "i!! ' !'T ! •- •"• "' .':•.'•. ' "I," ' ••:••, '! •' '' ,'. +, . . r. a
„ , "HI,!, " i „ , i,,, , n ' ,i ,'i f ' ,, ' ! 'i '' ™i» '" ' ' " "" I
needed to confirm the true magnitude of these emissions.
' .-•' ^ . ', '•'. ' . >'•' '•'•>•'••'• '• '• '.' ' : ': ; '., • •':^..'1 >'::"•.• :
6,3. LANDFILL FIRES
1 ' ' • , *"i:!' ' • . '.'' ] •'••'•, •., - .-: ' >• / '• ' v -,; ... '''!: -'•; ,;.i'. .'' .•!'•••
In the late 1980s, two serious fires occurred in landfills near Stockholm, Sweden.
• • • • , , , 4, , 1
The first involved a fire in a large pile of refuse-derived fuel. Based on measurements of
chjorpbenzenes in the air emissions, it was estimated that 50 to 100 kg of chlorobenzenes
were released, COD/CDF emissions were estimated to be several 10s of grams based on
the assumption that the ratio of CDD/CDFs to chlorobenzenes in landfill fire emissions is
»'i , , Hi!!! , . " "|i ' ,,,'t, '. i „ • , !•,„•• , ,,;- , ,• i " , , ; ,
similar to the ratio observed in stack gases of municipal waste incinerators. In connection
with the second fire, which occurred at a large conventional landfill, birch leaves were
collected from trees close to the fire and at distances up to 2 km downwind of the fire, as
.I.;!,," „ . • jPfli' '. •.',... ! '"V.:,": „" ':, '' '' ," '.'"'.i "•'• . •' '• I' ' ''' ' ':'.'J M • ',.''. ' :« , - : '..:i" 'j ,' '
well as from nearby areas not impacted by smoke from the fire. The discharge of CDD/CDF
necessary to cause the CDD/CDF concentrations measured on the leaves was estimated to
i.1;, . "' • " ..i •, ' ' • ' i , •;> ' .!•,.• „ i, ' ' : •,: •.•' ' M:.'I«, "v.:.- ',, ." s r.., , , , . '"'
be several 10s of grams (Persson and Bergstrom, 1991).
In response to these incidents, Persson and Bergstrom (1991) measured CDD/CDF
emissions from experimental fires designed to simulate surface landfill fires and deep landfill
. .» ..'I:1;. f ' ,; i . ; .'," ' .y • „.. ./ .,, „ :' I'111."',:", .','". i, '.,w , • , ' ,*''•' , . > > •
fires. The experiments used 9-month old domestic waste. The tests showed no significant
6-8 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
-^' "• '
difference in CDD/CDF content of the fire gas produced by the simulated surface and deep
fires. The average CDD/CDF emission rate was reported to be 1 ^g Nordic TEQ/kg of
waste burned. Persson and Bergstrom (1991) and Bergstrom and Bjorner (1992) estimated
annual CDD/CDF TEQ emissions in Sweden from landfill fires to be 35 grams. The estimate
was based on the emission rate of 1 ^g Nordic TEQ/kg waste burned, an assumed average
density of landfill waste of 700 kg/m3, an assumed waste burn of 150 m3 for each surface
landfill fire (167 fires in Sweden per year), and an assumed waste burn of 500 m3 for each
deep landfill fire (50 fires in Sweden per year). The estimates of waste burn mass for each
type of fire were the average values obtained from a survey of 62 surface fires and 25
deep fires. The estimated number of fires per year was based on the results of a survey of
all Swedish municipalities for fires reported during the years 1988 and 1989. Sweden has
an estimated 400 municipal landfills (Persson and Bergstrom, 1991).
Ruokojarvi et al. (1995) measured the ambient air concentrations of CDD/CDF in the
vicinity of real and experimental landfill fires in Finland. The most abundant toxic
f
congeners were the hepta- and octa-CDDs and the penta-, hepta-, and octa-CDFs. The
highest contributions to the measured TEQ were made by 1,2,3,7,8-PeCDD and 2,3,4,7,8-
PeCDF. In Finland/annual CDD/CDF emissions from landfill fires are estimated to be 50-70
g Nordic TEQ (Aittola, 1993 - as reported by Ruokojarvi et al., 1995).
Although no U.S. monitoring studies are available, an emission factor similar to the
Swedish emission factor would be expected in the United States, because the contents of
the municipal waste are expected to be similar between the United States and Sweden.
However, because no data could be located on characterization of landfill fires in the United
States (i.e., number, type, mass of waste involved), the limited data available were judged
inadequate for developing national emission estimates that could be included in the national
inventory. However, a preliminary order of magnitude estimate of the potential magnitude
of TEQ emissions associated with landfill fires in the United States can be obtained by
assuming a direct correlation of emissions to population size for the United States and
Sweden or by assuming a direct correlation between emissions and the number of landfills
in each county. Both countries are Western, industrialized countries. Although the per
capita waste generation rate in the United States is nearly 1.5 times that of Sweden, the
composition of municipal waste and the fraction of municipal waste disposed of in landfills
in the two countries are nearly identical (U.S. EPA, 1996b). The 1995 population of
6-9
April 1998
-------
,. . . ; • • ... . •: .. .(.-'.-, , .. - . ••
. DRAFT-DO NOT QUOTE OR CITE
Sweden is 8,822,000 {U.S. DOC, 1995a). Thus, the per capita landfill fire-associated TEQ
emission factor is 4.0 ^g TEQ/person/year (i.e., 35 grams/8,822,000 people). Applying
this factor to the U.S. population (263,814,000) (US. DOC, 1995a) results in an estimated
annual emission of 1,050 g of TEQ. When rounded to the nearest order of magnitude to
emphasize the uncertainty in this estimate, the estimated annual emission is 1,000 g
TEQ/yr. This estimate should be regarded as a preliminary indication of possible emissions
from this source category; further testing is needed to confirm the true magnitude of these
emissions. An annual emission of similar size is obtained if it is assumed that the ratio of
annual TEQ emissions to number of landfills in Sweden, 87.5 mg TEQ/landfill (i.e., 35
grarns/400 landfills), is applicable to the United States, which has 3,558 landfills (U.S.
EPA, 1996b). The resulting annual emission estimate is 311 g TEQ/yr.
6.4. FOREST AND BRUSH FIRES
Because CDD/CDFs have been .{detected both in the soot from residential wood
burning (Bumb et al.; 1980; Nestrick and Larnparski, 1982 and 1983; Bacher et al., 1992),
and in the flue gases from residential wood burning (Schatowitz et al.; 1993; Vickelsoe et
al., 1993) [Section 4.2 contains details on these studies], it is reasonable to presume that
wood burned in forest and brush fires may also be a source of CDD/CDFs.
Only one study could be found that reported direct measurements of CDD/CDFs in
the emissions from forest fires. This study, by Tashiro et al. '(1990), reported detection of
total CDD/CDFs in air at levels ranging from about 15 to 400 pg/m3. The samples were
collected from fixed collectors 10m above the ground and from aircraft flying through the
smoke. Background samples collected before and after the tests indicated negligible levels
in the atmosphere. These results were presented in a preliminary report; however, no firm
conplusions were drawn about whether forest fires are a CDD/CDF source. The final report
on this study, Clement and Tashiro (1991), reported total CDD/CDF levels in the smoke of
about 20 pg/m3. The authors concluded that CDD/CDFs are emitted during forest fires but
recognized that some portion of these emissions could represent resuspension from
residues deposited on leaves rather than newly formed CDD/CDFs.
•..,j!', i '' .•:'.'& ','•. 'iii; ! v1!]1'!", ' i''i'.'iLlii'.'i'.,!':'i':'"'''j'::i :'V'1'! '':V;i 'K '""'kV; ;: '. i" '
Although not designed to directly assess whether CDD/CDFs are formed during
„ ',« ' !'.',, " „ I'.,, „• ,' ,„ ,"j,,,,j,M., •„ „',. ,;,,',,'"..„!; '!', ',, If "V Ij ,"111." •",,:,.! " i!'"., If ' .IS', i,,, , , ', ' ! *•'
brush fires, Buckland et ah (1994} measured the Cpp^CDF levels in soil samples from both
burnt and unburnt areas in national parks in New Zealand 6 weeks after large-scale brush
u'lifliil. : • ' ' •-.,,, "h,,J," ' ' ,•,'''' ' ' • , ' " ".i !''':''.' « • ' *
.'"if • ''..'. ; •• i;- :, "6-10 . , ., , t ^ ^. t , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
fires. Four 2-cm deep surface-soil cores were collected and composited from each of three
burnt and three unburnt areas. Survey results indicated that brush fires did not have a
major impact on the CDD/CDF levels in soil. The TEQ content in the three unburnt area soil
sample composites were 3.0 ng/kg, 8.7 ng/kg, and 10.0 ng/kg. The TEQ content in the
three burnt area soil sample composites were 2.2 ng/kg, 3.1 ng/kg, and 36.8 ng/kg. Total
CDD/CDF content ranged from 1,050 to 7,700 ng/kg in the unburnt area soil samples and
from 1,310 to 27,800 ng/kg in the burnt area soil samples. OCDD accounted for 94 to 97
percent of the total CDD/CDF content in all samples.
Similarly, a survey of controlled straw field burning in the United Kingdom (Walsh et
al., 1994) indicated that the straw burning did not increase CDD/CDF burden in the soil;
however, a change in congener distribution was observed. Soils from three fields were
sampled immediately before and after burning, along with ash from the fire. The mean TEQ
concentrations in the pre-burn soil, post-burn soil, and field burn ash were 1.79 ng/kg, 1.72
ng/kg, and 1.81 ng/kg, respectively. Concentrations of 2,3,7,8-TCDF were lower in the
post-burn soils than in the pre-burn soils. Conversely, the concentrations of OCDD were
\
higher in the post-burn soils indicating possible formation of OCDD during the combustion
process.
Van Oostdam and Ward (1995) reported finding no detectable levels of 2,3,7,8-
substituted CDD/CDFs in three soil samples and four ash samples following a forest fire in
British Columbia. The detection limits on a congener-specific basis (unweighted for TEQ)
ranged from 1 to 2 ng/kg. Nondetected values were also reported by Van Oostdam and
Ward (1995) for ashes at a slash and burn site; the soil contained about 0.05 ng TEQ/kg,
whereas background soil contained about 0.02 ng TEQ/kg.
The concentrations presented by Clement and Tashiro (1991) cannot accurately be
converted to an emission factor, because the corresponding rates of combustion gas
production and wood consumption are not known. As a result, three alternative
approaches were considered to develop these emission factors:
• Soot-Based Approach: This approach assumes that the level of CDD/CDFs in
chimney soot are representative of the CDD/CDFs in emissions, and estimates the
CDD/CDF emission rate as the product of the soot level and the total particulate emission
rate; This involves first assuming that the CDD/CDF levels measured by Bacher et al.
6-11 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
(1992) in chimney soot (720 ng TEQ/kg) are representative of the CDD/CDF concentrations
of particles emitted during forest fires. Second, the total paniculate generation rate must
be estimated. Ward et al. (1976) estimated the national average paniculate emission factor
for wildfires as 150 Ib/ton bipmass dry weight based primarily on data for head fires. Ward
et al. (1993) estimated the national .average paniculate emission factor for prescribed
• • " • «•:,: • , . : '. , '",i ' ". . , '": .\f i " ,. .1 •'. • • ': .[ .-. : : ',; ,,/; • ; i;" . :.
burning as 50 Ib/ton biomass dry weight. Combining the total paniculate generation rates
with the CDD/CDF levels in spot yields emission factor estimates of 54 //g of TEQ and
18 (*g of TEQ/metric ton of biomass burned in wildfires and prescribed burning,
respectively. This corresponds to a range of 54 to 18 ng TEQ/kg of biomass. This
estimate is likely to be an overestimate, because the levels of CDD/CDF measured in
chimney soot by Bacher et al. (1992) may represent accumulation/enrichment of CDD/CDFs
measured in chimney soot over time, leading to much higher levels than what is actually on
* • '
erpltted particles.
• Carbon Monoxide (CO) Approach: CO is a general indicator of the efficiency of
combustion and the emission rate of many emission products can be correlated to the CO
emission rate. The Schatowitz et al. (1993) data for emissions during natural wood burning
in open stoves suggest ah emission rate of 10 A/g tEQ/kg of CO. Combining this factor
with the CO production rate during forest fires (roughly 0.1 kg CO/kg of biomass - Ward et
al. (1993)} yields an emission factor of 1,000 ng TEQ/kg biomass. This factor appears
,' ' f
unreasonably high, because it is even higher than the soot-based factor discussed above.
Although the formation kinetics of CDD/CDF during combustion are not well understood, it
appears that CDD/CDF emissions do not correlate well with CO emissions.
,.,",, V
• Wood Stove Approach: This approach assumes that the emission factor for
, «•!:. ;;' : • , : ••:-. •• •, <•:'• •' .^r .•, " ••:• •,•<,.•.•"•• ;, ;.' : ••••: ,'.,•• •
residential wood burning (using natural wood and open door, i.e., uncontrolled draft) applies
to forest fires. As, discussed in Section 4.2.1, this approach suggests an emission factor of
'"i1 , , '!ii ,.:,|||'i „ ''i , 'I'll " I ,ir !• il ' „,','• ''• ! '. 'i ' .',""' ',! ' ii'j'lll'1''!!, '"' I I'! ', ,»'' '" in' : i !l!!i'''l"i: „' i" . I ; I ' '
about 2 ng TEQ/kg of wood burned. This value appears more reasonable than the factors
suggested by the spot and CO approaches. However, forest fire conditions differ
significantly from combustion conditions in wopd stoves. For example, forest fire
combustion does not occur in an enclosed chamber, and the biomass consumed in forest
fires is usually green anc| includes underbrush, leaves, and grass. Given these differences
'' , t
6-12 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
and the uncertainties about the formation kinetics of CDD/CDF during combustion, it is
difficult to determine whether CDD/CDF emissions would be higher or lower from forest
fires than from wood stoves. Thus, although an emission factor of 2 ng TEQ/kg appears to
be the best estimate that can be made currently, it must be considered highly uncertain;
therefore, a "low" confidence rating was assigned to this estimate.
According to the Council on Environmental Quality's 25th Annual Report (CEQ,
1997), 5-million acres of forest were lost to wildfires in 1987 and 7-million acres were lost
in 1995. Estimates of the acreage consumed annually during prescribed burnings are not
readily available for the reference years 1995 and 1997. An estimated 5.1 -million acres of
biomass were burned in 1989 during prescribed burns (Ward et al., 1993). Prescribed
burning is also known as managed or controlled burning and is used as a forest
management tool under exacting weather and fuel conditions. This value of 5.1-million
acres is assumed to be an appropriate value to use for reference years 1987 and 1995.
Combining these acreage estimates with biomass consumption rates of 9.43 metric
tons/acre in areas consumed by wildfires (Ward et al., 1976) and 7.44 metric tons/acre in
areas consumed in prescribed burns (Ward et al., 1993), indicates that 47-million metric
tons of biomass were consumed in 1987 by wildfires, 66-million metric tons of biomass
were consumed in 1995 by wildfires, and 38-million metric tons of biomass were
consumed in 1987 and in 1995 by prescribed burns. These estimates were assigned a
"medium" confidence rating, because they are based on a combination of estimates
involving historical data on acres burned but less certain estimates of biomass burned/acre.
Combining the emission factor developed using the "wood stove" approach (i.e., 2
ng TEQ/kg biomass) with the amount of biomass consumed annually in wildfires and
prescribed fires (total of 85-million metric tons in 1987 and 104-million metric tons in
1995) indicates that the TEQ emissions from this source were 170 g in 1987 and 208 g in
1995. Based on the low confidence rating given to the emission factor, the estimated
range of potential annual emissions is assumed to vary by a factor of 10 between the low
and high ends of the range. Assuming that the best estimate of emissions in 1987 (170 g
TEQ/yr) is, the geometric mean of this range, then the range is calculated to be 53.8 to 538
g TEQ/yr. The range for 1995 is calculated to be 64.5 to 645 g TEQ/yr.
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
6.5 BACKYARD TRASH BURNING
In many rural areas of the United States, disposal of residential solid waste may take
place via open backyard burning in barrels or similar home-made devices. Although no
i, • ;; f "?_ ; , .; '; ; • , \ :: _/":, : :, '„ , , L, -,_,,:;;; , ^ ',,;. , iy:;' •; °
national statistics on the prevalence of this practice have been reported, the results of a
telephone survey conducted in the early 1990s of residents in five central Illinois counties
indicate that aboyt 40 percent of the residents in a typical rural Illinois county burn
household waste (Two Rivers Region Council of Public Officials and Patrick Engineering,
1994). The survey also found that, on average, those households that burn waste dispose
of approximately 63 percent of their household waste through burning in barrels (Two
Rivers Region Council of Public Officials and Patrick Engineering, 1994).
The low combustion temperatures and oxygen-starved conditions associated with
these devices may result in incomplete combustion and increased pollutant emissions
{Lemieux, 1997). EPA's Control Technology Center, in cooperation with the New York
State Departments of Health (NYSDOH) and Environmental Conservation (NYSDEC),
recently conducted a study to examine, characterize, and quantify emissions from the
simulated open burning of household waste materials in barrels {Lemieux, 1997). A
representative waste to be burned was prepared based on the typical percentages of
various waste materials disposed by New York State residents; hazardous wastes (i.e.,
chemicals, paints, oils, etc.) were not included in the test waste. A variety of compounds,
Including CDD/CDFs, were measured in the emissions from the simulated open burning.
The measured CDD/CDF TEQ emission factor for waste, which has not been separated for
recycling purposes, was 0.14 ^g TEQ/kg of waste burned (setting not detected values
equal to zero) and 0.3 jjg TEQ/kg (setting not detected values equal to one-half the
detection limit).
"•I,.'', i ' n " ,' i , i j • "„, ,!••'! . " , '• '.' 'i! • . t "• '''i,::', !i ''.!'
The limited emission faptprH and activity level data available were judged inadequate
: •! . . ' !"* ;> ' ' , "'. ill' 'Vi'!ii ;" :"'' '," '•: •-'.•••'.. ' -.' :••; , > ; : ' •>• :, "•; J '.ff.'~ - '••' >:' ••.,, i
for developing national emission estimates that could be included in the national inventory.
The number of households nationwide burning waste in barrels is unknown. The emission
factor was developed on the basis of just two experiments. The representativeness of the
trash and burning conditions used in the experiments to rural conditions nationwide are
unknown. However, combining the emission factor of 6.14//g TIEQ/kg of waste burned
with the following information/assumptions, allows a preliminary order of magnitude
Si • • i,- ' • '"";. ' .. • ,i;l ::' .. r r.M^vj, •• : : i .'.;;•'. i ,,
6-14
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
\ ' i s .
estimate to be made of potential national CDD/CDF TEQ emissions from backyard
household trash burning.
.'' i - . , • ' - - - • .
-, Forty percent of the rural population in the United States are assumed to burn
tneir household waste in a barrel (Two Rivers Region Council of Public Officials
and Patrick Engineering, 1994). ' ,
- On average, each U.S. citizen generates 3.72 pounds of solid waste (excluding
yard waste) per day (or 616 kg/person-yr) (U.S. EPA, 1996b). ,
- On average, for those individuals burning household waste, approximately 63
percent of waste generated are burned (i.e.,. 63 percent of 616 kg/person-yr =
388 kg/person-year) (Two Rivers Region Council of Public Officials and Patrick
Engineering, 1994).
- In 1992, 51.8-million people lived in nonmetropolitan areas (U.S. DOC, 1997).
Emissions = (51.8 x 106 peoplej(40%)(388 kg/person-yr) (0.14 //g TEQ/kg)(1Q-6 q///q)
= 1,125 g TEQ/yr ,
When rounded to trie nearest order of magnitude to emphasize the uncertainty in
this estimate, the estimate of 1,125 g TEQ/yr results in a value of 1,000 g TEQ/yr. This
estimate should be regarded as a preliminary indication of possible emissions from this
source category; further testing is needed to confirm the true magnitude of these
emissions.
6.6. UNCONTROLLED COMBUSTION OF POLYCHLORINATED BIPHENYLS (PCBS)
The accidental combustion of PCB containing electrical equipment or intentional
combustion of PCBs in incinerators and boilers not approved for PCB burning (40 CFR 761)
may produce CDDs and CDFs. At elevated temperatures, such as in transformer fires,
PCBs can undergo reactions to form CDF and other by-products. More than 30 accidental
fires and explosions involving PCB transformers and capacitors in the United States and
Scandinavia, which involved the combustion of PCBs and the generation of CDDs and
CDFs, have been documented (Hutzinger and Fiedler, 1991b; O'Keefe and Smith, 1989;
Williams et al., 1985). For example, analyses of soot samples from a Binghamton, New
York, office building fire detected 20lyag/g of total CDDs (0.6 to 2.8 /^g/g of 2,3,7,8-TCDD)
and 765 to 2,160 //g/g of total CDFs with 12 to 270 //g/g of 2,3,7,8-TCDF. At that site,
the fire involved the combustion of a mixture containing PCBs (65 percent) and
•6-15 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
chlorobenzene (35 percent). Laboratory analyses of soot samples from a PCB transformer
fire, which occurred in Reims, France, indicated total CDD and CDF levels in the range of 4
to 58,000 ng/g and 45 to 81,000 ng/g, respectively.
Using a bench-scale thermal destruction system, Erickson et al. (1984) determined
the optimum conditions for CDF formation to be 675°C, an excess oxygen concentration of
1 * > ' i , . • • in , ' .• .'.; i" * 1 ' .', /I''.!!,;,: . ,-. (.•••>,,: ',•:.•!• • i-;rv •. »,;, , /,;,,, ,..,.[
8 Percent:r anc? a residence time of Qf8 seconds or longer. Combusting mineral oil and
s''?cone °'' c°.ntairjjng 5, 50, and 500 ppm of Aroclqr 1.254 at these conditions for 0.8
seconds yielded PCB to CDF conversion efficiencies as high as 4 percent. Up to 3 percent
conversion efficiency was observed when an askarel (70 percent Aroclor 1260) was
combusted under the same conditions.
The use of PCBs in new tr;ansfprrners in the United States is banned, and their use in
existing transformers and capacitors is being phased out under regulations promulgated
under the Toxic Substances Control Act (TSCA).
Because of the accidental nature of Jhese incidents, the variation in duration and
intensity of elevated temperatures, the variation in CDD/CDF content of residues, and
uncertainty regarding the amount of PCBs still in-service in electrical equipment EPA
•'"''' ' " ', , i;'Ti :'; •", v"':; J"''1''''",':!" ',••'•'•*• '•'' 'i1'"1;'1' i1"1""'1'"" /'" ''? '• ''".i ;:'; "*;•''.•' • \.
judged the available data inadequate to support even an order of magnitude estimate of
annual CDD/CDf emissions. However, Thomas and Spiro (1995) conservatively estimated
v '" • .;•'•• '„, .i':; '.,• ' i.: : ,ii;,'.';: n ;•:'•. i! ..• ;v> i1 i' •:•" •:•'),•: ;i i iiVi1'.' ': ;;f • ;>:f' " '!'•'.'•
that about 15 g of TEQ may be generated annually from fires in commercial and residential
j>: .: •" ' i"!"1] ' ..,"'• :>'",ii,::v .'.ill'" ."i i ':'' :•': i-:," *•• t /'' !;. /''". •," ' i '"i,',v\'i •<: ' , >E •„•>•'.,. : ,' i •
buildings each year. This estimate is based on the following assumptions: (1) a TEQ
em'?sion rate of 20= -"9/k9 of PCB burned; (2) 74,000 metric tops of PCB are still in use in
varipus electrical equipment; and (3) 1 percent of the in-use PCBs is burned during the
course of structural fires annually.
6.7. VOLCANOES
To date, no studies demonstrating formation of CDD/CDFs by volcanoes have been
1 ' , , 'I'iiu n.| ""• "'. ,„ " , : »„'!', : If « 'i ,:,.!• ' " • n,;!i,, '.|•,'':« r i:" t K '!• ' f „'",! .. !!; ,.;„», , , • , . .
published. Gribble (1994) summarized some of the existing information on the formation of
chlorinated compounds by natural sources, including volcanoes. Gribble (1994) reported
that several studies had demonstrated the presence of chlorqf luorocarbpns and simple
halogenated aliphatic compounds (one and two carbon chain length) in volcanic gases. In
addition, several chlorinated monoaromatic compounds as well as three PeCB conaeners
i ',„ ' , J ..ilsil,11! •: i» ' • ."'' ' i1''r i „;'lit i/ in!'i!" „ ,,ii , i ,". • '• 'i'1!1 ,;,' », u '< •• "?i: " n lift' ',!,«' n, ,HI "i "!,,ri ,, /iHniih ., • : i . *3
were reported as having been detected in the ash from the 1980 eruption of Mt. St
6-16
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Helens. The formation of these PCB compounds was hypothesized by Gribble (1994) to be
th.e result of rapid, incomplete high temperature combustion of chloride-containing plant
material in the eruption zone. However, Gribble (1994) presented no information indicating
formation of CDD/CDFs by volcanoes. a' ,
Lamparski et al. (1990) analyzed groundfall ash samples collected at various
distances and locations from Mt. St. Helens following the eruption in 1980. The findings of
this study .indicate that volcanic particulate emissions were free of detectable PCBs and
nearly free of detectable CDDs (0.8 ng/kg HpCDD detected) upon exiting the volcano and
remained so throughout their period of deposition in the blast zone. However, upon
transport through the atmosphere, measurable and increasing levels of CDDs and PCBs
were detected in deposited1 ash as the ash passed from rural to urban environments. The
authors hypothesized that CDDs and PCBs in the atmosphere became associated with the
volcanic ash particulates through gas-phase sorption or particulate agglomeration.
Takizawa et al. (1994) sampled the dust fall from the active volcano, Fugendake, as
well as the volcanic ash from the active volcano, Sakurajima, for CDD and CDF congener
group concentrations. The study was not designed to determine whether the CDD/CDFs
observed were formed by the volcanoes or were scavenged from the atmosphere by the
falling dust and ash. The dust fall was collected for 1 -month periods during July and
October 1992; two samples of the volcanic ash were collected in 1992. The results of the
sample analyses for 2,3,7,8-substituted CDDs and CDFs, presented in Table 6-2, show that
no 2,3,7,8-substituted congeners with less than 7 chlorines were detected; Takizawa et al.
(1994), however, did report that npn-2,3,7,8-substituted congeners in the lower
chlorinated congener groups were detected.
Based on the available information from the studies discussed above, it is concluded
that volcanoes do not appear to be sources of CDD/CDF release to the environment.
6"1-7 April 1998,
-------
E>RAFT~DQ NOT QUOTE OR CITE
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 TEQ
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*
0.018
0.092
0.074
0 074
0.259
0.755
4.414
14.074
0.385
1.136
1 455
0.422
0.110
0.681
1.215
0 073
0.639
5.686
20.192
2.392
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Source: CARB (1990d)
'' "''!"'! ' ' V i '. " ,':"" '"', ":' ; .''. ', •'.•. " ;i' " I,!1-1"1! '.'i ''"'''' "'' ^'" •'• '; !-
: ' : , ' . iij'i ,j" • •', j:-; "it'-l ' J ','',.' i? '.jf1 '','• '..'.'•'.. ' "•• "" \:i •',"•' '•'": '• J.'"•'r1'1* :.• ' ', •
* Assumes heat consent pf 1r86E-i-07 J/m3 for landfill gas (Federal Register, 1996a),
NR = Not reported.
6-18
April 1998
-------
DRAFT-DO NOT QUOTE OR GITE
Ratio (congener emission factor / total 2378-CDD/CDF emission factor)
0.1 0.2 0.3 0.4 0.5
0.6
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
2,3,4,6,7v8-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
Source: CARB (1990d).
Figure 6-1. Congener Profile for Landfill Flare Air Emissions
6-19
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 6-2. CDD/CDF 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 1 992
<0.5
<0.5
<0.5
9.2
14
<0.5
<0.5
<0.5
1.9
4.2
Oct. 1 992
<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
Source: takizawa et al. (1994).
8 Dust fall measured from the active volcano, Fugendake.
b Volcanic ash measured from active volcano, Sakurajima.
6-20
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
7. METAL SMELTING AND REFINING SOURCES OF CDD/CDF
.7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING
Nonferrous metals include copper, magnesium, nickel, and aluminum. The potential
for formation and release of CDD/CDFs by primary copper smelters has been addressed by
Environmental Risk Sciences (1995). Although European investigators {Oehme et al.,
r . - - • •
1989; Lexen et al., 1993) have reported the presence of CDD/CDFs in the wastestreams of
magnesium, nickel, and aluminum refining facilities, insufficient information is available for
evaluating CDD/CDF emissions, if any, from the smelting/refining of these nonferrous
metals in the United States. The findings of these studies are discussed in the following
paragraphs.
Environmental Risk Sciences (1995) recently prepared an analysis for the National
Mining Association on the potential for dioxin emissions from the primary copper smelting
industry. The analysis included a detailed review of the process chemistry and technology
of primary copper smelting, collection of operating conditions/and process stream
compositions from seven of the eight U.S. primary copper smelters, and stack testing for
CDD/CDFs at two facilities. The stack testing (Secor International, Inc., 1995a and 1995b)
involved the principal process off-gas streams for copper smelters: main stack, plant tail
gas stack, and the vent fume exhaust. The two tested facilities were assumed to be
representative of the other facilities in, the industry due to similarities in process chemistry,
process stream composition, and process stream temperatures.
The results of the analyses of the process chemistry/technology and the operating
parameters and process stream compositions indicated a very low potential for CDD/CDF
emissions. The results of this conclusion are supported by the stack test data from the two
tested facilities. CDD/CDFs were not detected in the emissions from either facility. If it is
conservatively assumed that all nondetected values were present at one-half the detection
limits, the annual TEQ emission rate for the copper'smelting industry would be less than 1
gram (g). '. , .
Oehme et al. (1989) reported that the production of magnesium leads to the
formation of CDDs and CDFs. Oehme et al. (1989) estimated that 500 g of TEQ are
released in wastewater to the environment and 6-g TEQ are released to air annually from a
magnesium production facility studied in Norway; CDFs predominated with a CDF to CDD
7~ V .•-•.- April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
concentration ratio of 10 to1. .The magnesium production process involves a step in which
MgCI2 is produced by heating MgO/coke pellets in a pure chlorine atmosphere to about 700
to 800°C. The MgCI2 is then eiectrolyzed to metallic magnesium and CI2. The CI2 excess
from the MgCI2 process and the CI2 formed during electrolysis are collected by water
scrubbers and discharged to the environment.
Oehme et al. (1989) also reported that certain primary nickel refining processes
generate CDDs and CDFs, primarily CDFs. Although the current low temperature process
used at the Norwegian facility studied is estimated to release only 1 -g TEQ per year, a high
temperature NiCI2/NiO conversion process that had been used for 17 years at the facility is
believed to have resulted in much more significant releases based on the ppb levels of CDFs
detected in aquatic sediments downstream of the facility (Oehme et al., 1989).
Lexen et al. (1993) reported that samples of filter powder and sludge from a lagoon
at the only primary aluminum production plant in Sweden showed no or little CDD/CDF.
I'Jll! " " .'. . !- "' ' '•:'..' ' .'!'"' ' " ' '' "'. .,''.' !"
7.2. SECONDARY NONFERROUS METAL SMELTING
Secondary smelters primarily engage in the recovery of nonferrous metals and alloys
from new and used scrap and dross. The principal metals of this industry both in terms of
volume and value of product shipments are a|uminumvcppper, lead, zinc, and precious
metals {U.S. DOC, 1990a). Scrap metal and metal wastes may contain organic impurities
such as plastics, paints, and solvents. Secondary smelting/refining processes for some
metals (e.g., aluminum, copper, and magnesium) utilize chemicals such as NaCI, KCI, and
other salts. The combustion of these impurities and chlorine salts in the presence of
various types of rnetal during reclamation processes can result in the formation of CDDs
and CDFs, as evidenced by the detection of CDDs and CDFs in the stack emissions of
secondary aluminum, copper, and lead smelters (Aittola et al., 1992; U.S. EPA, 1987a;
U.S. EPA 1997b).
••' '_ '". '•. >f' ' '.' v i •1/.':•;;.'••' 'i' ' '•>• '''':" ' . •.'.'. ,''-'A. '.i-'1-' :. >• *'''•• : ;' • • ' : • ',
7.2.1. Secondary Aluminum Smelters
Secondary aluminum smelters reclaim aluminum from scrap containing aluminum.
This recycling involves two processes — precleaning and smelting. Both processes may
produce CDD/CDF emissions.
7-2 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
Precleaning processes involve sorting and cleaning scrap to prepare it for smelting.
Cleaning processes that may produce CDD/CDF emissions use heat to separate aluminum
from contaminates and other metals; these techniques are roasting and sweating. Roasting
uses rotary dryers with a temperature high enough to vaporize organic contaminants, but
not high enough to melt aluminum. An example of roasting is the delacquering and
processing" of used beverage cans. Sweating involves heating aluminum-containing scrap
metal to a temperature above the melting point of aluminum, but below the melting
temperature of other metals such as iron and brass. The melted aluminum trickles down
and accumulates in the bottom of the sweat furnace and is periodically removed.
After precleaning, the treated aluminum scrap is smelted and refined. This usually
takes place in a reverberatory furnace. Once smelted, flux is added to remove impurities.
The melt is "demagged" to reduce the magnesium content of the molten aluminum by the
addition of chlorine gas. The molten aluminum is transferred to a holding furnace and
alloyed to final specifications.
CDD/CDF emission factors for secondary aluminum operations can be derived from
results of testing performed in 1995 at four secondary aluminum smelters. Three of the
tests were conducted by EPA in conjunction with the Aluminum Association for the
purpose of identifying emission rates from facilities with potentially MACT-grade operations
and APCD equipment.
The first facility tested was a top charge melt furnace (Advanced Technology
Systems, Inc., 1995). During testing, the charge material to the furnace was specially
formatted to contain no oil, paint, coatings, rubber, or plastics (other than incidental
amounts). The CDD/CDF emissions from such a clean charge, 0.26-ng TEQ/kg charge
material, would be expected to represent the low end of the normal industry range.
The second facility operates a sweat furnace to preclean the scrap and a
reverberatory furnace to smelt the pre-cleaned aluminum (U.S. EPA, 1995h). Stack
emissions are controlled by an afterburner operated at 1,450° F. The TEQ emission factor
for this facility was 3.22-ng TEQ/kg aluminum produced..
The third facility employs a crusher/roasting dryer as a precleaning step followed by
a reverberatory furnace (Galson Corporation, 1995). The emissions from the two units are
vented separately. The exhaust from the crusher/dryer is treated with an afterburner and a
baghouse. The exhaust from the furnace passes through a baghouse with lime injection.
7-3
April 1998
-------
, DRAFT-PO NOT QUOTE OR CITE
M ' " ' I'M: , ' '!" i '. ' : ' • • , , '' ' '. ',
' ,i " ' r ' ' ' !', ; „, "I1 ' . '!' ,:"", , ' ," : , i'll ', , . !
Both stack exhausts were tested and the combined TEQ emission factor was 12.95-ng
TEQ/kg aluminum produced. Because the activity level of the facility at the time of
sampling was treated as confidential business information, the calculated emission factor
was based on the reported typical production rates of the two operations, 26,000 Ibs/hr for
the crusher/dryer and 6,700 Ibs/hr for the furnace.
The fourth facility operates a scrap roasting dryer followed by a sidewell
rei/erberatory furnace (Envisage Environmental, Inc., 1995). The emissions from the two
units are vented separately. Exhaust from the dryer passes through an afterburner and a
lime-coated baghbuse. The exhaust from the furnace passes through a lime-coated
baghouse. Both stack exhausts were tested and the combined TEQ emission factor was
36.03-ng TEQ/kg of charge material. Problems with the scrap dryer were discovered after
the testing was completed. Also, operating conditions during testing were reported to
represent more worst case than typical operations.
The congener and congener group emission factors derived from this testing are
presented in Table 7-1. The average congener and congener group profiles are presented in
Figure 7-1. The average of the TEQ emission factors measured at the four facilities is
13.1-ng TEQ/kg of scrap feed. [Note: Although the emission factors at two of the
:.; . ." : ' \ ;"|S: ,' : />'; ;• . ;>;;B > :••..' ;;. "I••:!•:::; .•• n .;: •;.. ,i (';•:':.;[..:;• ,'f i,^< ••'•.. " j , t
facilities are based on the output rather than input rate, the two rates are assumed, for
purposes of this report, to be roughly equivalent.] Although the testing was recently
'•, , " '. iris , , " ri.1'. ' i ;* '•'.',:; v, i > " '•••-,.: '.'i'.'i'U ;'. ;",'n ,. : ,• :;;ij,'
conducted at U.S. facilities, a "low" confidence rating is assigned to this average emission
factor, because it is based on the results of testing at only four facilities, several of which
may have more effective APCD than the other facilities in the industry. For example, two
facilities tested by CARB in 1992 and reported in two confidential reports (CARB, 1992a,
as reported in U.S. EPA, 1997b; CARB, 1992b, as reported in U.S. EPA, 1997b) were
reported to have TEQ emission factors of 52.2- and 21.7-ng TEQ/kg scrap aluminum
consumed.
Umweltbundesamt (1996) reported stack testing results for 25 aluminum smelters/
foundries in Germany. Sufficient data were provided in Umweltbundesamt (1996) to
enable calculation of TEQ emission factors for 11 of the tested facilities. The calculated
emission factors ranged from 0.01- to 167-ng TEQ/kg of scrap feed. Three facilities had
'";'l!jj.||| ,, , '"''!'„ '' i ' Hi ' ' ,! ' ' • '
errtlssion factors exceeding 100-ng TEQ/kg, and two facilities had emission factors less
!•• , ' ' " '.'•' iiiiii i. '• •' , ;,..,"•... I | ( f , .,
than 1-ng TEQ/kg. The mean emission factor for the 11 facilities was 42-ng TEQ/kg,
7-4 April 1998
-------
DRAFTS-DO NOT QUOTE OR CITE
i. :
which is very similar to the mean emission factor for the two CARB studies {i.e., 37-ng
TEQ/kg).
A total of approximately 727,000 metric tons of scrap aluminum were consumed by
67 secondary aluminum smelters in 1987 (U.S. DOC, 1995c), In 1995, consumption of
scrap aluminum by the 76 facilities comprising the secondary aluminum smelting industry
had nearly doubled to a quantity of 1.3-million metric tons (U.S. Geological Survey, 1997a;
The Aluminum Association, 1997). A "high" confidence rating is assigned to these
production estimates, because they are based on government survey data. Applying the
TEQ emission factor of 13.1-ng TEQ/kg of scrap feed to these consumption values yields
estimated annual emissions of 9.5-g TEQ in 1987 and 17.0-g TEQ in 1995.
Based on the "low" confidence rating assigned to the estimated TEQ emission
factor, the estimated range of potential emissions is assumed to vary by a factor of 10
between the low and high ends of the range. Assuming that the estimated emissions of
9.5-g TEQ in 1987 and 17.0-g TEQ in 1995 are the geometric means of the ranges for
these years, then the ranges are calculated to be 3.0- to 30.0-g TEQ in 1987 and 5.4- to
53.8-gTEQin 1995.
It should be noted that a significant amount of scrap aluminum is consumed by
other segments of the aluminum industry. Integrated aluminum companies consumed 1.4-
million metric tons of scrap aluminum in 1995, and independent mill fabricator? consumed
0.68-million metric tons (U.S. Geological Survey, 1997a).
7.2,2. Secondary Copper Smelters/Refiners
Stack emissions of CDD/CDFs from a secondary copper smelter were measured by
EPA during the National Dioxin Study (U.S. EPA, 1987a). The tested facility recovers
copper and precious metals from copper and iron-bearing scrap and was chosen for testing
by EPA because the process technology and air pollution control equipment in place were
considered typical for the source category. The copper and iron-bearing scrap are fed in
batches to a cupola blast furnace, which produces a mixture of slag and black copper.
Four to 5 tons of metal-bearing scrap were fed to the furnace per charge, with materials
typically being charged 10 to 12 times per hour. Coke fueled the furnace, and represented
approximately 14 percent by weight of the total feed. During the stack tests, the feed
consisted of electronic telephone scrap and other plastic scrap, brass and copper shot, iron-
7-5 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
bearing copper scrap, precious metals, copper bearing residues, refinery by-products,
converter furnace slag, anode furnace slag, and metallic floor cleaning material. The
telephone scrap comprised 22 percent by weight of the feed and was the only scrap
component that contained plastic materials. Oxygen enriched combustion air for
combustion of the coke was blown through tuyeres at the bottom of the furnace. At the
top of the blast furnace were four natural gas-fired afterburners to aid in completing
: ' ;l:i';i ,' - i ; •: .„• " !' I ; , • i,,!, '.' '--I. .,'. :. : „!/" ' .. ' . . I •
combustion of the exhaust gases. Fabric filters controlled paniculate emissions, and the
,flue gas then was discharged into a common stack. The estimated emission factors
derived for this site are presented in Table 7-2. The emission factors are based on the total
weight of scrap fed to the furnace. The TEQ emission factor estimated in U.S. EPA
i-., • • ":, , s:c " ' • '! ,; , •! :• :• '•;>•.•*, "i" r. ,' ,;":<"';''' '..."•:' •'••'?;>. ', ' • I
(1997c), based on the measured congener and congener group emission factors, is 779
ng/kg of scrap metal smelted. Figure 7-2 presents the congener group profile based on
, . •'• " ;•'!« :'-' , •>:> ,, ;"". • • '":•' i;' '. • •. '•• .-' ^ 'i; . "•'' •
these emission fgctors.
1 i ' ' ,„ : „.'' '• S ' , ,,' •,, ' , , ' i ,'•''• ' ,i
Approximately 390,000 metric tons of scrap copper were consumed by U.S.
secondary copper smelters/refiners in 1987 {U.S. DOC, 1990a).' In 1995, approximately
695,000 metric tons of scrap copper were consumed by the 24 operating U.S. copper
smelters, refiners, and ingot makers (U.S. Geological Survey, 1997a). If the TEQ emission
rate derived above (779 ng/kg of scrap consumed) is assumed to be representative of the
24 copper facilities, then the estimated air emissions of CDD/CDF TEQ by secondary
copper operations in the United States in 1987 were 304 grams, and the estimated TEQ
emissions in 1995 were 541 grams. A "high" confidence rating is assigned to the
production estimates, because they are based on government survey data. A "low"
confidence rating is assigned to the TEQ emission estimate, because it is based on direct
measurements at only one U.S. copper smelter. Based on these confidence ratings, the
estimated range of potential annual emissions is assumed to vary by a factor of 10
between the low and high ends of the range. Assuming that the estimates of annual
" ,, • ;::,;? .-.••"'•'.•'•'•'. -^ , ':;;>-,;"f '.!:;ii'',;' ^ i v«v> ;:,••• ': W^' , •'. [• : •. ' :
emissions (304-g TEQ in 1987 and 541-g TEQ in 1995) are the geometric means of these
ranges for those years, then the ranges are calculated to be 96- to 960-g TEQ in 1987 and
'.I1' •• ' . .ini'i ! " • •.'.'. '-:,„ " .:••.••,,!'! ' ' '.." •"• •,! i: i',1 ,,"":; * •; M"; - ,;•. ' , . •
171-to 1,710-g TEQ in 1995.
It should be noted that a significant amount of scrap copper is consumed by other
segments of the copper industry. In 1995, brass mills and wire-rod mills consumed
7-6 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
886,000 metric tons of copper-base scrap; foundries and miscellaneous manufacturers
consumed 71,500 metric tons (U.S. Geological Survey, 1997a).
\ . - • -
i = •
7.2.3. Secondary Lead Smelters/Refiners
The secondary lead smelting industry produces elemental lead through the chemical
reduction of lead compounds in a high temperature furnace (1,200 to 1,260° C). Smelting(
is performed in reverberatory, blast, rotary, or electric furnaces. Blast and reverberatory
furnaces are the most common types of smelting furnaces used by the 23 facilities that
comprise the current secondary lead smelting industry in the United States. Of the 45
furnaces at these 23 facilities, 15 are reverberatory furnaces, 24 are blast furnaces, 5 are
rotary furnaces, and 1 is an electric furnace. The one electric furnace and 11 of the 24
blast furnaces are co-located with reverberatory furnaces, and most share a common
exhaust and emissions control system (U.S. EPA, 1994a).
Furnace charge materials consist of lead-bearing raw materials, lead-bearing slag and
drosses, fluxing agents (blast and rotary furnaces only), and coke. Scrap motor vehicle
lead-acid batteries represent about 90 percent of the lead-bearing raw materials at a typical
lead smelter. Fluxing agents consist of iron, silica sand, and limestone or soda ash. Coke
js used as fuel in blast furnaces and as a reducing agent in reverberatory and rotary
furnaces. Organic emissions from co-located blast and reverberatory furnaces are more
similar to the emissions of a reverberatory furnace than the emissions of a blast furnace
(U.S. EPA, 1994a).
Historically, many lead-acid batteries contained PVC plastic separators between the
battery grids. These separators are not removed from the lead-bearing parts of the battery
during the battery breaking and separation process. When the PVC is burned in the smelter
furnace, the chlorides, are released as HCI, CI2, and chlorinated hydrocarbons (Federal
Register, 1995d). The source of CDD/CDFs at secondary lead smelters is the PVC
separator (U.S. EPA, 1995c). In 1990, about 1 percent of scrap batteries processed at
lead smelters contained PVC separators. In 1994, less than 0.1 percent of scrap batteries
contained PVC separators. This trend is expected to continue because no U.S.
.> - •
manufacturer of lead-acid automotive batteries currently uses PVC in production (U.S. EPA,
19956; Federal Register, 1995d). , !
7"7 . April 1998
-------
. DRAFT-DP NOT QUOTE OR CITE
,, i , ' ' i: ' ,;, ' i' , i "i, "'''.,,'" 7 " , ,
The total current annual production capacity of the 23 companies currently
'.,: : • • 'Si'S,! .' ,„' i .:'• •'' "• , , > • ''•': ,i i ' - v",'', • .'.' ' ',-,,:! .' ," .' ' '"'" i: :""" : i1 ' .
comprising the U.S. lead smelting industry is 1.36-million metric tons. Blast furnaces not
C';;,"" , -' i ';;;:;! .; ," ,•• . .• / ,, •:••;.:• , ^ v :',:•': v. • •" "; '•• "•,'•• •• • .?;.:•: ',:;'„ ••• |. • • • • . • .
co-located with reyerberatory furnaces account for 21 percent of capacity (or 0.28-million
metric tons). Reyerberatory furnaces and blast and electric furnaces co-located with
reyerberatory furnaces account for 74 percent of capacity (or 1.01-million metric tons).
Rotary furnaces account for the remaining 5 percent of capacity (or 0.07-million metric
tons). Actual production volume statistics by furnace type are not available. However, if it
,,,""! ' ', .,' .'. ...jiii'i • '• , . ..., ', '.' i •: . i ....'•.. " • -,:: i " '*, .. •• "i • !"• "/i " ..[ • • | i '.. . • ''
is assumed that the total actual production volume of the industry, b.97-million metric tons
in 1995 (U.S. Geological Survey, 1997a) and 0.72-million metric tons in 1987 (U.S. EPA,
1994a), are reflective of the production capacity breakdown by furnace type, then the
, i,,'"' i , '" .i'lllTlli '• , , ' ". ,i ,. \fi T! • K" IH!'!,:',',|, i ,'i, i, .',,1 ' '""hi ,'„ , ,,"'•. -r ,«, , • V I1): „ , ' - ! "" * ' 'I
estimated actual production volumes of blast furnaces (not cp-located), reverberatory and
co-located blast/electric and reverberatory furnaces, and rotary furnaces were 0.20-, 0.72-,
arid 0.p5-mi|!Jon metric tons, respectively, in 1995, and 0.15-, 0.53-, and 0.04-million
metric tons, respectively, in 1987. In 1987, the industry consisted of 24 facilities.
CDD/CDF emission factors can be .estimated for lead smelters based on the results
of emission tests recently performed by EPA at three smelters (a blast furnace, a co-located
blast/reverberatory furnace, and a rotary kiln furnace) (U.S. EPA, 1992e; 1995d; 1995e).
The air pollution control systems at the three tested facilities consisted of both baghouses
"" i' 4, * ""lil ! 'ii • • ' •"', 'i:'•••,! ' !•"'•'"!!,„ 1 :'• ' Wii; "" „' » : r • /, - '."I1:f|1 ", "'• a,, , j'li!,!.:!!1, ,ih:/,, i ' r «• •• ,
and scrubbers. Congener-specific measurements were made at the exit points of both
APCD exit points at each facility. Table 7-3 presents the congener and congener group
erqission factors Irprri the baghouse and the scrubber for each site. Figure 7-3 presents the
.• -i' • • ' i..;1. ' '; "iiiii1 •'" ' ' i "' " '' ' "' >" ' ;" !•. •; •••„, ,, '
corresponding profiles for the baghouse emissions from the tested blast furnace and
reverberatory furnace. Although all 23 smelters employ baghouses, only 9 employ scrubber
technology. Facilities that employ scrubbers account for 14 percent of the blast furnace
(not co-located) production capacity, 52 percent of the reverberatory and co-located
furnace production capacity, and 57 percent of the rotary furnace production capacity.
From the reported data, TEQ emission factors (ng TEQ/kg lead processed) for each of the
: . • • . . >!iii' -!; , ';'" • ','"••• liS!1",;; !': i1 :: ,'i,:1"1";"!': .:,",•'', •.»"1: ; f'f,;,;,;';,;,;;,-.';,'' ; i|;!',i"!';.'/:', •"••,!.';
three furnace configurations are presented below as a range reflecting the presence or
absence of a scrubber.
" ,' "fl;1 •' • i. :,i"; ' ' '„ ii • , ' , ' - ' ' ,:"'l ''i :,•',, ", ,"' - ',•" •'"'.'•"' . ! '
Emission factors when nondetected values are set equal to zero:
• Blast furnace: 0.63- to 8.31 mg TEQ/kg lead produced.
7-8 „ April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
• Reverberatory/co-located furnace: 0.051- to 0.41-ng TEQ/kg lead produced.
• Rotary furnace: 0.24- to 0.66-ng TEQ/kg lead produced.
If it is assumed that these emission rate ranges are representative of the range of
emission rates at the non-tested facilities with the same basic furnace configuration and
presence or absence of scrubbers, then combining these emission rate ranges with the
estimates derived above for secondary lead production volumes and the percents of each
configuration type that utilize or do not utilize scrubbers yields the following estimated air
emissions in units of grams TEQ per year:
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
Estimated Annual TEQ
Ref. Year 1 995
0,018
1.429
0.019
0.142
0.019
0.005
1 .632
Emissions (g TEQ) *
Ref. Year 1987
0.013
1.072
0.014
0.104
0.015
0.004
1.223
* Calculated using emission factors based on nondetected values set equal to zero.
A "medium" confidence rating is ascribed to the emission factors derived above,
because stack test data were available for 3 of the 23, smelters 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. , ,
Based on these confidence ratings, the estimated range of potential annual
emissions is assumed to vary by a factor of 5 between the low and high ends of the range.
Assuming that the estimates of annual emissions (1.63-g TEQ in 1995 and 1.22-g TEQ in
1987) are the geometric means of these ranges for these years, then the ranges are
calculated to be 0.73- to 3.65-g TEQ in 1995 and 0.55- to 2.73-g TEQ in 1987.
7-9
; April 1998
-------
. DRAFT--DO NOT QUOTE OR CITE
i " ' i, ." |'!,j , .ii ' , • ' i ',,,:', :.• . , ' , • ,i| j, , i ' . .,
-------
DRAFT-DO NOT QUOTE OR CITE
comparability of recycling practices at U.S. and European sinter plants has not been
determined.
Sinter plants in Sweden were reported to emit up to 3-ng TEQ/Nm3 stack gas or 2-
to 4-g TEQ/yr per plant to the air (Rappe, 1992b; Lexen et al., 1993). Bremmer et al.
(1994) reported the results of stack testing at three iron ore sintering plants in The
Netherlands. One facility equipped with wet scrubbers had an emission factor of 1.8-ng
TEQ/dscm (at 11 percent O2). The other two facilities, both equipped with cyclones, had
emission factors of 6.3- and 9.6-ng TEQ/dscm (at 7 percent O2). Lahl (1993; 1994)
reports stack emissions for sintering plants in Germany (after passage through mechanical
filters and electrostatic precipitators) ranging from 3- to 10-ng TEQ/Nm3. A recent
compilation of emission measurements by the German Federal Environmental Agency
indicates stack emission concentrations ranging from 1.2- to 60.6-ng TEQ/m3 (at 7 percent
O2); the majority of current emissions lie around 3-ng TEQ/m3 (Umweltbundesamt, 1996).
In 1996, 11 sintering plants were operating in the United States, with a total annual
production capacity of about 17.6-million metric tons (Metal Producing, 1996). Over the
past 15 years, the size of this industry decreased dramatically. In 1982, 33 facilities
operated with a combined total capacity of 48.3-million metric tons (U.S. EPA, 1982b). Iri
, 1987, sinter consumption was 14.5-million metric tons (AISI, 1990); in 1994, consumption
was 12.2-million metric tons (AISI, 1995) or approximately 77 percent of production
capacity assuming that production capacity in 1994 was the same as in 1996.
No testing of CDD/CDF emissions from U.S. sinter plants has been reported upon
which to base an estimate of national emissions, and the comparability between dust/scrap
recycling practices at U.S. and European sinter plants has not been determined. The limited
data available were thus judged inadequate for developing national emission estimates that
could be included in the national inventory. However, a preliminary order of magnitude
estimate of potential TEQ annual emissions from U.S. sintering plants can be made using
European emission test results and the following assumptions based on the data presented
in Table 7-4: (1) the total strand surface area of U.S. plants is 1,685 m2; (2) on average,
an estimated 5,877 m3 of exhaust gas are emitted per hour per m2 of strand; (3) on
average, sinter plants are operating at 77 percent capacity for 350 operating days per year
(i.e., 6,486 hrs/yr); and (4) the TEQ emission factor is about.4-ng TEQ/m3 of exhaust gas
(i.e., the approximate midpoint of the emission factors reported by Rappe (1992b), Lexen et
7-11
April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
;• ' , • '' in • • ., , " ' .:;. ' ;i : . M " ' • ,;' >'" : " |
al. (1993), Bremmer et al. (1994), Lahl (1994), and Umweltbundesamt, 1996)). Applying
these assumptions yields an estimated total annual current emission of 256-g TEQ/yr,
which, when rounded to the nearest order of magnitude to emphasize the uncertainty in
this estimate, results in a value of 100-g TEQ/yr. This estimate should be regarded as a
preliminary indication of possible emissions from this source category; further testing is
needed to confirm the true magnitude of these emissions.
7.3.2 Coke Production
Coke is the principal fuel used in the manufacture of iron and steel. Coke is the
solid carbonaceous, material produced by the destructive distillation of coal in high
temperature ovens. No testing of CDD/CDF emissions from U.S. coke facilities has been
reported. However, at a facility in the Netherlands, Bremmer et al. (1994) measured a
CDD/CDF emission rate to air during the water quenching of produced hot coke of 0.23-ng
TEQ/kg of coal consumed. Minimal CDD/CDF air emissions, 0.002-ng TEQ/kg of coal, were
estimated by Bremmer et al. (1994) for flue gases generated during charging and emptying
the coke ovens.
In 1995, an estimated 30-mjllion metric tons of qoaf were consumed by coke plants
in the United, States (EIA, 1997b). No testing of CDD/CDF emissions from U.S. coke plants
has been reported upon which to base an estimate of national emissions. The limited data
available were thus judged inadequate for developing national emission estimates that could
be included in the national inventory. However, a preliminary order of magnitude estimate
of potential TEQ annual emissions from U.S. coke plants can be made by combining the
consumption value of 30-million metric tons and the emission factor reported by Bremmer
et al. (1994) for a Dutch coke plant (0.23-^g TEQ/kg of coke). This calculation yields an
annual emission of 6.9-g TEQ in 1995, which, when rounded to the nearest order of
„ ,„ ..u !,,,,, ,: : ,h „ . : ,; l: „, :i | „ " ,, „ |S , | ,, M|M ,, ., M , ^ f j'V,
magnitude to emphasize the uncertainty in this estimate, results in a value of 10-g TEQ/yr.
This estimate should be regarded as a preliminary indication of possible emissions from this
source category; further testing is needed to confirm the true magnitude of these
emissions.
7-12 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
7.3.3 Electric Arc Furnaces
Electric arc furnaces (EAFs) are used to produce carbon and steel alloys. The
production of steel in an EAF is a batch process, and the input material is typically 100
^ - -
percent scrap. Scrap, alloying agents, and fluxing materials are loaded into the cylindrical,
refractory-lined EAF, and then carbon electrodes are lowered into the EAF. The current of
the opposite polarity electrodes generates heat between the electrodes and through the
scrap. A batch ranges from about 1.5 to 5 hours to produce carbon steel and from 5 to 10
hours to produce alloy steel (U.S. EPA, 1995b).
The melting of scrap ferrous material contaminated with metal working fluids and
plastics containing chlorine provides the conditions conducive to formation of CDD/CDFs.
Tysklind et al. (1989) studied the formation and releases of CDD/CDFs at a pilot 10-ton
electric furnace in Sweden. Scrap ferrous metal feedstocks containing varying amounts of
chlorinated compounds (i.e., PVC plastics, cutting oils, or CaCI2) were charged into the
furnace under different operational conditions (i.e., continuous feed, batch feed into the
open furnace; or batch feed through the furnace lid). During continuous charging
operations, the highest emissions, 1.5-ng Nordic TEQ/dry Mm3 (i.e., after a bag house filter)
were observed with a feedstock comprised of scrap metal with PVC plastics (1.3 g of
chlorine per kg of feedstock). This emission equates to 7.7-ng Nordic TEQ/kg of feedstock.
The highest emissions during batch charging also occurred when the scrap metal with PVC
plastic was combusted (0,3-ng Nordic TEQ/dry Nm3 or 1.7-ng Nordic TEQ/kg of feedstock).
Much lower emissions (0.1-ng Nordic TEQ/dry Nm3 or 0.6-ng Nordic TEQ/kg of feedstock)
were observed when scrap metal with cutting oils containing chlorinated additives (04 g of
chlorine per kg of feedstock) was melted. Although these cutting oil-related emissions
were not significantly different than the emissions observed from the melting of "no-
chlorine" scrap metal, relatively high levels of CDD/CDF (i.e., 110-ng Nordic TEQ/dry Nm3)
were detected in flue gases prior to the bag house. The congener profiles of raw flue gas
samples (i.e., prior to APCD) showed that CDFs, rather than CDDs, were predominant in all
three feedstock types. The congener profile from the test burn with PVC-containing
feedstock showed a higher chlorinated congener content than was observed with the other
feedstocks.
Eduljee and Dyke (1996) used a range of 0.7- to 10-rig TEQ per kg of scrap feed to
estimate national emissions for the United Kingdom. The range was assumed to be
7"13 April 1998
-------
• •„" ' .' '••• ^j I :- DRAFT-DO NOT QUOTE OR
representative of *no chlorine" and "high chlorine" operations. However, little information
was provided in Eduljee and Dyke (1996) on the supporting emission test studies (i.e.,
tested facility operational materials, feed rates, congener-specific emission rates).
Umweltbundesamt (1996) reported stack testing results for a variety of EAFs in
Germany. Sufficient data were provided in Umweltbundesamt (1996) to enable calculation
of TEQ emission factors for six of the tested facilities. Two facilities had emission factors
exceeding 1-ng TEQ/kg of scrap processed, and two facilities had emission factors less
than 0.1-ng TEQ/kg of scrap. The mean emission factor was 1.15-ng TEQ/kg of scrap.
The TEQ concentrations in the stack gases at these facilities (corrected to 7 percent O2)
ranged from less than 0.1- to 1.3-ng TEQ/m3.
In 1995, electric arc furnaces accounted for 40.4 percent of U.S. steel production
(or 38.4 of the total 95.2-million metric tons of raw steel produced) (Fenton, 1996). No
• „ , , ..i, . ' T1 • • • ii , i • • „ •, „ hi . . " , i" i,11"1." 'i , , i< '', , i1 ,!','•«,: i • ,! .,!'. ii'"!' i' h, ' »!!:,', , i; ,.i, i " , i
'« , , ' i „, , •' : "" - ij ,11 ' i '! " i', /,i" • ' ' i Iv1', , ! ' , r !.,'"!: • '' :,''i(! "• .:, ",'K , V „ it'iii » 'i,,, ", •. . I, , '• :
testing of CDD/CDF emissions from U.S. electric arc furnaces has been reported upon
which to base an estimate of national emissions, and the limited European data available
were thus judged inadequate for developing national emission estimates that could be
included in the national inventory. However, a preliminary order of magnitude rough
estimate of potential TEQ annual emissions from U.S. electric arc furnaces can be made by
combining the production estimate of 38.4-million metric tons and the average emission
•P.i "' 'i ' ' ' Ml,'! '„ ' " ''„ " .1,' • • * , i, '' .',i „',,'"i.1'1,:i, » "' ''',,, • Vi „' . - / 'I'hi!"" ,, ,: I- • • . I
factor derived from the data reported in Umweitbundesamt (1996) for six EAFs (i.e., 1.15-
ng TEQ/kg scrap). This calculation yields an annual emission estimate of 44.3 g of TEQ in
1995, which, when rounded to the nearest order of magnitude to emphasize the
uncertainty in this estimate, results in a value of 10-g TEQ/yr. this estimate should be
regarded as a preliminary indication of'possible emissions from this source category; further
testing is needed to confirm the true magnitude of these emissions.
