Dioxin Perspectives ||

Dioxin Perspectives A Pilot Study on International Information Exchange on Dioxins and Related Compounds

NATO • Cballenges of Modern Society A series of edited volumes comprising multifaceted studies of contemporary problems facing our society, assembled in cooperation with NATO Committee on the Challenges of Modern Society.

Volume 1 AIR POLLUTION MODELING AND ITS APPLICATION I Edited by C. De Wispelaere

Volume 2 AIR POLLUTION: Assessment Methodology and Modeling Edited by Erich Weber

Volume.3 AIR POLLUTION MODELING AND ITS APPLICATION II Edited by C. De Wispelaere

Volume 4 HAZARDOUS WASTE DISPOSAL Edited by John P. Lehman

Volume 5 AIR POLLUTION MODELING AND ITS APPLICATION III Edited by C. De Wispelaere

Volume 6 REMOTE SENSING FOR THE CONTROL OF MARINE POLLUTION Edited by Jean-Marie Massin

Volume 7 AIR POLLUTION MODELING AND ITS APPLICATION IV Edited by C. De Wispelaere

Volume 8 CONTAMINATED LAND: Reclamation and Treatment Edited by Michael A. Smith

Volume 9 INTERREGIONAL AIR POLLUTION MODELING: The State of the Art Edited by S. Zwerver and J. van Ham

Volume 10 AIR POLLUTION MODELING AND ITS APPLICATION V Edited by C. De Wispelaere, Francis A. Schiermeier, and Noor V. Gillani

Volume 11 AIR POLLUTION MODELING AND ITS APPLICATION VI Edited by Han van Dop

Volume 12 RISK MANAGEMENT OF CHEMICALS IN THE ENVIRONMENT Edited by Hans M. Seip and Anders B. Heiberg

Volume 1.3 AIR POLLUTION MODELING AND ITS APPLICATION VII Edited by Han van Dop

Volume 14 HEALTH AND MEDICAL ASPECTS OF DISASTER PREPAREDNESS Edited by John C. Duffy

Volume 15 AIR POLLUTION MODELING AND ITS APPLICATION VIII Edited by Han van Dop and Douw G. Steyn

Volume 16 DIOXIN PERSPECTIVES: A Pilot Study on International Information Exchange on Dioxins and Related Compounds Edited by Erich W. Bretthauer, Heinrich W. Kraus, and Alessandro di Domenico

Dioxin Perspectives A pilot Study on International Information Excbange on Dioxins and Related Compounds

Edited by Ericb W. Brettbauer U.S. Environmental Protection Agency Washington, D.C.

Heinricb W. Kraus Bundesmlnlsterlum fiir Umwelt Bonn, Germany

aud Alessandro di Domenico lstituto Superiore di Sanltâ Rome, ltaly

Coordinating Editors:

Frederick W. Kutz u.s. Envlronmental Protection Agency Washington, D. C.

David P. Bottimore Versar lnc. Springfield, Virginia

Otto Hutzinger Unlverslty of Bayreuth Bayreuth, Germany

Published in cooperation with

Heidelore Fiedler Unlversity of Bayreuth Bayreuth, Germany

and

A. Essam Radwan University of Central f'lorida Orlando, f'lorida

NATO Committee on the Challenges of Modern Society

SPRINGER SCIENCE+BUSINESS MEDIA, LLC

Library of Congress Cataloging in Publication Data

Dioxin perspectives: a pilot study on international information exchange on dioxins and related compounds / edited by Erich W. Bretthauer, Heinrich W. Kraus, and Alessandro di Domenico.

p. cm.-(NATO challenges of modern society; v. 16) "Published in cooperation with NATO Committee on the Challenges of Modern

Society." Includes bibliographical references and index. ISBN 978-1-4613-6456-6 ISBN 978-1-4615-3308-5 (eBook) DOI 10.1007/978-1-4615-3308-5 1. Dioxins-Toxicology-Congresses. 2. Dioxins-Environmental aspects

Congresses. I. Bretthauer, Erich Walter, date. II. Kraus, Heinrich W. III. Di Domenico, Alessandro.lV. Series. RA1242.D55D563 1991 91-4262 615.9'5112-dc20

Proceedlngs of a NATO/CCMS Pilot Study on Internationallnformatlon Exchange on Dioxins and Related Compounds, which began May 1985, in Brussels, Belgium, and concluded April 1988, in Berlin, Germany

ISBN 978-1-4613-6456-6

© 1991 Springer Science+Business Media New York OriginaIly published by Plenum Press, New York in 1991

AII rights reserved

CIP

No part of this book may be reproduced, stored in a retrieval system, or transmiUed in any form or by any means, electronic, mechanicaL photocopying, microfilming, recording, or otherwise, without wrlUen permission from the Publisher

ACKNOWLEDGMENTS

This volume reflects over three years of effort from the participants

in the NATO/CCMS Pilot Study on International Information Exchange on

Dioxins and Related Compounds. The Pilot Study produced 15 reports that

describe the findings and accomplishments of the project. This volume

summarizes the products from the international information exchange

activities in a format suitable for quick reference. The editors of the

volume are listed below:

Editors: Erich W. Bretthauer U.S. Environmental Protection Agency Washington, D.C., USA

Heinrich W. Kraus Bllndesministerium fur Umwelt, Naturschutz und

Reaktorsicherheit Bonn, Federal Republic of Germany

Alessandro di Domenico Istituto Superiore di Sanita Rome, Italy

Coordinating Editors: Frederick W. Kutz U.S. Environmental Protection Agency Washington, D.C., USA

David P. Bottimore Versar Inc. Springfield, Virginia, USA

Otto Hutzinger University of Bayreuth Bayreuth, Federal Republic of Germany

Heidelore Fiedler University of Bayreuth Bayreuth, Federal Republic of Germany

A. Ess3m Radwan Arizona State University Tempe, Arizona, USA

Principal authors for the contributions can be found at the beginning

of each section.

v

Special thanks are extended to Wendy Grieder and Lynn Schoolfield,

u.S. EPA, Office of International Activities; Thomas Thompson and

Frank W. Karasek, Department of Chemistry, University of Waterloo,

Ontario, Canada; Leslie C. Dickson, University of Bayreuth, FRG; Terry L.

Stoddart and Jeffrey J. Short, U.S. Air Force, Tyndall Air Force Base,

Florida; Horst Neidhard, Environmental Protection Agency, Berlin; and

Antonio Spallino, President of "Alessandro Volta" Center.

Information contained in this book was collected through the

contributions of the following lead delegates: Martin J. Boddington, and

Hugh P. Dibbs, Environment Canada, Canada; Arne Grove, Kemiteknik

Teknologisk Institut, Denmark; Christa Morawa, Umweltbundesarnt, Federal

Republic of Germany; Alessandro di Domenico, Istituto Superiore di

Sanita, Italy; Job A. van Zorge, Ministerie van Volkshuisvestung,

Rumtelijke Ordering en Milieubeheer, The Netherlands; Sigrid Louise

Bjornstad, State Pollution Control Authority, Norway; Ernest A. Cox, HM

Inspectorate of Pollution, United Kingdom; Frances Pollitt, Department of

Health and Social Security, United Kingdom; and Erich W. Bretthauer, U.S.

EPA Office of Research and Development, USA.

The information contained in this book was collected through the

contributions of numerous people, including:

vi

Donald G. Barnes, U.S. EPA, Office of the Administrator; Werner Beckert, U.S. EPA, Office of Research and Development; Jakob Enresmann, Gesellschaft zur Beseitigung van Sonderabfallen

in Rheinland-Pfalz, Gerolsheim, FRG; Sergio Facchetti, COJrunission of the European Communities; Renate Fuchs, Chair of Ecological Chemistry and Geochemistry,

University of Bayreuth, FRG; Donald L. Grant, Health and Welfare, Canada Helmut Greim, GSF Institut for Toxicology, Munich, FRG; H. Hagenmaier, Organische Chemie, Universitat Tubingen, FRG; Donald J. Hay, Chief, Urban Activities Division, Environmental

Protection Servie, Environment Canada, Ottawa, Ontario; Annette Heindl, Chair of Ecological Chemistry, University of

Bayreuth, FRG; Ralf Kilger, Umweltbehorde, Arnt fur Altlastensanierung,

Hansestadt Hamburg, Hamburg, FRG; Michael McLachlan, Chair of Ecological Chemistry, University of

Bayreuth, FRG; Connie Moller, Ministry of the Environment, National Agency of

Environmental Protection, Copenhagen, Denmark; J. J. M. Post, MT-TNO, Appeldoorn, The Netherlands; Stephen H. Safe, Texas A & M University, USA; A. A. Sien, Rijksinstiuut voor Volksgezondheid en Milieuhygiene,

Bilthoven, The Netherlands; Susanne Sieners, Arnt fur Umweltuntersuchungen der Umweltbehorde

Hamburg, Hamburg, FRG;

Ludwig Stieglitz, Institut fur Heisse Chemie, Kernforschungsanlage Karlsruhe, FRG;

James Wilson, Monsanto, St. Louis, Missouri, USA; Armon F. Yanders, Environmental Trace Substances Research Center,

University of Missouri, Columbia, Missouri, USA; Alvin L. Young, U.S. Department of Agriculture, Washington, D.C., USA.

