Document KRY1GNvDp6adwOemRokQqvgkX

United States Environmental Protection Agency Office of Information Analysis & Access Washington, DC 20460 EPA-745-B-00-021 December 2000 V>EPA EMERGENCY PLANNING AND COMMUNITY RIGHT-TO-KNOW ACT - SECTION 313: Guidance for Reporting Toxic Chemicals within the Dioxin and Dioxin-like Compounds Category Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986 (EPCRRA) requires certain facilities manufacturing, processing, or otherwise using listed toxic chemicals to report the annual quantity of such chemicals entering each environmental medium. Such facilities must also report pollution prevention and recycling data for such chemicals, pursuant to section 6607 of the Pollution Prevention Act, 42 U.S.C. 13106. TABLE OF CONTENTS Section 1.0 IN T R O D U C TIO N ........................................................................................................ 1 1.1 Background...................................................................................................... 1 1.2 Who Must Report? ......................................................................................... 2 1.3 What are the Reporting Thresholds?............................................................... 3 1.4 What are Dioxin and Dioxin-like Compounds and Which Chemicals are Included in the EPCRA Section 313 Dioxin and Dioxin-like Compounds Category? ......................................................................................................... 5 1.4.1. Formation of Dioxin and Dioxin-like Compounds During Combustion 7 1.5 What Activities are Covered by the Qualifier for the Dioxin And Dioxin-like Compounds Category? ................................................................................... 9 1.6 What Other Changes to the EPCRA Section 313 Reporting Requirements Apply to the Dioxin and Dioxin-like Compounds Category? ...................... 12 1.6.1 De Minimis Exemption ........................................................................12 1.6.2 Form A Exclusion ................................................................................ 12 1.6.3 Range Reporting .............................................................................. 12 1.6.4 Data Precision................................................................................... 13 Section 2.0 GUIDANCE ON ESTIMATING ENVIRONMENTAL RELEASES OF DIOXIN AND DIOXIN-LIKE COMPOUNDS .................................................................... 14 2.1 General Guidance............................................................................................ 14 2.1.1 Approach 1 - Use Actual Facility-Specific Monitoring Data ........ 17 2.1.2 Approach 2 - Use Facility-Specific Emission F a c to rs .................... 17 2.1.3 Approach 3 - Use Facility-Specific EPA Default Emission Factors ............................................................. 19 2.2 Consideration of Non-detects......................................................................... 20 Section 3.0 EXAMPLESOF CALCULATING EMISSIONS TO THE AIR, WATER, AND L A N D .......................................................................................................................... 21 3.1 Approach 1- Use Actual Facility-specific Release D a ta ............................... 21 3.1.1 Example of Air Releases Using Stack Monitoring D a ta ................. 21 3.1.2 Example of Calculating Water Releases Using NPDES Monitoring Data .................................................................................................. 22 3.1.3 Example of Estimating Releases to L a n d ......................................... 23 3.2 Example of Estimating Releases Using Emission F a c to rs............................ 25 3.2.1 Example of Estimating Air Releases ....................................................25 3.2.2 Example of Estimating Water R eleases............................................ 26 3.2.3 Example of Estimating Releases to L a n d ......................................... 26 Section 4.0 FACILITY-SPECIFIC EPA DEFAULT EMISSION FA C TO R S......................... 28 4.1 Pulp And Paper Mills And Lumber And Wood Products ......................................................................................................... 29 4.1.1 Applicability....................................................................................... 29 4.1.2 Emission Factors for Releases to Water From Bleached Chemical Pulp M ills .......................................................................... 30 4.1.3 Emission Factors for Releases to Land From Bleached Chemical Pulp M ills .......................................................................... 31 4.1.4 Emission Factors for Releases to Air From Pulp Mill or Lumber and Wood Products Facilities........................................................... 32 4.2 Secondary Smelting And Refining of Nonferrous M e ta ls............................ 33 4.2.1 Applicability....................................................................................... 33 4.2.2 Secondary Aluminum Smelters ......................................................... 34 4.2.3 Secondary Lead Smelters................................................................. 37 4.2.4 Secondary Copper Smelters/Refiners.............................................. 39 4.3 Cement K iln s.................................................................................................. 42 4.3.1 Applicability....................................................................................... 42 4.3.2 Summary Description/Air Emission Factors..................................... 42 4.4 Utilities............................................................................................................. 45 4.4.1 Applicability....................................................................................... 45 4.4.2 Description/Emission Factors for Coal-Fired Electric Utility Boilers 45 4.4.3 Description/Emission Factors for Oil-Fired Electric Utility B oilers................................................................................................ 46 4.4.4 Description/Emission Factors for Wood-Fired Electric Utility Boilers 47 4.5 Hazardous Waste Com bustion...................................................................... 49 4.5.1 Applicability........................................................................................ 49 4.5.2 4.5.3 4.5.4 Emission Factors for Commercial Boilers and Industrial Furnaces Burning Hazardous Waste (Other than Cement K iln s).................... Cement Kilns Burning Hazardous Waste as Supplemental F u e l . . . Hazardous Waste Incineration (HWI) Facilities .............................. 49 50 53 Section 5.0 G LO SSA RY ................................................................................................................... 58 Section 6.0 CONVERSION F A C T O R S ..................................................................................... 67 Section 7.0 R EFEREN CES........................................................................................................... 71 LIST OF TABLES Table 1-1. Table 1-2. Table 4-1. Table 4-2. Table 4-3. Table 4-4. Table 4-5. Table 4-6. Table 4-7. Table 4-8. Table 4-9. Table 4-10. Table 4-11. Table 4-12. Homoloques and Positional Isomers of CDDs, CDFs Members of the EPCRA Section 313 Dioxin and Dioxin-like Compounds Category Average Emission Factors (pg/L) for Estimating Wastewater Discharges of Dioxin and Dioxin-like Compounds into Surface Water From Bleached Chemical Pulp Mills Average Emission Factors (ng/kg) for Land Disposal of Dioxin and Dioxin-like Compounds in Wastewater Sludge From Bleached Chemical Pulp Mills Average Emission Factors (ng/kg) for Air Releases of Dioxin and Dioxin-like Compounds From the Combustion of Wood Waste and Bark (as fired) at Pulp Mill or Lumber and Wood Product Industry Facility Boilers Average Emission Factors (ng/kg scrap aluminum processed) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Secondary Aluminum Smelters Average Emission Factors (ng/kg) For Estimating Air Releases of Dioxin and Dioxin like Compounds From Secondary Lead Smelters CDD/CDF Emission Factors (ng Dioxin and Dioxin-like Compounds per kg copper scrap processed) For Secondary Copper Smelters Average Emission Factors (ng/kg cement clinker produced) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Cement Kilns Not Combusting Hazardous Waste as Supplemental Fuel Average Emission Factors (ng/kg coal combusted) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Coal-Fired Utility Boilers Average Emission Factors (pg/L oil combusted) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Oil-Fired Utility Boilers Average Emission Factors (ng/kg of wood combusted) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Wood-Fired Electric Utility Boilers Average Emission Factors (ng/kg waste feed) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Boilers and Industrial Furnaces Burning Hazardous Waste (other than cement kilns) Average Emission Factors (ng per dscm) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Cement Kilns Combusting Hazardous Waste as Supplemental Fuel Table 4-13. Average Emission Factors (ng/kg waste feed) For Estimating Air Releases of Dioxin and Dioxin-like Compounds From Hazardous Waste Combustion Facilities LIST OF FIGURES Figure 1. Figure 2. Chemical Structure of Dioxin-Like Compounds Decision Tree for Selecting Emission Estimation Technique LIST OF ABBREVIATIONS AND ACRONYMS BACT BADT CAAA CAS CDDs CDFs dscf dscm EPCRA ESP g kg L lb m3 MACT ng oC oF Pg s SIC yr Best Available Control Technology Best Available Demonstrated Technology Clean Air Act Amendments Chemical Abstract Service Chlorinated dibenzo-p-dioxins Chlorinated dibenzofurans dry standard cubic foot dry standard cubic meter Emergency Planning and Community Right-to-Know Act of 1986 Electrostatic precipitator gram kilogram liter pounds (avoir) cubic meter Maximum Achievable Control Technology nanogram. 1 E-09 gram Temperature in Celsius Temperature in Fahrenheit picogram. 1 E-12 gram seconds Standard Industrial Classification Code year Section 1.0. INTRODUCTION Section 1.1. Background On October 29, 1999, the Environmental Protection Agency (EPA) promulgated a final rule (64 FR 58666) adding a category of dioxin and dioxin-like compounds to the list of toxic chemicals subject to the reporting requirements under section 313 of the Emergency Planning and Community Right-to-Know Act of 1986 (EPCRA). The reporting threshold for the category was also established as 0.1 grams manufactured, processed, or otherwise used. The category listing is: Dioxin and dioxin-like compounds (Manufacturing; and the processing or otherwise use of dioxin and dioxin-like compounds if the dioxin and dioxin-like compounds are present as contaminants in a chemical and if they were created during the manufacturing of that chemical) (40 CFR 372.65(c)) The purpose of this document is to provide guidance on the reporting requirements of EPCRA section 313 for the dioxin and dioxin-like compounds category. EPCRA section 313 covered facilities that exceed the reporting threshold for the dioxin and dioxin-like compounds category are subject to the EPCRA section 313 annual reporting requirements beginning with reporting year 2000, with the first reports due by July 1, 2001. This document explains the EPCRA section 313 reporting requirements, and provides guidance on how to estimate annual releases and other waste management quantities of dioxin and dioxin-like compounds to the environment from certain industries and industrial activities. Because each facility is unique, the recommendations presented may have to be adjusted to the specific nature of operations at your facility or industrial activity. A primary goal of EPCRA is to increase the public's knowledge of, and access to, information on the presence and release and other waste management activities of EPCRA section 313 toxic chemicals in their communities. Under EPCRA section 313, certain facilities (see Section 1.2, below) exceeding certain thresholds (see Section 1.3) are required to submit reports (commonly referred to as Form R reports or Form A certification statements) annually. Reports must be submitted to EPA and State or Tribal governments, on or before July 1, for activities in the previous calendar year. The owner/operator of the facility on July 1 of the reporting deadline is primarily responsible for the report, even if the owner/operator did not own the facility during the reporting year. EPCRA also mandates that EPA establish and maintain a publicly available database consisting of the information reported under section 313. This database, known as the Toxics Release Inventory (TRI), can be accessed through the following sources: EPA's Internet site, www.epa.gov/tri; Envirofacts Warehouse Internet site; www.epa.gov/enviro/html/tris/tris_overview.html; 1  CD-ROM from the Government Printing Office (GPO); TRI Explorer, www.epa.gov/tri/triexplorer Microfiche in public libraries; Magnetic tape and diskettes from the National Technical Information Service; and EPA's annual TRI data release materials (summary information). The objectives of this guidance document are to: List EPCRA section 313 reporting requirements for the dioxin and dioxin-like compounds category; Promote consistency in the method of estimating annual releases and other waste management quantities of dioxin and dioxin-like compounds for particular industries and industrial classes; Reduce the level of effort expended by those facilities that prepare an EPCRA section 313 report for the dioxin and dioxin-like compounds category. Section 1.2. Who Must Report? A plant, factory, or other facility is subject to the provisions of EPCRA section 313, if it meets all three of the following criteria: It is included in the following Standard Industrial Classification (SIC) Codes: Metal Mining, SIC Code 10 (except SIC codes 1011, 1081, and 1094); Coal Mining, SIC Code 12 (except SIC code 1241); Manufacturing SIC Codes 20 through 39; Electric Utilities, SIC Codes 4911, 4931, or 4939 (each limited to facilities that combust coal and/or oil for the purpose of generating power for distribution in commerce); Commercial Hazardous Waste Treatment, SIC Code 4953 (limited to facilities regulated under the Resource Conservation and Recovery Act, subtitle C, 42 U.S.C. section 6921 et seq.); Chemicals and Allied Products-Wholesale, SIC Code 5169; Petroleum Bulk Terminals and Plants, SIC Code 5171; and, Solvent Recovery Services, SIC Code 7389 (limited to facilities primarily engaged in solvent recovery services on a contract or fee basis); and It has 10 or more full-time employees (or the equivalent of 20,000 hours per year); and It manufactures (includes imports), processes or otherwise uses any of the toxic chemicals listed on the EPCRA section 313 list in amounts greater than the established threshold quantities. In addition, pursuant to Executive Order 13148 entitled "Greening the Government Through Leadership in Environmental Management," federal facilities are required to comply with the reporting requirements of EPCRA section 313 beginning with calendar year 1994. This requirement is mandated regardless of the facility's SIC code. 2 Section 1.3. What are the Reporting Thresholds? Thresholds are specified amounts of toxic chemicals manufactured, processed, or otherwise used during the calendar year that trigger reporting requirements. The EPCRA section 313 dioxin and dioxin-like compounds category consists of seventeen specific compounds (see Section 1.4, Table 1-2) that are reported as a single chemical category. EPA regulations require threshold determinations for chemical categories to be based on the total mass of all the chemicals in that category (40 CFR 372.25(d)). Reporting is required for the dioxin and dioxin-like compounds category: If a facility manufactures 0.1 grams of dioxin and dioxin-like compounds over the calendar year. If a facility processes 0.1 grams of dioxin and dioxin-like compounds over the calendar year. (See the category qualifier in section 1.5) If a facility otherwise uses 0.1 grams of dioxin and dioxin-like compounds over the calendar year. (See the category qualifier in section 1.5 The terms manufacture, process, and otherwise use are defined at 40 CFR 372.3 as: Manufacture means to produce, prepare, import, or compound a toxic chemical. Manufacture also applies to a toxic chemical that is produced coincidentally during the manufacture, processing, use, or disposal of another chemical or mixture of chemicals, including a toxic chemical that is separated from that other chemical or mixture of chemicals as a byproduct, and a toxic chemical that remains in that other chemical or mixture of chemicals as an impurity. Otherwise use means any use of a toxic chemical, including a toxic chemical contained in a mixture or other trade name product or waste, that is not covered by the terms ``manufacture'' or ``process.'' Otherwise use of a toxic chemical does not include disposal, stabilization (without subsequent distribution in commerce), or treatment for destruction unless: (1) The toxic chemical that was disposed, stabilized, or treated for destruction was received from offsite for the purposes of further waste management; or (2) The toxic chemical that was disposed, stabilized, or treated for destruction was manufactured as a result of waste management activities on materials received from off-site for the purposes of further waste management activities. Relabeling or redistributing of the toxic chemical where no repackaging of the toxic chemical occurs does not constitute otherwise use or processing of the toxic chemical. Process means the preparation of a toxic chemical, after its manufacture, for distribution in commerce: (1) In the same form or physical state as, or in a different form or physical state from, that in which it was received by the person so preparing such 3 substance, or (2) As part of an article containing the toxic chemical. Process also applies to the processing of a toxic chemical contained in a mixture or trade name product. The qualifier for the dioxin and dioxin-like compounds category places some limitations on what is covered by the category and thus certain processing or otherwise use activities that may involve dioxin and dioxin-like compounds are not reportable. See Section 1.5 for a detailed discussion of the qualifier and its impacts on reporting. The quantities of dioxin and dioxin-like compounds included in threshold determinations are not limited to the amounts o f these compounds released to the environment, they include all amounts of dioxin and dioxin-like compounds manufactured, processed, or otherwise at the facility. For example, some emission factors may include values for both before and after scrubbers, and while the after scrubber values would apply to release estimates, the before scrubber values would apply towards threshold calculations since this represents amounts that have been manufactured. Amounts estimated to be removed by scrubbers should also be reported according to how they are handled (e.g., released to land on-site, transferred off-site for disposal or destruction, etc.). If the only information that a facility has concerning the manufacturing, processing, or otherwise use of dioxin and dioxin-like compounds at the facility comes from emission factors, then those quantities can be used to determine threshold quantities. EPA regulations require threshold determinations, and release and other waste management quantities for chemical categories to be based on the total mass of all the chemicals in the category (40 CFR 372.25(d)). Thus, in determining thresholds and release and other waste management quantities the amounts of all members o f the category must be summed and included in the calculations. As with reporting for all EPCRA section 313 categories, one Form R is prepared for the dioxin and dioxin-like compounds category that contains the total amounts of all members of the category. All reporting for the dioxin and dioxin-like compounds category is to be in gram quantities (40 CFR 372.85), no reporting in grams of toxic equivalents (TEQs) is allowed. It is important to remember that EPCRA section 313 does not require any additional testing. As stated in EPCRA section 313(g)(2): [i]n order to provide the information required under this section, the owner or operator of a facility may use readily available data (including monitoring data) collected pursuant to other provisions of law, or, where such data are not readily available, reasonable estimates o f the amounts involved. Nothing in this section requires the monitoring or measurement of the quantities, concentration, or frequency of any toxic chemical released into the environment beyond that monitoring and measurement required under other provisions of law or regulation. While individual reporting of each member o f the dioxin and dioxin-like compounds category (see Table 1-2) is not required, the Form R does contain a section for reporting the distribution of dioxin and each dioxin-like compound for the total quantity that the facility is reporting. This distribution must be reported if the information is available from the data used to calculate thresholds, releases, and other waste management quantities. The distribution shall either be the distribution that best represents 4 the distribution of the total quantity of dioxin and dioxin-like compounds released to all media from the facility or the facility's one best media specific distribution. For example, facilities with releases of dioxin and dioxin-like compounds to several different media may wish to report a distribution that best represents the distribution to all media while a facility with only or mostly air releases may wish to report the distribution associated with those air releases. Each facility should determine the most appropriate distribution to report. When using the default emission factors listed in Section 4.0 the distribution associated with the emission factor should be reported unless the facility has a better or more appropriate distribution available. Section 1.4 of the Form R allows for the reporting of the distribution of each member of the dioxin and dioxin-like compounds category. Section 1.4 is reproduced below: 1.4 NA Distribution of Each Member of the Dioxin and Dioxin-like Compounds Category. (If there are any numbers in boxes 1-17, then every field must be filled in with either 0 or some number between 0.01 and 100. Distribution should be reported in percentages and the total should equal 100%. If you do not have speciation data available, check NA.) 123 456 7 _L 8 9 10 11 12 13 14 15 16 17 1 The Form R instructions list all members of the dioxin and dioxin-like compounds category and each is labeled with a number from 1-17 to be used in filling out the distribution for Section 1.4. Table 1-2 in section 1.4 lists the 1-17 number labels for each member of the category. Section 1.4. What are Dioxin and Dioxin-like Compounds and Which Chemicals are Included in the EPCRA Section 313 Dioxin and Dioxin-like Compounds Category? Polychlorinated dibenzo-para(p)-dioxins (CDDs) and polychlorinated dibenzofurans (CDFs) constitute a group of persistent, bioaccumulative, toxic (PBT) chemicals that are termed `dioxin-like.' The term, `dioxin-like' refers to the fact that these compounds have similar chemical structure, similar physical-chemical properties, and invoke a common battery of toxic responses. An important aspect to this definition is that the CDDs and CDFs must have chlorine substitution of hydrogen atoms at the 2, 3, 7, and 8 positions on the benzene rings. A molecule of dibenzo-p-dioxin (DD) and dibenzofuran (DF) is a triple-ring structure consisting of two benzene rings interconnected by a third oxygenated ring (i.e., a ring containing an oxygen atom). In DD, the middle oxygenated ring contains two oxygen atoms that connect the benzene rings while in DF, the oxygenated ring contains one oxygen atom that joins the benzene rings. The molecular structure of DD and DF is depicted in Figure 1. As can be discerned in Figure 1, there is the possibility of substituting hydrogen atoms with chlorine atoms (or other halogens) at eight substituent positions along the DD and DF molecules (i.e., positions 1, 2, 3, 4, 6, 7, 8, or 9). This pattern of substitution creates the possibility of 75 chlorodibenzo-p-dioxin and 135 chlorodibenzofuran compounds. These individual compounds are technically referred to as congeners. Homologue groups are groups of congeners that have the same number of chlorine atoms attached to the molecule, but substituted in different positions as indicated by C^ and C^ in Figure 1. The prefix mono, di, tri, tetra, penta, hexa, 5 hepta, and octa designates the total number of chlorines in the nomenclature of homologue groupings (i.e., molecules with either 1, 2, 3, 4, 5, 6, 7, or 8 chlorine atoms attached to the carbons). Isomerism is another important chemical descriptor, and refers to compounds with the same molecular formula (e.g., the same number of carbon, hydrogen, and chlorine atoms) but that differ by the location of the chlorine atoms on the benzene rings. Table 1-1 displays the total number of positional CDD and CDF isomers that are possible within each homologue group. The compounds with chlorine substitution in the 2, 3, 7, 8-positions on the molecule are the most toxic and bioaccumulate in mammalian systems, including humans. Figure 1. Chemical Structure of Dioxin-Like Compounds Dibenzo-p-dioxin Dibenzofuran Table 1-1. Homologues and Positional Isomers of CDDs, CDFs Homologue Chlorine Isomers o f Isomers o f (prefix) Atoms CDDs CDFs Mono 12 4 Di 2 10 16 Tri 3 14 28 Tetra (T) 4 22 38 Penta (Pe) 5 14 28 Hexa (Hx) 6 10 16 Hepta (Hp) 7 2 4 Octa (O) 8 1 1 Totalnossiblecongeners 75 135 The EPCRA section 313 dioxin and dioxin-like compounds category consists of seventeen specific CDD and CDF compounds. Only those CDD and CDF compounds with chlorine substitution in the 2, 3, 7, 8-positions on the molecule are reportable under the EPCRA section 313 dioxin and dioxin-like compounds category. Table 1-2 lists all of the members of the EPCRA section 313 dioxin and dioxin-like compounds category by CAS number, name and abbreviated name. These are the only CDD and CDF compounds that are reportable under the EPCRA section 313 dioxin and dioxin-like compounds category. The term "dioxin," as in "dioxin and dioxin-like compounds" refers to the most widely studied of these compounds, 2,3,7,8-tetrachlorodibenzo-p-dioxin (CAS No. 1746-01-6). Throughout this document the phrase "dioxin and dioxin-like compounds" refers to the seventeen chemicals listed in Table 1-2. 6 Table 1-2. Members of the EPCRA Section 313 Dioxin and Dioxin-like Compounds Category CAS No. Chemical Name Abbreviated Name CDDs 1746-01-6 2,3,7,8-tetrachlorodibenzo-p-dioxin 2,3,7,8-TCDD 40321-76-4 1,2,3,7,8-pentachlorodibenzo-p-dioxin 1,2,3,7,8-PeCDD 39227-28-6 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin 1,2,3,4,7,8-HxCDD 57653-85-7 1,2,3,6,7,8-hexachlorodibenzo-p-dioxin 1,2,3,6,7,8-HxCDD 19408-74-3 1,2,3,7,8,9-hexachlorodibenzo-p-dioxin 1,2,3,7,8,9-HxCDD 35822-46-9 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin 1,2,3,4,6,7,8-HpCDD 3268-87-9 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin 1,2,3,4,6,7,8,9-OCDD CDFs 51207-31-9 2,3,7,8-tetrachlorodibenzofuran 2,3,7,8-TCDF 57117-41-6 1,2,3,7,8-pentachlorodibenzofuran 1,2,3,7,8-PeCDF 57117-31-4 2,3,4,7,8-pentachlorodibenzofuran 2,3,4,7,8-PeCDF 70648-26-9 1,2,3,4,7,8-hexachlorodibenzofuran 1,2,3,4,7,8-HxCDF 57117-44-9 1,2,3,6,7,8-hexachlorodibenzofuran 1,2,3,6,7,8-HxCDF 72918-21-9 1,2,3,7,8,9-hexachlorodibenzofuran 1,2,3,7,8,9-HxCDF 60851-34-5 2,3,4,6,7,8-hexachlorodibenzofuran 2,3,4,6,7,8-HxCDF 67562-39-4 1,2,3,4,6,7,8-heptachlorodibenzofuran 1,2,3,4,6,7,8-HpCDF 55673-89-7 1,2,3,4,7,8,9-heptachlorodibenzofuran 1,2,3,4,7,8,9-HpCDF 39001-02-0 1,2,3,4,6,7,8,9-octachlorodibenzofuran 1,2,3,4,6,7,8,9-OCDF *For filling out the distribution of each member of the category in section 1.4 of the Form R. # Label* 17 15 7 8 9 10 12 16 13 14 3 4 5 6 1 2 11 Section 1.4.1. Formation of Dioxin and Dioxin-like Compounds During Combustion More than a decade of combustion research has contributed to a general understanding of the central molecular mechanisms that form CDDs and CDFs emitted from combustion sources. Current understanding of the conditions necessary to form CDDs and CDFs were primarily derived from studying full-scale municipal solid waste incinerators (MSWIs), augmented with observations involving the experimental combustion of synthetic fuels and feeds within the laboratory. However, the formation 7 mechanisms elucidated from these studies are generally relevant to most combustion systems in which organic material is burned with chlorine. Intensive studies have examined MSWIs from the perspective of identifying the specific formation mechanism(s) that occur within the system. This knowledge may lead to methods that prevent the formation of CDDs and CDFs and their release into the environment. Although much has been learned from such studies, how to completely prevent CDDs/CDFs from forming during the combustion of certain organic materials in the presence of a source of chlorine and oxygen is still unknown. The wide variability of organic materials incinerated and thermally processed by a wide range of combustion technologies that have variable temperatures, residence times, and oxygen requirements adds to this complex problem. However, central chemical events that participate in forming CDDs and CDFs can be identified by evaluating emission test results from MSWIs in combination with laboratory experiments. CDD/CDF emissions from combustion sources can potentially be explained by three principal mechanisms, which should not be regarded as being mutually exclusive. The first is that CDDs and CDFs are present as contaminants in the combusted organic material, and pass through the furnace and are emitted unaltered. The second is that CDD/CDFs ultimately form from the thermal breakdown and molecular rearrangement of precursor ring compounds, which are defined as chlorinated aromatic hydrocarbons with a structural resemblance to the CDD and CDF molecules. Ringed precursors emanated from the combustion zone are a result of the incomplete oxidation of the constituents of the feed (i.e., products of incomplete combustion). The third mechanism, similar to the second, is that CDD/CDFs are synthesized de novo. De novo synthesis describes a pathway of forming CDD/CDFs from heterogeneous reactions on fly ash involving carbon, oxygen, hydrogen, chorine, and a transition metal catalyst. With these reactions, intermediate compounds having an aromatic ring structure are formed. Studies in this area suggest that aliphatic compounds, which arise as products of incomplete combustion, may play a critical role in initially forming simple ring molecules, which later evolve into complex aromatic precursors. CDD/CDFs are then formed from the intermediate compounds. In both mechanisms (2) and (3), formation occurs outside the furnace, in the so-called post-combustion zone. Particulate bound carbon is suggested as the primary reagent in the de novo syntheses pathway. Although chlorine is an essential component for the formation of CDD/CDFs in combustion systems, the empirical evidence indicates that, for commercial scale incinerators, chlorine levels in feed are not the dominant controlling factor for rates of CDD/CDF stack emissions. Important factors which can affect the rate of CDD/CDF formation include the overall combustion efficiency, post combustion flue gas temperatures and residence times, and the availability of surface catalytic sites to support CDD/CDF synthesis. Data from bench, pilot and commercial scale combustors indicate that CDD/CDF formation can occur by a number of mechanisms. Some of these data, primarily from laboratory and pilot scale combustors, have shown direct correlation between chlorine content in fuels and rates of CDD/CDF formation. Other data, primarily from commercial scale combustors, show little relation with availability of chlorine and rates of CDD/CDF formation. The conclusion that chlorine in feed is not a strong determinant of CDD/CDF emissions applies to the overall population of commercial scale combustors. For any individual commercial scale combustor, circumstances may exist in which changes in chlorine content of feed could affect CDD/CDF emissions. For uncontrolled combustion, such as open burning of household waste, chlorine content of wastes may play a more 8 significant role in affecting levels of CDD/CDF emissions than observed in commercial scale combustors. For a more detailed discussion of the mechanisms of formation and the role of chlorine in the formation kinetics, the reader may refer to: Volume 2: Sources o f Dioxin-Like Compounds in the United States; Chapter 2: Mechanisms offormation o f dioxin-like compounds during combustion o f organic materials; In: Estimating Exposure to Dioxin-Like Compounds. EPA/600/P-00/001Bb, September 2000. Draft Final Report. Section 1.5. What Activities are Covered by the Qualifier for the Dioxin and Dioxin-like Compounds Category? The dioxin and dioxin-like compounds category has the following activity qualifier that describes what must be reported under the category: "Manufacturing; and the processing or otherwise use of dioxin and dioxin-like compounds if the dioxin and dioxin-like compounds are present as contaminants in a chemical and if they were created during the manufacturing of that chemical." This qualifier states that if a facility manufactures dioxin and dioxin-like compounds then those quantities must be applied towards the 0.1 gram manufacturing threshold and included in release and other waste management calculations. Manufacture includes the coincidental production of dioxin and dioxin-like compounds during any process (e.g., a combustion process, a chemical manufacture process). Note that, as discussed in Section 1.3, the EPCRA section 313 definition of manufacture includes importing. The qualifier also covers the processing or otherwise use of dioxin and dioxin-like compounds, but only if the dioxin and dioxin-like compounds are present as contaminants in a chemical and if they were created during the manufacturing of that chemical. This means that if a facility processes or otherwise uses a chemical or mixture that contains dioxin and dioxin-like compounds that were created during the manufacturing of that chemical or mixture, then the dioxin and dioxin-like compounds must be included in threshold determinations and release and other waste management calculations. However, if the dioxin and dioxin-like compounds were already present in a product being processed or otherwise used and were not created during the manufacture of that product (such as at food processing plants where dioxin and dioxin-like compounds may be present in the incoming raw materials) the dioxin and dioxin-like compounds are not reportable and do not need to be included in threshold determinations or release and other waste management calculations. Examples of the impacts of the dioxin and dioxin-like compounds category qualifier on what is reportable: Example 1: A facility manufactures chemical A and in doing so, the facility also manufactures dioxin or dioxin-like compounds. Because EPCRA section 313 defines "manufacturing" to include production, the facility would have to include the dioxin or dioxin-like compounds it produced in its threshold determinations and release and other waste management calculations. This is true regardless of whether the compounds are present as contaminants in chemical A since the chemical listing for dioxin or dioxin-like 9 compounds contains no modifications to the term manufacture as defined under EPCRA section 313. Example 2: A facility processes or otherwise uses chemical A. Dioxin or dioxin-like compounds are present in chemical A as contaminants. The dioxin or dioxin-like compounds present in chemical A were created during the manufacturing of chemical A. In this case, the facility would have to include the dioxin or dioxin-like compounds present in chemical A in its threshold determinations and release and other waste management calculations. Note that if chemical A is processed into a different product but chemical A still exists in that product (i.e., it has not been converted into a different chemical) then the dioxin and dioxin-like compounds must be included in threshold determinations and release and other waste management calculations. Example 3: A facility processes or otherwise uses chemical B. Dioxin or dioxin-like compounds are present in chemical B as contaminants. However, the dioxin or dioxin-like compounds in chemical B were not created during the manufacturing of chemical B (they were introduced from an environmental source or created during the manufacture of a precursor to chemical B). In this case, because one of the two limitations in the category qualifier was not satisfied, the facility would not have to include the dioxin or dioxin-like compounds present in chemical B in its threshold determinations and release and other waste management calculations. Example 4: Dioxin or dioxin-like compounds are present in chemical A as contaminants. The dioxin or dioxin-like compounds present in chemical A were created during the manufacturing of chemical A. Facility X uses or processes chemical A to manufacture chemical C. No new dioxin or dioxin-like compounds were created in the manufacture of chemical C, but chemical C does contain the dioxin or dioxin-like chemicals that were present in chemical A. Because facility X is using or processing chemical A, which contains dioxin or dioxin-like compounds as contaminants that were created during the manufacturing of chemical A, facility X would have to include the dioxin or dioxin-like compounds present in chemical A in its threshold determinations and release and other waste management calculations. This is true regardless of what facility X does with chemical C (uses it on site, sells it, etc.) Facility X then sells chemical C to facility Y. Although chemical C contains dioxin or dioxin like compounds as contaminants, those compounds were not created during the manufacture of chemical C (they were created during the manufacture of chemical A). Because one of the two limitations in the category qualifier was not satisfied, facility Y would not have to include the dioxin or dioxin-like compounds present in chemical C in its threshold determinations and release and other waste management calculations. 10 Example 5: Facility X imports chemical D into the country. Chemical D contains dioxin or dioxin like compounds. Because EPCRA section 313 defines "manufacturing" to include importing, facility X would have to include the dioxin or dioxin-like compounds present in chemical D in its threshold determinations and release and other waste management calculations. This is true regardless of whether the compounds are present as contaminants or when they were created since the chemical listing for dioxin or dioxin like compounds contains no modifications to the term manufacture as defined under EPCRA section 313. Facility X then sells chemical D to facility Y. Facility Y processes or uses chemical D on site. Facility Y must determine if the dioxin or dioxin-like compounds present in chemical D: 1) are present as contaminants, and 2) were created during the manufacture of chemical D. If the answers to both questions are "Yes," then facility Y would have to include the dioxin or dioxin-like compounds present in chemical D in its threshold determinations and release and other waste management calculations. In answering those questions, facility Y should use the best available information. Example 6: A waste management facility accepts wastes that contain dioxin or dioxin-like compounds for the purposes of on-site waste management. By accepting waste for on site waste management, the facility is otherwise using the dioxin or dioxin-like compounds in that waste. The facility must determine if the dioxin or dioxin-like compounds in the waste: 1) are present as contaminants, and 2) were created during the manufacture of the waste or any chemicals in the waste. If the answers to both questions are "Yes," then the facility would have to include the dioxin or dioxin-like compounds present in the waste in its threshold determinations and release and other waste management calculations. In answering those questions, the facility should use the best available information. There are several chemicals and/or products that EPA has identified as having the potential to contain dioxin and dioxin-like compounds manufactured as by-products during the manufacturing process for those chemicals. These chemicals include, but are not limited to: CAS No. 118-75-2 87-86-5 107-06-2 94-75-7 1928-43-4 Chemical/Product Name Chloranil Pentachlorophenol (PCP) Ethylene dichloride (EDC) (manufactured by oxychlorination) 2,4-D 2,4-D Ester Herbicides Bleached chemical wood pulp Typical Uses dyes, pigments, pesticides wood preserving, pesticides vinyl chloride production, gasoline, paints and varnishes, metal degreasing, scouring compounds, organic synthesis, solvent, fumigant pesticides pesticides white paper products 11 Section 1.6. What Other Changes to the EPCRA Section 313 Reporting Requirements Apply to the Dioxin and Dioxin-like Compounds Category? EPA has also made modifications and/or clarifications to certain reporting exemptions and requirements for the PBT chemicals that are subject to the lower reporting thresholds; this includes the dioxin and dioxin-like compounds category. Each of the changes as they apply to dioxin and dioxin like compounds category is discussed in the following subsections. Section 1.6.1. De Minimis Exemption The de minimis exemption allows facilities to disregard certain minimal concentrations of nonPBT chemicals in mixtures or other trade name products they process or otherwise use when making threshold determinations and release and other waste management calculations. EPA eliminated the de minimis exemption for the dioxin and dioxin-like compounds category (40 CFR 372.38(a)). This means that facilities are required to include all amounts of dioxin and dioxin like compounds in threshold determinations and release and other waste management calculations regardless of the concentration of the dioxin and dioxin-like compounds in mixtures or trade name products. Section 1.6.2. Form A Exclusion The "TRI Alternate Threshold for Facilities with Low Annual Reportable Amounts," provides facilities otherwise meeting EPCRA section 313 reporting thresholds the option of certifying on Form A provided that they do not exceed 500 pounds for the total annual reportable amount for that chemical, and that their amounts manufactured or processed or otherwise used do not exceed one million pounds. EPA has excluded the dioxin and dioxin-like compounds category from the "TRI Alternate Threshold for Facilities with Low Annual Reportable Amounts" (40 CFR 372.27(e)). Therefore, submitting a Form A rather than a Form R is not an option for the dioxin and dioxin-like compounds category. Section 1.6.3. Range Reporting For facilities with total annual releases or off-site transfers of an EPCRA section 313 chemical of less than 1,000 pounds, EPA allows the amounts to be reported on the Form R either as an estimate or by using ranges. EPA has eliminated range reporting for the dioxin and dioxin-like compounds category (40 CFR 372.85(b)). This means that for those sections of the Form R for which range reporting is an option, the option cannot be used when reporting on the dioxin and dioxin-like compounds category. Thus facilities must report an actual number rather than a selected range. 