Document 7OVNNXOpZ6E1JV5Rr3z5kwo6

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 1983 REGION V R e v i e w and Development of Cnlorinated s u b j e c t Dioxins and "Furans Em issions Data" March 1983, Radian Corporation ' from: Howard Zar, Chief '< V.,^ Technical Unit, TAS ^ T0: Regional D ioxin Task Force The subject "D r a f t " report has been prepared as part of the NESHAPs standard development e ffo rt. I have been advised that i t should not be circulated outside the agency at the present time. Attachment L P A F O R M 1320-6 (REV 3-761 vi REVIEW AND DEVELOPMENT 07 CHLORINATED DIOXINS AND FTJRAN5 EMISSIONS DATA March 1983 u I i '3 I :.k *3 CORPORATION wrs A ? 4 / !  I DISCLAIMER This report. cas been reviewed by Che Strategies and Air Standards Division (5AST ) , .S. Environmental Protection Agency (EPA) and approved for publication, Approval for publication does not signify that the contents neeease. m l 7 reflect the views and policies of the U.S. Environ-- mental P r oceeds n. Agency, nor does mention of trade, names or commercial produces cons tit:ure endorsement or recommendation for use. i Radian Mo. 240-016-23 DCN No. 83-240-016-23-L3 EPA Contract No. 68-02-3513 rr7orI< Assignment No. 23 RETIES AND DEVELOPMENT OF CHLORINATED BIOTINS AND FEANS EMISSIONS DATA March 1983 Prepared for: tfarren D. Peters EPA Project Officer PcLiecant Assessment Branch Strategies and Air Standards DivisionU.S. Environmental Protection Agency Research Triangle; Park,. NC 27711 Prepared, by: Radian Corporation 3024 Pickett Road Durham, NC 27705 PRHPACE The U.S. Euvir Orman cal Protection Agency (EPA) is interas rad in. chlorinecad cicalas and faraas because or cheir potential toxicities to humans and because several industrial operations have been demonstrated, to emit low concentrations or. these compounds into the ambient air. Many or the determinations of industrial chlorinated dioxin and furan sources have only recently been, mader possible due to- advancements-, in sampling and analytical techniques. To expand its- knowledge: an industrial sources of. chlorinated, dioxins and. furans, EPA1s* Office of* Air Quality Planning- and Standards (OAQPS) requested the development or a specific technical data base- relating to chlorinated dioxin and furan air emissions. The results of the data base- development effort axe summarized in this report. In developing- the- chlorinated dioxin and furan air emissions, data- base,, the following, four topics- or questions were deemed, as key. -- What source categories might emit chlorinated dioxins, anA furans? -- Eow many individual sources are in each source category and where are they located? . * -- What is the availability of amissions and emission, factor data- pertaining to chlorinated dioxins and furans? -- Have chlorinated dioxins and furans been measured in the ambient air? The answers to these questions will help EPA decide whether more extensive and detailed efforts are. needed to investigate* possible regulation develop ment for certain dioxin 'and furan sources. * fl EXECUTIVE. SUMMAET Chlorinated dibenza-p-dioxins (chlorinated dioxins) and chlorinated dibenzofurzms (chlorinated furans) are families of organic compounds theoretically containing 75 and 135 different structural isomers, respectively. The toxicity to humans of ail these isomers has nor bean decaminad because nor ail have bean isolated and analyzed. Of the isomers studied, the 2 ,3,7,3--isomers or the chlorinated dioxin and furan groups have been determined to exhibit the highest toxicity levels. This report provides information on chlorinated dioxin and furan source categories, individual sources, emissions, and ambient exposure levels. The information gathered vas abstracted from an extensive literature search and data base development study. Source categories of chlorinated dioxin, and furan air emissions, that have been confirmed by testing,, include municipal, hazardous, and chemical vaste incinerators, vire reclamation incinerators, industrial boilers, wood stoves, fireplaces, residential furnaces, and internal combustion: engines. Although there are numerousindividual sources vithin each of these source categories, only seven Individual sources vere specifically identified and discussed in theliterature. Potential sources- of chlorinated dioxin and furan air emissions have also been indicated by laboratory research. The types of laboratory experiments which have produced chlorinated dioxin and/or furan emissions are the combustion of wood, grass, and paper treated with a formulation of 2,4,5-- crichiorophenoxy acetic acid (2,4,5-1), the combustion of wood treated with a tricnlorophanolate and tetrachlorophenolate formulation, the pyrolysis of commercial polychlorinated biphenyls (?C3s) and PC3 isomers, the pyrolysis of tri-, tatra-- , and pentachlorobenzene, the high temperature oxidation and chlorination of coal, and the combustion of birch leaves and wood wool treated "with chloropaanacas. iii t 4 Chlorinated dioxin and furan emissions have been measured in relatively low concentrations in both particulate and gaseous exhaust streams; however, most emission tests have only analyzed particulate emissions for these compounds. The majority of available emissions data for chlorinated dioxins and furans is in the form of emission concentrations and emission factors. Because the identification and measurement of chlorinated furans has only recently become important,, more emissions data are available for chlorinated dioxins than fcrr furans. For the source category in which the most data exist, municipal waste incinerators, total chlorinated dioxin levels in chet exhaust, fly ash have been measured to range from 23.3 ppb to 2S66 ppb. Total chlorinated furan- levels from the same source range from 13.4- ppb to 2036 ppb.. Emission factors, developed for- municipal waste incinerators on the basis of the amount, of waste burned, have been found to range from 0.23 to 16.3 Ug/kg for total chlorinated dioxins and from 2,3 to 17.1 ug/kg for total chlorinated furans. Virtually no data are available which estimate chlorinated dioxin and furan source category emissions on an annualized mass emission basis. One reference, however,, has. estimated than nationwide, tetrachlorinated dibenzo-p-dioxin (TCDD) amissions from residential wood stoves, and fire places are 0.27 kg. (0.6 lb)/yr, TCDD emissions from commercial wood burning are 0.51 kg (1.2 lb)/yr, estimated TCDD emissions from controlled wood burning, are 0.32 kg (0.7 !b)/yr, and estimated TCDD emissions from foresn fires are 3.L kg (6.9 lb)/yr. Mo dara on the levels of chlorinated dioxins and furans in the ambient air were reported in the identified published literature. Thera was only one reported indication that actual ambient measurements had ever been attamp cad. In this case it was only qualitatively determined that chlorinated furans were present in a sample taken downwind of a hazardous waste incinerator. Other studies have- been conducted "a estimate ambient chlorinated dioxin and furan levels by using actual emission test data and atmospheric dispersion models. The results of such modelling and exposure analyses at five sources of TCDD compounds has led Z?A. zd conclude that municipal wasze incinerators do not present a public health hazard in regard to their TCDD emissions. IV t % TABLE OF CONTENTS Page sc of Tables .................... . vii. sc of Figures..................................................... vili CHA2TZ?. L - SUMMART OF THE CHLORINATED DIOXIN AND FURAN PROJECT........................... .... .............. ......... I.L Project. S u m a r y ........... .......... ............... 1.2 Summary of Cb.Ioric.aced Dioxin and'Furan Source Categories and Emissions........... .................. L.3 Recommendations for Furcher Study of Chlorinated Dioxin and Furan Air Inissiens................ . L L 2 3 CHAPTER 2 - CHEMICAL BACKGROUND ON CHLORINATED DIOXINS AND FURANS................................................... 2 . 22. L Chemical Dascription of Dioxins................... Chemical Dascription of Furans.................... 2.3 Occurrence and Fonacin or Chlorinated Dioxins and Furans..J. 5 5 7 9 CHAPTER 3 - SOURCE CATEGORIES OF CHLORINATED DIOXIN AND FURAN AIR EMISSIONS.................... .............................. 3.1 Introduction..... .................................... 3.2 Confined Source Cacegories of Chlorinated Dioxin and Furan Air Ends siens....................... *......... 3.2.1 Incineration Source Categories................ 3.2.2 Boiler Source Categories........ `............. 3.2.3 Residential Stoves, Fireplaces, and Furnaces... 3 .2 . 1 Internal Combustion Engines........... 3.3 Potential Sources of Chlorinated Dioxin and Furan Air Emissions from Laboratory Experiments................ 3.3.1 Combustion of Wood, Grass, and Paper Treated vita a Fon u l a tion of 2,4,5-T................. 3.3.2 Combustion of Wood Treated with a Trichloro- phenoiate and Tetrachloraphenolate Formula tion.......................................... 3.3.3 Pyrolysis of Commercial PCBs and ?C3 Isomers... 3.3.4 Pyrolysis of Trichlorobenzene, Tecrachloro-- benzene, and Pencachloro'oenzene............... 3.3.5 High Temperature Oxidation and Chlorination of Coal.......................................... 3.3.6 3unit.g of 3irch Leaves and Wood Wool Treated with Calorophenates........................... L8 18 19 19 31 36 37 38 38 43 41 46 47 48 V TABLE OE CONTENTS Page CHAPTER 4 - CHLORINATED DIOXIN AND ECRAN EMISSIONS DATA___ 4.1 Chlorinated Dioxin and Euxan laissions from Incineration Sources................................ 4.2 Chlorinated Dioxin, and Eux an. Baissions frca Boiler Sources................ .......... ........ ........ ..... 4.1 Chlorinated Dioxin and. Euran laissions fxoa Resi dential Wood Stoves and Fireplaces.... . ............. * 4.4 Chlorinated Dioxin and Euran Baissions froa Internal Ccabustion Engines.................................... ,, 4.5 Source. Eaissions of Chlorinated Dioxins and Furans Determined froa Laboratory Experiments......... . 50 50 54 55 55 57` CHAPTER 5 - DATA ON PUBLIC EXPOSURE TO CHLORINATED DIOXINS AND ECRANS........ ;.............. ......................... 59 APPENDIX A - LIST OF REFERENCES OBTAINED FROM THE CHLORINATED DIOXIN AND EURAN LITERATURE SEARCH............ A-L APPENDIX B - DESCRIPTION OF THE LITERATURE. SEARCH......... 3-L vi Table Z-- 1 2-2 2-- 3 2-4 3-- 1 3-2 3-- 3' 3-4 3-- 5 4-L 4-2 4-- 3 A-i A-- 2 LIST OF TABLES gage Schedule of Theoretical Caiorinated Dioxin Isomers......... 8 Schedule of Theoretical Chlorinated Furan Isomers........... 10 Tyres zz Compouads that have been Identified to Contain Calcrinated Dioxins................... .............. . 13 Fro du trior. Sources of Major Criorinatad Dioxin-- and Furan-- Containing. Chemicals. ..... .................. ........ ..... . 16 Summary of Chlorinated' Dioxin Air Emission Source Categories...... ......... ............ ..... . . 21 Summary of Chlorinated Furan; Air Emission. Source Cat agoraes.... .............. ................. ..... ........ .# 26 Laboratory Research Experiments that have Identified Sources of Chlorinated Dioxins..................... Laboratory Research Experiments char have* Identified Sources: of ChlorinatedSurans.............................. 41 List of FCB- Isomers- that ware Pyrolyrad to Determine Potential Chlorinated Furan Emissions ................ ...... 45 Concentration Ranges- or Cal orinar ad. Dioxin and Furan Compounds Found in the Emissions of Incinerators........... 52 Chlorinated Dioxin, and Furan Emission Factors for Municipal Waste Incinerators.. ................................... Chlorinated Dioxin Emissions from Residential Wood Stoves.... .................. ............ ..................* 36 List of References Pertaining to Chlorinated Dioxin and Furan Air Emissions.................... .......-......... . A--2 Index to the Categories of Information Contained in the Dioxin/Furan References of Table A - L ................... A - 11 39 53 * LIST OF FIGUFJIS s 2-1 2-2 Paaa Picnic and fursn configurations showing "ha dioxin, and funan racial and conventional substituent numbering system. ............ . ....................... 6 &=!="-- 7-r diagrams of comnounds identified to contain rrt'r-- `-srsrf a-*oxins ^. ..... r-.... ....... .......... 14 VliV CHAPTER L STUA R T Oc THE CHLORINATED DIOXIN AND ETJRAN PROJECT L.L PROJECT STrnAET The UhS. Environmental Protection Agency (EPA) is- inner esc ad in chlorinated dioxins and furans because cf cheir potential toxicides to humans and because- several industrial operations have been demonstrated to emit relatively low concentrations of these compounds into the ambient air. Many of the determinations of industrial chlorinated dioxin and furan sources have only recently been made possible due co advancements in sampling and analytical techniques. To expand its knowledge on industrial sources of chlorinated dioxins and furans, EPA's Office cf Air Quality Planning and Standards (OAQPS) requested the development of a specific technical data base relating to chlorinated dioxin and furan air emissions. The. results of the data base development effort are summarized in this report. In developing the chlorinated dioxin and furan air- emissions data base the following four topics or questions were deemed as key. - what source categories might emit chlorinated dioxins and furans? - How many individual sources are in each source category and where are they located? - r*hat is the availability of emissions and emission factor data pertaining to chlorinated dioxins and furans? - Have chlorinated dioxins and furans bean measured in the ambient air? The technical Literature search was extensive and identified 462 possibly applicable references pertaining to chlorinated dioxin and furan (I air emissions. iftar a thorough review of these references only 87 were determined. to be germane to one or more of the key air emission topics given above: The Lise of references developed from the literature search per taining to chlorinated dioxin and furan air emissions is given in Appendix A, Table A-L. The numbers assigned to the references in Table A-- L are used throughout this report when citing a particular reference. No reference sections are used at the end of each individual chapter. For example, Reference number 5 can. be used Co document material in Chapters 2, 3, and 4, but it always, refers to Reference 5 of Table A-L,, The- details of the literature search effort that generated the 87 references are given in Appendix. 3. * la the. remaining chapters to this report, each on the- important topic areas is discussed individually. Chapter 2 discusses the chemical nature of chlorinated dioxins and furans, Chapter 3 covers source categories and individual.sources:- of chlorinated dioxin and furan emissions, Chapter 4presents. chlorinated dioxin and furan emissions- and. emission factor data,, and Chapter 5 presents available data, on ambient levels of chlorinated dioxins- and furans.. Only information chat was. determined from the 87 references given in Table A-- L is presented in Chapters 2 through 5. It is the purpose- of these chapters- to only report technical and scientific results that have been given in the published literature: No theories or conclusions regarding chlorinated dioxin and. furan source categories,, indi vidual sources, emission levels,, and ambient exposure levels are given. Whenever the terms literature or published literature are used in Chapters 2 through. 