EPA-560/6-75-004
NATIONAL CONFERENCE
ON
POLYCHLORINATED BIPHENYLS
(NOVEMBER 19-21, 1975, CHICAGO, ILLINOIS)
PRO
Sponsored by: Environmental Protection Agency
in cooperation with:
Department of Agriculture
Council on EnvironmentaT Quality
Department of Health,
Education and Wolta*
Department of the littrfor
CONFERENCE PROCEEDINGS
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
MARC
1976
-------
-------
Conference Proceedings
NATIONAL CONFERENCE ON
POLYCHLORINATED BIPHENYLS
(November 1975, Chicago, Illinois)
Sponsored by
ENVIRONMENTAL PROTECTION AGENCY
in cooperation with
^\ DEPARTMENT OF AGRICULTURE
* COUNCIL ON ENVIRONMENTAL QUALITY
^0 DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
^K DEPARTMENT OF THE INTERIOR
^
r\,
^ General Chairman
^ John L. Buckley, Consultant
Office of Research and Development
'•''• , Environmental Protection Agency
Project Officer
Thomas E. Kopp
Office of Toxic Substances
Environmental Protection Agency
Conference Coordinator and Compiler
Franklin A. Ayer
CONTRACT NO. 68-01-2928
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
March 1976
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard 12th
Chicago, IL 60604-3590
-------
This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency, nor
does mention of trade names or commercial products constitute
endorsement or recommendation for use.
-------
FOREWORD
The proceedings for the "National Conference on Polychlorinated
Biphenyls" is the fourth report submitted under Contract No. 68-91-2928
to the Office of Toxic Substances for the Environmental Protection Agen-
cy. The three previous proceedings submitted under this contract dealt
with Environmental Aspects of Chemical Use in Rubber, Well-Drilling, and
Printing Operations. The PCB Conference was held at the Pick-Congress
Hotel, Chicago, Illinois, on November 19-21, 1975.
The objectives of this conference were to bring together the latest data and
best available expertise to help clarify the problems associated with the
manufacture, use, and disposal of PCB's; to assess the effectiveness of steps
taken to reduce the problems associated with PCB's; to provide a platform
for interested parties to present previously neglected data concerning
PCB's; and to help clarify the feasibility and complications of steps to
reduce the problems associated with PCB's.
Dr. John L. Buckley, Consultant, Office of Research and Development,
Environmental Protection Agency, Washington, D.C., was the General
Chairman of the conference.
Mr. Thomas E. Kopp, Office of Toxic Substances, Environmental Protec-
tion Agency, Washington, D.C., was the Technical Coordinator of the
conference.
Mr. Karl E. Bremer, Surveillance and Analysis Division, Region V,
Environmental Protection Agency, Chicago, Illinois, was site coordinator
and facilitator.
Mr. Franklin A. Ayer, Manager, Technology and Resource Management
Department, Research Triangle Institute, Research Triangle Park, N.C.,
was the Conference Coordinator and Compiler of the proceedings.
in
-------
ACKNOWLEDGMENTS
The National Conference on Polychlorinated Biphenyls owes its success to
many, many people-to the organizers who arranged and accomplished
such a massive undertaking, to the program chairmen and speakers who
contributed so much insight and information, and most importantly, to
the attendees whose interest and response made it all so worthwhile.
My special thanks to the Honorable Russell Train and the Honorable
Nathaniel Reed for their supportive remarks at the Conference. Also, spe-
cial thanks go to Mr. Francis Mayo, Director of EPA's Region V, Chicago;
Mr. Karl Bremer of his staff; and Mr. Thomas Kopp of the Office of Toxic
Substances for their superlative organizational work.
In extending appreciation to one and all, I also express gratitude to Mr.
Franklin A. Ayer of the Research Triangle Institute, and his staff members
Loren Clarke, Roger McGuffey, Brenda Idol, Helen Cantwell, Dianna
Morgan, and Denise McCampbell for the smooth manner in which the
conference proceeded, and the efficient operation of the conference facil-
ities and support services.
John L. Buckley
General Chairman
-------
Table of Contents
(*indicates speaker)
Page
19 November 1975
Opening Remarks 1
John L. Buckley, Ph.D., General Chairman
Keynote Address: Environmental Protection Rx for Public Health 5
The Honorable Russell E. Train
Session I: HEALTH EFFECTS AND HUMAN EXPOSURE 11
David P. Rail, M.D., Ph.D., Session Chairman
Introductory Remarks 13
David P. Rail, M.D., Ph.D.
Some of the Recent Findings Concerning Yusho 14
Masanori Kuratsune, M.D.,*
Yoshito Masuda, and
Junya Nagayama
Pathological Findings Associated With Chronic Experimental Exposure to PCB's 30
Renate Kimbrough, M.D.
Summary of Toxicological Studies on Commercial PCB's 35
J.C.Calandra, M.D., Ph.D.
Pathobiological Responses of Primates to Polychlorinated Biphenyl Exposure 43
James R. Allen, D.V.M., Ph.D.,* and
D. H. Norback
PCB Chlorination Versus PCB Distribution and Excretion 50
H. B. Matthews, Ph.D.,* and
M. Anderson, Ph.D.
Enzymatic and Other Biochemical Responses to Selected PCB's 57
D. J. Ecobichon, Ph.D.
Toxicology of Selected Symmetrical Hexachlorobiphenyl Isomers: I. Biological
Responses in Chicks and Mice 67
Marco Biocca, M.D.,*
J. A. Moore, D.V.M.,
B. N. Gupta, B.V.Sc., Ph.D., and
J. D. McKinney, Ph.D.
Toxicology of Selected Symmetrical Hexachlorobiphenyl Isomers: Correlating
Biological Effects with Chemical Structure 73
James D. McKinney, Ph.D.
vii
-------
Table of Contents (con.)
Page
Toxicity of 2,3,7,8-Tetrachlorodibenzofuran-Preliminary Results 77
John A. Moore, D.V.M.,
B. N. Gupta, B.V.Sc., Ph.D., and
J. G. Vos, D.V.M., Ph.D.
Session II: USES, SOURCES, AND IDENTIFICATION 81
David Garrett, Session Chairman
Introductory Remarks 83
David Garrett
Characterization of Polychlorinated Biphenyls 84
James P. Mieure, Ph.D.,*
0. Hicks,
R.G. Kaley, Ph.D., and
V.W.Saeger, Ph.D.
Overview of Analytical Identification and Spectroscopic Properties 94
Stephen Safe, Ph.D.
Production and Usage of PCB's in the United States 103
Robert L. Durfee, Ph.D.
PCB Disposal, Reclaiming, and Treatment 108
Thomas E. Kopp
Sources of Polychlorinated Biphenyls in Wisconsin 124
Stanton Kleinert
Polychlorinated Biphenyl Usage and Sources of Loss
to the Environment in Michigan 127
John L. Hesse
General Discussion of Session II 134
20 November 1975
Session III: ENVIRONMENTAL FATE AND OCCURRENCE 135
Ian C. T. Nisbet, Ph.D., Session Chairman
Introductory Remarks 137
lanC. T. Nisbet, Ph.D.
Residues of Polychlorinated Biphenyls in the General Population
of the United States 139
Frederick W. Kutz, Ph.D.,* and
S. C. Strassman
VIII
-------
Table of Contents (con.)
Page
PCB Residues in Human Adipose Tissue and Milk 144
Donald Grant, Ph.D.,*
J. Mes, and
R. Frank
Levels of PCB's in the U.S. Food Supply 147
Charles Jelinek, Ph.D.,* and
P. E. Corneliussen
Levels of PCB's in Canadian Commercial Fish Species 155
John M. Graham
The Occurrence of PCB in the National Fish and Wildlife
Monitoring Program 161
Charles R.Walker
Trends of Polychlorinated Biphenyls in Three Lake Michigan Fishes 177
Wayne A. Willford, Ph.D.,*
Robert J. Hesselburg, and
Lawrence W. Nicholson
A Note on Polychlorinated Biphenyls in Air 182
Frederick W. Kutz, Ph.D.,* and
Henry S. C. Yang
Polychlorinated Biphenyls in the Surface Waters and Bottom Sediments
of the Major Drainage Basins of the United States f 183
D.Steve Dennis, Ph.D.
PCB's in Agricultural and Urban Soil 195
A. E. Carey and
J. A. Gowen
(Presented by D. Steve Dennis)
Marine Inputs of Polychlorinated Biphenyls off Southern California 199
David R. Young,
Deirdre J. McDermott,* and
Theadore C. Heesen
PCB Contamination of Southern California Marine Organisms 209
Deirdre J. McDermott,*
David R. Young, and
Theadore C. Heesen
Transport of Chlorinated Hydrocarbons in the Upper Chesapeake Bay 218
T. O. Munson, Ph.D.,*
H. D. Palmer, Ph.D., and
J. M. Forns
ix
-------
Table of Contents (con.)
Page
Recent Studies of Transport of RGB's to Marine Environments 230
Robert W. Risebrough, Ph.D.
Uptake of Three Polychlorinated Biphenyls, DDT and DDE
by the Green Sunfish, Lepomis Cyanellus Raf 236
James R. Sanborn,
William F. Childers, and
Robert L. Metcalf
(Paper previously published but not presented at conference.)
Laboratory Model Ecosystem Studies of the Degradation and Fate of Radiolabeled
Tri-, Tetra-, and Pentachlorobiphenyl Compared with DDE 243
Robert Metcalf,
James R. Sanborn, Ph.D.,
Po-Young Lu, and
Donald Nye
(Paper previously published but no* presented at conference.)
Environmental Transport and Occurrence of PCB's in 1975 254
lanC. T. Nisbet, Ph.D.
General Discussion of Session III 257
Session IV: ECOLOGICAL EFFECTS AND EXPOSURE 259
Donald I. Mount, Ph.D., Session Chairman
Introductory Remarks 261
Donald I. Mount, Ph.D.
*
Summary of Recent Information Regarding Effects on PCB's
on Birds and Mammals 262
Rey C. Stendell, Ph.D.
Pre-1972 Knowledge of Nonhuman Effects of Polychlorinated Biphenyls 268
Charles R.Walker
PCB's: Effects on and Accumulation by Estuarine Organisms 282
David J. Hansen
Summary of Recent Information Regarding Effects of PCB's
on Freshwater Organisms 284
Alan V. Nebeker, Ph.D.
-------
Table of Contents (con.)
Page
Distribution and Excretion of [14C]-2,4,5,2'5'-Pentachtorobiphenyl
in the Lobster (Homarusamericanus) and the Dogfish Shark tgqualus acanthias) ' 292
John R. Bend, Ph.D.,*
Larry G. Hart, Ph.D.,
Anthony M. Guarino, Ph.D.,
David P. Rail, Ph.D., and
James R. Fouts, Ph.D.
Session V: ECONOMICS AND SUBSTITUTES 303
Warren Muir, Ph.D., Session Chairman
Introductory Remarks 305
Warren Muir, Ph.D.
PCB's in Capacitor Applications 306
Richard Rollins
The Economic Impact of a Ban on Polychlorinated Biphenyls 309
Duncan MacArthur* and
Stephen F. Nagy
The Use of Dow Corning® Q2-1090 Dielectric Liquid
in Power Transformers 312
Richard H. Montgomery
Dow XFS-4169L: An Environmentally Acceptable Capacitor Fluid 314
Dean Branson, Ph.D.
Chlorinated Biphenyl Dielectrics—Their Utility and Potential Substitutes 317
David Wood
Some Comments on Alternatives to PCB's 325
Bruno Rey Coquais
PCB's and Their Substitutes — A Brief Look at Some Examples
of Past Tradeoffs 332
Dale Hattis, Ph.D.,* and
Albert Murray, Ph.D.
ENJ-2065-An Electrical Insulating Fluid 334
E.J. Inchalik, Ph.D.
General Discussion of Session V 338
XI
-------
Table of Contents (con.)
Page
Session VI: GENERAL SESSION 341
Introduction
John L. Buckley, Ph.D..General Chairman 343
Christopher M. Timm, Session Chairman 343
Statements on Behalf of Commercial Fishing Interests, Green Bay, Wisconsin
Jean Hermes 343
Glorianne Hermes 343
Gene Lambrich 344
Statement on Behalf of National Fisheries Institute, Washington, D.C 344
Lee Weddig
PCB Body Burdens Deny Full Use of the Great Lakes Fishery Resource 345
Carlos M. Fetterolf, Jr.
Primate Study 347
Wilbur P. McNulty, M.D.
Ultrastructural Features of Gastric Mucosa and Sebaceous Glands After
Ingestion of Aroclor 1242 by Rhesus Monkeys 350
Mary Bell, Ph.D.
The View of the Paper Industry on the Occurrence on PCB's
in the Environment and the Need for Regulation 359
Paul E. Trout
Statement on Behalf of Westinghouse Electric Corporation,
Pittsburgh, Pennsylvania 361
Bernard A. Kerns
Statement Relating to Polychlorinated Biphenyls on Behalf of
the Wisconsin Paper Council 362
James S. Haney
Statement on Behalf of United Electrical Workers Union,
New York, New York 364
David Kotelchuck
Better Late Than Never: The Case for Treating PCB's
As Toxic Substances Now 365
Lee Botts
A Failure of Government 367
Richard R. Knabel
XII
-------
Table of Contents (con.)
Page
Statement of a Concerned Citizen 369
Eileen Johnston
Letter to Mr. Russel B. Train, Administrator,
U.S. Environmental Protection Agency 371
Ray Oltmanns
A Call for Local Government Action 372
State Senator Burnett Bauer
Statement on Behalf of Minnesota Pollution Control Agency,
Rolesville, Minnesota 373
Barry Schade
Statement on Behalf of Bio-International, Inc.,
Woods Hole, Massachusetts 376
Richard T. Ferry
The Duwamish Spill
Major Gordon Goff 377
John S. Thompson 378
Chlorination of Waters for Disinfection — A Study of the Production
of Undesirable Chlorinated Products 379
Richard E. Johnsen, Ph.D.
Statement on Behalf of Tivian Laboratories, Providence, Rhode Island 384
Herbert Gilner
The Need for Cost-Benefit Analysis in Toxic Substance Usage 394
A. Eatock
Comments and Conclusion
Christopher M. Timm 400
Carlos Fetterolf, Jr 400
John Chastam 401
John L. Buckley, Ph.D 401
COMMUNICATIONS TO THE CONFERENCE 403
Some Additional Comments With Respect to Ambient Air Sampling for PCB's 405
Gordon H. Thomas
"Dow Imbiber Bead" 405
Jack Taylor
XIII
-------
Table of Contents (con.)
Page
Citizen Involvement Awareness of Communication 405
Dorcas Thompson
Letter to Conference on Polychlorinated Biphenyls 406
Susan E. Caswell
Letter to the Administrator of the Environmental Protection Agency 407
Mrs. Meredith C. Tucker
Letter to Lake Michigan Federation „ 408
Chairperson, Pesticide Committee, Knob & Valley
Audubon Society of Southern Indiana
Letter to the Environmental Protection Agency, Region V 408
Douglas V. Whitesides, Jr.
21 November 1975
Session VII: APPROACHES TO CONTROL 409
John L. Buckley, Ph.D., Session Chairman
Introductory Remarks 411
John L. Buckley, Ph.D.
A Review of Federal and State Government Roles in Controlling Impacts
of PCB's on the Environment 412
A. Karim Ahmed, Ph.D.
FDA Regulation of PCB's in Food 428
John R. Wessel
Programs and Authorities of the Environmental Protection Agency 431
Walter C. Barber
U.S. Federal Agency Roles and Actions: The Department of the Interior 434
The Honorable Nathaniel P. Reed
U.S. Federal Agency Roles and Actions: National Institute of
Occupational Safety and Health 438
Richard A. Rhoden, Ph.D.
Proposed Canadian Regulatory Measures for PCB's 440
Morris F. Millson, Ph.D.
PCB's in Foods: A Look at Federal Government Responsibilities 443
Joseph Highland, Ph.D.
XIV
-------
Table of Contents (con.)
Page
Concerns and Recommendations of the National Marine Fisheries Service
Regarding Approaches to Control the Polychlorinated Biphenyls Problem 451
Thomas J. Billy
The Role of the Coast Guard in PCB Pollution Control 453
Lt. Cmdr. J. A. MacDonald
Considerations by the Department of Transportation 454
Alfred W.Grella
Observations on and Summary of Session VII 455
Alfred Kolbye, M.D., M.P.H., J.D.
Session VIII: SUMMARY SESSION 457
John L. Buckley, Ph.D., Discussion Chairman
Summary of Session I 459
J.G. Vos, D.V.M., Ph.D.
Summary of Session II 461
David Garrett
Summary of Session III 461
lanC. T. Nisbet, Ph.D.
Summary of Session IV 462
Donald I. Mount, Ph.D.
Summary of Session V 463
Nicholas A. Ashford, Ph.D.
Summary of Session VI 465
Christopher M. Timm
Summary of Session VII 466
Charles IM. Gregg, Jr.
Conference Highlights 468
Richard A. Carpenter
xv
-------
19 November 1975
OPENING REMARKS
John L. Buckley, Ph.D.*
General Chairman
'Consultant, Office of Research and Development, Environmental Protection Agency, Washington, D.C.
-------
OPENING REMARKS
John L. Buckley, Ph.D.'
I'd like to call this meeting to order. I am John
Buckley, with the Environmental Protection Agency. I'd
like to welcome you here to this National Conference on
RGB's, with the subtitle of RGB's in the Environment in
1975.
Most of you in the room are from the UnitBd States,
but there has been major participation from our Cana-
dian neighbors to the north, and in addition, to my
knowledge, representatives from France, Belgium, the
Netherlands, and Japan.
I'd like to extend my personal thanks to my many
colleagues in the EPA both in Washington and in the
regions and in the laboratories, and my colleagues in
other Federal agencies, in the industry, and in academia
who were helpful in getting this conference organized in
the very short period of time we had. I think almost
everyone that I talked to and invited and asked to partic-
*Consultant, Office of Research and Development, Envi-
ronmental Protection Agency, Washington, D.C.
ipate has agreed to do so, and I really look forward to
the next 2 days as a great opportunity.
As I have gone through the process of helping to
arrange the program, many questions have come to
mind. Most of these are listed in the program, and I
guess my aspiration is that we have some additional in-
sights, perhaps some answers in relation to those ques-
tions before we leave.
I think there is a great opportunity for us to learn
together and to go forward from here with a better com-
mon understanding and perception of the situation in
regard to PCB's in the environment.
I'd ask you to remember that we're here to try and
assemble and evaluate what we jointly know, and we're
here also to avoid conclusions as to what it all means. It
doesn't mean we need not reach conclusions, but it does
mean it's probably not appropriate to try and tie every-
thing down and understand just where we've been by the
end of this meeting.
-------
19 November 1975
KEYNOTE ADDRESS
The Honorable Russell E. Train*
* Administrator, Environmental Protection Agency, Washington, D.C.
-------
ENVIRONMENTAL PROTECTION
Rv FOR PUBLIC HEALTH
Russell E. Train1
More than 4 years ago, while I was serving as Chair-
man of the President's Council on Environmental Quali-
ty, a Federal interagency task force began addressing
itself to the same basic question that concerns this con-
ference: What do we know and what should we do about
polychlorinated biphenyls, or PCB's?
In its report of May 1972, the taskjorce concluded
that PCB's were highly persistent, could be found in all
parts of the environment, could "bioaccumulate" to
relatively high levels in fish, and could have serious ad-
verse effects on human health. The task force recog-
nized, at the same time, that for uses in closed electrical
systems, PCB's had some very real advantages over other
materials. They conduct heat, but not electricity. The
only available substitutes for use in capacitors and in
transformers—which are widely used in indoor electrical
systems—were flammable. It appeared that to ban PCB's
from these uses would be, in effect, to substitute a safe-
ty hazard for a health hazard.
The task force, as a result, recommended the discon-
tinuance of all current uses of PCB's except in closed
electrical systems. It also called for early enactment of
the Toxic Substances Control Act to provide the regula-
tory authority required not only to deal more effectively
with the problems posed by PCB's and other chemicals
already in the environment, but to take sensible steps to
prevent such chemicals from posing such problems in the
first place.
Already in 1972, the sole American producer of
PCB's had voluntarily restricted the sales of PCB's to
uses in closed electrical systems. Both the Food and
Drug Administration and the Environmental Protection
Agency announced actions designed to reduce the levels
of PCB's in our food and our waters.
The United States asked the Organization for Eco-
nomic Cooperation and Development (OECD) to take
appropriate action, on the international level, to control
PCB's. In February 1973, in the first international agree-
ment aimed at limiting the production and use of chemi-
cals in order to protect the environment, the member
countries of the OECD announced their decision to
prohibit the use of PCB's for industrial or commercial
purposes except in certain closed systems. I might add
that one member country, Japan, after PCB contamina-
*Administrator, Environmental Protection Agency, Wash-
ington, D.C.
tion of rice oil adversely affected 1,000 people, has
banned the future production or import of PCB's.
We believed that all these measures added up to an
effective, comprehensive program that would "take
care" of the PCB problem, and would enable us to con-
tinue to take commercial advantage of the unique prop-
erties of PCB's while insulating the public and the envi-
ronment against exposure to hazardous levels of these
chemicals.
Instead, more than 3 years later, we find that, al-
though PCB levels in food have steadily declined, PCB's
are present in our environment to a far greater degree
and at higher levels than we have previously thought. We
have found high PCB levels-levels greatly exceeding
FDA guidelines—in salmon, striped bass, and other fish
in the Great Lakes, the upper Mississippi River, Southern
California, the Gulf of Mexico and in the Hudson River
and other waterways in New York State. Our selective
sampling of drinking water disclosed the presence of
PCB's in the water supply of two communities.
The evidence we have accumulated over the past 3
years has underscored our original concern over the
toxicity of PCB's and over the potential health hazard
posed by the presence of high PCB concentrations in
waterways, in water supplies, and in fish. This, in brief,
is the situation we find ourselves in today.
We have called this conference to help us deal with
it, to determine, as I said at the outset, what we know
and what we should do about PCB's.
We do know one thing that we must do, that we
should have done 3 years ago when the task force urged
us to do so, and that, had we done it, might have en-
abled us to really come to grips with the PCB problem
and rendered this conference unnecessary—that is, to en-
act an effective toxic substances control law. I cannot
help but recall that when I became the first Chairman of
the Council on Environmental Quality in February
1970, my very first directive to our small staff was to
develop a legislative proposal for dealing with this class
of problem. The time had clearly come for an effective
mechanism to deal broadly with such problems, not only
after the fact, but also to help prevent their occurrence
in the first place.
Almost 5 years have now passed since President
Nixon first proposed such legislation to Congress. Over
those 5 years we have introduced into the commercial
market an estimated 600 chemical compounds annually.
We have done so without any systematic, advance assess-
-------
ment of Their potential impact upon public health. Yet,
as we have learned through our experience with such
materials as vinyl chloride, we may not discover how
harmful a compound can be until years after it has be-
come a rather commonplace item in our everyday lives,
even a significant factor in our economy. Also, again and
again we find ourselves engaged in an extremely difficult
and drawn-out struggle to protect the public from a
hazard to which it has already been exposed while at the
same time trying to avoid putting people out of business
or out of work. We find ourselves trying to choose be-
tween a health hazard and a safety hazard. We find our-
selves without the authority we need to really cope with
the problems posed by PCB's, the authority to limit
selected uses and distribution of PCB's as well as to
require testing concerning the health and ecological
effects of proposed substitutes.
With regard to PCB's, we will continue to address
the problem as effectively as we can under existing
authorities, especially under the Water Act, while at the
same time recognizing the inherent inadequacies of the
piecemeal approach we are forced to take. We are also
working on measures we would propose under any toxic
substances bill that may be enacted. They would take
into account, not only the available information on
toxicity and exposure levels, but also the impact of any
regulatory steps upon business, employment, and the
economy, I look forward to the contributions this con-
ference can make to the development of an effective
regulatory program for PCB's both under existing auth-
ority and under a toxic substances law.
About a month ago, in testimony prepared for
delivery before the Environment Subcommittee o1 the
Senate Commerce Committee, Dr. David Rail, who is
scheduled to follow me this morning, said, and I quote-,
"Toxic substances control legislation which prevents the
exposure of segments of the population to disease-pro-
ducing substances is a key element of preventive medi-
cine." There is, indeed, an increasing body of evidence,
and an impressive array of expert opinion that we may
be approaching the whole question of human hed'th
from the wrong side, that, as a matter of national poiicy
as well as of personal practice, an ounce ot prevention
may well be worth a pound of cure.
The Department of HEW estimates that our total
national health bill this year wili add up to nearly $120
billion. Yet a good many informed obsew«ri believe
that, because most of that money goes for cure rather
than prevention, we are not getting what we pay for.
Our traditional health care system, they say, simply
cannot cope with environmentally-induced diseases. Dr.
Ernst L. Wynder, president of the American Health
Foundation, has pointed out that heart disease, cancer,
stroke, and accidents account for 70 percent of deaths
among Americans. And the chief causes of these diseases
are "environmental" in the broadest sense of that term.
"Thus," Dr. Wynder concludes, "in a society where
infectious diseases have been largely overcome through
sanitary measures, immunization, and antibiotics, the
major causes for today's death toll are chronic diseases.
This death toll is largely due to unhealthy life style-
unhealthy working environments and disease-producr.j
products."
The more sophisticated and sensitive our monitoring
devices become, and the more data we accumulate on
the health effects of pollutants and other agents in the
environment, the worse things look. Over a year ago,
scientists uncovered disturbing evidence that children,
whom we had believed unaffected in any lasting way,
can contract chronic and acute disabilities as a result of
air pollution. As rrany as 20 percent of the children in a
city such as New York, one study concluded, can devel-
op severe and chronic respiratory diseases. Another
study in a southern city with relatively heavy air pollu-
tion had similar results. More recently, a group of scien-
tists reported that the most significant factor in a dra-
matic drop in deaths in the San Francisco area during
the gas shortage early last year—a 13.4 percent decrease
in deaths compared with the same period over the pre-
vious 4 years—was reduced exposure to pollutants from
auto exhausts.
We are spending around $1 billion this year on
research into cures and causes of cancer. The National
Cancer Institute has estimated that the actual cost ot
cancer to people amounts to tens of billions of dollars a
year. Yet the World Health Organization estimates that
from 60 to 90 percent of all cancer is the result of
"environmental" factors, again, in the broadest sense of
that term. We have all read the news stories recently
concerning the 1975 Nooe! award to thiee American
scientists for research into possible links between viruses
and cancer. I was struck by the fact that, in their first
public statements upon receiving the award, two of these
scientists stressed the fact that, in the words of one of
ihem, Dr. David Baltimore of the Massachusetts institute
of Technology, "the role of viruses in cancer is small'
and that " the best hope today for cures is research into
envircinmental causes of cancer." "This," Dr. Baitirnore
went on to say, "is a good place to put funds now."
We should understand, as well, that while environ-
mental orotection often appears to involve substantial
costs, we really have no choice about whether or not we
are going to bear these costs. Society has already been
bearing these costs in one form or another-iri the loss of
recreational uses of rivers and beaches; in the increased
treatment costs of our drinking water, in the damage
-------
from air pollution to buildings, farm crops, and forests;
and most importantly, through medical and hospital
bills, time lost on the job because of illness, human
suffering, earlier mortality, and the like. When we con-
trol and cut pollution at the source, we are shifting its
costs from the shoulders of society as a whole onto
those of the polluter, where they belong in the first
place. Such costs then tend to be passed on to the pci-
luter's customers. But this is the most efficient way of
allocating these costs and of encouraging, at the same
time, the development of both processes and practices
that generate less pollution. Moreover, all our experience
indicates that the cost of the particular pollution to
society as a whole is usually far greater than the cost of
cleanup and control. We estimate, for example, that
measurable annual damages of $11.2 billion from partic-
ulates and sulfur oxide are more than twice the annual
costs of control.
What all of this suggests to a layman such as myself
is that both our popular understanding of, and our
public approach to, health care and disease control are
going to have to undergo a searching reexamination and,
I suspect, radical revision. It suggests that, some of our
most effective "health care" dollars, at least when they
are well spent, may be the "disease prevention" dollars
we spend to curb and control pollution and other agents
that we introduce into our own environment. It suggests
that the battle against disease must increasingly be
fought, not simply in the hospitals and the doctors'
offices, but in our streets and our homes and our offices,
in our air and our water, in our food and our products,
in our personal habits and lifestyles. It suggests that if, in
the words of Dr. Irving Selikoff of the Mount Sinai
School of Medicine in New York, "environmental
disease is becoming the disease of the century," then
environmental protection, in the broadest sense of the
phrase, must become the most important ingredient in
any national health program.
Such a broad prescription may seem far removed
from the mote immediate and urgent concerns of this
conference. But I think we all understand that it is our
failure to get at the real roots of the problem that con-
cerns us here, and our preoccupation instead with the
symptoms and surfaces and single instances of things
that has made this conference and the problem it ad-
dresses so critical.
At the start of my remarks, I successfully resisted
the temptation to issue the dramalic announcement that
this was my last PCB's conference. It is, however, my
fervent hope that you do your work so well at this con-
ference that we will never need to call another one. I
thank you for coming, and I look forward to seeing the
results of your work.
-------
19 November 1975
Session I:
HEALTH EFFECTS AND
HUMAN EXPOSURE
David P. Rail, M.D., Ph.D.*
Session Chairman
*Chairman, Department of Health, Education, and Welfare Committee to Coordinate Toxicology and Re-
lated Programs, and Director, National Institute of Environmental Health Sciences, National Institute of Health,
Research Triangle Park, North Carolina.
11
-------
INTRODUCTORY REMARKS
David P. Rail, M.D., Ph.D.*
The history of RGB's is a remarkable case study in
the continuing story of toxic substances and the public
health. From 1929, when it was first manufactured in
the United States, until 1966, it was presumed that this
substance was being used primarily in a closed environ-
ment. However, in 1966 PCB's were found in fish in the
Baltic Sea. Then they were discovered in birds and other
animals. Since then it has been demonstrated they have
an almost global distribution. Three years after being
discovered as an environmental contaminant, they were
determined to be the causative agent in an outbreak of a
disease in Japan now called "Yusho" or "oil" disease.
Thus, in a relatively short period of time, we saw a
manmade compound introduced into commerce for a
relatively narrow purpose, a closed use, broadened
through new applications, and discovered to be hazard-
ous to animals, birds, fish, and to man. In slighly more
than two generations, we had closed the all-too-frequent
circle of progress: product development, distribution,
use, and resulting hazard to human health.
In 1971, we became concerned that the PCB's
appeared to be an ever-expanding problem whose poten-
tial limits were essentially unknown. Thus, in December
of 1971 we called a 2-day open meeting to discuss the
entire range of current and potential health problems
associated with the widespread use and dispersion of
PCB's. The meeting was broadly attended by scientists
and administrators throughout the world who were con-
cerned with this problem.
The scientists at that meeting focused on the entire
spectrum of problems that needed investigation. Their
papers ranged from biological concerns: animal toxicol-
ogy, mechanisms of action, and human body burden; to
regulatory and control concerns: environmental trans-
port, distribution, and alteration, and occurrence. In his
"Where do we go from here" summary, Dr. Norton
Nelson singled out two general areas of concern.(ref.1).
First, relative to environmental distribution pat-
terns, including: (1) further refinement of sources, and
(2) better quantitation of discharge amounts by route
into water and air. Second, he pointed out that there
were inadequate data to determine if the PCB's caused
malignant tumors in laboratory animal studies and urged
that we follow the ongoing studies with care. He also
pointed out the potential deleterious effects of the
PCB's on reproduction in mammals.
In following up these and the other points Dr.
Nelson made, scientists, many of them in DHEW, have
been engaged in attempting to develop the information
required for the resolution of the biological aspects of
this problem. Last month, in order to insure that our
Department's efforts are as effective as possible, we
established a Subcommittee on PCB's of the DHEW
Committee to Coordinate Toxicology and Related Pro-
grams.
Through this Subcommittee we will:
1. Assemble, review, and interpret data that assess
the health significance of polychlorinated bi-
phenyls, and
2. Formulate recommendations as to future
research needs.
In all of these efforts, we will be cooperating with
those agencies which must carry out regulatory respon-
sibilities in this difficult area. Continuing collaborative
efforts by biological scientists here and abroad have
brought us far toward the resolution of these problems.
The reports which you will hear relating to Health
Effects and Human Exposure in the session which fol-
lows should indicate the progress which we have made
since the 1971 conference.
•Chairman, Department of Health, Education, and Welfare
Committee to Coordinate Toxicology and Related Programs, and
Director, National Institute of Environmental Health Sciences,
National Institutes of Health, Research Triangle Park, North
Carolina.
REFERENCE
1. Norton Nelson, "Comments on Research Needs,"
Environmental Health Perspectives 1 Vol. 1 (April
1972), pp. 181-185.
13
-------
SOME OF THE RECENT FINDINGS CONCERNIMC5 YUSHO
Masanori Kuratsune, M.D.,*
Yoshito Masuda,** and Junya Nagayama1
Abstract
Analysis of Yusho disease, which was first detected
in 1968, has been limited and analyses have produced
varying results. Yusho oil has been determined to con-
tain a high level of polychlorinated dibenzofurans
(PCDF's). Nagayama etal. found thatPCDF levels in the
oil were especially high when the oil was contaminated
with PCB's used as a heat transfer medium. Their studies
also showed that the concentration of PCDF's is much
closer to that of PCB's in liver than in adipose tissues in
patients with Yusho.
The current clinical state of patients with Yusho is
dicussed at length. Subjective symptoms, dermatological
findings, serum triglyceride levels, liver conditions,
mortality rates, and the effects on children born to
mothers with Yusho are all reported.
INTRODUCTION
More than 7 years have passed since the outbreak
of an epidemic of Yusho in 1968. According to the
latest tabulation. Prof. Omae, current chief of the Study
Group for the Therapy of Yusho, reported that a total
number of 1,291 patients have been registered as Yusho
in 22 prefectures of Western Japan by April 30, 1975
(ref. 1).
We would like to describe some of the recent find-
ings concerning Yusho which we think to be particular-
ly relevant for understanding of toxicity of PCB's. For
more detailed information, readers are advised to refer
to original papers appearing mainly in the fourth and
fifth reports of the study on Yusho and PCB (ref. 3).
Most of the patients described in these reports are those
living in Fukuoka prefecture. Published information of
patients living in other areas are unfortunately very few,
so with a few exceptions no reference will be made to
them.
PCB's IN THE BODIES OF PATIENTS
WITH YUSHO
1.
Tissues
First of all, the concentration of PCB's retained in
the tissues and fluids of patients with Yusho should be
referred to before their current clinical state will be dis-
cussed.
Although no accurate estimation is feasible because
of the very limited number of analyses so far made, the
concentration of PCB's in adipose tissues of patients
seems to have been fairly high soon after the occurrence
of poisoning—that is, in November 1968, at least 1
month after the discontinued use of the toxic rice oil by
patients, as shown in table 1. The corresponding concen-
trations were considerably lower in 3 patients who died
in the next year, 1969. However, no such marked dif-
ference could be seen between those who died in 1969
and the subsequent decedents, although cases 7 and 10,
who died in 1970 or 1975, showed quite low levels of
PCB's in adipose tissues. As compared with the figures
available from a nationwide survey on residual PCB's in
autopsied tissues, the levels noted in the recent dece-
dents are considered to be fairly close to the usual level
of ordinary autopsied materials. Similar facts were also
noted for PCB concentration in the skin and liver.
2. Blood
Since the analysis of PCB's in blood started only
after 1972, no figures are available in regard to the blood
levels of PCB's in patients in the earlier stage of poison-
ing. As shown in table 2, however, it is clear that the
blood levels of patients had approached the level of
ordinary persons already in 1972, although they were
still significantly higher than that level. This fact as well
as the previous fact of lowered tissue levels of PCB's in
recent decedents seem to be rather surprising if we con-
sider also that the majority of patients are still showing
various clinical symptoms, as will be discussed later.
*Masanori Kuratsune and Junya Nagayama are with the
Department of Public Health, Faculty of Medicine, Kyushu
University, Division of Analytical Chemistry, Daiichi College of
Pharmaceutical Science, Fukuoka, Japan.
**Yoshito Masuda is with Daiichi College of
Pharmaceutical Sciences, Fukuoka, Japan.
3. Gaschromatographic Patterns of PCB's in the Bodies
of Patients
Masuda first noted a peculiar common gas-chro-
matographic pattern of PCB fractions isolated from vari-
ous tissues, blood, and breast milk of patients with
Yusho and called the attention of the Study Group for
the Therapy of Yusho to it in early 1972. Figure 1
shows a typical example of such a pattern in comparison
14
-------
to
cu
CO
CD
'"*•
w
^
•i—
_i
co
+•> -r-
ro to
u. ro
JD
cu to
r~~ *r~
o to
-c ro
3 -0
eu
3
CO
.(/)
'£
cu
to
o
a
•r-
TJ
to
ro to
u_ ro
fi
cu to
1 •!—
o to
jc ro
3 -Q
j_
<4- * O
O -C T-
4^ •*->
cu ro ro
E eu s_
•i- T3 CU
I— Q-
o
cu
to
ro
0
0
r—
£ i
O Q.
•— - CU S- 3
C ^* <4- S-
CU -i- CU
-— - E r— CU
cu o i o E
u -a cu c C
ro -Q UD to ro o •'"'•'
<4~ ro «N(" eu -t-5 <+- «/)
— «— ' eu to cu c
» J= -Q C O
WD CO CM O 3 O T-
r~- 1 — co — to ro •*->
•CO -CO
> VD > V£>
o en o en
^^ ^— ^^ ^^
^^ «\
o cu
o •—
Ig^l (ft
O CO E
to CU
«• 4-> r—
r— s: CM i— ro
0) >, 3 E
cu -i- o cu TD eu
to :r JD co <: k ^*\ >•)
s- s_ s-
cu eu cu
4-> -f«> 4^
C C C
cu cu cu
CO CO tO
cu cu cu
-S -S xE
CO CO CO
• » • "
i — CM CO
r-» «*
• •
00 «d-
CM O
1 — 1 —
>> en >^cn • en
r— VD r— UD > VO
3 en 3 en o en
•-0 f— rD r— Z 1—
i- 5-
&->,>,
LO CO
co CM r~-
P—
«S A
«^" " LO CU VO CU
^) r~ r^
CD O O) fl3 <1> fO
t/) CQ i/) SI to S!
fO fO fO
0 O O
CO
•
1— "
f*^.
o
•
o
en
o
*^***
>*j
t»
eu
c
cu
CO
eu
J=
r^.
*
o
00
•
CD
CO
O
• O
o r-.
eu en
Q r—
s-
>^
00
*^~
ft
QJ
r—
r*^ rt3
£
(U 0)
t/) U-
fl3
O
^j~
•
00
CO
o
•
o
LO en
• •
IO CM
^-^
CO
3
O
CU
c
ro
3
O
_a
ro en 3
• CO
CM
•
CO
00
•""
.
CM -P CSJ
!>>r*^« CL r**«»
ro en cu en
SI r— OO r—
s_
>^
i-
>> co
co
CO
<^* «>
eu
oo cu en ro
i— E
cu ro cu cu
to s; to u_
ro ro
O 0
^3-
r—
O
co
^^
0
•
o
^~
•
o
**— -.
>^
SM
CU
c
cu
CO
eu
E
cn *"~^
i«^
•
o
^_
•r" LO
^> r*1"*
D-cn
•a: •—
s_
>^
CM
O •>
•— CU
cu ro
co s:
ro
o
co
r— •
^^ •• — N
• 0
co oo
1 II
CM C
O
o
to ^— »
O LO
1 II
r— C
o— ^
o
•"co"
1 II
co c
o
t*— "x
p*v
«EJ" <^J"
1 II
CM C
• «>v
o
^ ^
r— LO
1 II
^* d
o -~—
CJ
CO
en
x^
cu
s- s-
3 -a >,
ro to en
r— CU •«*
ro co i—
c cu ro i
O r- £
•r- ro cu LO
*-> s: t- CM
ro
•z.
15
-------
Table 2. PCB's in blood patients with Yusho,
workers and ordinary persons
Material
Whole blood
Yusho patients
Ordinary persons
Plasma
Yusho patients
Normal persons
Whole blood
Yusho patients
Normal persons
Whole blood
Workers9
No. of
subjects
41
37
15
82
25
11
23
Time of
examination
March - August
1973
1972
Jan. 1972
1972
PCB's (ppb)
Whole basis
riean + S.D.
7
3
6.3 + 4.0
3.0 + 1.3
4.8 + 2.9
2.8 + 1.5
364 + 262
Range
2-?6
1-7
2-15
1- 7
1-12
1- 6
60-920
Refer-
ence
7
8
9
Workers engaged in the production of Kanechlor 200-600 in the air con-
taining 0.05 to 0.2 mg/nr of PCB's [Kanechlor-300 + Kanechlor-400
(1:1)]. Two of them showed dermal signs.
with the common one seen in ordinary persons, which is
very much close to that of a mixture of Kanechlor 500 +
600 (1 : 1). It is easily notable that the peak 1, which
appears immediately after p,p'-DDE in the gas chromato-
gram in figure 1, is very low in patients with Yusho as
compared with ordinary persons, while the peak 5 is
much more prominent in Yusho than in ordinary per-
sons. Masuda and his associates observed this peculiar
pattern (designated as type "A") in blood of about 60
percent of patients with Yusho, and a somewhat similar
pattern (designated as type "B") in about 37 percent
(refs. 4,7,11,12).
Takamatsu et al. also observed the same peculiarity
in the blood of patients with Yusho (ref. 8). It was
further demonstrated that those patients who show the
peculiar gas-chromatographic pattern as designated as
pattern A by Masuda et al. have a higher average concen-
tration of PCB's in their blood than do other patients
(refs. 4,7). Abe et al. (ref. 23) examined in 1974 the
PCB residues in the plasma of 30 children born to 18
mothers who had consumed Yusho oil at Goto Islands,
Nagasaki prefecture. The specific gas-chromatographic
pattern of type A was seen among 24 percent of the
children and 44 percent of their mothers, but the pecu-
liarity seemed somewhat less marked as compared with
the one seen among patients in Fukuoka prefecture.
The chemical and toxicological nature of the com-
pound or compounds yielding the above-mentioned peak
5 must be clarified but have not yet fully been ex-
amined. Masuda, however, considers the peak 5 to be
3,4,2',3',4',5'-hexachlorobiphenyl, judging from its
retention time on the Apiezon L column developed fa-
Jensen and Sundstron (ref. 22).
16
-------
A ; FATTY TISSUE OF YUSHO PATIENT
B ; FATTY TISSUE OF ORDINARY PERSON
C : KANECHLOR 500 + 600 (1:1)
13
Figure 1. Gaschromatograms (ECD) of PCB's on SE-30.
POLYCHLORINATED DIBENZOFURANS
IN KANECHLORS, "YUSHO OIL," AND
TISSUES OF PATIENTS
1. Polychlorinated Dibenzofurans in Kanechlors and
"Yusho oil"
Recently Nagayama et al. analyzed Kanechlors and
three samples of toxic "Yusho oil" used by three inde-
pendent families with Yusho for polychlorinated di-
benzofurans (PCDF's) and polychlorinated dibenzo-p-
dioxins (PCDD's) (ref. 16). They did a column chroma-
tographic fractionation of PCDF's and PCDD's from a
bulk of PCB's by using activated alumina as adsorbent,
and n-hexane, n-hexane containing 20 percent carbon
tetrachloride, or n-hexane containing 20 percent methyl-
enchloride as eluent. The fractions thus obtained were
subjected to gas-chromatographic and mass-spectro-
metric examination. Quantitative estimation of PCDF's
Jind^ PCJDD'^j/vas jnadejjy two methods, namely by
measuring the gas chromatographic peak heights and by
measuring the gas chromatographic peak area of per-
chlorinated derivatives of these compounds.
Although no PCDD's were found in any of these
samples, PCDF's were found in all of them. As shown in
table 3, KC-400 contained the highest concentration of
PCDF's, about 18 ppm of PCDF's consisting of dichloro-
up to pentachloro- dibenzofurans. A peak with the same
retention time as that of 2,3,7,8-tetrachlorodibenzo-
furans, which was kindly provided by Dr. J. G. Vos, was
noted in its gas chromatogram. All of the three samples
of ;"Yusho oil" also contained about 5 ppm of PCDF's,
the major constituents of which were tetra- and penta-
chlorodibenzof urans. Here again, the peak with the same
retention time as 2,3,7,8-tetrachlorodibenzofuran was
noted. Kashimoto also found 1.6 ppm of PCDF's in
another batch of "Yusho oil," as shown in table 5 (ref.
18). Table 4 summarized the concentrations of PCDF's
in Kanechlor-400, reported by several authors. As clearly
noted, there is a fairly large discrepancy in their findings.
Whether or not it was due to their analytical procedures
or to batch difference cannot be decided at the present
time.
Another important fact was disclosed by Nagayama
et al. They determined the concentration of PCB's in
"Yusho oil" as approximately 1,000 ppm or slightly less
than 1,000 ppm, as shown in table 3. Since "Yusho oil"
is known to have been contaminated with Kanechlor-
400, the ratio of the concentration of PCB's to that of
PCDF's in "Yusho oil" is expected to be about
1,000=0.018. The observed ratio, approximately 1,000:5,
17
-------
Table 3. PCDF's and RGB's in Kanechlors and Yusho oil
Sample
Kanechlor
Yusho oil
300
400
500
600
A
B
C
PCDF's
Peak
height
method
1
18
4
5
5
4
5
(ppm)
Perchlo-
ri nation
method
1.5
16.6
2.5
2.7
4.4
5.1
5.2
PCB's
Peak
height
method
_
-
-
830
900
1030
(ppm)
Perch! o-
rination
method
_
-
-
870
920
980
Table 4. Reported concentrations of PCDF's
in Kanechlor-400
Concentration
Authors
Roach et al .a
Nagayama et al .
Kashimoto et al .c
Year
1974
1975
1975
(PPM)
1
18
33
'Ref. 17.
W. 16.
:Ref. 18.
was thus about 250 times higher than expected (table 5).
The reasons for this great discrepancy are not clear yet.
It should be noted, however, that the sample of
Kanechlor-400 analyzed was an "unused" one, while the
Kanechlor-400 present in "Yusho oil" was "used" as
heat transfer medium. This fact suggests a practically
important possibility that Kanechlor-400 and probably
other commercial RGB's, too, will increase their PCDF
concentrations when used as heat transfer medium.
2. PCDF's in Tissues of Patients with Yusho
Nagayama et al. (ref. 24) further examined the
tissues of patients with Yusho for their possible content
of PCDF's. Table 6 summarized their findings. Adipose
tissues and liver from two ordinary persons who died of
accidents contained no detectable amount (< 0.1 ppb)
of PCDF's, but those from three patients with Yusho
who died in 1969 or 1972 were all shown to contain
PCDF's. Figures 2 and 3 show their gas-chromatograms
and mass spectra. The concentration on a whole basis
was 0.009 ppm on average for adipose tissues and 0.013
ppm for liver. This seems to be a rather surprising fact
because in the case of IPCB's the concentration on a
whole basis is usually much lower in liver than in adipose
tissues. When compared on fat basis, another interesting
fact was noted that PCDF concentration was much high-
er in liver than in adipose tissue. Although the number
18
-------
Table 5. Concentrations of PCB's and PCDF's and their
ratios in various materials
Materials
Kanechlor-400
Yusho oil Ad
Bb
Patient Adipose
with tissue
Yusho Liver
PCB's
(ppm)
1,000,000
ca. 1,000
134
1.3
0.05
PCDF's
(ppm)
ca. 20
5
1.6
0.009
0.013
PCB's
PCDF's
50,000
200
84
144
4
Reference
i c.
18
24
Samples of the rice oil produced on February 5 or 6,
1968.
"'A sample of the rice oil produced on February 10,
1968.
Table 6. PCB's and PCDF's in tissues of patients
with Yusho and ordinary persons
Subjects
Yusho
patients
Ordinary
persons
Case
Tissue No.
1
2
Adipose 3
Avg.
1
2
Liver 3
Avg.
Adipose ^
•Liver 1
2
Time
of
death
1969
1969
1972
1969
1969
1972
1975
1975
1975
1975
PCB's
-------
UPPER :
PCDF FRACTION FROM
LIVER OF YUSHO PATIENT
LOWER :
PCDF FRACTION FROM
YUSHO OIL,
10
20
30
MIN.
Figure 2. Gaschromatograms of PCDF fractions from liver of patient
with Yusho and from "Yusho oil."
of analyses made is quite limited and nothing can be said
with certainty, this fact seems to deserve attention. As
shown in table 6, these different behaviors in tissue dis-
tribution of the compounds caused a remarkable differ-
ence in ratio of PCB's to PCDF's between adipose tissues
and liver. It was thus demonstrated that the concentra-
tion of PCDF's is much closer to that of PCB's in liver
than in adipose tissues in patients with Yusho. The
PCDF's identified in liver were mainly penta- and hexa-
chlorodibenzofurans, containing only a trace of tetra-
chloroisomers.
CURRENT CLINICAL STATE
OF PATIENTS WITH YUSHO
In 1974, Prof. Urabe (ref. 2), former chief of the
Study Group, reported that the dermal and mucosal
signs that were most marked at the incipient stage of the
poisoning had gradually been improved, while symptoms
such as general fatigue, poor appetite, in constant ab-
dominal pain, heavy headedness and headache, feeling of
numbness and pain at the limbs, and cough and expecto-
ration of sputum, all of which are considered to be due
to some internal disturbances, have become more promi-
nent year by year. In view of these tendencies together
with the discovery of a characteristic gas-chromato-
graphic pattern of PCB's remaining in the blood and
tissues of patients, the diagnostic criteria for Yusho was
revised in 1972 (ref. 2), as shown in table 7. As com-
pared with the former one, the revised criteria describe
briefly the dermal and mucosal lesions but newly refer
to other noncutaneous objective signs and findings from
several laboratory tests. It should be noted, however,
that the new criteria do not refer to any specific liver
function tests.
20
-------
+ 03 /*
^^ *»
CO
—
in *^
vJ o if) *
O VJ5 -
CO Jg
IE % — ' ~
cs
CJ
+
o
i
0
0
^o — * —
N / ^
> i
1
—
•
—
.
^=
- "^"
r i
O
•m
o
•o
CO
X
E
o
-in
Of
o
o
o o ob o oci
o «o o «o
M- 0
o c:
*• J1"
= Q
£ a?
-"g
C N
O '(/>
•s a>
tJ Jr
S c
**- >
V) f
U_ **"'
O "c
Q- ns
^
CO
6
00
0}
3
g>
iJL
(25) A1ISN31NI 3AIiV13y
21
-------
Table 7. The diagnostic criteria for Yusho
(revised in October, 1972).
Yusho is considered as an acute or subacute poisoning with
PCB. The general symptoms currently seen are retarded growth,
neuroendocrine disturbances, phenomenon of enzyme induction,
disturbances in the respiratory system, and abnormal lipid metab-
olism. As the local symptoms, acneform eruption and pigmentation
as cutaneomucosal lesions and ocular symptoms are seen.
1. Conditions of attack
Fact of ingestion of Kanemi rice oil contaminated with PCB
and familial occurrence seen in most cases.
2. General symptoms
a. Subjective symptoms
1) general fatigue
2) heavy headedness and headache
3) inconstant abdominal pain
4) feeling of numbness and pain at the limbs
5) swelling and pain at the joints
6) cough and sputum
7) changes in menstruation
b. Objective symptom
1) bronchitis-like symptom
2) sensory neuropathy
3) bursitis
4) inhibition in growth and abnormal teeth in children
5) Small-For-Dates baby and pigmentation of the entire
skin of newborns
c. Results from clinical examination
1) abnormal properties and concentration of PCB in
blood
2) increase of neutral lipids in blood
3) anemia, lymphocytosis, hypoalbuminemia
4) reduced velocity of the sensory nerve conduction
and adrenocortical hypofunction
3. Cutaneomucosal signs
a. Acneform eruption
Black comedones and acneform eruptions which are seen
at the face, buttocks, and other intertriginous sites
and their suppurative tendency.
b. Pigmentation
Pigmentation of the face, palpebral conjunctiva, gingiva,
and nails of the fingers and toes.
c. Ocular signs
Swelling and hypersecretion of the Meibomian gland and
palpebral edema.
(Translation was made by Kuratsune)
22
-------
1. Subjective Symptoms
Table 8 shows that a considerable portion of the
patients are still suffering from various subjective
symptoms in recent years. Koda and Masuda examined
their possible association with PCB concentrations in
blood, finding no positive association at all (ref. 4).
Umeda also reported on various symptoms due to dis-
turbances of higher nervous activities (e.g., forgetfulness)
complained of by most patients, but no definite associa-
tion between such symptoms and the blood levels of
PCB's was observed (ref. 5).
2. Dermatological Findings
Koda and Masuda examined 72 patients with Yusho
for dermatological signs and PCB levels in the blood
from April 1973 to March 1974 (ref. 4). As shown in
table 9, the majority of patients were still suffering from
skin lesions such as pigmentation, deformation of nail,
and hypersecretion of Meibomian gland even 5 years
after the poisoning. They also demonstrated another im-
portant fact that group A, consisting of patients whose
blood shows the gas-chromatographic pattern A, had
significantly higher prevalences of dermatologic signs
such as pigmentation, acneform eruption, and deformed
nails than did group B, which consisted of patients show-
ing no such typical gas-chromatographic pattern.
Since group A had a higher average concentration of
PCB's than group B, the dermal lesions seen among cur-
rent patients, contrary to the subjective symptoms, seem
to be causally associated with the current level or pat-
tern of PCB's remaining in their blood. However, no
conclusion could be readily made in this regard. First of
all, the current excess of PCB's in the blood of patients
is not remarkable in degree and is almost negligible as
compared with the enormous elevation seen among the
occupationally exposed workers, who nevertheless
showed a rather low prevalence of dermal symptoms
(table 2).
It seems rather hard, therefore, to explain the
persisting dermal lesions by elevated PCB levels in
blood alone. The chemical peculiarity of such PCB's and
the presence of PCDF's in the bodies of current patients
seem to be particularly important in this connection.
However, our present knowledge does not allow us to
continue discussion of the matter along this line without
speculation. Furthermore, an entirely different explana-
tion might also be possible. The skin lesions currently
seen may merely be the persisting original skin lesions,
the severity of which must have been determined pri-
marily by the amount of intake of PCB's; such intake
must in turn be reflected by the current PCB levels in
blood of patients. According to this explanation, the
Table 8. Frequency of subjective symptoms
complained by patients with Yusho
from 1973 to 1974
Proportion'
Symptoms %
Fatigue
Headache
Phymata in articular region
Fever
Cough and sputum
Digestive disorder
Numbness of extremities
Menstrual disturbance
51.4
41.7
8.3
2.8
56.9
40.3
33.3
26.9
(7/26)
Calculated by Kuratsune from original
figures published by Koda and Masuda
(ref. 4).
23
-------
Table 9. Prevalence of dermatological and other signs
among patients with Yusho from April 1973 to
to March 1974, in connection with concentration
and gaschromatographic pattern of PCB's in
blood
Prevalence (%)c
Signs
Skin
Pigmentation J^lp
-------
serum triglyceride at least once a year successively for 6
years from 1969 to 1974 (ref. 19). As shown in table 10,
a group of 14 male patients has shown no significant
change in serum triglyceride levels since 1969, still main-
taining levels as high as 160 ± 118 mg/100 ml even in
1974. For 26 female patients, however, a significant de-
crease was seen in 1973 and 1974 when compared with
the levels in the previous years. However, 42 percent of
them still showed higher levels than 110 mg/100 ml in
1974.
Okumura et al. (ref. 20) examined the possible asso-
ciation between serum triglyceride levels and PCB con-
centrations in blood in patients. As shown in table 11,
they observed a significantly higher mean level of serum
triglyceride in a group of patients who showed the
characteristic gas chromatographic pattern A, as com-
pared with other patients who did not show such a typi-
cal pattern. They also observed a significantly positive
correlation between serum triglyceride levels and PCB
concentrations in blood (r = 0.485).
Table 10. Results of followup study on serum triglyceride
levels in patients with
Subjects
Patients
with
Yusho
Controls
Controls
PCB's
No.
PCB's in
Age blood
pattern cases mean (ppb)
A
B
C
C
20
14
2
37
31.9 8.6 + 5.2b
21.4 3.8 + 2.2°
34.5 2.8 + 1.6
Triglyeeride
mg/100
134 +
91 +
74 +
ml Reference
60. Oa
39.8°
29
20
19.21
T < 0.05.
V < 0.005.
Table 11, PCB's concentrations in blood and serum
triglyceride levels in patients with Yusho
in 1973
Sex
Male
Fema 1 e
Patients
Age No.
11 - 73 14
7 - 59 26
Triglyceride (mg/100 ml)
Mean + S.D.
1969
159+57
155 + 75
1970
166 + 55
161 + 70
1971
169 + 60
155+80
1972
174 + 69
153 + 63
1973
164 + 68
129 + 50b
1974
160 + 118
111 + 56b
Cited from a report by Okumura et al. (ref. 19).
Significantly lower than in 1969, 1970, 1971, and 1972 (P < 0.05).
25
-------
Here again, a similar question can be raised in regard
to such observed correlation, as already discussed in con-
nection with the dermal lesions. Are the current elevated
levels of PCB's in blood and their peculiarities in gas-
chromatographic patterns causally connected with the
abnormally high serum triglyceride levels found in
patients? Since, as mentioned, the female patients
started to decrease in serum triglyceride concentration in
recent years, a followup examination of PCB's in their
blood might give a good clue to answer the above ques-
tion.
4, Liver of Patients with Yusho
Both PCB's and PCDF's are well-known toxic agents
to the liver. PCDF's seem to be particularly toxic be-
cause a single oral administration of PCDF's as small as
about 1 mg/kg could kill rabbits by severe liver necrosis
(refs. 28,29). Therefore, it is reasonable to expect that
patients with Yusho would have a severe liver damage.
Okumura et al. (ref, 30) performed detailed medical
examinations on 24 patients soon after the onset but,
unexpectedly, obtained no objective findings to indicate
definite liver disorders. No patients presented jaundice
and only three of them had palpable livers. However, an
electron microscopic examination of liver biopsy speci-
mens conducted on a patient in February 1969 revealed
a marked hypertrophy of smooth endoplasmic reticu-
lum, indicating stimulated enzyme induction in the liver
(ref. 31).
Okumura examined 38 patients with various subjec-
tive symptoms for serum enzymes, including isozymes
from 1971 to 1972 (ref. 32). An increase in a fraction of
lactate dehydrogenase (LDH-5) and high titers in thymol
turbidity tests were observed in some of the severe cases
but no definite evidence for liver disorders was obtained.
Recently Hirayama et al. (ref. 33) examined 121 adult
patients with Yusho and 257 healthy adult controls for
serum bilirubin, demonstrating a significant lower aver-
age concentration in the patient group than in the con-
trol. They also showed significantly negative correlations
between serum bilirubin and blood PCB's in concentra-
tion (r = -0.349, p<0.025) and similarly between serum
bilirubin and serum triglyceride (r = -0.215, p<0.05).
They considered that a lowered concentration of serum
bilirubin in patients seemed mainly due to an accelerated
bilirubin disposal from the blood.
Hirayama et al. investigated 125 patients for Austra-
lia antigen and antibody by the immunoelectro-
osmophoresis in 1971 (ref. 34). The antigen was positive
in three, while the antibody was negative in all of them,
indicating no difference at all in the prevalences between
the patients and healthy controls. This finding seems to
be important in connection with the future risk of
cancer which patients might experience.
In view of all these findings, liver function tests cur-
rently available do not readily detect serious liver lesions
in the patients, but it i;; highly desirable that adequate
caution will continuously be paid to this well-known
target organ of chlorinated hydrocarbons.
CHILDREN BORN TO MOTHERS
WITH YUSHO
The birth of unusual babies from mothers who took
"Yusho oil" during pregnancy is already well known
(refs. 25,26). Their clinical features were dark brown
pigmentation of the mucous membrane and the entire
skin, gingival hyperplasis with pigmentation, a tendency
to be small for the date, eruption of teeth at birth,
hypersecretation of the Meibornian gland, and edema of
the orbital area. Pigmentation of the skin disappeared in
2 to 5 months, followed by growth similar to that of
normal babies.
It seems noteworthy, however, that babies with the
dark brown pigmented skin continued to be born for a
few years after the intake of "Yusho oil" was discon-
tinued by mothers. Yoshimura reported on nine babies
with such skin who were oorn to mothers with Yusho in
Nagasaki prefecture from 1969 to 1972 (ref. 27). Three
of such babies had been delivered by a patient from
1969 to 1971. Abe et al. (ref. 23) recently reported on
PCB levels in the plasma of 30 children (aged 0—7) born
to 18 mothers with Yusho in Nagasaki prefecture. Their
examination was made in 1974. As shown in table 12,
the PCB levels of these children were significantly higher
than those of ordinary children but lower than the levels
of their mothers. Their ga:s-chromatographic patterns of
PCB's in plasma were already referred to earlier in this
paper. Children fed on breast milk from mothers with
Yusho tended to show a higher plasma concentration of
PCB's than those who were not fed on such milk.
Yoshimura also reported an interesting case, where a
baby was thought to have suffered from Yusho due ex-
clusively to intake of PCB's through breast milk from a
woman with Yusho (ref. 27). Very few data are available
in regard to the concentration of PCB's in breast milk of
mothers with Yusho. Masuda et al. found 0.03 — 0.06
ppm of PCB's in 5 samples of breast milk collected from
a woman with Yusho within 5 days after delivery in
1973 (ref. 12). Masuda also found about 0.03 ppm of
PCB's in another sample of breast milk collected a few
days after a woman with Yusho delivered a baby with no
dermal signs (ref. 14). The PCB levels in breast milk
from patients with Yusho were therefore just within the
normal range. However, the gas-chromatographic pat-
terns of these samples were quite unique, the same as
that characteristic for Yusho.
26
-------
Table 12. Concentration of RGB's in plasma of
children born to mothers with Yusho
Subjects
PCB's in plasma
(ppb)
Subjects Range Mean + S.D.
Ref-
erence
Mothers with
Yusho
Children born
to above
mothers
Ordinary chil
dren
18 3-33 11.2 + 7.32
30 1-20 6.7 + 4.28
14 1-8 3.7 + 1.97
23
Table 13. Deaths seen among patients with
Cause of death
Malignant neoplasms
Stomach cancer
Stomach cancer + liver cancer
Liver cancer + liver cirrhosis
Lung cancer
Lung Tumor
Breast cancer
Malignant lymphoma
Cerebrovascular lesion
Amyloidosis
Osteodystrophia fibrosa
Myocardial degeneration + pericarditis
Status thymicolymphaticus
Liver cirrhosis
Suicide
Senility
Traffic accidents
TOTAL
Number
9
2
1.
lb
1
1
1
2
3.
1
1°
' k
lb
1
1
1
3
22
Cited from a report by Urage 1974 (ref. 2).
Autopsied cases.
27
-------
MORTALITY OF PATIENTS
WITH YUSHO
Omae reported in 1975 that 29 deaths occurred
among 1,291 patients with Yusho up to April 30, 1975
(ref. 1). Causes of these deaths were not given, however.
Urabe also reported on 22 deaths seen among 1,200
patients until September 13, 1973, and referred to their
causes (ref. 2). As shown in table 13, 9 of 22 deaths
were caused by malignant neoplasms, suggesting a
possible excess of deaths from cancer. Since some essen-
tial information needed for epidemiological analysis is
not available to us, no further reference can be made
with certainty to such a possibility at the present time.
CONCLUSION
As mentioned earlier, we demonstrated the presence
of PCDF's in "Yusho oil" at a much higher concentra-
tion than expected. We also showed that PCDF's are
relatively more concentrated in liver. Although neither
the chemical nature nor the toxicity of PCDF's con-
tained in "Yusho oil" and in the bodies of patients are
known yet, our findings clearly indicate the necessity to
pay greater attention to PCDF's for clarification of the
nature of Yusho. Furthermore, our studies suggested the
possible formation of PCDF's from PCB's when used as
heat transfer medium. Beside this, another possibility
that PCDF's might be formed by heating PCB's with
peroxides, which are well known to be formed during
heating cooking oils, should also be investigated.
REFERENCES
1. T, Omae, "Foreword, the Fifth Report of the Study
for Yusho and PCB," Fukuoka Acta Med., Vol. 66,
No. 10 (October 1975), pp. 547-458 (in Japanese).
2. H. Urabe, "Foreword, the Fourth Report of the
Study on Yusho and PCB," Fukuoka Acta Med.,
Vol. 65, No. 1 (January 1974), pp. 1-4 (in
Japanese).
3. "Fourth Report," Fukuoka Acta Med., Vol. 65, No.
1 (January 1974), pp. 1-95; "Fifth Report," Ibid.,
Vol. 66, No. 10 (October 1975), pp. 547-648.
4. H. Koda and Y. Masuda, "Relation Between PCB
Level in the Blood and Clinical Symptoms of Yusho
Patients," Fukuoka Acta Med., Vol. 66, No. 10
(October 1975), pp. 624-628 (in Japanese).
5. G. Umeda, "Clinical Aspects of PCB Poisoning,"
Rodo no Kagaku, Vol. 28 (1973), pp. 36-42 (in
Japanese).
6. H. Kohda, S. Asahi, and S. Toshitani, "Dermatologi-
cal Findings of the Patients With Yusho (PCB
Poisoning) in General Examination in 1972,"
Fukuoka Acta Med., Vol. 65, No. 1 (January 1974),
pp. 81-83 (in Japanese).
7. Y. Masuda, R. Kagawa, K. Shimamura, M. Takada,
and M. Kuratsune, "Polychlorinated Biphenyls in
the Blood of Yusho Patients and Ordinary Persons,"
Fukuoka Acta Med., Vol. 65, No. 1 (January 1974),
pp. 25-27 (in Japanese).
8. M. Takamatsu, Y. Inoue, and S. Abe, "Diagnostic
Meaning of the Blood PCB," Fukuoka Acta Med.,
Vol. 65, No. 1 (January 1974), pp. 28-31 (in
Japanese).
9. H. Hasegawa, M. Sato, and H. Tsuruta, "PCB Con-
centration in the Blood of Workers Handling PCB,"
Rodo Eisei, Vol. 13, No. 10 (1972), pp. 50-55 (in
Japanese).
10. M. Goto and K. Higuchi, "The Symptomatology of
Yusho (Chlorobiphenyls Poisoning) in Dermatolo-
gy," Fukuoka Acta Med., Vol. 60, No. 6 (June
1969), pp. 409-431 (in Japanese).
11. Y. Masuda, R. Kagawa, and M. Kuratsune, "Com-
parison of Polychlorinated Biphenyls in Yusho
Patients and Ordinary Persons," Bull. Environ.
Contam. Toxicol., Vol. 11 (1974), pp. 213-216.
12. Y. Masuda, R. Kagawa, M. Kuratsune, "Polychlorin-
ated Biphenyls in Yusho Patients and Ordinary Per-
sons," Fukuoka Acta Med., Vol. 65, No. 1 (January
1974), pp. 17-24 (in Japanese).
13. Committee for Investigation and Study of PCB and
Others, "Study on the Distribution of Concentra-
tions of Intracorporally Accumulated PCB" (1975)
(in Japanese).
14. Y. Masuda, Unpublished data.
15. M. Asahi, H. Koda, and S. Toshitani, "Alteration in
Skin Severity Grading of Yusho in the General Ex-
amination in 1973 and 1974, and Presentation of a
New Standard for the Skin Severity of Yusho by
Point Count System," Fukuoka Acta Med., Vol. 66,
No. 10 (October 1975), pp. 629-634 (in Japanese).
16. J. Nagayama, Y. Miasuda, and M. Kuratsune, "Chlo-
rinated Dibenzofurans in Kanechlors and Rice Oils
Used by Patients With Yusho," Fukuoka Acta Med.,
Vol. 66, No. 10 (October 1975), pp. 593-599.
17. J. A. G. Roach and I. H. Pomerantz, "The Finding
of Chlorinated Dibenzofurans in a Japanese PCB
Sample," Bull. Environ. Contam. Toxicol., Vol. 12
(1974), pp. 338-342.
18. T. Kashimoto, personal communication (1975).
19. M. Okumura, M. Yamanaka, S. Nakamuta, and H.
Uzawa, "Consecutive Six Year Follow-up Study on
Serum Triglyceride; Levels in Patients With PCB
Poisoning," Fukuoka Acta Med., Vol. 66, No. 10
(October 1975), pp. 620-623 (in Japanese).
28
-------
20. M. Okumura, Y. Masuda, and S. Nakamuta, "Cor-
relation Between Blood PCB and Serum Triglyceride
Levels in Patients with PCB Poisoning," Fukuoka
Acta Med., Vol. 65, No. 1 (January 1974), pp.
84-87 (in Japanese).
21. H. Uzawa, A. Notomi, S. Nakamuta, and Y. Ikeura,
"Consecutive Three Year Follow Up Study of
Serum Triglyceride Concentrations of 82 Subjects
With PCB Poisoning," Fukuoka Acta Med., Vol. 63,
No. 10 (October 1972), pp. 401-404 (in Japanese).
22. S. Jensen and G. Sundstron, "Structures and Levels
of Most Chlorobiphenyls in Two Technical PCB
Products and in Human Adipose Tissues," AMBIO,
Vol. 3, No. 2 (1974), pp. 70-76.
23. S. Abe, Y. Inoue, and M. Takamatsu, "Polychlorin-
ated Biphenyl Residues in Plasma of Yusho Children
Born to Mothers Who Had Consumed Oil Contam-
inated by PCB," Fukuoka Acta Med., Vol. 66, No.
10 (October 1975), pp. 605-609 (in Japanese).
24. J. Nagayama, Y. Masuda, and M. Kuratsune, "Poly-
chlorinated Dibenzofurans in Tissues of Patients
with Yusho," paper 330 presented at the 34th
Annual Meeting of Japanese Society of Public
Health, Yokohama, October 29-31, 1975, preprint,
215 pp., October 1975 (in Japanese).
25. I. Funatsu, F. Yamashita, Y. Ito, S. Tsugawa, T.
Funatsu, T. Yoshikane, M. Hayashi, T. Kato, M.
Yakushiji, G. Okamoto, S. Yamasaki, T. Arima, T.
Kuno, H. Ide, and I. (be, "PCB Induced Fetopathy.
1. Clinical Observation," Kurume Med. J., Vol. 19
(1972), pp. 43-51.
26. I. Taki, S. Hisanaga, and Y. Amagase, "Report on
Yusho (Chlorobiphenyls Poisoning) Pregnant Wom-
en and Their Fetuses," Fukuoka Acta Med Vol. 60,
No. 6 (June 1969), pp. 471-474 (in Japanese).
27. T. Yoshimura, "Epidemiological Study on Yusho
Babies Born to Mothers Who Had Consumed Oil
Contaminated by PCB," Fukuoka Acta Med., Vol.
65, No. 1 (January 1974), pp. 74-80 (in Japanese).
28. H. Bauer, K. H. Schulz, and U. Spiegelberg,
"Berufliche Vergiftungen bei der Herstellung von
Chlorphenol-Verbindungen," Arch. Gewerbepath.
Gewerbehyg., Vol. 18 (1961), pp. 538-555.
29. H. Th. Hofmann, "Neuere Erfahrungen mit
Hochtoxischen Chlorkohlenwasserstoffen," Arch.
Exp. Pathol. Pharmakol Vol. 232 (1958), pp.
228-230.
30. M. Okumura and S. Katsuki, "Clinical Observation
on Yusho (Chlorobiphenyls Poisoning)," Fukuoka
Acta Med., Vol. 60, No. 6 (June 1969), pp. 440-446
(in Japanese).
31. C. Hirayama, T. Irisa, and T. Yamamoto, "Fine
Structural Changes of the Liver in a Patient With
Chlorobiphenyls Intoxication," Fukuoka Acta
Med., Vol. 60, No. 6 (June 1969), pp. 455-461 (in
Japanese).
32. M. Okumura, "Course of Serum Enzyme Change in
PCB Poisoning," Fukuoka Acta Med., Vol. 63, No.
10 (October 1972), pp. 396-400 (in Japanese).
33. C. Hirayama, M. Okumura, J. Nagai, and Y. Masuda,
"Hypobilirubinemia in Patients With Polychlorin-
ated Biphenyls Poisoning," Clinica Chim. Acta, Vol.
55 (1974), pp. 97-100.
34. C. Hirayama, M. Nakamura, and M. Yoshinari,
"Australia Antigen in Patients With PCB Poisoning,"
Fukuoka Acta Med., Vol. 63, No. 10 (October
1972), pp. 405-407 (in Japanese).
DISCUSSION
MR. ALLEN GREY (IIT Research Institute, Chicago,
Illinois): Do you have any feel whether dibenzo-
furans concentrating in the body are more rapid in
metabolism than the result of polychlorinated bi-
phenyls?
DR. KURATSUNE: Unfortunately I have no definite
idea. It is a more potent compound than PCB, I
guess. I really cannot say.
DR. ORVILLE PAYNTER (EPA, Washington,
D.C): Are there any reproductive problems or ir-
regularities continuing for many years after the
ingestion of these materials?
DR. KURATSUNE: There is some disturbance of men-
struation. There have been some disturbances and
ther>» have been some related problems.
MS. DEBORAH A. BARSOTTI (University of Wiscon-
sin, Madison, Wisconsin): Were there are doings
that suspected any widespread gastic ulcerations or
an erosion in the patients—gastric ulcers?
DR. KURATSUNE: No, I do not think so. Some of the
patients had very persistent disorders of the intes-
tines-, disorders of the digestive system, but I do not
know if they were suffering as a result of this or
not.
VOICE: Any residual changes in the sebaceous gland
during the autopsy?
DR. KURATSUNE: No, I do not know very much
about it.
VOICE: I would like to ask one more question. Have
you been able to specifically identify any of the
dibenzofurans other than those in the body?
DR. KURATSUNE: You are asking if we could identify
any of the diben2ofurans? No.
29
-------
PATHOLOGICAL FINDINGS ASSOCIATED WITH
CHRONIC EXPERIMENTAL EXPOSURE TO PCB's
Renate D. Kimbrough, M.D.'
Abstract
The principle organs affected by long-term exposure
to commercial mixtures of poly chlorinated biphenyls
(PCB's) in rodents, mink, and monkeys are the gastro-
intestinal tract, the liver, and the lymphatic system.
Lesions of the gastric mucosa have been described in
monkeys, and ulcerations of the gastric mucosa have
been observed in the rat. Pathological changes in the
liver in many species, such as the monkey, rodent, and
mink, consist of hepatomegaly, lip id accumulation, and
liver cell necrosis, particularly at higher dietary levels.
Hyperchromatic nuclei and mitotic figures are noted.
Ultrastructural changes in the cytoplasm of affected
hepatocytes consist of an increase in smooth endo-
plasmic reticulum, atypical mytochondria, and accumu-
lation of concentrically arranged membranes, which
usually surround lipid vacuoles. Particularly in rodents,
accumulation of a brown pigment has been observed in
Kupffer cells and macrophages (ceroid pigment and
uroporphyrinl.
In the mouse, (male Balb/cJ strain) neoplastic
nodules (hepatomas, hyperplastic nodules) developed
after dietary exposure to Aroclor 1254. Female Sherman
strain rats fed WO ppm Aroclor 1260 for 21 months
developed hepatocellular carcinomas as well as neo-
plastic nodules (hyperplastic nodules) of the livers.
In the rat and the mouse, adenofibrosis of the liver
occurred after exposing rodents to either Aroclor 1254
or Aroclor 1260. Adenofibrosis, a persistent lesion, does
not disappear upon cessation of exposure fo the PCB's.
In connection with the persistence of the different
lesions mentioned in the rodents as well as in primates, it
was noted that certain homologues of the PCB mixtures
fed to the animals were not eliminated from adipose
tissue and liver in any appreciable amount. In rats, 6
months feeding of Aroclor 1254 at a dietary level of 100
ppm followed by a 16-month recovery period resulted in
total adipose tissue levels of 152 ppm penta, hexa-, and
heptachlorobiphenyl. These animals still showed
pathological changes in the liver, and liver PCB levels of
4.5 ppm.
INTRODUCTION
'Toxicology Branch, Center for Disease Control, U.S. Public
Health Service, Department of Health, Education, and Welfare,
Atlanta, Georgia.
For the past 45 years, polychlorinated biphenyls
(PCB's) have been used in transformers, capacitors, as
heat transfer fluids, and have had other industrial appli-
cations (ref. 1). The toxicity of these and related com-
pounds has recently been reviewed (ref. 2). A number of
new observations have been made since a conference was
held on PCB's in 1971 and it is the purpose of this paper
to outline additional findings that are associated with
chronic experimental exposure of animals to PCB's.
To study the long-term toxicity of the PCB's, com-
mercial mixtures have usually been employed. This was
done for two reasons: similar mixtures were found in the
environment, and the individual constituents of the
PCB's are very expensive and not readily available in the
quantity necessary to conduct long-term studies. Table 1
gives the composition of some of the commercial PCB
mixtures. If the PCB's are given as a single dose, they are
of a low order of toxicity (table 2). The acute dermal
toxicity is also low. It is the repeated and often long-
term exposure to these compounds that may lead to a
cumulative toxic effect.
HEPATOTOXIC1TY
Dietary exposure of rats to the PCB's produces
enlargement of the liver cells in some adult rats at a
dietary level of 5 ppm (0.4 mg/kg/day) (ref. 3). Liver
weights were increased in 21-day-old FI male weanlings
when the dams were fed as little as 1 ppm of Aroclor
1254 (ref. 3). At a dietary level of 20 ppm or above of
Aroclor 1254 or 1260, which is equivalent to a dietary
intake of 1.5 mg/kg/body weight per day, for an ex-
tended period of time, the hepatocytes in many rats had
foamy cytoplasm consistent with lipid accumulation. In
addition, hyperchromatic nuclei and binucleation was
observed in many liver cells. Inclusions were present in
the cytoplasm of the liver cells. These inclusions on
electron microscopic examination were consistent with
concentrically arranged membranes surrounding lipid
vacuoles. Other ultirastructural changes observed at this
and higher dietary levels in rats consisted of an increase
in smooth endoplasmic reticulum and atypical myto-
chondria. These ultrastructural changes have also been
described in primates (ref. 4) and are known to occur
with a number of other xenobiotics. Similar observations
were made in a study with smaller numbers of animals
30
-------
Table 1. Typical percentage composition of
polychlorinated biphenyl products3
Homologue Aroclor
# Cl /biphenyl 1221
0
1
2
3
4
5
6
7
11.
51
32
4
2
<0.5
NDb
ND
Aroclor
1016
<0.1
1
20
57
21
1
ND
Aroclor
1242
<0.1
1
16
49
25
8
1
<0.1
Aroclor
1254
<0. 1
<0. 1
<0.5
1
21
48
23
6
Percent (w/w) by GC/mass using area correction
factors by homolog response, (Papageorge, writ-
ten communication, June 1973).
DNone detected; <0.01% = ND.
Table 2. The incidence and type of liver
lesions in female sherman strain rats
Type of Lesion
Incidence
Controls Experimental
Hepatocellular
carcinoma
Neoplastic
nodules
1/173
0/173
26/184
144/184
Foci or areas of
cytoplasmic alteration 28/173
182/184
31
-------
where the rats were fed Aroclor 1242 and Aroclor 1016
(ref. 5).
A brown pigment representing ceroid pigment and
uroporphyrin was observed in Kupffer cells and macro-
phages. Particularly at higher dietary levels, livers
showed pink fluorescence under UV lights.
In addition, exposure of rats and mice to RGB's for
6 months or longer produced grayish white lesions in the
liver. On microscopic examination, these lesions con-
sisted of proliferation of glandular epithelial cells that
formed ducts and were surrounded by very pronounced
fibrosis (refs. 6,7). The ducts often contained cellular
debris. This lesion, called adenofibrosis, was first de-
scribed by Edwards and White (ref. 6) in rats fed the
carcinogen butter yellow (P-dimethylaminoazobenzene).
When rats were exposed for 6 months to a dietary
intake of 500 ppm Aroclor 1254 and then sacrificed first
at monthly and then at bimonthly intervals, the adeno-
fibrosis persisted through a 10-month observation
period. Usually adenofibrosis in rodents occurs con-
comitantly with hepatocellular carcinomas and/or neo-
plastic nodules (hyperplastic nodules). This was true for
the Balb/cJ mouse (ref. 7). When 50 Balb/cJ inbred male
mice were fed 300 ppm Aroclor 1254 (49.8 mg/kg/
bodyweight per day), a total of 10 neoplastic nodules
(hyperplastic nodules) were found in 9 per 22 surviving
mice after 11 months of exposure to the experimental
diet. No tumors were found in 58 surviving controls.
In another study, 400 weanling 21- to 26-day-old
Sherman strain COBS female rats were distributed into
two groups of 200 animals according to a table of
random numbers. The animals were housed 10 rats per
cage. Two hundred rats were fed plain ground purina
chow and 200 rats were fed the same diet containing
100 ppm Aroclor 1260. This study was only conducted
at this dietary level and with female rats because in a
preliminary feeding study, a bladder tumor was found in
1 of 10 female rats fed 100 ppm Aroclor 1260 (ref. 8).
The food consumption of the rats and their bodyweights
were determined at intervals. A slight decline in the rate
of the weight gain of the test group compared with the
control group began about 3 months after onset of the
experiment. Mean final bodyweights were 420 grams for
the control group and 392 grams in the test group. This
difference was statistically significant (P < 0.001) since
such a large group of animals was involved in this study.
The food consumption of rats declines with age. Accord-
ingly, PCB intake declined from 11.6 mg/kg/day during
the first week of exposure to 6.1 mg/kg/day at 3 months
of exposure and to 4.3 mg/kg/day at 20 months. We
determined the PCB concentrations in the experimental
diet at intervals and these ranged usually from 70 to 107
ppm. We also spot checked the diet for aflotoxins. Aflo-
toxins were never detected in either the control or the
experimental diet. A total of 173 control and 184
experimental animals survived to the age of 21-23
months. At autopsy of these rats, a consistent difference
in the appearance of the livers was observed between the
experimental and the control groups. Almost all (170 of
184 livers) of the experimental animals had from a few
to multiple elevated tari nodules on the liver surface.
Additional nodules were usually seen on sectioning.
These nodules varied from .1 to several centimeters in
diameter. In contrast, the liver of only one control
animal showed gross abnormalities and was markedly
enlarged, nodular, tan, and firm. A variety of tumors of
other organs was observed in both the experimental and
the control group but a difference in the incidence of
tumors in other organs in the experimental and the con-
trol group did not exist.*
Histologic examination of the liver showed that 26
experimental rats and 1 control rat had hepatocellular
carcinomas. An additional 144 experimental animals had
hepatocellular nodules consistent with neoplastic
nodules (hyperplastic nodules). In addition, 182 treated
and 28 control animals had areas of hepatocytes with
altered, cytoplasm. The cells in these areas were often
similar to those that were observed in the neoplastic
nodules but the architecture of these atypical areas in
the liver was the same as that of normal liver tissue and
the liver plates merged with the surrounding liver tissue
rather than compressing it.
In classifying the different liver lesions, the recom-
mendations made in a liver tumor workshop (ref. 9)
were followed.
The results of this bioassay test illustrate that Aro-
clor 1260 produces hepatocellular carcinomas according
to traditional histological criteria and neoplastic nodules,
which are a part of the spectrum of a response to hepa-
tocarcinogenic agents. Neoplastic nodules must be
included in the evaluation of tumorigenesis. Neoplastic
lesions of the liver have also been produced by some of
the commercial Japanese PCB mixtures; in mice with
Kanechlor 500, and in Donryu rats with Kanechlor 400
(refs. 10,11).
The effect on the gastric mucosa as it has been
described in primates (re'f. 4) does not seem to be as
prevalent in rodents. Only very high dietary levels, such
as single doses of 3,000 mg/kg, will cause alteration of
the gastric and duodenal rnucosa (ref. 2). Primates (ref.
4) receiving 100 to 300 ppm Aroclor 1248 developed
thickened gastric mucosa that contained numerous large
cysts filled with mucin. Extension of the atypical
*About 40 percent of the rats in each group had extra-
hepatic tumors. In a number of the rats, multiple tumors were
present.
32
-------
appearing glandular epithelium into the muscularis
mucosa and the underlying submucosa was also noted.
This hyperplastic gastritis was quite- persistent in the
primate.
In conjunction with some of the feeding studies in
rodents, tissue levels were determined in adipose tissue
and the liver. It was noted that the gas chromatograms
of the RGB's that were extracted from tissues was quite
different from gas chromatograms of the standards. The
PCB compounds remaining in adipose tissue as well as
liver even after dietary exposure to PCB's has been term-
inated for as long as 10 or 16 months were the pents-,
hexa-, and heptachlorobiphenyls, with molecular weights
of 324, 358, and 392 (ref. 6). When rats were fed
Aroclor 1254 at a dietary level of 100 ppm for 6
months, and were then removed from exposure to PCB's
for 16 months, levels of 4.4 ppm of PCB-derived mate-
rial was present in the liver and 152 ppm of PCB-derived
material in adipose tissue on a wet weight basis. The
livers of these rats showed some of the morphological
changes already described (ref. 12). In primates that con-
sumed Aroclor 1248 and reached adipose tissue levels of
127 ppm, after an 8-month recovery period the adipose
tissue levels were 34 ppm of PCB-derived materials (ref.
4).
SUMMARY
The administration of PCB's to animals—particularly
rodents but also monkeys and rnink—produces a variety
of responses in the liver. Early enlargement of the liver is
primarily due to hypertrophy of the cells and an increase
of the smooth endoplasmic reticulum of the cytoplasm
of the liver cells. The smooth endoplasmic reticulum
may condense in the liver cells and form hyalin inclu-
sions, which on electron microscopic examination con-
sist of concentrically arranged membranes containing
lipid vacuoles. In addition to these lipid vacuoles, lipid
accumulation may also occur throughout the liver cells.
These changes are initially reversible. However, if the
exposure to PCB's is continued, then liver damage, in-
cluding liver cell necrosis, may also develop. This is
accompanied by proliferation of the liver cells resulting
in pleomorphism. Long-term exposure to PCB's in
rodents produces a tumorigenic response which consists
of the development of atypical areas, neoplastic nodules,
and hepatocellular carcinoma. Adenofibrosis, which
usually occurs concomitantly with hepatocellular carcin-
omas, has also been produced in the rat and the mouse.
Pigment deposition within the macrophages and Kupffer
cells has been noted (ref. 6). This pigment is composed
of ceroid pigment (lipofuchsin) and uroporphyrin.
Hemosiderin may also be present. In addition to liver
changes, hyperplasia of the gastric mucosa has been ob-
served in the primates (ref. 4) following the exposure to
PCB's.
Because of these findings in experimental animals,
ingestion of PCB's in humans must be curtailed. Expo-
sure from all sources in the occupational environment
needs to be reviewed and workers with long-term occu-
pational exposure to PCB's should be studied. An effort
should be made to establish all environmental sources of
PCB's in order to assess exposure of the general popula-
tion.
REFERENCES
1. M. G. Broadhurst, "Use and Replaceability of Poly-
chlorinated Biphenyls," Environ. Health Perspect,
No. 1 (1972), pp. 81-102.
2. R. D. Kimbrough, "The Toxicity of Polychlorinated
Polycyclic Compounds and Related Chemicals,"
CRC Crit. Rev. Toxicol., Vol. 2 (1974), pp.
442-498.
3. R. E. Linder, T. B. Gaines, and R. D. Kimbrough,
"The Effect of Polychlorinated Biphenyls on Rat
Reproduction," Fd. Cosmet Toxicol., Vol. 12
(1974), pp. 63-77.
4. J. R. Allen, "Response of the Nonhuman Primate to
Polychlorinated Biphenyl Exposure," Federation
Proc., Vol. 34, No. 8 (1975), pp. 1675-1679.
5. V. W. Burse, R. D. Kimbrough, E. C. Villanueva, R.
W. Jennings, R. E. Linder, and G. W. Sovocool,
"Polychlorinated Biphenyls, Storage, Distribution,
Excretion and Recovery: Liver Morphology after
Prolonged Dietary Ingestion," Arch. Environ.
Health, Vol. 29 (1974), pp. 301-308.
6. R. D. Kimbrough, R. E. Linder, V. W. Burse, and R.
W. Jennings, "Adenofibrosis in the Rat Liver,"
Arch. Environ. Health, Vol. 27 (1973), pp. 390-395.
7. R. D. Kimbrough and R. E. Linder, "Induction of
Adenofibrosis and Hepatomas of the Liver in Balb/
cJ Mice by Polychlorinated Biphenyls (Aroclor
1254)," J. Natl. Cancer Inst., Vol. 33 (1974), pp.
547-552.
8. R. D. Kimbrough, R. A. Squire, R. E. Linder, J. D.
Strandberg, R. J. Montali, and V. W. Burse, "Induc-
tion of Liver Tumors in Rats by Polychlorinated
Biphenyl Aroclor 1260," J. Nat. Cancer Institute,
December 1975, in press.
9. R. A. Squire and M. H. Levitt, "Report of a Work-
shop on Classification of Specific Hepatocellular
Lesions in Rats," Cancer Research, Vol. 35 (1975),
pp. 3214-3223.
10. N, Ito, H. Nagasaki, M. Arai, et al., "Histopathologic
Studies on Liver Tumorigenesis Induced in Mice by
33
-------
Technical Polychlorinated Biphenyls and its Pro-
moting Effect on Liver Tumors Induced by Benzene
Hexachloride," J. Natl, Cancer Institute, Vol. 51
(1973), pp. 1637-1646.
11. N. T. Kimura, and T. Baba, "Neoplastic Changes in
the Rat Liver Induced by Polychlorinated Bi-
phenyl," Gann, Vol. 64 (1973), pp. 105-108.
12. R. D. Kimbrough, V. Burse, R. E. Linder, and R.
Jennings, personal communication, unpublished ma-
terial.
DISCUSSION
MR. LAWRENCE ROY: You indicated after an animal
has been exposed for 6 months you get regression,
and if they did regress. . .
DR. KIMBROUGH: I don't know if I can answer all of
that; you may have to repeat part of your question.
But, first of all, I think in the studies that I did-and
we really haven't got any time to go into all of this
this morning—if you feed animals for only 6 months
you do not see any tumors; you have to feed ani-
mals PCB's for much longer periods of time.
The first indication of any tumor development
that I saw in reproduction studies we did was when
the animals were exposed for at least 300 days. On
the other hand, in the rat you do get what I call
adenofibrosis if you feed the animals for about 6
months. That lesion is also known as cholangio-
fibrosis. Adenofibrosis does not regress. We did a
feeding study where you feed the animals for 6
months, and then sacrifice them at bimonthly inter-
vals, and the lesion will still be there 10 months
later. So this is one problem with PCB's.
And at least some of the PCB homologs are
retained for such a long period of time that I don't
know whether you could also have what you might
call internal exposure.
I think you had some other questions?
VOICE: First of all, do tumors cause death in these
animals, and do these tumors cause an increase in
size?
DR. KIMBROUGH: Some of the animals I think have
died with large tumors at the end of the study. I
don't think the tumors that are called hepatocellular
carcinomas would regress. I also did not say that we
had any regression in the animals we fed for 6
months.
MS. DIANE HORVAK (University of Wisconsin, Depart-
ment of Pathology): What was the difference be-
tween the carcinoma and the nodule?
DR. KIMBROUGH: We did use histological criteria. In
our classification, the; tumors that we call neoplastic
nodules were well circumscribed tumors that would
extend over several lobules and some of them were
actually quite large, and would compress the sur-
rounding normal liver tissue, and because of that,
they were circumscribed.
The lesions that were classified as carcinomas
showed disorganized liver. Liver plates were two or
three layers thick. You would have dilated sin-
usoids, would see mitotic figures and a great deal of
pleomorphisms, but none of these tumors metasti-
sized.
CHAIRMAN RALL: There's a question over there.
DR. ROBERT RISEBROUGH (University of Califor-
nia): Since we now know that these PCB prepara-
tions do contain dibenzofurans, I wonder if it is
your plan to repeat these experiments with PCB's
that do not contain the dibenzofurans. I wonder
also if you would care to guess whether these
tumors are caused by PCB or by the contaminants.
DR. KIMBROUGH: I have no plans at the moment to
repeat these experiments. I do not know if I could
get a completely clean Aroclor 1260.
The PCB that we used was Aroclor 1260 with
the lot number AK3, which Dr. Bowes has analyzed;
I think the level of the combined furans in that
particular sample is less than 1 ppm. I may be wrong
there, but if you recalculate that, you will find that
the amount of furans consumed by the animals was
very small. The amount of PCB's which the animals
ingested was 5 mg/kg body weight/day, and the
furans constituted less than I ppm of that. This
amount is so small that I wonder whether it had any
effect in this particular experiment.
CHAIRMAN RALLS: We'll come back to the issue of
dibenzofurans later.
34
-------
SUMMARY OF TOXICOLOGICAL STUDIES ON
COMMERCIAL PCB's
J. C. Calandra, M.D., Ph.D.*
Abstract
A broad toxicological program was conducted to
evaluate the biological effects of Aroclor 1242, 1254,
and 1260 in mammalian as well as avian species. No-
effect levels were defined which permit an assessment of
the hazard these materials present to man and his
environment.
The urgent need for additional toxicological data
became apparent when the refinement of analytical
techniques made possible the identification of PCB's in
many portions of the ecosystem.
To assess the biological hazards of these materials,
chronic feeding studies in rats and dogs were conducted
according to accepted traditional procedures with
Aroclors 1242, 1254, and 1260. It should be pointed
out that Aroclor 1260 is no longer produced in this
country since it does not meet the physical specifica-
tions for its restricted uses (ref. 1).
In addition, three-generation two-litter reproduction
and teratology studies in albino rats as well as a domi-
nant lethal mutagenic study in albino mice were con-
sidered to be necessary for the broad spectrum safety
evaluation of these materials.
Effects such as decreases in eggshell thickness
described in certain avian species suggested that toxicity
and reproduction studies in chickens would be helpful in
evaluating possible untoward effects in birds. A list of
the studies conducted are presented in table 1.
The experimental design of the chronic rat and dog
studies is given in tables 2 and 3. It should be noted that
these studies were of typical Food and Drug Administra-
tion design for the evaluation of the safety of direct and
indirect food additives.
The important results in the chronic rat studies
which were conducted on Charles River rats are sum-
marized briefly in tables 4, 5, and 6.
Food consumption, mortality, and hematologic,
urine, and blood chemistry studies did not differ among
treatment and control groups. The only weight depres-
sion observed was at the 24-month point in females fed
100 ppm of Aroclor 1254.
Liver weight increases were noted in males and
females fed 100 ppm Aroclor 1254 or Aroclor 1260, and
in females only in the 100 ppm group fed Aroclor 1242.
'Industrial BIO-TEST Laboratories, Inc., Northbrook, Illi-
As expected, the important histopathologic changes
in the rat study were present in the livers of the
24-month sacrifice animals and consisted of hepatocel-
lular alterations such as focal hypertrophy, cytoplasmic
lipid changes and in some animals at 100 ppm, hepa-
tomas or cholangiohepatomas. No evidence of hepato-
cellular carcinogenicity of the Aroclors was found in this
study.
The conclusion that "no evidence of hepatocellular
carcinogenicity of the Aroclors was found in this study"
was reached only after extensive reevaluation of the orig-
inal liver slides as well as additional liver sections from
all of the animals after the Kimbrough results on Aroclor
1260 became known to us (ref. 2).
The slides were read independently and separately
by Dr. Donovan Gordon (ref. 3), Professor Ward Richter
(ref. 4), and Professor P. Pour (ref. 5) of Industrial BIO-
TEST Laboratories, the University of Chicago, and the
Eppley Institute for Cancer Research, respectively.
The interpretation of pathologic changes that occur
in the liver as a result of absorption of chlorinated
hydrocarbons is a key issue that needs resolution by the
community of pathologists (ref. 6, 7). The problem is
highlighted in the context of PCB's since there appears
to be disagreement as to whether Aroclor 1260 is or is
not a hepatocellular carcinogen (ref. 8). Pour reevaluated
the Kimbrough slides and does not agree with the re-
ported findings.
The findings in the chronic dog study are summa-
rized in table 7. The feeding of Aroclor 1260 at 100
ppm showed an increase in serum alkaline phosphatase
activity and liver weights. A slight decrease in body
weight gain was noted at the 100 ppm dose level in
males and at 10 and 100 ppm in females. No remarkable
histopathologic changes were found.
The design of the dominant lethal mutagenic study
is presented in table 8. No effects related to Aroclor
treatment were seen in the parameters listed in table
9-mortality, mating index, number of implantation and
resorption sites, number of viable embryos, preimplanta-
tion loss or mutation rates. This finding is in agreement
with that of Green et al. (ref. 10).
No effects related to Aroclor treatment were seen in
the parameters listed in table 9—mortality, mating index,
number of implantation and resorption sites, number of
viable embryos, preimplantation loss or mutation rates.
This finding is in agreement with that of Green et al.
(ref. 10).
35
-------
The standard design for a three-generation two-litter
reproduction study in albino rats is given in table 10 and
the teratology study in table 11. A brief summary of the
results (table 12) indicates that none of the Aroclors
studied produced adverse effects in the two litters of the
first generation.
All progeny delivered by female rats in each of three
generations exposed to dietary levels of up to 100 ppm
of either Aroclor 1242, 1254, or 1260 were structurally
normal. A reduction in the mating index was observed in
the second and third generations of animals fed either 10
or 100 ppm. The ability of females to conceive, carry
the delivery process to parturition, and to successfully
nourish the young was not affected by the three Aro-
clors. It should be stressed that no changes in the repro-
ductive tract of either male or female rats were produced
by any of the three Aroclors. Findings in the third
generation were similar to those in the first with no
suggestion of any alterations in response as a function of
succeeding generations.
Teratologic studies in which albino rats were
exposed to either Aroclor 1242, 1254, or 1260 at doses
of up to 30 mg/kg during rapid organogenesis—gestation
days 6 through 15—were conducted in our laboratories.
No evidence of embryotoxicity as reflected by an in-
crease of fetal resorption or teratogenicity as measured
by complete external, skeletal, and internal evaluation of
fetuses obtained from the Aroclor-treated females, was
obtained. Other experimental data pertaining to the
potential teratogenicity of polychlorinated biphenyls
supports the lack of adverse effects. Mizunuya (ref. 11)
and his colleagues found no evidence of teratogenicity in
the rat when fed at dietary levels of up to 250 ppm. In
the mouse, Toeruek (ref. 12) found that doses of up to
500 mg/kg were nonteratogenic although when given on
gestation days 1 through 6 a decrease in implantation
sites and fetal weights was observed. These doses given
on gestation days 7 through 11 failed to produce any
changes with respect to either reproductive parameters
or teratogenicity. Further, no evidence of malformation
was obtained in infant monkeys delivered to females fed
either 2.5, 5, or 25 ppm Aroclor 1248 although the birth
weights were reported to be reduced (ref. 9).
The last study in this series was a toxicity/reproduc-
tion study in white leghorn chickens (tables 13, 14, and
15).
Aroclor 1260 at all test levels did not produce
adverse effects on the various parameters investigated.
Egg production in hens fed 100 ppm Aroclor 1242 or
1254 was decreased as was egg hatchability. In fact, poor
hatchability of eggs from hens fed 8 ppm Aroclor 1242
was found (table 15).
In addition, Aroclor 1242 at 10 and 100 ppm and
Aroclor 1254 at 100 ppm were associated with reduced
eggshell thickness. Chick viability was affected by both
substances at the 10 ppm dose level.
CONCLUSIONS
1. The no-effect level for the Aroclors in the chronic
rat and dog studies> is about 10 ppm.
2. No teratogenic or mutagenic effects were found.
3. No hepatocellular carcinomas were present.
4. The no-effect level in the rat reproduction study is
between 1 and 10 ppm and is the result of low
mating indices.
5. In the chicken reproduction and teratology studies,
effects were more severe with Aroclor 1242 with
the no-effect level being 2 to 4 ppm.
REFERENCES
1. Private communication, Monsanto Company.
2. R. D. Kimbrough et al., Induction of Liver Tumors
in Rats by Polychlorinated Biphenyl Aroclor 1260,
in press.
3. D. E. Gordon, report on Histopathological Evalu-
ation of Aroclor 1242, 1254, and 1260, March 24,
, 1975.
4. Ward R. Richter, report on Histopathological Evalu-
ation of Aroclor 1242, 1254, and 1260, March 24,
1975.
5. Report on Histopathological Reevaluation of Livers
for Rats Treated with Aroclors, August 1,1975, by
P. Pour.
6. R. A. Squire et al,, "Report of a Workshop on Clas-
sification of Specific Hepatocellular Lesions in
Rats," Cancer Research. Vol. 35 (1975), p. 3214.
7. Subcommittee on Environmental Carcinogenesis of
the National Cancer Advisory Board, November
10-11, 1975.
8. P. Pour, report on Histopathological Reevaluation
of Tissues From Female Sherman Rats Fed Aroclor
1260, October 31, 1975.
9. J. R. Allen, "Response of the Nonhuman Primate to
Polychlorinated Biphenyl Exposure," Fed. Proc.,
Vol. 34 (July 1975), p. 1675.
10. S. Green et al., "Lack of Dominant Lethality in
Rats Treated with Polychlorinated Biphenyls (Aro-
clors 1242 and 1254)," Fed. Cosmet. Toxicol., Vol.
13 (1975), p. 507.
11. Y. Mizunuya et al., "Effects of PCB's on Fetuses
and Offspring in Flats," Shakuhim Eiseigaku Zassh,
Vol. 15 (1975), p. 252.
12. P. Toeruek, "Effects of PCS on the Developing
Mouse," Chemosphere, Vol. 2 (1973), p. 173.
36
-------
DISCUSSION
MR. PAUL AGENTINE: You didn't find any effects or
pathological agents in the dog?
DR. CALANDRA: Would you repeat that?
MR. ARGENTINE: How did you arrive at the no-
effects level in canine at 10 ppm? In studies you
showed no pathological agents and no toxicity?
DR. CALANDRA: As I indicated, this is a very brief
and rapid summary. We have a question about liver
weights and one or two other parameters and to be
conservative, we have used the number of 10 ppm.
In other words, we are not in any way indicating
that RGB's are nontoxic materials, and this is a
conservative estimate.
DR. ALLEN GREY (I.I.T. Research, Chicago, Illi-
nois): Are you able to relate the differences in
biological effects on the various Aroclors to their
composition?
DR. CALANDRA: Only generally. As everyone knows,
the higher chlorinated materials appear to be more
persistent in the mammalian system. And there
appears to be a target organ-the liver-which
appears to be more susceptible to the higher chlori-
nated materials. I think these are the only generali-
zations you can make at this time.
Table 1. Toxicity studies conducted
with Aroclors 1242, 1254 and 1260
Type of test
Test animal
Two-year chronic
oral
Two-year chronic
oral
Three-generation
reproduction
Teratology
Dominant lethal
mutagenic
Toxicity/repro-
duction
albino rats
beagle dogs
albino rats
albino rats
albino mice
white leghorn
chickens
37
-------
Table 2. Two-year chronic oral toxicity
study-albino rats and beagle dogs
Test material
None
Aroclor 1242
Aroclor 1254
Aroclor 1260
Dietary levels
(ppm)
-
1,
1,
1,
-
10,
10,
10,
-
100
100
100
Number of animals
per dietary level
rats
M F
50 50
50 50
50 50
50 50
dogs
M F
4 4
4 4
4 4
4 4
Table 3. Two-year chronic oral
toxicity study-albino rats
and beagle dogs
Parameters investigated;
• Body weight
• Food consumption
• Hematology
• Clinical blood chemistry (BUN, SAP,
SGPT, fasting blood glucose,
SGOT--dogs only)
• Urinalyses
• Pathology (gross, organ weights,
microscopic)
Table 4. Ingestion of Aroclor 1242
by albino rats-liver effects
Increase in liver weights--100 ppm--
females
Primary liver lesions
None at 3-, 6-, 12-month sacrifice
24-month sacrifice--100 ppm--
increased incidence of:
Nodular hyperplasia (8/20)
Hepatoma (2/20)
Chologiohepatoma (1/20)
Hepatocellular
carcinoma (0/20)
38
-------
Table 5. Ingestion of Aroclor 1254
by albino rats-liver effects
Increase in liver weights—100 ppm
Primary liver lesions
None at 3-, 6-, 12-month sacrifice
24-month sacrifice--100 ppm—
increased incidence of:
Nodular hyperplasia (13/27)
Hepatoma (4/27)
Cholangiohepatoma (2/27)
Hepatocellular
carcinoma (0/27)
Table 6. Ingestion of Aroclor 1260
by albino rats-liver effects
Increase in liver weights--lOO ppm
Primary liver lesions
None at 3-, 6-, 12-month sacrifice
24-month sacrifice--!00 ppm--
increased incidence of:
Nodular hyperplasia
Hepatoma
Cholangiohepatoma
Hepatocellular
carcinoma
(7/27)
(5/27)
(2/27)
(0/27)
Table 7. Effects of ingestion of
Aroclors-beagle dogs
Test material Effect
Aroclor 1242
Aroclor 1254
Aroclor 1260
no effects
slight decrease in
body weight gain
--100 ppm
slight decrease in
body weight gain
--100 ppm, males
--10 and 100 ppm,
females
increase in SAP--
100 ppm
increase in liver
weights--100 ppm
Table 8. Dominant lethal mutagenic
study-albino mice
Test material
Dose*
Corn oil
Methyl methane
sulfonate (MMS)
Aroclor 1242
Aroclor 1254
Aroclor 1260
0.9 ml/kg
100 mg/kg
500 or 1000 mg/kg
500 or 1000 mg/kg
500 or 1000 mg/kg
*Single dose given i.p. to 12
males/group.
39
-------
Table 9. Dominant lethal mutagenic
study-albino mice
No effects related to Aroclor treat-
ment seen in:
• Morta1i ty
• Mating index
• Number of implantation sites
• Number of resorptfon sites
• Number of viable embryos
• Preimplantation loss
• Mutation rates
Table 10. Three-generation reproduction
studya--albino rats
Test material
Dietary levels
(ppm)
Number of animals
per dietary level
M F
None
Aroclor 1242
Aroclor 1254
Aroclor 1260
-
1,
1,
1,
-
10,
10,
10,
-
100
100
100
8
8
8
8
16
16
16
16
Two litters per generation.
40
-------
Table 11. Teratology study--
albino rats
Test
material
Corn oil
Aroclor
1242
Aroclor
1254
Aroclor
1260
Dose3
(mg/kg/day)
-
10 or 30
10 or 30
10 or 30
Number
of gravid
rats
26
26
26
26
Administered on gestation days 6
through 15 (10 doses).
Table 12. Effect of Aroclors on
reproduction/teratology-
albino rats
Reproduction study
First generation—no effects
Second and third generations--
10 and 100 ppm
- decrease in mating index
- decrease in incidence of
pregancy
(Aroclor 1242--no third genera-
tion with 100 ppm).
Teratology study--no effects.
Table 13. Toxicity/reproduction
study-white leghorn chickens
Test
material
None
Aroclor
1242
Aroclor
1254
Aroclor
1260
Dietary Number of
levels animals per
(ppm) dietary level
-
1. 2,
8, 10,
1, 10,
1, 10,
M
8
4,
100 4
100 4
100 4
F
40
20
20
20
41
-------
Table 14. Toxicity/reproduction
study-white leghorn chickens
Parameters investigated:
Body weight
Food consumption
Egg production
Egg quality
Egg hatchability
Eggshell thickness
Chick body weight
Chick viability
Pathology
Table 15. Effects of Aroclors
on chicken reproduction
Parameter
Egg
production
Egg
hatchability
Shell
thickness
Chick
viability
Dietary
level
1242
100
8
100
10
Causing
effect*
1254
100
100
100
10
Aroclor 1260--no effects at-any
dose level
42
-------
PATHOBIOLOGICAL RESPONSES OF PRIMATES
TO POLYCHLORINATED BIPHENYL EXPOSURE
J. R. Allen, D.V.M., Ph.D., and D. H. Norback*
Abstract
Male and female rhesus monkeys received varying
levels of polychlorinated biphenyls (PCB's) and were
evaluated for toxic effects, reproductive dysfunctions,
and metabolism of the compounds. Female rhesus
monkeys exposed to dietary levels as low as 2.5 and 5.0
ppm of PCB (Aroclor 1248) developed facia/ acne,
erythema, subcutaneous edema, conjunctivitis, and loss
of eyelashes. Reproductive dysfunctions were mani-
fested by irregular menstrual cycles, early abortions, and
stillbirths. As a result of transplacental migration of the
compounds, all infants born of PCB-exposed animals
contained PCB's in their tissues at birth. The infants,
which continued to be exposed to PCB's by ingestion of
milk from their lactating mothers, developed skin lesions
and 50percent expired within 4 months.
Metabolic studies demonstrated 90 percent absorp-
tion of the PCB's from the gastrointestinal tract and
distribution in organs of high lipid content. Hydroxy-
lated metabolites were formed in the liver and excreted
through the biliary and urinary routes. Lower chlori-
nated congeners were more rapidly metabolized and
excreted, while concentrations of the highly chlorinated
biphenyls persisted in the adipose tissue in excess of
2-1/2 years. The detection of the urinary metabolite
trans-3,4-dihydro-3,4-dihydroxy-tetrachlorobiphenyl
suggests that the mechanism of metabolism is through an
arena oxide intermediate. In vivo and in vitro studies
demonstrated binding of PCB's with macromolecu/es.
INTRODUCTION
Even though the polychlorinated biphenyls (PCB's)
have been used extensively for various industrial pur-
poses for the past 40 years, the health significance of
•Department of Pathology and Regional Primate Research
Center, University of Wisconsin, Madison, Wisconsin. This inves-
tigation was supported in part by U.S. Public Health Service
grants ES-00472, ES-00958 and RR-00167 from the National
Institutes of Health, and the University of Wisconsin Sea Grant
Program. The majority of the data presented in this report were
obtained through the efforts of our colleagues in the Experi-
mental Pathology Laboratory: D. Barsotti, K. Blomquist, L.
Carstens, I. C. Hsu, R. Marlar, L. Moore, D. Peterson, J. Sey-
mour, J. Van Miller. A portion of this research was conducted in
the University of Wisconsin-Madison Biotron, a controlled
environmental research facility supported by the National
Science Foundation and the University of Wisconsin.
human exposure to these compounds only recently has
become of widespread concern. The scientific communi-
ty was alerted to the potential environmental health
problem by Jensen in 1966 (ref. 1) after PCB's were
identified in tissue extracts of birds experiencing repro-
ductive difficulties in Sweden. The magnitude of the
problem was brought to the forefront by the "Yusho"
incident when over 1,000 Japanese suffered prolonged ill
effects from exposure to PCB-contaminated rice oil (ref.
2). Further concern about the potential danger of PCB's
on human health followed disclosure of increasing levels
of these compounds in various foods. The contamination
has been attributed to incorporation of these com-
pounds within the food chain or from packaging of food
products in PCB-impregnated paper containers (ref. 3).
Increasing levels of PCB's in human tissue samples attest
to the magnitude of the human exposure (refs. 4,5).
Within this laboratory various animal models,
including the nonhuman primate and rodent, have been
evaluated following exposure to PCB's for the develop-
ment of lesions which parallel those recorded in man.
Emphasis has been placed on determining pathophysi-
ological alterations that arise in animal models as a result
of exposure to several levels of PCB's for variable periods
of time. The absorption, tissue distribution, and rate of
excretion of PCB's have been determined. The inter-
action of the PCB's or their metabolites with cellular
macromolecules has also been a major area of investi-
gation. The following report, which includes previously
unpublished observations, presents a summary of the
progress that has been made in this laboratory on the
above mentioned areas of PCB research.
GENERAL EFFECTS OF PCB'S
ON NONHUMAN PRIMATES
The investigation of toxicity produced by PCB's in
various animal species demonstrated the limitations of
rodents as animal models. Male Sprague-Dawley rats
were able to survive for 1 year on diets containing 100
ppm PCB (Aroclor 1248, 1254, or 1262) without show-
ing signs of illness (ref. 6). These observations substan-
tiated those of Keplinger et al. (ref. 7). Increasing the
PCB content of the rat diets to 1,000 ppm did not
produce skin lesions; however, death occurred within 6
to 8 weeks due to widespread hepatic degeneration (ref.
8).
Male rhesus monkeys developed many of the signs
43
-------
experienced by humans that had been inadvertently
exposed to PCB's. Monkeys fed diets containing 100 and
300 ppm PCB (Aroclor 1248) (table 1) developed facial
edema, erythema, acne, and alopecia within 3 weeks.
The lesions became progressively more severe with
increased length of exposure (refs. 9,10). In addition,
the animals developed anorexia, loss in weight, hypo-
proteinemia, hypolipidemia, and anemia. Within 3
months the majority of the monkeys had died or were
moribund. Necropsies of these animals revealed decided
mucosal gastric hyperplasia with penetration of the
glandular epithelium into the underlying submucosa (ref.
10). Numerous ulcerations of the hyperplastic gastric
mucosa were also present (ref. 11). In addition, there
was a decided hypertrophy of the liver.
Female monkeys fed 25 ppm PCB (Aroclor 1248)
(table 1) in the diet developed facial lesions similar to
those observed in the animals receiving higher levels of
PCB's (ref. 12). After 2 months on the PCB diet it was
necessary to discontinue the exposure due to the severi-
ty of intoxication. One of the six experimental animals
died 4 months after the initial exposure to PCB's.
Necropsy evaluation demonstrated severe gastric hyper-
plasia and ulceration. The surviving adult female
monkeys continued to be devoid of eyelashes and dis-
played facial acneform lesions 2 years following expo-
sure to the PCB's. Infants born to these females were
small (350 vs. 450 g) and contained PCB's in their tissues
at birth.
Female monkeys given 2.5 and 5.0 ppm PCB (Aro-
clor 1248) (table 2) in their diets developed facial
edema, swollen eyelids, erythema, loss of hair, and acne
within 2 months (ref. 13). By the fourth month, irregu-
larities in the menstrual cycles and an increased level of
urinary ketosteroids were recorded (ref. 14). Following
6 months of PCB exposure the female monkeys were
bred to control males. Six of eight animals on the 5.0
ppm diet conceived (table 2). The remaining two were
bred on five separate occasions without conceiving. Four
of the six females experienced abortion early in gesta-
tion. Eight of eight of the 2.5 ppm PCB fed animals
conceived; however, only five were able to carry their
infants to term. As was the case with infants of animals
given the higher levels of PCB's, all the infants were
small and at birth their skin contained detectable levels
of PCB's.
The infants were permitted to nurse their mothers
for 4 months. Within 2 months focal areas of hyperpig-
mentation, swollen lips and eyelids, loss of eyelashes,
and acneform lesions of the face developed. The skin of
these infants showed a decided increase in the PCB level
over this period. Within 4 months, 3 of the 6 infants
died due to PCB intoxication. After weaning, the
remaining three have shown improvement of the skin
lesions during the 4-month periocl.
Four adult male rhesus monkeys were also exposed
to a diet containing 5.0 ppm PCB's (Aroclor 1248)
(table 1) for 17 months (average total intake of PCB's
460 mg). They began to develop a slight periorbital
edema after 6 months of exposure; however, it was
much less severe than in the. female monkeys receiving a
similar level of PCB. The morphological features and
viability of the spermatozoa as well as the ability to
fertilize control female rhesus monkeys was unaffected
during the initial 12 months of PCB exposure. Subse-
quently one of the four males lost weight and developed
alopecia, acne, periorbital edema and decreased libido. A
testicular biopsy of this animal showed a decided hypo-
activity of the seminiferous tubules. There was an
absence of mature spermatozoa and a predominance of
Sertoli cells of the tubules. The remaining three males
have remained healthy and sexually active (ref. 15).
