Document GGN2JrxX50DBvvLYy570EXzY

DRAFT DO NOT CITE OR QUOTE EPA/600/R-11/005A January 2013 External Review Draft Update to An Inventory of Sources and Environmental Releases of Dioxin-Like Compounds in the United States for the Years 1987, 1995, and 2000 NOTICE THIS DOCUMENT IS AN EXTERNAL REVIEW DRAFT. It has not been formally released by the U.S. Environmental Protection Agency and should not at this stage be construed to represent Agency Policy. It is being circulated for comment on its technical accuracy and policy implications. National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Washington, DC 20460 DISCLAIMER This document is distributed solely for the purpose of pre-dissemination peer review under applicable information quality guidelines. It has not been formally disseminated by EPA. It does not represent and should not be construed to represent any Agency determination or policy. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. ABSTRACT The purpose of this document is to present an update and revision to the dioxin source inventory published in 2006 (U.S. EPA, 2006), which is an inventory of sources and environmental releases of dioxin-like compounds in the United States. The current document presents updated estimates of environmental releases of dioxin-like compounds to the air, water, land and products. The sources are grouped into five broad categories: combustion sources, metals smelting/refining, chemical manufacturing, natural sources, and environmental reservoirs. Estimates of annual releases to land, air, and water are presented for reference years 1987, 1995, and 2000 (the years presented in the original report). The quantitative results are expressed in terms of the toxicity equivalence (TEQ) of the mixture of polychlorinated dibenzo-p-dioxin (CDD) and polychlorinated dibenzofuran (CDF) compounds present in environmental releases using a procedure sanctioned by the World Health Organization (WHO) in 1998. This TEQ procedure translates the complex mixture of CDDs and CDFs characteristic of environmental releases into an equivalent toxicity concentration of 2,3,7,8-tetrachorodibenzo-p-dioxin (2,3,7,8TCDD), the most toxic member of this class of compounds. The total releases under the national inventory for 1987 in g WHO98 TEQDFwere 15,000 to air, 2,400 to land, 360 to water, and 36 to products. For 1995, the releases in g WHO98 TEQDFwere 3,400 to air, 2,500 to land, 30 to water, and 47 to products. For 2000, the releases in g WHO98 TEQDFwere 2,300 to air, 2,300 to land, 28 to water, and 7 to products. While the overall decreasing trend in emissions seen in the original report continues, the individual dioxin releases in this draft updated report are generally higher than the values reported in 2006. This is largely due to the inclusion (in all three years) of additional sources in the quantitative inventory that were not included in the 2006 report. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 ii DRAFT: DO NOT CITE OR QUOTE CONTENTS LIST OF TABLES........................................................................................................................ xv LIST OF FIGURES....................................................................................................................xvii LIST OF ABBREVIATIONS AND ACRONYMS..................................................................xviii PREFACE.................................................................................................................................... xxi AUTHORS, CONTRIBUTORS, AND REVIEWERS..............................................................xxii EXECUTIVE SUMMARY.......................................................................................................xxiii 1. BACKGROUND, APPROACH, AND CONCLUSIONS................................................... 1-1 1.1. BACKGROUND.......................................................................................................... 1-1 1.1.1. Dioxin-Like Compounds................................................................................ 1-1 1.1.2. Toxicity Equivalence Factors........................................................................ 1-2 1.1.3. Regulatory Summary..................................................................................... 1-5 1.1.4. Information Sources....................................................................................... 1-5 1.2. APPROACH................................................................................................................ 1-6 1.2.1. Reference Years............................................................................................. 1-7 1.2.2. Release Types................................................................................................ 1-7 1.2.3. Source Classes............................................................................................... 1-8 1.2.4. Quantitative Method for Inventory of Sources.............................................. 1-9 1.2.5. Uncertainties................................................................................................ 1-12 1.3. SUMMARY AND CONCLUSIONS........................................................................ 1-15 1.3.1. Contemporary Formation Sources............................................................... 1-16 1.3.2. Reservoir Sources........................................................................................ 1-17 1.3.3. Time Trends................................................................................................. 1-17 1.3.4. Sources Not Included in the Inventory........................................................ 1-20 1.3.5. Congener Profiles of CDD/CDF Sources.................................................... 1-20 1.3.6. Uncertainty Analysis.................................................................................... 1-20 1.3.6.1. Air Releases.................................................................................. 1-21 1.3.6.2. Land Releases............................................................................... 1-24 1.3.7. Relative Impact of Releases......................................................................... 1-24 2. MECHANISMS OF FORMATION OF DIOXIN-LIKE COMPOUNDS DURING COMBUSTION OF ORGANIC MATERIALS...................................................................2-1 3. COMBUSTION SOURCES OF CDDs/CDFs: WASTE INCINERATION........................3-1 3.1. MUNICIPAL WASTE COMBUSTION....................................................................3-1 3.1.1. Air Releases..................................................................................................3-1 3.1.2. Water Releases..............................................................................................3-2 3.1.3. Solid Residue Releases.................................................................................3-2 3.1.4. Products........................................................................................................3-5 3.1.5. Release Summary.........................................................................................3-5 3.2. HAZARDOUS WASTE INCINERATION................................................................3-6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 iii DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 3.2.1. Dedicated HWIs............................................................................................3-7 3.2.1.1. Air Releases...................................................................................3-7 3.2.1.2. Water Releases...............................................................................3-8 3.2.1.3. Solid Residue Releases..................................................................3-8 3.2.1.4. Products--None.............................................................................3-8 3.2.1.5. Release Summary..........................................................................3-9 3.2.2. Industrial Boilers and Furnaces Burning Hazardous W aste.......................3-10 3.2.2.1. Air Releases.................................................................................3-10 3.2.2.2. Water Releases.............................................................................3-10 3.2.2.3. Solid Residue Releases................................................................3-10 3.2.2.4. Products--None...........................................................................3-10 3.2.2.5. Release Summary........................................................................3-10 3.2.3. Halogen Acid Furnaces Burning Hazardous Waste....................................3-12 3.2.3.1. Air Releases.................................................................................3-12 3.2.3.2. Water Releases.............................................................................3-12 3.2.3.3. Solid Residue Releases................................................................3-12 3.2.3.4. Products--None...........................................................................3-12 3.2.3.5. Release Summary........................................................................3-12 3.3. MEDICAL WASTE INCINERATION....................................................................3-13 3.3.1. Air Releases................................................................................................3-13 3.3.2. Water Releases............................................................................................3-14 3.3.3. Solid Residue Releases...............................................................................3-14 3.3.4. Products--None..........................................................................................3-15 3.3.5. Release Summary .......................................................................................3-15 3.4. CREMATORIA.........................................................................................................3-16 3.4.1. Human Crematoria......................................................................................3-16 3.4.1.1. Air Releases.................................................................................3-16 3.4.1.2. Water Releases.............................................................................3-17 3.4.1.3. Solid Residue Releases................................................................3-17 3.4.1.4. Products--None...........................................................................3-17 3.4.1.5. Release Summary........................................................................3-17 3.4.2. Animal Crematoria .................................................................................... 3-20 3.4.2.1. Air Releases.................................................................................3-20 3.4.2.2. Water Releases--None................................................................3-20 3.4.2.3. Solid Residue Releases................................................................3-20 3.4.2.4. Products--None...........................................................................3-21 3.4.2.5. Release Summary........................................................................3-21 3.5. SEWAGE SLUDGE INCINERATION....................................................................3-23 3.5.1. Air Releases................................................................................................3-23 3.5.2. Water Releases............................................................................................3-23 3.5.3. Solid Residue Releases...............................................................................3-23 3.5.4. Products--None..........................................................................................3-24 3.5.5. Release Summary ...................................................................................... 3-25 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 iv DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 3.6. TIRE COMBUSTION...............................................................................................3-26 3.6.1. Air Releases................................................................................................3-26 3.6.2. Water Releases............................................................................................3-26 3.6.3. Solid Residue Releases...............................................................................3-26 3.6.4. Products--None..........................................................................................3-27 3.6.5. Release Summary.......................................................................................3-27 3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED CHEMICAL PULP MILLS......................................................................................3-28 3.8. BIOGAS COMBUSTION.........................................................................................3-29 4. COMBUSTION SOURCES OF CDDs/CDFs: POWER/ENERGY GENERATION........4-1 4.1. MOTOR VEHICLE FUEL COMBUSTION..............................................................4-1 4.1.1. Air Literature................................................................................................4-1 4.1.2. Air Emission Factor......................................................................................4-3 4.1.2.1. Leaded Gasoline............................................................................4-3 4.1.2.2. Unleaded Gasoline.........................................................................4-4 4.1.2.3. Diesel Fuel.....................................................................................4-5 4.1.3. Air Activity Level.........................................................................................4-7 4.1.3.1. Gasoline.........................................................................................4-7 4.1.3.2. Diesel.............................................................................................4-8 4.1.4. Air Releases..................................................................................................4-8 4.1.5. Water Releases--None.................................................................................4-8 4.1.6. Solid Residue Releases.................................................................................4-8 4.1.7. Products--None............................................................................................4-8 4.1.8. Release Summary..........................................................................................4-9 4.2. WOOD COMBUSTION........................................................................................... 4-11 4.2.1. Residential Wood Combustion...................................................................4-11 4.2.1.1. Air Releases from Indoor Residential Wood Burners.................4-12 4.2.1.2. Air Releases from ResidentialOutdoor Wood-Fired Boilers...... 4-13 4.2.1.3. Water Releases--None................................................................4-14 4.2.1.4. Solid Residues from All Residential Wood Burning...................4-15 4.2.1.5. Solid Residue Emission Factor....................................................4-15 4.2.1.6. Solid Residue Activity Level.......................................................4-15 4.2.1.7. Solid Residue Releases................................................................4-16 4.2.1.8. Release Summary........................................................................4-16 4.2.2. Industrial Wood Combustion......................................................................4-18 4.2.2.1. Air Releases.................................................................................4-18 4.2.2.2. Water Literature--None..............................................................4-19 4.2.2.3. Solid Residue Releases................................................................4-19 4.2.2.4. Release Summary........................................................................4-20 4.3. OIL COMBUSTION.................................................................................................4-22 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 4.3.1. Institutional/Commercial and Residential Oil Combustion........................4-22 4.3.1.1. Air Releases.................................................................................4-22 4.3.1.2. Water Releases--None................................................................4-23 4.3.1.3. Solid Residue Releases--N one...................................................4-23 4.3.1.4. Products--None...........................................................................4-23 4.3.1.5. Release Summary........................................................................4-23 4.3.2. Utility Sector and Industrial Oil Combustion............................................. 4-24 4.3.2.1. Air Literature...............................................................................4-25 4.3.2.2. Air Emission Factor.....................................................................4-25 4.3.2.3. Activity Level..............................................................................4-25 4.3.2.4. Air Releases.................................................................................4-26 4.3.2.5. Water Releases--None................................................................4-26 4.3.2.6. Solid Residue Releases--N one...................................................4-26 4.3.2.7. Products--None...........................................................................4-26 4.3.2.8. Release Summary........................................................................4-26 4.3.3. Waste Oil Combustion................................................................................4-27 4.3.3.1. Air Literature...............................................................................4-28 4.3.3.2. Air Emission Factor.....................................................................4-28 4.3.3.3. Activity Level..............................................................................4-29 4.3.3.4. Air Releases.................................................................................4-29 4.3.3.5. Water Releases - None................................................................4-29 4.3.3.6. Solid Residue Releases - None....................................................4-29 4.3.3.7. Products - None........................................................................... 4-29 4.3.3.8. Release Summary........................................................................4-29 4.4. COAL COMBUSTION............................................................................................4-30 4.4.1. Coal-Fired Power Plants.............................................................................4-30 4.4.1.1. Air Releases.................................................................................4-31 4.4.1.2. Water Releases.............................................................................4-32 4.4.1.3. Solid Residue Releases................................................................4-32 4.4.1.4. Product Literature--None............................................................4-33 4.4.1.5. Release Summary........................................................................4-33 4.4.2. Coal-Fired Industrial Boilers......................................................................4-35 4.4.2.1. Air Releases.................................................................................4-35 4.4.2.2. Water Literature...........................................................................4-36 4.4.2.3. Solid Residue Releases................................................................4-36 4.4.2.4. Release Summary........................................................................4-36 4.4.3. Residential Coal Combustion .....................................................................4-37 4.4.3.1. Air Releases.................................................................................4-37 4.4.3.2. Water Releases--None................................................................4-38 4.4.3.3. Solid Residue Releases................................................................4-38 4.4.3.4. Products--None...........................................................................4-39 4.4.3.5. Release Summary........................................................................4-39 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 5. COMBUSTION SOURCES OF CDDs/CDFs: OTHER HIGH-TEMPERATURE SO URCES........................................................................................................................... 5-1 5.1. CEMENT KILNS........................................................................................................5-1 5.1.1. Air Releases..................................................................................................5-1 5.1.2. Water Releases..............................................................................................5-2 5.1.3. Solid Residue Releases.................................................................................5-3 5.1.4. Products........................................................................................................ 5-4 5.1.5. Release Summary.........................................................................................5-4 5.2. LIGHTWEIGHT AGGREGATE KILNS...................................................................5-7 5.2.1. Air Releases..................................................................................................5-7 5.2.2. Water Releases--None.................................................................................5-7 5.2.3. Solid Residue Releases--N one.................................................................... 5-7 5.2.4. Product Literature--None.............................................................................5-7 5.2.5. Release Summary.........................................................................................5-7 5.3. ASPHALT MIXING PLANTS...................................................................................5-9 5.3.1. Air Releases.................................................................................................. 5-9 5.3.2. Water Releases.............................................................................................. 5-9 5.3.3. Solid Residue Releases.................................................................................5-9 5.3.4. Products...................................................................................................... 5-10 5.3.5. Release Summary.......................................................................................5-10 5.4. PETROLEUM REFINING CATALYST REGENERATION PLANTS.................5-11 5.4.1. Air Releases................................................................................................ 5-11 5.4.2. Water Releases............................................................................................ 5-12 5.4.3. Solid Residue Releases ...............................................................................5-12 5.4.4. Product Literature .......................................................................................5-12 5.4.5. Release Summary.......................................................................................5-12 5.5. CIGARETTE SMOKING .........................................................................................5-13 5.5.1. Air Releases................................................................................................ 5-13 5.5.2. Water Releases--None ...............................................................................5-13 5.5.3. Solid Residue Releases ...............................................................................5-14 5.5.4. Products--None.......................................................................................... 5-14 5.5.5. Release Summary .......................................................................................5-14 5.6. PYROLYSIS OF BROMINATED FLAME RETARDANTS.................................5-15 5.7. CARBON REACTIVATION FURNACES..............................................................5-15 5.7.1. Air Releases................................................................................................5-15 5.7.2. Water Releases--None ...............................................................................5-16 5.7.3. Solid Residue Releases--None .................................................................. 5-16 5.7.4. Products ...................................................................................................... 5-16 5.7.5. Release Summary .......................................................................................5-16 5.8. KRAFT BLACK LIQUOR RECOVERY BOILERS............................................... 5-17 5.8.1. Air Releases................................................................................................5-17 5.8.2. Water Releases--None...............................................................................5-17 5.8.3. Solid Residue Releases ...............................................................................5-18 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 vii DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 5.8.4. Products......................................................................................................5-18 5.8.5. Release Summary.......................................................................................5-18 5.9. LIME KILNS............................................................................................................5-19 5.9.1. Process Description.....................................................................................5-19 5.9.2. Regulations.................................................................................................5-20 5.9.3. Air Releases................................................................................................5-20 5.9.4. Water Releases............................................................................................5-21 5.9.5. Solid Residue Releases...............................................................................5-21 5.9.6. Products......................................................................................................5-21 5.9.7. Release Summary.......................................................................................5-21 5.10. GLASS MANUFACTURING..................................................................................5-22 5.11. OTHER IDENTIFIED SOURCES...........................................................................5-24 6. COMBUSTION SOURCES OF CDDs/CDFs MINIMALLY CONTROLLED AND UNCONTROLLED COMBUSTION SOURCES..............................................................6-1 6.1. COMBUSTION OF LANDFILL GAS.......................................................................6-1 6.1.1. Air Releases..................................................................................................6-1 6.1.2. Water Releases..............................................................................................6-1 6.1.3. Solid Residue Releases--N one....................................................................6-1 6.1.4. Products--None............................................................................................6-1 6.1.5. Release Summary.........................................................................................6-1 6.2. ACCIDENTAL FIRES................................................................................................6-3 6.2.1. Structural Fires..............................................................................................6-3 6.2.1.1. Air Releases...................................................................................6-3 6.2.1.2. Water Releases...............................................................................6-4 6.2.1.3. Solid Residue Releases..................................................................6-4 6.2.1.4. Products--None.............................................................................6-4 6.2.1.5. Release Summary..........................................................................6-4 6.2.2. Vehicle Fires.................................................................................................6-6 6.2.2.1. Air Releases...................................................................................6-6 6.2.2.2. Water Releases...............................................................................6-7 6.2.2.3. Solid Residue Releases ..................................................................6-7 6.2.2.4. Products--None ............................................................................ 6-8 6.2.2.5. Release Summary ..........................................................................6-8 6.3. LANDFILL FIRES....................................................................................................6-11 6.3.1. Air Releases................................................................................................6-11 6.3.2. Water Releases--None...............................................................................6-13 6.3.3. Solid Residue Releases--N one..................................................................6-13 6.3.4. Products--None..........................................................................................6-13 6.3.5. Release Summary.......................................................................................6-13 6.4. FOREST AND BRUSH FIRES................................................................................6-14 6.4.1. Air Releases................................................................................................6-14 6.4.2. Air Emission Factors..................................................................................6-17 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 viii DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 6.4.3. Air Activity Levels.....................................................................................6-18 6.4.4. Water Releases............................................................................................6-19 6.4.5. Solid Residue Releases...............................................................................6-19 6.4.6. Products--None..........................................................................................6-19 6.4.7. Release Summary.......................................................................................6-19 6.5. BACKYARD BARREL BURNING........................................................................6-21 6.5.1. Air Releases................................................................................................6-21 6.5.2. Solid Residue Releases...............................................................................6-23 6.5.3. Release Summary .......................................................................................6-24 6.6. RESIDENTIAL YARD WASTE BURNING...........................................................6-26 6.6.1. Air Releases................................................................................................6-26 6.6.2. Water Releases--None...............................................................................6-27 6.6.3. Solid Residue Releases...............................................................................6-27 6.6.4. Products--None......................................................................................... 6-27 6.6.5. Release Summary .......................................................................................6-27 6.7. LAND-CLEARING DEBRIS BURNING................................................................6-28 6.7.1. Air Releases................................................................................................6-28 6.7.2. Water Releases--None...............................................................................6-29 6.7.3. Solid Residue Releases...............................................................................6-29 6.7.4. Release Summary ...................................................................................... 6-29 6.8. UNCONTROLLED COMBUSTION OF POLYCHLORINATED BIPHENYLS.............................................................................................................6-31 6.9. VOLCANOES...........................................................................................................6-32 6.10. FIREWORKS............................................................................................................6-32 6.11. OPEN BURNING AND OPEN DETONATION OF ENERGETIC MATERIALS............................................................................................................ 6-32 6.12. UNDERGROUND COAL FIRES............................................................................6-33 6.13. AGRICULTURAL BURNING.................................................................................6-33 6.13.1. Air Releases................................................................................................6-33 6.13.2. Water Releases--None...............................................................................6-34 6.13.3. Solid Residue Releases...............................................................................6-35 6.13.4. Products--None..........................................................................................6-35 6.13.5. Release Summary.......................................................................................6-35 6.14. OPEN BURNING DEMOLITION/CONSTRUCTION WOOD.............................6-36 6.14.1. Air Releases................................................................................................6-36 6.14.2. Water Releases--None...............................................................................6-37 6.14.3. Solid Residue Releases...............................................................................6-37 6.14.4. Release Summary.......................................................................................6-37 6.15. OIL SPILL BURNING.............................................................................................6-39 6.16. CANDLE BURNING................................................................................................6-40 7. METAL SMELTING AND REFINING SOURCES OF CDD/CDFs................................7-1 7.1. PRIMARY NONFERROUS METALSMELTING/REFINING................................ 7-1 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 ix DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 7.1.1. Primary Copper Smelting and Refining.......................................................7-1 7.1.1.1. Air Releases...................................................................................7-1 7.1.1.2. Water Releases...............................................................................7-1 7.1.1.3. Solid Residue Releases..................................................................7-1 7.1.1.4. Products.........................................................................................7-2 7.1.1.5. Release Summary..........................................................................7-2 7.1.2. Primary Magnesium Smelting and Refining...............................................7-3 7.1.2.1. Air Releases...................................................................................7-3 7.1.2.2. Water Releases...............................................................................7-4 7.1.2.3. Solid Residue Releases..................................................................7-4 7.1.2.4. Release Summary..........................................................................7-4 7.1.3. Primary Nickel Smelting and Refining........................................................7-6 7.1.3.1. Air Releases...................................................................................7-6 7.1.3.2. Water Releases...............................................................................7-6 7.1.3.3. Solid Residue Releases..................................................................7-6 7.1.3.4. Products.........................................................................................7-6 7.1.3.5. Release Summary..........................................................................7-6 7.1.4. Primary Aluminum Smelting and Refining................................................. 7-7 7.1.5. Primary Titanium Smelting and Refining.................................................... 7-7 7.1.5.1. Air Releases...................................................................................7-8 7.1.5.2. Water Releases...............................................................................7-8 7.1.5.3. Solid Residue Releases..................................................................7-8 7.1.5.4. Products.........................................................................................7-9 7.1.5.5. Release Summary..........................................................................7-9 7.2. SECONDARY NONFERROUS METAL SMELTING AND REFINING..............7-9 7.2.1. Secondary Aluminum Smelting and Refining.............................................7-9 7.2.1.1. Air Releases.................................................................................7-10 7.2.1.2. Water Releases.............................................................................7-10 7.2.1.3. Solid Residue Releases................................................................7-10 7.2.1.4. Products.......................................................................................7-10 7.2.1.5. Releases.......................................................................................7-10 7.2.2. Secondary Copper Smelting and Refining.................................................7-11 7.2.2.1. Air Releases.................................................................................7-12 7.2.2.2. Water Releases.............................................................................7-12 7.2.2.3. Solid Residue Releases................................................................7-12 7.2.2.4. Products.......................................................................................7-12 7.2.2.5. Releases.......................................................................................7-12 7.2.3. Secondary Lead Smelting..........................................................................7-14 7.2.3.1. Air Releases.................................................................................7-15 7.2.3.2. Water Releases.............................................................................7-15 7.2.3.3. Solid Residue Releases................................................................7-15 7.2.3.4. Products.......................................................................................7-15 7.2.3.5. Releases.......................................................................................7-15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 x DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 7.2.4. Secondary Zinc Production.......................................................................... 7-18 7.2.4.1. Air Releases.................................................................................7-18 7.2.4.2. Water Releases.............................................................................7-19 7.2.4.3. Solid Residue Releases................................................................7-19 7.2.4.4. Products.......................................................................................7-19 7.2.4.5. Releases.......................................................................................7-19 7.3. PRIMARY FERROUS METAL SMELTING/REFINING......................................7-20 7.3.1. Sinter Production........................................................................................7-20 7.3.1.1. Air Releases.................................................................................7-20 7.3.1.2. Water Releases.............................................................................7-21 7.3.1.3. Solid Residue Releases................................................................7-21 7.3.1.4. Products.......................................................................................7-21 7.3.1.5. Releases.......................................................................................7-21 7.3.2. Coke Production.........................................................................................7-22 7.3.2.1. Air Releases.................................................................................7-23 7.3.2.2. Water Releases.............................................................................7-23 7.3.2.3. Solid Residue Releases................................................................7-23 7.3.2.4. Products.......................................................................................7-23 7.3.2.5. Release Summary........................................................................7-24 7.4. SECONDARY FERROUS METAL SMELTING/REFINING................................7-25 7.4.1. Air Releases................................................................................................7-25 7.4.2. Water Releases............................................................................................7-25 7.4.3. Solid Residue Releases...............................................................................7-25 7.4.4. Products......................................................................................................7-25 7.4.5. Release Summary.......................................................................................7-25 7.5. FERROUS FOUNDRIES.........................................................................................7-27 7.5.1. Air Releases................................................................................................7-27 7.5.2. Water Releases............................................................................................7-27 7.5.3. Solid Residue Releases...............................................................................7-27 7.5.4. Products ......................................................................................................7-28 7.5.5. Release Summary .......................................................................................7-28 7.6. NONFERROUS METAL FOUNDRIES..................................................................7-29 7.6.1. Aluminum Foundries..................................................................................7-29 7.6.2. Copper Foundries........................................................................................7-31 7.7. SCRAP ELECTRIC WIRE RECOVERY................................................................7-33 7.7.1. Air Releases................................................................................................7-33 7.7.2. Water Releases............................................................................................7-33 7.7.3. Solid Residue Releases...............................................................................7-33 7.7.4. Products......................................................................................................7-33 7.7.5. Release Summary.......................................................................................7-34 7.8. DRUM AND BARREL RECLAMATION FURNACES........................................7-35 7.8.1. Air Releases................................................................................................7-35 7.8.2. Water Releases............................................................................................7-35 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xi DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 7.8.3. 7.8.4. 7.8.5. Solid Residue Releases...............................................................................7-36 Products......................................................................................................7-36 Release Summary.......................................................................................7-36 8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES..............................8-1 8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS.............................8-1 8.1.1. Air Releases..................................................................................................8-1 8.1.2. Water Releases..............................................................................................8-1 8.1.3. Solid Residue Releases.................................................................................8-1 8.1.4. Products........................................................................................................8-2 8.1.5. Release Summary .........................................................................................8-2 8.2. STAND-ALONE CHLOR-ALKALI PLANTS..........................................................8-4 8.2.1. Process Description.......................................................................................8-5 8.2.2. Regulations...................................................................................................8-6 8.2.3. Literature...................................................................................................... 8-6 8.2.4. Releases........................................................................................................8-7 8.3. STAND ALONE VINYL CHLORIDE MANUFACTURING PLANTS..................8-8 8.3.1. Process..........................................................................................................8-9 8.3.2. Regulations...................................................................................................8-9 8.3.3. Literature...................................................................................................... 8-9 8.3.4. Releases......................................................................................................8-12 8.4. COMPLEX CHEMICAL PLANTS PRODUCING CHLORINE AND A VARIETY OF CHLORINATED ORGANICS............................................................................................................... 8-13 8.4.1. Chlorophenols.............................................................................................8-14 8.4.1.1. Process Description......................................................................8-14 8.4.1.2. Regulations for Chlorophenols.................................................... 8-15 8.4.1.3. Products--Chlorophenols............................................................ 8-17 8.4.1.4. Products--2,4 D...........................................................................8-20 8.4.2. Chlorobenzenes...........................................................................................8-20 8.4.2.1. Process Description......................................................................8-20 8.4.2.2. Regulations for Chlorobenzenes..................................................8-21 8.4.2.3. Products--Chlorobenzenes.......................................................... 8-22 8.4.3. Complex Plants...........................................................................................8-23 8.5. MUNICIPAL WASTEWATER TREATMENT PLANTS......................................8-26 8.5.1. Air Releases................................................................................................8-27 8.5.2. Water Releases............................................................................................8-27 8.5.3. Solid Residue Releases...............................................................................8-27 8.5.4. Products ..................................................................................................... 8-28 8.5.5. Releases ..................................................................................................... 8-28 8.6. DRINKING WATER TREATMENT PLANTS.......................................................8-31 8.7. SOAPS AND DETERGENTS..................................................................................8-31 8.8. TEXTILE MANUFACTURING AND DRY CLEANING......................................8-31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xii DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 8.9. DYES, PIGMENTS, AND PRINTING INKS..........................................................8-32 8.10. OTHER ALIPHATIC CHLORINE COMPOUNDS................................................8-32 8.11. RESIDENTIAL SEPTIC SYSTEMS........................................................................8-32 8.11.1. Process Description.....................................................................................8-33 8.11.2. Regulations.................................................................................................8-33 8.11.3. Emission Factor..........................................................................................8-33 8.11.4. Activity.......................................................................................................8-34 8.11.5. Releases......................................................................................................8-34 9. NATURAL SOURCES OF CDDs/CDFs............................................................................9-1 9.1. BIOTRANSFORMATIONS.......................................................................................9-1 9.1.1. Biotransformation of Chlorophenols............................................................9-1 9.1.2. Biotransformation of Higher CDDs/CDFs...................................................9-2 9.1.3. Biotransformation of Animal Manure..........................................................9-2 9.2. PHOTOCHEMICAL TRANSFORMATIONS...........................................................9-3 9.2.1. Photolysis of PC P.........................................................................................9-4 9.2.2. Photolysis of Higher CDDs/CDFs................................................................9-4 9.2.3. Photolysis in Water.......................................................................................9-4 9.2.4. Photolysis on Soil Surfaces...........................................................................9-4 9.2.5. Photolysis on Vegetation..............................................................................9-5 9.2.6. Photolysis in A ir...........................................................................................9-5 9.3. CDDs/CDFs IN BALL CLAY....................................................................................9-5 10. SOURCES OF DIOXIN-LIKE POLYCHLORINATED BIPHENYLS (PCBs)..............10-1 10.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY..............................10-1 10.2. RELEASES FROM COMMERCIAL PCB PRODUCTS.......................................10-2 10.2.1. Approved PCB Disposal/Destruction Methods.......................................... 10-2 10.2.2. Releases of In-Service PCBs...................................................................... 10-2 10.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES.................... 10-4 10.4. COMBUSTION SOURCES..................................................................................... 10-6 10.4.1. Municipal Waste Combustion..................................................................... 10-6 10.4.2. Industrial Wood Combustion...................................................................... 10-8 10.4.3. Medical Waste Incineration........................................................................ 10-9 10.4.4. Tire Combustion....................................................................................... 10-10 10.4.5. Cigarette Smoking.................................................................................... 10-11 10.4.6. Sewage Sludge Incineration...................................................................... 10-12 10.4.7. Backyard Barrel Burning.......................................................................... 10-13 10.4.8. Petroleum Refining Catalyst Regeneration............................................... 10-15 10.4.9. Hazardous Waste Incineration.................................................................. 10-16 10.4.10. Power Plants............................................................................................. 10-16 10.4.11. Forest Fires............................................................................................... 10-17 10.5. METAL REFINING SOURCES............................................................................. 10-19 10.6. NATURAL SOURCES (originally Section 10.5)..................................................10-23 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xiii DRAFT: DO NOT CITE OR QUOTE CONTENTS (continued) 10.6.1. Biotransformation of Other PCBs............................................................. 10-23 10.6.2. Photochemical Transformation of Other PCBs........................................ 10-23 10.7. PAST USE OF COMMERCIAL PCBs (originally Section 10.6)....................... 10-23 11. RESERVOIR SOURCES OF CDD/CDFs AND DIOXIN-LIKE PCBs.......................... 11-1 11.1. SOIL RESERVOIRS (originally Section 11.2.1)....................................................11-2 11.1.1. Mechanisms Responsible for Releases from Surface Soils........................ 11-4 11.1.2. Estimated Annual Releases from Soil to Water.......................................... 11-4 11.1.2.1. Urban Runoff............................................................................... 11-4 11.1.2.2. Rural Soil Erosion........................................................................ 11-5 11.1.3. Estimated Annual Releases from Soil to A ir.............................................. 11-5 11.2. WATER RESERVOIRS (originally Section 11.2.2)................................................ 11-7 11.3. SEDIMENT RESERVOIRS (originally Section 11.2.3).........................................11-8 11.3.1. Mechanisms Responsible for Supply to and Releases from Sediment......11-8 11.3.2. Releases from Sediment to Water............................................................... 11-8 11.4. BIOTA RESERVOIRS (originally Section 11.2.4).................................................11-8 11.4.1. Mechanisms Responsible for Supply to and Releases from Biota............. 11-9 11.4.2. Approaches for Measuring and Estimating Releasesfrom Biota................ 11-9 11.5. PRODUCT RESERVOIRS......................................................................................11-9 11.5.1. Bleached Chemical Wood Pulp.................................................................. 11-9 11.5.2. Chlorophenols........................................................................................... 11-10 11.5.3. Vinyl Chloride Products........................................................................... 11-11 11.5.4. Chloranil................................................................................................... 11-11 11.5.5. Polychlorinated Biphenyls (PCBs)........................................................... 11-11 11.6. SUMMARY AND CONCLUSIONS (originally Section 11.3)............................11-12 BIBLIOGRAPHY This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xiv DRAFT: DO NOT CITE OR QUOTE LIST OF TABLES ES-1. Overview of changes to total quantities of TEQ emissions to air and land from the 2006 inventory................................................................................................................xxiv ES-2. Overview of total releases to air, land, water, and products in the updated inventory. .xxvii ES-3. Changes in quantitative release estimates from 2006 Report to present Report...........xxxii 1-1. Nomenclature for dioxin-like compounds..................................................................... 1-25 1-2. TEF schemes for CDDs, CDFs, and PCBs.................................................................... 1-26 1-3. Municipal waste combustors.......................................................................................... 1-28 1-4. Hazardous waste combustors......................................................................................... 1-29 1-5. Cement kilns not burning hazardous w aste................................................................... 1-30 1-6. Secondary aluminum smelters........................................................................................1-30 1-7. Medical waste incinerators............................................................................................ 1-31 1-8. Pulp and paper mills....................................................................................................... 1-31 1-9. Commercial/Industrial solid waste incinerators............................................................. 1-31 1-10. Sewage sludge incinerators.............................................................................................1-32 1-11. Industrial, commercial, and institutional boilers and process heaters........................... 1-32 1-12. Summary of CDD/CDF releases for reference years1987, 1995, and 2000...................1-33 1-13. Summary of PCB releases for reference years 1987,1995, and 2000.............................1-48 1-14. Summary of CDD/CDF reservoir releases.....................................................................1-51 1-15. Summary of PCB reservoir releases...............................................................................1-51 1-16. Ranking of top five sources by year and media release................................................. 1-52 1-17. Amounts of CDDs/CDFs contained in products in year manufactured......................... 1-52 1-18. Trend analyses based on quantitative inventory............................................................ 1-53 1-19. Uncertainty analysis for top nine air sources in 2000.................................................... 1-54 3-1. Inventory of municipal waste combustors in 1987........................................................ 3-31 3-2. Inventory of municipal waste combustors in 1995........................................................ 3-39 3-3. Inventory of municipal waste combustors in 2000........................................................ 3-49 3-4. TEQ emissions from medical waste incinerators for reference year 1987, 1995, and 2000..........................................................................................................................3-57 5- 1. CDD/CDF TEQ emission factors and emission estimates from Kraft lime kilns......... 5-25 6- 1. CDD/CDF emission factors for forest fires................................................................... 6-41 6-2. Comparison of Forest Fire Data..................................................................................... 6-43 8-1. CDD/CDF concentrations in graphite electrode sludge from chlorine production...... 8-36 8-2. Releases of dioxin-like compounds in wastewater discharges from chlor-alkali manufacturing facilities to surface water in 2000..........................................................8-37 8-3. Congener-specific and TEQ annual releases to air from a chlor-alkali facility in 2000............................................................................................................................8-38 8-4. Annual releases in 2000 from stand-alone chlor-alkali plants....................................... 8-39 8-5. Reported CDD/CDF concentrations in wastes from polyvinyl chloride manufacture..................................................................................................................... 8-40 8-6. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers..... 8-41 8-7. Annual releases in 2000 from stand-alone vinyl chloride plants................................... 8-43 8-8. CDD/CDF concentrations in mono-through tetrachlorophenols................................... 8-44 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 DRAFT: DO NOT CITE OR QUOTE LIST OF TABLES 8-9. Summary of specific dioxin-containing wastes that must comply with land disposal restrictions.........................................................................................................8-45 8-10. CDD/CDF concentrations (historical and current) in technical-grade pentachlorophenol products............................................................................................8-47 8-11. Historical CDD/CDF concentrations in pentachlorophenol-Na....................................8-49 8-12. CDD/CDF concentrations in chlorobenzenes................................................................8-51 8-13. Annual releases in 2000 from complex plants producing chlorine and a variety of chlorinated organics....................................................................................................8-52 8- 14. CDD/CDF mean concentrations measured in the 2001 National Sewage Sludge Survey............................................................................................................................. 8-54 9- 1. CDD and CDF concentrations in samples of animalmanurein the United Kingdom...............................................................................................................9-7 10- 1. Summary of PCB releases for reference years1987, 1995,and 2000............................10-24 10- 2. PCB analysis for composite ash samples from barrelburning........................... 10-27 11- 1. Amounts of CDD/CDFs Landfilled............................................................................. 11-13 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xvi DRAFT: DO NOT CITE OR QUOTE LIST OF FIGURES I- 1. Process inputs and outputs..............................................................................................1-55 6-1. Congener profile for structure fires............................................................................... 6-44 6-2. Forest fire types in the United States............................................................................. 6-45 8-1. Congener profile for technical grade PCP..................................................................... 8-55 I I - 1. Fluxes among environmental reservoirs.......................................................................11-14 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xvii DRAFT: DO NOT CITE OR QUOTE LIST OF ABBREVIATIONS AND ACRONYMS APCD BDDs BDFs Btu CARB CDD CDF CFR CKD DBF DCBz DCI DCP DL dscm DSI EDC EIA EPA EPRI ESP FF FIFRA GAC GC/ECD GC/MS HCl HCBz HDD HDF HWI HxCB IUPAC Air pollution control device polybrominated dibenzo-p-dioxins polybrominated dibenzofurans British thermal unit California Air Resources Board polychlorinated dibenzo-p-dioxin polychlorinated dibenzofuran Code of Federal Regulations cement kiln dust dibenzofuran dichlorobenzene data call-in dichlorophenol detection limit dry standard cubic meter dry sorbent injection ethylene dichloride Energy Information Administration U.S. Environmental Protection Agency Electric Power Research Institute electrostatic precipitator fabric filter Federal Insecticide, Fungicide, and Rodenticide Act granular activated carbon gas chromatography/electron capture detector gas chromatography/mass spectrometry hydrogen chloride hexachlorobenzene halogenated dibenzo-p-dioxin halogenated dibenzofuran hazardous waste incinerator hexachlorobiphenyl International Union of Pure and Applied Chemistry This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xviii DRAFT: DO NOT CITE OR QUOTE LOQ MB-WW MCBz MMT MSW MT MWI NCASI Nm3 NMOC OAQPS OH OPP ORD OSW PCA PCB PCP PeCB PeCBz PM POTW ppb ppm ppmv ppt PVC QA/QC RCRA RDF SIC SIP TCBz TCDD TCDF TeCB 1/7/2013 limit of quantitation mass burn waterwall monochlorobenzene million metric tons municipal solid waste metric ton (1000 kg) medical waste incinerator National Council of the Paper Industry for Air and Stream Improvement standard cubic meter nonmethane organic compound Office of Air Quality Planning and Standards hydroxide ion Office of Pesticide Programs Office of Research and Development Office of Solid Waste Portland Cement Association polychlorinated biphenyl pentachlorophenol pentachlorobiphenyl pentachlorobenzene particulate matter publicly owned treatment works parts per billion parts per million parts per million (volume basis) parts per trillion polyvinyl chloride quality assurance/quality control Resource Conservation and Recovery Act refuse-derived fuel Standard Industrial Classification State Implementation Plan trichlorobenzene 2,3,7,8-tetrachlorobidenzo-p-dioxin 2,3,.7,8 -tetrachl orobi denzofuran tetrachlorobiphenyl This document is a draftfor review purposes only and does not constitute Agency policy. xix DRAFT: DO NOT CITE OR QUOTE TeCP TEF TEQ TEQ/yr TrCB TrCP TRI TSCA 2,4-D 2,4-DCP 2,4,5-T U.K. USDA VCM WHO WS tetrachlorophenol toxicity equivalency factor toxicity equivalence toxicity equivalents per year trichlorobiphenyl trichlorophenol Toxics Release Inventory Toxic Substances Control Act 2,4-dichlorophenoxyacetic acid 2,4-dichlorophenol 2,4,5-trichlorophenoxy (phenoxy herbicides) United Kingdom U.S. Department of Agriculture vinyl chloride monomer World Health Organization wet scrubber This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 DRAFT: DO NOT CITE OR QUOTE PREFACE In 2006, EPA released a Dioxin Inventory Report that provided a comprehensive inventory and overview of sources and environmental releases of dioxin-like compounds in the United States (U.S. EPA, 2006). The purpose of this current document is to present an update and revision to the 2006 dioxin source inventory. This report includes some new data and also addresses additional comments EPA received on the 2006 Dioxin Inventory Report after it was published. This document was prepared by the National Center for Environmental Assessment, Office of Research and Development of the U.S. Environmental Protection Agency. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxi DRAFT: DO NOT CITE OR QUOTE AUTHORS, CONTRIBUTORS, AND REVIEWERS AUTHORS John Schaum, National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, Washington, DC. David Cleverly, National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, Washington, DC. Matthew Lorber, National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, Washington, DC. CONTRIBUTORS Dwain Winters, Office of Pollution Prevention and Toxics, U.S. Environmental Protection Agency, Washington, DC REVIEWERS Linda Phillips, National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, Washington, DC. ACKNOWLEDGMENTS This report is derived largely from the original version published in 2006. The contributions from the numerous authors and reviewers of that report (see full list in U.S. EPA, 2006) are gratefully acknowledged. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxii DRAFT: DO NOT CITE OR QUOTE EXECUTIVE SUMMARY Synopsis The purpose of this document is to present an update and revision to the dioxin source inventory published in 2006 (U.S. EPA, 2006), which is an inventory of sources and environmental releases of dioxin-like compounds in the United States for the years 1987, 1995, and 2000. The current document presents updated estimates of environmental releases of dioxin like compounds to the air, water, land and products. These updates do not expand the scope of the document beyond the three reference years covered in the original document: 1987, 1995, and 2000. The sources in this report are grouped into five broad categories: combustion sources, metals smelting/refining, chemical manufacturing, natural sources, and environmental reservoirs. The quantitative results are expressed in terms of the toxicity equivalence (TEQ) of the mixture of polychlorinated dibenzo-p-dioxin (CDD) and polychlorinated dibenzofuran (CDF) compounds present in environmental releases using a procedure sanctioned by the World Health Organization (WHO) in 1998. This TEQ procedure translates the complex mixture of CDDs and CDFs in the environmental releases into a single equivalent toxicity concentration (or mass) of 2,3,7,8-tetrachorodibenzo-p-dioxin (2,3,7,8-TCDD), the most toxic member of this class of compounds. The updated releases to land and air are presented in Table ES-1, alongside the results from the 2006 report. The quantitative releases to water and products did not change. While the overall decreasing trend in emissions seen in the original report continues, the individual dioxin releases in this draft updated report are generally higher than the values reported in 2006. This is largely due to the inclusion of additional sources in the quantitative inventory that were not included in the 2006 report. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxiii DRAFT: DO NOT CITE OR QUOTE Table ES-1. Overview of changes to total quantities of TEQ emissions to air and land from the 2006 inventory Description Air Releases (g WHO98TEQ) 1987 1995 2000 Land Releases (g WHO98TEQ) 1987 1995 2000 2006 Report 13,500 3,200 1,300 130 150 82 Present Report 15,000 3,400 2,300 2,400 2,500 2,300 For example, air releases are higher than listed in the 2006 report because the draft updated report includes emissions from forest fires as well as adjustments to emission factors used for municipal and medical waste incinerators. Forest fires were only reported as preliminary in 2006, but new experimental data has resulted in more certainty in the development of an emission factor for this source. Hence emissions were more accurately quantified as compared to the preliminary estimate made in 2006 and reclassified for inclusion in the quantitative inventory. The quantitative releases to land are markedly higher for all years compared to the 2006 report, due almost entirely to including ash from backyard trash burning in the current draft. The current report still contains estimates for some sources that are considered preliminary and not included in the quantitative inventory. Some of these sources are potentially large and, if confirmed, could change the trend observations based on the currently quantified sources, as happened with forest fires for this updated report. Approach Dioxin releases from a source can be in the form of products, air emissions, water discharges, and solid residues. Solid residues can be used in products or disposed via landfills or incinerators. Each source addressed in this document is evaluated in terms of all of these outputs. However, not all of the outputs are considered to be environmental releases. Outputs judged to have a reasonable likelihood for releases to the circulating environment include all air emissions, water discharges, and landfarmed wastes. Outputs that are not generally considered environmental releases include waste disposal at a lined landfill and intermediate products or This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxiv DRAFT: DO NOT CITE OR QUOTE internal waste streams. While it is recognized that some of the dioxins contained in products or disposed in secure landfills may be released to the circulating environment at some time in the future, they are less likely to be released to the circulating environment during the same year that they entered into commerce or were landfilled. Consequently, these contained dioxins would not initially be considered environmental releases. Ideally, releases derived from products and landfill practices of past years would be included in the inventory for the reference year in which the releases occur. Unfortunately, the current state of science does not support estimating when and to what degree such releases may occur. For informational purposes, and when sufficient information is available, this document provides estimates of the amounts of solid waste disposed in landfills. Sources can be categorized in terms of when releases occur: (1) contemporary formation sources (sources that have essentially simultaneous formation and release) and (2) reservoir sources (materials or places that contain previously formed CDDs/CDFs or dioxin-like PCBs that are rereleased to the environment). The contemporary formation sources are discussed in Chapters 3 through 10, and the reservoir sources are discussed in Chapter 11. This document also classifies sources into five broad categories based mainly on their formation process: Combustion. CDDs/CDFs are formed in most types of combustion. This document addresses waste incineration, sources related to power/energy generation, a variety high temperature sources (including cement kilns, asphalt plants, carbon reactivation furnaces, and others) and minimally controlled or uncontrolled sources (including landfill gas flares/fires, forest fires, backyard trash burning in barrels, and others). Metals Smelting/Refining. This category includes sources that are involved in metals smelting, refining, and processing. Chemical Manufacturing. CDDs/CDFs can be formed as by-products in a variety of chemical manufacturing operations. These include chlorine-bleached wood pulp, chlorinated phenols (e.g., pentachlorophenol), PCBs, chlorobenzenes, phenoxy herbicides (e.g., 2,4-D and 2,4,5-T), and chlorinated aliphatic compounds (e.g., ethylene dichloride, vinyl chloride, polyvinyl chloride). Biological, Photochemical, and Other Natural Processes. CDDs/CDFs can form via biological processes such as the action of microorganisms on chlorinated phenolic compounds and also during photolysis of highly chlorinated phenols. 1/7/2013 Reservoirs. Reservoirs are environmental compartments and materials that have the capacity to store previously formed CDDs/CDFs or dioxin-like PCBs. These This document is a draftfor review purposes only and does not constitute Agency policy. xxv DRAFT: DO NOT CITE OR QUOTE compounds are thus sequestered from the open and circulating environment. Potential reservoirs include soils, sediments, and biota as well as some anthropogenic materials, such as PCP-treated utility poles. Dioxin-like compounds in these reservoirs have the potential for redistribution and circulation in the environment through the physical processes such as leaching, volatilization, erosion, sedimentation, and deposition. Whenever dioxins are released from their place of storage back into the circulating environment, the reservoir is considered a source of dioxin. The approach used to estimate the emissions from most sources is based on an emission factor which relates mass of dioxins released into the environment with some measure of activity (e.g., kilograms of material processed per year, vehicle miles traveled per year, liters of wastewater discharged per year). The emission factor representing a class of facilities is developed by averaging the emission factors across the tested facilities in the class. This average emission factor is then multiplied by the measure of activity for the class to get total releases. In this update, a revised approach has been developed to characterize the confidence ratings of the release estimates. The revised approach maintains the three major categories previously used, i.e., (1) the quantitative inventory [which now includes the sum of the previous confidence ratings that were subdivided into Class A, B, or C], (2) the preliminary release estimates [previously assigned a rating of Class D], and the unquantifiable sources [previously assigned a rating of Class E]. The major changes are the elimination of the Class A, B, or C confidence distinctions in the quantitative inventory and the addition of the quantitative uncertainty analysis of the quantitative inventory (presented in Section 1.3.6). The old Class A, B, and C confidence ratings were eliminated because they were too subjective and difficult to apply in a consistent fashion. Also, it was judged that confidence ratings for the individual source classes were less essential because a new quantitative uncertainty analysis has been added (see discussion below). Key components of both the old and new schemes for classifying facilities are the criteria for deciding whether a source belongs in the quantitative inventory or the preliminary class. This update uses more specific guidance for making this decision. In order for a source to be included in the quantitative inventory, it must (a) have emission tests for at least two units/source types with sufficient documentation to directly derive emission factors, (b) the measured emission factors must be reasonably consistent or have understandable differences, (c) the emission factor This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxvi DRAFT: DO NOT CITE OR QUOTE tests must represent units that are reasonably typical of the class and (d) the activity estimates must be based on source-specific surveys. The actual magnitude of releases from the preliminary sources could be significantly lower or higher than estimated. Although EPA does not support including them in the quantitative inventory at this time, some of these preliminary sources have the potential of being major contributors of releases to the environment. Accordingly, they are important to identify and could be used to help set priorities for future research and data collection. As the uncertainty around these sources is reduced, they will be included in future inventory calculations. Results Eighty source categories were identified with the potential for dioxin emissions. An overview of the total releases to air, land, water, and products is provided in Table ES-2. The major conclusions regarding CDD/CDF releases from contemporary formation sources are presented below: The total releases under the national quantitative inventory for 1987 in g WHO98 TEQDF were 15,000 to air, 2,400 to land, 360 to water, and 36 to products. The total releases under the national quantitative inventory for 1995 in g WHO98 TEQDF were 3,400 to air, 2,400 to land, 30 to water, and 47 to products. The total releases under the national quantitative inventory for 2000 in g WHO98 TEQDF were 2,300 to air, 2,300 to land, 28 to water, and 7 to products. Table ES-2. Overview of total releases to air, land, water, and products in the updated inventory Year 1987 1995 2000 Air 15,000 3,400 2,300 Releases (g WHO98 TEQ) Land Water 2,400 360 2,400 30 2,300 28 Products 36 47 7 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxvii DRAFT: DO NOT CITE OR QUOTE  The top three quantified air sources in 2000 were: o forest fires (730 g WHO9g TEQDf), o backyard barrel burning of refuse (600 g WHO98 TEQdF), and o medical waste incinerators (400 g WHO98 TEQdF). Sources with preliminary release estimates have the potential for large releases of dioxin like compounds. While not included in the current quantitative estimates listed above, future inclusion of these sources could change current release estimates. The largest preliminary sources in the current report are: o accidental fires at landfills (1,300 g WHO98 TEQdF to air in 2000), and o land clearing debris burning (85 g WHO98TEQdF to air in 2000). A total of 20 contemporary formation sources were identified as having unquantifiable releases to one or more media. Information suggests these may be sources of dioxin-like compounds, but it is insufficient to make a national estimate of releases. The chemical product with the largest amount of CDD/CDF is pentachlorophenol, but the environmental releases associated with this product (primarily used to treat wood) could not be estimated. Release estimates could only be made for 2,4-D, where it can be assumed that the entire amount produced is released to the environment. The environmental releases of dioxin-like PCBs have not been well characterized. PCBs were not produced during the reference years, but are still present in capacitors, transformers, building materials and other products in use today. No estimates could be made for releases from these in-use products. Only one source (backyard barrel burning) was judged to have adequate data to support quantitative air-release estimates for dioxin-like PCBs: 41, 43, and 34 g WHO98 TEQp for the years 1987, 1995, and 2000, respectively. Similarly, only two sources (backyard barrel burning and municipal wastewater treatment) were judged to have adequate data to support quantitative land release estimates for dioxin-like PCBs: 52, 78, and 20 g WHO98 TEQp for the years 1987, 1995, and 2000, respectively. Also, only preliminary estimates could be made for 6 sources, and 10 sources were identified as being unquantifiable. Although the information is limited, it suggests that, in terms of TEQs, PCB releases are much lower than CDD/CDF releases. Soil is likely to be the reservoir source with the greatest potential for release of CDD/CDFs and PCBs to other environmental media, particularly to water. This is due to its relatively large mass of stored CDD/CDFs and PCBs and the existence of demonstrated This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxviii DRAFT: DO NOT CITE OR QUOTE transport mechanisms for intermedia exchange, e.g., soil erosion to surface waters and particle resuspension to air. Discussion Some observations about how releases have changed over the reference years can be made for the quantified sources. It is important to understand, though, that these observations do not include the sources classified as preliminary or unquantifiable. Some of the preliminary sources are potentially very large and, if confirmed and included in future quantitative estimates, could change the trend observations based on the currently quantified sources. With this caveat in mind, the following trends were identified. In terms of total releases from all media, a 67% reduction occurred from 1987 to 1995, a 23% reduction occurred from 1995 to 2000, and a 74% reduction occurred from 1987 to 2000. Significant amounts of the dioxin-like compounds produced annually in the United States are not considered releases to the open and circulating environment and are not included in the national inventory. Examples include dioxin-like compounds generated internal to a process but destroyed before release and waste streams that are disposed of in approved landfills. A number of contemporary formation sources were classified as preliminary or unquantifiable and, therefore, were not included in the inventory. The largest contemporary formation preliminary source is accidental fires at municipal solid waste landfills. This source has the potential to significantly increase the release estimates for 2000 if preliminary estimates are confirmed. A series of analyses were used to assess the uncertainties of the quantitative inventory. This analysis was limited to the air and land releases from the top sources (accounting for over 90% of the releases) in 2000. This first involved using a propagation of error approach, which estimates the variance for the air emissions from each source and sums these to get the overall variance in total emissions. Multiple factors contribute to the uncertainty in the emission estimate for a class of facilities. These include sampling error which reflects the number of facilities tested out of the total, the representativeness of the tests of long term conditions, and measurement error from inaccuracies in the stack monitoring and chemical analysis. The propagation of error approach used here assumes that the variability in the emissions from the sampled facilities is an indication of the possible uncertainty in the emissions from the whole This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxix DRAFT: DO NOT CITE OR QUOTE class of facilities. The analysis concludes that the total air releases from the top sources in 2000 sum to 2,100 g TEQ/year with a standard deviation of 1,300 g TEQ/year. Secondly, a probabilistic analysis was conducted to evaluate the uncertainties in the air releases. All emission factors were assumed to have log normal distributions with means and standard deviations based on an arithmetic analysis of the data. A Monte Carlo analysis was conducted using the Crystal Ball program. A total of 10,000 simulations were run, producing a mean of 2,100 g TEQ and standard deviation of 1,100 g TEQ, which are very similar to the results of the propagation-of-error approach described above. Percentiles were estimated as 1,100 g TEQ for 10%, 1,800 g TEQ for 50%, and 3,300 g TEQ for 90%. These percentiles can be interpreted as the probability that the emissions will less than or equal to the specified amount. Finally, further analysis is offered on the uncertainties associated with the forest fire air releases. These uncertainties are especially important to evaluate because they are the largest source and have high uncertainty in the emission factor. Both chamber studies and field studies have been used to measure these emissions. The field data suggest an emission factor of 0.95 ng TEQ/kg, and the chamber data suggest an emission factor of 7.5 ng TEQ/kg. If the lower emission factor is used, the forest fires would have a release of 230 g TEQ, and the total releases across the nine top sources in 2000 would be 1,600 g TEQ. Similarly, if the higher emission factor is used, the forest fires would have a release of 1,800 g TEQ, and the total releases across the nine top sources in 2000 would be 3,200 g TEQ. The 2000 land releases were dominated by backyard barrel burning which had releases of 1,900 g WHO98 TEQ (88% of the total) and the uncertainty analysis for land releases was limited to this one source. The releases from backyard barrel burning were based on a study by Lemieux (1997). Ash samples from the experiments were combined, resulting in two composite samples, one for recyclers (2,700 ng WHO98 TEQDF/kg ash) and one for nonrecyclers (620 ng WHO98 TEQdf /kg ash). The final emission factor was based on the average of these values (1,700 ng WHO98 TEQDF /kg ash). The limited data do not allow statistical analyses such as that done for the air releases. Instead a potential range of releases was estimated based on the lower and upper emission factor estimates. The activity estimate for 2,000 was 1.2 MMT. Combining this value with the lower emission factor yields a release estimate of 740 g WHO98 TEQ. Combining the activity with the higher emission factor yields a release This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxx DRAFT: DO NOT CITE OR QUOTE estimate of 2,800 g WHO98 TEQ. Accordingly the potential range of releases is 740 to 2,800 g WHO98 TEQ. Relative to the average value (1,900 g WHO98 TEQ), the lower estimate is 62% less and the upper estimate is 46% more. Changes from 2006 Document This discussion summarizes the changes from the 2006 report to the present report. Quantitative release estimates of CDD/CDFs to air increased for all years. The changes reflect the addition of new sources and adjustments to emission factors used for municipal and medical waste incinerators. The largest new source was forest fires which was previously classified as preliminary and not included in the quantitative inventory. Based on a number of new studies, it was decided that sufficient data were now available to move this source into the quantitative inventory. The forest fire releases in 2000 were about 4 times higher than 1987 and 1995 (due to more fires) causing a particularly large percent increase in that year. Other new sources added to the present document were secondary zinc smelters, glass manufacturers, lime kilns, agricultural burning, outdoor wood combustors, aluminum foundries, copper foundries and septic systems. Quantitative release estimates of CDD/CDFs to land also increased for all years. These increases were due almost entirely to ash from backyard barrel burning which had not been addressed in the 2006 report. The quantitative releases to water and products did not change. The changes to the air and land releases are summarized in Table ES-3 below. For dioxins, furans, and PCBs combined, the 2006 report indicated a 90% decrease in quantitative releases from 1987 to 2000. The updated report now indicates a 74% decrease over this time period. This reduction is due primarily to the addition of ash from backyard barrel burning (which remained relatively constant over the years) and air releases from forest fires (which had a particularly large release in 2000 as discussed above). The present document emphasizes that some of the preliminary sources are potentially very large and, if confirmed, could change the trend observations based on the currently quantified sources. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxxi DRAFT: DO NOT CITE OR QUOTE Table ES-3. Changes in quantitative release estimates from 2006 Report to present Report 2006 Present Report Report Air Releases (g WHO98 TEQ) 1987 13,500 15,000 1995 3,200 3,400 2000 1,300 2,300 Land Releases (g WHO98 TrEQ) 1987 130 2,400 1995 150 2,500 2000 82 2,300 Primary Reason for Change Addition of forest fires, changes to municipal and medical waste incinerators Addition of forest fires, changes to municipal and medical waste incinerators Addition of forest fires, changes to municipal and medical waste incinerators Addition of backyard barrel burners Addition of backyard barrel burners Addition of backyard barrel burners This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 xxxii DRAFT: DO NOT CITE OR QUOTE 1 1. BACKGROUND, APPROACH, AND CONCLUSIONS 2 3 4 1.1. BACKGROUND 5 This report presents an update to the dioxin source inventory published in 2006 (U.S. 6 EPA, 2006). The update does not expand the scope of the document beyond the three reference 7 years covered in the original document: 1987, 1995, and 2000. 8 This document is organized in a parallel fashion to the 2006 document, i.e., both 9 documents use the same chapter/section sequence, although several additional sections have been 10 added for new sources. This first chapter of the document is a complete rewrite and should be 11 used as a replacement of Chapter 1 in the 2006 document. Chapter 2 on formation theory was 12 not updated because it is not critical for the inventory. All subsequent chapters have sections 13 organized by environmental media, i.e., releases to air, water, land, and products. Individual 14 sections do not repeat the material in the 2006 document. Instead, they summarize new literature 15 references and describe any changes in release estimates. At the end of each section, a table is 16 presented (in a shaded text box to facilitate their identification and location) that provides all 17 emission factors, activities, and release estimates. Most readers will only need to use this 18 updated document because it describes all changes from the 2006 document and provides the 19 bottom-line release estimates for all sources. Readers interested in further details about sources 20 (i.e., process descriptions, summaries of the older literature, information on congener profiles, 21 etc.) may find it helpful to consult the 2006 document. 22 23 1.1.1. Dioxin-Like Compounds 24 This document addresses specific compounds in the following chemical classes: 25 chlorinated dibenzo-p-dioxins (CDDs), chlorinated dibenzofurans (CDFs), and polychlorinated 26 biphenyls (PCBs). The physical/chemical properties of these compounds vary according to the 27 degree and position of chlorine substitution. However, these compounds are generally 28 hydrophobic, persistent in the environment, resistant towards metabolism, and bioaccumulate in 29 the fatty tissues of animals and humans. 30 The CDDs include 75 individual compounds, CDFs include 135 individual compounds, 31 and PCBs include 209 individual compounds. These individual compounds are technically 32 referred to as congeners. 2,3,7,8-tetrachlorodibenzo-p-dioxin is the most widely studied (and This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-1 DRAFT: DO NOT CITE OR QUOTE 1 historically considered to be the most toxic) chemical in this general class of compounds. A 2 relatively small subset of the CDDs, CDFs, and PCBs are considered to have dioxin-like toxicity. 3 These compounds have similar chemical structures and invoke a common battery of toxic 4 responses as 2,3,7,8-TCDD. Only 7 of the 75 CDD congeners and 10 of the 135 CDF congeners 5 are recognized to have dioxin-like toxicity; they are the ones with chlorine substitutions in, at a 6 minimum, the 2, 3, 7, and 8 positions. There are 209 PCB congeners; of which, only 12 are 7 recognized to have dioxin-like toxicity--those with four or more lateral chlorine atoms with one 8 or no substitution in the o rth o position. These compounds are sometimes referred to as coplanar, 9 meaning that they can assume a flat configuration with rings aligned along the same plane. 10 Other halogenated compounds have been identified as having dioxin-like toxicity, such as 11 chlorinated naphthalenes, brominated dibenzo-p-dioxins and dibenzofurans, and similar 12 compounds with a mix of bromines and chlorines. However, as discussed below, these are not 13 addressed in this document. 14 The term "dioxins" has been used in several different ways in the literature. For 15 example, it has been used to refer to TCDD only, all CDDs and CDFs, or subsets of these 16 compounds. The present document uses "dioxins" to refer generally to the CDDs, CDFs, and 17 PCBs that have dioxin-like toxicity. (This can also be defined as the 17 CDDs/CDFs and 12 18 coplanar PCBs with toxicity equivalence factors [TEFs] greater than zero; this concept of 19 toxicity equivalence is discussed further in Section 1.1.2 below.) Similarly, the phrase "dioxin 20 like compounds" is used in this document to refer to only those compounds with established TEF 21 values. As noted above, a number of other compounds have been suggested to have "dioxin-like 22 toxicity," but these are not addressed in this document. 23 This document focuses primarily on the 17 CDDs/CDFs, with a more limited discussion 24 of the 12 coplanar PCBs. This is because there are relatively little congener-specific data on 25 PCB releases. 26 Table 1-1 provides a complete listing of the chemical nomenclature used in this report. 27 28 1.1.2. Toxicity Equivalence Factors 29 CDDs, CDFs, and PCBs are commonly found as complex mixtures when detected in 30 environmental media, biological tissues, or releases from specific sources. Humans are likely to 31 be exposed to mixtures of these compounds that vary by source and pathway, complicating the This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-2 DRAFT: DO NOT CITE OR QUOTE 1 assessment of human health risk assessment. To address this problem, the concept of a "toxicity 2 equivalence" (TEQ) has been developed. 3 TEFs compare the toxicity of each dioxin-like compound in the mixture to the 4 well-studied 2,3,7,8-TCDD, historically considered the most toxic member of the group. The 5 comparison procedure involves assigning individual TEFs to the 2,3,7,8-substituted CDD/CDF 6 congeners and dioxin-like PCBs. To accomplish this, scientists have reviewed the toxicological 7 databases and, with considerations of chemical structure, persistence, and resistance to 8 metabolism, have agreed to ascribe specific "order-of-magnitude" TEFs for each dioxin-like 9 congener relative to 2,3,7,8-TCDD, which is assigned a TEF of 1. The other congeners have 10 TEF values ranging from 1 to 0.00001. 11 To apply this concept, the TEF of each congener present in a mixture is multiplied by the 12 respective mass concentration, and the products are added to represent the 2,3,7,8-TCDD TEQ of 13 the mixture (eq 1-1). 14 15 TEQ = ^ C oncentration x TEFt (1-1) =1 16 17 A variety of TEF schemes have been developed since the 1980s. This can lead to 18 confusion when a TEQ value is presented without a clear designation of which TEF scheme was 19 used to calculate it. This document uses a nomenclature that distinguishes between the different 20 TEF schemes and identifies the congener groups included in specific TEQ calculations: 21 22 I-TEQ refers to toxic equivalents derived using the international TEF scheme adopted by 23 EPA in 1989 (U.S. EPA, 1989). 24 WHO94 TEQ refers to toxic equivalents derived using the 1994 World Health 25 Organization (WHO) extension of the I-TEF scheme, which includes 13 dioxin-like 26 PCBs (Ahlborg et al., 1994). 27 WHO98 TEQ refers to toxic equivalents derived using the 1998 WHO update to the 28 previously established TEFs for dioxins, furans, and dioxin-like PCBs (Van den Berg 29 et al., 1998). 30 WHO2005 TEQ refers to toxic equivalents derived using the 2005 WHO update to the 31 previously established TEFs for dioxins, furans, and dioxin-like PCBs (Van den Berg 32 et al., 2006). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-3 DRAFT: DO NOT CITE OR QUOTE 1 2 Table 1-2 shows all four of these TEF schemes. 3 The nomenclature also uses subscripts to indicate which family of compounds is included 4 in any specific TEQ calculation. Under this convention, a subscript D is used to designate 5 dioxins, a subscript F is used to designate furans, and a subscript P is used to designate PCBs. 6 As an example, WHO98 TEQDFwould be used to describe a mixture for which only dioxin and 7 furan congeners were determined and where the TEQ was calculated using the WHO98 scheme. 8 If PCBs had also been determined, the nomenclature would be WHO98 TEQDFP. Note that in this 9 document I-TEQ sometimes appears without the D or F subscripts. This indicates that the TEQ 10 calculation includes both dioxins and furans. 11 This document uses the WHO98 TEF scheme as the primary basis for presenting TEQ 12 estimates. While the WHO2005 TEFs are more current, the previous version of this document 13 used the WHO98 TEFs. This document continues the use of the WHO98 TEFs to be consistent 14 with the 2006 document, allowing for easy comparison. A limited number of estimates were 15 generated using the newer TEF values, and it was seen that differences were inconsequential 16 (data not provided). 17 Throughout this document, environmental release estimates are presented in terms of 18 TEQs. This is consistent with previous versions of the inventory and is the common approach to 19 dioxin sources inventories worldwide (UNEP, 2005). Doing so facilitates comparisons across 20 sources. For the purposes of environmental fate modeling, however, it is important to use the 21 individual CDD/CDF and PCB congener values rather than TEQs. This is because the 22 physical/chemical properties of individual CDD/CDF congeners vary and, consequently, the 23 congeners will behave differently in the environment. For example, the relative mix of 24 congeners released from a stack cannot be assumed to remain constant during transport through 25 the atmosphere and deposition to various media. Further, the bioavailability of dioxin congeners 26 are different, so that bioaccumulation in the food chain up through humans results in different 27 relative proportions of dioxins compared to the profile of dioxins to which animals and humans 28 are exposed. Generally, human exposure to releases of dioxins from sources is a complex 29 phenomena encompassing proximity to source, congener-specific fate and transport 30 characteristics, and congener-specific bioavailability. For this reason, the amount of dioxins 31 being emitted from a specific source may not translate directly into human exposure. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-4 DRAFT: DO NOT CITE OR QUOTE 1 TEQ values are frequently based on some congeners that were not found above detection 2 limits (DLs). Undetected values are commonly referred to using the term "nondetect," or ND, 3 and that terminology is adopted here. EPA risk assessments typically address this issue by 4 assuming that NDs = 2DL. This document is not a risk assessment and uses a different 5 approach. Here, it is assumed that NDs = 0. This assumption allows a consistent approach to 6 this issue throughout the document. Because many studies did not provide DLs, the only 7 practical, consistent approach is to assume NDs = 0. Many assessments also present TEQ 8 estimates in two ways: first assuming NDs = 0 and then assuming NDs = 2 DL. Such 9 comparisons are useful for illustrating the impact of DLs on TEQ calculations. This approach 10 was used in some places in this document, but generally, it was not used for two reasons. First, it 11 was not possible in many instances due to lack of DL information. Second, many release 12 estimates are presented in terms of two TEF schemes and three reference years. Presenting all 13 values with two ways of treating DLs, would increase complexity enough to compromise the 14 readability of the document. 15 16 1.1.3. Regulatory Summary 17 Over the time frame represented by these inventories (1987-2000), EPA, states, and 18 industry have worked to develop regulations limiting dioxin emissions. Although not all of these 19 regulations are fully implemented yet, they have contributed to reductions in emissions from 20 certain source categories (see time trend discussion in Section 1.3.3). Tables 1-3 through 1-8 21 present a synopsis of the principal EPA emission standards for the control of dioxin releases. 22 23 1.1.4. Information Sources 24 The references used to support this report are based on an intensive literature review of 25 documents published in 2003 (or earlier) and selected documents published in 2004-2010. The 26 report also used information from databases maintained by EPA's Office of Air Quality Planning 27 and Standards and Office of Resource Conservation and Recovery (ORCR). 28 An important reference in this field is the S ta n d a rd ize d T o o lkitf o r Id e n tific a tio n a n d 29 Q u a n tific a tio n o f D io x in a n d F u r a n R e le a se s issued by the United Nations Environment 30 Programme in 2005 (UNEP, 2005). This document was produced to help support 31 implementation of the Stockholm Convention on Persistent Organic Pollutants. This T oolkit This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-5 DRAFT: DO NOT CITE OR QUOTE 1 provides a methodology to help countries just developing their inventories to estimate releases of 2 CDD/CDF and to lead them through the process of enhancing and refining these inventories. It 3 is intended to provide a consistent basis for assessing CDD/CDF releases over time and between 4 countries. This updated inventory frequently references the T oo lkit and discusses the 5 recommended emission factors. 6 The EPA Toxics Release Inventory (TRI) began collecting data on PCBs in 1988 and on 7 CDDs/CDFs in 2000 (U.S. EPA, 2003b). The TRI reporting of dioxin sources provides 8 important information in the overall understanding of dioxin releases. These data were 9 considered in this report for the purposes of identifying possible sources and as supportive 10 evidence for where releases can occur, but they were not used for making quantitative release 11 estimates because of the following considerations: 12 13 With respect to PCBs, for reporting years 1988-2000, the TRI data are reported as total 14 PCBs rather than on a congener-specific basis. Thus, it is unknown what portion of these 15 releases are dioxin-like PCBs, and TEQs cannot be calculated. 16 With respect to CDDs/CDFs, for reporting year 2000, the TRI data are reported as the 17 sum of the 17 congeners with 2,3,7,8-chlorine-substituted compounds. Facilities had the 18 option to report an estimate of the congener distribution for total releases, though many 19 chose not to provide this information. Accordingly, much of the 2000 data could not be 20 used to make TEQ estimates. 21 The TRI data are self-reported, and facilities are not required to take measurements to 22 support their emission estimates. Rather, they can be derived from emission factors or 23 other methods. Facilities are also not required to describe the approach used to make the 24 emission estimates. Consequently, it would be difficult to evaluate inconsistencies 25 between these estimates and those in this inventory. 26 The TRI reports include SIC codes but lack further details describing the facilities in 27 terms of process, production, and pollution controls. Therefore, in many cases, it is not 28 clear where a reporting facility fits into the classification system used in this report. 29 30 1.2. APPROACH 31 This section describes the key components of the approach used to develop the dioxin 32 inventory. The discussion covers the selection of reference years, release types, how sources are 33 classified, quantitative methods used to develop release estimates, and confidence ratings. 34 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-6 DRAFT: DO NOT CITE OR QUOTE 1 1.2.1. Reference Years 2 A central part of EPA's dioxin inventory is the organization of estimates of annual 3 releases of dioxin-like compounds into reference years 1987, 1995, and 2000. The selection and 4 use of three reference years provides a basis for comparing environmental releases over time. 5 The year 1987 was selected as the initial reference year because it was the earliest time 6 when it was feasible to assemble a reasonably comprehensive inventory. Prior to that time, very 7 little data existed on dioxin emissions from stacks or other release points. The first study 8 providing the type of data needed for a national inventory was the EPA National Dioxin Study 9 (U.S. EPA, 1987). The year 1987 also corresponds roughly with the time when significant 10 advances occurred in emissions measurement techniques and in the development of 11 high-resolution mass spectrometry and gas chromatography, which allowed analytical 12 laboratories to detect low levels of CDD and CDF congeners in environmental samples. Soon 13 after this time, a number of facilities began upgrades specifically intended to reduce CDD/CDF 14 emissions. Consequently, 1987 emissions are representative of levels that occurred before the 15 widespread installation of pollution control systems and pollution prevention techniques 16 specifically designed to reduce dioxin releases from man-made sources into the air, land, and 17 water. 18 EPA selected 1995 as the second reference year because it reflects the completion time of 19 the first set of regulatory activities specifically tailored to reduce dioxin releases from major 20 sources. By 1995, EPA had proposed or promulgated regulations limiting CDD/CDF emissions 21 from municipal waste combustors (MWCs), medical waste incinerators, and pulp and paper mill 22 facilities using bleached chlorine processes. 23 The year 2000 was chosen as the most current date that could be addressed when this 24 effort began in 2002. Also, it corresponds to a reasonable time interval since 1995 when one 25 could expect to see further changes occurring in releases as a result of continuing regulatory 26 activities, voluntary actions on the part of industry, and facility closures. 27 28 1.2.2. Release Types 29 A comprehensive assessment of potential dioxin releases from a source requires 30 consideration of all possible outputs. As diagrammed in Figure 1-1, the outputs of a process can 31 be in the form of products, air emissions, water discharges, and solid residues. Solid residues This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-7 DRAFT: DO NOT CITE OR QUOTE 1 can be used in products, land disposed or incinerated. Each source addressed in this document is 2 evaluated in terms of all of these outputs. However, not all of the outputs are considered to be 3 environmental releases. Outputs judged to have a reasonable likelihood for release to the 4 circulating environment include all air emissions, water discharges, landfarmed wastes and 5 products which are directly released to the open environment such as some pesticides. Outputs 6 that are generally not considered an environmental release include waste disposal at lined 7 landfills, intermediate products or internal waste streams or products containing tightly bound 8 dioxins such as treated wood. Dioxins contained in some products or disposed in secure landfills 9 may be released to the circulating environment at some time in the future. They are less likely to 10 be released to the circulating environment during the same year that they enter into commerce or 11 are landfilled. Consequently, these contained dioxins would not initially be considered 12 environmental releases. Ideally, releases derived from such products and landfill practices of 13 past years would be included in the inventory for the reference year in which the releases occur. 14 Unfortunately, the current state of science does not support estimating when and to what degree 15 such releases may occur. However, for informational purposes, and when sufficient information 16 is available, this document provides estimates of the amount of dioxins contained in products or 17 disposed in landfills. 18 19 1.2.3. Source Classes 20 Sources can be categorized in terms of when releases occur: (1) contemporary formation 21 sources (sources that have essentially simultaneous formation and release) and (2) reservoir 22 sources (materials or places that contain previously formed CDDs/CDFs or dioxin-like PCBs that 23 are rereleased to the environment). The contemporary formation sources are discussed in 24 Chapters 3 through 10, and the reservoir sources are discussed in Chapter 11. 25 This document also classifies sources into five broad categories based mainly on their 26 formation process: 27 28 1. Combustion. CDDs/CDFs are formed in most types of combustion. These sources are 29 addressed in Chapters 3-6: 30 Chapter 3 covers sources involved in waste incineration including municipal solid 31 waste (MSW), hazardous waste, medical waste, sewage sludge, and other types of 32 waste. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-8 DRAFT: DO NOT CITE OR QUOTE 1 Chapter 4 covers sources related to power/energy generation including motor vehicles 2 and combustion of wood, oil, and coal. 3 Chapter 5 covers a variety high temperature sources including cement kilns, asphalt 4 plants, carbon reactivation furnaces, and others. 5 Chapter 6 covers minimally controlled or uncontrolled sources and includes landfill 6 gas flares/fires, forest fires, backyard trash burning in barrels, and others. 7 2. Metals Smelting/Refining. This category includes sources that are involved in metals 8 smelting, refining, and processing. They are addressed in Chapter 7. 9 3. Chemical Manufacturing. CDDs/CDFs can be formed as by-products in a variety of 10 chemical manufacturing operations. These are addressed in Chapter 8 and include 11 chlorine-bleached wood pulp, chlorinated phenols (e.g., pentachlorophenol), PCBs, 12 chlorobenzenes, phenoxy herbicides (e.g., 2,4-D and 2,4,5-T), and chlorinated aliphatic 13 compounds (e.g., ethylene dichloride, vinyl chloride, polyvinyl chloride). 14 4. Biological, Photochemical, and Other Natural Processes. CDDs/CDFs can form via 15 biological processes such as the action of microorganisms on chlorinated phenolic 16 compounds and also during photolysis of highly chlorinated phenols. These are 17 addressed in Chapter 9. 18 5. Reservoirs. Reservoirs are environmental compartments and materials that have the 19 capacity to store previously formed CDDs/CDFs or dioxin-like PCBs. These compounds 20 are thus sequestered from the open and circulating environment. Potential reservoirs 21 include soils, sediments, and biota as well as some anthropogenic materials, such as 22 PCP-treated utility poles. Dioxin-like compounds in these reservoirs have the potential 23 for redistribution and circulation in the environment through the physical processes such 24 as leaching, volatilization, erosion, sedimentation, and deposition. Whenever dioxins are 25 released from their place of storage back into the circulating environment, the reservoir is 26 considered a source of dioxin. Reservoirs are addressed in Chapter 11. 27 28 Note that Chapters 3-9, discussed above, address releases of only CDDs and CDFs. 29 Contemporary formation sources that releases dioxin-like PCBs are discussed in Chapter 10. 30 Reservoir sources that release CDDs, CDFs, or PCBs are covered in Chapter 11. 31 32 1.2.4. Quantitative Method for Inventory of Sources 33 Estimates of CDD/CDF releases to the air from individual facilities are derived from 34 stack testing, which provides the concentration of CDD/CDF in the flue gas. This is combined 35 with the flue gas flow rate and operating time to estimate annual releases as shown in 36 equation 1-2: 37 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-9 DRAFT: DO NOT CITE OR QUOTE C Fv CF H 1 E '.TEQ (1-2) 109 ng / g 2 3 where 4 ETeq = annual TEQ emissions (g/year) 5 C = combustion flue gas TEQ concentration (ng/dscm) (20oC, 1 atm; adjusted to 6 7% O2) 7 Fv = volumetric flow rate of combustion flue gas (dscm/hour) (20oC, 1 atm; adjusted 8 to 7% O2) 9 CF = capacity factor; fraction of time that the facility operates 10 H = total hours in a year (8,760 hour/year) 11 12 A similar approach is used for estimating facility releases to other media. For example, releases 13 to water would involve multiplying the concentration of the CDD/CDF in the effluent by the 14 discharge rate. Ideally, national release estimates would be derived by testing every facility in a 15 source category, estimating their releases, and summing across facilities. This was feasible in 16 only a few situations such as wastewater releases from chlorine-bleached pulp and paper mills. 17 For all other source categories, EPA used a method to extrapolate from tested to untested sources 18 and derive national estimates of environmental releases. As explained below, this method is 19 based on the use of emission factors and activity levels. 20 The first step in this approach is to use emission monitoring data to derive an emission 21 factor (or series of emission factors) deemed to be representative of the source category (or 22 segments of a source category that differ in terms of configuration, fuel type, air pollution 23 control equipment, etc.). The emission factor relates mass of dioxins released into the 24 environment with some measure of activity (e.g., kilograms of material processed per year, 25 vehicle miles traveled per year, liters of wastewater discharged per year). For individual 26 facilities, it is calculated using the following equation (eq 1-3): 27 28 E F E'TEQ (1-3) A 29 30 where This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-10 DRAFT: DO NOT CITE OR QUOTE 1 EF = emission factor (ng TEQ/kg) 2 Eteq = annual TEQ emissions (g/year) (see eq 1-1) 3 A = annual activity rate (kg/year) 4 5 A similar approach is used for estimating emission factors for releases to other media. 6 For example, an emission factor for releases to water would involve dividing the annual TEQ 7 release rate via effluent discharges by the annual waste processing rate (or some other measure 8 of activity). The emission factor representing a class of facilities is developed by averaging the 9 emission factors across the tested facilities in the class. This average emission factor is then 10 multiplied by the measure of activity for the nontested facilities in the class (e.g., total kilograms 11 of material processed by these facilities annually). Finally, releases are summed for the tested 12 facilities and nontested facilities. In general, this procedure can be represented by the following 13 equations (eq 1-4 and 1-5): 14 15 (1-4)R Total ^ R Tested,i + ^ R UUntested ,i i=1 i=1 16 17 (1-5)R Total = ^ R Tested,i + ^ E F Untested,i X A i i=1 i=1 18 where 19 RTotal annual releases from all facilities (g TEQ/year) 20 RTested, i annual releases from all tested facilities in class i (g TEQ/year) 21 RUntested, i annual releases from all untested facilities in class i (g TEQ/year) 22 EFUntestedi mean emission factor for untested facilities in class i (g TEQ/kg) 23 Ai activity measure for untested facilities in class i (kg/year) 24 25 Note that even though this approach is presented using the term "emission factor," it is 26 intended to apply to releases to all media. The method was originally developed for evaluating 27 air emissions and is thus traditionally defined using this term. Also note that for most sources, a 28 small percentage of the facilities had been tested. In these cases, it was not worth the effort to This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-11 DRAFT: DO NOT CITE OR QUOTE 1 estimate releases from tested and untested facilities separately as shown in equation 1-5. Instead, 2 the average emission factor was applied to the activity level for the whole class. 3 Some source categories are made up of facilities that vary widely in terms of design and 4 operating conditions. For these sources, as explained above, an attempt was made to create 5 subcategories that grouped facilities with common features and then to develop separate 6 emission factors for each subcategory. Implicit in this procedure is the assumption that facilities 7 with similar design and operating conditions should have similar CDD/CDF-release potential. 8 For most source categories, however, the specific combination of features that contributes most 9 to CDD/CDF or dioxin-like PCB releases is not well understood. Therefore, the procedure for 10 how to best subcategorize a source category was often problematic. For each subcategorized 11 source category in this document, a discussion is presented about the variability in design and 12 operating conditions, what was known about how these features contributed to CDD/CDF or 13 dioxin-like PCB releases, and the rationale for creating subcategories. 14 The emission factors developed for the inventory are intended to be used for estimating 15 total emissions for a source category rather than emissions from individual facilities. If applied 16 to individual facilities, the emission factor would likely overestimate releases from some 17 facilities and underestimate others. When it is applied to a class of facilities, these over- and 18 underestimates balance out to some extent. Thus, in using these emission factors, one can place 19 significantly greater confidence in an emission estimate for a class than in an estimate for any 20 individual facility. Given the limited amount of data available for deriving emission factors and 21 the limitations of our understanding about facility-specific conditions that determine formation 22 and control of dioxin-like compounds, the current state of knowledge cannot support the 23 development of emission factors that can be used to accurately estimate emissions on an 24 individual facility-specific basis. 25 26 1.2.5. Uncertainties 27 The quantitative inventory has multiple uncertainties, including the following: 28 29 It is based on emissions testing that covers a small fraction of the facilities in most 30 classes. 31 Facility testing is generally over short time periods during normal operating conditions. 32 The releases during start-up and shutdown may be different than normal operations. For This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-12 DRAFT: DO NOT CITE OR QUOTE 1 conventional pollutants, releases are generally greater during these times, but dioxin 2 releases may occur at rates lower or higher than normal operations due to changes in 3 formation conditions. Recent efforts by EPA's Office of Air Quality Planning and 4 Standards are addressing emissions that occur during start-up and shutdown and may 5 allow these uncertainties to be addressed in the future. 6 Testing has sometimes found individual facilities within a class with unusually low or 7 high dioxin releases for unknown reasons. 8 It does not include the emissions from a number of suspected sources that lack sufficient 9 data to make reliable estimates (defined below as preliminary or unquantifiable sources). 10 Because many types of sources release dioxins, it is likely that some have been missed 11 completely. 12 13 All of these factors introduce uncertainty into the release estimates. While most of these 14 uncertainties are impossible to characterize, some can be evaluated as discussed below. 15 The original inventory report (U.S. EPA, 2006) used a qualitative scheme to assess 16 uncertainty. This scheme assigned qualitative confidence ratings to the emission factors, activity 17 levels, and release estimates. The five confidence ratings (Class A, B, C, D, or E) were defined 18 as follows: 19 20 Classes A, B, and C--Class A indicates high confidence, Class B indicates medium 21 confidence, and Class C indicates low confidence. These three classes make up the 22 quantitative inventory. 23 Class D--For many source categories, very limited release data were available and 24 judged to be inadequate to support development of reliable quantitative release estimates 25 for one or more media. For some of these source categories, sufficient information was 26 available, however, to make preliminary estimates of releases. These preliminary 27 estimates were assigned to Class D. 28 Class E--For other sources, no dioxin release data were available, but either formation 29 theory or similarity to other sources with measured releases suggested that releases may 30 occur. These sources were identified to the extent possible, but no release estimates 31 could be made. They were assigned to Class E. 32 33 The overall confidence rating assigned to an emissions estimate was determined by the lowest 34 rating assigned to either the emission factor or activity level. 35 In this update, a revised approach has been developed to characterize the confidence 36 ratings of the release estimates. The revised approach maintains the three major categories 37 previously used, i.e., (1) the quantitative inventory [which now includes the sum of the previous This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-13 DRAFT: DO NOT CITE OR QUOTE 1 confidence ratings that were subdivided into Class A, B, or C], (2) the preliminary release 2 estimates [previously assigned a rating of Class D], and the unquantifiable sources [previously 3 assigned a rating of Class E]. The major changes are the elimination of the Class A, B, or C 4 confidence distinctions in the quantitative inventory and the addition of the quantitative 5 uncertainty analysis of the quantitative inventory (presented in Section 1.3.6). The old Class A, 6 B, and C confidence ratings were eliminated because they were too subjective and difficult to 7 apply in a consistent fashion. Also, it was judged that confidence ratings for the individual 8 source classes were less essential because a new quantitative uncertainty analysis has been 9 added. It was determined that the more important issue was the uncertainty in the total national 10 release estimate. Accordingly, the new quantitative approach focuses on this issue. 11 Key components of both the old and new scheme for assessing uncertainty are the criteria 12 for deciding whether a source belongs in the quantitative inventory or preliminary class. This 13 update uses more specific guidance for making this decision. In order for a source to be included 14 in the quantitative inventory, it must (a) have emission tests for at least two units/source types 15 with sufficient documentation to directly derive emission factors, (b) the measured emission 16 factors must be reasonably consistent or have understandable differences, (c) the emission factor 17 tests must represent units that are reasonably typical of the class and (d) the activity estimates 18 must be based on source-specific surveys. 19 The actual magnitude of releases from the preliminary sources could be significantly 20 lower or higher than estimated. Although EPA has chosen not to include them in the quantitative 21 inventory, it must be emphasized that some of the preliminary sources have the potential of being 22 major contributors of releases to the environment. Accordingly, they are important to identify 23 and can be used to help set priorities for future research and data collection. As the uncertainty 24 around these sources is reduced, they will be included in future inventory calculations. 25 The data used in this document come from hundreds of studies which reported values 26 using a wide range of significant figures. In the present report, the decision about how many 27 significant figures to use began with the general policy to report previously published data in the 28 same manner as in the original publication and to report calculated values with a number of 29 significant figures no more than the input with the least number of significant figures. This 30 document reports all emission factors and releases in TEQs. TEQs are derived from toxicity 31 equivalency factors that are presented with only one significant figure. Although this suggests This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-14 DRAFT: DO NOT CITE OR QUOTE 1 that all TEQ estimates should be presented with only one significant figure, they are commonly 2 reported to 2 or more significant figures in the literature. Limiting the number of significant 3 figures to 1 for the larger release estimates introduces large rounding adjustments. Therefore, it 4 was decided to present the release estimates to 2 significant figures when they equal or exceed 10 5 g TEQ/year. Releases less than 10 g TEQ/year were limited to only 1 significant figure. 6 Releases less than 0.1 g TEQ/year were presented as <0.1 to reflect the additional uncertainty in 7 such small estimates and because they have negligible contributions to the total releases. 8 Similarly the emission factors were reported to 2 significant figures for values that equal or 9 exceed 0.1 ng TEQ/kg and to 1 significant figure for values less than 0.1 ng TEQ/kg. Activity 10 estimates are typically very large numbers and are generally known with more certainty than the 11 emission factors. Therefore, it was decided to report activities to 3 or fewer significant figures. 12 13 1.3. SUMMARY AND CONCLUSIONS 14 Table 1-12 lists all of the quantitative and preliminary CDD/CDF release estimates 15 developed in this document. It also identifies all of the unquantifiable sources. Where feasible, 16 the table presents release estimates to air, water, land, and products for each reference year. As 17 discussed earlier, the preliminary release estimates are not part of the official inventory, but they 18 are included in this table to provide a complete picture of what is known and unknown about 19 potential CDD/CDF releases. 20 Table 1-13 lists all of the quantitative and preliminary PCB release estimates and 21 unquantifiable PCB sources. It is organized in the same manner as Table 1-12. Both Tables 22 1-12 and 1-13 include only contemporary formation sources, i.e., those which form CDD/CDFs 23 during the same time frame as when the releases occur. Releases can also occur from reservoirs, 24 which are defined as materials or places that contain previously released CDD/CDFs or dioxin 25 like PCBs and have the potential for redistributing these compounds into the environment. 26 Tables 1-14 (CDD/CDFs) and 1-15 (PCBs) present releases for reservoirs. Releases from 27 reservoirs are not considered to be part of the official inventory because they are not original 28 releases but rather the recirculation of past releases. 29 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-15 DRAFT: DO NOT CITE OR QUOTE 1 1.3.1. Contemporary Formation Sources 2 Eighty source categories were identified with the potential for dioxin emissions. The 3 major conclusions regarding CDD/CDF releases from contemporary formation sources are 4 presented below: 5 6 The total releases under the national quantitative inventory for 1987 in g WHO98 TEQdf 7 were 15,000 to air, 2,400 to land, 360 to water, and 36 to products. 8 The total releases under the national quantitative inventory for 1995 in g WHO98 TEQdf 9 were 3,400 to air, 2,400 to land, 30 to water, and 47 to products. 10 The total releases under the national quantitative inventory for 2000 in g WHO98 TEQdf 11 were 2,300 to air, 2,300 to land, 28 to water, and 7 to products. 12 Table 1-16 presents a ranking of the top five sources based on the magnitude of 13 environmental release by year and media. The top three air sources in 2000 were forest 14 fires (730 g WHO98 TEQdf), backyard barrel burning of refuse (600 g WHO98 TEQdf), 15 and medical waste incinerators (400 g WHO98 TEQdf). 16 Preliminary sources have the potential for large releases of dioxin-like compounds. The 17 largest preliminary sources are accidental fires at landfills (1,300 g WHO98 TEQdf to air 18 in 2000) and land clearing debris burning (85 g TEQdf to air in 2000). 19 A total of 20 contemporary formation sources were identified as having unquantifiable 20 releases to one or more media. Information suggests these may be sources of dioxin-like 21 compounds, but it is insufficient to make a national estimate of releases. 22 Table 1-17 lists the amounts of CDD/CDF found in several chemical products. The 23 largest amounts are found in pentachlorophenol, but the environmental releases 24 associated with this product (primarily used to treat wood) could not be estimated. 25 Release estimates could only be made for 2,4-D, where it can be assumed that the entire 26 amount produced is released to the environment. 27 28 The environmental releases of dioxin-like PCBs have not been well characterized. PCBs 29 were not produced during the reference years, but are still present in capacitors, transformers, 30 building materials and other products in use today. No estimates could be made for releases 31 from these in-use products. As shown in Table 1-13, only one source (backyard barrel burning) 32 was judged to have adequate data to support quantitative air-release estimates of 41, 43, and 33 34 g WHO98 TEQp for the years 1987, 1995, and 2000, respectively. Similarly, only two sources 34 (backyard barrel burning and municipal wastewater treatment) were judged to have adequate 35 data to support quantitative land release estimates of 52, 78, and 20 g WHO98 TEQp for the years 36 1987, 1995, and 2000, respectively. Also, preliminary estimates could be made for 6 sources, This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-16 DRAFT: DO NOT CITE OR QUOTE 1 and 10 sources were identified as being unquantifiable. Although the information is limited, it 2 suggests that, in terms of TEQs, PCB releases are much lower than CDD/CDF releases. 3 4 1.3.2. Reservoir Sources 5 Soil is likely to be the reservoir source with the greatest potential for release of 6 CDD/CDFs and PCBs to other environmental media, particularly to water. This is due to its 7 relatively large mass of stored CDD/CDFs and PCBs and the existence of demonstrated 8 transport mechanisms for intermedia exchange, e.g., soil erosion to surface waters and particle 9 resuspension to air. 10 The preliminary estimates of CDD/CDF TEQs in soil runoff to waterways (Table 1-14) 11 are more than 100 times greater than known industrial point-source releases to water. It is 12 unclear how much of the soil erosion and runoff represents recently deposited CDD/CDFs from 13 primary sources or longer-term accumulation. Much of the eroded soil comes from tilled 14 agricultural lands, which would include a mix of CDD/CDFs from various deposition times. 15 Five possible product reservoirs were identified: bleached chemical wood pulp, 16 pentachlorophenol, vinyl chloride, chloranil, and PCBs. No estimates could be made for the 17 total mass of CDD/CDFs contained in these reservoirs or their releases. 18 19 1.3.3. Time Trends 20 Some observations about how releases have changed over the reference years can be 21 made for the quantified sources. It is important to understand, though, that these observations do 22 not include the sources classified as preliminary or unquantifiable. Some of the preliminary 23 sources are potentially very large and, if confirmed, could change the trend observations based 24 on the currently quantified sources. With this caveat in mind, the following trends were 25 identified. 26 Table 1-18 shows the total releases in 1987, 1995, and 2000 and the percent changes 27 from 1987 to 1995, 1995 to 2000, and 1987 to 2000. A few sources were included in some 28 reference years and not others due to lack of information. Removal of these sources from the 29 yearly totals only had a large effect on the water release estimates. Thus, the water totals 30 presented in Table 1-18 reflect this adjustment (discussed further below). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-17 DRAFT: DO NOT CITE OR QUOTE 1 In terms of total releases from all media, a 67% reduction occurred from 1987 to 1995, a 2 23% reduction occurred from 1995 to 2000, and a 74% reduction occurred from 1987 to 2000. 3 Further insight can be gained from examining trends occurring in each medium: 4 5 Air--The reductions in total air releases were 85% from 1987 to 2000. Three sources 6 accounted for over 100% of the reduction: municipal waste incinerators (74%), medical 7 waste incinerators (18%), and secondary copper smelters (8%). These reductions were 8 offset by increases in releases from forest fires, which increased by a factor of 4 from 9 1987 to 2000: 180 g WHO98 TEQ in 1987 to 730 g WHO98 TEQ in 2000. Table 1-16 10 shows that the nonindustrial sources have moved to the top of the rankings. 11 Land--Very little change occurred in land releases over the reference years (4% 12 reduction in 1987 to 2000). Land release estimates could only be made for 13 seven sources, and these were dominated by structural fires and backyard barrel burning. 14 Water--Only one source--bleached pulp and paper mills--had water release estimates 15 for each of the reference years. Thus, the trend analysis is limited to this source. The 16 reductions from 1987 to 2000 were almost 100% (360 to 1 g WHO98 TEQ). 17 Product--The reductions in product releases were 81% from 1987 to 2000. Release 18 estimates could only be made for two products: 2,4-D and land-applied municipal 19 wastewater treatment sludge. Assuming that dioxins have been eliminated from 2,4-D by 20 2000 (data are lacking to confirm this), this reduction is virtually 100%. Releases from 21 sludge actually increased from 1987 to 2000, although the amounts were low (i.e., 22 7 gWHO98 TEQ in 2000). 23 24 One way to assess the validity of these trends is to consider the uncertainties associated with 25 the release estimates. As discussed in Section 1.3.6 a propagation of error analysis was used to 26 derive the standard deviation for the air release estimate for the year 2000 based on the top 9 27 sources (releases = 2,100 g WHO98TEQ with SD = 1,300). A similar analysis of the 1987 data 28 suggests that the air releases (14,000 g WHO98 TEQ) have an SD of 3,000. This means that the 29 1987 releases minus two SDs still exceeds the 2000 releases plus two SDs. As a point of 30 comparison, for normal distributions, 95% of the probability falls within two SDs of the mean. 31 Although the distribution of possible releases is likely skewed, the large difference between the 32 total releases and their associated SDs suggest that little overlap occurs between the possible 33 range of estimates for the 1987 and 2000 releases. Thus the results of this analysis strongly 34 support the observation of a downward trend. 35 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-18 DRAFT: DO NOT CITE OR QUOTE 1 Finally further evidence of future downward trends in dioxin emissions to the air can be 2 based on recent rulemaking and data collection efforts conducted by EPA's Office of Air Quality 3 Planning and Standards. The Clean Air Act requires that regulation support efforts include 4 estimates of current nationwide baseline emissions and future reductions that will occur after full 5 implementation of the regulations. The list below shows these estimates for regulation support 6 activities that have occurred after 2000: 7 Sewage sludge incineration - Baseline estimates for 2010 were 0.4 g WHO2005 TEQ/yr 8 with future reductions of 0 g WHO2005 TEQ/yr (ERG, 2011a). This compares to the 9 estimates presented here of 10 g WHO98 TEQ/yr for the year 2000. 10 Medical waste incineration - Baseline estimates for 2008 were 0.83 g WHO2005 TEQ/yr 11 with future reductions of 0.66 g WHO2005 TEQ/yr (Holloway, 2009). This compares to 12 the estimates presented here of 400 g WHO98 TEQ/yr for the year 2000. 13 Secondary copper smelting - US EPA concluded that no dioxin emissions occurred from 14 secondary copper smelting plants in 2006 because all had been shut down (Federal 15 Register, 2006). This compares to the estimates presented here of 0.9 g WHO98 TEQ/yr 16 for the year 2000. 17 Industrial, Commercial, Institutional Boilers and Process Heaters - Baseline estimates for 18 2008 were 37 g WHO2005 TEQ/yr with future reductions of 23 g WHO2005 TEQ/yr 19 (Singleton and Gibson, 2011). This source category does not match exactly with the 20 source definitions used here. It includes industrial oil burning boilers (7 g WHO98 21 TEQ/yr for the year 2000) and industrial coal burning boilers (41 g WHO98 TEQ/yr for 22 the year 2000) 23 Commercial/Industrial solid waste incineration - Baseline estimates for 2010 were 165 g 24 total CDD/Fs with future reductions of 115 g total CDD/Fs (ERG, 2011b). Unfortunately 25 as of press time for the present document, no TEQ conversions were available for these 26 estimates, making comparisons difficult. Also this source category does not match 27 exactly with the source definitions used here. 28 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-19 DRAFT: DO NOT CITE OR QUOTE 1 1.3.4. Sources Not Included in the Inventory 2 Significant amounts of the dioxin-like compounds produced annually in the United States 3 are not considered releases to the open and circulating environment and are not included in the 4 national inventory. Examples include dioxin-like compounds generated internal to a process but 5 destroyed before release and waste streams that are disposed of in approved landfills. 6 A number of contemporary formation sources were classified as preliminary or 7 unquantifiable and, therefore, were not included in the inventory. The largest contemporary 8 formation preliminary source is accidental fires at MSW landfills. This source has the potential 9 to significantly increase the release estimates for 2000 if preliminary estimates are confirmed. 10 The possibility remains that truly undiscovered sources exist. Many of the sources that 11 are well accepted today were discovered only in the recent past. For example, CDDs/CDFs in 12 stack emissions from MWCs were not detected until the late 1970s; CDDs/CDFs in the 13 wastewater effluent from bleached pulp and paper mills were found unexpectedly in the 14 mid-1980s; iron ore was not recognized as a source until the early 1990s. 15 16 1.3.5. Congener Profiles of CDD/CDF Sources 17 The 2006 document presented congener profiles for a number of sources, showing the 18 relative amounts of CDD/CDF congeners in environmental releases. While these profiles can be 19 useful for identifying sources, they are not essential to the inventory itself. Therefore, they were 20 not updated in the present document. 21 22 1.3.6. Uncertainty Analysis 23 The purpose of this section is to present a quantitative analysis of the uncertainty in the 24 total release estimates. Given the wide scope of this document (over 80 source categories, 25 three reference years and four release media), a number of steps were taken to simplify this 26 analysis. First, it was limited to the 2000 releases because these are the most current. Second, it 27 was limited to the air and land releases. The releases to the other media are so much smaller, 28 they will have negligible impact on the overall uncertainty (air--2,300 g WHO98 TEQ, land-- 29 2,200 g WHO98 TEQ, water--28 g WHO98 TEQ and product--7 g WHO98-TEQ). Finally, the 30 number of source categories included in the analyses was limited to the largest ones, with 31 cumulative contributions of about 90% of the total releases. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-20 DRAFT: DO NOT CITE OR QUOTE 1 2 1.3.6.1. A ir R e le a se s 3 The uncertainty was first evaluated using a propagation of error approach. This involves 4 estimating the variance for the emissions from each source and summing these to get the overall 5 variance in total emissions. Multiple factors contribute to the uncertainty in the emission 6 estimate for a class of facilities. These include sampling error which reflects the number of 7 facilities tested out of the total, the representativeness of the tests of long term conditions and 8 measurement error from inaccuracies in the stack monitoring and chemical analysis. The 9 propagation of error approach used here assumes that the variability in the emissions from the 10 sampled facilities is an indication of the possible uncertainty in the emissions from the whole 11 class of facilities. While some of the variability is due to differences in the design and operation 12 of the facilities, some also results from the various sources of uncertainty. It is impossible to 13 know how much of the variability can be attributed to design/operation versus uncertainty, so 14 this approach interprets all of the variability as an indication of the possible uncertainty. While 15 this may imply an overestimate of the uncertainty, this is offset to some degree by the limitations 16 of the database, such as the small n's for many classes, lack of testing during start-up and 17 shutdown, use of short term testing to represent long term conditions, etc. 18 The total releases (Rtotal) are calculated by summing the releases across the 9 largest air 19 sources (Ri) which account for over 90% of the total: 20 21 R t. ,, = Z R (1-6) i=1 22 23 The emissions from each source are computed as the product of the emission factor and activity: 24 i25 =R r o ,,, EF, x A, (1-7) i=1 26 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-21 DRAFT: DO NOT CITE OR QUOTE 1 where 2 Riotai = Total Releases (g TEQ/year) 3 EF; = Emission factor for source i (ng TEQ/kg) 4 Ai = Activity for source i (kg/year) 5 6 The emission factor is calculated on the basis of emission measurements that involve some error. 7 Sampling error results from the fact, in general, only a small subset of the total facilities in each 8 source class was tested. Measurement error is associated with stack sampling procedures and 9 has been estimated to be +/- 30% for dioxins (U.S. EPA, 1990b). Lanier and Hendrix (2001) 10 assessed the accuracy of Test Method 23 for stack measurements of PCDD and PCDFs. For 11 determination of total PCDD/PCDF mass, the analysis found that RSD varied between about 6.3% 12 and 20% for stack concentrations in the range of 2 to 27 ng/dscm. Although activity estimates also 13 have uncertainty, it is assumed here that this is negligible compared to the uncertainty in the 14 emission factor. The amount of error in estimating the releases from each source is assumed to 15 be independent of each other. The variance in releases from each source is estimated using the 16 variance of the emission factor data and treating the activity as a constant: 17 9 18 v a ria n c e i n R T,otal = ^ v a ria n c e in E F t x Ai 2 (1-8) i=1 19 20 Generally, the variance estimates for the emission factors were derived using the standard 21 equation, i.e. E(x - 0) /(n-1). However, in a few cases, some special considerations were 22 necessary: 23 24 The emission factor data for forest fires consisted of a series of chamber tests and field 25 tests. Given the fundamental differences in the data from these two types of tests, it was 26 not considered appropriate to combine them. Instead, the emission factor was estimated 27 for each data set and averaged to get the best overall estimate: 28 29 E F = 0.5( E F field + E F chamber) (1-9) 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-22 DRAFT: DO NOT CITE OR QUOTE 1 v a ria n ce in E F = 0.52( v a ria n ce in E F field + va ria n ce in E F chamber) (1-10) 2 3 In 2000, stack tests were available for all operating municipal waste incinerators and 4 cement kilns burning hazardous waste. The total emissions for these two classes were 5 estimated by summing the individual emissions from each facility. Thus, an 6 emission-factor approach based on a subset of the facilities was not necessary. Because 7 all facilities were tested, in theory, there is no sampling error. However, it is recognized 8 that factors other than sampling error can contribute to the error in these estimates. 9 Therefore, the variance for these sources were estimated and included in the propagation 10 of error calculation. 11 12 Table 1-19 summarizes the results of this analysis. The analysis concludes that the total 13 emissions sum to 2,100 g TEQ/year with a standard deviation of 1,300 g TEQ/year. 14 Frey and Zhao (2004) demonstrated that probabilistic methods can be used to evaluate 15 uncertainties in emission inventories for benzene, formaldehyde, chromium, and arsenic. 16 Accordingly, a probabilistic approach was also explored here as discussed below. 17 Probabilistic methods for evaluating uncertainty require developing distributions for the 18 input variables. Frey and Zhao (2004) fit their emission factor data to parametric distributions 19 using maximum likelihood estimation. This is a complex procedure and difficult to apply 20 accurately to the emission factor data sets with low n values. Instead, all emission factors were 21 assumed to have log normal distributions with means and standard deviations based on an 22 arithmetic analysis of the data. Log normal distributions have been found to apply to many types 23 of environmental data including emission factors (Frey and Zhao, 2004). A Monte Carlo 24 analysis was conducted using the Crystal Ball program. A total of 10,000 simulations were run, 25 producing a mean of 2,100 g TEQ and standard deviation of 1,100 g TEQ, which are very similar 26 to the results of the propagation-of-error approach described above. Percentiles were estimated 27 as 1,100 g TEQ for 10%, 1,800 g TEQ for 50%, and 3,300 g TEQ for 90%. These percentiles 28 can be interpreted as the probability that the emissions will less than or equal to the specified 29 amount. 30 Finally, further analysis is offered on the uncertainties associated with the forest fires. 31 These uncertainties are especially important to evaluate because they are the largest source and 32 have high uncertainty in the emission factor. As stated above, both chamber studies and field 33 studies have been used to measure these emissions. The field data suggest an emission factor of This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-23 DRAFT: DO NOT CITE OR QUOTE 1 0.95 ng TEQ/kg, and the chamber data suggest an emission factor of 7.5 ng TEQ/kg. If the 2 lower emission factor is used, the forest fires would have a release of 230 g TEQ, and the total 3 releases across the 9 top sources would be 1,600 g TEQ. Similarly, if the higher emission factor 4 is used, the forest fires would have a release of 1,800 TEQ, and the total releases across the 5 nine top sources would be 3,200 g TEQ. 6 7 I.3.6.2. L a n d R e le a se s 8 The 2000 land releases were dominated by backyard barrel burning which had releases of 9 1,900 g WHO98 TEQ (88% of the total) and the uncertainty analysis was limited to this 10 one source. The releases from backyard barrel burning were based on a study by Lemieux 11 (1997). Ash samples from the experiments were combined, resulting in two composite samples, 12 one for recyclers (2,700 ng WHO98 TEQdf /kg ash) and one for nonrecyclers 13 (620 ng WHO98 TEQdf /kg ash). The final emission factor was based on the average of these 14 values (1,700 ng WHO98 TEQDF/kg ash). The limited data do not allow a statistical analysis 15 such as done for the air releases. Instead a potential range of releases was estimated based on the 16 lower and upper emission factor estimates. The activity estimate for 2,000 was 1.2 MMT. 17 Combining this value with the lower emission factor yields a release estimate of 18 740 g WHO98 TEQ. Combining the activity with the higher emission factor yields a release 19 estimate of 2,800 g WHO98 TEQ. Accordingly the potential range of releases is 740 to 20 2,800 g WHO98 TEQ. Relative to the average value (1,900 g WHO98 TEQ), the lower estimate 21 is 62% less and the upper estimate is 46% more. 22 23 1.3.7. Relative Impact of Releases 24 When comparing national release estimates across sources, it should not be assumed that 25 the magnitude of dioxin-like compound emissions is proportional to their impact on human 26 health. Human exposure to dioxins occurs primarily via the diet. Therefore, factors such as the 27 proximity of sources to food production areas and their location relative to wind direction may 28 cause disproportionate impacts from emissions. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-24 DRAFT: DO NOT CITE OR QUOTE Table 1-1. Nomenclature for dioxin-like compounds Term/symbol CDD CDF PCB M D Tr T Pe Hx Hp O 2,3,7,8 Congener Congener group Isomer Specific isomer Definition Chlorinated dibenzo-p-dioxin, halogens substituted in any position Chlorinated dibenzofuran, halogens substituted in any position Polychlorinated biphenyl Symbol for mono (i.e., one halogen substitution) Symbol for di (i.e., two halogen substitution) Symbol for tri (i.e., three halogen substitution) Symbol for tetra (i.e., four halogen substitution) Symbol for penta (i.e., five halogen substitution) Symbol for hexa (i.e., six halogen substitution) Symbol for hepta (i.e., seven halogen substitution) Symbol for octa (i.e., eight halogen substitution) Halogen substitutions in the 2,3,7,8-positions Any one particular member of the same chemical family (e.g., there are 75 congeners of CDDs) Group of structurally related chemicals that have the same degree of chlorination (e.g., there are eight congener groups of CDDs, MCDD through OCDD) Substances that belong to the same congener group (e.g., 22 isomers constitute the congener group of TCDDs) Isomers denoted by unique chemical notation (e.g., 2,4,8,9-tetrachlorodibenzofuran is referred to as 2,4,8,9-TCDF) MCDD = monochlorinated. OCDD = octachlorinated. Source: Adapted from U.S. EPA (1989). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-25 DRAFT: DO NOT CITE OR QUOTE Table 1-2. TEF schemes for CDDs, CDFs, and PCBs Compound Chlorinated dibenzo-p-dioxins 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD Chlorinated dibenzofurans 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,6,7,8,9-HpCDF OCDF I-TEFs 1 0.5 0.1 0.1 0.1 0.01 0.0001 0.1 0.05 0.5 0.1 0.1 0.1 0.1 0.01 0.01 0.0001 WHO94 WHO98 WHO2005 1 1 0.1 0.1 0.1 0.01 0.0001 1 1 0.1 0.1 0.1 0.01 0.0003 0.1 0.05 0.5 0.1 0.1 0.1 0.1 0.01 0.01 0.0001 0.1 0.03 0.3 0.1 0.1 0.1 0.1 0.01 0.01 0.0003 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-26 DRAFT: DO NOT CITE OR QUOTE Table 1-2. TEF schemes for CDDs, CDFs, and PCBs (continued) Compound Polychlorinated Biphenyls 3,3',4,4'-TCB (PCB-77) 3,4,4',5-TCB (PCB-81) 2,3,3',4,4'-PeCB (PCB-105) 2,3,4,4',5-PeCB (PCB-114) 2,3',4,4',5-PeCB (PCB-118) 2',3,4,4',5-PeCB (PCB-123) 3,3',4,4',5-PeCB (PCB-126) 2,3,3',4,4',5-HxCB (PCB-156) 2,3',4,4',5,5'-HxCB (PCB-157) 2,3',4,4',5,5'-HxCB (PCB-167) 3,3',4,4',5,5'-HxCB (PCB-169) 2,2',3,3',4,4',5-HpCB (PCB-170) 2,2',3,4,4',5,5'-HpCB (PCB-180) 2,3,3',4,4',5,5'-HpCB (PCB-189) OCDF = octachlorodibenzofuran. OCDD = octachlorinated. I-TEFs WHO94 0.0005 0.0001 0.0005 0.0001 0.0001 0.1 0.0005 0.0005 0.00001 0.01 0.0001 0.00001 0.0001 WHO98 0.0001 0.0001 0.0001 0.0005 0.0001 0.0001 0.1 0.0005 0.0005 0.00001 0.01 0.0001 WHO2005 0.0001 0.0003 0.00003 0.00003 0.00003 0.00003 0.1 0.00003 0.00003 0.00003 0.03 0.00003 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-27 DRAFT: DO NOT CITE OR QUOTE Table 1-3. Municipal waste combustors3 New, large Categoryb Existing, large With electrostatic precipitators as the APCD With dry scrubber/fabric filters as the APCD New, small Existing, small With electrostatic precipitators as the APCD With dry scrubber/fabric filters as the APCD Stack emission limitc (ng total CDD/CDF/dscm) Effective date 13 September 20, 1994d June 19, 1996e 60 When SIPs are 30 approvedf 13 June 6, 2001g 60 When SIPs are 30 approved11 aAir emission standards promulgated on December 19, 1995. bLarge = aggregate capacity >225 tons/day; small = aggregate capacity <225 tons/day. cng total CDD/CDF/dscm = nanograms total Cl4-C l8 CDDs plus CDFs per dry standard cubic meter of stack gas volume, corrected to 7% O2. dBegan construction on this date. eModified or upgraded on this date. fWhen SIPs have been approved by EPA (approximately 3 years from the final rule, or 1998). gFor facilities constructed on or before this date. hWhen SIPs have been approved by EPA (approximately 3 years from the final rule, or 2003). APCD = air pollution control device. SIP = State Implementation Plan. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-28 DRAFT: DO NOT CITE OR QUOTE Table 1-4. Hazardous waste combustors3 1 Source category Standards for new sourcesb Standards for existing sourcesb Incinerators burning For an incinerator with dry For an incinerator with drv APCD hazardous waste APCD and/or waste heat boiler: and/or waste heat boiler: 0.11 ng I-TEQ/dscm 0.20 ng I-TEQ/dscm, or 0.40 ng I-TEQ/dscm when PM control device operated >400F For all other incinerators: For all other incinerators: Cement kilns burning hazardous waste Lightweight aggregate kilns burning hazardous waste Solid fuel boilers burning hazardous waste Liquid fuel boilers burning hazardous waste 0.20 ng I-TEQ/dscm 0.20 ng I-TEQ/dscm, or 0.40 ng I-TEQ/dscm when PM control device operated >400F 0.20 ng I-TEQ/dscm, or rapid quench of combustion gas to below 400F at kiln exit Either CO of 100 ppmv or HC of 10 ppmv For a LFB with dry APCD: 0.40 ng I-TEQ/dscm. 0.40 ng I-TEQ/dscm 0.20 ng I-TEQ/dscm, or 0.40 ng I-TEQ/dscm when PM control device operated >400F 0.20 ng I-TEQ/dscm, or rapid quench of combustion gas to below 400F at kiln exit Either CO of 100 ppmv or HC of 10 ppmv For a LFB with drv APCD: 0.40 ng I-TEQ/dscm. For all other LFBs: For all other LFBs: Hydrochloric acid production furnaces burning hazardous waste Either CO of 100 ppmv or HC of 10 ppmv Either CO of 100 ppmv or HC of 10 ppmv Either CO of 100 ppmv or HC of 10 ppmv Either CO of 100 ppmv or HC of 10 ppmv aAir emission standards promulgated October 12, 2005. bng I-TEQ/dscm= nanogramI-TEQper dry standard cubic meter of stack gas volume corrected to 7%O2. APCD = Air pollution control device (dry = dry scrubber or fabric filter). 2 CO= carbon monoxide continuously monitored. 3 HC = Total hydrocarbons continuously monitored. 4 LFB =Liquid fuel boiler. PM=Particulate matter. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-29 DRAFT: DO NOT CITE OR QUOTE Table 1-5. Cement kilns not burning hazardous wastea Existing cement kilnsb 0.20 ng I-TEQ/dscm and temperature control <400EF at the APCD inlet 0.40 ng I-TEQ/dscm when PM control device operated >400EF New cement kilnsb 0.20 ng I-TEQ/dscm and temperature control <400EF at the APCD inlet 0.40 ng I-TEQ/dscm when PM control device operated >400EF aAir emission standards promulgated on June 14, 1999. bng I-TEQ/dscm = nanograms I-TEQ per dry standard cubic meter of stack gas volume corrected to 7% O2. APCD = Air pollution control device. PM = Particulate matter. Table 1-6. Secondary aluminum smeltersa Process Sweat furnace Thermal chip dryer Scrap dryer/delacquering kiln/decoating kiln Scrap dryer/delacquering kiln/decoating kiln equipped with an afterburner Emission standard 0.8 ng I-TEQ/dscm stack gas corrected to 7% O2 2.50 qg I-TEQ per MT of scrap charged to the dryer 0.25 g I-TEQ per MT of scrap charged to the kiln 5.0 g I-TEQ per MT of scrap charged to the kiln aAir emission standards promulgated on March 23, 2000. MT = metric ton. 1 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-30 DRAFT: DO NOT CITE OR QUOTE Table 1-7. Medical waste incinerators3 Category Large Medium Small Small rural "Federal Register, 2009. Existing (ng WHO2005TE Q/dscm) 0.054 0.020 0.013 2.1 New (ng WHO2005TE Q/dscm) 0.035 0.014 0.013 Table 1-8. Pulp and paper mills3 Pollutant Tetrachl orodib enzo-p-di oxin Tetrachl orodib enzofuran Maximum 1-day wastewater discharge <5 parts per quadrillion 31.9 picograms per liter "Effluent limitation guidelines promulgated on April 15, 1998. Table 1-9. Commercial/Industrial solid waste incinerators3 Category Incinerators Energy Recovery Units solids Energy Recovery Units liquid/gas Waste Burning Kilns Small, remote Incinerators Existing (ng WHO2005TE Q/dscm) 0.13 0.059 0.32 0.0070 57 "Federal Register, 2011a. New (ng WHO2005TE Q/dscm) 0.13 0.011 0.002 0.0030 31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-31 DRAFT: DO NOT CITE OR QUOTE Table 1-10. Sewage sludge incinerators3 Category Multiple Hearth Fluidized Bed Existing (ng WHO2005TEQ/dscm) 0.32 0.10 New (ng WHO2005TEQ/dscm) 0.0022 0.0044 "Federal Register, 2011b. Table 1-11. Industrial, commercial, and institutional boilers and process heaters3 Category Coal Stoker Coal Fluidized Bed Pulverized Coal Biomass Stoker/other Biomass Fluidized Bed Biomass Dutch Oven/Suspension Burner Biomass Fuel Cells Biomass Suspension/Grate Liquid Gas 2 (Other Process Gases) Non-continental liquid Existing (ng WHO2005TEQ/dscm) 0.003 0.002 0.004 0.005 0.02 0.2 4 0.2 4 0.08 4 New (ng WHO2005TEQ/dscm) 0.003 0.002 0.003 0.005 0.02 0.2 0.003 0.2 0.002 0.08 0.002 "Federal Register, 2011c. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-32 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) This document is a draftfor review purposes only and does not constitute Agency policy. Source Municipal solid waste incinerators 1987 1995 2000 Hazardous waste incinerators 1987 1995 2000 Industrial boilers burning haz. waste 1987 1995 2000 Halogen acid furnaces burning haz. waste 1987 1995 2000 Air releases Land releases Water releases Product releases Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ. WASTE INCINERATION 9,500 1,200 77 xx xx xx 5x 6x 3x 0.8 x 0.4 x 0.7 x 0.3 x 0.3 x 0.3 x 1-33 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Air releases Land releases Water releases Product releases Source Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ Medical waste incinerators 1987 1995 2000 2,700 510 400 x x x Human crematoria 1987 1995 2000 0.2 0.2 0.3 Animal crematoria 1987 1995 2000 3 4 4 Sewage sludge incinerators 1987 1995 2000 6 14 10 x x x Tire combustion 1987 1995 2000 0.1 0.1 0.5 x x x Biogas combustion 1987 1995 2000 0.2a 0.2a 0.2a 1-34 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Leaded gasoline, on-road 1987 Leaded gasoline, off-road 1987 Unleaded gasoline, on-road 1987 1995 2000 Unleaded gasoline, off road 1987 1995 2000 Diesel, on-road 1987 1995 2000 Diesel, off-road 1987 1995 2000 Air releases Q. Inv. Prelim. Land releases Water releases NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. POWER/ENERGY GENERATION Product releases Q. Inv. Prelim. NQ 50 3 5 6 7 0.2 0.3 0.4 51 55 64 19 20 23 1-35 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Indoor residential wood burners 1987 1995 2000 Outdoor wood-fired boilers 2000 Industrial wood combustion 1987 1995 2000 Commercial and residential oil combustion 1987 1995 2000 Utility sector and industrial oil combustion 1987 1995 2000 Air releases Land releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ 36 21 19 11 15 9 9 78 78 82 6 6 7 19 14 15 Water releases Product releases Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ 1-36 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Waste oil combustion 1987 1995 2000 Industrial coal-fired utilities 1987 1995 2000 Industrial coal-fired boilers 1987 1995 2000 Residential coal combustion 1987 1995 2000 Cement kilns burning hazardous waste 1987 1995 2000 Air releases Q. Inv. Prelim. 0.6 0.7 0.7 51 60 70 48 46 41 10 5 3 120 160 19 Land releases NQ Q. Inv. Prelim. NQ Water releases Product releases Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ 17 18 22 0.1 0.1 <0.1 OTHER HIGH TEMPERATURE SOURCES 4a 4a 3a x x x x x x 1-37 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Air releases Land releases Water releases Product releases Source Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ Cement kilns not burning hazardous waste 1987 1995 2000 13 17 17 <0.1 x <0.1 x <0.1 x Lightweight aggregate kilns 1987 1995 2000 3a 2a 2 Asphalt mixing plants 1987 1995 2000 5a 5a 5a Petroleum refining catalyst regeneration plants 1987 1995 2000 2 2 2 x x x Cigarette smoking 1987 1995 2000 1 0.8 0.7 1-38 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Air releases Land releases Water releases Product releases Source Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ Carbon reactivation furnaces 1987 1995 2000 0.1 0.1 0.1 Kraft black liquor recovery boilers 1987 1995 2000 2 2 0.9 Lime kilns 2000 0.1 Tf Glass manufacturing 1987 1995 2000 Automobile shredders and thermal APCDs at plating and painting facilities 1987 1995 2000 x x x 1-39 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 1-40 DRAFT: DO NOT CITE OR QUOTE Source Combustion of landfill gas 1987 1995 2000 Structural fires 1987 1995 2000 Vehicle fires--cars and other vehicles 1987 1995 2000 Landfill fires 1987 1995 2000 Forest and brush fires 1987 1995 2000 Backyard burning 1987 1995 2000 Air releases Land releases Water releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. MINIMALLY CONTROLLED OR UNCONTROLLED COMBUSTION Product releases Q. Inv. Prelim. NQ 2a 7a 22a 24 260 18 200 16 180 x x x 39a 29a 24a 1,300 1,300 1,300 180 170 730 610 630 600 11a x 7a x 6a x 2,000 2,000 2,000 18a 17a 73a x x x 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 1-41 DRAFT: DO NOT CITE OR QUOTE Air releases Land releases Water releases Product releases Source Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ Residential yard burning 1987 1995 2000 4 5 5 <0.1 <0.1 <0.1 Land clearing debris burning 1987 1995 2000 83 79 85 8 8 9 Open burning of demolition/construction wood 1987 1995 2000 22 22 22 240 240 240 Fireworks, underground coal fires, open burning of energetic materials, PCBs, candles, oil spills 1987 1995 2000 x x x x x x Sugar cane burning 1987 1995 2000 28 31 35 1 2 2 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 1-42 DRAFT: DO NOT CITE OR QUOTE Source Primary copper smelting and refining 1987 1995 2000 Primary magnesium smelting and refining 1987 1995 2000 Primary nickel smelting and refining 1987 1995 2000 Primary titanium smelting and refining 1987 1995 2000 Secondary aluminum smelting 1987 1995 2000 Air releases Q. Inv. Prelim. Land releases Water releases NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. METALLURGICAL PROCESSES Product releases Q. Inv. Prelim. NQ 0.3a 0.5a 0.5a 13 x 13 x 8x xx xx x xx xx xx 11 20 8 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 1-43 DRAFT: DO NOT CITE OR QUOTE Air releases Land releases Water releases Product releases Source Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ Secondary zinc production 1987 1995 2000 4a 7a 7a Secondary copper smelting 1987 1995 2000 990 270 0.9 Secondary lead smelting 1987 1995 2000 1 2 2 Sinter production 1987 1995 2000 33 28 24 Coke production 1987 1995 2000 10a 9a 8a Secondary ferrous metal smelting/refining 1987 1995 2000 37 46 59 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Ferrous foundries 1987 1995 2000 Aluminum foundries 1987 1995 2000 Copper foundries 1987 1995 2000 Scrap electric wire recovery 1987 1995 2000 Drum and barrel reclamation furnaces 1987 1995 2000 Air releases Q. Inv. Prelim. Land releases NQ Q. Inv. Prelim. NQ Water releases Product releases Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ 13 19 16 0.3a 0.3a 0.3a <0.1a <0.1a <0.1a xx xx xx 0.6 x 0.6 x 0.6 x 1-44 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Bleached chemical pulp and paper mills 1987 1995 2000 Stand-alone chlor-alkali plants 1987 1995 2000 Stand-alone vinyl chloride plants 1987 1995 2000 Complex chemical plants producing chlorine and a variety of chlorinated organics 1987 1995 2000 Air releases Land releases Water releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ. CHEMICAL MANUFACTURING/PROCESSING SOURCES Product releases Q. Inv. Prelim. NQ 14 360 2 28 0.2 1 x x x <0.1a <0.1a 2a 2a 0.6a <0.1a x 33 29 5 1 25 x 1-45 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Municipal wastewater treatment plants 1987 1995 2000 Residential septic systems 1987 1995 2000 Manufacturing of soaps, detergents, textiles, dyes, pigments, and inks 1987 1995 2000 All natural processes and sources, including ball clay, biotransformation, etc. 1987 1995 2000 Air releases Land releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ 62 120 50 0.2 0.2 0.3 x x x xx xx xx Water releases Product releases Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ 13 3 12 18 15 7 x x x 1-46 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-12. Summary of CDD/CDF releases for reference years 1987, 1995, and 2000 (g WHO98 TEQDF/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source TOTALS 1987 1995 2000 Air releases Q. Inv. Prelim. Land releases NQ Q. Inv. Prelim. NQ Water releases Product releases Q. Inv. Prelim. NQ. Q. Inv. Prelim. NQ 15,000 3,400 2,300 1,500 1,500 1,500 2,400 2,400 2,300 270 270 330 360 13 30 12 28 15 36 47 7 "Results provided in I-TEQ. x = Releases are possible during this year, but the data are insufficient to develop estimates. Q. Inv. = Quantitative Inventory. Prelim. = Preliminary. NQ = Not quantified. APCD = air pollution control device. Blanks = No evidence that releases occur. 1-47 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-13. Summary of PCB releases for reference years 1987, 1995, and 2000 (g WHO98 TEQp/year) This document is a draftfor review purposes only and does not constitute Agency policy. Source PCB incineration Accidental fires, leaks, and spills Municipal wastewater treatment 1987 1995 2000 Municipal waste combustors 1987 1995 2000 Industrial wood combustion Medical waste incineration 1987 1995 2000 Tire combustion Air releases Land releases Water releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ RELEASES FROM COMMERCIAL PCB PRODUCTS xx x xx Product releases Q. Inv. Prelim. NQ CHEMICAL MANUFACTURING AND PROCESSING SOURCES 51 78 19 COMBUSTION SOURCES 7 15 15 x 2 12 3 97 18 14 x 1-48 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-13. Summary of PCB releases for reference years 1987, 1995, and 2000 (g WHO98 TEQp/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Cigarette smoking 1987 1995 2000 Sewage sludge incineration 1987 1995 2000 Backyard barrel burning 1987 1995 2000 Petroleum refining catalyst regeneration Hazardous waste incineration Power plants Forest fires 1987 1995 2000 Air releases Land releases Water releases Product releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ <0.1 <0.1 <0.1 0.4 1 0.7 41 1 43 1 34 0.8 x x x 12 11 49 x 1-49 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 1-13. Summary of PCB releases for reference years 1987, 1995, and 2000 (g WHO98 TEQp/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Iron ore sintering 1987 1995 2000 Copper smelting Aluminum smelting TOTAL 1987 1995 2000 Air releases Land releases Water releases Product releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ METAL REFINING 4 3 3 x x 41 120 43 48 34 82 52 79 20 2 12 3 x = Releases are possible during this year, but the data are insufficient to develop estimates. Q. Inv. = Quantitative Inventory. Prelim. = Preliminary. NQ = Not quantified. Blanks = No evidence that releases occur. 1-50 DRAFT: DO NOT CITE OR QUOTE Table 1-14. Summary of CDD/CDF reservoir releases (g WHO98 TEQDF) Source Soil reservoirs 1987 1995 2000 Water, sediment, biota reservoirs 1987 1995 2000 Product reservoirs 1987 1995 2000 Air releases Q. Inv. Prelim. NQ x x x x x x x x x Land releases Q. Inv. Prelim. NQ x x x x x x Water releases Q. Inv. Prelim. NQ 5,000a 4,600a 4,300a x x x x x x includes both urban and rural waters. x = Releases are possible during this year, but the data are insufficient to develop estimates. Q. Inv. = Quantitative Inventory. Prelim. = Preliminary. NQ = Not quantified. Table 1-15. Summary of PCB reservoir releases (g WHO98 TEQP) Source Soil reservoirs 1987 1995 2000 Water, sediment, biota reservoirs 1987 1995 2000 Product reservoirs 1987 1995 2000 Air releases Q. Inv. Prelim. NQ x x x x x x x x x Land releases Q. Inv. Prelim. NQ Water releases Q. Inv. Prelim. NQ 200a 180a 170a xx xx xx xx xx xx aIncludes rural waters only. x = Releases are possible during this year, but the data are insufficient to develop estimates. Q. Inv. = Quantitative Inventory. Prelim. = Preliminary. NQ = Not quantified. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-51 DRAFT: DO NOT CITE OR QUOTE Table 1-16. Ranking of top five sources by year and media release 1987 releases (g TEQ) 1995 releases (g TEQ) Air Municipal waste-- 9,500 Municipal waste incineration-- 1,200 Medical waste--2,700 Backyard barrel--630 2 copper--990 Medical waste incineration--510 Backyard barrel--610 2 copper--270 Forest-- 180 Forest-- 170 Land Backyard barrel--2,000 Structure fires--260 Municipal waste treatment--62 Residential wood--21 Coal utilities-- 17 Backyard barrel--2,100 Structure fires--200 Municipal waste treatment-- 120 Coal utilities-- 18 Residential wood-- 11 Water Paper mills--360 Paper mills--28 Chlor-alkali plants--2 2000 releases (g TEQ) Forest--730 Backyard barrel--600 Medical waste incineration--400 Industrial wood--82 Municipal waste incineration--77 Backyard barrel--2,000 Structure fires-- 180 Municipal waste treatment--50 Coal utilities--22 Residential wood--9 Chlorinated organics--25 Chlor-alkali plants--2 Paper mills-- 1 Table 1-17. Amounts of CDDs/CDFs (g WHO98 TEQDF/year) contained in products in year manufactured Product Bleached chemical wood pulp Ethylene dichloride/vinyl chloride Chloranila Pentachlorophenol 2,4 -Dichlorophenoxy acetic acid (2,4-D)a TOTAL 1987 500 NA 64b 20,000 33 21,000 1995 40 0.02 0.4b 4,800 29 4,900 2000 0.6 0.02 1.2b 4,200 NA 4,200 aOnly 2,4-D is considered to be an environmental release. bUnits are I-TEQ. NA = not available. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-52 DRAFT: DO NOT CITE OR QUOTE Table 1-18. Trend analyses based on quantitative inventory3 Air Land Waterb Product Total Releases (g WHO98 TEQ) 1987 1995 2000 15,000 3,400 2,300 2,400 2,500 2,300 360 28 1 36 47 7 18,000 6,000 4,600 Percent change 1987 to 1995 1995 to 2000 1987 to 2000 -77 -32 -85 +4 -8 -4 -92 -96 -100 +31 -85 -81 -67 -23 -74 aThese trends are based on the quantitative inventory only, i.e., they do not include the sources classified as preliminary or unquantifiable. Some of the preliminary sources are potentially very large and if confirmed could significantly change the trend observations. bWater releases are based on bleached pulp and paper plants only because this is only source covered in all three reference years. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-53 DRAFT: DO NOT CITE OR QUOTE Table 1-19. Uncertainty analysis for top nine air sources in 2000 Forest fires Backyard barrel burning Medical waste Uncontrolled Controlled Activity (kg) Total 2.44 x 1011 7.79 x 109 1.98 x 108 4.03 x 108 Emission factor (ng WHO9 8 -TEQ/kg) mean n SD 3 13 4.7 77 5 53 1,900 51 7 13 1,600 81 Releases (g WHO9 8 -TEQ) Total SD 730 1,100 600 410 380 320 20 33 Municipal waste combustion 105 77 27 Coal fired utility boilers 8.94 x 1011 0.078 11 0.2 70 130 Industrial wood Salt laden Nonsalt laden 8.0 x 108 15 5 11 12 8.9 1.16 x 1011 0.6 9 0.6 70 66 Diesel on-road vehicles Cement kilns Burning haz waste Not burning haz waste 1.19 x 1011a 6.37 x 1010 540b 0.27 7 22 13 240b 0.9 64 19 17 29 7 55 Industrial coal-fired boilers Total releases 5.92 x 1010 aUnits are L. bUnits are pg WHO98-TEQ/L. 0.7 15 1.3 41 78 2,100 1,300 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-54 DRAFT: DO NOT CITE OR QUOTE Process Inputs and Outputs Air Emissions Landfill Incinerator By-Product Open LDaisnpdosal Figure 1-1. Process inputs and outputs. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1-55 DRAFT: DO NOT CITE OR QUOTE 1 2. MECHANISMS OF FORMATION OF DIOXIN-LIKE COMPOUNDS DURING 2 COMBUSTION OF ORGANIC MATERIALS 3 4 5 This chapter has not been updated because it is not critical to the inventory and may be 6 best presented elsewhere. Accordingly, any future updates to this chapter will be pursued 7 independently from the inventory. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 2-1 DRAFT: DO NOT CITE OR QUOTE 1 3. COMBUSTION SOURCES OF CDDS/CDFS: WASTE INCINERATION 2 3 4 3.1. MUNICIPAL WASTE COMBUSTION 5 3.1.1. Air Releases 6 More information was available for the municipal waste incinerators than any other 7 source, allowing a detailed approach for estimating the total emissions. Stack test data were 8 available for 11 of 111 facilities in 1987, 27 of 125 facilities in the 1995, and 78 of 105 facilities 9 in 2000. These data were used to develop emission factors for over 20 design classes based on 10 the combination of furnace type and air pollution controls. Additionally, a complete list of all 11 facilities operating in the reference years and their activity levels were available. Releases from 12 the tested facilities were derived directly from the stack tests, and the releases from the untested 13 facilities were derived by assigning it an emission factor and multiplying by the activity. Finally, 14 the total releases for each reference year were estimated by summing the releases from each 15 facility operating in that year. 16 This approach is a modification of the approach used in the 2006 report. Emission 17 factors were changed for a few design classes to make them more consistent, and new tables 18 were developed for each reference year that list each facility and its emission factor, activity 19 level, and emission rate (see Tables 3-1, 3-2, and 3-3). This led to some minor changes in total 20 emissions. 21 The releases for the year 2000 were also estimated using the UNEP (2005) emission 22 factors: 23 24 Low technology, no APCD--35,000 ng I-TEQ/kg 25 Controlled, minimal APCD--350 ng I-TEQ/kg 26 Controlled, good APCD--30 ng I-TEQ/kg 27 High technology, sophisticated APCD--0.5 ng I-TEQ/kg 28 29 The emission factor for controlled facilities with good APCDs (30 ng I-TEQ/kg) was 30 applied to all small incinerators (defined as those with operating capacities less than 250 tons/day 31 and totaling 2.6 million tons in 2000), and the emission factor for high technology facilities with 32 sophisticated APCDs (0.5 ng I-TEQ/kg) was applied to all large facilities (defined as those with This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-1 DRAFT: DO NOT CITE OR QUOTE 1 operating capacities greater than 250 tons/day and totaling 27 million tons in 2000). This 2 approach yields a release estimate of 92 g I-TEQ/year, which is comparable to the 3 69 g I-TEQDF/year estimate reported here based on adding emissions of each facility. 4 5 3.1.2. W ater Releases 6 Some municipal waste combustors use wet scrubbers to treat emissions. Water 7 discharges may be associated with such devices. Some of these facilities have water treatment 8 systems that reduce particulate levels (and associated dioxins) prior to discharge. No 9 information was found to estimate the magnitude of CDD/CDF releases from these devices. 10 Accordingly, releases are possible, but estimates could not be made (Not quantifiable). 11 12 3.1.3. Solid Residue Releases 13 In the United States, all municipal waste combustor ash (except the portion used in 14 products--see discussion below) is disposed in permitted landfills. As defined in this inventory, 15 landfilled material does not represent a release to the open environment and is not included in the 16 source inventory. However, for informational purposes and when sufficient information is 17 available, this document provides estimates of the amounts of ash landfilled. The discussion 18 below presents estimates of the amount of dioxin in municipal waste ash sent to landfills. 19 Municipal waste combustors create solid residues in the form of fly ash, which is 20 collected from the stack by APCDs, and bottom ash, which is discharged directly from the 21 combustor. As discussed in EPA (2006), a variety of studies have measured dioxin levels in 22 municipal waste combustor ash from the United States. Only two of these provided congener 23 data allowing TEQ calculations: 24 25 Ashes from five state-of-the-art municipal waste combustor facilities located in different 26 regions of the United States were analyzed for all 2,3,7,8-substituted CDDs/CDFs. The 27 TEQ levels in the ash (fly ash mixed with bottom ash) ranged from 106 to 28 466 ng I-TEQDF/kg, with a mean value of 258 ng I-TEQDF/kg CDFs (U.S. EPA, 1990a). 29 Washington State Department of Ecology (1998) reported CDD/CDF congener data for 30 ash and other solid residuals from three municipal incinerators (Fort Lewis, Bellingham 31 [municipal plus medical wastes], and Spokane). The data were compiled and evaluated 32 to determine a total I-TEQ concentration and loading. The results showed fly ash ranging 33 from 0.51 to 4.98 pg I-TEQ/kg, bottom ash ranging from 0.00 to 0.2 pg I-TEQ/kg, and 34 mixed ash ranging from 0.038 to 0.163 pg I-TEQ/kg. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-2 DRAFT: DO NOT CITE OR QUOTE 1 EPA (2006) also summarized municipal waste combustor ash information from a variety of 2 studies conducted in other countries, with two reporting TEQ calculations: 3 4 Kobylecki et al. (2001) analyzed the reduction of dioxins in fly ash by pelletizing the ash 5 and reburning the pellets in a laboratory-scale bubbling fluidized-bed furnace. Fly ash 6 for the test input material was collected from a fly ash filter vessel during 4 days of 7 municipal waste combustor operation. The total TEQ value derived by Kobylecki was 8 862 ng I-TEQDF/kg of fly ash. 9 Sakai et al. (2001) analyzed the levels of dioxins and PCBs in fly ash and bottom ash 10 from a newly constructed municipal waste combustor in Japan. TEQ values derived from 11 the data give a total of 423 ng I-TEQDF/kg for fly ash and 10.5 ng I-TEQDF/kg for bottom 12 ash for dioxins and 31.6 ng I-TEQDF/kg for fly ash and 0.85 ng I-TEQDF/kg for bottom 13 ash for PCBs. 14 15 UNEP (2005) provided emission factors for fly ash ranging from 15 to 500 pg I-TEQ/MT of 16 municipal solid waste burned and emission factors for bottom ash ranging from 1.5 to 17 75 pg I-TEQ/MT of municipal solid waste burned. For municipal waste combustors with 18 controlled combustion and good APCD (this class would be typical of many of the U.S. 19 facilities), the recommended values were 200 pg I-TEQ/MT of municipal solid waste burned for 20 fly ash and 7 pg I-TEQ/MT of municipal solid waste burned for bottom ash. 21 Given the very limited data on TEQ levels in ash from U.S. facilities, it was decided to 22 use the UNEP (2005) default recommendations as follows: the UNEP recommendations for 23 municipal waste combustors with controlled combustion and minimal APCDs 24 (200 pg I-TEQ/MT of municipal solid waste burned for fly ash and 7 pg I-TEQ/MT of municipal 25 solid waste burned for bottom ash) were assumed to apply to 1987. Extensive improvements in 26 APCDs (including reductions in the use of hot-sided electrostatic precipitators ESPs) occurred 27 from 1987 to 1990. So reductions would also be expected in the dioxin content of the ash. Thus, 28 the UNEP recommendations for municipal waste combustors with controlled combustion and 29 good APCDs (15 pg I-TEQ/MT of municipal solid waste burned for fly ash and 30 1.5 pg I-TEQ/MT of municipal solid waste burned for bottom ash) were assumed to apply to 31 1995 and 2000. These assumptions are summarized below: 32 1987--200 ng I-TEQ/kg of municipal solid waste burned for fly ash and 7 ng I-TEQ/kg 33 of municipal solid waste burned for bottom ash This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-3 DRAFT: DO NOT CITE OR QUOTE 1 1995--15 ng I-TEQ/kg of municipal solid waste burned for fly ash and 1.5 ng I-TEQ/kg 2 of municipal solid waste burned for bottom ash 3 2000--15 ng I-TEQ/kg of municipal solid waste burned for fly ash and 1.5 ng I-TEQ/kg 4 of municipal solid waste burned for bottom ash 5 6 Multiplying the emission factors by the total municipal waste activity levels, yielded the 7 following estimates of amount of dioxin in landfilled ash: 8 9 1987--2,800 g I-TEQ 10 1995--490 g I-TEQ 11 2000--490 g I-TEQ 12 13 As indicated earlier, in the United States, all municipal waste combustor ash (except the portion 14 used in products--see discussion below) is disposed in permitted landfills and, therefore, not 15 included in the source inventory. 16 The amount of ash generated by municipal waste incineration is not directly used in the 17 procedure described above to estimate the amount of dioxin in landfilled ash. However, this 18 may be of interest and is estimated here for informational purposes only. An estimated 7 MMT 19 of total ash (bottom ash plus fly ash) were generated by municipal waste combustors in 1992 20 (telephone conversation between J. Loundsberry, EPA Office of Solid Waste, and L. Brown, 21 Versar, Inc., February 24, 1993). EPA indicated that 2 to 5 MMT of total ash were produced 22 annually in the late 1980s from municipal waste combustors, with fly ash comprising 5 to 15% 23 of the total (U.S. EPA, 1991). UNEP (2005) indicates that the amount of fly ash generated per 24 ton of municipal solid waste is typically 1-2%, and the amount of bottom ash generated per ton 25 of municipal solid waste is approximately 10-20%. The amounts of ash generated were 26 calculated using the midpoints of these ranges: 27 28 1987--The total municipal solid waste burned was estimated as 13.7 billion kg (this 29 implies that 0.2 billion kg of fly ash and 2.1 billion kg of bottom ash were generated). 30 1995--The total municipal solid waste burned was estimated as 29.8 billion kg (this 31 implies that 0.4 billion kg of fly ash and 4.5 billion kg of bottom ash were generated). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-4 DRAFT: DO NOT CITE OR QUOTE 1 2000--The total municipal solid waste burned was estimated as 29.4 billion kg (this 2 implies that 0.4 billion kg of fly ash and 4.4 billion kg of bottom ash were generated). 3 4 3.1.4. Products 5 The primary purpose of municipal waste combustors is waste disposal rather than the 6 manufacture of products. However, some municipal waste combustor ash has been used in 7 road-building materials (UNEP, 2005). The concentration of CDD/CDFs in these products 8 would be a fraction of the level found in the original residues. For example, if the product 9 contained 1% municipal waste combustor residues, the CDD/CDF concentration would be 1% of 10 the level found in the original residue. No information could be found on the residue content of 11 these products. Similarly, no information could be found on the quantity of ash going into such 12 products. It is possible that the ash is tightly bound to the construction materials, reducing the 13 chance of release to the open environment. However, no data could be found on this issue. 14 Accordingly, releases are probably small, but estimates could not be made (Not quantifiable). 15 16 3.1.5. Release Summary 17 The inventory decision criteria and release estimates to all media are summarized below. Inventory Decision Criteria for Municipal Waste Incinerators Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-5 DRAFT: DO NOT CITE OR QUOTE Municipal Waste Incinerators_________________________ Air Releases_________________________________ Emission Factors 1987--Table 3-1. 1995--Table 3-2. 2000--Table 3-3._________________________________________________________ Activity Levels 1987--Table 3-1 (overall total is 13.7 billion kg of waste). 1995--Table 3-2 (overall total is 29.8 billion kg of waste). 2000--Table 3-3 (overall total is 29.4 billion kg of waste).________________________ Releases 1987--Table 3-1. Total releases were 9,500 g WHO98 TEQDF/yr (8,500 g I-TEQDF/yr). 1995--Table 3-2. Total releases were 1,200 g WHO98 TEQDF/yr (1,100 g I-TEQDF/yr). 2000--Table 3-3. Total releases were 77 g WHO98 TEQDF/yr (69 g I-TEQpF/yr).______ W ater Releases________________________________ Water releases are possible, but data are insufficient to make quantitative estimates (Not quantifiable).___________________________________________________________________ Solid Residue Releases_____________________________ All municipal waste combustor ash (except the portion used in products--see below) is disposed in permitted landfills. As defined in this inventory, landfilled material does not represent a release to the open environment and is not included in the source inventory._________________ Products__________________________________ Product releases are possible, but data are insufficient to make quantitative estimates (Not quantifiable).___________________________________________________________________ 1 3.2. HAZARDOUS WASTE INCINERATION 2 Hazardous wastes are burned in a variety of situations and are covered in a number of 3 different sections in this report. 4 5 Hazardous waste is burned in facilities dedicated to burning this type of waste. Most of 6 these dedicated facilities are located on site at chemical manufacturing facilities and burn 7 only the waste associated with their on-site industrial operations. Hazardous waste is also 8 burned at dedicated facilities located off site. These facilities accept waste from multiple 9 sources. On- and off-site dedicated hazardous waste burning facilities are addressed in 10 Section 3.2.1. 11 Hazardous waste is also burned in industrial boilers and furnaces that are permitted to 12 burn the waste as supplemental fuel. These facilities have significantly different furnace 13 designs and operations than those of dedicated hazardous waste incinerators (HWIs). 14 They are discussed in Section 3.2.2. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-6 DRAFT: DO NOT CITE OR QUOTE 1 Hazardous waste is also burned in halogen acid furnaces (HAFs), in which halogen acids 2 (such as HCl) may be produced from halogenated secondary materials. These facilities 3 are discussed in Section 3.2.3. 4 A number of cement kilns and lightweight aggregate kilns are also permitted to burn 5 hazardous waste as auxiliary fuel. These are discussed separately in Section 5.1. 6 Mobile HWIs are typically used for site cleanup at Superfund sites. These units can be 7 transported from one location to another and operate for a limited duration at any given 8 location. Due to a lack of information about these facilities, they are not included in this 9 inventory. 10 11 3.2.1. Dedicated HWIs 12 3.2.1.1. A ir R e le a se s 13 No changes were made in the air-release estimates reported in U.S. EPA (2006). Where 14 feasible, this document subdivides the combustors in each source category into design classes 15 judged to have similar potential for CDD/CDF emissions. However, this would not have been 16 useful for dedicated HWIs because information was lacking about the amount of waste burned in 17 each of the design classes. Additionally, all HWI designs achieve excellent combustion 18 efficiency using high temperatures and long residence times, suggesting that little difference in 19 emission factors would be observed among the design classes. Minor changes in design and 20 operating procedures would be expected in 2000 due to the stricter emission limits that became 21 effective at that time. Therefore, the strategy used to develop emission factors for HWIs was to 22 assume that the emission tests conducted prior to 2000 represented facilities in operation during 23 the reference years 1987 and 1995 and the emission tests conducted in 2000 represented the 24 facilities operating in 2000. 25 The emission factors were developed using stack test data from a database compiled by 26 the EPA Office of Solid Waste (OSW). This database summarizes the results of stack testing for 27 CDDs/CDFs at a number of HWIs between 1993 and 2000 (U.S. EPA, 2002b). For the purposes 28 of estimating emissions in 1995, an emission factor was developed using data from 17 HWIs 29 tested between 1993 and 1996. For the purposes of estimating emissions in 2000, an emission 30 factor was developed using data from 10 HWIs tested in 2000 (a total of 22 HWIs were tested in 31 2000, but flue gas flow rates were available for only 10 of these incinerators). For the purposes 32 of estimating emissions in 1987, the emission factor derived for 1995 was assumed to apply to This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-7 DRAFT: DO NOT CITE OR QUOTE 1 1987. The 1987 activity estimate is from Dempsey and Oppelt (1993), and the 1995/2000 2 estimate is based on Federal Register (1996). 3 The emission factors assumed here were in the range of 2-4 ng I-TEQ/kg, which falls in 4 between the values recommended by UNEP (2005) for the top two performing classes: 5 6 Low technology, no APCD--35,000 ng I-TEQ/kg 7 Controlled, minimal APCD--350 ng I-TEQ/kg 8 Controlled, good APCD--10 ng I-TEQ/kg 9 High technology, sophisticated APCD--0.75 ng I-TEQ/kg 10 11 3.2.1.2. W ater R e le a se s 12 Many HWIs use wet scrubber systems, which can have water discharges. However, no 13 information was found to support release estimates (Not quantifiable). 14 15 3.2.1.3. S o lid R e s id u e R e le a se s 16 EPA (1987) contains limited data on ash generated from hazardous waste incineration. 17 The study indicates that the mean concentrations of CDDs and CDFs from an HWI with an 18 afterburner were 538 p,g/kg and 2,853 p,g/kg, respectively (Table 3-8 in U.S. EPA, 1987). 19 Specific data for congeners and for ash quantities were not provided. Accordingly, quantitative 20 estimates cannot be made about amounts of CDD/CDFs in solid residues from dedicated HWIs. 21 In the United States, all HWI ash is disposed in permitted landfills. As defined in this inventory, 22 landfilled material does not represent a true release to the open environment and is not included 23 in the source inventory. 24 25 3.2.1.4. P r o d u c ts -- N o n e 26 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-8 DRAFT: DO NOT CITE OR QUOTE 1 3.2.1.5. R e le a s e S u m m a ry 2 The inventory decision criteria and releases are summarized below: Inventory Decision Criteria for Dedicated HWIs Air Water Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Solids Products Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Q Dedicated HWIs____________________ Air Releases______________________ Emission Factors 1987--3.9 ng WHO98 TEQDF/kg (3.8 ng I-TEQdf^ ) of waste feed. 1995--3.9 ng WHO98 TEQDF/kg (3 .8 ng I-TEQDF/kg) of waste feed. 2000--2.1 ng WHO98 TEQDF/kg (2 .1 ng I-TEQDF/kg) of waste feed. Activity Levels 1987--1.3 billion kg. 1995--1.5 billion kg. 2000--1.5 billion kg.___________________________________________ Releases 1987--5 g (WHO98 TEQdf or I-TEQdf). 1995--6 g WHO98 TEQdf (5.7 g I-TEQdf). 2000--3 g WHO98 TEQdf (3 g I-TEQdf).___________________________ W ater Releases_____________________ Possible, but data are insufficient to make quantitative estimates (Not quantifiable). Solid Residue Releases__________________ Ash is landfilled, so it is not considered an environmental release.______________ Products________________________ None.______________________________________________________________ 3 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-9 DRAFT: DO NOT CITE OR QUOTE 1 3.2.2. Industrial Boilers and Furnaces Burning Hazardous Waste 2 3.2.2.1. A ir R e le a se s 3 The emission factors for industrial boilers and furnaces burning hazardous waste were 4 derived from test data for three facilities presented in the OSW database. Minor changes in 5 design and operating procedures would be expected in 2000 due to the stricter emission limits 6 that became effective at that time. Therefore, the strategy used to develop emission factors for 7 these facilities was to assume that the emission tests conducted prior to 2000 represented 8 facilities in operation during the reference years 1987 and 1995 and the emission tests conducted 9 in 2000 represented the facilities operating in 2000. The activity level used in US EPA, 2006 10 (derived from survey data in Dempsey and Oppelt, 1993 and other OSW data) for 2000 was 11 changed from 1.5 to 0.6 billion kg based on the assumption that no change occurred from 1995. 12 As a result, minor changes were also made in the air-release estimate for reference year 2000. 13 3.2.2.2. W ater R e le a se s 14 Some industrial boilers use wet scrubber systems, which can have water discharges. 15 However, no information was found to support release estimates (Not quantifiable). 16 17 3.2.2.3. S o lid R e s id u e R e le a se s 18 Because these facilities are typically burning liquid waste, little ash would be generated. 19 20 3.2.2.4. P r o d u c ts -- N o n e 21 22 3.2.2.5. R e le a s e S u m m a ry 23 The releases are summarized below: 24 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-10 DRAFT: DO NOT CITE OR QUOTE 1 Inventory Decision Criteria for Industrial Boilers and Furnaces Burning Hazardous Waste Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Q Industrial Boilers and Furnaces Burning Hazardous Waste Air Releases______________________ Emission Factors 1987--0.65 ng WHO98 TEQDF/kg (0.64 ng I-TEQDF/kg) of waste feed. 1995--0.65 ng WHO98 TEQDF/kg (o.64 ng I-TEQDF/kg) of waste feed. 2000--1.2 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of waste feed. Activity Levels 1987--1.2 billion kg. 1995--0.6 billion kg. 2000--0.6 billion kg.___________________________________________ Releases 1987--0.8 g WHO98 TEQdf (0.8 g I-TEQdf). 1995--0.4 g WHO98 TEQdf (0.4 g I-TEQdf). 2000--0.7 g WHO98 TEQdf (q.7 g I-TEQdf).________________________ W ater Releases_____________________ Possible, but data are insufficient to make quantitative estimates (Not quantifiable). Solid Residue Releases__________________ None.______________________________________________________________ Products________________________ None. 2 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-11 DRAFT: DO NOT CITE OR QUOTE 1 3.2.3. Halogen Acid Furnaces Burning Hazardous Waste 2 3.2.3.1. A ir R e le a se s 3 No changes were made to the air-release estimates. The emission factors for halogen 4 acid furnaces (HAFs) burning hazardous waste were derived from the same OSW database used 5 for dedicated HWIs. For the purposes of estimating emissions in 2000, an emission factor was 6 developed using data from two HAFs tested in 2000. For the purposes of estimating emissions 7 in 1987 and 1995, the emission factor derived for 2000 was assumed to apply to the earlier years. 8 The activity estimate was based on survey data provided by OSW for 2000 and assumed to be 9 also representative of the earlier years. 10 11 3.2.3.2. W ater R e le a se s 12 No information was found to support release estimates. 13 14 3.2.3.3. S o lid R e s id u e R e le a se s 15 Because these facilities are typically burning liquid waste, no ash would be generated. 16 17 3.2.3.4. P ro d u c ts-- N o n e 18 19 3.2.3.5. R e le a s e S u m m a ry 20 The inventory decision criteria and releases are summarized below: Inventory Decision Criteria for Halogen Acid Furnaces Burning Hazardous Waste Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-12 DRAFT: DO NOT CITE OR QUOTE Halogen Acid Furnaces Burning Hazardous Waste______ Air Releases______________________ Emission Factors 1987--0.84 ng WHO98 TEQDF/kg (0.80 ng I-TEQDF/kg) of waste feed. 1995--0.84 ng WHO98 TEQDF/kg (0.80 ng I-TEQDF/kg) of waste feed. 2000--0.84 ng WHO98 TEQDF/kg (0.80 ng I-TEQDF/kg) of waste feed. Activity Levels 1987--376 million kg. 1995--376 million kg. 2000--376 million kg.__________________________________________ Releases 1987--0.3 g WHO98 TEQdf (0.3 g I-TEQdf). 1995--0.3 g WHO98 TEQdf (0.3 g I-TEQdf). 2000--0.3 g WHO98 TEQdf (q.3 g I-TEQDF).________________________ W ater Releases_____________________ Possible, but data are insufficient to make quantitative estimates (Not quantifiable). Solid Residue Releases__________________ None.______________________________________________________________ Products________________________ None. 1 3.3. MEDICAL WASTE INCINERATION 2 3.3.1. Air Releases 3 Changes were made to the emission factors. The U.S. EPA, 2006 report divided the 4 uncontrolled class into two subclasses and the controlled class into three subclasses. Some of 5 these classes had very few tested facilities, and the range of emission factors overlapped between 6 subclasses. Thus, it was decided to combine these classes into one emission factor for 7 uncontrolled facilities (1,870 ng WHO98 TEQ/kg, 1,760 ng I-TEQ/kg) based on testing at 8 seven facilities and one for controlled facilities (51 ng WHO98 TEQ/kg, 50 ng I-TEQ/kg) based 9 on testing at 12 facilities. For comparison purposes, the UNEP (2005) emission factor 10 recommendations are provided below: 11 Uncontrolled, batch, no APCD--40,000 ng I-TEQ/kg 12 Controlled, batch, minimal APCD--3,000 ng I-TEQ/kg 13 Controlled, batch, good APCD--525 ng I-TEQ/kg 14 Controlled, continuous, excellent APCD--1 ng I-TEQ/kg 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-13 DRAFT: DO NOT CITE OR QUOTE 1 Activity estimates are based on survey data summarized in U.S. EPA, 2006. Table 3-4 2 shows the activities and release estimates for each year. These changes resulted in small 3 increases in total releases compared to the original values reported in U.S. EPA, 2006. 4 5 3.3.2. W ater Releases 6 Some medical waste incinerators use wet scrubber systems, which can have water 7 discharges. However, no information was found to support release estimates (Not quantifiable). 8 9 3.3.3. Solid Residue Releases 10 In the United States, all ash from medical waste incinerators is disposed in permitted 11 landfills. As defined in this inventory, landfilled material does not represent a true release to the 12 open environment and is not included in the source inventory. However, for informational 13 purposes, the discussion below presents estimates of the amount of dioxin in landfilled ash. 14 Fiedler et al. (2002) tested a hospital waste incinerator in Thailand. The furnace had a 15 static grate and was equipped with a secondary combustion chamber and two afterburners. The 16 flue gases passed over an alkaline water bath before being discharged through a flue stack. 17 Overall, the plant appeared poorly designed and poorly maintained. Bottom ash concentrations 18 of 1,390 and 1,980 ng -TEQ/kg were found. The authors suggest the high results were due to the 19 poor combustion conditions in the primary chamber and the practice of leaving the bottom ashes 20 overnight in the chamber to slowly cool down. 21 As indicated above, emission testing data could be located for only one facility. The poor 22 condition of this facility suggests it is not representative of U.S. facilities. UNEP (2005) 23 suggests emission factors ranging from 150 to 920 ng I-TEQ/kg of waste burned (for combined 24 bottom ash and fly ash) for controlled facilities. The average of this range is assumed for all 25 reference years: 530 ng I-TEQDF/kg of waste. These UNEP recommendations are not linked to 26 specific references and appear to represent the professional judgment and consensus among the 27 authors. It is unknown how representative this emission factor is of U.S. facilities. Accordingly, 28 it is regarded as preliminary. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-14 DRAFT: DO NOT CITE OR QUOTE 1 The amounts of dioxin in landfilled ash were estimated by multiplying the emission 2 factor by the activity level: 3 4 1987--760 g I-TEQdf 5 1995--410 g I-TEQdf 6 2000--320 g I-TEQdf 7 8 Because the ash is landfilled, it is not considered a release to the open environment and is not 9 included in the source inventory. 10 The total amount of landfilled ash is not directly used in the calculation above. However, 11 it may be of interest and is provided below for information purposes only. The estimates were 12 generated by assuming that the combined fly and bottom equals 20% of the waste feed (UNEP, 13 2005). This yields the following estimates: 14 1987--0.28 billion kg 15 1995--0.15 billion kg 16 2000--0.12 billion kg 17 18 3.3.4. Products--None 19 20 3.3.5. Release Summary 21 The inventory decision criteria and releases to all media are summarized below: Inventory Decision Criteria for Medical Waste Incinerators Air W ater Solids Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Products Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-15 DRAFT: DO NOT CITE OR QUOTE Medical Waste Incinerators________________ Air Releases______________________ Emission Factors 1987--Table 3-4. 1995--Table 3-4. 2000--Table 3-4.______________________________________________ Activity Levels 1987--Table 3-4. 1995--Table 3-4. 2000--Table 3-4.______________________________________________ Releases 1987--2,700 g WHO98 TEQDF/yr (2,600 g I-TEQDF/yr). 1995--510 g WHO98 TEQDF/yr (490 g I-TEQDF/yr). 2000--400 g WHO98TEQDF/yr (380 g I-TEQDF/yr).___________________ W ater Releases_____________________ Possible, but data are insufficient to make quantitative estimates (Not quantifiable). Solid Residue Releases__________________ The ash is landfilled so it is not considered an environmental release.___________ Products________________________ None. 1 3.4. CREMATORIA 2 3.4.1. Human Crematoria 3 3.4.1.1. A ir R e le a se s 4 No changes were made to the air-release estimates. The emission factor was derived on 5 the basis of testing at two U.S. facilities and assumed to apply to all reference years. It 6 corresponds to the low end of the range recommended by UNEP (2005): 7 400 ng I-TEQ/cremation for facilities with optimal control, 10,000 ng I-TEQ/cremation for 8 facilities with medium control, and 90,000 ng I-TEQ/cremation for facilities with no control. 9 Activity information was derived from CANA (2006). 10 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-16 DRAFT: DO NOT CITE OR QUOTE 1 3.4.1.2. W a ter R e le a se s 2 These facilities do not use wet scrubbers, and there are no other identifiable water 3 releases associated with their operation. 4 5 3.4.1.3. S o lid R e s id u e R e le a se s 6 No information was found on the disposition of cremation ash. It is assumed here that all 7 of it is eventually released to the open environment. 8 UNEP (2005) recommends an ash emission factor of 2,500 ng I-TEQ/cremation for 9 facilities with medium or optimal control. The CDD/CDF concentrations in the bottom ashes 10 collected from a two-chamber crematory in Thailand were 44 and 48 ng I-TEQ/kg of bottom ash 11 (UNEP, 2005; Fiedler et al., 2002). Based on the average of these tests, a concentration of 12 46 ng I-TEQ/kg of bottom ash is assumed for each reference year. This facility appears to have a 13 similar design to U.S. facilities. However, the emission factor was assigned a preliminary rating 14 because it is based on testing at only one facility. 15 The total bottom ash generated was estimated by multiplying the number of bodies 16 cremated per year (CANA, 2006), 5.5% ash content (Forbes et al., 1953), and 70 kg (average 17 adult body weight). This yields the following estimates: 18 19 1987--1.24 million kg 20 1995--1.88 million kg 21 2000--2.42 million kg 22 23 The solid residue releases were estimated by multiplying the ash concentration by the ash 24 activity level. 25 3.4.1.4. P ro d u c ts-- N o n e 26 27 3.4.1.5. R e le a s e S u m m a ry 28 The inventory decision criteria and releases are summarized below. The ash is typically 29 disposed in landfills and therefore not considered an environmental release. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-17 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Human Crematoria Air W ater Solids Emission tests for at least two units/source types with Yes No sufficient documentation to directly derive emission factors. Products Measured emission factors consistent or have understandable differences. Yes Yes Emission factor tests represent units that are typical of the Yes class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Q Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-18 DRAFT: DO NOT CITE OR QUOTE Human Crematoria______________________ Air Releases__________________________ Emission Factors 1987--450 ng WHO98 TEQDF/body cremated (430 ng I-TEQDF/body cremated). 1995--450 ng WHO98 TEQDF/body cremated (430 ng I-TEQDF/body cremated). 2000--450 ng WHO98 TEQDF/body cremated (430 ng I-TEQDF/body cremated). Activity Levels 1987--A total of 323,371 cremations were performed. 1995--A total of 488,224 cremations were performed. 2000--A total of 629,362 cremations were performed.____________________ Releases 1987--0.2 g WHO98 TEQdf (0.1 g I-TEQdf). 1995--0.2 g WHO98 TEQdf (0 .2 g I-TEQdf). 2000--0.3 g WHO98 TEQdf (0.3 g I-TEQdf).____________________________ W ater Releases________________________ None._________________________________________________________________ Solid Residue Releases_____________________ Emission Factors 1987--46 ng I-TEQ/kg of ash (Preliminary). 1995--46 ng I-TEQ/kg of ash (Preliminary). 2000--46 ng I-TEQ/kg of ash (Preliminary).____________________________ Activity Levels 1987--1.24 million kg ash. 1995--1.88 million kg ash. 2000--2.42 million kg ash.__________________________________________ Releases 1987--0.1 g I-TEQdf (Preliminary). 1995--0.1 g I-TEQdf (Preliminary). 2000--0.1 g I-TEQdf (Preliminary).___________________________________ Products___________________________ None. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-19 DRAFT: DO NOT CITE OR QUOTE 1 3.4.2. Animal Crematoria 2 3.4.2.1. A ir R e le a se s 3 Minor changes were made in how these air releases were estimated. For destruction of 4 animal carcasses, UNEP (2005) recommends emission factors of 5 ng I-TEQ/kg for state-of-the5 art facilities, 50 ng I-TEQ/kg for updated facilities, and 500 ng I-TEQ/kg for uncontrolled 6 facilities. As described in EPA, 2006, only one U.S. facility emission test could be located. This 7 facility had very low emissions and may not be representative of most facilities. The mid-range 8 value recommend by UNEP was judged to more likely represent typical U.S. facilities. 9 Therefore, this emission factor was assumed to apply to each of the reference years: 10 50 ng I-TEQDF/kg of animal cremated. Based on the limited test data and questions about its 11 representativeness, this emission factor is considered a preliminary estimate. 12 As part of the 2000 inventory, OAQPS (U.S. EPA, 2002b) calculated a national animal 13 cremation activity level estimate of 81.9 million kg/year for reference year 2000. Assuming that 14 the fraction of the population owning pets and the fraction of pets cremated stay reasonably 15 constant, this value can be extrapolated to the other reference years by assuming that animal 16 cremation rates are proportional to the human population. The following U.S. population 17 estimates were used in this exercise: 1987--242 billion, 1995--263 billion, and 18 2000--291 billion. The data for each reference year are presented below: 19 20 1987--68 million kg/year. 21 1995--74 million kg/year 22 2000--81.9 million kg/year 23 24 3.4.2.2. W a ter R e le a s e s -- N o n e 25 26 3.4.2.3. S o lid R e s id u e R e le a se s 27 All ash from these facilities is assumed to be disposed in permitted landfills. As defined 28 in this inventory, landfilled material does not represent a true release to the open environment 29 and is not included in the source inventory. However, for informational purposes, the discussion 30 below presents estimates of the amount of dioxin in landfilled ash. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-20 DRAFT: DO NOT CITE OR QUOTE 1 As indicated above, emission testing data could be located for only one facility. No 2 bottom ash testing was reported for this facility. It has a similar design to the human cremation 3 facility in Thailand where testing found 44 and 48 ng I-TEQ/kg of bottom ash (UNEP, 2005; 4 Fiedler et al., 2002). Based on the average of these tests, an bottom ash concentration of 5 46 ng I-TEQ/kg is assumed for all reference years. It is completely unknown how representative 6 this facility is of U.S. facilities. Accordingly, it must be regarded as preliminary. 7 The total bottom ash generated was estimated by multiplying the mass of animals 8 cremated per year (see above) and 5.5% ash content (value for humans from Forbes et al., 1953). 9 This yields the following estimates: 10 11 1987--3.7 million kg 12 1995--4.1 million kg 13 2000--4.5 million kg 14 15 These estimates are considered preliminary because they are derived from Class D-rated 16 estimates for mass of animals cremated. 17 The amounts of dioxin in landfilled ash were estimated by multiplying the bottom ash 18 concentration by the ash activity level: 19 20 1987--0.17 g I-TEQdf (Preliminary) 21 1995--0.19 g I-TEQdf (Preliminary) 22 2000--0.21 g I-TEQdf (Preliminary) 23 24 The ash from these facilities is assumed to be landfilled and, therefore, is not considered a 25 release to the open environment. 26 27 3.4.2.4. P r o d u c ts -- N o n e 28 29 3.4.2.5. R e le a s e S u m m a ry 30 The inventory decision criteria and releases are summarized below: This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-21 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Animal Crematoria Air W ater Solids Emission tests for at least two units/source types with No sufficient documentation to directly derive emission factors. Products Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. No Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes P Animal Crematoria________________ Air Releases___________________ Emission Factors 1987--50 ng I-TEQDF/kg of animal cremated (Preliminary). 1995--50 ng I-TEQDF/kg of animal cremated (Preliminary). 2000--50 ng I-TEQpi /kg of animal cremated (Preliminary)._________ Activity Levels 1987--68 million kg/yr. 1995--74 million kg/yr. 2000--81.9 million kg/yr._____________________________________ Releases 1987--3 g I-TEQDF(Preliminary). 1995--4 g I-TEQdf (Preliminary). 2000--4 g I-TEQdf (Preliminary).______________________________ W ater Releases__________________ None.___________________________________________________________ Solid Residue Releases_______________ This ash is landfilled and, therefore, is not considered an environmental release. Products_____________________ None. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-22 DRAFT: DO NOT CITE OR QUOTE 1 3.5. SEWAGE SLUDGE INCINERATION 2 3.5.1. Air Releases 3 No changes were made to the air-release estimates. The emission factor of 6.7 ng 4 WHO98 TEQDF/kg was derived from testing at 14 U.S. facilities and applied to all three reference 5 years. UNEP (2005) recommends emission factors of 0.4 ng I-TEQ/kg for state-of-art facilities 6 and 4 ng I-TEQ/kg for updated facilities with controls. The emission factor used here is similar 7 to the UNEP recommendation for updated facilities with controls. The activity estimates were 8 derived from survey data summarized in EPA, 2006. 9 10 3.5.2. W ater Releases 11 Because some sewage sludge incinerators use wet scrubber systems, it is possible that 12 water discharges occur. However, wastewater from wet scrubbers is often treated and then 13 reintroduced to the wastewater treatment plant, so that no water discharges occur directly from 14 the incinerator (in these cases, the CDD/CDFs in the effluent would likely end up in the sewage 15 sludge). As discussed below, some limited information is available on dioxin levels in scrubber 16 water. No information is available on quantities of scrubber effluent from U.S. facilities or what 17 portion is recycled back to the wastewater treatment operation. Therefore, releases are possible, 18 but no quantitative estimates could be made (Not quantifiable). 19 In Table 5-16 of EPA (1987), data are presented indicating that 2,3,7,8-TCDD was not 20 detected in scrubber water filtrate from three sewage sludge incinerators. However, total CDDs 21 for the three incinerators averaged 0.3 ng/kg, and total CDFs averaged 4 ng/kg. No data were 22 given for any congeners (other than 2,3,7,8-TCDD), nor were there any data on the quantities of 23 filtrate. 24 The European inventory (EU, 1999) reports concentrations between 1.2 and 25 6.5 pg I-TEQ/L in scrubber effluents from sewage sludge incinerators. 26 27 3.5.3. Solid Residue Releases 28 All ash from these facilities is assumed to be disposed in permitted landfills. As defined 29 in this inventory, landfilled material does not represent a true release to the open environment 30 and is not included in the source inventory. However, for informational purposes, the discussion 31 below presents estimates of the amount of dioxin in landfilled ash. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-23 DRAFT: DO NOT CITE OR QUOTE 1 Testing of multiple hearth furnaces in the United Kingdom (Dyke et al., 1997) showed 2 CDD/CDF in the grate ash at concentrations of 39 ng TEQ/kg and 470 ng TEQ/kg in fly ash 3 from the ESP. Rates of ash production were 430 kg/ton of grate ash and 13 kg/ton of ESP ash 4 for the multiple hearth plant. Levels in ash (all the ash was collected in the ESP) from fluidized 5 bed combustion were much lower (<1 ng TEQ/kg); 373 kg of ESP ash were produced per ton of 6 sludge combusted in the fluidized bed. 7 In Table 5-16 of EPA (1987), data are presented indicating that 2,3,7,8-TCDD was not 8 detected in the bottom ash from three sewage sludge incinerators. However, total CDDs for the 9 three incinerators were nondetects, 20 ng/kg, and 10 ng/kg. For total CDFs, the values were 10 nondetects, 70 ng/kg, and 50 ng/kg. No data were given for any congeners (other than 11 2,3,7,8-TCDD), nor were there any data on the quantities of ash. 12 UNEP (2005) recommends default residue emission factors of 0.5 ng I-TEQ/kg of 13 sewage sludge for updated and modern furnaces. This was adopted for all reference years. This 14 is considered a preliminary (Class D) estimate because there were no U.S. data and very limited 15 European data to support it. 16 No data on ash generation rates were found. Rather, the activity was based on the annual 17 amount of sewage sludge incinerated--see the discussion above. 18 The amounts of dioxin in landfilled ash were estimated by multiplying the emission 19 factor by the activity level: 20 21 1987--0.43 g I-TEQDF(Preliminary) 22 1995--1.0 g I-TEQDF(Preliminary) 23 2000--0.71 g I-TEQdf (Preliminary) 24 25 The ash from these facilities is assumed to be landfilled and, therefore, is not considered a 26 release to the open environment. 27 28 3.5.4. Products--None 29 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-24 DRAFT: DO NOT CITE OR QUOTE 1 3.5.5. Release Summary 2 The inventory decision criteria and releases to all media are summarized below: Inventory Decision Criteria for Sewage Sludge Incinerators Air W ater Solids Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Products Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of Yes the class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes Q Sewage Sludge Incinerators_____________________ Air Releases____________________________ Emission Factors 1987--6.7 ng WHO98 TEQDF/kg (6.6 ng I-TEQDF/kg). 1995--6.7 ng WHO98 TEQDF/kg (6.6 ng I-TEQDF/kg). 2000--6.7 ng WHO98 TEQDF/kg (6.6 ng I-TEQDF/kg).______________________ Activity Levels 1987--0.865 billion kg of dry sewage sludge. 1995--2.11 billion kg of dry sewage sludge. 2000--1.42 billion kg of dry sewage sludge.______________________________ Releases 1987--6 g WHO98 TEQdf (6 g I-TEQdf). 1995--14 g WHO98 TEQdf (14 g I-TEQdf). 2000--10 g WHO98 TEQdf ( 9 g I-TEQdf).________________________________ W ater Releases__________________________ Possible but quantitative releases could not be made (Not quantifiable)._______________ Solid Residue Releases_______________________ The ash from these facilities is assumed to be landfilled and, therefore, is not considered a release to the open environment.______________________________________________ Products_____________________________ None.___________________________________________________________________ 3 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-25 DRAFT: DO NOT CITE OR QUOTE 1 3.6. TIRE COMBUSTION 2 This section covers releases from dedicated tire incinerators. Tires are also burned in 3 cement kilns, which are covered in Section 5.1. Some are combusted as auxiliary fuel in 4 industrial boilers and in pulp and paper mill combustion facilities, but the amount of tires going 5 to these types of facilities is assumed to be negligible (note that emissions from industrial boilers 6 are covered in Sections 3.2 and 4.3, and emissions from pulp and paper mills are covered in 7 Sections 3.7 and 8.1). Additionally, tires may be unintentionally burned in an uncontrolled 8 fashion at landfills (open burning). The open burning of tires is not discussed in this report due 9 to the lack of information, and, thus, is an unquantifiable source. 10 11 3.6.1. Air Releases 12 No changes were made to the air-release estimates. The emission factor of 0.28 ng 13 WHO98 TEQDF/kg was derived from testing at one facility that was equipped with a dry scrubber 14 and fabric filter (CARB, 1991). Because other facilities may be equipped with less sophisticated 15 air pollution control systems, the TEQ emissions could be higher. For example, Cains and Dyke 16 (1994) reported much higher emission rates for two tire incinerators in the United Kingdom that 17 were equipped with only simple grit arrestors. Because the emission factor is based on testing at 18 only one facility and it is inconsistent with other data, the release estimate is considered 19 preliminary. The activity estimates were derived from survey data from EPA, (1992b) and 20 Rubber Manufacturers Association (RMA) (2002). 21 22 3.6.2. W ater Releases 23 Some tire combustion facilities may have wet scrubbers indicating that water releases are 24 possible. No information could be found on CDD/CDF levels in effluent or amounts of effluent 25 discharged from these facilities. Therefore, releases are possible but could not be quantified (Not 26 quantifiable). 27 28 3.6.3. Solid Residue Releases 29 Both bottom ash and fly ash can be created from tire combustion. No information could 30 be found on CDD/CDF levels in ash or amounts of ash associated with these facilities. Any ash 31 would be landfilled, and therefore, would not be considered an environmental release. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-26 DRAFT: DO NOT CITE OR QUOTE 1 2 3.6.4. Products--None 3 4 3.6.5. Release Summary 5 The inventory decision criteria and releases are summarized below: Inventory Decision Criteria for Tire Combustion Air Water Emission tests for at least two units/source types with No sufficient documentation to directly derive emission factors. Solids Products Measured emission factors consistent or have understandable differences. No Emission factor tests represent units that are typical of the No class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-27 DRAFT: DO NOT CITE OR QUOTE Tire Combustion____________________________ Air Releases______________________________ Emission Factors 1987--0.28 ng WHO98 TEQDF/kg (0.28 ng I-TEQDF/kg) (Preliminary). 1995--0.28 ng WHO98 TEQDF/kg (0.28 ng I-TEQDF/kg) (Preliminary). 2000--0.28 ng WHO98 TEQDF/kg (0.28 ng I-TEQDF/kg) (Preliminary).___________ Activity Levels 1987--0.385 billion kg. 1995--0.385 billion kg. 2000--1.8 billion kg.___________________________________________________ Releases 1987--0.1 g WHO98 TEQDF/yr (0.1 g I-TEQDF/yr) (Preliminary). 1995--0.1 g WHO98 TEQDF/yr (0.1 g I-TEQDF/yr) (Preliminary). 2000--0.5 g WHO98 TEQDF/yr (0.5 g I-TEQDF/yr) (Preliminary).________________ W ater Releases____________________________ Possible but quantitative releases could not be made (Not quantifiable)._________________ Solid Residue Releases_________________________ Ash generated at these facilities is landfilled and, therefore, not considered an environmental release.____________________________________________________________________ Products_______________________________ None. 1 3.7. COMBUSTION OF WASTEWATER SLUDGE AT BLEACHED CHEMICAL 2 PULP MILLS 3 Approximately 20.5% of the wastewater sludges generated at bleached chemical pulp 4 mills are dewatered and burned in bark boilers at the mills (NCASI, 1995). These sludges can 5 contain CDDs/CDFs and elevated levels of chloride (NCASI, 1995). However, the sludges 6 generally make up less than 10% of the total feed to the boilers. Most of the feed is composed of 7 wood residues. On this basis, it is believed that the dioxin emission estimates derived in 8 Section 4.2.2 for industrial wood-burning facilities include emissions from boilers burning 9 wastewater sludges generated at bleached chemical pulp mills. 10 11 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-28 DRAFT: DO NOT CITE OR QUOTE 1 3.8. BIOGAS COMBUSTION 2 No changes were made to the release estimates. The emission factor was derived from 3 testing at one facility in Germany and was considered preliminary. The activity was derived 4 from data on the amount of sewage sludge generated and assumptions about how much gas is 5 generated from the sludge. No other water, solid residue, or product releases occur from this 6 source. The inventory decision criteria and releases are summarized below: Inventory Decision Criteria for Biogas Combustion Air Water Solids Emission tests for at least two units/source types with No sufficient documentation to directly derive emission factors. Measured emission factors consistent or have Yes understandable differences. Emission factor tests represent units that are typical of Yes the class. Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). P Products This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-29 DRAFT: DO NOT CITE OR QUOTE Biogas Combustion_______________ Air Releases__________________ Emission Factors 1987--0.46 ng I-TEQDF/Nm3of digester gas combusted (Preliminary). 1995--0.46 ng I-TEQDF/Nm of digester gas combusted (Preliminary). 2000--0.46 ng I-TEQDF/Nm of digester gas combusted (Preliminary). Activity Levels 1987--467-million Nm3 (Preliminary). 1995--467-million Nm3 (Preliminary). 2000--467-million Nm3 (Preliminary)._________________________ Releases 1987--0.2 g I-TEQDF/yr (Preliminary). 1995--0.2 g I-TEQDF/yr (Preliminary). 2000--0.2 g I-TEQDF/yr (Preliminary)._________________________ W ater Releases_________________ None.__________________________________________________________ Solid Residue Releases______________ None.__________________________________________________________ Products____________________ None. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3-30 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 This document is a draftfor review purposes only and does not constitute Agency policy. 3-31 DRAFT: DO NOT CITE OR QUOTE Designaclass APCDb Facility name City located MBWW H-ESP 1 Pinellas Co. 2 St. Petersburg Pinellas Co. St. Petersburg 3 Tampa Tampa 4 Chicago Chicago 5 North Andover North Andover 6 Saugus Saugus 7 Baltimore (RESCO) Baltimore 8 Wilmington Wilmington 9 Glen Cove Glen Cove 10 Westchester Co. Peekskill 11 Tulsa Tulsa 12 Harrisburg Harrisburg 13 Philadelphia E. Philadelphia 14 Philadelphia NW Philadelphia 15 Nashville Thermal Nashville 16 Hampton WTE Hampton 17 Harrisonburg Harrisonburg 18 Norfolk H-ESP subtotals Norfolk NAS State FL FL FL IL MA MA MD NC NY NY OK PA PA PA TN VA VA VA Activity levelc I-TEQ EFd WHO TEQ (kg/y) (ng/kg) EFe (ng/kg) 5.63E+08 478 535 3.24E+08 478 535 2.82E+08 478 535 4.51E+08 478 535 4.22E+08 Actual tested stack emissions 4.22E+08 478 535 6.34E+08 478 535 5.63E+07 478 535 7.04E+07 478 535 6.34E+08 Actual tested stack emissions 2.11E+08 478 535 2.03E+08 Actual tested stack emissions 2.11E+08 Actual tested stack emissions 2.11E+08 478 535 3.16E+08 478 535 5.63E+07 Actual tested stack emissions 2.82E+07 478 535 1.01E+08 5.20E+09 Actual tested stack emissions Annual air emissions (g/y) I-TEQdf 269 WHO9 8 TEQdf 301 155 173 135 151 216 241 200 224 202 226 303 339 27 30 34 38 44 47 101 113 147 167 100 112 101 113 151 169 27 30 13 15 222 2,450 251 2,740 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-32 DRAFT: DO NOT CITE OR QUOTE Designaclass APCDb Facility name MBWW 19 Marion Co. DS/FF DS/FF subtotals Totals For Mass Burn Waterwall MB/REF H-ESP 20 Stamford I 21 Stamford II City located Brooks Stamford Stamford 22 Washington Washington 23 Baltimore (Pulaski) Baltimore 24 Clinton Clinton Township 25 Brooklyn (Henry St.) Brooklyn 26 Brooklyn (SW) Brooklyn 27 Betts Avenue Queens 28 Euclid Euclid 29 Ogden Layton 30 Portsmouth Portsmouth 31 Waukesha H-ESP subtotals MB/REF WS 32 New Canaan 33 Louisville Waukesha New Canaan Louisville 34 Shreveport Shreveport State OR CT CT DC MD MI NY NY NY OH UT VA WI CT KY LA Activity levelc I-TEQ EFd (kg/y) (ng/kg) 1.55E+08 0.67 WHO TEQ EFe (ng/kg) 0.72 1.55E+08 5.35E+09 5.63E+07 1.01E+08 2.82E+08 3.38E+08 1.69E+08 2.82E+08 473 554 473 554 473 554 Actual tested stack emissions 473 554 473 554 2.11E+08 2.82E+08 5.63E+07 1.27E+08 4.51E+07 4.93E+07 2.00E+09 3.04E+07 2.82E+08 5.63E+07 473 473 473 473 473 473 236 236 236 554 554 554 554 554 554 254 254 254 Annual air emissions (g/y) I-TEQDF 0.1 w h o 98 TEQdf 0.1 0 .1 2,450 27 48 133 160 80 133 0 .1 2,740 31 56 156 179 94 156 100 117 133 156 27 31 60 70 21 25 23 27 945 1 ,1 0 0 78 66 72 13 14 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-33 DRAFT: DO NOT CITE OR QUOTE Design3class APCDb MB/REF WS (continued) WS subtotals MB/REF DS/FF Facility name 35 Fall River 36 S.E. Oakland Co. 37 Huntington 38 Sheboygan 39 Framingham City located Fall River Auburn Hills Huntington Sheboygan Framingham DS/FF subtotals Totals For Mass Burn Refractory MOD/SA H-ESP 40 Sitka 41 Tuscaloosa 42 Purham 43 Red Wing 44 Savage 45 Pascagoula 46 Oswego Co. 47 Oneida Co. 48 Hampton 49 Cleburne 50 Barron Co. Sitka Tuscaloosa Purham Red Wing Savage Moss Point Fulton Rome Hampton Clebume Almena H-ESP subtotals State MA MI NY WI MA Activity levelc I-TEQ EFd (kg/y) (ng/kg) 1.69E+08 236 1.69E+08 236 1.27E+08 236 6.76E+07 9.01E+08 1.41E+08 236 0.67 WHO TEQ EFe (ng/kg) 254 254 254 254 0.72 Annual air emissions (g/y) I-TEQDF 40 WHO9 8 t e q df 43 40 43 30 32 16 17 212 229 0.1 0.1 1.41E+08 3.04E+09 AK 7.04E+06 79 0.1 1,160 85.7 0.6 AL 8.45E+07 79 85.7 6.7 MN 2.25E+07 79 85.7 1.8 MN 2.03E+07 Actual tested stack emissions 0.1 MN 1.69E+07 79 85.7 1.3 MS 4.22E+07 79 85.7 3.3 NY 5.63E+07 79 85.7 4.5 NY 5.63E+07 Actual tested stack emissions 4.5 SC 7.60E+07 79 85.7 6.0 TX 3.24E+07 79 85.7 2.6 WI 2.25E+07 79 85.7 1.8 4.37E+08 33 0.1 1,330 0.6 7.2 1.9 0.1 1.5 3.6 4.8 4.8 6.5 2.8 1.9 36 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-34 DRAFT: DO NOT CITE OR QUOTE Designaclass APCDb MOD/SA UNC MOD/SA Facility name City located 51 Batesville Batesville 52 Blytheville Blytheville 53 Hope Hope 54 Hot Springs Hot Springs 55 North Little Rock North Little Rock 56 Osceola Osceola 57 Stuttgart Stuttgart 58 Cassia Co. Burley 59 Simpson Co. Simpson Co. 60 Harpswell Harpswell 61 Fort Leonard Wood Fort Leonard Wood 62 Livingston Park Co. 63 Wrightsville Wrightsville 64 Auburn Auburn 65 Candia Candia 66 Canterbury Canterbury 67 Durham Durham 68 Groveton Groveton 69 Litchfield Litchfield 70 Meredith Meredith 71 Nottingham Nottingham State AR AR AR AR AR AR AR ID KY ME MO MT NC NH NH NH NH NH NH NH NH Activity levelc I-TEQ EFd (kg/y) (ng/kg) 1.41E+07 16.2 1.97E+07 16.2 1.07E+07 16.2 2.82E+07 16.2 2.82E+07 16.2 1.41E+07 16.2 1.69E+07 16.2 1.41E+07 16.2 2.17E+07 16.2 3.94E+06 16.2 2.11E+07 16.2 2.11E+07 16.2 1.41E+07 16.2 1.41E+06 16.2 4.22E+06 16.2 2.82E+06 16.2 3.04E+07 16.2 6.76E+06 16.2 6.20E+06 16.2 8.73E+06 16.2 2.25E+06 16.2 WHO TEQ EFe (ng/kg) 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 Annual air emissions (g/y) I-TEQDF WHO98 TEQDF 0.2 0.2 0.3 0.3 0.2 0.2 0.5 0.5 0.5 0.5 0.2 0.2 0.3 0.3 0.2 0.2 0.3 0.4 0.1 0.1 0.3 0.4 0.3 0.4 0.2 0.2 <0.1 <0.1 0.1 0.1 0.1 0.1 0.5 0.5 0.1 0.1 0.1 0.1 0.1 0.2 <0.1 <0.1 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-35 DRAFT: DO NOT CITE OR QUOTE Designaclass APCDb Facility name UNC (continued) 72 Pittsfield 73 Wilton 74 Wolfeboro 75 Cattaraugus Co. 76 Skaneateless 77 Miami 78 Johnsonville 79 Dyersburg 80 Carthage City 81 Center 82 Gatesville 83 Newport News 84 Salem 85 Bellingham UNC subtotals MOD/SA WS 86 Collegeville 87 Lewisburg 88 Palestine WS subtotals MOD/SA 89 Waxahachie 90 Windham City located Pittsfield Wilton Wolfeboro Cuba Skaneateless Miami Johnsonville Dyersburg Carthage City Center Gatesville Newport News Salem Bellingham Collegeville Lewisburg Palestine Waxahachie Windham State NH NH NH NY NY OK SC TN TX TX TX VA VA WA MN TN TX TX CT Activity levelc I-TEQ EFd (kg/y) (ng/kg) 1.35E+07 16.2 8.45E+06 16.2 4.51E+06 16.2 3.15E+07 16.2 3.66E+06 16.2 3.04E+07 16.2 1.41E+07 16.2 2.82E+07 16.2 1.01E+07 16.2 1.01E+07 16.2 5.63E+06 16.2 9.86E+06 16.2 2.82E+07 16.2 2.82E+07 16.2 5.17E+08 1.41E+07 16.2 1.69E+07 16.2 7.89E+06 16.2 1.41E+07 5.30E+07 3.04E+07 16.2 16.2 WHO TEQ EFe (ng/kg) 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 Annual air emissions (g/y) I-TEQDF WHO9 8 TEQDF 0.2 0.2 0.1 0.1 0.1 0.1 0.5 0.5 0.1 0.1 0.5 0.5 0.2 0.2 0.5 0.5 0.2 0.2 0.2 0.2 0.1 0.1 0.2 0.2 0.5 0.5 0.5 0.5 8.5 8.9 0.2 0.2 0.3 0.3 0.1 0.1 0.2 0.2 0.8 0.8 0.5 0.5 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-36 DRAFT: DO NOT CITE OR QUOTE Design3class APCDb Facility name City located FF 91 Auburn Auburn 92 Portsmouth FF subtotals Totals For Modular-Starved Air MOD/EA UNC 93 Mayport 94 Bellingham Portsmouth Mayport NAS Bellingham UNC subtotals MOD/EA WS 95 East Chicago East Chicago WS subtotals MOD/EA EGB 96 Pittsfield Pittsfield EGB subtotals Totals For Modular Excess Air RDF/Co H-ESP 97 Lakeland 98 Ames Lakeland Ames H-ESP subtotals Totals For Refuse Derived Fuel Cofired With Coal RDF/Ded H-ESP 99 Dade Co. 100 Honolulu Miami Honolulu 101 Haverhill Lawrence 102 Albany Albany 103 Niagara Falls Niagara 104 Akron Akron State ME NH FL WA IN Activity levelc I-TEQ EFd (kg/y) (ng/kg) 5.63E+07 16.2 5.63E+07 1.43E+08 1.15E+09 1.35E+07 16.2 16.2 2.82E+07 16.2 4.17E+07 1.27E+08 16.2 WHO TEQ EFe (ng/kg) 17 17 17 17 17 Annual air emissions (g/y) I-TEQDF 0.9 WHO9 8 t e q df 1.0 0.9 1.0 2.3 2.5 44 48 0.2 0.2 0.5 0.5 0.7 0.7 2.1 2.2 1.27E+08 2.1 2.2 MA 6.76E+07 0.67 0.72 0.1 0.1 6.76E+07 2.36E+08 0.1 2.8 FL 8.45E+07 231 231 20 IA 5.63E+07 1.41E+08 1.41E+08 FL 8.45E+08 231 1,490 231 1,680 13 33 33 1,260 HI 1.69E+08 1,490 1,680 252 MA 3.66E+08 Actual tested stack emissions 546 NY 1.69E+08 1,490 1,680 252 NY 6.20E+08 1,490 1,680 924 OH 2.82E+08 1,490 1,680 420 0.1 2.9 20 13 33 33 1,420 284 615 284 1,040 473 1/7/2013 Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Design3class APCDb Facility name City located 105 Columbus H-ESP subtotals RDF/Ded WS 106 Duluth 107 St. Louis WS subtotals Totals for refuse-derived fuel--dedicated MB/RK H-ESP 108 N. Dayton 109 S. Dayton Columbus Duluth St. Louis Dayton Dayton 110 Gallatin Gallatin H-ESP subtotals MB/RK FF 111 Galax Galax FF subtotals Totals for mass burn rotary kiln TOTALS FOR ALL MwCs operating in 1987 State OH MN MO OH OH TN VA Activity levelc I-TEQ EFd WHO TEQ (kg/y) (ng/kg) EFe (ng/kg) 5.63E+08 3.01E+09 1.13E+08 Actual tested stack emissions 236 254 2.25E+08 3.38E+08 3.49E+09 1.69E+08 236 478 254 535 1.69E+08 478 535 5.63E+07 3.94E+08 1.58E+07 478 47 535 93.1 Annual air emissions (g/y) I-TEQDF 840 4,490 27 WHO9 8 t e q df 946 5,060 29 53 80 4570 81 53 82 5140 90 81 90 27 30 189 210 0.7 1.5 1.58E+07 4.10E+08 1.37E+10 0.7 1.5 190 212 8450 9510 3-37 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 This document is a draftfor review purposes only and does not constitute Agency policy. Table 3-1. Inventory of municipal waste combustors (MWCs) in 1987 (continued) aMWC Design class: FB/RDF = Fluidized-bed refuse-derived fuel; MB/WW = Mass bum waterwall; MB/RK = Mass bum rotary kiln; MB/REF = Mass bum refractory walled; MOD/EA = Modular excess air; RDF/Ded = Dedicated refuse-derived fuel; RDF/co = Refuse-derived fuel cofired with coal (slash indicates devices used in conjunction). bAPCD = air pollution control device. This includes DS/FF (dry scrubber with fabric filters); H-ESP (hot-sided electrostatic precipitator); EGB (electrified gravel bed); WS (wet scrubber); FF (fabric filter); UNC = uncontrolled or no APCD. cActivity Level is the annual amount (kg) of municipal solid waste or refuse derived fuel expected to be combusted by the MWC. It is estimated by multiplying the annual design capacity of the furnace by 85%. The figure of 85% represents the assumption that the MWC will experience downtime during the year for maintenance and repairs. dThe I-TEQdf Emission Factor (EF) expressed in units of ng TEQ/kg combusted. eThe WHO98 TEQdf Emission Factor (EF) expressed in units of ng TEQ/kg combusted. 3-38 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 This document is a draftfor review purposes only and does not constitute Agency policy. 3-39 DRAFT: DO NOT CITE OR QUOTE Designa class APCDb MB/WW DS/FF 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Facility name Huntsville RRF Long Beach RRF Commerce RRF Modesto RRF Bridgeport RESCO Convanta SECONN Bristol RRF Mid-Conn RRF Pasco Co. Broward Co. S Broward Co. N Lake Co. RRF Savannah RRF Indianapolis RRF Saugus RESCO Kent Co. RRF Jackson Co. New Hanover Gloucester Co. Warren Energy RRF City located Huntsville Long Beach Commerce Crows Landing Bridgeport Preston Bristol Hartford Hudson Fort Lauderdale Fort Lauderdale Okahumpka Savannah Indianapolis Saugus Grand Rapids Jackson Wilmington Westville Oxford Township State AL CA CA CA CT CT CT CT FL FL FL FL GA IN MA MI MI NC NJ NJ Activity levelc (kg/y) 1.94E+08 3.89E+08 1.07E+08 2.25E+08 6.34E+08 1.69E+08 1.83E+08 5.63E+08 2.96E+08 6.34E+08 6.34E+08 1.49E+08 1.41E+08 6.65E+08 4.22E+08 1.76E+08 5.63E+07 7.01E+07 1.62E+08 1.13E+08 I-TEQ EFd (ng/kg) Annual air emissions (g/y) WHO TEQ EFe w h o 98 (ng/kg) I-TEQdf TEQdf 0.67 0.72 0.1 0.1 0.67 0.72 0.3 0.3 Actual tested stack emissions 0.1 0.1 Actual tested stack emissions 0.1 0.2 0.67 0.72 0.4 0.5 0.67 0.72 0.1 0.1 0.67 0.72 0.1 0.1 0.67 0.72 0.4 0.4 0.67 0.72 0.2 0.2 0.67 0.72 0.4 0.5 0.67 0.72 0.4 0.5 0.67 0.72 0.1 0.1 0.67 0.72 0.1 0.1 Actual tested stack emissions 0.7 0.7 Actual tested stack emissions 0.3 0.3 0.67 0.72 0.1 0.1 0.67 0.72 <0.1 <0.1 0.67 0.72 0.1 0.1 0.67 0.72 0.1 0.1 0.67 0.72 0.1 0.1 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-40 DRAFT: DO NOT CITE OR QUOTE Designa class APCDb MB/WW DS/FF (continued) DS/FF subtotals MB/WW C-ESP 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 C-ESP subtotals Facility name Onondaga Co. Babylon RRF Hempstead Marion Co. Montgomery Co. Lancaster Co. I-95 Energy RRF Spokane Regional Skagit Co. RRF Pinellas Co. Hillsborough Co. McKay Bay Southernmost RRF Olmstead RRF Westchester RESCO Walter B. Hall RRF Nashville Thermal City located Onondaga Babylon Westbury Brooks Conshohocken Bainbridge Lorton Spokane Mount Vernon St. Petersburg Tampa Tampa Key West Rochester Peekskill Tulsa Nashville State NY NY NY OR PA PA VA WA WA FL FL FL FL MN NY OK TN Activity levelc (kg/y) 2.79E+08 2.11E+08 7.06E+08 1.55E+08 3.38E+08 3.38E+08 8.45E+08 2.25E+08 5.01E+07 9.13E+09 8.45E+08 3.38E+08 2.82E+08 4.22E+07 5.63E+07 6.34E+08 3.17E+08 2.96E+08 2.81E+09 I-TEQ EFd (ng/kg) 0.67 Annual air emissions (g/y) WHO TEQ EFe w ho98 (ng/kg) I-TEQDF TEQdf 0.72 0.2 0.2 Actual tested stack emissions 0.3 0.3 Actual tested stack emissions 0.1 0.1 Actual tested stack emissions <0.1 <0.1 0.67 0.72 0.2 0.2 0.67 0.72 0.2 0.2 Actual tested stack emissions 0.9 1.0 0.67 0.72 0.2 0.2 0.67 0.72 Actual tested stack emissions <0.1 6.3 5.2 <0.1 6.8 5.5 6.1 6.54 2.1 2.2 6.1 6.54 1.7 1.8 6.1 6.54 0.3 0.3 6.1 6.54 0.3 0.4 6.1 6.54 3.9 4.1 6.1 6.54 1.9 2.1 6.1 6.54 1.8 1.9 17 18 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-41 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb MB/WW DS/C-ESP 38 39 40 41 42 43 44 45 DS/C-ESP subtotals MB/WW DSI/FF 46 47 DSI/FF subtotals MB/WW DS/CI/FF 48 49 50 DS/CI/FF subtotals MB/WW H-ESP 51 52 53 54 Facility name Millbury Greater Portland Covanta Haverhill New Hanover Essex Co. RRF Camden RRF Adirondack RRF Charleston RRF City located Millbury Portland Haverhill Wilmington Newark Camden Hudson Falls Charleston SES Claremont RRF Concord Claremont Concord Hennepin Energy Union Co. RRF Wheelabrator Falls Minneapolis Rahway Falls Creek University City RRF Long Beach RRF Harrisburg WTE NASA RRF Charlotte Long Beach Harrisburg Hampton State MA ME MA NC NJ NJ NY SC NH NH MN NJ PA NC NY PA VA Activity levelc (kg/y) 4.22E+08 1.41E+08 4.65E+08 5.63E+07 6.41E+08 2.96E+08 1.22E+08 1.69E+08 2.73E+09 5.63E+07 1.41E+08 1.97E+08 3.38E+08 4.06E+08 4.22E+08 1.17E+09 6.62E+07 5.63E+07 2.03E+08 5.63E+07 I-TEQ EFd (ng/kg) 6.1 Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF WHO9 8 t e q df 6.54 2.6 2.8 Actual tested stack emissions 1.4 1.5 6.1 6.54 2.8 3.0 6.1 6.54 0.3 0.4 6.1 6.54 3.9 4.2 Actual tested stack emissions 0.7 0.8 6.1 6.54 0.7 0.8 Actual tested stack emissions Actual tested stack emissions 1.0 13 0.2 1.1 15 0.2 1.9 2.07 0.3 0.3 0.5 0.5 1.5 1.61 0.5 0.5 1.5 1.61 0.6 0.7 Actual tested stack emissions 478 535 0.6 1.7 32 0.7 1.9 35 478 535 27 30 Actual tested stack emissions 147 167 Actual tested stack emissions 27 30 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-42 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb Facility name MB/WW H-ESP (continued) 55 Harrisonburg RRF 56 Baltimore (RESCO) H-ESP subtotals MB/WW DSI/H-ESP 57 North Andover DSI/H-ESP subtotals MB/WW DSI/CI/H-ESP 58 Alexandria RRF DSI/CI/H-ESP subtotals Totals for mass burn waterwall MB/REF WS 59 New Canaan MWC 60 Fall River Subtotals for MB/REF WS MB/REF DS/C-ESP 61 DS/C-ESP subtotals MB/REF C-ESP 62 C-ESP subtotals MB/REF DS/FF 63 64 Pulaski Clinton Mid Maine Waste Huntington DS/FF subtotals City located Harrisonburg Baltimore North Andover State VA MD MA Activity levelc (kg/y) 2.82E+07 6.34E+08 1.04E+09 4.22E+08 I-TEQ EFd (ng/kg) Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF WHO9 8 t e q df Actual tested stack emissions 5.8 5.9 Actual tested stack emissions 9.9 11 Actual tested stack emissions 249 3.3 279 3.5 Alexandria 4.22E+08 VA 2.75E+08 Actual tested stack emissions 3.3 2.1 3.5 2.3 New Canaan Fall River Baltimore 2.75E+08 1.74E+10 CT 3.52E+07 MA 1.69E+08 2.04E+08 MD 4.22E+08 236 254 236 254 Actual tested stack emissions 2.1 293 8.3 40 48 22 2.3 327 9.0 43 52 22 Clinton 4.22E+08 MI 1.69E+08 Actual tested stack emissions 22 40 22 43 Auburn Huntington 1.69E+08 ME 5.63E+07 NY 2.11E+08 2.67E+08 0.67 0.67 40 43 0.72 <0.1 <0.1 0.72 0.1 0.2 0.1 0.2 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-43 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb Facility name MB/REF DSI/FF 65 Davis Co. DSI/FF subtotals Totals for mass burn refractory MB/RK C-ESP 66 Montenay Bay 67 Sumner Co. MB/RK C-ESP subtotals MB/RK DSI/C-ESP 68 Dayton RRF DSI/C-ESP subtotals MB/RK DSI/FF 69 70 Dutchess Co. MacArthur WTE DSI/FF subtotals MB/RK DS/FF 71 72 Delaware Co. York Co. DS/FF subtotals Totals for mass burn rotary kiln RDF/ded C-ESP 73 Dade Co. RRF 74 Niagara Falls RDF 75 Central Wayne Co. 76 Ramsey-WA City located Layton Panama City Gallatin Dayton State UT Activity levelc (kg/y) 1.13E+08 I-TEQ EFd (ng/kg) 1.91 Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF WHO9 8 t e q df 2.07 0.2 0.2 1.13E+08 1.18E+09 FL 1.44E+08 TN 5.63E+07 2.00E+08 OH 5.07E+08 47 47 47 0.2 0.2 110 117 93.1 6.8 13 93.1 2.7 5.2 9.5 18 93.1 24 47 Poughkeepsie Ronkonkoma Chester York Miami Niagara Falls Dearborn Red Wing 5.07E+08 NY 1.13E+08 NY 1.46E+08 2.59E+08 PA 7.57E+08 PA 3.79E+08 1.14E+09 2.10E+09 FL 8.45E+08 NY 6.20E+08 MI 1.41E+08 MN 2.03E+08 Actual tested stack emissions 47 93.1 0.62 0.68 Actual tested stack emissions 231 253 Actual tested stack emissions Actual tested stack emissions 231 253 24 5.3 6.7 12 0.5 0.2 0.7 46 199 143 33 47 47 10 14 24 0.5 0.3 0.8 90 214 157 36 51 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-44 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb RDF/ded C-ESP subtotals RDF/ded DS/C-ESP 77 78 79 80 DS/C-ESP subtotals RDF/ded DS/FF 81 82 83 84 85 86 DS/FF subtotals RDF/ded DSI/FF DSI/FF subtotals RDF/ded DSI/H-ESP 87 88 89 Facility name West Palm Beach SEMASS RRF Western L Superior Honolulu RRF SEMASS RRF Maine Energy RRF Penobscot Energy Greater Detroit RRF Wilmarth Plant Norfolk Navy Yard Mid-Connecticut Elk River RRF Haverhill Lawrence DSI/H-ESP subtotals RDF/ded H-ESP 90 H-ESP subtotals Kodak MWC City located Palm Beach Rochester Duluth Honolulu Rochester Biddeford Orrington Detroit Mankato Norfolk Hartford Elk River Lawrence Rochester State FL MA MN HI MA ME ME MI MN VA CT MN Activity levelc (kg/y) 1.81E+09 5.63E+08 5.07E+08 7.32E+07 6.08E+08 1.75E+09 7.60E+08 1.69E+08 1.97E+08 6.20E+08 2.03E+08 5.63E+08 5.63E+08 3.07E+09 4.22E+08 I-TEQ EFd (ng/kg) 0.53 Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF 422 WHO9 8 t e q df 458 0.56 0.3 0.3 0.53 0.56 0.3 0.3 0.53 0.56 <0.1 <0.1 0.53 0.56 0.3 0.3 0.9 0.9 0.24 0.26 0.2 0.2 Actual tested stack emissions 0.1 0.1 Actual tested stack emissions <0.1 <0.1 Actual tested stack emissions 0.1 0.2 47 93.1 0.1 0.1 0.24 0.26 0.1 0.1 Actual tested stack emissions 47 93.1 0.1 0.7 20 0.1 0.8 39 4.22E+08 MA 2.00E+08 285 20 39 316 57 63 2.00E+08 NY 4.22E+07 4.22E+07 1,490 1,680 57 63 63 71 63 71 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-45 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb Facility name Totals for dedicated refuse derived fuel MOD/SA UNC 91 Batesville MWC 92 Stuttgart MWC 93 Osceola MWC 94 Miami Airport 95 NIEHS MWC 96 Livingston/Park Co. 97 Miami MWC 98 Coos Bay MWC 99 Pentagon MWC UNC subtotals MOD/SA H-ESP 100 Juneau MWC 101 Harford Co. 102 City of Clebume 103 Barron Co. H-ESP subtotals MOD/SA C-ESP C-ESP subtotals 104 105 106 107 Perham MWC Polk Co. MWC Oswego Co. Westmoreland City located Batesville Stuttgart Osceola Miami Durham Park Co. Miami Coquille Arlington Juneau Aberdeen Clebume Almena Perham Fosston Fulton Greensburg State AR AR AR FL NC MT OH OR VA AK MD TX WI MN MN NY PA Activity levelc (kg/y) 7.30E+09 2.82E+07 1.77E+07 1.41E+07 1.69E+07 1.13E+07 2.03E+07 2.96E+07 3.52E+07 1.41E+07 1.87E+08 1.97E+07 1.01E+08 3.24E+07 2.82E+07 1.81E+08 3.21E+07 2.25E+07 5.63E+07 1.41E+07 1.25E+08 I-TEQ EFd (ng/kg) 16.2 16.2 16.2 16.2 16.2 16.2 16.2 16.2 16.2 79 79 79 79 Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF 564 WHO9 8 t e q df 633 17 0.5 0.5 17 0.3 0.3 17 0.2 0.2 17 0.3 0.3 17 0.2 0.2 17 0.3 0.3 17 0.5 0.5 17 0.6 0.6 17 0.2 0.2 3.1 3.1 85.7 1.6 1.7 85.7 8.0 8.7 85.7 2.6 2.8 85.7 2.2 2.4 14 16 16.2 17 0.5 0.6 16.2 17 0.4 0.4 16.2 17 0.9 1.0 16.2 17 0.2 0.2 2.0 2.2 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-46 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb Facility name MOD/SA DS/DSI/C-ESP 108 DS/DSI/C-ESP subtotals MOD/SA DSI/FF 109 DSI/FF subtotals MOD/SA WS 110 111 Chamber Medical St. Croix WTE Fergus Falls Center MWC 112 Panola Co. WS subtotals MOD/SA WS/FF 113 Recomp Bellingham WS/FF subtotals Totals for modular-starved air MOD/EA UNC 114 Mayport NAS UNC subtotals MOD/EA H-ESP 115 H-ESP subtotals MOD/EA DSI/H-ESP 116 DSI/H-ESP subtotals MOD/EA C-ESP 117 118 Richards Asphalt Co. Sitka MWC Pope-Douglas SW Red Wing City located Hampton State SC Activity levelc (kg/y) 7.60E+07 7.60E+07 New Richmond WI 2.87E+07 Fergus Falls Center Carthage Bellingham 2.87E+07 MN 2.65E+07 TX 1.13E+07 TX 1.13E+07 4.90E+07 WA 2.82E+07 Mayport 2.82E+07 6.46E+08 FL 1.41E+07 Savage Sitka Alexandria Red Wing 1.41E+07 MN 1.97E+07 1.97E+07 AK 1.41E+07 1.41E+07 MN 2.03E+07 MN 2.03E+07 I-TEQ EFd (ng/kg) 16.2 Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF WHO9 8 t e q df 17 1.2 1.3 1.2 1.3 0.02 0.03 <0.1 <0.1 <0.1 <0.1 16.2 17 0.4 0.5 16.2 17 0.2 0.2 16.2 17 0.2 0.2 0.8 0.9 16.2 17 0.5 0.5 0.5 0.5 22 24 16.2 17 0.2 0.2 Actual tested stack emissions 118 119 Actual tested stack emissions Actual tested stack emissions 0.2 2.3 2.3 1.7 1.7 0.3 0.1 0.2 2.4 2.4 1.7 1.7 0.3 0.1 1/7/2013 Table 3-2. Inventory of municipal waste combustors (MWCs) in 1995 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-47 DRAFT: DO NOT CITE OR QUOTE Design3 class APCDb Facility name 119 Pascagoula RRF C-ESP subtotals MOD/EA DS/FF 120 Wallingford RRF DS/FF subtotals MOD/EA DSI/FF 121 Springfield RRF DSI/FF subtotals MOD/EA WS/C-ESP 122 Pittsfield RRF WS/C-ESP subtotals Totals for modular excess air FB/RDF DS/FF 123 Fayetteville RRF City located Moss Point Wallingford Agawam Pittsfield Fayetteville State MS CT Activity levelc (kg/y) 4.22E+07 8.28E+07 1.18E+08 I-TEQ EFd (ng/kg) 16.2 16.2 Annual air emissions (g/y) WHO TEQ EFe (ng/kg) I-TEQDF WHO9 8 t e q df 17 0.7 0.7 1.1 1.1 17 1.9 2.0 1.18E+08 MA 1.01E+08 16.2 1.9 2.0 17 1.6 1.7 1.01E+08 MA 6.76E+07 Actual tested stack emissions 1.6 1.1 1.7 1.2 6.76E+07 4.17E+08 NC 1.69E+08 0.67 1.1 1.2 10 10 0.72 0.1 0.1 DS/FF subtotals FB/RDF DSI/FF DSI/FF subtotals 124 Tacoma RRF FB/RDF DSI/EGB 125 LaCrosse Co. DSI/EGB subtotals Totals for fluidized bed/refuse-derived fuel Totals for all MWCs operating in 1995 Tacoma La Crosse 1.69E+08 WA 8.45E+07 8.45E+07 WI 1.13E+08 1.13E+08 3.66E+08 2.98E+10 0.67 0.72 Actual tested stack emissions 0.1 0.1 0.1 0.1 0.1 0.3 1050 0.1 0.1 0.1 0.1 0.1 0.3 1200 aMWC Design class: FB/RDF = Fluidized-bed refuse-derived fuel; MB/WW = Mass bum waterwall; MB/RK = Mass bum rotary kiln; MB/REF = Mass bum refractory walled; MOD/EA = Modular excess air; RDF/Ded = Dedicated refuse-derived fuel; RDF/co = Refuse-derived fuel cofired with coal (slash indicates devices used in conjunction). 1/7/2013 bAPCD = air pollution control device. This includes DS/FF (dry scrubber with fabric filters); H-ESP (hot-sided electrostatic precipitator); EGB (electrified gravel bed); WS (wet scrubber); FF (fabric filter); UNC = uncontrolled or no APCD. cActivity Level is the annual amount (kg) of municipal solid waste or refuse derived fuel expected to be combusted by the MWC. It is estimated by multiplying the annual design capacity of the furnace by 85%. The figure of 85% represents the assumption that the MWC will experience downtime during the year for maintenance and repairs. dThe I-TEQdf Emission Factor (EF) expressed in units of ng TEQ/kg combusted. eThe WHO98 TEQdf Emission Factor (EF) expressed in units of ng TEQ/kg combusted. This document is a draftfor review purposes only and does not constitute Agency policy. 3-48 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 This document is a draftfor review purposes only and does not constitute Agency policy. 3-49 DRAFT: DO NOT CITE OR QUOTE Design3 Class APCDb MB/WW DS/FF/CI/SNCR 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Facility Name Huntsville Stanislaus Bristol RRF Wheelabrator Lisbon Inc. Hillsborough Co. RRF McKay Bay REF Lake Co. RRF Lee Co. RRF Pasco Co. RRF Pinellas Co. RRF Savannah RRF Indianapolis RRF Haverhill RRF Wheelabrator North Andover Wheelabrator Saugus Montgomery Co. RRF Kent Co. WTE Facility Central Wayne Energy Covanta Hennepin New Hanover Co. WTE Wheelabrator Concord City Located Madison Stanislaus Hartford New London Hillsborough Hillsborough Lake Lee Pasco Pinellas Chatham Marion Essex Essex Essex Montgomery Kent Wayne Hennepin New Hanover Merrimack State AL CA CT CT FL FL FL FL FL FL GA IN MA MA MA MD MI MI MN NC NH Activity Levelc (kg/y) 1.77E+08 2.61E+08 1.86E+08 1.79E+08 3.58E+08 1.80E+08 1.66E+08 3.95E+08 3.10E+08 8.91E+08 1.21E+08 6.54E+08 5.68E+08 3.83E+08 4.32E+08 5.20E+08 1.80E+08 6.18E+07 3.65E+08 1.27E+08 1.84E+08 Emission Factor (ng TEQ/kg) w h o 98 I-TEQdf TEQdf Annual Air Emissions (g/y) w h o 98 I-TEQdf TEQdf Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested 0.2 0.2 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.2 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested 0.3 0.3 Tested Tested 0.02 0.02 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 1/7/2013 Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-50 DRAFT: DO NOT CITE OR QUOTE Design3 Class APCDb Facility Name MB/WW 22 Gloucester Co. DS/FF/CI/SNCR 23 Union Co. RRF (continued) 24 Niagara Falls 25 Onondaga Co. RRF 26 Babylon RRF 27 Huntington RRF 28 Wheelabrator Westchester 29 Walter B. Hall RRF (Tulsa) 30 Marion Co. WTE 31 Lancaster Co. 32 Wheelabrator Falls RRF 33 Montenay Montgomery 34 Nashville Thermal Transfer Corp. 35 Alexandria/Arlington RRF 36 I-95 Energy RRF 37 Spokane Regional Facility DS/FF/CI/SNCR subtotals MB/WW 38 Long Beach SERRF DS/FF/SNCR 39 Wheelabrator South Broward 40 Wheelabrator North Broward 41 Hempstead DS/FF/SNCR subtotals MB/WW 42 Wheelabrator Bridgeport, L.P. DS/FF/CI 43 Southeastern Connecticut RRF 44 Warren Energy RF DS/FF/CI subtotals MB/WW 45 Jackson Co. RRF DS/FF 46 New Hanover Co. 47 SES Claremont DS/FF subtotals City Located Gloucester Union Niagara Onondaga Suffolk Suffolk Westchester Tulsa Marion Bainbridge Bucks Montgomery Davidson Alexandria Fairfax Spokane Los Angeles Ft. Lauderdale Broward Nassau Fairfield New London Warren Jackson New Hanover Sullivan State NJ NJ NY NY NY NY NY OK OR PA PA PA TN VA VA WA CA FL FL NY CT CT NJ MI NC NH Activity Levelc (kg/y) 1.81E+08 5.09E+08 7.14E+08 3.35E+08 2.20E+08 3.16E+08 6.50E+08 3.39E+08 1.84E+08 3.81E+08 5.25E+08 4.03E+08 2.25E+08 3.32E+08 1.09E+09 2.85E+08 1.34E+10 5.74E+08 7.56E+08 7.76E+08 8.87E+08 2.99E+09 7.08E+08 7.08E+08 1.25E+08 1.25E+08 6.27E+07 6.27E+07 6.27E+07 1.88E+08 Emission Factor (ng Annual Air Emissions TEQ/kg) ________(g/y)________ w h o 98 w h o 98 I-TEQof TEQdf I-TEQdf t e q df Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested 0.4 0.4 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 Tested Tested 0.5 0.6 Tested Tested <0.1 <0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 Tested Tested <0.1 <0.1 2.3 2.5 Tested Tested 0.1 0.1 Tested Tested 0.2 0.2 Tested Tested 0.1 0.1 Tested Tested 0.5 0.5 0.9 0.9 Tested Tested 0.1 0.1 Tested Tested 0.1 0.1 Tested Tested <0.1 <0.1 0.2 0.2 0.67 0.72 <0.1 0.1 0.67 0.72 <0.1 0.1 0.67 0.72 <0.1 0.1 <0.1 0.3 1/7/2013 Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-51 DRAFT: DO NOT CITE OR QUOTE Design3 Class APCDb MB/WW D S/ESP/CI/SNCR 48 49 50 51 52 53 MB/WW DS/ESP/CI 54 55 MB/WW C-ESP 56 57 58 MB/WW 59 H-ESP MB/WW 60 UNC Totals for all MB/WW MB/REF 61 DSI/H-ESP MB/REF 62 DS/FF Totals for all MB/REF MB/RK 63 DS/FF MB/RK 64 DS/FF/CI/SNCR MB/RK 65 DSI/FF 66 Facility Name McKay Bay REF Wheelabrator Millbury Wheelabrator Baltimore Greater Portland Region RRF Camden RRF Essex Co. RRF DS/ESP/CI/SNCR subtotals Adirondack RRF Foster Wheeler Charleston RRF DS/ESP/CI subtotals Southernmost WTE Olmstead WTE Facility NASA C-ESP subtotals Harrisburg WTE H-ESP subtotals Harrisonburg UNC subtotals City Located Hillsborough Worcester Independent City Cumberland Camden Essex Washington Charleston Monroe Olmstead Hampton City Dauphin Harrisonburg Davis/Wasatch DSI/H-ESP subtotals Mid Maine Waste Action Corp. DS/FF subtotals Davis Androscoggin American Ref-Fuel of Delaware Valley DS/FF subtotals York Co. DS/FF/CI/SNCR subtotals Dutchess Co. RRF MacArthur WTE Delaware York Dutchess Suffolk State FL MA MD ME NJ NJ NY SC FL MN VA PA VA UT ME PA PA NY NY Activity Levelc (kg/y) 1.80E+08 4.64E+08 7.15E+08 1.73E+08 2.77E+08 9.85E+08 2.79E+09 1.62E+08 2.11E+08 3.74E+08 3.74E+08 6.27E+07 6.27E+07 4.99E+08 1.54E+08 1.54E+08 3.14E+07 3.14E+07 2.05E+10 1.25E+08 1.25E+08 6.27E+07 6.27E+07 1.88E+08 1.11E+09 1.11E+09 3.97E+08 3.97E+08 1.25E+08 1.52E+08 Emission Factor (ng TEQ/kg) WHO98 I-TEQdf t e Q df Tested Tested Tested Tested Tested Tested Annual Air Emissions ________(g/y)________ WHO9 8 I-TEQdf t e q df <0.1 <0.1 0.1 0.1 0.4 0.4 Tested Tested Tested Tested Tested 6.1 6.1 6.1 Tested 1.9 Tested Tested Tested Tested Tested 6.54 6.54 6.54 Tested 2.07 Tested 0.67 Tested 0.72 Tested Tested Tested Tested Tested Tested Tested Tested 0.2 0.4 0.2 1.3 1.0 0.3 1.3 2.3 0.4 0.4 3.1 21 21 0.1 0.1 30 2.7 2.7 <0.1 <0.1 2.7 0.5 0.5 0.1 0.1 <0.1 <0.1 0.2 0.4 0.2 1.3 1.0 0.3 1.3 2.4 0.4 0.4 3.2 23 23 0.1 0.1 33 2.9 2.9 0.1 0.1 3.0 0.5 0.5 0.1 0.1 0.1 <0.1 1/7/2013 Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-52 DRAFT: DO NOT CITE OR QUOTE Design3 Class APCDb MB/RK 67 FF MB/RK 68 H-ESP MB/RK 69 C-ESP Totals for all MB/RK MOD/EA 70 DS/FF MOD/EA 71 DSI/FF MOD/EA 72 WS/C-ESP MOD/EA 73 C-ESP 74 MOD/EA 75 H-ESP Totals for all MOD/EA MOD/SA 76 C-ESP 77 78 79 MOD/SA DSI/C-ESP MOD/SA DSI/H-ESP MOD/SA DS/FF/CI 80 81 82 Facility Name DSI/FF subtotals Galax City SW FF subtotals Bay Resource Management Center H-ESP subtotals Sumner Co. C-ESP subtotals Wallingford RRF DS/FF subtotals Springfield RRF DSI/FF subtotals Pittsfield RRF WS/C-ESP subtotals Pope-Douglas Waste Red Wing Solid Waste Boiler Facility C-ESP subtotals Pascagoula H-ESP subtotals Juneau RRF Perham Renewable RF Polk Co. Barron Co. C-ESP subtotals City of Cleburne DSI/C-ESP subtotals Harford Co. WTE Fac. DSI/H-ESP subtotals Oswego Co. WTE DS/FF/CI subtotals City Located Grayson Bay Sumner New Haven Hampden Berkshire Douglas Goodhue Jackson Juneau Borough Otter Tail Polk Barron Johnson Harford Oswego State VA FL TN CT MA MA MN MN MS AK MN MN WI TX MD NY Activity Levelc (kg/y) 2.78E+08 1.76E+07 1.76E+07 1.54E+08 1.54E+08 6.27E+07 6.27E+07 2.02E+09 1.32E+08 1.32E+08 1.13E+08 1.13E+08 1.13E+08 1.13E+08 2.26E+07 2.26E+07 4.52E+07 4.70E+07 4.70E+07 4.50E+08 2.20E+07 3.57E+07 2.51E+07 3.14E+07 1.14E+08 3.57E+07 3.57E+07 1.13E+08 1.13E+08 6.27E+07 6.27E+07 Emission Factor (ng TEQ/kg) WHO98 I-TEQdf t e Q df Tested Tested Tested Tested 47 93.1 Tested 0.025 16.2 16.2 16.2 118 Tested 0.024 17 17 17 119 16.2 16.2 16.2 16.2 16.2 Tested Tested 17 17 17 17 17 Tested Tested Annual Air Emissions ________(g/y)________ WHO9 8 I-TEQdf TEQDF <0.1 0.1 0.2 0.3 0.2 0.3 8.1 8.9 8.1 8.9 3.0 5.9 3.0 5.9 12 16 0.1 0.1 0.1 0.1 <0.1 <0.1 <0.1 <0.1 1.8 1.9 1.8 1.9 0.4 0.4 0.4 0.4 0.8 0.8 5.6 5.6 5.6 5.6 8.3 8.4 0.4 0.4 0.6 0.6 0.4 0.4 0.5 0.5 1.9 1.9 0.6 0.6 0.6 0.6 5.4 6.0 5.4 6.0 0.1 0.1 0.1 0.1 1/7/2013 Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 3-53 DRAFT: DO NOT CITE OR QUOTE Design3 Class APCDb MOD/SA DSI/FF MOD/SA 83 84 Facility Name Coos Bay Incinerator DSI/FF subtotals Arlington -Pentagon MOD/SA WS MOD/SA UNC MOD/SA subtotals 85 Fergus Falls 86 Panola Co. WTE 87 Center RRF WS subtotals 88 Miami Airport 89 Livingston/Park Co. 90 Miami RRF UNC subtotals Totals for all MOD/SA RDF/Ded 91 DS/FF/SNCR 92 93 94 RDF/Ded DS/FF/CI/SNCR RDF/Ded DS/FF 95 96 97 98 99 RDF/Ded DSI/FF 100 RDF/Ded 101 Mid-Connecticut RRF SEMASS RRF Maine Energy Recovery Wilmarth Plant DS/FF/SNCR subtotals Dade Co. RRF DS/FF/CI/SNCR subtotals Penobscot Energy Recovery Greater Detroit RRF Great River Energy SPSA Waste to Energy DS/FF subtotals Red Wing Plant DSI/FF subtotals LaCrosse Co. City Located Coos Arlington Otter Tail Panola Shelby Dade Park Ottawa Hartford Plymouth York Blue Earth Dade Penobscot Wayne Sherburne Portsmouth Goodhue LaCrosse State OR VA MN TX TX FL MT OK CT MA ME MN FL ME MI MN VA MN WI Activity Levelc (kg/y) 4.70E+07 4.70E+07 3.14E+07 3.14E+07 2.95E+07 1.25E+07 1.25E+07 5.46E+07 1.88E+07 2.26E+07 3.29E+07 7.43E+07 5.33E+08 7.50E+08 3.65E+08 2.47E+08 2.03E+08 1.57E+09 6.68E+08 6.68E+08 2.20E+08 6.93E+08 2.85E+08 4.89E+08 1.69E+09 1.82E+08 1.82E+08 4.44E+07 Emission Factor (ng TEQ/kg) WHO98 I-TEQdf t e Q df Tested Tested 16.2 17 Annual Air Emissions ________(g/y)________ WHO9 8 I-TEQdf TEQDF <0.1 <0.1 <0.1 <0.1 0.5 0.5 16.2 17 16.2 17 16.2 17 16.2 17 16.2 17 16.2 17 0.5 0.5 0.5 0.5 0.2 0.2 0.2 0.2 0.9 0.9 0.3 0.3 0.4 0.4 0.5 0.6 1.2 1.3 10 11 Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested Tested 0.1 <0.1 <0.1 0.1 0.2 1.3 1.3 <0.1 0.5 0.1 0.5 1.1 0.1 0.1 <0.1 <0.1 0.1 0.2 1.4 1.4 <0.1 0.5 0.1 0.5 1.1 0.1 0.1 0.1 Tested Tested 0.7 0.7 1/7/2013 Table 3-3. Inventory of municipal waste combustors (MWCs) in 2000 (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Design3 Class APCDb DSI/FF/WSp/SNCR Facility Name DSI/FF/WSp/SNCR subtotals RDF/Ded 102 Central Wayne Co. C-ESP C-ESP subtotals RDF/Ded 103 Honolulu RRF DS/ESP DS/ESP subtotals RDF/Ded 104 SEMASS RRF DS/ESP/FF/CI DS/ESP/FF/CI subtotals Totals for all RDF/Ded FB/RDF 105 Tacoma DSI/FF DSI/FF subtotals Totals for all FB/RDF Totals for all MWCs operating in year 2000 City Located Wayne Honolulu Plymouth Pierce State MI HI MA WA Activity Levelc (kg/y) 4.44E+07 1.56E+08 1.56E+08 5.15E+08 5.15E+08 7.41E+08 7.41E+08 5.56E+09 9.41E+07 9.41E+07 9.41E+07 2.94E+10 Emission Factor (ng TEQ/kg) WHO98 I-TEQdf t e Q df Annual Air Emissions ________(g/y)________ WHO9 8 I-TEQdf t e q df 0.7 0.7 Tested Tested Tested Tested Tested Tested 0.67 0.72 0.1 0.1 2.0 2.0 0.1 0.1 5.6 0.1 0.1 0.1 69 0.1 0.1 2.2 2.2 0.10 0.10 5.9 0.1 0.1 0.1 77 aMWC Design class: FB/RDF = Fluidized-bed refuse-derived fuel; MB/WW = Mass bum waterwall; MB/RK = Mass bum rotary kiln; MB/REF = Mass bum refractory walled; MOD/EA = Modular excess air; RDF/Ded = Dedicated refuse-derived fuel. bAPCD = air pollution control device. DS/FF/CI/SNCR (dry scrubber followed by fabric filter with carbon injection and nitrogen oxide control); DS/FF/SNCR (dry scrubber followed by fabric filter with nitrogen oxide control); DS/FF/CI (dry scrubber followed by fabric filter with carbon injection); DS/FF (dry scrubber followed by fabric filter); DSI/FF (duct sorbent injection followed by fabric filter); DSI/FF/WSp/SNCR (duct sorbent injection followed by fabric filter with water spray and nitrogen oxide control); DS/ESP/CI/SNCR (dry scrubber followed by electrostatic precipitator with carbon injection and nitrogen oxide control); DS/ESP/CI (dry scrubber followed by electrostatic precipitator with carbon injection); C-ESP (cold-sided electrostatic precipitator); H-ESP (hot-sided electrostatic precipitator); DSI/C-ESP (duct sorbent injection followed by cold-sided electrostatic precipitator); DSI/H-ESP (duct sorbent injection followed by hot-sided electrostatic precipitator); WS (wet scrubber); WS/C-ESP (wet scrubber followed by cold-sided electrostatic precipitator); UNC (uncontrolled). cActivity Level is the annual amount (kg) of municipal solid waste or refuse derived fuel expected to be combusted by the MWC. It is estimated by multiplying the annual design capacity of the furnace by 85%. The figure of 85% represents the assumption that the MWC will experience downtime during the year for maintenance and repairs. 