Document 1go3YeKDMZM6Ln1rGbdjxbxNK

I. II. III. JV. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): S. K. Cocucci, et al Title: Absorption and Translocation of Tetrachlorodibenzo-p -dioxin by Plants from Polluted Soil Reference: Experimentia, 3i5, 482-484 (1979) Citation N o : 115 Source of Dioxins Source: Soil contaminated with 2,3,7,8-TCDD from the Seveso, Italy area. Plants selectively collected from the same area. Sampling Techniques: Soil samplings were carried out by cylindrical sections (10cm in diameter, 14cm in length) in the Seveso area having a pollution level from 1000 to 400ug/m2 . Plant samples were taken from the same area - from cherry, fig, pear, apricot and peach trees and from vines. Included new leaves, fruits, twigs. Samples were extracted with hexane: acetone (4:1), concentrated, and purified on a multilayer silica gel column (H2SO4 on celite; NaHC03-Na2S04 on silica gel), then fluorisil and finally on alumina. The dried eluate in isooctane was analysed. Flow Data (mass transfer): NA Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD Analytical Techniques Used GC/MS with fragmehtometric analysis at m/e 320-322-324. Specificity: Only checked for 2,3,7,8-TCDD Sensitivity: Measurements made at ug/kg fresh plant or soil. No detection limit indicated. Comments (Significant Data, Graphs, etc.) Table 1 shows plants have ability to take in 2,3,7,8-TCDD and to translocate it to aerial parts. The lower content in the aerial parts suggests that there is a possibility of its being eliminated. CONFIDENT* AL, SUBJECT TO PROTECTIVE ORDER. 88 r OQ'1 1 Q ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE MONSANTO COMPANY Environmental Policy Staff SPECIAL REPORT ON NON-INDUSTRIAL SOURCES OF CHLORINATED DIBENZO-P-DIOXINS (CDDs) VOLUME 2 Report No. MSL-3506 1 Prepared by: A. M. Ford, Ph. H. C. Godt, Jr. Ph.D. Date: April 23, 1984 CONFIDENTIAL - RESTRICTED DISTRIBUTION DO NOT COPY C23236 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE CONFIDENTIAL - RESTRICTED DISTRIBUTION DO NOT COPY SPECIAL REPORT ON NON-INDUSTRIAL SOURCES OF CHLORINATED DIBENZO-P-DIOXINS (CDDs) VOLUME 2 Report No. MSL-3506 Prepared by A., .M. Ford> fh.D, H. C. Godt, Jr., Fh.D. late: April 23, 1984 SUBJECT TO PROTECTIVE ORDER - COMPANY CONFIDENTIAL - C23227 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE RESTRICTED DISTRIBUTION DO NOT COPY Copy No. 1 R.J. Barnes - Townley & Updike 2 T.M. Bistline 3 A.M. Ford 4 H.C. Godt, Jr. 5 W.J. McCarville 6 P.M. Pleska - Bowles, McDavid, Graff & Love 7 G. Roush 8 D.F. Snively 9 M.S. Weinberg 10 J.D. Wilson 11 Litigation Technical Support Archives 12 Litigation Technical Support Archives 13 Technical Reports Library 14 Technical Reports Library Copy to be checked out from Technical Reports Library only on approval from: R.T. Berendt or D.F. Snively of Corp. Law. CONFIDENTIAL INFORMATION This document is the property of Monsanto Company and the recipient is responsible for its safe-keeping and disposition. It contains confidential information which must not be reproduced, revealed to unauthorized persons, or sent outside the company without proper authorization. SUBJECT TO PROTECTIVE ORDER. CS3228 TABLE OF CONTENTS ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Volume I Page No. I. INTRODUCTION............................................ II. RELATIVE TOXICITY OF CDDs............................... A. Structure - Biological Activity Relationship....... 1 3 4 B. Histopathology and Cause of Death.................. 6 III. NON-INDUSTRIAL SOURCES.................................. 9 A. Municipal Incinerators............................. 9 B. Industrial Waste Incinerators...................... 35 C. Oil/Coal-fired Powerhouses and Utility Facilities................................. 39 D. Wood Burning Fireplaces/Furnaces................... 41 E. Diesel/Auto Exhausts............................... 49 F. Miscellaneous Sources.............................. 49 G. Are CDDs Ubiquitous?............................... 52 IV. CHEMISTRY............................................... 55 A. "Trace* Chemistries of Fire"........................ 55 B. Formation of CDDs........... 58 C . Photochemistry...................................... 88 D. Sources Other than Combustion.......... 94 V. SOURCE, AND ENVIRONMENTAL DISTRIBUTION................... 95 A. Homolog and Isomer Distribution Among Sources...... 95 B. Atmospheric and Surface Photodegradation........... 103 VI. ENVIRONMENTAL PCDD/PCDF INPUT........................... 106 CONFIDENT! AL SUBJECT TO PROTECTIVE ORDER. n O OO9 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE VII. ANALYTICAL TECHNIQUES................... .............. 109 A. Sampling..... ...................................... 109 B . Extraction......................................... Ill C. Purification of Extracts.......... .............. . 114 D. Identification and Quantification.................. 117 VIII. RISK ASSESSMENT AND HUMAN EXPOSURE.................... 120 IX. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS.............. 125 Volume 2 APPENDIX A. Glossary of Abbreviations andTerms................. 1 B. Principal Investigators............................ 6 C. References.......................................... 8 D. Subject Matter versus References................... 16 E. Abstracts of References.... ........................ 17 r c\ 323U 1AL SUBJECT TO PROTECTIVE ORDER. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Glossary of Abbreviations and Terms A.D.I. or ADI ag AHH acceptable daily intake = attogram = 10 "1S gram aryl hydrocarbon hydroxylase ALAS a.m.u. = S-aminolevulinic acid synthetase = atomic mass unit = ion mass unit range that MS system can measure analog a compound which is similar in structure and/or biological activity to the chlorinated dibenzo-p-dioxins (e.g., a chlorinated dibenzofuran) analytical weight equivalents (Inte: mg -- milligram = 10 "Sgrana ug microgram = lO^gram ag = nanogram = lO^gram Pg picogram = 10"l*gram fg -- feratogram = 10-15gram ag attogram = 10-18gram mg/g = part per thousand = ppth ug/g = part per million = ppm ng/g = part per billion = ppb pg/g = part per trillion = ppt fg/g = part per quadrillion = ppq ag/g = part per quintillion = ppqt angstrom a unit of atomic length equal to one-ten billionth of a meter = 10"10 meter APCI atmospheric pressure chemical ionization carcinogenesis the production of cancer CDDs chlorinated dibenzo-p-dioxins CID chemical ionization detection congener a general term used to mean any chlorinated dibenzo-p-dioxin isomer, homolog, or corresponding analog DCDD dichlorodibenzo-p-dioxin DCDF dichlorodibenzofuran dscm dry standard cubic meter ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE ECD El EPA/OSW ESP fg FID GC g HaLl-FID halogen HCB HCDD or H6CDD HCDF or H6CDF histopathology homolog HP HpCDD or H7CDD HpCDF or H 7CDF HR hyperkeratosis in vivo isomer LC LP electron capture detector electron impact Environmental Protection Agency/Office of Solid Waste electrostatic precipitator femtogram = 10" 15 gram flame ionization detector gas chromatography gram = a weight unit (1 lb. = 453.6 grams) Hall electrolytic conductivity - flame ionization detector any one of the following elements: fluorine, chlorine, bromine or iodine hexachlorobenzene hexachlorodibenzo-p-dioxin hexachlorodibenzofuran the study concerned with tissue changes characteristic of toxic chemicals or disease a group of isomers of a chlorinated compound type having a specified number of chlorine atoms. high performance heptachlorodibenzo-p-dioxin heptachlorodibenzofuran high resolution a thickening of the skin in the living body of an animal or plant a chlorinated compound with a specific numerical arrangement of the .chlorine atoms. liquid chromatorgraphy low performance CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. CS323Z LR MCDD MCDF mg MID MIS MNCI MPM MS MW NA NaPCP NBS NCI ND n8 Nm3 OCDD OCDF PAHs PCBs PCBPs PCBzs PCDDs PCDFs PCDPEs PCHBs ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE = low resolution = raonochlorodibenzo-p-dioxin = monochlorodibenzofuran = milligram = 10-3 gram = multiple ion detection = multiple ion selection = methane negative ion chemical ionization = multiple peak monitoring = mass spectrometry = megawatt = not applicable = sodium pentachlorophenate = National Bureau of Standards = negative chemical ionization = not detected = in general, the signal observed is less than 2.5 times noise level = nanogram = 1G-9 gram ~ normal cubic meter = standard cubic meter = octachlorodibenzo-p-dioxin = octachlorodibenzofuran = polynuclear aromatic hydrocarbons = polychlorinated biphenyls = polychlorobiphenylenes = polychlorinated benzenes = polychlorinated dibenzo-p-dioxins = polychlorinated dibenzofurans = polychlorinated diphenyl ethers = polychlorinated hydroxybiphenyls y--lm inf'T TO PROTECTIVE o r d e r . 3 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE PCNs PCP PCPNAs PCPPs PCPYs = polychlorinated naphthalenes = pentachlorophenol = polychlorinated polynuclear aromatics = polychlorinated phenoxyphenols = polychloropyrenes PCSs PeCDD or P 5CDD PeCDF or P SCDD Pg PoCPs ppb polychlorinated styrenes - pentachlorodibenzo-p-dioxin = pentachlorodibenzofuran = picogram = 10-12gram = polychlorinated phenols = part per billion ppm = part per million ppq ppqt PPt ppth PVC RDF RP-HPLC RWC SASS SID SIM SISPA sra3 Tig TCDD qx_ TA Cnp ^ m-- * t; A L . SUBJECT TO PROTECTIVE ORDER. = part per quadrillion = part per quintillion = part per trillion - part per thousand = polyvinyl chloride = refuse derived fuel -- reverse phase high performance liquid chromatography = residential wood combustion = Source Assessment Sampling System = selected ion detector - selected ion monitoring = selected ion summation analysis - standard cubic meter = half-life = tetrachlorodibenzo-p-dioxin 0 2 3 .2 3 4 TCDF or T4CDF teratogenesis TLC T0C1 TrCDD or T3CDD TrCDF or T3CDF ug um VSD ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE tetrachlorodibenzofuran a disturbed growth process causing deformities thin-layer chromatography total organic chlorine trichlorodibenzo-p-dioxin trichlorodibenzofuran micrograra = 10"6gram micrometer = 10"6meter (1 meter = 39.37 inches) virtually safe dose SUBJECT TO PROTECTIVE ORDER. 5 C23.23d B. Principal Investigators Name B. Ahling Expertise Laboratory combustion experiments H.R* Buser A. Cavallaro Laboratory combustion experiments, chemistry of formation of PCDDs, incinerator emissions Analytical techniques G.G. Choudhry W.B. Crummett A.J. Dobbs Chemistry of formation of PCDDs, reaction mechanisms, photolysis of PCDDs "Trace Chemistries of Fire", analytical techniques Photolysis of PCDDs G.A. Eiceman Analytical techniques, incinerator emissions M.L. Gross Analytical techniques C.L. Haile R.A. Hites Incinerator emissions Environmental fate, analytical techniques CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 6 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Location Swedish water and Air Pollution Research Laboratory, Stockholm, Sweden Swiss Federation Research Station, WHdenswil, Switzerland Provincial Chemical Laboratory, Milan, Italy Laboratory of Environmental and Toxicological Chemistry, University of Amsterdam, Amsterdam, The Netherlands Dow Chemical USA; Michigan Division Analytical Laboratories Midland, MI 48640 Department of Environment; Princes Risborough Laboratory; Princes Risborough; Aylesbury, Buckinghamshire, UK Guelph-Waterloo Center for Graduate Work in Chemistry; Department of Chemistry; University of Waterloo; Waterloo, Ontario, Canada Department of Chemistry, University of Nebraska, Lincoln, NE 68588 Midwest Research Institute Kansas City, MO 64110 School of Public and Environmental Affairs and Department of Chemistry, Indiana University, Bloomington, IN 47405 C23.236 att/-*dmpy WORK PRODUCT Name Expertise Location 0. Hutzinger Chemistry of formation of PCDDs, combustioQ emissions Laboratory of Environmental and Toxicological Chemistry, University of Amsterdam, Amsterdam, The Netherlands J. Janssens Chemistry of formation of PCDDs, combustion emissions Department of Chemistry; University of Antwerp, Antwerp, Belgium F.W. Karasek Analytical techniques Guelph-Waterloo Center for Graduate Work in Chemistry, Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada B.J. Kimble Analytical techniques Laboratory for Energy-Related Health Research, University of California, Davis, CA 95616 A. Liberti Chemistry of formation of PCDDs, combustion emissions Air Pollution Laboratory National Research Council Rome, Italy J.W.A. Lustenhouwer Chemistry of formation of PCDDs, incinerator emissions Laboratory of Environmental and Toxicological Chemistry, University of Amsterdam, Amsterdam, The Netherlands T.J. Nestrick Analytical techniques Dow Chemical USA, Michigan Division Analytical Laboratories Midland, MI 48640 K. Olie Chemistry of formation of PCDDs, incinerator emissions, "toxic equivalents" of PCDDs. Laboratory of Environmental and Toxicological Chemistry, University of Amsterdam, Amsterdam, The Netherlands A. Poland Toxicity of PCDDs, structure - biological activity relationship, histopathology McArdle Laboratory for Cancer Research, University of Wisconsin, Madison, WI 53706 C. Rappe Laboratory combustion experiments, chemistry of formation of PCDDs, combustion emissions Department of Organic Chemistry University of Umea, Umea, Sweden T.O. Tiernan Chemistry of formation of PCDDs, combustion emissions CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 7 Brehm Laboratory and Depts. of Chemistry and Pharmacology/ Toxicology, Wright State University, Dayton, Ohio 45435 C23.237 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE C. References Cit. No. B. 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Sei., 5, 215-225 (1982)1 111. A. S. Kende and J. J. Wade, Environmental Health Perspectives, September, 1973; pp 49-57 CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 13 023243 :s5 s 112. D. I . Townsend, Chemosphere, 12, 637-643, (1983) 113. G. G. Choudhry and 0. Hutzinger, Residue Rev., 84, 113-161, (1982) 114. A. J. Dobbs and C. Grant, Nature (London) 278, 163-165 (1979) 115. S. K. Cocucci, et al, Experimentia, 35, 482-484 (1979) 116. H.Tosine, Book: "Chlorinated Dioxins and Dibenzofurans in the Total Environment", edited by G. Choudhry, L. H. Keith and C. Rappe, pp. 3-14 (1983) 117. K. Payne, J. Chem. Ind. (London), 1982, 298-300 118. J. P. Van Miller, et al, Chemosphere, 9, 537-544 (1977). 119. C St E News, Sept. 12, 1983, pp. 26-30 120. J. M. Czuczwa and R. A. Hites, Abstracts, ACS Division of Environmental Chemistry, 186th National Meeting, Washington, D.C., 23, No. 2, 74-76 (1983). 121. A. Hay, et al, ibid, pp. 14-22 122. M. L. Gross, et al, ibid, p p . 256-259. 123. C. Rappe, et al, ibid, pp. 252-255 124. A. Poland, et al, J. Biological Chemistry, 251, 4936 (1976). 125. R. E. Carlson, Science, 213, 1060 (1981). 126. W. Sandermann, H. Stockmann, and R. Casten, Chem. Ber. 90, 690 (1957). 127. G. G. Choudhry and 0. Hutzinger, Toxicological and Environmental Chemistry, 5, 97-152 (1982). 128. C. A. Nilsson, K. Andersson, C. Rappe and S. 0. Westermark, J. Chromatogr., 96, 137 (1974). (Thoroughly discussed in reference'30). 129. H. R. Buser and C. Rappe, Chemosphere, 8, 157 (1979) (Thoroughly discussed in reference 30) 130. G. Saint-Ruf, Naturwissenschaften, 59^, 648 (1972) 131. H. R. Buser, H. P. Bosshardt and C. Rappe, Chemosphere, 7, 109 (1978). CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. attorney w o rk product ATTORNEY-CLIENT PRIVILEGE 132. B. Ahling, A. Bjorseth, and G. Lunde, Chemosphere, 7, 799-806 (1978). 133. C. C. Shih, et al, EPA Report on Contract No. 68-02-3138 (1980). 134. C. F. Cullis and J. E. Manton, Trans. Faraday Soc. , 54, 381-389 (1958). 135. E . K. Fields and S . Meyerson, J. Am. Chem. Soc., 88, 3388-3389 (1966). 136. R. H. Munch, "Photochemistry of Dioxin" (Monsanto internal report), April 13, 1984. 137. T. Mill , "Prediction of the Environmental Fate of Tetrachlorodibenzodioxin", SRI, Menlo Park, CA 94025. (Draft Copy) 138. C & E News, Special Issue on Dioxins, June 6, 1983. 139. A. P. Gray, et al, Tetrahedron Letters, 33, 2873-2876 (1975). 140. H. R. Buser and C. Rappe, Anal. Chem., 52, 2257-2262 (1980). 141. W. P. Cochran, et al, Pergamon Ser. Environ. Sci. , 5, 209-213 (1982).. 142. W. P. Cochran, et al, J. of Chromatography, 217, 289-299 (1981). 143. W. P. Cochran, et al, Pesticide Chem.: Hum. Welfare Environ., Proc. Int. Congr. Pestic. Chem., 5th, 1982; 4, 341-346 (1983). 144. D. G. Crosby, et al, Science, 173, 748-749 (1971). 145. Scientific American, 250 (4), 8-9 (1984). 146. J. E. Huff, et al, Environ. Health Perspectives, 36, 221-240 (1980). 147. R. W. Bovey and A. L. Young, The Science of 2,4,5-T and Associated Phenoxy Herbicides, John Wiley & Sons, 1980; pp. 389 and 168, respectively. 148. "City Currents", Sept./Oct., 1983 [A publication by the U.S. Conference of Mayors, 1620 I Street, N.W. , Washington, D.C. 20006. Phone: (202)293-7330. CONFIDENT! ASJntion: Roiialdw' Musselwhite] C2324 SUBJECT to protective order. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. Subject Matter versus References Subj ect Analytical Techniques Chemistry of Formation of CDDs (Laboratory Studies) Diesel/Auto Exhausts Flow Data (Mass Transport Rates) Human Exposure Industrial Waste Incinerators Source and Environmental Distribution Miscellaneous Sources Municipal Incinerators Oil/Coal-fired Powerhouses and Utility Facilities Photochemistry Recommendations (Research Needed) Risk Assessment Structure-Biological Activity Relationship Toxicity and Histopathology Trace Chemistries of Fire Ubiquitous Nature of CDDs Wood Burning Fireplaces/Furnaces 16 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE References 23,27,33,37,40,48,52,53,57,66,68, 69,75,82,83,91,100,105,106 2,4,5,13,15,17,18,22,23,26,28,29, 30,31,42,44,45,56,58,60,61,62,63, 64,67,73,76,77,80,84,85,86,87,88, 96,99,102,103,109,110,112,113,117, 126,128,129,130,131,132,134,135, 139,145 13,23,66,82,84 3,6,10,33,39,45,65,66,76,77,84,92, 93,100,116,147,148 6,25,31,38,45,107,115,116,146 7,13,23,38,66,80,81,84,86,94, 101,122 16,62,70,71,100,102,103,112,140, 141.142.143 13,23,34,42,51,54,66,84,94,98,123 5,10,11,13,14,16,17,19,20,21,23, 26,28,32,33,36,43,45,47,49,50,58, 59,60,61,62,63,66,69,72,73,74,76, 77,80,81,82,83,84,86,92,93,95,96, 100,101,104,110 1,13,17,23,28,33,39,46,55,66,67, 84,95 22,24,41,45,54,66,112,113,114,136, 137.138.144 66,116 6,7,66,77,107,116 111,117 8,9,12,36,43,66,78,79,89,90,108, 117,118,119,121,124 13,23,35,57,58,66,70-, 71,83,84, 97.120 13.23.66.67.70.71.82.110.119.120 125 13,23,65,66,70,71,84,98,101 r.T:324 6 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE E. Abstracts of References On the following pages, the contents of references (Citation Nos.) 1 through 117 are abstracted, should someone desire more detailed information about a particular study. The abstracts are arranged in alphabetical order by first author of the publication. The remaining references are not abstracted, because only isolated information from these references were used in the main body of the report. SUBJECT TO PROTECTIVE ORDER. 17 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Noa-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): M. Ahlberg, et al Title Chemical and Biological Characterization of Emissions from Coal and Oil-fired Power Plants Reference : Environmental Health Perspectives, 47, 85-102 (1983) Citation No.: 1 II. Source of Dioxins Source: Oil-fired boiler fired with heavy fuel oil (ash, 0.06%; sulfur, 2%) and pulverized coal boiler fired with Polish coal (ash, 0.13%; sulfur, 0.8%) Sampling Technique: Two methods operated simultaneously: (1) rainiscale plume stack gas sampler (MIPSGAS)particulates collected in a Sierra high volume impactor. (2) filter-condenser-absorber (FCA). Samples taken isokinetically. Oil-fired boiler - after the heat exchanger and before electrostatic precipitator. Pulverized coal boiler - after electrostatic precipitator. Flow Data (mass transfer): MIPSGAS sample flow: 80 liters/min. FCA sample flow: 60 liters/min. Chemistry of Formation: Not discussed. Isomers Identified: Analyzed for 2,3,7,8-TCDD and 2,3,7,8-TCDF. The quantities were apparently below the detection limits of the method. Ill. Analytical Techniques Specificity: The extractants from sampling line 2 (FCA) were analysed by GC-HPMS with the fragments monitored by the SIM technique, thus highly isomer specific for 2,3,7,8-TCDD and 2,3,7,8-TCDF. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. C23248 18 attorney w o rk product ATTORNEY-CLIENT PRIVILEGE Sensitivity: ug/kg dry fuel 2.3.7.8- TCDD: Oil-fired boiler - <0.075-0.14. coal fired boiler - <0.073-0.0952.3.7.8- TCDF: oil-fired boiler - <0.012-0.022. coal fired boiler - <0.012-0.015. IV. Comments-(Significant Data, Graphs, etc.) Sampling techniques and analytical scheme: Figures 1,2 and 3. Compounds identified: Tables 2 and 3. More organics in the oil soot than in the coal fly-ash. Acute and subacute toxicity: Hamsters treated with oil soot had lower survival rate than those exposed to coal fly-ash (Table 11). Mutagenicity (Ames test): Below the detection limit (^5000 revertants/kg fuel); 102-103 times lower than auto exhaust and residential wood burning. SUBJECT TO PROTECTIVE ORDER. 19 ro U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): B. Ahling, et al Title: Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans During Combustion of a 2,4,5-T Formulation Reference: Chemosphere, 6, 461-468 (1977) Citation No: 2 II Source of Dioxins Source: Burning of 2-butoxyethyl ester of 2,4,5-T under simulated environmental conditions using sawmill wood chips and leaves as fuel. Transit time: 0.6-1.0 sec. Temp. C: 100-850. in flue gas: 0-17.5. Sampling Techniques: Isokinetic sampling from oven. Particulates collected on glass wool, extracted with toluene. Gaseous components collected on Chromosorb W/Apiezon M, extracted with hexane and toluene. The three extracts were evaporated. Residue dissolved in hexane and chromatographed on basic alumina. Hexane elution removed non-polar co-extractives. Ethyl acetate eluted the PCDDs and PCDFs. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs were major isomers formed. At 750C. (no Og) at 3.7 sec. transit time; TCDDS, PeCDDs, HCDDs, HpCDDs and OCDD were formed, "open fire" at 100C. gave only TCDDs. In general, emission of PCDFs was higher than PCDDs. At 850C., TCDFs, PeCDFs, HCDFs, HpCDFs and OCDF were formed. III. Analytical Techniques Used GC-HPMS Specificity: Due to lack of reference compounds, isomer specificity was not possible. Quantitation of chlorine isomer clusters -TCDDs, PeCDDs, HCDDs, HpCDDs, OCDD and analogous PCDFs. Sensitivity: ~ 0.5 mg/kg formulation iTl SUBJECT TO PROTECTIVE ORDER. 20 G232U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) Table 1: Analysis of the starting ester formulation for impurities. Contained 2,4,5-T, 2,4,5-trichlorophenol, pentachlorophenol, TCDDs, PeCDDs, OCDD, TCDFs, and PeCDFs. Table 2: Eight experiments varying temp., transit time, and O2 content. Shows amounts of PCDDs and PCDFs formed. The content of PCDDs, PCDFs and chlorophenols in the formulation cannot account for the amount of PCDDs and PCDFs found in the oven emissions. The largest formation of TCDD found corresponded to the formation of ~ lug TCDD per M2 in a forest fire directly after application of the herbicide formulation. s luumAL SUBJECT TO PROTECTIVE ORDER. 21 023251 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s) B. Ahling, et al Title: Combustion Experiments Using Pentachlorophenol on a Pilot Scale and Full Scale Reference: Chemosphere, 6, 425-436 (1977) Citation No: 3 II. Source of Dioxins Source: Pilot plant combustion: Pentachlorophenol and saw dust or isopropanol at 600, 700 and 800C. with 3 sec. transit time Full scale combustion: 3.75m3 furnace with afterburner. Particles from afterburner collected by cyclone and recycled to furnace. Test material was mixture of tetrachlorophenol (75 to 340g/hr.) and pentachlorophenol (2 to llg/hr.) at 0.9 sec. transit time. Sampling Technique: Same as Citation No. 2 Flow Data (mass transfer): Pilot plant combustion: 2556-2930 m3/hour (moist) Full scale combustion: 4345 Nm3/hour. Chemistry of Formation: Not discussed. Isomers Identified: Pilot plant combustion: No PCDDs formed Full scale combustion: No PCDDs positively identified. Some could have been formed but large amount of interfering components in sample. Need better purification III . . l y M c l CONFIDENTIAL SUBJECT T0 pR0TECTiVE 0 R D E a Specificity: Only GC used. Not isomer specific. Measured TCDDs, HCDDs, HpCDDs and OCDD. Sensitivity: Not stated but poor. IV. Comments (Significant Data, Graphs, etc.) 023252 Table I: Results of pilot plant burns. (5 runs) Table II: Results of full-scale burns (4 runs) This article contains poor information. Many problems. atto rney w o rk product ATTORNEY-CLIENT pr iv ileg e Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): Title: Reference: Citation No: B. Ahling and A. Lindskog Emission of Chlorinated Organic Substances from Combustion Pergamon Ser. Environ. Sci., 5, 215-225 (1982) 110 II. Source of Dioxins Source: This is a review article covering: A. Emissions from municipal waste incinerators fly ash and gaseous effluent - Found PCDDs and PCDFs. B. Burning of black liquor from pulp industry. Produced PCBs even though black liquor contained no organic chlorine. No. PCDDs found. Exhaust gases analysed. C. Burning of wood - produced PCBs, chlorophenols but no PCDDs in effluent gases. Sampling Techniques: NA since this is a review article Flow Data (mass transfer): Not discussed Chemistry of Formation: PCBs --- -----> 2 Mentions combustion of the following compounds gave: HCB Isomers Identified: Specific isomers identified in effluents from municipal incinerators were 2,3,7,8-TCDD and 2,3,7,8-TCDF III. Analytical Techniques NA CONFIDENTIAL Specificity: NA SUBJECT TO PROTECTIVE ORDER. Sensitivity: Generally NA, but data cited for municipal incinerators was: ug/m3 for flue gases ng/g for fly ash 23 C2325 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) Emissions of chlorinated organic substances from combustion of various materials was studied. Formation of PCBzs were found to occur at the combustion of PCB and PVC and PCDD from chlorinated phenols. Combustion of municipal wastes is found to give emissions of PCBzs, PoCPs and PCDD. The PoCPs in the flue gas could explain earlier findings of PCDDs in fly ash from different municipal incinerators. Formation of PCBzs is formed from combustion of pulp industry black liquor even though it contained no chlorinated hydrocarbon. It is assumed to be formed from inorganic chlorides. The burning of wood is shown to result in the formation of chlorinated benzenes and chlorinated phenols. Conclusion: The formation of chlorinated hydrocarbons from combustion of unchlorinated natural materials gives the conclusion that the presence of these compounds in nature are not only a result of industrial activities. As e.g. forest fires have occured throughout history the pollution of chlorinated hydrocarbons is also a pre-industrial phenomena. SUBJECT TO PROTECTIVE ORDER. 24 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE II. Ill. Noa-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): R. D. Arsenault Title Pentachlorophenol and Contained Chlorinated Dibenzodioxins in the Environment Reference: American Wood-Preservers Assoc. (1976) Citation No: 4 Source of Dioxins Source: (1) In chemical manufacture of PCP. (2) By heating PCP at 200-300C. Sampling Technique: Not discussed Flow Data (mass transfer): Not discussed. Chemistry of Formation Mentions 2 step condensation reaction liberating 2 molecules of HC1, the intermediate being the "predioxin". . OH Cl^A^Cl A Cl _HL -CX'V'C -HC1 Cl Civth r C1` T Cl - Cl -Cl s nr Cl Cl Isomers Identified: In U.S. commercial PCP, there are HCDDs (10 possible isomers), HpCDDs (2 possible isomers) and OCDD. Analytical Tehniques Specificity: Not isomer specific. Article'mentions interfering substances if GC alone is used. These are the "predioxins", OCDF and 2,3,4,5,6,6- and 2,3,4,4,5,6-hexachloro-2,5-cyclohexadieneone. Mentions that the analytical equipment, through heating the sample, can form dioxins from precursors. Sensitivity: Appears to be ~ lOppb. GC/MS claimed to be most accurate analytical method. Ill. Comments (Significant Data, Graphs, etc.) Review article - some original data - gives brief history of dioxin issue. C O N F I I j i p .w -* SUBJECT TO PROTECTIVE ORDER. 25 023.255 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE On March 5, 1970, Thomas Whiteside named PCP and other chlorophenols as precursors of dioxins under certain thermal conditions. He claimed sunlight broke down PCP to dioxin precursors. Also, PCP, when heated to 300C. for 12 hours, could form OCDD (from 5g, you could get 1.5 g OCDD). He said considerable OCDD could be released to the environment giving a health hazard of very alarming dimensions. This article refutes these findings. 2,3,7,8-TCDD not present in U.S. commercial PCP at lOppb detection level. From analyses to date, U. S. commercial PCP was assumed to contain less than lOOppm of HCDDs, less than 200 ppm HpCDDs and less than 2000 ppm OCDD. Author concluded HCDDs were most toxic, but not more toxic than PCP itself. Also, light causes photodegradation of PCP and chlorodioxins to harmless by-products. Some environmentalists claim that sunlight or combustion will cause higher chlorinated dioxins to dechlorinate to the more toxic lower chlorinated species. Mentions irradiation of solution of aqueous NaOH/pure dioxin-free PCP giving rise to OCDD and HpCDD but no TCDDs. Also HCDDs and HpCDDs formed on photolysis of OCDD dissolved in alcohols. TCDDs more rapidly degrade under these conditions than OCDD. Original work: OCDD in petroleum oil is decomposed on filter paper by UV or sunlight. More rapid in oil than not in oil. TCDDs not detected as breakdown product. Conclusion: If PCP with dioxin impurities are on the surface of treated wood in an oil film, the lower CDDs photodegrade more rapidly. Studies on surface of PCP/petroleum treated pole section give same results. Heating oil solutions of PCP up to 190C. for two weeks does not form OCDD. Says a temperature of 200-300C. is most favorable for OCDD formation in low yield. Hexachlorobenzene (HCB) is most prominent by-product. Shows chemistry of formation of HCB, 0CDF and OCDD all from "predioxins". Also, showed OCDD biodegraded by soil. Also, no significant migration of OCDD in soil. Other statements Environmental studies indicate 2,3,7,8-TCDD does not leach in soils by rainfall, and is not taken up into the economic portion of the plants or translocated in plants. 2,3,7,8-TCDD not formed by microbial action or chemical condensation of 2 ,4,5-trichlorophenol in soil. Thus, if OCDD was dechlorinated to TCDDs, there is no contamination of food chain or biomagnification of dioxins in the environment. SUBJECT TO PROTECTIVE ORDER. 26 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Overall conclusion Potential occupational health and environmental hazard of PCP and PCDDs greatly exaggerated. PCP as produced in U. S. does not present an unreasonable risk to man or environment. Also, the use of PCP as a wood preservative doesn't either. D. Dickson, Nature, 283, 415 (1980) "PCP Dioxins Found to Pose Health Risks" Mr. Feucht of Canton, Ohio lost a herd of cattle apparently due to PCP-high levels were found in the blood of the dead cattle. It apparently came from the PCP treated wood used to build a new barn where the cattle were kept. Residents near the Lexington Blue Grass Array Depot in Kentucky showed a high incidence of leukemia apparently due to exposure to PCP use to preserve ammunition boxes at the depot. Researchers at the National Institute of .Environmental Health Sciences and North Carolina State University found that cattle fed with feed containing commercial technical PCP experienced a decrease in body weight and feed efficiency, progressive anemia, and lesions in the mucosa of the urinary bladder. Since analytically pure PCP or a control didn't cause these effects, the results must be caused by the PCDDs or PCDFs in the PCP. BENTIAL SUBJECT TO PROTECTIVE ORDER. 27 C23257 II. III. IV. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Won-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Authority: J. Bagley, et al Title: Association between Renal Function Tests and Pentachlorophenol Exposure Reference: Clinical Toxicology, VI, 97-106 (1977) Citation No: 8 Source of Dioxins Source: Not discussed Sampling Technique: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Not discussed Analytical Techniques Specificity: Not discussed Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Objective: Determine if exposure to pentachlorophenol can cause renal impairment in humans. No mention is made of chlorinated dioxins or its effect. Blood and urine samples were taken along with creatinine, clearance and phosphorus reabsorption values on 18 workers at a wood treating plant just prior to vacation, during vacation, and for a period of time after vacation. Blood and urine concentrations of PCP were higher while on the job. Also, creatinine clearance and phosphorus reabsorption values were depressed before vacation and improved during vacation suggesting that PCP exposure reduced both glomerular filtration rate and tubular function with recovery following a non-exposure period. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 28 023258 I. II. III. ATTORNEY-CLIENT PRIVILEGE Noa-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): K. Ballschmiter, et al Title: Occurrence and Absence of Polychlorodibenzofurans and Polychlorodibenzodioxins in Fly Ash from Municipal Incinerators. Reference: Cheraosphere, 12^ 585-594 (1983) Citation No: 5 Source of Dioxins Source: Fly ash from municipal incinerators, Study not completed. Only partial results reported. Sampling Technique: Does not discuss how fly ash is obtained. Sample of chemicals in fly ash is obtained by extraction by refluxing 18-20 hrs. in a solvent of toluene, methoxyethanol (Methylcellusolve) and cone. HC1 (50:20:1 by volume). The filtered extract is extracted with 2M KOH and washed with distilled water (takes out phenolics). After drying with Na2S04 , the extract is concentrated. The PCDDs and PCDFs are isolated by use of Florisil column. Hexane removes the pentachlorobenzene, PCBs and octachloronaphthalene. Toluene-diethyl ether (9:1) elutes the PCDDs and PCDFs. Flow Data (mass transfer): Not discussed. Chemistry of Formation: Pyrolysis of chloroethene and chloroethines are precursors. They form chlorobenzenes which react with H 2O or O2 at 500C. (via polychlorobiphenyls) to give PCDDs and PCDFs. Isomers Identified: OCDD - 0.5 to 800 ppb range from 6 incinerators in W. Germany. Analytical Techniques: Used HRGC/ECD and HRGC/MS-SIM technique. Specificity: At present only OCDD Sensitivity: Limit of detection = 0.1 ppb (0.1ng/g) for OCDD using HRGC/ECD. Na S M |iii S U R .IF T T T O D D n T rrT I\/ir r m r \ r n 29 C2325 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) Objective: Correlate operating conditions of an incinerator with organics found in the fly ash (primarily PCDD and PCDF). Study not completed. The occurrence of PCDFs and PCDDs in fly ash from municipal incinerators is well established. Chloroethenes and chloroethines appear to play a central role as precursors. Good summary of pathways to PCDDs and PCDFs from .CX=CX2 (X=H,C1) given in Fig. 1. Found a strong correlation between the formation of polychlorinated benzenes and biphenyls and the formation of PCDDs and PCDFs. The authors say, as a rule of thumb, 2,3,7,8-TCDD is between 1 to 10% of the OCDD value. No correlation between PCDD formation and HC1 emission. SUBJECT TO 30 023261) ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Mon-Industrial Sources ,of Chlorinated Dibenzo-p-dioxins I. Citation Author(s) : D. G. Barnes Title : Reference: Assessing TCDD Emissions from Municipal Waste Combustors Chemosphere, 12, 645-655 (1983) Citation No 6 II. Source of Dioxins Source: Municipal Waste combustors (incinerators) Sampling Technique: Two EPA modified Method 5 sampling trains traversing the stack in an isokinetic manner. Extraction and analyses performed in a way that no distinction was made between particulate-bound and vapor phase TCDDs. Details published elsewhere. Flow Data (mass transfer): Flue gas flow rate (dscra/sec) = 3.7-83.3. Chemistry of Formation: Not discussed. Isomers Identified: Data in paper indicated the method used could not distinguish 2,3,7,8-TCDD from several of the other TCDD isomers. Ill. Analytical Techniques Specificity: Used HRGC/HRMS to determine isomer specific levels of TCDDs. Also, used LRGC/HRMS which was not isomer specific. Sensitivity: Did not mention detection limits. IV. Comments (Significant Data, Graphs, etc.) Combustion temperature (C.) = 555-1200 Stack temperature (C.) = 139-232 Certain studies point to a possible connection between exposure to chlorophenols and/or phenoxy herbicides (with TCDD contaminants) and soft tissue carcinoma., Other studies in the U. S. suggest the overall risk of excess cancer from TCDD contaminated materials is likely to be small. SUBJECT TO PROTECTIVE ORDER. 31 023261 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Reproductive effects: Those few human epidemiological studies do not demonstrate clear exposure-related effects. Exposure: The concentration of TCDDs in stack emissions from municipal incinerators strain our analytical ability to detect them. Dilution effect to ground level would not permit detection, thus dispersion modelling used. Stack concentrations of TCDDs: ND - 3.5 ng/dscm Annual maximum average ground level concentration of TCDD isomers using PTMAX Air Dispersion Model: up to 3.8 x 10- 5 ng/m3 of 2,3,7,8-TCDD (not truly isomer specific). Total TCDDs= ND-9.2 x 10-5ng/m3 . SUBJECT TO PROTECTIVE ORDER. 32 attorney w o rk product a t t o r n e y -c lie n t PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): D. G. Barnes, et al. Title: Dioxins and the Regulatory Process at EPA Reference: Presentation at Nat. ACS Meeting in Kansas City, MO, Sept. 14, 1982. Citation No: 7 II. Source of Dioxins Source: Flue gases and particulates from 2 PCB waste incinerators and 5 municipal waste combustors (the latter covered in Citation No. 6) Sampling Technique: Not discussed (see Citation No. 6) Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: None specifically III. Analytical Techniques Specificity: Not discussed Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) Environmental samples have been found which contain virtually all of the 22 TCDD isomers and most of the other 75 PCDDs. Also, the PCDFs (total is 135 isomers) Two commercial incinerators used to burn PCBs gave detectable levels of TCDDs and TCDFs. Using certain assumptions, computer models, and analyses, the conclusion is that the risks associated with PCB incineration are not unreasonable with regard to cancer or reproductive effects. EU subject to protective order. 33 r n O n 'J U O <0 O O I. II. III. IV. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): E. Benfenati, et al Title: ~ Polychlorinated Dibenzo-p-dioxins (PCDD) and Polychlorinated Dibenzofurans (PCDF) in Emissions from an Urban Incinerator. Correlation Between Concentration of Micropollutants and Combustion Conditions. Reference : Chemosphere, _12, 1151-1157 (1983) Citation No: 10 Source of Dioxins Source: Stack emissions from an urban incinerator. Sampling Techniques: Described in earlier article [Chemosphere, U , 577(1982)] Flow Data (mass transfer): 28,500 - 40,450 Nra3/hr. Chemistry of Formation: Not discussed Isomers Identified: No specific isomers identified, only isomer classes; e.g. TCDFs, HCDDs, etc. Analytical Techniques Described in previous article [see above] Specificity: Only determined isomer classes. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Table 1 (Part 1) gives the amount of PCDDs and PCDFs emitted in ug per ton pf waste burned and the minimum and average combustion temperature (C.). Some correlation between minimum combustion temperature and PCDD/PCDF concentrations. Table l(Part 2) gives the mean stack flow (Nm3/hr.), tons/day of waste burned, mean stack temperature (C.) and HC1, S02, CO, NO and particulates emitted. Except for some correlation with minimum combustion temperature, no other correlation between PCDD/PCDF emissions and operating conditions could be found. HCDDs and TCDFs are the most abundant isomer classes and OCDD and OCDF are the least abundant. Conclusion: The emission of PCDDs and PCDFs is inversely related to combustion temperature. Agrees with others who report that 2,3,7,8-TCDD decomposes above 800C and no PCDDs have been found in incinerators operated at high temperatures (<1200C.). 34 attorney w o rk product a t t o r n e y -c lie n t pr iv ileg e Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I Citation Author(s): D. Brocco, et al Title: Polychlorodibenzodioxins and Dibenzofurans in the Environment Reference : Commission of the European Communities (Report), EUR 7624, 82-88 (1982) Citation No: 11 II, Source of Dioxins Source: Emissions from urban incinerators and from soil samples near the incinerator Sampling Techniques: Not described in detail. Mentions that the technique is very important. Great attention has to be paid to the isokinetic sampling of fumes for particulates and trapping of the gas phase. Flow Data (mass transfer): Not discussed Chemistry of Formation: No chemical equations are shown but certain comments are made. It appears that the higher the hydrochloric acid concentration in the fumes, the higher is the yield of the more J chlorinated species. Also, the higher the furnace temperature, the more abundant the concentration of chlorinated species is in the vapors. Also, phenols present in most vegetables have been shown to be precursors of PCDDs and PCDFs when a chlorine donor is present. Isomers Identified: In stack emissions: TCDDs, PeCDDs, HCDDs, HpCDDs, OCDD and corresponding PCDFs. In soil samples: HpCDFi, HpCDF2 , HpCDD*, HpCDD2 , OCDF and OCDD. Ill. Analytical Techniques Specificity: Appears specific for TCDDs, PeCDDs, HCDDs, HpCDDs, OCDD and corresponding PCDFs. Did not identify specific isomer. Sensitivity: Not discussed SU BJECT TO PROTECTIVE ORDER. 35 r n o Q fU. UwOiiD ATTORNEY W ORK PRODUCT A.rrORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs) etc.) Describes a good analytical procedure to determine PCDDs and PCDFs. Avoid heating the samples. Has good clean-up procedure. Used GC/MS with Ni63 electron capture detector and SIM. Figure 2 and Table I give analysis of emissions from incinerators for PCDDs and PCDFs and HC1. Table II gives analysis for PCDDs and PCDFs in soil samples various distances from the incinerator (500-2000 meters). SUBJECT TO PROTECTIVE ORDER. 