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Chemosphere, Vol.13, No.7, pp in Printed In Great Britain 4ju 788, 1984 p. 775 0045-65 3S/84 J 3 00 * .00 01984 Pergamon Press Ltd. Tin. THACE CUF.HISTniKS OF PIKE Ii/POThESIS LVIKW Afin UPDATt W-irrcn B ("runout t .*nd D>r-',ld 1. townsind !1Lrhigan Applied Science end Technology Labors tury 574 Building Dow Chemical U.S.AMidland, lII 4364D Chlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) were first discovered by Olie et al^ to be on fly ash from municipal incinerators io The Netherlands. Shortly thereafter, Buser et al10,11 reported that these compounds were also present on particulate matter frort a municipal incinerator a ad aa industrial heating facility in Switzerland. By the end of 1974, scientists from a Dow ChemicaL Company Chlorinated Dioxia Task Force 79 announced that chlorodlbentOdiOXius were present m all particulate matter taken inside or close to combustion facilities. The dioxins were found to be present id fly ash from municipal and industrial incinerators and aa oil'fired powerhouse; dust from the cities of Midland, Detroit, Lansiag, Chicago, and St. Louis; soil from lidlaad, Detroit, Lansing, Chicago, and Gaylord, Michigan; commercial sludge fertilizer from Milwaukee, particulate deposits from mside automobile and truck mufflers, both diesel aod gasoline; soot from home fireplaces; and smoke from cigarettes. These findings together with those earlier reported by Glie^ and Buser^ lead to the formulation of an hypothesis called `'trace chemistries of tire". This hypothesn was described in the original report, and in more recent papers by Bu/nb4 * 5 , Crnmmett 17 , and the National Kesearch Council Canada 59 . The trace chemistries of fire hypothesis simply says that numerous chemical reactions occur during combustion These reactions produce numerous products, some of which are at very low concentration (parts per million or less) and are emitted in smoke or are retained m the ash Among such trace products are the well known polynuclear aromatic hydrocarbons us reported by 16 the National Academy of Sciences The trace chemistries of fire hypothesis^*^^ includes chlorinated aromatic compounds among such products - particularly chlorinated dibenzodioxins, chlorinated dibenzofurms, and poly' chlorinated bi- and terpheayls The concentration of the trace products is expected to vary with the (1) molecular structure of fuel, (2) chlorine content of fuel, (3) presence of precursors and contaminants in fuel, (4) reaction temperature within the combustion zone and post combustion zone, (j) residence time of reactaots and intermediate products in the high temperature zone, (6) 777 MQNS 213664 776 mixing efficiency of air with fuel, (7J ai sue! ratio, and (A) fuel feed size according to Shill et ai?^ The nature a^d c nceTtration of the products can a l so be affected by the metals m the fly ash act r.$ as catalysts The hypothesis as originally presentee -as based on the follo-mg facts* (1) Combust loo processes, a re seldom aiora than 99 9 perceat effictrzt in converting the carbon concent of fuel to carooa dioxide^. (2) The remaining 0.1 percent of the carbon in the fuel ts converter to a large number of trace organic compounds mci-iiag chlorinated hydrocarbons, only a few of which have been identified21'"3^5,68 Only a tiny fraction of this remainder need be converted to dioxins to account for the trace quantities of dioxins otserved in combustion (3) Refuse and fossil fuels are extremely complex mixtures of many chemicals and compounds, some of fchich are present at low concentrations (4) The aatural chlorine content of fuels ranges from one