' -, • N* '" "•• " „; ;' • •:'•.• • " i- ' ''.'<'••''.' •'.•'••'• \
7.4 FERROUS FOUNDRIES
Ferrous foundries produce high strength iron and steel castings used in industrial
machinery, pipes, and heavy transportation equipment. Iron and steel castings are solid
Solutions of iron, carbon, and various alloying materials. Castings are produced by injecting
or pouring molten metal into cavities of a mold made of sand, metal, or ceramic material.
Metallic raw materials are pig iron, iron and steel scrap, foundry returns, and metal turnings
(U,S. EPA, 1995b; 1997b).
!' , ( , ' , '. . . • •
'7-14 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
\
. - • / - - ' ' •
The melting process is performed primarily in cupola (or blast) furnaces and to a
lesser extent in electric arc furnaces (EAF). About 70 percent of all iron castings are
produced using cupolas, while steel foundries rely almost exclusively on EAFs or induction
furnaces for melting. The cupola is typically a vertical, cylindrical steel shell with either a
refractory-lined or water-cooled inner wall. Charges are loaded at the top of the unit; the
iron is melted as it flows down the cupola, and is removed at the bottom. {EAFs are
discussed in Section 7.3.3.) Electric induction furnaces are batch type furnaces in which
the charge is melted fay a fluctuating electromagnetic charge produced by electrical coils
surrounding the unit (U.S. EPA, 1995b; 1997b).
Iron and steel foundries, particularly those using EAFs, are highly dependent on iron
and steel scrap. Of the estimated 72-million metric tons of iron and steel scrap consumed
by the iron and steel industry in 1995, 25 percent (or 18-miHion metric tons) were used by
ferrous foundries. The other 75 percent were used by primary ferrous metal smelters
(principally those using EAFs) (U.S. Geological Survey, 1997b). Thus, foundries face the
same potential for CDD/CDF emissions as EAFs because of use of scrap containing
chlorinated solvents, plastics, and cutting oils. (See Section 7.3.3.) The potential for
formation and release of CDD/CDFs during the casting process (i.e., pouring of molten
metal into molds and cores comprised of sand and various organic binders and polymers) is
not known.
The results of emissions testing have been reported for only one U.S. ferrous
foundry (CARB, 1993a - as reported in U.S. EPA, 1997b). The tested facility consisted of
a batch-operated, coke-fired cupola furnace charged with pig iron, scrap iron, scrap steel,
coke, and limestone. Emission control devices operating during the testing were an oil-fired
afterburner and a baghouse. The congener and congener group emission factors derived
from the testing are presented in Table 7-5. The congener and congener group profiles are
presented in Figure 7-4. The calculated TEQ emission factor for this set of tests is 0.37
ng/kg of metal charged to the furnace.
Umweltbundesamt (1996) reported stack testing results for a variety of ferrous
foundries in Germany. Sufficient data were provided in Umweltbundesamt (1996) to
enable calculation of TEQ emission factors for eight of the tested facilities. Three facilities
had emission factors exceeding 1 ng/kg of metal charge, and four facilities had emission
7-15
April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
factors less than 0.1 ng TEQ/kg of metal charge; the emission factors span more than four
orders of magnitude. The mean emission factor was 1,26-ng TEQ/kg of metal feed.
Based on the wide range of emissions for the tested German foundries reported in
Urnweltbundesamt (1996), the confidence in the degree to which the one tested U.S.
facility represents the mean emission factor for the approximate 1,000 US. foundries is
considered very low. Therefore, the limited data available were thus judged inadequate for
developing national emission estimates that could be included in the national inventory.
However, a preliminary order of magnitude estimate of potential TEQ annual emissions from.
U.S. ferrous foundries can be made by combining the mean emission factor derived from
the data reported in Urnweltbundesamt (1996) for eight foundries (1.26-ng TEQ/kg of metal
feed) with an activity level for U.S. foundries. In 1995, U.S. shipments from the
approximate 1,000 U.S. ferrous foundries were 13.9-million metric tons of which about 90
percent were iron castings and 16 percent were steel castings (Fenton, 1996). This
calculation yields an annual emission estimate of 17.5 g of TEQ in 1995, which, when
rounded to the nearest order of magnitude to emphasize the uncertainty in this estimate,
results in a value of 10-g TEQ/yr. This estimate should be regarded as a preliminary
indication of possible emissions from this source category; further testing is needed to
confirm the true magnitude of these emissions.
7.5. SCRAP ELECTRIC WIRE RECOVERY
The objective of wire recovery is to remove the insulating material and reclaim the
metal (e.g., copper, lead, silver, and gold) comprising the electric wire. The reclaimed
metal is then sold by the recovery facility to a secondary metal smelter. Wire insulation
commonly consists of a variety of plastics, asphalt-impregnated fabrics, or burlap. In
ground cables, chlorinated organics are used to preserve the cable casing. The combustion
of chlorinated organic compounds in the cable insulation, catalyzed by the presence of wire
metals such as copper and iron can lead to the formation of CDDs and CDFs (Van Wijnen et
al., 1992).
IIP' ! '" l|!."!' 'ISl '' ' , II I' '
Although in the past, scrap electric wire was commonly treated via thermal
processing to burn off the insulating material, industry and trade association representatives
state that current recovery operations typically no longer involve thermal treatment, but
Instead involve mechanical chopping the scrap electric wire into fine particles. The
7-16 April 1998
-------
DRAFT-rDO NOT QUOTE OR CITE
insulating material is then removed by air blowing and gravitational settling of the heavier
metal fraction (telephone conversation between R. Garind, Institute of Scrap Recycling
Industries, and T. Leighton, Versar, Inc. on March 2, 1993; telephone conversation
between J. Sullivan, Triple F. Dynamics, and T. Leighton, Versar, Inc., on March 8, 1993).
Dioxin-like compounds emitted to the air from a scrap wire reclamation incinerator
were measured from a facility during EPA's National Dioxin Study of combustion sources
(U.S. EPA, 1987a). The tested facility was determined to be typical of this industrial
source category at that time. Insulated wire and other metal-bearing scrap material were
fed to the incinerator on a steel pallet. The incinerator was operated in a batch mode, with
the combustion cycles for each batch of scrap feed lasting between 1 and 3 hours.
Incineration of the material occurred by burning natural gas. Although most of the wire had
a tar-based insulation, PVC-coated wire was also fed to the incinerator. Temperatures
.during combustion in the primary chamber furnace were about 570°C. The tested facility
was equipped with a high temperature natural gas-fired afterburner (98O to 1,090°C),
Emission factors estimated for this facility are presented in Table 7-6. The TEQ emission
factor (based only on 2,3,7,8-TCDD, 2,3,7,8-TCDF, OCDD, and OCDF) is 2.5-ng TEQ/kg
scrap feed. Figure 7-5 presents a congener group profile based on these emission factors.
These emission factors from the U.S. EPA (1987a) study are in general agreement
with those reported by Bremmer et al. (1994) for three facilities in The Netherlands, which
have subsequently ceased operations. Emission rates at a facility burning underground
cables and cables containing PVC ranged from 3.7-ng TEQ/kg to 14-ng TEQ/kg. The
emission rate at a second facility ranged from 21-ng TEQ/kg of scrap (when burning copper
core coated with greasy paper) to 2,280-ng TEQ/kg of scrap (when burning lead cable).
The third facility, which burned motors, was reported to have an emission rate of 3,300-ng
TEQ/kg of scrap. Based on these measurements, Bremmer et al. (1994) used emission
rates of 40-ng TEQ/kg of scrap and 3,300-ng TEQ/kg of scrap for estimating national,
emissions in The Netherlands for facilities burning wires/cables and those burning motors.
Although limited emission testing has been conducted~at one U.S. facility, the
activity level for this industry sector In reference years 1987 and 1995 is unknown;
therefore, an estimate of national emissions cannot be made. It is uncertain how many
facilities still combust scrap wire in the United States. Trade association and industry
representatives state that only minimal quantities of scrap wire are still burned by U.S.
7-17
April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
scrap wire recovery facilities. However, a recent inventory of CDD/CDF sources in the San
1 V ':. "" ..... ^ * ' , ' ',:..'- ............ i V 1 I'v :i; :;;•!: Vt^ .:•'•.' ..... :, \ ..... ••'•.;••. ; [ ..- -,
Francisco Bay area noted that two facilities in the Bay area thermally treat electric motors
to recover electrical windings (BAAQMD, 1996).
In addition to releases from regulated recovery facilities, CDD/CDF releases from
small-scale burning of wire at unregulated facilities and open air sites have occurred; the
current magnitude of small-scale, unregulated burning of scrap wire in the United States is
not known. For example, Harnly et al. (1 995) analyzed soil/ash mixtures from three closed
metal recovery facilities and from three closed sites of open burning for copper recovery
near a California Insert town, the geometric mean of the total CDD/CDF concentrations at
the facility sites and the open burning sites was 86,000 and 48,500 ng/kg, respectively.
........ , ...... , jj , , , • , , , ,
The geometric mean TEQ concentrations were 2,900- and 1,300-ng TEQ/kg, respectively.
A significantly higher geometric mean concentration (19,000 ng TEQ/kg) was found in fly
ash located at two of the facility sites. The congener-specific and congener group results
from this study are presented in Table 7-7. The results show that the five dominant
congeners in the soil/ash samples at both the facility and 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-TCDF. A slightly different profile
ii!'1' , " ' •' VHi'iili. ' ,'.'",'.,',:,' ,,i i:, „,,'.„•„" '; i 'I' ', '••'• ' ' 'Mi11,!,, ' ,.!,', ........ „.',.,'! I
was observed in the fly ash samples with 1,2,3,7,8-PeCDF and 1 ,2,3,4,7,8,9-HpCDF
replacing OCDD, and 2,3,7,8-TCDF as dominant congeners.
Van Wijnen et al. (1992) reported similar results for soil samples collected from
Unpermitted former scrap wire and car incineration sites in The Netherlands. Total
CDD/CDF concentrations in the soil ranged from 60 to 98,000 ng/kg, with 9 of the 1 5 soil
samples having levels above 1,000 ng/kg. Chen et al. (1986) reported finding high levels
of CpD/CpFs in residues from Ppen air burning of wire in Taiwan, and Huang et al. (1 992)
reported elevated levels in soil near wire scrap recovery operations in Japan. Bremmer et
al. (1 994) estimated an emission rate to air of 500-ng TEQ/kg of scrap for illegal,
unregulated burning of cables in The Netherlands.
7.6. DRUM AND BARREL RECLAMATION FURNACES
1 ". » ii iii i r ; • • '
Hiitzinger and Fiedler (1 991 b) reported detecting CDD/CDFs in stack gas emissions
from drum and barrel reclamation facilities at levels ranging from 5 to 27 ng/m3. EPA
measured dioxin-like compounds in the stack gas emissions of a drum and barrel
reclamation furnace as part of the National Dioxin Study (U.S. EPA, 1987a).
, !;;!; '""•• , ••••';:,'.;/ '.' '..' 7-18' i '/, ....... ' ..' ,'] ^.," '„ ' \ April 1998'
ii ;•;• t, 'Aiiiii1:1! » ......
-------
DRAFT-DO NOT QUOTE OR CITE
Drum and barrel reclamation furnaces operate a Burning furnace to thermally clean
used steel 55-gallon drums of residues and coatings. The drums processed at these
facilities come from a variety of sources in the petroleum and chemical industries. The
thermally cleaned drums are then repaired, repainted, relined, and sold for reuse. The drum
.burning process subjects used drums to an elevated temperature in a tunnel furnace for a
sufficient time so that the paint, interior linings, and previous cpntents are burned or
disintegrated. The furnace is fired by auxiliary fuel. Used drums are loaded onto a
conveyor that moves at a fixed speed. As the drums pass through the preheat and ignition
zone of the furnace, additional contents of the drums drain into the furnace ash trough. A
drag conveyor moves these sludges and ashes to a collection pit. The drums are air cooled
as they exit the furnace. Exhaust gases from the burning furnace are typically drawn
through a breeching fan to a high-temperature afterburner.
The afterburner at the facility tested by EPA operated at an average of 827°C during
testing and achieved a 95 percent reduction in CDD/CDF emissions (U.S. EPA, 1987a).
Emission factors estimated for this facility are presented in Table 7-8. Based on the
measured congener and congener group emissions, the average TEQ emission factor was
estimated in U.S. EPA (1997b) to be 49.4-ng TEQ per drum. The congener group profile is
presented in Figure 7-6.
Approximately 2.8- to 6.4-million 55-gallon drums are incinerated annually in the
United States (telephone conversation between P. Rankin, Association of Container
Recbnditioners, and C. D'Ruiz, Versar, Inc., December 21, 1992). This estimate is based
on the following assumptions: (1) 23 to 26 incinerators are currently in operation; (2) each
incinerator, on average, handles 500 to 1,000 drums per day; and (3) on average, each
incinerator operates 5 days per week, with 14 days downtime per year for maintenance
activities. The weight of 55-gallon drums varies considerably; however, on average, a
drum weighs 38 Ibs (or 17 kg); therefore, an estimated 48- to 109-million kg of drums are
estimated to be incinerated annually. Assuming that 4.6-milliori drums are burned each
year (i.e., the midpoint of the range) and applying the mean emission factor developed
above (i.e., 49.4-ng TEQ per drum), the estimated annual emission of TEQ is 0.23 grams
per year of TEQ. No activity level data are available that would enable annual emission
estimates to be made specifically for reference years 1987 and 1995.
7-19
April 1998
-------
DRA.FT-DO NOT QUOTE OR CITE
A "low" confidence rating is assigned to the activity level estimate because it is
based an expert Judgement rather than a published reference. A "low" confidence rating is
also assigned to the emission factor, because it was developed from stack tests conducted
i •
at just one U.S. drum and barrel furnace and, thus, may not represent average emissions
from current operations in the United States. Based on these confidence ratings, the
estimated range of potential annual emissions is assumed to vary by a factor of 10
between the Tow and high ends of the range. Assuming that the best estimate of annual
emissions (0.23-g TEQ/yr) is the geometric, mean of this range, then the range is calculated
to be 0.07-to b.73-g TEQ/yr.
7-20 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 7-1. CDD/CDF Emission Factors for Secondary Aluminum 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-HxCDFV
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 TEQ
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)
(Ref. 1)
<0.01
0.02 \
0.05
0.13 :
0.15
0.51
0.42
, 0.44
0.06
0.17
0.32
0.1 1
0.02
0.30
0.07
0.03
0.30'
0.26
NR
NR
NR
NR
0.42
NR
NR
NR
NR
0.30
NR
Mean Facility
Emission Factor
(ng/kg scrap feed)
(Ref. 2)
0.13
0.39
OOA
»^*r
0.86
1.26
7,67
14.97
0.74
1.51
2.44
2.44
2.69
1.02
3.82
11.39
5.50
30.40
3.22
3.30
4.91
1 1 .45
14,71
14.97
29.67
28.73
32.23
39.44
30.40
209.81
Mean Facility
Emission Factor
(ng/kg scrap feed)
(Ref. 3)
0.51
1.19
IOC
.ob
1.52
2.51
2.60
1.01
14.20
10.47-
1 1 .Q6
21.84
7.10
0.47
7.09
14.61
1.21
3.15
12.95
46.03 .
28.07
35.51
6.01
1.01
161.80
'* 222.75
1 1 5.32
39.94
3.15
659 60
Mean Facility
Emission Factor
(ng/kg scrap feed)
(Ref. 4)
2.17
3.84
2.88
5.39
7.22
1.8.01
NR .
47.12
20.01
29.60
52.32
16.31
1 .20
22.96
35.29
5.17
18.77
36.03
NR
NR
• NR
NR
NR
NR
NR
NR
NR
18.77
NR
NR = Not reported.
Sources: Ref. 1: Advanced Technology Systems, Inc. (1995)
Ref. 2: U.S. EPA (1995h)
Ref. 3: Galson Corporation (1995)
Ref. 4:-Envisage Environmental, Inc. (1995)
7-21
April 1998
-------
,1 jj,
DRAFT-DO NOT QUOTE OR CITE
2,3,7,8-TCDD
1,2,3.7.8-PcCDD
i.2,3,4,7,8-itxCDD
1,2,3,6,7,8-HxCDr>
1,2,3,7,8,9-HxCDp
1,2,3.4.6,7,8-HpCDD
1,2,3.4,6,7,8,9-OCDD
2,3.7,8-TCpF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
• I'llHB! ':,'•'• I
1,2,3,4.7,8-HxCDF
1,2,3,6.7,8-HxCDF
1,2,3,7,8,9-HxCpF
2,3,4,6,7,8-HxCDF
1^^.4,6,7,8-HpCDF
Ratio (congener emission factor / total CDD/CDF emission factor)
0.01 0.02 0.03 0.04 O.OS 0.06 0.07
0.08
Ratio (congener group emission factor / total CDD/CDF emission factor)
0.05 0.1 0.15 0.2
0.25
OCDF
Sources: U.S. EPA (1995h); Galson Corporation (1995)
Figure 7-1., Congener and Congener Group Profiles for Air Emissions"
from Secondary Aluminum Smelters
7-22
April 1998
-------
DRAFTS-DO NOT QUOTE OR CITE
Table 7-2. CDD/CDF Emission Factors for a Secondary Copper Smelter
'•
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
Mean Facility Emission Factor3
127
NR
' NR
NR
NR
NR
1,350
2,720
NR
NR
NR
/ NR
NR
NR
NR
NR
2,520
NR
NR
779b
736
970
1,260
2,O8O
1,350
13,720
8,640
4,240
3,420
2,520
38 890
NR = Not reported.
a No nondetected values were reported for 2,3,7,8-TCDD, 2,3,7,8-TCDF, or any congener group in the
three test runs.
Estimated in U.S. EPA (1995c) based on the measured congener and congener group emissions.
Source: U.S. EPA (1987a).
7-23
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
' ' • "
Ratio (congener group emission factor / total CDD/CDF emission factor)
Source: U.S. EPA (1987c)
! "
: •*.
Figure 7-2. Congener Group Profile for Air Emissions from a Secondary Copper Smelter/Refiner
, I"
7-24
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 7-3. 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 TEQ (nondetects = 0)
Total TEQ (nondetects = 1/2 DL)
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total f CDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF (nondetects = 0)
Total CDD/CDF (nondetects = 1/2 DL)
Blast Furnace (Ref. A)
(ng/kg lead produced)
before ,
scrubber
2.11
0.99
0.43
, 0.99
1 .55
2.06
1 .40
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
8.32
74.33
39.29
20.05
4.20
1.39
145.71
69.59
19.73
4.74
1.39
380.43
380.44
after
scrubber
0.25
0.03
0.00
0.03
0.03
0.08
0.39
0.93
0.43
0.36
0.37
0.11
0.00
0.11
0.19
0.06
0.18
0.82
2.74
0.63
0.71
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/reverb (Ref. B)
(ng/kg lead produced)
before
0.00
0.00
0.00
0.00
0.00
0.10
0.57
1 .46 -
0.24
0.31
0.63
0.19
0.00
0.15
0.48
0.00
0.29
0.68
3.75
0.41
0.44
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 ,
0.00
0.00
0.00
0.00
0.00
0.06
0.55
0.49
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.61
0.51
0.05
0.10
1.58
0.16
O.O2
0.09
0.55
4.71
0.36
0.19
0.01
0.00
7.66
Rotary kiln (Ref. C)
before
0.10
0.01
0.00
.*0.00
0.00
0.00
0.24
0.40
0.14
0.14
0.11
0.02
0.04
0.00,
0.03
0.00
0.00
0.35
0.88
0.24
0.25
3.40
0.29
0.10
0.01
6.24
10.82
1.69
0.15
0.05
0.00
16.76
after
0.24
0.00
O.OQ
0.00
0.00
0.22
.2.41
1.20
0.40
0.46
0.27
0.10
0.13
0.00
0.13
0.00
0.00
2.87
2.68
0.66
0.69
7.90
0.27
0.23
0.29
2.41
28.57
5.04
0.73
0.14
0.00
45.57
Sources: Ref. A: U.S. EPA (1995e); Ref. B: U.S. EPA (1992e); Ref. C: U.S. EPA (1995d)
Note: Except where noted, emission factors were calculated assuming nondetected values are zero.
7-25
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
O.O1 O.O2 O.O3 O.O4 O.OS O.O6 O.O7 O.QS O.O9
O.I
2.3.7.S-TCDD
1 ^,3,7,8-PcCDD
I ,2,3,4,7,8-HxC:DD
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
i, ' ' : 'e/'Ki, i '
2,3,4,7,8-PeCDF
1^2,3,4,7.8-H%CDF
1 ^Z^ ,«.7,8-HxCDF
2.3.4,6,7.8-HxCDF
1^,3,4,7.8.9-HpCDF
1
•
^———m ' ' —
«••••— ^-,
^^^^^^Hasj
•-^^^^
-fa
•
Ratio (congener group emission factor / total CDD/CDF emission factor)
.„ ' q:il, , , ', „„ 0.2 , '/,... :i,o.3,'" '[' ' . '. i0.4,."",_' '.; 0.5
0.6
«1: itialiii^fc&fr^i^^rti'Cri^^ |
^^H Blast furnace tS^-A Reverb/co-located furnace
Source: U.S. EPA (1992e); U.S. EPA (1995d); U.S. EPA (199Se)
Figure 7-3. Congener and Congener Group Profiles for Air Emissions from Secondary Lead Smelters/Refiners
7-26
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 7-4. Operating Parameters for U.S. Iron Ore Sinter Plants
Company,
A.K. Steel Corp.
A.K. Steel Corp.
Bethlehem Steel
Bethlehem Steel
Geneva Steel
Inland Steel
LTV Steel.
U.S. Steel
Weirton Steel
Wheeling-Pittsburgh
Steel
WCI Steel
Location
/ '
Middleton, 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
TOTALS
Capacity
(1,000
MT/yr)
9O7
816
2,676
3,856
816
1,089
1,270
3,992
1,179
519
477
17,597
<
Grate
Area
(sq. m.)
71.3'
75.0
187.7
353.0
113.7
124.9
124.9
361.2
163.9
49.7
59 9*
1,685
Waste Gas
Fan Capacity
(1,000 m3/hr)
517
289
1,160
3,398
805
748
NA
'722
668
340
NA
Volumetric
Flow Rate
(m3/m2-hr)
7,251
3,852
6,184
9,625
7,082
5,987
NA
1,999
4,074
6,837
NA
* =. Grate area for WCI Steel was calculated using the average ratio of capacity to grate area for the Geneva Steel
and Inland Steel facilities both of which were constructed by the same builder (i.e., Dwight Lloyd).
NA = Not avaiable.
Sources: Metal Producing (1991; 1996)
7-27
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 7-5. CDD/CDF Emission Factors for a 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 TEQ
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)
(CARB, 1993a)
0.033
0.086
NR
0.051
NR
0.093
NR
0.520
0.305
0.350
0.190
0.170
NR
0.101
0.193
NR
0.059
0.262
1 .888
0.372
3.96
1.76
0.55
0.19
NR
25.8
850
1.74
0.24
0.06
884.3
MR = Not reported.
Source: CARB (1993a) (as reported in U.S. EPA,J997b)
7-28
April 1998
-------
DRAFT-J)O NOT QUOTE OR CITE
Ratio (congener emission factor / total CDD/CDF emission factor)
O.O1 O.O2 O.O3 ' O.O4 O.O5 O.O6 O.O7 O.O8 O.O9
O.I
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^,7.8-PeCDF
2,3,4,7,8-PeCDF
1.2.3.4,7,8-HxCDF
1 Ji,3 ,6,7,8-HxCDF
1^,3,7,8,9-HxCDF
, 2,3,4,6,7,8-HxCDF
1^,3,4.6,7,8-HpCDF
1 ^,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Ratio Ccongener group emission factor / total CDD/CDF emission factor)
0.2 . 0.3 • 0.4 0.5
0.6
Source: CA.RB (,1993s.) (as reported in U.S. EPA, 1997b)
Figure 7-4. Congener and Congener Group Profiles for Air Emissions from a Ferrous Foundry
7-29
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
fable 7-6. CDD/CDF Emission Factors for a Scrap Wire Incinerator
Jliisi! , '>• •• I1'1,, .: '•" . . ''•' . '.;•„"£:, '", C-'' ?'•'' , '": ' "• '' !"! ' ." *••!• :••.••'' t
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
Mean Facility
Emission Factor a
(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
NR
4.42
13.7
71.1
347
1 ,000
107
97.4
203
623
807
3,273
NR =• Not reported
h, . ' :",!,ii;;;. . " "" L '. "'i .'; ; ' " ; » i ' ,, '• • ' "I1 »''• • •,. .'' i ,i!!; '' „ i, .
* No nondetected values were reported for 2,3,7,8-TCDD, 2,3,7,8-TCDF, or any congener group in
the three test runs. . •
Source: U.S. EPA (1987a)
7-30
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener group emission factor / total CDD/CDF emission factor)
0 °-05 0.1 0.15 0.2 0.25 . 0.3
0.35
Source: U.S. EPA (1987a)
Figure 7-5. Congener Group Profile for Air Emissions from a Scrap Wire Incinerator
7-31
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 7-7. Geometric Mean CDD/CDF Concentrations in Fly Ash and Ash/Soil at Metal Recovery Sites
Congener/Congener Group
2,3,7.8-TCOD
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
OCOD
2,3,7.8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PcCDF
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 OCDO
Total TCDF
Total PeCDF
Total HxCDF
Total HpCOF
Total OCDF
Total TEQ
Total CDD/CDF
Metal Recovery Facilities
Fly ash (2 sites)
Geom.
mean
teg/kg)
*
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
*
2,000
4,000
24,000
18,000
23,000
110,000
88,000
110,000
100,000
19,000
510,000
Relative %
of Total
CDD/CDF
0.1%
0.2%
0.5%
0.3%
2.4%
3.5%
2.9%
6.9%
2.0%
9.0%
2.4%
1.0%
1.0%
13.9%
4.9%
19.6%
.
0.4%
0.8%
4.7%
3.5%
4.5%
21.6%
17.3%
21.6%
19.6%
Ash/Soil (3 sites)
Geom.
mean
tog/kg)
*
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
*
1.4
2.7
4.1
7.2
14
12
12
17
14
2.9
85
Relative %
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%
.
1.6%
3.2%
4.8%
8.5%
16.5%
14.1%
14.1%
20.0%
16.5%
Open Burn Sites
Ash/Soil (3 sites)
Geom.
mean
(Atg/kg)
*
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
*
2.8
0.98
2.0
3.4
5.6
7.0
7.6
7.4
6.6
1.3
48.5
Relative %
of Total
CDD/CDF
0.5%
0.3%
0.7%
0.8%
2.5%
7.0%
3.5%
1.2%
1.4%
5.6%
1.6%
1.4%
1.0%
8.9%
1.5%
13.6%
*
5.8%.
2.0%
4.1%
7.0%
11.5%
14.4%
15.7%
15.3%
13.6%
* «• Analytical method utilized had low sensitivity for TCDDs; results were not reported.
Source: Harnly et al. (1995)
7-32
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 7-8. CDD/CDF Emission Factors for a Drum and Barrel Reclamation Furnace
Congener/Congener Group
2,3,7,8-TGDD
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 , ,
Mean Facility
Emission Factor3
(ng/drum)
2.09
NR
NR
MR '
liHi
NR
NR
37.5
36,5
NR
NR
NR
NR
NR
NR
NR
NR
22.4,
NR
NR
49.4b
,50.29
29.2
32.2
53.4
37.5
623
253
122
82.2
22.4
1,303 >
NR = Not reported. .
a No nondetected values were reported for 2,3,7,8-TCDD, 2,3,7,8-TCDF, or any congener group in.
the three test runs. ,
Estimated in U.S. EPA (1995c) based on the measured congener arid congener group emissions.
Source: U.S. EPA (1987a).
7-33
April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
Ratio (congener group emission factor / total CDD/CDF emission factor)
0.1 0,2 0.3 0.4 0.5
0.6
Source: U.S. EPA (1987a)
Figure 7-6. Congener Group Profile for Air Emissions from a Drum Incinerator
7-34
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES
8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS
In March of 1988, EPA and the U.S. pulp and paper industry jointly released the
results from a screening study that provided the first comprehensive data on formation and
discharge of CDDs and CDFs from pulp and paper mills (U.S. EPA, 1988'a). This early
screening study of five bleached kraft mills ("Five Mill Study") confirmed that the pulp
bleaching process was primarily responsible for the formation of the CDDs and CDFs. The
study results showed that 2,3,7,8-TCDD was present in seven of nine bleach pulps, five of
five wastewater treatment sludges, and three of five treated wastewater effluents. The
study results also indicated that 2,3,7,8-TCDD and 2,3,7,8-TCDF were the principal CDDs
and CDFs formed.
• To provide EPA with more complete data on the, release of these compounds by the
U.S. industry, EPA and the U.S. pulp and paper industry jointly conducted a survey during
1988 of 104 pulp and paper mills in the United States to measure levels of 2,3,7,8-TCDD
and 2,3,7,8-TCDF in effluent, sludge, and pulp (U.S. EPA, 1990a). This study, commonly
called the 104-Mill Study, was managed by the National Council of the Paper Industry for
Air and Stream Improvement, Inc. (NCASi) with oversight by EPA, and included all US.
mills where chemically produced wood pulps were bleached with chlorine or chlorine
derivatives. The final study report was released in July 1990 (U.S. EPA, 1990a).
An initial phase of the 104-Mill Study involved the analysis of bleached pulp (10
samples), wastewater sludge (9 samples), and wastewater effluent (9 samples) from eight
kraft mills and one sulfite mill for all 2,3,7,8-substituted CDDs and CDFs. These analyses
were conducted to test the conclusion drawn in the Five-Mill Study that 2,3,7,8-TCDD and
2,3,7,8-TCDF were the principal CDDs and CDFs found in pulp, wastewater sludge, and
wastewater effluent on a toxic equivalents basis. Although at the'time of this study there
were no reference analytical methods for many of the 2,3,7>8-substituted CDDs/CDFs, the
-data obtained were considered valid by EPA for the purposes intended based upon the
identification and quantification criteria used, duplicate sample results, and limited matrix
spike experiments. Table 8-1 presents a summary of the results obtained in terms of the.
median concentrations and the range of concentrations observed for each matrix (i.e., pulp,
/• i
sludge, and effluent). Figures 8-1 through 8-3 present congener profiles for each matrix
.8-1
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
(normalized to total CDD/CDF and to total TEQ) using the median reported concentrations.
Based on examination of the raw/, mill-specific data, EPA (1990a) concluded that the
cdrigener profiles were fairly consistent across matrices within mills and that 2,3,7,8-TCDD
and 2,3,7,8-TCDF account for the majority of TEQ in the samples. Using the median
concentrations and treating nondetected values as either zero or the detection limit, EPA
(1990a) demonstrated that 2,3,7,8-TCDD and 2,3,7,8-TCDF accounted for 92.8 to 99.0
percent of the total TEQ found in pulp, 92.7 to 95.8 percent of the TEQ in sludge) and
72.7 to 91.7 of the TEQ in effluent.
A similar full-congener analysis study was reported by IMCASI for samples collected
from eight mills during the mid-1990s {Gillespie, 1997). The results of these analyses are
presented in Table 8-2. The frequencies of detection of 2,3,7,8-TCDD and 2,3,7,8-TCDF
were significantly lower than in the previous i£>88 study. Therefore, deriving meaningful
summary statistics concerning the relative importance of 2,3,7,8-TCDD and 2,3,7,8-TCDF
to the total TEQ is difficult. Treating all nondetected values as zero indicates that 2,3,7,8-
TCDD and 2,3,7,f-TCDF may account for 91 percent of the total effluent TEQ, 46 percent
of the total sludge TEQ, and 87 percent of the total pulp TEQ. Because of the high
frequency of nondetects, treating all nondetected values as the detection limits indicates
that 2,3,7,8-TCDD and 2,3,7,8-TCDF account for only 12 percent of the total effluent
V1! : .'"' I-"' ii II I '"•' \,r:;'.:; ',.J,i:';".":r:i •"•'•' IVi' '''• •-,«ii1"re;:;f:.,*••'•. KW:(••'"'• 1' . I
TEQ, 14 percent of the total sludge TEQ, and 12 percent of the total pulp TEQ.
In 1992, die pulp and paper industry conductedfits own NCASI-coordinated survey
of 2,3,7,8-TCDD and 2,3,7,8-TCDF emissions. The collected data were summarized and
analyzed in a report entitled Summary of Data Reflective of the Pulp and Paper Industry
Progress in Reducing the TCDD/TCDF Content of Effluents, Pulps, and Wastewater
Treatment Sludges (NCASI, 1993). Ninety-four mills participated in the NCASI study, and
NCASl assumed that the remaining 10 (of 104) operated at the same levels as measured in
the 1988 104 Mill Study. All nondetected values were counted as half the detection limit.
If detection limits were not reported, they were assumed to be 10 ppq for effluent and 1
ppt for sludge or bleached pulp. The data used in the report were provided by individual
pulp and paper companies that had been requested by NCASI to generate the data using
the same protocols used in the 104-Mill Study. NCASI (1993) reported that the pulp and
paper industry had taken numerous steps to reduce CDD/CDF releases since 1988, and that
. .
8-2 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
the 1992 survey results were more reflective of releases at the end of 1992 than the data
generated in the 104-Mill Study.
As part of its ongoing efforts to develop revised effluent guidelines and standards
for the pulp, paper, and paperboard industry, EPA in 1993 published the Development
Document for the guidelines and standards being proposed for this industry (U.S. EPA,
1993d). The Development Document presents estimates of the 2,3,7,8-TCDD and 2,3,7,8-
TCDF annual discharges in wastewater from the mills in this industry as of January 1,
1993. EPA used the most recent information about each mill from four data bases (104-
Mill Study, EPA short-term monitoring studies at 13 mills, ,EPA long-term monitoring studies
at 8 mills, and industry self-monitoring data submitted to EPA) to estimate these
discharges. The 104-MHI Study data were used only for those mills that did not report
making any process changes subsequent to the 104-Mill Study and did not submit any
more recent effluent monitoring data.
Gillespie (1994; 1995) reported the results of 1993 and 1994 updates, respectively,
to the 1992 IMCASI survey. As was the case in the 1992 survey, companies were
requested to follow the same protocols for generating data used in the 104-Mill Study.
Gillespie (1994; 1995) reported that less than 10 percent of mills had 2,3,7,8-TCDD and
2,3,7,8-TCDF concentrations in effluent above the nominal detection limits of 10 ppq and
100 ppq, respectively. Similar results were obtained in the short- and long-term sampling
reported for 18 mills in U.S. EPA (1993d); 2,3,7,8-TCDD was detected at four mills, and
2,3,7,8-TCDF was detected at nine mills. Gillespie (1994) reported that wastewater
sludges at most mills (i.e., 90 percent) contained less than 31 ppt of 2,3,7,8-TCDD and
less than 100 ppt of 2,3,7,8-TCDF. GilJespie (1995) also reported that 90 percent of the
mills reported 2,3,7,8-TCDD and 2,3,7,8-TCDF concentrations in sludge of less than 17 ppt
and 76 ppt, respectively, in 1994. U.S. EPA (1993d) reported similar results but found
detectable levels of 2,3,7,8-TCDD and 2,3,7,8-TCDF in sludges from 64 percent and 85
percent of the facilities sampled, respectively. Giljespie (1994) reported that nearly 90
percent of the bleached pulps contained less than 2 ppt of 2,3,7,8-TCDD and less than 160
ppt of 2,3,7;8-TCDF. Gillespie (1995) reported that 90 percent of the bleached pulps
contained 1.5 ppt or less of 2,3,7,8-TCDD and 5:9 ppt or less of 2,3,7,8-TCDF. The final
levels in white paper products would correspond to levels in bleached pulp, so bleached
paper products would also be expected to contain less than 2 ppt of 2,3,7,8-TCDD.
8-3 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
;,;;' , , lyjfiii1 , . . ',> . . • ;..'.•• ' "'• " ;, •:• ,' •< '• :„ •••' • •' ' "a . .lij' "' .; . - i »
Overall, a 92 percent reduction in TEQ generation from 1988 to 1993 was reported by
1 *;, i; in, , ;I_;JH , ,. • ••. • f' , ' . V . ' • . ..' jniciv/!1: ;, •'," .(••..'',':' '.' '• >; '• Lii'> ;;,;,' ,; • j,; •• f
Gillespie (1994), with an additional 2 percent reduction reported in 1994 by Gillespie
(1995).
Estimates of National Emissions in 1987 and 1995 - The U.S. annual discharges of
2,3,7,8-TCDD, 2,3,7,8-TCDF, and TEQs due to these two compounds are summarized in
Table 8-3 for each of the five surveys discussed above. The release estimates for 1994
from Gillespie (1995) and 1988 from U.S. EPA (1990a) are believed to best represent
emissions in the reference years 1995 and 1987, respectively. During the period between
the conduct of the 104-Mill Study and the issuance of the U.S. EPA Development
•i ' •• ", . "' i'!:.. i t I1;.. • "i "V LV," ,'i'r- :'. ;,<•' i. i-;;: '•• <1'\ > !''•'• '• > ,J!i '", .
Document (U.S. EPA, 1993d), the U.S. pulp and paper industry reduced releases of
CDD/CDFs primarily by instituting numerous process changes to reduce the formation of
CDD/CDFs during the production of chemically bleached wood pulp. Details on the process
changes implemented are provided in U.S. EPA (1993d) and Gillespie (1995). Because
most of the reduction between 1983 and 1994 can be attributed to process changes of a
pollution prevention nature, it should be expected that the percentage reduction observed in
effluent, sludge, and pulp emissions over this time period should be very similar, which is
indeed the case. Observed percentage reductions in emissions are 92 percent, 89 percent,
and 93 percent for effluent, sludge, and pulp, respectively.
The confidence ratings for these release estimates were judged to be high based on
the fact that direct measurements were made'at virtually all facilities, indicating a high level
of confidence in both the production and emission factor estimates. Based on these high
confidence ratings, the estimated ranges of potential annual emissions for effluent, sludge,
and pulp are assumed to vary by a factor of 2 between the low and high ends of the
ranges. Assuming that the best estimates of annual emissions in 1995 (i.e., the' 1994
estimates presented in Table 8-3) are the geometric means of the likely ranges, then the
ranges are calculated to be 13.8- to 27.6-g TEQ/yr for effluent, 20.0- to 40.0-g TEQ/yr for
sludge, and 17.0- to 34.0-g TEQ/yr for pulp (i.e., TEQs that will enter the environment in
the form of paper products). Assuming that the best estimates of annual emissions in
1987 (i.e., the 1988 estimates presented in Table 8-3) are the geometric means of the
likely ranges, then the ranges are calculated to be 252-to 504-g TEQ/yr for effluent, 243-
to 485-g TEQ/yr forsludge, and'375- to 714-g TEQ/yr for pulp.
8-4 . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
In 1990, the majority of the wastewater sludge generated by these facilities was
landfilled or placed in surface impoundments (75.5 percent), with the remainder incinerated
(20.5 percent), applied to land directly or as compost (4.1 percent), or distributed as a
commercial product (less than 1 percent) (U.S. EPA, 1993e). No more recent (i.e., 1995)
or earlier (i.e., 1987) data on disposition of wastewater sludges are available. Using these
statistics, the best estimate of TEQ applied to land (i.e., not incinerated or landfilled) in
1995 was 1.4 g (i.e., 4.1 percent of 28.4 g), and the range is 1.0- to 2.0-g TEQ/yr. The
central estimate and range for 1987 are 14.1-g TEQ (i.e., 4.1 percent of 343 g) and 16- to
20-g TEQ, respectively.
8.2. MANUFACTURE OF CHLORINE, CHLORINE DERIVATIVES, AND METAL CHLORIDES
No testing of CDD/CDF emissions to air, land, or water from U.S. manufacturers of
chlorine, chlorine derivatives, and metal chlorides have been reported upon which to base
estimates of national emissions. Sampling of graphite electrode sludges from European
chlorine manufacturers indicates high levels of CDFs. Limited sampling of chlorine
derivatives-and metal chlorides in Europe indicates low lever contamination in some
products.
8.2.1. Manufacture of Chlorine
Chlorine gas is produced by electrolysis of brine electrolytic cells. Until the late
1970s, mercury cells containing graphite electrodes were the primary type of electrolytic
process used in the chloralkali industry to produce chlorine. As shown in Table 8-4, high
levels of CDFs have been found in several samples of graphite electrode sludge from
facilities in Europe. The CDFs dominate the CDDs in these sludges, and the 2,3/7,8-
substituted congeners account for a large fraction of the respective congener totals (Rappe
etal., 1990b; Rappe et al., 1991; Rappe, 1993; Strandell et al., 1994). During the 1980s,
titanium metal anodes were developed to replace graphite electrodes (U.S. EPA, 1982a;
Curlin and Bommaraju, 1991). Currently, no U.S. facility.is believed to use graphite
electrodes in the production of chlorine gas (telephone conversation between L. Phillips,
Versar, Inc., and T. Fielding, U.S. EPA, Office of Water, February 1993).
Although the origin of the CDFs in graphite electrode sludge is uncertain,
chlorination of the cyclic aromatic hydrocarbons (such as dibenzofuran) present in the coal
8'5 April 1993
-------
DRAFT-DO NOT QUOTE OR CITE
tar used as a binding agent in the graphite electrodes has been proposed as the primary
source (Strandell et a!., 1994). For this reason, sludges produced using metal electrodes
were not expected to contain CDFs. However, Strandell et ai. (1994) reported the results
of an analysis of a metal electrode sludge from a facility in Sweden, analyzed as part of the
Swedish Dioxin Survey. As with the graphite electrode sludge, this sludge contained high
levels of CDFs {similar to those of the graphite sludge) and primarily nondetectable levels of
CDDs. The sludge showed the same type of CDF congener pattern reported by Rappe et
al. (1991) and Rappe (1993). Strandell et al. (1994) suggested that chlorination of PAHs
present in the rubber linings of the electrolytic cell may have formed the CDFs found in the
one sample analyzed.
Although not regulated specifically for CDD/CDFs, EPA issued restrictions under the
Resource Conservation and Recovery Act (RCRA) on the land disposal of wastewater and
sludges generated by chlorine manufacturers utilizing the mercury cell process and the
diaphragm process (with graphite electrodes) (Waste Codes K071, K073, and K106) (40
CFR 268). In addition, EPA is currently evaluating whether to regulate the chlorine
;/ ' . >1i;[' • •., »' , x« "• •'• • . n'S.v:;:,,,:•• :• ?/-.•• '>;I1:»",!': :; • .'£ j'W i'-1 . •'... ' ! ' "
manufacturing industry as a major source of hazardous air pollutants (HAPs) under Section
112(b) of the Clean Air Act (CAA). As part of this investigation, monitoring of air
emissions for HAPs (including CDD/CDFs) is being performed; preliminary results of the
investigation indicate no detectable emissions of CDD/CDFs (telephone conversation
between G. Sch,W|er, Versar, Inc., and I. Rosario, U.S. EPA, Office of Air Quality Planning
and Standards, April 11, 1996).
8.2.2. Manufacture of Chlorine Derivatives and Metal Chlorides
The limited sampling of chlorine-derivative products indicates that these products
contain very low, if any, concentrations of CDD/CDFs. Rappe et al. (1990c) analyzed a
sample of chlorine bleach consisting of 4.4 percent sodium hypochlorite. Most of the
2,3,7,8-substituted CDD/CDF congeners were below the limits of detection (0.3 to 7 pg/L
for all congeners, except OCDD and OCDF, which were 12 and 20 pg/L, respectively). No
• » '.Mull" i i \ | . ' • j .
2,3,7,8-substituted CDDs were detected. Tetra-, penta-, and hexa-CDFs were detected at
(V , '•• „ "; :/* '!;< . ' : I ! I " I .}'';'. ' . . ;
leve|s of 13 pg/L or lower. The TEQ content of the sample was 4.9-pg TEQ/L. Hutzinger
and Fiedler (1991 a) reported finding no CDD/CDFs at a detection limit of 4 jwg/kg in chlorine
8-6 April 1998
-------
DRAFT--DO NOT QUOTE OR CITE
gas or in samples of 10 percent sodium hypochlorite, 13 percent sodium hypochlorite, and
31-33 percent hydrochloric acid at a detection limit of 1 //g/kg.
Hutzinger and Fiedler (1991 a) reported the results of analyses of samples of FeCI2,
AICI3, CuCI2, CuCI, SiCI4, and TiCI4 for their content of HpCDF, OCDF, HpCDD, and OCDD.
The sample of FeCI3 contained HpCDF and OCDF in the low //g/kg range, but no HpCDD or
OCDD were detected at a detection limit of 0.02 .^g/kg. One of the two samples of AICI3
analyzed also contained a low ^g/kg concentration of OCDF. The samples of CuCI2 and
CuCI contained sub /^g/kg concentrations of HpCDF, OCDF, and OCDD. The results are
presented in Table 8-5,
8.3. MANUFACTURE OF HALOGENATED ORGANIC CHEMICALS
Several chemical production processes generate CDDs and CDFs {Versar, 1985;
Hutzinger and Fiedler, 1991 a)., CDDs and CDFs can be formed during the manufacture of
chlorophenols, chlorobenzenes, and chlorobiphenyls {Versar, 1985; Ree et al., 1988).
Consequently, disposal of industrial wastes from manufacturing facilities producing these
compounds may result in the release of CDDs and CDFs to the environment. Also, the
products themselves may contain these compounds, and when used/consumed, may result
in additional releases to the environment. CDD and CDF congener distribution patterns
indicative of noncombustion sources have been observed in sediments in southwest
Germany and The Netherlands. The congener patterns found suggest that wastes from the
production of chlorinated organic compounds may be important sources of CDD and CDF
contamination in these regions (Ree et al., 1988). The production and use of many of the
chlorophenols, chlorophenoxy herbicides, and PCB products are banned or strictly regulated
in most countries. However, these products may have been a source of the environmental
contamination that occurred prior to the 1970s and may continue to be a source of
environmental releases based on limited use and disposal conditions (Rappe, 1992a).
8.3.1. Chlorophenols
Chlorophenols have been widely used for a variety of pesticidal applications. The '
higher chlorinated phenols (i.e., tetrachlorophenol and pentachlorophenol) and their sodium
salts have been primarily used for wood preservation. The lower chlorinated phenols have
been used primarily as chemical intermediates in the manufacture of other pesticides. For
8"7 . , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
example, 2,4-dichlorophenol is used to produce the herbicides 2,4-Dichlorophenoxyacetic
acid (2,4-D), 4-{2,4-Dichlorophenoxy)butanoic acid (2,4-DB), 2-(2,4-DichIorophenoxy)-
propanoic acid (2,4-DP), Nitrophen, Genite, and Zytron, while 2,4,5-trichlorophenol was
used to produce hexachlorophene, 2,4,5-T, Silvex, Erbon, Ronnel, and Gardona (Oilman et
al., 1988; Hutzinger and Redler, 1991 a). [See Sections 8.3.7 and 8.3.8 for information on
EPA actions to control CDD/CDF contamination of pesticides (including pentachlorophenol
and its salts) and to obtain additional data on CDD/CDF contamination of pesticides.]
The two major commercial methods used to produce chlorophenols are: (1)
electrophilic chlorination of molten phenol by chlorine gas in the presence of catalytic
amounts of a metal chloride and organic chiorination promoters and stabilizers; and (2)
alkaline hydrolysis of chlorobenzenes under heat and pressure using aqueous methanojic
sodium hydroxide. Other manufacturing methods include conversion of diazonium salts of
various chlorinated anilines, and chlorination of phenolsulfonic acids and benzenesulphonic
acids, followed by the removal of the sulphonic acid group (Oilman et al., 1988; Hutzinger
and Redler, 1991 a).
Because of the manufacturing processes employed, commercial chlorophenol
products can contain appreciable amounts of impurities (Oilman et ai., 1988). During the
direct chlorination of phenol, CDD/CDFs can form either by the condensation of tri-, tetra-,
• "r ; . . I ;• '/ , |ji||j' ' i A, , - , |'i .;. ; :;i"; . ".• ;•' ,_;•";
-------
DRAFT-DO NOT QUOTE OR CITE
2,3,4,5-tetrachlorophenol, no more recent data on concentrations of CDDs and CDFs could
be found in the literature for the mono- through tetra-chlorophenols. Tables 8-7 and 8-8
present summaries of several studies that reported CDD/CDF concentrations in PCP and in
PCP-Na products, respectively. Many of these studies do not report congener-specific
concentrations, and many are based on products obtained from non-U.S. sources.
Regulatory Actions - Section 8.3.8 of this report describes regulatory actions taken
by EPA to control the manufacture and use qf chlorophenol-based pesticides.
In the mid-1980s, EPA's Office of Solid Waste promulgated land disposal
restrictions on wastes under RCRA (i.e., wastewaters and nonwastewaters) resulting from
the manufacture of chlorophenols (40 CFR 268). Table 8-9 lists all wastes in which CDDs
and CDFs are specifically regulated as hazardous constituents by EPA, including
chlorophenol wastes (waste codes F020 and F021). The regulations prohibit trie land
disposal of these wastes until they are treated to a level below the routinely achievable
detection limits in the waste extract listed in Table 8-9 for each of the following congener
i ' ' . *
groups: TCDDs, PeCDDs, HxCDDs, TCDFs, PeCDFs, and HxCDFs. Wastes from PCP-wood
preserving operations (waste codes K001 and F032) are also regulated as hazardous .
, wastes under RCRA (40 CFR 261).
EPA's Office of Water promulgated effluent limitations for facilities that manufacture
chlorinated phenols and discharge treated wastewater (40 CFR 414.70). These effluent
limitations do not specifically regulate CDDs and CDFs; however, the treatment processes
required to control the chlorinated phenols that are regulated (2-chlorophenol and 2,4,-
dichlorophenol) are also expected to reduce releases of any CDDs and CDFs that may be
present in the untreated wastewater. The effluent limitations for the individual regulated
chlorinated phenols are less than or equal to 39 ^g/L for facilities that utilize biological end-
of-pipe treatment.
DCPs and TrCPs are subject to reporting under the Dioxin/Furan Test Rule, which is
discussed in Section 8.3.7 of this report. On the effective date of that rule (i.e., June 5,
1987) and since that date, only the 2,4-DCP isomer has been commercially produced (or
imported) in the United States, and as noted in Table 8-6, no CDD/CDFs were detected in
the product. Testing is required for the other DCPs and TrCPs, if manufacture or
importation resumes. Similarly, TeCPs were subject to reporting under the Dioxin/Furan
Pesticide Data Call-In (DCI) (discussed in Section 8.3.8 of this report). Since issuance of
8~9 April 1998
-------
DRAFT-DO NOT QUOTE OR CUE
the DCI, the registrants of TeCP-containing pesticide products have elected to no longer
• ::vi f : "ii ,. i " ' Ji1!1! ?;•'•• ' •• '•• •' •• ,•,•: , ,.,: ';,"";' ,; i '.• ',4 •'•>*•'. >>ii'..'' .';•''• : ' .if";'1';1 ..••.. .. ! \ '• ,
support the registration of their products in the United States.
In January 1987, EPA entered into a Settlement Agreement with pentachlorophenol
(PCP) manufacturers, which set limits on allowed uses of PCP and its salts and set
maximum allowable concentrations of 2,3,7,8-TCDD and HxCDDs effective in February
1989. Section 8.3.8 discusses the 1987 PCP Settlement Agreement and estimates current
releases of CDD/CDFs associated with use of PCP in the United States.
Since the late 1980s, U.S. commercial production of chlorophenols has been limited
to 2,4-dichlorophenol (2,4-DCP) and PCP. As noted above, disposal of wastes generated
during the manufacture of chlorophenols are strictly regulated and thus releases to the
environment are expected to be negligible. With regards to releases associated with the
use of 2,4-DCP, no CDD/CDFs have been detected in 2,4-DCP. Releases associated with
!K . •••'•' '., *"§\ i" -: i" ':•''•'.; \",\\ . •[."'>•*'• &'?:'<.,?',!'/' ; , •'.:'.':,''>'•;'." \:: .' .!';:•!>' •! "i ' •
the use of PCP are presented in Sections 8.3.8.
,„''„";" , , , \ " ' ' '
8.3.2. Chlorobenzenes
Chlorobenzenes have been produced in the United States since 1909. U.S.
'. ' i'i u i 11 ' .-']• !; ..;
production operations were developed primarily to provide chemical raw materials for the
:'< •" ' . • •' 'il"i ' ' ' i ! J' • •:•' :: I ' '
production of phenol, aniline, and various pesticides based on the higher chlorinated
benzenes. Due to changes over time in the processes used to manufacture phenol and
aniline, and to the phase-out of highly chlorinated pesticides such as DDT and
hexachlorobenzene, U.S. production of Chlorobenzenes decreased in 1988 to 50 percent of
the peak production level in 1969.
Chjorpbeozenes can be produced via three methods: (1) electrophilic substitution of
benzene (in liquid or vapor phase) with chlorine gas in the presence of a metal salt catalyst;
(2) oxidative chlorination of benzene with HCI at 150-300°C in the presence of a metal salt
catalyst; and (3) denydrohalogenation of hexachlorocyclohexane wastes at 200-240°C with
a carbon catalyst to produce trichlorobenzene, which can be further chlorinated to produce
• i,, '„!,"' " ' " , ,., illlllf! ' " ." HI! 11,:1'" i IK ." ,„ i !! i,'" !'"il •"'., .''i.Jr'ii, '•"', >i: i.!',"",,,!1 „ „ «"i,,!1!! ',i,l: ijii' i|> j ••' i ,1, , !»!'!'i »„'",":' !.
;,ii!!,'i., „ !| i.. ]| • i ;''»,',, • •,. „ fi'iii1. "u IK' , -',! ',,,!MI,I •:;"",•„• • ,;,!• •",•!•;/I.1'' ,'i, liirii"11;,1,,;,!",! i1 .i:1,1! .i1-,.*, !:y,i,,,Y i
higher chlorinated benzenes (Ree et al., 1988; Hutzinger and Fiedler, 1991 a; Bryant, 1993).
All Chlorobenzenes currently manufactured in the United States are produced using
the electrophilic substitution process using liquid phase benzene (i.e., temperature is at or
below 80°C). Ferric chloride is the most ppmmon catalyst employed. Although this
method can be used to produce mono- through hexachlorobenzene, the extent of
8-10 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
chlorination is controlled to yield primarily MCBz and DCBz. The finished product is a
mixture of chlorobenzenes, and refined products must be.obtained by distillation and
crystallization (Bryant, 1993).
CDD/CDFs can be inadvertently produced during the manufacture of chlorobenzenes
by nucleophilic substitution and pyrolysis mechanisms (Ree et al., 1988). The criteria
required for production of CDD/CDFs via nucleophilic substitution are: (1) oxygen as a
nuclear substituent (i.e., presence of chlorophenols) and (2) production and/or purification
of the substance under alkaline conditions. Formation via pyrolysis requires reaction
-i. •»_''• , "
temperatures above 150°C (Ree et al., 1988; Hutzinger and Fiedler, 1991 a). The liquid-
phase electrophilic substitution process currently used in the United States does not meet
any of these criteria. Although Ree et al. (1988) and Hutzinger and Fiedler (1991 a) state
that the criteria for formation of CDD/CDFs via nucleophilic substitution may be present in
the catalyst neutralization and purification/distillation steps of the manufacturing process,
Opatick (1995) states that the chlorpbenzene reaction product in U.S. processes remains
mildly acidic throughout these steps.
» .
Table 8-10 summarizes the very limited published information on CDD/CDF *
contamination of chlorobenzene products. The presence of CDD/CDFs has been reported in
TCBz, PeCBz, and HCBz. No CDD/CDFs have been reported in monochlorobenzene (MCBz)-
and DCBz. Conflicting data exist concerning the presence of CDD/CDFs in TCBz. One
study (Villanueva et al.,. 1974) detected no CDD/CDFs in one sample of 1,2,4-TCBz at a
detection limit of 0.1 yug/kg. Hutzinger and Fiedler (1991 a) reported unpublished results of
Dr. Hans Hagenmaier showing CDD/CDF congener group concentrations ranging from 0.02
to 0.074 f^g/kg in a sample of mixed TCBz. Because the TCBz examined by Hagenmaier
contained about 2 percent hexachlorocyclohexane, it is reasonable to assume that the
TCBz was produced by dehydrohalogenation of hexachlorocyclohexane (a manufacturing
process not currently used in the United States).
Regulatory Actions - EPA has determined, as part of the Federal Insecticide,
Fungicide/and Rodentjcide Act (FIFRA) Pesticide Data Call-In (discussed in Section 8.3.8),
that the 1,4-DCBz manufacturing processes used in the United States are not likely to form
CDD/CDFs. MCBz, DCBz, and TCBz are also listed as potential precursor chemicals under
the TSCA Dioxin/Furan Test Rule and are subject to reporting. (See Section 8.3.7.) In
addition, a Significant New Use Rule (SNUR) was issued by EPA under Section 5(a)(2) of
8-11 Aprjl 1998
-------
DRAFTl-Dd NOT QUOTE OR
TSCA on December 1, 1993, with an effective date of January 14, 1994, for PeCBz and
1,2',4,5-TeCBz (Federal Register, 1993c). this rule requires persons to submit a significant
new use notice to EPA at least 90 days before manufacturing, importing, or processing
either of these compounds in amounts of 10,000 pounds or greater per year per facility for
any use. All registrations of pesticide products containing HCBz were cancelled in the mid-
1980s {Carpenter etal., 1986).
EPA's Office of Solid Waste promulgated land disposal restrictions on wastes (i.e.,
wastewaters and nonwastewaters) resulting from the manufacture of chlorobenzenes (40
CFR 268). Table 8-9 lists all solid wastes in which CDDs and CDFs are specifically
regulated as hazardous constituents by EPA, including chlorobenzene wastes. The
regulations prohibit the land disposal of these wastes until they are treated to a level below
the routinely achievable detection limits in the waste extract listed in Table 8-7 for each of
IJ!" • i ,, : ii , 'i' H,!|i|!|! , ' ,„ " „, ; i ' ' ,|i«| , v, , Ji >•» • , „ . ,,|i,, !' ."" ,f t ',,!'„ i|. •', ' , " .' „ "lW,i "t \< „.,'" | ,, , . - , i
the following congener groups: TCDDs, PeCDDs, HxCDDs, T CDFs, PeCDFs, and HxCDFs.
EPA's Office of Water promulgated effluent limitations for facilities that manufacture
' • ''«*;.. ,• """:: '• li. •l"; >.'•"• ;i:«",:: H! "'.'!•'':''''':'.•;;• i;iVi ''KiT'.O ::.'*'-y'<<•'&'•>•>:•/. ' M&'I'r"'•''"'" l.!l "• .r .',.'.' '.
chlorinated benzenes and discharge treated wastewater (40 CFR 414.70). Although these
, ": :" ; ' / •,'•< u"f.it 'v»': •. '>",'',;'. .*;-•;!;, .'.'..':,•!'.;',{'• v>: ."''i;-,!t •;•,•' i .';"1^:-'1',';:;''.•'.)''"''•.;j;::(»"i . ..i ' . : '' •• . •
effluent limitations do not specifically address CDDs and CDFs, the treatment processes
required to control the chlorinated benzenes that are regulated (chlorobenzene; 1,2-
'"'„'. „' „ ', :X!nu i .., • '' 1 " '.' • ' "« ''' • '".!• " "•• i ""V '!!'„'" .."i • '!!"•", .• '. !" ',., M»" '»!" •", ''. ",, '. », , I
dichlorobenzene; 1,3-dichlorobenzene; 1,4-dichiorobenzene; 1,2,4-trichlorobenzene; and
hexachlorobenzenej are expected to reduce releases of any CDDs and CDFs that may be
present in the untreated wastewater. The effluent limitations for the individual regulated
chlorinated benzenes are less than or equal to 77 j^g/L for facilities that utilize biological
end-of-pipe treatment and are less than or equal to 196 ^g/L for facilities that do not
employ biological end-of-pipe treatment.
Since at least 1993, U.S. commercial production of chlorobenzenes has been limited
., , 'Vriii, . .. , ..' • •",;;; • -;: •• . T., : ; " >(.,," -..i • •> ». •• v , •• •> •• r ir : • . .- P
to MCBz, 1,2-dichIorobenzene (1,2-DCBz), 1,4-dichlorobenzene (1,4-DCBz), and, to a much
lesser extent, 1,2,4-trichlorobenzene (1,2,4-TCBz). As noted above, CDD/CDF formation
is not expected under the normal operating conditions of the processes currently used in
the United States tp produce these four chemicals. No tetra-, penta-, or hexachlorinated
benzenes are now intentionally produced or used in the United States (Bryant, 1993).
Thus, releases of CDD/CDFs from manufacture of chlorobenzenes in 1995 were estimated
as negligible. Because the available information on CDD/CDF content of MCBz to PeCBz is
very limited and is based primarily on unpublished European data and because information
8-12 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
on the chlorobenzene manufacturing processes in place during 1987 is not readily available,
no emission estimates can be made for 1987. .
8.3.3. Chlorobiphenyls
PCBs are manufactured by the direct batch chlorination of molten biphenyl in the
presence of a catalyst followed by separation and purification of the desired chlorinated
biphenyl fractions. During the manufacture of PCBs, the inadvertent production of CDFs
also occurred. The purpose of this section is to address potential releases of CDD/CDFs
associated with leaks and spills of PCBs. CDFs have been shown to form when PCB-
containing transformers and capacitors undergo malfunctions or are subjected to fires that
result in accidental combustion of the dielectric fluid. This combustion source of PCB-
associated CDFs is discussed in Section 6.6. Section 11.2 addresses releases of dioxin-like
PCBs.