5, they refer solely to the contents of the references in Table A-L. L.2 SUMMARY OF CHLORINATED DI02TN AND FURAN SOURCE CATEGORIES AND EMISSIONS Source categories of chlorinated dioxin and furan air emissions, that .have been confirmed by testing, include municipal, hazardous, and chemical waste incinerators, wire reclamation incinerators, industrial boilers, wood slaves, fireplaces, residential furnaces, and internal combustion engines. ? I Although char a are rune reus individual sources within each of these source categories, only seven individual sources were specifically identified and discussed in the literature. Potential sources of chlorinated dioxin and furan air emissions have also been indicated by laboratory research. The types of laboratory experiments which have produced chlorinated dioxin and/or furan. emissions are the combustion of wood, grass r and paoer treated with a f o m u l a c i m of 2,4.,5-trichlorophenoxy acetic acid (2-,4,5-T), the combustion of v o c i treated with a. trichlarophenaiate and tecrachlora-- phenolate formulation, the pyrolysis, of commercial polychlorinated biphenyls. (?C3s) and ?C3 isomers, the pyrolysis- of- tri-, tetra-- , and pentachloro-- benzene, the high temperature- oxidation and chlorination- of coal,, and the combustion of birch leaves and wood wool treated with chloropaenates.. Chlorinated dioxin and furan amissions have been measured in relatively low concentrations in both particulate and gaseous exhaust streams; however, mast emission tests have only analyzed particulate emissions for these compounds.. The majority of available emissions.- data far chlorinated dioxins and jurats is in the- form of emission concentrations and amission factors 3ecause the identification and measurement, of chlorinated furans- hnq only recently become important, more emissions- data are available for chlorinated dioxins chan for furans- Tor the source category in which the most data exist, municipal waste incinerators, total chlorinated dioxin levels in the exhaust fly ash have been neasured to range from 23.3 ppb to 2966 ppo. Total chlorinated furan levels from the same source range from 13.4 ppb to 2036 ppb. amission: factors developed for municipal waste incinerators on the basis of the amount of waste burned, have been found to range from 0.23 to 16.3 yg/kg-for total chlorinated dioxins and' from 2.3 to 17.4 yg/kg for total chlorinated furans. 1.3 RECOMMENDATIONS 303 FURTHER STUDY OF CHLORINATED DIOXIN AND' FURAN AIR EMISSIONS From the review of th conclusions have been made efarences in Table A-- 1, several observations or n c e m i n g areas of the chlorinated dioxin and j 1 fI furaa p rob lea where aora study appears to be seeded. The first: area of che chlorinated dioxin and furan air amissions situation requiring more examination concerns the great variability of the emission test data that have been reported for several similar sources. Thera needs to-be more concentrated study on why chlorinated dioxins and furans were found in the amissions of m e municipal vasta incinerator and not others burning wastes of a similar cmpcsition. On this subject,, more work needs to be done on analyzing the composition of. the* materials being burned to find, out if they contain chlorinated dioxins and. furans or dioxin and furaa precursors.' Other questions also persist such as why have dioxin and furan compounds not been detected in the-emissions of utility boilers, while they have been found in industrial boiler and incinerator amissions. Some limited theories have been expressed to explain this occurrence, but more work, is required to scientifically validate these theories. delated to studies of this type would be additional examinations of the formation and destruction characteristics of chlorinated dioxins and furans.. If chlorinated dioxin and furan emissions from, a source- are- potentially deemed, to be significant,, technically affective* and economically reasonable control measures need to be determined. The second area requiring mare study, as shown by the literature search, involves determining whan are the ambient air levels of chlorinated dioxins and furans- Basically no data, are available* because measurements have not been made. Limitations of currently available analytical tech niques to detect these compounds in the environment may be responsible for the absence of ambient measurements. The extent of the limitations caused by analytical techniques needs to be further investigated. If currently available analytical techniques are capable of detecting chlorinated dioxins and furans in ambient air samples, an ambient testing program focused on confirmed dioxin and furan sources, such as incinerators and boilers, needs to be initiated. 4 r CHAPTER 2 CHUHCAL BACKGROUND ON CHLORINATED DIOXINS AND FURANS The purposes- of this chap car are co describe cha general chemical composition or ilrnics and furans and co describe che specific chemical characteristics of chlorinacad dioxins and furans, Brief discussions regarding chlorinated dioxin and furan fomatioa mechanisms are given, however, che reader is urged co consul" che references provided for a ccmpleca- and decalled creacnenc of chese copies, 2.1 CHZbUCAL DESCRIPTION OF DIOXINS A dioxin is an.7 member of a family of organic compounds known chemi cally as- dibenzo-p-dioxins. The common aspect. of all dioxin compounds is chan they concain a cripla-ring nucleus scmccure consiscing of cwo benzene rings incarcouneccad Co each ocher chrough a pair of oxygen, acorns. The scrueCural formula of che dioxin nucleus and che convene!on used in num bering ics subscicuenc posicions are shown in Figure 2-L. Each of che substituent: posicions shown in Figure 2-L, numbered L chrough 4 and 6 chrough 9, can hold a chlorine or ocher halogen acorn, an organic radical, or a hydrogen atom (provided no ocher subscicuenc is indicated in Che formula or chemical name). The only differences between individual members of che dioxin group are in Che nature and position of su'oscituencs.53 From an environmental scandooinc, chlorinated dioxins have received che greatest amount 01 32 at can cion. `......................... . m cnaornnacea oaoxrns, cnlorme atoms occur ac various subscicuenc posicions within the nucleus structure. Theoretically, one to eight chlorine atoms can occur ac cioxin subscicuenc posicions such chac 75 diffarenc chlorinated dioxin isomers are possible. Each isomer has ics own physical and chemical properties, and differs from 3 4 . *: a ..p io ^ in c o n fig u ra tio n . b. Fufnn c o n fig u ra tio n . , .# Figure 2 -1 . Dfoxfp and furan coqf4.g11rat14.ona showing fhe d io xin and furan n u c le i and conventional su b stitu e n t nniubejring system . 5 8 i f others in the number and relative position of its chlorine atoms. The schedule of potential chlorinacad dioxin isomers is given in Table 2-L. The ab'oreviacicns given in Table 2-L for classes of chlorinated dioxin issuers are used throughout this report. The chlorinated dioxin isomer receiving the most attention is 2,3,7,8-- TCDD. Unformnarelj in the published literature chemical nomenclature has often been rather loosely applied, and 2,3,7,3-TCDD has been reported as TCDD or simply as tic-- In. It is incorrect to use the terms TCDD or dioxin when referring to a specific positional isomer such as 2,3,7,8-TCDD because there are 22 different TCDD isomers and eight different isomer classes of chlori nated dioxins. This nomenclature problem, has lad to confusion when crying to assess reported results of 2,3,7,8-TCDD detection. In this report the term chlorinated dioxin is used as a substitute for chlorinated diban-- zo-?-dioxin and refers to any organic compound with the basic dioxin structure given in Figure 2-La and. the term TCDD (or other isomer abbre viation) is- used to referr to the specific group of tetrachlorinated dioxin isomers (or other isomer group). when specific positional isomers such as 2,3,7,8-TCDD are indicated or discussed, they are specifically delineated by chlorine substituent numbers. 2.2 CHEMICAL DESCRIPTION OF FUPANS Furans are a group of organic compounds known chemically as- dibenzo-- furans. They have a similar structure to the dibenzo-p-dioxins, except that the cvo benzene rings in the nucleus are interconnected with only one oxygen 3o atom and a single carbon bond (c-c). The structural formula of the fursn nucleus and the convention used in numbering its substituent positions are shewn in Figure 2-L. As with the dioxin nucleus, furan substituent positions are numbered L through 4- and 6 through 9, and the positions can be occupied by a chlorine or ocher halogen atom, an organic radical, or a hydrogen atom provided no ocher substituent is indicated in the formula or chemical name. The positioning and number of substituents determines the / * TABLE 2-1. SCHEDULE OF THEORETICAL CHLORINATED DIOXIN ISOMERS 53 Calorinated Dioxin Ccmoound Monochlo radio e m c - p --dioxin (MCDD) Dichlorodibennz-- p-- dioxin (DCDD) Trichlorodibemc-- p--dioxin (T^CDD) Tenrachlorodibenno-- p-dioxin (TCDD) ?encacnlorcdibanno-p--dioxin. (?CDD) Haxacnloradibema-p-diaxn (ECDD) Heptacaloradibenzo-- p--dioxin (H_,CDD) Occachlorodibenzc-p--dioxin (OCDD) TOTAL. Number of Isomers 1 10 L422 14L0 * 2. 1 7 S_ 3 / physical and chemical properties of che furan. 70 A detailed discussion, of the properties of dibeuzofurans is given, in Reference 70. The chlorinated furans, like che chlorinated dioxins, have been the subject of nost of the furan research. Theoretically, che chlorinated furan group can contain up to L35 different structural isomers, each with varying physical and ciauaaal properties. The schedule. of potential chlorinated furan isonars is given in Table 2-2. The abbreviations given in Table 2-2 for classes of chlorinated furan isomers are used throughout this report. The nomenclature explained in Section 2.I for references to dioxins in this report, is also used for furans. The t a n chlorinated furan. is used as a substitute for chlorinated dibeuzofuran and refers to any organic compound with the basic structure given in Figure 2-lb. Classes of furan isomers are indicated by the appropriate abbreviations (e.g., TCDF, OCDF) and specific furan isomers are delineated by positional substituent numbers. 2.3 OCCURRENCE AND FORMATION OF CHLORINATED DIOXINS AND FURANS Chlorinated dioxins and furans are not intentionally manufactured, except in small quantities for chemical and toxicological research purposes However, chlorinated dioxins and furans occur in several commercial organic chemicals as unavoidable synthesis contaminants, and as -such potentially can be released to the atmosphere curing normal operations- or upon use of the chemical. The mechanisms by which chlorinated dioxins and furans are formed, during the synthesis cf various organic chemicals, are complex and have been intensively studied by researchers. In this report, the objective is to briefly discuss and familiarize the reader with the types of chemicals known to contain, or with a propensity to form, chlorinated dioxins and furans. Extensive and detailed discussions and analyses of chlorinated dioxin and furan formation mechanisms and organic chemicals associated with these mechanisms can be found in References 13, 70, and 77. 9  .TA3LZ 2-2 SCHEDULE OF THEORETICAL CHLORINATED FURAN ISOMERS 70 Chlorinated Furan Compound ionochlorodlbe"cfuran. (MCDF) Di calored ibernar*-- an (DCDF) Trienio rodio enroaran (T^CDF) T ecrachlo rodio earafuran (TCDF) ?eatachloradibentefuran (FCDF) Henachlarodibenzofuraa (ECDF) Hep cachlo rodio enz ofuran (E^CDF) Qccachlorodibenrofurar (OCDF) TOTAL Number of Isomers 4 16 28 38 28' 16 4 L 13T . 10 1 One roue a of chlorinated dioxin formation char has been demonstrated is generalized below:^ + 2XY The reaction shown above indicates that for a compound to be a dioxin precursor it rust neat the following conditions: the precursor compound must be an ortho-substituted benzene ring in which one of the substituents includes an oxygen atom directly attached to the ring it must be possible for two of the substituents, excluding the oxygen atom, to react with each other to form an independent compound. An example of this concept involving 2,4,5-crichlorophenol is shown below: (Predioxin) + Nad 2NaCI Many organic compounds neat the dioxin precursor conditions specified above. The more prominent compounds in which chlorinated dioxins have been LL I found are given, in Tab la 2-3. The 2,3,7,3-TCDD isomer has been determined in 2,4,5-T, 2,4,3-TC?, and hexachlorophene.^ ^ In ?C?s the major 1 57 chlorinated dioxins found have been H O D , H^CDD, and C O D . " ' 3ecause of their chemical structure and composition, several more synthetic organic compounds chan are given in Table 2-3 have the potential to contain chlori nated dioxins. During the nanuinature of an organic chemical, chlorinated furans may be formed as a result na reactions competing with chlorinated dioxin-forming reactions. With seme precursor compounds, condensation of a chlorine atom.' in the ortho position to a hydroxyl group may not occur and a chlorinated dioxin is not farmed. This situation is demonstrated by the following 18 reaction: ci a NaCl The end product of the above reaction has. been termed an isopredioxin. The isopredioxin can polymerize into long chains, or it can lose chlorine which IQ leads to the creation of a chlorinated furan, as illustrated below: iI 'TA3LE 2-3. TYPES 0? COMPOUNDS THAT HAVE BEST IDENTIFIED TO CONTAIN CHLORINATED DIOXINS1,18,57,80 Compounds Confirmed to Contain Chlorinated Dioxin Contaminants a Chlorinated Phenols -- P grcachl a m p aeno 1 (TCP) -- 2,4,5-triralaropheroi (2,4,5-TCP) -- 2,4,5-- triciloraphenol -- 2,3,4,5-- tatrachlorcphenol Phenoxy Acids and -aeir Esters and Salta -- 2 ,4 ,5-crichlorophenox7 acetic acid (2,4,5-X) -- 2,4-dichloroph.enosy acetic acid (2,4-D) -- 2-(2,4,5-- tricolorophenory) propionic acid (Silvex). -- 2,2-dichloropropanoic. acid 2-(2,4,5-trichlorophencxy) ethyl ester (Erbon) -- 2,4-dichloropharoxvachyl sulfate (Sasone) -- Phosphorathioic acid (Ronnal) Eexachlorophene -- 2,.2*-methylene bis (3,4,6-tricaloraphenol) a2olecular d i a g r a m of the* compounds given above are shown in Figure 2-- 2- 13  oeil2C H 2O S 0 3^ a ci ci Sogono (pOQH c,, 2 Cl 4> ci OC II2C| l20-COII- c C|2C1 Cl CI Oil PI PI <poon Sllvox Oil PIv ^ ^ y PI Cl o h l C)v<^-- \ V O I I Cl Cl 2,4-Diclilorophonoxy ocelle aclcj ? l;3l4 v6 -T tr^ch|prpphpo| 2,4,6-TrlcSDprpphonol pn|ach|oropheno| Figure 2-2. Molecular diagrams of compounds identified po contain cjilprlnafed dioxins.IN I I1 In Is also believed that chlorinated furans can be formed 07 a reaction betvsan a chiorophenol and a polychlorobenzane through an intermediate, creation of a diphenyl ether. An, example of this reaction is given below: 50 aa N a d 4* 3 Cl (Chlorinated fursn) As expected, many of the compounds chat have- been found to contain chlorinated dioxins also contain chlorinated furans. The major sources of chlorinated furans are phenoxy acids (and their esters- and salts) including 2,4-,5--'I and 2,4-D, chlorinated phenols including ?CF, hexachloro benzene, and polychlorinated biphenyls (PC3s) In- PCPs and hexachlorobenzene the prodominant furans found have been. H^CDF and OCDF isomers, although TCDF, ?CDF, and HCDF isomers have also been determined. In some samples- of FC3s, the furan isomers 2,3,7,3--TCDF and 2,3,4, 7,8-PCEF-have been found to be the most, prevalent chlorinated furans present,^ As a result of the concern raised over suspected health risks of dioxin-- and furan-containing chemicals, certain uses of several of these substances, such as 2,4,5-- 1 and Silvex have been suspended or greatly reduced L 14 by State and Federal authorities. * Consequently, the need to produce such chemicals for present or future' use has diminished to the point where only one or tvo *companies make several of the chemicals, and in same cases (e.g., 2,4,5--TCP and 2,4,5-1) production has ceased. The current producers of major chemicals confirmed to contain chlorinated dioxins, and/or furans are listed in Table 2-^-. 