to five thousand parts per million^8. This is much more chlorine than necessary to create chlorina ted dioxins observed in combustion products. (5) Particles emitted vanadium and nickel 49 . Those nickel* iron, and manganese 43 fro oil-fired heating and power plants contain, emitted froo coal-fired boilers contain" vaaadium, These trans-. *oa metals together with silicon and unoxidized carbon can serve as catalysts in ire combustion process. (6) Chemical reactions which are rcno'-n to occur la f laities lacLude pyrolysis, oxidation* reduction, and acidolysis Ions, electrons, free radicals, and free atoms interact la a continuously changing environment. (7) In the Buab study^*^, chLarinated dibenzo-p-dloxms were fpund in *11 particulate sitter taken from areas close to coobustioo processes. (8) Precursors for the formation of chlorinated dibenzo-p-dioxms have been convincingly demonstrated to include chlorinated phenol*6^ and chlorabenxeres**. Since poLyvicyl chloride produces chlorobenzenes 35,67 during pyrolysis, its role as a p recursor is also suspect. Since tlie "trace chemistries of : i =r r. o v is - -. s -as presented, V1--1CS nave been made which test the hypothesis Tnese may be placed in seve ra 1 categories as follows HONS 213665 779 (:) Studies of tlig combustion products of me niera tors. Lustenhou-er et si55 tevie.ed '.he literature and reported chat PCDDs and PCDFs tere found m fly ash from atl thirty-five muninpil inc.rt-itoti "aiiiuiicd liy all ur.r-s11 gators Ttiese include data on nine incinerators in Tbe techerlands as reported by Olle et al 66 Cavallaro et al 12'13 found similar distributions of PCDDs and PCDFs in fly ash from each of si** Italian municipal incinerators examined; Eiceman et al^ reported findirg a variety of chlorinated organic compounds including PCDDs, and PCDFs, in fly ash from municipal incinerators in Canada, Japan, and The Netherlands * Also in Caoada, Wang et al and Chiu et al* reported PCDDs and PCDFs were present in the effluent from two municipal incinerators. Samuelson H 22 and Lindskog and Eklund and Stromberg found PCDDs and PCDFs m fly ash fron Swedish municipal incinerators, Rappe 71 sad Buser8 * 9 found PCDDs and PCDFs m fly ash samples from municipal incinerators in Switzerland. Janssens et *1^ found them ia Belgium. In Italy these compounds were found ia emissions from urban incinerators by Libert! et al and by Narselli et al57 in Bologna, in rfilan, Bologna, Florence, and Rome Gizza et al 29 studied the variability m PCDD -d PCDF content of emissions from an Italian urban incinerator Karasek et al 2 7 ' 40 reported on a municipal incinerator *n France aod compared it with one ia 72 a i Ontario, Canada, In tbe United States Bedford et al and Tiernan ec al found g^ PCDDs in municipal incinerator effluent Tiernan also found PCDDs in extracts of effluents from a Hempstead, Hew York incinerator In Germany Ballschmitter et 2 al used OCDD as a PCDD indicator and found it in five of six municipal incinerators. These compounds were also found by Buser et al 7 * 9 'in flv ash from an industrial incinerator and Hr>harczuk et al^ found the tetra isomers in fly ash frcm a wire reclamation incinerator The fict that PCDDs have been found in all municipal incinerators thus far examined, supports the conclusion that this is a general phenomenon. (2) Studies on the combustion srcducts of wood Ahling and Lindskog* repoited that pyrolysis of wood or paper Kill liquors, containing little or no organ.c chlorine, form the t ccogn * = e:! ^io%.n precursors, poiychloroben2enes and polvchlorophenols. Tiernan80 qualitatively confirmed that PCDDs ace present in soot in fireplaces. Nestrick