» Production of PCBs is believed to have been confined to 10 countries. The total
amount of PCBs produced worldwide since 1929 (i.e., the first year of known production)
is estimated to total 1.5-billion kg. Initially, PCBs were primarily Used as dielectric fluids in
transformers. After World War II, PCBs found steadily increasing use as dielectric fluids in
capacitors, as heat-conducting fluids in heat exchangers, and as heat-resistant hydraulic
fluids in mining equipment and vacuum pumps. PCBs also were used in a variety of "open"
applications (i.e., uses from which PCBs cannot be re-collected) including: plasticizers,
carbonless copy paper, lubricants, inks, laminating agents, impregnating agents, paints,
adhesives, waxes, additives in cement and plaster, casting agents, dedusting agents,
sealing liquids, fire retardants, immersion oils, and pesticides (DeVoogt and Brinkman,
1989). ''•"';••..'-'
PCBs were manufactured in the United States from 1929 until 1977. U.S.
production peaked in 1970, with a volume of 85-million pounds. Monsanto Corporation,
the major U.S. producer, voluntarily restricted the use of PCBs in 1971, and annual
production fell to 40-rnillion pounds in 1974. Monsanto ceased PCB manufacture in mid-
1977 and shipped the last inventory in October 1977. Regulations issued by EPA
beginning in 1977, principally under TSCA (40 CFR 761), strictly limited the production,
import, use, and disposal of PCBs. (See Section 4.1 for details on TSCA regulations.) The
estimated cumulative production and consumption volumes of PCBs in the United States
8-13
April 1998
-------
. DRAFT-DO NOT QUOTE OR CUE
from 1930 to 1975 were: 1,400-million pounds produced; 3-million pounds imported
{primarily from Japan, Italy, and France); 1,253-million pounds sold in the United States;
' , i 'Mil. • " : ' '„'','' : ' ', • i"11' i. '.•!, ;. ,«, ' ' , , , ", (',, . "'„ • :' i : ,•!•,;, ' ,": ,\|1, 'i. ";,!• •!' 4, v : ,i. •:, , :\ "
and 150-million pounds exported (ATSDR, 1993; DeVoogt and Brinkman, 1989).
"('-' : " ,, " ' -iTK: ,' ; • , • . ','". !" , •' •-;" •',•", ( ', -.,.•,. , .:, •• ,V,; , ..f . •• ;•_;,.,:,, ].',! , ; , . , •. I
Monsanto Corporation marketed technical grade mixtures of PCBs primarily under
the trade name Aroclor. The Aroclors are identified by a four-digit numbering code in which
the last two digits indicate the chlorine content by weight percent. The exception to this
c6ding scheme is Aroclor 1016, which contains only mono- through hexachlorinated
congeners with an average chlorine content of 41 percent. Listed below are the
percentages of total Aroclor production during the years 1957 to 1977 by Aroclor mixture
as reported by Brown (1994).
1957-1977
U.S. Production
Aroclor (%)
;,: , , '• | \-: . :' 1221 ' • ...'",. P 90 ' •••
i6i6"'"' ' "; "' : '12.88 "'" ' •!
:,, ' -, ' .- ''I 1232 ,, ' , .,'. , , ... „ ', 0.24 ',"„. , ,
1242 51-^6
:;" •':/ , 1248, ,; ", '."i.i.'"':,"!!:, .' "6.76,1""',"',," ':''•'.
'.•!T "'1254" " : """ ' ' ' '"' ' ' "i:5l73 '"'"
1260 10.61
• ;;li": :" 1262 " ' :' o43"
1268 0.33
i'"': ' !l. ': ••" ;,;i :; 'i •• ,' ,!"'• -• i • , ' . i ' • : '•
The trade names of the major commercial PCB technical grade mixtures
manufactured in other countries included: Clophen (Germany), Fenclor and Apirolio (Italy),
Kanechlor (Japan), Phenoclqr and Pyralene (France), Sovtel (USSR), De/or and Delorene
{Czechoslovakia), and Orophene (German Democratic Republic) (DeVoogt and Brinkman,
1989). The mixtures marketed under these trade names were similar in terms of chlorine
content (by weight percent and average number of chlorines per molecule) to those of
various' Aroclors. Listed below are comparable mixtures in terms of chlorine content
marketed under several trade names.
Aroclor Clophen Pyralene Phenoclor Fenclor Kanechlor
1232
1242 A-30
1248 A-4Q
1254 A-50
1260 A-60
8'14 April 1998
2000
3000
DP-3
, DP-4
PP-5
'.PP-01.. „"
42
' ,,,',,54 ;,
64
200
300
400
500
600
-------
'". ••'.'. DRAFT-DO NOT QUOTE OR CITE
During the commercial production of PCBs, thermal oxidative cyclization under
alkaline conditions resulted in the inadvertent production of CDFs in most of the
commercial PCB mixtures (Brown et al., 1988; ATSDR, 1993). Bowes etal. (1975a) first
reported detection of CDFs in Arpclpr products; samples of unused Aroclors manufactured
in 1969 and 1970 were found to have CDF (i.e., TCDF through HxCDF) concentrations
ranging from 0.8 to 2.0 mg/kg. Bowes et al. (1975b) employed congener-specific
analytical methodology and detected 2,3,7,8-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 mg/kg, respectively, in unused samples
of Aroclor 1254 and Aroclpr 1260. The presence of CDDs in commercial PCB mixtures,
although at much lower concentrations than those of the CDFs, was reported by
Hagenmaier (1987) and Malisch (1994). Table 8-11 presents the CDF and CDD congener
group concentrations reported by Bowes et al. (1975a) and those reported in subsequent
years for unused PCBs by Erickson (1986), ATSDR (1993), Hagenmaier (1987), and
Malisch (1994).
Several researchers reported concentrations of specific CDD/CDFs congeners in
commercial PCB mixtures (Bowes et al., 1975b; Brown et al. 1988; Hagenmaier, 1987;
Malisch, 1994). Only the Hagenmaier (1987) and Malisch (1994) studies, however,
reported the concentrations of all 2,3,7,8-substituted CDDs and CDFs. Table 8-12
presents the results pf these four studies. It is evident from the table that major variations
are found in the levels of 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF in the Clophen mixtures
reported by Hagenmaier (1987) and Malisch (1994) and the corresponding levels in the
Aroclor mixtures reported by Bowes et al. (1975b) and Brown et al. (1988).
Brown et al. (1988) compared the levels of 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, arid
1,2,3,7,8,9-HxCDF in unused samples and used samples (i.e., samples from previously
used capacitors and transformers) of Aroclors 1016, 1242, 1254, and 1260. The
concentration ranges reported for the used and unused Aroclors were similar, leading
Brown et al. (1988) to conclude that CDFs are not formed during the normal use of PCBs in
electrical equipment.
Estimates of the amounts of CDD/CDF TEQ that may have been released to the
environment during 1987 and 1995 from spills and leaks can be made using the release
data reported by manufacturing facilities to EPA's Toxics Release Inventory (TRI). Table
11-6 in Section 11.2.2 lists the amounts of PCBs reported to TRI to be released to the
8-15 • . April 1998
-------
, DRAFT-pp NOT QUOTE OR CITE
environment during the years 1988 through 1993. These TRI data include emissions to the
air, discharges to bodies of water, and releases to land. Based on these data, annual
emissions of PCBs to air during 1988 and 1993 could have been as high as 2.7 kg and as
lovy as 0 kg, respectively. If it is further assumed that the ratio of TEQ to total PCB in the
air emissions was 0.17:1,000,000 (i.e., the average of the TEQ contents for Clophen A-30
and Clophen A-50 [i.e., 170 /^g/kg] reported by Hagenmaier (1987) and presented in Table
i'" ,'"••'. '! : 'i ,,K ' ' .,'•, ''"' ; '• . "M '" 'i|,.,"' ",'"!,,., ' ,|i| "";:,!.. ''"'" ••'! '„ 'T ' " ";LI!PJI • ' I'M !•
8-12), then annual emissions of TEQs to air in 1988 and 1993 could have been 0.5 and 0
mg, respectively. Similar assumptions for PCB releases to water of 4.5 kg in 1988 and 0
. ' !•',;' '•• •• ' ' • •!.:,;• ' , l 'ii, '.,*V ">";<•;!-"; •'••!•'• '".'^ •• •£ \ •:•' ',; »'!'!' i* i ':' '•• 1' ' ;
kg in 1993 yield estimated TEQ emissions during 1988 and 1993 of 0.8 and 0 mg,
respectively. For land releases of 341 kg in 1988 and 120 kg in 1993, estimated TEQ
emissions during 1988 and 1993 are 58 and 20 mg, respectively. All of these estimated
releases are considered to be negligible (i.e., less than 1 gram per year).
»'. |i, , • ' ' , ' '',:,''' |III! ' ,'!' i I ', • '• ' II ' , ' ' , , .""','"; , . ' ,i , ' • , ''»• ,| ,|n,'',!!' "'',,,''* I ! .
8.3.4. Polyvinyl Chloride
Although it is recognized that CDD/CDFs are formed during the manufacture of
ethylene dichloride (EDC) and vinyl chloride monomer (VCM), polyvinyl chloride (PVC)
manufacturers and environmental public interest groups disagree as to the quantity of
. . ' '• .-!; :,(i,', ' •iM,;;:'X; ",; i i"! -:•:£';,'•. '* •• '• -'f;;t1-•••',.&.,.•, :i.^';i •.,.*• i; • • : . •'• .
CDD/CDFs formed and released to the environment in wastes and possibly PVC products.
Insufficient information is available at this time to enable EPA to make definitive release
estimates. Although EPA regulates emissions from EDC/VC production facilities under the
Clean Water Act (40 CFR 61), the Clean Air Act (40 CFR 414), and RCRA (40 CFR 268 -
Waste Codes F024, K019, and KQ2Q), CDD/CDFs are not specifically regulated pollutants;
as a consequence, monitoring data for CDD/CDFs in emissions are generally lacking. The
Interim Phase I Report addressing products and treated wastewater was submitted to EPA
in November 1996 (The Vinyl Institute, 1996). The remainder of |his section summarizes
the available information and presents the release estimates made by various interested
i.v •;•" ., , i/li .r':11 '•'. ,-;.V,ri. >lV^,::'>ri:y.':f'^'"'>'\im^^i'^:^,^^' •,!..'••
parties.
In 1993, Greenpeace International issued a report on dioxin emissions associated
with the production of EDC/VCM (Greenpeace, 1993). Greenpeace estimated that 5- to
10-g TEQ are released to the environment (air, water, and ground combined) annually for
every 100,000 metric tons of VCM produced. This emission factor was based on data
gathered by Greenpeace on four European plants. The Vinyl Institute responded with a
8-16
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
critique of the Greenpeace report {ChemRisk, 1993). Miller (1993) summarized the
differing views of the two parties. According to Miller (1993), European PVC
manufacturers claim the emission factor is 0.01- to 0.5-g TEQ/100,000 metric tons of
VCM. Although Greenpeace (1993) and ChemRisk (1993) used basically the same
monitoring information to develop their emission factors, Greenpeace adjusted the emission
factor to account for unquantified fugitive emissions and waste products containing
unspecified amounts of CDD/CDFs.
In 1995, Greenpeace issued another study reiterating the organization's concern
that the generation and emissions of CDD/CDFs may be significant and urging that further
work be initiated to quantify and prevent emissions (Stringer et ah, 1995). However, this
study acknowledged that because EDC/VCM production technologies and waste
treatment/disposal practices are very site-specific, the limited information currently
available on CDD/CDF generation and emissions makes it difficult to quantify amounts of
CDD/CDFs generated and emitted.
Tiernan et al. (1995) reported the results of testing two samples of ethylene
dichloride, two samples of vinyl chloride monomer, and two samples from each of two
different batches of powdered PVC pipe resin. The PVC resin analyses were performed
using an extraction procedure that results in complete dissolution of the PVC resin,
followed by liquid-liquid extraction of the dissolved material. With the exception of OCDD,
no CDD/CDFs were detected in any of the samples at detection limits ranging from less
than 1 ng/kg for the tetra- and hexa- congener groups and 0.5 to 4.6 ng/kg for hexa-
through octa-CDDs and CDFs. The OCDD levels detected (6 to 8 ng/kg) were of the same
magnitude as the OCDD levels detected in the blank samples implying background
contamination.
Stringer et al. (1995) presented the results of analyses of three samples of
chlorinated wastes obtained from U.S. EDC/VCM manufacturing facilities. The three
wastes were characterized according to EPA hazardous waste classification numbers as
follows: (1) an F024 waste (i.e., waste from the production of short chain aliphatics by free
radical catalyzed processes); (2) a.K019 waste (i.e., heavy ends from the distillation of
ethylene from EDC production); and a probable KO20 waste (i.e., heavy ends from
distillation of VC in VCM manufacture). Table 8-13 presents the analytical results reported
by Stringer et al. (1995). The reported CDD/CDF concentrations in the three wastes were
8-17 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
. '- '.!':'! ' ''» , :" • 'I1 !•.;.••.•", ' . ;":',.•'•!' ! •
20-^g TEQ/kg, 5,928-pg TEQ/kg, and 3.2-^g TEQ/kg for the F024, KOI 9, and K020 waste,
respectively. Stringer et al. (1995) stated that the concentration found in the K020 waste
was similar to levels found in comparable waste from a VCM manufacturing facility in the
United Kingdom (3.1 to 7.6/zg/kg).
;'•!' ! • :" '• ;; ':*!;! •' '. ,' :'. .V .';•. :•'•:" •'•'.>*••' ;. '.'.•-•..."/...'A' • ,' !'!'.• • '.'. ,. i ; • , "
In response to the lack of definitive studies and at the request of EPA, U.S. PVC
manufacturers initiated an extensive monitoring program to evaluate the extent of any
CDD/CDF releases to air, water, land, as well as product contamination. Emission and
!;''('''! ,'' : 'I: " '"I1 '' < . •;V • !/" ";, . '':, -''.'l'^"!;'!'''I! !--!'-.'': "•• 'I ":H' I:'!,' •. ;'"• ' ', W-.V' ,.''!;.'
product testing are being performed at various facilities representative of various
manufacturing and process control technologies. An independent peer review panel has
.|i|j!|N i i'i. i i, "' ,; " ', TJiUjliii, : : IH ! 'I, i , -' ' •,,, •; . •.' '.,1" Ill/;, , " 1 , • i. . '. ' i, , ,,,],;;*,:," ; AA!' ', 'i1 |1|;!!i, Vt'.t ' i' ,'«i ' i 'j ' ' '
been formed and is reviewing the results of all monitoring studies prior to their public
'!"?":,' ,''•'•" i'":l! ! "' r""1"" /"!" I-'' ":,''<'i': "•*•"•*$';:. 'i: f.^'.'k,;'.'' V's1;'''~' I":1'" !• ' *tl~^'] •*!' . ;• "i ' •'' ' ; ' '
release, the Interim Phase I Report from this study has been submitted to EPA, and the
,'i " ' ,, , gt'til • . '• ":, "'''•":., -1"i "i • , """ > : ' ••' .iv1,! .','•.'•"'' • ::'"', ii';,. I, A i1!!:,/"!1 , ,,i '« ,,!.,!' 'a .v1 :"^ I.L Oi, ',*•. ;., .iin •:,!.:!! ,,!i, ' „ •,. i.
resins. The results ranged from ND to 0.008-pg TEQ/g (mean = 0.001-pg TEQ/g assuming
NDs = 0, and 6.4-pg TEQ/g assuming NDs = 1/2 DL). The method detection limit was 2
•I'.," " : ' ' •" iffilllli 'i , Hi" ... ii i ii M i in i - •, •• l • ' •
i:'': ' / M „ •,, < < il i ii i i " , ' "
pg/g for all congeners except OCDD and OCDF (4 pg/g). The Vinyl Institute (1996) also
presented results for 5 samples from 5 of the 15 U.S. facilities manufacturing EDC.
CDD/CDFs were detected in only one sample (0.03-pg TEQ/g). The method detection limit
for all congeners was 1 pg/g. Based on 1995 production data and the average TEQ
• 8-18 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
observed for the samples analyzed, total releases of CDD/CDF TEQs from suspension/mass
PVC resins, emulsion PVC resins, and "sales" EDC were estimated by The Vinyl Institute
(1996) to be 0.0 to 3.0 grams, 0.004 to 0.1 grams, and 0.008 to 0.29 grams,
respectively.
The estimated PVC production in the United States during 1995 was 5.656-million
metric tons per year (The Vinyl Institute, 1996). Applying the worldwide emission factors
discussed above to the U.S. PVC industry, gives a range of dioxin emissions of 0 56- to
28.3-g TEQ/yr (based on the ChemRisk (1993) emission factors) to 283- to 565-g TEQ/yr
(based on the 1993 Greenpeace emission factors). It is anticipated that the Vinyl Institute
will be completing and releasing the full report on PVC resin,' wastewater treatment solids,
waste water, and incinerator stack releases in the spring of 1998. EPA anticipates that
this information, along with the information from previously cited sources, should be
adequate to make a reasonable emission estimate for this inventory.
8.3.5. Other Aliphatic Chlorine Compounds
Aliphatic chlorine compounds are used as monomers in the production of plastics, as
solvents and cleaning agents, and as precursors for chemical synthesis (Hutzinger and
Fiedler, 1991a). These compounds are produced in large quantities. In 1992> 14.6-million
metric tons of halogenated hydrocarbons were produced (U.S. ITC, 1946-1994). The
production of 1,2-dichloroethane and vinyl chloride accounted for 82 percent of this total
production. Highly chlorinated CDDs and CDFs (i.e., hexa-to octachlorinated congeners)
have been found in nanograde quality samples of 1,2-dichloroethane (55 ng/kg of OCDF in
one of five samples), tetrachloroethene (47 ng/kg of OCDD in one of four samples),
epichlprohydrin (88 ng/kg of CDDs and 33 ng/kg of CDFs in one of three samples), and
hexachlorobutadiene (360 to 425 ng/kg of OCDF in two samples) obtained in Germany
from Promochem (Hutzinger and Fiedler, 1991 a; Heindl and Hutzinger, 1987). No
CDD/CDFs were detected in two samples of ally chloride, three samples of 1,1,1-
trichloroethane, and four samples of trichloroethylene (detection limit ranged from 5 to 20
ng/kg) (Heindl and Hutzinger, 1987). Because no more recent or additional data could be
found in the literature to confirm these values for products manufactured or used in the
United States, no nationalestimates of CDD/CDF emissions are made for the inventory.
8-19 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
EPA's Off|ce Qf Water promulgated effluent limitations for facilities that manufacture
chlorinated aliphatic chlorine compounds and discharge treated wastewater (40 CFR
414.70). Although these effluent limitations do not specifically address CDDs and CDFs,
the treatment processes required to control the chlorinated aliphatic compounds that are
regulated (e.g., 68 //g/L for 1,2-dichloroethane and 22 //g/L for tetrachloroethylene) are
. .I11', , ° 'b iR 'i, i1 ", '.» ,'„ . i, \'." , " ,f ,. "i. "„ si,' , w ':>* TI i .„• . . i, *
expected to reduce releases of any CDDs and CDFs that may be present in the untreated
wastewater. Similarly, EPA's Office of Solid Waste promulgated restrictions on land
disposal of wastes generated during manufacture of many chlorinated aliphatics (40 CFR
• , "K1 :: '• I ' • I1":)'!! !• • <'" , •<:'t". \ •"•' i. .i 'i.':'. I ' • •' *"•• "'", '•'•'• ::>." •'• a .' EVi '.•' '
268); however, these restrictions do not specifically regulate CDD/CDFs.
8.3.6. Dyes, Pigments, and Printing Inks
Several researchers analyzed various dyes, pigments, and printing inks obtained in
Canada and Germany for the presence of CDDs and CDFs (Williams et al., 1992; Hutzinger
and Fiedler, 1991 a; Santl et al., 1994c). The following paragraphs discuss the findings of
these studies.
Dioxazine Pyes and Pigments - Williams et al. (1992) analyzed the CDD/CDF content
in djoxazine dyes and pigments available in Canada. As shown in Table 8-15, OCDD and
OCDF concentrations in the /zg/g range, and HpCDD, HxCDD, and PeCDD concentrations in
the ng/g range were found in Direct Blue 106 dye (3 samples), Direct Blue 108 dye
(1 sample), and Violet 23 pigments (6 samples) (Williams et al., 1992). These dioxazine
pigments are derived from chloranil, which has been found to contain high levels of
, • 'lull'! f • , ' , ' if»jni'i i , •; , '•'':, ;:;,'"'!„ ,*' " '» i ', ,. i1:".!.:!1 >,'"',, ' ", a ' "i.; • ""i i ''',:•,'''".: ', ''n, ' i" .'•!, Si 'i1:1: i> Si"1 w i i
"i1, , ii1,;, ' ' ji' „ "' „ "' 'i l,Ki!l!!lii , ' , • ," ' 'i. , '|i'"i', ,,1,1. ,' . .':,!"' /i:,'! i.,.: n, ',, ' „ "n " • » '»!" Hi.1 "i:, •• "'i i,, , ':» ifc!1"! "I1 !" • ' . i'l, , •• •.
CDD/CDFs and has been suggested as the source of contamination among these dyes
(Christmann et al.,1989a; Williams et ai., 1992; U.S. EPA, 1992b). In May 1990, EF>A
received test results showing that chloranil was heavily contaminated with dioxins; levels
as high as 3,065-^p TEQ/kg were measured in samples from four importers (mean value of
1,754-^g TEQ/kg) (U.S. EPA, 1992b; Remmers et al., 1992). (See Section 8.3.7 for .
analytical results.)
In the early 1990s, EPA learned that dioxin TEQ levels in chloranil could be reduced
by more than two orders of magnitude (to less than 20 ,ug/kg) through manufacturing
feedstock and process changes. EPA's Office of Pollution Prevention and Toxics (OPPT)
subsequently began efforts to complete an industry-wide switch from the use of
,.';;/ . ' ; " " , Ml! "*•"••.; i i f I i •,••'! •'..••
contaminated chloranil to low-dioxin chloranil. Although chloranil is not manufactured in
* " "'" ' " ' ' ' ' ' ' "
8-20 , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
the United States, significant quantities are imported. As of May 1992, EPA had
negotiated agreements with all chloranil importers and domestic dye/pigment manufacturers
known to EPA that use chloranil in their products to switch to low-dioxin chloranil. In May
1993, when U.S. stocks of chloranil with high levels of CDD/CDFs had been depleted, EPA
proposed a significant new use rule (SNUR) under Section 5 of TSCA that requires industry
to notify EPA at least 90 days prior to the manufacture, import, or processing, for any use,
of chloranil containing total CDD/CDFs at a concentration greater than 20 ,ug/kg (Federal
Register, 1993a; U.S. EPA, 1993c).
In 1983, approximately 36,500 kg of chloranil were imported (U.S. ITC, 1984). The
U.S. International Trade Commission (ITC) has not published quantitative import data for
chloranil since 1984. If it is assumed that this import volume reflects actual usage of
chloranil in the United States during 1987 and the CDD/CDF contamination level was
1,754-Atg TEQ/kg, then the maximum release into the environment via processing wastes
and finished products was 64.0 g of TEQ. If it is assumed that the import volume in 1995
was also 36,500 kg, but that the imported chloranil contained 10-yug TEQ/kg on average,
then the total potential annual CDD/CDF release associated with,chloranil in 1995 was
0.36 g of TEQ. Given the low confidence in the estimates of import volumes in 1987 and
1995, the estimated range of potential annual emissions for both years is assumed to vary
by a factor of 10 between the low and high ends of the range. Assuming that 64.0-g
TEQ/yr was the geometiric mean of this range for 1987, then the range is calculated to be
20- to 200-g TEQ/yr. Assuming that 0.36-g TEQ/yr was the geometric mean of this range
in 1995, then the range is calculated to be 0.11- to 1.1-g TEQ/yr.
Phthalocyanine Dyes and Printing Inks - Hutzinger and Fiedler (1991 a) found
CDD/CDFs (tetra-, penta-, and hexachlorinated congeners) in the ^g/kg range in a sample of
a Ni-phthalocyanine dye. No CDD/CDFs were detected (detection limit of 0.1 to 0.5>g/kg)
in two samples of Cu-phthalocyanine dyes and in one Co-phthalocyanine dye (Hutzinger
and Fiedler, 1991 a).
Santl et al. (1994c) reported the results of analyses of four printing inks obtained
from a supplier in Germany. Two of the inks are used for rotogravure printing, and two are
used for offset printing. The results of the analyses are presented in Table 8-16. The TEQ
content of the inks ranged from 17.5 to 90.1 ng/kg. Primarily non-2,3,7,8-substituted
8'21 April 1998
-------
; DRAFT-DO NOT QUOTE OR CUE
congeners were found. The identities of the dyes/pigments in these inks were not
repbrted.
.[;!'', ; ' '- , „', :t\ " "' I'' , " ; , •' ;| . ,: :'• ",;.:'(< [ i. '' !; , ' • ; , ' ". . • I "\ •' ' :'!'•" V , '|. ' • '; ,
8.3.7. TSCA Dioxin/Furan Test Rule
Based on evidence that halogenated dioxins and furans may be formed as by-
products during chemical manufacturing processes (Versar, 1985), EPA issued a rule under
Section 4 of TSCA that requires chemical manufacturers and importers to test for the
' fj , , II ""'» '' !' , li !'" I'll!!; I, "' |, I'l. ' ' „" ..I '!,,' '', , ,',?>:"!,",,I1, . I,, I.'"!. ll!1',1,', .'' Ill' 'I1'! '!,:,, '.I,',," II' .' '!'' I , , .-
presence of chlorinated and brominated dioxins and furans in certain commercial organic
chemicals (Federal Register, 1987c). The rule listed 12 manufactured or imported
chemicals that required testing and 20 chemicals not currently manufactured or imported
that would require testing if manufacture or importation resumed. These chemicals are
listed in Table 8-17. The specific dioxin and furan congeners that require quantitation and
the target limits of quantitation (LOQ) are specified in the Rule are listed in Table 8-18.
Under Section 8(a) of TSCA, the final rule also required that chemical manufacturers submit
data on manufacturing processes and reaction conditions for chemicals produced using any
of the 29 precursor chemicals listed in Table 8-19. The rule stated that subsequent to this
• ' - . ::;!:»' .• >. , ,•»,(> -I-, i"' -, i ••.•'.i.'W:••'.'!,. •'.;•; ••;;•; v,»'.;:';!;"; .r(> ;,*!• >><;•, < ••< " !• ,.' • "
data gathering effort, testing may be proposed for additional chemicals if any of the
manufacturing conditions used favored the production of dioxins and furans.
Sixteen sampling and analytical protocols and test data for 10 of the 12 chemicals
that required testing were submitted to EPA (Holderman and Cramer, 1995). Data from 1 5
submissions were accepted; one submission is under review. Manufacture/import of two
substances (tetrabromobisphenol-A-bis-2,3-dibromopropylether and tetrabromobisphenol-A-
"i ' ' '..-., ' ;i3iii "! ; ' '•,».. '." : . 'f "•: ''i;* ' • . . :' '!.'" • 'i •: ' •'. '. • ' " •„" i! !"!>• "•'..'! „
diacrylate) have stopped since the test rule was promulgated. [NOTE: All data and reports
in the EPA TSCA Docket are available for public review/inspection at EPA Headquarters in
Washington, DC.]
Table 8-20 presents the results of analytical testing for dioxins and furans for the
eight chemicals with data available in the TSCA docket. Five of these 10 chemicals
contained dioxin/fufans. Positive results were obtained for: 2,3,5,6-tetrachloro-2,5-
cyclohexadiene-1,4-dione (chloranil), pentabromodiphenyloxide, octabromodiphenyloxide,
decabromodiphenyloxide, and 1,2-Bis(tribromophenoxy)-ethane. table 8-21 presents the
quantitative analytical results for the four submitted chloranil samples, as well as the
8-22 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
results of analysis by EPA of a sample of carbazole violet, which is manufactured from
chloranil.
It should be noted that although testing conducted under this test rule for 2,4,6-
tribromophenol indicated no halogenated dioxins or furans above the LOQs, Thoma and
Hutzinger (1989) reported detecting BDDs and BDFs in a technical grade sample of this
substance. Total TBDD, TBDF, and PeBDF were found at 84//g/kg, 12 fjg/kg, and 1 fjg/kg,
respectively. No hexa-, hepta-, or octa-BDFs were detected. Thoma and Hutzinger (11989)
also analyzed analytical grade samples of two other brominated flame retardants,
pentabromophenol and tetrabromophthaljc anhydride; no BDDs or BDFs were detected
(detection limits not reported).
8,3.8. Halogenated Pesticides and FIFRA Pesticides Data Call-in
In the late 1970s and early 1980s, attention began to focus on pesticides as
potential sources of CDDs and CDFs in the environment. Up to that time, CDD and CDF
levels were not regulated in end-use pesticide products. Certain pesticide active
ingredients, particularly chlorinated phenols and their derivatives, were known or
suspected, however, to be contaminated with CDDs and CDFs (e.g., pentachlorophenol
(PCP), Silvex, and 2,4,5-T). During the 1980s, EPA took several actions to investigate and
control CDD/CDF contamination of pesticides.
In 1983, EPA cancelled the sale of Silvex and 2,4,5-T for all uses (Federal Register,
1983). Earlier, in 1979, EPA ordered emergency suspension of the forestry, rights-of-way,
and pasture uses of 2,4,5-T; emergency suspensions of the forestry, rights-of-way,
pasture, home and garden, commercial/ornamental turf, and aquatic weed control/ditch
bank uses of Silvex were also ordered (Federal Register, 1979; Plimmer, 1980). The home
and garden, commercial/ornamental turf, and aquatic weed control/ditch bank uses of
2,4,5-T had been suspended in 1970.
EPA entered into a Settlement Agreement in 1987 with PCP manufacturers to allow
continued registrations for wood uses (Federal Register, 1.987a) under a restricted use basis
but which set tolerance levels for HxCDD and 2,3,7,8-TCDD. TCDD levels were not
allowed to exceed 1.0 ppb in any product, and after February 2, 1989, (a gradually phased
in requirement), any manufacturing-use PCP released for shipment could not contain
HxCDD levels that exceeded an average of 2 ppm over a monthly release or a batch level of
.» 8'23 April 1998
-------
- DRAFT-DO NOT QUOTE OR CITE
" ",: '; v •*'* '/"""''': V ! ' .: • , :;!:''ii';' :': ,;'";":; ' ',, ••<•':>:''. ••'.' ! " • '• • : ' ''':
4 ppm. On January 21, 1987, EPA issued a 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 Nonwood Uses, which prohibited the
registration of PCP and its salts for most nonwood uses (Federal Register, 1987b). EPA
deferred action on several uses (i.e., uses in pulp/paper mills, oil wells, and cooling towers)
• n,' \ .'.- '/'i'", I'm . • •• '" j i1 •• ,'',-' .••': "i >;„•',.: :':• ';•'""'' ".'•""• f\< ;•:,' • ffvT, ,;}•": ".'',''''"! ''Ifilfi1'" •• : ' ]' '
the ranges are calculated to be 17,766- to 35,400-g TEQ for 1995 and 25,500 to 51,000
11:''' ' " »' , • •: "iii " , I.- ' • •" •' •, . ii •',' ''"•' ,•;« ij • / ii,,.,; ' ' ,'„j •": ,••;,., •,, ", 'V r ,'' •',» •, : i
for 1987.
In addition to the pesticide cancellations and product standards, EPA's Office of
Pesticide Programs (OPP) issued two Daia Call-ins (DCIs) in 1987. Pesticide manufacturers
|i!!'!: ; "" i," i 'r, • "ii ' - "'li'JI "i" If'1",*;! :,-. •: '! 't>, ''IjTiii!11'" ,'*.)'> ••?"' 'it i,;':'!'1'1 : I II : 'I "•''•',
are required to register their products with EPA in order to market them commercially in the
United States. Through the registration process, mandated by FIFRA, EPA can require that
,,;,,i :; •• '. '' "" 'It ' i I i I - "' • I , . ' , " • i ;
the manufacturer of each active ingredient generate a wide variety of scientific data
,,,ui' ! ; ,„ ', ' ,11 ,/iii r1 i •,' „• jr. ,111, • ,i "in" :i. , .. ' i.'iip >| ,i,,« ,, " ,, i'"i, ', "H.1 • i,'"','i II'i l,il • , •;, i in"! 1.11 / 1l,,i •• i , ' i
through several mechanisms. The most common process is the five-phase reregistration
8-24 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
effort to which the manufacturers (i.e., registrants) Of older pesticide products must
comply. In most registration activities, registrants must .generate- data under a series of
strict testing guidelines, 40 CFR 158-Pesticide Assessment Guidelines (U.S.EPA, 1988b).
• Some pesticide active, ingredients may require additional data, outside of the norm, to
adequately develop effective regulatory policies for those products. Therefore, EPA can
require additional data, where needed, through various mechanisms, including the DCI
process.
The purpose of the first DCI (dated June and October 1987), Data Call In Notice for
Product Chemistry Relating to Potential Formation of Halogenated Dibenzo-p-dioxin or
Dibenzofuran Contaminants in Certain Active Ingredients, was to identify through an
analysis of raw materials and process chemistry, those pesticides that may contain '
halogenated dibenzo-p-dioxin and dibenzofuran contaminants. The list of 93 pesticides,(76
pesticide active ingredients) to which this DCI applied, along with their corresponding
Shaughnessey arid Chemical Abstract code numbers, are presented in Table 8-22. [Note:
the Shaughnessey code is an internal EPA tracking system-it is of interest because
chemicals with similar code numbers are similar in chemical nature (e.g., salts, esters, and
acid forms of 2,4-D).] All registrants supporting registrations for these chemicals were
subject to the requirements of this DCI, unless their product qualified for a Generic Data
Exemption (i.e., a registrant exclusively used a FIFRA-registered pesticide product(s) as the
source(s) of the active ingredient(s) identified in Table 8-22 in formulating their product(s)).
Registrants whose products did not meet the Generic Data Exemption were required to
submit the types of data listed below to enable EPA to assess the potential for formation of
tetra- through hepta-halogenated dibenzo-p-dioxin or dibenzofuran contaminants during
manufacture. Registrants, however, had the option to voluntarily cancel their product or
"reformulate to remove an active ingredient," described in Table 8-22, to avoid compliance
with the DCI.
• Product Identity and Disclosure of Ingredients: EPA required submittal of a
Confidential Statement of Formula (CSF), based on the requirements
specified in 40 CFR 158.108 and 40 CFR 158.120 - Subdivision D: Product
Chemistry. Registrants who had previously submitted still current CSFs were
not required to resubmit this information.
8-25
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Description of Beginning Materials and Manufacturing Process: Based on the
requirements mandated by 40 CFR 158.120 - Subdivision D, EPA required
submittal of a manufacturing process description for each step of the.
manufacturing process, including specification of the range of acceptable
conditions of temperature, pressure, or pH at each step.
Discussion of the Formation of Impurities: Based on the requirements
manClated by 40 CFR 158.120 - Subdivision D, EPA required submittal of a
i'JSI ' • , ' " :, '•i.lri • •'••.•; • .," ' - • ; "I'.,. :• J y.t I,''-- •-» •>' K' •'.•: '.' -: I :.',•,"
detailed discussion/assessment of the possible formation of halogenated
dibenzo-p-dioxins and dibenzofurans.
The second DCI (dated June and October 1987), Data Call-In for Analytical
Chemistry Data on Polyhalogenated Dibenzo-p-Dioxins/bibenzofurans (HDDs and HDFs),
1 .i "F. , ! . ' "' ; '.;'!• ' ,ii'linn!' „„;.'ii , i 'i,; r • ' \ \,,, ,', .'i1 s • ,,' ;,',,. i,' ir ii.: »i,: •• •' r i, • ", \ ',,',' »,'" 4:'":,,:; •' „:: • "i. ,>' • ' vTIn,"i •; ",!-,• i. ' • r • , '' •
wfs issued for 68, pestiqides (16 pesticide active ingredients) suspected to be contaminated
by CDD/CDFs. (See fable 8-23.) All registrants supporting registrations for these
pesticides were subject to the requirements of this DCI, unless the product qualified for
various exemptions or waivers. Pesticides covered by the second DCI were strongly
suspected by EPA to contain detectable levels of HDD/HDFs.
Under the second DCI, registrants whose products did not qualify for an exemption
or waiver were required to generate and submit the following types of data in addition to
the data requirements of the first DCI:
•'•' ••;' ! • ' "Mil' . . • •.;. ; rsl: >:: ••'.. ::-<'&"•:•'.W.••• •' '."?>•.'[.!•'>•*!' >, Vli^ • \ '•. ,: , '
• Quantitative Method For Measuring HDDs or HDFs: Registrants were required
to develop an analytical method for measuring the HDD/HDF content of their
':!,! i,i :' ' ' ! i1 ,'„ i"; ,1.1,' l|"""!',;! ," Jj i '„ L, i'1 - i'1,;1,! >., j ij/t,,, '".'i; :\ j ' „;, vifii,, i1;1' x '.'', j
products. The DCI established a regimen for defining the precision of the
analytical method (i.e., for internal standard—precision within +/- 20 percent
and recovery range of 50 to 150 percent, also a signal to noise ratio of at
,; " .-''... ",i;* ',• ..•'•• "*'". /'•:•'>( ; &:.,?, •:'...•';•>'&:*;: i Hu:,- '" '• " iislli1",1!.!!1,*;, -..• i >.S 'Bli,. • •'•'' '• : • I
least 10:1 was required). Target quantification limits were established in the
DCI for specific HDD and HDF congeners. (See Table 8-24.)
• Certification of Limits .Qf.HP.Ds.or.HDFs;. Registrants were required to submit
a "Certification of Limits" in accordance with 40 CFR 158.110 and 40 CFR
:;, • ' ;.:-!! ,;. , •• ' i i i i 1 •..'•''.'
158,120 - Subdivision D. Analytical results were required that met the
guidelines described above.
8-26 ' April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Registrants could select one of two options to comply with the second DCI. The
first option was to submit relevant existing data, develop new data, or share the cost to
develop new data with other registrants. The second option was to alleviate the DCI
requirements through several exemption processes including a Generic Data Exemption,
voluntary cancellation, reformulation to remove the active ingredient of concern, an
assertion that the data requirements do not apply, or the application/award of a low-
volume, minor-use waiver.
The data contained in CSFs, as well as any other data generated under Subdivision
D, are typically considered Confidential Business Information (CBI) under the guidelines
prescribed in FIFRA, because they usually contain information regarding proprietary
manufacturing processes. In general, all analytical results submitted to EPA in response to
both DCIs are considered CBI and cannot be released by EPA into the public domain.
Summaries based on the trends identified in that data, as well as data made public by EPA,
are summarized below.
The two DCIs included 161 pesticides. Of these, 92 are no longer supported by
registrants. Based on evaluations of the probess chemistry submissions required under the
DCIs, OPP determined that formation of CDD/CDFs was not likely during the manufacture
of 43 of the remaining 69 pesticides; thus, analysis of samples of these 43 pesticides was
not required by OPP. Evaluation of process chemistry data is ongoing at OPP for an
additional seven pesticides. Tables 8-22 and 8-23 indicate which pesticides are no longer
supported, those for which OPP determined that CDD/CDF formation is unlikely, and those
for which process chemistry data or analytical testing results are under review in OPP (U.S.
EPA, 1995a).
OPP required that analysis of production samples be performed on the remaining 19
pesticides. (See Table 8-25.) The status of the analytical data generation/evaluation to
date is summarized as follows: {1) no detection of CDD/CDFs above the LOQs in registrant
submissions for 13 active ingredients; (2) detection of CDD/CDFs above the, LOQs for 2,4-D
acid (two submissions) and 2,4-D 2-ethyl hexyl acetate (one submission); and (3) ongoing
data generation or evaluation for four pesticides.
Table 8-24 presents a summary of results recently obtained by EPA for CDDs and
CDFs in eight technical 2,4-D herbicides; these data were extracted from program files in
OPP. Because some of these files contained CBI, the data in this table were reviewed by
8"27 April 1998.
-------
'-. DRAFT-DO NOT QUOTE OR CITE
',,''., ' ",.'..'!. \
OPP sfaff to ensure that no CBI was being disclosed (Funk, 1996). Figure 8-5 presents a
congener profile for 2,4-D, based on the average, congener concentrations reported in Table
8-24.
Schecter et al. {1997) recently reported the results of analyses of samples of 2,4-D
manufactured in Europe, Russia, and the United States. (See Table 8-26.) The total TEQ
concentrations measured in the European and Russian samples are similar to those
measured in the EPA DCI samples; however, the levels reported by Schecter et al. (1997)
for U.S. samples are significantly lower.
An estimated 26,300 metric tons of 2,4-D were consumed in the United States in
1995, making it one of the top 10 pesticides in terms of quantity used (U.S. EPA, 1997a).
An estimated 30,400 metric tons were consumed during 1987 (U.S. EPA, 1988c). Based
on the average CDD/CDF congener concentrations in 2,4-D presented in Table 8-24 (i.e.,
not including OCDD and OCDF), the corresponding TEQ concentration is 0.70 //g/kg.
Combining this TEQ concentration with the activity level estimates for 1995 and 1987
indicates that 18.4 g and 21.3 g of TEQ may have entered the environment in 1995 and
1987, respectively. These release estimates are assigned a H/H confidence rating
indicating high confidence in both the production and emission factor estimates. Based on
'",' ', ' • rim r, ' "• - li1'".1" "I"" i.'1 •'•'.'!' i'fi,.".; i?-' <; T<: >;.'•.•• I.1*1!1!"''i. ','..'*: ,'miw;,;. ,i. • ; " i •: • .
,„» vi,,' " i '.,„:„ • j'i „ ' .',,'! ."hi ,:; '„ •'' •' -,,:1'!'1:,' >r! .' i i "" .' ZFI, !;:'' .M!1; :'!,,! .>!r «;:;; :: 'i '•
this high confidence rating, the estimated range of potential release is assumed to vary by a
factor of 2 between the low and high ends of the range. Assuming that the estimated
releases of 18.4 g and 21.3 g of TEQ are the geometric means of these ranges, then the
ranges are calculated to be 13.0- to 26.0-g TEQ in 1995 and 15.1- to 30.2-g TEQ in 1987.
;t . . .'; • \ -,.,vi -i, •' ' •: ., • ;" •• .'',., ; i. . i. :• i 'i ' :.•. : i ' :., «.. >. .; » i.-, T,: •• i • ° .• . •
•I , . . '• • i'111 in , • , ..i ' r '• • •• i •.' ' . «' .'.•. •• 'f '•',»-, •. •••.•. i. i •• , . /
8.4. OTHER CHEMICAL MANUFACTURING AND PROCESSING SOURCES
8.4.1. Municipal Wastewater Treatment Plants
Sources - CDD/CDFs have been measured in nearly all sewage sludges tested,
although the concentrations and, to some extent, the congener profiles and patterns differ
widely. Potential sources of the CDD/CDFs include microbial formation (discussed in
Chapter 9), runoff to sewers from lands or urban surfaces contaminated by product uses or
deposition of previous emissions to air, household wastewater, industrial wastewater,
" '»"'= - •"!' < " III I ' I I ,'•'. ,|' ,•:•,.-.•'
chlorination operations within the wastewater treatment facility, or a combination of all the
8-28 April 1998
-------
DRAFT--DO NOT QU0TE OR CITE
above (Rappe, 1992a; Rappe et al., 1994; Horstmann et al., 1992; Sewart et al., 1995-
Cramer et a!., 1995; Horstmann and McLachlan, 1995).
The major source(s) for a given Publicly Owned Treatment Works (POT W) is likely to
be site-specific, particularly in industrialized areas. For example, Rieger and Ballschmiter
', ' > •
(1992) traced the origin of CDDs and CDFs found in municipal sewage sludge in Ulm,
Germany, to metal manufacturing and urban sources. The characteristics of both sources
were similar and suggested generation via thermal processing. However, in a series of
recent studies, Horstmann et al. (1992; 1993a; 1993b) and Horstmann and McLachlan
(1994a; 1994b; 1995) demonstrated that wastewater generated by laundering and bathing
could be the major source at many, if not all, POTWs that serve primarily residential •
populations. Although runoff from streets during precipitation events, particularly from
streets with high traffic density, was reported by these researchers to contribute
measurably, the total contribution of TEQ from household wastewater was eight times
greater than that from surface runoff at the study city.
Horstmann et al. (1992) provided initial evidence that household wastewater could
be a significant source. Horstmann et al. (1993a) measured CDD/CDF levels in the effluent
from four different loads of laundry from two different domestic washing machines. The
concentrations of total CDD/CDF in the four samples ranged from 3,900 to 7,100 pg/L and
were very similar in congener profile, with OCDD being the dominant congener followed by
the hepta- and hexa-CDDs. Based on the similar concentrations and congener profiles
found, Horstmann et al. (1993a) concluded that the presence of CDD/CDF in washing
machine wastewater is widespread. A simple mass balance performed using the results
showed that the CDD/CDFs found in the four washing machine wastewater samples could
account for 27 to 94 percent of the total CDD/CDF measured in the sludge of the local
wastewater treatment plant (Horstmann and McLachlan, 1994a).
Horstmann et al. (1993a) also performed additional experiments that showed that
detergents, commonly used bleaching agents, and the washing cycle process! itself were
not responsible for the observed CDD/CDFs. To determine if the textile fabric or fabric
finishing processes could account for the observed CDD/CDFs, Horstmann et al. (1993b),
Horstmann and McLachlan (1994a; 1994b), and Klasmeier and McLachlan (1995) analyzed
the CDD/CDF content of eight different raw (unfinished) cotton cloths containing fiber from
different countries and five different white synthetic materials (acetate, viscose, bleached
8-29
April 1998
-------
DRAFT-DO NOT QUOTE ORCITE
polyester, polyamide, and polyacrylic), as well as over 100 new textile finished products.
: ' •'•>''' : "-. '•.•'•:. '".Bi : " , '•<>, •:': ' ' .••'"^:'! ."vt •• i::x V i'!''" '•ii;< •',;'';' :.'i ;:,'. -' Uf'.''.•.'•• ,-i ' ©'(-'; " •"!. • •,
neither unfinished new fabrics nor common cotton finishing processes can explain the .
CDD/CDF levels found in wastewater. Rather, the use of CDD/CDF-containing textile dyes
arid pigments and the use in some developing countries of pentachlorophenol to treat
unfinished cotton appear to be the sources of the detected CDDs/CDFs.
Horstmann and McLachlan (1994a; 1994b; 1995) reported the results of additional
experiments that demonstrated that the small percentage of .clothing items with high
CDD/CDF levels could be responsible for the quantity of CDD/CDFs observed in household
wastewater and sewage sludge. They demonstrated that the CDD/CDFs can be gradually
removed from the fabric during washing, can be transferred to the skin, subsequently
: It:-; '. , I i.l , li'NS • ! ,"; . ,V , , • • i." .. . . ,•!•••.. :; . .vi , ,' '. • I
transferred back to other texfiles, and then washed out, or can be transferred to other
textiles during washing and then removed during subsequent washings.
Releases to Water - The presence of CDD/COFs in sewage sludge suggests that
CDD/CDFs may also be present in the wastewater effluent discharges of POTWs; however,
few studies reporting the results of effluent analyses for CDD/COFs have been published.
Rappe et al. (1989a) tested the effluent from two Swedish POTWs for all 2,3,7,8-
substituted CDD/CDF congeners. OCDD was detected in the effluents from both facilities at
concentrations ranging from 14 to 39 pg/L. 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-
HpCDF were detected in the effluent of one facility at concentrations of 2.8 and 2.0 pg/L,
respectively. No 2,3,7,8-substituted tetra-, penta-, and hexa-CDDs and CDFs were
detected (detection limits of 0.2 to 20 pg/L).
Ho and Clement (1990) reported the results of sampling during the late 1980s of 37
POTWs in OntariOj Canada, for each of the five CDD/CDF congener groups with four to
,'•'.' . ;' 'I,'1'"'"i" • ; '/'',.,.' ';•... >!';S, ";• :.v ''V'I'M'.I •''.•''.'•.''': "I: .!<, "'f. I.'.'J •, H'l;1.' ' -
eight chlorines. The sampled facilities included 27 secondary treatment facilities, 7 primary
treatment facilities, 1 tertiary plant, and 2 lagoons. The facilities accounted for about 73
percent of the sewage discharged by POTWs in Ontario. No CDDs/CDFs were detected
(detection limit in (pw ng/L range) in the effluents from the lagoons and the tertiary
treatment facility. Only OCDD and tCDF were detected in the effluents from the primary
treatment facilities (two and one effluent samples, respectively) HpCDD, OCDD, TCDF,
8-30
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
and OCDF were detected in the effluents from the secondary treatment facilities (detected
in four or fewer samples at levels ranging from 0.1 to 11 ng/L).
Gobran et al. (1995) analyzed the raw sewage and final effluent of an Ontario,
Canada, wastewater treatment plant for CDD/CDF congeners over a 5-day period.
Although HpCDD, OCDD, HpCDF, and OCDF were detected in the raw sewage (12 to
2,300 pg/L), no CDD/CDFs were detected in the final effluent at congener-specific
detection limits ranging from 3 to 20 pg/L.
The California Regional Water Quality Control Board (CRWQCB, 1996) reported the
results of effluent testing at nine POTWs in the San Francisco area. A total of 30 samples
were collected during 1992-1995; 1 to 6 samples were analyzed for each POTW. Table 8-
27 summarizes the sampling results. With the exception of OCDD, most 2,3,7,8-
substituted CDD/CDF congeners were seldom detected.
The CRWQCB (1996) data were collected to be representative of effluent
concentrations in the San Francisco area; these data cannot be considered to be
representative of CDD/CDF effluent concentrations at the 16,000+ POTWs nationwide.
Therefore, the data can only be used to generate a preliminary estimate of the potential
mass of CDD/CDF TEQ that may be released annually by U.S. POTWs. Approximately 122-
billion liters of wastewater are treated daily by POTWs in the United States (U.S. EPA,
1997c). Multiplying this value by 365 days/year and by the "overall mean" TEQ
concentrations listed in Table 8-27 (i.e., 0.29 pg/L, assuming not detected values are zero,
and 3.66 pg/L, assuming not detected values are one-half the detection limit) yields annual
TEQ release estimates of 13 to 163 grams/year.
Sewage Sludge Land Disposal - EPA conducted the National Sewage Sludge Survey
in 1988 and 1989 to obtain national data on sewage sludge quality and management. As
part of this survey, EPA analyzed sludges from 174 POJWs that employed at least
secondary wastewater treatment for more than 400 analytes including CDD/CDFs.
Although sludges from only 16 percent of the POTWs had detectable levels of 2,3,7,8-
TCDD, all sludges had detectable levels of at least one CDD/CDF congener (U.S. EPA,
1996a).. TEQ concentrations as high as 1,820-ng TEQ/kg dry weight were measured. The
congener-specific results of the survey are presented in Table 8-28. If all nondetected
values found in the study are assumed to be zero, then the mean and median CDD/CDF
concentrations of the sludges from the 174 POTWs are 50- and 11.2-ng TEQ/kg (dry
8-31 . April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
weight basis), respectively. If the nondetected values are set equal to the detection limit,
v :: ni : • . ,", mu1;; ,„ !• • " • : »' ,:».. i» "!•"; n; , „! ' . m .• , i , • :• , it,1!;:1,, ,"• , i
then the mean and median CDD/CDF concentrations are 86-and 50.4-ng TEQ/kg,
respectively {U.S. EPA, 1996a; Rubin and White, 1992).
Green et al, (1995) and Cramer et al. (1995) reported the results of analyses of 99
samples of sewage sludge collected from 75 wastewater treatment plants across the
United States during the summer of 1994. These data are summarized in Table 8-29. For
the calculation of results in units of TEQ, results from al! samples collected from the same
facility were averaged by Green et al. (1995) to ensure that results were not biased
towards the concentrations found at facilities from which more than one sample were
••Vi >./• •' , ' - "JIS .'. .' • ;*. ;•!'..•,:•'£ i''1'1. '. •/ I'-i'")!;,1 ''.',".",V;!'- 'l,.i'v, •,,,'.,! V* 'I"1'*1' ~ .:'; I
collected. If all nondetected values are assumed to be zero, then the POTW mean and
median CDD/CDF concentrations were 47.7- and 30,0-ng TEQ/kg (dry weight basis),
respectively (standard deviation of 45.0-ng TEQ/kg). If the nondetected values are set
equal to the detection limits, then the POTW mean and median CDD/CDF concentrations
were 64.6- and 49.1-ng TEQ/kg, respectively (standard deviation of 50.6-ng TEQ/kg). The
mean and median results reported by Green et al. (1995) and Cramer et al. (1995) are very
similar in te.rms of Jptal TEQ to those reported by EPA for samples collected 5 years earlier
(U.S. EPA, 1996a; Rubin and White, 1992). The predominant congeners in both data sets
are the octa- and hepta CDDs and CDFs. Although not present at high concentrations,
.•,' ", . ' ifj-i1 !':;!!' . • . •, •. ' i A • f ' ' • •!:",;,: :' ' '< -• ""., , , ij ' ••.*.. , " , „'. .. i , :.
2,3,7,8-TCDF was commonly detected.
The CDD/CDF concentrations and congener group patterns observed in these two
U.S. surveys are similar to the results reported for sewage sludges in several other Western
countries. Stuart et al. (1993) reported mean CDD/CDF concentrations of 23.3-ng TEQ/kg
(dry weight) for three sludges from rural areas, 42.3-ng TEQ/kg for six sludges from light
industry/domestic areas, and 52.8-ng TEQ/kg for six sludges from industrial/domestic areas
collected during 1991-1992 in England and Wales'. Naf et al. (1990) reported CDD/CDF
concentrations ranging from 31 - to 40-ng TEQ/kg (dry weight) in primary and digested
sludges collected from the POTW in Stockholm, Sweden, during 1989. Gobran et al.
(1995) reported an average CDD/CDF concentration of 15-7-ng TEQ/kg in anaerobically
digested sludges from an industrial/domestic POTW in Ontario, Canada. In all three studies,
the congener group concentrations increased with increasing degree of chlorination, with
OCDD the dominant congener. Figure 8-6 presents congener profiles, using the mean
concentrations reported by Green et al. (1995).
• • , • HI .•;- ',:,; i, .>,;•.• - ,:«.!• •• * ..• ;• ;• , :,<•:„;:,•, ;, • ir;l,v ', ' ': • . . •
8-32 . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
r - • ' ' • ' . '
Approximately 5.4-million dry metric tons of sewage sludge are estimated by EPA to
be generated annually in the United States based on the results of the 1988/1989 EPA
"National Sewage Sludge Survey (Federal Register, 1993b). Table 8-30 lists the volume of
sludge disposed annually by use and disposal practices. No more recent comprehensive
survey data to characterize sludge generation and disposal practices during 1995 are
available. For this reason, and because the median TEQ concentration values reported in
the 1988/1989 survey (U.S. EPA, 1996a) and the 1995 survey (Green et al., 1995; Cramer
et al., 1995) were nearly identical, the estimated amounts of TEQs that may have been
present in sewage sludge and been released to the environment in 1987 and 1995 were
assumed to be the same. These values, presented in Table 8-30, were estimated using the
average (i.e., 50-ng TEQ/kg) of the median TEQ concentration values (nondetected values
set at detection limits) reported by U.S. EPA (1996a) (i.e., 50.4-ng TEQ/kg) and by Green
et al. (1995) and Cramer et al. (1995) (i.e., 49.1-ng TEQ/kg). Multiplying this mean total
TEQ concentration by the sludge, volumes generated, yields an annual potential total release
of 208 grams of TEQ for nonincinerated sludges. Of this 208 grams of TEQ, 3.6 grams
enter commerce as a product for distribution and marketing. The remainder is applied to
land (105.5 grams) or is landfilled (98.8 grams).
These release estimates are assigned a H/H confidence rating indicating high
confidence in both the production and emission factor estimates. The high rating was
based on the judgement that the 174 facilities tested by EPA (U.S. EPA, 1996a), and the
75 facilities tested by Green et al. (1995) and Cramer et al. (1995) were reasonably
representative of the variability in POTW technologies and sewage characteristics
nationwide. Based on this high confidence rating, the estimated range of potential annual
emissions is assumed to vary by a factor of 2 between the low and high ends of the range.
Assuming that the best estimate of annual emission to land (105.5-g TEQ/yr) is the
geometric mean of this range, then the range is calculated to be 74.6- to 149-g TEQ/yr.
Assuming that the best estimate of 3.6-g TEQ annual emissions in product (i.e., the
fraction of sludge that is distributed and marketed as a product) is the geometric mean of
the range, then the range is calculated to be 2.5- to 5.0-g TEQ/yr.
8-33
April 1998
-------
- DRAFT-DO NOT QUOTE OR CITE
1 ' -, ;.• [-' . .• • • .. • t; '. ..•; •. . •• '! :•,', ;; ' ' v ' ''•<' -.' , . ; , { • '.V ':, l • • '
8.4.2. Drinking Water Treatment Plants
There is no strong evidence that chlorination of water for drinking purposes results
in the formation of CDD/CDFs. Few surveys of finished drinking water for CDD/CDF
content have been conducted. The few that have been published only rarely report the
i, . "<, i ;•.. - •,'• .•• • . tit •• , ii'. " ,"', •., ' Hi ' TI i '.'.•.!• i
presence of any CDD/CDF even at low pg/L detection limits, and in those cases, the
CDD/CDFs were also present in the untreated water.
Rappe et al. (1989b) reported the formation of CDFs (tetra- through octa-chlorinated
CDFs) when tap water and double-distilled water were chlorinated using chlorine gas. The
.I,::"!'! i, . » ", " p'iiii . r<: ,,\ ', : ,11. : i':.j:Hr;;,» ' ,|J • ir''„" ' .1 ,,ii!|ii,l!!li;!i\ ;i"'':i" lii'ft- : "ii;/" ,,:„, ', '; u •
CDF levels found in the single samples of tap water and double-distilled water were 35- and
7-pg TEQ/L, respectively. No CDDs were detected at detection limits ranging from 1 to 5
pg/L. However, the water samples were chlorinated at a dosage rate of 300 mg of chlorine
per liter of water, which is considerably higher (by a factor of one to two orders of
magnitude) than the range of dosage rates typically used to disinfect drinking water.
Rappe et al. (1989b) hypothesized that the CDFs or their precursors are present in chlorine
gas. Rappe et al. (1990a) analyzed a 1,500-liter samp|e of drinking water from a municipal
drinking water treatment plant in Sweden. Although the untreated water was not
analyzed, a sludge sample from the same facility was analyzed. The large sample volume
,;"''"' ;. ' , • i 'i,; i'jj!;; :;• ' '•• « '"', :, : ,m , • fl ',';'[ , J"''.' ",,'•:' i'•' i 'i'1'"., V1 ' : "J; ""!•'' «" •'!', !Viii; •'' iifyfF''''''' ' '•,; , '• :i i1 ' • •,
enabled Rappe et al. (1990a) to detect CDD/CDFs at concentrations on the order of 0.001
pg/L The TEQ content of the water and sludge was 0.0029-pg TEQ/L and 1.4 ng/kg,
respectively. The congener patterns of the drinking water and sludge sample were very
similar, suggesting that the CDD/CDFs detected in the finished water were present in the
untreated water.
8.4.3. Soaps and Detergents
As discussed in Section 8.4.1, CDD/CDFs were detected in nearly all sewage .
sludges tested whether obtained from industrialized areas or rural areas. Because of their
ubiquitous presence in sewage sludge, several studies have been conducted to determine
the spurce(s) of the CDD/CDFs. A logical category of products to test because of their
widespread usage are detergents, particularly those that contain or release chlorine during
use (i.e., hypochlorite-containing and dichloroisocyanuric acid-containing detergents). The
"• ' 'v;: , "" • "' "\'>S , T •..' • "'••"-.'' ' ;: .'',•' ". •)' •»'',;:": i ''•')'.<':i v/.ilwr'^Kf!:1'':1'1.1'.'.'Ki.'/.' ' ,. ''if1' < '•'•'',•
results of studies conducted to date, which are summarized below, indicate that CDD/CDFs
iii!:!!!! •<,•', : •'-.'• i'-':-.' '"":,', • '• >' ' i •. •,';.>>iii,-1.' ivitm .'jJ..m.«.,!*'flOT •«•»:'ii', «'*>;:'' *. ' • i, • .\ • .
• ' ,c HiJiiniii!! :t , ', ," :•'• c ', /", i1"! '"-V''; i:1:', .li,,,11,,, ' I!iii111;!"li:ifljl,lw; i1!" \ vt i-1 .iipiii'.1111,,, .ii i" ,"i
are not formed during use of chlorine-free detergents, chlorine-containing or chlorine-
8-34 April 1998
-------
. DRAFT-DO NOT QUOTE OR CUE
releasing detergents, and chlorine bleach during household bleaching operations. Although
few results of testing of detergents for CDD/CDFs were reported, low levels of CDD/CDFs
were reported only in a sample of a Swedish dichloroisocyanurate-containing detergent.
CDD/CDFs were also detected in. a sample of a Swedish "soft soap," manufactured from
tall oil.