ABSORPTION, METABOLISM, TISSUE DEPOSITION,
AND EXCRETION OF PCB's
Over 90 percent of a single oral dose (1.5 or 3.0 g
per kg) of PCB's (Aroclor 1248) given to adult rhesus
monkeys was absorbed from the gastrointestinal tract.
Chromatographic analysis of the tissues 14 days after
exposure revealed a predominance of higher chlorine
isomers that had a predilection for the adipose tissue and
organs containing a high fat content (ref. 16).
Rhesus monkeys fed 25 ppm PCB (Aroclor 1248) in
the diet attained levels of 127 /xg/g within the adipose
tissue after 2 months. Eight months after discontinua-
tion of exposure to PCB's the levels were 34 /xg/g within
the adipose tissue. After 33 months, the levels within the
adipose tissue ranged from 3 to 14 M9/9; the residues
contained greatly increased proportions of highly chlori-
nated congeners. Transplacental movement of the PCB's
was demonstrated by the presence of PCB's in the
infants born to exposed females. The tissues of an
infant, born to a female 8 months following the discon-
tinuation of PCB's in the diet, contained 25,ug/g of PCB
in the fat and adrenal tissue:; at the time of birth. In an
infant born to a female 29 months following the discon-
tinuation of PCB's, the levels within the adipose tissue
were 3.38 jug/g at 4 months of age.
Female monkeys given 5.0 ppm PCB in their diets
attained maximum levels of PCB's within their adipose
tissue at 6 months (141 to 177 ;ug/g adipose tissue).
However, it required approximately 14 months on the
2.5 ppm diet for the monkeys to reach similar maximum
PCB levels in their adipose tissue (126 to 144 M9/9)-
Males which received 5.0 ppm PCB's attained levels
44
-------
Table 1. Experiments on exposure of primates to RGB's (Aroclor 1248*
Level of PCB
in diet
(pprn)
300
TOO
25
2.5
5.0
5.0
No. of
animals
6 males
6 males
6 females
8 females
8 females
4 males
Length of
exposure
(months)
3
2
2
16-19
16-19
17
Total PCB
intake
3.6 to 5.4 g
0.8 to 1.0 g
250 to 400 mg
243 to 303 mg
460 to 614 mg
530 to 692 mg
Monsanto Co., Inc., St. Louis, Missouri.
Table 2. Modification in reproduction
in primates that were exposed
to Aroclor 1248 in the diet
Total
impregnated
(no. /no.
animals)
Resorptions
or abor-
tions (no./
no. animals)
Stillborn
(no. /no.
animals)
Control
12/12
0/12
0/12
2.5 ppm
8/8
3/8
0/8
5.0 ppm
6/8
4/8
1/8
Normal
births (no./
no. animals) 12/12
5/8
1/8
45
-------
ranging from 128 to 200 jug per g adipose tissue at 14
months. Infants born of mothers exposed to 2.5 and 5.0
ppm RGB's within the diet contained concentrations of
PCB's ranging from 1.0 to 4.8 jug/g within the skin at
birth. While nursing from mothers consuming PCB diets,
the infants continued to accumulate the compound. At
3 months, the levels within the tissues ranged from 86 to
136 /ug/g. The concentration of PCB's within the milk
ranged from 0.15 to 0.40 /ug/g- The tissues of the infants
which died while nursing PCB-fed mothers contained
high levels of PCB's within the thymus, ovaries, brain,
kidneys, adrenal glands and pancreas (20-48 //g/g tissue).
Lower levels were found in the liver, lymph nodes, and
bone marrow (8-16 A
-------
lesions of PCB intoxication in humans and rhesus
monkeys exposed to similar levels over comparable
periods of time. Acne, subcutaneous edema of the face,
and edema of the eyelids were observed in man (ref. 22)
and lower primates (ref. 15) exposed to PCB's. The
facial signs of PCB exposure appear to be a sensitive
indicator of PCB intoxication. The rhesus monkeys after
exposure for 2 months to dietary levels of PCB's (2.5
and 5.0 ppm) developed facial alterations after a total
consumption of 32-50 mg of PCB's. It is noteworthy
that PCB levels of 5.0 ppm are presently permitted in
foods destined for human consumption.
The most debilitating lesions in the monkeys were
the severe hyperplasia and ulceration of the stomach.
Whether similar changes occur in the stomach of man
exposed to PCB's remains to be clarified. Nausea and
anorexia described by the human subjects suggest poten-
tial gastric alterations. Liver hypertrophy, proliferation
of the endoplasmic reticulum, and increased hepatic
microsomal enzyme activities were observed in man (ref.
23) and in lower primates (ref. 11).
Menstrual irregularities, decreased libido, occurrence
of stillborns, reduced birth weights, and transplacental
movement of PCB's in humans and rhesus monkeys have
been recorded (refs. 13,24). The reproductive failures of
monkeys exposed to PCB's were due to inability to
maintain a pregnant state. The majority of the animals
did not experience appreciable difficulty in conception;
however, a large percentage of the animals aborted
during the first 45 days of pregnancy. These observa-
tions suggest an inability of implantation or inability to
maintain the implanted embryo during the early stages
of pregnancy.
Although the mechanism of reproductive dysfunc-
tion has not been clarified, there is some indication of
hormonal modifications. Alterations in the urinary keto-
steroids were reported in humans exposed to PCB's (ref.
22). Increased levels of urinary ketosteroids have been
observed in the nonhuman primates that experienced
reproductive failures (ref. 14). One mechanism of altered
steroid metabolism may be secondary to the increase in
the hepatic mixed function oxidases that are present in
the hypertrophic livers of exposed animals. It has also
been a consistent observation that the organs associated
with steroid production, the adrenals and ovaries (par-
ticularly the corpora lutea), have contained relatively
high concentrations of PCB's in exposed animals. Thus
the compounds may possibly have a direct effect on
these organs.
The presence of PCB's in the milk of other species
has been previously reported (ref. 3). This avenue of
infant exposure and the potential morbidity and mor-
tality was vividly demonstrated in the infant monkeys
who nursed from mothers exposed to 2.5 and 5.0 ppm
in the maternal diets. The presence of relatively low
levels of PCB's in the diets of lactating females repre-
sents a potential source of PCB intoxication to nursing
infants.
Metabolic studies of the rhesus monkey demon-
strate over 90 percent absorption of the PCB's from the
gastrointestinal tract following oral administration. The
material is concentrated in organs with high lipid
content, including the adipose tissue, skin, adrenal,
corpora lutea of the ovaries, and brain. Within the liver
the greatest portion of the material is associated with the
membranes of the endoplasmic reticulum.
Studies with the single congener TCB demonstrate
the metabolism of the compound to hydroxylated forms
which are conjugated with glucuronic acid and excreted
into the bile. Enterohepatic circulation of the PCB's
undoubtedly occurs as only 20 percent of the material
secreted into the bile was recovered from the feces. The
greatest portion of the metabolized TCB was excreted
through the urinary system. The more highly chlorinated
biphenyl HCB was more slowly eliminated from the
body via the biliary-fecal route; HCB or metabolites
were not detected within the urine. The facilitated
metabolism and excretion of the lower chlorine con-
geners was also indicated by the relative decreased stor-
age of these compounds, and conversely the accumu-
lation of higher chlorinated congeners, within the
adipose tissue.
Metabolic studies that have been conducted on non-
human primates suggest mechanisms of interaction of
PCB's with tissues and, more importantly, indicate
potential mutagenic and carcinogenic effects of the
PCB's. Metabolites have been isolated from rhesus
monkeys exposed to the PCB congener 2,5,2',5'-tetra-
chlorobiphenyl that are formed through an arene oxid-
intermediate (ref. 18). Similar metabolites of the PCB's
and the potential for arene oxide formation has been
demonstrated in rabbits (refs. 25,26). Arene oxides
formed by the metabolism of other aromatic hydro-
carbons have been shown to covalently bind with macro-
molecules' and produce mutagenic and carcinogenic
changes in mammalian cells (ref. 27). Dechlorination of
the more highly chlorinated biphenyls, demonstrated by
dechlorination of 2,4,5,2',4',5'-hexachlorobiphenyl (ref.
28), provides a mechanism through which metabolism of
highly chlorinated biphenyls through an arene oxide
intermediate would be facilitated.
Evidence demonstrating the association of PCB's
with liver macromolecules supports the theoretical
potential of the PCB's for covalent binding with cellular
macromolecules. Thus, it appears that alkylation of
macromolecules is one mechanism by which the PCB
47
-------
metabolites cause widespread injurious effects. Further
credence for the ability of the compound to produce
alterations in the macromolecules is presented in recent
reports of hepatocellular tumors developing in rats and
mice exposed to RGB's (refs. 29-31).
REFERENCES
1. S. Jensen, "Report of a New Chemical Hazard,"
New Scientist, Vol. 32 (1966), p. 612.
2. M. Kuratsune, "An Epidemiologic Study on 'Yusho'
or Chlorobiphenyls Poisoning," Fukuoka Acta
Medica Vol. 60 (1969), p. 403.
3. A. C. Kolbye, "Food Exposures to Polychlorinated
Biphenyls," Environ. Health Persp., Vol. 1 (1972),
pp. 85-88.
4. F. J. Biros, A. C. Walker, and A. Medbery, "Poly-
chlorinated Biphenyls in Human Adipose Tissue,"
Bull. Environ. Contam. Toxicol., Vol. 5 (1970), pp.
317-323.
5. J. Finklea, L. E. Priester, J. P. Creason, T. Hauser,
T. Hinners, and D. I. Hammer, "Polychlorinated
Biphenyl Residues in Human Plasma Expose a Major
Urban Pollution Problem," Amer. J. Pub. Health,
Vol. 62 (1972), pp. 645-651.
6. J. R. Allen, L. A. Carstens, and L. J. Abrahamson,
"Responses of Rats Exposed to Polychlorinated
Biphenyls for Fifty-Two Weeks. I. Comparison of
Tissue Levels of PCB and Biological Changes, "Arch.
Environ. Contam. Toxicol., Vol. 4, in press.
7. M. L. Keplinger, 0. E. Fancher, J. C. Calandra, and
E. P. Wheeler, "Toxicological Studies with Poly-
chlorinated Biphenyls," paper presented at the
NIEHS Polychlorinated Biphenyl Conference,
Research Triangle Park, North Carolina, December
20-21,1971.
8. J. R. Allen and L. J. Abrahamson, "Morphological
and Biochemical Changes in the Liver of Rats fed
Polychlorinated Biphenyls," Arch. Environ.
Contam. Toxicol., Vol. 1 (1973), pp. 265-272.
9. J. R. Allen, L. A. Carstens, and D. H. Norback,
"Biological Effects of the Polychlorinated Biphenyls
in Nonhuman Primates," paper presented at Inter-
national Symposium on Recent Advances in the
Assessment of the Health Effects of Environmental
Pollution, Paris, June 24-28, 1974.
10. J. R. Allen and D. H. Norback, "Polychlorinated
Biphenyl and Triphenyl Induced Gastric Mucosal
Hyperplasia in Primates," Science, Vol. 179 (1973),
pp. 498-499.
11. J. R. Allen, L. J. Abrahamson, and D. H. Norback,
"Biological Effects of Polychlorinated Biphenyls
and Triphenyls on Subhuman Primates," Environ.
Res., Vol. 6 (1973), pp. 344-354.
12. J. R. Allen, L. A. Carstens, and D. A. Barsotti,
"Residual Effects of Short-Term, Low-Level
Exposure of Nonhuman Primates to Polychlorinated
Biphenyls," Toxicol. Appl. Pharmacol., Vol. 30
(1974), pp. 440-451.
13. D. A. Barsotti, R. J. Marlar, and J. R. Allen,
"Reproductive Dysfunctions in Rhesus Monkeys
Exposed to Low Levels of Polychlorinated Bi-
phenyls (Aroclor 1248)," Food Cosmet. Toxicol., in
press.
14. D. A. Barsotti and J. R. Allen, "Effects of Poly-
chlorinated Biphenyls on Reproduction in the
Primate,"Fed. Proc., Vol. 34 (1975), p. 338.
15. J. R. Allen, "Response of Primates to Polychlori-
nated Biphenyl Exposure," Fed. Proc., Vol. 34
(1975), pp. 1675-1679.
16. J. R. Allen, D. H. Norback, and I. C. Hsu, "Tissue
Modification:, in Monkeys as Related to Absorption,
Distribution and Excretion of Polychlorinated
Biphenyls," Arch. Environ. Contam. Toxicol., Vol.
2 (1974), pp. 86-94.
17. J. P. Van Miller, I. C. Hsu, and J. R. Allen, "Distri-
bution and Metabolism of 3H-2,5,2',5'-tetrachloro-
biphenyl in Rats," Proc. Soc. Exp. Biol. Med.,Vo\.
148 (1975), pp. 682-687.
18. I. C. Hsu, J. P. Van Miller, J. L. Seymour, and J. R.
Allen, "Urinary Metabolites of 2,5,2',5'-tetrachloro-
biphenyl in the Nonhuman Primate," Proc. Soc.
Exp. Biol. Med.,Vo\. 150 (1975), pp. 185-188.
19. D. H. Norback, J. L. Seymour, and J. R. Allen,
"Metabolic Study on 3H-2,4,5,2',4',5'-hexachloro-
biphenyl and 3H-2,5,2',5'-tetrachlorobiphenyl in
Rats," Amer. J. Path,, (1976) in press.
20. I. C. Hsu, J. P. Van Miller, and J. R. Allen, "Meta-
bolic Fate of 3H-2,5,2',5'-tetrachlorobiphenyl in
infant Nonhuman Primates," Bull. Environ.
Contam. Toxicol., Vol. 14 (1975), pp. 233-240.
21. J. L. Seymour, S. P, Schmidt, and J. R. Allen, "In
vitro Generation of a Chemically Reactive Metabo-
lite of 2,5,2',5'-tetrachlorobiphenyl by Rhesus
Monkey Liver Microsomes," Proc. Soc. Exp. Biol.
Med, submitted.
22. M. Kuratsune, T. Yoshimura, J. Matsuzaka, and A.
Yamaguchi, "Epidemiologic Study on Yusho, a
Poisoning Caused by Ingestion of Rice Oil Contami-
nated with a Commercial Brand of Polychlorinated
Biphenyls," Environ. Health Persp., Vol. 1 (1972),
pp. 119-128.
23. C. Hirayama, T. Irisa, and T. Yamamoto, "Fine
Structural Changes of the Liver in a Patient with
48
-------
Chlorobiphenyls Intoxication," Fukuoka Acta
Medica, Vol. 60 (1969), p. 455.
24. M. Kikuchi and M. Hashimoto, "Histopathological
Studies of Skin Lesions of Patients With Chloro-
biphenyls Poisoning," Fukuoka Acta Medica, Vol.
60 (1969), pp. 484-488.
25. A. M. Gardner, J. R. Chen, J. A. G. Roach, and E. P.
Ragelis, "Polychlorinated Biphenyls: Hydroxylated
Urinary Metabolites of 2,5,2',5'-tetrachlorobiphenyl
Identified in Rabbits," Biochem. Biophys. Res.
Comm., Vol. 55 (1973), pp. 1377-1384.
26. S. Safe, 0. Hutzinger, and D. Jones, "The Mech-
anism of Chlorobiphenyl Metabolism," J. Agric.
FoodChem., Vol. 23 (1975), pp. 851-853.
27. D. M. Jerina and J. W. Daly, "Arene Oxides: A New
Aspect of Drug Metabolism," Science, Vol. 185
(1974), pp. 573-582.
28. 0. Hutzinger, W. D. Jamieson, S. Safe, L. Paulmann,
and R. Ammon, "Identification of Metabolic
Dechlorination of Highly Chlorinated Biphenyl in
Rabbit," Nature, Vol. 252 (1974), pp. 698-699.
29. R. D. Kimbrough, R. A. Squire, R. E. Linder, J. D.
Strandberg, R. J. Montali, and V. W. Burse, "Induc-
tion of Liver Tumors in Rats by Polychlorinated
Biphenyl Aroclor 1260," J. Nat'l. Cancer Inst., in
press.
30. N. Ito, H. Nagasaki, S. Makiura, and M. Arai,
"Histopathological Studies on Liver Tumorigenesis
in Rats Treated with Polychlorinated Biphenyls,"
Gann, Vol. 65 (1974), pp. 545-549.
31. H. Nagasaki, S. Tomii, T. Mega, M. Marugami, and
N. Ito, "Hepatocarcinogenecity of Polychlorinated
Biphenyls in Mice," Gann, Vol. 63 (1972), p. 805.
DISCUSSION
VOICE: I'm from the Massachusetts Society. Have you
examined the samples for minute contaminants?
DR. ALLEN: That is a good question. I presume your
primary interests are in the dibenzofurans. The
Monsanto Company has volunteered to analyze the
Aroclor 1248 used in our experiments for the
furans. In our discussion last week they were hope-
ful of having these data available for this confer-
ence. If Dr. Wright is in the audience perhaps he
would give us a progress report on the subject. (No
answer from the audience.) ,1 can say that we have
done some preliminary work in this area and have
found undetectable levels of furans in the samples.
However, more detailed studies to clarify this ques-
tion are underway at the present time.
VOICE: How can you determine that the PCB's are
covalently bound to macromolecules?
DR. ALLEN: Repeated extractions carefully monitored
for radioactivity are the best methods of removing
any absorbed materfal from the protein. Standard
gel chromatography methods do not differentiate
between adsorption and covalently bound materials.
We hope to be able to generate enough PCB bound
to macromolecules to permit the determination of
the exact covalent nature of the bond following
macromolecalar digestion.
VOICE: Which macromolecule did you use?
DR. ALLEN: We were using protein and RNA from
monkey microsomes. These microsomes were
incubated with 3H PCB in a NADPH generating
system. The protein and RNA were isolated sub-
sequently and their radioactivity determined.
VOICE: Could you tell us roughly how much PCB your
animals consumed per kilogram of body weight?
DR. ALLEN: The female animals on the PCB experi-
ments weighed between 6 and 7 kilograms. Table 1
gives the average total intake of PCB's by these ani-
mals during the various experiments.
49
-------
PCB CHLORINATION VERSUS PCB DISTRIBUTION AND EXCRETION
H. B. Matthews, Ph.D.* and M. Anderson, Ph.D.t
Abstract
The distribution and excretion of selected
i*C-labeled polychlorinated biphenyls (PCB's) were
studied in the male rat. The distribution and excretion
of each of the PCB's was studied after either i.v. or oral
administration. Following administration, each of the
PCB's was rapidly removed from the blood and stored in
the liver and muscle. The rates of PCB redistribution
from liver and muscle to skin and adipose tissue and/or
elimination in urine was related to the degree of chlo-
rination. The subsequent rates of PCB removal from skin
and adipose tissue, excretion in urine, and total excre-
tion were related to the degree and position ofchlorina-
tion of the biphenyl molecule. None of the PCB's
studied was excreted to a significant extent prior to
metabolism to more polar compounds. It appears as if
the degree and position of chlorination controls the rate
of metabolism. The limiting factor in metabolism may
be the facility of arene oxide formation as a metabolic
intermediate. The toxicologic implications of arene
oxide formation versus PCB accumulation in animal
tissues are discussed.
INTRODUCTION
Due to the complexity of commercial polychlo-
rinated biphenyl (PCB) formulations and the difficulty
experienced by others in their efforts to interpret the
results of toxicological studies in which these mixtures
were used, we have chosen to study selected individual
PCB's. We believe that detailed studies of individual
PCB's, chosen to represent industrial PCB formulations,
may not only afford an insight into the biological fate of
the more complex commercial formulations, but may
also be used in the construction of pharmacokinetic
models of the distribution and excretion of these and
other chlorinated hydrocarbons. Our ultimate goal is to
have pharmacokinetic models which will permit the
accurate extrapolation of animal data to man.
Four of the PCB's studied were 4 chloro-, 4,4'-
dichloro-, 2,4,5,2',5'-pentachloro-, and 2,4,5,2',4',5'-
hexachlorobiphenyl. These PCB's have degrees of chlo-
rination similar to, and are constituents of Aroclors
'Pharmacology Branch, National Institute of Environ-
mental Health Sciences, Research Triangle Park, North Carolina.
tEnvironmental Biometry Branch, National Institue of
Environmental Health Sciences, Research Triangle Park, North
Carolina.
1221, 1232, 1254, and 1260, respectively. Each of the
PCB's studied was labeled with carbon -14.
METHODS
All of the data presented in this paper were ob-
tained with an i.v. dose of 0.6 mg PCB/kg body weight;
however, studies with the pentachlorobiphenyl at doses
ranging from 0.06 to 6.0 mg/kg failed to show any effect
of dose on the distribution and excretion of this PCB
(ref. 1). The results presented in this paper were ob-
tained by i.v. injection of the PCB's; however, these
results have been repeated without different reslilts by
studies in which the PCB's were administered by oral
intubation (ref. 2). In these studies, the time points of
sampling ranged from 15 minutes to 7 days for each of
the PCB's and up to 42 days for the penta- and hexa-
chlorobiphenyls. Three animals were treated and sacri-
ficed at each time point and the data presented represent
the average values obtained. The total radioactivity in
the tissue samples was determined by oxidation and
liquid scintillation counting.
RESULTS
Following i.v. injection, approximately 90 percent
of the total dose of each PCB was removed from the
blood within 15 minute's. Initially, most of the admin-
istered dose was stored in the liver and muscle. Within
15 minutes after administration, the liver contained 15
to 30 percent of the total dose of each of the PCB's
(figure 1). Removal of mono- and dichlorobiphenyl from
liver was primarily via excretion in the bile in the form
of several metabolites; only trace amounts of the parent
compounds were excreied in the bile. The pentachlo-
robiphenyl was removed from the liver by metabolism
and excretion in the bile and by redistribution to other
tissues, whereas the primary mechanism for the removal
of hexachlorobiphenyl from the liver was redistribution.
Due to the relatively large mass of muscle, total storage
of the PCB's in muscle was similar to that observed in
liver (figure 2). It is assumed that the only mechanism of
PCB removal from muscle was by redistribution to tis-
sues having a higher affinity for these compounds (ref.
2).
Most of the long-term storage of PCB's in the body
was in the skin and adipose tissue. Since one of the
earliest symptoms of chronic intoxication by PCB's and
certain other chlorinated hydrocarbons is chloracne, a
skin disorder (ref. 3), data on the accumulation of these
50
-------
PCB distribution-% total dose in liver vs. time
• chlorobiphenyl
dichlorobiphenyl
• pentachlorobiphenyl
• hexachlorobiphenyl
I 2
Time (day)
Figure 1. Rate of removal of PCB's from liver.
51
-------
PCB distribution- % total dose in muscle vs. time
• chlorobiphenyl
A dichlorobiphenyl
• pentachlorobiphenyl
«\ *hexachlorobiphenyl
Time(day)
Figure 2. Rate of removal of PCB's from muscle.
52
-------
compounds in skin was of particular interest (figure 3).
It may not be obvious in figure 3, due to the long time
scale of 8 hours to 42 days, but the uptake of RGB's by
skin was slower than the uptake by liver and muscle (ref.
2). The rate of PCB removal from skin decreased as the
degree of chlorination of the RGB's increased, and fol-
lowing the removal of approximately 25 percent of the
hexachlorobiphenyl, little further decay from skin was
observed during the remainder of the 42-day study.
The accumulation of RGB's in adipose tissue was a
slower process than that observed in skin (figure 4). The
peak concentrations of mono-, di-, penta-, and hexachlo-
robiphenyl in adipose tissue were reached at 1 hour, 2
hours, 4 hours, and 7 days after administration, respec-
tively. The magnitude of the peak concentrations in fat
also tended to increase with increasing chlorination,
whereas the rates of PCB removal from adipose tissue
decreased with increasing chlorination of the PCB. Hexa-
chlorobiphenyl concentrations in fat never showed a
decline from peak concentrations.
The rates of PCB removal from tissues would be
expected to be reflected in their rates of excretion. All
rats kept for 1 day or longer were held in individual
metabolism cages and fed food and water ad libitum.
Both urine and feces were collected daily. The most
dramatic effect of increasing chlorination of the bi-
phenyl molecule was seen in the percent of the total
dose excreted in the urine (figure 5). Cumulative excre-
tion in urine for 7 days accounted for approximately 60,
34, 8, and less than 1 percent of the total mono-, di-,
penta-, and hexachlorobiphenyl dose, respectively Great-
er than 90 percent of the material excreted in the urine
was in the form of one or more conjugated metabolites
of the given PCB (ref. 2).
Cumulative excretion of the PCB's in feces was a
more consistent process which, with the exception of
the hexachlorobiphenyl, did not appear to be greatly
affected by degree of chlorination (figure 6). Animals
treated with penta- or hexachlorobiphenyl were held for
up to 42 days. Extrapolation of the daily rates of total
PCB excretion showed that, with the exception of hexa-
chlorobiphenyl, excretion would eventually account for
approximately 100 percent of the administered dose of
each PCB. The excretion of hexachlorobiphenyl was so
slow that extrapolation to infinite time indicated that
less than 20 percent of the administered dose would ever
be excreted.
DISCUSSION
Work in our laboratory and elsewhere indicates that
only about 10 percent of each of these PCB's is excreted
as the parent compound. We also know from extraction
and analysis of the radioactivity in the tissues that appre-
ciable amounts of the metabolites are not stored in the
tissues (ref. 2). We have thus assumed that metabolism is
a prerequisite to the excretion of PCB's. We have also
shown that the rates of excretion and the rates of re-
moval from skin and adipose tissues of mono-, di-, and
pentachlorobiphenyl are inversely proportional to their
degrees of chlorination (ref. 2). On the other hand, the
very slow excretion of hexachlorobiphenyl would not
have been predicted by this relationship. Therefore, an
additional factor appeared to be affecting the rate of
metabolism of hexachlorobiphenyl.
An examination of the molecular structures of these
four PCB's shows that there is only one obvious differ-
ence, other than chlorination, among the structures of
the hexachlorobiphenyl and the three other PCB's. The
difference is that this hexachlorobiphenyl does not have
two adjacent unsubstituted carbon atoms.
It was demonstrated in Williams' laboratory in the
1950's that chlorinated benzens that had two adjacent
unsubstituted carbon atoms were metabolized and ex-
creted 3 to 20 times more rapidly than benzenes with
similar degrees of chlorination that did not have adjacent
unsubstituted carbon atoms (refs. 4,5). Schulte and
Acker suggested that a similar substitution pattern is
required for the metabolism of PCB's (ref. 6). This sug-
gestion was partially confirmed by Jensen and Sund-
strom (ref. 7) when they showed that PCB's which did
not have two adjacent unsubstituted carbon atoms were
found in the highest concentrations in the tissues of
higher animals and man. The hexachlorobiphenyl used in
our studies was found in the highest concentrations of
any PCB in human tissues. Our data on the distribution
and excretion of this PCB and the fact this particular
PCB is one of the more common constituents of the
more' highly chlorinated commercial PCB formulations
explain why such high concentrations were found in
human and animal tissues.
As a point of reference, we have also studied the
distribution and excretion of similar doses of several
chlorinated pesticides in the rat. The initial half-life of
dieldrin was quite similar to that of pentachlorobi-
phenyl.'The initial half-life of DDT was five- to six-fold
longer than that of pentachlorobiphenyl and only Mirex
and hexachlorobenzene, of the pesticides tested, had
infinitely long half-lives such as that observed for hexa-
chlorobiphenyl (ref. 8).
Two adjacent unsubstituted carbon atoms are
important to the metabolism of the PCB's because their
presence facilitates the formation of arene oxides. Arene
oxides are formed by the hepatic mixed-function
oxidases as intermediates in the metabolism of a number
of lipophilic compounds, and these oxides have been
53
-------
10
20 30
Tim* (day*)
40
Figure 3. Rate of removal of PCB's from skin.
10
20 30
Time (days)
40
Figure 4. Rate of removal of PCB's from adipose tissue.
54
-------
60
5O
40
o>
in
O
TJ
o30
£
S«
20
10
PCB excretion in urine
• chlorobiphenyl
A dichlorobiphenyl
• pentachlorobiphenyl
* hexachlorobiphenyl
345
Time (day)
Figure 5. Cumulative excretion of RGB's in urine.
PCB excretion in feces
• chlorobiphenyl
dichlorobiphenyl
• pentachlorobiphenyl
* hexachlorobiphenyl
123456
Time (day)
Figure 6. Cumulative excretion of PCB's in feces.
55
-------
implicated as potential carcinogens (refs. 9,10). Evidence
for arene oxides as intermediates in the metabolism of
implicated as potential carcinogens (refs. 9,10). Evidence
for arene oxides as intermediates in the metabolism of
RGB's has been provided by Gardner etal. (ref. 11), Safe
et al. (ref. 12), and in our own laboratory (ref. 13).
Thus, we are given a dilemma. Those PCB's which
can be metabolized and excreted may be metabolized via
a carcinogenic intermediate and those PCB's which are
not readily metabolized have an extremely long biologi-
cal half-life. Several researchers have provided evidence
that the PCB's may be carcinogenic (refs. 14-16). On the
other hand, Vos et al. (ref. 17) have shown the very
slowly metabolized hexachlorobiphenyl used in this
study to be acnegenic, to cause liver damage, and to
induce hepatic porphyria. It is not yet known if it is the
parent PCB's or their metabolites which account for the
primate reproductive failures described by Allen (ref.
18). The only way that we are going to establish which
of the PCB's or their metabolites are carcinogenic or are
going to cause any of the other toxicological problems
and at what levels of exposure the problems are likely to
arise is through systematic pharmacokinetic studies,
which will allow us to extrapolate the results of chronic
low-dose environmental exposures from laboratory
animals to man. Until such data are available, it is my
opinion that every effort should be made to avoid envi-
ronmental contamination by any type of PCB's.
REFERENCES
1. H. B. Matthews, and M. W. Anderson, "The Distri-
bution and Excretion of 2,4,5,2',5'-Pentachlorobi-
phenyl in the Rat," Drug Metab. Dispos., Vol. 3,
No. 3 (1975), pp. 211-219.
2. H. B. Matthews, and M. W. Anderson, "Effect of
Chlorination on the Distribution and Excretion of
Polychlorinated Biphenyls," Drug Metab. Dispos.,
Vol. 3, No. 5 (1975), pp. 371-380.
3. R. D. Kimbrough, "Toxicity of Chlorinated Hydro-
carbons and Related Compounds," Arch. Environ.
Health, Vol. 25 (1972), pp. 125-131.
4. W. R. Jondorf, D. V. Parke, and R. T. Williams,
"Studies in Detoxication, 66. The Metabolism of
Halogenobenzenes. 1:2:3-, 1:2:4-and 1:3:5-Trichlo-
robenzenes," Biochem. J. Vol. 61 (1955), pp.
512-521.
5. W. R. Jondorf, D. V. Parke, and R. T. Williams,
"Studies in Detoxication, 76. The Metabolism of
Halogenobenzenes, 1:2:3:4-, 1:2:3:5- and
1:2:4:5-Tetrachlorobenzenes," Biochem. J., Vol. 69
(1958), pp. 181-189.
6. E. Schulte, and L. Acker, "Identifizierung and
Metabolisierbarkeit von polychlorierten Biphenylen,
Naturwissenschaften, Vol.~61, No. 2 (1974f, pp.
79-80.
7. S. Jensen, and G. Sundstrom, "Structures and
Levels of Most Chlorbiphenyls in Two Technical
PCB Products and in Human Adipose Tissue,"
Ambio, Vol. 3 (1974), pp. 70-76.
8. H. B. Matthews, unpublished.
9. J. W. Daly, D. M. Jerina, and B. Witkop, "Arene
Oxides and the NIH Shift: The Metabolism, Toxici-
ty and Carcinogenicity of Aromatic Compounds,"
Experientia, Vol. 28 (1974), pp. 573-582.
10. D. M. Jerina, and J. W. Daly, "Arene Oxides: A New
Aspect of Drug Metabolism," Science ,Vol. 185
(1974), pp. 573-582.
11. A.M. Gardner, J. T. Chen, J. A. G. Rouch, and E. P.
Ragelis, "Polychlorinated Biphenyls: Hydroxylated
Urinary Metabolites of 2,5,2',5'-Tetrachlorobi-
phenyl Identified in Rabbits," Biochem. Biophys.
Res. Comm., Vol. 55, No. 4 (1973), pp. 1377-1384.
12. S. Safe, 0. Hutzinger, and D. Jones, "The Mecha-
nism of Chlorobiphenyl Metabolism," J. Agric.
FoodChem. Vol. 23, No. 5 (1975), pp. 851-853.
13. P. R, Chen, J. D. McKinney, and H. B. Matthews,
"2,4,5,2',5'-Pentachlorobiphenyl Metabolism in the
Rat: Qualitative and Quantitative Aspects," in press.
14, N, Ito, H. Nagasaki, M. Arai, S. Makiura, S.
Sugihara, and K. Hirao, "Histopathologic Studies on
Liver Tumorigenesis Induced in Mice by Technical
Polychlorinated Biphenyls and Its Promoting Effect
on Tumors Induced by Benzene Hexachloride," J.
Natl. Cancer Inst. Vol. 51, No. 5 (1973), pp.
1637-1642.
15. R. D. Kimbrough, and R. E. Linder, "Induction of
Adenofibrosis and Hepatomas of the Liver in
BALB/cJ Mice by Polychlorinated Biphenyls
(Aroclor 1254)," J. Natl. Cancer Inst., Vol. 53, No.
2 (1974), pp. 547-549.
16. R. D. Kimbrough, R. A. Squire, R. E. Linder, J. D.
Strandberg, R. J. Montali, and V. W. Burse, "Induc-
tion of Liver Tumors in Sherman Strain Female
Rats by Polychlorina'ted Biphenyl Aroclor 1260," J.
Natl. Cancer Inst., in press.
17. J. G. Vos, and E. Notenboom-Ram, "Comparative
Toxicity Study of 2,4,5,2',4',5'-Hexachlorobiphenyl
and a Polychlorinated Biphenyl Mixture in Rab-
bits," Toxicol. Appl. Pharmacol., Vol. 23 (1972),
pp. 563-578.
18. D. A. Barsotti, R. J. Marlar, and J. R. Allen,
"Reproductive Disfunctions in Rhesus Monkeys
Exposed to Low Levels of Polychlorinated Bi-
phenyls (Aroclor 1248), in press.
56
-------
ENZYMATIC AND OTHER BIOCHEMICAL
RESPONSES TO SELECTED PCB's
D. J. Ecobichon, Ph.D.*
Abstract
Isomerically-pure mono-, di-, tri-, tetra-, hexa-, and
octa-chlorobiphenyls were injected i.p. into weanling
male rats at a dosage of 50 mg/kg/day for 3 consecutive
days, the animals being killed 96 hr after the last injec-
tion. The influence of position and degree of chlorina-
tion of the biphenyl nucleus on hepatic function was
compared to that produced by purified biphenyl.
Hepatic function was assessed by pentobarbital sleeping
times and in vitro assays of p-nitroanisole 0-demethyl-
ase, aniline hydroxylase, aminopyrine N-demethylase,
carboxylesterase and sulfobromophthalein-glutathione
conjugating enzyme activities. For the mono-oxygenases
closely associated with the hepatic endoplasmic retic-
ulum, enhanced induction of activity was observed with
highly chlorinated biphenyls and by low chlorine-
containing congeners having chlorine atoms substituted
at the 4- and 4'-positions irrespective of chlorination at
other positions. For those enzymes less discretely
localized in the hepatocyte, the position of the chlorine
atoms appeared to be less important. Interrelationships
with other hepatic functions and the rate of chloro-
biphenyl biotransformation is discussed.
Toxicologic assessment of commercial chloro-
biphenyl mixtures has been complicated by the hetero-
geneity of the congeners, by marked differences in
physical and chemical properties which, undoubtedly,
influence rates of absorption, distribution, metabolism
and excretion and by the possible presence of toxic
impurities and byproducts (refs. 1-4). As techniques of
definitive analysis have developed, the complexity of
commercial chlorobiphenyls (Aroclors, Monsanto
Industrial Chemicals, St. Louis, Mo.) has been revealed
showing that, with the exception of Aroclor 1016 and
1232, one predominant congener composed of a number
of positional isomers is found in each preparation (fig.
1). As the percentage of chlorine increases, the pre-
dominant congener shifts from a mono- to a tri- to a
tetra- to a penta-chlorobiphenyl (refs. 5,6).
If it was possible to separate these complex mix-
tures, one could examine several facets of the toxicology
of these compounds, and several questions could be
posed and, perhaps, answered. Do the various congeners
•Department of Pharmacology, Faculty of Medicine,
Dalhousie University, Halifax, Nova Scotia, Canada.
possess the same toxicological properties; i.e., do
dichlorobiphenyls have the same effect as hexachloro-
biphenyls? Do all of the tetrachlorobiphenyl isomers
produce the same toxicologic responses? Are the
pathologic and toxicologic alterations observed due to
the biphenyl nucleus itself, to the positions occupied by
individual chlorine atoms, or to the number of chlorines
present on the biphenyl nucleus. Since hepatic enzyme
induction has been a well-characterized phenomenon of
adaptation to these chemicals, we attempted to answer
some of the above questions using changes in hepatic
ultrastructure and in enzyme activity as indices of
structure-activity relationships.
Our first study, completed in 1972, and published
in 1974, used a small series of isomerically-pure chloro-
biphenyls of known position and degree of chlorination,
synthesized and purified by my colleagues. Dr. 0.
Hutzinger and Dr. S. Safe (refs. 3,7). The objective of
these experiments was to elicit responses (induction of
hepatic drug-metabolizing enzymes) which, hopefully,
could be related to the structures of the pure chloro-
biphenyls. We injected young male Wistar strain rats
intraperitoneally with 50 mg/kg of the agent, dissolved
in peanut oil, for 3 consecutive days, the animals being
killed 96 hr after the last injection. The livers were
quickly removed and samples were taken and stained for
light and electron microscopy. The remaining hepatic
tissue was used for the preparation of microsomes and
soluble supernatant for the enzymatic assays. These
assays included representative functions of the micro-
somal mono-oxygenases (p-nitroanisole 0-demethylase,
aniline hydroxylase, aminopyrine N-demethylase),
hydrolases (nonspecific carboxylesterase) and the con-
jugation of sulfobromophthalein (BSP) with reduced
glutathione (GSH). Some of the results of that study are
shown in the next few figures.
Figure 2 presents the results observed for the cyto-
plasmic enzyme system involved in conjugating BSP
following exposure to DDT, Aroclor 1254 and 1260,
biphenyl, and a series of pure chlorobiphenyls. Signifi-
cant (p<0.05) increases in activity were observed with
all agents tested. It should be noted that biphenyl caused
a marked increase in this enzyme activity.
Figure 3 shows the influence of the DDT isomers,
commercial Aroclors, biphenyl, and the series of
isomerically pure chlorobiphenyls on pentobarbital-
induced sleeping time. Highly significant (p<0.05) re-
ductions in sleeping time were observed with the
57
-------
commercial Aroclors and DDT isomers. Biphenyl and
4-chlorobiphenyl caused no significant (pX3.05) changes
in sleeping time. Of the dichloro-isomers, only the 4,4'-
isomer significantly reduced the duration of effect. Both
tetrachloro-isomers caused significant reductions in
sleeping time though the 2,5,2',5'-isomer was less effec-
tive. The hexa- and octa-chlorobiphenyls caused a mark-
ed reduction in sleeping times, being comparable to
those observed with p,p'-DDT and the commercial Aro-
clors.
Figure 4 summarizes the influence of the various
agents tested on the hepatic mixed function oxidases
aniline hydroxylase (A), p-nitroanisole 0-demethylase
(B), and aminopyrine N-demethylase (C). As has been
observed by others, we found that the most responsive
enzymes were those closely associated with the smooth
endoplasmic reticulum. The results in vitro reflected the
observations of altered sleeping times in vivo. One can
see that, even with this limited number of pure
chlorobiphenyls, not all caused effects of the same
magnitude. To summarize the results of this study,
treatment with biphenyl caused slight induction while
4-chlorobiphenyl did not. The mixed function oxidases
were markedly induced by pure hexa- and octa-chloro-
biphenyls and also by di- and tetra-chlorobiphenyls with
chlorines substituted at the 4-positions of the rings.
Considering the dichloro-isomers, when the 4- and
4'-positions were occupied, there was a much greater
inductive effect for all of the enzyme activities than was
observed with the 2,2'- and 2,4'-isomers. The same
positional phenomenon was observed for the two
tetra-chlorobiphenyls studied, the induction caused by
2,4,2',4'-tetra-chlorobiphenyl being much greater than
that observed with the 2,5,2',5'-isomer. The results
obtained for the higher chlorinated analogs suggested
that the positions of the chlorine atoms were not as
important. Our results, with the exception of the
marked effects obtained following treatment with
4,4'-dichlorobiphenyl, confirmed the observations of
other investigators who have found that penta-, hexa-
and octa-chlorobiphenyls had greater enzyme-inducing
potential than did low chlorine-containing biphenyls
(refs. 8-11).
On the basis of our initial studies, we came to the
conclusion that the biphenyl nucleus could exert some
effect on hepatic enzyme levels (fig. 4) though the only
function markedly affected was the BSP-GSH conju-
gation (fig. 2). Much more important conclusions were
that not all congeners possessed the same toxicologic
properties and that, while greater inductive effects were
observed with highly chlorinated biphenyls, marked
ultrastructural and enzymatic changes were observed
with specific di- and tetra-chlorobiphenyls, particularly
those with chlorines substituted on the 4-position on the
ring. We have extended the investigation to a broader
series of mono-, di-, tri-, and tetra-chlorobiphenyls in an
attempt to confirm the importance of position of the
chlorine on the ring structure of low chlorine-containing
congeners. Isomerically-pure chlorobiphenyls, synthe-
sized by my colleagues or purchased from Analabs Inc.
(North Haven, Conn.), were injected intraperitoneally
using the same regimen (50 mg/kg/day for 3 consecutive
days, killing the animals 96 hr after the third injection).
A 12,000 g-20 min supernatant from 20% w/v
homogenates of liver was used as the enzyme source.
This study has been published recently (ref. 12). Some
of the pertinent results are shown in the next figures.
It was essential, before studying the effects of
chlorination and position, to determine what effects the
biphenyl nucleus had on hepatic enzymes. Table 1 shows
the results of the i.p. administration of vehicle (peanut
oil), commercially available biphenyl (Eastman Organic
Chemicals, Rochester, iN.Y.), and purified biphenyl on
the activities of hepatic: 0-demethylase (OD), aniline
hydroxylase (AH), carboxylesterase (CE), and the
BSP-GSH conjugating enzyme. Treatment with un-
purified biphenyl resulted in significant (p<0.05)
increases in activities of three of the enzymes. In
contrast, biphenyl repurified by thin layer chroma-
tography caused a significant increase only in BSP-GSH
conjugating enzyme activity, suggesting the presence of
an impurity in the commercial material. Since relatively
pure chlorobiphenyls were to be used, repurified
biphenyl was used for the control groups of animals.
The influence of monochlorobiphenyls on hepatic
0-demethylase, aniline hydroxylase, carboxylesterase,
and BSP-GSH conjugating enzyme activities are com-
pared in table 2 with the effects following treatment
with biphenyl. While changes in microsomal 0-de-
methylase were not observed, all three monochloro-
isomers significantly increased aniline hydroxylase and
carboxylesterase levels, The BSP-GSH conjugating
enzyme activity was not alfected.
The influence of a series of di-, tri-, and
tetrachlorobiphenyls on ithe selected enzymatic func-
tions are shown in figures 5, 6, and 7, respectively. With
each series of isomers, a chlorine atom on the 4-position
caused a more marked induction of hepatic drug-
metabolizing enzyme activities than did a chlorine atom
at any other position. As one increased the degree of
chlorination, subsequent substitution at the 2-position
was next in importance Followed by substitution at the
3-position. The results conclusively demonstrated that
not all isomers of the mono-, di-, tri-, and tetrachloro-
58
-------
Table 1. The effects of intraperitoneally administered peanut oil,
commercial biphenyl, and purified biphenyl dissolved in
peanut oil on enzyme activities of rat liver8
Activities (in total wt of fresh liver/100 g body wt)
Enzyme
p-Nitroanisole
0-demethylase
Aniline
hydroxylase
Carboxylesterase
Vehicle
168.0+23.9
102.7+26.7
234.4+53.5
Commercial
biphenyl
211.5+38.7
352.8+102.8°
336.7+55.3°
Purified
biphenyl
195.6+19.1
97.3+15.1
236.2+24.7
BSP-GSH
conjugating
enzyme
5.0+ 0.9
14.4+ 1.91
8.8+ 0.9'
The animals received 50 mg of biphenyl/kg (0.15-0.25 ml of solution) for
3 consecutive days and were killed 96 hr after the last injection.
Vehicle-treated animals received peanut oil on the same volume basis.
Twelve animals were treated with vehicle, 11 with commercial biphenyl,
and 18 with purified biphenyl.
The activities of 0-demethylase and aniline hydroxylase are expressed
as nanomoles of product formed/minute. Carboxylesterase activity is
expressed as micromoles of substrate hydrolyzed/minute while the BSP-
GSH conjugating enzyme activity is expressed as micrograms of conju-
gate formed/minute. Activities are presented in terms of the total
liver/100 g of body wt.
cValues are statistically different from vehicle-treated control values
at p<0.05.
59
-------
Table 2. Effects of acute intraperitoneal administration
of biphenyl and monochlorobiphenyls on hepatic
enzyme activity
Activities (in total wt of fresh liver/100 g
Treatment
Biphenyl
2-Chlorobiphenyl
3-Chlorobiphenyl
4-Chlorobiphenyl
n
18
6
6
6
ODC
(nmol/min)
195.6+19.1
184.8+17.2
193.6+28.1
233.4+32.5
AH
(nmol/min)
97.3+15.7
188. 3+30. 4b
225. 8+55. 3b
168. 1+37. 4b
CE
(ymol/min)
236.2+24.7
309. 2+35. lb
381. 7+64. 3b
306. 2+24. 5b
body wt)a
BSP
(yg/min)
8.8+0.9
7.5+1.5
9.8+1.5
9.8+1.6
Values presented are the mean +_ SD of the number of animals per group.
"Values are significantly different from values obtained from biphenyl-
treated animals, p<0.05.
'The enzymes investigated include p-nitroanisole 0-demethylase (OD),
aniline hydroxylase (AH), carboxylesterase (CE), and sulfobromophtha-
lein-glutathione conjugating enzyme (BSP).
:E
o
70-i
60-
50-
40-
30-
20-
10-
0-
(9)
(5)
(10)
(3)
(9)
(13)
(11)
r
(10) (10)
™1
(3) (14)
(6) r-
iu^ L
—
>vw
,t.n.
(5)
(14)
T,
•MM
(10)
-*
(7)
(8)
1^
n"
N
mi (8)
•pm
!
^23 , i pm
TIT
;'
*
»w
i
?
(in)
(5)
x
12345 012345 012345 123456 1234567 1234567
1016 1221 1232 1242 . 1248 1254
AROCLOR COMPOSITION (No. Chlorine Atoms/Molecules)
Figure 1. The congener composition of commercially available Aroclors
based on the weight percent of biphenyls bearing different
numbers of chlorine atoms/molecule. Data were obtained from
reports by Webb and McCall (ref. 6), Sissons and Welti (ref. 5),
and from information supplied by the Monsanto Industrial
Chemicals Company.
60
-------
pg CONJUGATE/mg PROTEIN
10
15
20
CONTROL
P, P1 DOT
0, p'DDT
AROCLOR 1254
AROCLOR 1260
BIPHENYl
4-MONO-Cl
2,2'DI Cl
2,4'DI Cl
4, 4' Di Cl
2,5,2,'5' TETRA Cl
2,4,2:4' TETRA Cl
2,4,5,2;4:5' HEXA Cl
z.s.s.za1!1 HEXACI
2.4,6,2:4»' HEXA Cl
2,3,4,5. 23W51 OCTACI
1 . i .. 1 . J
=£
U
1 1
H-H
1 — ] 1
1
H-+-H
1 ) 1
1 1 1
BSP ASSAY
RH
r H-I
1
J H 1 1
^
i — i — i
> 1 1
1 1 1
— —
1 1 '
i ' 1 '
JFigure 2. The effect of pretreatment of young
male rats with DDT (o,p', and p,p'-
ispmers), Aroclors 1254 and 1260,
biphenyl, and a series of isomerically
pure chlorobiphenyls on the hepatic
cytoplasmic enzyme which conjugates
sulfobromophthalein (BSP) with re-
duced gluthathione. Activities are
expressed as pig of conjugate formed
mg-1 protein min-1. Animals were
treated by i.p. injection for 3 con-
secutive days, enzyme activity
being determined 96 hr after the
last injection. The values (bars)
represent mean activities ±S.D. of
the means of 19 control animals
and 7 animals per treated group.
p, p'DDT
o, p'DDT
AROCLOR 1254
AROCLOR 1260
BIPHENYL
4-MONO-CI
2,2'Di Cl
2,4'Di Cl
4,4' Di Cl
2,5,2,V TETRA Cl
2,4,214' TETRA Cl
2,3,5,2|3;5' HEXA Cl
2,4,6,2,'4;6C HEXA Cl
2,3,4,5, 2,'3,'4!5' OCTA Cl
TIME ( minutes )
3 40 80 120
1 , J , 1
i
' 1 '
-j , 1
1
1
i-4— i
' — ~\ — ^
1
' T '
i — j 1
^
*~H
3-
SLEEPING TIME
h |
r (Pentobarb - 40 mg/Kg)
^
1
T, 1
Figure 3. The effect of pretreatment of young
male rats with DDT (o,p' and p,p'-
isomers), Aroclor 1254 and 1260,
biphenyl, and a series of isomerically
pure chlorobiphenyls on the sleeping
time produced by an injection of 40
mg/kg sodium pentobarbital. For
other details, see figure 2.
61
-------
nMOLES/mg PROTEIN
nMOLES/mg PROTEIN
nMOLES/mg PROTEIN
(
CONTROL
p, p'DDT
o.p'DDT
AROCLOR 1254
AROCLOR 1260
BIPHENYL
4-MONO-CI
2,2'Di Cl
4,4' Di Cl
2 5 2,'5' TETRA Cl
2,4,2:4' TETRA Cl
2,4,5,2;4:5' HEXA Cl
235 2;3.'5' HEXA Cl
2,4,6,2:4:6' HEXA Cl
,4,5, 2;3;4!5' OCTA Cl
50 100 150 200 0
1 . 1 . 1 . 1
i
T
i 1 1
i-f<
-H
i— )— i
1 — 1 — •
=^
F=L*
- | . ANILINE HYOROXYLASE
1
1 i — } t
i 1 1
h-fH
) 1
1 1 1
1 1 1
50 100 150 200 t
1 . 1 . 1 . 1
— 1
— T
|
i l~l — '
1
*
1
H-H
1
1 — 1 — 1
1
r
=>
i
_ T
j. O-DEMETHYLASE
1 1
1 ^
1
1
1*
i— |— 1
1
h-JH
l-|-l
^H
1 *~^
100 200 300 400
1 . 1 , 1 . 1 .
;=^
, — i — ,
|-H
>~H
i — | — i
1 ' — 1 — '
h— 1 N-DEMETHYLASE
i 1 1
1
1
i — | — i
1 ' '
i 1 1
i ( j
1
i i '
1
1
I i 1
B
Figure 4. The effect of pretreatment of young male rats with DDT (o,p'-
and p,p'-isomers), Aroclor 1254 and 1260, biphenyl, and a series
of isomerically pure chlorobiphenyls on hepatic microsomal aniline
hydroxylase (A), p-nitroanisole 0-demethylase (B), and aminopyrine
N-demethylase (C), activities. Activities are expressed as nmoles of
product formed/mg microsomal protein/SOmin incubation. For
other details, see figure 2.
62
-------
nmole/min
ACTIVITY ( In total wt. of fresh liver/lOOg body wt.)
nmole/min \i mole/min
mg/min
0 100 200 300 400 0 100 200 300 400 0 100 200 300 400 500 0 5 10 15 20
BIPHENYL
2,2'
2,4'
3,3'
4,4'
^^^^
OD
AH
CE
BSP
igure 5. The effect of pretreatment of young male rats with biphenyl
and series of isomerically pure dichlorobiphenyls on hepatic
p-nitroanisole 0-demethylase (OD), aniline hydroxylase (AH),
carboxylesterase (CE), and solfobromophthalein-glutathione
conjugating enzyme (BSP) activities. Animals were treated by
i.p. injection for 3 consecutive days and were killed and assayed
96 hr after the last injection. The values (bars) represent the
mean enzymatic activities ±S.D. (lines) of 18 control, biphenyl-
treated rats and 6 animals per treated group. The asterisk (*)
indicates values statistically different (p< 0.55) from biphenyl-
treated controls.
63
-------
ACTIVITY I In Wai «t. o( Iresh llver/lOOg tody «U
nmole'min nmole/mm (j mole/mm mci/min
02tD400600800010020030040002!)0400
-------
biphenyls possess the same toxicologic properties, the
position of chlorination being as important as degree of
chlorination.
The porphyrogenic nature of chlorinated biphenyls is
well known (refs. 2,13-15). Goldstein et al. and Grote et
al. demonstrated marked increases in 6-aminolevulinic
acid synthetase following treatment with commercial
chlorobiphenyls (refs. 15,16). This enzyme, located in
hepatic mitochondria, is the rate-limiting catalyst in the
synthesis of heme and prophyrins. Recently, Goldstein
et al. completed a study of the effects on chick liver,
feeding five different, isomerically pure hexachloro-
biphenyls at concentrations of 400 ppm or 3 weeks (ref.
17). All agents caused uroporphyrin accumulation,
increased hepatic cytochrome P-4so, and microsomal
drug-metabolizing enzymes but only 3,4,5,3',4',5'-,
2,3,4,2',3',4'-, and 2,4,5,2',4',5'-hexachlorobiphenyl
caused gross accumulation of hepatic porphyrins. These
isomers were also the most toxic. It is notable that these
three isomers had both the m- and p-positions occupied
by chlorines, while the other two isomers (2,3,6,2',3',6'-
and 2,4,6,2'/4',6'-) had either the m- or the p- positions
unoccupied.
Several investigators have demonstrated that the low
chlorine-containing congeners in commercial mixtures
disappeared more rapidly from tissues than did the
highly chlorinated biphenyls (refs. 18-22). In our earliest
paper, we suggested that the magnitude of hepatic
enzyme induction might be related to the rate of
degradation and elimination of the congeners from the
body (3). There is ample evidence of hydroxylated
derivatives of chlorobiphenyls being eliminated from
mammalian systems and, no doubt, we shall hear more
about them at this meeting (refs. 23-27). Evidence in the
literature suggests two possible mechanisms of biotrans-
formation. The first and most rapid mechanism involves
the formation of an arene oxide intermediate and
requires the presence of unsubstituted adjacent (vicinal)
carbon atoms in the nucleus (ref. 24,27,28). The second
and much slower mechanism uses a different hydroxyla-
ting system for isolated unsubstituted positions as are
found in highly chlorinated biphenyls (ref. 26). The
position of chlorination in low chlorine-containing
biphenyls could have considerable directing influence
over the pathway of biotransformation. Certain low
chlorine biphenyls would be less effective (and less
toxic) due to rapid biotransformation via arene oxide
intermediates. Others, substituted at a position (i.e.,
4-position) which would disrupt the vicinal carbon
arrangement, would be unable to undergo rapid
biotransformation and would persist in vivo. The
toxicity of these agents may be closely correlated with
lipid solubility, high concentration in the liver, and along
duration of action, but it is evident that the position of
the substituent chlorines on the biphenyl nucleus may
be the key factor governing these other properties.
REFERENCES
1. V. Zitko and P. M. K. Choi, "PCB and Other Indus-
trial Halogenated Hydrocarbons in the Environ-
ment," Fisheries Research Board of Canada,
Technical Report 272, 1971.
2. J. G. Vos and J. H. Koeman, "Comparative Toxico-
logic Study With Polychlorinated Biphenyls in
Chickens With Special Reference to Porphyria,
Edema Formation Liver Necrosis and Tissue Resi-
dues," Toxicol. Appl. Pharmacol.. Vol. 17 (1970),
pp. 656-668.
3. G. J. Johnstone, D. J. Ecobichon, and 0. Hutzinger,
"The Influence of Pure Polychlorinated Biphenyl
Compounds on Hepatic Function in the Rat,"
Toxicol. Appl. Pharmacol., Vol. 28 (1974), pp.
66-81.
4. 0. Hutzinger, S. Safe, and V. Zitko, "The Chemistry
of PCB's," CRC Press Inc., 1975.
5. D. Sissons and D. Welti, "Structural Identification
of Polychlorinated Biphenyls in Commercial Mix-
tures by Gas-liquid Chromatography, Nuclear
Magnetic Resonance, and Mass Spectrometry," J.
Chromatog.. Vol. 60 (1971), pp. 15-32.
6. R. G. Webb and A. C. McCall, "Identities of Poly-
chlorinated Biphenyl Isomers in Aroclors," J. Assoc.
Offic. Anal Chem., Vol. 55 (1972), pp. 746-752.
7. M. M. Hansell and D. J. Ecobichon, "Effects of
Chemically Pure Chlorobiphenyls on the Morphol-
ogy of Rat Liver," Toxicol. Appl. Pharmacol.,, Vol.
28 (1974), pp. 418-427.
8. S. Fujita, H. Tsuji, K. Kato, S. Saeki, and H.
Tsukamoto, "Effect of Biphenyl Chlorides on Rat
Liver Microsomes," Fukuoka Acta Med., Vol. 62
(1971), pp. 30-34.
9. D. R. Bickers, L. C. Harber, A. Kappas, and A. P.
Alvares, "Polychlorinated Biphenyls: Comparative
Effects of High and Low Chlorine-Containing
Aroclors on Hepatic Mixed Function Oxidase," Res.
Commun. Chem. Pathol. Pharmacol., Vol. 3 (1972),
pp. 505-512.
10. P. R. Chen, H. M. Mehendale, and L. Fishbein,
"Effect of Two Isomeric Tetrachlorobiphenyls on
Rats and Their Hepatic Enzymes," Arch. Environ.
Contam. Toxicol., Vol. 1 (1973), pp. 36-47.
11. J. G. Vos and E. Notenboom-Ram, "Comparative
Toxicity Study of 2,4,5,2',4',5'-hexachlorobiphenyl
65
-------
and a Polychlorinated Biphenyl Mixture in Rab-
bits," Toxicol. Appl. Pharmacol., Vol. 23 (1972),
pp. 563-578.
12. D. J. Ecobichon and A. M. Comeau, "Isomerically
Pure Chlorobiphenyl Congeners and Hepatic Func-
tion in the Rat: Influence of Position and Degree of
Chlorination," Toxicol. Appl. Pharmacol., Vol. 33
(1975), pp. 94-102.
13. J. G. Vos, J. J. T. W. A. Strik, C. W. M. van
Hosteyn, and J. H. Pennings, "Polychlorinated
Biphenyls as Inducers of Hepatic Porphyria in
Japanese Quail With Special Reference to 5-amino
Levulinic Acid Synthetase Activity, Fluorescence,
and Residues in the Liver," Toxicol. Appl.
Pharmacol., Vol. 20 (1971), pp. 232-240.
14. J. A. Goldstein, P. Hickman, and D. L. Jue, "Experi-
mental Hepatic Prophyria Induced by Polychlo-
rinated Biphenyls," Toxicol. Appl. Pharmacol., Vol.
27 (1974), pp. 437-448.
15. J. A. Goldstein, P. Hickman, V. W, Burse, and H.
Bergman, "A Comparative Study of Two Polychlo-
rinated Biphenyl Mixtures (Aroclor 1242 and 1016)
Containing 42% Chlorine on Induction of Hepatic
Porphyria and Drug Metabolizing Enzymes,"
Toxicol. Appl. Pharmacol., Vol. 32 (1975), pp.
461-473.
16. W. Grote, A. Schmoldt, and H. F. Benthe, "Hepatic
Prophyrin Synthesis in Rats After Pretreatment
With Polychlorinated Biphenyls (RGB's)," Acta
Pharmacol. et Toxicol. Vol. 36 (1975), pp. 215-224.
17. J. A. Goldstein, J. D. McKinney, G. W. Lucier, P.
Hickman, H, Bergman, and J. A. Moore, 'Toxicol-
ogy of Hexachlorobiphenyl Isomers and 2,3,7,8-
tetrachlorodibenzofuran in Chicks II. Effects on
Drug Metabolism and Porphyrin Accumulation,"
Toxicol. Appl. Pharmacol., accepted for publica-
tion, 1975.
18. J. H. Koeman, M. C. Ten Noever de Brauw, antfR.
H. de Vos, "Chlorinated Biphenyls in Fish, Mussels
and Birds from the River Rhine and the Netherlands
Coastal Area," Nature (London), Vol. 221 (1969),
pp. 1126-1128.
19. D. L. Grant, W. E. J. Phillips, and D. C. Villeneuve,
"Metabolism of a Polychlorinated Biphenyl (Aro-
clor 1254) Mixture in the Rat," Bull. Environ.
Contam. Toxicol., Vol. 6 (1971), pp. 102-112.
20. S. Bailey and P. J. Bunyan, "Interpretation of
Persistance and Effects of Polychlorinated Bi-
phenyls in Birds," Nature (London), Vol. 236
(1972), pp. 34-36.
21. V. W. Burse, R. D. Kimbrough, E. C. Villanueva, R.
W. Jennings, R. E. Linder, and G. W. Sovocool,
"Polychlorinated Biphenyls, Storage Distribution,
Excretion and Recovery: Liver Morphology After
Prolonged Dietary Ingestion," Arch. Environ.
Health, Vol. 29 (1974), pp. 301-307.
22. A. S. De Freitas and R, J. Norstrom, "Turnover and
Metabolism of Polychlorinated Biphenyls in Rela-
tion to Their Chemical Structure and the Movement
of Lipids in the Pigeon," Can. J. Physiol. Phar-
macol., Vol. 52 (1974), pp. 1080-1094.
23. 0. Hutzinger, D. M. Nash, S. Safe, A. W, W. De
Freitas, R. J. Norstrom, D, J. Wildfish, and V.
Zitko, "Polychlorinated Biphenyls: Metabolic
Behavior of Pure Isomers in Pigeons, Rats, and
Brook Trout," Science, Vol. 175 (1972), pp.
312-314.
24. A. M. Gardner, J. T. Chen, J. A. G, Roach, and E. P.
Ragelis, "Polychlorinated Biphenyls: Hydroxylated
Urinary Metabolites of 2,5,2',5'-tetrachlorobiphenyl
Identified in Rabbits," Biochem. Biophys. Res.
Commun., Vol. 55 (1973), pp. 1377-1384.
25. S. Safe, 0. Hutzinget, and D. J. Ecobichon, "Identi-
fication of 4-chloro-4'-hydroxy biphenyl and
4,4'-di-chloro-3-hydroxybiphenyl as Metabolites of
4-chloro- and 4,4'-dichlorobiphenyl Fed to Rats,"
Experientia, Vol. 30 (1974), pp. 720-721.
26. S, Jensen and G. Sundstrom, "Metabolic Hydroxyla-
tion of a Chlorobiphenyl Containing Only Isolated
Unsubstituted Positions - 2,2',4,4',5,5'-hexachloro-
biphenyl," Nature (London), Vol. 251 (1974), pp.
219-220.
27. W. Greb, W. Klein, F. Coulston, L. Golberg, and F.
Korte, "Beitrage zur Okologischen Chemie
LXXXIII. In Vitro Metabolism of Polychlorinated
Biphenyls- 14 C,"Bu/l. Environ. Contam. Toxicol. ,
Vol. 13 (1975), pp. 424-432.
28. J. W. Daly, D. M. Jerina, and B. Witkop, "Arene
Oxides and the NIH Shift: The Metabolism
Toxicity and Carcinogenicity of Aromatic Com-
pounds," Experientia, Vol. 28 (1972), pp.
1129-1149.
DISCUSSION
DR. JOHN V. MOORE (National Institute of Environ-
mental Health Sciences, Research Triangle Park,
North Carolina): Have you done any investigatory
work to see what the name of the impurity might
be?
DR. ECOBICHON: Not that I know of. I don't even
belive Eastman Kodak is aware of it.
66
-------
TOXICOLOGY OF SELECTED SYMMETRICAL HEXACHLOROBIPHENYL
ISOMERS: I. BIOLOGICAL RESPONSES IN CHICKS AND MICE
Marco Biocca, M.D.,* J. A. Moore, D.V.M.,t B. IM. Gupta, B.V.Sc., Ph.D.,t and J. 0. McKinney, Ph.D.t
Abstract
One-day-old cockerels were fed: (I) 3,1030,100,
and 300 ppm of 3,4,5$,A', 5'-hexachlorobiphenyl
(HCB); (II) 400 ppm of 2,3,42',3',4'-HCB; (III) 400
ppm of 2,4,5,2',4',5'-HCB; (IV) 400 ppm of
2,3,6,2',3',6'-HCB; and (V) 400 ppm of
2,4,62',4',6'-HCB. Surviving chicks were sacrificed at 21
days. Male mice were fed 10, 30, 100 and 300 ppm of
three of the above isomers (I, III, V), and survivors were
sacrificed at 28 days. HCB's levels in adipose tissue and
liver were determined. There were variations among the
isomers as to dose and pathologic effects. Isomer (I)
showed the greatest effect of those studied on mortality,
body weight gain, liver, thymus, and spleen; it also at-
tained the highest tissue concentration. It was the only
isomer which produced porphyrin accumulation; and, in
the chicks, produced hydropericardium, ascites, and
edema. The decreasing order of overall toxicity was I»
V > II, III, IV. A general similarity of response was
observed in both chicks and mice.
INTRODUCTION
A number of publications have described various
toxicologic effects of commercial polychlorinated bi-
phenyls. The presence of toxic impurities, variable chlo-
rine content, or chlorine substitution patterns make
interpretation and comparison of the results of these
studies quite difficult.
By comparison, little work has been done on
assessing the general toxic effects of single polychlorin-
ated biphenyls. The objective of this report is to describe
the first results obtained from a comparative, systematic
study of the general biological effects of some hexa-
chlorobiphenyl (HCB) isomers in chicks and mice.
The HCB's were selected because of (1) their pre-
dominant presence in higher chlorinated formulations
(ref. 1); (2) their relative stability in the environment
(particularly their persistence in human tissue) (ref. 1);
and (3) their strong inductive effect on several biological
parameters (ref. 2). The specific isomers studied were
selected as biphenyl models representing different
"Institute di Igiene, g. Sanarelli, Universita di Roma, Citta
Univprsitaraia, Rome, Italy.
t J. A. Moore, B. N. Gupta, and J. D. McKinney are with
the Environmental Biology and Chemistry Branch of the Na-
tional Institute of Environmental Health Sciences, Research Tri-
angle Park, North Carolina.
physicochemical properties. Chicks were used in this
experiment because of their high sensitivity to poly-
chlorinated hydrocarbons; mice were selected to confirm
results in a mammalian species.
MATERIALS AND METHODS
The experimental protocol is summarized in table 1.
The table illustrates the chemicals and dose levels used,
the number of animals per dose level, and the duration
of the experiment. The HCB's were mixed in a chick
edema bioassay diet or a standard powdered mouse diet.
The animals were housed in temperature- and humidity-
controlled rooms. The chicks were kept in wire-floored
cages, the mice in separate plastic cages. Food and water
were provided ad libitum for the entire experimental
period. The animals were observed daily; body weight
was recorded twice a week; food consumption was
measured once a week for the chicks and three times a
week for the mice. Control groups were observed under
identical experimental conditions.
Complete necropsies were performed on dead or
moribund animals and on the surviving animals at the
end of the experimental period. Blood samples were
obtained at this time and analyzed for packed cell
volume, total serum protein, and protein fractionation.
Liver, spleen, and heart weights were recorded for the
chicks; in mice, kidneys, right testicle, and adrenals were
also weighed. All organs and tissues were examined
under UV light for the presence of red fluorescence as an
indication of porphyrin accumulation. After fixation,
tissues were prepared for histopathologic examination
using standard methods.
All animals were assigned to a given dose according
to a table of random numbers. Diet, adipose tissue, and
liver were collected for HCB's residue analysis.
RESULTS
The complete results of this study are described in a
series of -papers either in press or in preparation (refs.
3-6). This presentation is a summary comparison of
major biological responses observed in chicks and mice.
Table 2, which summarizes the chick effects, shows that
3,4,5,3',4',5'-HCB is the most toxic isomer studied, caus-
ing death in all the chicks, even at the lowest dose used.
You will note that this dose* is less than 1/100 of the diet
concentrations of the other HCB's. Only one out of ten
67
-------
chicks died in the 2,3,6,2',3',6'-HCB group; no animals
of the other groups died during the experiment. Reduc-
tion in body weight gain was observed in all treatment
groups.
At the dose levels studied, significant differences in
liver weights and histopathologic changes were observed
with all HCB isomers. The most toxic was
3,4,5,3',4',5'-HCB, even at the lowest dose. It was the
only isomer in which UV fluorescence (porphyrin
accumulation) was observed. This finding was quite
pronounced, especially in the lining layer of the gizzard,
liver, and bones. The slight pathologic effect of the liver
observed at 10 ppm is probably due to the very early
death of the chicks. The thymus of these chicks was
extremely involuted while only slight effect was caused
by the other isomers.
Table 3 summarizes the major pathological changes
observed: Marked edema of subcutaneous tissue, de-
noted by gelatinous appearance of subcutaneous fat;
marked depletion of lymphocytes in the spleen; diarrhea
and soiling of the cloaca! area; turbid ascitic fluid;
hydropericardium; and loss of visceral fat were findings
seen only with the 3,4,5,3',4',5'-HCB. Fatty metamor-
phosis and single-cell or focal necrosis of the liver, were
present, albeit to a variable extent in all animals. In
addition, characteristic large black spots, 1 to 5 mm in
diameter, were observed under the capsule and on cut
surfaces of the liver of birds which received
2,4,6,2',4',6'-HCB. This change was caused by marked
dilatation of sinusoids with a result of accumulation of
blood. In some cases, the epicardium of chicks fed
2,3,4,2',3',4'-HCB was markedly edematous.
Table 4 summarizes the effects in mice. Again,
3,4,5,3',4',5'-HCB was the most toxic, causing one death
at 30 ppm and decreasing body weight gain at the
10-ppm level. Although there were no deaths at 10-ppm
level in this experiment, which lasted to the 28th day, in
one subsequent experiment, mice fed a diet with 10 ppm
died an average of 39.4 days (range 36-47). Only one
mouse fed the highest dose (300 ppm) of
2,4,5,2',4',5'-HCB died before the end of the experimen-
tal period; in contrast, all mice fed 2,4,6,2',4',6'-HCB at
the same level died.
The body Weight gain of the mice fed 100 ppm of
2,4,5,2',4',5'-HCB or 2,4,6,2',4',6'-HCB were not signifi-
cantly reduced. The dose-related increase in liver weight
was caused by all three isomers, with the greatest effect
being in the 3,4,5,3',4',5'-HCB group. The absence of
liver pathology in the mice fed with 300 ppm
3,4,5,3',4',5'-HCB is, again, considered to be related to
the early time of death. Only 3,4,5,3',4',5'-HCB caused
porphyrin accumulation and a dramatic atrophy of the
lymphatic organs.
The major pathological changes observed in the
mice are summarized in table 5. Gelatinous appearance
of subcutaneous fat, presence of blood in the gastro-
intestinal tract, and hemmorrhage in the retrobulbar area
of the eye were characteristic of the mice that died due
to 3,4,5,3',4',5'-HCB toxicity. Accentuation of the
hepatic lobules, swelling and hyalim'zation of the hepato-
cytes, fatty metamorphosis, and single or focal necrosis
were not related to a particular chemical since these
changes were observed in all HCB groups to various
degrees. Cardiomyopathy and passive congestion of the
lung were caused only by 2,4,6,2',4',6'-HCB at the
300-ppm dose.
Retention indices of the mixed liquid phase used for
gas chromatography may serve as an index of lipophilici-
ty (table 6). Except for 2,4,6,2',4',6'-HCB, decreasing
indices for this isomeric series correlated exactly with
decreasing adipose tissue accumulation in chicks. The
highest values were shown by 3,4,5,3',4',5'-HCB and
2,3,6,2',3',6'-HCB the lowest. A similar trend in tissue
accumulation and retention indices is evident in mice
(table 7), but not at all dose levels. A greater concentra-
tion of 3,4,5,3',4',5'-HCB was observed in all cases,
particularly in the liver.
CONCLUSIONS
There are definite differences in the toxicity of the
HCB isomers tested. Comparing toxicity using such bio-
logical parameters as mortality, body weight gain, liver
effects, porphyrin accumulation, involution of the
lymphatic organs, and fluid accumulation in chicks, the
decreasing order of overall toxicity would be
3,4,5,3',4',5'-HCE? » 2,4,6,2',4',6'-HCB >
2,4,5,2',4',5'-, 2,3,4,2',3',4'-, 2,3,6,2',3',6',-HCB.
The differences in pathologic effects observed dur-
ing these experiments, were quantitative and, to some
degree, qualitative. It is important to note that the
nature of the toxicity of 3,4,5,3',4',5'-HCB mimics the
effects caused by the clibenzofurans.
Although certain toxicologic characteristics differ-
entiate the biological responses in each species tested,
the major toxicopathologic effects were common to
both chicks and mice.
REFERENCES
1. S. Jensen and G. Sundstrom, "Structures and Levels
of Most Chlorobiphenyls in Two Technical PCB
68
-------
Products and in Human Adipose Tissue," Ambio,
Vol. 3 (19741, pp. 70-75.
2. D. J. Ecobichon and A. M. Comeau, "Isomerically
Pure Chlorobiphenyl Congeners and Hepatic Func-
tion in the Rat: Influence of Position and Degree of
Chlorination," Toxicol. Appl. Pharmacol.. Vol. 33
(1975), pp. 94-105.
3. J. D. McKinney, K. Chae, B. N. Gupta, J. A. Moore,
and J. A. Goldstein, "Toxicology of Hexachlorobi-
phenyl Isomers and 2,3,7,8-Tetrachlorodibenzo-
furan in Chicks. I. Relationship of Chemical Param-
eters," Toxicol. Appl. Pharmacol., 1975, in press.
4. J. A. Goldstein, J. D. McKinney, G. W. Lucier, P.
Hickman, H. Bergman, and J. A. Moore, "Toxicolo-
gy of Hexachlorobiphenyl Isomers and 2,3,7,8-Tet-
rachlorodibenzofuran in Chicks. II. Effects on Drug
Metabolism and Porphyrin Accumulation," Toxicol.
Appl. Pharmacol., 1975, in press..
5. J. D. McKinney, J. R. Hass, and K. Chae, "Metabo-
lism of Pure Hexachlorobiphenyl Isomers in Chicks.
Dechlorination, Isomerization, Hydroxylation and
Dibenzofuran Formation," 1975, manuscript in
preparation.
6. M. Biocca, K. Chae, B. Gupta, J. McKinney and J.
Moore, manuscript in preparation.
Table 1. Protocol for hexachlorobiphenyl isomers
toxicity experiments in mice and chicks3
Chemical
Dose level
(ppm)
Mice Chicks
No. of animals/
dose level
MiceChicks
Experimental
period (day)
MiceChicks
( >99 percent purity)
2,3,4,2',31,4'-HCB
2,4,5,2',4'J5'-HCB
2,3,6,2',3',61-HCB
2,456,21,4',6'-HCB
3
10
30
100
300
10
30
100
300
10
30
100
300
3
10
30
100
300
400
400
400
400
10
10
10
10
10
28
28
28
21
21
21
21
21
Five-week old C57BL/6 male mice; 1-day-old white leghorn cockerels.
69
-------
Table 2. Summary of the biological effects ol
hexachlorobiphenyl isomers in chicks
Chemical
3,4,5,3', 4'
2, 3, 4,2', 3'
2,4,5,2', 4'
2, 3, 6, 2', 3'
2, 4, 6, 2', 4'
,5'-HCB
,4'-HCB
,5'-HCB
>6'-HCB
,6'-HCB
Dose
level
(ppm)
3
10
400
400
400
400
Body weight Porphyrin
gain Liver Accumula- Thymus
Mortality (% of control) effect tion effect
10/10
10/10
0/8
0/10
1/10
0/10
: +t+ +++ +++
68 ++ - ' +
66 ++ - +
80 ++ - +
83 +++ - +
Table 3, Summary of major pathological changes in chicks given different
hexachlorobiphenyl isomers for 21 days
Dose
level
Chemical (ppm)
S.I.S.S'.A'.S'-HCB 3
2,3,4,2',3',4'-HCB 400
2,4,5,2',4',5'-HCB 400
2,3,6,2',3',6'-HCB 400
2,4,6,2',4I,6'-HCB 400
Liver
Marked; fatty
metamorphosis,
focal necrosis.
Moderate;
•hyalinization,
single-cell
necrosis.
Moderate;
single-cell
necrosis.
Moderate;
fatty metamor-
phosis, focal
necrosis, giant
cell formation.
Marked; fatty
metamorphosis,
focal necrosis,
giant cell forma-
tion, marked focal
dilatation of
sinusoids.
Thymus
Marked;
involution.
Slight;
Involution.
Slight;
involution.
Slight;
involution.
Slight;
involution.
Spleen
Marked;
depletion of
lymphocytes.
NSa
NSa
NSa
NSa
Fluid
Accumulation
Subcutaneous edema,
ascites, hydroperi-
cardium.
Epicardial edema.
NSa
NSa
NSa
NS = not significant.
70
-------
Table 4. Summary of the biological effects of
hexachlorobiphenyl isomers in mice
Chemical
3,4,5,3',4',5'-HCB
2J4,5,2I,4',51-HCB
2)4,6,2',4',6'-rlCB
Dose
level
( pprn)
10
100
300
100
300
100
300
Mortality
0/5
3/5
5/5
0/5
1/5
0/5
5/5
Body weight
gain
(% of control)
12
-
-
91
58
85
-
Porphyrin
Liver Accumula-
effect tion
++ +
+++ +++
- -
+
++
+
++
Thymus
effect
++
+++
+++
-
i
_
++
Table 5. Summary of major pathological changes in mice given different
hexachlorobiphenyl isomers for 28 days
Chemical
3,4,5,3',4',5'-HCB
2,4,5,2',4',5'-HCB
2,4,6,2',4',6'THCB
Dose level
(ppm)
30
300
300
Liver
Marked; fatty
metamorphosis,
single-cell
necrosis.
Slight;
swelling of
hepatocytes.
Marked; fatty
metamorphosis,
single-cell
necrosis.
Thymus
Marked;
involution.
Slight;
involution.
Marked;
involution.
Spleen
Moderate;
depletion of
lymphocytes.
NSa
Moderate;
depletion of
lymphocytes.
Heart
NSa
NSa
Moderate;
cardiomyopathy.
NS = not significant.
71
-------
Table 6. Gas chromatographic retention indices and
tissue hexachlorobiphenyl levels in chicks
Chemical
3,
2,
2,
2,
2,
4,
3,
4,
3,
4,
5
4
5
6
6
,3'
,2'
,2'
,2'
,2'
,4'
,3'
,4'
,3'
,4'
,5'-HCB
,4'-HCB
,5'-HCB
,6'-HCB
,6'-HCB
Dose level
(ppin)
100
300
400
400
400
400
GC retention
index value
2,
2,
2,
2,
2,
820
678
542
478
346
Concentration (ppm)
Adipose T.
1,
4,
3,
3,
2,
4,
210
912
998
921
893
172
Liver
-
44
59
9
24
Table 7. Gas chromatographic retention indices and
tissue hexachlorobiphenyl levels in mice
Chemical
3,4,3,3', 4', B'-HCB
2,4,5,2',4',51-HCB
2,4,6,2',4',6'-HCB
Dose level
(ppm)
10
30
100
300
10
30
100
300
10
30
100
300
GC retention Concentration
index value Adipose T.
508
1 ,383
2820
2,278
6,912
296
416
2542
1 ,864
3,923
99
582
2346
1,402
4,329
(ppm)
Liver
95
498
887
1,344
7
30
83
637
6
15
122
1,022
72
-------
TOXICOLOGY OF SELECTED SYMMETRICAL HEXACHLOROBIPHENYL ISOMERS:
CORRELATING BIOLOGICAL EFFECTS WITH CHEMICAL STRUCTURE
Abstract
James D. McKinney, Ph.D.*
TOXICOLOGICALLY SIGNIFICANT PROPERTIES
The symmetrical hexachlorobiphenyls (HCB's) rep-
resent model PCB's with high and constant chlorine con-
tent permitting unequivocal study of a given substitution
pattern. These isomers show separate and distinct bio-
logical responses which can be related to chemical struc-
ture via effects of varying chlorine substitution on com-
pound lipophilicity and metabolism. Compound purity
must also be assured. Relative molecular polarizability
can be correlated with lipophilicity and biological activi-
ty and is measurable by chromatographic and spectro-
scopic techniques. These parameters were highest in
HCB's with planar symmetry and 4,4'-substitution. The
rates of metabolism of these isomers are considered of
lesser importance than the potentially highly toxic na-
ture of some of the intermediary and terminal metabo-
lites.
INTRODUCTION
A previous paper (ref. 1) has shown the importance
of the degree of chlorination of PCB's in terms of their
distribution and excretion in the rat. Of particular con-
cern is the implication that not more than 20 percent of
the hexachlorobiphenyl isomer studied would ever be
excreted. Therefore, hexachlorobiphenyls may represent
PCB's with both high chlorine content and biological
half life. Our studies with symmetrical hexachlorobiphe-
nyl isomers (HCB's) sought to determine the varying bio-
logical effects of HCB's as a function of their varying
substitution patterns (figure 1). Two of the isomers
studied are found in about 3 to 4 percent (area percent
by flame ionization gas chromatography) in Aroclors
1254 and 1260. Several major components of these same
Aroclors contain various combinations of the substitu-
tion patterns studied. Since the effects of chlorine sub-
stitution in biphenyls on spectral and chromatographic
properties may be approximately predicted (refs. 2,3)
using additive parameters obtained from chlorobenzenes,
it may be possible to predict the biological behavior of
the various combinations through study of the appro-
priate individual symmetrical isomers.
*J. D. McKinney is with the Environmental Biology and
Chemistry Branch of the National Institute of Environmental
Health Sciences, Research Triangle Park, North Carolina.
As previously described (ref. 4), our studies with
both chickens and mice have shown separate and distinct
biological effects at submaximal dosss for the different
isomers even though all of these isomers might be con-
sidered potent (relative to lower chlorinated isomers). In
explaining these differences, we feel that the three major
considerations are compound purity, lipophilicity, and
metabolism. Intestinal adsorption was not considered
since earlier work (ref. 5) failed to show appreciable
differences for various PCB's.
Compound purity can be very important since both
the individual synthetic isomers (ref. 6) and the Aroclor
mixtures are known (ref. 7) to be contaminated with
small amounts of chlorinated dibenzofurans which, in
some species at least, are orders of magnitude more toxic
than the PCB's. Since separate and distinct differences in
the biological effects of 2,3,7,8-tetrachlorodibenzofuran
and the HCB's were found in our work (refs. 8,9), one
may be in a position to assess the involvement of
dibenzofurans as contaminants and, as will be described
later, as potential metabolites.
Relatively little work (ref. 10) has been done associ-
ating the effects of varying PCB structure with varying
degrees of tissue accumulation. Our work (ref. 8) does
appear to show a trend in adipose tissue accumulation of
HCB's which correlated with molecular polarizability as
measured by chromatographic and spectroscopic tech-
niques. The HCB gas-chromatographic (GC) retention in-
dices (increasing) generally correlated with their overall
biological response and were highest in isomers with
3,4-substitution. The amount of HCB in the adipose
tissue does not determine activity, but its distribution in
this tissue and activity in the liver may both reflect
lipophilicity. Since the GC retention index correlation is
consistent with a number and variety of GC columns, it
is possible that it may have some value in predicting
lipophilicity. The lipophilicity in turn relates to biologi-
cal activity through effective tissue concentration of a
given HCB. The- differences in adipose tissue accumula-
tion do not appear to be a function of metabolic remov-
al since the least accumulated isomer (2,3,6,2',3',6') was
one of the least metabolized (ref. 11).
Considerations of metabolism must take into
account the differences in rates of degradation and ex-
cretion as well as the nature of intermediary and termin-
al metabolites, higher degradation rates (shorter biologi-
73
-------
cal half-life) are generally associated with those PCB's
having vicinal (two-adjacent carbon atoms) positions un-
occupied. These PCB's are also the only ones for which
there is clear evidence to support arene oxide inter-
mediates (refs. 1,12). The toxic properties of these
PCB's may have more to do with the reactive nature of
such arene oxide intermediates, with the main quanti-
tative difference being associated with varying degrees of
lipophilicity.
The more highly chlorinated PCB's such as the
RGB's would show similar differences due to lipophil-
icity, but would be expected to be metabolized more
slowly and by other mechanisms as well since vicinal
unoccupied positions occur more infrequently. The
probable metabolic pathways in chicks (based on metab-
olities identified in excreta) for the 2,4,5,2',4',5'-,
2,4,6,2',4',6'- and 3,4,5,3',4',5'-HCB's suggest that sever-
al reaction types, including isomerization, reductive de-
chlorination and oxidation with and without the loss of
chlorine, are operating. The detailed methodology for
identifying these metabolites will be described in a sep-
arate report (ref. 11). Microbial metabolism in the gut
cannot be ruled out.
The metabolites of 2,4,5,2',4',5'-HCB include the
meta-hydroxy compound, which appears to undergo fur-
ther oxidation to the para-quinol, suggesting that a
direct insertion hydroxylation reaction may be operating
as reported (ref. 12) for further oxidation of 4'-chloro-
4-biphenylol to 4'-chloro-3,4-biphenyldiol. However,
arene oxide intermediate formation may be possible at
1,2-carbons with one unoccupied and the other occupied
with either a phenyl or chlorine substituent probably
resulting in concomitant chlorine (or phenyl) migration
or dechlorination. Dechlorination does occur since a
trace of pentachlorobiphenyl and pentachlorotrihy-
droxybiphenyl and pentachlorophenylbenzoquinone
metabolites are found. These highly oxidized products
including the p-quinone, which accompanies the
p-quinol, are more chemically and perhaps biochemically
reactive. Such products could be more toxic as a result
of their increased reactivity unless they are rapidly ex-
creted. The quinone form may not be rapidly excreted
since it cannot undergo conjugation.
The metabolites identified in the excreta of chick-
ens fed 2,4,6,2',4',6'-HCB contaminated food include
2,4,6,2',3',4'-HCB and a trace of 2,4,6,2',3'-PCB, which
are accompanied by two compounds whose low-resolu-
tion mass spectral and chromatographic properties
suggested hexachlorodibenzofuran and pentachlorodi-
benzcfuran structures. High-resolution mass spectral
analysis of the suspected hexachlorodibenzofuran
metabolite showed that its molecular formula was
C13H6CI6 and, therefore, was a neihylhexachlorobi-
phenyl or the mass equivalent chloromethylpentachloro-
biphenyl. Methyl ethers and* esters are conceivable
metabolites of PCB's, taut this type of metabolite is un-
expected and suggests a direct methylation (or chloro-
methylation) of an aromatic ring in the biphenyl mole-
cule.
High-resolution mass spectral analysis of the sus-
pected pentachlorodibenzofuran is in progress. However,
preliminary low-resolution gas chromatography-mass
spectral data obtained from perchlorination of the
metabolite mixture indicated that some octachlorodi-
benzofuran was present. In the absence of the high-
resolution data, it is conceivable that the suspected pen-
tachlorodibenzofuran is the source of the octachlorodi-
benzofuran.
Data obtained from spiking of control chick feces
with the 2,4,6,2',4',6'-HCB and performing the same
extraction and cleanup procedure used for the chick
metabolites cast doubt on the authenticity of the penta-
chlorobiphenyl metabolite and on an additional metabo-
lite corresponding in molecular formula (by high-resolu-
tion mass spectral analysis) to C12H4Cl4O2 found in
liver tissue and later in the excreta of the chicks fed the
2,4,6,2',4',6'-HCB.
It is clear from the structures of some of these
metabolites that chlorine removal and migration have
occurred. Therefore, these products may be derived
from enzymatic one electron reduction of this system
followed by loss of chloride ion to generate a reactive
radical which can react directly with nucleophilic con-
stituents or undergo a second electron reduction to an
anion which can react directly with electrophilic constit-
uents. Both electrophilic and nucleophilic radicals of
hydrogen (dechlorination), chlorine (isomerization), and
oxygen (oxidation) are among the possible recombinants
which could account for the metabolites found. The
methylhexachlorobipheny! could also be the result of
interaction with an electrophilic methyl donor. Perhaps
of equal or greater toxic.'ological significance would be
the nature of nonexcretable metabolites derived from
covalent bonding of these reactive radicals.
The propensity to lose chloride ion (ref. 13) stems
from the favorable stereoelectronic properties associated
with a high degree of ortho substitution. The possibility
that any oxygenated products including dibenzofurans
are the result of direct suoeroxide anion displacement of
chlorine cannot be ruled out. Recent work (ref. 14) has
shown that chlorine displacement by superoxide can
take place in the mass spectrometer under negative
chemical ionization conditions. An analogy to this and
possibly an environmental source of dibenzofurans from
PCB's would be photonucleophilic displacement of
chlorine by water (ref. 15).
74
-------
In contrast, the 2,3,6,2',3',6'-HCB was metabolized
to a trace amount of a monohydroxy metabolite, but no
other PCB's or other oxygenated products were found.
Therefore, four ortho chlorines alone are not enough; it
may be necessary to have high lipophilicity (4,4'-substi-
tution) as well as vicinal unoccupied positions available
fot appreciable metabolism.
No metabolites were detected in the excreta of
chickens fed food contaminated with the 3,4,5,3',4',5'-
HCB. However, this isomer has separate and distinct bio-
logical effects indicative of a chlorinated dibenzofuran.
Since this isomer has a high lipophilicity and accumula-
tion in tissue, its slow metabolism to an elusive, but
potentially highly toxic, dibenzofuran may be signifi-
cant. Enzymatic oxidation at any one of the equivalent
unoccupied ortho positions could lead via rearrangement
to a "transannular epoxide" intermediate which would
undergo a rather facile oxidation to the symmetrical
2,3,4,6,7,8-hexachlorodibenzofuran.
Examination of chicken tissue and mouse excreta
and tissue for metabolites is in progress. Preliminary
work with tissue from 2,4,5,2', 4',5'- and 2,4,6,2',4',6'-
HCB treated chicks has confirmed the presence of tissue
metabolites. Metabolites found in tissue are also found
in excreta, but not all the metabolites found in excreta
are in tissue. At least one metabolite found in the liver
and adipose tissue of the 2,4,5,2', 4',5'-HCB and in the
liver and excreta of the 2,4,6,2',4',6'-HCB treated chicks
was of particular interest, since its mass spectral proper-
ties (low- and high-resolution measurements) corre-
sponded to a tetrachlorodibenzodioxin (TCDD), a
hydroxytetrachlorodibenzofuran, a tetrachloro-
phenylbenzoquinone or a methoxytetrachlorobiphenyl.
The exact structure assignment cannot be made at this
time, but failure to methylate this metabolite under two
sets of reaction conditions would cast doubt on the
hydroxytetrachlorodibenzofuran possibility. As
mentioned earlier, this compound may not be a metabo-
lite, but it remains a potential problem as an artifact of
the extraction and cleanup procedure for certain PCB's,
which could interfere in analysis for TCDD in environ-
mental samples.
SUMMARY
High compound lipophilicity is clearly a contribut-
ing factor to HCB toxicity in both chickens and mice.
The potentially highly toxic chlorinated dibenzofurans
are a problem since they are known to be contaminants
of certain Aroclor mixtures and at least one synthetic
isomer and are potential environmental transformation
products including metabolites of certain PCB's. The
exact chlorine substitution patterns found in these com-
pounds may be of considerable importance toxicologi-
cally (ref. 16), as has been the case for the structurally
similar chlorinated dibenzodioxins. The requisite sub-
stitution patterns for dibenzofuran formation found in
components of Aroclors most likely would include a
combination of those providing high chlorine content, in
particular ortho chlorine, high lipophilicity and tissue
accumulation, and unavailability of unoccupied vicinal
positions. Other PCB's having all ortho positions occu-
pied might also favor ortho oxygenation. Other PCB's
may be metabolized to a high degree of ortho-substitu-
ents, one of which is hydroxy and another chlorine,
which through further metabolism could lead to di-
benzofurans, again provided that other requirements are
met. Further study is needed with the appropriate puri-
fied isomers to clearly establish the formation of di-
benzofuran metabolites and determine if microsomal en-
zymes are responsible.
REFERENCES
1. H. B. Matthews, "PCB Chlorination vs. PCS Distri-
bution and Excretion," National Conference on
Polychlorinated Biphenyls, Chicago, Illinois,
November, 1975.
2. N. K. Wilson, "Carbon-13 Nuclear Magnetic Reso-
nance. ' 3C-Shieldings and Spin-lattice Relaxation
- Times in PCBs," J. Amer. Chem. Soc., Vol. 97, No.
13 (1975), pp. 3573-3579.
3. P. W. Albro and L. Fishbein, "Quantitative and
Qualitative Analysis of PCB's by Gas-Liquid
Chromatography and Flame lonization Detector. I.
One to Three Chlorine Atoms," J. Chromatography,
Vol. 69 (1972), pp. 273-283.
4. M. Biocca, "Toxicology of Selected Symmetrical
HCBs. Biological Responses in Chickens and Mice,"
National Conference on Polychlorinated Biphenyls,
Chicago, Illinois, November, 1975.
5. P. W. Albro and L. Fishbein, "Intestinal Absorption
of PCBs in Rats," Bull. Environ. Contain. Toxicol.,
Vol. 8, No. 1 (1972), pp. 26-31.
6. M. Moron, G. Sundstrom, and C. L. Wachtmeister,
"2,3,7,8-Tetrachlorodibenzofuran, a Critical By-
product in the Synthesis of 2,2',4,4',5,5'-HCB by
Oilman Reaction," Acta Chem. Scand., Vol. 27, No.
8 (1973), pp. 3121-3122.
7. G. W. Bowes, M. J. Mulvihill, B. R. T. Simoneit, A.
L. Burlingame, and R. W. Risebrough, "Identifica-
tion of Chlorinated Dibenzofurans in American
Polychlorinated Biphenyls," Nature, Vol. 256
(1975), pp. 305-307.
75
-------
8. J. D. McKinney, K. Chae, B. N. Gupta, J. A. Moore,
and J. A. Goldstein,. "Toxicology of Hexachlorobi-
phenyl Isomers and 2,3,7,8-Tetrachlorodibenzo-
furan in Chicks. I. Relationship of Chemical Param-
eters," Toxicol. Appl. Pharmacol. (1975), in press.
9. J. A. Goldstein, J. D. McKinney, G. W. Lucier, P.
Hickman, H. Bergman, and J. A. Moore, "Toxicolo-
gy of Hexachlorobiphenyl Isomers and 2,3,7,8-
Tetrachlorodibenzofuran in Chicks. II. Effects on
Drug Metabolism and Porphyrin Accumulation,"
Toxicol. Appl. Pharmacol. (1975), in press.
10. B. Bush, C. F. Tumasonis, and F. D. Baker, "Toxici-
ty and Persistence of PCB Homologs and Isomers in
the Avian System," Arch. Environ. Contam. and
Toxicol., Vol. 2, No. 3 (1974), pp. 195-212.
11. J. D. McKinney, J. R. Hass, and K. Chae, "Metabo-
lism of Pure Hexachlorobiphenyl Isomers in Chicks"
(1976), manuscript in preparation.
12. S. Safe, 0. Hutzinger, and D. Jones, "The Mecha-
nism of Chlorobiphenyl Metabolism," J. Agric.
FoodChem., Vol. 23, No. 5 (1975), pp. 851-853.
13. S. Safe and 0. Hutzinger, "Polychlorinated Bi-
phenyls: Photolysis of 2,4,6,2',4',6'-Hexachlorobi-
phenyl," Nature, Vol. 232 (1971), pp. 641-642.
14. P. F. Levonowick, H. P. Tannenbaum, and R. C.
Dougherty, "Negative Chemical lonization as a
Model for Reactions in Solution: New Nucleophilic
Reactions of Superoxide," J. C. S. Chem. Comms.
(1975), pp. 597-598.
15. D. G. Crosby and K. W. Moilanen, "Photodecompo-
s it ion of Chlorinated Biphenyls and Dibenzo-
furans," Bull. Environ. Contam. Toxicol., Vol. 10,
No. 6 (1973), pp. 372-377.
16. J. A. Moore, "Toxicity of 2,3,7,8-Tetrachlorodiben-
zofuran. Preliminary Results," National Conference
on Polychlorinated Biphenyls, Chicago, Illinois,
November, 1975.
DISCUSSION
DR. STEVEN SAFE (Department of Chemistry, Univer-
sity of Guelph, Ontario, Canada): You mentioned
the'requirement for 1,2-carbons unsubstituted for
arene oxide formation and hydroxylation. We have
observed both chlorine migration (NIH shift) and
dechlorination. So you do not need unsubstituted
positions but you cart have a shift.
DR. McKINNEY: I do not believe I said it that way. I
believe 1 said that the only clear evidence that I have
seen for oxides has been in cases where adjacent
carbon atoms were present.
DR. SAFE: With migration of the chlorine?
DR. McKINNEY: Yes, that is an unusual situation.
2,4,6,2'^'
Figure 1. Hexachlorobiphenyl structures.
76
-------
TOXICITY OF 2,3,7,8-TETRACHLORODIBENZOFURAN-
PRELIMINARY RESULTS
John A. Moore, D.V.M.,* B. N. Gupta, B.V.Sc., Ph.D.,*
and J.G. Vos, D.V.M., Ph.D.t
Abstract
There are at present no reports on the toxicity of
pure chlorinated dibenzofurans. The paper below
describes ongoing research on 2,3,7,8-tetrachlorodi-
benzofuran (TCDF), the most toxic isomer of the group.
The work is based on the premise that due to the similar
structures of chlorinated dibenzofurans and chlorinated
dibenzodioxins, the nature of response and the level of
exposure needed to induce that response may be similar
for the two compounds.
Although no conclusions can be drawn yet, the
following observations have been made: (1) Heghorn
chicks given 5 \ig/kg TCDF showed fluid accumulation,
enlarged heart, reduced size of thymus and spleen, then
death; (2) Hartley guinea pigs showed weight loss,
depression, and diminution of thymus and spleen prior
to death; (3) Rats and mice had only mild toxicological
reactions to a 6,000 pg/kg dose of TCDF.
Trends at this point indicate that TCDF is highly
toxic at low doses to chicks and guinea pigs, as is tet-
rachlorodibenzodioxin ITCDD). For rats and mice, how-
ever, the correlation is not strong. Before accurate assess-
ments can be made of the health significance of chlorin-
ated dibenzofurans, the specific structures of their
isomers must be elucidated.
The toxicological significance of exposure to chlo-
rinated dibenzofurans is an issue of great interest.
Interest has been generated by the identification of
chlorinated dibenzofurans as impurities of two European
RGB's (refs. 1,2,3); American RGB's (ref. 4); the presump-
tive findings of dibenzofurans in the urine of rats fed
Aroclor 1254 (ref. 5) as well as the identification of
chlorinated dibenzofurans in PCB-contaminated rice oil
(ref. 6). There are no reports which describe the toxi-
cologic effects of pure chlorinated dibenzofurans.
*Dr. Moore is Chief of the Environmental Biology and
Chemistry Branch of the National Institute of Environmental
Health Sciences, Research Triangle Park, North Carolina. Dr. B.
N. Gupta is also with the Environmental Biology and Chemistry
Branch of NIEHS.
tDr. Vos is with the Department of Pathology, National
Institute of Public Health, Biltholven, The Netherlands.
ttKindly supplied by Dr. A. Kende, University of Roches-
ter, Rochester, New York.
Several authors have speculated that due to similar
chemical structure, the nature of the response and the
level of exposure to induce that response could be
similar for chlorinated dibenzofurans and chlorinated
dibenzodioxins. To determine the role RGB's per se or a
chlorinated dibenzofuran contaminant may play in the
toxicity of RGB's, and to simultaneously correlate chlo-
rinated dibenzofuran response to chlorinated dibenzo-
dioxins, initial experiments were undertaken using
2,3,7,8-tetrachlorodibenzofuran. The dibenzofuran with
chlorines at the 2,3,7, and 8 positions was felt to be the
isomer of initial interest given that it is the isomeric
configuration that is the most toxic chlorinated diben-
zodioxin.
In all of the studies which I am to report upon
today, the 2,3,7,8- tetrachlorodibenzofuran (TCDF)
usedtt was of 88 percent purity with the remaining
components primarily a pentachlorodibenzofuran. The
TCDF was dissolved in acetone, which was then further
mixed with corn oil. All doses of TCDF were adminis-
tered by gavage. We have conducted general toxicity
studies with TCDF in chicks, mice, guinea pigs, and rats.
In most instances, the data to be presented
represent current status of ongoing research; as such, it
does not allow for a clear concise conclusion at this
time. However, I do feel the data to be sufficient for o.ie
to perceive trend, and I present it with this in mind.
In one experiment (ref. 7), TCDF was administered
daily by gavage utilizing white leghorn chicks that were
1 day of age when the study commenced. Birds which
received 5 A'Q/kg per day TCDF died in an average of
11.5 days. General unthriftiness and apparent depression
preceded death. One of six chicks receiving 1 jug/kg per
day TCDF died on day 19. Body weight and food con-
sumption decreased in this group during the 14th to 21st
day of the study. The experiment was designed to
terminate on the 21st day. It was our impression that
had the study endured an additional week, most, if not
all, chicks at the 1 /jg/kg dose would have died. The
most striking gross pathologic change observed was the
accumulation of clear fluid, as evidenced by marked
subcutaneous edema, ascites, and hydropericardium,
with the severity of the fluid accumulation greatest at
the 5 jug/kg dose. The hearts of these birds also appeared
enlarged and flabby (rounded). The second striking
change was a marked reduction in size of the thymus
and spleen. Histologically, size reduction could be
77
-------
accounted for by the marked depletion of lymphocytic
cell types in the spleen and cortex of the thymus.
Similar pathologic changes were found to occur at the 1
fig/kg dose, albeit to a milder extent. There were no
significant effects observed on liver weight; mild liver
pathology was found to occur only at the 5 M9/l<9 dose.
Total serum protein levels were reduced with a marked
reduction in serum albumin.
The toxic response described is similar to that
observed in "chick edema disease," a syndrome later
shown to be produced by chlorinated dibenzodioxins.
This TCDF response is in general agreement with the
response that Vos observed in birds that received RGB's
that contained low levels of tetrachloro- and penta-
chlorodibenzofurans.
Toxicity studies with TCDF in Hartley guinea pigs
are summarized in table 1. This table shows that the
single oral LD50 dose lies between 5 and IQ^g/kg. It is
also evident that there is an inverse relationship between
increased dose and decreased mean time to death. The
bottom of the table shows, for comparative purposes,
that the LDSO_30 (that dose which causes 50 percent
mortality in a 30-day period) of 2,3,7,8-tetrachlorodi-
benzodioxin (2 MQ/kg) compares quite closely with the
TCDF value. TCDF toxicity in guinea pigs is one of a
progressive weight loss followed by depression at least
24 to 36 hours preceding death. As was observed in the
chicken toxicity studies, there was severe diminution in
size of thymus and spleen. Similarly, this finding was
found to correlate with a lymphocyte depletion in the
periarterialor lymphocytic sheaths and follicles of the
spleen; or severe atrophy of the thymus cortex. Al-
though the numbers of animals evaluated were small, the
trend of changes present in the bladder, adrenal, kidney,
and liver were similar to that previously associated with
tetrachlorodibenzodioxin toxicity (ref. 8).
A single experiment in which TCDD was adminis-
tered to rats at doses up to 1,000 M9/kg failed to show
any toxic effects. These rats were terminated 4 weeks
after dosing. Histopathologic evaluation of tissues from
the rats failed to reveal any changes that could be associ-
ated with tetrachlorodibenzofuran toxicity.
Table 2 summarizes the TCDF toxicity findings in
male C57B1/6 mice. Per os dose levels up to and
including 6,000 jug/kg in a single dose failed to produce
any observable effects during the ensuing 28 to 30 days.
Histopathologic examinations of these animals failed to
reveal any effects on thymus, spleen, or other organs,
save for the liver. Here, a mild effect with the sugges-
tions of a mild toxicity was observed in mice that
received 6,000 jug/kg per os. A definite toxic response
was observed in mice that received a 6,000 M9/k9 dose
administered subcutaneously. Although mortality was
not observed, there was a depression in body weight gain
during the second to fifth day following dosing. Organ
weights recorded at time of necropsy 30 days after the
dose had been administered showed an increase in the
liver weight as well as livor to body weight ratio.
Table 1. 2,3, 7, 8-tetrachlorodibenzofuran toxicity
in Hartley guinea pigs
Per os
dose (ug/kg) ^Mortality
Mean time to death
80
40
20
15
10
5
0
5/5
5/5
5/5
6/6
9/11
3/11
0/11
10.8 days
11.6
12.2
12.0
15.5
18.0
-0-
LD5Q 2,3,7,8-TCDD = 2.0 yg/kg ; MTD = 20.6 days.
78
-------
Table 2. 2, 3, 7, 8-tetrachlorodibenzofuran toxicity
in male C57 BL/6 mice3
Dose:
Mortality:
Body weight:
Liver/body weight:
Ratio:
Thymus/body weight:
Ratio:
0 ug/kg
None
Normal gain
1.513 + 0.05
5.76 + 0.05
0.045 + 0.002
0.19 + 0.01
6,000 yg/kg
None
SI. depression 2nd-5th day
1.728 + 0.04
6.86 + 0.06
0.017 + 0.001
0.06 + 0.007
Administered subcutaneously to 6-week-old mice. Animals sacrificed 30
days post-administration. "No effects" per, os, at 6,000, 4,000, 2,500,
1,500, 1,200, 1,000, 800, 600, and 400 ug/kg. LD,n 2,3,7,8-TCDD =
200-250 yg/kg. bu
A more striking finding was the reduction in thymus
weight with a concurrent reduction in thymus to body
weight ratio. Histopathologic evaluations of tissues from
these animals confirmed that the reduction in thymus
weight was due to loss of lymphocytic elements. Evalua-
tion of the liver evidenced a clear, but moderate, toxic
response characterized by focal areas of single- cell
necrosis and pleomorphism. The mouse studies show
that there is at least a 30-fold diminution in TCDF tox-
icity when compared to TCDD. It further indicates,
however, that the pattern of the toxicity likely will
mimic that which is observed with tetrachlorodibenzo-
dioxin (ref. 9).
The health significance of dibenzofurans in PCB
toxicity can only be speculated upon at this time. It is
clearly toxic at very low dose levels in the chick and
guinea pig. However, studies to date with the mouse and,
to a lesser extent, with the rat suggest that toxicity in
these species may not be as closely correctable to the
corresponding dibenzodioxin analog. Furthermore, I
believe the specific structure of chlorinated dibenzo-
furan isomers must be elucidated before their health
significance can be projected with any reasonable degree
of confidence. This opinion is based on work with
chlorinated dibenzodioxins where marked variability in
toxicity was seen dependent on the specific chlorinated
isomer tested (ref. 10).
A final point addresses the tendency to speculate
that the 3,4,5,3',4',5'-HCB toxicities as seen in mice and
chickens are due to TCDF, Though the pattern of
pathologic response is similar in both instances, the
response which is observed is not pathognomonic for a
specific chemical.
These dibenzofuran studies are continuing and are
being extended to the rhesus monkey as soon as suffi-
cient 2,3,7,8-TCDF is synthesized. A systematic evalua-
tion of other chlorodibenzofurans is planned.
REFERENCES
1. J. G. Vos, "Toxicology of PCB's for Mammals and
for Birds," Environmental Health Perspectives, April
1972, pp.'105-117.
2. J. G. Vos, J. H. Koeman, H. L. van der Maas, M. C.
ten Noever de Brauw, and R. H. de Vos, "Identifica-
tion and Toxicological Evaluation of Chlorinated
Dibenzofuran and Chlorinated Naphthalene in Two
Commercial Polychlorinated Biphenyls," Fd.
Cosmet. Toxicol.. Vol. 8 (1970), pp. 625-633.
3. J. G. Vos and R. B. Beems, "Dermal Toxicity
Studies of Technical Polychlorinated Biphenyls and
Fractions Thereof in Rabbits," Toxicology and
Applied Pharmacology, Vol. 19 (1971), pp.
617-633.
4. G. W. Bowes, M. J. Mulvihill, B. R. T. Simoneit, A.
L. Burlingame, and R. W. Risebrough, "Identifica-
tion of Chlorinated Dibenzofurans in American
Polychlorinated Biphenyls," Nature, Vol. 256 (July
24, 1975), pp. 305-307.
5. A. Curley, V. W. Burse, R. W. Jejinings, and M. E.
Grim, "Metabolite or Contaminant of Aroclor 1254
Found in Rat Urine," MS 394, April 12, 1972,
79
-------
Environmental Protection Agency, Chamblee
Toxicology Laboratory, Chamblee, Georgia.
6. M. Kuratsune, Y. Masuda, and J. Nagayama, "Some
of the Recent Findings Concerning Yusho,"
presented at the National Conference on PCB's,
November 19-21,1975, in Chicago, Illinois.
7. J. D. McKinney, K. Chae, B. N. Gupta, J. A. Moore,
and J. A. Goldstein, "Toxicology of Hexachloro-
biphenyl Isomers and 2,3,7,8-Tetrachloro-
dibenzofuran in Chicks. I. Relationship of Chemi-
cal Parameters," Toxicol. Appl. Pharmacol., (1975),
in press.
8. B. N. Gupta, J. G. Vos, J. A. Moore, J. G. Zinkl, and
B. C. Bullock, "Pathologic Effects of 2,3,7,8-tetra-
chlorodibenzo-p-dioxin in Laboratory Animals,"
Environmental Health Perspectives, (September
1973), pp. 125-140.
9. J. G. Vos, J. A. Moore, and J. G. Zinkl, "Toxicity of
2,3,7.8-Tetrachlorodibenzo-D-dioxin (TCDD) in
C57B1/6 Mice," Toxicology and Applied Pharma-
cology, Vol. 29 (1974), pp. 229-241.
10. E. E. McConnell arid J. A. Moore, "The Compara-
tive Toxicity of Chlorinated Dibenzo-p-dioxin
Isomers in Mice and Guinea Pigs," abstract to be
presented at the March 14-18, 1976, meeting of the
Society of Toxicology to be held in Atlanta,
Georgia.
80
-------
19 November 1975
Session II:
USES, SOURCES, AND
IDENTIFICATION
David Garrett*
Session Chairman
'Chief, Special Projects Branch, Office of Toxic Substances, Environmental Protection Agency, Washington,
D.C.
81
-------
INTRODUCTORY REMARKS
David Garrett
This session will deal with the uses, sources, and
identification of RGB's, their disposal, reclaiming, and
their treatment. All of us here on the podium have been
required many times to share or contribute to many
meetings involving discussions on PCB problems, and we
are on a day-to-day basis directly involved with these
problems.
Since discovery and commercialization of these sub-
stances with such marvelous commercial properties for
which there appears to be no universally perfect sub-
stitute, some 500 million pounds have been pumped into
our environment. Over this period after some 45 years,
considering the RGB's still in service, the quantities de-
stroyed via incineration, and natural dissipative forces,
estimates have been given that some 125 to 135 million
pounds are still available for biological activities.
Our eminent speakers will address both the quanti-
ties and active service life and the quantities still avail-
able for biological activity.
83
-------
CHARACTERIZATION OF POLYCHLORINATED BIPHENYLS
J. P. Mieure, Ph.D.,* 0. Hicks, R. G. Kaley, Ph.D., and V. W, Saeger, Ph.D.
Abstract
Assessment of the environmental impact of PCB
products cannot be carried out without a basic under-
standing of the physical and chemical properties of these
mixtures. PCB structure and nomenclature and the
approximate composition of Arocfor products are pre-
sented. Several physiochemical properties which affect
the performance and environmental impact of current
dielectric products are described.
CHEMICAL STRUCTURE
Polychlorinated biphenyls (PCB's) are made by
direct chlorination of biphenyl. The biphenyl molecule
has 10 possible sites at which chlorine atoms can be
substituted. The numbering system for the biphenyl
structure is shown in figure 1. By convention, the two
rings are numbered identically, except the ring with the
fewest chlorine substituents or substituted in the highest
numerical positions is designated as primed. Examples of
nomenclature for a tri- and a tetrachlorobiphenyl are
included in figure 1. An excellent discussion of PCB
nomenclature can be found in a recent text by Hutzin-
ger, Safe, and Zitko (ref. 1).
There are 209 possible chlorobiphenyl isomers dis-
tributed as indicated in table 1. However, many of these
isomers are not likely to occur at significant levels in
commercial PCB mixtures. For example, isomers with
four or five chlorine atoms on one ring but none on the
other ring are not detectable in PCB products.
AROCLOR PRODUCTS
The major producer of PCB's in the United States is
Monsanto Company, which markets mixtures for closed
electrical system applications under the Aroclor trade-
mark. Aroclor products are identified by a four-digit
numbering code in which the first two digits, 12, indi-
cate the parent molecule is biphenyl and the last two
digits specify the weight percent of chlorine. The excep-
tion is Monsanto's newest product, Aroclor 1016 (41%
chlorine), which retained the 1016 designation by which
it was known during development. Aroclor products
manufactured in the United States are listed in table 2.
3 2
5'
2,2'T3-TRICHI.OROB1PHENYL
Cl Cl
•Research Group Leader, Monsanto Industrial Chemicals
Company, St. Louis, Missouri.
2»2',3,4'-TETRACHLOROBIPHENYL
Figure 1. The numbering system for
the biphenyl structure.
Production of the materials listed as discontinued was
terminated in or prior to 1971.
AROCLOR COMPOSITION
The composition of the four Aroclor products cur-
rently marketed in the United States is given in table 3.
Aroclor 1221 is primarily monochlorobiphenyl while
Aroclor 1016 and Aroclor 1242 are primarily trichloro-
biphenyls. The major difference between these two
products is the lower penta- and hexachlorobiphenyl
84
-------
150
150
AROCLOR 1221
111
174
198
TEMPERATURE °C
222
230
Figure 2. Detailed chromatogram of Aroclor 1221.
AROCLOR 1016
ULJ
174
198
TEMPERATURE °C
222 230
Figure 3. Detailed chromatogram of Aroclor 1016.
85
-------
Table 1. 209 possible PCB isomers
Degree of
substitution
Mono
Di
Tri
Tetra
Penta
Hexa
Hepta
Octa
Nona
Deca
Number
of isomers
3
12
24
42
46
42
24
12
3
1
209
Table 2. Aroclor products
manufactured in the
United States
Current
1221
1016
1242
1254
Discontinued
1232
1248
1260
1262
1268
Percent
chlorine
21
32
41
42
48
54
60
62
68
content of Aroclor 1016. Aroclor 1254 is primarily pen-
tachlorobiphenyl. The values in table 3 were calculated
from measurements by gas chromatography with flame
ionization detection after component identification by
gas chromatography/mass spectrometry. All gas chroma-
tographic separations were made with a high-resolution
capillary column. Average response factors determined
for each degree of chlorine substitution were applied to
all components.