and La^pa rski^ ^ * found PCDDs in soot from the top of all chimneys examined that 'ere cocnected to wood-burmng stoves in Oregon, Minnesota, New Hampshire, and t*e Lpper Peninsula of Michigan, 0Ue et al analyzed fly ash from the combustion of painted wood over 60 years old and new ,, iood treated with pentachlorophenol and fuuntJ the PCDD and PCDF content of the * 86 fly ash from the two woods to be viriLaliy the same Wang et al also found PCDDs n woodstove effluents but onli 'corrporents with high chlorine numbers'' Thg beev of data strongly suggest that tfe production of PCDDs from the tombustion of natural wood is a general phenomenon MONS 213666 13) Studiei on tht Combustion yrjjtic'-s of coal Kimbli- and CroJsi2 .ei, unable to ini TCDD io fly ash from 4 powerhouse fired with lou-sulfur. high-slag coal 31 Likewise, Harless end Lewis Jere unable to find TCDD in seven ash 19 samples furthermore, DeRoos and Bjorseth did not detect TCDD in fly ash from a ooal-fired power plant The lacfer two studies had a limit of detection o about 2 parts per trillion ;n yet another study Junk and Ricbard3? were unable to detect TCDD at a level of 10 parts per trillion m effluent from coal/refus# Combustion. The negative results were attributed to the temperature of 'w]200"C at uhicb the uait operated Also, Redford et al failed to find PCDGi and PCDFi in a facility which burned coal jq<3 refuse derived fuel. On the other hand* Ekluad and Stc&mberj22 detected PCDDs and PCDFs in tw coal-fired combustors in 5-edefi. Chiu ec al.1'* ound measunbls j-aowccs of PCDDs and PCDFs in a sample from one ^coal-fired power plant xn Canada but not from * coal-power-d central heating plant Cxuciv* and Hit* found PCDDf in fly ash from coal combustion In addition to PCDDs and PCBfs, Ekluqd and Stromberg^* also repotted finding chlorinated bejizeaes, biphenyls, and polynuclear aromatics in flue gas from coal combustion A laboratory study by liable and Whiting^ of the combustion of bituminous coal in air showed that PCDDs are found eithrr with coal alone or in combination with various chlorine donors Thus available data on coal^fyred powerhouses taken collectively are not sufficient for extrapolation to a reasonable conclusion at this time. (4) Studies on the combustion products of light hydrocarbons, Krishman 44 and Hites used methane and a metbaae/dichlocoethaae mixture as a fuel id a burner They found chlorinated aromatic organic compounds in the effluent from the mixture but not from the oethaae alooe However, their analytical methodology was not seisiti' e or specific enough to detect PCTDs, if present, Also, others 78 have reported the formation of dioxin precursors when hydrogen chloride was added to the flame of a Bunsen burner- The possibility that PCDDs may be formed from gasoline m an automobile or truck motor has not been repotted- Tiernan80 tkd aot detect PCDDs m scrapings from the tail pipe of fev old Cars However, his methodology was not as sensitive as that of Senaitivlty of analytical methodology will be the key to further study With tgspect to this body of data nothing can be concluded at this time. C5) Theoretical studies related to the T>tcace chemistries of fire'* hypothesis. Choudhry at al^ examined * range of potential PCDD formation mechanisms and formu lated a mechanism from published data and their own work which makes i good eas* for the production of PCDDs fro simple orgauic carbon and fion-orgjmc chlorine molecules Shih et al^ did a thermochesncal equilibrium analysis to determine tbe poteotial for PCDD and PCDF formation in combustion systems over the temperature range of 533-l093C Although thecaodynamic quantities