Table Of ContentChlorinated Dioxins
and Dibenzofurans
in Perspective
Edited by
Christoffer Rappe
Gangadhar Choudhary
Lawrence H. Keith
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
First published 1986 by CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
Reissued 2018 by CRC Press
© 1986 by LEWIS PUBLISHERS, INC.
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to
publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials
or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material
reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained.
If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in
any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilm-
ing, and recording, or in any information storage or retrieval system, without written permission from the publishers.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identifica-
tion and explanation without intent to infringe.
Library of Congress Cataloging-in-Publication Data
Chlorinated dioxins and dibenzofurans in perspective.
Based on the 189th National Meeting of the American
Chemical Society, held in Miami Beach, Fla. in Sept. 1985.
Includes bibliographies and index.
1. Dioxins—Environmental aspects. 2. Dibenzofurans—
Environmental aspects. 3. Environmental chemistry.
4. Man—Influence of environment. I. Rappe, Christoffer.
II. Choudhary, Gangadhar, 1935- . III. Keith,
Lawrence H., 1938– . IV. American Chemical Society.
Meeting (189th : 1985 : Miami Beach, Fla.) [DNLM:
1. Benzofurans—analysis—congresses. 2. Dioxins—
analysis—congresses. 3. Environmental Exposure—
congresses. 4. Environmental Pollutants—analysis—
congresses. WA 671 C5435 1985]
TD196.C5C45 1986 628.5 86-18537
ISBN 0-87371-056-8
A Library of Congress record exists under LC control number: 86018537
Publisher’s Note
The publisher has gone to great lengths to ensure the quality of this reprint but points out that some imperfections in the
original copies may be apparent.
Disclaimer
The publisher has made every effort to trace copyright holders and welcomes correspondence from those they have been unable
to contact.
ISBN 13: 978-1-315-89154-5 (hbk)
ISBN 13: 978-1-351-07064-5 (ebk)
Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the
CRC Press Web site at http://www.crcpress.com
This volume was developed from the proceedings of a symposium held in
Miami Beach, Florida at the 189th National Meeting of the American
Chemical Society. It is the result of the combined efforts of many experts
whose efforts have advanced our knowledge of the production, analysis,
distribution, effects and control of chlorinated dioxins, dibenzofurans and
related compounds. This is the third in a series of publications originating
from current technology presented at national meetings of the American
Chemical Society. Using this forum as a catalyst, researchers from all over
the world came together to present and discuss their data and plan future
work in this rapidly developing and sometimes highly emotional technical
area.
This book incorporates a number of changes: the title, the publisher and
the emphasis. The title and content reflect the maturation and evolution of
this subject. The first two books, Chlorinated Dioxins and Dibenzofurans
in the Total Environment, were indicative of the initial phases of research -
developing the measurement process and defining the extent of the problem
caused by these compounds. In contrast, this book emphasizes refining the
measurement process and assessing the effects, measurable or potential, on
humans and their environment. The first two books were published by Ann
Arbor Science and Butterworth Publishers, respectively (the former was
acquired by the latter). Although this book has yet a third publisher, there is
a string of continuity in that Ed Lewis was president of Ann Arbor Science,
then was associated with Butterworth, and is now president of Lewis Pub-
lishers.
The opening section is devoted to the concerns and manifestations of
human exposure to chlorinated dioxins and dibenzofurans. The chapters in
this section describe the analysis and distribution of dioxins and dibenzo-
furans in humans. This includes the special analytical techniques that are
required and the levels and distributions of these compounds that are being
found; one unique study involves the analysis of human samples from
Vietnam.
The second section is comprised of chapters involving formation and
emissions of these compounds from incineration sources. Increased interest
in energy conversion from municipal incinerators and the massive decon-
tamination costs that have resulted from accidental fires in buildings con-
taining transformers with polychlorinated biphenyls (PCBs) have cata-
pulted this source of chlorinated dioxins and dibenzofurans into local,
national and international prominence. The concern revolves around the
potential large-scale epidemiological exposure to these compounds when
they are formed - either accidentally or intentionally - by fires.
CHLORINATED DlOXlNS AND DIBENZOFURANS
The third section is concerned with the continuing problems of sampling,
analysis, fate and destruction of chlorinated dioxins and dibenzofurans in
soils and related matrices. It was the earlier problems associated with
improper disposal of contaminated wastes onto and into soils that focused
much of the initial attention of environmental contamination from these
compounds in the USA. The emphasis now has moved from sampling and
distribution to fate and, ultimately, to removal and destruction of these
pollutants.
The fourth and fifth sections involve analytical techniques: the fourth is
comprised of chapters describing the latest bioassays, and the fifth is a
collection of the most advanced sampling and analytical methodologies.
Together these sections describe state-of-the-art techniques for measuring
the subject compounds or their effects in a wide variety of environmental
matrices. New cleanup techniques and efficient automated fractionations
are described, along with advances, refinements and in-depth comparisons
of the latest analytical methods.