Detailed chromatograms of these four products are
illustrated in figures 2-5. Specific isomer identifications
determined by Webb and McCall (ref. 2) and Sissons and
Welti (ref. 3) are listed for the major Aroclor 1242 com-
ponents in figure 4. The complexity of these mixtures
was emphasized by amplifying the first and last portions
of the Aroclor 1254 chromatogram in figure 5. Eighty-
five components were detected in Aroclor 1254. A
.32-mm id x 50-m glass capillary column coated with
OV-101 was used for these separations. The flow rate
was 2 ml/min helium and the column temperature was
programmed from 150° to 230° C at 2° C/min.
High-resolution chromatographic conditions are
very useful for characterizing PCB products. However,
for routine monitoring of environmental materials, it is
more appropriate to use gas chromatography with pack-
ed columns and electron capture detection. Typical
chromatograms of this type for Aroclor 1016 and Aro-
clor 1242 are compared in figure 6. The chromatograms
are essentially identical for retention times less than 70
relative to p,p'-DDE. However, the higher chlorinated
components with relative retention times 70 and greater
represent a significantly smaller contribution in the Aro-
clor 1016 chromatogram. These chromatograms illus-
trate the feasibility -o1 distinguishing these unaltered
products. However, in environmental materials the char-
acteristic features of Aroclor 1242 are frequently
obscured by interfering compounds or by component
alteration so the distinction is less clear or sometimes
entirely lacking. These separations were carried out on a
6 ft x 4-mm id glass column packed with 3 percent
SE-30 on 80/100 mesh Chromosorb W-HP at 190° C.
PHYSICOCHEMICAL DIFFERENCES
The physical and chemical properties of PCB isom-
ers and commercial mixtures vary greatly depending on
the degree and position of chlorine substitution. The
effect of chlorine content on several physicochemical
properties is summarized in table 4. Three of these prop-
erties, volatility, water solubility, and biodegradability,
are very relevant to the environmental occurrence of
PCB's. Volatility and water solubility represent potential
mechanisms for introduction into and transport within
the ecosystem.'Biodegraidation represents a mechanism
for removing PCB's from the environment. Illustrations
of the relative significance of these properties for differ-
ent PCB isomers are evident from the following three
examples.
Relative volatilities For the P£B components in Aro-
clor 1016 are indicated in figure 7 by comparing chro-
matograms of liquid and vapor composition. The higher
86
-------
Table 3. Typical percent composition of Aroclor products
Homo log
# Cl/biphenyl
0
1
2
3
4
5
6
7
8
Aroclor
1221
11
51
32
4
2
0.5
NDa
ND
ND
Aroclor
1016
0.1
1
20
57
21
1
0.1
ND
ND
Aroclor
1242
0.1
1
16
49
25
8
1
0.1
ND
Aroclor
1254
0.1
0.1
0.5
1
21
48
23
6
ND
aND = none detected, 0.01 percent.
Table 4. Physiochemica! properties for PCB products
Property
Density (g/ml)
Distillation range
(°C)
Fire point (°C)
Vaporization rate
(mg/crn2/hr @100 °
Percent chlorine
21 42 54
1.19
275-320
176
C) 1.74
1.39
325-366
None
.338
1.50
365-390
None
.053
Water solubility
(ppm)
Biodegradability3
>.2
81
.2
26
.04
15
aPercent degradation/48 hr cycle with semicontinuous
activated sludge.
87
-------
150
CM
N
(M
AROCLOR 1242
UU
(M
174
198
TEMPERATURE °C
222 230
Figure 4. Detailed chromatogram and isomer identification- Aroclor 1242.
150
x4
174
AROCLOR 1254
198
TEMPERATURE °C
222 230
Figure 5. Detailed chromatogram of Aroclor 1254.
88
-------
AROCLOR 1016
AROCLOR 1242
Figure 6. Comparison of electron capture chromatograms
of Aroclor 1016 and Aroclor 1242.
89
-------
Q>
W
C
o
a
£
Aroclor 1016
Standard
Aroclor 1016
Vapors
0
Time (Min)
Figure 7. Relative volatilities for PCB components in Aroclor 1016.
numbered components make successively less contribu-
tion to the total vapor composition.
Water solubility of Aroclor 1016 components is il-
lustrated in similar fashion in figure 8. Water saturated
with Aroclor 1016 was extracted with hexane and the
extract compared chromatographicaliy to an Aroclor
1016 standard. The numbers above significant peaks ex-
press the percentage contribution of that peak area to
the total area. Earlier eluting, lower chlorinated compo-
nents are more soluble and contribute more to the water
saturated composition. A related study has shown that
RGB's leaching from Aroclor 1016 impregnated soils
after the equivalent of 40 years annual rainfall consist of
lower chlorinated biphenyls (ref. 4) (figure 9).
Microbial degradation also affects PCB isomers to
different degrees. For example, figure 10 shows chro-
matograms depicting Aroclor 1016 composition after ex-
posure to a naturally occurring mixed microbial popula-
tion for 1/2 hour (above) and 14 days (below). The
number above each GC peak indicates the percent biode-
gradation for that component. These percentages range
from 17 to >98 and in general are higher for lower
chlorobiphenyls. The exposure was carried out with acti-
vated sludge from a domestic sewage treatment facility.
The sludge was previously acclimated to a mixture of
industrial organic compounds before addition of 3 ppm
Aroclor 1016. PCB composition was determined by ex-
tracting a representative aliquot of mixed liquor with
hexane followed by analysis by gas chromatography
using a glass capillary column and electron capture de-
tection.
It is apparent from these examples that introduction
of PCB's into,the ecosystem by volatility or water solu-
bility would enhance the ratio of lower to higher chlori-
nated biphenyls in the environment. PCB removal from
the environment by either of these mechanisms or by
microbial degradation would reduce this ratio. These and
related factors combine to make assessment of PCB envi-
ronmental impact a very complex problem.
In view of the recognized complexity in studying
commercial PCB mixtures, it would seem expedient to
substitute for the mixture a single isomer product having
90
-------
AROCLOR 1016
STANDARD
19.4
16.3
11.2
WATER SOLUBLE
11.3
7.3
Figure 8. Water solubility of Aroclor 1016 components.
91
-------
AROCLOR 1016 STD SOLN
PCBs FROM RAY SILTY LOAM
AROCLOR 1221 STD SOLN
0123
Figure 9. Composition of PCB's
leaching from Aroclor
1016 impregnated soil.
92
-------
SEMI-CONTINUOUS ACTIVATED SLUDGE
93
>98
58
>94
IJffl
86
72
20
30 MINUTES
27
17
17
14 DAYS
r
16
I
24
TIME (MIN)
I
32
40
48
Figure 10. Aroclor 1016 biodegradation.
the desired electrical and physical properties. The envi-
ronmental properties of this isomer would be much
simpler to characterize and control. However, no such
PCB isomer exists. Most PCB isomers are solid crystalline
materials when isolated at 25° C. Commercial products
are liquids only because of the mutual melting point
depression exerted by the PCB components of the mix-
ture.
CONCLUSIONS
Commercial PCB products are mixtures of many dif-
ferent isomers with varying chlorine content. The prop-
erties of these isomers, and hence the products, are vast-
ly different and are complex to study. The environmen-
tal impact for each product must be accurately assessed
and compared to the functional benefit.
REFERENCES
1. O. Hutzinger, S. Safe, and V. Zitko, "The Chemistry
of RGB's," CRC Press, Cleveland, 1974.
2. R. G. Webb and A. C. McCall, J. Assoc. Of fie. Anal.
Chem., Vol. 55 (1972), p. 746.
3. D. Sissons and D. Welti, J. Chromatog., Vol. 60
(1,971), p. 15.
4. E. S. Tucker, W. J. Litschgi, and W. M. Mees, Bull.
Environ. Contam. Toxicol., Vol. 13 (1975), p. 86.
93
-------
OVERVIEW OF ANALYTICAL IDENTIFICATION AND
SPECTROSCOPIC PROPERTIES
Stephen Safe, Ph.D.*
Abstract
The analytical problems associated with PCB analy-
sis involve many factors including sampling techniques,
extraction and cleanup procedures, quantisation of PCB,
confirmation of structure, and identification of metab-
olites and impurities. Recent studies in these areas of
PCB analysis will be discussed and examples given.
Polychlorinated biphenyls (PCB) are among the
most persistent and widespread environmental pollut-
ants. Commercial PCB formulations can consist of up to
100 different chlorobiphenyl isomers and this is a com-
plicating factor in the conventional gas chromatographic
analysis of environmental samples. The chemical stabili-
ty of PCB does, however, facilitate their analysis in that
a variety of cleanup procedures can be used to remove
coextractive material without modification of the PCB.
The determination of PCB has been described in "detail
(ref. 1) and therefore most of the data and results re-
ported herein will be associated with more recent publi-
cations.
The analytical problems associated with PCB analy-
sis can be summarized under six major headings, which
will be discussed in detail:
1. Sampling methods,
2. Extraction of PCB from environmental samples,
3. Cleanup procedures,
4. Quantitation of PCB levels,
5. Confirmation of structure, and
6. Identification of toxic impurities and metabo-
lites.
1. Sampling Methods
PCB analysis is primarily concerned with determina-
tion of the pollutant concentrations in biological, sedi-
ment (or solid), water, and air samples. Specific sampling
methods are required.
a. Biological samples and sediments. The sampling
must insure that sufficient material is collected and ex-
tracted so that the analytical data obtained are repre-
sentative of the sample.
b. Water samples. The sampling of water is compli-
cated by the need to distinguish between dissolved PCB,
which are usually low, and PCB adsorbed on paniculate
*Guelph Waterloo Centre for Graduate Work in Chemistry,
Department of Chemistry, University of Guelph, Guelph, Ontar-
io, Canada.
matter. The separation of the two fractions can usually
be obtained using suitable filtration or centrifugation
techniques (ref. 1).
c. Air samples. Air samples are usually obtained
by passage of a known volume of air through an imping-
er or a similar device in which a suitable solvent prefer-
entially extracts or removes airborne PCB (refs. 2,3).
2. Extraction of PCB from Environmental Samples
a. Biological samples. A number of methods have
been described for the semiquantitative extraction of
PCB from biological samples (e.g., > 90 percent recov-
ery) (ref. 1). The sample can be macerated then freeze-
dried, or dehydrated and extracted directly or by the
soxhlet technique using an appropriate solvent. The
choice of solvents can vary from nonpolar hexane or
pentane to the more polar chloroform, acetone, or meth-
anol. The more polar water-soluble solvents are useful in
the extraction of wet tissue; however, the polar aqueous
extracts are usually diluted with water and extracted
with hexane to preferentially remove the nonpolar chlo-
rinated aromatics. This partitioning technique is also uti-
lized as a cleanup procedure to remove polar coextrac-
tives.
b. Sediments. Sediments and other solid samples
are usually extracted with more polar solvents and ulti-
mately the PCB are parthioned as described above (ref.
1).
c. Water. The simplest approach with water is by
direct extraction with hexane. The removal of PCB from
water has also been effected using polyurethane foam
plugs and resins (refs. 4-6). Using this technique, the
water is passed through a column containing the solid
support and the PCB are adsorbed on these supports.
Subsequent passage of a polar organic solvent through
the columns removes the adsorbed organics, which can
be further cleaned up using the partitioning technique.
d. Air, PCB are readily extracted from air by pas-
sage of the air through sintered glass funnels or suitably
contracted glass impingers filled with solvents (e.g., amyl
acetate, sec-butanol or ethylene glycol) (refs. 2,3). The
PCB can then be isolated by the standard partitioning
technique.
3. Cleanup Procedures
The major aim of a cleanup procedure is to selec-
tively remove coextractive natural material and xeno-
biotics from an extract containing PCB. Solvent parti-
tioning has already been discussed and is an excellent
94
-------
method for removing water-soluble and highly polar co-
extractive organics. The two additional important clean-
up techniques are methods based on column or thin-
layer chromatography and chemical treatment of the
extract to modify either the PCB or the coextractives.
a. Chromatographic methods. Most chromato-
graphic procedures include column chromatography on
activated florisil and/or alumina using hexane to elute
the PCB (refs. 7,8). Thin-layer chromatography with si-
licic acid and alumina can also be used. An example of a
typical chromatographic cleanup procedure is outlined
in figure 1.
b. Chemical methods. Since PCB are thermally
and chemically stable, it is possible to saponify extracts
by both acidic and basic treatment without altering the
PCB. This procedure is particularly useful in the conver-
sion of lipid esters, which have chromatographic proper-
ties similar to PCB, into more polar products. One of the
major problems in PCB cleanup is to remove DDE,
which has similar chromatographic properties to PCB. A
recent paper describes an oxidative technique which
quantitatively converts DDT, DDE, and their analogs
into more polar products (ref. 9). Dehydrochlorination
with mild base converts DDT and DDT-like compounds
into the corresponding bisdiarylethylenes (e.g., DDE);
treatment of the olefin with chromic acid gives the cor-
responding benzophenones, which are readily separated
from PCB. The PCB are not affected by this chemical
modification procedure. Raney nickel reduction and sul-
furic acid treatment of crude PCB extracts are also use-
ful in the cleanup of river water extracts (ref. 10).
The analysis of PCB is always complicated by the
large number of isomeric chlorobiphenyls that are pre-
sent and this results in a complicated gas chromatogram
even after cleanup (figure 2). In addition, polychlorinat-
ed terphenyls (PCT) and polychlorinated naphthalenes
(PCN) are also industrial environmental pollutants which
are composed of several isomeric components that can
co-occur with PCB. A perchlorination procedure was re-
ported in which the isomeric mixtures can be converted
into their respective perchloro derivatives (refs. 11,12),
as shown in figure 3. These compounds can then be
readily analyzed and quantitated by conventional gas
chromatography (figure 2). The comparative gas chro-
matographic retention times of several perchlorinated
pollutants are: decachlorobiphenyl, 1.0; octachlorodi-
benzofuran, 2.55; octachlorodibenzo-p-dioxin, 2.60;
dodecachloro-DDE, several peaks > 1.9; tetradeca-
chloro-o-terphenyl, 11.9; tetradecachloro-m-terphenyl,
19.2; tetradecachloro-p-terphenyl, 22.2.
It should be noted that this procedure is markedly
dependent on the purity and source of the commercial
antimony pentachloride reagent and the composition or
degree of chlorination of the PCB. A drawback of this
General Cleanup Procedure
(suitable for most air, water .biological and sediment analyses)
Crude Extract
solvent partition
(hexane: polar solvent)
hexane extract
chromatography on
activated alumna
purified PCB
chromatography on
activated silica gel
purified PCB
Rationale
polar imputities remain in polar
solvent
Removal of nonpolar lipids,
impurities, and some chlori-
nated pollutants
Removal of nonpolar lipids and
separation of PCB from DDT
and its metabolites
Figure 1. General cleanup procedure.
95
-------
Uf
in
2
O
0.
o:
o:
uj
o
o:
o
o
IU
a:
AROCLOR 1254 STANDARD
AROCLOR 1254 AFTER PERCHLORINATION
(DECACHLOROBIPHENYL)
12
Min.
39
45
51
I
57
Figure 2. Gas chromatogram after cleanup.
1. SbCl5/l2
or
2.
S02C12
A1C13
Figure 3. Perchlorination procedure in which isomeric mixtures
can be converted into their respective perchloroderi-
vatives.
96
-------
technique is the reported formation of varying quantities
of a sideproduct which has been identified as bromo
nonachlorobiphenyl (refs. 13,14). This introduces a
second peak which is observed in the gas chromatogram
and this side reaction can also reduce the overall yield of
the decachlorobiphenyl product.
4. Quantitation of PCB
Gas chromatography is the method of choice for
PCB analysis and electron-capture detection is by far the
most sensitive procedure for detecting these chlorinated
aromatic compounds (ref. 1). A comparison of the rela-
tive molar responses of electron-capture and flame-
ionization detector to some isomeric chlorobiphenyls is
given in table 1. It is evident that the electron capture
detector is the more sensitive and that the relative molar
response is both a function of the degree of chlorination
and the position of the substituent (refs, 15,16). Since
the precise composition of PCB mixtures is not known,
the quantitation of the complex chromatograms can
only be an estimated value. A more consistently accurate
method would involve perchlorination since the relative
molar response and chromatographic properties of deca-
chlorobiphenyl are known. Quantitation of the PCB
mixtures is usually obtained by measuring the total peak
heights or areas of key diagnostic peaks that are present
in the environmental PCB extract and comparing this
result with the heights or areas obtained in the gas chro-
matogram of the appropriate commercial PCB mixture
(e.g., Aroclor 1254, Clophen A-60). An example is
shown in figure 4, in which the chromatograms of
Clophen A-60 and river water extracts are compared and
the quantitation is carried out using three diagnostic
peaks present in the environmental and commercial PCB
sample (ref. 10).
5. Confirmation of Structure
PCB in the environment was originally detected by
gas chromatography and later confirmed by mass spec-
trometry and this technique is the most sensitive and
Table 1. Relative molar responses of electron-
capture and flame-ionization detectors
to some chlorobiphenyls
Relative molar response
Chlorobiphenyl
2-
3-
4-
2,2'-di
2,4'-di
2,6-di
3,3'-di
3,4-di
4,4'-di
2,4,4'-tri
2,2' ,4,4'-tetra
2,2' ,6,6'-tetra
3,3' ,4,4'-tetra
3,3',5,5'-tetra
2,3,4,5-tetra
2,3,5,6-tetra
2,2' ,4,4' ,6,6'-hexa
3,3' ,4,4',5,5'-hexa
2,2',3,3',4,4l,6,6'-octa
2,2' ,3,3',5,5',6,6'-octa
deca
Electron
capture
1.00
0.20
1.10
5.16
17.7
32.0
6.10
15.2
5.97
135
106
20.6
396
320
367
259
347
726
1180
1150
1410
Flame
ionization
1.00
0.92
0.87
0.99
0.86
0.91
0.94
0.86
0.81
0.78
0.87
0.90
0.87
0.85
0.87
0.71
97
-------
Quantitation of PCB
1. The method of choice is gas chromatography (GC)
using an electron capture (EC) detector. The
major problem is selecting suitable standard peaks
to use as quantitative standards for comparison
with the commercial PCB standard samples.
CUOPHEN A-60 O.Sng
GBTA RIVER SAMPLE 19
min.
15
10
Figure 4. Gas chromatographic analysis with
electron capture detector. The in-
jected volume of river water extract
corresponds to 1.6 liters water.
98
-------
widely used spectroscopic method for the confirmation
of PCB. The mass spectrometry of isomeric chlorobi-
phenyls and the applications of this technique in envi-
ronmental analysis has been reviewed (ref. 17) and only
recent applications of this analytical technique will be
mentioned.
a. Gas chromatography — mass spectrometry
(GC-MS). Gas chromatographic analysis of PCB can be
carried out by combination GC-MS so that the mass
spectrum of the individual peaks which elute from the
gas chromatograph can be recorded. This technique in
combination with a computer has been extensively used
in environmental analysis for both the detection and
confirmation of environmental PCB, related metabolites,
and toxic impurities (refs. 1,17). A GC-MS of an envi-
ronmental sample may generate hundreds of spectra;
however, using the computer the analyst can recall indi-
vidual spectra as well as conduct limited mass searches
on key diagnostic ions.
b. Mass fragmentography GC-MS (ref. 18). The
mass spectrum of a sample is obtained by scanning the
entire mass range in order to record alfthe ions that are
generated. If a mass range of 400 is scanned in a period
of 4 seconds, then the mass spectrum is held for only
1/100th of a second at each mass unit; for the remaining
3.99 seconds the ion current at that mass value is lost.
Mass fragmentography is a technique which simultane-
ously monitors the ion current at one or more mass
values for the complete duration of the sample spectrum
(i.e., for 4 seconds rather than 0.01 second). The mass
values which are monitored are the most intense and
diagnostic ions generated by a compound. For PCB this
is usually the isotopic molecular ion species or the iso-
topic M-CI2 ions. The sensitivity of a GC-MS instrument
operating in the mass fragmentography mode can surpass
that of an electron capture detector. An example of this
technique is shown in figure 5, in which the mass frag-
mentograms of standard Clophen A-60 and river water
CLOPHEN A-60 10ng
GOTA RIVER WATER 160L SAMPLE 1/100
360
362
CLOPHEN A-60 lOng
326
328
GOTA RIVER WATER 160L SAMPLE t/10
GdTA RIVER WATER 160L SAMPLE 1/10
290
5 10 15 min.
Figure 5. Mass fragmentograms of PCB Standards
and river water extracts.
99
-------
extracts are compared (ref. 19). The diagnostic ions
which were used are the isotopic hexachlorobiphenyl
(m/e 362, 360, and 358), pentachlorobiphenyl (m/e
328, 326, and 324), and tetrachlorobiphenyl (m/e 294,
292, and 290) molecular ions.
c. High-resolution photoplate mass spectrometry.
The relatively large mass deficiencies of both chlorine
isotopes cause the exact masses of ions which contain
chlorine to be usually less than ions of the same nominal
mass that contain only isotopes of C, H, N, and 0 (see
table 2). Thus, a typical lipid coextractive would appear
at mass positive integer values whereas the molecular ion
for a tetrachlorobiphenyl isomer (accurate mass
289.9224) appears at 776 millimass units below the inte-
ger value. Mass negative PCB ions are therefore readily
distinguished from mass positive ions which occur at the
same nominal mass by high-resolution techniques. A
photographic plate can be used as an integrating ion
detector and the subsequent identification of the PCB
on the plates is readily carried out. This technique has
been used in the detection of PCB in biological samples
as well as confirming the presence of hydroxylated PCB
metabolites (refs. 20,21).
6. Identification of Toxic Impurities and PCB Metabo-
lites
Analysis of commercial PCB preparations showed
that higher chlorinated naphthalene isomers were pre-
sent as trace impuritie:; and their structures were con-
firmed by mass spectrometry (ref. 22). More recently
the highly toxic chlorinated dibenzofurans have also
been identified in commercial preparations; the flow
chart in figure 6 outlines chromatographic procedures
for the isolation of these components (ref. 23).
The metabolism of PCB in diverse animal and micro-
bial systems has been investigated and the results indi-
cate the conversion of these substrates into a range of
hydroxylated metabolites (ref. 24). Figure 7 summarizes
a composite scheme for the separation and identification
of PCB metabolites and it should be noted that all the
steps are used in the cleanup procedure only when it is
necessary. Recent data from seal extracts has confirmed
the presence of hydroxylated PCB in their fatty tissue
(ref. 25). These metabolites are therefore a new class of
chlorinated aromatic pollutants derived from PCB.
The financial support of Environment Canada is
gratefully acknowledged.
Table 2. Confirmation of PCB by high-resolution
phosphate MS
Basic principles: Xenobiotics containing mass
deficient atoms (e.g., Cl) appear at lower
mass values than most "natural coextractives";
these differences can be measured using the
above technique.
Atom or
compound
12C
'H
14N
160
35C1
37C1
Lipid coextractive
Accurate
mass
12.000
1.0078
14.0031
15.9949
34.9688
36.9659
variable
Deviation from
integer value
(in millimass
units)
-
+78
+31
-51
-312
-341
100
-------
KC-400 In H«xan» soLucton
?loctJll Coluzn
/ \
PCS in *lu*t* A Cl-DBF to «la*t« B
(discard)
Alumina Micro Column
(PORTER, 197 la)
PCS ia «liuc« t
(discard)
Cl-DBF tn *luacc 2
Figure 6, Procedure for separation
of chlorinated dibenzo-
furans from chlorinated
biphenyis in KC-400.
Laboratory experiments show that PCB isotaers are metabolized to
hydroxylated PCS which can be isolated and identified as indicated.
Urine Sample
strong acid
hydrolysis and ether
extraction
Ethereal Extract
further cleanup via
base extraction of phenols
|(optional)
Crude Hydroxy PCB
JTLC, then extraction of
L"Hydroxy Band"
"Hydroxy Baal"
formation of acetate
or methoxy derivative
then TLC, and
.hydrolysis (optional)
Purified Hydroxy PCB
Rationale
Hydrolysis of glucuronides
Separation of phenolic
rrom othsr coextractives
Structures proven by
M.S. and NMR spectra
aad by
Figure 7. A composite scheme for the separation
and identification of PCB metabolites.
101
-------
REFERENCES
1. 0, Hutzinger, S. Safe, and V. Zitko, The Chemistry
of PCB's, CRC Press, Cleveland, Ohio, 1974, pp.
197-220.
2. J, D. Tessari and D. L. Spencer, J. Assoc. Offic.
Anal. Chem., Vol. 54 (1971), p. 1376.
3. D. C. Staiff, G. E. Quinby, D. L. Spencer, and H. G.
Starr, Bull. Environ. Contam, Toxicol., Vol. 12
(1974), p. 455.
4. H. D. Gessar, A. Chow, F. C. Davis, J. F. Uthe, and
J. Reinke,,4na/. Letters, Vol. 4 (1971), p. 883.
5. J. W. Bedford, Bull. Environ. Contam. Toxicol.,
Vol. 12 (1975), p. 622.
6. G. Sundstrom, 0. Hutzinger, S. Safe, and D.Jones,
Proc. Toxicology Symposium, Wageninger, Nether-
lands, 1975.
7. A. V. Holden and K. Marsden, J. Chrom.. Vol. 44
(1969), p. 481.
8. J, A. Armour and J. A. Burke, J. /Assoc. Offic. Anal.
Chem.. Vol. 53 (1970), p. 781.
9. W. J. Trotter, J. Assoc. Offic. Anal. Chem., Vol. 58
(1975), p. 461.
10. M. Ahnoff and B. Josefsson, Bull. Environ. Contam.
Toxicol.. Vol. 13 (1975), p. 159.
11. 0. W. Berg, P. L. Diosady, and G. A. V. Rees. Bud.
Environ. Contam. Toxicol., Vol. 7 (1970), p. 538.
12. 0. Hutzinger, S. Safe, and V. Zitko,./. Assoc. Offic.
Anal. Chem., (in press).
13. W. J. Trotter and S. J. V. Young, J, Assoc. Offic.
Anal. Chem.. Vol. 58 (1975), p. 466.
14, J. N, Huckins, J. E. Swanson, and D. L. Stallings, J.
Assoc. Offic. Anal. Chem.. Vol. 57 (1974), p. 416.
15. A. S. Y. Chau and R. C. J. Sampson, Environ.
Letters, Vol. 8 (1975), p. 89.
16. B. Bush, F. Baker, R. Dell'acqua, C. L. Houck and
F-C. Lo, J. Chrom., Vol. 109 (1975), p. 287.
17. S. Safe and O. Hutzinger, Mass Sfrectrometry of Pes-
ticides and Pollutants, CRC Press, Cleveland, Ohio,
1973.
18. E. J. Bonelli, P. A. Taylor, and W. J. Morris, Ameri-
can Laboratory, July 29,1975.
19. M. Ahnoff and B. Josefsson, Anal. Letters. Vol. 6
(1973), p. 1083.
20. S. Safe, N. Platonow, O. Hutzinger, and W. D.
Jamieson, Biomed. Mass Spectrom., Vol. 2 (1975),
p. 201.
21. O. Hutzinger, W. D. Jamieson, S. Safe, L. Paulmann,
and R. Ammon, Nature, Vol. 252 (1974), p. 698.
22, J. G. Vos, J H. Koeman, H. L. vander Maas, M. C.
tenNoever de Brauw and R.-H. deVos, Food Cos-
met Toxicol., Vol. 8 (1970), p. 625.
23. J. A. G. Roach and I. H. Pomerantz, Bull. Environ.
Contam. Toxicol., Vol. 12 (1974), p. 338.
24. S. Safe, O. Hutzinger, and D. Jones, J. Agrk. Food
Chem., Vol. 23 (1975), p. 851 and references cited.
25. B. Jansson. S. Jensen, M. Olsson, L. Renberg, G.
Sundstrom, and R. Vaz, Ambio., Vol. 4 (1975), p.
93.
102
-------
PRODUCTION AND USAGE OF PCB's IN THE UNITED STATES
Robert L. Durfee, Ph.D.*
Abstract
About 99 percent of the PCB's used in U.S. industry
are produced by Monsanto in a single facility atSauget,
Illinois. These materials, termed Aroclors, are used in the
production of capacitors (70 percent) and transformers
130 percent). Imported PCB's, comprising slightly over 1
percent of U.S. usage, are used in investment casting
operations (80 to 90 percent; decachlorobiphenyl) and
semiclosed heat transfer applications (10 to 20 percent).
Capacitor and transformer production processes are
similar in that process steps involving PCB's include fil-
tration, flood or individual filling of the products, and
removal of excess PCB's prior to sealing and individual
testing of the products. Most tosses occur from pump
leaks to cooling water, spills, personal hygiene practice,
and tiie like. Many of the discharges containing PCB's
are to municipal sewers.
Introduction
Poiychlorinated biphenyls (PCB's) represent a class
of compounds produced commercially by the chlorina-
tion of biphenyl. Most PCB's currently used in the
United States are mixtures of chlorobiphenyls contain-
ing up to seven chlorine atoms per molecule, although
some decachlorobiphenyl (10 chlorines per molecule) is
imported. The production and the types of uses for
PCB's increased steadily from initiation of production in
1929 until industry-imposed restrictions in 1971 cur-
tailed production and essentially eliminated use of
domestic production in all but "closed" electrical equip-
ment (specifically, capacitors and transformers).
PCB's have been increasingly identified as a signifi-
cant environmental pollutant. In our work for the Office
of Toxic Substances, Versar is studying the economics
and other aspects of possible regulatory alternatives as
applied to PCB's. We are also studying treatment meth-
ods which might be applied to control of waterborne
PCB's in industrial effluents. The purpose of this paper is
to define current PCB production and use, including
process technology and sources of wastes containing
PCB's.
Domestic Production and Imports
Monsanto, the sole domestic manufacturer of PCB's,
"Vice President. Versar, fnc., Springfield, Virginia.
manufactures this chemical in its Sauget, Illinois, plant.
The basic raw material is biphenyl, which is manufac-
tured from pure benzene in another Monsanto plant.
The PCB manufacturing operation is conducted in two
steps. First biphenyl is chlorinated with anhydrous
chlorine in presence of ferric chloride to produce crude
PCB's and then the crude PCB's are distilled to obtain
the finished product. A schematic flow diagram of this
process is given in figures 1 and 2.
Monsanto currently produces Aroclors 1221, 1016,
1242, and 1254 (chlorine contents approximately 21,
41, 42, and 54 percent by weight, respectively). For the
production of a given product, biphenyl and catalyst are
heated to melting and chlorine gas is introduced while
the charge is circulated with a pump. The time of chlo-
rine contact controls the degree of product chlorination.
Vapors from the chlorination (HCI) are scrubbed and
removed to another part of the plant.
The crude product is held at temperature and blown
with dry air for several hours, and then is sent to storage
where a small amount of lime is added to remove
.remaining HCI or ferric chloride. The blown air is
scrubbed and vented to the atmosphere through a
demister.
Purification, as typified by figure 2, varies some-
what between the different products. The 1016 material
is processed in a retort and a vacuum distillation (steam
jet ejection) to remove the more highly chlorinated
compounds. The first cut from the tower is recycled to
the retort. When a preset overhead temperature is
reached, the product is removed and sent to storage and
shipment. The other Aroclors are vacuum distilled
(steam jet ejectors), the product being the condensate.
The still bottoms (called Montars) are incinerated.
Monsanto's production in 1974 was 40,466,000 Ib,
of which 34,406,000 was sold domestically and
5,395,000 Ib exported. Production has been about at the
40-million-pound level since 1971, and reached a high of
85 million pounds in 1970. Company expectations are
for a sizeable increase in sales in 1976, followed by
small, steady growth.
Imports in 1973 and 1974 amounted to 1.2 to 1.5
percent of Monsanto's domestic sales in those years.
Importation appears to be steady or slightly increasing.
The major source of imported PCB's is Italy, from which
decachlorobiphenyl made by Caffaro is imported by one
company for use in investment casting waxes. This
constitutes 80 to 90 percent of the imports; the other 10
to 20 percent originates in France (Prodelec) and is used
103
-------
VENT
8IPHENYL
t
1
_,.-
? *'
A AIR * AIR
COOLER U 0, TwMFICATIOII
11 I
CRUDE
BATCH AROCLOR AROCLOR
CHLORINATOR g,HCIGAS SCRUBBER ^
\ i
11
UtlHI^ I dl 1
„ J
A|R SCRUBBER
If J A'B 2 ¥
BLOWER to RAW AROCLOR
* TANK * STOftAut
Figure 1. Preparation of crude chlorinated biphenyls Monsanto Krummrich plant.
S
STEAM
i .. , . .-- fc. H n WAena
RAW ^ GAS FIRED
AROCLOR RETORT
|Hlo
VACUUM OVERHEAD SHELLS TUBE ^ ^
P DISTILCATION CONDENSER
4 BOTTOMS j
i NONCONTACT
iCI, AIR*. HCI TO PURIFICATION ^ COOLING WATER
w • r^ A|R TO HJ° I i
» » 1 1 IAIWAII 1
-------
VAPOR FROM JET EJECTORS
EXHAUSTS FROM THE SCRUBBER
SURFACE AREA EVAPORATION (IN GENERAL)
AIR
CONDENSATE FROM STEAM EJECTORS
NONCONTACT COOLING WATER
SCRUBBER LIQUOR
TO
SEWERS
MONTARS
BOTTOMS FROM SEPARATOR SUMP —
COLLECTION FROM ALL DRIP PANS
INCINERATION
RAPS FOR CLEANING
FLOOR DRY
SPENT FILTER PAPERS &
FULLERS EARTH
LANDFILL
Figure 3. Nonproduct PCB discharges at Monsanto's Krummrich plant.
in semiclosed heat transfer applications. Until recently
RGB's were used in some U.S. built mining machines, but
this use has been discontinued.
In the Monsanto process, RGB's can be released to
the environment through the sources listed on figure 3.
Waterborne discharges of RGB's at this plant have been
reduced greatly over the past few years, and are now
below 1 pound per day, according to Monsanto.
Capacitor and Transformer Production
Producers of capacitors and transformers utilize
essentially all of Mqnsanto's domestic sales of RGB's.
About 70 percent of the usage is in capacitor produc-
tion, and, of this total, roughly half is for small capaci-
tors and half for large capacitors. Lists and locations of
capacitor and transformer producers are presented in
tables 1 and 2, respectively.
Transformers containing RGB's comprise only about
5 percent of the U.S. transformer market, and are used
only where safety and reliability are of prime impor-
tance. On the other hand, about 95 percent of capacitors
made in the United States utilize RGB's. According to
General Electric, about 100 X 10* capacitors containing
RGB's are made in the United States yearly, most for
first-time use in products. Life expectancy for capacitors
is over 10 years for lighting applications and over 20
years in electric utility service. Life expectancy of trans-
formers containing RGB's is over 30 years, and some
135,000 have been put into service since 1932 (virtually
all are still in service).
The steps involving RGB's used in the manufacture
of capacitors and transformers include filtration of
RGB's, filling (under vacuum), removal of excess RGB's,
sealing of units, and heat and electrical testing. Sources
of nonproduct discharges of RGB's are roughly similar
for capacitor and transformer production plants, and are
listed in table 3.
Most of the in-plant RGB wastes which reach water
streams originate in the filling area. A brief description
of the various filling processes is presented below.
Small capacitor bodies, each containing a machine-
105
-------
Table 1. U.S. transformer manufacturing
industry using RGB's
Company name
Location of the plant
Westinghouse
General Electric Company
Research-Cottrell
Niagara Transformer Corp.
Standard Transformer Co.
Helena Corp.
Hevi-Duty Electric
Kuhlman Electric Co.
Electro Engineering Works
R.E. Uptegraff Mfg. Co.
H.K. Porter
Van Tran Electric Co.
Esco Manufacturing Co.
South Boston, Va.
Sharon. Pa.
Rome, Ga.
P1ttsf1eld, Mass.
Flnderne, N.J.
Buffalo, N.Y.
Warren, Ohio
Medford, Oreg.
Helena, Ala.
Soldsboro, N.C.
Crystal Springs, M1ss.
San Leandro, Calif.
Scottsdale, Pa.
Belmont, Calif.
Lynchburg, Va.
Vandalia, 111.
Waco, Tex.
Greenville, Tex.
Table 2. U.S. capacitor manufacturing
industry using PCB's
Company name
(In order of PCB's usage)
Location of the plant
General Electric Company
Aero vox
Universal Manufacturing Corp.
Westinghouse Electric Corp.
Cornell Oublller
P.R. Mai lory ft Co., Inc.
Sangamo Electric Co.
Sprague Electric Co.
Electric Utility Co.
Capacitor Specialists, Inc.
JARD Corp.
York Electronics
McGraw-Edison
RF Interonics
Axel Electronic, Inc.
Tooe Eteutschmann Labs.
Cine-Chrome Lab, Inc.
Hudson Falls, N.Y.
Ft. Edward, N.Y.
New Bedford, Mass.
Bridgeport, Conn.
Totowa, N.ij.
Bloomington, Ind.
New Bedford, Mass.
Waynesboro, Tenn.
Plckens, S.C.
North Adams, Mass.
LaSalle, 111.
Escondldo, Calif.
Bennlngton, Vt.
Brooklyn, N.Y.
Greenwood, S.C.
Bayshore, L.I., N.Y.
Jamaica, N.Y.
Canton, Mass.
Palo Alto, Calif.
106
-------
Table 3. Sources of nonproduct
discharges of RGB's
Source
Type of effluent/
typical disposal
Vacuum pumps
Evaporation and
ventilation
Transfer spillage
Vacuum pump cooling
water or condensate
(steam jet)
Personal hygiene
Reject products
Floor and equipment
cleanup wastes
Drip pan collection
Filter media
Air
Air
Water
Water
Water
(Municipal Sewer)
Landfill
Landfill
Incineration
Landfill
wrapped helix of alternating paper and aluminum foil,
are placed in a chamber, the chamber is evacuated, and
prefiltered dielectric oil is introduced until it covers the
capacitors. The vacuum assures that the paper will be
well soaked (impregnated) with the fluid.
After the filling operation the vacuum is released,
excess fluid is removed to a holding tank, and the capaci-
tors are sealed and then deoiled. Then they undergo
heating electric tests and, if specifications are met, are
packaged. Reject capacitors and, in many cases, solid
wastes containing RGB's are landfilled.
Large capacitors are produced similarly, although
some differences can be observed:
1. Large capacitors (over 2 to 3 Ib of RGB's) are
typically filled through a small fill hole, while
the fill tank is under vacuum. Large capacitors
may be filled separately or flood-filled in a
chamber. Some plants use a multicell "carou-
sel" arangement where loading and unloading
occurs at one station, and the capacitor(s) in
each cell are progressively dried, evacuated,
filled, and the fluid drained from the cell at
stations along the carousel.
2. Following the filling operation, the fill holes in
the large capacitors are sealed or plugged with
solder, deoiled, and then tested prior to packag-
ing and shipment.
Transformer filling is very similar to the filling of
the larger capacitors, but transformers are all filled
individually. Individual filling appears to generate less
waste RGB's from spills, drip, and deoiling operations. If
a transformer does not meet test specifications, the fluid
is drained, filtered, and returned to the supply tank, and
the windings assembly and other parts are inspected to
identify the cause. Once repaired, the transformer
reenters the assembly line.
Investment Casting Process
Imported decachlorobiphenyl (deka) is used as a
filler for investment casting waxes; the estimated yearly
usage is about 400,000 Ib, some of which is in exported
waxes. In investment casting, a pattern is made of the
wax and a ceramic mold is formed on the wax. The wax
is melted out, and the mold, after baking out in a
furnace, is ready for use. The wax used to form the
pattern contains about 60 percent used wax and 40 per-
cent virgin pattern wax. Significant losses of RGB's to
the atmosphere can occur in the melting out process and
in the furnace. Used wax can possibly be reclaimed, but
most appears to be landfilled. Polychlorinated triphenyls
are also used as pattern wax fillers.
107
-------
PCB DISPOSAL, RECLAIMING, AND TREATMENT
Thomas E. Kopp*
Abstract
The Environmental Protection Agency in 1975
sought information about the uses, disposal, and effects
of PCB's from 84 purchasers and importers of PCB's.
Responses indicate that while PCB's were formerly dis-
posed of in landfills, high-temperature incineration is
now prevalent. There is no proven technology for re-
moval of PCB's from water, and emphasis is on prevent-
ing production-line PCB's from entering waste water.
EPA is presently formulating criteria for ambient PCB
levels in water and is developing a new toxic effluent
standard.
On August 16, 1975, the Office of Enforcement,
EPA, sent out 84 letters (figure 1) to companies in the
United States that purchase PCB's from Monsanto, to
those that import them, and to others that may be users.
This letter has been modified to include polychlorinated
terphenyls, PCT's, both because of their similar structure
and because they are a type of chemical that we will
have evaluated in the whole program of PCB's. This
letter concluded with four pages of questions which
covered the uses, importation, reclaiming, disposal of
PCB's (figure 2) and which concerned effluents, trans-
portation, spills, health and environmental effects, and
other data the companies had on file (figure 3).
Since then, we have received 83 responses and we
are in the process of evaluating and assembling the infor-
mation into a useable form for making decisions within
the Federal Government. This information will be made
available to the public and to local and State govern-
ments. This information will be handled in accordance
with the confidentiality requested by the companies and
the Trade Secrets Act.
Starting in 1972, industry had developed a standard
for handling and disposal of PCB's (figure 4). In 1974,
this standard was finalized and published. It covers the
following points (figure 5): housekeeping, disposal,
effluents, analytical methods, and several other impor-
tant areas. This is a voluntary standard for industry and
for the Federal Government. We encourage the imple-
mentation of this standard support by everybody and
also support the proposal by the National Electrical
'Environmental Protection Agency, Office of Toxic Sub-
stances (WH-557), Washington, D.C.
Manufacturers Association to revise and update it in the
near future.
Disposal of PCB's has historically been to the local
landfill site or to a scrap oil dealer. Since the concern
with the environmental problems associated with PCB's
has become evident, industry has developed several ways
of disposing of its PCB waste (figure 6). High-tempera-
ture incineration is the most effective way we know
today because it will completely destroy PCB's. The
other methods are only to contain the material and not
to let PCB's get out into the environment.
In Canada, there is a study going on about which we
have little knowledge (figure 7). It appears to be a
method by which PCB's may be reclaimed after their
useful lives.
On Thursday, December 27, 1973, EPA issued its
proposed toxic pollutant effluent standards under Sec-
tion 307a of the Water Act. During the hearings in May,
1974, effluent treatment was discussed (figure 8). West-
inghouse stated that "A review of techniques for re-
moval of materials such as PCB's from the water has
revealed that no commercial operation is now in effect.
Furthermore, there is no proven technology on which
such a technique might be based." General Electric
stated that "The control of PCB's from current produc-
tion is basically a containment process. Water is not an
essential component of ihe manufacturing process, so
the problem is not one oi removing a contaminant from
an aqueous process stream, but of preventing the adven-
titious loss of PCB's from the production line to a waste
water line." Monsanto stated for its production facility
that "the bathtub approach, which really involves pav-
ing, curbing, ^isolating the drains, ... etc.," is the only
known method for treatment.
We are basically at the same place today as we were
in May of 1974. As EPA develops its reproposed toxic
effluent standard, which should be published the first
half of next year, we will be looking at carbon absorb-
tion, reverse osmosis, and ozonation.
EPA is almo.st ready to send out for interagency and
State review of the Criteria for Water Quality, Section
304a of the Water Act (figure 9). This is not a rule-
making procedure so it does not have to go through
hearings and rulings. This is the ambient level which we
desire will not be exceeded in the Nation's waters.
There have been 20 spills identified at this time
which have involved PCB's (figure 10). Only six of these
were reported to EPA, and only over these did we have
any control during the cleanup. There is only one out of
108
-------
? I
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C. 20460
ftUG 1 6
OFFICE OF ENFORCEMENT
Gentlemen)
Recent governmental sampling data indicate the presence of
Polychlorinated Biphenyls (PCBs) and comparable chemical substances
in the air, in water bodies, and in fish in several areas of the
country. In order to determine the nature and extent of the possible
adverse effects resulting from the presence of PCB compounds in the
environment, the Environmental Protection Agency (EPA), in cooperation
with other federal and State agencies, is attempting to determine the
sources and amounts of PCBs entering the environment. It is important
that this effort be carried out without delay.
It is our understanding that your company; handles PCB compounds
or mixtures or comparable chemical substances in its operations, I
am therefore requesting, pursuant to the authority provided by
Section 308 of the Federal Water Pollution Control Act, as amended,
33 U.S.C. 1318, and Section 114 of the Clean Air Act, as amended,
42 U.S.C. 1857c-9, that your company furnish EPA with information
pertaining to your use and handling of PCBs and comparable chemical
substances. In addition to a general description, which should include
information as to sources, quantities, uses, and ultimate disposition,
you should respond in detail to the enclosed questions. If any question
is not applicable to your company or operations, please so Indicate by
responding "not applicable."
The information requested herein must be provided notwithstanding
its possible characterization as .confidential information or trade
secrets. Should you so request, however, any information (other than
effluent or emission data) which the Administrator of this Agency
determines to constitute methods or processes entitled- to-protection
as trade secrets will be maintained as confidential, pursuant to
procedures specified in 40 CFR Part 2.
Figure 1. Letter from EPA to purchasers, importers, and users of RGB's.
109
-------
Within 14 days of receipt of this letter, your company must
provide all Information concerning your current status and activities
and covering the twelve month period immediately preceding receipt of
this letter.
Within 30 days following receipt of this letter, your company
must provide all information for all of the prior years indicated.
The information required herein should be sent directly to
the address indicated below. If you have any questions you may
cell the person indicated below or Mr. Blake A. Biles of our office
at (202) 755-8731.
We appreciate your prompt cooperation in this matter.
Sincerely yours,
Stanley W. Legro
Assistant Administrator
for Enforcement
Enclosure
Regional Contact:
Mr. Richard O'Connell
Director, Enforcement Division
Environmental Protection Agency
100 California Street
San Francisco, California 91111
Telephone: (415) 556-0102
Figure 1. Letter from EPA to purchasers, importers, and users of PCB's (con.).
110
-------
^•^
•o
V
3
C
•rt
4J
B
O
O
**s
.
address of each source from
ach PCB compound or mixture,
mpound or mixture obtained from
•o oi o
B 0
M 13
oi m
01 B O
B -rt P,
10 CO
B w x
x ti
01 0 CO
X 01
t> X
B MH
4-1 tO 0
u ex
3 B 4J
•O O B
O CJ 3
h 0
ex M B
3 10
X 0
U X 01
CD X
01 X -u
CJ
rl -rt 13
O X B
tn s a
•
u
s
41
u
IH
3
O
m
X
CJ
to
01
of your company's facilities
ncludlng production facilities
ets), and the amount of each
ach facility.
VI rH 41
X ^ *J
0 3 X
CO CO O 60
01 4-1 3
U rH O
MH 3 M rl
O 13 CO X
O 4J 4J
10 rl 41
10 CX IH U)
01 41
K X 13 4J
13 ej B 3
•O 3 CO JO
CO CO -rt
01 rl
•O 01 rH 4J
E rH CO CO
CO t» CO iH
., S .2 "°
M to rH
B X 0 4-1
CO X U
B X S 3
CJ T3
41 iH 13 O
X X E rl
H s co ex
•
13
customer of each product, and
tained by each customer from
products list only the total
each facility and the total
x *->
X O rl M
CJ 01
to 4J B «J
41 CJ 3 U
3 tn 3
MH 13 C "0
O O O O
rl 0 H
mo, c.
n IH
01 X 0 X
M o m o
TJ CO CO
•O 0) 01
to
MH XMH
13 O 4-1 O
B -H
CO 4-1 rH B
E -rt O
CiV 3 U iH
E o a 4J
CO B MH 0
B CO 3
X -a
Ol 4) O O
X X CO rl
H v oi ex
.
01
provide the name and address
products.
4J M
O 01
E g
o to
Q E
0
O
*
CO MH
rl 0
01
B M
O 01
•" e
to o
3 4J
CJ CO
3
MH Cl
O
X
rl CJ
01 CO
X 01
g
3 MH
E 0
rl
O
CO MH -
4-1 ft
vl -r-.
01 CM
C W rH
•rt 'J
3 -
X-0 CM
B O r-.
CO rl OS
CX CXrH
B
O CO «
O 4-1 rH
•rt r^
rl CT»
3 0 rH
0 4J
X E MH
•H O ••
x m
X B rl I--
O CO Ox
13 v| 41 rH
0) 4J X
CO CO MH
3 rl X 0
41
K
3
4J
X
•rt
B
rl
O
•0
B
3
O
!•
o
o
«
u
cu
CJ
CO
01
^4
o
u.
.
O cj
CX CO (0
rl 4) rl
O 41
CJ 60 4J
C.' E M
•rt -H CO
rl 3
rl 3 O-
O 13
MH O
- Jt
B X 4J
CO 4J
X -rt 4J
4J rH W
•rt H
l-l CJ -rt
O) CO MH
X MH
4-1 01
O XX
E "
co co
B CXT3
O B B
•rt 0 CO
4-1 U
n) —
rl X -3-
41 cj r-
ex co cy*
O 41 rH
41
CO
3
_r*
CJ
CO
01
MH
O
B
O
•rt
4J
CX
•rt
rt
CJ
CO
01
•o
^J
CO
of each PCB compound or mixture
4-1
B
3
O
E
CO
rH
CO
4-1
O
4J
01
X
4J
41
CO
3
CJ
to
01
rl
O
.
.0
ress of each source from which
B compound or mixture , and the
r mixture obtained from each
•o o o
•O pj
CO 13
X E
•O 0 3
B cO O
ca oi cx
E
41 13 O
E 01 U
CO C
E -rt (P
to o
41 4J A,
X .n
4-1 O X
u
Ol X CO
to B 01
3 co
X E "o
CJ O
CO U 4J 41
Ol B CJ
rl 3 rl
rl 3 0 3
O O E O
(14 X QJ CO
.
O
•*
CO
rx
ox
rH
X •
B CM
to t-
cxox
B *rt
O •
rH
rl P»
3 CK
O rH
*MH
x o
•O «
cy 41 ..
B X"i
•rt r.
rt X en
rH CJ rH
U CO
41 41 MH
K O
CO
Ci C 10
rl 1-j rl
3 rl 01
4J 3 4J
X T) rl
•rt B
E - 3
x cr
rl 4J
O -rt 0
rH 3
•O -rt 4J
B 0
3 CO 4-1
O MH 10
CX rl
B X-rt
0 E MH
U CO
CX 4)
n B x
O 0 4J
(X: cj
•O
X X C
u u co
CO 0
01 01 •
•a-
rl rl r^
O O Ct*
(14 MH rH
.
compound or mixture reclaimed.
to
o
PH
X
o
CO
41
MH
0
4J
B
3
O
E
CO
rH
CO
4J
0
01
x
H
.
()
source from which your ycompany
tures, and the amount of each
ned from each source.
x -H
X -rt Cll
0 B *J
CO J3
01 IH O
o
MH O)
O 10 rl
U 9
(0 B 4-1
max
41 O -rt
rl CX B
•o B
13 O rl
to u o
•a « 13
BOB
to &i a
o
v 13 ex
E oi i
CO B O
B -rt O
a
oi u ca
X rO 0
t-i o en
•
_f»
"O
c
CO
fc
c
4—1
CO
4_i
t_
o
4t»*
LJ_
*•
S
.J
01
c
*~
c
CD
U
C
O yj
rrt
•. UJ
S2 o
vl
M
5
EH
M
X
OS
0
CO
o
o
s
u
s
£i
rJ
p*
n
V*
n
Q
g;
s
s
c
S4
r4
O
B.
» vl 01
3 4-1 CJ
B O 4)
CO H
X
B 13 60
CO B B
E 13
0 3 0
4J 01
f4 O H
S 4-1 ex
o ra
X X
4J rH
- B 01
rl 41 4J
41 (J CO
4-1 rl -H
4J 3 TJ
01 CJ 41
•rt E
rl E
tn 3 -rt
vl O
X X13
•u o
60 -rt
MH B rl
O -rt 01
Sex
ex oi x
•rt O 4J
41 E E
U O O
oi o E
V4
B 41
MH 0 >
O vl rH
4-> 01
co ra s
X B w
a C
13 O 01
MH X •
-» C 4J rl
rH -H 01
60 4J
E rH q 4J
vl i-H -rt 01
X CO H rH
•rt 0) > W
S -O O vl
•rt 0 X
> 4J
0 13
rl B MH
CX O O
X •
6 13
CO 41
frS
O 0
O -rt
13
M C
3 -rt
O
X CO
U
• «
rl 01
4J ^
4-1 rl
01 O
rH vH
H
to cx
•rt
X 01
4-1 X
4J
MH
O MH
0
4J
CX r-l
•rt rH
01 CO
U
41 M
rl O
MH
60
B a
•rt 0
O 4J
rH tO
•3 E
MH O
HH
CO*^
•O tM
rH
0 t«
01
B 13
•rt iH
X >
•rt IH
S cx
4J
B
1
^
rl .Q
O rH
13 tO
•O 01 CJ
B > -rt
3 01 E
O *rt 41
eXrH X
§41 CJ
X
O rl
rJ CO
CQ O rH
U -rt
cx, c B
S 3 -rt
O CO
01 B
CD ^ CO
CO
rl CO MH
X 01 O
CX CJ
B rl
01 B O
X 4J
4-1 CO CO '
X 01 01
rl 10 3 CO
0) 4J B
4-1 rH X
4-1 CO -rt 4}
41 O B 13
rH Tl CO
B -1 rl
to 41 O 4J
•rt X
X CJ CO MH
4-1 13 O
-1 E
MH rH 3 0)
O CO O >
CX-rt
m to E 4J
41 41 O O
CO 13 O 01
03 cx
CX rH CO B
rl O O 01
3 B CX: rl
CX Vl rl
41 -rt
o "oi
(U rl O 41
3 4-1 rl
4-> • 3
X 3 4-1
•rt O CO
B X B
rl -
3 rH
O I*.
X0\
r-l
X
X MH
O
•o
Ol rl t~4
r* E *^
O O C7*
rV CJ r-l
ture produced
x
•rt
E
rl
O
•O
B
3
O
!•
o
o
PQ
O
CM
X
u
B
01
MH
O
4J
B
3
O
CO *O
01
rH 4J
CO rl
4-1 O
0 CX
*J £
•*~4
CU
•
a
's facilities
x
E
to
CX
E
o
CJ
V4
3
0
X
MH
O
_rj
y
CO
41
MH
O
CO
CO
41
rl
13
13
CO
13
C
0
41
E
a
c
41
X
H
•
ft
uding production
, and the
rH ^*^
CJ B
E 4J
•rt 41
^^ rH
4-1
to 3
01 0
3 rH
4-1 -rt
x to
E oi
rl
IH
O 13
E
a a
•o
B 41
3 rH
O CO
(X a
§0>
rH
o o
X
o
E
41 CO
rH
•O CO
B 41
0 -rt
X »->
X rH
U -rt
•rt CJ
X 10
> MH
Ibuted through
IH
4J
B
•H
13
01
rl
4-1
X
•rt
rl
O
•a
B
3
O
I"
O
u
o
X •
0 X
CO 4J
41 vl
rH
MH Vl
O tl
CO
E
3 X
O U
E co
CO 01
•o
B
O
o
cx
o
m
o
CX:
X
CJ
CO
01
o
^
41
E
O
4J
to
3
CJ
X
U
CO
a
MH
O
n
«
41
rl
•a
to
•o
B
CO
01
E
CO
B
41
S
.
CJ
und or mixture
o x
&s
O rH
CJ -rt
CJ
O MH
CM
X
X O
U CO
CO 41
01
S
MH O
O rl
MH
4J
E rl
3 01
il
q} u
CO
s
4) »Q
V4
4J Q)
X E
E <0
4-1
rl ,0
0 O
your company
^
rO
T)
01
4J
CO
H
O
CX
rl
0
CJ
B
•rt
01
rt
3
4-1
X
rl
O
•O
B
3
O
CX
E
0
u
PQ
O
X
o
CO
01
rl
0
ring each
o quarters
3 S
•O 4-1
^ 4-1
X 10
4-1. H
•rt -rt
rH MH
•rt
U CU
CO X
MH 4-1
XT3
E B
to co
CX
§-
^t
CJ !-~
t^
X r-l
U
o -
Ol 01
IH O>
O rH
MH
•
— c^
to r^
4-1 OX
O rH
3
O rH
rl r»«
CXOv
rH
to •*
4-1 MH IO
•rt O r-r.
CTi
O rl rH
4J CO
B 01 MH
•rt X 0
.
4J
U
3
13
O
CX
X
o
CO
01
MH
O
B
o
•rt
4J
Vl
CJ
CO
01
.
CO
0)
o
T>
0)
4J
til
o
fr
o
CJ
B
4J
4
rH
CO
0 4)
4J rl
3
eu 4J
X X
4J vl
E
4J
U rl
3 0
•o
O 13
rl B
CX 3
O
X CX
CO O
V O
£8
rU CX:
»
,0
O c
Q. •-
o .E
-------
- w
X to 01 E 4J
o o id 4J o c
•TJ «H 4J UJ ra *w «H3
«l 1 XBO4JOK 4J O
4-1 cox to 3 1-1 to to o o to (j o> £
r4 CO O C*-'tO 4J U U CO
o ico-H p* cro-r-froritocy cj'ora
P. tn to JZ O 01 -H 14 01 00 01 O O *
CO E 4-t 3 ^ U to D rl r* Iw rl -H tfl
d -a id o oi 3 c cr-o -o ra m 4J -o c
id E n >« >» w TS o 1-1 01 -a x oi e E 'o •
to Id 4-1 O *4-l 0) CO O *H rH 4J ra U i-l M >H p
4-» 1^ to 3 VI W fO CO rH 4J 3
" O in O • C Id 4J « H I-l -O -r( IdOl COO
01 BK-OOIX4J BO-HOC-O 4-1 J3 • O C
to o id o p. 4j to oiiHUOJD'id E 4-» 4-1 o ,i4
rt 1-f X CO i-t O ^ O VIS Vv 01 Ol C fH
4-I104J rH p. COB 4J O 01 .C E E O) 01
to idoioicot-i ui o)X 064.1 COB-VJ
a> 4J 1-1 E 01 o c 3 o) G c E ra c w B to id
r-l" r1 3 1-1 Id oj O .O 3 -H 1-1 C **-! MM-lOO)
30UO4J4J4JU-lr4 :>, 10 O iH to B 10
4-1 E P.XB-H 4-1 01 W W 01 > tj -i-l 1-1 4J
X T1 10 i-l 01 rH .C X > 01 01 Id 4J C f: 0) > 4-1 O
1-* *0 E E V4 «H U B O CO J2 IJ tdO 014JB 01
C 3 Cd OlOld 3 i-t X i-l 3 »-l O ft rH 0. - *H
r-t n M v-i B D a x ri -u o -H 4J up tow
Mo 4-10*4-114-1 tJ &^ur: *u id ocoaiaio)
OB -H 4J .M CO to ft - C3 U OIX4J
T* E w -H o X >-i 4J nJ X
CO OT1B rH O T3 6 rH iJ T3U
•3 - E 01 Oi T3 >H rJ rt 01 - rH01O3
E >> "O 3 to to 4-j oo «
3-B o o 01 oi Ji to h to o c -a 01 cd n B
Old XP.XU-IJ >W rHOlIdWX-HldOl X X H -H X
P. P* 4-1 E 3 4-< O rH > rH T3 10 10 > TJ U
BE. OIO 1-ltO i-f 10 3 E M Vl O 3
X PQ *O -U *O COW M 4J p, 10 D -H C 01 01 3 E
U3 « P, X X 01 V< E M id 0 r-t .E -OOIX O
PL, O 01 4J-O4J to 3 i-l3fXOOIJ -10 Id i-t -H W H-l
>, J30I010JT34J -O4J Idra4J rHBC
X «-l O B M E TJ X 3XC03O0101C >\ 01 O -O
OE OH 3 Id-H 1H-HIHU4J 4J3 E J3 >-l -H 01
HO XX B B 0 S Pi E K to O a o in >
X rl B 3 0 01 O •£» B iHO-dE K CO «H
3 M-l O CO rl 1-t E r-l 1-t rl • T3 F^l Id U-lOCOOO
•H E 01 Id 4J IdO *^ O 4-1 01 *EJ '- O •OO>
x n •>-> -H co d > o) -a a) 3 c o c
J3 O P. XB4J COCO tOC001rH4-I.OIJt: COS -H
— i4EjOO»j Ot) B"OEOldco>4j OBOO
0)-O to to -HO EC OBEr>HBrH l-IJi P.-H 10
•OB oo-04-ip. 0)3 i-isoaoaot) 4J EIMO
Oco mujoicoio BO too-4.r-ip.4J>c p. 3 o IH IH
J5 01 4J4-1B O. CdPiM r-lCOBCd 1HOUU4J
«j* ^o)r^t-iid oiE oE>>*Or>\i-i to ^ at to
v >, XOOM xo oocoioto •- o cacxid
E.O •<4-ip.p,4J Hcj ocye/XC ^*H toxowcx
4J-HC4JrH OUOj
01" rHpaal QlMiH *Oi-IXT3
XO " • rHCJXCOCOIXldP, X*WCC
H4J cd jo •ocdid
.. •
• o
GO O\ *H
j
cd
CO «•
o -o
p. oi .n
m 4J c
rH 1-1 ra to 01 -w-a o
O-OCJ OCJ — C O i-l
" tO PL, P. B >"H 01 4J I)
>,X •» (O O 01 E-H J3 T~ 3 -H CO
6 0 r- CJ P.XX -H«> t*> -rHC^
OCdtT> PL. C04JCJ -OTH . 01 >MOI
E X -OEOJ -OB E- tUW
o to cj 1-1 olid HrH -js a
UOn cd xu-i CJP. O 014JX
"Mr-. 01 to -a o 3E «-i >> j:j-i
r4C7% 0101 T3C rWrW-UUw
3 -rH «M >>4J OU «IO OC
Q *-* O OlrHB* r4 P.3 C-ri
>>co- O3>> fXH B -Hto
OlCN 4J U^>O4J 3 COCO UM
>M-lr-- B OEE-4 OIO -H "D lOOJO
JDUCT> 3 Hcdto v<>< m 014J
HrH -O B P. 3 >>01 to a ^*
14Jtd iHE OXOI 4J>, -rHO 3,JtO
OP.- co 10 -H4J.E.C xja «c 4-)j«:
rH 0} 4-»*w.UCJ -H Bi-i XO*-»
T3VJr~ OfH COW CO E**-l COtO iH+JO
01 01 cr. p. ol o cx-a 01 o e C S
COXrH C04-1 OB H -OtO 1-1
O4J iH O rHjCCOr*^ OT3 H to V4V--4J
P,O<4-I *rJ4-l CJjh 01 TOO OB
COO Olid- *C1CO 4-1 r^Ol
•rin-i — >u oi j=oiaiu-i CO DOCJ coBE
•rJOrJtri OX 4-1 to O 3Ou CCO -*rJtO-U
cdr%. 4J ^M3 Oco 1-IV BP.CO
014J01C% T3 -O4JT3 P.M i-l -4-1 3 ^ 01
PB>^rH OfH rH XOI E*O T4.B OO4J
301 X id « in -H m o E o P.CJH
4-1 E X >M 4-1 to (n m g o 0X4 wo E
XOIOO01O O01P. O to O01TJ
•H > « e a. p.V4Vin « -^ h UAOI
BfHOltO CO tOrQOlH O*O ^HO -UE
Ol4XT< -HT3-O P^E iH — paS
to > & u o -o • -a ra -a « ^otoeouxo
OBB4-IQ 01 B01 X 4JEPiX
»w T3 3 U O- ~Ojt:i-l >>
-O heo 03 OE03 ;* «n os TH
BOI33U-I 4J IOP.U aioi TO oo o ooiu
3X*O«TO'OX"O EX CO COrH OOiH
O 4-1 Ovt-l3 >,rHtOHrH
r- O BXEXEOS O Ctoo Eroja
4J.V.3 0 4J 4JCd - - B4JIUI OJ=3
34-14-1 i-l CUM 01CCQM B*C?rH i-( 1-ftJP-i
OOi-t 4-i EO E OO OGlt~* ^M o) •uco
XrH4J p. oid< MEa. o-X eonlJ
p34Jl-lai 1-1 XXI XX T3 4_>.HrH JX4-I rJnaO
U n O ^ K OB O4J.CE Htfl WE -4J
CL, 3 O i-t CJ « 3 id O3 UfH> 4J « 00 B>>to
(M^M CO 01O 01-IdO OOrH THP.B OIC01
Xl4 01 CU 01O>P< tXOl 3Ei-IOId4J
CJ O S^. 01 T) ViE ^ *J E E M X COOE B Id
CO BX OO O -H V4-i o O h 01 O U O>H4J
01X144-1 •< CZ4O (X^COOO O-cd I-l 01 OOtO
UP. -O 3 M O
K H E -O OITHB 013B
O 3 O C • • • XOid XOO
U. «-^ .0 cd to JD o Hcor-j HXOco
•
T4
-rl
to
01
X
4-1
o
4_1
B
1-1
>-.
B
CO
a
E
o
CJ
01
X
4J
*M
o
f
c
Q
•H
to
3
00 JO
C i-l
•H M
e 4J
H u
0) n
O rr)
B
o
u o>
to
U 3
to *
01 - tO
CO C 01
to o to
O -H 3
P. 4,1 4-1
n x
3 B -H
o id E
X rH
0 M
X 01 0
O tJ
i-l 10
X. -t)
3 C B
03
E .-rl O
O 4-1 P.
i-l id 6
4-1 4J O
CO to o
B O
M an
o G u
*4H «H PH
c
^ -«-(
B 0
h O
01 V4 rH
x -u 10
4J O CO
O 3O
•o P.
rH O 10
TH to i-l
CO P.TJ
•a oi -o
B X E
to HO
c
< id
fH
J^
rH
CO CJ
B -H P3
O rH O
•H X P.
-CO 3
1-1 ^
E to cd
01 O 4J
B
K 0 O
O 01 0
4-1
CO CO JS
01 4-1 CJ
OO tO -ri
V4 X
« t) 3
X 01
0 4J .->
10 1^ V4
^ B li
•a P co
>-. 01 01
C X X
CO 4-1 4J
14-1 UJ O
O 0 4-1
B
B to i-l
0 to
iH 01 M
4J 4-1 O
1-t Cd
to 3 - •
O CO 03
CU O J* 0)
E J-' K J-i
O C 0 3
O H S 4-1
^^ X
to 4J 1-1
0 X B B
— E 01
•0 co E v«
B (X u o
to B cd
O 01 CO
5> o M -a
0 H C
.H (U 3
4J 01 p,
01 BE
x >> 5 o
f-l J3 CD O
•
.0
0)
,c
4-»
o
4J
p
•H
m
a)
J-.
3
4-t
x
-H
lu
o
tf.
*c
Ci
-1
C'
ir
Ci
o
£1
o
A,
<4.<
o
9J
(J)
L
cb
X
\
,-l
•>3
•rl
01
o
01
to
E
1-1
CO
01
to
3
4-1
X
1-t
E
o
to
•0
B
3
o
p.
o
a
o
U- I
0
to
B
0
1-1
4J
cd
to
4J
B
01
u
e
o
(J
•
o
.
4J
B
'B
,0
fc
g
)OI
CO
01
00
T4
Q
X
o
CO
1-1
•o
ts
B
CO
U-l
o
s
cd
01
to
4-1
CD
Q
-o
•o
c
a
e
cd
01
to
4J
n
a.
3
X
4-1
o
J3
a
k.
01
4-1
cd
3
•a
B
CO
a
01
hi
3
4-1
X
•H
E
to
o
CO
•o
B
3
o
g
o
n
o
Pi
B
1-t
CO
B
o
o
X
o
*H
X
3
^
B
cd
a.
E
0
CJ
01
X
4-1
>>
J
B
M
•H
n
41
X
4J
c
CO
01
kl
3
4-1
X
•H
e
to
o
to
•o
B
3
o
p.
o
o
m
rj
p ,
CM
0
to
B
0
1-1
4J
CO
>J
4J
B
01
o
B
o
u
01
60
to
cd
J3
rt CJ
01 CO
X i-l
4J -O
o
•T3
X B
SIB
c
00 O
6 -rt
iH 4J
? 3
•H X
01 iH
O V4
01 4-1
to en
. It
01 "O
4J>
CO CU
i-t X
O 4-1
01
M OO
P. B
tX 'H
CO C
t-l
T3 01
rH CJ
§g
3 p.
0
X 3
cd o
X
0>
X X
4-1 CJ
T-1
0 X
4J 3
B B
0 O
M -H
4-1 4J
•rj rt
•o to
cd o
M-l
B B
M i-l
>.
B
10
(X
o
u
a>
JS
•J
*4-<
0
0)
01
>J
a
tt)
X
4J
—
>%
B
id
p.
E
o
o
to
3
o
x
B
cd
J3
4-1 .
(A
X 01
01 0
X l-i
4-1 3
o o
CO
CO
01 T3
O B
l-i co
3
o to
CO to
0)
rS E
JO o
4J
to 10
Ol 3
••4 U
3
u n
X -
•H >,
E B
5
kl P.
0 E
CO CJ
•o
B rl
3 3
o o
§•*
0 60
1-1
» -o
O 3
P.4 rH
o
t-i B
0 i-l
fc
s
R
(/)
'•5
O)
c
'E
l_
s
22
o
CJ
C/3
CD
to
3
00
o
a.
o
*H
<
a.
LU
_Q
^
Q)
to
J—
^r
1 '
s
^3
o
t
CO
CD
p*
1 1
U—
^^
•H
c
0)
£
c.
o
.w
• •^
>
c
(H
•o
c
CD
J_J
r.
c
a
CJ)
.
CO
a.
JJ
3
o
CO
CO
H-*
-------
ANSI
C107.M974
American National Standard
Guidelines for Handling and Disposal of
Capacitor- and Transformer-Grade Askarels
Containing Polychlorinated Biphenyls
Secretariat
National Electrical Manufacturers Association
Approved January 9, 1974
American National Standards Institute, Inc
Figure 4. Cover of industry standard for
handling and disposal of PCB's.
113
-------
American
National
Standard
An American National Standard implies a consensus of those substantially concerned with its
scope and provisions. An American National Standaid is intended as a guide to aid the manu-
facturer, the consumer, and the general public. The existence of an American National Stan-
dard does not in any respect preclude anyone, whether he has approved the standard or not,
from manufacturing, marketing, purchasing, or using products, processes, or procedures not
conforming to the standard. American National Standards are subject to periodic review and
users are cautioned to obtain the latest editions.
CAUTION NOTICE: This American National Standard may be revised or withdrawn at any
time. The procedures of the American National Standards Institute require that action be
taken to reaffirm, revise, or withdraw this standard no later than five years from the date
of publication. Purchasers of American National Standards may receive current information
on all standards by calling or writing the American National Standards Institute.
Published by
American National Standards Institute
1430 Broadway, New York, New York 10018
Copyright © 1974 by American National Standards Institute, Inc
All rights reserved.
No part of this publication may be reproduced in any form,
in an electronic retrieval system or otherwise, without
the prior written permission of the publisher.
Printed in the United States of America
A1M1074/6
Figure 4. (con.).
114
-------
Contents SECT10N PAGE
1. Scope 7
2. General Information 7
2.1 General 7
2.2 Benefits 7
2.3 Risks 7
2.4 Alternatives 8
2.5 Interdepartmental Task Force on PCBs 8
3. Capacitor Guidelines 8
3.1 General 8
3.2 Capacitor-Grade Askarel 9
3.3 Plant Housekeeping and Employee Safety 9
3.4 Control of Water Effluents 11
3.5 Scrap-Disposal Procedures 12
3.6 Labeling 13
4. Transformer Guidelines 13
4.1 General 13
4.2 Specific Guidelines 15
5. References 17
5.1 References to the Text 17
5.2 General References 17
6. Revision of American National Standards Referred to in This Document 18
Table 1 Typical Properties of Aroclor 1016 9
Appendixes
Appendix A Disposal Services 19
Appendix B Analytical Procedures and Laboratory Service Organizations 20
Bl. General 20
B2. Laboratories 20
B3. An Analytical Procedure for the Determination of Airborne PCBs 20
B4. Analysis of Water and Sediment for PCBs 31
Figures
Fig. Bl Aroclor 1016 Electron Captiwe Chromatogram 21
Fig. B2 Comparison of Electron Capture Chromatograms for
Aroclor 1221, 1242, 1248, 1254, and 1260 22
Fig. B3 Aroclor 1221 Electron Capture Chromatogram 23
Fig. B4 Aroclor 1242 Electron Capture Chromatogram 24
Fig. B5 Aroclor 1248 Electron Capture Chromatogram 25
Fig. B6 Aroclor 1254 Electron Capture Chromatogram 26
Fig. B7 Aroclor 1260 Electron Capture Chromatogram 27
Fig. B8 Sampling Train 28
Fig. B9 Calculating Column Efficiency 30
Fig. BIO Calculating the Tailing Factor 30
Figure 5. Points covered in industry guideline
for handling and disposal of RGB's.
115
-------
DISPOSAL METHODS
THERMAL INCINERATION FOR LIQUIDS
Incineration at 2200-2600°F with a retention time of
1-1.5 seconds. Venturi scrubber eliminates possibility
air contamination. Cooling water is recycled and routine'ly
checked for contamination. High aqeous waste are also
incinerated by side injection into the system.
PHYSICAL CHEMICAL TREATMENT FOR HIGH AQUEOUS WASTE
Waste are pH controlled, settled, and filtered and passed
through two carbon beds in series. Water passed through
has invariably met at specs. No detectable PCB's (less
than 2 ppb).
SOLIDIFICATION
Solidification means solidifying liquids and sludges using
a silicates-cement powder technique. After solidification,
materials are disposed of in lined scientific landfill.
GELLATION
Liquids and sludges are polymerized or gelled in steel of
fiber drumswhich are placed in a scientific landfill
SCIENTIFIC LANDFILL
Series of reinforced hypalon or reinforced chlorinated
polyethylene lined cells in clay oil areas into which
solid, sludges, stabilized chemicals, gelled liquids,
solidfill liquids or sludges are disposited. A sump at
the bottom of each cell recycles leachate to the physical-
chemical treatment plant. A three-dimensional inventory
is kept of waste in each cell. Surrounding ground and
surface waters are routinely checked each month.
Figure 6. Methods developed by industry for
disposal of PCB waste.
116
-------
AS A FUEL TO PRODUCE LOW ALKALI CEMENT POWDER
In Canada, there is being pioneered the concept of
utilizing chlorinated chemical waste as a fuel and a
supply of chlorine to produce low alkali cement powder.
The waste material is fed into the fire box to supple-
ment the fuel oil and burns at 2200 - 2600° f.
The waste breaks down to water, carbon dioxide and
hydrochloric acid. The acid neutralizes the potassium
hydroxide present in the raw feed thus reducing the
alkali in the cement powder. The cement kiln is
perhaps the safest way to destroy PCBs. The temperature
and retention time, approximately 16 - 18 seconds,
are sufficient to reduce the PCBs.
This test program is currently under way at the
St. Lawrence Cement Co. in Hamilton, Ontario, Canada.
Participants are: Ontario Water Resources Commission
St. Lawrence Cement Company
Chem-Trol Pollution Services, Inc.
Figure 7. Description of Canadian PCB study.
117
-------
Ho. 947—Pt. II 1
THURSDAY, DECEMBER 27, 1973
WASHINGTON, D.C.
Volume 38 • Number 247
PART II
ENVIRONMENTAL
PROTECTION
AGENCY
WATER PROGRAMS
Proposed Toxic Pollutant
Effluent Standards
Figure 8. EPA proposed toxic pollutant effluent standards.
118
-------
35388
ENVIRONMENTAL PROTECTION
AGENCY
[40CFRPlrtl29]
WATER PROGRAM
PropoMd Toxic Pollutant Effluent
Standards
Notice is hereby given that the En-
vironmental Protection Agency, pursuant
to the authority contained in section
307 (a) of the Federal Water Pollution
Control Act (the Act) as amended by the
Federal Water Pollution Control Act
Amendments of 1972 (33 U.S.C. 1251 et
seq.) proposes a new Part 129, setting
forth proposed effluent standards for
toxic pollutants Included in the list ol
toxic pollutants required by section
307(a)(l).
Section 307(a> (2) provides as follows:
Within one hundred and eighty days after
the date of publication of any list, or revision
thereof, containing toxic pollutants or com-
bination of pollutants under paragraph (1)
of this subsection, the Administrator, In ac-
cordance with Section B53 of title S of the
United States Code, shall publish a proposed
effluent standard (or a prohibition) for such
pollutant or combination of pollutants which
shall take Into account the toxlclty of the
pollutant, its persistence, degradablllty, the
usual or potential presence of the affected
organisms In any waters, the Importance of
the affected organisms and the nature and
extent of the effect of the toxic pollutant on
such organisms, and he shall publish a notice
for a public hearing on such proposed stand-
ard to be held within thirty days. As soon as
possible after such hearing, but not later
than six months after the publication ot the
proposed effluent standard (or prohibition),
unless the Administrator finds, on the record,
that a modification of such proposed stand-
ard (or prohibition) Is justified based upon a
preponderance of evidence adduced at such
hearings, such standard (or prohibition)
shall be promulgated
These proposed regulations establish
effluent standards for the toxic pollutants
listed below:
1. Aldrin (l,2,3,4,10,10-hexachloro-l,4,
4a,5,8,8a-hexahydro-l,4-endo - exo - 5,8-
dlmethanonaphthalene).
Dleldrin U,2,3,4,10,10-hexachloro-6,7-
epoxy-l,4,4a,5,6,7,8,8a - octahydro - 1,4-
endo-exo-5,8-dimethanonaphthalene).
2. Benzidine and its salts (4,4'-diaml-
nobiphenyl).
3. Cadmium and all cadmium com-
pounds.
4. Cyanide and all cyanide compounds.
5. DDD (TDK) [l,l-dichloro-2,2-bis-
(p-chlorophenyl) ethane and some o,p'-
isomerl.
DDE [l,l-dichloro-2,2-bis(p - chloro-
phenyDethylenel.
DDT [l,l,l-trichloro-2,2-bis(p-chloro-
phenyl) ethane and some o,p'-isomer].
6. Endrin (l,2,3,4,10,10-hexachloro-6,
7-epoxy-l,4,4a,5,6,7,8,8a-octahydro - 1,4-
endo-endo-5,8-dimethanonaphthalene).
7. Mercury and all mercury com-
pounds.
8. Polychlorinated biphenyls (PCB's)
mixtures of chlorinated biphenyl com-
pounds with various percentages of chlo-
rination.
9. Toxaphene (chlorinated camphene).
The criteria and rationale employed to
select these pollutants were summarized
PROPOSED RULES
in the FEDERAL REGISTER- Notice of Sep-
tember 7, 1973, vol. 38, No. 173, page
24342.
The following is a summary of the
basis and purpose of the effluent stand-
ards proposed in this Part: The four
basic factors considered in setting the
standards were lexicological data, hydro-
dynamic data, ample margins of safety
and calculations of the acute and chronic
limitations for the standards. The pri-
mary basis for toxicological considera-
tions came from the Water Quality Cri-
teria which were proposed in October (38
FK 29646 et seq., Friday, October 26,
1973). These criteria were based in part
on a report by the National Academy of
Sciences and the National Academy of
Engineering entitled "Water Quality Cri-
teria", 1972 which is currently being pub-
lished by the Environmental Protection
Agency. The toxicity of the pollutants on
the list, their persistence, degradabillty,
the usual or potential presence of the af-
fected organisms in any waters, the im-
portance of the affected organisms, and
the nature and extent of the effect of the
toxic pollutant on such organisms, were
considered in the establishment of the
Water Quality Criteria upon which these
standards are based.
Water Quality Criteria published pur-
suant to section 304(a) of the Act are
those concentrations which are accept-
able in the receiving water body. The
criteria were developed to protect a va-
riety of water uses including industrial,
agricultural, recreational, propagation of
fish and wildlife, aesthetics and potable
water supplies. The protection of flsh
and wildlife and potable water supplies
was the most sensitive of the fresh water
usages. In estuarine and marine waters,
the protection of flsh and wildlife gen-
erally yielded the more restrictive
recommended limitations. The criteria,
as proposed, were designed for both
acute and chronic toxicological protec-
tion. Since protection against chronic
effects requires more stringent criteria,
the proposed Water Quality Criteria were
devised from data or calculation designed
to afford chronic protection.
Because proposed Water Quality Cri-
teria utilize both acute and chronic tox-
icity data to derive a single acceptable
ambient water concentration, it was nec-
essary to utilize the data upon which
the criteria were based to calculate pro-
posed standards which provide for pro-
tection against both acute and chronic
toxicological effects.
To avoid the effects of acute toxicity
it was determined that organisms need
not necessarily be protected at all times
from concentrations exceeding the pro-
posed Water Quality Criteria, since brief
exposures to higher concentrations may
be tolerated. It may be assumed that
most mobile organisms will not remain
in the immediate vicinity of the outfall
for as long as the usual 96-hour test
period. Thus, for protection in the im-
mediate vicinity of the outfall, a concen-
tration of one tenth the 96-hour LCM
was determined to provide an ample
margin of safety. (The 96-hour LC-» is
that concentration derived from labora-
tory tests in which 50% of a group of
test organisms survive after 96 hours of
continuous-exposure to a pollutant.) In
order to achieve a concentration in the
vicinity of the outfall which does not ex-
ceed the acute threshold, the discharger
may either discharge the acute toxicity
concentration and provide immediate
diffusion through appropriate flow de-
vices or reduce the concentration below
the acute threshold.
To avoid the effects of chronic tox-
icity, an effluent standard is provided
which is designed to ensure that, in most
cases, the proposed Water Quality Cri-
teria, which are intended to provide pro-
tection from chronic effects, are not ex-
ceeded over the long term in the receiv-
ing waters. This is achieved by limitation
of the total weight of the pollutant which
. can be discharged into receiving waters
of given size. To provide an additional
margin of safety, the allowable weight
discharged per unit of flow was reduced
by safety factors designed to compen-
sate, in part, for non-point sources of the
pollutant, multiple discharges in a small
area, Industrial growth, and the differ-
ence in water storage times among lakes,
estuaries, streams, and coastal waters.
The standard for each type of receiving
water is expressed as a number which,
when multiplied by the rate of receiving
water flow, yields the allowable weight of
discharge of the pollutant per day from
any facility.
These standards are not Intended,
however, to assure that Water Quality
Criteria would be achieved in all receiv-
ing waters, since standards sufficiently
restrictive to attain water quality cri-
teria In (for example) small streams with
extraordinarily large clusters of dis-
chargers, would be overly restrictive for
the usual case. These special "worst-
case" situations are to be handled by
the application of water quality stand-
ards through waste load allocations
under section 303 of the Act. The result-
ing allocations may then be used to
establish effluent limitations, if. neces-
sary, more stringent than the effluent
standards set forth herein. Those limita-
tions would then be Incorporated into
permits issued under section 402 of the
Act.
Since there are no proposed Water
Quality Criteria for benzidine, a different
methodology was required for the deri-
vation of an effluent standard. The
methodology employed was designed to
determine a level of discharge which
would result in an acceptable level of risk
exposure to man. the primary affected
organism. Effluent standards for benzi-
dine were derived by the extrapolation of
laboratory test animal data using con-
servative statistical methods, and are
btfsed upon a calculated level of risk of
less than one case of tumor induction per
million people exposed over an entire
generation to drinking water from sup-
plies derived from waters contaminated
with the maximum permitted concentra-
tion of benzidine. It is recognized that
certain inadequacies exist in the avail-
able data on which the benzidine stand-
ard is based. Therefore, it is reasonable
to assume that these standards could be
revised in the future. The Environmental
FEDERAL REGISTER, VOL. 38, NO. 247—THURSDAY, DECEMBER 17, 1973
Figures, (con.).
119
-------
NOTICE
This document is a preliminary draft.
It has not been formally released by
EPA and should not at this stage be
construed to represent Agency policy.
It is being circulated for comment
on its technical accuracy and policy
implications.
POLYCHLORINATED BIPIIENYLS
CRITERION:
. 001 ug/1 for freshwater and marine aquatic life
and for consumers thereof.
Figure 9. Preliminary draft of EPA
standard for water quality.
120
-------
DATE
6/ 9/71
10/12/71
31 8/72
3/ 8/73
8/ 9/73
9/73
I/ 6/7lt
II/7I*
5/20/71*
9/ism
Unknown
7/ 5/71
1/16/7M
11/18/71*
12/6/71*
12/27/71*
1/22/76
8/9/75
CIRCUMSTANCES
Drums containing 6,600 Ib
started to leak en route
Drum leaking en route,
sent back
Truck accident, 5 trans-
formers
Truck en route developed
leak
Truck accident
Transformer leak
Transformer leak
Transformer leak
Truck accident
Transformer fell into
Duamish River
Transformer leak
Transformer leak
RR
Transformer leak
RR
Truck accident
Truck accident
Truck accident
Truck accident
Leaking drum on dock
CITY
STATE
En route
En route
Roanoke
Rapids, NC
Kingston,
Tenn.
Havana,
111.
Anderson,
Ind.
Tuscaloosa
Ala.
Louisburg.,
Kansas
Bedford ,
Ind.
Seattle,
Wash.
N.J.
Unknown
Stanford,
Conn.
Bet. Phil.
S Paoli,
Pa.
Trion, Sa
Erie, P«
Lawrence
Al
Rome* Ga
Charlestow
sc
AMOUNT
SPILLED
Unknown
Unknown
1000 gals
Inerteen
630 gal PCBs
MOO gal
15 gal
80-100 gal
60 gal
Unknown
283 gal
10-100 Ibs
10-100 Ibs
10-100 Ibs
130 gals
200 gall PCBs
630 galiFCGBI
67 gals PCBs
i SO gals
PCBs
AMOUNT
RECOVERED
Unknown
Nona
Unknown
11,500 drums of
contaminated soil
Unknown
Unknown
Unknown
Unknown
Unknown
70-90 gal
Unknown
Unknown
Unknown
2,300 drums of
contaminated soil
Unknown
U.SOO drums of
contaminated soil
132 drums of soil
5 drums of soil
METHOD OT
DISPOSAL
None
None
Unknown
55 gal sealed
in concrete
Unknown
Unknown
Unknown
Unknown
Unknown
Entombed in
titan missle
Unknown
Unknown
Unknown
Entombed
Unknown
Entombed
Entombed
landfill
COST
$1.7 millioi
Sma.ooo
$175,000
$275,000
$5,000
Unknown
REPORTED
TO EPA
No
No
No
Yes
Yes
No
No
No
No
Yes
No
No
No
Yes
No
Yes
yes
Yes
Figure 10. The 20 identified spills that have
involved RGB's.
121
-------
"OIL AND HAZARDOUS SUBSTANCE LIABILITY"
Sec. 311 of FWPCA, PL92-500, October 18, 1972
311(b)(2)(A) Designation of Hazardous Substances
Polychlorinated biphenyls PCB
Aroclor
P.olychlorinated diphenyls
311(b)(2)(B)(i) Removability Determination
"...cannot actually be removed."
311(b)(2)(B)(ii-iv) Rates of Penalty for Non-Removable
PCB's Category A, Unit of Measurement Ib - 1,$360/UM
311(b)(3) Non-Harmful Quantities
(being developed)
311(b)(4) Harmful Quantities
PCB's Category A, HQ in Ib - 1
311(f)(2) Small Facilities Liability Limitations
(being developed)
311(j)(l)(A) Methods of Removal
(being developed)
311(j)(l)(c) Prevention
(being developed)
Figure 11. List of subjects covered in proposed EEPA
regulation under Section 311 of the Water Act.
122
-------
the 20 in which RGB's reached the water. This is the stance Liability" (figure 11). At the present time, only
Duwamish River incident. The majority of the spills are four areas will be covered in the proposed regulation and
transportation-related. the other four sections will be following next year, we
EPA is finalizing its proposed regulations under Sec- hope.
tion 311 of the Water Act, "Oil and Hazardous Sub-
123
-------
SOURCES OF POLYCHLORINATED BIPHENYLS IN WISCONSIN
Stanton J. Kleinert*
Abstract
The past and present users of PCB's are discussed
and effluent sampling data are presented for municipal
wastewater treatment plants and industries in Wisconsin.
Data are also presented covering PCB levels in surface
waters, fish, sediments, and snow melt. A general assess-
ment of the PCB problem in Wisconsin is made with
comments concerning the need for further study and
regulation.
My report will summarize the work completed by
the Wisconsin Department of Natural Resources and
others to determine concentrations of PCB's in fish and
to identify discharge sources in Wisconsin. Our interest
in PCB's began in the late 1960's, when interfering sub-
stances were detected in the gas chromatograms of fish
being tested for DDT. Later we were to learn these inter-
fering substances were PCB's.
In 1970, the department collected fish samples
along the Mississippi River bordering Wisconsin. Analysis
revealed that fish from the Upper Mississippi River be-
tween Prescott and Pepin, Wisconsin, commonly exceed-
ed the Food and Drug Administration tolerance level of
5 ppm (ref. 1). During 1971, Lake Michigan fish were
collected and later tested in studies conducted by Dr.
Veith in a University of Wisconsin study (ref. 2). Mean
concentrations of PCB's expressed as Aroclor 1254 (wet
weight) in the fish ranged from 2.7 ppm in smelt to 15
ppm in lake trout. Subsequent studies confirmed the
presence of PCB's in fish in Lake Michigan and other
waters of Wisconsin (ref. 3).
The search for PCB's in water was also underway at
this time. Veith and Lee (ref. 4) sampled water from the
Milwaukee River in 1969 and sampled effluents from
selected municipal and industrial outfalls to the river in
1970. The analysis of water from the Milwaukee River
indicated that PCB's were present in the river from West
Bend to Lake Michigan and were being discharged
through municipal and industrial effluents. In 1971, 11
municipal wastewater treatment plant effluents in Wis-
consin were sampled by Dube, Veith, and Lee (ref. 5).
Nine of the plant effluents contained PCB's identified as
Aroclor 1254 and one contained Aroclor 1248. Studies
of the Cedarburg wastewater treatment plant indicated
'Chief, Surveillance, Wisconsin Department of Natural
Resources, Madison, Wisconsin.
that more than 70 percent of the PCB's coming into the
plant were removed during the treatment process and
comparatively high concentrations of PCB's were found
in the digester and primary settling sludges.
The department surveyed many municipal waste-
water treatment plant effluents in Wisconsin from 1972
through 1974. PCB's were detected in concentrations
exceeding .05 ppb (the detection level for screening pur-
poses) in more than half of the treatment plant effluents
tested, even where there were no suspected industrial
sources. In most cases, the discharge of PCB's was well
below 1 ppb and .01 pounds per day. However, the high-
er concentrations of PCB's were found in sewage treat-
ment plant effluents from industrial areas.
Tracing sources of PCB's reaching a large municipal
wastewater treatment plant is a difficult and time-
consuming task. The department is attempting to trace
sources of PCB's reaching treatment systems where the
final effluent exceeds 1 ppb. At the present time, we
know of only two municipal wastewater treatment
plants in Wisconsin which exceed 1 ppb—the Sheboygan
and Portage facilities.
The main source of PCB's being discharged to the
Portage treatment plant was found to be a facility that
had used PCB's in the manufacture of carbonless copy
papers prior to the summer of 1971. After ceasing the
use of PCB's and after repeated cleanings of the holding
tanks of the facility, the company substantially reduced
the discharge. Residuals still remain, however, in the
sewer system and the sewer sludges, resulting in an efflu-
ent of several ppb a1 the municipal sewage treatment
plant. We are continuing to check sources of discharge to
the Sheboygan treatment plant.
The department has checked effluents from iron
and steel foundries and aluminum foundries. The testing
has shown that the cooling water effluents from five to
seven aluminum foundries contained PCB's ranging from
11.5 to 335 ppb. Close investigation revealed the com-
mon source to be leaking hydraulic fluids containing
PCB's, which were used in die cast machines. We are
working with company officials to correct the problem.
PCB's have been found in the cooling water effluent of
only one of nine iron and steel foundries checked to
date and these were at a concentration of .9 ppb.
The Department of Natural Resources has tested the
effluents of 17 pulp and paper mills for PCB's. The test-
ing has revealed that nine of the mills that recycle waste-
papers had measureable discharges ranging from .1 to
124
-------
more than-25 ppb. Mill representatives indicate that the
paper industry no longer uses RGB's and those found in
wastepapers come primarily from carbonless copy papers
that were produced prior to 1972. The old carbonless
copy papers were widely used in forms and continue to
enter the wastepaper market as old files are discarded.
Aroclor 1242 is the principal form found in wastepaper,
however, some Aroclor 1254 has also been reported. Be-
cause their solubility in water is low, we believe that
most of the PCB's discharged from wastepaper mills are
absorbed on fibers and other particulate matter. Mill
wastewater treatment systems, which effectively remove
particulate matter, should also remove PCB's.
The electrical industry continues to use PCB's as
dielectric fluids in some capacitors and transformers. Al-
though the units are sealed, some fluids may be lost as a
result of accidents or disposal practices. In March 1975,
the department corresponded with the major electrical
companies in Wisconsin to determine current handling
practices for capacitor and transformer fluids. The cor-
respondence was followed by visits to many facilities.
The companies contacted were aware of the PCB prob-
lem, but some were not aware of the recommended
Guidelines of the American National Standards Institute
(1974) for Handling and Disposal of Capacitor and
Transformer Askarels (Fluids) Containing PCB's (ref. 6).
We also found that some facilities were storing defective
capacitors until a proper disposal method could be
found. As a result of this survey, specific guidance was
given to Wisconsin electric utilities for the proper han-
dling and disposal of PCB's.
Snow samples were collected early in 1975 to deter-
mine if PCB's were deposited on land and water as fall-
out from the air. Analysis of the snow melt water from
Racine, Kenosha, Madison, and Milwaukee revealed con-
centrations from -.17 to .24 ppb. These values suggest
that fallout of PCB's from the air may be a principal
source of PCB's entering the waters of the State.
PCB's are present in sediments in harbors and
streams near industrial areas. The sediments act as a res-
ervoir where PCB's may be released slowly over a long
period of time. Sediment samples have tested 3.5 ppm in
the Milwaukee River near the Capital Drive Bridge, 9
ppm in Superior Harbor, and 72 ppm in the Fox River
below the outfall of the Portage sewage treatment plant.
We have tried to work out a materials balance for
PCB's entering the environment using the domestic sales
figures provided by the Monsanto Company as well as
other data. There are so many pieces missing from the
puzzle, though, that our efforts to work out a materials
balance have been unsuccessful. Some general comments
can be made, however.
1. PCB's have been sold by the Monsanto Company for
more than 45 years (ref. 7). The company has reported
domestic sales of 795 million pounds of PCB's for the
years 1957 through 1974. Aroclor 1242 accounted for
15 percent, Aroclor 1260 accounting for 11 percent, and
Aroclor 1248 accounting for 7 percent of the sales. In
1974, the Monsanto Company's domestic sales of PCB's
were reported to be 34 million pounds for use in closed
electrical systems. In addition, the Office of Toxic Sub-
stances, EPA (ref. 8) has reported that foreign sales of
PCB's in the United States in 1974 exceeded 375,000.
2. The PCB problem in Wisconsin is a fishery problem
caused because residues have accumulated in certain fish
in Green Bay and Lake Michigan and the Upper Missis-
sippi River in excess of FDA tolerance level of 5 ppm.
Laboratory experiments have shown that fish accumu-
late PCB's more than 100,000 times the levels present in
the water (ref. 9). Therefore, PCB's in the water, even at
ppt levels, have significance to the fishery resource.
3. Our data indicate that levels of PCB's in fish in the
Upper Mississippi River have declined in recent years. We
have not detected a corresponding decline in levels in
Lake Michigan fish.
If Lake Michigan water contains an average of 10
ppt PCB's, then there are more than 100,000 pounds of
PCB's in solution in the lake waters and there is proba-
bly a much larger poundage in the sediments. We have
tested the major effluents of both municipalities and
industries discharging to the Lake Michigan drainage in
Wisconsin and estimate a discharge of about 2 pounds
per day or 730 pounds of PCB's per year to Wisconsin's
drainage to Lake Michigan. Most of PCB's identified in
our testing of major effluents occur in the wastewaters
of pulp and paper mills that recycle wastepapers.
Discharges of PCB's from pulp and paper mills that
recycle wastepapers will diminish as the mills meet their
discharge permit requirements. Wisconsin mills that recy-
cle wastepapers are required to reduce their discharge of
suspended solids from 131,000 pounds per day (for cal-
endar year 1973) to 45,000 pounds per day by the 1977
compliance date. Recently one mill in the State, which
uses only recycled papers, began operation of a new
treatment system that has reduced the discharge of sus-
pended solids from 40,000 pounds per day to 3,000
pounds per day. Tests at this facility revealed 39 ppb
PCB entering the treatment system with only 1 ppb
being discharged in the final effluent.
4. In our search for sources of PCB's entering the envi-
ronment, we have not looked closely enough at fallout
from the air. Our testing of snow melt suggests that
fallout may be contributing much greater amounts of
PCB's than are being contributed by industrial and muni-
cipal effluents. Trace concentrations in fallout over Lake
Michigan and its watershed, which cover 67,900 square
125
-------
miles, could result in appreciable amounts of RGB's en-
tering the waters of Lake Michigan.
Because RGB's are stable compounds with low vapor
pressures, little loss is expected to occur through vapori-
zation from disposal sites where capacitors and other
equipment and materials have been disposed and covered
with overburden. Entry into the air may be expected to
occur at locations where papers are incinerated, at
foundries where imported casting waxes containing
RGB's are heated to high temperature, and at manufac-
turing facilities. RGB's adsorbed on fine particulate mat-
ter may also be entering the air, as windblown dust.
5. Further information is needed to define the amount
of RGB's contributed to Lake Michigan and other waters
through past accumulations in sediments. A University
of Wisconsin study is currently underway in Southern
Lake Michigan; this should provide some of the answers.
The Department of Natural Resources does not have
the authority to regulate the sale or use of RGB's, but
can adopt effluent standards. The department held hear-
ings on two proposals for effluent limitations for RGB's
on August 28-29, 1975. The first proposal would prohib-
it the discharge of RGB's and the second would limit the
discharge to .005 mg/l or 5 ppb. The hearing record is
being reviewed by the Natural Resources Board. No final
decision has been made on an effluent standard as yet.
On September 10, 1975, Congressman Aspin of Wis-
consin introduced a bill (HR 9525) to prohibit the intro-
duction or delivery for introduction into commerce of
RGB's. This bill is pending in the House Interstate and
Foreign Commerce Committee, Subcommittee on Con-
sumer Protection and Finance. This legislation would be-
come effective 3 years after enactment providing indus-
try with a 3-year changeover period to alternate sub-
stances.
REFERENCES
1. P. Degurse and J. Ruhland, Occurrence of Chlori-
nated Biphenyls in Mississippi River Fish, Wisconsin
Department of Natural Resources, Bureau of Fish
Management Report No. 52, 1972, 13 pp.
2. G. D. Veith, Chlorinated Hydrocarbons in Fish
From Lake Michigan, Water Quality Office, U.S. En-
vironmental Protection Agency, Project 16020,
1973, 129pp.
3. P. Degurse and V. Outer, Chlorinated Hydrocarbon
Residues in Fish from Major Waters of Wisconsin,
Wisconsin Department of Natural Resources, Fish
Management Section Report No. 79, 1975, 21 pp.
4. G. D. Veith and G. F. Lee, "Chlorobiphenyls (RGBs)
in the Milwaukee River," Water Research, Vol. 5
(1971), Pergamor Press, Great Britain, pp.
1107-1115.
5. J. G. Dube, G. D. Veith, and G. F. Lee, "Polychlori-
nated Biphenyls in Treatment Plant Effluents,"
Journal of the Water Pollution Control Federation,
Vol. 46, No. 5 (May 1974), pp. 966-972.
6. American Standards Institute, American National
Standard Guidelines for Handling and Disposal of
Capacitor and Transformer Grade Askarels Contain-
ing Polychlorinated Biphenyls, ANSI C107, 1-1974,
35pp.
7. W. B. Papageorge, Testimony provided at the Efflu-
ent Standards Hearings for Polychlorinated Biphen-
yls held on August 28-29, 1975, by the Wisconsin
Department of Natural Resources in Madison, Wis-
consin; Wisconsin Department of Natural Resources
Public Hearing Record files, Madison, Wisconsin,
1975.
8. G. H. Schweitzer, Testimony provided at the Efflu-
ent Standards Hearings for Polychlorinated Biphen-
yls held on August 28-29, 1975, by the Wisconsin
Department of Natural Resources in Madison, Wis-
consin; Wisconsin Department of Natural Resources
- Public Hearing Record files, Madison, Wisconsin,
1975.
9. A. V. Nebeker, F. A. Pughisi, and D. L. DeFoe,
"Effect of Polychlorinated Biphenyl Compounds on
Survival and Reproduction of the Fathead Minnow
and Flagfish," Transactions of the American Fisher-
ies Society, Vol. 103, No. 3 (July 1974), pp.
- 562-568.
126
-------
POLYCHLORIIMATED BIPHENYL
USAGE AND SOURCES OF LOSS TO THE
ENVIRONMENT IN MICHIGAN
John L. Hesse*
Abstract
Polychlorinated biphenyls (PCB'sj are used in a
wide variety of applications including dielectric fluids in
transformers and capacitors; plasticizers in paints, inks,
plastics, and coatings; hydraulic systems; heat transfer
systems; investment casting waxes; and many more. This
paper describes industrial uses of PCB's in Michigan and
focuses on those uses which were found to be sources of
environmental contamination. It describes PCB use fig-
ures supplied by several industries and concentrations
detected in industrial and municipal effluents and
sludges.
INTRODUCTION
Polychlorinated biphenyls (PCB's) are complex mix-
tures of chlorine-substituted biphenyl compounds and
have been produced commercially in the United States
since 1929. Their properties of nonflammability, stabili-
ty, resistance to acids, alkalis, and other caustic chemi-
cals, and low volatility under prolonged heating have
made them useful in a wide range of industrial products.
Monsanto Chemical Company, the sole U.S. manu-
facturer of PCB's, recently released production and sales
figures through 1974 (ref. 1). These showed that produc-
tion and sales roughly doubled between 1960 and 1970,
with nearly 80 million pounds sold annually in the
United States by 1970.
Broadhurst (ref. 2) has summarized" many of the
uses of PCB's. The five largest uses for PCB's prior to
1970 were dielectric fluids in capacitors, plasticizer
applications, transformer fluids, hydraulic fluids and
lubricants, and heat transfer fluids. The list of other uses
is lengthy.
Because of the widescale usage of PCB's, they have
become distributed throughout the world. Since 1967,
reports of PCB residues in fish, birds, water, sediments,
and other environmental samples have been common.
They are of concern in the environment because of their
persistence, potential for biological magnification, and
chronic toxicity.
"Supervisor, Toxic Material Unit, Department of Natural
Resources, Lansing, Michigan.
By 1971, Monsanto recognized the environmental
problems which had developed because of PCB's and
initiated a program to phase out sales for all open-ended
uses, finally limiting sales to uses in electrical capacitors
and transformers. Many officials believed this action
would result in rapid reductions in environmental con-
tamination but little evidence of this has yet been docu-
mented.
Michigan officials have been studying the PCB situa-
tion since 1969 when excessive PCB residues were de-
tected in Great Lakes fish. After development of ade-
quate laboratory capabilities, we instituted a monitoring
program for PCB's early in 1971 consisting of a state-
wide water sampling survey in inland waters and tribu-
taries to the Great Lakes. Supplementary sampling has
since been conducted on fish from inland and Great
Lakes waters, stream sediments, potable water intakes,
sanitary landfill runoff, municipal wastewater treatment
plant effluents, and industrial discharges. Limited ques-
tionnaire surveys of industrial usage have also been con-
ducted. This paper will report briefly on the industrial
uses of PCB's that we have identified in Michigan and
focus on those uses which were found to be sources of
environmental contamination.
Electrical Applications
Prior to the 1971 Monsanto limitation of sales to
the so-called "closed-system" uses, approximately 60
percent of U.S. sales were for electrical capacitor and
transformer applications. In 1968, annual capacitor and
transformer sales totaled approximately 30 and 16.8 mil-
lion pounds, respectively (ref. 3).
While losses from the use of PCB's in these applica-
tions have been estimated as minimal (ref. 3), incorrect
disposal practices and accidental losses from equipment
and storage areas do occur and can result in environ-
mental contamination.
In response to an industrial questionnaire sent to a
cross section of Michigan industries in 1971, one major
power company in Michigan reported an annual use of
562,000 pounds of PCB's (250,000 in precipitator trans-
formers and 312,000 in capacitors). Company records
showed annual losses of approximately 300 pounds of
PCB liquids to soils from burst capacitors and 12,000
pounds from salvaged capacitors. This fluid from the
capacitors was reportedly disposed of through waste
127
-------
haulers. Waste haulers then dispose of these wastes in
many ways, including dust control on roads, sale of oils
as fuel in low-temperature boilers, and treatment and
discharge to municipal sewerage systems. Fluid recover-
ed from precipitator transformers was returned to Mon-
santo for incineration. In the same industrial question-
naire survey, a smaller power company reported that it
had been disposing of approximately 700 pounds of
PCB's per year by mixing with other waste oils and using
the oils for dust control on their driveway and parking
lot.
In October 1975, a 55-gallon drum of PCS trans-
former oil on inventory at a Michigan power company
developed a leak from a defective seam. Approximately
45 gallons of the fluid soaked into the ground, resulting
in more than 100 cubic yards of contaminated soil hav-
ing to be removed and disposed of in an approved land-
fill. This situation illustrates the lack of such proper safe-
guards as diking around storage areas and represents an
example of environmental loss from a so-called "closed-
system" use.
Most industries other than utility companies using
electrical transformers containing PCB's contract either
the transformer manufacturer or smaller companies for
servicing and do not concern themselves with the prob-
lem of disposal of the waste fluids. Frequency of servic-
ing appears to differ between industries, varying any-
where from every 6 months to 10 years.
While water sampling programs in Michigan have
failed to identify any electrical applications of PCB's as
major point sources of loss to aquatic situations, envi-
ronmental losses do occur which have the potential of
indirectly reaching watercourses through atmospheric
fallout or leaching from contaminated soils at spill or
disposal sites. Losses directly to water may occur on
occasion but would be difficult to detect because of
their intermittent nature.
Plasticizer Applications
Plasticizer applications represent the single largest
"open-ended" or dissipative use of PCB's. PCB's are or
have been used as plasticizers in most countries in a wide
variety of consumer products, including paints, inks,
copying paper, adhesives, sealants, plastic products, and
textile coatings, many of which are traded international-
ly (ref. 4). Monsanto's U.S. sales figures for 1970
showed a volume of nearly 20 million pounds for plasti-
cizer applications (ref. 1). Sales for this use were discon-
tinued in 1971. Environmental losses from past sales will
likely continue for a long period of time.
Papers used in the thermographic, xerographic, or
pressure-sensitive copying processes have had PCB's
added as plasticizers either in the ink or paper coatings.
Recycling of these papers can result in contamination of
food packaging materials and other paper products (ref.
3).
Effluents from paper recycling or deinking plants
also become contaminated. In Michigan, paper industry
effluents have been found to commonly contain from 1
to 10Aig/l of PCB'sr Contamination of fish has been
identified as high as 110 mg/kg in the Kalamazoo River
downstream from Kalarnazoo, Michigan, where Michi-
gan's paper industry is primarily centered. Stream sedi-
ments in the Kalamazoo area contain as much as 360
mg/kg PCB's; this is believed to be a result of past deink-
ing processes in the area. Lower level contamination con-
tinues from processing o1 recycled paper but most deink-
ing mills have ceased operation over the past 10 years.
While Monsanto stopped sales of PCB's for paper
applications in 1971, one Michigan paper company re-
cently reported to the Michigan Department of Natural
Resources that several raw products that they purchase
still contain PCB's, Two coloring compounds reportedly
have 23 and 500 mg/kg PCB's and nearly all of their
wood pulp contains from 0.5 to 1.0 mg/kg.
Burning of waste papers containing PCB's, which
occurs every day, undoubtedly results in atmospheric
losses. PCB's have been detected in snowfall samples in
Wisconsin (ref. 5).
The largest quantities of PCB's in plasticizer applica-
tions end up in dumps and landfills. Much of the materi-
al is in sealed containers or impregnated in plastics and is
slowly released to the environment. Nisbet and Sarofim
(ref. 6) reported that vaporization directly from paints,
coatings, and plastics does occur, with losses as great as
20 percent. Open burning in landfills also releases PCB's
to the atmosphere. Another source is loss to leachate
from landfills. Samples of surface runoff water from
nine landfills in Michigan showed five of the nine sam-
ples having PCB concentrations ranging from 0.04 to
0.30 Mg/l, while the otrmrs contained less than 0.01 /ug/l.
In 1970, the U.S. Food and Drug Administration
identified milk contamination in Ohio, Georgia, and
Florida resulting from use of a PCB-containing sealant in
silos (ref. 3). In 1975 the Michigan Department of Agri-
culture investigated problems from this usage and found
76 dairy herds in Michigan with PCB's in milk ranging
from a trace to 14 mg/l on a fat basis. Scrapings from
silos on these farms contained PCB's up to 10,000
mg/kg. Eighty additional silos have been identified as
having the PCB sealant and have been removed from use
until a protective coating can be applied to eliminate
transfer of PCB's to the cattle feed.
128
-------
Hydraulic Fluids
PCB's have found wide usage in hydraulic systems
involving extreme pressure and high-temperature condi-
tions. Annual U.S. domestic sales of PCB's for hydraulic
uses totaled approximately 8 million pounds in 1970
(ref. 1). In Michigan, the automotive and metal finishing
industries have used PCB-containing hydraulic fluids ex-
tensively. Industrial inspections and questionnaires
documented past usage to have been as much as 878,000
pounds/year in individual plants, with most being col-
lected and disposed of through waste haulers. Large
losses of PCB's from these plants to municipal sewers or
directly to surface waters have also been identified.
Wastewater discharges from identified users of
PCB-hydraulic fluids have had concentrations as high as
7.1 mg/l PCB's, indicating losses as great as 30 pounds
per day. In a materials balance study, one industry
which showed in its records that it was replacing approx-
imately 30,000 pounds PCB's/year in hydraulic systems
calculated that 10,000 pounds/year were entering the
atmosphere through vaporization losses, 8,000 pounds/
year in absorbents placed in landfills, 6,000 pounds/year
lost to soils and drainage systems on plant property,
5,000 pounds/year going to waste haulers, with the re-
mainder incinerated.
All industries that we have identified as using PCB's
in hydraulic systems have converted to substitute prod-
ucts, mostly phosphate esters. Complete elimination of
PCB residues from the systems has proved ineffective
even with repeated flushings. Sampling of replacement
fluids indicates PCB contamination as high as 100 mg/l.
Residues in discharge lines combined with loss of con-
taminated replacement fluids appear to result in con-
tinued low-level discharges. Because of existing invento-
ries and possible purchase from foreign sources or re-
processing companies, it is unlikely that all hydraulic
systems not included in our surveys or questionnaires
have been switched to replacement fluids. One facility
which we investigated had an inventory of 9,000 gallons
of PCB fluids in storage.
In summary, Michigan's surveys of hydraulic system
usage of PCB's suggests that this has been a major source
of environmental contamination and may continue to
contribute to the problem to a lesser but still significant
degree.
Heat Transfer Systems
PCB's heat transfer fluids have been used in place of
steam or superheated water in many industries and large
building complexes. They provide advantages of reduced
explosion hazards, absence of corrosion problems, and
have good heat transfer characteristics (ref. 4). In 1970,
Monsanto sold approximately 4 million pounds of PCB's
for this application but phased out all sales in 1972 (ref.
3).
From 1971 through 1973, Michigan identified at
least 12 facilities discharging PCB's to surface waters or
municipal sewers from this usage. Concentrations in
some discharges were as high as 5.2 mg/l.
One automotive company in Michigan reported
using 34,000 pounds of PCB's per year in heat transfer
systems at three of its plants. The waste fluids were
reportedly disposed of by industrial waste haulers.
Another smaller plant reported loss of 800 pounds in
1972 and that approximately 700 pounds of this total
was incinerated, 75 pounds disposed of in dumps, and
25 pounds lost to sewers and drains.
In another Michigan survey, a chemical company
complex was found to have an effluent concentration of
35 HQ/\ resulting from heat transfer system losses. Heat
transfer losses are not all from industrial facilities. Samp-
ling of interceptor lines of the Detroit, Michigan, sewer-
age system resulted in the identification of heat transfer
usage from two residential building complexes and one
hospital as large sources of PCB input to the system.
Miscellaneous Uses
In 1971, Michigan officials found a PCB concentra-
tion of 6.6 Mg/l in the waste lagoon of a soap and deter-
gent company. The source was traced back to the com-
pany's usage of PCB's as a dedusting agent at 0.7 percent
in one of its powdered products. The company had dis-
continued this usage in June 1970 and the PCB's were
apparently leaching from contaminated lagoon sedi-
ments.
The investment casting wax industry has been re-
cently identified as another user of PCB's (ref. 7). This
casting method, which has largely replaced sand casting
for production of low-tolerance-quality metal castings,
uses formulated waxes as a basic molding mode. The
waxes are injected into metallic dies to form the part
shape and then coated with ceramic to form a final
mold. The wax is removed by insertion of the mold in an
autoclave, which melts the wax. Residues of wax are also
secondarily removed by insertion of the molds in a fur-
nace at 1,600° to 1,800° F. During these two proce-
dures, the bulk of the wax is collected and usually recy-
cled but a portion is lost to vaporization, cooling water
contact, and poor housekeeping practices.
The waxes in use are obtained from a few major
suppliers, one of whom is a major importer of decachlo-
robiphenyl from an Italian source. We have found twelve
firms in Michigan using this casting process and several
firms that reprocess their waxes. Our preliminary investi-
gations indicate that most of the waxes contain approxi-
mately 20 percent of PCB's or polychlorinated terphen-
129
-------
yls (PCT's); one recent sample indicates the range may
extend as high as 60 percent content in the wax. The
nature of these casting operations, including both opera-
tional and storage modes, at many plants indicates
strong potential for environmental loss. An effluent sam-
ple from one of the Michigan companies using invest-
ment casting wax contained 2.5 /ag/l of RGB's.
During a telephone survey of 39 industries in
Michigan during May 1975, several industries reported
use of a toilet hand soap containing 0.05 percent RGB's
by weight. Followup on these reports indicated that this
product actually contains a chlorinated diphenyl oxide
rather than RGB's.
Three industries in the telephone survey reported
use of a hydrated lime product that contained about 0.5
mg/kg RGB's. This product was being used for water
treatment and in production of glass pellets. No explana-
tion was available on why the lime contained RGB's but
it is assumed to be a contaminant rather than an addi-
tive.
Concentrations in Municipal Wastes
Because of the diversity of RGB usage, municipal
wastewater is likely to receive RGB's from numerous
domestic and industrial sources, many of which are list-
ed above. Buckley (ref. 3) estimated that municipal out-
falls would likely contribute less than 5 percent (300
tons) of total annual loadings (6,000 tons) to aquatic
environments of the North American continent. His esti-
mate was based on an assumed average RGB concentra-
tion of 10 M9/I in wastes serving a sewered population of
150 million people producing 130 gallons of sewage per
person per day.
Sampling of 58 municipal wastewater treatment
plant (WWTP) effluents throughout Michigan in 1973
showed an average concentration of 0.52 /ig/l (table 1).
This is considerably lower than Buckley's value of 10
jug/I used in his calculations but still exemplifies wide-
spread contamination in municipal wastes, and docu-
ments that they are indeed a source of RGB loss to sur-
face waters.