were aot available for tbe PCDDs and PCDFs, they were able to show that the formation of the polychlorobenzene precursors ace favored. Shaub acid Tsang 75 bav constructed a kinetic model frota MONS 213667 which they conclude chat homogeneous gas phase formation of PCDDs in incinerators is unlikely hut surface reactions and/or reactions inside solids (such as fly ash and other materials) seem to be strong candidates as potential sources for PCQD and PCDF formation Theoretical studies thus tJr^ reported tend t^o support the hypothesis (6) Studies to identify precursors and elucidate reaction mechanisms 53 Lindahl et al bave shown that PCDFs and PCDDs ace formed from the pyrolysis of polychlorinated diphenyl ethers. Liberti et al^'^ describe ''the basis of PCDD and PCDF formation through a thermal syathesis between two families of precursors one supplying the phenol as polypbeaolic structure and the other acting as a chlorine doaor," Polyvinyl chloride (PVC) was given as a typical example of a chlorine donor. Later Liberti et al^ showed that pyrolyzed PVC indeed produced tj?ace quantities of PCDDs and PCDFs* The quantity produced was not sufficient, however, to oeasureahly Increase the quantity of PCDDs and ^ PCDFs produced by an incinerator operating at equilibrium as shown by Karasek41 Eicemaa aad Jighei^1^ demonstrated the production of chlorinated aromatic compounds in flame chemistry through chlorination of fly ash and raiaed the possibility reactions- on fly ash of a secood mechanism of production, namely, gas-phase particulate They^ also showed that 1,2,3,4-TCDD dehydrochlocinates to T.CDD t / i in helium atmosphere between 250 and 3DDC Olie et al added hexachlorobenzene to wastes burned in a municipal incinerator and found no clear increase in either PCDDs or PCDFs* Aappe and MarkLund^ studied both baghouse ash and bottom ash from an industrial boiler burning pentachlorophenol containing waste and sludge The baghouse ash contained both PCDDs and PCDFs but the bottom ash had only PCDDs. This observation "could possibly be interpreted in terms of a de novo formation of PCDFs" in the flames. More than 90 percent of the PCDDs in the baghouse ash were those containing less than eight chlorines providing further evidence for dehydrochlorination* 34 Juak and ford have listed the reported identified organic emissions from selected combustion processes. They found 331 different Components in total, 109 from the comhustioa of coal, 235 from the incineration of wastes, and 69 from coal/refuse corahustioa processes. The precursors of irost of these compounds have not h*eo established although BaiIschmiter^ discusses this to some extent. Also not established is which of these are precursors for the formation of PCDDs and PCDFs, More precursors for ^formation of PCDDs ^and PCDFs are continually being identified The fts"t is no longer Limited to chlorinated phenols and their derivatives. (7) Studies on the detection of PCDDs and PCDFs in environmental samples The "'trace chemistries of fire" hypothesis* pointed out that PCDDs and PCDFs found in soil and dusts appeared to be related to combustion sources Tsomer group ratios related to dehydrochlorination chemistry were used by Townsend MONS 213668 7Sk to est.blish tins relationship and identify thermochemicaL sources Moreover the concentration of PCDD isomers remasmng tn envi romsterta 1 sauries after Suhjection to various natural processes should relate directly to the intensity of comhuition in the vicinity of sampling as well as the nature of the destruc- 2k tion process Eiceman and Rhea have produced data which support this theory By heating 1,2,3,4-TCDD adsorbed