In addition to the participants of the Pilot Study, attendees of the

meetings, and authors of this book, acknowledgment also goes to numerous

Versar personnel involved in the preparation of this book: Christel

Ackerman, Kathy Bowles, Libba Colby, Kevin Cross, Juliet Crumrine, Steve

Duda, Sally Gravely, Kammi Johannsen, Linda Mandeville, and Pat Wood.

vii

CONTENTS

List of Tables List of Figures List of Acronyms

CHAPTER 1.

CHAPTER 2.

INTRODUCTION AND BACKGROUND INFORMATION 1. Participation ...... . 2. The Pilot Study Organization 3. The Nature of the Problem .

References . . . . . . . .

EXPOSURE AND HAZARD ASSESSMENT WORKING GROUP 1. Introduction. . . . . . . . . . . . . . . . 2. International Exchange of Research and Technology

Information on Dioxins and Related Compounds . . 2.1 Introduction ........... .

2.1.1 The Exchange of Information on Research Projects

2.1.2 Data Collection 2.2 Discussion .... . 2.3 Conclusions ...... .

2.3.1 Overall Trends ..... . 2.3.2 National Areas of Emphasis ...

3. Listing of Laboratories with Expertise in the Analysis of Dioxins and Related Compounds 3.1 Method of Compilation ...... . 3.2 Description of Laboratories Listed

3.2.1 Matrices Analyzed ..... 3.2.2 Quality Assurance Schemes . 3.2.3 Internal Quality Assurance . 3.2.4 Externally Moderated Quality

Assurance .......... . 3.3 Analysis of the Listing of Laboratories

4. Inventory of Regulations/Statutes Concerning Dioxins and Related Compounds. ... . 4.1 Method of Compilation. .. . .. . 4.2 Descriptions of Regulations and Statutes

Reported . . . . . . . 4.2.1 Canada .... . 4.2.2 Denmark ... . 4.2.3 Federal Republic of Germany 4.2.4 lta1y .... 4.2.5 Netherlands . 4.2.6 Norway ..... 4.2.7 United Kingdom. 4.2.8 United States .......... .

5. International Toxicity Equivalency Factor (I-TEF) Method of Risk Assessment for Complex Mixtures of Dioxins and Related Compounds 5.1 Background ...... .

5.1.1 The Need .... . 5.1.2 The TEF Concept 5.1.3 Consensus and Accuracy

xv xxiii xxvii

· 2 · 3 · 5 10

13

15 15

15 16 17 29 29 30

41 42 43 44 45 48

48 52

81 82

84 87 87 87 87 87 88 88 88

97 100 100 101 104

ix

6.

7.

x

5.2 International TEF Scheme 5.2.1 The I-TEF Scheme 5.2.2 Application of the I-TEF Scheme to

Different Data Sets 5.3 Directions for the Future

5.3.1 The Problem 5.3.2 Addressing the Problem

5.4 Conclusions References .....

A Review and Update of Methods for Performing 2,3,7,8-TCDD ..... 6.1 Introduction

Current Knowledge and Exposure Assessments for

6.2 Physical/Chemical Properties and General

6.3

Exposure Parameters ... ..... . 6.2.1 Physical/Chemical Properties .... . 6.2.2 Body Veights and Pulmonary Ventilation

Fate. 6.3.1 6.3.2 6.3.3

Rates in Exposure Assessments . ............ . Fate of 2,3,7,8-TCDD in Soil Fate of 2,3,7,8-TCDD in Sediments Bioaccumulation of 2,3,7,8-TCDD in Fish and Cattle

6.3.4 Plant Uptake 6.4 Exposure

6.4.1 Inhalation - Vapors 6.4.2 Inhalation - Particulates ..... . 6.4.3 Dermal - Soil Contact Rates and Dermal

Adsorption 6.4.4 Ingestion - Soil 6.4.5 Ingestion - Beef and Dairy Products 6.4.6 Ingestion - Fish Consumption Data

6.5 Post-Exposure . . . . . . . . . . . . . . . . 6.5.1 Absorption from Environmental Matrices

(Bioavailability) 6.5.2 Pharmacokinetics and Body Burden of

Dioxins 6.6 Conclusions

References Quantitative Implications of the Use of Different Extrapolation Procedures for Low-Dose Cancer Risk Estimates from Exposure to 2,3,7,8-TCDD 7.1 Introduction and Definition of Terms .

7.1.1 Introduction 7.1.2 Definition of Terms

7.2 EPA's Use of the Linearized Multistage Model for Carcinogen Risk Extrapolation and Comparison with Other Models . . . . . . . . 7.2.1 Description of the Multistage and

Linearized Multistage Models . . . . . 7.2.2 Use of the Linearized Multistage Model

for Risk Extrapolation of 2,3,7,8-TCDD: Comparison of Four U.S. Agencies . . . . . . . . .

7.2.3 Allometric and Body Burden Considerations . . . . . .

7.2.4 Other Extrapolation Models 7.2.5 Time-to-Tumor Analyses

7.3 Treatment as a Promotor.. . 7.3.1 Uncertainty Factor Approach .. 7.3.2 Modeling as a Promotor Under the

Moolgavkar, Venson, and Knudson Two-Stage Model . . . . . . . .

7.4 Comparison of Animal Prediction with Actual Human Data 7.4.1 Thiess et al. (1982)

104 105

108 114 114 115 116 117

123 123

125 125

130 133 133 138

140 143 144 145 152

154 157 159 162 166

167

182 191 193

205 205 205 208

210

210

211

214 218 223 225 225

228

230 231

CHAPTER 3.

8.

7.4.2 Zack and Suskind (1980) 7.5 Discussion and Summary ....

References . . . . . . . . . . . Rationale for a Hormone-Like Mechanism TCDD for Use in Risk Assessment

References . . . . . . . . . . .

of 2,3,7,8-

TECHNOLOGY ASSESSMENT WORKING GROUP 1. Introduction to Working Group B Activities

1.1 Introduction ........... . 1.2 Summary: Formation of Dioxins and Related

Compounds from Combustion and Incineration Processes ................ .

1.3 Summary: Formation of Dioxins and Related Compounds in Industrial Processes . . . . .

1.4 Summary: Methods for Degradation, Destruction, and Detoxification of Dioxins and Related Compounds . . . . . . . . . . .

1.5 Summary: Waste Disposal Sites Contaminated with Dioxins and Related Compounds .

2. Formation of Dioxins and Related Compounds from Combustion and Incineration Processes 2.1 General Aspects .......... .

2.1.1 Introduction ........ . 2.1.2 Sources of Dioxins and Furans

2.2 Incineration of Solid Waste ....

2.3 2.4 2.5 2.6 '2.7 2.8 2.9 2.10 2.11

2.2.1 General and Historical. . . . .. . 2.2.2 Emissions and By-products of Municipal

Refuse Incineration 2.2.3 Incinerator Studies Sewage Sludge Incineration Hazardous Waste Incineration Transformer and Capacitor Fires Combustion of Wood . . . . . . Fossil Fuel Combustion . . . . Combustion of Automobile Fuels PVC as Chlorine Donor . . . . . Comparison of Combustion Sources Conclusions .. .... References . . . . . .