12 Section 1.6.4. Data Precision Facilities should report for the dioxin and dioxin-like compounds category at a level of precision supported by the accuracy of the underlying data and the estimation techniques on which the estimate is based. However, the smallest quantity that needs to be reported on the Form R for the dioxin and dioxin-like compounds category is 0.0001 grams (i.e., 100 micrograms). Example: If the total quantity for Section 5.2 of the Form R (i.e., stack or point air emissions) is 0.00005 grams or less, then zero can be entered. If the total quantity is between 0.00005 and 0.0001 grams then 0.0001 grams can be entered or the actual number can be entered (e.g., 0.000075). 13 Section 2.0. GUIDANCE ON ESTIMATING ENVIRONMENTAL RELEASES OF DIOXIN AND DIOXIN-LIKE COMPOUNDS Section 2.1. General Guidance EPA is providing the following guidance which may be used by facilities in estimating and reporting annual releases and other waste management quantities for the dioxin and dioxin-like compounds category. If you are not sure whether information in this guidance can be applied to the situation at your facility, EPA recommends consultation with the Agency before using this guidance. The EPA contact for the emission factors and other estimation methods contained in this document is David Cleverly, National Center for Environmental Assessment (8623D), U.S. EPA, 1200 Pennsylvania Ave, NW, Washington, DC or e-mail at cleverly.david@epa.gov. EPA supports the use of three different approaches for estimating annual releases of dioxin and dioxin-like compounds from facilities subject to reporting: 1. Use of actual facility-specific monitoring data 2. Use of facility-specific emission factors 3. Use of facility-specific EPA default emission factors In general EPA considers these three approaches to be hierarchical. In most situations, monitoring or directly measured data obtained at your facility provides the best and most accurate estimate of annual releases of dioxin and dioxin-like compounds. Note that, as discussed under Section 1.3, EPCRA section 313 does not require any additional monitoring or measurements beyond that monitoring and measurement required under other provisions of law or regulation. Depending on the adequacy and quality of the data in terms of sampling and laboratory methods used to ascertain the data, monitoring data may or may not be a facility's best available data. To be representative of annual releases of dioxin and dioxin-like compounds, the monitoring and sampling should have been taken under conditions representative of the facility's general operating and/or production conditions. In the absence of such monitoring data two additional approaches are recommended, which, to the extent possible, should also be based on conditions representative of the facility's general operating and/or production conditions. First, facilities may use facility-specific emission factors that they believe are the best `fit' to their facility. This means that the facility may use emission factors developed from the sampling and monitoring of dioxin and dioxin-like compounds at a similar facility. Reports of sampling emission and effluent streams should be collected and reviewed from facilities that are most similar in technology, design, operation, capacity, auxiliary fuels used, products produced, the manufacturing process, waste products generated, Industrial Classification Code, feedstocks used, air/water pollution control systems, etc. An important aspect in selecting an emission 14 factor for a combustion process is temperature. A temperature inlet to the air pollution control device that is below 200o Celsius or above 450o Celsius will result in minimal stack release of dioxin and dioxin-like compounds. Therefore, in defining similarity of process, the facility operator is encouraged to examine, and then match, the temperature reported at the facility that you selected to be representative of potential emissions from your facility. Data from similar facilities within the same industry sector compiled by industry technical organizations may be a good source of facility-specific emission factors. Second, facilities that cannot use either of these approaches may estimate their annual releases through the use of default emission factors provided by EPA in Section 4 of this guidance. Selection of more site-specific emission factors are preferred. The owner/operator of the facility should determine whether one of these three approaches would provide an accurate reflection of the potential for releases of dioxin and dioxin-like compounds from the facility or whether some other method would be more appropriate. Figure 2 is a `decision tree' highlighting the basic questions one should ask when selecting the appropriate emission factor approach. The first step in the `decision tree' is to determine whether your facility meets the reporting requirements of EPCRA section 313, however, it is possible that before you can make a final determination on whether your facility meets the EPCRA section 313 reporting requirements you may have to go ahead and use one of the estimation methods to help determine if your facility will exceed reporting thresholds. When selecting the estimation method to be used, EPA recommends that the facility be able to document the rationale employed in making the selection. When documenting the annual releases and other waste management quantities of dioxin and dioxin-like compounds, EPA recommends that the facility indicate which of these three approaches was used in deriving the estimate. The owner/operator is encouraged to exercise `best engineering judgement' when arriving at the decision on the most appropriate approach to use. A more detailed explanation of each of these approaches follows. 15 Figure 2. Decision Tree For Selecting Emission Estimation Technique In the context of this guidance, the term "best engineering judgment" engenders one or more of the following: Knowledge of the manufacturing/industrial process and process flow; Knowledge of the chemical feed stocks used in the manufacturing/industrial process Knowledge of the feedstocks/fuels used in providing a source of energy for the process; Knowledge of the water pollution control system/technology and contaminant removal efficiencies used to treat industrial wastewater; Knowledge of the waste products derived from operations and manufacturing; Knowledge of the air pollution control equipment and contaminant removal efficiencies used to control toxic air pollutants. When applying `best engineering judgement' to a determination of the appropriate emission factor approach to use to calculate emissions and releases of dioxin-like compounds for your facility, it is important to: Obtain engineering test reports and/or literature references of dioxin emissions/releases from facilities that are within your SIC code. Compare your facility design, function and operations with other facilities that have been tested or sampled for emissions of dioxin-like compounds. This will allow you to match the two 16 processes and make the determination as to how representative these emission factors are to your facility; If you are unable to locate representative emission factors for your facility, then you may elect to use EPA's default emission factors appropriate for your facility. Section 2.1.1. Approach 1 - Use Actual Facility-Specific Monitoring Data This approach allows the facility to estimate annual releases of dioxin and dioxin-like compounds to the air, water and land, as well as other waste management quantities, based on measured data derived at the facility. A facility may be required to perform monitoring under provisions of the Clean Air Act (CAA), the Clean Water Act (CWA), the Resource Conservation and Recovery Act (RCRA), or other regulations. If this is the case, then these data should be available for developing release estimates. Data may have also been collected for your facility for compliance monitoring purposes associated with a state or federal permit. If only a small amount of direct measurement data are available or if you believe the monitoring data are not representative, you should determine if an alternative estimation method would give a more accurate result. With regard to the manner in which non-detects (ND) are reported, refer to Section 2.2. Section 2.1.2. Approach 2 - Use Facility-Specific Emission Factors Emission factors are the fundamental tools in this guidance for estimating releases of dioxin and dioxin-like compounds. An emission factor is a representative value that is intended to relate the quantity of dioxin and dioxin-like compounds released to the open environment with a measure of industrial activity associated with the release. These factors are usually expressed as the weight of pollutant divided by a unit weight, volume, or duration of the activity emitting the contaminant. Examples of emission factors include: nanograms (ng) of dioxin and dioxin-like compounds emitted into air per kilogram (kg) of coal burned; picogram (pg) of dioxin and dioxin-like compounds discharged into surface water per liter (L) of wastewater; ng dioxin and dioxin-like compounds transferred to land disposal per kg of sludge produced at your facility. Emission factors facilitate estimation of environmental releases from various sources of releases of dioxin and dioxin-like compounds when the annual activity level of the facility is known. Your emission factor should be assumed to be representative of long-term averages for your facility. The general equation for emission estimation is: Annual Release = Emission Factor x Annual Activity Level R = EF x A where: R = annual release o f dioxin and dioxin-like compounds, (i.e., g / yr) A = activity level or production rate, (e.g., kg o f materialprocessedper year) EF = dioxin emissionfactor, (e.g., g dioxin released / kg materialprocessed/ time) 17 EF is to represent the emission of dioxin and dioxin-like compounds into the open environment at the `end-of-the-pipe'. The extent of completeness and detail of the emissions is determined by the information available from published references. Emissions from some processes are better documented than others. When electing to use this approach, EPA recommends that the facility maintain documentation on the other facility(ies) engineering test reports or the source of the industryspecific data compiled by technical organizations that were evaluated and used in deriving your emission factors. The documentation should clarify why the other facility is a close analogy to your facility based on similarity of design, operations, feed stocks, end products, SIC code, manufacturing process, combustion process, and pollution control systems. Sources of information that may be helpful in Approach 2 include: G State Regulatory Agencies. In the development of regulatory requirements for specificities, it is often the case that State environmental agencies have issued permits for the allowable discharge of dioxin-like compounds to the environment from facilities similar to your own. The State Agency may have reliable test reports information attendant to permitting such facilities. These test reports are usually kept in the public record. G Trade Associations. Several industries are represented by Trade Associations that function to foster the interests of a particular industrial sector. Such trade associations are comprised of member companies. Often member companies make engineering test reports available to the Trade Association members. G EPA Regulatory Dockets. EPA regulatory dockets are maintained as a central repository of information EPA used in a rule making process. Such dockets and their contents are open to the public for inspection and photo copying. The Federal Register preamble announcing proposed or final rule under one of the statutory authorities of EPA will identify the location of the regulatory docket and provide information as to how one may access information in the docket. The docket does contain technical information, including test reports data, that was used in the development of the regulatory requirements. G EPA Internet Sites. The EPA maintains a central site on the Internet, i.e., http//www.epa.gov. This home page provides a useful base from which to access EPA databases, reports and studies, and to conduct searches by topic. Complete documents can be electronically accessed from this site. An example of an EPA site having abundant information on air emission factors is the Technology Transfer Network maintained by EPA's Office of Air Quality Planning and Standards. This site has an URL: http://www.epa.gov/ttn. G Engineering and Science Libraries. Public and private universities often times allow public access to technical literature housed within university libraries. This is particularly true of universities having schools of engineering and science. 18 Section 2.1.3. Approach 3 - Use Facility-Specific EPA Default Emission Factors With this approach, EPA is providing tables of emission factors for specific sources, that, when multiplied by an appropriate measure of annual activity level at your facility, will result in an estimate of annual releases of the sum of dioxin and dioxin-like compounds (i.e., the 17 compounds of CDDs and CDFs) from your facility. Emission factors are used to calculate annual releases in situations in which the facility has not measured CDDs and CDFs in its effluents or emission streams. The EPA default emission factors were derived from the available monitoring data deemed to be representative of the source category (or segments of the source category that differ in configuration, fuel type, manufacturing process, feedstocks, pollution control systems, etc.). Implicit in the use of the default emission factors is the assumption that facilities with similar design and operating characteristics should have a similar potential for release of dioxin and dioxin-like compounds. The default emission factors are more accurately applied to an entire source category, because it is representative of the average emissions of all tested facilities in the category. This introduces a significant degree of uncertainty when applying the average emission factor to an individual facility, namely, that a portion of facilities within the industrial category will have emissions that are either above or below the average. However, in the absence of either monitoring data from your facility, or more accurate site-specific emission factors, EPA believes that these default emission factors can be used to make a reasonable estimation of releases. The CDD and CDF EPA default emission factors in this guidance were developed from three primary references (available in pdf format at: http://www.epa.gov/tri/): EPA's Database of Sources of Environmental Releases of Dioxin-Like Compounds in the United States, U.S. Environmental Protection Agency, National Center for Environmental Assessment, Office of Research and Development, Washington, DC 20460, EPA/600/P-98/002B, September, 2000. The Inventory of Sources of Dioxin in the United States, U.S. Environmental Protection Agency, National Center for Environmental Assessment, Office of Research and Development, Washington, DC 20460, EPA/600/P-98/002Aa. Estimating Exposure to Dioxin-Like Compounds; Volume 2: Sources o fDioxin-Like Compounds in the United States, EPA/600/)-00/001, Draft Final, September, 2000. When researching emission factors in Approach 2 (above), the owner and operator of a reporting facility may elect to use emission factors developed for sources other than those listed in this guidance, for example, medical waste incinerators. The owner/operator of such a facility is encouraged to review sources and releases of dioxin-like compounds contained in EPA's Database (listed above) in order to assist in the selection of more appropriate emission factors. 19 Section 2.2. Consideration of Non-Detects When detected in emissions and effluents from facilities, dioxin and dioxin-like compounds are found in minute quantities, e.g., one part-per trillion (1 ppt) or less, and as mixtures of dioxin and the dioxin-like compounds. Detection is with high resolution gas chromatography combined with high resolution mass spectrometry. For example, EPA Method 1613 (USEPA, 1994a) (used to quantify CDDs and CDFs in wastewater, solids, air, and tissue samples) can reliably detect these compounds at or below one part per trillion (i.e., 10 parts per quadrillion (ppq) in water; 1 ppt in solid waste). This presents a challenge in terms of interpretation of results in which a CDD/CDF compound is reported by the analytical laboratory as `Not Detected' (shown as the abbreviation `ND' on lab sheets). Even with these extremely low levels of detectability with current laboratory methods, it is not possible to know with certainty if `not detected' (ND) is actually zero (i.e., that dioxin and dioxin-like compounds are not present in the sample) or if dioxin and dioxin-like compounds really are present in the sample at some concentration below the minimal detection limit (MDL). The monitoring data and emission factors determined for your facility should be reported in a manner consistent with the methods and procedures that EPA has developed for determining if these compounds are present in various industrial processes. For example, EPA Method 1613 (USEPA, 1994a) indicates that laboratory results below the minimum detection level should be reported as not detected (ND) or as required by the regulatory authority. For purposes of threshold determinations and the reporting of releases and other waste management quantities for dioxin and dioxin-like compounds under EPCRA section 313, either with monitoring data, or by using the emission factor approach, non-detects are treated as `zero' if that is how the method being used treats non-detects (e.g., Method 1613, Method 23). However, facilities should use their best readily available information to report, so if a facility has better information than provided by these methods then that information should be used. For example, if a facility is not detecting dioxin or a particular dioxin-like compound using a particular method but has information that shows that they should be detecting them the facility should use this other information and it may be appropriate to estimate quantities using one half the detection limit. If the method being used by a facility to detect dioxin and dioxin-like compounds is not an EPA approved method and the detection level being used is not as sensitive as those approved for use under EPA methods then EPA's EPCRA section 313 guidance with regard to non-detects should be followed. This guidance states that facilities must use reasonable judgement as to the presence and amount of a listed toxic chemical based on the best readily available information. An indication that a reportable chemical is below detection is not equivalent to stating that the chemical is not present. If the reportable toxic chemical is known to be present, EPA recommends that a concentration equivalent to half the detection limit be used. Facilities should not estimate releases solely on monitoring devices, they should also rely on their knowledge of specific conditions at the plant. 