on fly ash in the presence of hydrogen chloride and air, higher chlorinated PCDDs w^xe produced Although the concentration of 2,3,7,3-TCDD found in fish appears to vary with the intensity of combustion on the hanks of the `rivers from which the fiah were taken as suggested by Ccununett17 and confirmed by Kackmar et al33, che contribution from combustion relative to chat from industrial sources remains undetermined Considerable fish data are now available as reported by Harless et al30, 0`Keete et al \ anil Staliuig et al77 However, these data have only been collected from areas suspected of being contaminated by industrial activity. Collectively these data imply ubiquity which vs the conclusion of Normtrom3* m his study of gull eggj Support for this position relative to other chlorinated dioxins is also given in a study of human milk.54 , Czuczwi and Hite*13 examined lacustrine sediments from Lake Michigan, Lake Huron, Lake Siskiwit, and Lake Zurich* They concluded that the "input of dioxin* and furans to the sedimentary environment is due to the combustion of chlorinated organic products present in various wastes1'. The total isomer distribution from all these various lakes was remarkably similar and corre sponded to that of the general background obtained by theoretical projections. Particulate matter from the eruption of Mount Saint Helens was examined by Lamparski et al 46 . The amount of PCDD found varied with the sample collection zone urbin^interstate highways>rural>blast area. Tbis suggests that PCDDs were adsorbed on volcanic ash as it moved into areas where combustion was occurring Analysis of s sample of dcied municipal sewage sludge sealed in. glass and displayed at the Chicago World's Fair m 1933 revealed a dioxin pattern almost identical to 1981 and 1982 samples of dried sludge from the same source. L*rrparski et *1^ sbowed that tbe concentration of CCDD, H^CDD, and H^CDDs were identical m the three samples and the isomer ratios were constant The tetra isomers were m the same ratios but the concentrations were less in the 1933 sample. Since chlorinated phenols were not being produced commercially in 1933, the source of these dioxins is worthy of further study (0) Studies consisting of reviews, conciliations, and recommendations Two studies reviewed the literature on PCDDs from combustion with considerable 32 variation in their conclusions and recommend**!tons One of these , commis sioned by The American Society of Mechanical Engineers, concludes that "PCDDs are present at low levels in the emissions from many types of combustion sources" and defined the "most obvious need" to be the establishment of "the quantitative relationship between effects levels and emission levels" thus establishing "criteria for tolerable PCDD emission levels". The report recoin- HONS 213669 mended studies oa: "exposure and risk assessment, advances 10 measurement methodology, improvements in the toxicological effects data base, and Improve ments in the emissions data base" The second review^, sponaored by the U S. Environmental Protection Agency, concludes that the data indicates "that emissions of PCDD* and PCDFs are general phenomena related to all combustion processes1'. A research strategy is suggested which emphasises the study of combustion process characteristics of specific combustion systems with the goal of minimising the formation of PCDDs and PCDFs. The review supplies a "ranked priority Hat of combustion systems for source testing". This research position is similar to that taken by the Incineration Worksbip at The Rome, Italy, Conference^, which concluded, in part, "Rather than attempting to avoid certain