3. Formation of Dioxins and Related Compounds in Industrial Processes . . . . . . . . . . . 3.1 Introduction ........... . 3.2 The Current State of Knowledge

3.2.1 Chlorophenols and their Derivatives 3.2.2 Chlorobenzenes and Substituted

Chlorobenzenes . . . . . . . 3.2.3 Chlorinated Aliphatics ... 3.2.4 Processes with Chlorinated

Intermediates . . . . . . . 3.2.5 Inorganic Chlorine Chemistry .... 3.2.6 Processes Using Chlorinated Catalysts

and Solvents . . . . . . . . . . . 3.3 Analysis of Aliphatic Chlorine Compounds

3.3.1 Chloroparaffins ........ . 3.3.2 Volatile Aliphatic Chlorine

Compounds . . . . . .... 3.4 Formation of PCDD/PCDF in Other Industrial

Processes . . . . . . . . 3.4.1 Phthalocyanine Dyes ..... . 3.4.2 Investigation of Motor Oils, Waste

Oils and Recycled Oils . . . . . . 3.4.3 Search for PCDD/PCDF in Commercial

Products of PCP and PCP-Na . . . . 3.4.4 PCDD Formation in Pentachlorophenol

Manufacture . . . . . . . . . . . .

235 240 244

249 260

263 263

264

267

269

271

273 273 273 273 274 274

276 297 365 368 377 400 403 407 410 413 426 427

435 435 436 436

442 454

459 459

462 463 463

463

466 466

467

469

474

XI

xli

3.4.5 PCDD/PCDF in l,2,4-Trichlorobenzene Production . . . . . . . . . . . . . 475

3.4.6 Occurrence of PCDD/PCDF in the Effluents of Pulp and Paper Mills and Consumers' Paper Products . . . . .. 476

3.4.7 Metallurgical Processes as Sources of PCDD/PCDF . . . . . . . . . . . . . 481

3.4.8 Discharge of PCDD/PCDF During Carbon Reactivation . . . . . . . . . . . . 483

3.5 Polychlorinated Dibenzofurans from PCBs. . 485 3.6 Formation of Polybrominated Dibenzodioxins

and Dibenzofurans . . . . . . . . . . . . .. 486 3.6.1 Possible Formation of PBCC/PBDF during

the Manufacture of Brominated Chemicals . . . . . . . . . . 488

3.6.2 Polybrominated Biphenyls. . . 501 3.7 Guidelines for the Determination of

Polyhalogenated Dibenzo-p-dioxins and Dibenzofurans in Commercial Products 505 3.7.1 Possible Number of PXDD/PXDF . 505 3.7.2 Analytical Methods for Determination

of PXDD/PXDF in Commercial Products 505 3.8 Investigations of Industrial Products. . . 508

References . . . . . . . . . . . . . . . . 510 4. Methods for Degradation, Destruction, and

Detoxification of Dioxins and Related Compounds 517 4.1 Introduction . . . . . . . . . . . . . . . 517 4.2 Biological Methods . . . . . . . . . . . . 518

4.2.1 Extraction of Natural Microorganisms Adopted for Dioxin Degradation . . 519

4.2.2 Enzyme Systems for Degradation of Structurally Related Compounds . 519

4.2.3 Achieving Desired Biodegradation Through Genetic Engineering 520

4.3 Chemical Methods . . . . . . . . . . . 521 4.3.1 Potassium Polyethylene Glycolate

(KPEG) . . . . . . . . . . . . 521 4.3.2 Sodium Dispersion . . . . . . 530 4.3.3 Pyrohydrolytic Dechlorination 530

4.4 Disposal/Fixation. . . . . . . . . . 532 4.4.1 Landfilling . . . . . . . . . . . . .. 532 4.4.2 In Situ Stabilization and Solidification 533 4.4.3 In Situ Vitrification 534

4.5 Physical Methods . . . . . . 537 4.5.1 Clay Adsorption 537 4.5.2 Underground Storage in Mines 538

4.6 Treatment Methods. . . . . . 539 4.6.1 Full-Scale Technologies 539 4.6.2 New and Emerging Technologies 550 References . . . . . . . . . . . 557

5. Waste Disposal Sites Contaminated with Dioxins and Related Compounds . . . . . . . . 561 5.1 Introduction . . . . . . . . . . . . . . 561 5.2 Waste Sites in West Germany. . . . . . . 562

5.2.1 Hamburg-Moorfleet Chemical Plant. 562 5.2.2 Georgswerder Landfill (Hansestadt

Hamburg) . . . . . . . . . . . 568 5.2.3 Muggenburger StraBe Landfill

(Hansestadt Hamburg) . . . . . . . 575 5.2.4 Moorfleeter Brack Contaminated Site

(Hansestadt Hamburg) . . . . . . . . 576 5.2.5 Malsch Hazardous Waste Disposal Site

(Baden-Wurttemberg) . . . . . . . . 577 5.2.6 Gerolsheim Hazardous Waste Disposal

Site (Rheinland-Pfalz) . . . . . . . 579 5.2.7 Munchehagen Hazardous Waste Disposal

Site (Rehburg-Loccum) ....... 581

CHAPTER 4.

5.3

5.4 5.5

5.6 5.7

5.2.8 Chemical Production Site at Gernsheim (Hessen) . . . . . . . . . .

5.2.9 Karsau Hazardous Waste Site (Baden-Wurttemberg) ....

5.2.10 Other Waste Disposal Sites. . .. Waste Sites in the United States of America 5.3.1 The National Dioxin Study ... . 5.3.2 Love Canal ............ . 5.3.3 Dioxin Contamination at Times Beach Waste Sites in the United Kingdom . Waste Sites in the Netherlands 5.5.1 Volgermeerpolderest Germany 5.5.2 Diemerzeedijk .... The Sewage Sludge Controversy . . . . Aspects of Special Analytical Methods 5.7.1 Air Sampling Methods ..... 5.7.2 Laboratory Leaching Experiments 5.7.3 Analyses of Gaseous Emissions References . . . . . . . . . . . .

MANAGEMENT OF ACCIDENTS WORKING GROUP 1. Introductory Comments on Seveso (Italy)

Industrial Accident 1.1 PCDDs and PCDFs .. 1.2 The ICMESA Accident 1.3 The Present Status

2. Contingency Planning .. 2.1 Potential PCDD and PCDF Sources in Italy:

Survey, Chemical Analysis, Legislative, and Future Needs . . . . . . . . . . . . .

2.2 Contingency Planning and Emergency Response at MONTEDIPE . . . . . . . . . . . . . . .

2.3 Contingency Planning: An Expert System (ChEM) for Describing the Level of Response Needed

3. Immediate Emergency Response ........ . 3.1 Emergency Health Care .......... . 3.2 The Emergency in Seveso - Measures to

Limit Human Exposure . . . . . . . . . . . 3.3 Individual Protection in the Seveso Cleanup

4. Long-Term Rehabilitation ........... . 4.1 Design Issues in the Long-Term Surveillance

of Affected Population . . . . . . . . . . 4.2 Health Surveillance in TCDD Cleanup Workers 4.3 Strategies for Rehabilitating Affected Areas

and Buildings . . . . . . . . . . . . 4.4 Decontamination of PCDDs and PCDFs in Situ

by Solar and UV Radiations . . . . . . . . 5. Other Contributions ............. .

5.1 Accidental Release of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) at Seveso, Italy: Estimation of Total TCDD Released . . . . .

5.2 Needs for Skilled Personnel in Emergencies Following Industrial Accidents . . . . .

5.3 Liability and Compensation in the Seveso Technological Disaster . . . . . . . .

5.4 A Brief History of Risk Assessment and Management after the Seveso Accident .

5.5 The Role of Statistical Analysis in the Management of Chemical Accidents .

5.6 A Summary Comment on the Seveso Experience INDEX .....

590

594 596 597 597 611 614 617 618 618 618 619 622 622 623 623 625

631 631 633 634 641

641

655

659 667 667

673 677 685

685 691

697

701 707

707

713

717

729

737 761 765

xiii

LIST OF TABLES

CHAPTER 2. EXPOSURE AND HAZARD ASSESSMENT WORKING GROUP International Exchange of Research and Technology Information on Dioxins and Related Compounds

Table 1. Number of Formats Describing Research Activities

Table Table Table Table Table Table

Submitted by Participating Nation for CCMS Reports 2a. Total Funding by Working Group . . . . . . 2b. Total Project-Years by Working Group 2c. Average Cost/Project/year by Working Group 3a. Total Funding by Key Word 3b. Total Project-Years by Key Word 4. Listing of Research Projects ..