15 * TA3LZ 2-4. PRODUCTION SOURCES OF MAJOR CHLORINATED DIOXIN AND PIRAN CONTAINING CHEMICALS3, Chemical Producer - Location Pentachloror ceno 1 Reichhold Chemicals - Tacoma, WA Vulcan Materials, Vulcan Chemical Division - Wichita, IS 2,4,6--Trienio rcr hiinol Dow Chemical -- Midland, MI Rhone--Poulenc, Agrochemical Division -- Portland, OR 2,3,4,6-Tetraceloroph.enol Dow Chemical - Midland, MI Silvex Riverdale Chemical - Chicago Heights, XL Dow Ccemical - Midland, MI 2,4-D Anrvac Chemical - les Angeles, CA Diamond Shamrock - Tuscaloosa, AL Dow Chemical - Midland, MI Guth Corp. -- Hillside, IL Rhone-Poulanc, Agrochemical Division - Portland, OR Riverdale Chemical - Chicago Heights, II*. Verrac Ccemical - Jacksonville, AR Hexachlo rophene Givaudan Corp., Ccemical Division Clifton, NJ Source: 1982 Directory of Chemical Producers, Scaniord Research. Institute, Menlo Pari-c, CA, 1982^ 15 Several non-chemical, industrial sources such, as power plants, incin erators, and boilers have been identified as potential sources of chlori nated dioxin and furan environmental emissions*. These sources are exten sively discussed in Chapter .3. T/ CHAPTER 3 30US.CZ CATEGORIES OF CHLORINATED DIOXIN AND FURAN AIR EMISSIONS la cals cicar confirmed aad potential sourca categories cf chlor inated dioxin aad furan air emissions are idaacified. Two broad types of emission source categories ara discussed. Toe first type iacludes indus-- trial, commercial, aad residential enissiou source categories that have been determined by testing. The second type involves potential emission source categories that have been extrapolated*from laboratory experiments. Quanti fication of the chlorinated dioxin and furan air emissions from the source categories identified in this chapter are presented in Chapter 4. 3.1 INTRODUCTION In 1973 Dow Chemical Company issued a report which stated chat "chlor inated dioxins ara ubiquitous." Dow concluded chat "their presence is due to the existence of a natural phenomenon,, trace chemistries of fire." In its study Dew investigated many combustion sources and determined chat ^ 7 were sources of chlorinated dioxin air emissions. Included in Dow's list of 6,11,31 enuorinated dioxin sources are: hazardous waste incinerators, municipal refuse incinerators, industrial boilers, internal combustion engines, home heating furnaces, fireplaces, and charcoal grills. I The Dow worst cantered solely on determining the existence of chlorinated dioxins. 'Tone of the obtained samples were analyzed for the presence of chlorinated furans. The Dow study and its "trace chemistries of fire" hypothesis aroused the interest, of many researchers in the field. Spurred by the Dow results, and similar but rare qualitative results from European research, a consid erable amount of work was begun to address the question of chlorinated dioxin ubiquity anc the relationship to combustion chemistry. As a result of the increased interest and research in chlorinated dioxins, the existence and prevalence of similar and related, chlorinated furan compounds became more important and more well-known. Research into the formation mechanismsof both families of organic compounds- indicated that chlorinated furans also m a y be connected with combustion chemistry, following the 1973 Dow report,, many researchers in. the United States and Europe began examining combustion sources, and other potential formation, mechanisms of chlorinated dioxins and furans. Much. of. the work., focused on possible sources of chlorinated dioxin and furan. air emissions. The results- and conclusions of these studies on source categories of chlorinated dioxin, and furan air amissions are summer- ized in. this chapter. 3.2 CONFIRMED SOURCE CATEGORIES OF CHLORINATED D I O U N AND FURAN AIR. EMISSIONS The discussion of confirmed chlorinated dioxin and furan air amission sources'is divided into four major classes or types of source categories. These major classes are incinerators, boilers, residential stoves, fire places, and furnaces, and internal combustion engines. Distinct emission source categories within each class are identified. 3.2.1 Incineration Source Categories In the list of references given in Table A-L of Appendix A, 34 different and distinct references are given on the occurrence of chlorinated dioxin 1 and furan. air emissions froa over 50 incinerators. Tables 3-- 1 and 3-2 present a sumary of the chlorinated, dioxin and furan air emission informa tion froa these 3 1 references. Included, in the information of Tables 3-L and 3 - 2 are the types of incinerators where dioxin and furan emissions have been determined, the classes of chlorinated dioxin and furan isomers that have been found, and, the types of samples in which the dioxins and furans were measured. Chlorinated dioxins and furans have been discovered in the air emissions of incinerators burning municipal refuse, chemical wastes, hazardous wastes, and scrap wire. These incinerators, are located in the United States, Canada, Japan, Italy, France, Germany, Sweden, Switzerland, and the Netherlands. An analysis to determine the presence of both chlori nated dioxins and furans has not been performed on all incinerator air emission samples.. However, in the cases where both groups of organic compounds were analyzed for, both have been found to be present. From all reports to date, it appears chat whenever incinerator sources have been specifically examined for chlorinated dioxin on furan air emissions, these emissions have been found. The. spectrum of testing chat has been conducted on incinerator sources varies from single sample tests of one incinerator Co nulci-samole cests of . 32,40,59 _ .* up Co 25 incinerators.. Tests aave oeen conducted over as long a period as 9 monchs in order to monitor the variability of chlorinated dioxin and furan emissions vich varying inouc leads, load characteristics, and i.nci.nerator operati.ng cond.i.ti.ons. 68",33 \ In attempting to detect chlorinated dioxin and furan emissions from incinerator sources, researchers have primarily examined fly ash emissions collected by incinerator control devices such as electrostatic precipitators (ES?s) . There are cases, however, where samples have been taken of fly ash emissions from an ES? stack, fly ash emissions from an incinerator stack, and fly ash and gaseous emissions from an incinerator stack. Sampling of ES? fly ash catches predominates primarily because it is a much less difficult procedure than extractive sampling of particulate and gaseous 20 Tub]a 3-1 SUMMARY 0 V CHLORINATED DIOXIN AIK EMISSION SOURCE CATEGORIES Typa 1 Caule* Type uI ClINpl HCUP, UCPU TjfUl TCUU J.J.i.f-TClHl Total fLUU (ICUII ii^ruii orjHi CuaueHla Klrana. IIUI HWI IIUI IIUI lur (wall! ull IIUI IIUI ffi 0.061 ,.b/Vj ol TjtliU ya hum ri>r MA ru IIA ra Mu usr, NH lack >* fro* tur. MK luck ya |i m nsr. M* tuck f A 11 ota i ack A 1com alack NA UA ' U.1102 Mf/kt HIS MW# HM MK MR MU MU-MO ft-U 0 .0)) py/k| HO 0.0? P|/k| Q.Olp |<f/kf H.Ul) l>|/kR V frl* )? Uf/*1 nk n * ?M /** MU ppk iiU ..i/** 7Co |ipi> ) U u|/ua1 1^1 fpk 4>? Ml/ - 1 1.4- 1? fH* .- .a m ** M " ? * f|V M - l l , ? pp* 7.4-11 9 p|b UK NR NR W IIK MK HI IIH Mi MX MU 1)00- noou UK |--20 ? 7-1co | ? IM |0 j.pk 1 )()-) too rr* 1000-1)001) ppv 1000-19000 PpM A ll JIcia |ii and luran uyaclaa aivuauiaJ lit naeou |.|iiiau, non lounti In fly ua|>. ) Uaiaya ruull of lu.la on 19 9 Inc Inurnlui u 111 lliu lit.I lieflanJu, una.li u m ItaJ li taaylaa lukun. Hula Icpoftuj Ini 11y mill ami ||u yaa fcaullg. ` ilia ante ol lci.nl lu lounj H Ilf laala if 1 Jafmituac , 1 Cana-lluii, ml on Uulcli Inc Inc i atin' aia given. Tit (uiau vnlnu uni JailvuJ nj a ll only utiail-ijuiuit 11u||vc . Total tit 1oi 1n;a1oil illoaln ai|u) 0.2 p|ita, lu|u| tilllot Inal il fui an aapial 0.1 p|na. l.lJ.U-VCim 1 a aalilol cuiaponiiiil ol 1 Ini del aaIon. 2,1,) .B-TIIU' 1 an* Joe ca>i|iniiu( ol lit ulal<>iiu. f ) # )| Total elilot Inn 4 J1ua lai <|u| 0.6 |.|iMa total ell 1an Inal uU Imnt.ii cifti| 0.) pt*. 2.).).Q-|U>I> la a aInna Cdta|iuiiClil ol lit alauloua. 2, l.I.M -K U l la mJaap tlinapdiluitl ol tlm ctalaaloAU. 2), )i layteal 1 a liquid lay Inclnaialur. Cu|tp|aacitlul lUUliif) yuj fuel la uuml. 2, C. ||, Rotary kiln clia!ia|ca| waulo 2, 6, 1nc 1liei at of u11la no ini|t|tla- ||, 5| ita| (lying |tta|. Tub Id 3-1 (Continued) S U M M A R Y OV' C H L O R I N A T E D D I O X I N AT U E M I S S I O N S O U R C E C A T E G O R I E S Ty|> o l Su m cu T y ! o 2 Sn*>|>lc m ail, n cu ii ( j f ltU TUUi l,l,l,R -T u im T u i i ru m IIU U 1 O U ill CuMthClli * * |IU| 1A llw IIA l i U nwi tk i foik n r IIA UK 1 n I(iim HA luck mil Yk l i o tsr HA IIUI i a iiiiu n r IIA IIUI rA id. IIA ||(>11 u f IIUI rA horn HA III *Lk IIUI a h o t i r llll IIW| l'i h o n r till IIUI rA t loi. m * HU INI ia it* rsr HU INI i a i ( u u r IIA IIUI i'a <rit n r HA IIUI rA, ru HA IIUI n tie n r IIA ml i rA i(o HA K'SV, tlutl `i pfl* U.4 |i|>k> HRS <110 yys 2.) |>pb ?- n + HR h i Rf** All} py| ?.} f(>U 6 M ri-H 11 . |(A UR HR Hl> HU IIU Him 12 y y l frb 0 .1 } y,.b l.l |`pb HR |>|i|> " 1 (.(.H HR IIUS HR IIRU 1.12 |>ylt 2.)4 ppb < M ri'H HR HR IIR HR HR HR HR HR HR HR} 1.4 rrb 1) f|*b HRS AU py|, <0.1-1 |,|.b 1 -|ID rrb ia n>i> HA IA y VU 150 |.,.U 21 |*|.| HA 28 j>pb |(K0 t*)>W HP IIP )U A" n 1* 1 ill |.,b ]U ppb HA 10 j.j.b |kU Jlpb re* 121) ,.,.b l u U i y kllu fbaulcal wnula 7. 6, IniInclalur wlili au|i|> 1intii- II, 11 u i m i n i |uci. 2. 6. II. 11 2 , 1 , 7 , P - | w u <i i uura nut pkicll (call} aila 1y <a>| (or. 61 12, AO )!, AO tollar an4 alaub aauplaa |kcu la.uk 1aixoualy. 12, AO 2. AO IIU HR HR HR IIR HR IIR il rrb SAO HR HR . HR HR HR HR IIR 1.2 ppb 00 |>|.U no n.k n . i |>rb O.R pyb 164 |<|*l* HR HR HR Oj.A >|>b `JOO ppb Only (aeulla lot Tnm.lHUip, A nU 2.1.).R-TCi>u rjri" 4. A A A 22 22 HR (>A) I n J U a l a a fuuiul only to fly aali A v a l * ( t t h o c ua.lt1ncJ aaw|t|*e uf Iwu Cuitatllaii Inc literal mi a. 22 72 4} Table 3-1. (Continuali) SUMMARY OF CHLORINATED DIOXIN AIR EMISSION SOURCE CATEGORIES . ~ ... -- )- - - - - -- - - - - -- -- 1 lyjiu ut SliliCT Tyi'i u( Snn>|*lc 1111*11, 1)0*11 XjCUD Hllll 1,).J.P-TCHO Total - - - -- . . . . - -. . . . -- - - - - -- - , -- - - - -- -- - - - - -- -- - - - - - - - - - - -- - - - - - - - - - - - - - - rw HOMI Iif run iii:i<ii (oiuniclii Pe/r *114 IIW| rA, re HA HU MM * HUI li ft um r-tir HA M ri*"> Mf H U HK8 HP liuti <# MR HA M# ) llalla Inc lucro!ora Il w < K tcalcJ and lulu! aaouuia ut dlualit and (urima war* (aj.i.flad aa me a.. Value. 9AH ftC4 (l*nm t?00-)3J(J bliiyla leal til a aulitici.#! wunta lyfulyul nyali. 1 >we Jr.ii, ii IMI rx. iu flop HA fltc) IO id ipil a (run esr HA IMI IA hum HOP HA HP 121 nf/.1 il H i u p / 1*1 ?0( i/.,1 |2i y/.1 It au.ijilaa taken tium ail tu. o) Italia incinerator over a ) .imiti licitad, t e m i l i afa Ilio av e ia ye of 11 leal, lutai dilu limi ed dlualii estuali.a (ac lui la IA,2t/ I H /lull ol wanlu liilined. Tulal dilli Inutcd lui au r.la- alaii Iteli la I1.H2S iy/luti ut nate lui ned. HR# |1.) ,-yl il ? f P 1* 21.# f p(. I L ? ppo pH* p e mi Ita repfeecnl III. avatnyc ut etytil an.|>li:u. 6} HU HO M r ,l. 21.8 y,.*, # 2. A p,.b IDA |.,L (2 HUI rA, n HA HUI ia , ru HA ID '(coalt Jrad) FA. 0 11 (icluie- f a . ru ( 1 1*4) IVI rA hum luck HA HA IU Oli .,/k, O . O U H/k| HA HA MA HA 0.021 n /K , O.OAi HA HA HA HA 0.20 ny/ly 0.(9 t*|/P| HA (IA HA HA 0.11 vy/k| . H p|/k| MA MM loo ppV |6t) P)<b HA (00 (.}! HA M 9 rr* HA |AO yyl A aa.,ilca nero uiily aualyicJ 1/ lui tet f ad 1i'i 1imi 4 J l m l m and lunula. Avcfayo valile aia aliowii. 1lieine ia tof lui mi le In e and 1/ u n t e olla. 1 t|iUt uste only analyrcd (or letraclilorInalrd dloalna and luan, averay value ara nliauu. Snaijila w ua only Aiialycrd (or 11 lutf editor liiulcd dloalna nud (uraiia. - Pani,ile vai only aiitlyred f o f Il le*l fmi:li|or 1noi od d i n d o n uuj luf mia. 12, A0 * i Tablu 3-1 (Coni 1nued) SIJNMAUY O F CHI.ORINATO) D I O X I N A I R K M T S S I O H S O U K C K C A T E G O K I K S l'f" " 1 T|l|' v* llCtili, liCUII T<>h u (toni i a Snap 1a T j O iD I.J ,/ . 6 -TCIH futa! fruii lidio lljCI'll Oditi OuMeciil Rei rbruii )IU| rk (Vo m tsr HA IMI re HA Ib rA iiu HA OlacV HWJ rA HA 6W3 ra HA KMS rA HA m r A HA Hill' 'A HA icr. (gnauline) fA lui Il lei a HA tee (.lituo 1) IMI IA (eoa aaif 1 1 era HA rA, rr (> HA atack KM i n o r |.ii 11-Ano ppb ao-ijon ppb 190-90/ ppb 106-266 ppb Hf3 *1.1-160 ppt HA Ha HA HA Hit 19 ppb H# O-IHU ppf |OAI-A25 pp| HA HO-Il ppt HO-)/A |>p| HA 6- n rpt 114-111 ppt HA Ho- 0. | ppb HO-O.A ppb HA 0 .6 |>|<li 1 ppb HA H H-O.OUA |>|.b M i - 0.(100 ppb HA P.tXt) |i(.b NI! 0 .0 /) HA H O - 6 .1 ppb HA 1 ppb \ n* 1* 2A ppb 10(10 -A )00 |.pt 2 ,1-2000 ppt 2#00-A 100 ppt 0.9-9000 ppt 20 00 -1)0 0 ppt lA-l/AliO ppt 0)0-2600 ppt O.J-J ppb )A ppb i/on-Aoiio rpt 0./-I6 ppb l/OO-AOOO ppt 0.9-21 ppb AIO ppb 1)00 ppb HU 0 .0 2 p,.b HA 0 .00 )-0 .0 | ppb 0 ,0 2 -0 .0 / ppb 0 .|0 ppb 0.26 ppb HA HA (Unge uf va luca fnumi fruw )2, AO 60 Aiiulyace ut 21 Ine luce a tuia. Tanta Cuiiduct e<l imb on i O III il/T VulcAiiua lini lug cucbuatluu uf Ageut Oiaitge, Rcuulla Aie th langn uf v al ut i 1 ( 21 (rnlH. AO, HA , Roller |<t l i m i ulti, emi Aliti luci oli. U d r e i 1mi llull lui },) ,? . fl-1 r im wu 4 cuti/ IO 1*1*1* 6 , Il 11 (Uilfeitcy |i4 i 4 1<1.il e H 4u,|*lca vere lek:*. Trui **1 li* wui u In |luw 11tii*|)ttli1 1 u i , Cblwuuy p 4 1 t leniate nnkiplua 1 kilt Clini. Tuillcii altea | wci e tu llliiumul iniJ ' llltlilgeii. 11 11 dii *uia} palli culai acwplca wc-ie tal tu. l ea le ) u|leu v aie III O i c uii. 11 Cblwuuy piiellculntu uaplca tuteli 1 III Iwu re liluilt |a 1 1 Ifrplai'en. 6 . Il 11 r n l t u i l i U iiu.p leu Cui IccteJ 6 , Il fruii tilt t6r platea ni a 51 naturai gnu- Ilici Ituiau lical- Ing lui linee. l.uaJcl ami unle.nlcj Inala ueic unni In lliu lenlcl eutnumbl Ica. 6 . Il 51 6, Il 51 Inuinaratur l'urna iruftiitl naluateJ vanita. a * Tab l e 3-1. (Continued) S U M M A R Y O F CHLORINATEI) DIOXIty AI R E M I S S I O N S O U R C E C A T E G O R I E S Type u( t l ' x l . f el nia|, Ic MU*W, i)C.ui> T j CUD Jt . * > TCIU i T< ) I' CPD IICW J II ^CPU ClIMWCIltq fMCI UWI ta.rc i.a HA HkS HDO.ifl pPb HA HA HA HA lue luci at or burn ICB- lack , otti attillai J vuatca. iti lei la lit lug uouj vital, m |A ima labile iiltag II HK H H MH IIIt HU anti I'Cl'/cicount a u u . U - v . l d al.luif, / us |A, |U Ilota NA HA Mr Citivi Inal eJ Intana t|tt|i- I t NA HA MA HA H A * 1al 1ve 1g Ja 1c iatInc J In be pi vanti in CSI' lip aali mil gue cm!Iuii*. *1 cgellJl lIUl - llunlclpal U uslu Intlueielor IA J 1y Aul CUI - Clienti:a I Until. Incineratiti Iti " Pine iaa lull - Her at J ou e Waal Inc 1tic1 u tu t ter tlacliualall fraclpltalor UHI Ulte Kuclaiu.ilten In: liter litu( HA - Ilei A ua lyicJ IUI - inJnaliinl Uaula IncIncrulei no - Ilei PcluClcJ m u a - Ica 1.Ioni 1a 1 WttoJ Sieve NK - Specie# Jul ct u lu cJ In ta g i t a m i bui i|uanl i1 |ca| lui) no fuportc) ir - lUel.Kml.il tlieptacu M M - Hot Kepul |a J i.|,ai.l.|jf Kill - If. 1.Kill 1a 1 llual lug P o m a c e ICC - Inlviuai C.uJ.uul ion Cugino r i - l'atla lei III 11 luti p (.b - l'alia Puf Bit liuti m r - 1uJtial 1 iv | llu .il leg I'lunl IB * InJuuliidl B u l l e ri-, Culla re T ll ll l un I - Utility Dollar bPal a Ini B clcicncta 1 anJ 1/ ala Ip lutar u| caiaaiuita par nuli ni naala buiiiej. C C u | I uii cltlorInaicJ iu(mi Jala potuta (ui am.li ol ilia aatg in tlila labia , i d given In Tatla 1-2, li t 'iy|*e ul Simi et Tabi e 3-2. SU M M A R Y O F C11I.ORINATJl) FURAN A I R F M I S S i p N S O U R C E CATEfORIKS i ___ _________________________________________________ i____________________ -- ---------------------------------------------- ;----------- ^-------- V fiMI ut Saette iicur, u c h f Tcuf TjtUf i . U . S . - K V r Volai rtur HCllf i cur . Cuwmuii a Kier rili' IIWI 1.) vtflVf. 1 Mi> l, :( rerI t i l i fa {tu ha ru MA hk$ NKS FiAImI4rum FliF , ij IIW| 1A (ina rsr. * Iiick HHS UH llli' (waulu FA I rum etir, ull Im i 11k r ) (*111 |IU| IA f r a alaci IIWI I A f ii>m IIA a la r li MA IIA 0.4) |.|/k HI) 0.1| l*i/k|( 0 . 0 l'|/k| (I.OIU ft/kf 111 r|it. ibi i.e/-1 I H ffrh li WH/1 4)9 |*|U SIS i./m * 1|| J'F** 191 ap/a.1 Il p|b AD ii|;/a.^ .4-4.1 rrk .d-U rpb V - 2 . 1 |T b 4.1-1 ppl. 2-4.4 pi*l* IIH MK IIR l'H M| UH MK UH IIH UH MA HA HA MA IIA IIA HA HA MA MA All Jluxlii aiiJ I m a n apccla* 1 annullili In .lacuna pliniiu, urtila (Umili In (ly Bali. Avcrnffc |inulta uf lupi* mi )9 9 lucluariiiiMN in ili UciliarIhiiiIu , arti Ical Inni 14 ama|i|aa Itili;il. Itilia aia f ci miimi (ur IIjr tn.lt 1111*1 l (un mi icimila. llic lanfc ul im u l t a luim*| 74 III Itala ul Jt>|iuiiirac, 2 Cimali |u n , nini mie Unirli Ine Inai alni a m glvcn. TUu (unni vnlura waiu Jc-rl ve*] ami are uni y aneli-i(tiuut 11 al 1v|. Volili dilu 1nul a >1 limimi a<|ual 0.2 l'i'ia, lai ni dii Ui Inai Cil (ululili rifiuti 0.1 |i|*m. 2,1,2.R-VCUIi la a m inor e mainine ut ut die amlaniuiia. 2 ,1 ,1 ,0-lCliF la a aajat ciiai|iniiuiil ni III Hai 03 1(11111. 