20 Section 3.0. EXAMPLES OF CALCULATING EMISSIONS TO THE AIR, WATER, AND LAND Environmental releases of dioxin and dioxin-like compounds occur to all media air, water and land. Dioxin and dioxin-like compounds are not intentionally manufactured, they are inadvertently formed during certain manufacturing and combustion processes. In this regard, dioxin releases cannot be determined by a mass balance of your facility. Rather EPA recommends you use one of the three approaches listed in Section 2.0, above (direct measurements, or the two emission factor approaches). Section 4.0 gives EPA default emission factors for specific facilities falling within certain reporting facility SIC codes. The purpose of this section is to give examples of calculating emissions to air, water and land from your facility. In some examples the phrase "dioxin and dioxin-like compounds" may be abbreviated to "D&DLC" to save space. Section 3.1. Approach 1 - Use Actual Facility-specific Release Data Section 3.1.1. Example of Calculating Air Releases Using Stack Monitoring Data Example: Stack testing has determined that dioxin and dioxin-like compounds are detected in the stack gases at your facility at a concentration o f 10 E - 09 g per dry standard cubic meter o fgas (10 ng/dscm). The moisture content in the stack is typically 10%. The stack gas velocity is typically 8.0 m/s. The diameter o f the stack is 0.3 m. Calculate the annual air release o f dioxin and dioxin-like compoundsfrom the stack o fyour facility. Step 1. Calculate volumetric flow of stack gas stream. Volumetricflow Volumetricflow Volumetricflow Volumetricflow (gas velocity)x (internalareao f stack) (gas velocity) x [(pi) x (internal stack diameter)2 +4] (8.0 m /s) x [(pi) x (0.3m)2 4] 5.7 m3 / s Step 2. Correct volumetric flow for moisture content in stack gas stream Stack gases may contain large amounts o f water vapor. The concentration o f the chemical in the exhaust is often presented on a `dry g a s'basis. For an accurate release rate, correct the stack or vent gasflow rate in Step 1fo r the moisture content in your facility's stack gas. This is done simply by multiplying the volumetricflow in Step 1 by the term (1 -fraction o f water vapor). The dry gas volumetricflow rate can then be multiplied by the concentration o f dioxin and dioxin-like compounds measured in the stack gases (see Step 3). 21 Dry volume ticflow = (volumetricflow ) x(1 - fraction ofwater) Dry volumetricflo w (corrected)= (5.7 m3 / s) x (1 - 0.10) = 5.13 m3 / s Step 3. Estimate annual stack emissions to air. R air = C X V x CF x H x {units conversion factor} Where: Rair= Annual release o f dioxin and dioxin-like compounds to air (g /yr) C= Combustion flue gas concentration o f D&DLC (ng/dry standard cubic meter) V = Hourly Volumetricflow rate o f combustionflue gas (dscm/hour) (20oC, 1 atm; adjusted to 7% O2) CF= Capacityfactor, fraction o f time that thefacility operates on an annual basis (e.g., 0.85) H= Total hours in a year (8,760 hr/yr) 10 ng RD = x ds< Rair = 1.38 g / y r 5.13 dscm s 3600 s xx hr 8760 h r 1 x (0.85) x g yr J 10 ng) Section 3.1.2. Example of Calculating Water Releases Using NPDES Monitoring Data Example: Yourfacility is subject to NPDES permits fo r the discharge o f dioxin and dioxin-like compounds into surface waters. You are required to conductperiodic monitoring o f the effluent discharge from your facility. In this example, quarterly samples were taken to be analyzedfo r the content o f dioxin and dioxin-like compounds. Each sample was an hourly, flowrate-based composite taken fo r one day to be representative o f the discharge fo r that day. The total effluent volume fo r that day was also recorded. Yourfacility operates 350 days/year. Thefollowing data were collected on each sample day. Quarter sample number 1 2 3 4 Discharge flow rate (106 gal/day) 20 20 40 100 Dioxin and dioxin-like compounds concentration (picograms per liter (pg/L)) 10 10 10 10 22 To calculate the amount of dioxin and dioxin-like compounds discharged on each sample day, the concentration of dioxin and dioxin-like compounds in the discharge is multiplied by the discharge flow rate for that day, as shown below for the first quarter sample. Step 1: Calculate the am ount of dioxin and dioxin-like compounds discharged per day from each day of sampling. Amount of dioxin and dioxin-like compounds/day = (daily effluent flow rate) x (dioxin and dioxin-like compounds concentration in effluent). From the table above, the calculation of daily dioxin and dioxin-like compounds effluent discharge for the first sampling quarter is: First Quarter Discharge First Quarter Discharge 10 p g x 1 g x 3.8 L | x I20 x 106 gal | L 11012 p gj ' l gal j ~ [ day 0.00076 g dioxin and dioxin-like compounds/ day Step 2: Find the average amount of dioxin discharged in effluent/day Using the same equation, the second, third and forth quarter dioxin and dioxin-like compounds monitoring events are calculated to be 0.00076 g/day; 0.0015 g/day; and 0.0038 g/day, respectively. Then the average daily dioxin and dioxin-like compounds discharge rate for all monitoring events at this facility is: I 0.00076 + 0.00076 + 0.0015 + 0.0038 | Average daily discharge = i ---------------------------------------------------- 1g / day l 4 sampling periods j Average daily dioxin and dioxin - like compounds discharge = 0.0017 g / day Step 3 Calculate the annual discharge of dioxin to surface waters Your facility operates 350 days/year. The estimated annual discharge of dioxin and dioxin-like compounds is calculated as follows: A n n u a l D ischarge o f D & D L C to Surface Water = j 350 day !>x j -0017g 1 l y r j l day j A nnual Dioxin and D io xin -like Compounds Discharge to Surface Water = 0.6 g / y r Section 3.1.3. Exam ple of Estim ating Releases to L and Under EPCRA section 313, the disposal of toxic chemicals in on-site landfills constitutes a release to land. Waste contaminated with dioxin and dioxin-like compounds may be placed in a RCRA 23 subtitle C landfill for disposal. The following is an example of calculating the annual quantity of dioxin and dioxin-like compounds disposed in a RCRA subtitle C landfill. Example: Land disposal o f sludge. Yourfacility generates approximately 1 kg o f dry sludge per 4000 L o f wastewater treated at thefacility's on-site industrial wastewater treatment plant. Thefacility operations produce approximately 100 million L o f wastewater per day. Monitoring results indicate that the sludge, on average, contains approximately 3 ng dioxin and dioxin-like compounds per kg dry sludge produced. All o f the sludgefrom yourfacility is placed in an on-site RCRA subtitle C landfill. Thefacility operates 350 days per year. What is the annual amount o f dioxin and dioxin-like compounds released to landfrom yourfacility as a function o f land disposal o f the sludge contaminated with dioxin and dioxin-like compounds? Step 1: Determine the amount of sludge produced per day from the wastewater treatment process. Trrotwal S0l7udJge nGenera*teda = \\[ ------1--k--g--s-l-u--d--g-e-----4000 L wastewater 1\J x \I\-1--x--1-0--8--L--d-w-a-ay-s--t-e-w--a--t-e-r- Total Sludge Generated = 25,000 kg / day Step 2: Determine the amount of dioxin and dioxin-like compounds contained in the sludge produced each day. Total amount o f D & D LC in sludge = Total sludge generatedx average D & D LC concentration in sludge Total amount o f D & D LC in sludge = 25,000 kg sludge 1 x \ 3 ng D& DLC 1 x J J ^day | kg o f sludge 109 ngJ Total amount o f dioxin and dioxin - like compounds in sludge = 0.000075 g / day 24 Step 3 Calculate the annual release of dioxin and dioxin-like compounds to land based on annual days of operation per year Annual release o f dioxin and dioxin-like compounds to land = average daily D& DLC loading in sludge x total operating days p er year. Annual release o f dioxin and dioxin-like compounds to land = 7.5x10-5 g D & D LC day i 350 operating days 1 [ year \ Annual release o f dioxin and dioxin-like compounds to land = 0.03 g / y r Section 3.2. Examples of Estimating Releases Using Emission Factors You have either developed your own facility-specific emission factors or have decided to use EPA's default emission factors (refer to Section 4.0; EPA Default Emission Factors) to estimate annual releases of dioxin and dioxin-like compounds from your facility to air, land and water. Emission factors (EF) relate potential release of dioxin and dioxin-like compounds to the activity level of your facility. The units vary according to the units of measure of activity level, but usually are weight per unit weight of production or weight per unit volume related to production. A common EF for combustion processes is ng dioxin and dioxin-like compounds per kg material combusted, processed, or produced. A common EF for point source effluent discharges into surface waters is pg dioxin and dioxin-like compounds per L of wastewater discharged. A common EF for RCRA waste generated that will be disposed is pg dioxin and dioxin-like compounds per kg of waste or sludge generated. The following serve as examples of how to make calculations of annual releases of dioxin and dioxin-like compounds using either your own chosen emission factors or EPA default emission factors. In either case, the procedures are the same. Section 3.2.1. Example of Estimating Air Releases Example: The emission factor that bestfits your facility is 10 ng dioxin and dioxin-like compounds releasedfrom the stackper kg o f materials processed. Each day your facility processes 25,000 kg o f materials, andyour facility operates 350 days per year. The emission factor is appropriate fo r your level o f dioxin and dioxin-like compounds control. Estimate the annual release o f dioxin and dioxin-like compoundsfrom the stack o fyour facility. 25 Solution: Ratr = A x EF Where: Rair = annual release o f dioxin and dioxin-like compounds to air; (g / yr) A = materialprocessed annually; (kg/yr) EF = dioxin and dioxin-like compounds emissionfactor; (ng/kg) I25,000 kg materials I 1350 days I 110 ng D& D L C I Rair l day \ [ year \ [ kg materials \ Rair 0.09 g dioxin and dioxin-like compounds/ year g 109ng Section 3.2.2. Example of Estimating Water Releases Example: Yourfacility discharges 100 million gallons per day o f treated wastewater into surface water. The emissionfactor you have found to be most appropriate fo r your facility is 10 p g dioxin and dioxin-like compounds per liter o f wastewater discharged. The emissionfactor reflects the level o f dioxin and dioxin-like compounds control that is occurring at yourfacility. Yourfacility operates 365 days each year. Estimate the annual release o f dioxin and dioxin-like compounds to surface water. Solution: 100 x 106 gal wastewater | | 3.78 L [ | 365 days R x i fx day ] l gal yr x 110pgD&DLC| x g l L wastewater \ 1012p g R 1.4 g dioxin and dioxin - like compounds / y r Section 3.2.3. Example of Estimating Releases to Land Example: In the example above, the wastewater treatment plant process generates 1 kg o f dry sludge per 5000 L o f wastewater treated. The wastewater treatment process removes 50% o f the dioxin and dioxin-like compoundsfrom the wastewater prior to discharging wastewater into surface water. All o f the sludge generated at your facility is placed in an on-site RCRA subtitle C landfill. Calculate how much dioxin and dioxin-like compounds are released to land at yourfacility. 26 Step 1. Determine the amount of sludge generated each day at your facility. Sludge generated = sludge generation rate per L wastewater x wastewater per day SOlIud,ge generated, = if-----1--k-2g-s--l-u-d2g-e-----1> x i 1--3-.-7-8--x---1--0-8-L---w--a--s-t-e-w--a--t-e-r- [5000 L wastwater J [ day Sludge generated = 7.56 x 104 kg / day Step 2. Estimate the Emission Factor (EF) for dioxin and dioxin-like compounds in the sludge If it is assumed that all the dioxin and dioxin-like compounds that are removed from the wastewater during the treatment process are contained in the sludge generated from the wastewater treatment process, then the EF for sludge can be calculated as a function of dioxin and dioxin-like compounds removal efficiency from the wastewater. Thus the EF for dioxin and dioxin-like compounds in wastewater times the removal efficiency gives an approximate indication of the dioxin and dioxin-like compounds EF for sludge at your facility. In the following calculation, assume the density of sludge = 500 g/ L. E Fsludge I|_E Fwasttewatter x {\ 1 - Jfr a c tio n D & D L C r e m o v e d)}\I x d e n s it.y /ojf s lou d g e x u n its c o n v e r s io n jfa c to r s EFssludge 10pg D & D LC L w astew ater x {1-.5} 1 L 1 0 3g xx ~500g kg E F sludge = 10 p g d io x in a n d d io x in - lik e c o m p o u n d s / kg Step 3. Calculate the annual release of dioxin and dioxin-like compounds to land quantity sludge | operating days R'land day x {IEFs,lud,ge}\ x year R land 7.56 x 104 kg sludge 10 p g D & D LC >A 4 >A i g 365 days >A i day kg sludge [1012p g \ year J Rland 3 x 1 0 4 g dioxin and dioxin - like compounds / year 27 Section 4.0. FACILITY-SPECIFIC EPA DEFAULT EMISSION FACTORS EPA is providing default emission factors for facilities to use, at their discretion, in reporting annual releases and other waste management quantities of dioxin and dioxin-like compounds. You are encouraged, however, to use site-specific information on releases from your facility. EPA recognizes that emissions and environmental release data are not available in most cases. This guidance is providing a series of `look-up' tables to assist you in meeting the requirements of annually reporting releases of dioxin and dioxin-like compounds. Information is limited to those source categories for which EPA believes sufficient information is available to develop default emission factors that can be used to make reasonable estimations of releases. The documentation for the derivation of the emission factors can be found in three EPA references (available in pdf format at: http://www.epa.gov/tri/): EPA's Database of Sources of Environmental Releases of Dioxin-Like Compounds in the United States. U.S. Environmental Protection Agency, National Center for Environmental Assessment, Office of Research and Development, Washington, DC 20460, EPA/600/P-98/002B, September, 2000. The Inventory of Sources of Dioxin in the United States, U.S. Environmental Protection Agency, National Center for Environmental Assessment, Office of Research and Development, Washington, DC 20460, EPA/600/P-98/002Aa. Estimating Exposure to Dioxin-Like Compounds; Volume 2: Sources o fDioxin-Like Compounds in the United States, EPA/600/)-00/001, Draft Final, September, 2000. In applying these default emission factors, you are encouraged to read the summary description provided for the facilities that were used to derive the default emission factors. Facilities should use those emission factors that match as closely as practical the class type and pollution control systems of your facility. Although EPA's default emission factors are arithmetic averages of environmental releases from tested facilities, EPA recognizes that these tested facilities may not be an ideal match to your facility. The decision to use EPA default emission factors is best left to the operator of the facility. This guidance is intentionally made to be flexible in the use and selection of emissions of dioxin and dioxin like compounds that are most representative of emissions from your facility. All of the emission factors contained in the tables in this section are for controlled conditions. In all of the emission factors tables the emission factor for the dioxin and dioxin-like compounds category is equal to the sum of the emission factors for the 7 dibenzo-p-dioxins (CDDs) covered by the category and the 10 dibenzofurans (CDFs) covered by the category. Thus, Dioxin and dioxin-like compounds = CDDs + CDFs 28 Section 4.1. Pulp and Paper Mills and Lumber and Wood Products Section 4.1.1. Applicability The following SIC Codes are included within this category: I. SIC Code 2611 Pulp M ills: Establishments primarily engaged in manufacturing pulp from wood or from other materials, such as rags, linters, wastepaper, and straw. Establishments engaged in integrated logging and pulp mill operations are classified according to the primary products shipped. Establishments engaged in integrated operations of producing pulp and manufacturing paper, paperboard, or products thereof are classified in Industry 2621 if primarily shipping paper or paper products; in Industry 2631 if primarily shipping paperboard or paperboard products; and in Industry 2611 if primarily shipping pulp. II. 2621 Paper Mills: Establishments primarily engaged in manufacturing paper from woodpulp and other fiber pulp, and which may also manufacture converted paper products. Establishments primarily engaged in integrated operations of producing pulp and manufacturing paper are included in this industry if primarily shipping paper or paper products. Establishments primarily engaged in manufacturing converted paper products from purchased paper stock are classified in Industry Group 265 or Industry Group 267. III. 2400 Lumber and Wood Products. Except Furniture: Establishments primarily engaged in cutting timber and pulpwood; merchant sawmills, lath mills, shingle mills, cooperage stock mills, planing mills, and plywood mills and veneer mills engaged in producing lumber and wood basic materials. Also included within this SIC code are establishments engaged in manufacturing finished articles made entirely or mainly of wood or related materials. Major Group 24 includes Industry Groups 241, 242, 243, 244, 245, and 249. Furniture and office and store fixtures are classified in Major Group 25. Woodworking in connection with construction, in the nature of reconditions and repair, or performed to individual order, is classified in nonmanufcturing industries. Industry Group 241 2411 Logging Industry Group 242 2421 Sawmills and Planing Mills 2431 Millwork 2434 Wood Kitchen Cabinets 2435 Hardwood Veneer and Plywood 2436 Softwood Veneer and Plywood Industry Group 244 2441 Nailed and Lock Corner Wood Boxes and Shook 2448 Wood Pallets and Skids 2449 Wood Containers 29 Industry Group 245 2451 Mobile Homes 2452 Prefabricated Wood Buildings and Components Industry Group 249 2491 Wood Preserving 2493 Reconstituted Wood Products 2499 Wood Products Section 4.1.2. Emission Factors for Releases to W ate r From Bleached Chemical Pulp Mills On April 15, 1998 and August 7, 1998, EPA promulgated final effluent standards (Federal Register, 1998) under the Clean Water Act for pulp and paper mills (63 FR 18504-18751, and 63 FR 42238-42240). Mills subject to regulation are pulp mills and integrated mills (mills that manufacture pulp and paper/paperboard), that chemically pulp wood fiber (using kraft, sulfite, soda, or semi-chemical methods); that produce pulp secondary fiber; pulp non-woody fiber; and mechanically pulp wood fiber. The regulations established dioxin discharge limits for bleached chemical pulp mills. In reporting releases of dioxin and dioxin-like compounds to surface waters, the facility may use the EPA default emission factors in Table 4-1, which were developed for bleached chemical pulp mills. The data were generated at a series of eight bleached chemical pulp mills prior to promulgation of the effluent standards. 30 Table 4-1. Average Emission Factors (pg/L) for Estimating Wastewater Discharges of Dioxin and Dioxin-like Compounds into Surface Water From Bleached Chemical Pulp Mills CDD Mean Emission Factor (pg/L) CDF Mean Emission Factor (pg/L) 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 1.2 2,3,7,8-TCDF 0 1,2,3,7,8-PeCDF 0 2,3,4,7,8-PeCDF 0 1,2,3,4,7,8-HxCDF 0 1,2,3,6,7,8-HxCDF 3.2 1,2,3,7,8,9-HxCDF 99.0 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF 1,2,3,4,6,7,8,9-OCDF 2.3 0 0 0 0 0 0 0 0 0 CDDs 103.4 pg /L CDFs 2.3 pg /L Dioxin and dioxin like compounds* 105.7 pg/L Source: Gillespie, 1997; * D ioxin and dioxin-like compounds = CDDs + CDFs Section 4.1.3. Emission Factors for Releases to Land From Bleached Chemical Pulp Mills The conventional wastewater treatment of effluents results in the generation of wastewater sludge. If your facility applies the sludge to land, or places it in a RCRA subtitle C landfill for disposal, then the default emission factors for bleached chemical pulp mills in Table 4-2 apply. These emission factors are based on data from a series of the same bleached chemical pulp mills referenced in section 4.1.2. 