Much of the RGB's entering municipal waste treat-
ment facilities are removed and become incorporated
into the waste sludge. Table 2 shows RGB concentrations
in the sludges from Michigan municipal plants sampled
in 1973. Concentrations are much higher than in the
effluents from the same plants. The average for all plants
was 15.6 mg/kg, with individual values as high as 350
mg/kg. Disposal of these sludges may add to environ-
mental RGB levels. Sewage sludges are commonly dispos-
ed of by incineration, spreading on agricultural land, or
placing in landfills.
Discussion
While I have characterized in this report possible
and proven sources of environment loss of RGB's in
Michigan from several applications, I want to acknowl-
edge that not all industrial effluents tested in Michigan
contain measureable RGB levels. We have tested over 900
industrial samples, with approximately 40 percent of ef-
fluents sampled containing RGB's above our 0.1 /Ltg/l
laboratory sensitivity limit. Twenty-three percent of the
industries tested had greater than 0.5 /^g/l, 18 percent
greater than 1 jug/I, 6 percent greater than 10^9/1, and 2
percent greater than 100 /ig/l. This represents a diversity
of industries showing contamination and in many cases
the source of effluent contamination could not be deter-
mined.
Since new industrial sources of loss are continuously
being found, we feel we are far from eliminating the RGB
inputs to surface waters by searching for point sources
and taking corrective measures on a case-by-case basis.
We are far from understanding the impact or compara-
tive contribution of atmospheric losses but we feel these
are probably very significant also.
In light of considerable environmental damage and
economic impact of RGB contamination, an absence of
any apparent decline in environmental concentration
with current control methods, the ubiquitous nature of
usage, the general lack of adequate disposal facilities,
and the indication that atmospheric transport and depo-
sition is also significant, the Michigan Department of
Natural Resources urges that a national ban be pursued
on all domestic and imported RGB's destined for use
other than in transformers and capacitors, and that the
critical or essential use of RGB's in transformers and
capacitors be immediately and critically reviewed in light
of current potential replacement products.
Feeling that existing legislation was inadequate to
control RGB's, a group of Michigan legislators introduced
a bill on August 14, 1975, to prohibit the manufacture,
sale, and use of RGB's in Michigan for all applications
other than for transformers and capacitors. The bill
would provide for labeling, reporting, and disposal re-
quirements and specifies penalties for violations. The bill
calls for a stepwise elimination of RGB's with the sale,
manufacture, and use of products containing 25 percent
or more RGB's forbidden by January 1, 1976; 10 ppm or
more forbidden after January 1, 1977; and 5 ppm or
more forbidden after January 1, 1978. Public hearings
on the bill are currently being conducted by the Michi-
gan House Committee on Marine Affairs. [The bill was
amended and voted out of committee on December 11,
1975. The amendment changed the maximum allowable
concentration after Ja/iuary 1, 1977, to 1,000 ppm and
100 after January 1, 1978.]
130
-------
Table 1. Concentrations of PCB's in the final effluent from wastewater
treatment plants throughout Michigan, Spring, 1973. Concen-
trations in micrograms per liter, dry weight.
City.
Adrian
Albion
Ann Arbor
Bay City
Battle Creek
Benton Harbor-
St. Joseph
Brighton
Cadillac
Charlotte
Constantine
Detroit
Dexter
East Lansing
Escanaba
Essexville
Flint
Gladstone
Grand Haven
Grand Rapids
Holland
Hough ton -Hancock
Iron Mountain-
Kingsford
Ironwood
Jackson
Kalamazoo
L'Anse
Lansing
Mam'stique
Marquette
Marshall
Menominee
Midland
Mil ford
Monroe
Mt. Clemens
Mt. Pleasant
Muskegon
Muskegon Heights
Miles
Norway
Owosso
Pontiac (Auburn)
Pontiac (£. Blvd.)
Port Huron
Saginaw
Sault Ste. Marie
St. Ignace
Three Rivers
Traverse City
Trenton
Warren
Wayne County
Wyoming
Ypsilanti
Ypsilanti Twp #1
Ypsilanti Twp #2
Date
3/7/73
2/22/73
3/1/73
3/1/73
2/28/73
2/28/73
3/1/73
3/28/73
5/1/73
2/28/73
2/28/73
3/1/73
5/2/73
3/28/73
3/1/73
2/22/73
3/28/73
2/21/73
2/21/73
2/21/73
3/27/73
3/28/73
3/27/73
2/22/73
2/29/73
3/27/73
4/18/73
3/28/73
3/27/73
2/22/73
2/28/73
3/1/73
3/8/73
5/4/73
3/8/73
3/23/73
2/28/73
2/28/73
2/20/73
3/28/73
2/21/73
3/12/73
3/12/73
3/8/73
3/1/73
3/28/73
3/28/73
2/21/73
3/7/73
2/28/73
2/27/73
2/28/73
2/21/73
2/28/73
3/1/73
3/1/73
PC3'S
1 242 1254
0.34
0.25
3.20
<0.10
0.20
0.53
0.34
0.46
2.15
0.23
0.13
0.10
<0.10
0.44
<0.10
1.05
<0.10
0.18
0.69
<0.1
0.22
0.63
0.29
0.15
0.57
<0.10
<0,10
0.29
o.sa
0.18
0.48
<0.10
0.12
0,73
0.31
<0.10
<0.10
<0.10
<0.10
0.40
0.22
<0.10
<0.10
1242:1254
0.26
0.33
0.28
0.29
1.12
0.31
2.20
2.90
0.60
0.54
1.80
0.77
0.31
Concentrations based on best fit of three standards: Aroclor
1242, Aroclor 1254, or a mixture of Aroclor 1242 and 1254 in a 1:1
ratio.
131
-------
Table 2. Concentrations of PCB's in the sludge from fifty-seven municipal
wastewater treatment plants in Michigan, Spring 1970f Concen-
trations in milligrams per kilogram, dry weight.
City
Adrian
Albion
Ann Arbor
Bay City
Battle Creek
Benton Harbor-
St. Joseph
Brighton
Cadillac
Charlotte
Constantine
Detroit
Dexter
E. Lansing
Escanaba
Essexville
Flint
Gladstone
Grand Haven
Grand Rapids
Holland
Howel 1
Houghtdn-
Hancock
Iron Mountain-
Kingsford
Ironwood
Jackson
Kalamazoo
L'Anse
Lansing
Hanistique
Marquette
Marshall
Menominee
Midland
Mil ford
Monroe
Mt. Clemens
Mt. Pleasant
Muskegon
Muskegon Heights
Niles
Norway
Owosso
Pontiac (Auburn)
Pontiac (E. Blvd.)
Port Huron
Saginaw
Sault Ste. Marie
St. Ignace
Three Rivers
Traverse City
Trenton
Warren
Wayne County
Wyomi ng
Ypsilanti
Ypsilanti Twp #1
Ypsilanti Twp »2
Date 1242
3/7/73
2/22/73
3/1/73
3/1/73 352.0
2/28/73
2/28/73
3/1/73
3/28/73
5/1/73
2/28/73
2/28/73 32.1
3/1/73
5/2/73
3/28/73
3/1/73
2/22/73
3/28/73
2/21/73
2/21/73
2/21/73
4/26/73
3/27/73
3/28/73
3/27/73
2/22/73
2/29/73 23.3
3/27/73
4/18/73
3/28/73
3/27/73
2/22/73
2/28/73
3/1/73
3/8/73
5/4/73
3/8/73 175.0
3/28/73
2/28/73
2/28/73
2/20/73
3/28/73
2/21/73
3/12/73
3/12/73
3/8/73
3/1/73
3/23/73
3/28/73
2/21/73
3/7/73
3/28/73
2/27/73
2/28/73 2.0
2/21/73
2/28/73
3/1/73
3/1/73
PCB's
1254
1.5
1.1
2.8
13.8
<0.1
<0.1
6.8
2.1
3.2
4.6
5.9
3.9
6.3
4.1
4.1
11.8
0.8
15.0
5.5
9.5
5.2
3.0
4.4
5.3
1.5
2.3
3.9
4.2
2.9
3.3
6.5
12.7
11.0
7.8
<0.1
2.0
5.0
2.4
1.5
4.1
1.8
<0.1
<0.1
0.53
2.0
<0.1
<0.1
1242:1254
24.0
50.5
12.1
9.2
9.2
Concentration based on best fit of three standards: Aroclor
1242, Aroclor 1254, or a mixture of Aroclor 1242 and 1254 in a 1:1
ratio.
132
-------
REFERENCES
1. William Papageorge, "RGB Manufacture and Sales,
Monsanto Industrial Chemicals Company, 1957
through 1974," handout to Governor's Great Lakes
Regional Pesticide Council, Chicago, Illinois, Janu-
ary 30, 1975.
2. Martin G. Broadhurst, "Use and Replaceability of
Polychlorinated Biphenyls," Environmental Health
Perspectives. Exp. Issue No. 1 (April 1972), pp.
81-102,
3. Interdepartmental Task Force on PCB's, "Polychlor-
inated Biphenyls and the Environment," National
Technical Information Service, Springfield, Virginia,
COM-72-10419, May, 1972.
4. Organization for Economic Co-Operation and Devel-
opment, "Polychlorinated Biphenyls — Their Use
and Control," Paris, November, 1973.
5. Stanton Kleinert, "Statement Before the DNR Rule-
making Hearings to Consider Effluent Standards for
PCB's," Room 421, South Capital, Madison, Wis-
consin, August 28, 1975.
6. I. C. T. Nisbet, and A. F. Sarofim, "Rates and
Routes of Transport of PCB's in the Environment,"
presented at International Scientific Meeting on
PCB's, Rougemont, North Carolina, December
20-21, 1971.
7. Vincent J. DeCarlo, EPA Monitoring and Informa-
tion Systems Branch, memo to James M. Conlon,
EPA Air and Hazardous Materials Division, Washing-
ton, D.C., May 12, 1975,
133
-------
GENERAL DISCUSSION OF SESSION II
CHAIRMAN GARRETT: I applaud all the speakers for
their interesting insights in these matters. At this
point I'd like to call for questions from the floor.
MR. DON SKINNER (Environment Canada, Ottawa,
Canada): I am from Canada, and I would like to
address myself to Mr. Tom Kopp. Tests going on at
St. Lawrence Cement in Ontario, to set the record
straight, are being financed by the Government of
Canada and the Government of Ontario. The partici-
pation in that program other than the suppliers of
the waste is still up to EPA?
MR. THOMAS E. KOPP (Environmental Protection
Agency, Washington, D.C.): Yes, sir.
MR. HOWARD A. FORMAN (United Electrical Work-
ers, New York, New York): I would like to address
my question to Mr. Kopp. You had mentioned how
EPA is surveying the use and disposal of PCB's. I
know that at least our use was not surveyed, we
represent a very valuable source of information on
PCB use, especially regarding capacitor plants and
transformer plants. Does EPA plan to survey and try
to get information from the various labor unions
involved in the electrical manufacturing industry?
MR. KOPP: That is a very interesting idea, to survey the
unions. I will discuss this with our Office of En-
forcement. We'll get together and discuss it and if
you'll let me have your name and address, we'll get
back to you.
CHAIRMAN GARRETT: I have one question I'd like to
ask Bob Durfee. There may be some question that
may arise from this, but Bob, would you please
describe the differences between the two terms
mentioned just now, Aroclors and askarels.
DR. ROBERT L. DURFEE (Versar, Inc., Springfield,
Virginia): Well, Aroclors are a trademark of Mon-
santo Company, and askarels are a class of fluids
which by their nature do not form combustible
products during an electrical breakdown in a dielec-
tric system. There are several types of askarels;
among them is the metalated PCB.
MR. RICHARD FERRY (Bio International, Inc., Woods
Hole, Massachusetts): You told us about filtration
of PCB's. Do you have a handle on the quantity of
PCB's and how they are disposed of?
DR. DURFEE: The disposal of all solid wastes contain-
ing PCB's is by landfill. There is no incinerator
operating at the present time that will accomodate
solids and destroy the PCB. As far as the quantities
are concerned, I really do not know what the total
is going to be. If you say that all transformer fluids
are cleaned up once every 5 years or something like
that, then perhaps the quantity will be less than 1
percent, and this will be replaced by fresh PCB's.
MR. WILLIAM H. BUSCH (Illinois EPA, Springfield,
Illinois): This is not so much a question as a con-
cern. It seems Ijke there is another open-ended
source of PCB's in that most electrical capacitors,
the small ones, end up as a throw-away item in
home entertainment products.
Television sets, radios, and motor-starting capa-
citors ultimately fail and are discarded in landfills. It
seems like we should be giving more attention to
groundwater around landfills. This was touched on
earlier today.
CHAIRMAN GARRETT: We have been considering this
aspect.
MR. JACK MEDVILLE: Dr. Durfee described the con-
trol of U.S. manufacture of PCB's. Does the presen-
tation indicate that the United States has shut off
foreign manufacturers of PCB's?
MR. KOPP: We have no legal authority to control im-
portation of PCB's inlo the United States.
MR. MEDVILLE: I will phrase the question differently.
We have received here a number of figures of the
amount that is going out and being reentered each
year from U.S. manufacturing; is there an outlet on
what is coming in from foreign nations?
MR. KOPP: The information we get is from the Bureau
of Customs. That is maintained confidential, which
is upon their request, Only bulk PCB's are reported.
The amount of PCB's entering in equipment, such as
transformers, we have no idea, but we are trying to
identify the importers of capacitors and trans-
formers to the United States.
MR. MARK WILSON: I am from Canada. I am not ad-
dressing my question to any particular member.
Does anyone know if PCB's are still used in aircraft,
and secondly, what will the offshore oil lines do?
Are they- bringing their own European hydraulic
facilities in?
MR. KOPP: We have thought about this a great deal. We
have also thought about ships that are coming into
the United States from overseas, because of their
hydraulic systems. We do not know of any PCB's
being used in aircraft except in capacitors.
These things we are trying to get information
on, and we hope to get more consultation with
the members of the Organization of Economic Co-
operation Development.
134
-------
20 November 1975
Session III:
ENVIRONMENTAL FATE AND OCCURRENCE
Ian C.T. Nisbet, Ph.D.*
Session Chairman
'Director, Scientific Staff, Massachusetts Audubon Society, Lincoln, Massachusetts.
135
-------
INTRODUCTORY REMARKS
Ian C. T. Nisbet, Ph.D.
This is Session III on Environmental Fate and
Occurrence of RGB's. We have eight papers on residue
levels of RGB's in the environment, followed by four
papers on transport and transformation in the environ-
ment.
We are very short of time to present 12 papers in 4
hours, so I am going to be pressing on the speakers to
cut down the time they spend as much as possible. I
hope you will forgive them if they omit supporting
details of some of what they say. We will not be able to
entertain any questions or discussion until the end of the
session.
I have been asked to introduce this session by ex-
plaining what we knew about RGB's in 1971 when
Monsanto first made its voluntary restrictions on sales,
so that we can see what has been learned in the last 4
years. At the end of 1971, Adel Sarofim and I reviewed
the data that were available on the occurrence of RGB's
in the environment and tried to construct a transport
model.
We wrote two papers; a preliminary version was
published in Environmental Health Perspectives
(1:21-38, 1972), and a considerably fuller version came
out a few months later in the journal Environmental
Research (5:249-362, 1972), incorporating additional
data, corrections, and a comparison of our transport
model with observations of residue levels in the environ-
ment. It seems that almost no one has read this second
paper in Environmental Research, the main reason prob-
ably being that it cost $8. The moral of the story for us
scientists is that if we want our work to be read and
quoted, we have to release large quantities of reprints
into the environment, and direct them down environ-
mental gradients into compartments where they will
have maximum biological impact.
In these papers we did four things. The first was to
review the data on production of RGB's in the United
States and their uses. We reviewed what data were avail-
able OQ releases of RGB's into the environment, both
deliberate releases and accidental ones. We filled in this
information with what was essentially guesswork about
the remaining releases into the environment, based on
our knowledge of the lifetimes of products containing
RGB's, disposal practices, and the likely behavior of
RGB's in the environment, including their behavior
during incineration. Our conclusion was there were three
major routes of release of RGB's into the environment as
of 1971. The most important, amounting to about three
quarters of the total, we believed would be deliberate
discarding of RGB's and products containing them,
mostly into dumps and landfills. Much of this discarded
material would be incorporated in sealed containers and
plastic. We had no knowledge whatsoever whether the
material put into dumps was leaching out or not.
The second most important route, accounting for
two-thirds to three-quarters of the remaining disposal,
we believed was into water. This was primarily attribut-
able to losses of industrial fluids, including hydraulic
fluids, dielectrics, heat exchange fluids, fluids in com-
pressors, and disposal of scrap fluids from manufacturing
operations.
The third route of release, which we thought
accounted for the balance of the total, was into the air.
We thought that there were several substantial contribu-
tions to release to the atmosphere, the major one being
evaporation from plasticized products. We thought there
were probably also substantial releases from incomplete
burning in dumps and poorly operating incinerators,
together with some releases from burning of scrap prod-
ucts. There was also known to be some release into the
environment from dedusting agents containing RGB's
used on roads and parking lots.
The second thing we did was to review what was
known about transport of RGB's in the environment.
This appeared to fall into two major categories, trans-
port in air and transport in water. We guessed that most
aerial transport was due to passive movement of RGB's
trapped on airborne particulates, eventually returning to
earth in rain and dustfall. We reviewed transport in water
with particular respect to transport downstream into the
Great Lakes and the sea. We thought there were a num-
ber of different methods of transport, all of which were
significant. These included transport in solution, move-
ment of sediment containing RGB's, dredging of contam-
inated sediment followed by dumping at sea, deliberate
dumping at sea of industrial waste, dumping at sea of
sewage sludge, transport in sewage to ocean outfalls,
leaks directly into estuaries from coastal industries, and
finally disposal from ships.
The third thing that we did was to compare our
estimates of releases and 'transport to levels that had
been reported in the environment. We found five major
discrepancies.
1. Surveying the environment, we could not account
for more than a very small fraction of RGB's that
were being released or had been released in the past.
137
-------
We concluded that most of the RGB's that had been
discarded in the past were still in dumps and land-
fills.
2. The amount that we estimated as being released into
freshwater was very much larger than anything we
could estimate as being transported to the sea. We
concluded that PCB's were accumulating in sedi-
ments in rivers and lakes. We also thought that they
were accumulating in sediments at sea on the con-
tinental shelf.
3. Most environmental residues were of pentachlorobi-
phenyls and higher chlorinated species, although
about half of the releases into the environment at
that time and in the past had been of tetrachloro-
biphenyls and lower chlorinated species. Our con-
clusion was that the tetrochlorobiphenyls and lower
chlorinated species were being rapidly degraded in
the environment. This conclusion was based on the
fact that we could not find any evidence for differ-
ential transport and dispersion of the lower isomers
away from points of release.
4. PCB levels in the ocean and in marine organisms-
plankton, fish, and birds—were much higher than
could be accounted for by aerial transport. We
suggested speculatively that the major source of
PCB's in the ocean might be marine hydraulic fluids.
5. There were higher residues in terrestrial birds than
could be accounted for by considering known dis-
persive uses.
Accordingly we posed in 1972 six major questions
about PCB's in the environment:
1. What happens to chlorinated dibenzofurans in the
environment? Are they released, are they persistent.
and are they bioaccumulative?
2. Are the PCB's being discarded into dumps going to
stay there or are they going to leak out in the
future? This is perhaps one of the biggest environ-
mental questions to be solved, because our estimate
was that over the past few decades something of the
order of 300,000 tons of PCB's had gone into
dumps and landfills.
3. Are the PCB's that are now in sediments in fresh-
waters and the shallow sea going to be covered up
and sequestered away from us, or are they going to
be continually recycled back into the environment
in future years?
4. Is it correct that the tetrachlorobiphenyls and the
lower chlorinated species really are rapidly de-
graded, and is there significant human exposure to
these lower chlorinated species?
5. What is the extent of human exposure, both the
average and the extremes? We suggested some num-
bers in our papers, but we concluded that they were
very ill-defined and that the extent of human expo-
sure was very variable.
6. Finally, what would be the effect of Monsanto's
curtailment of dispersive uses in 1971? We con-
jectured that this action would cut out only part of
the influx into the environment, and that it would
be a long time before some compartments in the
environment show decreases in environmental levels.
These are the questions which I think will be ad-
dressed in part by our 12 speakers this morning. In my
summary statement, I will come back and see how far
we have come in answering those questions in the last 4
years.
138
-------
RESIDUES OF POLYCHLORINATED BIPHEIMYLS
IN THE GENERAL POPULATION OF THE UNITED STATES
Frederick W. Kutz, Ph.D., and S. C. Strassman*
Abstract
Residues of polychlorinated biphenyls have been
found in human adipose tissue and in milk collected
from the general population of the United States. In a
national survey of human adipose tissue during fiscal
years 1973 and 1974, 35.1 and 40.3 percent, respective-
ly, of the tissue collected contained levels of 1 ppm or
more of polychlorinated biphenyls on a wet-weight
basis. Electron capture-gas chromatographic analysis of
this tissue revealed that the compounds found in adipose
tissue were most comparable to those prevalent in
Aroclor 1254 and Aroclor 1260. Additionally, semi-
quantitative estimation of these residues was accomplish-
ed by thin-layer chromatography. Evidence from gas-
liquid chromatography-mass spectrometry indicated that
the most frequently encountered polychlorinated
biphenyl residues were penta-, hexa-, and heptachloro-
biphenyl compounds.
Human milk samples collected in selected counties
of Arkansas and Mississippi were found to contain trace
quantities (<1 ppm) of polychlorinated biphenyls on a
wet-weight basis.
Human exposure to polychlorinated biphenyls may
come from direct contact with industrial products con-
taining these compounds, from association with contam-
inated environmental components or from many combi-
nations of the two. Intake of these compounds may
occur by three routes: (1) ingestion, (2) respiration, and
(3) absorption through the skin and mucous membranes.
Most probably, all contribute to the total body burden
of these chemicals; none of these routes of exposure can
now be identified as the most important.
Polychlorinated biphenyls have been found in
human adipose tissue collected for the National Human
Monitoring Program as reported by Yobs (ref. 1). This
program is a continuing ambient monitoring activity
which functions to determine, on a national scale, the
exposure of the general population to pesticides and to
assess changes in these parameters when they occur.
Polychlorinated biphenyls, in addition to certain organ-
ochlorine pesticides, are detected in human adipose
tissue following a multiresidue analytical procedure sti-
* Ecological Monitoring Branch, Technical Services Division
(WH-569), U.S. Environmental Protection Agency, Washington,
D.C.
pulated by the National Human Monitoring Program for
Pesticides.
The objective of this paper is to report the findings
of polychlorinated biphenyls during the human monitor-
ing sorveys conducted in fiscal years 1973 and 1974.
These results are compared to those obtained in the
1971 survey. Additionally, the results of the analysis of
human milk for polychlorinated biphenyls are presented.
Data from gas-liquid chromatography-mass spectro-
metric analysis of the polychlorinated biphenyls in
human adipose tissue and milk are also reported.
Early confirmation of polychlorinated biphenyls in
hurrun depot fat was accomplished in 1967 by Widmark
(ref. 2) using combined gas chromatography mass spec-
trometry. An article by Biros et al. (ref. 3) reported that
two human adipose tissues examined by combined gas
chromatography mass spectrometry were shown to con-
tain substantial quantities of polychlorinated biphenyls
ranging from pentachlorobiphenyl to decachloro-
biphenyl and included at least 14 isomers and chlorine
homologs. These samples, supplied by the National
Human Monitoring Program for Pesticides, were selected
because of indications of unusually high levels of these
chemicals.
One of the laboratories routinely engaged in human
tissue analysis, under contract to the National Human
Monitoring Program for Pesticides, published data re-
garding the polychlorinated biphenyl content of human
adipose tissue (ref. 4). According to this study, 41 to 45
percent of the general population had levels of 1 ppm or
more of polychlorinated biphenyls with isomers contain-
ed in Aroclors 1254, 1260, 1262, and 1268. The pre-
sence of these compounds, ranging from pentachloro-
biphenyl to decachlorobiphenyl, was confirmed in three
samples by combined gas chromatography mass spectro-
metry.
Polychlorinated biphenyls were found in measurable
amounts in 31.1 percent of 637 samples of human
adipose tissue collected from the general population as
part of the Human Monitoring Survey during 1971 (ref.
1). Sample collection involved 18 states and the District
of Columbia. Positive samples were obtained from each
political jurisdiction sampled.
Residues of these compounds have also been detect-
ed in other human tissues and milk. In a study of human
milk collected in Colorado, 8 of 40 samples contained
residues of polychlorinated biphenyls ranging from 40 to
100ppb(ref. 5).
139
-------
METHODS AND MATERIALS
Samples of adipose tissue from individuals of the
general population were obtained through the coopera-
tion of pathologists and medical examiners in 75 select-
ed collecting sites throughout the contiguous 48 States.
Sampling: A stratified random design, with samp-
ling proportioned to populations, was followed for
selecting cities in which tissue samples were collected.
The strata were the nine census divisions as designated in
the 1970 Census; the sampling units in each census re-
gion were cities with populations in excess of 25,000
people. The number of cities designated within each
census division was based on population. The cities
which served as collecting sites are shown in figure 1.
This design provided samples which are statistically
representative of the general population. For each collec-
tion site, an annual sample quota was established to re-
flect the demographic distribution in that census divis-
ion. The sample quota in each of these groups was allo-
cated proportionally according to the age, sex, and race
distribution, as determined by the 1970 Census.
Adipose tissue was collected by cooperating patho-
logists and medical examiners from postmortem exami-
nations and from specimens which had been removed
during therapeutic surgery. Thus, tissues were received
from patients having pathological conditions as well as
those dying from sudden acute illness or from trauma.
Information recorded for each tissue sample included
age, sex, race, and pathological diagnosis. Geographic
residence was assumed to be in the general location of
the hospital. Since the objective of the program was to
reflect the pesticide and other pollutant burden in the
general population, samples were not collected from
cases in which a diagnosis, of pesticide poisoning was
suspected or known, from cachectic patients, or from
patients who had been institutionalized for extended
periods. Further details of the program were presented
by Yobs (ref. 6).
Chemical Analysis: Samples were analyzed chem-
ically by contract laboratories using only methodologies
specified by the program. All laboratories were required
to maintain acceptable performance levels in an inter-
laboratory quality assurance program established and
moderated by the EPA Pesticides and Toxic Substances
Effects Laboratory, Research Triangle Park,
N.C. 27711. This laboratory also provided technical
assistance for the analytical portion of the program.
Samples were analyzed for selected chlorinated
hydrocarbon insecticides ("able 1), and polychlorinated
EAST£
NORTH
CENTRAL
Figure 1. Map of the United States showing census divisions and
collection sites for the National Human Monitoring
Program for Pesticides.
140
-------
Table 1. List of chemicals detectable
in human adipose tissue
o,p'-DDT
p,p'-DDT
o,p'-DDE
p,p'-DDE
o.p'-DDD
p,p'-DDD
a-BHC
B-BHC
lindane
6-BHC
aldrin
dleldrin
heptachlor
heptachlor
epoxide
endrin
mi rex
oxychlordane
trans-
nonachlor
polychlorinated
biphenyls
hexachloro-
benzene
biphenyls, using a modified Mills-Olney-Gaither proce-
dure (ref. 6). Gas-liquid chromatography with electron
capture detection was employed for basic compound
identification and quantification. The analytical deter-
minative procedure for polychlorinated biphenyls in
tissue involved: (a) extraction, partitioning, and Florisil
column chromatographic purification of the residues to-
gether with the chlorinated hydrocarbon pesticides pre-
sent in the tissue sample, and (b), thin layer chromatog-
raphic (TLC) semiquantitative estimation of residues in
the purified extract following elimination of interfer-
ences from op- and pp'-DDE, ODD, and DDT residues
by chemical conversion to the respective isomer of
dichlorobenzophenone. The details of the TLC proce-
dure included treatment of the extract with ethanolic
potassium hydroxide to effect dehydrochlorination of
DDT and its analogs to DDE. This was followed by oxi-
dation with chromium trioxide in acetic acid to convert
DDE residues to dichlorobenzophenone, which may be
conveniently separated from the polychlorinated
biphenyl residues by the TLC procedure. The plates
were coated with silver nitrate-impregnated aluminum
oxide G and developed with 5 percent benzene in
hexane. Ultraviolet visualization of the eluted poly-
chlorinated biphenyl residues and semiquantitative com-
parison of sample spot intensity with those observed for
standard materials completed the polychlorinated bi-
phenyl determination.
A total of 140 human adipose tissue sample extracts
from the general population have been subjected to
analysis by combined gas chromatography-mass spectro-
metry (GC-MS) to confirm and identify polychlorinated
biphenyl components stored in human tissue. Levels of
total polychlorinated biphenyls in the samples based on
TLC determination ranged from 0.4 to 3.5 ppm. The
adipose tissue samples had been extracted and subjected
to the purification procedures described earlier. Con-
version of the DDT-type residues to dichlorobenzo-
phenone was effected by the combined dehydrochlorina-
tion, oxidation, chemical procedures. A final Florisil
column chromatographic step was included to further
purify the polychlorinated biphenyl residues and remove
the dichlorobenzophenones present at relatively high
levels in the extract.
RESULTS AND DISCUSSION
The levels of polychlorinated biphenyls found in
general population samples of adipose tissue during fiscal
years 1973 and 1974 are presented in table 2. Results
presented by Yobs (ref. 1) are included for comparative
purposes. During fiscal years 1973 and 1974, 35.1 and
40.3 percent, respectively, of the tissues collected con-
tained levels of 1 ppm or more of polychlorinated bi-
phenyls on a wet-weight basis. These frequencies are
slightly higher than the 32.5 percent figure reported by
Yobs (ref. 1) and are slightly lower than thrse (41-45
percent) reported by Price and Welch (ref. 4). The per-
centage of tissues which contained quantifiable amounts
of polychlorinated biphenyls appears to be remaining
relatively constant. However, there does seem to be an
increase in the percentage of tissues which contained
trace levels of this chemical although the limit of detec-
tion (1 ppm) remained constant. It should be interesting
to determine whether these trace values will be conver-
ted to quantifiable amounts as the exposure of the
general population continues over time.
National frequencies for fiscal years 1973 and 1974
were compared to frequencies for each census division
and are presented in figure 2. The New England, Middle
Atlantic, South Atlantic, and East North Central Census
Divisions had frequencies of quantifiable levels exceed-
ing the national frequencies for both survey years. The
Mountain and East South Central Census Divisions had
levels higher than the national levels for one survey year
and lower for the other survey year. The Pacific, West
North Central, and West South Central had levels lower
than the national levels for both survey years.
141
-------
Table 2. Levels of polychlorinated biphenyls
in human adipose tissue
Data Sample Percent Percent Percent Percent
source size nondetected < l ppm 1-2 ppm > 2 ppm
Yobs, 688
1972
FY 1973 1277
Survey
FY 1974 1047
Survey
34.2 33.3 27.3 5.2
24.5 40.2 29.6 5.5
9.1 50.6 35.4 4.9
[ BELOW NATIONAL FREQUENCY
| ABOVE NATIONAL FREQUENCY FOR 1 YEAR AND BELOW NATIONAL FREQUENCY FOR 1 YEAR
I ABOVE NATIONAL FREQUENCY
Figure 2. Map of the-United States depicting census divisional
frequencies of polychlorinated biphenyls.
142
-------
The most frequently encountered polychlorinated
biphenyl residues in the human adipose tissue extracts
examined by combined gas chromatography-mass spec-
trometry were the penta-, hexa- and heptachlorobi- 2.
phenyl compounds.
As polychlorinated biphenyls enter a biological
system, the less chlorinated isomers are apparently either 3.
metabolized or excreted. These biochemical reactions
alter the original Aroclors, so that electron capture chro-
matograms of these compounds from biological systems
do not exactly match available laboratory reference 4.
standards. However, it can be noted that results do indi-
cate that the polychlorinated biphenyls found in human
adipose tissue most closely resemble Aroclor 1254 and 5.
Aroclor 1260.
The National Human Monitoring Program also
collected and analyzed 57 samples of human milk from
selected areas of Arkansas and Mississippi. The survey
design was related to rice culture areas in which the 6.
herbicide 2,4,5-T was used. All of these samples contain-
ed trace amounts of polychlorinated biphenyls, the pre-
sence of which were confirmed by combined gas chro- 7.
matography-mass spectrometry in a composite sample.
REFERENCES
1. A. R. Yobs, "Levels of Polychlorinated Biphenyls in
Adipose Tissue of the General Population of the
Nation," Environ. Health Perspectives, Vol. 1
(1972), pp. 79-81.
G. Widmark, "Possible Interference by Chlorinated
Biphenyls," J. Assoc. Off. Anal. Chem., Vol. 50
(1967), p. 1069.
F. J. Biros, A. C. Walker, and A. Medberry, "Poly-
chlorinated Biphenyls in Human Adipose Tissue,"
Bull. Environ. Contamin. ToxicoL, Vol. 5 (1970),
pp. 317-323.
H. A. Price and R. L. Welch, "Occurrence of Poly-
chlorinated Biphenyls in Humans," Environ. Health
Perspectives, Vol. 1 (1972), pp. 73-78.
E. P. Savage, J. D. Tessari, J. W. Malberg, H. W.
Wheeler, and J. R. JBagby, "Organochlorine Pesticide
Residues and Polychlorinated Biphenyls in Human
Milk, Colorado - 1971-1972," Pesticide Monitoring
J.,Vol.7 (1973), pp. 1-5.
A. R. Yobs, "The National Human Monitoring
Program for Pesticides," Pesticide Monitoring J.,
Vol. 5 (1971), pp. 44-46.
J. F. Thompson, ed.. Analysis of Pesticide Residues
in Human and Environmental Samples (Manual of
Analytical Methods), prepared by Pesticides and
Toxic Substances Effects Laboratory, U.S. Environ-
mental Protection Agency, Research Triangle Park,
N.C. 27711.
143
-------
PCB RESIDUES IN HUMAN ADIPOSE TISSUE AND MILK
Donald L Grant, Ph.D.*, J. Mes* and R. Frank**
Abstract
Surveys of PCB residues in human adipose tissue
suggest that females have lower residues than males, that
residents of Central Canada (Manitoba and Saskatche-
wan) have lower levels than the rest of Canada, and that
the majority of Canadians have an adipose tissue residue
of 1 to 2 mg/kg. PCB residue in human milk of Ontario
residents was found to be approximately 1 mg/kg fat.
Data on PCB residues in adipose tissue obtained in a
national survey by Health and Welfare Canada and data
obtained in a survey of residents of Ontario will be pre-
sented. Human milk PCB residue data obtained in
Ontario will also be presented. The Ontario surveys were
carried out by the Ontario Ministries of Health and of
Agriculture and Food.
The adipose tissue samples were collected at autop-
sy. In all surveys, organochlorine pesticides as well as
PCB residues were determined. The PCB and organo-
chlorine pesticide residues were separated by column
chromatography prior to gas-liquid chromatography and
quantitation with an electron capture detector.
PCB residue data for human adipose tissues ob-
tained in the Health and Welfare Canada survey are pre-
sented in tables 1 and 2.
All adipose tissues had detectable levels of PCB's
and 30 percent of the samples had PCB residues greater
than 1 mg/kg. The range of residues present was 0.11 to
6.60 mg/kg. There are some regional differences; 49 per-
cent of the adipose tissues samples collected in Ontario
had PCB residues greater than 1 mg/kg, while only 9
percent of the samples collected in Manitoba and Sas-
katchewan (Central Region) had PCB residues greater
than 1 mg/kg. The other three regions were very similar
with approximately 25 percent of the samples having
residues greater than 1 mg/kg.
The mean PCB residue for all adipose tissues collect-
ed was 0.907 mg/kg (table 2). The residue present in
adipose tissue from males was greater than that present
*Toxicological Evaluation Division, Foods Directorate,
Health Protection Branch, Department of Health and Welfare,
Ottawa, Ontario, Canada.
"Provincial Pesticide Residue Testing Laboratory, Ontario
Ministry of Agriculture and Food, Guelph, Ontario, Canada.
in adipose tissue from females. Residues present were
highest in samples collected in Ontario, with means of
1.165 and 0.859 mg/kg for males and females, respec-
tively, and lowest in samples collected in Central Canada
(Manitoba and Saskatchewan), with means of 0.621 and
0.377 mg/kg for males and females, respectively. Al-
though differences were noted when the data were
broken down (0 to 25 years, 26 to 50 years, 50+ years)
to study the effect of age, these differences were not
statistically significant.
The results of the surveys carried out by the Ontario
government during the years 1969-1974 (table 3) suggest
that the mean PCB residue in human adipose tissues col-
lected in Ontario is higher than that reported in the
survey by Health and Welfare Canada. However, the
Ontario survey results are expressed on a fat basis, while
the Health and Welfare Canada surveys are presented on
a whole wet tissue basis. The adipose tissue contained
approximately 80 percent extractable fat. Although the
1969-70 mean residue value is half that reported for the
years 1971-72 and 1973-74, the authors believe this is
due more to method refinement than to an actual
doubling of PCB residue.
The PCB residue data obtained for the years
1971-72 and 1973-74 are broken down so that an age
comparison for PCB residues can be made (table 4). Al-
though the results have not been statistically analyzed,
the 21- to 40-year age group did show somewhat lower
residues than the 41- 10 60- and 61- to 80-year groups.
Residue surveys were also carried out during the
period (1969-1974) on human milk. The residue results
suggest no change in PCB residue concentration during
the years 1969-74 (table 5).
In summary, survey;; of PCB residues in human adi-
pose tissue suggest that lemales have lower residues than
males, that residents of Central Canada (Manitoba and
Saskatchewan) have lower levels than the rest of Canada
and that the majority of Canadians have an adipose tis-
sue residue of 1 to 2 rng/kg. PCB residue in human milk
of Ontario residents was found to be approximately 1
mg/kg fat.
REFERENCE
1. M. Holdrieni, H. E. Braun, R. Frank, G. J. Stopps,
and J. W. McWade, unpublished results, 1975.
144
-------
Table 1. PCB residues in human adipose tissue
Region
Ontario
Quebec
Atlantic
Central
Western
Canada
Samples with
PCB > 1 mg/kg
28
11
4
2
6
51
Total No.
samples
57
50
16
22
27
172
Percent
samples with
PCB ^ T mg/kg
49
22
25
9
22
30
Table 2. PCB residues (mg/kg) in human adipose tissue
Sex
M
F
M&F
Atlantic
0.758(13)
0.593(3)
0.727(16)
Quebec
1.125(30)
0.723(19)
0.969(49)
Ontario
1.165(38)
0.859(17)
1.070(55)
Central9
0.621(11)
0.377(11)
0.499(22)
Western
0.977(19)
0.684(7)
0.898(26)
Canada
1.020(111)
0.685(57)
0.907(168)
Central = Saskatchewan and Manitoba.
"'Western = Alberta and B. C.
145
-------
Table 3. PCB residues (mg/kg)a
in human*3 adipose tissue
Year Samples Range Mean
69-70 20 1.0-2.0 1.2
71-72 282 ND-18 2.5
73-74 129 0.6-11.0 2.3
3Fat basis. Table 4. PCB residues (mg/kg)a
in human*3 adipose tissue
(ref. 1).
Year
1971-72
Mean
Samples
1973-74
Mean
Samples
21-40
0.5-6.0
2.2
40
0.6-6.0
2.1
13
Age
41-60
ND-8.0
2.6
96
0.7-7.0
2.2
47
61-80
0.5-10.0
2.6
119
0.6-11
2.5
54
Table 5. PCB residues (mg/kg)a
in human'3 milk
Fat basis.
Ontario residents, Holdrient et al.
Year
1969-70
1971-72
1973-74
Samples
43
34
19
Range
0.7-1.2
0.2-3.0
0.1-2.5
Mean
1.0
1.2
1.2
Fat basis.
bOntario residents, Holdrient et al
146
-------
LEVELS OF PCB's IN THE U.S. FOOD SUPPLV
Charles F. Jelinek, Ph.D., and P. E. Corneliussen*
Abstract
The Food and Drug Administration has taken regu-
latory action since late 1969 to protect the consumer
from foods found to contain hazardous levels of PCB's.
It has monitored for PCB's in (1) specific products such
as milk, (2) raw agricultural products, (3) commercial
fish at the wholesale levels, and (4) the total diet. The
foods examined were commercial products, essentially
all in interstate commerce. Data will be presented on the
concentration of PCB's obtained in different food com-
modities from 1969 through mid-1975. These data show
that there has been a significant decrease in PCS levels in
all foods with the exception of fish, where no particular
trend has been noted. In the case of fish, almost all lots
containing more than the FDA tolerance level of 5ppm
in the edible portion originated from the Great Lakes
area. It is concluded that the procedures instituted to
exclude the use of PCB's in the "open"applications have
been effective, but that more needs to be done to pre-
vent their entry into the aquatic environment.
The Food and Drug Administration (FDA) has
taken regulatory actions since late 1969 against foods or
feeds containing hazardous amounts of PCB's. The pur-
pose of this paper is to summarize the data FDA has
obtained on PCB levels in the different types of foods,
and to cite the trends which have taken place since our
first actions.
Table 1 summarizes the highlights from FDA's anal-
ysis of approximately 15,000 samples from November,
1969, through June, 1971. It will be noted that fish,
cheese, milk, eggs, and byproducts used in animal feeds
were the main commodities contaminated by PCB's.
Such foods of animal origin were frequently found to
contain significantly high levels of PCB's.
This table does not include data developed by the
United States Department of Agriculture (USDA) in its
surveillance of meat and poultry during this period. In
addition, the data do not reflect the food contamination
that occurred later as a result of the leakage of PCB-
containing heat exchange fluid into a pasteurized fish
meal, which in turn was fed to poultry and catfish. This
was by far the most serious incident of PCB contamina-
*C. F. Jelinek is Director of the Division of Chemical Tech-
nology, Bureau of Foods, Food and Drug Administration, Wash-
ington, D.C. P. E. Corneliussen is Assistant to the Director of
the Division of Chemical Technology, Bureau of Foods.
tion of our food supply and led to very extensive regu-
latory actions by FDA and USDA, such as seizures and
recalls of poultry, eggs, fish, and feeds.
During the surveillance period summarized in table
1, PCB's were not found in cereal grain and fresh fruits
and vegetables. In late 1971, FDA established the fact
that food packaging made from recycled paper which
contained PCB's caused contamination of the contents,
such as infant foods and cereals.
As a result of the above findings, FDA proposed
certain regulations for PCB's in 1972. Table 2 shows our
current regulations pertaining to PCB's in foods, animal
feeds, and food packaging (ref. 1).
The first category of regulations covers the tempo-
rary tolerances for PCB's in products selected as a result
of our monitoring activities, namely, milk, dairy prod-
ucts, poultry, eggs, animal feeds and their components,
infant foods, and paper food packaging. Of these, fish
are the only products which the PCB's contaminate pri-
marily through the environment, in this case the water-
ways. The sources of the PCB's in the other foods and in
food-packaging material were mainly industrial and agri-
cultural uses which enabled PCB's to enter into food or
animal feeds.
The second category of regulations is the prohibi-
tion of use of PCB's in such applications as heat transfer
fluids, hydraulic fluids, paint components, adhesive com-
ponents, etc., in plants that produce food, animal feed,
or food-packaging materials.
These regulations were proposed in 1972 and are
now officially established, with the exception of the
maximum permissible level of PCB's in paper food-
packaging material, which is an administrative guideline,
pending the results of a hearing which has been granted.
Turning to the more recent period since 1972, the
results obtained in FDA and USDA monitoring programs
in fiscal years 1973, 1974, and 1975 are summarized in
table 3. It can be seen that PCB's now contaminate far
fewer types of foods than they did formerly. Although
PCB's were reported in fish, milk, eggs, cheese, feed
components, and poultry in fiscal years 1974 and/or
1975, the rates and levels of occurrence have declined
drastically in all categories except fish.
The samples of fish FDA has analyzed were ob-
tained through several different activities in the field. In
fiscal years 1973 and 1974 we carried out Compre-
hensive Fish Surveys in which we analyzed freshwater
and saltwater fish obtained at the wholesale level for
147
-------
Table 1. PCB findings, Nov. 1969--June 1971a
Food Positive
commodity findings
Finfish
Oysters
Fish byproducts
Cheese
Milk
Eggs
Potato
byproducts
Miscellaneous
317
12
6
44
60
17
12
11
Avg. of
positives
(ppm)
2.1
Trace
1.8
0.3b
2.5b
Trace
1.1
1.9
Max. level
(ppm)
35.3
Trace
5.0
1.0b
22. 8b
0.5
4.2
6.5
Approximately 15,000 samples examined.
Fat basis.
Table 2. FDA regulations, RGB's
I. Temporary tolerances
PCB cone.
Commodity (ppm)
Milk (fat basis) 2.5
Dairy products (fat basis) 2.5
Poultry (fat basis) 5.0
Eggs 0.5
Finished animal feed 0.2
Animal feed components 2.0
Fish (edible portion) 5.0
Infant and junior foods 0.2
Paper food-packaging 10.0
material without PCB-
impermeable barrier
a
II. Use prohibited in food,
feed, food packaging plants
Administrative guideline, pending
hearing.
148
-------
Table 3. Summary of PCB's in foods,
FY '73, '74, and '75
Food
Commodi ty
Fish
Milk
Eggs
Cheese
Feed components
Animal feeds
Processed fruits
Infant & jr. foods
Meats & poultry
(USDA)
FY
Percent
positive
60.4
2.2
1.1
0.9
12.7
7.2
4.5
1.1
Percent
positive
1.9
'73
Max.
(ppm)
123.0
1.6
Trace
0.5
9.0
199.5
19.2
Trace
Percent
above
5 ppma
0.19
FY
Percent
positive
44.0
2.6
4.2
2.6
0.0
0.0
0.0
0.0
Percent
positive
1.2
'74
Max.
(ppm)
16.8
2.3
11.0
2.8
N.D-
N.D.
N.D.
N.D.
Percent
above
5 ppm
0.07
FY
Percent
positive
17.8
0.7
0.0
0.0
0.3
0.0
0.0
0.0
Percent
positive
0.3
'75
Max
(ppm)a
9.0
1.9
N.D.
N.D
0.9
N.D.
N.D.
N.D.
Percent
above
5 ppm
0.06
Milk, cheese, meats and poultry reported as ppm, fat basis.
PCB's, pesticides, and certain heavy metals. In addition,
we analyzed fish obtained from our regular surveillance
program for pesticides and PCB's, primarily in the raw
products. Finally, we collected samples as a compliance
followup after high levels of PCB's had been found in a
particular species or area. The data obtained from these
activities are valuable in showing which species and
which areas are apt to be of concern, but it is difficult to
determine whether there have been any significant
trends because of the diversity of the sources of the fish
samples and of the reasons for collecting them.
Figure 1 depicts the results obtained in the Compre-
hensive Fish Survey conducted in fiscal year 1973. It
should be stressed that almost all the samples collected
were commercial species intended for interstate com-
merce, and thus would not ordinarily include sports fish.
No PCB's could be detected in over 70 percent of the
samples collected. Only about 3 percent contained over
1 ppm, and 0.5 percent had over 5 ppm PCB's. It is
interesting to note that the various species containing
over 1 ppm were generally freshwater fish, or those
which were apt to be near the shore. The only fish in
this particular survey that contained more than the 5
ppm tolerance for PCB's were carp, with a maximum
level of 20.5 ppm.
The results obtained in the Comprehensive Fish Sur-
vey for fiscal year 1974 are shown in figure 2. Over 80
percent of the samples analyzed in this survey did not
contain PCB's, and no samples contained more than 2
ppm PCB's. However, it cannot be concluded that there
was a down-trend, since it was necessary to stop this
survey before it was half finished because of the neces-
sity fo divert manpower to the canned mushroom crisis.
Nevertheless, freshwater fish again were most likely to
contain the highest levels of PCB's.
Figure 3 depicts the results obtained with all sam-
ples of domestic finfish analyzed in fiscal years 1973,
1974, and 1975, from all FDA programs. The percentage
of fish samples containing PCB's decreased in 1974 and
1975, but on the other hand, the percentage of PCB-
containing samples which were above 5 ppm increased.
Significantly, all these samples were from the districts in
the Great Lakes area, and included such species as chubs,
carp, and coho salmon.
149
-------
BO-
ZO-
50_
3 OF 17 CARP
3 OF 34 CATFISH
3 OF 29 HERRING
2 OF 36 FLOUNDER
2 OF 16 SCUP-PORGIE
1 OF 2 BUFFALO
1 OF*! WHITE BASS
1 OF 39 MACKEREL
NOT TRACE
DETECT- TO
ABLE .49
.50 1.00 2.00 5,00
TO TO TO TO
•99 1-99 n.99 9.99
PCS CONCENTRATION RANGES (PPM)
20.0
(MAX,
20.5)
Figure 1. FY 1973 Comprehensive Fish Survey
(41 species, 600 sample total).
150
-------
80'
70-
60 -
c250
£40 -
z
LU
O
Cf.
UJ
a-
30 -
20 ~
10 -
2 OF 5 CARP
1 OF 2 BUFFALO
1 OF 19 MACKEREL
1 OF 24 PERCH
NOT
DETECT-
ABLE
TRACE .50 1.00
TO TO TO (MAX. 1.34)
.49 .99 2.00
PCB CONCENTRATION RANGES (PPM)
Figure 2. FY 1974 Comprehensive Fish Survey
(38 species, 269 sample total).
151
-------
50 f1
50
GO
O
Q_
_
<-J Q_
X
LU LO
—i LT>
I—
.—. t_D
CO -Z.
O —
Q- ca
LU
LL. LU
O <_>
X
B-« LU
<-3
i—. LO
CO
O
Q-
.— . ~- (.3
ca co ^:
LU E: o — .
LU Q_ Q_ ca
!_J Q_ I . I
X U_ LU
LU LT\ O <_>
x
FISCAL YEAR '73
FISCAL YEAR '74
— ,=3 CO ;=
I— LU El O '—'
— LU D_ D_ ca
CO '—> C_ LU
O X LL. LU
Q_ LU LO O> <-_)
X
s^s ;>s s-9 LU
FISCAL YEAR '75
Figure 3. RGB's in fish, all programs.
As mentioned previously, it is difficult to draw any
conclusions as to whether there is a significant trend,
because of the changing sources and objectives from year
to year. The percentage of samples examined which con-
tained more than 5 ppm RGB's stayed in the same gener-
al range (2.2 to 3.5 percent).
These results from FDA's surveillance programs
show that RGB's do not generally occur in significant
levels in saltwater fish, and indeed that only a small
percentage of freshwater fish in interstate commerce
contain more than 5 ppm RGB's. Further, the waterways
in which commercial fish are likely to contain high levels
of RGB's are those which are contiguous with industrial-
ized areas.
Thus far, we have reviewed the general levels of
RGB's in individual food types. What do these findings
mean in terms of average intake of RGB's from the entire
diet? FDA conducts a continuing survey of the Total
Diet, in which composites of 12 different food catego-
ries are analyzed. Table 4 presents the composites in
which RGB's were found in the FDA Total Diet Surveys
from fiscal years 1971 through the first half of fiscal
year 1975. It can be seen that the meat-fish-poultry
composites contained RGB's much more frequently than
any other of the food groups. With regard to the findings
of RGB's in the composites of fruits, vegetables, and
cereals in fiscal years 1972 and 1973, it should be noted
that these composites include processed and packaged
152
-------
Table 4. Total Diet Studies-American teenage male
Percent of composites containing PCB's
Food class composites
Fiscal
Year
1971
1972
1973
1974
1975
(1st
half)
Dairy Meat, Grain
pro- fish & & cereal
ducts poultry products Potatoes
47 13
6 46 6
10 33 17 3
43
40
Oils,
Legume Root fats
vege- vege- Garden & short-
tables tables fruits ening
6 3 3 17
3
Sugars
and
adjuncts
6
3
Table 5. Estimates of daily PCB intakes
(Total Diet Study-teenage male)
Average dail
Fiscal Total diet
year (yg/day)
1971 15.0
1972 12.6
1973 13.1
1974 8.8
1975 (1st 8.7
half)
y intake of PCB's3
Meat-fish-poultry food class
(lag/day)
9.5
9.1
8.7
8.8
8.7
aLower limit of quantitative reporting =0.05 ppm with
analytical method employed.
153
-------
foods as well as raw foods purchased in retail stores.
Since we have hardly ever detected PCB's in the raw
products, the PCB's probably contaminated these foods
during processing or from the packaging. This hypothesis
is borne out by the fact that no PCB's have been found
in these composites in 1974 or 1975, after our regula-
tions had a chance to take effect.
FDA chemists have found that the source of the
PCB's in the meat-fish-poultry composite is almost
always due to the fish component. It is interesting to
note that the frequency of findings in this composite has
remained quite constant since fiscal year 1971. Signifi-
cantly, PCB's are now generally found only in this fish-
containing composite of the Total Diet Survey. This
reflects the beneficial results of FDA and USDA in their
efforts to prevent the uses of PCB's that could lead to
direct contamination of foods, and of the U.S. manu-
facturer in limiting the sales of PCB's to "closed" electri-
cal uses.
In calculating the average daily intake from the
Total Diet Survey, we must be aware of the short-
comings in the use of composites, where the level of
occurrence of the contaminant in the composites may be
at or just below the limits of detection. How we handle
"Trace" and "Not Detected" can have a significant
effect on our estimates of the daily intake. Table 5 gives
the estimated average daily intakes of PCB's by a young
male adult, for fiscal years 1971 through the first half of
1975, where we have ascribed a certain level to all
"Trace" in all composites and to "Not Detected" in the
meat-fish-poultry composites where PCB's are still com-
monly detected. It can be seen that there has been a
marked decrease in the estimated total intake.
However, the estimated intake will tend to continue
at the FY 1975 level, as long as (1) fish remain almost
the sole source of detectable PCB's and (2) the entry of
PCB's into the waterways is not decreased.
In summary, the breadth of occurrence of PCB's has
narrowed to the point where freshwater fish are now the
primary source of PCB's in our diet. Thus, the daily PCB
intake for the average citizen is low, since his consump-
tion of freshwater fish is low, and even here, most of the
commercial freshwater fish contain less than 5 ppm
PCB's.
However, the estimated intake of the average con-
sumer is only a guidepost, and the Food and Drug Ad-
ministration must consider the dietary consumption pat-
terns of significant sectors of the population which are
significantly different from the average. For example,
PCB intake could be quite different for those people
whose diets include substantial quantities of sports fish.
For the future, (1) we must continue to monitor for
PCB's in foods and food-packaging materials to maintain
the beneficial results already obtained, and (2) means
must be employed by the responsible Federal and State
agencies to effectively halt the entry of PCB's into the
aquatic environment.
REFERENCE
1. Food and Drug Administration, "Polychlorinated
Biphenyls (PCB's)," Federal Register, Vol. 38, No.
129 (July 6, 1973), pp. 18096-18104.
154
-------
LEVELS OF PCB's IN CANADIAN COMMERCIAL FISH SPECIES
John M. Graham*
Abstract
For purposes of examining PCB levels in various
environments, Canada is divided into four study areas:
area 1 is the Pacific sector; area 2 is Central Canada; area
3 covers the Great Lakes; and area 4 is the Atlantic
sector. The tables included give detectable levels of
PCB's in various species—ground fish, estuarial and pelag-
ic fish, and crustaceans and mollusks—for the respective
areas.
I will briefly summarize the work that the Inspec-
tion Branch has done in analyzing marine and freshwater
species. And I am going to start by reporting on four
areas in Canada (figure 1). Areas 1 and 4 involve marine
species; area 2 is the central part of Canada excluding
the Great Lakes; and area 3 contains the Great Lakes,
which are of quite a bit of interest to us.
Table 1 is a brief summary of the PCB's that we
have found in our marine species, subdivided as ground
fish, pelagic, estuarial, mollusks and crustaceans, and
miscellaneous. The landings are given in pounds, the
levels are mean levels of PCB's, and the samples analyzed
are in parentheses. One thing worth noticing is the high
level in bluefin tuna, which is 2.65 ppm. We explain this
by the fact that bluefin tuna is usually landed at 600 to
700 pounds. It is a very large fish and at the top of the
food chain.
Another point of interest that you might note is the
fish oils with a mean level of 5.1 ppm. Finally, fish meal
is at a level of about 0.16 ppm. This is because, during
the manufacture of fish meal, most of the oil is ex-
tracted.
As shown in figure 1, area 2 is the central part of
Canada, excluding the Great Lakes. Table 2 gives PCB
levels for freshwater species in that area. The production
amounts to some 70 million pounds of fish annually.
There are detectable levels of PCB's, but usually very,
very low. These are from large northern lakes, and usual-
ly no industry is close by. The median level is 0.10 ppm.
All our samples are based on the edible portion of
the fish and that portion that would normally be con-
sumed by the consumer. The samples are taken either by
commercial fishermen or by our inspectors, so that we
know the exact location at wtjich the samples are col-
lected. Sample size is usually 15 pounds of the fillet or
edible portion and a minimum of five fish.
I have subdivided the Great Lakes-St. Lawrence
River system into the lakes and the river. Table 3 shows
our finding on Lake Superior, which amounts to close to
3.3 million pounds of fish per year. As you can see, the
lake trout is the highest in this lake, based on our find-
ings. We also find that it varies between the inshore lake
trout or shallow-water lake trout and the deepwater, or
fatty, lake trout.
Table 4 shows Lake Huron, Canadian side, amount-
ing to some 2.1 million pounds. Chub at the 2-ppm level,
and carp and suckers are relatively high. Coho salmon is
not normally considered a commercial species in Canada.
There is quite a volume available to sports fishermen and
commercial fishermen. They sell it as part of an inciden-
tal catch.
Now we come to Lake Erie (table 5), which some
people say is a dead lake, but it has an annual planting of
some 31 million pounds of fish. Alewives, rock bass, and
carp are slightly high. The highest is catfish and again
coho salmon, which is 3.14 ppm.
Table 6 shows Lake Ontario, which, as you can see,
has a little bit of a problem (or a lot of problems). Smelt
is at 4.16, and eels are 17.14 ppm. Again the coho sal-
mon is up there. The eels in Lake Ontario are quite high.
The eels in the St. Lawrence river system (table 7) show
about 8 ppm. I have broken the eels down into their size
range and given the medians.
Note the last line. A 41/2-pound eel ranges from 3 to
30 ppm, so that we really cannot manage this fishery on
a size or weight basis. It is going to be extremely diffi-
cult. It looks as if we are going to have to terminate the
licenses for this fishery.
These eel figures are in contrast to the figures that
we had for eels in the Maritime Provinces. The eels in
Maritime Provinces are 0.56 ppm. So it is apparent that
we will be able to keep one section of this fishery open
and must try to manage or close the other one.
We presently have a 2,500-sample survey for the
Great Lakes. Health & Welfare, Canada, established a
temporary guideline of 2 ppm in fish; this means that we
are going to have to break some of our lakes down into
areas, geographic areas, and put restrictions on them
either by length or weight. I do not see the problem
getting any better in the next year.
155
-------
CO
T3
CO
c
CO
O
CO
CO
03
0}
'o
05
Q.
to
O
CD
w
3
O5
156
-------
Table 1. Polychlorinated biphenyls in commercial fish and fishery products,
areas 1 and 4 (marine)
Description and species
Landings
(pounds)
PCB's
(mean ppm)
Groundfish (catfish, cod, flounder,
haddock, halibut, lingcod,
pollock, redfish, red snapper,
rockfish, sablefish, skate,
sole, plaice, tomcod)
Pelagic-esturial (Alewife; cape!in; dogfish;
herring; mackerel; salmon;
smelt; swordfish; tuna:
albacore-ski pjack-yel1owfin;
whale)
Bluefin
Eel - Maritime Provinces
Mollusks &
Crustaceans
Miscellaneous
Clams; crabs; (dungeness-
queen-red-rock) lobster;
mussels; oysters; scallops;
shrimp
Fish oils
Fishmeal
1,191,701,000 0.07 (141)
1,131,868,000 0.39 ( 73)
762,000
100,144,000
2.65
0.56 ( 19)
0.12 ( 56)
4.51 ( 12)
0.16 ( 71)
Table 2. Polychlorinated biphenyls in commercial fish and fishery products,
area 2 (freshwater)
Species
Landings'
(pounds)
Buffalo fish, carp,
goldeye, mallet, perch,
pike, pickerel, sauger,
trout, whitefish
PCB's
(mean ppm)
70,000,000 0.10 (113)
Landings of less than 25,000 pounds per species
are not included.
157
-------
Table 3. Polychlorinated biphenyls in commercial fish and fishery products,
(area 3)
Location
Lake Superior (A)
Major
species
chub
lake herring
lake trout
whitefish
smelt
yellow perch
i j« a
Landings
(pounds)
306,000
1,611,000
195,000
328,000
788,000
67,000
3,295,000
PCB
(mean ppm)
0.96 ( 8)
1.17 (10)
2.02 (37)
0.68 (11)
0.35 ( 6)
0.31 ( 5)
Landings of less than 25,000 pounds per species are not
included.
Table 4. Polychlorinated biphenyls in commercial fish and fishery products,
(area 3)
Location
Lake Huron (B)
Major species
chub
whitefish
carp
suckers
yellow pickerel
sheepshead (drum)
coho salmon
Landings9
(pounds)
671 ,000
950,000
56,000
176,000
269,000
29,000
noncommercial
2,151,000
PCB
(mean ppm)
2.09 (17)
0.95 ( 8)
1.55 ( 4)
1.33 (12)
0.61 ( 9)
0.75 ( 2)
5.11 ( 6)
landings of less than 25,000 pounds per species are not
included.
158
-------
Table 5. Polychlorinated biphenyls in commercial fish and fishery products,
(area 3)
Major
Location species
Lake Erie alewife
rock bass
carp
yellow perch
smelt
yellow pickerel
white bass
catfish
bullhead
sheepshead (drum)
a
Landings
(pounds)
12
15
2
332
49
41
,190
,760
234
,346
88
109
354
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
coho salmon noncommercial
31
,503
,000
PCB
(mean ppm)
1.
0.
1.
0.
0.
1.
1.
2.
0.
0.
3.
22
27
27
19
42
16
26
04
26
74
14
(14)
( 2)
( 7)
(10)
(21)
( 9)
(28)
( 8)
( 4)
(15)
( 8)
Landings of less than 25,000 pounds per species are
not included.
Table 6. Polychlorinated biphenyls in commercial fish and fishery products,
(area 3)
Location
Lake Ontario (D)
Major
species
bullhead
yellow perch
smelt
white perch
sunfish
carp
rock bass
eel
coho salmon
Landings3
(pounds)
248,000
699,000
103,000
290,000
203,000
395,000
42,000
222,000
noncommercial
PCB
(mean ppm)
0.73 (12)
1.23 (10)
4.16 (17)
1.84 (22)
0.74 ( 6)
1.69 (10)
1.76 (18)
17.14 (49)
4.97 ( 3)
2,205,000
Landings less than 25,000 pounds per species are not
included.
159
-------
Table 7. Polychlorinated biphenyls in commercial fish and fishery products,
(area 3)
Location
Major Landings PCB
species (pounds) (mean ppm)
St. Lawrence River (E) sturgeon 77,000 2.32 ( 5)
eel 435,000 7.94 (216)
Species
eel
Size
<2Jg pound
2% pound-4% pound
>4% pound
(0
(1
(2
Range
.11- 7
.68-22
.82-29
.99)
.8 )
.7 )
Mean
2.95
8.19
12.37
PCB
(66)
(72)
(43)
Landings of less than 25,000 pounds per species are not included.
160
-------
THE OCCURRENCE OF PCB IN THE NATIONAL
FISH AND WILDLIFE MONITORING PROGRAM
Charles R.Walker*
Abstract
The National Fish and Wildlife Monitoring Program
has as its objective to ascertain, on a national scale, the
amounts of pesticides and contaminants in some fish,
birds, and mammals. Testing is done through repeated
sampling over time. The species chosen to be monitored
are freshwater fish, mallard and black duck, and starling.
PCB residues in freshwater fish were found to be
highest in certain river systems that lie in industrial
areas. For mallards and black ducks, concentrations were
greatest in ducks in the Atlantic flyways. Starlings from
all over the Nation showed PCB contamination; how-
ever, over the 1970-1974 period, there was an apparent
decline in residue levels, except in certain specific areas
such as Austin, Alabama. Related monitoring indicates
that PCB may be especially threatening to endangered
species, with serious effects on the survival of their
young.
The National Fish and Wildlife Monitoring Program
was initiated in 1967 as a cooperative Federal effort
conducted jointly by the Bureau of Commercial Fisher-
ies and the Bureau of Sport Fisheries and Wildlife in the
U.S. Department of the Interior, and the Water Supply
and Sea Resources Program of the National Center for
Urban and Industrial Health, Public Health Service, U.S.
Department of Health, Education, and Welfare (ref. 34).
The current National Pesticide Monitoring Program is
sponsored by the Monitoring Panel of the Federal Work-
ing Group on Pest Management that includes compo-
nents drawn from the Environmental Protection Agency,
the Tennessee Valley Authority, the National Science
Foundation, and the Departments of Agriculture, De-
fense, Commerce, Interior, and Health.
The monitoring objective was to ascertain on a na-
tional scale the amount of pesticides and related materi-
als in components of the environment and trends of
these levels with time through repeated sampling and
analysis of environmental components (refs. 34,37,38).
The Fish and Wildlife Service program consists of three
elements: (1) freshwater fish, (2) mallard and black
duck, and (3) starlings.
The Freshwater Fish Program originally consisted of
sampling fish from 50 stations in the continental United
*Charles R. Walker, Senior Environmental Scientist, U.S.
Fish and Wildlife Service, Department of the Interior, Washing-
ton, D.C.
States as it was initiated in 1967 (refs. 24,25). In 1970
this was expanded to inckide 100 stations sampled on an
annual basis and included the conterminous United
States and Alaska (ref. 30). Criteria for selection of spe-
cific sampling station locations included the following,
in the order of priority: (1) availability of desired species
of fish; (2) relationship to station locations for other
phases of the National Pesticide Monitoring Program
(refs. 11,14,19,67,69), particularly those stations used
for monitoring surface water samples; (3) existence of
State-sponsored monitoring programs or cooperative par-
ticipation by a State conservation agency; and (4) availa-
bility of suitable manpower and facilities to make field
collections. In the late 1960's, the toxicological signifi-
cance and the detection of polychlorinated biphenyl
compounds in fish and wildlife along with the interfer-
ences with organochlorine pesticide analysis became
apparent (refs. 31,32,33,43,45,50,54,66). This problem
stimulated the development of analytical methods for
the separation and identification of PCB in fish samples
from the National Monitoring Program (refs.
26,28,52,53,57,58).
The cleanup of solvents (refs. 20,56), selective parti-
tion of PCB from pesticides (refs.
1,3,4,7,16,18,26,53,55,58,59), quantitative determina-
tion (refs. 2,9,46,54,57,62), and confirmation methods
(refs. 2,6,8,29,51,52) utilizing gas chromatography-mass
spectrometry became practical for Federal agencies to
use in the National Pesticide Monitoring Program by
1970. In the Freshwater Fish Program, samples of three
to five fish were taken of three species representing dif-
ferent tropic levels to comprise each composite sample.
All composite samples of white fish were analyzed for
the most common organochlorine insecticides, including
DDT, DDE, TDE, dieldrin, aldrin, endrin, BHC, hepta-
chlor epoxide, chlordane, toxaphene, and beginning with
the 1970 collections, polychlorinated biphenyl com-
pounds (PCB), as well as the percent lipid content of the
fish (ref. 61). Whereas these analysis were contracted to
private and other Federal laboratories, a cross-check
quality assurance program was conducted on about 10
percent of the samples by our Fish-Pesticide Research
Laboratory at Columbia, Missouri. The number of pesti-
cides and related contaminates that were detected in the
cross-check analyses grew from 19 compounds in 1970
to 33 parent compounds, homologs, or metabolites by
1973 (table 1).
The mallard and black duck monitoring program
161
-------
Table 1. Organochlorine pollutants detected by initial
and confirmatory laboratories from 1967-1974
Pollutant
DDE
ODD Q,p'isomers
DDT
DDE
DDD p_,p'isomers
DDT
1232
1242 T,
1248 Aroclor"
1254
1260
dieldrin
aldrin
endrin
BHC
lindare.
heptachlor
beptachlor expoide
chlordane
cis-chlordane
toxaphene
hexachlorbenzene (KGB)
heptachlor norborene
oxychlordane
hexachlor norbornadiene
2,4-D PGBE
pentachlorobenzene
hexachloro-1, 3-butadiene
ethylhexylphthalate
dibutylphthalate
dioctylphthalate
DEHP
1967 1968 1969 1970
Ia III Cb
I I IIC
I I IIC
C
C
C
C
C
I 1C
C
I I IIC
I I QIC
I I QIC
I 1C
I 100
I I IIC
I I IIC
I I IOC
I I 0 0 C
C
1971
I C
I C
I C
C
C
C
0?
C
C
I C
C
I C
I C
I C
I C
0
0 C
I C
I C
C
I C
C
0
C
C
1972
I C
I C
I C
C
C
C
0
0
C
I C
C
I C
0 0
I C
I C
0
0 C
I C
I 0
C
I C
C
0
0
0
C
1973
I C
I C
I C
C
C
C
0
0
0
I 0
I 0
I C
I C
I C
I C
0 C
0 C
C
C
C
I C
C
C
C
C
C
C
C
0
0
0
0
I-indicates a pollutant was reported in the results from the initial
analyses.
C-indicates a pollutant was reported in the results from the confirm-
atory analyses.
0-indicates a pollutant was found in previous years but not reported
later.
162
-------
was conducted in cooperation with State agencies in
conjunction with the fall migration of waterfowl and the
hunting season in each of the conterminous States (refs.
17,21,22,23,64). Through a process of systematic sub-
sampling, a series of wings, approximately 12,500 an-
nually, are drawn from each State. These are composited
for analysis into samples of 25 wings each representing a
sample from each State in proportion to the harvest.
Mallard duck wings are collected in the Pacific, Central,
and Mississippi flyways whereas both the mallard and
black duck were represented in those samples from the
Atlantic flyway, depending on the availability of species.
Pesticide analysis included chlorinated hydrocarbon pes-
ticides and beginning with the 1969 sampling also in-
cluded polychlorinated biphenyl compounds.
The National Monitoring Program for starlings, a
widely distributed and abundant species, was especially
designed to sample five degree latitude/longitude blocks
covering the contiguous 48 States with up to four ran-
domly selected collecting sites within each block (refs.
34,41,42,63). Ten birds were collected at each sample
site and composited for analysis in the fall of even years
at approximately 125-130 sites. Organochlorine pesti-
cides were analyzed in the 1967-68 samples and begin-
ning with the 1970 samples polychlorinated biphenyl
compounds were analyzed in 1970-72 and 1974 samples.
Freshwater Fish Monitoring Program
Polychlorinated biphenyl compounds have been
detected in certain rivers and areas in unusually high
concentrations and confirmed in a quality control cross-
check analysis among several laboratories (refs. 54,61).
PCB residues have been found in 40 to 60 percent
of the samples in residue concentrations exceeding 0.5
mg/kg (figure 1). More than 98 percent of the samples
during the period of 1969-71 contained residues in at
least one composite sample exceeding these criteria.
Geographically, the higher concentrations appear to be
TOOi
«. 50
U
oc
Q
i- -« o
o S! a: g
O. Q Q oa K
Figure 1. Percentage of fish sampled from 1969-1973 in the National
Pesticide Monitoring Program that contained either no detect-
able residues (white), residues (cross-hatched), or levels
exceeding the criteria established to be biologically signifi-
cant (solid black: >0.5 mg/kg PCB: > 1.0 mg/kg DDT; and
>0.1 mg/kg dieldrin, BHC, or toxaphene) (ref. 69).
163
-------
associated with certain river systems having industrial
activity (refs. 54,61) (tables 2 and 3). PCB residues ex-
pressed as Aroclor 1254 were found in five major river
systems in the Atlantic coastal region, with residues ex-
ceeding 5 mg/kg. Four of these stations had residues
exceeding 10 mg/kg during the last 5 years. Fish in four
of the Great Lakes stations had PCB concentrations
exceeding the 5 mg/kg level and all stations reported
concentrations exceeding 0.5 mg/kg. In the Mississippi
River system, the Allegheny and Ohio were the hot
spots, with seven out of the eight stations reporting resi-
due concentrations in excess of 5 mg/kg. Thirty-one of
thirty-five stations in this river system reported residues
in excess of 0.5 mg/kg in the 1970-73 sampling pro-
grams. The highest residues, often exceeding 10 mg/kg
were found in the Allegheny, Kanasha, Cumberland,
Tennessee, and Ohio Rivers along with stations on the
Mississippi River at Memphis, Tennessee, and the Mis-
souri River at Herman, Missouri. Other monitoring sta-
tions that were found to have residue levels exceeding 5
mg/kg during the sampling periods 1970-73 included:
the Williamette River on the Columbia system; the
Rouge River in the Pacific coastal drainage; the Sacra-
mento River in California; the Chena River tributary of
the Yukon in Alaska; and the Rio Grande, Alabama, and
Mississippi Rivers in the Gulf States region. Only in two
sample periods of 1972-73 and in the current monitoring
samples, which are still yet to be fully analyzed, has
there been a downward trend, but this occurs only in
those samples where residues are not being detected. The
stations where high residues have been noted in the past
still remain relatively contaminated with PCB. Unlike
the decline of DDT in Great Lakes fishes, PCB concen-
trations do not show significant changes and may trend
upward in salmonids, as indicated in special investiga-
tions conducted by Willford (ref. 69), and Veith (ref.
60).
Just as it is exceedingly important to distinguish
PCB from organochlorine pesticides, we must also make
positive identifications of the different Aroclors so that
they may be correctly expressed in stoichiometric calcu-
lation. For example, in table 4, let us examine some of
those stations with high PCB concentrations. The com-
position of PCB residues in selected fish samples taken
during the National Pesticide Residue Monitoring Pro-
gram illustrates the difficulties in equating all residues to
one type of Aroclor, such as 1254. In this illustration we
can readily show that the expression of PCB from the
Ohio, Mississippi, and Hudson drainage would certainly
misrepresent the true distribution of PCB isomers if they
were all stoichiometrically expressed as 1254. The best
analogy I can offer to illustrate this is if we were to
express all of the hardness or alkalinity of water as calci-
um carbonate, when indeed the actual chemical analysis
indicated that most of the carbonates existed as magnesi-
um carbonate.
This relationship has two dimensions. The first is
that the lower Aroclor series are more highly biodegrada-
ble than are the higher series such as 1254 and 1260. A
PCB residue in fish taken downstream following degrada-
tion would thus appear to be composed primarily of the
1254 or 1260 isomer. However, the toxicity and poten-
tial biological effect would be more serious with regard
to the Aroclors 1232, 1242, and 1248, as noted in table
4. This was particularly evident in the 1970 cross-checks,
in which we were finding that results of two other labor-
atories typically expressed PCB levels at concentrations
of only 5 to 20 percent of that found in the sample by
the more sophisticated procedures used by our Fish-
Pesticide Research Laboratory (refs. 52,54,55,57,58).
Mallard and Black Duck Monitoring Program
White and Heath report that polychlorinated bi-
phenyl residues were highest in the Atlantic flyways; the
mean value of 1.36 ppm occurred in black duck in both
1969 and 1972 (ref. 64}. Mallards from the same flyway
averaged 1.24 and 1.29 ppm for samples taken in 1972
and 1969 respectively (figure 2 and table 5). These levels
compared to mallard duck wings from the Mississippi
flyway, where average values were found to be 0.66 and
0.44 ppm on a wet weight basis for the years 1972 and
1969. Both the Central and Pacific flyways had residues
of approximately 0.1 ppm during 1972 and 0.2 ppm in
1969. The overall trend in the concentration of PCB
would appear to be downward in the Central and Pacific
flyways; however, thh, was significantly different at the
P < 0.05 in the analysis of variance calculation. The
increase in concentration observed in the Mississippi
flyway and status quo for the Atlantic flyway have not
been significantly changed over the same period of time
(refs. 21,22,23,64). The recent studies by White and
Kaiser (ref. 65) on the mortality of ruddy ducks in the
Delaware system, however, did indicate the seriousness
of PCB residues. They found Aroclor 1260 residues or
the bioaccumulation of pentachloro and hexachloro bi-
phenyl compounds that exceed the levels found in our
National Monitoring Program by almost tenfold.
Starling Monitoring Program
PCB has been found in all of the starling samples
taken in 1970, 1972, and 1974 (figure 3). The level of
residues appears to be declining throughout this period;
however, some areas continue to report exceedingly high
concentrations—for example, in the Austin, Alabama,
164
-------
Table 2. Stations with residues in at least one composite exceeding 0.5
mg/kg total RGB's, from an estimate based on Aroclor 1254
(asterisk and double asterisks denote residues in excess of 5.0
and 10.0 mg/kg, respectively)
River (location)
1970
1971
1972
1973
Atlantic Coastal Streams
Penobscot R. (Old Town, ME)
(Stillwater R.)
Kennebec R. (Hinckley, ME)
L. Champlain (Burlington, VT)
Merrimac R. (Lowell, MA)
Connecticut R. (Windsor Locks, CT)
Hudson R. (Poughkeepsie, NY)
Raritan R. (Highland Park, NJ)
Delaware R. (Camden, NJ)
Susquehanna R. (Conowingo, MD)
Potomac R. (Little Falls, MD)
James R. (Richmond, VA)
Roanoke R. (Roanoke Rapids, NC)
Cape Fear R. (Elizabethtown, NC)
Pee Dee R. (Dongola, SC)
Cooper R. (Summerton, SC)
Savannah R. (Savannah, GA)
Altamaha R. (Doctortown, GA)
St. Johns R. (Welaka, FL)
St. Lucie Canal (Indiantown, FL)
Gulf Coastal
Suwanee R. (Old Town, FL)
Apalachicola R. (Jim Woodruff Dam, FL)
Alabama R. (Chrysler, AL)
Tombigbee R. (Mclntosh, AL)
Mississippi R. (Luling, LA)
Brazos R. (Richmond, TX)
Colorado R. (Wharton, TX)
X*
x*
x**
X*
X
X
X
X
X
X
X
X
X,
X
X
X
Streams
X
X
X
X
X
X
X
X**
X**
x**
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X**
x**
x**
X*
x**
X
X
X
X
X
X
X
X
X
X
X*
X*
X
X
X**
X*
x**
X
X**
X
X
X
X
X
X
X
X
X
X
X
X
X
Nueces R. (Mathis, TX)
165
-------
Table 2. (con.)
River (location)
Rio Grande (Brownsville, TX)
Rio Grande (Elephant Butte, NM)
Rio Grande (Alamosa, CO)
Pecos R. (Red Bluff Lake, TX)
Great Lakes
Gennessee R. (Scotsville, NY)
St. Lawrence R. (Massena, NY)
L. Ontario (Port Ontario, NY)
L. Erie (Erie, PA)
L. Huron (Bay Port, MI)
L. Mighigan (Sheboygan, WI)
L. Superior (Bayfield, WI)
1970
X
X*
X
Drainage
X
x*
X
X
X
X
X
1971
X
X
X*
X**
X
X*
x**
X
1972
X
X
X
X**
X*
X
X
X*
X
1973
X*
X
X
X
X*
X*
X*
X
Mississippi River System
Allegheny R. (Natrona, PA)
Kanawha R. (Winfield, WV)
Wabash R. (New Harmony, IN)
Ohio R. (Marietta, OH)
Ohio R. (Cincinnati, OH)
Ohio R. (Metropolis, IL)
Cumberland R. (Clarksville, 'TN)
Tennessee R. (Savannah, TN)
Wisconsin R. (Woodman, WI)
Des Moines R. (Keosauqua, IA)
Illinois R. (Beardstown, IL)
Mississippi R. (Little Falls, MN)
Mississippi R. (Guttenburg, IA)
Mississippi R. (Cape Girardeau, MO)
Mississippi R. (Memphis, TN)
Arkansas R. (Pine Bluff AR)
Arkansas R. (Keystone Reservoir, OK)
Arkansas R. (John Martin Reservoir, CO)
Verdigris R. (Oologah, OK)
Canadian R, (Eufaula, OK)
X**
X**
X
X**
X**
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X**
X
X
x**
X**
X*
X
X
X
X
X
X
X
X
X
X
X**
X**
X
X**
X**
X*
X**
X**
X
X
X
X
X
X**
X
X*
X*
X
x**
x**
X
X*
X*
X
X
X
X
X
x**
166
-------
Table 2. (con.)
River (location)
White R. (DeValls Bluff, AR)
Yazoo R. (Redwood, MS)
Red R. (Alexandria, LA)
Red R. (Lake Texoma, OK)
Missouri R, (Hermann, MO)
Missouri R. (Nebraska City, NE)
Missouri R. (Garrison Dam, ND)
Missouri R. (Great Falls, MT)
Big Horn R. (Hardin, MT)
Yellowstone R. (Sidney, MT)
James R. (Olivet, SD)
N. Platte R. (Lake McConaughy, NE)
S. Platte R. (Brule, NE)
Platte R. (Louisville, NE)
Kansas R. (Bonner Springs, KS)
Hudson
Red R. (North) (Noyes, MN)
Colorado
Green R. (Vernal, UT)
Colorado R. (Imperial Reservoir, AZ)
Colorado R. (Lake Havasu, AZ)
Colorado R. (Lake Mead, NV)
Colorado R. (Lake Powell, AZ)
Gila R. (San Carlos Reservoir AZ)
1970 1971 1972 1973
XXX
X X
XX X
X X** X* X*
X X X X
X X X X
X X
X X X* X
XXX
X XX
X X X X
Bay Drainage
X X X X
River System
X X
Interior Basins
Truckee R. (Fernley, NV)
Utah L. (Provo, UT)
Bear R. (Preston, ID)
X X X X
X
X X X X
167
-------
Table 2. (con.)
River (location)
1970
1971
1972
1973
California Streams
Sacramento R. (Sacramento, CA)
San Joaquin R. (Los Banos, CA)
X
X
X*
X
Columbia River System
Salmon R. (Riggins, ID)
Snake R. (Hagermann, ID)
Snake R. (Lewiston, ID)
Sanke R. (Ice Harbor, WA)
Yakima R. (Granger, WA)
Williamette R. (Oregon City, OR)
Columbia R. (Bonneville, OR)
Columbia R. (Pasco, WA)
Columbia R. (Grand Coulee, WA)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X*
X
X
X
X
X
X
X
X
X
Pacific Coastal Streams
Klamath R. (Hornbrook CA)
Rogue R. (Gold Ray Dam, OR)
X*
Alaskan Streams
Chena R. (Fairbanks, AK)
Kenai R. (Soldatna, AK)
X*
Hawaiian Streams
Waikele Stream (Waipahu, HI)
Manoa Stream (Honolulu, HI)
168
-------
Table 3. Environmental contaminants in
fish (refs. 52, 53, 54, 55)
Residue (yg/g whole body)'
1970
1971 1972 1973
Hudson, R. ,
Poughkeepsie,
N.Y.
Ohio R.
Marietta,
Ohio
Cincinnati ,
Ohio
Metropolis,
111.
Lake Michigan
Sheboygan,
Wis.
Merrimac R.
Lowell ,
Maine
213
122
38
133
66
7.8
98
93
76
77
156
53
45
61
118
16
20
43
2.6
4.9
8.8
104
69
7.5
6.0
45
8,6
11
4.4
8.5
Each value represents analysis of
single fish.
Table 4. Composition of PCB residues in selected fish
samples from the 1970 National Pesticide
Residue Monitoring Program (ref. 54)
River
Location
Species
PCB residue as Aroclor type
whole body)
1232 1248
1254
1260
total
Ohio
Ohio
Ohio
Ohio
Yazoo
Hudson
Allegheny
Delaware
Cape Fear
Lake Ontario
Mississippi
Merrimac
Cincinnati, O.
Cincinnati, O.
Marietta, 0.
Marietta, 0.
Redwood, Miss.
Poughkeepsie, N.Y.
Natrona, Pa.
Camden, N.J.
Elizabeth Town, N.C.
Port Ontario, N.Y.
Memphis, Tenn.
Lowell, Mass.
Carp
White crappie
Channel catfish
Channel catfish
Smallmouth buffalo
Goldfish
Walleye
White perch
Gizzard shad
White perch
Drum
Yellow perch
10.2
15.9
38
15.6
72
8.6
—
—
18.9
12.9
11.2
13.8
75
17
23
5.2
—
173
5.2
8.0
—
—
—
75
42
27
11
12.6
1.4
32
25
6.8
2.6
4.6
4.5
6.1
6.0
5.6
4.9
4.6
—
—
4.6
3.9
1.1
1.2
3.4
3.2
133
66
77
38
73
213
35
19
23
19
19
98
169
-------
0>
E
3
T>
Q
O
O
to
U
a.
1.0-
0.5-
=
1 , 1 £
O IA C u
55 & £
1969
; |
•s "o-s
5 " ~ ~
O wt C o
5 5 5i
1972
PCB
_
i
1 HI £p>
£ o -
5 «•' -^ ~
O w) C u
S*o I
1965*
|
= - =
|||
5 -5 .x
= »• i X
.2 "i c *>
~ — a D
•* 5 u a.
1969
•
: = =
1 = 1
1 . •§ s
-° 3 g i
•« S u *•
1972
DDT + mefabo/ifes
•
u —
? , 1 =
o « c 'C
5 *u £
1965-6
a
a
v -^
•£ o .«
E « - >
-S «> c C
«- ^ « o
« 5 o a.
1969
<•* —,
? M. 5 £
Q "• *• -^
j: w c u
— i • 0
t 5 o a.
1972
Die/dr/n
•0.10
• 0.05
a.
e
a
1
Figure 2. Trends of PCB and organochlorine pesticide residues measured
in samples of duckwings from each flyway in the National
Pesticide Monitoring Program: black duck (solid bar); mallard
(broken bar).
station, the 1970 analysis showed 24.3 ppm in 1972 and
19.9 ppm and a 1.8 ppm concentration in 1974 (table
6). PCB's appear to be ubiquitous throughout the Nation
and occur generally in a concentration of less than 5
ppm, with an arithmetic mean for 1970 of 0.65 ppm, for
1972 of 0.43 ppm, and for 1974 of 0.12 ppm on the wet
weight basis (figure 4).
Related Investigative Monitoring Programs for Wildlife
The widespread occurence of PCB in ecosystems
may be most serious to fish-eating species (refs. 5,10,13)
and to the rates of bioaccumulation up the food chain
(refs. 36,43,49). Special investigative monitoring activi-
ties of the U.S. Fish and Wildlife Service laboratories at
Patuxent, Maryland, have been reported on the bald
eagle relative to pesticides and PCB levels vs. autopsy
and analysis (refs. 15,40,44). In endangered or threaten-
ed species, PCB residues may have serious effects on
survival of young since some effects have been docu-
mented on certain behavioral patterns (refs. 35,36).
Residues observed in the National Monitoring Program
may pose a hazard to animals thai have demonstrated
particular sensitivity to PCB corrt-'itrations affecting
organ function, behavior, growth, &<-••'or reproduction
(refs. 27,36,48,50,52).
ACKNOWLEDGMENTS
Special recognition is due the U.S. Fish and Wildlife
Service Regional Pesticide Specialists and the cooperat-
ing State agencies and individuals for the collection of
samples in the National Pesticide Monitoring Program.
Dr. Donald H. White, Mr. David F. Walsh, and Dr. David
L. Stalling deserve full credit and authorship for the tab-
ulated materials used in this presentation. Chemical anal-
yses were performed by WARF Institute, Inc., and the
U.S. Fish and Wildlife Service Laboratories at Denver,
Colorado, Columbia, Missouri, and Laurel, Maryland.
Analytical methods development and quality control
assurance were conducted by the Fish-Pesticide Research
Laboratory. Management of the contracts, handling of
data, and statistical analyses were the responsibility of
the Patuxent Wildlife Research Center for duckwings,
the Division of Technical Services for starlings and fish.
The author shared responsibility for coordination of this
program with Mssrs. Jerry Longcore, Donald Donahoo,
Bernard Berger, Paul Nickerson, and Anthony Inglis for
the period of time reporting these results.
170
-------
NATIONAL PESTICIDE MONITORING PROGRAM
TREND OF PESTICIDE RESIDUES IN STARt/NCS 1967-74
100
Figure 3. Percentage of starling samples containing PCB and organochlorine
pesticides in the National Pesticide Monitoring Program.
171
-------
Table 5. Mean residues of PCB in wing-pools by major
flyway, 1972 and 1969
Residues
(ppm wet
weight)
Species
Black Duck
Mallard
Mallard
Mallard
Mallard
Flyway
Atlantic
Atlantic
Mississippi
Central
Pacific
Year
1972
1969
1972
1969
1972
1969
1972
1969
1972
1969
No.
of
Pools
44
42
21
19
61
51
56
49
55
51
Mean
1.36
1.37
1.24
1.29
0.66
0.44
0.1 Oa
0.20
o.na
0.20
Std.
Error
0.149
0.161
0.230
0.457
0.303
0.061
0.013
0.039
0.009
0.014
1P < 0.05 (Analysis of variance).
Table 6. Means, ranges, and geometric mean PCB in
starlings from each collecting period, 1967-
68 through 1974
No. of
Year Pools
1967-68
1970
1972
1974***a
360
125
130
126
0
0
0
(ppm
PCBb
wet weight)
x + S.E.
.663
.425
.112
-
+
+
+
0.196
0.153
0.016
0
0
0
Range
-
.09 -
.037 -
.006 -
24.
19.
1.
30
90
88
Geom. x^
0
0
0
-
.358
.215
.068
Mean residues for 1974 were significantly lower than
for 1972:
*** = P<0.001.
DPCB were not analyzed in 1967-68.
172
-------
NATIONAL PESTICIDE MONITORING PROGRAM -- Trends i'n starlings
Arilh. 7 Geo/n. x
Figure 4. Trends of PCB and organochtorine pesticide residues measured in
pooled samples of starlings taken in the National Pesticide
Monitoring Program.
173
-------
REFERENCES
1. B. Ahling and S. Jensen, "Reversed Liquid-Liquid
Partition in Determination of Polychlorinated Bi-
phenyl (PCB) and Chlorinated Pesticides in Water,"
Anal. Chem.. Vol. 42, No. 13 (1970), pp.
1483-1486.
2. J. A. Armour, "Quantitative Perchlorination of
Polychlorinated Biphenyls as a Method for Confirm-
atory Measurement and Identification,",/. Assoc. Of-
ficial Anal. Chem., Vol. 56, No. 4 (1973), pp.
987-993.
3. J. A. Armour and J. A. Burke, "Method for Separat-
ing Polychlorinated Biphenyls From DDT and Its
Analogs,'' J. Assoc. Official Anal. Chem.,Vo\. 53, No.
4 (1970), pp. 761-768.
4. J. A. Armour and J. A. Burke, "Behavior of Chlorin-
ated Napthalenes in Analytical Methods for Organo-
chlorine Pesticides and Polychlorinated Biphenyl,"
,/. Assoc. Official Anal. Chem., Vol. 54, No. 1 (1971),
pp. 175-177.
5. S. Bailey and P. J. Bunyan, "Interpretation of Per-
sistence and Effects of Polychlorinated Biphenyls in
Birds," Nature. Vol. 236, No. 5340 (1972), pp.
34-36.
6. K. D. Bartle, "Identification of Polychlorinated
Biphenyls by High Resolution Proton Magnetic Res-
onance," J. Assoc. Official Anal. Chem., Vol. 55, No.
5, (1972), pp. 1101-1103.
7. 0. W. Berg, P. L. Diosady, and G. A. V. Rees,
"Column Chromatographic Separation of Polychlor-
inated Biphenyls From Chlorinated Hydrocarbon
Pesticides, and Their Subsequent Gas Chromato-
graphic Quantification in Terms of Derivatives,"
Bull. Environ. Contain. Toxicol., Vol. 7, No. 6
(1972), pp. 338-347.
8. E. J. Bonelli, "Gas Chromatograph-Mass Spectrom-
eter Techniques for Determination of Interferences
in Pesticide Analysis," Anal. Chem., Vol. 44, No. 3
(1972), pp. 603-606.
9. J. A. Burke, "Development of the Food and Drug
Administration's Method of Analysis for Multiple
Residues of Organochlorine Pesticides in Foods and
Feeds," Residue Rev., Vol. 34 (1971), pp. 59-90.
10. B. Bush, C. F. Tumasonis, and F. D. Baker, "Toxici-
ty and Persistence of PCB Homologs and Isomers in
the Avian System," Archives of Environ. Contam.
and Toxicol., Vol. 2, No. 3 (1971), pp. 195-212.
11. P. A. Butler, "Organochlorine Residues in Estuanne
Mollusks, 1965-72," National Pesticide Monitoring
Program, Pesticides Monitoring J., Vol. 6, No. 4
(1973), pp. 236-362.
12. T. C. Carver, Pesticide Monitoring Panel, Federal
Working Group on Pest Management, A National
Pesticide Program Overview, International Confer-
ence on Environmental Sensing and Assessment, Las
Vegas, Nev., 1975, p. 4, (memo).
13. R. R. Claeys, R. S, Caldwell, N. H. Cutshall, and R.
Holton, "Chlorinated Pesticides and Polychlorinated
Biphenyls in Marine Species, Oregon/Washington
Coast, 1972," Pesticides Monitoring J., Vol. 9, No.
1 (1975), pp. 2-10.
14. A. B. Crockett, G. B. Wiersma, H. Tai, W. G.
Mitchell, P. F. Sand, and A. E. Carey, "Pesticide
Residue Levels in Soils and Crops, FY-70 - National
Soils Monitoring Program (II)," Pesticides Monitor-
ing J., Vol. 8, No, 2 (1974), pp. 69-97.
15. E. Cromartie, W L. Reichel, L. N. Locke, A. A,
Belisle, T, E. Kaiser, T. G. Lament, B. M. Mulhern,
R. M. Prouty, and D. M. Swineford, "Residues of
Organochlorine Pesticides and Polychlorinated Bi-
phenyls and Autopsy Data for Bald Eagles,
1971-72," Pesticides Monitoring J., Vol. 9, No. 1
(1975), pp. 11-14.
16. J, W. Dolan, R. C. Hall, and T. M. Fodd, "Selective
Detection of Chlorinated Insecticides in the Pres-
"ence of Polychlorinated Biphenyls," J. Assoc. Offi-
cial Anal. Chem., Vol. 53, No 3 (1972), pp.
537-538.
17, E. H. Dustman, W E. Martin, R. G. Heath, and W.
L. Reichel, "Monitoring Pesticides in Wildlife,"Pes-
ticides Monitoring J., Vol. 2, No, 1 (1971), pp.
50-52,
18, R. Edwards, "Factors in the Separation of Poly-
chlorinated Biphenyls From Organochlorine Pesti-
cides by Column Chromatography Combined With
Gas-Liquid Chromatography," Pesticide Science,
Vol. 5, No. 3 (1974), pp. 293-304.
19. H. R. Fletz, W, T. Sayers, and H. P, Nicholson,
"National Monitoring Program for the Assessment
of Pesticide Residues in Water," Pesticides Monitor-
ing J. Vol. 5, No. 1 (1971), pp. 54-62.
20. L, Fishbein, "Chromatographic and Biological As-
pects of Polychlorinated Biphenyls," J. Chromatog-
raphy, Vol. 68, No. 2 (1972), pp, 345-426.
21. R. G. Heath, "Nationwide Residues of Organochlo-
rine Pesticides in Wings of Mallard and Black
Ducks," Pesticides Monitoring J., Vol. 3, No. 2
(1969), pp. 115-123.
22. R. G. Heath and S, A. Hill, "Nationwide Organo-
chlorine and Mercury Residue in Wings of Adult
Mallards and Black Ducks During the 1969-70 Hunt-
ing Season," Pesticides Monitoring J., Vol. 7, No,
3/4 (1974), pp. 153-164.
23. R. G. Heath and R. M. Prouty, "Trial Monitoring of
Pesticides in Wings of Mallards and Black Ducks,"
174
-------
Bull. Environ. Contam, Toxicol., Vol. 2, No. 2
(1967), pp. 101-110.
24. C. Henderson, A. Inglis, and W. L. Johnson, "Orga-
nochlorine Insecticide Residues in Fish-Fall, 1969,"
National Pesticide Monitoring Program, Vol. 5, No.
1 (1971),pp. 1-11.
25. C. Henderson, W. L. Johnson, and A. Inglis, "Orga-
nochlorine Insecticide Residues in Fish," National
Pesticide Monitoring Program. Vol. 3, No. 3 (1969),
pp. 145-171.
26. R. J. Hesselberg and J. L. Johnson, "Column Ex-
traction of Pesticides From Fish, Fish Food, and
Mud," Bull. Environ. Contam. and Toxicol., Vol. 7,
No. 2/3 (1972), pp. 115-120.
27. J. W. Hogan and J. L. Brauhn, "Abnormal Rainbow
Trout Fry From Eggs Containing High Residues of a
PCS (Aroclor 1242)," unpublished manuscript,
19..., p. 5.
28. J. N. Huckins, J. E. Swanson, and D. L. Stalling,
"Perchlorination of Polychlorinated Biphenyls," J.
Assoc. Official Anal. Chem., Vol. 57, No. 2 (1974),
pp. 416-417.
29. 0. Hutzinger and W. D. Jamieson, "Identification of
Polychlorinated Biphenyls and DDT in Mixtures by
Mass Spectrometry," Nature, Vol. 225, No. 5246
(1970), p. 664.
30. A. Inglis, C. Henderson, and W. L. Johnson, "Ex-
panded Program for Pesticide Monitoring of Fish,"
Pesticides Monitoring J., Vol. 5, No. 1 (1971), pp.
47-49.
31. S. Jensen, "A New Chemical Hazard," New Sc/.,Vol.
32 (1966), p. 612.
32. S. Jensen, "Chlorinated Hydrocarbon in Fauna and
Flora,"Grundfoerbattring, Vol. 23, Special-nummer
5(1970), pp. 81-84.
33. S. Jensen, A. G. Johnels, M. Olssem, and G. Otter-
lind, "DDT and PCB in Marine Animals From Swed-
ish Waters," Nature, Vol. 224 (1969), pp. 247-250.
34. R. E. Johnson, T. C. Carver, and E. H. Dustman,
"Residues in Fish, Wildlife, and Estuaries," Pesti-
cides Monitoring 7., Vol. 1, No. 1 (1967), pp. 7-13.
35. J. R. Longcore and B. M. Mulhern, "Organochlorine
Pesticides and Polychlorinated Biphenyls in Black
Duck Eggs From United States and Canada - 1971,"
Pesticides Monitoring J., Vol. 7, No. 1 (1973), pp.
62-66.
36. F. L. Mayer, P. M. Mehrle, and H. 0. Sanders, "Resi-
due Dynamics and Biological Effects of PCB's in
Aquatic Organisms," Archives of Environ. Contam.
and Toxicol., manuscript, 21 p., (in press).
37. Monitoring Panel, FWGPM, "Criteria for Defining
Pesticide Levels to be Considered an Alert to Poten-
tial Problems," Pesticides Monitoring J., Vol. 5, No.
1 (1971), p. 36.
38. Monitoring Panel, FWGPM, "Guidelines on Sam-
pling and Statistical Methodologies for Ambient Pes-
ticide Monitoring," Federal Working Group on Pest
Management, Washington, D.C., 1974, 60 pp.
39. Monitoring Panel, FWGPM, "Catalog of Federal Pes-
ticide Monitoring Activities in Effect July 1973,"
Federal Working Group on Pest Management, Wash-
ington, D.C., 1975, 450 pp.
40. B. M. Mulhern, W. L. Reichel, L. N. Locke, T. G.
Lament, A, A. Belisle, E. Cromartie, G. E. Bagley,
and R. M. Prouty, "Organochlorine Residues and
Autopsy Data for Bald Eagles, 1969 and 1970," Pes-
ticide Monitoring J., Vol. 6, No. 3 (1970), pp.
133-138.
41. P. R. Nickerson and K. R. Barbehenn, "Organochlo-
rine Residues in Starlings, 1972," Pesticides Moni-
toring J..Vo\. 8, No. 4 (1975), pp. 247-254.
42. P. R. Nickerson and K. R. Barbehenn, "DDT Resi-
dues in Starlings, 1974," brief, Pesticides Monitor-
ing J. Vol.9, No. 1 (1975), p. 1.
43. Ian C. T. Nisbet and Adel F. Sarofim, "Rates and
Routes of Transport of PCB's in the Environment,"
Environmental Health Perspectives, Exp. Issue No.
1, DHEW, Nat. Inst. Environ. Health Sci., 1972, pp.
21-33.
4"4. W. L. Reichel, E. Cromartie, T. G. Lamont, B. M,
Mulhern, and R. M, Prouty, "Pesticide Residues in
Eagles," Pesticides Monitoring J., Vol. 3, No. 3,
(1969), pp, 142-144.
45. L. M. Reynolds, "Polychlorinated Biphenyls (PCB's)
and Their Interference With Pesticide Residue Anal-
ysis," Bull. Environ. Contam. and Toxicol., Vol. 4
(1969), pp. 128-143.
46. L. M. Reynolds, "Pesticide Residue Analysis in the
Presence of Polychlorinated Biphenyls (PCB's)" in
"Residues of Pesticides and Other Foreign Chemi-
cals in Foods and Feeds," Residue Reviews, F. A.
Gunther and J. D. Gunther, eds., Vol. 34 (1971),
pp. 27-57.
47. A. Richardson, J. Robinson, A. N. Crabtree, and M.
K. Baldwin, "Residues of Polychlorinated Biphenyls
in Biological Samples," Pesticides Monitoring J.,
Vol.4, No. 4 (1971), pp. 169-176.
48. R. K. Ringer, R. J. Aulerich, and M. Zabik, "Effect
of Dietary Polychlorinated Biphenyls oh Growth
and Reproduction of Mink," Amer. Chem. Soc. Air,
175
-------
Water, and Waste, New York, N.Y., 1972, pp.
149-154.
49. R. W, Risebrough and B. deLappe, "Accumulation
of Polychlorinated Biphenyls in Ecosystems," Envi-
ronmental Health Perspectives, No,, 1, DHEW, Nat.
Inst. of Environ. Health Sci, 1972, pp. 159-164
50. R. W. Riseborough, P. Rieche, D. B. Peakall, S- G.
Herman, and M. N. Kirven, "Polychlorinated Bi-
phenyls in the Global Ecosystem,"Nature,Vol. 220
(1968), pp. 1098-1102.
51. S. Safe and O. Hutzinger, "The Mass Spectra of
Polychlorinated Biphenyls," J. Chem. Soc. Vol. 5
(1972), pp. 689-691.
52. D. L. Stalling and J. N. Huckins, "Gas-Liquid Chro-
matography-Mass Spectrometry Characterization of
Polychlorinated Biphenyls (Aroclors) and 36CI-
Labeling of Aroclors 1248 and 1254," J. Assoc.
Official Anal. Chem., Vol. 54, No. 4 (1971), pp.
801-807.
53. D. L, Stalling and J. N. Huckins, "Reverse Phase
Thin Layer Chromatography of Some Aroclors,
Halowaxes and Pesticides," J. Assoc. Official Anal.
Chem.,Mo\. 56, No. 2 (1973), pp. 367-372.
54. D. L. Stalling and F. L. Mayer, "Toxicities of PCB's
to Fish and Environmental Residues," Environmen-
tal Health Perspectives, No, 1, DHEW, 1972, pp.
159-164.
55. D. L. Stalling, R. C. Tindle, and J. L. Johnson,
"Cleanup of Pesticide and Polychlorinated Biphenyl
Residues in Fish Extracts by Gel Permeation Chro-
matography," J. Assoc. Official Anal. Chem., Vol.
55, No. 1 (1972), pp. 32-38.
56. R. C. Tindle, "Purification Procedure for Low Polar-
ity Solvents," J. Agric. Food Chem., Vol. 17, No. 4
(1969), pp. 900-901.
57. R. C. Tindle, "Handbook of Procedures for Pesti-
cide Analysis," U.S.D.I. Bur. Sport Fish, and Wild-
life, Technical Paper No. 65, 1972, 88 pp.
58. R. C. Tindle and D. L. Stalling, "Apparatus for
Automated Gel Permeation Cleanup for Pesticide
Residue Analysis," Anal. Chem., Vol. 44, No, 11
(1972), pp. 1768-1773.
59. W. J. Trotter, "Removingthe Interference of DDT
and Its Analogs in the Analysis for Residues of Poly-
chlorinated Biphenyls," J. Assoc. Official Anal.
Chem.,Mo\. 58, No. 3 (1975), pp. 461-465.
60. G- D. Veith, "Baseline Concentrations of Polychlo-
rinated Biphenyls and DDT in Lake Michigan Fish,
1971," Pesticides Monitoring J., Vol. 9, No. 1
(1975), pp. 21-29.
61. D. F. Walsh, "Organochlorine and Heavy Metals
Detected in Fish - A Partial Review of the FWS
Contribution to the National Pesticide Monitoring
Program, 1967-1973," USFWS administrative re-
port, Atlanta, Ga., 1975, 35 pp.
62. H. Weingarten, D. W, Ross, J. M. Schlater, and G.
Wheller, Jr., "Gas Chtomatographaphic Analysis of
Chlorinated Biphenyls," Anal. Chem. Acta., Vol. 26
(1962), pp. 391-394.
63. D. H. White, "Nationwide Residues of Organochlo-
rines in Starlings, 1974," Pesticides Monitoring J.,
(in press).
64. D. H. White and R. G. Heath, "Nationwide Residues
of Organochlorines in Wings of Adult Mallards and
Black Ducks," Pesticides Monitoring J., (in press).
65. D. H. White and T. E. Kaiser, "Residues of Organo-
chlorines and Heavy Metals in Ruddy Ducks From
the Delaware River, 1973," brief, Pesticides Moni-
toring J., (in press).
66. G, Widmark, "Possible Interference by Chlorinated
Biphenyls," J, Assoc. Official Anal. Chem., Vol. 50,
No 5 (1967), p. 1069,
67, G- B. Widmark, H, Tai, and P. F. Sand, "Pesticide
Residue Levels in Soil," FY-1969-National Soils
Monitoring Program, Pesticides Monitoring J., Vol.
6, No. 3 (1972), pp. 194-201.
68- G. B. Wiersma, P. F. Sand, and E. L. Cox, "A Sam-
pling Design to Determine Pesticide Residue Levels
in Soil of the Conterminous United States," Pesti-
cides Monitoring J., Vol. 5, No. 1 (1971), pp. 63-66.
69. W. A. Willford, "Contaminants in Upper Great
Lakes Fishes," Great Lakes Fishery Commission
Meeting, Milwaukee, Wis., March 25-26, 1975,
Appendix V, 1975, pp. 31-39.
176
-------
TRENDS OF POLYCHLORINATED BIPHENYLS
IN THREE LAKE MICHIGAN FISHES
Wayne A. Willford,* Robert J. Hesselberg,t
and Lawrence W. Nicholsont
Abstract
Concentrations of poly chlorinated biphenyls
(PCB's) were determined from 1972 through 1974 in
three species of fish collected in the fall from eastern
Lake Michigan. Mean concentrations in whole fish
ranged in different years from 5.24 to 5.66 ppm in
bloaters fCoregonus hoyi^ 10.4 to 12.2 ppm in coho
salmon (Oncorhynchus kisutchj, and 12.9 to 22.9 ppm
in lake trout fSalvelinus namaycushA There was no
evidence of a decline in average PCB residues in the fish
sampled after the introduction in 1970-71 of voluntary
controls on the sale of PCB's in the United States.
INTRODUCTION
Past investigations have shown that substantial levels
of polychlorinated biphenyls (PCB's) were present in
fish from the open waters of Lake Michigan during the
late 1960"s. Veith and Lee (ref. 1) reported residues of
Aroclor 1254 ranging from 14 to 25 ppm in three coho
salmon (Oncorhynchus kisutch) and 6 to 25 ppm in
eight rainbow trout (Salmo gairdneri) collected from
western Lake Michigan during the spring of 1969.
Stalling and Mayer (ref. 2) reported a PCB concentration
(sum of Aroclors 1248 and 1254) of 13 ppm in a single
coho salmon collected from eastern Lake Michigan
during the fall of 1969. Extensive collections and analy-
ses of fish from Lake Michigan in 1971 confirmed the
approximate levels of PCB contamination found in
1969, and further demonstrated that residues in excess
of 5.0 ppm were common in several species of fish (refs.
3,4).
Because of the potential effects of PCB's on fish and
consumers of fish, the Great Lakes Fishery Laboratory
in 1972 incorporated analysis of PCB's with its routine
program of pesticide analysis in Lake Michigan fishes.
The program is designed to permit the accurate deter-
mination and statistical evaluation of contaminant levels
and trends with time in fish from Lake Michigan. Partic-
ular emphasis is placed on the yearly evaluation of con-
taminants in samples of bloaters (Coregonus hoyi) that
•Chief, Section of Physiology and Contaminant Chemistry,
U.S. Fish and Wildlife Service, Great Lakes Fishery Laboratory,
Ann Arbor, Michigan.
fResearch Chemists, U.S. Fish and Wildlife Service, Great
Lakes Fishery Laboratory, Ann Arbor, Michigan.
are similar in terms of fish size, location of catch, and
time of year sampled. Bloaters are particularly useful for
contaminant evaluation for several reasons:they repre-
sent an important commercial species that concentrates
pesticides and PCB's; they reflect local conditions be-
cause they are essentially nonmigratory; and they are
generally easy to catch in adequate numbers. Lake trout
(Salvelinus namaycush) and coho salmon are also
sampled annually because of their current importance as
sport fishes and their role in salmonid restoration pro-
grams. In addition, the analysis of lake trout provides an
estimate of contaminant levels in a long-lived predatory
species from the same geographic location as the bloat-
ers; and coho salmon serve as potential indicators of
lakewide contaminant trends because of their extensive
migrations.
This report presents the trends of average PCB con-
centrations in Lake Michigan bloaters, lake trout, and
coho salmon in 1972-74. The data provide a basis for
determining the effectiveness of past efforts to reduce
the contribution of PCB's to the Lake Michigan environ-
ment, as evidenced by the level of contamination in the
fisheries. Voluntary restrictions on PCB sales in the
United States were introduced in 1970-71.
FISH SAMPLING PROCEDURES
Bloaters (240-280 mm total length) and lake trout
(500-700 mm) were collected by gill net each fall
(September-October) in southeastern Lake Michigan, off
Saugatuck, Michigan. Coho salmon (600-750 mm) were
collected in east-central Lake Michigan near Ludington,
Michigan, in 1972, near the entry to Portage Lake in
1973, and from the lower weir on the Platte River in
1974.
All fish were placed in plastic bags previously deter-
mined to be free of pesticides and PCB's. The packaged
fish were frozen whole or packed in ice, transported to
the Great Lakes Fishery Laboratory, and stored at ap-
proximately -30° C. Before analysis, the bloaters were
measured and weighed, sorted according to sex and
length, grouped into 10-fish composite samples, and
homogenized (whole fish) by repeatedly passing them
through a meat grinder. A portion of the sample was
then further homogenized in a food blender. Individual
lake trout and coho salmon were measured, weighed,
sexed, and the whole fish similarly homogenized.
177
-------
ANALYTICAL PROCEDURES
Ten grams of homogenized fish were mixed with
anhydrous sodium sulfate and extracted by the method
of Hesselberg and Johnson (ref. 5). Lipids were removed
from the extract by gel permeation chromatography in
an automated system similar to that described by
Stalling et al. (ref. 6), after which the pesticides and
PCB's were separated on either silicic acid without Celite
545 (ref. 7) or on silica gel (ref. 8). The PCB's were
quantitated on a gas chromatograph equipped with
electron-capture detectors (63Ni, 8/uc) and a 5-ft x
l/8-in. ID glass column packed with 1.5 percent OV-101
on 80-100 mesh glass beads or Chromosorb W. Recov-
eries of PCB's from fortified samples of fish tissue aver-
age 88 percent by the described method. We performed
confirmatory analyses on each sample using a second,
10-g portion of tissue saponified in alcoholic potassium
hydroxide (ref. 9).
Results were calculated by summing the heights of
all peaks on the chromatogram attributable to PCB's,
and comparing them with the sum of peak heights
obtained from analytical standards composed of
Aroclors 1248, 1254, and 1260 (1:1:1). No corrections
were made for losses incurred during analysis or the pres-
ence of PCB's in blanks. All results are reported as total
PCB's in wet weight of tissue.
TRENDS OF PCB's
Mean concentrations of total PCB's during 1972-74
ranged from 5.24 to 5.66 ppm in bloaters, 10.4 to 12.2
ppm in coho salmon, and 12.9 to 22.9 ppm in lake trout
(table 1). A plot of mean PCB concentrations in bloaters
versus year of collection (figure 1) suggests no change in
PCB's during the 3 years of sampling. Statistical analysis
involving Student's t test (ref. 10) and the annual sam-
ples representing 110 to 160 fish showed that minor
differences between mean PCB concentrations for the
three sample dates were not significant. We therefore
conclude that mean PCB concentrations have remained
essentially unchanged since 1972 in large, adult bloaters
off Saugatuck, Michigan.
A plot of mean PCB concentrations in coho salmon
from 1972 to 1974 also fails to show any definite
change pattern (figure 2). The mean concentrations of
PCB's in these fish appear to have varied randomly
between 10.4 and 12.2 ppm. Statistical analyses show
that the decline between 1973 and 1974 is highly signif-
icant (P >0.01) but that the 1972 samples do not differ
significantly from either the 1973 or 1974 samples. Thus
despite the evidence of significant variation among the
three sample groups, there is no statistical evidence of a
10
(11)
1972
1973
YEAR
1974
Figure 1.
Trends of PCB's in Lake Michigan
bloaters off Saugatuck, Michigan.
Mean concentrations in whole fish
(wet weight) with 95 percent confi-
dence intervals (vertical lines).
Number of 10-fish composites
shown in parentheses.
15
10
(10)
1972
1973
YEAR
1974
Figure 2. Trends of PCB's in coho salmon
from eastern Lake Michigan. Mean
concentrations in whole fish (wet
weight) with 95 percent confidence
in intervals (vertical lines). Number
of fish in parentheses.
178
-------
Table 1. Concentrations of RGB's in fall collections of Lake Michigan
bloaters and lake trout taken off Saugatuck, Michigan, and
coho salmon from between Ludington, Michigan, and the
Platte River
Mean Mean Mean Range of
Species Date Number length weight lipid total PCBJs
and Year collected of fish (mm) (g) (percent) (ppm)
Mean
total PCB's
(ppm)a
Bloater
1972
1973
1974
Coho
salmon
1972
1973
1974
Lake
trout
1972
1973
1974
10/19
9/27
10/9
9/19
9/21
10/1
9/28
9/19
10/9
120(12)"
160(16)£
110(ll)b
10
29
30
9
30
30
255
250
257
693
620
665
648
602
616
177
165
175
4,156
2,967
3,148
2,576
2,353
2,514
21.6
20.0
21.6
7.3
6.0
5.4
18.5
16.0
16.5
3.12-8.17
4.20-6.33
4.83-6.22
4.93-15.4
8.24-16.6
6.99-16.3
3.53-25.3
9.36-30.6
7.05-47.4
5.66(0.95)
5.24(0.37)
5.57(0.31)
10.9(2.1)
12.2(0.8)
10.4(0.9)
12.9(4.8)
18.9(2.1)
22.9(3.7)
Concentrations in whole fish, wet weight, with 95 percent confidence interval
in parentheses.
DNumber of composite samples, 10 fish/sample, given in parentheses.
general increase or decrease during 1972-74 in mean PCB
concentrations in coho salmon from eastern Lake
Michigan.