21, 4 Total dilu Inai cil ifloalua e<1iiji1 0.4 1*1*111, lui ut dii or Inni ci (uiaoii celiai 0.1 |*|*w. 7,1,2,11-1 dlll la a a litui coai|iune ni ui lliu aialauluiio. 2,1,2 ,H-'IC'HF la a wajul cuia|iiiutnl ul ili emina luna. 21. 14 S ya lc H la a tli|ull tur liiclueiator. Sup|i lciacni A 1 u n t u m i (u luci la tmcil. 2. 4, II. )l Hulaiy 4llu elicali l'a 1 umile 2. 4. tu r lui I al III utili uu ni.jij*1a - II. )l umii!a I 111 log Iut I. i T ubili 3 -2 . (Con t i micci) SUMMARY OF CM.ORINATE FURAN AIR EMISSION SOURCE CATEGORIES Tyt* i'l Si.m e T(*e ol S.t|. Ir m o r. licor. T^or Tur j.i.i.x -ic u r rcor licor l fc o r 0 |l| 9*1 e t - 114. uni f* irO NA HA alad HUI >a |i.h rsr HA HA Hill FA 1f un HA H A S uck IIWl |A Ilut l!t HA HA m il ya ir.. r&r HA HA HUI l"A (|<m 1*0 1 le NA HU HUI I I llu a l <rl HA IIHtt HUI li h i m ESf NO HA HUI rA li<>* rcr NO 110 HUI r/. Iro M tst* l0 HA IIU| rA 1 ron nal' Nil HA HUI rA 1ra tur HA MUS m il i a Iru M r.sr HA HA HUI A, Hl NA MUS IIUI ia itu t&r HA |IA HU| rA ( rH IIA NA ASI', t l i i | HA HA H A ' HA II.t`>0 p ,.| HA HA |A HA HA H HO 1 pl* NA A ri* HX HU HU UX NA HA (4A) UX HA UN HA |IA un (rA) l'A HA HA HA H* HA lift HA HA no JO n \( HA NA MX UX HX HA H* U A ) HA HA HA HA HA HA HA HO 4Q ppl* HX HA MX HA HX NA IMI HA HA HA HA IlA ilA HA Mil IV ppi |tA jif.l. 22 P|.|t 0.12 f |.S )V J.J.V HA HA l'M HA HA l `i l l | Stili eltrw lcn l w.i/tic Ine io rat or w llli U|>|i|<:muii - ta| U r l i l i lu c i. 2 . t, 11. si 2 , 1 , 1 tuutouiM U r l i imt r i g e l i Icallji itnulyecil tot. 2. A. II. si tl B o i l e r mi Ilici os|.lcfl (a lm i IIIntu |o ne uu a ly , i l . 40 11. 40 3 2 . 40 Outjr (cauli 0 fui 1C'Ul1,04:1M>, .and 2 ,V ,] ,0 -i CiH) cc|ur(itl. 31. 40 4 4 MH (FA) Indicai (uuii4 only In fljr ali A v a m g e a I n coi.l>lttcJ Dmmylf ul Ivo CaiiaJlan ine Ine 1 a 1o r n, 4 4 22 22 22 22 4 * Table 3-2 (Continued) SUMMARY OK CHLORINATED FURAN AIR EMISSION SOURCE CATEGORIES Typo of Source Tyt' 1 6na.pl u IIU1 1A, 10 IIUI IA f ioa tST IMI T A , ru flou lock inn fA (turn IS) IIUI i a ir par MV 1 p a , re IMI 1A , >0 10 (coalf 11cd) r*. io It (I|u m fiie.1) .t a r u IWl TA (rou flock ne.or, ucur, T jCIU i.i.i KOI Total rcuf H IIHS (IMS HRS MA Q. HA HAS HA HR JOS n g/w* 2)11 o / 1 HA HA IIA HA HA IIA IIA HA HA 0 0 1\ I'gA* o.i 1 h p /a ha HA 0 .1) l-g/kfl o .?a rx/kf |IA IIA 2.0 Kg/kg >.B Mg/kg HA IIA I.J l'g/kg 1.2 l'g/kg HA HR HAS 100 |.pL uni :> unir ii^ciir m -.|ir Conuaeiil llncitcr , -i --u -t HRS HRS HR HR )IA itg/w* 2iJ n/w * IIA IIA HA HA HA HA HA HA ima ) Itollon Incineratola urto Ittliil ami tuta) anuunla of dloxlna and furano urto tcpuilod oa one auia. Valuna tanged f(ua |71)11-1) 111 ppL . HR 12A n g / . 1 HA IIA IIA NA Single leal of a a>unlcl|ial w.mio |iyt.(lyaln nyn lf n In Sweden. * 1) auw.j.1 ra Inkrn ftoa an CU, B> linilun I mo Inorai nr over a 9 awetli period. Renulla ui a Ilio uvciaga uf all Ionia. Total cl. lui loot cJ diolo ewlanli.it fnel t u ' In IA ,11) |ig/loii ut waolti bunted. Tntrtl rblut In.itrd fuiuu cwla- alun laclw* la li.M/J iig/ton uf tinaie buincd. Kcaillla ICpteecnl Ilio a vurngc uf clgl.t aiiwplra. 6) 62 A anwploa w ere only a ua ly t cd If for lettacliliif 1llnied dlnxlitu and /uraua. Average velina are buon. Inclni-.txt or burn leftiac nnd If umile olle. ) nnaiplca ur.it only iinalyted fur Irliuchlot- Innted dfualna and furann. HA IIA VQ pel* HA HA >0 |ipti HA HA HI) Simple uun only an.ilyred fur If IctrncbloiInal ad dlualnu nml fui ana. 8aa.pl wee only aiialytc.l for If let rapi.lui'Inal ed d l u a l n n nod furano. 22, AU i t 1 1 l 1 1 l i 1 1. i i T a b U 3-2, ( C o n U n u e d ) S U H H A R Y 01- C M . O R I N A T K D KURAN A I R E M I S S I O N S O U R C K C A T E G O R I E Ty|>* u( Snurc Ty! u( 0 u|>1 iicur, uu>i' Tcir t i:r a.>,i.*.-Tcnr ror iicur li cor ocur r.Duxciti lcincr mi r a lrui* t s r uh ina ir. HA 1 'A II U H DA dee) HWS ri DA KUU n DA *ua )A u r r* kiir n DA DA HA ur. ((ucullii*) ICC (.11 u u u 1 ) in) fA lina 1 1H U t I fA (iute aii 1 Ibi a ITA. f O I m a al celi HA HA DA DHS n - a n pi. n - j n i |.|.d DA HA HA HA HA HA % DA ' HA HA HA HA HA HA DA HA DA HA IIA DA HA HA HA HA HA DA ) . ? ' ? PP* HA M I p,.b HA MA . IO* 0/0 |>fl> P-4o; 1. IH l i ||D Mi'' u( valute (uuud | iu m 22. AU PO itiutl/ar* u l 22 I n d u c i - ' lui#. HA HA lA leale CuinliiCleil untumi J die 40, 64 Il/T Vul cm i ut durine co*liuallmi uf Accnt Driinj;o. K unuli* re lite tanfic u( voluta III 21 leni*. DA HA DA tiillcf |a III mi utili nini A. Il end (ucl ul). Urlcil loti 21 Il Il lui 2,2.) ,0-TClill wita only IO |>|>li. D A HA HA Dlilnaicy fui 1 |cu 1itie ajilc 12 Miri ( u h m . Trai ed altea v n 1 H e u llfalti fr .1 HA HA HA Cltlauiuy fiali liutai e mafie 12 aule InAcn. Tuulcd Ile# vele In Itiime u .ia iiii.1 ll|c|tlgmi. DA HA DA Cli1ne y |m l| 1cu 1a le caw|il<a 12 Vero m l e H . Venirli ultra vere In ilie||uii. HA HA DA Cliloney |mri liulni a uu|ilra A. Il Cukcn lliim (vii ruuldciillal 21 11refi 1alea . HA HA HA fa 11 liti late nnt|i|ca cui luci ed A. Il Ir itic kiir fi Ilici ut a 51 naturai (iia-lltcd lui* D eet- |n| l um ac a . HA HA DA taildcd Iiud u ulcudrd (urla . A. Il v er* u ce d In III I m i ed 21 cuinicol,lice. HA l HA DA 6 , Il 51 HA HA HA luclncratur liurna l'L'fl- B cuitlnalnated unica. / Table 3-2. (Continued) SUMMARY OF CHLORINATED F U UAH AIR EMISSION SOURCE CATEGORIES I yp of Clinica Typa of ln:Uf. ucur Tq>r TjCIlf 3i, ) , f . a . - T c p r Tnlut rcur ucur H, a * l ucur Cnaaactil a M u l e C- i'lKf U IIUI PA, f f ruta alaci HA IH-1 .1 fj*b HH-a ppb (IA HA IH fA lion IIK HR labile lilial HR HR f. HK US TA, fil fin* HR HH tflf HR HR HR HR NA 1ne |ticintu buina PCS lout no Inal ail waalaa. Htf Rullai la Illii'S wuml want 1 mu| a rCT'/c ieueul a o.iol - V e l d aliatole. HR Cli lut Inal <! I m a n i|iia|l- la lAtlvcljr ilal cmliirii lo ba pieaenl lu tSf 1 1y oli nd alack (et cailaeliina. UJ o lu g c iiill l'MI " Municipal Wanio lue Inai al or .Ml - Cornicili Uiiati I n e Il u I Ini HW| " llnuiJiiuii timic Ini.Ine ta tor UHI - MI ir Mcc tanni |ou Itic Inui a lor IUI - Iminairlui U m l c lue luci alar I W - Rcutilcnt Ini Mnod ( U v e RII* * Re Illuni la f Tilcplacc RII! * HnItieni Iu 1 llcatlng l'unnica Iti III! e m u | Dveiiual iun tngliif llll* - In.lxalilal l |ml|| rlaul IO - lutlualilal Rnllrr >A II tSI* HA IIU - HR HRS PI** * ppli " ffl ~ f Iy A ali Fluo fiaa Alaci inalai le CiactpI|a|or Hot Aualyzeil Hot Uatccteii S pecie J c t a m l u a J lo be praficnl |iut i|uanl li tcal lon noi raporteJ Hot Repudili Supaialaly f atta far III 11 lou l'alta far Bill lou fa ti fr Tif11loti IJI - Utility Bollar b U.ila fai I t i t i vntva ] mi 1} ara In taiaa of ai unione pai unii b l Valla burnatl. CCanapa ni O d eli1ut inu laJ d Inaili J ut a point for faclt of tl.a taat lo tl.ia tabla ata g iv ail lu Tabla J- |. J components in a flue gas scream. In the cases where only' collected fly ash. is analyzed for chlorinated dioxins and furans, Che evaluation Co decarmine potential air emissions can be incorrect due co the enrichment of organics on sub-micron sire particles. A, device such as an ESP is very effective at removing relatively large fly ash particles, however, its efficiency drops off considerably in the fine particle sire range lass than L micron. Available data imitate chat chlorinated dioxins and furans preferentially adsorb onto the fine particles which are escaping collection by the ESP. 7 Data rrcm one municipal incinerator in Germany illustrate this point." The concentration of TCDD in ESP collected fly ash was 0.025 pg/g, while the 7 TCDD concentration in the exhausted fine particulate was 300 pg/g." The results of several, incinerator tests have also pointed out the need co obtain and analyte both fly ash and gaseous samples for chlorinated dioxins and furans. Both chlorinated dioxins and furans have been measured in the gaseous emission streams of incinerators and other sources. in several incinerator tests Che levels or chlo rinated dioxins and furans in the gaseous phase were greater than those measured on tne .7 ash- In the case of one municipal incinerator, no calo-- rinated dioxins or furans were found on the fly ash, while practically all isomer classes of chlorinated dioxins and furans were found in the gaseous emissions.` These results demonstrate that to conclusively prove or disprove the existence of chlorinated dioxin and furan air emissions, a source's fly ash and gaseous emissions must be sampled and analyzed. 3.2.1.I Municipal Waste Incinerators-- As an examination of Tables 3-L and 3-2 shows, the incinerator type which has been tested the most and found co contain chlorinated dioxin and furan air emissions is the municipal refuse or municipal waste incinerator (MTrJI) . In source tests of MVTs all classes of chlorinated dioxin and furan isomers given in Tables 2-L and 2-2 have been identified. The isomer class suspected to be the most toxic, TCDD, has been shown to consistently be a minor component of neasured chlorinated dioxin emissions. The isomer JL 2,3,7,3-TCDD is generally etcher a very dinar parr of Che. TCDD load or ir is 2,4,7,11,23,40 r ., . , ' nor present ar all. - Generally, the oigner chlorinated dioxin compounds predominate in the samples, that have been analyzed. As a contrast, the chlorinated furan isomer class TCDF is often a major component or total chlorinated fnraa emissions. The 2,3,.7,8-TCDF isomer has been shown in several hWI cases Co be a major constituent of total TCDF emissions and of total chlorinated furan emissions. Faferences 7, L7, 23, 26, 34, 68, and 83 are just a few of the instances in which these types of furan results are retorted. Three hypotheses have been put forth in. the literature to explain the 2 `32 existence of chlorinated dioxins and furaas in hHT air emissions.. * The first hypothesis states that chlorinated dioxins and furans occur in HWI air emissions because these same compounds are present in the.materials to be incinerated. The heat of incineration releases the chlorinated dioxins and furans- which adsorb onto fly ash or homogeneously condense into fine parti cles. The second hypothesis predicts that chlorinated dioxin and. furan emissions from MWIs occur as a result of chlorinated organic precursors such as chlorophenals and chlorobenzenes being a component of the wastes to be burned. The temperatures, of incineration initiate chemical transformations of these precursors to form chlorinated dioxins and furans. This transfor mation process by-heating has been demonstrated by several researchers (see Section 3.3). The third hypothesis, for which there is very little direct evidence, predicts de_ novo chlorinated dioxin, and furan formation can result from high temperature reactions between non-chlorinated organics and inorganic chlorine/chloride present in the wastes. 3.2.1.2 Hazardous and Chemical Waste Incinerators-- The literature in Table A-- 1 contained information on seven different hazardous and chemical waste incinerators (HWTs and CWIs) that have been shown to be emitting chlorinated dioxins and furans. The substances burned by chase incinerators include waste chemical tars, ?C3s, waste oils, and the herbicide Agent Orange. The source burning Agent Orange is the hazardous waste disposal ship h/T Wulcanus. 32 In only three, of the seven HWT and CWT tests vera both chlorinated dioxins and furans analyzed for. In tvo of these three tests involving ?C3 incinerators, only TCDD, TCDF, and their 2,3,7,8-isomers were the subject of g analysis. The pattern discussed in Section 3.2.L.L concerning the occur rence of TCDD and TCDF vas evident in these ?C3 incinerator tests. Levels of TCDF vare 2 to II tines greater than TCDD. In the third test of a CwT for vhich cnlcrmated dioxins and furans vera analyzed, TCDD, PCDD, ECDD, S,CDD, OCDD, TCTT PCDF, HCDF, and S^CDF vere found* Equal cuantities of TCDD and TCTT vere measured. In the retraining four EWX tests, samples vere only analyzed for chlo rinated dioxin compounds. These incinerators were burning vaste tars," pesticide chemical vastes, and the herbicide Agent Orange* Chlorinated dioxin isomer groups TCDD, FCDD, ECDD, E^CDD, and OCDD vere found. The toxic 2,3,7,3-TCDD isomer vas identified separately In tvo of the four tests. In the incineration of Agent Orange, 2,3,7,3-TCDD levels vere not reported separately from total T O D , and in the incineration, of chemical tars no T O D of any type vas detected* 6 1 1 1 84 * 3.2.1.3 Wire Reclamation Incinerator-- Wire reclamation incinerators (WRIs) are used to burn off the casings of scrap vire for the purpose of recovering the necal value of the wire. Several types of casings have been shovn zo contain organic and chlorinated organic materials chat may be chlorinated dioxin and furan precursors. Preference 67 reports the findings of one source test conducted to determine the existence and amount of TCDD and TCDF in a WRI's air emissions. 3och isomer groups vere identified in the incinerator's emissions and TCDF levels vere 30 times higher than TCDD levels. Only fly ash samples vere analyzed for TCDD and TCDF. Speciation for individual TCDD and TCDF isomers vas not performed in this cast. 33 4 3.2.2 3 oiler Source Caxagori.es The air emissions of utility and industrial boilers have been analyzed for the presence of chlorinated dioxins and furans. 3oilers burning a variety of fuels including coal, fuel oil, wood, refuse-derived-fuel (RDF), waste oils, and waste wood treatment solutions have been tested. The results of the analyses to determine chlorinated dioxin and furan emissions from these sources are discussed, in the following sections. 3.2.2.1 Utility Boilers-- lir emission samples- from ten utility or electric power boilers have been analyzed for the presence of. TCDD and/or its 2,3,7,3-isomer. No other chlorinated dioxin isomer groups or individual isomers have been analyzed for in the samples taken to date. In the can tests, TCDD and 2,3,7,3-TCDD levels have been below the particular detection limits used. In only one of the ten tests was gaseous phase sampling and analysis for chlorinated dioxins and furans conducted. In one test of a. 750 MW power plant burning low sulfur, high ash western coal, no TCDD was. detected in fly ash samples at a lower detection limit of L.2 parts per trillion (ppt) . The analyzed fly ash sample was collected from the stack downstream of the plant's ES? control device. In another case, fly ash samples from seven coal-fired utility boilers were analyzed for the presence of TCDD and 2,3,7,3-TCDD. Lower limits of detec tion ranged from 1.0-2.3 ppt with the average detection limit being L.3 ppt. No TCDD or 2,3,7,3-TCDD was detected in any of the seven samples. Other tests have bean conducted on a coal-fired utility boiler to determine the presence of TCDD in fly ash emissions at a lower detection limit of L.5 opt. No TCDD was detected on the fly ash. No TCDD or 2,3,7,3-TCDD was detected in tests of a 35 Y.W utility boiler burning a combination of coal and PDF. Fly ash and gaseous emissions samples taken downstream of the ES? control device were analyzed for these compounds. The lover detection limits for fly ash. and gaseous samples wera 0.1 parrs per billion (pp'o) and 0.0005 ag/litar, respectively. The anchors or Reference 30 srace cnar iCDD vas noc round because more comp lac a combuscicn occurs in Che utility boiler (as opposed Co an incinerator), thereby destroying the 7COD compounds- Mora complete combustion occurs because fire'scm temperatures are maintained at higher levels and firebox residence tines are longer- It should be noted, however, that in saoaraca tests of the 35 boiler, chlorinated furan compounds were qualitatively identified in both fly ash and vapor samples. 78 In similar work reported in Reference- 7, a boiler burning coal and RDF vas tested and found noc to be emitting chlorinated dioxins or furans as either fly ash or gaseous emissions. The detection limit reported for measuring TCDD and TCDF in the vapor samples vas 0.00025 ng/liter. 