31 Table 4-2. Average Emission Factors (ng/kg) for Land Disposal of Dioxin and Dioxin-like Compounds in Wastewater Sludge from Bleached Chemical Pulp Mills. CDD Mean Emission Factor (ng/kg) CDF M ean Emission Factor (ng/kg) 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 0.8 0 0.5 2.3 1.6 41.4 445.0 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 6.2 0 0.5 0 0 0 0.5 1.2 0 0 CDDs 491.6 ng /kg CDFs 8.4 ng /kg Dioxin and dioxin-like compounds* 500 ng/kg Source: Gillespie, 1997; * Dioxin and dioxin-like compounds = Sum of CDDs + CDFs Section 4.1.4. Emission Factors for Releases to A ir From Pulp Mill or Lum ber and Wood Products Facilities Wood waste and bark produced from processing timber at a pulp mill or lumber and wood products facility are burned in the facilities' bark and/or wood-waste boilers (NCASI, 1995). This wood waste can produce CDDs/CDFs during combustion. If your lumber and wood products industry facility burns wood waste and bark, then the default emission factors in Table 4-3 apply. 32 Table 4-3. Average Emission Factors (ng/kg) for A ir Releases of Dioxin and Dioxin like Compounds from the Combustion of Wood W aste and B ark (as fired) at Pulp Mill or Lum ber and Wood Product Industry Facility Boilers. CDD 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 Mean Emission Factor (ng/kg) 0.005 0.005 0.012 0.050 0.035 0.300 1.200 CDF 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 CDDs 1.6 ng /kg CDFs Dioxin and dioxin-like compounds* 2.4 ng/kg Source: NCASI (1995); *Dioxin and dioxin-like compounds = Sum o f CDDs + CDFs Mean Emission Factor (ng/kg) 0.104 0.022 0.020 0.070 0.043 0.036 0.004 0.274 0.081 0.187 0.84 ng /kg Section 4.2. Secondary Smelting and Refining of Nonferrous M etals Section 4.2.1. Applicability SIC Code 3341, Secondary Smelting and Refining of Nonferrous Metals, include establishments primarily engaged in recovering nonferrous metals and alloys from new and used scrap and or in producing alloys from purchased refined metals. This industry includes establishments engaged in both the recovery and alloying of precious metals. Plants engaged in the recovery of tin through secondary smelting and refining, as well as by chemical processes, are included in this industry. Establishments primarily engaged in assembling, sorting, and breaking up scrap metal, without smelting and refining, are classified in Wholesale Trade, Industry 5093. Applicable facilities include: Aluminum smelting and refining, secondary Copper smelting and refining, secondary Lead smelting and refining, secondary Nonferrous metal smelting and refining, secondary Recovering and refining of nonferrous metals Secondary refining and smelting of nonferrous metals 33 Section 4.2.2. Secondary Aluminum Smelters Stack tests from five secondary aluminum facilities (described below) were used by EPA to derive mean air emission factors of dioxin and dioxin-like compounds. Secondary aluminum smelters reclaim aluminum from scrap containing aluminum. This recycling involves two processes -- pre cleaning and smelting. Both processes may produce CDD/CDF emissions. Pre-cleaning processes involve sorting and cleaning scrap to prepare it for smelting. Cleaning processes that may produce CDD/CDF emissions use heat to separate aluminum from contaminates and other metals; these techniques are roasting and sweating. Roasting uses rotary dryers with a temperature high enough to vaporize organic contaminants, but not high enough to melt aluminum. An example of roasting is the delacquering and processing of used beverage cans. Sweating involves heating aluminum-containing scrap metal to a temperature above the melting point of aluminum, but below the melting temperature of other metals such as iron and brass. The melted aluminum trickles down and accumulates in the bottom of the sweat furnace and is periodically removed (U.S. EPA, 1997). After pre-cleaning, the treated aluminum scrap is smelted and refined. This usually takes place in a reverberatory furnace. Once smelted, flux is added to remove impurities. The melt is "demagged" to reduce the magnesium content of the molten aluminum by the addition of chlorine gas. The molten aluminum is transferred to a holding furnace and alloyed to final specifications (U.S. EPA, 1997). CDD/CDF emissions to air have been measured at five U.S. secondary aluminum operations. These facilities were tested in 1995. The tests were conducted by EPA in conjunction with the Aluminum Association for the purpose of identifying emission rates from facilities with potentially maximum achievable control technology (MACT)-grade operations and air pollution control device (APCD) equipment. The first facility tested in 1995 was a top charge melt furnace (Advanced Technology Systems, Inc., 1995). During testing, the charge material to the furnace was specially formatted to contain no oil, paint, coatings, rubber, or plastics (other than incidental amounts). The CDD/CDF emissions from such a clean charge, 0.26 ng toxic equivalents (TEQ)/kg charge material, would be expected to represent the low-end of the normal industry range. The second facility operates a sweat furnace to preclean the scrap and a reverberatory furnace to smelt the pre-cleaned aluminum (U.S. EPA, 1995). Stack emissions are controlled by an afterburner operated at 1,450* F. The third facility employs a crusher/roasting dryer as a pre-cleaning step followed by a reverberatory furnace (Galson Corporation, 1995). The emissions from the two units are vented separately. The exhaust from the crusher/dryer is treated with an afterburner and a baghouse. The exhaust from the furnace passes through a baghouse with lime injection. 34 The fourth facility operates a scrap roasting dryer followed by a sidewell reverberatory furnace (Roy Weston, 1996). The emissions from the two units are vented separately. Exhaust from the dryer passes through an afterburner and a lime-coated baghouse. The exhaust from the furnace passes through a lime-coated baghouse. The fifth facility is a dryer/delacquerer secondary aluminum facility tested by Commonwealth Aluminum Corporation (1995). The results of this test were submitted to EPA as part of the public comments by the industry in association with development of the MACT standard. Table 4-4 summarizes average default emission factors (ng/kg scrap aluminum processed) for estimating air releases of dioxin and dioxin-like compounds from secondary aluminum smelters. For the default emission factor, EPA is recommending 44.55 ng dioxin and dioxin-like compounds emitted per kg of aluminum scrap processed. This is based on an arithmetic average of the five tested facilities presented in the Table. As an alternative to using this default emission factor, the owner or operator of secondary aluminum facilities may review the individual test reports supporting the development of the table (see references), and, based on good engineering judgement, decide the most appropriate emission factors for your facility. Defaults are given here in the context of providing an option for estimating air releases from secondary aluminum smelters. 35 Table 4-4. Average Emission Factors (ng/kg scrap alum inum processed) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Secondary Aluminum Smelters 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 Dioxin and Dioxin Like Compounds Mean emission factors of dioxin and dioxin-like compounds Mean Facility Emission Factor (ng/kg scrap feed) (Ref. 1) ND 0.02 0.05 0.13 0.15 0.51 0.42 0.44 0.06 0.17 0.32 0.11 0.02 0.30 0.07 0.03 0.30 3.1 44.55 Mean Facility Emission Factor (ng/kg scrap feed) (Ref. 2) 0.13 0.39 0.24 0.86 1.26 7.67 14.97 0.74 1.51 2.44 2.44 2.69 1.02 3.82 11.39 5.50 30.40 87.47 Mean Facility Emission Factor (ng/kg scrap feed) (Ref. 3) 0.51 1.19 1.35 1.52 2.51 2.60 1.01 14.20 10.47 11.06 21.84 7.10 0.47 7.09 14.61 1.21 3.15 101.89 Mean Facility Emission Factor (ng/kg scrap feed) (Ref. 4) 0.25 0.75 0.53 0.65 1.29 2.84 NA 5.50 1.90 3.18 4.65 1.48 0.08 1.87 2.97 0.24 1.04 29.22 Mean Facility Emission Factor (ng/kg scrap feed) (Ref. 5) 0.01 0.02 0.02 0.03 0.05 0.1 NA 0.08 0.07 0.12 0.16 0.06 0.01 0.08 0.17 0.04 0.06 1.08 TEQ calculations assume not-detected values are zero. NA= Not available. ND = Not detected (value in parenthesis is the emission at the detection limit). Sources: Ref. 1: Advanced Technology Systems, Inc. (1995) Ref. 2: U.S. EPA (1995h) Ref. 3: Galson Corporation (1995) Ref. 4: Roy Weston, Inc. (1996) Ref. 5: Commonwealth Aluminum Corp (1995) 36 Section 4.2.3. Secondary Lead Smelters The secondary lead smelting industry produces elemental lead through the chemical reduction of lead compounds in a high temperature furnace (1,200 to 1,260* C). Smelting is performed in reverberatory, blast, rotary, or electric furnaces. Blast and reverberatory furnaces are the most common types of smelting furnaces used by the 23 facilities that comprise the current secondary lead smelting industry in the United States. O f the 45 furnaces at these 23 facilities, 15 are reverberatory furnaces, 24 are blast furnaces, five are rotary furnaces, and one is an electric furnace. The one electric furnace and 11 of the 24 blast furnaces are co-located with reverberatory furnaces, and most share a common exhaust and emissions control system (U.S. EPA, 1994b). Furnace charge materials consist of lead-bearing raw materials, lead-bearing slag and drosses, fluxing agents (blast and rotary furnaces only), and coke. Scrap motor vehicle lead-acid batteries represent about 90 percent of the lead-bearing raw materials at a typical lead smelter. Fluxing agents consist of iron, silica sand, and limestone or soda ash. Coke is used as fuel in blast furnaces and as a reducing agent in reverberatory and rotary furnaces. Organic emissions from co-located blast and reverberatory furnaces are more similar to the emissions of a reverberatory furnace than the emissions of a blast furnace (U.S. EPA, 1994b). Historically, many lead-acid batteries contained PVC plastic separators between the battery grids. These separators are not removed from the lead-bearing parts of the battery during the battery breaking and separation process. When the PVC is burned in the smelter furnace, the chlorine atoms are released as HCl, C12, and chlorinated hydrocarbons (Federal Register, 1995d). The source of CDDs/CDFs at secondary lead smelters is the PVC separator (U.S. EPA, 1995c). In 1990, about 1 percent of scrap batteries processed at lead smelters contained PVC separators. In 1994, less than 0.1 percent of scrap batteries contained PVC separators. This trend is expected to continue because no U.S. manufacturer of lead-acid automotive batteries currently uses PVC in production (U.S. EPA, 1995c; Federal Register, 1995d). The total current annual production capacity of the 23 companies currently comprising the U.S. lead smelting industry is 1.36 million metric tons. Blast furnaces not co-located with reverberatory furnaces account for 21 percent of capacity (or 0.28 million metric tons). Reverberatory furnaces and blast and electric furnaces co-located with reverberatory furnaces account for 74 percent of capacity (or 1.01 million metric tons). Rotary furnaces account for the remaining 5 percent of capacity (or 0.07 million metric tons). Actual production volume statistics by furnace type are not available. However, if it is assumed that the total actual production volume of the industry, 0.97 million metric tons in 1995 (U.S. Geological Survey, 1997a) and 0.72 million metric tons in 1987 (U.S. EPA, 1994a), are reflective of the production capacity breakdown by furnace type, then the estimated actual production volumes of blast furnaces (not co-located), reverberatory and co-located blast/electric and reverberatory furnaces, and rotary furnaces were 0.20, 0.72, and 0.05 million metric tons, respectively, in 1995, and 0.15, 0.53, and 0.04 million metric tons, respectively, in 1987. In 1987, the industry consisted of 24 facilities. 37 CDD/CDF emission factors can be estimated for lead smelters based on the results of emission tests performed by EPA at three smelters (a blast furnace, a co-located blast/reverberatory furnace, and a rotary kiln furnace) (U.S. EPA, 1992e; 1995d; 1995e). The air pollution control systems at the three tested facilities consisted of both baghouses and scrubbers. Congener-specific measurements were made at the exit points of both APCD exit points at each facility. Table 4-5 presents the congener emission factors from the baghouse and the scrubber for each site. Although all 23 smelters employ baghouses, only 9 employ scrubber technology. Table 4-5. Average Emission Factors (ng/kg) for Estim ating A nnual Releases of Dioxin and Dioxin-Like Compounds from Secondary Lead Smelters CDD/CDF Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD 1,2,3,4,6,7,8,9-OCDD CDDs 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 Blast Furnace (ng/kg lead produced) before after scrubber scrubber 2.11 0.25 0.99 0.03 0.43 0.00 0.99 0.03 1.55 0.03 2.06 0.08 1.40 0.39 9.53 0.81 Blast/reverb (ng/kg lead produced) before after scrubber scrubber 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.06 0.57 0.55 0.67 0.61 Rotary kiln (ng/kg lead produced) before scrubber 0.10 0.01 0.00 0.00 0.00 0.00 0.24 0.35 after scrubber 0.24 0.00 0.00 0.00 0.00 0.22 2.41 2.87 8.73 0.93 1.46 0.49 0.40 1.20 3.88 0.43 0.24 0.02 0.14 0.40 6.65 0.36 0.31 0.00 0.14 0.46 5.83 0.37 0.63 0.00 0.11 0.27 1.67 0.11 0.19 0.00 0.02 0.10 0.11 0.00 0.00 0.00 0.04 0.13 2.06 0.11 0.15 0.00 0.00 0.00 2.34 0.19 0.48 0.00 0.03 0.13 0.63 0.06 0.00 0.00 0.00 0.00 1.39 0.18 0.29 0.00 0.00 0.00 CDFs 33.29 2.74 3.75 0.51 0.88 2.69 Dioxin and dioxin-like compounds* 42.82 3.55 4.42 1.12 1.23 5.56 * Dioxin and dioxin-like compounds = CDDs + CDFs 38 Facilities that employ scrubbers account for 14 percent of the blast furnace (not co-located) production capacity, 52 percent of the reverberatory and co-located furnace production capacity, and 57 percent of the rotary furnace production capacity. From the reported data, congener-specific CDD/CDF emission factors (ng /kg lead processed) for each of the three furnace configurations are presented in Table 4-5. The range reflects the presence or absence of a scrubber. Note that calculations using emission factors before scrubbers would apply towards threshold calculations since this represents amounts that have been manufactured. They can also be used to estimate the amounts that a scrubber has removed and then the amounts removed, depending on how the scrubber material is handled, should be reported in the appropriate section of the Form R. As discussed earlier in this section, the PVC separators used historically in lead-acid batteries are believed to be the source of the CDD/CDFs observed in emissions from secondary lead smelters. PVC separators are no longer used in the United States in the manufacture of lead-acid batteries, and less than 0.1 percent of the scrap batteries in 1994 contained PVC separators (U.S. EPA, 1995c; Federal Register, 1995c). EPA predicts that by the time existing smelters demonstrate compliance in 1997 with the National Emission Standards for Hazardous Air Pollutants (NESHAP) for secondary lead smelters promulgated by EPA (Federal Register, 1995c), batteries containing PVC will only be present in the scrap battery inventory in trace amounts, resulting at most, in only trivial amounts of HCl or Cl2 air emissions. Section 4.2.4. Secondary C opper Smelters/Refiners Secondary copper smelting is part of the scrap copper, brass, and bronze reprocessing industry. Brass is an alloy of copper and zinc; bronze is an alloy of copper and tin. Facilities in this industry fall into three general classifications: secondary smelting, ingot making, and remelting. Similar process equipment may be used at all three types of facilities, so that the distinguishing features are not immediately apparent (U.S. EPA, 1994c). The feature that distinguishes secondary smelters from ingot makers and remelters is the extent to which pyrometallurgical purification is performed. A typical charge at a secondary smelter may contain from 30 to 98 percent copper. The secondary smelter upgrades the material by reducing the quantity of impurities and alloying materials, thereby increasing the relative concentration of copper. This degree of purification and separation of the alloying constituents does not occur at ingot makers and remelters. Feed material to a secondary copper smelter is a mixture of copper-bearing scrap comprised of such scrap as tubing, valves, motors, windings, wire, radiators, turnings, mill scrap, printed circuit boards, telephone switching gear, and ammunition casings. Non-scrap items like blast furnace slags and drosses from ingot makers or remelters may represent a portion of the charge. The secondary smelter operator uses a variety of processes to separate the alloying constituents. Some purify the scrap in the reductive atmosphere of a blast furnace. The charge may be subsequently purified in the oxidizing atmosphere of a converter. Other secondary smelters perform all purification by oxidation in top-blown rotary converters or in reverberatory furnaces (U.S. EPA, 1994c). 39 The ingot makers blend and melt scrap copper, brass, and bronze of various compositions to produce a specification brass or bronze ingot. When necessary, the ingot makers add ingots of other metals (e.g., zinc or tin) to adjust the metallurgy of the final product. The feed materials for ingot makers contain relatively high amounts of copper. Examples of feed materials include copper tubing, valves, brass and bronze castings, ammunition shell casings, and automobile radiators. "Fire-refined" anode copper or cathode copper may also be charged. Items such as motors, telephone switchboard scrap, circuit board scrap, and purchased slags are not used by ingot makers. The reductive step (melting in a reducing atmosphere, as in a blast furnace) that some secondary smelters employ is not used by ingot makers. Ingot makers do, however, use some of the other types of furnaces used by secondary smelters, including direct-fired converters, reverberatory furnaces, and electric induction furnaces (U.S. EPA, 1994c). Remelting facilities do not conduct any substantial purification of the incoming feeds. These facilities typically just melt the charge and cast or extrude a product. The feeds to a remelter are generally alloy material of approximately the desired composition of the product (U.S. EPA, 1994c). In 1991, stack testing of the rotary furnace stack emissions of a secondary smelter located in Alton, Illinois (Chemetco, Inc.) was conducted by Sverdrup Corp. (1991). The Chemetco facility uses four tap down rotary (i.e., oxidizing) furnaces. Furnace process gas emissions are controlled by a primary quencher and a venturi scrubber. The feed is relative high purity copper scrap containing minimal plastics, if any. The same manufacturing process and APCD equipment were in place in 1987 and 1995 (U.S. EPA, 1994c). This facility operated under oxidizing rather than reducing conditions and processes relatively high purity scrap, the potential for CDD/CDF formation and release is expected to be dramatically different than that of the two tested facilities reported above. The estimated emission factors derived for this site from the results in Sverdrup (1991) are presented in Table 4-6. Although little research has been performed to define the CDD/CDF formation mechanism(s) in secondary copper smelting operations, two general observations have been made (Buekens et al., 1997). The presence of chlorinated plastics in copper scraps used as feed to the smelters is believed to increase the CDD/CDF formation. Second, the reducing or pyrolytic conditions in blast furnaces can lead to high CDD/CDF concentrations in the furnace process gases. 