Mean concentrations of PCB's in lake trout collect-
ed off Saugatuck, Michigan, appear to have increased
from 1972 to 1974 (figure 3). Although statistical analy-
ses show no significant differences between consecutive
years, the increase between 1972 and 1974 is highly
significant (P >0.005). Because of the comparatively
small number of lake trout collected in 1972 (9 fish) and
the high variability in PCB residues generally encoun-
tered between individual lake trout (table 1), the level of
confidence in the results is low and interpretation of the
apparent trend must be approached with considerable
caution. Although PCB's appear to have increased in lake
trout, there is no evidence of an upward trend of resi-
dues in bloaters (which represent the most reliable indi-
cator of trends) or coho salmon; consequently additional
sampling will be required to determine if the apparent
upward trend of PCB's in lake trout is real. We can safely
conclude, however, that mean PCB concentrations have
not declined in lake trout taken off Saugatuck,
Michigan.
TRENDS OF OTHER CHLORINATED
HYDROCARBONS
Mean concentrations of DDT and its metabolites
(total DDT) in the same samples of Lake Michigan fishes
employed for the PCB study declined 69, 48, and 26
percent respectively in bloaters, coho salmon, and in
lake trout during the period 1972-74 (ref. 11). Total
DDT residues in fish decreased significantly within 1
year after the ban (1969-70) on the use of DDT in the
179
-------
20
15
10
(30)
1972
1973
YEAR
1974
Figure 3. Trends of RGB's in Lake Michigan
Lake trout off Saugatuck, Michi-
gan. Mean concentrations in whole
fish (wet weight) with 95 percent
confidence intervals (vertical lines).
Number of fish in parentheses.
States bordering Lake Michigan. During 1970-74, mean
concentrations of total DDT dropped 87, 73, and 56
percent in" bloaters, coho salmon, and lake trout respec-
tively.
Mean concentrations of dieldrin in the same fish
samples showed no definite trend from 1970 to 74 (ref.
11). The lack of change is probably due to the common
use of dieldrin during the early 1970's. The rapid reduc-
tion of DDT residues in Lake Michigan fishes and Jhe
lower bioaccumulation characteristics of dieldrin lead us
to believe that the recent ban (1974) on the manufac-
ture and use of aldrin and dieldrin will result in a rapid
decline of dieldrin residues in Lake Michigan fishes.
SUMMARY AND CONCLUSIONS
Mean concentrations of PCB's in Lake Michigan
bloaters collected off Saugatuck, Michigan, have
remained essentially unchanged since yearly analyses
were initiated in 1972. Similarly, PCB residues in coho
salmon from eastern Lake Michigan show no definite
pattern of change. Residues of PCB's in lake trout col-
lected off Saugatuck, Michigan, are highly variable and
indicate a possible, but unconfirmed, upward trend in
mean PCB concentrations. Thus, voluntary restrictions
in 1970-71 on the sale of PCB's ithe United States have
not led to a decrease in PCB concentrations in the Lake
Michigan fishes sampled.
REFERENCES
1. Oilman D. Veith and G. Fred Lee, "PCB's in Fish
from the Milwaukee River," Proceedings of the
Fourteenth Conference on Great Lakes Research,
April 1971, pp. 157-169.
2. David L. Stalling arid Foster Lee Mayer, Jr.,
"Toxicities of PCB's to Fish and Environmental
- Residues," Environmental Health Perspectives, Vol.
1 (April 1972), pp. 159-164.
3. Great Lakes Fishery Laboratory, Progress in Sport
Fishery Research — 1971, Resource Publication
121, U.S. Bureau of Sport Fisheries and Wildlife,
Washington, D.C., 1973, pp. 86-120.
4. Gilman D. Veith, "Baseline Concentrations of Poly-
chlorinated Biphenyls and DDT in Lake Michigan
Fish, 1971," Pesticides Monitoring Journal, Vol. 9,
No. 1 (June 1975), pp. 21-29.
5. R. J. Hesselberg and J. L. Johnson, "Column Ex-
traction of Pesticides from Fish, Fish Food and
Mud," Bulletin of Environmental Contamination
and Toxicology, Vol. 7, No. 2/3 (1972), pp.
115-120.
6. David L. Stalling, Roger C. Tindle, and James L.
Johnson, "Cleanup of Pesticide and Polychlorinated
Biphenyl Residues in Fish Extracts by Gel Permea-
tion Chromatography," Journal of the Association
of Official Analytical Chemists, Vol. 55, No. 1
(1972), pp. 32-38.
7. J. A. Armour and J. A. Burke, "Method for Sepa-
rating PCB's from DDT and Its Analogs," Journal of
the Association of Official Analytical Chemists, Vol.
53, No. 4 (1970), pp. 761-768. *
8. Diane Snyder and Robert Reinert, "Rapid Separa-
tion of Polychlorinated Biphenyls from DDT and its
Analogues on Silica Gel," Bulletin of Environmental
Contamination and Toxicology, Vol. 6, No. 5
(1971), pp. 385-390.
180
-------
9. Robert E. Reinert, "Pesticide Concentrations in 11. Wayne A. Willford, "Contaminants in Upper Great
Great Lakes Fish," Pesticides Monitoring Journal, Lakes Fishes," report presented at the Upper Great
Vol. 3, No. 4 (1970), pp. 233-240. Lakes Committee Meetings of the Great Lakes
10. George W. Snedecor, Statistical Methods, Iowa State Fishery Commission, Milwaukee, Wisconsin, March
University Press, Ames, Iowa, 1957. 25-26, 1975, 9 p.
181
-------
A NOTE ON POLYCHLORINATED BIPHENYLS IN AIR
Frederick W. Kutz, Ph.D.* and Henry S. C. Yang
Abstract
Samples of ambient air were collected using an
ethylene-glycol impinger sampler, and analyzed for
selected pesticides and polychlorinated biphenyls in sub-
urban locations in Florida, Mississippi, and Colorado.
Preliminary results for samples taken in April, May, and
June of 1975 show that PCB's were present at all loca-
tions.
Samples of ambient air were collected and analyzed
for selected pesticides and polychlorinated biphenyls.
Suburban locations in Miami, Florida, Jackson, Mississip-
pi, and Fort Collins, Colorado, were sampled using an
ethylene-glycol impinger sampler essentially the same as
reported by Enos et al. (ref. 1) except that an improve-
ment of air flow rate was made. The air flow rate was
maximized and calibrated at ca. 30 l/min. Each sampler
was operated for a 24-hour period to collect one sample.
The analyses of samples were done by extraction with
hexane followed by cleanup with fluorsil column
chromatography, using a mixture of diethyl ether and
petroleum ether for elution; the fraction containing the
polychlorinated biphenyls and some organochlorine
•Project Officer, National Human Monitoring Program for
Pesticides, Ecological Monitoring Branch, Office of Pesticide Pro-
grams, Environmental Protection.Agency, Washington, D.C.
pesticides underwent further separation by silicic acid
column chromatography. Quantitation of the poly-
chlorinated biphenyls was done by summation of major
peaks employing the dual-column gas chromatography
with electron capture detector.
Preliminary results for samples taken in April, May,
and June of 1975 show that PCB's were present at all
locations. Although the data varied, the average con-
centration at each of the three locations was approxi-
mately lOOnanograms per cubic meter. The presence of
polychlorinated biphenyls in ambient air samples taken
in Miami and Jackson has been confirmed by combined
gas chromatography-mass spectrometry. Initial identifi-
cation of the polychlorinated biphenyls indicates that
they were most comparable to the Aroclor 1254 stand-
ard.
In July the number of sampling sites was expanded
to five with the addition of Lafayette, Indiana, and
Harrisburg, Pennsylvania. Results from all sites should be
available in the near future.
REFERENCE
1. H. F. Enos, J. F. Thompson, J. B. Mann, and R. F.
Moseman, "Determination of Pesticide Residues in
Air," (022-Pesticide Chemistry), Division of Pesti-
cide Chemistry, 163rd Meeting Proceedings, Ameri-
can Chemical Society, Boston, Massachusetts, April
1972.
182
-------
POLYCHLORINATED BIPHENYLS IN THE SURFACE WATERS AND BOTTOM SEDIMENTS
OF THE MAJOR DRAINAGE BASINS OF THE UNITED STATES
D. Steve Dennis, Ph.D*
Abstract
Data gathered from monitoring activities indicate
the widespread occurrence of PCB's in surface waters
and bottom sediments of the major drainage basins of
the United States. A preliminary assessment of PCB
levels shows median residue levels of the positive detec-
tions for the years 1971 to 1974 ranging between 0.1 to
3.0 /jg/l for unfiltered water samples and from 1.2 to
160.0 ng/kg for bottom sediments. The highest levels
were found in basins east of the Mississippi and bottom
sediments may contain concentrations of PCB's many
times higher than those in the overlying water.
INTRODUCTION
Within the past few years, particularly in the past
year, polychlorinated biphenyls (PCB's) have been iden-
tified as a major contaminant of natural waters. PCB's in
the hydrologic environment can originate from several
sources including: (1) runoff from sewage sludges dis-
posed of on land, (2) discharge of industrial and munici-
pal wastes (this includes treated as well as untreated
wastes), (3) accidental spills or improper waste disposal
practices, and (4) formerly as ingredients of pesticides or
as carriers for pesticides. Probably the largest amount of
PCB's in the environment results from industrial and
municipal discharges to inland and coastal waters (refs.
1-5).
Although much attention has been focused on
estimating levels of PCB's in aquatic organisms, and the
potential hazards involved, few data are availaWejpn the
occurrence of PCB's in water and trottSm" sediments. The
U.S. Department of Interior's Geological Survey and the
U.S. Environmental Protection Agency's (EPA) Office of
Pesticide Programs, Technical Services Division, through
their National Water Monitoring Program for Pesticide
Residues and various water-resource-assessment projects,
are accumulating data which permit a preliminary assess-
ment of PCB contamination of the Nation's drainage
basins. The data presented here were gathered by the
Geological Survey. They show the occurrence of PCB's
(PCB mixtures predominately resemble Aroclor 1254) in
whole water samples (i.e., water samples which are un-
filtered) and in bottom sediments in the 17 major drain-
*Project Officer, National Water Monitoring Program for
Pesticides, Ecological Monitoring Branch, Office of Pesticide
Programs, Environmental Protection Agency, Washington, D.C.
age basins of the United States and Puerto Rico (figure
1) for the years 1971 to 1974. All data were obtained
from STORET, which is EPA's computerized informa-
tion system that draws on both State and Federal agen-
cies for parametric data relating to water quality.
Although there is not a nationwide program specifi-
cally designed to assess PCB levels in the aquatic environ-
ment, the present Geological Survey and EPA water
monitoring programs are expanding and gradually in-
creasing to more adequately determine PCB levels in the
surface waters of the United States. These programs are
also being designed to determine both national and
regional trends in the concentration of PCB's.
METHODS AND PROCEDURES
Water samples were collected either by depth inte-
gration at the center of flow or by the equal-transit-rate
method. In the latter method a standard suspended-
sediment sampler, such as the US D-49 suspended-
sediment sampler, was used to collect a velocity- and
discharge-weighted sample. Samples were taken at a
number of equally spaced verticals across a stream,
depending on stream width (usually three sites were
sampled across a stream). The transit rate of movement
of the sampler from the water surface to the stream bed
and back to the surface was the same at all verticals.
Samples collected at each vertical were composited into
a single sample intended to represent the entire flow
across the stream.
Bottom sediments were sampled by collecting a
series of cores across the stream bed using piston type or
US BMH-60 or US BM-54 bed material samplers or a
commercial core sampler. When a core sampler was used,
cores were composited to form a representative sample
of the stream bed (see refs. 5,6 for a description of
sampling procedures).
Once the samples were collected, PCB residues were
analyzed by the multiple-pesticide-residue methods for
water, suspended sediment, and bottom sediment de-
scribed by Goerlitz and Brown (ref. 7).
Basic identification of PCB residues was made by
dual-column electron capture/gas-liquid chromatography
and confirmed by gas-liquid chromatography or mass
spectrometry. The amount of PCB's was determined by
matching the peaks on the chromatogram with the near-
est commercial formulation. The reported values are sub-
ject to some error because of the complexity of multiple
peaks resulting from mixtures of PCB's in environmental
samples.
183
-------
o
u
be
o
-t-*
L_
0)
D
Q.
T3
C
CD
CO
CD
•M
CO
o>
•M
'E
O)
x:
OJ
O)
03
C
T5
O)
*->
CD
c
o
o>
184
-------
Table 1. RGB's in whole water samples in the major drainage basins of the
United States and Puerto Rico for 1971
Drainage basin
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
% of
Sample positive
size detections
12 58.3
12 0
-
15 26.7
-
1 0
1 100.0
9 44.4
-
-
-
Median of Range of
positive positive
detections detections
in iag/1 in yg/1
0.2 0.1 - 2.1
ND ND
-
0.3 0.1 - 0.5
- -
ND ND
3.0 3.0
0.3 0.1 - 0.7
-
-
-
in California
12. Pacific Slope Basins
in Washington
13.
14.
15.
16.
17.
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico -
_
"
-
-
-
Note: - = no samples; ND = not detected.
185
-------
Table 2. RGB's in whole water samples in the major drainage basins of the
United States and Puerto Rico for 1972
Drainage basin
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
Sample
size
112
122
10
29
12
34
39
93
24
9
20
% of
positive
detections
17.0
0.8
20.0
13.8
16.7
'0
2.6
8.6
0
0
0
Median of Range of
positive positive
detections detections
in yg/1 in yg/1
0.1
ND
0.2
0.1
0.3
ND
0.1
0.3
ND
ND
ND
0.1 - 0.3
ND
0.1 - 0.2
0.1 - 0.2
0.2 - 0.3
ND
0.1
0.1 - 2.6
ND
ND
ND
in California
12. Pacific Slope Basins
in Washington
14
ND
ND
13.
14.
15.
16.
17.
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico
-
3
-
1
3
-
0
-
0
0
-
ND
-
ND
ND
-
ND
-
ND
ND
Note: - = no samples; ND = not detected.
186
-------
Table 3. RGB's in whole water samples in the major drainage basins of the
United States and Puerto Rico for 1973
Drai
1,
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
nage basin
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
in California
Pacific Slope Basins
in Washington
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico
Sample
size
109
114
6
31
30
95
291
362
64
12
73
33
2
9
-
1
37
% of
positive
detections
3.7
4.4
0
3.2
10.0
0
0.7
1.7
0
0
0
0
0
0
-
0
0
Median of Range of
positive positive
detections detections
in u9/l in ug/1
0.1
0.1
ND
0.1
0.2
ND
1.6
0.3
ND
ND
ND
ND
ND
ND
-
ND
ND
0.1
0.1 - 20.0
ND
0.1
0.1 - 0.4
ND
0.2 - 2.9
0.1 - 0.6
ND
ND
ND
ND
ND
ND
-
ND
ND
Note: - = no samples; ND = not detected.
187
-------
Table 4. PCB's in whole water samples in the major drainage basins of the
United States and Puerto Rico for 1974
% of
Sample positive
Drainage basin
1,
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Note
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
in California
Pacific Slope Basins
in Washington
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico
: - = no samples; ND =
size detections
51
151
24
38
33
28
269
325
52
12
74
13
11
8
-
1
68
not detected.
2.0
0
0
0
0
0
2.6
1.2
0
0
2.7
7.7
0
0
-
0
1.5
Median of " Range of
positive positive
detections detections
in yg/1
0.1
ND
ND
ND
ND
ND
0.1
0.3
ND
ND
0.1
0.1
ND
ND
-
ND
0.8
in yg/1
0.1
ND
ND
ND
ND
ND
0.1 - 0.2
0.2 - 0.7
ND
ND
0.1
0.1
ND
ND
-
ND
0.8
188
-------
Table 5. PCB's in bottom sediments in the major drainage basin of the
United States and Puerto Rico for 1971
Drainage basin
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
in California
Pacific Slope Basins
in Washington
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico
Median of Range of
% of positive positive
Sample positive detections detections
size detections in yg/kg in ug/kg
3 100.0 50.0 10.0 - 100.0
19 63.2 64.5 10.0 - 200.0
1 100.0 8.8 8.8
1 100.0 10.0 10.0
_
2 100.0 1.2 0.3 - 2.0
4 100.0 30.0 10.0 - 80.0
20 100.0 10.0 2.0 - 290.0
_
_
_
_
_
_ _ v. _
_
_
_
Note: - - no samples; ND = not detected.
189
-------
Table 6. PCB's in bottom sediments in the major drainage basins of the
United States and Puerto Rico for 1972
Drainage basin
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Note
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
in California
Pacific Slope Basins
in Washington
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico
: - = no samples; ND =
% of
Sample positive
size detections
56
101
-
10
3
22
25
66
7
9
6
9
1
1
-
1
-
not detected.
57.1
32.7
-
90.0
0
81.8
48.0
43.9
71.4
66.7
83.3
44.4
0
100.0
-
0
-
Median of Range of
positive positive
detections detections
in ug/kg in yg/kg
10.0
30.0
-
20.0
ND
2.0
2.0
4.0
2.0
2.0
20.0
2.0
ND
2.0
-
ND
-
5.0 - 800.00
5.0 - 500.00
-
2.0 - 800.0
ND
2.0
2.0 - 2400.0
2.0 - 250.0
2.0
2.0
2.0 - 190.0
2.0
ND
2.0
-
ND
-
190
-------
Table 7. PCB's in bottom sediments in the major drainage basins of the
United States and Puerto Rico for 1973
Drainage basin
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17,
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexi co
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
in California
Pacific Slope Basins
in Washington
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
Alaska
Hawaii
Puerto Rico
Sample
size
58
123
4
24
14
17
57
188
4
7
14
12
1
-
2
1
6
% of
positive
detections
70.7
48.8
25.0
91.7
0
0
1.8
3.7
0
0
0
0
0
_
0
0
16.7
Median of Range of
positive positive
detections detections
in yg/kg in yg/kg
10.0
10.0
20.0
20.0
ND
ND
20.0
50.0
ND
ND
ND
ND
ND
_
ND
ND
5.0
4.0 - 4000.
5.0 - 600.
20.0
5.0 -13000.
ND
ND
20.0
14.0 - 180.
ND
ND
ND
ND
ND
-
ND
ND
5.0
0
0
0
0
Note: - = no samples; ND = not detected.
191
-------
Table 8. RGB's in bottom sediments in the major drainage basins of the
United States and Puerto Rico for 1974
% of
Sample positive
Drainage basins
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Note
North Atlantic Slope
South Atlantic Slope
and Eastern Gulf of
Mexico
Ohio River
St. Lawrence River
Hudson Bay and Upper
Mississippi River
Missouri River
Lower Mississippi
Western Gulf of Mexico
Colorado River
Great Basin
Pacific Slope Basins
in California
Pacific Slope Basins
in Washington
Snake River
Pacific Slope Basins
in Oregon and Lower
Columbia River
.Alaska
Hawaii
Puerto Rico
: - = no samples; ND =
size detections
99
171
6
40
26
5
81
157
3
4
26
5
4
1
-
-
18
not detected.
56.6
25.7
33.3
60.0
0
0
9.9
21.7
0
0
11.5
0
0
0
-
-
27.2
Median of Range of
positive positive
detections detections
in i-ig/kg
31.0
11.0
35. ,0
20. .0
ND
ND
10.5
27.0
ND
ND
2.0
ND
ND
ND
-
-
160.0
in yg/kg
2.0 - 800.0
2.0 - 530.0
9.0 - 61.0
3.0 - 700.0
ND
ND
1.0 - 39.0
2.0 - 330.0
ND
ND
2.0 - 65.0
ND
ND
ND
-
-
10.0 - 640.0
192
-------
RESULTS
Tables 1 through 8 present the PCB residue data by
year for water and bottom sediments. For each year the
following is given: number of samples, percent of posi-
tive detections, median of positive detections, and maxi-
mum of positive detections in /Jg/l for water and ;ug/kg
for bottom sediments (one jug/l and one Mg/kg are rough-
ly equivalent to one ppb).
Not all drainage basins had detectable levels of
PCB's in both water and bottom sediments. However, it
should be noted that this may be in part due to the
location of sampling stations within drainage basins
and/or the small number of samples within drainage
basins.
Median residue levels of the positive detections in
whole water samples ranged from 0.2 to S.Ojug/l, 0.1 to
0.3 Mg/l, 0.1 to 1.6 jug/l, and 0.1 to 0.8 for all drainage
basins for 1971, 1972, 1973, and 1974, respectively
(tables 1 to 4). For both these data and the data for each
basin there is no indication of an increase in PCB levels
and in many instances the levels decreased. The highest
PCB level was found in the South Atlantic Slope and
Eastern Gulf of Mexico basin and in general, the highest
levels were found in basins east of the Mississippi. One
might speculate that this is due to the presence of cer-
tain industries in the eastern United States.
Bottom sediments showed a pattern similar to that
of water with the highest PCB residue levels occurring in
the eastern United States (table 5 to 8). Median residue
levels of the positive detections for all basins ranged
from 1.2 to 64.5 A/g/kg, 2.0 to 30.0 M/kg, 5.0 to 50.0
Aig/kg,and 2.0 to 160.0/jg/kg for 1971, 1972, 1973, and
1974, respectively. The data indicate that, as with the
whole water samples, the levels decreased in some basins.
However, it appears as if PCB's are more persistent in
bottom sediments.
DISCUSSION
The data which I have presented here indicate that
PCB's are widespread in the surface waters and bottom
sediments of the Nation. Crump-Wiesner et al. (ref. 9)
also found PCB's to have a ubiquitous occurrence and
distribution in surface water, ground water, and bottom
sediments. According to Veith and Lee (ref. 8) ". . . the
chlorinated biphenyls may be one of the more wide-
spread. . ." environmental contaminants.
It is well documented that bottom sediments may
contain concentrations of pesticide residues many times
higher than the overlying water (refs. 10-13). The data
presented here and previously published data (refs.
1,4,9,14) indicate that a similar relationship holds true
for PCB's. Even in drainage basins, where PCB's were not
detected in water samples such as the Missouri River,
they were present in bottom sediments. It is assumed
that this is due to the low water solubility and high
specific gravity of PCB's (ref. 14). According to Nisbet
and Sarofim (ref. 14), ".. . it is expected that most of
the PCBs discharged into the environment will be resting
as sludges or adsorbed in the sediment at the bottom of
rivers or lakes near their point of discharge, and that
transport in streams will be primarily by means of water-
borne particles."
Finally, it is important to note that although PCB's
are found in water and bottom sediments, this informa-
tion must be related to the entire aquatic environment
before the data can be adequately evaluated. This is
because (1) PCB's in solution and sorbed on organic and
inorganic particles are available for introduction into
food chains, (2) PCB's are accumulated in the tissues of
animals which are exposed to water and bottom sedi-
ments containing PCB's, (3) biological magnification
may occur in food chains, and (4) all components in an
aquatic ecosystem are interrelated.
REFERENCES
1. Interdepartmental Task Force on PCBs,Polychlorin-
ated Biphenyls and the Environment, National
Technical Information Service COM-17-10419,
1972, 181 pp.
2. A. V. Holden, "Source of Polychlorinated Biphenyl
Contamination in the Marine Environment," Na-
ture, Vol. 228 (1970), pp. 1220-1221.
3. T. T. Schmidt, R. W. Risebrough, and F. Gress, "In-
put of Polychlorinated Biphenyls into California
Coastal Waters from Urban Sewage Outfalls," Bull.
Environ. Contam. Toxicol., Vol. 6 (1971), pp.
235-243.
4. T. W. Duke, J. I. Lowe, and A. J. Wilson, Jr., "A
Polychlorinated Biphenyl (Aroclor 1254) in the
Water, Sediment, and Biota of Escambia Bay, Flori-
da," Bull. Environ. Contam. Toxicol., Vol. 5
(1970), pp. 171-180.
5. H. R. Feltz and J. K. Culbertson, "Sampling Proce-
dures and Problems in Determining Pesticide Resi-
dues in the Hydrologic Environment," Pestic.
Monit. J., Vol. 6 (1972), pp. 171-178.
6. H. P. Guy and V. W. Norman, "Field Methods for
Measurement of Fluvial Sediment," Techniques of
Water-Resources Investigations of the U.S. Geologi-
cal Survey: Book 3, Chapter C2,1970, 59 pp.
7. D. F. Goerlitz and E. Brown, "Methods for Analysis
193
-------
of Organic Substances in Water," Techniques of
Water-Resources Investigations of the U.S. Geologi-
cal Survey: Book 5, Chapter A3,1972, 40 pp.
8. G. D. Veith and G. F. Lee, "A Review of Chlorin-
ated Biphenyl Contamination in Natural Waters,"
Water Research. Vol. 4 (1970), pp. 265-269.
9. H. J. Crump-Wiesner, H. R. Feltz, and M. L. Yates,
"A Study of the Distribution of Polychlorinated Bi-
phenyls in the Aquatic Environment," Pestic.
Monit. J., Vol. 8 (1974), pp. 157-161.
10. H. R. Feltz, W. T. Sayers, and H. P. Nicholson,
"National Monitoring Program for the Assessment
of Pesticide Residues in Water," Pestic. Monit. J.,
Vol. 5 (1971), pp. 54-62.
11. T. E. Bailey and J. H. Hannum, "Distribution of
Pesticides in California," Amer. Soc. Civil Eng.
Proc., J. Sanit. Eng. Div., Vol. 93 (1967), pp. 27-43.
12. W. E. Odum, G. M. Woodwell, and C. F. Wurster,
"DDT Residues Absorbed From Organic Detritus by
Fiddler Crabs," Science, Vol. 164 (1969), pp.
F76-577.
13. J. 0. Keith and E. G. Hunt, "Levels of Insecticide
Residues in Fish and Wildlife in California," Tran-
script Thirty-First N. Amer. Wildlife Conf., 1966,
pp. 150-177.
14. I.C.T. Nisbet and A. F. Sarofim, "Rates and Routes
of Transport of PCBs in the Environment," Environ.
Health Perspec., Vol. 1 (1972), pp. 21-38.
194
-------
Abstract
PCB's IN AGRICULTURAL AND URBAN SOIL
A. E. Carey and J. A. Gowen*
SAMPLING PROCEDURES
Polychlorinated biphenyls in soil have been moni-
tored since 1972 as part of the National Soils Monitoring
Program, originally established to measure pesticide resi-
due levels in agricultural soils, raw agricultural commodi-
ties, and urban soils across the Nation. The PCB's are
monitored as part of this program because of their chem-
ical similarity to certain chlorinated pesticides.
The PCB's have rarely been detected in agricultural
soils of the United States. Only 0.1 percent of the soil
samples collected in the National Soils Monitoring Pro-
gram for 1972 contained detectable PCB levels. How-
ever, detectable levels of PCB's occur more frequently in
urban soils. Of the 19 metropolitan areas sampled since
1971, 12 of the cities, or 63 percent showed detectable
PCB levels. The most commonly encountered PCB was
Aroclor 1254, which was identified in approximately 40
percent of the positive samples, while Aroclor 1260 was
prevalent in about 20percent of the positive samples. In
the remaining 40 percent of the positive samples, no
identification was made of the specific Aroclor. The
occurrence of these compounds appears to be more prev-
alent in the "urban"portion (within the city limits) than
in the "suburban" portion (remainder) of these metro-
politan areas.
INTRODUCTION
The occurrence of polychlorinated biphenyls
(PCB's) in environmental media has been known and
well-documented for several years; it is only recently
that the magnitude of the contamination has created
widespread concern.
These compounds have been monitored in agricul-
tural and urban soils since 1972 as part of the National
Soils Monitoring Program. This program was established
to measure pesticide residue levels in agricultural soils,
raw agricultural commodities, and urban soils across the
Nation. It was initiated by the U.S. Department of Agri-
culture and is now operated by the U.S. Environmental
Protection Agency. The PCB's are monitored as part of
this program because of their chemical similarity to cer-
tain chlorinated pesticides.
For cropland sampljng, 50 cores 5.1 x 7.6 cm in size
were collected over an evenly spaced 5x10 grid on each
4-hectare site (ref. 1). In urban sampling, this procedure
was modified to collect 16 cores on a 4 x 4 grid over a
225-m2 plot (15 x 15m) (ref. 2). Field processing was
similar for both types of samples; the cores were com-
posited, thoroughly mixed, and sieved through a 6.3-mm
mesh, and a 2-I subsample was sent to the EPA Technical
Services Division's Pesticide Monitoring Laboratory in
Bay St. Louis, Mississippi, for chemical analysis.
ANALYTICAL PROCEDURES
Sample Preparation
A 300-g subsample was dampened with water and
extracted with 600 ml of 3:1 hexane:isopropanol sol-
vent. The isopropanol was removed by three distilled
water washes and the hexane extract was dried through
anhydrous sodium sulfate and stored at low temperature
for subsequent gas-liquid chromatographic analysis.
Gas-Liquid Chromatography
Analyses were performed on gas chromatographs
equipped with tritium foil electron affinity detectors. A
multiple system of polar and nonpolar columns was uti-
lized for identification and confirmation. Instrument
parameters ware as follows:
Columns:
Glass, 6 mm o.d. x 4 mm i.d., 183-cm long,
packed with one of the following: 9% QF-1 on
100/120-mesh Gas-Chrom Q; 3% DC-200 on
100/120-mesh Gas-Chrom Q; or 1.5%
OV-17/1.95% QF-1 on 100/120-mesh Sepul-
coport.
Carrier Gases:
5% methane-argon at a flow rate of 80 ml/min;
prepurified nitrogen at a flow rate of 80
ml/min.
Temperatures:
Detector
Injection port
Column QF-1
Column DC-200
Mixed column
*Soil Scientist and Agronomist, respectively. National Soils
Monitoring Program, Technical Services Division, U.S. Environ-
mental Protection Agency, WH-569, Washington, D.C. 20460.
200 C
250°C
166°C
170°-175°C
185°-190°C.
Sensitivity or minimum detection levels were 0.05 to 0.1
ppm. The average recovery rate in soil was 90 to 110
percent.
195
-------
DISCUSSION
Agricultural Soils
RGB's have rarely been detected in the Nation's agri-
cultural soils. Of the 1,556 soil samples collected in
1972 as part of the National Soils Monitoring Program,
only 2 samples or 0.1 percent contained detectable levels
of RGB's.
Urban Soils
Detectable levels of RGB's occur more frequently in
urban soils than in agricultural soils. Of the 19 metropol-
itan areas sampled since 1971, 12 of the cities, or 63
percent showed detectable levels of RGB's. Correspond-
ing data are presented in tables 1-4. The most commonly
encountered RGB was Aroclor 1254, which was identi-
fied in 39 percent of the positive samples, while Aroclor
1260 was prevalent in 21 percent of the positive sam-
ples. Although no attempt was made to identify the spe-
cific Aroclor in 39 percent of the positive samples, it is
likely that a majority contained Aroclor 1254.
All sites sampled within a metropolitan area were
classified into two of four categories. First, sites were
identified as either "lawn" or "waste," to indicate
whether or not they seemed likely to receive regular
maintenance. Secondly, each site was classified as urban
if it was within the city limits, and suburban if it was
located in the remainder of the metropolitan area.
When the positive sites in the 12 cities were catego-
rized in this manner, 42 percent were lawn sites (main-
tained), while 58 percent were waste sites (not main-
tained). This difference was not considered significant.
However, the second categorization showed that 70 per-
cent of the RGB-positive sites were urban, or within the
city limits, whereas only 30 percent were classified as
suburban sites. In comparison, the ratio of urban to sub-
urban sites for these 19 cities was 37 percent to 63
percent.
In summary, RGB occurrence in agricultural soils is
extremely rare and is not considered a problem. How-
ever, the occurrence of these compounds is more preva-
lent in metropolitan areas, particularly within city limits,
and monitoring should be continued to determine trends
over time.
REFERENCES
1. G. B. Wiersma, P. F. Sand, and E. L. Cox, "A Sam-
pling Design to Determine Pesticide Residue Levels
in Soils of the Conterminous United States,"Pestic.
Monit. J., Vol. 5, No. 1 (1971), pp. 63-66.
2. G. B. Wiersma, H. Tai, and P. F. Sand, "Pesticide
Residues in Soil From Eight Cities-1969," Pestic.
Monit. J., Vol. 6, No. 2 (1972), pp. 126-129.
Table 1. Occurrence of polychlorinated biphenyls in soils of
five U.S. cities sampled in 1971. U.S. Environmental
Protection Agency Urban Monitoring Program
Location
Baltimore, Md .
Gadsden, Ala.
Hartford, Conn.
Macon, Ga.
Newport News, Va.
Total
No. of
sites
156
55
48
43
78
No. of
positive
detections
6
1
NDa
ND
1
Percent of
positive
detections
3.9
1.8
-
-
1.3
Detected values
(ppm)
[linimum Maximum
0.09 0.74
11.94
3.30
Arithmetic
mean (ppm)
0.02
0.21
0.04
Geometric
mean
estimate (ppm)
0.001
*b
*
PCB
type- if
identified
1260
not
identified
1254
NO = Not detected.
* = Geometric mean estimate not calculated when less than two positive values present.
196
-------
Table 2. Occurrence of polychlorinated biphenyls in soils of
five U.S. cities sampled in 1972. U.S. Environmental
Protection Agency Urban Monitoring Program
Location
Des Moines, Iowa
Fitchburg, Mass.
Lake Charles, La.
Pittsburgh, Pa.
Reading, Pa.
Total
No. of
sites
82
35
70
189
49
No. of
positive
detections
3
NDa
1
1
ND
Percent of
positive
detections
3.7
-
1.4
0.5
-
Detected values
(ppm)
Minimum Maximum
0.34 0.94
1.31
1.01
Arithmetic
mean (ppm)
0.03
0.02
0.01
Geometric
mean
estimate (ppm)
0.002
*b
*
PCB
type- if
identified
not
identified
1254
not
identified
ND = Not detected.
* = Geometric mean estimate not calculated when less than two positive values present.
Table 3. Occurrence of polychlorinated biphenyls in soils of
five U.S. cities sampled in 1973. U.S. Environmental
Protection Agency Urban Monitoring Program
Total No. of Percent of Detected values Geometric PCB
No. of positive positive (ppm) Arithmetic mean type-if
Location sites detections detections Minimum Maximum mean (ppm) estimate (ppm) identified
Evansville, Ind.
Greenville, S.C.
Pittsfield, Mass.
Tacoma, Wash.
Washington, D.C.
82
86
45
95
116
NDa
3 3.5 0.13 1.59 0.02 0.001
ND
6 6.3 0.18 0.63 0.03 0.003
2 1.7 0.32 0.80 <0.01 0.001
1254
1-1254
5-not
identified
1-1254
1-not
identified
aND = Not detected.
197
-------
Table 4. Occurrence of polychlorinated biphenyls in soils of
five U.S. cities sampled in 1974. U.S. Environmental
Protection Agency Urban Monitoring Program
Location
Durham, N.C.
Gary, Ind.
San Francisco,
Calif.
Springfield, 111.
Pir.e Bluff, Ark.
Total
No. of
sites
66
89
119
72
59
No. of Percent of Detected values Arithmetic
positive positive (ppm) mean
detections detections Minimum Maximum (ppm)
1 1.5 0.40 0.01
5 5.6 0.50 3.33 <0.01
3 2.5 0.39 1.15 <0.01
NDa
Analyses not completed
Geometric PCB Percent of
mean type-if Analyses
estimate (ppm) identified Completed
*b 1254
0.003 1-not
identified
4-1254
0.001 1-not
identified
1-1254
1-1260
94
100
71
100
ND = Not detected.
b * =
= Geometric mean estimate not calculated when less than two positive values present.
198
-------
MARINE INPUTS OF POLYCHLORINATED BIPHENYLS
OFF SOUTHERN CALIFORNIA
David R. Young, Deirdre J. McDermott, and Theadore C. Heesen*
Abstract
Rates of poly chlorinated biphenyl (PCB) transport
via potential input routes to the coastal waters off south-
ern California have been quantified. Submarine discharge
of municipal wastewater was found to be the single larg-
est source, contributing 5,400 kg of these synthetic or-
ganics in 1974. However, inputs via this route appear to
be decreasing, as the corresponding estimate for 1971
exceeded 19,000 kg. Bottom sediments around the larg-
est outfalls contain up to Wppm PCB. Dry aerial fallout
also appears to be an important source. The estimated
deposition rate of 1254 PCB onto the coastal waters
during 1973-74 was 1,800 kg/yr; highest inputs were
measured off the Los Angeles Basin. This region also
contributed the most PCB in surface runoff, a/though
less than 800 kg were discharged annually during
1972-73 via storm and dry-weather flow. Direct indus-
trial discharges to San Pedro and San Diego Harbors did
not appear to be a significant PCB source, totaling less
than 250 kg/yr. Although antifouling paints may have
been a very significant source in the past, present inputs
are negligible. Also, despite high contamination levels
measured in three major harbors, we found no evidence
of significant PCB transport from these harbors to the
adjacent coastal waters.
INTRODUCTION
Polychlorinated biphenyls (PCB'sl have been used
for more than 4 decades in a wide variety of industrial
products (refs. 1,2). Within the last 10 years, the prob-
lem of environmental contamination by these synthetic
organic compounds has become a subject of increasing
concern (refs. 3,4,5). Here we report the results obtained
to date on the routes by which RGB's enter one coastal
*David Young is Senior Environmental Specialist in Chemi-
cal Oceanography, Southern California Coastal Water Research
Project, El Segundo, California; Deirdre McDermott and Thea-
dore Heesen are also with Southern California Coastal Water
Research Project, El Segundo, California.
This research was supported in part by the National Coastal
Pollution Research Program of the Environmental Protection
Agency, Grant R801153. Investigations into the harbor dis-
charges of RGB's were conducted in connection with State of
California Agreement M-11 with the Marine Research Com-
mittee, Department of Fish and Game. Contribution 54 of the
Southern California Coastal Water Research Project.
marine ecosystem, the Southern California Bight, and
the rates at which inputs occur.
MUNICIPAL WASTEWATERS
Every day, over 1 billion gallons (approximately 4 x
109 I) of municipal wastewaters are discharged from
submarine outfalls to the Southern California Bight.
Almost 95 percent of these wastewaters are released by
five major treatment plants.! By sampling these five
plants, we have been able to obtain a reasonably repre-
sentative picture of PCB inputs to the Bight via this
route. Resultant effluent concentrations and estimated
annual mass emission rates for 1972-75 are summarized
in table 1; details of sampling and analytical procedures
are presented elsewhere (ref. 6). These data indicate that
in recent years there has been a significant decrease in
the amount of PCB's discharged through these outfall
systems.
The municipal wastewater discharges have resulted
in obvious contamination of the bottom sediments
around the larger outfall systems. Figure 1 illustrates
concentrations of total PCB measured in surface sedi-
ments collected around the Hyperion outfalls in Santa
Monica Bay. The maximum concentration measured
near the longer Hyperion outfall (the sludge line) and
the JWPCP outfalls were similar, on the order of 10 ppm
(mg/dry kg). However, within a few kilometers of the
Hyperion sludge discharge, the surface sediment concen-
trations of PCB had fallen to about 0.2 ppm. Near the
JWPCP outfalls, large vertical gradients were observed,
with values decreasing by one to two orders of magni-
tude over a 30-cm depth. We estimate that the load of
1254 PCB in these Palos Verdes Shelf sediments (50 sq
km) is on the order of 6 metric tons (ref. 7). Surface
sediments around the Orange County outfall did not
exhibit large gradients of total PCB in 1975; the median
value was 0.1 ppm, with values ranging from 0.04 to 0.3
ppm. Similar concentrations were measured 6 months
after discharge commenced in 1971, indicating little
buildup of PCB's in these sediments since then.
tThese treatment plants are located near the following sta-
tions indicated in figure 2: Oxnard-Port Hueneme; Hyperion-
Santa Monica; JWPCP-Palos Verdes Peninsula; Orange Co.-
Newport Beach; Point Loma-midway between La Jolla and the
U.S.-Mexico border.
199
-------
Table 1. Representative PCB concentrations and mass emission rates3
from major municipal wastewater discharges to the Southern
California Bight, 1972-75
Discharger
1972
JWPCP
Hyperion
Effluent
Sludge
Orange Co.
Point Loma
Oxnard
Total
1973
JWPCP
Hyperion
Effluent
Sludge
Orange Co.
Point Loma
Oxnard
Total
1974
JWPCP
Hyperion
Effluent
Sludge
Orange Co.
Point Loma
Oxnard
Total
1975
JWPCP
Hyperion
Effluent
Sludge
Orange Co.
Point Loma
Oxnard
Total
Total
Susp.
Solids
(mq/1)
290
90
7,670
150
140
70
260
80
7,500
150
160
130
280
80
7,300
110
140
170
Concen-
tration
(Jiq/l)
24
ND
280
28
ND
ND
3.9
ND
ND
ND
ND
ND
1.9
0.11
72
8.0
6.6
0.1
0.6
0.06
34
5.2
1.1
0.03
Mass
Emission
Rate
(kq/vr)
11,600
-
1,780
5,800
-
-
>19,180
1,930
-
-
-
-
-
>1,930
910
50
470
1,890
950
1
4,270
290
30
220
1,230
160
0.4
1,930
Concen-
tration
(UCf/1)
ND
0.3
ND
ND
0.9
0.2
1.6
0.38
26
1.4
0.48
0.35
0.76
0.24
50
0.89
0.74
0.24
0.52
0.18
23
0.63
0.39
0.16
Mass
Emission
Rate
(kq/yr)
-
140
-
-
120
3
}260
790
180
170
290
70
6
1,510
360
110
320
210
110
3
1.110
250
80
180
150
60
2
720
The following 1974 flow values (million gallons per day) were used for
calculations of preliminary 1975 mass emission rates: JWPCP—350; Hyperion
effluent—340; Hyperion sludge—4.7; Orange Co.—170; Point Loma—100;
Oxnard—10.
200
-------
• Pt.Dume.
IIB'ZO
KM
STATION B3
DEPTH PROFILE.
,
00
6 IZ /8
DEPTH (cm)
30
Palos Verdes ?t
Figure 1. Concentrations of total PCS (mg/dry kg) measured in the
top 2 cm of bottom sediments collected during July 1971
off the Hyperion submarine outfalls in Santa Monica Bay.
We have found that benthic organisms trawled from
these regions are highly contaminated with PCB's. Crab
and flatfish muscle tissue contain on the order of 1 ppm
total PCB, approximately 100 times the levels measured
in specimens from uncontaminated control stations. De-
tails of these studies are presented elsewhere in these
proceedings (ref. 8) and a background paper (ref. 9).
SURFACE RUNOFF
In water year 1971-72, we conducted a detailed sur-
vey of chlorinated hydrocarbon inputs to the Southern
California Bight via storm runoff. During the major
storms of the year, time series of depth-integrated
samples were collected in an all-metal sampler near the
mouths of four major drainage channels-the Santa Clara
River, Ballona Creek, the Los Angeles River, and the
Santa Ana River.* Analyses of the preserved samples
"These channels discharge surface runoff near the following
stations indicated in figure 2: Santa Clara R.-Port Hueneme;
Ballona Ck.-Santa Monica; Los Angeles R.-midway between
Palos Verdes Peninsula and Newport Beach; Santa Ana R.-New-
port Beach.
were conducted by Dr. R. Risebrough and B. de Lappe
at Bodega Marine Laboratory (University of California at
Berkeley). The following year, we resurveyed one of
these channels on a limited basis. Los Angeles River run-
off was sampled during four storms and analyzed in our
laboratory. Subsequently, two seasonal collections of
dry-weather flow were made from channels located
throughout the Bight (ref. 6).
Table 2 presents final flow-weighted mean PCB con-
centrations in 1971-72 storm runoff in the four channels
samples. In table 3 we list flow-weighted mean PCB con-
centrations for the four Los Angeles River storm flows
sampled in 1972-73, and compare the yearly averages for
this channel with those for 1971-72. To aid in the com-
parison, we also list corresponding results for total DDT
and dieldrin. In light of the variation measured in con-
centrations during any given storm, and the fact that
two water years and two laboratories were involved, the
agreement between the flow-weighted means is remark-
ably good. Because of this general agreement, we con-
cluded that the clats from the 1971-72 Bight-wide storm
runoff survey could be extrapolated to the following
year, on the basts of relative flow rates
201
-------
Table 2. Flow-weighted mean concentrations (,Mg/l)
of PCS in storm runoff via major channels
in southern California, 1971-72
Channel
Santa Clara
Ballona
Los Angeles
Santa Ana
Volume3
(106
cu m)
9.0
2.6
9.0
1.0
1242 PCB
0-0.13
0-0.43
1.2-1.9
ND
1254 PCB
0-0.16
0.47
0.9-1.1
0.11-0.23
Total PCB
0-0.29
0.47-0.90
2.1-3.0
0.11-0.23
Accumulated storm flow from which samples were obtained for
chlorinated hydrocarbon analysis.
Table 3. Flow-weighted mean concentrations O-tg/0 of chlorinated
hydrocarbons in Los Angeles River storm runoff, 1971-73
Date
4-7 Dec 72
27 Feb to
1 Mar 73
6-9 Mar 73
11-12 Mar 73
Average
blank
Averages
1972-73
1971-72
Total
DDT
0.66
1.5
0.78
0.60
<0.004
0.92
0.93
Dieldrin
0.12
0.16
0.16
0.08'
<0.001
0.14
0.16
1242
PCB
0-1.1
0-3.2
0-1.0
0-2.6
<0.002
0-1.9
1.2-1.9
1254
PCB
0.51
1.0
0.83
0.71
O.001
0.77
0.9-1.1
Total
PCB
0.5-1.6
1.0-4.2
0.8-1.8
0.7-3.3
<0.003
0.8-2.7
2.1-3.0
202
-------
The results indicate that the Los Angeles River
carried an order of magnitude more RGB's via storm run-
off than any other channel in the Bight. Further, the
estimated input of 1254 PCB in storm runoff from the
major channels in the Los Angeles Basin was 235 kg,
constituting 86 to 98 percent of the estimated total
storm runoff input of this contaminant to the Bight.
These channels also carried more than 80 percent of the
dry-weather input of 1254 PCB. A comparison of mass
emission rates for all areas via the dry-weather and storm
runoff for water year 1972-73 is presented in table 4.
This summary illustrates that, although dry-weather flow
constituted almost 20 percent of the total surface runoff
volume during the year, it carried only about 5 percent
of the measurable RGB's. Thus, it appears that storm
runoff is the dominant mode for surface runoff inputs of
PCB to the Bight, and that the Los Angeles Basin is the
principal source region.
AERIAL FALLOUT
We conducted our aerial fallout surveys by exposing
glass plates sprayed with mineral oil for about 1 week at
13 coastal and 5 island stations between Point Concep-
tion and the U.S./Mexico border. Two 13-week surveys
were conducted in summer 1973 and spring 1974, and a
3-week survey was conducted during fall 1974. Although
fallout rates of 1242 PCB were not obtainable, apparent-
ly because of poor retention of this relatively volatile
mixture, the collection efficiency for 1254 PCB over
1-week exposure was determined to be about 50 percent
-------
figure 2. Highest values (each over 100 kg/yr) occurred
in the five sectors off Los Angeles and Orange Counties
(centering around the Palos Verdes Peninsula). This
portion of the coastal plain of southern California is
most affected by air pollution. The three sectors
between Zuma Beach and Newport Beach (100 km by
50 km), which account for only about 10 percent of the
50,000-sq-km study area, received approximately 25 per-
cent of the total measured PCB input. Thus, we find a
pattern similar to that for surface runoff: The central
basin area appears to be the single most important
source of 1254 PCB transported via the atmosphere to
the waters of the Bight.
DIRECT INDUSTRIAL DISCHARGE
Most of the industrial wastewaters released directly
to marine waters off southern California occur in San
Pedro and San Diego Harbors. These harbors also receive
a wide variety of industrial discharges. Thus, we were
able to study a number of different types of industrial
effluents under similar conditions by surveying the two
harbors (ref. 6). Estimates for overall industrial inputs of
1254 PCB to San Pedro Harbor were obtained by calcu-
lating flow-weighted concentrations in three types of
effluents—power plant cooling water, fish cannery
wastes, and "other industrial" discharges. The flow-
weighted concentrations were then multiplied by the
reported total flows of each of the three classes of indus-
trial wastewaters into San Pedro Harbor to obtain esti-
mates of annual mass emission rates. The values are pre-
sented in table 5. Corresponding data for San Diego Har-
bor are given in table 6.
These data provide no indication of significant
release of PCB's to the harbors from the industrial efflu-
ents studied. However it should be noted that shipyard-
related discharges into Los Angeles Harbor had the high-
est 1254 PCB concentrations of the industrial discharges
surveyed; vessel cooling water, ballast effluent, and oil
tanker clean-down water contained 0.6, 1.5, and 2.1
Pt.Conception
11
iCarpinteria
(JQ fcL/wi Hueneme.
Figure 2. Estimated annual input of 1254 PCB (kg/yr) to sectors
of the Southern California Bight via dry aerial fallout
during 1973-74.
204
-------
Table 5. Flow-weighted mean concentrations and estimated 1973
mass emission rates of 1254 PCB in industrial discharges
to San Pedro Harbor
Discharge type
Power plant
cooling water
Fish cannery
Total flow
(mgd)
1,020
15
Concentration
(yg/D
0.01
0.09
Mass
emission
rate
(kg/yr)
14
2
wastes
Other industrial
wastes
Total
250
0.10
35
50
Table 6. Flow-weighted mean concentrations and estimated 1974
mass emission rates of PCB in industrial discharges to
San Diego Harbor
Discharge
type
Cooling waters
Brine waters
Flume waters
Total
Total
flow
(mgd)
757
0.5
2.8
1242
Concen-
tration
(yg/D
<0.03
<0.01
<0.02
PCB
"Mass
emission
rate
(kg/yr)
<30
<0.01
<0.07
<30
1254
Concen-
tration
(yg/D
0.01
0.05
0.01
PCB
Mass
emission
rate
(kg/yr)
10
0.03
0.05
10
/xg/l 1254 PCB respectively. These relatively high levels
are consistent with our observations that highest levels
of this contaminant in harbor mussels occurred in
regions of greatest vessel activity (ref. 8-11).
VESSEL ANTIFOULING PAINT
In 1973, we surveyed numerous drydock or haulout
facilities in southern California harbors and marinas (ref.
12). Our objective was to obtain a representative picture
of antifouling paint usage in southern California. In only
7 of the 28 wet paint samples analyzed, 1242 PCB or
1254 PCB were detected; levels were generally on the
order of 1 mg/ I or below. Although two samples had
total PCB concentrations of approximately 40 mg/1,
median values for 1242 and 1254 PCB were 0.3 mg/l
and 0.7 mg/l, respectively. Combination of these medi-
an values with the estimated 300,000 liters of antifoul-
ing paint applied annually to recreational, commercial,
and naval vessels in marinas and harbors of the Bight
205
-------
indicates that marine inputs of PCB from this source
now are completely negligible.
However, four samples of old paint scraped from
vessel bottoms yielded total PCB concentrations of 270,
3,300, 56,000, and 150,000 ppm, respectively. Further-
more, the two highest concentrations (approximately 5
and 15 percent on a dry weight basis) correspond with
an observation by Dr. V. McClure,* who found that a
paint chip collected in a zooplankton trawl in 1970 con-
tained approximately 10 percent PCB. Polychlorinated
biphenyls are reported to have been used extensively as a
plasticizer in paints before such use was banned in this
country in 1971. Our survey revealed that, on the aver-
age, the density of antifouling paints used in southern
California is about 1.5 dry kg/1. Therefore, if such
paints did contain 10 percent PCB in the past, an appli-
cation rate of 300,000 I /yr would correspond to a PCB
usage of 45,000 kg/yr. Antifouling paints are designed to
slough off with time, and an estimated 5 to 10 percent
of the old paint removed from vessel bottoms is believed
to be carried back to the harbor waters (ref. 13). Thus
these observations point to the possible importance of
antifouling paints in the past as a source of PCB's to the
coastal marine environment.
HARBOR FLUSHING
In view of the relatively high levels of PCB contam-
ination found in southern California harbors (refs. 8-11),
we attempted to determine if any significant levels of
PCB's could be detected in the waters moving from such
harbors into the open ocean during periods of peak tidal
flow (ref. 6). Figure 3 illustrates the results obtained
from the San Diego Harbor survey; net concentrations of
1254 PCB for the replicate samples of each collection
period are plotted against tidal flow. Although there is
some evidence of increased PCB concentrations near the
time 'of tide reversal, when the greatest influence of
"back harbor" water would occur near the harbor
mouth, the measured concentrations were extremely
low; flow-weighted mean concentrations for San Pedrot
and San Diego Harbors were 1.5 and 1.8 ng/l, respec-
tively.
By combining the measured concentrations with
tidal flow values obtained from the current meter meas-
urements and channel geometries, we obtained estimates
for maximum net transport of 1254 PCB from the har-
bors to the adjacent coastal ecosystem. Because of the
extremely low concen!rations observed, none of the
'National Marine Fisheries Service, La Jolla, personal com-
munication.
tLocated just east of Palos Verdes Peninsula (figure 2).
6000
— - 3000
0700
1100
TIME
1500
1900
Figure 3. Concentrations of 1254 PCB in surface seawater collected over a semidiurnal
tidal cycle at the mouth of San Diego Harbor, November 12, 1974. Positive
flow represents outflowing water; negative, inflowing. Vertical bars indicate
individual replicate values.
206
-------
values exceeded 50 kg/yr when extrapolated to an
annual basis. Thus, these pilot seawater surveys have
provided no indication that any of the three harbors is
now a significant source of polychlorinated biphenyls to
the coastal marine ecosystem.
OCEAN CURRENT ADVECTION
As a part of this inputs study, we attempted to
estimate the quantities of measurable chlorinated hydro-
carbons in surface seawater annually flowing through the
Southern California Bight. In October 1973, we sampled
surface seawater at seven stations along a north/south
transect (120°35'W) at the northwestern edge of the
Bight (ref. 6). The transect began off Point Conception
and ended approximately 300 km west of Oceanside.
Circulation patterns (ref. 14) indicated that the transect
chosen should have intersected California Current water
flowing into the Bight.
Replicate 40-liter samples were collected in a stain-
less steel bucket, which was lowered from the bow of a
research vessel that was slowly underway. Immediately
upon collection, the replicate samples were passed
through polyurethane foam columns and taken to
Bodega Marine Laboratory for analysis. The results indi-
cated average concentrations for total DDT and 1254
PCB of 0.7 and 0.4 ng/l, respectively.
These data may be used to obtain rough estimates
of the quantity of these synthetic organics carried into
the Bight via ocean current advection. Taking the length
of the Bight as 500 km and the width influenced by the
coast as 100 km, the effective study area is 5 x 101 ° sq
m. Assuming the mixed surface layer to be 50 m, the
volume of the mixed layer is 2.5 x 1012 cu m. It has
been shown that the mean residence time of water in
this mixed layer is on the order of 3 months (ref. 14).
Thus, the estimated advective flow rate of California
Current water through the Southern California Bight is
1013 cu m/yr, equal to 1016 l/yr. Corresponding
estimates for advective flux rates of measurable DDT
and 1254 PCB compounds are 7,000 and 4,000 kg/yr,
respectively.
CONCLUSIONS
Table 7 summarizes input rates of polychlorinated
Table 7. Inputs of RGB's to the Southern California Bight
PCB's (kg/yr)
Route
Municipal
waste water
Surface
runoff
Aerial
fallout
Industrial
discharges
Anti foul ing
paint
Harbor ,
flushing0
Ocean
currents
Year 1242
1974 4,300
1972-73 < 550
1973-74
1973-74 < 180a
1973 < 1
1974
1973
1254
1,100
250
1,800
60
< 1
< 150
4,000
Total
5,400
< 800
-
< 250
< 1
-
-
Assuming that the maximum 1242/1254 PCB ratio (3:1)
found in San Diego Harbor also applies to San Pedro
Harbor industrial discharges.
DSan Pedro, Newport, and San Diego Harbors.
207
-------
biphenyls to the marine waters off southern California.
These data indicate that, in recent years, municipal
wastewaters have been the dominant source of RGB's to
this coastal marine ecosystem. In 1974, more than 5
metric tons of this synthetic organic material were dis-
charged via the five major treatment plants in the Bight;
the fact that the 1254 PCB values for municipal waste-
waters and ocean current transport were of the same
order of magnitude testify to the importance of the
wastewater input route.
Aerial fallout is the other important route by which
RGB's enter the waters of the Bight. The 1973-74 esti-
mate of 1,800 kg for 1254 PCB exceeded the 1974 input
from municipal wastewaters (1,100 kg), and the fact
that PCB levels in municipal wastewater are continuing
to decrease suggests that aerial transport of these con-
taminants may become the dominant input mode in the
future.
Finally, these studies have demonstrated that, in
southern California, surface runoff is only a secondary
PCB source, while contributions from industrial dis-
charges and antifouling paint use in the major harbors
appear to be insignificant. Although intertidal mussels in
these harbors had an order of magnitude more PCB in
their soft tissues than did nearby coastal specimens, we
found no evidence that harbor flushing constitutes a sig-.
nificant source of polychlorinated biphenyls to the
coastal marine ecosystem.
REFERENCES
1. S. Jensen, "PCV as a Contaminant: History," in
PCB Conference, pp. 6-17, National Swedish Envi-
ronment Protection Board, Solna, Sweden, 1970.
2. P. Jay, "PCB: Uses in Industry," in PCB Confer-
ence pp. 18-25, National Swedish Environment Pro-
tection Board, Solna, Sweden, 1970. •
3. R. W. Risebrough, P. Rieche, D. B. Peakall, S. G.
Herman, and M. N. Kirven, "Polychlorinated Bi-
phenyls in the Global Ecosystem," Nature, Vol. 220
(1968), pp. 1098-1102.
4. M. Kuratsune, T. Yoshimura, J. Matsuzaka, and A.
Yamaguchi, "Epidemiologic Study on Yusho, a
Poisoning Caused by Ingestion of Rice Oil Contami-
nated with a Commercial Brand of Polychlorinated
Biphenyls," Environ. Health Perspectives, Vol. 1
(1972), pp. 129-36.
5. R. L. de Long, W. G. Gilmartin, and J. G. Simpson,
"Premature Births in California Sea Lions: Associa-
tion with High Organochlorine Pollutant Residue
Levels," Science, Vol. 181 (1973), pp. 1168-70.
6. D. R. Young, D. J. McDermott, and T. C. Heesen,
"Polychlorinated Biphenyl Inputs to the Southern
California Bight," background paper prepared for
the National Conference on Polychlorinated Bi-
phenyls, 19-21 November 1975, Chicago, Illinois,
Rept. TM 224, So. Calif. Coastal Water Res. Proj.,
El Segundo, Calif., 1975.
7. D. R. Young, D. J. McDermott, and T. C. Heesen,
"Polychlorinated Biphenyls Off Southern Califor-
nia," to be published in the proceedings Volume of
the International Conference on Environmental
Sensing and Assessment, 14-19 September 1975,
Las Vegas, Nevada.
8. D. J. McDermott, D. R. Young, and T. C. Heesen,
"PCB Contamination of Southern California Marine
Organisms," in the proceedings of the National Con-
ference on Polychlorinated Biphenyls, 1975.
9. D. J. McDermott, D. R. Young, and T. C. Heeseni
"Polychlorinated Biphenyls in Marine Organisms
Off Southern California," Rept. TM 223, So. Calif.
Coastal Water Res. Proj., El Segundo, Calif., 1975.
10. D. R. Young, and T. C. Heesen, "Inputs and Distri-
butions of Chlorinated Hydrocarbons in Three
Southern California Harbors," Rept. TM 214, So.
Calif. Coastal Water Res. Proj., El Segundo, Calif.,
1974.
11. D. R. Young, D. J. McDermott, T. C. Heesen, and T.
K. Jan, "Pollutant Inputs and Distributions Off
Southern California," to be published in the pro-
ceedings volume of the 169th National Meeting of
the American Chemical Society, Symposium on
Marine Chemistry in the Coastal Environment, 8-10
April 1975, Philadelphia, Penn.
12. D. R. Young, T. C. Heesen, D. J. McDermott, and P.
E. Smokier, "Marine Inputs of Polychlorinated Bi-
phenyls and Copper From Vessel Antifouling
Paints," Rept. TM 212, So. Calif. Coastal Water Res.
Proj., El Segundo, Calif., 1974.
13. J. N. Barry, "Wastes Associated with Shipbuilding
and Repair Facilities in San Diego Bay," staff
report, California Regional Water Quality Control
Board, San Diego Region, 1972.
14. J. H. Jones, "General Circulation and Water Charac-
teristics in the Southern California Bight," Rept. TR
101, So. Calif. Coastal Water Res. Proj., El Segundo,
Calif., 1971.
208
-------
PCB CONTAMINATION OF
SOUTHERN CALIFORNIA MARINE ORGANISMS
Deirdre J. McDermott, David R. Young,
and Theadore C. Heesen*
Abstract
In the past, the submarine discharge of municipal
wastewater has been the dominant source of PCB to the
marine environment off southern California. However,
the level of input from this source has steadily decreased
during the period 1972 f> 19,000 kg/yr) to 1975 (2,600
kg/yr). Despite the significant decrease in this input, no
significant decrease was observed over the 3-year period
1971-72 to 1974-75 in the level of PCB in muscle tissue
of Dover sole, Microstomus pacificus, collected from the
major municipal wastewater discharge sites. In contrast,
similar surveys of the intertidal mussel, Mytilus califor-
nianus, indicated that the PCB levels in this marine orga-
nism had significantly decreased over the same time
period.
Bight-wide surveys of M. californianus and the yel-
low rock crab. Cancer anthonyi, indicate that PCB con-
tamination of these marine animals is low but wide-
spread. Levels of PCB in the harbor mussel, M. edulis,
were highest in specimens collected from areas of intense
vessel activity. A convenient and effective system for
continuously monitoring PCB levels in the marine envi-
ronment is described.
INTRODUCTION
Over the last 4 years, the Southern California
Coastal Water Research Project has been studying the
inputs of RGB's to the Southern California Bight. A
number of sources of RGB's (most closely resembling
Aroclors 1242 and 1254) to the marine environment off
southern California have been identified and their inputs
quantified. The submarine discharge of municipal waste-
water has been the dominant source of PCB to the
marine environment off southern California. However,
'Deirdre McDermott is Assistant Environmental Specialist
in Chemical Oceanography, Southern California Coastal Water
Research Project, El Segundo, California. David Young and
Theadore Heesen are also with Southern California Coastal Water
Research Project, El Segundo, California.
This research was supported in part by the National Coastal
Pollution Research Program of the Environmental Protection
Agency, Grants R801153 and R801152. Investigations into the
harbor distributions of PCB's were conducted in connection with
State of California Agreement M-11, with the Marine Research
Committee, Department of Fish and Game. Contribution 53 of
the Southern California Coastal Water Research Project.
the level of input from this source has steadily decreased
during the period 1972 (> 19,000 kg/yr) to 1975 (2,600
kg/yr). Dry aerial fallout also appears to be an important
source, and if wastewater inputs continue to decrease,
fallout may become the dominant input mode of the
future. PCB inputs from surface runoff are of secondary
importance, and those from direct industrial discharges
and vessel antifouling paints are relatively insignificant.
Detailed results of our inputs studies are presented else-
where in these proceedings (ref. 1) and in a background
paper (ref. 2).
Other workers have studied PCB contamination off
California and elsewhere in the United States in the past
decade. During the summer of 1975, several reports of
high PCB levels in fish collected from Lake Michigan and
the Hudson River caused public concern about PCB
residues in commercial fish and sport fish (refs. 3-6).
Munson's work in California (ref. 7) indicated that, in
1972, concentrations of these chlorinated hydrocarbons
were low but widespread in the southern California
marine community.
The work of Allen and his colleagues (ref. 8) with
rhesus monkeys attests to the toxic effects of short-
term, low-level (25 ppm) exposures to PCB's on non-
human primates. Later results of their experiments on
the monkeys showed that exposure to PCB's at the 2.5-
and 5-ppm levels was related to spontaneous abortions
and the birth of undersized infants (ref. 9). Also, de
Long et al. (ref. 10) found PCB's to be associated with
premature births in the California sea lion.
In conjunction with our studies of PCB sources, we
undertook research into the fates and effects of PCB's in
marine animals. Our research involved several organisms
common locally (the Dover sole, Microstomus pacificus,
a benthic flatfish; the yellow rock crab. Cancer
anthonyi', and an open coast and a harbor mussel,
Mytilus californianus and M. edulis, respectively), and
three dfstinct programs:
• Regional surveys of PCB levels in the flatfish, the
crab, and the mussels. Specimens from stations through-
out the Southern California Bight (fig. 1) were analyzed
to determine the levels of PCB's present in their tissues
and plot the distribution of the substances in the Bight.
Changes over time were noted, as were relationships
between the concentration levels and man's centers of
activity along the coast (wastewater discharge, major
harbors). We also sought to identify the dominant PCB
209
-------
35
POINT HUENEME.-'l
SANTA MONICA
.LOS ANGELAS
CONCEPTION
SANTA BARBARA CHANNE
PALOS VERDES PENINSULA
ORANGE COUNTY
KLDANA POINT
SANTA
CATALIWA
ISLAND
DRAINAGE
DIVIDE
MAJOR
MUNICIPAL
WASTEWATER
OUTFALL
SYSTEM
8fc—.rrJTr'n"
33°N —
32°N
I2/°W
)20°W
I9*W
IIS'W
II7DW
Figure 1. The Southern California Bight. Outfall systems are
(1) Oxnard City, (2) Hyperion, Los Angeles City,
(3) Whites Point, Los Angeles County, (4) Orange
County, and (5) San Diego City. Major harbors are
(6) San Pedro, (7) Newport, and (8) San Diego.
present by determining if the RGB's found most closely
resembled Aroclor 1242 or Aroclor 1254.* Finally, we
investigated the PCB levels in specimens of the flatfish
afflicted with a fin erosion disease prevalent around
several southern California wastewater outfalls.
• A study of the relative amounts of PCB's in the
various tissues of the flatfish and the crab.
• The design of a convenient and effective system
for continuously monitoring PCB levels in the marine
environment.
This paper presents a brief summary of the results
of these studies.
SAMPLING PROCEDURES AND
CHEMICAL ANALYSIS
McDermott et al. (ref. 11) report in detail the
procedures used for the collection and preparation of
'Throughout the text, 1242 PCB and 1254 PCB have been
used to distinguish between substances most closely resembling
Aroclor 1242 and Aroclor 1254, respectively.
biological samples as well as the subsequent PCB anal-
yses by electron-capture gas chromatography for all
research programs discussed in this paper.
RESULTS AND DISCUSSION
Regional Surveys of PCB's in Marine Animals
Two Bight-wide suiveys of PCB contamination in
the benthic flatfish, Dover sole, were conducted during
1971-72 and 1974-75 (ref. 11). The results of these
regional surveys (table 1) revealed that PCB levels in
specimens collected near the three largest municipal
wastewater discharge sites off Palos Verdes, Santa
Monica, and Orange County were significantly higher
than levels found in specimens from regions with little or
no wastewater discharge. Despite the high levels of PCB
in the fish from the outfall areas, less'than 2 percent of
all Dover sole taken in the two surveys had muscle tissue
PCB concentrations that exceeded the Federal Food and
Drug Administration's tolerance of 5 mg/wet kg in the
edible portion of fish intended for interstate commerce.
Over the 3-year study period, municipal wastewater
210
-------
Table 1. Total PCB concentrations (mg/wet kg) in
muscle tissue of Dover sole Microstomus pacificus.3
Region
Point Hueneme
Santa Monica
Pal os Verdes
Orange County
Dana Point
San Diego
Santa Catalina
Island
1
(n
Region
median
0.1
1.5
1.9
0.7
0.06
-
0.04
971-72
b = 110)
Station
range
0.1
0.4-2.8
1.1-6.3
0.1-1.2
0.03-0.09
-
0.03-0.04
1
(n
Region
median
0.06
2.0
1.3
0.6
0.7
0.2
0.05
974-75
C = 165)
Station
range
0.05-0.07
1.0 -2.3
0.06-2.5
0.3 -2.8
0.03-0.14
0.09-0.6
0.03-0.07
a
between the 1971-72 and the 1974-75 levels.
Composite samples of Dover sole muscle tissue.
Individual samples of Dover sole muscle tissue.
emissions of total PCB decreased (ref. 1). Yet we
observed no statistically significant decrease in the levels
of total PCB in the Dover sole. This finding indicates
that other factors or inputs of these chlorinated hydro-
carbons are involved in maintaining the total PCB levels
in this fish.
During 1971 and 1974, Bight-wide surveys of the
open coast mussel were also conducted (refs. 11,12).
The results are shown in table 2. A regional survey of the
yellow rock crab was also conducted during 1971 (ref.
11). Table 3 presents the median concentration of total
PCB in the muscle tissue of the crabs collected in each
region. These surveys indicate that the PCB contamina-
tion levels in these animals are low but widespread.
Levels of total PCB in specimens near the major outfall
systems were generally 10 to 100 times higher than
levels in specimens collected from coastal or island
control sites; however, the Federal tolerance level for
PCB compounds was not exceeded in the edible portion
of any specimens of these two species. The two surveys
of M. californianus indicate that the level of PCB
contamination in these mussels had decreased signifi-
cantly over the 3-year interval, 1971-74, with a median
percent decrease of 54 percent.
The dominant PCB observed in the three species
surveyed was 1254 PCB; the other PCB identified was
1242 PCB. The percent composition of total PCB in the
muscle tissue samples from the crab and mussel speci-
mens was similar to that in the Dover sole muscle
samples. The median 1974-75 composition of total PCB
in muscle tissue of Dover sole taken near the five major
discharge sites was 67 percent 1254 PCB and 33 percent
1242 PCB. This contrasted with the median 1974
composition of municipal wastewater emission of
PCB: 29 percent 1254 PCB and 71 percent 1242 PCB.
These data, along with a comparison of total PCB levels
in Dover sole muscle tissue, surface sediments, and
municipal wastewater emissions (table 4), indicate that
the PCB levels in Dover sole are not dependent only
upon the level of PCB discharged in wastewaters and
that other factors, such as the solubility, volatility, the
sediment load, or the relative biological uptake and
211
-------
Table 2. Concentrations (mg/wet kg) of the PCB most
closely resembling Aroclor 1254 in the whole
soft tissues of Mytilus ca/ifornianus.a
Station
Coastal
Gaviota
Santa Barbara
Port Hueneme
Point Dume
Palos Verdes Peninsula
Point Vicente
Royal Palm
San Clemente
Point Loma
Island
Anacapa
Santa Barbara
Santa Catalina
San Nicolas
San Clemente
1971
0.05
0.03
0.12
0.08
0.38
0.52
0.05
0.12
0.01
0.07
0.02
0.02
0.02
1974
0.01
0.02
0.37
0.04
0.10
0.14
0.02
0.06
0.01
0.02
0.01
0.01
0.02
aAfter refs. 11, 12.
Table 3. Regional survey of total PCB concentrations (mg/wet kg)
in the muscle tissue of individual yellow rock crabs,
Cancer anthonyi, 1971-72.3
Region
Santa Monica
Palos Verdes
Outside San Pedro
Harbor
Orange County
Ensenada
No. of
samples
12
16
5
9
3
Region
median
0.68
0.82
0.49
0.32
0.014
Station
range
0.13 -2.2
0.30 -1.8
0.32 -0.83
0.23 -0.54
0.012-0.018
aAfter ref. 11.
Three chelae (Cancer species) purchased in fish market.
212
-------
Table 4. Comparison of total PCS levels in muscle tissue of Dover
sole, Microstomus pacificus, and bottom surface sediments
and PCB mass emission rates in municipal wastewater.8
Region
Pal os Verdes
Santa Monica
Orange County
San Diego
Point Hueneme
Dover
sole
(mg/wet
kg)
1.9
1.5
0.7
-
0.1
1971-72
Sedi-
ments
(mg/dry
kg)
3.6
0.53
0.02
0.01
0.004
1974-75
Muni-
cipal
waste
(kg/yr)
11,600
1,920
5,800
118
3
Dover
sole
(mg/wet
kg)
1.3
2.0
0.6
0.2
0.1
Muni-
cipal
waste
(kg/yr)
1,270
956
2,100
1,050
5
"After refs. 1,2,11
retention rate of a given PCB are involved in the result-
ing levels of RGB's in this marine animal.
Distribution of PCB's in Tissues of a Benthic Flatfish
and Crab
In February 1975, special collections of Dover sole
were made off Palos Verdes and Orange County for the
analysis of PCB's in the muscle, liver, gonad, heart, and
kidney tissues (ref. 11). The results are presented in
table 5. The level of PCB in the liver tissue was 10 to 20
times higher than the levels observed in the other tissues
analyzed. To determine the liver and muscle tissue
burdens of the two sets of fish, the median concentra-
tions of PCB in the specific tissue was applied to the
average wet weight of that tissue:
Palos Verdes
Orange County
Liver
burden
0.04 mg
0.02 mg
Muscle
burden
0.02 mg
0.03 mg
Ratio, liver
to muscle
2
0.7
The liver-to-muscle tissue burden ratio for PCB in
Palos Verdes Dover sole was 2; for Orange County
specimens, the ratio was 0.7. There are two possible
explanations for the high liver-to-muscle tissue burden
ratio in the Palos Verdes fish. A review of the literature
indicates that (1) in metabolic disturbances, the lipid
(fat) content in liver tissue may significantly increase,
and (2) chlorinated hydrocarbons, which are hepatic
poisons, induce fatty livers. As chlorinated hydrocarbons
are associated with lipids, if either one or both of these
situations had occurred in the Palos Verdes Dover sole, it
would have resulted in an increase in the total PCB levels
in the liver and a higher liver-to-muscle tissue burden
ratio. The lipid content of these tissues is being studied,
and further work on the physiological and ecological
implications of these tissue burdens is underway.
Analysis of the PCB concentrations in the reproduc-
tive organs of C. anthonyi indicate that the gonadal
tissues generally contain PCB levels five to ten times
higher tha'n the muscle tissue levels (ref. 11). Also, in
females, the gonad had an absolute tissue burden of PCB
that was 25 percent higher than the muscle tissue burden
(see table 6).
As the reproductive organs of this crustacean are
exposed to considerably higher levels of this synthetic
organic than is the muscle, spawning may represent a
significant distribution mechanism of these contami-
nants in the marine environment, and a significant factor
in the elimination of a large percentage of the body
burden of these materials from the crab. The long-term
effects of PCB concentrations on reproduction or other
biological processes in this crustacean are unknown.
Fin Erosion and PCB Levels in a Benthic Flatfish
The Dover sole collected off Palos Verdes are fre-
quently affected by fin erosion; the disease has recently
also become prevalent off Orange County. Data on
specimens with eroded fins and those with healthy fins
taken in 1974 in single trawls were paired. Utilizing the
213
-------
Table 5. Total PCB concentrations (mg/wet kg)
in composite samples of tissues of
Dover sole, Microstomus pacificus, 1975a
Tissue
Muscle
Liver
Gonads
Heart
Kidney
Pal os
Median
0.7
15
1.4
1.8
0.8
Verdes
Range
0.1-1.1
11-18
0.8-5.2
1.5-3.2
0.6-1.1
Oranqe
Median
1.1
8.3
0.8
0.5
0.6
County
Range
0.6-1.4
4.8-13
0.7-4.6
0.4-0.8
0.6-0.8
'After ref. 11.
Table 6. Analysis of PCB concentrations in the
reproductive organs of Cancer anthonyi
Male
Female
Percent of combined gonad/rnuscle
tissue weight
Gonad
Muscle
Tissue burden (mg)
Gonad
Muscle
7
93
0.009
0.025
27
73
0.031
0.025
Wilcoxon signed-rank test, the levels of PCB in the
muscle tissue of the unaffected fish and the diseased fish
were found to be different at the 90 percent confidence
level (p = 0.10). Although this level is not considered to
be statistically significant, it shows a strong tendency for
the total PCB levels to be higher in the diseased fish. The
median values for the diseased and unaffected groups
were 2 and 1 mg/wet kg, respectively (refs. 11,13).
If this association was dependent upon the input
level of PCB, one would expect fin erosion to be
dominant off Orange County where the input level of
PCB is the greatest. One would also expect to find it off
Santa Monica and San Diego where the level of input is
similar to Palos Verdes. However, this is not the case.
There are several possible reasons for the association
between high PCB levels and fin erosion. The disease is
predominantly found in the Palos Verdes region: Palos
Verdes sediments have the highest levels of PCB in the
Bight, thus contaminated sediments could be the
dominant factor. Also, PCB—in combination with other
constituents present in this region (DDT, hydrogen
sulfide, trace metals)~could be involved in the develop-
ment of the disease. It is also possible that PCB uptake is
enhanced in diseased fish; hence the higher levels could
be the result of the disease rather than a cause. These
relationships are being studied further.
214
-------
Surveys of PCB's in Harbor Mussel
Composite samples of the whole soft tissues of
Mytilus edulis collected from three major southern
California harbors (San Pedro, Newport, and San Diego)
were analyzed for PCB's (ref. 11).
The survey showed that the harbor mussels had
contamination levels up to 20 times those found in
specimens of the same species collected from nearby
coastal sites. Highest levels were found in mussels taken
near regions of heavy vessel activity. Figure 2 shows the
data for San Diego Bay, where the range of total PCB
values near the commercial docks and navy moorings
(0.80 to 1.3 mg/wet kg) is three to four times higher
than the values observed at other inner harbor sites, and
ten times greater than levels in nearby coastal mussels.
The levels of 1254 PCB in seawater at the mouths of
the harbors were generally on the order of 1 part per
trillion (ref. 1,2). The values of 1254 PCB in the whole
soft tissues of the harbor mussels were 100,000 times
these seawater levels.
Although most antifouling paints presently applied
to vessel bottoms in southern California contain PCB
concentrations of less than 1 mg/dry kg, a few samples
of pre-1970 paint chips averaged about 10 percent PCB
or 100,000 mg/dry kg (ref. 14). Thus it is possible that
thousands of kilograms of this synthetic material could
have been released annually to the harbor and coastal
marine ecosystems, before the widespread use of non-
recoverable PCB's was discontinued in the United States
in the early 1970's.
Bouy Mussels: An Offshore Biomonitoring System
In June 1974, 4- to 6-cm long specimens of M.
califomianus were collected from Point Sal, an area
known to be relatively free of PCB contamination.
Within 1 day of collection, these mussels were trans-
ported to a taut-line bouy anchored off Whites Point,
where wastewaters from Los Angeles County's Joint
Water Pollution Control Plant discharged (ref. 11). The
mussels were placed in net bags fastened at five levels
between the sea surface (0.5 m) and the bottom sedi-
ments (35 m), which are highly contaminated with trace
metals and chlorinated hydrocarbons at this site (refs.
15-17).
The mussels transported to the bouy system off
Palos Verdes appeared to survive well under the test
conditions: Less than 10 percent mortality was ob-
served at any of the five levels (0.5 to 35 m) at which
the mussels were suspended during the 3-month study.
On the average, mussels living at Royal Palm Beach,
inshore of the buoy, contained 17 times as much PCB as
the control specimens at the time of their transfer to the
buoy northwest of the outfalls. Thus, exposure of these
mussels to PCB was greatly increased upon their transfer
to the discharge region.
The results indicated that there was a diisct rela-
tionship between uptake of PCB and proximity of the
bioindicator to the contaminated bottom sediments and
to the wastewater plume, which is trapped beneath the
thermocline. The bottom specimens became approxi-
mately 10 times as contaminated as did the surface
specimens.
At the end of the 13-week period, the 1254 PCB
concentrations in the whole soft tissues of specimens
collected from Level 5 (closest to the bottom sediments)
were approaching 0.4 mg/wet kg; those specimens from
Level 1 (at the surface) were at 0.04 mg/wet kg. To date,
the highest 1254 PCB concentration measured in the
water above the outfalls is 4 ng/1 (ref. 12). This suggests
a concentration factor on the order of 100,000 for 1254
PCB in the whole soft tissues of M. califomianus, a
number in good agreement with the estimate for M.
edulis in the harbors.
SUMMARY
1. No statistically significant decrease in the Bight-
wide levels of PCB in the muscle tissue of Dover sole was
observed over the 3-year period 1971-72 to 1974-75.
2. The level of PCB contamination of the open
coast mussel decreased significantly over the 3-year
interval, 1971-74, with a median percent decrease of 54
percent.
3. Regional surveys of the yellow rock crab and
open coast mussel indicate that PCB contamination
levels in these animals are low but widespread.
4. For all three species surveyed, PCB levels in
specimens collected near major outfall systems were
generally 10 to 100 times higher than levels in specimens
collected from coastal or island control sites.
5. The dominant PCB observed in the three species
surveyed most closely resembled Aroclor 1254; the
other PCB identified most closely resembled Aroclor
1242. In contrast, the dominant PCB discharged via
municipal wastewaters most closely resembled Aroclor
1242.
6. The liver tissue of Dover sole generally had
concentrations of PCB's 10 to 20 times greater than the
levels found in the muscle, gonad, heart, and kidney
tissues.
7. The liver-to-muscle tissue burden ratio for total
PCB in Palos Verdes Dover sole was three times higher
than the ratio for Orange County specimens.
8. The reproductive organs of the yellow rock crab
generally contain PCB levels five to ten times higher than
the muscle tissue levels.
215
-------
in*10'
32".
so'
fy. Commercial
|. . Basin
'. '. Harbor Island
M"c%
Docks
\ . Large Shipyards
Point Lorn a
Submarine
OutfaU
KM
* A!. californianus
i
Figure 2. Total PCB concentrations (mg/wet kg) in whole soft
tissues of Mytilus edulis in San Diego Bay, January
1974. (Afterref. 11).
216
-------
9. RGB's were found to be associated with the fin
erosion disease prevalent in Dover sole collected around
major municipal wastewater discharge sites at the 90
percent confidence level (p = 0.10).
10. Harbor mussels had PCB contamination levels
up to 20 times those found in specimens of the same
species collected from nearby coastal sites. Highest levels
were found in mussels taken near regions of heavy vessel
activity.
11. Although the mussel used in the buoy system
was an intertidal organism, less than 10 percent mor-
tality was observed at depths to 35 m. This mussel's
hardiness, its ubiquitous distribution along many coast-
lines around the world, its very high ability for concen-
trating chlorinated hydrocarbons above seawater values,
and its apparent ability to rapidly respond to changes in
environmental levels of such contaminants make it a
very useful bioindicator, both in natural intertidal
communities and on offshore substrates.
The widespread use of nonrecoverable RGB's was
curtailed in the United States during the early 1970's.
However, the inputs of these persistent substances are
still diffuse and difficult to control. There is a need for
more knowledge of the effects of these materials in the
marine environment; in particular, uptake rates, persis-
tence, and biological effects should be studied.
REFERENCES
1. D. R. Young, D. J. McDermott, and T. C. Heesen,
"Marine Inputs of Polychlorinated Biphenyls Off
Southern California," in the proceedings of the
National Conference on Polychlorinated Biphenyls,
1975.
2. D. R. Young, D. J. McDermott and T. C. Heesen,
"Polychlorinated Biphenyl Inputs to the Southern
California Bight," background paper prepared for
the National Conference on Polychlorinated
Biphenyls, 19-21 November 1975, Chicago, Illinois,
Rept. TM 224, So. Calif. Coastal Water Res. Proj.,
El Segundo, California, 1975.
3. R. H. Boyle, "Poisoned Fish, Troubled Waters,"
Sports Illustrated, 1 September 1975, pp. 14-17.
4. R. Servero, "State Says Some Striped Bass and
Salmon Pose a Toxic Peril," New York Times, 8
August 1975.
5. R. Servero, "Warning Ignored on Striped Bass,"
New York Times, 9 August 1975.
6. R. Servero, "Reports of Chemical in Fish Initially
Withheld," New York Times, 17 August 1975.
7. T. 0. Munson, "Chlorinated Hydrocarbon Residues
in Marine Animals of Southern California," Bull.
Environ. Contam. Toxicol., Vol. 7 (1972), pp.
223-228.
8. J. R. Allen, L. A. Carstens, and D. A. Barsotti,
"Residual Effects of Short-Term, Low-level Expo-
sures of Nonhuman Primates to Polychlorinated
Biphenyls," Toxicol. and Applied Pharm., Vol. 30
(1974), pp. 440-451.
9. D. A. Barsotti and J. R. Allen, "Effects of Poly-
chlorinated Biphenyls on Reproduction in the
Primate," paper presented at the meeting of the
American Societies for Experimental Biology, 18
April 1975, Atlantic City, N.J.
10. R. L. de Long, W. G. Gilmartin, and J. G. Simpson,
"Premature Births in California Sea Lions: Associa-
tion With High Organochlorine Pollutant Residue
Levels," Science, Vol. 181 (1973), pp. 1168-70.
11. D. J. McDermott, D. R. Young, and T. C. Heesen,
"Polychlorinated Biphenyls in Marine Organisms
Off Southern California," background paper
prepared for the National Conference on Polychlo-
rinated Biphenyls, 19-21 November 1975, Chicago,
Illinois, Rept. TM 223, So. Calif. Coastal Water Res.
Proj., El Segundo, California, 1975.
12. B. de Lappe and R. Risebrough, personal communi-
cation.
13. D. J. McDermott and M. J. Sherwood, "DDT and
PCB in diseased Dover sole," in 1975 Annual
Report, So. Calif. Coastal Water Res. Proj., pp. 33-5,
1975.
14. D. R. Young, T. C. Heesen, D. J. McDermott, and P.
E. Smokier, "Marine Inputs of Polychlorinated
Biphenyls and Copper from Vessel Antifouling
Paints," Rept. TM 212, So. Calif. Coastal Water Res.
Proj., El Segundo, California, 1974.
15. J. N. Galloway, "Man's Alteration of the Natural
Geochemical Cycle of Selected Trace-Elements,"
Ph. D. dissertation, University of California, San
Diego, 1972.
16. Southern California Coastal Water Research Project,
"The Ecology of the Southern California Bight: Im-
plications for Water Quality Management," Rept.
TR 104, So. Calif. Coastal Water Res. Proj., El
Segundo, California, 1973.
17. D. J. McDermott, T. C. Heesen, and D. R. Young,
"DDT in bottom sediments around five southern
California outfall systems," Rept. TM 217, So.
Calif. Coastal Water Res. Proj., El Segundo, Califor-
nia, 1974.
217
-------
TRANSPORT OF CHLORINATED HYDROCARBONS
IN THE UPPER CHESAPEAKE BAY
T. O. Munson, Ph.D., H. D. Palmer, Ph.D., and J. M. Forns*
Abstract
Under contract to the Maryland State Department
of Natural Resources, the staff of the Westinghouse
Ocean Research laboratory (together with subcon-
tractors at Johns Hopkins University and the University
of Mary/and) recently completed the Upper Bay Sur-
vey—a program having as the central task the study of
the routes, rates, sources, sinks, and reservoirs of chlorin-
ated hydrocarbons (CMC's) in the upper Chesapeake
Bay. Data from the field portion of this program will be
presented; in particular, the levels of PCB's, chlordane,
and DDTR found in bottom sediments, suspended
particulates, zooplankton, and shellfish will be summa-
rized. The discussion will include the role of sediment
deposits as traps for CMC's; suspended particulates as
transport vehicles for CHC's; movement of CHC's from
the suspended paniculate reservoir into the biological
system, particularly shellfish and zooplankton; i/nd the
sources of CHC's in the upper Chesapeake Bay.
INTRODUCTION
The concept of the Upper Bay Survey grew directly
from the Chester River Study (ref. 1), a program of
more limited scope, which was completed in the fall of
1972. An objective of that program was to provide the
Maryland Department of Natural Resources with envi-
ronmental and resource management information essen-
tial to the local shellfish industry. These studies were
directed toward determining the source and fate of
chlorinated hydrocarbons and selected trace metals in
the waters and sediments of this estuary. The approach
was multidisciplinary. The project as a whole was con-
sidered experimental, since it was to encompass many
aspects of an estuarine ecosystem with the declared pur-
pose of supporting the practical needs of natural re-
source managers. Thus, the Chester River Study was a
program of focused, applied research rather than a more
basic program to extend knowledge in estuarine sciences.
As a result of this program, it became clear that the
upper Chesapeake Bay was the most likely source of
sediment-borne materials considered potentially harmful
to the living resources of the Chester River. An exten-
sion of the Chester River project encompassing the bay
between the Severn and Susquehanna Rivers became the
*Westinghouse Ocean Research Laboratory, Annapolis,
Maryland.
next logical step in assessing the impacts of man-made
substances in the bay ecosystem. The Upper Bay Survey
(funded by the Mayland Department of Natural Re-
sources) was begun in December 1973—once again multi-
disciplinary, but also multiinstitutional with the partici-
pation of scientists from the University of Maryland and
The Johns Hopkins University. A 12-month research
prograrri was implemented with the following five defini-
tive objectives:
1. To determine concentrations, distributions, and
sources for chlorinated hydrocarbons (CHC's) in-
cluding pesticides and polychlorinated biphenyls
(PCB'S), and to determine the nature of transport
paths, mechanisms, and rates in the Chesapeake
Bay's waters, sediments, and organisms.
2. To determine immediate and longer-term biological
consequences of chlorinated hydrocarbons and
PCB'S on commercially important species.
3. To determine the Distribution of bacteria on sedi-
ments and suspended particles of the upper bay, and
to perform lexicological studies of the combined
effects of pesticides and bacteria on oysters.
4. To institute numerical models for projecting con-
taminant distribution relative to the sources and to
develop interrelations to biological impacts resulting
from changes in the upper Chesapeake Bay's input
stresses.
5. To report results in a format convenient for re-
source management and in a format for computer
storage, retrieval, and augmentation.
In this paper, the data resulting from the chlorin-
ated hydrocarbon analyses of bottom sediments, sus-
pended sediments, zooplankton, and shellfish will be
presented and discussed.
METHODS
Sample Collect/on. The bottom sediments were col-
lected as grab samples using either a Wildco-Eckman Bot-
tom Sampler or a Ponar Grab Sampler. In the labora-
tory, a portion of the sample was retained for sediment
grain-size and clay mineralogy analyses, and the
remainder air-dried for about 1 week. The shellfish
samples were collected with a modified bottom trawl or
a Ponar Grab Sampler and frozen for later analysis.
Suspended particulate samples were collected from
surface, midwater, and 0.5 m from the bottom at the
sampling stations illustrated in figure 1. The suspended
218
-------
CONOWINGODAM
UPPER CHESAPEAKE BAY
SUSQUEHANNA R
01 234567
1111
NAUTICAL MILES
4a ^ HOWELL PT
b
-------
participates were collected by filtration through Gelman
type-A glass-fiber filters having nominal pore diameters
of 5-8 n (the functional pore size appeared much smaller
because our tests with Chesapeake Bay water showed
that nothing which passed through this filter could be
retained on a 0.45 ju Millipore filter). In order to get
sufficient sample for chlorinated hydrocarbon analysis
(in excess of 0.3 g dry weight) as much as 100 I of water
was filtered depending upon the concentration of sus-
pended particulates in the water (usually in the range, 3
to30mg/l).
Figure 2 shows the filter apparatus and a filter load-
ed with suspended particulates. It was determined em-
pirically that filtering until two filters 14.5 cm in diam-
eter became clogged provided the minimum amount of
sample required. The bay water entered a % inch garden
hose suspended at the appropriate depth, passed through
the filter, through the pump, and into a calibrated vessel
for volume estimation. The wet filters were folded,
wrapped in aluminum foil and transported to the labora-
tory. In the laboratory the samples were air-dried (about
2 days) and stored wrapped in foil until analysis. The
weight of sample collected (and subsequently extracted)
was determined by a calculation using the volume of
water filtered and the concentration of suspended partic-
ulates in the water.
Two procedural restrictions prevented direct deter-
mination of the suspended particulate sample
weights: first, the filters had to be preextracted with
solvents to remove interfering substances and sealed in
foil until use, which made preweighing undesirable; and
second, had preweighing been done, the subsequent
weights would have been dubious because these filters
tend to shed and flake. At each point in time and space
where a suspended particulate sample was collected for
chlorianted hydrocarbon analysis, two suspended partic-
u'gte samples were collected on 4.7 cm diameter Milli-
pore or Nucleopore membrane filters (pore size 0.45 and
0.6 M respectively)—one for determing the suspended
particulate concentration and one for determining the
suspended particulate grain-size diameters (ref. 2).
Zooplankton samples were collected as oblique tows
with paired half-meter standard oceanographic nets using
hexane rinsed 202-/J. Nitex netting. A calibrated
T.S.K.-type mechanical flowmeter was placed in the
mouth of each of the two nets to record the volume of
water passing through. Upon completion of each tow,
the nets were carefully washed to concentrate the plank-
ton in the cod end. After removal of the larger, gelatin-
ous material by passage through a 4-mm sieve, the
samples were concentrated with a 202-ji sieve. From
each pair of net samples, one net collection was pre-
served for taxonomic and biomass enumerations, and the
other sample was passed through a hexane-extracted
Gelman glass-fiber filter to collect the zooplankton.
The resultant pad of zooplankton (including the filter)
was frozen and retained for later analysis.
Sample Preparation. All of the samples were ex-
tracted using Soxhlet extraction with 2:1 hexane-
acetone (the biological samples were first dried by being
ground with anhydrous sodium sulfate). All of the ex-
tracts were subjected to fuming sulfuric acid cleanup
procedures (refs. 3,4) prior to gas chromatographic anal-
ysis. Before the acid treatment procedure, the bottom
sediment extracts were treated wtih activated alumina.
Most of the bottom sediment extracts, some of the sus-
pended sediment extracts, and several of the zooplank-
ton extracts contained sulfur, which was removed by
treatment with elemental mercury (ref. 5).
Chlorinated Hydrocarbon Analysis. The chlorinated
hydrocarbons were identified and quantitated by multi-
column, electron-capture, gas-liquid chromatography.
Peak relative retention times and peak heights (or areas)
were compared to those of standard compounds. The
amounts of RGB's and chlorinated pesticides were esti-
mated by a manual subtraction procedure correcting for
the overlapping peaks.
RESULTS AND DISCUSSION
Table 1 summarizes the chlorinated hydrocarbon
levels found in the various types of samples collected in
the upper Chesapeake Bay.
The standard deviation values given in table 1 em-
phasize the fact that the range of CMC values observed
within any particular sample type was very broad. The
values for CMC's on suspended sediment and zooplank-
ton varied greatly from one station to the next during
the same collection period or at the same station from
one collection period to the next. Apparently these
values fluctuate rapidly enough (temporally and
spatially) that only the unusually large events in terms of
time and/or space will be observed at enough points to
describe a trend when the sampling is limited to a fairly
small number of samples, as in this program. The multi-
disciplinary approach of this program, however, circum-
vents this problem somewhat by providing many differ-
ent types of data that are comparable in space and time.
As will be seen below, these data then can be examined
for interrelationships relevant to the understanding of
the dynamics of chlorinated hydrocarbon movements in
the upper Chesapeake Bay.
For the purposes of this discussion, the PCB's will
be discussed as total PCB (the sum of the values reported
as Aroclor 1242, 1248,1254, and 1262), and in some
220
-------
Q.
E
03
o> -M
.1 £
•D E
o -5
O) -"D
Q. C
05
c
o .c
8 I
n °
£ o
D. CD
Q- c
ca i
O) 03
E O
fe «
±: T3
E g
CN
0)
3
221
-------
Table 1. Average chlorinated hydrocarbons found
in the upper Chesapeake Bay
(Standard deviations are in parentheses)
Sample type
Shellfish
(wet.ppm)
Plankton
(wet,ppm)
Suspended, sediment
(dry.ppm)
Bottom sediment
(dry,ppm)
Plankton
(H20,ppt)c
Suspended sediment
(H20,ppt)
Number of
samples
26
70
66
54
69
68
Total PCB
0.052(0.037)
0.50(1.4)
0.92(0.87)
0.28(0.57)
0.042(0.164)
12(14)
Total
chlordane
0.016(0.017)
0.041(0.032)
0.061(0.086)
0.0052(0.014)
0.0038(0.0083)
0.53(0.88)
Total DDT
0.035(0.041)
0.16(0.68)
0.057(0.066)
0.051(0.067)
0.010(0.035)
0.78(1.5)
The values are expressed as ug CHC found per g wet weight of material
extracted.
The values are expressed as yg CHC found per g dry weight of material
extracted.
cThe values are expressed as ng of CHC found per 1 of water filtered to
collect the material extracted.
cases, all of the CMC's found will be summed and dis-
cussed as total CHC. The PCB residue pattern observed
most often matched Aroclor 1254 or a mixture of
Aroclors 1254 and 1262. (Aroclor 1242 or 1248 was
found in many of the samples.)
By comparing the bottom sediment data with the
suspended sediment (dry) data, one can see that the PCB
and chlordane concentration are 4 to 10 times higher in
the suspended sediments. The higher values in the sus-
pended sediment probably occur for one, or most likely,
both of the following reasons: the average grain-size of
the suspended sediments is much smaller than that of
the bottom sediments, resulting in a greater surface area
for adsorption per unit weight; and although the sus-
pended sediments are primarily inorganic materials, the
phytoplankton, which were included in these samples.
probably bioconcentrated chlorinated hydrocarbons to
some extent.
If one accepts the above discussion, one is left with
the dilemma that the DDTR does not appear higher in
the suspended sediments as do the PCB and chlordane.
But all uses of DDT were banned in the United States at
the end of 1972. It this ban had the effect of decreasing
the DDT levels flowing into the Chesapeake Bay, the
concentrations of DDT residues in the suspended sedi-
ments would be less relative to those in the bottom sedi-
ments because the bottom sediment samples consist of
materials deposited during the sampling year and pre-
vious years as well, while the suspended sediment
samples consist primarily of materials that entered the
bay during the sampling year. While this explanation is
plausible, it seems somewhat suspicious that samples
222
-------
were taken fortuitously at just the right time to yield
exactly the same DDT residue levels in both the sus-
pended sediments and the bottom sediments.
The data in table 1 also show that the CHC's are
bioconcentrated in passing from the suspended sediment
into the zooplankton. To evaluate the magnification,
one must first convert the plankton (wet) values to
plankton (dry) to allow comparison with the suspended
sediment (dry) values. If one conservatively uses 0.10 as
the plankton dry weight to wet weight ratio (ref. 6), one
then multiplies all of the plankton (wet) values by 10 to
convert to plankton (dry) and then calculates the follow-
ing bioconcentrations as the CHC's pass from the sus-
pended sediments to the zooplankton: PCB, 5.4; chlor-
dane, 6.7; and DDTR, 28. The DDTR value seems un-
reasonably high, and it probably is. If two anomalously
high DDTR values are excluded from the total and the
average is computed from the other 68 values, the aver-
age DDTR in plankton (wet) become 0.045, leading to a
magnification of 7.9—a value more compatible with the
others.
The CHC data for suspended sediments and zoo-
plankton are expressed in two ways, as mentioned
earlier, but further amplification should be made. Envi-
ronmental residues of chlorinated hydrocarbons (chlo-
rinated pesticides and polychlorinated biphenyls) usually
are reported as parts per million (ppm) dry weight (or
wet weight) based upon the dry weight (or wet weight)
of sample which was extracted for the analysis. If the
levels are very low, parts per billion (ppb) or parts per
trillion (ppt) also are used. The data then represent the
concentration of CHC's present in that sample. In the
consideration of transport of CHC's (rates, routes, etc.)
the amount of CHC being transported by a water move-
ment frequently is of more interest than the concentra-
tion of the CHC's on the suspended sediments in the
water.
Therefore, in addition to the data being presented in
the usual fashion, the zooplankton and suspended sedi-
ment CHC data are presented as nanograms (lO^g) of
CHC on zooplankton or suspended sediment per liter of
water (by definition, ppt). These values represent the
amount of CHC associated with the suspended sediments
or the zooplankton contained in a 1 liter sample of bay
water. In a sense, the numbers can be compared directly
because they have been normalized to a unit volume of
water. For instance, referring to table 1, one finds the
average PCB values in the bay water on suspended sedi-
ment and zooplankton to be 12 ppt and 0.042 ppt,
respectively. On the average, a given volume of bay
water will have about 300 times as much PCB in the
suspended sediment fraction as in the zooplankton frac-
tion.
Using these values, one also could calculate approxi-
mate biomagnification values from the shellfish data.
The concentrating ability of shellfish usually is expressed
as the level accumulated in the shellfish tissue (wet
weight) divided by the exposure concentration in the
water. Using the values for CHC in the water column on
suspended sediment, the shellfish concentration factors
are approximately: PCB, 4,000; chlordane, 30,000; and
DDTR, 45,000. These values should be considered rough
estimates, because the average values used for CHC's in
the water column probably do not represent accurately
the values at the water-bottom sediment interface in-
habited by these shellfish.
Figure 3 is a log-log plot of total CHC concentration
in the water column on suspended sediment (ppt) versus
the concentration of suspended sediment in the water
(mg/l). Although the data points are widely scattered,
the data could best be enclosed in an oblong field with
an upward tilt to its long axis. This indicates a positive
relationship between the parameters plotted (if the
parameters were unrelated—that is, varied independent-
ly-the long axis of the oblong would be either vertical
or horizontal). The correlation obviously is not followed
closely by all of the data, but in general, it indicates that
the bay water samples which had high suspended sedi-
ment concentrations also had high levels of CHC's in the
water on suspended sediments. If all suspended sedi-
ments in the water contained the same amounts of
CHC's (ppm, dry weight), a perfect correlation would
have been observed in figure 3. The variations in the
concentrations of CHC's on suspended sediments are
responsible for the scattering of the data.
Figure 4 is a log-log plot of total CHC's in the water
on zooplankton (ppt) versus the zooplankton biomass in
the water (mg/m3). Although the data are somewhat
scattered, there is an obvious positive relationship—as
the zooplankton population in the water increases (in-
creasing biomass), the amount of CHC's in the water on
zooplankton increases. The existence of this relationship
establishes that there is movement of CHC's into the
aquatic food chains which include the zooplankton com-
munity. The fact that the zooplankton population con-
tains only a small fraction of the CHC's present in the
water column, considered with the relationship observed
in figure 3, suggests that the movement of CHC's into
the biological system (via zooplankton) from the non-
biological system (suspended sediments) is not influ-
enced by changes in the concentration of suspended
sediment but is regulated by whatever regulates the zoo-
plankton population. One could visualize the suspended
sediments in the water column as being a reservoir of
CHC's, which flow into the biological system when zoo-
plankton blooms occur.
223
-------
z
o
100
o t
O _l
£ K
Z LLI
ui Q-
5 en
5|
I
0
1.0
O O
O
00
o o
0°
_ o
00W 00
O Q
o
0.10
1-0
10.0
100
TOTAL CHC IN WATER ON SUSPENDED SEDIMENT
(PARTS PER TRILLION)
Figure 3. A plot of the log of the suspended sediment concentration in>
the water (milligrams per liter) versus the log of the total CHC
concentration in the water associated with the suspended
sediment (parts per trillion).
Obviously, this concept is an over simplification of a
very complex system. More likely, the phytoplankton
are important in the transport of CMC's from the non-
biological reservoir into the zooplankton food-chain. Un-
fortunately, the sampling procedure for gathering sus-
pended sediments involved pumping the water through a
filter, so the phytoplankton were included in the frac-
tion called suspended sediments. To overcome this limi-
tation, it had been hoped to estimate the influence of
changes in the phytoplankton population through the
use of measurements of the chlorophyll level in the
water column. Figure 5 presents a log-log plot of the
zooplankton biomass versus the chlorophyll-a concentra-
tion in the water column. These parameters appear to be
independent variables. A similar plot (not shown) of the
chlorophyll-a concentration versus the concentration of
CMC's in the water column on zooplankton yielded a
very similar result. If the phytoplankton have a direct
role in the pathway of CMC's into the zooplankton com-
munity, the chlorophyll-a data shown here do not indi-
cate it.
Whatever the details of the pathway for CMC's from
the suspended sediment reservoir into the zooplankton,
it seems that only a very small percentage of the CMC's
in the water column are associated with the zooplankton
(average of 12 ppt PCB in the water column on suspend-
224
-------
1000
1 0
TOTAL CMC IN WATER ON PLANKTON
(PARTS PER TRILLION)
Figure 4. A plot of the log of zooplankton biomass (milligrams weight
per cubic meter) versus the log of the total CMC in the water
associated with the zooplankton (parts per trillion).
ed sediment versus 0.042 on zooplankton). However, to
quantify the rate of movement of the CHC's via this
pathway one would need information about turnover
rates in the plankton community. Regarding resource
management, one should consider that a change in bay
conditions that would increase the zooplankton popula-
tion would probably have the effect of increasing the
flow of CHC's from the suspended sediment reservoir
into the biological system. This could create adverse con-
sequences as all aquatic species of commercial interest at
some time in their lifecycle make up a part of the zoo-
plankton community.
By far, the largest route for the transport of CHC's
from the suspended sediment reservoir probably is a
result of sediment deposition. The areas of deposition of
fine-grain sediments can be visualized as sinks where the
CHC's attached to suspended sediments collect. As in
the Chester River Study (ref. 1), the chlorinated hydro-
carbons in the bottom sediments were found highest
where the median grain-size diameters were the lowest.
Baltimore harbor is a trap for fine-grain sediments in the
upper Chesapeake Bay and, as such, functions as a sink
for CHC's from the suspended sediment reservoir. Figure
6 shows that PCB, for instance, was much higher in the
sediments of Baltimore harbor than elsewhere in the
bay. It would be necessary to analyze core slices and
establish the three-dimentional concentration gradient in
order to estimate the mass of CHC's contained in the
bottom sediment sinks. (A core from the Chester River
was found to contain layers of widely varying levels of
CHC's to a depth of 50 centimeters—reference 1.)
A number of mechanisms exist for movement of
225
-------
(uain/siAivyooy3iiAi)
V-TIAHdOaOIHD
226
-------
UPPER CHESAPEAKE BAY
O 0 — .01 ppm
.01 —.10 ppm
ft ) .I0-l.0ppm
J HOWELL PT
SASSAFRAS R
Figure 6. A representation of the concentration of RGB's in bottom
sediments samples from the upper Chesapeake Bay.
227
-------
Figure 7. A portion of an Earth Resources Technology Satellite—1 photo-
graph taken April 3, 1974, showing suspended sediment influx
into the upper Chesapeake Bay from the Susquehana River.
Samples were taken at station "13".
228
-------
CMC's out of the bottom sediment sinks. When one
considers the fine-grain fractions in the upper Chesa-
peake Bay as a whole, resuspension of this material by 1.
tidal scour probably is the major reentry route from the
sinks to the suspended sediment reservoir (ref. 7). In the
Baltimore harbor area, however, maintenance dredging
of navigational channels is a major mechanism for 2.
removal of sediments containing chlorinated hydro-
carbons from the bottom sediment sink. Although the
subsequent fate of this dredged material is a subject
clouded by great controversy, during the dredging and
subsequent overboard discharge of this material, un-
doubtedly, a substantial quantity returns to the suspend- 3.
ed sediment reservoir.
The Susquehanna River appears to be the major
source of chlorinated hydrocarbons to the upper Chesa-
peake Bay. Nearly all of the suspended sediment in the 4,
upper bay originates from the Susquehanna River—enter-
ing primarily during the few brief periods of high flow
(ref. 7). Figure 7 is an ERTS-1 (Earth Resource Tech-
nology Satelite-1) photograph showing the sediment in-
flux at the beginning of a freshet period in April 1974.
During this freshet period, suspended sediment samples 5.
were collected at the location dasigned "13" in figure 7.
Analysis of these samples (together with other samples
collected during the study) indicated that, when they
enter the bay, the suspended sediments appear to carry 6.
sufficient burden of RGB's and DDT residues to account
for levels observed at the lower stations without postu-
lating additional sources. The chlordane values appear
low, however, suggesting substantial inputs from other
sources. As is discussed in greater detail elsewhere (ref.
4), the urban-industrial activities concentrated in and 7
around Baltimore harbor appear to generate locally high
concentrations of PCB and DDT residues, but seem not
to contribute a major portion of the total budget of
these materials in the upper bay. It seems likely, how-
ever, that the harbor area does contribute a large portion
of the chlordane found in the upper bay.
REFERENCES
W. D. Clarke, H. D. Palmer, and L. C. Murdock,
eds., Chester River Study, Volume II, Westinghouse
Electric Corporation, Annapolis, Maryland, 1972,
251 pp.
H. D. Palmer and J. R. Schubel, "Chapter
4: Estuarine Sedimentology," Upper Bay Survey,
Final Report to the Mary/and Department of
Natural Resources, Volume II, T. 0. Munson, D. K.
Ela, and C. Rutledge, eds., Westinghouse Oceanic
Division, Annapolis, Maryland, 1975, in press.
T. 0. Munson, "Chlorinated Hydrocarbon Residues
in Marine Animals of Southern California," Bull.
Envir. Contam. Toxicol., Vol. 7 (1972), pp.
223-238.
T. 0. Munson, "Chapter 6: Biochemistry," Upper
Bay Survey, Final Report to the Maryland Depart-
ment of Natural Resources, Volume II, T. 0.
Munson, D. K. Ela, and C. Rutledge, eds., Westing-
house Oceanic Division, Annapolis, Maryland, 1975,
in press.
D. F. Goerlitz and L. M. Law, "Note on Removal of
Sulfur Interferences from Sediment Extracts for
Pesticide Analysis," Bull. Envir. Contam. Toxicol.,
Vol. 6 (1971), pp. 9-10.
J. M. Forns, "Chapter 2: Marine Biology," Upper
Bay Survey, Final Report to the Maryland Depart-
ment of Natural Resources, Volume II, T. 0.
Munson, D. K. Ela, and C. Rutledge, eds.. Westing-
house Oceanic Division, Annapolis, Maryland, 1975,
in press.
J. R. Schubel, "Distribution and Transportation of
Suspended Sediment in Upper Chesapeake Bay,"
Geol. Soc. Amer. Memoir 133, 1975, pp. 151-167.
229
-------
RECENT STUDIES OF TRANSPORT OF PCB'S TO MARINE ENVIRONMENTS
Robert W. Risebrough*
Abstract
The deep ocean waters and sediments are a potential
sink for chlorinated biphenyl compounds, removing
them from food webs which provide input to man. Data
on PCB levels in seawater are as yet unsatisfactory or too
few to permit a reliable estimate of the amounts of PCB
that have so far entered the oceans. Formulation of a
global mass balance equation for the major kinds of PCB
compounds would be useful in predicting future contam-
ination levels.
Chlorinated biphenyl compounds have been report-
ed in many marine environments, including those of the
Arctic (ref. 1) and the Antarctic (ref. 2); with the DDT
compounds they have become contaminants throughout
the global ecosystem. Concentrations reported are occa-
sionally high, including those in seawater of the North
Atlantic (ref. 3), in marine birds of coastal areas (refs.
4,5,6), in birds feeding on the eggs of other sea birds
(ref. 7) and in peregrine falcons (Falco peregrinus) of
Amchitka Island in the Aleutians (ref. 8).
The high levels which have been reported from both
coastal and marine environments raise two questions. Do
these levels represent a threat to local ecosystems and to
human consumers? And do the high levels indicate that
the oceans, particularly the deep waters and marine sedi-
ments, can be considered an ultimate sink in which poly-
chlorinated biphenyls are unlikely to enter food webs
that provide nourishment to man? Deposition in marine
sediments might then be a significant pathway of remov-
al of these pollutants from the biosphere. Attempts to
answer the latter question would require formulation of
a global mass balance equation of the chlorobiphenyls,
which would express the present burden of PCB's in the
oceans in terms of global production figures and use
patterns. A preliminary formuation of such a global mass
balance equation based on North American production
and use of PCB has been presented by Nisbet and Saro-
fim (ref. 9). The present paper reviews some of the work
relating to the transport of polychlorobiphenyl com-
pounds to marine environments that has been carried
out since Nisbet and Sarofim presented their preliminary
model.
Just as it has become misleading to speak of "DDT"
in the environment without reference to the individual
*Bodega Marine Laboratory, University of California, Bode-
ga Bay, California 94923, and Canadian Wildlife Service, Depart-
ment of the Environment, Ottawa, Canada K1A OH3.
compounds, so has it become misleading to speak of
"PCB" in the environment without reference to the kind
of PCB. Thus, the majority of the chlorinated biphenyls
used in the United States has consisted of the trichlorin-
ated preparations (ref. 10), whereas PCB reported in
marine environments usually consists of penta- or hexa-
chlorobiphenyls. It is therefore meaningless to discuss
PCB concentrations in seawater in reference to input
from rivers if the former consist predominately of penta-
chlorobiphenyls and the latter of trichlorobiphenyls.
Nature of PCB Compounds in Marine Environments
The higher vapor pressures of the lower chlorinated
PCB compounds (ref. 11) and the production and use
figures (refs. 9, 10) suggest that larger quantities of these
have entered the marine environment than have the
penta- and hexachlorobiphenyls. Thus Bidleman and
Olney (ref. 12) found that the majority of the PCB resi-
dues in air over the Sargasso Sea consisted of tri- and
tetrachlorobiphenyls. Similarly, PCB entering the sea as
a component of the wastewaters of Southern California
has consisted predominately of trichlorobiphenyls (D. R.
Young, R. W. Risebrough, B. W. de Lappe, T. C. Heesen,
and D. J. McDermott, unpublished data). Trichloro-
biphenyls have occasionally been detected in seawater of
the Southern California Bight (ref. 13), but PCB usually
reported in seawater has consisted of pentachlorobiphen-
yls (refs. 3, 14, 15, 16). Bidleman and Olney (ref. 12)
have reported that the chlorobiphenyls in their seawater
extracts from the Sargasso Sea were predominately hexa-
chlorobiphenyls. Tri- and tetrachlorobiphenyls have
been detected in marine fish from the Aleutians and in
ptarmigan (Lagopus mutus), an arctic grouse that feeds
on the tundra (ref. 8). Many extracts of marine species,
however, do not contain tri- or tetrachlorobiphenyls in
concentrations equivalent or approaching those of the
penta- and hexachlorobiphenyls. Bacterial degradation
of the lower chlorinated compounds (ref. 17) is a possi-
ble pathway of breakdown but the low concentrations
of PCB in seawater might not prompt bacteria to synthe-
size the necessary enzymes for their metabolism, unlike
the bacterial response in artificial environments where
PCB compounds are the only carbon source. A major
difficulty in recording the lower chlorinated compounds
in seawater has teen the presence in the majority of
extracts of high concentrations of other compounds
which interfere with the analysis. The higher vapor pres-
sures of the lower chlorinated compounds and thei-
230
-------
longer residence time in the atmosphere might result in
higher rates of breakdown by ultraviolet light, but evi-
dence to support this hypothesis is apparently lacking.
In higher vertebrates, metabolism to hydroxylated deriv-
atives of unknown significance in the marine environ-
ment accounts for the disappearance of some of the tri-
and tetrachlorobiphenyls. Formulation of a global mass
balance equation of "PCB" therefore makes little sense
unless it is done with reference to individual compounds
or at least to the major classes of chlorobiphenyls.
Chlorinated Dibenzofurans in the Environment
Other papers presented at this symposium have ex-
pressed the current concern over the possible exposure
of man to chlorinated dibenzofurans. Preparations of
PCB have been shown to produce birth defects in birds
(refs. 18, 19, 20), similar to those which have occasional-
ly been observed in populations of terns, Sterna hirundo,
and 5. dougallii, breeding in Long Island Sound and
feeding on small fish (ref. 21). The observed defects are
comparable to those produced by the chlorinated diben-
zodioxins (ref. 22). The presence of the chemically relat-
ed chlorinated dibenzofurans in PCB preparations (refs.
23, 24, 25) suggests that the defects may be caused by
these contaminants rather than by chlorobiphenyls.
Extracts of mallards (Anas platrhynchos) that had
been fed PCB of known dibenzofuran content were
examined for the presence of chlorinated dibenzofurans.