Listing of Laboratories with Expertise in the Analysis of Dioxins and Related Compounds

Table 1. Number of Laboratories Listed by Geographic

Table 2. Inventory of Compounds

Table 1.

Table 2.

Location ..................... . The Listing of Laboratories . . . . . . . . . . Regulations/Statutes Concerning Dioxins and Related

Number of Regulations/Statutes Reported by Geographic Location . . . . . . . . . . . Index of Regulations/Statutes Submitted for NATO/CCMS Inventory . . . . . . . . . . . . .

International Toxicity Equivalency Factor (I-TEF) Method of Risk Assessment for Complex Mixtures of Dioxins and Related Compounds

Table 1. Toxicity Equivalents Using Different TEF Methods. Table 2. The I-TEFs ................... . Table 3. Application of the I-TEF Method to Isomer-Specific

Data ................... . A Review and Update of Current Knowledge and Methods for Performing Exposure Assessments for 2.3.7.8-TCDD

Table 1. Estimated Minute Ventilation Associated with

Table 2. Table 3.

Table 4.

Table 5. Table 6.

Activity Level for Average Male Adult Rates of Ingestion of Beef and Dairy Products Percentage of Tritiated 2,3,7,8-TCDD Dose in the Liver 24 Hours after Oral Administration of 0.5 ml of Various Media . . . . . . . . . . . . . . . . . Summary of Data on the Bioavailability of 2,3,'7,8-TCDD Following Ingestion of Environmental Materials ................... . Calculated Average Daily Intake . . . . . . . . . . Risks Associa~ed with the Background Daily Intake of 2,3,7,8-TCDD Compared with Annual Cancer Incidence in U.S. Population ............... .

Quantitative Implications of the Use of Different Extrapolation Procedures for Low-Dose Cancer Risk Estimates from Exposure to 2.3,7.8-TCDD

Table l.

16 21 21 21 24 24 31

52 55

84

90

104 105

108

132 161

176

179 189

190

2,3,7,8-TCDD 2-Year Oral Rat Study (1978) Using Kociba's Histopathology Analysis (Female SpragueDawley Rats - Spartan Subs train) and Eliminating Animals that Died During the First Year . . . . . . . . 206

xv

Table 2. Factors Used by Various Agencies in Calculating Their Upper-Limit Risk Estimates for 2,3,7,B-TCDD Using the Linearized Multistage Model . . . . . . . . . 212

Table 3. Risk Extrapolations for 2,3,7,B-TCDD Using the Linearized Multistage Model and Various Estimates of Rat and Human Half-Lives and Tissue Distributions . . . . . . . . . . . . . . . .. ... 21B

Table 4. Estimates of Low-Dose Risk to Humans Exposed to 2,3,7,B-TCDD Based on Female Sprague-Dawley Rats from the Dow Chemical Co. Feeding Study Derived from Four Different Models (Data: Kociba Analysis, Adjusting for Early Mortality) . . . . . . . .. ... 219

Table 5. Estimates of Low-Dose Risk to Humans Exposed to 2,3,7,B-TCDD Based on Female Sprague-Dawley Rats from the Dow Chemical Co. Feeding Study Derived from Four Different Models (Data: Squire Analysis, Adjusting for Early Mortality) . . . . . . . . .. .. 220

Table 6. MLEs and 95% Upper-Limit Estimates of Parameters and VSDs for Various Permutations of the Female Rat Liver Data Using the Multistage Model. Kociba Histopathology, Eliminating Animals that Died Prior to First Tumor . . . . . . . . . . . . . . . . . . . . . 222

Table 7. Results of Various Time-to-Tumor Adjustments for Female Rat Liver (Neoplastic Nodules or Carcinomas) and the Multistage Model Human Equivalent Dosage (Kociba Pathology) . . . . . . . . . . . . . . . .. 224

Table 8. Comparison of RsDs and Potency Ratio Estimates for 2,3,7,B-TCDD of Various U.S. and Foreign Regulatory Agencies . . . . . . . . . . . . . . . . . . . . 227

Table 9. Estimates of Low-Dose Incremental Risk to Humans Exposed to 2,3,7,B-TCDD Based on Female SpragueDawley Rats Comparison of the Two Forms of the Two-Stage Model with Promotion with EPA's Risk Extrapolation Using the Linearized Multistage Model . . . . . . . . . . . . . . . . . . 230

Table 10. Exposure to 2,3,7,B-TCDD from Industrial Accidents . . . . . . . . . . . . . . ... 232

Table 11. Observed and Expected Deaths from Stomach, Colon, and Lung Cancer in the 74 Cases with Chloracne or Severe Dermatitis from the 1953 BASF Plant in Ludwigshafen (26-Year Follow-Up with at Least 10 Years' Latency) ................... 233

Table 12. Estimates of 2,3,7,B-TCDD Exposure to Workers at the BASF Plant in Ludwigshafen Based on Mean Adipose Levels in Four Subjects 30 Years Later and Various Assumptions . . . . . . . . . . . . . 235

Table 13. Comparison of Incremental Cancer Risk Estimates for Lifetime Exposure to 2,3,7,B-TCDD Based on the Kociba Female Rat Liver, Lung, and Hard Palate/ Nasal Turbinates (HP/NT) Response with Estimates Based on Lung and Stomach Cancer Mortality in 74 Workers at the BASF Plant in Ludwigshafen (Assume LADD = 50 pg/kg bw-day) ............ 236

Table 14. Follow-Up of 121 Chloracne Cases at the Monsanto Company (Nitro, West Virginia) Used to Derive Quantitative Cancer Risk Estimates . . . . . .. .. 238

Table 15. Comparison of Incremental Cancer Risk Estimates for Lifetime Exposure to 2,3,7,B-TCDD Based on the Kociba Male Rat Liver, Lung, and Hard Palate/Nasal Turbinates (HP/NT) Response with Estimates Based on Sarcoma Mortality in 121 Monsanto Employees (Assume LADD = 50 pg/kg bw-day) ........ . .. 239

Rationale for a Hormone-Like Mechanism of 2,3,7,B-TCDD for Use in Risk Assessment

Table 1. Association of Estrogens with 2,3,7,B-TCDD Toxicity .. 253

xvi

CHAPTER 3. TECHNOLOGY ASSESSMENT WORKING GROUP Formation of Dioxins and Related Compounds from Combustion and Incineration Processes

Table 1. Amounts of Dioxins Produced on Different Fly Ashes Using 100 ~g of [13C6 1-labeled Pentachlorophenol . Catalytic Dechlorination/Hydrogenation of a Mixture of 200 ~g of Cl~DD and 4 ~g of ClsDF

Table 2.

Table 3.

Table 4.

Table 5. Table 6. Table 7. Table 8.

Table 9.

Table 10.

Table 11.

Table 12.

Table 13.


Table 18. Table 19. Table 20. Table 21. Table 22.

Table 23.

Table 24. Table 25. Table 26. Table 27. Table 28. Table 29.

Table 30. Table 31. Table 32.

Table 33.

Table 34.

Table 35.

Table 36.

Table 37.