The final section describes current efforts aimed at synthesis (for analyti-
cal standards) and destruction of these highly complex and resistant com-
pounds. As the science of understanding and coping with these compounds
and their problems matures and evolves, so does the focus of our research
efforts. The first of our books, published in 1983, contained two chapters
on synthesis and none on destruction. This volume contains three chapters
on synthesis and/or standards preparation and four devoted to destruction,
removal, reclamation, and disposal of these pollutants.
Thus, throughout this volume we see an emphasis not only on describing
the problems and dangers caused by chlorinated dioxins, dibenzofurans and
associated compounds, but also on discussions of their relationship to man
and the environment. As the science of the study of these compounds
continues to mature, we can expect to see more emphasis placed on the
consequences of exposure to these chemicals-health effects, financial
costs, and environmental effects-in relation to the benefits and risk assess-
ments of removing, containing, destroying, avoiding and legislating against
them. The story isn't over yet.
C. Rappe
G. Choudhary
L. H. Keith
Christoffer Rappe is a Professor and Chairman of Organic Chemistry at the
University of Umei, Sweden. He was previously an associate professor at
the University of Uppsala, Sweden, where he also received his PhD in 1965.
Professor Rappe is Rapporteur in ad hoc groups on dioxin problems of the
World Health Organization (WHO) and of the International Agency for
Research on Cancer (IARC). An internationally recognized authority on
chlorinated dioxins and dibenzofurans, Professor Rappe has been involved
with their synthesis, occurrence, formation, degradation and analysis for
over thirteen years. Other interests include the synthesis, analysis and occu-
pational exposure to nitrosamines, and synthesis, rearrangements and
mechanistic aspects of halogenated ketones. Professor Rappe has authored
more than 150 papers in various fields of synthetic and analytical organic
chemistry.
Gangadhar Choudhary is a chemist in the Measurement Research Support
Branch of the National Institute of Occupational Safety and Health in
Cincinnati, Ohio. He has previously worked at the Canadian National
Research Council in Ottawa, Canada, Reynolds Metals Company in Shef-
field, Alabama and the Center for Disease Control in Atlanta, Georgia,
serving as a photochemical kineticist, senior research scientist, GUMS
chemist, organic-analytical group leader, project director and project offi-
cer for governmental contracts in special trace organic projects. Dr.
Choudhary has been involved with chlorinated dioxins and dibenzofurans
for the past seven years and is the author or editor of five books and thirty
technical articles involving multidisciplinary chemistry. A native of Uch-
hati, Bihar State, India, Dr. Choudhary is a naturalized U.S. citizen and
received his PhD in physical-organic chemistry from the University of
Ottawa, Canada, in 1965.
Lawrence H. Keith is Chemistry Development Coordinator at Radian Cor-
poration in Austin, Texas. Before joining Radian, Dr. Keith was a research
chemist with the U.S. Environmental Protection Agency in Athens, Geor-
gia. He received his PhD in chemistry from the University of Georgia in
1966. He is a member of the Executive Committee of the American Chemi-
cal Society's Division of Environmental Chemistry, having served as secre-
tary and chairman, and currently as alternate councilor and program chair-
man. Dr. Keith is an Advisory Board Member of Environmental Science
and Technology and a delegate to the U.S. National Committee to the
International Association for Water Pollution Research. An editor or co-
editor of nine books and over fifty publications and author of chapters in
various journals and books, Dr. Keith's technical interests center on meth-
ods for analysis of organic pollutants in the environment and on the safe
handling of hazardous chemicals.
Contents
SECTION I
HUMAN EXPOSURE
1. Distribution of Chlorinated Dibenzo-p-Dioxins and Chlo-
rinated Dibenzofurans in Human Tissues from the General
Population, John J. Ryan, Arnold Schecter, Wing-F: Sun
and Raymonde Lizotte. ................................ 3
2. Identification of 2,3,7,8-Substituted Polychlorinated Diox-
ins and Dibenzofurans in Environmental and Human Sam-
ples, Martin Nygren, Christoffer Rappe,
Gunilla Lindstrom, Marianne Hansson,
Per-Anders Berggvist, Stellan Marklund,
Lennart Domelliif, Lennart Hardell, and Mats Olsson ..... 15
3. Chlorinated Dioxins and Dibenzofurans in Human Tissues
from Vietnam, 1983-84, Arnold J. Schecter, John J. Ryan,
Michael Gross, N. C. A. Weerasinghe,
andJohn D. Constable ................................ 3 5
4. Chlorinated Dioxin and Dibenzofuran Levels in Human
Adipose Tissues from Exposed and Control Populations,
Arnold Schecter, John J. Ryan, and George Gitlitz ........ 5 1
5. Investigation of Health Effects Due to 2,3,7,8-Tetrachloro-
dibenzo-p-Dioxin - Missouri, 1983, Paul A. Stehr,
Gary Stein, Karen Webb, Wayne Schramm, Henry Falk,
and Eric Sampson ..................................... 67
SECTION I1
INCINERATION EMISSIONS
6. Determination of PCDDs and PCDFs in Incineration Sam-
ples and Pyrolytic Products, S. Marklund, L.-0 Kjeller,
M. Hansson, M. Tysklind, C. Rappe, C. Ryan, H. Collazo,
and R. Dougherty ..................................... 79