3.2.2.2 Industrial Boilers-- An industrial boiler burning waste oils vas found to be emitting: 23 34 chlorinated dioxins and furans on fly ash particles." * Fly ash from the boiler stack, and the IS? catch vas analyzed. Chlorinated furan isomer groups I^CDF, TCDF, BCD?, ICDF, H.CDF, and 0CDF were identified in the emissions. The 2,3,7,3-TCDF isomer was a major component of the TCDF group. Chlorinated dioxin isomer groups TCDD, ?CDD, HCDD, S-.CDD, and 0CDD were also identified- The 2,3,7,3-TCDD isomer vas found to be a minor component .. ,, n 23,34 cr the CDD grcun. Two separata tests were conducted on another industrial boiler burning coal only and RDF only to determine the presence of TCDD, TCDF, and their 2,3,7,8-iscmers. In tests with each fuel type, fly ash and gaseous samples were taken from the IS? stack and analyzed. The TCDD, TCDF, 2,3,7,8-TCDD, and 2,3,7,3-TCDF compounds were identified in fly ash and gaseous samples from the combustion of each fuel type.'" Chlorinated dioxin and furan emissions from burning coal only were slightly higher than those from burning RDF only. la a case of an industrial boiler fired with coal and fuel oil, onl7 chlorinated dioxins vara the subject of analysis ' Stack, fly ash samples were anal7cad and found to contain TCDD, aCDD, 3-CDD, and OCDD. No results vara reported for levels of ?CDD. The combined quantities of TCDD and CCZZ accounted for approximately 90 percent of the total chlor inated dioxins found. The 2,3,7,8-TCDD isomer was not detected at a lower cetectron -. -.ne.t or^ L0 ?po..6,11,51 Tests or emissions from an industrial boiler in a wood preserving plant indicated a potential for chlorinated dioxin and furan emissions from the 3 combustion, of wood preserving- wastewaters. In the plant, tested, the boiler was burning wood waste and a PC?/creosote wastewater mixture. Chlorinated dioxins and furans were not detected in the fly ash air emissions from the boiler's fabric filter control device; however, chlo rinated dioxins and furans were found in the boiler bottom ash and in the fly ash collected by the fabric filter. Chlorinated dioxins were detected primarily in the- bottom ash, while chlorinated furans predominated in the collected fly ash - Mono- through octachlorinated isomers of dioxins and rurans were round in the rly ash and bottom ash samples. 3 Although its detection is not explained, Reference 3 reports chan 2,3,7,3-TCDD appears (emphasis added) to be present in the collected fly ash. 3.2.3 Residential Stoves, Pireolaces, and Pumacas Prom the literature cited in Table A-L, chlorinated dioxins have bean identified in the fly ash emissions of six residential wood stoves, two residential fireplaces, and one residential heating furnace. These sources are identified as chlorinated dioxin emitters because chlorinated dioxin compounds have been measured in chimney particulates from each source. Stack, gas fly ash samples have not, however, been taken and analyzed. None or the chimney particulate samples from these sources have been analyzed for the presence of chlorinated furan compounds. Characteristics of each source's chlorinated dioxin amissions are discussed in the following sections. 36 3 . 2 . 3 . L R e s i d e n t i a l Wood S t o v e s -- Chlorinated dioxin emissions were identified in the chimney particu lates of wood stoves located in the eastern (New Hampshire), central (Michigan and Minnesota), and western (Oregon) parts of the United States."^ In choosing stoves to test, researchers attempted to pick stoves burning wood that had not been previously treated with preservatives or herbicides that could acr as chlorinated dioxin precursors. In New Hampshire primarily red oak was burned, in Michigan and Minnesota birch was the primary fuel, and in Oregon fir was used. In all four locations chimney particulates were found to contain TCDD, HCDD, H^CDD, and CCDD. The 2,3,7,8--TCDD isomer was also measured in several samples but was found to be a minor component of total TCDD emissions 3.2.3.2 Residential Fireplaces-- Chlorinated dioxin emissions were detected in the chimney particulates of two residential fireplaces burning wood that had not beea treated with preservatives or herbicides. The chlorinated dioxin isomer groups iden tified in the fireplace emissions included TCDD, HCDD, H-.CDD, and OCDD. The 2,3,7,3-TCDD isomer was identified in the particulates of one fireplace, while in the ocher none was found at a lower detection limit of 0.04 ppo. 3.2.3.3 Residential Heating Furnace-- Particulate matter removed from the plates of an ESP installed on a natural gas-fired, residential heating furnace was found to contain chlorinated dioxin compounds. The chlorinated dioxin isomer groups measured were TCDD, HCDD, H^CDD, and CCDD. Levels of TCDD were less than 0.6 percent of the total chlorinated dioxins found, however, the isomer 2,3,7,3-TCDD represented approximately 60 percent of the TCDD measured. ^ ~ ^ 3.2.4 Internal Combustion Engines The authors of References 6 , II and 51 have extrapolated that internal combustion engines burning gasoline and diesel fuel are sources of chlor- r inated dioxin air emissions. These extrapolations have been made on cha basis of researchers measuring chlorinated dioxin compounds in particulate matter scraped from the inside of mufflers installed on gasoline- and diesel fuel--burning cars and trucks. The muffler scrapings were only analyzed for chlorinated dioxins. Five mufflers were sampled, front cars burning leaded and unleaded gasoline and all were found to certain chlorinated dioxin particulates. The specific isomer groups detected were TCDD, H^CDDy and OCDD. The toxic 2,3,7,8-TCDD isomer was detected in one of the five gasoline-burning samples. Muffler samples from two trucks burning diesel fuel were also found to contain chlorinated dioxin particulates. The isomer groups detected were TCDD, HCDD, H^CDD, and OCDD. The 2,3,7,8--'ICDD isomer was datacted in- one of the muffler samples from, a diesel fuel-burning truck. 3.3 POTENTIAL SOURCES OF CHLORINATED DIG2IN AND FURAM A H EMISSIONS FROM LA302AT0RT ZZFSRIMENTS' In this section potential sources- of chlorinated dioxin and furan air emissions chat have been identified by laboratory experiments are discussed. The majority of these experiments involve- heating or burning confirmed and suspected precursors of chlorinated dioxin and furan compounds, and then analyzing offgases or residual material for the presence of chlorinated dioxins and furans. All experimental data of this type found in the refer ences of Table A-- L are summarized in Tables 3-3 and 3-4. Each experiment given in Tables 3-3 and 3-4 is discussed below. 3.3.1 Combustion of Vood, Grass, and Paper Treated with a Formulation of 2,4,5-T In the first experiment, wood chips were treated with a commercial herbicide containing 2-butoxyethyl, 2,4,5-trichIorophanoxyacetate (2,4,j-T) 33 Tab l e 3-3. L A B O R A T O R Y R E S E A R C H E X P E R I M E N T S T H A T H A V E I D E N T I F I E D S O U R C E S O F CHI.OR IN ATEI) D I OXINS T.apef imeni el l'iocc il u i c HCIKi, UUHI X CM) XCM) 2,1,|,#-TCUD Totl fLUU IK-l'U ^ Oi iiii Cuaaaanta *<rtncen C n v li u nl im of vuoti filli* Ifmtcil vitti 1,4,3! fui Millet ion HA Coieliiiet ion of papal e n J glaao 1 rental! wllll 2,4,3-T fui ani iat Iona HA H * 4 M l . l - l - , / k f ` 0 . 1 -1 .2 m fitti - P . I - 2 v g / K f 3 0 . 1 - 0 . 4 m t ttf. o. 1 2 -p .il HA HA HA HA Y*lf HA 1.4 ml l.> H HA M HA H|/| Cueiiuat Ion at wuOii tlilpa liceleil villi a 1 1 1till 0 10 plicnolato foisulallou D U M I 0.4-3H| T. 4.0H 1 <0.2-31 M|/| M - 2 J Q p|/g fa?-* (lomboat 1on of v ooJ clilpa 0( 1)01 0 .4 pg/g ticateJ villi a lelra- T.l O O i 1-42 pg/g clil oiupliciio 1a Ia f01 aeilat ion HK3 IP-140 |i)/| h - * 4 n U I'fiutyel# uf commerci ai ITUa HA HA HA HA 0.2-fnp/# <o.oo-dp|/, H -160 vf /f l-33 v tIf HA HA *0.03-1.4 a|l/l| Hcaulla fe|uecnl tlm tango 0/ A teat runa. 2 pcic m I h u I u i i *T Luin 4 . of HA Hcanlte aia for paini 20 tienici! will. 2,4,5-1. calMlltun |*1C fi of 2 ,4 .5 -T Im iiiu 'J. H o a u i l a Inve lice cut ( c d ni fu f |lie level of 2.1.2.11- T TI M uilglully lo Ilie i i * , 5 - r f o io n i1 ion. HA HoM.il il ale lor g ima 20 IleatcJ ulti. 2 ,4,3-T noil lieve licen cui Iff Ini fur tlie level ol 2,1,2 ,A-lt:il|i Ol If limi If |n |lie 2,4,3-1 f01 anil at ion. Hie vnlueo g iven fc|i(cucili enl un l im a dliccllf after tieulmrnt ami utic ucci 11Ilei tioullaeiil , 1 e|iuc 1 |vcl y , <0.p4-4|i|/| Pcanltu ala c . p i c a m J aa 34 ei.lneli.ua pel g uf foimnlaliuii uanl nini lliey ref Irci Ilia range ol five trill uui|ilce. " H/g HA Hcaulla are enpieaanl au 34 emlaelnofi per fi o l f o r m u latimi uacii ami limy rui left llie 1inty c f f 1. teal eoa-plua. I.ulmr at or y-geuei ut ml nml 4) couuuciclal ICI fuiemlat Inna vera |l-at.l. Table 3-3. L AllO R A T O KY R E S E A R C H E X P E R I M N T S T U A T H A V E I U E N T I E E D S O U R C E S OF CHLOR1NATE UXOXTNS U rp rrliH u n tn l t'niL'L'llufC iiu h h , n c im T jW W TC U ll l.l.l.B -T U W ) T a l. ru p i) . unm a-- a . . -- -- 7 ItjC M ) IK.IU J Huiiilui LI idi larva* unJ W.loi) WUul Il CnlClI utili Cuiuaoi >:1al cliluropliunal il Durillon ai LI reti Ictvea t irridi villi piillflcd rlilnr iiplicunl c* l'yiu|y ale al ruma.rei al l'CLu Tylulfaif b( f CB JlJlliMil HA MA HA HA l'yrulyela al U U L U t o l'turcii* IViulyitla uf tairacliUru* bi-iiiune l'yrul ya Ja uf pum rc l il ui u |icuri: u l'yiolvuU ut cuuiLliird (rlrli'a- uni] pcii|B r.liluruL curi:no High 1nujirlatura oxl.lalUn al tua! 111Itti 1liinpoi nuire tirU r l i m i ami clilurliiatUn af cani Uflliig riud un chiurlilo Illati idupci iiiuru a d d a i U n nnJ chlui f nu lU i i at cu*l iiali.fi L y d i u r l l U r U uclj lllfili (cr.peraiuru oxl.lnt lua and c h U i 'lmil U n a( nini uutilfi eliIalina utili. HA HA HA HA HA HA HA HA ima 16-110 pg/g 1-1S t'/ft -3 41 im/| -63 ng/g O . l - M ff/ft nus 3.1-2100 pg/p pg/0 HA HA HA HA HA HA l-JA pp/| . I`A 3-112 yd i HA HA HA 6 - M 0 pg/p HA HA 3 np/pjf 3.3 p/pji 2.11 np/i'* 0.13 np/pp HHlj <0.01 ng/pg Q.013 c a / ^ 0.8 npfpp ? . /ua ima <11.01 ng/pg <0.1123 g/ pg <0.023 pp/pg ft.pli np/ae ima 0 .1 6 ug/i'A 1.1 Mfi/l'B 2.2 us/pfi l.l re/i'F <0.013 wg/pp I g/pi 0 -13 iig/pu (1.11 i'ft/pp Hi) HO in HO HA HA HH6 ** "a/# H A HHS 1.1 llg/f HA UH 0 .6 p/g Nli P .3 t'fi/ 0.4 ng/p 13 ta/e 23 ng/fl l " / i 1-1 l'f/B ?-l ng/e A* ng/g 9P np/p *11A - Uni IUIrtlylC.1, UH - Spe el c u d c t r r M n r J la prcneut ttt <|U4l (J I c a l U n u f tepurtc4. 111) - Uni deleclcJ. H>$ - llal I epurici) tntperalely, t' CaujjunUn c h iu rlim i sd ' (uro data p a la ta fo t aneli o( t|u> taatii tu |lilq tab l^ le giva loTabu V`1 . Cn>w >t-il| P < fc rrn rp T" A m a i in rie erpicane A a* 21 cnlrulr.Hr pur g al elitum- pLunale ilruj. Hlghcr Vaine* urne uLtalnci) frun (Ha w un j unni lutile. H aulii la un ih)da1n.m fu rapi cui.et ro per p al chiniu- 21 phciintc rilii:il. lite Mfiltty Iurte ]t !:' unii t mu al th m.J ur (dune rii pii).lueet. Al gli! uni .lllfcru.il PCS Irtaacru unni leu tei. The PU Iti(inerii u r i e tetratu uiltueMiii inuteil. 36. A3 Hcd ul t d tur a|| cliluruhcii-- 33 ccnc pyrulpulu nuliu uru arprcaucJ a* entadlouu p ur ps uf eliliirnliunauiia 23 Duci. Unitigli lite Iurte 1.3, J.&-Unirei' al TCDII miti TUOI"uurc ilctur.tliicd 23 In illese tenia, ll.elr pie etnee Miiu vciy Inni Cimj.nl ed |U Utile| ItKliaCId,.23 gcuullu erprauMtif un 60 cMluaUiiu per r 1 co) alari tua aiui'l.il. Dcdultd erpreuueJ aa 60 etri ad Iona per j; ai cani etaitliifi cidlerlul. (tedulta erprcanctl u 60 ecilnaUnd per p uf nal Piuri lui n n l c i I n ) . Acculla erpruaacil aa* 0 rnliiitluiwi per r of Cani atarllnp culi crini, Tnbl'u 3-4. I.A U O R A T O R Y U E S E A H C I1 E X P E R IM E N T S T H A T U A V E I D E N T I F I E D C IU .O IU N A T E U - F U R A N S SO U RCES OF Inculili rrucoiluro lieti K, Hi:u|', TCIlf TjCul l.l.I.A -T C l'r T"U l ftlif neur iy ;n r IH.W t!uitci)l it krfer- aucc IIh h IiiiiiI luu f v o 4 c M f n i r c n l t i l Willi 2 , 1 , } - T luruiildt tun Lun i m m luu ul aiul fcfiian u m i l i v i l l i 1 , 4, 1- T fu m ili ! luna l!i>nLualInn ul wui>4 c|ilpo ti'cuinJ wtili a ir U liliu o pliuiuilat u fornii Int Ion CiiiuljiiatIon ol wiiinl rltlpa UciiUil ultli a tctrorUloroplicnolotc (urwuladuu f-ytolyaln ul cowiacrclul l'lIOn HA HHfl IlA HA HA l'A HA HA HA HA HA . HA HA HA HA HA >IH HA HA A il "M - M r A f HA l'A HA |IA HA HA HU HA HA HD p '/h <.|-0.1 M /k, Itn ll l t tepreacut ||i* range of ft teat tun, (laoultn ( espreaea^ m anlaolcna per Vj of 1 .4 ,3 -1 biiiiiotl. 28 IIA Keuulta aiu fur puppf in troulaJ will. 2,4,3-2, Hatultu are orprcuaril ao Calapluno par g of 1,1 ,5 - T liurtitil. (teaulla liowt licen entree In J fur llic U v c | nf 11H1U ail gl u al ly lit Dip ?,4,3-T fnr>iulal Inn. HA (trflnllo a ru fur ratio 10 truuleJ wllli 2,4,3-T auJ |>ave b e e n coi'iccloJ fur 1l>e level of 2 , 1 . J.li-lUm o r i gi n al ly In Ilia ] ,l,l-T foroulatlon. Tin; vnlnco given icplraent cnloalunn Jlfact|y aflni trciitwcnt *u J line w eek nf tor lye ill" went, rrupee!Ivcly. HA Itcoiiliu ore cup re u nc J a lilualnnu per A t>f formllalluit o ooj unJ ||<cy reflect llio reitRc of flvo 1 fdt tiuwplea. HA ftemilto o re crprenue.) nu 36 cnluulliitu per A of fofuu- letloii ua4 u ni llicy r a i l e d Itiu range of five Iqut qnnplco. im I.Hlmrnt ury-gcunraluil out) cu(iicU'l>l fCU foiwula- |limo w ar tea lt `l. t i 11 i 1 J ! ! i ,i Table 3-4. LA B O R A TO R Y R E SE A R C H E X P E R IM E N T S TH A T H AVE I D E N T I E lE D SO U R C E S O F C H L O R IN A T E D FURAN S K !>;r 1 1 1 I'lUCltlill c |IU)|`, itcpr. TOir T tc u r 2 i./.ft-TUlf Tif ai1 ri:or iiutr ii;rir ililif ('llloalOCit(A V ti CI (ULH Aunt lug L III. Il |igti mill wiiuil wool trcalcii wllli culmini trial clilii(u|i|iunai t UA HKS \ v t U tu UH li li 71 cnlanllllin pel g u| (lilulu|>liciinta naCtl. HI flic i valium nule olila litri! f m w llia numi wnu| 1urla. lltaltil w|t |i |iiii If 1cil III111 np|.CIIUl I'ymlynla of c h i m i i r 1u J ri:# Pylutyala of fCu Inoaciit 4> |M ut ivi 4.`||!urolimn cut jVtulyal of let raclilutu- l`yiulylt il |iit(M litui a* l*!itCltU 1`yrnlyalu of cool-Inc J t il cita* Mini prill odi lurul<aitxiiii lilil t m p e r a t u r a oxlilnl loo of coal Ululi i cn perntuiu m 1.Ut |un nml dilu inai |un of coat on luft nullum dilu lile il*iji !uai|irralu(o ox U n i Ion nuil d ilu inai inn of Coal natili !y>11 u di to r io aclJ Il1pi* IriH|iai al ora uxlilallun ami dilu Inni Ion u ( cual na Inn di lui'lue na. IIK DII HR H HA NHl DA lata HA DKS MA , HK6 MA HA HA HA HA |IA HA UA IH HH |U UH O H o/,., 0 . n|/|if <0.01 ng/|i| 0 .071 i`n/ ri *0.0| l.g/pg U.lll ng/,.B 0.1 (/ 0.AA HA HA HA HA HA HA HA HA H HK `0.07} pp/i| 9-1 `0.071 ni/pg o d i 'ihn MA HA HA HA HR HK HR li <0.07} nj/pj <0.07) ng/pB 0.0 /pf 0.11 ns/|i| 0.0 7) u g / p B 0 .07) ng/|ig 0. |A n /i` 0.0| n B / r B Cmi fill1IMI* |IC| g wl ili lli| lig*lieti1 1O UticJ. T he til1.1y tu.le 7.),/,#- n Kilt' un# nur ut lite lanjuf iwuinciM pi m ju c J. t l Bliiccn ilifi eruni re 1Ulnae In w e n I m i e il. 11. flltt 1unuciM naie t l la lo uctadilur inaiai!. >6.0 cullila fui ull dilombati 7) teli p yiuiyulu lcu(a afe txpleiiotnj au tuloiilunu |>ar pg ut di 1ui ubcui ciui 7) U n d . Ululigli lini |o> iC U..H1UI a ut l'Ulto ami Kill' wciu ilei c i 1 nel 7) In IItene leni, tlic|r pimienta Wo vciy ulnur canapai e J |n wllici Inoaicra. 7) HA HA HA HA HA HA HA HA He.iu||g capitane! a col un lumi per ( uf m a l lai 1 loft amici I ni . m u l t i axpienucil au m i na 1unu per f, uf eoa) ai ai liny outlet la). Ram il l a e. prua or il a eo 1a o 1min pur y ni cuoi `alai ling tante tini. Rrautlo capicene! cialoaluua per g uf Cual alortlny auilcilnl, 60 60 60 6 V a * |ini analyicil, IIK " lipeclaa ile 1a iw Ine il lo Lo picacnl |mt ifiiaiil |f Ica 1 1on nu| 1pufteil, III) * Uni .lui celti. l l i i l I (.<>( I o .) n r p u i u l c l y , 1 y and burned in'a laboratory oven." light case b u m s were made and che offgases of burning were sampled and analyzed for chlorinated dioxin and zuran compounds. Terra-- penta-- hexa-- , nepta-- and octachlorinated isomer groups of both chlorinated dioxins and furans were detected. As shown in Tables 3-3 and 2-4, the higher chlorinated dioxin isomer groups (ECDD, E^CDD, CCDD) predominated, for that family of compounds, while the lower chlorinated h m iscmer groups (TCDF, ?Q") were more abundant among che , .. .