Table 38.

with 1 g of Copper at 280·C . . . . . . . . . Fly Ash Samples From Two Municipal Waste Incinerators and a Waste Incinerator Operated By a University were Heated at 280·C for Two Hours CleDD (2 mg), Containing About 40 ~g of CleDF as a Contaminant, was Added to 5 g Fly Ash and Treated at 280·C for the Times Specified Thermal Behavior of PCDD on Fly Ash Thermal Behavior of PCDF on Fly Ash Formation of PCDD/PCDF . . . . . . . Influence of Temperature on the Formation of PCDD/PCDF . . . . . . . . . . . . . . Concentration of PCDD Congeners after 2 Hours of Annealing Time at 300·C . . . . . . . . . . Influence of Copper(II) Concentration on the Formation of PCDD/PCDF . . . . . . . . Role of Particulate Carbon on the Formation of PCDD/PCDF Formation of PCDD/PCDF on Fly Ash from Various Municipal Waste Incinerators Performance Test Condition Selections and Settings Summary of Key Operating Parameters I Summary of Key Operating Parameters II Comparison of Emission Data Concentrations of Organic Compounds at Boiler Inlet in Comparison to Stack Summary of Characterization Test Conditions Selection of Performance Test Conditions . . Summary of Performance Test Conditions . . . . Summary of Key Operating Parameters . . . . . PCDD Concentrations in Flue Gas and Efficiency of Removal . . . .. . ..... . PCDF Concentrations in Flue Gas and Efficiency of Removal . . . Percent Removal of Other Organics Proportion of Ash Collected in Each Vessel PCDD Concentrations in Ash . . . . . PCDF Concentrations in Ash . . . . PCDD/PCDF Homologues Per Performance Test Mode Average Parameters and Conditions of the Flue Gas Cleaning System Gasphase PCDD and PCDF Removal, Run 1 Gasphase PCDD and PCDF Removal, Run 2 Average Composition of Refuse in Two Ontario Incinerators .... . . Concentrations of PCDD and PCDF in Refuse Samples from Two Onta~io Incinerators Concentrations of Chlorinated Organics in Refuse Samples from Two Ontario Incinerators Experiments at the Municipal Waste Incinerator in Umea, Sweden Comparison of Emissions from Incineration and Related Processes in Sweden Quantitative Comparison of Some Selected PCDD/ PCDF in Fly Ash from Different Countries PCDD/PCDF-Contents in Flue Gases from Municipal Waste Combustors

281

284

285

286 289 289 290

290

291

291

292

293

300 301 301 302

305 312 313 313 314

316

316 318 318 319 319 324

326 327 328

328

329

330

331

331

332

334

xvii

Table 39.

Table 40. Table 41. Table 42. Table 43. Table 44. Table 45.

Table 46.

Table 47.

Table 48.


Table 54.

Table 55.

Table 56. Table 57.

Table 58. Table 59.

Table 60.

Table 6l.



Table 70.

Table 7l. Table 72.

Table 73.

Table 74.

Table 75.

Table 76.

Table 77.

Table 78.

Table 79.

XVIii

Typical Ranges of PCDD/PCDF-Contents in Flue Gases and Residues from Municipal Waste Combustors Normal Operating Parameters of the Plant PCDD-Contents in Fly Ash and Filter Dust PCDF-Contents in Fly Ash and Filter Dust PCDF-Contents, Flue Gas PCDF-Contents, Flue Gas Comparison of PCDD and PCDF Emissions During RDF-Only and RDF-Natural Gas Firing Comparison of 2,3,7,8-CL4DD, 2,3,7,8-CL4DF, and CL4DF Emissions During RDF-Only and RDF-Natural Gas Firing Average Emission Concentration and Emission Factors Operating Conditions of Municipal Waste Incinerators A and B Analyses of Flue Gas (Exhaust Gas) Analyses of Fly Ash Analyses of Discharged Water Composition of Municipal Waste Concentrations of PCDD and PCDF in Municipal Waste Incinerators Organic Micro-Pollutants in the Flue Gas Samples; Operation with a Large Excess of Oxygen Influence of Combustion Efficiency on the Production of TCDD-Equivalents Composition of Combusted Waste C14DD and C14DF in the Condensate Before the Abatement System (Upstream) and the Stack (Downstream) . . . . . . . . . . . . . . . Distribution of Worldwide PCDD Emissions Data Summary of Average PCDD and PCDF Congener Concentrations and Calculated Total Values for Municipal Waste Incinerator Emissions Concentration of Chlorinated Organics in Sampling Train Concentrations of Chlorinated Organics in Raw Sludge and Bottom Ash Technical Parameters During Experiments 1 and 2 Incinerated Wastes Technical Parameters during PCB-Burning Experiments Incinerated Wastes, Additional Wastes for Fire Sustain Analytical Results for Experiment 1 to 4 PCDD Formed in Combustion Studies I PCDD Formed in Combustion Studies II PCDF Formed of "Mixture Pyrolyzed: Aroclor 1254 in Insulating Fluids" PCDF Formed Per Gram of Aroclor 1254 Pyrolyzed in Insulating Fluid . Combustion of Arocolor 1254 in Insulating Fluids Comparison of Battelle vs. New York State Department of Health . . . . . . . . . . . Binghamton State Office Building Test Plan: Measurements of Residual Contaminants Some Major Fires Involving PCB Transformers and Capacitors in the United States Analysis of Fluids Involved in Transformer Fire Incidents . . . . . . . . . . Dioxin Isomer Differentiation for Pyrolyzed HCH Residues and TCB Stillbottoms PCBs/PCDD/PCDF Analysis of Various Samples from the Strandley Site in Washington Dioxin and Furan in Dust Samples from Wire Recovery Site, Pittsburgh, PA PCDD/PCDF Analyses (Fire in Reims); Interlaboratorial Comparison

335 336 337 337 338 338

339

340

341

345 346 347 348 348

350

356

357 361

362 363

364

366

367 368 369 370

371 372 380 381

387

388 389

391

391

393

395

396

397

398

399

Table 80. Table 81. Table 82.

Table 83.

Table 84.

Table 85.


Table 91.

Table 92. Table 93.

Table 94.

Formation of Table 1. Table 2.

Table 3.

Table 4.

Table 5.


Table 10.

Table 11.

Table 12. Table 13.

Table 14. Table 15.

Table 16. Table 17.

Table 18.

Table 19. Table 20.

Table 2l. Table 22.

Table 23.

Table 24. Table 25.

Sample Description. .. PCDD/PCDF from Wood Burning Average Concentrations of PCDD/PCDF in Chimney Soot . . . . . . . . . . . . . Concentration of PCDD/PCDF in the Soot of Home Heating . . . . Average Concentrations of PCDD/PCDF in Chimney Soot from Oil and Wood Fired Home Heating Systems Total Particulate - Phase Stack Emission Concentrations of PCDD and PCDF from Two CoalFired Sources PCDD and PCDF in Car Exhausts Analysis of PBDD/PBDF in Vehicle Exhaust . . Formation of PCDD/PCDF by Combustion of PVC Formation of PCDD/PCDF by Pyrolysis of PVC . PCDD and PCDF Released to the Environment from Combustion Sources Average Concentrations of the Toxic PCDD/PCDFIsomers in Chimney Soot from House Heating . Final Ranked Source Category List Average Outlet PCDD/PCDF Mass Emission Rates for the Tier 4 Test Sites Summary of PCDD/PCDF Stack Emissions by Source Category Dioxins and Related Compounds in Industrial Processes Contents of PCDD/PCDF in Chlorophenols Concentration of Chlorobenzenes ~-HCH, Decachlorobiphenyl in a Commercial Sample of Trichlorobenzene . . . . . . . . . . . . . . Concentrations of PCDD/PCDF in a Commercial Sample of Trichlorobenzene . .. ..... Concentration of Organic Pollutants in the Sludge (after filtering) from PCP-Na Production Concentrations of PCDD/PCDF in Sludge from PCP-Na Production PCDD/PCDF Concentrations in Chlorobenzenes PCDD/PCDF Concentrations in Chlorotoluenes PCDD/PCDF Concentrations in Chloroanilines Amounts of PCDD/PCDF and Chloroaromatics in Chorine Gas, Sodium Hypochlorite Solutions and Hydrochloric Acid PCDD/PCDF and Chloroaromatic Compounds in Several Metal Chlorides PCDD/PCDF Concentrations in Aliphatic Chlorine Compounds . . . . . . . . . . PCDD/PCDF in Phthalocyanine Dyes . . . PCDD/PCDF in Motor Oils, Waste Oils and Recycled Oils PCDD/PCDF in Samples of PCP and PCP-Na PCDD/PCDF in Industrial Grade Products of PCP and PCP-Na . . . . . . . . . . . . . . . Emissions of PCDD/PCDF from Production of PCP PCDD/PCDF from Production of PCP-Na from Hexachlorobenzene Chloroorganics and PCDD/PCDF in the Sludge from a PCP-Na Production Site . . . . . . . . . . . . Analysis of Technical Grade Pentachlorophenol PCDD Isomer Differentiation for Pyrolyzed HCH Residues and TCB Sti1lbottoms Concentrations of PCDF and PCDD in Paper . . . . Cl4DD Equivalent Concentrations [pptJ Calculated Using the Toxicity Equivalent Factor (TEF) . . . 2,3,7,8-Cl4DD Concentrations Found in Pulp and Paper Mill Sludges . . . . . . . . . . Quantification of PCDD/PCDF in Pulp Mill A Sludge Concentrations of PCDD/PCDF (Nordic Equivalents) in the Work Environment in Four Steel Mills