The chlorinated dibenzofurans originally present in the
Aroclor 1254 were found to be metabolized or other-
wise excreted at a much faster rate than the pentachloro-
biphenyls and were not found in the extracts (ref. 26). It
would therefore appear unlikely that these compounds
would be accumulated in marine food webs. In the light
of other results that have been presented at this symposi-
um, it might be worthwhile to look in the environment
for those individual PCB compounds from which diben-
zofurans might be formed in vivo, and to examine tissues
of species exposed to these compounds for the presence
of the furans.
Comparative PCB Levels in Marine Environments
Relative contamination levels of different oceanic
areas by PCB compounds have recently been reviewed
by Ohlendorf et al. (ref. 27) and by Risebrough et a!.
(ref. 13); marine birds were used as indicator organisms.
In the North Atlantic, PCB contamination appears to
increase from west to east; contamination levels in the
vicinity of Iceland appear comparable to those in the
Aleutians in the North Pacific. In the southern hemi-
sphere, levels in biocoenetic equivalents of northern spe-
cies are approximately one order of magnitude lower.
The difference between the two hemispheres teflects
therefore the relative industrialization of the two areas.
Data that would permit a more detailed comparison be-
tween the Atlantic and the Pacific are as yet insufficient.
PCB in Seawater
Determinations of the PCB levels in seawater have
been reported from both the Pacific and the Atlantic.
Williams and Robertson (ref. 15) have reported PCB, p,
p'-DOT, and p, p'-DDE values in subsurface water from
the outer California Current and at two stations in the
North Central Pacific Gyre, both in the vicinity of 31°
N.155° W. Water was collected in 2.5- liter glass bottles,
10-15 cm below the surface. Reported PCB values in the
subsurface water, including filtrate and filtered fractions,
were 2.5 x 10"12 g/g in the California Current and 4.5 x
10"12 g/g at one of the North Central Pacific Gyre sta-
tions.
Scura and McClure (ref. 16) utilized a column con-
taining 5% activated carbon powder, 10% MgO, and 85%
refined diatomaceous earth for the determination of
chlorinated hydrocarbons in 1-liter samples of seawater
collected off the Southern California coast. Reported
PCB concentrations at five stations in the Southern Cali-
fornia Bight ranged from 3 ppt +o 9.6 ppt (10~12 g/g) at
the surface; concentrations reported in five samples ob-
tained at depths from 500 to 1,500 meters ranged from
2.3 to 10.3 ppt. in the majority of samples, p,p'-DDE
and p,p'-DDT were detected; DDE concentrations
ranged from <0.1 ppt to 1.0 ppt at the surface and from
0.3 to 1.2 ppt at depths from 500 to 1,500 meters.
Concentrations of p,p'-DDT were somewhat lower.
Bidleman and Olney (ref. 12) have reported PCB
and DDT concentrations at eight stations in the Sargasso
Sea in 1973. PCB concentrations in subsurface water
were lower than detectability «0.9 x 10"' 2 g/g) at four
of the stations and ranged from 1.0 to 3.6 x 10"12 g/g at
the others. Concentrations of p,p -DDT were 0.5 x 10"12
g/g at one station but were below detectability «0.15 x
10"*2 g/g) at the others. Samples were collected in 3.8-
liter glass jugs at depths approximately 30 cm below the
surface. Substantially higher concentrations were meas-
ured in the surface microlayer. These concentrations
were calculated by reference to Arocloi 1260. Concen-
trations calculated by reference to Aroclor 1254 may
have been up to two times higher (ref. 28),
Because of the difficulties in extracting large vol-
umes of seawater with organic solvents, Harvey et al.
(ref. 3) de^eioped a column extraction system using
Amberlite XAD-2 resin. Seawater samples in volumes
ranging between 19 and 80 iiters were obtained in a large
volume sampler and passed through the resin on board
231
-------
ship. Also, the extracts were analyzed on board ship.
Reported PCB concentrations, calculated by reference to
Aroclor 1254, averaged 35 x 10~12 g/g at the surface and
10 ppt at 200 meters. At depths of 100, 1,500, and
3,000 meters reported concentrations were >1 ppt. Sam-
ples were obtained in the summer of 1972 (ref. 3).
In 1973 and 1974, substantially lower values were
recorded and it was concluded that PCB concentrations
in North Atlantic surface waters had declined 40-fold
over the 2-year period as a result of restrictions on PCB
use (ref. 14). At two stations sampled in 1973 (09° N.
40° W, and 32° N. 70° W.) samples were obtained
through the water column. PCB concentrations ranged
from 4.3 ppt at 10 meters to 1 ppt at 3,000 meters at
the former site and from 0.4 to 1.9 ppt at depths be-
tween 10 meters and 5,100 meters at the latter.
Harvey et al. (ref. 14) estimated that the decline of
PCB concentrations would require removal of 2 x 104
tons of PCB from the upper 200 meters over the 2-year
period, assuming a mean concentration in 1972 of 20 x
10"12 g/g in the upper 200 meters of the North Atlantic
between 26° N. and 63° N.; the volume was assumed to
be 1018 liters. The estimate of the volume over this area
at a depth of 200 meters appears, however, to be low,
perhaps by an order of magnitude since the correspond-
ing area would be 5 x 106 km2. The area of the Atlantic,
including the North and South Atlantic, is 82 x 1D6 km2
(ref. 29). Thus, since the PCB reported consisted pre-
dominantly of pentachlorobiphenyls, in the order of 10s
metric tons of pentachlorobiphenyls would have to be
removed from the upper 200 meters. From 1957
through 1974, a total of only 124 million pounds, equiv-
alent to 5,6 x 104 metric tons of pentachlorobiphenyls
(Aroclor 1254), was sold in the United States (ref. 10).
Sales in 1970, the peak year of U.S. production,
amounted to 5.6 x 103 tons. Since the mean depth of
the Atlantic is 3,926 meters (ref. 29)-and since PCB was
recorded at depths to 3,000 meters, the estimated penta-
chlorobiphenyl content of the North Atlantic would be
correspondingly higher. If the average concentration
throughout the water column were assumed to be 1 ppt,
the average depth assumed to be 3,900 meters and the
area of the North Atlantic between the equator and 65°
N. were assumed to be in the order of 47 x 106 km2, the
pentachlorobiphenyl content would be in the order of
180,000 metric tons, higher than the total U S. domestic
use.
Similarly, the PCB concentrations reported from the
Pacific by Scura and McClure (ref. 16) and by Williams
and Robertson (ref. 15) appear to be too high. If a mean
value of 1 ppt were assumed for the upper 200 meters of
the North Pacific and the area from the equator to 65°
N. is 82 x 106 km2, 16,000 tons of pentachlorobiphen-
yls would be present in this volume. This represents
three times the U.S. use in 1970.
Nisbet and Sarofim (ref. 9) and the Panel on Haz-
ardous Trace Substances (ref. 30) estimated that 1.5-2.5
x 103 tons per year of PCB had been discharged into the
atmosphere from North America. A large fraction of this
amount can be expected to consist of lower chlorinated
PCB compounds such as the tri- and tetrachlorobiphen-
yls.
To eliminate the vety significant problems of con-
tamination during collection and extraction, and the dif-
ficulties of working with low volumes of seawater, we
have worked towards the development of an in situ sam-
pling system, such that all materials in contact with sea-
water that is sampled can be cleaned in the laboratory to
a desired background level and wrapped in clean contain-
ers, to be unwrapped only immediately prior to use. The
system would extract water at a desired depth and could
be rewrapped immediately upon retrieval and stored
under appropriate conditions until analysis.
Our own values obtained with this system have been
substantially lower than those recorded by other investi-
gators. Thus 23 extracts of seawater obtained off
Western Mexico in 1975 contained no detectable chloro-
biphenyls; volumes extracted were in the order of 100
liters. In 22 of these samples, concentrations of penta-
chlorobiphenyls were less than 100 parts per quadrillion
C\0'1S g/g); in 11 samples, concentrations were less than
50 x 10~15 g/g (ref. 13). We believe these values to be
more consistent with the requirements of a global mass
balance equation, yet intercalibration of all methodolo-
gies used to determine organochlorines in seawater is
urgently required.
River Transport of Chlorobiphenyls to the Marine
Environment
Nisbet and Sarofirn (ref. 9) estimated that 4 to 5 x
103 tons/year of PCB were discharged into fresh and
coastal waters in the peak year of PCB use. This estimate
was based upon use figures and industrial and disposal
practices in effect at that time. Of the total PCB, about
1,000 tons may be assumed to have consisted of penta-
chlorobiphenyls. Analysis of wastewaters and of surface
runoff entering the Southern California Bight since 1971
has shown that trichlorobiphenyls have constituted the
majority of the total PCB residues. In this area, PCB
input into the sea from wastewaters is considerably high-
er than the input from surface runoff. Estimated total
PCB input into the Bight from these sources in 1972 was
20 tons; in 1974 total input was estimated to be 6.5 tons
(Young et al., op. cit.).
232
-------
Atmospheric Transport of PCB's to Marine Environ-
ments
Peel (ref. 31) was unable to detect PCB compounds
in samples of Antarctic snow obtained in December
1969 inland from the British Antarctic Station at Halley
Bay (75°31 'S. 26°42'W.). The samples represented the
previous 5 to 10 years' accumulation. Total concentra-
tions of p.p'-DDT and p,p'-DDE ranged from 0.1 to 2.0
x 10~12 g/g. On this basis, the argument was advanced
that on a global scale the atmosphere is not the predomi-
nant mode of transport of PCB. These results, therefore,
appear inconsistent with those of Bidleman and Olney
(ref. 12) and Harvey and Steinhauer (ref. 32), who were
able to detect PCB in samples of marine air at concentra-
tions considerably in excess of those of the DDT com-
pounds.
In 1975 we extracted Antarctic snow in situ on
Doumer Island in the Antarctic Peninsula (63°35.5'W.
64°51.3'S.); eggs of three species of antarctic penguins
(Pygoscelis adeliae, P. papua, P. antarctica) were ob-
tained to look for PCB in the food webs and to compare
residues with those obtained 5 years previously (ref. 2).
Eleven 99-liter samples of snow were extracted by tech-
niques described elsewhere (R. W, Risebrough, W.
Walker II, B, W. de Lappe, unpublished manuscript).
PCB concentrations, as pentachlorobiphenyls, ranged
from 30 to 1,200 x 10"15 g/g; median concentration was
300 x 10~15 g/g. The median total DDT-.PCB ratio in
these samples was 6.
Pentachlorobiphenyls were detected in all of 27
penguin eggs of the three species obtained in 1975. In
addition, 15 eggs of the Adelie penguin obtained in
Arthur Harbor on Anvers Island, near Palmer Station, on
25 December 1973 also contained pentachlorobiphenyls.
The median DDE:PCB ratio was 3.0. Concentrations of
p,p'-DDT were low compared to those of p,p'-DDE. Fur-
thermore, reexamination of extracts of 14 Adelie pen-
guin eggs obtained at the same site in Arthur Harbor in
1970 showed the presence of PCB compounds in all
extracts, A variety of unknown compounds had previ-
ously interfered with the detection of pentachlorobi-
phen -Is. These however, could be destroyed by rigorous
saponification (R. W. Risebrough and T. T. Schmidt,
unpublished data).
Total DDT:PCB ratios recorded in several of the
subantarctic samples from the Auckland Islands ranged
between 2 and 4 (ref. 33), comparable to those recorded
in the Antarctic penguin eggs. Moreover, concentrations
of DDE and PCB were equivalent north and south of the
Convergence. Thus, fallout patterns of chlorinated
hydrocarbons appear to be equivalent north and south
of the Antarctic Convergence, which separates waters
derived both from the melting of the Antarctic Icecap
and from upwelling from waters of the southern Atlan-
tic, Pacific, and Indian Oceans. Residues in the Antarctic
have therefore derived from atmospheric transport rath-
er than from oceanic circulation. The possibility that the
residues of organochlorine pollutants in Antarctica have
resulted from human activities at the scientific bases has
been examined and discounted (ref. 34).
Changes in PCB Contamination Levels in the Marine
Environment
PCB levels in mussels, Mytilus, at several sites in the
Southern California Bight, have declined between 1971
and 1974 (B. W. de Lappe, R. W. Risebrough, P.
Millikin, and D. R. Young, unpublished data). As dis-
cussed above, the reported decline of PCB values in the
North Atlantic mixed layer (ref. 14) appears unlikely.
The seabird data (refs. 35, 7, 27) do not indicate a de-
cline in the North Atlantic between 1971 and 1973.
Most meetings, particularly international meetings
discussing pollution problems of the marine environ-
ment, have recommended monitoring programs that
would follow with time changes in the levels of particu-
lar pollutant classes. These recommendations have yet to
be implemented; indeed, we might be reluctant to sup-
port such recommendations without assurance that the
numbers obtained would be meaningful. A "Mussel
Watch" (ref. 36) will shortly be underway in the United
States which will examine mussels, principally M. edulis
and M. californianus, from coastal sites for PCB and
other chlorinated hydrocarbons, as well as for plutonium
isotopes, petroleum compounds, and selected metais.
Many variables, including salinity, temperature, particu-
late content of the water, gonadal condition, time of
year, size of the organism, microhabitat, etc., can be
expected to affect the va'iance of the determinations
obtained in such monitoring programs. Nevertheless, the
program does provide a beginning, which hopefully will
determine how levels of chlorobiphenyls change in a
marine environment in response to changes in produc-
tion and use practices.
Summary
The deep ocean waters and sediments are a potential
sink for chlorinated biphenyl compounds, removing
them from food webs which provide input to man. Data
on PCB levels in seawater ace as yet unsatisfactoiy or too
few to permit a reliable estimate of the amounts of PCB
that have so far ?.>'*ered the oceans. Formulation of a
global mass balan^ equation for the major kinds of PCB
233
-------
compounds would be useful in predicting future contam-
ination levels.
ACKNOWLEDGMENTS
Research was supported by the International De-
cade of Ocean Exploration Program of the National
Science Foundation, grant numbers GX32885 and
ID072-06412 A02; the Office of Polar Programs, Nation-
al Science Foundation, grant numbers OPP74-21254 and
OPP75-23b20; and by the Canadian Wildlife Service.
REFERENCES
1. G. W. Bowes and C. J. Jonkel, "Presence and Distri-
bution of Polychlorinated Biphenyls (PCB) in Arctic
and Subarctic Marine Food Chains," Journal of the
Fisheries Research Board of Canada Vol. 32, No. 11
(1975), pp. 2111-2123.
2. R. W. Risebrough and G. M. Carmignani, "Chlorin-
ated Hydrocarbons in Antarctic Birds," Proceedings
of the Colloquium, Conservation Problems in Ant-
arctica, B. C, Parker, ed., Allen Press, Lawrence,
Kansas, 1972, pp. 63-78.
3. G. R. Harvey, W. G. Steinhauer, and J. M. Teal,
"Polychlorobiphenyls in North Atlantic Ocean
Water," Science, Vol. 180 (1973), pp. 643-644.
4. J. H. Koeman, H. C. W. Van Velzen-blad, R. de
Vries, and J. G. Vos, "Effects of PCB and DDE in
Cormorants and Evaluation of PCB Residues From
an Experimental Study," J. Reprod. Pert, Suppl.
19, 1973, pp. 353-364.
5. P. R. Spitzer, R. W. Risebrough, J. W. Grier, and C.
R. Sindelar, "Egysshell-Thickness-Pollutant Rela-
tionships Among North American Ospreys," Proc.
North American Osprey Symposium, J. Ogden, ed.,
(in press).
6. S. M Wiemeyer, P. R. Spitzer, W. C. Krantz, T. G.
Lamoni, ana E. Cromartie. "Effects of Environmen-
tal Pollutants on Connecticut and Maryland Os-
preys,"/ Wildl. Mftiage,, Vol. 39, No. 1 (1975), pp.
12-1-139.
7. W. R. P. Bourne and J. A, Bogan, "Polychlorinated
Biphenyls in Nor hi Atlantic Seabirds," Marine Pol-
lut. Bull., Vol. 3 (1972), pp. 171-175.
8. C. M. White and R. W. Risebrough, "Polychlorin-
ated Biphenyls in the Ecosystems of Amchitka Is-
land," The Environment of Amch/tka Island, Alas-
ka, M. L. Merritt and R. G. Fullers, eds., Oak Ridge,
Tennessee, Technical Information Center, Atomic
Energy Commission, 1976. fin (.,.":$!.
9. i C. T. Misbel: and A. F. ^.i/im, "Rates and
Routes of Ttansport of PCB's i> Environment,"
Environ. Health Perspectives, No. 1 (1972), pp.
21-38.
10. Monsanto Chemical Company, St. Louis, Mo., Octo-
ber 23, 1975, (inlitt).
11. D. Mackay and P. J, Leinonen, "Rate of Evapora-
tion of Low-Solubility Contaminants From Water
Bodies to Atmosphere," Environ. Sci. and Tech.,
Vol.9, No. 13 (1975), pp. 1178-1180.
12. T. F. Bidleman and C. E. Olney, "Chlorinated
Hydrocarbons in the Sargasso Sea Atmosphere and
Surface Water," Science, Vol. 183, No. 4124
(1974), pp. 516-518.
13. R. W. Risebrough, E. W. de Lappe, and W. Walker
II, "Pollutant Transfer to the Marine Environ-
ment: Synthetic Organics," Proceedings of a
symposium held at the Skidaway Institute of Ocean-
ography, H. L. Windom, ed.. Savannah, Georgia,
January 7-9, 1976, (in press).
14. G. R. Harvey, W. G. Steinhauer, and H. P. Miklas,
"Decline of PCB Concentrations in North Atlantic
Surface Water," Nature. Vol. 252 (1974), pp.
387-388.
15. P. M. Williams and K. J. Robertson, "Chlorinated
Hydrocarbons in Sea-Surface Films and Subsurface
Waters at Nearshoie Stations and in the North Cen-
tral Pacific Gyre," Fishery Bull., Vol. 13 (1975), pp.
445-447.
16. E. D. Scura and V. E. McClure, "Chlorinated Hydro-
carbons in Seawater Analytical Method and Levels
in the Northeastern Pacific," Marine Chemistry,
Vol. 3, No. 1975 (1975), pp. 337-346.
17. P, T. S. Wong and K. L. E. Kaiser, "Bacterial Degra-
dation of Polychlorinated Biphenyls. II. Rate
studies," Bull. Environ. Contam. Toxicol., Vol. 32,
No. 2 (1975), pp. 249-255.
18. R. W. Carlson and R. T. Duby, "Embryotoxic Ef-
fects of Three PCB's m the Chicken," Bull. Environ.
Contam. Toxicol., Vol. 9 (1973), p. 261.
19. C. F. Tumasonis, B. Bush, and F. D. Baker, "PCB
Levels in Egg Yolks Associated With Embryonic
Mortality and Deformity of Hatched Chicks," Arch.
Environ. Contam. Toxicol., Vol. 1 (1973), pp.
312-324.
20. H. C. Cecil, J. Bitman, R. J. Lillie, G. F. Fries, and
J. Verrett, "Embryotoxic and Teratogenic Effects in
Unhatched Fertile Eggs From Hens Fed Polychlorin-
ated Biphenyls (PCB's)," Bull. Environ. Contam.
Toxicol., Vol. 11 (1974), p. 489.
21. H. Hays and R. W. Risebrough, "Pollutant Concen-
trations in Abnormal Young Terns From Long Is-
land Sound," The Auk, Vol. 89 (1972), pp. 19-35.
22. j. Verrett, Statement before the Subcommittee on
Energy, Natural Resources, and the Environment of
234
-------
the Committee on Commerce, United States Senate,
Ninety-First Congress, Second Session on Effects of
2,4,5-T on Man and the Environment, Serial 91-60,
U.S. Government Printing Office, 1970, pp.
190-360.
23. J. G. Vos, J. H. Koeman, H. L. Van der Maas, M. C.
Ten Noever de Brauw, and R. H. de Vos, "Identifi-
cation and Toxicological Evaluation of Chlorinated
Dibenzofuran and Chlorinated Naphthalene in Two
Commercial Polychlorinated Biphenyls," Food Cos-
met. Toxicol., Vol. 8 (1970), pp. 625-633.
24. J. G. Vos and J. H. Koeman, "Comparative Toxico-
logic Study With Polychlorinated Biphenyls in
Chickens With Special Reference to Porphyria, Ede-
ma Formation, Liver Necrosis and Tissue Residues,"
Toxicol. Appl. Pharmacol., Vol. 17 (1970), pp.
656-668.
25. G. W. Bowes, M. J. Mulvihill, B. R. Simoneit, A. L.
Burlingame, and R. W. Risebrough, "Identification
of Chlorinated Dibenzofurans in American Poly-
chlorinated Biphenyls," Nature, Vol. 256 (1975),
pp. 305-307.
26. R. J. Norstrom, R. W. Risebrough, and D. J. Cart-
wright, "Elimination of Chlorinated Dibenzofurans
(CDFs) Associated With PCBs Fed to Mallards (Anas
platyrhynchos)," (unpublished ms.).
27. H. M. Ohlendorf, R. W. Risebrough, and K. Ver-
meer, "Exposure of Marine Birds to Environmental
Pollutants," Proc. Pacific Seabird Congress, (in
press).
28. R. W. Risebrough and B. W. de Lappe, "Accumula-
tion of Polychlorinated Biphenyls in Ecosystems,"
Environ. Health Perspectives, No. 1 (1972), pp.
39-45.
29. H. V. Sverdrup, M. W. Johnson, and R. H. Fleming,
"The Oceans: Their Physics, Chemistry and General
Biology," Prentice Hall, New York, 1942, 1087 pp.
30. Panel on Hazardous Trace Substances, "PCBs —
Environmental Impact," Environ. Research, Vol. 5
(1972), pp. 249-362.
31. D. A. Peel, "Organochlorine Residues in Antarctic
Snow," Nature, Vol. 254 (1975), pp. 324-325.
32. G. R. Harvey and W. G. Steinhauer, "Atmospheric
Transport of Polychlorobiphenyls to the North
Atlantic," Atmospheric Environment, Vol. 8
(1974), pp. 777-782.
33. S. Bennington, P. G. Connors, C. Connors, and R.
W. Risebrough, "Patterns of Chlorinated Hydrocar-
bon Contamination in New Zealand Subantarctic
and Coastal Marine Birds," Environ. Pollut, Vol. 8
(1975), pp. 135-147.
34. R. W. Risebrough, 'Transfer of Organochlorine Pol-
lutants to Antarctica," Adaptations Within Antarc-
tic Ecosystems, Scientific Committee for Antarctic
Research, G. A. Llano, ed., 1976, (in press).
35. J. A. Sproul, Jr., R. L. Bradley, Jr., and J. J. Hickey,
"Polychlorinated Biphenyls, DDE, and Dieldrin in
Icelandic Seabirds," Pesticides Monitoring J., (in
press).
36. E. D. Goldberg, "The Mussel Watch - A First Step
in Global Marine Monitoring," Marine Pollut. Bull.,
Vol. 6 (1975), p. 111.
235
-------
UPTAKE OF THREE POLYCHLORINATED BIPHENYLS, DDT
AND DDE BY THE GREEN SUNFISH, Lepomis Cyanellus Raf
James R. Sanborn, Ph.D., William F. Childers, and Robert L Metcalf*
Abstract
The ubiquitous occurrence of polychlorinated bi-
phenyls (PCB's) in aquatic organisms demonstrates the
extreme persistence of these materials and their resist-
ance to being metabolized in fish to water-soluble prod-
ucts (refs. 12,3,4,5). The complex mixtures of chlorin-
ated biphenyls in commercial PCB's makes quantitative
research on the physiological effects of these compounds
and their susceptibility to metabolism very difficult.
However, the availability of three 14C biphenyls-
2,2',5-trichlorobiphenyl, 2,5,2',5'-tetrachlorobiphenyl,
and 2,4,5,2,5?-pentachlorobiphenyl—provides a partial
solution to this problem as these three pure isomers are
major components of three important commercial
PCB's, namely, 1242, 1248, and 1254 (ref. 6). Recently
the fate of these pure chlorinated biphenyl isomers has
been examined in a model ecosystem. The substantial
accumulation of both the tetra- and pentachlorobi-
phenyl isomers by the mosquito fish, Gambusia affinis
Baird and Girard, 15.6 and 119.7 ppm (parts per mil-
lion), respectively, clearly demonstrated the necessity
for the examination of the uptake of these materials
from -tvater by fish (ref. 7). This communication reports
the uptake of three pure 14C PCB's, DDT, and DDE by
the green sunfish, Lepomis cyanellus Raf.
MATERIALS AND METHODS
The three pure (> 99 percent by tic, thin-layer
chromatography, and radioautography) chlorinated bi-
phenyls were obtained from Mallinckrodt and had the
following specific activities in mCi/mM: 2,2',5-trichloro-
biphenyl 9.83; 2,2',5,5'-tetrachlorobiphenyl 9.78; and
2,4,5,2',5'-pentachlorobiphenyl 9.78. The ring-labeled
14C DDT and DDE were available from previous work
and had specific activities of 0.264 and 5.59 mCi/mM,
respectively (ref. 8). Fifteen green sunfish weighing
50-150 mg were placed in 2 liters of aged tap water for a
24-hour acclimation period, then two concentrations,
* Illinois Natural History Survey, Illinois Agricultural Experi-
ment Station and the University of Illinois, Urbana,
Illinois 61801.
All figures and tables reproduced from and text adapted
from Bullentin of Environmental, Contamination & Toxicology,
Vol. 13, No. 2 (1975), pp. 209-217. ©1975 by Springer-Verlag
New York Inc. Used by permission
approximately 1 and 3 ppb, of the five compounds in
acetone were added to the jars. Each concentration was
run at 22 ° C in triplicate and the fish were fed Daphnia
magna Straus twice a week during the experiment. The
experimental design as described in table 1 is taken in
part from the study on the uptake of DDT and
methoxychlor by several species of fish (ref. 9). This
type of .experiment models the pulsed introduction of
pesticides or industrial chemicals into the aquatic envi-
ronment. Each point on the graphs represents the aver-
age of three fish and when the standard deviation for
each point was divided by the average for each point, an
average of 22 percent was obtained for all of the experi-
ments.
Analysis of concentrations of the various com-
pounds in the fish was accomplished by solubilizing the
fish individually in scintillalion vials with one ml Proto-
sol® (New England Nuclear) at 60° C for 4 to 6 hours
and then adding Aquasol® (New England Nuclear) for
scintillation counting. This method assumes that all the
radioactivity is parent compound, which, except for the
trichlorobiphenyl which undergoes substantial metabo-
lism, (see table 3) was an excellent assumption. At the
end of the experiment the remaining fish were ground in
acetone and the extracts were spotted on tic plates
(silica gel GF-254, Brinkmann, 0.25 mm) and developed
in Skellysolve B for metabolite distribution by radio-
autography (Blue Brand X-ray film, Eastman Kodak)
and liquid scintillation counting. The fluid used for
counting contained PRO (7 g), POPOP (0.05 g), and
napthalene (120 g) in 1 liter dioxane. Quenching for
both the fish and tic analysis was corrected using an
external standard.
RESULTS AND DISCUSSION
Tables 1 and 2 show the experimental design of the
uptake study and the amounts of 14C compounds added
to the environment of the fish. The data in table 3 des-
cribe the metabolite distribution of the compounds at
the end of this uptake investigation. Table 4 contains
data showing the bioconcentration of the three 14C
PCB's, DDT, and DDE. Figures I through 5 show the
time-dependent uptake of the five compounds by
Lepomis cyanellus Raf. Figure 6 shows the relationship
for the ihree PCB's and DDE between the unextractable
radioactivity in Gambusis affinis Baird and Girard in the
236
-------
Table 1. Timetable for experiment on uptake of three PCB's,
DDT, and DDE by Lepomis cyanellus Raf
Day Treatment
0 Add ll|C in acetone
2 Take out one fish, weigh and count 14C
3 Take out one fish, weigh and count 1L*C
9 Change water and add lt(C in acetone
10 Take one fish, weigh and count 14C
13 Take one fish, weigh and count 14C
16 Take one fish out, weigh and count 14C, grind
remaining fish up in acetone, spot acetone ex-
tracts on tic for metabolite distribution
Table 2. Amounts of three PCB's, DDT, and DDE added to
environment of Lepomis cyanellus Raf
Trichlorobiphenyl
Low
High
Tetrachlorobiphenyl
Low
High
Pentachlorobiphenyl
Low
High
First
ppb
0.94
2.80
2.50
7.50
1.77
5.31
Second
ppb
2.80
5.61
1.57
5.00
1.77
5. 31
DDT
Low
High
DDE
Low
High
First Second
ppb ppb
6.11 0.11
0.33 0.33
1.13 2.25
3.40 6.75
Table 3. Percent distribution of 14 C-labeled PCB's, DDT, and
DDE at end of experiment in Lepomis cyanellus Raf
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
DDE
DDT
Parent
18.39
98.84
99.41
99.00
97.23
Polar*
81.61
1.16
0.69
1.00
2.27
*Rf = 0 Skellysolve B
237
-------
Table 4. Bioconcentration of 14C-labeled PCB's, DDT, and DDE in
Lepomis cyanellus Raf. after 15 days
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
DDE
DDT
54
460
1,510
890
17,500
4.0
3.0
2.0
Jl.O
o—o
High
Low
10
Tim* ( Doyi )
15
20
Figure 1. Time-dependent uptake of trichlorobiphency
by Lepomis cyanellus Raf
4.0
3.0
2.0
1.0
Cl Cl
0—0
High
low
10
Tima(Doys)
20
Figure 2. Time-dependent uptake of tetrachlorobiphenyl
by Lepomis cyanellus Raf
238
-------
10.0
8.0
E
o.
,6.0
4.0
2.0
Cl
o—o
High
low
10
Tim* ( D o y s )
15
20
Figure 3. Time-dependent uptake of pentachlorobiphenyl
by Lepomis cyanellus Raf
6.0
4.0
2.0
DOE
O—O
Low
10
Tim* ( Day t )
15
20
Figure 4. Time-dependent uptake of DDE
by Lepomis cyanellus Raf
239
-------
E 6.0
O
o
4.0
* 2.0
DOT
O—O
High
Low
10
Tim* ( Oayt )
15
20
Figure 5. Time-dependent uptake of DDT
by Lepomis cyanellus Raf
1.40
-1.00
I
<
*-
u
oc
5 0.00
z
o
o
-1.00
xTRJCHlOROBIPHENYl
y-U6X»1.37
r-0.90 2
O.OKP<0.05
TETRACHLOROBIPHENYl®\^ DOT®
PENTACHLOROBIPHENYLO
DDE.J)
0.50 1.00
ppm (9/3, 16/10)
1.5
Figure 6. The relationship for the three RGB's and DDE be-
tween the unextractable radioactivity in Gambusia
affinis Baird and Girard in the 33-day ecosystem
and the average change in concentration of radio-
activity from day 3 to day 9 and day 10 over day
16.
240
-------
33-day ecosystem (ref. 7) and the average change in con-
centration of radioactivity from day 3 to day 9 (ppm
day 9/ppm day 3) and day 10 over day 16 (ppm day
16/ppm day 10). Each point on figure 6 on the abscissa
is an average of four values.
It is quite clear from examination of figures 1
through 5 that three of the compounds-namely the pen-
tachlorobiphenyl, DDT, and DDE-have similar uptake
curves in that the fish retain the radiolabeled compound
after it is added to the environment of the fish. The
point for the last day for DDT is not shown, as the fish
died before final value could be measured.The tetrachlo-
robiphenyl is retained somewhat less than pentachlo-
robiphenyl, DDT, and DDE, in that a few days after a
peak concentration is reached after addition of labeled
biphenyl the curve begins to drop. The trichlorobiphenyl
differs dramatically from the preceding four compounds,
in that after the peak concentration the curve drops off
sharply.
This type of metabolic susceptibility for chlorinated
biphenyls, namely that the lower chlorinated biphenyls
undergo metabolism more readily than the higher chlo-
rinated RGB's, has been shown for the complex commer-
cial mixtures using rats (ref. 10) and Japanese quail (ref.
11). However, the literature appears to be lacking in
metabolism studies on pure isomers of the RGB's except
for some work on 4-chlorobiphenyl in the rabbit (refs.
12, 13). A comparative metabolism study with pigeons,
rats, and trout and 4-chlorobiphenyl, 4,4 -dichlorobi-
phenyl, 2 ,5 ,2 ', 5'-tetrachlorobipheny I, and
2,4,5,2',4',5'-hexachlorobiphenyl has been reported (ref.
13). These authors found that the trout could not
hydroxylate any of these compounds while the pigeon
and rat were able to hydroxylate all but the hexachlo-
robiphenyl. Recently an elimination study with the
rhesus monkey and two pure 14C biphenyls-2,4'-
dichlorobiphenyl and 2,5,2'-trichlorobiphenyl-has been
reported but no metabolite structure or distribution was
reported (ref. 14). The first hydroxylated metabolite
from a higher chlorinated biphenyl has been reported in
a study of the excretion products of 2,4,3',4'-tetrachlo-
robiphenyl in rats (ref. 15). These authors identified two
hydroxylated species as the 2- and 5-hydroxy derivatives
of the tetrachlorobiphenyl. Further, the 5-hydroxy bi-
phenyl was determined to be about four times more
toxic to the rat than the tetrachlorobiphenyl.
The data reported in this paper corroborate quite
well the information already available, except for the
trout, on the metabolism of RGB's by organisms. In the
present work the data indicate rather convincingly that
the green sunfish is able to transform the trichlorobi-
phenyl into polar species as only 18 percent (table 3) of
the radioactivity in the fish was parent material at the
end of the experiment. Perhaps species differences and
temperature optimum of detoxifying enzymes account
for the discrepancy between the relative abilities of the
trout and green sunfish to metabolize chlorinated bi-
phenyls. Further, previous investigations have shown
that trout liver microsomes as compared to mouse liver
microsomes are very inefficient at introducing a hydrox-
yl group into an aromatic nucleus such as biphenyl (ref.
16) and therefore the reported inability of trout to
hydroxylate any chlorinated biphenyl is not surprising.
Finally, figure 6 clearly demonstrates an inter-
esting relationship between the dynamics of uptake in
the present study, that is, the change in concentration of
the biphenyls in the fish after labeled compounds are
added to the water of the fish, and the percent unex-
tractable radioactivity in Gambusia affinis Baird and
Girard in the 33-day model ecosystem experiment. This
is a logical relationship, as it would be expected. The
greater the metabolic susceptibility, the larger the
amount of incorporation of 14C radioactivity into unex-
tractable polar compounds.
This study emphasizes the need for further research
and information on uptake and metabolism of polychlo-
rinated biphenyls by aquatic organisms. It has been
established that 2,5,2'-trichlorobiphenyl is quite suscep-
tible to metabolism by the green sunfish, and
2,5,2',5'-tetrachlorobiphenyl and 2,4,5,2',5'-pentachlo-
robiphenyl are much less susceptible. These latter two
chlorinated biphenyls, especially the pentachloro isomer,
resemble the relatively metabolic inert chlorinated
hydrocarbons DDT and DDE. Much of the previous
work, and this paper, deal with the qualitative assess-
ment of metabolic susceptibility as a function of number
'of chloro substituents. This type of information is useful
as it provides the background data for work that desper-
ately needs to be done on the effect of chlorine isomer
distribution on metabolic susceptibility, and, even more
important, the further structural elucidation of the
hydroxylated chlorinated biphenyls.
ACKNOWLEDGMENTS
The authors want to thank Dr. Ching-Chieh Yu,
Janet Matusumoto, and M. Kathryn McClendon for their
skillful assistance during this work. This investigation
was supported in part by the Illinois Natural History
Survey, the Illinois Agricultural Experiment Station,
Regional Project NC 96; U.S. Environmental Protection
Agency Grant No. EPA 800736; U.S. Department of the
Interior Grant No. 14-31-000-3879; and a grant to RLM
from U.S. Department of the Interior No.
14-31-0001-3273, Project No. B-050-ILL.
241
-------
REFERENCES
1. C. Henderson, A. Inglis, and W. L.Johnson, "Fall
1969 National Pesticide Monitoring Program," Pest.
Monit.J.,Vo\. 5 (1971), p. 1.
2. J. H. Koeman, M. C. Ten Noever De Brauw, and R.
H. Devos, Nature, Vol. 221 (1969), p. 1126.
3. V. Zitko, Bull. Environ. Contam. Toxicol., Vol. 6
(1971), p. 464.
4. R. W. Risebrough, R. Reiche, D. B. Peakall, S. G.
Herman, and Min Kirven, Nature Vol. 220 (1968),
p. 1098.
5. J. Jensen, A. G. Johnels, S. Olsson, and G. Otter-
lind. Nature, Vol. 224 (1969), p. 247.
6. R. G. Webb and A. C. McCall, J. Assoc. Office. Agri.
Chem.,Vo\ 55 (1972), p. 746.
7. Robert L. Metcalf, James R. Sanborn, Po-Yung Lu,
and Donald E. Nye, unpublished data, 1974.
8. Robert L. Metcalf, Gurchuran K. Sangha, and Inder
P. Kapoor, Environ. Sci. Techno!., Vol. 5 (1971), p.
709.
9. Keturah A. Reinbold, Inder P. Kapoor, William F.
Childers, Willis N. Bruce, and Robert L. Metcalf, ///.
Nat. Survey Bul/.,Vo\. 30 (1971), p. 405.
10. D. L. Grant, W. E. T. Phillips, and D. C. Villeneuve,
D.C. Bull. Environ. Contam. Toxicol., Vol. 6
(1971), p. 102.
11. S. Bailey and P, J. Bunyan, Nature, Vol. 236
(1972), p. 34.
12. W. D. Block and H. H. Cornish, J. Biol. Chem.,\lo\.
(1959), p. 3301.
13. 0. Hutzinger, A. Inglis, and W. L. Johnson, "Fall
1969 National Pesticide Monitoring Program,"Pest.
Monit.J., Vol. 5 (1971), p. 1.
14. W. Greb, W. Klein, F. Coulston, L. Goldberg, and F.
Korte, Chemosphere, Vol. 2 (1973), p. 143.
15. Hidetoshi Yoshimura and Hiroaki Yammamoto,
Chem. Pharm. Bull., Vol. 21 (1973), p. 2239.
16. P. J. Creaven, D. V. Parke, and R. T.Williams, Bio-
chem. J., Vol. 96 (1965), p. 889.
242
-------
LABORATORY MODEL ECOSYSTEM STUDIES OF THE
DEGRADATION AND FATE OF RADIOLABELED
TRI-, TETRA-, AND PENTACHLOROBIPHENYL COMPARED WITH DDE
Robert L. Metcalf, James R. Sanborn, Ph.D., Po-Yung Lu, and Donald Nye*
Abstract
Radiolabeled tri-, tetra-, and pentachlorobiphenyls
(PCB) and DDE were studied in a laboratory model eco-
system for degradation pathways, and biomagnification
in alga, snail, mosquito, and fish. Trichlorobiphenyl was
degraded in all the organisms of the model ecosystem
much more rapidly than tetrachlor- and pentachlorobi-
phenyl. Pentachlorobiphenyl was approximately as per-
sistent as DDE. There was a linear relationship between
lipid/water partition and ecological magnification and
between water solubility and ecological magnification.
No evidence of conversion of DDE to PCB was detected.
The laboratory model ecosystem previously de-
scribed (ref. 1) has been employed for the estimation of
the environmental fate of DDT and a number of its
analogues (refs. 2,3,4) and for study of aldrin, dieldrin,
endrin, mirex, lindane, and hexachlorobenzene (ref. 5).
The methodology developed has yielded useful informa-
tion about (1) the degradation pathways of the various
xenobiotics, (2) the toxic effects of the compounds and
their degradation products, (3) their comparative bio-
magnification and food chain concentration, and (4)
their comparative biodegradability; all in organisms of
five phyla linked in several food chains. This information
has proved of value in characterizing the potential envi-
ronmental pollutant effects of candidate insecticides
(refs. 4,6) and of plasticizers (ref. 7). In this paper we
report the application of these techniques to a better
understanding of the comparative environmental prop-
erties of trichloro-, tetrachloro-, and pentachlorobi-
phenyl (RGB's), and of dichlorodiphenyl-dichloro-
ethylene (DDE) the persistent DDT degradation prod-
uct.
Methods and materials
The laboratory model ecosystem evaluation was
carried out in a small glass aquarium with a sloping ter-
restrial-aquatic interface of pure white sand exactly as
"Department of Entomology and Environmental Studies
Institute, University of Illinois and Illinois Natural History Sur-
vey, Urbana-Champaign, Urbana, Illinois 61801.
All figures and tables reproduced and text adapted from
Archives of Environmental Contamination & Toxicology, Vol.
3, No. 2 (1975), pp. 151-165. ©1975 by Spnnger-Verlag New
York Inc. Used by permission.
previously described (ref. 1).The 14C-radiolabeled com-
pounds were applied quantitatively from acetone solu-
tion at 5.0 mg (or ca. 1 kg per ha) to Sorghum vulgare
seedlings grown in the terrestrial portion. The treated
leaves were consumed by fourth instar salt marsh cater-
pillar larvae Estigmene acrea, whose activities and fecal
products contaminated the aquatic portion of the
system.
The radiolabeled products were transferred through
several food chains, e.g., alga (Oedogonium cardiacum)
->• snail (Physa)', plankton ->• water flea (Daphnia magna]
->• mosquito (Culex pipiens quinquefasciatus) -> fish
(Gambusia affinis}. After 33 days in an environmental
chamber at 26° C and a 12-hr photoperiod at 5,000 foot
candles simulated daylight, the organisms were extracted
with acetonitrile and the 14C-radiolabeled compounds
evaluated by TLC on silica gel containing fluorescent
marker (E. Merck GF-254) and radioautography on no-
screen X-ray film. Liquid scintillation counting of the
individual components was done in cocktail D (5 g PRO
and 100 g naphthalene in dioxane to make 1 liter) and
counts were corrected to dpm by using channels ratio
quenching correction. The residues, after extraction,
were counted by total combustion to 14C02 by the
Schoniger oxygen flask technique (ref. 8) to determine
the unextractable radioactivity. Whenever possible, the
identity erf individual components on the TLC plates was
determined by cochromatography with known standards
and by extraction and mass spectrometry.
Radiolabeled Compounds. The individual 14C-
labeled RGB's were obtained from Mallinkrodt, St.
Louis, Missouri. They were: 2, 5,2'-trichlorobiphenyl
(2,5-dichlorophenyl-ring-UL-14C), 9.91 mCl per mmole
with >98 percent radiopurity and 41.5 percent Cl, and a
principal constituent of Aroclor 1242 (ref. 9);
2,5,2',5'-tetrachlorobiphenyl (ring-UL-14C), 9.87 mCi
per mmole with >98 percent radiopurity and 48.7 per-
cent Cl, and a principal constituent of Aroclor 1248
(ref.9); and 2,4,5,2',5'-pentachlorobiphenyl (2',5'-
dichlorophenyl- ring-UL-14C), 9.87 mCi per mmole with
>98 percent radiopurity and 54.4 percent Cl, a principal
constituent of Aroclor 1254 (ref. 9).
14C -labeled 2,2-bis-(p-chlorophenyl)-1,1-dichlo-
roethylene (DDE) was prepared from 14C-ring-UL
p,p'-DDT obtained from the Radiochemical Centre,
Amersham, England, 5.48 mCi per mmole, by dehydro-
chlorinating with 1.0 M alcoholic KOH, and purifying on
243
-------
a silicic acid column with hexane elution to 99 percent
radiopurity.
Results
PCB's. The movement of 14C radioactivity from
Sorghum plants into the water phase of the model eco-
system is shown in figure 1. All three chlorinated bi-
phenyls reached a maximum concentration in water at
about 7 days after treatment and the levels of contam-
ination declined as the PCB's were taken up by the
organisms of the system. The levels of the chlorinated
biphenyls in the water phase (table 1) were in the ppb
range, below the water solubility of the compounds as
determined by radiotracer technique (table 2).
Radioautographs of the extracts from the compo-
nents of the model system after TLC are shown in figure
2. The data in table 1 represent the quantitative distribu-
tion of the 14C in the spots on the TLC plates. The
results for the three PCB's are also expressed in table 2
in terms of ecological magnification (E.M.) (ppm in
organism/ppm in water) and of biodegradability index
(B.I.) (ppm polar degradation products/ppm nonpolar
products). The E.M. values for the parent compounds
increased substantially with the number of chlorine
atoms, from trichlorobiphenyl (41.£ percent Cl) to tetra-
chlorobiphenyl (48.7 percent Cl) to pentachlorobi-
phenyl (54.4 percent Cl). Conversely, the B.I. values
decreased with increasing degree of chlorine. This con-
sistent and regular behavior gives added confidence that
these parameters are ecologically significant (ref. 4) and
must be a function of the number of C-H bonds available
for hydroxylation by microsomal oxidations in the
various organisms. The spots of low Rf value
(0.02-0.06), figure 2, are presumably hydroxylated PCB
compounds and the polar radioactivity (Rf 0.0) is
thought to consist of conjugates of these compounds.
Wallnofer et al. (ref. 10) have found 4-chloro- 4'-hydro-
xybiphenyl as a metabolite of 4-chlorobiphenyl from
soil fungus, Rhizopus japonicus. Yoshimura and Yam-
mamoto (ref. 11) have reported the 5-hydroxylated de-
rivative as the major and the 3-hydroxylated derivative
as the minor excretion product of 2,4,3',4'-tetrachlo-
robiphenyl in the rat. Hutzinger et al. (ref. 12) have
shown that rat and pigeon could hydroxylate
2,5,2',5'-tetrachlorobiphenvl but they could not detect
hydroxylated metabolites in brook trout. However, the
0.15
trichlorobiphenyl
tetrachlorobiphenyl
pentachlorobiphenyl
0.10 -
a.
a
0.05 -.
0.00 ILL
1
14
21
33
days
Figure 1. Movement of total 14C radioactivity
from plants into the water phase of
the model ecosystem and uptake by
organisms.
244
-------
Table 1. Distribution of chlorinated biphenyls
and their degradation products in the
model ecosystem
Chlorinated biphenyl equivalents (ppm)
I. 2,5,2'-trichloro-
biphenyl total 14C
Unknown I
(Rf 0.66")
trichlorobiphenyl
(Rf 0.56)
Unknown II
(Rf 0.23)
Unknown III
(Rf 0.10)
Unknown IV
CRf 0.06)
Unknown V
(Rf 0.04)
Unknown VI
(Rf 0.03)
Polar (Rf 0.0)
Unextractable
II. 2,5,2',5'-tetrachloro
biphenyl total i"C
tetrachlorobiphenyl
(Rf 0.48")
Unknown I
(Rf 0.23)
Unknown II
(Rf 0.04)
Polar (Rf 0.0)
Unextractable
chlorobiphenyl
total "»C
pentachloro-
biphenyl
(Rf 0.55")
Unknown I
(Rf 0.46)
Unknown II
(Rf 0.39)
Unknown III
(Rf 0.21)
Unknown IV
(Rf 0.04)
Unknown V
(Rf 0.02)
Polar (Rf 0.0)
Unextractable
H20
0.03845
0.00015
0.00020
0.00005
-
0.00055
0.00040
0.00040
0.02265
0.01405
0.02065
0.00120
0.00005
0.00155
0.01225
0.00560
0.04340
0.00985
—
0.00020
0.00015
0.00030
0.00385
0.02055
0.00850
Oedogonium
(alga)
23.2155
15.9575
1.4630
0.0520
-
-
—
0.0685
0.5185
5.1560
23.6845
21.5975"
0.3220
0.1030
0.3275
1.3345
62.4660
53.8440
0.6850
0.5080
0.1425
_
0.2570
1.6265
5.4330
Physa
(snail)
31.2015
18.9720
1.1590
0.6480
0.9735
0.5460
0.2205
0.4410
3.931-5
4.3100
53.7465
47.3275
0.7560
0.4360
3.9850
1.2420
633.0165
587.3545
8.6210
2.2490
'1.9365
0.5000
7.4965
16.5550
8.3040
Culex .
(mosquito)
2.7030
1.1995
0.1630
+
-
-
-
-
0.4795
0.8610
14.5335
12.6745
0.1070
—
0.9670
0.7850
181.4565
170.8480
2.4070
1.3195
1.0520
—
_
2.6745
3.1555
Gambusia
(fish)
3.2055
0.2085
1.2800
0.1595
-
-
-
-
0.9985
0.5590
15.5685
14.2360
0.0890
-
0.8545
0.3900
127.6945
119.7060
2.5380
0.5810
0.3285
_
0.7450
2.3610
1.4350
aTLC with hexane (Skellysolve B,bp 60-68 C).
245
-------
Table 2. Ecological magnification (E.M.) and biodegradability
index (B.I.) of RGB's and DDE compared with water
solubility and partition coefficient
H20 solubility Partition Ecological magnification (E.M.) BiodeEradability index (B.I.)
Chemical (ppb) coefficient Alga Snail Mosquito Fish Aljia Snail Mosquito Fish
tn-Cl-PCB 16 7,803 7,315 5,795 815 6,400 030 0.17 0.35 0.60
tetra-Cl-PCB 16 8,126 17,997 39,439 10,562 11,863 0.015 0.082 0.076 0.060
penta-Cl-PCB 19 16,037 5,464 59,629 17,345 12,152 0029 0.027 0.0134 0.019
DDE 1.3 18,893 11,251 36,342 59,390 12,037 0069 0049 0.033 0.050
Cl
Cl
M
STD S H2O H20
hyd.
Figure 2A. Radioautogram of TLC plate con-
taining extracts of water and
organisms treated with 2,5,2'-
trichlorobiphenyl. A (alga), F
(fish), M (mosquito larva), S
(snail) and STD (14C-radiolabeled
compound).
t * * ! •
A F M STD S H2O H20
hyd.
Figure 2B. Radioautogram of TLC plate con-
taining extracts of water and or-
ganisms treated with 2,5,2',5'-
tetrachlorobiphenyl. A (alga),
F (fish), M (mosquito larva), S
(snail) arid STD (14C-radiolabeled
compound).
246
-------
Figure 2C.
M STD
H20
hyd.
H,O
Radioautogram of TLC plate con-
taining extracts of water and or-
ganisms treated with 2,4,5,2',5'-
pentachlorobiphenyl. A (alga),
F (fish), M (mosquito larva), S
(snail) and STD (14C-radiolabeled
compound).
M STD
H20
Figure 20.
Radioautogram of TLC plate con-
taining extracts of water and or-
ganisms treated with DDE. A (alga),
F (fish), M (mosquito larva), S
(snail) and STD (14C-radiolabeled
compound).
amounts of polar material in Gambusia (figure 2, table
1) suggest that this fish is able to slowly hydroxylate this
tetrachlorobiphenyl.
The pentachlorobiphenyl with B.I. values of 0.019
to 0.027 in fish and snail is very comparable in model
ecosystem behavior to DDT, B.I. 0.015 and 0.044 (ref.
4) and this suggests that the two compounds should
behave similarly in the environment (ref. 13). Properties
of the tetrachlorobiphenyl were similar to those of the
pentachlorobiphenyl (figure 2) but the trichlorobiphenyl
was much more degradable. A prominent degradative
product (Rf 0.66) is stored in alga, snail, and mosquito
larva in much greater quantities than the parent com-
pound. This compound is less polar (higher R^) in the
hexane solvent than any of the three PCB isomers. As
shown in table 1, it is magnified to very high values,
106,382X in alga and 126,480X in snail, is stored in
lipids, and is highly persistent. Its presence in high
amounts in alga and in the snail and mosquito, which are
alga feeders, suggests that it might be formed by photo-
chemical processes during photosynthesis in the alga.
This compound forms slowly and no traces of it were
visible in 3-day uptake studies of trichlorobiphenyl by
alga, snail, daphnia, mosquito, or fish (ref. 14) although
it appeared in alga in 14-day studies. To date we have
been unsuccessful in identifying the unknown by mass
spectrometry.
DDE. This compound has been implicated as a
possible environmental precursor of PCB isomers
through photooxidation reactions involving radical re-
arrangements to 3,6-dichlorofluorenone intermediates
(refs. 15,16,17). Although such rearrangements could
logically produce 4,4'-dichlorobiphenyl, it is difficult to
see how trichloro- and tetrachlorobiphenyls could be
247
-------
formed as suggested by Maugh (ref. 18). Moreover,
Kerner et al. (ref. 19) could detect only bis-{p- chloro-
phenyl)-chloroethylene (DDMU) after ultraviolet irradia-
tion of DDE. Because of the ecological importance of
these possible rearrangements, we have reinvestigated the
behavior of DDE in the model ecosystem (ref. 1) to
determine if any PCB-like products could be formed un-
der the simulated daylight of the model ecosystem
(5,000 foot candles) in an environmental chamber. The
radioautograph showing the fate of pure DDE is present-
ed in figure 2. When the extracts of water and organisms
were developed on TLC plates with Skellysolve B (hex-
ane fraction) there was no trace of any 14C-labeled com-
pounds with Ry values between 0.05 and 0.47 (DDE) or
of any less polar materials with higher R^ values. Under
these conditions, as shown in figure 2, trichlorobiphenyl
has Rf 0.43, tetrachlorobiphenyl R^ 0.50, and penta-
chlorobiphenyl R,, 0.53. Detection levels with the tech-
niques used are approximately 0.1 ng (e.g., spot at alga
origin in DDE, figure 2) or about 0.00002 percent of the
total 14C applied. Thus under the model ecosystem con-
ditions, there is no evidence of formation of PCB
isomers from DDE.
DDE is extremely stable in the tissues of the living
organisms of the model ecosystem and is stored as ap-
proximately 92, 93, 95, and 97 percent of the total 14C
in snail, alga, fish, and mosquito larva. The percent of
unextractable 14C in these organisms ranged from 0.10
to 0.93 (table 3). The B.I. value for DDE in fish was
0.049 and the E.M. value 12,037 (compared with 0.032
and 27,358 found by Metcalf et al.) (ref. 1). From these
values it is apparent that DDE is a more stable environ-
mental pollutant than 2,4,5,2',5'-pentachlorobiphenyl
(table 1), which was sto-ed in the organisms at 86 to 94
percent of the total radioactivity, with from 1.12 to
8.67 percent of unextractable 14C, and had a B.I. of
0.019 and an E.M. of 12,152 in fish.
It is of interest lhat Sodergren (ref. 20), using a
model aquatic ecosystem, found no major metabolic
changes in DDE occurring in passage through a food
chain into fish, although similar experiments with a
polychlorinated biphenyl mixture (Clophen A) showed
that the lower fractions with low chlorine content were
degraded when transported through the food chain, as
was 2,5,2'-trichlorobip'h3ny! in our experiments. How-
ever, in our studies (figure 2, table 3), the water phase
contained several polar radiolabeled degradation prod-
ucts. These were resolved on silica gel into at least 11
distinct compounds using a solvent of
benzene:dioxane:acetic acid (90:30:1) and we are pre-
sently attempting to identify the pathway of DDE degra-
dation in the environment.
Biomass Recovery. To determine the relative avail-
ability of the various organisms of the model ecosystem
as reservoirs for the bioaccumulation of the micropol-
lutants studied, the total amounts of 14C-labeled prod-
ucts recovered from the principal organisms of the
model ecosystems created with tri-, tetra-, and
pentachloro-PCB's, and with DDE were evaluated, as
shown in table 4. The evaluations were made on the
basis of total recovery of the applied pollutant; of recov-
ery of the maximum amount of pollutant in water
(figure 1) for each of the four principal organisms, alga,
snail, mosquito, and fish; and of biomass recovery (four
organisms) of the total amount of pollutant lost from
water (figure 1). The figures of table 4 are very revealing
Table 3. Distribution of DDE and degradation
products in the model ecosystem
DDE equivalents (ppm)
Oedogonium Physa
H2O (alga) (snail)
Culex Gambusia
(mosquito) (fish)
Total l"C
DDE(Rf 0.
Unknown I
Polar (Rf 0
493)
(Rf 0.05)
.0)
Unextractable
0.
0
.00384
.00062
7,
.4720
6.9759
0.00009
0
0.
.00223
.0009
0
0
.4881
.0080
38.
22.
0.
1,
0.
1958
,5325
.8035
,1612
.3616
24.8588
36.8223
-
1.2448
0.1087
7.
7.
0.
0.
8653
4632
-
.3746
.0275
aTLC with hexane (Skellysolve B, bp 60-68°C).
248
-------
Table 4. Biomass recovery of chlorinated
biphenyls, and DDE from organisms
of model ecosystem
% Recovery
Alga
Snail
Mosquito
Fish
'4C in solution 0,18
total 14C 0.033
(biomass) of 14C lost from solution -
1 4 C in solution 3.33
total 14C 0.28
(biomass) of 14C lost from solution -
' 4C in solution 4.57
total 14C 0.74
(biomass) of 14C lost from solution -
in solution 224
total 14C 0.24
(biomass) of 14C lost from solution
trichlorobiphenyl
0.015 0.0017 0.12
0.0028 0.00032 0.021
0.45
tetrach lorobiph enyl
1.04 0.23 1.91
0.088 0.019 0.16
8.7
pentachlorobiphenyl
190 2.32 11.8
3.06 0.37 1.90
-57.2
DDE
4.03 2.25 20.2
0.044 0.055 0.22
-65.8
in terms of the biodegradability of the various com-
pounds. The highest recoveries of the 14C lost from
solution were obtained from the organisms with DDE,
65.8 percent, and pentachlorobiphenyl, 57.2 percent.
With tetrachlorobiphenyl, recoveries of 8.7 percent were
still substantial, but with trichlorobiphenyl (recovery
0.45 percent), the compound was nearly completely
degraded and excreted.
Degradation in Salt Marsh Caterpillar. This animal
was chosen, after considerable study, as the dispersing
agent for the model ecosystem because it was able to
ingest a large variety of organic compounds without
apparent injury (ref. 14). The effects of passage of the
PCB isomers through the insect are of interest as repre-
senting the first stage in the biodegradation of these
compounds. Figurp 3 shows radioautographs of TLC
plates of extracts of feces and body homogenates from
larvae feeding on about 30 pg of 14C PCB incorporated
in a synthetic diet. Figure 3 and the quantitative evalua-
tion of the radioactivity in the various spots shown in
table 5 demonstrate conclusively the much greater degra-
dability of the trichlorobiphenyl over the
tetrachlorobiphenyl and pentachlorobiphenyl. With the
trichloro compound, the caterpillar feces contained 91
percent of the recovered 14C, with the remainder in the
body homogenate, while with the tetrachloro- and
pentachlorobiphenyls, the feces contained 21 percent
and 24 percent of the radioactivity. The unknown (R^
0.05) found in feces after trichlorobiphenyl is probably
the principal hydroxylated degradation product leading
to the very large amount of polar radioactivity. Whereas
only low levels of trichlorobiphenyl were retained in the
salt marsh caterpillar body, with tetrachloro- and
pentachlorobiphenyl the major portion of 14C was
retained in the insect body.
DDE passed through the salt marsh caterpillar
largely unchanged, with 81 percent of the total radio-
activity recovered retained in the body homogenate and
19 percent in the fecal excreta (table 5).
Ecological Magnification. The uptake and concen-
tration of organic compounds by living organisms either
directly or through food chains appear to be a function
of two important factors: (1) their high lipid solubility
and low water solubility, e.g., a large lipid/water parti-
tion coefficient, and (2) their resistance to degradation
by enzymatic processes, especially the multifunction
249
-------
tn-CI
tetra-CI
penta-CI
Figure 3. Radioautogram of TLC plate con-
taining extracts of bodies and feces
of salt marsh caterpillar larvae fed
14C-labeled 2,5,2'-tri-, 2,5,2',5'-
tetra-, and 2,4,5,2',5'-pentachloro-
biphenyis. B (body homogenate),
and F (fecal excreta).
250
-------
Table 5. Metabolism of 14C-radiolabeled compounds by salt marsh caterpillar8
A.
B.
C.
D.
2,5,2'-trichlorobiphenyl total 14C (%)
Unknown I (Rf 0.53a)
trichlorobiphenyl (Rf 0.43)
Unknown II (Rf 0.31)
Unknown III (Rf 0.13)
Unknown IV (Rf 0.05)
Unknown V (Rf 0.02)
Polar (Rf 0.0)
2,5,2',S'-tetrachlorobiphenyl total i«C (%)
tetrachlorobiphenyl (Rf 0.50a)
Unknown I (Rf 0.41)
Unknown II (Rf 0.05)
Unknown III (Rf 0.03)
Polar (Rf 0.0)
2,5,2',4',5'-pentachlorobiphenyl total 14C(%)
pentachlorobiphenyl (Rf 0.53a)
Unknown I (Rf 0.46)
Unknown II (Rf 0.39)
Unknown III (Rf 0.03)
Polar (Rf 0.0)
2,2-i/j-(/?-chlorophenyl)-l,l-dichloToethylene (DDE)
total 14C(%)
DDE(Rf 0.49a)
Polar (Rf 0.0)
Body
8.66
0.64
S.84
0.27
0.05
0.10
0.11
1.65
78.68
75.60
0.99
0.13
trace
1.96
75.86
74.00
0.74
0.62
0.08
0.42
80.59
76.88
3.71
Feces
91.34
-
8.91
0.37
0.12
4.67
0.92
76.35
21.32
15.08
1.36
-
0.20
4.64
24.14
20.70
0.74
0.56
0.08
2.06
19.41
19.37
0.04
aTLC with hexane (Skellysolve B, bp 60-68 C).
oxidase enzymes (ref. 14). Hamelink et al. (ref. 21) have
suggested that the water insolubility of highly lipid-
soluble compounds provides the driving force in
producing lipid storage, through a series of simple parti-
tionirjgs from water to lipids. We have correlated the
E.M. values for the RGB's and DDE from the fish of the
model ecosystems with both water solubility (table 2) in
figure 4, and with the octanol/water partition value
(table 2) in figure 5. Because the values for the PCB's
and DDE fall closely together, the relationships have
been extended using values for aniline, anisole, benzoic
acid, chlorobenzene, and nitrobenzene taken from other
model ecosystem studies (ref. 22). For the limited num-
ber of compounds included, the correlation between
physical properties and biomagnification is excellent.
The regression equation for log water solubility vs. log
E.M. (figure 4) was:
y= 4.4806 - 0.4732X: n = 9, r = -0.9677.
The regression equation for log partition coefficient
(Hansch's TT) vs. log E.M. (figure 5) was:
y = -0.7504 +1.1587X: n = 9, r = 0.9771.
Thus for the organic compounds studied, the prop-
erties of water solubility and octanol/water partition
coefficient appear to provide a realistic estimate of the
biological magnification found in living organisms.
251
-------
5.0 r
2
of
4.0
3.0
2.0
1.0
0.0
penta-CI biphenyl
DDE
1 tetra-CI biphenyl
tri-CI
biphenyl
JL
_L
chlorobenzene
benzole ecid'
nitrobenzene
_J I
anisole
"V
aniline
' I
0.0 1.0 2.0 3.0 4.0 5.0
Log water solubility — ppb
6.0 7.0 8.0
Figure 4. Plot of log E.M. (ecological magnification) for fish vs. log water solubility (ppb).
5.0
4.0
- 3.0
I
s
ui
o
_J
2.0
1.0
0.0
tetra-CI biphenyl
penta-CI biphenyl
>
DDE
W
tri-CI biphenyl
chlorobenzene
benzoic acid
aniline
JL
anisole
nitrobenzene
JL
0.0 1.0 2.0 3.0
Log partition coefficient
4.0
5.0
Figure 5. Plot of log E.M. (ecological magnification) for fish vs. log octanol/water
partition coefficient.
252
-------
ACKNOWLEDGMENTS
This research was supported in part by research
grants from the U. S. Department of Interior, Office of
Water Resources Research through the University of
Illinois Water Resources Center Project B-050, Illinois;
the National Science Foundation Grant Gl 39843X; the
U. S. Environmental Protection Agency Grant R802022
and Grant R800736; and the Bureau of Veterinary
Medicine, Food and Drug Administration, Contract FDA
72-116.
REFERENCES
1. R. L. Metcalf, G. K. Sangha, and I. P. Kapoor, "A
Laboratory Model Ecosystem," Environ. Sci.
Technol., Vol. 5 (1971), p. 709.
2. I. P. Kapoor, R. L. Metcalf, R. F. Nystrom, and G.
K. Sangha, "Comparative Metabolism of
Methoxychlor, Methylchlor, and DDT in Mouse, In-
sects and in a Model Ecosystem," J. Agr. Food
Chem.,Vo\. 18 (1970), p. 1145.
3. L P. Kapoor, R. L. Metcalf, A. S. Hirwe, Po-Yung
Lu, J. R. Coats, and R. F. Nystrom, "Comparative
Metabolism of DDT, Methylchlor, and Ethoxychlor
in Mouse, Insects, and in a Model Ecosystem," J.
Agr. Food Chem., Vol. 20 (1972), p. 1.
4. I. P. Kapoor, R. L. Metcalf, A. S. Hirwe, J. R. Coats,
and M. S. Khalsa, "Structure Activity Correlations
of Biodegradability of DDT analogs," J. Agr. Food
Chem., Vol. 21 (1973), p. 310.
5. R. L. Metcalf, I. P. Kapoor, Po-Yung Lu, C. K.
Schuth, and P. Sherman, "Model Ecosystem Studies
of the Environmental Fate of Six Organochlorine
Pesticides," Environ. Health Persp. Expert'., Issue 4
(1973a),p. 35.
6. J. R. Costs, R. L. Metcalf, and I. P. Kapoor, "Metab-
olism of the Methoxychlor Isostere,
Dianisylneopentane in Mouse, Insects, and a Model
Ecosystem," Pesticide Biochem. Physiol., Vol. 4
(1974), p. 201.
7. R, L. Metcalf, G. M. Booth, C. K. Schuth, D. J.
Hansen, and Po-Yung Lu, "Uptake and Fate of
Di-2-ethylhexyl Phthalate in Aquatic Organisms and
in a Model Ecosystem," Environ. Health Persp.
Expert., Issue 4 (1973b), p. 27.
8. R. G. Kelly, E. A. Peets, S. Gordon, and D. A.
Buyske, "Determination of 14C and 3H in Biolog-
ical Samples by Schoniger Combustion and Liquid
Scintillation Technique," Anal. Biochem., Vol. 2
(1961), P. 267.
9. R. G. Webb and A. C. McCall, "Identities of Poly-
chlorinated Biphenyl Isomers in Aroclors," J. Assoc.
Offic. Agr. Chem., Vol. 55 (1972), p. 746.
10. P. R. Wallnofer, G. Engelhardt, S. Safe, and D.
Hutzinger, "Microbial Hydroxylation of
4-chlorobiphenyl and 4,4'-dichlorobiphenyl,"
Chemosphere, Vol. 2 (1973), p. 69.
11. H. Yoshimura, and H. Yammamoto, "Metabolic
Studies on Polychlorinated Biphenyls III. Complete
Structure and Acute Toxicity of the Metabolites of
2,4,3',4'-tetrachlorobiphenyl," Chem. Pharm. Bull.,
(Japan), 21, 2239 (1973).
12. O. Hutzinger, D. M. Nash, S. Safe, A. S. W.
DeFreitas, R. J. Norstrom, D. J. Wtldish, and V.
Zikkos, "Polychlorinated Biphenyls: Metabolic Be-
havior of Pure Isomers in Pigeons, Rats, and Brook
Trout," Science, Vol. 178 (1972), p. 312.
13. R. W. Risebrough, P. Rieche, D. B. Peakall, S. G.
Herman, and M. N. Kirven, "Polychlorinated
Biphenyls in the Global Ecosystem," Nature, Vol.
220 (1968), P. 1098.
14. R. L. Metcalf, Po-Yung Lu, and I. P. Kapoor,
"Environmental Distribution and Metabolic Fate of
Key Industrial Pollutants and Pesticides in a Model
Ecosystem," Univ. III. Water Resources Center, Re-
port No. 69, Project B-050 Illinois, 1973.
15. J. R. Plimmer, U. I. Klingelbiel, and B. E. Hummer,
"Photooxidation of DDT and DDE," Sc/e/?ce,Vol.
167 (1970), p. 67.
16. D. B. Peakall and J. L. Lincer, "Polychlorinated
Biphenyls, Another Long-Life Widespread Chemical
- in the Environment,"5/ose/ence, Vol. 20 (1970), p.
958.
17. K. W. Moilanen and D. G. Crosby, "Vapor-Phase
Photodecomposition of p,p'-DDT and its Relatives,"
Abstract No. 27, 1973, 165th Meeting American
Chemical Society.
18. T. H. Maugh, II, "DDT: An Unrecognized Source
of Polychlorinated Biphenyls," Science, Vol. 1180
(1973), p. 578.
19. I. Kerner, W. Klein, and F. Korte, "Photochemische
Reactionen von 1,1-dichloro-2-(p,p-Dichloro-
ethylene) DDE," Tetrahedron, Vol. 28 (1972), p.
1575.
20. A. Sodergren, "Transport, Distribution, and Degra-
dation of Chlorinated Hydrocarbon Residues in
Aquatic Model Ecosystems," Oikos, Vol. 24 (1973),
p. 30.
21. J. L. Hamelink, R. C. Waybrant, and R. C. Ball, "A
Proposal: Exchange Equilibria Control the Degree
Chlorinated Hydrocarbons are Biologically Magni-
fied in Lentic Environments," Trans. Am. Fisheries
Soc., Vol. 100 (1971), p. 207.
22. Po-Yung Lu, and R. L. Metcalf, "Degradation and
Environmental Fate of Radiolabeled Benzene Deriv-
atives in a Model Aquatic Ecosystem," manuscript
in preparation.
253
-------
ENVIRONMENTAL TRANSPORT AND OCCURRENCE OF PCB's IN 1975
lanC. T. Nisbet, Ph.D.*
Abstract
Despite curtailment of some dispersive uses, envi-
ronmental levels and rates of transport of PCB's have not
changed greatly since 1972. This is probably due in part
to the continued release of materials in service prior to
1971 and in part to time lags in environmental transport
and dissipation.
Surprisingly high concentrations of PCB's matching
Aroclor 1254 are still being found in air, in precipita-
tion, and in dry fallout.
As yet, there is little evidence that significant quan-
tities of PCB's are being leached from dumps.
Human exposure to PCB's is higly variable. Some
sport fishermen and breast-fed infants have especially
high intakes.
Almost nothing is known about the environmental
behavior of chlorinated dibenzofurans.
I think the organizers of the conference may have
expected me to compose a global transport model while
this session was going on. I have not attempted to do
this, except to make some quick calculations on the
back of an envelope.
My general conclusion from what I have heard to-
day and yesterday about the release and concentrations
of PCB's in the environment in 1975 is that most of
what we have learned since 1972 is reasonably consistent
with the very crude model that Sarofim and I con-
structed in 1972. That is not to say that the model was
right. All it says is that our ignorance about the exact
rates and routes of transport of PCB's in the environ-
ment is nearly as profound in 1975 as it was in 1972.
I have found only one area where there does seem
to be substantial quantitative discrepancy between our
1972 model and the data generated subsequently; that
is,the numbers reported to us here and published in the
interim, t on concentrations in air and air transport. We
have heard some numbers of the order of 200 parts per
trillion of PCB's in snowmelt, reports of numbers of the
'Director, Scientific Staff, Massachusetts Audubon Society,
Lincoln, Massachusetts 01773.
tPersson, B., Ornis Scandinavica, 2:127-135 (1971);
Sodergren, A., PCB-Conference II 7972:15-18 (National Swedish
Environment Protection Board, 1973); Bengtson, A. A. and A.
Sodergren, Ambio, 3:84-86 (1974); Munson, T. 0., Ch. 6 in
Upper Bay Survey (Westinghouse Electric Corporation, Final Re-
port to the Maryland Department of Natural Resources, in
press).
order of 100 nanograms per cubic meter for concentra-
tion of PCB's in air, and the number of the order of 70
— 200 and locally up to 2,000 nanograms per square
meter per day for rates cf dry deposition. These are all
somewhat higher than we anticipated on the basis of our
model.
If we extrapolate up on the back of an envelope
basis from 200 nanogram; per square meter per day over
the whole continent, thai comes out to be something of
the order of 1,000 tons. Similarly, if you extrapolate up
from 100 parts per trillion in rainfall over the entire
continent, you get something of the order of 1,000 tons.
Now, it may be that the numbers we heard were
biased toward urban areas, where the concentration of
PCB's may be higher than they are in the United States
as a whole. Even so, we are now being given numbers
that suggest that at least 1,000 tons of PCB's per year
are falling out onto the terrestrial environment of the
United States in rain and particulate matter. That is
about as large as numbers we had envisaged for total
releases of PCB's into the air in 1971. What makes the
problem worse is that nearly all the PCB's that are found
in dry fallout, in the air, and in precipitation look like
Aroclor 1254,whereas we had thought that only about
half of the materials released into the environment even
in 1971 would be Aroclor 1254, and a good deal of
them would be Aroclor 1242.
So it seems to me that aerial releases and aerial
transport are rather larger than anything we could
account for according to our knowledge of the uses and
releases that we surveyed in 1972. We need to find out
where all this material in the air resembling Aroclor
1254 is actually coming from.
One possibility is that it may be coming from leaks
from supposedly sealed uses. Perhaps we ought to be
looking at transformers to see how much PCB's vaporize
from them.
I would now like to go to the six questions which I
posed at the beginning of this session and see what we
have learned in the course of this conference toward
solving these outslanding problems.
1. What happens to chlorinated dibenzofurans in the
environment? I think 1he answer is that still we know
almost nothing. We know they are being released into
the environment, since they are present in small quanti-
ties in commercial PCB's. Dr. Kuratsune in his presenta-
tion yesterday indicated 1:hat they are actually formed in
the environment during use, and Dr. McKinney's presen-
tation suggested they might be formed by metabolism
254
-------
under certain circumstances. On the other hand, Dr.
Risebrough's presentation suggested that they are not
retained in the bodies of birds even when they are
ingested; that conflicts with Dr. Kuratsune's information
that they are retained extraordinarily efficiently in
human tissue.
2. What happens to PCB's in dumps? Again, we know
almost nothing. Some numbers were mentioned yester-
day for water leaking out of dumps; I did some back-of-
the-envelope calculations which suggested that the
quantities of PCB's escaping are not yet very significant.
One is talking about quantities of the order of hundreds
of kilograms per year nationwide—certainly not more
than a few tons.
3. Are PCB's in sediments going to be covered up or
are they going to be continually recycled? There have
been some hints in what has been said today that they
are going to be recycled. The information from Ms.
McDermott about PCB's in areas where there is shipping
activity, and information from Dr. Munson about the
movement of PCB's in suspended sediments around
Chesapeake Bay suggests that these PCB's in shallow
waters are not going to stay there and be covered up and
disappear. They are going to be with us for a long time
into the future.
4. Is it correct that tetrachloro-biphenyls and lower
chlorinated species are rapidly degraded and is there sig-
nificant human exposure to these lower species? I think
that we have had very adequate evidence here that
tetrachloro isomers are indeed degraded rather rapidly,
but not as rapidly as we would like. Dr. Sanborn's pres-
entation just now suggested that in fish the major differ-
ence in the efficiency of uptake, retention, and metabo-
lism comes between trichlorobiphenyls and tetrachloro-
biphenyls, and that fish do indeed retain tetrachlorob-
iphenyls fairly efficiently. That was supported by data
from the National Fish Monitoring Program, which
suggested that a substantial fraction of the PCB's in the
fish look like Aroclor 1242 and 1248; that means that
they include substantial quantities of tetrachlorobi-
phenyls. This in turn implies that humans are exposed to
tetrachlorobiphenyls. Although the tetrachlorobiphenyls
appear to be rare in human tissue, what that tells us is
that humans do not retain tetrachlorobiphenyls. It does
not tell us that they are not exposed to them.
This has some important implications from the regu-
latory point of view. We may have to consider, for ex-
ample, whether Aroclor 1016 is environmentally "safe,"
in the sense that modest releases can be regarded as
acceptable. These data indicate that releases of Aroclor
1016 into water will lead to human exposure, at least to
tetrachlorobiphenyls.
5. What is the extent of human exposure? The data
derive from two sides, monitoring of human tissue and
monitoring of human food. Human tissue monitoring
tells us that human exposure is very widespread. Human
food monitoring tells us that most PCB's in human food
are in fish.
Unfortunately, that makes it very difficult to esti-
mate human exposure quantitatively, because we know
from the fish monitoring program that the levels of
PCB's in fish are extraordinarily variable in space.
Despite the large number of samples that have been
taken by the Canadian program and by the FDA, it is
very difficult to define an average exposure. I would go
so far as to say that an "average" exposure is a meaning-
less concept, because some individuals who live in areas
where fish residues are high will get exposures 100 times
greater than the average, where as those persons who live
in areas where there is little contamination, or who do
not like fish, will get very little.
Nevertheless, we do have some numbers for human
dietary exposure. The Total Diet Program in the United
States gave a figure of the order of 9 micrograms per day
for the intake of the average adult. I also did some calcu-
lations from Mr. Graham's figures on the Canadian com-
mercial fish to see how many kilograms of PCB's were
brought in in Canadian commercial fish and what frac-
tion was eaten. That led me to a figure around 5 micro-
grams per day for the average intake of the average per-
son in the Canadian population. We have to remember
that the average adult does not eat much fish.
Unfortunately, these figures are quite misleading
because it is very easy for an individual who is a sports
fisherman and who catches salmon, or trout, or chub to
take in very much more than that. One calculation in
our 1972 paper indicated that it would be very easy for
a fisherman or a member of his family to average 300
micrograms per day: this would represent about 4
micrograms per kilogram per day for an adult.
One important point is that exposure of breast-fed
infants is likely to be very much greater than that of any
adult, even- an individual who likes fish. Although Dr.
Kutz did not give numerical estimates of PCB levels in
human milk in this session, earlier data suggest that a
typical level would be around 30 parts per billion.* This
leads to an estimate of 4—5 micrograms per kilogram per
day intake for the average breast-fed infant. There would
*PCB levels reported in human milk have been in the range
10—100 ppb: Risebrough, R. W., and V. Brodine, Environment
12:16-27 (1969); Westo'6, G., Nore'n, K., and M. Andersson, Var
Foda, 22:10-31 (1970); Acker, L., and E. Schulte, Naturwi-
ssenschaften, 57:497 (1970); Savage, E. P., Tessari, J. D.,
Malberg, J. W., Wheeler, H. W., and J. R. Bagby, Pesticides Moni-
toring Journal, 7:1-5 (1973). A concentration of about 30 ppb
would correspond to the median level of about 1 ppm reported
in human fat.
255
-------
be many above the average and many below.
Accordingly, when considering averages, we should
remember that certain individuals are going to get 10 to
100 times the exposure of the average person, as calcu-
lated from an average diet.
6. The most complicated question posed in
1972: what would be the effect of Monsanto's curtail-
ment of dispersive uses? A number of speakers yesterday
and today have talked about decreases of PCB levels in
certain areas or compartments ot the environment. For
example, there have been decreases in the total dietary
intake estimated from the FDA Total Diet Program, in
the frequency of findings of RGB's in milk and fish in
the FDA's surveillance samples, and in runoff into the
Southern California coastal waters. On the other hand,
we have also heard about some levels that have not
changed, particularly levels in fish in Lake Michigan.
There are three reasons why the curtailment of sales
by Monsanto in 1971 should not have been expected to
lead to an immediate reduction in environmental levels.
One is that not all the closed system uses are actually
closed. There are some losses that we heard about today,
even from transformer and capacitor uses, which are
systems as closed as we are likely to get. Secondly, and
more important, there is still a large backlog of products
containing PCB's, that were in service prior to 1971,
which are still in service and are still being discarded and
still leaching. Some of the users of hydraulic fluids, heat
transfer fluids, compressors, and so on, are probably still
using PCB's that they had several' years ago. Certainly
the scrapping of capacitors and any losses that may
result from disposal of transformers are going to lead to
releases for years into the future.
Finally, there is an environmental inertia: it takes a
long time after the input into the environment is cut off
for the levels in fish, for example, to go down. The time
lags will depend on the part of the system under con-
sideration; it is evidently quite short for mussels in
Southern California, but is longer for the fish in the
same area. Time lags have been quite short for the star-
lings, which reflect terrestrial uses, and for soil residues.
The time lag is likely to be long for somewhere like Lake
Michigan, which is a closed system, with a large reservoir
of PCB's in the sediment. So I think we should not have
hoped for a very rapid decline in PCB's since 1971.
On the other hand, it has been somewhat dis-
appointing that it has been so difficult to find any
change in the first 3 or 4 years.
One of the longest time lags of all is likely to be in
human tissue, because there is evidence that PCB's are
retained for an extremely long time in human tissue. We
will probably have to wait for some considerable time
after PCB levels have declined in fish before we see a
significant decline in human tissue residues.
256
-------
GENERAL DISCUSSION OF SESSION III
DR. JOSEPH HIGHLAND (Environmental Defense
Fund, Washington, D.C.): I want to ask Dr. Jelinek
about the survey for fresh fish. Were there many
differences in the last several years in the program
which might lead to differences in the levels of the
species. I was wondering if you could tell us a little
bit more about that. I am not very clear on what
differences you are talking about.
DR. CHARLES JELINEK (Food and Drug Administra-
tion, Washington, D.C.): First of all, one of the big
differences is in the fact that all of our activities
included compliance followups when we found any
species or areas that had high levels. And we are
going to dig in on that to find out just how much of
a problem it is.
Obviously, from a statistical standpoint, that
would throw things way out of whack. You are not
getting representative sampling. That is one big
difference, in the years where you have a higher
proportion of that, you are apt to have a higher
proportion of violative samples.
In our comprehensive fish survey program,
which we carried out in 1973 and half of 1974, we
included saltwater and freshwater fish. So again,
you are probably going to have pretty low fre-
quency of high findings, because we did pick up a
lot of saltwater fish there. In our regular pesticide
surveillance program, that is carried out more within
the confines of the United States, although there are
some coastal water fish that might be picked up, so
that would sort of be in between these two activi-
ties. Where you try to combine all these together, it
is just impossible to decide, at least with the data
that we have, whether there have any changes.
DR. JAMES R. SANBORN (Illinois Natural History
Survey, Urbana, Illinois): Our national monitoring
program does look at three types of fishes, the
predator, and one intervening. Locating the fish in
each sampling does create a problem. So we get a
cross section of the fish's species. We do notice that
many species have a much higher fat content than
others. And even if there is a variation within those
species as to their body conditions, you would find
a correct relationship in the amount of fat and the
age of the fish. Consequently, when we look at
those fish—lake trout can exist in those environ-
ments within a period of time and gather a rather
substantial amount of adipose tissue. The goldfish,
for example, is a very fat fish. You will find it
loaded with RGB's and pesticides.
MR. DONALD TESLACK (EPA): I'd like to find out if
there is any data—how does 99 percent average?
DR. JELINEK: I don't believe I have that figure here,
and I would hate to speak from memory, sir. If you
want to, you know, you can leave me your name
and I can see—
DR. IAN C. NISBET (Massachusetts Audubon Society,
Lincoln, Massachusetts): Speaking from memory, I
believe it would be 95 percent.
DR. ROBERT GOLDEN (Environmental Protection
Agency, Washington, D.C.): I understand that fish-
meal is used to feed poultry extensively. Is there
any information available possibly on secondary
exposure to humans?
DR. JELINEK: Well, these levels that we are finding
now in poultry, or rather USDA is the one who
monitors poultry, are exceedingly low. In the one
slide there, the 1 percent of poultry that the find-
ings were on were down around 1 ppm or something
like that.
Also, I would say this; our tolerance for PCB's
in finished animal feed is two-tenths of a ppm,
which is just above the limits of our analytical
methods for accurate reproducible quantitative
results of animal feed. So we set the tolerance there
at almost what you would call the analytical
nondetectable method for enforcement purposes.
257
-------
20 November 1975
Session IV:
ECOLOGICAL EFFECTS AND EXPOSURE
Donald I. Mount, Ph.D.*
Session Chairman
'Director, Environmental Research Laboratory, Environmental Protection Agency, Duluth, Minnesota.
259
-------
INTRODUCTORY REMARKS
Donald I. Mount, Ph.D.
Not being a back-of-the envelope modeler like Dr.
Nisbet, I am not going to try to play the role that he did.
But I do think there are two or three very quick com-
ments that might help in moving into our discussion.
First of all, it is worth pointing out that there are
three primary reasons to be concerned about the impact
of pollutants on aquatic organisms. First and most ob-
vious are the effects of pollutants on the organisms
themselves. Perhaps less obvious is the warning that
when residues accumulate in aquatic organisms, poten-
tial hazards to human health may exist.
We have heard about the impact of residues in
human food on humans. I think it is worth emphasizing
that essentially 100 percent of the organism's diet has
residues unlike those in humans. Therefore, the signifi-
cance of a given concentration of PCB's in the food of
an animal such as the mink may be quite different than
it is to a human.
I had talked with Dr. Nisbet before the conference
and we agreed in the upcoming session to discuss resi-
dues only where they relate to effects on the organisms
carrying them.
I have noted as I have sat in the audience that it has
been very difficult to tell whether the speaker is saying
parts per billion or parts per million. So I have asked our
speakers if they can refer to micrograms per liter and
milligrams per liter. For those who cannot make the
conversion, that is parts per billion and parts per million,
respectively. So, if a speaker says milligrams per liter,
that is parts per million.
I would like now to start with our papers and we
would like to reverse the position of the first two papers,
because the first one is to deal with the information that
was available up to 1972 regarding the effects of PCB's
in nonhuman organisms. We are referring, of course, to
those organisms in the environment more so than domes-
tic animals. If you wonder why 1972 was picked, it
correlates roughly with the report of the PCB task force.
261
-------
SUMMARY OF RECENT INFORMATION REGARDING
EFFECTS OF PCB's ON BIRDS AND MAMMALS
Rey C. Stendell*
Abstract
The significance of PCB 's to wild animals depends
both upon their lethal toxicity and their sublethal phys-
iological effects. The lethal dietary toxic/ties of most
Aroclors to experimental birds generally are less than
those of DDE, DDT, or dieldrin. Effects of PCB's on
reproduction are apt to have the most serious impact on
populations. These effects are difficult to evaluate. The
chief reproductive effects in chickens are reduced egg
production and hatchability. Deformities in chicks are
common, and growth rates of young sometimes are de-
pressed. Administration of low dietary levels of PCB's to
chickens, bob white quail, ringdoves, and mallards have
not resulted in thinning of eggshells. No tests of shell
thinning have been made with birds of prey or other
critical species. Residues of PCB's in wild birds often are
at levels known to have caused reproductive impairment
in chickens. Species differences must be considered,
however, and the significance of these levels to wild
birds is very uncertain.
PCB's have been implicated in the reproductive
failure and mortality of mink from the Great Lakes re-
gion. High levels of PCB's and organochlorine pesticides
have been found in marine mammals and have been link-
ed with premature births in some species. Recent studies
have shown that some species of bats may be sensitive to
a low level of PCB contamination.
INTRODUCTION
The widespread distribution of PCB's in the environ-
ment and their effects upon populations of wild birds
and mammals are matters of growing concern. Their
presence has stimulated research to evaluate their role in
the biosphere. This paper reviews recent literature
(1972-1975) on the effects of PCB's upon birds and
mammals.
EFFECTS ON BIRDS
Lethal Toxicity
Outright mortality can affect populations. Measure-
ment of direct toxicity is an important first step in the
evaluation of a chemical. Toxicities of different PCB's to
young pheasants (Phasianus colchicus), mallards (Anas
*Patuxent Wildlife Research Center, U.S. Fish and Wildlife
Service, Laurel, Maryland.
platyrhynchos), bobwhite quail (Colinus virginianus),
and coturnix quail (Coturnix coturnix} have been com-
pared with the toxicities of DDT, dieldrin, and other
insecticides (ref. 1). LC50's for the PCB's were high.
Tests of six PCB mixtures, containing 32 to 62 percent
chlorine, showed that the toxicity increased with the
percentage of chlorine. The dietary toxicities of the
Aroclors were, with few exceptions, less than those of
the four organochlorine pesticides used for comparison.
Special tests with coturnix quail showed that the toxic
effects of DDE and Aroclor 1254 were additive but not
synergistic. In other studies, Aroclor 1254 was approxi-
mately as toxic as DDE to four species of blackbirds
(ref. 2). Redwinged blackbirds (Agelaius phoeniceus)
were somewhat more susceptible to DDE than to PCB's.
Regular oral doses from 10 to 210 mg Aroclor 1254
produced some mortality among subadult pheasants (ref.
3). The amount and timing of the mortality were related
to the dose. Heavier birds lived longer and lost the great-
est percentage of their body weight before death.
Residues of PCB's in brains of blackbirds given
heavy doses of Aroclor 1254 were diagnostic of death
(ref. 4); residues in brains of birds that died varied from
349 to 763 ppm (wet weight) and were not above 301
ppm in survivors. In studies with pheasants given daily
doses of 210 mg of Aroclor 1254, a brain residue level of
300 to 400 ppm generally indicated death due to PCB
toxicosis (ref. 3). Residues of PCB's in livers and other
tissues were more variable and of lesser value for diagn-
osing death.
PCB residues in brains of bald eagles (Haliaeetus
leucocephalus) found dead from various causes in the
United States between 1969 and 1972 varied from 0.10
to 230 ppm (refs. 5,6). Even the highest levels in the
eagle brains were below the lethal range determined with
captive blackbirds. However, there may be at least two
distinct modes of death from PCB's (ref. 7). A sudden
heavy intake may cause death from neurotoxicity, with
brain residues high and diagnostic of death. Long, low
intake, which may occur in the field, may kill by causing
edema and related phenomena; signs vary between in-
dividuals and between species. Under these circum-
stances, mortality resulting from PCB's would not nec-
essarily be accompanied by high residues of PCB's in
brains, and for these birds no good diagnostic technique
is available, for the signs are nonspecific and the residue
levels vary greatly.
262
-------
RGB's were implicated in a dieoff of guiiemots (Uria
aalge) which occurred in the Irish Sea region in 1969
(ref. 8). The body load of RGB's in birds that died was
about twice that in healthy birds collected in the same
general region. Moreover, livers of shot birds contained
only 0.9 percent of the total body burden compared to
22.5 percent for birds found dead. PCS residues in
brains were not determined.
Uptake and Loss Rates
RGB's are readily taken up by animal tissues, and
loss rates are reasonably slow. Like DDT and other
lipid-soluble pesticides, RGB's accumulate in adipose
tissue and have been shown to move out of adipose
tissue during lipid mobilization. In experimentally dosed
birds, highest PCB levels accumulated in adipose tissue,
followed by kidney, liver, brain, muscle, and blood (refs.
3,9).
In experimentally dosed grackles (Quiscalus
quiscula], half of the RGB's were gone from the tissues in
about 1 month, compared to an estimated 6 months for
DDE (ref. 4). Continued loss of RGB's after the first
month, however, was exceedingly slow and there was no
significant further loss occurring during the next 12
weeks. After 32 weeks, about 15 percent of the original
burden of RGB's remained in the body.
RGB's are readily excreted in the egg. PCB levels in
the eggs of double-crested cormorants (Phalacrocorax
auritus] reflected carcass levels, but this relationship did
not hold for white pelicans (Pelacanus erythrorhynchos)
(ref. 10). In ringdoves (Streptopelia risoria), Aroclor
1254 fed at 10 ppm reached an equilibrium level of 17
ppm wet weight in the eggs; this was about 2 percent of
the level found in the fat of the adult birds (ref. 9).
RGB's stored in the adipose tissue are readily mobil-
ized during periods of stress that cause loss of body
weight. Alternate starving and feeding of pheasants dos-
ed with RGB's increased the toxicity of the RGB's (ref.
11). Birds that died from starvation had mobilized their
fat reserves and had considerably higher RGB's in the
brain and other tissues than did RGB-treated birds that
were not starved. Similarly, increased levels of PCB in
muscle, brain, and liver of PCB-treated ringdoves follow-
ed depletion of fat reserves by starvation. At death, PCB
concentration in the brains of starved birds had increas-
ed 56-fold (ref. 9).
Reproductive Effects
Effects of PCB's on reproduction are difficult to
evaluate but are apt to have the most serious impact on
populations. Few data are available for wild species, so
work done with chickens must be relied upon. Numer-
ous good studies have shown that chickens are sensitive
to PCB's. The chief reproductive effects in chickens are
lowered egg production and reduced hatchability. De-
formities in chicks are common, and growth of young
may be depressed. Survival of young sometimes is affect-
ed. Feed consumption, adult survival and body weight,
eggshell characteristics, and gametogenesis usually are
not affected. Most embryo mortality occurs during the
latter stages of incubation, although this may depend
upon the PCB residue in the egg. Many chicks may die
after pipping. The most severe effects are produced by
Aroclors in the middle of the range—from 1232 through
1254.
Chickens fed 2 ppm of several Aroclors in the diet
for 9 weeks were not adversely affected (ref. 12). Others
fed 20 ppm were affected differently by the different
types of Aroclors. Aroclors 1221 and 1268 did not
affect egg production or hatchability. Aroclor 1248 pro-
duced the most severe effects, causing some mortality of
adults and nearly eliminating hatching of eggs. Aroclor
1242 produced effects that were very nearly as severe.
Aroclor 1232 produced less effect.
The lack of effects of 2 ppm of dietary PCB on
chicken reproduction was supported by a 39-week feed-
ing test with Aroclor 1254 (ref. 13). Five ppm of 1254
reduced egg production erratically over the 39-week
period. With 50 ppm, however, mortality began, and
dosage was stopped after 14 weeks. Egg production fell
sharply. Hatchability dropped nearly to zero; residues in
eggs were then about 25 to 50 ppm. As residues in eggs
dropped after 6 weeks of clean food, hatchability rose.
Residues ever 10 to 15 ppm in eggs were accompanied
by heavy ernbryotoxicity, but those below 5 ppm show-
ed no effect. At the start of the 50-ppm dosage, deaths
of embryos came late in development, but as residues
built up deaths came progressively earlier.
The effects on reproduction were fmther investi-
gated in another study in which chickens were given 50
ppm Arocior 1254 in water for 6 weeks, and then were
given untreated water for 20 weeks (ref. 14). Hatchabi-
lity dropped to zero within 3 weeks after dosage began
and stayed nearly at zero through 8 weeks of clean
water, then rose to approximately normal levels after 16
weeks of untreated water. The amount of embryonic
mortality associated with a given amount of PCB residue
in the egg became higher as the study progressed. Thus,
50 percent mortality of embryos was correlated with 50
ppm of PCB in the yoik after 1.6 weeks of dosage, but
with 10 ppm aiter 18.7 weeks, a fivefold difference. The
263
-------
greatest toxicity per unit of PCB came after 11 weeks of
untreated water. Late in the study, 6 to 8 ppm of PCB in
yolks was correlated with 14 to 36 percent mortality of
embryos This would represent about 3.6 ppm in the
whole egg. The authors concluded that the increase of
toxicity with time was caused by the accumulation of
some persistent isomer or homolog of 1254 or by a met-
abolite.
In another study with chickens, egg production was
reduced by 10 percent and hatchability by 44 percent
when eggs from hens dosed with Aroclor 1248 contained
only 3 ppm (ref. 15). When levels in the eggs reached 4.5
ppm, production was further reduced and hatchability
was almost completely eliminated.
PCB residues in eggs of wild birds have often
equalled or exceeded the levels known to have caused
reproductive problems in chickens. For a few examples,
11 eggs of bald eagles from the United States contained
from 2-2 to 27.7 ppm of PCB's with a median of 9.7
ppm (ref. 16). PCB residues in osprey (Pandion
haliaetus) eggs collected in Connecticut in 1968 and
1969 varied from 3.6 to 51 ppm (ref. 17) and brown
pelican (Pelecanus occidenta/is) eggs from the Eastern
United States contained from 1,9 to 36.5 ppm PCB's,
with many readings over 5 ppm (ref. 18). Species differ-
ences in response must be considered in the interpreta-
tion of the effects of these levels upon reproduction of
wild birds. The number of species that may respond like
chickens is not known.
PCB's caused deformities in chicks from hens dosed
with 50 ppm Aroclor 1254 (ref. 19). Many deformities
appeared when residues in yolks were 10 ppm or more.
In another study in which hens were dosed with 20 ppm
of Aroclors 1232, 1242, 1248, or 1254, 34 percent of
843 embryos that died during incubation showed signs
of abnormal development (ref. 20). PCB's or related
chemicals were suspected of causing deformities in a
small number of young in a tern colony in which PCB
residues were high (ref. 21).
Other species of birds may be less sensitive to PCB's
than chickens. Mallards showed no decline in reproduc-
tive success during 2 years of dosage with 25 ppm of
Aroclor 1254 (ref. 1). Similar results have been reported
for coturnix quail (refs. 15,22) and bobwhite quail (ref.
1). Pheasants given oral doses of Aroclor 1254 showed
depressed egg production and hatchability, suggesting a
response similar to that of chickens (ref. 23).
Decreases in eggshell thickness and associated de-
clines in populations of certain species of wild birds have
been linked with elevated levels of DDE in their eggs (for
review see ref. 24). The effect of DDE upon eggshell
thickness has been demonstrated experimentally with
several species (ref. 24). Recent experimental studies
with PCB's, however, have failed to demonstrate that
low dietary dosages cause significant eggshell thinning in
mallards (ref. 1), bobwhile quail (ref. 1), pheasants (ref.
23), ringdoves (ref. 25), or chickens (refs. 12,15,26,27).
In earlier tests, chickens led Aroclor 1242 at 10 ppm or
100 ppm and Aroclor 1254 at 100 ppm laid eggs with
thinner shells than did controls (ref. 28). Coturnix qu- I
hens given 10 ppm Aroclor 1242 in the feed for 40 days
produced eggs with shells 5 percent thinner than did
hens given untreated feed (ref. 29). Similarly, 50 ppm of
Aroclor 1254 in ihe diet produced a small decrease in
shell thickness and an increase in the percentage of
cracked eggs of coturnix quail (ref. 22). No tests of egg-
shell thinning have been made with birds of prey or
other critical species.
Statistical evaluation of the role that different che-
micals may play in thinning the eggshells of brown pel-
icans in the field has shown that DDE residues correlate
much better with shell thinning than do residues of
PCB's (ref. 18). Similar relationships have been shown
for other species (ref. 30).
Effect on Chromosomes
Few cytogenetic studies have been conducted to de-
termine effects of PCB's on chromosome structure. In
one study, no chromosomal aberrations were detected in
chicken embryos following injection of Aroclor 1242
into the egg to levels of 10 and 20 ppm (ref. 31). At
these levels mortality of embryos was high. In another
study, embryos from ringdoves treated with Aroclor
1254 at 10 ppm had a higher frequency of chromosome
aberrations than did controls (ref. 32).
Chromosomal aberrations may contribute to the ab-
normalities of developing embryos observed in some
studies, or perhaps to a decreased reproductive success
during successive generations of exposure to PCB's.
When ringdoves were exposed to 10 ppm Aroclor 1254
during two generations, the reproductive success of the
first generation was normal, but the success of the
second generation was greatly reduced (ref. 32).
Effects on Behavior
Alterations in behavior may bring about depressed
survival and reproductive success of wild species. Exper-
imental studies have shown that PCB's may alter be-
havior. Caged European robins (Erithacus rubecula) fed
PCB's showed increased migratory activity compared
with untreated controls (ref. 33). PCB's caused a similar
tendency in redstarts (Phoenicurus phoenicurus) (ref.
264
-------
34). Behavior, on a visual cliff, of pheasant chicks hatch-
ed from hens given 50 mg Aroclor 1254 weekly was
significantly different from controls or those receiving
12.5 mg (ref. 23); more chicks from the 50-mg group
jumped to the visually deep side or made no choice of
sides than chicks from other groups. The avoidance re-
sponse to a moving silhouette of coturnix quail chicks
fed 200 ppm of Aroclor 1254 was greatly reduced (ref.
35); there was no significant recovery in response after
the birds were again given clean feed, suggesting an
effect upon the maturing central nervous system.
Embryonic mortality of ringdoves fed 10 ppm
Aroclor 1254 was higher when the eggs were incubated
by the parent birds than when they were incubated arti-
ficially (ref. 36). Egg temperatures suggested that the
increased mortality was due to decreased parental atten-
tiveness.
Recent studies have shown that certain species of
bats are sensitive to RGB's. In big-brown bats (Eptesicus
fuscus), RGB's crossed the placenta 2 to 3 times more
readily than DDE (ref, 41). Concentrations of PCB's
were significantly greater in litters that included dead
young than in litters in which both young were born
alive. In further studies, big-brown bats fed 250 ppm
DDE in the diet gained weight and none died, but indi-
viduals fed only 10 ppm Aroclor 1254 gained weight
more slowly and some died (ref. 42).
PCB's have been shown to be toxic to some non-
human primates over a wide dose range. Adult rhesus
monkeys developed signs of PCB intoxication within 1
to 2 months at doses as low as 2.5 and 5.0 ppm of
Aroclor 1248 in the diet (ref. 43); these levels also
caused a marked decline in reproductive success.
EFFECTS ON MAMMALS
CONCLUSIONS
Certain species of mammals appear to be especially
sensitive to ingestion of low levels of PCB's. An extreme
example was provided by the declining reproductive
success and increasing mortality of mink that was ob-
served by commercial mink ranchers in the Great Lakes
region in the 1960's. The problems developed when
mink ranchers began to use coho salmon from the Great
Lakes in mink rations (ref. 37). Other fish from Lake
Michigan had similar effects, but coho from the Pacific
coast caused no trouble. Feeding trials were conducted
with several contaminants that had been identified in the
fish (ref. 38). Neither DDT nor dieldrin caused these
effects in mink, even at levels far higher than those in
the fish. In the first test, a mixture of PCB's at 30 ppm
in the diet killed all the adult mink. With dietary dosages
of 5 and 10 ppm of Aroclor 1254, no reproduction
occurred. At 10 ppm, five of the six adults died. In
further tests, 1 ppm of PCB in the diet reduced repro-
ductive success. More drastic results were observed when
the mink were fed meat from cows that had been dosed
with Aroclor 1254 (ref. 39). When the concentration of
PCB in the diet was 3.57 ppm, there was no reproduc-
tion and all breeders died. When the concentration was
0.64 ppm, some adults died and no surviving young were
produced.
High levels of PCB's and organochlorine insecticides
have been found in marine mammals and a link with
premature births in some species has been suggested. Pre-
mature pups from California sea lions (Zalophus
californicus) contained higher levels of these compounds
in the blubber, liver, and brain than did full-term pups
(ref. 40).
The effects of PCB's upon wild populations are dif-
ficult to evaluate and many important questions remain
to be answered. "Residues in wild species may be derived
from different commercial mixtures that have undergone
metabolic changes for varying time periods before reach-
ing the target organism. Residues of PCB's in wild birds
often are at levels known to have caused reproductive
impairment in chickens. Nevertheless, species differences
must be considered and it is not known how many spe-
cies respond in the same manner as chickens. The great
sensitivity of mink raises the question of how many
other mammals may be equally sensitive to reproductive
impairment or mortality.
REFERENCES
1. R. G. Heath, J. W. Lpann, J. F. Kreitzer, and C.
Vance, "Effects of Polychlorinated Biphenyls on
Birds," Proc. XVth Int. Ornith. Congr., 1972, pp.
475-485.
2. E. H. Dustman, L. F. Stickel, L. J. Blus, W. L.
Reichel, and S. N. Wiemeyer, "The Occurrence and
Significance of Polychlorinated Biphenyls in the En-
vironment," Trans. 36th N. Am. Wildl. Nat. Res.
Conf.. 1971, pp. 118-131.
3. R. B. Dahlgren, R. J. Bury, R. L. Linder, and R, F.
Reidinger, Jr., "Residue Levels and Histopathology
in Pheasants Given Polychlorinated Biphenyls," J.
Wildl. Manage., Vol. 36 (1972), pp. 524-533.
4. W. H. Stickel, unpublished report, Patuxent Wildlife
Research Center.
265
-------
5. A. A. Belisle, W. L. Reichel, L. IM. Locke, T. G.
Lament, B. M. Mulhern, R, M. Prouty, R. B.
DeWolf, and E. Cromartie, ''Residues of Organo-
chlorine Pesticides, Polychlorinated Biphenyls, and
Mercury and Autopsy Data for Bald Eagles, 1969
and 1970," Pestic. Monit. J., Vol. 6 (1972), pp.
133-138.
6. E. Cromartie, W. L. Reichel, L. N. Locke, A. A.
Belisle, T. E. Kaiser, T. G. Lament, B. M. Mulhern,
R. N. Prouty, and D. M. Swineford, "Residues of
Organochlorine Pesticides and Polychlorinated Bi-
phenyls and Autopsy Data for Bald Eagles,
1971-72," Pestic. Monit. J., Vol. 9 (1975), pp.
11-14.
7. W. H. Stickel, "Some Effects of Pollutants in Terres-
trial Ecosystems," Proc. NATO Conf. Pollution by
Heavy Metals and Organohalogens, in press.
8. J. L. F. Parslow and D. J. Jefferies, "Relationship
Between Organochlorine Residues in Livers and
Whole Bodies of Guillemots," Environ. Pollut, Vol.
5(1973), pp. 87-101.
9. J. L. Lincer and D. B. Peakall, "PCB Pharmaco-
dynamics in the Ring Dove and Early Gas Chroma-
tographic Peak Diminution," Environ. Pollut, Vol.
4 (1973), pp. 59-68.
10. Y. A. Greichus, A. Greichus, and R. J. Emerick,
"Insecticides, Polychlorinated Biphenyls and Mer-
cury in Wild Cormorants, Pelicans, Their Eggs, Food
and Environment," Bull. Environ. Contam. Toxi-
co/., Vol. 9 (1973), pp. 321-328.
11- R. B. Dahlgren, R. L. Linder, and W. L. Tucker,
"Effects of Stress on Pheasants Previously Given
Polychlorinated Biphenyls," J. Wildl. Manage., Vol.
36 (1972), pp. 974-978.
12. R. J. Lillie, H. C. Cecil, J. Bitman, and G. F. Fries,
"Differences in Response of Caged White Leghorn
Layers to Various Polychlorinated Biphenyls (PCBs)
in the Diet," Poultry Sc''., Vol. 53 (1974), pp.
726-732.
13. N. S. Piatonow and B. S. Reinhart, "The Effects of
Polychlorinated Biphenyls (Aroclor 1254) on Chick-
en Egg Prodis t.on. Fertility, and Hatchability,"
Can. J. Comp. Med., Vol. 37 (1973), pp. 341-346.
14. B. Bush, C. F. Tumasonis, and F. D. Baker, "Tox-
icity and Persistence of PCB Homologs and Isomers
in the Avian System," Arch. Environ. Contam. Tox-
Icol., Vol. 2 (1974), pp. 195-212.
15. M. L. Scott, J. R. Zimmerman, S. Marinsky, P. A.
Mullenhoff, G. L. Rumsey, and R. W. Rice, "Effects
of PCBs, DDT, and Merciny Compounds Upon Egg
Production, Hatchabiiity and Shell Quality in Chick-
ens and Japanese Quail," pou'try Sc/., Vol. 54
(1975), pp. 350-368.
16. S. N. Wiemeyer, B. M. Mulhern, F. J. Ligas, R. J.
Hensel, J. E. Mathisen, F. C. Robards, and S.
Postupalsky, "Residues of Organochlorine Pesti-
cides, Polychlorinated Biphenyls, and Mercury in
Bald Eagle Eggs and Changes in Shell Thickness —
1969 and 1970," Pestic. Monit. J., Vol. 6 (1972),
pp. 50-55.
17. S. N. Wiemeyer, P. R. Spitzer, W. C. Krantz, T. G.
Lamont, and E. Cromartie, "Effects of Environmen-
tal Pollutants or; Connecticut and Maryland
Ospreys," J. Wildl. Manage., Vol. 39 (1975), pp.
124-139.
18. L. J. Blus, B. S. Noely, Jr., A. A. Belisle, and R. M.
Prouty, "Organochlorine Residues in Brown Pelican
Eggs: Relation to Reproductive Success," Environ.
Pollut., Vol. 7 (1974), pp. 81-91.
19. C. F. Tumasonis, B. Bush, and F. D. Baker, "PCB
Levels in Egg Yolks Associated with Embryonic
Mortality and Deformity of Hatched Chicks," Arch.
Environ. Contam. Toxicol., Vol. I (1973), pp.
312-324.
20. H. C. Cecil, J. Bitman, R. J. Lillie, G. F. Fries, and
J. Verrett, "Embryotoxic and Teratogenic Effects in
Unhatched Fertile Eggs From Hens Fed Polychlori-
nated Biphenyls (PCBs)," Bull. Environ. Contam.
Toxicol., Vol. 11 (1974), pp. 489-495.
21. H. Hays and R. W. Risebrough, "Pollutant Concen-
trations in Abnormal Young Terns From Long
Island Sound, Auk, Vol. 89 (1972), pp. 19-35.
22. E„ S. Chang and E. L. R. Stokstad, "Effect of Chlor-
inated Hydrocarbons on Shell Gland Carbonic An-
hydrase and Egg Shell Thickness in Japanese Quail,"
Poultry Sci., Vol. 54 (1975), pp. 3-10.
23. R. B. Dahlgren and R. L. Linder, "Effects of Poly-
chlorinated Biphenyls on Pheasant Reproduction,
Behavior, and Survival," J. Wildl. Manage., Vol. 35
(1971), pp. 315-319.
24. L. F, Stickel, "Pesticide Residues in Birds and
Mammals," Environmental Pollution by Pesticides,
C. A. Edwards, ed.. Plenum Press, New York, 1973,
pp. 254-312.
25. D. B. Peakall, "Effect of Polychlorinated Biphenyls
(PCBs) on the Eggshells of Ring Doves," Bull. Envi-
ron. Contam. Toxicol., Vol. 6 (1971), pp. 100-101.
26. W. M. Britton and T. M. Huston, "Influence of Poly-
chlorinated Biphenyls in the Laying Hen," Poultry
Sci., Vol. 52 (1973), pp. 1620-1624.
27. R. H. Teske, B. H. Armbrecht, R. J. Condon, and H.
J. Paulin, "Residues of Polychlorinated Biphenyls
from Poultry Fed Aroclor 1254," J. Agric. Food
Chem., Vol. 22 (1974), pp. 900-904.
266
-------
28. Monsanto Company, unpublished report prepared
by Industrial Biotest Laboratories, Inc., North-
brook, Illinois, 1970.
29. E. F. Hill, R. G. Heath, and J. D. Williams, "Effect
of Dieldrin and Aroclor 1242 on Japanese Quail
Eggshell Thickness," unpublished manuscript,
Patuxent Wildlife Research Center.
30. R. A. Faber and J. J. Hickey, "Eggshell Thinning,
Chlorinated Hydrocarbons, and Mercury in Inland
Aquatic Bird Eggs, 1969 and 1970," Pestic. Monit.
J..Vo\. 7 (1973), pp. 27-36.
31. W, F. Blazak and J. B. Marcum, "Attempts to In-
duce Chromosomal Breakage in Chicken Embryos
with Aroclor 1242," Poultry Sci., Vol. 54 (1975),
pp. 310-312.
32. D, B. Peakall, J. L. Lincer, and S. E. Bloom, "Em-
bryonic Mortality and Chromosomal Alterations
Caused by Aroclor 1254 in Ring Doves," Environ.
Health Persp., Vol. I (1972), pp. 103-104.
33. S. Ulfstrand, A. Sodergren, and J. Rabol, "Effect of
PCB on Nocturnal Activity in Caged Robins,
Erithacus rubecula L., Nature, Vol. 231 (1971), pp.
467-468.
34. B. Karlsson, B. Persson, A. Sodergren, and S. Ulfst-
rand, "Locomotory and Dehydrogenase Activities
of Redstarts Phoenicurus phoenicurus L. (Aves)
Given PCB and DDT," Environ. Pollut, Vol. 7
(1974), pp. 53-63.
35. J. F. Kreitzer and G. H. Heinz, "The Effect of Sub-
lethal Dosages of Five Pesticides and a Polychlori-
nated Biphenyl on the Avoidance Response of
Coturnix Quail Chicks," Environ. Pollut., Vol. 6
(1974), pp. 21-29.
36. D. B. Peakall and M. L. Peakall, " Effect of a Poly-
chlorinated Biphenyl on the Reproduction of Arti-
ficially and Naturally Incubated Dove Eggs," J.
Appl. Ecol., Vol. 10 (1973), pp. 863-868.
37. R. J. Aulerich, R. K. Ringer, H. L. Seagran, and W.
G. Youatt, "Effects of Feeding Coho Salmon and
Other Great Lakes Fish on Mink Reproduction,"
Can. J. Zoo/., Vol. 49 (1971), pp. 611-616.
38. R. J. Aulerich, R. K. Ringer, and S. Iwamoto, "-
Reproductive Failure and Mortality in Mink Fed on
Great Lakes Fish," J. Reprod. Pert. Suppl., Vol. 19
(1973), pp. 365-376.
39. N. S. Platonow and L. H. Karstad, "Dietary Effects
of Polychlorinated Biphenyls on Mink," Can. J.
Ccmp. Med., Vol. 37 (1973), pp. 391-400.
40. R. L. DeLong, W. G. Gilmartin, and J. G. Simpson,
"Premature Births in California Sea Lions: Associa-
tion With High Organochlorine Pollutant Residue
Levels," Science, Vol. 181 (1973), pp. 1168-1169.
41. D. R. Clark, Jr., and T. G. Lament, " Organochlo-
rine Residues and Reproduction in the Big-Brown
Bat,"./, Wild/. Mange., in press.
42. D. R. Clark, Jr., unpublished data, Patuxent Wildlife
Research Center.
43. J. R. Allen, "Response of the Nonhuman Primate to
Polychlorinated Biphenyls Exposure," Fed. Proc.,
Vol. 34 (1975), pp. 1675-1679.
267
-------
PRE-1972 KNOWLEDGE OF NONHUMAN EFFECTS
OF POLYCHLORINATED BIPHENYLS
Charles R. Walker*
Abstract
Research conducted worldwide on the effects of
PCB on aquatic organisms, birds, and mammals is herein
summarized. The ecological effects of PCB are still not
fully understood, nor is the long-term impact of PCB on
animal populations. It is known that PCB are highly per-
sistent contaminants that bioaccumu/ate in the food
chain. They produce both chronic and acute effects on
the growth, reproduction, and behavior of fish, birds,
and mammals. Of these, freshwater fish accumulate PCB
to the greatest extent. The birds and mammals that feed
on freshwater fish in turn take in hazardous amounts of
PCB residues and become subject to their serious toxi-
colo ••»/ effects.
INTRODUCTION
)!ychlorinated biphenyls were under investigative
devtiopment as early as 1881 (Schmidt and Schultz) and
yet very little knowledge of their toxic effects was evi-
den! until they had gained wide use during the 1930's
and pdthoiogical studies on laboratory animals were con-
duct, d (refs. 5,41). These polychlorinated biphenyls,
napthlenes, terpenes, etc., were marketed under a variety
of trade names—Aroclor, Chlorphen, Kanechlor, Pheno-
chlcr and a series of numerical synonyms such as we
have become familiar with in Aroclors—1221, 1232,
1242, 1248, 1254, 1260, 1268, etc. (refs. 8, 33, 51).
Almost 20 years lapsed until McLaughlin et al. re-
ported that Aroclor 1242 was highly toxic and produced
teratogenic effects in chick embryo at low dosage levels
(ref. 44). Many studies were initiated at about this time,
when analytical chemists monitoring environmental
components observed a number of unidentified peaks in
gas chromatographic analysis that were most frequently
associated with aquatic species of birds and fishes (refs.
3, 19, 20, 21, 22, 24, 25, 26, 27, 32, 33, 34, 45, 46, 48,
53, 54, 55, 56, 58, 59, 61, 64, 66, 67, 68, 83, 84, 85,
86, 88, 93, 94). The annual research reports by the U.S.