- ,* 28 , cocal enuo remaned. turan population. rrem tnis experiment che authors of Reference 23 attempted to show qualitative and quantitative impacts, associated with burning forests (e.g., bv forest fire) treated with 2,4,5-T- In a second group of experiments involving 2,4,5-T, other researchers separately treated paper and grass with a 2,4,5-T ester formulation known as Estaron 245' (a registered Dow Chemical formulation) and burned the 20 naterials in the laboratory. The objectives of che experiments were to determine the quantity of highly toxic 2,3,7,3-TCDD produced by burning materials treated with the 2,4,5-T herbicide and to estimate if the- quantity produced could have significant impacts to natural environmental systems, i.a., forest fires in 2,4,5-T treated forests. Thera was 2,3,7,3-TCDD produced from che paper and grass burnings additional to chat already 20 contained in the applied 2,4,5-T formulation. Though they state chat their experiments are not inclusive of every possible burning condition, the authors of Reference 20 conclude that the data ''strongly suggest chat only a very small fraction of 2,4,5-T (or other 2,4,5-trichlorophencxy species) is converted to TCDD." 3.3.2 Combustion of *~ood Treated with a Trichlorophenolace and Tetrachlothenolata Formulation To determine che quality and quantity of chlorinated dioxin and furan emissions resulting from burning wood treated with preservatives, re searchers in Sweden burned wood chips created first with a crichlorophenolata preservative formulation and then with a tetrachlorophenolate A1 preservative f o r m u l a t i o n . T h e fly ash and gaseous emissions generated by each experiment were analyzed only for chlorinated dioxin compounds. Compounds in the chlorinated dioxin isomer groups DCDD, T^CDD, TCDD, ?CDD, ECDD, H_CDD, and CCDD were detected from burning both chlorophenolata formulations,, Chlorinated dioxins were also identified in the emissions from the conhnation of wood chips treated with a PC? wood preservative formulation. Cronin emission levels were much less from PC? combustion than from tri- or tatrachlorophenolate combustion except when PC? combustion was carried out with insufficient oxygen. Quantitative results of PC? com bustion were not reported in Preference 56. The researchers did not attempt to extrapolate any of the laboratory results to natural or other combustion situations. 3.3.3 Pvrolvsis of Commercial ?C3s and ?C3 Isomers Two experiments involving the pyrolysis of commercial ?C3s are reported 34 43 in the references given in Table A.-L. ` The results of these experi ments are summarized in Tables 3-3 and 3--4. In each experiment commercially available PC3 formulations were heated in quartz ampoules to temperatures ranging, from 550-350C (L023-I5637) for about 60 seconds. Residual ash from the pyrolysis procedure was analyzed only for chlorinated furan compounds. In the first of these experiments (Reference 43), MCDF, DCDF, T^CDF, TCDF, and PCDF isomer groups were detected. In the second experi ment (Reference 34), HCDF, D O F , T.CDF, TCDF, PCDF, H O F , -L^CDF, and O O F isomer groups ware detected, and the toxic 2,3,7,3-TOF isomer was found to be a major component of the T O F group. References 34. and 43 contain conclusions that hazardous waste incinerators used to destroy PC3 wastes may be sources of chlorinated furan compounds. Researchers have also pyrolyced L3 individual, laboratory-prepared PC3 isomers to determine if they are capable of producing chlorinated furans. A. disc of the PC3 isomers pyrolyced is given in Table 3-5. ' Again, the ?C3 samples vara heated in quartz ampoules to temperatures of 550-350C TA3LZ 3-- 5. LIST OF PCB ISOMERS TEAT WERE PTROLTZZD TO DEIERMEIZ POTENTIAL CHLORINATED FTTRAN EMISSIONS36 Isomer Class Tecrachl0rcbi.rrer.7 l Fencachlorobiphenyi Hexachlorobiphenyl Eepcachloro'oiphenyl Ocrachlorobiphenyl Individual Isomers 2 .3.4.5-- 2 .3.5.62 ,6,2 *,6 *- 2 ,3,4,5,6-- 2,4,5,2*,5* -- 2,4,5,3 *,4*2,4,6 ,2*,4*2 ,3,6,2 *,5*- 2*4,5,2r,4*,5*2,4,6 ,2*,4*,6 '-- 2,4,5,2*,4*,6 *-- 2 ,3,4,2 *',3* ,4*2,3,5,2',3*,5*2,3,6,2*,3';6 f3,4,5,3*,4',5*- 2,3,4,5,2*,3*,4*2 ,3,4,5,2',4',5*- 2 ,3,4,5,2 *,3*,4',5'- -o (1022-1563J7) for 50 seconds. An analysis of the pyrolysis residues from ail 13 PC3 isomers showed che presence of chlorinated furan compounds. However, noc ail chlorinated furan isomer groups were produced by each PC3 isomer. Her example, che pyrolysis of tecrachlorobiphenyls yielded DCDr, T.CDF, an: TCDF, and PCTr . hexachlorobiphanyls yielded TCDF, PCDF, and H C D D a n d so on. ars- who conducted the PC3 isomer experiments made che following .usions based on their results.^ hosr of. the major chlorinated furan isomers found in fly ash samples are che same as chose formed from che pyrolysis of ?C3 samples, thereby giving strong support- chat chlorinated furans originate from che uncontrolled burning of ?C3s. The uncontrolled burning of ?C3s in waste incinerators is forming toxic chlorinated furan compounds chat are being emitted Co che environment. 3.3.1 Pvrolvsis of Trichlorobenzene, Tacrachlorooenzene, and ? ancachicrobenzane .. Pyrolysis experiments involving polychiorobenzanes were conducted in a similar manner to chose conducted and previously described for ?C3s. Technical grade formulations of trichlorcbenzene, tacrachlorobenzena, and pencachlorobensena were put into separate quartz ampoules and pyrolyzed at 620aC (1143F) for 50 seconds in che presence of air." In addition, a combined sample of equal amounts of cri-, cacra-, and pentachlorobenzene was also pyrolyzed under these same conditions. In all cases, residual material from pyrolysis was analyzed for chlorinated dioxin and furan compounds. Tatra through ocra isomer groups of both chlorinated dioxins and furans were detected from the pyrolysis samples of trichlorobenzenes, cetrachlorobenzenes, pencachiorobenzenes, and che combination mixture of tri-, cacra-, and pentachlorobenzene. The 2,3,7,3-ICDF and 2,3,7,3-TCDD isomers were detected in all samples, however, they were found to be minor components relative to ocher isomers within the TCDr and TCDD grouns and ocher isomer 25 groups. 3.3.5 High Temperature Oxidation and Chlorination of Coal The series of laboratory experiments described here were undertaken, to show whether chlorinated dioxins could be formed from a naturally occurring , 30 ^ organic materna-- sucn as coal. The tour primary tests to ce termina whether chlorinated dioxins could be produced from, coal were: ron- the reaction of with air at high temperaturesr che- reaction of coal with air and sodium chloride at high tempera-- tureIS, the reaction of coal with air and hydrochloric acid at high temperatures, and the reaction of coal with air and chlorine gas at high tempera- cures. All reactions were carried out in a quarcr tube suspended in a furnace with, a mfl-g-fnirm reaction temperature of 600C (L112a7) . Coal residue in the quartz tube and reaction offgases-were analyzed for TCDD, HCDD, E-CDD, and OCDD . As shown in Table 3-3, the high temperature oxidation of coal yielded only isomer groups H-CDD and OCDD, the majority of which were detected in the reaction offgases. High temperature oxidation and chlorination of coal by sodium chloride produced similar results to chat achieved by simple oxidation. Only 3_CDD and OCDD were detected, however, the split between cube residue and offgases was about equal. When hydrochloric acid and chlorine gas were used as chlorination agents, the formation of chlorinated dioxins increased about 30 and L30 times, respectively, over chat produced with sodium chloride.^ The chlorinated dioxin isomer groups TCDD, HCDD, HCDD , and OCDD were detected when hydrochloric acid and chlorine gas / I chloriuators were usad. In the case of chlorination by Hydrochloric, acid,. 89 percent of the detected chlorinated dioxins were found in the tube residua- Sowevar, when chlorine gas was the chlorination agent, 79 percent of the detected chlorinated dioxins were found in the reaction offgases The levels of " C D detected in the coal reaction samples using hydrochloric acid and chlorine., gas chloriuators were, on the average, less than L percent of the total chlorinated dioxins measured. 3.3,6 Burning of Birch Leaves and Wood Wool Treated with Chloroohenatas Wood treatment plants often b u m chlorophenate-treated wood wastes for their fuel value. Researchers have been interested in determining if this practice produced chlorinated dioxin and furan air emissions; therefore, an experiment Co b u m chlorophenate-treated birch leaves and wood wool was 21 ,, conducted. In the first part of this experiment, birch leaves and wood wool were created, with commercial grade chlorophenate wood preservatives and burned. T h e offgases, and ash produced b y burning, were analyzed for chlo-- 21 rinacad dioxin and furan compounds. Chlorinated dioxin isomer groups TCDD, FCDD, HCDD, H^CDD, and QCDD were detected in samples from both birch leaf and wood wool burning. For all chlorinated dioxin isomer groups, emissions ware greater from the 21 burning of wood wool than from burning birch leaves. " In addition to chlorinated dioxins, chlorinated furan isomer groups TCDF, ?CDF, HCDF, EjCDF, and OCDF vere also found in the samples of the burned birch leaves and wood wool. The TCDF isomer group constituted a major part of total chlorinated furan compounds detected.. Levels of TCDF found in the burned sample offgases and ash were 100 times greater chan chat contained in the treated birch leaf and wood wool samples prior to burning. 71 In the second part of this experiment, birch leaves treated with purified chlorophenate preservatives were burned and the resulting emissions 43 ft I analyzed for chlorinated dioxin and furan ccnpounds. The puriiiad chloropr.enaces used vera 2, 4, 5-crichlorophenaca and pentachlorophanate. Chlori nated dioxin emissions vara decacrad in Che case of boch purified chlorophenatas with, cha iscnar groups TCDD, ?CDD, SCDD, S^CID being found. In che burning of 2,4,o-trichlorophenace-- treated birch leaves, TCDD constituted 99 percent of cha chlorinated dioxins found. In Cha burning of pentachloro-- phanata-- created burch leaves, the higher chlorinated isoner groups EL.CDD and GCDD constituted 92 percent of total chlorinated dioxins. With both purified chlorepaerate-- created samples, levels of chlorinated dioxins found after burning vera greatly increased over vhat they vara prior to b u m - 21 iag. No chlorinated furans vere detected in the samples obtained from burning birch leaves treated with 2,4,5-crichlorophenace end pentachlorophenata. The authors of Preference 21 state that chlorinated furans vere not detected because the impurities vhich cause then to be formed are not present in the purified chlarophenates. The impurities are present, how ever , in the commercial chiarophauntas, therefore, chlorinated furans vere decanted in burnings or cnose samples. 2 1 As a summary to che experiments conducted with chlarophenates, the authors of Reference 21 conclude that, "the burning of chlarophenates or material like vood shavings, plyvood, or vaste oil containing chlarophenates seems to be a more important source to environmental pollution by polychlo rinated dibenzo-p-dioxins including 2,3,7,3-ICDD than che accidental burning of 2,4,5-T derivatives Dr vegetation treated with 2,4,5-T derivatives." CHAPTER 1 CHLORINATED DIOXIN AND JURAN EMISSIONS DATA The purpcsa tf this chapear is to present available chlorinated dioxin and furan axis a i m s data found in the literature. The majority of data in the literature is in the forex of chlorinated dioxin and furan emission concentrations- and amission factors. Very few data are available on an annualized mass amission basis (i.a., Ib/yr) for either source categories or individual sources. Summaries of the available- literature data on chlo rinated dioxin and furan emissions from source- categories and individual sources have been presented in Tablas 3-L and 3-2 of Chapter 3. It is not the purpose of this chapter to repeat every data point given in this table. Instead, vhen sufficient data are available, emission averages for parti cular source categories are discussed to show variability in the emissions of similar sources. Annualized emissions data for individual sources or source categories are given where- available. 1.1 CHLORINATED DIOXIN AID JURAN EMISSIONS JROM INCINERATION SOURCES No annualized chlorinated dioxin or furan mass emissions- data were available in the literature for incineration sources. The majority of data that were available for all incinerator types were in the form of chlorinated dioxin and furan concentrations in the fly ash. Jor MWIs, total chlorinated dioxin levels in fly ash amissions ranged from 23.3 poo to 2966 ppb, vita an average value of 863 ppb being calculated. Total chlorinated furan levels from MWT emissions ranged from 13.1 ppb to 2036 ppb j with the average being 621 ppb. Jor HWTs and CNTs fewer data were available on which to base emission ranges and averages. Based on only three data points total chlorinated dioxin levels in the emissions of HwTs/CVIs ranged from 15.5 ppb to 16^,000 ppb. Data were insufficient to X establish a range for total chlorinated furan emissions from ZWIs/CWIs because in the majority of the E^T/C^T tests- only chlorinated dioxins, and specifically TCDD and 2,3,7,3 - T O D , were analyzed for. Table 4-- 1 presents a breakdown, an the range of concentrations of chlorinated cicxhn and furan iscmer groups measured in the emissions of MWXs and HWIs/CwTs. "The lowest reported detection of each chlorinated dioxin and furan compound is. given in Table 4-- L. However, if during any test, of one of these incinerator types a particular compound was not detected,, it is noted in the table. In interesting contrast shewn by Table 4-L involves the level of 2,3,7,8-TCDD in incinerator emissions. Table 4-L shows that levels as high as L10 ppb have been measured;, however, in the SAI report on dioxin,1'Hunan Exposure to Atmospheric Concentrations of Selected Chemicals, 11 2,3,7,3-TCDD levels in incinerator emissions (and other combustion sources) were assumed to be 2 ppb. A potential difference of this magnitude has a significant impact on the national. 2,3,7,8-TCDD emissions estimates made in the SAX document. In several of the M7-7T tests reported in the literature, chlorinated dioxin and furan amission factors were developed based on the quantity of waste burned in the facility. The identified factors for total chlorinated dioxins and furans , TCDD, 2,3,7,3-ICDD, TCDE, and 2,3,7,3-1CDF are sum marized in Table 4-2. The 0.23 and 2.3 ug/kg values reported in Table 4-2 for total chlorinated dioxins and furaas were determined from tests on incinerators in the United States. The high values in the ranges, 16.3 and 17.4 ug/kg, have been determined for MWIs in Europe. The emission factors for TCDD, 2,3,7,3-TCDD, TCDE, and 2,3,7,3-ICDE were ail developed from casts on domestic JiWTs. In the tests from which all of the emission factors in Table 4-2 were developed, both gaseous and fly ash emissions were analyzed for the presence chlorinated dioxin and furan compounds. TABLE 4-1. CONCENTRATION RANGES 0? CHLORINATED DIOXIN AND FURAN COMPOUNDS FOUND IN THE EMISSIONS OF INCINERATORS" Chlorinated Dioxin or Furan Compound 2,3,7,8-TCTT TCDD ?CDD HCDD SLCDD CCDD MS*j. s <0.13 - 100 ppb * 0.7 - L10 ppb 2.9 - 488 ppba 3.4 - 1200 ppba 3.2 - 1040 ppba 0.4 - 900 ppb HWIs/CWIs 2 -- L10 ppb * 0.48 - 12,000 ppoa c 0.5 - 5600 ppb 4 -- 37,000 ppb 9 -- 59,000 ppb 2,3,7,3-TCDF ND - 300 ppba ND - 2.5 ppb" TCD7 - L3 - 223 ppb2" 2 -- 100 ppb2. FCDF 3.3 - 3L0 ppba c HCDF 1.9 -370 ppb2" c E-CDF / CCDF 4.1 - 407 ?pb'" 0 .L2 - 166 ppb3- c c Compound vas aoc detected in one or nor a cases. ND = Not da cace ad. CInsuficienc daca Co characterize ehe emissions of chis compound. d All daca in che cabla vas cakan from Tablas 3-1 and 3-2 of Chapear 3. In cha SAI dioxin rapare (Systems Appiicacicns, Inc., Human Exposure co Acmespheric Concancracions of Salaccad Chemicals. EPA Contract 68-02-3066. -abruary L982.) 