36 A" ."''s ^EY-CENT PR,VILge Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): G. Broker and H. Gliwa Title: Investigations of the Dioxin Emissions from the Municipal Incinerators in Nordshein - Westfalen Reference: LIS-Ber.; ISS 1^, (1982) Citation No: 93 II. Source of Dioxins Source: Dusts (course and fine) from 8 municipal incinerators that burn mainly domestic garbage and from 2 incinerators that burn domestic garbage with sedimentation sludge. The sampling point, in all cases, was in the vent pipe behind the electrofilter (ESP). Sampling Techniques: The gas stream was passed through a cyclone probe through a quartz fiber plug (collected course particles) and a glass fiber ' wadding on the outlet side (collected fine particulate). Numerous samples were taken at each incinerator. A representative mixed sample of the course particles from each incinerator (10 samples - 8 from garbage incinerators and 2 from garbage/sludge incinerators) was prepared. Then a combination on the individual plant mixed samples for the 8 garbage incinerators (1 sample) and the 2 garbage/sludge incinerators (1 sample). Thus 12 samples in all. The same sampling procedure was used for the fine particulate. Thus there were 12 analogous samples of this fine material. Each sample was extracted at LIS (details not given) and sent for analysis to two Swiss institutes (no details). Flow Data (mass transfer): Total for all 8 garbage incinerators: 380 hours to sample ~ 1700m3 of flue gas (~ 4.5m3/ h r .) Total for the 2 garbage/sludge incinerators: 120 hours to sample 540m3 of flue gas (~ 4.5m3/hr.) CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 37 023267 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE -- / Chemistry of Formation: Not discussed Isomers Identified: PCDDs: TCDDs, PeCDDs, HCDDs, HpCDDs as chlorine no. isomer clusters and OCDD III. Analytical Techniques No details on this method of analysis, but assume GC/MS method was used based on the quality of the data and detection limits. Specificity: Chlorine no. isomer clusters and OCDD Sensitivity: Detection limit = 0.2 ng/g dust to 24 ng/g dust depending on sample and isomer cluster being analysed IV. Comments (Significant Data, Graphs, etc.) The 10 different incinerators are specifically identified in the article. Figure 1 and 2 give the procedure for preparation of the mixed samples. Table III and IV give the resulte of PCDD analysis on the various samples. Sample 9 showed extremely high levels (ng/sample): TCDDs, 200; PeCDDs, 491; HCDDs, 3995; HpCDDs, 5330 and OCDD, 2963. Based on several assumptions, the main one being that the PCDD concentration in sample 9 (considerably larger than all others) was accepted as the total emission, the following specific emission factors were obtained which enter into the diffusion calculations: Component TCDD PeCDD HCDD HpCDD OCDD Emission concentration (g/m3n) 1,43 io~8 3,50 10~8 28,50 10~8 38,10 10~8 21,20 10~8 Spec, emission (g/t garbage) 8,58 io" 5 2,10 io" 4 1,71 io" 3 2,28 io" 3 1,27 10~3 From the above values, the maximum concentrations for a reference surface of 1km2 occurring in the evaluation area around the incinerator is shown in Table V SUBJECT TO PROTECTIVE ORDER. 38 C23268 ATTORNEY W ORK PRODUCT 'TORNEY-CLIENT PRIVILEGE [g/m3 ](mean value) [g/m3](95% cumulative frequency) TCDD PeCDD HCDD HpCDD OCDD 5,11 1,25 1,02 1,36 7,57 10- 14 1 0 ' 13 10 12 io" 13 --> 1O 1 *-* w 4,77 1,17 9,50 1,27 7,07 10` 13 1 0 ' 12 io" 12 io" 11 io" 12 According to the consistent evidence of various authors, the fraction of 2,3,7,8-TCDD in the entire detected TCDD amounts to less than 5%. Concerning the relevance of the TCDD emissions to the others present in an incinerator stack gas, here is the order: S02 > NO > Pb > HCL > Zn > TCDD > Se > Cd > HF CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 39 C.23269 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation A u t h o r (s ): G. Bronzetti, et al Title: Mutagenicity Study of TCDD and Ashes from Urban Incinerator "in vitro" and "in vivo" Using Yeast D7 Strain Reference: Chemosphere, 12, 549-553 (1983) Citation No: 12 II. Source of Dioxins Source: 2,3,7,8-TCDD: synthesized at NIEHS Chemical Lab (Research Triangle Park, N. C.). Ashes from San Donnino, an urban incinerator in Florence, Italy. Sampling Techniques: Not discussed Flow Data (mass transfer): Not duscussed Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD was 98.99% pure. There was 1% 2,3,7-TrCDD. Nothing identified in ashes or in the ash aqueous extract. Ill. Analytical Techniques Specificity: Not discussed Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) 2,3,7,8-TCDD induced genetic effects both "in vitro" and "in vivo". So did the ashes and the aqueous extract of the ashes. SUBJECT TO PROTECTIVE ORDER 40 C2327U Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT / FORNEY.CLIENT PRIVILEGE Citation Author(s): R. R. Burab, et al Title: Trace Chemistries of Fire: A Source of Chlorinated Dioxins Reference: Science, 210, 385-390 (1980) Citation No* 13 II Source of Dioxins Source: Particulates from rotary incinerator, stationary tar burner, U. S. municipal incinerator, Diesel truck and auto mufflers, home fireplaces, home electrostatic precipitators, cigarette smoke, and soil and dust near combustion sources. Sampling Techniques: Sampling of the sources were discussed in layman1s terras Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Only 2,3,7,8-TCDD specifically identified. Other TCDDs, HCDDs, HpCDDs and OCDD were identified only by isomer groups. Ill. Analytical Techniques LC plus LRGC/MS (analytical method ML-AM_73__97) and HPLC plus GC/MS (analytical method ML-AM-78-63) were used. These methods descriminate 2,3,7,8-TCDD plus up to 16 other isomers. Specificity: ' Quantitative data only for 2,3,7,8-TCDD and OCDD. Sensitivity: In footnote of Table 3 Limits of detection: TCDDs, 0.001-0.01 ppb;. HCDDs 0.01-0.05 ppb; HpCDDs, 0.005-0.03 ppb; OCDD, 0.01-0.05 ppb. IV. Comments (Significant Data, Graphs, etc.) Conclusion is that chlorinated dioxins appear to be ubiquitous. The data suggest that chlorinated dioxins result from trace chemical reactions occurring in fire. CO R H? SUBJECT TO PROTECTIVE ORDER. 41 r r*.o6 6O 7 i ATTORNEY WORK PRODUCT ' ' CL.-: IT PRIVILEGE Table 1. gives chlorine content of fuels. Table 3. gives analytical results of PCDDs from the various sources. [apparent dioxin content in ng/g(ppb)] Science, 213, 1058 and 1060 (1981) - Two letters adversely criticize Bumb's article. D. Kriebel - Points out that materials to be combusted were not analyzed for PCDDs, thus not absolute proof of formation of PCDDs. Also, points out that PCDD level in soil and dust at the Dow plant is much higher than reported for any other soil sample. R. E. Carlson - Points out the 3 possible routes to PCDDs observed in combustion effluents: (1 ) PCDDs present as contaminants and simply are derived by volatilization-particulate absorption. (2) from combustion of chlorophenolics. (3) PCDDs formed in the fire from organic material. Bumb does not mention route 1 or 2. Since the route or routes by which PCDDs are formed has not been established, the conclusion of Bumb, et al, that the ubiquity of PCDDs is due to "natural phenomena" must be reevaluated. W. B. Crummett (co-author of original article) - Counters Kriebel's comments by saying that data providing "circumstantial evidence of combustion as a source of PCDDs" was included in original manuscript but reviewers requested condensation of the table thus it was left out (presented here). Apparently the concentration of PCDDs appear to attain a maximum around 300-600 feet from the combustion source. Crummett also indicates that Lustenhouwer [Chemosphere, 9, 501 (1980)] previously presented and thoroughly discussed Carlson's 3 routes for the formation of PCDDs. rn 42 O w IV r 24 October 1980, Volume 210, Number 4468 y <" I ALLAK M. ford, pfl) *!**O A2SA ATTORNEY WORK PRODUCT ATrSN EY-CU EN T PRIVILEGE l\ Discovery Chlorinated dioxins appear to be ubiq ov c Trace Chemistries of Fire: A Source of Chlorinated Dioxins uitous. Their ubiquity is due to the exis tence of natural phenomena, trace chem istries of fire which consist of numerous chemical reactions occurring during combustion at concentrations as low as 1 0 " percent. We include two major pathways in these trace chemistries of R. R. Bumb, W. B. Crummett, S. S. Cutie, J. R. Gledhill fire, involving (i) chemicals present in higher,concentration and reacting at very R. H. Hummel, R. 0 . Kagel, L. L. Lamparski. E. V. Luoma D. L. Miller, T. J. Nestrick, L. A. Shadoff, R. H. Stehl, J. S. Woods low yields (10-1* percent) and (ii) chem icals present in trace concentration and reacting at higher yields (10~* percent). A variety of research organizations have addressed themselves to the inves tig atio n of combustion processes. How Polychlorinated dibenzo^p-dioxins densation of preexisting polychlorinated ever, virtually all of their work has been have been found in fly ash from munici phenols. concerned with the kinetics and ther pal incinerators by Olie et al. (1) in the The-findings reported here are not of modynamics of the fuels, oxidants, ma Netherlands, by Buser et al. (2) in Switz fered as comprehensive or exhaustive re jo r intermediates, or major products. erland, and by Eiceman et al. (5) in Can sults. Limiting factors include the small Mention should be made o f several re ada, Japan, and the Netherlands. Buser number of scientists specifically trained cent reviews of these investigations (5). also reported finding them in fly ash from in the required methodology and the although none of them discuss either an industrial beating facility. In all these highly sophisticated instruments needed pathway described above. In an attempt to determine the source of 2,3,7,8-tetrachlorodibenzo-p-dioxin Summary. New, highly specific and sensitive analytical methodology has been ap (TCDD) that we detected in some fish plied to the determination of chlorinated dibenzo^p-dioxins in particulate matter. The from the Tittabawassee River (6). we ex results show that the dioxins are present in particles from many types of combustion amined the local as well as more distant sources and in dust and soil in the vicinity of combustion sources. The data indicate environments and found that a large that chlorinated dioxins may occur in particulate matter from the combustion of most number of sources emit chlorinated diox types of organic material, and suggest the hypothesis that chlorinated dioxins result ins into the environment. Samples were from trace chemical reactions occurring in fire. gathered from incinerator stacks as well as from chemical tar burners and a fossil- fueled power plant, vehicle mufflers, studies the findings were qualitative and to conduct the work. In addition, the fireplaces, chimneys, cigarette smoke, the presence of the dioxins was consid subject involves a large number of vari and portions of charcoal-broiled steaks. ered to be most probably caused by con ables over which the investigators had Chlorinated dioxins were found in densation of chlorophenols. Olie, how no control. each sample. However, those on panicu ever, suggested that a thermal synthesis Samples were:not always taken by sta late matter taken from the air emissions from inorganic chloride and organic ma tistical design, and results are not in of a wide variety of commercial and do terial was possible, and this route was tended to represent anything other than mestic combustion processes are espe supported by the presence of relatively large amounts of chlorinated benzenes on the particulate matter. Eiceman sug gested that these compounds are formed during incineration processes. This article presents quantitative data on particulate m atter from a wide variety of combustion processes. .These data cannot be satisfactorily explained in en tirety by attributing the presence o f poly chlorinated dibenzop-dioxins to cen the sample analyzed. The analytical methodology developed so rapidly dur ing this investigation (hat later results cannot always be directly compared to earlier ones. The analytical methodology including sampling has been reviewed by a group of scientists (4), however, and found to represent the stale o f the art. The results as a whole verify scientific observations that are now emerging worldwide. cially significant. Combustion processes must be more than 99.9 percent efficient to ensure reduction of the concentration*V. W . B. C m mm ell. S. S . C u lie. K. H . H um m el. R. O . K a g cl. 1.. L . la u n p u r A i. D . 1.. M iller. T . J. N o t- rick , L . A . ShadefT. K. H . S ieh l, and J. S. Wood* are an aly tical scien tists in the M ichigan Division A nalyt ical 1 -ah o rato riej o f D ow C h em ical U .S .A .. M id la n d . M ichigan dRMO. R . R . B tim h is d irecto r o r M ichigan D ivision R cseaich and D evelopm ent E. V. L uom a is d ire c to r o f th e A nalytical U iJw Jitv ir* . a n d 1. K. G ledhill is m an ag er o f M ichigan Dtsi-iun E n v iro n m en tal C o ntrol a t D ow C hem ical U .S.A . C orrespondence s h o u ld ^ ^ Table I. Chlorine content of fuels (summa combustion are jumbled at low concen Table 2. Chlorinated dioxins. rized front (7)]. trations in a sea of chemical reactions in Fuel Coal Refuse Piper Leaded gasoline Unleaded gasoline Fuel oil Chlorine (ppm)) cluding pyrolysis, oxidation, reduction, and acidolysis which result from inter 1300 (mean) action of ions, electrons, free radicals, 2500 (average) 300 to 1600 land free atoms. Up to now, the behavior 300 Iof this chemical potpourri has been stud Ito 6 ied only in terms of the major products of N.A.* , combustion--water and carbon diox "N.A.. oo4 available. Data were not available for the chlorine conlent in fuel oil. However, measurements indicated that 500 pounds of hydrocen chloride would be produced per day per 100.000 persons who homes were he-ied by oil-fired furnaces. ide--and those generally described as minor--carbon monoxide, hydrogen chloride (7). sulfur oxides (11), and nitro gen oxides 1/2). This situation is further Chlorine substitution MonoDiTriTetroPentaHexaHeptaOcta- Acro nym MCDD DCDD TjCDD TCDD PCDD HCDD H,CDD OCDD Number of positional isomers 2 10 M 22 14 10 2 1 complicated by the use of water to quench or scrub the combustion gases. tion of TCDD or other chlorinated di- of the dioxin from 1 part per million Donaldson (13) points out that water benzo-p-dioxins have been evolving. We (ppm) to 1 part per billion (ppb). Com treated for domestic consumption con used primarily GC-MS for these determi mon combustion processes are not ade tains about 1000 ppb organic chemicals. nations (d). By means of several liquid quate (5). Commonly used waters often contain chromatographic (LC) cleanup proce higher amounts of organic chemicals. dures, we developed specific methods for When the chemicals in scrubber waters the determination of each of the tetra-, Building Blocks for Chlorinated Dioxins come in contact with (he gaseous react bexa-, hepta-, and octa- compounds in ing chemicals, many more trace chem environmental samples. Details of these Refuse and fossil fuels are extremely icals may form. methods are being published in a series complex mixtures of many chemicals One trace-level ccmbus*ion product, of three comprehensive papers (IJ). and compounds, some of which are pres benzo[o]pyrene (4), has been studied in Since some of the procedures were de ent at low concentrations. The chlorine some detail. Like chlorinated dioxins, it veloped during the course of this work, content of various materials used as fuels is found on particulate matter. It is we report results here under the general for combustion has been examined by a formed in higher concentrations during heading TCDD, which includes 2,3,7,8- committee sponsored by the National inefficient burning, has a high melting TCDD and other isomers as outlined be Academy of Sciences (7). ffa b le j)sum point, and readily photodegrades in solu low: marizes the result of that survey. The tion. It is highly stable on particulates 1) Analytical method ML-AM-73-97 National Academy of Sciences estimated and has a very low solubility in water. (LC plus GC-MS) discriminates 2,3,7,8- that " 311 ppm of chlorine, mostly hydro The best estimates (14) showed that in TCDD plus 16 other isomers (16). gen chloride. Is in flue gas from burning 1971 benzoinIpyrene was produced in' 2) Analytical method ML-AM-78-63 normal base refuse." Some of.this chlo the United States by refuse bumjng, heat [high-pressure liquid chromatography rine is found on the fly ash accompany and power generation, coke production, (HPLC) plus GC-MS} discriminates ing the flue gas. and automobiles and trucks in amounts 2,3,7,8-TCDD plus 11 other isomers (17). Fly ash from a municipal incinerator in of 600, 500, 200, and 20 tons, respective ' 3) Analysis by HPLC plus capillary Amsterdam was examined for chlori ly- GC-MS discriminates 2,3,7,8-TCDD nated aliphatic and aromatic hydrocar The term chlorinated dibenzo-p-diox plus two other isomers. bons by Lahaniatis et at. (8). More than ins, or more simply chlorinated dioxins, The data from the various investiga 77 gas chromatography (GC) peaks, rep refers to 75 compounds or any combina tions of environmental samples are sum resenting concentrations of 5 to 250 ppb, tion of the 75. Dibenzo-p-dioxin has the marized inQ ab lcT ^The samples are de were obtained with an electron capture molecular structure scribed in theTollowing sections. (EC) detector. Mass spectrometr/ (MS) provided identification of 27 of these peaks and empirical formulas for 22 023274 more. Lasiewicz and Logensda (9) re ported the following percentages of solid All soil samples listed in Table 3 were and gaseous products in emissions from collected at the surface from open, un oil-fired healing and power plants: sulfur disturbed areas, 10 by 10 centimeters dioxide, 1 to 6; sulfuric acid, 1 to 6; car It is said to be chlorinated if one or square and 1 centimeter deep; an effort bon monoxide, 0.1 to 0.2; nitrogen ox more of the hydrogen atoms at the 1, 2, was made to exclude grass and other de ides, 0.5 to 1; dust, 0.2 to 1; vanadium 3, 4, 6, 7, 8, and 9 positions is replaced bris. They were placed in clean bottles compounds, 0.005 to 0.01: nickel oxide, by a chlorine atom. The 75 different and sealed until they were analyzed. The 0.001 to 0.003; and soot, 0.1 to 0.5. Parti chlorinated dioxins, each of which has first 13 samples collected in the Midland cles emitted from coal-fired boilers were its own special properties, are listed in area were analyzed qualitatively. Octa- shown by Kobayashi and Ibezawa (70) to contain 3,880 to 38,700 ppm vanadium, 1,810 to 98,500 ppm nickel, 1,440 to 19,200 ppm iron, and about 270 ppm manganese. The data show that the myriad of ini Table 2. In only a few cases have these compounds been synthesized and their chemical and physical properties stud ied. Only TCDD has been examined comprehensively for its toxicological ef fects (14). and heptachlorodibcnzo-p-dioxins were detected in all the samples, hexachlorodibenzo-p-dioxins were detected in nine, and tetrachlorodibenzo-p-dioxins were found in only four. A second set of soil samples was taken from areas previously tial pyrolysis products formed during Analytical methods for (he determina- sampled. Five of these, including four -CONFIDENTIAL 44 ATTORNEY W ORK PRODUCT SCIENCE. VOL- 210 ATT/^DMCV /"I i c m t nnn/ii corresponding to the samples that pre viously showed TCDD, were analyzed by analytical method ML-AM-78-63, which permitted separation of 2,3,7,8TCDD from all but about 11 of its 21 iso mers. Interference was sometimes noted in the analysis of reagent blanks. To deter mine whether this was caused by con tamination, dust samples were collected from the tops of bookcases, solvent stor age cabinets, and hoods, and at the air intake, of the Dow Chemical laboratory. Analytical method ML-AM-78-63 was used. Dust samples to be used as con trols were also collected from Midland and Detroit and analyzed by method ML-AM-73-97. The concentration re ported for TCDD includes 16 other iso mers. The results of this random sam pling did not satisfy the need for control samples. Samples of soil and dust were therefore collected from Chicago, Illi nois, and from East Lansing and Gay lord. Michigan. A few of the TCDD re sults for Lansing and Chicago were con firmed by GC combined with high-reso lution MS. Other sources of environmental partic ulate materia] include "urban particulate m atter," collected in St. Louis, Missou ri, and distributed by the National Bu reau of Standards as SRM 1648, and Millorganite, a sludge fertilizer from Mil waukee. Wisconsin. The results of these analyses are also shown in Table 3. V Incineration JThe European findings of chlorinated dioxins in fly ash together with the re sults of our analyses of dust and soil led us to examine particulate matter from in cinerators and a powerhouse. Dow operates two major waste in cineration systems within the Midland complex. The first is a stationary tar burner operating at 72 million Btu's per hour, which was constructed and started in 1970. This unit represents one of the most advanced designs in liquid tar in cineration and is one of the largest in the world. It is equipped to burn supplemen tal natural gas automatically, should the burning quality of the tars be insufficient to maintain the desired combustion tem perature. The other Dow system is a ro tary kiln incinerator capable of in cinerating solids and liquids and oper ating at 70 million B tu's per hour. Sup plemental fuel is also burned in this unit in the rotary kiln and the secondary com bustion chamber to maintain the desired combustion temperatures. Samples of particulate matter were taken from the stacks of both units, using a procedure based on Environmental Protection Agency (EPA) methods (8), The data ------ ---- 3. Chlorinated dioxins in the environment. --a--rs a s A J h d------ ECT TO PROTECTIVE ORDER. Sample Num ber of Apparent dioxin content, ng/g (ppb)* TCDD sam Other ples isomen 2,3.7,8- Total HCDD HTCDD OCDD Soil Rural (Gaylord, Michigan) Urban (Lansing and East Lansing, Michigan) Major metropolitan (Chicago, Illinois) Dow Chemical (Midland, Michigan) Dust Dow Chemical laboratory Midland. Michigan Metropolitan (Detroit. Michigan) Metropolitan (St. Louis. Missouri) Metropolitan (Chicago, Illinois) Wastewater treatment sludge Commercial sludge fertilizer (Milwaukee, Wisconsin) Incinerators, powerhouse Dow powerhouse Dow rotary incinerator stack (present normal operation with supplemental fuel)* Dow stationary tar burner stack (normal operation with supplemental fuel) U.S. municipal incinerator (electrostatic precipitator) (Nashville. Tennessee) European municipal incinerators Mufflers Diesel truck muffler Auto muffler Other sources Home fireplace soot Home electrostatic precipitator Cigarette smoke Charcoal-broiled steak 5 5 8 5 0.8-18 6 0.5-2 2 4 1 0.16 2 1 0.29 0.3-100 . N.D.t N.D. 0.005-0.03 1-120 N.D. 0.03-1.2 0.03-0.3 7-280 0.7-3 0.12, M 0.03-0.04 (0.02) N.D.-Q.03 0.3 0.04 (0.04) 9-35 0.2-0.4 N.D.-0.3 2 N.D.-0.3 0.02 0.31 2 N .D .-0.05 0.03-2 0.1-3 70-3,200 N.D.-0.2 0.05-2 0.4-22 490-20,000 140-1,200 2-4 0.3-4 34 0.6-3 650-7.500 20-30 0.1-4 210 3-8 30 -180 1 38(20) 5 N.D. (10) 38(20) N.D. (2) 5 N.D. N.D. N.D. 1 7.3 0.4 7.7 2-20 2 0.02 0.003 0.023 4 N.D.-0.004 N.D.-0.004 N.D.-0.008 2 N.D.-0.3 1 0.4 (0.4) 2 N.D. 4 N.D. N.D.-0.1 0.6 N.D. N.D. N.D.-0.4 1.0 N.D. N.D. 2 4 24 1-5 4-100 9-950 1-20 27-160 190-440 14 28 30 30-200 60-130 4U-12U 0.020 N.D. 0.100 0.26 0.003-0.01 0.02-0.07 0.2-3 . 0.7-16 34 430 0.004-0.008 0.009 N.D. N.D. 0.9-25 1,300 0.02-0.05 0.03 (0.03) W h e r e m u ltip le s a m p le s w e re a n a ly z e d fro m s im ila r s o u r c e s , th e r a n g e o f o b s e r v e d v a lu e s is s h o w n . t N . D . in d c a le s th a t th e s ig n a l o b s e r v e d w.i> le>* th a n 3.5 lim es n o ise. L im its o f d e te ctio n g en erally o b serv ed w ere T C D D . 0.001 to 0.01 p p b : H C D D . 0.01 to 0.05 ppb; H ,C D D . 0.005 to 0 .0 3 p p b ; a n d O C D D . 0,01 to 0.0? ppb. L im its o f dctectio n n o t w ithin th ese ranges a re sh o w n p a ren th etically a fte r th e value re p o rte d for signals b etw een 2.5 a n d 10 tim es n o ise. m entai fuel nof included here because this practice has been elim inated. r" OQi)ri . {2 4 O C T O B E R 1900 U v O v i) ATTORNEY W ORK PRODUCT 45 ATTnoMFY-CUENT PRIVILEGE tD a ia w ithout suppl 387 for he rotary kiln incinerator are given in Table 4. There i a dramatic difference in chlorinated dioxin concentration be* tween runs with supplemental fuel and without supplemental fuel. The data for the stationary tar burner are summarized in Table 3. An examination of particulate material collected by the electrostatic precipitator on a municipal refuse incinerator in Nashville, Tennessee, also confirmed the presence of chlorinated dioxins. Tabic 3 presents the results of this analy sis. The performance of this and other Table 4. Chlorinated dioxin content of particulate matter from the rotary kiln incinerator. currently licensed municipal incinerators has been described in a recent article on refuse fuel recovery (19). Data on samples taken from the stack of a Dow Midland powerhouse operating under normal conditions with fuel oil and coal are presented in Table 3. Approxi mate data for the European municipal in cinerators are also shown for com parison. Fuel* Apparent dioxins, ng/g (ppb) Sam ple Kiln Sec TCDD ond ary Other isomers 2,3,7,8- HCDD HiCDD OCDD R.F, T. SW, G R,F, T.SW.G R,Ft T, SW, G R.F, T.SW.G Ri T, SW.G KRR*. T. SW.G T .SW .G T.SW.G Rr T.SW.G T O, G T, G Without supplemental fuel 1,800 2,800t 3,000 3,300 8,200t no 12,000 N.D. (260)t 13.000 63,000 1.300 5,600 With supplemental fuel N.D. (8.0) N.D. (2.0) N.D. (7.0) N.D. (5.0) N.D. (2.0) N.D. (2.0) N.D. (2.0) N.D. (4.0) N.D. (2.0) N.D. (2.0) 1.4 N.D. (1.0) N.D. (0.5) 5.0 4.0 110,000 510.000 2.000 37,000 13.0 4.0 6.0 27.0 110.0 180.000 810,000 3.000 59,000 30.0 9.0 15.0 170.0 950.0 T , tars: SW , solid w aste: G . gas: O , oit. ?T he high results reported for the 2.3.7.8- isom er are probably due to analysis by the nonspecific G C -M S packed-colum n m ethod. L ater results w ere o btained w ith a capil lary colum n specific fo r 2.3.7.8-T C D D . T h e T C D O resu lts from nin I lR ,) are n o t com parable to those from runs 2 and 3. (N u m b e rs in p a re n th e se s a re lim its o f d etectio n , as explained in a T ab le 3 footnote. Table 5. Other identified chlorinated compounds.* Sample source Chlorinated dibertzofurans -------Hexa- Hepta- Octa- Decachloro- bi- phenyl. Poly chlori nated ter- ' phenyls Dow research building ++ ++ ++ Midland city Fireplace soot All soil samples ++ ++ ++ Electrostatic ` ++ o f precipitator bjMetropolitan area dust (Detroit) QUrban area soil (Lansing and ~ East Lansing) ^Metropolitan area dust LlI Chicago > St. Louis H-Xfetropolitan area soil O (Chicago) ++ ++ ++ ++ ++ ++ ++t + +t i_ ~ . Positive according to re te n tio n lim e o n a liquid chrom atogram , GC-M S not u sed ; (+ + ) p o sitiv e by both IS L C and G C -M S . tV e ry large am o u n t relative to o th e r sam ples. o H Table 6. Chlorinated dioxins in rotary kiln incinerator scrubber water. tj LU m Sample ZD I Particulates filtered from scrubber water Without supplemental fuel With supplemental fuel Filtered scrubber water without supplemental fuel Apparent dioxins, ng/g (ppb) TCDD Other isomers 2,3,7,8- HCDD H,CDD 300 14 0.0018(0.01) 2.200* 32* 0.001 (0.0006) 3.400 200 0.005 26,000 970 0.024 OCDD 42,000 1,200 Q.026 C O T h e a n a l y tic a l m e th o d d id n o t s e p a r a te 2 .3 .7 .8 -T C D D fro m 11 o t h e r is o m e rs. A. TTDDMCV Combustion of Dioxins Early in 1963 Dow analytical scientists showed that TCDD decomposes 99.95 percent at 800C in a stream of air pass ing through an unpacked quartz tube containing the TCDD (20). Conse quently, it was accepted that TCDD would be destroyed in a system such as a tar burner. A further study in 1970 (21) confirmed these results and also showed that the 2,3,7.8-telra- isomer is stable be low 800eC. Another Dow study in 1970 (/9) estab lished that the combustion products of TCDD in a 130 percent excess of air are water, carbon dioxide, hydrogen chlo ride, and chlorine. The adiabatic ame temperature was calculated as 1025C. At this temperature the HC1/CI mole ra tio is 3.05/0.48. This study, coupled with the earlier studies, led us to conclude -that, below 800C, the destruction of TCDD is relatively incomplete. In preparation for the incineration at sea of the mixture known as Agent Or ange (22), the U.S. Air Force contracted with the Marquardt Company. Van Nuys, California, to conduct tests on the combustion of Agent Orange with fire wall temperatures of 1150, 1400, and 1600eC and a minimum of 30 percent ex cess air. TCDD, a trace impurity in one of the components of Agent Orange, was not found in the paniculate matter in ei ther the stack or the scrubber water at limits of detection of 300 and 2 ppb, re spectively. In these tests, the walls of the combustion chamber were preheated to the desired temperature (1400C) and the Agent Orange was added without aux iliary fuel. The temperature of the flame was not measured. The Air Force disposed of Agent Or ange in the summer of 1977 by high-temperaiure incineration at sea on a Dutchowned ship M/T Vulcamts. Although the walls of the aim bustion chamber were maintained at 1273C on the average and the high flame temperature was mea sured optically as 15U0CC, the EPA. which monitored this program, reported a combustion efficiency for TCDD of on 1. " _Ilyy aabboouutt S99.9 percent (23). NFIDENTIa l Particulate Matter From Mufflers wrapped in aluminum foil, placed in a method ML-AM-78-63; the results are plastic bag, and then put in a freezer to reported in Table 6. The water filtrate Mufflers frorti gasoline-powered auto mobiles were collected at muffler shops in Pontiac and Detroit, Michigan (more than 100 miles from Midland), as they were removed from cars. The car owners voluntarily gave the mufflers and infor mation about mileage and gasoline type used. The make, model, and mileage of each car were noted. The mufflers were transported to the Dow Analytical Labo ratories sealed in plastic bags. Mufflers from diesel-powered trucks were collect ed at Auburn and Saginaw, Michigan. They were sealed and transported as await analysis. Analyses were performed by method ML-AM-78-63. The results are shown in Table 3.1 Cigarette sm oke. Smoke generated by the simulated smoking of cigarettes (an arbitrarily selected national brand with out filters) was analyzed for trace levels of chlorinated dioxins. The smoke was collected on special collection matrices consisting of l(KV120-mesh silica (coate in situ with 20 percent hexadecane b weight) contained in a disposable glass transfer pipette. The cigarette was at tached to the pipette by cleaned latex from the scrubber water composite was also analyzed and the results are shown in Table 6. The data from Table 6 togeth er with the relative weight of scrubber water show that more than 99.7 percent of the chlorinated dioxins are associated with filterable particulate matter. The following conclusions are sup ported by this study: 1) Some refuse incinerators and fossil- above. rubber tubing and puffed by applying fueled powerhouses are sources of air At the Dow Analytical Laboratories, gentle vacuum with a rubber pipette borne and waterborne particulates that the inside chambers of the mufflers were bulb. Approximately 20 to 30 puffs nomi contain chlorinated dioxins. scraped and residue was collected from nally 2 to 3 seconds in duration were col . 2) Some gasoline- and diesel-fueled these chambers and analyzed for chlori lected from each cigarette. An entire automobiles and trucks are sources of nated dioxins by both GC with electron package of 20 cigarettes was combusted airborne particulates that contain chlori capture detection and GC-MS after liq during each experiment. Combustion ex nated'dioxins. uid chromatographic separation. Results periments were conducted in two dif 3) Some fireplaces, charcoal grills, are summarized in Table 3. The discov ferent urban locations. Before use, the and cigarettes have been identified as ery that there are chlorinated dibenzo-p- inlet end of each collection tube was sources of particulate matter that con dioxins in particulate emissions from in spiked with 2.0 nanograms of ,3C-labeled tains chlorinated dioxins. ternal combustion engines indicated that 2,3,7,8-TCDD, which served as an inter 4) Chlorinated dioxins enter the envi these compounds may be ubiquitous in nal standard for TCDD quantitation after ronment by way of airborne particulate combustion processes. residue cleanup. Each collection tube matter from combustion sources and wa was extracted with hexane, followed by terborne particulate matter from scrub a multistep cleanup, including reverse bers, which are increasingly required for Other Sources f - - ------- -- phase LC, to remove interferences. The major combustion sources. LC eluent was subjected.to both low-res 5) Additional chlorinated compounds Soot from fireplaces* The carbo olution GC-MS and electron capture GC were observed and apparently arise from naceous material on the walls of the met analysis. The results are given in Ta Combustion; they include chlorinated di- al firebox 'o f a 25-year-old fireplace, ble 3. benzofurans, decachlorobiphenyl, poly SUBJECT TO PROTECTIVE ORDER. whose flue had not been cleaned for 10 The further discovery that chlorinated chlorinated terphenyls, and others that years, was sampled in a manner designed dibenz&p-dioxins are the result of com have not been identified. to avoid contamination. Birch, oak, wil monplace burning involving fireplaces, low, mountain ash, and applewood un charcoal broilers, and cigarettes sup R eferences i u l N otes treated with preservatives had been burned in this fireplace, along with some paper to start the fire. The residue on firebrick in a 12-year-old fireplace, whose chimney had never been cleaned, was also sampled. The fuel had been hardwood, mostly oak, none of it treated with any wood preservatives. These samples were analyzed as described for mufflers. The results are presented in Table 3. Particulates from a home electrostatic prfripttsiinr P a r t ic u la t e m a la r ia l w a s collected from a home electrostatic pre cipitator. The collection represents the material accumulated during six spring and summer months of operation of the precipitator. The results obtained are al so reported in Table 3. Charcoal-broiled steaks. New York strip steaks grilled over a charcoal fire were sampled at 13, IS, and 28 minutes. Grilling for these times produced rare, well-done, and overdone samples. Each of the three samples was immediately ports the conclusion that these com pounds may be ubiquitous in combustion 1. K . O lie. P . L . V e rm e u le n . O . H u tz in g e r, Chem osphere 4 (N o . 8). 453 (1977). 2. H . R. B user. H . P. B o ssh ard t, C . J U p p e .ibid. 7 processes. (N o . 2 ). 165 <1978). 3. C . A. E icem an. R. E. C lem ent, F . W. K arasek. A nal. C hem . S I. 2343 (1979). 4. U , M . C ow gill. H . F reiser, M . L . G ross. L . B. R ogers. D. Schuctzlc. "E v alu atio n of analytical Other Chlorinated Compounds Identified chem ical procedures of the D ow C hem ical C om pany for the determ ination o f polychlorinated dibenzo-p-dioxins,** unpublished report to D ow The following compounds were identi fied in many of the samples: hexa-, hep- C hem ical U .S .A .. Ju n e 1979. 3. J. B. E d w ard s, Com bustion: The Formation and Emission o f Trace Species (A nn A rbor Science. ta-, and octachlorodibenzofurans, decachlorobiphenyl, and polychlorinated A nn A rb o r. M ich .. 1977); J . W . L arso n , E d .. Organic C hem istry o f C oo/ (A m erican C hem ical t S o c ie ty , W ash in g to n . D .C .. 1978); H . B. PalmerX terphenyls. Since analytical standards were not available and recoveries are not known, no quantitative measurements I and P. J. Seery. Anna. Rev. Phys. Cbem. 24,233) M I973). 6. W . B. C rum m elt and R. H . S leh l, Environ tieo U h P e r s p r c t 5 , 15 11973); R , A. H u m m e l. J . A v r. F ond C bem . 25. IIU9 (1 9 T ); L. A. Sh.i- were made. These observations are in Table 5. The samples also contained nu doff and K. A . H um m el. Uiumed. Stoss Spec trum. 5. 7 (1978); L . L . L a m p a n k i. N. H. M ahle. L . A . S h ad o ff. J . A gric, F ood Cbem. 26. merous unknowns that were not qualita tively identified. 1113 (1978); W . B . C n im m e ti. K. H . S tc h l. L. A. S h a d o ff, p a p e r p re s e n te d at th e 2.1rd C o llab o ra tive International P esticid es A nalytical C ouncil. Waterborne particulates front scrub . -- B altim ore. M d.. June 1979. w /7 .JC o m m itte e on M edical an d Biological Effect* of bers. Composite scrubber water samples f r '^ E n v ir o n m e n ta l P o llu ta n ts. Chlorine and Hydro were taken from the rotary kiln in gen Chloride (N atio n al A cadem y of S ciences. W ash in g to n . D .C .. 1976). cinerator during the sampling reported in Table 4. The particulate matter was sep 8. E . S. L a h a n ia tiv H . P artar. F. K arte. Chem- osphrre 6 (N o . 1). II (1977. 9. K . L a sie w icz a n d D . L o g e w sd a . Ochr. P o'- arated by filtration and the chlorinated dioxins were determined by analytical vietrzu 10 (N o. 3). 127(1976). 10. T . K o b a y ash i a n d T - Ik e z a w a , H yuyo-K rn K ogai K enkyusho K enya H o k u la 7 . I (1973). 24 O C T O B E R >980 H9397V ATTORNEY WORK PRODUCT 11. J . H . D ritc o t! i n d A . W . B e r g e r , Im p ro v e d C hem ical M ethods fo r Sam pling and Analysis o f G aseous Pollutants fro m the Combustion o f Fossil Fuels, vul. I, Sulfur Oxides (R eport PF209167, U .S . E nvironm ental Protection A gency, W u h itig lo n , D .C ., 1971). 12. C o tn m U tc c o n M e d ic a l a n d B io lo g ic a l E ffe c t! o f E nvironm ental P o d u ia n ti, S it ro teo Oxides (N ational A cadem y o f Science, W ashington. D C .. 1977). 12. W .T . D o n a W io n , E n viro n . Seri. T rrb n o i. 1 1 ,3 4 1 (1977). 14. C o m m itte e o n B io lo g ic a l E ffe ct o f A tm o s p h e ric P o llu tan ts. Particulate P u h cyclic Organic M at ter (N atio n al A cadem y o f S cien ces, W ashing to n , D .C ., 1972). 13. L- L . L am p arsk i. T . i . N est rick , R. H . S tehl, A nal. C kem . 51. 2273 (1979): T . 1. N estrick and L . L . L am p arsk i. in p re p a ra tio n . 16. A n aly tical m ethod M L -A M -73-97 c o n sist! o f a base digestion, an acid w ash o f the hesanc extra c t, and clean u p w ith alum ina and silica gel c o lu m n s. M easu rem en ts are m ade by k>w-reso lution G C -M S. 17. A n a ly tic a l m e th o d M L -A M -7 8 -6 3 in c lu d e s S o*hiel ex tractio n th rough a silica gel bed fol low ed by cleanup th ro u g h beds o f silica, silver nitrate-m odified silica, and b asic alum ina. V ari ou s c h lo rin a te d dio x in s are sep a ra te d by highp ressu re liquid ch ro m ato g rap h y and m easured oy low -resolution G C -M S. E nvironm ental P ro tectio n A gency m ethods \ ~ J 1, 2. 3 , a n d 3. F ed. /le g ist. 42. 41734 (18 A ugust 1977). 19. H . F r e e m a n . E nviron. S i i . T rchtnd. 12. 1251 (1978). 20. H . H . GiD. D ow C h em ical C o ., unn u h tish ed report (1963). 21. R. H . Stehl, R. R. P apcnfusi, R. A. Bredeweg, R . W . R o b ert* , in D ioxins --Origin and F a te, E . B lair. E d. (A m erican C hem ical Society', W ashington. D .C .. 1973). p. 121: H . P ro p h et,, D ow C hem ical C om pany, unpublished report (1970). 22. "D isp o sitio n o f O range herbicide by in c in e ra tio n ," D epartm ent o f the Air F orce, Final E n v iro n m e n tal S ta te m e n t. N o v e m b er 1974, 23. " A l-sea incineration of herbicide Orange on b o a rd th e M /T .V /fru m n " (R e p o rt E P A -600/2-7086, E nvironm ental Protection A gency, W ash in gton, D .C ., A pril IS' S). ^sssss t>c Multidimensional Scaling, Tree-Fitting, and Clustering Roger N. Shepard 'W ithout any quantitative information about the physical properties of colors, tones, speech sounds, or words, we can learn something about how humans pro cess such stimuli from an analysis of rat ings of perceived similarity, frequencies, with which the stimuli are actually con fused with each other, latencies of dis criminative responses, or, in the case of infants and other animals, magnitudes of the "orienting reflex" when one stimulus is substituted for the other (/, 2). This physical dimensions are as yet poorly characterized, and it is essential in the case of symbolic stimuli such as words, for which the relevant semantic dimen sions are not even present in the physical stimuli. Early History Proposals that stimuli be modeled by points in a space in such a way that per- -------------------- S T --------------------------------- " Summary. American mathematical psychologists have developed computer-based methods for constructing representations of the psychological structure of a set of stimuli on the basis of pairwise measures of similarity or confusability. Applications to perceptual and semantic data illustrate how complementary aspects of the underlying psychological structure are revealed by different types of representations, including multidimensional spatial configurations and nondimensional tree-structures or clus terings. purely psychological approach has ad vantages over a psychophysical one in the case of complex, naturalistic stimuli such as faces, for which the relevant T he au th o r it professor o f psychology at Stanford U n iv en ily , Stanford. C alifornia 94305. This a n k le w as p re sen te d as a n in v ited le c tu re o n 2 A pril 1979 at te U .S .-U .S .S .R . sym posium on "N orm ative and D escriptive M odels o f D ecision-M aking," jointly sponsored by the N ational A cadem y o f Sciences of ine U nited S tile s and th e S o v iet A cadem y o f Sci ^ C23278e n c e s , h eld a t T b ilisi in th e S o v ie t R ep u b lic o f 390 0 0 3 6 -8 0 7 5 /8 1024 I caved similarity is represented by spa tial proximity go back to (he suggestions of Isaac Newton (J) that spectral hues be represented on a circle, of Helm holtz and Schrodinger (4) that colors in general be represented in a curved Riemannian manifold, of Drobisch (5) that pure tones be represented on a helix, and of Henning (6) that odors and tastes be represented within a prism and a tetrahe dron, respectively. However, little prog- 1 9 0 5 0 2 .0 0 0 C o n v r ic h i *> I9R0 A A AS ress was made toward the development of data-analytic methods for the con struction of such spatial representations on the basis of psychological data until the efforts of a group of psychome tricians, beginning in the late 1930's at Chicago and subsequently moving to Princeton, culminated in the 1952 devel opment by Torgerson of the first fully workable method of metric multidi mensional scaling (7,9). This method is called "m etric" be cause it requires psychological estimates of metric distances between the stimuli. Either one had to assume that the data (for example, subjective ratings of dis similarity) increased linearly with such distances (9), or one had to use some preliminary (for example, "Thursto- nian") scaling procedure to convert the data into numbers that could then be as sumed to increase linearly with distance (5). Even after such numbers had been obtained, the computation required sev eral more stages in which one succes sively (i) estimated the " additive con stant" and thus obtained a matrix*of esti mated distances between the points: and then, on the basis of a theorem of Young and Householder (/0), (ii) computed a matrix of scalar products between the points (interpreted as vectors issuing from their common centroid), and (iii) factored this matrix into its eigenvalues and vectors to obtain explicit coordi nates for the stimuli in a Euclidean space of a number of dimensions correspond ing to the number of large eigenvalues. Meanwhile, I had been approaching the problem of analyzing such measures of similarity by estimating the nonlinear form of the monotonic function, = /rrwwi(cAj) (0 where is the obtained measure of simi larity between stimuli i and j and where dti is a distance between corresponding points / and j that satisfies quite general metric conditions. The conditions that 1 proposed were (i) the distance axioms of e r t u u r u I/IM ^ A l i ( V " toan t7 -r -v'E: This m aterial toa/ r^ j if*---- * jjis ^ 11 ffO . acted by copyright Whet hex come to he a emingly ubiquitous misconception is passed along in Eliot Marshall* article (News and Comment. 