Fish and Wildlife Service since 1969 gave technical de-
tails in the developments of our work on the toxicity of
PCB and chlorinated hydrocarbon pesticides, which
"Senior Environmental Scientist, U.S. Fish and Wildlife
Service, U.S. Department of Interior, Washington, D.C. 20240
NOTE: Scientific names for !ssh and wildlife listed in text
are given at the end of the paper.
coincided with monitoring investigations of persistent
chemicals such as DDT (refs. 3, 12, 16, 17, 38, 39, 40,
47, 52, 57, 71, 77, 78, 79, 80, 81, 82, 89, 90, 91, 92).
The development of the silicic acid method allowed for
the separation of PCB from other pesticide components
and permitted detailed investigation of these environ-
mental contaminants (refs. 1,71).
The December 1971 conference on polychlorinated
biphenyls sponsored by the National Institute of Envi-
ronmental Sciences at the Quail Roost Conference in
Rougemont, North Carolina, provided full array of the
effect of PCB on experimental animals, fish, and wild-
life. The Fish and Wildlife Service National Pesticide
Monitoring Program discussed at this conference concen-
trations of PCB in fish samples (ref. 89). These residue
levels were confirmed in the cross-check analysis by the
Fish Pesticide Research Laboratory, which in turn has
spurred more toxicological research into the significance
of these residues (refs. 18, 40, 71, 74, 75, 76, 80).
EFFECTS ON AQUATIC ORGANISMS
Chronic and acute toxicity studies on aquatic orga-
nisms were conducted in which 96-hour LC values
were determined for eight of the Aroclor series from
1221 through 1268 (refs. 40,71). The 96-hour LC
values ranged from 1,170 to 50,000 mg/l for cutthroat
trout (table 1) (refs. 40,71). In another test, the acute
oral toxicities of Aroclors 1242, 1248, 1254, and 1260
were found to be greater than 1500 mg/kg in rainbow
trout. Intermittent flow for Aroclors 1242, 1248, and
1254 indicated that these compounds were much more
toxic at high temperatures and at longer exposure
periods. Comparable results were obtained on channel
catfish and rainbow trout (table 1) (refs. 40,71).
The effect of Aroclors on invertebrate forms gave an
even wider distribution of effects (table 2) (refs.
40,69,71), with Aroclor 1248 being the most toxic to
Daphnia magna and levels above 5 mg/l causing inhibi-
tion in reproduction (ref. 45). Similar results were ob-
tained on Gammarus pseudolimnaeus (ref. 45). The
96-hour LCSO values for Aroclors 1248 and 1254 were
52 and 2400 mg/l respectively (ref. 40). Another species
of scud (Gammarus fasciatus) was found to concentrate
PCB by 27,000 times the exposure level compared to the
Daphnia, which concentrated Aroclor 1254 by 48,000
times (figure 1) (ref. 40).
Both crayfish and the scud were found to be much
more sensitive to Aroclor 1242, with the uptake being
268
-------
Table 1. Toxicity of PCB to fish (refs. 40,71)
PCB
Aroclor 1242
Aroclor 1248
Aroclor 1254
2,4'-Dichloro-
biphenyl
4,4'-Dichloro-
biphenyl
2,3,4'-Trichloro-
biphenyl
2,4,5,2',5'-Penta-
chlorobiphenyl
2,4,6,2',4',6'-Hexa-
chlorobiphenyl
Invertebrate
(species)
Scud
(Gammarus faciatus)
Scud
(Ganmarus faciatus)
Crayfish
(Orconectes nais)
Damsel fly
(Ischnura verticalis)
Dragonfly
(Macromia sp. )
Scud
(Gammarus faciatus)
Scud
(Gammarus faciatus)
Glass shrimp
(Palaemonetes kadiakensis)
Crayfish
(Orconectes nais)
Damselfly
(Ischnura verticalis)
Dragonfly
(Macromia sp. )
Scud
(Gammarus psuedolimnaeus)
Scud
(Gammarus psuedolimnaeus )
Scud
(Gammarus psuedolimnaeus)
Scud
(Gammarus psuedolimnaeus)
Scud
(Gammarus psuedolimnaeus }
Bioassay
method!/
C
C
A
A
A
A
A
C
C
C
A
A
A
A
A
A
Exposure
time
4
10
7
4
7
4
4
7
7
4
7
4
4
4
4
4
LC50
Oug/g)
10.0
5.0
30.0
400.0
800.0
52.0
2400.0
3.0
80.0
200.0
100.0
120.0
100. U
70,0
210,0
150,0
\l A = Acute toxicity by static test procedure
C = Chronic toxicity by flow-through procedure
269
-------
Table 2. Toxicity of PCB to aquatic invertebrates (ref:>. 40,69,71)
PCB
(Aroclor)
Fish
Temp Bioassav
(°C) method!'
Ad
"3d"
lOd
value in jug/1 at exposure time of
~[5d~
20d
25d 30d
1221
1232
1242
1248
1254
1260
1262
1268
Cutthroat trout
Cutthroat trout
Cutthroat trout
Rainbow trout
Bluegill
Bluegill
Channel catfish
Channel catfish
Cutthroat trout
Rainbow trout
Bluegill
Bluegill
Bluegill
Channel catfish
Channel catfish
Channel catfish
Channel catfish
Cutthroat trout
Rainbow trout
Rainbow trout
Bluegill
Bluegill
Bluegill
Channel catfish
Channel catfish
Channel catfish
Cutthroat trout
Rainbow trout
Rainbow trout
Bluegill
Bluegill
Channel catfish
Channel catfish
Cutthroat trout
Cutthroat trout
8.9
8.9
8.9
17.0
20.0
17.0
20.0
17.0
8.9
17.0
18.3
20.0
17
18.3
27.0
20.0
17.0
8.9
20.0
17.0
18.3
20.0
17.0
18.3
20.0
17.0
8.9
20.0
17.0
20.0
17.0
20.0
17.0
8.9
8.9
A
C
C
C
C
C
A
C
A
C
C
A
C
C
C
A
C
C
A
C
C
A
C
C
A
C
C
C
C
C
C
A
A
1170
2500
4530
5750
278
6000
,'
42500
2740
12000
60900
67
154
54
307
136
156
156
48
72
174
38
160
115
94-
225
121
8
160
443
303
5
326
535
18
54
164
107
2L9
16
76
111
57
127
121
64
204
303
741
286
143
482
10
125
150
12
120
132
6.4
3.4
10
106
115
39
135
260
300
293
78
245
296
512
100
104
27
54
239
113
181
49
212
166
465
84
87
78
75
177
139
51
151
400
137
433
50000
50000
17 A« Acute toxiclty by static test procedure.
C= Chronic toxicity by flow-through procedure.
270
-------
7000*
60001
U
O
ae
5000"
at
O
o
2 3000
z
o
32000
O
o
n
1000
I 2
WEEK WEEKS
EXPOSURE TIME
3
WEEKS
Figure 1. Bioaccumulation of Aroclor 1254 for various aquatic inverte-
brates exposed to water concentrations: 1.1 jug/I for Daphnia
magna; 1.6 ;ug/l for Gammarus pseudolimnaeus; 1.2 jug/I for
Orconectes nais; 1.3 jug/I for Palaemontes kadiakensis; 2.8 ng/\
for Pteronarcys dorsata; 1.1 /jg/l for Corydalus cornutus;
1.5 /ig/l for Cu/ex tarsalis; 1.3 M9/I for Chaoborus punctipennis
(ref. 40).
271
-------
somewhat enhanced with time. Glass shrimp (Palae-
monetes kadiakensis) were also found to be quite sensi-
tive to Aroclor 1254, with an LC50 value of 3 mg/l in a
7-day exposure. On the other hand, dragon fly (Macrom-
ia species) and damsel fly (Ischnura verticalis) were a
great deal more resistant to Aroclors 1254 and 1242
(table 1 and figure 1).
Aroclor 1254 was found to be extremely toxic to
immature pink shrimp, of which more than 50 percent
died within 15 days of continuous exposure to 0.94 mg/l
(ref. 47). A similar concentration factor was noted for
Aroclor 1254 in two estuarine fish species (Lagondon
rhomboides and Leiostomus xanthurus). While between
14 and 45 days of exposure to 5 mg/l did product some
mortality, the 1 mg/l during the same exposure time
resulted in no mortality, but concentration of residues
did occur at rates similar to those for freshwater fish—
10,000 to 50,000 times the environmental levels (refs.
12,16).
In studies conducted in Sweden on salmon eggs,
PCB residues on a lipid basis ranging from 7.7 to 34 /ug/g
caused mortalities between 16 to 100 percent (ref. 26).
The regression analysis gave a coefficient of correlation
of 0.85, with a significance of P = .001. PCB residues in
these Atlantic salmon eggs on a wet weight basis were
from 0.4 to 1.9 jug/g. This indicates that the threshold
for egg mortality was about 0.5 /ig/g PCB. Such residues
would be comparable to whole fish residues of 2.5 to 5.0
jug/g or very close to those values found in many fish
sampled in our National Pesticide Monitoring Program
and in Sweden (refs. 6,89).
The oral toxicities of Aroclors 1242, 1248, 1254,
and 1260 were found to be in excess of 1500/ng/kg for
adult rainbow trout (ref. 40). However, trout fry from
eggs containing 2.7 /jg/g of Aroclor 1242 along with a
DDT residue of 0.09 /ug/g caused a 75 percent cumula-
tive mortality 30 days after hatching (ref. 18). In five
other groups of less contaminated eggs, 10 to 28 percent
mortality was noted 30 days after hatching. About 60 to
70 percent of the fry that survived were deformed and
teratology was evident. Generally speaking, the more
chlorinated 'PCB were not as acutely toxic as the less
chlorinated ones. For example, in cutthroat trout, Aro-
clors 1221, 1232, 1242, 1248, 1254, and 1260 had
LC values for 96-hour exposure of 1.2, 2.5, 5.4, 5.7,
42, and 61 mg/l respectively.
In tests with individual homologs, toxicity decreases
as the percentage of chlorine increases in amphipods
against 5 PCB formulations (ref. 40). The dichlorobi-
phenyls and trichlorobiphenyls dominate the Aroclor
1242, whereas the trichlorobiphenyls and tetrachlorobi-
phenyls dominate in Aroclor 1248 and the pentachloro-
biphenyls and hexachlorobiphenyls dominate in the Aro-
clor 1254. The most toxic PCB formulations appear to
be those that contain 4 to 5 chlorine atoms; these pre-
dominated in Aroclor 1248, which was found to be the
most toxic of all of the Aroclors tested on fish. A notica-
ble shift in residue components following exposure to
Aroclor 1254 was observed in experiments conducted on
amphipods (ref. 71). An apparent twofold increase in
concentration of less chlorinated isomers and homologs
occurred in the Irichlorobiphenyls and tetrachlorobi-
phenyls. The higher chlorinated pentachlorobiphenyls
and hexachlorobiphenyls were decreased by half in ex-
periments conducted on fish (ref. 40). Tests showed that
residue accumulation of PCB in invertebrates ranged
from 160 to 6,300 times that in water. In channel cat-
fish, after 77 days of exposure, the concentration of
Aroclors 1248 and 1254 accumulated in channel catfish
to 56,270 and 61,190 times, respectively, than in water
(figure 1). The more chlorinated components accumu-
lated more than the less chlorinated ones, and upon ter-
mination of the exposure, PCB elimination by fish was
more rapid for the less chlorinated components (refs.
40,71). The researchers also found evidence that the ac-
tual uptake is less or the turnover rate is more rapid in
the invertebrates. This is in agreement with observations
by other investigators (refs. 48, 64, 65, 66, 67).
In other experiment;, conducted by our Fish Pesti-
cide Research Laboratory, we found that inclusion of
Aroclor 1254 in fish food at the rate of 0.448 /ug/g
resulted in a 52 percent increase in fish thyroid activity.
In a high-treatment grouo that received 480 jug/g, thy-
roid stimulation was 119 percent over that of the con-
trol group (figure 2) (ref. 40). In these tests we found
that the lowest detectable stimulation thyroid activity
occurred in salmon dosed at 1/1,000th the dosage that
would cause mortality. This test was further duplicated
in channel catfish with comparable results, which sug-
gests that the laboratory studies may be realistic indica-
tors of the physiological effects of PCB on fish and the
aquatic environment (figure 3) (refs. 40,71). The true
effects of thyroid stimulation, however, on respiration,
carbohydrate metabolism, oxygen consumption, ammo-
nia metabolism, osmoregulation, growth, oxidative phos-
phorylation, central nervous system function, and behav-
ior of lish are yet to be determined. Nevertheless, we can
postulate that these must be important and interrelated
factors in the physiological and biochemical function of
fish and any alteration of this normal function could
effect fishes' ability to adapt to stress or such changes in
the environment as salinity and temperature. The effect
of environmental stress on the health of fish is very well
illustrated by Snieszko (figure 4) (ref. 70). Subtle effects
272
-------
1 1
•"•10-
0
X
«c
•*.
^ 8-
X
-Q
0)
O 6-
Q.
i
MM
2 4-
>(
*•
c
* 0
U2.*
9
Q.
•*—-•- T
y ^ A
T
^
^-f ^-f
r
-
— *«
?.
-
i
i
~*
•1000
•500 ?"
O
n
i
o-
•100 2
^\
X
(D
50 ^
ol
c
(D
(A
10
0
"*»
"O
5 0
Da
o
0.048
0.48
4.8
48
480
Control pg/g Aroclor 1254 in diet 260days
Figure 2. Whole-body residues and thyroidal uptake of 12SI in coho salmon
fed diets containing Aroclor 1254 for 260 days (ref. 40).
on microflora, fauna, and plankton must also be investi-
gated for potential impacts on trophic level ecology
(refs. 29,30).
Enzymatic and compositional changes of the micro-
somes occur where possible lipids are concentrated in
the membrane and manifestation of enzyme malfunction
is suspect in the proximity of hydrophobic chlorinated
aromatic hydrocarbons such as PCB, DDT, and other
organochlorine pesticides that would accumulate (ref.
50). Meyer, Mehrle, and Sanders conducted experiments
with incorporation of Aroclor 1248 into the diet of juve-
nile lake trout in concentrations of 0.2 to 6 mg/kg of
food (ref. 40). These levels, comparable to those found
in natural food, suppressed growth and serium cortisol
levels, but stimulated thyroid activity during the first
160 days of the experiment (ref. 40). After 320 days,
however, control and treated fish were similar.
Histopathological examination of fish exposed to
Aroclor and chlordane showed a very high incidence of
gill lesions after 6 months exposure; 6 percent of the
PCB-treated fish were affected, compared to 15 percent
after 9 months (refs. 76-78). Progressive and diffuse
degeneration changes in liver were noted in 80 percent
of the fish after 4 to 6 months exposure to the chlor-
dane or PCB diet. A nonspecific degeneration of liver
pyrenchema and cytoplastic vaculation of liver cells
occurred in addition to pleomorphism. The severity of
liver tissue degeneration throughout the 6- to 9-month
exposure period exceeded the controls by at least three-
fold. After this, we noted that focal areas in liver degen-
eration decreased in size and by the following year no
liver lesions could be observed in this lot of fish. This
observation was complemented by the decrease in sever-
ity of gill lesions in PCB-treated fish. The gill lesions also
improved after 9 to 12 months of exposure and no sig-
nificant difference between treated and control fish
could be detected the following year.
In parallel experiments, whole-body residues had
273
-------
12
10
TS
*o
V.
X
"£ 8-
X
_S 6-
o
^M
Q.
3
i 4-
\n
CM
•— •
C2-
«
u
V.
j
JL
^^r
J
4— *
r
T
*"l <-^
•
>
r
~~1~*
r
<-
*-<
)
V
1"*
_
1
^
'
r-
L
>
1~»'
-*.
)
•4—1 '
rr
-*
•36
O
30 J~
1
27 O"
0
24^"
21 J
(A
18 SI
c
15 *
M
12 O
•*»
9 "XJ
o
6 09
3
2.4 24
2.4 24
2.4 24
2.4 24
1232 1248 1254 1260
PCB (Aroclor) in diet 193 days
Confro/
Figure 3. Whole-body residues and thyroidal uptake of 12; I in channel
catfish fed diets containing Arociors 1232, 1248, 1253, and
1260 for 193 days (ref. 40).
increased from 0.13 mg/kg at the lower dosage of 0.1
mg/kg in the food to a residue of 9.7 mg/kg at the higher
food dosage 6 mg/kg after 320 days (ref. 40). After the
trout were fed uncontaminated food for 60 days, the
residues declined an average of 31 percent, 15 percent,
and 12 percent in the 0.6-, 1.8-, and 6.0-mg/kg treat-
ments respectively. Lake trout growth was retarded by
the dietary intake of Aroclor 1248. These results suggest
that although fish have a remarkable ability to recuper-
ate and regenerate tissue, the extent and lethality of
damage through intoxication by PCB are not clear. How-
ever, precise toxicological implication of Aroclors on the
general well being and health of fish is certainly suspect
(ref. 70).
EFFECTS ON BIRDS AND MAMMALS
Behavioral effects of organochlorine pesticides and
PCB have been noted in ihe studies conducted on Japa-
nese or coturnix quail ted sublethal concentrations and
subjected to a simultaneous test for avoidance behavior
by rapidly moving away from strange objects (refs.
79,82). This behavior appears in the very early stage of
development of galinaceous chicks and is almost certain-
ly essential to their survival in the wild. Seven-day-old
coturnix chicks were given Aroclor 1254 in their diet for
8 days and in untreated food for 6 more days. Avoid-
ance behavior was measured daily, and a group avoid-
ance response was significantly suppressed by chlordane.
274
-------
AQUATIC
ORGANISM
(HOST)
Figure 4. Relationship between environmental
stress imposed by PCB and pesticides,
susceptible host, and the disease or-
ganism as suggested by Sniezko
(ref. 70).
dieldrin, and Aroclor 1254, although DDE had no appar-
ent effect. Whereas the behavior of untreated birds re-
turned to normal after 2 days on untreated feed, the
response of chicks that were on dieldrin- and chlordane-
treated feed improved somewhat during the 6 days of
untreated food. However, the response of birds treated
with Aroclor 1254 showed no improvement during the
period.
Investigative monitoring for pesticide and PCB resi-
dues indicated that the highest residues occur in or near
urban and industrialized areas. If these data are transfer-
able to many other species of birds, we would expect to
see the avoidance reaction suppressed, mortalities would
increase from accidents, and predation would be maxi-
mized through the encroachment of man on the habitat
of the species. The causes of mortality were subjected to
autopsy study plus chemical analysis in studies conduct-
ed from 1969 through 1970 on 39 bald eagles found
dead in various areas in the United States (refs. 42, 57,
79-82). The median residues of DDE in carcuses were 7
ppm in 1969 and 19 ppm in 1970, and mean residues of
dieldrin were 0.4 ppm in 1969 and 0.7 ppm in 1970. Six
of the eagles had dieldrin residues in the brain of 4.6 to
11 ppm, which is within the lethal range. One eagle con-
tained 385 ppm of DDE and 235 ppm of PCB. In sum-
mary, environmental poisons were credited with 18 per-
cent of the deaths, illegal shooting with 46 percent, acci-
dents with 15 percent, natural disease with 8 percent,
and miscellaneous and unknown causes with the remain-
ing 13 percent.
In a survey to determine the degree of eggshell thin-
ning and the extent of chemical contamination in aquat-
ic birds in the Texas Coast area, eggs from 21 species
were collected in 1971 (refs. 52, 78-80). Chemical analy-
sis completed for 14 species showed that DDT in metab-
olites existed in all samples, whereas dieldrin residues
were found in the Texas Rice Belt and the highest PCB
residues were near urban and industrial areas again (ref.
79). The most noticably high PCB residues were found
in some eggs of inland feeding species, including: dou-
ble-crested cormorant (Phalacrocorax auritus), which
contained 32 ppm; Caspian terns (Hydroprogne caspia),
16.5 ppm; and Foster terns (Sterna forsteri), 12.5 ppm
(ref. 80). However, PCB were present in only 66 percent
of the 158 eggs that were analyzed in another study
conducted on ospreys (Pandion hafiaetus) in the Gulf of
California. During 1971, the residues of DDT were
found to be generally low compared to those in osprey
populations showing poor reproductive success in other
parts of the range. PCB residues were detected in four of
eight eggs and when present were higher than DDE resi-
dues; however, eggshell thinning was minor (averaging-3
percent), as expected from their low residues.
An experimental study on the absorption and me-
tabolism of the PCB mixture Aroclor 1254 showed that
all the components in the mixture were absorbed in es-
sentially equal proportions from encapsulated dosages
(ref. 81). The dietary dosage for quail of 300 ppm of
Aroclor 1254 for 14 days followed by 14 or 42 days of
untreated food showed that the various components of
the Aroclor were excreted at greatly different rates. At
the end of the 42 days of clean food, the PCB compo-
nents changed entirely from the proportions of com-
pounds that were originally fed to birds. Changes in pat-
terns of gas chromatographic peaks that were detected
militate against the dependable measurement of the
quantities of PCB by gas chromatographic methods that
can be related to the environmental or diet intake of the
birds.
In another study, the combined effects of
p,p'—DDE, and PCB were measured in mallard ducks.
The ducks were fed diets containing 40 ppm of each
chemical in the diet for 2 months prior to breeding and
throughout the reproductive season (ref. 81). Average
decreases in eggshell thickness were almost identical
between the two compounds, with -17.5 percent for
DDT only and -17.0 percent for DDE plus PCB in the
diet (refs. 38, 79-80). No eggshell thinning occurred in
birds fed PCB alone or in untreated diets except for a
275
-------
slight decrease in shell thickness near the end of the egg
laying period. However, the birds fed the DDE-plus-PCB
diet layed fewer eggs and egg production dropped off
significantly 8 weeks before that of birds that were re-
ceiving other treatments. Egg breakage and egg eating
were also highest in the DDE-plus-PCB groups and the
combination of the chemicals seemed to increase the
amount of egg loss through some effect—possibly on
behavior. Therefore, overall production problems were
most severe when PCB were fed in addition to the DDE.
In the Upper Great Lake States, 9 of 13 species of
fish-eating birds were investigated in 1969-1970, and
were found to sustain statistically significant decreases in
eggshell thickness since 1946 (ref. 82). Maximum
changes in thickness index occurred in great blue herons
(-25 percent), red breasted mergansers (-23 percent),
common mergansers (-15 percent) and double-crested
comorants (-15 percent). Great blue heron eggs taken
from Louisiana generally displayed smaller changes since
1946 than herons in the Midwest. On a lipid basis, mean
PCB and DDE residue levels exceeded 100 ppm in seven
of these species in the Lake States and one of seven
species in Louisiana. The average DDE:PCB ratios in the
two regions were 1.25:1 and 3.9:1 respectively. These
ratios contrast with some around 0.3:1 previously re-
ported in oceanic birds in the Bay of Fundy and with
ratios of roughly 5:1 and 10:1 that were reported by
others on the Pacific Coast. The relationship between
shell thinning and DDE content of eggs was apparent for
most species, but for herons DDE was the only com-
pound correlated (ref. 52).
Partial correlation carried out on a somewhat
questionable family basis showed that PCB also corre-
lated with shell thinning in mergansers, in a study of
chlorobiphenyl poisoning with formation of myelin
figures in both mouse and monkey liver (ref. 49). Mice
were subjected to daily dosages of .001 ml for 12-26
weeks and cornification of smooth surface membranes
of the cytoplasmic reticulum was observed (ref. 50).
This was also accompanied by a displacement of rough
surface membranes and endoplasmic proliferation and an
increase in microbodies, lyosomes, and lipid content.
Similar observations were made in the squirrel monkey
from dosages of 320 mg given over 46 days. Liver en-
largement was noted but the main cause of death was
attributed to penumonia or diarrhea (ref. 49). A similar
experiment was run on the cynomolgus monkey, which
received 641 mg in 40 days to 348 mg in 239 days with
very similar results (ref. 49). Sublethal effects of hepatic
enzyme induction were correlated with the breakdown
of estradiol and the increase in cytoplasmic RNA in
kestrels fed 0.5 to 5.0 ppm of Aroclors 1254 or 1262 for
5 months (ref. 53).
The effects of polychlorinated biphenyls and organ-
ochlorine pesticides appear to be manifested in the al-
teration of enzyme and hormone biochemistry. In un-
published work by Street and his coworkers, Vos repor-
ted that in inductions of hepatic microsomal enzymes,
the sleeping time of experimental animals was decreased
after treatment with hexobarbitol. An enhancement of
in vitro rates of aniline hydroxylation and para-nitro-
anisole demethylations occurred in direct proportion to
an increase to chlorine content of different PCB isomers
in Aroclors 1221 through 1268 (ref. 86). PCB prepara-
tion of Aroclor 1221 and Aroclor 1254 at 1 and 10
mg/kg for 28 days in pregnant rabbits resulted in liver
enlargement with increased activity of drug metabolizing
enzymes aniline hydroxylase and aminopyrine n-deme-
thylase at the rate of 10 mg/kg of Aroclor 1254, while
no effects could be measured at the other levels and with
the other levels and with the other Aroclors (ref. 86).
Vos conducted an extensive review of toxicity of
PCB for mammals and birds (ref. 86). He concluded that
PCB's have several sublethal effects, such as microsomal
enzyme induction, porphyrogenic action, estrogenic
activity, and immunosuppression. Aroclor 1254 adminis-
tered to rabbits during the first 28 days of gestation had
embryo-toxic effects at levels of 12.5, 25, and 50 mg/kg
of body weight, which demonstrates the direct effects
on microsomal enzyme activity in pregnant rabbits (ref.
77). In previously cited work by Mclaughlin (ref. 44),
edema and beak deformities in chicken embryos have
been described after yoke sac-injection of 10 and 25 mg
of Aroclor 1242 resulted in a 95 and 100 percent em-
bryonic mortality respectively. PCB have also been
found to cause neural pathology in rats when administer-
ed at a rate of 0.3 to 0.5 ml/kg per day for 14 or 21
days. The pathology is characterized by impairment of
motor function and decreased motor velocity with loss
of large nerve fibers (ref. 76).
A high dose of Aroclor was required before liver
necrosis developed in chickens (ref. 88). Moderate dos-
ages in rabbits produce mottled liver with subacute
yellow atrophy and fatty degeneration with marked
necrosis at dosage rates of 0.3 and 0.6 g/day, but 0.9
g/day caused death before liver pathology developed
(refs. 86,87). Miller (1944) observed 100 percent mortal-
ity between 17 and 98 days with similar skin applica-
tions of 34.5 mg during an 11-day period caused 100
percent mortality within 28 days while on treatment
(ref. 41). Central atrophy of liver cells occurred, with
perinuclear basophilic granulation and focal necrosis
occurring in a few of the animals.
Nichizumi (1970) utilized light and electron
microscopy to confirm the formation of so-called myelin
figures in mouse liver associated with a minimum effec-
276
-------
tive dose of 5 mg/kg of a 48% chlorine PCB (refs.
73,88). Japanese quail demonstrated porphyrogenic
action when dosed with PCB for 7 days at dosage rates
of 1 to 100 mg/kg of Aroclor 1260 (ref. 86). Nichizumi
measured the formation of aminoevulinic acid by liver
mitochondria; significant increases of greater than 10.5
to 120 m/moles ALA per gram of liver per hour were
found. PCB concentrations in the liver ranged from 1.4
to 478 ppm between the 1 mg/kg and 100 mg/kg dosage
rates. The most marked effect was noted at the 100
mg/kg dosage rate, in which microscopic tissue fluores-
cence was seen in three out of five cases and two out of
five cases respectively.
Domestic chickens demonstrate an acute susceptibi-
lity to Aroclor intoxification; liver enlargement occurs at
dosages ranging from 100-1,000 ppm of Aroclor 1242
and mortality occurs at rates above 200 ppm (ref. 88).
However, Aroclor 1258 causes mortality at dosages
above 100 ppm and partial mortalitites at dosages above
30 ppm when fed in a diet for 4 to 5 weeks. One hun-
dred percent mortality occurs in chickens fed Aroclor
1254 above 250 ppm. Pathologically, clinical observa-
tions demonstrate that general edema occurs at all toxic
dosages (refs. 7, 10, 35, 43, 55, 56). Internal haemorrh-
aging and tubular dilatation in kidneys are accompanied
by enlargement of the kidneys, in addition to defeather-
ing and dermatitis (refs. 86,88). Depression and second-
ary sexual characteristics occurred at levels as low as 30
ppm of Aroclor 1248 (ref. 7).
Sublethal effects caused by enzyme induction and
increased steroid metabolism have been demonstrated in
pigeons. American kestrels fed Aroclor 1254 and 1262
at levels of 0.5 and 5 ppm for 5 months affected hor-
mone metabolism (refs. 53, 66, 67). In an interaction of
polychlorinated biphenyls and duck hepatitis virus,
10-day-old ducklings fed Aroclor 1254 at levels of 25,
50 and 100 ppm had significantly higher mortality than
those birds not exposed to PCB (ref. 13). Vos and
Koeman (1970) found direct effects on the lymphoid
system in chickens (ref. 88). Peakall and Lincer (1972)
observed embryonic mortality and chromosomal aber-
rations in ring doves fed Aroclor 1254 at 10 ppm over
two generations (ref. 54). They found that 13 of 17
PCB-treated embryos had aberration rates exceeding the
mean control. Results thus indicate possible clastogenic
(i.e., chromosome-breaking) action of PCB in dove em-
bryos. Eggshell thinning was not observed in either the
first or second generation. Dahlgren et al. observed that
pheasant fertility and eggshell thickness were not affec-
ted by PCB exposure (ref. 10). The chief effects on re-
production occurred through PCB taken in by the hen
but not by the cock. In laying pheasant hens, the major
effects were observed in egg production, hatchability.
and viability of the embryo. There also was a subtle
effect on behavior, as the visual cliff and ability of off-
spring to avoid hand capture was adversely affected.
Among the most profound demonstrations of the
adverse effects of PCB was the inhibition of mink repro-
duction that was caused by feeding them coho salmon
containing PCB residues (refs. 2, 62, 63).
CONCLUSIONS
Polychlorinated biphenyls are highly -persistent en-
vironmental contaminants that bioaccumulate in food
chains and produce direct acute and chronic effects as
well as subtle impact on the growth, reproduction, be-
havior, and health of fish, birds, and mammals. Fresh-
water fish are particularly susceptible to chronic effects
since PCB residues concentrate at high levels that are
known to elicit serious toxicological effects. Fish-eating
birds and mammals are thus subject to hazardous levels
of residues. However, the actual mode of action and
ecological effects are poorly understood, as is the long-
term impact of PCB on animal populations.
ACKNOWLEDGMENTS
The staff of the Fish-Pesticide Research Laboratory
under the direction of Dr. Richard A. Schoettger contri-
buted the major portion of the information on effects of
PCB on aquatic organisms. The detailed Quarterly and
Annual Reports of the Research Divisions of the Bureau
of Sport Fisheries and Wildlife during 1969-1972 were
especially helpful in addition to the publications and
unpublished manuscripts from which the tables and
figures were developed. The technical assistance of Drs.
David L. Stalling, Paul M. Mehrle, Foster L. Mayer, and
Mr. Jerry R. Longcore and Mrs. Laura Crane was partic-
ularly helpful.
SCIENTIFIC NAMES
Cutthroat trout (Salmo clarki)', rainbow trout
(Salmo gairdneri); Atlantic salmon (Salmo salar): coho
salmon (Oncorhynchus kisutch); lake trout (Salvelinus
namaycush); Japanese or coturnix quail (Coturnix
cotumin); bald eagle (Haliaeetusleucocephalus)', double-
crested cormorant (Phalacrocorax auritus); Caspian tern
(Hydroprogne caspia); Fosters tern (Sterna fosteri);
osprey (Pandion haliaetus); mallard duck (Anus platyr-
hynchos); great blue herons (Ardeo herodias); red breast-
ed merganser (Mergus serratus)', common merganser
(Mergus merganser); American kestrel (Falcosparverius);
ring dove (Steptopelia risoria)', pigeon (Columba livia)',
pheasant (Phasianus colchicus); squirrel monkey (Saimiri
277
-------
sciureus); cynomolgus monkey (Macaca sp.); mink
(Mustela vison).
REFERENCES
1. J. A. Armour and J. A. Burke, "Method for Separa-
ting Polychlorinated Biphenyls From DDT and Its
Analogs," J. Assoc. Official Anal. Chem., Vol. 53,
No. 4(1970), pp. 761-768.
2. R. J. Aulerich, "Effects on Feeding Coho Salmon
and Other Great Lakes Fish on Mink Reproduc-
tion," Canadian Zoo/., Vol. 49 (1971), p. 611.
3. G. E. Bagley, W. I. Reichel, and E. Cromarie, "Iden-
tification of Polychlorinated Biphenyls in Two Bald
Eagles by Combined Gas-Liquid Chromatography-
Mass Spectrometry,'V. Assoc. Official Anal. Chem.,
Vol. 53 (1970), pp. 251-261.
4. S. Bailey and P. J. Bunyan, "Interpretation of Per-
sistence and Effects of Polychlorinated Biphenyls in
Birds," Nature, Vol. 236, No. 5340 (1972), pp.
34-36.
5. G. A. Bennett, C. K. Dinker, and M. F. Warren,
"Morphological Changes in the Livers of Rats Re-
sulting From Exposure to Certain Chlorinated
Hydrocarbons," J. Indust. Hyg. Toxicol., Vol. 20
(1938), p. 97.
6. Fredrick Berglund, "Levels of Polychlorinated Bi-
phenyls in Foods in Sweden," Environ. Health Per-
spectives, No. 1, DHEW, Nat. Inst. Environ. Health
Sci., (1972), pp. 67-72.
7. Joel Bitman, Helene C. Cecil, and S. J. Harris, "Bio-
logical Effects of Polychlorinated Biphenyls in Rats
and Quail," Environ. Health Perspectives, No. 1,
DHEW, Nat. Inst. Environ. Health Sci., (1972), pp.
145-149.
8. J. William Cook, "Some Chemical Aspects of Poly-
chlorinated Biphenyls (PCB)," Environ. Health Per-
spectives, No. 1, DHEW, Nat. Inst. Environ. Health
Sci., (1972), pp. 165-168.
9. L. K. Cutkomp, H. H. Yap, D. Desaiah, and R. B.
Koch, "The Sensitivity of Fish ATPase to Polychlo-
rinated Biphenyls," Environ. Health Perspectives,
No.-1, DHEW, Nat. Inst. Environ. Health Sci.,
(1972), pp. 165-168.
10. Robert B. Dahlgren, Raymond L. Linder, and C. W.
Carlson, "Polychlorinated Biphenyls: Their Effects
on Penned Pheasants," Environ. Health Perspectives,
No. 1, DHEW, Nat. Inst. Environ. Health Sci.,
(1972), pp. 89-101.
11. E. J. Duda, "The Use of Chlorinated Polyphenyls to
Increase the Effective Insecticidal Life of Lindane,"
J. Econ. Entomol., Vol. 50 (1957), pp. 218-219.
12. T. W. Duke, J. I. Lowe, and A. J. Wilson, Jr., "A
Polychlorinated Biphenyl (Aroclor 1254®) in the
Water, Sediment, and Biota of Escambia Bay,
Florida," Bull. Environ. Contam. Toxicol., Vol. 5,
No. 2 (1970), pp. 171-180.
13. M. Friend, and D. O. Trainer, "Polychlorinated
Phenyl: Interaction With Duck Hepatitis Virus,"
Science, Vol. 170 (1970), p. 1314.
14. G. F. Fries "Polychlorinated Biphenyl Residues in
Milk of Environmentally and Experimentally Con-
taminated Cows," Environ. Health Perspectives, No.
1, DHEW, Nat. Inst. Environ. Health Sci., (1972),
pp. 55-59.
15. D. L. Grant, W. E. J. Phillips, and D. C. Villeneuve,
"Metabolism of a Polychlorinated Biphenyl
(Aroclor 1254) Mixture in the Rat," Bull. Environ.
Contam. Toxicol., Vol. 6 (1971), p. 102.
16. D. J. Hansen, J. I. Lowe, A. J. Wilson, Jr., and P. D.
Wilson, "Chronic Toxicity, Uptake, and Retention
of Aroclor® 1254 in Two Estuarine Fishes," Bull.
Environ. Contam. Toxicol., Vol. 6, No. 2 (1971),
pp. 113-119.
17. D. J. Hansen, P. R. Parrish, and J. Forester,
"Aroclor® 1016: Toxicity to and Uptake by Est-
uarine Animals," Environ. Res., Vol. 7, No. 3
(1974), pp. 363-373.
18. J. W. Hogan and J. L. Brauhn, "Abnormal Rainbow
Trout Fry From Eggs Containing High Residues of a
PCB (Aroclor 1242)," Progessive Fish Culturist,
1974 (in press).
19. A. V. Holden, "Iinternational Cooperative Study of
Organochlorine Pesticide Residues in Terrestrial and
Aquatic Wildlife, 1967/1968," Pesticides Monitor-
ing J., Vol. 4, No. 3 (1970), pp. 117-135.
20. A, V. Holden and K. Marsden, "Organochlorine Pes-
ticides in Seals and Porpoises," Nature, Vol. 216,
No. 5122 (1967), pp. 1274-1276.
21. A. V Holden and G. Topping, "Occurrence of
Specific Pollutants in Fish in the Forth and Tay
Estuaries," Proc. R.S.E. (B), Vol. 71, No. 14
(1972), pp. 189-194.
22. D. C. Holmes, J. H, Simmon, and J. O. G. Tatton,
"Chlorinated Hydrocarbons in British Wildlife,"
Nature, Vol. 216 (1967), pp. 227-229.
23, I, Hornsteiri and W. N. Sullivan, "The Role of Chlo-
rinated Polyphenyls in Improving Lindane Resi-
dues," J. Econ. Entomol., Vol. 46 (1953), pp.
937-940.
24. S. Jensen, "A New Chemical Hazard," New Set'.,
Vol. 32 (1966), p. 612.
25. S. Jensen, "Chlorinated Hydrocarbons in Fauna and
Flora," Grundfoerbattring, Vol. 23, Special-nummer
5 (1970), pp. 81-84.
26. S. Jensen, N. Johansson, and M. Olsson, "PCB-
278
-------
Indications of Effects on Salmon," Swedish Salmon
Research Institute Report LFI MEDD, July 19,
1970, p. 9.
27. S. Jensen, A. G. Johnels, M. Olsson, and G.
Otterlind, "DDT and PCB in Marine Animals From
Swedish Waters," Nature, Vol. 224 (1969), pp.
247-250.
28. S. Jensen and L. Renberg, "Contaminants in Penta-
chlorophenol: Chlorinated Dioxins and Predioxines
(Chlorinated Hydroxy-Diphenylethers)," Ambio.,
Vol. 1, No. 2 (1972), pp. 62-65.
29. Julian E. Keil, Charles D. Graber, Lamar E. Priester,
and Samuel H. Sandiefer, "Polychlorinated Bi-
phenyls (Aroclor 1242): Effects of Uptake on £.
coli Growth," Environ. Health Perspectives. No. 1,
DHEW, Nat. Inst. Environ. Health Sci., (1972), pp.
175-177.
30 J. E. Keil, L. E. Priester, and S. H. Sandifer, "Poly-
chlorinated Biphenyl (Aroclor 1242): Effects of
Uptake on Growth, Nucleic Acids, and Chlorophyll
of a Marine Diatom," Bull. Environmental Contam.
Toxicol., Vol. 6 (1971), pp. 156-159.
31. W. B. Kinter, L. S. Merkens, Roth Janick, and A. M.
Guarino, "Studies on the Mechanism of Toxicity of
DDT and Polychlorinated Biphenyls
(PCB's): Distruption of Osmoregulation in Marine
Fish," Environ. Health Perspectives. No. 1, DHEW,
Nat. Inst. Environ. Health Sci. (1972), pp. 169-173.
32. J. H. Koeman, A. A. G. Oskamp, J. Veen, E.
Brouwer, J. Booth, P. Zwart, E. V. D. Brock, and H.
Van Genderen, "Insecticides as a Factor in the
Mortality of the Sandwich Tern (Sterna sandvic-
ensis)," preliminary communication Meded.
Riijksfac. Landbouwwetensch., Vol. 32 (1967), pp.
841-853.
33. J. H. Koeman, M. C. TenNoever de Brauw, and R.
H. deVos, "Chlorinated Biphenyls in Fish, Mussels,
and Birds From the River Rhine and the Nether-
lands Coastal Area," Nature, Vol. 221 (1969), pp.
1126-1128.
34. J. H. Koeman, J. A. J. Vink, and J. J. M. de Gocij,
"Causes of Mortality in Birds of Prey and Owls in
the Netherlands in the Winter of 1968-1969,"
Ardea, Vol. 57 (1969), pp. 67-76.
35. M. Kohanawa, "Poisoning Due to an Oily By-
Product of Ricebran Similar to Chick Edema
Disease. II. Tetrachlorodiphenyl as Toxic Sub-
stance," Nat. Inst. Animal Health Quart., Vol. 9
(1969), p. 220.
36. Massanori Kuratsune and Yoshito Masuda, "Poly-
chlorinated Biphenyls in Non-Carbon Copy Paper,"
Environ. Health Perspective, No. 1, DHEW, Nat.
Inst. Environ. Health Sci., (1972), pp. 61-65.
37. Masanori Kuratsune, "An Abstract of Results of
Laboratory Examinations of Patients With Yusho
and of Animals Experiments," Environ. Health Per-
spectives, No. 1, DHEW, Nat. Inst. Environ. Health
Sci., (1975). p. 129.
38. J. R. Longcore and B. M. Mulhern, "Organochlorine
Pesticides and Polychlorinated Biphenyls in Black
Duck Eggs From the United States and Canada—
1971," Pesticides Monitoring J., Vol. 7, No. 1
(1973), pp. 62-66.
39. J. I. Lowe, P. R. Parrish, J. M. Patrich, Jr., and J.
Forester, "Effects of the Polychlorinated Biphenyl
Aroclor® 1254 on the American Oyster Crassostrea
virginica," Mar. Biol. (Berl.), Vol. 17, No. 3 (1972),
pp. 209-214.
40. F. L. Meyer, P. M. Mehrle, and H. 0. Sanders,
"Residue Dynamics and Biological Effects of Poly-
chlorinated Biphenyls in Aquatic Organisms," Pro-
ceedings of the 164th National Meeting of American
Chemical Society, New York, N.Y., 1972.
41. J. W. Miller, "Pathologic Changes in Animals Ex-
posed to a Commercial Chlorinated Diphenyl,"
Public Health Rts., Vol. 54 (1944), p. 1085.
42. B. M. Mulhern, W. L. Reichel, L. N. Locke, T. G.
Lamont, A. A. Belisle, E. Cromartie, G. E. Bagley,
and R. M, Prouty, "Organochlorine Residues and
Autopsy Data for Bald Eagles, 1969 and 1970,"
Pesticides Monitoring J., Vol. 6, No. 3 (1970), pp.
133-138.
43. E. L. McCane, J. E. Savage, and B. L. O'Dell,
"Hydropericardium and Ascites in Chicks Fed a
Chlorinated Hydrocarbon," Poultry Science, Vol.
41 (1962), p. 295.
44. J. McLaughlin, Jr., G. P. Marliae, M. J. Verrett, M.
K. Mutchler, and O. G. Fritzlaugh, "The Injection
of Chemicals Into the Yolk Sac of Fertile Eggs Prior
to Incubation as Toxicity Test," Toxicol. Appl.
Pharmacol., Vol. 5 (1963), pp. 760-771.
45. A. V. Nebeker and F. A. Puglisi, "Effect of Poly-
chlorinated Biphenyls (PCB's) on Survival and Re-
production of Daphnia, Gammarus, and Tanytarus,"
Trans. Amer. Fish. Soc., Vol. 103, No. 4 (1974), pp.
722-728.
46. A. V. Nebeker, F. A. Puglisi, and D. L. Defoe,
"Effect of Polychlorinated Biphenyl Compounds on
Survival and Reproduction of the Fathead Minnow
and Flagfish," Trans. Amer. Fish. Soc., Vol. 103,
No. 3 (1974), pp. 567-568.
47. D. R. Nimmo, R. R. Blackman, A. J. Wislon, and J.
Forester, "Toxicity and Distribution of Aroclor®
1254 in the Pink Shrimp, Penaeus duorarum," Mar.
Biol. (Berl.), Vol. 11, No. 3 (1971), pp. 191-197.
48. Ian C. T. Nisbet and Adel F. Sarofim, "Rates and
279
-------
Routes of Transport of RGB's in the Environment,"
Environ. Health Perspectives, No. 1, DHEW, Nat.
Inst. Environ. Health Sci. (1972), pp. 21-38.
49. M. Nishizumi, "Light and Electron Microscope
Study of Chlorobiphenyl Poisoning in Mouse and
Monkey Liver," Arch. Environ. Health, Vol. 21
(1970), p. 620.
50. Norback and J. R. Allen, "Chlorinated Aromatic
Hydrocarbon Induced Modifications of the Hepatic
Endoplasmic Reticulum: Concentric Membrane
Arrays," Environ. Health Perspectives, Experimental
Issue No, 1, DHEW Pub. No. (NIH), DHEW, Nat.
Inst. of Environ. Health Sci., Vols. 72-218 (1972),
pp. 137-143.
51. M. Ogawa, "Electrophysiological and Histological
Studies of Experimental Chlorobiphenyls Poison-
ing," Fukuoka-lgaku-Zasshi (Acta Med.), Vol. 62
(1971), p. 74.
52, H. M. Ohlendorf, E. E. Klaas, and T. E. Kaiser, "En-
vironmental Pollution in Relation to Estuarine
Birds, In Survival in Toxic Environments," M. A. Q.
Khan and J. P. Bederka, eds.. Academic Press, New
York, N.Y., (1974), pp. 53-81.
53. D. B. Peakall and J. L. Lincer, "Polychlorinated Bi-
phenyls Another Long-Life Widespread Chemical in
the Environment," Bio. Science, Vol. 20, No. 17
(1970), pp. 958-964.
54. David B. Peakall, Jeffery L. Lincer, and Stephen E.
Bloom, "Embryonic Mortality and Chromosomal
Alterations Caused by Aroclor 1254 in Ring
Doves," En viron. Health Perspec fives, No. 1,
DHEW, Nat. Inst. Environ. Health Sci., (1972), pp.
103-104.
55. I. Prestt, "Organochlorine Pollution of Rivers and
the Heron (Ardea cinerea L.)," IUCN Eleven Tech-
nical Meeting, Vol. 1, pp. 95-102.
56. B. M. Rehfeld, R. L. Bradley, and M. L. Sunde,
"Toxicity Studies on Polychlorinated Biphenyls in
the Chick. I. Toxicity and Symptoms," Poultry
Science, Vol. 50 (1971), p. 1090.
57. W. L. Reichel, E. Cromartie, T. G. Lamont, B. M.
Mulhern, and R. M. Prouty, "Pesticide Residues in
Eagles," Pesticides Monitoring J., Vol. 3, No. 3
(1969), pp. 142-144.
58. L. M. Reynolds, "Polychlorinated Biphenyls (PCB's)
and Their Interference With Pesticide Residue
Analysis," Bull. Environ. Contam. Toxicol., Vol. 4
(1969), pp. 128-143.
59. L. M. Reynolds, "Pesticide Residue Analysis in the
Presence of Polychlorinated Biphenyls (PCB's) In
Residues of Pesticides and Other Foreign Chemicals
in Foods and Feeds," Residue Reviews, F. A.
Gunther and J. D. Gunther, eds., Vol. 34 (1971),
pp. 27-57.
60. K. S. Rhee and F. W. Plapp, Jr., "Polychlorinated
Biphenyls (PCBs) as Inducers of Microsomal En-
zyme Activity in the House Fly," Archives of En-
viron. Contam. and Toxicol., Vol. 1, No. 2 (1973),
pp. 182-192.
61. A. Richardson, J. Robinson, A. N. Crabtree, and M.
K. Baldwin, "Residues of Polychtorinated Biphenyls
in Biological Samples," Pesticides Monitoring J.,
Vol.4, No. 4 (1971), pp. 169-176.
62. R. K. Ringer, R. J. Aulerich, and M. Zabik, "Effect
'of Dietary Polychlorinated Biphenyls on Growth
and Reproduction of Mink," Amer. Chem. Soc. Air,
Water and Waste Division, New York, N.Y., Vol. 12
(1972), pp. 149-154.
63. R. Ringer, J. Johnson, and R. Hoopingarner, Inter-
agency Meeting on PCBs, DHEW, 1971.
64. R. W. Risebrough, "Chlorinated Hydrocarbons in
the Global Ecosystem," Chemical Fallout, G. G.
Berg and M. W. Miller, eds., Charles C. Thomas,
Springfield, III., 1969, p. 5-23.
65, Robert W. Risebrough and Brock DeLappe,
"Accumulation of Polychlorinated Biphenyls in
Ecosystems," Environ. Health Perspectives, No. 1,
DHEW, Nat. Inst. Environ. Health Sci., (1972), pp.
39-45.
66. R. W. Risebrough, R. Reiche, D. B. Peakall, S. G.
Herman, and M. M. Kirven, "Polychlorinated Bi-
phenyls in the Global Ecosystem," Nature, Vol. 220
(1968), pp. 1098-1102.
67. R. W. Risebrough, P. Reiche, and H. S. Olcott,
"Current Progress in the Determination of the Poly-
chlorinated Biphenyls," Bull. Environ. Contam. &
Toxicol., Vol. 4, No. 4 (1969), pp. 192-201.
68. J. Roburn, "A Simple Concentration-Cell Technique
for Determining Small Amounts of Halide Ions and
Its Use in the Determination of Residues of Organo-
chlorine Pesticides," Analyst., Vol. 90 (1965), pp.
467-475
69. H. 0. Sanders and J. H. Chandler, "Biological Mag-
nification of a Polychlorinated Biphenyl (Aroclor
1254) From Water by Aquatic Invertebrates," Bull.
Environ. Contam. & Toxicol., Vol. 7, No. 5 (1972),
pp. 257-263.
70. S. F. Snieszko, "The Effects of Environmental
Stress on Outbreaks of Infectious Diseases of
Fishes," J. Fish Bid., Vol. 6 (1974), pp. 197-208.
71. D. L. Stalling and F. L. Mayer, "Toxicities of PCB's
to Fish and Environmental Residues," Environ.
Health Perspectives, No. 1, DHEW, Nat. Inst. En-
viron. Health Sci., (1972), pp. 159-164.
280
-------
72. W. N. Sullivan and Hornstein "Chlorinated Poly-
phenyls to Improve Lindane Residues," J. Econ.
Entomoi, Vol. 45 (1953), pp. 158-159.
73. K. Tanaka, "Experimental Subacute Poisoning by
Chlorobiphenyls Particularly the Influence on the
Serum Lipids in Rats," Fukuoka-lgaku-Zasshi, Vol.
60(1969), p. 544.
74. G. H. Thomas and L. M Reynolds, "Polychlorinat-
ed Biphenyls in Paperboard Samples," Bull. En-
viron. Con tarn, and Toxicol., Vol. 10, No. 1 (1973),
pp. 37-41.
75. Ching-Hsi Tsao, W. N. Sullivan, and I. Hornstein, "A
Comparison of Evaporation Rates and Toxicity to
House Flies of Lindane and Lindane-Chlorinated
Polyphenyl Deposits," J Econ. Entomoi., Vol. 46
(1953), pp. 882-884.
76 U.S.D.I., Bureau of Sport Fisheries and Wildlife,
Div. of Fishery Research, Progress in Sport Fishery
Research, 1969, U.S.D.I., B.S.F.W., Resource Publi-
cation 88, 1970, 284 pp.
77. U.S.D.I., Bureau of Sport Fisheries and Wildlife,
Div. of Fishery Research, Progress in Sport Fishery
Research, 1970, U.S.D.I., B.S.F.W., Resource Publi-
cation 106,1971,318 pp.
78. U.S.D.I., Bureau of Sport Fisheries and Wildlife,
Div. of Fishery Research, Progress in Sport Fishery
Research, 1971, U.S.D.I., B.S.F.W., Resource Publi-
cation 121,1973,157 pp,
79. U.S.D.I., Bureau of Sport Fisheries and Wildlife,
Div. of Wildlife Research, Wildlife Research 1969.
Activities in the Division of Wildlife Research of the
Bureau of Sport Fisheries and Wildlife for Calendar
Year 1969, U.S.D.I., B.S.F.W., Resource Publication
94, 1971, 104pp.
80. U.S.D.i,, Bureau of Sport Fisheries and Wildlife,
Div, of Wildlife Research, Wildlife Research Prob-
lems, Programs, Progress, 1970. Activities in the
Division of Wildlife Research of the Bureau of Sport
Fisheries and Wildlife for Calendar Year 1970,
U.S.D.I., B.S.F.W., Resource Publication 104, 1970.
81. U.S.D.I., Bureau of Sport Fisheries and Wildlife,
Div. of Wildlife Research, Wildlife Research, 1971.
Activities in the Division of Wildlife Research of the
Bureau of Sport Fisheries and Wildlife for Calendar
Year 1971, U.S.D.I., B.S.F.W., Resource Publication
111, 1972, 106pp.
82. U.S.D.I., Bureau of Sport Fisheries and Wildlife,
Sport Fishery and Wildlife Research, 1972. Activ-
ities in the Division of Sport Fishery and Wildlife
Research of the Buieau of Sport Fisheries and Wild-
life for the Calendar Year 1972, V. T. Harris and P.
H. Eschmeyer, eds., 1974, 124 pp.
83. G. D. Veith, "Environmental Chemistry of the
Chlorobiphenyls in the Milwaukee River," Univ. of
Wis., Ph.D. thesis, 1970.
84 G. D. Veith and G. F. Lee, "A Review of Chlorinat-
ed Biphenyl Contamination in Natural Waters,"
Water Research, Vol. 4 (1970), pp. 265-269.
85. G. D. Veith, "Baseline Concentrations of Polychlori-
nated Biphenyls and DDT in Lake Michigan Fish,
1971," Pesticides Monitoring J., Vol. 9, No. 1
(1975), pp. 21-29.
86. J. G. Vos, "Toxicology of PCBs for Mammals and
for Birds," Environ. Health Perspectives, No. 1,
DHEW, Nat. Inst. Environ. Health Sci., (1972), pp.
105-117.
87. J. G. Vos and R. B. Beems, "Dermal Toxicity
Studies of Technical Polychlorinated Biphenyls and
Fractions Thereof in Rabbits," Toxicol. and
AppliedPharmacol., Vol. 19 (1971), p. 617.
88. J. G. Vos and J. H. Koeman, "Comparative Toxico-
logic Study With Polychlorinated Biphenyl in Chick-
ens With Special Reference to Porphyria, Edema
Formation, Liver Necrosis, and Tissue Residues,
Toxicol. and Applied Pharmacol., Vol. 17 (1970), p.
656.
89. D. F. Walsh, "Organochlorine and Heavy Metals De-
tected in Fish-A Partial Review of the FWS Con-
tribution to the National Pesticide Monitoring Pro-
gram, 1967-1973," U.S.F.W.S. administrative re-
port, Atlanta, Ga., 1975.
90. D H. White and T E. Kaiser, "Residues of Organo-
chlorines and Heavy Metals in Ruddy Ducks From
the Delaware River, 1973," Brief Pesticides Moni-
toring J. (in press).
91. D. H. White, "Nationwide Residues of Organo-
chlorines in Starlings, 1972," Pesticides Monitoring
J. (in press).
92. D. H. White and R. G. Heath, "Nationwide Residues
of Organochlorines in Wings of Adult Mallards and
Black Ducks" Pesticides Monitoring J. (in press).
93, G, Widmark, "Possible Interference by Chlorinated
Biphenyls," J, Assoc. Official Ana!. Chem., Vol. 50
(1967), p- 1069,
94. V. Zitko, O Hutzinger, and P, M. K Choi, "Con-
tamination of the Bay of Fundy-Gulf of Maine Area
With Polychlorinated Biphenyls, Polychlorinated
Terphenyls, Chlorinated Dibenzodioxins and
Dibenzofurans," Environ. Health Perspectives, No.
1, DHEW, Nat. Inst. Environ. Health Sci., (1972),
pp 47-54
281
-------
PCB's: EFFECTS ON AND ACCUMULATION BY ESTUARINE ORGANISMS
David J. Hansen*
Abstract
Effects of PCB's on and accumulation by estuarine
organisms were studied in laboratory bioassays. Aroclors
1016, 1242, and 1254 were acutely toxic to certain
estuarine organisms at concentrations greater than 10
yg/l, but these bioassays underestimated toxic/ties of
PCBs, as shown by data from exposures that lasted long-
er than 2 weeks. Concentrations that were lethal to
selected invertebrates and fishes in chronic exposures
ranged from 0.1 to 5 pg/l. Reproduction of sheepshead
minnows was impaired by concentrations of Aroclor
1254 in their eggs >5 fjg/l, but this was not observed in
eggs that contained up to 77 yg/g of Aroclor 1016. Bio-
accumulation of PCB's in estuarine organisms generally
exceeded 104 times the concentration in water in labora-
tory studies and 10s times in the estuary.
Following the discovery of PCB's in Escambia Bay,
Florida, in 1969 (ref. 1), the Environmental Research
Laboratory at Gulf Breeze, Florida, began studies with
PCB's to determine their effects on and bioaccumulation
by estuarine organisms. Estuarine organisms studied in-
cluded bacteria (ref. 2); protozoans (ref. 3,4); oysters
(refs. 5,6); shrimp (refs. 7,8,9,10,12,13); fishes (refs.
14,15,16,17,18,19); and communities of benthic orga-
nisms (ref. 20). The following discussion is confined to
research on Aroclor® 1016, 1242,1254 because these
PCB's are presently produced in the greatest quantities.
Aroclors 1016, 1242, and 1254 are acutely toxic to
certain estuarine organisms. The 48- or 96-hour LC50's,
in fig/l, range from 9 to 32 for penaeid shrimp, 12 to 16
for grass shrimp, >100 for pinfish and EC50 (reduction
of shell growth for oysters) from 10 to 32 Mg/l (refs.
1,15,21).
Laboratory bioassays lasting longer than 2 weeks
demonstrate that acute bioassays underestimate the toxi-
cities of Aroclors 1016 and 1254. Aroclor 1254 is toxic
to commercially valuable shrimps (Penaeus spp.) and
grass shrimp (Palaemonetespugio) at concentrations of 1
Aig/l (refs. 8,11). Exposed shrimp are particularly sensi-
tive to salinity stress (ref. 11) and possibly to viral dis-
ease (ref. 13). Aroclor 1254 decreases growth rates of
'Environmental Research Laboratory, Environmental Pro-
tection Agency, Gulf Breeze, Florida. 32561
©Registered Trademark, Monsanto Company, St. Louis,
Missouri.
oysters (Crassostrea virginica], at 4 fjg/l (ref. 5). At con-
centrations of about 5 ;itg/l, Aroclor 1254 is lethal to
juvenile fishes: spot (Leiostomus xanthurus), pinfish
(Lagodon rhomboides), and sheepshead minnow
(Cyprinodon variegatus) (refs. 14,19). At Aroclor 1254
concentrations of 0.1 fig/I, some sheepshead minnow fry
die (ref. 19). Aroclor 1016, at 15 Mg/l, was lethal to
pinfish and sheepshead minnows; susceptibilities of fry,
juvenile, and adult sheepshead minnows were similar
(refs. 15,18).
Aroclor 1254 affects reproduction of the sheep-
shead minnow, an estuarine fish (ref. 16). Adult fish
exposed for 4 weeks to 0.1 Mg/l appeared to be unaffect-
ed, but when eggs from these fish were fertilized and
placed in PCB-free water, the survival of fry was dimin-
ished. Mortality was observed also in fry from eggs that
contained greater than 5 M9/9 of the PCB and increased
as PCB content of the eggs increased. Reproductive suc-
cess of Atlantic salmon (ref. 22) and striped bass (ref.
23) may also be affected by PCB's in their eggs. Adult
sheepshead minnows that had been exposed for 4 weeks
to from 0.3 to 3 /ug/1 of Aroclor 1016 produced eggs
that contained from 3 to 77 /ig/g of this PCB, yet fry
that hatched from these eggs were apparently unaffected
(ref. 18).
Estuarine organisms accumulate PCB's from water.
Maximum concentration factors (concentration in ani-
mals divided by concentration in water) in laboratory
exposures of various species to Aroclor 1254 were: oys-
ters, 101,000 (ref. 5) to 165,000 (ref. 6); shrimp, 26,000
(ref. 9); and fishes, 37,000 (refs. 14,19). The maximum
concentration factor determined from exposures of
fishes to Aroclor 1016 was 34,000 (refs. 15,17). Fishes
exposed continuously to Aroclors 1016 and 1254 accu-
mulated both Aroclors in increasing concentrations for
about 4 weeks; thereaftsr, the quantity stabilized (refs.
14,15). Maximum concentrations were found in the
liver, gills, and skin of the fish, but the lowest concentra-
tion found in fishes and shrimps was in the muscle (refs.
1'4,15,8). Bioconcentration factors calculated from data
from Escambia Bay (refs. 1,10) were greater than
230,000 for shrimp, 670,000 for fishes, and greater than
100,000 for oysters, indicating that laboratory data can
underestimate bioconcentration potentials of Aroclor
1254.
REFERENCES
1. T. W. Duke, J. I. Lowe, and A. J. Wilson, Jr., "A
282
-------
Polychlorinated Biphenyl Aroclor 1254® in the
Water, Sediment, and Biota of Escambia Bay, Flori-
da," Bull. Environ. Contam. Toxicol., Vol. 5, No. 2
(1970), pp. 171-180.
2. Al W. Bourquin, and S. Cassidy, "Effect of Poly-
chlorinated Biphenyl Formulations on the Growth
of Estuarine Bacteria," Appl. Microbiol., Vol. 29
(1975), pp. 125-127.
3. Nelson R. Cooley, James M. Keltner, Jr., and
Jerrold Forester, "Mirex and Aroclor® 1254: Effect
on and Accumulation by Tetrahymena pyriformis,
Strain \N.,"J. Protozool., Vol. 19, No. 4 (1972), pp.
636-638.
4. Nelson R. Cooley, James M. Keltner, Jr., and
Jerrold Forester, "The Polychlorinated Biphenyls,
Aroclor® 1248 and 1260: Effects on and Accumu-
lation by Tetrahymena pyriformis," J. Protozool.,
Vol. 20, No. 3, pp. 443-445.
5. J. I. Lowe, P. R. Parrish, J. M. Patrick, Jr., and J.
Forester, "Effects of the Polychlorinated Biphenyl
Aroclor® 1254 on the American Oyster, Crassostrea
virginica," Mar. Bio/., Vol. 17, No. 3 (1972), pp.
209-214.
6. Patrick R. Parrish, "Aroclor® 1254, DDT, and
ODD, and Dieldrin: Accumulation and Loss by
American Oysters (Crassostrea virginica) Exposed
Continuously for 56 Weeks," Proc. Nat. Shellfish
Assoc., Vol. 64 (1974), p. 7.
7. D. R. Nimmo, P. D. Wilson, R. R. Blackman, and A.
J. Wilson, Jr., "Polychlorinated Biphenyls Absorbed
From Sediments by Fiddler Crabs and Pink
Shrimp," Nature, Vol. 231 (197la), pp. 50-52.
8. D. R. Nimmo, R. R. Blackman, A. J. Wilson, Jr.,
and J. Forester, "Toxicity and Distribution of
Aroclor® 1254 in the Pink Shrimp, Penaeus
duorarum," Mar. Biol., Vol. 11, No. 3 (1971 b), pp.
191-197.
9. D. R. Nimmo, J. Forester, P. T. Heitmuller, and G.
H. Cook, "Accumulations of Aroclor® 1254 in
Grass Shrimp (Palaemonetes pugio) in Laboratory
and Field Exposures," Bull. Environ. Contam.
Toxicol., Vol. 11 (1974), pp. 303-308.
10. D. R. Nimmo, D. J. Hansen, J. A. Couch, N. R.
Cooley, P. R. Parrish, and J. I. Lowe, "Toxicity of
Aroclor® 1254 and Its Physiological Activity in
Several Estuarine Organisms," Arch. Environ. Con-
tam. Toxicol., Vol. 3, No. 1 (1975), pp. 22-39.
11. D. R. Nimmo, and L. H. Bahner, "Some Physiologi-
cal Consequences of Polychlorinated Biphenyl- and
Salinity-Stress in Penaeid Shrimp," Pollution and
Physiology of Marine Organisms, F. John Vernberg
and Winona B. Vernberg, eds.. Academic Press, New
York, (1974) pp. 427-443.
12. DelWayne R. Nimmo, and Lowell H. Bahner,
"Metals, Pesticides, and PCB's Toxicities to Shrimp,
Singly and in Combination," Proc. Estuarine Res.
Fed., Third Internatl. Estuarine Conf., October 7-9,
1975, Galveston, Texas.
13. John A. Couch, and DelWayne R. Nimmo, "Ultra-
structural Studies of Shrimp, Exposed to the Pollut-
ant Chemical, Polychlorinated Biphenyl (Aroclor®
1254)," Bull. Soc. Pharm. Environ. Pathol.,\/o\. 11
(1974), pp. 17-20.
14. D. J. Hansen, P. R. Parrish, J. I. Lowe, A. J. Wilson,
Jr., and P. D. Wilson, "Chronic Toxicity, Uptake
and Retention of Aroclor® 1254 in Two Estuarine
Fishes," Bull. Environ. Contam. Toxicol., Vol. 6,
No. 2(1971), pp. 113-119.
15. D. J. Hansen, P.. R. Parrish, and J. Forester,
"Aroclor® 1016: Toxicity to and Uptake by
Estuarine Animals," Environ. Res., Vol. 7 (1974a),
pp. 363-373.
16. D. J. Hansen, S. C. Schimmel, and J. Forester,
"Aroclor® 1254 in Eggs of Sheepshead Minnows:
Effect on Fertilization Success and Survival of
Embryos and Fry," Proc. 27th Ann. Conf. S.E.
Assoc. Game Fish Comm., 1974b, pp. 420-426.
17. D. J. Hansen, S. C. Shcimmel, and E. Matthews,
"Avoidance of Aroclor® 1254 by Shrimp and
Fishes," Bull. Environ. Contam. Toxicol., Vol. 12
(1974c), pp. 253-256.
18. D. J. Hansen, S. C. Schimmel, and Jerrold Forester,
"Effect of Aroclor® 1016 on Embryo, Fry, Juvenile
and Adult Sheepshead Minnows (Cyprinodon
variegatus)," Trans. Am. Fish. Soc., Vol. 104, No. 3
(1975), pp. 582-586.
19. S. C. Schimmel, D. J. Hansen, and J. Forester,
"Effects of Aroclor® 1254 on Laboratory-Reared
Embryos and Fry of Sheepshead Minnows
(Cyprinodon variegatus)," Trans. Am. Fish. Soc.,
Vol. 103, No. 3 (1974), pp. 582-586.
20. David J. Hansen, "Aroclor® 1254: Effect on Com-
position of Developing Estuarine Animal Com-
munities in the Laboratory," Contrib. Mar. Sci.,
Vol. 18 (1974), pp. 19-33.
21. Jack J. Lowe and Patrick R. Parrish, U.S. Environ-
mental Protection Agency, Environmental Research
Laboratory, Gulf Breeze, Florida, unpublished data.
22. Nils Johannsson, S. Jensen, and M. Olsson, "PCB -
Indicators of Effects on Fish," in "PCB conference,
Wenner-Gren Center," Sept. 29, 1970, pp. 59-68.
Natl. Environ. Prot. Bo1., Stockholm.
23. Anonymous, 'The Striper - This Century's
Dinosaur," Stripers Unlimited, 1971 Directory and
Guidebook, 1971, pp. 11-62.
283
-------
SUMMARY OF RECENT INFORMATION REGARDING
EFFECTS OF PCB'S ON FRESHWATER ORGANISMS
Alan V. Nebeker, Ph.D.*
Abstract
Polychlorinated biphenyls (PCB's) are toxic to
freshwater organisms at concentrations below 5 vg/l
(ppb), and newly hatched fish and small insects and
crustaceans with short life cycles are most sensitive.
Aroclor 1254 at 0.45 ^g/l produced a 50 percent de-
crease in midge reproduction; 1.3 pg/l caused a 50 per-
cent reduction in Daphnia reproduction; and 1.8 [ig/l
produced 50 percent reduction in fathead minnows. The
indirect toxicity of PCB's to predators through accumu-
lation of PCB's in tissues of food organisms causes death.
Fish can accumulate 200,000 times more PCB's in their
flesh than can be held in the surrounding water. The
concentration of Aroclor 1260 in the water resulting in a
tissue residue of 0.5 ug/l is approximately 0.002 pg/l.
Aroclor 1016 and 1242 have been shown to have similar
toxicity to freshwater organisms.
The Environmental Protection Agency proposed
water quality criterion for PCB's is as follows: "Maxi-
mum acceptable concentration of PCB's in water is
0.001
Polychlorinated biphenyls (PCB's) are toxic to
freshwater fish and other aquatic organisms at very low
levels and direct toxic effects are evident within a few
hours, but much greater harm is caused by longer ex-
posure at lower concentrations. PCB levels that kill fish,
Crustacea, and aquatic insects are similar to those of
DDT and several other pesticides. Environmental occur-
rence of these materials is increasing and there is mount-
ing evidence that they are causing widespread harm in
the freshwater aquatic environment.
One of the significant accomplishments since the
discovery of the toxicity of PCB's to freshwater orga-
nisms was the synthesis of known data and their publica-
tion in the "Blue Book," or Water Quality Criteria—
1972, sponsored by the U.S. Environmental Protection
Agency and prepared by the National Academy of
Sciences, National Academy of Engineering Committee
on Water Quality Criteria (ref. 1). It was recommended
in this report that aquatic life should be protected where
the maximum concentration of total PCB in unfiltered
water does not exceed 0.002 u.g/\ at any time or place,
'Western Fish Toxicology Station, Corvallis Environmental
Research Laboratory, U.S. Environmental Protection Agency,
Corvallis, Oregon.
and the residues in the general body tissues of any aquat-
ic organism do not exceed 0.5 Aig/g.
The Environmental Protection Agency (ref. 2) also
proposed water quality criteria for PCB's as follows:
"Maximum acceptable concentrations of PCB's in water
are 0.002 jug/I, and maximum acceptable levels of resi-
dues in general body tissues of any aquatic organism are
0.5 M9/I"; following the proposed criteria recommended
by the National Academy "Blue Book." However, these
criteria have not been promulgated. Recently, the En-
vironmental Protection Agency (ref. 3), using the latest
information available, has proposed 0.001 ug/\ PCB as a
maximum permissible concentration in freshwater, but
has proposed no tissue level criterion.
The purpose of this paper is to present a summary
of recent information dealing with the toxicity of poly-
chlorinated biphenyl compounds to freshwater^ fish,
crustaceans, and aquatic insects, and to present impor-
tant recent information on the bioconcentration of
PCB's in fish tissues and its effect on consumer orga-
nisms.
Fish
A significant amount of new information dealing
with the toxicity of PCB's to fish has been collected
during the last 3 years. Acute and longer term studies
have been conducted with a variety of freshwater sport
and forage fish species. Tests with fathead minnows at
the National Water Quality Laboratory, Duluth, Minne-
sota, (ref. 4) have shown that Aroclor 1242, A-1248,
and A-1254 are toxic below 5 fJ.g/\. Ninety-six-hour
LC5o values (that concentration which kills half the fish
in 96 hours) for newly hatched fathead minnows were
15 /ug/l for Aroclor 1242 and 7.7 jug/I for A-1254. Fifty
percent died at 8.7 u.g/\ A-1248 after 30 days. After 60
days, half were dead at 8.8 /xg/l A-1242 and 4.6 ;ug/l
A-1254 (table 1).
Two 9-month continuous-flow bioassay tests were
conducted (ref. 4) with the fathead minnow to deter-
mine the effects of Aroclor 1242 and A-1254 on survival
and reproduction (table 2). Concentrations of Aroclor
1242 above 10 ng/\ were lethal to newly hatched fry and
all minnows were dead after 96 hours in 51 Aig/l A-1242;
none survived to the end of the test at 15 /ug/l. Fry
survived when reared in the same concentrations at
which their parents lived and spawned; however growth
of newly hatched fish was retarded prior to their death
284
-------
Table 1. Acute toxicity of Aroclor 1242, 1248, and 1254 to fathead
minnows, Gammarus and Daphnia, in continous-flow tests
Fathead minnow,
newly hatched
Gammarus
Daphnia
Test
temp.
(C)
24°
18°
18°
96-hr LC5Q
(yq/D
1242
15
73
—
1248 1254
*b 7.7
29
12.9 6.4
60-day LCr
(yq/lT
1242 1248
8.8 8.7C
8.7C 5.1C
- 2.6d
50
1254
4.6
—
1.8d
Concentration where 50 percent died after 96 hours.
'No mortality after 96 hours.
:Thirty-day LC5Q.
Fourteen-day LC5Q.
Table 2. Spawning and egg production of fathead minnows exposed to
Aroclor 1242 and 1254
Aroclor
concentration
(yg/D
Aroclor 1242
51.0
15.0
5.4
2.9
0.9
0.0
Aroclor 1254
15.0
4.6
1.8
0.5
0.2
0.0
Number of
spawnings
per female
0
0
2.5
3.9
1.3
4.6
0
0
1.0
5.2
3.0
2.4
Number of
"eggs per
spawning
0
0
30
63
28
90
0
0
63
105
64
104
Number of
eggs per
female
0
0
151
283
35
442
0
0
106
556
221
253
Percent
eggs
hatched
0
0
81
38
84
53
0
0
79
63
55
75
285
-------
larvae of the mosquito Culex tarsalis, exposed to 1.5
Aroclor 1254, survived well and pupated, but many of
the pupae were unable to metamorphose into the adult
form. Control organisms pupated with success.
Bioconcen tration
Bioconcentration, biological magnification, bioaccu-
mulation, PCB or tissue residues, and residue dynamics,
are some of the terms used to describe the intake of
PCB's from food or direct water contact into the animal
and accumulation in the tissues to concentrations many
thousands of times those in the water or food they were
exposed to. Polychlorinated biphenyls are much more
soluble in fatty tissues (lipids) than water and are selec-
tively concentrated in those tissues. Animals that feed
on aquatic invertebrates or fish that have bioaccu-
mulated significant tissue concentrations of PCB's are
threatened even when the prey species are not adversely
affected.
Exposure of fish to water containing PCB's demon-
strates that they can bioconcentrate PCB's directly from
the water, in addition to uptake in food, and in most
cases direct uptake from water is more rapid and leads to
much higher accumulation in the tissues. The bioconcen-
tration factor (concentration in fish tissue/concentration
in the water) for PCB's is essentially independent of the
PCB concentration in the water. The bioconcentration
factor (whole body) for adult male fathead minnows at
25° C is approximately 1.2 X 10s (120,000) for Aroclor
1248 and 2.7 X 10s (270,000) for Aroclor 1260. Fe-
male fathead minnows accumulated about twice as much
PCB's as the male fatheads and the difference is largely
The residue of PCB's in the tissues of fathead min-
nows studied by DeFoe et a'l. (ref. 7) was directly pro-
portional to the concentration of the toxicant in the
water. The concentration of Aroclor 1248 in the water
resulting in a tissue residue of 0.5 fig/g was approxi-
mately 0.004 jug/I. The concentration of Aroclor 1260 in
the water resulting in a tissue residue of 0.5 M9/9 was
approximately 0.002 jug/I. They showed that the more
highly chlorinated PCB mixtures are bioconcentrated to
a greater extent in the lipids of the fish than the lower
chlorinated compounds. They also showed that the PCB
residues in the fish reached an apparent steady state
after approximately 100 days, and when exposed fish
were placed in untreated Lake Superior water they
eliminated less than 18 percent of the body burden after
60 days.
Nebeker et al. (ref. 4) showed that the bioconcen-
tration factor for Aroclor 1254 in fathead minnows
ranged from 1.1 X 10s to 2.4 X 105 and that the bio-
concentration factor for several PCB's in the fathead
minnow ranged from about 0.3 X 10s to 2.7 X 10s
with the more highly chlorinated PCB's accumulating to
a greater extent. Adult fathead minnows accumulated up
to 430 ppm A-1242 in whole body residues, with con-
centrations up to 270,000 times that of water, and up to
1,000 ppm of 1254, with concentrations up to 230,000
times that of the water (ref. 4), Gammarus accumulated
over 500 ppm 1248 and 400 ppm 1242, with concentra-
tions over 100,000 times that of the water (ref. 14).
Sodergren and Svensson (ref. 19) showed that the
nymph of Ephemera danica accumulated Clophen A 50
to bioconcentration factors of 3 X 103. After 60 days of
exposure to Aroclor 1242 and A-1248, the maximum
bioconcentration factor in Gammarus pseudolimnaeus
was approximately 3 X 'I04 and 5 X 104, respectively
(ref. 14).
Sanders and Chandler (ref. 18) showed that the
uptake and biological magnification of Aroclor 1254 by
some aquatic invertebrates was very rapid. When
Daphnia magna were exposed for 4 days to water con-
taining 1.1 Mg/l of A-1254, they accumulated total body
concentrations 48,000 (4.8 X 104) times greater than
those in water. The mosquito larvae Culex tarsalis ex-
posed to water containing 1.5 M9/I A-1254 accumulated
19 /ig/g of this compound within 24 hours, which repre-
sents a 12,600-fold magnification. Scuds, Gammarus
pseudolimnaeus, exposed continuously to 1.6 A
-------
at higher PCB concentrations. Reproduction occurred
and good egg hatching took place at and below 5.4 /ug/l
A-1242. Eggs produced by control fish but maintained
at the higher concentrations of 15 and 51 /ug/l hatched
with good success but none of the fry survived.
Aroclor 1254 was more toxic to the fathead min-
now than A-1242 (ref. 4), as they did not survive and
reproduce above 1.8 /ug/l A-1254 (table 2). All fish in
the long-term study were dead after 96 hours at 15/ug/l,
and growth was delayed at 4.6 /ug/l. Spawning occurred
at 1.8 /ug/l but was significantly less than at the lower
concentrations. Egg hatchability and fry survival were
good at and below 1.8 Mg/l. Eggs produced by the con-
trol fish and maintained at 15 jug/I hatched readily, but
all young fish were dead withiii 96 hours.
Growth of young fathead minnows was affected
above 2.2 /ug/l A-1248, and none survived above 5.1 /ug/l
after 30 days. Young flagfish did not survive at Aroclor
1248 concentrations above 5.1 /ug/l and did not grow
well above 2.2 /ug/l (ref. 4).
Due to low PCB solubility, 96-hour LCSO values do
not adequately reflect PCB toxicities to fish. For Aro-
clor 1221-1268, 96-hour LCSO values ranged from 1,170
to 50,000 M9/I for cutthroat trout. The acute oral toxic-
ity of Aroclors 1242, 1248, 1254, and 1260 was greater
than 1,500 mg/kg in rainbow trout. Intermittent-flow
bioassays of A-1242, 1248, and 1254 to bluegills re-
sulted in 15-day LCSO values of 54, 76, and 204 /ug/l,
respectively. Exposures to channel catfish gave 15-day
LC50 values of 107, 127, and 741 /ug/l for the same
Aroclors. All LC50 values decreased significantly with
longer exposure, indicating the much greater PCB hazard
with increased exposure time (ref. 5). Direct water expo-
sures appear to represent a greater hazard to fish than
dietary exposures, but dietary sources are important as
PCB's have a high affinity for sediments and readily
enter the food chain.
Schoettger et al, (ref. 8) showed that the growth of
lake trout was retarded by Aroclor 1248 in the diet for 3
months. Concentrations of 1.2, 3.8, and 12 /ug/g de-
creased weight gain by 6, 10, and 28 percent,
respectively, below that of controls. The growth of the
high-exposure group (12 jitg/g in diet) was only about
half that of the controls after 6 months.
Fathead minnows were exposed to Aroclor 1248
and A-1260 (ref. 7), in flow-through bioassays to deter-
mine the acute (30-day) and chronic (240-day life cycle)
effects on the fry and adult fathead minnows. Newly
hatched young were the most sensitive lifestage to the
exposure of PCB's. Total mortality occurred when newly
hatched fatheads were exposed for 30 days to 8.5 /ug/i
A-1248. All fish exposed to 9.0/ug/1 A-1260 died after a
30-day exposure. The calculated 30-day TL50 for newly
hatched fathead minnows «8 hours old) was 4.7 /ug/l
for A-1248 and 3.3 /ug/l for Aroclor 1260. PCB's did not
measurably affect the ability of fathead minnows to re-
produce at concentrations which were acutely toxic to
the larvae. With reproduction occurring at and below 3
/ug/l for A-1248 and at below 2.1 jug/I for A-1260, the 20
percent reduction in the standing crop in the second
generation of minnows at concentrations as low as 0.4
/ug/l is due to the mortality of the fathead larvae soon
after hatching.
Aroclor 1016, a compound chemically similar to
A-1242, has been introduced recently to replace PCB's
of the Aroclor 1200 series in many applications. Work
has been completed with this compound with freshwater
organisms and what is available indicates that the toxic-
ity of Aroclor 1016 is similar to that of Aroclor 1242.
Mayer (ref. 8) presents data on the toxicity of
Aroclor 1016 to nine species of freshwater fishes. Blue-
gills had a 4-day LC50 of 260 jug/I A-1016; rainbow
trout, 135 /ug/l; Atlantic salmon, 134 /ug/l; and yellow
perch, 185jug/l A-1016.
Johnson (ref. 9) presented data comparing the
effects of A-1242 and A-1016 on rainbow trout and
bluegill sunfish. Rainbow trout had a 10-day LC50 of 39
/ug/l for A-1242 and 17-day LC50 of 49/ug/l for A-1016.
Bluegills had a 15-day LCSO of 54 /ug/l A-1242 and a
35-day LC50 of 43 /ug/l for A-1016. They had 96-hour
LC50 values of 125/ug/l A-1242 and 46/ug/l A-1016.
A test comparing the toxicity of Aroclor 1242 and
Aroclor 1016 using fathead minnows was completed by
Veith (ref. 10). There was no difference in the survival
of fry after 96 hours between A-1242 and A-1016 at 28
/ug/l; both had 50 percent mortality. In 30-day tests, 100
percent mortality of fry occurred at 42 /ug/l A-1242 and
95 percent mortality occurred at 42 /ug/l A-1016.
Approximately 50 percent had died after 30 days at
25.5 /ug/l A-1242 and 30.5/ug/l A-1016.
The effects of Aroclor 1242 on the guppy Poecilia
reticulata were studied by Morgan (ref. 11) in static
tests. The guppy had 100 percent mortality at 20 and 2
ppm, but only 25 percent mortality at 0.2 ppm after 7
days.
In preliminary investigations, Jensen, et al. (ref. 12)
reported a possible relationship between PCB residues in
salmon eggs and egg mortality in Sweden. When residues
in groups of eggs ranged from 0.4 to 1.9 /ug/g on a
whole-weight basis (7.7 to 34 /ug/g on a fat basis), related
mortalities ranged from 16 to 100 percent.
No adverse effects were observed on survival,
growth, and reproduction of brook trout exposed for 71
weeks to 0.94 /ug/1 and lower concentrations of the PCB
287
-------
Aroclor 1254. Survival and growth to 90 days of alevin-
juveniles from exposed parents were also unaffected.
PCB concentrations in the brook trout were directly pro-
portional to the water exposure concentration. PCB tis-
sue concentrations appeared to have reached a steady
state by the first sampling following 14 weeks of expo-
sure. PCB residues (wet tissue basis) in chronically
exposed fish were approximately 2 jug/g in the fillet and
9 jug/g in the "whole body" (minus one fillet and the
gonads) at the highest water concentration, 0.94/ug/l.
The highei residue in the "whole body" compared to the
corresponding fillet was due to the higher fat content of
the former (ref. 13).
Thyroid stimulation in coho salmon ranged from a
52 percent increase in fish fed 0.48 jug/g Aroclor 1254 of
food to a 119 percent increase in the high-treatment
group (480 jug/g). The lowest detectable stimulation of
thyroid activity occurred in salmon dosed with 171000th
that caused mortality. In channel catfish, 2.4/ug/g and
24 jug/g A-1254 in food caused significant increases in
thyroid activity when compared to control fish (ref 15).
Crustacea
Freshwater crustaceans are very sensitive to low
concentrations of PCB's. Because of their generally short
life cycles they will be eliminated from PCB-contami-
nated waters quite rapidly, causing not only their loss
from aquatic systems but impairment of fish populations
because of a decrease in fish food organisms.
To assess the danger of PCB compounds to fish food
organisms, bioassays were conducted with Daphnia
magna (ref. 14) using the eight commercially available
PCB's, Aroclor 1221, 1232, 1242, 1248, 1254, 1260,
1262, and 1268 (table 3). Aroclor 1248 was the most
toxic to Daphnia magna of the eight Aroclors tested in
static tests; the 3-week LC50 was 25 jug/I. Aroclor 1232,
1242, and 1254 had similar toxicity values to A-1248. In
continuous-flow Daphnia tests, Aroclor 1254 was the
most toxic, with a 3-week LC50 of 1.3 /ug/l. No repro-
duction occurred at 3.8 jug/I A-1254, and no adults sur-
vived 3.5 /ug/l. The Aroclors were much more toxic in
continuous-flow conditions due to continual replace-
ment of fresh PCB. Almost one-third of the PCB added
to the test water was lost to the air, with some lost to
bacteria, algae, waste materials, test container surfaces,
and test animal tissues. The difference between static
and continuous-flow results (table 3) illustrates how
critical test methodology can be for certain chemicals.
The freshwater scud Gammarus pseudolimnaeus was
also studied by Nebeker and Puglisi (ref. 14) in con-
tinuous-flow test systems to determine the effects of
A-1242 and A-1248 on survival and reproduction. Nine-
ty-six-hour LC50 values were 73 /ug/l for A-1242 and 29
Table 3. Toxicity of eight Aroclors to
Daphnia magna in static and continous
flow bioassays
Aroclor
(PCB)
3-week LC,na
(yg/D 5Q
50 percent reproductive
impairment
(ug/D
Continuous- flow test conditions
1248
1254
1254
Static
1221
1232
1242
1248
1254
1260
1262
1268
2.6
1 fic
I . o
1.3
test conditions
180
72
67
25
31
36
43
253
2.1
1.1
1.3
125
66
63
24
28
33
41
206
Concentration where 50 percent died.
Fifty percent loss of young.
cTwo-week.LC
'SO'
jug/I for A-1248. Fifty percent were surviving after 60
days at 8.7 /ug/l A-1242 and 5.1 jug/I A-1248. No live
animals remained after 2 months at 26 jug/l A-1242 or
18/ug/l A-1248 (table 4). Good reproduction occurred at
and below 2.8/ug/l A-1242 and 2.2/ug/l A-1248.
Static and flow-through toxicity tests with aquatic
invertebrates (ref. 5) indicate that they are generally
more susceptible to acute toxic effects of PCB's than
fish. Gammarus faciatus in flow-through tests had a
96-hour LC50 of 10 jug/I A-1242 and a 10-day LC50 of
5 jug/l A-1242. The glass shrimp Palaemonetes kadiaken-
sis was very sensitive to A-1254, with a 7 day LCSO of 3
jug/I.
In static tests with the amphipod Gammarus
pseudolimnaeus, Mayer et al. (ref. 15) found that of four
PCB homologs tested, the trichlorobiphenyl was slightly
more toxic than the di-, penta-, and hexachlorobi-
phenyls. The trichlorobiphenyl had a 96-hour LC50 of
100 /ug/l, two dichlorobiphenyls tested had 96-hour
LC50 values of 100 and 120 jug/I, the hexa- and penta-
homologs had 96-hour LC50 values of 150 and 210/ug/l
respectively.
The crayfish Orconectes nais was reported by Stal-
ling and Mayer (ref. 5) to have a 7-day LCSO of 30 jug/I
for Aroclor 1242 and a 7-day LCSO of 80 jug/I for
A-1254.
288
-------
Table 4. Survival and reproduction of Gam-
marus pseudolimnaeus after 2 months
exposure to Aroclor 1242 and 1248
Aroclor
concentration
(ug/l)
Aroclor 1242
234.0
81.0
26.0
8.7
2.8
0.0
Aroclor 1248
18.0
5.1
2.2
0.5
0.2
0.0
Survival
of adults
(percent)
0
0
0
52
77
48
0
53
73
71
73
64
Young per
surviving
adult
0
0
0
0
4
7
0
7
22
20
11
11
Daphnia pulex were quite sensitive to Aroclor 1242
(ref. 11). Young Daphnia pulex died at levels as low as
0.02 ppm in 4-day static tests. The toxicity of Aroclor
1242 and DDT to the ostracodCypidopsfsvidua appear-
ed to be approximately the same in static tests. At 20
ppm, there were no survivors out of 20 ostracods in the
Aroclor cultures, and some mortality occurred at 2 ppm.
Studies by Moorman and Biesinger (ref. 16) compar-
ing the lethality of Aroclor 1016 and Aroclor 1242 to
Daphnia magna have shown similar toxicity for both
compounds in static tests. No young survived after 3
weeks at 125 /ig/l A-1016 or A-1242. At 100 ug/l, 80
percent of the young (percent of control) survived after
3 weeks in A-1016 and 19 percent of the young survived
A-1242. Good survival occurred at 50 /ug/l for both
compounds.
A study of the toxicity of isomers of Aroclor 1242
and 1254 to Daphnia magna by Biesinger (ref. 17)
showed significant reproductive impairment in static
tests at 50 /ug/l for trichloro- and tetrachlorobiphenyls,
indicating that there was little difference in the toxicity
of the tri- and tetra- chlorobiphenyl compounds.
Aquatic Insects
Aquatic insects also appear to be very sensitive to
longer exposures of PCB's, though response is variable
when exposed to brief, or acute, concentrations. The
midge Tanytarsus dissimilis was tested through its full
life cycle (ref. 14) and found to be affected at levels
below 1 /ug/l. Survival and growth of the midge, when
tested with Aroclor 1254, were excellent in control
chambers but were reduced by 50 percent at the lowest
test concentration of 0.45 /ug/l (table 5). At 1.2 jug/I, the
numbers of larval cases were reduced to 35 percent of
the control, and the numbers of pupal cases were
reduced to 18 percent of the control. No adult emer-
gence occurred above 3.5 /ug/l, and abundant adult
emergence did not occur above 3 M9/I, even though lar-
vae were present. No pupal cases were constructed at 9
/ug/l and no larval cases were formed at 33/ug/l A-1254.
The calculated 3-week LC50 for A-1254 (50-percent re-
duction based on control -as 100 percent) was 0.65 A*g/l
for larvae and 0.45 jug/I for pupae. Adult midges
emerged at concentrations up to 9 /ug/l Aroclor 1248.
Larvae were present at 18 jug/l, but adult emergence did
not occur. Abundant emergence did not occur above 5.1
/ug/l(ref. 12).
Mayer et al. (ref. 15) report some acute data for
other aquatic insects. Dragonfly and damselfly nymphs,
Macromia sp. and Ischnura verticalis, were tolerant to
Aroclor 1242 and A-1254 in short-term static tests. The
dragonfly had a 7-day LCSO of 800 /ug/l for Aroclor
1242 and 1,000 /ug/l for A-1254. The damselfly, tested
under continuous-flow conditions, had a 4-day LCso of
400/ug/l for A-1242 and 200 /ug/l for A-1254.
Studies by Sanders and Chandler (ref. 18) have
shown that larvae of the stonefly Pteronarcys dorsata,
the dobonfly Corydalus cornutus, and the phantom
midge Chaoborus punctipennis survived concentrations
of up to 2.8 jug/I A-1254 for up to 21 days without
significant mortality. However, in similar experiments.
Table 5. Effect of Aroclor 1254 on the growth
and survival of the midge Tanytarsus dissimilis
Aroclor
concentration
(ug/l)
33.0
9.0
3.5
1.2
0.4
0.0 (control)
Number of mature
larval cases
(percent of
control)
0
0.2
7
' 35
52
100
Number of
pupal cases
(percent of
control)
0
0
7
18
55
100
289
-------
evidence for mink fed diets enriched with Aroclor 1254.
The data show that 0.64 jug/g of PCB in the rations
resulted in only 1 of 12 mink producing 3 kits, all of
which died on the first day.
Research with nonhuman primates indicates that
the toxicity of PCB residues to consumers are not
limited to mink. Barsotti and Allen (ref. 25) and Allen et
al. (ref. 26) have shown that PCB enriched diets were
toxic to primates. Female primates fed 2.5^9/9 Aroclor
1254 in their diet had periorbital edema, acneform
lesions on face and neck, and substantially reduced
fertility after 2 months.
SUMMARY
There is ample evidence that PCB's are toxic to
freshwater organisms at very low concentrations. Newly
hatched fish and small insects and crustaceans with short
life cycles appear to be the most sensitive life forms. In
larger animals or those with longer life cycles, toxic
effects are delayed and acute or short-term testing does
not adequately reflect the chronic or longer term effects
that PCB's have on the test animals. Concentrations of
polychlorinated biphenyls commonly found in contami-
nated waterways today, such as Aroclor 1242 and 1254,
are directly toxic to fish and aquatic invertebrates in the
range of 0.1 to 10.0 ;ug/l. Aroclor 1016 and 1242 have
been shown to have similar toxicity to freshwater orga-
nisms. The indirect toxicity of PCB's to predators
through accumulation of PCB's in tissues of food orga-
nisms may cause deaths from water concentrations that
do not cause direct lethality.
REFERENCES
1. National Academy of Sciences, National Academy
of Engineering, Water Quality Criteria 1972. Report
of the Committee on Water Quality Criteria, EPA-
R3-73-033, March 1973. U.S. Environmental Pro-
tection Agency, Washington, D.C. (Blue Book),
1973.
2. U.S. Environmental Protection Agency, Proposed
Criteria for Water Quality, U.S. Environmental Pro-
tection Agency, Washington, D. C., Vol. 1 (1973).
3. U.S. Environmental Protection Agency, Proposed
Water Quality Criteria, U.S. EPA, Washington, D.C.,
(White Book), 1976.
4. A. V. Nebeker, F. A. Puglisi, and D. L. Defoe, "Ef-
fect of Polychlorinated Biphenyl Compounds on
Survival and Reproduction of the Fathead Minnow
and Flagfish," Trans. Amer. Fish. Soc., Vol. 103,
No. 3 (1974), pp. 562-568.
5. D. L. Stalling and F. L. Mayer, "Toxicities of PCB's
to Fish and Environmental Residues," Environ-
mental Health Perspectives, April, 1972, pp.
159-164.
6. R. A. Schoettger, B. Grant, H. D. Kennedy, F. L.
Mayer, H. 0. Sanders, and D. Swedberg, "Special
Report on Polychlorinated Biphenyls (PCB's),"
Progress in Sport Fishery Research, Fish-Pesticide
Research Laboratory, Division of Fisheries Re-
search, Bureau of Sport Fishery and Wildlife, Wash-
ington, D.C., 1970, pp. 1-23.
7. D. L. DeFoe, G. D. Veith, and R. W. Carlson, "Ef-
fects of Aroclor 1248 and 1260 on the Fathead
Minnow," J. Fish. Res. Board, Canada, 1976, (in
press).
8. F. L. Mayer, "Toxicity of Aroclor 1016 to Fresh-
water Fishes," Fish-Pesticide Laboratory, USDI,
Fish and Wildlife Service, Columbia, Mo., 1975.
9. W. Johnson, Unpublished report on toxicity of
Aroclor 1016, Fish-Pesticide Laboratory, Columbia,
Mo., 1973.
10. D. Veith, personal communication. PCB test data.
National Water Quality Laboratory, Duluth, Minn.,
, 1975.
11. J. R. Morgan, "Effect of Aroclor 1242 (a Polychlo-
rinated Biphenyl) and DDT on Cultures of an Alga,
Protozoan, Daphnid, Ostracod, and Guppy," Bull.
Env. Com. and Toxicol., Vol. 8, No. 3 (1972), pp.
129-137.
12. S. Jensen, N. Johansson, and M. Olsson, "PCB—
Indications of Effects on Salmon," PCB Conference,
Stockholm, September 29, 1970, Swedish Salmon
Research Institute Report LF1 MEDD 7/1970,
1970.
13. V. M. Sharski, and F. A. Puglisi Effects of Aroclor
1254 on Brook Trout, salvelinus fontinalis. Final
Report, Environmental Research Laboratory, EPA,
Duluth, Minn., 1975.
14. A. V. Nebeker and F. A. Puglisi, "Effect of Poly-
chlorinated Biphenyls (PCB's) on Survival and Re-
production of Daphnia, Gammarus, and Tanytar-
sus," Trans. Amer. Fish. Soc., Vol. 103, No. 4
(1974), pp. 722-728.
15. F. L. Mayer, P. M. Mehrle, and H. 0. Sanders, "Resi-
, due Dynamics and Biological Effects of PCB's in
Aquatic Organisms," Arch. Env. Cont. and Toxic.,
1975, (in press).
16. K. Moorman and K. E. Biesinger, "Polychlorinated
Biphenyl Research—A Static Bioassay Using Aroclor
1016 and Related Experiments," National Water
Quality Laboratory, Duluth, Minn., 1973, unpub-
lished report.
290
-------
17. K. Biesinger, unpublished reports on toxicity of
isomers of Aroclor 1242 and 1254 to Daphnia
magna. National Water Quality Laboratory, EPA,
Duluth, Minn., 1974.
18. H. O. Sanders and J. H. Chandler, "Biological Mag-
nification of a Polychlorinated Biphenyl (Aroclor
1254) from Water by Aquatic Invertebrates," Bull.
Env. Cont. and Toxic., Vol. 7, No. 5 (1972), pp.
257-263.
19. A. Sodergren and B. Svensson, "Uptake and Accu-
mulation of DDT and PCB by Ephemera danica in
Continuous-Flow Systems," Bull. Environ. Contam.
Toxicol., Vol. 9 (1973), pp. 345-354.
20. G. D. Veith and G. F. Lee, "PCB's in Fish From the
Milwaukee River," Proc. 14th Conf. Great Lakes
/fes.,(1971a),pp. 157-169.
21. G. D. Veith and G. F. Lee, "Chlorobiphenyls
(PCB's) in the Milwaukee River," Water Res., Vol. 5
(1971b),pp. 1107-1115.
22. Michigan, "Monitoring for Polychlorinated Bi-
phenyls in the Aquatic Environment," Report to
the Lake Michigan Toxic Substances Committee,
May, Michigan Water Resources Comm., Bureau of
Water Management, East Lansing, 1973, p. 26.
23. R. K. Ringer, R. J. Aulerich, and M. Zabick, "Effect
of Dietary Polychlorinated Biphenyls on Growth
and Reproduction of Mink," presented at the Amer-
ican Chemical Society Meeting, Division of Air,
Water, and Waste, New York, N.Y., 1972, pp.
149-154.
24. N. S. Platonow and L. H. Karstad, "Dietary Effects
of Polychlorinated Biphenyls on Mink," Can. J.
Comp. Med., Vol. 37 (1973), pp. 391-400.
25. D. A. Barsotti and J. R. Allen, "Effects of Polychlo-
rinated Biphenyls on Reproduction in the Primate,"
meeting abstract, 1975 American Society for Exper-
imental Pathology.
26. J. R. Allen, L. A. Carstens, and D. A. Barsotti,
"Residual Effects of Short-Term, Low-Level Expo-
sure of Non-Human Primates to Polychlorinated
Biphenyls," Toxicol. Appl. > Pharmacol., Vol. 30
(1974), pp. 1-12.
291
-------
DISTRIBUTION AND EXCRETION OF I1 4C] -2,4,5,2',5'-PENTACHLOROBIPHENYL IN
THE LOBSTER (Homarus americanus) AND THE DOGFISH SHARK (Squalus acanthias)*
John R. Bend, Ph.D.,t, Larry G. Hart, Ph.D.,t, Anthony M. Guarino, Ph.D.,tt,
David P. Rail, M.D., Ph.D.,t, and James R. Fouts, Ph.D.t
Abstract
Significant ambient concentrations of polychlori-
nated biphenyl (PCB) residues were present in lobster
hepatopancreas (1.57 ppm wet weight! and dogfish
shark liver (1.87 ppm wet weight). PCB concentrations
in muscle were only 10-20 percent of hepatic values.
After injection of f14CJ-2,4,5,2',S'-pentachlorobiphenyl
(l*C-2,4,52',3-PCB) (0.2 mg/kg) into the pericardial
sinus of the lobster, the hepatopancreas contained more
than 90 percent of the recovered radioactivity at all
times investigated (24 hr-8 wk). Virtually all of the hepa-
topancreas radioactivity was unaltered 2,4,5,2',5'-PCB.
The radioactivity was very persistent in hepatopancreas,
female egg mass, stomach, gill, and intestine of lobsters
(ty2 > 3 wk). Following intravascular administration of
14C-2,4,5,2',5'-PCB (0.03 mg/kg) to dogfish, almost all
of the dosed radioactivity was found in liver at each time
studied (6 hr-12 days). Most of the benzene extractable
material was also unaltered 2,4,5,2',5'-PCB in each in-
stance. Small amounts of radioactivity were excreted in
bile but only traces in urine. Microsomes from lobster
hepatopancreas had no detectable aniline hydroxylase,
benzphetamine demethylase, 7-ethoxycoumarin 0-dee-
thylase, or benzpyrene hydroxylase activity although
dogfish shark liver microsomes had low activity with
each substrate tested. The persistence of
l*C-2,4,5,2',5'-PCB in the two marine species is prob-
ably related to the low hepatic microsomal mixed-
function oxidase activities observed and the high lipid
content of lobster hepatopancreas and dogfish shark
liver.
INTRODUCTION
The polychlorinated biphenyls (PCB's) possess high
chemical and thermal stabilities and have been used
extensively in the United States for certain industrial
applications during the past 45 years (ref. 1). PCB's were
first recognized as environmental contaminants in 1966
*Work for this project was done at Mount Desert Island
Biological Laboratory, Salsbury Cove, Maine.
tPharmacology Branch, National Institute of Environmental
Health Sciences, National Institutes of Health, Research Triangle
Park, North Carolina.
ttLaboratory of Toxicology, National Cancer Institute,
National Institutes of Health, Bethesda, Maryland.
(ref. 2). Subsequently, the widespread occurrence of
PCB residues was verified in wildlife species (ref. 3)
(both terrestrial and marine) all over the world, in hu-
man adipose tissue (ref. 4), in waters of the North Atlan-
tic (ref. 5), and in marine species indigenous to Maine
(ref. 6j. The chemical stability and lipid solubility of
certain PCB's contributes to their bioaccumulation.
Commercially available PCB's are complex mixtures
of many different species with varying chlorine content.
Aroclor 1254, for example, was resolved into more than
50 individual compounds, of which the pentachlorobi-
phenyl derivatives were the major constituents (ref. 7).
The present study describes the distribution and
excretion of [' 4C]-2,4,5,2',5'-pentachlorobiphenyl
(14C-2,4,5,2',5'-PCB) in the lobster (Homarus ameri-
canus) and the dogfish shark (Squalus acanthias) after
parenteral administration. The in vivo data is correlated
with in vitro microsomal mixed-function oxidase activi-
ties of lobster hepatopancreas and dogfish shark liver. A
single, radiolabeled PCB isomer was used in the disposi-
tion experiments. Use of pure isomers has obvious
advantages over similar experiments with commercial
PCB mixtures. The isomer chosen is a constituent of
Aroclor 1254, and should be representative of several
Aroclor 1254 components. PCB residues were also deter-
mined in certain tissues of lobsters and dogfish sharks.
MATERIALS AND METHODS
Male or female lobsters (320-560 g) were purchased
locally (Mt. Desert Island, Maine) and female dogfish
sharks (3.0-5.1 kg) were caught by hook in Frenchman
Bay, Maine. Both species were maintained in tanks
equipped with circulating fresh seawater before and after
treatment with 14C-2,4,5,2',5'-PCB. The lobsters main-
tained for longer than 1 week after dosing were sub-
merged in a lobster crate in Frenchman Bay. They were
fed small pieces of mackerel or flounder three times a
week when the traps were lifted to remove any dead or
ill animals. Only lobsters that were alive and in apparent
good health were dissected at the indicated times.
2,4,5,2',5'-psntachloro [14C] biphenyl
(14C-2,4,5,2',5'-PCB), (10.98 mCi mmole) was obtained
from Mallinckrodt Nuclear and was shown by thin-layer
chromatographic analysis (TLC) to be greater than 98.5
percent radiochemically pure.
14C-2,4,5,2',5'-PCB was injected into the pericardial
292
-------
sinus of lobsters (0.2 mg/kg, 1.4 X 107 dpm/kg) or into
the caudal vessels of dogfish sharks (0.03 mg/kg, 2.2 X
106 kpm/kg) as a solution in Emulphor water (36-38
percent v/v).
Lobster plasma samples were withdrawn from the
pericardial sinus just prior to sacrifice and placed in vials
containing citrate. Dogfish blood samples (serially in
disappearance studies or terminally in distribution stud-
ies) were taken from the caudal vessels and placed in
heparinized vials. At various times after administration
of 14C-2,4,5,2',5'-PCB, animals were sacrificed andvar-
ious tissues and fluids were removed from lobsters and
dogfish. Duplicate aliquots of plasma, blood, bile, or
cerebrospinal fluid (100 jul ) or tissue (70-200 mg) were
solubilized in 2 ml NCS (Amersham/Searle) by incuba-
tion at 50° C overnight. Liquid scintillation solvent (18
ml; 5.0 g PRO; and 250 mg POPOP/I toluene) was added
and the radioactivity determined in a Nuclear Chicago
Mark I scintillation spectrometer. Counting efficiency
was determined using the channels ratio technique and
varied from 50-80 percent for the solubilized biological
samples. All counts were converted to disintegrations per
minute.
TLC was performed on precoated silica gel GF
plates (5 X 20 cm, 250 nm thick; Analtech) that were
activated at 110° C for 60 min before use. Plates were
developed in hexane (solvent A) or benzene:ethyl ace-
tate, 12:1 (solvent B) and were sequentially scraped (1
cm bands). The radioactivity present in each segment
was determined by counting the silica gel in vials con-
taining 10ml Fluoralloy (Beckman)-dioxane liquid scin-
tillation cocktail. Radioactive recovery from the plates
was normally greater than 95 percent with this proce-
dure. Statistical analysis of the data was performed using
Dunnetts' multiple comparisons test. Log transformation
was used to equal the variances.
Microsomes were prepared from lobster hepato-
pancreas or dogfish liver homogenates (in 1.15% KCI
buffered to pH 7.6 with 0.013 M HEPES) by centrif uga-
tion; microsomal protein concentrations were deter-
mined and mixed-function oxidase activities were meas-
ured toward aniline, benzphetamine, benzo[a] pyrene,
and 7-ethoxycoumarin as described in detail elsewhere
(ref. 8).
PCB residue analyses were performed according to
Armourand Burke (ref. 9) following caustic hydrolysis of
a preliminary extract which removed DDT, PCB's, and
related chemicals from the tissues to be studied (ref. 10).
In estimating the degree of metabolism of
14C-2,4,5,2',5'-PCB, 25 percent w/v aqueous homoge-
nates of lobsters hepatopancreas and green gland were
extracted four times with equal volumes of warm hexane
and/or acidified toluene. Homogenates of livers from
dogfish were extracted in a similar manner with benzene.
RESULTS
Of the various lobster tissues investigated, the fe-
male egg mass was found to contain the highest residual
level of PCB's (table 1) although the hepatopancreas also
contained a significant amount. This is interesting since
the tomale (i.e., hepatopancreas of the cooked lobster) is
considered a delicacy by some people. The PCB concen-
tration in lobster muscle was about an order of magni-
tude lower than that of egg mass or hepatopancreas and
was well below the 5 ppm limitation on PCB residues in
human foodstuffs.
Dogfish shark liver also had appreciable PCB resi-
dues (table 1), whereas muscle contained only about
one-fifth the hepatic concentration (per gram wet
weight). These residual PCB's are not unexpected in
either dogfish shark liver or lobster hepatopancreas since
both tissues have high lipid contents (50 to 60 percent
wet weight)(ref. 11).
The specific activity of several lobster tissues, plas-
ma, and feces with time, after parenteral administration
of ' 4C-2,4,5,2',5'-PCB, is shown in table 2, and the per-
centage of dosed radioactivity present in the various
organs at each time point is outlined in table 3. The
hepatopancreas contained much higher amounts of
radioactivity (per mg tissue) than any other organ (table
2) and accounted for between 91 and 96 percent of the
total recovered radioactivity at all times. The half-life
(ti/2) for radioactivity in tissues was estimated from
semilogarithmic plots of the specific activity (dpm/mg)
versus tinfe (days). The tissues could be classified into
two categories (table 2): those in which labeled com-
pound had a tyz of 3 weeks or longer and those in which
the t,/2 was 1 week or less.
Almost all of the radioactivity in lobster hepato-
pancreas at 2, 4, or 8 weeks after treatment was un-
changed 2,4,5,2',5'-PCB. More than 90 percent of this
hepatopartcreas activity was extracted into hexane after
shaking homogenates four times with this solvent (93 ±
3%, mean ± SD, n = 4). Over 95 percent of the hexane
soluble radioactivity cochromatographed with authentic
2,4,5,2',5'-PCB (Analabs) on TLC plates developed in
solvent A (Rf 0.7-0.8) or solvent B (Rf 0.9-1.0). Similar-
ly, more than 90 percent of the radioactivity in hexane
extracts of green glands from lobsters sacrificed 2 or 4
weeks after dosing was 2,4,5,2',5'-PCB, although in this
case only about 50 percent of the total activity was
hexane and toluene (acidified) extractable, the remain-
der residing in the aqueous phase of green gland homo-
genate. Only about 10 percent of the fecal radioactivity
was extracted into hexane and acidified toluene (four
293
-------
Table 1. Residue levels of polychlorinated biphenyls (PCB's)
in some tissues of the lobster (Homarus americanus)
and the dogfish shark (Squalus acanthias)
Species
Lobster-
Dogfish shark
Egg mass
4.41 (2.78-5.98)
Liver
1.87
ppm wet weight PCB
Hepatopancreas
1.57 (1.13-2.27)
Muscle
0.42
'sa
Muscle
0.097 (0.07-0.
Kidney
0.2d
13)
Reported in terms of total Aroclor 1242 and 1254 residues.
Mean and ranges for 4 animals.
cMean values for 2 dogfish weighing 4-6 kg.
Detection limit in dogfish kidney.
Table 2. Specific activity of various lobster tissues and fluids with the
following pericardia! injection of14 C-2, 4, 5, 21, 51, -penta-
chlorobiphenyl (0.2 mg/kg)a
Time after administration
J issue
24 hr
1 wk
2 wk
4 wk
8 wk
\
(days)
dmp/mg tissue or /M! plasma
Hepatopancreas
Green gland
Intestine
Heart
Tail muscle
Claw muscle
Stomach
Gill
Male gonad
Egg masses
Plasma
Fecss
183.4 ± 24.7 (6)b
20.1 ± 13.0 (6)
14.0 ± 7.0 (6)
8.8 ± 5.4 (6)
5.1 ± 1.8 (6)
5.0 ± 3.1 (6)
4.5 ± 1.1 (6)
3.4 ± 1.8 (6)
8.3 (1)
16.6 ± 9.7 (5)
1.33 ± 0.41 (6)
—
192.9 ± 33.4 (7)
8.4 + 2.4 (7)
14.3 ± 5.9 (7)
2.7 ± 0.4 (7)
1.6 ± 0.1 (7)
1.5 ± 0.2 (7)
4.8 ± 2.1 (7)
3.2 ± 1.5 (7)
1.6 (1)
7.7 ± 6.6 (6)
0.49 ± 0.17 (7)
--
170.9 ± 40.0 (5)
6.1 ± 1.9 (5)
17.6 ± 18.7 (5)
2.2 ± 0.7 (5)
1.3 ± 0.3 (5)
1.3 ± 0.1 (5)
4.3 i 2.0 (5)
3.1 ± 2.3 (5)
2.9 (2)
10.2 ± 6.0 (3)
0.62 ± 0.07
142.5 i 70.7 (5)
131.2 ± 34.7 (6)
4.8 ± 1.2 (6)
4.3 ± 0.9 (6)
1.6 ± 0.3 (6)
0.8 ± 0.2 (6)
0.8 ± 0.1 (5)
2.2 ± 1.0 (6)
1.4 ± 0.9 (6)
2.1 (2)
8.6 ± 4.0 (6)
0.36 ± 0.13 (5)
21.5 ± 6.6 (6)
77.4 ± 28.4 (9)
3.4 ± 1.4 (9)
2.2 ± 1.5 (9)
1.1 ± 0.3 (9)
0.4 ± 0.2 (9)
0.6 ± 0.2 (9)
1.3 ± 0.4 (9)
0.8 ± 0.3 (9)
1.1 ± 0.2 (5)
7.7 ± 4.0 (4)
0.20 ± 0.05 (9)
20.1 ± 10.5 (9)
45
<7
23
<7
<7
<7
28
24
<1
39
<7
Data from Bend et al. (ref. 12).
b!-lean ± SD (N).
294
-------
Table 3. Percent administered radioactivity remaining in tissues of
lobster with time after pericardial injection of 14C-2, 4, 5,
21, S'-pentachlorobiphenyl (0.2 mg/kg)a
Time after injection
Tissue
Hepatopancreas
Green gland
Intestine
Heart
Tail muscle
Stomach
Gill
Male gonad
Egg masses
Mean total
recovery
24 hr
61.4 ± 8.3 (6)b
0.19 ± 0.12 (6)
0.10 ± 0.09 (6)
0.09 ± 0.04 (6)
4.36 ± 0.84 (6)
0.36 t 0.14 (6)
0.61 ± 0.31 (6)
0.06 (1)
0.48 ± 0.34 (5)
67.6%
1 wk
60.5 ± 10.8 (7)
0.07 ± 0.01 (7)
0.11 ± 0.05 (7)
0.03 ± 0.01 (7)
1.57 + 0.26 (7)
0.53 ± 0.39 (7)
0.59 ± 0.31 (7)
0.02 (1)
0.37 ± 0.56 (6)
64. 82
2 wk
61.4 + 14.6 (5}
0.07 ± 0.03 (5)
0.21 i 0.27 (5)
0.04 ± 0.02 (5)
1.54 ± 0.41 {5}
0.45 + 0.22 (5)
0.60 ± 0.41 (5)
0.03 (2)
0.46 ± 0.44 (3)
64.8S;
4 wk
55.2 ± 13.4 (6)
0.05 ± 0.01 (6)
0.04 ± 0.01 (6)
0.02 ± 0.01 (6)
0.96 i 0.26 (6j
0.20 ± 0.10 (6)
0.25 ± 0.15 (6)
0.04 (2)
0.64 i 0.38 (4)
57.4%
8 wk
3]. 2 ± 12.5 (9)
0.04 ± 0.02 (9)
0.03 + 0.02 (9)
0.01 + 0.01 (9)
0.45 i 0.02 (9)
0.12 i 0.04 (9)
0.16 i 0.07 (9)
0.01 ± 0.01 (5)
0.67 t 0.53 (4)
32.7%
Data from Bend et al. (ref. 12).
bMean ± SD (N).
extractions with each solvent), but about 70 percent of
the organic extractable material was chromatographi-
cally identical to 2,4,5,2',5'-PCB. Neither the water solu-
ble fecal metabolites nor green gland metabolites were
investigated further.
Total recovery experiments in which lobster carcas-
ses were homogenized after dissection accounted for as
much as 90 percent of the injected radioactivity.
The specific radioactivity (dpm/mg tissue) was high-
er in dogfish shark liver than in any other tissue follow-
ing parenteral administration of 14C-2,4,5,2',5'-PCB
(table 4). There was an apparent increase in specific
radioactivity of liver between 6 and 24 hours, concomi-
tant with a statistically significant decrease in the radio-
activity of most other tissues. Liver radioactivity re-
mained at, or above, the 6-hour level throughout the
course of the experiment (20.3 dpm/mp at 12 days, the
longest period sharks could be maintained).