40 Table 4-6. CDD/CDF Emission Factors (ng Dioxin and Dioxin-like Compounds per kg copper scrap processed) for Secondary Copper Smelters Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD 1,2,3,4,6,7,8,9-OCDD CDDs 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 CDFs Chemetco Smelting (ng/kg scrap feed) ND (0.05) 0.21 0.39 0.70 1.26 8.95 22.45 33.96 2.11 1.47 2.63 7.30 2.15 4.06 0.27 11.48 2.74 21.61 55.82 Dioxin and dioxin-like compounds* 89.78 * Dioxin and dioxin-like compounds = CDDs + CDFs ND = Not detected (value in parenthesis is the emission at the detection limit). Source: Sverdrup (1991). It should be noted that a significant amount of scrap copper is consumed by other segments of the copper industry. In 1995, brass mills and wire-rod mills consumed 886,000 metric tons of copper base scrap; foundries and miscellaneous manufacturers consumed 71,500 metric tons (U.S. Geological Survey, 1997). As noted above, however, these facilities generally do not conduct any significant purification of the scrap. Rather, the scrap consumed is already of alloy quality and processes employed typically involve only melting, casting and extruding. Thus, the potential for formation of CDDs/CDFs is expected to be much less than the potential during secondary smelting operations. Table 4-6 is a listing of CDD/CDF default emissions factors for secondary copper smelters. In choosing the appropriate emission factor, the owner/operator is encouraged to exercise good engineering judgement to appropriately select the most suitable emission factors. Such judgement requires first-hand knowledge of your process. EPA believes that the most appropriate default emission factors are those derived from the stack testing of the Chemetco Smelting Facility as shown in 41 Table 4-6. This is because the state-of-the-art involved in secondary copper smelting calls for the mechanical removal of plastic material prior to smelting and refining, and to use copper-laden scrap that is relatively free of organic contamination. Therefore, if your facility processes copper scrap containing a relatively high amount of plastics, then the emission factors listed in Table 4-6 are not appropriate to use as default emission factors. Section 4.3. Cem ent Kilns Section 4.3.1. Applicability Kilns used in the pyroprosessing of Portland Cement clinker as defined in SIC Code 3241. Section 4.3.2. Sum m ary Description / A ir Emission Factors In the United States, the primary cement product is called Portland cement. Portland cement is a fine, grayish powder consisting of a mixture of four basic materials: limestone, silica, alumina, and iron compounds. Cement production involves heating (pyroprocessing) the raw materials (known as raw meal) to a very high temperature in a rotary (rotating) kiln to induce chemical reactions that produce a fused material called clinker. The cement clinker is further ground into a fine powder and mixed with gypsum to form the Portland cement. The cement kiln is a large, rotating steel cylindrical furnace lined with refractory material. The kiln is aligned on a slight angle, usually a slope of 3* - 6*. This allows for the materials to pass through the kiln by gravity. The upper end of the kiln is known as the cold or back end and this is where the raw materials, or meal, is generally fed into the kiln. The lower end of the kiln is known as the "hot" end. The hot end is where the combustion of primary fuels (coal, petroleum coke, natural gas, etc.) transpires to produce a high temperature. The cement kiln is operated in a counter-current configuration. This means that the hot combustion gases are convected up through the kiln while the raw materials are passing down toward the lower end. The rotation of the kiln induces mixing and the forward progress of mixed materials. As the meal moves through the cement kiln and is heated by the hot combustion gases, water is vaporized and pyroprocessing of materials occurs. When operating, the cement kiln can be viewed as consisting of three temperature zones necessary to produce clinker. Zone 1 is at the upper end of the kiln where the raw meal is added. Temperatures in this zone typically range from ambient up to 600* C. In this area of the kiln, moisture is evaporated from the raw meal. The second thermal zone is known as the calcining zone. Calcining occurs when the hot combustion gases from the combustion of primary fuels dissociates calcium carbonate from the limestone to form calcium oxide. In this region of the kiln, temperatures are in a range of 600* C to 900* C. The third region of the kiln is known as the burning or sintering zone. The burning zone is the hottest region of the kiln. In this region, temperatures in excess of 1,500* C induce 42 the calcium oxide to react with silicates, iron and aluminum in the raw materials to form clinker. The formation of clinker actually occurs near the lower end of the kiln (close to the combustion of primary fuel) where temperatures are the hottest. The chemical reactions that occur here are referred to as pyroprocessing. The clinker that leaves the hot end of the kiln is a gray-colored, glass-hard material comprised of dicalcium silicate, tricalcium silicate, calcium aluminate, and tetracalcium aluminoferrite. At this point, the clinker has a temperature of about 1,100* C. The hot clinker is then transferred into the clinker cooler. Once cooled, the clinker is ground into a fine powder and mixed with gypsum to produce Portland cement. Cement kilns are either wet or dry processes. In the wet process, the raw materials are ground and mixed with water to form a slurry. The meal-water slurry is fed into the kiln through a pump. A greater amount of heat energy is needed in the wet process to evaporate the additional water. In the dry process, the raw meal is ground to a fine, dry powder prior to entering the kiln. There are three types of dry processes: long-dry, preheater, and preheater/precalciner. Long dry kilns are similar to wet kilns, with the exception of the dry state of the raw materials. In preheater kilns, the raw material is heated prior to entering the kiln. This allows for a shorter kiln and lower combustion fuel use. Precalciners take this a step further by heating the raw feed to a level at which partial calcination takes place prior to entering the kiln. A typical preheater/precalciner kiln consists of a vertical tower containing a series of cyclone-type vessels. Raw meal is added at the top of the tower, and hot kiln exhaust flue gases from the kiln operation are used to preheat the meal prior to being introduced into the kiln. Preheating and precalcining the meal has the advantage of lowering fuel consumption of the kiln. There are also two primary types of air pollution control devices (APCDs) for the kiln: fabric filters and electrostatic precipitators (ESPs). Either of these can be used on any of the four process types. Cement manufacturing is an energy intensive manufacturing process. Fossil fuels are the primary sources of fuel. In addition, 15 cement plants in the U.S. currently supplement their fuel needs through the use of energy-bearing hazardous waste. For the last ten years, these facilities have been regulated by the Resource Conservation and Recovery Act's (RCRA) Boiler and Industrial Furnace (BIF) rules. As a result, a database has been developed characterizing emissions from these facilities. Testing and additional studies have contributed significantly to our understanding of dioxin formation in cement plants. In developing Maximum Achievable Control Technology (MACT) standards for cement plants, EPA "considered both hazardous waste burning cement kiln and non-hazardous waste burning cement kiln data together because both data sets are adequately representative of general dioxin/furan behavior and control in either type of kiln. This similarity is based on our engineering judgement that 43 hazardous waste burning does not have an impact on dioxin/furan formation, dioxin/furan is formed post-combustion." (See 64 FR 52876) APCD air inlet temperature (and the time that the air takes to enter the device) in conjunction with other site-specific elements is the determining factor. On June 14, 1999, EPA published a National Emission Standard for Hazardous Air Pollutants (NESHAP) for the Portland cement industry in the Federal Register (64 FR 31898). In addition, on September 30, 2000, EPA published a National Emission Standard for Hazardous Air Pollutants (NESHAP) for hazardous waste combustors (including cement kilns that recover energy from hazardous wastes) in the Federal Register (64 FR 52828). These rules require, among other things, that all cement plants periodically conduct dioxin/furan testing. The EPA source emissions data base contains test reports of CDD/CDF emissions from 15 cement kilns not burning hazardous waste. The average CDD/CDF emission factors displayed in Table 4-7 are derived as an average from these test data. These default emission factors are more appropriate for facilities tested in 1998, and do not reflect changes that have occurred since that time. As an operator/owner of a facility, you may elect to use more current information in the development of an emission factor, or you may elect to use the EPA default. If you elect to use more current emission factors, then you will be using Approach 2 (Section 2.1.2) to derive your emission estimate appropriate for your facility. 44 Table 4-7. Average Emission Factors (ng/kg of cement clinker produced) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Cement Kilns Not Combusting Hazardous W aste as Supplemental Fuel CDD Congener Emission Factor (ng/kg clinker) CDF Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD 1,2,3,4,6,7,8,9-OCDD 0.012 0.034 0.028 0.042 0.048 0.426 0.692 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 CDDs 1.28 CDFs Dioxin and dioxin-like compounds* 3.05 * Dioxin and dioxin-like compounds = CDDs + CDFs Emission Factor (ng/kg clinker) 0.729 0.102 0.224 0.185 0.054 0.007 0.082 0.146 0.005 0.234 1.77 Section 4.4. Utilities Section 4.4.1. Applicability This applies to SIC Codes 4911, 4931, and 4939 Electric Services. This guidance is for electric power utility boilers burning coal, wood and oil for the expressed purpose of producing steam to operate a steam generator, which, in turn, generates electricity. Section 4.4.2. Description/Emissions Factors for Coal-Fired Electric Utility Boilers In 1993, the U.S. Department of Energy (DOE) and the Electric Power Research Institute (EPRI) collaborated on assessing stack emissions of hazardous air pollutants at coal-fired power plants. As part of this project, CDD/CDF stack emissions were measured at seven U.S. coal-fired power plants (utility boilers). The levels reported for individual 2,3,7,8-substituted congeners were typically not detected or very low (i.e., 0.033 ng/Nm3). In general, CDF levels were higher than CDD levels. OCDF and 2,3,7,8-TCDF were the most frequently detected congeners. Variation in emissions between plants could not be attributed by Riggs et al. (1995) to any specific fuel or operational characteristic. The Electric Power Research Institute (EPRI) has published the results of the DOE/EPRI 45 cooperative testing of a total of eleven plants (EPRI, 1994). The average congener emission factors derived from this eleven facility data set, as reported in EPRI (1994), are presented in Table 4-8. Table 4-8. Average Emission Factors (ng/kg of coal combusted) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Coal-Fired Electric Utility Boilers CDD Congener Emission Factor CDF Congener (ng/kg coal) Emission Factor (ng/kg coal) 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 0.005 0 0 0.004 0.004 0.216 0.517 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF 1,2,3,4,6,7,8,9-OCDF 0.109 0.007 0.074 0.098 0.014 0.013 0.043 0.354 0.087 0.158 CDD 0.75 CDF 0.96 Dioxin and dioxin-like compounds* 1.71 * Dioxin and dioxin-like compounds = CDDs + CDFs. Assumes non-detects = 0. Source: EPRI (1994) - 11 facility data set. Section 4.4.3. Description/Emissions Factors for Oil-Fired Electric Utility Boilers Preliminary CDD/CDF emission factors for oil-fired utility boilers developed from boiler tests conducted over the past several years are reported in U.S. EPA (1995c). In 1993, the Electric Power Research Institute (EPRI) sponsored a project to gather information of consistent quality on power plant emissions. This project, the Field Chemical Emissions Measurement (FCEM) project, included testing of two cold side ESP-equipped oil-fired power plants for CDD/CDF emissions (EPRI, 1994). Table 4-9 presents CDD/CDF congener-specific emission factors (ng/L oil combusted) for oil-fired utility boilers. 46 Table 4-9. Average Emission Factors (pg/L oil combusted) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Oil-Fired Utility Boilers CDD Congener Emission Factor (pg /L oil) CDF Congener Emission Factor (pg /L oil) 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 24.7 63.3 65.8 79.7 477 2055 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 1,2,3,4,6,7,8,9OCDF 0 64.1 49.3 76.5 35.4 0 23.8 164 0 0 CDD 2,765.5 CDF 413.1 Dioxin and dioxin-like compounds* 3,178.6 * Dioxin and dioxin-like compounds = CDDs + CDFs Source: EPRI (1994) - based on two cold side ESP-equipped power plants. Calculation of emission factors assumes density of oil of 0.87 kg/L. Section 4.4.4. Description/Emissions Factors for W ood-Fired Electric Utility Boilers Congener-specific measurements of CDDs/CDFs in stack emissions from wood-fired electric utility boilers were measured by the California Air Resources Board at four facilities in 1988 (CARB, 1990b; CARB, 1990e; CARB, 1990f; CARB, 1990g). In CARB (1990b), CDDs/CDFs were measured in the emissions from a quad-cell wood-fired boiler used to generate electricity. The fuel consisted of coarse wood waste and sawdust from non-industrial logging operations. The exhaust gas passed through a multicyclone before entering the stack. In CARB (1990e), CDDs/CDFs were measured in the emissions from two spreader stoker wood-fired boilers operated in parallel by an electric utility for generating electricity. The exhaust gas stream from each boiler is passed through a dedicated electrostatic precipitator (ESP) after which the gas streams are combined and emitted to the atmosphere through a common stack. Stack tests were conducted both when the facility burned fuels allowed by existing permits and when the facility burned a mixture of permitted fuel supplemented by urban wood waste at a ratio of 70:30. In CARB (1990f), CDDs/CDFs were measured in the emissions from a twin fluidized bed combustors designed to burn wood chips for the generation of electricity. The APCD system consisted of ammonia injection for controlling nitrogen oxides, and a multiclone and 47 electrostatic precipitator for controlling particulate matter. During testing, the facility burned wood wastes and agricultural wastes allowed by existing permits. In CARB (1990g), CDDs/CDFs were measured in the emissions from a quad-cell wood-fired boiler. During testing, the fuel consisted of wood chips and bark. The flue gases passed through a multicyclone and an ESP before entering the stack. The mean of the emission factors derived from the four CARB studies is used in Table 4-10 as most representative of industrial wood combustion. Table 4-10. Average Emission Factors (ng/kg of wood combusted) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Wood-Fired Electric Utility Boilers CDD/CDF Congener Emission Factor ng/kg wood (dry wt) Emission Factor ng/kg wood (wet wt) 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD 1,2,3,4,6,7,8,9-OCDD 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF 1,2,3,4,6,7,8,9-OCDF 0.007 0.044 0.042 0.086 0.079 0.902 6.026 0.673 0.790 0.741 0.761 0.941 0.343 0.450 2.508 0.260 1.587 0.006 0.037 0.036 0.069 0.076 0.852 5.367 0.768 0.676 0.867 0.789 0.862 0.341 0.420 2.550 0.222 1.366 CDDs 7.19 CDFs 9.05 Dioxin and dioxin-like compounds* 16.24 * Dioxin and dioxin-like compounds = CDDs + CDFs 48 6.44 8.86 15.30 Section 4.5. H azardous W aste Combustion Section 4.5.1. Applicability This category applies to SIC Code 4953. In particular, this guidance is applicable to commercial hazardous waste combustors (RCRA Permitted Facilities), and to boilers and industrial furnaces (BIFs) burning hazardous waste. This also includes cement kilns burning hazardous waste as supplemental fuel (SIC Code 3241), and Utilities (SIC Codes 4911, 4931, and 4939) that burn hazardous waste as supplemental fuel in the boiler. Section 4.5.2. Emissions Factors for Commercial Boilers and Industrial Furnaces Burning Hazardous W aste (Other than Cement Kilns) In 1991, EPA established rules that allow the combustion of some liquid hazardous waste in industrial boilers and furnaces (Federal Register, 1991). These facilities typically burn oil or coal for the primary purpose of generating electricity. Liquid hazardous waste can only be burned as supplemental (auxiliary) fuel, and usage is limited by the rule to no more than 5 percent of the primary fuels. These facilities typically use an atomizer to inject the waste as droplets into the combustion chamber and are equipped with particulate and acid gas emission controls. In general, they are sophisticated, well controlled facilities, that achieve good combustion. Congener-specific emission concentrations for two tested boilers burning liquid hazardous waste as supplemental fuel are available (U.S. EPA, 1998). The average congener specific emission factors are presented in Table 4-11. These emission factors reflect testing at 2 of the 136 boilers/furnaces known to combust liquid hazardous waste as supplemental fuel. These facilities reflect emissions of dioxin-like compounds in 1995. 49 Table 4-11 Average Emission Factors (ng/kg waste feed) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Boilers and Industrial Furnaces Burning Hazardous W aste (other than cement kilns) CDD Congener Emission Factor CDF Congener (ng/kg waste feed) 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 2,3,7,8-TCDF 0.04 1,2,3,7,8-PeCDF 0.08 2,3,4,7,8-PeCDF 0.18 1,2,3,4,7,8-HxCDF 0.20 1,2,3,6,7,8-HxCDF 1.17 1,2,3,7,8,9-HxCDF 5.24 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 CDD 6.91 CDF Dioxin and dioxin-like compounds* 12.2 * Dioxin and dioxin-like compounds = CDDs + CDFs Emission Factor (ng/kg waste feed) 0.81 0.38 0.52 0.83 0.37 0.02 0.56 0.93 0.16 0.70 5.28 Section 4.5.3. Cem ent Kilns Burning H azardous W aste as Supplemental Fuel The high temperatures achieved in cement kilns make cement kilns an efficient technology for combusting hazardous waste as supplemental fuel. Sustaining the relatively high combustion temperatures (1,100* C to 1,500* C) that are needed to form cement clinker requires the burning of a fuel with a high energy output. Therefore, coal or petroleum coke is typically used as the primary fuel source. Because much of the cost of operating the cement kiln at high temperatures is associated with the consumption of fossil fuels, some cement kiln operators have elected to burn hazardous liquid and solid waste as supplemental fuel. Facilities that burn hazardous waste for energy recovery must comply with both RCRA and CAA regulations that specifically regulate this practice. Currently about 75 percent of the primary fuel is coal. Organic hazardous waste may have a similar energy output as coal (9,000 to 12,000 Btu/lb for coal). The strategy of combusting the waste as supplemental fuel is to off set the amount of coal/coke that is purchased and burned by the kiln. Much of the high energy and ignitable wastes are primarily comprised of such diverse substances as waste oils, spent organic solvents, sludges from the paint and coatings industry, waste paints and coatings from the auto and truck assembly plants, and sludges from the petroleum refining industry (Greer et al., 1992). The conditions inherent in the cement kiln mimic conditions of hazardous waste incineration. For example, the gas residence time in the burning zone is typically three seconds while at temperatures in excess of 1,500* C (Greer et al., 50 1992). In addition, trial bums have consistently shown that 99.99 to 99.9999 percent destruction and removal efficiencies for the very stable organic wastes can be achieved in cement kilns (Greer et al., 1992). Although the combustion of hazardous waste as supplemental or substitute fuel does have apparent advantages, only 16 percent of the Portland cement kilns (34 of the 212 kilns) combusted hazardous waste in 1995 (Federal Register, 1996b), as of 2000 only 15 plants (32 kilns) were burning hazardous waste. Other types of supplemental fuel used by these facilities include automobile tires, used motor oil, and sawdust, and scrap wood chips. The method of introducing liquid and solid hazardous waste into the kiln is a key factor to the complete consumption of the waste during the combustion of the primary fuel. Liquid hazardous waste is either injected separately or blended with the primary fuel (coal). Solid waste is mixed and burned along with the primary fuel. The pyroprocessing of raw meal in a cement kiln produces cement as fine particulates. At some facilities, cement kiln dust, which is an even finer particulate, is collected and controlled with fabric filters and/or electrostatic precipitators. Acid gases such as SO2 can be formed during pyroprocessing of the sulfur-laden minerals, but the minerals have high alkalinity which neutralizes SO2 gases. Emission factors (ng/kg clinker produced) for Portland cement kilns burning hazardous waste as supplemental fuel are displayed in Table 4-12. These emission factors were developed from stack testing of CDD/CDF emissions from eleven cement kilns burning hazardous waste. The majority of stack emissions data from cement kilns burning hazardous waste were derived during trial burns, and may overestimate the CDD/CDF emissions that most kilns achieve during normal operations. The emission factors in Table 4-12 were derived from facilities that were stack tested in 1998 and may not reflect current regulatory requirements. In 1999, EPA promulgated final standards for the stack emission limits of dioxin and dioxin-like compounds from hazardous waste combustion facilities (64 FR 52828 - 53077; Final Standards for Hazardous Air Pollutants For Hazardous Waste Combustors; Final Rule; September 30, 1999). The promulgated regulations require periodic stack sampling for dioxin-like compounds for all cement kilns burning hazardous waste. The owner/operator of such facilities is encouraged to use actual facility-specific emissions data (i.e., Approach 1) in lieu of EPA's default emission factors. Such data are the most representative and best data to use in estimating annual releases of dioxin-like compounds. 