400 401

402

403

405

406 408 409 411 412

414

416 419

420

425

438

444

445

446

446 448 449 449

460

462

464 467

468 469

471 472

472

473 474

475 477

478

480 480

482

xix

Table 26. List of Brominated Compounds with Potential Formation of PCDD/PCDF . ........ 488

Table 27. u.s. Production of PBBs . . . . . . . . . . . 502 Methods for Degradation. Destruction. and Detoxification of Dioxins and Related Compounds

Table 1. Destruction Efficiency (DE) (%) of KPEG-Treated PCP-Oil . . . . . . . . . . . . . . . . . 524

Table 2. Results of KPEG Chemical Detoxification of PCP-Oil, Montana Pole Site . . . . . . . . . . . 525

Table 3. Spent Solvent-Oil Waste Analysis, Western Processing Site, Kent, Washington 526

Table 4. Bench-Scale Parametric Studies of KPEG Treatment of Solvent-Oil, Western Processing, Kent, Washington 526

Table 5. Recycle Test Run Data for KPEG Treatment of PCB-Contaminated Transformer Oil . . . . . 528

Table 6. Binding of Dioxins to Clay Based Sorbents 537 Table 7. Incineration of Georgswerder Landfill Oils 543 Table 8. Mobile, Rotary Kiln Incinerator for Dioxin

Combustion . . . . . . . . . . . . . . . . 545 Table 9. DEKONTA Test Burns (Shirco Process) 550 Table 10. Alternative Technologies Proposed or Used

for Certain Dioxin-Contaminated Superfund Sites . .. 556 Waste Disposal Sites Contaminated with Dioxins and Related Compounds

Table 1. PCDD Concentrations in Degradation Wastes . . . . 563 Table 2. 2,3,7,8-C14DD in the 2,4,5-T Wastes of the

Moorfleet Plant . . . . . . . . . . . . . . . . . 565 Table 3. Moorfleet Plant Waste Disposed of at Georgswerder 568 Table 4. Estimated Water Budget for the Georgswerder

Landfill . . . . . . . . . . . . . . . . . . . 570 Table 5. PCDD/PCDF in Sediments from the Elbe River and

Associated Water Bodies . . . . . . . . . . . 571 Table 6. Maximum Content of Organochlorine Compounds in the

Waste Disposal Site Muggenburger StraBe . 575 Table 7. Moorfleet Plant Waste in the Muggenburger StraSe

Site . . . . . . . . . . . . . . . . . . . . 575 Table 8. Maximum Contents of Organochlorinc Compounds

at the Moorfleeter Brack Site . . . . . . . 576 Table 9. Moorfleet Plant Waste Disposed of at Malsch . 577 Table 10. PCDD/PCDF in Leachate and Surface Water at the

Malsch Landfill . . . . . . . . . . . . . . . 578 Table 11. Concentrations of Low Volatile Pollutants in

Landfill Gas and Flare Gas . . . . . . . . . . 580 Table 12. Concentration of PCDD/PCDF in Water and Sludge

from Pit IV . . . . . . . . . . . . . . . 585 Table 13. Concentration of PCDD/PCDF in the Oil Seep. . . 586 Table 14. Concentration of PCDD/PCDF in Sludge from Pit IV 586 Table 15. Concentration of PCDD/PCDF in Fly Ash from

Solid Waste Incinerators . . . . . . . . . . . 587 Table 16. Concentration of 2,3,7,8-Substituted PCDD/PCDF

in Fly Ash from Solid Waste Incinerators . . 588 Table 17. Concentration of 2,3,7,8-C14DD and PCDD/PCDF

in Bore Cores from Munchehagen . . . . 589 Table 18. PCDD/PCDF in Samples from the Methanol Waste

Basin at Gernsheim . . . . . . . . . . . . . . 591 Table 19. PCDD/PCDF in Bore Cores from the Waste Disposal

Site at Gernsheim . . . . . . . . . . . . . . . 592 Table 20. PCDD/PCDF in Soil Samples from HCH Contaminated

Areas around Gernsheim . . . . . . . . . . . . 593 Table 21. Estimated Quantities of Hazardous Compounds in

the Karsau Waste Site . . . . . . . . . . . . 594 Table 22. Dioxin Sites by Tier. . . . . . . . . . . . . . 599 Table 23. Dioxin Sites on the Superfund National Priorities

List .. ................ 599 Table 24. C14DD at the Statistically Selected Sites at

Tier 3 . . . . . . . . . . . . . . 601 Table 25. C14DD at the Tier 3 Regional Sites 601 Table 26. Levels of C14DD in Tier 5 Samples 603

xx

Table 27. Tier 5 Site Characterization . . . . . . . . . . . 604 Table 28. Tier 6 Site Characterization . . . . . . . . . . . 606

Results of 2,3,7,8-C14DD Analyses of Tier 7 Soils 608 Summary of Industrial Discharges at Tier 7 Fish

Table 29. Table 30.

Sites . . . . . . . . . . . . . . . . . . . . . 609 Table 3l. Comparison of the Concentration of 2,3,7,8-C14DD

in Soil from Three Experimental Plots at the Times Beach Dioxin Research Facility Sampled in

Table July, 1984, and July, 1988 . . . . . . . . . . . 615 2,3,7,8-C14DD in Biota from the Volgermeerpolder 32. Waste Site . . . . . . . . . . . . . . . . . . . 618

Table 33. Concentrations of Organchlorine Pesticides, PCBs, and PCDD/PCDF in Sewer Sludge . . . . . . . . . . 620

CHAPTER 4. MANAGEMENT OF ACCIDENTS WORKING GROUP Introductory Comment on the Sevesco (Italy) Industrial Accident

Table 1. PCDD and PCDF Positional Isomers . . . . . . . . 631 Table 2. 2,3,7,8-Chlorosubstituted PCDD/PCDF . . . . . . 633 Table 3. Timeline of Events Following Seveso Accident. 637 Table 4. Action Levels or Maximum Tolerable Environmental

Limits for Complex Mixtures of PCDD/PCDF . . . . . 638 Potential PCDD/PCDF Sources in Italy: Survey. Chemical Analysis. Legislative. and Future Needs

Table 1. Potential Sources of PCDD/PCDF and Related Compounds 643 Table 2. Laws and Regulations Concerning Industrial Safety

and Environmental and Occupational Health Before and After Seveso . . . . . . . . . . . . . . . . .. 645

Table 3. Some "Reference Levels" for PCDD/PCDF . . . . . " 645 Contingency Planning: An Expert System (ChEM) for Describing the Level of Response Needed

Table 1. Exposure and Propagation Routes . . . . . . 662 Table 2. Factors Determining Accident Typology 664 Table 3. Factors Determining Prevention, Containment,

and/or Remedial Actions with Reference to Main Human Exposure Routes . . . . . . . . 664

Table 4. Accident Effects . . . . . . . . . . . . . . 665 Individual Protection in the Seveso Cleanup

Table 1. Infirmary Intervention for Minor Accidents or Discomfort in the Decontamination Team of Zone A " 682

Surveillance of TCDD Cleanup Workers Table 1. Medical Monitoring Program. . . . . . . . . . 693

Accidental Release of 2.3.7,8-Tetrachlorodibenzo-p-Dioxin (TCDD) of Sevesco. Italy: Estimation of Total TCDD Released

Table 1. 2,4,5-Trichlorophenol Production at ICMESA Plant (1970-1976) ................. 708

Table 2. ICMESA Reaction Estimated Batch Contents at Start of Shut-Down on July 10, 1976 . . . . . 709

A Brief History of Risk Assessment and Management After the Seveso Accident .

Table 1. Zone B Risk Assessment as Carried Out in March 1984 for Families Having a Vegetable Garden and Courtyard Animals . . . . . . . . . . . 732

Table 2. Extra Cancer Incidence Over a Million People as Reevaluated for Zone B Inhabitants According to U.S. EPA, 1984 . . . . . . . . . . . . . . . . . 732

The Role of Statistical Analysis in the Management of Chemical Accidents

Table 1. Values of Fitted Parameters and Comparison Between Experimental and Model Values for <z> and Uz . . . 751

Table 2. The Discontinuous Nature of Geometry. . . . . . . 756

xx;

LIST OF FIGURES

CHAPTER 1. INTRODUCTION AND BACKGROUND The Nature of the Problem

Figure 1. Chemical Structure of CDDs and CDFs ........... 5

CHAPTER 2. EXPOSURE AND HAZARD ASSESSMENT WORKING GROUP International Exchange of Research and Technology Information on Dioxins and Related Compounds

Figure lao Format for CCMS Pilot Project ....... . Figure lb. Key Words ................. . Figure 2. Instructions for the Preparation of the

Figure 3. Figure 4. Figure 5. Figure 6. Figure 7.