3-54 DRAFT: DO NOT CITE OR QUOTE Table 3-4. TEQ air emissions from medical waste incinerators (MWIs) for reference year 1987, 1995, and 2000 MWI class 1987 No. of tested facilities/total Uncontrolled 7/5,000 Controlled TOTAL 1995 Uncontrolled 0 7/1,770 Controlled 12/605 TOTAL 2000 Uncontrolled 7/975 Controlled 12/333 TOTAL I-TEQd f emission factor (ng/kg) 1,800 1,800 50 1,800 50 W H O 98 TEQd f emission factor (ng/kg) Activity level ( k g yr) Annual I-TEQd f emissions (g/yr) 1,900 1,900 51 1.43E+09 0 1.43E+09 2.54E+08 5.17E+08 7.71E+08 2,600 0 2,600 460 26 490 1,900 51 1.98E+08 4.03E+08 6.01E+08 360 20 380 Annual W H O 98 TEQd f emissions (g/yr) 2,700 0 2,700 480 26 510 380 20 400 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 3_55 DRAFT: DO NOT CITE OR QUOTE 1 4. COMBUSTION SOURCES OF CDDS/CDFS: POWER/ENERGY GENERATION 2 3 4 4.1. MOTOR VEHICLE FUEL COMBUSTION 5 This section covers on-road and off-road vehicles. The activity estimates were changed 6 so that all are on a per-liter basis rather than a per-km driven basis, resulting in small changes in 7 the air-release estimates. Other changes include addition of new literature studies, clarifications 8 about derivations of emission factors, and discussions about the uncertainties associated with the 9 estimates for off-road vehicles. Separate release estimates for 2-stroke engines (also referred to 10 as 2-cycle engines) were considered, but insufficient information was available on both emission 11 factors and activities to do this. The activity estimates are based on total fuel sold and include 12 fuels used in all types of engines. Thus, 2-stroke engines are represented, and the uncertainties 13 associated with their emissions are discussed. The confidence ratings for releases from all off 14 road vehicles were changed to preliminary due to lack of emissions test data. There were 15 insufficient data to make an emission estimate for waste motor oil; see Section 4.3 for 16 information on combustion of waste motor oil. 17 18 4.1.1. Air Literature 19 A number of additional studies on dioxin emissions from diesel engines were found as 20 summarized below. 21 Gullett and Ryan (2002) characterized CDD/CDF emissions from two heavy duty diesel 22 trucks under highway driving conditions and while idling: a 1989 Ford with a turbocharged 23 Cummins engine and mechanical fuel controls and a 1990 Kenworth with a T800 engine 24 equipped with the first generation of electronic fuel controls. The Ford trailer was loaded at 25 16,900 kg, and the Kenworth trailer at 8,400 kg. The Kenworth was tested using both a high 26 mileage and the same engine in rebuilt, or "low mileage" condition. The average emission 27 factors reported for each vehicle and driving condition are presented below: 28 29 Ford/highway: 385 pg WHO98 TEQ/L 30 Kenworth/highway (old engine): 58 pg WHO98 TEQ/L 31 Kenworth/highway (rebuilt engine): 24 pg WHO98 TEQ/L 32 Kenworth/idle: 6 pg WHO98 TEQ/L This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-1 DRAFT: DO NOT CITE OR QUOTE 1 Tests were also performed using a low-sulfur fuel, which was representative of U.S. diesel fuels 2 in 2000. 3 Kim et al. (2003) conducted a study in Korea that measured CDD/CDF emissions from a 4 light duty diesel engine under various loadings. The average CDD/CDFs concentrations per unit 5 of exhaust gas with 25, 50, and 75% load rate are 14.5, 6.9, and 6.4 pg TEQ/Nm3, respectively. 6 According to the authors, these values, respectively, convert to 2.0, 0.6, and 0.5 pg TEQ/L fuel. 7 Norbeck et al. (1998) measured CDD/CDF emissions from a 6-cylinder, 310-hp diesel 8 engine over the heavy-duty transient test cycle. Emission testing was conducted at the Los 9 Angeles County Metropolitan Transportation Authority emission test facility. Dioxin sampling 10 was conducted for the pre-1993 and reformulated fuels. Although PCDDs and PCDFs were 11 detected, the most toxic isomers, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, and 2,3,4,7,8-PeCDF were 12 not detected in either the pre-1993 or reformulated fuel. TEQ profiles were incomplete due to 13 the low levels of CDD and PCDF detected in the emission samples. 14 Mayer et al (2003) reports on the use of fine-pored hot gas traps with filtration 15 efficiencies exceeding 99% of the solid particles in the diesel exhaust gas. Catalyzed particle 16 traps also achieve greater than 99% reduction in emissions of semi-volatile hydrocarbons (Laroo 17 et al., 2011, CRC, 2009). This technology is used by original equipment manufacturers on new 18 diesel exhaust systems and has been used to retrofit on-road and off-road engines in the U.S. 19 Mayer et al testing with fuel borne catalysts indicate that in these situations, the large effective 20 area of the filter, and the engine exhaust gas components in conjunction with the fuel borne 21 catalysts can promote undesirable chemical reactions that release toxic secondary emissions. 22 Dioxins and furans were found not to form in most trap systems but fuel-borne additives 23 containing copper with extremely high fuel chlorine levels (up to 110 ppm), caused emissions to 24 increase by four orders of magnitude. Copper fuel additives are not registered for use in the U.S. in 25 on-road engines. 26 Laroo et al. (2011), Liu et al. (2011) and Hovemann et al. (2010) compared emissions of 27 dioxins and furans using various catalyzed aftertreatment systems, including diesel oxidation 28 catalysts, catalyzed diesel particulate filters, and copper and iron zeolite selective catalytic 29 reduction (SCR) systems that are currently used in on-road diesel trucks in the U.S. These 30 studies report no increase in dioxin or furan emissions when using catalyzed aftertreatment This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-2 DRAFT: DO NOT CITE OR QUOTE 1 systems and fuel chlorine levels that were representative and one order of magnitude higher than 2 what is currently in ultra low sulfur pump diesel fuel. 3 UNEP (2005) presents emission factors for a variety of engine types and fuels. These 4 were originally presented in units of pg I-TEQ/MT and are converted to pg I-TEQ/L below 5 (assumes diesel fuel has a density of 0.85 kg/L and gasoline has a density of 6 0.75 kg/L--Hazardous Substances Database, 7 http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen7HSDB.htm): 8 9 Leaded gasoline, 4-stroke engine-- 1,600 pg I-TEQ/L 10 Leaded gasoline, 2-stroke engine--2,600 pg I-TEQ/L 11 Unleaded gasoline, 4-stroke engine without catalyst--75 pg I-TEQ/L 12 Unleaded gasoline, 4-stroke engine with catalyst--0 13 Unleaded gasoline, 2-stroke engine without catalyst--1,900 pg I-TEQ/L 14 Diesel engines--85 pg I-TEQ/L 15 16 4.1.2. Air Emission Factor 17 In the original document, some of the emission factors were presented on a per-km driven 18 basis and some on a per-liter of fuel basis. The present document changes all vehicle emission 19 factors to a per-liter basis. Separate emission factors were developed for vehicles burning leaded 20 gasoline, unleaded gasoline, and diesel fuel. 21 22 4.1.2.1. L e a d e d G a so lin e 23 The literature indicates that CDD/CDF emissions occur from vehicles using leaded 24 gasoline, and that considerable variation occurs depending, at least in part, on the types of 25 additives used in the fuel or motor oil (Ballschmiter et al., 1986; Marklund et al., 1990). 26 The average emission factor, as reported for the tailpipe emission studies performed 27 using commercial leaded fuel (see Table 4-4 in U.S. EPA, 2006), was 532 pg WHO98 TEQDF/L 28 (450 pg I-TEQdf/L), (Marklund et al., 1990; Hagenmaier et al., 1990; Schwind et al., 1991). 29 This emission factor was applied to 1987 but was not needed for the other years due to the 30 phaseout of leaded gasoline. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-3 DRAFT: DO NOT CITE OR QUOTE 1 For application to off-road engines, this emission factor is considered preliminary 2 because it is based on automobile testing and it is uncertain how well it applies to off-road 3 engines (see discussion below). 4 5 4.I.2.2. U n le a d e d G a so lin e 6 The literature documenting results of European studies indicates that CDD/CDF 7 emissions from vehicles burning unleaded fuels are lower than emissions from vehicles burning 8 leaded gas with chlorinated scavengers. It also appears, based on the limited data available, that 9 catalyst-equipped cars have lower emission factors than do noncatalyst-equipped cars (Marklund 10 et al., 1987; Marklund et al., 1990; Hagenmaier et al., 1990; Schwind et al., 1991). All 11 automobiles running on unleaded gasoline in the United States are equipped with catalysts 12 (commonly known as "catalytic converters"). The average emission factor reported for the 13 tailpipe emission studies performed on catalyst-equipped cars (Hagenmaier et al., 1990; Schwind 14 et al., 1991; Hutzinger et al., 1992) was calculated as 15.6 pg WHO98 TEQDF/L 15 (14.9 pg I-TEQDF/L). This emission factor was assumed to apply to each reference year. 16 For application to off-road engines, this emission factor is considered preliminary 17 because it is based on automobile testing, and it is uncertain how well it applies to off-road 18 engines. Off-road engines can have very different designs. For example, few, if any, off-road 19 gasoline engines have the mechanisms for fuel efficiency and emission control that on-road 20 engines have, such as feedback control systems that monitor and correct the air-to-fuel ratio for 21 combustion; either oxidation or three-way catalysts or exhaust gas recirculation systems (EGR); 22 or overhead valves. Two-stroke engines are much more commonly used in off-road applications 23 than on-road vehicles. The compression ratios for these engines are generally significantly less 24 than those of four-stroke engines (U.S. EPA, 2002c). As a result, emissions of traditional 25 pollutants from two-stroke engines are higher than from four-stroke engines. For example, EPA 26 estimates emissions of PM from two-stroke, off-road motorcycles to be more than 20 times that 27 of four-stroke motorcycles (U.S. EPA, 2002a). Although dioxin emissions do not always 28 correspond to emissions of conventional pollutants, it is possible that two-stroke off-road engines 29 have higher dioxin emissions. This belief is strongly reflected in the UNEP (2005) emission 30 factor recommendations of 1,900 pg I-TEQ/L for unleaded gasoline in two-stroke engines 31 without catalysts versus zero for unleaded gasoline in four-stroke engines with catalyst. The This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-4 DRAFT: DO NOT CITE OR QUOTE 1 UNEP (2005) recommendations for two-stroke engines were not adopted here due to the lack of 2 supporting references. 3 4 4.I.2.3. D ie s e l F u e l 5 Data available upon which to base an evaluation of the extent of CDD/CDF emissions 6 resulting from diesel fuel combustion are discussed in this section. These data address only 7 emissions from on-road vehicles; no emissions data are available for off-road diesel uses 8 (construction vehicles, farm vehicles, and stationary equipment). 9 Laroo et al. (2011) reported emission factors for a 2008 model year diesel engine of 1.89 10 pg I-TEQ/L without aftertreatment under steady-state operation; 1.28 pg I-TEQ/L for an engine 11 with copper zeolite urea SCR, diesel oxidation catalyst, and catalyzed particulate filter 12 aftertreatment under transient operation; and 0.21 pg I-TEQ/L for an engine equipped with a 13 diesel oxidation catalyst and catalyzed particulate filter under transient operation. Liu et al. 14 (2011) reported emission factors for a 2010 model year diesel engine of 0.31 pg WHO 1998 15 TEQ/hp-hr without aftertreatment; 0.12 pg WHO 1998 TEQ/hp-hr for an engine with copper 16 zeolite urea SCR, diesel oxidation catalyst, and catalyzed particulate filter aftertreatment and 17 0.13 pg WHO 1998 TEQ/hp-hr for an engine equipped with a diesel oxidation catalyst and 18 catalyzed particulate filter under steady-state operation. Hovemann et al. (2010) reported 19 emissions factors of 0.11 pg/m for steady-state operation and 0.10 pg/m for transient operation 20 of a diesel engine with aftertreatment including a diesel oxidation catalyst, copper zeolite SCR 21 and urea. The Health Effects Institute (2009) reported a range of emissions from 0.13 - 1.4 pg I- 22 TEQ/L for three diesel engines equipped with catalyzed particulate filters. 23 Although aggregate samples representing several thousand heavy-duty diesel vehicles 24 were collected in Oehme et al. (1991), several characteristics of the study introduce considerable 25 uncertainty with regard to the use of the study's results as a basis for estimating emissions in the 26 United States: (a) heavy-duty vehicles represented only 3 to 19% of total vehicle traffic in the 27 tunnel; (b) the majority of the light-duty vehicles were fueled with leaded gasoline, which can 28 lead to increased releases of CDD/CDFs; and (c) technology differences likely existed between 29 the 1988 Norwegian and the 1987 and 1995 U.S. vehicle fleets. 30 The tunnel study conducted in Baltimore, MD, by Gertler et al. (1996, 1998) shares the 31 disadvantages of all tunnel studies relative to those that directly measured CDDs and CDFs in This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-5 DRAFT: DO NOT CITE OR QUOTE 1 tailpipe emissions. Specifically, tunnel studies rely on indirect measurements (rather than 2 tailpipe measurements), which may introduce bias, and the emission factors calculated from 3 these studies reflect the mix of vehicles using the tunnel--and not necessarily the overall vehicle 4 fleet. Also, they reflect the driving conditions of the tunnel (surface slope, speed, braking, etc.), 5 which may not be representative of usual driving conditions. 6 However, the Gertler et al. (1996, 1998) study does have strengths that are lacking in the 7 Oehme et al. (1991) tunnel study, and it has advantages over the two U.S. diesel truck tailpipe 8 studies, including: (a) the study was conducted during the reference year time frame (1995) in 9 the United States and, thus, reflects U.S. fuels and technology of that time period, (b) virtually no 10 vehicle using the tunnel was fueled with leaded gasoline, (c) the tunnel walls and streets were 11 cleaned one week prior to the start of sampling and, in addition, the study analyzed road dust and 12 determined that resuspended road dust contributed only about 4% of the estimated emission 13 factors, (d) the heavy-duty vehicles comprised, on average, a relatively large proportion (25.7%) 14 of vehicles using the tunnel, and (e) a large number of heavy-duty vehicles--approximately 15 33,000--passed through the tunnel during the sampling period, which generates confidence that 16 the emission factor is representative of interstate trucks. It should be noted, though, that the 17 study was most representative of heavy duty trucks because these were the primary type of 18 vehicle using the tunnel. For other diesel vehicles (e.g., light duty trucks, automobiles, buses), 19 the study is less representative, and uncertainty is greater. 20 Considering the strengths and weaknesses of the available emission factor data from the 21 tailpipe and tunnel studies, the mean TEQ emission factor reported by Gertler et al. (1996, 22 1998)-- 182 pg WHO98 TEQDF/km (172 pg I-TEQDF/km)--is assumed to represent the best 23 current estimate of the average emission factor for on-road diesel-fueled vehicles. This emission 24 factor was converted to a per-liter basis assuming a fuel efficiency of 2.98 km/L (U.S. EPA, 25 2003a). This yields an emission factor of 540 pg WHO98 TEQDF/L (510 pg I-TEQDF/L), which 26 was assumed to apply to all reference years for both on-road and off-road vehicles. It is likely 27 that the fleet average emission factor has decreased over the reference years (due to 28 improvements in engine/emission designs), but insufficient information was available to account 29 for this. For application to off-road vehicles, the factor is considered preliminary because it is 30 based on truck testing, and it is uncertain how well it applies to other types of diesel vehicles This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-6 DRAFT: DO NOT CITE OR QUOTE 1 such as heavy duty vehicles used in construction, tractors, off-road military vehicles, ships, and 2 locomotives. 3 4 4.1.3. Air Activity Level 5 The activity estimates for internal combustion engines were derived on the basis of fuel 6 consumed as reported by the Energy Information Administration (EIA, 2008a). 7 8 4.1.3.1. G a so lin e 9 EIA (2008a) provides data on the total "motor gasoline product supplied," which 10 represents all gasoline consumed in the United States. These data were reported as barrels per 11 year and are converted here to liters by multiplying by 42 gal/barrel and 3.78 L/gal. For 1987, it 12 is assumed that 24% of the gasoline was leaded (1.00 x 1011L) and the remainder unleaded 13 (3.18 x 1011L) (EIA, 1993). For years 1995 and 2000, it is assumed that leaded gasoline was 14 produced in negligible amounts. The total amount of unleaded gasoline consumed in 1995 was 15 4.00 x 1011L, and the total amount consumed in 2000 was 4.93 x 1011L. EIA does not provide 16 data that allow the gasoline uses to be divided between on road and off road. However, 17 U.S. EPA (2006) provided estimates for the year 2000 suggesting that 5% of the gasoline was 18 used for off-road engines (kilometers driven on road were converted to liters, assuming an 19 average fuel efficiency of 10 km/L). This percentage was assumed to apply to all reference 20 years, resulting in the following estimates: 21 1987 1995 2000 Leaded (L) Total On-road 1.00 x 1011 9.5 x 1010 00 00 Off-road 0.5 x 1010 0 0 Unleaded (L) Total On-road 3.18 x 1011 3.03 x 1011 4.00 x 1011 3.80 x 1011 4.93 x 1011 4.68 x 1011 Off-road 0.15 x 1011 0.20 x 1011 0.25 x 1011 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-7 DRAFT: DO NOT CITE OR QUOTE 1 4.I.3.2. D ie s e l 2 EIA provides data on "distillate fuel oil product supplied," which represents all distillate 3 fuel consumed in the United States. Distillate fuel includes diesel and other fuels used primarily 4 for space heating. The diesel portion of the distillate fuel was determined using EIA data on 5 "sales of distillate fuel oil by end use." For 2001, these data suggest the following: 6 7 Diesel fuel used on road is 55% of the total. 8 Diesel fuel used off road (includes off-highway, farm, railroad, vessels, and military 9 categories) is 20% of the total. 10 Other uses of distillate fuels (includes residential, commercial, industrial, and electric 11 power categories) make up 25% of the total. 12 13 It is assumed that these percentages for 2001 apply to all reference years. Applying these to the 14 "distillate fuel oil product supplied," yields: 15 16 1987--9.48 x 1010L on road, 3.45 x 1010L off road 17 1995-- 1.02 x 1011L on road, 3.71 x 1010L off road 18 2000-- 1.19 x 1011L on road, 4.32x 1010L off road 19 20 4.1.4. Air Releases 21 Air-release estimates were made by multiplying the emission factors with the activity 22 estimates. Separate release estimates were made for leaded gasoline, unleaded gasoline, diesel 23 off road, and diesel on road. 24 25 4.1.5. Water Releases--None 26 27 4.1.6. Solid Residue Releases 28 Solid residue releases could result from disposal/recycling of mufflers or catalytic 29 converters. No information could be found on the possible CDD/CDF content of these materials. 30 31 4.1.7. Products--None 32 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-8 DRAFT: DO NOT CITE OR QUOTE 1 4.1.8. Release Summary 2 The inventory decision criteria and release estimates to all media are summarized below: 3 Inventory Decision Criteria for Motor Vehicle Combustion--On-road Air W ater Solids Products Emission tests for at least two units/source types with sufficient documentation to directly derive emission factors. Yes Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). Q 4 5 Inventory Decision Criteria for Motor Vehicle Combustion--Off-road Air W ater Solids Products Emission tests for at least two units/source types with No sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Emission factor tests represent units that are typical of the No class. Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). P 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-9 DRAFT: DO NOT CITE OR QUOTE Emission Factors Motor Vehicle Combustion Air Releases L eaded G asoline 1987--530 pg WHO98 TEQDf/L (450 pg I-TEQDf/L) (Preliminary for off-road). U nleaded G asoline 1987-- 16 pg WHO98 TEQdf/L (15 1995-- 16 pg WHO98 TEQdF/L (15 2000-- 16 pg WHO98 TEQdF/L (15 pg I-TEQdf/L)(Preliminary for off-road). pg I-TEQdF/L)(Preliminary for off-road). pg I-TEQdF/L)(Preliminary for off-road). D iesel 1987--540 pg WHO98 TEQdF/L (510 pg I-TEQdF/L) (Preliminary for off-road). 1995--540 pg WHO98 TEQdF/L (510 pg I-TEQdF/L) (Preliminary for off-road). 2000--540 pg WHO98 TEQdF/L (510 pg I-TEQdF/L) (Preliminary for off-road). Activity Levels L eaded G asoline, O n-road 1987--9.5 x 1010L/yr. L eaded G asoline, O ff-road 1987--0.5 x 1010L/yr. U nleaded G asoline, O n-road 1987--3.03 x 1011L/yr. 1995--3.80 x 1011L/yr. 2000--4.68 x 1011L/yr. U nleaded G asoline, O ff-road 1987--3.18 x 1011L/yr. 1995--4.00 x 1011L/yr. 2000--4.93 x 1011L/yr. D iesel, O n-road 1987--0.15 x 1010L/yr. 1995--0.20 x 1011L/yr. 2000--0.25 x 1011L/yr. D iesel, O ff-road 1987--3.45 x 1010L/yr. 1995--3.71 x 1010L/yr. 2000--4.32 x 1010L/yr._____________________________________________ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-10 DRAFT: DO NOT CITE OR QUOTE Releases Motor Vehicle Combustion (continued)______________________ L eaded G asoline, O n--road 1987--50 g WHO98 TEQdf (43 g I-TEQdf) L eaded G asoline, O ff--road 1987--3 g WHO98 TEQdf (2 g I-TEQdf) (Preliminary). U nleaded G asoline, O n-road 1987--5 g WHO98 TEQdf (5 g I-TEQdf). 1995--6 g WHO98 TEQdf (6 g I-TEQdf). 2000--7 g WHO98 TEQdf ( 7 g I-TEQdf). U nleaded G asoline, O ff-road 1987--0.2 g WHO98 TEQdf (0.2 g I-TEQdf) (Preliminary). 1995--0.3 g WHO98 TEQdf (0.3 g I-TEQdf) (Preliminary). 2000--0.4 g WHO98 TEQdf (0.4 g I-TEQdf) (Preliminary). D iesel, O n-road 1987--51 g WHO98 TEQdf (48 g I-TEQdf). 1995--55 g WHO98 TEQdf (52 g I-TEQdf). 2000--64 g WHO98 TEQdf (61 g I-TEQdf). D iesel, O ff-road 1987-- 19 g WHO98 TEQdf (18 g I-TEQdf) (Preliminary). 1995--20 g WHO98 TEQdf (19 g I-TEQdf) (Preliminary). 2000--23 g WHO98 TEQdf ( 2 2 g I-TEQdf) (Preliminary).______________________ W ater Releases________________________________ No information was found suggesting that water releases from internal combustion engines would contain CDDs and CDFs.____________________________________________________ Solid Residue Releases_____________________________ No information was found suggesting that solid residue releases from internal combustion engines would contain CDDs and CDFs._____________________________________________ Products___________________________________ None._________________________________________________________________________ 1 2 3 4.2. WOOD COMBUSTION 4 4.2.1. Residential Wood Combustion 5 Several new literature studies were added, but no changes were made to the estimates of air 6 releases from traditional residential wood-burning fireplaces and stoves. New sections were 7 developed on the air releases from outdoor wood-fired boilers and on solid residues from all 8 forms of residential wood burning. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-11 DRAFT: DO NOT CITE OR QUOTE 1 This section focuses on residential burning of natural untreated wood. It should be noted 2 though, that treated wood may be burned at some residences with the potential for increased 3 CDD/CDF emissions. Wevers et al. (2003) measured CDD/CDF emissions from domestic 4 wood-burning appliances and reported emission factors of 22.4 ng I-TEQ/kg for burning 5 untreated wood and 1,702 ng I-TEQ/kg for burning treated wood. Tame et al. (2003) measured 6 CDD/CDF levels in ash from wood combustion in a cone calorimeter. Ash from burning 7 untreated pine had an average of 0.050 ng I-TEQ/kg ash. For the CCA (chromated copper 8 arsenate) treated pine, burnt under identical conditions, a significant increase was observed, with 9 an average of 35 ng I-TEQ/kg. Tame et al. (2007) reviewed the literature on the role of 10 preservatives in the formation of dioxin in the combustion of wood. They conclude that current 11 and emerging wood preservatives significantly increase dioxin formation during combustion in 12 domestic stoves and in fires. Not all investigators, however, have observed these increases. 13 Wasson et al. (2005) conducted chamber tests to measure CDD/CDF emissions from burning 14 CCA treated wood. Emission factors ranged from 1.4 to 2.3 ng WHO98 TEQ/kg, which are 15 similar to those for untreated wood. 16 17 4.2.1.1. A ir R e le a s e s f r o m I n d o o r R e s id e n tia l W o o d B u r n e rs 18 A study conducted in Australia by Gras et al. (2002) measured dioxin emissions from a 19 variety of wood-burning appliances and wood types. The average values for various wood types 20 were 7.5 ng WHO98 TEQ/kg for eucalyptus, 19 ng WHO98 TEQ/kg for manufactured wood, and 21 <1 ng WHO98 TEQ/kg for softwoods. 22 Gullett et al. (2003) measured dioxin emissions from residential fireplace and woodstove 23 appliances burning fuels available from the San Francisco Bay area. Common California natural 24 firewoods and manufactured artificial logs were tested under operating conditions intended to 25 reflect domestic use patterns in the Bay area, which are primarily episodic burning for aesthetic 26 reasons. Average CDD/CDF emissions factors ranged from 0.25 to 1.4 ng WHO98 TEQ/kg of 27 wood burned for natural wood fuels and 2.4 ng WHO98 TEQ/kg for artificial logs. 28 Pfeiffer et al. (2000) measured CDD/CDF emissions from wood fired household 29 appliances used in Germany. Emission factors ranged from 0.141 to 0.785 ng I-TEQ/kg. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-12 DRAFT: DO NOT CITE OR QUOTE 1 Wevers et al. (2003) measured CDD/CDF emissions from domestic wood burning 2 appliances used in Belgium. The average emission factor was 22.4 ng I-TEQ/kg for burning 3 untreated wood. 4 UNEP (2005) recommended an emission factor of 100 pg I-TEQ/TJ (TJ = terajoule or 5 1012joule) for virgin biomass-fired stoves. Assuming that wood combustion produces 6 12-15 MJ/kg where MJ = megajoule or 106joule (UNEP, 2005), this converts to 1.2 to 7 1.5 ng I-TEQ/kg of wood burned. 8 The emission factor selected for indoor residential wood burning was based on 9 Environment Canada (2000) because these tests took place in North America using indigenous 10 wood, and they included the analysis of an EPA-certified wood stove. The mean value of the 11 Environment Canada study (0.5 ng I-TEQ/kg wood or ng WHO98 TEQ/kg wood) was applied to 12 all reference years. 13 Activity estimates were derived from EIA (2008b), which reports energy production from 14 residential wood burning in BTUs. These were converted to mass of wood burned by dividing 15 these values by 14,080 BTU/kg (average heat value of seasoned wood at 20% moisture--ORNL, 16 2008). This yields estimates of 71 MMT in 1987, 37 MMT in 1995 and 30 MMT in 2000. 17 18 4.2.I.2. A ir R e le a s e s f r o m R e s id e n tia l O u td o o r W o o d -F ire d B o ile r s 19 Outdoor wood-fired boilers (OWBs) are wood-fired furnaces used for heating, typically 20 in residential settings. They are located some distance from the house, usually in an insulated 21 shed. Each OWB houses an oversized firebox surrounded by a water jacket. Water is circulated 22 through the jacket and piped underground to deliver hot water for space heating and domestic 23 use. OWBs are designed to burn large amounts of wood over extended periods of time; 24 fireboxes range in size from 20 ft to 150 ft and can heat buildings up to 20,000 ft . They can 25 produce from 115,000 BTU/hour up to 3.2 million BTU/hour, although most residential 26 installations are less than 1 million BTU/hour (NESCAUM, 2006). 27 Because OWBs operate in a cyclic fashion, they can produce large amounts of smoke. 28 When an OWB is in the "off' cycle and does not need to generate heat, the air damper closes to 29 cut off the air supply. This creates an oxygen-starved environment in which the fire smolders, 30 creating smoke and creosote that condenses on the internal steel surfaces. When heat needs to be 31 produced, the air damper opens and natural draft forces air into the firebox, pushing the smoke This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-13 DRAFT: DO NOT CITE OR QUOTE 1 and air pollutants out the stack. Measured emissions peak when the unit has received a fresh 2 load of fuel and the wood has not yet reached a charcoal stage. In the field test conducted by 3 NESCAUM, the unit's internal stack temperature never reached levels that would have resulted 4 in complete combustion. In comparing emissions of particulate matter (PM) from various 5 sources, it was noted that one OWB can emit as much PM as four heavy duty diesel trucks. 6 Generally, OWBs do not use catalytic or noncatalytic emission control devices commonly 7 employed by other residential combustion devices (NESCAUM, 2006). 8 OWBs have not been tested for CDD/CDF emissions. Their cyclic air flow and low 9 operating temperatures (see discussion above), suggests that their emissions may be best 10 represented by a value near the upper end of measurements for natural wood burned in wood 11 stoves. Accordingly, an emission factor of 20 ng WHO98 TEQDF/kg wood (based on Wevers 12 et al., 2003) is used to represent OWBs. This emission factor is assigned a preliminary 13 confidence rating because it is not based on testing of actual OWBs. 14 EPA estimates that there were more than 100,000 OWBs in use in the United States in 15 2007; NESCAUM estimates that more than 155,000 units have been sold since 1990 (U.S. EPA, 16 2007a). An average household in the Northeast (where many of these units are used) consumes 17 63.1 million BTU per year for space heating (EIA, 2001). Multiplying this value by the 18 100,000 OWBs in use suggests they produced a total of 6.3 trillion BTU in 2007. Dividing this 19 value by 14,080 BTU per kilogram (the average heat value of seasoned wood at 20% moisture 20 [ORNL, 2008]) yields a total wood consumption of 448,000 MTs in 2007, and this is assumed to 21 apply to 2000. Because it is not known how many units were in operation in 1987 and 1995, the 22 activity level could not be estimated for these years. 23 This procedure assumes that all OWBs supply 100% of a home's space heating needs, 24 which may lead to an overestimate of wood consumed. The assumption that the 2007 activity 25 value applies to 2000 also leads to an overestimate. However, the assumption that only seasoned 26 wood is burned, when in fact unseasoned wood may also be used, would underestimate the 27 amount of wood consumed. It is unclear to what extent these uncertainties offset each other. 28 29 4.2.I.3. W a ter R e le a s e s --N o n e 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-14 DRAFT: DO NOT CITE OR QUOTE 1 4.2.1.4. S o lid R e s id u e s f r o m A l l R e s id e n tia l W o o d B u r n in g 2 EPA (2006) summarizes studies measuring CDDs/CDFs in chimney soot from wood 3 burning stoves and fireplaces by several researchers (Bumb et al., 1980; Nestrick and Lamparski, 4 1982, 1983; Clement et al., 1985; Bacher et al., 1992; Van Oostam and Ward, 1995; Dumler5 Gradl et al., 1995). The CDD/CDF levels ranged from 80 to 350 ng WHO98 TEQ/kg. 6 Wunderli et al. (1996) measured CDD/CDF levels in ash of wood-burning facilities in 7 Switzerland. The facilities were characterized as small-to-medium sized, but they were not 8 described in detail. Some of them had air pollution controls and may have been more 9 sophisticated than most residential wood stoves. The mean level for natural wood burning was 10 2.5 ng I-TEQ/kg of fly ash (n = 6) and 5.3 ng I-TEQ/kg of bottom ash (n = 8). UNEP (2005) 11 used this reference to support their recommendation of 10 ng I-TEQ/kg of ash residue from 12 biomass-fired stoves. 13 14 4.2.1.5. S o lid R e s id u e E m issio n F a c to r 15 The CDD/CDF levels in soot are likely to be higher than bottom ash from wood burning, 16 so the soot based studies noted above were not used to select an emission factor. Instead, the 17 UNEP (2005) recommendation of 10 ng I-TEQ/kg of ash residue (based on Wunderli et al., 18 [1996] data for wood-burning bottom ash) was selected as the best for residential wood burning. 19 The congener profile for bottom ash from natural wood burning reported by Wunderli et al. 20 (1996) indicated that the WHO98 TEQs were only about 4% greater than the I-TEQs. On this 21 basis, the UNEP recommendation can also be expressed as 10 ng WHO98 TEQ/kg of ash residue. 22 23 4.2.1.6. S o lid R e s id u e A c tiv ity L e v e l 24 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to 25 8% ash (Ragland et. al, 1991). A mid-range value of 3% is assumed here for all wood burned. 26 Multiplying this percentage by the amount of wood consumed (as reported above) yields the ash 27 production amounts for each reference year: 2.13 MMT in 1987, 1.11 MMT in 1995, and 28 0.9 MMT in 2000. 29 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-15 DRAFT: DO NOT CITE OR QUOTE 1 4.2.1.7. S o lid R e s id u e R e le a se s 2 Solid residue releases were estimated by multiplying the ash emission factor by the ash 3 activity level. These release estimates include both indoor and outdoor sources of residential 4 wood combustion. Some ash from residential wood combustion is disposed with household 5 garbage that is sent to municipal landfills. This portion of the ash would not be considered a 6 release to the open environment. The remainder is land disposed in a manner that is assumed to 7 be releasable to the environment. One study reported that approximately 80% of all ash is land 8 applied in the Northeast United States, less than 10% is land applied in the Southeast (University 9 of Georgia, 2002). Because the portion going to a landfill is probably small, it is assumed here 10 that all of the ash releases can be considered an environmental release. 11 12 4.2.1.8. R e le a s e S u m m a ry 13 The inventory decision criteria and release estimates to all media are summarized below: 14 Inventory Decision Criteria for Indoor Residential Wood Burners Air Water Solids Products Emission tests for at least two units/source types with Yes Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Yes Emission factor tests represent units that are typical of the class. Yes Yes Activity estimates based on source-specific surveys. Yes Yes Conclusion (Q = Quantitative, P = Preliminary). QQ 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-16 DRAFT: DO NOT CITE OR QUOTE Emission Factor Residential Wood Combustion Air Releases__________ Indoor R esidential W ood Burners 1987--0.5 ng WHO98 TEQDF/kg (I-TEQDF/kg) of wood. 1995--0.5 ng WHO98 TEQDF/kg (I-TEQDF/kg) of wood. 2000--0.5 ng WHO98 TEQDF/kg (I-TEQDF/kg) of wood. O utdoor W ood-F ired Boilers 1987--20 ng WHO98 TEQDF/kg of wood (Preliminary). 1995--20 ng WHO98 TEQDF/kg of wood (Preliminary). 2000--20 ng WHO98 TEQDF/kg of wood (Preliminary). Activity Level Indoor R esidential W ood Burners 1987--71 MMT. 1995--37 MMT. 2000--30 MMT. O utdoor W ood-F ired Boilers 1987--Not Available. 1995--Not Available. 2000--0.448 MMT (Preliminary)._________________ Releases Indoor R esidential W ood Burners 1987--36 g (WHO98 TEQdf or I-TEQdf). 1995-- 19 g (WHO98 TEQdf or I-TEQdf). 2000-- 15 g (WHO98 TEQdf or I-TEQdf). O utdoor W ood-F ired Boilers 1987--Not Available 1995--Not Available 2000--9 g WHO98 TEQdf (Preliminary).____________ W ater Releases________ None._________________________________________________ 1 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-17 DRAFT: DO NOT CITE OR QUOTE Residential Wood Combustion (continued) Solid Residue Releases________ Emission Factors 1987-- 10 ng WHO98 TEQDF/kg (I-TEQDF/kg) of ash. 1995-- 10 ng WHO98 TEQDF/kg (i-TEQDF/kg) of ash. 2000-- 10 ng WHO98 TEQDF/kg (I-TEQDF/kg) of ash. Activity Levels 1987--2.13 MMT of ash. 1995-- 1.11 MMT of ash. 2000--0.9 MMT of ash._____________________________ Releases 1987--21 g (WHO98 TEQdf or I-TEQdf). 1995-- 11 g (WHO98 TEQdf or I-TEQdf). 2000--9 g (WHO98 TEQdf or I-TEQdf).________________ Products______________ None. 1 2 3 4.2.2. Industrial Wood Combustion 4 4.2.2.1. A ir R e le a se s 5 No changes were made to the emission factor estimates for industrial burning of salt and 6 nonsalt laden wood. However, an additional study is discussed below which shows that 7 combustion temperature and wood condition can have a large impact on emission factors. 8 Yasuhara et al. (2003) measured CDD/CDF emissions from a wood burning incinerator 9 in Japan. With combustion temperature of about 600EC, the following emission factors 10 (ng WHO98 TEQ/kg) were measured: pine-- 167, cedar-- 164, seawater impregnated pine--392, 11 seawater impregnated cedar bark--559 and seawater impregnated cedar without bark--828. 12 Much lower emission factors were measured when the combustion temperature was increased to 13 800EC: pine--2.3, beech--3.5, chlordane impregnated waste wood--40 and pentachlorophenol 14 impregnated waste wood--44. 15 For nonsalt laden wood, the mean of the emission factors derived from the four CARB 16 studies and five NCASI studies (assuming nondetect values were zero) is 17 0.6 ng WHO98 TEQDF/kg wood (0.56 ng I-TEQDF/kg wood) and is used in this document as the 18 most representative of industrial wood combustion for all reference years. 19 NCASI (1995) concluded that CDD/CDF emissions from facilities burning salt-laden 20 wood residue may be considerably higher than those from facilities burning salt-free wood. The This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-18 DRAFT: DO NOT CITE OR QUOTE 1 overall average of the five tested facilities in Canada (Luthe et al., 1998) and the United States 2 (U.S. EPA, 1987), 13.2 ng I-TEQDF/kg of wood, was applied to all three reference years. Based 3 on the congener profile reported by Luthe et al. (1998), this converts to 15.3 ng WHO98 TEQ/kg. 4 Similarly, no change was made to the activity estimate for salt laden wood. However, the 5 activity estimate for nonsalt laden wood was changed for all years to reflect more recent data in 6 EIA (2008c). Values are reported in the release summary below. 7 8 4.2.2.2. W a ter L ite r a tu r e --N o n e 9 10 4.2.2.3. S o lid R e s id u e R e le a se s 11 As indicated in U.S. EPA (2006), the ash concentrations from the NCASI Handbook 12 (13.2 ng WHO98 TEQDF/kg) appears to fall within the range of values reported in the various 13 studies and a reasonable value for mixed bottom and fly ash. Oeheme and Muller (1995) 14 measured CDD/CDF levels in ash from wood-fired boilers in Switzerland. The levels in bottom 15 ash were on the order of 1 ng I-TEQ/kg when natural wood was incinerated. However, in filter 16 ash the levels were about two orders of magnitude higher. Burning of waste wood from house 17 demolition and construction resulted in concentrations in the range of 1-10 ng I-TEQ/kg. 18 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to 19 8% ash (Ragland et al, 1991). A mid-range value of 3% is assumed here for all wood burned. 20 Multiplying this percentage by the amount of wood consumed (as reported in the release 21 summary below) yields the ash production amounts for each reference year: 3.48 MMT in 1987, 22 3.51 MMT in 1995, and 3.48 MMT in 2000. 23 All ash from industrial wood combustion is assumed to be disposed in a secure landfill 24 and is, therefore, not considered an environmental release. However, the amounts of dioxin in 25 landfilled ash from industrial wood burning can be estimated by multiplying the ash 26 concentration and ash amounts presented above. This yields the following estimates: 27 28 1987--46 g WHO98 TEQDF/kg 29 1995--46 g WHO98 TEQDF/kg 30 2000--46 g WHO98 TEQDF/kg 31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-19 DRAFT: DO NOT CITE OR QUOTE 1 4.2.2.4. R e le a s e S u m m a ry 2 The inventory decision criteria and release estimates to all media are summarized below: 3 4 Inventory Decision Criteria for Industrial Wood Combustion Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 5 6 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-20 DRAFT: DO NOT CITE OR QUOTE Emission Factor Industrial Wood Combustion_____________________ Air Releases____________________________ N onsalt-Laden W ood 1987--0.6 ng WHO98 TEQDF/kg (0.56 ng I-TEQDF/kg) of wood. 1995--0.6 ng WHO98 TEQDF/kg (0.56 ng I-TEQDF/kg) of wood. 2000--0.6 ng WHO98 TEQDF/kg (0.56 ng I-TEQDF/kg) of wood. Salt-Laden W ood 1987-- 15 ng WHO98 TEQ/kg (13 ng I-TEQDF/kg) of wood. 1995-- 15 ng WHO98 TEQ/kg (13 ng I-TEQDF/kg) of wood. 2000-- 15 ng WHO98 TEQ/kg (13 ng I-TEQDF/kg) of wood._______________ Activity Level N onsalt-Laden W ood 1987-- 116 MMT. 1995-- 117 MMT. 2000-- 116 MMT. Salt-Laden W ood 1987--0.5 MMT. 1995--0.5 MMT. 2000--0.8 MMT._________________________________________________ Releases N onsalt-Laden W ood 1987--70 g WHO98 TEQdf (65 g I-TEQdf). 1995--70 g WHO98TEQdf (65 g I-TEQdf). 2000--70 g WHO98 TEQdf (65 g I-TEQdf). Salt-Laden W ood 1987--8 g WHO98 TEQdf (7 g I-TEQdf). 1995--8 g WHO98TEQdf (7 g I-TEQdf). 2000-- 12 g WHO98TEQdf (10 g I-TEQdf). Total Industrial Releases 1987--78 g WHO98TEQdf (72 g I-TEQdf). 1995--78 g WHO98TEQdf (72 g I-TEQdf). 2000--82 g WHO98TEQdf 75 g I-TEQdf).____________________________ W ater Releases___________________________ None.____________________________________________________________________ Solid Residue Releases________________________ All ash is assumed to be landfilled and, therefore, is not considered to be an environmental release.__________________________________________________________________ 1 2 3 4 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-21 DRAFT: DO NOT CITE OR QUOTE Industrial Wood Combustion (continued) Products______________ None. 1 2 3 4.3. OIL COMBUSTION 4 Section 4.1 covered combustion of gasoline and diesel fuels in engines. This section 5 addresses the combustion of other types of distillate oil products and residual fuel oils. These 6 products are burned primarily in furnaces or boilers in both residential/institutional settings and 7 in large industrial facilities. Distillate fuel oils are distilled from crude oil. Residual oils are 8 what remain of the crude oil after gasoline, and the distillate fuel oils are extracted through 9 distillation. Residual and distillate oils are further distinguished by grade: Numbers 1 and 2 are 10 distillate oils. No. 1 is similar to kerosene and is the fraction that boils off right after gasoline. 11 No. 2 is the diesel that trucks and some cars run on, leading to the name "road diesel"; this 12 category is addressed in Section 4.1. 13 Fuel Grades 5 and 6 are residual oils and sometimes referred to as "heavy fuel oils." 14 Number 6 fuel oil is sometimes referred to as Bunker C. Fuel Grade 4 is either distillate oil or a 15 mixture of distillate and residual oils. Distillate oils are more volatile and less viscous than 16 residual oils, which have negligible nitrogen and ash content, and usually contain less than 17 0.3% sulfur (by weight). Distillate oils are used mainly in domestic and small commercial 18 applications. The heavier residual oils (Grades 5 and 6), being more viscous and less volatile 19 than distillate oils, must be heated for ease of handling and to facilitate proper atomization. 20 Because residual oils are produced from the residue after the lighter fractions are removed from 21 the crude oil, they may contain significant quantities of ash, nitrogen, and sulfur. 22 23 4.3.1. Institutional/Commercial and Residential Oil Combustion 24 4.3.1.1. A ir R e le a se s 25 No changes were made to the emission factors. No testing for CDD/CDF emissions from 26 commercial or residential oil-fired combustion units in the United States could be located. 27 However, EPA (1997a) estimated CDD/CDF congener group and TEQ emission factors using 28 average CDD/CDF concentrations reported for soot samples from 21 distillate fuel oil-fired 29 furnaces used for central heating in Canada and a PM emission factor for distillate fuel oil 30 combustors (300 mg/L oil) obtained from AP-42 (U.S. EPA, 1995a). The TEQ emission factor This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-22 DRAFT: DO NOT CITE OR QUOTE 1 estimate--0.19 ng WHO98 TEQdf/L of oil (0.15 ng I-TEQdf/L of oil)--was derived using the 2 calculated emission factors for 2,3,7,8-TCDD, 2,3,7,8-TCDF, and the 10 congener groups. 3 These results are near the upper end of the range from Pfeiffer et al. (2000) who measured 4 CDD/CDF emissions from oil fired household appliances used in Germany. Emission factors 5 were in the range of 0.025 to 0.135 ng I-TEQ/kg. 6 Minor updates were made to the activity estimates. EIA (2008a) data were used to derive 7 the activity levels. EIA supplied yearly data on total distillate fuel oil and total residual fuel oil 8 supplied in the United States. EIA also provided a breakdown of fuel oil sales by sector for the 9 years back to 2001. The sector percentages for 2001 were assumed to apply to each of the 10 reference years. These percentages were multiplied by the totals (also used conversion factors of 11 42 gal/barrel and 3.79 L/gal) to estimate the amount of distillate fuel oil consumed in the 12 residential and commercial sectors. On this basis, the following estimates were made for each 13 reference year: 1987--29.4 billion L, 1995--31.7 billion L, and 2000--36.9 billion L. 14 15 4.3.1.2. W a ter R e le a s e s --N o n e 16 17 4.3.1.3. S o lid R e s id u e R e le a se s --N o n e 18 19 4.3.1.4. P r o d u c ts --N o n e 20 21 4.3.1.5. R e le a s e S u m m a ry 22 The inventory decision criteria and release estimates are summarized below: 23 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-23 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Institutional/Commercial and Residential Oil Combustion Air W ater Solids Products Emission tests for at least two units/source types with sufficient Yes documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). 1 q 2 _______________________________________________________________ Institutional/Commercial and Residential Oil Combustion Air Releases Emission Factors 1987-- 190 pg WHO98 TEQdf/L (150 pg I-TEQdf/L) of oil combusted. 1995-- 190 pg WHO98 TEQdf/L (150 pg I-TEQdf/l ) of oil combusted. 2000-- 190 pg WHO98 TEQdf/L (150 pg I-TEQdf/l ) of oil combusted. Activity Levels 1987--29.4 billion L. 1995--31.7 billion L. 2000--36.9 billion L. Releases 1987--6 g WHO98 TEQdf (4 g I-TEQdf). 1995--6 g WHO98 TEQdf (5 g I-TEQdf). 2000--7 g WHO98 TEQdf (6 g I-TEQdf). W ater Releases_________________ These facilities do not have wastewater releases.________________________ Solid Residue Releases______________ These facilities do not have solid releases._____________________________ Products____________________ None.__________________________________________________________ 3 4 5 4.3.2. Utility Sector and Industrial Oil Combustion 6 Minor changes were made to the activity estimates as explained below. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-24 DRAFT: DO NOT CITE OR QUOTE 1 4.3.2.1. A ir L ite r a tu r e 2 In 1993, the Electric Power Research Institute (EPRI) sponsored a project to gather 3 information of consistent quality on power plant emissions. The Field Chemical Emissions 4 Measurement (FCEM) project included testing of two cold-sided, ESP-equipped, oil-fired power 5 plants for CDD/CDF emissions. EPA (1997a) reports on testing at oil fired utility boilers for a 6 variety of furnace configurations and APCDs. 7 Some boilers use low-NOx burners, which reduce flame turbulence, delay fuel/air 8 mixing, and establish fuel-rich zones within the boiler during initial combustion. The longer, 9 less intense flames that result from the altered combustion lower flame temperatures and reduce 10 thermal NOx formation (Colburn, 1996), Because low-NOx burners reduce temperatures and, 11 thus, the completeness of combustion the potential exists for increased CDD/CDF formation. 12 However, this has not yet been evaluated via stack testing. 13 14 4.3.2.2. A ir E m issio n F a c to r 15 EPA (2006) based the emission factor on the average of the EPRI (1994) and EPA 16 (1997a) studies. The emission factor--230 pg WHO98 TEQDF/L oil combusted 17 (200 pg I-TEQdf/L oil combusted)--was applied to all three reference years. 18 19 4.3.2.3. A c tiv ity L e v e l 20 Updated EIA data were used to derive the activity levels. EIA supplied yearly data on 21 total distillate fuel oil and total residual fuel oil supplied in the United States. EIA also provided 22 a breakdown of fuel oil sales by sector for the years back to 2001. The sector percentages for 23 2001 were assumed to apply to each of the reference years. Multiplying these percentages by the 24 totals yields the following estimates for each reference year (also used conversion factors of 25 42 gal/barrel and 3.79 L/gal): 26 27 Distillate Fuel Oil--Industrial and Electric Power Use 28 29 1987-- 10.4 billion L 30 1995--11.2 billion L 31 2000-- 13.0 billion L This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-25 DRAFT: DO NOT CITE OR QUOTE 1 Residual Fuel Oil--Total 2 3 1987--73.4 billion L 4 1995--49.5 billion L 5 2000--53.0 billion L 6 7 4.3.2.4. A ir R e le a se s 8 The air releases were estimated by multiplying the emission factor and activity estimates. 9 10 4.3.2.5. W a ter R e le a s e s --N o n e 11 12 4.3.2.6. S o lid R e s id u e R e le a se s --N o n e 13 14 4.3.2.7. P r o d u c ts --N o n e 15 16 4.3.2.8. R e le a s e S u m m a ry 17 The inventory decision criteria and release estimates are summarized below: 18 Inventory Decision Criteria for Utility Sector and Industrial Oil Combustion Air Water Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 19 20 21 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-26 DRAFT: DO NOT CITE OR QUOTE Utility Sector and Industrial Oil Combustion_____ Air Releases__________________ Emission Factors 1987--230 pg WHO98 TEQdf/L (200 pg I-TEQdf/L) of oil combusted. 1995--230 pg WHO98 TEQdf/L (200 pg I-TEQdf/l ) of oil combusted. 2000--230 pg WHO98 TEQdf/L (200 pg I-TEQdf/L) of oil combusted. Activity Level 1987--83.8 billion L. 1995--60.7 billion L. 2000--66.0 billion L. Releases 1987-- 19 g WHO98 TEQdf (17 g I-TEQdf). 1995-- 14 g WHO98 TEQdf ( 1 2 g I-TEQdf). 2000-- 15 g WHO98 TEQdf (13 g I-TEQdf). W ater Releases These facilities do not have wastewater releases.__________ Solid Residue Releases These facilities do not have solid releases._______________ Products______ These facilities do not have products.___________________ 1 2 3 4.3.3. Waste Oil Combustion 4 Waste oil includes used crankcase oils from automobiles and trucks, used industrial 5 lubricating oils (such as metal working oils), and other used industrial oils (such as heat transfer 6 fluids). When discarded, these oils become waste oils due to a breakdown of physical properties 7 and contamination by the materials they come in contact with. The different types of waste oils 8 may be burned as mixtures or as single fuels where supplies allow. Waste, or used, oil can be 9 burned in a variety of combustion systems including industrial boilers; commercial/institutional 10 boilers; space heaters; asphalt plants; cement and lime kilns; other types of dryers and calciners; 11 and steel-production blast furnaces (U.S. EPA, 1998c). USDOE (2006) reports the following 12 breakout for 2006 in billions of gallons: 13 14 Asphalt Plants - 0.286 15 Space Heaters - 0.113 16 Industrial Boilers - 0.093 17 Utility Boilers - 0.080 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-27 DRAFT: DO NOT CITE OR QUOTE 1 Steel Mills - 0.080 2 Cement Kilns - 0.033 3 Others - 0.095 (includes: marine boilers, pulp & paper mills, commercial boilers) 4 5 Total - 0.780 6 7 CDD/F emissions from all of these facility types except space heaters were covered in other parts 8 of this document. So this section will address only releases from space heaters. 9 10 4.3.3.I. A ir L ite ra tu re 11 12 Bremmer et al. (1994) measured the CDD/CDF emissions from the combustion of used 13 oil by small combustion units in the Netherlands. Flue gases from a garage stove consisting of 14 an atomizer fueled by spent lubricating oil from diesel engines (35 mg Cl!/kg) were reported to 15 contain 0.1 ng I-TEQDF/Nm (2 ng I-TEQDF/kg) oil burned. The flue gases from a hot water 16 boiler consisting of a rotary cup burner fueled with the organic phase of rinse water from oil 17 tanks (340 mg Cl!/kg) contained 0.2 ng I-TEQDF/Nm3(4.8 ng I-TEQDF/kg) oil burned. The flue 18 gases from a steam boiler consisting of a rotary cup burner fueled by processed spent oil (240 mg 19 Cl/kg) contained 0.3 ng I-TEQDF/Nm (6 ng I-TEQDF/kg) oil burned. The emission factor for a 20 ferry burning heavy fuel oil containing 11 ng/kg organic chlorine was 3.2 to 6.5 ng I-TEQDF/kg 21 oil burned. From these data, Bremmer et al. (1994) derived an average emission factor for 22 combustion of used oil of 4 ng I-TEQDF/kg oil burned. 23 Measured data from the burning of recycled waste oils are available from Austria, where 24 emissions from a small incinerator gave a concentration of 0.02 ng TEQ/Nm3 (at 11% O2) 25 equivalent to an emission factor of 0.37 ng TEQ/kg of waste oil burned (LUA, 1997). 26 27 28 4.3.3.2. A ir E m issio n F a c to r 29 30 The emission factor measured by Bremmer et al. (1994) for small combustion units was 31 selected as most relevant to space heaters, i.e. 2 ng I-TEQDF/kg. Based on the limited data from 32 only one study and uncertainty about how the units tested by Bremmer et al. compare to space 33 heaters in the U.S., this is considered to be a preliminary estimate. 34 35 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-28 DRAFT: DO NOT CITE OR QUOTE 1 4.3.3.3. A c tiv ity L e v e l 2 3 The total amount of waste oil burned in 1983 was 0.59 billion gallons (USEPA, 1993). 4 Comparing this estimate with the 2006 estimate (described above) and assuming linear growth, 5 implies that used oil combustion has increased at a rate of about 1.4% per year. The 2006 data 6 indicates that 14.5 % of the total waste burned was in space heaters. Assuming this percentage 7 remains constant and using the annual growth rate, allows estimates of the amount of oil burned 8 in space heaters for each of the reference years (converted to kg based on 3.78 L/gal and density 9 of 0.88 kg/L): 10 11 1987 - 0.30 billion kg 12 1995 - 0.33 billion kg 13 2000 - 0.35 billion kg 14 15 Based on the lack of survey data specific to the reference years and facility types, these estimates 16 are considered preliminary. 17 18 19 4.3.3.4. A ir R e le a se s 20 21 The air releases were estimated by multiplying the emission factor and activity estimates. 22 23 4.3.3.5. W a ter R e le a se s - N o n e 24 25 4.3.3.6. S o lid R e s id u e R e le a se s - N o n e . 26 27 4.3.3.7. P ro d u c ts - N o n e . 28 29 4.3.3.8. R e le a s e S u m m a ry 30 31 The inventory decision criteria and release estimates are summarized below: 32 33 Inventory Decision Criteria for Waste Oil Combustion Air Water Emission tests for at least two units/source types with No sufficient documentation to directly derive emission factors Solids Product This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-29 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Waste Oil Combustion Measured emission factors consistent or have Yes understandable differences Emission factor tests represent units that are typical of the class No Activity estimates based on source-specific surveys Conclusion (Q = Quantitative, P = Preliminary) 1 2 No P 3 Waste Oil Combustion Air Releases______ Emission Factors 1987 - 2 ng I-TEQDF/kg oil combusted (Preliminary) 1995 - 2 ng I-TEQDF/kg oil combusted (Preliminary) 2000 - 2 ng I-TEQpF/kg oil combusted (Preliminary) Activity Levels 1987 - 0.30 billion kg (Preliminary) 1995 - 0.33 billion kg (Preliminary) 2000 - 0.35 billion kg (Preliminary) Releases 1987 - 0.60 g I-TEQDF(Preliminary) 1995 - 0.66 g I-TEQdf (Preliminary) 2000 - 0.70 g I-TEQdf (Preliminary)___________ W ater Releases These facilities do not have wastewater releases.__________ Solid Residue Releases These facilities do not have solid releases._______________ Products________ These facilities do not have products.___________________ 4 5 6 7 4.4. COAL COMBUSTION 8 4.4.1. Coal-Fired Power Plants 9 No changes were made to the air emission factors or activity estimates, but additional 10 background information is provided. Minor changes were made to the activity estimates for 11 solid residues resulting in minor changes in residue amounts. 12 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-30 DRAFT: DO NOT CITE OR QUOTE 1 4.4.1.1. A ir R e le a se s 2 UNEP (2005) reports that Dutch data from large coal-fired power plants gave an 3 emission factor of 0.35 pg I-TEQ/MT; German data were between 0.004 and 0.2 pg I-TEQ/MT , 4 and U.K. data had a median value of 0.14 pg I-TEQ/MT (range: 0.06-0.32 pg I-TEQ/MT). 5 As discussed in EPA (2006), EPRI and DOE data were used to derive an emission factor 6 of 0.078 ng WHO98 TEQDF/kg of coal combusted (0.079 ng I-TEQDF/kg). This is an average 7 over 11 U.S. facilities, but it is on the low end of the range reported in UNEP (2005) for 8 European facilities. Thus, there is some concern that this emission factor may be an 9 underestimate. One reason why it may be low is because all of the tested facilities had 10 cold-sided ESPs and experience in other industries suggested that higher emissions were likely 11 from facilities with hot-sided ESPs. In recognition of this concern, EPA/Department of Energy 12 (DOE) conducted testing of stack emissions in 1999 at the coal-fired Presque Island electric 13 utility boiler in Wisconsin, which was equipped with a hot-sided ESP. The testing showed no 14 increases in dioxin concentrations from the flue gas inlet to the outlet of a hot-sided ESP 15 (personal communication from Thomas Feeley, National Energy Technical Laboratory, 16 U.S. Department of Energy, Pittsburgh, PA to David Cleverly, National Center for 17 Environmental Assessment, U.S. Environmental Protection Agency, Washington, DC on 18 December 17, 2008). Accordingly, it is assumed that the TEQ emission factor for coal fired 19 utilities with hot-sided ESPs is of the same order of magnitude as the average TEQ emission 20 factors derived above. 21 In the year 2000, 10 facilities with an SIC code for electric services reported dioxin 22 releases under the EPA TRI program (U.S. EPA, 2008). The sum of the air releases across these 23 facilities was 63.2 g, which EPA estimates is equal to 8.9 g WHO98 TEQDF. No releases to other 24 media were reported. Also, in the year 2000, two facilities with an SIC code for electric and 25 other services combined reported dioxin releases under EPA's TRI program (U.S. EPA, 2008). 26 The sum of the air releases across these facilities was 457 g, which EPA estimates is equal to 27 22.2 g WHO98 TEQdf. No releases to other media were reported. As explained in Chapter 1, the 28 TRI data are not used to make quantitative estimates in this document but rather as supportive 29 evidence that releases do occur. 30 The activity estimates were derived from EIA (1999b). 31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-31 DRAFT: DO NOT CITE OR QUOTE 1 4.4.1.2. W a ter R e le a se s 2 No data on CDD/CDF levels in water releases from these facilities were found. Because 3 CDD/CDFs are found in the air emissions from these facilities, it is possible they could also be 4 found in scrubber waters. Thus, water releases of CDD/CDFs from these facilities are 5 considered possible but unquantifiable. 6 7 4.4.1.3. S o lid R e s id u e R e le a se s 8 Dyke et al. (1997) provided data on residues from industrial coal combustion in the 9 United Kingdom: Concentrations in fly ash were 0.23-8.7 ng TEQ/kg ash, and grate ash were 10 0.02-13.5 ng TEQ/kg. UNEP (2005) used these data to derive an average value of 11 4 ng I-TEQ/kg. A limited amount of CDD/CDF concentration data have been developed for ash 12 from coal combustion facilities in the United States (U.S. EPA, 1999c), and these data are for 13 wastes that are comanaged (i.e., combinations of fly ash, bottom ash, boiler slag, and flue gas 14 desulfurization wastes). A total of 15 samples were taken from 11 disposal sites. The total mean 15 concentration was 0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg). 16 The total mean concentration from EPA (1999c) was selected as the only U.S. data 17 available and within the range reported for the United Kingdom. This value of 18 0.73 ng WHO9TEQDF/kg (0.62 ng I-TEQDF/kg) was assumed to apply to all reference years. 19 The American Coal Ash Association (ACAA--http://www.acaa-usa.org/) releases annual 20 production and use estimates for coal ash. Production estimates for the reference years are as 21 follows: 22 23 1987--75.4 MMT 24 1995--83.6 MMT 25 2000--98.2 MMT 26 According to ACAA, between 25 and 30% of industrial coal ash was recycled in a variety 27 of ways including use in cement, grout, road base materials, manufactured aggregate, fill 28 material, snow/ice control, and agriculture. These amounts were estimated as 30% of the total 29 ash: 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-32 DRAFT: DO NOT CITE OR QUOTE 1 1987--22.6 MMT 2 1995--25.1 MMT 3 2000--29.5 MMT 4 5 The potential for environmental releases from these uses is unknown, but it is assumed here that 6 all of the CDD/CDF in the recycled ash represent an environmental release (release estimates are 7 shown in the summary below). The emission factor presented above is based on recent testing at 8 11 disposal sites, but it is uncertain how much actual release occurs from these products. 9 The ash that was not recycled was disposed of in landfills, and these residues are not 10 considered environmental releases. These amounts were multiplied by the ash emission factor 11 (presented above) to get the amount landfilled (on a TEQ basis): 12 13 1987--38.5 g WHO98 TEQdf (32.7 g I-TEQdf) 14 1995--42.7 g WHO98 TEQdf (36.3 g I-TEQdf) 15 2000--50.2 g WHO98 TEQdf (42.6 g I-TEQdf) 16 17 4.4.1.4. P r o d u c t L ite r a tu r e --N o n e 18 19 4.4.1.5. R e le a s e S u m m a ry 20 The inventory decision criteria and release estimates for all media are summarized below: 21 22 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-33 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Industrial Coal-Fired Utilities Air W ater Solids Products Emission tests for at least two units/source types with sufficient Yes Yes documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Yes Yes Yes Conclusion (Q = Quantitative, P = Preliminary). 1 QQ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-34 DRAFT: DO NOT CITE OR QUOTE Industrial Coal-Fired Utilities_____________________ Air Releases____________________________ Emission Factor 1987--0.078 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg). 1995--0.078 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg). 2000--0.078 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg).___________________ Activity Levels 1987--651 MMT. 1995--771 MMT. 2000--894 MMT.____________________________________________________ Releases 1987--51 g WHO98 TEQdf (51 g I-TEQdf). 1995--60 g WHO98 TEQdf (61 g I-TEQdf). 2000--70 g WHO98 TEQdf (71 g I-TEQdf)._______________________________ W ater Releases___________________________ Because some evidence exists that wastewater from these facilities may contain CDDs and CDFs, they are classified as possible but unquantifiable (Not quantifiable) sources.______ Solid Residue Releases________________________ Emission Factor 1987--0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) of ash. 1995--0.73 ng WHO98 TEQDF/kg (0.079 ng I-TEQDF/kg) of ash. 2000--0.73 ng WHO98 TEQDF/kg (q.079 ng I-TEQDF/kg) of ash._______________ Activity Levels 1987--22.6 MMT ash. 1995--25.1 MMT ash. 2000--29.5 MMT ash.________________________________________________ Releases 1987-- 17 g WHO98 TEQdf (14 g I-TEQdf). 1995-- 18 g WHO98 TEQdf ( 1 6 g I-TEQdf). 2000--22 g WHO98 TEQdf (18 g I-TEQdf)._______________________________ 1 2 3 4.4.2. Coal-Fired Industrial Boilers 4 4.4.2.1. A ir R e le a se s 5 No changes were made to the air emission factors, but they were upgraded from a 6 confidence rating of preliminary to quantifiable. This was because they were based on a 7 reasonably large study (n = 15) from the U.K. (CRE, 1994) and the likelihood that the 8 technologies were similar to U.S. facilities. The activity estimates were updated using EIA 9 (2006), which indicated that the amount of coal burned in industrial utilities was 68.2 MMT in 10 1987, 66.3 MMT in 1995, and 59.2 MMT in 2000. 11 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-35 DRAFT: DO NOT CITE OR QUOTE 1 4.4.2.2. W a ter L ite r a tu r e 2 No data on CDD/CDF levels in water releases from these facilities were found. Because 3 CDD/CDFs are found in the air emissions from these facilities, it is possible they could also be 4 found in scrubber waters. Thus, water releases of CDD/CDFs from these facilities are 5 considered possible but unquantifiable. 6 7 4.4.2.3. S o lid R e s id u e R e le a se s 8 No data on the CDD/CDF content of ash from industrial boilers were found; however, 9 this should be similar to the values presented in Section 4.4.1 for coal-fired utilities. Also, the 10 activity estimates presented for coal-fired utilities include ash from all coal combustion used to 11 generate electricity. Thus, they should represent most of the industrial utility boilers. So it is 12 assumed that the solid residue releases presented for the utilities include the releases from 13 industrial boilers (see Section 4.4.1). 14 15 4.4.2.4. R e le a s e S u m m a ry 16 The inventory decision criteria and release estimates for all media are summarized below: 17 Inventory Decision Criteria for Industrial Coal-Fired Boilers Air Water Solids Products Emission tests for at least two units/source types with sufficient Yes documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 18 19 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-36 DRAFT: DO NOT CITE OR QUOTE 1 Industrial Coal-Fired Boilers_______________________ Air Releases______________________________ Emission Factors 1987--0.7 ng WHO98 TEQDF/kg (0.6 ng I-TEQDF/kg)of coal combusted. 1995--0.7 ng WHO98 TEQDF/kg (0.6 ng I-TEQDF/kg) of coal combusted. 2000--0.7 ng WHO98 TEQDF/kg (0.6 ng I-TEQpF/kg) of coal combusted.__________ Activity Levels 1987--68.2 MMT. 1995--66.3 MMT. 2000--59.2 MMT._____________________________________________________ Releases 1987--48 g WHO98 TEQdf (41 g I-TEQdf). 1995--46 g WHO98 TEQdf (40 g I-TEQdf). 2000--41 g WHO98 TEQdf (36 g I-TEQDF)._________________________________ W ater Releases_____________________________ Because some evidence exists that wastewater from these facilities may contain CDDs and CDFs, they are classified as possible but unquantifiable sources._______________________ Solid Residue Releases__________________________ These releases are included in the estimates for coal-fired utilities presented in Section 4.4.1. Products________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs. 2 3 4 4.4.3. Residential Coal Combustion 5 4.4.3.1. A ir R e le a se s 6 No changes were made to the air emission factor, but it was upgraded from preliminary to 7 quantitative. Also a new study was found as summarized below. 8 Paradiz et al. (2008) measured CDD/F emissions from a coal fired domestic stove. The 9 study was conducted in Italy using a high chlorine content coal. Testing with a non-insulated 10 chimney yielded an emission factor of 1326 I-TEQ gg/ton of coal burned. Testing with an 11 insulated chimney yielded an emission factor of 126 I-TEQ gg/ton of coal burned. A 12 pronounced effect of the temperature profile in the chimney on PCDD/F emissions was 13 identified, suggesting formation in the chimney. 14 15 As discussed in the original document, the emission factor was based on an analysis by 16 Eduljee and Dyke (1996) on data from the Coal Research Establishment in the United Kingdom 17 (2.1 ng I-TEQDF/kg for anthracite coal and 5.7 to 9.3 ng I-TEQDF/kg [midpoint, This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-37 DRAFT: DO NOT CITE OR QUOTE 1 7.5 ng I-TEQDF/kg] for bituminous coal). Wevers et al. (2003) measured CDD/CDF emissions 2 from various types of household appliances used in Belgium. The average emission factor for 3 anthracite coal burners was 77.1 ng I-TEQ/kg. UNEP (2005) reports that European studies 4 generally show a range of 1.6 to 50 ng TEQ/kg for typical coal and emission factors as high as 5 660 ng I-TEQ/kg for high chlorine coals. Ultimately UNEP (2005) recommends 3 ng I-TEQ/kg 6 for domestic burning with typical coals. Based on the similarity of the emission factor data 7 summarized by UNEP for typical coals and estimates by Eduljee and Dyke (1996), the emission 8 factor was upgraded from preliminary to quantitative. The congener data for emissions from 9 normal lignite (Thub et al., 1995), indicate that the WHO98 TEQs were less than 9% higher than 10 the I-TEQs. Based on this small difference, the I-TEQ emission factor was assumed to be 11 essentially equivalent when expressed as WHO98 TEQs. 12 The activity estimates were updated using EIA (2006), which indicated that the amount 13 of coal burned at residences was 1.6 MMT in 1987, 0.8 MMT in 1995, and 0.5 MMT in 2000. 14 EPA (1997a) reported that 72.5% of the coal consumed by the residential sector in 1990 was 15 bituminous and 27.5% was anthracite. These factors were assumed to apply to all reference 16 years. 17 18 4.4.3.2. W a ter R e le a s e s --N o n e 19 20 4.4.3.3. S o lid R e s id u e R e le a se s 21 The solid residues from coal-fired utility boilers are likely to be similar to the solid 22 residues from residential units. On this basis, the same emission factor is assumed to apply, i.e., 23 0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg). UNEP (2005) suggests a "first estimate" 24 emission factor for residues from coal fired stoves of 5,000 ng I-TEQ/kg. This is based on 25 measurements in soot, which may not be representative of bottom ash. A preliminary confidence 26 rating is assigned to this emission factor because it is based on testing from different facilities. 27 The total amount of ash generated by these facilities is assumed to be 10% of the total 28 coal used. On this basis, the solid residues are estimated to be 0.16 MMT in 1987, 0.08 MMT in 29 1995, and 0.05 MMT in 2000. Some of this ash is likely to be disposed along with household 30 trash and taken to a municipal landfill. This portion would not be considered an environmental 31 release. Others may dispose of it on their property in a manner that is open to the environment. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-38 DRAFT: DO NOT CITE OR QUOTE 1 2 4.4.3.4. P r o d u c ts --N o n e 3 4 4.4.3.5. R e le a s e S u m m a ry 5 The inventory decision criteria and release estimates for all media are summarized below: Inventory Decision Criteria for Residential Coal Combustion Air W ater Solids Products Emission tests for at least two units/source types with sufficient Yes No documentation to directly derive emission factors. Measured emission factors consistent or have understandable Yes differences. Emission factor tests represent units that are typical of the class. Yes No Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 6 Yes Yes QP This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-39 DRAFT: DO NOT CITE OR QUOTE Emission Factors Residential Coal Combustion_________________________ Air Releases________________________________ A nthracite 1987--2.1 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg). 1995--2.1 ng WHO98 TEQDF/kg (2 .1 ng I-TEQDF/kg). 2000--2.1 ng WHO98 TEQDF/kg (2 .1 ng I-TEQDF/kg). B itum inous 1987--7.5 ng WHO98 TEQDF/kg (7.5 ng I-TEQDF/kg). 1995--7.5 ng WHO98 TEQDF/kg (7.5 ng I-TEQDF/kg). 2000--7.5 ng WHO98 TEQDF/kg (7.5 ng I-TEQDF/kg).________________________ Activity Levelsa 1987-- 1.6 MMT. 1995--0.8 MMT. 2000--0.5 MMT._____________________________________________________ Releases 1987-- 10 g WHO98 TEQdf or I-TEQDF. 1995--5 g WHO98 TEQdf or I-TEQdf. 2 0 0 0 --3 g WHO98 TEQdf or I-TEQdf.____________________________________ W ater Releases_______________________________ These facilities do not have wastewater releases.______________________________________ Solid Residue Releases____________________________ Emission Factors 1987--0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) (Preliminary). 1995--0.73 ng WHO98TEQDF/kg (0.62 ng I-TEQDF/kg) (Preliminary). 2000--0.73 ng WHO98 TEQDF/kg (0.62 ng I-TEQDF/kg) (Preliminary).___________ Activity Levels 1987--0.16 MMT. 1995--0.08 MMT. 2000--0.05 MMT.____________________________________________________ Releasesb 1987--0.1 g WHO98 TEQdf (0.1 g I-TEQdf) (Preliminary). 1995--0.1 g WHO98 TEQdf (0 .1 g I-TEQdf) (Preliminary). 2000-- <0.1 g WHO98 TEQdf (<0.1 g I-TEQd) (Preliminary).__________________ Products__________________________________ These facilities do not have products. 1 2 aNote: 72.5%ofthe coal burned is bituminous, and 27.5%is anthracite. 3 ^Note: Anunknownportion ofthis is landfilled and, therefore, is not considered a release to the open environment. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 4-40 DRAFT: DO NOT CITE OR QUOTE 1 5. COMBUSTION SOURCES OF CDDS/CDFS: OTHER 2 HIGH-TEMPERATURE SOURCES 3 4 5 5.1. CEMENT KILNS 6 5.1.1. Air Releases 7 No changes were made to the air-release estimates from cement kilns. However, 8 additional background information is provided below. 9 The present report uses higher emission factors for cement kilns burning hazardous waste 10 in 1987 and 1995 than kilns not burning hazardous waste (emission factors were not needed in 11 2000 for hazardous waste burners because virtually all facilities had been tested). As discussed 12 below, these higher emissions were more likely due to APCD temperatures than the hazardous 13 waste. 14 World Business Council for Sustainable Development (2006) evaluated 2,200 CDD/CDF 15 measurements made at cement kilns from the late 1970s until recently. This report concluded 16 that coprocessing of alternative fuels and raw materials, fed to the main burner, kiln inlet or the 17 precalciner does not influence or change the emissions of persistent organic pollutants (POPs). 18 EPA (1999) also concluded that hazardous waste burning at cement kilns is not likely to affect 19 emissions of dioxins/furans. Rather, these reports conclude that reducing the temperature at the 20 inlet of the air pollution control device is one factor shown to have a significant impact on 21 limiting dioxin formation and emissions at all types of cement kilns, independent of waste 22 feeding. Lower APCD temperatures are believed to prevent the postcombustion catalytic 23 formation of CDD/CDFs. This is supported by emissions testing at a Portland cement kiln which 24 showed that CDDs/CDFs were almost entirely absent at the inlet to a hot-sided ESP, but 25 measurements taken at the exit showed conclusively that dioxins were formed within the 26 hot-sided ESP (U.S. EPA, 1997b). After 1995, a number of cement kilns added exhaust 27 gas-quenching units upstream of the APCD to reduce the inlet APCD temperature, thereby 28 reducing CDD/CDF stack concentrations. 29 UNEP (2005) also concluded that APCD temperature is the key factor affecting 30 CDD/CDF emissions and recommended emission factors on this basis: 31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 DRAFT: DO NOT CITE OR QUOTE 1 ESP temperature <200C--0.05 ng I-TEQ/kg of clinker 2 ESP temperature 200-300C--0.6 ng I-TEQ/kg of clinker 3 ESP temperature >300C--5 ng I-TEQ/kg of clinker 4 5 In the year 2000, nine facilities with an SIC code for "cement, hydraulic" reported dioxin 6 releases under the EPA TRI program (U.S. EPA, 2008). The total air releases across these 7 facilities was 201 g, which EPA estimates is equal to 36 g WHO98 TEQdf. No releases to other 8 media were reported. As explained in Chapter 1, the TRI data are not used to make quantitative 9 estimates in this document, but, rather, the data are offered as supportive evidence that releases 10 do occur. 11 For kilns burning hazardous waste, the emission factors were derived using test report 12 data from 1989-1996 (U.S. EPA, 1996a). These data provided APCD inlet temperature data for 13 88 test runs at 14 cement kilns and allowed development of emission factors for kilns with 14 APCD inlet temperatures greater than 232C and for kilns with APCD inlet temperatures less 15 than 232C. These were used in 1987 and 1995. In 2000, almost all of the facilities had been 16 tested, and it was unnecessary to use an emission-factor/activity-level approach to derive release 17 estimates (U.S. EPA, 2002a). 18 For the kilns not burning hazardous waste, insufficient information was available to 19 derive temperature-specific emission factors, and the same emission factor was assumed to apply 20 to all facilities. This was derived from data in Bell (1999) and EPA (1996b) on a total of 21 16 facilities. The lack of temperature data for the kilns not burning hazardous waste introduces 22 uncertainty into the emission-factor assumption and may be an underestimate if the testing did 23 not include facilities with high-temperature control devices. 24 The activity data for clinker production were derived from information provided by U.S. 25 DOC (1996) and Portland Cement Association (2001). All emission factors, activities, and 26 release estimates are shown in the release summary below. 27 28 5.1.2. W ater Releases 29 It is possible that the effluent from the APCD systems at these facilities contains CDDs 30 and CDFs because they have been measured in the stack gases. No information was found on 31 the levels in the effluent, so this is considered a possible but unquantifiable source. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5-2 DRAFT: DO NOT CITE OR QUOTE 1 5.1.3. Solid Residue Releases 2 No changes were made to the solid residue release estimates from cement kilns. 3 However, additional background information is provided below. 4 Cement kiln dust (CKD) is the solid residual material collected by the APCD system of a 5 cement kiln. Gross CKD (or as-generated CKD) is either recycled back into the kiln system or 6 removed from the system for disposal (becoming net CKD or as-managed CKD). Most of the 7 net CKD is disposed in secure landfills, but some is used for a variety of beneficial purposes 8 such as municipal waste daily cover material, municipal waste landfill final cover material, soil 9 stabilization for roadways or other structures, waste neutralization/stabilization/solidification 10 (e.g., food wastes, hazardous wastes, etc.), and agricultural soil amendment. It is assumed that 11 CDD/CDF releases could occur during the beneficial uses but not from the landfilled portions. 12 As discussed in EPA, 2006 data on the amounts of CKD used for beneficial purposes was 13 provided by the Portland Cement Association and split between kilns burning and not burning 14 hazardous waste based on the relative amounts of clinker produced. 15 A wide range of CDD/PCDF concentrations in the CKD has been measured. A range 16 from 0.001 to 30 ng TEQ/kg has been reported for U.K. kilns (Dyke et al., 1997), and 17 1-40 ng TEQ/kg were summarized for German tests (SCEP, 1994). As discussed in EPA 18 (2006), for kilns burning hazardous waste, the CKD concentration is assumed to be 19 35 ng I-TEQ/kg (n = 5), and for the kilns not burning hazardous waste, the CKD concentration is 20 assumed to be 0.003 ng I-TEQ/kg (n = 6). These emission factors were applied to all reference 21 years. They are considered preliminary because of the inconsistency in measured values and 22 lack of understanding for the differences. The dioxin concentrations in CKD were also used to 23 estimate the amounts of CDD/CDFs in landfilled CKD, as shown below: 24 Kilns burning hazardous waste Kilns not burning hazardous waste CKD activity (million kg) Landfilled (g i-t e q ) CKD activity (million kg) Landfilled (g i-t e q ) 1987 426 14.9 2,230 0.007 1995 505 17.7 2,642 0.008 2000 365 12.8 1,858 0.006 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 3 DRAFT: DO NOT CITE OR QUOTE 1 5.1.4. Products 2 Clinker is the primary product of cement kilns and is ultimately used to make Portland 3 cement. EPA (1993a) described the results of sampling and analysis of clinker conducted in 4 1992 and 1993. Clinker samples were collected from five cement kilns burning nonhazardous 5 waste and six kilns burning hazardous waste. CDDs/CDFs were not detected in any of the 6 samples. Some of the CKD is beneficially reused as discussed above. Releases associated with 7 beneficial uses of CKD are covered under the solid residue section. 8 9 5.1.5. Release Summary 10 The inventory decision criteria and releases to all media are summarized below: 11 Inventory Decision Criteria for Cement Kilns Air W ater Solids Products Emission tests for at least two units/source types with Yes Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have Yes No understandable differences. Emission factor tests represent units that are typical of the class. Yes Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 12 13 Yes Q Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 . 4 DRAFT: DO NOT CITE OR QUOTE Cement Kilns Not Burning Hazardous Waste__________________ Air Releases________________________________ Emission Factor 1987--0.27 ng WHO98 TEQDF/kg (0.26 ng I-TEQ/kg) of clinker produced. 1995--0.27 ng WHO98 TEQDF/kg (0.26 ng I-TEQ/kg) of clinker produced. 2000--0.27 ng WHO98 TEQDF/kg (0.26 ng I-TEQ/kg) of clinker produced.___________ Activity Levels 1987--47.2 billion kg of clinker. 1995--61.3 billion kg of clinker. 2000--63.7 billion kg of clinker.____________________________________________ Releases 1987--13 g WHO98 TEQDF/yr (12 g I-TEQDF/yr). 1995--17 g WHO98 TEQDF/yr ( 1 6 g I-TEQDF/yr). 2000--17 g WHO98 TEQDF/yr (17 g I-TEQDF/yr)._______________________________ W ater Releases_______________________________ It is possible that the effluent from the APCD systems at these facilities contains CDDs and CDFs because they have been measured in the stack gases. No information was found on levels in the effluent, so this considered a possible but unquantifiable source.____________________ Solid Residue Releases____________________________ Emission Factor 1987--0.003 ng I-TEQ/kg (Preliminary). 1995--0.003 ng I-TEQ/kg (Preliminary). 2000--0.003 ng I-TEQ/kg (Preliminary).______________________________________ Activity Levels 1987--632 million kg. 1995--547 million kg. 2000--480 million kg._____________________________________________________ Releases for Beneficial Uses 1987--<0.1 g I-TEQ (Preliminary). 1995--<0.1 g I-TEQ (Preliminary). 2000--<0.1 g I-TEQ (Preliminary).__________________________________________ Products__________________________________ No information was found suggesting that clinker contained measureable levels of CDDs and CDFs. Beneficial uses of CKD are covered under solid residues._________________________ 1 2 3 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 . 5 DRAFT: DO NOT CITE OR QUOTE Cement Kilns Burning Hazardous Waste_____________________ Air Releases_________________________________ Emission Factors 1987--APCD > 232C: 31 ng WHO98 TEQDF/kg (29 ng I-TEQ/kg) of clinker produced. APCD < 232C: 1.1 ng WHO98 TEQDF/kg (1.0 ng I-TEQ/kg) of clinker produced. 1995--APCD > 232C: 31 ng WHO98 TEQDF/kg (29 ng I-TEQ/kg) of clinker produced. APCD < 232C: 1.1 ng WHO98 TEQDF/kg (1.0 ng I-TEQ/kg) of clinker produced. 2000--EFs not needed because all individual facilities were tested.__________________ Activity Levels 1987--APCD > 232C: 3.8 billion kg of clinker. APCD < 232C: 1 billion kg of clinker. 