Sweden's Office of Nature Conservancy (1991) reported that the results of a
preliminary study conducted at one household indicated that CDD/CDFs may be formed
during use of dichloroisocyanurate-cbntaining dish washing machine detergents. A more
extensive main study was then conducted using standardized food, dishes, cutlery, etc. and
multiple runs. Testing of laundry washing, fabric bleaching, and actual testing of the
CDD/CDF content of detergents was also performed. The study examined:
(1) hypochlorite- and dichloroisocyanurate-containing dish washing machine detergents; (2)
sodium hypochlorite-based bleach (4.4 percent NaOCI) in various combinations with and
without laundry detergent; and (3) sodium hypochlorite-based bleach, used at a high
enough concentration to effect bleaching of a pair of imported blue jeans CDD/CDFs were
nondetected in either the chlorine-free detergent or the detergent with hypochlorite; 0.6-pg
TEQ/g was detected in the detergent containing dichloroisocyanurate. The results of all
dish and laundry washing machine tests showed very low levels of CDD/CDFs, often
nondetected values. There was no significant difference between the controls and test
samples. In fact, the control samples contained higher TEQ content than some of the
experimental samples. The drain water from the dish washing machine tests contained
< 1.0- to <3.0-pg TEQ/L (the water only control sample contained <2.8-pg TEQ/L). The
CDD/CDF content of the laundry drain water samples ranged from <1.1-to <4.6-pg TEQ/L
(tjie water only control sample contained <4.4-pg TEQ/L).
Thus, under the test conditions examined by Sweden's Office of Nature
Conservancy (1991), CDD/CDFs are not formed during dish washing and laundry washing
nor during bleaching with hypochlorite-containing bleach. No definitive reason could be
found to explain the difference in results between the preliminary study and the main study
for dish washing with dichloroisocyanurate-containing detergents. The authors, of the study
suggested that differences in the foods used and the prewashing procedures employed in
the two studies were the likely causes of the variation in the results.
8-35
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Hagenmaier and Brunner {1993) also conducted a laundry study in Germany and
,,'"IN h " ' , " 'i, "'!!,I,,1' I • • :" , , ' " ,. ™ !,i"! "• , ' , ' ,!"°'i IN ,ii,iu! " '•>' ' "'" 'J1" i, •' ,'. f ""',1' ' , •;, • »!;!' !l';"' ,i,;!i|lili!1 ': '"i'l1, J „
obtained results similar to those reported by Sweden's Office of Nature Conservancy
(1991) main study. Hagenmaier and Brunner (1993) used a popular detergent with bleach
and one without bleach. The total volume of laundry wastewater (approximately 85 to 90
L) from the experiment with the bleach-containing detergent contained 390 ng of total
'!.';•'.. , 'i '. •• i /Sis : / , ''• •..;•,.' ' •; ','. • :'}:'":~i'"i ',> r- \ ::: :-;i!' ;«! «l;i: .J'iiji'HA i.'ltoY',1,'.1'•'•• • ';!
CDD/CDF, while the bleach-free wastewater contained 460 ng.
Rappe et al. (1990c) analyzed a sample of a Swedish commercial soft soap, as well
as a sample of tall oil and a sample of tall resin for CDD/CDF content. Tall oil and tall resin,
byproducts of the pulping industry, are the starting materials for the production of soft,
liquid soap. Crude tall oil, collected after the Kraft pulping process, is distilled under
reduced pressure at temperatures of up to 280-290°C, yielding tall oil and tall resin. The
measured TEQ content of the liquid soap was 0.447-ng TEQ/L. PeCDDs were the dominant
; *v ' " "' '•"',;,' "''ill .'•' " • .'" "''i, •• "i I .'. ',:':", '"'"; ivi";,' !•'.'•", '' .*• / "!> ,':.!'• ;'•'<" • .Jr™ .•'•'' ", .' i;' ;j
congener group followed by HpCDDs, HxCDDs, PeCDFs, and OCDD with some tetra- CDFs
and CDDs also present. The TEQ content of the tall oil (9.5 rig/kg) and, tall resin (200
•:•:.; i, I ' iXittiiJ !, •, " ," '' i,'1 , t.'fK v • J I •• I
ng/kg) was significantly higher than the level found in the liquid soap. The tall oil contained
i •;' i "' •' i/iii' ,« , ,"•! :!'" '" !'" ' I " f, ','
primarily tetra- and penta- CDDs and CDFs, while the tall resin contained primarily HpCDDs,
ii;.i,l"'!i!l!l ' » ' ' - '' "1|1,, • «• 'i i11' " • lu|i , • i 5 I ' ' • :"
HxCDDs, and OCDD. Rappe et al. (1990c) compared the congener patterns of the three
samples and noted that although the absolute values for the tetra- and penta- CDFs and
: ,,' „ '•• Vliiii'!! ;,| ,, IN|1 ' ' • . , "n, : • , • „ ,• , , . , ,;,",|i,,'.,i , •, • • 'ij'.r .IIMI'II, ,,i!i,M, :,, i • !;:, '«,:, - , i,
CDDs differed bejween the tall oil/tall resin and liquid soap samples, the same congeners
wete present in the samples. The congener patterns for the more chlorinated congeners
were very similar. Table 8-31 presents the results reported by Rappe et al. (1990c).
In 1987, 118-million liters of liquid household soaps were shipped in the United
States (U.S. DOCf1990b); shipment quantity data are not available for liquid household
soap in the 1992 O.S. Economic Census (UlS. DOC, 1996). Because only one sample of
liquid soap has been analyzed for CDD/CDF content (Rappe eit'aC 1990c), only a very
preliminary estimate of the annual release of CDD/CDF TEQ from liquid soap can be made.
'•••'"'• ;';l •'• .'.• i!jl!i -:-.' •. •-'•:,'.i1:lt „"&• ''• -vi .;••• :vy--'!!":-i i<.;.r^i.*-ivjnij-'(..';.''':;:»:,'' '«> •> : ":'
If it is assumed that an average 118-million liters of liquid soap contain 0.447-ng TEQ/L,
then the resulting estimate is 0.05-g TEQ/yr.
8.4.4. Textile Manufacturing and Dry Cleaning
As discussed in Section 8.4.1, CDD/CDFs have been detected in nearly all sewage
sludges tested whether obtained from industrialized areas or rural areas. To determine if
."..•• 8-36 April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
' - ' • ' f • - • '
the textile fabric or fabric finishing processes could account for the observed CDD/CDFs,
several studies were ponducted in Germany. These studies/summarized in the following
paragraphs, indicate that, although some finished textile products do contain detectable
levels of CDD/CDFs and that these CDD/CDFs can be released from the textile during
laundering or dry cleaning, textile finishing processes are typically not sources of CDD/CDF
formation. Rather, the use of CDD/CDF-containing dyes and pigments and the use in some
countries of pentachlorophenol to treat unfinished cotton appear to be the sources of the
detected CDD/CDFs.
Horstmann et al. (1993b) analyzed the CDD/CDF content of eight different raw
(unfinished) cotton cloths containing fiber from different countries arid fiye different white
synthetic materials (acetate, viscose, bleached polyester, polyamide, and polyacrylic). The
maximum concentrations found in the textile fabrics were 30 ng/kg in the cotton products
and 45 ng/kg in the synthetic materials. Also, a potton finishing scheme was developed
that subjected one of the cotton materials to a series of 16 typical cotton finishing
processes; one sample was analyzed following each step. The fabric finishing processes
showing the greatest effect on CDD/CDF concentration were the application of an
indanthrene dye and the "wash and wear" finishing process, which together resulted in a
CDD/CDF concentration of about 100 ng/kg. Based on the concentrations found, the
authors concluded that neither unfinished new fabrics nor common cotton finishing
processes can explain the CDD/CDF levels found in laundry wastewater.
Fuchs et al. (1990} reported that dry cleaning solvent redistillation residues collected
from 12 commercial and industrial dry cleaning operations contained considerable amounts
of CDD/CDFs. The reported TEQ content ranged from 131 to 2,834 ng/kg with the
dominant congeners always OCDD and the HpCDDs. Towara et al. (1992) demonstrated
that neither the use of chlorine-free solvents nor variation of the dry cleaning process
parameters lowered the CDD/CDF content of the residues.
Umlauf et al. (1993) conducted a study to characterize the mass balance of
CDD/CDFs in the dry cleaning process. The soiled clothes (containing 16-pg total CDD/CDF
per kg) accounted for 99.996 percent of the CDD/CDF input. Input from indoor air '
containing 0.194 pg/m3 accounted for the remainder (i.e., 0.004 percent). The dry
cleaning process removed 82.435 percent of the CDD/CDF in the soiled clothing. Most of
the input CDD/CDF (82.264 percent) was found in the solvent distillation residues. Air
8"37 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
erriissions (at 6.041 pg/m3) accounted for 0.0008 percent of the total input, which is less
than the input from indoor air. The fluff (at a concentration of 36 ng/kg) accounted for
0.1697 percent, and water effluent (at a concentration of 0.07 pg/L) accounted for
0.0000054 percent.
Horstmann and McLachlan (1994a; 1994b; 1995) analyzed 35 new textile samples
(primarily cotton products) obtained in Germany for CDD/CDFs. Low levels were found in
most cases (total CDD/CDF less than 50 ng/kg). The dominant congeners found were
OCDD and the HpCDDs. However, several colored T-shirts from a number of clothing
producers had extremely high levels, with concentrations up to 290,000 ng/kg. Because
the concentrations in identical T-shirts purchased at the same store varied by up to a factor
of 20, the authors concluded that the source of CDD/CDFs is not a textile finishing process,
because a process source would have resulted in a more consistent level of contamination.
Klasmeier and McLachlan (1995) subsequently analyzed 68 new textile products obtained
in Germany for OCDD and OCDF. Most samples had nondetectable levels (42 samples
<60 ng/kg). Only four samples had levels exceeding 500 ng/kg.
Horstmann and McLachlan (1994a,- 1994b) reported finding two different congener
group patterns in the more contaminated of the 35 textile products. One pattern agreed
well with the congener pattern for PCP reported b'y Hagenmaier and Brunner (1987), while
the other pattern was similar to that reported by Remmers et al. (1992) for chloranil-based
dyes. The authors hypothesize that the use of PCP to preserve cotton, particularly when it
is randomly strewn on bales of cotton as a preservative during sea transport, is the likely
source of the high levels occasionally observed. As discussed in Section 8.3.8, the use of
PCP for nonwood uses was prohibited in the United States in 1987. However, Horstmann
and McLachlan (1994a) comment that PCP is still used in developing countries, especially
to preserve cotton during sea transport.
Horstmann and McLachlan (1994a; 1994b)conducted additional experiments that
demonstrated that the small percentage of clothing items with high CDD/CDF levels could
be responsible for the quantity of CDD/CDFs observed in household wastewater. They
demonstrated that the CDD/CpFs can be gradually removed from the fabric during washing,
can be transferred to the skin, and subsequently transferred back to other textiles and then
I"'.1" ' • ... iiiiC ;' ''•'"•.':';: '!!".':.',»'<•' I'1 I,'!-. ,.' il; Mi';"'i ! '.''.•', v",r ,1. "IF I1, ."',! •. ., iiiHMi f ",. • • I .
washed out, or can be transferred to other textiles during washing and then removed during
subsequent washings.
,„ ' .«!"•!" i • ." • , - / ' i , ".I. ,h ,' ' ' • ; . :'i -I ' ' ' ." „ ,
8-38 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
8-39
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Wastewater Effluent |
Wastewater Sludge
•
Bleached Pulp
^
to — -
11
Ji
Hi
raj
it
CC £
SB
II
iff
11
Jo
11
Congener/Congener
Group
CO O O 0 0 CO CO
in CM ?co
05 Q Q Q Q O 0
— 2 S 2 2 ^ o
— co eo co co p- S
Q CM CO CO CO <•* c
Q Q Q Q *-
Z Z Z Z
CO CM KT CM 0
co T- •- r- »- en co
S co o in o ,-,
™ CM •* CO CO g
o 3 2 3 2 en >-;
co •* in P-; P-. o o
co r::: ~ — ta m
Q Q Q Q Q •" cc
§ Z Z Z Z <*
in P CM S
CO CM CO CO CO p~ g
i §i i
2 CM »- CM — ° g
^- ^t co in
tr *- o ^ o ^.
— 2 2 2 2 co' 5
o — SfcM CM 2 2
^j- o o o o co co
z z z z
co ? in in
^1* O O O O CO co
z z z z
Q
Q Q Q P.
0 Q Q o y
g O CJ CJ ;§•
Q O x x X CO
f> OL 00 CO O> f^
H* co r** r** oo o
co r*"* ^ CD r** ^
Is* CO CO CO CO CO «
CO* W CM OJ C*l OJ" cj
N *~ " "" *" ^ °
CiCMOJOOOOCOOCO
w S" to iS •" o
gSSzzzzoz^
owc72 2 2 S^2s
CM £i £i co co 10 co ^ ^ J2
-z.-z.-z.-z. -z.
5rs-c£>c6ri«''O
^iiiiiiii^
— •« -°- — «
q
OCMCOCOCO — cop^t-dgyO'co''-S
™QQQQC>QC1QQ
zzzz-zzzz
z
10 *f r** r** CD
co CN r^ CN ^ ^* *~ co »-• c\
04 Q Q Q Q Q
12 Z Z -Z. 2
o.cooooocooco
P22izii2l2
z z z z z
r^CMCOCOCOCOCOCO
coOOOOOOOOCM
> zzzzzzzi
U- U_
U- LL U. LL R fj
--8888^1
LJ LJ x X X X ~*~ ~^~
Ro.D_ooooo)cor^co
h-cocor^p^cor'-tor11^
oor-r^-^tor^O'd-^t
r^* co ^f co co co ^t co co ^
COCMCOCNCNCNCOCMOiM
CM - CM .- - ^ CM - - 0
^ ° CO CO
gg-:-
-
P~ _ CO CO
^ CO CM CO
in *~ co oo'
Total 2,3,7,8-CDD"'b
Total 2,3,7,8-CDF"'b
Total TEQ(ND = zero)b
Total TEQ{ND = DL)b •
eo
C
in
O)
cc
§
I Total CDD/GDFb
C "O
ID
-------
DRAFT-DO NOT QUOTE OR CITE
. 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
Source: Uedicn eoncmntunu f
0.5
Ratio (median congener TEQ concVtotal TEQ 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 ^,3 ,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
Source: Uadion con
from U.S. BPA (199O»); nondaucu «« eqa»l to 1/2 dM»ctio& «™t*
Figure 8-1. 104-Mill Study Full Congener Analysis Results for Pulp
8-41
April 1998
-------
:,, i"'
NOT QUOTE OR CITE
Ratio (median congener cone. / total CDD/CDF cone.)
O.I 0.2 0.3 O.4
0.5
2,3.7.8-TCDD
1^,3.7,8-PeCDD'
1,2,3.4.7,8-HxCDD
1,2,3,6,7,8-HxCDP
1,2.3,7,8,9-HxCpp
1,2,3,4,6,7,S-HpCDD
1 ,2.3.4,6.7.8,9-6CDI>
2,3,7,8-fCDF
1,2,3,7.8-PeCDF
2,3.4,7.8-PcCDF
1 A3 ,4.7,8-HxCDF
lA3,6,7,S-HxCI>F
1,2,3,7.8,9-HxCDF
2,3.4,6,7,8-HxCDF
lA3,4,6,7.S-HpCDF
1.2,3,4,6.7,8,9-dCDF
«~»«: M.<1.. «»n
HPA F
2,3,4,6,7.8-HxcbF
l,2,3,4.6V7.8-HpCDF
1,2.3,4.7.8,9-HpCDF
1^^.4,6,7,8,9-OCDF
«nn*:U«l>
0.1
Ratio (median congener TEQ concVtotal TEQ cone.)
* .Pfg. ...i,,,.,, '..M,,,, .,' , .:, M ., &,S, , . 0.6 .
O.7
0.8
idoo« firen U.S. BPA (199O«); nondatMt* Mt •
l ta IB .Uuctim limit.
Rgure 8-2. 104-Mill Study Full Congener Analysis Results for Sludge
8-42
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ratio (median congener cone./totnl CDJD/CDF cone.)
0-1 0-2 0.3 0:4 0.5 ' 0.6
2,3,7,S-XCDr>
1.2,3 ,.4.7,8-HxCDD
1,2,3,6.7.8-HxCDD
1.2,3.7.8 ,9-HbcCr>r>
1,2.3,4,6,7,8-HpCDD
l,2.3,4,6.7.8,9-OCI>r>
2,3,7.8-TCDF
1 ,2.3 ,7.8-PeCDF
2.3.4,7.8-P-eCDF
1 .2.3 ,4,7,8-HxCDF
1 ^2.3 ,6,7.8-HxCDF
1^,3.7,8.9-HxCDF
2,3.4,6.7,8-HxCDF
1,2,3.4,6,7,8-HpCDF
.4.7.8.9-HpCDF
Ratio (median congener TEQ concVtotal TEQ cone.)
0.2 0.3 0.4 0.5 0.6
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1^^,4,7,8-HxCDD
1^,3,6,7,8-HxCDD
1^,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1^,3,4,6,7,8,9-:OCDD
23,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1^,3,6,7,8-HxCDF
1^,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
li2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1^,3,4,6,7,8,9-OCDF
Scarce: Mediin concontmioni from U.S. EPA (1990m); nondetccu let equal to 1/2. dctecnra limit.
Figure 8-3; 104-Mili Study Full Congener Analysis Results for Effluent
8-43
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
1
I
1
==
(
1
itewater S
>
a
g
a
m
J
(
"a § "5 -
d 2 d E
ZSZ$
9 ^J
1? 1
ll
if
i?a
ffl " Q
5gs
° s°i
-PI
II
en £
C •-£
- J
11
§°I
5§I
°1°|
*g*l
» B
?=£
= g
c •=
5 °
II
HI
ft
i a
§.
j
iHWlilil;; , ' ""„
CO 00 CO 00 00 GO *
^ S 0 S O ^ 5
m ID in to o
«- in in in in co r~
M a a a a "> °°
022220g
s S 2 S S ??;=;
2 — — S S
£o o o o £°
Q to 10 u> jo O —
z a a a a z 9
Z 2 Z 2 ^
»- co ro n co co £
T- in 10 if> to 10
a a a a a a Q
2 2 2 Z Z Z t
^oooo^S
01 N « CO CO CO 2
't O "- CM 2
* S'f* J2 * § g
SiSoo^S.
"™* Q St J-T_ v^ *^
isigiHj-
"• Q Z 2 z CM
»— to to in m o
a a a a a ^ !2
zzzzz
co _ in co co "*. S
0 ° 0 CM ^ 5 ?
«- o o o o o co
r* r* p^ r^ r^ tc
10 0 D Q 0 Q •-
ozzzzzo
— 0 0 0 0 0 g
Q CO CO CO CO CO ~
2 Q Q Q Q Q 9
22222
__
T— in in tn in in °
Q Q O Q Q Q Q
2 2 2 2 2 2 §
CO Tt*
cjOOOoOe4
Q
Q Q Q fi
_ D o Q y
§y<^x
g S ^ ¥ X co
fj Q. co co o> r*-
h- oo r»- r* oo to
co p*. •* co r-^ ^
r^ n co c*J cr? c*? §
cr? oi" w CM M ca QJ
-' "! ..„'! '. , • !|, • ll"), „'" !'
cococooococococococo
wooSooooSo
toiQir^minmmif)*-
cou5ioiomi£5ir)mu>^-
^QQQQQQQQQ
OZ2ZZZZ222
— .000000000
^oooooooo^-
QiotniDmininmtno
ZQQQQQQQQn.
2ZZZZZZ2C
_
T— CO CO CO CO CO CO CO CO Ji
ooaaoaooox
z;zzzzzzzz|
^ o o o o o'o o o o
CN CO CO CO CO CO CO CO CO PI
cno«-ooO'-cMoo
w w CM" w oT S
T-!Sl-.B!2!£inininin2
dQQQQQQQClQ
2Z2222222§
m ^f
CJOQ-OOOOOOO
u. u_
u. u. u. u. S Q
.. .. Q Q Q Q " "
QQ^y^^ix
g^^zxxicoro
QjQ.d.COCOCDCOr^CO
1— cocop^r-''cor~rcor-r
eoi^p~'a-cor-co'!j->*
I^ CO Tt" CO" CO* CO * CO" CO t
cocgcoc-JcMoTcocJcJcj
|cl"°
55! •* cs °J
SairfSi
r~ "^ in «
oi 0 W ^
n>
'02.
°S^s°
Q Q M ii
A^°°
co co 2: H
p*. r% ~* —
co co'g g
es
c
(D
(D
"o
1
CO
«>
•* s
&!
W Q.
s i
c? S
5 CD
g 0
c .2
II °-
sL
~B3 ~at
c a.
F:
o>
en
Q
1
_ffl
O
to
o
3
CO
8-44
April 1998
-------
DRAFTr-DO NOT QUOTE OR CUE
Table 8-3. Summary of Bleached Chemical Pulp and Paper Mill Discharges
of 2,3,7,8-TCDD and 2,3,7,8-TCDF
Matrix
Effluent
Sludge11
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
1988
Discharge3
(g/year)
201
1,550
356
210
1 ,320
343
262
2,430
505
1992
Discharge11
(g/year)
22
99
32
33
118
45
24
124
36
1992
Discharge0
(g/year)
71
341
105
NR
NR
100
NR
NR
150
1993
Discharge15
(g/year)
19
76
27
24
114
35
22
106
33
1994
Discharge13
(g/year)
14.6
49.0
19.5
18.9
95.2
28.4
16.2
78.8
24 1
NR = Not reported.
V
a 104-Mill Study (U.S. EPA, 1990a): Total discharge rate of congener or TEQ (based only on
2,3,7,8-TCDD and 2,3,7,8-TCDF concentration) summed across all 104 mills.
NCASJ 1992 Survey (NCASI, 1993), 1993 Update (Gillespie, 1994), and 1994 Update (GiUespie.
1995): Total discharge rate of congener or TEQ (based only on 2,3,7,8-TCDD and 2,3,7,8-
TCDF concentration) summed across all 104 mills. The daily discharge rates reported in NCASI
(1993), Gillespie (1994), and Gillespie (1995) were multiplied by a factor of 350 days/yr to *
obtain estimates of annual discharge rates.
c The discharge in effluent was estimated in U.S. EPA (1993d) for January 1, 1993. The TEQ
discharges in s|udge and pulp .were estimated by multiplying the 1988 discharge estimates for
each by the ratio of the 1993 and 1988 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).
Approximately 20.5 percent of the sludge generated in 1990 were incinerated. The remaining
79.5 percent were predominantly landfilled (56.5 percent) or placed in surface impoundments
(18.1 percent); 4.1 percent were land-applied directly or as compost, and 0.3 percent were
distributed/marketed (U.S. EPA, 1993e).
g/year = grams per year
T ' . ....
Sources: Gillespie (1995); Gillespie (1994); NCASI (1993); U.S. EPA (1993d); U.S. EPA (1993e).
8-45
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-4. CDD/CDF Concentrations in Graphite Electrode Sludge
•from Chlorine Production
Congener/Congener Group
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Total 2,3,7,8-CDD*
TotaJ 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*
Sludge 1
teg/kg)
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
1.015
152.37
13.5
ND (0.006)
ND (0.070)
ND (0.046)
0.22
0.92
64
75
68
24
31
263.14
Sludge 2
Cug/kg)
ND (0.009)
ND (0.009)
ND (0.026)
ND(0.016)
ND (0.022)
0.21
2.0
56
55
25
71
16
2.8
1.9
19
19
76
2.21
341.7
30.2
ND (0.009)
ND (0.009)
ND (0.064)
0.48
2
150
240
140
53
76
661.48
Sludge 3
Ug/kg)
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
2.0
19
20
71
2.45
339.6
30.2
ND (0.009)
ND (0.009)
ND (0.074)
0.56
2.2
140
240
140
54
71
647.76
Sludge 4
Ug/kg)
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
0.705
303
27.7
NR
NR
NR
NR
0.65
NR
NR
NR
NR
81
NR
ND s Nondetected (values in parentheses are the reported detection limits)
NR =3 Not reported
* ii Calculated assuming not detected values were zero.
M9/kg = micrograms per kilogram
;::!; ^ • ' ••':-''.li-:ffl.;l''''.1.^i;;.'|;.'f? '';'.i;"y;? '.;'
Spurces: Rappe et at (1991); Rappe (1993)
8-46
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
CO
03
•jo
0
CO
CD
U
8
U-
Q
U
Q
Q
O
LO
CO
CB
CJ •••«
co 5
•*••
^J ***•
•f-.J
ol
P J
cfi"
of
CO "3
?J
if
CD ~S
a
I
CD
i_
c
CD
1 0)
1 C
J
.i
DC
^
•
DC
QC
Z
oc
DC
Z
DC
Q
Q
O
03
iS
DC
OC
CC
CC
CC
Z
oc
oc
IPeCDD
CD
O
DC
DC
DC
CC
Z
CC
z
QC
OC
Z
HxCDD
,2
Q
Q
0
m
o
.6
a
z
a
z
Q
Z
Q
O
O
a.
X
CO
H
-
a
a
c
o
CD
d
d
a
z
Q
Z
Q
Q
O
0
CD
O
DC
DC
DC
*£.
DC
OC
Z
QC
OC
LL
a
u
CO
£
oc
QC
QC
QC
Z
oc
z
DC
Z
CC
z
LL.
Q
O
I
CD
.2
DC
DC
CC
CC
Z
oc
z
oc
oc
z
HxCDF
CD
O
n
n
o
o
d
a
a
z
CN
r—
U-
Q
0
Q.
X
CO
.2
Q
Z
Q
Z
CN
O
LO
d
CO
Q
Z
CN
LL.
Q
O
O
CD
.2
CN
O
d
M—
o
I E
1= CD
C O)
o _o
"S2
CD >_
I-
. — w .
T3 "D P
0> ® CD
0» |
CD CD o
•^ c 'E
o o •
Z Z II
II II g
oc a "Bj
Z Z 3
CD
O)
O)
•a
CD
TJ
CD
D)
"N
D
X
O
CO
8-47
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Q.
O _O
!••» T;; e2J t
» *O .£
to «> m ~;
^ CO ^ |
pj S JS £
CM —
Q.
o _
H~ ^ *
I .3
c$ — ~
CM
Oc"~
^ J s I
CM""" tt ~
(X
O — —
1— .3*
co "S g>
CM
Q.
O — —
£
C
o
z
to
CD
i
S
c
o
o
2
1
„— .
CN
Iq
c
Q
Z
CM
O
d
a
z
CM1
O
O
O
z
0
o
a
z
a
Q
o
CO
£
c>
ID
j;
C
0
c
"2
CO
c
o
V
J_l^
2>
0.
0
c
z
10
^
i
c\
c
c
S
o
o
a
z
CM
0
0
a
z
CM
0
O
a
z
0
o
Q
Z
Q
a
o
S.
S
£
to
a>
ID
•
_
C1
C
c
c
0
V
_
c>
C
' C
Q
Z
S
c
c
0
z
cs
c
0
o
z
CM
q
o
Q
z
CM
q
o
a
z
s
o
o
z
1 HxCDD
CO
o
t-
cc
to
,_
10
_
?
c
o
c
^
0
V
^
o
c
o
0
z
i>
C
o
a
z
R
0
0
o
z
CM
q
d
a
z
CM
O
O
a
z
§
o
Q
Z
Q
a
o
a
S
r^
O
r;
O
i
S
C
c
c
z
0
V
^
c
d
0
z
(^
0
d
a
z
c\
C
0
o
z
CM
q
d
Q
Z
CM
q
d
a
z
CM
O
d
a
z
a
a
o
o
2
£
to
o
+
ID
+
a
o
z
o
dZ
a
z
+
u.
Q
CO
12
0
»~
H-
to
+
O
Q
Z
Q
Z
a
z
Q
Z
U.
0
O
CO
1°.
0
,P*
+
CO
CO
+
o
z
Q
Z
Q
Z
0
Q
Z
u.
Q
O
X
CO
1°.
0
h-
+
CO
••*
Q
a
Q
z
Q
Z
0
Q
Z
u_
O
O
0.
CO
£
O
*-
+
!
O
Q
Q
0
Z
a
o
LL
O
O
o
CO
1°.
.
'
!
'
!
:
•
:
:
,
CDD/CDF !
CO
12
e
o
Q_
CO
CD
•o
CD
o
a.
ro
Q-To C. —
W *J
E ° "S co
CD T5
If
is
§ ai
Q) £ Q) Q. Q.
*- .h: ro ra
O> < CQ O
Ecc
8-48
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
"5
c
Q>
___
u~ft-
"ill
§
|| Congener/
|| Congener Gro
o o o 0 g
o o o » N m-
Z Z Z n
S
• o
::•::::
i !
s ~co 8 2 §<•
0 Z ' "" g?
Z CM
I Egnig
•Mi«i§
i z -R
SE gm||
S Q CO ICT CM I CM CM CM Q
CM" T-^ ^ ^ ^-" ^-" 0
OOOOOOo
zzz zzz01 <-
.: -! i : : i : : ,
i :•! i : , : : :
c
§i§ : « i : : ', |
gjrp -^8g§
iiI£"Ii|riR
|.55|a||s|
2 2 Z •- • £
§ Z Z Z Z S<°g
|E5
CD tt> m
Ijf5
8 o
CM .
^
: : :
oL
I Total 2,3,7,8-CD
Total 2,3,7,8-CD
Total TEQ"
ooliJ^Ul
CM
^°o8 °go8
Q — S°i'! — S^i
oog|§oogo?
oo-§iogg§i
T- r*. *~ ^- »-
o o S o 2 c
oiiaoooco^ogc
-SR *S5
00c3§§Q "§1
ZZOirfoZ^^Sff
CM co co «- ^- rr
^~ OJ •— C»
o
§gSf|<0°§8S
*~
llsill. .§§
O C\ + "* ® O pJ ®
22 252 , • CM* O O
CM r r-
2222222 2" 22
oo o oBBoo.oo
CO
c
to
10
c
c
u
•3,178,598 I
1,270,000 |
u
>
I 9££'Wt
1 CM
o:
CO
^3
CM
8
^-
0,
i
CO
8
O
CM
in
-------
DRAFT-DO NOT QUOTE OR CITE
^I
ill Iliii^i-iS^S
U.S.
NY),
moo
1
-
8-50
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-8. Historical CDD/CDF Concentrations in Pentachlorophenol-Na
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-CpD*
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*
PCP-Na
(Ref. A)
(1969)
teg/kg)
- -
•' -
-
—
__
3,600
-
— ,
^_
„
—
— .
. -
-
-
—
17,000
9,600
3,600
- , -
-
' " —
—
- •
-.
PCP-Na
(Ref. B)
(1973)
teg/kg)
-
-
-
-
._ ,
• —
- '
m
—
• -
-
_ .
~
—
140
40
,140
1,600
4,000
ND (20)
60
1,400
4,300
4,300
15,980
PCP-Na
(Ref. C)
(1973)
teg/kg)
• -
T-
. -'
-
_
..
—
• —
.
•
~ -
—
-
~ . .
—
—
50
ND(30)
3,400
38,000
110,000
ND (20)
40
11,000
47,000
26,500
235,990
PCP-Na
(Ref. D)
(1987)
fcg/kg)
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
27
213
3,900
18,500
41,600
82
137
3,000
13,200
37,200
117,859
PCP-Na
{Ref. E)
(1987)
teg/kg)
0.51
3.2
13.3
53.0
19.0
3 800
32,400
0.79
1.9
1:1
4K
•o
1 ^
1 *O
1.3
4 R
*t.o
197
36 -
4,250
35,289
4,499
79.5
52
31
230
5,800
32,400
12
27
90
860
4,250
43,752
PCP-Na
(Ref. F)
(1992)
(^g/kg)
0.076
18.7
96
4,410
328 -
1 7>? Ann
1 / O,*MJW
879,000
ND (1.0)
ND{4.0);
ND (4.0)
9V fi
£~ 1 .D
01 q
<& 1 *+3
9.8
10"$
1 WO
9,650
2,080
114,600
1,059,253
126,492
3,374
3.6
142.7
9,694
260,200
879,000
,10.1
88.4
9,082.3
75,930
114,600
1,348,751
PCP-Na
(Ref. G)
(1980s)
ND (1.4)
/ 28.3 ,
ND(6.1)
4,050
ND (1.4)
qo pnn
OO,Owl/
81,000
149
319
324
Kir\ /o o\
WLJ \^..of
OOC '.
£.£.&
480
iun /*5ORi
IMLJ \OOO|
6,190
154
36,000 '
118,878
43,841
1,201
1.9
140
14,000
100,000
•: 81,000
1200
6400
49,000
91,000
.36,000
378,742
ND = Not detected; value in parentheses is the detection limit.
— = Not reported.
* = Calculated assuming not detected values are zero.
A/g/kg = micrograms per kilogram.
Sources:
Ref. A: Firestone et al. (1972); mean of two samples of PCP-Na obtained in the United States between 1967 and 1969.
Ref. B: Buser and Bosshardt (1976); mean of five samples of "low" CDD/CDF content PCP-Na received from Swiss commercial
sources. •
Ref. C: Buser and Bosshardt (1976); sample of "high" CDD/CDF\content PCP-Na received.from a Swiss commercial source.
Ref. D: Hagenmaier and Brunner (1987); sample of Dowicide-G purchased from.Fluka; sample obtained in Germany.
Ref. E: Hagenmaier and Brunner (1987); sample of Preventol PN (Bayer AG); sample obtained in Germany.
Ref. F: Santl et al. (1994c); 1992 sample of PCP-Na from Prolabo, France.
Ref. G: Palmer et al. (1988); sample of a PCP-Na formulation collected from a closed sawmill in California in the late 1980s.
8-51
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
•I a;
J|i C
us: ii!>
If
1%
1
11 "*
ji
f
if'
I 6 «•
It " ^
1 °
|| "S •!
11 1 •
1 °
X
&
a
II
2
8
V
II
s>
•;
5 o
5<§
j
Waste Description
z
a
£
1
en en en en in <
o o o* o o c
Hills
00
»
00
I
E
>
Wastes (except waslewater and spent carbon from hydrogen chloride purification) from
the production or manufacturing use (as a reactant, chemical inlermediale, or
component in a formulating process) of Iri- or tctrachlorophenol, 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-lrichlorophenol.)
o
§VO ^Q ^p p^J y
o o o o o
o o o o o o
t- eu IE *~ EU •
oo
s
00.
J
1
2
Wastes (except wastewater and spent carbon from hydrogen chloride purification) from
the production or manufacturing use (as a reactant, chemical intermediate, or
component in a fonnulating process) of pentachlorophenol, or of intermediates used to
produce its derivatives.
I
\o \o \o vo fi \
0 O O 0 O O
o o o o o o
iil«sg
f\ ^) \j r\ {j \*
oo
2i
oo
J>
B
>
z.
Wastes (except wastewater and spent carbon from hydrogen chloride purification) from
the manufacturing use (as a reaclani, chemical intermediate, or component in n
formulating process) of telra-, penta-, or hexachlorobenzenes under alkaline conditions.
g
O 0 O O S C
o o o o o o
§§8888
oo
oo
ON
oo"
Jl
E
>
z
Wastes (except waslewater and spent carbon from hydrogen chloride 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 letrachlprophenols. (This listing does not include wastes from
equipment used only for the production or use of hexachlorophene from highly purified
2,4,5-trichlorophenoi.)
N
en en en en ui c
o o o o o o
|l§888
oo
ON
OO
J
>
0
Wastes (except wastewater and spent carbon from hydrogen chloride purification) from
the production of materials on equipment previously used for the manufacturing use (as
a reaclant, chemical intermediate, or component in a formulating process) of telra-,
penta-, or hexachlorobenzene under alkaline conditions.
§
o o o o =5 cs
Illlll
f- a. K t~ a. a:
0\
"I
P
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-trichlorophenoI as the sole component.)
g
8-52
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
I
*
c
o
CO
c
o
1
tr
"CD
CO
o
Q.
CO
TJ
C
CD
_J .
*-»
'i
"5.
o
O
CO
3
D)
C
'c
'co
*j
O
o
c
'x
o
b
'o
o
Q.
CO
"o
to
E
CO
CO
06
.n
Q.
a.
to
-a'
CO
•o
c
CD
to
4->
C
:
£•
1-
?,
CO C
,
to
• 3
O
•c
.cc
X
CL
2
to •
^
CD ,
to
co :
g ~
c
o
2
2
I:5
•J-
ol
» 3
»-'S3
s«
o
o
CD :
2Q
3 CD
3 CD
c !£
11J
c
,0
.la.
~
o
CO
CD
Q
&
CD
5
^_
CD
E
§.
+*
(D
5
CO CO CO CO ID C*
CO CD CO CD CO CO
0 O O O O C
d d d d d o
^ Q Q » if u2
§§8°88
"^ x"^ x
>~ 0. X H 0- X
en
§
CO
.13 , '
.Q
CD
O
•o
C
— CO
o *
CO CO
»- CM
o O
, u.
or thermal treatmer
te Nos. F020-F023,
c «
•11 •.
o 2
.£ o
-— CO
CD m
•S x
E <
o n.
•I 1
Is"
"- CO
CO C
IK
to C CM
« 0 0
CC u U.
00
N
J.
co co co co in co
CO CO CO CO CO CO
o o o o o c
d d d d d o
to eo
g.sspss
*• 0. X ^ Q- X
o * 1?
en -^ CM *2
en CD en co
«- «3 °> 5
«. I !~- 1
1 1™ I
§ g J c
^ £
CO
CO tu
f £ ?
— ~ CD *- ..
S"1 E -a •«
»j to O C •—
CO CO ^ CD eg
5 J5 tn J3
5 O 2* CD CZ
•o S 5 2 =
irough land dispose
i one restricted was
68. (Leachate resul
EPA Hazardous We
Hazardous Waste Iv
F028.)
ffl £ <-> .0 co 1 2 "B 2 «-
r- O fg (D ^ = — co p
(S p O tD "T *^-
Hills'
_1 £ .C 13 0 U.
en
CO
o
u_
CO CO CO CO 1O CO
CO CO CO CD CO CO
o o o o o c
d d d d d o
8 S o 8 8 <.
"c£x"c25
s-
en
CO '
CD
^
Q
•*„
CM
"o
.c
o
1
T3
e
Q.
CD
.C
E
o ,
CD
+•"
CO
g
"o
c
CD
JC
CL
O
O
.c
0
CO
CM"
co
°
CO CO CO CO 10 CO
CO CO CO CD CO CD
o o o o o c
d d d d d d
8||8||
00
00
CO
CO
TO
3
<
^
Q
4 . • ' : •
"o
c
0
s
3
a.
CD
.c
0
^^
k.
CD
to
s
to
CO
i
CO
5
en
en
0
C
o
en
en
en
en
cri
en
c
o
I
'5
£
CO
S
c
c
o
C
o
u
_CD
-Q
CO
_0
"x E
CD
CO CD Q.
P =• <0 CO
CO to c CO
1 E S N
w 2 i5)0=
« OJ O "r
II co
. 5" -
==i =S 3
o> o> o
3. =S.CO
8-53
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
CO
03
N CQ 1
00 . -^
ssi
CQ c^ . -i
Sa|l
g£lCO
QQQ'*CD-QQQ'*<,.
222 ®222 ^
?J CM N ?g
OpcMcgincsiOO
00000000^^
QQ°°d°QQ°0
22 22
CM
cjcNincO'COT-jT-OcoT-
OT-CNJCMOt^CMOOO
oooooooooo
SSSSS2S2SS
QQQQQQQQQQ
2222222222
CMCMCMCMO) CMCMCM
OOOOO OOO
^ddddd^ddd
Q Q Q Q Q Q Q Q
22222 222
CMCMCMCMCMCSCMCMCNCM
OOOOOOOOOO
OOOOOOOOOO
QQQQQQQQQQ
2222222222
Q Q Q _ u_ u. u.
QQQQgU-QQQU.
QoCJO^QoooQ
0»X Q.OOoXQ.0
KQ.XXOI-0-IXO
(OCO(0(D(0(0G3(0(OCO
OOOOOOOOOO
Hl-|-l-l-l-h-l-|-l-
!
:
1
<*
o
ro
!
1
1
CDD/CDF
(0
0
CD
C
CD
O>
CD
Q
5-
•o
c
CO
C
CD
I
CD •»
* I
CO
CD
K S °>
® TI o
sil
c £ E
O)
o
CD -Q
•o 5
CD CD
c m
CD CD
DL'5
« O
» E
+•• E
M- O
O U
So
3_S
>- Q.
•o E
CD CD
.C (0
.22 CD
S CD
J^: CD
co en
t- c
O5 fO
O) '-
•D »-
CD —
w CD
CD >
D} CD
C 3
X >
^t cy^
CD CD
cc tr
8-54
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
CO
CD
w
13
4^
X
ca
O
CL
's
CD
O
O
CO
a.
3
S
CD
k.
CD
C
CD
0>
O
O
Q
O
Q
a
CO
o
CD
O
O
O
00
_CD
.0
£
7
CO
, c
toncentratie
c
c
O
k.
Manufacture
1
X
CD
O
Q.
fl
1
>
1
;
"
!
a
1
;
a
o
a
CM
i^
a>
co
o
o
o
<
0 0
3 .-• , J3 oo to
0 "^ ro
e» o
! : ! a> Q
' oz
d
; ! ! co »-
0 0
«- o
do
CO Q «- ID ID
0 Z CO O 0
q _• oo o
0 O 0
co 01 rx CM t^
gcMO^JZ
CM d
i«» co 10 r- co
dNdc?^
CO O
: : : .!. !
CM CM CM g g
•*•<*•* °? «?
CM CN CM :
OCM
o> •
CO , ,
O> ' '.
*?i
^<0
t § JZ
O S o
III
< o 2
> 0
03 OJ . J3
-Q
: j : ;
! I ! ! t~-
i
C
«
c
o
i i i ! Q
.'
: ! : i a
: : i : a
I1* ID 00 CM CO
«- T- d 6 „
c
! i ! ! 0)
a
d
I « i ; *
ft
d
• 1O bO 1O UJ
CM CM CM CM <
O O O O J!
O o O O o
0 0 0 0 o
< < < < 0
o u
^ re ^ n ID ~o fo
.Q .Q . •
: ! : i CM co :
CM •*
0 0
do
: : ; : m CM ;
t— CO
0 O
do"
' • '• '• § 2 ';.
0 0
o" d
: i : s CM o !
8Z
d
: ! : : CM Q !
§z
d
i : ! : 5 d- i
Sz
o
d
COOCNCOCMi-COCO
co^cMoggroco
^ 00 . *~
CO ^
! ! ! ! O> Tt i •
CO CM
CD O ""
d T^
in : : i f» CM ! !
CO ,- CM
^1 in in
T^ CM
oiniococoocMO)
^ d dp !§ S CM oi
•* I<
O^cneoin^-oo
t-dodig^ind
*~ N
COr-COCMCOO^-I^
OOOOggi-O
in to
^- ^
0)
.CD ,,,,,,
. 03 i • . ! ! !
co
00 0 0 g g g CL
COCOCOCO5?C?
^£
O)
E
CO
10
- r*»
~
"S
CO
CO
o
•1
£
CO
cc
s
(O
I
o
m
CO
co
CO
O)
c
0
CO
.*£
U
•c
UJ
^3
CO
o>
CD
EC
a
S
<
0
—
00
CD
5
agenma
X
•o
f
CO
j:
u
_co
To
2
CD
8-55
April 1998
-------
V
s
1
1
i
1
(
c
U
1!
u
75
1
If
|
s
|
i
I
o
S
1
o t
s-
^~ 1
*± 1
in
CM —
*~ 1
CM •;
•- j
s5
CM '
to
CM 'S
*"E
00 C.
*" E
CM O
rs
coB
-I
II
^^
•*!
•*!
B
<1
S
*? ~
_
o "^
|
o
o
: : i t l i
: : ! i i i
i : : i i :
!!!•!!!
i;:::;
!!:!!!!
i : : : ; : i
!!!!!!!
Q O Q Q Q 00 CO
Z Z Z Z Z CO c\
Q T- CM o Q m en
z d d z z CM •*
o o a a a co en
z z Z z z uj co'
CM
O Q O Q O ^" CO
z z z z z Tf d
CO
Q Q Q Q Q •* t-
Z Z Z Z Z CM' <*
CM
Q Q Q CO Q CO .-
CO
a
Q Q a R
Q a a a ^
§ cu 06 co en r-~
t— co r-. r- co co
co r— •» co r- tf
r*" co eo co co co y
CO CM^ C9'-" CM T^ i-" o
: ! i :
! i ! :
: i i i
: : ; i
: i : i
i i i i :
! i : ; :
: : i i :
i : : i :
: : i i :
o o a m co
Z Z Z CO CM
'- CO
't o co o en
O CM »- CO *f
Q Q Q O 05
Z Z Z ^ (0
*- CM
Q Q Q CO CO
z z z ,-: o"
«- CO
Q Q Q I- r-.
Z Z Z to 4-'
CM
r— a CM co •-
°Z-'»S
ogggo
Q O ^ ^ ff
t— S. x x o
!££££
; i : ;
: i : :
! : : i
i : : i .
i : i ; :
: : i : :
: i : i :
; : ; ; s
: : : : !
i i i : l
O t M CO CO
2MB!
r» co eo o CM
10 «d- 10 r— en
co 10 in •- v.
in T- *fr »-
co r- co co CM
CM co co co en
<3- «- CM >* *°
10 CM CM
* co CD in *
en o co en ^"
oo r— ^$* *— T-
CM r- »-
co in t- co Q
J^ co in d Z
CO
CD ^ CO CO •!—
CD CM *t 00 10
CD CM
U, U, U.
U. Q O Q "r
a o o o a
h- Q3 *^" X° O
— — —~ — ^.
O O O O O
1- 1- 1- t- 1-
i !
•"
1 !
i 1
1 '
! !
: i
.: t
' !
; !
IO CM
CO «*
CM 'a-
r— *a-
oo »-
^f CM
* en
1— CO
o •*
CO
Is- >-
to T
in p~
CO CM
O CO
CO i-
t~- ^
CM Is-
CM
in o
in "*;
00 <*
OD T-
•* CM
en
*
LJL
a
"a
gS
8^
^^
£
— en
»fi
il
n n
< m
eo
CO
en
~s
10 O
o —
c V)
II
m co
II ''II
o o
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-13. Reported CDD/CDF Concentrations in Wastes from PVC Manufacture
! — —
Congener/Congener Group
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1 ,2,3,4,7,8-HxCDF78
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-HpGDF
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
I Total CDD/CDF
F024 Waste
fag/kg)
0.37
0.14
0.30
0.14
0.11
4.20
• , 1 5.00
0.91
9.5
1.6
110
24.0
9.5
3.1
250
51.0
390
20,3
849.6
19.98
3.1
3.6
1.3
5.0
15.0
15.0
65.0
300
450
390
1,248
K019Waste
(//g/kg)
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
1,230
3,540
3,950
1,270
1 ,060
20,600
45,300
63,700
16,600
43,500
200,750
K020 Waste
f^g/kg)
0.06
0.05
0.08
0.06
0.07
0.89
3.00
6.44
1.80
0.58
11.0
2.4
1 .3
0.89
38.0
6.0
650
4.21
712.4
3.19
1.9
1.7
NR
1.7
3.0
6.0
11.0
27.0
58.0
650
760.3
NR - Congener group concentration reported in, source is not consistent with reported
congener concentrations. , . , ' ,
/^g/kg = micrograms per kilogram
Source: Stringer et al. (1995)
8-57
April! 998
-------
DRAFT-DO is[pt QUOTE OR CITE
p
t5
S
5
s
•g
1
1-
o"
o
lichloride (E
i
&
j=
G
g
S
j
>
x.
c
i
PL
n
^5
n
a>
fe
2
a
a
S.
m
3
CO
"oli o
£§s
gs g
en Q o
o
1
CO
Q
d
Z
"3>
•sit
^ Q> "
B3 0 O
EO §
O
1-
s>
Q(
d
z:
"3
•S-o:*
0 ® a
g>I-S
§S o-
ttoj
J
I"
o
ac
d
z:
"3
•s^t
ft> o c:
i^l
!i
0 <
O 11
4-1
gener and
ener Groups
5 g
°c!
s .
c
I
n
J2
o.
1
OT
d
X
CO
C
2
W
D
1
n
3
X
(0
c
s
a
D
1
o
6
r
X
(D
2
C
2
O
E
3.
a
1
D
•
•o -a -a T> -a co 2
C C C C C CM r*
H- oo r^ r^ co co
co r~ •* 'f^r
CO CM CO CM CM CM CO CM CM o
CM"T-CM»-'-'-CM'T-T-O
10
•*
o
CO
o
CM
d
to
o
o
o
d
\D
CO
d
i
d
ID
co
d
CM
o
0
d
^
— a
2cM
CO — •
N «—
II II
0 O
•^•z
o o
h- H
to (D
22
-OT>T3C02-0-DO2£
ccc-^gcccojg
T3-OT3'O-O-OT3T)'aT3
cccccccccc
oooooooooo
OOOCOCM'OOCM'coiS
•o-o-a-a-u-a-o-ao'-
CCCCCCCC;«-
CM
•OT5-DT3TJT3T3'O'Ot3
CCCCCCCCCC
iDiaioioioioiaioiDto
OOOOOOOO'-'-
^ CM f*» «vs «A CO
cMcocnp?'a'op?Tj-oc':
odd" c c° c cd
•o-o-a-D-o-D-a-a-o-a
cccccccccc
cocococococococococo
«-T-lD»-OO»-OOCi|
^ r~
TS'a'aco'Of'Dco TJ ~o
ccczjccc-cc
O o
•OT3TJ-OT3T3'DTIT3TJ
CCCCCCCCCC
CMCMCMCMCMCMCMCMCMCM
CMCMCMCSCMCMCSCMCMCM
OOO'-OOO'-OO
O O O _ M_ U. LL.
aQQQ9u.QQQU.
QoOOQQoOOQ
1-Q.XXOh-OLXXO
tO(Q(0 —
2 _ o
QJ ""' "*j
°- Si g
« Q. —
lit
O) TO "^
O w. r
O) O
^ =£ 3
a) co o
, c a.cn
8-58
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
co
c
CO
O
(D
O>
oE
CO
ID
Q
CD
§
CO
c
o
0
o
c
O
O
u_
Q
O
in
co
JD
co
CO
«N «
CO 75
O §.
' •>' ~
g-
*-* 36
s'i
5 —
CO
S3
§.t
CO ~~
/Congener
CD
C
? 3
C O
O ll
O CD
co co • co co •* o
O O O O J
Q Q Q Q «-
22 2 2
mm ' co co CM rv.
O 0 CD O £
Q Q Q Q <-
22 22
mm ' m m o o>
o o o o S)
Q Q Q Q r»
•Z. 2 22
?> « • TO « CD C\
00 0 0 " g
Q Q Q Q ^~
22 22 ^~
m m ' co co r- co
O o o o §
Q Q Q Q
22 22
mm ' m m m o
o o o o f£
Q Q Q Q |C
22 ,22
co co • co co m p.
do o d o" ^
Q Q Q Q a
22 222
mm ' m m 03 co
do do g
Q Q Q Q 00
22 22^
m m '• mm co.co
9.2. 9.S. S
Q Q Q Q 00
22 22 ^
mm '• m m r- m
do od^g
Q Q Q Q — ~
22 22 •*
Q
Q Q Q £
Q Q Q Q "
g 0 00 £
.~ ri x x x ,
g 0 I I X 00
j a-'oo oo O) r*.
I— oo r^ t>T eo" co
oo r>» •* co t^ •*
r^ m m m m m Q
CM" .- ^- T- ^ T- o
co co 00- rv* ' co CM ! m
odd , d *" J
Q Q Q Q
222 2
COCOCOCn* 'COr- '(>.
odd d ^
ili i
m m m *- * >. co •* -co
odd00 o [g
Q Q Q Q t-
222 2
C5?>?)O)* !?}«- !O>
odd" o^ j*
O O O Q CO
222 2
w co-Co ^ * '.• m o ' io
2.9.2.-. ,9." ™
Q Q Q • Q
222 2
co in co co * ''coco ! «-
opo1^ ;~ o- g
a a . a
22 2
COCOCOCO* -COO'T-
d d d d d T~-
a, a a o a
2222 2
COCOCO"CM* 'co"** !co
odd o *~ g
Q Q Q Q ^
222 2
co co co CM * •' co- o ' r»
22.2 2^ 5
Q Q Q Q t-7
222 2
C?,WCO"CM* !WO 'CO
odd'- d10 ®
Q Q Q Q CN
222 2 <-
UL U.
U- LL U. U. Q Q
"-"-SSSo^-"
g Q
CM •* _..
t1*
OJ.I^ f^
CM It) _..
CO r-
05 T- rv
m O> fM
o> in Jj
rC r-"
oo en a>
CO O3 _
q r* J2
»-" co"
FN O> *
o co _
00 .«- *^
0> T- O
"8»
1^ r-^
-co o T-
CM CM Q
in CM ir>
1^ CM _:
q o 2
oo" ^
co a> CM
CM in ~
"tS
00 »—
°*
^t in t
00 ^ to
°l"lS
T- CM
•* T-
Q u_
Q Q
O O
CO 00 *
pC.rC *
co" co" O
CM CM H-
* co o> CM t-»
odd g d o *
Q Q Q "" Q
222 2
COCOCOi— C5>COCO"»-COCO
SSS"Soow-[n
Q Q Q r-~ a a - »-
222 22
coeor^-cocNcococncncJ)
22 m^22nf^^
Q Q "-"^Q 0 CO
22 •- 2 2
coco"eMincococoin'*in
£2 § ££ "*2
o a a Q
22 22
co co r-/o o co in co co *—
OQCMCOOOQ0-f>.CM^
Q Q' rC Q
22 2
coco'— cocoJoeococM*—
do dtNdddr~'~
a o a a a o
22 2 222
COCOCOCMCbcOCOCMCOCO
£££"o££ ^8
Q Q Q CO" 0 Q •r-"
222 V- 22
CO CO COOOCOCOCOCMCMP^
£ £ £ S°o « .5
Q Q Q oo" a •r-"
222 ^2
m m m •** m m m CM «- co
£ £ £ °° a £ £ " ^ ^
O Q O '- Q Q CM
222 "* 2 2 <-
Q Q Q u_ ij- u. .
QQQQ9u-QQQU-
gooogaSooQ
OCDXD.OOCDXQ.O
(— CL XXOh- CXXXO
CO CD'-^CD CD CD CD CO CD CO CD
oooooooooo
!-. 1-l-l-H-l-l-t-l-l-
c
c
1^.
CO
r*
o
^f
in
<&
CM
CO
a
'^
l^s
in
a>
in
l-s
CN
oo"
1^
•*
CM
O5
CM
O
o"
CO
co
CO
in
•*
in
*
*
u.
a
o
a
o
"<5
*-•
o
Q
O
Q
Q
O
CO 09
•S2
CO |-
o o
E 25
— n C^
CO g ^ O)
E
^ jo £ £ II
II
o
CD
II II
CD'
'
*
*
8-59
April 1998
-------
: CRAFT-DO NOT QUOTE OR CITE
Jable 8-16. CDD/CDF Concentrations in Printing Inks (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 TEQ »
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)
(ng/kg)
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
90.1
4
58
2,679
5,630
5,810
5.5
13
29
64
129
14,422
Rotogravure
(4-color)
(ng/kg)
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
66.2
ND (2)
145
2,485
3,460
2,350
28
ND (4)
45
14
ND (10)
8,527
Offset
(4-color)
(ng/kg)
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
1320
38.2
77
35
660
1,100
890
90
340
95
566
960
4,813
Offset
(4-color)
(ng/kg)
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
17.5
38
25
246
445
230
35
110
94
63
165
1,451
ND = Nondetected; value in parenthesis is the detection limit.
— •* Not reported.
* = Calculation of JEQ values assumes npndetected congeners are present at half of their detection limits.
ng/kg = nanograms per kilogram.
•i;):' _ . ;; : ' "i ' , • l * :,..•• • ,,,."', ;-_ ,,• , _«; " '.•.,-• |..
Source: Santi et al. (1994c).
8-60
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-17. Chemicals Requiring TSCA Section 4 Testing Under the Dioxin/Furan Rule
CAS No.
Currently Manufactured or imported as of June 5, 1987a
Chemical Name
79-94-7
118-75-2
118-79-6
120-83-2
1163-19-5
4162-45-2
21850-44-2
25327-89-3
32534-81-9
32536-52-0
37853-59-1
55205-38-4
Tetrabromobisphenol-A
2,3,5,6-Tetrachloro-2,5-cyclohexadiene-1,4-dione
2,4,6-Tribromophenol
2,4-Dichlorophenol
Decabromodiphenyloxide
Tetrabromobisphenol-A-bisethoxylate
aTetrabromobisphenol-A-bis-2,3-dibromopropylether
Allyl ether of tetrabromobisphenol-A
Pentabromodiphenyloxide
Octabromodiphenyloxide
1,2-Bis{tribromophenoxy)-ethane
aTetrabromobisphenol-A-diacrylate •
CAS No.
Not Currently Manufactured or Imported as of June 5, 1987b
Chemical Name
79-95-8
87-10-5
87-65-0
95-77-2
95-95-4
99-28-5
120-36-5
320-72-9
488-47-1
576-24-9
583-78r8
608-71-9
615-58-7
933-75-5
1940-42-7
2577-72-2
3772-94-9
37853-61-5
Tetrachlorobisphenol-A
3,4',5-Tribromosalicylanide
2,6-Dichlorophenol
3,4-Dichlorophenol
2,4,5-Trichlorophenol
2,6-Dibromo-4-nitrophenol
2[2,4-(Dichlorophenoxy)]-propanoic acid
3,5-Dichlorosalicyclic acid
Tetrabromocatechol
2,3-Dichlorophenol
2,5-Dichlorophenol
Pentabromophenol "
2,4-Dibromophenol
2,3,6-Trichlorophenol
4-Bromo-2,5-dichlorophenol
3,5-Dibromosalicylanide
Pentachlorophenyl laurate
Bismethylether of tetrabromobisphenol-A
Alkylamine tetrachlorophenate
Tetrabromobisphenol-B
Tetrabromobisphenol-A-bis-2,3-dibromopropylether and tetrabromobisphenol-A-diacrylate are no longer
manufactured in or imported into the United States (Cash, 1993).
As of August 5, 1995, neither manufacture nor importation of any of these chemicals had resumed in the
United States (Holderman, 1995).
8-61
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-18. Congeners and Limits of Quantitation (LOQ) for Which
Quantitation is Required Under the Dioxin/Furan
test Ru|e 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
(/^g/kg)
0.1
0.5
2.5
2.5
2'.5
100
1
5
5
25
25
25
25
1 ,000
1 ,000
fig/kg » microgram per kilogram.
.'"'I I'.; V,1" ..(•;'.
"y.'..;;t'f' '.. V ,'-
April 1998
:,iT L"i!'i,t •,>!:,•. liJ',1'1 ,i! '.•
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-19. Precursor Chemicals Subject to Reporting
Requirements Under TSCA Section 8(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
106-37-6
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
1,2,3,4,5-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-Dichlorobenzene
o-Bromophenol
o-Chlorophenol
4-Chlororesorcinbl
1,2,4,5-Tetrachlorobenzene
5-Chlbro-2,4-dimethoxyaniline
2,6-Dichloro-4-nitroaniline
1,2-Dichloro-4-nitrobenze,ne
Dibromobenzene
p-Dichlorobenzene
1,3,5-Trichlorobenzene
Bromobenzene
Chlorobenzene
1,2,4,5-Tetrachloro-3-nitrobenzene
1,2,4-TrichIorobenzene
o-Chlorofluorobenzene ;
3-Chloro-4-fluorohitrobenzehe
Chlorohydroquinone
1,3,5-Tribromobenzene
2,6-Dibromo-4-nitroaniline
8-63
April 1998
-------
Table 8-20.
DRAFT-DO NOT QUOTE OR CITE
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
32S34-81-9
4162-45-2
«
Chemical Name
Tetrabrornobisphenol-A
2,3,5,6-Tetrachloro-2,5-
cyclohexadiene-
1,4-dione (chloranil)
2,4.6-Tribromophenol
2.4-Diohlorophenol
Decabromodiphenyl oxide
Ally! ether of
tetrabromobisphenol-A • ,
Octabromodiphenyl oxide
1 ,2-Bis(tribromo-phenoxy(-
ethane
Pentabromodiphenyl oxide
Tetrabromobisphenol-A-
bisethoxylate
No. of
Chemical
Companies
That Submitted
Data
3
4
1
1
3
1
3
1
2
1
No. of
Positive
Studies
0
4
0
0
3
0
3
1
2
0
Congeners Detected
(detection range: #g/kg)
NDa
See Table 8-21
NDa
NDa
2,3,7,8-PeBDD (ND-0.1)
1 ,2,3,4,7,8/1 ,2,3,6,7,8-HxBDD (ND-0.5)
1 ,2,3,7,8,9-HxBDD (ND-O.76)
1,2,3,7,8-PeBDF (ND-0.7)
1 ,2,3,4,7,8/1 ,2,3,6,7,8-HxBDF (ND-0.8)
1 ,2,3,4,6,7,8-HpBDF (17-186)
NDa
2,3,7,8-TBDD (ND-0.71)
1, 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)
1 ,2,3,4,7,8/1 ,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)
1 ,2,3,4,7,8/1 ,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)
1 ,2,3,4,7,8/1 ,2,3,6,7,8-HxBDD (ND-6.8)
1 ,2,3,4,7,8/1 ,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 (1 5.6-61 .2)
1,2,3,4,6,7,8-HpBDF (0.7-3.0)
ND"
• No 2,3,7,8-substituted dipxins and furans detected above the Test Rule target limits of quantitation (LOO). (See Table 8-18.)
b Third study is currently undergoing EPA review.
0 Study Is currently undergoing EPA review.
pg/kg - micrograms per kilogram
Source: Holderman and Cramer (1995).