items 10 incineration, it may be more important to optimize combustion coadUioat", It x* not yet possible to quantify the relative amounts of dioxin* created during chemical manufacture, incineration, and other types of combustion, However, Consideration of all the data on the formation of PCDSs sad PCDFs lead* to a conclusion similar to that of GilbertsoaZ3 who wrote* `The apparently disparate piece* of evidence from the late 1978 presentation by Dow now form a connected body. It is difficult* therefore* not to believe that chlorpdioma* are eutcciag the environment in trace quantities from very many sources,'* CES 1. Ahlingr B* and A. Lindskog, "Emission of Organic Substances From Coabustioo/1 "Chlorinated Dioxins and Related Compounds", 0, Hutiingex, R, W, Frei* . tteriaa, and F Poccbiafi, editor* Pergamoa Press, Oxford, 1982, p, 215, 2. Ball i chunter, X,* W. Zaller, C. Scholz, and A. Hollrodt, "Occurence and Absence of Polychloro*dibenzofurane and Polycbloro-'dibenzodioxins m Fly Aih from Municipal Incinerators." Chemosphere I_2, 585 {1983) 3. Broeco, D , A, Cecinato* and A, Liberti* ,fPolychloeodibenzodioxins in L*e Environment.'* Chemosphere, 7* 199 (1978) 4. Bujnb* R.R, , "Direct Testimony of Dr. Robert R. Bumb." Before the Eavironaentil Protection Agency of The United Stats* of America," la Re: The Dow Chemical Comapny, et *1. Docket Nos. 415, et al. Exhibit Ho* 806. 5. fluab, R.R,, W, B, Crunroett, S. 5. Cutte, J. R. Giedhill, R, K, Hunoel, R. 0. Kagel, L. L. Lamp^rskt, E, V. Lucias, *D, L Miller, T J Westrick, L- A- Shadoff, R. H. Stehl, and J 5. Woods, 'Trace Chemistries of Fire: A Source of Chlorinated Dioxins." Science 210, 385 (1980). 6 Suser, H. R.* "Formatton of Pdtychlor mated Dibenzof uraoa (PCDFs) and Dibenzo-p-dloxins (PCDDs) From The Pyrolysis of Chlorobenzenes " Chemosphere, 8* 4}5 (1979). 7 3userv H. R, and Sosshardt, H, P * "Polychlonerte Dibenzo-p-dioxme r Qibeazefursae, and Benzole m *der Asche kummunaier and Industrie Her tferbrencuagsmlagen." Mitt, Cebiete Lebensm, Hyg, 69, 19!, {1978). 8 Suser, H, R_ and C. Rappe, "High ` Resolution Ga* Chromatography of the 22 Tetracblorodibenro^p-dioxiti [sowers " Anal. Chen. 52, 2262 (J980). HONS 784 9 Buaer, 8 R and C Rappe, Identification o Substitution Patterns in Polychlorinated Dibenzo-p-dioxias *(?CDDs) by Mass Spectroraetry " Chemosphere 7 ( 1978) 10 Bujerr H R , HP Bossharrlt, and C Rappe, ''Identification of Poly chlorinated Dibenzo-p-diomn Isomers Found in Fly Ash " Chemosphere "2, 165, 1978 t 11 Buser, H. R , fi P, Bosshardt, C Rappe, and R. Lindahl* "Identification of Polychlorinated Dibenxofuran Isooters in Fly Ash aad PCB P^rolvsis " Chemosphere 5, 419, 1978 12 CavaiLaro, A v C Bandi, G Invernizzi, L, Luciani, E. Mongini, and A. Garni, "SampLing, Occurrence and Evaluation of PCDDs and PCDFs froca Incinerated Solid Urban Waste " Cbeoospbere, 9, 61 [ (1930). 13, Cavallaco, A,, L Luciani,G Ceroai, I Rocchi, G Invernizzi. aad A. Garin, "Summary of Results of PCDOs Analyse* from Incinecator Effluents.1' Chemosphere l_l, 859 (1982) 14 Chiur C , T S Thomas, J Lockwood, < Li, R. Halenan, and R, C. C Lao, "Polychlorinated Hydrocarbons from Power Plant*, Wood Burning and Municipal Incinerators." Chemosphere 1_2, 607 (1983) 15. Choudfary, G. G , K. Olie, and 0 Hutrmger, ''Mechanisms in The Thermal Formation of Polychlorinated Dibenzo-p-dioxins and Related Compounds " "Chlorinated Dioxins and Related Compounds,'1 0- Hut2inger, R W. Fret, E Henan, and F. Pocchiari, editors Pergamon Pres*, Oxford, !982, p 275. 