24 July. p. 4171 about (he Mediterranean fruit fly. The idea that successful application of the sterile male technique is limited to insect species in which the female mates only once is erroneous i/l. The success of the socalled sterile male management tech nique is dependent on li) the competi tiveness of the sterile insects vtvi-vis the fertile insects for mates ifertilization of oval and (iil the relative abundance of sterile versus fertile insects. Female pro miscuity is immaterial to the issue. Consider the proposition that mem dressing the tune point . This is par ticularly important in the case of the Mcdfly. since it mates more than once (/>. Ms iv in K. Harms Department o f Enli*motogy and Tesai Agricultural Experiment Station. Texas A.M University. College Station 77843 1. E. F. 1 .3 / V r A im .. A*rk , HunJfi lt?i.p.,uv 2. E G. Zouft*. A **.-Ia. tc n u li S r* Set. 12011*!. Origin of CMortntcd Dioxins The article "Trace chemistries of fire: A source of chlorinated dioxins" by any ether sod sample. The author neither comment on or refute the possibility that Dow's own plant may have been a significant source of chlori nated dioxins, although their data appear to support such a hypothesis. David Krieiel Center for the Biology o f Natural Systems. Querns Coitege. City University o f .New Fori. Flushing 11367 Bumb et at. suggest that "chlorinated dioxins appear to be ubiquitous. Their ubiquity is due to the existence of natu ral phenomena, trace chemistries of fire. . . . " Although their data demon strate the presence of polychlorinated dibenzo-p-dioxins (PCDDl in a wide va riety of samples it has hot been shown that the source of these compounds is de bers of an interbreeding population of sienle and wild insects with a 1.1 >v\ ratio are equally competitive for fertiliza tion of males and that their relative abun ft. ft. Bumb et at. (24 Oct. 1980. p. MSI is of potentially great import to environ mental chemists and toxicologists. The impact of the article, however is dimin novo synthesis in fire. Consequently, an evaluation of the principle routes that could lead to the PCDD observed in combustion effluents is necessary to pre dance n 1:1. Under these circum ished by an unjustified interpretation of vent the misconception that the environ stances. the probability that a given fe the data and by an important observation mental source of these compounds has male will mate with a sterile male is .5. that is overlooked. been determined. since one-half of the males are sterile. The article's title and several passages Three routes that could lead to the The probability that a given male will dearly suggest that the authors believe observed PCDD are: mate with a sterile fcmaJcis also .5. their work demonstrates,that Chlorinated 11The PCDD are known contaminants Thus. 25 percent of the matings which dioxins may be formed during normal of various chloroaromatics (/. 2\ which would be expected to occur in the popu combustion. To prove such a thing one have become widely distributed in the lation would he between sterile males must measure the amount of chlorinated environment. Thus, the observed PCDD and ferule females. 25 percent between dioxins in materials to be combusted, could be derived from a simple volatil sterile males and sterile females. 25 per combust them, and then determine ization-particulate absorption mechanism. cent between fertile males and sterile whether or not the amount of chlorinated 2) The combustion of various chloro- females, and the remaining 25 percent dioxins has increased. Such an experi phenotics will lead to the formation of between fertile male* and fertile females, ment is not reported by Bumb et at. The PCDO (2. 3). This mechanism has been resulting in 75 percent of the matings authors show that chlorinated dioxins suggested as a route to environmental involving at least one sterile parent and occur in combustion products, but this is PCDD tJ. 4). Although this pathway thus contributing no viable progeny to mu the same as showing that they are includes the partial synthesis of the the succeeding generation. The probabil- formed during combustion. In particular, PCDD by fire, it still requires the pres . itics apply regardless of the number of the occurrence of chlorinated dioxins in ence of anthropogenic chloroaromatics. matings (provided the sterile insects arc combustion products may be caused by a 3) The PCDD could be formed de novo < q as com sctitise as the fertile insects). |E2X3 Qi it is true when two matings arc considO cred that some fertile females which z UJ have first mated with sterile males may recover their fertility by a subsequent mating with a fertile male. However, in general contamination of the environ ment with chlorinated dioxins. The arti cle might at least have given data indicat ing that soil near major combustion sources had higher concentrations of chlorinated dioxins than soil more dis In the fire. The formation of aromatic chlorine compounds from polyethylene and inorganic chloride under pyrolytic conditions has apparently been demon strated (4). However, no experimental support for this observation is available, LJ the example provided, this restoration of f e Fr fertility will be exactly compensated for by other fertile females that first mated q_ wuh ferule males and then with sterile q males. Postulating a third or even more y--matings still results in love's labors lost zf e l__ because of the compensatory effect of U the equal competitiveness of sterile and ^ fertile insects. CD Deductive reasoning alone is sufficient for the college freshman biologist to con- dude that insect fidelity is not important to the success or failure of pest manage ment strategics for sterile insects. Indegnh mathematical analyses have been available for more than a decade ad? tant from them, but even such circum and it is not known if PCDD were among stantial evidence of combustion as a the observed products. This route would source of chlorinated dioxins is lacking. suggest a historical environmental role The authors do not comment on a for the PCDD. most interesting aspect of their data: the Bomb et at. do not mention route I as concentrations of chlorinated dioxins in a possible source of the observed PCDD. soil and dust samples from in and around even though they cite several studies Dow Chemical's Midland. Michigan, which demonstrate that preformed plant are considerably higher than those PCDD's are not 100 percent destroyed, from anywhere else. In fact, the lowest even in a very hot fire. They dismiss reported concentration of cither total route 2 became the "data cannot be TCDD. HCDD. HCDD. or OCDD (the RHfaciority explained in entirely by tefn*. hex-, hepu*. and octa-chlorinat* attributing the presence of (PCDD) to ed dioxins, respectively) in soil from condensericu of preexisting polychlori Midland. Michigan. K five or more times nated phenol*." However, they do not C23279than the highest concentration present any evidence on chloropbcoolic --I.WiSl** -- - Tfthk I. CMarinaud dioxin cowm of foil, Detection fawte an give tmfurentNext. SamCity P* xt Chicago Chura* C hicago Chicco C hicago Chicago C hicago Chicago Lancing Lancing' t Approxinule dttunee licet) II NE ya NE 400 NE 10(10 NE 1110 NE y n ne 400 NE 1000 NE MW ENE WO ENE Apport* lncincnior Incuenior lncincnior Incmcnlur Incinerator Incinerator lncincnior Incinerator Powerhouse Powerhouse Appanni duini conecu ralun. pg'l Ipptl TCDO HCDO N.D. coi N.D. <101 to N.D. 13)1 h l.t] 3 til ? (?) N.D. thl N.D. 1101 N.D. (101 N .D . (W t .V) I.Mil 110 Cn (401 140 40l.Mll WIND NUMI i:un N .D . 1401 H-CDD OCDD 140 2U\ .tMXI 1400 KM }H\ 4M) 1(10 IM) 2M) 410 ink) .22IXXI km J2i 14(11 Mkll 330 2tkni 4M) 1*33$ u concentration in their combustion feedclock or t.i PCDD isomer distribution profiles \J. 3) which would suppon this conclusion. In fact, the work of Buser ef ai. (.<) indicates that the majority of the PCDD isomers observed in the fly ash of a municipal incinerator and an industrial healing facility could he accounted for by the pyrolysis of the three most com monly used and environmentally wide spread commercial polychlorophenols. In summary, the rouie or routes by which observed PCDD is formed has not been established. Consequently, the conclusions of Bumh rr at. that the ubiq uity of the PCDD is due to "natural phenomena" must be reevaluated. Rurert E. Carlson Gray Fresliwater.BioloiiUui institute. University o f Minnesota, Navarre 5SJ92 I l n Pfeiffer. r J N corwk. C W Kucher. C-u, ( <i,-. 4. WU HVTHi i R H Srehl and I. L LamrwrsJu. A, irm r 1ST. IX>* I|U *'| H R Ruxr. H.-P. fkntM ig, C Kappr. CAe1. IS* tlSTIi 4 K Hie. P I Vennrulcn. O Hui/mger. iA J 4. 4 IN '* i H R Biiw M l C. lU flit, Amal (Arm. SI. :;,fiisMi Uu bJ Q It would be great if a meaningful mate0 rule balance experiment could be de^ M'Cd that would be reasonable to perbJ form However. at the trace levels (parts -- per billion or lecci of PCDD's it is gener- alb considered impracticable at present. bJ The data that Knebcl suggests would provide "circumstantial evidence of combustion as a source of chlorinated Ou dioxins" were included in the original q mamiscnpt. hui (he table was condensed H- -i ihc request of reviewers and editors. I-- Some of these data are summarized in O Table l. These data have been treated by CQ Townsend 1/1. who was able to show a relation between ratios of isomer groups and distance from the source. As would be expected, the concentration of the vanous dioxuts appears to attain a maxi* mum around 300 to 600 feel. Not enough data are available to draw* firm conclu sions. however. As a result of our investigation, it was dear (hat PCDD's were coming from combustion sources of which Dow has xvaL This was the point of the article. As part of a continuing program lo protect the environment from chemical contamination, the manufacturing plants are monitored for possible leaks. The data from this monitoring, together with new. specially acquired data, were accu mulated and restudied io determine if leaks had possibly occurred. None were detected. This was described in a 147ft report (2): however, it is not germane to a discussion of combustion phenomena. Carlson's proposed routes for the for mation of PCDD's were previously pre sented and thoroughly discussed by Lus* tenhouwer et at. (J). The fact that a hypothesis such as Ihc "trace chemis tries of tire" cannot be proved is com mon knowledge. Hypotheses are meant to be tested in every' conceivable way . Until they are prosed false, they are useful in guiding experimentalion. W a u e n B. Crummett Anut\ littil l.uhorut,iric\. Dow Clwntii nl U S.A.. Miihiyun Division, Midland 4B/*40 Rrf< I D I Townsend. J tnri>m .Si ttruhh BIS iM. 3" I (IWOII Z. rhkwifuicii Lfcosm T.ivX Kwvc. Thr Trmr ('Armutfir, ,if F>rt --A \i<ur, > .*/ ,i*J ft.iiur* h r Tht f*(rs >1/ ( 'ftAtnnuf,*,/ Oi.nm, fni* Ar /Hwrtifi'nrHf IMh. Ki^in Du i\ n . (Vw Chemi cal I* S A . Mtdlind. |H?|ti. * J W A l usienhutiwet. k . Iff*. O H inunter. CArmutpArre 4. Vit (IWilt. Abortion, Science, and (he Law As h lawyer with many sears* experi ence at the interface of law and science. I am heartened to read mi perceptively sound a statement of the rotes of the two discipline at that interface as that made " by B. G. Zacfc (Editorial. 17 July. p. 291). The taking of "We." even of human life, however defined, is not now and never has been absolutely illegal in the United Stales. The broad term denoting the killing of a person is "homicide." literally "man killing." A homicide in American taw and custom may be an act which in certain circumstances merits society's highest approval, but in other circumstances, its deepest repugnance. The unacceptabilily of a homicide vanes not only with the conduct of the killer, but also with the quality of the killed. In every culture most homicide has been forbidden, but in varying cultures, vary ing homicides have been not only tolerat ed but customary . Examples are sacri fices to the Aztec gods, defeated ene mies by cannibal savages, the senile and near senile among some Eskimos, and unwanted infants in the Athens of classic antiquity. Thus, in all cultures, the cul pability of homicide depends upon the cultural definitions of approved kilters and their approved victims. As Zack states, thus reinforcing the views of Hickman. Boving. and Libel (Letters. 10 July. p. IM). a human zy gote. (or equally ovum or sperm), or fetus are all incontrovcrtibly living and human. Science, having told us this, has nothing more to add to the question or whether any of them is to be considered legally the potential subject of culpable homicide if killed. That question is for moralists, legislators, lawyers, and the democratic process. W. Brown Morton. Jr. Route I. Box Vffl. WiirujM*. Virginia 22$72 New Location for Memphis? After looking at the map accompany ing the article on the Tennessee-Tumbighec waterway (News and Comment. 14 Aug., p. 74li. I see more clearly the reason for its high cost. It must include moving Memphis from its traditional lo cation on the Mississippi River to the head of the waterway near Savannah. Tennessee. G. H. Hickox 43/0 AilwottJ Court. Alexandria. Virginia 22.109 The map was indeed tn error. -- Editor tit tn ihc report crmilrU * I"hc fvsirr* k(|ulifc' ai nnurnor m iutiry pn4n,a secret*." hs I l.. N trrs rfW . iTAu* . R .tW t. * error (vcxrm l in ihr le*rr*i ta F * . Z. In the ck-vi** ta n n a H t -B. ihc c o ti fame chnild hase referred tn ihr tut** K k m 4 ihr N ut Rar u dopnamr. ATTORNEY W ORK PRODUCT*'** 5,l1i 50 ATTORNEY-CLIENT PRIVILEGE T N. TKr Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. Citation Author(s): H. R. Buser Title: Identification of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in Environmental and Industrial Samples Using High-resolution Gas Chromotography and Mass Spectrometry Reference: Recent Developments in Mass Spectrometry in Biochemistry and Medicine, 6 , 515-521 (1980) Citation No: 14 II. Source of Dioxins Source: Soil from Zone A at Seveso, Italy after 1976 2,4,5-trichlorophenol explosion. Fly-ash from an electrofilter of a municipal incinerator in Switzerland. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Discusses 3 routes: (1 ) Condensation of 2 chlorophenate anions to give PCDDs (in chlorophenol synthesis). (2) Pyrolysis of wood, paper, or vegetation treated with chlorophenates to give PCDDs. (incineration). (3) Chlorinated biphenyls pyrolysed to PCDFs (incinerators) Isomers Identified: Soil from Seveso, Italy: 2,7 or 2,8-DCDD; 2,3,7-TrCDD: 2.3.7.8- and 1,3,7,8-TCDD. Total equalled several hundred ppb. Minor amounts of PCDF were formed (100 times lower level than PCDDs). Fly-ash from incinerator: Over 30 PCDD isomers. Major isomers were: 1,3,6 ,8- and 1,3,7,9-TCDD; 1.2.3.4.6.8- HCDD and OCDD. 2,3,7,8-TCDD was formed in minor amounts. PCDFs were formed. Most of the major isomers were those formed by pyrolysis of commercial PCBs. Included 2.3.7.8- TCDF and 2,3,4,7,8-PeCDF. SUBJECT TO PROTECTIVE ORDER. r.oQooi AT*TORNEr Y/ WORK ir.v- PRODUCT n?<Vl!QF III. Analytical Techniques Specificity: Used HRGC/quadrupole HRMS with SIM detector. Isomer specific for over 30 PCDD isomers. Sensitivity: Not discussed, but apparently in the 1 ppb range. IV. Comments (Significant Data, Graphs, etc.) Fig. 4 shows analysis of PCDF isomers in the liver of Yusho patients, who became ill from eating rice oil contaminated with PCBs which had PCDFs at the ppm level. Contained 2.3.6 .8- and 2,3,7,8-TCDF; 1,2,3,7,8-, 1,2,4,7,8-and 2.3.4.6 .8- PeCDF; and 1,2,3,6 ,7,8-, 1,2,3,4,7,8-, 1,2,4,6,7,8and 2,3,4,6,7,8-HCDF. (2,3,7,8-TCDF and 2,3,4,7,8-PeCDF are very toxic). All isomers which were excreted (those in the rice oil but not in the liver) had 2 adjacent hydrogenated carbon atoms in one of the two carbon rings. Good review-article. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 52 C23282 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT -- Fr;F I. Citation Author(s): H. R. Buser Title: Formation of Polychlorinated Dibenzofurans(PCDFs) and Dibenzo-p-dioxins(PCDDs) Chlorobenzenes from the> Pyrolysis of Reference : Chemosphere, 8 , 415-424 (1979) Citation No: 15 II. Source of Dioxins Source: Pyrolysis of tri-, tetra-, and pentachlorobenzenes in the presence of air at 620C. (~ lg/liter of air) in a sealed quartz mini-ampoule. Sampling Technique: After pyrolysis, benzene was added and the sample analysed. No clean-up was required and no interference in the determination of PCDFs or PDDDs. Flow Data (mass transfer): Not discussed. Chemistry of Formation: Suggests the following: Chlorobenzenes -- ^Chlorophenols --- f-- ^Polychlorinated diphenyl ethers (PCDPEs) ----p. Jr PCDDs * PCDFs Isomers Identified: PCDFs: 20 TCDFs, 20 of the 28 P e C D F s 13 of the 16 HCDFs, all 4 HpCDFs and OCDF. PCDDs: Formed to a lesser degree than the PCDFs and not as many isomers; however, TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD were all formed. III. Analytical Techniques Used quadrupole HRGC/HRMS with SIM detector. Specificity: Highly specific for both PCDD and PCDF isomers. Sensitivity: Limits of detection: 0.03-0.1 ng/injection CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 53 f ' ? 3 9 V ATTORNEY W ORK PRODUCT ATTORNEY. CU FNT P F L E G E IV. Comments (Significant Data, Graphs, etc.) The decomposition was higher for the lower chlorinated species. Higher chlorinated benzenes appeared to be formed from lower chlorinated congeners. Tables 1 and 3: lists the PCDF isomers formed. Tables 2 and 3: lists the PCDD isomers formed. Other chlorinated compounds formed: chlorophenols, polychlorinated naphthalenes (PCNs), polychlorinated styrenes (PCSs) and polychlorinated biphenyls (PCBs). Although postulated by above mechanism, no PCDPEs were detected. Chlorobenzenes have been observed in emissions from incinerators. They can be formed from aliphatic chloro compounds such as PVC and possibly from inorganic chloride and organic materials. However, the amounts and concentration of chlorobenzenes by these routes are probably too low to represent a risk for the formation of PCDFs and PCDDs. The situation may be different where attempts are made to dispose of large quantities of chlorobenzenes by incineration. The concentration of chlorobenzenes may well be high enough where the formation of PCDFs and PCDDs is probable. Thus incineration of chlorobenzenes should be strictly controlled to insure safe disposal and to prevent environmental and occupational exposures to the PCDFs and PCDDs. The known toxic PCDF isomers (2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; and 2,3,4,7,8-PeCDF) and PCDD isomers (2,3,7,8-TCDD; 1,2,3,7,8-PeCDD; 1,2,3,6 ,7,8-HCDD; and 1,2,3,7,8 ,9-HCDD) were all formed but were not main components. SUBJECT TO PROTECTIVE ORDER. 54 C23284 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): H. R. Buser, H. P. Bosshardt and C. Rappe Title: Reference: Identification of Polychlorinated Dibenzo-p-dioxin Isomers Found in Fly Ash. Cheraosphere, 7, 165-172 (1978) Citation No : 80 II. Source of Dioxins Source: Fly ashes from a municipal incinerator in Zurich-Hagenholz, Switzerland and an industrial heating facility burning used industrial oils in Suhr near Aarau, Switzerland. Also, from micropyrolysis of 2,4,6-tri-, 2,3,4,6-tetra- and pentachlorophenol (the most commonly used commercial chlorophenols). Sampling Techniques: The fly ash from the municipal incinerator was taken from the ESP. The fly ash from the industrial heating facility was from the 35 meter smoke stack. All fly ash and pyrolysis samples were extracted with methylene chloride. For the fly ash extracts, they were evaporated and purified on a silica column (elutant= hexane) and then on an alumina column [(1 ) 2% methylene chloride in hexane, (2) 50% methylene chloride in hexane]. The pyrolysis extracts were purified on an alumina column. After concentration, all samples were ready for analysis. Flow Data (mass transfer): Not discussed Chemistry of Formation: Based on the observation that the pattern of the main PCDDs formed in the pyrolysis of the chlorophenols is the same as that found in the two fly ash samples, the authors suggest that chlorophenols are the precursors of the PCDDs found in the fly ashes. The normal dimerization and Smiles rearrangement explains the major PCDDs formed. Example: CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. ,3,7,9-TCDD(Smiles n n 32Rr rearrangement) III. IV. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Isomers Identified: See Figure 1 1 ,3 ,'6 ,8-, 1,3,7,9-, and 2,3,7,8-TCDD 1 ,2 ,4,7 ,8- and 1,2,3,7,8-PeCDD 1 .2 .4 .6 .7.9- , 1,2,3,4,6 ,8-, 1 ,2,3,6 ,8 ,9-, 1 ,2 ,3 ,6 ,7,8- and 1,2,3,7,8 ,9-HCDD 1.2.3.4.6 .7.9- and 1,2,3,4,6 ,7,8 HpCDD OCDD Analytical Techniques Used capillary column GC/MS with electronimpact ion source and SIM technique. Specificity: Isomer specific but no quantitative data. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) On GC/MS analysis, up to 12 of the possible 22 TCDD isomers were present. The main isomers were the 1,3,6,8-and 1,3,7,9-TCDDs which are the normal dimerization and Smiles rearrangement products from 2,4,6-trichlorophenol, A minor peak was identified as 2,3,7,8-TCDD. Up to 10 of the possible 14 PeCDD isomers were found. 1 .2.3.7.8- and 1,2,4,7,8-PeCDD were identified. The PeCDDs are formed from dimerization of one molecule each of 2.4.6- trichlorophenol and 2,3,4,6-tetrachlorophenol. Assuming normal dimerization and Smiles rearrangement, 4 isomers can be expected (1 ,2 ,3,6 ,8-, 1 ,2 ,3,7,9-, 1 ,2 ,4,6 ,8- and 1.2.4.7.9- PeCDD). Up to 8 of the possible 10 HCDD isomers were apparent. The main isomer in fly ash was 1 ,2,3,4,6,8-HCDD, the normal condensation product of 2,4,6-trichlorophenol and pentachlorophenol. Another HCDD isomer was 1,2,3,6 ,8 ,9-HCDD, the dimerization product of 2.3.4.6- tetrachlorophenol. Also, 1,2,3,6 ,7,8-and 1.2.3.7.8 .9- HCDD were present in small quantities. Both possible HpCDD isomers (1 ,2,3,4,6,8 ,9-and 1.2.3.4.6.7.8- HpCDD) were present and also OCDD. Most important, all isomers identified were in both fly ash samples as well as the pyrolysis sample. The authors say the most toxic isomers are 2,3,7,8-PCDD, 1,2,3,7,8-PeCDD, and 1.2.3.6 .7.8- and 1 ,2,3,7,8 ,9-HCDD. n < o .<s 'a ;- - -- SUBJECT TO PROTECTIVE ORDER. CS3286 56 I. II. III. attorney w o rk product a t t o r n e y -c lie n t PRIVILEGE Non-Industrial Sources, of Chlorinated Dibenzo-p-dioxins Citation Author(s): H. R. Buser and H. P. Bosshardt Title: Polychlorinated Dibenzo-p-dioxins, Dibenzofurans and Benzenes in the Ashes of Municipal and Industrial Incinerators. Reference: Mitt. Gebiete Lebensra. Hyg., 69, 191-199 (1978) Citation No: 81 Source of Dioxins Source: Fly ashes from the Municipal Hagenholz Trash Incinerator at Zurich and an industrial incinerator near Aarau (fuel chiefly used is oil). Sampling Techniques: The Hagenholz-Zurich incinerator was sampled several times at various points; (1 ) bottom ash (900C.), (3) ash in front of economizer (480C.) (4) ash behind ESP (260C.) These ash samples were extracted with methylene chloride and extracts purified in the same manner as in Citation No. 80. Flow Data (mass transfer): Not discussed Chemistry of Formation: Suggest the formation of PCDDs and PCDFs from chlorinated aromatic precursors. Isomers Identified: Haganholz-Zurich incinerator: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD and the corresponding PCDF chlorine no. isomer clusters. Aarau incinerator: DCDDs, TrCDDs, TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD and the corresponding Cl4 to Clg PCDF isomer clusters. Analytical Techniques Used capillary GC/MS as in Citation No. 80 except standards were unavailable at the time so only chlorine no isomer clusters were identified. Specificity: Chlorine no. isomer clusters for PCDDs and PCDFs. Sensitivity: Detection thresholds = 0.2 ppb for TCDDs and TCDFs = 1 ppb for OCDD and OCDF. CONFIDENTIAL C*3287 57 SUBJECT TO PROTECTIVE ORDER. attorney w o rk product ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) This article discusses the early results from the sampling of the 2 incinerators. Citation No. 80 gives identification of some of the specific PCDD isomers by sharpening up the GC/MS technique by using standards. In the Hagenholz-Zurich incinerator ash, chlorobenzenes, PCBs and PCNs were also identified. In the Aarau incinerator ash, chlorobenzenes and chlorophenols were identified. Table 1 gives the analytical results for the PCDDs and PCDFs, found in the Hagenholz-Zurich incinerator fly ash. The fly ash from the ESP (200C.) contained Cl4 through Clg PCDDs and PCDFs, whereas samples taken at points of higher temperatures showed only CI7 and Cls PCDDs and PCDFs. Table 2 gives the results of analysis of the ash from the Aarau incinerator. Amounts of PCDDs and PCDFs were higher here than in the Hagenholz-Zurich incinerator. SUBJECT TO PROTECTIVE ORDER. 58 C23288 ATTORNEY W ORK PRODUCT ATTORNcY-CLItNl PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I; Citation Author(s): A. Cavallaro, et al Title: Preliminary Report on the Presence of Certain Toxic Organochlorine Derivatives (PCDD-PCDF) in the Environment Reference: Boll. Chim. Unione Ital. Lab Prov. Parte. Sci., 31, 369-384 (1980) Citation No : 82 II. Source of Dioxins Source: Samples from the province of Milan, Italy, an industrialized and highly urbanized area. 1. Airborne particulate matter obtained with high-volume samplers 2 . road sediment 3. the fine and powdered fraction from solid municipal wastes 4. compost from solid municipal wastes 5. condensate from auto exhaust 6 . dust from an air conditioner filter Sampling Techniques: No details are given about the sampling procedures. The samples were extracted with toluene (Soxhlet). The toluene extract was concentrated and the residue dissolved in hexane. The hexane solution was washed with acid and base, and then extracted with acetonitrile (3x 1 :1 ). The hexane phase was discarded and the acetonitrile phase diluted with water and extracted with hexane. The hexane solution was eluted through a multilayered column packed in the following sequence: glass wool, Na2S04 , silica gel with 10% AgN03, Na2S04 , Na2S04/NaHC03 (2:8), Na2S04 , celite/H2S04 , Na2S04 , silica gel and Na2S04 . The hexane eluate was then passed through a floricil column. The column was washed with 1% hexane in methylene chloride (discarded) and then pure methylene chloride. The methylene chloride eluate , ...was evaporated to low.volume, dissolved in hexane.. and passed through an alumina column. The column CONFIDENTIAL ,, SUBJECT TO PROTECTIVE ORDER. /*'>n o n n i~* ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE was eluted with hexane/CCl4 (1:1) (discarded)., and then with hexane/methylene chloride (1 :1 ), which contained the PCDDs and PCDFs. The acetonitrile partition is necessary to remove the hydrocarbons and fats. The AgN03 removes interfering chlorine and sulfur compounds. Flow Data (mass transfer): Not discussed Chemistry of Formation: Mentions: 1. From industrial and agricultural use of chlorophenols and their derivatives (2,4,5-T and PCP) 2 . During combustion of organic matter in the presence of catalysts, ions and free radicals interact to produce more stable molecules. 3. Chloroorganics---vi>nyclhildoernoevinryaldicalneds--- ^ PcBz, PCNs PCB s-- PCDDs + PCDFs III. IV. Isomers Identified: See Table 1. Determined chlorine no. isomer clusters of PCDDs only in a qualitative sense. Cl8 Airborne particulates Powder fraction of solid municipal wastes Compost Road sediment Sieved waste(A/C filter) Auto exhaust 1 1 1 1 1 1 Max. no. of isomers detected Cl7 Cl6 Cl5 Cl4 2 6* 4 2 2 42 1 2 212 212 41- - --- Analytical Techniques Used capillary GC/MS with MNCI (methane negative ion chemical ionization) technique Specificity: Chlorine no. isomer clusters Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Conclusions stated in the article: 1. -- The presence of PCDDs and PCDFs (from CI4 to Clg) were shown in nearly all samples except th&_auto exhaust where only the presence of OCDD was found. CONFIDENTIAL fin SUBJECT TO PROTECTIVE ORDER. ou U ^ Ao An o11 1<I ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE 2. Cl6 , Cl7 and Cla PCDDs appear dominant over Cl4 and Cls PCDDs. These authors consider the data they generated as showing that PCDDs are detectable in the environment and stem from sources other than industrial chemical processes (as by-products), industrial accidents, or incinerator emissions. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 61 C23291 I. II. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): A. Cavallaro, et al Title: Determination of Certain Toxic Organochlorine Micropollutants: -Polychlorodibenzo-p-dioxins and Polychlorodibenzofurans Emitted from Municipal Solid Waste Incinerators Reference: Boll. Chira. Unione Ital. Lab Prov. Parte. Sci. , 32, 237-257 (1981)' Citation No: 83 k Source of Dioxins Source: Emissions from 6 municipal solid waste incinerators 1 . slag from the incinerator grill 2. dusts from dust traps (ESPs or cyclones) 3. particulates and gas condensate from stacks Sampling Techniques: No details given for slag and dust samples. Sampling for the stack particulates and gas condensate was done under isokinetic conditions employing a train similar to others used. The sampling probe and condenser were made of pyrex glass (for stacks with no fume cooling system, steel was used). A basket in the probe collected the particulates and the condenser collected the gas condensate. The finely ground slag, dust and particulates were extracted with toluene (Soxhlet). The condensate was extracted with methylene chloride. These extracts were evaporated to a low volume (~ 1 ml) and the residues dissolved in hexane and purified according to the method described in Citation No. 82. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: PCDDs: TCDDs, PeCDDs, HCDDs , HpCDDs, OCDD PCDFs: TCDFs, OCDF 2,3,7,8-TCDF was identified ;n t ia l SUBJECT TO PROTECTIVE ORDER. 62 C2329* ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Analytical Techniques Capillary GC/MS with MNCI technique. Specificity: Method is capable of individual isomer identification with appropriate standards. Only identified 2,3,7,8-TCDF, OCDD and OCDF. Otherwise, data was quantified only by chlorine no. isomer clusters. Sensitivity: For TCDDs: 10-40 pg detection limit For HpCDDs and OCDD: 100-300 pg detection limit Comments (Significant Data, Graphs, etc.) Table 1 gives quantitative data for PCDDs and PCDFs in dusts (ppb) and in particulates and condensate (ng/Nm3) Table 2 gives quantitative date for PCDDs in municipal solid wastes (from Milan and Savona), compost, sieved waste, soils from urban/industrial area, road sediments, and atmospheric particulates. Tables 4 and 5 give other analyses of fly ash for PCDDs and . PCDFs from other references. This data confirmed the higher concentrations of Clg, CI7 and Clg PCDDs with respect to Cl4 and Cl5 PCDDs. All emissions (dusts, condensate, and particulates) contain PCDDs and PCDFs. The slag contained TCDDs and PeCDDs at lower than 0.004 ppb., HCDDs and HpCDDs not exceeding 0.006 ppb and OCDD not over 0.008 ppb. The PCDDs and PCDFs are found primarily in the gas phase. The concentration of PCDDs and PCDFs in the output are clearly greater than those in the input. The authors claim their findings confirm Dow's "trace chemistries of fire" data. 1i-1i *3 *fil .p*n& Y SUBJECT TO PROTECTIVE ORDER. 63 C23293 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. Citation Author(s): A. Cavallaro, et al Title: Sampling, Occurrence and Evaluation of PCDDs and PCDFs from Incinerated Solid Urban Waste Reference : Chemosphere, 9, 611-621(1980) Citation No: 16 II. Source of Dioxins Source: Slags from grates, dusts and fly-ash from dust collectors, and solid particles and condensed gases from chimneys of several incinerators in the Lombardy Region in Italy. Sampling Technique: Slag and dust (fly-ash) were taken from moistening bunkers and hopper. The chimney effluent was sampled under isokinetic conditions using a self-developed apparatus equipped with a high efficiency gas condenser cooled to 0C. The non-condensables were caught in ethylene glycol. Flow Data (mass transfer): Not discussed specifically. A mathematical model calculated the ratio of the fumes concentration at the stack and the ground concentration to be 10-6. Chemistry of Formation: Hypotheses put forward: (1) PCDDs and PCDFs pre-exist to combustion (2) Derived from precursors in the waste load- PCBs, PCNs, PVC, polychlo robenzenes (3) Cracking of organic-chlorinated substances (800-900C.); formation of free radicals and condensation to PCBs, polychlorobenzenes, etc.; then to PCDDs and PCDFs. Isomers Identified: PCDDs: 1,3,7,9-TCDD; 1,3,6 ,8-TCDD; 2,3,7,8-TCDD(only 4-10% of total TCDDs), 1,2,3,4,7-PeCDD; 1,2,3,7,8-PeCDD; 1,2,3,4,6,8-HCDD; olL,9"HCDDi 1,2'3,6,7,8"HCDD; i 2 37 >9"hcdd; SUBJECT TO PROTECTIVE ORDER. 64 023294 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE 1.2.3.4.6.7.8- HpCDD; 1,2,3,4, 6 ,7,9-HpCDD; OCDD. PCDFs: 2,3,7 ,8-TCDF; 1,2,3,4,8-PeCDF; 1,2,3,7,8-PeCDF; 2.3.4.7.8- PeCDF; 2,3,4,6 ,7,8-HCDF; 1,2,4,6 ,7,8-HCDF; 1 .2.3.4.6 .7.8- HpCDF; OCDF. IJX. Analytical Techniques Used a quadrupole HRGC/MS with El source and SIM detector. Specificity: Highly specific for TCDD, PeCDD, HCDD, HpCDD and OCDD individual isomers. Also, for TrCDF, TCDF, PeCDF, HCDF, HpCDF and OCDF individual isomers. Sensitivity: TCDDs-better than 35pg. HCDDs-better than 70pg. OCDD-better than 160 pg. IV. Comments (Significant Data, Graphs, etc.) Chimney effluent sampling: Probe and condenser made of pyrex glass to avoid metal catalytic action at high temperature and to permit proper washing. Figure 1 shows sampling system. 6-10 Nm3 were taken for each experiment. Extractions: Slags and fly-ash - extracted with toluene and volume reduced under a stream of nitrogen. Condensate extracted with methylene dichloride, dried with sodium sulfate and volume reduced under a stream of nitrogen. Purification: Extracts dissolved in petroleum ether (30-50C.), put on a layered column, [Na2S04/NaHC03(4 :1 ) Celite/H2S04(2:1) - Na2S04-silica gel] and eluted with the same solvent. The column is then eluted with methylene dichloride, the eluate evaporated to a small volume, and the residue taken up in hexane and transferred to a basic alumina column. After the column is washed with 20% CCl4-hexane, the desired contaminants are eluted with 50% methylene dichloride-pentane and dried under nitrogen. Every examined sample, obtained on different days from different incinerators, exhibited a similar profile concerning the presence of PCDDs and PCDFs, a variable number of isomers from TCDDs to OCDD and from TrCDFs to OCDF being detected. Table 1 : Shows PCDD and PCDF isomers determined. SUBJECT TO PROTECTIVE ORDER. 65 C2329b Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): A. Cavallaro, et al Title: Purification Techniques for Determining 2 ,3 ,7 ,8-Tetrachlorodibenzo-p-dioxin (TCDD) at the Parts per Trillion Level: Refinement of Method for Eliminating Possible Interferences Due to Increased Amounts of PCBs and Certain Chlorinated Pesticides. Reference : Boll. Chim, Prov., V(30)-53, 542-557 (1978) Citation No*. 40 Source of Dioxins Source: Contaminated samples from the Seveso, Italy area where Na 2,4,5-TCP eruption occurred. Includes soil samples, wipe samples and plants. Sampling Techniques: Does not discuss sampling. Soil - Dried with sodium sulfate. Extracted with hexane/acetone (4:1 by volume), filtered and evaporated to dryness in a rotary evaporator at <40C. Final traces of solvent removed by leaving vessel open at room temperature. Wipe tests - Degreased cotton soaked with hexane/acetone (4:1) was rubbed on surfaces. Extracted with hexane/acetone (4:1), filtered and concentrated as above. Plants - Cut up in small pieces and extracted in a homogenization vessel with hexane/acetone (4:1). The water was separated and the hexane solution washed with distilled water and dried with sodium sulfate. Concentrated as above. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: This article only considers 2,3,7,8-TCDD. No analytical data is presented. Only discusses improvement of purification technique to eliminate interferences. Analytical Techniques Used HRGC/MS with ECD technique iF Ia jJE L i SU BJECT TO PROTECTIVE ORDER. 66 023296 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Specificity: Only 2,3,7,8-TCDD considered. No raw data. Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) The purification procedure which is supposed to give excellent results without interference from PCBs (even at 1:5000 TCDD:PCB ratios) is as follows: 1. Elute residue through activated silica gel with petroleum ether (40-60C.). Concentrate to about 2 ml in a rotary evaporator at <40C. 2. Elute residue through a multilayered column [anhydrous sodium sulfate, activated silica gel, a mixture of 8:2 of sodium sulfate and sodium bicarbonate, a mixture of Celite 545 and H2SO4 (8g and 4 ml), and anhydrous sodium sulfate] with petroleum ether (40-60C). The elutant was allowed to drain directly into the next column. 3. The above elutant is passed through an activated fluorisil column using petroleum ether (40-60C) and then hexane at 1% (V/V) in methylene chloride. These elutants are discarded. The TCDD is eluted off the column with a 40% solution of hexane (V/V) in methylene chloride. This elutant is evaporated to dryness as above. 4. The above residue is dissolved in hexane and passed through a column with fluorisil on top and activated alumina below. The column is then eluted with 20% hexane in carbon tetrachloride. This is discarded. Then the column is eluted with pentane-methylene chloride (4:1 by volume). This removes the TCDD. Evaporate to dryness in the open air. Now ready for GC/MS analysis. The article gives no analytical results, thus is considered poor. SUBJECT TO PROTECTIVE ORDER. 67 023297 ATTORNEY W ORK PRODUCT ~PNEv O.!ENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): C. Chiu, et al Title: Polychlorinated Hydrocarbons from Power Plants, Wood Burning and Municipal Incinerators Reference : Chemosphere, 12, 607-616 (1983) Citation No 17 II. Source of Dioxins Source: Stationary combustion sources: coal-fired thermal generating station, old coal boiler at a central heating plant, modern heat recovery incinerator, and a small controlled air incinerator. Also, fly-ash from low temperature incinerator at hydro power plant, off-gases from open air burning of PCP treated wooden boxes, plasma pyrolysis of PCB. Sampling Techniques: Burning of PCP treated wooden boxes-sampling train with stainless steel probe, glass fiber filter and two stainless steel tubes of Amberlite XAD-2 in series. Pyrolysis of PCB-gas chilled by wet scrubbing system and passed through a series of glass impingers containing ethylene glycol (1 and 2), Amberlite XAD-2(3), isooctane (4 and 5) and silica gel (6). Each analysed separately. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Coal-fired power plant fly-a'sh: Cl4 to Cl7 PCDD and PCDF isomer clusters. Coal-powered central heating plant: No PCDDs or PCDFs. Heat recovery incinerator: Cl4 to Cl8 PCDD and Cl4 to Cl7 PCDF isomer clusters. Controlled-air incinerator: Cls to Cl8 PCDD and Cl4 to CI7 PCDF isomer clusters. Low temperature power plant incinerator: Cl8 PCDD and PCDF isomer clusters. CONFIDENT! SUBJECT TO PROTECTIVE ORDER. 68 Cl4 to C23298 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE PCP treated boxes: Cl4 to Clg PCDD isomer clusters and OCDF. B plasma burning: Cl4 to Clg PCDF isomer clusters. III. Analytical Techniques Used HRGC/LRMS with a Townsand discharge ion source using negative oxygen chemical ionization (1 : 1 O2 to N2) and multiple ion detection (MID) Specificity: Only Cl4 to Clg PCDD and PCDF isomer clusters documented. Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) Cleanup of samples - methylene dichloride/hexane (1:49) used for PCB removal. Activated alumina (overnight at 280C.) used. Table 2. lists PCDDs and PCDFs found in the various combustion process samples. CONFIDENT! 4 L SUBJECT TO PROTECTIVE ORDER. 69 C23299 II. III. IV. ATTORNEY WORK PRODUCT ,v TORNEY-CLIENT privilege Non-Industrial Sources o Chlorinated Dibenzo-p-dioxins Citation Author(s): G. G.Choudhry Title: Mechanisms in the Thermal Formation of Chlorinated Compounds Including Polychlorinated DiBenzo-p-Dioxins Reference: Pergamon Ser. Environ. Sei., 5, 275-301 (1982) Citation No: 109 Source of Dioxins Source: Municipal and industrial incinerators (1). flue gas (2). fly ash Also discussed the pyrolytic decomposition of chloroaliphatics, substituted aromatics and how related to the formation of PCDDs and PCDFs. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Considerable chemistry is discussed. Specifically the chlorophenols result in PCDD under combustion conditions. Varying the incinerator conditions many other chloroaromatics can be converted to PCDDs and PCDFs. Isomers Identified: Not discussed Analytical Techniques Not discussed Specificity: Not discussed Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) In order to account for the speculative sources of PCDFs and PCDDs in flue gas and fly ash, the following were considered a) PCDDs and PCDFs are present in feed; b) are produced from precursors; c) are formed in incinerator through de novo synthesis and from chemically unrelated organic matter. It is uncertain how far the various processes contribute to de novo syntheses. However, there is no doubt that de novo syntheses play a significantly active and major role for the thermal formation of PCDFs and SUBJECT TO PROACTIVE ORDER. C233(J (J ATTORNEY WORK PRODUCT ' " " ry OL'EMT 3RiVii.5GE PCDDs in the incinerator and other fires. Moreover, it is evident that PCBzs and PoCPs are key intermediates of prime importance in de-novo synthesis from any starting organic matter. A review article on the mechanisms in the thermal formation of chlorinated compounds including PCDDs. SUBJECT TO PROTECTIVE ORDER. 71 rv 3301 I. II. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins atto rn ey w ork a t t o r n e y -c lie n t product pPiVlLEGE Citation Author(s): G. G. Choudhry, et al Title : Reference : Formation of Polychlorodibenzofurans (PCDFs) by the Photolyses of Polychlorobenzenes (PCBzs) in Aqueous Acetonitrile Containing Phenols. Chemosphere, 12, 487-492 (1983) Citation No : 41 Source of Dioxins Source: No chlorinated dibenzo-p-dioxins. Photolysis of PCBzs in mixtures of water and acetonitrile in the presence of phenol give PCDFs containing 2 less chlorine atoms than the starting PCBz. Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: From 1.2.3.4- C14Bz 1 ,2,3,5-C14Bz 1.2.4.5- C14Bz 1.2.3.4.5- ClsBz I2 3,4,5,6-C16Bz 1.2.4.5- C14Bz CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. Phenol Phenol II If II II 3,4-DCP 72 P C D F s q yield) 1 DCDF (<0.4) 2 DCDFs (0.77; 1.2) 2 ,3-DCDF (0.95) 1 DCDF (0.17) 2 TrCDFs (0.72; 0.24) 1 TrCDF U0.05) 1 ,2 ,3,4TCDF (0.4) 2 DCDFs (1.56; <0.6) r U o"W330<J III. IV. ATTORNEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE Analytical Techniques Not discussed Specificity: Not discussed Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) General equation: Cl Bz n + CgHgOH > (H20:CH3CN)T Cl n - 2,,DFs Tentative identifications of PCBs, polychlorophenylacetonitriles, chloroacetophenones (in the presence of acetone only) and l-polychlorophenyl-2-propanones (in the presence of acetone only) during the direct and acetone sensitized photolyses of some PCBzs in H20:CH3CN reveals that these photoreactions proceed via the chlorophenyl radicals. Irradiation of 2,4,5-trichlorodiphenyl ether in H20:CH3CN gives 2,3-DCDF. This confirms the intermediacy of the above diphenyl ether in the photochemical generation of 2,3-DCDF. The polychlorodiphenyl ethers with OfCl substituent are not thermally converted to PCDFs. This clearly demonstrates that all PCDFs formed above are solely photoproducts. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 73 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY w o r k pr o d u ct A ' 'ORNEY-CLIENT PRIVILEGE . Citation Author(s): G. G. Choudhry and 0. Hutzinger Title: Mechanistic Aspects of the Thermal Formation of Halogenated Organic Compounds Including Polychlorinated Dibenzo-p-dioxins. Part I: Theoretical Background and Thermochemical Decompositions of Monomeric Aliphatics and Aromatics. Reference: Toxicological and Environmental Chemistry, 5, 1-65(1982) Citation No: 18 II. Source of Dioxins Source: NA Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: Considerations will be presented in Parts II and V of this extensive publication. Part I only gives an overview of all of the parts. It is not detailed enough to warrant documenting here. Isomers Identified: NA III. Analytical Techniques Specificity: NA Sensitivity: NA IV. Comments (Significant Data, Graphs, etc.) This publication is being published in 5 parts. This citation covers only Part I. I. Theoretical background and thermochemical decompositions of monomeric aliphatics and aromatics. II. Thermochemical generation and destruction of dibenzofurans - and dibenzo-p-dioxins.I. III. Thermodegradation of organometallics and polymers. CONFIDEK^I &L SUBJECT TO PROTECTIVE ORDER. 74 C23304 AAT.T..O^R-NK;E,YY WCLO!,RnKt PRODUCT pR|VjLGE IV. Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations. V. Hypotheses for the formation of polychlorinated dibenzofurans and dibenzo-p-dioxins in the incinerators. SUBJECT TO PROTECTIVE ORDER. 75 G2330D ATTORNEY W ORK PRODUCT - -V " '^V1!,EGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): G. G. Choudhry and 0. Hutzinger Title: Mechanistic Aspects of the Thermal Formation of Halogenated Organic Coupounds Including Polychlorinated Dibenzo-p-dioxins. Part II: Thermocheraical Generation and Destruction of Dibenzofurans and Dibenzo-p-dioxins Reference: Toxicological and Environmental Chemistry, 5, 67-93 (1982) Citation No : 30 II. Source of Dioxins Source: PCDFs: Formed thermally from PCBs PCDDs: Formed by thermolysis of chlorinated phenols, phenoxyacetic acids, and their salts, and phenoxy-2-phenols. PCDFs and PCDDs: Thermodegradation of chlorinated diphenyl ethers, ester of 2,4,5-T and chlorinated benzenes. Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: A. PCDFs from PCBs - 4 routes: (1 ) loss of q -C12 (2) loss of HC1 involving a 2,3-chlorine shift at the benzene nucleus (3) loss of o-HCl (4) loss of 0-H2 B. PCDDs from chlorinated phenols - Mechanism is through a 1 ,2-ketocarbene for salts Good proof on p. 80-81 CONFIDENTS -\L SUBJECT TO PROTECTIVE ORDER. 0 Na+ / " ' O T f \ /'i H (at times, may go through aryne inter- ATTORNEY W ORK PRODUCT Ai. .. ; . pri vi lege Basic reaction for free chlorinated phenol involves loss of water and/or, HC1. The following shows what is assumed to happen depending on the conditions. C. PCDDs + PCDFs - In most experiments, PCDFs are higher than PCDDs. It has been shown that esters of 2,4,5-T on pyrolysis gives, with a few exceptions, only TCDDs. PCDFs over the whole range (TCDFs-OCDF) were formed (Table XVI, p. 87) Polychlorinated diphenyl esters (PCDPEs) on pyrolysis give chlorobenzenes as well as PCDDs + PCDFs (see p. 88), PCDFs are formed mainly from loss of 0-H2 and o-HCl, but sometimes from loss of o-Cl2 . PCDDs are formed only from loss of 0-CI2 . Example: loss of o -H2 loss of o-HCl CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. loss of Cl,, Chlorobenzenes give, on pyrolysis, higher chlorobenzenes, chlorophenols, PCNs, PCSs, PCBs as well as PCDDs and PCDFs. Formation of the latter two is assumed to be bimolecular (see p. 90). Buser gives following mechanism: m= 1-5 77 ----- -PCDFs Cl m m - 1, , loss . of o-H,,2 PCDPE (loss of HCl) loss .loss of of o-Culr2l o-HCl PCDDs A=loss of 0-CI2 o-HCl III. IV. Isomers Identified: NA Analytical Techniques Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) Good review article. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE ir" UI tr ,34. '-'j .k /l SUBJECT TO PROTECTIVE ORDER. 78 C23308 ATTORNEY WORK PRODUCT a t t o r n e y -c lie n t privileg e Noa-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. G. Choudhry and 0. Hutzinger Title: Photo Chemical Formation and Degradation of Polychlorinated Dibenzofurans and Dibenzo-p-dioxins Reference: Residue Rev., 84, 113-161, (1982) Citation No: 113 II Source of Dioxins Source: Photo formation and degradation of various organic compounds. This is a review article. Sampling Techniques: Not discussed Flow Data (mass transfer): NA Chemistry of Formation: III IV. Photo formation of dioxins hv H2 Photo degradation of dioxins hv Cl, C-6H-6-n-C-.6il.14i Isomers Identified: Specific and chlorine no. clusters of PCDDs Analytical Techniques All photo products were identified by comparing their retention times and mass spectra with those of reference compounds. Specificity: Authentic reference samples used, thus isomer specific, if needed Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Research workers have given very little attention to the photochemical formation and degradation of PCDDs. The 168-200 hr. photolyses of some PCBs, e.g., 2,5 CI2-PCB and 2,21 ,5,5'-CI4-PCB dispersed in water provide 2-C1-DBF in a 0.2% steady state yield.. SUBJECT TO PROTECTIVE ORDER 79 C2330) ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Photolysis of an aqueous solution of PCP(as sodium salt) buffered to pH8 produces OCDD with about a 0.03% yield. When PCP on wood is exposed to artificial as well as sunlight some PCDDs (equilibrium concentration being ~10-1G0 ppm) such as HCDDs to OCDD appear as photo products. The riboflavin sensitized photo oxidation of aqueous 2,4-DCP fails to produce TCDD or lower chlorinated dioxins. Similarly, 2,3,7,8-TCDD cannot be detected during the irradiation of 2,4,5-T as aqueous solution. More complex polychlorinated phenols have given PCDDs by photolysis. UV and Y"i-r'E'adiation of OCDD as solution in benzene-hexane produces lower chlorinated PCDDs. Continued irradiation of 2,3,7,8-TCDD in CH3OH eventually yields a yellow gum with the absolute loss of the benzenoid chromophore. Half-lives (T,s) of TCDD in iso-octane are 40 min and 3 hr. for 0.5m and lm, respectively, to artificial sunlight. The time required for total photo decomposition of TCDD at 254 to 256nm in aqueous solutionss 1-hexadicyl-pyridium chloride and sodium decylsulfate are 4 and 8 hrs. respectively. Of the (22) TCDDs, the rate of photodegradation of TCDD in n-hexadecane is the greatest. When a mono-molecular layer of TCDD absorbed on silica gel is exposed to radiation of \>290nm and \>230nm, ca. 8% of the dioxin after 7 days and 2% of the dioxin after 4 days remain undecomposed, respectively. Photolysis of herbicide formulations, such as Agent Orange, containing known amounts of TCDD (10-15ppm) dispersed on surfaces of glass, soil or leaves results in rapid photodegradation of TCDD. The nature of the material upon which the TCDD is spread, plays an important role in the photodegradation as does the intensity of the U.V. light. Tri-CDDs and di-CDDs are the usual photo products resulting from the irradiation of TCDD in solution phase as well as the solid phase. SUBJECT TO PROTECTIVE ORDER. 80 C2.3310 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ttX ,, ' VVUKK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. Citation Author(s): G. G. Choudhry and 0. Hutzinger Title: Mechanistic Aspects of the Thermal Formation of Halogenated organic Compounds Including Polychlorinated Dibenzo-p-dioxins. Part IV: Incorporation of Inorganic Chlorine into Organic Matter and Thermochemical Aromatizations. Reference: Toxicological and Environmental Chemistry., 5, 277-293 (1982) Citation No : 85 II. Source of Dioxins Source : Mentions Mahle and Whiting's (Citation No. 67) article where bituminous coal is subjected to high temperature air oxidation and chlorination using sodium chloride, HC1 and chlorine as sources of chlorine (Table XXV p. 280). T C D D s , H C D D s , HpCDDs and OCDD are formed when HC1 and C I 2 were used as the chlorine source. Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: Mentions Russian study where petroleum coke is pyrolysed in a KCl-NaCl melt to give the fl ooililoowwii nng:: pi Cl X . C 1 coke > 700^ CC14 + Y o T + HCl + C O C I 2 + CO + C02 KC1 - NaCl CI^y ^ C I Cl HCB h 2s H i CH, + At 700C., both CCI4 and HCB are formed; at 800-900C, only CC14 was formed; at 1000C, neither were formed. nf: Also mentions a U.S. study where smoke from tobacco containing varying amounts of DDT (a chlorinated organic) contained methyl chloride (CH3 C I ) , methylene chloride(CH2 Cl2 ) and chloroform (CHCI3 ) (Table XXVI, p. 280). The conclusion was that the chlorine in the methyl chloride formed originated from the inorganic chlorine present in the tobacco, and the SUBJECT TO PROTECTIVE ORDER '81 C2331L III. IV. contribution of the DDT chlorine was not substantial. This conclusion is supported by another study where inorganic chlorides containing labeled chlorine to tobacco and found radioactivity in the methyl chloride formed in the smoke from cigarettes made from such tobacco. Chloroform was found only in smoke from tobacco treated with DDT, thus the trimethyl group in DDT was converted to chloroform. Regarding thermal aromatizations, only examples of pyrolysis of nonchlorinated organics to form aromatics are found in the literature. Since PCBzs are known to form PCDDs (see Citation Nos. 66 and 86), the tobacco studies suggest that inorganic chlorine can take part in incineration processes to form PCDDs. Also certain aliphatic chlorine compounds (carbon tetrachloride and tetrachloroethylene) are known to form HCB, a PCBz. Isomers Identified: NA Analytical Techniques NA Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) This is an excellent review article SUBJECT TO PROTECTIVE ORDER. 82  - r , " VVUKK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): G. G. Choudhry and 0. Hutzinger Title : Mechanistic Aspects of the Thermal formation of Halogenated Organic Compounds Including Polychlorinated Dibenzo-p-dioxins. Part V: Hypothesis and Summary. Reference: Toxicological and Environmental Chemistry, 5, 295-309 (1982) Citation No: 86 II. Source of Dioxins Source: This review article discusses hypotheses that may account for the presence of PCDDs and PCDFs in the emissions from municipal and industrial incinerators. Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: Discusses 3 possibilities: 1. PCDDs and PCDFs are trace components in refuse and do not undergo complete thermal destruction. 2. PCDDs and PCDFs are produced during combustion and pyrolysis of chlorinated precursors (PCBs, PoCPs, PCDPEs, "predioxins" and chlorinated phenoxyacids). 3. PCDDs and PCDFs are formed "de novo" from a complex array of pyrolytic processes of chemically unrelated organic compounds. a. from anthropogenic (man-made) chlorinated organics such as PVC, DDT, etc. b. anthropogenic (man-made) non-chlorinated organics (e.g. polystyrene) and inorganic chlorine (HC1 or NaCl). c. autochthonous (naturally occurring) organics (cellulose, lignin, coal, tobacco, etc.) and inorganic chlorine. SUBJECT TO PROTECTIVE ORDER. 83 C23313 a a t t to to r r n n e e y y . w^o r k PRODUCT PRIVILEGE Isomers Identified: NA III. Analytical Techniques NA Specificity: NA Sensitivity: NA IV. Comments (Significant Data, Graphs, etc.) Concerning the 3 possible routes to PCDDs and PCDFs: The first possibility had not been proven at this point in time according to the authors. Only a few negative results are found in the literature. The second possibility has been proven. This article discusses: 1. PCBs to PCDDs and PCDFs 2. PoCP to PCDDs 3. Chlorinated 2-phenoxyphenols ("predioxins") to PCDDs 4. Chlorinated phenoxyacids and derivatives to PCDDs and PCDFs 5. PCDPEs to PCDDs and PCDFs The third possibility is thoroughly discussed. Figure 10 shows the possible origin of PCDDs and PCDFs vis "de novo" synthesis in incinerators. It is evident that chlorinated and non-chlorinated benzenes and phenols play a key role. Whenever these intermediate compounds are formed in incinerators, PCDDs and PCDFs may ultimately be formed in the presence of chlorine and oxygen. Benzene and chlorinated benzenes can be formed theoretically from (1) thermal degradation of lignins, (2) PVC, (3) polystyrene (4) PCBs under reducing conditions (5) PoCPs under reducing conditions (6 ) CH3CI and chloroaliphatics (7) petroleum coke (8) DDT-- >CHCl3 -- >Cl2C=CCl2 --- *HCB. PCBzs can thermally react to form PCBs which can form PCDFs. Lignins can give phenol which can give biphenyl and then on chlorination PCDFs, or phenol can be chlorinated by PoCP which can yield PCDDs. Also, it is apparent in these "de novo" syntheses of PCDDs and PCDFs chlorination of an intermediate is necessary to give PCBzs or PoCPs. Thus chlorine is needed. Figure 11 gives possible chlorine sources. It includes thermal degradation of chlorinated organics such as- PVC, chlorinated rubber, and chlorinated pesticides (DDT) to HC1. Also NaCl in the presence of silica and moisture can give NCI. It is known that HC1 in the CONFI SUBJECT TO PROTECTIVE ORDER. 84' C23314 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE presence of 02 can pyrolyse to CI2 . Also chloroorganics can give CI2 under pyrolytic conditions. This article mentions the thermal formation of PCDFs from PCBs by 4 reaction routes: (1) loss of o-cl2, (2) loss of o-HCl, (3) loss of o-H2 , (4) loss of HC1 involving a 2 ,3 ,-chlorine shift at the benzene nucleus. Also mentions that lower chlorinated benzenes on pyrolysis give higher chlorinated benzenes, but not the reverse. SUBJECT TO PROTECTIVE ORDER. 85 331b ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non.-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): R. E. Clement and F. W. Karasek Title: Distribution of Organic Compounds Adsorbed on Size-fractionated Municipal Incinerator Fly-ash Particles Reference : J. of Chromatography, 234, 395-405 (1982) Citation No: 19 Source of Dioxins Source : Fly-ash from a southern Ontario municipal incinerator operated at about 900C. with electrostatic precipitation. Sampling Tehnique: Two grab samples were taken on different days. They were stored in the dark at room temperature in plastic bags. Six size fractions were obtained by seiving (urn):< 63, 63-106, 106-150, 150-250, 250-850, > 850 (light ash), > 850 (agglomerates). The last two fractions separated by hand. Flow Data (mass transfer): Not discussed Chemistry of Formation Not discussed Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD as isomer clusters Analytical Techniques Used a quadrupole GC/MS with SIM technique with 1,2,3,4-TCDD and OCDD as. standards. Specificity: Not isomer specific except for-OCDD Sensitivity: Not discussed - at least down to 1 ng/g of fly-ash fraction Comments (Significant Data, Graphs, etc.) Sample extraction and preparation - Each sized sample was extracted thoroughly with benzene using ultrasonic agitation. The benzene was removed from each extraction sample by rotary evaporation under -vacuum down to 2-3 ml. The extractant samples were ultimately reduced to 100 ul by blowing with helium gas. SUBJECT TO PROTECTIVE ORDER. 86 attorney w o r k product ATTORNEY-CLIENT PRIVILEGE Table I: % of total sample weight by particle size for the two fly-ash samples. Table III: Gives the concentration of the various PCDDs by chlorine isomer clusters for the various size fractions denoted by average particle size in um (30, 80, 125, 200, 550, > 850 (light ash), > 850 (agglomerates). The 200 and 550 um particles have about three times more PeCDDs and HCDDs as do the small particles (30 and 80 um). HpCDDs are more evenly distributed. The TCDDs and PeCDDs had largest concentrations on the 550 um particles, while the 30 um particles had greater concentrations of 0CDD. Fig. 3: Gives a comparison of TCDD and OCDD concentrations for different fly-ash size fractions. Highest concentration of TCDDs is in the 550 um particles, while the 30 um particles had the least. Just the reverse is true'for OCDD-30 um particles has the most while the 550 um particles have the least. SUBJECT TO PROTECTIVE ORDER. 87 C23317 attorney w o r k product ATTORNEY-CLIENT PRIVILEGE TabLe 1 shows analysis of plant parts (aerial and underground parts) four months after transplanted in unpolluted soil. Shows disappearance of 2,3,7,8-TCDD from underground and old aerial parts. Also absent in new aerial parts. If exclude transport backward to soil, there are three other possibilities: (1 ) translocation to aerial parts followed by degradation by sunlight (2) translocation to aerial part followed by loss by transpiration (3) metabolism by plant SUBJECT TO PROTECTIVE ORDER. 89 ATTORNEY WORK PRODUCT .i c/-*c Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): D. G. Crosby, et al Title: Environmental Generation and Degradation of Dibenzodioxins and Dibenzofurans Reference: Environmental Health Perspectives, 5, 259-266 (1973) Citation No: 22 II. Source of Dioxins Source: Charring of small chips of commercial plywood containing 53 ug/g of PCP." Sampling Techniques: Smoke and volatiles were trapped - no more detail. Flow Data (mass transfer): Not discussed Chemistry of Formation: Suggested thermal generation (nucleophilic substitution) by condensation of 2 molecules of PCP forming OCDD and liberating 2 molecules of hydrogen chloride. Isomers Identified: HCDDs, HpCDDs and OCDD III. Analytical Techniques Used GC/MS - no details of type of detector. Specificity: Apparently specific only for isomer clusters (HCDDs, HpCDDs and OCDD) Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) Basically a review article dealing with evidence for' thermal and photochemical generation of PCDDs and PCDFs and photochemical degradations. > Photochemical generation - Irradiation of 2,5,2* 5 *-tetrachlorobiphenyl in aqueous suspension gave 2-chlorodibenzofuran. SUBJECT TO PROTECTIVE ORDER. Photochemical degradation - Lower chlorinated dibenzo-p-dioxins are completely degraded in a few hours especially when organic hydrogen donors are present (e.g. DCDDs, TrCDDs and TCDDs). OCDD is more resistant. 90 CS332U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): W. B. Crummett Title: Environmental Chlorinated Dioxins from Combustion-The Trace Chemistries of Fire Hypothesis Reference: Pergamon Ser. Environ. Sci., 5_, 253-263 (1982) Citation No: 23 II. Source of Dioxins Source: New: A. Discusses same sources as in Citation No. 13 (Bumb article). Fish from (1) rivers remote from pesticide manufacturing incinerators, fossil-fueled powerhouses, and gasoline powered vehicles. (Texas, Arkansas, and Shiawassee); (2) rivers downstream from Dow which operates all of the above (Tittabawassee and Saginaw Bay); and (3) rivers remote from pesticide manufacturing but have the other energy activities. _ B. Pyrolysis of dioxin-free coal at 600C. in air with and without a chlorine source. Sampling Techniques: Same as in Citation No. 13 Flow Data (mass transfer): Not discussed Chemistry of Formation: "Trace Chemistries of Fire" hypothesis Isomers Identified: 2,3,7,8-TCDD and OCDD. Also TCDD, HCDD, HpCDD isomer clusters III. IV. Analytical Techniques Used LC/GC/MS with the following resolutions (L=low, M=mediura, H=high): LMH, MML, HML, HLL, LHH, HHL,LLH. LLL, Specificity: Quantitative data only for 2,3,7,8-TCDD and OCDD. Sensitivity: Fish samples - 1 to 120 ppt depending on sample. Pyrolysed coal samples - 0.006 to 0.7 ppb. Comments (Significant Data, Graphs, etc.) C ^3 3^ Table 10: Gives fish analysis - rivers close to high energy activities has highest level of TCDDs. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Table 11: Give pyrolysed dioxin-free coal analysis samples where coal is burned in the presence of HC1 or CI2 give highest levels of TCDDs, HCDDs, HpCDDs and-OCDD. Conclusion; Supports "trace chemistries of fire" hypothesis and that chlorinated dibenzo-p-dioxins are ubiquitous is reasonable. Note: In Letters of Science, 207. 1148 (1980), Crummett comments on a report by Kimble and Gross claiming that TCDDs were not present in fly ash from a "modern power plant" and that the Dow report was "invalid". Crummett claims he asked them to collaborate with Dow in sampling and analysing fly ash from the same power plant- Kimble and Gross claimed they could not disclose the name or location of the power plant. Also, DOE apparently did not know its location. Thus Crummett said the integrity of their report is "placed in jeopardy", since confirmation can't be made. SUBJECT TO PROTECTIVE ORDER. 92 3322 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE II III. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): P. E. des Rosiers (EPA Office of Research & Development) Title: Transformer Fires Constitute Health Risk, Produce Dioxins, Furans, EPA Scientist Says Reference: Chemical Regulation Reporter, 7, 1378-1379 (1984) Citation N o : 42 Source of Dioxins Source: Soot samples from a PCB transformer fire in a 22 story office building in Binghamton, N.Y. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Although PCDDs are not found in PCB transformers under normal conditions, they do occur when a transformer containing a mixture of PCBs and chlorinated benzenes undergoes combustion or thermal stress. The formation of dioxins is believed to be due to intermolecular reactions of chlorinated benzenes and oxygen under thermal conditions. des Rosiers said that since the tri- and tetrachlorinated benzenes comprise 35% of the dielectric fluid, it can be assumed that these PCBzs represent precursors to the PCDDs. Isomers Identified: des Rosiers mentions that the most toxic isomers were the major components in the soot 2.3.7.8- TCDD; 2,3,7,8,,-TCDF; 1 ,2 ,3 ,7,8 ,-PeCDD; 1.2.3.7.8- PeCDF and 2,3,4,7,8-PeCDF. Total PCDFs = 2,160 ug/g of soot Total PCDDs = 10-20 ug/g of soot Analytical Techniques Not discussed Specificity: Not discussed Sensitivity: Not discussed CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 93 C23323 IV. Comments (Significant Data, Graphs, etc.) des Rosiers noted that the dioxins and furans in the soot were biologically active and thus the soot could be considered toxic. This is in contrast to fly ash from municipal incinerators, where the dioxins and furans are inactive in this form. Trace amounts (ng/m2) of PCDDs and PCDFs were still present even after the Binghamton office building was decontaminated using steam and detergents. SUBJECT TO PROTECTIVE ORDER. 94 C23324 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. II. III. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): Title: Reference: A. J. Dobbs and C. Grant Octachlorodibenzo-dioxin in Wood Treatment Materials and Treated Wood. Chemosphere, If), 1185-1193 (1981) Citation No: 24 Source of Dioxins Source: Commercial PCP, wood protection formulations containing PCP, and in wood treated with PCP Sampling Techniques:' PCP and NaPCP: Dissolved in toluene/hexane mix (10:1) and small amount of caustic and extracted with hexane, washed with deionized water and passed through an alumina column. PCP determined by GC analyses of methyl ether (reaction of diazomethane). OCDD determined by washing hexane solution thoroughly with caustic, ` washed with deionized water, treated with diazomethane, and analysed by GC. Wood protection formulations: Simply diluted with hexane and sample prepared and analysed as above. Wood treated with PCP: After removal of paint film, wood was cut in small pieces. For OCDD analysis, extracted by refluxing hexane for 2 hours, washed with caustic and deionized water, dried with Na2S04 and passed through an alumina column. Then analysed by GC. PCP was extracted from wood samples by refluxing with methanol and GC analysis performed after reaction with diazoraethane in ether. Flow Data (mass transfer): NA Chemistry of Formation: Not discussed Isomers Identified: OCDD and OCDF 3. .U.Hk =UBJc.wi 0 PROTECTIVE ORDER Analytical Techniques Used LC on activated alumina," then GC/MS with a Ni63 ECD. Also checks were made to assure OCDD was not formed during the cleanup procedure. Specificity: Quantitative for OCDD and OCDF Sensitivity: Not dismissed but apparently -- 5-8ng/g. 95 C2332 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) Table 3: Gives analysis of OCDD in commercial samples of PCP and NaPCP. 12 year old sample of PCP had OCDD content still in the range quoted by manufacturer. Table 4: Gives analysis of OCDD in proprietary wood protection products. Formulations stored 5-10 years. OCDD content consistent with amount in PCP, thus formulation and storage did not increase OCDD. Table 5 Gives analysis of OCDD in wood treated with PCP. Storage of wood caused depletion of PCP. This was mainly due to volatilization. However, some evidence for OCDD formation by sunlight. PCP volatilized about 50 x the rate of OCDD. Table 6 : Gives analysis of OCDD in anti-sapstain treated wood PCP:OCDD ratios are much higher because NaPCP used which has lower OCDD content than PCP. Conclusion: OCDD concentrations found in a variety of materials associated with wood preservation are in the range expected for commercial PCP (or NaPCP) initially present, despite a range of storage conditions, periods, and processes involved. Exposure to sunlight may lead to production of minor amounts of OCDD in treated wood. CONFIDENTS 4L SUBJECT TO PROTECTIVE ORDER. r* n 96 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of .Chlorinated Dibenzo-p-dioxins Citation Author(s): A. J. Dobbs and C. Grant Title: Photolysis of Highly Chlorinated Dibenzo-p-Dioxins by Sunlight Reference: Nature(London) 278, 163-165 (1979) Citation No: 114 Source of Dioxins Source: NA Sampling Techniques: Not discussed Flow Data (mass transfer): NA Isomers Identified: 1,2,3,4,6,7,9-HpCDD, 1,2,3,4,6 ,7,8-HpCDD, 1,2,4,6,7,9-HCDD Analytical Techniques GC columns Specificity: Authentic standards Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) The study reported in this article is concerned with the photolysis of OCDD, HpCDDs and HCDDs and shows that the structural isomers which are expected to be the most toxic are most rapidly decomposed. They also report that despite photolytic reductive dechlorination which gives rise to less highly chlorinated dioxins, the reaction mechanism favors the formation of the-less toxic isomers. OCDD is short lived when exposed to sunlight in hexane solution (t^, 16 hrs.). The half lives indicate that CDDs with chlorine SUBJECT TO PROTECTIVE ORDER. 97 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE atoms in the 2-position photolyse more rapidly than those with chlorine atoms in the 1 -position. Other factors are also involved because compounds possessing the same number of chlorine atoms in the 2-position photolyse more rapidly as chlorine atoms are removed from the 1-position. Extrapolation of these results leads to the prediction that 2,3,7,8-TCDD should be the most photolabile of the chlorinated dioxins. CONFIDENT! &L SUBJECT TO PROTECTIVE ORDER. 98 C23328 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-1qdu.strial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): R. C. Dougherty Title: Human Exposure to Pentachlorophenol Reference: Environ. Sci. Res., 12, 351-361 (1978) Citation No: 25 II. Source of Dioxins Source: Considerations of: 1. Natural formation of PCP in the environment. 2. PCP appearing as a result of metabolism of other chlorinated compounds. 3. Formation of PCP in water chlorination systems. 4. Intake of PCP as a result of human activities. Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: 1 . PCP is a natural compound in the environment seems reasonably unlikely. If it were a natural metabolite, it would have been identified as such because of its widespread presence. 2. PCP is a major metabolite of hexachlorobenzene (HCB) in rats. The fact that HCB has not been detected in human urine suggests that'metabolism of HCB should be only a minor contributor to the human PCP load. 3. Chlorination of phenol in water supplies in sewage effluents seems quite unlikely to be a route to substantially contribute to the human PCP burden. 1 ppm of phenol in water with 10 ppm of CI2 leads to 0.2 ppb of PCP - but, 1 ppm of phenol in water is intolerable to humans from the taste viewpoint. C O N F ID SUBJECT TM EN 4. The most likely sources for human exposure to PCP are the food.chain from storage of products in PCP-treated wooden containers. Also, a minor possible source of PCP contamination is metabolism HCB from environmental sources. T ? a "? " 99 i" 9 332 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Isomers Identified: Isomers identified are TCDDs, HCDDs, HpCDDs, and OCDD. Other workers have identified these. Analytical Techniques Discusses analytical methods for PCP analysis. Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) This is a review article. Significant is the statement that the toxic effects of PCP cannot be divorced from the effects of PCDDs that contaminate commercial formulations. rONFDENT &L SUBJECT TO PROTECTIVE ORDER. 100 C2333U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. A. Eiceman and H. 0. Rghei Title: Chlorination Reactions of 1,2,3,4-Tetrachlorodibenzop-dioxin on Fly Ash with HC1 in Air Reference: Chemosphere, FI, 833-839 (1982) Citation No: 26 Source of Dioxins Source: Formation of higher chlorinated PCDDs by reaction of 1,2,3,4-TCDD in fly ash from a municipal incinerator with HC1 using a lab reaction apparatus to simulate gas-phase conditions comparable to those in effluent stream from working incinerators. Fly ash samples came from Northwest Municipal Incinerator, Chicago, IL. Sampling Techniques: After reaction in the lab apparatus, the reaction tubes were cooled to room temperature, flushed with air, and the contents extracted with benzene. The condensed extracts were then analysed by GC or GC/MS with SIM technique. Flow Data (mass transfer): Total flow of gas as a mixture was 20ml/min. Chemistry of Formation: 1,2,3,4-TCDD + HC1 + 02 ^0-2ci0oC > PeCDDs + HCDDs + HpCDDs Endothermic + OCDD + H20 reaction Isomers Identified: PeCDDs, HCDDs, HpDDs 'and OCDD Analytical Techniques Specificity: - Individual isomers within a series were not specifically determined. Sensitivity: Not discussed. Comments (Significant Data, Graphs, etc.): Variables studied were temperature, time, volume % of HC1 in CONFIDENTIALair, and mass of 1,2,3,4-TCDD. SUBJECT TO PROTECTIVE ORDER. 101 C2333I ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE (1 ) % conversion to higher chlorinated PCDDs versus temperature: 50C., not available; 100C., 32.6%; 150C., 66.5%; 200C., 44.2%; 250C., 23%. Cause for lower conversion at higher temperatures is unknown, but adsorption of 1,2,3,4-TCDD to an intact but unreactive state is suspected. (2) As mass of 1,2,3,4-TCDD increased, efficiency of conversion increased. (3) As time increased, maximum of conversion reached in 10-30 rain, and then decreased. May be due to loss of higher chlorinated PCDDs due to irreversable adsorption, loss of PeCDDs and HCDDs by further chlorination to HpCDDs and OCDD, and loss of activity of 1,2,3,4-TCDD with increased time of contact and temperature. (4) Production of higher chlorinated PCDDs was independent of HC1 concentration between 1-50% HC1 in air. 1% is well within the values for a modern municipal incinerator. SUBJECT TO PROTECTIVE ORDER. U 3332 102 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. A. Eiceman, R. E. Clement and F. W. Karasek Title: Analysis of Fly Ash from Municipal Incinerators for Trace Organic Compounds Reference : Analytical Chemistry, 5_1, 2343-2350 (1979) Citation No* 20 Source of Dioxins Source: Fly ash from municipal incinerators in Japan, Canada and The Netherlands. Sampling Techniques: Grab samples of fly ash taken and stored in closed containers at room temperature and protected from UV and visible light. Each sample was extracted with benzene, the benzene extract centrifuged to remove small solid particles and the volume reduced to 100 ul by rotary evaporation at ~60C. and nitrogen blowing. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD as isomer clusters. Also analogous PCDFs. Analytical Techniques Used GC/MS with SIM technique. Also ran a blank Specificity: Not isomer specific except for OCDD and OCDF. Sensitivity: Not discussed but at least 0.2 ng/g of fly-ash. Comments (Significant Data, Graphs, etc.) Table I: shows 29 substances searched for by the SIM technique Table II: shows the list of compounds identified by GC/MS (99 total). Conclusion: PCDDs and PCDFs were present in every sample. This suggests that they are formed universally during incineration processes although the combustable material and conditions may vary. CONFIDENT! 103 SUBJECT TO PROTECTn IVo Eo ORDER. oo PRODUCTATTORNEY WORK ATTORNEY-OK^ p r iv il e g e .V Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. A. Eiceraan, R. E. Clement and F. W. Karasek Title: Variations in Concentrations of Organic Compounds Including Polychlorinated Dibenzo-p-dioxins and Polynuclear Aromatic Hydrocarbons in Fly Ash from a Municipal Incinerator Reference : Analytical Chemistry, 53, 955-959 (1981) Citation No; 21 II Source of Dioxins Source: Eight samples of fly ash taken weekly from a single municipal incinerator in Ontario, Canada. Sampling Techniques: Sample of fly ash collected once a week from below the electrostatic precipitator. Eight samples collected, stored in closed glass jars at room temperature and protected from UV and visible light. Analysed within 7 days after sampling. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD as isomer clusters. III. Analytical Techniques Used GC/MS with SIM technique using 1,2,3,4-TCPD as standard. Specificity: Not isomer specific except OCDD Sensitivity: ~ 1 ng/g of fly ash. Specific detection limits were not determined. IV. Comments (Significant Data, Graphs, etc.) Table II: r,23 334 Gives quantities of PCDDs (ng/g of fly ash) by chlorine number isomer cluster. PeCDDs and HCDDs are present in highest concentrations. Chlorobenzenes and chlorophenols also detected. The concentrations of PAHs parallels the estimated total mass of organic compounds; however, PCDDs do not. Thus the formation of PCDDs may be controlled by a second variable such as source of chlorine. 104 C l ID n r r 'T T r \ I. II. III. IV. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. A. Eiceman, A. C. Vian and F. W. Karasek Title: Ultrasonic Extraction of Polychlorinated Dibenzo-p-dioxins and Other Organic Compounds from Fly Ash from Municipal Incinerators Reference: Anal. Chem., 52, 1492-1496 (1980) Citation No: 27 Source of Dioxins Source: Fly ash from municipal incinerators equipped with electrostatic precipitators and located in major urban centers in Ontario, Canada. Sampling Techniques: Grab samples were taken and shipped and stored in closed glass containers at ambient temperatures, protected from visible and UV light. Flow Data (mass transfer): Not discussed. Chemistry of Formation: Not discussed. Isomers1Identified: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD Analytical Techniques Used GC/MS with SIM technique. Also Dual-Mode technique Specificity: Only specific for chlorine isomer clusters. Sensitivity: Not discussed. Comments (Significant Data, Graphs, etc.) This article shows that ultrasonic extraction is as good as Soxhlet extraction methods for removing PCDDs from fly ash. CONFIDENT! AL SUBJECT TO PROTECTIVE ORDER. r n q < 105 7' 'V-/MMCT WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE F W Non"Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. Eklund and B. Stromberg Title: Detection of Polychlorinated Polynuclear Aromatics in Flue Gases from Coal Combustion and Refuse Incinerators Reference: Chemosphere, 12, 657-660 (1983) Citation No: 28 II Source of Dioxins Source: Flue gases from two coal-fired boilers and one municipal incinerator. Plant A = fluidized bed combustor for incineration of municipal refuse. Plant B = a coal-fired fluidized bed combustor. Plant C = a coal-fired, automatically regulated on/off boiler for greenhouse heating. Sampling Technique: The flue gases were collected in an all glass sampling train. No detailed discussion here but gives reference to presentation of Sixth International Symposium on PAHs. Flow Data (mass transfer): Not discussed Chemistry of Formation: Indicates PCDDs and PCDFs can be present in fly ash and flue gases from (1 ) . present in fuel and not effectively destroyed during combustion (2) chlorinated precursors such as polychlorinated benzenes, polychlorinated phenols and PVC are converted to PCDDs and PCDFs during combustion. (3) complex thermal and catalytic reactions from non-chlorinated precursors and inorganic forms of chlorine. Current data available suggest PCDDs and PCDFs are produced from chlorinated organic precursors in incinerators. :h radical and catalysed electrophilic substitution reactions CONFIDENTi possible mechanisms. SUBJECT TO PROTECTIVE ORDER. 106 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Isomers Identified: No specific isomers identified. Analytical Techniques Used GC/MS - no details of techniques used. Just mentions PCDDs and PCDFs found. (Table 2) Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Plant A gave the greatest amount and most complex PCPNAs. Other PCPNAs formed included - chlorinated benzenes, naphthalenes, acenaphthalenes, biphenylenes, PCBs, phenanthrenes, anthracenes, fluoranthenes, pyrenes, benzanthracenes, chrysenes, benz (j,b,k) fluoranthenes, benzo (a,c) pyrenes, phenols, cresols, naphthenols, quinolines and isoquinolines SUBJECT TO PROTECTIVE ORDER. 107 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): M. P. Esposito and D. R. Watkins Title: Airborn Dioxins: The Problem in Review Reference: Presentation at the 73rd Annual Meeting of the Air Pollution Control Association; Montreal, Quebec; June 22-27, 1980 Citation No: 29 II Source of Dioxins Source: Mentions the following in this review article: (1 ) From fly ash and gaseous emissions from incinerators - may be present and escapes incineration or may be formed from precursors. (2) Other combustion sources are fossil-fueled powerhouses, gasoline and diesel autos and trucks, residential fireplaces, cigarette tars and charcoal grills (Dow's "Trace Chemistry of Fire"). (3) From dust at three plants located peripheral to the toxic Hyde Park landfill in New York. Appears to be not in the air but migrating out of landfill certainly into a creek. III. Sampling Technique: NA Flow Data (mass transfer): NA Chemistry of Formation: Discusses formation from precursors such as chlorinated phenols, nitrophenols, salicylates, cresols, xanthane, catechols, guaiacols, chlorobenzenes, etc. (with Cl2 and/or 02) - Isomers Identified: NA Analytical Techniques Specificity: Sensitivity: NA NA SUBJECT TO PROTECTIVE ORDER. 3338 108 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs , etc.) The following are pertinent statements made in this review article: 1. Free dioxins are destroyed by incineration at 800C.; however, PCDDs bound to particulate matter are largely unaffected by incineration temperatures as high as 1150C., and escape the incinerator unchanged. 2. An earlier suggestion is that a worldwide background of atmospheric dioxin contamination was caused by incineration of 10,400 metric tons of Agent Orange containing up to 47 ppm of TCDDs in the Pacific in 1977. This was prior to the development of analytical methods sensitive enough to detect low ppt levels. There is no present data to confirm this. 3. Mentions Dow article on finding PCDDs from various combustion sources. 4. Mentions Dow's conclusion that PCDDs may be ubiquitous combustion products. 5. Mentions Kimball & Gross finding no TCDDs in fly ash from typical coal-fired power plant in California (detection limit of 1.2 ppt). This refutes Dow's finding of 38 ppb from another powerhouse. SUBJECT TO PROTECTIVE ORDER. 109 C33339 n. ill. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): H. P. Esposito, et al Title: Dioxins: Volume I . Sources, Exposure, Transport and Control Reference : IPA-600/2-80-156, June, 1980; U. S. Dept, of Commerce, National Technical Information Service Citation No; 31 Source of Dioxins Source: NA Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: This review article gives what was known about the chemistry of formation of PCDDs and PCDFs up to this time. Mentions the Smiles rearrangement which helps explain many of the isomers formed. Isomers Identified: NA Analytical Techniques Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) This review article covers: (1 ) chemistry of formation (2) sources (3) routes of human exposure (4) environmental degradation and transport (5) disposal and decontamination (6) health effects CONFIDENT* SUBJECT TO PROTECTIVE ORDER. no C2334U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): F. Gizzi, et al Title: Polychlorinated Dibenzo-p-dioxins (PCDD) and Polychlorinated Dibenzofurans (PCDF) in Emissions from an Urban Incinerator. 