8-64
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-21. CDDs and CDFs in Chloranil and Carbazole Violet
Samples Analyzed Pursuant to the EPA Dioxin/Furan Test Rule
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 TEQ*
Importer
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
Concentration fag/kg) in Chloranil
Importer
2
nd (1)
nd{2)
nd'(10)
75
48
8,200
180,000
nd (2)
ndd)
ndd)
nd (860)
nd (860)
nd (680)
nd (680)
240,000
nd(100)
200,000
2,874
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
ndd 5)
50,000
814'
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
Concentration
U/g/kg) in ,
Carbazole
Violet
nd (6.8)
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)
1 5,000
nd (20)
59,000
211
Source: Remmers et al. (1992).
nd = nondetected; minimum limit of detection shown in
fj.g/kg = micrograms per kilogram.
* = Calculated assuming not detected values are zero.
parenthesis.
8-65
April 1998
-------
2,3,7.8-TCDD
1,2,3,7,8-PcCDD
1.2,3.4,7,S-HxCDr>
1,2,3,7,8,9-HxCDD
1 ,2,3,4,6,7,8-HpCDp
I,2,3,4,6,7,S,9-OCI>I>
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^,3,7,8.9-HxCDF
2,3,4,6.7.8-HxCDF
1,2,3,4,6.7,8-HpCpF
1.2,3,4,7.8»9-Hi>CDF
1,2,3,4,^,7.8.9-OCDF
DRAFT-DO NOT QUOTE OR CITE
Ratio (congener concentration / total CDD/CDF concentration)
0.1 ' O.2;,^ [,.',,.." Ol.3i '/ , i .."O.4 „ ' , O.S " O.6
O.7
Ratio (congener group concentration / total CDD/CDF concentration)
' ' ' ' 6=2'; '! ' 0.3 Q.4., ." .: " 0,5
0.7
d Ml data tffotui m Table 1-7; aea&aecu to. equal to
Figure 8-4. Congener and Congener Group Profiles for Technical PCP
'jiiii '. ' i i1 '.'. "• , '.-' '• • .: , '• ','!' '• ' ^•'\V!.i"l '/'' .".' "'•'::' f':"
•^ • • • • •.,••• 8-66
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
$'.
S
CX,,
«>
.
J
^
. U
c
1
.>
t>
<
1
'S
o>
o> a>
" •
o
r-
*•
1 Dichlorodifluoromethane
o
o
o
en
c
a
1
O
•fc
O-(4-Bromo-2,5-dichIorophenyl) O,O-dimethyl phos
vo
1
c
<
—
tS
r Dimethylamine 2,3,5-triiodobenzoate
__
en
en
V
2
o
o
o
VI
00
ON
CM
1 Crufomate
o
cs
o
c
c
12
"t
c
">.
3
^
' a
.i
"I
_-c
_JJ
•4
1
1
O
V
e^i
\
vo
3
e
3
*>^
j
X
•^
•<.}•
•5
a
W3
es
S"
u
£
o
>•
en
o
r
4-Chlorophenoxyacetic acid
o
c
Chloroxuron
o
>
\
. ON
Dichlobenil
o
1
z
c
c
0
•
Propanil [3',4-DichIoropropionanilide]
OO
g
«
r-*
*^1
a
§
|
o
Q
Dichlofenthion [O-(2,4-Dichlorophenyl) O,O-diethyl
S
OO
g
C
o
c
IE
CJ
1
.£
o
5
a
a
o
1
C
«
,
Dichlone [2,3-dichloro-l ,4-naphthoquinone]
1
V
^
o
T
O
e3
U
|
V
c
1
en
1
•s
•§
1
c
y
(N
O
- o
o
*n
ON
•^
Sodium chloramben [3-amino-2,5-dichlorobenzoic ac
o
ON
§
OO
t^»
vo
e«
Sodium 2-(2,4-dichlorophenoxy)emyI sulfate
I
o
>•
a\
o
en
o\
CTv
DCNA[2,6-Dichloro-4-nitroaniline]
o
en
en
o
o
c
s
Potassium 2-(2-methyI-4-chlorophenoxy)propionate
S
o
—
e*1
''a?
c
-o
•Q
- 1
s
MCCP, DBA Salt [Diethanolamine 2-(2-methyl-4-chl(
tn
en
o
2
0
fN
G
X
U
G
o
^2
1
a."
a.
U
o
0
V£
a
e
O
.c
I
O
Dicapthon [O-(2-chloro-4-nitrophenyl) O,O-dimelhyl
1
I
o
5:
' O
T
s
8
O
2
«
03
E
2
*>,
1
u
en
1
s
e?
O
z
-
tl
o
en
Diuron f 3-(3.4-dichloroDhenvll- 1 . 1 -dimethvlureal
g
S
_ c
.5 2
,%_, •.,_,
C CD
F
P fe
+•• x
05 .2
.E Q
If
*- o
o >
.2
co .t;
.3 TJ
W o
So
= •*
O c
R5 r n" '
il
« o
to b
O CD
CO .E
B E
w §
*"§'
» o
OJ O
8-67
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
If!
.2 •<
I 1
H|
I
H
CO 2
r
1 CAS Number
(_
*
1
O
C
£
2
1
!»
2
(
2
330-55-2
*c
*i
1
1
1
o
o
I
rn
a
g
1
i
3060-89-7
i
3
OJ
i
i
Metobromuron [3-(p-bromophenyl)-I-i
i
s
i
2
c
298-00-0
tt
jE
c
1
1
Methyl paralhion [O,0-Dimethyl O-p-i
o
.
-f
I
Carbophenothion[S-(((p-chlorophenyl]
CM
O
OO
s
c
CO
O(
o
1
c
c
«
c
(U
Ronnel [O.O-dimethyl O-(2,4,5-trichlo
CO
o
o
2;
o
1 3567-25-7
c
tt
[S
1
X
C
OJ
1
IS
"E
">i
1
o
1
en
Mitin FF [Sodium 5-ch!oro-2-(4-chloro
1
OO
a
C
Orthodichlorobenzene
o
S
S
o
Z
o
106-46-7
Paradichlorobenzene
1
o
J
o
jj
Chlorophene[2-Benzyl-4-chlorophenol
1
J
j
H
o
35471-49-9
Potassium 2-benzyl-4-chlorophenate
CM
i
.2
|i
Ji
g
3184-65-4
Sodium 2-benzyl-4-chlorophenate
1
o
>
1
OO
2-Chlorophenol
i
i
i
u
1
2-Chloro-4-phenylphenol
S
o
i
1
1
oc
oc
Potassium 2-chIoro-4-phenylphenate
1
g
i
vt
a
not available I
4-Chloro-2-phenylphenoI
00
1
1
CO
a
I 53404-21-0
4-ChIoro-2-phenylphenoI, potassium sa
§
S
o
1
tl
t-i-
t/1
OO
6-ChIoro-2-phenylphenol
0
OJ
OJ
!
u
oc
ex
6-Chloro-2-phcnyIphenoi, potassium sa
OJ
1
V
O
IT
1
J
"o
1
_Q
a
CM
g
_o
O
CM
1
O
!
.8
-------
DRAFTr-DO NOT QUOTE OR CITE
i
=
IS
I c
£.2
•o i*
,«•§
o o
o >
Q. 03
w .2
o> %-•
2 =5
u c
v= o
o .
(b «
+•* 05
03 .C
Q £
o >•
3 oo
'
w w
0) C
Q- x
•M O
£5
"- .c
M- *-"
0 i
CO
3 T3
•K ®
(0 +-•
A; ro
CO C
CM" I
^ £
00 O
_2 O
o
.§ "o
r
i
i
„
i
^
'I
<*•
^
.-
i
1 4 and 6-Chloro-2-phenylphenol, dielhanolami
S
O
!
i
'(
<
\
o
E
|
i
T
g
g
*
1
jC
i
. "c
c
1
c
a
•E
«
1
CJ
CO
Q
2
o
•z
o
2
not available
u
g
C
en
O
1
***
•s .
•g
u
• |
'S
o
§
ADBAC [Alkyl* dimethyl 3,4-dichlorobenzyl
CIS)]
3.
Ox
O
c
c
c
i
;:
'c
^c
c
s
e
?
•^
§
^
^c.
V
r-
o
*«
"c
c
c
1
es
1
z.
o
i
, 0
o
c
5-Chlorosalicylaniiide
1
':
c
O
en
c
o
i
o
o
oo
ss
S
o
c
\
,,—
J
u
Tetradifon [4-chlorophenyl 2,4,5-trichIorophei
Ox
S
0
Chloranil [tetrachloro-p-benzoquinone]
o
1
c
0
V
e
oo
6-Chlorothymol
S
S
§
en
VJ
o
c
-
I
e
Aniiazine[2,4-DichIoro-6-(o-chloroaniIino)-s-i
oo
o
oo
o
,
I
Ox
c
Chlorothalonil [tetrachloroisophthalonitrile]
o
OX
oo
o
c
c
<
Sodium 2,3,6-TrichlorophehyIacetate ,
1
CM
-•:
c
c
o
r
Chlorfenvinphos
o
i
o
c
1
Ic
c
1
1
.1
•?
O-(2-Chloro- l-(2,5-dichIorophenyl)vinyl) O.O
o
1
O
C
o
oo
PCMX [4-Ch!oro-3,5-xylenol]
o
00
\D
§
<
<
en
- c
^
a
c
•g
Piperalin f3-(2-MethvlDiDeridino>DroDvl 3.4-dii
rn
8
8-69
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
si
21
I
as
frS
CAS Number
r—t
C
1
$
B
S
2
I
fi
(
o
e
.0
c
1
c
1
J
1
1
£
vo
c
a
I
p-Chlorophenyl diiodomelhyl sulfone
i
o
o
1
i
Metribuzin
S
O
L
>•
. en
s
V
"5
i
X
o
1
_o
•5
S
tA
"3
1
is
o
i
c
>
i
i
s
v-
cr
ii
a
cs
£
1
C
GJ
1
•3
1
«
CJ
g
>
o
z
a
cn
5
V
en
1
Diflubenzuron [N-(((4-chIorophenyl)amino}carbonyl)-2,6-difluorobenzai
o
1
O
en
c
c
i
1
c;
O
•4
en
Oxadiazon [2-tert-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)- delta 2 -I,
8
1
In review 1
o
Z
51630-58-i
Fenvalerate
o
1
o
0
Z
69409-94-5
1
?n
_2
i
a:
c
(L
C
en
[ Fluvalinate [N-2-Chloro-4-trifluoromethyl)phenyl-DL-vaIine (+-)-cyano(
S
1
0
0
Z
Ti-
en
cn
Iprodione [3-(3,5-Dichlorophenyl)-N-( 1 -methylethyl)-2,4-dioxo- 1 -
ilnidazolidinecarboxamide (9CA)]
I
o
o
Z
43121-43-3
I
K
S
Triadimefon[l-(4-Chiorophenoxy)-3,3-dimethyI-l-(lH-l,2,4-triazol-l-y
o
1
*
o
Z
51338-27-3
(U
c
1
1
1 6'-tribroinophenyl)-6-
(trifuloromethyl)benzenamine]
o
oo
01
o
o
Z
50471-44-8
5
ON
0>
J
VinclozoIin[3-(3.5-Dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazoIidine
en
In review II
83588-43-6
!J
">,
x
0
•s
u
en
.S
-a
I
Fenridazon [Potassium 1 -(p-chlorophenyl)- 1 ,4-dihydro-6-methyl-4-oxo-
o\
o
es
9
OC
Tridiphane [2-(3,5-Dichlorophenyl)-2-(2,2,2-trichloroethyI) oxirane]
1
01
o
o
Z
o
oo
en
t^
Paclobutrazol
o
vo
In review ||
VO
o
2
r*
"o
o
ea
.S
00
en
oo
oo
eN
*
O
2:
oo
oo
oo
vo
o
vo
Fenarimol[a-(2-chIorophenyI)-a-(4-chIorophenyl)-5-pyrimidinemethanol
1
8-70
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
. g,
•~! •
31'"
CO :
c/
'
1
'I?
>s
1
<
-a
0
- 1
If
M
2
c
c
c
e
c
Dicamba [3,6-dichloro-o-anisic acid]
00
§
z;
in
V
c
o
en
o
^
c.
C3
•5
e
e
\o
er
i
=3
rt
^3
U
S
S
oo
§
en
0
i
V
c
!o
S
"Z
Diethanolamine dicamba [3,6-dichloro-2-an
S
1
Z
c
2,4-Dichlorophenoxyacetic acid
o
o
s
Z
r
\
v
(*•
Lithium 2,4-dichlorophenoxyacetate
o
o
>
c
0
c
1
i
c
1
3
g
S.
o
^
2
«
i
£
^
c
i
C5
>"
Ij
S
r
£
1
i
- cu
1
•a
cs
i
1
>
j
"j
!
<
•c
"c
c
e
J
c
e
•3
.c
O
J
0
: ^
Alkanol* ainine 2,4-dichlorophenoxyacetate
0
o
o
8
', >
\
tl
r
r-
CM"
y
s£
0
Alkyl* ainine 2,4-dichlorophenoxyacelate *(
o
>•
C
0
in
«
VO
OO
o
^
u
$
0
Alkyl* amine 2,4-dichlorophenoxyacetate *(
§
>
j
"!
c
I
c
•3
c
o
w
c
£
a
V
Alkyl* ainine 2,4-dichlorophenoxyacetate *(
o
o
8
z
z
0
c
c
Diethanolamine 2,4-dichlorophenoxyacetate
VO
o.
£
6
r
c
e
c
i
1
w
•a
Ti-
es"
.S
1
o
8
z
*
C
en
1
r
*.
Dimethylamine 2,4-dichlorophenoxyacetate
ON
O
O
8
>
f-
V
C
in
en
•in
C*1
•
&
X
N,N-Dimethyloleylamine2,4-dichloropheno
o
O
O
>
o
in
c
c
•n
en
Ethanolamine 2,4-dichlorophenoxyacetate
en
o
>
c
en
\j
•8
r*
Heptylamine 2,4-dichlorophenoxyacetate
en
a
to
8
£
V
CS
r-
u
c*
r*-
C"
u
(*•
Morphpline 2,4-dichlorophenoxyacetate
oo
g
s
.' I
C
in
c
c
cs
u
c;
X
O
•3
N-Oleyl- 1 ,3-propylenediamine 2,4-dichlorop
cs
o
c
<
«n
e*
c*
r
Octylamine 2,4-dichlorophenoxyacetate
o
§
e/j
(
C
C
o
VO
in
C1
Triethanolamine 2,4-dichlorophenoxyacetate
en
en
o
8
2
2
0
0
V
\J
cs
Triethvlamine2.4-dichlororjhenoxvacetate
^i-
en
o
c
'x
o
b
T3
0)
•!-•
CD
- C
'£
CD
t
O
O
O)
"S
CD
o
QJ
Q.
C/9
03
CO
o
to
CO
O
ra
•!->
CO
Q
CD
o
o
0.
TJ
O
U
0>
CO
CO
•f-*
cc
4-<
CO
co
CN
CO
_
.Q
CD
8-71
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
8-72
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
f
i
&S
3 *
CO j
<
\
1_
C
' OJ
I
c
- j
t
•
'
es
V
c
"e;
-DCPA [Dimethyl tetrachloroterep
1
O
r-
oo
S
( 2
r-.
ON
V
a
e
' 5
Ic
-2,4,3-benzodioxa
fan [hexachlorohexahydromethano
i
1
•
r
"c
2-(2,4,5-trichlorophenoxy)propioni
X
u
So
o
o
- >
VI
•~4
VJ
¥
S
• •§
a
^c
1
1
orvinphos [2-ChIoro- 1 -(2 AS-trich
.c
o
s
o
t-
en
§
1
CA
i
«
r
o
o
1
podium 1 ,4',5'-trichloro-2'-(2,4,5-t
isulfonanilide]
J.I
II -
o
o
0)
.O
x
o
T3
0)
4->
CD
E
CD
4-»
O
O
CO
'5
co
T3
V
•*-•
U
a>
a.
M
3
CO
w
0)
2
'o
v>
(O
I
CD
O
CD
0)
_-D
[o
"•*-»
CO
o
a.
•o
o
o
a>
CO
co
+->
CD
CO
CN
CO
CD
8-73
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-24. 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
(#g/kg)
0.1
0.5
2.5
2.5
2.5
100
—
1
5
5
25
25
25
25
1000
1000
_
Total
Number 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
Concentration
0/g/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
Average
Concentration
(Aig/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
5.60 (0 70 TEQ)
Source: U.S. EPA Office of Pesticide Program file
a Limit of quantitation required by EPA in the Data Call-In.
Average 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; not detected values were
assumed to be zero.
ii ii ' ' ii' Miiii' ' " *ii ' •,!" „ II '
Total equals the sum of the individual congener averages.
fig/kg *• mterograrns per kilogram.
1, ' ' '' ..; I'l'::11 " r i i' I II ' i ''„',"
"—" indicates analyses not performed.
8-74
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
CO
c
co
O
CD
O
CD
•a
ca
CD
a.
t
>
c
'
•o
'5
CD
_o
t
•n
hyl-4-chlorophenoxy)bi
03
' t
4
TJ
'o
CO
MCPB, 4-butyrid
,_
o
CM
en
0
c
phenoxyacetic acid
4-Chloro
Q-
CJ
4
,_
o
en
o
c
lorobenzonitrile
x:
u
b
CD
CM
Dichlobenil
,_
o
CM
O
c
0
CO
"i
o
o
,o
x:
o
b
co
CO
Dicamba
,_
o
co
o>
CN
o
c
4*^
CO
CO
CD
c:
^0
>fc
•fj
CD
S
o
CD
U
"»
"c
cp
6
S
o
x:
o
5
co
CO
o
c
E
.£
«_^
Dicamba, dimeth
CNI
O
CO
en
S
1
"c
CD
a
o
CD
' C
. c
o
x:
a.
c
0
x:
c
a
CN
Q
4
CM"
^
0
o
o
CO
o
i
o
<
c
. c
c
c
CD
'x:
• £
•£
. IE
_c
X
a
Xj
f
"3
c
•c
u.
in
CM
9"
CM
CO
CO
0
O
CO
o
c
"O
1
chlorophenoxylbutyric
9
4
CM
4
CO
a
4
CM
0
CO
O
CO
O
:
.{
oro-4-nitroaniline
x:
c
b
.CO
CN
2
U
Q
O
CO
CO
o
o
'
•o
'c
co
o
'E
°£
C
J
e
c
CD
x:
£
c
x:
c
b
4
CN
CM
Q.
Q
4
CM"
o
CO
o
<
•a
'c
'i
^
£
o
t.
£
>
j
X
O
1
1
o
CM
Mecoprop {MCPP]
o
in
CO
0
o
Q
"C
"i
IS
C
a
c
T
x:
4
6
c
X
B
in
CO
Bromoxynil
o
CO
in
CO
o
o
"c
^
£
>
C
a
x:
c
c
x:
c
4
CN
CM
1
X
in
c
CO
CO
CO
a>
O
en
in
0
•
. (
CD
tetrachloroterephthalat
t
c
Dacthal (DCPA)
o
CO
r*.
o
t
roisophthalonitrile
Tetrachio
Chlorothalonil
o
en
CO
0
<
i
c
x:
c
CO
c
c
i
c
E
c
•;
~
C
0
x:
£
,C
J
_C
in
0
2-Chloro-
Tetrachlorvinphos
o
CO
CO
o
o
(
1
(
{
C
C
--—
.Hi
CD
O
C
C
orophenyllaminolcarbo
x:
o
4
Diflubenzuron
o
CM
CO
o
:
i
u
(
1
"
p
1
c
i
e
c
4
~
t
C
c
s
;
£
0
k.
£
C
"™
in
i
2E
;c
o
X
1
CM
Oxadiazon
109001
— ]
|
II
o
-
CD
4-*
CD
O
£Z
CO
Q.
O
Q
fft^
x
o
§
x:
Q.
3^
(4-{2,4-dichlorophenox
CM
x:
4-*
CD
Dichlofop-methyl
CM
O
cn
o
CO
o>
O)
•
-------
DRAFT-DO NOT QUOTE OR CITE
•'£• 0
Ratio (mean congener cone. / mean total 2378-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^,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
2,3,477,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6 J,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1A3,4,6,7,8,9-OCDF
Source: Bued on mean concentrations rcDoned in Table 8-24; nondetccts set equal to zero.
Figure 8-5. Congener Profile for 2,4-D (salts arid esters)
8-76
April 1998
-------
O
9
4
CN
O)
C
O
O
in
O
I
•3
£
CD
"5
•a'
c
03
a
4
Q.
(0
CO
CO
O
c
O
O
c
O
O
u_
a
O
Q
Q
O
CD
CN
00
o-gs.1
a>
CO CM CO CO
r>- CN r- tfr
01 00 O O
q q p q
6 d d d
JV, ^J »
?8c
I- o .c
,— ID »t ro
ro co «- CN
8288
d d d d
8 2 8 S 8 £
£828888
"
Q d Q d d d d
CM CM
2 co CM 10 °. co 10
o q q q o CM cq
Q d d d
o o
'COOr-COOOT-
COT— t— «— OO«~v— OcO
8888ss8828
dddoQQddod
•Z.-Z. Z
CM
O ,
O O O Q O O O O
Z
CO CO CM CO
^- 1O T- »-
T- CM O O
q *# o. q
d d d d
^- oo ro to
•* CM o .-
-- to o o
O T- O O
o o o o
00 CO CO CO
CM CO CM CM
,-,-00
q q q q
"
o" d d
o CM o CD. rt m T-
Q "- Q d o" d d
fe-
°- >• —
3 .±: ?»
CD O
HI
<£.
§•"£"1
co
O O O CM O CM CO
Q Q Q °" Q ^ "
-z.-z.-z. z
d d
Qdo"dd
dd
Q Q Q
Z Z 2
a n
z
a:
c
^:8 :£:*:£;£
§ ~I a. co co co co
H- co co Is* r^» co r*^
co o>
r^" co"
co r^
co r--
co
co
r^ co ^t co co co ^f co co ^
COCN"COCN~CN"CNCOCN~CN"O
CM T- CN ^
,- CM ^ ^- O
o o
II II
'g.z S*
Qu. O-
a Q ii n
o o
co
co
a a
co co" O O
i vi LU Ul
CM CM |- I-
CO CD CO CO
O O O O
odd
,2
,2
2.
S.
TJ
ID
TO
T3
o E
o 5> PT
3 = S
LU ^£ ro
.5 o
-o °-
CD in
3 . E
o •= S
jo £ ra
| sl
Q O II
CO
o
g
o
CD
JZ
O
CO
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-27. Mean CDD/CDF Measurements in Effluents from Nine U.S. 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 TEQ
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total OCDD
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
Total OCDF
Total CDD/CDF
b
No.
Detections/
No. 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
Detection
Limits
0.31 - 8.8
0.45 - 1 5
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 - 1 1
0.75-18
6.2 - 57
0.39 - 6.8
0.64 - 25
0.93- 17
0.36- 19
0.86 - 28
Range of Detected
Concentrations
{POTW mean basis)
Minimu
m
Detects
d
Cone.
(pg/L)
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
Detected
Cone.
(pg/L)
nd
nd
nd
nd
nd
5.0
99.75
1.3
2.0
2.8
2.4
1.5
2.0
nd
4.6
nd
3.2
99.75
16.6
2.32
9.7
nd
1.7
8.4
99.75
25.0
20.0
13.0
4.6
3.2
99.75
Overall Means*
Mean
Cone.
(ND = 0)
(pg/L)
0.00
0.00
0.00
0.00
0.00
1.06
29.51
.0.14
0.22
0.31
0.27
0.17
0.22
0.00
0.68
0.00
0.36
30.57
2.37
0.29
1.23
0.00
0.19
1.83
29.51
6.61
2.22
1.44
0.68
0.36
42.00
Mean
Cone.
(ND = 1/2D
L)
(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
3.40
47.98
15.49
3.66
2.61
6.27
1.93
4.77
37.95
7.70
4.72
3.43
2.41
3.40
71.96
nd = not detected.
* =» The "overall means" are the means of the individual POTW mean concentrations.
pg/L = picograms per liter.
Source: California Regional Water Quality Control Board (1996).
8-78
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
I
CO
CD
^
C "
2 i
W 4
.= [
X C
CO 1
^> 1
4-
£
<
j
s.
o __
CD 0
IS
CD 4^
T> CD p?
C CO •.
0
CO
4-» ;
S o E
4w 4-» •-
CD 4- — '
T3 CD „
C- C/3 i
z Q
CO
o
C CO N
O
"
CO
H 8 1
•o o •
e GO •£
2 Q
5 »
IS.
5
:1
M
• o
Q
CD
C
CD
CJ
C
0
O
DC CC CC CC CC CC CC
z z z z zz z
T
OC CC CC CC CC CC CC
z z z z z z z
•08
O O O O O CO X
°°co
,
co Tt- ir> co o ift g
°? °? CM i< oo £2 cr
CO C» CN CM CM CO
'
bg
co co i^ r^ r» o x
*- CO CO CO CO «*> jjj
s ^
o^
co oo in co en oo 2
«- •<— CN "* CO OS °
Q
Q Q Q O
Q Q Q Q <£
9 0 0 O T
_ f-J x x x -V
•) o. oo oo o> r^
— 06 P< r-T co co"
oo r*» ^~ co T^ ^f
t>." co co co" co co §
co CM CM" CM" CM" CM" Q
CM T- t- 1- T- T- O
ccoriroccccccrcccccc
*— ^"* ^~ ^"
cccccccccccccccccccc
z z z z z z z z z z
o o o
OJOOOOOOto'OQ
CO CO 00
(
'
OO'sJ-OOOOOOo
»— O) «- CM «- t— T- in CM »-
'fessisslfilsl
^ ^- r*T °° g
CO CM CM.'fr CO i- CM 1^ CM CO
ii u_
UL U- UL U. Q Q
....QQQQ""
;fefeuoooJg-£-
fjO-OLCOcodjobrCeo"
l-p00cor~"iCoor>rcb"r>r
cor^i^-^*Bcor^co^p ^
r^'co'^-'cococo'^cocot
COCMCOCM"CMCMCO"CM'CM§
CM" •<- CM" *- T- i- CM" >- ,t- p
o
in
co
00
c>
.•*
if
CN
OC
O
HI
1—
CD
f\
°
CC
' ^r
CC
z
CC
CC
CC
LJ_
Q
o
Q
O
O
1
CO
CO
CsT
03
O
ii +>>'
II "°
4-
&
CO
CD
Q.
CO
_o
V-*
.S2
CO
4w
CO
£•
CD
|
CD
-.c -
4-»
CD
O
«
ja
"o
£
CD
CD
£
CD
g
CO
0
£
4^
§
o
c
o
o
5 £
= '5
o a
Q. >
_® >•
CO ^
CD —
Q. ^
E ^
O c
Q. g
CD ""P
,' co "^
05
O5 -o
T- CD
I
•a
i
"g
c »
o £ ro
a. Q. o
CD c
>- co co
+-> CD C
03
Z To II
8-79
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
CD
I
I
"c
c
.£
+z
1
CD
U
C
o
O
c.
CD
5
"S
c
2
CD
0
g
O
c
CO
1
Maximum
Concentration
4--
m O «-
S ** 0
•S CO CD
C CO N
o
*J 4-<
~a CD .
c co «g
Nondetects
Set to
Zero
T3 ~ *- CM T- CO i-
«- •* CO CM O T- O
r>- co q pj ^ co o
-
O O co eo r-» ^ in
CM r-^ 00 CM T- CO t—
CM CO T- CO CM T- O
CM T- T- CO CM m K
r~ co CN £
o o o ^ •* TJ- co
• , CM en - r^ co eo
co h* ^ eo r** ^h
r*^ co co co co co ^
CO CM CM CM CM" CM CJ
CM" T- ,- t- ^ ^- o
CM co co en en h» o i»» «3- eo
CMdJMCMJM^^CNcO1"
^S2°"S^"S^
cocococoeoco'*— cog
2 ^ 2 CN S " § f5 W ^
oot^rx^j-^-^oocor-. —
^.^^CNCO.-CM^CN^
OO CO ,-
^oooooo^-'oco
CO CO ^
cor-oinocoinr^r-co
S|Sg|SS|s|
S539^*SS5-S
u. u.
u. u_ u_ u- Q Q
QQCJOOCJ-T'T'
fjOuCuoococnoor^oo
l— ooco?^p>^oot^coi~r
cor^rs«'^-cor^cO'*'j-
r^co^tco~co~co"'3-~coco*Jir
COCMCOCNCM'cMCOCMCMcj
CN" t- CN «- t- T- CN t- r- O
O
in
^
eo
o
in
CO
CO
o
d
CO
CD
eo
CM
CN
CO
"55
CO
"5
co
a
o
i-
c
CM
*
cc
CO
cr
CO
^
o
s
CO
CO
eo
en
o
CM
in
CO
7,8-CDD/CDF
C*J
eg
4_(
o
?-- o
CD
E 5
.2 g c
CD <» TJ
•S -C CD
W 4-» 4-*
•a - c
" CO CD
CO CD CO
1 a £
TO £ =-
S CO CO
05 CO CD
£ CD =
CO Q. JO
c
CD
CO *= ""
CD "5 C
CO = CO
03 E :=
f «1
CD °> C
« » C
O- -S2 m
O
CD
Q
O
CO
co
CD
"co
8-80
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
2,3,7,8-TCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
l,2,3,4,6,7,8-HpCDI>
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-HxCpF
1,2,3,6,7,8-HxCDF
I ,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7.8-HpCDF
1^,3.4,7.8,9-HpCDF
,4,6,7.8.9-OCDF
o.i,
Ratio (mean congener cone. / total 2378-CDD/CDF cone.)
0-2 0-3 _ 0.4 . 0.5 0.6 O.7
L
O.8
I
O.9
Ratio (mean congener cone. / total 2378-CDD/CDF cone.)
0-1 0.2 0.3 0.4 0.5 O.6 O.7
0.8
0.9
2,3,7,8-TCDD
1^,3,7,8-PcCDD
1^,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 ^,3,4,6,7,8,9-OCDD
2,3,7,8-TCDF
1^,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1 ^,3,6,7,8-HxCDF
1^,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
Somca: On«a«tBl. (1995),
Figure 8-6. Congener Profiles for Sewage Sludge
8-81
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-30. Quantity of Sewage Sludge Disposed Annually by Primary, Secondary,
or Advanced treatment POTWs and Potential Dioxin TEQ Releases
Use/Disposal Practice
Land Application
Distribution and Marketing
Surface Disposal Site/Other
Sewage Sludge Landfill
Co-Disposal Landfills8
Sludge Incinerators and Co-
Incinerators6
Ocean Disposal
TOTAL
Volume Disposed (thousands
of dry metric tons/year)
1,714
71
396
157
1,819
865
(336)d
5,357
Percent of
Total
Volume
32.0e
1.3
7.4
2.9
33.9
16.1
(6.3)d
100.0
Potential Dioxin
Release0
{g of TEQ/yr)
85.7
3.6
19.8
7.8
91.0
(f)
(0)d
207 9
' Landfills used for disposal of sewage sludge and solid waste residuals.
c Potential dioxin TEQ release for nonincinerated sludges was estimated by multiplying the sludge volume
generated {i.e., column 2| by the average of the median dioxin TEQ concentrations in sludge reported by
Rubin and White (1992) (i.e., 50'i4-ng/kg dry weight) and Green'et' al. (1995) and Cramer et al (1995)
(i.e., 49.1-ng TEO/kg).
d The 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 in the oceans; inij 9881 has not been determined.
8 includes 21.9 percent applied to agricultural land, 2.8 percent applied as compost, 0.6 percent applied to
forestry land, 3.1 percent applied to "public contact" land, 1.2 percent applied to reclamation sites, and
2.4 percent applied in undefined settings.
' ^ee Section 3-6,;5 for estim£ltes $CPD/9DF.rS!e^es to ?!f.f£°m Sewa9e Slud9e incinerators.
Sources: Federal Register (1990); Federal Register (1993b); Rubin and White (1992); Green et al. (1995);
Cramer et al, (1995).
8-82
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 8-31. 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-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
Liquid Soap
(ng/L)
ND (0.009)
0.400
ND (0.020)
0.320
0.180
1 .900
1.000
0.620
0.290
0.200
0.013
ND (0.004)
ND (0.004)
ND (0.004)
ND (0.005)
ND (0.010)
NA
3.8
1.123
0.447
0.120
15.000,
3,400
3.600
1 .000
1.000
1.300
0.150
ND (0.010)
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 (O.8)
ND (2)
NA
14.2
25,2
9.5
31
380
3.3
ND(1)
5.3
;'-.-. 26
41
4.9
ND (2)
NA
Tall Resin
(ng/kg)
ND (1)
1 "IU/ 1 1 /
3.1
ND (4)
i«l_r \Tf
810
500
5,900
6,000
ND (2)
fltu' \f-l
ND (0.4)
ND (05)
• •IP' \\Jt\Jf
' 24
ND (1)
t W I I /
r ND (0.7)
10
9.0
NA
13213.1
43
200
ND (1)
•"«* \ * 1
25
6,800
11,000
6,000
ND (2)
ND (0.5)
56
19
NA
Source: Rappe et al. (1990c).
ND = Nondetected; value in parenthesis is the detection limit.
NA = Not analyzed. '
= Not reported. -
ng/kg = nanograms per kilogram.
8-83
April 1998
-------
. ii
" ViSi
-------
•'. . DRAFT-DO NOT QUOTE OR CITE
9. BIOLOGICAL SOURCES OF CDD/CDF
Recent laboratory and field research studies demonstrate that biochemical formation
of CDD/CDFs from chlorophenol precursors is possible and that, under certain conditions,
some CDD/CDFs can be biodegraded to form less chlorinated congeners. Both of these
formation routes are discussed in this chapter.
Also, CDD/CDFs were recently discovered in ball clay deposits. The origin of these
CDD/CDFs is not yet determined, and natural occurrence is still considered a possibility.
.9.1. BIOTRANSFORMATION OF CHLOROPHENOLS
Several researchers demonstrated under laboratory conditions that biochemical
formation of CDD/CDFs from chlorophenol precursors is possible. These studies are
described below. However, the extent to which CDD/CDFs are formed in the environment
via this mechanism cannot be estimated at this time.
In 1991, Lahl et al. (1991) reported finding CDD/CDFs in all 22 samples of various
types of composts analyzed. The hepta- and octa-substituted CDDs and CDFs were
typically the dominant congener groups found. The TEQ content of the composts ranged
from 0.8- to 35.7-ng TEQ/kg. Similarly, CDD/CDFs are frequently detected in sewage
sludges. (See Section 8.4.1.} The CDD/CDFs found in compost may primarily be the result
of atmospheric deposition onto plants which are subsequently composted and also by
uptake of CDD/CDFs from air by the active compost (Krauss et al., 1994). The CDD/CDFs
found in sewage sludge may primarily be due to the sources identified in Section 8.4.1.
However, laboratory studies with solutions of trichlorophenols and pentachlorophenol (PCP)
in the presence of peroxidase enzymes and hydrogen peroxide (Svenson et al., 1989; Oberg
et al., 1990; Wagner et al., 1990; Oberg and Rappe, 1992; Morimoto and Kenji, 1995) and
with sewage sludge spiked with PCP {Oberg et al., 1992) indicate that biochemical
formation of CDD/CDFs, particularly the higher chlorinated congeners, from chlorophenol
precursors is possible.
Peroxidases are common enzymes in nature. For example, the initial degradation of
the lignin-polymer by white- and. brown-rot fungi is peroxidase catalyzed (Wagner et al.,
1990). The actual conversion efficiency of chlorinated phenols to CDD/CDFs observed in
these studies was low, however. In the solution studies, Oberg and Rappe (1992) reported
9-1
April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
a conversion efficiency of PCP to OCDD of about 0.01 percent; Morimoto and Kenji (1995)
"" n ' n °mr , ', „ , ' , ' ', , , „" '',,,'. "'-'
reported a conversion efficiency of PCP to OCDD of 0.8 percent; and Wagner et al. (1990)
reported a conversion efficiency of trichlorophenol to HpCDD of about 0.001 percent.
Oberg et al. (1996) reported a conversion efficiency of trichlorophenols to CDD/CDFs of
about 0.001 percent. In the sewage sludge study (Oberg et al. 1992), a conversion
efficiency of PCP to total CDDs of 0.0002 to 0.0004 percent was reported.
Several researchers recently conducted both laboratory and field studies in an
1 , ; • * " :- •"'..;.' '.:;'?.'' !;! '':v'. i":i •,•>.•', <"• '• •;'•.:':; -j'i ^Wv'v ^i'^'S'1 • I1 .. , ••': " ; ' .
attempt to better understand the extent and factors affecting the fate and/or formation of
'•:'• ' - •:•• !'!;;-i "•:. ; ,.^"-\'.\$ W'Vv^Tik'S,.''•;<'•. $ *'"*•}'• •.•,.-j-t. *..?•:•, r , •,, . -
CDD/CDFs in composts and sewage sludges. The findings of several of these studies are
discussed in the following paragraphs. The findings are not always consistent in terms of
the congener profiles/patterns detected and the extent, if any, of CDD/CDF "formation,"
which may be due in part to variations in the compost materials studied, experimental or
,",!„, . ,i ' .'Kill! 'I " ,' ,' I',,11, ,i,' ,„'! , '' ., . '' ';•'" , !'/,' ;:'„,. = ' „ ., !l! «",!!:: ,,:1: , ,i
field composting design, and duration of the studies.
Harrad et al. (1991) analyzed finished composts and active compost windrows from
a municipally-operated yard waste^composting facility in Long Island, New York.
'.''::••• , :• "'' ;" 'siiEi ;' i, ;• -'; /i,; "", >i • ' • : ;',,'',/.." ::V''.'•>.'- *•;].:.;;<;.,{>•"•,,'. J,:•,'•'.' V'W, i1,'.;' • 1 • ,• ;
Concentrations measured in 12 finished composts ranged from 14- to 41-ng TEQ/kg (mean
of 31-ng TEQ/kg). the concentrations in the five active compost samples (1 to 30 days in
age) ranged from 7.7- to 54-ng TEQ/kg (mean of 21-ng TEQ/kg). The observation that
CDD/CDF concentrations measured in two soil samples from the immediate vicinity of the
composting (1.0- and 1.3-ng TEQ/kg) facility were significantly lower than the levels found
in the composts, suggested to the authors that the source(s) of CDD/CDFs in the composts
' • > • • , • ' -, SKI i1, ••: i,',1 •,., :• ,i:. •• ;: •, =« y. i to?, ;• : ,;•., ; s, • iv;:i ;i '.Ui,1 ,,";' .••' '.. i,. ,' ; .•' ' • ',
was different than the source(s) affecting local soils. A strong similarity between the
congener profiles observed in the composts with the congener profile of a PCP formulation
(i.e., predominance of 1,2,4,6,8,9-HxCDF and 1',2,3,4,6,8,9-HpCDF in their respective
,;ti" : •. .• • . " • •!•«'• ' : •.: i:,.•".. •', •<, •' " " ;'";."' : •• r.1 ;:•„•' ' (d1 ;>i, :":. i- •. !,!'.. i •:,>.• : !"i
;;, . . • •',!(;,, i .. ''•:.• i .:. ,,(,"!, i «„ '':."!,;,!, • M-i ,. '• [•• ,. ..•• -,-; ..•;;, ,.,. . !•„!,", •;,;. • | ' , • ,
congener groups) indicated to the authors that leaching of CDD/CDFs from PCP-treated
wogd in the compost piles was the likely source of the observed CDD/CDFs. The levels of
PCP in the 12 finished composts ranged from 7 to 190 //g/kg (mean of 33 /^g/kg), and the
•; • " „ »i, i "if! • • ..'" ,""'f» i !'.,» a ,'',; -! i'T1 , •• f \: •" :,; >! >• • •• ,, ',i:''!'i i1",,1, „",•!, n, ,•>, ' • ,•!,!;:,:"!•!•' '•> r
PCP levels in the active compost samples ranged from 17.to 210 y^g/kg (mean of 68
',„'"„ " " • ' • INI,, ,;• i' „, if'u! ;• fti'i:1 ;. "j »,"!',,.;;! ..i,;!!,,' ,' • :;;!,. •'! • "'t 'LIK.*!! • ^ i,. ,„!' „, t i fl,,,,.', :,, "i,," , „, I ' , '
j"g/kg). The PCP level in both soil samples was 1.5 ^g/kg.
Goldfarb et al. (1992) and Malloy et al. (1993) reported the results of testing of
composts at three municipal yard waste composting facilities (5- to 91-ng TEQ/kg; mean of
30-ng TEQ/kg), two municipal solid waste composting facilities (19- to 96-ng TEQ/kg;
, ' " ' ' ,1'ill ' "":: I I ' I 'I •'•!•'•
'!, Ill ' ' I I '
9-2 , . . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
mean of 48-ng TEQ/kg), and one municipal facility composting solid waste and dewatered
sewage sludge (37- to 87-ng TEQ/kg; mean of 56-ng TEQ/kg). All facilities were located in
the United States. Two general trends were observed. First, an increase was observed in
analyte levels, with an increasing degree of chlprination for each compound type (i.e.,
CDDs, CDFs, chlorophenols, and chlorobenzenes). Second, an increase in concentration of
i ' , •' •
each congener or homologue group, with a progression from yard waste to solid waste to
solid waste/sewage sludge composts, was observed. As noted above, TEQ concentrations
showed this same trend, which was primarily due to increasing levels of 1,2,3,4,6,7,8-
HpCDD and OCDD. The mean PCP concentrations in the three compost types were 20
M9/kg (yard waste), 215 ^9/kg (solid waste), and 615 vg/kg (solid waste/sewage sludge).
Comparison of congener profiles by the authors indicated that the CDD/CDF residue in PCP-
treated wood in the compost feedstock was a major, but not the exclusive contributor of
the observed CDD/CDFs. The authors postulated that biological formation of HxCDDs,
HpCDDs, and OCDD from chlorophenols (tri-, tetra-, and penta-) in the compost could be
responsible for the elevated levels of these congener groups relative to their presence in
PCP.
Oberget al. (1993) measured the extent of CDD/CDF formation in three
conventional garden composts; two were spiked with PCP, and one was spiked with
hexachlorobenzene. The two PCP-spiked composts were monitored for periods of 55 days
and 286 days, respectively. A significant increase in the concentrations of the higher
chlorinated congeners, particularly the HpCDDs, OCDD, and, to.a lesser extent, OCDF,
were observed. Similar results were reported for the hexachlorobenzene-spiked compost,
which was monitored for a period of 49 days. Oberg et al. (1993) state that for a "typical"
composting event, a two- to threefold increase in TEQ content corresponds to an elevation
by 0.2- to 0.5-ng TEQ/kg dry weight.
Weber (1995) subjected sewage sludges from two German communities to
anaerobic digestion in laboratory reactors for 60 days. The two sludges were spiked with
2,3,5-trichlorophenol (10 to 25 mg/kg), a mixture of 2,3,5-trichlorophenol and
dichlorophenols (2.5 to 25 mg/kg), or a mixture of di-, tri-, and tetra-chlorqbepzenes (4 to
40 mg/kg). In nearly all of the digestion experiments, the addition of these precursors did
not lead to any significant changes in CDD/CDF concentrations. The initial CDD/CDF
concentrations in the two sludges were 9- and 20-ng TEQ/kg. The only exceptions were
9-3 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
increased 2,3,7,8-TCDF concentrations in the mixed chlorophenol experiments and
decreased 2,3,7f8-TCDF concentrations in the mixed chlorobenzene experiments.
However, the same increases or decreases for this congener were also observed in the
, • . • . .• „•, •, . . . ,- . • • i ... .. I '." . , r, .- .< . •'. ,'. .' • • I
controls (i.e., no precursors added).
"' ' ' " " " " ' ' ' ' ' ' " /
9,2, BIOTRANSFORMATION OF HIGHER* CDD/CDFS
Several recent studies examining the fate of a range of CDD/CDF congeners in pure
cultures, sediments, and sludges indicate that under certain conditions some CDD/CDF
congeners will undergo biodegradation to form less chlorinated (and possibly more toxic)
,!:•', !i ' , '" ' ' !'!'iil ill ('i '" ' ''. , '! , , "i ,,'il,, ', " ." •'!, I,' ,|. I, :•:, •':• ,|, " ' 1 • , ,h ' ,1 '' ' ' I'» JV ,N: ' «', ' 'i. In! , MB1 l,i' ''I , • , I' ,
CDD/CDFs. However, the extent to which more toxic CDD/CDFs are formed in the
environment via this mechanism cannot be estimated at this time. The following
paragraphs discuss those studies that examined the products of biodegradation in
sediments, compost, and sewage sludge.
Several recent reports indicate that CDDs and CDFs may undergo microbial
dechlorination in anaerobic sediments. Adriaens and Grbic-Galic (1992; 1993) and
Adriaens et al. (1995) reported the results of a series of microcosm studies utilizing Hudson
River sediment (contaminated with Aroclor 1242) and aquifer material (contaminated with
CDDs) from Pensacola, Florida. Both types of substrates were spiked with several CDDs
(1,2,3,4,6,7,8-HpCDD; 1,2,3,4,7,8-HxCDD; and 1,2,4,6,8,9-/1,2,4,6,7,9-HxCDD) arid
CDFs (1,2,3,4,6,7^8-HpCbF and 1,2,4,6,8-PeCDF) and monitored over a 16-month period,
at an incubation temperature of 30°C. The Hudson River sediment was spiked with 144
!» ' ' • . '.j , ." ' '- li'MJi. ',>.' • ':; i. T"V , :.i,, :. .;..., .if','•]•)•;,' .'•,..,* ••;,„.•,,'"i1 ,„:;, '.i'l, ,'.i ,;""?v; i ... !• • f
^g/kg of each congener, and the Pensacola aquifer material was spiked with 63 yug/kg of
each congener.
All of the congeners, with the exception of 1,2,3,4,6,7,8-HpCDF, showed a slow
i :• ; ,.' • tyiJl i"1'1 •. ••• •!•,,:•,;'if' yvf,1 ',;l!,>:'.', i.'«?!:•••(' ••-, : i in1, ••.",':'',;:-'! i tf'jvj ;•'•}.' i./1
decrease in concentration over time, attributed to biologicaliy mediated reductive
dechlprination, with net disappearance rates ranging from 0.0031 wk"1 to 0.0175 wk"1
,, ii "'''"" ,'• .!•„ • • "'••'•, n'"ii" •'! , 'i ' : , '«,: 'I:1"1' /'vi,.F : ii',,,: '',"i,,, •,:, > i \ .'•wiii' .."w •'' •"' •'" i» •<•< '' ». ' ' ' ' • >
(i.e., half-lives of approximately 1 to 4 years). However, Adriaens et al. (1995) conclude
that the actual half-lives may be orders of magnitude higher. The experiment with
1,2,3,4,6,7,8-HpCDD yielded formation of two HxCDD (1,2,3,4,7,8- and 1,2,3,6,7,8-).
Thus, removal of the peri-substituted (1,4,6,9) chlorines was favored, with enrichment of
2,3,7,8-substituted congeners. No lesser chlorinated congeners were identified from
incubations with the other tested congeners. 1,2,4,6,8-PeCDF was also examined in
' 9-4 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
/ ' •
dichlorophenol-enriched cultures. After 6 months incubation, several TCDFs were
identified, which also indicated that peri-dechlorination was the preferred route of
1 ' . '
reduction. ,
Barkovskii and Adriaens (1995; 1996) reported that 2,3,7,8-TCDD (extracted from
Passaic River sediments) was susceptible to reductive dechlprination when incubated at
30°C under methanogenic conditions in a mixture of aliphatic and organic acids inoculated
with microorganisms obtained from Passaic River sediments. The initial concentration of
2,3,7,8-TCDD (20 ± 4 ^g/L) decreased by 30 percent to 14 ± 2 ^g/L over a period of 7
months with the consecutive appearance and disappearance of tri-, di-, and mono-CDDs.
Experiments were also conducted by spiking the sediment with HxCDDs, HpCDDs, and
OCDD. Up to 10 percent of the spiked OCDD were converted to hepta-, hexa-, penta-,
tetra-, tri-, di-, and monochlorinated isomers, but the reaction stoichiometry was not
determined. Two distinct pathways of dechiorination were observed: the peri-
dechlorination pathway of 2,3,7,8-substituted hepta- to penta-CDDs, resulting in the
production of 2,3,7,8-TCDD, and the per/-lateral dechiorination pathway of non-2,3,7,8-
siibstituted congeners.
Several studies reported that CDD/CDFs can be formed during composting
operations through biological action on chlorophenols present in the compost feed material.
The results of studies that specify likely involvement of ehlorophenols are described in
Section 9.1. Another possible formation mechanism was suggested by Vickelsoe et al.
(1994), who reported that higher chlorinated CDD/CDF congeners are formed when humic
acid is reacted with a peroxidase enzyme, hydrogen peroxide, and sodium chloride. It is
f , . . ' •
expected that some organic material in compost and sewage sludge has a humic-like
structure. Several additional studies are described below in which the potential
involvement of chlorophenols could not be assessed, because chlorophenoi concentrations
in the composts were not reported.
Schafer et al. (1993) monitored the seasonal changes in the CDD/CDF content, as
well as the extent of CDD/CDF formation, in the composts from a vegetable and garden
waste compost operation in Germany. Finished compost samples were collected and
analyzed every 2 months for 1 year. An annual cycle was observed in TEQ concentrations,
with peak concentrations in the summer (approximately 8.5-ng TEQ/kg) that were 2.5
times higher than the lowest concentrations observed in the winter (approximately 3.5-ng
9-5
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
TEQ/kg). No seasonal source was apparent that could explain the observed differences in
seasonal levels. The CDD/CDF contents of the starting waste materials for two compost
i'li1, ,' , , , " „• " , I'flMif1 ", ," " ,", "T i'1 , n 'mi" ; !• ' .," , 's, 'l!''||, ",,i f ',i'.',i :'„ , ' U{. , „.,••,.,,,,', i, | , , «*
cycles (March and September) were measured to monitor the extent, of CDD/CDF formation
during composting. For the March cycle sample, most 2,3,7,8-substituted CDD/CDF
congeners decreased in concentration during composting. Four CDF congeners showed a
P: "I, , •',,, "' ; i : ' ' ,, ' Ml"! ,,!',;"' ' „, ii „» „• ,i,[. A, • i,, "| i ,:'"','„, , „ " '"'IHH1 I, ,„' i/ I > ":„"'.; . ,,, , • , , ^ •, "'P!,,'1- ,,:",',•,'' ..,''! : • ,;
slight increase in concentration (i.e., less than 10 percent). For the September cycle
sarnple, OCDD andIHpCDD concentrations increased 300 percent during composting. Less
than 10 percent increases, were, observed for HxCDDs and PCDF; all other 2,3,7,8-
substituted CDD/CDF congeners showed decreases in concentrations during composting.
Krauss et al. (1994) measured the extent of CDD/CDF formation during the
composting of household waste using a laboratory compost reactor. After 11 weeks, the
• » ,,,i!'',,, : ": " ,. . , . ' ,n ji'-iTjiiiim ; i ;, ; ."Hi.' „•• .,,', „ .i; f '. ;,; ,, "",:;„ d HxCDD showed no change in mass content. All CDF congener groups showed
decreases in mass content; however, the concentrations in both the starting and finished
conipost were close to the analytical "detection limits.
Oberg et al. (1994) reported the results of monitoring of two household waste
>."1 i :'' . " Klttl '" .-"'.'.. "'r •'•.'. I ' is, : , ', i'1'" V ,"•[','/: ''' l.f.'l ' ; Mil;") i" ?,",: ';" ,;;!-' •' I, '
composts and two garden composts. For the two household waste composts, total
CDD/CDF content decreased in fcjqth composts over the 12-week test period. Total CDD
Pi'i'iill-! „ • , •' „'„ „'!: ' , 3 IJii'1! I,"".;. T' • ,- : 'i", .• ,!„•'• ' 'i'ii , ; • i "i; i1 ,,•:. V :•• ! ,«. "• •, M.J. ',., i i,,,',r, ,,.,l''r, '.!,,'!,'. ' iif,:|1 ,' ,' 'i! ,„, • i , , ,
content and PCB content decreased, but total CDF content increased in contrast to the
i'i r'l., ," . . '•" f1 , ii'SB :,', .,'.'' i , "'',' a£i I1;' 'ft, .".',,;' j;"1, ';,"!•,)!,' ,;-, '•, •;1i;|1 ; i'l <;• i i ' .'ll-'t. i'i'i ,; '' 'I'.
findings of Krauss et al. (1994). A small increase in OCDD content in both composts,
how/ever, was observed. The two garden composts were monitored bv Oberq et al. (1994)
:• • ;'.!».•'. '. i '>' :•'..- >, :'ja '.< v •. - •• '' ':; ,.W." •.'.'•' " i,11-. .!•'; ' (•,.::! - :.,>.• ,;'•";: .t >• • • .1 '!;..• r.-< . • > t s • •
for a 60-week period. Total CDD/CDF concentration increased, with the largest increases
observed for OCDD and HpCDDs. The lower chlorinated CDFs decreased in concentration.
As a followup to a preliminary study (Hengstmann et al., 1990) that indicated
CDD/CDF concentrations may increase and congener profiles may change during anaerobic
.•;. • i • ' ii F • • •
digestion of sewage sludge, Weber et al. (1995) subjected sewage sludges from two
• ',i, ' '• '-. i . i.1 ii i ' " i i i .,,, t • .-' . ' '.
German cprnmunities to anaerobic digestion and aerobic digestion in laboratory reactors for
• •>;•, ; ' ' ii ' • I I i I . I .'• ' •• . . •
60 days and 20 days, respectively. The initial average TEQ concentrations in the raw
fV ' ' '!•!, ll'l I i i i i .'.i , , . • . .
sludges were 20- and 200-ng TEQ/kg. No significant increase or decrease in total
CDD/CDF content or congener group content was observed with either sludge. In contrast,
a significant decrease in CDD/CDF content was observed in the aerobic digestion
9-6 April 1998
-------
DRAFT-.DO NOT QUOTE OR CITE
experiments on both sludges. The greatest percentage decreases in congener group
concentrations (i.e., greater than 40 percent) were observed for TCDF, PeCDF, HxCDF,
TCDD, and PeCDD in the sludge initially containing 20-ng TEQ/kg and for TCDF, TCDD,
HpCDD, and OCDD in the initially high content sludge. The greatest percentage decreases
in congener concentrations (i.e., greater than 40 percent) were observed for non-2,3,7,8-
substituted congeners.
9"7 . April 1998
-------
-------
DRAFT-DO NOT QUOTE OR CITE
10. PHOTOCHEMICAL SOURCES OF CDD/CDF
r " ' ' ' ' ' -.
10.1. PHOTOTRANSFORMATION OF CHLOROPHENOLS
Several researchers demonstrated that CDD/CDFs can be formed via photolysis of
pentaehlorophenol (PCP) under laboratory conditions. These studies are described below.
However, the extent to which CDD/CDFs are formed in the environment via this mechanism
cannot be estimated at this time.
Lamparski et al. (1980) conducted laboratory studies to determine the effect of
• ' , \
simulated summer sunlight on the formation of OCDD, HpCDDs, and HxCDDs in wood that
was pressure treated in the laboratory with PCP. In the first set of experiments, wood
veneers (Southern pine), treated with purified PCP or with Dowicide EC-7 using methylene
chloride as the PCP carrier, were exposed to light for 70 days. The PCP concentration in
i , ''
the treated wood was 5 percent by weight, which approximates the concentration in the.
* •
outer layer of PCP-treated wood utility poles. Photolytic condensation of PCP to form
OCDD was observed, with the OCDD concentration increasing by a maximum factor of
3,000 for the purified PCP and by a factor of 20 for EC-7 at about day 20 before leveling
off. HpCDD and HxCDD were also formed apparently by photplytic degradation of OCDD
rather than by condensation of PCP and tetrachlorophenols. The HxCDD concentration
increased by a factor of 760 for the purified PCP and by a factor of 50 for EC-7 over the
70-day exposure period. The predominant HpCDD congener formed was 1,2,3,4,6,7,8-
HpCDD due to an apparen^ preferential loss of chlorine at the peri position (i.e., positions 1,
4, 6, and 9).
In a second set of experiments conducted by Lamparski et al. (1980), a hydrocarbon
oil (P-9 oil) was used as the carrier to treat the wood. The increases observed in the
OCDD, HpCDD, and HxCDD were reported to be much lower relative to the increases
observed in the first set of experiments, which utilized methylene chloride as the carrier.
j • , . " , '
Results were reported only for OCDD. The OCDD concentration increased by a maximum
factor of 1.5 for EC-7 and technical PCP, and by a factor .of 88 for purified PCP. The
results suggested to the authors that the oil either reduced condensation of PCP to OCDD
or accelerated degradation to other species by providing a hydrocarbon trap for free-radical
species. . "•:.-,.
10-1 ' April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Vollmuth et al. (1994) studied the effect of irradiating laboratory water and landfill
seepage water containing PCP under conditions simulating those used to purify water with
ultraviolet (UV) radiation (i.e., 5-hour exposure to 254-nm radiation from low pressure
mercury lamps). The three solutions tested contained approximately 1 mg/L of PCP or PCP-
Na. before irradiation, but the CDD/CDF content varied drarriatjcajly (1.5-, 2066-, and 2071-
pg" TEQ/L). Irradiation resulted in nearly total destruction of PCP (greater than 99 percent
Joss) in all three experiments. An overall net increase in TEQ content was observed in the
initially low TEQ content water, but a net decrease was observed for the two initially high
v;:. ;• • -.I1' ; ';;:'; ::';.,''."' •'•' i u, •:" I. • ,. • :• .• ,-
TEQ content waters.
• Irradiation of laboratory water containing purified PCP showed an increase in
TEQ concentration from 1.5 pg/L to 214.5 pg/L. The increase in TEQ was
due entirely to the formation of 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 HpCDDs and
HpdDFs was also observed. The ratios of the concentrations of these non-
2,3,7,8-congeners to the concentrations of the 2,3,7,8-congeners were 0.6
for HpCDDs and 5.0 for HpCDFs. The HpCDD and HpCDF congeners formed
indicated that the operative mechanism is photoinduced dechlorination of
OCDp at a peri position and dechlorination of OCDF at only the 1 - and 9-peri
;; ,, ;,; positions. '
,"„«'
Irradiation of water containing technical PCP-Na (Dowicide-G) resulted in a
net loss in CDD/CDF TEQ content from 2,065.5 pg/L to 112.7 pg/L. The
only 2,3,7,8-substituted congener showing an increased concentration was
1 '2c3,6,7,8-HxCDb. ^he other congeners originally present in the technical
PCP-Na showed reductions of 80.6 to 100 percent.
I'lllll'llil il.'i' Ill, ' ',>' '; 'HI',|! I]!!1 UN'ilill
* The TEQ content of seepage water from a landfill (2,071 pg TEQ/L) was
reduced by a factor of two to 1,088 pg TEQ/L However, several 2,3,7,8-
substituted congeners did 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 OCDF).
Waddell et al. (1 995) also studied the effect of irradiating distilled laboratory water
I !,:',,:, ••.. ""' ........ ,• ' ..-I!' "':" .• '. • ,:«,',", vji«il •".'(•";* ''''.i"!1. id;,' r tliOiVi ,'•' ;•"•!; • .'ii'.f •.;'•„ aw • v • i> •:•
containing PCP under conditions simulating those used to purify water with UV radiation.
The results obtained were similar to those of Vollmuth et al. (1994). Analytical grade PCP
at a cphcentration of ,1 6 mg/L was exposed for 1 2 minutes to 2ob-300-nm radiation from a
medium pressure mercury lamp. All CDD/CDF congener groups increased in concentration
over jhe 12-minute exposure period, with the greatest increases observed for OCDD (75
'HI'' ..... .'I ! , «. ! , "' j'li- ' . t ' , ," I ll I | I I II I I I • '' I .I ' ', ' • '
fold increase) and HpCDDs (34-fold increase). The TEQ content of the solution increased
[ "ii"1 ' " '_', ' ' ' , ............ \
from 4.2-pg TEQ/L to 137-pg TEQ/L over the 12-minute period. The dominant congeners
........... , . 1. 1 ' i i-:1!" ', ....... ' :\ ......... ...... :.j." , •'• , •• "- • • ;• •• -, ..... -,•,;,, ..... ; ii/t -,,",'• ..... ..'... • M-I > •.•• i a . .
10-2
April 1998
•
-------
DRAFT-DO NOT QUOTE OR CITE
formed in terms of both concentration and contribution to TEQ were 1,2,3,4,6,7,8-HpCDD,
OCDD, and 1,2,3,7,8,9-HxCDD.
10.2. PHOTOLYSIS OF HIGHER CDD/CDFS
Photolysis appears to be one of the few environmentally significant degradation
mechanisms for CDD/CDFs in water, air, and soil. Although, in most studies, good mass
balances were not obtained and the photolytic pathways, for CDD/CDFs were not fully
identified, a major photolysis pathway appears to be photodechlorination, resulting in
formation of lower chlorinated CDD/CDFs. A preferential loss of chlorines from the peri
positions (i.e., chlorines at the 1, 4, 6, and 9 positions) rather than from the lateral
positions {i.e., chlorines at the 2, 3, 7, and 8 positions) was reported for some congener
groups when irradiated as dry films, sorbed to soil, and as gas-phase CDD/CDFs (Choudry
and Webster/ 1989; Kieatiwong et al., 1990; Sivils et al., 1994 and 1995; Tysklind et al.;
1992). Several researchers reported that carbon-oxygen cleavage and other mechanisms
may be similarly or more important pathways for CDD/CDFs containing four or fewer
.chlorines.
Because of the difficulties inherent in controlling experimental variables for
nonvolatile and highly lipophilic compounds like CDD/CDFs, few photolysis studies have
been performed with natural waters, on soil, or particulate matrices, and in the gas phase
to examine the rates and products of photolysis under environmentally relevant conditions.