16. Committee on Biological Effects of Atmospheric Pollutants, "Particulate Polycyclic Organic Matter." National Academy of Sciences, Washington, D C , 1972 17 CnuiKnett' W. B , "Environmental Chlorinated Dioxins From Combustion The Trace Chemistries of Fire Hypothesis." "Chlorinated Dioxins and Related Compounds", 0. Hutzmger, R. - Frei, E. Henan, and F Pocchiari, editors. Pergamon Press, Oxford (1932J, p 253. 18 Czuczwa, J M, and R, A Kites, Environmental Fate of Combustion Generated Polychlorinated Dioxin aad Furans." Personal communication 19 DeRpos, F L. and A Bjorseth, "TCDD Analysis of Fly Ash Sample.'1 Report prepared byBattelle Columbus Laboratories for The U.S. Environmental Protection Agency. June 15, 1979 20. EPA-60Q/2-7-Q86 "At-Sea Incineration of Herbicide Orange Onboard The M/T Vulcanus" (1978). 21. Edwards, J. B, , "Combustion The Formation and Emission of Tract Species.'1 Ann Arbor Scieace, Ann Arbor, HI (1977). 22. Ekluad, G aad B. Stromberg, "Detection of Polychlorinated Polynuclear Aromatics m Flue Gases from Coal Combustion and Refuse Incinerators." Chaaoaphere j_2, 657 (1983). 23. Eiceasn, G. A., A. C Viao, and F. W. Karasek, "Ultrasonic Extraction of Polychlorinated Dibeoro'P'dioxini and Other Organic Compounds From Fly Ash from Municipal Incinerators." Anal Chen., 52, 1494 (1930) 24. Eiceasn, G A.aad H. 0 Rghei, "Chlorination Reactions of L ,2,3,4-Tec ra- chlorodibenzo-p-dioxia on Fly Ash vith HC1 in Air." Chemosphere, l_l, 833 ( 1982) 25 Eiceman, G A and H O Rghei, Prid'icts From laboratory Chlorination ,, ,of Fly Ash Fro* A Municipal Incinerator " Environ, Sci- Techno 1 16 53 (1982) 26 Eieenian, G A , R. E, Clement, and F W Karasek, "Analysis of Fly Ash From Municipal Incinerators for Trace Organic Compounds " Anal. Cbet* , 5J., 2243 (1979) MOMS 213671 1 785 27 Eie^m.n, C. A., R. E. Clement, and F W K.r.sek, "Variations in Concen tration* of Organic Compound* Including Polychlorinated Dibenao-p-dioxin* and Polynuclear Aromatic Hydrocarbons m Fly Ash from A Municipal Incinerator " Anal. Chen. 53, 955 (1981) 23 Gilbertson, M , "Report of The Heeting on 'The Dow Dioxin Theory"' Contaminants Control 3raach - EICO, Government of Canada, March 4, 1980. 29- Cizzi, F , R Reginato, E. Benfenati, and R Fanelli, "Polychlorinated Dibenzo-p-dioxm* (PCDD) and Polychlorinated Dibenzofurans (PCDF) In Emission* from An Urban Incinerator 1 Average and Peak Value* " Chemosphere, U, 577 (19B2). 30. Harleis, R L. , E. 0. Oswald, R. G. Levis, A, E. Dupuy, J. , D. D, McDaniel, and H. Tai, "Determination of 2,3,7,8'Tetrachloredibenzo-pdioxin in Fresh Water Fish." Chemosphere 11^, 193 (1982) 31. Hacle**, S L- and R. G. Lewi*, "Quantitative Determination of 2,3,7,8Tetroehlorodibenxo-p-dioxin Residue* by Gas Chroaatography/Mass Spectro metry."!Paperpresented at Workshop - Impact of Chlorinated Dioxins and Related Compounds In The Environment. Iostituto Supenore di Sanita, Roma (Italy), October 22-24 (1980). 1 * 32- Harris, J. C., R, C, Anderson, B, , Goodwin, and C E Rechstemer, "Dioxm Emissions From Combustion Sources: A Review of The Current State of Knowledge", Arthur D. Little, lac. basic report to Research Coosaittee oa Industrial and Municipal Wastes, The American Society of Mechanical Engineers, Hew York, WY (1981). 33 Hryharczuk, D. V, t W, A. Withrow, C. 3 Hesse, and V R, Beasley, Wire Reclamation Incinerator as a Source of Environmental Contaaiaa- tion ^lth Te trachlorodibenxo-p-dioxms and Tetrachlorodibenrofucana Arch. Eaviron. Health, 36, 228 (1981), 34. Hutzinger, 0 and A Liberti, "Conclusions of Discussion Sessions - Inciaerattoa Story." "Chlorinated Dioxins and Related Compounds." 