1. Average and Peak Values Reference: Chemosphere, H. 577-583 (1982) Citation No: 32 Source of Dioxins Source: Stack emissions from a modern municipal incinerator in Como, Italy. Samples were taken over a 9 month period on 2 consecutive days each month. Sampling Techniques Gas and particulate matter were collected under isokinetic conditions. To avoid absorption of compounds present in the gas phase onto the particulate, a glass wool filter was placed in the glass probe. A 3-step collection device at 0C. was used to trap compounds present in the vapor phase. The gas passed first through a glass coil followed by a bottle filled with ice to collect condensate and then bubbled through two bottles filled with ethylene glycol and glass beads. The last bottle was connected to a vacuum pump to collect about 4 cubic meters in 8 hours. The solutions in the bottles were extracted with hexane and the combined extractions evaporated to dryness. The residue was dissolved in hexane, transferred to an alumina column and eluted with CCI4 and then CH2CI2 * This last fraction, containing the PCDDs and PCDFs, was evaporated to dryness and finally dissolved in 100 . ul of dioxan, ready for analysis. Flow Data (mass transfer): PCDDs = 2.3-348 mg/hr. PCDFs = 3.9-324 mg/hr. Stack flow = 33,000 cubic meters per hour. Chemistry of Formation: Not discussed Isomers Identified: Only isomer clusters were identified: TCDDs, PeCDDs, HCDDs, HpCDDs, and OCDD. Also TCDFs, PeCDFs, HCDFs, HpCDFs and OCDF. SUBJECT TO PROTECTIVE ORDER. Ill ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE III. IV. Analytical Techniques Used GC/MS with SIM technique. Specificity: Only isomer clusters determined Sensitivity: Not determined Comments (Significant Data, Graphs, etc.) In the individual samples, HCDDs and OCDD were often the most abundant classes found. No definite trend for PCDFs. Mean values for PCDDs (ng/cubic meter): TCDDs, 128.4; PeCDDs, not determined but definitely present (no analytical standard); HCDDs, 366; HpCDDs, 286.3; OCDD, 125.9 Mean values for PCDFs (ng/cubic meter): TCDFs 309; PeCDFs, 250.3; HCDFs, 314.2; HpCDFs, 215.1; OCDF, 123.8. Note: In two samples, as much as 2 grams of PCDDs and 2 grams of PCDFs were released in 8 hours each day. On these days, the 1 incinerator operated at the lowest combustion temperature (~500C.), probably because of the high moisture content of the waste, which contained a lot of vegetables, and because of the rainy weather. Tables 1 and 2 give analytical results for each sample taken. Figure 1 shows sample train used. SUBJECT TO PROTECTIVE ORDER. 112 attorney w o rk product ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): C. L. Haile, et al Title: Comprehensive Assessment of the Specific Compounds Present in Combustion Processes. Volume I - Pilot Study of Combustion Emission Variability Reference: EPA-560/5-83-004, June, 1983 - Task 3 Final Report Citation No: 33 II. Source of Dioxins Source: (1) Pulverized coal suspension fired boiler (Unit No. 7) of the Ames, Iowa municipal power plant. The fuel used was 20% refuse-derived fuel (largely paper and plastics) and 80% pulverized coal (~ 50% each of Colorado and Iowa coal). Sampled flue gas, electrostatic precipitator hopper ash, bottom ash, cooling tower blowdown water, well water, and bottom ash quench overflow. (2) Chicago Northwest incinerator operated in Chicago, II. on 400 ton per day capacity. Burns mixed refuse from domestic sources. Sampled flue gas, electrostatic precipitator (ESP) ash and combined ash (bottom ash and ESP ash mixed - bottom ash could not be collected alone). Sampling Technique: Ames coal-fired boiler - flue gas sampling was taken at points both inlet and outlet to the electrostatic precipitators using two modified EPA Method 5 sampling trains. Collected 10m3 samples for 11 days at a rate approximating the flue gas velocity. Solid samples collected 6 times a day. Liquid samples collected several times a day. Chicago incinerator - flue gas sampling was taken as indicated for the Ames coal-fired boiler. Solid samples collected 6 times a day. No liquid samples were taken. Flow Data (mass transfer): Ames coal boiler: outlet velocity = 22-26 ft/sec. No PCDDs or PCDFs SUBJECT TO PROTECTIVE ORDER. 113 C233da ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE III. IV. Chicago incinerator: outlet velocity = 32-44 ft/sec. PCDDs(mg/hr): TrCDDs, 1.1; TCDDs, 0.53; HCDDs, 1.4; HpCDDs, 0.65; OCDD, 0.22; 2,3,7,8-TCDD, 0.034 PCDFs(mg/hr): TrCDFs, 25; TCDFs, 7.6; HCDFs, 5.3; HpCDFs, 0.64; OCDF, 0.052 Chemistry of Formation: Not discussed Isomers Identified: Only from Chicago incinerator: Data only given for isomer clusters except for 2,3,7,8-TCDD; TrCDDs, TCDDS, 2,3,7,8-TCDD, HCDDs, HpCDDs, OCDD, TrCDFs, TCDFs, HCDFs, HpCDFs, OCDF Analytical Techniques Used HRGC/Hall-FID, HRGC/MS-SIM and HRGC/HRMS-SIM Specificity: Isomer specific only for 2,3,7,8 ,-TCDD. Sensitivity: detection limit for PCDDs and PCDFs in composite flue gas extracts was 0.1-0.25 ng/dscm Comments (Significant Data, Graphs, etc.) This is an excellent, detailed article. Many graphs, tables and illustrations regarding Ames boiler and Chicago incinerator operating parameters, analytical results, sampling methods, and emissions results. Ames boiler: Chlorinated compounds determined included dichlorobenzene 1 ,2 ,4-trichlorobenzene, hexachlorobutadiene, 2,4,-dichlorophenol, p-chloro-m-cresol and chlorinated biphenyls (tri, tetra, penta, hexa, hepta, and decachloro derivatives). All of these could be PCDD and PCDF precursors yet no PCDDs or PCDFs were found. Chicago incinerator: Chlorinated compounds determined included 1 ,3-,1,4-and 1 ,2-dichlorobenzenes; 1,2,3-, 1 ,2,4-and 1 ,3,5-trichlorobenzenes; tetrachlorobenzene, hexachlorobenzene; di-,tri-,and tetrachlorophenols; and chlorinated biphenyl (di, tri, tetra and pentachloro derivatives). Also, the above mentioned PCDDs and'PCDDFs. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. r*-n o o a * 114 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): R. L. Harless, et al Title: Analysis for 2,3,7,8 Tetrachlorodibenzo-p-dioxin Residues in Environmental Samples Reference: Environ. Sci. Res., 26, 161-177 (1983) Citation No : 108 Source of Dioxins Source: 1. Fish - Edible portion from 3 fresh water sources in Michigan 2. Deer - Muscle, adipose tissue, liver and bone marrow from deer exposed to 2,4,5-T herbicide containing <0.1 ppm 2,3,7,8-TCDD Sampling Techniques: EPA methodology (Harless, et al 1980) for sample preparation, prior to analysis, was used. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD Analytical Techniques Capillary column HRGC/MS in the El mode with MIS technique Specificity: Isomer specific for 2,3,7,8-TCDD. Test and quality assurance (QA) samples were spiked with authentic samples of 2,3,7,8-TCDD. Sensitivity: ppt Comments (Significant Data, Graphs, etc.) Small scale environmental monitoring studies were conducted to quantitatively determine the presence or absence of 2,3,7,8-TCDD in fish and deer. 2,3,7,8-TCDD was detected in concentrations of 3 to 142 ppt in 19 of 20 fish samples collected in the State of Michigan. Two to 27 ppt of 2,3,7,8-TCDD were detected in various parts of the bodies of deer which were used to study effects of an aerial application of the herbicide 2,4,5,-T. Average minimum limits of detection for these analyses were: fish, 3 ppt; deer, 2 ppt. The results on fish are consistent CONFIDENTS AL SUBJECT TO PROTECTIVE ORDER. 115 f:n 9 9 1 II III. IV. Nog-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): A. Hay Title: Dispute over Dow Chemicals' Theory of Dioxin Traces Reference: Nature, 281, 619-620 (1979) Citation No: 35 Source of Dioxins Source: NA Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: Rappe claims that chlorophenols and chlorinated diphenyl ethers are the main precursors for chlorinated dioxin formations in municipal incinerators. Isomers Identified: NA Analytical Techniques Rappe claims that Dow could have used better analytical techniques. Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) This article presents criticism by Prof. Christopher Rappe, University of Umea, Sweden of the Dow report on "The Trace Chemistries of Fire". He claims the methodology used by Dow is poor, rendering some of the results questionable. He also says Dow's conclusions - that dioxins are ubiquitous and a natural consequence of combustion processes - are far from proven. Apparently, Dr. Hans R. Buser and Dr. Hans P. Bosshardt support Prof. Rappe's views. Prof. Rappe does admit that Dow's findings of chlorinated dioxins in commercial incinerators is not new - two independent European groups have reported that fly ash of municipal incinerators CONFIDENT!. &L SUBJECT TO PROTECTIVE ORDER. 118, r P Q 9 ,1 O Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins attorney w o rk product a t t o r n e y -c lie n t privileg e I. Citation Author(s): T. Helder, et al Title: The Toxicity and Toxic Potential of Fly Ash from Municipal Incinerators Assessed by Means of a Fish Early Life Stage Test Reference: Chemosphere, Tl, 965-972 (1982) Citation No: 36 II. Source of Dioxins Source: Fly ash from an electrostatic precipitator of the municipal incinerator in Zaanstad, The Netherlands Sampling Techniques: The fly ash was Soxhlet extracted with toluene. The raw extract is cleaned up by passing it over a column system loaded with silica gel and acid-,base-, and silver nitrate-modified silica gel. The PCDDs and PCDFs are then separated from the chlorobenzenes on a basic alumina column. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: ng/g of fly ash as cleaned-up extract (Table 1) PCDDs TCDDs PeCDDs HCDDs HpCDDs OCDD 245 422 562 370 299 PCDFs TCDFs PeCDFs HCDFs HpCDFs OCDF 314 500 660 484 86 III. IV. Analytical Techniques Used HRGC/KRMS with SIM mode Specificity: Specific only for chlorinated isomer clusters Sensitivity: -- 0.2 ng/g Comments (Significant Data, Graphs, etc.) This article mainly deals with the bio-assays of rainbow trout yolk sac fry who were subjected to fly ash and extracts of fly ID r- ri o i asu b ject to protective order. 119 ash. In contrast-to fly ash itself, the extracts were extremely toxic, producing typical toxic features of TCDD intoxication. The toxic potential was attributable for a minor part to 2,3,7,8-TCDD and for the greater part to other chlorinated dioxin congeners and the dibenzofurans present in the fly ash. Analysis for PCDDs and PCDFs in exposed fry gave values below the detection level (0.17 ng/g of wet material). The authors concluded that the reason fly ash per se was not toxic to the fry was that the PCDDs and PCDDs are very tightly bound to the fly ash. SUBJECT TO PROTECTIVE ORDER. 120 II. III. attorney w o rk product A i O '' Y-CL'ENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. Higgins (Systech Corp.) Title: An Environmental Assessment of Refuse Thermal Processing Facilities Reference: Final Report, EPA Contract No. 68-01-6071, Dec., 1981 Citation No: 37 Source of Dioxins Source: This protocol is meant to be applicable to any waste burning facility with the primary pollutants of interest being TCDDs Sampling Techniques: Primary and auxiliary fuels, bottom ash and collection device particulates will be sampled according to general procedures developed by Systech and Dr. Brenda Kimble under this EPA contract. Stack samples will be obtained using a Modified Method 5 train incorporating an XAD-2 sorbent resin trap, and modified procedures by TRW Environmental Engineering Division in "Pilot Test Program Chicago Northwest Incinerator Boiler No. 1 EPA Contract No. 68-02-2197. Characterization of the combustion air in terms of its trace organic composition will be done as described in this protocol. Flow Data (mass transfer): Stack volume/velocity measurements will be taken. This data along with TCDD analyses will give the flow data. Chemistry of Formation: Not discussed Isomers Identified: Specifically designed to measure TCDDs as an isomer cluster (2,3,7,8-TCDD and co-eluting isomers). Analytical Techniques Uses GC/HRMS with dual ion monitoring. Specificity: TCDD isomer cluster Sensitivity: detection limit will be 2.5 x the noise level. According to Kimble and Gross, this is about 0.6 ppt. CONFIDENT! 4 L SUBJECT TO PROTECTIVE ORDER. 121 CC335L IV. Comments (Significant Data, Graphs, etc.) A T T O R f RODUCT ATT0RNy_cL;Efsj7 PRIVILEGE This EPA protocol makes use of sampling and analytical procedures developed by B. J. Kimble and M. L. Gross [see Science, 207, 59 (1980) abstract in this report]. Dr. Gross will do the TCDD analyses. The specific procedures outlined in this protocol were developed by Systech in conjunction with testing conducted for the EPA/OSW in North Little Rock, Ark. and Mayport, Florida (see EPA contract No. 68-01-6071 reports). Appendices A through G gives all of the procedural details and appropriately designed data sheets for recording the data. SUBJECT TO PROTECTIVE ORDER. 122 Nog-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY ATT*v-aNr PRODUt privilege I. II. Citation Author(s): D. 0. Hryhorczuk, et al Title: A Wire Reclamation Incinerator as a Source of Environmental Contamination with Tetrachlorodibenzo-p-dioxins and Tetrachiorodibenzofurans Reference : Archives of Environmental Health, 36, 228-234 (1981) Citation No: 38 Source of Dioxins Source: Soil samples No. 1 and No. 4 located 50 meters east and 1 kilometer northeast of a wire reclamation incinerator. Also, scrapings from stack No. 2 and furnace No. 2. Also, horse fat and liver from a dead mare from a horse boarding stable 1.3 kilometers northeast of the incinerator. Sampling Techniques: Soil, stack, and furnace samples were placed in new glass jars and refrigerated. Aluminum foil in lid of jar. Soil sampling sites selected on the predicted behavior of incinerator's plume (atmospheric dispersion model). Soil sample No. 1 - taken from top 5 cm of soil Soil sample No. 4 - a core sample to a depth of 20 cm and a surface sample to a depth of 3 cm were taken. Stack No. 2 sample - a pale green powder scraped from the base of the spark arrester. Furnace No. 2 sample - from knockdown chamber, wall of the primary chamber, and the ledge at the base of the stack. Horse fat and liver samples - frozen in C H 2 C I 2 rinsed aluminum foil and sent to Gross for analysis. Flow Data (mass transfer): Not discussed Chemistry of Formation: Mentions recent studies have shown chlorophenols, P C B s , chlorinated diphenyl ethers and chlorobenzenes can convert. to_PCDDs and PCDFs in thermal processes INT? *l SUBJECT TO PROTECTIVE ORDER. Isomers Identified: TCDD and TCDF isomer clusters r o Q n jr j 123 U v O O u O ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE HI. IV. Analytical Techniques Used GC/HRMS procedure of Kimble and Gross (see Citation No. 39) Specificity: Sensitivity: Specific for TCDD and TCDF isomer clusters Soil, furnace and stack samples: detection limit of 3 ppt. Horse fat and liver samples: detection limit of 6 ppt. Comments (Significant Data, Graphs, etc.) Table 3 Sample Total TCDDs (ppt) Total TCDFs(ppt) Soil No. 1 Soil No. 4 Furnace No. 2 Stack No. 2 Horse fat Horse liver 21 ND(<3) 58 410 45 ND(<6) 230 ND(<3) 730 11,600 165 57 Conclusion: A wire reclamation incinerator can be a source of environmental contamination with TCDDs and TCDFs. Suggest that they may have entered the incinerator intact in the fuel or charge, or were formed from precursors found in wire insulation. Other chlorinated organics found in samples were: PCBs, hexachlorobenzene, hexachiorostyrene. Since only total TCDDs and TCDFs were measured, the authors did not know if 2,3,7,8-TCDD or TCDF were present. Also, the authors could not establish a definite association between the human health effects and the exposure to trace amounts of TCDDs and TCDFs. CONFIDENT! \L SUBJECT TO PROTECTIVE ORDER. C23354 124 II. III. A r T O R NEy .a iE N T P R Kl^ Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): 0. Hutzinger, et al Title: Polychlorinated Dibenzo-p-dioxins and Dibenzofurans: A Bioanalytical Approach Reference: Chemosphere, 1J), 19-25 (1981) Citation No: A3 Source of Dioxins Source: Fly ash sample was the total particulate matter obtained from 3m3 of gaseous material emitted from a municipal incinerator in the Netherlands. Sampling Techniques: Not discussed. Extracts were purified using silica gel and acid-, base- and silver nitrate-modified silica gel as described elsewhere. [Anal. Chem. , 5_1, 1453 (1979)] Flow Data (mass transfer): Not discussed Chemistry of Formation: Mentions that pyrolysis of chlorinated * phenols and PCBs can lead to the formation of PCDDs and PCDFs. Isomers Identified: Table 1 Concentration in Fly Ash Extracts (ng/m3) PCDDs PCDFs TetrachloroPentachloroHexachloroHeptachloroOctachloro- 130 730 1130 1390 780 280 600 1200 1260 300 Total 4160 3640 Analytical Techniques Used HRGC/MS in the SIM mode Specificity: PCDDs and PCDFs as chlorine isomer clusters Sensitivity: Not discussed SUBJECT TO PROTECTIVE ORDER. 125 C23355 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Comments (Significant Data, Graphs, etc.) This article discusses the determination of the existence of PCDDs and PCDFs in fly ash from a municipal incinerator by the use of a bioanalytical approach. It was pointed out that many other PCDD congeners are also highly toxic and will contribute to the potential adverse biological impact of PCDD emissions into the environment. This article reports the sensitivity and utility of the cytosolic receptor protein binding assay in the bioanalysis of PCDDs. The bioassay indicates that the fly ash extract was about 45 times more active than expected if the 2,3,7,8-TCDD was the only competing substance. They say this is clearly due to the presence of other PCDDs and PCDFs and congeners which compete for the hepatic cytosolic protein. SUBJECT TO PROTECTIVE ORDER. 126 ATTORNEY WORK PRODUCT A. .'.,,'RNEY-Clitl'iT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): B. Jansson and G. Sunstrom Title: Formation of Polychlorinated Dibenzo-p-dioxins During Combustion of Chlorophenol Formulations. Reference: Science of the Total Environment, 10, 209-217 (1978) Citation No : 44 II. Source of Dioxins Source: Gases and particulate matter emitted when technical grade tri-, tetra- and pentachlorophenol products are mixed with wood chips and burned in a pilot-scale incinerator. The commercial formulations were: A. Potassium 2 ,4,6-trichlorophenate in turpentine B. Sodium 2,3,4,6-tetrachlorophenate C. 2,3,4,6-tetrachlorophenate mixed with aqueous alkaline copper salts D. Pentachlorophenol Sampling Techniques: Used a dust precipitator filled with glass wool coupled in series with an absorption column containing Apiezon M on chroraosorb for collection of gaseous components. The dust was extracted with toluene and the absorption column was eluted with hexane followed by toluene. The extracts were chromatographed on alumina and appropriate fractions analysed by MS. Flow Data (mass transfer): Not discussed Chemistry of Formation: Certain evidence indicates that the ring closure reactions to form PCDDs and PCDFs are more favored with increasing number of chlorine atoms in the phenols, which is to be expected for aromatic nucleophilic substitution reactions. Isomers Identified: PCDDs: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD PCDFs: TCDFs, PeCDFs, HCDFs, HpCDFs and OCDF All were formed in the original chlorophenol formulations (Table 1) Tables 2-5 show the results of the burning experiments. These tables are corrected for the background levels of PCDDs and wt^eiifwood chips alone are burned. SUBJECT TO PROTECTIVE ORDER 127 CS335V XXI. IV. PRODUCT privilege Analytical Techniques Used GC/MS in the SIM mode PCDDs and PCDFs as chlorine isomer clusters. Sensitivity: Not discussed. Comments (Significant Data, Graphs, etc.) For the tri~ and tetrachlorophenol formulations, large quantities of PCDDs were found at burning temperatures of 500-600C. At higher temperatures, the emissions decreased. Insufficient O2 supply or "open fire" conditions increased the emission of PCDDs. Addition of copper salts and increase in transit time decreased the PCDD emissions. The authors say the emissions of TCDDs during some experimental conditions are "alarming", but it should be pointed out that the isomer most probably formed is not 2,3,7,8-TCDD but 1,3,6,8-TCDD (much less toxic). SUBJECT TO PROTECTIVE ORDER. 128 023358 ATTORNEY WORY PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s) : J. Janssens, et al Title: Qualitative and Quantitative Analysis of Emissions of a Municipal Incinerator Installation Reference : Comm. Eur. Communities (Rep.), EUR 7624, 28-38 (1982) Citation No: 45 II Source of Dioxins Source: Particulates and gaseous emissions from a modern municipal waste incinerator located in Beveren, Belgium. There are two furnaces which operate simultaneously with a total capacity of 4.3 tons/hr. Data from 1979 indicated the installation worked continuously 5 days a week at 65% of capacity, thus combusting 16,000 tons' of household refuse and 2100 tons of light industrial waste. Sampling Techniques: The sampling was done in Feb. and March, 1980. The feed was mainly household refuse with no recovery of non-incinerable matter such as glass, metal, etc. Sampling done under isokinetic conditions. The sampling train included a BCURA cyclone probe, which separates the particles according to their aerodynamics diameter (cut off at 50% collection efficiency = 0.5 um). Figure 1 shows the train. The courses are collected in a hopper and the finer particles are retained on glass wool. The gas phase compounds are collected from a small fraction of the total flue gas volume sampled by an adsorption column with Tenox G. C. adsorbent. Sampling was done at various points in the dust between the ESP and the chimney. Flow Data (mass transfer): Average and yearly emission rate of PCDDs and PCDFs are given in Table VI. Grand total is 173g. Using literature data, the total PCDD/PCDF emission could be converted to equivalent 2,3,7,8-TCDD amount (same biological accuracy), thus can estimate the health risk. This equated to 3g of 2,3,7,8-TCDD. CONFIDENT?! 4 1 SUBJECT TO PROTECTIVE ORDER. 129 023359 Chemistry of Formation.: ci CHj-HK ^ Cl PVC ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Cl Cl n III. IV. Isomers Identified : PCDDs: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD PCDFs: TCDFs, PeCDFs, HCDFs, HpCDFs and OCDF Analytical Techniques The samples were extracted with t-butylmethyl ether and acetone consecutively. The cleanup procedure was based on Buser work [Chemosphere 7, 165 (1978)]. See Figure 2. Analysis done with quadrupole HRGC/MS with El source. Quantitative determinations were carried out using MID. Specificity: PCDD and PCDF chlorine isomer clusters Sensitivity: Not discussed. Comments (Significant Data, Graphs, etc.) Table II gives the whole of the emission data (sum of the gas phase and the particulates) in ng/1113. Table III: Concentration ratios of PCBzs were constant (ug/m3). Table IV: Concentration ratios of PoCPs strongly changed and seemed related to the moisture content of the flue gas. Table V gives distribution of PCBzs, PoCPs, PCDDs and PCDFs in gas and particulate phases. Most of these chlorinated compounds are in the gas phase (82-99-5%). Conclusions: For the first time, clear experimental evidence was obtained for the assumption that PCBzs and PoCPs are actual precursors of the PCDDs and PCDFs when waste is burned. This municipal incinerator emits during 1 year only 0.12% of the total equivalent 2,3,7,8-TCDD (3g versus 2500g) released at Seveso. There was only 1 incinerator every 500 km2 in Belgium then. The main problem is certainly not the possibility of an acute intoxication but one might question seriously the health risks due to long term jofiiire to low concentrations of PCDDs and PCDFs. SUBJECT TO PROTECTIVE ORDER. 130 CS3360 a-- <- hmcv w o p * po o d u ct . - ^ ' *1 ^ ` * . - _ Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): G. A. Junk and J. J. Richard Title: Dioxins Not Detected in Effluents from Coal/Refuse Combustion Reference: Chemosphere, 1J), 1237-1241 (1981) Citation No: 46 II. Source of Dioxins Source: Grate ash, fly ash, stack ash and stack vapor from a facility which produced 35 megawatts of electrical power from steam produced by the co-burning of coal and refuse derived fuel (RDF). Sampling Techniques: No details are given regarding the particulate sampling. The vapor samples were collected using a source assessment sampling system (SASS) and an Ames vapor sampling system. The vapor sampling system was validated by both laboratory and field tests. The particulate samples were Soxhlet extracted with methylene chloride, concentrated and fractionated on basic alumina. Certain fly ash samples were acid pretreated and extracted with toluene. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: No TCDDs or TCDFs were found in particulates or gaseous emissions. III. Analytical Techniques Used GC with electron capture detection. Also used HRGC/MS with MID technique Specificity: Specific for TCDD chlorine isomer clusters Sensitivity: Detection limits of O.lng TCDDs/g of particulate and 0.0005ng/liter of vapor. IV. Comments (Significant Data, Graphs, etc.) Prior to this study, very little data on the operating conditions of the various municipal incinerators and power plants where the gaseous and particulate emissions were found to CONFIDENT? AL-- -- _ _ __ contain PCDDs and/or PCDFs, were published. SUBJECT TO PROTECTIVE ORDER. 131 C23361 attoomp/ won* PRO"DEUGCET Table 1 gives list of samples in which no TCDDs were detected. The influent coal and RDF samples also showed no detectable TCDDs. The probable explanation of undetectable TCDDs in the emissions are (1) the high operating temperature of 1200C. due to the coal supplement and the type of boiler used (2) sufficiently long residence time (> 1.3 secs) (3) adequate O2 supply and (4) small pieces of RDF produced by shredding. These four . conditions have not existed for most incineration processes where TCDDs have been found. The one major exception may be the negative TCDD results obtained by Kimble and Gross from a coal combustion power plant with a presumed higher operating temperature. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. II III. IV. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): F. W. Karasek Title: Dioxins from Garbage: Previously Unknown Source of Toxic Compounds is Being Uncovered Using Advanced Analytical Instrumentation Reference: Canadian Research, Sept., 1980, 50-56 Citation N o : 47 Source of Dioxins Source: Fly ash from municipal incinerators in Canada and France Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Table I Cone, (ng/g fly ash) Canada France TCDDs PeCDDs HCDDs HpCDDs OCDD 23 36 30 11 2.7 0.13 0.24 0.39 1.2 3.0 Analytical Techniques Used GC/MS with SIM mode Specificity: PCDDs as chlorine isomer clusters Sensitivity: Not discussed Comments (Significant !Data, Graphs, etc.) Figure 6 indicates that wide daily variations in quantities of classes of dioxins occur. This data was on fly ash from a Canadian incinerator. CONFIDENT! 4 L SUBJECT TO PROTECTIVE ORDER. 133 C23363 ATTORNEY w o r k p r o d u c t A ' *: : Ei-O-'-'.-T 'LEGE I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): F. W. Karasek and F. I. Onuska Title: Trace Analysis of Dioxins Reference: Anal. Chem., 54, 309A-324A (1982) Citation No : 48 Source of Dioxins Source: Fly ash from an Ontario incinerator Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs,PeCDDs, HCDDs, HpCDDs and OCDD Analytical Techniques Discussesthe development of analytical methods for determining trace quantities of PCDDs (see Figure 1) Specificity: They say that, at the moment (1982), it appears that multiple ion high resolution SIM is the only unequivocal method for picogram analyses. This uses HRGC/HRMS. Sensitivity: HRGC/LRMS used for fly ash analyses = -'lng/microliter. Comments (Significant Data, Graphs, etc.) New techniques that have been applied to dioxin analysis are negative chemical ionization, atmospheric pressure ionization (API) and the tandem MS system (MS/MS). Of these, the MS/MS system shows the most promise for providing sensitive and selective analyses. This is an excellent article reviewing the state-of-the-art in dioxin analysis. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER- (j 2 3 X fi A 134 ATTORNEY WORK PRODUCT .......... " Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): F. W. Karasek, et al Title: Distribution of PCDDs and Other Toxic Compounds Generated on Fly Ash Particulates in Municipal Incinerators Reference: J. of Chromatography, 239, 173-180 (1982) Citation N o : 49 II. Source of Dioxins Source: Fly ash from a municipal incinerator in Paris, France was separated into six different particle sizes and analysed for PCDDs. Brass sieves with metal screens with openings of 850, 250, 150, 106 and 63um. Sampling Techniques: A large grab sample of fly ash was taken under one of the ESP hoppers. The incinerator temperature at the top of the furnace was 950C. Air flow was 45,000 m3/hr. ,, The sample was stored in glass jars at room temperature protected from light. After benzene extraction,' sample extracts were stored in a freezer at 15C. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Table III: PCDD Cone. (ng/g)in French Fly Ash Size Fractions III. Mean Particle Size 30 85 125 200 550 >850 TCDDs ND 11 it U it it PeCDDs 5 0.8 1 0.6 0.4 ND HCDDs 8 8 4 1 0.8 ND HpCDDs 30 20 8 ND 0.4 4. OCDD Total 120 160 39 67 12 '25 4.1 6 2.3 4 8.4 13 Analytical Techniques Used GC/MS with the SIM technique Specificity: Only PCDD chlorine isomer clusters Sensitivity: Detection limits for TCDDs = 100 pg/g; for OCDD = 200 pg/g. CNTIAl SUBJECT TO PROTECTIVE ORDER. 135 C23365 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) The total PCDD concentration decreases with increasing particle size in the French fly ash, unlike the Ontario sample where this trend is reversed (see Figure 2). Also, in the French fractions, there is a skewed pattern towards OCDD whereas in the Ontario fractions, there is a skewing towards OCDD in the smaller fractions, but towards TCDDs in the larger particles. The highest PCDD concentrations lie on the small particles in the French fly ash and on the larger particles in the Ontario fly ash. These differences may reflect different incinerator operating conditions, designs and differences between French and Canadian incinerator feedstocks. SUBJECT TO PROTECTIVE ORDER. 136 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Nog-Industrial Sources of s. V Chlorinated Dibenzo-p-dioxins I . Citation Author(s): F. W. Karasek and A. C. Vian Title: Reference: Gas Chromatographic - Mass Spectrometric Analysis of Polychlorinated Dibenzo-p-dioxins and Organic Compounds in High-Temperature Fly Ash from Municipal Waste Incineration J. of Chromatography, 265, 79-88 (1983) Citation No : 50 II. Source of Dioxins Source: Fly ash from a rotary kiln municipal incinerator in West Germany equipped with after-burner and an ESP. Sampling Techniques: Three samples were taken in a 3 months time period at an average after-burner furnace temperature of 1040 + 25C. Containers were cleaned with sulfuric acid, chromate and distilled water. Storage of the fly ash was at room temperature in the dark. After extracting the samples with benzene, the extracts were placed in a freezer at 15C. Flow Data (mass transfer): Not discussed Chemistry of Formation: Suggest chlorobenzenes, chlorocyclohexanes and chlorobiphenyls may be precursors to PCDDs and PCDFs, since all three samples contained them. Factors that influence the PCDD/PCDF content of fly ash are mentioned. These include particle size, precursor concentration (chlorobenzenes and PCBs)., temperature and oxygen flux. Isomers Identified: Table II : Sample (ng/g of fly 12 3 Note: No TCDDs or PeCDDs were detected HCDDs 0.3 0.4 0.2 HpCDDs 2.5 0.6 0.6 OCDD 20 8.3 7.2 TCDFs 28 1 0.8 PeCDFs 8 0.3 0.3 HCDFs 8 0.4 0.6 HpCDFs 10 0.6 0.8 OCDF 14 0.3 0.4 SUBJECT TO PROTECTIVE ORDER. 137 023367 X II. IV. Analytical Techniques Used HRGC/MS with the SIM technique PRODUCT privilege Specificity: PCDD and PCDF chlorine no. isomer clusters Sensitivity: Detection limit of O.lng/ul. Comments (Significant Data, Graphs, etc.) Table I gives the list of compounds identified by GC/MS (a total of 82). Table II shows the following patterns for PCDD congeners OCDD > HpCDD > HCDD > (PeCDD, TCDD). This* is the same trend observed in the laboratory chlorination of coal with HC1 or CL2 and as predicted by heats of formation. No such trend is observed for PCDFs. SUBJECT TO PROTECTIVE ORDER. 138 G23368 II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins attZ L PRODUCT a t t o r n e y -c lie n t PRIVILEGE Citation Author(s): A. S. Kende and J. J. Wade Title: Synthesis of New Steric and Electron Analogs of 2,3,7,8-Tetrachlorodibenzo-p-dioxin Reference: Environmental Health Perspectives; September, 1973; pp 49-57 Citation No : 111 Source of Dioxins Source: NA Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: NA Isomers Identified: NA Analytical Techniques NA Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) In contrast to the determination of a chemical reaction mechanism, the molecular mechanism for Xenobiotic toxicity among polychlorinated dibenzo-p-dioxins is a problem of imposing complexity. A concise summary of our present knowledge of structure bioactivity relationships for some two dozen dibenzo-p-dioxin derivitives leads to the following rules: 1) two halogen substituents at positions 2,3 and one halogen at position 7 are minimum structure requirements; 2) bromine as a substituent is more active than chlorine which is more active fluorine; 3) at least one hydrogen atom must remain on the dibenzo-p-dioxin. It is noteworthy that no amount of halogen substitution on only one ring leads to biological activity. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 139 C23369 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Three mechanistic variants are proposed whereby chemical binding between CDDs and protein or nucleic acid con CONFIDENT! AL SUBJECT TO PROTECTIVE ORDER. 140 C2337U II. III. IV. Aw W t:Y WORK PRODUCT Ai ^ ^ - C L I E N i ' PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): N . Kim Title: Building Reclamation after Dioxin Contamination by PCB Fires Reference: Book: Accidental Exposure to Dioxins, Edited by F. Coulston and F. Pocchiari, Academic Press, 1983 Citation No: 51 Source of Dioxins Source: A transformer containing Pyronox (55% PCB and 35% chlorinated benzenes) was damaged by fire. This was in a building in Binghamton, N.Y. Sampling Techniques: Not discussed - Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD mentioned; however, no details of analysis. The soot contained ~ 3ppm of 2,3,7,8-TCDD Analytical Techniques Method of analysis not mentioned. Specificity: Not discussed Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) The most highly contaminated areas were the spaces above the ceiling and in the walls. In question and answer period, Dr. Pocchiari said that in Seveso, Italy, the level of contamination of 2,3,7,8-TCDD was 0.001ug/m2 on the walls of houses. Dr. Silano stated that, on exterior building surfaces, the permissable level was 0.75 ug/m2, but for interior surfaces, it was 0.01ug/m2 . CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 141 G23371 ATTORNEY WORK PRODUCT A i iGRNEY-CLiENf PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): B. J. Kimble Title: Comments on "Chlorinated Dibenzo-p-dioxins and Related Compounds in Incinerator Effluents" Reference: Chemosphere, 10, 243-244 (1981) Citation No: 52 II. Source of Dioxins Source: Fly ash from an incinerator which contained at least 1309 ppb of PCDDs. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDD isomer cluster III. Analytical Techniques Used 4 x 20 ml of hexane/acetone (1:1 by volume) as an extractant with an ultrasonic probe. Analysed by GC/HRMS. Specificity: TCDD isomer cluster. Sensitivity: detection limits of 0.6 ppt. IV. Comments (Significant Data, Graphs, etc.) This article deals with an apparent error made by Lustenhouwer in one of his articles claiming to have used an extraction method developed by Kimble and Gross. Kimble points out that they did not develop the method he used. Kimble says the use of an ultrasonic probe was found to be superior in terms of mixing efficiency to either an ultrasonic bath or a Soxhlet extractor. Apparently Griest (another author is this research area) agrees. Apparently, Lustenhouwer felt Kimble and Gross had used an inappropriate extraction procedure and that was the reason why they found no TCDDs' in a fly ash sample from a modern commercial coal-fired power plant [Science, 207, 59 (1980)]. Kimble refutes this as indicated above. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDERi 142 023372 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): B. J. Kimble and M. L. Gross Title: Tetrachlorodibenzo-p-dioxin Quantitation in Stack-Collected Coal Fly Ash Reference : Science, 207, 59-61 (1980) Citation No*. 39 Source of Dioxins Source: Fly ash from the stack of a typical commercial coal-fired power plant which uses low sulfur, high ash coal. Sampling Techniques: The fly ash was collected downstream from the electrostatic precipitator located in the smokestack breaching. The particles were collected in 4 fractions (F* through F4) which had been characterized in terms of aerodynamics, morphology and elemental composition. The extraction, separation and analysis for TCDDs were done on the F2 fraction with controls. The samples were extracted with a mixture of hexane and acetone and, after cleanup and fractionation procedures, were analysed. Flow Data (mass transfer): A representative 750 MW (electric) power plant burns 200 tons of coal per hour, of which about 10% is fly ash. With an ESP as a control device assuming 95% efficiency, the total released fly ash is about 24 tons/day. From the analysis for TCDD (upper limit = 1.2 ppt), about 26ug of TCDD per day is emitted on fly ash. Chemistry of Formation: Not discussed Isomers Identified: Analysed only for TCDD. None found above the detection limit of 0.6 ppt. Analytical Techniques Used GC/HRMS with SIM mode Specificity: Only for TCDD isomer cluster. Sensitivity: Detection limit of 0.6 ppt of fly ash. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 143 C23373 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) This article challenges the report by Dow, who found TCDDs in fly ash from a similar power plant, on the "Trace Chemistries of Fire" (see Citation Nos. 13 and 23). Also, Kimble and Gross have been selected by the EPA to develop the protocol and do the analyses for PCDDs and PCDFs for evaluating refuse thermal processing facilities (see Citation No. 37). SUBJECT TO PROTECTIVE ORDER. 144 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): M. M. Kooke, et al Title: Extraction Efficiencies of Polychlorinated Dibenzo-p-dioxins and Polychlorinated Dibenzofurans from Fly ash Reference: Anal. Chem., 53, 461-463 (1981) Citation No: 53 Source of Dioxins Source: Two lOOOg samples of fly ash from the ESPs of different municipal incinerators. Sampling Techniques: Not discussed. The article deals with evaluating 7 methods currently used to extract PCDDs and PCDFDs from fly ash. Generally, Soxhlet extraction with benzene or toluene on acid treated fly ash proved best. - Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs, PeCDDs, HCDDs, and OCDD and corresponding PCDFs as chlorine isomer clusters Analytical Techniques Used HRGC/MS with SIM technique Specificity: PCDDs and PCDFs as chlorine isomer clusters Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Tables I - IV give the analytical results (PCDD and PCDF content or individual chlorine isomer clusters) on the two fly ash samples using the various extraction methods. Soxhlet extraction with benzene or toluene on acid treated fly ash appears to have the best extraction efficiency of the seven methods employed. CONFIDENTIAL SUBJECT TO P R O T E C T IV E ORDER. 145 CS337 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): F. Korte Title: Ecologie Chemistry of Dioxins and Related Compounds Reference: Book: Accidental Exposure to Dioxins, Edited by F. Coulston and F. Focchiari, Academic Press, 1983 Citation No: 54 Source of Dioxins Source: This is a review article and mentions that' the PCDDs and PCDFs are not industrial chemicals in the normal sense. The article mentions their formation from chlorophenols and in combustion processes. Korte says "It can be expected that there are also natural sources of these chemicals, although this has not yet been demonstrated unequivocally". Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: Mentions formation by condensation of 2 molecules of chlorophenols (Fig. 1). Mentions "predoxins" and "isopredioxins" as precursors. Also, mentions pyrolysis of chlorobenzenes, polychlorodiphenyl ethers and PCBs. Isomers Identified: Mentions that TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD are found when impregnated wood wool or birch leaves are burned. Analytical Techniques NA Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) Suggests that photochemical degradation could be a major route of environmental elimination. Also, uv irradiation could be used for indoor decontamination. SUBJECT TO PROTECTIVE ORDER. 14ff C23376 I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s) E. R. Krishnan, et al Title: Trace Emissions from Coal and Oil Combustion Reference Environmental Progress, 1_, 290-295 (1982) Citation No: 55 Source of Dioxins Source: This is a survey article reporting what is published in the literature regarding trace emissions from (1) utility boilers, (2) industrial boilers, (3) commercial/.institutional boilers, and (4) residential boilers. Sampling Techniques: NA Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Only "dioxins" mentioned Analytical Techniques Not discussed Specificity: Sensitivity: Not discussed Not discussed Comments (Significant Data, Graphs, etc.) Tables 2,3,4 and 5 give trace pollutants emitted from the four type boilers (1) Utility (2) Industrial (30 Commercial and (4) Residential. "Dioxins" are only reported for the utility boilers (0.01 pg/Joule). SUBJECT TO PROTECTIVE ORDER. 147 C2337V I. II. III. attorney w o rk product ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): J. Lamberton, et al Title: The Determination of Polychlorodibenzo-p-dioxins in Pentachlorophenol and Wood Treatment Solutions Reference: Am. Ind. Hyg. Assoc. J. , 40, 816-822(1979) Citation No : 56 Source of Dioxins Source: Fresh 5% PCP treating solution. Recirculated 5% PCP treating solution. Sludge. Sampling Techniques: The above samples were obtained from two wood treatment plants. No description of how the samples were taken is given. The dioxins and furans were isolated from the samples by dissolving the samples in appropriate solvents and passing them, through activated alumina and Dowex 2IK ion exchange resin (OH form), and eluting the dioxins and furans off with an acceptable solvent. Flow Data (mass transfer): NA Chemistry of Formation: Mentions formation of PCDDs from chlorophenols under basic conditions at elevated temperatures. Also mentions formation at elevated temperatures in absence of base, from copper phenates, and under free radical conditions. Isomers Identified: HCDDs and HCDFs; HpCDDs and HpCDFs; OCDD and OCDF. This was using the microcoulometric method. GC/MS with single ion monitoring profile analysis(SISPA) gave 3 HCDDs, 2HpCDDs and OCDD. Analytical Techniques Used microcoulometric method as well as GC/MS with SISPA technique Specificity: GC/MS gave HCDDs, HpCDDs, OCDD, HCDFs, HpDFs and OCDF. Sensitivity: limit of detection = 10 ppb. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 148 CC3378 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) Table I: GC/MS(ppm) Microcoulometric(ppm) Sample HCDDs HCDDs + HCDFs HpCDDs + HpCDDs OCDD + OCDF Fresh 5% solution Recirculated 5% Solution Sludge 26 29 21 55 519 1036 57 610 1385 47 963 1965 Table II: Recirculated 5% solution by GC/MS with SISPA No. of Cl Dioxin Furan Total 6 29 20 49 7 , 524 91 615 8 1306 18 1324 The increase in the OCDD and HpCDDs in the recirculated solution . could be due to conversion of the appropriate predioxins during the wood treating process, or it could be due to selective deposition of the PCP in the wood leaving a dioxin enriched solution. Both OCDD and HpCDDs accumulate in the sludge, but HCDDs (more toxic) do not (maybe more soluble and thus impregnate wood). CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 149 023375) ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): L. L. Laraparski and T. J. Nestrick Title: Determination of Tetra-, Hexa-, Hepta-, and Octachlorodibenzo-p-dioxin Isomers in Particulate Samples at Parts per Trillion Levels Reference: Anal. Chem., 52, 2045-2054 (1980) Same data published in Pergamon Ser. Environ. Sci., 5, 1-13 (1982) Citation No: 57 II. Source of Dioxins Source: (1) Dust from the air intake filtration system in a research building in Midland, Michigan (Dow). (2) Fly ash from the ESP of a refuse incinerator in Nashville, Tenn. (3) Activated municipal sludge sample from the center of a 20 kg bag of Milwaukee Milorganite. (4) Urban particulate matter - Std. Ref. Mat. No. 1648 from NBS. (5) European fly ash collected on filter paper from a sampling port downstream from the ESP of a municipal trash incinerator. Used a nonisokinetic sampling procedure. Sampling Techniques: Sample preparation involved: (1) PCDDs removed using hydrocarbon extraction, (2) chemically modified adsorbent treatment of the extract to remove easily oxidized species, (3) adsorbent treatment to remove common chemical interferences, (4) RP-HPLC residue fractionation to remove residual chemically similar interferences and to separate PCDDs into groups according to degree of chlorination, (5) silica-HPLC refractionation of the RP-HPLC TCDD fractions to provide a second separation having different selectivity to remove residual interferences and permit TCDD isomer specificity. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed CONFIDENTI -4L c i i r i f c T TO PROTECTIVE ORDER. 0^3380 ATTORNEY W ORK PRODUCT ATfORNEY-CUENT PRIVILEGE Isomers Identified: Table V: 20 of th 22 TCDD isomers (2,3,7,8-TCDD found in dust, both fly ashes and sludge at ppt levels). Table VII: "Semi" isomer-specific data for 10 HCDD isomers in European fly ash. Table IV: PCDD chlorine isomer groups found in 5 sources (TCDDs, HCDDs, HpCDDs, and OCDD). Analytical Techniques Used packed column GC/LRMS with SIM technique. Specificity: Isomer specific for TCDDs and OCDD. "semiMisomer specific for HCDDs. HpCDD isomer group (2 isomers) Sensitivity: For TCDD isomers: 2-150 ppt limit of detection. For HCDD isomers: 9 ppb limit of detection. Comments (Significant Data, Graphs, etc.) This paper reports the development of an analytical procedure which permits the isomer-specific determination of 2,3,7,8-TCDD at low ppt concentration in the presence of the other 21 TCDD isomers. Higher PCDDs can also be determined at low ppt levels using this technique. ' Figure 2 shows block diagram of sample preparation. Table I gives the specific RP-HPLC retention indices for TCDDs. Table II gives the specific RP-HPLC retention indices for HCDDs, HpCDDs and OCDD. Because of lack of authenticated PCDF standards, no attempt was made to quantify these species. Table III gives the specific silica-HPLC retention indices for the various TCDD isomers. Tables IV, V, VI and VIII give analyses of the various source samples for PCDD chlorine isomer groups and isomer-specific TCDD and "semi" isomer-specific HCDD. SUBJECT TO PROTECTIVE ORDER 151 attorney w o rk product a t t o r n e y -c lie n t PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): A. Liberti, et al Title- Determination of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in the Emission from Urban Incinerators Reference : Mikrochimica Acta (Wien), 1981 I , 271-280 Citation No: 58 II Source of Dioxins Source: Various emissions from several municipal incinerators (1) ash- any solid material obtained as a residue (bottom ash) (2) fly ash - dust collected by an ESP (3) sludge - fly ash that is collected by a cyclone with a water spray (4) particulates - material isokinetically sampled in the stack fumes (5) organic vapors - trapped with the water condensed by cooling the stack fumes or passing cooled gases through an organic solvent (usually ethylene glycol). Sampling Techniques: The fumes were sampled under isokinetic conditions with quartz wool to collect particulate matter. After cooling to condense water, the organic vapors in the fumes were trapped in ethylene glycol. Soxhlet extraction mainly with xylene was used for recovery of organics from the solid fractions. The cleanup procedure involved (1) a silica gel column to remove non-chlorinated interfering species (2) an alumina column to separate PCDDs and PCDFs from PCBs, PCNs, and other non-polar compounds. Flow Data (mass transfer): Not discussed Chemistry of Formation: A large sample of the garbage, which was to be incinerated, was crushed, homogenized, dried and extracted with xylene. Analysis of the xylene extract revealed no PCDDs or PCDFs. The SUBJECT TO PROTECTIVE ORDER. 152 r O ' III. IV. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE authors thus attribute the formation of PCDDs and PCDFs to pyrolytic reactions of precursors (polyphenols in vegetables, other phenolics and PCBs). In the presence of HC1 set free from chlorine-containing compounds; these precursors yeild PCDDs and PCDFs. Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs, and OCDD as isomer groups or clusters (GC/MS identification) TCDDs and TCDFs, PeCDDs and PeCDFs, HCDDs and HCDFs, HpCDDs and HpCDFs, and OCDD and OCDF (GC only) Analytical Techniques Used glass capillary HRGC with Ni63 electron capture detector. Also GC/MS with El ion source. Specificity: Only PCDDs as different chlorine number isomer clusters. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) This is one of the few papers which clearly shows that PCDDs and PCDFs were not present in the starting refuse to be incinerated. Thus the PCDDs and PCDFs were clearly formed during pyrolysis. The authors support Dow's "trace chemistries of fire" hypothesis, and seem to concur that PCDDs are ubiquitous. They say, "Our investigations show that the incineration processes of urban, wastes definitely yield a number of PCDDs and PCDFs through a variety of possible reactions, the concentrations being low definitely but much larger than those usually, found in the environment and arising from other sources." Table I gives the concentrations (ng/g) of the PCDDs and PCDFs (as chlorine number isomer clusters)found in the 8 incinerator samples analysed. SUBJECT TO PROTECTIVE ORDER. r *n U-w 3 3 8 d 153 ,1. II. III. ATTORNEY w o r k ATTORNEY-CLIENT PRODUCT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): A. Liberti, et al Title: Determination of Polychlorodibenzo-p-dioxins and Polychlorodibenzofurans in Environmental Samples by Gas Chromatography - Mass Spectrometry Reference: J. of Chromatography, 242, 111-118 (1982) Citation No: 59 Source of Dioxins Source: (1) Fly ash from urban waste incinerators in Milan, Florence and Rome, Italy (2) Vapors from an urban waste incinerator in Rome. (3) Sludge collected by cyclone with water spray from an urban waste incinerator in Messina, Italy. Sampling Techniques: The details of the sampling were not given. The extraction and cleanup procedure was essentially the same as that given in Citation No. 58, except benzene was used to extract the solid samples and the ethylene glycol used to collect the organics in the vapors was extracted with methylene chloride. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: PCDDs: TrCDDs, TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD as isomer clusters PCDFs: TrCDFs, TCDFs, PeCDFs, HCDFs, HpCDFs and OCDF as isomer clusters Analytical Techniques Used capillary and packed column GC/HRMS with selected ion detection (SID). Specificity: Chlorine number isomer clusters for PCDDs and PCDFs, together and separately. Sensitivity: Packed column GC = 50-100 pg. Capillary column GC = a few pg. DEMTM SUBJECT TO PROTECTIVE ORDER. 154 023384 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT P|V!L:GE Comments (Significant Data, Graphs, etc.) This article describes an analytical method for the simultaneous determination at ppt level of tri-, tetra-} hexa-, hepta-, and octachlorodibenzo-p'dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in solid samples and water condensate from urban incinerators. Table I gives the analytical results. SUBJECT TO PROTECTIVE ORDER. 155 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): A. Liberti and D. Brocco Title: Formation of Polychlorodibenzodioxins and Polychlorodibenzofurans in Urban Incinerator Emissions Reference: Pergamon Ser. Environ. Sci., 5, 245-251 (1982) Citation No: 60 II. Source of Dioxins Source: Bottom ash, fly ash, sludge and organic vapors (trapped by water condensation or by adsorption in organic solvents) from urban waste incinerators classified as follows: A. incinerators from highly populated areas where wastes are incinerated without any treatment. B. incinerators where waste is mainly agricultural products which are burned without any treatment. C. incinerators where waste passed through a recycling material are removed. D. incinerators where the input material is the residue of wastes which went through an homogenization and oxidation process (the unfermented residue being burned). Sampling Techniques: The details of the sampling were not given. Extraction of the samples and cleanup procedures were the same as in Citation No. 58. Flow Data (mass transfer): Not discussed Chemistry of Formation: Since samples of urban wastes to be incinerated have been shown not to contain PCDDs or PCDFs, their formation has to be attributed to reactions occuring in the incinerator. Mentions the formation of PCDDs by heating chlorophenols and the formation of PCDFs from pyrolysing PCBs. The authors put forth the following hypothesis: Precursor A + Precursor B --- >PCDDs (organic matrix) (Cl2 or HC1 donor) Phenols or polyphenols PVC, etc. CONFIDENTS * *. SUBJECT. TO. PROTECTIVE ORDER. 156 + PCDFs C2338u ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRiVILEGE Isomers Identified: incinerator Chlorine No. isomer clusters A TCDDs, PeCDDs, HCDDs, HpCDDs, OCDD, HpCDFs, OCDF B HpCDDs, OCDD C HpCDDs, OCDD D HpCDDs, OCDD Analytical Techniques Used packed or capillary column HRGC with Ni63 ECD, and MS with El ion source and SIM technique Specificity: Chlorine No. isomer clusters for both PCDDs and PCDFs Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) In general, the concentration of PCDDs and PCDFs in the emissions was respectively in the range of 1 ppm and 0.5 ppm for type A incinerator (See Table I). Table II shows analytical results from emissions of all 4 types of incinerators. Type B shows much lower values. This can be explained by the authors' mechanism. Vegetable matter will have only small amounts of Precursor B and thus only small amounts of chlorinated compounds will appear in the emissions. For type C and D incinerators, most A precursors are removed and combustion of the material mainly containing precursor B gives rather small amounts of chlorinated organics. CONFIDENTI AL SUBJECT TO PROTECTIVE ORDER. 157 023387 attorney w o rk proouct ATTO RN EY-CLIENTP^iS J I. II. III. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): A. Liberti, et al Title: Sampling and Determination of Polychlorodibenzo-pdioxins, Dibenzofurans and Their Precursors in the Incineration Process of Urban Wastes Reference: Pergamon Ser. Environ. Sci. , 281-286 (1982) Citation No: 61 Source of Dioxins Source: Fly ash and fumes from various urban incinerators of Italian cities. Some of the incinerators burned wastes as received. Some burned the waste after composting. Sampling Techniques: The details of the sampling process were not given. Extraction procedures were studied to determine efficiency. It was found that room temperature leaching appears as effective as toluene long term Soxhlet extraction, and avoids heat which might cause the formation of PCDDs and PCDFs from the PCB and chlorophenol precursors. All extracts were concentrated under a nitrogen stream at room temperature to 1 ml and transferred to a silica gel column and eluted with n-pentane. The eluate was evaporated to dryness and redissolved in a small amount of toluene ready for analysis. Flow Data (mass transfer): Not discussed Chemistry of Formation: Mentions hypothesis discussed in Citation No. 60 Isomers Identified: PCDDs: TrCDDs, TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD as isomer clusters PCDFs: Same isomer clusters as for PCDDs. Analytical Techniques Did simultaneous analysis of PCDDs and PCDFs using packed column GC/HRMS with SID mode. Specificity: Chlorine No. isomer clusters for both PCDDs and PCDFs. CONFIDENT! AL SUB.JFCT T n DDrrrrrr*-riwr- __ 158 GS3888 attorney w o r k product A T T O R N E Y -CLitNi Pk im GE Sensitivity: Not discussed IV. Comments (Significant Data, Graphs , etc.) Table II gives the analytical results on fly ash and fumes from various incinerators. The results are consistent with the proposed mechanism of formation of PCDDs and PCDFs. When wastes are treated precursors (tAoorremBo) v>e or the reduce the content of one of the type concentration of the PCDDs and PCDFs formed is drastically reduced. CIID1 -- - a .iA L , SUBJECT TO PROTECTIVE ORDER. 159 023389 II. III. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): A. Liberti, et al Title: Evaluation of Organochlorine Compounds in the Emissions of Urban Incinerators Reference : Pergamon Ser. Environ. Sci, 157-166 (1980) Citation No: 62 Source of Dioxins Source: Bottom ash, fly ash, particulates from fumes and organic vapors in the fumes (as water condensate or trapped in an organic solvent) from incinerator emissions (see Citation No. 58) Sampling Techniques: No details are given regarding bottom ash and fly ash sampling. The particulates in the stack were sampled isokinetically with quartz wool. After cooling to condense water, the organic vapors were trapped in toluene. Figure 1 shows the sampling scheme. The solid samples were Soxhlet extracted with benzene and the extract evaporated to 1 ml. The condensed water was extracted with benzene, and the benzene extract evaporated to 1 ml. The toluene used to absorb the organic vapors was evaporated to 1 ml. Extracts of the solid samples were cleaned up by (1) elution with hexane on a silica column and (2) elution with 2% and 50% methylene chloride in hexane on an alumina column to separate out the PCBs from the PCDDs and PCDFs. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD Analytical Techniques Used packed column GC/MS with El ion source with SIM mode. Specificity: PCDD chlorine No. isomer clusters Sensitivity: Not discussed 1 Hr SUBJECT TO PROTECTIVE ORDER. 160 G2339U Comments (Significant Data, Graphs, etc.) In 1977, Olie reported that PCDDs and PCDFs were formed as trace contaminants of fly ash and fine gas of some municipal incinerators. These results were confirmed in 1978 by Rappe, Buser and Bosshardt. Table I shows the analytical data on the extracts of the bottom ash, fly ash and particulates in the fumes of an urban incinerator. The highly chlorinated PCDDs are present in largest concentrations with OCDD being the most. A sample of the waste to be incinerated was analysed (see Figure 6). Chlorophenols and PCBs were found but no PCDDs. Thus the PCDDs definitely were formed by the pyrolytic reactions of the precursors. In Table I, the higher the PCBs in the solid samples, the higher were the PCDDs in the same samples. Unusual is that GC analysis of the extracts of the water condensate and the organic vapors trapped in toluene showed no PCDDs. SUBJECT TO PROTECTIVE OPvDER. 161 ATTORNEY W ORK PRODUCT A! iORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): A. Liberti, et al Title: Reference: PCDD and PCDF Formation in the Combustion of Vegetable Wastes Chemosphere, 12, 661-663 (1983) Citation No: 63 II. Source of Dioxins Source: Vapors and particulates from the laboratory combustion of vegetable materials (chestnut extract, tannic acid, mimosa extract, fresh fruits and vegetables). Sampling Techniques: The vegetable materials were combusted under an air stream in a sand bath. The vapors and particulates were collected in 2N NaOH solution. The same experiments were performed by adding CI2 to the air stream. Total phenols and polyphenols were determined by Folin-Ciocalteau reagent and phenols and chlorophenols by TLC and GC. After combustion, the alkaline solution was acidified with HC1, and extracted with methylene chloride. The latter was dried with Na2S04 and analysed by silica gel TLC eluting with chloroform-methyl acetate (4:1). The phenols and chlorophenols spots were scraped from the plate and extracted with methylene chloride to obtain the PCDDs and PCDFs. Flow Data (mass transfer): NA Chemistry of Formation: Mentions hypothesis discussed in Citation No. 6(K Isomers Identified: From Table 2 (ug/g) PCDDs: TrCDDs, TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD as chlorine no. isomer clusters (6-74 ug/g) PCDFs: Same chlorine no. isomer clusters as for PCDDs (2-101 ug/g) III. Analytical Techniques Used GC/HRMS-details not given CONFIDENT? AIL SUBJECT TO PROTECTIVE ORDER. G2 3 3 9 V Chlorine No. isomer clusters for both PCDDs and PCDFs. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Table 1 gives analysis for phenols and polyphenols in the vapors and particulates from the combustion of vegetable materials. Specific phenols found were phenol, m-cresol,.and p-cresol. No chlorophenols were found. Table 2 gives the analysis for PCDDs and PCDFs in the vapors and particulates from the combustion of vegetable materials in the presence of chlorine in the air stream or PVC added. In addition to the above mentioned PCDDs and PCDFs, di-, tri-, tetra-, and pentachlorophenols were found (ug/g). Sequence of reactions postulated: Vegetable----- > phenolics -- > chlorophenols--- ^PCDDs material SUBJECT TO PROTECTIVE ORDER. 163 rU rw*;. 3 3 9 3 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins product PRIVILEGE I. Citation Author(s): R. Lindahl, C. Rappe and H. R. Buser Title: Formation of Polychlorinated Dibenzofurans (PCDFs) and Polychlorinated Dibenzo-p-dioxins (PCDDs) from the Pyrolysis of Polychlorinated Diphenyl Ethers Reference: Chemosphere, 9, 351-361 (1980) Citation No 64 II. Source of Dioxins Source: Laboratory pyrolysis of eight polychlorinated diphenyl ethers (PCDPEs). Sampling Techniques: NA The eight PCDPEs were synthesized from biaryliodonium salts. The materials were checked for purity and found to be > 98% with no detectable quantities of PCDDs or PCDFs. wo Nanti Ari-I-Ar^X + Ar2-0Na 3 > Ar2-0-Ari + A r i l + NaX 0J X = I or Cl Ari = phenyl or p-chlorophenyl Ar2 = mono-to pentachlorophny Flow Data (mass transfer): NA Chemistry of Formation: C23394 214 1 STATE OF ILLINOIS ) ) SS. 2 COUNTY OF ST. CLAIR ) 3 4 5 If RICHARD P, GOLDENHERSH, one of the Judges in and 6 for the Twentieth Judicial Circuit/ do hereby certify that 7 the foregoing transcript is a true and correct transcript of 8 the proceedings had in said cause. 9 Dated this ____ day of March/ 1986. 10 l 12 13 RICHARD P. GOLDENHERSH, JUDGE 14 15 16 17 18 19 20 21 22 23 24 Isomers Identified: 1,2,4,6,8,9-HCDF 1.3.6.8- TCDF 1.3.4.8.9- PeCDF 1.2.4.7.8- PeCDF 2.3.4.6.7.8-HCDF 2.3.4.7.9- PeCDF (Proposed) 2.3.7.8- TCDD 2,3,4,8,9-PeCDF 1,2,6,8-TCDD (Smiles Rearr.) 1.3.8- TrCDF 1,2,6,7-TCDD 1,2,7,9-TCDD 1.2.4.8- TCDF 1,2,8,9-TCDD (Smiles 1,2,4,6,7,8-HCDF Rearr.) 2.3.8-TrCDF 1.3.4.6.7.8-HCDF 1,2,4,8,9-PeCDF 1.2.3.4.6.7.8- HpCDF 1.2.3.4.8.9- HCDF 1,2,7,8-TCDD (Proposed) 1,2,3,4,6,7-HCDD III. IV. Analytical Techniques Used capillary GC/MS with El source with many reference isomers Specificity: Isomer specific for all of the above (except the two proposed) Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) In the pyrolysis of PCDPEs to form PCDFs and PCDDs, 600C. appears to be the optimum conversion temperature, (see Table 2). T%abDleecom3pogsiivteisond,ata% on pyrolysis PCDFs formed of 8 and, %PCDPPCEDsDs at 600C. formed. Excellent article on mechanism of formation of PCDDs and PCDFs from PCDPEs. SUBJECT TO PROTECTIVE ORDER. 165 r' O-w II III IV, ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): F. W. Lipfert and J. L. Dungan Title: Residential Firewood Use in the United States Reference: Science, 219, 1425-1427 (1983) Citation No: 65 Source of Dioxins Source: PCDDshave beenreported in residential fireplace soot, (see Citation No. 13). This article gives an estimate of cords of wood used per year for the 1978-1979 heating season for home fireplaces in the U. S. This was 34.7 x 106 cords or about 0.8 quad of energy per year (1 quad = 1015 BTU) Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: NA. Isomers Identified: NA Analytical Techniques NA Specificity: NA Sensitivity: NA Comments (SignificantData, Graphs, etc.) We might use this data to calculate potential PCDD/PCDF emissions from woodburning fireplaces in the U. S. Data of PCDDs present in home fireplace soot from Citation No. 13 (ng/g or ppb): TCDDs 2,3,7,8- Other Total HCDDs HpCDDs OCDD ND-0.1 ND-0.3 ND-0.4 0.2-3 0.7-16 0.9-25 CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 166 023396 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): A. D. Little, Inc. (for the Amer. Soc. of Mech. Engrs.) Title: Dioxin Emissions from Combustion Sources: A Review of the Current State of Knowledge Reference: Final Report, December 29, 1980 Citation No : 66 II. Source of Dioxins Source : This review article discusses the current knowledge (mid 1980) of combustion sources of PCDDs. These are : (1) Laboratory-scale combustion studies (2) Municipal incinerators (Netherlands, Switzerland, Germany, Canada, Japan, U.S.) (3) Industrial waste incinerators (Switzerland, U.S.) (4) Hazardous Waste incinerator (at sea-Vulcanus) (5) Oil/coal-fired powerhouse (U.S.) (6) Coal-fired utility facility (U.S.) (7) Miscellaneous sources briefly mentioned (Dow Study-Citation No. 13) Sampling Techniques: Discusses this area rather thoroughly. Points out that of the various forms of emissions that may be sampled the only reliable method of determining the levels of direct PCDD emissions in the stack gas is an integrated sample of the stack gas itself. Discusses the modified Method 5 train and the Source Assessment Sampling System (SASS). The extraction and cleanup of the sample are the most critical steps, because the levels of PCDDs in samples of environmental concern are in the low ppt and all interfering materials (e.g. DDT and PCBs) must be minimized. Strong base extraction was the most widely used but there has been concern over formation and/or destruction of dioxins; the latter definitely taking place. Thus neutral extractions now seem preferred, particularly Soxhlet or ultrasonic extraction with organic solvents. The cleanup method of choice is liquid column chromatography with the preferred packing being alumina with silica gel (retains polar CONFIDENT! 4L SUBJECT TO PROTECTIVE ORDER. 167 C23397 ATTORNEY W ORK PRODUCT Ai TCRNEY-CLiEh'T privilege entities-phenols) and florisil (removal of PCBs) used as adjuncts. The Dow methods ML-AM-73-97 and ML-AM-78-63 are mentioned. The ultimate cleanup, as suggested by Dow, is HPLC using a reverse phase HPLC system, which permits separation of individual PCDD classes. Flow Data (mass transfer): Not discussed Chemistry of Formation: 1. Dimerization of chlorophenols Example HC1 + Cl 0 .Cl Cl30CGXCl + HC1 2 . Dechlorination of higher PCDDs This accounts for the presence of PCDDs with less than 8 chlorines in the PCP pyrolysis experiments. 3. Cyclization of "predioxins" Example + HC1 "predioxin" 4. Pyrolysis of polychlorobenzenes Thought to occur as follows: PCBz ------ > PoCP ----- * PCDD Isomers Identified: See Table 4 (p. 28) HPLC = PCDD chlorine no. isomer clusters - screening. LRGC/LRMS = ii n mh ii ii HRGC/LRMS = isomer spcifie LRGC/HRMS = PCDD chlorine no.isoraer clusters-screening KRGC/HRMS = isomer spcifie III. Analytical Techniques Method of choice is GC/MS which has sensitivity and specificity for 2,3,7,8-TCDD in the ppt range. Discussed the role of GC (component separation) and MS (detection, identification and IAL SUBJECT TO PROTECTIVE ORDER. 168 C23398 ATTORNEY WORK PRODUCT quantification) play in the analysis. Thoroughly explains the various GC/MS combinations and compares their performance - packed column (LR) and capillary column (HR) GC, and LRMS (nearest m/z whole unit) or HRMS (specific m/z). Specificity: For individual isomer determination HRGC/HRMS is necessary. Sensitivity: See Table 4 (p. 28) HPLC = 100 ppb LRGC/LRMS = 10-50 ppt O HRGC/LRMS =8 ppt I LRGC/HRMS = 4-5 ppt r* HRGC/HRMS = 2-50 ppq J assuming multiple ion detection (MID) Comments (Significant Data, Graphs, etc.) A. Summary 1. Basic Chemistry PCDDs appear to be relatively persistent in the _ environment if released into air, water or soil. 2. Measurement in Combustion Emissions Stack sampling systems capable of collecting both particulate and vapor phase organics are required and are available. Sample extraction and cleanup most critical because of low levels (ppt) in environmental samples. Such methodology seems reasonably well developed. GC/MS is analysis method of choice. HRGC/HRMS is most reliable and isomer specific at ppt. 3.' Toxicological Considerations PCDD isomers have widely differing toxicities. 2,3,7,8,-TCDD is the most toxic in animals with 1,2,3,7,8-PeCDD; 1,2,3,6,7,8-HCDD; and 1,2,3,7,8,9-HCDD quite toxic. Human acute effect is chloracne. Epidemiological studies on man are in progress but no definite results yet on long-term effects. 1975 - NTOSH listed 2,3,7,8-TCDD as a suspect carcinogen 1978 - NI0SH listed it as a carcinogen 1979 - EPA water quality criteria lists it as a carcinogen CONFIDENT! A.L SUBJECT TO PROTECTIVE ORDER. 169 023399 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE 4, Generation, Emission and Control of Dioxins from Combustion Sources. (a) Thermal Degradation of Dioxins N.Y. State Dept, of Environ. Conserv. Htawnod-bsotoakge-i"nicnicnienreartaitoinonatat81510C0.0Cf.orfo\ r 2 sec. or sec. then 1200C. for 1 sec. U.S. Air Force Occup. and Environ. Health Lab cites 980-1000C. for 2,3,7,8-TCDD. (b) Formation of PCDDs by Thermal Degradation of Precursors From Polychlorophenols (PoCPs) by dimerization at as low as 200C. Sodium and potassium chlorophenates give higher yields. The . major PCDDs are formed <0.1% by wt. of phenol. Other minor PCDDs formed by other mechanisms at 0.0001% to 0.0025%. From dechlorination of higher chlorinated PCDDs. PCP pyrolysis gives PCDDs with <8Cls. Cyclization of "predioxins" (PCPPs) Combustion of 2,4,5,-T and related compounds (esters) at ~ 750C. Pyrolysis of PCBzs at ~ 620C. gives yields of PCDDs of <0.001% to 0.08% by wt. PoCPs may well be intermediates. (c) Emissions from Full-Scale Combustion Facilities CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. Detectable quantities of PCDDs found in fly ash from municipal incinerators in Canada, Japan, Germany, Netherlands, Switzerland, and U.S. Also, from industrial and hazardous waste incinerators in Switzerland and U.S. No reports where PCDDs were not found at the ng/g of fly ash, but 2,3,7,8-TCDD is not a major component. Formation of PCDDs in fossil fueled power plants is not definite. One report (Dow) says yes; another (Gross and Kimble) says no. Overall, available data do not reveal any consistent pattern in distribution of isomer clusters to permit confirmation or refutation of hypothesis of possible precursors or mechanism of formation of PCDDs in incinerator emissions. However, only one report lists formation of DCDDs and TrCDDs-all other studies report TCDDs to 0CDD. 170 02340U attorney w o rk product a t t o r n e y -client privilege Levels of TCDDs from municipal incinerators are generally <10 ng/g fly ash, while industrial and chemical waste incinerators give generally <100 ng/g fly ash. A thorough investigation involving input and output stream characterization has not been reported to date. Most data to date is on analyses of fly ash from ESPs and may not quantitatively reflect PCDD emissions from the stack gas and entrained particulates. (d) Potential Control of Emissions Reduction in particulate emissions: State-of-the-art does not permit removal of organic pollutants at ppt level in flue gas Identify and eliminate PCDD Precursors: The range of possible precursors for formation of detectable quantities of PCDDs is probably not broad, but chlorophenols and PCBzs are widely distributed. Only practical way is to ban the use of selected "good" precursors. Modification of Combustion Conditions Parameters that influence combustion efficiency are: Combustion zone temperature Combustion zone residence time Air to fuel ratio Mixing efficiency B. Conclusions 1. Measurement of Dioxins in Combustion Emissions * State-of-the-art methodology for sampling requires collection of replicate, time-averaged samples of stack gas effluent. A comprehensive sampling train is needed. * Sample preparation and clean-up are critical steps for PCDD analyses to achieve necessary low detection limits and eliminate false positive results from interfering chemicals. GC/MS represents state-of-the-art for analysis of total PCDDs and/or specific isomers. SUBJECT TO PROTECTIVE ORDER. 171 C2340 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE 2. Toxicological Considerations * Individual PCDD isomers have widely differing toxicities; some exceptionally toxic. Data is insufficient for evaluation of possible effects of potential emissions at ppt levels from combustion sources. 3. Generation, Emission and Control of Dioxins from Combustion Processes * PCDDs are probably present in effluents from most, if not all, municipal and industrial waste incinerators. Data are insufficient to establish whether they are present in fossil-fuel fired combustion source effluents. * Data are insufficient to confirm or refute hypotheses concerning precursors of PCDDs in incinerator influents. PoCPs and PCBzs are considered potential precursors -for PCDD emis&ion on the basis of lab studies. * Potential approaches to control of PCDD emissions have been identified, but feasibility cannot be evaluated in the absence of criteria defining the degree of control required. C. Risk Assessment Measurements at energy-from-waste plants indicate the possible presence of 2,3,7,8-PCDD in stack effluent at -- 1 pg/g on a mass basis. Based on logical assumptions, ground level concentration is estimated at 0.1 pg/m3 . N.Y. State Health Dept, estimates, from toxic dosage data on 2,3,7,8-TCDD in water and/or fish, that a concentration of 0.3 pg/m3 at ground level would involve a risk of one additional cancer case in a population of 1 million. Relating the degree of risk posed by the presence of dioxins to the risks of other life activities, one finds: Risks Deaths per million per year Drinking (1 bottle wine/day) 75 Smoking (20 cigarettes/day) Motorcycling 250,,000000 Earthquake (Calif.) Tornados (Midwest) Floods (U.S.) 1.7 2.2 2.2 200 ------ L I[UoCtOoLr VV eC hU iJ . cU lX eC ^(UU.* S1J .) SUBJECT TO PROTECTIVE ORDER, in the home (U.S.) 250 100 At work (U.S.) In public (drownings, etc.)(U.S.) 65 100 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Thus, the Level of risk (1 in a million) due to potential dioxin emissions from waste incinerators is several orders of magnitude less than the risk of death to which the general public is exposed. C O N * 1- "cnvE OR** SUBJEcT T 173 C23403 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): J. D. Longstreth, et al Title: Risk Assessment For 2,3,7,8-Tetrachloro Dibenzo-p-Dioxin (TCDD) Reference : Environ. Sci. Res., 26, 639-664 (1983) Citation No: 107 II. Source of Dioxins Source: From exposure to production grade 2,4,5 trichlorophenoxy acetic acid (2,4,5-T) and 2,4,5 trichloropropeonic acid (Silvex) herbicides. Both inhalation and dietery routes of exposure are considered. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Not discussed III. Analytical Techniques Specificity: Not discussed Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) Both 2,4,5-T and Silvex use 2,4,5-trichlorophenol as a starting raw material. Concentration of 2,3,7,8-TCDD (TCDD) in the herbicide formulations range between 0.01 ppm to 0.1 ppm. (USEPA 1981). This report presents efforts to'develop a quantitative risk assessment of 2,4,5-T and silvex herbicides using the decision tree for estimating human risk from exposure to toxic chemicals shown in Fig. 1. Based on the available exposure information and assuming a level of 0.01 ppm TCDD in 2,4,5-T and silvex, it is estimated that the general population may be exposed to a daily TCDD dose of about 0.007pg/kg. Sub populations consuming only TCDD-contaminated beef or dairy products are estimated to receive doses of 0.44-1.llpg/kg/day, respectively. The doses, estimated from occupational exposure range from a low of 0.OOlpg/kg/day (flaggers) to a high of CONFIDENT ^L SUBJECT TO PROTECTIVE ORDER. 174 023404 ATTORNEY WORK PRODUCT A'iTORNEY-CLIENT P". VILEGE 2.18pg/kg/day (right-of-way hand applicators). Because TCDD induces tumors in rodents, high-to-low dose extrapolations using the probit, logit, Neibull, multi-hit and multi-stage models were used to determine VSDs associated with several levels of human risk. An unusual pattern of predictions resulted, with the multi-stage model, normally the most conservative, being the least conservative. Based on this and the uncertainty as to the mechanism of TCDDs carcinogenic effect, it was concluded that the use of these models to estimate human risk is inappropriate. This conclusion, in conjunction with a lack of evidence that TCDD is a genotoxic carcinogen, led to an estimate of human risk from TCDD based on an ADI of Ipg/Kg/day. At the assumed level of TCDD contamination in 2,4,5-T and silvex, two populations receive estimated doses that slightly exceed this ADI and hence may be at risk: individuals eating only contaminated dairy products and pesticide applicators hand spraying of right-of-ways. SUBJECT TO PROTECTIVE ORDER. 175 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE V , Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): Title: J. W. A. Lustenhouwer, K. Olie, and 0. Hutzinger Chlorinated Dibenzo-p-dioxins and Related Compounds in Incinerator Effluents Reference: Chemosphere, , 501-522 (1980) Citation No: 84 II Source of Dioxins Source: This is a review article covering literature to Jan. 1980. Sources mentioned are: 1. municipal incinerators 2. chemical waste incinerators 3. fossil fuel powerhouses 4. car and Diesel truck exhaust 5. industrial processes 6. fireplaces 7. cigarettes 8. charcoal grills Sampling Techniques: Not discussed. Table 2 gives extraction efficiencies of PCBzs, PCDDs and PCDFs from particulate matter by various methods. Toluene extraction (Soxhlet) of acid treated material generally gives the highest recovery. The cleanup procedure recommended is adoption of .that used by Dow in Citation No. 13. The concentrated residue from toluene extraction is dissolved in hexane and passed through a column packed with silica and silica/H2S0 4, then through a column packed with silica gel/NaOH, silica gel/AgN03 and silica gel. The hexane eluent is concentrated by evaporation and transferred to an alumina column. The PCBzs are eluted with 2% methylene chloride in hexane, and the PCDDs and PCDFs are eluted in a second fraction using 50% methylene chloride and hexane. After concentration, the residue is ready for analysis. Table 3 gives other cleanup methods. Flow Data (mass transfer): One ton of refuse yields, on average, 250kg slag; 30kg fly ash and 7000 m3 of flue gas containing: 3.5kg CO, 0.05kg HF, 1.3kg NO^* 65kg SO , 3.15kg HC1 and 0.66kg particuiates. SUBJECT TO PROTECTIVE ORDER. 176 r . ? 3 s' ! n f t attorney w o rk product t -'."Mc v .r' ,p-MT P^'VILEGE Chemistry of Formation: Possible from three sources in incinerator emissions. 1. PCDDs and PCDFs are trace components in refuse and not effectively destroyed. The authors found none in compost. They say there is indirect evidence that PCDDs and PCDFs are not biodegraded in the composting process (limit of detection 10 ppt). Also, it has been reported that a sample of municipal waste did not show PCDDs present. 2. PCDDs and PCDFs are formed from chlorinated precursors such as PCBzs, PoCPs and PVC during combustion. There is evidence for the following: PVC PCDDs PCDFs 1 PCDDs I P'CCDDFs The authors point out there is very little direct evidence that PCDDs and PCDFs are formed from these compounds under normal operating conditions of real incinerators. Table 8 gives studies on pyrolysis of PVC. There is a minor yield of PCBzs. Proposed mechanism: PVC --- -- --- > free radicals '-- -- -- ^ PCBzs -HC1 Table 9 summarizes pyrolysis studies of PCBzs. Pyrolysis in air yields PCDDs and PCDFs. The authors propose that thermal oxidation with oxygen takes place. The chlorophenols (PoCPs)formed react with the PCBzs to give polychlorinated diphenyl ethers (PCDPEs) which cyclize to either PCDDs or PCDFs or the PoCPs can react with each other to form PCDDs. Table 10 summarized combustion and pyrolysis experiments of PoCPs to PCDDs. Mentions 3 routes. SUBJECT TO PROTECTIVE ORDER. 177 3 4 n n ATTORNEY WORK PRODUCT a t t o r n e y -c u e n t PRIVILEGE 1. dimerization directly to PCDDs including Smiles rearangeraent. This is most important route. 2. dechlorination of higher chlorinate PCDDs 3. cyclization of "predioxins" (chlorohydroxy diphenyl ethers) already present in chlorophenols. III. Table 11 gives studies on pyrolysis to PCDFs. Four routes involved. Does not elaborate. Table 12 gives results of pyrolysis of 2,4,5-T derivatives. Formed 2,3,7,8-PCDD, but pure 2,4,5-T appears not to' form it. Finally, de novo formation of PCDD from carbon sources and natural chlorine donors could be operating. Very little direct evidence. Dow's studies and the author's findings of PCBzs in fly ash from coal-fired powerhouses. Fuel Chlorine (ppm) Coal Refuse Paper Leaded Gasoline Unleaded Gasoline Fuel oil 1300 2500 300 to 1600 300 1-6 NA Isomers Identified: Up to the time of this article, only qualitative data have been reported for groups of compounds (PCBzs, PCBs, PCDDs) or chlorine no. isomer clusters and not individual isomers. See Table 5. Quantitative data for PCDDs and PCDFs as chlorine no. isomer clusters are given in Table 6. Analytical Techniques Mentions packed column and capillary column GC and MS. sPeci icity: Using proper cleanup procedures, capillary GC and MS, individual isomers can be quantified using standards. Sensitivity: Can measure ppt levels. IV. Comments (Significant Data, Graphs, etc.) Mentions that packed LC columns separate chlorine no. isomer clusters in only 4 to 6 peaks. Separation into specific isomers requires a combination of capillary columns MRLC and GC methods with use of authentic PCDD individual isomers as standards. For quantitation, GC/MS analysis is performed and areas are compared with known standards. In this way, the amount of chlorine no. i v* -i k -.;"AL SUBJECT TO PROTECTIVE ORDER. 178 attorney w o rk product *TTCPNEY-CLiENT ORI'/ILEC-E isomer groups or individual isomers can be quantified. In Lustenhouwer's work, 4-raethyl-21, 5'-dichlorobiphenyl (MDCB); 1,2,3,4-TCDD, OCDD and OCDF were used as standards. Table 5 gives fly ash analyses from 35 municipal incinerators, (different designs and operating conditions). Since PCDDs and PCDFs were present in all samples, the authors claim that the presence of these compounds in incinerator emissions is a general phenomenon. Table 7, part b shows that the distribution of chlorine no. isomer groups is fairly constant-concentration in particulates in stack gas is greater than in fly ash. Mentions that a national panel of analytical experts from the U.S. (Ref. 26) found Dow's analytical methodology to be generally sound and suitable for detection of PCDDs at ppt levels (referring to Citation No, 13 - Trace Chemistries of Fire). Mentions Kimble and Gross's negative report of PCDDs in stack particulates from a coal fired powerhouse (Citation No. 39) but indicates the extraction procedure used gave poor PCDD recovery. The authors own analysis of fly ash from a coal-fired powerhouse at ppb levels was negative. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 179 II III. ATTORNEY W ORK PRODUCT Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): N. H. Mahle and L. F. Whiting (Dow) Title: The Formation of Chlorodibenzo-p-dioxin by Air Oxidation and Chlorination of Bituminous Coal Reference : Chemosphere, 9, 693-699 (1980) Citation No: 67 Source of Dioxins Source: Coal residue and off-gas emission from the combustion of NBS bituminous coal No. 1632A at 600C. in the presence of Cl2 , HC1 and sodium chloride in a laboratory furnace. Sampling Techniques: Attached to the end of the quartz reaction tube was a three stage trapping system-two ambient temp, glass wool traps and one ice-water chilled glass bead trap. A separate reaction tube and trap were used for each experiment. The glass wool and beads were Soxhlet extracted with benzene for one extract. The coal residue was extracted the same way thus giving a second extract. Each extract was sequentially chromatographed on activated silica gel, sulfuric acid coated silica gel, sodium hydroxide coated silica gel, and activated silica gel. The evaporated extract was then chromatographed on silver nitrate coated silica gel and basic alumina followed by reverse phase HPLC separation where one fraction was collected for the TCDDs and another for the Cl6 , CI7 and Clg dioxin isomers. Flow Data (mass transfer): Two grams of coal combusted with air introduced at 50cc/min yielding an average residence time of 10 sec. Chemistry of Formation: Not discussed Isomers Identified: TCDDs, HCDDs, HpCDDs and OCDD as chlorine no. isomer clusters Analytical Techniques Used HPLC followed by packed column GC/MS with SIM mode. Specificity: PCDDs as chlorine no. isomer clusters Sensitivity: 0.003 - 3ppb depending on sample and chlorine no. dioxin isomer cluster concentration SUBJECT TO PPnTrrrn/c- 180 n ATTORNEY WORK PROfV ir r IV. Comments (Significant Data, Graphs, etc.) Four experiments were carried out to determine control levels of chlorodioxins associated with; (1) coal - no detectable chlorodioxin (2) HC1 - no detectable chlorodioxin (3) CI2 + air - no detectable chlorodioxin (4) coal + air at high temp. - gave HpCDDs and OCDD slightly above detection limits. Experiment #5: coal - air - NaCl - same level of chlorodioxins as with coal - air. Experiment #6: coal - air - HC1 - substantial amounts of chlorodioxins at C14| Cl6j Cl7 and Cl8 chlorine no. isomer clusters. Experiment //7: Coal + air + CI2 - largest amount of chlorodioxins at all chlorine no. isomer clusters. Similar results obtained with a locally purchased uncharacterized coal. Published reports suggest that coal mixed with sodium chloride can possibly form chlorodioxins under conditions other than those tested here. SUBJECT TO PROTECTIVE ORDER. 181 C23411 ATTORNEY WORK PRODUCT *-- - 'cy.f McMT PRIVILEGE 'Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): S. Miller Title: Quality Assurance, Analytical Methods, and Hazardous Wastes Reference: Environ. Sci. Technol., 16, 332A-336A (1982) Citation No : 68 Source of Dioxins Source: Fly ash and stack emissions from a municipal refuse incinerator in the U.S. Sampling Techniques: Fly ash was collected from ESP. The stack emissions were collected by an SASS train as well as by a modified Method 5 train. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Mentions that fly ash had at least 18 and probably all 22 TCDD isomers, including 2,3,7,8-TCDD. Also TCDFs were found - at least 16 isomers, including 2,3,7,8-TCDF. Analytical Techniques Best appears to be a 2 stage reverse phase HPLC followed by normal phase HPLC using Zorbax-ODS (methanol eluent) and Zorbax-SIL (hexane eluent) columns. The GC/MS with low or high resolution. Specificity: Sensitivity: Can separate the 22 TCDD isomers into groups that were then separated by GC and detected by MS. Not discussed Comments (Significant Data, Graphs, etc.) None CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. C23412 182 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): L. Morselli, et al Title: Analysis of the Eflluents of an Urban-Solid Refuse Incinerator: Study of Methods of Extraction and Analysis for the Quantitative Determination of Polychlorodibenzo-p-dioxins Reference: Annali di Chimica, 1981, 557-572 (Italy) Citation No : 69 II. Source of Dioxins Source: Fly ash, slag and smoke from an urban solid refuse incinerator in Bologna, Italy Sampling Techniques: The fly ash was taken from the ESP discharge and the slag was withdrawn at the incinerator exit. The same extraction and purification procedure was used on both types of samples. Extraction was by Soxhlet using hexane, toluene, benzene and xylene. The extracts were evaporated to 0.2 ml on a rotary evaporator and purified by elution through a silica column (hexane). The eluate was concentrated to 0.2 ml under a eluting N2 flow and first with 2%trmaentshfyelrerneed to an alumina column chloride in hexane (elutes PCBs) and then with methylene chloride-hexane (50/50) (elutes PCDDs and PCDFs). The smoke was withdrawn through a condenser cooled to 20C. and then bubbled through ethylene glycol. The particulates were collected on glass wool inside the sample probe. The aqueous condensate and ethylene glycol (water added) were extracted with methylene chloride. On evaporation of the methylene chloride, the residue was dissolved in 1ml of benzene and analysed. The particulates were treated in a manner similar to the fly ash and slag (xylene Soxhlet extraction). Also, thermal desorption (300C to 850C.) and steam extraction (300C.) were carried out on fly ash (5g) in a flow of 5 ml/min of N2 . The gases were passed through ethylene glycol (ice-water bath). The ethylene glycol and the residual fly ash were extracted with xylene, and cleaned up and analysed as the other samples. CONFIDENTS AJL SUBJECT TO PROTECTIVE ORDER. 183 C23413 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Although Table 1 shows 2 specific HCDD isomers (1,2,4,6,7,9" and 1,2,3,6,7,8-HCDD) as well as total HCDDs, 2 HpGDDs and OCDD, the authors state that the chlorine no. isomer clusters of PCDDs and PCDFs are not separable under the GC conditions employed. This is consistent with the capability of the analytical methods claimed to be used. If Table 1 is correct, a GC/MS procedure surely must have been used. Analytical Techniques Used packed column GC with Ni63 electron capture detector. Specificity: Presumably separated PCDDs and PCDFs as chlorine no. isomer clusters; e.g. TCDDs + TCDFs as one cluster, HCDDs + HCDFs as another cluster. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) One of the goals of this study was to determine the optimum extraction procedure. The conclusion was that "extraction becomes more efficient with increase in molecular complexity of the solvent. Thus, of the solvents tried, Soxhlet extraction with xylene proved to be the best. With thermal desorption and steam extraction, no PCDDs were found. Results from solvent extractions and steam extraction indicate that dioxins are not adsorbed on fly ash but are entrapped in an organic matrix. Analysis of the various fractions of smoke as well as wash liquids of the probe show that PCDDs are in the gaseous state. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 184 023414 I. II. III. IV. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): R. A. Neal, et al Title: Studies of the Mechanisms of Toxicity of 2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD) Reference: Annals New York Academy, 204-213, (1979) Citation No : 78 Source of Dioxins Source: NA Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: NA Isomers Identified: 2,3,7,8-TCDD Analytical Techniques NA Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) The extreme lethality of 2,3,7,8-TCDD, particularly in the guinea pig, suggests that the compound is probably affecting some fundamental process in animal cells leading to a general dysfunction of those cells. The most reasonable hypothesis at this time concerning the biochemical mechanism is that it binds to a receptor in the cytosol fraction of mammalian cells, is transferred into the nucleus and increases or decreases the synthesis of a critical protein(s) or enzyme(s). This increase or decrease in critical protein or enzyme levels leads eventually to a generalized dysfunction of a number of different cell types leading eventually to death. What biochemical function(s) are affected is unknown at this time. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 185 G23415 >. ) Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins A TM ? n NEY W O RK PRODUCT ATTORNEY-CLIENT PRIVILEGE I Citation Author(s): T. J. Nestrick, et al Title: 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. Reference: Environ. Sci. Res., 26, 95-112 (1983) Citation No: 70 II Source of Dioxins Source: Preliminary evaluation: Flue particulates from an oil heating system and an exclusive wood heating system in Cape Cod, MA as well as from a' primary heating system near Midland, MI. Survey evaluation: All samples were chimney particulates from modern firebrick and metal furnaces. (1) Eastern region - from 6 furnaces vented through uninsulated flues to masonry chimney. Near Farmington, NH, an agricultural community. Burned red oak. (2) Central region - from 4 furnaces near Grand Marais,' MN, a tourist and logging area. All had uninsulated flues, but one had a masonry chimney and the others used the uninsulated flue as the chimney. Also from 2 furnaces similar to those from the Eastern region - one near Duluth, MN (an old farm) and one near Escanaba, MI (upper peninsula). Burned birch. (3) Western region - from 6 furnaces near Cresvell, OR with insulated metal flues that also served as chimneys. Burned fir. Sampling Techniques Particulate samples (25-65g) were transferred from the source, using a clean kitchen spoon, to clean glass bottles with Poly-seal caps and Teflon tape - wrapped threads. CO NFID EF^ &L SUBJECT TO PROTECTIVE O R D E a 186 CS3416 III. ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Preliminary evaluation samples: No details on the flue particulate sampling of the exclusive oil or wood heating systems in Cape Cod, MA. For the Midland, MI wood furnace, particulates were collected at the base of the masonry chimney, the rear portion of the flue after the draft control (flue-back), the front of the flue after the heat exchanger (flue-front) and from the ash pit. Eastern samples - collected from the base of the masonry chimneys. Central samples - collected from the masonry chimney base of 3 furnaces and from the spark-arrester baffle at the top of the uninsulated flue pipe (chimney) of 3 furnaces. Western samples - collected from the spark-arrester baffle at the top of the insulated flue pipe (chimney). Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Preliminary evaluation: (1) Wood furnace - TCDDs, HCDDs, HpCDDs and OCDD Oil furnace HpCDDs and OCDD (considerably less than wood furnace) (2) Wood furnace at Midland, MI - 16 TCDD isomers., TCDDs, HCDDs, HpCDDs and OCDD. Regional sampling: All three regional samples gave the following: 20 TCDD isomers, HCDDs, HpCDDs and OCDD. % 2,3,7,8-TCDD to. total TCDDs = 0-13% (avg. 5%) Analytical Techniques Used HPLC and reverse phase HPLC followed by HRGC/LRMS in the MPM and SIM modes and HRGC/HRMS in the MPM and SIM modes and HRGC/HRMS in the MPM mode. Specificity: Isomer specific for TCDDs; chlorine no. isomer clusters for HCDDs, HpCDD; and OCDD. Sensitivity: 2.5 times the noise level. 0.2-7.7 ppt depending on PCDD concentration level. CONFIDE!* 4? SUBJECT to ^ T E C T IV E O R D E fT 0 23417 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Comments (Significant Data, Graphs, etc.) This paper reports preliminary results from the analysis of 10 of the 18 regional samples collected. The complete results are covered in Citation No. 71 and the critical and significant points are documented there. PCDFs were found to be major components in these flue particulates. In one of the Eastern regional samples, the TCDFs measured 200 ppb compared to 1 ppb of TCDDs. The apparent isomer distribution for TCDFs is similar to that for TCDDs, in that a large number of isomers are present (38 possible TCDFs) at reasonably similar levels. This also indicates that the origin of these TCDFs is not likely to be related to the presence of specific man-made precursors. The fact that unchlorinated dibenzofuran was identified in the Eastern regional sample whereas unchlorinated dibenzo-p-dioxin was not, may indicate that the PCDDs and PCDFs are produced by different mechanisms during wood combustion. PCDD concentrations increase with increasing degree of chlorination whereas PCDF concentrations increase with decreasing degree of chlorination. Apparently MCDFs, DCDFs, TrCDFs, TCDFs, and PeCDFs are present. TrCDFs and TCDFs were definitely confirmed by HRGC/HRMS. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 188 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): T. J. Nestrick and L. L. Lamparski Title: Isomer-Specific Determination of Chlorinated Dioxins for Assessment of Formation and Potential Environmental Emission from Wood Combustion Reference: Anal. Chem., 54, 2292-2299 (1982) Citation No: 71 II. Source of Dioxins Source: See Citation No. 70 Sampling Techniques : See Citation No. ,70. Sample preparation was not discussed in Citation No. 70 but is in this paper. The analytical procedure developed to permit HRGC/LRMS has 5 steps: 1. Benzene Soxhlet extraction of the flue particulates 2 . gross impurity removal from the extract by chemically modified adsorbent treatments [silica, basic alumina, cesium-alumina, 33% 1M NaOH on silica, 44% H2SO4 on silica, 22% H2SO4 on silica (benzene and hexane as elutants)] 3. specialized adsorbent treatment to remove common chemical interferences [10% AgN03 on silica, 33% 0.2M KMn04 and 0.1M NaOH on silica-AW(50% CC14 in hexane elutant discarded, 50% CH2CI2 in hexane, and hexane as elutants]. 4. RP-HPLC residue fractionation to remove residual chemically similar interferences and to permit collection of PCDDs in clusters according to degree of chlorination (congeners) (hexane elutant). The higher chlorinated PCDDs fractions are dissolved in isooctane and analysed by HRGC/LRMS. 5. silica-HPLC refractionation of the RP-HPLC TCDD fractions to provide a second high efficiency chromatographic separation with different selectivity to further remove interferents and to permit TCDD isomer specificity (hexane elutant). The 4 silica-HPLC fractions are ready HRGC/LRMS. SUBJECT TO PROTECTIVE ORDER. 189 023419 III. IV. Flow Data (mass transfer): Not discussed ATTORNEY W ORK PRODUCT ATTORN'E','-CLIENT PRIVILEGE Chemistry of Formation: Not discussed Isomers Identified: See Citation No. 70 Analytical Techniques See Citation No. 70 Specificity: Isomer specific for TCDDs; chlorine no. isomer clusters for HCDDs, HpCDDs; and OCDD Sensitivity: 2.5 times the noise level. 0.2-11 ppt depending on PCDD concentration level Comments (Significant Data, Graphs, etc.) For all regional samples in which one or more TCDD isomer was observed, the % 2,3,7,8-TCDD relative to total TCDD was 0-16% with the average of 5%. This average composition for 2,3,7,8-TCDD is representative of rural regions and is similar to the 3.3% 2,3,7,8-TCDD observed for the Midland RWC chimney particulates where locally obtained wood was from an industrialized area associated with production of chlorinated compounds. Conclusions PCDD formation appears to be related to the natural chlorine content of the wood fuel rather than external environmental sources. In a published study by TRW, eleven different varieties of wood were quoted to contain 14-84 ug/g. Typical RWC units located in rural areas are a source of PCDD emissions to the environment. The observation of a relatively flat distribution pattern for TCDD isomer concentration suggests that their formation in wood fueled RWC units may be a random statistical process where each of the 22 TCDD isomer is equally favored. Although these results suggest that wood combustion may be a potential significant contributor to environmental PCDD background levels, additional research is necessary to confirm "The trace chemistries of fire" hypothesis and to better characterize the magnitude of this source. Because it has been estimated that particulate emissions from forest fires in the U.S. alone range from 0.5 x 106 and 54 x 106 tons/year, the authors find it difficult to believe that PCDDs are not ubiquitous in the environment. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 190 C2342U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Iadustrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): R. N. Ogg and J. H. Menczel Title: Disposal of Hazardous Wastes: Problems and Pitfalls Reference: Journal of the Air Pollution Control Assoc., 31, 127-132 (1981) Citation No: 72 II. Source of Dioxins Source: Emissions of the boiler stacks of a municipal solid waste disposal facility located on Long Island, NY. The facility burns refuse derived fuel (RDF) Sampling Techniques: Type of samples taken and analysed were not discussed Flow Data (mass transfer): Not discussed III. Chemistry of Formation: Not discussed Isomers Identified: TCDDs and 2,3,7,8-TCDD specifically Analytical Techniques Not discussed Specificity: TCDDs and 2,3,7,8-TCDD specifically at the ppt level. Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) EPA tests were performed in July and August, 1979 - results were available in Dec., 1979.. The results showed that several toxic compounds were in the plant's emissions, but appeared to be at low enough levels not to pose an unacceptable risk to the community. Since chlorinated phenols were identified, the samples were analysed for TCDDs. Their presence, including 2,3,7,8-TCDD, was confirmed. Because of the sampling method, an accurate emission rate for TCDDs could not be determined. Also, it was not known if the presence of TCDDs were peculiar to the wastes burned during the test, was due to the specific process used at the plant, or was a characteristic of municipal solid waste combustion. Also, it was not known whether the emissions posed an unacceptable health threat to the community. CONFIDENTI M SUBJECT TO PROTECTIVE ORDER. 191 C2342 ATTORNEY W ORK PRODUCT ATORNEY-CUENT privilege Because the scientific experts could not agree on the significance of low level exposures, the citizens requested that EPA perform a health study in the community including physical exams and medical tests on members of the community. CONFIDENT* AT SUBJECT TO PROTECTIVE ORDER. 192 CS3432 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): K. Olie, et al Title: Chlorodibenzo-p-dioxins and Chlorodibenzofurans are Trace Components of Fly Ash and Flue Gas of Some Municipal Incinerators in the Netherlands Reference: Chemosphere, 6, 455-459 (1977) Citation No: 73 II. Source of Dioxins Source: Fly ash, and particulates and liquid condensate from flue gas from three municipal incinerators at Arnhem, Amsterdam and Alkmaar, Holland. Chemical waste, as a rule, was not incinerated. Sampling Techniques: The fly ash was taken from the ESP. Flue gas samples were taken at the duct between the ESP and the chimney. The flue gas sample probe had a glass fiber filter to remove the particulates. A portion of the gaseous emissions were diverted through the probe and routed through an ice-cooled condenser to collect the liquid condensate. The fly ash samples were Soxhlet extracted with a nonpolar (benzene or toluene) and a polar (methanol or methylene chloride) solvent. The residue remaining after most of the solvent was evaporated was ready for analysis. The flue gas condensate was extracted with methylene chloride. After solvent evaporation, the residue was ready for analysis. Flow Data (mass transfer): Not discussed Chemistry of Formation: The article suggests that organic material such as polyethylene and inorganic chloride may form chlorobenzenes (large quantities found in the fly ash in this study) which form chlorophenols (also found in the flue gas condensate). The chlorophenols are most probably the precursors of the PCDDs and PCDFs. Isomers Identified: Fly ash: TCDDs (5 isomers including 2,3,7,8-TCDD), PeCDDs (5 isomers), HCDDs (4 isomers), HpCDDS (2 isomers) and OCDD TCDFs, PeCDFs, HCDDs, HpCDDs, and OCDF __ __ Flue gas condensate: TCDDs, PeCDDs, HCDDs, HpCDDs and OCDD. CONFIDENT* C lio ttrr-r t nnATr/'m/i-- 193 023423 XU. IV. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Analytical Techniques Used packed column GC/MS with SIM mode PCDDs and PCDFs as chlorine no. isomer clusters. Specific isomers were separated but, except for 2,3,7,8-TCDD, OCDD and OCDF, were not identified. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) The most abundant chlorinated compounds in the fly ash were highly chlorinated benzenes. The most abundant chlorine compounds in the flue gas condensate were chlorophenols. The authors made the following comments: The amount of PCDDs and PCDFs entering the atmosphere via flue gases is probably quite small. Due to the extreme toxicity of some of the isomers and the fact that most incinerators are located in densely populated areas, extensive monitoring might be advisable. Since the origin of PCDDs and PCDFs in fly ash and flue gas of municipal incinerators is unknown and conditions of high temperature are most likely important, emissions of other installations from industry and energy production should be investigated. Municipal incinerators and other combustion processes may be the source of some of the organochlorine compounds in the environment. SUBJECT TO PROTECTIVE ORDER. 194 ATTORNEYWORKPRODUCT MV r\ ;-m t or>\/ipg Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): K. Olie and 0. Hutzinger Title: Detection of Polychlorodibenzodioxins and Fly Ash and Flue Gas of Municipal Incinerators Reference: Recent Dev. Mass Spectrom. Biochem. Med., 1_, 555-562 (1978) Citation No: I k II. Source of Dioxins Source : Fly ash and flue gas from municipal incinerators in Holland. This article presents the same information as Citation No. 73. Stresses the development of a computer program for specific detection of organochlorine and organobromine compounds. III. IV. Sampling Techniques: Not discussed. See Citation No. 73. Flow Data (mass transfer): Not discussed Chemistry of Formation: Some of the same suggestions present here as in Citation No. 73. Isomers Identified: Records the same data on PCDDs as in Citation No. 73. Analytical Techniques Used packed column GC/MS with SIM mode and computer program for organochlorine and organobromine compounds. See Citation No. 73. Specificity: See Citation No. 73. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) Some of the comments and conclusions given in Citation No. 73 are restated here. No new significant points or data. SUBJECT TO PROTECTIVE ORDER. 195 \ n if ^ I. II. III. ATTORNEY W ORK PRODUCT '"'"'"'"M T PRIVILEGE ,Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): K. OLie Title: New Techniques in Organic Trace Analysis Reference: Erdoel Kohle, Erdgas, Petrochem., 33, 136 (1980) Citation No : 75 Source of Dioxins Source: Fly ash from a municipal incinerator. No new data on PCDDs or PCDFs from incinerators is presented. Does mention certain information presented in Citation Nos. 73 and 74. Stresses most up-to-date technology of extraction, cleanup and analysis of PCDDs and PCDFs in incinerator fly ash. Sampling Techniques: Not discussed. Mentions that, in the identification phase of an experiment, a cleanup procedure should be as mild as possible. The author used a modification of the Dow separation and cleanup procedure (The Trace Chemistries of Fire, 1978). Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Mentions identification of PCDDs and PCDFs as chlorine no. isomer clusters. Also, 2,3,7,8-TCDD isolation and identification. Analytical Techniques Uses LC with selective adsorbants and GC/MS with SIM mode and "Haltest" (a computer program specific for organochlorine and organobromine compounds). Also, for specific isomer determination and quantification, reverse phase HPLC coupled with GC/MS is recommended. Specificity: See analysis scheme below Sensitivity: Not discussed SUBJECT TO PROTECTIVE ORDER. 196 G4 34 26 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data, Graphs, etc.) Fly ash sample HC1 treatment (causes higher recovery of desired ^ compounds) Soxhlet extraction l Concentration i Silica/sulfuric acid l Silica/sodium hydroxide i Silica/silver nitrate Alumina hexane:CH2Cl2 (50:1) GC/MS chlorinated benzenes 2,3,7,8-TCDD The use of GC/MS is necessary to separate chlorodioxins from chlorodibenzofurans. Electron capture detector can tell that there is no TCDD in a sample but can never conclude that there is TCDD in the sample. The two classes can be quantified in one GC/MS run using the SIM mode. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 197 023427 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of v T Chlorinated Dibenzo-p-dioxins I . Citation Author(s): K. Olie, J. W. A. Lustenhouwer and 0. Hutzinger Title: Polychlorinated Dibenzo-p-dioxins and Related Compounds in Incinerator Effluents Reference: Pergamon Ser. Environ. Sci., 5, 227-244 (1982) (From Proceeding of a workshop, "Impact of Chlorinated Dioxins and Related Compounds in the Environment", Rome, Italy, Oct. 22-24, 1980) Citation No : 76 II. Source of Dioxins Source: Fly ash and flue gas particulates from 9 municipal incinerators in Holland (Alkmaar, Amsterdam, Arnhem, Leewarden, Leiden, Rijnmond, Roosendaal, Rotterdam and Zaanstad). Sampling Techniques: Fly ash samples were taken from the ESP. Particulates in flue gas were collected with a Sartorius E.M. 100 sample apparatus. Isokinetic sampling was used and the amount of particulate per Nm3 was determined by weighing the filter before and after sampling. The fly ash samples cleanup and separation of the chlorobenzenes from the PCDDs and PCDFs were done according to the method given in Citation No. 75. The particulate samples were done the same way except treatment with 3% HC1 was omitted. Toluene was used to Soxhlet extract both the fly ash and the particulates. Flow Data (mass transfer): Avg. cone, and estimated yearly output of PCDDs and PCDFs. CI4 to Clg PCDDs Cl4 to Cl8 PCDFs Fly ash ng/g kg/yr. 2056 1309 123.3 78.5 Flue gas ng/Nm3 kg/yr 1540 1322 21.6 18.6 Chemistry of Formation: While the absolute amounts of the chlorobenzenes, chlorinated dioxins and chlorinated dibenzofurans vary considerably, the relative amounts (the proportions of compounds to each other) are fairly constant. This supports the hypothesis CONFIDENT! a SUBJECT TO PROTECTIVE ORDER. 198 023428 attorney w o r k product ATTORNEY-CLIENT privilege that all the compounds are formed from one or several compounds which are in equilibrium with each other. These precursors (chlorobenzenes) are not necessarily compounds which are components of the waste. It is more likely that one or more compounds in the waste form the precursors. For example: PVC chlorobenzenes - PCDDs PCDFs Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs as isomer clusters and OCDD TCDFs, PeCDFs, HCDFs, HpCDFs as isomer clusters and OCDF III. Analytical Techniques Used GC/MS with SIM technique Specificity: PCDDs and PCDFs as chlorine no. isomer clusters Sensitivity: Not discussed JV. Comments (Significant Data, Graphs, etc.) Tables 1 through 6 give the analytical results. Table 7 gives the average concentration and estimated yearly output of PCDDs and PCDFs in fly ash and flue gas from the municipal incinerators in Holland. Table 8 lists the number of toxic components per isomer group based on the premise that 3 or 4 chlorines are in the lateral positions, (positions 2,3,7 and 8) and at least one unhalogenated position in the other positions. It has been estimated that these other toxic isomers of PCDDs and PCDFs have a toxicity of roughly 10% compared to 2,3,7,8-TCDD. Tables 9 and 10 give the "toxic equivalents" in the fly ash and flue gas (estimated for 1 year). Fly ash_____________ ___________ Flue gas Compounds PCDDs Total Toxic Amt./Yr. Equiv./yr. k k 102.6 5.9 Total 2,3,7,8-TCDD Amt./Yr. kg 0.2 15.3 Toxic Equiv./yr 890 2,3,7,8-TCDD 26 PCDFs 75.4 4.1 17.6 998 Total 178.0 [-fi/iAX. 32.9 SUBJECT TO PROTECTIVE ORDER 1QQ 1888 023429 ATTORNEY W ORK PRODUCT A TlO R N t r-C^iciNT PRIVILEGE The conclusion the authors draw is that the fly ash extracts are estimated to be ~ 50 times as toxic as based on 2,3,7,8-TCDD content. For the flue gas, the factor is ~ 80. The HCDDs, HpCDDs and HCDFs contribute greatly to the toxicity of the extracts, while 2,3,7,8-TCDD does not contribute as much as one might think. SUBJECT TO PROTECTIVE ORDER. 200 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W ORK PRODUCT A T T C 'l .c N i PRIVILEGE Citation Author(s): K. Olie, et al Title: Reference: Formation and Fate of PCDD and PCDF from Combustion Processes Chemosphere, 1 2 , 627-636 (1983) Citation No: 77 Source of Dioxins Source : Experiments were run to learn more about the mechanism of formation of PCDDs and PCDFs. 1. Flue gas'from burning waste plus added hexachlorobenzene in a municipal incinerator. 2. Fly ash from burning painted wood at least 60 years old, new wood impregnated with PCP, and paper treated with hypochlorite in a fluidized bed oven. 3. Emissions from burning lignin sulfonate in the presence of HC1 or PVC at 590C. Also, dispersion modeling experiments were performed regarding the emissions of PCDDs and PCDFs from a municipal incinerator at Zaanstad, Holland. At two points in the neighborhood, the air was sampled and the filters extracted and analysed for PCDDs and PCDFs. Also, the fly ash was extracted and analysed for PCDDs and PCDFs. Sampling Techniques: Details of the sampling was not discussed. Flow Data (mass transfer): From the analysis of extracts from the air filters and the fly* ash and dispersion modeling, the highest concentration determined (Location A) for PCDDs and PCDFs is 47.2 pg/m*123 or 1.54 pg tox. equiv./m3 . Because of the limited number of samples, these results are only an indication of the air concentration (see Table 5). Table 6 gives the flue gas avg. emission cone, of PCDDs and PCDFs by chlorine no. isomer clusters for the Zaanstad incinerator. This is 2076 ng/Nm3 or 119.2 ng/Nm3 Tox. equiv. This is ~ 85 - f times higher than the toxicity based on | 5^ J . ^ , 3 ,7 ,8-TCDD cone, alone (1.4 ng/Nm3). This ** * incinerator, in 1979, burned 100,439 tons of waste -- prllVE. O R D E R * waste (1 ton of waste = 8000 Nm3 of emissions) ^ for an avg. emission of 25.48 Nm3/sec. (3 ug Tox. equiv.) 201 0 2 3 4 a 1 ATTORNEY W ORK PRODUCT ... il PRIVILEGE III. IV. Chemistry of Formation: The authors say that the formation of PCDDs and PCDFs from PCBs, chlorinated benzenes and chlorophenols have been demonstrated in lab experiments. Whether they play a significant role in incinerators is not known. Isomers Identified: PCDDs: TCDDs, PeCDDs, HCDDs, HpCDDs as chlorine no. isomer clusters and OCDD PCDFs: TCDFs, PeCDFs, HCDFs, HpCDFs as chlorine no isomer clusters and OCDF Analytical Techniques Not discussed Specificity: Chlorine no. isomer clusters for PCDDs and PCDFs. Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) The studies reported here were performed to expand the information on the mechanism of formation of PCDDs and PCDFs, their fate in the environment, and toxicological aspects (e.g. bioavailability of those adsorbed). To date, the data was very limited. A. Mechanism of Formation Table 1 gives the results of burning waste with added hexachlorobenzene in a municipal incinerator no clear increase in PCDDs or PCDFs. Table 2 gives the results of burning old painted wood, new wood treated with PCP, and paper treated with hypochlorite in a fluidized bed oven.. Adding PCP did not increase the level of PCDDs or PCDFs in the fly ash. Also, when the hypochlorite treated paper was burned, the fly ash contained very low levels of PCDDs and PCDFs (may be artefacts from the previous wood burning). Table 3 gives the results of burning lignin sulfonate in the presence Of HC1 or PVC. C4 to Ca PCDDs and PCDFs were definitely formed. PCDFs > PCDDs. Table 4 gives the conversion efficiencies of the above experiments. CONFIDENTS 4 L SUBJECT TO PROTECTIVE ORDER. 202 C23432 _ . . I IXWUUV. I ATTORNEY-CLIENT PRIVILEGE B/ Risk Assessment (Toxicological Aspects) With the assumptions made in Table 6 , the flue gas filter extract is about 85 times higher than the toxicity based on 2,3,7,8-TCDD alone. For fly ash the factor is 45. Cytosol binding, AHH induction and fish toxicity have confirmed this. From the emissions data (Tables 5 and 6), a maximum of 3.6 pg toxic equiv. of PCDDs and PCDFs would be inhaled per day (accepted daily intake = 250 pg toxic equiv./day). This suggests that inhalation of air near the Zaanstad incinerator does not cause health problems due to PCDDs and PCDFs being emitted. C. Uptake from Contaminated Food From the emissions data from the Zaanstad incinerator and dispersion modeling calculations, the average concentrations at locations A and B are higher than the acceptable level. The regular consumption of food, especially milk and milk products, could lead to elevated health risks. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 203 023433 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): K. Payne Title: Chemistry and Toxicology of Polychlorodibenzo-p-dioxins Reference : J . Chem. Ind. (London), 1982, pp 298-300. Citation No : 117 II. Source of Dioxins Source: This is a review article thus NA Sampling Techniques: NA Flow Data (mass transfer): Nor discussed Chemistry of Formation: Figure 1 gives typical mechanism for formation of 2,3,7,8-TCDD from 1,2,4,5-tetrachlorobenzene Figure 2 shows mechanism for formation of 1,3,6,8-TCDD and 1,3,7,9-TCDD from dimerization of 2,4,6-trichlorophenate with Smiles rearrangement. Cl III. IV. Isomers Identified: NA Analytical Techniques NA Specificity: NA CONFIDENTI ATu SUBJECT TO PROTECTIVE ORDER. Sensitivity: NA Comments (Significant Data, Graphs, etc.) Table 2 gives acute oral toxicity (LD50) for guinea pig, rat and mouse for various DCDD through OCDD isomers expressed in ug/kg body wt. It has been suggested that the toxicity is related to the detoxification process of hydroxylation which takes place exclusively at the lateral positions. The presence of chlorine 204 C23434 t ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE substituents exclusively at these positions may prolong the in vivo life of laterally substituted PCDDs and thereby increase the toxicity of much smaller doses. T&btt 2 Acule o n t toxidty of polychlorinated dlbeu*^-dlo.\lm (PCDD) a p m i f d u (he dose upeeled lo c u n ihe deaths af 90 per m l of the animals within 30 days * Acute oral LD, la (p^/k| body weight) PCDD Guinea pig* Rat* Mouse1 Di 2,7 2.1 Tri 2.3.7 >1,000,000 >2,000,000 >300.000 30,000 >3000 T" " !:!:?:! 1 -- 2.3.7.I Peata 1,3,7,1 I.2.4.7,! H eu U ,3,4,7,1 1,2,3,6,7,1 1.2.3.7,1,9 Mixed isomeri Hepta 1,2,3,4,6,7,8 Ocia l,2,3,4,6,7,t,9 0.6 2.1 2 3 1100 73 70-100 60-100 >600 >100.000 22 (M) 45(F) 100,000 210 340 >3000 123 1230 >1440 >1,000.000 >4,000,000 - The results show that the lateral positions (2,3,7,8) must be chlorinated to give maximum toxicity, while chlorination in the peri positions (1,4,6,9) reduces toxicity. The reduction in toxicity due to chlorination in the peri positions is not nearly as significant as the removal of chlorine from one or more of the lateral positions. Mentions similar structure-biological activity with regard to enzyme induction of ''-aminolevulinic synthetase (ALAS) and aryl hydrocarbon hydroxylase (AHH). Table 3 shows enzyme induction activity of various PCDD isomers (DCDDs through OCDD). TvNr J ladaedo al t-am laolitrallrie add ayatbetaae (ALA) and aryl h)drocarboa hydroxylase (AHH) In I m nf cfckk emheyaa hy lajecltoa f rhlorodibeazo-p-dlnxlai loin eggs* Chlorodioxin ALA' AHH Umubcthated Mono 1 Di 2,3 2,7 y Tri 1A 4 W T a n 1A 3.4 1.3.6,! 2,3,7,! Peau 1A3.4,7 H eu IA 3.4.7.I 1A4,6,7,9 (90 per cent) O ni l,2,3,4,6.7,|,9 - - - - ++ - ++4 44 44 * - - 4 4. 4444 44 4.4 4 4 4 n CONFIDENT- M SUBJECT TO PROTECTIVE ORDER. 205 G23435 I. II. III. IV. ATTORNEY WORK PRODUCT / ."'"1 3NEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): A. Poland and E. Glover Title: 2,3,7,8-Tetrachlorodibenzo-p-dioxin: Studies on the Mechanism of Action Reference: Dev. Toxicol. Environ. Sci., 6, 223-239 (1980) Citation No : 79 Source of Dioxins Source: NA Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: NA Isomers Identified: 2,3,7,8-TCDD Analytical Techniques NA Specificity: NA Sensitivity: NA Comments (Significant Data, Graphs, etc.) The basic information presented in this article is also given in another article by these authors: A Model for the Mechanism of Action of 2,3,7,8-Tetrachlorodibenzo-p-dioxin, Dev. Toxocol. Environ. Sci., 5, 327-343 (1980). Also Estrogens in the Environment, McLachlan, ed. Elsevier/North Holland Inc., 1980. 2,3,7,8-TCDD is a prototype of a series of halogenated aromatic hydrocarbons that all (a) produce similar patterns of toxicity, (b) are approximate isostereomers, and (c) elicit common biochemical responses. The specific compounds include the analogous chlorinated dibenzofuran, azobenzene, azoxybenzene, and biphenyl. The toxicological and histopathic response to 2,3,7,8-TCDD and its congeners include:1 (1) Lethality - The cause of death is unknown, but animals show a slow wasting syndrome with a latent period before death which is species specific. There is an order of species sensitivity (acute- SUBJECT TO PROTECT/VE ORDER. 206 343 t ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE oral ID50): 1 ug/kg guinea pigs, 20 ug/kg rats, 100 ug/kg mice, and > 1000 ug/kg hamsters and bullfrogs. (2) Lymphoid involution - produces thymus, lymph node, and spleen atrophy accompanied by suppression of cellular immunity. (3) Embryotoxicity and teratogenesis - it is a potent erabryotoxin and teratogen in mice, rats and chicken embryo. (4) Chloracne and hyperkeratosis - Most common and characteristic sign of toxicity in humans. Also observed in rabbits, monkeys and hairless mice. (5) Liver damage - hepatocellular necrosis observed in rats, mice and rabbits. Also, a disturbance in hepatic porphyrin synthesis (hepatic porphyria). (6) Edematous syndrome - a characteristic lesion in chickens. Also seen in mice. (7) Bone marrow depression - reported in monkeys. The ultimate target organ, that tissue whose functional disruption leads to death, is unknown. The pharmacokinetics and drug metabolism of 2,3,7,8-TCDD has been thoroughly studies in the rat. It is concentrated in the liver and to some extent in fat with a whole body half-life of about 3 weeks. There is evidence that it is slowly and partically metabolized to as yet unidentified metabolites appearing in the bile. To date there are no reports of toxicity of 2,3,7,8-TCDD on any cell type in culture. 2.3.7.8-TCDD produces a 10 to 12 fold increase in hepatic aryl hydrocarbon hydroxylose (AHH) activity. Also, it induces hepatic <f-aminolevulinic acid synthetase (ALAS) activity. Most important is that for the PCDDs (as well as their congeners and PAHs) there is an excellent correlation between their potency to induce AHH and ALAS activity and their toxic potency. 2.3.7.8- TCDD is 30,000 times as potent as the PAH, 3-methylcholanthrene, and a single administration produces sustained enzyme induction which lasts over 35 days (a reflection of its long biological half-life). As a result of these findings, the following structure-activity relationship has emerged: 1. halogen atoms must occupy at least 3, and for maximal potency, 4 of the lateral ring positions (positions 2,3,7 and 8). 2. At least one ring position must be unsubstituted. CONFIDENTS SUBJECT TO PROTECTIVE ORDER. C 23437 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE 3. 2,3,7,8-TCDD and its approximate stereoisomers and their molecular structures can be thought of as roughly fitting into a rectangle 3 x 10A with halogen atoms (substituents) in the 4 corners. 4. the order of substitution is Br > Cl > F > NO2 Related to the above AHH induced activity, 2,3,7,8-TCDD, its congeners and PAHs have a great affinity for the hepatic cytosolic protein receptor site. The cytosolic protein binding affinity correlates well with the induced AHH activity and biological potency. (see Fig. 4, p. 230). Mechanism of Toxicity: The authors postulate that the toxicity of 2,3,7,8-TCDD and its congeners is mediated through the cytosolic protein receptor site; that is, the initial event in their toxic action is the stereospecific recognition and binding to the cytosolic binding species. It is suggested that the ligand-receptor complex controls a battery of genes, and the sustained expression (or repression) of one or more of these genes which are coordinately expressed in the observed toxic syndrome. The toxicity is probably related to the sustained occupation of the receptor and the relatively long biological half-life of these chlorinated aromatic compounds. SUBJECT TO PROTECTIVE ORDER. 208 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): C. Rappe, et al Title: Polychlorinated Dioxins (PCDDs), Dibenzofurans (PCDFs) and Other Polynuclear Aromatics (PCPNAs) Formed During PCB Fires Reference; Chemica Scripta., 20, 56-61 (1982) Citation No: 94 II Source of Dioxins Source: Soot samples and wipe tests from accidental PCB fires where 1. Oil filled capacitors burned with PCB filled capacitors. 2. Capacitor fire probably cause of electrical malfunction 3. PCB fire in State Office Bldg, in Binghamton, NY. Thermal PCB destruction in rotary cement kiln. Note: Item 3 was the only fire where TCDD was identified. Sampling Techniques: Wipe tests (Kleenex tissue, 1dm2) taken as follows: 1. On the floor in the capacitor room 2. On the floor close to the capacitor battery 3. On the wall in the capacitor room - 2m from capacitor battery, 3m above the floor. Flow Data (mass transfer): No data from accidental fires is useful. Cement kiln tests give quantity burned and rate of feed, but insufficient data for mass transfer calculations. Chemistry of Formation: CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 209 C2343y III. IV. Isomers Identified: ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE 2.3.7.8- TCDF plus 6 other TCDFs and 11 PeCDFs. 2.3.7.8- TCDD and other TCDDs Analytical Techniques HRGC-MS. Mass fragmentography was used operating in the El or NCI mode. Specificity: 2,3,7,8-TCDF, 2,3,7,8-TCDD Sensitivity: ng/g, ng/m2 Comments (Significant Data, Graphs, etc.) A comparison of the Skovde and the Stockholm fires shows that these two PCB fires produced quite different products. The Skovde fire is "normal" fire where mineral oil generated the heat. The major products were PCDFs and PCPYs. The Stockholm fire was caused by an electrical malfunction. The temperature in this fire was probably much higher than in Skovde. In this fire the PCBPs were the major products while PCDFs and PCPYs were minor. No PCDDs could be found in the above two fires. In the Rotary Cement Kiln tests for the destruction of PCBs, no PCDFs or PCDDs could be found in any of the effluent samples. In a PCB fire in the State Office Bldg, in Binghamton, NY, 2,3,7,8-TCDD and other TCDDs were identified in soot samples. SUBJECT TO PROTECTIVE ORDER. 210 0 2 3 4 4 [J V. ATTORNEY w o r k p r o d u c t ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): C. Rappe, et al Title: Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans by Burning or Heating Chlorophenates Reference : Chemosphere, 269-281 (1978) Citation No: 87 II. Source of Dioxins Source : Uncontrolled open burning of birch leaves or wood wool impregnated with two commercial sodium chlorophenate formulations (from a mixture of 2,4,6-tri-, 2,3,4,6-tetra-, and pentachlorophenol). Also open burning of birch leaves impregnated with _ purified sodium 2,4,6-tri and pentachlorophenate. Also micropyrolysis of one of the commercial formulations and the purified sodium chlorophenates at 280C. Sampling Techniques: The smoke gases were drawn through a glass funnel into a glass filter containing Norit PK, 0.5-lmm, charcoal or Amberlite XAD-2(20-50 mesh). After burning, the glass equipment was washed with methylene chloride and the adsorbent Soxhlet extracted using this wash solution. The extract was concentrated and the residue purified on a silica gel column using hexane as eluant. Further purification was done on an alumina column by elution with 2% and 50% methylene chloride in hexane. The 50% methylene chloride in hexane contained the PCDDs and PCDFs. This extract was concentrated and the residue dissolved in tetradecane for analysis. Flow Data (mass transfer): Not discussed Chemistry of Formation: The authors conclude thate the PCDDs are formed in three ways: (1) dimerization of chlorophenates (2) dechlorination or (3) cyclization of "predioxins" present as impuritries in the commercial formulations. 211 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Isomers Identified: TCDDs, PeCDDs, HCDDs, HpCDDs and chlorine no. isomer clusters and OCDD at ug/g chlorophenate Also 7TCDD, 3PeCDD, 8HCDD, 2HpCDD and OCDD isomers were identified. Analytical Techniques Used capillary GC/MS with El source using mass specific ion monitoring Specificity : Isomer specific Sensitivity: detection limit for TCDDs to OCDD = 0.01 to 0.2 ug/g chlorophenate Comments (Significant Data, Graphs, etc.) Mentions that Higginbotham (1968) first reported PCDDs from pyrolysis of chlorophenols. Rappe used two of the most commonly used'commercial chlorophenate formulations in this study (Servarex and Kymmene KY-5) on the Scandinavian market. PCDF isomers with the same chlorine no. as for PCDDs were found in the original formulations and burning extracts. Due to lack of suitable standards, no isomer identifications were made. 40-50 isomers were present in the formulations while only 10 were present in the burning extracts. The levels of most PCDFs were much reduced after burning but a few individual PCDFs increased. 