Figure 8. Figure 9.

Format for International Information Exchange on Dioxins and Related Compounds . . .. . Total Funding (5 Year Program) by Working Group Cost Per Project Year . . . . . . . . . . . . Total Funding by Nation . . . . . . . . . . . Working Group A - Total Funding Over 5 Years Funding of Exposure and Hazard Assessment Projects by Nation . . . . . . . . . . . . . Working Group B - Total Funding Over 5 Years Funding of Technology Assessment Projects by Nation . . . . . . . . . . . . . . . . . .

Listing of Laboratories with Expertise in the Analysis of Dioxins and Related Compounds

Figure 1. Matrices Analyzed at Listed Laboratories Figure 2. Quality Assurance Schemes Employed at Listed

Figure 3. Figure 4.

Laboratories . . . . . . . . . . . . Laboratory Affiliation ..... . Laboratory Affiliation in Each Nation

18 19

20 22 23 25 26

27 27

28

46

47 53 54

Inventory of Regulations/Statutes Concerning Dioxin and Related Compounds

Figure 1.

Figure 2.

Number of Regulations/Statutes Reported in Participating Nations by Political Jurisdiction Matrix of Reported Regulations/Statutes Concerning Dioxins and Related Compounds

International Toxicity Equivalency Factor (I-TEF) Method of Risk Assessment for Complex Mixtures of Dioxins and Related Compounds

Figure 1. Various TEF Approaches for CDDs and CDFs Figure 2. Structure-Activity Relationships of PeCDFs Figure 3. Toxicity Equivalents in Emissions from a

Figure 4. Figure 5.

Municipal Waste Incinerator . . . . . . . . Toxicity Equivalents in a Human Milk Sample . . Toxicity Equivalents in a Pentachlorophenol Wood Treatment Site . . . . . . . . . . . . . .

Figure 6a. Medium Resolution GC/MS Analysis of 2,3,7,8-TCDD Figure 6b. High Resolution GC/MS Analysis of 2,3,7,8-TCDD

Rationale for a Hormone-Like Mechanism of 2,3,7,8-TCDD for Use in Risk Assessment

Figure 1. Potential Secondary Mechanisms of Carcinogenic Activity of 2,3,7,8-TCDD .......... .

85

86

103 107

109 110

111 113 113

. . . . 258

xxiII

CHAPTER 3. TECHNOLOGY ASSESSMENT WORKING GROUP Formation of Dioxins and Related Compounds from Combustion and Incineration Processes

Figure 1. Formation of Dioxins from Pentachlorophenol on Fly Ash: Effect of Temperature . . . . Chromatograms from GC/MS-EISIM Analyses of Labelled Dioxins Produced from Labelled

.... 282 Figure 2.

Figure 3.

Figure 4.

Figure 5.

Figure 6.

Figure 7.

Figure 8.

Figure 9.

Figure Figure Figure Figure Figure Figure Figure Figure

Figure Figure Figure Figure Figure

10. 11. 12. 13. 14. 15. 16. 17.

18. 19. 20. 21. 22.

Pentachlorophenol on Ontario Fly Ash at Two Different Flow Rates . . . . . . . Amount of Dioxins Formed from Carbon and Pentachlorophenol on a Model Fly Ash Ratios of Amounts of Dioxins Formed from Pentachlorophenol Divided by the Amounts Formed on Carbon on a Model Fly Ash . . . . . . . Amounts of Dioxins Formed from Pentachlorophenol on a Model Fly Ash . . . . . . . . . . . . . Process Schematic of P.E.I. Two-Stage Combustion System . . . . . . . . . . . . . . Performing Testing Summary; P.E.I. Two Stage Combustion System . . . . . . . . . . . . . Stack Dioxin Homologue Distribution by Test Condition . . . . . . . . . . . . . . Stack Furan Homologue Distribution by Test Condition . . . . . . . . . . . . . . . . . Total Dioxin/Furan Input/Output . . . . . . Distribution of Dioxins/Furans in Solids Distribution of Organics in Solids . . . . Quebec Incinerator Schematic Cross-Section . . Incinerator Gas Slip Stream Take-Off Arrangement FLAKT's Dry-System ........... . FLAKT's Wet-Dry System ......... . Parameters Measured during Characterization Testing ................. . PCDD and PCDF Concentrations in Flue Gas . PCDD and PCDF Concentrations in Hopper Ashes PCDD Homologue Distribution in Hopper Ashes . PCDF Homologue Distribution in Hopper Ashes . . Concentrations of Chlorobenzenes, Chlorophenols, Polychlorinated Biphenyls, and Polycyclic Aromatic Hydrocarbons in Hopper Ashes . . . . . .

Figure 23. Municipal Waste Incinerator with Spray Absorption by Rotary Atomizer . . . . . . . . . . . . . .

Figure 24. Flue Gas Sampling System .......... . Figure 25. GC/MS/SIM Data Showing the Isomer Distribution

Figure 26. Figure 27. Figure 28.

Pattern of Some Selected PCDD/PCDF in the Fly Ash Samples Collected from Different Countries PCDD/PCDF in Exhaust Gas and in Fly Ashes . . PCDD in Flue Gas; Comparison of Two Years .. Ratio of Biphenyl, Carbon Monoxide, and PCDD after Thermal Treatment . . . . . . . . . . .

Figure 29. PCDD/PCDF Concentrations as Function of Burn-Out Temperature . . . . . . . . . . . .

Figure 30. Relationship between PCDD- and CO-Concentration for Three Incinerators . . . . . . . . . . . .

Figure 31. Congener Profile of PCDD/PCDF in Emissions from Three Swedish Municipal Waste Incinerators

Figure 32. Flow Diagram of Liquid PCB Waste Incineration System ................... .

Figure 33. Levels of Combustion Products Found in Activated

Figure 34. Figure 35. Figure 36.

Carbon ................... . PCDF Formation in Mineral Oil by Homolog Average PCDF Formation Versus PCB Concentration PCDF Formation from PCB Askarel and Trichlorobenzene Fluid ........ .

Figure 37. Thermal Combustion System to Model PCB Fire Conditions . . . . . . . . . . . . . . . .

xxiv

283

294

295

296

298

299

303

304 305 306 307 308 309 310 310

311 317 319 320 321

322

326 327

333 343 349

351

352

353

354

375

376 378 378

379

382

Figure 38. Comparison of PCDD and PCDF Formation from PCB, Trichlorobenzene, and Tetrachloroethylene Feeds 383

Figure 39. PCDF Formation from Aroclor 1254 in Silicone Oil by Homolog . . . . . . . . . . . . . . . . . . 384

Figure 40. PCDF Formation from Trichlorobenzene Feed and Tetrachloroethylene Feed . . . . . . . . . . . 384

Figure 41. Average PCDF Formation Versus PCB Concentration.. 385 Formation of Dioxins and Related Compounds in Industrial Processes

Figure 1. Suggested Pathway for PCDD/PCDF Formation in the Reaction of Trichloroethylene with NaOH . . 458

Figure 2. Reaction Mechanisms Involved in the Formation of PCDF Isomers from Various PCB Congeners 485

Figure 3. Dioxin Formation as a Function of Temperature. 504 Figure 4. Tentative Scheme for the Analysis of PXDD/PXDF

in Commercial Products . . . . . . . . . . . . 507 Methods for Degradation. Destruction. and Detoxification of Dioxins and Related Compounds

Figure 1. General Pilot Plant Design of KPEG Dechlorination Process . . . . . . . . . . . . . . . . . . . 529

Figure 2. Thermo-Chemical Decomposition of Chlorinated Hydrocarbons in a Stirred Flowthrough-Reactor 531

Figure 3. Disposition of Materials During Processing, Using In-Situ Vitrification Plant . . . . . . 535

Figure 4. Schematic of Incineration Plant. . . . . . . 541 Figure 5. Rate of Treatment of Soil, NCBC, Gulfport,