0 Hutziager, R W. Frei, E Flccua, and F. Pocihian, editors, Pergamon Press, 1982, p. 603, 33 Iida, I., M Nakoshiai, and R, Goto, "Evolution of Aromatics oa Pyrolysis of Po lv(viaylchloride) and Its Mechanism." J, Polym. Sci. Chea. Ed., 12, 737, (1964), 36. Jansseos, J., L Van VaecSc, P Schepens, and F Adams, "Qualitative and Quantitative Analysis of Emissions of A Municipal Incineration Installa tion " Cams- Env Communities, EUR762^, 28 (1982). 37 Junk, G A and J J Richard, "Dioxins Hot Detected Tr\ Effluents From Coal/Refuse Combustion." Chemosphere U), 123? (1981) 38 , Kacnnar, S , M. J. Zabik, and F. D'ltri, "The Extent and Geographical Distnbutioo of 2,3,7,8-*Tetrachlorodiben2o-p-dioxin Residues in Michigan.111 Personal communication. 39 Karasek, F. V, f "Dioxins from Garbage." C-ia. Res , KJ, 50 (1980). 40, Karasek, F V,t R, E, Clement, and A. C. Viau, "Distribution af PCDDs -- aad Other Toxic Compounds Generated on'Fly Ash Particulates in Municipal Incinerators tT J, of Chromato., 239, 173 (1982) 41, Karasek, F. W , A. C Viau, G. Guichon, and M. F Gonnard, "Gas-Chromalognpblc-Mas* Spectrometnc Study on the Formation o( Po lych 1 o cum Led Dibenzo-p-Dioxias and PoLychlorobenzenes from Polyvinyl Chloride In A Municipal I nc xaerato r" -J, Chromato , 2 70 , 227 (1983) 42, Kimble, 3. I ind M L. Gross, -"Tetrachlocodibenzo-p-dioxin Quantitation in btock Collected Fly Ash " Science, 2Q7, 59 (1980). 43 Kobayaski, T 1 (1975) md Ikeajaua, Hyogo-*Ken Kogai Kenkyuaho Kenyu Hokoku 7, MONS 213672 786 44, Kirshaan, S and R. A, Hites, "Chlorinated Org.nic Compound* Formed m Methane - Dichloromethane Flame " Chemoaphere 9, 679 (1980) 45. Lahanlatu, H. ParLac, F. Karte, "Uber das Vackommeo Chlorieter Kohnlenwasteratoffe in Flugaachenz,,von HullverhrenaungsenlagenChemo- aphe're 6 (No. 1), 11 (1977J) ' ,46 Lamparski, L L. , T J Ne`rick and S. S Cutle, "The Impact of The Environment on Airborne Particulate Matter from the Eruption of Mount Saint Helena." Chemosphere. la press (1984) 47 Lsmparskt, 4 L., T. J Neatrick, and V. A Stenger, "Presence of Chlorodlbenzo Dioxins in a Sealed 1913 Sample of Dried Municipal Sewage Sludge," Personal communication. 48 Larson, J W , Ed ,, "Organic Chemistry of Coal " ACS, Washington, D C 1978. 49. Laaievlcz, K. and D. Logeveda, Ochr Porvietrle 10 (No. 5), 127 (1976). 50. Liberti, A. and D. Brocco, "Formation of Polychlorodibeozodioxios and Polychlorodibenzofuraos in Urban Incinerator* Emissions." "Chlorioated Dloxina and Related Compounds," 0. Hutzinger, R. W. Frei, E, Merisn, and F. Poecbiari, editors Pergamoa Pres*, Dxford, 1982, p. 245 51. Liberti, A., P. Ciccioil, . Brancaleoni, and A, Cecinato, "Determioa* tion of Polychlorodibenzo-p-dioxina and Polycblorioate-p-dibenzofurans in Environmental Sample* by Gas Chromatography-Mas* Spectrometry." J. Chromat , 242, 111 (1982). 52. 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Townsend, D [., "The Use of Dioxin Isomer Group Ratios to Identify Sources and Define Background Levels of Dioxins in The Environment. A Review, Update and Extension of the Present Theory." "Chlorinated Dioxins snd Related Compounds," 0. HutZinger, R. W. Frei, E Henan, and F Pocchiari, editors. Pergamon Press, Oxford, 1982, p. 265. 85 Townsend, D I., "The Use of Dioxin Isomer Group Ratios to Identify Sources and Define Background Levels of Dioxins in The Environment." J. Environ. Sci. Health, B15(5), 571 (1980). 86. Wang, D K. V. , D. H Chiu, P. K. Leung, St, 3. Thomas and R. C. Lae, "Sampling and Analytical Methodologies for PCDDi and PCDFs( in Incin erators and Wood Burning Facilities," "Human and Environmental Risks of Chlorinated Dioxins and Related Compounds." R. E. Tucker, A. L. Young, snd A. P. Gray, editors. Plenum Press, 1982, p 113. (Received in The Netherlands 8 April 1984; accepted 23 Hay 1984) MONS 213675