2,3,7,3--TCDD levels in incinerator amissions and fossil -uel combustion source emissions vare assumed Co be 2 poo. All national tes in che SAI document vara basad en cha 2 oob value. * * TA3LI 4-2. CHLORINATED DIOXIN AND FURAN EMISSION FACTORS FOR MUNICIPAL WASTE INCINERATORS ''*17'58,33 Chlorinated Dioxin or Furar Carrcurd local cnlcrirarad dioxins local chlcriracad furans TCDD TCDF 2,3,7,8-TCDD 2,3,7,8-101 ^ND = Noe dacaccad. Emission Factors, ug/xg of vasta buread 0.23 - Lo.3 2.3 - 17.4 0.032 - 0.045 0.17 - 0.45 0.002 - 0.021 ND - 0.13 53  4.2 CaLQ3.I2TA.TZD DIOXIN AND JURAN EMISSIONS FROM 3 0 H I R SOURCES No annualized chlorinacad dioxin or furan nass emissions daca vare available in che literature for boiler sources. As shown in Tables 3-1 and 3-2, very few daca are available for boiler sources on any basis. The concentracin of cocal, chlorinated dioxin emissions from two industrial boilars in che CIS. and Europe have been neasured to be 53 ppb and 500 ppb, respectively. ^ ' '1^ 3oth of these coneeneracions were detected in fly ash from an ESJ. In che test of the U.S. boiler with 63 ppb total chlorinated dioxins, 38 ppb were determined to be TCDD. None of the 2,3,7,8-ICDD isomer was detected at a lower limit of 10 ppb. [In contrast, the SAL dioxin report (see Table. 4-1) assumed than the 2,3,7,8-TCDD level in fossil fuel combustion source emissions, was 2 ppb.] The European boiler with the total chlorinated dioxin emissions concentration of 600 ppb was also determined to have a total chlorinated furan concentration in ES? fly 23 34ash of 300. ppb." ' No ocher chlorinated furan emissions concentration data were available in the literature for boiler sources. The only ocher data available for boiler sources were in the form of chlorinated dioxin and furan emission factors. In two different tests of the same industrial boiler burning coal and RDF, TCDD, TCDF, 2,3,7,8-ICDD, and 2,3,7,3-ICDF emissions were determined on the basis of the amount of fuel burned. The results of these tests are shewn below: TCDD TCDF 2,3,7,3-TCDD 2,3,7,3-TCDF Emissions (yg/kg) from 3 u m i n g Coal RDF 0.69 5.3 o.:o 2.0 0.36 3.7 0.11 L.3 .aese asulcs indicate chat when coal and RDF are burned in an industrial boiler chlorinated dioxin and furan emissions are greater from burning coal. These tests also indicate char regardless of whether coal or RDF is burned chlorinated furan compound emissions are greater than chlorinated crcx: compound emissions.  4.3 CHLORINATED DIOXIN AND UHLAN EMISSIONS FROM RESIDENTIAL WOOD STOVIS AND FIXE?LACES The concentration of chiorinaced dioxins in the fly ash enissIons of wocd staves located la three sections of the United States has been, deter mined by tastier. The results of these tests are summarised in Table 4-3. *5 For all tests total chlorinated dioxin emissions ranged from 25.6 d o c to 21,73T ppc. The concentration of TCDD in the emissions of the tested stoves ranged free, none detected to 4923 ppt, with concentrations of tonic 2,3,7,3-TCDD ranging from none detected to 100 ppc.^ A source category similar to wood stoves, residential fireplaces, has been shown to have chlorinated dioxin emissions comparable to those given in Table 4-3. In one test of a residential fireplace, total chlorinated dioxin emissions ranged from 1300 ppt to 44,400 ppt. Emissions of the TCDD isomer group ranged from none detected to 400 ppc, with levels of 2,3,7,8-TCDD ranging from none detected :o 100 ppc. 3ased on the results of the wood stove and fireplace tests, nationwide emissions of TCDD from wood burning in residential stoves and fireplaces have been estimated co be 0.27 kg (0.6 lb)/yr. 37 It is also estimated in Reference 87 chat commercial wood burning contributes 0.54 kg (1.2 lb)/yr of TCDD co the air, controlled wood burning emits 0.32 kg (0.7 lb)/yr of TCDD to the air, and forest fires are responsible for emitting 3.1 kg (6.9 lb)/yr 87 of TCDD into the air. 4.4 CHLORINATED DIOXIN AND FTRAN EMISSIONS FROM INTERNAL C0M3USTICN ENGINES Chlorinated dioxin emissions from automobile and truck internal com bustion engines burning' gasoline and diesel fuel are summarised in Table 3-1. Total chlorinated dioxin levels ranged from 0.023 ppb to 0.092 pp'o. Levels of the TCDD iscmer group ranged frem none detected to 55 TABLE 4-3 CHLORINATED DIOXIN EMISSIONS FROM RESIDENTIAL WOOD STOVES 15 Chlorinated Dioxin. Compound MCDD DCDD T^CDD TCDD 2,3,7,8-TCDD PCDD HCDD HyCDD OCDD Total Chlorinated Dioxins Dioxin Emissi,ou Concentrations in Various Seerions of The II.S. Eastern Central Western C.S. Stoves U.S. Stoves C.S. Stoves NA NA NA L041-4925 ?pt 90-- 100 ppt JA L800-4300 ppt 2S00-41C0 ppt 2000-- 5300 ppt NA NA NA ND-374 ppt ND-- 13 ppt NA 2.7--2000 ppt 8.9-- 9000 ppt L4-12,400 ppt NA NA ' NA 124-137 ppt 6-1L ppt NA 850-2600 ppt 1700-4000 ppt 1700-4000 ppt 764I-L8,625 ppt 25.5-23,774 ??t 4374-10,737 ppt If 0.008 ppb > vith. detactions of toxic 2,3,7,3--TCDD ranging from, none detected co 0.004 ppb.^ Levels of chlorine.tad dioxin, amissions from diesel fuel internal combustion, anginas vere determined to be greater than the amissions from gasoline anginas, is shown in Table 3-- L, total chlorinated dioxin levels from diesel fuei engines vere found to be about 0.40 ppb. The TCDD isomer group and its most toxic isomer, 2,3,7,3-TCDD, vere measured at levels of 0.023 ppb and 0.CG3 ppb, respectively. 4.5 SOURCE EMISSIONS OF CHLORINATED DIOXINS AND FURANS DETERMINED FROM LABORATORY EXPERIMENTS Laboratory-generated data concerning potanciai chlorinated dioxin and fur an amissions have been presented in Tables 3-- 3 and 3-4. In only cvo of the experiments (References 20 and 28) reported in Tables 3-3 and 3-4 vere the emission results used to extrapolate chlorinated dioxin or furan emissions on a source category or individual, source basis. Both extrapola tions involved chlorinated dioxin emissions, specifically 2,3,7,3-TCDD and TCDD from the combustion of materials treated vith 2,4,5-T. In Reference 20 experiments vere conducted to find.out the level of 2,3,7,3-TCDD generated from the combustion of grasses and paper treated vith a 2,4,5-T formulation. The researchers attempted to apply their results to the real vorld situation of forest fires in a forest previously sprayed vith a 2,4,5-T herbicide. Based on the level of 2,3,7,3-TCDD generated by their experiments the researchers concluded that "the TCDD burden added to the environment by the combustion of natural materials treated vith 2.4.5- trichlorophsnox7 species is no larger than L ppc of TCDD per ppm of 2.4.5- T residue burned." In P.eference 20 TCDD is used to abbreviate 2,3,7,8-TCDD In la Preference 23 experiments vera conducted to determine the level of TCDD and other chlorinated dioxins emitted from the combustion of vood chips treated vita a 2,4,5--T herbicide. From their experimental results, re searchers here extrapolated that the uncontrolled burning (forest fire) of 1 square meter of forest, directly after treatment with. 2,4,5-T, will yield 1 ug of TCDD. In these experiments the exact 2,4,5-1 formulation used vas 2-buttxyeriyl 2,4,5-trichlorophenoxyacetate. 53 0 CHAPTER 5 DATA ON PUBLIC EXPOSURE TO CHLORINATED DIOXINS AND FURANS Nc quantiz,t~1t a measurements of ambient air levels of chlorinated diesir. arc furen. compounds are reported, in. the references given, in Append in A, Table A-- L. Tnere is only one indication in Che literature vhere an attempt was even made. to sample and analyze ambient air for the presence of chlorinated dioxins or furans. In Preference S one instance of qualitative ambient air sampling for chlorinated furan compounds is briefly reported. The source of the chlorinated furars in this case vas the ENSCO PCB incinerator in El Dorado, Arkansas. The U.S. EPA obtained ambient air samples downwind of this incinerator and analyzed them by high resolution gas chromatography/mass spectroscopy (HR GC/MS) for the presence of chlorinated furars. The results of the analysis ''suggested" the presence of TCDF in the samples. As a result of these findings, a source test vas initiated at the ENSCO incinerator to measure TCDF and 2,3,7,3-TCDF emiss'-o-s 3 The only other reported work, in the area of ambient air chlorinated dioxin and furan exposures has involved calculating potential ambient exposures to these compounds based on the results of atmospheric dispersion modelling. Source tests at MKTs and HwTs have furnished input daca for these modelling studies. References 5, 3, 12, 13, 17, and 82 present the results of five studies in which potential human exposures to TCDD, TCDF, 2,3,7,3-TCDQ, and 2,3,7,3-TCDF have been estimated by the U.S. E?A based on dispersion modelling results. To conduct exposure assessments involving chlorinated dioxin and furan compounds, the U.S. E?A uses its PTNAX dispersion model and an approach known as the "upper Limit of risk estimate (ULGRE) ." The ULORE approach 59 ' fh incorporates several vorst case assumptions which ensure chan the exposure estimates determined are an upper bound to what could potentially occur. i2 These assumeciocs are given below. The carcinogenic propercies and reproductive effects of all TCDDs and TTDcs are the sane as chat of 2,3,7,8-TCDD. Ail rf the emissions from a stack are respirable and are retained in tee body. All cf the TCDDs and TCDFs chat are respired are biologically available to the organism, even though some fraction is tena ciously bound in or on the emission particles. The cocposition of the emission products found in the stack is identical to the composition (but not the concentration) found at the ground level. The air dispersion modelling is representative of what hampers in the natural environment. The exposed population is subjected to the ^-r-TT'-r average annual concentration found at the point of highest concentration. The nan-lnun annual average concentration is equal to L/40 of the max.imr.Tt hourly concentration. The population is exposed to this maximum, average annual concen tration from the source for 24 hours a day throughout a 70 year lifetime. The linearized nuiti-scage model and ocher assumptions of the cancer unit risk assessment used by EPA's Cancer -Assessment Group (CAG) are utilized and represent an upper limit of risk at the 95 percent confidence level. Using the ~~0?H approach, the following range of annual maximum average ground level concentrations of TCDD isomers vas determined for the five p 32 incineration sites analyzed. **' Q Comnound Tocal TCDDs 2,3,7,8-TCDD*3 Range (ng/m^)a up to 9.2 x LO up co 3.8 x 10 ce lover end or Cha range is ralacad co cha noa-decected arnounc of TCDDs found an cha sicas. 3In sore rasas cha analytical rechod used could h o c distinguish 2,3,7, 3--TCDD : m several of cha ocher TCDD isomers. It is recognized Cha some ocher TCDD isomers nay be co-eluting vich che 2,3,7,8-TCDD isomer; cherefore, chis value could be an. overascinaCa of 2,3,7,8-TCDD exposures.. APPENDIX A LIST OE REFERENCES OBTAINED FROM THE CHLORINATED DIOXIN AND FURAN LITERATURE SEARCH THAT PERTAIN TO AIR EMISSIONS Table A-l pr25au.cs cue lisc o references- obtained from cha literature search chac discuss seme aspect. of chlorinated dioxin and furan air amissions . Tna 37 chlarinacad dioxin and furan refaraucesgiven in Tabla A-- l vera reviewed co specifically de camina daca on source categories of amissions, individual sources of emissions, emission levels, and ambient exposure levels. The specific copies of chlorinaced dioxin and furan air emissions contained in the references are summarised in Appendix A, Table A-- 2. As shown in Table A-2, there is considerable informacin on source cacegories of emissions, a noderace amount of data on emission levels, and very little daca on individuad sources of emissions and ambient exposure levels. TABLE A-l LIST OT REFERENCES PERTAINING TO CHLORINATED DIOXIN AND TURAN AIR EMISSIONS 1. Xrlabel, D. Dioxins: Toxic and Still Troublesome. Environment. Volume 22, Number L. January/February L981. pp. 6-- 13. 2. Study zrz Scare-of-the-Art. of Dioxin from Combustion Sources. (Prepared by Arthur I. Little, Inc.) Issued by the American Society of Mechan ical Engineers. 1981. 3. DaRos, 2-, et_ al. (Acurax Corporation) Measured Multimedia Emissions from the Weed Preserving Industry. (Prepared for U.S. Environmental Protection Agency, Cincinnati, Ohio) Contract No. 68-03-2567, Task. 4023. March. 1981. 4. Cavallaro, A., et al. Sampling, Occurrence, and Evaluation of PCDDs and PCDFs from Incinerated Solid Urban Waste. Chemasphere. Volume 9, 1980. pp. 611-621. 5. Incineration of ?C3s: Summary of Approval Actions for Rollins Environ mental Services in Deer Park, Texas. Air and Hazardous Materials Division, Region VL, U.S. Environmental Protection Agency, Dallas, Texas. February 6 , 1981. 6 . 3umb, R. R., at al. (Dow Chemical) Trace Chemistries of Fire: A Source of Chlorinated Dioxins. Science. Volume 210. October 1980. pp. 383-391. 7. Redford, D. ?., et al. Emissions of PCDDS' and PCDFs from Combustion Sources. Presented at the International Symposium-on Chlorinated Dioxins and P.elaced Compounds, Arlington, VA, October 25-- 29, 1981. 3. Agenda and minutes of the Dioxin Sources Subgroup of the Chlorinated Dioxins Work Group. March 6 , 1981. Meeting No. 10. 9. Memo from Homolya, J. 3., U.S. E?A to Spatola, J., U.S. EPA. April 7, 1980. Organic Analyses and TCDD Determination in Extracts of Samples Collected from the Hempstead Resources Recovery System Incinerator. 10. Kimble, 3. J. and M. L. Gross. Tatrachlorodibenza--p--dioxin Quanti tation in Stack-Collected Coal Fly Ash. Science. Volume 207. January 1980. pp. 59-61. 11. The Trace Chemistries of Tire - A Source of and Routes for the Entry of Chlorinated Dioxins into the Environment. The Calorinated Dioxin Task Torce, the Michigan Division of Dow Chemical U.S..A. 1978. TA3L2 A-l. LIST OF REFERENCES PERTAIN ENG TO CHLORINATED DICXIN AND FURAN AIR EMISSIONS (CONTINUED) *t 12. Upper Lin.i of Risk Estimate (ULORE) for Teerachlorinated Dioxin Emissions from Municipal Waste Combustion. Unauthored paper. August 12. 1931. Property of SASD files. 13. Interim Evaluation of Health Risks Associated with Emissions of Tetrachlorinated Dioxins from Municipal Waste Resource Recovery Facilities. Unauthcred taper. November L981. Property of SASD files. 14. Duckettr I. J. Dioxins in Perspective: Kncwns, Unknowns, Resolving the Issues. Solid Wastes Management. May 1981. pp. 56-57, 88-39. 15. Nestride, I. J . e t al. Methodology and Preliminary Results for the Isomer-Specific Determination of TCDDs and Higher Chlorinated Dibenzo-p-dioxins in Chimney Particulates from Wood-Fueled Domestic Furnaces Located in Eastern Central, and Western Regions of the United States. Presented an the International Symposium on Chlorinated Dioxins and Related Compounds, Arlington, VA, October 25-29, 1981. 16. Dellinger, 3., et al. (Northrop Services). Results of Source Emissions Characterization an the- Hempstead,. NT Refuse Energy Recovery System. (Prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC). EPA Contract 68-02-2566. April 1980. L7. Higgins, G. H. (Systech Corporation) An Evaluation of Trace Organic Emissions from ?.aiuse Thermal Processing Facilities. (Prepared for U.S. Environmental Protection Agency, Washington, D.C.) Contract No. 68-01-6071. July 1982. 18. Esposito, M. P., et al. Dioxins. ZPA-o00/2-SQ-- 197. (Prepared for U.S. Environmental Protection Agency, Cincinnati, Ohio) November 1930. 19. Rawls, R. L. Dow Finds Support, Doubt for Dioxin Ideas. Chemical and Engineering News. February 12, 1979. pp. 22-29. 20. Stahl, R. H., and L. L. Lamparski. Combustion of Several 2,4,5-Trichlorophanox7 Compounds: Formation of 2,3,7,3-TCDD. Science. Volume 197. September 1977. pp. 1008-- 1009. 21. Rappe, C ., at al. Formation of Polychlorinated Dibenzo-p-dioxins (PCDDs) and Dibenzofurans (PCDF) by Burning or Heating Chloropcenatas. Chenosphere. Volume 7, 1978. pp. 269-231. 22. Olie, R., et al. Colorodibenzo-p--dioxins and Chlorodibenzo-furans are Trace Components of Fly Ash and Flue Gas of Some Municipal Incinerators in the Netherlands. Chamosphera. Volume , 1977. pp. 455-459. A-3  * TA3LZ A-L. LIST 07 HZFERENCES PERTAINING TO CHLORINATED DIOXIN AND TURAN AIR EMISSIONS (CONTINUED) 23. 3user, E. ?w., a_t _al. Identification o Polychlorinated Dibenzo-p--dio xin Isomers round In F7 Ash.. Chamosoaere. Volume 7, 1978. pp. L65-172. 