Thus, it is not possible at this time to quantitatively estimate the mass of various CDD/CDF
congeners formed in the environment annually via photolytic mechanisms. The following
paragraphs summarize the key findings of recent environmentally significant studies for the
water, soil, and air media.
10.2.1 Photolysis in Water
Numerous studies demonstrate that CDD/CDFs will undergo photodechlorination
following first order kinetics in organic solution, with preferential loss of chlorine from the
lateral positions. Photolysis is slow in pure water, but it increases dramatically when
solvents serving as hydrogen donors such as hexane, benzene, methanol, acetonitrile,
hexadecane, ethyl oleate, dioxane, and isooctane are present. However, only a few studies
have examined the photolysis of CDD/CDFs using natural waters and sunlight.
10-3 April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
Choudry and Webster (1989) experimentally determined the sunlight photolysis half-
life of 1,3,6,8-TCDD in pond water to be 3.5 days (i.e., more than 10 times greater than
,,,,.; >i;r , ||,;| U , , ,' ' I'; |,\ ,.». ,I] •! .,-' ' . ',' , J| "i 1, i ',• lili,' l»K 1V' , ' ,' " ,. '' i ,
the half-life predicted by laboratory experiments using a water/acetonitrile solution). The
•,',„; , , Hi, '"-, ,, nilii ' • " ;,,' ',,i , i ' • ".,, I*, / ' •„ Min'i,, , 'i1!'11'.!.,:!!' , „ t V "'•: '" '•• .••!",! ' • •• 'r i .".I'i'.•"'i4,:"'i A, '• n , . I '• •
authors attributed this significant difference in photolysis rates to the light
screening/quenching effects of dissolved organic matter.
Friesen etal. (1990) examined the photolytic behavior of 1,2,3,4,7-PeCDD and
1,2',3,4,6,7,8-HpCbp In watenacetonitrile (2:3, v/v) and in pond water under sunlight at 50
degrees north latitude. The observed half-lives of these two compounds in the
watenacetonitrile solution were 12 and 37 days, respectively, but much shorter in pond
water, 0.94 and 2.5 days, respectively. Similarly, Friesen et al. (1993) studied the
phptodegradation of 2,3,7,8-TCDF and 2,3{4,7,8-PeCDF by sunlight using
water:acej;oi3itri|e;|2:3, v/y) and lake water. The obseryed half-liyes of the 2,3,7,8-TCDF
and 2,3,4,7,8-PeCDF in the watenacetonitrile solution were 6.5 and 46 days, respectively,
iiFII" •'• I i I I i • i , . ' .
and 1.2 and 0.19 days in lake water, respectively. The significant differences between the
n^iy^' water and watenacetonitrile solution results were attributed to indirect or sensitized
photolysis due to the presence of naturally occurring components in the lake and pond
water.
:i-':ll '" nil i . " ' il1' ' ' ;' ' i .'
Dung and p'Keefe (1992), in an investigation of aqueous photolysis of 2,3,7,8-
TCDF and 1,2,7,8-TCDF, reported findings similar to those of Friesen et al. (1993). The
Photolysis rates of .the two TCDF congeners observed in the river and lake water (half-lives
of about 4 to 6 hours) were double the rates observed in pure water (half-lives of about 8
"'ilpy,, i,1 , ",, • ,„, •• , WIl'i , ', ' " ,,'i ,„ ;,,'„ ' : ."Jl1 ,: ? ',, ';, 'iri11",1'; !,'•''"":•: •,!'.' !\i",\,ii«1', '»i."i''i', „'•»;,. r1- '"'.I ":"'', • "'M!1'",, i, :: , • r . "' - i
to11 hours). Dung and O'Keefe (1992) attribute the difference in rates to the presence of
N | |i • • , I'.n ,., • H'H'iN"1!! '''" ' i 'I •' ,i"p • •„ " ' ji1 , vii'l" '! i .; I1,, .i M I1'i, JiM',,"1, ""',,1'1' ..,,'i"|i ',,,'» ,,•!,!»: :„'',„ ,"',„, ,;':!,
natural organics in the river and lake water that may be acting as sensitizers. .
10,2.2 ' ."Photolysis on Soil ""' ....•-. > .
Photolysis of CDD/CDFs on soil has not been well characterized. Based on the data
generated to date, however, photolysis is an operative degradation process only in the near-
surface soil where UV light penetrates (i.e., the top few millimeters or less of soil), and
',::!": , .: . i . ','M ,?, •: :• .,• tl fiis . ..' : -.•,•,•. .;"vi'e.(,!i: i-(| wv; '; \-t -i ,,i/m\-.t. ., « ,f\,r v ,-, i - • '
dechlorination of peri-substituted chlorines appears to occur preferentially.
Miller et al. (1989) studied the CDD degradation products resulting from irradiation
of 13C-labeled OCDD on two soil types using sunlamps. Approximately 38 to 42 percent of
the OCDD were degraded by day 5 of the experiment; no significant further loss of OCDD
10-4
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
was observed over the following 10 days. Although determined not to be the dominant
photolysis pathway, photodechlorination was observed in both soils; approximately 10 to
30 percent of the lower chlorinated congeners were produced from the immediate higher,
chlorinated congeners. The HpCDD and HxCDD congeners observed as degradation
products were present in approximately similar proportions to the number of congeners in
each congener group. However, Miller et al. (1989) found that 2,3,7,8-TCDD and
1,2,3,7,8-PeCDD were observed in greater yields than would be expected on the basis of
the number of potential TCDD and PeCDD congeners. One-fifth to one-third of the total
yield of PeCDDs was 1,2,3,7,8-PeCDD, and one-half of the total yield of TCDDs was
2,3,7,8-TCDD. .
Kieatiwong et al. {1990) performed similar experiments to those of Miller et al.
(1989) using natural sunlight rather than sunlamps for irradiation of 13C-labeled OCDD on
soils. Photodechlorination was estimated to account for approximately 10 percent of the
loss of OCDD. One-third to one-half of the total yield of PeCDDs was 1,2,3,7,8-PeCDD,
and one-half of the total yield of TCDDs was 2,3,7,8-TCDD. The findings of Miller et al.
(1989) and Kieatiwong et al. (1990) indicate that the 2,3,7,8-substituted TCDD and PeCDD
congeners were either preferentially formed or were phptochemically less reactive than the
other congeners that were formed.
Tysklind et al. (1992) studied the sunlight photolysis of OCDD on soil and reported
results in good agreement with those of Miller et al. (1989) and Kieatiwong et al. (1990).
Photodechlorination was observed with production of HpCDDs, HxCDDs, PeCDDs, and
TCDDs over the 16-day irradiation period. Photodechlorination at the peri-substituted
positions was the preferred photodechlorination mechanism; the proportions of 2,3,7,8-
substituted congeners present in the soils after 16 days for each congener group were as
follows: HxCDD - 65 percent; PeCDD - 40 percent; and TCDD - 75 percent. The sunlight
photolysis of OCDF on soil was also studied by Tysklind et al. (1992). Photodechlorination
was observed. However, unlike the case with OCDD, photodechlorination of the lateral-
substituted positions was found to be the dominant photodechlorination mechanism
resulting in a relative decreasing proportion of 2,3,7,8-substituted congeners during the
irradiation period. 2,3,7,8-TCDF was not observed in any of the irradiated samples.
10-5 April 1998,
-------
v DRAFT-DO NOT QUOTE OR CITE
10.2.3 Photolysis on Vegetation
Photolysis of CDD/CDFs sorbed on the surface of vegetation has not been well
ii;'•''••. ' , ., "', I'iii •:' ;•»•',' ',-.';, :• * '!'::«».'i •'..•', it,. 11 •.'. .:,-:, >: j.-.V1 ,• ,' • *••/''. ivi ' "=" ''.««'• "' ' 1 ;i
characterized, and the findings to date are somewhat contradictory. McCrady and Maggard
(1993) reported that 2,3,7,8-TCDD sorbed on the surface of reed canary grass (Phalaris
arundinacea L.) undergoes photolytic degradation with a half-life of 44 hours in natural
sunlight. In contrast, Welsch-Pausch et al. (1995) found little difference in the CDD/CDF
congener patterns between grass (Lolium multiflorum) grown on an outdoor plot and grass
grown in a greenhouse (i.e., UV-light transmission blocked). In an attempt to clarify this
contradiction, Welsch-Pausch and McLachlan (1995) studied the photodegradation of
CDD/CDFs on pasture grass (Arrhenatherion elatioris) during two growing cycles (summer
and autumn) using two greenhouses. One greenhouse was constructed of glass that
blocks UV transmission, and the other was constructed of plexiglass (4 mm) with an UV-
light transmission of greater than 50 percent in the 280-320 mm range. In both the
summer and.autumn exposure periods, the concentrations of CDD/CDFs (on a congener
,->! '..,• " ", ' , •'. sin, (•• .'/•.'.,' :;!:i ;.»• „;«:!?"; "• i's'.'1. ..,"iu t •!;..• •*.!''A » '•• :. .j .',•>•:' .;•• I
.i", ' . . - * .s-i'! ' ••:, . . ' ,.v •:, "• • ,"!-"/:, • "' , ..;::„'" I ',.'•. ( ."•„• i
10.2.4 Photolysis in Air
:,!,!,'„' ' ,';: ' , ' ' W\ !; .:•<• •• ," •& iV,' !. '-,;!'; :'::,: \ .'-. '-. " ',.:• > :•'• V 0' Vit!',;." . ,| -, . , • ,':
Photolysis of CDD/CDFs in the atmosphere has not been well-characterized. Based
on the data generated to date, however, photolysis appears to be a significant mechanism
for degradation (i.e., principally dechlorination of the peri-substituted chlorines) of those
CDD/CDFs present in the atmosphere in the gas phase. For airborne CDD/CDFs sorbed to
particulates, photolysis appears to proceed very slowly, if at all. Because of the low
W-> ' ' "•.'••:". :» ';Si ''," ''• ';.; ./".:' !;":; ,'! "!'! '"'"' >."f. ; i,^, ;'!•' ",' •;'i'.w''." ^-"•',•{ '.'• '• < ,:".•.'."• ' ;l', , '' .
volatility of CDD/CDFs, few studies have been gttempted to measure actual rates of
photodegradation of gaseous-phase CDD/CDF, and only recently studies have examined the
relative importance of^photolysis to particulate-bound^CDD/CDFs.
,,, '• ,„ ' , ," ' 'i11''!1"!"!,!,! " :•' • • " ,;:i',' , ". • iS! " " I I J« "'',',,
Sivils et al. (1994; 1995) studied the gas phase photolysis of several CDDs (2,3,7-
: i: . '.. ": " iiiis . . ' ,'r • :. '>• ',:. ;: ' "' i ' i ' ' '.' '•! • • •
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
,,' ll', : jjeii. • ' i •. ' ;,,' ^ >i • .,;.. II I ''',!. ' '
irradiating the effluent from a gas chromatograph with broadband radiation in the UV/visible
region for periods of time up to 20 minutes. The irradiated sample was then introduced
1 , -Hi; '.i , , • • : ••• .V"." ;.:: ••.':" -, '.••. iV.r'V " •'•,'V:: ' .• ••: i
10-6 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
into a second gas chromatograph to measure the extent of dechlorination. The results
showed that degradation followed first order kinetics and that an inverse relationship exists
between the degree of chlorination and the rate of disappearance. Although the lack of
photoproducts prevented an independent confirmation of the preferential loss mechanism,
the results indicated that laterally-substituted congeners (i.e., .chlorines at the 2,3, 7, and
8 positions) degrade at a slower rate than the peri-substituted congeners (i.e., chlorines at
the 1, 4, 6, and 9 positions). Although the rate constants were not presented in Sivils et
al. (1994), the degradation rate for 2,3,7,8-TCDD (30 percent loss in 20 minutes) was
reported to be slower than the rates for all other tested CDDs. Also, 1,2,4,7,8-PeCDD
(with 2 peri-chlorines) degraded significantly faster than 1,2,3,7,8-PeCDD (with only 1 peri-
chlorine).
The photolysis of 2,3,7,8-TCDD sorbed onto small diameter fly ash particulates
suspended in air was studied by Mill et al. (1987). The results indicated that fly ash
appears to confer photostability on 2,3,7,8-TCDD. Little (8 percent) to no loss was
observed on the two fly ash samples after 40 hours of illumination. Similar results were in
photolysis studies with fly ash reported by Tysklind and Rappe (1991) and Koester and
Hites (1992). Tysklind and Rappe (1991) subjected fly ashes from two German
incinerators under various simulated environmental conditions. The fraction of
photolytically degradable CDD/CDF after 288 hours of exposure was in the range of 20 to
40 percent of the extractable CDD/CDF. However, a 10 to 20 percent reduction was also
observed in the darkened control samples. With the exception of HpCDD and HpCDF, the
concentration of all other congener groups either increased or stayed the same during the
• . • '
exposure period from hour 144 to hour 288. Koester and Hites (1992) studied the
photodegradation of CDD/CDFs naturally adsorbed to five fly ashes collected from
electrostatic precipitators. No significant degradation was observed in 11 photodegradation
experiments performed on the ashes for periods ranging from 2 to 6 days. Koester and
Hites (1992) concluded that: (1) the absence of photodegradation was not due to the
absence of a hydrogen-donor organic substance; (2) other molecules or the ash, as
determined by a photolysis experiment with an ash extract, inhibit photodegradation either
by absorbing light and dissipating energy or by quenching the excited states of the
CDD/CDFs; and (3) the surface ,of the ash itself may hinder photolysis by shielding the
CDD/CDFs from light.
10-7
April 1998
-------
-------
DRAFT-DO NOT QUOTE OR CITE
11. SOURCES OF DIOXIN-LIKE PCBs
t
The purpose of this chapter is twofold: (1) to identify sources that release dioxin-
like polychlorinated biphenyls {PCB) congeners into the environment and (2) to derive
national estimates for releases from these sources in the United States. PCBs have been
found in all media and all parts of the world. PCBs were produced in relatively large
quantities for use in commercial products such as dielectrics, hydraulic fluids, plastics, and
paints. They are no longer commercially produced in the United States, but continue to be
released to the environment through the use and disposal of these products. PCBs may
also be inadvertently produced as by-products during the manufacture of certain organic
chemicals and also as products of the incomplete combustion of some waste materials.
11.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY
Tables 11-1 and 1.1-2 present emission estimates for the major known or suspected
sources that could release dioxin-like PCBs to the environment. Table 11-1 presents
estimated annual releases for the time period 1990 to 1995. Table 11-2 presents
estimated annual releases for the time period 1985 to 1989. For each source listed in
Tables 11-1 and 11-2, estimated emissions to air, water, land, and product are listed where
appropriate and where data are adequate to enable an estimate to be made. The term
"product" in Tables 11-1 and 11-2 is defined to include substances or articles (e.g., sewage
sludge that is distributed/marketed commercially) that are known to contain dioxin-like
PCBs and whose subsequent use may result in releases to the environment.
Releases of "old" dioxin-like PCBs (i.e., dioxin-like PCBs manufactured prior to the
ban) to the environment can occur from ongoing use and disposal practices. Prior to
regulations enacted beginning in the late 1970s that limited the manufacture/use/disposal
of PCBs, significant quantities of PCBs were released to the environment in association
with: {1) the manufacture of PCBs; (2) the manufacture of products containing PCBs; and
(3) the use and disposal of products containing PCBs, as well as materials that may have
been contaminated with trace levels of PCBs from prior PCB use or disposal. Following the
ban on PCB production, releases from these first two categories ceased to exist. The third
type of releases, those associated with product use and disposal, will continue in at least
three ways: • • > . .
11-1
April 1998
-------
, PRAFT-PP NOT QUOTE OR CITE
• Products containing greater than 2 pounds of PCBs (e.g., dielectric fluids in
transformers and large capacitors) are controlled by disposal regulations that have
minimized environmental releases;
• Disposal of products containing small quantities of PCBs (e.g., small capacitors,
fluorescent lighting fixtures) or trace quantities of PCBs (e.g., wastepapers) are
subject to disposal as municipal solid waste but may result in some release to the
general environment;
•... Leaks and spills of still in-service PCBs; and
• Illegal disposal of PCBs.
Although no estimates of emissions of "old" dioxin-like PCBs from reservoir sources
(i.e., soils and sediments) have been made, the widespread occurrence of PCBs is most
likely due to the re-release of these compounds from reservoir sources. Sediments act as a
reservoir whereby dioxin-like PCBs can become resuspended in the water column and
volatilize from the water body into the atmosphere. Soils act as a reservoir accumulating
dioxin-like PCBs from aerial deposition and then reintroducing them to the atmosphere
':'".• • ' > : '' ?il»-i, " . " ' ''"' .'I; '"I|IJ! s ." ''•'••'•I, ; ' |'."'rl V "'"'i1'1",11 "t.',;"'" 'P','••', •<••.•
through windblown soil or as vapors. It is reasonable to assume that the quantities of
dioxin-like PCBs available for, release from reservoir sources are significantly larger than the
quantities of dioxin-like PCBs available for release from current use and disposal of dioxin-
like PCB-containing material.
Insufficient information is currently available to enable a determination as to whether
,('•>,: .if1 ',,"" ,'.' ' i ' ie'iiiii .. ", >.'..'',t:i -,. 'if •,' >; ' ••'," - i1,'',,ri,,, ij .„(•,' :* v ;:« li-r'if "in;!'",:,' i:<. nxii ,' 'S MI,;, ';•,.', "i, i , ,\ ( . ' :
arty significant release of newly formed dioxin-like PCBs is occurring in the United States.
Unlike CDD/CDFs, PCBs were intentionally manufactured in the United States in large
quantities from 1929 until production was banned in 1977. Although -no strong evidence
exists that the dioxin-like PCBs are produced in other than trace quantities as byproducts
'i ' ,lf I' . '" '"!, " ll'lif't'i ','.." II 'nil"1,,
during combustion or chemical processes, most research on formation of dioxin-like
compounds has, to date, focused on CDD/CDFs rather than PCBs. Thus, there are
>; •;• .: • - ! m : ' '••.-.••* , > ' ' > ' i ,'! ,n ;, .;|. • •, ••
currently insufficient empirical data upon which to estimate emission factors for any
potential source category. Congener-specific measurements in discharges from potential
sources are needed.
11-2 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
-' , * . v -
11.2 RELEASES OF COMMERCIAL PCBs
PCBs were commercially manufactured by the direct batch chlorination of molten
biphenyl with anhydrous chlorine in the presence of a catalyst, followed by separation and
purification of the desired chlorinated biphenyl fractions. The degree of chlorination was
controlled by the chlorine contact time in the reactor. Commercial PCBs production is
believed to have been confined to 10 countries. Total PCBs produced worldwide since
< - •
1929 (i.e., the first year ,of known production) has been estimated to total 1.5-million
metric tons. Initially, PCBs were primarily used as dielectric fluids in transformers. After
World War II, PCBs found steadily increasing use as dielectric fluids in capacitors, as heat-
conducting fluids in heat exchangers, and as heat-resistant hydraulic fluids in mining
equipment and vacuum pumps. PCBs also were used in a variety of "open" applications
(i.e, uses from which PCBs cannot be recollected) including: plasticizers, carbonless copy
paper, lubricants, inks, laminating agents, impregnating agents, paints, adhesives, waxes,
additives in cement and plaster, casting agents, dedusting agents, sealing liquids, fire
retardants, immersion oils, and pesticides (DeVoogt and Brinkman, 1989).
PCBs were manufactured in the United States from 1929 until 1977. U.S.
production peaked in 1970 with a volume of 39,000 metric tons. In 1971, Monsanto
Corporation, the major U.S. producer, voluntarily restricted the sales of PCBs to all
applications with the exception of "closed electrical systems," and annual production fell to
18,000 metric tons in 1974. Monsanto ceased PCB manufacture in mid-1977 and shipped
the last inventory in October 1977. Regulations issued by EPA beginning in 1977,
principally under the Toxic Substances Control Act (TSCA) (40 CFR 761), have strictly
limited the production, import, use, and disposal of PCBs. The estimated cumulative
production and consumption volumes of PCBs in the United States from 1930 to 1975
were: 635,000 metric tons produced; 1,400 metric tons imported (primarily from Japan,
Italy, and France); 568,000 metric tons sold in the United States; and 68,000 metric tons
exported {Versar, 1976). The reliability of these values is +5 percent and -20 percent
{Versar, 1976).
Monsanto Corporation marketed technical grade mixtures of PCBs primarily under
the trade name ArocJor. The Aroclors are identified by a four-digit numbering code in which
the last two digits indicate the chlorine content by weight percent. The exception to this
coding scheme is Aroclor 1016, which contains only mono- through hexa-chlorinated
11-3 . April 1998
-------
- DRAFT-DO NOT QUOTE OR CITE
congeners with an average chlorine content of 41 percent. From 1957 until 1972,
Monsanto also manufactured several blends of PCBs and polychlorinated terphenyls (PCTs)
under the trade names Aroclor 2565 and Aroclor 4465; manufacture and sales volumes are
,][" '" "' , "i;,"1, '„ , "" "" , ' „" ' ' i',1, Jl1 ~~ , i j , , -" ,'. i '*f"', , ' \
not available for these blends. Listed below are the percentages of total Aroclor production
during the years 1957 to 1977 by Aroclor mixture as reported by Brown (1994).
::;/ .'. . ... , ' •;,,•; .'.'., . ."•;;; "! .' ' 1957-1977 ' '. j
U.S. Production
Aroclor ..(%)
1016 " " l"2.8g ,
1221 0.96
1232 0.24
V'i :.: • - i'f! 1242 , , P1'76 . '.
;" :" '':/" !::i 1248 ' " "6.76""""'
.::; '.. --. •'• ;;:;.•• 1254 ; ".' .." , "".15.73'"". "_i
1260 10.61
:-t • • •;• •• i't1 ,',126(2.. ;; , .. '.:.; ,', p.83
. ••: :, ' : , ' !'i; : 1268, ..';', _ i . " '''" 0.33 .. ;'
.:• •; ,a;i '•;' ,• •.• . •; i >'•.. ::' .-,.••, ;.• :. •• ,; >• .,\\~: .•!•'.;,••'., •: \'.-. - ,f . >' ••'.'!
The trade names of the major commercial PCB technical grade mixtures
manufactured in other countries included: Clophen (Germany), Fenclor and Apirolio (Italy),
i' '•',. "•• i.' i n '•'!•..,
Kanechlor (Japan), Phenoclor and Pyralene (France), Sovtel (USSR), Delor and Delorene
, "J ' " , '" ' I',, , " ' , ' '' - ' ' . , " ' '
(Czechoslovakia), and Orophene (German Democratic Republic) (DeVoogt and Brinkman,
1§89). The mixtures marketed under these trade names had similar chlorine content (by
weight percent and average number of chlorines per molecule) to those of various Aroclors.
Listed below are comparable mixtures in terms of chlorine content marketed under several
trade names.
Aroclor Clophen Pyralene Phenoclor Fenclor Kanechlor
1232 2000 200
1242 '"'"' A-30:'"" ''""."36bS' "••'"'•'^.-3•••'••' •"'"•42 " ' " 300
1248 A-40 DP-4 400
1254 A-50 DP-5 54 50°
1260 A-60 DP-6 64 600
Major advances in analytical separation and resolution techniques during the 1980s
and 1990s enabled various researchers to identify and quantify ,PCB congeners present in
Aroclors, Clophens, and Kanechlors (Albro and Parker, 1979; Huckins et al., 1980; Albro et
al., 1981; Duinke'f" and Hillebrand, 1983; Kannan et al.7 1§87; fanabe et al., 1987; Duinker
11-4 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
et a!., 1988; Schulz et al., 1989; Himberg and Sippola, 1990; Larsen et al., 1992; deBoer
et al., 1993; and Schwartz et al., 1993). Schulz et al. (1989) were the first to identify and
quantify all PCB congeners present in a series of Aroclors and Clophens. Frame (1995)
reported preliminary results of a nearly completed round robin study, one goal of which was
to determine the distribution of all PCB congeners above 0.05 weight percent in various
Aroclors (1221, 1016, 1242, 1260, and 1262) using 18 state-of-the-art gas
chromatography/mass spectrometry (GC-MS) or electron capture detector (GC-ECD)
systems.
Table 11-3 presents mean summary statistics on the concentrations of the dioxin-
like PCBs in each mixture group (i.e., Aroclor 1248, Clbphen A-40, and Kanechlor 400
comprise one mixture group) reported by these researchers. Table 11 -3 also presents
calculation of the corresponding mean TEQ concentration of each congener in each mixture
group as well as the total mean TEQ concentration in the mixture group. For each mixture
group, the congeners detected were generally similar. There was, however, wide variability
in the concentrations reported by some researchers for some congeners. Brown et al.
(1995) compiled similar statistics using a somewhat different set of studies and derived
significantly lower mean concentrations of some congeners in several Aroclors. Frame
(1995) and Larsen (1995) attribute such differences either to potential limitations in the GC
columns used by various researchers to separate similar eluting congeners or to actual
differences in the congener concentrations in the Aroclor, Clophen, and Kanechlor lots
analyzed by various research groups. Because of the wide variability in the reported
results, the uncertainty associated with the mean concentrations reported in Table 11 -3 is .
very large. '
In the environment, PCBs also occur as mixtures of congeners, but their composition
will differ from the commercial mixtures. This is because after release to the environment,
the composition of PCB mixtures changes over time, through partitioning, chemical
transformation, and preferential bioaccumulation (U.S. EPA, 1996g). Dioxin-like PCB
congeners differ by up to one to two orders of magnitude in their water solubilities, vapor
pressures, Kow values, and Henry's Law constants. Thus, although all the dioxin-like PCB
congeners are poorly soluble in water and have very low vapor pressures, they will
/ • - ' - " • '
volatilize and leach at different rates. Similarly, because the congeners differ somewhat in
their rates of biodegradation, bioaccumulation, and photodegradation, the congener
' *
11-5 April 1998
-------
',' DRAFT-DO NOT QUOTE OR CITE
patterns found in environmental media and biota will vary from those found in commercial
mixtures.
Although environmental mixtures are often characterized in terms of Aroclors, this
characterization can be both imprecise and inappropriate. Qualitative and quantitative
erfofs can arise from judgements in comparing GC/MS peaks for a sample with the
characteristic peak patterns for different Aroclors, particularly for environmentally altered
patterns {U.S. EPA, 1996g). For the same reason, it can be both imprecise and
:'':,•'.' • ...'•.'•,,:. m I;1 /••';. '..?:•• ':•&, ::-\! •,>"',•:''j;iii;lh;iJ1Vii:!':i:'>.)J>l.i'ii!w. ;•"'.** i« "i 'fl ;v '•• •: ' •• •
inappropriate to infer concentrations of dioxin-like PCB congeners in an environmental
sample based on characterization of the sample's Aroclor content and knowledge of the
dioxin-like congener content in the commercial Aroclor. Safe (1994) wrote, "Regulatory
agencies and environmental scientists have recognized that the composition of PCBs in
most environmental extracts does not resemble the compositions of the commercial
product." Similarly, ATSDR (1993) stated, "It is important to recognize that the PCBs to
which people may be exposed are likely to be different from the original PCB source
because of changes in congener and impurity composition resulting from differential
'i,,:11 . ,, •" •'•':, '"'"I'll"1! I'1 ' / "'", " " ' '".jjiv ',,; ii;"'1 • , ,"" 'i..!,1:',",1"1 ".;!'. "', 'i'11,,«, !• \« ,f'"f«^ ' 'i • .;••"!, ''si,',"'"1!;1""1!1. '"< • •• i!"!:1^1"1!'/111' •• '• '•
partitioning and transformation in the environment and differential metabolism and
retention."
11.2.1. Approved PCB Disposal/Destruction Methods
In 197P/ EPA began regulating the disposal of PCBs and PCB-contaminated waste
under the TSCA, PL 94-469. The disposal regulations^ publishedI in the Code of Federal
Regulations, 40 CFR, Part 761, state that the preferred disposal method is incineration at
1,200°C or higher. If the waste contains material that can not be destroyed by
incineration, EPA clearance must be obtained to dispose of the waste in a chemical waste
landfill, or in another approved manner.
The PCB disposal regulations describe disposal of three distinct types of PCB waste:
PCBs, PCB articles (i.e., items containing PCBs), and PCB containers. Within these
categories of PCB waste, further distinctions are made based on the PCB concentration in
the waste. The acceptable disposal methods are based on the PCB concentrations in the
specific waste to be destroyed. The acceptable disposal methods are: Annex I
incinerators, high-efficiency boilers, Annex II chemical waste landfills, and other approved
methods. The foljowing subsections and Table .11 -4 provide brief descriptions of these
11-6
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
disposal methods. More complete descriptions of the specific methodologies are provided
in the Code of Federal Regulations, 40 CFR, Part 761.
Approved Incinerators/High Efficiency Boilers - PCB Annex I incinerators must meet
the specific technical standards and criteria listed in Annex I of EPA's PCB regulations. The
minimum operating requirements for disposal of liquid wastes are 2 seconds at 1,200°C
(2,190°F) with 3 percent excess oxygen (measured in the stack gas), or 1.5 seconds at
1,600°C (2,910°F) and 2 percent excess oxygen (measured in the stack gas). Monitoring
requirements, approval conditions, and trial burn requirements are prescribed in Annex I,
Commercial or industrial incinerators intending to destroy liquid PCB wastes must
demonstrate compliance with the Annex I requirements through a comprehensive trial burn
program. Annex I incinerators operating at optimum performance level should destroy
' 99.997 percent of liquid PCB waste with a resulting maximum emission factor of 0.03
grams per kilogram (g/kg).
Criteria for Annex I incinerators were established for the destruction of liquid PCB
wastes; however, these incinerators also may be used for disposal of nonKquid PCB items
(such as capacitors), provided that a destruction and removal efficiency of 99.9999 percent
and a maximum emission factor of 0.001 g/kg are met.
High-efficiency boilers may be used to destroy PCBs and PCB-contaminated waste
with PCB concentrations not exceeding 500 ppm. Conventional industrial and utility boilers
may be designated as high-efficiency boilers, if they are operated under the prescribed
combustion conditions defined in the PCB disposal regulations. The PCB regulations do not
specify a minimum PCB destruction efficiency for high-efficiency boilers; however, EPA-
approved boilers operated according to the regulations have reported destruction
efficiencies in excess of 99.9 percent, with a corresponding emission factor of 0.1 g/kg
(U.S. EPA, 1987c).
Approved Chemical Waste Landfills - Approved chemical waste landfills can be used
for the disposal of some, but not all, PCB wastes. PCB-contaminated materials acceptable
for land disposal in an approved landfill include PCB mixtures (e.g., certain PCB-
contaminated soil/solid debris, PCB-contaminated dredged materials, and PCB-contaminated
municipal sewage sludge), PCB articles that cannot feasibly be incinerated (e.g., drained
and flushed transformers), and drained PCB containers. EPA must issue written approval to
landfill PCB articles other than transformers. PCB-contaminated materials not acceptable
,11-7 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
for land disposal in an approved landfill include nonliquid PCB mixtures in the form of
contaminated soil; rags, or other solid debris, and sealed capacitors. Typically, PCBs
disposed in these landfills are placed in sealed containers, thereby, minimizing any PCB
emissions. ^ i : _ •
Other Approved Disposal Methods - Other thermal and nonthermal destruction
techniques may be approved by EPA Regional Administrators, if these processes can effect
destruction of PCBs equivalent to that of incinerators or boilers. Subsequent to April 29,
1983, all other PCB disposal technologies (thermal and nonthermal) that are to be used in
more than one EPA Region must be approved by EPA Headquarters. Examples of thermal
technologies approved for commercial-scale use or for research and development projects
include a pyrolysis process to treat contaminated soils, a fluid wall reactor, a cement kiln, a
diesel engine, a steam-stripping operation, an aluminum melting furnace, and a molten salt
process. Examples of approved nonthermal processes include chemical dechlorination
processes, physical/chemical extraction techniques, and biological reduction methods. The
physical/chemical techniques extract the PCBs from transformers or capacitors and
concentrate them for disposal; they do not destroy the PCBs.
Emission Estimates - Table 11-5 lists the amounts of PCBs reported in EPA's Toxics
Release Inventory (TRI) as transferred pffsite for treatment, energy recovery, or disposal
during the years 1988 through 1993. These quantities do not necessarily represent entry
of PCBs into the environment. If it is assumed that ail transferred PCBs are incinerated in
high-efficiency boilers with a destruction and removal efficiency of 99.99 percent, then
annual emissions of PCBs to air during 1988 and 1993 could have been as high as 2(3,422
kg and 4,635 kg, respectively. Because no stack testing data are available for dioxin-like
PCBs, it is not possible to estimate what fraction of these potential PCB releases would
have been the dioxin like congeners.
11.2.2. Accidental Releases of In-Service PCBs
i1' i !'" '" '. Ill "I I II I I I II r • •
I I ill i :
EPA banned. PCB production and use in open systems in 1977. Subsequent to the
1977 ban, releases of cpmmercjajiy produced PCB to the environment (aside from minimal
"'"',!' ] ' i i i I II II I I III I I I II I I •
releases occurring during approved disposal and/or destruction) have been limited to .
accidental release of in-service PCBs (U.S. EPA, 1987c). Accidental releases are the result
:- "' •' '•', • Ill II I | I II I I Ill 11 I - . . .
of leaks or spills during failure/breakage of an existing piece of PCB-containing equipment,
;, ' ' I ' I 1 II " '
,. II '
11-8 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE '
or incomplete combustion occurring during accidental fires involving PCB-cbntaining
equipment. These two types of accidental releases are discussed in this section.
Leaks and Spiffs - PCBs that remain in active service at this time are those contained
in "closed system" (i.e., those pieces, of electrical equipment that completely enclose the
PCBs and do not provide direct atmospheric access of the PCBs during normal use). This
equipment includes PCB transformers, capacitors, voltage regulators, circuit breakers, and
reclosures. With the exception of PCB transformers and probably small PCB capacitors, the
majority of the PCB-containing electrical equipment in-service during 1981 was owned by
the electrical utility industry. Approximately 70 percent of the estimated 140,000 PCB
transformers in-service in 1981 were owned by nonutilities. No information was available
on the relative distribution of small PCB capacitors (Versar, 1988).
The number of each of these items owned by the utility industry, the quantity of
PCBs each contains, and an estimate of the annual quantity of PCBs leaked and/or spilled
were investigated by the Edison Electric Institute and the Utility Solid Wastes Activity
Group (EEI/USWAG) for EPA in 1981. The findings of this investigation were reported in
the April 22, 1982, Federal Register relative to a proposed modification to the PCB
regulations (Federal Register, 1f982a). The findings indicated that over 99 percent of the
total quantity of PCBs contained in utility-owned electrical equipment in 1981 (73,700
metric tons) were in 40,000 PCB transformers (those containing > 500 ppm of PCBs) and
large PCB capacitors (those containing > 3 Ibs of PCBs). An upper bound estimate of the
mass of PCBs that leached or spilled from this equipment in 1981 was 177 metric tons.
Approximately 95 percent of the estimated releases were the result of leaks from large PCB
capacitors (Federal Register, 1982a). Leaks/spills typically occur in transformers when the
gasket joining the top to the body corrodes, tears, or physically fails. PCBs can then leak
past this failed section and potentially spill onto the surrounding ground. PCB capacitors
typically fail by rupturing, exposing the contained PCBs to the environment. Failure is
caused by environmental and weathering effects (e.g., lightning) or material'failures (e.g.,
metal fatigue).
As of mid-1988, the total population of in-service PCB transformers and large PCB
capacitors was estimated to have decreased from 140,000 to 110,000 and from 3.3
million to 1.9 million, respectively (Versar, 1988). PCB transformers have normal operating
lifetimes of 30 years: and 40 years, respectively. The accelerated retirement rate over this
11-9
April 1998
-------
DRAFT-DO JSTOT QUOTE OR CITE
7-year time period was attributed to EPA's PCB Electrical Use Rule (Federal Register,
1982b), which required the removal of 950 food/feed industry transformers by 1985 and
removal of 1.1 -million unrestricted-access large PCB capacitors by October 1 988. In
addition, EPA's PCB Transformer Fires Rule (Federal Register, 1985b) required the removal
by 1990 of 7,600 480-volt network transformers. More recent inventories of PCB-
;,. • ' ii"!!!1'1 !. -';.;:,. yi ':' iSiii ' .•• •:'•"' ' /jji ,'i1 ,•!>,! ;*,/:•'•• ,»."JAi ['' "' rWi1 / • ' i.,1 '.\ ::',. 'i'.jf™^1, • . !•• • '• :•
'containing electrical equipment are not available. However, a recent Information Collection
Request submitted by EPA to the Office of Management and Budget for information on
uses, locations, and conditions of PCB electrical equipment estimated that there may be
150,000 owners of PCB-containing transformers used in industry, utilities, government
buildings, and private buildings (Federal Register, 1997a). It is expected (and is
demonstrated by the reported PCB transfers in TRI - See Table 11-5) that many owners of
PCB electrical equipment have removed PCB-containing equipment to eliminate potential
liability.
The proportion of spilled PCB that enters the atmosphere, runs off to surface water,
,, i«i .; \ •:. f /"Sill! „•,', ",:«,!' «:: • ;, |,'i -.:,! ffci, . ,<(' ., •• ; i," <; VI >'• "!••• •:'' ; iii, '!'•.•'. 'I ' • •
or remains in or on the surface depends on a variety of factors including the porosity of the
I , .»'!!llf .i : T , il'-; Hi , '"" I, 'i :'i| ">' i' » • JV " M' ' I'1-'.)'! , ', „ ij,,,,'!,,, - „, r '!! •"! ~ '
surface onto which the PCBs are spilled (concrete, soil), the PCB isomers that are spilled,
$ . ", ,'< ••' f'lfi i •'•: • ;<:< •", •:!;.,' ( v. i. ::;; •.s'ji.;;,: <••*•• "-i: •• :'i:<' i1.1*. ''A&M' •"••• 'i
ambient conditions (i.e., temperature, wind speed, precipitation), and the cleanup schedule.
The number and diversity of factors affecting PCB emissions from spills and leaks make
estimation of an emission factor difficult. A rough approximation of the annual amount that
may be released to the environment from spills and leaks can be made using the release
data reported by manufacturing facilities to EPA's TRI. Table 11-6 lists the amounts of
PCBs reported in TRI to be released to the environment during 1988 through 1993. These
data include emissions to the air, discharges to bodies of water, releases at the facility to
land, as well as contained disposal into underground injection wells.
Based on these TRI data, annual emissions of PCBs to air during 1988 and 1993
could be as high as 2.7 kg and 0 kg, respectively. For purposes of deriving a preliminary
rough estimate of potential releases of dioxin-like PCBs, it can be assumed that the ratio of
TEQ to total PCB in the air emissions was 84:1-million (i.e., the average of the estimated
mean TEQ contents for Aroclors 1242 and 1254 presented in Table 11 -3). Based on this
assumption, annual emissions of PCB TEQs in 1988 and 1993 could have been 0.2 and 0
grams, respectively. Similar assumptions for releases to water listed in Table 11-6 yield
estimated TEQ emissions during 1988 and 1993 of 0.4 and 0 grams, respectively. For
11-10 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
land, estimated TEQ emissions during 1988 and 1993 could have been 29 and 10 grams,
respectively. .
Accidental Fires - The available information is not adequate to support an estimate
of potential annual releases of dioxin-like PCBs from accidental electrical equipment fires.
For fires involving PCB transformers or capacitors, the amount of PCBs released is
dependent upon the extensiveness of the fire and the speed at which it is extinguished. A
number of these fires are documented. A New York fire, involving 200 gallons of
transformer fluid containing some 65 percent by weight PCBs, resulted in a release of up to
1,300 pounds of PCBs. A capacitor fire that burned uncontrolled for 2 hours in Sweden
resulted in the destruction of 12 large utility capacitors containing an estimated 25 pounds
of PCBs each, for a total potential release of 300 pounds. However, data are incomplete
on the exact amount of PCBs released as a result of these two fires.
EPA has imposed reporting requirements to ensure that the National Response
Center is informed immediately of fires involving PCB transformers (40 CFR 761). The
reeordkeeping requirements are used to document the use, location, and condition of PCB
equipment. Responses are mandatory, but may be claimed by the submitter to be
confidential information. The annual number of, PCB transformer fires is estimated at
approximately 20 per year; the number of PCB capacitor fires is unknown (U,S. EPA,
1987c). As these PCB items reach the end of their useful lives and are retired, their
susceptibility to fires will be eliminated, and the overall number of PCB transformer and
capacitor fires will be reduced.
11.2.3, Municipal Wastewater Treatment
EPA conducted the National Sewage Sludge Survey in 1988 and 1989 to obtain
national data on sewage sludge quality and management. As part of this survey, EPA
analyzed sludges from 175 publicly owned treatment works (POTWs) that employed at
least secondary wastewater treatment for more than 400 analytes including 7 of the
Aroclors. Sludges from 19 percent of the POTWs had detectable levels of at least one of
the following Aroclors: 1248, 1254, or 1260; none of the other Aroclors were detected in
any sample (detection limit was typipally about 200-yug/kg dry weight) (U.S. EPA, 1996a).
Analyses were not performed for dioxin-like PCB congeners. The Aroclor-^specific results of
the survey are presented in Table 11-7. Gutenmann et-al. (1994) reported similar results in
' . 11-11 April 1998
-------
;. DRAFT-DO NOT QUOTE OR CITE
a survey of sludges from 16 large U.S. cities for Aroclor 1260 content. At a detection limit
of 250-/zg/kg (dry weight), GutenmannetaL (1994) detected Arpdpr 1260 at only one
facility (4,600 /^g/kg). These results indicate that PCBs are not likely to be formed at
POTWs, but rather are present because of disposal of PCB products or recirculation of
previously disposed PCB.
Although PCBs, measured as Aroclors, were not commonly detected in sewage
sludge at/zg/kg levels by U.S. EPA (1996a) and Gutenmann et al. (1994), the presence of
dioxin-Iike PCB congeners at lower concentrations may be more common. Green et al.
(1995) and Cramer et al. (1995) reported the results of analyses of 99 samples of sewage
slydge for PCB congener numbers 77, 126, and 169. The sludge samples were collected
from 75 wastewater treatment plants across the United States during the summer of 1994.
These data are summarized in Table 1.1-8. For the calculation p| results in units of TEQ,
results from all samples collected from the same facility were averaged by Green et al.
(1995) to ensure that results were not biased towards the concentrations found at facilities
from which more than one sample were collected. If all nondetected values are assumed to
be zero, then the POTW mean and median dioxin-Iike PCB TEQ concentrations were 47.5-
Ili,:1" 'i" Jv; 'i11'" iSis;" , • ': -.,'»,",-'",,!':;» i •,•» »»•;:•/'. n ."Vi .>* :iiiK!r i . •»• i.iji|:,( ,ia,,,. . •• .•
and 22.6-ng TEQ/icg (dry weight basis), respectively (standard deviation of 89.4-ng
TEQ/kg). If the nondetected values are set equal to the detection limits, then the POTW
mean and median TEQ concentrations were 48.1- and 23.9-ng TEQ/kg, respectively
(standard deviation of 89.2-ng TEQ/kg).
Approximately 5.4-million dry metric tons of sewage sludge are estimated by EPA to
be generated annually in the United States based on the results of the 1988/1989 EPA
National Sewage Sludge Survey (Federal'Register, 1993b). Table 11-9 lists the volume of
sludge disposed annually by use and disposal practices. Table 11 -9 also lists the estimated
amount of dipxin:like PCB TEQs that may be present in sewage sludge and potentially be
released to the environment. These values were estimated using the mean/median (i.e.,
about 48-ng TEQJk'g) TEQ concentration reported by Green et a\. (1995) and Cramer et al.
(1995). Multiplying this TEQ concentration by the sludge.volumes generated, yields an
annual potential total release of 200 g of TEQ for nonincinerated sludges. Of this 200 g of
TEQ, 3.4 grams enter commerce as a product for distribution and marketing. The
reminder is applied to land (101.3 grams) or is landfilled (94.8 grams).
11-12 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
These release estimates are assigned a H/M confidence rating indicating "high"
confidence in the production estimate and "medium" confidence in the emission factor
estimates. The "medium" rating was based on the judgement that, although the 75
facilities tested by Green et al. (1995) and Cramer et al. (1995) may be reasonably
representative of the variability in POTW technologies and sewage characteristics
nationwide, the sample size was still relatively small, and not all dioxin-like PCB congeners
were monitored. Based on this confidence rating, the estimated range of potential annual
emissions is assumed to vary by a factor of 5 between the low and high ends of the range.
Assuming that the best estimate of annual emission to land (101-g TEQ/yr) is the geometric
mean of this range, then the range is calculated to be 45.2- to 226-g TEQ/yr. Assuming
that the best estimate of 3.4-g TEQ annual emissions in product (i.e., the fraction of sludge
that is distributed and marketed as a product) is the geometric mean of the range, then the
range is calculated to be 1.5- to 7.5-g TEQ/yr.
11.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES
In the early 1980s, EPA investigated the extent of inadvertent generation of PCBs
during the manufacture of synthetic organic chemicals (Hammerstrom, et al., 1985). For
example, phthalocyanine dyes and diarylide pigments were reported to contain PCBs in the
mg/kg range. EPA subsequently issued regulations under TSCA (40 CFR 761.3) that
banned the distribution in commerce ;of any products containing an annual average PCB
concentration of 25 mg/kg (50-mg/kg maximum concentration at any time). In addition,
EPA required manufacturers with processes inadvertently generating PCBs and importers of
products containing inadvertently generated PCBs to report to EPA any process or import
for which the PCB concentration is greater than 2 mg/kg for any resolvable PCB gas
chromatographic peak.
11.4. COMBUSTION SOURCES
11.4.1. Municipal Solid Waste Incineration
Municipal solid waste incinerators have long been Identified as potential PCB air
emission sources. Stack gas concentrations of PCBs for three incinerators were reported in
U.S. EPA (1987c), and the average test results yields an emission factor of 18-/^g PCBs/kg
refuse. Stack gas emissions of PCBs from the three incinerators were quantified without
•11-13 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
determining the incinerator's PCB destruction efficiency. The PCB content of various
consumer paper products was analyzed as part of the study. This study indicates that
paper products such as magazine covers and paper towels contained up to 139 micrograms
'j :: h . ''i'1:! A,, " i , 'i1:1 l; ...» .' '" j:1" v'.'...., i' ' ' .! ''
of PCB per kilogram of paper (/zg/kg). These levels, which were reported in 1981, were
attributed to the repeated recycle of waste paper containing PCBs. For example,
carbonless copy paper manufactured prior to 1971 contained PCB levels as high as 7
percent. This copy paper then became a component of waste paper, which was recycled.
'•i , i • i ;';ifi! ',,••' j'" '' 'i.'''If '",' iiv •• : '\.>.v. ..'H./5 ;' ti- t ?;',;• ;'... '.'I., ,":'' ;.;. • v it. .ii,'- , •''•.. |. , .
The PCBs inevitably were introduced into other paper products, resulting in continued
.'"..!' ' ' ;•.. 1 .'"' • :,-'-,!S[^H;E: U1''1 n^t^ii'^ if.?j';.:•>>•'-,• j.1 ^.^,:'••••;! }••••..•:. • ••• . • ,
measurable levels in municipal refuse some 4 years after the PCB manufacturing ban was
imposed. Refuse-Derived Fuel (RDF) manufactured from these paper products had PCB
levels of 8,500 A*g/kg, indicating that this fuel could be a source of atmospheric PCBs.
Therefore, it was assumed in U.S. EPA (1987c) that municipal refuse does contain
detectable levels of PCBs, arid that some of these PCBs may enter the atmosphere when
the refuse is incinerated.
Shane et al. (1990) analyzed fly ashes from five municipal solid waste (MSW)
incinerators for PCB congener group content. Total PCB levels ranged from 99 to 322
jug/kg in these ashes with the tri-, tetra-, and penta-congener groups occurring in the
:"'s: , " " * •;•' m !;/ 11 ' ' i i • :•.!•• .'•• .
highest concentrations. Shane et al. (1990) also analyzed seveh bottom ashes and eight
I ' . ... ' I'llMI ,, I I **
I'l'ltJl
II «! 'I!
bottom ash/fly ash mixtures for total PCB measured as Aroclor 1254. The detection limit
for this Aroclor analysis was 5 /ug/kg. Aroclor 1254 was detected in two of the seven
bottom ash samples (26 and 8 //g/kg) and in five of the eight fJy ash/bottom ash mixtures
(range of 6 to 33 #g/kg).
The development of more sensitive analytical methodologies has enabled researchers
in recent years to detect dioxin-like PCB congeners in the stack gases and fly ash from full-
scale and pilot-scale MSW incinerators (Sakai et al., 1993a; Sakai et al., 1993b; Boers et
al.j 1993; Schoonenboom et al., 1993; Sakai et al., 1994). Similarly, the advances in
\']' i ,, •' I • ;j ' ; "
analytical techniques have enabled researchers to determine that dioxin-like PCBs can be
formed during the oxidative solid combustion phase of incineration presumably due to
dimerization of ch[orobenzenes.,/J..iabprlatpry-slcale studies have also recently demonstrated
that dioxin-like PCBs can be formed from heat treatment of fly ash in air (Schoonenboom et
al., 1993; Sakai et al., 1994). However, the available data are not adequate to support
11-14 . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
development of a quantitative estimate of a dioxin-like PCB emission factor for this source
category.
11.4.2. Industrial Wood Combustion
Emissions of PCB congener groups, not individual congeners, were measured during
stack testing of two industrial wood burning facilities by the State of California Air
Resources Board {CARB, 1990e; 1990f). Table 11-10 presents the average of the
congener group (i.e;, mono- through decachlorobiphenyl) emission factors for these two
facilities. No tetra- or more chlorinated congeners (i.e., the congener groups containing the
dioxin-like PCBs) were detected at either facility at detection limits corresponding to
emission factors in the low ng/kg of wood combusted range.
In CARB (1990e), PCBs were measured in the emissions from two spreader stoker
wood-fired boilers operated in parallel by an electric utility for generating electricity. The
exhaust gas stream from each boiler is passed through a dedicated ESP after which the gas
streams are combined and emitted to the atmosphere through a common stack. Stack
tests were conducted both when the facility burned fuels allowed by existing permits and
when the facility burned a mixture of permitted fuel supplemented by urban wood waste at
a ratio of 70:30.
In CARB (1990f), PCBs were measured in the emissions from twin fluidized bed
combustors designed to burn wood chips to generate electricity. The APCD system
consisted of ammonia injection for controlling nitrogen oxides, and a multiclone and
electrostatic precipitator for controlling paniculate matter. During testing, the facility
burned wood wastes and agricultural Wastes allowed by existing permits.
11.4.3. Medical Waste Incineration
As discussed in Section 3.3, EPA recently issued nationally applicable emission
standards and guidelines for medical waste incinerators (MWI) that address CDD/CDF
emissions. Although PCBs are not addressed in these regulations, the data base of stack
test results at MWIs compiled for this rulemaking does contain limited data on PCB
congener group emission factors. Data are available for two MWIs lacking add-on APCD
, ' ' » ' -
equipment and for two MWIs with add-on APCD equipment in place. The average
congener group emission factors derived from these test data are presented in Table 11-11.
11-15 April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
Because datg are available for only 4 of the estimated 2,400 facilities that comprise this
:'... , ?"*;„, •"','" , "•.' .V , ' i;if '''» '; - '• .,•:•••'':", !i;i •;,; > li; ;•' ' i.., " • • ••( *i «l:"! i 1 '••!'.";':" "; >•, ••".' : ":•' .''': < ,: ,£'F." V '•' •.':' ' [ ' • • > ' ' '
Industry and because these data do not provide congener-specific emission factors, no
'•'•:; •; *'!.' '•'.,.., r. ••'•. 'iiiii :•-•, •l:^3:l:f!^ .':•'.-<••$¥, livfe'''.•'•'.'.!-* •' •.'•••'•'•;; .:i;ii'^ :'••:' i -. v, -
national estimates of total PCB or dioxin-like PCB emissions are being made at this time.
•':' 11.4,4.,. , , Tire Combustion r . ,. : ' . : *
Emissions of PCB congener groups, not individual congeners, were measured during
stack testing of a tire incinerator by the State of California Air Resources Board (CARB,
1991 a). The facility consists of two excess air furnaces equipped with steam boilers to
,i . • ..'>!. •; . t> ; .... ' lisi; ...,: , ...i,; n •; • f '.v-'; .!". ;i>;.! .!;•;:. |;i./::,,;; •;>.-!••. ;:; •',;.. 7'i r.ir.U'.;.".,". <•; ] ' -.
recovery the energy from the heat of combustion. Discarded whole tires were fed to the
incineration units at rates ranging from 2,800 to 5,700 kg/hr during the 3 testing days.
The furnaces are equipped to burn natural gas as auxiliary fuel. The steam produced from
the boilers drives electrical turbine generators that produce 14.4 megawatts of electricity.
The facility is equipped with a dry acid gas scrubber and fabric filter for the control of
M1; ' ' • ? •' ', '"'"''i;11 ' JHIIiirli .[ ',' '' ,' '. IKi^r,/.!, j',i i' " ..'"' .: lhi."' ,ii, 'I! y i I'1 ', "",'' .ni.iiiif'H. ,.y '1:1 'r'Hilil" „ ,;ii|,illi:i»',i, ' ' ,' , I , ' '. '' ' 'i ' "
errifssions prior to exiting the stack. Table 11-12 presents the congener group (i.e., mono-
Illi.1!!'!! v , : " r " ' Will1 "i "•','. i" , ,i« '-I'*', I ? "ill " "<• : • '" ' - ."•'••' . iVi ' . I .'"..•.'• "!l : ii" '.. - ' «• >' • i.
processed.
EPA estimated^ that approximately 0.50-miilion metric tons of tires were incinerated
" ' \ ' ! ™' !. ••ii^. . . * ... _.
in1990 in the United States {U.S. EPA, 1992a). This production estimate is given a
"medium" confidence rating, because it is based on both published data and professional
judgement. The use of scrap tires as a fuel increased significantly during the late 1980s;
however, no quantitative estimates were provided in U.S. EPA (1992a) for this period. In
1990, 10.7 percent of the 242-million scrap tires generated were burned for fueh This
percentage is expected to continue to increase (U.S. EPA, 1992a). Of the tires burned for
energy recovery purposes, pulp and paper facilities used approximately 46 percent; cement
kilns, 23 percent; and one tire-to-energy facility, 19 percent (U.S. EPA, 1997b).
If it is assumed that 500-million kg of discarded tires are incinerated annually in the
i • .•
United States, then, using the sum of the average emission factors for the total tetra-
through hepta-chlorinated congener groups (1.2-yug/kg tire processed) derived from stack
data from the one tested facility, yields a total emission of 610 g per year. However, it is
not known what fraction of this emission is dioxin-like PCBs.
11-16 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
11.4.5. Cigarette Smoking
Using high-resolution mass spectrometry, Matsueda et al. (1994) analyzed tobacco
from 20 brands of commercially available cigarettes collected in 1992 from Japan, the
United States, Taiwan/China, the United Kingdom, Germany, and Denmark for the PCB
congeners 77, 126, and 169. Table 11-13 presents the results of the study.
However, no studies have been reported which examined the tobacco smoke for the
presence of these congeners. Thus, it is not known whether the PCBs present in the
tobacco are destroyed or volatilized during combustion, or whether PCBs are formed during
combustion. The combustion processes operating during cigarette smoking are complex
and could be used to support either of these potential mechanisms. As reported by Guerin
)
et ah (1992), during a puff, gas phase temperatures reach 850°C at the core of the
firecone, and solid phase temperatures reach 800°C at the core and 900°C or greater at
the char line. Thus, temperatures are sufficient to cause at least some destruction of
CDD/CDFs initially present in the tobacco. Both solid and gas phase temperatures rapidly
decline to 200 to 400°C within 2 mm of the char line. Formation of dioxin-Iike PCBs has
been reported in combustion studies with other media in this temperature range (Sakai et
al., 1994). However, it is known that a process likened by Guerin et al. (1992) to steam
distillation takes place in the region behind the char line because of high localized
concentrations of water and temperatures of 200 to 400°C. At least 1,200 tobacco
v constituents (e.g., nicotine, n-paraffin, some terpenes) are transferred intact from the
tobacco into the smoke stream by distillation in this area, and it is plausible that PCBs
present in the unburned tobacco would be subject to similar distillation.
In 1995, approximately 487-billion cigarettes were consumed in the United States
and by U.S. Armed Forces personnel stationed overseas. Per-caplta U.S. cigarette
...•'•• • (
consumption in 1995, based on total U.S. population aged 16 and over, declined to 2,415
from a record high of 4,345 in 1963. In 1987, approximately 575-billion cigarettes were
consumed domestically (The Tobacco Institute, 1995; USDA, 1997).
A preliminary rough estimate of potential emissions of dioxin-Iike PCBs can be made
using the following assumptions: (1) the average dioxin-Iike PCB TEQ content of seven
brands of U.S. cigarettes reported by Matsueda et al. (1994), 0.68 pg/pack (or 0.034
pg/cigarette) is representative of cigarettes smoked in the United States; (2) dioxin-Iike
PCBs are neither formed nor destroyed, and the congener profile reported by Matsueda et
' 11-17 . April 1998
-------
... DRAFT-DO NOT QUOTE OR CITE
L;, " jv /; , i: , JiUi .'!••.'•• .;. i "• , •',', ""!' .•.•'. :••• , i-:!';"'1' :..•> :.'•.•„ •'.;.• :••.• «< •• • • :h' •, '•'••,>. • ' -i '
al. (1994) is not altered during combustion of cigarettes; and (3) all dioxin-like PCBs
contributing to the TEQ are released from the tobacco during smoking. Based on these
assumptions, the calculated annual emissions would be 0.020-9 TEQ and 0.016-g TEQ for
reference years 1987 and 1995, respectively.
:• il, - " . . 'Ivii'Ki ' " .,"'"• ,„ '!:'' „ ' ,i , • '''I ''i ' " i , , ' , , 4 c " | ,,'
11.4.6. Sewage Sludge Incineration
U.S. EPA (1996f) derived an emission factor of 5.4 ^g of total PCBs per kg of dry
,Jk • • "' 'III M <<"•.•. ' \~ \:' '
sludge incinerated. This emission factor was based on .measurements conducted at five
multiple hearth incinerators controlled with wet scrubbers. In 1992, approximately 199
sewage sludge incineration facilities conbusted b.865-miilion metric tons of dry sewage
sludge (Federal Register, 1993b). Given this mass of sewage sludge incinerated, the
estimated annual release of total PCBs to air annually is 4,670 g. However, it is not known
what fraction of this annual emission is dioxin-like PCBs. '
11,5. NATURAL SOURCES
11.5.1. Biotransformation of Other PCBs
Biologically mediated reductive dechJorination under anaerobic conditions to less
chlorinated congeners followed by slow anaerobic and/or aerobic biodegradation is believed
to be a major pathway for destruction of PCBs in the environment.. Research reported to
date and summarized below indicates that biodegradation should result in a net decrease
rather than a net increase in the environmental load of dioxin-like PCBs.
Laboratory studies (e.g., Bedard et al., 1986; Pardue et al., 1988; Larsson and
Lemkemeier, 1989; Hickey, 1995; and Schreiner et al., 1995) have revealed that more than
two dozen strains of aerobic bacteria and fungi, which are capable of degrading most PCB
;,VT"', . 'J, ,, .'; ': ipjiiijljl P,'" I" ,,.' I'W!1"!1'1 .; y, , t& ,'"!"! •• ,,; , ;, " rj:',, •.•.ul"l:'.'<>•!*.'! -:» i't \ -'i i!',:"'1, v"':"'", i'.*1'!,^.'^ ";" t "'./"'Si1 "' '; '. i1 ' ,
these organisms are of the genus Pseudomonas or the genus Alcajigenes. The major
;,.' „ j, I,, . ;
-------
DRAFT-DO NOT QUOTE OR CITE
chlorination. The half-lives for biodegradation of tetra-PCBs in fresh surface water and soil
are 7 to 60+ days and 12 to 30 days, respectively. For penta-PCBs and higher chlorinated
PCBs, the half-lives in fresh surface water and soil are likely to exceed 1 year. RGBs with
all or most chlorines on one ring and PCBs with fewer than two chlorines in the ortho
position tend to degrade more rapidly. For example. Can and Berthouex (1994} monitored
over a 5-year period the disappearance of PCB congeners applied to soil with sewage
sludge. Three of the tetra- and penta-chlorinated dioxin-like PCBs (IUPAC Nos] 77, 105,
and 118) followed a first-order disappearance model with half-lives ranging from 43 to 69
months. A hexa-substituted congener {IUPAC No. 167) and a hepta-substituted congener
/"
(IUPAC No. 180) showed no significant loss over the 5-year period.
Until recent years, little investigation focused on anaerobic microbial dechlorination
or degradation of PCBs even though most PCBs eventually accumulate in anaerobic
sediments (Abramowicz, 1990; Risatti, 1992). Environmental dechlorination of PCBs via
losses of meta and para chlorines has been reported in field studies for freshwater,
estuarine, and marine anaerobic sediments including those from the Acushnet Estuary, the
Hudson River, the Sheboygan River, New Bedford Harbor, Escambia Bay, Waukegan
Harbor, the Housatonic River, and Woods Pond (Brown et al., 1987; Rhee et al., 1989; Van
Dort and Bedard, 1991; Abramowicz, 1990; Bedard et al., 1995; and Bedard and May,
1996). The altered PCB congener distribution patterns found in these sediments (i.e.,
different patterns with increasing depth or distance from known sources of PCBs) have
been interpreted as evidence that bacteria may dechlorinate PCBs in anaerobic sediment.