51 Table 4-12. Average Emission Factors (ng per dscm) for Estim ating A ir Releases of Dioxin and Dioxin-Like Compounds from cement Kilns Combusting Hazardous Waste as Supplemental Fuel F acility A B C D E F G H I J K Mean emission factor 2378TCDD 0.096 0.028 0.005 0.310 0.005 0.007 0.053 0.026 0.067 0.035 0.016 0.059 12378PeCDD 0.089 0.014 0.011 0.496 0.010 0.009 0.327 0.039 1.191 0.041 0.019 0.204 123478HxCDD 0.144 0.009 0.014 0.709 0.010 0.006 0.536 0.054 1.385 0.048 0.022 0.267 123678HxCDD 0.258 0.008 0.016 1.381 0.012 0.012 0.832 0.078 1.875 0.047 0.023 0.413 123789HxCDD 0.206 0.010 0.559 1.893 0.006 0.013 0.812 0.048 2.697 0.044 0.018 0.573 1234678HPCDD 2.162 0.043 0.155 6.011 0.068 0.057 5.366 0.430 9.971 0.216 0.064 2.231 OCDD 0.461 0.459 3.325 0.784 0.033 0.201 1.752 0.140 1.542 0.091 0.154 0.813 F acility 2378TCDF 12378-PeD F A 1.080 0.078 B 0.755 0.070 C 0.380 0.035 D 1.604 1.050 E 0.111 0.005 F 0.011 0.005 G 0.562 0.654 H 0.072 0.014 I 0.572 0.239 J 0.239 0.223 K 0.462 Mean emission factor 0.532 0.121 0.227 Dioxin and dioxin-like compounds: 23478P eC D F 0.183 0.093 0.067 2.353 0.012 0.010 1.790 0.054 0.570 0.226 0.133 0.499 7.06 123478H xC D F 123678H xC D F 123789H xC D F 234678H xC D F 0.098 0.043 0.031 0.065 0.034 0.019 0.007 0.025 0.039 0.017 0.003 0.027 2.024 1.029 0.316 1.441 0.008 0.004 0.005 0.006 0.011 0.005 0.002 0.006 1.366 0.533 0.115 1.168 0.022 0.015 0.003 0.011 0.450 0.208 0.060 0.344 0.182 0.103 0.023 0.085 0.078 0.031 0.017 0.032 0.392 0.182 0.053 0.292 per dry standard cubic m eter of stack gas 1234678HPCDF 0.051 0.006 0.026 0.946 0.009 0.010 0.609 0.009 0.208 0.185 0.050 0.192 1234789HpCDF 0.048 0.008 0.006 0.256 0.010 0.003 0.192 0.006 0.066 0.043 0.024 0.060 OCDF 0.116 0.029 0.021 0.141 0.039 0.008 0.119 0.008 0.060 0.095 0.106 0.067 52 The emission factors in Table 4-12 are in units of nanogram dioxin-like compound per dry standard cubic meter (at standard temperature and pressure and adjusted to 7% oxygen) of stack gas flow. This unit is a concentration of dioxin-like compounds measured in the stack gases. The facilities listed in Table 4-12 are cement kilns burning hazardous waste, and the emission factors (expressed on a concentration basis) are the average of multiple "runs" at the same facility. A "run" is defined as a single stack sampling episode to determine the amount of dioxin-like compounds present in the gases leaving the stack. These data can be found in a database maintained by EPA's Office of Solid Waste as documented in: Final Technical Support Document for Hazardous Waste Combustors (HWC) MACT Standards; HWC Emissions Database, Volume II: Appendix A: Cement Kilns: In: Final Standards for Hazardous Air Pollutants For Hazardous Waste Combustors; Final Rule; September 30, 1999. This cement kiln dioxin/furan database may be accessed on the Internet at the following URL: http://www.epa.gov/epaoswer/hazwaste/comust/. In order to estimate annual air emissions of dioxin-like compounds using the EPA default emission factors, the owner/operator are advised to follow the calculation steps given in section 3.1.1. Please note that the EPA default emission factors are generally applicable to all Portland cement kilns burning hazardous waste regardless of primary fuel type; constituents of hazardous waste burned as supplemental fuel; air pollution control equipment installed at the kiln; temperature of the kiln and whether or not the kiln is a wet or dry process. However, the emissions of dioxin-like compounds in Table 4-12 are more representative of cement kilns that operate the air pollution control equipment at temperatures of 204o Celsius (400oF) or less. Such temperatures are known to suppress the post combustion formation of dioxins and furans, and result in lower emissions of dioxin-like compounds than if the temperatures were more elevated. Section 4.5.4. Hazardous W aste Incineration (HWI) Facilities The four principal furnace designs employed for the combustion of hazardous waste in the United States are: liquid injection, rotary kiln, fixed hearth, and fluidized-bed incinerators (Dempsey and Oppelt, 1993). The majority of commercial operations are of the rotary kiln incinerator type. On-site (noncommercial) HWI technologies are an equal mix of rotary kiln and liquid injection facilities, with a few additional fixed hearths and fluidized bed operations (U.S. EPA, 1996h). Each of these HWI technologies is discussed below: Rotary Kiln H W I: Rotary kiln incinerators consist of a rotating kiln, coupled with a high temperature afterburner. Because these are excess air units designed to combust hazardous waste in any physical form (i.e., liquid, semi-solid, or solid), rotary kilns are the most common type of hazardous waste incinerator used by commercial "off-site" operators. The rotary kiln is a horizontal cylinder lined with refractory material. Rotation of the cylinder on a slight slope provides for gravitational transport of the hazardous waste through the kiln (Buonicore, 1992a). The tumbling action of the rotating kiln causes mixing and exposure of the waste to the heat of combustion, thereby enhancing burnout. Solid and semi-solid wastes are loaded into the top of the kiln by an auger or rotating screw. Fluid and pumpable sludges and wastes are typically introduced into the kiln through a water-cooled tube. Liquid hazardous waste is fed directly into the kiln through a burner nozzle. Auxiliary fuel (natural gas or oil) is burned in 53 the kiln chamber at start-up to reach elevated temperatures. The typical heating value of hazardous waste (i.e., 8,000 Btu/kg) is sufficient to sustain combustion without auxiliary fuel (U.S. EPA, 1996h). The combustion gases emanating from the kiln are passed through a high temperature afterburner chamber to more completely destroy organic pollutants entrained in the flue gases. Rotary kilns can be designed to operate at temperatures as high as 2,580 oC, but more commonly operate at about 1,100 oC. Liquid Injection H W I: Liquid injection incinerators (LIIs) are designed to burn liquid hazardous waste. These wastes must be sufficiently fluid to pass through an atomizer for injection as droplets into the combustion chamber. The LIIs consist of a refractory-lined steel cylinder mounted either in a horizontal or vertical alignment. The combustion chamber is equipped with one or more waste burners. Because of the rather large surface area of the atomized droplets of liquid hazardous waste, the droplets quickly vaporize. The moisture evaporates, leaving a highly combustible mix of waste fumes and combustion air (U.S. EPA, 1996h). Secondary air is added to the combustion chamber to complete the oxidation of the fume/air mixture. Fixed H earth H W I: Fixed hearths, the third principal hazardous waste incineration technology, are starved air or pyrolytic incinerators, which are two-stage combustion units. Waste is ram-fed into the primary chamber and incinerated below stoichiometric requirements (i.e., at about 50 to 80 percent of stoichiometric air requirements). The resulting smoke and pyrolytic combustion products are then passed though a secondary combustion chamber where relatively high temperatures are maintained by the combustion of auxiliary fuel. Oxygen is introduced into the secondary chamber to promote complete thermal oxidation of the organic molecules entrained in the gases. Fluidized-bed H W I: The fourth hazardous waste incineration technology is the fluidized-bed incinerator, which is similar in design to that used in municipal solid waste incineration. In this configuration, a layer of sand is placed on the bottom of the combustion chamber. The bed is preheated by underfire auxiliary fuel at startup. During combustion of auxiliary fuel at start-up, the hot gases are channeled through the sand at relatively high velocity, and the turbulent mixing of combustion gases and combustion air causes the sand to become suspended (Buonicore, 1992a). This takes on the appearance of a fluid medium, hence the incinerator is termed a `fluidized-bed' combustor The incinerator is operated below the melting point temperature of the bed material. Typical temperatures of the fluid medium are within the range of 650 to 940* C. A constraint on the types of waste burned is that the solid waste particles must be capable of being suspended within the furnace. When the liquid or solid waste is combusted in the fluid medium, the exothermic reaction causes heat to be released into the upper portion of the combustion chamber. The upper portion is typically much larger in volume than the lower portion, and temperatures can reach 1,000* C (Buonicore, 1992a). This high temperature is sufficient to combust volatilized pollutants emanating from the combustion bed. Most HWIs use APCDs to remove undesirable components from the flue gases that evolved during the combustion of the hazardous waste. These unwanted pollutants include suspended ash particles (particulate matter or PM), acid gases, metal, and organic pollutants. The APCD controls or collects these pollutants and reduces their discharge from the incinerator stack to the atmosphere. Levels 54 and kinds of these combustion byproducts are highly site-specific, depending on factors such as waste composition and incinerator system design and operating parameters (e.g., temperature and exhaust gas velocity). The APCD is typically comprised of a series of different devices that work together to clean the exhaust combustion flue gas. Unit operations usually include exhaust gas cooling, followed by particulate matter and acid gas control. Exhaust gas cooling may be achieved using a waste heat boiler or heat exchanger, mixing with cool ambient air, or injection of a water spray into the exhaust gas. A variety of different types of APCDs are employed for the removal of particulate matter and acid gases. Such devices include: wet scrubbers (such as venturi, packed bed, and ionizing systems), electrostatic precipitators, and fabric filters (sometimes used in combination with dry acid gas scrubbing). In general, the control systems can be grouped into the following three categories: wet, dry, and hybrid wet/dry systems. The controls for acid gases (either dry or wet systems) cause temperatures to be reduced preceding the control device. This impedes the extent of formation of CDDs and CDFs in the post-combustion area of the typical HWI. It is not unusual for stack concentrations of CDD/CDFs at a particular HWI to be in the range of 1 to 100 ng CDD/CDF/dscm (Helble, 1993), which is low in comparison to other waste incineration systems. The range of total CDD/CDF flue gas concentrations measured in the stack emissions of HWIs during trial burns across the class of HWI facilities, however, has spanned four orders of magnitude (ranging from 0.1 to 1,600 ng/dscm) (Helble, 1993). The APCD systems are described below: W et System s: A wet scrubber is used for both particulate and acid gas control. Typically, a venturi scrubber and packed-bed scrubber are used in a back-to-back arrangement. Ionizing wet scrubbers, wet electrostatic precipitators, and innovative venturi-type scrubbers may be used for more efficient particulate control. Wet scrubbers generate a wet effluent liquid wastestream (scrubber blowdown), are relatively inefficient at fine particulate control compared to dry control techniques, and have equipment corrosion concerns. However, wet scrubbers do provide efficient control o f acid gases and have lower operating temperatures (compared with dry systems), which may help control the emissions of volatile metals and organic pollutants. D ry System s: In dry systems, a fabric filter or electrostatic precipitator (ESP) is used for particulate control. A fabric filter or ESP is frequently used in combination with dry scrubbing for acid gas control. Dry scrubbing systems, in comparison with wet scrubbing systems, are inefficient in controlling acid gases. H ybrid Systems: In hybrid systems, a dry technique (ESP or fabric filter) is used for particulate control, followed by a wet technique (wet scrubber) for acid gas control. Hybrid systems have the advantages of both wet and dry systems (lower operating temperature for capture of volatile metals, efficient collection of fine particulate, efficient capture of acid gases), while avoiding many of the individual disadvantages. In some hybrid systems, known as "zero discharge systems," the wet scrubber liquid is used in the dry scrubbing operation, thus minimizing the amount of liquid byproduct waste. 55  Uncontrolled H W Is: Facilities that do not use any air pollution control devices fall under a separate and unique category. These are primarily liquid waste injection facilities, which burn low ash and chlorine content wastes; therefore, they are low emitters of PM and acid gases. For purposes of estimating emission factors, this document considers subdividing the combustors in each source category into design classes judged to have similar potential for CDD/CDF emissions. As explained below, it was decided not to subdivide dedicated HWIs. Combustion research has identified three mechanisms involved in the emission of CDD/CDFs from combustion systems: (1) CDD/CDFs can be introduced into the combustor with the feed and pass through the system not completely burned/destroyed; (2) CDD/CDFs can be formed by chemical reactions inside the combustion chamber; and (3) CDD/CDFs can be formed by chemical reactions outside the combustion chamber. The total CDD/CDF emissions are likely to be the net result of all three mechanisms; however, the relative importance of the mechanisms can vary among source categories. In the case of HWIs, the third mechanism (i.e., post-combustion formation) is likely to dominate, because HWIs are typically operated at high temperatures and long residence times, and most have sophisticated real-time monitoring and controls to manage the combustion process. Therefore, any CDD/CDFs present in the feed or formed during combustion are likely to be destroyed before exiting the combustion chamber. Consequently, for purposes of generating emission factors, it was decided not to subdivide this class on the basis of furnace type. Emissions resulting from the post-combustion formation in HWIs can be minimized through a variety of technologies: Rapid Flue Gas Q uenching: The use of wet and dry scrubbing devices to remove acid gases usually results in the rapid reduction of flue gas temperatures at the inlet to the PM APCD. If temperature is reduced below 200C, the low-temperature catalytic formation of CDD/CDFs is substantially retarded. Use of Particulate M atter (PM) A ir Pollution Control Devices: PM control devices can effectively capture condensed and adsorbed CDD/CDFs that are associated with the entrained particulate matter (in particular, that which is adsorbed on unburned carbon containing particulates). Use of Activated C arbon: Activated carbon injection is used at some HWIs to collect (sorb) CDD/CDFs from the flue gas. This may be achieved using carbon beds or by injecting carbon and collecting it in a downstream PM APCD. All of these approaches appear very effective in controlling dioxin emissions at dedicated HWIs, and insufficient emissions data are available to generalize about any minor differences. Consequently, for purposes of generating emission factors, it was decided not to subdivide this class on the basis of APCD type. 56 In 1999, EPA promulgated final standards for the stack emission limits of dioxin and dioxin-like compounds from hazardous waste combustion facilities (64 FR 52828 - 53077; Final Standards for Hazardous Air Pollutants For Hazardous Waste Combustors; Final Rule; September 30, 1999). Table 4-13 displays mean CDD/CDF emission factors for estimating air releases of dioxin and dioxin-like compounds from hazardous waste combustion facilities. The promulgated regulations require periodic stack sampling for dioxin-like compounds for all commercial hazardous waste combustion facilities. The owner/operator of such facilities is encouraged to use actual facility-specific emissions data (i.e., Approach 1) in lieu of EPA's default emission factors. Such data are the most representative and best data to use in estimating annual releases of dioxin-like compounds. Table 4-13. Average Emission Factors (ng/kg waste feed) for Estim ating A ir Releases of Dioxin and Dioxin-like Compounds from Hazardous W aste Combustion Facilities CDD Congener Emission Factor (ng/kg waste feed) CDF Congener 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD 1,2,3,4,6,7,8,9-OCDD 0.14 2,3,7,8-TCDF 0.14 1,2,3,7,8-PeCDF 0.18 2,3,4,7,8-PeCDF 0.28 1,2,3,4,7,8-HxCDF 0.48 1,2,3,6,7,8-HxCDF 1.75 1,2,3,7,8,9-HxCDF 3.74 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 CDD 6.71 CDF Dioxin and dioxin-like compounds* 62.74 * Dioxin and dioxin-like compounds = CDDs + CDFs Emission Factor (ng/kg waste feed) 2.69 2.33 2.51 9.71 3.95 0.29 2.70 16.68 1.71 13.46 56.03 57 Abatement: Air Emission Air Pollutant Air Pollution Control Device: Ambient Measurement Area Source BACT-Best Available Control Technology Section 5.0 GLOSSARY Reducing the degree or intensity of, or eliminating, pollution. The release or discharge of a pollutant by an owner or operator into the ambient air either by means of a stack or as a fugitive dust, mist, or vapor as a result inherent to the manufacturing, forming or combustion process. Dust, fumes, smoke, and other particulate matter, vapor, gas, odorous substances, or any combination thereof. Also any air pollution agent or combination of such agents, including any physical, chemical, biological, radioactive substance or matter which is emitted into or otherwise enters the ambient air. Mechanism or equipment that cleans emissions generated by a source (e.g., an incinerator, industrial smokestack, or an automobile exhaust system) by removing pollutants that would otherwise be released to the atmosphere. A measurement of the concentration of a substance or pollutant within the immediate environs of an organism; taken to relate it to the amount of possible exposure. Any source of air pollution that is released over a relatively small area but which cannot be classified as a point source. Such sources may include vehicles and other small engines, small businesses and household activities, or biogenic sources such as a forest that releases hydrocarbons An emission limitation based on the maximum degree of emission reduction (considering energy, environmental, and economic impacts) achievable through application of production processes and available methods, systems, and techniques. BACT does not permit emissions in excess of those allowed under any applicable Clean Air Act provisions. Use of the BACT concept is allowable on a case by case basis for major new or modified emissions sources in attainment areas and applies to each regulated pollutant. 58 Boiler A vessel designed to transfer heat produced by combustion or electric resistance to water. Boilers may provide hot water or steam. British Thermal Unit (Btu) Unit of heat energy equal to the amount of heat required to raise the temperature of one pound of water by one degree Fahrenheit at sea level. CAS Registration Number A number assigned by the Chemical Abstract Service to identify a chemical. Combustion 1. Burning, or rapid oxidation, accompanied by release of energy in the form of heat and light. 2. Refers to controlled burning of waste, in which heat chemically alters organic compounds, converting into stable inorganics such as carbon dioxide and water. Concentration The relative amount of a substance mixed with another substance. An example is five ppm of carbon monoxide in air or 1 mg/l of iron in water. Congener A discrete chemical compound within a group of compounds having the same molecular weight and chemical/physical properties. Cubic Feet Per Minute (CFM) A measure of the volume of a substance flowing through air within a unit period of time. Dioxin and Dioxin-like compounds: CDDs and CDFs substituted with chlorine substitution in the 2,3,7, and 8-positions along the molecule. There are 7 CDDs and 10 CDFs (for a total of 17 compounds) that meet this definition. Discharge The release of any waste stream or any constituent thereof, into the environment. Design Capacity The average daily flow that a treatment plant or other facility is designed to accommodate. Detection Limit The lowest concentration of a chemical that can reliably be distinguished from a zero concentration. 