1995--APCD > 232C: 5.04 billion kg of clinker. APCD < 232C: 1.26 billion kg of clinker. 2000--Activity estimates not needed because all individual facilities were tested._______ Releases 1987--APCD > 232C: 120 g WHO98 TEQDF/yr (110 g I-TEQDF/yr). APCD < 232C: 1 g WHO98 TEQDF/yr (1 g I-TEQDF/yr). 1995--APCD > 232C: 160 g WHO98 TEQDF/yr (150 g I-TEQDF/yr). APCD < 232C: 1 g WHO98 TEQDF/yr (1 g I-TEQDF/yr). 2000--19 g WHO98TEQDF/yr (17 g I-TEQDF/yr).________________________________ W ater Releases________________________________ It is possible that the effluent from the APCD systems at these facilities contain CDDs and CDFs because they have been measured in the stack gases. No information was found on levels in the effluent, so this considered a possible but unquantifiable source.__________________________ Solid Residue Releases_____________________________ Emission Factor 1987--35 ng I-TEQDF/kg (Preliminary). 1995--35 ng I-TEQDF/kg (Preliminary). 2000--35 ng I-TEQDF/kg (Preliminary)._______________________________________ Activity Level for Beneficial Uses 1987--120 million kg. 1995--104 million kg. 2000--94 million kg.______________________________________________________ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 6 DRAFT: DO NOT CITE OR QUOTE Cement Kilns Burning Hazardous Waste (continued)_____________ Releases for Beneficial Uses 1987--4 g I-TEQ (Preliminary). 1995--4 g I-TEQ (Preliminary). 2000--3 g I-TEQ (Preliminary).___________________________________________ Products________________________________ No information was found suggesting that clinker contained measureable levels of CDDs and CDFs. Beneficial uses of CKD are covered under solid residues. 1 2 3 5.2. LIGHTWEIGHT AGGREGATE KILNS 4 5.2.1. Air Releases 5 No changes were made to the air-release estimates, but some clarifications are provided. 6 Lightweight aggregate (LWA) kilns burning hazardous waste are estimated to have emitted 7 3.3 g I-TEQdf to air in 1990 (Federal Register, 1998) and 2.4 g I-TEQDf in 1997 (Federal 8 Register, 1999); these estimates are used in this report for reference years 1987 and 1995, 9 respectively. The emission factor estimate for 2000 is 1.99 ng WHO98 TEQDF/kg 10 (2.06 ng I-TEQDF/kg) based on testing at 5 kilns (U.S. EPA, 2002a). As discussed in EPA, 2006, 11 activity data were available on all 9 facilities operating in 2000 from EPA's Office of Solid 12 Waste. This information was combined with assumptions about annual feed rates and operating 13 time percentage to get total activity estimates. EPA (2006) mislabeled the activity estimates as 14 applying to halogen acid furnaces rather than light weight aggregate kilns. 15 16 5.2.2. W ater Releases--None 17 18 5.2.3. Solid Residue Releases--None 19 20 5.2.4. Product Literature--None 21 22 5.2.5. Release Summary 23 The inventory decision criteria and releases to all media are summarized below: 24 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 7 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Lightweight Aggregate Kilns Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have Yes understandable differences. Emission factor tests represent units that are typical of Yes the class. Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). 1 Q 2 Lightweight Aggregate Kilns_______________________ Air Releases______________________________ Emission Factors 1987--not needed. 1995--not needed. 2000--2.0 ng WHO98 TEQDF/kg (2.1 ng I-TEQDF/kg) of waste feed.______________ Activity Levels 1987--not needed. 1995--not needed. 2000--903,000 MT.____________________________________________________ Releases 1987--3 g I-TEQdf. 1995--2 g I-TEQdf. 2000--2 g WHO98 TEQdf (2 g I-TEQdf).___________________________________ W ater Releases_____________________________ No information was found suggesting that water releases from these facilities would contain CDDs and CDFs._____________________________________________________________ Solid Residue Releases__________________________ No information was found suggesting that solid residues from these facilities would contain CDDs and CDFs._____________________________________________________________ Products________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs.__________________________________________________________________ 3 4 5 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 _ 8 DRAFT: DO NOT CITE OR QUOTE 1 5.3. ASPHALT MIXING PLANTS 2 5.3.1. Air Releases 3 Changes were made to the air emission factor, and the releases estimated for 2000 were 4 also assumed to apply to the reference years 1987 and 1995. 5 The original report estimated the emission factor on the basis of tests at two U.S. 6 facilities. The original report also included information on testing at one facility in the 7 Netherlands: 0.047 ng I-TEQ/kg (Bremmer et al., 1994) and three facilities in Germany: 0.0002, 8 0.0035, and 0.0038 ng I-TEQ/kg (Umweltbundesamt, 1996). Because the European facilities are 9 likely similar to those in the United States, the y were averaged in with the U.S. facilities to 10 derive an emission factor of 0.0095 ng I-TEQ/kg, and this was applied to all reference years. 11 This factor falls within the range recommended by UNEP (2005) for asphalt mixing plants: 12 0.0.007 to 0.07 ng I-TEQ/kg. The confidence rating was upgraded from preliminary to 13 quantifiable based on the additional testing used to support it and similarity to UNEP, 2005. 14 The original report provided an activity estimate of 500 million tons for 2000 based on 15 1996 survey data. Because this industry is fairly stable in terms of growth and the activity data 16 are near the midpoint of the reference year range, it is reasonable to assume it applies to all 17 reference years. Asphalt can be produced at both fixed and mobile facilities. It is unclear if this 18 activity estimate includes both types of plants or only those at fixed locations. The National 19 Cooperative Highway Research Program Web site and other related sites were searched, but no 20 relevant information was found. 21 22 5.3.2. W ater Releases 23 No information was found suggesting that water releases from these facilities would 24 contain CDDs and CDFs. 25 26 5.3.3. Solid Residue Releases 27 UNEP (2005) indicates that flue gas cleaning residues are likely to have CDD/CDFs and 28 suggests an emission factor of 0.06 ng I-TEQ/kg. No information was available on the quantity 29 of this material generated. Also, it is likely that these residues would be landfilled and, therefore, 30 not considered a release. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5-9 DRAFT: DO NOT CITE OR QUOTE 1 5.3.4. Products 2 No information was found suggesting that products from these facilities would contain 3 CDDs and CDFs. 4 5 5.3.5. Release Summary 6 The inventory decision criteria and releases are summarized below: 7 Inventory Decision Criteria for Asphalt Mixing Plants Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 8 9 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 0 DRAFT: DO NOT CITE OR QUOTE Asphalt Mixing Plants_____________________________ Air Releases_________________________________ Emission Factors 1987--0.009 ng I-TEQ/kg of asphalt produced. 1995--0.009 ng I-TEQ/kg of asphalt produced. 2000--0.009 ng I-TEQ/kg of asphalt produced._________________________________ Activity Levels 1987--500 MMT. 1995--500 MMT. 2000--500 MMT.________________________________________________________ Releases 1987--5 g I-TEQ. 1995--5 g I-TEQ. 2000--5 g I-TEQ._________________________________________________________ W ater Releases________________________________ No information was found suggesting that water releases from these facilities would contain CDDs and CDFs._______________________________________________________________ Solid Residue Releases____________________________ Any solid residues from these facilities would be landfilled and not considered an environmental release._______________________________________________________________________ Products__________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs. 1 2 3 5.4. PETROLEUM-REFINING CATALYST REGENERATION PLANTS 4 5.4.1. Air Releases 5 No changes were made to the air-release estimates. The average of the emission factors 6 for two California facilities (1.59 ng WHO98 TEQDF/barrel (1.52 ng I-TEQDF/barrel) of reformer 7 feed) is assumed to apply to all reference years. The activity estimates were derived from EIA, 8 2002. 9 In the year 2000, one facility with an SIC code for petroleum bulk stations and terminals 10 reported dioxin releases under EPA's TRI program (U.S. EPA, 2008). The total air releases for 11 this facility was 102.8 g, which EPA estimates is equal to 3 g WHO98 TEQDF. No releases to 12 other media were reported. As explained in Chapter 1, the TRI data are not used to make 13 quantitative estimates in this document, but, rather, the data are offered as supportive evidence 14 that releases do occur. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 1 DRAFT: DO NOT CITE OR QUOTE 1 5.4.2. W ater Releases 2 As discussed in EPA (2006), CDD/CDFs have been detected in wastewaters from these 3 facilities. However, insufficient information is available on the levels and quantities of these 4 wastes to generate release estimates. On this basis, they are considered possible but 5 unquantifiable sources. 6 7 5.4.3. Solid Residue Releases 8 As discussed in EPA (2006), CDD/CDFs have been detected in solid residues from these 9 facilities. However, insufficient information is available on the levels and quantities of these 10 wastes to estimate the amounts. However, these residues would be landfilled and, therefore, not 11 considered an environmental release. 12 13 5.4.4. Product Literature 14 No information was found suggesting that products from these facilities would contain 15 CDDs and CDFs. 16 17 5.4.5. Release Summary 18 The inventory decision criteria and releases are summarized below: Inventory Decision Criteria for Petroleum-Refining Catalyst Regeneration Plants Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 19 20 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 2 DRAFT: DO NOT CITE OR QUOTE Petroleum-Refining Catalyst Regeneration Plants_________________ Air Releases_________________________________ Emission Factors 1987--1.6 ng WHOgg TEQDF/barrel (1.5 ng I-TEQDF/barrel) of reformer feed. 1995--1.6 ng WHO98 TEQDF/barrel (1.5 ng I-TEQDF/barrel) of reformer feed. 2000--1.6 ng WHO98 TEQDF/barrel (1.5 ng I-TEQDF/barrel) of reformer feed._________ Activity Levels 1987--1,390 million barrels. 1995--1,410 million barrels. 2000--1,380 million barrels.________________________________________________ Releases 1987--2 g WHO98TEQdf (2 g I-TEQdf). 1995--2 g WHO98 TEQdf ( 2 g I-TEQdf). 2000--2 g WHO98 TEQdf (2 g I-TEQdf).______________________________________ W ater Releases________________________________ CDD/CDFs have been detected in wastewaters from these facilities. However, insufficient information is available on the levels and quantities of these wastes to generate release estimates. On this basis, they are considered possible but unquantifiable sources._____________________ Solid Residue Releases_____________________________ Any solid residues from these facilities would be landfilled and not considered an environmental release._______________________________________________________________________ Products___________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs._____________________________________________________________________ 1 2 3 5.5. CIGARETTE SMOKING 4 5.5.1. Air Releases 5 No changes were made to the air-release estimates. The air emission factor was derived 6 using data from Matsueda et al. (1994) and Lofroth and Zebuhr (1992). The activity estimates 7 were based on Brown (2002). 8 9 5.5.2. W ater Releases--None 10 11 12 13 14 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 3 DRAFT: DO NOT CITE OR QUOTE 1 5.5.3. Solid Residue Releases 2 No information was found suggesting that ash from cigarette smoking would contain 3 CDDs and CDFs. 4 5 5.5.4. Products--None 6 7 5.5.5. Release Summary 8 The inventory decision criteria and releases are summarized below. Although these 9 emission estimates are relatively small compared to many other sources, they have increased 10 importance because humans are directly exposed to cigarette smoke. 11 Inventory Decision Criteria for Cigarette Smoking Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 12 13 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 4 DRAFT: DO NOT CITE OR QUOTE Cigarette Smoking______________________________ Air Releases________________________________ Emission Factors 1987--1.7 pg WHO98 TEQDF/cigarette (1.6 pg I-TEQDF/cigarette). 1995--1.7 pg WHO98 TEQDF/cigarette (1.6 pg I-TEQDF/cigarette). 2000--1.7 pg WHO98 TEQDF/cigarette (1.6 pg I-TEQDF/cigarette)._________________ Activity Levels 1987--575 billion cigarettes. 1995--487 billion cigarettes. 2000--440 billion cigarettes._______________________________________________ Releases 1987--1 g WHO98 TEQdf (0.9 g I-TEQdf). 1995--0.8 g WHO98 TEQdf (0.8 g I-TEQdf). 2000--0.7 g WHO98 TEQdf (0.7 g I-TEQdf).__________________________________ W ater Releases_______________________________ None.________________________________________________________________________ Solid Residue Releases____________________________ No information was found suggesting that ash from cigarette smoking would contain CDDs and CDFs.________________________________________________________________________ Products__________________________________ Not applicable._________________________________________________________________ 1 2 3 5.6. PYROLYSIS OF BROMINATED FLAME RETARDANTS 4 The primary purpose of this report is to provide emission estimates for chlorinated 5 dibenzo-p-dioxins and dibenzofurans. However, the brominated dibenzo-p-dioxins (BDDs) and 6 dibenzofurans (BDFs) may also have dioxin-like toxicity. To date, though, no TEQs have been 7 established for these compounds. Because these compounds are related to the CDDs and CDFs, 8 some information on their emissions from facilities that pyrolyze brominated flame retardants is 9 included in EPA (2006). 10 11 5.7. CARBON REACTIVATION FURNACES 12 5.7.1. Air Releases 13 No changes were made to the air-release estimates. The emission factor was derived 14 from two GAC reactivation furnaces stack-tested by EPA (U.S. EPA, 1987; Lykins et al., 1987). 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 5 DRAFT: DO NOT CITE OR QUOTE 1 One test was conducted at a multiple hearth facility which is typical of large scale operations and 2 the second test was conducted at a fluidized bed facility which is more typical of smaller 3 operations. The activity was estimated on the basis of the mass of virgin GAC shipped each year 4 by GAC manufacturers according to the U.S. Department of Commerce (U.S. DOC, 1990). 5 6 5.7.2. W ater Releases--None 7 8 5.7.3. Solid Residue Releases--None 9 10 5.7.4. Products 11 No information was found suggesting that products from these facilities would contain 12 CDDs and CDFs. 13 14 5.7.5. Release Summary 15 The inventory decision criteria and releases are summarized below: 16 Inventory Decision Criteria for Carbon Reactivation Furnaces Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 17 18 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 6 DRAFT: DO NOT CITE OR QUOTE Carbon Reactivation Furnaces_______________________ Air Releases______________________________ Emission Factors 1987--1.2 ng (WHO98 TEQdf or I-TEQdf) per kg of reactivated carbon. 1995--1.2 ng (WHO98 TEQdf or I-TEQdf) per kg of reactivated carbon. 2000--1.2 ng (WHO98 TEQdf or I-TEQdf) per kg of reactivated carbon.___________ Activity Levels 1987--48,000 MT. 1995--65,000 MT. 2000--65,000 MT._____________________________________________________ Releases 1987--0.1 g (WHO98 TEQdf or I-TEQdf). 1995--0.1 g (WHO98 TEQdf or I-TEQdf). 2000--0.1 g (WHO98 TEQdf or I-TEQdf).___________________________________ W ater Releases_____________________________ No water releases are produced._________________________________________________ Solid Residue Releases__________________________ No solid residues are produced._________________________________________________ Products________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs. 1 2 3 5.8. KRAFT BLACK LIQUOR RECOVERY BOILERS 4 5.8.1. Air Releases 5 No changes were made to the air-release estimates. The emission factor for 1987 and 6 1995 was based on the data for the six NCASI facilities (NCASI, 1995). For 2000, the emission 7 factor was based on "NCASI Handbook of Chemical Specific Information for SARA 8 Section 313 Form R Reporting." Activity estimates were derived from information provided by 9 American Paper Institute (API, 1992), American Forest and Paper Association (AF&PA,1997), 10 and NCASI (2002). 11 12 5.8.2. W ater Releases--None 13 14 15 16 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 7 DRAFT: DO NOT CITE OR QUOTE 1 5.8.3. Solid Residue Releases 2 Fly ash is typically collected in ESPs at these facilities. Because CDD/CDFs have been 3 detected in the stack gases, they are likely to be also contained in the fly ash, but no 4 measurements have been reported. Any solid residues are likely to be landfilled and, therefore, 5 are not considered an environmental release. 6 7 5.8.4. Products 8 No information was found suggesting that products from these facilities would contain 9 CDDs and CDFs. 10 11 5.8.5. Release Summary 12 The inventory decision criteria and releases are summarized below: 13 Inventory Decision Criteria for Kraft Black Liquor Recovery Boilers Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 14 15 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 8 DRAFT: DO NOT CITE OR QUOTE Kraft Black Liquor Recovery Boilers______________________ Air Releases_________________________________ Emission Factors 1987--0.03 ng WHO98 TEQDF/kg (0.03 ng I-TEQDF/kg) of black liquor solids. 1995--0.03 ng WHO98 TEQDF/kg (0.03 ng I-TEQDF/kg) of black liquor solids. 2000--0.010 ng WHO98 TEQDF/kg of black liquor solids._________________________ Activity Levels 1987--69.8 MMT. 1995--80.8 MMT. 2000--90.7 MMT for Kraft recovery furnaces.__________________________________ Releases 1987--2 g (WHO98 TEQdf or I-TEQdf). 1995--2 g (WHO98 TEQdf or I-TEQdf). 2000--0.9 g WHO98 TEQDF/yr.______________________________________________ W ater Releases________________________________ No water releases are produced.____________________________________________________ Solid Residue Releases_____________________________ Any solid residues from these facilities would be landfilled and not considered an environmental release._______________________________________________________________________ Products__________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs. 1 2 3 5.9. LIME KILNS 4 This is a new section covering lime kilns used in the pulp and paper industry as well as 5 other industries. 6 7 5.9.1. Process Description 8 Lime making consists of burning of calcium and/or magnesium carbonate at a 9 temperature between 900 and 1,500C. The burned lime is either delivered to the end user in the 10 form of quicklime or reacted with water in a hydrating plant to produce hydrated lime or slaked 11 lime. Different fuels--solid, liquid, or gaseous--are used in lime burning. Most of the kilns are 12 either shaft or rotary design and have countercurrent flow of solids and gases. Fluidized bed 13 kilns and rotary hearths may also be found (UNEP, 2005). 14 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 1 9 DRAFT: DO NOT CITE OR QUOTE 1 5.9.2. Regulations 2 None specific to dioxins. 3 4 5.9.3. Air Releases 5 Annual emissions from lime kilns in Belgium and the United Kingdom have been 6 reported by Wevers and De Fre (1995) and Douben et al. (1995), respectively. However, the 7 emission factors used to generate those estimates were not provided. Umweltbundesamt (1996) 8 reported emission factors of 0.016 to 0.028 ng I-TEQDF/kg during tests at two lime kilns in 9 Germany. 10 UNEP (2005) reports that data from Europe on seven kilns, of which four were rotary 11 kilns and three were shaft kilns, showed CDD/PCDF concentrations below 0.1 ng TEQ/Nm3. 12 Measurements at two annular shaft kilns in Germany were all below 0.05 ng I-TEQ/Nm3. 13 High concentrations of CDD/PCDF have been measured at three kilns, two rotary kilns, 14 and one shaft kiln, in Sweden. The measurements made between 1989 and 1993 gave 15 concentrations between 4.1 and 42 ng N-TEQ/Nm3. All measurements of high CDD/PCDF 16 concentrations have been explained by the raw material, fuel content, or less-than-optimum 17 burning conditions, underlining the importance of controlling the kiln inputs and maintaining a 18 stable kiln operation (IPPC, 2001). 19 UNEP (2005) recommends two emission factors. For no dust controls or poor fuel, 20 10 pg I-TEQ/MT of CaO are recommended, and for kilns with good dust controls, 21 0.07 pg I-TEQ/MT of CaO are recommended. 22 In the year 2000, one facility with an SIC code for lime reported dioxin releases under the 23 EPA TRI program (U.S. EPA, 2008). The total air releases for this facility was 0.73 g, which 24 EPA estimates is equal to 0.15 g WHO98 TEQDF. The total land releases for this facility was 25 2.8 g, which EPA estimates is equal to 0.6 g WHO98 TEQDF. No releases to other media were 26 reported. As explained in Chapter 1, the TRI data are not used to make quantitative estimates in 27 this document but rather as supportive evidence that releases do occur. 28 For 2000, the emission factor of 0.0058 ng WHO98 TEQDF/kg of CaO was used on the 29 basis of "NCASI Handbook of Chemical Specific Information for SARA Section 313 Form R 30 Reporting." The factors provided in this handbook were compiled from test data supplied to 31 NCASI by a variety of sources, including NCASI member companies who had performed the This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5-20 DRAFT: DO NOT CITE OR QUOTE 1 tests in response to a regulatory program. Congener-specific CDD/CDF TEQ emission factors 2 were provided (see Table 5-1). 3 For 2000, NCASI provided estimates of activity levels for Kraft lime kilns (Gillespie, 4 2002). The activity levels were reported to be 13 MMT. Insufficient information was available 5 to make release estimates for the other reference years. 6 7 5.9.4. W ater Releases 8 No information was found suggesting that any water releases from these facilities would 9 contain CDDs and CDFs. 10 11 5.9.5. Solid Residue Releases 12 Any solid residues from these facilities would be landfilled and are not considered an 13 environmental release. 14 15 5.9.6. Products 16 No information was found suggesting that products from these facilities would contain 17 CDDs and CDFs. 18 19 5.9.7. Release Summary 20 The inventory decision criteria and releases are summarized below: 21 Inventory Decision Criteria for Lime Kilns Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 22 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 _ 2 1 DRAFT: DO NOT CITE OR QUOTE Lime Kilns_________________________________ Air Releases_________________________________ Emission Factors 1987--NA. 1995--NA. 2000--0.006 ng WHO98 TEQDF/kg of CaO.____________________________________ Activity Levels 1987--NA. 1995--NA. 2000--13 MMT._________________________________________________________ Releases 1987--NA. 1995--NA. 2000--0.1 g WHO98 TEQDF/yr.______________________________________________ W ater Releases_______________________________ No information was found suggesting that any water releases from these facilities would contain CDDs and CDFs._______________________________________________________________ Solid Residue Releases____________________________ Any solid residues from these facilities would be landfilled and are not considered an environmental release.___________________________________________________________ Products__________________________________ No information was found suggesting that products from these facilities would contain CDDs and CDFs. 1 2 3 5.10. GLASS MANUFACTURING 4 This is a new section. 5 UNEP (2005) provides an emission factor for glass manufacturing operations using dust 6 abatement of 0.015 ng I-TEQ/kg of product. This factor was based on testing at three facilities 7 in Germany. It was assumed to apply to all reference years. The amount of glass produced in 8 the United States during 1999 was 18 MMT (DOE, 2002). Data were not found for the earlier 9 years, and this value was assumed to apply to all of the reference years. 10 No information was found on CDD/CDF levels in the solid waste generated from glass 11 manufacturing. However, these residues would be landfilled and, therefore, are not considered 12 to be an environmental release. 13 The inventory decision criteria and releases are summarized below: 14 15 16 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 2 2 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Glass Manufacturing Air W ater Solids Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Products Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). 1 Q 2 Glass Manufacturing Air Releases Emission Factors 1987--0.02 ng I-TEQDF/kg of metal feed. 1995--0.02 ng I-TEQDF/kg of metal feed. 2000--0.02 ng I-TEQDF/kg of metal feed._________ Activity Levels 1987--18 MMT. 1995--18 MMT. 2000--18 MMT._____________________________ Releases 1987--0.4 g I-TEQdf. 1995--0.4 g I-TEQdf. 2000--0.4 g I-TEQdf._________________________ W ater Releases None.____________________________________________ Solid Residue Releases None.____________________________________________ Products______ None.____________________________________________ 3 4 5 6 7 8 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 - 2 3 DRAFT: DO NOT CITE OR QUOTE 1 5.11. OTHER IDENTIFIED SOURCES 2 A number of additional operations may be sources of CDD/CDF formation because the 3 processes use chlorine-containing components or involve application of high temperatures. 4 These include ceramics/rubber production facilities and plating/painting facilities which use 5 thermal air-pollution control devices. Additionally automobile shredding was identified as a 6 potential source of CDD/CDF releases. However, no testing of emissions from these processes 7 has been performed in the United States, and only minimal emission rate information has been 8 reported for these processes in other countries. Therefore, emissions from these sources are 9 possible but cannot be quantified. 10 Miscellaneous Sources________________________ Possible Air Releases_________________________ Ceramics and rubber manufacturers (Not quantifiable). Thermal air pollution control devices used at plating facilities and painting operations (Not quantifiable). Automobile shredders (Not quantifiable).________________________________________ Possible W ater Releases________________________ Ceramics and rubber manufacturers (Not quantifiable)._____________________________ 11 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5_24 DRAFT: DO NOT CITE OR QUOTE 1 Table 5-1. CDD/CDF TEQ emission factors and emission estimates from 2 Kraft lime kilns 3 Congener WHO98 TEQd f (ng/lb CaO) WHO98 TEQd f (ng/kg CaO) 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 0.00 x 100 0.00 x 100 0.00 x 100 1.00 x 10-4 0.00 x 100 2.80 x 10-4 2.56 x 10-4 0.00 x 100 0.00 x 100 0.00 x 100 2.20 x 10-4 0.00 x 100 6.16 x 10-4 5.63 x 10-4 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 8.00 x 10-4 1.00 x 10-4 0.00 x 100 9.00 x 10-4 2.00 x 10-4 0.00 x 100 0.00 x 100 0.00 x 100 0.00 x 100 0.00 x 100 1.76 x 10-3 2.20 x 10-4 0.00 x 100 1.98 x 10-3 4.40 x 10-4 0.00 x 100 0.00 x 100 0.00 x 100 0.00 x 100 0.00 x 100 Total 4 5 CaO = Calcium oxide. 2.64 x 10-3 5.80 x 10-3 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 5 _ 2 5 DRAFT: DO NOT CITE OR QUOTE 1 6. COMBUSTION SOURCES OF CDDs/CDFs MINIMALLY CONTROLLED AND 2 UNCONTROLLED COMBUSTION SOURCES 3 4 5 6.1. COMBUSTION OF LANDFILL GAS 6 6.1.1. Air Releases 7 No changes were made to the air-release estimates. The emission factor was derived by 8 averaging test results for one landfill flare in California (CARB, 1990) and one in the 9 Netherlands (Bremmer et al., 1994). This value was assumed to apply to all reference years: 10 1.4 ng I-TEQDF/m . The emission factors for the two facilities differed by a factor of six. UNEP 11 (2005) used studies from Germany and the U.K. to derive an emission factor of 8 pg I-TEQ/TJ of 12 gas burned. Assuming that the landfill gas has a heating value of 16 MJ/m (half that of natural 13 gas), this converts to 0.13 ng I-TEQ/m . Based on the limited data and inconsistency in emission 14 factors this was considered preliminary. As described in the 2006 document, survey data and 15 assumptions were used to derive activity estimates. 16 17 6.1.2. W ater Releases 18 No wet scrubbers are used for these facilities, so no releases to surface waters should 19 occur. 20 21 6.1.3. Solid Residue Releases--None 22 23 6.1.4. Products--None 24 25 6.1.5. Release Summary 26 The inventory decision criteria and releases to all media are summarized below: 27 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 1 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Landfill Gas Air Water Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Solids Products Measured emission factors consistent or have understandable differences. No Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 1 Yes P 2 3 4 ___________________________________________________ Combustion of Landfill Gas Air Releases______ Emission Factors 1987--1.4 ng I-TEQDF/m3 (Preliminary). 1995--1.4 ng I-TEQDF/m3 (Preliminary). 2000--1.4 ng I-TEQDF/m3 (Preliminary).____________ Activity Levels 1987--1.35 billion m3. 1995--4.7 billion m3. 2000--16 billion m3. Releases 1987--2 g I-TEQdf (Preliminary). 1995--7 g I-TEQdf (Preliminary). 2000--22 g I-TEQdf (Preliminary). W ater Releases_____ None.______________________________________________ Solid Residue Releases None.______________________________________________ Products________ None. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 DRAFT: DO NOT CITE OR QUOTE 1 6.2. ACCIDENTAL FIRES 2 6.2.1. Structural Fires 3 6.2.1.1. A ir R e le a se s 4 No changes were made to the air-release estimates, but additional background 5 information is provided below. 6 The most recent evidence of the release of CDD/CDFs from combustion of structures 7 was from the collapse of the World Trade Center Towers. Pleil and Lorber (2007) examined 8 dioxin congener concentrations and profiles from several fires including the fires that burned at 9 Ground Zero after the collapse of the Towers for upwards of 200 days, the Binghamton office 10 fire that occurred in the early 1980s starting from a transformer fire in the basement of the office 11 building, and an office fire from a building in Philadelphia. The air concentrations that resulted 12 from World Trade Center fires exceeded 100 pg WHO98 TEQDF/m for several ambient air 13 measurements within 500 m of the fires. The Binghamton office fire was dominated by the 14 combustion of PCBs in the transformers. The Philadelphia office fire was typical of urban 15 building structures. Pleil and Lorber (2007) looked at profiles of CDD/CDFs in impacted air, 16 dust, and soot, and compared these profiles with background profiles. While their analysis did 17 not allow for generation of an emission factor, it did produce a congener profile (see Figure 6-1). 18 The presence of manufactured boards and treated lumber in structures is expected to 19 increase dioxin emissions relative to the combustion of untreated natural wood. As discussed in 20 Section 4.2, Tame et al. (2007) reviewed the literature on the role of preservatives in the 21 formation of dioxin in the combustion of wood. They conclude that current and emerging wood 22 preservatives significantly increase dioxin formation during combustion in domestic stoves and 23 in fires. Also Bhargava et al. (2002) conducted calorimeter testing and derived emission factors 24 of 20.5 ng WHO98 TEQ/kg for chip boards and15.4 ng WHO98 TEQ/kg for medium density 25 fiberboard (MDF) compared to nondetect to 2.5 ng WHO98 TEQ/kg for natural woods. 26 The original report (U.S. EPA, 2006) recommends an emission factor of 32 pg I-TEQ/fire 27 based on averaging data from Carroll (1996) and Thomas and Spiro (1995). These were based 28 on soot measurements or other indirect methods and were assigned a preliminary confidence 29 rating. This emission factor can be converted to a mass basis by dividing by a default 30 fuel-loading factor for structural fires of 1.15 tons/fire (ERG, 2001), yielding 28 ng I-TEQ/kg. 31 This is much less than the emission factor of 400 ng I-TEQ/kg recommended by UNEP (2005). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-3 DRAFT: DO NOT CITE OR QUOTE 1 No changes were made to the activity estimates which were derived from survey data in FEMA 2 (1997, 2001) and are presented in the release summary below. 3 4 6.2.1.2. W a ter R e le a se s 5 It is possible that dioxin-contaminated particles could be entrained in water used to fight 6 fires or rainwater that falls on the site. This water could run off the site and eventually get into 7 surface waters. No quantitative release estimates could be made. 8 9 6.2.1.3. S o lid R e s id u e R e le a se s 10 Solid residue releases are possible because CDDs and CDFs have been measured in solid 11 residues remaining after structural fires. EPA (2006) summarized six field studies with residue 12 concentrations ranging from 0.03 to 130 pg I-TEQDF/kg. This wide data range is understandable 13 considering that the amount/types of treated wood and household products found in structures is 14 likely to be highly variable. The geometric mean of 2 pg I-TEQDF/kg of residue was selected as 15 a central value. This was converted to an emission factor by assuming that 15% of the fuel is 16 converted to ash (this is based on the assumption that structural fires will generate ash at a 17 similar rate as observed for bottom ash in municipal waste combustion, which is reported by 18 UNEP [2005] to be typically 10-20%). This yields an emission factor of 300 ng I-TEQDF/kg of 19 material burned, which was assumed to apply to all reference years. Based on an analysis of the 20 congener data reported by Christmann et al. (1989b) for soot from a building fire, this emission 21 factor will be the same when converted to WHO98 TEQs. This value is similar to the UNEP, 22 2005 recommendation of 400 ng I-TEQDF/kg of material burned. 23 The activity estimates used to calculate residue releases for structural fires were 24 computed by multiplying the number of fires by the default fuel-loading factor for structural fires 25 of 1.15 tons/fire (ERG, 2001). 26 27 6.2.1.4. P ro d u c ts-- N o n e 28 29 6.2.1.5. R e le a s e S u m m a ry 30 The inventory decision criteria and releases to all media are summarized below. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 4 DRAFT: DO NOT CITE OR QUOTE 1 The air-release estimates presented here are similar to those reached for national emission 2 inventories developed for the Netherlands (Bremmer et al., 1994) and the United Kingdom (U.K. 3 Department of the Environment, 1995). 4 Inventory Decision Criteria for Structural Fires Air W ater Solids Products Emission tests for at least two units/source types with No Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the class. Yes Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 5 6 Yes P Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 . 5 DRAFT: DO NOT CITE OR QUOTE Structural Fires______________________________ Air Releases_______________________________ Emission Factors 1987--32 gg I-TEQDF/fire (Preliminary). 1995--32 gg I-TEQDF/fire (Preliminary). 2000--32 gg I-TEQpF/fire (Preliminary)._____________________________________ Activity Levels 1987--746,000 fires. 1995--574,000 fires. 2000--512,000 fires._____________________________________________________ Releases 1987--24 g I-TEQDF(Preliminary). 1995--18 g I-TEQDF (Preliminary). 2000--16 g I-TEQDF(Preliminary)._________________________________________ W ater Releases______________________________ Possible but unquantifiable releases._______________________________________________ Solid Residue Releases___________________________ Emission Factors 1987--300 ng (WHO98 or I-TEQDF/kg) of material burned. 1995--300 ng (WHO98 or I-TEQDF/kg) of material burned. 2000--300 ng (WHO98 or I-TEQDF/kg) of material burned.______________________ Activity Levels 1987--860,000 tons. 1995--660,000 tons. 2000--589,000 tons._____________________________________________________ Releases 1987--260 g (WHO98 or I-TEQdf). 1995--200 g (WHO98 or I-TEQdf). 2000--180 g (WHO98 or I-TEQdf)._________________________________________ Products_________________________________ None._______________________________________________________________________ 1 2 3 6.2.2. Vehicle Fires 4 6.2.2.1. A ir R e le a se s 5 No changes were made to the air-release estimates. Wichmann et al. (1993, 1995) 6 measured CDD/CDF emissions from controlled vehicle fires in a tunnel (two cars, one subway 7 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 6 DRAFT: DO NOT CITE OR QUOTE 1 car, and one railway car). This study suggests an emission factor of 0.044 mg I-TEQDFfor cars 2 and trucks and 2.6 mg I-TEQDF/fire for other vehicles. These values were assumed for all 3 reference years. They are uncertain because Wichmann et al. (1993, 1995) based their estimates 4 on surface deposits. This procedure may not have fully accounted for volatile CDDs/CDFs, 5 which were reported by Merk et al. (1995) to account for the majority of CDDs/CDFs formed 6 during a fire. Given the indirect method of measuring emissions, they are considered 7 preliminary estimates. UNEP (2005) derived an emission factor of 0.094 mg I-TEQDF/incident. 8 This was also based on Wichmann et al. (1995) and represents an average across all vehicle 9 types. 10 The activity estimates were based on the number of vehicle fires reported in the United 11 States: approximately 561,530 in 1987 (FEMA, 1997), 406,000 in 1995 (U.S. DOC, 1997), and 12 341,600 in 2000 (FEMA, 2001). Also, the assumption was made that 99% of those fires 13 involved cars and trucks (the approximate percentage of all U.S. motor vehicles that are 14 in-service cars and trucks; U.S. DOC, 1995). 15 16 6.2.2.2. W ater R e le a se s 17 It is possible that dioxin-contaminated particles could be entrained in water used to fight 18 fires or rainwater that falls on the site. This water could run off the site and eventually get into 19 surface waters. No quantitative release estimates could be made. Therefore, this is a possible 20 but unquantifiable source. 21 22 6.2.2.3. S o lid R e s id u e R e le a se s 23 The original document (US EPA, 2006) did not address solid residue releases. Solid 24 residue releases are possible because CDDs and CDFs have been measured in solid residues 25 remaining after vehicle fires. Wichmann et al. (1995) measured an average of 26 0.01 mg I-TEQDF/fire for cars and trucks and 0.8 mg I-TEQDF/fire for other vehicles. These 27 values were adopted here for all reference years using the same data; UNEP (2005) derived a 28 solid residues emission factor of 0.018 mg I-TEQDF/incident for all vehicles. These emission 29 factors were combined with the same activity data reported above to estimate releases. 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 7 DRAFT: DO NOT CITE OR QUOTE 1 6.2.2.4. P r o d u c ts -- N o n e 2 3 6.2.2.5. R e le a s e S u m m a ry 4 The inventory decision criteria and releases to all media are summarized below: 5 Inventory Decision Criteria for Vehicle Fires Air Water Solids Products Emission tests for at least two units/source types with No Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of the Yes class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 6 7 Yes P Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 8 DRAFT: DO NOT CITE OR QUOTE Emission Factors Vehicle Fires Air Releases Cars and Trucks 1987--0.044 mg I-TEQDF/incident (Preliminary). 1995--0.044 mg I-TEQDF/incident (Preliminary). 2000--0.044 mg I-TEQDF/incident (Preliminary). O ther Vehicles 1987--2.6 mg I-TEQDF/incident (Preliminary). 1995--2.6 mg I-TEQDF/incident (Preliminary). 2000--2.6 mg I-TEQDF/incident (Preliminary). Activity Levels Cars and Trucks 1987--556,000 vehicle fires. 1995--402,000 vehicle fires. 2000--338,000 vehicle fires. O ther Vehicles 1987--5,600 vehicle fires. 1995--4,060 vehicle fires. 2000--3,400 vehicle fires.__________________ Releases Cars and Trucks 1987--24 g I-TEQdf (Preliminary). 1995--18 g I-TEQdf (Preliminary). 2000--15 g I-TEQdf (Preliminary). O ther Vehicles 1987--15 g I-TEQdf (Preliminary). 1995--11 g I-TEQdf (Preliminary). 2000--9 g I-TEQdf (Preliminary). A ll Vehicles 1987--39 g I-TEQdf (Preliminary). 1995--29 g I-TEQdf (Preliminary). 2000--24 g I-TEQdf (Preliminary).___________ 1 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 9 DRAFT: DO NOT CITE OR QUOTE Vehicle Fires (continued) W ater Releases Possible but unquantifiable releases.____________________ Solid Residue Releases Emission Factors Cars and Trucks 1987--0.01 mg I-TEQDF/incident. 1995--0.01 mg I-TEQDF/incident. 2000--0.01 mg I-TEQDF/incident. O ther Vehicles 1987--0.8 mg I-TEQDF/incident. 1995--0.8 mg I-TEQDF/incident. 2000--0.8 mg I-TEQDF/incident.______________ Activity Levels Cars and Trucks 1987--556,000 vehicle fires. 1995--402,000 vehicle fires. 2000--338,000 vehicle fires. O ther Vehicles 1987--5,600 vehicle fires. 1995--4,060 vehicle fires. 2000--3,400 vehicle fires. Releases Cars and Trucks 1987--6 g I-TEQdf. 1995--4 g I-TEQdf. 2000--3 g I-TEQDF. O ther Vehicles 1987--5 g I-TEQdf. 1995--3 g I-TEQdf. 2000--3 g I-TEQDF. A ll Vehicles 1987--11 g I-TEQdf. 1995--7 g I-TEQdf. 2000--6 g I-TEQDF. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 1 0 DRAFT: DO NOT CITE OR QUOTE 1 6.3. LANDFILL FIRES 2 6.3.1. Air Releases 3 The original report derived a preliminary release estimate from landfill fires using a per 4 capita release factor of 4 pg I-TEQ per person developed from Swedish data. This factor was 5 estimated by dividing the national release estimate for Sweden by the population. This per capita 6 approach assumes that landfill fires increase over the reference years in proportion to the 7 population. However, improved regulations and increases in methane recovery systems at 8 landfills are likely to have reduced landfill fire frequency/magnitude over this time frame. 9 Accordingly, a new approach is suggested below that does not show a downward trend. 10 Collet and Fiani (2006) reported on the measurement of PAH, PCB, and CDD/CDF 11 emission from simulated forest and landfill fires. For the landfill simulations, samples were 12 collected from two landfills located in southwest France. They collected samples from what they 13 characterized as the superficial part of the landfill ground, only the first 15 cm. These samples 14 included municipal wastes and nonhazardous industrial wastes containing various plastics, wood, 15 rubber, rags, and so on. The combustion chamber had an air flow of 1,800 nm /hour, 16 corresponding to 22.5 volume changes per hour, to simulate open burning conditions. Emissions 17 were sampled near the chamber exit and prior to the scrubber. They conducted two landfill fire 18 simulations, and the emission factors for CDD/CDFs, in ng I-TEQ/kg, were 242 and 19 233 ng I-TEQ/kg. Collet and Fiani also provided emission factors for 12 dioxin-like PCBs, in 20 ng I-TEQ/kg, and they were 9.9 and 16.6 ng I-TEQ/kg. Their landfill samples were collected 21 over a surface area of 2 m , allowing generation of emission factors on an area basis. The 22 emission factors for CDD/CDFs, in ng I-TEQ/m2, were 1380 and 1321, and for the 23 12 dioxin-like PCBs, also in ng I-TEQ/m2, were 56.3 and 94.2. 24 Persson and Bergstrom (1991) conducted experiments simulating surface and deep fires 25 and estimated an emission factor of 1000 ng Nordic TEQ/kg of material burned for landfill fires. 26 This value (assumed equal to 1000 ng I-TEQ/kg) was also adopted by UNEP (2005). This factor 27 is about four times higher than the factor developed by Collet and Fiani (2006). The midpoint of 28 this range, or 600 ng I-TEQ/kg, was adopted here for each reference year. Neither Persson and 29 Bergstrom (1991) nor Collet and Fiani (2006) reported individual congener data that would have 30 allowed converting this I-TEQ estimate to a WHO98 TEQ estimate. However, Ruokojarvi et al. 31 (1995) reported congener profiles for air concentrations measured during a landfill fire in This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-11 DRAFT: DO NOT CITE OR QUOTE 1 Finland. This profile suggest that the WHO98 TEQs would be about 20% greater than the 2 I-TEQs. On this basis, the emission factor of 600 ng I-TEQ/kg was converted to 3 700 ng WHO98 TEQ/kg. The kinds of wastes and combustion conditions occurring in landfill 4 fires are likely to be highly variable. It is very uncertain how well these are represented in the 5 limited experiments used to derive the emission factors. Therefore, this emission factor was 6 assigned a preliminary confidence rating. 7 Blomqvist et al. (2007) used an emission factor range of 40 to 900 ng TEQ/kg for landfill 8 fires in the Swedish inventory. This was based on two studies conducted in Sweden, one 9 described as a "model study on household waste" and the other as one that "quantified emissions 10 from real waste dump fires." 11 In order to use the per kg emission factors reported above, it is necessary to estimate the 12 amount of waste burned in landfill fires. Persson and Bergstrom (1991) assumed that 100,000 kg 13 of material are burned in each surface fire and 350,000 kg are burned in deep fires. The 14 midpoint of this range (225,000 kg) was multiplied by the number of landfill fires occurring in 15 the United States. The U.S. Fire Administration (USFA, 2001) reports that an average of 16 8,300 landfill fires occur each year (where landfills are defined broadly to include public or 17 private areas where waste is buried; this includes municipal solid waste landfills and general 18 refuse disposal areas and dumps in open ground). This suggests that a total of 1.9 MMT of 19 material/year are burned in landfill fires in the United States. No information was found on how 20 the number of landfill fires has changed over the reference years, and this amount (1.9 MMT) 21 was assumed to apply to each of the years. As discussed above, the actual trend is probably 22 downward because improved regulations and increases in methane recovery systems at landfills 23 are likely to have reduced landfill fire frequency/magnitude over this time frame. Considering 24 the lack of data to accurately reflect this trend and the uncertainty in the assumptions about the 25 amount of waste burned per fire, these activity estimates are considered preliminary 26 (Preliminary). 27 As shown below, this approach suggests a total release of 1,100 g I-TEQ. Another way 28 to estimate landfill fire releases is by using a per fire emission factor. Personn and Bergstrom 29 (1991) estimated that 35 g Nordic TEQ were released from landfills fires in Sweden. This 30 estimate assumed that 217 fires occurred per year (167 surface fires and 50 deep fires). This 31 implies an average release of 0.16 g Nordic TEQ/fire. Multiplying this by the number of fires This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-12 DRAFT: DO NOT CITE OR QUOTE 1 occurring in the United States (8,300/year as reported by the USFA, 2001) suggests a total 2 release of 1,300 g Nordic TEQ. This value is similar to the original one using a per capita 3 approach, which gave estimates of about 1,000 g I-TEQ/year (assuming minor differences 4 between Nordic TEQs and I-TEQs). Although these alternative approaches suggest similar 5 releases, the release estimate is still considered preliminary due to the uncertainties in both the 6 emission factor and activity estimates. 7 8 6.3.2. W ater Releases--None 9 10 6.3.3. Solid Residue Releases--None 11 12 6.3.4. Products--None 13 14 6.3.5. Release Summary 15 The inventory decision criteria and releases to all media are summarized below: 16 Inventory Decision Criteria for Landfill Fires Air W ater Solids Products Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. No Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 17 18 19 No P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 1 3 DRAFT: DO NOT CITE OR QUOTE 1 Landfill Fires_____________________________ Air Releases_____________________________ Emission Factors 1987--700 ng WHO98 TEQ/kg (600 ng I-TEQ/kg) of material burned (Preliminary). 1995--700 ng WHO98 TEQ/kg (600 ng I-TEQ/kg) of material burned (Preliminary). 2000--700 ng WHO98 TEQ/kg (600 ng I-TEQ/kg) of material burned (Preliminary). Activity Levels 1987--1.9 MMT (Preliminary). 1995--1.9 MMT (Preliminary). 2000--1.9 MMT (Preliminary).__________________________________________ Releases 1987--1,300 g WHO98 TEQdf (1,100 g I-TEQdf) (Preliminary). 1995--1,300 g WHO98 TEQdf (1,100 g I-TEQdf) (Preliminary). 2000--1,300 g WHO98 TEQdf (1,100 g I-TEQDF) (Preliminary).________________ W ater Releases____________________________ None._____________________________________________________________________ Solid Residue Releases_________________________ None._____________________________________________________________________ Products_______________________________ None. 2 3 6.4. FOREST AND BRUSH FIRES 4 6.4.1. Air Releases 5 As described below, a number of additional studies have been identified, allowing 6 updates to the air-release estimates from forest fires. 7 Ikeguchi and Tanaka (1999) simulated the open burning of several waste types using a 8 large furnace with open doors. The flue gas was sampled immediately downstream of the 9 furnace. One test was conducted with tree and leaf materials. A total of 162.7 kg of this material 10 were burned in a batch mode lasting 33 minutes. The emission factor was estimated as 11 4.7 I-TEQ/kg of waste. UNEP (2005) used this study to support their recommended emission 12 factor of 5 ng TEQ/kg of biomass burned for forest fires. 13 Gonczi et al. (2005) measured dioxin emissions from burning various types of domestic 14 wastes under a variety of conditions. One test involved the open burning of garden waste, which 15 was composed of approximately one half wood branches and one half leaves and grass. A This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 1 4 DRAFT: DO NOT CITE OR QUOTE 1 sampling hood was mounted 0.5 m above the fire to collect the emissions. This test yielded an 2 emission factor of 27 ng TEQ/kg. 3 Blomqvist et al. (2007) used an emission factor of 2 ng TEQ/kg for forest fires in the 4 Swedish inventory. This was based on work by Bhargava et al. (2002) who measured dioxin 5 emissions from the combustion of different wood materials in a cone calorimeter. 6 Collet and Fiani (2006) studied the emissions of PAHs, PCBs, and CDD/CDF emissions 7 from simulated forest and landfill fires in France. They collected samples from two forests in the 8 southeast and southwest of France during August, 2003. The samples consisted of litters, 9 mosses, heathers, brackens, conifer needles, pine cones, shrubs, barks, pine, and oak branches. 10 The 80 m3combustion chamber had an air flow of 1,800 m3/hour, corresponding to 22.5 volume 11 changes per hour, to simulate open burning conditions. Emissions were sampled near the 12 chamber exit prior to the scrubber and measured in accordance with existing European standards 13 (EN 1948-1-2-3 for CDD/CDFs and PCBs). For the five simulated forest fire tests, they 14 estimated these emission factors for CDD/CDFs, in ng I-TEQ/kg: 10.4, 1.02, 25.9, 12.1, and 3.3, 15 for an average of 10.5 ng I-TEQ/kg. Collet and Fiani also provide emission factors for 16 12 dioxin-like PCBs, in ng I-TEQ/kg: 0.48, 0.35, 2.34, 0.74, and 0.23, for an average of 17 0.8 ng I-TEQ/kg. Based on these results they provide a "first estimate" of emissions from forest 18 fires in France of 28.8 g I-TEQ/year. 19 Using a controlled-burn facility, Gullett and Touati (2003) estimated CDD/CDF 20 emissions through the testing of three biomass samples collected from the Oregon coast near 21 Seal Rock and from four biomass samples collected from the North Carolina Piedmont region, 22 approximately 200 km from the Atlantic coast. The samples generally consisted of equal 23 portions of live shoots (needles cut from tree branches) and needle litter gathered from the forest 24 floor. The Oregon samples were composed of pine needles (P in u s co n to rta and P in u s 25 m o n tic o la ) and hemlock needles (T yu g a h ete ro p h y lla ); the North Carolina samples were 26 composed entirely of lobolly pine (P inus taeda). The combustion of these seven samples, piled 27 approximately 10 cm high, took place on top of an open, flat combustion platform. The average 28 total TEQ emission factors for the three Oregon samples and the four North Carolina samples 29 were 15 ng and 25 ng WHO98 TEQDF/kg, respectively. Because the waxy cuticle layer on pine 30 needles has been demonstrated to absorb lipophilic compounds from the atmosphere, Gullett and 31 Touati (2003) also extracted a raw, as-received Oregon biomass sample to determine whether the This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-15 DRAFT: DO NOT CITE OR QUOTE 1 observed emissions were due to simple vaporization of existing CDDs/CDFs or the formation of 2 new CDDs/CDFs in the combustion process. The CDD/CDF concentration in the sample 3 measured 1.3 ng WHO9g TEQDF/kg, which is approximately 20 times lower than the Oregon 4 CDD/CDF emission factor. The CDD/CDF isomer patterns of the extracted biomass samples 5 and the emission samples were similar. Therefore, this preliminary evidence suggests CDD/CDF 6 emissions are not due solely to vaporization of cuticle-bound CDDs/CDFs but are primarily a 7 result of new formation during forest fires. 8 Gullett et al. (2008) present emission factor data for several types of forest and grass 9 fires. The study used the same burn chamber as described above for Gullett and Touati (2003). 10 Burn tests (n = 27) on forest biomass from five sources gave emission factors ranging from 0.3 11 to 26.3 ng TEQ/kg of carbon burned with an average of 5.8 ng TEQ/kg of carbon burned (the 12 TEQs were reported to be essentially the same whether presented as I-TEQs or WHO95). The 13 authors indicate that forest biomass contains approximately 50% carbon. Thus, the reported 14 emission factors can be converted to a whole biomass basis by multiplying by 0.5. The study 15 also found that the total CDD/CDF in the emissions exceeded the amounts in the raw biomass by 16 a factor of four, confirming that formation was occurring during the combustion process. 17 Meyer et al. (2004, 2007) conducted a series of chamber and field tests in Australia to 18 characterize dioxin emission from a variety of fire types. Five chamber tests were conducted 19 with forest leaf litter (eucalyptus, box, and ironbark) and producing a mean emission factor of 20 0.37 ng WHO98 TEQDF/kg of fuel. A total of 18 forest fire field tests were conducted using 21 portable high volume air samplers. The field monitors also measured CO2, which was related to 22 combusted biomass and used to calculate emission factors. The field test results are summarized 23 below: 24 25 Ten prescribed burns in Queensland (coastal forest), Victoria (eucalyptus), and Western 26 Australia (jarrah forest) with a mean emission factor of 0.5 ng WHO98 TEQDF/kg of fuel. 27 Three fires in tropical savannas with a mean emission factor of 1.1 ng WHO98 TEQDF/kg 28 of fuel. 29 Two wildfires in Victoria (mixed eucalyptus) with a mean emission factor of 30 0.7 ng WHO98 TEQDF/kg of fuel. 31 Three woodland fires with a mean emission factor of 1.5 ng WHO98 TEQDF/kg of fuel. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-16 DRAFT: DO NOT CITE OR QUOTE 1 6.4.2. Air Emission Factors 2 Several lines of evidence indicate that forest fires release dioxins to the environment. 3 Sediment core studies have shown that dioxins were found at measurable levels prior to the 4 industrial revolution (Smith et al., 1992, 1993). The most likely source for these residues is 5 natural fires. Gullett et al. (2003, 2008) used chamber tests to show that more dioxins are 6 emitted than contained in the biomass being burned. Finally, multiple chamber studies and 7 one large field study (summarized above) have now measured dioxins in forest fire emissions. 8 Thus, it is reasonably well established that dioxin emissions occur from forest fires. 9 The chamber studies have shown a wide range of results (means across tests vary from 10 0.37 to 25 ng TEQ/kg) suggesting that emissions are highly variable across fuel types and fire 11 conditions. The Australian field measurements suggest emission factors near the low end of the 12 chamber results. Meyer et al. (2004) believe that the chamber tests have overestimated dioxin 13 emissions due to longer residence time in the formation temperatures than occurs in the field. 14 They also support their belief that forest fires have low dioxin emissions on the basis of ambient 15 air monitoring in southern Victoria during the large forest fires in northeast Victoria in January 16 2003. The monitor showed clear impacts of the plume during the fire based on sharp increases in 17 particulate and potassium salts (biomass tracer) but no increases in dioxins. 18 As summarized in Table 6-1, a total of 6 chamber studies have been conducted with a 19 variety of wood types and a cumulative n of 46. Also, as summarized in Table 6-1, one large 20 field study was conducted in Australia involving various types of forests with an n of 18. The 21 n-weighted average for the field tests is 0.8 ng TEQDF/kg and for the chamber tests is 22 5.9 ng TEQDF/kg. As discussed below, both types of tests have uncertainties, and the midpoint 23 of this range (3 ng TEQDF/kg) was selected as a reasonable assumption for a central value 24 emission factor and applied to all three reference years. 25 The confidence in this emission factor depends on how representative the test data are of 26 the types of wood and fires that occur in North America: 27 28 Wood types--Over 20 different types of forests exist in the United States (see Figure 6-2) 29 with a variety of wood types, biomass density, moisture content, height, etc. The 30 chamber tests did not represent all wood types found in North America but did include 31 some common types such as pine and oak. All of the field tests were conducted in This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 1 7 DRAFT: DO NOT CITE OR QUOTE 1 Australia; some included pines, but others were primarily eucalyptus and jarrah trees, 2 which are uncommon in the United States. 3 Fire types--A number of different types of fires can occur such as ground fires, which 4 burn the humus layer of the forest floor but do not burn appreciably above the surface; 5 surface fires, which burn forest undergrowth and surface litter; and crown fires, which 6 advance through the tops of trees or shrubs. It is not uncommon for two or three of the 7 types to occur simultaneously. The ground level monitors cannot directly sample the 8 high smoke plume generated near the tops of trees during a crown fire. Some of the 9 smoke generated during a crown fire is present at ground level, but it is uncertain how 10 representative this smoke is of the main plume. Ground/surface fires create a smoke 11 plume, which starts near ground level, and the monitors are much more likely to collect 12 samples, which are representative of these emissions. Similarly, the chamber tests cannot 13 mimic the intensity and scale of crown fires but may be representative of the conditions 14 associated with the smaller ground/surface fires. 15 16 In summary, the forest fire data appear to represent some but not all of the wood types 17 and fire types that occur in North America. The large database of emission tests suggest a wide 18 range of emission factors, but this is reasonable considering that they cover a wide variety of 19 wood types, fire types and burn conditions. The wide range of results increases the confidence 20 that the full range of emission factors have been characterized and that the midpoint of the range 21 provides a reasonable central point estimate. On this basis, the emission factor has been 22 upgraded from preliminary to quantifiable. 23 24 6.4.3. Air Activity Levels 25 EPA (2006) derived forest fire activity estimates using data on acres burned per year and 26 estimates of the amount of biomass per acre. New data for acres burned were found at a 27 database managed by the National Interagency Fire Center (NIFC) (www.nifc.gov/fire). These 28 new data are compared to the previously used data in Table 6-2. The data are generally 29 comparable except for the wildfire data for 1987 and 1995 where the NIFC data are less than half 30 the previously used values. These two estimates were changed to reflect these new data. The 31 amount of biomass burned per acre was assumed to be 9.43 MT/acre for wildfires and 32 7.44 MT/acre for prescribed burns (Ward et al., 1976). The total forest fire activities were 33 estimated as 61 MMT in 1987, 55 MMT in 1995 and 243.8 MMT in 2000. A review of the 34 NFIC historical data on wildfires from 1960 to 2008 suggests that the acres burned in 2000 were 35 above average and the acres burned in 1987 and 1995 were below average. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-18 DRAFT: DO NOT CITE OR QUOTE 1 6.4.4. W ater Releases 2 It is possible that dioxin-contam inated particles could be entrained in w ater used to fight 3 fires or rainw ater that falls on the site. This w ater could run o ff the site and eventually get into 4 surface w aters. N o quantitative release estim ates could be m ade. Therefore, this is a possible 5 but unquantifiable source. 6 7 6.4.5. Solid Residue Releases 8 B uckland et al. (1994) collected soil sam ples in a national park near Sydney, A ustralia. 9 Som e w ere collected in areas w here large brush fires had occurred 6 w eeks earlier and others in 10 areas w h ere no fires had occurred. T he sam pling depth w as 2 cm . T he d io x in co n ten t o f 11 sa m p le s fro m b u rn t a reas ra n g e d fro m 2 .2 to 36.8 p g I-T E Q /g , a n d th e sa m p le s fro m u n b u rn t 12 areas ranged from 3.0 to 10.0 pg I-T E Q /g. T hey co n clu d ed th at th e fires had n o t had a m ajo r 13 im p a c t o n th e soil levels. 14 N o o th er d irect m easu res o f C D D /C D F co n ten t o f fo rest fire ash w ere found. W underli 15 et al. (1 9 9 6 ) d e te rm in e d an a v e ra g e o f 10 n g I-T E Q /k g o f a sh g e n e ra te d fo r c le a n w o o d b u rn e d in 16 stoves. T his v alu e is sim ilar to th e levels m easu red by B u ck lan d et al. (1994) in surface soils 17 after fires and is assu m ed here fo r fo rest fires. U N E P (2005) reco m m en d ed 4 ng I-T E Q /k g o f 18 m aterial b u rn e d (th is w as d eriv ed fro m an estim ate o f 200 n g I-T E Q /k g o f ash and assu m p tio n o f 19 2% ash). T his em issio n facto r is assig n ed a p relim in ary co n fid en ce ratin g b ecau se direct 20 m easurem ents w ere available from only one area/fire type and it is unclear if it is representative 21 o f other areas. 22 The ash yield from w ood grow n in tem perate zones is 0.1 to 1%, and bark produces 3 to 23 8% ash (R agland et al., 1991). A m idrange value o f 3% is assum ed here for all w ood burned. 24 M ultiplying this value by the activity factors discussed above for biom ass burned in fires yields 25 th e follow ing: 1.8 M M T in 1987, 1.7 M M T in 1995, and 7.3 M M T in 2000. 26 27 6.4.6. Products--None 28 29 6.4.7. Release Summary 30 The inventory decision criteria and releases to all m edia are sum m arized below : 31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 1 9 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Forest and Brush Fires Air W ater Solids Em ission tests for at least tw o units/source types w ith Yes Yes sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable differences. Yes Yes Em ission factor tests represent units that are typical o f the class. Yes No A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 Yes Q Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 0 DRAFT: DO NOT CITE OR QUOTE Forest and Brush Fires Air Releases Emission Factors 1987--3 ng WHO98 TEQDF/kg. 1995--3 ng WHO98 TEQDF/kg. 2000--3 ng WHO98 TEQDF/kg._________________ Activity Levels 1987--61 MMT. 1995--55 MMT. 2000--243.8 MMT.__________________________ Releases 1987--180 g WHO98 TEQdf. 1995--170 g WHO98 TEQdf. 2000--730 g WHO98 TEQdf.___________________ W ater Releases None.____________________________________________ Solid Residue Releases Emission Factors 1987--10 ng I-TEQDF/kg ash (Preliminary). 1995--10 ng I-TEQDF/kg ash (Preliminary). 2000--10 ng I-TEQDF/kg ash (Preliminary)._______ Activity Levels 1987--1.8 MMT ash. 1995--1.7 MMT ash. 2000--7.3 MMT ash._________________________ Releases 1987--18 g I-TEQdf (Preliminary). 1995--17 g I-TEQdf (Preliminary). 2000--73 g I-TEQdf (Preliminary).______________ Products______ None.____________________________________________ 1 2 3 6.5. BACKYARD BARREL BURNING 4 6.5.1. Air Releases 5 A dditional studies are presented below , and changes w ere m ade to the 2000 activity 6 estim ate and resulting release estim ate. 7 8 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 1 DRAFT: DO NOT CITE OR QUOTE 1 Hirai et al (2003) estimated total CDD/F emission factors from soil measurements at 2 open burning sites. Soil concentrations in India of 52 pg TEQ/g implied an emission factor over 3 500 pg TEQ/g of waste. Soil concentrations in Cambodia of 400 pg TEQ/g implied an emission 4 factor over 4000 pg TEQ/g of waste. 5 Wevers et al. (2004) measured dioxin emissions from the combustion of garden waste in 6 barrels and in open fires, and the incineration of household waste in an empty oil drum. Each set 7 of experiments was composed of eight individual experiments over 4 hours. Air samples were 8 taken in the plume with a medium volume sampler equipped with a quartz filter and a 9 polyurethane plug. Emission factors in the order of magnitude of 4.5 ng TEQ/kg combusted 10 garden waste and 35 ng TEQ/kg burned municipal waste were determined. 11 Hedman et al. (2005) measured the emissions of CDD/CDFs and PCBs from 12 uncontrolled domestic combustion of waste. The waste fuels used were garden waste, paper, 13 paper and plastic packaging, refuse-derived fuel (RDF), PVC, and electronic scrap. Samples 14 were collected from the emissions drawn through a conical fume hood placed directly over the 15 barrel. Combustions including PVC and electronic scrap emitted several orders of magnitude 16 more dioxins than the other waste fuels. Emissions from the other fuels had considerable 17 variations, but the levels were difficult to relate to waste composition. Emission factors of 18 CDD/CDF and PCB from the backyard burning ranged from 2.2 to 13,000 ng (WHO TEQ)/kg. 19 The levels found in ash usually were less than 5% of the total. For assessment of total emissions 20 of dioxins and PCB from backyard burning of low and moderately contaminated wastes, an 21 emission factor range of 4-72 ng WHO TEQ/kg is suggested. 22 Gonczi et al. (2005) tested emissions from burning domestic wastes in barrels (19 tests) 23 and open fires (2 tests). Gas collected above these fires allowed for estimation of emission 24 factors for CDD/CDFs and dioxin-like PCBs for barrel burn and open fire conditions. The 25 material burned consisted of various mixtures of garden wastes, straw, paper, several forms of 26 plastic, waste motor oil, RDF, and computer scrap. A barrel burn with a mix of garden waste 27 and polyvinyl chloride (PVC) waste had the highest emission factor of 28 96,000 ng WHO98 TEQDF/kg burned. The other emission tests ranged from 2.2 to 29 890 ng WHO98 TEQP/kg burned. 30 The emission factor selected in the original report was 76.8 ng WHO98 TEQDF/kg 31 (72.8 ng I-TEQDF/kg) based on studies by Gullett et al. (1999, 2000) and Lemieux et al. (2000). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-22 DRAFT: DO NOT CITE OR QUOTE 1 This falls w ithin the range found by G onczi et al. (2005), about tw ice the level found by W everes 2 et al. (2004) and n ear the u p p er end o f the range recom m ended by H edm an et al. (2005). 3 A ccordingly, the original em ission factor still appears to be a reasonable central estim ate, and no 4 changes w ere made. 5 The original report (US EPA , 2006) presented data from six surveys on the prevalence o f 6 backyard trash burning. This data w as com bined w ith trash generation rates and C ensus data on 7 rural populations to derive national estim ates o f the am ount o f trash burned in backyards for each 8 o f the reference years. The original report also described an alternative activity estim ate for 9 2000 developed by O A Q PS. The alternative m ethod used sim ilar factors applied on a county by 10 county b asis and m ad e ad ju stm en ts fo r am o u n t o f w aste recy cled and in flu en ce o f o pen b u rn in g 11 b an s. T h e p re se n t re p o rt c o n sid e re d th e O A Q P S m e th o d m o re a c c u ra te a n d a d o p te d it fo r th e 12 y ea r 2000. T his resu lted in a 16% in crease in activity and a co rresp o n d in g in crease in releases in 13 2 0 0 0 . N o c h a n g e s w e re m a d e to th e re le a se e stim a te s fo r 1987 an d 1995. A ll a c tiv ity e stim a te s 14 are p resen ted in the release sum m ary below . 15 16 6.5.2. Solid Residue Releases 17 M in h et al. (2003) m easu red C D D s and C D F s in soils from open b u rn in g dum p sites for 18 m u n icip al w a ste in th e P h ilip p in es, C am b o d ia, India, and V ietnam . A v e rag e lev els acro ss sites 19 ra n g e d fro m 2 to 520 p g W H O 98 T E Q /g . T h e le v e ls w e re h ig h e r th a n th o se in a g ric u ltu ra l an d 20 urban areas distant from the dum p sites. 21 L em ieux (1997) collected ash sam ples from open barrel burning and analyzed them for 22 CD D s/CD Fs. A sh sam ples from the experim ents w ere com bined, resulting in tw o com posite 23 sam ples, one for recyclers, and one for nonrecyclers. The average o f the recycler and 24 nonrecycler values w ere averaged and assum ed to apply to all three reference years: 1,670 ng 25 W H O 98 T E Q DF/k g (1 ,6 4 0 n g I-T E Q DF/k g ) o f ash. 26 The generation rate o f ash from backyard barrel burning is assum ed to m atch that o f 27 m unicipal w aste incineration, w hich has a central estim ate o f 15% for bottom ash as discussed in 28 Section 3.1. A pplying this to the total am ount burned (as discussed above) yields these activity 29 levels fo r each reference year: 1.2 M M T in 1987, 1.2 M M T in 1990, and 1.2 M M T in 2000. 30 The solid residue releases w ere estim ated by m ultiplying the em ission factor and activity 31 level fo r each referen ce y ea r (results show n in sum m ary ch art below ). It is p o ssib le th at som e o f This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-23 DRAFT: DO N O T CITE OR QUO TE 1 the ash from barrel burning is taken to m unicipal w aste landfills, but m ost is probably not. 2 Therefore, all o f these releases are assum ed to occur to the open environm ent. 3 4 6.5.3. Release Summary 5 The inventory decision criteria and releases to all m edia are sum m arized below : 6 Inventory Decision Criteria for Backyard Barrel Burning Air W ater Solids Em ission tests for at least tw o units/source types w ith Yes Yes sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable differences. Yes Yes Em ission factor tests represent units that are typical o f the class. Yes Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 7 8 Yes Q Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 4 DRAFT: DO NOT CITE OR QUOTE Backyard Barrel Burning_________ Air Releases______________ Emission Factors 1987--77 ng WHO98 TEQDF/kg (73 ng I-TEQDF/kg). 1995--77 ng WHO98 TEQDF/kg (73 ng I-TEQDF/kg). 2000--77 ng WHO98 TEQDF/kg (73 ng I-TEQDF/kg).__________ Activity Levels 1987--7.87 MMT. 1995--8.18 MMT. 2000--7.79 MMT.____________________________________ Releases 1987--610 g WHO98 TEQdf (570 g I-TEQdf). 1995--630 g WHO98 TEQdf (600 g I-TEQdf). 2000--600 g WHO98 TEQdf (570 g I-TEQdf)._______________ W ater Releases_____________ None______________________________________________________ Solid Residue Releases__________ Emission Factors 1987--1,700 ng WHO98 TEQDF/kg (1,600 ng I-TEQDF/kg) of ash. 1995--1,700 ng WHO98 TEQDF/kg (1,600 ng I-TEQDF/kg) of ash. 2000--1,700 ng WHO98 TEQDF/kg (1,600 ng I-TEQDF/kg) of ash. Activity Levels 1987--1.2 MMT. 1995--1.2 MMT. 2000--1.2 MMT.______________________________________ Releases 1987--2,000 g WHO98 TEQdf (1,900 g I-TEQdf). 1995--2,000 g WHO98 TEQdf (2,000 g I-TEQdf). 2000--2,000 g WHO98 TEQdf (1,900 g I-TEQdf).____________ Products________________ None.______________________________________________________ 1 2 3 4 5 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 5 DRAFT: DO NOT CITE OR QUOTE 1 6.6. RESIDENTIAL YARD WASTE BURNING 2 Additional studies are presented below, and changes were made to the release estimates. 3 4 6.6.1. Air Releases 5 Ikeguchi and Tanaka (1999) simulated the open burning of several waste types using a 6 large furnace with open doors. The flue gas was sampled immediately downstream of the 7 furnace. One test was conducted with tree and leaf materials. A total of 162.7 kg of this material 8 were burned in a batch mode lasting 33 minutes. The emission factor was estimated as 9 4.7 I-TEQ/kg of waste. 10 Gonczi et al. (2005) measured dioxin emissions from burning various types of domestic 11 wastes under a variety of conditions. One test involved the open burning of garden waste, which 12 was composed of approximately one half wood branches and one half leaves and grass. A 13 sampling hood was mounted 0.5 m above the fire to collect the emissions. This test yielded an 14 emission factor of 27 ng TEQ/kg. 15 Wevers et al. (2004) measured dioxin emissions from the combustion of garden waste in 16 barrels and in open fires, and the incineration of household waste in an empty oil drum. Each set 17 of experiments was composed of eight individual experiments over 4 hours. Air samples were 18 taken in the plume with a medium volume sampler equipped with a quartz filter and a 19 polyurethane plug. For garden waste, an emission factors of 4.5 ng TEQ/kg of waste was 20 determined. 21 Hedman et al. (2005) measured the emissions of CDD/CDFs and PCBs from 22 uncontrolled burning of various forms of household waste. Samples were collected from the 23 emissions drawn through a conical fume hood placed directly over the barrel. For burns with 24 garden waste (n = 3), CDD/CDF emission factors ranged from 12 to 100 ng WHO98 TEQ/kg of 25 material burned with a median value of 20 ng WHO98 TEQ/kg of material burned. 26 The studies summarized above had central values ranging from about 4 to 27 27 ng WHO98 TEQ/kg of material burned. A midrange value of 10 ng WHO98 TEQ/kg of 28 material burned was selected as an overall central estimate. 29 As described in the original report, OAQPS estimated that 255,000 MT of leaf and 30 255,000 MT of brush (total of 510,000 MT of yard waste) were burned in 2000. Estimates for 31 1987 and 1995 were derived by assuming that the activities would be proportional to the total This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-26 DRAFT: DO NOT CITE OR QUOTE 1 U.S. population for these years. This approach yields the following activity levels for each 2 reference year: 441,000 MT in 1987, 485,000 MT in 1995, and 510,000 MT in 2000. 3 4 6.6.2. W ater Releases--None 5 6 6.6.3. Solid Residue Releases 7 Hedman et al. (2005) measured an ash emission factor of 0.02 ng WHO98 TEQ/kg of 8 waste burned for barrel burning of garden waste. It is assigned a preliminary confidence rating 9 because it is based on only one waste sample. 10 11 6.6.4. Products--None 12 13 6.6.5. Release Summary 14 The inventory decision criteria and releases to all media are summarized below: 15 Inventory Decision Criteria for Residential Yard Waste Burning Air W ater Solids Products Emission tests for at least two units/source types with Yes No sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Emission factor tests represent units that are typical of Yes the class. Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 16 17 18 Yes Q Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 7 DRAFT: DO NOT CITE OR QUOTE 1 Residential Yard Waste Burning_______ Air Releases________________ Emission Factors 1987--10 ng WHO98 TEQDF/kg. 1995--10 ng WHO98 TEQDF/kg. 2000--10 ng WHO98 TEQDF/kg.____________________________ Activity Levels 1987--441,000 MT. 1995--485,000 MT. 2000--510,000 MT._______________________ Releases 1987--4 g WHO98 TEQdf. 1995--5 g WHO98 TEQdf. 2000--5 g WHO98 TEQdf.________________________________ W ater Releases______________ None._______________________________________________________ Solid Residue Releases___________ Emission Factors 1987--0.02 ng WHO98 TEQDF/kg of material burned (Preliminary). 1995--0.02 ng WHO98 TEQDF/kg of material burned (Preliminary). 2000--0.02 ng WHO98 TEQDF/kg of material burned (Preliminary). Activity Levels 1987--441,000 MT. 1995--485,000 MT. 2000--510,000 MT.______________________________________ Releases 1987--<0.1g WHO98 TEQdf (Preliminary). 1995--<0.1 g WHO98 TEQdf (Preliminary). 2000--<0.1 g WHO98 TEQdf (Preliminary).___________________ Products_________________ None._______________________________________________________ 2 3 4 6.7. LAND-CLEARING DEBRIS BURNING 5 6.7.1. Air Releases 6 The emission factor was changed to correspond to the new forest fire emission factor. No 7 direct measurements of CDD/CDF emissions from the burning of land-clearing debris have been 8 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 8 DRAFT: DO NOT CITE OR QUOTE 1 performed, so the average emission factor of 3 ng WHO98 TEQDF/kg, which was used for forest 2 fires is also used for burning of land-clearing debris. This factor was assumed to apply to all 3 three reference years. A preliminary confidence rating was assigned to the emission factor 4 estimate because it was derived from forest fire testing and may not be representative of 5 land-clearing debris burning. 6 No changes were made to the activity level estimates. As described in EPA (2006), these 7 were provided by OAQPS and involved multiplying estimates of acres cleared during residential, 8 nonresidential, and roadway construction by the fuel-loading factors. 9 10 6.7.2. W ater Releases--None 11 12 6.7.3. Solid Residue Releases 13 Wunderli et al. (1996) determined an average of 10 ng I-TEQ/kg of ash generated for 14 clean wood. This value is recommended by UNEP (2005) for virgin biomass fired stoves and is 15 adopted here for ash from land-clearing debris burning. It is assigned a preliminary confidence 16 rating because ash from land-clearing debris burning may be different from stove ash. 17 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to 18 8% ash (Ragland et al., 1991). A midrange value of 3% is assumed here for all debris burned. 19 Multiplying this value by the activity factors discussed above for land clearing debris fires yields 20 the following: 831,000 MT in 1987, 792,000 MT in 1995, and 852,000 MT in 2000. 21 22 6.7.4. Release Summary 23 The inventory decision criteria and releases to all media are summarized below: 24 25 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 2 9 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Land-Clearing Debris Burning Air W ater Solids Em ission tests for at least tw o units/source types w ith No No sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. No No A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 Yes P Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 0 DRAFT: DO NOT CITE OR QUOTE Land-Clearing Debris Burning Air Releases________ Emission Factors 1987--3 ng WHO98 TEQDF/kg (Preliminary). 1995--3 ng WHO98 TEQDF/kg (Preliminary). 2000--3 ng WHO98 TEQDF/kg (Preliminary).__________ Activity Levels 1987--27.7 MMT. 1995--26.4 MMT. 2000--28.4 MMT._______________________________ Releases 1987--83 g WHO98 TEQdf (Preliminary). 1995--79 g WHO98 TEQdf (Preliminary). 2000--85 g WHO98 TEQdf (Preliminary).____________ W ater Releases_______ None._______________________________________________ Solid Residue Releases Emission Factors 1987--10 ng I-TEQDF/kg of ash (Preliminary). 1995--10 ng I-TEQDF/kg of ash (Preliminary). 2000--10 ng I-TEQDF/kg of ash (Preliminary)._________ Activity Levels 1987--0.831 MMT ash. 1995--0.792 MMT ash. 2000--0.852 MMT ash.___________________________ Releases 1987--8 g WHO98 TEQdf (Preliminary). 1995--8 g WHO98 TEQdf (Preliminary). 2000--9 g WHO98 TEQdf (Preliminary)._____________ Products_________ None._______________________________________________ 1 2 3 6.8. UNCONTROLLED COMBUSTION OF POLYCHLORINATED BIPHENYLS 4 N o new studies w ere found on this topic, and no changes w ere m ade to the release 5 estim ate. The use o f P C B s in new transform ers in the U nited States is banned, and their use in 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 1 DRAFT: DO NOT CITE OR QUOTE 1 existing transform ers and capacitors is being phased out under regulations prom ulgated under the 2 Toxic Substances Control A ct. 3 B ecause o f the accidental nature o f these incidents, the variation in duration and intensity 4 o f elevated tem peratures, the variation in CD D /C D F content o f residues, and the uncertainty 5 regarding the am ount o f P C B s still in service in electrical equipm ent, E P A judged the available 6 data inadequate for developing any quantifiable em ission estim ates. Therefore, they are 7 considered unquantifiable for air and solid residue releases. Inform ation on this source is also 8 p resen ted in C h ap ter 11. Uncontrolled Combustion of PCBs_______________________ C D D s and C D Fs have been detected in soot from PC B fires, but the available inform ation is insufficient to m ake quantitative release estim ates. Therefore, it is considered an unquantifiable source for air and solid residue releases. 9 6.9. VOLCANOES 10 N o evidence exists th at th is source can release C D D s/C D F s and, therefore, it is n o t even 11 c o n sid e re d u n q u a n tifia b le . 12 6.10. FIREWORKS 13 N o n e w stu d ies w e re fo u n d o n th is to p ic , a n d n o c h a n g e s w e re m a d e to th e re le a se 14 estim ate. E v id en ce exists th at firew orks can release C D D s/C D F s to th e air and solid residues, 15 b u t in s u ffic ie n t in fo rm a tio n ex ists to m a k e a q u a n tita tiv e estim ate. T h e re fo re , it is c o n sid e re d 16 u n q u an tifiab le fo r air and solid resid u e releases. 17 Fireworks_______________________________ C D D s and CD Fs have been detected in firew orks ash and in air after using firew orks, but the available inform ation is insufficient to m ake quantitative release estim ates. Therefore, it is c o n sid e re d an u n q u a n tifia b le so u rc e fo r a ir a n d so lid re sid u e re le ases.________________________ 18 6.11. OPEN BURNING AND OPEN DETONATION OF ENERGETIC MATERIALS 19 N o ev id en ce ex ists th at th is source can release C D D s/C D F s, and, therefore, it is n o t even 20 considered unquantifiable. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 2 DRAFT: DO NOT CITE OR QUOTE 1 6.12. UNDERGROUND COAL FIRES 2 U nderground coal fires are a possible source o f C D D /C D Fs to the air because C D D /CD F 3 releases have been m easured from other form s o f coal burning. H ow ever, no em issions data or 4 activity inform ation w ere found specifically for this source, so no quantitative release estim ate 5 could be m ade (N ot quantifiable). 6 Underground Coal Fires____________________________ The available inform ation is insufficient to m ake quantitative release estim ates (N ot quantifiable). 7 8 6.13. AGRICULTURAL BURNING 9 This source category w as not included in the original report. A gricultural fields are 10 som etim es b u rn ed p rio r to h arv estin g to facilitate crop co llectio n and som etim es after harv estin g 11 to c le a r th e fie ld s a n d c o n tro l w e e d s. In th e U n ite d S ta te s, it is b e lie v e d th a t th is p ra c tic e is m o s t 12 p rev alen t fo r su g ar cane, and it is th e o n ly crop ad d ressed in th is section. 13 14 6.13.1. Air Releases 15 G u lle tt et al. (2 0 0 6 ) m e a su re d d io x in e m issio n fro m sim u la te d su g a rc a n e fie ld b u rn s. 16 S u g arcan e leav es from H aw aii and F lo rid a w ere b u rn ed in a m an n er sim ulating th e natural 17 physical d im en sio n s and b io m ass d en sity fo u n d du rin g th e p ractice o f p reh arv est field burning. 18 E ig h t co m p o site b u rn te sts co n sistin g o f 3 -3 3 kg o f b io m ass w ere conducted, som e w ith 19 rep licate sam plers. E m issio n facto r calcu latio n s u sin g sam pled co n cen tratio n and m easu red 20 m ass loss com pared w ell to rigorous carbon balance m ethods com m only used in field sam pling. 21 T he tw o sources of sugarcane had distinctive em ission levels, as did tests on separate seasonal 22 gatherings of the Florida sugarcane. The average em ission factor for tw o tests of H aw aii 23 sugarcane w as 114 ng TEQ /kg o f biom ass and for tw o gatherings o f F lorida sugarcane w as 24 11 n g T E Q /k g b io m a s s a n d 2 n g T E Q /k g b io m a ss (th e se v a lu e s w e re o rig in a lly re p o rte d o n a 25 carbon basis and w ere converted to a total biom ass basis by m ultiplying by 45% ). 