24. Xearmey, I. I., a_c_ al. Uetrachlorodibenzo-p-dioxin in. "he Environment:: Sources, and Decenaanimacin. Environmental. HeaJ.cn ParsDeceives. Volume I, 1973, pp. 273-277.. 25. 3user, E . Tomacicn of Polychlorinated Dibenzo-p-dioxins (PCDDs) and Dibenzofurans (PCDFs) from che Pyrolysis of Chlorobenzenes. Cheno-- sphere. Volume 3. 1979. pp.. 415-424. 26. Eiceman, G. A., ec_ al. Analysis of Fly Ash from Municipal Incinerators, for Trace Organic Cococurds. Analytical Chemistry. Volume 51, 1979. pp. 2343-2350. 27. Eiceman, G. A., e_t_ al. Ultrasonic Extraction of Polychlorinated Dibenzo-p-dioxins and Other Organic Compounds from Fly Ash from Muni cipal Incinerators. Analytical Chemistry. Volume 52,. 1980. pu. 1492-1496. 23. Ah'ling, 3., e_c_ al. Formation of Polychlorinated Dibenzo-p-dioxins and Dibensofurans During Combustion of a 2,4,5-T Formulation. Chemosphere. Volume 6 , 1977. p p . 461-463. 29. Rappe, C. , et al. Dioxins, Dibenzofurans, and Other Polyhalogenaced Aromatics: Production, Use, Formation, and Destruction. Annals of the New York. Academy of Sciences. Volume 320. pp. 1-13. 30. Junk, J. A. and J. J. Richard. Dioxins Not in Effluents from Coal/Refuse Combustion. Chemosphere. Volume 10, 1981. pp . 1237-1241. 31. Lahaniatis, E. S ., ec al. Cn the Occurrence of Chlorinated Hydrocarbons in Ely Ash iron Vaste Combustion Facilities. Chemosphere. Volume 6 , 1977. pp. 11-15. 32. Lustenhouver, J., ec al. Chlorinated Dibenzo--p--dioxins and Related Compounds in Incinerator Effluents: A -Ievlev of Measurements and Mechanisms of Formation. Chemosphere. Volume 9, 1980. p. 501-522. 33. Crosby, D. G. and A. S. '"eng Photochemical Generation of Chlorinated Dioxins. Chemosphere. Volume 5, 1976. p. 327. ..4n - 4,r1 TABLE.A.-1. LIST 07 REFERENCES PERTAINING TO CHLORINATED DIOEIN AND FURAN AIR EMISSIONS (CONTINUED) . > d 34. 3user, a. R., a_c al. Identification of Polychlorinated Dibeazofuran Isomers in Ely Asa and PC3 Pyrolyses. Ghanasobere. Volume 7, 1973. pp. 419-429. 35. Arsenault, E- D . Pentachloraphenol and Contained Dibenzodioxins in the Environment. - A Study of Environmental Fata, Stabiity, and Significance When Usee, in Wood Preservation. Proceedings of the American Wood. Preserving Association. 1976,. 72. pp _ 122-143. 36. Busar, a. and C. Rappe. Formation of Polychlorinated Dibenzofurans from the. Pyrolysis of Individual PCB Isomers. Chemosohera. Volume 8 , 1979. p. 157-174. 37. Lamparski, L. L. and T. J. Nestrick. Determination of Tatra-, HeraHep ta- , and Octachlorodihenzo-p-dioxin Isomers in Particulate Sampas at Parts Per Trillion Levels. Analytical Chemistrv. Volume 52, 1980. pp. 2045-2059. 38. Lamberton, J. et al. The Determination of Polychic rcdibenzo-o-dicxirs in Pentachlorophenol Wood Treatment Solutions. Journal of the American Industrial Hygiene Association. Volume 40, 1979. pp. 816-322. 39. Shin, C. , et al. (TRW, Inc.) PCM Emissions from Stationary Conven tional Combustion Processes, with Emphasis on Polychlorinated Compounds of Dibenzo-p-dicxin (PCDDs) Biphenyl (PCBs), and Dibeazofuran (PCDFs) . (Prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC.) EPA Contract No. 63-02-3133. September 1979. 40. Shin, C ., et al. (TRW, Inc.) Emissions of Polychlorinated Di-- benzc-p-dicxins (PCDDs) and Dibenzofurans (PCDFs) from the Combustion of Fossil Fuels, Wood, and Coal Refuse. (Prepared for U.S. Environ mental Protection Agency, Research Triangle Park, NC) EPA Contract No. 63-02-3138. December 1980. 41. Smith, R. J. Dioxins Have Been Present Since the Advent of Fire, Says Dow. Science. Volume 202. December 1978. pp. 1166-1167. 42. DeRoos, F. L. and A. 3jorseth. (3attelle-Columbus) TCDD Analysis of Fly Ash Sample. (Prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC.) EPA Contract No. 63-02-2636, Task 113. June 15, 1979. 43. 3user, H. R. , at_ al. Formation of Polychlorinated Dibenzofurans (PCDFs) from the Pyrolysis of PC3's. Chenosphere. Volume 7, 1973. pp. 109-119. A-5 I % *r I T.ASLE A-l. LIST OF REFERENCES PERTAINING TO CHLORINATED DIOXIN AND FURAN AIR EMISSIONS (CONTINUED) 44. Dioxins F a m e d by Normal Combustion. Chemical and Engineering News. November 20, L973. p. 7. 45. ERA Qisacaes Daw's Diorin. Theory. Chemical and Engineering News. February 27, 1979. pp. 6-7. 46 ^ Debare Ccn.ninn.es Over Dow's Dioxin Theory. Chemical and Engineering News. September 24, L979. pp. 27--28. 47. Villanueva, E.. C., et al, Chlorodibenzo-p-dioxia Concamination of Two Commercially Available Pentachlorophenols . Journal of Agricultural and Food Chemistry. Volume 21, No. 4. July/August 1973. pp. 739-740. 48. Karasak, F_ W.. Dioxins from Garbage: Previously Unknown Source of Toxic Compounds is Being uncovered Using Advanced Analytical Instrumen tation. Canadian Research. September 1980. pp. 50--56. 49. Liberti, A., et al. Evaluation of Organochlorine Compounds in the Emissions- of Urban Incinerators. From; the Perganon Series on Environ mental Science? Volume 3 -- Analytical Techniques in Environmental Chemistry. 1980. pp. 157-- 166. 50. Lamparski, L. L., et al. Photolysis of Pentachlorophano 1-Treatad Wood. Chlorinated Dibengo-g--dioxin Formation. Environmental Science and Technology. Volume 14, No. 2. February.1980. pp. 196-200. . 51. Crunmett, W. 3. (Dow Chemical) . Environmental Chlorinated Dioxins from. Combustion -- The Trace Chemistries of Fire Hypothesis. From. Pergamon Series on Environmental Science Volume 5 - Chlorinated Dioxins and Related Compounds Impact on the Environment. 1982. pp. 253-263. 52. Jansson, 3. and G. Sundstram. Formation of Polychlorinated Dibenzo-- furans (PCD?) During a Fire Accident in Capacitors Containing Poly chlorinated Biphenyls (PC3) . From Pergamon Series on Environmental Science Volume 5 -- Chlorinated Dioxins and Related Compounds Impact on the Environment. 1982. pp. 201-208. 53. Fishbein, L. Trace Organic Contaminants in the Environmental Chlo rinated Dioxins and Dibenzofurans. International Journal of Ecology and Environmental Sciences. Volume 2, 1976. pp. 69-- 81. 54. Liberti, A-, et al. Determination of Polychlorinated Dibenzo--p-dioxins and Dibenzofurans in the Emissions from Urban Incinerators. Mikro-- chimica Acta. Volumi --> 1 9 8 1 . p p . 2 7 1 - 2 8 0 . * *t p TABLE A-- 1. LIST OF REFERENCES PERTAINING TO CHLORINATED DIOXIN AND FURAN. AIR EMISSIONS (CONTINUED) 55. Liberti, A. and D. Brocco. Formation of Polychlorcdibenzo-dioxins and Polychiorcdibenza-Eurans in Urban Incinerator Emissions. From Pergamon Series an Environmental Science V o l m a 5 -- Chlorinated Dioxins and Related Ictpcunds Impact on the Environment. 1982. pp. 245-- 251. 56. Ahiing, E. mid. A. Lindskog. Emission of Chlorinated Organic Substances from Ccnhustiou.. From Pergamon Series on Environmental Science Volume* 5 -- Chlorinated. Dioxins and Related Compounds Impact on the Environ ment- 1952. pp. 215-225- 57. Rappe, C.,et al. Occupational Exposure to Polychlorinated Dioxins and Dibenzofurans. From Pergamon Series on Environmental Science. Volume 5 -- Chlorinated Dioxins and Related Comoounds Insect on the Environment. 1982. pp. 495-513. 58. Esposito, M. P. and D. R. Watkins. Airborne Dioxins: The Problem in Review. Paper Presented at the 73rd Annual Meeting of the Air Pollu tion Control Association*. Montreal, Quebec. June 22-27, 1980_ 59. Olia, X-, et al. Polychlorinated Dibenza-p-dioxins and Related Com pounds in Incinerator Effluents. From Pergamon Series on Environmental Science Volume 5 - Chlorinated Dioxins and Related Compounds Impact cm the Environment. 1982. pp.. 227-244. . SO. Mahle, N. and L. Whiting (Dow Chemical) - The Formation of Chloro-- dibenzo-p--dioxins by Air Oxidation and Chlorination of 3ituminous Coal. Chemosphere* Volume 9, 1980. pp. 693-699. 61. Rimble, B,, J. Comments on "Chlorinated Dibenzo-p-dioxins and Related Compounds in Incinerator Effluents." Chemosphere. Volume 10, 1981. pp. 243-- 244. 62. Karasek, F. W., et al. Distribution of PCDDs and Other Toxic Compounds Generated on Fly Ash Particulates in Municipal Incinerators. Journal of Chromatography. Volume- 239, 1982, pp. 173-L80. 63. Eiceman, G.A., at al. Variations in Concentrations of Organic Com pounds Including Polychlorinated Dibenzo-p-dioxins and Polynuclear Aromatic Hydrocarbons in Fly Ash from a Municipal Incinerator. Analyt ical Chemistry. Volume 53, 1981. pp. 955-959. 64. Eooke, R. al. Extraction Efficiencies of Polychlorinated Difaenzo-p--dioxins and Folychkirubated Dibenzofurans from Fly Ash. Analytical Chemistry. Volume 53, 1981. pp. 461-463. A-7 * ' 9 TABLE A-L LIST OF REFERENCES PERTAINING TO CHLORINATED DIOXIN AND FuRAN AIR EMISSIONS (CONTINUED) 65. Nbestrick, X. J .> et al. Comments. on Variations In. Concentrations of Organic Compounds Including Polychlorinated Dibenzo-p-dioxins and Polynuclear Aromatic Hydrocarbons in Fly Ash, from a Municipal Inciner ator. Analytical Chemistry. Volume 54, 1932. pp. 823-824. 66. Townsend, D . X. (Dow Chemical) . The Use of Dioxin Isomer Group Ratios to Identify Sources and Define Background Levels of Dioxins in the Environment... Journal of Environmental Science and Health. Volume 315, 1980. pp. 571-609. 67.. Hryhorczuk, D. 0., et al. A Wire Reclamation Incinerator as a Source of Environmental. Contamination with Teerachloradibenzo-p-dioxins and Tetrachloradioearofurans. Archives of Environmental Health. Volume 36, 1981. pp,. 228-- 234. 63. Gizzi,. F., ec al. .Polychlorinated Diheazo-p--dioxins (PCDD) and Poly chlorinated Dibanzofurans (PCDF) in Emissions from an Urban Incinerator -- 1. Average and Peak. Values.. Chemosohere. Volume* II, 1982. on. 577-583. ." 69. Levin, J. 0. and C. A. Nilsson. Chromatographic Determination of Polychlorinated Phenols, Phenoxyphenois, Dibenzofureas, and Dibenzo-- dioxins in Wood Dust from Worker Environments. Chemosohera. Volume 6 , 1977. pp. 443-498. 70. TDI, Inc. The Dibenzofurass. (Prepared for U.S. Environmental Pro tection Agency, Washington, D.C.) EHA Contract No. .68-03-2919. 1981. 71. Levin, J. 0., at al/ Use of Chloropnenols as Fungicides in Sawmills. . Scandinavian Journal of Work Environment and Health. Volume 2, 1976. pp . 71-81. 72. Cassitto, L. and P, Magnani. 2,3,7,8 TCDD Monitoring in Flue Gases from an Incinerating Plant. Recent Developments in Mass Spectrometry in Biochemistry and Medicine. (Proceedings of the th International. Symposium.) Alberto Frigario, ad. Volume I, L973. pp. 563-568. 73. Olie, X. and 0. Eutzinger. Detection of Polychlorodibenzodioxins in Fly Ash and Flue Gas of Municipal Incinerators. Recant Developments in Mass Spectrometry in Biochemistry and Medicine. (Proceedings of the 4th International Symposium.) Alberto Frigario, ad. Volume 1, 1973. ,pp. 555-561. A-8 TABLE A-L. LIST OF REFERENCES PERTAINING TO CHLORINATED . DIOXIN AND FURAN AIR EMISSIONS (CONTINUED) 74. Brocco, 0. at al, Poiychlorodibeanodioxins and - Dibensofurans la the Environment- Physico-Chemical Behavior of Atmospheric Pollutants. (Proceedm-s of the Second European Symoosium, Varese, Italy, September 29 - October L, 193L.) 3. Versino and H. Ott, ad. L98I. pp. 32-38. 75. Morseili, L . , at al. Analysis of the Effluents of an Urban-Solid Refuse Incinerator: Study of Methods of Extraction and Analysis for the Quantitative Detarrination of Palychlorodibenno-p--dioxins. Annals of the Italian Cherical Society - 1931. 7olune 71, Nos. 9-10. pp. 557-572. 76. Esposito, M. ?., e_t al. (PedCo Environmental) . Dioxins: Volume I -- Sources, Exposure, Transport, and Control. (Prepared fo-r the U.S. Environmental Protection Agency, Cincinnati, Ohio). EPA-600/2-3G-L56. June 1980. 77. Dryden, F. E. , at al. (Walk., Eayda, & Associates). Dioxins: Volume III -- Assessment of Dioxin-coming Chemical Processes. (Prepared for the U.S. Environmental Protection Agency. Cincinnati, Ohio). ZPA-60Q/2-30-158. June 1980.. 73. Vick, R. D ., et al. Organic Emissions from Combustion of Combination Coa_L/P.efuse to Produce Electricity. Caemcsnhere. Volume 7, 1973. pp. 393-902. 79. Parvak, J., et al. (A. D. Little). An Exposure and Risk Assessment for 2,3,7,3-Tatracniorodiberro-p-dioxir. (Prepared for the U.S. Environmental Protection Agency, Washington, D.C.) I?A Contract No. 63-01-3857. Interim Draft Report. 1980. 30. Eayser, R., at al. 2,3,7,8-TCDD - Intermedia Priority Pollutant Guidance Documents. Prepared by cha Office of Toxics Integration and the Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency. July 1982. 31. Environmental Pollution Due to Dioxins and Furans from Communal Rubbish Incineration Plants. Schriitenraihe Umveltschutn. No. 5, 1982. 32. Barnes, D. G. Assessing TCDD Emissions from Municipal Waste Com bustors. Presented at the 3rd International Symposium on Chlorinated Dioxins and Related Compounds. Salzburg, Austria, October 12-14, 1982. 1  * TABLE A- L. LIST OF REFERENCES PERTAINING TO CHLORINATED DIOXIN AND FURAN AIR EMISSIONS (CONTINUED) 83. 3enianati, Z., at al. Polychlorinated Dibenzo-p-dioxins (PCDD) and Polychlorinated Qibanzofurans (PCD?) in Emissions from an Urban Incin erator , 1. Correlation Betveen Concentration of Micropollucants and Combtisclot Conditions. Chenospnare. 1982. (Voluna number unavailable}. 84. A c k a m r . t , D . G., et al. (TRW, Inc.) At-Sea Incineration of Herbicide Orange Onboard the M/T Vulcanus. EPA-6GQ/2-73-OS6 . April 1978. 35. 3allschn.itar, X., et al. Occurrence and Absence of Polychlorodi-- benzofurans and Polychlorodibenzodioxins in Fly Asa From. Municipal Incinerators. Paper Presented at the 3rd International Symposium, on Chlorinated Dioxins and Related Ccnoounds. Salzburg, Austria, October L2-14, 1982. 36. Sawyer, T ., _ac_ al. 3ioanalysis of Polychlorinated Dibenzofuran and Dibenzo-p-dioxin Mixtures in Fly Ash. Paper Presented at the 3rd International Symposium on Chlorinated Dioxins and Related Compounds. SalzburgAustria, October L2-- L4, 1982. 87. Letter and attachments from Xagel, R~ 0., Dow Chemical to B n e s , D., U.S. EPA. August 5, 1982.. Presentation given by Xagel to the Expert Advisory Committee on Dioxins. This list of references was reviewed by the U.S. EPA chlorinated Dioxin Work. Group for completeness. Comments by the Work Group indicated that the obtained references fairly well represented the best currently available data on the subject of chlorinated dioxin and furan air emissions. X TABLE ATM2. 1NDEX TO THIS CATEGOlUES O f ' INEOUMATION CONTAINED JN THE 1) 10X1N/KUHAN KEEEUENCES OE TABLE A -l Miititer U efe re n c e L i s t Number G iv e n In T a b le A -l l 2 3 4 5 6 V a `i 10 ii 12 13 14 IS 16 17 18 19 20 21 22 23 24 2S 26 27 28 29 30 31 32 L i t e r a t u r e S e a r c h I n f o r m a t i o n O a t e g o r i e u <l S o u r c e C a t e g o r y D a t a I n d i v i d u a l S o u r c e s D a t a Emi.ua Io na D alit P u b l i c E x p o s u r e D a t a + o + .d t.D/F t fD t,U/F t.D/F t.D/E t.D/F t,D t 1 +,u .o t.D t.D/F t.D/F +.D *D t.D/F t.D/F + .D t.D t.D/F t.D/F t.D t.D/F t.D/F t.D + ,D t,D/F . - t * I 1 t + 1 1 t t t + t t + t t t t + t + 1 t t 1 t t t 1 + T A U L E A - 2 . INDEX TO T U E CATEGORIES OF INFORMATION CONTAINED IN THE DIXN/FURAN REFERENCES OF TABLE A-l \ * Mauler Reference Liar Number G iv e n in T a b le A - l IP* 1 -- l\i *' ' 33 34 35 36 37 3a 3*3 40 41 42 4344 45 46 47 48 4*3 50 51 52 53 54 55 56 57 58 50 60 61 62 63 64 L i t e r a t u r e S e a r c h I n f o r m a t i o n C a t e g o r i c a 11 Source Category Data In d ivid u a i Sourcea Data Emiauionu Data R ub lic Exposure Data t.D + F 1 ,0 + .E + .D t.D /F t.D/F tD/F t.D t.D t .P t.D t.D t.D t,D/F t.D t.D + .D + .D t.F t.D / F . t.D/ F t.D / F + .D/F t.D/F t.D t.D/F t.D t.D/F t.D t.D t.D/F 1 t1 t t + t t t t t t t t it t t .+ t t .1 TABLE A-2, INDEX TO T H E CATEGORIES OF INFORMATION CONTAINED IN TH E DIOX 1N/EURAN REFERENCES OF T A B L E A-l Maurer Reference L iat Number G iv e n In T a b le A - l 65 66 67 6H 69 70 71 72 73 74 75 v. 76 77 o yu 79 ao 81 82 83 84 85 86 87 L iteratu re Search Inform ation CatpgorieuW S o u r c e C a t e g o r y D u t a I n d i v i d u a l S o u r c e o D a t a E i n i u u J o n u D a t a 1` u b l i c E x p o s u r e D a t a + ,l) t.D +,0/F t.D/F t.D/F t.D/F ,D ,D +.D/F +o + . t.D t.F t,D t,D t.D/F + .0 + .P/F t.D + .D/F . t,D/P . + .0 + ` + + t < t + t 1 t + 1 t t D - d i o x i n d a t a ; F = f u r a n d a t a . i i t I I %> jr JZ l i II