2,3,7,8-TCDF was only a minor component in all samples. Most interesting is that burning and micropyrolysis of the purified chlorophenols did not generate PCDFs. Even more interesting is the final statement: ,(The burning of chlorophenates or material like wood shavings, plywood or waste oil containing chlorophenates seems to be a more important source to environmental pollution by PCDDs including 2,3,7,8-TCDD than the accidental burning of 2,4,5-T derivatives or vegetation treated with 2,4,5-T derivatives. Table 1 - Amounts of PCDDs .found in burning experiments of commercial chlorophenates applied to birch leaves and wood wool in ug PCDDs/g chloropheanates. Comparison of before and after burning is given. Table 2 - Same as Table 1 except purified sodium 2,4,6-trichlorophenate and pentachlorophenate was used. SUBJECT TO PROTECTIVE ORDER. ATTORNEY W ORK PRODUCT A T T O T T '- C TNT PRIVILEGE Table 3 - Lists the following PCDD isomers identified: TCDDs: 1.3.6.71.2.6.7- ; 1,3,7,9-; 2,3,7,8-; 1,2,3,8-; 1,2,6,9-; ; 1,2,8,9-, PeCDDs: 1,2,4,7,8-; 1,2,3,4,7-; 1,2,3,7,8-; HCDDs: 1.2.4.6.7.91.2.3.4.6.91.2.3.7.8.9- i 1,2,3,4,6,8-; 1,2,3,6,8,9-; ; 1,2,3,4,7,8-; 1,2,3,6,7,8-; ; 1,2,3,4,6,7-. HpCDDs: 1,2,3,4,6,7,9-; 1,2,3,4,6,7,8-, OCDD The main TCDDs from these studies are 1,3,6,8- and 1,3,7,9- both of which are comparatively biologically inactive. There was no indication that blanks (burnings) were run on untreated birch leaves or wood wool. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 213 C23443 ATTORNEY W ORK PRODUCT r...... 5'EY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I Citation Author(s): D. P. Redford, et al Title: Emissions of PCDDs and PCDFs From Combustion Sources Reference: Environ. Sei. Res., 26, 143-152 (1981) (in book "Human & Environmental Risks of Chlor-Dioxins and Related Compounds", Plenum Press, (1981) Citation No: 95 II Source of Dioxins Source: 1. Raw refuse derived fuel (RDF) incinerators for electricity generation 2. 85% coal and ~15% RDF incinerator for large scale conversion of heat to electricity Sampling Techniques: Sampling train consisted of: a heated probe which could traverse the stack isokinetically and not permit water to condense; a heated cyclone to collect particulates; a heated filter to collect small particulates; a condenser; a cooled XAD-2 resin trap to collect organics; and several impingers to protect the pump and other equipment. After each days run, each train was disassembled, and the the resin and filter traps were stored on ice (4C.). The probe and glassware were rinsed with H20, acetone and cyclohexane. All other material collected was refrigerated. Flow Data (mass transfer): For the coal/RDF incinerator, the feed was: coal at 14,000 kg/hr. and RDF at 2,300 kg/hr. Coal/RDF Incinerator: Mass emission of <151 ug/hr. and detection limit, in the fly ash, was <0.5 ng/g. RDF Incinerator: No PCDDs or PCDFs detected in fly or bottom ashes or aqueous effluent; they were detected in the flue gas but not quantified. Detection limit in ash = 0.5ng/g Chemistry of Formation: Not Discussed Isomers Identified: 2,3,7,8-TCDD. Also TrCDDs, HCDDs and HpCDDs as chlorine no. isomer clusters and OCDD. Also indicated minimum no. of isomers present. Same data for PCDFs CONFIDENT!Al Cimip/'T Tr\ _______________ ?U CS3444 III. IV. ATTORNEY W ORK PRODUCT A ; ;e y -c u e n t pr iv ileg e Analytical Techniques Fused silica capillary column HRGC/MS in the SIM mode Specificity: Isomer specific for 2,3,7,8-TCDD. For PCDDs and PCDFs, chlorine no. isomer clusters with indication of minimum no. of isomers. Sensitivity: RDF incinerator: Detection limit in fly ash = <0.5ng/g. coal/RDF incinerator: Detection limit in stack gas = <0.25ng/dscm; fly ash = <0.5ng/g; other samples = <10pg. Comments (Significant Data, Graphs, etc.) PCDDs and PCDFs were detected and quantified in a municipal waste combustor, but were not detected in a coal/RDF burning facility. The PCDDs and PCDFs observed in the former were only present in the stack gas and associated particulates and not in the fly ash as described in studies conducted at other waste combustion facilities (Bumb et al, (1980); Lustenhouwer et al, (1980). The absence of detectable levels of PCDDs and PCDFs in all the samples from the coal/RDF facility are in agreement with the results of Junk and Richard (1981) at the same facility. Supports other studies in facilities burning strictly coal [Harless and Lewis, 1980; Kimble and Gross, 1980 (Citation No. 39)] where no detectable levels of PCDDs or PCDFs were observed in fly ash. Based on the procedures used in this pilot plant study and the resulting detection limits, it appears that the coal/RDF burning facility is emitting far less (if any) PCDDs or PCDFs per kg of refuse burned than the municipal waste facility. SUBJECT TO PROTECTIVE ORDER. 215 C23445 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): H. 0. Rghei and C. A. Eiceraan Title: Adsorption and Thermal Reactions of 1,2,3,4-Tetrachloro-dibenzo-p-dioxin on Fly Ash from a Municipal Incincerator Reference: Chemosphere, lj^, 569-576 (1982) Citation No: 88 Source of Dioxins Source: Fly ash was from the Northwest Municipal Incinerator, Chicago, IL and were taken from below the ESP. The 1,2,3,4-TCDD was obtained from Analabs, New Haven, CT. Sampling Techniques: 1,2,3,4-TCDD was flash evaporized in benzene onto the fly ash in a gas chromatograph modified for use as a high temperature gas-particulate reaction system. High purity air and helium were used for vapor flow. Fly ash were extracted with benzene, the extract evaporated on a rotary evaporator and further reduced in a nitrogen gas stream. The sample was then analysed by GC and/or GC/MS. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: 1,2,3,4-TCDD and two TrCDDs Analytical Techniques Used capillary GC/MS with SIM technique Specificity: Measured 1,2,3,4-TCDD and two TrCDDs Sensitivity: Not discussed, however some recovery data indicated 2 ug TCDD was measured at one point Comments (Significant Data, Graphs, etc.) This article examines adsorption and thermal reaction (decomposition) of 1,2,3,4-TCDD on fly ash at 100-300C. in air and helium. Results show fly ash is not an inert substrate at temperatures above 100C. and that irreversable adsorption or SUBJECT TO PROTECTIVE ORDER. 216 023446 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE decomposition, may be over 50% at temperature above 250C. The higher the temperature between 100 to 300C. the higher the adsorption in air or helium. Decomposition of 1,2,3,4-TCDD was not observed.when air was used; however, when helium was used for vapor flow, decomposition to two TrCDDs were observed at 250, 285 and 300C. with increasing amounts of TrCDDs as temperature increased. SUBJECT TO PROTECTIVE ORDER. 217 023447 ssss-ssasgr II. II. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): Title: M. Rizzardini, et al * Toxicological Evaluation of Urban Waste Incinerator Emissions Reference: Chemosphere, 12, 559-564 (1983) Citation No : 89 ' Source of Dioxins Source: Gas condensate from a modern municipal incinerator in Como, Italy Sampling Techniques: Collection, extraction with hexane and purification as described in Citation . N o 32 Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: TCDDs, PeCDDS, HCDDs, HpCDDS as chlorine no. isomer clusters and OCDD Also chlorine no. isomer clusters for the analogous PCDFs. See Table 1. Analytical Techniques Used packed column GC/MS with SIM technique as described in Citation No. 32 Specificity: Only isomer clusters determined Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) This article describes an investigation of the effects of a mixture of PCDDs and PCDFs on harmonal antibody response and production. Conclusions are: (1) Microsomal enzyme induction is a prompt, sensitive biological parameter of exposure to PCDDs or PCDFs, even when they are in mixtures. (2) The results indicate a competitive effect at the receptor site between TCDD and TCDF isomers; however, it is impossible to extrapolate the effects of different ratios of isomers. Prediction SUBJECT TO PROTECTIVE ORDER. 218 023448 ,i ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I I t of the toxic effects of mixtures of chemicals 1 released simultaneously in the environment is a ! complex problem. I | Mentions the excellent correlation between AHH induction and the toxic potency of certain PCDD andPCDF isomers. | iI I 1I II j i i i ! CONFIDENT! Ai.Hi SUBJECT TO PROTECTIVE ORDER. 219 023449 I. II. III. IV. ATTORNEY WORK PRODUCT - ' " ' n i F N T PRIVILEGE Non"Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): J. J. Ryan Title: Higher chlorinated Dioxins Implicated in the Mortality of Young Pigs Kept on a Pentachlorophenoltreated Wooden Floor Reference: Can. Vet. J. , 24, 72-75 (1983) Citation No: 90 Source of Dioxins Source: PCP freshly treated wooden flooring Sampling Techniques: Samples of the treated wood, sow's milk, and tissues from two piglets (liver, brain, kidney, serum, stomach content and skin) were collected - (details not given). Samples apparently extracted with chloroform-methanol with lipid degradation and removal by cone. H2SO4 and chromatography of the extract on a floricil column. The extracts were further purified by separation into dioxin isomer groups by HPLC. Flow Data (mass transfer): NA Chemistry of Formation: Not discussed Isomers Identified: HCDDS: . 1,2,4,6 ,7,9-; 1,2,3,6 ,7,9-; 1,2,3,6 ,7,8-; 1 ,2 ,3,4,6 ,8-. HPCDDs: 1,2,3,4,6 ,7,9- and 1,2,3,4,6 ,7,8-. Analytical Techniques Used silica gel column GC/MS with SIM technique Specificity: Isomer specific for isomers identified Sensitivity: Detection limit = 10-40 ppt depending on sample Comments (Significant Data, Graphs, etc.) TCDDs were not found in any of the samples. Table II gives dioxin levels of PCDDs as chlorine no. isomer clusters in the wood as well as all biological samples taken. RMRIFrT TO PRnTFCTVF D R D F R 220 C w 3 4 o lJ ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Table III gives distribution of HCDD and HpCDD individual isomers in wood and piglet skin and liver. Surprising was the absence of dioxins in the serum when high amounts were found in the skin and liver. Mentions that dioxins.with chlorine in the four lateral positions are absorbed and retained; others with different chlorine patterns and decreased toxic effects are either not absorbed or rapidly metabolized. The results implicate the higher chlorinated dioxins in the mortality of young pigs. The sow showed no clinical signs of toxicity. SUBJECT TO PROTECTIVE ORDER. 221 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): T. Sakuma, et al Title: The Rapid Analysis of Gaseous PAH and Other Combustion Related Compounds in Hot Gas Streams by APCI/MS and APCI/MS/MS. Reference: Chem. Anal, and Biol. Fate: Polynucl. Aromat. Hydrocarbons, Int. Symp. pp. 179-188 (1981) ; Battelle Press, Columbus, Ohio Citation No: 91 Source of Dioxins Source: Stack gas at 225. from a coal-fired cement kiln. Sampling Techniques: Used an on-line sampling devise with a 25 meter sampling tube where the temperature through the line was 120-150C. with the sample gas cooled to 50C. just upstream from the TAGA analysing unit. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Four TCDD isomers including 2,3,7,8-TCDD. Analytical Techniques Used the newly developed TAGA 6000 (APCI/MS/MS) with collision induced dissociation (CID) technique Specificity: Apparently isomer specific. Mentions identification of 2,3,7,8-TCDD and 1,2,3,4-TCDD. Sensitivity: Gives detection limits for pyrene, benzo(a)pyrene and coronene but not for TCDDs. Comments (Significant Data, Graphs, etc.) Results indicate that TCDD isomers can be identified unequivocally even in 'large excesses of PCBs and DDE. The article is primarily on the analysis of PAHs. No indication of the degree of quantitation of TCDDs. No data on amount of TCDDs in the stack gas. IDErci SUBJECT TO PROTECTIVE ORDEr" 222 023452 ATTORNEY WORK PRODUCT 4t ORNEY.CL:ENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I . Citation Author(s): U. Samuelsson and A. Lindskog Title: Chlorinated Compounds in Emissions from Municipal Incineration Reference: Chemosphere, 12, 665-668 (1983) Citation No : 92 II. Source of Dioxins Source: A municipal incinerator equipped with an inclined grate furnace with an afterburner. Sampling Techniques: Particulates collected on glass fiber filter, gas condensate collected by use of cold condenser, and gaseous components collected on Amberlite XAD-2 in a sample train (good diagrams). Filters and XAD-2 Soxhlet extracted with methylene chloride. Condensate extracted with cyclohexane. The extracts were given an acid and basic wash. The methylene chloride was concentrated and the residue disolved in cyclohexane. In some cases, the concentrated samples were further fractionated on a silica gel column eluted with hexane, toluene and methylene chloride. Flow Data (mass transfer): Furnace input was 2000 kg/hr. with a stack gas flow of 30,000-35,000 m3/hr. The maximum amount of 2,3,7,8-TCDF was 2 ug/m3 . Thus 2,3,7,8-PCDD emitted is not greater than 1.56 g/day (see comments). Chemistry of Formation: Not discussed Isomers Identified: Using peak finder mode, separated PCDDs: DCDDs, TrCDDs, TCDDs, PeCDDs, HCDDs, HpCDDs as chlorine no. isomer clusters and OCDD PCDF: Same analogous chlorine no. isomer clusters and OCDF. Using SIM mode: 2,3,7,8-TCDF TN T7T "3'T M l * L#'KisA'sSI 1 il SUBJECT TO PROTECTIVE ORDER. 223 C23453 III. IV. a t t o r n e y w o r k PRODUCT v * a - t N T pRIVILG Analytical Techniques Used capillary GC and capillary GC/MS with peak finder mode and SIM mode. Specificity: PCDDs and PCDFs as chlorine no. isomer clusters. Isomer specific for 2,3,7,8-TCDF, OCDD and OCDF Sensitivity: Lowest value given was 5 ug/m3 for phenanthrene. Nothing on PCDDs or PCDFs. Comments (Significant Data, Graphs, etc.) Chlorinated compounds in the order of the amount found: PCBzs > PCDFs > PCNs > PCDDs > PCBs Most found in the XAD-2 followed by condensate. Maximum amount of 2,3,7,8-TCDF is 2 ug/m3 . Thus maximum amount emitted per day = 2 x 10 * 6 x 32,500 m 3/hr. x 24 = 1.56 g/day 2,3,7,8-TCDD can be no higher than this. SUBJECT TO PROTECTIVE ORDER. 224 C23454 Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE I. Citation Author(s): W. A. Shaub and W. Tsang Title: Dioxin Formation in Incinerators Reference: Environ. Sci. Technol., 1_7, 722-730 (1983) Citation No: 96. II. Source of Dioxins Source: A paper study of possible reactions leading to formation of PCDDs in the gas phase of incinerators mainly considering chlorophenols as the precursor. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Model mechanism proposed d) -- > Cl Cl XXX Isomers Identified: Cl OH Not discussed Cl 0 Cl XX III. Analytical Techniques Specificity: Not discussed Sensitivity: Not discussed IV. Comments (Significant Data, Graphs, etc.) Processes which may contribute to the formation of PCDDs were examined. A model mechanism was constructed to investigate the possibility of homogeneous gas phase formation of PCDDs from chlorophenols. Calculations were made. The results lead to the conclusion that the probability of gas phase formation of PCDDs is likely to be very low at high temperatures >1200K if mixing between air and fuel is efficient. In addition, production of PCDDs is found to be dependent upon the square of the chlorophenol concentration. These authors point out that additional studies are needed to more fully understand the processes for formation and destruction of toxics such as PCDDs and PCDFs during the process of high temperature combustion and have listed some of the areas where additional research is needed. t /"* n n A T r m w r AT 225 C3345 attorney w ork ATTORNEY-CLIENT product PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): R. J. Smith Title : "Dioxins Have Been Present Since the Advent of Fire", says Dow Reference: Science, 202, 1166-1167 (1978) Citation No : 97 Source of Dioxins Source: Entire environment is contaminated with dioxin , 1-. Fish 2. Ash from refuse incinerators, fossil fueled power plants, fireplaces, charcoal grills, cigarettes, automobile engine emissions, airborne emissions. 3. Everywhere combustion occurs 4. Trichloro- and pentachlorophenol, 2,4,5-T Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Dioxins in general, 2,3,7,8-tetrachlorodioxin Analytical Techniques Specificity: Not discussed Sensitivity: Not discussed, Did indicate a detection level of 3 ppt. Comments (Significant Data, Graphs, etc.) Dow officials point to other possible sources of dioxin in and around the Midland plant as well as in the environment, in general. EPA officials note that the highest levels of dioxin were found by Dow to be around the Dow Plant. Dow was trying to make the point that zero dioxin is not a reasonable level as an environmental standard. SUBJECT TO PROTECTIVE ORDER. 226 C23456 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I. Citation Author(s): R. M. Smith, et al Title: Analysis for 2,3,7,8-tetrachlorodibenzofuran and 2,3,7,8-tetrachlorodibenzo-p-dioxin in a Soot Sample from a Transformer Explosion in Binghamton, New York Reference: Chemosphere, ri, 715-720 (1982) Citation No: 98 II. Source of Dioxins Source: Soot produced when a fire caused a transformer to rupture, releasing a dielectric fluid, Pyranol, consisting of (PCBs)(65%) and chlorinated benzenes (35%). Sampling Techniques: Composite sample of soot from the stairwell of the contaminated building. Sample (3-100mg) was placed on 5mm of silica gel in a glass thimble and spiked with [U13C] 2,3,7,8-TCDD internal standard prior to extraction. Benzene extractant used in Soxhlet. The benzene extract was concentrated and diluted with acetone to 20% benzene"and applied to a carbon liquid chromatograph column, washed with 20% benzene in acetone, reversed, and eluted with benzene. The benzene was then replaced with cyclohexane. This extract was passed through a silica gel column and eluted with hexane (removed PCBs and PCDPEs which interfere). Further purification done by HPLC. III* Flow Data (mass transfer): Not discussed Chemistry of Formation: Formation of 2,3,7,8-TCDF in soot is likely based on the work of Buser & Rappe on the pyrolysis at 600C. of 2,4,5,2',4',51 hexachlorobiphenyl. The formation can readily be explained by replacement of two ortho chlorine atoms in the hexachlorobiphenyl isomer with an oxygen atom. Isomers Identified: 2,3,7,8-TCDD and 2,3,7,8-TCDF Analytical Techniques Final analysis, after additional purification, was by capillary GC/HRMS with a 50m X 0.35mm OV275 capillary column coupled via a jet separator to a Kratos MS50 (MS) tuned to 10,000 resolution. SUBJECT TO PROTECTIVE ORDER. 227 023457 ATTORNEY WORK PRODUCT .......... rv C 'ENT PRIVILEGE Specificity: Identification, and quantification by ion monitoring analysis for 2,3,7,8-TCDF and TCDD. Sensitivity: Not specific on sensitivity but did report levels down to 2.7 x 10 3 ppm of TCDD and 7.2 x 10 3 ppm TCDF of 2,3,7,8 isomer of each IV. Comments (Significant Data, Graphs, etc.) Table 1 shows recovery from fireplace soot. Table 2 shows concentration of 2,3,7,8-TCDF and 2.3.7.8- TCDD in transformer soot. Experiments with mixtures of tri-, tetra- and penta-chlorobenzene, when pyrolyzed at 620C., complex mistures of tetrachloro to octochloro PCDFs and to a lesser extent PCDDs. H. R. Buser, Chemosphere 8 , 415, (1979). Based on the PCB pyrolysis work of Buser, et al, Chemosphere 7, 109 (1978) which showed that TCDFs are 20% of the total PCDF and that 2,3,7,8-TCDF isomer accounts for 20% of TCDF. Conclusion: 2.3.7.8- TCDD and TCDF were found in a soot sample from the transformer explosion that occurred in an office building in Binghamton, New York. SUBJECT TO PROTECTIVE ORDER. 228 C23458 I. II. III. IV. ATTORNEYWORKPRODUCT A' " Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): R. H. Stehl and L. L. Lamparski Title: Combustion of Several 2,4,5-Trichloro-phenoxy Compounds; Formation of 2,3,7,8-Tetrachlorodibenzo -p-dioxin Reference: Science, 197, 1008-1009, (1977) Citation No : 99 Source of Dioxins Source: Combustion of the herbicide 2,4,5-T Sampling Techniques: Grass sprayed with 12#/acre 2,4,5-T equivalent, were taken immediately and 7 days later. Herbicide extracted with MeOH or acetone and placed uniformly on filter paper and dried. Complete combustion of paper required 5 minutes. Temperatures of 600-800C. recorded. Combustion flask connected to 4 gas absorber traps (all glass); 1 trap in ice bath other 3 in dry ice. Each trap is filled with glass beads. Air is drawn through system during collection. Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD Analytical Techniques Low resolution GC/MS. No further details. Specificity: 2,3,7,8-TCDD Sensitivity: 0.001 ug/0.5g sample of 2,4,5-T Comments (Significant Data, Graphs, etc.) Grass and paper coated with several compounds of 2,4,5-T moiety were subjected to combustion. By using compounds that had been purified to achieve background amounts of 2,3,7,8-TCDD together with an efficient cleanup and analysis of the residue, it was possible to detect as little as 0.001 ug of 2,3,7,8-TCDD in the combustion of 0.5 gms of 2,4,5-trichlorophenoxy material. SUBJECT TO PROTECTIVE ORDER. 77<) C23459 attorney w o r k product A ' -MT pqiVHQg Table 1: Combustion of material containing 2,4,5-T species. Table 2: Combustion of grass treated with 2,4,5~T herbicide (12///acre) . CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 230 C234fi'0  TTORNEY W ORK PRODUCT i ORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): M. L. Taylor, et al Title: Assessments of Incineration Processes as Sources of Super toxic Chlorinated Hydrocarbons: Concentrations of Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans and Possible Precursor Compounds in Incinerator Effluents Reference: Chlorinated Dioxins and Dibenzofurans in the Total Environment, Chap, 8 , 125-164, Edited by G. Choudhry, L. H. Keith and C. Rappe (1983) Citation No: 100 Source of Dioxins Source: Stack effluent samples from refuse fueled boilers. Typical incinerator operating conditions: ' Front 1250-1350F Rear 750F Electrostatic precipitator outlet 540F. Typically achieve a 58% reduction in weight of refuse to ash. 5325 tons/month of refuse burned at this plant. Sampling Techniques: Scott environmental technology using a Modified Method 5 sampling train. Flow Data (mass transfer): Assume 5325 tons/month refuse reduced to 2237 tons/month of ash. Total (TCDDs to OCDD) dioxins/hr. in ash = 5.673gms/hr. TCDDs/hr. in ash = 1.36gms/hr. Total (TCDFs to OCDFs) CDFs/hr. in ash = 3.18gms/hr. Insufficient data 'to calculate vapor emission. Chemistry of Formation: Not discussed specifically. References to other work on the chemistry are cited. Isomers Identified: All isomers of PCDDs, PCDFs, chlorobenzenes, chlorophenols where authentic samples of individual isomers were available. Specifically, 2,3,7,8-TCDD and 2,3,7,8-TCDF were identified as well as chlorobenzenes and chlorophenols. See comments below. SUBJECT TO PROTECTIVE ORDER. 23i , 0^3461 ATTORNEY WORK PRODUCT . wkNEY-CLIENT privilege III. IV. Analytical Techniques Fused silica capillary HRGC/MS in a multiple ion monitoring mode. Specificity: Isomer specific using standards Sensitivity: ng/sample ng/g fly ash Comments (Significant Data, Graphs, etc.) Modified method 5 sampling train is described in detail on pages 128-130. Preparation of samples for analysis and analytical procedures are on pages 130-143. Quality Assurance and Regents are on page 143. Tables 8.6-8.9 give analyses of samples of stack effluent. Figures 8.2-8.6 give selected-ion mass chromatograms for calibration standards. The steam boiler in these studies can be regarded as a source of significant quantities of PCDDs, PCDFs and other chlorinated hydrocarbons. In addition, it is noteworthy that a major portion of the total PCDDs aind PCDFs observed are tetrachlorinated compounds. Operating conditions of the incinerator may not have been optimal, during this test, for the destruction of compounds tested. Specific TCDD isomers identified and quantified in extract of particulate filter. 1.3.6.8- 1,2,7,9- 1.3.7.9- [1,2,3,4-/1,2,3,6-/1,2,6,9-] 1.3.6.9- [1,2,3,7-/1,2,3,8-/2,3,7,8-] [1,3,7,8-/1,4,6,9-/1,2,4,7-/1,2,4,8-] [1,2,4,6-/1,2,4,9-] 1,2,6,8- 1,4,7,8- 1,2,7,8- Mass transfer calculation: 5325 tons/mo. x 0.42 x 1.83g PCDDs/ton = 5.673 g/hr. TCDDs through OCDD 720 hrs./mo. 5.673 x .24 = 1.36g TCDDs/hr. 5.673 x .56 = 3.17g TCDFs through OCDF/hr. in ash CONM'l ilI AX SUBJECT TO PROTECTIVE ORDER. 232 033462 ATTORNEY W ORK PRODUCT ?NT NIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): T. 0. Tiernan, et al Title: Chlorodibenzodioxins, Chlorodibenzofurans and Related Compounds in the effluents from Combustion Processes. Reference: Chemosphere, 12, 595-606(1983) Citation No: 101 Source of Dioxins Source: Refuse fueled incinerators-stack samples Chemical waste incinerators-stack samples -Pine wood burned in the presence of air and HC1 vapor - combustion gases Sampling Techniques: Samples taken by Scott Environmental Technology using a modified EPA Method 5 sampling train Flow Data (mass transfer): Insufficient data is given for calculating total effluent discharge from incinerator. Pollutant concentration per volume in sample train is given. Burning pine wood with HC1 vapor present produced 155ngCDDs/CDFs (Cl4 through Cl8)/gm wood. With air only, no detectable CCDs/CDFs were found. Chemistry of Formation: No specific chemistry cited. They conclude that chlorophenols, chlorobenzenes and PCBs, all of which were detected in the incinerator effluent, have all been proposed as precursors or intermediates in the formation of CDDs/CDFs in combustion environment. Isomers Identified: 1.3.6.81.3.7.91.3.6.91,2,6,81.4.7.81.2.7.91,2,7,8- TCDD " " " " " [1,3,7,8-/1,4,6,9-/1,2,4,7-/1,2,4,8-1 [1,2,4,6-/1,2,4,9-1 [1,2,3,4-/1,2,3,6-/1,2,6,9-1 [1,2,3,7-/1,2,3,8-/2,3,7,8-] SUBJECT TO PROTECTIVE ORDER. 233 C2343 ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE III. IV. Analytical Techniques GC/MS in the SIM mode. The standards used included 30 different CDDs, 7 CDFs, 13 PCBs, 6 chlorobenzenes and 5 chlorinated phenols Specificity: Isomer specific with standards Sensitivity: Not specified. However, values for TCDD of 0.38 ug/m3 and of 2.6ug/m3 for TCDF are reported. Combustion of wood, 30 pg/g wood is mentioned as detection level. Comments (Significant Data, Graphs, etc,) Studies in 1979 on effluents from the Hempstead Refuse Recovery Corp. municipal wastefueled boiler located in Nassau, NY, showed that TCDDs, absorbed on particulates in the flue gases, were emitted in quantities as high as 11.8mg/hr. during one period of operation. However, 2,3,7,8-TCDD was a minor constituent, the principal isomer detected was 1,3,6,8-TCDD. Table 1: Sequence of operation in GC/MS/25-DS analysis of sample extracts for CDDs and CDFs. Table 3: Summary of concentrations of chlorinated hydrocarbons determined in flue gas effluents from refuse incinerators. Table 5: Specific TCDD isomers identified in the particulates from flue gas effluent. Experiments in which pine wood was burned in normal air, no detectable CDDs/CDFs were found at three temperatures of study. Pine wood burned in the presence of HCl/air relatively large quantities of the entire series of CDDs/CDFs were detected. We can thus conclude that combustion of conventional fuels under certain conditions significant quantities of CDDs/CDFs are produced. CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER. 234 C2 3 4 H4 I. II. III. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK ATTORNEY-CLIENT PRODUCT p r iv il e g e Citation Author(s): H. Tosine Title: Dioxins: A Canadian Perspective Reference: Book: "Chlorinated Dioxins and Dibenzofurans in the Total Environment", edited by G. Choudhry, L. H. Keith and C. Rappe, pp. 3-14 (1983) Citation N o: 116 Source of Dioxins Source: This is a summary article, thus NA Sampling Techniques: NA Flow Data (mass transfer): Estimated input of PCDDs to the environment from municipal incinerators (fly ash) is 13.5 kg/yr. for Canada and 1000 kg/yr. for the U.S. Value fot Canada appears low. Distribution of PCDD chlorine no. clusters in good agreement with Citation No. 84 on Dutch incinerators. Total estimate of PCDDs to the Canadian environment from chemical sources (2,4-D and PCP) is 1.5 metric tons/yr. Chemistry of Formation: NA Isomers Identified: . On input of PCDDs to the Canadian environment by municipal incinerators, see Table 1.1 [data from NRCC report No. 18574 (1981)]: TCDDs through OCDD as chlorine no. clusters. Table 1.2 lists input of PCDD to the Canadian environment from chemical sources (same reference): DCDDs through OCDD as chlorine no. clusters. Analytical Techniques NA Specificity: NA Sensitivity: NA CONFIDENTIAL SUBJECT TO PROTECTIVE ORDER, 235 ATTORNEY WORK PRODUCT IV. Comments (Significant Data, Graphs, etc.) <,-CL!cNT viVi^EGE Under "Exposure", a "virtually safe dose"(VSD) is defined as a dose for which there would be an increase of I cancer in 1 million individuals. This translates to 1 ng 2,3,7,8-TCDD/kg body wt. per day in rate or between 2 and 6 pg/day 2,3,7,8-TCDD over the life of a 70kg person. In Canada, there is a 20 ppt guideline for fish, which seem to bioaccumulate 2,3,7,8-TCDD. Also mentions milk from animals raised in PCP treated pens contain PCDDs. Conclusion: Need more extensive monitoring programs to increase the data base for environmental matrices. Need cooperation in the fields of analytical chemistry, toxicology and risk assessment. 236 r " f U* I. II. * III. IV. ATTORNEY W ORK PRODUCT AiiO RN EY-CU EN T PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): D. I. Townsend Title: Change of Isomer Ratio and Fate of Polychlorinated-pdioxins in the Environment Reference: Chemosphere 12, 637-643, (1983) Citation No : 112 Source of Dioxins Source: 1) "Source Samples"-fly ash, flue gas 2) "Environmental Samples" - Air-borne particulates. Could find ho reference to gas samples. Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: Isomer clusters of TCDDs through OCDD Analytical Techniques Not discussed Specificity: Not discussed Sensitivity: Not discussed Comments (Significant Data, Graphs, etc.) PCDD isomers' are found in many environmental samples in proportions that are numerically consistent with values predicted by a steady state kinetic model of a red-ox reaction system. Recent data extend the geographical significance of these findings to include regions of the Western United States. In addition, the extension of the red-ox hypothesis, is proposed to explain similarities and differences in the behavior of PCDDs from unrelated combustion sources, which include the role of photo-initiated red-ox mechanisms in the removal of PCDDs from the environment. These studies are based primarily on samples of urban areas in the U.S. samples from urural areas usually are too low in PCDDs to measure, but the available data on H7CDD/0CDD ratios in rural samples are similar to urban areas. C2346V ATTORNEY W ORK PRODUCT A . /-CL.ci'il" PRIVILEGE The author has modelled a progressive shift in isomer group ratios in the immediate vicinity of two combustion sources. Again, nothing can be said about physical and chemical mechanisms, but undoubtedly both the speed and degree of re-equilibration varies from source to source and depends on many factors. However, if typical, the studies reported in this article, suggest that changes in composition are complete within a few thousand feet of the source and beyond this perimeter, the PCDD laden particulates mix into and help create the environmental background. In a separate study, it is shown that photodegradation of PCDDs deposited on a glass surface occurs at moderately fast rates. Half life for TCDDs (22 isomers) was reported to be 2-140 hours. These phenomena taken together may provide an important mechanism by which PCDDs can directly degrade in the atmosphere. In conclusion, the fate of PCDDs in the environment is complex. While red-ox equilibration masks the formation mechanism in the combustion process, environmental process may reshape the fine grain composition of PCDDs in environmental samples. SUBJECT TO PROTECTIVE ORDER. 238 /*'r \ ATTORNEY W ORK PRODUCT ATORNEY-CUENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): D. I. Townsend Title : 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 Reference : Pergamon Ser. Environ. Sci., 5, 265-274 (1982) Citation No: 102 II Source of Dioxins Source : 1) Environment, 2) Source (site), 3) Biological niques : NA Flow Data (mass transfer): NA Chemistry of Formation: Non Dioxins Non Dioxins Non |b2 RH LD <... Cl' to2 RH Cl* Cl* 2 HC1 + o2 - ">Cl2 + H2O 2 NaCl + CO; Cl* Lowers" Cl* Ll2 <-- 2C1 Isomers Identified NA III Analytical Techniques (>ee Comments) Specificity: NA Sensitivity: NA SUBJECT TO PROTECTIVE ORDER. 239 C2346y IV. Comments (Significant Data, Graphs, etc.) ATTORNEY WORK PRODUCT a ;rcrney-client privilege TABLE 4 Isomer Group Ratios of Samples from Reductive Sources and Che Environment Environner!cal Samples H,CDP HCDP TCDD OCDD OCDD OCDD N.B.5. Urban Particulate (Sc. Louis) Milorganice Hllvaukee UI. Nashville incinerator European (average) .162 .010 .0014 .167 .011 .0017 Reductive Source Samples .93 1.06 .47 1.1*1* .26 .14 The concepts and observations developed and the extensive observations made convince this author that dioxins observed in environmental samples were of thermochemical origin and not tied to any specific chemical reactions. The above data (Table 4) reported by Crummet (1980) has strengthened these views. Geographically diverse-environmental samples continue to show characteristic ratios. Samples taken from reductive sources also conform to the theoretical predictions and contain relatively high concentrations of the lower chlorinated species. The theoretical data appear to confirm the generation of dioxins from coal and inorganic chlorides and that all isomer groups are formed. Under the influence of sunlight and other natural destructive mechanisms, the average rate of decay of the isoiner groups may be similar. However, within a group, specific isomers may decompose much faster and may reflect the oxidation history of the sample while the concentration of individual isomers reflects the non-thermo chemical decomposition mechanism at work in the local environment. it is hypothesized that simultaneous reduction-oxidation chemistry tailored the composition of the dioxin residue to conform with the reductive conditions of the local environment. As a consequence of this, it was postulated that samples taken from reductive sources should contain more of the lower chlorodioxins than environmental samples exposed to the oxidative conditions of the atmosphere. CONFIDSia.'^ I AJL SUBJECT TO PROTECTIVE ORDER. 240 C2347U ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins I Citation Author(s): D. I. Townsend Title: Changes in Dioxin Isomer Group Ratios in the Environment; An Update and Extension of the Present Theory. Reference: Environ. Sci. Res., 26, 152-160 (1983) Citation No: 103 II, Source of Dioxins Source: Gaseous emissions from woodburning stoves Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: This work is an extension of previous work to support the proposed reduction-oxidation theory. (Citation No. 102) Isomers Identified: NA III. Analytical Techniques Specificity: NA Sensitivity: NA IV. Comments (Significant Data, Graphs, etc.) Dioxin isomer group ratios in samples taken from wood burning units are very similar to miscellaneous source samples (Filtered scrubber water,rotary kiln scrubber water, with and without supplemental fuel, etc.) in bulk composition considering the differences in the combustion processes. There are exceptions to the typical distribution found in reductive sources but even these may have common characteristics which may suggest a common cause. HpCDD Figures 3 and 4. Isomer group ratios were HD + o u . TCDD. + . 002. OCDD OCDD ' OCDD 1.52; All the data presented follow the trends projected from the reduction-oxidation theory and contain comparatively high concentrations of the lower chlorinated CDD isomers. CONFIDENT!AT. SUBJECT TO PROTECTIVE ORDER. II III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY W ORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Citation Author(s): W. Tsang and W. Shaub Title: Environmental Consequences Arising From the Combustion of Municipal Solid Waste Reference: Resource Recovery Solid Wastes Proc. Conf.; 219-228 (1982) Citation No: 104 Source of Dioxins Source: Municipal solid waste (MSW) incineration - effluents from combustion Sampling Techniques: NA Flow Data (mass transfer): NA Chemistry of Formation: NA Isomers Identified: NA Analytical Techniques Specificity: NA Sensitivity: NA Comments (Significant Data,Graphs, etc.) Article deals with inorganic and organic pollutants in effluents from MSW incinerators in a general way. The decomposition of any polyatomic organic molecule in the environment of a MSW are a step-wise breakdown into smaller species. These steps are termed elementary processes. From this the author developed a rate of destruction equation of organic pollutants into the high temperature gaseous environment of an MSW combuster. Calculations were made estimating residence time at a given temperature in order to effect 99.99% destruction of 2,3,7,8-TCDD. Table 3 ranks some organics in terms of their stability in an oxidative high temperature environment. CONFIDENTI * SUBJECT TO PROTECTIVE ORDER 242 347ar 'r*. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins A11 u k n e y -client privilege I . Citation Author(s): M. van. den Berg, et al Title: Uptake and Selective Retention in Rats of Orally Administered Chlorinated Dioxins and Dibenzofurans from Fly-ash and Fly-ash Extract Reference: Chemosphere, 1_2, 537-544 (1983) Citation No: 9 II. Source of Dioxins Source: - Fly-ash from a municipal incinerator (Zaanstad, The Netherlands) Sampling Techniques: - Fly-ash was extracted with toluene and the toluene extract concentrated and diluted with acetone until concentration in ng/ml was similar to concentrations of PCDDs and PCDFs in ng/g fly-ash. GC/MS was used to measure PCDDs and PCDFs in crude extract as well as extract sample purified by column chromatography. Flow Data (mass transfer): Incineration operation not discussed. Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD and 2,3,7,8-TCDF were positively identified. 2,3,7,9 -TCDF; 2,3,6,8-TCDF; 2,3.,4,7,8-PCDF; 1,2,3,7,8-PCDD; 2,3,4,6,7,8-HCDF; 1,2,3,6,7,8-HCDD and 1,2,3,7,8,9-HCDD were tentatiavely identified. Because extraction in an alkaline solution may have decomposed the higher chlorinated compounds, HpCDDs and OCDD were not determined. Quantitation done on a quadruple GC/MS with SIM detection. Ill. Analytical Techniques Specificity: Analytical technique used was highly specific but only 2,3,7,8-TCDD and 2,3,7,8-TCDF were available as standards, thus only these two could definitely be quantified. Other isomers were tentatively identified by comparison with known chromatograms. Sensitivity: Not discussed CONFIDENT! A.L SUR.IFCT TO PRO TFTTIVF n p n FP 243 02347,5 ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE IV. Comments (Significant Data. Graphs,etc.) Table 1 gives concentrations of TCDDs, PeCDDs and HCDDs and corresponding CDF isomer groups in fly-ash (ng/g) and fly-ash extracts (crude and purified) (ng/ml). Range: 245-624 ng/ml or g. Tables 2 & 3 give the concentrations of PCDD and PCDF isomer groups found in the rat livers and adipose tissue. Table 4 gives the average % retention in the liver of each isomer group. 0.16% for TCDDs to 5.3% for HCDFs. Table 5 gives the relative intensity of 11 isomers as a percentage of the whole isomer group in the fly-ash extract and in the rat livers. PeCDFs, HCDDs and HCDFs (isomer groups) show highest retention in the rat livers. Retention efficiency HCDFs >HCDDs/PeCDFs >PeCDDs >TCDFs >TCDDs. SUBJECT TO PROTECTIVE ORDER. 244 n ri 3174 I. II. III. ATTORNEY WORK PRODUCT ATTORNEY-CLIENT PRIVILEGE Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins Citation Author(s): G. F. Van Ness, et al Title: Tetrachlorodibenzo-p-Dioxins in Chemical Wastes, Aqueous Effluents and Soils Reference: Chemosphere, 9, 553-563 (1980) Citation No: 105 Source of Dioxins Source : 1. Aqueous industrial effluent 2. Soil from an industrial site (TCP manufacturing plant) 3. Industrial chemical and sludge (TCP manufacturing plant) 4. Residues from chemical retorting of chlorinated - phenols 5. Industrial sludge Sampling Techniques: Not discussed Flow Data (mass transfer): Not discussed Chemistry of Formation: Not discussed Isomers Identified: 2,3,7,8-TCDD Analytical Techniques GC/HRMS analyses using a Varian 3740 GC coupled through an AEI silicone membrane separator to an AEI double-focusing, double-beam MS-30 MS equipped with a unique electrostatic analyzer (ESA) step-scan circuit. Specific operating conditions are described. Specificity: Isomer specific with standards Sensitivity: 10 pg/injection achieved for TCDDs with a signal/noise ratio of 10:1, at a static resolution of 1:12,500. 10 pg/g of industrial effluent sample 20 pg/g of industrial soil sample JA^ i M SUBJECT TO PROTECTIVE ORDER. 245 02347o Comments (Significant Data, Graphs, etc.) ATTORNEY w o r k pr o d u ct A i ORNEY-CLIENT PRIVILEGE Methods are described for determination, of TCDDs in 1) chemical wastes, 2) aqueous effluents and 3) soils from industrial sites at concentrations of ppt. application of this methodology for analyses of these types- of samples from a TCP manufacturing site have shown a substantial quantity of TCDD and a significant portion being 2,3,7,8-TCDD isomer. Table 2: Results from aqueous industrial effluents Table 3: Results of soil samples from industrial sites Table 4: Results of industrial chemical and sludge SUBJECT TO PROTECTIVE ORDER. 246 C2347& I. II. III. IV. Non-Industrial Sources of Chlorinated Dibenzo-p-dioxins ATTORNEY WORK PRODUC' A 3RNEY-CLIENT PRIVILEGE Citation Author(s): A. S. Wong Title: Determination of TCDD in Industrial and Municipal Waste Waters Reference: U. S. Dept, of Commerce; National Technical Information Service PB82-I96882. EPA-600/4-82-028, (1982) Citation No : 106 Source of Dioxins Source: Industrial and Municipal Waste Water (Sacramento, CA) Sampling Techniques: Grab samples and/or automatic or manual compositing equipment collected in amber bottles in volumes of 250ml to 1 liter. Containers must be washed and solvent rinsed before use. Screw-on caps with Teflon liner containers are refrigerated during sampling and storage: No Tygon or rubber, tubing can be used. All samples must be extracted within 7 days and completely analyzed within 30 days of collection. Flow Data (mass transfer): Not discussed Chemistry of Formation: None proposed. Isomers Identified: 2,3,7,8-TCDD, 1,2,3,4-TCDD Analytical Techniques GC/MS with electron impact (El) source in the SIM mode. Specificity: For 2,3,7,8-TCDD and 1,2,3,4-TCDD. Other TCDDs were grouped. Sensitivity: Detection limit = 0.003ug/L Comments (Significant Data, Graphs, etc.) In conjunction with the development of an analytical method for 2,3,7,8-TCDD in industrial and municipal waste water, the stability of TCDD in organic solvents and chlorinated water was also studied. It was found that TCDD solutions prepared in benzene, acetone and methanol remained stable during cold storage (4C.) and at room temperature (25C.). However, i n D D H T rrT iw r n r?n ro ?7 23477 attorney w o rk produc ATTORNEY-CLIENT PRIVILEG degradation of TCDD in drinking water was observed as a result of chlorination from CI2 in water, followed by prolonged storage. Table 16 - The limit of detection represents the sensitivity that can be achieved in a waste water under optimal conditions. Table 7 - Recoveries of TCDD from waste water, spiked and "as is". SUBJECT TO PROTECTIVE ORDER. 248 / / / C23478