26 M ey er et al. (2004) conducted a series o f cham ber and field tests in A u stralia to 27 characterize dioxin em issions from a variety of fire types including agricultural fires. The m ean 28 em ission factors from the cham ber tests are listed below : 29 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 3 DRAFT: DO NOT CITE OR QUOTE 1 Straw--17 ng WHO98 TEQDF/kg of fuel. 2 Sorghum--35 ng WHO98 TEQDF/kg of fuel. 3 Sugar cane--5 ng WHO98 TEQDF/kg of fuel. 4 5 Additionally, two field tests were conducted during sugar cane burning. These tests used 6 portable high volume air samplers. The field monitors also measured CO2, which was related to 7 combusted biomass and used to calculate emission factors. The emission factor was 8 1 .2 ng WHO98 TEQDF/kg of fuel. 9 UNEP (2005) recommended an emission factor for agricultural residue burning of 10 30 ng I-TEQ/kg of material burned (in fields where pesticides or other contaminants are present) 11 and 0.5 ng I-TEQ/kg of material burned (in fields where pesticides or other contaminants are not 12 present). 13 In summary, sugar cane chamber tests have produced a very wide range of emission 14 factors from 2 to 114 ng TEQ/kg. The limited field testing yielded an emission factor of 15 1 ng TEQ/kg. Accordingly, there is considerable uncertainty about what value is most 16 representative of U.S. conditions. For the purposes of a preliminary estimate, a value of 17 10 ng TEQ/kg (rounded geometric mean of range) was selected. 18 Gullett et al. (2006) derived activity estimates for sugar cane burning in the United States 19 using the following factors: the sugar cane field area for Hawaii, Texas, Louisiana, and Florida; a 20 biomass production rate of 20 dry tons/ha; and the assumption that 50% of the sugar cane crop 21 was burned with 90% combustion efficiency. This approach suggests that about 3.5 MMT of 22 sugar cane were burned. The data were from the 2001-2003 time frame and are assumed here to 23 apply to 2000. USDA (2009) indicates that sugar cane production increased by about 10% from 24 1995 to 2000, and a similar amount is assumed for 1987 to 1995. On this basis, the amount of 25 sugar cane burned in 1987 was 2.8 MMT, and the amount in 1995 was 3.1 MMT. Considering 26 the multiple assumptions required for this estimate, it is assigned a preliminary confidence 27 rating. 28 29 6.13.2. W ater Releases--None 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 4 DRAFT: DO NOT CITE OR QUOTE 1 6.13.3. Solid Residue Releases 2 Gullett et al. (2006) measured the dioxin content of ash from several samples with a 3 range of 0.004 to 1.22 ng WHO98 TEQ/kg of initial carbon of the biomass. Meyer et al. (2004) 4 measured the dioxin content of sugar cane ash as 1 ng WHO98 TEQ/kg of carbon. An emission 5 factor of 1 ng WHO98 TEQ/kg of carbon was selected as a central value within the range 6 observed by Gullett et al. (2006). It was converted to 0.5 ng TEQ/kg of biomass burned 7 assuming 45% carbon in the biomass. UNEP (2005) recommends a higher land emission factor 8 for agricultural residue burning of 10 ng I-TEQ/kg of material burned, but the basis was not 9 clear. Based on the limited testing showing widely ranging results, it was assigned a preliminary 10 confidence rating. 11 12 6.13.4. Products--None 13 14 6.13.5. Release Summary 15 The inventory decision criteria and releases to all media are summarized below: 16 Inventory Decision Criteria for Suga r Cane Burning Air Water Solids Products Emission tests for at least two units/source types with Yes Yes sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Emission factor tests represent units that are typical of the class. No Yes No Yes Activity estimates based on source-specific surveys. Conclusion (Q = Quantitative, P = Preliminary). 17 18 Yes P Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 5 DRAFT: DO NOT CITE OR QUOTE 1 2 Sugar Cane Burning_____ Air Releases_________ Emission Factors 1987--10 ng WHOgg TEQDF/kg of biomass (Preliminary). 1995--10 ng WHO98 TEQDF/kg of biomass (Preliminary). 2000--10 ng WHO98 TEQDF/kg of biomass (Preliminary). Activity Levels 1987--2.8 MMT (Preliminary). 1995--3.1 MMT (Preliminary). 2000--3.5 MMT (Preliminary).______________________ Releases 1987--28 g WHO98 TEQdf (Preliminary). 1995--31 g WHO98 TEQdf (Preliminary). 2000--35 g WHO98 TEQdf (Preliminary)._____________ W ater Releases_______ None.________________________________________________ Solid Residue Releases____ Emission Factors 1987--0.5 ng WHO98 TEQDF/kg of biomass (Preliminary). 1995--0.5 ng WHO98 TEQDF/kg of biomass (Preliminary). 2000--0.5 ng WHO98 TEQDF/kg of biomass (Preliminary). Activity Levels 1987--2.8 MMT (Preliminary). 1995--3.1 MMT (Preliminary). 2000--3.5 MMT (Preliminary).______________________ Releases 1987--1 g WHO98 TEQdf (Preliminary). 1995--2 g WHO98 TEQdf (Preliminary). 2000--2 g WHO98 TEQdf (Preliminary).______________ Products__________ None.________________________________________________ 3 4 5 6.14. OPEN BURNING DEMOLITION/CONSTRUCTION WOOD 6 6.14.1. Air Releases 7 This is a new section. N o direct m easurem ents o f C D D /C D F em issions from the open 8 burning o f dem olition/construction w ood w ere found. H ow ever, this activity involves sim ilar 9 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 6 DRAFT: DO NOT CITE OR QUOTE 1 material as burned in structural fires. As discussed in Section 6.2.1, the presence of 2 manufactured boards and treated lumber in structures is expected to increase dioxin emissions 3 relative to the combustion of untreated natural wood. Section 6.2.1 derived a structural fire 4 emission factor of 32 pg I-TEQ/fire by averaging data from Carroll (1996) and Thomas and 5 Spiro (1995) and converting to a mass basis by dividing by a default fuel-loading factor for 6 structural fires of 1.15 tons/fire (ERG, 2001), yielding 28 ng I-TEQ/kg. This factor was assumed 7 to apply to the open burning of demolition/construction wood for all three reference years. A 8 preliminary confidence rating was assigned to the emission factor estimate because it was 9 derived from structural fire estimates that were considered preliminary. 10 U.S. DOE (2000) reports that 8 MMT of wood construction and demolition debris were 11 generated in 1995. The majority of this waste was legally disposed via landfill or incineration. 12 However, an unknown portion is open burned at construction sites. For the purposes of a 13 preliminary estimate, it is assumed that 10% of the total, or 0.8 MMT, is open burned during all 14 three reference years. 15 16 6.14.2. W ater Releases--None 17 18 6.14.3. Solid Residue Releases 19 As discussed in Section 6.2, an ash emission factor of 300 ng WHO98 TEQDF/kg of 20 material burned was developed for structural fires and is adopted here for ash from open burning 21 of construction/demolition wood. A preliminary confidence rating was assigned to the emission 22 factor estimate because it was derived from structural fire estimates. 23 The ash yield from wood grown in temperate zones is 0.1 to 1%, and bark produces 3 to 24 8% ash (Ragland et al., 1991). A midrange value of 3% is assumed here for all wood burned. 25 Multiplying this value by the activity factors discussed above for open burning of 26 construction/demolition wood yields the following: 0.024 MMT in all reference years. These are 27 given a preliminary confidence rating because they are derived from emission factors with 28 preliminary confidence ratings. 29 30 6.14.4. Release Summary 31 The inventory decision criteria and releases to all media are summarized below: This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 7 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Open Burning Demolition/Construction Wood Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. No No A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 No P No P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 8 DRAFT: DO NOT CITE OR QUOTE Emission Factors Open Burning Demolition/Construction Wood Air Releases______________ 1987--28 ng WHO98 TEQDF/kg (Preliminary). 1995--28 ng WHO98 TEQDF/kg (Preliminary). 2000--28 ng WHO98 TEQDF/kg (Preliminary)._______________ Activity Levels 1987--0.8 MMT (Preliminary). 1995--0.8 MMT (Preliminary). 2000--0.8 MMT (Preliminary).___________________________ Releases 1987--22 g WHO98 TEQdf (Preliminary). 1995--22 g WHO98 TEQdf (Preliminary). 2000--22 g WHO98 TEQdf (Preliminary).___________________ W ater Releases_____________ None.______________________________________________________ Solid Residue Releases__________ Emission Factors 1987--300 ng WHO98 TEQDF/kg (Preliminary). 1995--300 ng WHO98 TEQDF/kg (Preliminary). 2000--300 ng WHO98 TEQDF/kg (Preliminary).______________ Activity Levels 1987--0.024 MMT (Preliminary). 1995--0.024 MMT (Preliminary). 2000--0.024 MMT (Preliminary)._________________________ Releases 1987--7 g WHO98 TEQdf (Preliminary). 1995--7 g WHO98 TEQdf (Preliminary). 2000--7 g WHO98 TEQdf (Preliminary).____________________ Products________________ None.______________________________________________________ 1 2 3 6.15. OIL SPILL BURNING 4 Aurell and Gullett (2010) measured dioxin emissions during in situ burning of oil spilled 5 into the Gulf of Mexico over the time period of July 13-16, 2010. They derived an emission 6 factor of 1.7 ng TEQ/kg of oil burned assuming that congeners below detection limits equal zero. 7 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 3 9 DRAFT: DO NOT CITE OR QUOTE 1 If congeners below detection limits were set to their full detection limit, the emission factor was 2 estimated to be 3.0 ng TEQ/kg. However, no activity information was found specifically for in 3 situ oil burning during the reference years, so no quantitative release estimate could be made 4 (Not quantifiable). 5 Oil Spill Burning_____________________ The available information is insufficient to make quantitative release estimates (Not quantifiable).________________________________________________________ 6 7 8 6.16. CANDLE BURNING 9 Candle burning is a possible source of CDD/CDFs to the air because CDD/CDF releases 10 have been measured from other types of fires. However, no emissions data or activity 11 information were found specifically for this source, so no quantitative release estimate could be 12 made (Not quantifiable). 13 Candle Burning_____________________ The available information is insufficient to make quantitative release estimates (Not quantifiable).________________________________________________________ 14 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 4 0 DRAFT: DO NOT CITE OR QUOTE 6-41 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 This document is a draftfor review purposes only and does not constitute Agency policy. Table 6-1. CDD/CDF emission factors (ng/kg) for forest fires Biomass description and location Tree from Central North Carolina Pile--Central North Carolina Supplement--Central North Carolina Supplement--Western North Carolina Supplement--Oregon Shrub--California Shrub--Florida Central North Carolina Wood type Loblolly pine Loblolly pine Loblolly pine White pine Hemlock/Pine Titi, pine straw, gallberry Maritime chaparral White pine Test device Chamber Chamber Chamber Chamber Chamber Chamber Chamber Chamber n 7 10 2 2 2 2 2 4 Oregon Hemlock/Pine Chamber 3 Tree and leaves from Japan Unspecified Chamber 1 Wood, leaves, and grass from Sweden Unspecified Hood over fire on plate 1 ng TEQDF/kg of biomass Mean (Range) Reference 0 .8 6 a Gullett et al. (2008) 0.615a Gullett et al. (2008) 0.93a Gullett et al. (2008) 1.225a Gullett et al. (2008) 1.64a 8.36a Gullett et al. (2008) Gullett et al. (2008) 2.62a 25 (14-47) 15 (1-56) 4.7 27 Gullett et al. (2008) Gullett and Touati (2003) Gullett and Touati (2003) Ikeguchi and Tanaka (1999) Gonczi et al. (2005) 1/7/2013 Table 6-1. CDD/CDF emission factors (ng/kg) for forest fires (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 6-42 DRAFT: DO NOT CITE OR QUOTE Biomass description and location Litters, mosses, heathers, brackens, conifer needles, pine cones, shrubs, barks, and branches from France Forest leaf litter from three locations in Australia Wood type Pine and oak Eucalyptus, box, ironback Test device Chamber Chamber ng TEQDF/kg of biomass n Mean (Range) Reference 5 10 (1-26) Collet and Fiani (2006) 5 0.37 (0.09-0.79) Meyer et al. (2004) Prescribed forest fires in Queensland, Victoria, and Western Australia Tropical savanna--Australia Wildfires in Victoria Woodlands in Australia Eucalyptus Unspecified Eucalyptus Unspecified Field 10 0.5 (0.07-1.4)a Field Field Field 3 1.1 (0.2-2.8)a 2 0.7 (0.6-0.8)a 3 1.5 (0.9-2.5)a a`Originally reported as ng TEQ/kg of carbon and converted to ng TEQ/kg of biomass by multiplying by 0.5. Meyer et al. (2004, 2007) Meyer et al. (2004, 2007) Meyer et al. (2004, 2007) Meyer et al. (2004, 2007) 1 Table 6-2. Comparison of Forest Fire Data (million acres burned/year) 2 Fire type and year CEQ, 1997 U.S. EPA, 2002d NIFC, 2009 W ildfires-- 1987 5 2.45 W ildfires-- 1995 7 1.84 W ildfires-- 2000 8.36 7.39 Prescribed Fires-- 1987 5.1 NA Prescribed Fires-- 1995 5.1 NA Prescribed Fires-- 2000 3 4 NA= Not Available. 5 1.26 1.19 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6 - 4 3 DRAFT: DO NOT CITE OR QUOTE Congener Ratio 0 0.1 0.2 2.3.7.8- TCDD 1.2.3.7.8- PCDD 1.2.3.4.7.8- HxCDD 1.2.3.6.7.8- HxCDD 1.2.3.7.8.9- HxCDD 1.2.3.4.6.7.8- HpCDD 1,2,3,4,6,7,8,9-OCDD 2.3.7.8- TCDF 1.2.3.7.8- PeCDF 2.3.4.7.8- PeCDF 1.2.3.4.7.8- HxCDF 1.2.3.6.7.8- HxCDF 1.2.3.7.8.9- HxCDF 2,3,4,6,7,8-HpCDF 1.2.3.4.6.7.8- HpCDF 1.2.3.4.7.8.9- HpCDF 1.2.3.4.6.7.8.9- OCDF Source: Pleil and Lorber (2007) 1 2 Figure 6-1. Congener profile for structure fires. 3 0.3 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6_44 DRAFT: DO NOT CITE OR QUOTE Figure 6-2. Forest fire types in the United States. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 6-45 DRAFT: DO N O T CITE OR QUOTE 1 7. METAL SMELTING AND REFINING SOURCES OF CDD/CDFS 2 3 4 This chapter addresses dioxin releases associated with primary and secondary metal 5 processing. Primary processes involve the extraction of the base metal from mineral ores. 6 Secondary processes extract the base metal from recycled or waste materials. 7 8 7.1. PRIMARY NONFERROUS METAL SMELTING/REFINING 9 7.1.1. Primary Copper Smelting and Refining 10 Minor changes were made to the air-release estimates. 11 12 7.1.1.1. A ir R e le a se s 13 The emission factor was derived from testing at two facilities by Environmental Risk 14 Sciences, Inc. (1995), who used stack testing results to calculate the annual TEQ emission to air 15 to be less than 0.5 g I-TEQdf in 1995 for the seven facilities (out of a total of eight) belonging to 16 the National Mining Association. Using the activity level presented below of 1.60 MMT for 17 1995, the emission factor is calculated to be 0.31 ng I-TEQDF/kg of copper. This emission factor 18 was applied to all three reference years. 19 In 1987, copper refineries produced 1.13 MMT of copper (USGS, 1997a). In 1995, 20 eight primary copper smelters were in operation in the United States; one of which closed at the 21 end of that year (Edelstein, 1995). Total refinery production was 1.60 MMT in 1995, including 22 0.36 MMT from scrap material (Edelstein, 1995). In 2000, four primary smelters of copper were 23 in operation in the United States, producing 1.61 MMT of copper (USGS, 2002a). 24 25 7.1.1.2. W ater R e le a se s 26 No information was found on water releases from these facilities. 27 28 7.1.1.3. S o lid R e s id u e R e le a se s 29 Although no measurement data were found, CDD/CDFs are likely to be present in the fly 30 ash and possibly other solid residues at these facilities because they have been found in the air This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-1 DRAFT: DO NOT CITE OR QUOTE 1 em issions. These residues are disposed in landfills and, therefore, are not considered to be an 2 environm ental release. 3 4 7.1.1.4. P ro d u c ts 5 N o inform ation w as found indicating that C D D /C D Fs w ere present in products from 6 these facilities. 7 8 7.1.1.5. R e le a s e S u m m a ry 9 The inventory decision criteria and releases to all m edia are sum m arized below : 10 Inventory Decision Criteria for Primary Copper Smelting and Refining Air Water Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 11 12 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-2 DRAFT: DO NOT CITE OR QUOTE Primary Copper Smelting and Refining Emission Factors Air Releases___________ 1987-- 0.31 n g I-T E Q DF/k g o f copper. 1995-- 0.31 n g I-T E Q DF/k g o f copper. 2 0 0 0 -- 0.31 n g I-T E Q DF/k g o f copper.________________________ Activity Levels 1987-- 1.13 M M T o f copper. 1995-- 1.60 M M T o f copper. 2 0 0 0 -- 1.61 M M T o f co p p er._________________________________ Releases 1987-- 0.3 g I-TEQ . 1995-- 0.5 g I-TEQ . 2 0 0 0 -- 0.5 g I-T E Q .___________________________________________ W ater Releases__________ N one.________________________________________________________________ Solid Residue Releases_______ N one.________________________________________________________________ Products_____________ None. 1 2 3 7.1.2. Primary Magnesium Smelting and Refining 4 7.1.2.1. A ir R e le a se s 5 No change was made to the emission factor, but minor changes were made to the activity 6 estimates and resulting release estimates. The emission factor was derived from stack testing at a 7 Utah facility (Western Environmental Services and Testing, Inc., 2000). This was originally 8 reported as 105 ng I-TEQ/kg of magnesium produced and is converted here to 9 94 ng WHO98 TEQ/kg of magnesium produced based on congener data presented in Western 10 Environmental Services and Testing, Inc., 2000. Even though the testing occurred at only 11 one facility, the estimated releases for the year 2000 are included in the quantitative inventory. 12 This is because the Utah facility was the only one operating in the United States in 2000. 13 Additional facilities were operating in 1987 and 1995 and it is uncertain how well the testing at 14 the Utah facility represented the others. Therefore, the release estimates for 1987 and 1995 were 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-3 DRAFT: DO NOT CITE OR QUOTE 1 considered preliminary. The activity estimates were derived from production data from the 2 U.S. Geological Society (USGS, 2002). 3 Under the EPA TRI program for 2000, this facility reported air releases of 4 623 g CDD/CDFs (3.3 g WHO98 TEQDf) and on-site surface impoundments of 5 1,661 g CDD/CDFs (8.3 g WHO98 TEQdf) (U.S. EPA, 2008). No releases to other media were 6 reported. As explained in Chapter 1, the accuracy of the TRI data is unknown, and, therefore, 7 they are not used to make quantitative estimates in this document but rather as supportive 8 evidence that releases do occur. 9 10 7.1.2.2. W ater R e le a se s 11 Monitoring of wastewater discharges from U.S. magnesium production facilities for 12 CDD/CDF content has not been reported. Wastewater discharges of CDDs/CDFs reported for 13 the Norwegian facility (Oehme et al., 1989) are not adequate to support development of 14 wastewater emission factors for U.S. facilities because of possible differences in the processes 15 used to manufacture MgCl2 and pollution control equipment. Therefore, water releases are 16 possible but could not be quantified. 17 18 7.1.2.3. S o lid R e s id u e R e le a se s 19 CDD/CDFs have been reported in waste sludge generated during magnesium production. 20 EPA (2008) reports that in the year 2001, Magnesium Corporation of America (Rowley, UT) 21 released 2,289 g total CDD/CDF (10 g WHO98 TEQdf, or 12 g I-TEQdf) to on-site surface 22 impoundments. The potential for environmental release is unknown (Not quantifiable). 23 24 7.1.2.4. R e le a s e S u m m a ry 25 The inventory decision criteria and releases to all media are summarized below: 26 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-4 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Primary Magnesium Smelting and Refining Air W ater Solids Products Emission tests for at least two units/source types with No sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Emission factor tests represent units that are typical of the class. Yes Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). P/Qa 1 2 "Preliminary for 1987 and 1995, Quantitative for 2000 because testing occurred at only facility operating in 2000. 3 4 ___________________________________________________________________________ Primary Magnesium Smelting and Refining__________________ Air Releases_______________________________ Emission Factors 1987--94 ng WHO98 TEQDF/kg (110 ng I-TEQDF/kg). (Preliminary) 1995--94 ng WHO98 TEQDF/kg (110 ng I-TEQDF/kg). (Preliminary) 2000--94 ng WHO98 TEQDF/kg (110 ng I-TEQDF/kg).__________________________ Activity Levels 1987--0.142 MMT. 1995--0.142 MMT. 2000--0.083 MMT._____________________________________________________ Releases 1987-- 13 g WHO98TEQdf (16 g I-TEQdf). (Preliminary) 1995-- 13 g WHO98 TEQdf ( 1 6 g I-TEQdf). (Preliminary) 2 0 0 0 -- 8 g WHO98 TEQdf (9 g I-TEQdf).____________________________________ W ater Releases______________________________ Releases are possible but could not be quantified.____________________________________ Solid Residue Releases___________________________ Releases are possible but could not be quantified.____________________________________ Products_________________________________ None._______________________________________________________________________ 5 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-5 DRAFT: DO NOT CITE OR QUOTE 1 2 7.1.3. Primary Nickel Smelting and Refining 3 N o changes w ere m ade in the release estim ates from these facilities. 4 5 7.1.3.1. A ir R e le a se s 6 The em issions inform ation contained in th e N orw egian study (O ehm e et al., 1989) is not 7 adequate to support developm ent o f em ission factors for the U.S. facility for 1987 and 1995. 8 Since the only U.S. facility closed in 1998, em issions for 2000 are zero. 9 10 7.1.3.2. W ater R e le a se s 11 E P A (2 0 0 6 ) re p o rts th a t o n e stu d y (O e h m e et al., 1989) m e a su re d C D D /C D F s in 12 w astew ater releases from a nickel pro d u ctio n p lan t in N orw ay. T he in fo rm atio n is n o t adequate 13 to su p p o rt d e v e lo p m e n t o f e m issio n fa c to rs fo r th e U n ite d S tates. T h u s, re le a se s are p o s s ib le b u t 14 could n o t b e q u an tified in 1987 and 1995. Since th e only U .S. facility closed in 1998, em issio n s 15 fo r 2 0 0 0 are zero. 16 17 7.1.3.3. S o lid R e s id u e R e le a se s 18 N o in fo rm atio n w as fo u n d in d icatin g th a t C D D /C D F s w e re p re sen t in solid resid u es from 19 these facilities. 20 21 7.1.3.4. P ro d u c ts 22 N o inform ation w as found indicating that C D D /C D Fs w ere present in products from 23 these facilities. 24 25 7.1.3.5. R e le a s e S u m m a ry 26 The release estim ates are sum m arized below : 27 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-6 DRAFT: DO NOT CITE OR QUOTE Primary Nickel Smelting and Refining_________________ Air Releases____________________________ R eleases are possible but could not be quantified in 1987 and 1995 and w ere zero in 2000. W ater Releases__________________________ R eleases are possible but could not be quantified in 1987 and 1995 and w ere zero in 2000. Solid Residue Releases_______________________ N one._____________________________________________________________________________________ Products_____________________________ None. 1 2 3 7.1.4. Primary Aluminum Smelting and Refining 4 N o changes w ere m ade to the release estim ates for these facilities, but additional 5 background inform ation is provided below. 6 The use o f hexachloroethane during alum inum production has been identified as a cause 7 for dioxin em issions (UNEP, 2005). The production o f hexachloroethane ceased in the 8 U nited States in the 1970s, so it is not likely to have been used for this purpose during the 9 reference years (A TSD R , 1997). U N E P (2005) did not determ ine em ission factors for prim ary 10 alum inum production. 11 K u c h e re n k o et al. (2 0 0 1 ) m e a su re d C D D /C D F s e m issio n s fro m a p rim a ry alu m in u m 12 p la n t in K ra sn o y a rsk , R u ssia . T h e a ir re le a se e m issio n fa c to r w a s e s tim a te d as 11 n g I-T E Q /k g , 13 a n d th e w a te r re le a se e m issio n fa c to r w a s e s tim a te d as 0.141 n g I-T E Q /L . It is u n k n o w n h o w 14 sim ilar this p lan t is to th o se in th e U n ited States. 15 In su m m a ry , in su ffic ie n t in fo rm a tio n is a v a ila b le to e stim a te i f C D D /C D F re le a se s o c c u r 16 from th ese facilities in th e U n ited States. 17 18 7.1.5. Primary Titanium Smelting and Refining 19 N o changes w ere m ad e to th e release estim ates from th ese facilities, b u t additional 20 background inform ation is provided below. 21 In the year 2000, nine facilities w ith an SIC code for inorganic pigm ents reported dioxin 22 releases under E P A 's T R I program . The air and w ater releases sum m ed across these facilities 23 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-7 DRAFT: DO NOT CITE OR QUOTE 1 were less than 1 g WHO98 TEQdf. A total of 240 g WHO98 TEQdf were disposed in landfills 2 (U.S. EPA, 2008). No releases to other media were reported. As explained in Chapter 1, the 3 accuracy of the TRI data is unknown, and therefore, they are not used to make quantitative 4 estimates in this document but rather as supportive evidence that releases do occur. 5 6 7.1.5.1. A ir R e le a se s 7 Based on the TRI data reported above, air releases are possible but could not be 8 quantified. 9 10 7.1.5.2. W ater R e le a se s 11 Based on the TRI data reported above, water releases are possible but could not be 12 quantified. 13 14 7.1.5.3. S o lid R e s id u e R e le a se s 15 Titanium dioxide production creates a variety of sludge wastes, which can contain 16 CDDs/CDFs. As discussed above, the TRI data suggest that inorganic pigment facilities 17 disposed a total of 240 g WHO98 TEQdf in landfills in 2000 (U.S. EPA, 2008). 18 EPA (2001) reports the following measurements in wastes generated in conjunction with 19 chlorinators: 20 21 Millennium Baltimore, chloride solids/waste acid: 812 ng WHO98 TEQdf/L. 22 Millennium Baltimore, filter press solids: 2,615 ng WHO98 TEQDF/kg. 23 DuPont Edge Moor, iron rich: 58.7 ng WHO98 TEQDF/kg. 24 DuPont New Johnsonville, wastewater treatment solids: 402 ng WHO98 TEQDF/kg. 25 26 EPA (2001) reports that the production of wastewater treatment sludges from comingled chloride 27 and sulfate process wastewaters at the Millennium Plant was 93,121 MT/year. Combining this 28 production rate with an assumed 1,000 ng WHO98 TEQDF/kg suggests that about 29 90 g WHO98 TEQDF/year may be associated with these sludges at this plant. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-8 DRAFT: DO NOT CITE OR QUOTE 1 F or the m ost part, these sludges have been disposed o f in either on-site or off-site R C R A 2 Subtitle D solid w aste disposal facilities. H ow ever, given the potential for leaching o f the heavy 3 m etals from the sludge in the Subtitle D landfill, E PA has listed this w aste as hazardous w aste 4 under Subtitle C. These sludges are now considered a hazardous w aste under R C R A and m ust 5 be disposed o f in perm itted landfills (U.S. EPA , 2001). These am ounts are not considered to 6 cause environm ental releases under the definition in this docum ent. 7 8 7.1.5.4. P ro d u c ts 9 N o inform ation w as found indicating that C D D /C D Fs w ere present in products from 10 these facilities. 11 12 7.1.5.5. R e le a s e S u m m a ry 13 T h e re le a s e e stim a te s are su m m a riz e d b e lo w : 14 Primary Titanium Smelting and Refining Air Releases____________ N o t q u an tifiab le.______________________________________________________ Water Releases___________ N o t q u an tifiab le.______________________________________________________ Solid Residue Releases________ N one._________________________________________________________________ Products______________ None. 15 16 17 7.2. SECONDARY NONFERROUS METAL SMELTING AND REFINING 18 7.2.1. Secondary Aluminum Smelting and Refining 19 N o changes w ere m ad e in th e release estim ates from th ese facilities, b u t som e additional 20 background inform ation is provided below. 21 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-9 DRAFT: DO NOT CITE OR QUOTE 1 7.2.1.1. A ir R e le a se s 2 The emission factors were derived from testing at seven facilities (CARB, 1992a, b; U.S. 3 EPA, 1995c). Activity data were based on survey information from USGS (2002a). 4 In the year 2000, 29 facilities with an SIC code for secondary smelting and refining of 5 nonferrous metals reported dioxin releases under the EPA TRI program (U.S. EPA, 2008). Most 6 of these facilities appeared to be aluminum producers. The sum of the air releases across these 7 facilities was 1,022 g, which EPA estimates is equal to 13.8 g WHO98 TEQDF. No releases to 8 other media were reported. As explained in Chapter 1, the TRI data are not used to make 9 quantitative estimates in this document but rather as supportive evidence that releases do occur. 10 11 7.2.1.2. W ater R e le a se s 12 No information was found indicating that CDD/CDFs were present in water releases from 13 these facilities. 14 15 7.2.1.3. S o lid R e s id u e R e le a se s 16 Although no measurement data were found, CDD/CDFs are likely to be present in the fly 17 ash and possibly other solid residues at these facilities because they have been found in the air 18 emissions. These residues are disposed in landfills and, therefore, are not considered to be an 19 environmental release. 20 21 7.2.1.4. P ro d u cts 22 No information was found indicating that CDD/CDFs were present in products from 23 these facilities. 24 25 7.2.1.5. R elea ses 26 The inventory decision criteria and releases to all media are summarized below: 27 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-10 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Secondary Aluminum Smelting and Refining Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). 1 Q 2 Secondary Aluminum Smelting and Refining Air Releases________________ Emission Factors 1987-- 15 ng WHO98 TEQDF/kg (14 ng I-TEQDF/kg). 1995-- 15 ng WHO98 TEQDF/kg (14 ng I-TEQDF/kg). 2000--5.2 ng WHO98 TEQDF/kg (4.9 ng I-TEQDF/kg).___________ Activity Levels 1987--0.7 MMT. 1995-- 1.3 MMT. 2000-- 1.6 MMT.________________________________________ Releases 1987-- 11 g WHO98 TEQdf(10 g I-TEQdf). 1995--20 g WHO98 TEQdf(18 g I-TEQdf). 2000--8 g WHO98 TEQdf(8 g I-TEQDF)._____________________ W ater Releases_______________ None._______________________________________________________ Solid Residue Releases____________ None._______________________________________________________ Products_________________ None._______________________________________________________ 3 4 5 7.2.2. Secondary Copper Smelting and Refining 6 No changes were made in the release estimates from these facilities. 7 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-11 DRAFT: DO NOT CITE OR QUOTE 1 7.2.2.1. A ir R e le a se s 2 O nly three facilities w ere active during the reference years. The em ission factors w ere 3 derived from stack testing at these plants as described in U S E PA (2006). The release sum m ary 4 below show s the em ission factor and activity estim ates (based on data for each plant) in each 5 reference year. 6 7 7.2.2.2. W a ter R e le a se s 8 N o inform ation w as found indicating that C D D /C D Fs w ere present in w ater releases from 9 these facilities. 10 11 7.2.2.3. S o lid R e s id u e R e le a se s 12 A lth o u g h no m easu rem en t data w ere found, C D D /C D F s are lik ely to b e p resen t in th e fly 13 a s h a n d p o s sib ly o th e r so lid re sid u e s a t th e se fa c ilitie s b e c a u se th e y h a v e b e e n fo u n d in th e a ir 14 em issions. T hese residues are d isp o sed in lan d fills and, therefore, are n o t co n sid ered to b e an 15 en v iro n m e n ta l release. 16 17 7.2.2.4. P ro d u c ts 18 N o in fo rm atio n w as fo u n d in d icatin g th a t C D D /C D F s w e re p re sen t in p ro d u c ts from 19 th ese facilities. 20 21 7.2.2.5. R e le a se s 22 The inventory decision criteria and releases to all m edia are sum m arized below : 23 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-12 DRAFT: DO NOT CITE OR QUOTE 1 2 Inventory Decision Criteria for Secondary Copper Smelting and Refining Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-13 DRAFT: DO NOT CITE OR QUOTE Emission Factors Secondary Copper Smelting and Refining Air Releases F ranklin 1987--17,000 ng WHO98 TEQDF/kg (17,000 ng I-TEQDF/kg). 1995--17.000 ng WHO98 TEQDF/kg (l7,000 ng I-TEQDF/kg). Chem etco 1987--3.7 ng WHO98 TEQDF/kg (3.6 ng I-TEQDF/kg). 1995--3.7 ng WHO98 TEQDF/kg (3 .6 ng I-TEQDF/kg). 2000--3.7 ng WHO98 TEQDF/kg (3 .6 6 ng I-TEQDF/kg). G a sto n 1987--8,900 ng WHO98 TEQDF/kg (8,700 ng I-TEQDF/kg). Activity Levels F ranklin 1987- -13,600,000 kg. 1995- -16,000,000 kg. Chem etco 1987- -120,000,000 kg. 1995- -135,000,000 kg. 2000- -235,000,000 kg. G a sto n 1987--85,000,000 kg. Releases 1987--990 g WHO98 TEQdf (970 g I-TEQdf). 1995--270 g WHO98 TEQdf (270 g I-TEQdf). 2000--0.9 g WHO98 TEQdf (0.8 g I-TEQdf). W ater Releases None. Solid Residue Releases None. Products None. 1 2 3 7.2.3. Secondary Lead Smelting 4 N o changes w ere m ade in the release estim ates from these facilities. 5 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-14 DRAFT: DO NOT CITE OR QUOTE 1 2 7.2.3.1. A ir R e le a se s 3 Three types o f furnaces are used in secondary lead sm elting. C D D /C D F em ission factors 4 w ere estim ated for secondary lead sm elters using the results o f em ission tests perform ed by EPA 5 at three sm elters (a blast furnace [U.S. EPA , 1995b], a colocated blast/reverberatory furnace 6 [U.S. E PA , 1992a], and a rotary kiln furnace [U.S. E PA , 1995c]). A ctivity estim ates w ere 7 derived from U SG S survey data. The release sum m ary below show s the em ission factor and 8 activity for each furnace type in each reference year. 9 10 7.2.3.2. W a ter R e le a se s 11 N o in fo rm a tio n w a s fo u n d in d ic a tin g th a t C D D /C D F s w e re p re s e n t in w a te r re le a se s fro m 12 th ese facilities. 13 14 7.2.3.3. S o lid R esid u e R elea ses 15 A lth o u g h n o m e a s u re m e n t d a ta w e re fo u n d , C D D /C D F s are lik e ly to b e p re s e n t in th e fly 16 ash and p o ssib ly o th er solid resid u es at th ese facilities b ecau se th ey h av e b een fo u n d in th e air 17 em issions. T hese residues are d isp o sed in landfills and, th erefo re, are n o t co n sid ered to b e an 18 en v iro n m en tal release. 19 20 7.2.3.4. P ro d u c ts 21 N o inform ation w as found indicating that C D D /C D F s w ere present in products from 22 these facilities. 23 24 7.2.3.5. R e le a se s 25 The inventory decision criteria and releases to all m edia are sum m arized below : 26 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-15 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Secondary Lead Smelting Air W ater Solids Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-16 DRAFT: DO NOT CITE OR QUOTE Secondary Lead Smelting_______________ Air Releases_____________________ Emission Factors B lastfu rn aces w ithout scrubber 1987, 1995, 2000-- 8.8 ng WHO98 TEQDF/kg (8.3 ng I-TEQDF/kg). B lastfu rn aces w ith scrubber 1987, 1995, 2000--0.64 ng WHO98 TEQDF/kg (0.63 ng I-TEQDF/kg). R everberatory an d colocatedfu rn aces w ithout scrubber 1987, 1995, 2000--0.42 ng WHO98 TEQDF/kg (0.41 ng I-TEQDF/kg). R everberatory an d colocatedfu rn aces w ith scrubber 1987, 1995, 2000--0.05 ng WHO98 TEQDF/kg (0.05 ng I-TEQDF/kg).). R otary fu rn aces w ithout scrubber 1987, 1995, 2000--0.66 ng WHO98 TEQDF/kg (0.66 ng I-TEQDF/kg). R otary fu rn aces w ith scrubber 1987, 1995, 2000--0.24 ng WHO98 TEQDF/kg (0.24 ng I-TEQDF/kg). Activity Levels B lastfu rn aces (14% w ith an d 86% w ithout scrubbers) 1987--0.15 MMT. 1995--0.2 MMT. 2000--0.29 MMT. R everberatory an d colocatedfu rn aces (52% w ith an d 48% w ithout scrubbers) 1987--0.53 MMT. 1995--0.72 MMT. 2000--1 MMT. R otary fu rn aces (57% w ith an d 43% w ithout scrubbers) 1987--0.04 MMT. 1995--0.05 MMT. 2000--0.07 MMT.________________________________ Releases 1987-- 1 g WHO98 TEQdf (1 g I-TEQdf). 1995-- 2 g WHO98 TEQdf (2 g I-TEQdf). 2000--2 g WHO98 TEQdf (2 g I-TEQdf).___________________________ W ater Releases_____________________ None.______________________________________________________________ Solid Residue Releases_________________ None.______________________________________________________________ Products_______________________ None.______________________________________________________________ 1 2 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-17 DRAFT: DO NOT CITE OR QUOTE 1 2 3 7.2.4. Secondary Zinc Production 4 This is a new section. 5 M ore than one-fourth o f the total zinc (Zn) consum ed in 2002 by dom estic industries w as 6 secondary Zn. A bout 87% o f recycled zinc w as derived from new scrap, generated m ainly in 7 galvanizing and die casting plants and brass m ills. The rem aining 13% w as obtained from brass 8 products, flue dust, old die casts, and old rolled Zn articles. R ecycled Zn w as used by 2 prim ary 9 sm e lte rs a n d 13 la rg e a n d m e d iu m (m o re th a n 1,000 to n s /y e a r) siz e d se c o n d a ry sm elters 10 p rin cip ally fo r p ro d u ctio n o f zinc chem icals, m ain ly oxide, and Z n m etal, in clu d in g alloys 11 (U S G S , 2 0 0 2 b ). 12 C lean n ew scrap, m ain ly brass, rolled zinc clippings, and rejected die castings, u su ally 13 re q u ire s o n ly re m e ltin g . In th e c a se o f m ix e d n o n fe rro u s sh re d d e d m etal scrap, z in c is se p a ra te d 14 from o th er m aterials b y h an d or m ag n etic separation. M o st o f th e zinc reco v ered from dust 15 p ro d u c e d d u rin g re m e ltin g o f g a lv a n iz e d steel scrap , is re c o v e re d in ro ta ry k iln s b y u sin g th e 16 W aelz p rocess (U S G S , 2009a). 17 18 7.2.4.I. A ir R e le a se s 19 U N E P (2005) p ro p o sed several zinc related em issio n factors b ased on testin g at facilities 20 in G erm any and Japan: 21 22 K ilns w ith no A PC s-- 1,000 ng I-T E Q /kg o f zinc 23 H ot briquetting/rotary furnaces w ith basic dust controls-- 100 ng I-T E Q /kg o f zinc 24 Furnaces w ith com prehensive pollution controls-- 5 ng I-TEQ /kg o f zinc 25 Z inc m elting-- 0.3 ng I-T E Q /kg o f zinc 26 27 The E uropean D ioxin Inventory (Q uass et al., 2001) suggests an em ission factor o f 28 50 ng I-TEQ /kg o f zinc w ith a range o f 5 to 500 ng I-TEQ /kg for secondary zinc production. 29 The central value o f 50 ng I-T E Q /kg o f zinc w as selected for all reference years. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-18 DRAFT: DO NOT CITE OR QUOTE 1 The secondary slab zinc production in the U nited States w as 82,500 M T in 1987, 2 131,000 M T in 1995 and 135,000 M T in 2000 (U SG S, 2009b). 3 4 7.2.4.2. W ater R e le a se s 5 N o inform ation w as found indicating that C D D /C D Fs w ere present in w ater releases from 6 these facilities. 7 8 7.2.4.3. S o lid R e s id u e R e le a se s 9 A lthough no m easurem ent data w ere found, C D D /C D Fs are likely to be present in the fly 10 ash and possibly o th er solid resid u es at these facilities b ecau se th ey have b een fo u n d in the air 11 e m issio n s. T h ese re sid u e s are d isp o se d in la n d fills and, th e re fo re , are n o t c o n sid e re d to b e an 12 en v iro n m en tal release. 13 14 7.2.4.4. P ro d u c ts 15 N o in fo rm a tio n w a s fo u n d in d ic a tin g th a t C D D /C D F s w e re p re s e n t in p ro d u c ts fro m 16 th ese facilities. 17 18 7.2.4.5. R e le a se s 19 T he in v en to ry d ecisio n criteria and releases to all m ed ia are su m m arized b elo w : 20 Inventory Decision Criteria for Secondary Zinc Production Air Water Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 21 22 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-19 DRAFT: DO NOT CITE OR QUOTE Secondary Zinc Production Emission Factor Air Releases______ 1987-- 50 ng I-TEQ /kg o f zinc. 1995-- 50 ng I-TEQ /kg o f zinc. 2 0 0 0 -- 50 n g I-T E Q /k g o f zinc._________________________ Activity Levels 1987-- 82,500 M T. 1995-- 131,000 M T. 2 0 0 0 -- 1 3 5,000 M T .____________________________________ Releases 1987-- 4 g I-TEQ. 1995-- 7 g I-TEQ. 2 0 0 0 -- 7 g I-T E Q .______________________________________ W ater Releases_____ N one.__________________________________________________________ Solid Residue Releases N one.__________________________________________________________ Products________ None. 1 2 3 7.3. PRIMARY FERROUS METAL SMELTING/REFINING 4 7.3.1. Sinter Production 5 N o changes w ere m ade to the release estim ates except the air releases in 2000, w hich 6 decreased slightly due to com putational corrections. 7 8 7.3.1.1. A ir R e le a se s 9 Tw o types o f A PC D s are used in sinter production: w et scrubbers and fabric filters. The 10 em issio n factors fo r facilities w ith th ese tw o types o f A P C D s w ere derived from testin g at 11 tw o U .S . sin te rin g p la n ts o p e ra tin g in 1997 (C a lc a g n i et al., 1998). A c tiv ity e stim a te s w e re 12 derived from several sources: C alcagni et al. (1998), A IS I (1990), and F en to n (1996). T he 13 re le a se s u m m a ry b e lo w sh o w s th e e m issio n fa c to r a n d ac tiv ity fo r ea ch A P C D ty p e in each 14 referen ce year. 15 16 17 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-20 DRAFT: DO NOT CITE OR QUOTE 1 7.3.1.2. W a ter R e le a se s 2 N o inform ation w as found indicating that C D D /C D Fs w ere present in w ater releases from 3 these facilities. 4 5 7.3.1.3. S o lid R e s id u e R e le a se s 6 A lthough no m easurem ent data w ere found, C D D /C D Fs are likely to be present in the fly 7 ash and possibly other solid residues at these facilities because they have been found in the air 8 em issions. These residues are disposed in landfills and, therefore, are not considered to be an 9 environm ental release. 10 11 7.3.1.4. P ro d u c ts 12 N o in fo rm atio n w as fo u n d in d icatin g th at C D D /C D F s w ere p resen t in p ro d u cts from 13 th e s e fa cilities. 14 15 7.3.1.5. R e le a se s 16 T he in v en to ry decision criteria and releases to all m ed ia are su m m arized b elo w : 17 Inventory Decision Criteria for Sinter Production Air Water Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 18 19 Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-21 DRAFT: DO NOT CITE OR QUOTE Emission Factors Sinter Production_____________________________ Air Releases________________________________ Wet scrubber 1987--0.62 ng WHO98 TEQDF/kg (0.55 ng I-TEQDF/kg) of sinter. 1995--0.62 ng WHO98 TEQDF/kg (0.55 ng I-TEQDF/kg) of sinter. 2000--0.62 ng WHO98 TEQDF/kg (0.55 ng I-TEQDF/kg) sinter. F abric filter 1987--4.6 ng WHO98 TEQDF/kg (4.1 ng I-TEQDF/kg) of sinter. 1995--4.6 ng WHO98 TEQDF/kg (4.1 ng I-TEQDF/kg) of sinter. 2000--4.6 ng WHO98 TEQDF/kg (4.1 ng I-TEQDF/kg) of sinter.________________ Activity Levelsa 1987-- 14.5 MMT. 1995-- 12.4 MMT. 2000-- 10.6 MMT._______________________________________________________ Releases 1987--33 g WHO98 TEQdf (30 g I-TEQdf). 1995--28 g WHO98 TEQdf (25 g I-TEQdf). 2000--24 g WHO98 TEQdf (21 g I-TEQdf).__________________________________ W ater Releases______________________________ None._______________________________________________________________________ Solid Residue Releases___________________________ None._______________________________________________________________________ Products_________________________________ None. 1 2 aFifty-nine percent of sinter productionwas at facilities withwet scrubbers and 41%was at facilities withfabric 3 filters. 4 5 6 7.3.2. Coke Production 7 Minor changes were made to the air emission factor and resulting air-release estimates. 8 The confidence rating was upgraded from preliminary to quantifiable for the air releases due to 9 addition of facility tests used to estimate the emission factor. 10 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-22 DRAFT: DO NOT CITE OR QUOTE 1 7.3.2.1. A ir R e le a se s 2 U S E P A (2 0 0 6 ) u se d th e e m issio n fa c to r o f 0.23 n g I-T E Q DF/k g o f coal c o n su m e d 3 estim ated by B rem m er, et al. (1994). A nother study m easured dioxin em issions at fo u r C anadian 4 facilities (C harles E. N apier C om pany, Ltd., 2000). The present study averages the em ission 5 factor across the facilities tested in both studies to derive an em ission factor o f 6 0 .2 9 n g I-T E Q DF/k g o f coal c o n su m ed . T h is e m issio n fa c to r w a s a p p lie d to all th re e re fe re n c e 7 years. C oke production estim ates w ere obtained from E IA (2002). The confidence rating was 8 upgraded from prelim inary to quantitative because the em ission factor w as derived from tw o 9 studies involving 5 facilities. 10 In th e y ea r 2000, fo u r facilities w ith an SIC co d e fo r steel w orks, b last furnaces 11 (in c lu d in g c o k e o v en s), a n d ro llin g m ills re p o rte d d io x in re le a se s u n d e r th e E P A T R I p ro g ra m 12 (U .S. E P A , 2008). T he sum o f th e air releases across th ese facilities w as 31.8 g, w h ich E P A 13 e stim a te s is eq u al to 4.1 g W H O 98 T E Q DF. N o re le a se s to o th e r m e d ia w e re re p o rted . A s 14 e x p la in e d in C h a p te r 1, th e T R I d a ta are n o t u s e d to m a k e q u a n tita tiv e e stim a te s in th is d o c u m e n t 15 b u t ra th e r as su p p o rtiv e e v id e n c e th a t re le a se s d o occur. 16 17 7.3.2.2. W a ter R e le a se s 18 A lth o u g h w a te r is u se d in q u en ch to w ers to cool h o t coke, it is recycled, an d th e 19 evap o rate is replenished. T herefore no w ater releases occur. 20 21 7.3.2.3. S o lid R e s id u e R e le a se s 22 A lthough no m easurem ent data w ere found, C D D /C D Fs are likely to be present in the fly 23 ash and possibly other solid residues at these facilities because they have been found in the air 24 em issions. These residues are disposed in landfills and, therefore, are not considered to be an 25 environm ental release. 26 27 7.3.2.4. P ro d u c ts 28 N o inform ation w as found indicating that C D D /C D Fs w ere present in products from 29 these facilities. 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-23 DRAFT: DO NOT CITE OR QUOTE 1 7.3.2.5. R e le a s e S u m m a ry 2 The inventory decision criteria and releases to all media are summarized below: Inventory Decision Criteria for Coke Production Air Water Emission tests for at least two units/source types with Yes sufficient documentation to directly derive emission factors. Solids Products Measured emission factors consistent or have understandable Yes differences. Emission factor tests represent units that are typical of the Yes class. Activity estimates based on source-specific surveys. Yes Conclusion (Q = Quantitative, P = Preliminary). 3 Q 4 ________________________________________________ Coke Production Air Releases Emission Factors 1987--0.29 ng I-TEQDF/kg of coal. 1995--0.29 ng I-TEQDF/kg of coal. 2000--0.29 ng I-TEQDF/kg of coal.______________ Activity Levels 1987--33.5 MMT. 1995--29.9 MMT. 2000--26.2 MMT.___________________________ Releases 1987-- 10 g I-TEQdf. 1995--9 g I-TEQdf. 2000--8 g I-TEQdf. W ater Releases None.____________________________________________ Solid Residue Releases None.____________________________________________ Products______ None.____________________________________________ 5 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-24 DRAFT: DO NOT CITE OR QUOTE 1 2 3 7.4. SECONDARY FERROUS METAL SMELTING/REFINING 4 No changes were made in the release estimates from these facilities. 5 7.4.1. Air Releases 6 No changes were made in the air-release estimates, but the confidence rating was 7 upgraded from preliminary to quantifiable. This was based on the support for the emission factor 8 from testing at 6 facilities in Germany and 13 facilities in Canada. The emission factor was 9 derived by averaging the data reported in Umweltbundesamt (1996) and the three Environment 10 Canada reports (Charles E. Napier Company, Ltd., 2000; Cianciarelli, 2000, 2001). Based on the 11 congener data reported by Cianciarelli, 2000, the I-TEQs are approximately equivalent to the 12 WHO98 TEQs. The activity estimates were derived from steel-production data from USGS 13 (2002a). 14 15 7.4.2. W ater Releases 16 No information was found indicating that CDD/CDFs were present in water releases from 17 these facilities. 18 19 7.4.3. Solid Residue Releases 20 Although no measurement data were found, CDD/CDFs are likely to be present in the fly 21 ash and possibly other solid residues at these facilities because they have been found in the air 22 emissions. These residues are disposed in landfills and, therefore, are not considered an 23 environmental release. 24 25 7.4.4. Products 26 No information was found indicating that CDD/CDFs were present in products from 27 these facilities. 28 29 7.4.5. Release Summary 30 The inventory decision criteria and releases to all media are summarized below: This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-25 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Secondary Ferrous Metal Smelting/Refining Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). 1 Q 2 Secondary Ferrous Metal Smelting/Refining Air Releases_____________ Emission Factors 1987-- 1.2 ng (WHO98 or I-TEQDF/kg) of steel. 1995-- 1.2 ng (WHO98 or I-TEQDF/kg) of steel. 2000-- 1.2 ng (WHO98 or I-TEQDF/kg) of steel.______________ Activity Levels 1987--30.8 MMT. 1995--38.4 MMT. 2000--49.0 MMT._____________________________________ Releases 1987--37 g (WHO98 or I-TEQdf). 1995--46 g (WHO98 or I-TEQdf). 2000--59 g (WHO98 or I-TEQdf). W ater Releases____________ None._____________________________________________________ Solid Residue Releases_________ None._____________________________________________________ Products_______________ None._____________________________________________________ 3 4 5 6 7 8 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-26 DRAFT: DO NOT CITE OR QUOTE 1 7.5. FERROUS FOUNDRIES 2 No changes were made to the release estimates for these facilities, but some additional 3 background information is provided below. 4 5 7.5.1. Air Releases 6 The emission factor for the ferrous foundries was estimated by combining the mean 7 emission factor derived from the data reported in Umweltbundesamt (1996), CARB (1993), and 8 EPA (1997a), yielding a value of 1.23 ng I-TEQDF/kg of metal feed. This was converted to 9 1.37 ng WHO98 TEQDF/kg based on the congener profile reported in EPA, 1997a. The emission 10 data represent a total of 10 facilities and generated emission factors ranging over 4 orders of 11 magnitude. Based on the inconsistency of these results for reasons that are not clear, the release 12 estimates are considered preliminary. The activity estimates were derived from survey data from 13 USGS (2001). 14 In the year 2000, five facilities with an SIC code for gray and ductile iron foundries 15 reported dioxin releases under the EPA TRI program (U.S. EPA, 2008). The sum of the air 16 releases across these facilities was 117 g, which EPA estimates is equal to 21.5 g WHO98 TEQDF. 17 No releases to other media were reported. As explained in Chapter 1, the TRI data are not used 18 to make quantitative estimates in this document but rather as supportive evidence that releases do 19 occur. 20 21 7.5.2. W ater Releases 22 Liquid pollution makes up a small portion of the total waste stream from foundries 23 (Freeman, 1995). Water is used in foundries to cool metal and other work pieces and in the wet 24 scrubber air emission system. No information was found on CDD/CDF levels in these 25 wastewaters. 26 27 7.5.3. Solid Residue Releases 28 Solid waste makes up a large portion of the pollution from foundries. One-quarter to 29 one ton of solid waste per one ton of castings is expected (Shah, 1995). The waste comes from This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-27 DRAFT: DO NOT CITE OR QUOTE 1 sand, slag, em issions control dust, and spent refractories. M olding and core sand m ake up 2 6 6 -8 8 % o f the total w aste from ferrous foundries (U.S. EPA , 1992b). 3 Slag w aste is often very com plex chem ically and contains a variety o f contam inants from 4 the scrap m etals. C om m on com ponents include m etal oxides, m elted refractories, sand, and coke 5 ash (if coke is used). F luxes m ay also be added to help rem ove the slag from the furnace. Slag 6 m ay be hazardous if it contains lead, cadm ium , or chrom ium from steel or nonferrous m etals 7 m elting. Iron foundry slag m ay be highly reactive if calcium carbide is used to desulfurize the 8 iron. N o inform ation w as found on C D D /C D F levels in these solid wastes. H ow ever, they are 9 typically landfilled and thus not considered a release to environm ent. 10 11 7.5.4. Products 12 N o in fo rm atio n w as fo u n d in d icatin g th at C D D /C D F s w ere p resen t in p ro d u cts from 13 th e s e fa cilities. 14 15 7.5.5. Release Summary 16 T he in v en to ry d ecisio n criteria and releases to all m ed ia are su m m arized below : 17 Inventory Decision Criteria for Ferrous Foundries Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable N o differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 18 19 Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-28 DRAFT: DO NOT CITE OR QUOTE Ferrous Foundries_________________________ Air Releases___________________________ Emission Factors 1987-- 1.4 ng WHOgg TEQDF/kg (1.2 ng I-TEQDF/kg) of metal feed. (Preliminary) 1995-- 1.4 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of metal feed. (Preliminary) 2000-- 1.4 ng WHO98 TEQDF/kg (1.2 ng I-TEQDF/kg) of metal feed. (Preliminary) Activity Levels 1987--9.19 MMT. 1995-- 13.9 MMT. 2000-- 11.3 MMT.__________________________________________________ Releases 1987-- 13 g WHO98TEQdf (11 g I-TEQdf). (Preliminary) 1995-- 19 g WHO98 TEQdf (17 g I-TEQdf). (Preliminary) 2000-- 16 g WHO98 TEQdf (14 g I-TEQDF). (Preliminary)___________________ W ater Releases__________________________ None.___________________________________________________________________ Solid Residue Releases_______________________ None.___________________________________________________________________ Products_____________________________ None. 1 2 3 7.6. NONFERROUS METAL FOUNDRIES 4 This is a new section. 5 6 7.6.1. Aluminum Foundries 7 N o C D D /C D F em issions data w ere found for alum inum foundries. H ow ever, U N EP 8 (2005) provides a range o f em ission factors for various types o f alum inum processing. F or the 9 purposes o f a prelim inary estim ate, a m idrange value o f 3.5 ng I-T E Q /kg w as assum ed to apply 10 to all referen ce years. T his corresponds to w ell-co n tro lled facilities w ith fab ric filters and lim e 11 in jectio n . 12 T he activity estim ate fo r alum inum fo u n d ries in 2000 w as found to b e 95,600 M T b ased 13 o n th e U S G S M in e ra ls Y e a rb o o k (U S G S , 2 0 0 0 ). T h e e a rlie r y e a rs w e re e stim a te d b y a ssu m in g 14 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-29 DRAFT: DO NOT CITE OR QUOTE 1 that foundry production w as a constant ratio w ith total consum ption: 82,500 M T in 1995 and 2 72,000 M T in 1987. 3 Foundries typically have solid w aste associated w ith residues from the casting process. 4 N o inform ation w as found on C D D /C D F levels in these m aterials. H ow ever, these residues 5 w ould be landfilled and, therefore, are not considered an environm ental release. 6 The inventory decision criteria and releases to all m edia are sum m arized below : 7 Inventory Decision Criteria for Aluminum Foundries Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. No A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 8 9 Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-30 DRAFT: DO NOT CITE OR QUOTE Aluminum Foundries Air Releases_____ Emission Factors 1987--3.5 ng I-TEQDF/kg of metal feed (Preliminary). 1995--3.5 ng I-TEQDF/kg of metal feed (Preliminary). 2000--3.5 ng I-TEQDF/kg of metal feed (Preliminary). Activity Levels 1987--72,000 MT. 1995--82,500 MT. 2000--95,600 MT.____________________________ Releases 1987--0.3 g I-TEQdf (Preliminary). 1995--0.3 g I-TEQdf (Preliminary). 2000--0.3 g I-TEQdf (Preliminary)._______________ W ater Releases None._____________________________________________ Solid Residue Releases None._____________________________________________ Products_______ None 1 2 3 7.6.2. Copper Foundries 4 U N EP (2005) provides an em ission factor for copper casting operations o f 5 0.03 ng I-T E Q /kg o f copper based on em issions testing at foundries in G erm any. This w as 6 assum ed to apply to all reference years. 7 The activity estim ate for copper foundries in 2000 w as found to be 26,000 M T based on 8 the U SG S M inerals Y earbook (USGS, 2000). The earlier years w ere estim ated by assum ing that 9 foundry production w as a constant ratio w ith total consum ption: 21,000 M T in 1995 and 10 18,500 M T in 1987. 11 F o u n d rie s ty p ic a lly h av e so lid w a ste asso c ia te d w ith re sid u e s fro m th e c a stin g p ro c ess. 12 N o in fo rm atio n w as fo u n d on C D D /C D F levels in th ese m aterials. H ow ever, th ese resid u es 13 w o u ld b e la n d fille d and, th e re fo re , are n o t c o n sid e re d to b e an e n v iro n m e n ta l re le ase. 14 T he in v en to ry d ecisio n criteria and releases to all m ed ia are sum m arized below : 15 16 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-31 DRAFT: DO NOT CITE OR QUOTE 1 Inventory Decision Criteria for Aluminum Foundries Air W ater Solids Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). 2 Q 3 ________________________________________________ Copper Foundries Air Releases Emission Factors 1987--0.03 ng I-TEQDF/kg of metal feed. 1995--0.03 ng I-TEQDF/kg of metal feed. 2000--0.03 ng I-TEQDF/kg of metal feed._________ Activity Levels 1987--72,000 MT. 1995--82,500 MT. 2000--95,600 MT.___________________________ Releases 1987--<0.1 g I-TEQdf. 1995--<0.1 g I-TEQdf. 2000--<0.1 g I-TEQdf. W ater Releases None.____________________________________________ Solid Residue Releases None.____________________________________________ Products______ None.____________________________________________ 4 5 6 7 8 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-32 DRAFT: DO NOT CITE OR QUOTE 1 2 7.7. SCRAP ELECTRIC WIRE RECOVERY 3 No changes were made in the release estimates for these facilities. It is unknown how 4 many facilities in the United States conducted scrap wire recovery operations over the reference 5 years, so no activity estimates could be made, and therefore, no release estimates could be made 6 as well. 7 8 7.7.1. Air Releases 9 As reported in EPA (2006), CDDs/CDFs have been measured in the emissions from these 10 facilities. The emission factor from EPA (1987) of 15.8 ng WHO98 TEQDF(16.9 ng I-TEQDF/kg) 11 of scrap feed was applied to all reference years. This factor is considered preliminary because it 12 is based on testing at only one facility. Lacking activity information on these facilities; however, 13 no estimates of air releases can be made. 14 15 7.7.2. W ater Releases 16 No information was found indicating that these facilities have water effluents. 17 18 7.7.3. Solid Residue Releases 19 Ash is produced as a byproduct when scrap wire is combusted. Harnly et al. (1995) 20 analyzed soil/ash mixtures from three closed metal recovery facilities and from three closed sites 21 using open burning for copper recovery near a California desert town. The geometric means of 22 the total CDD/CDF concentrations at the facility sites and the open burning sites were 86,000 23 and 48,500 ng/kg, respectively. The geometric mean TEQ concentrations were 2,900 and 24 1,300 ng I-TEQDF/kg, respectively. A significantly higher geometric mean concentration 25 (19,000 ng I-TEQDF/kg) was found in fly ash located at two of the facility sites. Lacking activity 26 information on these facilities, no estimates of releases from solid residues can be made. The 27 portion of the ash that is disposed in landfills would not be considered an environmental release. 28 29 7.7.4. Products This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-33 DRAFT: DO NOT CITE OR QUOTE 1 N o inform ation w as found indicating that C D D /C D Fs w ere present in products from 2 these facilities. 3 7.7.5. Release Summary 4 The inventory decision criteria and releases to all m edia are sum m arized below . 5 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-34 DRAFT: DO NOT CITE OR QUOTE Scrap Electric Wire Recovery Air Releases________ Releases are possible but cannot be quantified (Not quantifiable). W ater Releases______ None._______________________________________________ Solid Residue Releases Releases are possible but cannot be quantified (Not quantifiable). Products_________ None. 1 2 3 7.8. DRUM AND BARREL RECLAMATION FURNACES 4 Changes were made to the activity estimates and resulting air-release estimates from 5 these facilities. 6 7 7.8.1. Air Releases 8 The emission factor estimate (17.5 ng WHO98 TEQDF/drum) was based on testing at a 9 reclamation facility equipped with an afterburner (U.S. EPA, 1987). The testing at this facility 10 indicated that the afterburner achieved a 95% reduction in CDD/CDF emissions. It is possible 11 that some of these facilities do not have afterburners and using this emission factor may 12 underestimate their emissions by 20 times. Based on this uncertainty and data from only one 13 facility, this emission factor is considered preliminary. EPA (2006) reports that 35 million 14 drums were reclaimed in 1997 based on RIPA (1997), and this was assumed for the activity level 15 in 2000. EPA (2006) assumed an activity level of 4.6 million drums in 1987 and 1995 based on 16 a personal communication. These activity assumptions imply a large change in barrel 17 reclamation activity over a short time period, which seems unlikely. Because the RIPA (1997) is 18 a stronger reference, the activity assumptions for 1987 and 1995 were changed to 35 million 19 barrels as well. However, survey data were lacking for all years and these activity estimates are 20 considered preliminary. 21 22 7.8.2. W ater Releases 23 24 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-35 DRAFT: DO NOT CITE OR QUOTE 1 N o inform ation w as found indicating that C D D /C D Fs w ere present in w ater releases from 2 these facilities. 3 4 7.8.3. Solid Residue Releases 5 Sludges and ashes are stored in collection pits at these facilities. N o inform ation w as 6 found indicating that C D D /C D Fs w ere present in solid residues from these facilities. H ow ever, 7 it is reasonable to assum e that C D D /C D Fs are present in these ashes because they have been 8 found in the ash from other types o f com bustion. Lacking m easurem ent inform ation, no 9 estim ates o f releases from solid residues can be m ade (N ot quantifiable). The portion o f the 10 solid w aste th at is disp o sed in lan d fills w o u ld n o t b e co n sid ered an en vironm ental release. 11 12 7.8.4. Products 13 N o in fo rm a tio n w a s fo u n d in d ic a tin g th a t C D D /C D F s w e re p re se n t in p ro d u c ts fro m 14 th ese facilities. 15 16 7.8.5. Release Summary 17 T he in v en to ry decision criteria and releases to all m ed ia are su m m arized b elo w : 18 Inventory Decision Criteria for Drum and Barrel Reclamation Furnaces Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 19 20 21 22 No P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-36 DRAFT: DO NOT CITE OR QUOTE 1 2 Drum and Barrel Reclamation Furnaces___________ Air Releases_______________________ Emission Factors 1987-- 17.5 ng WHO98 TEQDF/drum (16.5 ng I-TEQDF/drum) (Preliminary). 1995-- 17.5 ng WHO98 TEQDF/drum (16.5 ng I-TEQDF/drum) (Preliminary). 2000-- 17.5 ng WHO98 TEQpF/drum (16.5 ng I-TEQpF/drum) (Preliminary). Activity Levels 1987--35 million drums burned. 1995--35 million drums burned. 2000--35 million drums burned.___________________________________ Releases 1987--0.6 g WHO98 TEQdf (0.6 g I-TEQdf) (Preliminary). 1995--0.6 g WHO98 TEQdf (0.6 g I-TEQDF) (Preliminary). 2000--0.6 g WHO98 TEQdf (0.6 g I-TEQDF) (Preliminary)._____________ W ater Releases_____________________ None.______________________________________________________________ Solid Residue Releases__________________ Releases are possible but cannot be quantified.______________________________ Products________________________ None.______________________________________________________________ 3 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 7-37 DRAFT: DO NOT CITE OR QUOTE 1 8. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 2 3 4 8.1. BLEACHED CHEMICAL WOOD PULP AND PAPER MILLS 5 N o changes w ere m ade to the release estim ates for these facilities; how ever, som e 6 additional discussion is provided below to clarify how the estim ates w ere derived. 7 8 8.1.1. Air Releases 9 A ir releases from incineration o f sludges are covered in Section 3.7. 10 11 8.1.2. W ater Releases 12 F o r 1987 and 1995, an em issio n -facto r app ro ach w as n o t n eed ed b ecau se release 13 e stim a te s w e re a v a ila b le fo r v irtu a lly all fa cilities. T h e se d a ta ca m e fro m six in d u stry -w id e 14 surveys as d escrib ed in E P A (2006). 15 A n e m issio n -fa c to r a p p ro a c h w a s u s e d to e stim a te re le a se s in 2 0 0 0 b e c a u se a 16 co m p reh en siv e p lan t survey w as n o t done fo r th is year. T he em issio n facto r and activity 17 estim ates w ere p ro v id ed b y N C A S I (G illespie, 2 002) b ased on d ata from m u ltip le facilities. 18 19 8.1.3. Solid Residue Releases 20 As described in EPA (2006), the am ounts o f C D D /C D Fs in solid residues cam e from the 21 com prehensive industry surveys in 1987 and 1995. In 1990, the m ajority (75.5% ) o f the 22 w astew ater sludge generated by these facilities w as placed in landfills or in surface 23 im poundm ents, w ith the rem ainder incinerated (20.5% ), applied to land or used as com post 24 (4.1% ), or distributed as a com m ercial product (less than 1%) (U.S. EPA , 1993b). D ata on the 25 disposition o f w astew ater sludges are available only for years 1988 through 1995. On the basis 26 o f these data, the best estim ate o f the am ount applied to land (i.e., not incinerated or landfilled) is 27 14.1 g W H O 98 o r I-T E Q (4 .1 % o f 343 g) fo r 1987 a n d 2 g 1 g W H O 98 o r I-T E Q (4 .1 % o f 50 g) 28 for 1995. 29 F or 2000, the prim ary w aste treatm ent residuals from pulp m ills 30 (0.974 m illion dry M T/year) and the com bined, secondary, and dredged w aste treatm ent 31 resid u als from pulp m ills (1.37 m illio n dry M T /y ear) w ere derived from th e N C A S I database 32 (G illespie, 2002) on m ultiple facilities. This yields a total sludge production o f This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-1 DRAFT: DO NOT CITE OR QUOTE 1 2.34 million dry MT. Fifty-one percent of the sludge generated in 2000 was sent to landfills or 2 lagoons (Gillepsie, 2002). It is uncertain how much of the remaining 49% of the sludge was 3 applied to land. However, a conservative estimate can be developed by applying the 4.1% used 4 to develop the 1987 and 1995 estimates. This implies that 1.19 MMT was landfilled and 5 0.096 MMT were land applied. 6 The CDD/CDFs in sludges that are land applied are assumed to represent environmental 7 releases. These amounts are shown in the release summary below. The CDD/CDFs in sludges 8 that are landfilled are not considered to be environmental releases, and these amounts are listed 9 below: 10 11 1987--260 g WHO98 or I-TEQ/year 12 1995--38 g WHO98 or I-TEQ/year 13 2000--2 g WHO98 or I-TEQ/year 14 15 8.1.4. Products 16 The surveys discussed above provide information on the amounts of CDD/CDFs found in 17 wood pulp: 500 g WHO98 or I-TEQ in 1987, 40 g WHO98 or I-TEQ in 1995, and 0.6 g WHO98 or 18 I-TEQ in 2000. It is unknown if environmental releases occur from paper products made from 19 the pulp. The CDD/CDFs in wood pulp products can be considered to be a reservoir as 20 discussed further in Chapter 11. 21 22 8.1.5. Release Summary 23 The inventory decision criteria and releases to all media are summarized below: This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-2 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Bleached Chemical Wood Pulp and Paper Mills Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Yes Yes Em ission factor tests represent units that are typical o f the class. Yes Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 Yes Yes QQ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-3 DRAFT: DO NOT CITE OR QUOTE Bleached Chemical Wood Pulp and Paper Mills Air Releases_______________ Air releases from incineration of sludges are covered in Section 3.7._____ W ater Releases_____________ Emission Factor 2000--0.49 pg (WHO98 or I-TEQ/L) of wastewater.___________ Activity Level 2000--2.87 trillion L.____________________________________ Releases 1987--360 g (WHO98 or I-TEQ). 1995--28 g (WHO98 or I-TEQ). 2000-- 1 g (WHO98 or I-TEQ).____________________________ Solid Residue Releases__________ Emission Factor 2000-- 1.8 ng (WHO98 or I-TEQ/kg) of sludge._______________ Activity Level L and A pplied 2000--0.096 million dry MT.__________________________ Releases L and A pplied 1987-- 14 g (WHO98 or I-TEQ). 1995--2 g (WHO98 or I-TEQ). 2000--0.2 g (WHO98 or I-TEQ). Products Releases 1987--Not quantifiable. 1995--Not quantifiable. 2000--Not quantifiable. 1 2 3 8.2. STAND-ALONE CHLOR-ALKALI PLANTS 4 In the original report, Section 8.2 covered the manufacture of chlorine, chlorine 5 derivatives, and metal chlorides, and Section 8.3 covered the manufacture of halogenated organic 6 chemicals. These two sections have been reorganized into the following three sections: 7 8 8.2--Stand-Alone Chlor-Alkali Plants 9 10 11 12 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-4 DRAFT: DO NOT CITE OR QUOTE 1 8.3-- Stand-A lone V inyl C hloride M anufacturing Plants 2 8.4-- C om plex C hem ical Plants Producing C hlorine and a V ariety o f C hlorinated O rganics 3 4 B ecause the changes to these sections are extensive, they are presented here in their entirety. 5 A lthough the reorganization is extensive, only m inor changes w ere m ade to the release estim ates. 6 This section covers plants that produce only chlorine, sodium hydroxide (N aO H ), and 7 related caustic chem icals (also know n as chlor-alkali plants). These chem icals are also produced 8 at com plex plants that produce a variety o f chlorinated organic com pounds. The CD D /CD F 9 releases associated w ith chlor-alkali production at these com plex plants are covered in 10 S ection 8.4. 11 12 8.2.1. Process Description 13 C h lo rin e g a s is p ro d u c e d b y e le c tro ly sis o f b rin e in e le c tro ly tic cells. T h re e p ro c e sse s are 14 in use: th e d iap h rag m -cell process, th e m em b ran e-cell process, and th e m ercu ry -cell process. In 15 th e d ia p h ra g m -cell p ro c e ss, a p o ro u s d ia p h ra g m d iv id e s th e e le c tro ly tic ce ll, w h ic h c o n ta in s 16 brine, in to an anode co m p artm en t and a cathode com partm ent. W h en an electric cu rren t passes 17 th ro u g h th e brine, th e ch lo rin e io n s and sodium io n s from th e salt m o v e to th e electrodes. 18 C h lo rin e g as is p ro d u ced at th e anode, and sodium io n s at th e cath o d e re act w ith th e w ater, 19 form ing cau stic soda. In th e m em b ran e-cell process, th e co m p artm en ts are separated b y a 20 m em brane rather than a diaphragm . B rine is pum ped into the anode com partm ent, and only 21 sodium ions pass into the cathode com partm ent, w hich contains pure w ater. Thus, the caustic 22 soda produced has very little salt contam ination. In the m ercury-cell process, m ercury, w hich 23 flow s along the bottom o f the electrolytic cell, serves as the cathode. W hen an electric current 24 passes through the brine, chlorine is produced at the anode, and sodium dissolves in the m ercury, 25 form ing an am algam o f sodium and m ercury (C horine Institute, 2010). 26 U ntil the late 1970s, the prim ary type o f electrolytic process used in the chlor-alkali 27 industry to produce chlorine consisted o f the use o f m ercury cells containing graphite electrodes. 28 D uring the 1980s, titanium m etal anodes w ere developed to replace graphite electrodes 29 (U.S. EPA , 1982; C urlin and B om m araju, 1991). Currently, no U.S. facility is believed to use 30 graphite electrodes in the production o f chlorine gas (telephone conversation betw een L. Phillips, 31 V ersar, Inc., and T. F ield in g , U .S. E P A , O ffice o f W ater, F eb ru ary 1993). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-5 DRAFT: DO NOT CITE OR QUOTE 1 8.2.2. Regulations 2 A lthough E PA does not regulate C D D s/C D Fs specifically, it issued restrictions under 3 R C R A on the land disposal o f w astew ater and sludges generated by chlorine m anufacturers that 4 use the m ercury-cell process and the diaphragm -cell process (w ith graphite electrodes) (waste 5 codes K 071, K 073, and K 106) (40 C FR 268). 6 7 8.2.3. Literature 8 A s show n in Table 8-1, high levels o f C D Fs have been found in several sam ples o f 9 graphite electrode sludge from facilities in Europe. The CD Fs predom inate in these sludges, and 10 th e 2 ,3 ,7 ,8 -su b stitu ted congeners acco u n t fo r a large fractio n o f th e resp ectiv e co n g en er to tals 11 (R a p p e et al., 1990, 1991; R a p p e , 1993; S tran d ell et al., 1994). A lth o u g h th e o rig in o f th e C D F s 12 in grap h ite electro d e sludge is uncertain, ch lo rin atio n o f th e cyclic arom atic h y d ro carb o n s (such 13 as d ib e n z o fu ra n ) p re s e n t in th e coal ta r u s e d as a b in d in g a g e n t in th e g ra p h ite e le c tro d e s h as 14 b een p ro p o sed as th e p rim ary source (S trandell et al., 1994). F o r th is reason, sludges pro d u ced 15 u s in g m etal e le c tro d e s w e re n o t e x p e c te d to c o n ta in C D F s. H o w e v e r, re su lts o f an a n a ly sis o f 16 m etal electro d e sludge from a facility in Sw eden, analyzed as p art o f th e S w edish D io x in Survey, 17 show ed th at th e sludge co n tain ed hig h lev els o f C D F s (sim ilar to th o se o f th e g rap h ite sludge) 18 and p rim arily n o n d etec tab le lev els o f C D D s (S trandell et al., 1994). T he sludge sh o w ed th e 19 sam e ty p e o f C D F co n g en er pattern rep o rted b y R ap p e et al. (1991) and R ap p e (1993). Strandell 20 et al. suggested th at chlorination o f polyarom atic hydrocarbons p resent in the rubber linings o f 21 the electrolytic cell m ay have produced the C D Fs found in the one sam ple analyzed. 22 The C hlorine C hem istry Council (CCC), a trade association representing m anufacturers 23 that produce and/or use chlorine, sam pled a variety o f w aste stream s at seven stand-alone 24 chlor-alkali facilities in the U nited States (CCC, 2004). N ote that one o f these plants (O ccidental 25 in D eer Park, TX ) also produced vinyl chloride m onom er (VCM ), but the processes and 26 associated w aste stream s are adequately separated such that it can be treated as a stand-alone 27 facility. This inform ation is also sum m arized in D yke and A m endola (2007). This study 28 m easured C D D /C D F releases to w ater from all seven facilities as sum m arized in T able 8-2. A ir 29 releases w ere only detected at one facility (see Table 8-3). D yke and A m endola (2007) 30 sum m arized the am ount of C D D /C D F in all w aste stream s and provided a confidence rating for 31 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8 - 6 DRAFT: DO NOT CITE OR QUOTE 1 each value (see Table 8-4). Table 8-4 shows the amount of CDD/CDFs that are sent to off-site 2 incinerators, landfills, and deep-well injection facilities. The releases from incineration are 3 included in the estimates presented for hazardous waste incinerators (see Section 3.2). The 4 amounts sent to secure landfills and deep-well injection facilities are not considered to be 5 environmental releases. 6 Dyke and Amendola (2007) present release estimates for both the years 2000 and 2002. 7 The 2002 values are not reproduced here but are generally lower or similar to the 2000 values. 8 In the year 2000, five facilities with an SIC code for alkalies and chlorine reported dioxin 9 releases under the EPA TRI program (U.S. EPA, 2008). The sum of the air releases across these 10 facilities was 204 g, which EPA estimates is equal to 3.3 g WHO98 TEQDF. The sum of the 11 water releases across these facilities was 1,416 g, which EPA estimates is equal to 12 24.8 g WHO98 TEQdf. No releases to other media were reported. As explained in Chapter 1, the 13 TRI data are not used to make quantitative estimates in this document but rather as supportive 14 evidence that releases do occur. 15 16 8.2.4. Releases 17 The information presented in Dyke and Amendola (2007) was selected as the best basis 18 for estimating CDD/CDF releases from these facilities. The seven stand-alone chlor-alkali plants 19 covered in this study are believed to represent most of the stand-alone chlor-alkali production in 20 the United States. Therefore, it was unnecessary to develop emission factors to estimate releases 21 from untested facilities. The Dyke and Amendola release estimates are specific to the year 2000. 22 No release data were found for earlier years. Because the chemical production rates and 23 technologies used at these facilities were probably similar in 1995 and 2000, the 2000 results are 24 assumed to apply to 1995. However, significant changes may have occurred since 1987, so no 25 release estimates could be made for 1987. The releases to all media are presented in Table 8-4 26 and summarized below. 27 The solid residues from these plants are disposed in secure landfills or by deep-well 28 injection and, therefore, are not considered an environmental release. The amounts are 29 summarized below: 30 1987--Not Available This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-7 DRAFT: DO NOT CITE OR QUOTE 1 1995--2.7 g I-TEQ 2 2000--2.7 g I-TEQ 3 4 The inventory decision criteria and releases to all media are summarized below: 5 Inventory Decision Criteria for Stand-Alone Chlor-Alkali Plants Air W ater Solids Products Emission tests for at least two units/source types with Yes Yes ' sufficient documentation to directly derive emission factors. Measured emission factors consistent or have understandable differences. Yes Yes Emission factor tests represent units that are typical of the Yes class. Yes Activity estimates based on source-specific surveys. Yes Yes Conclusion (Q = Quantitative, P = Preliminary). 6 QQ 7 Stand-Alone Chlor-Alkali Plants____________________ Air Releases_____________________________ 1987--Not available. 1995--0.03 g I-TEQ. 2000--0.03 g I-TEQ.__________________________________________________ W ater Releases___________________________ 1987--Not available. 1995--2 g I-TEQ. 2000--2 g I-TEQ.____________________________________________________ Solid Residue Releases________________________ None. The solid residues from these plants are disposed in secure landfills or by deep-well injection and, therefore, are not considered an environmental release.__________________ Products______________________________ No information was found suggesting that CDD/CDFs are found in the products from these facilities. 8 9 10 8.3. STAND-ALONE VINYL CHLORIDE MANUFACTURING PLANTS 11 12 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-8 DRAFT: DO NOT CITE OR QUOTE 1 As explained at the beginning of Section 8.2, this is a new section based on the 2 reorganization of Sections 8.2 and 8.3 in the original report. This section covers plants that 3 produce only polyvinyl chloride (PVC) and PVC intermediates such as ethylene dichloride 4 (EDC) and VCM. These chemicals are also produced at complex plants that produce a variety of 5 chlorinated organic compounds. The CDD/CDF releases associated with vinyl chloride 6 production at these complex plants are covered in Section 8.4. 7 8 8.3.1. Process 9 PVC resins are produced from the polymerization of VCM. VCM is typically produced 10 by the thermal dehydrochlorination (commonly known as cracking) of EDC. The cracking of 11 EDC requires elevated pressure (20 to 30 atm) and temperature (450 to 650EC) and yields VCM 12 and HCl at about a 1:1 molar ratio. EDC is produced by two different methods: (1) direct 13 chlorination of ethylene with chlorine in the presence of a catalyst at a temperature of 50 to 14 60EC and pressure of 4 to 5 atm; and (2) oxychlorination, which involves reaction of ethylene 15 with HCl and oxygen in the presence of a catalyst at temperatures generally less than 325EC. 16 The primary source of HCl for the oxychlorination process is the HCl produced from the 17 cracking of EDC to form VCM. Most VCM manufacturing facilities are integrated with EDC 18 production facilities (The Vinyl Institute, 1998). 19 20 8.3.2. Regulations 21 Although EPA regulates emissions from EDC/VCM production facilities under the Clean 22 Water Act (40 CFR 61), the Clean Air Act (40 CFR 414), and RCRA (40 CFR 268, waste codes 23 F024, K019, and K020), CDDs/CDFs are not specifically regulated pollutants. 24 25 8.3.3. Literature 26 Although it has been generally recognized that CDDs/CDFs can be formed during the 27 manufacture of EDC, VCM, and PVC, manufacturers and environmental public interest groups 28 have disagreed as to the quantity of CDDs/CDFs that are formed and released to the environment 29 in wastes and possibly in PVC products. Greenpeace International initially determined that 30 CDDs and CDFs can be formed during the manufacture of PVC. In 1993, it issued a report on 31 CDD/CDF emissions associated with the production of EDC/VCM (Greenpeace, 1993). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-9 DRAFT: DO NOT CITE OR QUOTE 1 Greenpeace estimated that 5 to 10 g I-TEQdf were released to the environment (air, water, and 2 ground combined) annually for every 100,000 MT of VCM produced. This emission factor was 3 based on data gathered by Greenpeace on four European plants. The Vinyl Institute responded 4 with a critique of the Greenpeace report (ChemRisk, 1993). Miller (1993) summarized the 5 differing views of the two parties. According to Miller, European PVC manufacturers claimed 6 the emission factor was 0.01 to 0.5 g I-TEQdf/ 100,000 MT of VCM, and although Greenpeace 7 and ChemRisk used basically the same monitoring information to develop their emission factors, 8 Greenpeace adjusted the emission factor to account for unquantified fugitive emissions and 9 waste products that contain unspecified amounts of CDDs/CDFs. 10 In 1995, Greenpeace issued a second report (Stringer et al., 1995) reiterating the 11 organization's concern that the generation and the emission of CDDs/CDFs may be significant 12 and urging that further work be initiated to quantify and prevent emissions. Stringer et al. (1995) 13 presented the results of analyses of three samples of chlorinated wastes obtained from 14 U.S. EDC/VCM manufacturing facilities. The three samples were characterized according to 15 EPA hazardous waste classification numbers as an F024 waste (waste from the production of 16 short-chain aliphatics by free radical-catalyzed processes), a K019 waste (heavy ends from the 17 distillation of ethylene from EDC production), and a probable K020 waste (heavy ends from 18 distillation of vinyl chloride in VCM manufacturing). Table 8-5 presents the analytical results 19 reported by Stringer et al. (1995). This study acknowledged that because EDC/VCM production 20 technologies and waste treatment and disposal practices are very site-specific, the limited 21 information available on CDD/CDF generation and emissions made it difficult to quantify 22 amounts of CDDs/CDFs generated and emitted. 23 In response to the lack of definitive studies, and at the recommendation of the EPA, 24 U.S. PVC manufacturers began an extensive monitoring program--the Dioxin Characterization 25 Program (DCP). The objective of the DCP was to evaluate the extent and magnitude of potential 26 CDD/CDF releases to air, water, and land, as well as the potential for PVC product 27 contamination. Manufacturers performed emissions and product testing at several facilities that 28 were representative of various manufacturing and process control technologies. In 1998, The 29 Vinyl Institute completed studies of CDD/CDF releases in wastewater, wastewater treatment 30 plant solids, and stack gases, as well as studies of the CDD/CDF content of products (PVC resins 31 and EDC sold as products) (The Vinyl Institute, 1998). This study presented results for This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-10 DRAFT: DO NOT CITE OR QUOTE 1 22 samples from 14 of the 24 U.S. and Canadian facilities manufacturing suspension and mass 2 PVC resins (13 pipe resins, 3 bottle resins, and 6 packaging resins). The results for U.S. 3 manufacturers are summarized in Table 8-6. The 14 sampled sites represented approximately 4 74% of estimated 1995 U.S. and Canadian suspension and mass PVC resin production. 