Mississippi . , . . . . . . . . . . . . . . . 548 Waste Disposal Sites Contaminated with Dioxins and Related Compounds

Figure I. PCDD/PCDF in the Moorfleet Plant 2,4,5-T Production Process . . . . . . . . . . . 564

Figure 2. Section View of the Georgswerder Landfill with Water Flows . . . . . . . . . . . . 570 Upper Cap Design for the Georgswerder Landfill 573 Layout of the Munchehagen Waste Disposal Site 581

Figure 3. Figure 4. Figure 5. The Regional Distribution of Dioxin Tier

1/2 Sites . . . . . . . . . . . .. .. 598 Love Canal Study Area . . .. . . . . . . . 611 Love Canal Remedial Action Project 613

Figure 6. Figure 7. Figure 8. Monitoring and Sampling Well . . . . . . 622 Figure 9. Scheme of Sampling Apparatus for Organic

Pollutants . . . . . . . . . . . . . . . 624

CHAPTER 4. MANAGEMENT OF ACCIDENTS WORKING GROUP Introductory Comments on the Seveso (Italy) Industrial Accident

Figure 1. PCDD/PCDF Structures . . . . . . . . . . . . 632 Figure 2. Zones A, B, and R of the ICMESA Accident 635 Figure 3. Zone A of the ICMESA Accident. . . . . . . . 636

Potential penn and penF Sources in Italy: Survey. Chemical Analysis. Legislative. and Future Needs

Figure 1. Waste Incineration Plants in Italy (1985) 646 Figure 2. Incinerator Plant Survey Form (Part 1) 648 Figure 3. Incinerator Plant Survey Form (Part 2) 649 Figure 4. Incinerator Plant Survey Form (Part 3) 650 Figure 5. Waste Incinerator Plants in Italy (1987) 651 Figure 6. PCDD and PCDF Recordings from a Municipal

Solid Waste Ihcinerator Fly Ash Extract . . . 653 Contingency Planning: An Expert System (ChEM) for Describing the Level of Response Needed

Figure 1. Two-Level Knowledge Base Structure . . . . . 661 Figure 2. Flow Chart of Accident Notification. . . . . 663

Design Issues in the Long-Term Surveillance of the Affected Population

Figure 1. Vital Status Follow-Up in Italy. . . . . . . 686 Figure 2. Vital Status Follow-Up in the United States. 687 Figure 3. Follow-Up for Mota1ity in Italy. . . . . . . 689 Figure 4. Follow-Up for Cancer Incidence in Lombardy Region 690

xxv

Decontamination of PCDD/PCDF In Situ by Solar and UV Radiation Figure 1. Ultraviolet Absorption Spectrum of TCDD .... Figure 2. TCDD First Photolytic Process in Hydrogen-Donor

Media ................... . Figure 3. Gas Chromatograms of an Aroclor 1254 Solution

in n-hexane . . . . . . . . . . . . . . . . . The Role of Statistical Analysis in the Management of Chemical Accidents

xxvi

Figure 1a,b Sevesco Accident Location and Sampling Sites Figure 1c. Sampling Site Coordinates (y-axis) in

1976-1977 Campaigns . . . . . . . . . . . . Figure ld. Sampling Site Coordinates (x-axis) in

1976-1977 Campaigns . . . . . . . . . . . . Figure 2a. Determination of Maximum Contamination Line

on the Basis of 1977 Campaign . . . . . . . Figure 2b. Locations of Measurement Octets During

1979 Campaign . . . . . . . . . . . . . . . Figure 3. Eight Measured Values of a Well-Calibrated

Octet, and the Corresponding Ideogram . . Figure 4. Graphic Display of Function Fitted to

431 Samples . . . . . . . . . . . . . . . . . Figure 5. Flow Chart for Recovery of Biased Samples and

Comparison of Different Analytical Procedures Figure 6a. Choice of Cylindrical Coordinates for the

1980-81 Campaign . . . . . . . . . . . . . Figure 6b. Comparison of Real Data Against Model Data Figure 7. Correlation Among Five Independent Sampling

Campaigns ............... . Figure 8a,b.Sketches to Compare Different Analytical

Procedures and Cost-Benefit Optimization Figure 9. Examples of Regular Fractals ...... . Figure 10. Correlation Plot Between Observed Areas and

Observed Perimeters for Meteorologic Events

702

703

704

738

741

741

742

742

743

744

746

749 750

753

754 757

758

AB AHH ASME BGA BHout BLB BSOB CA CB CDDs/CDFs CDWG CE CEC C1xDD C1xDF CP CRF DBE DBR DCE EPA EPA-TEF!> EPA-TEQs EFW EISIM EPS ESP FA FF FG FP FRG GerStaff HCB HCH HDPE HxCDD HxCDF HpCDD HpCDF ISW I-TEFs I-TEQs LR MSW MWC

LIST OF ACRONi~S

- afterburner - aryl hydrocarbon hydroxylase - American Society of Mechanical Engineers - German Federal Health Office - baghouse (outlet) - black liquor boiler - Binghamton State Office Building - chimney ash - ch1orobenzenes - chlorinated dibenzo-p-dioxins and -dibenzofurans - Chlorinated Dioxins Work Group - combustion efficiency - Commission of the European Communities - polychlorinated dibenzo-p-dioxins - polychlorinated dibenzofurans - ch1oropheno1s - carbon regeneration furnace - dibromoethane - drum and barrel reclamation incinerator - dich1oroethane - U.S. Environmental Protection Agency

toxicity equivalency factors adopted by EPA in 1987 - toxicity equivalents (based on EPA-TEFs) - energy from waste - electron impact single ion mode (GC/MS detection) - Environmental Protection Service (Canada) - electrostatic precipitator - fly ash - fabric fil ter - flue gas - fire place - Federal Republic of Germany - German statuatory regulation for dangerous substances - hexach1orobenzene - hexachlorocyclohexane - high density polyethylene - hexach10rinated dibenzo-p-dioxin - hexach10rinated dibenzofuran - heptach10rinated dibenzo-p-dioxin - heptachlor ina ted dibenzofuran - industrial solid waste incinerator - International Toxicity Equivalency Factors - International Toxicity Equivalents (based on I-TEFs) - low recovery - municipal sewage waste - municipal waste combustor

xxvii

NATO-CCMS

NA ND NITEP NS NYSDOH OA OCDD OCDF OECD PAH PBB PBDDs PBDFs PCBs PCDDs PCDFs PeCDD PeCDF PEl PCP ppb ppm ppq ppt pu pvc PxDD PxDF RDF RfD SAB SAR SCR SD SSI 2.4.5-T TCB TCDD 2 • 3 • 7 • 8 • -TCDD TCP TE TEF TEQ THC TOX UBA UNEP WB WFB WHO WI WS

xxviii

- North Atlantic Treaty Organization Challenges of Modern Society

- not available - not detected

Committee

- National Incineration Testing and Evaluation Program - not sampled - New York State Department of Health - open air - octachlorodibenzo-p-dioxin - octachlorodibenzofuran - Organization for Economic Cooperation and Development - polynuclear aromatic hydrocarbons - polybrominated biphenyls - polybrominated dibenzo-p-dioxins - polybrominated dibenzofurans - polychlorinated biphenyls - polychlorinated dibenzo-p-dioxins - polychlorinated dibenzofurans - pentachlorinated dibenzo-p-dioxins - pentachlorinated dibenzofurans - Prince Edward Island - pentachlorophenol - parts per billion - parts per million - parts per quadrillion - parts per trillion - polyurethane - polyvinyl chloride - polyhalogenated dibenzo-p-dioxins - polyhalogenated dibenzofurans - refused-derinsed fuel - reference dose - EPA's Science Advisory Board - structure-activity relationship - scrubber - spray dryer - sewage sludge incinerator - trichlorophenoxyacetic acid - trichlorobenzene - tetrachlorodibenzo-p-dioxin - 2.3.7.8-tetrachlorodibenzo-p-dioxin - trichlorophenol - toxic equivalents - toxicity equivalency factor - toxicity equivalents - total hydrocarbon - total organic halogen - German Federal Environmental Protection Office - United Nations Environmental Programme - wood burning - wood fired boiler - World Health Organization - wire reclamation incinerator - wood stove

Documents

Dioxin Perspectives ||