59 Destruction and Removal Efficiency (DRE) Effluent Guidelines Effluent Emission Factor Emission Inventory Emission Emission Standard End-of-the-pipe Electrostatic precipitator Emission Rate A percentage that represents the number of molecules of a compound removed or destroyed in an incinerator relative to the number of molecules entering the system (e.g., a DRE of 99.99 percent means that 9,999 molecules are destroyed for every 10,000 that enter; 99.99 percent is known as "four nines." For some pollutants, the RCRA removal requirement may be as stringent as "six nines." Technical EPA documents which set effluent limitations for given industries and pollutants. Wastewater--treated or untreated--that flows out of a treatment plant, sewer, or industrial outfall. Generally refers to wastes discharged into surface waters. The relationship between the amount of pollution produced and released into the environment and the amount of raw material processed, fuel consumed, or waste processed. For example, an emission factor for a blast furnace making iron would be the number of grams of dioxin-like compounds per ton of raw materials. A listing, by source, of the amount of contaminant released into the environment per year. Pollution discharged into the atmosphere from smokestacks, other vents, and surface areas of commercial or industrial facilities; from residential chimneys; and from motor vehicle, locomotive, or aircraft exhausts. The maximum amount of air polluting discharge legally allowed from a single source, mobile or stationary. Technologies such as scrubbers on smokestacks and catalytic convertors on automobile tailpipes that reduce emissions of pollutants after they have formed. An air pollution control device that imparts an electric charge to particles in a gas stream causing them to collect on an electrode. The amount of a pollutant or contaminant emitted per unit of time. 60 Equivalent Method Fabric Filter Flow Rate Flue Gas Fossil Fuel: Fugitive Emissions Gas Chromatography/ Mass Spectrometer Grab Sample Hazardous Waste Incineration Industrial Process Waste Any method of sampling and analyzing for the presence and occurrence of a contaminant in an environmental sample which has been demonstrated to the EPA Administrator's satisfaction to be, under specific conditions, an acceptable alternative to normally used reference methods. Large fabric bag, usually made of glass fibers, used to eliminate intermediate and large (greater than 20 PM in diameter) particles. This device operates like the bag of an electric vacuum cleaner, passing the air and smaller particles while entrapping the larger ones. The rate, expressed in gallons -or liters-per-hour, at which a fluid escapes from a hole or fissure in a tank. Such measurements are also made of liquid waste, effluent, and surface water movement. The products of combustion, including pollutants, emitted to the air after a production process or combustion takes place Fuel derived from ancient organic remains; e.g., peat, coal, crude oil, and natural gas. Emissions not caught by a capture system. Instrument that identifies the molecular composition and concentrations of various chemicals in water and soil samples. A single sample collected at a particular time and place that represents the composition of the water, air, or soil only at that time and place. Wastes that possess at least one of four characteristics (ignitability, corrosivity, reactivity, or toxicity), or appears on special EPA lists, as defined by RCRA Subtitle C. An engineered process using controlled flame combustion to thermally degrade waste materials. Residues produced during manufacturing operations. 61 Industrial Sludge Industrial Waste Land Application Maximum Available Control Technology (MACT) Maximum Contaminant Level Media Method Detection Limit (MDL) Million-Gallons Per Day (MGD) Molecule Monitoring National Emissions Standards for Hazardous Air Pollutants (NESHAPS) Semi-liquid residue or slurry remaining from treatment of industrial water and wastewater. Unwanted materials from an industrial operation; may be liquid, sludge, solid, or hazardous waste. Discharge of wastewater, sludge or solid waste onto the surface of the ground for treatment or reuse. The emission standard for sources of air pollution requiring the maximum reduction of hazardous emissions, taking cost and feasibility into account. Under the Clean Air Act Amendments of 1990, the MACT must not be less than the average emission level achieved by controls on the best performing 12 percent of existing sources, by category of industrial and utility sources. The maximum permissible level of a contaminant in water delivered to any user of a public system. MCLs are enforceable standards. Specific environments--air, water, soil--which are the subject of regulatory concern and activities. See limit of detection. A measure of water flow. The smallest division of a compound that still retains or exhibits all the properties of the substance. The direct measurement of the amount or concentration of a contaminant in an environmental medium. Emissions standards set by EPA for an air pollutant not covered by NAAQS that may cause an increase in fatalities or in serious, irreversible, or incapacitating illness. Primary standards are designed to protect human health, secondary standards to protect public welfare (e.g., building facades, visibility, crops, and domestic animals). 62 National Pollutant Discharge Elimination System (NPDES): Outfall Particulates Performance Standards Physical and Chemical Treatment A provision of the Clean Water Act which prohibits discharge of pollutants into waters of the United States unless a special permit is issued by EPA, a state, or, where delegated, a tribal government on an Indian reservation. The place where effluent is discharged into receiving waters. 1. Fine liquid or solid particles such as dust, smoke, mist, fumes, or smog, found in air or emissions. 2. Very small solids suspended in water; they can vary in size, shape, density and electrical charge and can be gathered together by coagulation and flocculation. 1. Regulatory requirements limiting the concentrations of designated organic compounds, particulate matter, and hydrogen chloride in emissions from incinerators. 2. Operating standards established by EPA for various permitted pollution control systems, asbestos inspections, and various program operations and maintenance requirements. Processes generally used in large-scale wastewater treatment facilities. Physical processes may include air-stripping or filtration. Chemical treatment includes coagulation, chlorination, or ozonation. The term can also refer to treatment of toxic materials in surface and ground waters, oil spills, and some methods of dealing with hazardous materials on or in the ground. Quality Assurance/Quality Control Receiving Waters Representative Sample Sampling Frequency A system of procedures, checks, audits, and corrective actions to ensure that all EPA research design and performance, environmental monitoring and sampling, and other technical and reporting activities are of the highest achievable quality. A river, lake, ocean, stream or other watercourse into which wastewater or treated effluent is discharged. A portion of material, medium or water that is as nearly identical in content and consistency as possible to that in the larger body of material, medium or water being sampled. The interval between the collection of successive samples. 63 Scrap Scrubber Site Sludge Smelter Source Source Characterization Solid Waste Stack Standards Surface Water Materials discarded from manufacturing operations that may be suitable for reprocessing. An air pollution device that uses a spray of water or reactant or a dry process to trap pollutants in emissions. An area or place within the jurisdiction of the EPA and/or a state. Any solid, semisolid or liquid waste generated from a municipal, commercial, or industrial wastewater treatment plant, water supply treatment plant, or air pollution control facility, or any other such waste having similar characteristics. A facility that melts or fuses ore, often with an accompanying chemical change, to separate its metal content. Emissions cause pollution. "Smelting" is the process involved. Any building, structure, facility or installation from which there is or may be the discharge of pollutants into the environment. Measurements made to estimate the rate of release of pollutants into the environment from a source such as an incinerator, landfill, etc. Non-liquid, non-soluble materials ranging from municipal garbage to industrial wastes that contain complex and sometimes hazardous substances. Solid wastes also include sewage sludge, agricultural refuse, demolition wastes, and mining residues. Technically, solid waste also refers to liquids and gases in containers. Any chimney, flue, vent, roof monitor, conduit or duct arranged to discharge emissions to the air. Norms that impose limits on the amount of pollutants or emissions produced. EPA establishes minimum standards, but states are allowed to be stricter. All water naturally open to the atmosphere (rivers, lakes, reservoirs, ponds, streams, impoundments, seas, estuaries, etc.) 64 Technology-Based Limitations Technology-Based Standards Treatment Plant Trial Burn Utility Boiler Venturi Scrubbers Waste Feed Waste Generation Waste Stream Waste Treatment Plant Industry-specific effluent limitations based on best available preventive technology applied to a discharge when it will not cause a violation of water quality standards at low stream flows. Usually applied to discharges into large rivers. Industry-specific effluent limitations applicable to direct and indirect sources which are developed on a category-by-category basis using statutory factors, not including water-quality effects. A structure built to treat wastewater before discharging it into the environment. Treatment, Storage, and Disposal Facility: Site where a hazardous substance is treated, stored, or disposed of. TSD facilities are regulated by EPA and states under RCRA. An incinerator test in which emissions are monitored for the presence of specific organic compounds, particulates, and hydrogen chloride. Trichloroethylene (TCE): A stable, low boiling-point colorless liquid, toxic if inhaled. Used as a solvent or metal degreasing agent, and in other industrial applications. Coal, oil or natural gas fired boiler used to exchange heat of combustion to steam to operate an electric generator for the expressed purpose of producing electricity. Alternative term is Power Plant. Air pollution control devices that use water to remove particulate matter from emissions The continuous or intermittent flow of wastes into an incinerator. The weight or volume of materials and products that enter the waste stream before recycling, composting, landfilling, or combustion takes place. Also can represent the amount of waste generated by a given source or category of sources The total flow of solid waste from homes, businesses, institutions, and manufacturing plants that is recycled, burned, or disposed of in landfills, or segments thereof such as the "residential waste stream" or the "recyclable waste stream." A facility containing a series of tanks, screens, filters and other processes by which pollutants are removed. 65 Waste Treatment Stream Wastewater Water Quality Criteria Water Quality Standards Water Quality-Based Limitations Water Quality-Based Permit The continuous movement of waste from generator to treater and disposer. The spent or used water from a home, community, farm, or industry that contains dissolved or suspended matter. Water Pollution: The presence in water of enough harmful or objectionable material to damage the water's quality. Levels of water quality expected to render a body of water suitable for its designated use. Criteria are based on specific levels of pollutants that would make the water harmful if used for drinking, swimming, farming, fish production, or industrial processes. State-adopted and EPA-approved ambient standards for water bodies. The standards prescribe the use of the water body and establish the water quality criteria that must be met to protect designated uses. Effluent limitations applied to dischargers when mere technology-based limitations would cause violations of water quality standards. Usually applied to discharges into small streams. A permit with an effluent limit more stringent than one based on technology performance. Such limits may be necessary to protect the designated use of receiving waters (e.g., recreation, irrigation, industry or water supply). 66 Abbreviation in ft ft yd mi cm m m m km ft ft ft in in mi mi ac ac ac ft2 ft2 ft2 Section 6.0 CONVERSION FACTORS From inch feet feet yard mile centimeter meter meter meter kilometer feet feet feet inches inches miles miles acre acre acre square feet square feet square feet Multiply by To Length (English to Metric) 2.5 centimeters 30.5 centimeters 0.3048 meters 0.914 meters 1.609 kilometer Length (Metric to English) 0.394 inch 3.281 feet 1.093 yard 39.37 inches 0.6214 mile Length (English to English) 12 inches 0.333 yards 0.000189 miles 0.083 feet 0.028 yards 5,280 feet 1,760 yards Area (English to English) 43,560 square feet 4,840 square yards 0.0016 square miles 0.000023 acres 144 square inches 0.111 square yards 67 Abbreviation cm cm m m km in ft yd in mi in yd mi ft yd ft yd ft2 yd2 mi2 ac in2 yd2 Abbreviation in2 mi2 in2 ft2 yd2 mi2 mi2 ac ac ac cm2 m2 m2 km2 m2 ha ha ha pt gal ft3 ft3 yd3 cfs or ft3/s cfsorft3/s From Multiply by To square inches 0.007 square feet square miles 640 acres Area (English to Metric) square inch 6.5 square centimeter square foot 0.0929 square meters square yard 0.836 square meters square mile 2.59 square kilometer square mile 259 hectares acre 4,047 square meters acre 0.405 hectares acre 0.004 square kilometer Area (Metric to English) square centimeter 0.16 square inch square meter 10.76 square feet square meter 1.2 square yard square kilometer 0.386 square mile square meter 0.0002471 acre hectares 2.5 acre hectares 107,639 square feet hectares 0.004 square miles Volume (English to Metric) pint 0.47 liter gallon 3.8 liter cubic feet 0.0283 cubic meter cubic feet 28.317 liters cubic yard 0.765 cubic meter cubic feet per second 0.0283 cubic meter/second cubic feet per second 0.646 million gallons per day Abbreviation ft2 ac cm2 m2 m2 km2 ha m2 ha km2 in2 ft2 yd2 mi2 ac ac ft2 mi2 L L m3 L m3 m3/s Mgal/d 68 Abbreviation Mgal/d Mgal/d bb mL L L L mL m3 m3 m3/s m3/s bb bu ft3 ft3 gal gal gal gal oz oz oz lb From Multiply by To million gallons per day 0.0438 cubic meter/second milliongallons per day 1.547 cubic feet per second barrels,US Petroleum 159 liters Volume (Metric to English) milliliters 0.034 fluid ounces liter 2.1 pint liter 1.06 quart liter 0.264 gallon milliliter 0.034 ounces cubic meter 35.31 cubic feet cubic meter 1.31 cubic yard cubic meter per second 35.31 cubic feet per second cubic meter per second 22.821 milliongallons per day Volume (English to English) barrels, petroleum 42 gallons bushels 1.244 cubic feet cubic feet 1,728 cubic inches cubic feet 0.037 cubic yards gallons 0.134 cubic feet gallons 128 ounces gallons 8 pints gallons 4 quarts once 0.001 cubic feet Weight (English to English) ounces 0.0625 pounds ounces 437.5 grains pounds 16 ounces Abbreviation m3/s cfs or ft3/s L fl oz pt qt gal oz ft3 yd3 cfs or ft3/s Mgal/d gal ft3 in3 yd3 ft3 oz pt qt ft3 lb gr oz 69 Abbreviation t t oz oz lb lb t t t g g g kg kg kg mt mt mt oF oC mg/L PPm From Multiply by To tons, long 2,240 pounds tons, long 1.12 tons, short Weight (English to Metric) ounces 28.35 grams ounces 0.028 kilogram pounds 453.59 grams pounds 0.454 kilograms tons, short 0.907 metric tons tons, short 907 kilograms tons, long 1.016 metric tons Weight (Metric to English) grams 0.002 pounds grams 15.43 grains grams 0.035 ounces kilograms 2.205 pounds kilograms 0.0011 tons, short kilograms 0.001 tons, long metric tons 0.984 tons, long metric tons 1.102 tons, short metric tons 2,204.6 pounds Temperature degrees Fahrenheit 5/9 * (oF-32) degrees Celsius degrees Celsius 9/5 * (oC +32) degrees Fahrenheit Concentration milligrams per liter 1 parts per million parts per million 1 milligrams per liter Abbreviation lb t t g kg g kg mt kg mt lb gr oz lb t t t t lb oC oF PPm mg/L 70 Section 7.0 REFERENCES AGES. Applied Geotechnical and Environmental Service Corp. (1992) Source sampling report comprehensive emissions testing; blast furnace, May/June 1992, Franklin Smelting & Refining Corp. Valley Forge, PA: AGES. Report No. 42614.01-01. Advanced Technology Systems, Inc. (1995) Report on measurement of hazardous air pollutants from aluminum melt furnace operations at Ravenswood Aluminum Corporation. Monroeville, PA: Advanced Technology Systems, Inc. Buekens, A.; Stieglitz, L.; Huang, H.; Dinova, C.; Cornelis, E. (1997) Preliminary investigation of formation mechanism of chlorinated dioxins and furans in industrial and metallurgical processes. Organohalogen Compounds 31:516-520. Buonicore, A.J. (1992) Control of gaseous pollutants. In: Buonicore, A.J., Davis, W.T., eds., Air pollution engineering manual. Air and Waste Management Association. New York, NY: Van Nostrand Reinhold. 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Federal Register (1999b)Final standards for hazardous air pollutants for hazardous waste combustorswaste combustors: proposed rule. F.R. (September 30) 64: 52828 53077. Federal Register (1999c) National emission standards for hazardous air pollutants for source categories; Portland Cement manufacturing industry. F.R. (June 14) 64:31897-31962. Galson Corporation (1995) Source test report: Source emission testing at Roth Brothers Smelting Corporation. East Syracuse, NY: Galson Corporation. Gillespie, W.J. (1997) Letter to G. Schweer (Versar, Inc.) dated February 10, 1997. Research Triangle Park, NC: National Council of the Paper Industry for Air and Stream Improvement, Inc. 72 Greer, W.L.; Johnson, M.D.; Raught, E.C.; Steuch, H.E.; Trusty, C.B. (1992) Portland cement. In: Buonicore, A.J.; Davis, W.T.; eds. Air pollution engineering manual, Air and Waste Management Association. New York, NY: Van Nostrand Reinhold. Helble, J.J. (1993) Analysis of dioxin emissions from the incineration of hazardous waste. Washington, DC: U.S. Environmental Protection Agency, Office of Solid Waste, Permits and State Programs Division. LUA (1997) Identification of relevant industrial sources of dioxins and furans in Europe. Materialien No. 43. Landesumweltamt Nordrhein-Westfalen, Essen. NCASI (National Council of the Paper Industry for Air and Stream Improvement) (1995) NCASI summary of PCDD/F emission from wood residue and black liquor combustion. Attachment 2 to comments submitted on January 13, 1995, to EPA's Office of Health and Environmental Assessment concerning the draft document entitled "Estimating Exposure to Dioxin-Like Compounds." Riggs, K.B.; Brown, T.D.; Schrock, M.E. (1995) PCDD/PCDF emissions from coal-fired power plants. Organohalogen Compounds 24:51-54. Roy Weston (1996) Item ii-D-82 in USEPA Secondary Aluminum MACT air docket number A-92-61: Scrap Dryer and reverberatory Furnace Emission Test Report, Wabash IN. Prepared by Roy F. Weston for Wabash Alloys, Work Order No. 11590-001-001, August 1996. Sverdrup Corp. (1991) Chemetco, Inc., compliance testing, final report. St. Louis, MO: Sverdrup Corp. April 19, 1991. U.S. Department of Commerce (1996) 1992 Economic census report series - disc 1G. Washington, DC: Bureau of the Census. CD-EC92-1G. U.S. Environmental Protection Agency (1995c) Final emission test report, HAP emission testing on selected sources at a secondary lead smelter, Schuylkill Metals Corporation, Forest City, Missouri. Research Triangle Park, NC: Office of Air Quality Planning and Standards, Emission Measurement Branch. EMB Report No. 93-SLS-2. 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U.S. Environmental Protection Agency (1994c) Preliminary source assessment for the secondary copper smelting industry. Draft report. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EPA Contract No. 68-D1-118, Work Assignment Nos. 25, 40, and 46. U.S. Environmental Protection Agency (1990) Draft technical support document for hazardous waste combustor MACT standards. Volume I: Description of source categories. Washington, DC: Office of Solid Waste and Emergency Response. February 1996. U.S. Environmental Protection Agency (1995) Secondary aluminum plant emission test report: Rochester Aluminum Smelting Corporation. Research Triangle Park, NC: Office of Air Quality Planning and Standards. EMC Report 95-SAL-01. U.S. Environmental Protection Agency (1992) Secondary lead smelter emission test report, East Penn Manufacturing, Lyon Station, Pennsylvania. Research Triangle Park, NC: Office of Air Quality Planning and Standards, Emission Measurement Branch. EMB Report No. 92-SLS-3. U.S. Environmental Protection Agency (1997) Locating and estimating air emissions from sources of dioxins and furans. Research Triangle Park, NC: Office of Air Quality Planning and Standards. DCN No. 95-298-130-54-01. U.S. Geological Survey (1997) Minerals yearbook: recycling - nonferrous metals chapter. Reston, VA: U.S Geological Survey, Geologic Division. U.S. Geological Survey (1997b) Mineral commodity survey - iron and steel scrap. Washington, DC: U.S. Department of the Interior, U.S. Geological Survey. 74