5 CDDs/CDFs were detected in only one sample (0.043 ng I-TEQDF/kg, assuming nondetects 6 equal to zero). The overall mean TEQ concentrations were 0.002 ng I-TEQDF/kg (assuming 7 nondetects equal to zero) and 0.7 ng I-TEQDF/kg (assuming nondetects equal to one-half the 8 DL). The DLs were 2 ng/kg or less for all congeners in all samples except for OCDD and 9 OCDF, which had DLs of 6 ng/kg or less. 10 The same study also presented results for six samples from four of the seven U.S. 11 facilities manufacturing dispersion PVC resins. CDDs/CDFs were detected in five of the 12 samples. The results are summarized in Table 8-6. In terms of production, the four sampled 13 sites represent approximately 61% of estimated 1995 U.S. dispersion PVC resin production. The 14 results ranged from not detected to 0.008 ng I-TEQDF/kg (overall mean = 0.001 ng I-TEQDF/kg, 15 assuming nondetects equal to zero, and 0.4 ng I-TEQDF/kg, assuming nondetects equal to 16 one-half the DL). The DLs were 2 ng/kg or less for all congeners in all samples except for 17 OCDD and OCDF, which had DLs of 4 ng/kg or less. 18 Results were also presented for five samples from 5 of the 15 U.S. facilities 19 manufacturing EDC. The results are summarized in Table 8-6. In terms of production, the 20 five sampled sites represented approximately 71% of the estimated EDC produced in the United 21 States in 1995. CDDs/CDFs were detected in only one sample (0.03 ng I-TEQDF/kg). The 22 overall mean TEQ concentrations were 0.006 ng I-TEQDF/kg (nondetects equal to zero) and 23 0.21 ng I-TEQDF/kg (nondetects equal to one-half the DL). The DLs for all congeners were 24 1 ng/kg or less. 25 EPA (2006) used concentration and production data to estimate that vinyl chloride 26 contained 0.02 g I-TEQ in 1995 and 0.02 g I-TEQ in 2000. It is unknown if releases occurred 27 from these products. 28 The Chlorine Chemistry Council (CCC), a trade association representing manufacturers 29 that produce and/or use chlorine, also sponsored studies to measure CDD/CDF releases from the 30 production of chlorine and chlorinated organics. The information from The Vinyl Institute and 31 CCC studies was summarized in a recent article by Dyke and Amendola (2007). This article This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-11 DRAFT: DO NOT CITE OR QUOTE 1 identifies tw o facilities as stand-alone vinyl chloride plants. D yke and A m endola (2007) 2 sum m arized the releases o f C D D /C D F to all m edia for the year 2000 and provided a confidence 3 rating for each value analogous to one used in this report (see Table 8-7). D yke and A m endola 4 (2007) presented release estim ates for both the years 2000 and 2002. The 2002 values are not 5 reproduced here but are generally low er or sim ilar to the 2000 values. 6 7 8.3.4. Releases 8 The inform ation presented in D yke and A m endola (2007) w as selected as the best basis 9 for estim ating C D D /C D F releases from these facilities. The tw o stand-alone vinyl chloride 10 p lants covered in th is study are b eliev ed to rep resen t m o st o f th e stand-alone vinyl chloride 11 p ro d u c tio n in th e U n ite d S tates. T h e re fo re , it w a s n o t n e c e ssa ry to d e v e lo p e m issio n fa c to rs to 12 estim ate releases from u n tested facilities. T he D y k e and A m en d o la (2007) release estim ates are 13 sp e c ific to th e y e a r 2 0 0 0 . S in c e th e c h e m ic al p ro d u c tio n ra te s a n d te c h n o lo g ie s u s e d at th e s e 14 facilities have changed sig n ifican tly since 1987, release estim ates can n o t b e m ad e fo r 1987 and 15 1995. 16 T able 8-7 show s th e am o u n t o f C D D /C D F s th at are sent to off-site in cin erato rs and 17 landfills. T he releases from in cin eratio n are in clu d ed in th e estim ates p resen ted fo r h azard ou s 18 w a ste in cin erato rs (see S ectio n 3.2). T h e am o u n t sen t to secure lan d fills (5.57 g I-T E Q in 2 000) 19 is n o t con sid ered to b e an environm ental release. 20 A s discussed above, several studies have detected C D D /C D Fs in PV C products. 21 H ow ever, no inform ation is available on possible releases from these products, and therefore, 22 they are a potential but unquantifiable source (N ot quantifiable). 23 The releases to all m edia from the stand-alone vinyl chloride plants are presented in 24 T able 8-7. 25 The inventory decision criteria and releases to all m edia are sum m arized below : 26 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-12 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Stand-Alone Vinyl Chloride Manufacturing Plants Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Yes Yes Em ission factor tests represent units that are typical o f the Yes class. Yes A ctivity estim ates based on source-specific surveys. Yes Yes C onclusion (Q = Q uantitative, P = Prelim inary). 1 QQ 2 Stand-Alone Vinyl Chloride Manufacturing Plants________________ Air Releases________________________________ 1987--Not available. 1995--Not available. 2000--0.62 g I-TEQ._____________________________________________________ W ater Releases_______________________________ 1987--Not available. 1995--Not available. 2000--<0.1 g I-TEQ._____________________________________________________ Solid Residue Releases____________________________ None. The solid residues from these plants are disposed in secure landfills and, therefore, are not considered to be an environmental release._______________________________________ Products__________________________________ Not quantifiable._______________________________________________________________ 3 4 5 8.4. COMPLEX CHEMICAL PLANTS PRODUCING CHLORINE AND A VARIETY 6 OF CHLORINATED ORGANICS 7 As explained at the beginning of Section 8.2, this is a new section based on the 8 reorganization of Sections 8.2 and 8.3 in the original report. This section describes CDD/CDF 9 releases from facilities that produce combinations of chlorine and multiple chlorinated organic 10 chemicals. The plants that exclusively manufacture chlorine are covered in Section 8.2, and the 11 plants that exclusively produce vinyl chloride are covered in Section 8.3. 12 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-13 DRAFT: DO NOT CITE OR QUOTE 1 The w aste stream s at these com plex plants are typically com bined, w hich prevents 2 derivation o f chem ical-specific release estim ates. Instead, a facility-specific approach has been 3 used w here the releases for each plant are estim ated on the basis o f the CD D /C D F levels and 4 total flow rates m easured at the final release point. 5 These plants currently-- or have in the past-- produced a variety o f chem icals that have 6 been associated w ith C D D /C D F releases. These include chlorine, vinyl chloride, chlorophenols, 7 chlorobenzenes, and chlorobiphenyls. B ackground inform ation on the regulations, processes, 8 and products related to chlorine and vinyl chloride products w ere presented in Sections 8.2 and 9 8.3, respectively. Therefore, they are not repeated in this section. The production and use o f 10 chlorophenols, ch lo ro p h en o x y herbicides, and P C B pro d u cts are n o w b an n ed or strictly reg u lated 11 in m o s t c o u n trie s. P C B p ro d u c tio n c e a se d p rio r to th e first re fe re n c e y ear, i.e., 1987. So 12 C D D /C D F releases asso ciated w ith P C B p ro d u ctio n are n o t covered in th is rep o rt (P C B releases 13 fro m n o n p ro d u c tio n c o n te m p o ra ry so u rc e s are c o v e re d in C h a p te r 10, a n d re le a se s fro m 14 reserv o irs are covered in C h ap ter 11). 15 S ectio n 8.4 firs t p re se n ts se p a ra te d isc u ssio n s o n c h lo ro p h e n o l a n d ch lo ro b e n z e n e s. 16 T hese d iscu ssio n s d escribe the m an u factu rin g p rocesses, regulations, and p ro d u cts fo r these 17 chem ical groups. T hen th e section p resen ts th e release estim ates o ccu rrin g durin g p ro d u ctio n 18 activ ities at th e co m p lex plants. 19 20 8.4.1. Chlorophenols 21 8.4.1.1. P ro c e ss D e sc rip tio n 22 The tw o m ajor com m ercial m ethods used to produce chlorophenols are (1) electrophilic 23 chlorination o f m olten phenol by chlorine gas in the presence o f catalytic am ounts o f a m etal 24 chloride and organic chlorination prom oters and stabilizers, and (2) alkaline hydrolysis of 25 chlorobenzenes under heat and pressure using aqueous m ethanolic sodium hydroxide. O ther 26 m anufacturing m ethods include conversion o f diazonium salts o f various chlorinated anilines and 27 chlorination o f phenolsulfonic acids and benzenesulfonic acids, follow ed by the rem oval o f the 28 sulfonic acid group (G ilm an et al., 1988; H utzinger and Fiedler, 1991b). 29 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-14 DRAFT: DO NOT CITE OR QUOTE 1 8.4.I.2. R e g u la tio n s f o r C h lo ro p h e n o ls 2 In 1983, E P A cancelled the sale o f Silvex and 2,4,5-T for all uses (Federal R egister, 3 1987a). Earlier, in 1979, E PA had ordered em ergency suspension o f the forestry, rights-of-w ay, 4 and pasture uses o f 2,4,5-T. E m ergency suspensions o f the forestry, rights-of-w ay, pasture, 5 hom e and garden, com m ercial/ornam ental turf, and aquatic w eed control/ditch bank uses o f 6 Silvex w ere also ordered (Federal R egister, 1979; Plim m er, 1980). The hom e and garden, 7 com m ercial/ornam ental turf, and aquatic w eed control/ditch bank uses o f 2,4,5-T had been 8 suspended in 1970. 9 Pentachlorophenol (PC P) w as one o f the m ost w idely used biocides in the U nited States 10 p rio r to th e reg u lato ry actio n s to cancel and restrict certain o f its w o o d and n o n w o o d p reserv ativ e 11 u ses. P C P w a s re g iste re d fo r u se as a h e rb ic id e , d e fo lia n t, m o ssic id e , an d m u sh ro o m h o u se 12 biocide. It also fo u n d u se as a b io cid e in p u lp -p ap er m ills, oil w ells, and cooling tow ers. T hese 13 la tte r th re e u se s w e re te rm in a te d o n o r b e fo re 1993 (U .S . E P A , 1993b). H o w e v e r, th e m a jo r u se 14 (g reater th an 80% o f co n su m p tio n ) o f P C P w as and continues to b e w o o d preservation. A n 15 o v e rv ie w o f th e h isto ry o f th e P C P p e stic id e ru le s is p re se n te d b elo w . 16 In 1984, E P A issu ed a n o tice o f in ten t to cancel reg istratio n s o f p esticid e p ro d u cts 17 co n tain in g P C P (including its salts) fo r all w o o d p reserv ativ e u ses (F ederal R egister, 1984). T his 18 n o tice sp ecified m o d ificatio n s to th e term s and co n d itio n s o f p ro d u c t re g istra tio n s th a t w ere 19 req u ired in o rd er to avoid can cellatio n o f th e products. In resp o n se to th is notice, several trade 20 associations and registrants requested adm inistrative hearings to challenge E P A 's 21 determ inations. A fter considering the com m ents and alternatives suggested during the 22 prehearing stage o f the adm inistrative proceedings, E PA concluded that certain changes to the 23 1984 notice w ere appropriate. These changes, finalized in 1986 (Federal R egister, 1986), 24 included the follow ing: (a) all w ood preservative uses o f PC P and its salts w ere classified as 25 "restricted use" only by certified applicators, (b) specific w orker protection m easures w ere 26 required, (c) lim its w ere placed on the H xC D D content o f PCP, and (d) label restrictions for 27 hom e and farm uses o f PC P prohibited its application indoors and to w ood intended for interior 28 use (w ith a few exceptions) as w ell as its application in a m anner that m ight result in direct 29 exposure o f dom estic anim als or livestock or in the contam ination o f food, feed, or drinking and 30 irrigation water. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-15 DRAFT: DO NOT CITE OR QUOTE 1 EPA subsequently am ended its notice on the w ood preservative uses to establish reliable 2 and enforceable m ethods for im plem enting certified lim its for H xC D D and 2,3,7,8-TC D D in 3 registered w ood preservative pesticide products (Federal R egister, 1987b). Levels o f 4 2,3,7,8-TC D D w ere not allow ed to exceed 1 ppb in any product, and after February 2, 1989, any 5 m anufacturing-use PC P released for shipm ent could not contain H xC D D levels that exceeded an 6 average o f 2 ppm over a m onthly release or a batch level o f 4 ppm (a gradually phased-in 7 requirem ent). On January 21, 1987, E PA prohibited the registration o f PC P and its salts for m ost 8 nonw ood uses (Federal R egister, 1987c). E P A deferred action on several uses (uses in 9 pulp/paper m ills, oil w ells, and cooling tow ers) pending receipt o f additional exposure, use, and 10 ecological effects data. O n Jan u ary 8, 1993, E P A issu ed a press adv iso ry stating th at its special 11 re v ie w o f th e s e d e fe rre d n o n w o o d u se s w a s b e in g te rm in a te d b e c a u se all o f th e se u se s h a d b e e n 12 eith er v o lu n tarily can celled b y th e reg istran ts or can celled b y E P A fo r failu re o f th e reg istran ts to 13 p a y th e re q u ire d an n u a l m a in te n a n c e fe es (U .S . E P A , 1993b). 14 D i- and trich lo ro p h en o l m an u factu rers are su b ject to rep o rtin g u n d er th e D io x in /F u ran 15 T e st R u le , w h ic h is d isc u sse d in S ectio n 8 .3 .7 o f th e o rig in a l rep o rt. S in c e th e e ffe c tiv e d ate o f 16 th at ru le (Ju n e 5, 1987), only th e 2 ,4 -d ich lo ro p h en o l iso m er has b een co m m ercially p ro d u ced in 17 (or im p o rted to ) th e U n ited States, and as n o ted in T able 8-8, no C D D s/C D F s w ere d etected in 18 th e pro d u ct. T estin g is req u ired fo r th e o th er di- an d trich lo ro p h e n o ls i f m an u fa ctu re or 19 im p o rtatio n resum es. Sim ilarly, tetrach lo ro p h en o ls w ere subject to rep o rtin g u n d er the 20 D ioxin/Furan Pesticide D ata C all-In (discussed in Section 8.3.8 o f the original report). Since 21 issuance o f the D ata C all-in, the registrants o f tetrachlorophenol-containing pesticide products 22 have elected to no longer support the registration o f their products in the U nited States. 23 In the m id-1980s, the E P A O ffice o f Solid W aste (O SW ) prom ulgated, under R C R A , 24 land disposal restrictions on w astes (w astew aters and nonw astew aters) resulting from the 25 m anufacture o f chlorophenols (40 C FR 268). Table 8-9 lists all w astes in w hich C D D s/C D Fs are 26 specifically regulated by EPA as hazardous constituents, including chlorophenol w astes (w aste 27 codes F020 and F021). The regulations prohibit the land disposal o f these w astes until they are 28 treated to a level below the routinely achievable D Ls for the E P A hazardous w aste num bers 29 listed in Table 8-9 for each o f the follow ing congener groups: TCDDs, PeC D D s, H xCD D s, 30 TCDFs, PeC D Fs, and H xC D Fs. W astes from PC P-based w ood-preserving operations (w aste 31 codes K 001 and F 032) are also reg u lated as h azard o u s w astes u n d er R C R A (40 C F R 261). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-16 DRAFT: DO N O T CITE OR QUO TE 1 The EPA O ffice o f W ater prom ulgated effluent lim itations for facilities that m anufacture 2 chlorinated phenols and discharge treated w astew ater (40 C FR 414.70). These effluent 3 lim itations do not specifically regulate C D D s or CDFs. The effluent lim itations for the 4 individually regulated chlorinated phenols are less than or equal to 39 pg/L for facilities that use 5 biological end-of-pipe treatm ent. 6 7 8.4.I.3. P r o d u c ts -- C h lo ro p h e n o ls 8 C hlorophenols have been w idely used for a variety o f pesticidal applications. The 9 higher-chlorinated phenols (tetrachlorophenol and PC P) and their sodium salts have been used 10 prim arily fo r w o o d p reservation. T he lo w er-ch lo rin ated ph en o ls hav e b een u sed prim arily as 11 ch e m ic al in te rm e d ia te s in th e m a n u fa c tu re o f o th e r p e stic id e s. F o r e x a m p le , 2 ,4 -d ic h lo ro p h e n o l 12 is u sed to pro d u ce th e h erb icid es 2 ,4 -dich lo ro p h en o x y acetic acid (2,4-D ), 13 4 -(2 ,4 -d ic h lo ro p h e n o x y )b u ta n o ic ac id (2 ,4 -D B ), 2 -(2 ,4 -d ic h lo ro p h e n o x y )-p ro p a n o ic acid 14 (2,4-D P ), N itro p h en , G enite, and Z ytron, and 2 ,4 ,5 -trich lo ro p h en o l w as u sed to produce 15 h e x a c h lo ro p h e n e , 2 ,4 ,5 -T , S ilv ex , E rb o n , R o n n e l, a n d G a rd o n a (G ilm a n et al., 1988; H u tz in g e r 16 and F iedler, 1991b). 17 B ecau se o f the m an u factu rin g p ro cesses em ployed, com m ercial chlorophenol products 18 can co n tain ap p reciab le am o u n ts o f im p u ritie s (G ilm an et al., 1988). D u rin g th e d irect 19 ch lo rin atio n o f phenol, C D D s/C D F s can form eith er b y th e co n d en satio n o f tri-, tetra-, and 20 pentachlorophenols or by the condensation o f chlorophenols w ith hexachlorocyclohexadienone 21 (w hich form s from excessive chlorination o f phenol). D uring alkaline hydrolysis o f 22 chlorobenzenes, C D D s/C D Fs can form through chlorophenate condensation (R ee et al., 1988; 23 G ilm an et al., 1988; H utzinger and Fiedler, 1991b) 24 The lim ited inform ation on CD D /C D F concentrations in chlorophenols published in the 25 1970s and early 1980s w as com piled by V ersar, Inc. (1985) and H utzinger and F iedler (1991b). 26 The results o f several m ajor studies cited by these review ers (Firestone et al., 1972; R appe and 27 M arklund, 1978; R appe et al., 1978) are presented in T able 8-8. T ypically, C D D s/C D Fs w ere 28 not detected in m ono- and dichlorophenols but w ere reported in tri- and tetrachlorophenols. 29 M ore recent results o f testing o f 2,4-dichlorophenol, perform ed in response to the Toxic 30 Substances Control A ct (TSC A ) dioxin/furan test rule, show ed no detectable concentrations o f 31 2 ,3 ,7 ,8 -su b stitu ted tetra- th ro u g h h epta-C D D /C D F s. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-17 DRAFT: DO NOT CITE OR QUOTE 1 Detailed information on 2,4,5-T production and 2,3,7,8-TCDD levels was presented in 2 Chapter 11 of the original report. Production of 2,4,5-T during the 1950s, 1960s, and 1970s was 3 estimated as 2,000, 4,000, and 1,500 MT/year, respectively. This was combined with estimates 4 of 2,3,7,8-TCDD levels in the product to estimate that the cumulative amount of 2,3,7,8-TCDD 5 in 2,4,5-T used over the period of 1950 to 1979 was 36,000 g. No product release estimates are 6 presented for the reference years because production ceased prior to 1987. After the chemical 7 was applied, it would have become incorporated into the soil reservoir. The potential amounts of 8 2,3,7,8-TCDD remaining in the soil reservoir and possible releases are discussed in Chapter 11. 9 The production of PCP for wood preserving began on an experimental basis in the 1930s. 10 In 1947, nearly 3,200 MT of PCP were reported to have been used in the United States by the 11 commercial wood preserving industry. Use in this industry steadily increased through the 12 mid-1970s (AWPI, 1977). Although domestic consumption volumes are not available for all 13 years, it is estimated, on the basis of historical production/export data for PCP reported in 14 Mannsville (1983), that 90 to 95% of production volume has typically been consumed 15 domestically rather than exported. A reasonable estimate of total domestic PCP consumption 16 during the period of 1970 to 1995 is about 400,000 MT. This estimate assumes an average 17 annual consumption rate of 20,000 MT/year during the 1970s, 15,000 MT/year during the 1980s, 18 and 10,000 MT/year during the 1990s. 19 Table 8-10 presents a compilation of published data on the CDD/CDF content of 20 technical-grade PCP. The only samples that have been analyzed for all dioxin-like CDDs/CDFs 21 were manufactured in the mid-to-late 1980s. Figure 8-1 presents these data in graphical form. It 22 shows that the predominant congener groups are OCDD, OCDF, and HpCDD, Waddell et al. 23 (1995) tested analytical-grade PCP (from Aldrich Chemical Co.) for CDD/CDF content and 24 found the same congener profile; however, the CDD/CDF levels were three to four orders of 25 magnitude lower. Table 8-11 presents a similar compilation of published data on the CDD/CDF 26 content of PCP-Na. The table shows the same patterns of dominant congeners and congener 27 groups reported for PCP 28 Samples of technical-grade PCP manufactured during the mid-to-late 1980s contained 29 about 1.7 mg WHO98 TEQDF/kg (3 mg I-TEQ/kg), based on the data presented in Table 8-10. 30 No published reports could be located that present the results of any congener-specific analyses 31 of PCP manufactured since the late 1980s. However, monthly measurements of CDD/CDF This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-18 DRAFT: DO NOT CITE OR QUOTE 1 congener group concentrations in technical PCP manufactured for use in the United States have 2 been reported to EPA from 1987 to the present (letter dated March 5, 1997, from Thomas 3 Mitchell, KMG-Bernuth, to Matthew Lorber, U.S. EPA; letter dated February 7, 1997, from John 4 Wilkinson, Pentachlorophenol Task Force, to Matthew Lorber, U.S. EPA; U.S. EPA, 1999a). 5 The average congener group concentrations reported to EPA for the years 1988 (i.e., 1 year after 6 EPA regulations were imposed limiting HxCDD and 2,3,7,8-TCDD concentrations in PCP) to 7 1999 are presented in Table 8-10. In general, the average congener group concentrations during 8 the period of 1988 to 1999 are lower by a factor of 2 to 4 than the concentrations observed in the 9 mid-to-late 1980 (based on the full-congener analysis of samples). If it is assumed that the toxic 10 CDD/CDF congeners have also been reduced by a similar factor, then the TEQ content of PCP 11 manufactured since 1988 is about 0.6 mg WHO98 TEQDF/kg (1 mg I-TEQ/kg). 12 An estimated 12,000 MT of PCP were used for wood preservation in the United States in 13 1987 (WHO, 1991). An estimated 8,400 MT were used in 1994 (AWPI, 1995); for the purposes 14 of this report, it is assumed that an identical amount was used in 1995. In 1999, approximately 15 7,710 MT of PCP were produced annually in the United States (Council of Great Lakes 16 Industries, 1999); for the purposes of this report, it is assumed that an identical amount was 17 produced in 2000. Assuming that 95% of the production volume was consumed domestically 18 (Mannsville, 1983) and that all of the PCP produced in 2000 was used for wood preservation, 19 approximately 7,325 MT of PCP were used in the United States for wood preservation. 20 Combining these activity level estimates with the TEQ concentration estimates presented above 21 indicates that 20,000 g WHO98 TEQDF(36,000 g I-TEQDF), 4,800 g WHO98 TEQDF 22 (8,400 g I-TEQdf), and 4,200 g WHO98 TEQDF(7,300 g I-TEQDF) were incorporated into 23 PCP-treated wood products in 1987, 1995, and 2000, respectively. It is unknown how much of 24 the CDD/CDFs escape from the wood into the environment. Several field studies (Gurprasad et 25 al., 1995; EPRI, 1995; Wan, 1995; Wan and Van Oostdam, 1995) demonstrate that CDDs/CDFs 26 do apparently leach into soil from PCP-treated wood, but the studies do not provide release-rate 27 data. No studies were located that provide any measured CDD/CDF volatilization rates from 28 PCP-treated wood. Although CDDs/CDFs have very low vapor pressures, they are not bound to, 29 nor do they react with, the wood in any way that would preclude volatilization. Lorber et al. 30 (2002) compared the spatial distribution of CDD/CDF congeners in PCP-treated poles of 31 different ages. A trend for dioxins to concentrate in the outer portions of the pole over time This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-19 DRAFT: DO NOT CITE OR QUOTE 1 suggests migration within the poles, and this migration may result in some environmental 2 release. However, this study could not quantify such releases. Several studies (Bremmer et al. 3 [1994], Rappe [1995], Eduljee and Dyke [1996] and Douben et al. [1995]) have attempted to 4 estimate potential CDD/CDF volatilization releases using conservative assumptions or modeling 5 approaches, but these estimates span many orders of magnitude. Therefore, no estimate could be 6 made as to what portion of the CDD/CDFs in products are released to the environment (Not 7 quantifiable). The cumulative amounts of CDD/CDFs in PCP-treated wood can also be 8 considered a potential reservoir source (see Chapter 11 for further discussion of this issue). 9 10 8.4.I.4. P ro d u c ts--2 ,4 -D 11 Although 2,4-Dichlorophenoxyacetic acid (2,4-D) is not a true chlorophenol, it is 12 included in this section because it is produced from chlorophenols and, therefore, is closely 13 associated. The available information on 2,4-D production and CDD/CDF levels was 14 summarized in Chapter 11 of the original report. An estimated 28,100 MT of 2,4-D were used in 15 the United States in 2000, making it one of the top 10 pesticides in terms of quantity used (EPA 16 proprietary data). The pesticide 2,4-D is judged to have the potential for environmental release 17 through its agricultural use. Since 1995, the chemical manufacturers of 2,4-D have been 18 undertaking voluntary actions to significantly reduce the dioxin content of the product. No 19 information is available on the level of dioxin contamination, if any, that may have been present 20 in 2,4-D in 2000. An estimated 26,300 and 30,400 MT were used during 1995 and 1987, 21 respectively (U.S. EPA, 1997c, 1988). On the basis of the average CDD/CDF congener 22 concentrations in 2,4-D (not including OCDD and OCDF), the corresponding WHO98 TEQDF 23 concentration is 1.1 pg/kg (0.7 pg I-TEQDF/kg). Combining this TEQ concentration with the 24 activity level estimates for 1995 and 1987 indicates that 28.9 g WHO98 TEQDF(18.4 g I-TEQDF) 25 were released in 1995 and 33.4 g WHO98 TEQDF(21.3 g I-TEQDF) was released in 1987. No 26 estimate can be made for 2000 because of the poor quality of existing information. 27 28 8.4.2. Chlorobenzenes 29 8.4.2.I. P ro c e ss D e sc rip tio n 30 Chlorobenzenes can be produced via three methods: (1) electrophilic substitution of 31 benzene (in liquid or vapor phase) with chlorine gas in the presence of a metal salt catalyst, This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-20 DRAFT: DO NOT CITE OR QUOTE 1 (2) oxidative chlorination of benzene with HCl at 150 to 300EC in the presence of a metal salt 2 catalyst, and (3) dehydrohalogenation of hexachlorocyclohexane wastes at 200 to 240EC with a 3 carbon catalyst to produce trichlorobenzene, which can be further chlorinated to produce 4 higher-chlorinated benzenes (Ree et al., 1988; Hutzinger and Fiedler, 1991b; Bryant, 1993). 5 All chlorobenzenes currently manufactured in the United States are produced by the 6 electrophilic substitution process using liquid-phase benzene (i.e., temperature is at or below 7 80EC). FeCl3is the most common catalyst employed. Although this method can be used to 8 produce mono- through hexachlorobenzene, the extent of chlorination is controlled to yield 9 primarily monochlorobenzene and dichlorobenzene. The finished product is a mixture of 10 chlorobenzenes, and refined products must be obtained by distillation and crystallization (Bryant, 11 1993). 12 13 8.4.2.2. R e g u la tio n s f o r C h lo ro b e n ze n e s 14 EPA determined, as part of the Federal Insecticide, Fungicide, and Rodenticide Act 15 (FIFRA) Data Call-In, that the 1,4-dichlorobenzene manufacturing processes used in the United 16 States are not likely to form CDDs/CDFs. Mono-, di-, and trichlorobenzene are listed as 17 potential precursor chemicals under the TSCA dioxin/furan test rule and are subject to reporting. 18 In addition, EPA issued a Significant New Use Rule (SNUR) under Section 5(a)(2) of TSCA on 19 December 1, 1993 (effective January 14, 1994) for pentachlorobenzene and 20 1,2,4,5-tetrachlorobenzene (Federal Register, 1993). This rule requires that EPA be notified at 21 least 90 days before the manufacture, import, or processing of either of these compounds in 22 amounts of 10,000 pounds or greater per year per facility for any use. All registrations of 23 pesticide products containing hexachlorobenzene were cancelled in the mid-1980s (Carpenter 24 et al., 1986). 25 OSW promulgated land disposal restrictions on wastes (i.e., wastewaters and 26 nonwastewaters) resulting from the manufacture of chlorobenzenes (40 CFR 268). Table 8-9 27 lists all solid wastes for which EPA specifically regulates CDDs and CDFs, including 28 chlorobenzene wastes, as hazardous constituents. The regulations prohibit the land disposal of 29 these wastes until they are treated to a level below the routinely achievable DLs in the waste 30 extract listed in Table 8-9 for each of the following congener groups: TCDDs, PeCDDs, 31 HxCDDs, TCDFs, PeCDFs, and HxCDFs. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-21 DRAFT: DO NOT CITE OR QUOTE 1 The EPA O ffice o f W ater prom ulgated effluent lim itations for facilities that m anufacture 2 chlorinated benzenes and discharge treated w astew ater (40 C FR 414.70). These effluent 3 lim itations do not specifically address C D D s and CDFs. The follow ing chlorinated benzenes are 4 regulated: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 5 1.2.4- trichlorobenzene, and hexachlorobenzene. The effluent lim itations for the individual 6 regulated chlorinated benzenes are less than or equal to 77 pg/L for facilities that use biological 7 end-of-pipe treatm ent and less than or equal to 196 pg/L for facilities that do not use biological 8 end-of-pipe treatm ent. 9 Since at least 1993, U .S. com m ercial production o f chlorobenzenes has been lim ited to 10 m o n o ch lo ro b en zen e, 1,2-dichlorobenzene, 1,4-dichlorobenzene, and, to a m u ch lesser extent, 11 1 .2.4- tric h lo ro b e n z e n e . A s n o te d ab o v e, C D D /C D F fo rm a tio n is n o t e x p e c te d u n d e r th e n o rm al 12 op eratin g co n d itio n s o f th e p ro cesses currently u sed in th e U n ited S tates to p ro d u ce th ese 13 fo u r c h e m ic als. N o te tra -, p en ta-, o r h e x a c h lo rin a te d b e n z e n e s are n o w in te n tio n a lly p ro d u c e d o r 14 u sed in th e U n ited S tates (B ryant, 1993). T hus, releases o f C D D s/C D F s from th e m an u factu re o f 15 c h lo ro b e n z e n e s in 1995 w e re e s tim a te d to b e n e g lig ib le . B e c a u s e th e in fo rm a tio n a v a ila b le on 16 C D D /C D F co n ten t o f m o n o -th ro u g h p en tach lo ro b en zen e is v ery lim ited and is b ased p rim arily 17 on u n p u b lish ed E u ro p ean data, and b ecau se in fo rm atio n on th e chlo ro b en zen e m an u factu rin g 18 p ro cesses in p lace d u rin g 1987 is n o t read ily available, no em issio n estim ates can b e m ad e fo r 19 1987. 20 21 8.4.2.3. P r o d u c ts -- C h lo ro b e n ze n e s 22 C hlorobenzenes have been produced in the U nited States since 1909. U .S. production 23 operations w ere developed prim arily to provide chem ical raw m aterials for the production o f 24 phenol, aniline, and various pesticides based on the higher-chlorinated benzenes. B ecause o f 25 (increm ental) changes in the processes used to m anufacture phenol and aniline and the phaseout 26 o f highly chlorinated pesticides such as D D T and hexachlorobenzene, U.S. production o f 27 chlorobenzenes in 1988 had decreased to 50% o f the peak production level, in 1969. 28 C D D s/C D Fs can be produced inadvertently during the m anufacture o f chlorobenzenes by 29 nucleophilic substitution and pyrolysis m echanism s (R ee et al., 1988). The criteria required for 30 production o f C D D s/C D Fs via nucleophilic substitution are oxygen as a nuclear substituent (i.e., 31 p resen ce o f ch lo ro p h en o ls) and p ro d u ctio n or p u rificatio n o f th e substance u n d er alkaline This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-22 DRAFT: DO NOT CITE OR QUOTE 1 conditions. Formation via pyrolysis requires reaction temperatures above 150C (Ree et al., 2 1988; Hutzinger and Fiedler, 1991b). The liquid-phase electrophilic substitution process 3 currently used in the United States does not meet either of these criteria. Although Ree et al. 4 (1988) and Hutzinger and Fiedler (1991b) state that the criteria for formation of CDDs/CDFs via 5 nucleophilic substitution may be present in the catalyst neutralization and purification/distillation 6 steps of the manufacturing process; Opatick (1995) states that the chlorobenzene reaction 7 product in U.S. processes remains mildly acidic throughout these steps. 8 Table 8-12 summarizes the very limited published information on CDD/CDF 9 contamination of chlorobenzene products. The presence of CDDs/CDFs has been reported in 10 tri-, penta-, and hexachlorobenzene. No CDDs/CDFs have been reported in mono- or 11 dichlorobenzene. Conflicting data exist concerning the presence of CDDs/CDFs in 12 trichlorobenzene. One study (Villanueva et al., 1974) detected no CDDs/CDFs in one sample of 13 1,2,4-TCBz at a DL of 0.1 pg/kg. Hutzinger and Fiedler (1991b) reported unpublished results of 14 a study by Dr. Hans Hagenmaier showing CDD/CDF congener group concentrations ranging 15 from 0.02 to 0.074 pg/kg in a sample of mixed TCBz. Because the TCBz examined by 16 Hagenmaier contained about 2% hexachlorocyclohexane, it is reasonable to assume that it was 17 produced by dehydrohalogenation of hexachlorocyclohexane (a manufacturing process not 18 currently used in the United States). 19 In conclusion, although there is some evidence that CDD/CDFs may be present in 20 chlorobenzene products, insufficient information is available to make quantitative estimates. 21 Accordingly, they are considered to be unquantifiable. 22 23 8.4.3. Complex Plants 24 In the year 2000, two facilities with an SIC code for plastic materials, synthetic resins, 25 and nonvulcanizable elastomers reported dioxin releases under the EPA TRI program (U.S. EPA, 26 2008). The sum of the air releases across these facilities was 5.6 g, which EPA estimates is 27 equal to 0.5 g WHO98 TEQDF. No releases to other media were reported. As explained in 28 Chapter 1, the TRI data are not used to make quantitative estimates in this document but rather as 29 supportive evidence that releases do occur. 30 In the year 2000, four facilities with an SIC code for industrial organic chemicals not 31 classified elsewhere reported dioxin releases under the EPA TRI program (U.S. EPA, 2008). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-23 DRAFT: DO NOT CITE OR QUOTE 1 The sum of the air releases across these facilities was 153 g, which EPA estimates is equal to 2 2.2 g WHO98 TEQdf. No releases to other media were reported. As explained in Chapter 1, the 3 TRI data are not used to make quantitative estimates in this document but rather as supportive 4 evidence that releases do occur. 5 The information presented in Dyke and Amendola (2007) was selected as the best basis 6 for estimating CDD/CDF releases from facilities that produce combinations of chlorine and 7 multiple chlorinated organic chemicals. The 10 complex chemical plants covered in this study 8 are believed to represent most facilities of this type in the United States. Therefore, it was 9 unnecessary to develop emission factors to estimate releases from untested facilities. Dyke and 10 Amendola reported their release estimates in I-TEQs, but stated that WHO98values were usually 11 less than 20% different. Using the water congener profile, the WHO98 values were computed to 12 be only 4% higher that the I-TEQs. On this basis the I-TEQs were assumed to be equivalent to 13 the WHO98 TEQs for all releases. The Dyke and Amendola release estimates are specific to the 14 year 2000. Because the chemical production rates and technologies used at these facilities have 15 changed significantly, no release estimates could be made for 1987 and 1995. 16 Table 8-13 shows the amount of CDD/CDFs that are sent to off-site incinerators and 17 landfills. The releases from incineration are included in the estimates presented for hazardous 18 waste incinerators (see Section 3.2). The amounts sent to secure landfills (118 g I-TEQ in 2000) 19 are not considered to be environmental releases. 20 The releases to all media from the complex chemical plants are presented in Table 8-13. 21 The inventory decision criteria and releases to all media are summarized below: 22 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-24 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Complex Chemical Plants Producing Chlorine and a Variety of Chlorinated Organics Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes Yes Yes Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Yes Yes Yes Yes Em ission factor tests represent units that are typical o f the Yes Yes Yes class. Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 Yes Yes Yes QQQ Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-25 DRAFT: DO NOT CITE OR QUOTE Complex Chemical Plants Producing Chlorine and a Variety of Chlorinated Organics Air Releases_______________________________ 1987--Not available. 1995--Not available. 2000--5 g (WHO98 or I-TEQ)._____________________________________________ W ater Releases______________________________ 1987--Not available. 1995--Not available. 2000--25 g (WHO98 or I-TEQ).____________________________________________ Solid Residue Releases___________________________ Landfarmed 1987--Not available. 1995--Not available. 2000-- 1 g (WHO98 or I-TEQ)._____________________________________________ Products________________________________ PVCs 1987--Not quantifiable. 1995--Not quantifiable. 2000--Not quantifiable. Pentachlorophenols 1987--Not quantifiable. 1995--Not quantifiable. 2000--Not quantifiable. 2,4-Dichlorophenoxy acetic acid (2,4-D) 1987--33 g WHO98 TEQdf (21 g I-TEQdf). 1995--29 g WHO98 TEQdf ( 1 8 g I-TEQdf). 2000--Not quantifiable. Chlorobenzenes 1987--Not quantifiable. 1995--Not quantifiable. 2000--Not quantifiable. 1 2 8.5. MUNICIPAL WASTEWATER TREATMENT PLANTS 3 This section corresponds to Section 8.4.1 of the original report. Minor changes were 4 made to the solid residue and product release estimates. 5 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-26 DRAFT: DO NOT CITE OR QUOTE 1 8.5.1. Air Releases 2 Releases associated with sewage sludge incineration are covered in Section 3.5. 3 4 8.5.2. W ater Releases 5 No changes were made to the emission factors, activities, or release estimates. The 6 CRWQCB data (memorandum dated March 21, 1996, from Lila Tang, California Regional 7 Water Quality Control Board, to David Cleverly, U.S. EPA) were the only U.S. data that 8 provided TEQ estimates for CDD/CDF levels in wastewaters from sewage treatment plants. 9 Accordingly, the concentration from this study (0.27 pg WHO98 TEQDF/L [0.29 pg I-TEQDF/L]) 10 was assumed to apply to all reference years. However, these data were from plants in the San 11 Francisco area and cannot be considered to be representative of the 16,000-plus POTWs 12 nationwide. Therefore, the emission factor was considered preliminary. Activity estimates were 13 derived from EPA surveys as described in US EPA (2006) and are presented in the release 14 summary below. 15 16 8.5.3. Solid Residue Releases 17 The large U.S. studies (U.S. EPA, 1996b, 2002d; Green et al., 1995; Cramer et al., 1995) 18 were selected as the best basis for estimating emission factors. Because the mean I-TEQDF 19 concentration values reported in the 1988/1989 sewage sludge survey (U.S. EPA, 1996b) and the 20 1995 survey (Green et al., 1995; Cramer et al., 1995) were very similar, the estimated amounts of 21 TEQs that may have been present in sewage sludge and released to the environment in 1987 and 22 1995 were assumed to be the same. These values were estimated using the average of the mean 23 concentration values (nondetects equal to DLs) reported by EPA (1996b) (50 ng I-TEQDF/kg) 24 and by Green et al. (1995) and Cramer et al. (1995) (36.3 ng WHO98 TEQDF/kg 25 [47.7 ng I-TEQDF/kg]). Therefore, the overall average mean emission factor for reference years 26 1987 and 1995 is 36.3 ng WHO98 TEQDF/kg (48.9 ng I-TEQDF/kg). The emission factor of 27 14 ng WHO98 TEQDF/kg (15 ng I-TEQDF/kg), as calculated from the 2001 survey (U.S. EPA, 28 2002d), appears to be the most reasonable TEQ emission factor estimate for reference year 2000 29 because this estimate is nationally weighted on the basis of wastewater flow rates of POTWs 30 operating in the United States in 2001 (see Table 8-14--note that the values in this table were This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-27 DRAFT: DO NOT CITE OR QUOTE 1 recalculated, resulting in minor decreases compared to the original document, which presented 2 the data in Table 8-40). 3 No changes were made to the sludge activity results, which were presented in 4 three categories: land applied (includes advanced treatment since this refers to composting, 5 which is generally done in unlined containers), landfilled (includes sludge landfills, codisposal 6 landfills, and surface disposal), and product (includes distribution/marketing and beneficial use). 7 The summary table below presents the activities and releases for sludge, which is land applied or 8 used in products. These are assumed to result in environmental releases. The landfilled sludges 9 are not included in the summary because they are not considered to be environmental releases. 10 The activity estimates for the landfilled sludge were 2.37 million dry MT in 1987, 11 1.10 million dry MT in 1995, and 0.90 million dry MT in 2000. The CDD/CDF amounts in the 12 landfilled sludge were estimated as follows: 13 14 1987--86 g WHO TEQDF(120 g I-TEQDF/kg) 15 1995--40 g WHO TEQdf (54 g I-TEQDF/kg) 16 2000-- 13 g WHO TEQdf (14 g I-TEQDF/kg) 17 18 8.5.4. Products 19 The sewage sludge emission factors described above were also applied to the swage 20 sludge used as products. No changes were made to the activity estimates. All of these values 21 and the resulting release estimates are presented in the summary table below. 22 23 8.5.5. Releases 24 The inventory decision criteria and releases to all media are summarized below: 25 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-28 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Municipal Wastewater Treatment Plants Air Water Solids Products Em ission tests for at least tw o units/source types w ith Yes Yes Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Yes Yes Yes Em ission factor tests represent units that are typical o f the class. N o Yes Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 Yes Yes PQ Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-29 DRAFT: DO NOT CITE OR QUOTE Municipal Wastewater Treatment Plants Air Releases_______________ None._______________________________________________________ W ater Releases______________ Emission Factors 1987--0.27 pg WHO TEQdf/L (0.29 pg I-TEQdf/L) (Preliminary). 1995--0.27 pg WHO TEQdf/L (o.29 pg I-TEQdf/l ) (Preliminary). 2000--0.27 pg WHO TEQdf/L (o.29 pg I-TEQdf/l ) (Preliminary). Activity Levels 1987--47.8 trillion L. 1995--44.5 trillion L. 2000--54.0 trillion L.____________________________________ Releases 1987-- 13 g WHO TEQDF/yr (14 g I-TEQDF/yr) (Preliminary). 1995-- 12 g WHO TEQDF/yr (13 g I-TEQDF/yr) (Preliminary). 2000-- 15 g WHO TEQDF/yr ( 1 6 g I-TEQDF/yr) (Preliminary). Solid Residue Releases___________ Emission Factors 1987--36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg). 1995--36 ng WHO TEQDF/kg ( 4 9 ng I-TEQDF/kg). 2000-- 14 ng WHO TEQDF/kg ( 1 5 ng I-TEQDF/kg)._____________ Activity Levels L and A pplied 1987-- 1.71 million dry MT/yr. 1995--3.20 million dry MT/yr. 2000--3.60 million dry MT/yr.__________________________ Releases L and A pplied 1987--62 g WHO TEQdf (84 g I-TEQDF/kg). 1995-- 120 g WHO TEQdf (160 g I-TEQDF/kg). 2000--50 g WHO TEQdf (54 g I-TEQDF/kg).______________ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-30 DRAFT: DO NOT CITE OR QUOTE Municipal Wastewater Treatment Plants (continued) Products___________________ Emission Factors 1987--36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg). 1995--36 ng WHO TEQDF/kg (49 ng I-TEQDF/kg). 2000-- 14 ng WHO TEQDF/kg (l5 ng I-TEQDF/kg).______________ Activity Levels 1987--0.07 MMT. 1995--0.50 MMT. 2000--0.50 MMT.________________________________________ Releases 1987--3 g WHO TEQdf (3 g I-TEQDF/kg). 1995-- 18 g WHO TEQdf (24 g I-TEQDF/kg). 2000--7 g WHO TEQdf (8 g I-TEQDF/kg)._____________________ 1 2 3 8.6. DRINKING WATER TREATMENT PLANTS 4 This section corresponds to Section 8.4.2 in the original report. As discussed in the 5 original report, there is no evidence that releases of CDD/CDFs occur from drinking water 6 treatment plants. No changes were made to this conclusion. 7 8 8.7. SOAPS AND DETERGENTS 9 This section corresponds to Section 8.4.3 in the original report. As discussed in the 10 original report, there is some evidence that soaps and detergents may be a source of CDD/CDFs, 11 but the data were judged inadequate for making quantitative estimates. 12 Soaps and Detergents Releases_____ Not quantifiable.__________________________________ 13 14 15 8.8. TEXTILE MANUFACTURING AND DRY CLEANING 16 This section corresponds to Section 8.4.4 in the original report. As discussed in the 17 original report, there is some evidence that textiles manufacturing and dry cleaning may be 18 sources of CDD/CDFs, but the data were judged inadequate for making quantitative estimates. 19 20 21 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-31 DRAFT: DO NOT CITE OR QUOTE Textiles Manufacturing and Dry Cleaning Releases______________ N o t q u an tifiab le._______________________________________________________ 1 2 3 8.9. DYES, PIGMENTS, AND PRINTING INKS 4 This section corresponds to Section 8.3.6 in the original report. A s discussed in the 5 original report, very little chloranil has been produced in the U nited States since the 1980s, so 6 production releases during the reference years are probably negligible. E PA (2006) used 7 concentration and im port data to estim ate that chloranil im ports contained 64 g I-TEQ in 1987, 8 0.4 g I-T E Q in 1995, and 1.2 g I-T E Q in 2000. It is unknow n if releases occurred from these 9 products. 10 Chloranil Imports Releases N o t q u an tifiab le.__________________________________________ 11 12 13 S im ilarly , so m e e v id e n c e e x ists th a t p h th a lo c y a n in e d y es a n d p rin tin g in k s m a y b e a 14 source o f C D D /C D F s, b u t th e d ata w ere ju d g e d in ad eq u ate fo r m ak in g qu an titativ e estim ates. 15 Phthalocyanine Dyes and Printing Inks Releases_____________ N o t q u an tifiab le._____________________________________________________ 16 17 18 8.10. OTHER ALIPHATIC CHLORINE COMPOUNDS 19 T his section corresponds to S ection 8.3.5 in th e original report. A s d iscu ssed in the 20 original report, there is no strong evidence that C D D /C D Fs are present in these com pounds. 21 22 8.11. RESIDENTIAL SEPTIC SYSTEMS 23 This is a new section. B ecause C D D /C D Fs have been m easured in discharges from 24 m unicipal w astew ater treatm ent system s, they m ay also be released from residential septic 25 system s. N o inform ation w as found on m easured CD D /C D F levels in the sew age entering these 26 system s. H ow ever, prelim inary estim ates can be m ade as discussed below . This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-32 DRAFT: DO NOT CITE OR QUOTE 1 8.11.1. Process Description 2 Most residential septic systems consist of a septic tank and drainage field or dry well. 3 The household waste flows by gravity into the septic tank where biological digestion occurs and 4 solids settle out. The overflow goes into the drainage field or dry well where it slowly percolates 5 into the ground. 6 7 8.11.2. Regulations 8 None specific to dioxins. 9 10 8.11.3. Emission Factor 11 No measurements were found on the amount of CDD/CDF excreted by people. However 12 studies have been done with dairy cattle involving measurements of dioxins in their feed, milk, 13 feces, and urine under carefully controlled settings (Winters et al., 2000; Lorber et al., 2000; 14 McLachlan et al., 1990). These studies found that 50% to 100% of both TEQs and individual 15 congeners in the feed were recovered in the milk and feces. For purposes of a preliminary 16 estimate, it is assumed here that 100% of the dioxin TEQs ingested by people are excreted in the 17 feces. Clearly this is an overestimate particularly for lactating mothers. For the general 18 population, adult daily intakes are estimated to average 43 pg WHO98 TEQDFfor CDD/CDFs and 19 23 pg WHO98 TEQpcb for PCBs (U.S. EPA, 2004). It is assumed that 30 pg WHO98 TEQDF/day 20 represents a whole population average (children plus adults) for the CDD/CDFs. Assuming that 21 two thirds of an individual's excretion occurs at their residence, 20 pg WHO98TEQDF/day is 22 discharged to the septic system. It is also assumed that no TEQ degradation or formation occurs 23 in the septic system. 24 Septic systems are designed to trap the solid components of sewage in a septic tank. The 25 tank is periodically pumped, and the contents are discharged to a municipal wastewater treatment 26 system (these releases are covered in Section 8.5). Many of the smaller particles and oily 27 components will flow into the drainage field. The fraction CDD/CDFs released to the drainage 28 field will depend largely on the solids trapping efficiency of the system, which depends on 29 variables such as tank size, flow rates, and pumping frequency. For the purposes of a 30 preliminary estimate, this is assumed to be 50%. Thus, the overall emission factor is assumed to 31 be 10 pg WHO98 TEQDF/day-person and would be applicable to all reference years. Considering This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-33 DRAFT: DO NOT CITE OR QUOTE 1 the lack o f direct feces m easurem ents and m ultiple assum ptions required for this estim ate, it is 2 given a prelim inary confidence rating. 3 4 8.11.4. Activity 5 Septic system s serve 25% o f the U.S. population (U.S. EPA , 2005). The total U.S. 6 population is estim ated to be 242 m illion in 1987, 263 m illion in 1995, and 300 m illion in 2000 7 (U.S. D O C , 2000). M ultiplying by 25% , the activity for each reference year is 61 m illion in 8 1987, 66 m illion in 1995, and 75 m illion in 2000. 9 10 8.11.5. Releases 11 T h e re le a se s fro m sep tic sy ste m s w ill o c c u r v ia th e liq u id e fflu e n t th a t d ra in s in to th e soil. 12 It is included w ith the solid residues because the release is to land. 13 T h e in v e n to ry d e c isio n c rite ria a n d re le a se s to all m e d ia are su m m a riz e d b elo w : 14 Inventory Decision Criteria for Residential Septic Systems Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 15 16 Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-34 DRAFT: DO NOT CITE OR QUOTE Residential Septic Systems Air Releases______ None._____________________________________________ W ater Releases_____ None._____________________________________________ Solid Residue Releases Emission Factors 1987-- 10 pg WHO98 TEQDF/day-person (Preliminary). 1995-- 10 pg WHO98 TEQDF/day-person (Preliminary). 2000-- 10 pg WHO98 TEQDF/day-person (Preliminary). Activity Levels 1987--61 million people. 1995--66 million people. 2000--75 million people.________________________ Releases 1987--0.2 g WHO98 TEQdf (Preliminary). 1995--0.2 g WHO98 TEQdf (Preliminary). 2000--0.3 g WHO98 TEQdf (Preliminary). 1 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-35 DRAFT: DO NOT CITE OR QUOTE Table 8-1. CDD/CDF concentrations (pg/kg) in graphite electrode sludge from chlorine production Congener/congener group 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF Total 2,3,7,8-CDDa Total 2,3,7,8-CDFa Total I-TEQdf3 Total WHO98 TEQdf3 Total TCDD Total PeCDD Total HxCDD Total HpCDD Total OCDD Total TCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF Total CDD/CDFa Sludge 1 ND (0.006) ND (0.007) ND (0.018) ND (0.012) ND (0.016) 0.095 0.92 26 25 12 32 7 1.3 0.87 9.1 8.1 31 1.02 152.37 14.2 14.1 ND (0.006) ND (0.070) ND (0.046) 0.22 0.92 64 75 68 24 31 263.14 Sludge 2 ND (0.009) ND (0.009) ND (0.026) ND (0.016) ND (0.022) 0.21 2 56 55 25 71 16 2.8 1.9 19 19 76 2.21 341.7 30.5 30.4 ND (0.009) ND (0.009) ND (0.064) 0.48 2 150 240 140 53 76 661.48 Sludge 3 ND (0.009) ND (0.009) ND (0.029) ND (0.019) ND (0.025) 0.25 2.2 57 56 24 73 15 2.6 2 19 20 71 2.45 339.6 30.2 30.2 ND (0.009) ND (0.009) ND (0.074) 0.56 2.2 140 240 140 54 71 647.76 Sludge 4 ND ND (0.033) ND (0.49) ND (0.053) ND (1.2) 0.055 0.65 52 55 27 44 12 1.7 1.3 15 14 81 0.7 303 27.7 27.6 ----0.65 ----81 -- "Calculated assuming nondetect values were zero. ND = Not detected (value in parenthesis is the reported detection limit). -- = No information given. Sources: Rappe et al. (1991); Rappe (1993). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-36 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 8-2. Releases of dioxin-like compounds in wastewater discharges from chlor-alkali manufacturing facilities to surface water in 2000 This document is a draftfor review purposes only and does not constitute Agency policy. 8-37 Congener 2,3,7,8 TCDD 1,2,3,7,8 PeCDD 1,2,3,4,7,8 HxCDD 1,2,3,6,7,8 HxCDD 1,2,3,7,8,9 HxCDD 1,2,3,4,6,7,8 HpCDD OCDD 2,3,7,8 TCDF 1,2,3,7,8 PeCDF 2,3,4,7,8 PeCDF 1,2,3,4,7,8 HxCDF 1,2,3,6,7,8 HxCDF 1,2,3,7,8,9 HxCDF 2,3,4,6,7,8 HxCDF 1,2,3,4,6,7,8 HpCDF 1,2,3,4,7,8,9 HpCDF OCDF Total I-TEQ Total WHO98 TEQdf Battleground, TX 0.00 0.00 0.00 0.00 0.00 0.00 0.48 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.83e!04 4.83e!05 Occidental Chemical Corporation Delaware City, Hahnville, Deer Park, TX DE LA 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.08 0.00 0.01 21.50 4.09e!03 0.10 0.63 1.02e!03 0.19 1.20 0.00 0.90 0.21 0.00 0.85 2.11 0.00 2.96 0.38 0.00 1.18 2.03e!03 0.00 0.63 0.00 0.00 0.60 0.59 2.31e!03 4.47 5.66e!03 0.00 0.69 4.88 0.00 1.75 0.53 1.29e!04 1.08 0.51 1.26e!04 1.08 Mobile, AL 0.00 0.00 0.00 0.00 0.00 0.00 1.15e!03 2.88e!04 0.00 0.00 0.00 0.00 0.00 0.00 6.49e!04 0.00 0.00 3.64e!05 3.54e!05 PPG Industries Muscle Shoals, AL Natrium, WV Total 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.22 0.31 1.13e!09 3.13 25.22 3.94e!08 0.06 0.89 1.33e!07 0.06 2.16 7.99e!08 0.33 1.39 1.85e!07 0.11 5.18 9.76e!08 0.00 1.56 2.29e!08 0.00 0.63 3.28e!08 0.00 0.60 1.32e!07 0.15 5.22 6.30e!08 0.00 0.69 1.34e!07 0.66 7.29 8.65e!08 0.19 1.80 8.63e!08 0.19 1.59 DRAFT: DO N O T CITE OR QUOTE Source: CCC (2004). Table 8-3. Congener-specific and TEQ annual releases to air (g/year) from a chlor-alkali facility in 2 0 0 0 Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDD 1,2,3,4,7,8,9-HpCDD OCDF Total I-TEQdf Total WHO98 TEQdf PPG Industries Natrium, WV 0.003 0.000 0.000 0.002 0.002 0.087 0.208 0.044 0.003 0.030 0.044 0.006 0.006 0.022 0.142 0.039 0.064 0.034 0.033 Source: Chlorine Chemistry Council (2004). This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-38 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 8-4. Annual releases in 2000 from stand-alone chlor-alkali plants (g I-TEQ/year) This document is a draftfor review purposes only and does not constitute Agency policy. 8-39 Plant/Location Chemicals Occidental--Mobile, AL Cl2 (membrane-cell), caustic potash, sodium silicate Confidence Rating Occidental--B attleground, TX Cl2 (diaphragm-cell), NaOH Confidence Rating Occidental--Deer Park, TX Cl2 (mercury/diaphragm- (CA) cell), NaOH Confidence Rating Occidental--Delaware City, Cl2 (mercury-cell), NaOH, DE caustic potash, Confidence Rating Occidental--Hahnville (Taft), Cl2 (mercury/diaphragmLA cell), NaOH, sulfur Confidence Rating Occidental--Muscle Shoals, Cl2 (mercury-cell) and AL caustic potash Confidence Rating PPG Industries--Natrium, WV Cl2 (mercury/diaphragm-cell cell), NaOH Confidence Rating Total Air 0.034 R/H 0.03 On-site Water Landfill 3.60 x 10-5 H/H 4.80x 10-4 H/H 0.54 H/H 1.30x 10-4 R/H 1.08 H/H 8.70 x 10-8 H/H 0.193 R/R 1.81 0.0 Landfarm 0.0 Off-site transfers11 Landfill Incineration Well Inj 0.83 H/H 0.38 R/H 0.81 H/H 0.2 H/H 0.38 H/H 0.085 H/H 2.69 3.50 x 10-6 H/H 9.60 x 10-9 H/H 0.04 R/H 0.0 0.04 aThe off-site transfers represent the amount going to off-site facilities and not the amount released to the environment. H = High. R = Reasonable. Source: Dyke and Amendola, 2007. DRAFT: DO N O T CITE OR QUOTE Table 8-5. Reported CDD/CDF concentrations (^g/kg) in wastes from polyvinyl chloride (PVC) manufacture Congener/congener group 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF Total 2,3,7,8-CDD Total 2,3,7,8-CDF Total I-TEQdf Total WHO98 TEQdf Total TCDD Total PeCDD Total HxCDD Total HpCDD Total OCDD Total TCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF Total CDD/CDF F024 waste 0.37 0.14 0.3 0.14 0.11 4.2 15 0.91 9.5 1.6 110 24 9.5 3.1 250 51 390 20.3 849.6 20 19.7 3.1 3.6 1.3 5 15 15 65 300 450 390 1,248 K019 waste 260 890 260 330 620 920 1,060 680 975 1,050 1 0 ,1 0 0 9,760 21,800 930 13,400 1,340 43,500 4,340 103,535 5,928 6,333 1,230 3,540 3,950 1,270 1,060 20,600 45,300 63,700 16,600 43,500 200,750 K020 waste 0.06 0.05 0.08 0.06 0.07 0.89 3 0.44 1.8 0.58 11 2.4 1.3 0.89 38 6 650 4.21 712.4 3.2 2 .6 1.9 1.7 a 1.7 3 6 11 27 58 650 760.3 aCongener group concentration reported in source is not consistent with reported congener concentrations. Source: Stringer et al. (1995). This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-40 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 8 -6 . CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers This document is a draftfor review purposes only and does not constitute Agency policy. Suspension and mass PVC resins Congener/congener group No. Rangeb (ng/kg) detects/ samples3 Min. Max. 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 0/22 ND ND 0/22 ND ND 0/22 ND ND 0/22 ND ND 0/22 ND ND 1/22 ND 0.64 0/22 ND ND 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF 0/22 ND ND 0/22 ND ND 0/22 ND ND 0/22 ND ND 0/22 ND ND 0/22 ND ND 1/22 ND 0.37 0/22 ND ND 0/22 ND ND 0/22 ND ND Mean I-TEQDF(nondetect = 0) Mean I-TEQDF(nondetect = U DL) 0.002 0.7 Dispersion PVC resins No. of detects/ samples Rangec (ng/kg) Min. Max. 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 1/6 ND 0.8 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 0/6 ND ND 2/6 ND 0.38 0.001 0.4 EDC sold as productd No. detects/ samples Rangee (ng/kg) Min. Max. 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 0/5 ND ND 1/5 ND 1.1 1/5 ND 0.4 1/5 ND 11 0.001 0.21 8-41 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 8-6. CDD/CDF concentrations in products from U.S. EDC/VCM/PVC manufacturers (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 8-42 Congener/congener group Total TCD D Total PeC D D Total H xC D D Total H pC D D Total OCD D Total TCDF Total PeCD F Total H xC D F Total H pCD F Total OCDF Suspension and mass PVC resins Dispersion PVC resins EDC sold as productd No. Rangeb (ng/kg) No. of detects/ detects/ samples3 Min. Max. samples Rangec (ng/kg) No. detects/ Min. Max. samples Rangee (ng/kg) Min. Max. 0/22 0/22 0/22 1/22 0/22 0/22 0/22 1/22 0/22 0/22 ND ND ND ND ND ND N D 0.64 ND ND ND ND ND ND N D 0.37 ND ND ND ND 1/6 1/6 5/6 1/6 0/6 0/6 1/6 0/6 0/6 2/6 N D 0.24 N D 0.32 N D 0.97 N D 1.3 ND ND ND ND N D 0.3 ND ND ND ND N D 0.38 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 1/5 1/5 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND N D 2.02 N D 11 aTwo of these 22 samples were duplicate samples from two sites. The results were averaged and treated as one sample for each site. bDetection limits (DLs) for individual samples were less than 2 ng/kg for all congeners and congener groups except OCDD and OCDF, which had DLs less than 6 ng/kg. cDLs for individual samples were less than 2 ng/kg for all congeners and congener groups except OCDD and OCDF, which had DLs less than 4 ng/kg. ^`Sales" EDC is defined as EDC sold commercially for non-VCM uses or exported from the United States. eDLs were less than 1 ng/kg for all congeners in all samples. DL = Detection limit. EDC = Ethylene dichloride. ND = Not detected. PVC = Polyvinyl chloride. VCM = Vinyl chloride monomer. Source: The Vinyl Institute (1998). DRAFT: DO N O T CITE OR QUOTE 1/7/2013 Table 8-7. Annual releases in 2000 from stand-alone vinyl chloride plants (g I-TEQ/year) This document is a draftfor review purposes only and does not constitute Agency policy. Plant/Location O ccidental-- D eer Park, TX Confidence R ating O ccidental-- LaPorte, TX Confidence R ating Total Chemicals VCM VCM Air 0.581 H /H 0.039 H /H 0.62 On-site Water Landfill 0.031 H /H 0.0064 H /H 0.04 Landfarm Off-site Transfersa Landfill Incineration 0.474 2 2 .2 H /H H /H 5.1 44.4 H /H H /H 5.57 66.60 aThe off-site transfers represent the amount going to off-site facilities and not the amount released to the environment. H = High Confidence. Source: Dyke and Amendola, 2007. 8-43 DRAFT: DO N O T CITE O R QUO TE 1/7/2013 Table 8-8. CDD/CDF concentrations (mg/kg) in mono-through tetrachlorophenols This document is a draftfor review purposes only and does not constitute Agency policy. C ongener/ congener group Total TCDD Total PeCDD Total HxCDD Total HpCDD Total OCDD Total TCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF TOTAL 2-C P a 2,4-D C P a 2,6-D C P a ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) 2,4,5-T rC P (N a salt)a ND (0.02) to 14 ND (0.02) ND (0.02) ND (0.02) ND (0.02) 2,4,5-T rC P a ND (0.02) to 6.5 ND (0.02) to 1.5 ND (0.02) ND (0.02) ND (0.02) 2,4,6-T rC P a ND (0.02) to 49 ND (0.02) ND (0.02) ND (0.02) ND (0.02) + 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 -- -- -- -- -- -- 2,4,6-T rC P (N a salt)b <0.02 <0.03 <0.03 <0.1 <0.1 1.5 17.5 36 4.8 -- -- 2,3,4,6-T eC P 2,3,4,6-T eC P a (N a salt)b ND (0.02) ND (0.02) ND (0.02) to 15 ND (0.02) to 5.1 ND (0.02) to 0.17 0.7 5.2 9.5 5.6 0.7 + 0.5 + 10 + 70 + 70 + 10 -- -- 8-44 aSource: Firestone et al. (1972); because of poor recoveries, the authors stated that actual CDD/CDF levels may have been considerably higher than those reported. bSources: Rappe and Marklund (1978); Rappe et al. (1978); common Scandinavian commercial chlorophenols. ND = Not detected (value in parenthesis is the detection limit, if reported). + = Detected but not quantified. -- = No information given. DRAFT: DO N O T CITE OR QUOTE Table 8-9. Summary of specific dioxin-containing wastes that must comply with land disposal restrictionsa EPA hazardous waste number Waste description Land disposal Regulated restriction effective waste date constituent F020 Wastes (except wastewater and spent carbon from November 8, 1988 TCDDs HCl purification) from the production or PeCDDs manufacturing use (as a reactant, chemical HxCDDs intermediate, or component in a formulating TCDFs process) oftri- or tetrachlorophenol or of PeCDFs intermediates used to produce their pesticide HxCDFs derivatives. (This listing does not include wastes from the production of hexachlorophene from highly purified 2,4,5-trichlorophenol.) F021 Wastes (except wastewater and spent carbon from November 8, 1988 TCDDs HCl purification) from the production or PeCDDs manufacturing use (as a reactant, chemical HxCDDs intermediate, or component in a formulating TCDFs process) of pentachlorophenol or of intermediates PeCDFs used to produce its derivatives. HxCDFs F022 Wastes (except wastewater and spent carbon from November 8, 1988 TCDDs HCl purification) from the manufacturing use (as PeCDDs a reactant, chemical intermediate, or component in HxCDDs a formulating process) oftetra-, penta-, or TCDFs hexachlorobenzenes under alkaline conditions. PeCDFs HxCDFs F023 Wastes (except wastewater and spent carbon from November 8, 1988 TCDDs HCl purification) from the production of materials PeCDDs on equipment previously used for the production HxCDDs or manufacturing use (as a reactant, chemical TCDFs intermediate, or component in a formulating PeCDFs process) oftri- and tetrachlorophenols. (This HxCDFs listing does not include wastes from equipment used only for the production or use of hexachlorophene from highly purified 2,4,5-trichlorophenol.) F026 Wastes (except wastewater and spent carbon from November 8, 1988 TCDDs HCl purification) from the production of materials PeCDDs on equipment previously used for the HxCDDs manufacturing use (as a reactant, chemical TCDFs intermediate, or component in a formulating PeCDFs process) oftetra-, penta-, or hexachlorobenzene HxCDFs under alkaline conditions. This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-45 DRAFT: DO NOT CITE OR QUOTE Table 8-9. Summary of specific dioxin containing wastes that must comply with land disposal restrictionsa(continued) EPA hazardous waste number Waste description Land disposal Regulated restriction effective waste date constituent F027 Discarded unused formulations containing tri-, November 8, 1988 TCDDs tetra-, or pentachlorophenol or discarded unused PeCDDs formulations containing compounds derived from HxCDDs these chlorophenols. (This listing does not TCDFs include formulations containing hexachlorophene PeCDFs synthesized from prepurified 2,4,5-trichlorophenol HxCDFs as the sole component.) F028 Residues resulting from the incineration or November 8, 1988 TCDDs thermal treatment of soil contaminated with EPA PeCDDs Hazardous Wastes No. F020BF023, F026, and HxCDDs F027. TCDFs PeCDFs HxCDFs F039 Leachate (liquids that have percolated through August 8, 1990 TCDDs land-disposed wastes) resulting from the disposal (wastewater) PeCDDs of more than one restricted waste classified as May 8, 1992 HxCDDs hazardous under Subpart D of 40 CFR 268. (nonwastewater) TCDFs (Leachate resulting from the disposal of one or PeCDFs more of the following EPA hazardous wastes and HxCDFs no other hazardous wastes retains its EPA hazardous waste number[s]: F020, F021, F022, F026, F027, and/or F028.) K043 2,6-Dichlorophenol waste from the production of 2,4-D. June 8, 1989 TCDDs PeCDDs HxCDDs TCDFs PeCDFs HxCDFs K099 Untreated wastewater from the production of 2,4-D. August 8, 1988 TCDDs PeCDDs HxCDDs TCDFs PeCDFs HxCDFs aFor wastewater, the treatment standard for all regulated waste constituents--except for PeCDFs--is 0.063 pg/L; the standard for PeCDFs is 0.035 pg/L. For nonwastewater, the treatment standard for all regulated waste constituents is 1 pg/kg. Treatment standards are based on incineration to 99.9999% destruction and removal efficiency. Source: 40 CFR 268. This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-46 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 8-10. CDD/CDF concentrations (historical and current) (^g/kg) in technical-grade pentachlorophenol (PCP) products This document is a draftfor review purposes only and does not constitute Agency policy. Congener/ congener group 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF Total 2,3,7,8-CDD1 Total 2,3,7,8-CDF1 Total I-TEQdf1 TotalWHO98TEQdf1 Total TCDD Total PeCDD Total HxCDD Total HpCDD Total OCDD Total TCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF Total CDD/CDF' 1973a ---------------------- ND(20) ND(30) 5,500 98,000 220,000 40 250 22,000 150,000 160,000 655,790 1978b ----------------130,000 ----- -----900 4,000 32,000 120,000 130,000 286,900 1979c ---------------------- --10,100 296,000 1,386,000 -1,400 9,900 88,000 43,000 1,834,400 1984d ND(10) ND(10) 2,200 100 100,000 610,000 ND(10) --------130,000 712,300 130,000 1,970 1,304 ND(10) ND(10) 4,500 135,000 610,000 ND(10) --62,000 130,000 941,500 1985e ND(0.05) ND(1) 6 2,565 44 210,000 1,475,000 ND(0.5) ND(1) ND(1) 49 5 5 ND(1) 34,000 4,100 222,000 1,687,615 260,159 4,445 2,918 ND ND 4,694 283,000 1,475,000 6 10 1,982 125,000 222,000 2,111,692 1986e ND(0.05) ND(1) 8 1,532 28 106,000 930,000 ND(0.5) ND(1) ND(1) 34 4 ND(1) ND(1) 29,000 6,200 233,000 1,037,568 268,238 2,735 1,689 ND ND 2,925 134,000 930,000 ND 3 1,407 146,000 233,000 1,447,335 1987f ND(0.03) 1 ND(1) 831 28 78,000 733,000 ND(0.1) 0.5 1.5 125 ND(1) 32 ND(1) 11,280 637 118,000 811,860 130,076 1,853 1,088 1.9 6.5 1,700 154,000 733,000 0.8 141 4,300 74,000 118,000 1,085,150 1987g ND(0.05) 2 ND(1) 1,480 53 99,900 790,000 ND(0.1) 0.2 0.9 163 ND(1) 146 ND(1) 19,940 980 137,000 891,435 158,230 2,321 1,488 0.4 15.2 3,300 198,000 790,000 0.4 343 13,900 127,000 137,000 1,269,559 1985B88h ND(0.05) ND(1) 8 600 13 89,000 2,723,000 ND(0.5) ND(1) ND(1) 67 2 ND(1) ND(1) 22,000 3,400 237,000 2,812,621 262,469 4,173 1,509 1991i 1988B99e 1988B99* Unknownk ND -- ND(0.5) ND(10) ND -- -- ND(10) -- -- -- ND(10) -- -- -- 860 -- -- -- 20 -- -- -- 36,400 1,100,000 -- -- 296,810 ND ND ND ------170,000 ----------- -- ND(10) -- ND(10) -- ND(10) -- 200 -- ND(20) -- ND(20) -- ND(20) -- 2,000 -- 140 -- 19,940 1,100,000 170,000 31,270 >127 ----- -- 334,090 -- 22,280 -- 810 -- 525 ND ND 912 117,000 2,723,000 ND 200 1,486 99,000 237,000 3,178,598 ND(10) ND(1) ND(10) ND(10) 8,900 1,440 130,000 55,560 1,100,000 -ND(10) ND(10) ND(10) ND(10) 14,000 3,070 36,000 36,530 170,000 -- ND 3 1,490 48,430 191,700 48 520 13,650 76,090 136,310 1,458,900 960,000 468,241 ------------ 8-47 DRAFT: DO N O T CITE OR QUOTE 1/7/2013 This document is a draftfor review purposes only and does not constitute Agency policy. Table 8-10. CDD/CDF concentrations (historical and current) (^g/kg) in technical-grade pentachlorophenol (PCP) products (continued) aSource: Buser and Bosshardt (1976); mean of 10 samples of Ahigh@CDD/CDF-content PCP received from Swiss commercial sources in 1973. bSource: Rappe et al. (1978); sample of U.S. origin, Apresumably prepared by alkaline hydrolysis of hexachlorobenzene.@ cSource: NTP (1989); composite of technical-grade materials produced in 1979 by Monsanto Industrial Chemical Co. (St. Louis, MO), Reichhold Chemicals, Inc. (White Plains, NY), and Vulcan Materials Co. (Birmingham, AL). dSource: Cull et al. (1984); mean of four Arecent@production batches from each of two manufacturers of technical PCP using three different analytical methods; analysis of variance (ANOVA) showed no statistically significant difference in CDD/CDF concentrations between the eight samples (samples obtained in the United Kingdom). eSource: Letter dated February 7, 1997, from John Wilkinson, Pentachlorophenol Task Force, to Matthew Lorber, U.S. EPA; average of monthly batch samples for the period January 1987 to August 1996. fSource: Hagenmaier and Brunner (1987); sample of Witophen P (Dynamit Nobel-Lot no. 7777) (obtained in Germany). gSource: Hagenmaier and Brunner (1987); sample of PCP produced by Rhone Poulenc (obtained in Germany). hSource: Letter dated February 7, 1997, from John Wilkinson, Pentachlorophenol Task Force, to Matthew Lorber, U.S. EPA; samples of Apenta@manufactured in 1985, 1986, and 1988. `Source: Harrad et al. (1991); PCP-based herbicide formulation from the New York State Department of Environmental Conservation. JSource: Letter dated March 5, 1997, from Thomas Mitchell, KMG-Bernuth, to Matthew Lorber, U.S. EPA; average of monthly batch samples for the period February 1987 to December 1996 (excluding the following months, for which data were not available: February 1993, January 1992, December 1991, September 1991, December 1988, and September 1988). kSource: Schecter et al. (1997); sample found stored in a barn in Vermont. 'Calculated assuming nondetects were zero. ND = Not detected (value in parenthesis is the detection limit). -- = No information given. 8-48 DRAFT: DO N O T CITE O R QUOTE Table 8-11. Historical CDD/CDF concentrations (pg/kg) in pentachlorophenol-Na (PCP-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-CDDh Total 2,3,7,8-CDFh Total I-TEQDFh Total WHO98 TEQDFh Total TCDD Total PeCDD Total HxCDD Total HpCDD Total OCDD Total TCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF Total CDD/CDFh 1969a ------3,600 1973b -------- -- --- --- -- -- --- --- --- --- --- --- -- -- --- --- -- -- -- --17,000 9,600 3,600 --- --- -- 140 40 140 1,600 4,000 ND (20) 60 1,400 4,300 4,300 30,200 15,980 1973c -------- ----------- ----- 50 ND (30) 3,400 38,000 110,000 ND (20) 40 11,000 47,000 26,500 235,990 1987d 0.23 18.2 28.3 2,034 282 9,100 41,600 1.8 8.2 6.6 48 69 ND (1) 87 699 675 37,200 53,062.7 38,794.6 452 390 27 213 3,900 18,500 41,600 82 137 3,000 13,200 37,200 117,859 1987e 0.51 3.2 13.3 53 19 3,800 32,400 0.79 1.9 1.1 4.6 1.3 1.3 4.6 197 36 4,250 36,289 4,498.6 89.5 58.1 52 31 230 5,800 32,400 12 27 90 860 4,250 43,752 1992f 0.076 18.7 96 4,410 328 175,400 879,000 1980sg ND (1.4) 28.3 ND (6.1) 4,050 ND (1.4) 33,800 81,000 ND (1) ND (4) ND (4) 27.6 21.9 9.8 103 9,650 2,080 114,600 149 319 324 ND (2.8) 225 480 ND (385) 6,190 154 36,000 1,059,252.8 118,878.3 126,492.3 43,841 3,374 1,201 2,489 1,110 3.6 142.7 9,694 260,200 879,000 10.1 88.4 9,082.3 75,930 114,600 1.9 140 14,000 100,000 81,000 1,200 6,400 49,000 91,000 36,000 1,348,751 378,742 aSource: Firestone et al. (1972); mean of two samples of PCP-Na obtained in the United States between 1967 and 1969. bSource: Buser and Bosshardt (1976); mean of five samples of Alow@CDD/CDF-content PCP-Na received from Swiss commercial sources. cSource: Buser and Bosshardt (1976); sample of Ahigh@CDD/CDF-content PCP-Na received from a Swiss commercial source. This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-49 DRAFT: DO NOT CITE OR QUOTE Table 8-11. Historical CDD/CDF concentrations (^g/kg) in pentachlorophenol Na (PCP Na) (continued) dSource: Hagenmaier and Brunner (1987); sample of Dowicide-G purchased from Fluka; sample obtained in Germany. eSource: Hagenmaier and Brunner (1987); sample of Preventol PN (Bayer AG); sample obtained in Germany. fSource: Santl et al. (1994); 1992 sample of PCP-Na from Prolabo, France. gSource: Palmer et al. (1988); sample of a PCP-Na formulation collected from a closed sawmill in California in the late 1980s. hCalculated assuming nondetect values were zero. ND = Not detected (value in parenthesis is the detection limit). -- = No information given. This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-50 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 8-12. CDD/CDF concentrations (pg/kg) in chlorobenzenes This document is a draftfor review purposes only and does not constitute Agency policy. Congener/ congener group Total TCDD Total PeCDD Total HxCDD Total HpCDD Total OCDD Total TCDF Total PeCDF Total HxCDF Total HpCDF Total OCDF Total CDD/CDF MCBza ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND 1,2-DCBz (for synthesis) 3 0.3 ND (0.02) ND (0.02) ND (0.02) ND (0.02) ND (0.02) 0.5 ND (0.02) ND (0.02) ND (0.02) 0.8 1,2,4-TrCBz (Apure@)b ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND (0.1) ND Mixed TrCBz (47% ) 3 0.027 0.14 0.259 0.253 0.081 0.736 0.272 0.091 0.03 0.016 1.9 1,2,4,5-TCBz (99% ) 3 ND (0.02) 0.2 0.5 0.8 0.4 0.03 0.2 0.8 1.5 2.1 6.5 PeCBz (98%)3 ND (0.02) ND (0.02) 0.02 0.02 0.05 0.02 ND (0.02) ND (0.02) 0.1 0.1 0.3 HCBz (97%)a ND (20) ND (20) ND (20)470 6,700 ND (20) ND (20) ND (20) 455 2,830 10,455 HCBzb ----50b212,000 -- -- -- -350b58,300 400b270,300 8-51 aSource: Hutzinger and Fiedler (1991b); unpublished results of tests performed at the University of Bayreuth, Germany, and by Dr. H. Hagenmaier. bSource: Villanueva et al. (1974); range of three samples of commercially available HCBz. ND = Not detected (value in parenthesis is the detection limit, if reported). -- = No information given. DRAFT: DO N O T CITE O R QUOTE 1/7/2013 Table 8-13. Annual releases in 2000 from complex plants producing chlorine and a variety of chlorinated organics (g I-TEQ/year) This document is a draftfor review purposes only and does not constitute Agency policy. 8-52 Plant/Location Dow Chemical--Midland MI Confidence Rating Dow Chemical--Plaquemine, LA Confidence Rating Dow Chemical--Freeport, TX Confidence Rating Company A, Plant A1 Confidence Rating Occidental-- Convent, LA Confidence Rating Occidental--Ingleside, TX Confidence Rating PPG Industries--Lake Charles, LA Confidence Rating Company B, Plant B 1 Confidence Rating Occidental--Niagara Falls Confidence Rating Company B, Plant B2 Chemicals Ag chemicals, polymers, others Chlorine, EDC, others Chlorine, EDC, VCM, solvents, others Chlorine, EDC, VCM, others Chlorine, NaOH, EDC Cl2 (diaphragm-cell), NaOH, EDC, VCM Cl2 (mercury-/diaphragm-cell), hydrogen, NaOH, EDC, and VCM Cl2, solvents, other chlorinated organics Cl2, NaOH, organic chemicals Cl2, EDC, solvents Air 0.046 H/H 0.092 H/H 3.08 H/H 0.068 H/H 0.022 R/H 1.61 RH/H 0.02 On-site Water Landfill 0.037 12.6 H/H H/H 7.71 12.8 H/H H/H 6.91 89.3 H/H H/H 0.023 H/H 0.002 LR/H 0.018 H/H 8.98 H/H H/H 0.037 1.07 R/H R/H 3.80 x 10-3 1.40 x 10-3 H/H H/H 8.38 x 10-3 3.72 x 10-1 Off-site transfers3 Landfarm Landfill Incineration 1.45 1.5 H/H H/H 0.081 H/H 1.47 H/H 0.303 2.18 H/H 12.1 R/H 8.66 H/H H/H 0.208 0.028 R/H 210 R/H DRAFT: DO N O T CITE OR QUOTE 1/7/2013 Table 8-13. Annual Releases in 2000 from complex plants producing chlorine and a variety of chlorinated organics (g I-TEQ/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Plant/Location Confidence Rating Total Chemicals On-Site Off-site Transfers11 Air Water Landfill Landfarm Landfill Incineration R/H R/H 4.99 25.12 114.70 1.45 3.38 233.15 aThe off-site transfers represent the amount going to off-site facilities not the amount released to the environment. H = High. R = Reasonable. L = Low. Source: Dyke and Amendola (2007). 8-53 DRAFT: DO N O T CITE O R QUO TE Table 8-14. CDD/CDF mean concentrations (ng/kg) measured in the 2001 National Sewage Sludge Survey Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF Average total WHO98 TEQDF Average total I-TEQDF Source: EPA (2002d). Nondetect set to V detection limit 1.41 5.76 11.8 21.3 3.6 492 6,780 3.11 2.61 6.03 1.37 0.27 5.21 5.5 9.13 167 802 23 27 Nondetect set to zero 1.1 4.57 7.49 15.1 2.22 273 2,730 2.3 1.5 2.8 1 0 2.6 3.36 2.8 88.2 279 14 15 This document is a draftfor review purposes only and does not constitute Agency policy 1/7/2013 8-54 DRAFT: DO NOT CITE OR QUOTE Figure 8-1. Congener profile for technical-grade PCP (developed from data in last column in Table 8-10). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 8-55 DRAFT: DO N O T CITE OR QUOTE 1 9. NATURAL SOURCES OF CDDS/CDFS 2 3 4 N um erous laboratory and field research studies have dem onstrated that biochem ical and 5 photolytic form ation o f C D D s/C D Fs from chlorophenol precursors is possible. In addition, 6 under certain conditions, som e C D D s/C D Fs can be biodegraded to form less-chlorinated (and 7 possibly m ore toxic) C D D s/C D Fs. B oth o f these m echanism s are discussed in this chapter; 8 how ever, the extent to w hich C D D s/C D Fs are form ed by either m echanism in the environm ent is 9 unknow n at present. The potential for releases o f C D D s/C D Fs from the application o f anim al 10 m anure to farm land and the m ining and use o f ball clay are also discussed. Forest fires could be 11 c o n sid e re d a p o te n tia l n a tu ra l so u rce, b u t it w a s d e c id e d th a t th e d is c u s s io n fit b e tte r in C h a p te r 6 12 on m inim ally and uncontrolled com bustion sources. Sim ilarly, volcanoes w ere discussed in 13 C h a p te r 6 w h e re it in d ic a te s th a t n o stu d ie s h a v e d e m o n s tra te d th e fo rm a tio n o f C D D s/C D F s b y 14 volcanoes. 15 16 9.1. BIOTRANSFORMATIONS 17 9.1.1. Biotransformation of Chlorophenols 18 A s d iscu ssed in th e o rig in al report, th e b io ch em ica l fo rm a tio n o f C D D s/C D F s-- 19 p articu larly th e h ig h er-ch lo rin ated co n g en ers-- from chlorophenol p recu rso rs is possible, as 20 indicated in laboratory studies w ith solutions o f trichlorophenols and PCP in the presence o f 21 peroxidase enzym es and hydrogen peroxide. H ow ever, the extent to w hich C D D s/C D Fs are 22 form ed in the environm ent via this m echanism cannot be estim ated at this time. 23 U N EP (2005) suggests the follow ing em ission factors for com posted m aterials: garden 24 and k itch en w a ste s-- 15 n g I-T E Q /k g dry m atter, and g reen m ateria ls from u n im p acted 25 environm ents-- 5 ng I-TEQ /kg dry m atter. The discussion indicates that som e very high levels 26 (approxim ately 100 ng I-TEQ /kg dry m atter) have been observed in com post as a result of 27 contam inated input. 28 Products from com posting operations are typically land spread and have the potential to 29 be a land release. H ow ever, insufficient inform ation is available on em ission factors and 30 activities to m ake release estim ates for com posting or other potential sources involving 31 b io tran sfo rm atio n o f ch lo ro p h en o ls (N o t quantifiable). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 9 - 1 DRAFT: DO NOT CITE OR QUOTE Biotransformation of Chlorophenols Releases to Soil_________ N o t q u an tifiab le.____________________________________________________ 1 9.1.2. Biotransformation of Higher CDDs/CDFs 2 As discussed in the original report, results o f several studies that exam ined the fate o f a 3 range o f CD D /C D F congeners in pure cultures, sedim ents, and sludges indicate that under 4 certain conditions, som e CD D /CD F congeners w ill undergo biodegradation to form 5 low er-chlorinated (and possibly m ore toxic) CD D s/CD Fs. H ow ever, the extent to w hich m ore 6 toxic C D D s/C D Fs are form ed in the environm ent via this m echanism cannot be estim ated at this 7 time. 8 Therefore, these releases are not quantifiable. Biotransformation of Higher CDDs/CDFs Releases to Soil___________ N o t q u an tifiab le._______________________________________________________ 9 9.1.3. Biotransformation of Animal Manure 10 B ecause livestock and poultry m anure can provide valuable organic m aterial and 11 n u trie n ts fo r cro p a n d p a s tu re g ro w th , m o s t o f th e an im al m a n u re g e n e ra te d at co m m e rc ia l fa rm s 12 and anim al feed lots is applied to farm land as fertilizer. To the extent dioxin-like com pounds 13 m a y c o n ta m in a te a n im a l m a n u re s, th e p ra c tic e o f la n d -sp re a d in g a n im a l w a ste m a y re su lt in 14 releases o f C D D s/C D F s to th e open and circu latin g environm ent. 15 M a s s b a la n c e stu d ies h a v e sh o w n th a t n o n e w fo rm a tio n o f d io x in s a n d fu ra n s a p p e a rs to 16 o ccu r w ith in a cow (W inters et al., 2000; L o rb er et al., 2000; M cL ach lan et al., 1990). T hese 17 studies have in v o lv ed m easu rin g th e dio x in s p resen t in th e feeds p rovided to dairy cow s and th en 18 m easu rin g th e d io x in s in th e co w m ilk, feces, and u rin e in carefu lly co n tro lled settings. S tudies 19 by E P A (W inters et al., 2000; L o rb er et al., 2 0 0 0 ) in v o lv ed fo u r cow s, sam pled th ree tim es 20 betw een July and N ovem ber of 1997. Prelim inary testing on urine show ed nondetects as 21 expected, so this m atrix w as not included in further testing. The tests w ere designed to represent 22 typical conditions (feed types, dairy cow housing, etc.) in the U nited States w ith regard to the 23 production o f m ilk. The feed and feces concentrations ranged from 0.13 to This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 9 - 2 DRAFT: DO NOT CITE OR QUOTE 1 0.30 ng WHO98 TEQDF/kg dry weight basis, and milk concentrations ranged from 0.53 to 2 0.96 ng WHO98 TEQDF/kg lipid basis. The feces concentrations in these lactating cows were 3 about one order of magnitude lower than that measured by Stevens and Jones (2003) in the 4 United Kingdom (U.K.) (see Table 9-1). A mass balance was determined by dividing the mass 5 of CDD/CDFs present in feces and milk by the mass in the feed and then multiplying by 100% (a 6 finding of 100% suggests that the dioxins excreted in milk and feces equals that in the feed; a 7 finding greater than 100% suggests formation). These matrices were sampled once the cows 8 were well into lactation, so an assumption of steady state was reasonable. The mass balance of 9 both TEQs and individual congeners ranged from about 50 to 100%, suggesting no internal 10 formation of CDD/CDFs by the cows. The average mass balance over 17 congeners was 73%. 11 McLachlan et al. (1990) conducted a similar experiment with one cow in a background setting 12 and also found mass balances between 50 and 100%, with an average of 75% over all 13 17 CDD/CDF congeners. 14 As discussed in the original report, reasonably good data are available on the generation 15 rates of livestock manure. However, limited data are available on CDD/CDF levels in livestock 16 manure. Further, mass balance studies on lactating cows suggest that no new formation of 17 CDD/CDFs are occurring. Thus, while the land application of farm animal manure is a potential 18 land release, it is concluded that insufficient data are available to quantify these releases, and 19 because of the mass balance studies, these may be better characterized as a redistribution rather 20 than a new formation. Accordingly, EPA currently considers this source to be unquantifiable in 21 terms of dioxin emissions. Biotransformation of Animal Manure Releases to Soil_________ Not quantifiable.__________________________________________ 22 23 9.2. PHOTOCHEMICAL TRANSFORMATIONS 24 A number of researchers have demonstrated that CDD/CDFs can be formed via various 25 types of photochemical transformations. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 9 - 3 DRAFT: DO NOT CITE OR QUOTE 1 9.2.1. Photolysis of PCP 2 As discussed in the original report, several studies have dem onstrated that photolysis o f 3 P C P m ay lead to the form ation of C D D /C D Fs; how ever, the inform ation is considered 4 inadequate to estim ate releases o f C D D /C D Fs to the environm ent. Photolysis of PCP Releases to Wood or Air N o t q u an tifiab le.______________________________________________ 5 9.2.2. Photolysis of Higher CDDs/CDFs 6 A s discussed in the original report, a num ber of studies have dem onstrated that photolysis 7 o f higher C D D /C D Fs m ay lead to the form ation o f C D D /C D Fs; how ever, the inform ation is 8 considered inadequate to estim ate releases o f C D D /C D Fs to the environm ent. Photolysis of Higher CDDs/CDFs Releases to Air, Water, or Soil N o t q u an tifiab le.