Results of laboratory studies reported recently confirm anaerobic degradation of
PCBs. Chen et al. (1988) found that "PCs-degrading" bacteria from the Hudson River
could significantly degrade the mono-, di-, and tri-PCB components of a 20-ppm Aroclor
1221 solution within 105 days. These congener groups make up 95 percent of Aroclor
1221. No degradation of higher chlorinated congeners (present at 30 ppb or less) was
observed, and a separate 40-day experiment with tetra-PCB also showed no degradation.
Rhee et al. (1989) reported degradation of mono- to penta-substituted PCBs in
contaminated Hudson.River sediments held under anaerobic conditions in the laboratory (N2
atmosphere) for 6 months,at 25°C. Amendment of the test samples with biphenyl resulted
in greater loss of PCB. No significant decreases in the concentrations of the more highly
chlorinated (i.e., more than five chlorines) were observed. No evidence of degradation was
11-19 April 1998
-------
DRAFT-pq NOT QUOTE OR CITE
observed in samples incubated in CO2/H2 atmospheres. Abramowicz (1990) hypothesized
that this result could be an indication that, in the absence of CO2, a selection is imposed
favoring organisms capable of degrading PCBs to .obtain CO2 and/or low molecular weight
metabolites as electron receptors.
Risatti (1992) examined the degradation of PCBs at varying concentrations (10,000
ppm, 1,500 ppm, and 500 ppm) in the laboratory with "PCB-degrading" bacteria from
Waukegan Harbor. After 9 months of incubation at 22°C, the 500-ppm and 1,500-ppm
samples showed no change in PCB congener distributions or concentrations, thus indicating
K'!, '„ ' '. • «,' m. i" ,.,,;,',, i1'" !•:,•;;;;• i i j i * M '" • •
a Jgck of degradation. Significant degradation was observed in the 10,000-ppm sediment
W ,J - ''-I. .,'" '' "lili'•"i'1 '. " -. •" •!(•> .'ii'.i'., ••; i i i 1 i ' ."i • , . :', . . . •
with at least 20 congeners ranging from TrCBs to PeCBs showing decreases.
Quensen et al. (1988) also demonstrated that microorganisms from PCB-
cbhtaminated sediments (Hudson River) dechlorinated most tri- through hexa-PCBs in
""',,, I I I |
Aroclor 1242 under anaerobic laboratory conditions. The Aroclor 1242 used to spike the
sediment contained predominantly tri- and tetra-PCBs (85 mole percent). Three
concentrations of the Aroclor, corresponding to 14-, 140-, arid 700-ppm on a sediment dry-
weight basis, were used. Dechlorination was most extensive at the 700-ppm test
conceptrajion; 53 percent of the total chlorine were removed in16 weeks, and the
proportion of TeCBs through HxCBs decreased from 42 to 4 percent. Much less
degradation was observed in the 140-ppm sediment, and no observable degradation was
found in the 14-ppm sediment. These results and those of Risatti (1992) suggest that the
organisrn(s) responsible for this dechlorination may require relatively high levels of PCB as a
terminal electron acceptor to maintain a growing population.
Quensen et al. (1990) reported that dechlorination of 500-ppm spike concentrations
,,. ;!' . 'I •' "'I "filli'fhl i1?1 i • j"1!! '" , ill*1 , .1 ", • > i. ' i!!;* +• ' , •[. .'Nil;.!', ": ',„'• , ' ,, :,' " I:"'1!,;""»!,' I ,• '!' "I ri'ililMii.ii"1^ " ' ' ,
of Aroclor 1242, 1248, 1254, and 1260 by microorganisms from PCB:contaminated
sediments in the Hudson River and Silver Lake occurred primarily at the meta- and para-
positions; ortho-substituted mono- and di-PQBs increased in concentration. Significant
decreases over the up to 50-week incubation period were reported for the following dioxin-
like PCBs: 156, 167, 170, 180 and 189. Of the four dioxin-like TeCBs and PeCBs detected
in the Aroclor spikes (i.e., IUPAC Nos. 77, 105, 114, and 118), all decreased significantly
in concentration, with the possible exception of PeCB 114 in the Aroclor 1260-spiked
sediment.
-20 * April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Nies and Vogel (1990) reported similar results with Hudson River sediments
incubated anaerobically and enriched with acetone, methanol, or glucose. Approximately
30O ppm of Aroclor 1242 (31-mole percent TeCBs, 7-mole percent PeCBs, and 1-mole
percent HxCBs) were added to the sediments prior to incubation for 22 weeks under an N2
atmosphere. Significant dechlorination was observed, with dechlorination occurring
primarily at the meta- and para-positions on the more highly chlorinated congeners (i.e.,
TeCBs, PeCBs, and HxCBs), resulting in the accumulation of less-chlorinated, primarily
ortho-substituted mono- through tri-substituted congeners. No significant dechlorination
was observed in the control samples (i.e., samples containing no added organic chemical
substrate and samples that were autoclaved).
v Bedard and May (1996) also reported similar findings in the sediments of Woods
Pond, believed contaminated with Aroclor 1260. Significant decreases in the sediment
concentrations of PCBs 118, 156, 170, and 180 (relative to their concentrations in Aroclor
1260) were observed. No increases or depreases were reported for the other dioxin-like
PCBs.
Bedard et al. (1995) demonstrated that it is possible to stimulate substantial
microbial dechlorination of the highly chlorinated PCB mixture Aroclor 1260 in situ with a
single addition of 2,6-dibromobiphenyl. Bedard et al. (1995) added 365 g of 2,6-
dibromobiphenyl to 6-fpbt diameter submerged caissons containing 400-kg sediment (dry
weight) and monitored the change in PCB congener concentrations for a period of 1 year.
At the end of the observation period, the hexa- through mono-chlorinated PCBs decreased
74 percent in the top of the sediment and 69 percent in the bottom. The average number
of chlorines per molecule dropped 21 percent from 5.83 to 4.61, with the largest reduction
observed in meta-chlorines (54 percent reduction) followed by para-chlorines (6 percent).
The dechlorination stimulated by 2,6-dibromobiphenyl selectively removed meta-chlorines
positioned next to other chlorines.
The findings of these latter studies are significant, because removal of meta- and
para-chlorines from the dioxin-like PCBs should reduce their toxicity and bioaccumulative
potential and also form less chlorinated congeners that are more amenable to aerobic
biodegradation.
Van Dort and Bedard (1991) reported the first experimental demonstration of
biologically-mediated ortho-dechlorination of a PCB and stpichiometric conversion of that
11-21 ' April 1998
-------
. DRAFT-DO NQT QUOTE OR CITE
PCB congener (2,3,5,6-TeCB) to less chlorinated forms... In that study, 2,3,5,6-TeCB was
incubated under anaerobic conditions with unacclimated methanogenic pond sediment for
"*\\ . i , '",",", tsK't f: ," , „/ !" .([. it'K ••':•. n v -if: '4; ::•,:;'', I- ;\'-fa.i '• .'« i . •'.', ., , •' :•; .,;ii \" ' ' | ' • .'• - '
37 weeks, with reported dechlormation to 2,5-DCB (21 percent); 2,6-DCB (63 percent);
ii H' „ •. • ". • !,mi " iLiiiii ~ i,' ,,:, , M. i: , ,. • • ", : IK v •• •! • . «•• ',•„ ,• • •> ,. * , t. \ , .i n . , m . ,. . i ,. •
and 2,3,6-TrCB (16 percent).
r, „' ' ' !! '',, « "l'!j.'"| ! ' " T ''n||l '„ ,,, ,',,,' •!.',, ^ ;.|| , '!,,. ' ' ,M , , " ' v " |, ,/; , ' ' ' |
11.5.2. Photochemical Transformation of Other PCBs
*' i " I'i " '•••'•• '\ .•••'• .'•'-
Photolysis and photo-oxidation may be major pathways for destruction of PCBs in
'V !!"' ' ' I I \> , I •'"" .
the environment. Research reported to date and summarized below indicates that ortho-
ii:,iii'i i —'' /': ; 'ii,,-.!!i ' »;T • : . i, '.i,:»iV' u| M, " r .-'i |!|1" ,/ ,*.,<>,^ i ::>'i'» > « ij* : • "|"1' • '
substituted chlorines are more susceptible to photolysis than are meta- and para-substituted
congeners. Thus, photolytic formation of more toxic dioxin-like PCBs may occur.
Oxidation by hydroxyl radicals, however, apparently occurs preferentially at the meta- and
para-positions thus resulting in a net decrease rather than a net increase in the
environmental load of dioxin-like PCBs.
> - • ', :'' " ': .' I HI * j I | '
Based on the data available in 1983, Leifer et al. (1983) concluded that all PCBs,
especially the more highly chlorinated congeners and those that contain two or more
ii*!: \ ' 'i ' ' .' ' I II" I I '! ' ' ' ' ' '
chlorines in the ortho-position, photodechlorinate. In general, as the chlorine content
increases, the photolysis rate increases. More recently, Lepine et al. (1992) exposed dilute
solutions (4 ppm) of Aroclor 1254 in cyclohexane to sunlight for 55 days in December and
January. Congener-specific analysis indicated that the amounts of many higher chlorinated
congeners, particularly mono-ortho-substituted congeners decreased, while those of some
lower chlorinated congeners increased. The results for the dioxin-Jike PCBs indicated a
43,5 percent decrease in the amount of PeCB 114; a 73.5 percent decrease in the amount
of HxCB 156; and a 24.4 percent decrease in the amount of HxCB 157. However, TeCB
77 and PeCB 126 (the most toxic of the dioxin-like PCB congeners), which were not
detected in unirradiated Aroclor 1254, represented 2.5 percent and 0.43 percent,
!"'"'•• '"; ",i '* i! •• :\'-''^•.!'£!'•.'•»•:'• fM-''^'.-' :•'•'.'•.*< ••"•il•.•:*:;* '• ••;•.. ! ' ;' ,
respectively, of the irradiated mixture.
With regard to photo-oxidation, Atkinson (1987) and Leifer et al. (1983), using
assumed steady-state atmospheric OH concentrations and measured oxidation rate
';;• . '"•: '; ; ii! !•.•'•. .- /.,';,;,;„'::/ l;1-:l-1,j;;;^;•••., 4fti^Y''»»<«! •im.M?' , ':;:'! ' i
constants for biphenyl and monochlorobiphenyl, estimated atmospheric decay rates and
i:i,!ixi ' • ,i,, ',, : r ::"; :>\ • ,«" ,,'ii1,,,;,;1 ,; ;h:',./':!;:"ii: :|n;» 1,1,iii "jriiv.'!! I'l1. ".iiii''!:!'!"'!.;!!" '"."i ' I „
; :i, ' ,.. : -ii\m .T'-II • '.' •,...••'',"• :•• . • " ':t i1-; n. <^ v t-'r ^••i!i,i,^i(.1 v(r> ;••$ ; hVi i i
half-lives for gaseous-phase PCBs. Atmospheric transformation was estimated to proceed
most rapidly for those PCB congeners containing either a small number of chlorines or those
containing all or most of the chlorines on one ring. Kwok et al. (1995) extended the work
', :ft ; :-i.'-' ' • f. r .;;.',:;:•. • .•(!".'• $•'.•• •••• \f\ m !':;:':!"' .; 'M:'•;•''• . ' ." '
• •' • •;«! : • i > . :• :!li I ' J ~ • •. :;,,! o' '• -"-'t i''''.^ '{"••• ('"!"V~'''" i
11-22 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
of Atkinson (1987) by measuring the OH radical reaction rate constants for 2,2'-, 3,3'-, and
3,5-dichlorobiphenyl. These reaction rate constants, when taken together with the
measurements of Atkinson (1987) for biphenyl and monochlorobiphenyl and the estimation
method described in Atkinson (1991), were used to generate more reliable estimates of the
gas-phase OH radical reaction rate constants for the dioxin-like PCBs. The persistence of
* v /"
the PCB congeners increases with increasing degree of chlorination. Table 11-14 presents
these estimated rate constants and the corresponding tropospheric lifetimes and half-lives. •
Sedlak and Andren (1991) demonstrated in laboratory studies that OH radicals,
generated with Fenton's reagent, rapidly oxidized PCBs (i.e., 2-monp-PCB and the DiCBs
through PeCBs present in Aroclor 1242) in aqueous solutions. The results indicated that
the reaction occurs via addition of a hydroxyl group to one nonhalogenated site; reaction
rates are inversely related to the degree of chlorination of the biphenyl. The results also
indicated that meta- and para-sites are more reactive than ortho-sites due to stearic
hindrance effects. Based uport their kinetic measurements and reported steady-state
aqueous system OH concentrations or estimates of OH radical production rates, Sedlak and
Andren (1991) estimated environmental half-lives for dissolved PCBs (mono-through octa-
PCB) in fresh surface water and in cloud water to be 4 to 11 days and 0.1 to 10 days,
respectively. .
-23
April 1 998
-------
DRAFT-DO NOT QUOTE OR CITE
to
o>
o
I
of
u
0>
CD
K»—
CD
CO
•.iib"
CO
CD
CO
111
.1
CO
U)
LU
CO
o
D_
CD
x
O
CD
I.
CD
S
CO
f
e
1
S
1
1
£
«
S
k
C
'
;
•
u
•3
C
|
c
a
u
1
I
1
E
cj
|
i
c
1
1
1
3
E
i
!
i
>
>
r
S
II Rel«ses of Commercial PCBi
^
2
2
<
Z
Z
z
|| Approved disposal
^
*•
|| Accidental releases
«
1
to
•E
1
in
r-
p
i
CO
0
OJ
c
tr
Z
*
I
s
z
i
z
z
e
1
1
1
g
|
M
C
u
i
CO
o
1
1
I
1
o
w
•55
CD
p
O
1
i
a
to
C
3
i
^
z
II Municipal waste incineration
z
z
Industrial wood combustion
z
z
c
s
1
z
z
c
o
1
i
£
Z
z
2
§
Z
z
z
z
z
z
I
ffl
s,
u
II Sewage sludge Incineration
o
•a
.0
o
.2 5 S
^
,-Q '5
« a 2
ill
,-
is-l
§"2 »
!"•!
8 3
s
" n i
5x5.
-------
DRAFT-DO NOT QUOTE OR CITE
fX
CO
o>
tu.
CD
co
>
• Q)
O
C
03
to
OC
CO
CD
4-»
55
T>
CD
'E
^
".G '
^
»_
£
CO
CO
to
E
UJ
c
-.0
CO
.2
UJ
CO
o
Q. .
CD
™
C
'x
o
Q
.u
t
o>
fc
•3
O
CN
i
co
.a
CD
1
S
S
£
c
S
•5
•I
;
(
•p
3
«5
s
_
<
i
o
i
=
_
9
^.
!
• s
•B
5
B
.!
._
I
9
C
,_
D?
U
1
Z
1
£
1
Emission Source
§
I
<
<
;
> z
II Releases of Commercial PCBs
S
OJ . . B
IS -°
a •' ' S
.E *J jc '
s • = i
2 S^ .
.w .2 S m
•_ X ,. 0
s -g i >-
S. g §S
— E — Q.
•- ° •§ §•
3 CR = Confidence rating. 1
H = High Confidence.
M = Medium Confidence.
L = Low Confidence.
NA = Not applicable.
NEG = Expected to be negligibli
BLANK = Insufficient data avail
G TEQ/yr = grams toxic equival
11-25
April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
Table 11-3. Weight Percent Concentrations of Dioxin-like PCBs in Aroclors, Clophens, and Kanechlors
Dtoxra-Lflce PCS Congener
AROCLOR 1016
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,S'-HxCB
2,2',3,3',4,4',5-HpCB
2,2',3,4,4',5,5'-HpCB
2,3.3',4,4',5,S'-HDCB
AROCLOR 1221
3,3%4,4'-TCB
2,3,3' ,4,4'-PeCB
2,3,4,4',5-PttCB
2.3',4,4',5-PeCB
2',3,4,4%5-PcCB
3,3',4,4%5-PeCB
2,3,3*,4,4',S-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^',3,4,4't5,5>-HpCB
2.3,3' ,4,4' .S.S'-HpCB
AROCLOR 1242, Clophen A-30.
and Ktoechlor 300
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',4,41,5'-HxCB
2,3',4.4'^4'-HxCB
3,3',4,4',S.5'-HxCB
2.2',3.3'.4,4'.5-HpCB
2,2',3.4,4'.S,S'-HpCB
2,3,3',4,4'4,5'-HpCB
AROCLOR 1248, Clophen A-40.
«xJKaj*cchJor400
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',S-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'.S,5'-HpCB
2,3,3',4,41,5,5'-HpCB
IUPAC
Number .
77
105
114
118
123
126
156
157
167
169
170
180
189
77
105
114
118
123
126
156
157
167
169
170
180
189
77
105
114
118
123
126
156
157
167
169
170
180
189
77.
105
114
118
123
126
156
157
167
169
170
180
189
Number of.
Samples
Analyzed
2
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
1
12
8
5
6
6
11
6
5
5
11
3
2
4
10
6
4
5
4
8
5
4
4
9
2
1
3
Number of
Detections
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
0
0
0
0
0
0
—
-
0
12
8
2
6
4
8
5
1
1
2
2
1
0
10
6
3
5
4
6
5
3
2
' 3
2
I
1
Mean Cone.
(ND = 0)
(g/kg>
0
0
0
0
0
0
0
0
0
0
0
0
0
Total TEQ =
4.00
0
0
4.50
0
0
0
0
0
0
-
-
0
Total TEQ =
3.14
3.66
1.55
8.26
1.53
0.06
0.48
0.004
0.004
0.00002
0.38
0.30
0
Total TEQ =
4.56
7.83
5.05 .
20.01
2.12
0.15
1.41
0.33
0.25
0.01
2.05
2.60
0.004
Total TEO =
TEQ Cone.
(ND = 0)
(mg/kg)
0
0
0
0
0
0
0
- 0
0
0
0
0
0
0
2.00
0
0
0.45
0
0
0
0
0
0
~
-
0
2.45
1.57
0.37
0.77
0.83
0.15
6.29
0.24
0.002
0.00004
0.0002
0.04
0.003
0
10.26
2.28
0.78
2.53
2.00
0.21
14.51
0.70
0.16
0.002
0.13
0.21
0.03
0.0004
23.54
Mean Conc.a TEQ Cone.3
(ND = 1/2DL) (ND = 1/2DL)
(g/kg) (mg/kg)
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
Total TEQ = 0
4.00 2.00
0 0
0 0
4.50 0.45
0 0
0 0
0 0
0 0
0 0
0 0
— —
..
0 0
Total TEQ = 2.45
3.14 ' 1.57
3.66 0.37
1.66 0.83
8.26 0.83
1.58 0.16
0.11 11.29
0.52 0.26
0.11 0.06
0.11 0.00
0.05 0.54
0.46 0.05
0.43 0.004
0 0
Total TEQ = 15.94
4.56 2.28
7.83 0.78
5.06 2.53
20.01 2.00
2.12 . 0.21
0.18 18.26
1.41 , 0.70
0.34 0.17
0.26 0.003
0.05 0.47
2.05 0.21
2.60 0.03
0.10 0.01
Total TEO = 27.65
11-26
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 11-3. Weight Percent Concentrations of Dioxin-like PCBs in Aroclors, Clophens, and Kanechlors (continued)
Dioxin-Like PCB Congener
AROCLOR 1254, Cloohen A-50.
and Kanechlor 500
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',5,51-HxCB
3,3',4,4',5,5'-fLxCB
2,2',3,3',4,4',5-HpCB
2,2',3,4,41,5,5'-HpCB
2,3,3',4,4',5,5'-HpCB
AROCLOR 1260. Cloohen A-60.
and Kanechlor 600
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',4,41,5,5'-HpCB
IUPAC
Number
77
105
114
118
123
. 126
156
157
167
169
170
180
189
77
105
114
118
123
126
156
157
167
169
170
180
189
Number of
Samples
Analyzed •
12
9
6
8
5
11
7
6
7
11
5
'4
4
12
8
6
8
5
11
8
5
7
11
5
4
5
Number of
Detections
9
9
3
8
5
9
7
5
6
6
5
4
1
6
8
3
7
1
7
8
5
6
5
5
4
5
Mean Cone.
(ND = 0)
(g/kg)
0.59
26.67
15.98
66.33
5.35
1.23
11.22
1.49
2.47
0.10
5.80
6.63
0.07
Total TEQ =
~
0,16
1.56
1.00
11.14
0.00
2.30
7.53
2.28
3.23
0.21 .
28.98
' 66.30
2.16
Total TEQ =
TEQ Cone.
(ND = 0)
0.30
2.67
7.99
6.63
0.53
122.95
5.61
0.75
0.02 •
1.01
0.58
0.07
0.01
149.12
0.08
0.16
0.50
1.11
0.00
230.22
3.77
1.14
0.03
2.09
2.90
0.66
0.22
242 87
Mean Cone."
(ND = 1/2DL)
(g/kg)
0.64
26.67
;J-
16.08
66.33
5.35
1.26
11.22
1.53
2.47
0.15
5.80
6.63
0.21
0.21
1.56 "•
1.10
11.14
. 0.11
2.33
7.53
2.28
3.23
0.24
28.98
66.30
2.16
Total XEO —
TEQ Cone.3
(ND = 1/2DL)
0.32
2.67
8.04
6.63
0.53
125.68
5.61
0.77
0.02
1.50
0.58
0.07
0.02
152.44
,
0.10
' 0.16
, . ' ' • 0.55
1.11
0.01
233.27
3.77
1.14
0.03
2.37
2.90
0.66
0.22
246 29
Calculated for a congener only when at least one sample contained detectable levels of .mat congener.
References: , - „
Schuizetal. (1989)
Duinker and Hillebrand (1983)
deBoer et al. (1993)
Schwartz et al. (1993)
Larsen, et al. (1992) : :
Kannan et al. (1987)
Huckins etal. (1980)
Albro and Parker (1979) •
Jensen etal. (1974)
. Albroetal. (1981) •
Duinker etal. (1988)
Tanabeetal. (1987) • , '
Himberg and Sippola (1990) •
g/kg = grams per kilogram.
mg/kg = milligrams per kilogram. '
11-27
April 1998
-------
.'.• DRAFT-DO NOT QUOTE OR CITE
II
II
II
II
11
II
II
1
II
H
li
II
jj <
||
li '
y '
1
£
4
i
\
A
o
11
y
|
I •*
«
1 2
It co
li
|| gj
11 M
II c
II
If
11
II
1
1
1
I
*
£5
S
5
(D
0
cc i;
1. ^ * -i. 1
Annex 1 Incinerato
Annex 1 incineratol
High efficiency boi
Other approved inc
Annex II chemical
s s
E Q-
1 t
u. =r
Q. °-
8 8
us *°
A g
i? i?
>• 1-
a eg
g g
9 O
1 ^
- h-
00
3
Cu
E £2
5 O CD
5 £ g
O MO
^ .S M
^ ^ c
c c: a
^ £ *
I II
*s *1
5§ 3|
;° | §
II is
A
~
5
CO
O
EC ij
r|1
CD .E 5
Annex 1 incineratol
Annex 1 incineratol
High efficiency boi
Other approved inc
Annex II chemical
m g
^ Cu
1 1
£ S
8 8
S >o
A g
£ .If
"5 "co
c c
CO CO
CD CD
CO CO
S 5
H- 1-
"5
5
33
Z
g
D
3
a
D
o
0 T3
^1
li
•s o
U TJ
CO
m
O
Q.
waste landfill
Annex 1 incineratol
Annex fl chemical '
— »
'5.
to
.-E
0 0
CD ••
— £
waste
materii
81
•o i
11
11
:
t
:
c
*~
^~
c
EC
' U.
O
waste landfill
;posal method (40
Annex 1 incineratol
Annex II chemical '
Other approved dis
CD
CD
CD
5
n w
5 O
5 CD
3 "£
*~ *m
•=•£
§8
to tn
1 s>
fl-
lf
a E
11
Q is
CD
U
'E
CD
O
^^
g
C
^
.£
•5 *
•D __
03 t
tn a
0 }
•— j
CD w
•Q t
transformers may
1 transformers is m
Annex 1 incinerator
Drained and rinsed
waste landfill
Disposal of drained
V.
I
V.
c.
K
"°
» S
E c
6 'E
1 §
2 o
£• O
r> m
Cu D.
5
5
!
CO
D
5
•*
?
a
J
-
Annex 1 incinerator
3
1
n
o
CO
3
CU
~O o
« CD
5 «
.9- ra
.2 S
§ S
E o
S '•£
M- g.
O *Q
•a •£
CD ^
CO ^
o E
.CO JQ
"° »-
machines may be
nay be disposed o
Drained and rinsed
waste or salvaged
Drained machines i
salvaged
CO CO
0 0
Q. Cu
E E
Q. Q.
Q- Q.
8 8
O O
T— «—
A V
c c
!E is
1 1
0 0
O O
CO CO
0 0
-C _C .
- 1—
CO
CD
C
u
ra
E
a
3
B
5
>.
D
L
=:
X
0>
c
c
*£ ^
o ^i
X (
CD ~~
C j
5 1
^ i
to
Q. "5
14— (
nay be disposed o
or Annex II chemi
Drained machines r
Annex 1 incinerator
a
CO c
1 s
^ Q.
S a
n .£
c
I 1
S c
§ s
U C
.'5
_cr
>,
waste provided an
0
CO
"co
'c "5
co a
< =5
CO
CD
CO
CQ
O
Q.
•^ P
c £•
c °-
28
§">
o v
CD CD
CO o
0 c
•C 0
1— o
c
c
I
c
_
CO
CO
0
Q.
CO
'•5
o
*~*
^o
Q.
•o
CD
_c
•Q
CD
CD
CO
ca
o
OL
~o >
is
II
Annex 1 incinerator
Annex II, provided
Decontaminate per
CO
CD
C
CO
§
D
3.
CD
O
2
CD
I
3
•t
i
o
Q
J
1.
•o
s
E
Q.
C
a:
u.
O
I
CO
CD
O
Cu
O.
Q.
O
o
in
I I
c .,
8 I
CD. C
i t
CQ O
'E CD
I 2
0=5 =
*^ = c
5 £
r^ c
O
"Sec
<= E
•5°
?s
co .E
r^ ° -9.
1^ CD CO
E-e^
O c £
o- ra
<*
c ° ^
k- ^
"o 9- £
Q} CL CD
.£ 2 o
o o «
I
c •
- J2
> S
3 •—
2 £ 1 S
« ^ 1 S 5 Q
•E § § ~ ° f2
r-» C _ *^ u_ T^
si
CO i_
•g CD
g Q
O
jyisti
< cc < Q. a a.
co
en
Q.
LU
CO
O
CO
11 -28
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 11-5. Offsite Transfers of PCBs Reported in TRI (1988-1993)
Year
1993 -
1 992
1991
1990
1989
1988
No. of TRI
Forms Filed
16
20
26
NA
,NA
122
Reported Transfers (kg)
Transfers
to POTWs
120
0
0
0
0.5
113
Transfers for
Treatment/
Disposal
463,385
766,638
402,535
1,181,961
2,002,237
2,642,133
TOTAL
TRANSFERS
463,505
766,638
402,535
1,181,961
2,002,237
2 642 246
kg = kilograms.
POTWs = publicly-owned treatment works.
Sources: U.S. EPA (1993h); U.S. EPA (1995g)
i • • .
NA = Not available.
11-29
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
CO
O)
O)
CO
00
o>
.-(-
;fc
1
O
Q.
CO
DC
in
CO
O
D_
CD
CO
co
_CD
CD
DC
I
CO
CD
S
CD
CD
CC.
£
O
Q.
CO
1— **
«- EC
CC
8-g
8 §
JD — 1
T3
1.1
O) o
CD .92.
c —
z>
CO
CD ,_ 2.
ro 2 °
CO m
Q
5'^1
|l|
^
CD g 0
^ll
— T3
CC .CD
ti-
es CO
0 £
1
O
CM
C
O
O
O
O
CO
CO
CO
en
if.
o
in
c>
o
o
o
o
o
CN
CM
CO
CO
o
o
o
to
o
o
co
CM
CO
0)
t—
CT.
Cvi
CO
CM
«
CM
CO
0
O
o
CO
CM
•z.
o
0)
O)
'CO
•in
CO
in
O
8
0
o
z
a>
00
CO
00
CO
T—
CO
o
in
o
CM
CM
CM
t--
00
00
0)
O)
tn
en
UJ
CO
CO
O)
en
CO
co
CD
O
CO
-O
JO
"ca
CC
4~>
o
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 11-7. Aroclor Concentrations Measured in EPA's National Sewage Sludge Survey
Aroclor
1016
1221
1 232
1242
1248
1254
1260
Any Aroclor (total)
Percent
Detected
0
0
0
0
9
8
10
19
Maximum
Concentration
(ng/kg)
—
'
• • __'
__
5.20
9.35
4.01
14.7
Median Concentration (ng/kg)
Nondetects
Set to
Det. Limit
—
„
~
0.209
0.209
0.209
1 .49
Nondetects
Set to
Zero
0
0
0
0
0
0
0
0
Source: U.S. EPA (1996a); for POTWs with multiple samples, the pollutant concentrations
were averaged before the summary statistics presented in the table were calculated. All
concentrations are in units of nanograms per kilogram (ng/kg) dry weight.
11-31
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
0>
00
J2
I
I
c
o
a
1
c
^
^
=S
J
0
s
i
1
Maximum
i
I o!
•a m ^
i Q
S
2 3 o
z
| o|
|<°§
oncentration
(ng/kg)
o
11
^ «»
CJ m
^i
CD
CD
C
O
CO
CO
co
cn
a
co
cc
CO
ca
cn
cc
o
CN
0
CM
§
en
CM
CM
CO
cn
£
o
^>
*fr
" CO
CO
10
o
m
0
0-
^
Tj-
CO
CO
CM
2
ca
o
S.
10
;jj.
^r
co
CM
CO
ca
o
a.
in
•4-
>d-
CO
CM
CO
CM
ca
o
a.
to
5t
^>
CO
CM
C
cn
o
^j*
00
CD
CO
in
00
CO
to
CO
o
q
CO
CO
CO
CO
CM
m
o
CL
"I
•*
Tj-
co
CO
CO
10
ca
o
X
to
^
^t
CO
co
CM
to
ca
0
X
to
ifr
^t
CO
CO
CM
CO
ca
O
X
in
to
T^
Tj-
co
CM
00
cn
co
Tf
T"
CO
CM
CO
O
^.
O
i?
^
cn
CO
m
o
X
in
to
<3-
•*
CO
CO
O
r-.
m
0
a
in
5*
•*
co
CO
CM
CM
O
00
ca
o
a.
[n
in
^
Tf
CO
CM
CM
cn
00
ca
o
a
to
to
^
^
CO
CO
CM
cn
CO
to
CM
cn
CO
00
CO
CM
CM
cn
CO
CM
o
UJ
t2
2
3
_0
to
a
O
a.
0)
s
w
c
o
UJ -O
ID (B m
§ |-
—
•a
(D
CO
£
c
o
o
J£
c
m
11-32
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 11-9. Quantity of Sewage Sludge Disposed Annually by
Primary, Secondary, or Advanced Treatment 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 Landfills3
Sludge Incinerators and Co-
Incinerators1'
Ocean Disposal
TOTAL
Volume Disposed
(thousands of dry metric
tons/year)
1,714
71
396
157
1,819
865
(336)d
5,357
Percent of
Total
Volume
32.0e
1.3
7.4
2.9
33.9
16.1 '
(6.3)d
100.0
Potential TEQ
Release0
(gofTEQ/yr)
82.3
3.4
19.0
7.5
87.3
(f)
(0)d
199 5
a
b
c
Landfills used for disposal of sewage sludge and solid waste residuals.
Co-incinerators treat sewage sludge in combination with other combustible waste materials.
Potential PCB TEQ release for nonincinerated sludges was estimated by multiplying the sludge
volume generated (i.e., column 2) by the average of the mean dioxin TEQ concentrations in
sludge reported by Green et al. (1995) and Cramer et al. (1995) (i.e., 48:ng TEQ/kg).
d The 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 in the oceans in 1988 has not been determined.
e Includes 21.9 percent applied to agricultural land, 2.8 percent applied as compost, 0.6 percent
applied to forestry land, 3.1 percent applied to "public contact" land, 1.2 percent applied to
reclamation sites, and 2.4 percent applied in undefined settings.
f See Section 11.4.6 for for a discussion of dioxin-like PCB releases to air from sewage sludge
incinerators. ;
Sources: Federal Register (1990); Federal Register (1993b); Green et al. (1995); Cramer et al.
(1995).
11-33
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 11-10, PCB Congener Group Emission Factors for Industrial Wood Combustors
Congener Group
Monochlorobiphenyls
Dichlorobiphenyls .
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Number
of
Sites
2
2
2
2
2
2
2
2
2
2
Number
of
Detections
1
1
1
0
0
0
0
0
0
0
Maximum
Concentration
Detected
(ng/kg wood)
32.1
23.0
19.7
•
—
Mean Concentration
(ng/kg)
Nondetects
Set to
Det. Limit
39.4
50.9
42.3
22.7
17.6
17.0-
17.9
15.8
25.0
36.3
Nondetects
Set to
Zero
16.0
11.5
9.8
..
__
»«.
_„
-„
...
...
ng/kg = nanograms per kilogram.
i'1"'" I' >. , ,.i . , ',:,iH"P!|i'| .1,,
Source: CARB (1990e; 1990f)
11-34
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table 11-11. PCB Congener Group Emission Factors for Medical Waste Incinerators {MWIs)
Congener Group
Monochlorobiphenyls
Dichlorobiphenyls
TrichlOrobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Mean Emission Factor (ng/kg)
(2 MWIs without APCD)
Nondetects
Set to
Det. 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
Det. Limit
0.311
0.340
0.348
1.171
17.096
1 .286
0.902
0.205
__
0.1 17
Nondetects
Set to
Zero
0
0
0
0
9.996
1.078
0
0
0
APCD = Air Pollution Control Device
ng/kg = nanograms per kilogram!
'— =' Not reported.
Source: See Section 3.3 for details on tested facilities.
11-35
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Table,11-12. PCB Congener Group Emission Factors for a Tire Combustor
Congener Group
Monochlorobiphenyls
Dichlorofaiphenyls
Trichlorobiphenyls
Tetrachlorofaiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
Decachlorobiphenyls
Number
of
Samples
3
3
3
3
3
3
3 .
3
3
3
Number
of
Detections
0
1
1
0
2
1
1
0
0
0
Maximum
Concentration
Detected
(ng/kg)
—
34.8
29.5
„
2,724
106.5
298.6
—
Mean Emission Factor
(ng/kg)
"Noridetects
Set to
Det. Limit
0.04
11.7
11.8
10.0
1,092
55.9
107.7
20.9
17.7
41.9
Nondetects
Set to
Zero
-
- 11.6
9.8
...
1,092
35.5
99.5
_
_
--
ng/kg = nanograms per kilogram.
Source: CARB {1991 a)
11-36
April 1998
-------
DRAFT-DO NOT QUOTE OR GITE
S3
£
s
£
CO
O)
O
c
.0
ra
ii
d
1C
p.
0
*3~
CO
CO
in
O
CQ
a.
•*
**
CO
CO
' .
«
CQ
O
tT
^.
CO
CM"
CO
ca
o
CD
0.
uv
'd'
CO
CM
CO
CM
CQ
O
CD
Ct.
in
•<3-
CO
CM
CM
CM
C
to
j£
CO
CO
cs
CO
CM
CO
o
CL
in
'^>
co
CO
co
in
m
0
X
to
^.
^>
CO
CO
CM"
to
ca
0
X
in
;*
^~
CO
CO
CM
CO
ca
O
X
to
to
r}-'
>
CO
CM
1
to
o
o
^
CM
a>
d
to
o
O}
d
a>
co
ca
O
X
to
to
^
'co
CO
o
CO
o
a
in
Tt
•*
CO
CO
CM
CM
•
o
CO
m
O
a
in
in
^.
Tf
CO
CM
CM
O)
CO
ca
0
a.
in
10
^
^>
CO
CO
CM
|^
O
CM
d
in
C
M^
•
co
d
CM
CO
O
CO
co
d
*
o
in
I—
"co
o
I-
a>
UJ
O
11-37
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
p
'"£
i '^*
!'"-=
„£
11: to
S
a.
I
Q
I
-s
03
!
.&
i-
o
•c
°-"m
to !L
O c
Q-T
o —
£• &
~a j
S ~
m •«
J^
*rf
UI
•S
1
*f CO *3" CO CT
co co co CM in
CO CO CO CO CO
CM CO CM M- CO
o o o o o
.
03 ff. 03 03 03
O g O O O
CU £ CL CL CU
^. ^ 10 in_ in
'f ^. ^ 'f ^
co «* 't ^ t
CO CO CO ^ CO
CM CM CM CM CO
03
O
CD
CO CO 10
CO CO CM
O O T-
000
03 QQ 03
O O O
Q. Q. O
XXX
't 10 in
•* ^T ^T
CO 't 51-
fl fl CO
CM CM CO
CM CM CM
m .
o
Q.
in
O)
co
X
oo
•S 5
o
c
o
o
o
ID
o>
CO
I
m ^
C W
If
S S
.S -D
Ifi QJ
g|
II £
-. <0
1°
O IG
CO
en
LO
CD
CO
c
o
O
CO
11-38
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
REFERENCES
Abrampwicz, D. (1990) Aerobic and anaerobic biodegradation of PCBs: A review. Critical
Reviews in Biotechnology. 10{3):241-251.
Adriaens, P.; Grbic-Galic, D. (1992) Effect of cocontaminants and concentration oh 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 oh measurement of hazardous air
pollutants from aluminum melt furnace operations at Ravenswood Aluminum
Corporation. Monroeville, PA: Advanced Technology Systems, Inc.
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, V.G.; Becking, G.C.; Birnbaum, L.S.; Brower, A.; Derks, H.J.G.M.; Feeley, M.;
Golor, C.; Hanberg, A.; Larsen, J.C.; Lierri, A.K.D.; Safe, S.H.; Schlatter, C.; Waern,
F.; Younes, M.; Yrankeikki, E. (1 994) Toxic equivalency factors for dioxin-like
PCBs. Chempsphere 28(6):1049-1067.
AISI. American Iron and Steel Institute. (1990) Annual statistical report - 1989.
Washington, D.C.: American Iron and Steel Institute.
AISI. American Iron and Steel Institute. (1995) Annual statistical report - 1994.
Washington, D.C.: American Iron and Steel Institute.
Aittola, J.; Paasivirta, J.; Vattulainen, A. (1992) Measurements of organochloro compounds
at a metal reclamation plant. Organohalogen Compounds 9:9-12.
Aittola, J.P. (1993) Environmental emissions from landfill fires, preliminary investigation.
Viatek Topiola Og^ Esppo, Finland.
April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
Al|ro, P.W.;~ Parker, C.E. (1979) Comparison of the compositions of Aroclor 1242 and
• Aroclor 1016. Journal of Chromatography 169:161-166.
Albro, P.W.; Corbett, J.T.; Schroeder, J.L. (1981) Quantitative characterization of
pblychlorinated biphenyl mixtures (Arpclors® 1248, 1254, and 1260) by gas
chrpmatography using capillary columns. Journal of Chrpmatpgraphy 205:103-11.1.
,«'' I ' ' '"',!" " IF it. 11 ' '• ' / '"' '' ' '"''" '' ' "• i1'
Amendola, G.A.; Barna, D.R. (1989) USEPApetroleum refinery dioxin screening survey:
BP Oil-Lima, Ohio Refinery. "We'stiake, OH: U.S. Environmental Protection Agency,
Region 5, Environmental Sciences Division.
„;,,;,, i - ' i ii . ,,; ;•;> f:. ;:i"f • ' i> .".,. i!;";' *uS;:;;lli-1 • .i';:'•../' ': .'• '- ';• "|! .s..,'." '' .'" .' i
American Forest & Paper Association (1997) Paper, paperpoard & wood pulp statistics:
data through 1996. Washington, DC: American Forest & Paper Association.
American Paper Institute (1992) Statistics of paper, paperboard & wood pulp: data through
1991. New York, NY: American Paper Institute.
Atkinson, R. (1987) Estimation of OH radical reaction rate constants and atmospheric
lifetimes for polychlorobiphenyls, dibenzo-p-dioxins, and dibenzofurans. Environ.
Sci. techno). 21:305-307.
Atkinson, R. (1991) Atmospheric lifetimes of dibenzo-p-dioxins and dibenzofurans. The
Science of the Total Environment. 104:17-33.
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.
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.
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.
:,'• i •' (" • lil, ' f, ,.' •; -i" <:&•.'•%• .•.;.'•*I;•*•'*.&!•?•,"}•..<:%<:'!•, >'./:;, . •.•uv " tiv < '•. ' \ ' - :
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.; Munder, A.; Swerev, M. (1986) Automobile
exhausts versus municipal waste incjneratipn as sources of the polychlpro-
dibenzodioxins (PCDD)""arid '-fu'ransI'PCDFJ found in the environment. Chemosphere
15(7):(901-915).
Barkovskii, A.L.; 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.
R-2 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Barkovskii, A.L.; Adriaens, P. (1996) Microbial dechlorination of historically present and
freshly spiked chlorinated dioxins and diversity of dioxiri-dechlorinating populations.
Applied and Environmental Microbiology 62{l2):4556-4562.
Beard, A.; Krishnat, P.N.; Karasek, F.W. (1993) Formation of polychlorinated dibenzofurans
by chlorination and de novo reactions with FeCI3 in petroleum refining processes.
Environ. Sci. Technol. 27(8):1 505-1511.
Bedard, D.L.; Unterman, R.; Bopp, L.H.; Brennan, M.J.; Haberl, M.L.; Johnson, C. (1986)
Rapid assay for screening and characterizing microorganisms for the ability to
degrade polychlorinated biphenyls. Applied and Environmental Microbiology
51{4):761-768.
Bedard, D.L.; Smullen, L.A.; DeWeerd, K.A.; Dietrich, O.K.; Frame, G.M.; May, R.J.;
Principe, J.M.; Rouse, T.O.; Fessler, W.A.; Nicholson, J.S. (1995) Chemical
activation of microbially-mediated PCB dechlorination: a field study. Organohalogen
Compounds 24:23-28.
Bedard, D.L.; May, R.J. (1996) Characterization of the polychlorinated biphenyls in the
sediments of Woods Pond: evidence for microbial dechlorination of Aroclor 1260 in
situ. Environ. Sci. Technol. 30(1 ):237-245. .
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, A.G.; Edmunds, C.J.; Graham, B.W.; Jones, M.T. (1989) Determination of PCDDs
and PCDFs in car exhaust. Chemosphere 19(1-6):669-673.
Boers, J.P.; de Leer, E:W.B.; Gramberg, L.; de Koning, J. (1993) Levels of coplanar PCBs
in flue gases of high temperature processes and their occurrence in environmental
samples. Organohalogen Compounds 11:233-236.
Bowes, G.W.; Mulvihill, M.J.; Simoneit, B.R.T.; Burlingame, A.L.; Risebrough, R.W. (1975a)
Identification of chlorinated dibenzofurans in American polychlorinated biphenyls.
Nature 256:305-307.
Bowes, G.W.; Mulvihill, M.J.; DeCarnp, M.R.; Kende, A.S. (1975b) Gas chromatographic
characteristics of authentic chlorinated dibenzofurans; identification oi two isomers
in American and Japanese polychlorinated biphenyls. J. Agric. Food Chem.
23(6):1222-1223.
Bremmer, H.J.; Troost, L.M.; Kuipers, G.; DeKoning, J.; Sein, A.A. (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.
R-3
April 1998
-------
§ IP , •, i,,'.i
DRAFT-DO NOT QUOTE OR CITE
BlSwn' ^-F- I1"11 Petermin.air.ipp of PCBrTjetabolic, excretion, and accumulation rates for
use as indicators of biological response and relative risk. Environ. Sci. Technol.
28{i3):2295-2305.
i,JK
(M
BrPwn'. J-F.; Bedard, D.L.; Brennan, M.J.; Carnahan, J.C.; Feng, H.; Wagner, R.E. (1987)
Pplychlorinated biphenyl dechlorination in aquatic sediments. Science 236:709-712.
BrPwp, .J..F.; Carnahan, J.C.; Dorn, S.B.; Groves, J.T.; Ligon/W.V., May, R.J.; Wagner,
'.'•',w • •,' V •*:' J', ^J,' :!i?mllP"/,S/B' (.T?,?^-'.!rfY^?.P,t,N8?P^t'P1QPF,1.lc9ipgeners in PCB dielectric
fluids from capacitors and transform^
Brown, J.F.; Frame, G.M.; Olson, D.R.; Webb, J.L. (1995) The sources of the coplanar
PCBs. Organohalogen Compounds 26:427-4361
Brunner, C.R. (1992) Sewage sludge. In: Buonicore, A.J.f Davis, W.T., eds., Air pollution
engineering manual. Air and Waste Management Association. New York, NY: Van
:;";:;• ",,^ '.Y ..' '.:':,' Nostrand Reinholdl pp. 296-311.
/nil I,*,„ •": 'ii , i, . ,i ' ixv , " , |n ii ' i " '•, ,:!''•,, 'ijiiitii i"'ik 'if , ,"!'• ",i, , • :ii, i i:ii . '.' ;i, „" ;,L , '','«i!"ii,:,• • "j1 'wa '/ ' ; |,,,:i",'i'. • \ ,,; • ' w "" '"'
Brt|zy, L.P.;; Hites} R.A. (1995) ^Estimating the atmospheric deposition of polychlorinated
l!!;'!:'-^: f,,:!( i ' H'f dipenzp-p-dipxins and dibenzofurans from soi|. Environ. Sci. Technol. 29:2090-
;" =":, ":"' ".• '• !:''i- ',2098. '
BrY?nt' J-6- (199?) Chlorinated benzenes, In: Kjrk-Othmer Encyclopedia of Chemical
Technology. 4th ed. Vol.6, pp. 87-100.
Buckland, S.J.; Dye, E.A., Leathern, S.V.; Taucher, J.A. (1994) The levels of PCDDs and
PCDFs in soil samples collected from^ conservation areas fQllowing brush fires.
Organohalogen Compounds. 20:8589.
Burjib, R.R.; Crummett, W.B.; Cutie, S.S.; Gledhill, J.R.; Hummel, R.H.; Kagel, R.O.;
LamParski, L.L.; Luoma, E.y.; Miller, D.L.; Nestrick, T.J.; Shadoff, L.A.; Stehl, R.H.;
Wppds,J.S. (1980) Trace chemistries of fire: a source of chlorinated dioxins.
Science 210(4468):385-390f
Buonicore, A.J. (1992a) CpntroJ 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.
'.'•I :< J . i II I I !' I ','>',
Buc?Pcoret A-J- ^19u92fc>) 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.
Busej, H.R.; Bosshardt, H.P. (1976) petermination of polychlorinated dibenzo-p-dioxins and
dipenzpfurar|s in cipm.
-------
DRAFT-DO NOT QUOTE OR CITE
Cains, P.W.; Dyke, P. (1994) Emissions of chlorinated dibenzodioxins and dibenzofurans
from waste combustion planits in the UK. Organohalogen Compounds 20:271-276.
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). . -
Capes, C.E. (1983) Size enlargement. In: Kirk-Othmer Encyclopedia of Chemical
Technology. 3rd ed. 21:77-105. New York, NY: John Wiley and Sons.
CARB (California Air Resources Board) (1987a) Determination of PCDD and PCDF
emissions from motor vehicles. Draft report. October 1987. Test Report No C-86-
029.
CARB (California Air Resources Board) (1990a) ARB 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.
CARB (California Air Resources Board) (1990b) Evaluation on a wood waste fired
incinerator at Koppers Company, Oroville,California. Test Report No. C-88-065.
; Engineering Evaluation Branch, Monitoring and Laboratory Division. May 29, 1990.
CARB (California Air Resources Board) (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.
• • • ' ' -- "••".'"
CARB (California Air Resources Board) (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, 1997.b.]
CARB (California Air Resources Board) (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.
CARB (California Air Resources Board) (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. '
CARB (California Air, Resources Board) (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 in NCASI, 1995.]
R-5
April 1998
-------
1)RAFT--DO NOT QUOTE OR CITE
CARB (California Air Resources Board) (1991 a) 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.
CARB (California Air Resources Board) 0992a) 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.]
B.,i • .. ..... ' : ' li ...... I " " " ir ' j ....... i i il '• I • . . • • :
CARB (California Air Resources Board) (1992b) Emission, measurements on delacquering
system. Confidential Report No. ERC-32y Engineering Evaluation Branch,
Monitoring and Laboratory Division. [As reported in U.S EPA, 1997b.]
..... "I'll .......... ' i i i i :•:. |r' :_, • •
CARB (California Air Resources Board) (1993aj Emissions measurement of toxic
compounds from a cupola baghouse i at a steel foundry. Confidential Report No.
ERp-61. Engineering Evaluation Branch, Monitoring and Laboratory Division. [As
........ reported in ....... U.S . EPA, 1 997b J ......
Carpenter, C.; Schweer, G.; Stinnett£ G.; Gabel, N. (1986) Exposure assessment for
hexachlorobenzene. Washington, DC: U.S. Environmental Protection Agency,
Office of Toxic Substances. EPA 560/5-86-01 9.
in i i , • i "
in i i i i ,i ' ' , i
Carroll, W.F. (1 996) Is PVC in house fires the great unknown source of dioxin? Fire and
Materials. 20:161-166.
Cash, G. {1993) Document on dipxin/furan data call-ins .(memorandum to. John Schaum,
U.S. EPA, Office of Research and DeyelopmenlJ. Washington, D.C.: U.S.
Environmental Prptectiqn, Agency, Office of Pollution Prevention and Toxics. May 4,
1993. ................... ' ; ...... _ ................
CEQ (Council on Environmental Quality) (1997) Environmental Quality 1990. 25th Annual
Report. Washington, DC: Council on Environmental Quality. Executive Office of the
,° ..... "',, P'r^sjdent ot' " " ..... ' '" ' '' "'""" " '' ' '' '' '
ChemRisk (1 993) Critique of dioxin factories. Prepared for: The Vinyl institute, September
1993.
.... , . /
Chen, Y.R.; Chen, C.J.; Lee, C.C.; Chuong, C.Y. (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, C.S.; Bush, B.; Rhee, G.Y. (1988) Anaerobic biodegradation of
polychlorinated biphenyls by bacteria from Hudson River sediments. Ecotoxicol. and
r Environ. Safety 16:95-1 05 i .......................................... ......... .................................. '"'' .......................... '
R-6 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Choudhry, G.G.; Webster, G.R.B. (1989) Environmental'photochemistry of PCDDs 2.
Quantum yields of direct phptotransformation 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
apetonitrile and their sunlight half-lives. J. Agric. Food Chem. 37:254-261.
Christmann, W.; Kloppel, K.D.; Partscht, H.; Rotard, W. (1989a) Tetrachlorobenzpquinones
a source of PCDD/PCDF. Chemosphere 18(1-6):789-792.
Christmann, W.; Kasiske, D.; Kloppel, K.D.; Partscht, H.; Rotard, W. (1989b) Combustion
of polyvinyl chloride - an important source for the formation of PCDD/PCDF
Chemosphere 19(1-6):387-392.
Clement, R.E.; Tosine, H.M; Osborne, J.; Ozvacic, V.; Wong, G. (1985a) Levels of
chlorinated organics in a municipal incinerator. In: Keith, L.H.; Rappe, €.;
Choudhary, G., eds.. Chlorinated dioxins and djbenzofurans in the total environment
II. Boston, MA: Butterworth Publishers.
Clement, R.E.; Tosine, H.M.; AH, B. (1985b) Levels of polychlorinated dibenzo-p-dioxins
and dibenzofurans in wood burning stoves and fireplaces. Chemosphere
14:815-819.
Clement, R.E.; Tashiro, C. (1991) Forest fires as a source of PCDD and PCDF. Presented at:
Dioxin '91, 11th International Symposium oh Chlorinated Dioxins and Related
Compounds; Research Triangle Park, NC; September 1991.
Cramer, P.H.; Heiman, J.; Horrigan, M.; Lester, R.; Armstrong, S. (1995) Results of a
national survey for polychlorinated dibenzo-p-dioxins, dibenzofurans, and coplanar
polychlorinated biphenyls in municipal bipsolids. Organohaldgen Compounds
24:305-308.
Cull, M.R.; Dobbs, A.J.; Goudot, M.; Schultz, N. (1984) Polychlorodibenzo-p-dioxins and
dibenzofurans in technical pentachlorophenol-results of a collaborative analytical
exercise. Chemosphere 13(10):1157-1165.
f
Curlin, L.C.; Bommaraju, T.V. (1991) Alkali & chlorine products. Jn: Kirk-Othmer
Encyclopedia of Chemical Technology. 4th ed. pp. 938-1025.
deBoer, J. de; Stronck, C.J.N.; Traag, W.A.; van der Meer, J. (1993) Non-ortho and moho-
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.
Dempsey, C.R.; Oppelt, E.T. (1993) Incineration of hazardous waste: A critical review
update., Air & Waste 43: 25-73,
Deutsch, D.G.; Goldfarb, T.D. (1988) PCDD/PCDF contamination following a plastic fire in a
university lecture hall building. Chemosphere 17(12):2423-2431.
R"7 April 1998
-------
. DRAFT-DO NOT QtFOTE OR CITE
! , ' , -• , Si!! I, ,, ,. • • I,, :, ,1 , ,. ',;>;; I,' , ' , „!;;;, •: ,'.. ,';,!': , .(>•« :.,. •', ,\', ,'- "• • , 11 , , , j .;
DeVoogt, P.; Brinkman, U.A. (1989) Production, properties and usage of polychlormated
biphenyls. In: Halogenated biphenyls, terphenyls, napthalenes, dibenzodioxins and
related products. Kimbrough, R.; Jensen, A.A., Eds. New York, NY: Elsevier
Science Publishers.
Dqnnelly, J.R. (1992) Waste incineration sources: refuse. In: Buonicore, A.J.; Davis, W.T.,
edsc Air pollution engineering manual. Air and Waste Management Association.
Ne^ '
Dquben, P.E.T.; Eduljee, G.H.; Dyke, P. {1995) A review of "potential PCDD and PCDF
emission sources in the OfC- Orgariohalogen Compounds 24:131-136.
Dqucet, L.G. {1995) Reassessment of dioxin i emissions from MWIs. In: Comments
submitted by the American Hospital 'Association to the UlS. Environmental
Protection Agency on EPA's Reassessment Document for 2,3,7,8-TCDD and Related
Compounds. January 13, 1995.
• ' ' • ' i
Duinker, J.C.; Hillebrand, M.T.J. (1983) Characterization of PCB components in Clophen
formulations by capillary GC-MS and GC-ECD techniques. Environ. Sci. Technol.
17(8):449-456.
Duihker, J.C.; Schulz, D.E.; Petrick, G. {1988) Multidimensiohal gas chromatography with
electron capture detection for the determination of toxic congeners of
polychloririated biphenyl mixtures. Analytical Chemistry 60:478-482.
!. i i ..... . - ' ..... : , I,1'!!!!! !.:• . • . .', M.>: li. ..... (•.'.'. '. '' (; ;«•-::; ;« sir,. ..... •!; ,, 'ii. >..':" ;.'>!.' i> ..... i'*,:.* •' Ml' i. •.'.•'.'.• •' • ' \ ' "
Dumler-Gradl, R.; Thorna, H.; Vierle, O. (1995a) Research program on dioxin/furan
concentration in chimney soot from house heating systems in the Bavarian area.
Organohalogen Compounds 24:1 15-11 8.
, I ..... I! ."ill I
Dumler-Gradl, R.; Tartler, D.; f horna, H.; Vierle, O. (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, P.W. (1 992) Comparative rates of photolysis of polychlorinated
dibenzofurans in organic solvents and in aqueous solutions. Organohalogen
Compounds 8:233*-236.
Dyke, P,; Cplemah, P. {1 995) Dioxins in ambient air, Bonfire Night 1 994. Organohalogen
Compounds 24:213-216.
Eduljee, G.H.; Dyke, P. (1 996) An updated inventory of potential PCDD and PCDF
emission sources in the OK. the Science of the total Environment. 177:303-321 .
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).
R-8 , ., . April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
EIA (Energy Information Administration) (1992) Fuel oil and kerosene sales 1991.
Washington, DC: U.S. Department of Energy, Office of Oil and Gas. DOE/EIA-
0535(91 ).
EIA (Energy Information Administration) (1993) Petroleum supply annual 1992, volume 1
Washington, DC: U.S. Deprtment of Energy, Office of Oil -and Gas. DOE/EIA-
EIA (Energy Information Administration) (1 994) 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 (Energy Information Administration) (1995a) Fuel oil and kerosene sales 1994
Washington, DC: U.S. Department of Energy, Office of Oil and Gas. DOE/EIA-
0535(94). ' •'
EIA (Energy Information Administration) (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 (Energy Information Administration) (1 995c) Annual energy review 1 994
Washington, DC: U.S. Department of Energy, Office of Energy Markets and End
Use. DOE/EIA-0884(94).
EIA (Energy Information Administration) (1997a) Fuel oil and kerosene sales 1996.
Washington, DC: U.S. Department of Energy, Office of Oil and Gas. DOE/EIA-
0535(96). . ' . ,
EIA (Energy Information Administration) (1997b) Annual energy review 1996.
Washington, DC: U.S. Department of Energy, Office of Energy Markets and End
Use. DOE/EIA-0384O6).
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. EPRI TR-104614.
Erickson, M. (1 986) Analytical chemistry of PCBs. Boston, MA, Butterworth Publishers.
R"9 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Erickson, M.D.; Cole, C.J.; Flora, J.D.; Gorman, P.G.; Haile, C.L.; Hinshaw, G.D.; Hopkins,
F.C.; Swanson, S.E. {1984) Thermal degradation products from dielectric fluids.
Washington, Die.: U.S. Environmental protection Agency, Office of Toxic
""" Substances ' ' '"' " ' '
Esposito, M.P.; Tiernan, T.O.; Drydent, F.E. (1980). Dioxins. Prepared for the U.S.
Environmental Protection Agency, Cincinnati, OH.. November, 1980. EPA-600/2-
"80-197.™ '". / ...... ; .".; ..',..."....,..!..'!'.',"!,' , V...," ......... ", . .., ! . , . . . '
III i ' ' , i1 •.''' 'iiiiitil ' k ><• :'••'.• , ji'.'J.. j,;'! '" . "' i :ii ; j.'.'.ilhi'1 :'.'. iVKi,'1 ...... T' ' 'i'li':' " .'• :'';<•' ' llil -'I'v; ,i i1' , , ' ' -
Federal Register (1 979) Decision and emergency order suspending registrations for certain
'' uses of £4,5-T and Silvex. ^
Federal Register (1 982a) Polychlorinated biphenyls (PCBs) use in electrical equipment.
"' "'' """ '" "' ..... '' .......... ..... ..... ' ...... "" "" ....... '
Federal Register (1982b) Polychlorinated biphenyls (PCBs) manufacturing, processing,
distribution in cprnmerce and use prohibitions; use in electrical equipment. F.R.
(August 25)47:373421 ................ " ..... ' .................... . ...................
Federal Register (1 985a) Regulation of fuels and fuel additives; Gasoline lead content: final
rule and supplementaTndtice i'bf proposed rulemaking. F.R. (March 7) 50:9386-
9408.
Federal Register (1985b) Polychlorinated biphenyls in electrical transformers. F.R. (July
'.', ,'- 17) 50:29170. ,
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'.' F.R. (January 21) 52:2282-2293.
Federal Register {1987c) Polyhalogenated dibenzo-p-dioxins/dibenzofurans; testing and
reporting requirements; final rule. F.R. (June 5) 52:21412-21452.
Federal Register (1987d) Appendix A to part 60 (Amended). F.R. (December 16) 52:47853-
47856.
vV '",",,,.'- ;: , ii'ijjiJ! , ..,,. !,..', •,, ""i.,.:;;, i'i'.v •.;.'';;',:. ,J.f. '»• j-,.;;'.,!.[«' }',,, ';\,\ i, !•.•:'<" |!:, ,'.>. .5?';, r/ ,; !"'•'•' ,"
Federal Register (1990) National sewage sludge survey: availability of information and
*!•, | (i , ,, / :'" i ', iii'mi'lBII i, '' .I11"'!1!!11 'it „,• '''"' i ' I'M!.. '''. "V,1 ii!!'1! 'i ' '"'i.l I'1'!' '"",i,:i /fii1'11 "i I • n i1"^!1 iii'ini, ii. '!. ' I",ill!1: MT, * 11,.>; i ,, r " n'linimiiiiiLii1; 'i*• . , ? f ' .;•
data, and anticipated impacts on proposed regulation. F.R. (November 9)
55:47210-47283,
" 'i'1"!!'!' i " i , „ i .'"fliii!1 ' ;. . i1 " '"• ' •' '.,», ',„ n" :i i ill in j, . i i
Federal Register (1991 a) Standards of performance for new stationary sources and final
guidelines for municipal waste combustors. F.R. (February 11) 56:5488-5527.
R-1P
-------
DRAFT-DO NOT QUOTE OR CITE
Federal Register (1991 b) Standards of performance for new stationary sources and
guidelines for control of existing sources: municipal solid waste landfills: proposed
rule and guideline. F.R. (May 30) 56:24468.
Federal Register (1991 c) F.R. (February 21) 56:7134.
Federal Register (1993a) 2,3,5,6-Tetrachloro-2,5-cyclohexadiene-1,4-dione; proposed
significant new use of a chemical substance. F.R. (May 12). 58:27980-27986.