__________________________________________________ 9 9.2.3. Photolysis in W ater 10 A s discussed in the original report, a num ber o f studies have dem onstrated that photolysis 11 in w a te r m a y le a d to th e fo rm a tio n o f C D D /C D F s; h o w e v er, th e in fo rm a tio n is c o n sid e re d 12 inadequate to estim ate releases o f C D D /C D Fs to the environm ent. Photolysis in Water__________________________ Releases to W ater__________________________ N o t q u an tifiab le.____________________________________________________________________________ 13 9.2.4. Photolysis on Soil Surfaces 14 A s d iscu ssed in th e original report, studies have d em o n strated th a t p h o to ly sis on soil 15 su rfa c e s m a y le a d to th e fo rm a tio n o f C D D /C D F s; h o w e v er, th e in fo rm a tio n is c o n sid e re d 16 in ad eq u ate to estim ate releases o f C D D /C D F s to th e environm ent. Photolysis on Soil Releases to Soil N o t q u an tifiab le.__________________________________________ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 9 - 4 DRAFT: DO NOT CITE OR QUOTE 1 9.2.5. Photolysis on Vegetation 2 As discussed in the original report, studies have demonstrated that photolysis on 3 vegetation may lead to the formation of CDD/CDFs; however, the information is considered 4 inadequate to estimate releases of CDD/CDFs to the environment. Photolysis on Vegetation Releases to Biota Not quantifiable.____________________________________ 5 9.2.6. Photolysis in Air 6 As discussed in the original report, studies have demonstrated that photolysis in air may 7 lead to the formation of CDD/CDFs; however, the information is considered inadequate to 8 estimate releases of CDD/CDFs to the environment. Photolysis in Air Releases to Air Not quantifiable._________________________________ 9 9.3. CDDS/CDFS IN BALL CLAY 10 As discussed in the original report, studies have demonstrated that CDD/CDFs are found 11 naturally in ball clay. Releases from ball clay may occur when it is disturbed during mining and 12 subsequent processing. Accordingly, such releases have both a natural and an anthropogenic 13 aspect to them. Multiplication of the mean WHO98 TEQDFconcentration in mined ball clay by 14 the total amount of ball clay mined in 1995 gives an estimate of 1,502 g WHO98 TEQDF 15 (U.S. EPA, 2006). It is unknown how much of these CDD/CDFs contained in mined ball clay 16 are released to the environment during the mining, initial refining, and product handling. Most 17 ball clay is used to produce ceramic products where releases may occur from processes such as 18 drying or high-temperature vitrification. The temperatures found in ceramic kilns vary but can 19 reach levels needed for both volatilization and destruction of CDD/CDFs. No stack 20 measurement data are available from these facilities, so there is insufficient evidence to make 21 even a preliminary estimate of releases. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 9 - 5 DRAFT: DO NOT CITE OR QUOTE Ball Clay Releases to Air N o t q u an tifiab le._________________________________________ This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 9-6 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 9-1. CDD and CDF concentrations (ng/kg dry weight) in samples of animal manure in the United Kingdom This document is a draftfor review purposes only and does not constitute Agency policy. Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD Total 2,3,7,8-CDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF Total 2,3,7,8-CDF Total CDD/CDF WHO98 TEQ Cowsa (n = 6) (mean) 0.17 0.46 2.4 4.5 2.6 120 460 590.1 0.3 0.3 0.28 0.6 0.51 1.9 0.4 7.6 12 35 58.9 649 3.6 Cowsb (n = 10) (mean) 0.02 0.04 0.06 0.15 0.11 3.6 58 62.3 0.05 0.04 0.06 0.18 0.12 0.05 0.16 1.8 0.17 2.4 5.0 67.4 0.2 Sheepa (n = 1) 0.11 0.41 0.9 0.86 0.56 9.4 53 65.2 1.2 1.1 1.2 1.4 1.1 0.15 1.4 5.2 0.56 5 18.3 83.5 2.1 Piga (n = 1) 0.01 0.07 0.26 0.1 0.07 0.8 11 12.3 0.03 0.04 0.06 0.05 0.06 0.04 0.06 0.48 0.04 0.73 1.6 13.9 0.2 Chickena (n = 1) 0.01 0.04 0.03 0.09 0.12 1.4 14 15.7 0.03 0.09 0.12 0.15 0.07 0.05 0.14 0.37 0.09 0.8 1.9 17.6 0.2 9-7 DRAFT: DO NOT CITE OR QUOTE Sources: aStevens and Jones (2003); bPersonal communication, M. Lorber (2008), who provided the raw data for the study summarized in Lorber et al. (2000). The data reflect four cows sampled three times; n = 10 instead of 12 because two cows in one sampling date were exposed to feed purposefully contaminated with PCP-treated wood shavings. 1 10. SOURCES OF DIOXIN-LIKE POLYCHLORINATED BIPHENYLS (PCBS) 2 3 4 This chapter estim ates releases o f dioxin-like PCB congeners to the environm ent. PCB 5 releases from m ed ia reservoirs (i.e., soil, sedim ent, and w ater) are covered in C h ap ter 11. T his 6 chapter covers other PCB sources, prim arily conventional point sources. These sources are 7 assum ed to have contem porary form ation releases. This is uncertain, though, because som e 8 portion o f these releases m ay be passed through from inputs to outputs rather than new 9 fo rm a tio n . B o th C h a p te rs 10 a n d 11 c o n ta in in fo rm a tio n o n re le a se s a sso c ia te d w ith P C B 10 products. 11 12 10.1. GENERAL FINDINGS OF THE EMISSIONS INVENTORY 13 T h e p rim a ry c h a n g e s to th is c h a p te r in c lu d e th e a d d itio n o f sev eral n e w so u rc e 14 categories, ad d itio n o f b ack g ro u n d in fo rm atio n to a n u m b er o f th e o th er sources, and m in o r 15 ch a n g e s to th e re le a se estim ates. A d d itio n a lly , th e re le a se su m m a ry ta b le (se e T a b le 10-1) h as 16 b een refo rm atted to m atch th e n ew one u sed fo r C D D /C D F s. 17 R elativ ely few sources hav e w ell-ch aracterized releases o f d io x in -lik e P C B s. A s show n 18 in T ab le 10-1, 2 so u rces h ad q u an titativ e re le ase estim ates, 6 so u rces h ad p re lim in ary release 19 estim ates and 9 sources w ere id en tified as b ein g u nquantifiable. A lth o u g h th e in fo rm atio n is 20 lim ited, it suggests that, in term s o f TEQs, PCB releases are m uch low er than CD D /CD F 21 releases. 22 Tw o potential source categories that could not be addressed are contam inated PCB sites 23 and w astes w ith less than 50-ppm PC B (w hich are not regulated under TSCA ). N o inform ation 24 w as found that w ould allow evaluation o f releases from these sources. 25 The original report concluded that it is likely that no significant releases o f new ly form ed 26 dioxin-like P C B s are occurring in the U nited States. This is based on three argum ents. First, 27 although the data are lim ited, the inventory presented here suggests that new releases are low in 28 com parison to the am ounts currently present in the environm ent. A s show n in Table 10-1, the 29 to ta l q u a n tita tiv e re le a se e stim a te s fo r 2 0 0 0 sum to o n ly a b o u t 30 g W H O 98 T E Q P/y e a r to a ir an d 30 2 0 g W H O 98 T E Q P/y e a r to land. A s d isc u sse d in C h a p te r 11, th e su rfa c e so ils in th e U n ite d 31 S tates are estim ated to contain ab o u t 95 kg o f P C B TE Q s. A lso, th e release estim ates m ay 32 overestim ate new releases because som e portion m ay be passed through from inputs to outputs This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 1 DRAFT: DO NOT CITE OR QUOTE 1 rather than new formation. Second, the new releases appear low compared to past releases 2 associated with PCB production, use, and disposal. As discussed in Section 10.7, an estimated 3 3,702 kg of WHO98 TEQp were released directly to the U.S. environment between 1930 and 4 1977. Third, North American sediment studies have shown decreasing PCB levels since the 5 1980s (Lebeuf et al., 1995; Cleverly et al., 1996), indicating that releases of newly formed PCBs 6 are not large enough to prevent this decline. Accordingly, the original statement is still believed 7 to likely be true, but it is acknowledged to be uncertain because releases could be estimated for 8 only a few sources. 9 10 10.2. RELEASES FROM COMMERCIAL PCB PRODUCTS 11 10.2.1. Approved PCB Disposal/Destruction Methods 12 As discussed in the original report, landfilling and incineration can be used as disposal 13 methods for PCBs. It is assumed that the amounts landfilled would not represent an 14 environmental release. The incineration facilities achieve a high combustion efficiency, but 15 some releases are possible. The original report summarizes TRI information on total PCB 16 releases to air, surface water, and land. Insufficient information was available to convert these 17 releases to TEQ estimates. 18 19 PCB Incineration Releases Not quantifiable._________________________________ 20 21 22 10.2.2. Releases of In-Service PCBs 23 As discussed in the original report, insufficient information is available to make 24 quantitative release estimates occurring from in-service PCBs. No changes were made to this 25 conclusion, but some additional background information on accidental fires is provided below. 26 Also, this section was expanded to include nonaccidental releases of in-service PCBs. 27 A variety of PCB products can remain in use for long time periods, such as paint, caulk, 28 transformers, and capacitors. Releases from these products can occur via vaporization or leaks 29 or during disposal operations. As discussed in the original report (see Section 10.6), 30 approximately 568,000 MT of PCBs were used in the United States between 1930 and 1975. An This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 2 DRAFT: DO NOT CITE OR QUOTE 1 estim ated 50.3% w ere used in capacitors, and 26.8% w ere used in transform ers. A ssum ing that 2 th e s e p ro d u c ts c o n ta in e d an a v e ra g e o f 8 m g W H O 98 T E Q p /k g (a v e ra g e c o n c e n tra tio n fo r 3 A roclor 1242, w hich accounted for over 50% o f total sales-- see Section 10.6 o f original report), 4 th e n a to ta l o f 3 ,5 0 0 k g o f W H O 98 T E Q P w e re u s e d in c a p a c ito rs a n d tra n sfo rm e rs. It is 5 unknow n how m uch o f this m aterial is still in use today or w hat am ount o f releases m ay be 6 occurring. N ote that these products can be considered reservoirs because the releases can occur 7 after th eir initial use, so th ey are also discussed in C h ap ter 11. 8 A report by the Environm ent A gency in the U nited K ingdom assessed the im portance of 9 releases o f PC B s from various sources (Dyke, 2002). This report concluded that leaks from 10 capacitors and tran sfo rm ers are lik ely to b e th e larg est source o f P C B releases occurring 11 cu rren tly , a lth o u g h th is is e x p e c te d to d e c lin e as th e s e d e v ic e s are ta k e n o u t o f serv ic e an d 12 disposed. L eak s from electrical eq u ip m en t w ere estim ated to acco u n t fo r 80% o f th e total P C B 13 re le a s e s o c c u rrin g in th e U n ite d K in g d o m in 1998 (D y k e , 2002). 14 A n u m b er o f P C B tran sfo rm er fires hav e o ccu rred in th e U n ited States, lead in g to PC B 15 c o n ta m in a tio n o f th e in te rio rs o f o ffic e b u ild in g s (M ic h a u d et al., 1994). S o o t can b e p ro d u c e d 16 in large am ounts, co n sistin g o f p articles th at m ay contain P C B co n cen tratio n s up to 17 5 ,0 0 0 -8 ,0 0 0 m g /k g o f so o t (M ich au d et al., 1994). T he fo llo w in g are several ex am p les o f PC B 18 fires in o ffice b u ild in g s. 19 In th e case o f a tran sfo rm er fire in th e b asem en t o f th e N e w Y o rk State office b u ild in g in 20 B ingham ton, N Y , the circulation o f PC B -contam inated soot particles resulted in an average 21 interior surface concentration o f 162 m g/m (expressed as the equivalent A roclor 1254 22 concentration) (Erickson, 1997). A dditionally, the soot sam ples from the B ingham ton PC B fire 23 contained about 20 m g/g and 700 m g/g o f total C D D s and total PC D Fs, respectively (Erickson, 24 1997). In 1985, a PC B transform er fire occurred in the basem ent transform er vault in the m ain 25 building o f the N ew M exico State H ighw ay D epartm ent O ffice B uilding (CD C, 1985). Interior 26 air concentrations o f PC B s in the transform er vault w ere found to average about 48 pg/m . 27 Surface w ipes on horizontal surfaces had PCB concentrations ranging from 4,700 to 28 30 m illion pg/m . O ther notable U.S. transform er fires include the office building at 29 1 M arke Plaza in San Francisco in 1983, the Saniford Street office building in B oston in 1981, 30 and the P age B elcher b uilding in T ulsa (M ichaud et al., 1994). In these fires, indoor air PC B 31 co n cen tratio n s ranged from 140 to 1,500 pg/m ; in terio r surfaces to th e b u ild in g s ran g ed from This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-3 DRAFT: DO N O T CITE OR QUO TE 1 2 0 -9 0 pg/m 2 total PCBs. TCD F concentrations ranged from 4 -3 0 pg/m 3 in the indoor office air 2 2 and from 20 0 -7 0 0 ng/m to interior surfaces. 3 4 Releases of In-Service PCBs Releases________ N o t q u an tifiab le._______________________________________________ 5 6 7 10.3. CHEMICAL MANUFACTURING AND PROCESSING SOURCES 8 The original report discussed M unicipal W astew ater T reatm ent u nder Section 10.2. In 9 this update, it has been m oved to this section because these facilities are not associated w ith 10 com m ercial P C B p ro d u cts and do co n d u ct a ty p e o f chem ical processing. M in o r changes w ere 11 m a d e to th e re le a se e stim a te s as su m m a riz e d b elo w . 12 F o r referen ce years 1987 and 1995, th e co n cen tratio n o f d io x in -lik e P C B s th at m ay b e 13 p re s e n t in se w a g e slu d g e w a s e s tim a te d as 24.3 n g W H O 98 T E Q P/k g . T h is is b a se d o n th e 1994 14 survey o f 74 p lan ts as rep o rted b y G reen et al. (1995) and C ram er et al. (1995). F o r referen ce 15 y e a r 2 0 0 0 , th e c o n c e n tra tio n o f d io x in -lik e P C B s th a t m a y b e p re s e n t in se w a g e slu d g e w a s 16 e s tim a te d as 5 .2 2 n g W H O 98 T E Q P/kg. T h is is b a se d o n th e 2001 su rv e y o f 94 p la n ts (U .S . E P A , 17 2002d). T he activity estim ates w ere b ased on th e 1988/1989 N atio n al S ew age S ludge Survey 18 and th e resu lts o f th e 1984 to 1996 C lean W a te r N e e d s S urveys (U .S. E P A , 1999b). A ll 19 b en eficial u ses w ere assum ed to have th e potential fo r release to th e environm ent, resu ltin g in 20 increases in the product release estim ates com pared to the original report. 21 A s discussed in E P A (2006), there is no clear evidence that other types o f chem ical 22 m anufacturing and processing facilities release dioxin-like PCBs. 23 The inventory decision criteria and releases to all m edia are sum m arized below : 24 25 26 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 4 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Municipal Wastewater Treatment Air W ater Solids Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable differences. Yes Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). 1 Q 2 Emission Factors Municipal Wastewater Treatment Soil Releases 1 9 8 7 -- 2 4 n g W H O 98 T E Q p /k g o f slu d g e. 1 9 9 5 -- 2 4 n g W H O 98 T E Q p /k g o f slu d g e. 2 0 0 0 -- 5.2 n g W H O 98 T E Q p/kg o f sludge. Activity Levels 1987-- 2.1 M M T o f sludge. 1995-- 3.2 M M T o f sludge. 2000-- 3.6 M M T o f sludge. Releases 1 9 8 7 -- 51 g W H O 98 TEQ p. 1 9 9 5 -- 78 g W H O 98 TEQ p. 2 0 0 0 -- 19 g W H O 98 TEQ p. Emission Factors Product Releases 1 9 8 7 -- 2 4 n g W H O 98 T E Q p /k g o f slu d g e. 1 9 9 5 -- 2 4 n g W H O 98 T E Q p /k g o f slu d g e. 2 0 0 0 -- 5.2 n g W H O 98 T E Q p/kg o f sludge. Activity Levels 1987-- 0.07 M M T o f sludge. 1995-- 0.5 M M T o f sludge. 2 0 0 0 -- 0.5 M M T o f sludge.*34 Releases 1 9 8 7 -- 2 g W H O 98 TEQ p. 1 9 9 5 -- 12 g W H O 98 T E Q p. 2 0 0 0 -- 3 g W H O 98 T E Q p .________________________________________________________________ 3 4 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 5 DRAFT: DO NOT CITE OR QUOTE 1 10.4. COMBUSTION SOURCES 2 10.4.1. Municipal Waste Combustion 3 The 2006 report concluded that insufficient information was available to develop 4 quantitative release estimates from municipal waste incinerators. A number of additional studies 5 are presented below that allow making preliminary estimates. 6 Dyke (2002) provides a review of PCB emission factors for municipal waste incinerators. 7 These vary from 0.000027 to 14 ng TEQP/kg. Dyke et al. (2003) provide a similar literature 8 survey of 1990's data on incinerator emissions and fly ash concentrations of concurrently 9 measured dioxin-like PCBs and CDD/CDF TEQ. Their literature summary supports the 10 observation that WHO98 TEQPemission concentrations from MWCs are an order of magnitude 11 and more lower than WHO98 TEQDF. They also provide some PCB emission factors from these 12 references, showing a fairly wide range from as low as 0.0085 to as high as 13 25.6 pg WHO98 TEQp/MT. Finally, they provide results of their own testing on two MWCs with 14 different levels of pollution control. For one MWC, three of four tests were nondetect for all 15 14 PCBs measured and the other test showed some positive concentrations. For the second 16 MWC, two tests had positive measurements for PCB-114, PCB-118, PCB-123, and PCB-180. 17 The range of reported WHO98 TEQPemission concentrations was between 0 (assuming ND = 0) 18 and 0.016 ng WHO98 TEQP/Nm3(assuming ND = QL). 19 Sakai et al. (1999) found that the input of coplanar PCBs into the municipal solid waste 20 incineration facilities in Kyoto City (Japan) was 0.13-0.29 mg-TEQ per ton waste, the total 21 output of coplanar PCBs (the sum released from emission gas, fly ash, and bottom ash) was 4.9 22 mg TEQ per ton waste. The PCB emission factor for gas releases was reported to be 1.2 pg 23 TEQ/ton of waste burned. They reported PCB concentrations in fly ash of 0.053 ng TEQ/g and in 24 bottom ash as 0.000023 ng TEQ/g. 25 CDD/CDFs and dioxin-like PCBs were measured in the emissions from an MWC in 26 Madrid, Spain, which was equipped with a high level of pollution control (Abad et al., 2006). 27 Over 16 samples, CDD/CDF emissions averaged 0.047 ng I-TEQ/Nm3, and dioxin-like PCBs 3 28 added an average of 0.0015 ng I-TEQ/Nm , with most of this dioxin-like PCB contribution from 29 PCB-126. 30 Eight incinerators, including two commercial MWCs, were sampled for CDD/CDFs, 31 PCBs, and HCB in a study conducted in Japan (Kim et al., 2004a). The average concentration This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-6 DRAFT: DO NOT CITE OR QUOTE 1 o v e r all e ig h t in c in e ra to rs w a s 0.281 n g W H O 98 T E Q DF/N m 3 fo r C D D /C D F s an d 2 0.023 n g W H O 98 T E Q p /N m 3 fo r P C B s, su g g e stin g a fa c to r o f d iffe re n c e o f 10 o n av erag e. T h e 3 d isp a rity fro m o n e o f th e tw o M W C in c in e ra to rs w a s 0 .0 6 9 n g W H O 98 T E Q DF/N m fo r 4 C D D /C D F a n d 0 .0 0 9 n g W H O 98 T E Q P/N m 3 fo r P C B s. E m issio n s w e re m u c h lo w e r fo r th e o th e r 5 M W C , w ith re p o rte d T E Q c o n c e n tra tio n s u n in fo rm a tiv e at 0 .0 0 0 n g W H O 98 T E Q DFP/N m 3. 6 F rancois et al. (2005) p rovide side-by-side m easurem ents o f C D D /C D F s and dioxin-like 7 P C B s, w hich contradict th e observations provided by D yke et al. (2003). F rancois et al. (2005) 8 rep o rts on te stin g at 15 in cin erato rs in clu d in g th ree M W C s in B elgium . T he d io x in -lik e P C B s 9 often dom inated the overall TEQ em issions. F or exam ple, the average shares o f the dioxin-like 10 P C B s to total T E Q w ere 22, 34, and 97% fo r th e th ree M W C s. T he stack co n cen tratio n s o f 11 d io x in -lik e P C B s w e re 0 .0 0 0 8 , 0 .0 4 5 , a n d 0 .0 0 3 4 n g W H O 98 T E Q P/N m 3, c o m p a re d to 12 c o rre s p o n d in g C D D /C D F c o n c e n tra tio n s o f 0 .0 0 1 4 , 0 .0 0 1 4 , a n d 0 .0 1 2 n g W H O 98 T E Q DF/N m 3. 13 B a s e d o n th e s e c o n c e n tra tio n s a n d o th e r p la n t ch a ra c te ristic s, an n u a l d io x in -lik e P C B em issio n s 14 w e re q u a n tifie d in all o f th e s e p la n ts at 0.4, 7.0, a n d 1.2 m g W H O 98 T E Q P/year. 15 K im et al. (2 0 0 5 ) m e a su re d 2 0 9 c o n g e n e rs in sta c k e m issio n s fro m n in e fa c ilitie s in 16 Japan, in clu d in g th ree M W C s. T hey did n o t m easu re C D D /C D F s, b u t th eir m easured 17 co n cen tratio n s can b e com pared w ith o th er studies id en tified above. T hey d etected P C B s at all 18 facilities, w ith to tal P C B s ran g in g from 1 0 -7 0 0 n g /N m and co p lan a r P C B s in th e ran g e o f 19 1 -2 5 n g /N m 3 (0 .0 0 8 -0 .3 2 4 n g W H O 98 T E Q P/N m 3). O n a c la ss b a sis, th e a v e ra g e fro m th e 20 M W C s w a s th e h ig h e st at 0 .1 3 6 n g W H O 98 T E Q P/N m 3. 21 T he P C B em ission factor for m unicipal w aste incinerators w as assum ed to equal the 22 geom etric m ean o f the range reported by D yke et al., 2003 (0.0085 to 23 2 5 .6 p g W H O 98 T E Q P/M T ) w h ic h is 0.5 n g W H O 98 T E Q P/kg. T h is e m issio n fa c to r is c o n sid e re d 24 p relim in ary due to th e in co n sisten cy in th e results. T h e activ ity d ata are p resen ted in C h ap ter 3. 25 PC B s are also likely to be present in the ash, but these w ould be landfilled and not considered an 26 environm ental release. The inventory decision criteria and releases to all m edia are sum m arized 27 below: This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 7 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Municipal Waste Combustion Air W ater Solids Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. No Yes A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). P 1 2 Emission Factors Municipal Waste Combustion_________________________ Air Releases________________________________ 1 9 8 7 -- 0.5 n g W H O 98 T E Q p /k g (P re lim in a ry ). 1 9 9 5 -- 0.5 n g W H O 98 T E Q P/k g (P re lim in a ry ). 2 0 0 0 -- 0.5 n g W H O 98 T E Q P/k g (P re lim in a ry ).___________________________________________ Activity Levels 1987-- 13.7 billion kg. 1995-- 29.8 billion kg. 2 0 0 0 -- 2 9 .4 b illio n kg.___________________________________________________________________ Releases 1 9 8 7 -- 7 g W H O 98 T E Q P (P re lim in ary ). 1 9 9 5 -- 15 g W H O 98 T E Q P (P re lim in ary ). 2 0 0 0 -- 15 g W H O 98 T E Q P (P re lim in ary ).________________________________________________ 3 4 5 10.4.2. Industrial Wood Combustion 6 As discussed in EPA (2006), evidence exists that PC B s can be released from industrial 7 w ood com bustion, but the inform ation is insufficient to m ake quantitative release estim ates. N o 8 changes w ere m ade to this conclusion. 9 Industrial Wood Combustion_________________________ Releases__________________________________ N o t q u an tifiab le.________________________________________________________________________________ 10 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 8 DRAFT: DO NOT CITE OR QUOTE 1 10.4.3. Medical Waste Incineration 2 E PA (2006) concluded that insufficient evidence existed to derive em ission factors for 3 PCB releases from m edical w aste com bustion. As discussed below , additional studies w ere 4 found that allow ed m aking prelim inary release estim ates. 5 D yke et al. (2003) surveyed the literature fo r studies providing m easurem ents o f 6 dioxin-like PC B s along w ith CD D /C D Fs from pow er stations and w aste incineration processes. 7 They identified a study published in 1996 (E hrlich et al., 1996) in w hich the PC B em ission 8 c o n c e n tra tio n fro m a m e d ic a l w a ste in c in e ra tio n w a s 0.035 n g W H O 98 T E Q P/N m , w h ile it w a s 9 0 .9 7 n g W H O 98 T E Q DF/N m fo r C D D /C D F s. T h ey also c o n d u c te d th e ir o w n m e a su re m e n ts o n a 10 m edical w aste in cin erato r in th e U n ited K ingdom . T hey q u an tified co n cen tratio n s o f P C B -118, 11 P C B -1 2 3 , P C B -1 7 0 , a n d P C B -1 8 0 -- b u t n o t th e o th e r 14 c o n g e n ers. A ssu m in g N D = 0, o n e o f 12 tw o ru n s h a d a c o n c e n tra tio n o f 0 .0 0 0 0 7 n g W H O 98 T E Q P/N m , w h ile th e o th e r h a d a 13 c o n c e n tra tio n o f 0 .0 2 2 W H O 98 T E Q P/N m at N D = 0. In co n tra st, th e sam e tw o ru n s h ad 14 C D D /C D F c o n c e n tra tio n s at N D = 0 at 0 .0 7 a n d 0.05 n g W H O 98 T E Q DF/N m 3. 15 T h e d a ta re p o rte d b y D y k e et al. (2 0 0 3 ) su g g e st th a t P C B T E Q e m issio n s are 1 to 2 5 % o f 16 th e d io x in em issions. T he E h rlich et al. (1996) d ata suggest th at th e P C B T E Q em issio n s are 4% 17 o f th e d io x in em issions. T he E h rlich et al. (1996) v alu e w as selected as a central estim ate and 18 m u ltip lied b y th e av erag e C D D /C D F em issio n fa c to r fo r each re fere n ce y e a r (total C D D /C D F 19 em issio n s divided by th e total activity as rep o rted in C h ap ter 3). T his p ro ced u re gave the 20 em ission factors show n below. These em ission factors are considered prelim inary because the 21 studies provided insufficient inform ation to directly derive them . The activity data are presented 22 in C hapter 3. P C B s are also likely to b e present in the ash, b u t these w ould be landfilled and not 23 considered an environm ental release. The inventory decision criteria and releases to all m edia 24 are sum m arized below: This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 0 - 9 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Medical Waste Incineration Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. Yes A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). P 1 2 Emission Factors Medical Waste Incineration_____________________ Air Releases____________________________ 1 9 8 7 -- 68 n g W H O 98 T E Q p /k g (P re lim in ary ). 1 9 9 5 -- 2 4 n g W H O 98 T E Q P/k g (P re lim in ary ). 2 0 0 0 -- 2 4 n g W H O 98 T E Q P/k g (P re lim in ary )._____________________________________ Activity Levels 1987-- 1.43 b illio n kg. 1995-- 0.77 billion kg. 2 0 0 0 -- 0.6 b illio n kg.______________________________________________________________ Releases 1 9 8 7 -- 97 g W H O 98 T E Q P (P re lim in ary ). 1 9 9 5 -- 18 g W H O 98 T E Q P (P re lim in ary ). 2 0 0 0 -- 14 g W H O 98 T E Q P (P re lim in ary ).__________________________________________ 3 4 5 10.4.4. Tire Combustion 6 As discussed in EPA (2006), evidence exists that PC B s can be released from tire 7 com bustion, but the inform ation is insufficient to m ake quantitative release estim ates. N o 8 changes w ere m ade to this conclusion. 9 ___________________________________________________________________________________________ Tire Combustion__________________________ Releases_____________________________ N o t q u an tifiab le.__________________________________________________________________________ 10 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-10 DRAFT: DO NOT CITE OR QUOTE 1 10.4.5. Cigarette Smoking 2 As discussed in the original report, PCB releases can occur during cigarette 3 sm oking. N o changes w ere m ade to these estim ates as sum m arized below. 4 A prelim inary estim ate o f potential em issions o f dioxin-like PC B s can be m ade using the 5 fo llo w in g assu m p tio n s: (a) th e a v e ra g e W H O 98 T E Q P c o n te n t o f sev e n b ra n d s o f U .S . cig a re tte s 6 reported by M atsu ed a et al. (1994), 0.64 pg/pack (0.032 pg/cigarette), is representative o f 7 cigarettes sm oked in the U nited States; (b) dioxin-like P C B s are neither form ed nor destroyed, 8 and the congener profile reported by M atsueda et al. (1994) is not altered during com bustion o f 9 cigarettes; and (c) all dioxin-like PC B s contributing to the TEQ are released from the tobacco 10 during sm oking. T his em issio n facto r is con sid ered p relim in ary b ecau se o f th e m u ltip le 11 a s s u m p tio n s re q u ire d in its d e riv a tio n . C ig a re tte c o n su m p tio n is d isc u sse d in S ectio n 5.5. 12 T he in v en to ry d ecisio n criteria and releases to all m ed ia are su m m arized below : 13 14 Inventory Decision Criteria for Cigarette Smoking Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-11 DRAFT: DO NOT CITE OR QUOTE Cigarette Smoking Air Releases____ Emission Factors 1 9 8 7 -- 0.03 p g W H O 98 T E Q p /cig a rette (P re lim in ary ). 1 9 9 5 -- 0.03 p g W H O 98 T E Q P/c ig a re tte (P re lim in ary ). 2 0 0 0 -- 0.03 p g W H O 98 T E Q P/c ig a re tte (P re lim in ary ). Activity Levels 1987-- 575 billion cigarettes. 1995-- 487 billion cigarettes. 2 0 0 0 -- 4 4 0 b illio n cig arettes._________________________ Releases 1 9 8 7 -- <0.1 g W H O 98 T E Q P (P re lim in ary ). 1 9 9 5 -- <0.1 g W H O 98 T E Q P (P re lim in ary ). 2 0 0 0 -- <0.1 g W H O 98 T E Q P (P re lim in ary ).__________ 1 2 3 10.4.6. Sewage Sludge Incineration 4 As discussed in the original report, PCB releases can occur from sew age sludge 5 incineration. N o changes w ere m ade to these estim ates as sum m arized below . A dditional 6 inform ation w as found regarding a stack test for a sew age sludge incinerator in the U nited 7 K ingdom (D yke et al., 2003). This w as not used in the em ission factor derivation because all 8 dioxin-like PCB congeners w ere below the detection lim its o f about 0.12 ng/N m for each 9 congener. 10 T he em issio n factor w as b ased on m easu rem en ts co n d u cted at a m u ltip le-h earth 11 in c in e ra to r in O h io e q u ip p e d w ith a v e n tu ri s c ru b b e r a n d a th re e -tra y im p in g e m e n t c o n d itio n in g 12 to w er (U .S. E P A , 2000b). T his em issio n facto r w as con sid ered p relim in ary b ecau se it is based 13 o n te s tin g at o n ly o n e fa cility . S ew a g e slu d g e a c tiv ity d a ta are p re se n te d in C h a p te r 8. 14 T he in v en to ry d ecisio n criteria and releases to all m ed ia are su m m arized below : This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-12 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Sewage Sludge Incineration Air W ater Solids Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. Products M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). P 1 2 Sewage Sludge Incineration Air Releases_______ Emission Factors 1 9 8 7 -- 0.51 n g W H O 98 T E Q p/kg o f slu d g e (P re lim in ary ). 1 9 9 5 -- 0.51 n g W H O 98 T E Q P/k g o f slu d g e (P re lim in ary ). 2 0 0 0 -- 0.51 n g W H O 98 T E Q P/k g o f slu d g e (P re lim in ary ). Activity Levels 1987-- 0.865 M M T. 1995-- 2.11 M M T. 2 0 0 0 -- 1.42 M M T ._______________________________________ Releases 1 9 8 7 -- 0.4 g W H O 98 T E Q P (P re lim in ary ). 1 9 9 5 -- 1 g W H O 98 T E Q P (P re lim in ary ). 2 0 0 0 -- 0.7 g W H O 98 T E Q P (P re lim in ary ).________________ 3 4 5 10.4.7. Backyard Barrel Burning 6 The original report concluded that insufficient inform ation w as available to m ake 7 quantitative PC B release estim ates for backyard barrel burning. N ew inform ation is provided 8 below , w hich allow ed m aking both air and land release estim ates for this source category. 9 G onczi et al. (2005) tested em issions from burn in g d om estic w astes in b arrels (19 tests) 10 and open fires (2 tests). G as collected above th ese fires allo w ed fo r estim atio n o f em ission 11 fa cto rs. T h e m a te ria l b u rn e d c o n siste d o f v a rio u s m ix tu re s o f g a rd e n w a ste s, straw , p ap er, 12 several fo rm s o f plastic, tires, w aste m o to r oil, R D F , and co m p u ter scrap. A barrel b u rn w ith a 13 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10 _13 DRAFT: DO NOT CITE OR QUOTE 1 m ix o f garden w aste and polyvinyl chloride (PV C ) w aste had the highest em ission factor o f 2 190 n g P C B T E Q /k g b u rn e d . T h e o th e r te sts ra n g e d fro m 0.3 to 3 .2 n g W H O 98 T E Q P/k g b u rn e d . 3 The dioxin-like PC B s generally m ade up m uch less than 10% o f the total TEQ em issions. 4 As reported in EPA (2006), Lem ieux (1997) also m easured PCB em issions from tests 5 sim ulating backyard barrel burning. The average em ission factor across tw o tests was 6 5 .2 6 n g W H O 98 T E Q P/k g w a ste b u rn e d . T h is e m issio n fa c to r w a s se le c te d as th e m o st 7 representative o f typical dom estic waste. 8 Lem ieux (1997) also collected ash sam ples from open barrel burning and analyzed for 9 PCBs. A sh sam ples from the experim ents w ere com bined, resulting in tw o com posite 10 sam p les-- one fo r recy clers and one fo r n o n recy clers (see T able 10-2). T he overall average w as 11 0.8 n g W H O 98 T E Q P /kg o f ash. 12 T he activity lev els fo r b ack y ard barrel b u rn in g (total w aste b u rn ed and ash g en erated ) 13 w e re p re s e n te d in S e c tio n 6.5.2. 14 T he in v en to ry d ecisio n criteria and releases to all m ed ia are su m m arized below : 15 16 Inventory Decision Criteria for Backyard Barrel Burning Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Yes Em ission factor tests represent units that are typical o f the class. Yes Yes A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). Yes Q Yes Q This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-14 DRAFT: DO NOT CITE OR QUOTE Emission Factors Backyard Barrel Burning__________________________ Air Releases________________________________ 1 9 8 7 -- 5.3 n g W H O 98 T E Q p/kg o f w a ste b u rn e d . 1 9 9 5 -- 5.3 n g W H O 98 T E Q P/k g o f w a ste b u rn e d . 2 0 0 0 -- 5.3 n g W H O 98 T E Q P/k g o f w a ste b u rn e d ._______________________________________ Activity Levels 1987-- 7.87 M M T. 1995-- 8.18 M M T. 2 0 0 0 -- 6 .4 9 M M T ._____________________________________________________________________ Releases 1 9 8 7 -- 41 g W H O 98 TEQ p. 1 9 9 5 -- 43 g W H O 98 TEQ p. 2 0 0 0 -- 34 g W H O 98 TEQ p._____________________________________________________________ Solid Residue Releases___________________________ Emission Factors 1 9 8 7 -- 0.8 n g W H O 98 T E Q p /k g o f ash. 1 9 9 5 -- 0.8 n g W H O 98 T E Q p /k g o f ash. 2 0 0 0 -- 0.8 n g W H O 98 T E Q p/k g o f a sh b u rn e d ._________________________________________ Activity Levels 1987-- 1.2 M M T . 1995-- 1.2 M M T . 2 0 0 0 -- 0 .9 7 M M T ._____________________________________________________________________ Releases 1 9 8 7 -- 1 g W H O 98 T E Q p. 1 9 9 5 -- 1 g W H O 98 TEQ p. 2 0 0 0 -- 0.8 g W H O 98 TEQp.____________________________________________________________ 1 2 3 10.4.8. Petroleum Refining Catalyst Regeneration 4 As discussed in Ep A (2006), evidence exists that pC B s can be released from petroleum 5 refining catalyst regeneration, but the inform ation is insufficient to m ake quantitative release 6 estim ates. N o changes w ere m ade to this conclusion. 7 ________________________________________________________________________________________________ Petroleum Refining Catalyst Regeneration___________________ Air Releases________________________________ N o t q u an tifiab le._______________________________________________________________________________ 8 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-15 DRAFT: DO NOT CITE OR QUOTE 1 10.4.9. Hazardous Waste Incineration 2 This is a com pletely new section on hazardous w aste incineration. 3 Tw o studies w ere identified from outside o f the U nited States that m easured em issions o f 4 dioxin-like PC B s along w ith dioxins and furans from hazardous w aste incinerators. One o f the 5 studies w as consistent w ith studies on m unicipal solid w aste incinerators, w hich show ed 6 CD D /C D F TEQ em issions to be an order o f m agnitude and m ore higher than PCB em issions. 7 K im et al. (2005) m easured 209 congeners in stack em issions from nine facilities, w hich 8 included tw o industrial w aste incinerators and a " specific industrial w aste incinerator." The 9 em ission concentrations of the dioxin-like PC B s in the industrial w aste incinerators w ere 10 0 .1 3 6 fo r th e " s p e c ific " in c in e ra to r a n d 0 .0 2 5 n g W H O 98 T E Q P/N m 3 fo r th e a v e ra g e o f th e 11 tw o in d u stria l w a ste in c in e ra to rs. T h e se w e re c h a ra c te riz e d as b e in g eq u al to 2 .9 a n d 1.3% o f 12 th e e m is s io n c o n c e n tra tio n s o f W H O 98 T E Q DF. O n th e o th e r h an d , F ra n c o is et al. (2 0 0 5 ) 13 m e a s u re d d io x in s, fu ran s, a n d c o p la n a r P C B s fro m 15 fa c ilitie s in c lu d in g o n e H W I. T h e 14 c o n c e n tra tio n o f th e P C B s w a s 0 .0051 n g W H O 98 T E Q P/N m , w h ic h w a s a lm o st th re e tim e s 15 h ig h e r th a n th e m e a s u re m e n t o f C D D /C D F s, at 0 .0 0 1 9 n g W H O 98 T E Q P/N m 3. T h e an n u al 16 e m issio n o f d io x in -lik e P C B s fro m th is fa c ility w a s e stim a te d at 1.5 m g W H O 98 T E Q P/year. 17 G iven th e in co n sisten t resu lts from th ese tw o studies, it is u n clear h o w to m ak e em ission 18 estim ates on ev en a p re lim in ary basis. 19 T herefore, th e av ailab le d ata w ere ju d g e d in ad eq u ate to su pport d ev elo p m en t o f a 20 quantitative estim ate o f a dioxin-like PCB em ission factor for this source category. 21 22 Hazardous Waste Incineration Releases_________ N o t q u an tifiab le._________________________________________________ 23 24 25 10.4.10. Power Plants 26 This is a com pletely new section. 27 E m issions from pow er plants w ere estim ated to account for 2% of the total PCB releases 28 occurring in the U nited K ingdom in 1998 (Dyke, 2002). 29 B rodsky et al. (2003) reported on m easurem ents from six com bustion sources in R ussia, 30 including tw o pow er plants. N um erous individual congener concentrations in the stack gas This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-16 DRAFT: DO NOT CITE OR QUOTE 1 emissions were provided including some dioxin-like PCBs, although no TEQ estimates were 2 provided and no congener-specific emission factors were provided. Concentrations were 3 provided for PCB-105, PCB-118, PCB-123, PCB-156, PCB-157, PCB-170, and PCB-180. The 4 TEQ concentration in the power plant for these congeners was 0.02 ng WHO98 TEQP/Nm . 5 Francois et al. (2005) reported on testing at 15 incinerators including one coal-fired 6 power plant. They measured emissions of CDD/CDF and PCB as 7 0.0003 ng WHO98 TEQDF/Nm3 and 0.0009 ng WHO98 TEQP/Nm3, respectively. Extrapolating to 8 annual emissions, they estimated an emission of 1.17 mg WHO98 TEQP/year. Dyke et al. (2003) 9 reported on emission measurements from a coal-fired power station in the United Kingdom. 10 They found nondetects for all dioxin-like PCBs tested, except a positive for PCB-180 in one of 11 two tests. 12 The available data were judged inadequate to support development of a quantitative 13 estimate of a dioxin-like PCB emission factor for this source category. 14 15 Power Plants Releases Not quantifiable._______________________________ 16 17 18 10.4.11. Forest Fires 19 This is a completely new section. 20 Collet and Fianni (2006) conducted five forest fire test burns in a chamber of about 21 80 m3. The samples were collected from forests in two regions of southern France and the tests 22 were conducted by the French Agency for Environment and Energy Management. Blank 23 samples were also taken to ensure that the chamber did not introduce contaminants to the burns. 24 Emission concentrations were determined for the 17 CDD/CDFs and 12 dioxin-like PCBs. 25 Generally, PCBs explained about 6% of the total TEQ emissions, except for one forest fire burn, 26 where emissions overall were close to blanks and PCBs contributed 26% in this case. The 27 emission factors for CDD/CDFs ranged from 1.0 ng I-TEQDF/kg burned (the low for the test 28 close to the blank) to 26 ng I-TEQDF/kg. The TEF scheme used to characterize PCB emissions 29 was not clear but assumed here to be WHO98. This implies that the PCB emission factor ranged 30 from 0.06 to 1.6 WHO98 TEQp. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-17 DRAFT: DO NOT CITE OR QUOTE 1 For the purposes o f deriving a prelim inary estim ate, it is assum ed that the PCB TEQ 2 em ission factor is 6% o f the one for C D D /C D Fs (based on the results from C ollet and Fianni 3 [2 0 0 6 ]). A s d isc u sse d in C h a p te r 6, th e fo re st fire e m issio n fa c to r is 3 n g W H O 98 T E Q DF/kg. 4 T h is is a d ju ste d to 0 .2 n g W H O 98 T E Q P/k g fo r P C B s. T h is e m issio n fa c to r is c o n sid e re d 5 prelim inary because it is uncertain how w ell the lim ited testing represents all fire/w ood types. 6 The activity levels for forest fires are presented in C hapter 6. P C B s are also likely to be present 7 in the ash, but insufficient inform ation w as available to m ake quantifiable estim ates. 8 The inventory decision criteria and releases to all m edia are sum m arized below : 9 10 Inventory Decision Criteria for Forest Fires Air W ater Solids Products Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable Yes differences. Em ission factor tests represent units that are typical o f the class. No A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10_18 DRAFT: DO NOT CITE OR QUOTE Forest Fires Air Releases Emission Factors 1 9 8 7 -- 0.2 n g W H O 98 T E Q p/kg (P re lim in a ry ). 1 9 9 5 -- 0.2 n g W H O 98 T E Q P/k g (P re lim in a ry ). 2 0 0 0 -- 0.2 n g W H O 98 T E Q P/k g (P re lim in a ry ). Activity Levels 1987-- 61 M M T. 1995-- 55 M M T. 2 0 0 0 -- 2 4 3 .8 M M T ._________________________________ Releases 1 9 8 7 -- 12 g W H O 98 T E Q P (P re lim in ary ). 1 9 9 5 -- 11 g W H O 98 T E Q P (P re lim in ary ). 2 0 0 0 -- 4 9 g W H O 98 T E Q P (P re lim in ary ).____________ Solid Residue Releases N o t q u an tifiab le.____________________________________________ 1 2 3 10.5. METAL REFINING SOURCES 4 This is a com pletely new section. 5 K im et al. (2004) m easured all 209 PC B congeners in stack em issions from 6 nine facilities, including a sintering furnace in a ferrous m etal foundry and tw o sm elting furnaces 7 in nonferrous m etal foundries in Japan. All nine facilities em itted PCBs, w ith total PC B s 8 ranging from 10-700 ng/N m and coplanar PC B s in the range o f 1-25 ng/N m 9 ( 0 .0 0 8 -0 .3 2 4 n g W H O 98 T E Q P/N m 3). T h e th re e m etal fa c ilitie s h a d th e s e re su lts: alu m in u m 10 sm e ltin g fu rn a c e -- 0 .0 2 0 n g W H O 98 T E Q P/N m ; c o p p e r sm e ltin g 11 fu rn a c e -- 0 .0 2 6 n g W H O 98 T E Q P/N m 3; a n d sin te rin g fu rn a c e -- 0 .0 1 8 n g W H O 98 T E Q P/N m 3. In 12 term s o f a relatio n sh ip to C D D /C D F s, K im et al. (2004) d eveloped a ratio o f th e T E Q 13 c o n c e n tra tio n o f d io x in -lik e P C B s to th a t o f C D D /C D F s a n d fo u n d th e n a rro w ra n g e o f 0 .0 3 2 to 14 0.050, su ggesting th at th e T E Q con cen tratio n o f d io x in -lik e P C B s w as o v er an o rd er o f 15 m a g n itu d e lo w e r th a n th a t o f C D D /C D F s. 16 S tack gas em issio n s o f d io x in -lik e P C B s w ere m easu red alo n g w ith C D D /C D F s from 17 th ree iron ore sin terin g p lants in th e U n ited K in g d o m b etw een 2002 and 2003 (A ries et al., 18 2 0 0 6 ). T h e d io x in -lik e P C B s fo u n d at th e h ig h e st c o n c e n tra tio n s w e re P C B -1 1 8 at 6 - 9 n g /N m 3, 19 fo llo w e d b y 105 at 2 - 4 n g /N m 3, a n d 77 at 2 - 3 n g /N m 3, w ith o th ers d e te c te d at b e lo w 2 n g /N m 3. 20 On a TEQ basis, including CD D /C D Fs and dioxin-like PCB s (the authors calculated C D D /CD F This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-19 DRAFT: DO N O T CITE OR QUO TE 1 u s in g I-T E F s w h ile d io x in -lik e P C B T E Q w a s c a lc u la te d u sin g W H O 98 T E F s), th e P C B s 2 contributed less than 10% o f the total TEQ concentration, w hich averaged betw een 0.6 and 3 1.6 ng total T E Q /N m . T he m ass em issions o f total T E Q from th e th ree plants, calculated based 4 on em ission concentrations in conjunction w ith m ass loadings, totaled 8.7, 9.2, and 5 10.9 g T E Q /year over the three plants. 6 K im et al. (2004a) reported on the testing o f eight incinerators including tw o sintering 7 furnaces and four sm elting furnaces fo r C D D /C D F s, PC B s, and H C B . The average over all 8 eig h t in c in e ra to rs, o n a W H O 98 T E Q b a sis, w a s 0.281 n g /N m 3 fo r C D D /C D F s a n d 0.023 n g /N m 3 9 for P C B s, suggesting a factor o f 10 difference on average. The alum inum nonferrous m etal 10 s m e lte r sh o w e d a P C B T E Q c o n c e n tra tio n at 0 .0 1 6 n g W H O 98 T E Q P/N m 3, w h ic h w a s o n ly 11 o n e -h a lf th a t o f C D D /C D F T E Q , n o t th e o rd e r o f m a g n itu d e su g g e ste d b y a v e ra g in g all 12 eig h t facilities. T he co p p er sm elter had th e sam e T E Q co n cen tratio n fo r b o th P C B s and 13 C D D /C D F s: 0 .0 0 2 n g W H O 98 T E Q P/N m 3. T h e m o st in fo rm a tiv e tests, p e rh a p s, w e re th e 14 tw o iron ferro u s m etal sm elters, w h ere C D D /C D F o v erw h elm ed P C B em issions. T he C D D /C D F 15 e m issio n c o n c e n tra tio n s w e re 1.492 a n d 0 .9 2 6 n g W H O 98 T E Q DF/N m , w h ile th e P C B e m issio n 16 c o n c e n tra tio n s w e re 0 .1 1 2 a n d 0 .0 6 7 n g W H O 98 T E Q P/N m , re sp e c tiv e ly . 17 B ro d sk y et al. (2003) rep o rted on m easu rem en ts from six co m b u stio n sources in R ussia, 18 in clu d in g a n o n ferro u s m etallu rg y plant, a ce m e n t plant, an alu m in u m p lan t in th e calcin atio n 19 furnace, and an alum inum p lan t in th e entry into th e electro static filter. N u m ero u s individual 20 congener concentrations in the stack gas em issions w ere provided including som e dioxin-like 21 P C B s, although no TEQ estim ates w ere provided and no congener-specific em ission factors w ere 22 provided. C oncentrations w ere provided for PC B -105, PCB -118, PCB -123, PCB -156, PCB-157, 23 PC B -170, and PC B -180. The TEQ concentration in these four facilities ranged from 0.001 to 24 0 .0 0 6 n g W H O 98 T E Q P/N m 3. B ro d sk y et al. (2 0 0 3 ) p ro v id e d a to ta l c o n c e n tra tio n (su m o f all 25 congeners) and an em ission factor o f total PC B s in pg/M T. 26 F ish er et al. (2004) reported on tests for an experim ental sinter box apparatus, w hich is 27 essentially a sm all pilot plant. A raw m ix o f typical iron ore feed-- including iron ore fines, 28 fluxes, fuel in the form o f coke, and som e recycled m aterials-- w as com bined w ith five different 29 am ounts o f potassium chloride to test the effect o f chloride on C D D /C D F and dioxin-like PCB 30 em issions. A correlation w as found for both C D D /C D F and dioxin-like PCB em issions w ith 31 chloride content. A t a ch lo rid e co n cen tratio n in th e entire feed o f 250 m g /k g and less, w h ich This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-20 DRAFT: DO N O T CITE OR QUO TE 1 encom passed a baseline run and a run at 250 m g/kg chloride, CD D /C D F em issions w ere fairly 2 steady, suggesting chloride did not affect em issions at concentrations in this range, but at higher 3 concentrations w ith up to about 800 m g/kg chloride added, the effect w as second order. For 4 PCBs, the effect w as m ore linear-- a linear rise in PCB em issions w as noted w ith increasing 5 chloride content. PCD F concentrations dom inated CD D /CD F, and on a TEQ basis, CD D /CD F 6 dom inated over PCB s. Specifically, the ratio o f PCB to CD D /C D F TEQ concentrations w as in 7 the range o f 0.07 for the five tests. O n a TEQ basis, PC B -126 contributed 9 0 -9 5 % o f total PCB 8 TEQ, but PCB -105 and PC B -118 contributed the m ost on a straight concentration basis. The 9 authors concluded that at typical chloride concentrations o f 5 0-100 m g/kg in the industry, the 10 to ta l C D D /C D F /P C B c o n c e n tra tio n s are e x p e c te d to b e b e lo w 1.5 n g T E Q /N m 3. 11 F ra n c o is et al. (2 0 0 4 ) m e a su re d e m issio n s at 15 fa c ilitie s, in c lu d in g tw o m etal sm elters 12 and an iro n ore sintering plant. F o r m o st facilities, th eir sam pling in d icated th at the T E Q 13 e m issio n s o f d io x in -lik e P C B s n e a rly m a tc h e d th a t o f d io x in s. W ith th e iro n o re sin te rin g p lan t, 14 how ever, th e d io x in -lik e P C B s w ere an o rd er o f m ag n itu d e less th an dioxins: 15 0 .0 5 8 n g W H O 98 T E Q P/N m 3 v e rsu s 0.65 n g W H O 98 T E Q DF/N m 3. F o r th e a lu m in u m a n d c o p p e r 16 sm elters, P C B e m issio n s w e re a fa c to r o f 2 (a t 0 .0 4 6 n g W H O 98 T E Q P/N m ) a n d a fa c to r o f 4 (at 17 0 .0 1 7 n g W H O 98 T E Q P/N m 3) le ss th a n d io x in T E Q , re sp e c tiv e ly . T h e y c a lc u la te d to ta l an n u al 18 T E Q em issio n s fo r th ese p lan ts and estim ated d io x in -lik e P C B em issio n s to b e 2.3 and 19 18.8 m g W H O 98 T E Q P/y e a r fo r th e a lu m in u m a n d c o p p e r sm elters, re sp e c tiv e ly , a n d to b e m u c h 20 higher at 474 m g WHO98 TEQP/year for the iron ore sintering plant. 21 A s described above, several studies outside o f the U nited States have m easured 22 dioxin-like PC B s along w ith CD D /C D Fs from a variety o f m etal processing facilities including 23 ferrous and nonferrous sm elters, iron ore sintering facilities, and other com bustion units w ithin 24 the m etal refining industry. These studies did not report em ission factors but the concentration 25 data consistently suggest that em issions from iron ore sintering plants are about an order o f 26 m agnitude or m ore low er than C D D /CD Fs, on a TEQ basis. A ccordingly, for the purposes o f a 27 prelim inary estim ate, the PC B em ission factor is assum ed to be 10% o f the CD D /C D F em ission 28 factor. The activity levels (from C hapter 7) and release estim ates are show n below . The studies 29 also indicate that PCB em issions are occurring from copper and alum inum sm elting operations, 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-21 DRAFT: DO NOT CITE OR QUOTE 1 but the results are not consistent and not easily converted to TEQ em ission factors. Thus, 2 quantitative estim ates could not be m ade for these facilities. 3 The inventory decision criteria and releases to all m edia are sum m arized below : 4 Inventory Decision Criteria for Iron Ore Sinter Production Air W ater Solids Products Em ission tests for at least tw o units/source types w ith No sufficient docum entation to directly derive em ission factors. M easured em ission factors consistent or have understandable differences. Em ission factor tests represent units that are typical o f the class. A ctivity estim ates based on source-specific surveys. Yes C onclusion (Q = Q uantitative, P = Prelim inary). P 5 6 ______________________________________________________________________________________________ Iron Ore Sinter Production________________________ Air Releases______________________________ Emission Factors Wet Scrubber 1 9 8 7 -- 0 .0 6 n g W H O 98 T E Q p /k g o f s in te r (P re lim in ary ). 1 9 9 5 -- 0 .0 6 n g W H O 98 T E Q P/k g o f s in te r (P re lim in ary ). 2 0 0 0 -- 0 .0 6 n g W H O 98 T E Q P/k g o f s in te r (P re lim in ary ). F abric F ilter 1 9 8 7 -- 0.5 n g W H O 98 T E Q P/k g o f s in te r (P re lim in ary ). 1 9 9 5 -- 0.5 n g W H O 98 T E Q P/k g o f s in te r (P re lim in ary ). ____ 2 0 0 0 -- 0.5 n g W H O 98 T E Q P/k g o f s in te r (P re lim in ary ).___________________________ Activity Levelsa 1987-- 14.5 M M T. 1995-- 12.4 M M T. 2 0 0 0 -- 10.6 M M T .____________________________________________________________________ Releases 1 9 8 7 -- 4 g W H O 98 T E Q P(P re lim in ary ). 1 9 9 5 -- 3 g W H O 98 T E Q P(P re lim in ary ). 2 0 0 0 -- 3 g W H O 98 T E Q P (P re lim in ary ). 7 8 aFifty-nine percent of sinter production was at facilities with wet scrubbers, and 41% was at facilities with fabric 9 filters. 10 11 12 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-22 DRAFT: DO NOT CITE OR QUOTE 1 Copper and Aluminum Smelting Air Releases________ N o t q u an tifiab le.__________________________________________________ 2 3 4 10.6. NATURAL SOURCES (ORIGINALLY SECTION 10.5) 5 A s discussed in E PA (2006), there is no clear evidence that releases o f dioxin-like PC B s 6 occur from natural sources. No changes w ere m ade to this conclusion. 7 8 10.6.1. Biotransformation of Other PCBs 9 As discussed in the original report, studies have shown that under anaerobic conditions, 10 b io lo g ically m ed iated red u ctiv e d ech lo rin atio n to lo w er-ch lo rin ated congeners, fo llo w ed b y slow 11 a n a e ro b ic a n d /o r a e ro b ic b io d e g ra d a tio n , is a m a jo r p a th w a y f o r d e stru c tio n o f P C B s in th e 12 environm ent. T his research in d icates th at b io d eg rad atio n should resu lt in a n et decrease rath er 13 th a n a n e t in c re a se in th e e n v iro n m e n ta l lo a d o f d io x in -lik e P C B s. 14 15 10.6.2. Photochemical Transformation of Other PCBs 16 P h o to ly sis and p h o to -o x id atio n m ay b e m ajo r p ath w ay s fo r d estru ctio n o f P C B s in the 17 environm ent. R esearch rep o rted to date and su m m arized in th e original rep o rt in d icates th at 18 o rth o -su b stitu te d ch lo rin es are m o re su scep tib le to p h o to ly sis th an are m eta- and p ara-su b stitu te d 19 congeners; thus, p h o to ly tic fo rm atio n o f m ore to x ic d io x in -lik e P C B s m ay occur. O x id atio n by 20 hydroxyl radicals, how ever, apparently occurs preferentially at the m eta and para positions, 21 resulting in a net decrease rather than a net increase in the environm ental load of dioxin-like 22 PCBs. 23 24 10.7. PAST USE OF COMMERCIAL PCBS (ORIGINALLY SECTION 10.6) 25 This section provides background inform ation about the am ount o f PC B s used in the past 26 and does not discuss release estim ates for the reference years. No changes w ere m ade to this 27 section. A s discussed in the original report, an estim ated 568,000 M T o f P C B s w ere sold in the 28 U nited States betw een 1930 and 1975. The environm ental releases associated w ith production, 29 u se, a n d d isp o sa l d u rin g th is tim e p e rio d w e re e stim a te d as 3 ,7 0 2 k g W H O 98 T E Q P. 30 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-23 DRAFT: DO NOT CITE OR QUOTE 1/7/2013 Table 10-1. Summary of PCB releases for reference years 1987, 1995, and 2000 (g WHO98 TEQp/year) This document is a draftfor review purposes only and does not constitute Agency policy. 10-24 Air releases Land releases Source Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Releases from commercial PCB products PCB incineration x Releases from in-service PCBs x x Chemical manufacturing and processing sources Municipal wastewater treatment 1987 1995 2000 51 78 19 Combustion sources Municipal waste combustors 1987 1995 2000 7 15 15 Industrial wood combustion x Medical waste incineration 1987 1995 2000 97 18 14 Tire combustion x Water releases Q. Inv. Prelim. NQ x x Product releases Q. Inv. Prelim. NQ 2 12 3 DRAFT: DO N O T CITE OR QUOTE 1/7/2013 Table 10 1. Summary of PCB releases for reference years 1987, 1995, and 2000 (g WHO98 TEQP/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. 10-25 Source Cigarette smoking 1987 1995 2000 Sewage sludge incineration 1987 1995 2000 Backyard barrel burning 1987 1995 2000 Petroleum-refining catalyst regeneration Hazardous waste incineration Power plants Forest fires 1987 1995 2000 Air releases Land releases Water releases Product releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ <0.1 <0.1 <0.1 0.4 1 0.7 41 43 34 12 11 49 1 1 0.8 x x x x DRAFT: DO N O T CITE O R QUO TE 1/7/2013 Table 10 1. Summary of PCB releases for reference years 1987, 1995, and 2000 (g WHO98 TEQP/year) (continued) This document is a draftfor review purposes only and does not constitute Agency policy. Source Metal refining Iron ore sintering 1987 1995 2000 Copper smelting Aluminum smelting Total 1987 1995 2000 Air releases Land releases Water releases Product releases Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ Q. Inv. Prelim. NQ 4 3 3 41 120 43 48 34 82 x x 52 79 20 2 12 3 10-26 DRAFT: DO NOT CITE OR QUOTE x = Releases are possible during this year, but the data are insufficient to develop estimates. Q. Inv. = Quantitative Inventory. Prelim. = Preliminary. NQ = Not quantified. 1 Table 10-2. PCB analysis for composite ash samples from barrel burning 2 Congener IUPAC number Emission factors (pg/kg) Recycler Nonrecycler Average 3,3',4,4'-TCB 77 1.2 1 1.1 3,4,4',5-TCB 81 2,3,3',4,4'-PeCB 105 3.4 3.5 3.5 2,3,4,4',5-PeCB 114 2,3',4,4',5-PeCB 118 2',3,4,4',5-PeCB 123 3,3',4,4',5-PeCB 126 2,3,3',4,4',5-HxCB 156 0.7 <0.5 0.5 2,3,3',4,4',5'-HxCB 157 2,3',4,4',5,5'-HxCB 167 3,3',4,4',5,5'-HxCB 169 2,3,3',4,4',5,5'-HpCB 189 0.6 <0.5 0.4 Total WHO98 TEQp 0.0009 0.0006 0.0008 --J 0 \ U l 4 ^ U> Averages and TEQs calculated assuming half the values for entries shown as less than. IUPAC = International Union of Pure and Applied Chemistry. Source: Lemieux (1997). This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 10-27 DRAFT: DO NOT CITE OR QUOTE 1 11. RESERVOIR SOURCES OF CDD/CDFS AND DIOXIN-LIKE PCBS 2 3 4 This introduction has been expanded to m ore clearly define reservoirs. C hapters 2 5 through 10 o f this docum ent discuss sources w ith the potential for initial releases o f dioxin-like 6 com pounds to the environm ent in the U nited States. This chapter addresses releases from 7 reservoirs that are defined as m aterials or places that contain previously released C D D /C D Fs or 8 dioxin-like PC B s and have the potential for redistributing these com pounds into the environm ent. 9 Potential reservoirs include soils, sedim ents, biota, w ater, and som e products. Products that 10 contain C D D /C D F s can b e co n sid ered reserv o irs w h en th ey h av e th e potential fo r releases after 11 th e ir in itia l u se. T h e a tm o sp h e re co u ld b e c o n sid e re d a re s e rv o ir b u t is e x c lu d e d h e re b e c a u s e it 12 is th e prim ary m ed iu m fo r tran sp o rtin g and d istrib u tin g C D D s and C D F s o v er larg e g eographical 13 areas. T h u s, it is c o n sid e re d a te m p o ra ry h o ld in g p la c e ra th e r th a n a lo n g -te rm re serv o ir. 14 A lth o u g h w a te r is also an im p o rtan t tran sp o rt m edium , th e resid en ce tim es can b e long, and, 15 th e re fo re , it is a p p ro p ria te ly c o n sid e re d a re serv o ir. 16 T he d efinition o f reserv o irs as u sed in th is d o cu m en t also ex clu d es C D D /C D F s contained 17 in natural ball clay deposits. T he C D D /C D F s co n tain ed in ball clay w ere fo rm ed by g eo ch em ical 18 p ro cesses th a t are th o u g h t to h av e o ccu rred m illio n s o f y ears ago. A n y re le ase fro m b all clay 19 w o u ld b e an initial release to th e co n tem p o rary environm ent, and, therefo re, ball clay is not 20 considered to be a reservoir. Potential ball clay releases are covered in C hapter 9 on N atural 21 Sources. 22 Soils in som e locations could have elevated C D D /C D F levels due to past activities such 23 as pesticide use, spills, illegal disposal, or fires. T hese areas w ould be considered part o f the soil 24 reservoir and w ould have the potential for greater release rates than norm al soils w ith background 25 C D D /C D F levels. The soil-release estim ates presented in this docum ent do not include releases 26 from these "hot spots" due to lack o f appropriate inform ation. H ow ever, they could be im portant 27 events on a local scale and should be considered w here feasible. 28 D ioxin-like com pounds are sequestered by a reservoir only until physical processes 29 cause these contam inants to becom e released into the open environm ent over a defined tim e and 30 space. W hen this occurs, reservoirs becom e sources o f dioxin-like com pounds in the circulating 31 environm ent. F ig u re 11-1 p resen ts a conceptual diagram o f flu x and ex ch an g e o f d io x in -lik e 32 com pounds to m ultiple environm ental com partm ents such as soils, w ater, air, sedim ents, and This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11-1 DRAFT: DO N O T CITE OR QUO TE 1 biota. This dynamic system consists of fluxes in and out of the atmosphere as well as other 2 exchanges between reservoirs and the atmosphere (recall that the atmosphere is not defined here 3 as an environmental reservoir, rather as a transport medium for dioxin-like compounds). 4 Movement of dioxin-like compounds between media can be induced by the physical processes of 5 volatilization, wet and dry atmospheric particle and vapor deposition, adsorption, erosion and 6 runoff, resuspension of soils into air, and resuspension of sediments into water. 7 This chapter describes the major reservoir sources of CDD/CDFs and PCBs, including, to 8 the extent feasible, estimates of the potential mass of CDD/CDFs and PCBs in each reservoir, the 9 chemical/physical mechanisms responsible for releases of these compounds, and estimates of 10 potential annual releases from each reservoir. 11 12 11.1. SOIL RESERVOIRS (ORIGINALLY SECTION 11.2.1) 13 This section provides revised estimates of the amounts of CDD/CDFs in soil reservoirs. 14 Harrad and Jones (1992) and Duarte-Davidson et al. (1997) estimated the CDD/CDF 15 content of soils in the United Kingdom by multiplying the soil surface area by the contamination 16 depth, soil density, and CDD/CDF concentration in the soil. A similar approach was used here 17 to estimate the amount CDD/CDFs in surface soils of the United States. The following inputs 18 were used in these calculations: 19 20 Surface soils were divided into rural and urban areas to reflect differences in the 21 CDD/CDF levels. Urban areas were assumed to have an average concentration of 22 10 pg WHO TEQDF/g, and rural soils, 2 pg WHO TEQDF/g (U.S. EPA, 2007b). 23 The urban land area in the United States is 1.82 million km based on Census Bureau 24 statistics for metropolitan areas (USDA, 2002). The portion of urban areas covered by 25 impervious surfaces (rather than soil) varies widely. For the purposes of a preliminary 26 estimate, it was assumed that an average of 50% of the metropolitan land area had soil 27 coverage. The land area of nonmetropolitan areas in the United States is 28 7.28 million km2(USDA, 2002). 29 The soil density was assumed to be 2.6 g/cm (Brady, 1984). 30 The contamination depth was assumed to be 10 cm (U.S. EPA, 2007b). 31 32 Based on these assumptions, the amount of CDD/CDFs in U.S. surface soils was estimated as 33 2,370 kg WHO TEQdf in urban soils and 3,790 kg WHO TEQDFin rural soils, for a total of This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 2 DRAFT: DO NOT CITE OR QUOTE 1 6 ,1 5 0 k g W H O TEQdf. E P A (2 0 0 7 b ) fo u n d th a t a v e ra g e P C B T E Q s w e re a b o u t 4 % o f av e ra g e 2 total D /F/P TEQ s in rural soils. A ssum ing this percentage applies to urban areas as w ell, this 3 w o u ld im p ly th a t th e soil re se rv o ir c o n ta in s a b o u t 95 k g W H O T E Q P. T h e se c a lc u la tio n s are n o t 4 definitive and only indicate approxim ate am ounts o f dioxins that m ay be contained in U.S. 5 surface soils. 6 Soils in som e locations could have elevated C D D /C D F levels (or "hot spots") due to 7 uncontrolled activities such as spills, illegal disposal, or fires. E levated soil levels could also 8 occur in areas w here 2,4-D and 2,4,5-T w ere used and areas w ith land-applied sludges/ash. 9 These areas w ould be considered part of the soil reservoir and w ould have the potential for 10 g re a te r re le a se ra te s th a n n o rm a l so ils w ith b a c k g ro u n d C D D /C D F lev els. T h e a m o u n ts in 11 la n d fills co u ld also b e c o n sid e re d p a rt o f th e soil re se rv o ir, a lth o u g h th e p o te n tia l fo r re le a se is 12 m u c h less. N o e stim a te s co u ld b e m a d e fo r th e a d d itio n a l C D D /C D F soil b u rd e n s d u e to th e 13 u n c o n tro lle d a c tiv ities, b u t e stim a te s w e re m a d e fo r th e o th e r a c tiv itie s as d isc u sse d b elo w . 14 E stim ates can be m ad e fo r the total m ass o f C D D /C D F T E Q s th at hav e b een applied to 15 soil fro m p a s t u s e o f th e p e stic id e s 2 ,4 -d ic h lo ro p h e n o x y a c e tic ac id (2 ,4 -D ) an d 16 2 ,4 ,5 -tric h lo ro p h e n o x y a c e tic ac id (2 ,4 ,5 -T ). A s d isc u sse d in C h a p te r 11 o f th e o rig in al re p o rt, 17 the total am ounts o f C D D /C D F released to the en v iro n m en t are as fo llo w s: 18 19 F ro m 2,4-D u se durin g th e perio d o f 1975 to 1995, th e total release w as estim ated as 20 0.55 k g W H O 98 TEQdf (0.35 k g I-TEQdf). 21 F ro m 2 ,4 ,5 -T u se o v e r th e p e rio d o f 1950 to 1979, th e to ta l re le a se w a s e s tim a te d as 22 36 k g o f 2 ,3 ,7 ,8 -T C D D . 23 24 The am ounts of C D D /C D Fs in landfills can also be considered a soil reservoir w ith the 25 potential for releases in the future. The earlier chapters provided estim ates o f the am ounts o f 26 C D D /C D Fs landfilled for m any sources. A s show n in Table 11-1, the total am ounts landfilled 27 w ere estim ated as 3,750 g TEQ in 1987, 1,050 g TEQ in 1995, and 1,310 g TEQ in 2000. If it is 28 assum ed that m ost landfills operate for 30 years and the average annual input equals the average 29 over the reference years (2,040 g TEQ), then the cum ulative sum w ould be 61,000 g TEQ. This 30 should be regarded as a prelim inary estim ate because it is based on num erous assum ptions and 31 lim ited data. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 3 DRAFT: DO NOT CITE OR QUOTE 1 A variety o f w aste types containing C D D /C D Fs are land applied such as sew age sludge, 2 w ood pulp sludge, residential w ood burning ash, and beneficial uses o f cem ent kiln clinker. 3 T hese sources also contribute to the soil reservoir. A s show n in T able 1-9, these sum to 4 2,400 g TEQ in 1987, 2,500 g TEQ in 1995, and 2,300 g TEQ in 2000. If it is assum ed that 5 operations persist for 30 years and the average annual input equals the average over the reference 6 years (2,400 g TEQ), then the cum ulative sum w ould be 72,000 g TEQ. This should be regarded 7 as a prelim inary estim ate because it is based on num erous assum ptions and lim ited data. 8 In sum m ary, the total m ass o f C D D /C D F that is contained in the soil reservoir is 9 a p p ro x im a te ly 6 ,1 5 0 k g W H O 98 T E Q w ith p e rh a p s an ad d itio n a l 170 k g T E Q fro m p a st 10 additions (landfills - 61 kg T E Q , p esticid e u se - 37 kg T E Q and lan d -ap p lied slu d g es/ash - 72 kg 11 T E Q ). A s d isc u sse d b e lo w , v a rio u s fo rm s o f d e g ra d a tio n /re m o v a l can o c c u r in soil, w h ic h 12 w o u ld red u ce th ese co n trib u tio n s from th e past, m ak in g it u n certain h o w m u ch o f th ese rem ain in 13 th e soil re s e rv o ir to d ay . 14 15 11.1.1. Mechanisms Responsible for Releases from Surface Soils 16 A s d iscu ssed in th e original report, a n u m b er o f studies have d em o n strated th at soil 17 releases can o ccu r v ia erosion, degradation, v o latilizatio n , and p article resuspension. 18 11.1.2. Estimated Annual Releases from Soil to Water 19 N o n p o in t sources o f C D D /C D F s to w aterw ay s in clu d e sto rm w ater ru n o ff from u rb an 20 areas and soil erosion in rural areas during storm s. A pproaches for estim ating national loadings 21 to w ater fo r both o f these sources are described below . 22 23 11.1.2.1. U rban R u n o f f 24 N o changes w ere m ade in this update. As discussed in the original report, a w ide range 25 o f CD D /C D F concentrations w ere m easured in urban runoff at 23 sites in C alifornia (M athur 26 et al., 1997; F isher et al., 1999). The m idpoint o f the 4 order o f m agnitude range w as selected. 27 B ased on the w ide range o f results and uncertainty about the representativeness o f the sam ples, 28 this factor is considered prelim inary. The run-off volum e w as calculated based on rainfall data 29 and urban area data. All factors and release estim ates are presented in the release sum m ary 30 below. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 4 DRAFT: DO NOT CITE OR QUOTE 1 2 11.1.2.2. R u r a l S o il E ro sio n 3 The original report also presented estimates for CDD/CDF releases from rural soils. No 4 changes were made to the activity estimates, but updates were made to the emission factors as 5 discussed below. 6 The data summarized in EPA (2007b) suggest that the typical concentration of 7 CDD/CDFs in soils in rural areas is about 1.7 ng WHO98 TEQDF/kg based on samples from 8 27 locations. Similarly, EPA (2007b) suggests that the typical concentration of PCBs in soils in 9 rural areas is about 0.07 ng WHO98 TEQP/kg. These values were assumed to apply to all 10 three reference years. It is not known how well these estimates represent eroded soil from 11 cropland and rangeland and were given a preliminary confidence rating. Multiplying the 12 emission factor and activities, yields CDD/CDF release estimates of 4,900, 4,400 and 13 4,200 g WHO98 TEQdf for 1987, 1995, and 2000, respectively. Similarly, the PCB release 14 estimates were calculated as 200, 180, and 170 g WHO98 TEQPfor 1987, 1995, and 2000, 15 respectively. These release estimates have preliminary confidence ratings because the emission 16 factor has a preliminary rating. 17 18 11.1.3. Estimated Annual Releases from Soil to Air 19 As discussed in the original report, a number of investigators have studied releases from 20 soil to air, but no quantitative estimates of the mass of dioxin-like compounds that may be 21 released to the atmosphere annually from U.S. soils have been published in the literature and 22 none were developed for this report. Particulate dioxin concentrations were compared with 23 average total particulate dioxin levels to arrive at the conclusion that soil reentrainment could 24 account for only 1 to 4% of the particulate dioxins in the atmosphere in urban areas and 0.1 to 25 0.3% of those in rural regions (Kao and Venkataraman, 1995). 26 The inventory decision criteria and releases to all media are summarized below: 27 28 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11-5 DRAFT: DO NOT CITE OR QUOTE Inventory Decision Criteria for Soil Reservoirs Air Water Em ission tests for at least tw o units/source types w ith Yes sufficient docum entation to directly derive em ission factors. Solids Products M easured em ission factors consistent or have understandable differences. No Em ission factor tests represent units that are typical of the class. No A ctivity estim ates based on source-specific surveys. C onclusion (Q = Q uantitative, P = Prelim inary). 1 2 Yes P This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 6 DRAFT: DO NOT CITE OR QUOTE Soil Reservoirs Releases to Air N o t q u an tifiab le._______________________________________________________________________________ Releases to Urban Water__________________________ Emission Factors 1 9 8 7 -- 1 p g W H O 98 T E Q df/L (1 p g I-T E Q df/L ) (P re lim in ary ). 1 9 9 5 -- 1 p g W H O 98 T E Q df/L ( l p g I-T E Q df/ l ) (P re lim in ary ). 2 0 0 0 -- 1 p g W H O 98 T E Q df/L (1 p g I-T E Q df/L ) (P re lim in ary ). Activity Levels 1 9 8 7 -- 1.24 x 1 0 14 L /yr. 1 9 9 5 -- 1.33 x 1 0 14 L /yr. 2 0 0 0 -- 1.42 x 1 0 14 L /yr. Releases 1 9 8 7 -- 120 g (W H O 98 T E Q df o r I-T E Q df) (P re lim in a ry ). 1 9 9 5 -- 130 g (W H O 98 T E Q df o r I-T E Q df) (P re lim in a ry ). 2 0 0 0 -- 140 g (W H O 98 T E Q df o r I-T E Q df) (P re lim in a ry ). Release to Rural W ater___________________________ Emission Factors 1 9 8 7 -- 1.7 n g W H O 98 T E Q DF/k g (P re lim in a ry ) a n d 0 .0 7 n g W H O 98 T E Q P/k g (P re lim in ary ). 1 9 9 5 -- 1.7 n g W H O 98 T E Q DF/k g (P re lim in a ry ) a n d 0 .0 7 n g W H O 98 T E Q P/k g (P re lim in ary ). 2 0 0 0 -- 1.7 n g W H O 98 T E Q DF/k g (P re lim in a ry ) a n d 0 .0 7 n g W H O 98 T E Q P/k g (P re lim in ary ). Activity Levels 1987-- 2.91 billion M T o f soil. 1995-- 2.62 billion M T o f soil. 2000-- 2.46 billion M T o f soil. Releases 1 9 8 7 -- 4 ,9 0 0 g W H O 98 T E Q df(P re lim in a ry ) a n d 2 0 0 g W H O 98 T E Q p (P re lim in ary ). 1 9 9 5 -- 4 ,5 0 0 g W H O 98 T E Q df(P re lim in a ry ) a n d 180 g W H O 98 T E Q p (P re lim in ary ). 2 0 0 0 -- 4 ,2 0 0 g W H O 98 T E Q df(P re lim in a ry ) a n d 170 g W H O 98 T E Q p (P re lim in ary ). 1 2 3 11.2. WATER RESERVOIRS (ORIGINALLY SECTION 11.2.2) 4 As discussed in the original report, w ater reservoirs have the potential for releases to air 5 or sedim ent, but no quantifiable estim ates could be made. 6 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 7 DRAFT: DO NOT CITE OR QUOTE 1 _______________________________ W ater Reservoirs ________________________________ Releases to Air N o t q u an tifiab le.___________________________________________ _____________________________ Releases to Sediment N o t q u an tifiab le.___________________________________________ 2 3 4 11.3. SEDIMENT RESERVOIRS (ORIGINALLY SECTION 11.2.3) 5 The original report used assumptions about the water surface area, sediment depth, and 6 background TEQ concentration for U.S. sediments to estimate that at least 7 120 kg WHO98 TEQdf (120 kg I-TEQDF) are present in the sediment reservoir. 8 9 11.3.1. Mechanisms Responsible for Supply to and Releases from Sediment 10 The original report identified atmospheric deposition of CDDs and CDFs as an important 11 mechanism for CDD/CDFs to enter sediments and those sediments are a likely sink for these 12 compounds because they are strongly bound to organic particles in the sediment. 13 14 11.3.2. Releases from Sediment to W ater 15 As discussed in the original report, studies have attempted to evaluate the transfers from 16 sediment to water to air, but the information needed to estimate this release nationally is lacking. 17 For this reason, no quantitative estimates can be made for annual releases from sediment 18 reservoirs to water. 19 ______________________________Sediment Reservoirs _______________________________Releases to W ater N o t q u an tifiab le.___________________________________________ 20 21 22 11.4. BIOTA RESERVOIRS (ORIGINALLY SECTION 11.2.4) 23 C D D /C D F s are fo u n d in all ty p e s o f b io ta in c lu d in g v e g e ta tiv e m a tte r a n d a n im a l tissu e s. 24 N o stu d ie s w e re fo u n d th a t e stim a te d th e m a ss o f C D D /C D F s in b io ta in th e U n ite d S ta tes. 25 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 8 DRAFT: DO NOT CITE OR QUOTE 1 11.4.1. Mechanisms Responsible for Supply to and Releases from Biota 2 The original report identified vapor absorption and desorption as an im portant 3 m echanism for plants and ingestion/bioaccum ulation as an im portant m echanism for anim als. 4 5 11.4.2. Approaches for Measuring and Estimating Releases from Biota 6 The original report describes a num ber o f studies that evaluate the CD D /C D F releases 7 from biota to soil and air, but insufficient inform ation is available to m ake quantitative estim ates 8 for national releases. 9 _______________________________ Biota Reservoirs ________________________________ Releases to Air N o t q u an tifiab le.________________________________________ ________________________________ Releases to Soil N o t q u an tifiab le.________________________________________ 10 11 12 11.5. PRODUCT RESERVOIRS 13 T h is is a n e w section. A s d isc u sse d in C h a p te r 8, a n u m b e r o f c h e m ic al p ro d u c ts c o n ta in 14 C D D /C D F s. Som e o f th ese can b e co n sid ered reserv o irs b ecau se th ey h av e th e potential fo r 15 C D D /C D F re le a se s a fte r th e ir in itia l u se. O th ers are u se d in a m a n n e r su ch th a t a n y re le a se s 16 w o u ld occur du rin g th eir initial use, and therefore, th ey are not con sid ered a reserv o ir fo r future 17 releases. F o r exam ple, 2,4-D is a pesticid e th at is applied to fo liag e and w o u ld have an 18 im m e d ia te re le ase to b io ta an d soil. A lth o u g h it m ay p e rsist in th e en v iro n m e n t after ap plication, 19 it w o u ld b eco m e p art o f th e b io ta or soil reserv o ir rath er th an a separate p ro d u ct reservoir. 20 Sim ilarly, chlorobenzenes are used as pesticides or chem ical interm ediates for pesticides and, 21 therefore, are not considered product reservoirs. The products that m ay represent potential 22 reservoirs are discussed below. 23 24 11.5.1. Bleached Chemical Wood Pulp 25 The prim ary discussion of potential dioxin releases from the bleached chem ical w ood 26 pulp and paper industry is presented in Section 8.1. M any products m ade from bleached 27 chem ical w ood pulp rem ain in use long after their production and, therefore, represent a potential 28 reservoir. The lim ited data available on the dioxin concentrations in these products indicate This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 1 1 - 9 DRAFT: DO NOT CITE OR QUOTE 1 decreasing levels over tim e, but the data are insufficient to m ake a reliable estim ate o f the 2 cum ulative am ounts. A s reported in Section 8.1, w ood pulp is estim ated to have contained 3 50 0 g W H O 98 T E Q in 1987, 4 0 g W H O 98 T E Q in 1995, a n d 0 .6 g W H O 98 T E Q in 2 0 0 0 . T h e 4 total reservoir o f C D D /C D Fs in these products w ould be the cum ulative am ount o f these 5 products rem aining in use m inus any degradation or releases that have occurred. Insufficient 6 inform ation is available to estim ate the size o f the total reservoir or the possible releases. 7 8 11.5.2. Chlorophenols 9 The prim ary discussion o f potential dioxin releases from chlorophenol production is 10 p resen ted in S ection 8.4. T he lo w er-ch lo rin ated p h en o ls have b een u sed prim arily as chem ical 11 in te rm e d ia te s in th e m a n u fa c tu re o f o th e r p e stic id e s. P e stic id e s are ty p ic a lly u s e d th e sam e y e a r 12 as th ey are p ro d u ced and, therefore, are not a reserv o ir fo r fu tu re releases. T he 13 h ig h e r-c h lo rin a te d p h e n o ls (te tra c h lo ro p h e n o l a n d P C P ) a n d th e ir so d iu m salts h a v e b e e n u s e d 14 prim arily fo r w o o d p reservation. W o o d pro d u cts treated w ith th ese chem icals have lo n g service 15 liv e s a n d re p re se n t a p o te n tia l re serv o ir. A s d isc u sse d in C h a p te r 8, an e stim a te o f a v e ra g e 16 annual d o m estic P C P co n su m p tio n during th e p erio d o f 1970 to 1995 is ab o u t 40 0 ,0 0 0 M T . A s 17 re p o rte d in S ectio n 8.4, P C P is e s tim a te d to h a v e c o n ta in e d 2 0 ,0 0 0 g W H O 98 T E Q in 1987, 18 4 ,8 0 0 g W H O T E Q in 1995, a n d 4 ,2 0 0 g W H O 98 T E Q in 2 0 0 0 . T h e lim ite d d a ta a v a ila b le o n th e 19 dioxin co n cen tratio n s in th ese pro d u cts in d icate d ecreasin g levels o v er tim e, b u t th e data are 20 insufficient to m ake a reliable estim ate o f the cum ulative am ounts. It is unknow n how m uch o f 21 the C D D /C D Fs degrade in situ or escapes from the w ood into the environm ent. Several recent 22 field studies, as discussed in C hapter 8, dem onstrate th at C D D /C D F s do apparently leach into 23 soil from P C P-treated w ood, but the studies do not provide release-rate data. N o studies w ere 24 located that provide any m easured CD D /C D F volatilization rates from PC P-treated wood. 25 A lthough C D D /C D Fs have very low vapor pressures, they are not bound to, nor do they react 26 w ith, the w ood in any w ay that w ould preclude volatilization. Several studies (see C hapter 8) 27 have attem pted to estim ate potential CD D /C D F volatilization releases using conservative 28 assum ptions or m odeling approaches, but these estim ates span m any orders o f m agnitude. 29 Insufficient inform ation is available to estim ate the size o f the total reservoir or the possible 30 releases. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11-10 DRAFT: DO NOT CITE OR QUOTE 1 11.5.3. Vinyl Chloride Products 2 The prim ary discussion o f potential dioxin releases from vinyl chloride production is 3 presented in Section 8.3. M any vinyl chloride products rem ain in use long after th eir production 4 and, therefore, represent a potential reservoir. Lim ited data are available on the dioxin 5 concentrations in these products, but the data are insufficient to m ake a reliable estim ate o f the 6 cum ulative am ounts. A s discussed in Section 8.3, concentration and production data can be used 7 to estim ate that vinyl chloride contained 0.02 g I-TEQ in 1995 and 0.02 g I-TEQ in 2000. The 8 total reservoir o f C D D /C D Fs in these products w ould be the cum ulative am ount o f these 9 products rem aining in use m inus any degradation or releases that have occurred. Insufficient 10 in fo rm atio n is available to estim ate th e size o f th e total reserv o ir or th e p o ssib le releases. 11 12 11.5.4. Chloranil 13 T h e p rim a ry d isc u ssio n o f p o te n tia l d io x in re le a se s fro m ch lo ra n il p ro d u c tio n is 14 p resen ted in S ection 8.9. C hloranil is u sed to m ak e dyes and pigm ents. T h ese p ro d u cts m ay 15 re m a in in u s e lo n g a fte r th e ir p ro d u c tio n and, th e re fo re , re p re se n t a p o te n tia l re se rv o ir. A s 16 d iscu ssed in S ection 8.9, chloranil im ports con tain ed 64 g I-T E Q in 1987, 0.4 g I-T E Q in 1995, 17 and 1.2 g I-T E Q in 2000. T he total reserv o ir o f C D D /C D F s in th ese p ro d u cts w o u ld b e the 18 cu m u lativ e am o u n t o f th ese p ro d u cts re m a in in g in u se m in u s any d eg rad atio n o r releases th at 19 have occurred. In su fficien t in fo rm atio n is av ailab le to estim ate th e size o f th e total reserv o ir or 20 the possible releases. 21 22 11.5.5. Polychlorinated Biphenyls (PCBs) 23 A s discussed in C hapter 10 (the prim ary chapter on PC B s), production o f P C B s ceased in 24 the 1970s. H ow ever, they w ere used in a variety o f products that can rem ain in use for long tim e 25 periods, such as transform ers and capacitors. The portion o f these products that are still in use 26 today represents potential reservoirs because releases can occur via leaks or during disposal 27 operations. A s discussed in the original report (see Section 10.6), approxim ately 568,000 M T o f 28 P C B s w ere used in the U nited States betw een 1930 and 1975. A n estim ated 50.3% w ere used in 29 capacitors, and 26.8% w ere used in transform ers. A ssum ing that these products contained an 30 a v e ra g e o f 8 m g W H O 98 T E Q P/k g (a v e ra g e c o n c e n tra tio n fo r A ro c lo r 1242, w h ic h a c c o u n te d fo r 31 o v er 50% o f total sales-- see S ection 10.6 o f original report), th en a total o f 3,500 kg o f This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11-11 DRAFT: DO NOT CITE OR QUOTE 1 WHO98 TEQp were used in capacitors and transformers. It is unknown how much of this 2 material is still in use or what amount of releases may be occurring. 3 In summary, five possible product reservoirs were identified: bleached chemical wood 4 pulp, pentachlorophenol, vinyl chloride, chloranil, and PCBs. No estimates could be made for 5 the cumulative mass of CDD/CDFs contained in these reservoirs or their releases. 6 ______________________________ Product Reservoirs ________________________________ Releases to Air Bleached Chemical Wood Pulp (Not quantifiable). Pentachlorophenol (Not quantifiable). Vinylchloride (Not quantifiable). Chloranil (Not quantifiable). PCBs (Not quantifiable).___________________________ ________________________________ Releases to Soil Bleached Chemical Wood Pulp (Not quantifiable). Pentachlorophenol (Not quantifiable). Vinylchloride (Not quantifiable). Chloranil (Not quantifiable). PCBs (Not quantifiable).___________________________ 7 8 9 11.6. SUMMARY AND CONCLUSIONS (ORIGINALLY SECTION 11.3) 10 The original report presented a series of conclusions about the relative importance of 11 reservoir sources and their implications to human exposure. Because this version of the 12 document contains only slight revisions to reservoir source estimates, the same general 13 observations made in the previous version still apply. In addition, reservoir sources are all still 14 considered "preliminary", and thus not part of the quantitative inventory. 15 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11-12 DRAFT: DO NOT CITE OR QUOTE 1 Table 11-1. Amounts of CDD/CDFs Landfilled (g WHO98 TEQ/year) Source M unicipal w aste incinerators M edical w aste incinerators Anim al crem atoria Sewage sludge Industrial w ood Industrial coal-fired utilities C em ent kilns M agnesium sm elting and refining Titanium sm elting and refining C hlor-akali plants Vinyl chloride plants C om plex organic chem ical plants M unicipal w astew ater treatm ent sludge Total "Based on TRI data (U.S. EPA, 2008). 1987 2800 760 0.2 0.4 46 39 15 1995 490 410 0.2 1 46 43 18 86 3,750 40 1,050 2000 490 320 0.2 0.7 46 50 13 10a 240a 3 6 118 13 1,310 This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11_13 DRAFT: DO NOT CITE OR QUOTE Figure 11-1. Fluxes among environmental reservoirs. This document is a draftfor review purposes only and does not constitute Agency policy. 1/7/2013 11_14 DRAFT: DO NOT CITE OR QUOTE REFERENCES Abad, E; Martinez, K; Caixach, J; et al. 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