Federal Register (1993b) Standards for the use or disposal of sewage sludge- final rules
F.R. (February 19) 58:9248-9404. •
Federal Register (1993c) Chemicals; toxic chemical release reporting; community right-to-
know; significant new use rule. F.R. (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 F R (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 F R
(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. F.R. (November 20) 60:57747-57800.
Federal Register (1995c) National emission standards for hazardous air pollutants from
secondary lead smelting: final rule. F^R. (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
F.R. (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.
F.R. (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. F.R. (March 12) 61:9905-9944.
Federal Register (1996b) Revised standards for hazardous waste combustors: proposed
rule. F.R. (April 19) 61: 17357-17536.
Federal Register (1997a) Toxic chemicals; PGBs; submission of IRC No. 1000 to OMB;
information collection activities. F.R. (January 21) 62:3035-3036.
R~1 1 - April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Federal Register (1997b) F.R. (September 15) 62:48388-48394.
Fenton, M. (1996) Minerals yearbook - iron and steel. Washington, DC: U.S. Department
of the Interior, U.S. Geological Survey.
Fiedler, H.; Hutzinger, O. (1992) Sources and sinks of dioxins: Germany. Chemosphere,
• ",;; : 25:1487-1491, , , , .. ,'. , ,; , ,,; '. , , -
Fiedler, H. (1993) Formation and sources of PCDD/PCDF. Organohalogen Compounds
i, A '11:221 -228."' ' ,', '' ."." ,,"'" .' ' ^ ;, 'f'[. '^ ''...'.,_"".'.: ' , .' 2 , ].* ' , . • ' "'. •
I :", .'.;'. "''",' :iL: • • • -" .'':;.L.,>:lAks'''- ^^y.f:i^-: ". AA^A.V I .;i:AI,':T;;!i/A. '--i1' , i;' -•
Fiedler, H.; Hutzinger, O.; Hosseinpour, J. (1993) Analyses and remedial actions following
an accidental fire in a kindergarten. Organohalogen Compounds 1.4:19-22.
i ,n , i,.:1:;:-,-1:"* •
Firestone, p.; Ress, J.; Brown, N.L.; Barron, R.P.; Darnico, J.N. (1 972) Determination of
polychlorodibenzo-p-dioxins and related compounds in commercial chlorophenols. J.
'' '''"' ..... .' ....... , '.' ',
' '
. ,. ..
Frame, G.M. (1995) A ^comprehensive, rnulticenter study of P'CB elution on capillary GC
cblumns. Pittcon '95. ^jsiew Orleans, ' LA; "March 8, 1995; Paper 71 7.
, .L'J ............. !!.M ......... ' ............. "i ........................................ !.. . : '•'•}\:-. •,' . . :." ••'''-
Friesen, U.K.; Muirs D.C.G.; Webster, G.R.B. (1990) Evidence of sensitized photolysis of
polych'iorihated dibenzp-p-dioxins in' natural waters under sunlight conditions.
Enyiron. Scl, Technol. 24(11 j:1 739-1 744.
Ai , '.';. ;. ' ',11 i / i "A
Friesen, K.J.; Loewen, M.D.; Foga, M.M. (1993) Environmental aquatic photodegradation of
cHlorinated dibenzofurans and their photoproducts. Orgahohaiogen Compounds
12:135-137.
Fuchs, R.; Towara, J.; Hutzinger, 6." (1990) PCDD/F in the dry-cleaning process.
Organohalogen Compounds 3:441-444.
Furicke, W.; Theisen, J.; Balfanz, E.; Konig) J. (1988) Polychlorierte Dibenzofurane (PCDF)
und polychlprierte Dibenzo(p)dioxine (PCDD) in Ruckstanden und emissionen eines
Brandes in Anwesenheit von PBC-haltigen materialieh!' Staub-Reinhaltung der Luft
'•' 48.^393-396!"." , .......... ," ' ." '"'."" ......... ''.'.^ , , ".'.. ' .' ' .. J."
Funk, S. (1 996) Memorandum from S, Funk (EPA/OPP/HED) to Wm. Hazel
(EPA/OPP/HED). Washington, D.C.: U.S. Environmental Protection Agency, Office
of Pesticidj Programs. May 28, 1996
11 " "' J •,„",' 'lill'S11! i, •, ;; ....... , «. .' .'l " .......... !, ' »i i " i i. i|' , i.1 j ,i' i • , ;, ' '"'.i 1
Galson Corporation (1995) Source test report: Source emission testing at Roth Brothers
Smelting Corporation. East Syracuse, NY: Galson Corporation.
Gan, D.R.; Berthouex, P.M. (1994) Disappearance and crop uptake of PCBs from sludge-
amended farmland. Water Environment Research 66(1):54-69.
.April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
t • . . -"'[.,',,',
Gertler, A.W.; Sagebiel, J.C.; Dippel, W.A.; Sheetz, L.H. (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.; Faring, R. (1998) Measurement of dioxin and furan
emissions factors from heavy duty diesel vehicles. J. of the Air and Waste Mgmt
Assoc. 48:276-278. '
Gillespie, W.J. (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, W.J. (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, W.J. (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, Irtc.
Gilman, A.P.; Douglas, V.M.; Newhook, R.C.; Arbuckle, T.E. (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.; Waddell, D. (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, T.D.; Malloy, T.A.; 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, L.C.; Lester, R.L.; Armstrong, S.R. (1995) Comments on Estimating Exposures to
Dioxin-Like Compounds: Review Draft. Cambridge, MA: Cambridge Environmental
Inc. Dated January 12, 1995, and May 11, 1995.
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, W.L.; Johnson, M.D.; Raught, E.G.; Steuch, H.E.; Trusty, C.B. (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, G.W. (1994) The natural production of chlorinated compounds. Environ Sci
Technol. 28{7):310A-319A.
R-13
April 1998
-------
, DRAFT-DO NOT QUOTE OR CITE
Guerin, M.R.; Jenkins, R.A.; fomkins, B.A. (1992) The chemistry of environmental
I'11!1'1 ' ''„, 1 i „ riiiiiUll ' '' ,:'i I', ! ;' 'mi1 i' ' ! • , :»P ! ;' .'Mi'i II1, ' «,„':',„. "II t," ,1 i'1- ii,l Vn,:: ' ' ' »
tobacco smoke: composition and measurement. Chelsea, Ml: Lewis Publishers.
Gullett, B.K.; Ryan, J.V. (1997) On-road sampling of diesel engine emissions of
polyctilorinated dibenzo-p-dioxin and polychlorinated dibenzofuran. Organohalogen
Compounds 32:451-456.
Gutenmann, W.H7; Rutzke, M.; Kuntz, H;T.; Lisk, D.J. (1994) Elements and
polychlorinated biphenyls in sewage sludges of large cities in the United States.
Chemosphere 28|4):725-728.
Hagenmaier, H. (1986) Determination of 2,3,7,8-tetrachjorpdibehzo-p-dioxin in commercial
chJorophenols and related products. Fresenius Z Anal Chem. 325:603-606.
Hagenmaier, H. (1987) Belastung der umweit mit dioxinen. Institut fiir Organische Chemie
der Universitat Tubingen.
Hagenmaier, H.; Brunner, H. (1987) lsomer:specific analysis of pentachlorophenol and
sodium perrtachlorophenate for 2,3,7,8-substituted PCDD and PCDF at sub-ppb
levels^ Ch^nripsphere 16:1759-1764. ,'
Hagenmaier, H.; Dawidowsky, V.; Weber, U.B.; Hutzinger, O.; Schwind, K.H.; Thoma,, H.;
Essers, U.; Buhler, B.; Greiner, R. (1990) Emission of polYhalogenated
dibenzpdiqxjns and dibenzofurans from cornbustipn-engines. Organohalogen
Compounds 2:329-334.
Hagenmaier, H. (1994) Contributions of diesel-powered vehicles and wood burning to
overall PCDD/PCDF emissions. Organohalogen Compounds 20:267-270.
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; Urnea, Sweden; August 1988.
..'
Hammerstrom, K.; Schweer, G.; Adkins, L.; Freed, J.; Chambers, T. (1985) Exposure
assessment for polychlorinated bjphenyls (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.
Harnly, M.; Stephens, R.; McLaughlin, C.; Marcotte, J.;Petreas,M.; Goldman, L. (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):677-684r
Harrad, S.J.; Malloy, T.A.; Khan, M.A.; Goldfarb, T.D. (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.
R-14 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Harrad, S.J.; Jones, K.C. (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;
Heath (1995) Heath, Elizabeth of Research Triangle Institute, to Joseph Wood of Emission
Standards Division, OAQPS, EPA, August 23, 1995. Memorandum "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. Chemospherel 6(8/9) :1949-1957.
Helble, J.J. (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.
t i .
Hengstmann, R.; Hamann, R.; Weber, H.; Kettrup, A. (1990) Impact of sewage sludge
and sewer slimes by polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans. Organohalogen Compounds 4:407-412.
Hickey, W.J. (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.
Ho, A.K.W.; Clement, R.E. (1990) Chlorinated dioxins/fufans in sewage and sludge of
municipal water pollution control plants. Chemosphere 20(10-12):1549-1552.
Holderman, T.S. (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.
i • •
Holderman, T.S.; Cramer, P.H. (1995) Updated results of polyhalogenated dibenzorp-
dioxin/dibenzofuran testing and reporting under the Toxic Substances Control Act
(TSCA). Organohalogen Compounds 24:137-140. ,
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.; Morgenroth, M. (1993b) An investigation of
PCDD/CDF formation during textile production and finishing. Organohalogen
Compounds 11:417-420.
R-15
April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Horstmann, M.; lytpLachlan, M.S. (1994a) Textiles as a source of polychlorinated dibenzo-p-
dioxins and dibenzofurans (PCDD/CDF) in human skin and sevyage sludge. Environ.
Scl. & Pollut. Res^ 1 (i): 15-20.
Horstmann, M.; McLachlan, M.S. (1994b) Polychlonnated and
dibenzofurans in textiles and their transfer to human skin, sewage sludge and other
matrices, prganohalogen Compounds 20:251-254.
Horstmann, M.; McLachlan, M.S. (1995) Concentrations of polychlorinated dibenzo-p-
dioxins (PCDD) and dibenzofurans (PCDF) in urban runoff and household
wastewaters. Chemosphere 31{3):2887-2896.
'I " in1 11 iii ' ' ,j..•'.'•.'•'. '
Huang, C.W.; Miyata, H.; Lu, J.; Ohta, S.; Chang, T.; Kashimoto, T. (1992) Levels of
PCBs, PCDDs and PCDFs in soil samples from incineration sites for metal
reclamation in Taiwan. Chemosphere 24(11 ):1669-1676.
II : i ill ' " ' I •/• •', • • :' ' '.;
Huckins, J.N.; Stalling,D.L.; Petty, J.D. (1980) Carbon-foam chromatographic separation of
non-o-o -chlorine substituted PCBs from Aroclor mixtures. J. Assoc. Off. Anal.
Chem. 63(4):750-755.
ii .1 i • .
Hutzinger, O.; Fiedler, H. (1991 a) Formation of dioxins and related compounds in.
industrial processes. In: Bretthauer,E.W.; Kraus, H.\/y.; di Dornenico, 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. (1991bj Formation of dioxins and related compounds from
cpn\bustionand incineration processes. In: Bretthauer, E.W.; Kraus, H.W.; di
pprnerjico. A., eds. Dioxin perspectives. A pilot study on international information
exchange on dioxins and related compounds. New York, NY: Plenum Press.
i IP M ,", •>.' ' :, :* '•'. ', i ill i i i f ' . - ' •.
Hutzinger, O; Essers, U.; Hagenmaier, H. (1992) Untersuchungen zur emission
halogenierter diben_zodipxine und dibenzof urane aus yerbrennungsmortoren beim
betrieb mit handelsublichen betriebsstoffen. Universities of Bayreuth, Stuttgart and
Tybjngen, Germany. GSF-Forschungszentrum, Munich, Germany, ISSN 0937-9932.
; ' f: ; " ,,, l,l ,"• ,; ' J[]l I j | j, , | ' • :
Jager, J.; Wilken, M.; Zeschmar-Lahl, B. (1992) Dioxin und furan emissionen in Berlin eine
hpchrechnung. Staub-Reinhaltung der Luft. 52:99-106.
.. •;, .r i • :': ;••• '•'' ,' .ii'iBll ,'.f . \.:.' ••'; ••• -i'l-i; v f 'I i i •: I ••';•.•:'
Jensen, S.; Sundstrom, G.; Frescati, L. (1974) Structures and levels of most
chlorobipheriyls in two technical PCB products and in human adipose tissue. Ambio
..;. ;y ; 3(2):70-76.
Karinan, N.; fanabe, S.;AA/akimoto, T.; Tatsukawa, R. (1987) Coplanar polychlorinated
biphenyls in Aroclor and Kanechlor mixtures. J. Assoc. Off. Anal. Chem. 70(3):451-
;';: "'454. .' ""? ' ! ' " ' ' ' ' '
R-16 • April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Kieatiwong, S.; Nguyen, L.V.; Hebert, V.R.; Hackett, M.; Miller, G.C.; Miille, M.J.; Mitzel,
R. (1990) Photolysis of chlorinated dioxins in organic solvents and on soils.
. Environ. Sci. Technol. 24(10):1575-1580.
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. '-."•'
Klasmeier, J.; McLachlan, M.S. (1995} A screening method for detection of OCDD/F in
textiles. Organohaiogen Compounds 23:131-134.
KMG-Bermuth, inc. (1997) Letter from Thomas H. Mitchell (KMG-Bermuth) to Matthew
Lorber (U.S. EPA/ORD/NCEA). March 5,1997. Houston, TX: KMG-Bermuth, Inc.
Knepper, W.A. (1981) Iron. In: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed.
13:735-753. New York, NY: John Wiley and Sons.
Koester, C.J.; Hites, R.A. (1992) Photodegradation of polychlorinated dioxins and
dibenzofurans adsorbed to fly ash. Environ. Sci. Technol. 26(3):502-507.
Koning, J.; Sein, A.A.; Troost, L.M.; Bremmer, H.J. (1993) Sources of dioxin emissions in
the Netherlands. Organohaiogen Compounds 14:315-318. >.
Krauss, T.; Krauss, P.; Hagenmaier, H. (1994) Formation of PCDD/PCDF during
composting? Chemosphere 28(1 ):155-158.
Kwok, E.S.C.; 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.; Wilken, M.; Zeschmar-Lahl, B.; Jager, J. (1991) PCDD/PCDF balance of different
municipal waste management methods. Chemosphere 23(8-10):1481-1489.
Lahl, U. (1993) Sintering plants of steel industry - the most important thermical PCDD/CDF
source in industrialized regions. Organohaiogen Compounds 11:311-314.
Lahl, U. (1994) Sintering plants of steel industry - PCDD/F emission status and
perspectives. Chemosphere 29(9-11):1939-1945.
Lamparski, L.L.; Stehl, R.H.; Johnson, R.L. (1980) Photolysis of pentachlorophenol-treated
wood. Chlorinated dibenzo-p-dioxin formation. Environ. Sci. Technol. 14(2)-196-
200. ?
April 1998
-------
. DRAFT-DO NOT QUOTE OR CITE
Lamparski, L.L.; Nestrick, T.J.; Cutie, S.S. (1990) The impact on the environment of
airborne particulate matter from the eruption of Mount Saint Helens in May 1980.
In: Clement, R.; Kogel, R., eds. Emissions from combustion processes: origin,
ijj§• ; iifV;; ; £,::. rr}|asureni'fpt, control. Chelsea, Ml: Lewis Publishers.
Larsen, B.; Bowadt, S.; Facchetti, S. (1992) Separation of toxic congeners from PCB
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, B.R. (1995) HRGC separation of PCB congeners. J. High Resol. Chromatogr.
'i;1:; •;'• : j" ,"18:141-151. : ' ' '• ;
Larsspn, P.; Lemkemeier, K. (1989) Mlcrobial mineralization of chlorinated phenols and
biphenyls in sediment-water systems• from humic and clear-water lake. Water
'»-••;'•! •': • - " '•: "'•': Research ' 23(9): 108i-1085." " '''
Larssen, S.; Brevick, E.M.; Oehme, M. (1990) Emission factors of PCpD and PCDF for
road vehicles obtained by a tunnel experiment. Organohalogen Compounds 1:453-
456,,.,; "™..;.. i ;, ;",;'";,_; ;,,/' ^(;;;_';,""," ",;,"„„',„„"„; '",, ,;;..'..,...'.' ', , •
Leifer, A.; Brink, R.H.; Thorn, G.C.; Partymiller, K.G. (1983) Environmental transport and
transfprrnatjpn of pplychlprinated biphenyls. Washington, D.C.: U.S. Environmental
Protection Agency, Office of Toxic Substances. EPA-560/5 83-025.
Lemieux, P.M. (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.
Lepine, F.; Milot, S.; Vincent, N. |1992) Formation of toxic PCB congeners and PCB-solvent
adducts in a sunlight irradiated cyciohexane solution of Aroclor 1254. Bull. Environ.
Contam. Toxicol. 48:152-156.
/.'. • i i iji, i I ' i i i i
Lew< G. (1993) Letter to John Schaum concerning CARB (1987) draft report on
CPP/QDFs.in vehicle exhausts. .Sacrarnento, CA: California Air Resources Board,
Monitoring and Laboratory bivisipn. Availablei 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;ii, 1996. Sacramento,
CA: State of California Air Resources Board, Engineering and Laboratory Branch.
Available for inspection at: U.S. Environmental Protection Agency, Office of
Research and Development, National Center for Environmental Assessment,
Washington, D.C.
Lexen, K.; De Wit, C; Jansson, B.; Kjeller, L.O.; Kulp, S.E.; Ljung, K.; Soderstrom, G.;
Rappe, C. (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.
" ! ' I ' I I '•:'•'",
R-18 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
J i
Lofroth, G.; ZebiJhr, Y. (1992) Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans
(PCDFs) ,in mainstream and sidestream cigarette smoke. Bull. Environ. Contam
Toxicol. 48:789-794. , .
Lorang, P.A. (1996) Comments on the API document: A study to quantify on-road
emissions of dioxins and furans from mobile sources: phase 2. Ann Arbor, Ml:
U.S. Environmental Protection Agency, National Vehicle and Fuel Emissions
Laboratory. Memorandum dated December 1996.
Lorenz, W.; Wichmann, H.; Bahadir, M. (1996) Balancing of the release of poJychlorinated
dibenzo-p-dioxins and dibenzofurans in fire accidents-a contribution to the
discussion. Reinhaltung der Luft. 56:49-53.
Luijk, R.; Covers, H.A.; 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.
Lykins, B.W.; Clark, R.; Cleverly, D.H. (1987) Polychlorinated dioxin and furan discharge
during carbon reactivation. Journal of Environmental Engineering 114(2): 330-316.
Malisch, R. (1994) Determination of PCDD/PCDF in PCB products and milk samples;
correlation between PCB- and PCDD/PCDF-contamination of milk samples,
Organohalogen Compounds. 20:209-214.
Malloy, T.A.; Goldfarb, T.D.; Surico, M.T.J. (1993) PCDDs, PCDFs, PCBs, chlqrophenols
(CPs) and chlorobenzenes (CBzs) in samples .from various types of composting
facilities in the United States. Chemosphere 27(1-3):325-334.
Maniff, K.; Lewis, M. (1988) MISA monitoring discovers dioxins and furans in wastewater
stream of petroleum refinery. Ministry of the Environment Communique.
Decembers, 1988.
Marklund, S.; Rappe, C.; Tysklind, M.; Egeback, K.E. (1987) Identification of
Polychlorinated dibenzofurans and dioxins in exhausts from cars run on leaded
gasoine. Chemosphere 16(1):29-36.
Marklund, S.; Andersson, R.; Tysklind, M.; Rappe, C. (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.; Rappe, C.; Egebaqk, K.E.; Bjorkman, Er;
Grigoriadis, V. (1990) Emissions of PCDDs and PCDFs in gasoline and diesel fueled
cars. Chemosphere 20(5):553-561.
Matsueda, T.; Kurokawa, Y.; Nakamura, M.; Takada, S.; Fukamachi, K. (1994)
Concentrations of PCDDs, PCDFs and coplanar PCBs in cigarettes from various
countries. Organohalogen Compounds 20:331-334.
R"19 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
McCrady, J.K.; Maggard, S.P. (1993) Uptake and photodegradation of 2,3,7,8-
tetrachlorodibenzo-p-dioxin sorbed to grass foliage. Environ. Sci. technol. 27:343-
350.
Mejk, M.; Schramm, K.W.; Lenoir, D.; Henkelmann, B.; Kettrup, A. (1995) Determination
of the PC'CJp/F concentration in the jumes, frpm ^ PVC fire. 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, J.T. (1994) Wood preservation statistics, 1993. A report to the wood
preserving industry in the United States.
Mill, T.; Rossi, M.j McMiIlen{ D.; Coville, ML; Leung, D.; Spang, J. (1987) Photolysis of
tetrachlprgdipxjn and^pCBs^under^tm^pheric conditions. Internal report prepared
by SRI International for U.S. Environmental Protection Agency, Office of Health and
Environmental Assessment, Washington, D.C.
Ill I I . •: ' . ' ' i1 • '.
Miller, A. (1993) bioxin emissions from EpC/VCM plants. Environ. Sci. Technol.
27:1014-1015.
Miller, G.C.; Hebert, V.R.; Miille, M.J.; Mitzef, R.; Zepp, R.G. (1989) Photolysis of
ocfachlprqdibenzo-p-dioxin on soils: production of 2,3,7,8-TCDD. Chemosphere
18:1265-1274.
Mprimpto, K.; Kenji, T. (1995) Effect of humic substances on the enzymatic formation of
OCDD from PCP. prganphalogen Compounds 23:387-392.
Muto, H.; Takizawa, Y. (1989) Dioxins in cigarette smoke. Archives of Environmental
Health 44(3): 171-174.
Mtftp, H.; Takizawa, Y. (1992J Potentialhealth risk via inhalatipn/ingestion exposure to
pblychlorinated dibenzo-p-dioxins and dibenzofurans. Bull. Environ. Cpntam. Toxicol.
' 49:701-767. _' '.. 7 V ;''." l!""' '",:: „'':""':;;: • ' ;:'''; ••••••
Nif, C.; Broman, D.; Ishaq, R.; Zebiihr, Y. (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 26(l6-12):1563-i510.
NATO (North Atlantic Treaty Organization) (1988) .Pilot study on international information
exchange on dioxins and related compounds: Emissions oTdioxins and related
compounds from combustion and incineration sources. .North Atlantic Treaty
Organization, Committee on the Challenges of Modern Society. Report #172.
August 1988.
R-20 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
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 (National Council of the Paper Industry for Air and Stream Improvement) ,(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, T.J.; Lamparski, L.L. (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, T.J.; Lamparski, L.L. (1983) Assessment of chlorinated dibenzo-p-dioxin formation
and potential emission to the environment from wood combustion Chemosohere
12(4/5):617-626.
Nies, L.; Vogel, T.M. (1990) Effects of organic substrates on dechlorination of Aroclor
1242 in anaerobic sediments. Applied and Environmental Microbiology 56(9):2612-
2617.
Oberg, L.G.; Glas, B.; Swanson, S.E.; Rappe, C.; Paul, K.G. (1990) Peroxidase-catalyzed
oxidation of chlorophenols to polychlorinated dibenzo-p-dioxins and dibenzofurans.
Arch. Environ. Contam. Toxicol. 19:930-938.
Oberg, L.G.; Rappe, C. (1992) Biochemical formation of PCDD/Fs from chlorophenols
Chemosphere 25(1-2):49-52.
Oberg, L.G.; Andersson, R.; Rappe, C. (1992) be novo formation of hepta- and
octachlorodibenzo-p-dioxins from pentachlorophenol in municipal sewage sludge.
Organohalogen Compounds 9:351-354.
Oberg, L.G.; Wagman, N,; Andersson, R.; Rappe, C. (1993) De novo formation of PCDD/Fs
in compost and sewage sludge - a status report. Organohalogen Compounds
11 =297-302.
Oberg, L.G., Wagman, N.; Koch, M.; Rappe, C. (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 polychjorinated dibenzofurans and
dibenzo-p-dioxins by production processesfor magnesium and refined nickel.
Chemosphere 18(7-8) :1379-1389.
* "
Oehme, M.; Larssen,S.; Brevik, E.M. (1991) Emission factors of PCDD/CDF for road
vehicles obtained by a tunnel experiment. Chemosphere 23:1699-1708.
R"21 ' April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Office of Nature Conservancy (1991) Organochlorine compounds from dishwashing
detergents and bleach? Sweden Office of Nature Conservancy Report No. 4009.
jiiiji":!1 , |, „ .''jj11' i" >, 'in1 HI.' t . i'< jjiii •., . '!".., "„" i1 '',,, i1,"1 j'!•!.,ill!" ,;, ; L, '!• ,.,» ,";1 '.iiit ' '',, \*tf* V i "iir1 .' i;i»,,:,ii° ,.', 'i '" ' hiin,'1'!,'"i"" :"i. . i" , . , V . . , ,
O'Keefe, P.W.; Smith, R.M. (1989) PCB capacitor/transformer accidents. In: Kimbrough,
R.D.; Jensen, A.A., eds. Halggenated biphenyls, terphenyls, napthalenes,
dibenzpdioxjns and related products. New York, NY: Elsevier Science Publishers.
£ '•',', V/V ' ' Jill '" i i ' ' ' ';•''' ' ' ' '•
Opatick, R.E. (1995) Chlorobenzene Producers Association comments on EPA's external
review draft of Estimating Exposure to Dioxin-Like Compounds. Chlorobenzene
Producers Association. January 10, 1995.
Orazio, C.E.; Kapila, S.; Puri, R.K.; Yanders, A.F. (1992) Persistence of chlorinated dioxins
and furans in the soil environment. Chernosphere 25{7-10):1469-1474.
O'Rpurke, 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 invironmental AssessmenVWashington, D.C.
Palmer, F. H.; Sapudar, R.A.; Heath, J.A.; Richard, N.J.; Bowes, G.W. (1988) Chlorinated
d contamination in California from chlorophenol
:"»;* •! .T* *"'•';'?„ '"J i» i v;, . 1^,1 i JE i "Vi n i i n i . r .
Vvopd preservative use. California State Water Resources Control Board. Report No.
; 1: '88-5WQ.'"" "' '": "::"":'"! '" •'"'l''"" """: "Ci '"'"'" -i1 "••"•*•'• ;
i',!'1!" !': 1,1 I I I : • I
Pardue, J.H.; Delaune, R.D.; Patrick, W.H. (1988) Effect of sediment pH and oxidation-
reduction potential on PCB mineralization. Water, Air and Soil Pollution 37:439-
447.
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.
,, '•' i • „ ' , .A ' . iliRLHI '«.:! ii ''i'". .;« " niiK '.iirvil". „ .", , ' ' I,H. " • |. V ' „„ %\" , fni , ' ^ •' • ! • n, 'V ' «.' . • 'ftin'ii1, , ' > .\ . . , '
Persson, P.E.; Bergstrpm, J. (1991) Emission of chlorinated clioxins from landfill fires.
Proceedings Sardinia 91: Third International Landfill Symposium, pp. 1635-1641.
Plimmer, J.R. (1980) Herbicides. In: Kirk-Qthmer Encyclopedia of Chemical Technology.
3rd ed. Vol. 12, pp. 297-351.
Quensen, J.F.; fiedje, J.M.; Boyd, S.A. (1988) Reductive dechlorination of polychlorinated
biphenyls by anaerobic microorganisms from sediment. Science 242:752-754.
Quensen, J.F.; Boyd, S.A.; Tiedje, J.M. (1990) Dechlorination of four commercial
polychlorinated biphenyl mixtures (Arbclors) by ar^erobic microorganisms from
sediments. Appl. Environ. Microbiol. 56(1 j:2360-2369.
' ' ' " '" " ' "'
/;, R-22 , ^ • ,. , April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
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, Re'search 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. (1992a) Sources of PCDDs and PCDFs. Introduction. Reactions, levels, patterns,
profiles and trends. Chemosphere 25(1-2):41-44..
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.; Marklund, S.; Buser, H.Ri; Bosshardt, H.P. (1978a) Formation of
polychlorirtated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) by burning or
heating chlorophenates. Chemosphere 3:269-281.
Rappe, C.; Gara, A.; Buser, H.R. (1978b) Identification of polychlorinated dibenzofurans
(PCDFs) in commercial chlorophenol formulations, Chemosphere 12:981-991.
,• • * • , • • .
Rappe, C.; Kjeller, L.O.; Bruckmann, P.; Hackhle, K.H. (1988) Identification and
quantification of PCDD/CDFs in urban air. Chemosphere 17(1 ):3-20.
Rappe, C.; Kjeller, L.O.; 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.; Kringstad, K.P.; de Sousa, P.; Zehsaku, A. (1989b)
Formation of PCDDs and PCDFs by the chlorination of water. Chemosphere
19(12):1875-1880. •
i • • .
Rappe, C.; Kjeller, L.O.; Kulp, S.E. (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, L.O.; Kulp, S.E. (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.; Wiberg, K.(1990c) Levels of,polychlorinated
dioxins and dibenzofurans in commercial detergents and related products
Chemosphere 21(1-2):43-50.
Rappe, C.; Kjeller, L.; Kulp, S.; deWit, C.; Hasselsten, I.; Palm, O. (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.
. R'23 April 1998
-------
j •"•'" !•' " '• i"! ':. '" " ,i
DRAFT-DO NOT QUOTE OR CITE
Rappe, C.; Andersson, R.; Karlaganis, G.; Bonjour, R. (1994) PCDDs and PCDFs in
samples of sewage sludge from various areas in Switzerland. Organohalogen
Compounds 20:79-84.
Ree, K.C.; Evers, E.H.G.; Van Der Berg, M. (1988) Mechanism of formation of
polychlorinated dibenzo(p)dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs) from potential industrial sources. Toxicological and Environmental
Chemistry 17:171-195.
Remmers, J.; Dupuy, A.; McDaniel, D.; Harless, R.; Steele, D. (1992) Polychlorinated
dibenzp-p-dioxin and dibenzofuran contamination in chloranil and carbazole violet.
Chemosphere 25(7-10):1505-1508.
RheerG.Y.; Bushf B.; Brown, M.P.; KnefM.; Shane, L. (1989) Anaerobic biodegradation
of polychlorinated biphenyls in Hudson River sediments and dredged sediments in
clay encapsulation. WaterResearch 23{8):957-964.
Rieger, R.; Ballschmiter, K. (1992) Search for sources of CLxDD/CLxDF in sewage sludge of
mixed industrial/domestic origin. Organohalogen Compounds 9:203-206.
Rijjgs, K.B.; Brown, T.D.; Schrock, M.E. (1995) PCDp/PCDF emissions from coal-fired
power plants. Organohalpgen Compounds 24:51-54.
Risatti, J.B. (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.
Retard, W. (1993) Fires. In: Current views on the impact of dioxins and furans on human
health and the environment. Washington, D.C.: Toxicology Forum, Inc.
Rufcifn, A.; Whitet C. (1993) 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.
Rupkojarvi, P.; Ettala, M.; Rahkonen, P.; Tarhanen, J.; Ruuskanen, J. (1995)
Polychlorinated dibenzo-p-dioxins and -furans (PCDDs and PCDFs) in municipal
waste landfill fires. Chemosphere 3b'(9):i697-1 yog;
Safe, S. (1994) Polychlorinated biphenyls (PCBs): environmental impact, biochemical and
toxic responses, and implications for risk assessmentl Crit. Revl Toxicoll 21(1):51-
• ' 88.
R-24 April 1998
\
-------
DRAFT-DO NOT QUOTE OR CITE
SAIC (.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.
Sakai, S.; Hiraoka, M.; Takeda, N.; Shiozaki, K. (1993a) Coplanar PCBs and PCDD/PCDFs
in municipal waste incineration. Chemosphere 27(1-3)-.233-240.
Sakai, S.; Hiraoka, M.; Takeda, N.; Shiozaki, K. (1993b) On emissipn and formation of
nori-ortho CBs and mono-ortho CBs in municipal waste incineration. Organohalogen
Compounds 11:245-248.
Sakai, S.; Hiraoka, M.; Takeda, N.; Shiozaki, K. (1994) Behavior of coplanar PCBs in
oxidative condition of municipal waste incineration. Organohalogen Compounds
20:309-313. .
Santl, H.; Gruber, L.; Stohrer, E. (1994a) Mass balance of polychlorinated dibenzofurans
(PCDFs) and polychlorinated dibenzodioxins (PCDDs) in a recycling paper mill.
Chemosphere 28(9-11 ):1633-1639.
Santl, H.; Gruber, L; Stohrer, E. (1994b) Investigation on the input, formation and fate of
polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) in the pulp and
paper industry. Chemosphere 29(9-11):1987-1994.
Santl, H.; Gruber, L.; Stohrer, E. (1994c) Some new sources of polychlorinated
dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) in waste papers and recycled
pulps. Chemosphere 29(9-11):1995-2003.
Schafer, K.; McLachfan, M.S.; Beissinger, Ml; Hutzinger, O. (1993) An investigation of
PCDD/F in a composting operation. Organohalogen Compounds 11:425-428.
Schatowitz, B.; Brandt, G.; Gafner, F,; Schlumpf, E.; Biihler, R.; Hasler, P.; Nussbaumer, T.
(1993) Dioxin emissions from wood combustion. Organohalogen Compounds
11:307-310. ,
Schecter, A.; Papke, O.; Isaac, J.; Hrimat, N.D.; Neiroukk, F.; Safi, J.; EI-Nahhal, Y. (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!
Schoonenboom, MTH.; Tromp, P.C.; Olie, K. (1993) The formation of coplanar PCBs,
PCDDs and PCDFs in a fly-ash model system. Organohalogen Compounds 11 -277-
280.
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.
R"25 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Schreiner, G.; Schimmel, H.; Ballschmiter, K. (1995) Influence of the substitution pattern
of) the micrpbial degradation of mono-to tetrachlorinated dibenzofurans and
dibenzodioxins. Organohalogen Compounds 24:43-46.
Schulz, D.E.; Petrick, G.; Duinker, J.C. (1989) Complete characterization of polychlorinated
biphenyl congeners in cornmerical Aroclpr and Clophen mixtures by multidimensional
gas chromatography-electron capture detection. Environ. Sci. Technol. 23:852-859.
Schwartz, T.R.; Tillitt, D.E.; Feltz, K.P.; Peterman, P.H. (1993) Determination of mono- and
npn~o-o'-chlorine substituted pplychlprinated biphenyls in Aroclors and
environmental samples. Chemosphere 26(8):1443-1460.
Schwind,'K-riV; THpma, H.; Hutzinger, p.; Dawidowsky, N.; Weberuss, U.; Hagenmaier, H.;
Buehler, U.; Greiner, R.; Essers, U.; Bessey, E. (1991) Emission halogenierter
dibenzodibxine (PXbb) urid dibenzofurane (PXDF) aus verbrennungsmotoren.
UWSF-Z. Umweltchem. pekotox. 3, 291-298. [English translation]
Schwind, K.H.; Hpsseinpour, J.;Fiedler, H.; Lau, C.; Hutzinger, O. (1995) Human
exposure to consumer products: analysis of chlorinated organic compounds in
candles and their exhaust fumes. Organohalogen Compounds 26:113-116.
Seppr International Inc. (1995a) Emission measurement results for furahs and dioxins from
the main stack at the Phelps Dodge-Hidalgo Smelter, Playos, New Mexico. Prepared
for the Phelps Dodge iVlinihg Company.
' ,,'ih ''' . i'1 I l!l ,if "'' SIII'lilM1 ir , ' . ' ,n >,i ' I'ill I:,1" ill," ,' .i'i '' il.'i'l1 . I IM ,? ' ,' ," i,i'» •' , ' " 'I1!!' '" ill 'I
Secor International Inc. (i995b) Furans and dioxins emission measurement results for
Cyprus Miami Mining Corporation. Prepared for the Cypress Amax Minerals
Company.
Sediak, D.L.; Andren, A.W. (1991) Aqueous-phase oxidation of polychlorinated biphenyls
by hydToxyi radicals. Environ. Sci. Technol. 25(8):1419-1427.
Sewart, A.; Harrad, S.J.; McLachlan, M.S.; McGrath, S.P.; Jones, K.C, (1995) PCDD/Fs
and non-o-PCBs in digestedI U.K. sewage sludges. Chemosphere 30(1):51-67.
Shane, B.S.; Henry, C.B.; Hotchkiss, J.H.; Klausner, K.A.; Gutenmann, W.H.; Lish, D.J.
(1990) Organic toxicants and mutagens in ashes from eighteen municipal refuse
incinerators. Arch. Environ. Contam. Toxicol. 19:665-673.
Sivfis, L.Dl; Kapila* S.; Van, Q.; Elseewi, A A. (1994) Studies on gas-phase
phototransformation of polychlorinated dibenzo-p-dioxins. Organohalogen
Compounds 1 9:349-353.
";>i ' ' ' -. , • I'Hi'Ji!: !"' .•• •."! ',''
I'Hi'Ji!: !"' .•• •."! ','' ".1 -;!-i.', ;- ...... ,•,»! v'ti ;
Sivils, L.D.; Kapila, S.; Yan, Q.; Zhang, X.; Elseewi, A.A. (1995) Studies on vapor phase
phototransformation of poiychlorinated dibenzo-p-dioxins (PCDDs): effect of
environmental parameters. Organohalogen Compounds 24:167-172.
R-26 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Solid Waste Technologies. (1994) A comprehensive statlis report on MSW waste-to-
energy facilities, incinerators refuse-derived-fuel, and tire processing facilities
throughout North America. Kansas City, MO: HCI Publications. 84pp.
Someshwar, A.V.; Pinkerton, J.E. (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.
Springer, J.M. (1997) Personal communication with A. Paintal, Versaf, Inc. Cremation
Association of North America. January 7, 1998.
Strandell, M.E.; Lexen, K.M.; deWit, C.A.; Jarnberg, U.G.; Jansson, B.; Kjeller, L.O.; Kulp,
E.; Ljung, K.; Soderstrom, G.; Rappe, C. (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, R.L.; Costner, P.; Johnston, P.A. (1995) PVC manufacture as a source of
PCCD/Fs. Organohalogen Compounds 24:119-123.
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.
Stuart, B.; Carter, D.; Hoodless, R.A. (1993) Report on the examination of sewage
sludges for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.
London, England: Laboratory of the Government Chemist.
Svenson, A.; Kjeller, L.O.; Rappe, C. (1989) Enzyme-mediated formation of 2,3,7,8- ,
tetrasubstituted chlorinated dibenzodioxins and dibenzofurans. Environ. Sci.
Technol. 23 (7): 900-902.
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.
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,; Kannan, N.; Wakimoto, T.; Tatsukawa, R. (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.
R'27 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Ta,shiro, C.; Clement, R.E.; Stocks, B.J.; Radke, L.; Cofer, W.R.; Ward, P. (1990)
Preliminary report: dioxins and furans in prescribed burns, Chemosphere 20:1533-
1536.
Taylor, A. and Zannes, M. (1996) The 1996 IWSA municipal waste combustion directory
of United States facilities. Integrated Waste Services Association. 16pps.
I "Hill, ,i ' ',•" t : '''„."!''i, i, ,'•: • '"'*. "i, • ,'i ¥!!'/:'"'ill'1 I1',:"1. I!,'"11' •'" !, I""1' '.„. i1 Tn ."', !, • •' ,• :,"'•':. • ' IK •!' • .' •'','• |. , •
The Aluminum Association (1997) U.S. aluminum industry plant directory, November
1997. Washington, DC: The Aluminum Association.
n ii i i i: ' . i!
The Tobacco Institute (1995) Tobacco industry profile 1995. Washington, DC: The
Tobacco Institute.
H I III II -'I '•
The Vinyl Institute (1996) Dioxin^haractenzatipn^prpigram. Interim Phase I Report.
Morristovyii, NJ: The Vinyl instituW November 1, 1996^
MV /., E.j_ Kpnig, J. (1989) Determinatipn of PCDFs and PCDDs
in fire accidents and laboratory combustion tests involving PVC-containing materials.
ill; •. ,, i.t,"(i"; ,f'!,f. I ; . I0II :K»W .ft;l CWiHI ISM iillVr'i - vn ,n • -.1 , a. ,.i a
Chemosphere 19(1 -6):423-428.
Thpma, H.; Hutzinger, O. (1989) Content and formation of toxic products in flame
';;,;!'!'' ' < ! mi |j||'|ii"| if!,,,, ,;l||ll"'|j, ," '' 'I IPi'll'iilj I, ::!' .« '« !< li|i"iii''i'.'l I"!,,', "II >, 'i: Jllll'1!' ' I' ' ' I.I 'i;i ''I' 'I ill,," ini !i,!,' ,'i ' lid" '"» ii «i,i M ,' i ' ,
-------
DRAFTT-DO NOT QUOTE OR CITE
7 :' - ' ' ' • . ' ' • ' , ' . . '. '
Tysklind, M.; Soderstrpm; Rappe, C.; Hagerstedt, L-E.; Burstrom, E. (1989) PCDD and
PCDF emissions from scrap metal melting processes at a steel mill. Chemosphere
19(1-6):705-710. . • ' • • • :
Tysklind, M.; Rappe, C. (1991) Photolytic transformation of polychlorinated dioxins and
dibenzofurans in fly ash. Chemosphere 23(8-10):!365-1375.
Tysklind, M.; Carey, A.E.; Rappe, C.; Miller, G.C. (1992) Photolysis of OCDF and OCDD
on soil. Organohalogen Compounds 8:293-296.
Umlauf, G.; Horstmann, M.; Klein, P.; Kurz, J. (1993) Mass balance of PCDD/F in a dry
cleaning machine. Organohalogen Compounds 11:413-416.
- -.- -• ) t • '
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 Dioxjn-Like Compounds." Comments submitted to EPA's
Office of Health and Environmental Assessment. January 10, 1995.
U.S. Department of Agriculture (1997) Tobacco leaf and products statistics and analysis.
Washington, DC: U.S. Department of Agriculture, Economic Research Service.
U.S. Department of Commerce (1990a) 1987 Census of manufactures. Smelting and
refining of npnferrous metats and alloys. Washington, DC: Bureau of the Census
Report No. 33C-18.
U.S. Department of Commerce (1990b) 1987 Census of manufacturers. Soap, cleaners,
and toilet goods. Washington, DC: Bureau of the Census. Report No MC-87-I-
28D.
U.S. Department of Commerce (1990c) 1987 Census of manufactures. Industrial
inorganic chemicals. Washington, DC: Bureau of the Census. Report No MC87-I-
28A.
U.S. Department of Commerce (1995a), Statistical abstract of the United States 1995
118th ed. ••'-"•
U.S. Department of Commerce (1995b) 1992 Census of transportation. Truck inventory
and use survey. Washington, DC: Bureau of the Census. Report No. TC92-T-52.
U.S. Department of Commerce (1995c) 1992 Census of manufactures. Smelting and
refining of nonferrous metals and alloys. Washington, DC: Bureau of the Census
Report No. MC92-I-33C.
R"29 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
U.S. Department of Commerce (1995d) 1992 Census of manufactures. Blastfurnaces,
steel works, and rolling and finishing mills. Washington, DC: Bureau of the Census.
'-' 4':!:;: Report Mo I MC92-I-33A. '
(J.S. Department of Commerce (1996) 1992 Economic census report series - disc 1G.
;|Washington, DC: Bureau of the Census. Cp-EC92-1C3.
U.S. Department of Commerce {1997) Statistical abstract of the United States, 1997.
117th edition. Washington, DC: Bureau of the Census.
U.S. Department of Health and Human Services (DHHS) (1989) Toxicology and
caicinogenesis studies of two pentachlprophenol 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.
I1 mi I i i i i : .•"'•'.
U.S. Environmental Protection Agency; Environment Canada (1991) The environmental
characterization of RDF combustion technology. Mid-Connecticut facility,
Hartford,Cf. Test program and results, volume II., June 1991.
Ill' j J I '' '
U.S. Environmental Protection Agency. (1979) Polychlorinated biphenyls (PCBs) in
manufacturing, processing, distribution in commerce, and use prohibition: Final rule.
Federal Register 44:31514-31568.
: III III I I I I I I ' ' '!' • .
U.S. Environmental Protection Agency (1982a) Development document for effluent
limitations guidelines and standards for the inorganic chemicals manufacturing point
source category. Washington, DC: officei of WateV ReguiatJons and Standards. EPA
440/1-82/007.
U.S, Environmental Protec,tipn Agency (1982b) Development document for effluent
limitations guidelines and standards for the iron and steel manufacturing point
source category. Volume ll. Washington^DC: Office of Water. EPA-440/1-
82/024. -
U.§. Environmental Protection Agency (1984) Thermal degradation products from
dielectric fluids. Washington, DC: Office of Toxic Substances. EPA-560/5-84-009.
U.S. Environmental Protection Agency (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. EnvironmentgJ protection Agency (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. Environmental Protection Agency (1987c) Locating and estimating air emissions from
soufceS; of pplychlorinated biphenyls (PCB). Research Triangle Park, NC: Office of
Air Quality Planning and Standards^ ^pj^_^Qi^_ig^_QQjn
\ , • • ':.; ''itSl "t1,-', ' '' -,''.' •:.;/' ' .,'" ;V;i ,v,,'-i''|(^-' f. •'• *|l|!l J,;;' ,••'., j ' •%.
R-30 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
U.S. Environmental Protection Agency (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. Environmental Protection Agency (1988a) U.S. EPA cooperative dioxin screening
study. Washington, DC: .Office of Water Regulations and Standards. EPA-440/1-
88-025. „ . .
U.S. Environmental Protection Agency (19885) 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. Environmental Protection-Agency (1988c) Pesticide industry sales and usage: 1987
market estimates. Washington, DC: Office of Pesticide Programs.
U.S. Environmental Protection Agency (1989) 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. Environmental Protection Agency (1990a) Summary report on USEPA/lndustry
Cooperative Dioxin Study. "The 104 Mill Study." Washington, DCt Office of Water
Regulations and Standards. July 1990.
U.S. Environmental Protection Agency (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. Environmental Protection Agency (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. Environmental Protection Agency (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. Environmental Protection Agency (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. Environmental Protection Agency (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. Environmental Protection Agency (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.
\ , • ' '
R~31 April 1998
-------
DRAFT»E>Q NOT QUOTE OR CITE
UIS. Environmental Protection Agency (1991 d) Medical and institutional waste
incineration: regulations, management, technology, emissions, and operations.
Cincinnati, OH: Center for Environmental Research information. EPA/625/4-
;«; ': 91/030." ' '" i ; ;; I ' ' \ ;
U.S. Environmental Protection Agency (1992a) Markets for scrap tires. Washington, DC:
Office of Solid Waste arid Emergency Response. EPA/530-SW-90-074A.
U.S. Enyirqnrnenlgl Protection Agency (1992b) Industry agrees to switch to low-dioxin
chloranil from contaminated chloranil. Chemicals in Progress Bulletin 12(2):23. ,
U.S. Environmental Protection Agency (1992c) 1990 National census of pulp, paper, and
paperboard manufacturing facilities. Response to 308 questionnaire. Part A:
Technical Information, Washington, DC: Office of Water.
HI , H. , n ' ',, „ '" ,,,,i i infill'1!1! • , • i" i ' " ,,, "• ',„ • 'iHil'"1 i,,.:i' I;,1; . 'I'll.11, ',,"r' '"'./"i!!1,,:1 „ '! \|i i ', ' !": i'i,!'' !'• : , ' f ';;"' ' 'In 'JT ! "", , I
U.S. Environmental Protection Agency (1992d) Economic impact and preliminary regulatory
impact analysis for proposed MACT-based emission standards and guidelines for
municipal wastecbmbustgrs. Research TrianglePark, 8VIC: Off ice of Air Quality
Planning and Standards. EPA-450/3-91-029.
U,S. Environmental Protection Agency (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.
: ' ' i> " :"'. i:'w '!'; ,:• ."" :;;, ,=;; v :-,"-j':i',".. :.":.,",.;.. , '•,.,:. "-:•, '.: . :*'";:! r
/, i : -; .aji: ';,, i-, .vi.'i |i) Jin, •''. ;•, •'..'; Mci'ii,:-,," •. vx:'.";/7 ,'rs '•*•'{.'• • " :!i >•:,* ' •' si ;
U.S. Environmental Protection Agency (1993a) 1992 Needs survey report to Congress.
Washington, DC: Office of Water. EPA-832-R-93-002.
U.S. Environmental Protection Agency (1993b) States support efforts on forming
voluntary agreement on pulp and paper mill sludge! Chemicals in Progress Bulletin
':= y 14(3):2Q. , . ,V "]'.' ' ,.. ..'.'''.!.'"!' ." .7! " "' ..' '..'.,.'. , ! ' .'
: .Si- ]', "'"' '',':. fill ,!,,'-,. •"! •'" -.'iv' i-ilS:;' i! •':,.»;; :'^.f" .';.:.i*':- ;i;'!;i-; y,"l ,,'!':'..if.:'~. -lii"'":'1''1 ••• ; "\ ... •'
U.S. Environmental Protection Agency (1993c) EPA publishes proposed rule for chloranil.
;!|il;' ' < . ;, ' S5T !•• i, !,;:"!,„ f.' .,..' '' -S ' , , ., ; .•.. ' . 'R> .,. ,: ..-,•,>. , mi,-, ". • .:", i . .
Chemicals in Progress Bulletin 14(2):26.
,i, ', '„,,,„IT1,,, ' I'll1" i
U.S. Environmental Protection Agency (1993d) Development document for proposed
effluent limitations guidelines and standards for the pulp, paper and paperboard point
source catlgdryl Washington, DC: Office of Water EPA-821-R-93-019.
11 „ i. ' ' i1,!,11!'1!!;!.'! 'ii. • ' i . ', »' ,: , ,,i! ,' i| ' '!,', i,1,, i ,. ,,!„ : .."'.' i, ti U'T Wl '/ ,.!«!' ,• .'JW.Ii,:!!1 . , ' "' • . ' • I ,
U.S, Environmental Protection Agency (1993e) Economic analysis of impacts of integrated
air/water regulations for the pulp and paper industry on disposal of wastewater
,,' |!i , ' • '' ' ' Him ,, »i, , ,< , i,:.i v, a 'i , ,«! ,,i ",;i «,!i " !L !' UK, "iv'„,I1 M, , ;:i'.!",'i i[il'i1 J| "hi>,li'ill, 'in '< ii "H"' 'I'1 • H1 Jlr "I' '"I " ..' I
sludge. Washington, DC: Office of Pollution Prevention and Toxics, Regulatory
Impacts Branch.
U.S. Environmental Protection Agency (1993f) Press advisory: EPA terminates special
review of non-wood pesticide uses of pentachlorophenol. Washington, DC: Office
of Pesticide Programs. January 8, 1993.
R-32 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
U.S. Environmental Protection Agency (1993g) Report to Congress on cement kiln dust:
Washington, DC: Office of Solid Waste. December 1993.
U.S. Environmental Protection Agency (1993h) 1991 Toxics release inventory - public
data release. Washington, DC: Office of Pollution Prevention and Toxics EPA-
745-R-93-003. . _ " • .
U.S. Environmental Protection Agency (1994a) 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.
U.S. Environmental Protection Agency (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. Environmental Protection Agency (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. Environmental Protection Agency (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. Environmental Protection Agency (1994e) Universe of hazardous waste combustion
facilities. Washington, DC: Office of Solid Waste and Emergency Response EPA-
530-F-94-030.
U.S. Environmental Protection Agency (1994f) Combustion emissions technical resource
document (CETRED). Washington, DC: Office of Solid Waste and Emergency
Response. Draft Report. EPA/530-R-94-014.
U.S. Environmental Protection Agency (1995a) SRRD's dioxin/furan status report.
Washington, DC: Office of Pesticide Programs, Special Review and Reregistration
Division. September 12, 1995.
U.S. Environmental Protection Agency (1995b) Compilation of air pollutant emission
factors. 5th edition. Research Triangle Park, NC: Office of Air Quality Planning and
Standards.
U.S. Environmental Protection Agency (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.
R'33 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
i t'Si!1-"
U.S. Environmental Protection Agency (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 Measure'ment Branch. EMB Report No. 93-SLS-1 .
j'ifi ' ;„'" ' "'! ™ ,! ;' , ...... . s1::1::,!! "" ' ...... / I i > /!:> of -.; " .' • . nfi, ,: ? V :' \ \ • , >• j
U.S. Environmental Protection Agency (1 995e) 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
Plannipg and Standards, Emission Measurement Branch. EMB Report No. 93-SLS-2.
"if!- .'/ .. •. "*"•.:•• v..., it in ii 1 1 I ill i I', •''.;'.,•!'.
U.S. Environmental Protection Agency (1995f) 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 (1460) September 'fSfd'Si EPA:SAB-EC-95-()2l .
U.S. Environmental Protection Agency (1995g) 199i3 Toxics release inventory - public
data release. Washington, DC: Office of Pollution Prevention and Toxics. EPA-
' " ' '
U.S. Environmental Protection Agency (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. Environmental Protection Agency (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.
1 ||| i / . • ,li, ,„;;]!' i i , • '';• ''in,!,,! " f |'!i ill,,) I '' ''',' ' ,( l! Si!,",,' ,'", i I'lyi'1 Mfti* i', , 'i M ,»' , 'i',,,, "i • i" II..IH i,« i iii" i ,, ii , , i.iii .', 11 if i i
U.S. Environmental Protection Agency (1996b) Municipal solid waste factbook, version
3.0. Wasnlngton, DC: Office of Solid Waste.
U.S. Environmental Protection Agency (1996c) EPA OSW hazardous waste combustion
data base. Washington, DC: U.S. EPA, Office of Solid Waste.
U.S. Environmental Protection Agency (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. Environmental Protection Agency (1996e) National dioxin emissions from medical
wastei incinerators. Research Triangle Park, NC: Office of Air Quality Planning and
Standards. Docket #A-91-61, Item IV-A-007.
U.S. Environmental Protection Agency (1996f) Emissions inventory of Section 112(c)(6)
pollutants: polycyclic organic matter (POM), 2,3,7,8-tetrachiprodibenzo-p-dioxin
{TCbDJ^^S^jS-tetrachlorodibenzofuran IJQQP^ pojychlorinated biphenyl
compounds (PCBsj, hexachlorobenzene, mercury, and alkylated lead. Research
Triangle Park, NC: Office of Air Quality Planning and Standards. September 1996.
R-34 April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
U.S. Environmental Protection Agency (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. Environmental Protection Agency (1996h) Draft technical support document for
hazardous waste combustpr MACT standards. Volume I: Description of source
categories. Washington, DC: Office of Solid Waste and Emergency Response.
February 199,6.
U.S. Environmental Protection Agency (1997a) 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. Environmental Protection Agency (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. Environmental Protection Agency (1997c) 1996 Clean Water Needs Survey Report to
Congress. Washington, DC: Office of Water.
U.S. Environmental Protection Agency (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. Geological Survey (1997a) Minerals yearbook: recycling - nonferrous metals chapter.
Reston, VA: U.S Geological Survey, Geologic Division.
1 \
U.S. Geological Survey (1997b) Mineral commodity survey - iron and steel scrap.
Washington, DC: U.S. Department of the Interior, U.S. Geological Survey.
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 Dort, H.M.; Bedard, D.L. (1991) Reductive ortho and meta dechlorination of a
polychlorinated biphenyl congener by anaerobic microorganisms. Appl. Environ
Microbiol. 57:1576-1578.
Van Oostdam, J.C.; Ward, J.E.H. (1995) Dioxins and furans in the British Columbia
environment. Victoria, British Columbia: BC Environment, Environmental Protection
Department.
R"35 April 1998
-------
JDR^FT-PO NOT QUOTE OR CITE
''" !'" I'SI'lf ' 'I ,l' '' ,'l"" ' ' ' ' 1.1*'III1 I ! ', '"Illll I '1,1
Van Wijnen, J.H.; Liem, A.K.D.; Olie, K.; van Zorge, J.A. (1992) Soil contamination with
PCDDs and PCDFs Of srnall (illegal) scrap wire and scrap car incineration sites.
CJie'mosphere 24(2): 127-134.
;.:> • i • ', .. i ill I I > ., I > ' , •
Versar, Inc. (1976) PCBs in the United States: industrial use and environmental
distribution! Washington, DC: U.'si Environmentai Protection Agency, Office of
Toxic Substances. EPA Contract No. 68-61-3259, Task I.
Versar Inc. (1985] List of chemicals cpntarninated or precursors to contamination with
incidentally generated polychlorinated and polybrominated dibenzodioxins and
dibenzofufihs. EPA Contract No. 68-02-3968, task No. 48.
Vejsar, Inc. (1988) PCBI 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.
Vi|ejsoe, J.; Madsen, H.; Hansen, K. (1993) Emission of dioxins from Danish wood-stoves.
Organohalogen Compounds 11:465-408.
Vikelspej J.; Lasseh, P.; Joharisen, E.; Carlsen, L. (1994) Formation of PCDD/PCDFs via an
enzymatically mediated chlorination of humic acids. Organohalogen Compounds
20:351-354.
"•ill.; • i i Hi * I i ,"' '.•( ;,'.:;: „ ,; i, "jai. " ,;, I. ••..••
Villanueva, E.G.; Jennings, R.W.; Burse, V.W.; Kimbrough, R.D. (1974) Evidence of
chlprodibenzo-p-dioxin and chlorodibenzofuran in hexachlprobenzene. J. Agr. Food
Chem. 22(5):916-917. ' "" ' " '" ': ''
Vollrnuth, S.^ Zajc, A.; Niessner, R. (1994) Formation of pplychlorinated dibenzo-p-dioxins
and polychlorinated dibenzofurans during the photolysis of pentachlorophenol-
cpntaining water. Environ. Sci. Technol. 28(6):1145-1149.
Waq'dell/b.S.; Boneck-bciesa, H.; Gobran, J.; Ho, T.F.; Bottpn, "j.R. (1995) PCDD/PCDF
formation ,by UV photolysis of pentachlorophenbi with and without the addition of
hydrogen peroxide. Organohalogen Compounds 23:407-412.
i, ' ,: I i " ! ' H "' J!,Np91 ',,:' . ", '« ."""'I',!!1* , \:" "I1" , 'L , '» v :»!'' il1'1 4'f. ' i, ', !' /d'1" II • '!'• . i ' i'::'i»! ' ".ill"'1, •• •"' -." , i 3 '•!, • ,i", • , I1. , • '
Wagner, H.C.; Schramm, K.W.; Hutzinger, O. (1990) Biogenic polychlorinated dioxin and
furan from trichlorophenol. Organohaiogen Compounds 3:453-456.
Walsh, P.J.J.; ^"ffiN^co1^1?^' fv pre3ser, C.S.; Olphert, R. (1994) Biomass burning and
polychlorinated dibenzo-p-dioxins & furans in soil. Organohalogen Compounds
'".•'( (20):283-2|7. ' ;, '"' \ " ''; "^ ^,"""''7 .".."."!!'! ". '".'I...!.!
Ward, D.E.; McMahon, C.K.; Johansen, R.yy. (1976) An update on particulate emissions
from forest fires. Presented at: 69th Annual Meeting of the Air Pollution Control
Association. Portland, OR. June 27-July1, 1976.
R-36 April 1998
'•'• •'•''' • • •'' :"; •' • ••' ' •
-------
DRAFT-DO NOT QUOTE OR CITE
Ward, D.E.; Peterson, J.; Hao, W.M. (1993) An inventory of particulate 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.
[ ' I - • •
Watanabe, 1; 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. Contarn. 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.; Haupt, H.J. (1995) Influence of the aerobic and
anaerobic digestion on the levels of chlorinated dibenzofurans and dibenzodioxins in
sewage sludge. Organohalogeh Compounds 24:81-85.
Welsch-Pausch, K.; McLachlan, M.s: (1995) Photodegradation of PCDD/Fs on pasture
grass. Organohalogen Compounds 24:509-512.
Welsch-Pausch, K.; McLachlan, M.S.; Umlauf, G. (1995) Determination of the principal
pathways of polychlorinated dibenzo-p-dioxins and dibenzofurans to Lolium
multiflorum (Welsh Ray Grass). Enviroh. Sci. Technol. 29:1090-1098.
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.
Wevers, M.; De Fre, R. (1995) Estimated evolution of dioxin emissions in Belgium from
1988 to 1995. Organohalogen Compounds 24:105-108.
WHO (World Health Organization) (1991) IARC monographs on the evaluation of
carcinogenic risks to humans: occupational exposures in insecticide application, and
some pesticides.
Wichrnann, H.; Zelinski, V.; Scholz-Bottcher, B.; Lorenz, W.; Bahadir, M. (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):2755-2766.
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.
-April 1998
-------
DRAFT-DO NOT QUOTE OR CITE
Williams, 'C.H.; Prescott, C.L.; Stewart, P.B.; Choudhary, G. (1985) Formation of
poiychiorinated dibenzpfurans and other potentially toxic chlorinated pyrolysis
"'"^'products 'in """PCB ^fires^ "ri In:"' Keith, LHirRappe,c:; Choudhary, G., eds., Chlorinated
dipxin? an| dibenzofurans in the ^ Boston, MA: Butterworth
Publishers.
,!!"' I! " , , ' ' •;„ , „ , , , * , , ,' ...... ...... , ...... , . ,
s^ D\T 1; LeBel,' G.L; Benpit, P.M. [ (1 99|) Polychlorodibenzodioxins and
p!oJychloro3ibenzo^urans iri d!
24(2): 169-1 80. ................. ' ' " ...... '" ............................ '" V""": " '. ......... '"
•li! " .
I
R-38
April 1998
------- |