At all times subsequent to administration of
14C-2,4,5,2',5'-PCB to dogfish sharks, almost all of the
recovere'd radioactivity was located in the liver (table 5),
and initially all of the benzene extractable activity from
hepatic tissue was unchanged 14C-2,4,5,2',5'-PCB. Only
trace amounts of radioactivity were present in all other
tissues (less than 1 percent) with the exception of mus-
cle which contained 7 to 9 percent of the dosed activity
3 and 7 days after treatment. This observation was at-
tributable more to the large muscle content of the dog-
fish (about 23 percent) (ref. 14) than to the specific
radioactivity of the tissue.
Urine was collected continuously from a few sharks
with cannulated urinary papillae. Only trace amounts of
radioactivity were excreted in the urine of these fish
after injection of 14C-2,4,2',5'-PCB. The delayed biliary
excretion of radioactivity and the excretion of only very
small quantities of biliary metabolites suggested that
dogfish sharks biotransformed the dosed compound very
slowly. Unaltered 2,4,5,2',5'-PCB was not excreted in
the bile and the biliary radioactivity was not converted
to organic soluble material by (3-giucuronidase hydrolysis
indicating that glucuronide conjugates of phenols were
not major biliary metabolites.
The decline in blood radioactivity following the in-
travenous administration of !4C-2,4,5,2',5'-PCB is illus-
trated in figure 1. The disappearance of radioactivity
follows a multiple exponential decay relationship with
time. Using least squares technics (fig. 2), we resolved
this blood decay curve into three components by com-
puter analysis. The t/2 of 14C-2,4,5,2',5'-PCB was esti-
mated foi each component; the a, (3, and 7 components
of the radioactivity disappearance curve had tyz values of
4, 27, and 730 minutes, respectively. It is interesting
that the a and (3 components for blood disappearance of
the PCB isomer tested had similar t% values to those
reported by Dvorchik and Maren (ref. 14) for DDT
blood disappearance in this same species (3 and 30
minutes, respectively).
The initial, rapid phase of radioactivity removal
from blood after injection of 14C-2,4,5,2',5'-PCB is
probably related to the rapid uptake into liver.
295
-------
Table 4. Specific activity of various dogfish shark tissues
and fluids with time following intravenous injection
of 14C-2, 4, 5, 21, 51 -pentachlorobiphenyl (0.03
mg/kg)a
Time after administration
Tissue
Liver
Kidney
Salt gland
Pancreas
Spleen
Gill
Brain
Heart
Muscle
Blood
Bile
CSF
6 hrb
dpm/mg tissue
14.00 ± 2.15
5.39 ± 0.72
3.12 ± 0.91
2.31 ± 0.77
1.86 ± 1.04
1.84 ± 0,38
0.92 + 0.30
0.82 ± 0.10
—
0.80 ± 0.02
0.41 ± C.21
0.02 ± 0.03
24 hrb
or /yl fluid
21.63 ± 4.80
1.04 ± 0.22e
0.72 ± 0.07e
0.49 ± 0.086
0.59 ± 0.05e
0.78 i 0.05e
1.07 + 0.24e
0.36 ± 0.02e
—
0.32 ± 0.08d
1.35 ± 0.51d
0.03 ± 0.05
3 daysb
18.98 ± 5.77
0.65 ± 0.05e
0.60 ± 0.07e
0.53 ± 0.16e
0.61 ± 0.08e
0.55 ± 0.13e
0.40 ± 0.16e
0.41 ± O.ll6
0.87 ± 0.42
0.50 ± 0.23
2.71 ± 0.58e
0.06 ± 0.05
7 daysc
14.05 ± 2.39
0.49 ± 0.05e
0.36 ± 0.05e
0.33 ± 0.05e
0.46 ± 0.06e
0.70 ± 0.21d
0.16 ± 0.03e
0.15 ± 0.04e
0.66 ± 0.08
0.14 ± 0.13e
12.03 ± 4.83e
0.04 + 0.04
aData from Hart et al. (ref. 13).
bKean ± SD (N = 3).
cHean ± SD (N = 4).
up < 0.05
ep < 0.01
compared with 6 hr.
Table 5. Percent administered radioactivity remaining in tissues
of Dogfish shark with time after intravenous injection
of 14C-2, 4, 5, 21, 51 -pentachlorobiphenyl (0.03
mg/kg)a
Tissue
Liver
Kidney
Salt gland
Pancreas
Spleen
Brain
Heart
Mean total
recovery
6 hrb
75.22 ±
0.43 ±
0.08 ±
0.25 ±
0.21 ±
0.03 ±
0.05 ±
76.:
6.11
0.16
0.02
0.03
0.04
0.01
0.01
5%
Time
24
94.02 ±
0.06 ±
0.02 ±
0.05 ±
0.08 ±
0.03 ±
0.01 ±
94.
after injection
hrb
24.65
0.01
0.002
0.02
0.02
0.01
0.002
3%
3 daysb
79.55 ±
0.06 ±
0.01 ±
0.05 ±
0.06 ±
0.01 ±
0.02 ±
79. i
12.77
0.01
0.001
0.02
0.02
0.001
0.004
3%
7 daysc
89.42
0.06
0.01
0.03
0.07
0.01
0.01
89
± 11.17
± 0.02
± 0.001
± 0.004
± 0.03
± 0.002
± 0.003
.6%
aData from Hart et al. (ref. 13).
bMean ± SD (N = 3).
cMean ± SD (N = 4).
296
-------
100,000
10,000-
o.
•o
1,000-
100
200
300
TIME (min)
Figure 1. Decline in blood activity following
the intravenous administration of
14 C-2,4, 5, 21,51-PCB.
297
-------
100,000
10,000
JD
£
1,000-
200
300
Figure 2. Three components of blood decay curve.
298
-------
Microsomes prepared from lobster hepatopancreas
had no detectable aniline hydroxylase, benzphetamine
N-demethylase, 7-ethoxycoumarin 0-deethylase, or
benzpyrene hydroxylase activity (table 6), whereas dog-
fish shark liver microsomes had appreciable (but low,
relative to the little skate, Raja erinacea, another marine
elasmobranch indigenous to Maine) mixed-function
oxidase activity toward each substrate tested. These
assays were run at 30° C, the optimal in vitro tempera-
ture for 7-ethoxycoumarin 0-deethylation in the dogfish
(ref. 8). At 12° C, which is within the range of summer
water temperature in Maine, specific 7-ethoxycoumarin
0-deethylase activity was only about 20 percent of that
found at 30° C.
DISCUSSION
Although the accumulation and toxicity of commer-
cial PCB mixtures, consisting of many isomers of varying
chlorine content, were demonstrated in many aquatic
species (refs. 15-22) few such studies have utilized single,
purified PCB isomers. Hutzinger et al. (ref. 23) demon-
strated that 4-chlorobiphenyl, 4,4'-dichlorobiphenyl,
and 2,2 ,5,5'-tetrachlorobiphenyl were hydroxylated by
rat and pigeon but not by brook trout, a freshwater
species. No hydroxylated metabolites of
2,2,4,4,5,5'-hexachlorobiphenyl were found in rat,,
pigeon, or brook trout.
In previous studies from our laboratory, we found
that many marine species have some hepatic microsomal
mixed-function oxidase activity, but that this activity is
generally considerably lower than that found in mam-
malian liver (refs. 8, 24-26). Reduced rates of oxidative
xenobiotic metabofism in marine vertebrates and inverte-
brates would partially account for the persistence of
lipophilic compounds, such as the RGB's, in these
species.
The distribution, excretion, and metabolism of
14C-2,4,5,2',5'-PCB in the rat was studied by Matthews
et al. (refs. 27-31), working in our laboratory. This com-
pound is metabolized readily by rats and the major
metabolites are 3-hydroxy-, 3',4'-dihydroxy-, and
3',4'-dihydro-3',4'-dihydroxy-2,4,5,2',5'-pentachlo-
robiphenyls; the first half-life in rats is only about 2.5
days. This varies markedly from both the lobster (tables
2 and 3) and the dogfish shark (tables 4 and 5), where
excretion of radioactivity occurs very slowly and the
fatty hepatopancreas and liver, respectively, act as stor-
age depots for 14C-2,4,5,2',5'-PCB.
The very slow metabolism (and excretion) of
14C-2,4,5,2',5'-PCB in the lobster is probably related to
the very low microsomal mixed-function oxidase activi-
ties of lobster hepatopancreas (table 6). In separate
experiments, we found only traces of benzpyrene hydro-
xylase or aniline hydroxylase activity in gill or hepato-
pancreas homogenate. The much lower concentrations
of PCB's (tables 1 and 2) in lobster muscle and dogfish
muscle (vs. hepatopancreas or egg mass) suggest that
portions of marine species might be used for foodstuffs
even in certain organs exceed the FDA recommended
Table 6. Mixed-function oxidase activity in lobster hepatopancreas
and dogfish shark liver microsomes3
Species
Lobster,
ameri-canus
Dogfish
Shark,
Squalus
acanthias 0
Aniline .
Hydroxylase
0.01 (3)d>e
.07 ± 0.01 (3)f
Benzphetamine.
N-demethylase
0.06 (3)
0.15 ± 0.05 (3)
7-Fthoxycoumarin
0-deethylaseb
0.01 (3)
0.08 ± 0.02 (3)
Benzpyrene
Hydroxylase
0.01 (3)
0.07 ± 0.02 (3)
aData taken from Pohl et al. (ref. 8).
Nmoles/min/mg microsomal protein.
cFluorescence units/min/mg microsomal protein.
Minimum metabolism detected by assay procedure used.
eMicrosomes from three lobsters were tested separately.
fHean ± SD (N).
299
-------
PCB levels, provided that care is taken in preparation
and that no PCB metabolites or degradation products
with high toxicity to humans are present (ref. 32).
Although hepatic microsomes from dogfish shark
have mixed-function oxidase activity, this activity is low
relative to mammals and some other marine species (ref.
8). Furthermore, dogfish liver is very fatty and the
microsomal protein yield is very low (only 1-3 mg pro-
tein/g liver vs. 6-15 mg/g liver in the little skate), mean-
ing that whole liver xenobiotic-metabolizing activity per
gram tissue in the dogfish is even lower relative to the
skate than is specific activity (per mg miqrosomal pro-
tein).
The liver appears to function both as the major site
of i4C-2,4,5,2',5'-PCB uptake and storage in the dogfish
shark, probably due to its high lipid content. The delay-
ed excretion may be related to poor partitioning of the
compound from liver lipid into metabolically active
parenchymal cells, and to the low mixed-function oxi-
dase activity, especially at 12° to 15° C which is the
Maine water temperature in summer.
The persistence of trace doses of
14C-2,4,5,2',5'-PCB, an isomer that is metabolized
rapidly by rats, in the two marine species studied sug-
gests that the problem of PCB residues in marine and
freshwater species will be with us for some time, especi-
ally in the face of continued PCB release into the aquatic
environment.
ACKNOWLEDGMENT
We are grateful to Ms. S. Bend, Ms. T. Devereux,
and Ms. R. Pohl for excellent technical assistance and to
Dr. J. Haseman for the statistical analysis.
REFERENCES
1. O. Hutzinger, S. Safe, and V. Zitko, The Chemistry
of PCB's, CRC Press, 1974.
2. S. Jensen, "Report of a New Chemical Hazard,"
New Scientist, Vol. 32 (1972), pp. 39-45.
3. R. W. Risebrough, and B. de Lappe, "Accumulation
of Polychlorinated Biphenyls in Ecosystems," Envi-
ron. Health Perspect. Vol. 1 (1972), pp. 39-45.
4. H. A. Price, and R. L. Welch, "Occurrence of Poly-
chlorinated Biphenyls in Humans," Environ. Health
Perspect, Vol. 1 (1972), pp. 73-78.
5. G. R. Harvey, W. G. Steinhauer, and J. M. Teal,
"Polychlorobiphenyls in North Atlantic Ocean
Water,"Science, Vol. 180 (1973), pp. 643-644.
6. R. H. Adamson, and A. M. Guarino, "Natural Levels
of DDT-Related Compot-ids and Polychlorinated
Biphenyls {PCB's) in Varir: js Marine Species," Bull.
Mt. Desert Island Biol. Lab., Vol. 12 (1972), pp.
6-9.
7. D. Sissons, and D. Welti, "Structural Identification
of Polychlorinated Biphenyls in Commercial Mix-
tures by Gas-Liquid Chromatography, Nuclear Mag-
netic Resonance, and Mass Spectrometry," J.
Chromatography, Vol. 60 (1971), pp. 15-32.
8. R. J. Pohl, J. R. Bend, A. M. Guarino, and J. R.
Fouts, "Hepatic Microsomal Mixed-Function Oxi-
dase Activity of Several Marine Species from Coastal
Maine,"Drug Metab. Disposition, Vol. 2 (1974), pp.
545-555.
9. J. -A. Armour, and J. A. Burke, "A Method for Sep-
arating Polychlorinated Biphenyls From DDT and
Its Analogs," J. Assoc. Official Anal. Chem., Vol. 53
(1970), pp. 761-768.
10. Pesticide Analytical Manual 1968, Vol. I, Sections
211-13a, 221.14, 221.15. Food and Drug Admini-
stration, U.S. Department of Health, Education and
Welfare, second edition.
11. A. M. Guarino, J. B. Pritchard, J. B. Anderson, and
D. P. Rail, "Tissue Distribution of [14C] DDT in
the Lobster After Administration via Intravascular
or Oral Routes or After Exposure From Ambient
Sea Water," Toxicol. Appl. Pharmacol., Vol. 29
(1974), pp. 277-288.
12. J. R. Bend, S. G. Bend, A. M. Guarino, D. P. Rail,
and J. R. Fouts, "Distribution of 14C-2,4,5,2',5'-
Pentachlorobiphenyl in the Lobster Ho ma rus ameri-
canus after a Single Injection Into the Pericardial
Sinus," Bull. Mt. Desert Island Biol. Lab., Vol. 13
(1973), pp. 1-4.
13. L. G. Hart, J. R. Fouls, and J. R. Bend, "Distribu-
tion and Blood Disappearance of 14C-2,4,5,2',5'-
Pentachlorobiphenyl in the Dogfish Shark squalus
acanthias After Intravascular Administration," Bull.
Mt. Desert Island Biol. Lab., Vol. 13 (1973), pp.
56-59.
14. B. H. Dvorchik, and T. H. Maren, "The Fate of
p,p'-DDT [2,2-bis(p-chlorophenyl)-1,1,1-trichlo-
roethane] in the Dogfish, Squalus acanthias,"
Comp. Biochem. Physiol., Vol. 42A (1972), pp.
205-211.
15. D. J. Hansen, P. R. Parrish, J. I. Lowe, A. J.Wilson,
Jr., and P. D. Wilson, "Chronic Toxicity, Uptake,
and Retention of Aroclor 1254 in Two Estuarine
Fishes," Bull. Environ. Cont. Toxicol. Vol. 6
(1971), pp. 113-119.
16. M. L. Hattula,and O.Karlog, "Toxicity of Polychlo-
rinated Biphenyls (PCB) to Goldfish,"/4cta Pharma-
col. Toxicol., Vol. 31 (1972), pp. 238-240.
17. N. Johansson, A. Larsson, and K. Lewander, "Meta-
bolic Effects of PCB (Polychlorinated Biphenyls) on
300
-------
the Brown Trout (Salmo trutta)," Comp. Gen.
Pharmacol., Vol. 3 (1972), pp. 310-314.
18. W. B. Kinter, L. S. Merkens, R. H. Janicki, and A.
M. Guarino, "Studies on the Mechanism of Toxicity
of DDT and Polychlorinated Biphenyls (PCB's): Dis-
ruption of Osmoregulation in Marine Fish," Envi-
ron. Health Perspect., Vol. 1 (1972), pp. 169-173.
19. V. Zitko, "Uptake of Chlorinated Paraffins and PCB
from Suspended Solids and Food by Juvenile Atlan-
tic Salmon," Bull. Environ. Cont. Toxicol. Vol. 12
(1974), pp. 406-412.
20. D. R. Nimmo, J. Forester, P. T. Heitmuller, and G.
H. Cook, "Accumulation of Aroclor 1254 in Grass
Shrimp (Pataemonetes pugio) in Laboratory and
Field Exposures," Bull. Environ. Cont. Toxicol.
Vol. 11 (1974), pp. 303-308.
21. A. J. Lieb, D. D. Bills, and R. 0. Sinnhuber, "Ac-
cumulation of Dietary Polychlorinated Biphenyls
(Aroclor 1254) by Rainbow Trout (Salmo gaird-
neri)," J. Agric. Food Chem., Vol. 22 (1974), pp.
633-642.
22. H. Nestel, and J. Budd, "Chronic Oral Exposure of
Rainbow Trout (Salmo gairdneri) to a Polychlori-
nated Biphenyl (Aroclor 1254): Pathological Ef-
fects," Canad. J. Comp. Medicine, Vol. 39 (1975),
pp. 208-215.
23. 0. Hutzinger, D. M. Nash, S. Safe, A. S. W. De
Freitas, R. J. Norstrom, D. J. Wildish, and V. Zitko,
"Polychlorinated Biphenyls: Metabolic Behavior of
Pure Isomers in Pigeons, Rats, and Brook Trout,"
Science, Vol. 178 (1972), pp. 312-314.
24. J. R. Bend, R. J. Pohl, and J. R. Fouts, "Further
Studies of the Microsomal Mixed-Function Oxidase
System of the Little Skate, Raja erinacea, Including
Its Response to Some Xenobiotics," Bull. Mt.
Desert Biol. Lab., Vol. 13 (1973), pp. 9-13.
25. R. J. Pohl, J. R. Bend, T. R. Devereux, and J. R.
Fouts, "Hepatic Chemical and Drug Metabolizing
Enzymes in Coastal Maine Marine Species," Bull.
Mt. Desert Island Biol. Lab., Vol. 13 (1973), pp.
94-98.
26. R. J. Pohl, J. R. Fouts, and J. R. Bend, "Response
of Hepatic Microsomal Mixed-Function Oxidases in
the Little Skate, Raja erinacea, and the Winter
Flounder, Pseudopleuronectes americanus to Pre-
treatment with TCDD (2,3,7,8-Tetrachlorodi-
benzo-jd-dioxin) or DBA (1,2,3,4-Dibenzanthra-
cent)," Bull. Mt. Desert Island Biol. Lab., in press.
27. H. B. Matthews, P. R. Chen, H. M. Mehendale, and
M. W. Anderson, "The Metabolism, Storage, and
Excretion of Highly Chlorinated Compounds by
Mammals," ACS Symposium Series No. 2., Mech-
anism of Pesticide Action, American Chemical
Society, 1974, pp. 54-68.
28. P. R. Chen, and H. B. Matthews, "Metabolism and
Excretion of 2,4,5,2',5'-Pentachlorobiphenyl (PCB)
in the Male Rat," Toxicol. Appl. Pharmacol., Vol.
29 (1974), p. 88.
29. H. B. Matthews, and M. W. Anderson, "The Distri-
bution and Excretion of 2,4,5,2',5'-Pentachlorobi-
phenyl in the Rat," Drug Metab. Disposition, Vol. 3
(1975), pp. 211-219.
30. H. B. Matthews, and M. W. Anderson, "Effect of
Chlorination on the Distribution and Excretion of
Polychlorinated Biphenyls," Drug Metab. Dii,}osi-
tion, Vol. 3 (1975), pp. 371-380.
31. H. B. Matthews, "PCB Chlorination vs. PCB Distri-
bution and Excretion," this conference.
32. J. D. McKinney, "Correlating Biological Effects
with Chemical Structure," this conference.
301
-------
20 November 1975
Session V:
ECONOMICS AND SUBSTITUTES
Warren Muir, Ph.D.*
Session Chairman
*Senior Staff Member for Environmental Health, Council on Environmental Quality, Washington, D.C.
303
-------
INTRODUCTORY REMARKS
Warren Muir, Ph.D.
I guess we have alt had an opportunity to hear about
health and ecological impact and other aspects of RGB's
in the last day and a half. The history of RGB's, as I am
sure most of you are aware, is several years old. By 1971
and 1972 there was sufficient concern over their
potential environmental effects that a Federal task force
was created under the sponsorship of the Council on
Environmental Quality and the Federal Council for Sci-
ence and Technology, which looked into the situation
and made a variety of recommendations.
In addition, at that time the Monsanto Chemical
Company developed a restricted sales policy with regard
to uses of RGB's, and also shortly thereafter, the Organi-
zation for Economic Cooperation and Development had
an international agreement with regard to uses of RGB.
All of these actions were directed in one fashion or
another toward inappropriate uses of the chemical. Yet,
as of this date, there is no Federal authority to control
the use of these chemicals, despite 5 years of consider-
ation of toxic substances control legislation.
This particular session of the conference deals with
economics and substitutes; we will have a presentation
or a brief description of two economic case studies that
have been done on RGB's, and then several speakers will
discuss the substitutability or nonsubstitutability for
uses of RGB's.
In dealing with environmental problems such as
PCB's and a variety of other chemicals, I am sure you are
aware that there is a great deal of scientific uncertainty
with regard to particular health or ecological impacts.
For example, there is a certain amount of uncertainty as
to whether or not something is carcinogenic or whether
it can bioaccumulate.
There typically appears to^e, however, a much
greater uncertainty about the economic implications or
the economic impacts of any action that might be taken
to mitigate the suspected problems. Much of this arises
from uncertainty, about substitutes and also about the
inability to predict the actual individual or corporate
responses that would be made under a given type of
regulatory action or other type of mitigating action.
Thus in my view, there is much greater economic uncer-
tainty in many of these, issues than there is scientific
uncertainty.
Also, irrespective of all the uncertainties, we know
that the further along in the chemical marketing and
development process, the longer it has been manufac-
tured, and the larger the market, generally the greater
the health and environmental effects of the particular
chemicals and the greater the economic impact there is
of mitigating action, to the extent that they are neces-
sary.
Thus, if we are to deal with problems such as PCB's,
we must change our approach toward environmental
chemical problems; we must get out of a reactive pos-
ture. We must undertake the task of identifying poten-
tial hazardous chemicals early in the development
process. By so doing, health and ecological problems can
be avoided before they develop. And, by so doing, the
economic dislocation and impacts from any potential
regulatory action will be eliminated or minimized to the
benefit of all.
305
-------
PCB's IN CAPACITOR APPLICATIONS
Richard L. Rollins*
Abstract
Alternating current (AC) capacitors have used a
grade of polychlorinated biphenyls (PCB's) since the
1930's. Long life, high reliability and a high degree of
flame retardancy are imparted to the capacitors by these
fluids.
The latter characteristic is very important in applica-
tions where high exposure to the general population
exists such as in fluorescent lights and television sets.
The main disadvantage with the fluid is its long persist-
ence in nature. When the capacitor industry became
aware of the environmental problem, it generated guide-
lines for hand/ing and disposal of the material, then
voluntarily imposed these restrictions upon itself. Now
of the 70,000 pounds per day processed, only 7 pounds
are being discharged into plant water effluents. Liquid
waste materials are sent to proper incineration facilities
and solid waste materials are placed in sanitary landfills
to prevent escape into the environment. For 4 years the
industry has been using a significantly more biodegrad-
able grade of Aroclor identified as 1016 by Monsanto. In
that time, Aroclor 1016 has not been identified as a PCB
commonly found in the environment. Non-PCB mate-
rials are continuing to be evaluated, but there are not
dielectric fluids available today which can be considered
an acceptable substitute for PCB's in the broad range of
AC capacitors.
On behalf of the electronic industrial association
and the manufacturers of PCB capacitors, I appreciate
this opportunity to present our point of view. I will
discuss PCB capacitors, the industry's response to the
environmental problem, and possible alternative candi-
dates to PCB's.
Manufacturers of AC capacitors have used PCB's
since the early 1930's, and have used them almost ex-
clusively sinc§ World War II. They are presently used, for
example, in capacitors for fluorescent lighting, air con-
ditioners, and television sets. These capacitors are in the
plant where you work, in the home, and in public
gathering facilities. They are therefore near you a high
percentage of the time. Manufacturers are very cognizant
of their responsiblities in providing a capacitor that will
operate satisfactorily in these applications for providing
long life and high reliability at a reasonable cost.
*Vice President for Engineering, Jard Corporation,
Bennington, Vermont.
The consequence of these requirements in a com-
petitive marketplace is that the products and their com-
ponents are constantly being reevaluated to increase life,
increase reliability, decrease size, and decrease cost. The
capacitor manufacturer indeed daily sees pressures for
improvements. It is, therefore, an obvious question to
ask why are PCB's still used after 40 years during which
the best capacitor research and development scientists in
the United States were constantly seeking substitutes.
One of the reasons lies in the nonflammability of
the PCB material. Because of applications, such as light-
ing, where personnel and equipment safety are para-
mount, capacitors must be manufactured since they not
only fail infrequently but also fail safely. In applications
such as the World Trade Center in New York, where
250,000 fluorescent lights are installed, it is obvious that
high reliability and a nonflammable capacitor character-
istic are mandatory.
A capacitor which fails violently and contains a
flammable fluid could create a serious problem, especial-
ly in densely populated buildings, giving visions of a
towering inferno. The Consumer Products Safety Com-
mission, as an example, has shown considerable concern
over television set fires and has requested Underwriters'
Laboratories to develop standards for safety for tele-
vision set receivers.
A second reason lies in the reliability of the product
as it is known today. Presently, the capacitors our com-
panies manufacture have a survival rate per year greater
than 99.9988 percent. The requirement that more than
95 percent of our capacitors must survive after 13 years
of normal application conditions must also be met.
The test time and the amount of test necessary to
guarantee the above reliability is mind boggling to say
the least. Many thousands of units and millions of unit
hours at or referred to application conditions are
required to satisfy our statisticians that any change in
product will conform to these present day standards.
Even with the large amount of previous testing and
history on the PCB-containing capacitor, there have been
many instances which despite all controls in existence
cause consumer concern due to extreme failure rates.
That is at a rate greater than 10 percent.
The first occurred in 1957, when a variation in the
quality of the PCB fluid, as synthesized, resulted in a
highly unstable capacitor. Standard analytical tests in
use at the time did not detect the quality difference. The
result was a large number of capacitors failing in a very
short period of application life.
306
-------
The consequence was the requirement by the
customer that the capacitor manufacturer not only pro-
vide compensation for the cost of the capacitor, but the
cost of the equipment which contained the capacitor,
plus the labor charge for placing the equipment in the
installation. The total replacement cost the manufac-
turer 100 times the original price of the capacitor.
The second instance of numerous failures occurred
6 years later, this time involving the capacitors of most
manufacturers. In this circumstance reduced-size capaci-
tors were tested and approved by industry-accepted
accelerated life testing and a new size was shipped to
customers.
Approximately 1 year later, up to 15 percent of
these capacitors began failing in some applications. A
subsequent modification in the accelerated-life testing
based upon findings in the field failure analyses now
provides proper screening to eliminate the chance of
such a problem occurring. Therefore the AC capacitor
industry now does very extensive evaluations before re-
leasing new designs or using new materials.
The capacitor industry became aware that PCB's
were possible environmental problems in 1970. Soon
thereafter, in 1971, a committee was formed under the
sponsorship of the American National Standards Insti-
tute, ANSI, to develop standard industry guidelines for
the handling and disposal of capacitor grade PCB's. An
interim standard was published as an official standard
proposal by the National Electric Manufacturers Associa-
tion, IMEMA, in January 1973. And a final document,
C107.1 1974, was published in January 1974.
Briefly, properly planned housekeeping, considera-
tions for employee safety, and scrap disposal procedures
were detailed. Today, to the best of my knowledge, all
manufacturers of PCS capacitors in the United States
have applied these guidelines for the handling and dis-
posal of PCB's.
The success of the manufacturer's control in han-
dling practices is apparent from the fact that of the
approximately 70,000 pounds per day used, less than
.01 percent or 7 pounds per day is discharged into the
water effluents of the plants. The ANSI guidelines also
recommended that the capacitor companies change from
Aroclor 1242 to a PCB with less toxic effects which
Monsanto identified as Aroclor 1016.
Here it must be pointed out that various grades of
PCB's cannot, as so often is assumed, be classified as
having the same chemical, physical, or biological charac-
teristics. For instance, in "A Comparative Study of Two
Chlorinated Biphenyl Mixtures.. .," by Goldstein et al.,
significant differences were shown to exist in the biologi-
cal effects of Aroclor 1242 and 1016 on equal doses of
the two mixtures. Aroclor 1016 also reduces by greater
than 94 percent those higher homologs existing in
Aroclor 1242 which were the most persistent in nature.
With these benefits, and without sacrificing the capacitor
characteristics, all capacitor manufacturers began using
the new material by 1972, despite the fact that it was 50
percent more expensive.
After 4 years of use by the capacitor industries,
Aroclor 1016 has not been identified as a PCB that is
commonly found in the environment. Nor should it be
suspected that 1016 would be commonly found, because
the industry is exercising control over waste disposal
from its capacitors, so that there is little or no oppor-
tunity for leaking PCB's.
Our industry believes it is much more important to
reduce the environmental problems and to allow con-
tinued use of the capacitor-grade PCB than to be con-
cerned with the material cost increase and immediately
turn to a substitute which is not thoroughly evaluated
and may be flammable.
Alternates have been considered ever since the origi-
nal introduction of PCB's. The substitutes must be not
only a satisfactory dielectric fluid providing acceptable
life, reliability, and safety, but in addition must not
cause environmental problems. Our experience with
PCB's has demonstrated that some material will escape
into the environment through processing and handling.
Therefore, alternate fluids must be evaluated on this
basis. The effects on man and his environment must be
determined before the product is introduced. It would
be a very serious error to replace capacitor-grade PCB's
with a fluid which eventually becomes a greater threat to
man.
Further PCB modification which would provide
even less toxicity and persistence in nature but still
maintain good dielectric properties and good non-
flammability would seem to be one alternative to
Aroclor 1016. Our companies respectfully urge
Monsanto to pursue this possibility.
Non-PCB alternatives are now being offered and
suggested. Some are new and some have been available
for many years. The industry's position on these is as
follows.
Mineral oil is a flammable fluid which was replaced
by PCB's in the 1930's. Capacitors using it are 50 to 100
percent larger, much less reliable, and much less safe
than those using PCB's. The substitution of mineral oil
necessitates redesign of equipment to utilize the larger
capacitor, an increase in the capacitor manufacture facil-
ity, and will result in increased use of basic materials
which are presently in short supply.
Modified synthetic hydrocarbon oils have been
developed which while flammable would allow capaci-
tors to approximate today's size. Samples have been dis-
307
-------
tributed for testing, but the material is not commercially
available.
Phthalate ester, also a flammable fluid and also with
biodegradability problems, has been used in certain
restricted applications where conditions of limited tem-
peratures exist. The unknown factors of reliability and
safety in the broad consumer use areas such as lighting
now prevent its use. Evaluations, however, are continu-
ing.
Substituted aromatic compounds are possible candi-
dates, and one has been proposed that has less fire resist-
ance than PCB's; it is suggested to be a good dielectric
fluid but only for high-voltage power factor correction.
This, to our estimation, represents only 17 percent of
the PCB used in closed systems, and leaves completely
unanswered an alternative or alternatives for the remain-
ing 83 percent of the applications. Some material has
been produced but the fluid has not been made commer-
cially available. In fact, our companies are having trouble
obtaining samples from the manufacturer. When samples
become available, the time-consuming testing can begin.
It has been estimated that 3 years are required before
final commercial use after initial testing of a change in
capacitor fluids.
Also proposed for limited applications is the use of
a plastic film replacing the kraft paper dielectric in the
AC capacitor. Although evaluations with the highest
quality film have been underway for more than 2 years
using the current processing techniques, the reliability of
the product is only 1/20th of that of present capacitors
in most applications. Significant additional testing is
required to determine if the cause of poor reliability is
totally inherent or if improvements can be made by
modifications in capacitor design.
In summary, there are no commercially available
fluids which today can be considered a totally accept-
able substitute for PCB's in the broad range of AC
capacitors, nor are there substitute dielectric systems
which would satisfy the requirements of reliability and
safety in most applications.
,l would like to reiterate that our companies have
shown responsiveness to the environmental problems of
PCB's by the following actions.
1. Working as a group with government and consumers
in providing guidelines for proper handling and dis-
posal of capacitor- and transformer-grade PCB's.
2. Reducing discharge levels of PCB's in a 16-capacitor
plant. Further reductions are now being planned.
3. Converting to a more expensive grade of PCB's
which is less persistent and has less toxic effects.
Finally significant differences do exist between Aro-
clor 1016, which capacitor manufacturers are now using,
and material which is predominantly being found in the
environment. Our industry believes that all concerned
should be aware of the differences.
We respectfully urge this awareness in environ-
mental studies and in drafting of regulations.
308
-------
THE ECONOMIC IMPACT OF A BAN
ON POLYCHLORINATED BIPHENYLS
Duncan MacArthur* and Stephen F. Nagyt
Abstract
The study described below assessed the effects of a
hypothetical total ban on PCB's. In order to compile a
realistic scenario, the proposed Toxic Substances Con-
trol Act was used as a model. A complete phaseout was
estimated to take 76 months, and would involve publica-
tion of rules, testing, hearings, halting of imports and
manufacturing of PCB's, and depletion of stocks of
PCB-con tain ing products.
Mineral oil was assumed to be the primary substi-
tute for PCB's, since a ma/or technological breakthrough
in the development of alternate fluids is unlikely in the
near future.
Minimum estimates are given for the one-time and
annual capital expenditures by industry of a ban on
PCB's, and for the primary and secondary impact costs.
Intangible issues, such as the effect of a PCB ban on
public safety, are also discussed.
In the course of our work with private and public
clients, we have examined polychlorinated biphenyls,
PCB's, in a number of areas, ranging from product design
to economic impact. The work to be discussed here was
completed in 1975 as part of a study to examine the
effects of the proposed Toxic Substances Controls Act,
as illustrated by Senate Bill S776 (20 Feb. 75).
We selected as an example a case study to com-
pletely ban an existing product following the procedures
outlined in the proposed bill. We use the case study for
following reasons. It provides an example of the com-
plete analysis required to assess the impact of a ban; it
illustrates the direct and secondary impact on industry;
and it enables us to estimate the economic consequences
of a ban on one specific product. In our study, we also
highlighted the unquantifiable factors.
In our methodology, and again this was done in the
early part of the year, we assume all the steps in the
proposed Toxic Substance Control Act as illustrated by
Senate Bill S776 are taken. The end result of this is a
total ban on PCB manufacture and use. We selected
PCB's for illustrative purposes only. Our discussion was
not intended to reflect on the actual health or environ-
mental aspects of the example product.
'Associate Research Director, Foster 0. Snell, Inc., Division
of Booz, Allen, & Hamilton, Inc., New York, New York.
tResearch Director, Foster D. Snell, Inc., Division of Booz,
Allen, & Hamilton, Inc., New York, New York.
The scenario for banning the product is estimated to
require about76 months for complete phaseout of prod-
uct use. Thirty-eight months were estimated for publica-
tions of the rules, testing, hearings, and so forth. The
key element in this period is the 24-month period that
we estimated would be required for testing. The key
element in months 39 through 76 is phasing out the sale
of some manufactured goods, particularly appliances. We
also assumed that no legal action would be taken by
industry until publication of the final ban on substances
occurring after the 38 months of testing and hearings.
A possibility in the scenario of the second 38
months is that industry requests a judicial review but
complies with the review. We estimated the judicial
review takes 2 years and results in a complete product
ban. In the second 38-month period the following types
of activity would go on: documentation for control
purposes; monitoring of shipments; limitation of stock-
piling of PCB products; refining methods to prevent
PCB's from entering the environment, such as controlled
use and control proposal; stopping the production and
import of PCB's or equipment containing PCB's, and
finally banning the manufacture and sale of PCB-con-
taining products.
In the analysis of our PCB's we have tried to consid-
er the complete life cycle of the product. PCB's are pro-
duced by one manufacturer in the United States—the
trade'name is Aroclor—and about 40.5 million pounds
were produced in 1974. The sale of PCB's is currently
restricted to electrical use and casting waxes. In the past
they were used as transfer fluids from heat exchangers,
hydraulic fluids, and so forth. However, as you know, to
avoid potential adverse environmental impact, Monsanto
restricted domestic and export sales in 1972 to electric
installation equipment applications in which the product
is enclosed in a relatively well-maintained container
throughout its use. Monsanto and others offer PCB dis-
posal service.
We found that PCB applications are characterized
by their long-term utilization with the majority con-
trolled by utilities. Transformers, for example, were re-
ported to last 20 to 30 years, and capacitors to last 7 to
10 years.
The number of transformer manufacturers vary;
anywhere from 2 to 10 have produced PCB-containing
transformers. Primary use is as nonflammable electric
insulating oil. Previous estimates report approximately
5,000 transformers were produced per year with an aver-
309
-------
age PCB amount of about 5,000 pounds per transformer.
Value of shipments (1974 data) is estimated at $35 to
$45 million.
The number of people using capacitors varies. Esti-
mates range from 16 up to 50 capacitor manufacturers.
There are approximately 90 to 100 million units per
year produced with a value about $105 to $147 million.
There are primarily two types: large utility capacitors,
using about 9 to 13 million pounds of PCB's per year,
and small industrial capacitors, using about 17 million
pounds per year.
In the case of casting wax, there is only one manu-
facturer in the United States. PCB's represent 30 percent
of the components of the wax. The annual usage is
about half a million pounds. Primarily, it is imported.
We also found another indirect importation of PCB's—in
capacitors in electrical equipment.
The primary transformer users are utilities; others
include manufacturers of and users of electrically power-
ed rail equipment, furnace equipment, and electrostatic
precipitators. About 85 percent of PCB transformers are
used as network transformers by the utilities, and we
estimate that approximately 90 percent of the trans-
former uses are controlled by the utilities, either through
ownership or service contracts.
With respect to the capacitor users, electric utilities
use large capacitors and manufacturers and consumers of
goods use small capacitors. Electric utilities use them
primarily for power factor correction, and smaller units
are used for starting and other uses such as fluorescent
lighting. We estimate that about 2 to 3 percent of large
capacitors are consumed as replacements and about 5 to
10 percent of the small capacitors were consumed as
replacements.
With respect to the casting wax, approximately 98
percent of that is now recycled and the people in the
business maintain that the remaining 2 percent that is
left in the mold is destroyed when the mold is prepared
at high temperatures.
The final step is disposal. Monsanto and others have
specialized incincerator facilities for PCB liquids, primar-
ily for large uses such as transformers and capacitors
used by utilities.
The ban of PCB's was estimated to result in a one-
time cost of $13.7 million. There would be additional
expenditures of $110 million annually. The ban would
also affect regulatory codes, public safety, and other
intangible areas, and, as always, the net result would be
an increase in consumer costs.
The primary impact, which is on the manufacturer
and users, is estimated at $8.8 billion for one-time costs
and approximately $16 million for annual costs. Key
elements in this, surprisingly enough, were "red tape"
required by Senate Bill S776. There are also disposal
costs, plant rebuild costs, and salary costs.
Secondary impact on users of PCB's, PCB-contain-
ing products or services, and disposal organizations is
estimated at $4.9 billion for one-time costs and $93 bil-
lion for annual costs. Elements of secondary impacts are
primarily new plant rebuilds for increasing the capacitor
output of the United Slates, disposal, and the increased
cost of substitutes.
The annual costs reflect the forecasted increased
costs of electrical equipment manufacture and use, in-
cluding replacements of existing equipment. Since the
lifetime of large transformers and capacitors is 20 to 30
years, the additional annual cost, over $110 million, was
forecast for the same period.
In the proposed 38-month time period, industry
representatives indicated that for primary and secondary
transformer use, there would essentially be a shift to
mineral oil as a replacement for PCB's, since the environ-
ment and performance characteristics of other substi-
tutes are not thoroughly researched. Major technological
breakthroughs, such as development of substitute fluids,
were not forecast.
We did'use minimum cost estimates. The cost of
replacing a PCB transfoimer, for example—not necessari-
ly the transformer but the vault which is surrounded by
the building—has been estimated as varying anywhere
from $5,000 to $50,000. We used a figure of about
$10,000, which we consider low and very conservative.
The economic impact of changing the regulatory
codes cannot be accurately quantified without a detailed
survey. However, the impact of the changeover for those
localities with regulations was estimated not to cause
major dislocation in building activities. We do know that
many cities permit only nonflammable, essentially PCB,
electrical equipment to be installed in tall buildings;
however, others do permit non-PCB transformers with a
vault.
Intangible issues include public safety, which would
be impacted by a ban on PCB's. Analysis would require a
detailed analysis of the tradeoffs between the benefits of
the product versus the benefits of the ban. Electrically
driven-trains use PCB transformers and it has been re-
ported that the flammable liquid in the transformer
would be a potential hazard. Uses of other transformers
in rail cars, if possible, would require redesign and over-
haul of existing equipment. Use of large quantities—over
20 gallons of liquid—in buildings would present a poten-
tial danger even in walls. Insurance underwriters have
reportedly studied the problem but nothing has been
presented as a request to change rates.
Other intangible areas are in replacements for all
types of equipment. Dry transformers, for example, are
310
-------
reported to have a low reliability. There are also specific tics, forcing either salvage or scrappage of the equip-
areas, such as replacement capacitors for compact equip- ment.
ment in which the capacitors cannot be replaced with a In assessing all these costs, we forecasted pass-
non-PCB-containing unit similar in size and characteris- through to the consumer.
311
-------
THE USE OF DOW CORNING Q2-1090 DIELECTRIC
LIQUID IN POWER TRANSFORMERS
Richard H. Montgomery*
Abstract
Dow Corning has developed Q2-1090 Dielectric
Liquid to replace askarels in transformers. Five years of
laboratory and field testing have shown it to be both
efficient and safe. It is now being sold in commercial
quantities both for new transformers and for retrofitting
old transformers. With some redesign, competitive en-
tries, and further restrictions on PCB use anticipated, it
is expected to have favorable economics. A 3- to 5- year
phase-in to completely commercially qualify the liquid
in all applications is planned.
Thank you for the opportunity to come here today
to represent the silicone industry, which in the United
States consists of the Dow Corning Corporation, the
General Electric Corporation, Union Carbide, and
Stauffer Chemical. The global silicone industry is now 5
years into a program to qualify dielectric fluid replace-
ments in both transformers and capacitors. The Japanese
silicone industry and Dow Corning Corporation have led
this effort to date. As a result of this extremely large
effort by the industry, I am very pleased today to make
two major announcements.
First, the technology to commercially manufacture
a capacitor dielectric fluid with superior dielectric pro-
perties is being developed. This material appears to with-
stand any of the high electrical stresses the material
would normally be used for in the industry. We plan to
make this product commercially available during 1976.
At its present state of development, we know of no
environmental problems with this particular product. No
chemistry would indicate there should be any. But this
will be continually studied, as have other products from
the silicone industry.
Second, Dow Corning now has commercial produc-
tion available to manufacture silicone transformer
liquids in sufficient capacity to handle the global trans-
former market, and that is a very large investment. So let
me now turn in some detail to the transformer industry
and the role silicones can play.
We must remember that today three environ-
mentally safe transformer systems are available to re-
place transformers filled with PCB liquids. Gas-cooled,
•New Product Market Manager, Fluids and Lubricants
Marketing, Dow Corning Corporation, Midland, Michigan.
air-cooled dry types, and liquid-silicone-filled trans-
formers will meet almost every need where PCB-
containing transformer fluids are used.
The silicone industry has produced insulating
materials for transformers for 25 years. The industry's
newest material, a silicone transformer liquid, is now in
use in Japan as a direct replacement for PCB-containing
transformer oils. In the United States, extensive field
testing has been under way for 4 years and at the present
time this material is being examined for inclusion in the
U.S. National Electrical Code.
Now, to underscore Dow Coming's personal assur-
ance in the safety, the elficacy, and the efficiency of this
liquid, Dow Corning has. notified its vendors that we will
be specifying silicone-filled transformers for all the new
transformers in our production plants around the world.
Our existing askarel transformers, in which we have a
very heavy investment, are being phased out rapidly
through a silicone retrofit program. Over 6 transformers
have been installed new or retrofitted in the past year,
and this program will accelerate in the spring. It is, of
course, not possible in Michigan during the winter
months to drain the PCB's satisfactorily and replace
these materials with a silicone fluid.
The material that we are talking about is known
today as Q2-1090 dielectric liquid. Basically, Q2-1090
transformer liquid is a dimethyl silicone that has been
specially formulated and qualified for use in electrical
applications. The technical feasibility of using the sili-
cone in transformers has been shown in over 20 years of
experience in military Iransformers, in several years of
use on the Japanese National Railway, and in a number
of power transformers in the Midland, Michigan, area;
several other areas around the United States will also test
silicone transformers in the next few months.
In addition to these actual applications, which
today are well known and have worked out nicely, sup-
port for the use of a silicone dielectric fluid in power
transformers is contained in over 30 years of accumula-
ted data on dielectric properties and compatibility with
the common materials of transformer construction.
The present concern for fire, explosion, health, and
environmental hazards are all strong reasons for an evo-
lutionary approach to using silicones and qualifying
them in this application for all major power transformer
uses over the next few years.
The silicone liquids of this type are much less
312
-------
flammable than typical mineral oils. They actually have
a higher flash point than many PCB-containing trans-
former fluids. Although they will burn, they have an
extremely low heat of combustion, extremely high flash-
points and firepoints, and they have been shown in
catastrophic testing to be self-extinguishing. They appear
to offer a level of fire safety greatly superior to mineral
oils.
The silicone that we are now recommending, a
dimethyl silicone, has been evaluated by Underwriters
Laboratory, and has received an extremely low flamma-
bility classification number. In Japan and the United
States, transformer cases containing PCB's, silicones, and
mineral oil were subjected to catastrophic failure testing.
In both tests, all liquids exploded. Most important, fol-
lowing this test, only the mineral oil continued to burn.
Both the polychlorinated biphenyl materials and the sili-
cone fluid self-extinguished. Normally, in a test of this
type you would fuse the circuit cutout. The fault in the
silicone fluid self-cleared, thereby extinguishing the arc.
With the other materials, the backup fuse blew and ex-
tinguished the arc.
Following the review of some very extensive data
(which is available to all of you by writing to me at Dow
Corning, provided you are willing to put in 4 or 5 hours
in reading it), the major insurance companies have given
their permission to use silicone fluid in indoor trans-
formers. Because it is a new material and since no gen-
eral policy has been established, the insurers have indi-
cated that they will evaluate each application on an in-
dividual basis; this is a conservative approach which we
highly applaud.
Dow Corning feels that we should look at a 3- to
5-year evolutionary approach of gradually putting a
larger and larger number of transformers into operation.
We are offering financial inducements to companies who
do this in order to collect a large body of case history
data that can be used to convince ourselves and the in-
dustry that there are no fatal flaws that have been over-
looked. It's an extremely conservative approach.
Silicones are often used in small concentrations in
the preparation of certain foods. Any time you eat a jam
or jelly or drink a glass of some of that good old Milwau-
kee beer, you are eating a food-grade dimethyl silicone.
And if you have an ulcer and you eat Di-Gel, you are
also eating it. They are excellent deflaccuants.
The toxicity of dimethyl silicones to mammals,
aquatic life, and plants has been very thoroughly investi-
gated. The extremely low toxicity of silicones has made
it difficult to detect any toxic reactions in test subjects.
Studies directed toward determining the tendency of sili-
cone to bioconcentrate have been negative. It has not
been possible to date to show that any bioaccumulation
was occurring.
It has been often stated that silicones are persistent
in the environment because they do not biodegrade,
under the evidence available at the present time. How-
ever, there is considerable evidence that silicones do
chemically degrade in the environment. Contact with
soil and water causes the liquid to depolymerize to low-
molecular-weight species, and known chemistry de-
finitely suggests that these degrade in water or in the
atmosphere.
Silicones cost more money than the current liquids
being used in transformers, but they are not outrage-
ously expensive. Referring to the entire market of
capacitors and transformers, and making some assump-
tions which would include the shipment of present pro-
ducts such as PCB's to the manufacturer's site, if we
include the shipping costs, my estimate is that the in-
dustry PCB purchases would be about $19.2 million.
If good engineering practices are followed to reduce
the amount of fluid needed, which has never been a
design criteria in the major manufacturer's mind, as
mineral oil, of course, is cheap, those costs would prob-
ably rise with the use of silicone to an industry figure of
$25 million.
So the total increased cost to the electrical and
electronics market would be about $5.8 million or 29
percent. If we made the assumption that the dielectric
fluids cost is 20 percent of the total material cost going
into a transformer or capacitor, we are talking about an
average cost increase of about 5.8 to 6 percent at the
manufacturing level on new equipment.
I feel that this slightly higher initial cost of silicone
liquid-filled transformers is more than offset by the cost
of monitoring and controlling of PCB-filled transformers
over their lifetimes. And with silicone, no known envi-
ronmental hazards are incurred.
PCB-filled transformers currently in service can be
changed over to Q2-1090 transformer liquid without un-
due problems. I think the work we have done over the
past 4 years—some of it in conjunction with Dow
Chemical, a lot of it in conjunction with leading trans-
former manufacturers—shows this.
I think you will be hearing not only from Dow
Corning in more detail on this subject. I highly suspect
that our worthy competitors, who can manufacture
dimethyl silicones to the same specifications once they
learn what they are, will go into the market. At that
particular time, the law of supply and demand will come
into effect. The silicone industry at the present time has
more capacity than it can sell. I anticipate the economics
will be extremely favorable for further consideration of
this product in both transformers and capacitors over
the next three years.
313
-------
DOW XFS-4169L: AN ENVIRONMENTALLY ACCEPTABLE CAPACITOR FLUID
Dean Branson, Ph.D.*
Abstract
Dow and McGrawrEdison Companies have devel-
oped a new capacitor fluid which is electrically, ecologi-
cally, and economically acceptable. Chemically, the new
fluid can be described as butylated monochlorodiphenyl
oxide.
(C4)n
n = 0,1,2,3
Dow XFS-4169L capacitor fluid
Dow XFS-4169L capacitor fluid performs equal to
or better than Aroclor 1016 in power capacitors. This
conclusion is based on dielectric losses, discharge incep-
tion voltages, capacitor size, fire hazard, reliability,
economics, and availability. Dow XFS-4169L capacitor
fluid and its components are acceptable in terms of
health and environment according to an assessment of
biodegradability, bioconcentration in fish, toxicity to
animals, and toxicity to fish. -Other capacitor manufac-
turers are currently evaluating XFS-4169L for applicabil-
ity in their respective companies. Field trails have been
started with utility companies across the country.
The contents of this presentation represent 4 years
of joint research between Dow and McGraw-Edison
Company which has culminated in the development of
an environmentally and electrically acceptable capacitor
fluid.
When RGB's replaced mineral oils some 40 years ago
in power capacitors, this represented another step for-
ward in the electrical industry's continuing effort to pro-
vide the public with low-cost electrical power and safer
electrical equipment. As a result of the use of PCB's,
there has been a downward trend in the cost per kilovar
•Capacitor Fluid H.N.E., Project Manager, Health and Envi-
ronment Research Laboratories, Dow Chemical, Inc., Midland,
Michigan.
of power factor correction.
In 1971, Monsanto limited the sale of PCB's for
dielectric uses where acceptable alternatives were not yet
available. Since then, industry has been searching for
alternatives which were ecologically, electrically, and
economically acceptable.
Today, we want to report to you that Dow and
McGraw-tdison have developed a butylated monochlo-
rodiphenyl oxide known as XFS 4169L. It meets all the
above criteria and can be used in high-voltage capacitors.
Initially, over 50 fluids representing several chemical
families were selected as possible dielectric fluids on the
basis of their chemical and physical properties. These
fluids were then screened for both electrical perform-
ance in miniature capacitors and for potential hazard to
the health and the environment in a battery of indicative
tests.
The conclusion of these screenings was that the
most promising chemical family was the alkylated mono-
chlorodiphenyl oxides.
Electrically, several members of this family per-
formed equal to or better than Aroclor 1016. It was the
health and environmental data that demonstrated the
significant advantages of the butylated monochlorodi-
phenyl oxides.
Electrical Performance
The confidence that McGraw-Edison Company has
in high-voltage capacitors made with the XFS fluid is
based on the following assessment of these six key elec-
trical performances.
1. Dielectrical losses. The dielectric losses are as low or
slightly lower than for capacitors with a PCB known as
Aroclor 1016. This is true for both paper-film and all-
film high-voltage power capacitors. This means that the
capacitors will operate under normal temperatures and
that the operating costs will be minimal. This is one of
the same significant advantages that PCB's have relative
to mineral oil.
2. Discharge inception voltages. Discharge inception
voltage is significantly higher than for Aroclor 1016 in
both paper-film and all-film capacitors. This means that
operating voltages may surge at least 20 to 30 percent
higher without resulting in temporary malfunction due
to electrical discharges known as corona.
3. System size. The size or volume per unit of high-
voltage power capacitor correction known as kilovar is
314
-------
the same as for comparative capacitors impregnated with
Aroclor 1016. This means that it will not be necessary to
redesign capacitors, the capacitor manufacturing, or the
application of capacitors.
4. Fire hazards. As indicated with RGB's, there is a low
risk of explosion and fires from power capacitors im-
pregnated with XFS 4169L. A major problem associated
with a failure in a paper-film power capacitor is the
decomposition of the paper and, to a lesser degree, the
film. The resulting pressure of the gases formed is a
major cause of tank rupture. After failure, the flamma-
bility of the fluid may contribute to a fire only if the
paper, the film, and the fluid, are above the ignition or
flash temperatures.
Under normal operating conditions, a capacitor will
operate between 40° and 80° C. At a time of failure, this
temperature will have to exceed the flashpoint of the
capacitor fluid before this fluid becomes contributive to
the explosiveness or the flammability of the system. In
this regard, the flash temperature for the existing dielec-
tric fluids for mineral oil is 154° C; for Aroclor 1016,
166° C; and for XFS 4169L, 104° C. The fire tempera-
ture for mineral oil, 167 PCB, is greater than 316° C; for
XFL 4169L, it is 199° C. This clearly shows that the
flash and fire points are substantially above the operat-
ing temperatures.
The National Electric Code allows the installation of
the electrical devices without a vault if they contain less
than 3 gallons of burnable liquid. The most common size
of our capacitor used today is a 200-kilovar unit. These
units contain less than 3 gallons of fluid, and are in-
stalled predominantly outdoors.
5. Capacitor reliability. Power capacitors impreg-
nated with XFS are more reliable than the same type of
capacitors impregnated with Aroclor 1016. This con-
clusion is based on results of comparative evaluations.
The following tests have been completed. Three years of
accelerated life tests, more than 18 million kilovar hours
in full-sized units without failures. Hundreds of sample
capacitors operating up to 200 percent of the rated volt-
ages for a wide range of temperatures, minus 60° to plus
125° C.
6. Economics and availability. The long-range price of
power capacitors impregnated with XFS 4169L will be
reasonable. The increased price or expense attributed to
the fluid is expected to be less than $20 for a 200-
kilovar unit.
Dow has assured the electrical industry that it will
have the manufacturing capabilities to produce XFS at a
million pounds per year rate during the first quarter of
1976. Should this fluid prove to be acceptable to the
industry, Dow is willing to make the commitment to
produce the fluid in multimillion pound quantities per
year by the end of 1976.
Health and Environmental Assessment
The Dow Chemical Company's assessment of the
health and environmental acceptability of XFS 4169L as
a dielectric fluid in capacitors is based on the following
criteria.
1. Biodegradability. The components in XFS 4169L
are significantly more biodegradable than the compo-
nents of Aroclor 1016. With micro-organisms, the rates
of formation of radioactive carbon dioxide from radio-
labeled components of XFS 4169L are much faster than
for 2,5,2' trichloro biphenyl, a major component of Aro-
clor 1016. The major component in 4169L is 45 times
more biodegradable than the representative PCB isomer.
This rate of biodegradability is comparable to several
nonpersistent industrial chemicals.
2. Bioconcentration. The bioconcentration factors in
fish of the components of XFS 4169L are low relative to
the components of Aroclor 1016. The environmentally
significant components in each fluid show a factor 30
times less bioconcentratable in trout muscle for XFS.
3. Toxicity to animals. In both acute and 90-day toxic-
ity tests with animals, XFS shows very little toxicity.
For example, in rats, a dose of 10 grams per kilogram of
XFS 4169L was administered orally and had no observ-
able effect on rats.
The levels of the components of XFS that accumu-
lated in the fat of rats fed the XFS in the diet for 150
days were significantly lower than for the comparable
dietary tests with Aroclor 1016. For example, the accu-
mulation in the fat was 22 times less for XFS; the appar-
ent plateau'level was achieved in 1 to 2 months com-
pared to 6 to 7 months for the PCB, and the estimated
half-life of the rat was 7 days with XFS compared to 60
days for the PCB. This indicates the relatively low degree
of toxicity associated with XFS 4169L in animals.
4. Toxic/ties to fish. The XFS material is only moder-
ately toxic to fish compared to capacitor-grade PCB,
which is extremely toxic. The concentration of XFS that
was toxic to fathead minnows was 15 milligrams per liter
compared to 0.76 milligrams per liter of Aroclor 1016,
which is a factor of 20 times less toxic to the fathead
minnow.
Dow and McGraw-Edison Companies have deter-
mined that XFS 4169L is an acceptable alternative to
capacitor-grade PCB in high-voltage power capacitors.
This is based on the electrical performance and its low
potential impact on health and the environment.
Today, McGraw-Edison is proceeding with field
trials of capacitors at utility companies across the
315
-------
country. Other U.S, manufacturers of power capacitors The information about XFS in this discussion is
are currently evaluating XFS for applicability in their only a very brief summary of the toxicological and
respective companies. ecological data which have been generated.
316
-------
CHLORINATED BIPHENYL DIELECTRICS-
THEIR UTILITY AND POTENTIAL SUBSTITUTES
David Wood*
Abstract
The paper describes the major reasons for the use of
chlorinated biphenyl in capacitors and transformers.
These lead to establishment of objectives for research
into potential substitutes. MCS-1238, a non-PCB capaci-
tor fluid developed by Monsanto, is discussed and areas
where further development work is required are indi-
cated. The particular problems associated with definition
of "fire resistance" relative to transformer fluids is
raised.
I. INTRODUCTION
In 1970, Monsanto voluntarily began its program of
terminating sales of chlorinated biphenyls to open appli-
cations—those which could result in losses to the envi-
ronment. By late 1972, this program was fully imple-
mented and Monsanto was selling these products only to
manufacturers of sealed electric equipment such as trans-
formers and capacitors.
Major applications affected by our withdrawal were
carbonless paper, fire-resistant hydraulic fluids, heat
transfer fluids, and plasticizers. Sales for other miscella-
neous minor applications were discontinued during the
same period. This action resulted in a reduction of some
45 million pounds per year in the use of chlorinated
biphenyl in areas where entry to the environment was
less controllable.
We decided at that time to continue supply to
closed electrical applications because we believed that:
1. Entry of chlorinated biphenyl to the environment
was limited and controllable;
2. A more biodegradable, lower chlorinated homolog
had been developed which the capacitor industry
could use;
3. Withdrawal would have brought to a halt produc-
tion of equipment essential to the safe and efficient
distribution and use of electrical energy because
there was no known satisfactory replacement for
chlorinated biphenyl dielectrics.
Today we continue to sell chlorinated biphenyl,
observing the following policy:
1. We supply only to manufacturers of sealed electrical
equipment such as capacitors and transformers.
2. We supply lower chlorinated homologs, Aroclor
1016, to the capacitor industry.
"Manager, Product and Marketing Dielectrics, Monsanto
Industrial Chemicals Company, St. Louis, Missouri.
3. We offer an incineration service for liquid PCB
wastes.
4. We continue to work with ANSI Committee C107
and other bodies to establish appropriate handling
and control procedures for equipment containing
chlorinated biphenyl.
5. We allocated increased research resources in 1969 to
seek and develop effective replacements; this pro-
gram continues.
6. In seeking possible replacements, we will insure that
differences between Aroclor and candidate fluids
from our program are widely reviewed in order that
the potential impact of any compromises is fully
evaluated.
The implementation of these and other programs both
by ourselves and electrical equipment manufacturers was
prompted by the utility of this dielectric family and the
difficulties inherent in developing substitutes to effec-
tively and fully replace it.
II. UTILITY OF CHLORINATED BIPHENYL
IN CAPACITORS
1. Fire Resistance
The adoption of chlorinated biphenyls in 1929 as
capacitor dielectrics stemmed from their superior dielec-
tric properties compared to mineral oil. However, recog-
nition of the fire-iesistant character of the fluids influ-
enced system and equipment design and standards over
the subsequent 45 years. It is probably true that today
many people find it difficult to assess potential capacitor
fire hazard purely because Aroclor has been used for 45
years.
Particular examples where fire resistance in a
capacitor is of benefit include:
a. fluorescent lighting ballasts,
b. air-conditioner motor capacitors,
c. television capacitors,
d. large power capacitors where high fault currents
can cause rupture and ejection of fluid from
pole-mounted units close to people and build-
ings,
e. industrial furnace capacitors.
2. Stability
The persistence of chlorinated biphenyl in the
environment is associated with the high degree of ther-
mal, chemical, oxidative, and hydrolytic stability which
permits capacitor manufacturers to fulfill the exacting
reliability requirements that exist today.
317
-------
3. Dielectric Constant/Dielectric Strengths
These properties are important in determining the
size of a capacitor. In a mixed dielectric system, e.g.,
paper/Aroclor or paper/polypropylene/Aroclor, the
dielectric properties of Aroclor permit optimization of
stress distribution between the components making up
the dielectric layer. This has enabled capacitor manufac-
turers to reduce paper and film volumes for a given
capacitance. I shall discuss under the heading of "poten-
tial substitutes" the impact that this could have on:
a. paper/film availability and usage;
b. design of equipment containing capacitors.
III. UTILITY IN TRANSFORMERS
Chlorinated biphenyl transformers represent less
than 15 percent of transformers in service. Their use is
associated with the need to limit fire hazard in installa-
tions.
1. Railroad Transformers
Multiple unit cars as used in rapid transit systems
have transformers mounted beneath each car. By nature
of the type of service, involving high passenger density,
safety is essential.
2. Urban Power Substations (e.g., Underground
Vaults)
These designs need to take into account city center
space limitations and also the safety of the public and
maintenance crews. Fire-resistant liquid transformers are
helpful to all these objectives.
3. Industrial Load Centers
Efficient system designs for large, power intensive,
manufacturing plants (e.g., automotive assembly, steel
production) often incorporate transformers close to the
electrical load centers. The use of Aroclor transformers
at these centers, in the heart of the plants, or overhead
in roof structures, protects both employees and plant.
4. Transformer/Rectifiers
Programs to reduce the emission of paniculate
matter from stack gases, for example in fossil fuel
generating plants, include installation of electrostatic
precipitators. The transformer/rectifiers energizing the
precipitator field must be located close to the electrodes.
In many designs, the multiple transformers are located in
a penthouse above the precipitator. A fire in the pent-
house could lead to shutdown of the precipitator, and
thus the generating plant, if pollution control is to be
maintained. A fire-resistant fluid is of obvious benefit in
this application.
In each of these applications, Aroclor protects the
system from:
a. initiation of a transformer fluid fire by an elec-
trical fault beneath the liquid level,
b. electrical breakdown of the fluid causing emis-
sion of flammable gases,
c. propagation of fire if the transformer liquid
content is involved in an external fire.
IV. POTENTIAL SUBSTITUTES IN CAPACITORS
1. Research Objectives
In seeking potential substitutes, our research objec-
tives of necessity involved keeping those properties that
gave Aroclor its value. We equally recognized the need
that an Aroclor replacement should eliminate environ-
mental concerns. A replacement should ideally operate
across the full range of current Aroclor capacitor appli-
cations while requiring minimum changes in design of
capacitors and equipment utilizing capacitors.
The use of chlorinated biphenyl is worldwide.
Monsanto manufactures chlorinated biphenyls both in
America and Great Britain. We supply to the capacitor
industry of many countries. We sought potential replace-
ment products that could be made available with the
consistent quality control applied to Aroclor on a world-
wide basis.
We referred earlier to availability of codielectric
components in capacitors. A solution requiring substan-
tial changes in availability of polypropylene film
(quantity or quality) or a major increase in short-term
availability or capacitor paper, we considered unsatis-
factory. If in 1974 such increased quantities had been
required, they would not have been available. Capacitor
production would have fallen short of demand, further
jeopardizing efficient power supply.
Our research objectives can be broadly summarized
in table 1.
2. Non-PCB Candidates
The capacitor industry is currently examining two
Monsanto non-PCB (candidate) dielectrics. These con-
tain no chlorinated biphenyl and are not chlorinated
products. The two fluids are designated MCS 1238 and
MCS 1588. Both of these products are blends of syn-
thetic hydrocarbons with a high dielectric constant
additive to give a dielectric constant equivalent to
Aroclor 1016. Table 2 lists some of the properties of
MCS 1238 and MCS 1588 compared to Aroclor 1016.
318
-------
Table 1. Research objectives in seeking
potential substitutes for capacitors
1. Match or exceed Aroclor 1016 capability:
a. Dielectric constant - Usage of other components
Dielectric strength - Convertability
b. Stability - Reliability
Power factor
c. Fire resistance - Safety
2. Good environmental compatibility:
3. a. Span existing appli-
cations - Complete solution.
b. Internationally - Not solely U.S.A.
available situation.
Table 2. Some properties of MCS 1238 and MCS 1588
compared to Aroclor 1016
Aroclor
Property
DK 25° C
100° C
Corona IV/EV3
Hydrolysis stability3
(neutralization number)
Dissipation factor fluid
tan 6 60 Hz. 100° C
Dissipation factor model
paper capacitor at 90° C
1016
5.9
4.85
-
0.00
0.0025
0.0032
MCS
1238
6.0
5.1
-
0.00
0.05
0.0039
MCS
1588
6.1
5.1
-
0.00
0.05
0.0035
aSee text explanation, section IV 2.
319
-------
Corona inception and extinction voltages are more a
function of capacitor design than of the liquid itself.
Preliminary industry results demonstrate functioning in
capacitors equivalent to Aroclor 1016. Further full-scale
work is required before final conclusions can be drawn.
Dielectric constants relate closely to those of
Aroclor 1016 over the temperature range of capacitor
operation. Hydrolysis stability is mentioned because of
work carried out on earlier candidates based on esters,
which gave concern because of hydrolysis instability.
Hydrolysis was assessed by measuring the neutralization
number of a sample with 0.5 percent water added, which
had been heated for 168 hours at 210° F in a stainless
steel bomb along with an aluminum and a mild steel
coupon.
3. Fire Resistance
Neither MCS 1238 or 1588 is fire resistant. This
deficiency versus Aroclor 1016 must be closely con-
sidered.
4. Environmental Considerations
The environmental/health evaluation of capacitor
replacement fluids must be related to:
a. Degradation-lf some quantity enters the
environment, at what rate and through which
mechanism will it degrade?
b. Tissue accumulation
c. Toxicity—Occupational safety
Environmental compatability
5. Degradation
Biodegradation has been studied using a semi-
continuous activated sludge technique. Forty-eight-hour
exposure of Aroclor 1254, Aroclor 1016, and MCS 1238
dielectric fluids to activated sludge using a semicontinu-
ous procedure resulted in the percent biodegradation
rates and 95 percent confidence limits shown in table 3.
For the polychlorinated biphenyl (PCB) materials,
the level of chlorination appears to be the most signifi-
cant factor in their relative biodegradability. The rate of
biodegradation decreases as the number of chlorine
atoms per biphenyl molecule increases. Chromatograms
representing samples after exposure to activated sludge
show significant alteration in the Aroclor 1016 isomer
distribution, but little for Aroclor 1254. Degradation of
the nonhalogenated fluid, MCS 1238, proceeds much
more rapjdly than for 1he halogenated PCB fluids with
no evidence of resistant components. The methodology
for this technique is described in appendix B.
6. Tissue Accumulation
Figure 1 depicts the results of rat tissue residue level
studies vs. time and compares Aroclor 1242, Aroclor
1016, and MCS 1238. A fraction of the ingested Aroclor
1242 and Aroclor 1016 was stored in rats' lipid reser-
voirs. However, most of this residue was depleted after
the rats had been on the basal laboratory diet for several
weeks. During the course of the feeding study, residues
of Aroclor 1016 accumulated more slowly and to a
significantly lesser extent than those of Aroclor 1242.
During the recovery period, these PCB residues de-
creased to lower values for Aroclor 1016.
The residue concentrations of MCS 1238 quickly
reached a stable level well below the concentration in
the feed. The residues did not increase with continued
exposure. After feeding ol the treated chow was ceased,
the MCS 1238 residues were rapidly metabolized and/or
excreted. The tissue residue accumulation and depura-
tion profile of MCS 1238 shown in figure 1 is markedly
different than those of the Aroclor fluids, especially that
of Aroclor 1242. Methodology is given in appendix A.
Table 3. Results of biodegradation using a
semicontinuous activated sludge technique
Material
48-Hour
percent
biodegradation
Feed
concentration,
PP"i
Aroclor 1254
Aroclor 1016
MCS 1238
15 + 38
33 + 14
70 + 10
1
1
3
320
-------
I
25 PPM FEED LEVEL FOR RATS
RECOVERY PERIOD
HI
UJ
LU
CC
EXPOSURE
PERIOD
AROCLOR 1242
AROCLOR 1016
MCS 1238
20
40 60 80
TIME (DAYS)
100
Figure 1. Results of rat tissue residue level studies
vs. time, comparing Aroclor 1242, Aroclor 1016
and MCS 1238.
321
-------
7. Toxicity
Before samples of MCS 1238 could be evaluated in
the capacitor industry and within Monsanto, acute
toxicity data was gathered:
a. Rat—Acute single oral dose LD50: 3,800
mg/kg.
b. Rabbit-Dermal LD50: 5,000-8,000 mg/kg.
c. Rabbit —Potential eye irritation: A slight
degree of irritation resulted when 0.1 ml of
undiluted MCS 1238 was placed in the conjunc-
tival sac of the rabbit eye. The average maxi-
mum score recorded at one and again at 24
hours after treatment was 12.0 on a scale of
110.0. All eyes had regained normal appearance
72 hours after dosing.
d. Rabbit—Potential skin irritation: When un-
diluted, MCS 1238 was held in continuous
24-hour contact with intact rabbit skin, a
moderate degree of irritation resulted. The
maximum average score was 3.6 on a scale of
8.0.
Further programs are in process, or scheduled, to
study the following:
a. vapor inhalation,
b. ultimate degradation,
c. 90-day pilot feeding study,
d. long-term (2-year) feeding studies, and
e. fish tissue residues.
8. Conclusions
To summarize Monsanto research activities:
— A large number of single compounds and mixtures
have been evaluated in terms of physical property
data, environmental compatability, fire resistance,
and model capacitor life testing.
— These have led us to conclude that: _
a. Aroclor 1016 may well be sufficiently de-
gradable to remain in controlled use,
b. MCS 1238 is a potentially acceptable replace-
ment with the qualification that it is not fire
resistant.
— Further programs must be completed with MCS
1238 in order to:
a. deepen our knowledge of its environmental
compatibility.
b. permit complete evaluation by the capacitor
industry across their range of applications,
c. enable utilities, capacitor users, and agencies to
evaluate the significance of decreased fire resist-
ance.
As a closing thought to this section, I would like to
comment that since 1929 when Aroclor was first
developed as a capacitor dielectric, normal commercial
pressures have spurred efforts to find superior replace-
ments. The awareness of environmental accumulation of
chlorinated biphenyls from other applications added
further impetus for more intensive research in the
chemical and electrical industries. Aroclor has defied 45
years of search for a superior replacement.
V. SUBSTITUTE TRANSFORMER FLUIDS
Neither Monsanto nor any other company, to our
knowledge, has developed a transformer dielectric with
equivalent fire resistance to that of Aroclor. The diffi-
culties that we face in common with other workers in
this field are twofold:
1. Aroclor has become the reference standard for fire
resistance in transformers because it works and has
'worked for 45 years. To establish standards to guide
research effort, there is a need for objective evaluation
of the fire hazard associated with the major sectors of
transformer use.
2. The chemistry which imparts fire resistance tends
also to produce stable molecules. Monsanto seeks
replacement products that will provide protection
against:
a. fire from transformer faults under the liquid
surface,
b. fire from secondary ignition of gaseous arc
decomposition products,
c. fire propagation if the transformer is involved
in an externally initiated conflagration.
We strive to accomplish this and produce an
environmentally compatible product. We have four
candidates which are currently being evaluated by the
transformer industry. These materials are in a suffi-
ciently early stage of development that it would be
premature to give detailed property data at this meeting.
322
-------
APPENDIX A
METHODOLOGY FOR FEEDING STUDY
Feeding and Sampling
Rat chow containing 25 ppm Aroclor 1242, Aroclor
1016, or MCB 1238 was prepared by mixing the
products into Ralston Purina rat chow. The treated
chow was fed ad libitum to adult albino rats for an
exposure period of 30 days. Following the 30-day
exposure period, all remaining rats were placed on the
basal laboratory diet. At predetermined intervals during
the exposure and recovery periods, five rats from each
exposed set and a control set were sacrificed. Fat tissue
was excised for analysis and composited for each group.
Samples were quick-frozen and stored in glass containers
with aluminum foil-lined caps to minimize risk of
contamination.
/so/at/on
The dielectric fluid residues were isolated from the
fat by solvent extraction. A weighed amount of fat was
placed in an Erlenmeyer flask and homogenized three
times with 25 ml of pesticide-grade hexanes and anhy-
drous sodium sulfate using an ultrasonic homogenizer.
The combined supernatants and washings were filtered
through anhydrous sodium sulfate and diluted to 100 ml
with hexane.
Lipid Weight Determination
A 5 mi-aliquot of the extract solution was pipetted
into a tared 50-ml beaker. After evaporation of the
solvent under a stream of nitrogen, the beaker and resi-
due were reweighed to obtain the lipid weight of the
aliquot. All residue levels are reported as ppm on a lipid
weight basis.
PCB Cleanup And Measurement
Sample cleanup for the extracts containing Aroclor
1242 and Aroclor 1016 residues was accomplished by
pipetting an aliquot of the extract onto a 5 percent
deactivated alumina column and eluting with 125 ml of
hexanes. The column eluate was collected in a Kuderna-
Danish evaporative concentrator, a 3-ball Snyder
condenser was attached, and the solution was concen-
trated to 5 ml. The residue levels in the extracts were
measured by gas chromatography using an electron
capture detector.
Non-PCB Cleanup And Measurement
Sample cleanup for the extracts containing MCS
1238 residues required separation of the residues from
the lipid by preparative scale gel permeation chromatog-
raphy. Following the GPC separation, the extracts were
further cleaned up on an alumina column, collected, and
concentrated as above. The residue levels in these
extracts were measured by gas chromatography using a
flame ionization detector.
Calculations
Calibration curves for each product were prepared
by plotting detector response (total peak area) versus
nanograms of standard injected. Residue levels in the
samples were determined by summation of the total area
of peaks corresponding to peaks in the standard and use
of the appropriate calibration curve. The calculations
were done as follows:
(N)(V
Residue (ppm) =
where N = Amount of product from calibration
curve (ng),
Vp = Volume of final concentrate (ml),
V| = Volume injected (ul),
W = Lipid weight of original sample (g).
APPENDIX B
TECHNIQUE FOR BIODEGRADATION METHOD
Biodegradation Method
Since activated sludge is one of the most important
agents for sewage treatment, test procedures evaluating
its action are of great importance.
The semicontinuous activated sludge (SCAS)
method has been extensively utilized in the development
of biodegradable detergents. In our SCAS procedure,
patterned after the Soap and Detergents Association's
323
-------
standard method (1,2) mixed liquor (activated sludge
and supernatant) from a local domestic sewage treat-
ment plant is charged to magnetically stirred glass vessels
of 1.5-1 capacity. Means for aeration and sampling are
provided. The SCAS unit is generally operated using a
retention or aeration time cycle of 24 to 72 hours. At
the beginning of each cycle, synthetic sewage (300 mg
glucose, 200 mg nutrient broth, and 130 mg K2HPO4)
and the appropriate test material in ethanol solution are
added to the mixed liquor (2,500 mg/l suspended solids
concentration). Aeration is maintained until the end of
the cycle, at which time the sludge is settled and 1 I of
supernatant drained. The cycle is then reinitiated by the
addition of tap water, synthetic sewage, and test mate-
rial. Operation of the units can be continued for an
indefinite period of time until consistent degradation
rates are observed.
Sample Analysis
Biodegradation of the test material was determined
during one cycle each week by analyzing 20 to 50 ml
mixed liquor samples withdrawn after feeding and at the
end of the aeration cycle. The mixed liquor analytical
procedure involved extraction with three successive
25-ml portions of hexane, and drying combined extracts
with anhydrous sodium sulfate. Extracts were concen-
trated in a Kuderna-Danish evaporative concentrator
equipped with a 3-ball Snyder condenser, and measured
by electron capture or flame ionization gas chromatog-
raphy. Calibration curves for each product were pre-
pared by plotting detector response (total peak area)
versus nanograms of standard injected.
The percent biodegradation was calculated from the
following equation:
percent biodegradation = (CQ - Cn)/Co x 100
where CQ and Cn use the initial and final concentration
of test material, respectively, on the mixed liquor.
1.
2.
REFERENCES
J. Am. Oil Chem. Soc., Vol. 42 (1965), p. 986.
J. Am. Oil Chem. Soc.. Vol. 46 (1969), p. 432.
324
-------
SOME COMMENTS ON ALTERNATIVES TO PCB's
Bruno Rey Coquais*
Abstract
In the transformer industry, the benefit of a non-
flammable liquid seems to exceed the risks of pollution
by polychlorinated biphenyls; however, to minimize
eventual contamination of the environment, it is suggest-
ed to use, when possible, a mixture of chlorobenzene
and trichlorobiphenyl or even chlorobenzene alone.
For the impregnation of capacitors, most of the sub-
stitutes which can be imagined are not very attractive,
though they are useful for certain applications. It is pro-
posed to use a mixture of pure dichlorobiphenyls and
their alkylated derivatives. This impregnant, named
chloralkylene, has dielectric properties very similar to
the industrial trichlorobiphenyl.
The tests in progress already show that chloralky-
lene is easily biodegradable and has a low toxicity. This
compound seems to be quite acceptable for the environ-
ment and should he a perfect substitute for polychlori-
nated biphenyls in capacitors.
To begin with, I would insist on the fact that heavy
chlorinated biphenyls have been used for a long time in
dispersive applications as plasticizers and for other uses.
Although these types of applications have been stopped
in accordance with the OECD recommendations of the
February 14, 1973, it is not surprising to continue to
find these persistent, highly chlorinated PCB's every-
where in the environment. It is therefore very difficult
to know if the electrical uses of PCB's for transformers
and for capacitors have a significant contribution to the
pollution of our environment.
TRANSFORMERS
PCB's are used in transformers only when the fire
hazard is high (department stores, theatres, movies,
skyscrapers, factories); otherwise oilfilled transformers,
which are cheaper, are always preferred. We do not think
dry-type transformers would be a competitive alternative
in spite of the fact that silicone and epoxy belong to the
range of products we market. They may be very attrac-
tive in some cases, but in addition to certain economical
and technical disadvantages, dry transformers do not
offer a perfectly safe solution wherever flammable va-
pors (solvents, oil, gas) may be present accidentally.
We believe a nonflammable dielectric liquid is abso-
*Development Manager, Prodelec, S.A., 25 Quai Paul
Doomer, Courbevoie, France.
lutely necessary to prevent the risk of fire in transform-
ers. In table 1 we have listed the different possible solu-
tions. In the United States, at this time, transformers are
filled with Inerteen 70-30, which is based on pentachlor-
obiphenyl, or with Inerteen 100-42. To minimize the
pollution risk, a mixture of trichlorobiphenyl and chlor-
obenzene or even the chlorobenzene alone could be used
in spite of some technological problems.
In any case, the systematic recovery of used PCB's
will further limit pollution hazards; our company Prodel-
ec has organized this practice throughout France since
1968, as soon as this pollution problem became known.
This systematic recovery has now been enforced in
France by the French law of July 8, 1975, on PCB's.
CAPACITORS
For capacitor impregnation, we have examined vari-
ous possible solutions. We think that the performances
of such compounds as silicone; sulfone or synthetic oil
(alkylbenzene, polybutene); phthalate; and sebacate—
which we are indeed selling ourselves for certain applica-
tions—are not really satisfactory enough for generalized
or widespread use.
In our opinion, a substitute to PCB's should be char-
acterized by:
High permittivity;
Nonflammability, at least not sustaining com-
bustion;
Compatibility with polypropylene film;
Being a permanent liquid with no crystalliza-
tion until -25°;
Good thermal and electric subfield stability;
Regarding its effect on the environment, being
fairly easily biodegradable, to eliminate the risk
of accumulation, and by having low toxicity.
To get a good and nonflammable dielectric fluid
means in practice that the compound must be a chlori-
nated aromatic hydrocarbon. We have studied, for in-
stance, new structures, as shown in figure 1. With chloro-
biphenyl oxide, we are afraid of the risk of metaboliza-
tion in highly toxic dioxins and we feel that products of
the family of the chlorobiphenylethane are technically
and environmentally much more promising. Actually, in-
troducing a totally new compound would require a long
and expensive testing program and it seems better to
take advantage of the huge amount of knowledge gather-
ed about PCB's and to see how it may be possible to
improve the present situation.
325
-------
Table 1. Possible solutions for dielectric liquid
IEC
type
Tl
T2
T4
T3
Chloro- Chloro-
biphenyl benzene
60% hexa 40% tri
45% hexa 55% tri
and
tetra
70% penta 30% tri
45% penta 55% tri
and
tetra
100% tri
60% tri 40% tri
40% tri 60% tri
and
tetra
100% tri
and
tetra
Pour Viscosity e
Point Cst at at 20° C
(°C) 20° C
<-33 21 4.5
<-40 11 5
<-30 20 5
<-40 10
<-18 65 6
<-50 7 6
<-20
Chrys- 6
tallize
-9
Hydrogen
index
<0
excess Cl
<0
excess Cl
0
<0
excess Cl
16
10
4
<0
excess Cl
Askarels
for
transfor-
mer
Pyralene
TI Pyro-
clor
Inerteen
70-30
Pyralene
T4
Pyralene
T2
Pyralene
T3 Iner-
teen 100
42
Pyralene
1460
aHwH™™n ir>HOv = No • hydrogen - No. chlorine
Molecular weight
326
-------
f
£
o
I
S
I
o
o°o°
v>
<£>
UJ
'. _J i
a/
o CM
i _i
o —o
•o
a>
a.
£
a>
o
o
o
n. 5 —
00 U. U.
M
CO
CM
O
_2
H-
o
*^_
•4-J
C!
TO
E
E
jo
M—
C
o
c
CD
z;
•M
o
CU
3
327
-------
a ci
CH,= CH-CH,
dichloro biplwnyl
2-2'
2-4'
Figure 2. Structure of chloralkylene.
Table 2. Composition of various impregnarits
Chloralkylene
Composition, percent 12
Biphenyl
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachl orobi phenyl
Pentachl orobi phenyl
Alkylchlorobiphenyl
isomers
Chlorine content, percent
'0
0
20
0
0
0
80
25.8
Pyralene
3010
(trichloro-
bi phenyl)
0
0
11.4
57.1
29.4
•2.2
-
42.
Pyralene
1500
0
0.5
37.5
40.0
20.5
1.5
-
38.5
Pyralene
2000
1.6
18.4
44.0
23.4
11.7
0.9
-
33.5
328
-------
Table 3. Comparison of chloralkylene to
commercial trichlorobiphenyls
Characteristics
Specific gravity at 20° C
100° C
Coefficient of expansion
Viscosity Cst. at 20° C
100° C
Pour point (ASTM D 97)
Firepoint (Cleveland)
Permitivity at 20° C
100° C
Resistivity
100° C - 500 V - 1 mn
Dissipation factor
+g6 100° C - 50 cps
Chloralkylene Pyralene 3010
12 (trichlorodiphenyl)
1.163
1.097
7.5 x
135
3
-25
258
6
4
>3000
<0
ID'4
.2
0 C
0 C
.00
.86
x 109
.02
1.391
1.319
6.8 x 10"4
65
2.3
-23° C
none until
boiling
5.93
4.80
>3000 x 109
<0.02
10
10 20
DAYS
30
22 CI28P
Chloralkylene g
2462'4'd5BP
35
Figure 3. Excretion by rats, with diet of 2 ppm/day for 5 weeks.
329
-------
8
&
I! 30J
o
x
LJ
I 2 3 4 5 6 7 8 9 10 II 12 13 14 15
2-5-4' CI3 BP
Figure 4. Excretion by rhesus monkey; single oral dose 1 mg/kg.
The studies carried on, in particular by Prof. Korte
and Dr. Klein in Germany, seem to prove the easy biode-
gradability of PCB's when they have a very low chlorine
conten*; therefore, oure mono- or dichlorobiphenyls
could be quite acceptable for the environment.
As an impregnant consisting only of mono- and
dichlorobiphenyls would crystallize at room tempera-
ture, it is necessary t<- produce a more complicated mix-
ture to get a permanent liquid at all temperatures. We
have therefore developed a product named "chloralkyl-
ene," obtained by addition of an alkyl chain, actually an
isopropyl group, on a mixture of nearly pure dichloro-
biphenyl isomers (figure 2).
As shown on table 2, chloralkylene contains no
penta- nor tetrachlorobiphenyl and the trichlorobiphen-
yl content can be extremely low. Technically, for its
dielectric and physical properties, the chloralkylene is a
perfect substitute to the commercial t,i°hlorobiphenyls
(Pyralene 3010, Arochlor 1016), as sho'.vn in table 3 and
as checked by some major capaci*~
-------
chloralkylene does not accumulate, is metabolized
quickly, and behaves generally like the dichlorobi-
phenyls isomers themselves.
Chloralkylene is two times less toxic than trichloro-
biphenyl when one compares the acute toxicity values.
At this time, there is no real reason to consider RGB's
dangerous for the labor manufacturing capacitors, if the
necessary precautions are taken. We think that with an
easily biodegradable compound such as chloralkylene,
long-term effects due to accumulation along the food
chain do not need to be feared.
The chloralkylene price is presently twice that of
the currently commercially available polychlorobiphen-
yls, which would result in an increase of the capacitor
costs of about 5/10 percent. However, by substituting
mineral oil or other substitutes with less outstanding
characteristics, the increase of the cost of capacitors
would be much higher. We hope to improve its economy
and are quite confident that chloralkylene could thus be
an excellent substitute for trichlorobiphenyls.
331
-------
PCB's AND THEIR SUBSTITUTES - A BRIEF LOOK AT
SOME EXAMPLES OF PAST TRADEOFFS
Dale Hattis, Ph.D., and Albert Murray, Ph.D.*
Abstract
Some aspects are described of a study of the
economic, health, legal, and other impacts of the past
voluntary restriction on PCB sales. Examples illustrate
the importance of examining the effects of substitute
technologies in assessing regulatory policy by showing
the potential for surprises in this regard. In the PCB case,
substitutes may be producing both unanticipated
economic benefits and unappreciated health and safety
risks.
I am Dale Hattis of the Center for Policy Alterna-
tives at M.I.T. My colleague at the center. Dr. Albert
Murr^,', who was originally scheduled to speak here—and
who would be the most appropriate speaker on this
subject—was unfortunately taken ill about a week and a
half ago and he is now still recuperating in the hospital.
What ! have done in his place for presentation today is
to extract some particular examples of tradeoffs from
Al's work on PCB's, which illustrate some occasionally
surprising features of the technological changes that arise
out of environmental/health concerns.
For context, I would like to say that our project,
sponsored by the Council on Environmental Quality and
EPA, and under the direction of Dr. Nicholas A.
Ashford, has for the past year been exploring ways to
analyze the economic, environmental health, legal, and
other impacts of regulatory decisions related to environ-
mental chemicals. In this exploration, we are now in the
process of completing eight experiments in the analysis
of the impacts of particular regulatory actions, primarily
drawn from the past 5 years of history. The first of our
eight experiments, though not strictly resulting from a
mandatory governmental action, was the restriction a
few years ago of the sale of PCB's for particular uses.
Because our case studies are experiments to explore the
practical use of methods, and because the resources we
could devote to each case were relatively small, we could
not perform as comprehensive an elucidation of effects
as we would have wished. Nevertheless, we do think that
our analyses have revealed important types of questions,
similar to those referred to yesterday by Mr. Train,
which are difficult to deal with in the single chemical
'Research Associates, Center for Policy Alternatives,
Massachusetts Institute of Technology, Cambridge, Massachu-
setts.
reactive context of most current regulatory authorities.
My initial two examples of such questions on PCB's
illustrate the fact that it is sometimes difficult to be sure
that technological changes introduced wfth the intent of
reducing environmental health risks accomplish their
purpose on balance, when the risks of substitute prac-
tices are considered. Sometimes there appear to be legiti-
mate reasons for concern that particular changes—
especially in the absence of continuing regulatory
followup-might create environmental health hazards as
dangerous or more dangerous than the ones that are
eliminated.
As a first example, the substitutes for PCB's in some
large heat exchangers and in some special hydraulic
fluids for high-fire-risk uses are flammable at elevated
temperatures. Concern for the lack of fire protection
previously provided by PCB's in these situations has
reportedly caused a substantial increase, as much as a
doubling in some cases, in fire insurance rates on some
industrial facilities employing high-temperature heat
exchangers. In our case study, Al Murray estimated the
total increase in premiums at possibly in the tens of
millions of dollars annually. This, of course, reflects
mainly property damage and not the human cost. How-
ever, if our information on the increased premiums is
correct, and if the apparent perception of the insurance
companies is correct as to l:he size of the added chance
of catastrophic fires, then we must consider that such
events would be likely to be accompanied by appreciable
human casualties. The rise in insurance rates, of course,
may not reflect an actual change in risk, and in that case
the increased insurance cost is simply a transfer payment
to the benefit of the insurance companies, but the mat-
ter seems to deserve further exploration with the aid of
hard statistics on actual fire-risk experience. If the data
confirm that appreciable human impact may be ex-
pected to occur, alternative means for reducing this risk
might be productively evaluated.
Another, although probably less important, example
of potential risk of substitute technology arises in the
case of the former use of PCB's as a dye-solvent for
carbonless carbon paper. It may be recalled that at some
frequency PCB's from this source found their way into
recycled paperboard products for food contact use, and
this was a source of concern for the FDA. Now the
PCB's formerly used for this purpose have been replaced,
but unfortunately it is not public information what
exactly has replaced them. The barrier of trade secrecy
332
-------
in this instance, as in many others, can frustrate at-
tempts to assess the difference in environmental health
risk produced by the change in technology.
Two other examples illustrate the potential for a
different category of surprises-those in the economic
area.
Formerly, PCB's costing on the order of 25 cents
per pound were used in many paints and coatings, some-
times as a major ingredient. In this application PCB's
were a chemically stable blender and conferred resist-
ance to fire, impacts, water, and weathering. Our inquir-
ies with paint manufacturers indicate that chlorinated
paraffins now perform essentially all the technical func-
tions of PCB's at about half the former cost. Our
industry informants mention some increased problems in
a few of their products with lowered stability to dechlo-
rination—causing occasional discoloration and loss of
weathering resistance-but over the great bulk of their
product lines, the industry perception appears to be that
the change has been economically beneficial. PCB's had
evidently become established as paint additives before
the availability and advantages of the chlorinated
paraffins became widely appreciated. Later, when
approximate technical equality and lower prices might
have tempted paint manufacturers to substitute, the
usual inertial resistance to any change appears to have
caused this opportunity to be generally neglected. The
real world and the economists' ideal one occasionally
behave differently.
Another example of a surprise (at least to us) in the
economic area is the potential importance of even small
adverse impacts on sport fishing. A U.S. Department of
Interior survey (ref. 1) indicates that in 1970 a total of
about 700 million person-days and five billion dollars
were spent in pursuit of this pastime - mainly in fresh
water. The five billion dollars must, of course, be con-
sidered an underestimate of the actual "value" of that
activity to people. If PCB's had continued to be used as
they were in the past, we might speculate that additional
concern of people about residues (such as that now
publicly in evidence), or possibly some declines in fish
populations might have led to small fractional declines in
participation or enjoyment of fishing by some portion of
the population. If this were to occur, the loss of value to
society of even less than a fraction of a percent of
national sport fishing activities might be appraised at
tens of millions of dollars annually—depending on the
"value" realized by former fishers in substitute recrea-
tional activities.
The importance of examining subtle and uncertain
effects, including the effects of substitute technologies,
is illustrated by such occasional insights into their poten-
tial magnitude.
REFERENCES
1. Fish and Wildlife Service, Bureau of Sport Fisheries,
U.S. Dept. Interior, "National Survey of Fishing and
Hunting," Resource Publication 95, GPO, Washing-
ton, D.C,, 1972.
333
-------
ENJ-2065-AN ELECTRICAL INSULATING FLUID
E. J. Inchalik, Ph.D.*
Abstract
The need for an electrical insulating fluid whose use
would avoid the adverse toxicological and ecological
effects associated with polychlorinated biphenyls
prompted a study of organic esters as possible substi-
tutes. The study culminated in the identification of
diisononyl phthalate (ENJ-2065) as a dielectric fluid of
potential interest to the capacitor industry. ENJ-2065
has been made available to that industry and it is now
being used in some commercial capacitors.
In late 1970, a study was begun at Exxon Research
and Engineering Company by Drs. A. J. Rutkowski and
E. 0. Forster to develop an electrical insulating fluid
whose use would avoid the adverse toxicological and
ecological effects associated with polychlorinated bi-
phenyls. This study culminated in the identification of
diisononyl phthalate (ENJ-2065) as a dielectric fluid of
potential interest to the capacitor industry. Exxon
Chemical Company U.S.A. has made ENJ-2065 available
to the industry for its evaluation and it is now being
used in some commercial capacitors.
In the preliminary phases of this study, the dielec-
tric properties of a significant number of mono- and
dibasic acid esters were determined in order to obtain a
general understanding of the interrelation between mo-
lecular structure and dielectric properties. From these
data it was concluded that major attention ought to be
directed at the esters of phthalic acid. The phthalates
that we tested all had dielectric constants of 4-6, close
enough to the desired level for fluids for the widely used
paper-based capacitors to justify further evaluation. The
optimum dielectric constant for these capacitor fluids is
one which closely matches the dielectric constant of the
paper. A close match reduces electric field inhomogenei-
ties, increases dielectric strength and lifetime, and de-
creases capacitor size. Other important property criteria
for a paper dielectric fluid include a low dissipation fac-
tor, to reduce energy loss and destructive heat buildup; a
high dielectric strength, to reduce capacitor size and im-
prove service life by permitting short-term exposure of
the fluid to abnormally high stresses without break-
down; a low gassing tendency, to avoid production of
gases that could lead to pressure buildup in sealed units;
stability at elevated temperatures, to prevent capacitor
"Research Associate, Chemical Intermediates Technology
Division of Exxon Chemical Company, Linden, New Jersey.
breakdown and stabilize performance; low viscosity, to
allow for easier impregnation and filling of capacitors
and elimination of air pockets; a low order of toxicity;
and compatibility with the environment.
Consideration of these factors as well as availability
and cost resulted in narrowing the choice of potential
candidates to those shown in table 1. From this list,
diisononyl phthalate (ENJ-2065) was selected as the
most promising for additional study. ENJ-2065 was cho-
sen on the basis that it has (1) a higher dielectric con-
stant than the phthalales of higher molecular weight, (2)
an advantage in its loss characteristics relative to the
lower molecular weight dihexyl and dioctyl phthalates,
(3) a relatively high flash point of 430° F, (4) a more
highly branched molecular structure than dihexyl and
dioctyl phthalates with the potential for improved
hydrolytic stability and (5) a good balance of other
physical and electrical properties. ENJ-2065 is manufac-
tured in the United States by Exxon Chemical Company
U.S.A. from phthalic anhydride and a mixture of
branched isomeric alcohols in which C9 alcohols pre-
dominate.
Electrical insulating fluids have to remain essentially
unchanged chemically when subjected to temperature
cycles. Once having chosen ENJ-2065 for further evalua-
tion, it was desirable to know what effect certain con-
taminants might have on its stability, how these contam-
inants might be removed, and what additives, if any,
might be useful in enhancing its stability.
The effects of small amounts of two potential con-
taminants, alcohol and water, on conductivity of
ENJ-2065 are shown in tables 2 and 3. The results show
that alcohol levels of less than about 1,000 ppm and
water levels of less than about 100 ppm can probably be
tolerated without affecting performance seriously. To re-
move small quantities of these impurities as well as any
acids or catalyst residues from the production of
ENJ-2065, we found percolation through a packed col-
umn of activated Attapulgus clay to be effective, but we
did not carry out extensive studies to optimize a purifi-
cation system. It is our feeling that systems now being
used in the industry for purification of PCB's prior to
use in capacitors, or slight modifications of them, will
prove to be satisfactory for ENJ-2065.
Although the most widely used capacitors today are
of the all-paper type, newer types based on polypropy-
lene film and paper or on all-polypropylene film are
growing in importance. With capacitors of this type, the
dielectric constant of the fluid is less important.
334
-------
Table 1. Electrical and physical properties
of phthalate esters
Phthalate
Ester Dihexyl
Dielectric
constant 5.64
Tan delta
AC conduc-
tivity,
10-"
1
(ohm-cm) 9.0
Breakdown
voltage
(KV/0.1
in.)
Boiling
point--mid
@ 5 mmHg,
°C 210
Pour point,
°C -33
Viscosity,
cps., 20° C 50
Flashpoint,
COC, °F 380
Firepoint,
COC, °F 420
Di-2-
ethylhexyl
5.33
0.14
2.1
28
230
-50
81
425
475
Diisooctyl ENJ-2065 Diisodecyl Ditridecyl
4.97 4.66 4.45 4.08
0.30 0.05 0.02 0.01
1.3 0.29 0.20 0.04
27 30 36 29
235 252 256 286
-45 -48 -50 -37
83 95 110 230
430 430 452 470
485 495 515 555
335
-------
Table 2. Effect of residual alcohol on
conductivity of ENJ-2065
12
Conductivity (10" ohm-cm)
Temperature cycle
(1,000 V, 60 Hz)
25° C
90° C
25° C
Wt.
0
0.78
40
3
percent
0.
1.
alcoffoT
01
97
65
4
added
0.1
1.98
320
12
Table 3. Effect of residual water on
conductivity of ENJ-2065
Conductivity (10 ohm-cm)
Temperature cycle Wt. percent water added
(1,000 V, 60 Hz) 0 0.001 0.01 0.1
25° C 0.78 2.7 3.7 135
90° C 40 165 >400 >400
25° C 3 10 25 70
Table 4. Weight gain of PP film in
contact with dielectric fluid
Fluid
ENJ-2065
Arochlor
1242
Run number
1 2 3
11.0 10.9 13.8
18.8 18.2 22.8
336
-------
Impregnation of the polypropylene film with the fluid, may well be based on metallized polypropylene film.
however, is of great importance and prompted a brief Polychlorinated biphenyls cannot be used for this type
study, summarized on table 4. These data show that of capacitor since they generate hydrogen chloride,
ENJ-2065 swells polypropylene capacitor-grade films which can lead to premature breakdown.
satisfactorily, as measured by the film weight gain after In summary, we believe that ENJ-2065 has a bal-
2 days at 60° C, so that film impregnation should not be ance of properties such that it will find a niche in the
a serious problem. The next generation of capacitors capacitor fluid field.
337
-------
GENERAL DISCUSSION OF SESSION V
CHAIRMAN MUIR: All right. I see that we have reached
our scheduled departure hour. I think it's only fair
to entertain a few questions from the audience and
given the diversity, I would request that people raise
a question from the floor and then address their
questions to the individual they would like an
answer from.
MR. BEN KININGHAM (Illinois Lung Association,
Springfield, Illinois): I do not have any particular
gentleman on the panel to address. I just want to
refer to the breakdown of the film, if anyone could
elaborate on how that comes about, and if so, is
there any research that is being carried on now in
development of films that would be any more
stable.
MR. RICHARD ROLLINS (Jard Corporation, Benning-
ton, Vermont): Are you talking about a biological
breakdown?
MR. KININGHAM: Biological or chemical or both
breakdowns.
MR. ROLLINS: It is a reduction type atmosphere in the
capacitor so it does not see the oxygen that would
normally be considered. The basic problem is not
one of the degradation as much as it is an inherent
characteristic of not being able to survive voltage
levels or stresses in an AC application.
MR. KININGHAM: Would it be feasible to develop an
alternative program?
MR. ROLLINS: The organic type films have been used
or have been attempted to be used in AC capacitors.
The basic problem is one of corona exception and
corona distinction 'voltages, and this is inherently
low and goes down to initiation of points 250 to
275 volts and the extinction voltage is extremely
low. The meaning of the corona is that the capacitor
slowly deteriorates by this ionic device which is the
definition of corona. The interpretations of corona I
am not going to get into today because every
capacitor designer has his own opinion, but every
capacitor designer is completely aware of what the
corona problems can do. So essentially what we are
saying is that organic films have the basic problem
of hot being able to withstand high AC voltages,
especially in the dry system.
On an impregnated system, the circumstances
are still there, so you are not really changing the
circumstances a great deal in all polypropylene film
or any organic film when you impregnate it.
VOICE: I have a question for Dave Wood. We heard a
number of things about environmental factors. How
about a still lower chlorinated material than 1016
that might be a more desirable material? I believe
Monsanto has passed a given developmental material
such as 1043, which is a lower chlorinated material.
MR. DAVID WOOD (Monsanto Industrial Chemicals
Company, St. Louis, Missouri): We have done
considerable work with MCS 1043, but at the
present time commercialization of such a product
must hang in the balance pending further conclu-
sions being drawn about the true significance in the
differences observed between the trichlorinated
materials and bichlorinated materials. Aroclor 1016
was itself a reduction in materials from the Aroclor
1042 widely used by the industry.
In order to carry through development of the
dichlorinated material, I think we need some
approvals from the community that they recognize
a movement in that direction as one that should be
taken.
So yes, some data are already available. Acceler-
ation or stopping of that program depends largely,
on some of the things that we hope will come out of
this conference this week.
MS. NANCY STROUP (Environmental Defense Founda-
tion, Washington, D.C.): I apologize for the open-
handedness ol my question, but I hope that the
panel members will respond as concisely as possible.
One of the speakers mentioned that his concern
was that we not jump from the frying pan into the
fire, and I am sure it's the concern of everyone at
this meeting. To that end I would like to know
when the four or five compounds that are now
being developed to replace PCB's will be tested for
the health and safety of these compounds, including
carcinogenic, immunogenic, and teratogenic tests
before your marketing. And whether this informa-
tion will be available 1or independent review.
DR. MUIR: Essentially, as I already outlined in my talk,
we developed a date for the work and the work is
going forward and we recognize the biphenyl prob-
lem and that replacing the product inevitably is
going to have to satisfy the most thorough and
rigorous testing.
DR. DEAN BRANSON (Dow Chemical, Inc., Midland,
Michigan): In the case of methosilicones additional
data will be published very shortly and will be
publicly available. I think this is most in the minds
of all manufacturers when they consider substitutes
338
-------
for the material which is dielectrically one of the
best ever developed. This will seem to solve the
problem when it comes out.
DR. E. J. IIMCHALIK (Exxon Chemical Company,
Linden, New Jersey): A great deal of information is
already available. You may recall in 1972 a program
sponsored by the National Foundation of Health
Sciences and one subject made by Dr. Tapper, what
he observed at comparison of PCB and mercury, it
was like an ideology searching for a disease, and
that's a quote.
The recent study by Dr. Hartung of the
University of Michigan has concluded that no prob-
lems attributable to polyesters have been noted due
to the constant low level exposure of the general
population, and that occupationally, only mild skin
irritation has been observed at high exposures. But
he did point out that ecological work should be
continued. And I might add that Dr. Tapper sug-
gested the same.
To help answer these questions, particularly
related to these items, a research grant has been
made by the University of Missouri to the Manufac-
turing Chemists Association, and they are starting
tests. I think we can hope within the next year or so
results will be coming from this study obviously
available to all which will help answer these ques-
tions.
MR. DUNCAN MacARUTHUR (Booze Allen and
Hamilton, Inc., New York, New York): Well, some
of the things that you have asked for are in progress
and when these things are available, they will also be
made available to the general public.
MR. DAVID C. MORRIS (Weyerhauser Company,
Tacoma, Washington): You stated, sir, that a cost
of $4.9 million would be necessary for I guess you
would call them secondary market users like my
company, to replace our PCB with some substitute.
Did I understand you correctly, Mr. Mac-
Arthur?
MR. MacARTHUR: Yes.
MR. MOSS: Just for my own sake, I just believe in it
very strongly, the cost alone is estimated at $2
million and we are right in the midst of investing.
And I think somewhere along the line the investing
might not take into account the factors that we
initially have to face. I would guess it's at least 50
times over.
CHAIRMAN MUIR: Yes, sir.
VOICE: There are three experimental items coming on
the market. Will someone label these transformers-
MR. ROLLINS: Well, I'm not too sure, but there have
been requests that major capacitors manufacturers
now conform by labeling all capacitors that have
greater than I believe 5 pounds of Aroclor-l may be
wrong, but on small capacitors, the basic problem is
the label gets hidden because this is placed into
another piece of equipment.
MR. STEVE NUMUS (Environmental Protection
Agency): I have a question for Richard Mont-
gomery regarding the use of silicone which was
approved by Underwriters Lab for indoor use. Do
you know the reasons why it was approved for
indoor use and why it was not approved for outdoor
use?
And secondly, can somebody give me an idea of
the percent of transformers in the United States
used for outdoor purposes as opposed to indoor
purposes?
MR. RICHARD H. MONTGOMERY (Dow Corning
Corporation, Midland, Michigan): First of all,
Underwriters Laboratory does not approve of any
particular material for any given use—once you
exceed 600 volts in a transformer. Underwriter's
Laboratories has no certification. The only certifica-
tion received from Underwriters' Laboratories is as
to the fire hazard of your particular material on a
scale which ranges from 0 to 100, with the burna-
bility of water as 0, and gasoline as 100. Therefore,
Underwriter's Laboratory does not approve silicone
material for indoor use.
In respect to the use of dielectric fluids in
transformers, the electric code for outdoor uses
does not specify nonflammable material. It does in
subsection 450, paragraph 23 approve the use for
the indoors. These are the only materials approved
for use.
MR. NUMUS: I want to know the percentage as
opposed to indoor use.
MR. MONTGOMERY: Well, my research seems to
indicate 85 to 90 percent of the transformers sold in
the United States are currently outdoor applica-
tions, and the other 10 to 15 percent are indoor
applications, for safety is of paramount importance.
MR. WOOD: Essentially the figure that he is using is
pretty accurate. Very large power transformers are
filled with mineral oil because, if they're out in the
field, there is not a substantial hazard, they can be
screened out. In the medium voltage range the use
of askarel is something under 15 percent of the
transformers used in that medium voltage area.
MR. CLIFFORD H. TUTTLE (Aerovox Industries, Inc.,
New Bedford, Massachusetts): I really have two
questions—another alternative mentioned up there,
the capacitor for getting the high voltage can
consume 20 to 50 million pounds a year. How long
339
-------
would it take fluid to be available in that type of
quantity; 1 year, 2 years, 3 years, or what? I don't
want to pressure you, I just want to determine.
The second question is a third of that market is
lighting, fluorescence. If you have an application at
100° C, are any of these fluids or alternatives capa-
ble of operating at that temperature without break-
ing?
MR. MONTGOMERY: Let me answer your second
question first. The answer is yes. The answer to the
first question is we do have the productive capabili-
ties capable to handle that market. It could be
accomplished very quickly. It would probably be
faster than the industry takes to evaluate and
qualify new material.
MR. WOOD: In terms of Monsanto, alternatives could
be made available on a production basis in calendar
year 1976, in relationship to the stability of these
materials at 100° in the HIB and the fluorescent
lighting capacitors, these are test sequences which
are going on under our test programs. And the
results will be forthcoming. We are in a period now
of collective work. We are not ready to go tomor-
row.
340
-------
20 November 1975
Session VI:
GENERAL SESSION
Christopher M. Timm*
Session Chairman
'Director, Surveillance and Analysis Division, Environmental Protection Agency-Region V, Chicago, Illi-
nois.
341
-------
OPEN DISCUSSION
DR. JOHN BUCKLEY (Environmental Protection
Agency, Washington, D.C.): I'd like to call to order
the evening session which is our General Session.
There are some papers to be presented tonight that
are technical papers appropriate to other parts of
the session but which just didn't fit in. In the rest of
the sessions we've tried to avoid people expressing
their opinions. So with that, I'd like to turn it over
to our Chairman for the evening, Chris Timm, who
is the Director of the Surveillance and Analysis
Division for EPA here in Chicago.
MR. CHRISTOPHER TIMM (Environmental Protection
Agency, Chicago, Illinois): Thank you, John. I have
at the present time 26 registered speakers. There
won't be any discussion during this session.
I'd like to start off by introducing the groups
that have been most directly impacted by PCB's in
the environment, at least as far as their, livelihoods.
They are the real reason we have conferences like
this. We have a group of commercial fishermen,
commercial as far as both the market and as far as
recreational aspects in the charter fishing, who are
here from Lake Michigan and some of the surround-
ing areas. I will lead off with them. I'll mix it up
after that with technical presentations, industrial
viewpoints, environmental groups, etc.
MS. JEAN HERMES (Spokesperson for Commercial
Fishing Interests, Green Bay, Wisconsin): I would
like you to know that hardships are already being
inflicted on families because of the PCB poisoning
of our waters. We are fourth-generation commercial
fishermen out of Green Bay. We have four children
and have had our livelihood taken away because of
high levels of PCB's in the Green Bay waters.
On the last part of July of this year, the FDA
shut down our business when fish tested from our
nets measured 54 ppm of PCB's. Overnight we've
lost a- business it's taken 15 years to build.
As PCB's are almost indestructible, any further
discharge, no matter how small, would only add to
an already insurmountable problem. The mills
dumping PCB's into the waters have gotten rich at
everyone's expense but their own. It is time they
make a few sacrifices. Industries have been allowed
to pollute and poison the waters long enough. Every
commercial fisherman in Wisconsin will soon face
our situation.
The commercial fisherman provides the public
with a food that is 75 percent protein. In these days
of food shortages, it is a crime to let this commod-
ity be destroyed. But the commercial fisherman will
not suffer alone. Sportfishing, all water recreation,
and tourist towns are threatened. Even our drinking
water will become, if it is not already, hazardous.
Someone must be held responsible for stopping PCB
discharge into our waters before they are destroyed
beyond repair. Thank you.
MS. GLORIANNE HERMES (Spokesperson for Com-
mercial Fishing Interests, Green Bay, Wiscon-
sin): We are from another family with seven chil-
dren that fishes carp commercially from the waters
of Green Bay. We have also lost our livelihood
because of the high levels of PCB in carp taken from
Green Bay waters. Our fish measured up to 57 ppm
when tested by the Agriculture Department and we
were forced to release the 15,000 pounds of carp
that were in our holding ponds at that time.
The PCB problem so far has been handled back-
wards. My husband and his brothers were stopped
from fishing carp on Green Bay, while nothing has
been done to stop the sources of PCB's. The fisher-
man who had no part in the PCB pollution has been
inflicted with great hardships after many years of
building his business.
The innocent have been made to pay the price
for the destruction caused by a few industries that
are getting richer everyday and do not want to rein-
vest a small part of their profits into the treatment
of their waste.
We believed that the EPA and DNR were keep-
ing the waters clean and safe, which is supposed to
be their job. How has our water been allowed to
become so chemically polluted as to make its fish
inedible even for animal consumption or even for
use as a fertilizer? Some people have not been doing
their job. For if the industries' discharges were safe,
so would the water and fish be safe.
The DNR still plans to plant trout and salmon
into the waters although the levels of PCB in these
fish tested out even higher than some of our carp.
Also, they claim that no money is available to com-
pensate commercial fishermen for their losses due to
the PCB problem when they still plan on planting
trout and salmon into the polluted water.
It isn't going to help to lower the limit of PCB's
343
-------
from 5 ppm to 2 ppm, as nothing has been
done to stop the dumping of RGB's even at the
5-ppm level. To lower the limit of PCB's in fish
from 5 ppm to 2 ppm would destroy the fishing
industry all over the United States. The levels of
PCB in all other edible products, such as meat,
would also have to be lowered and sport fishing
would have to be stopped altogether. The fishermen
would have to be compensated for their losses,
which resulted from other parties' ruthlessness and
carelessness.
Please attack this problem where it started by
stopping all PCB discharges into the water immedi-
ately. Thank you.
MR. GENE LAMBRICH (Spokesperson for Commercial
Fishing Interests, Green Bay, Wisconsin, and
representative of Lambrich Brothers Live Fish
Company): We haul fish from the Hermes Brothers
and I think something that a lot of people don't
realize is that carp is a good fish. It's just not a
scavenger, it's something that's a necessity. We have
two fishing resorts in St. Louis, Missouri. It has cost
us roughly over 100 thousand dollars since July of
this year and I think that our load was a sample load
that the Federal Food and Drug Administration
took the samples off of and said they were polluted.
Now if these fish were polluted at the time we
inquired, in February 1975, they did state that
there were PCB's in the water; why weren't they
periodically checked and sampled, and if there was
pollution at that time, why wasn't it stopped? We're
just one of a few fish haulers. This goes all over the
United States. For the life of me I can't figure out
why they cannot do something with the people
putting these pollutions in the waters. Thank you.
LEE WEDDIG (National Fisheries Institute, Washington,
D.C.): We're a trade association consisting of 550
companies engaged in the commercial fish and sea-
food business.
This is somewhat of an old refrain here. In the
last several years we've talked about things like DDT
in our waters, which had its toll. After that it was
mercury, and today it's PCB. In each of these situa-
tions, there was a cost to our business, which is a 6
billion dollar industry in the United States. It
represents the livelihood of 140 thousand people
throughout the entire country. In each of these
situations, our industry faces three losses. The first
is the direct loss of income, such as has been related
to you by the people who were up here a few min-
utes ago, as their products become unsaleable. Then
we have the loss that is harder to define yet was
alluded to today, and that's the destruction of
habitat for our resource. Many of our resources are
failing. We're running out of fish, there's been
speculation that perhaps we're overfishing. But as
we learn what these chemicals do to the ability of
fish to reproduce, we would have to believe that the
real cause of some of the failures in our resources is
because of the pollution that has been caused by the
unchecked dumping of chemicals into the water.
And then finally we have a loss of consumer
confidence. People don't understand that in a case
of PCB's, the^e are certain fish that are taken from
the market because 1hey do exceed the Food and
Drug Administration tolerances. The consumer
doesn't really understand that this affects only a
very small portion of the total and the reaction
is—Well, let's not use any fish—which is certainly an
unjustifiable attitude, but nonetheless, it does exist.
It's also very easy for one to say the percentage
of loss is small. We are a 6 billion dollar industry; we
supply something like 10 billion pounds of fish a
year to the consumer. One can listen to the folks
from Green Bay and say, "Well, perhaps you could
lose several hundred thousand pounds of fish a year
and it doesn't really amount to much in the way of
percentage." But yet for these folks, it's 100 percent.
Those are the losses that our industry has. What
we're recommending to this group to do, is to
muster its strength, 1o come up with six different
points. We have to solve the problem. We cannot
just live with the DDT's, the mercury, the PCB's, or
whatever it will be next year. We have to come to a
solution. So we're recommending six things.
First for the immediate. The Government
should immediately ban further sale, production,
importation, or recycling of PCB's in any form, with
perhaps an exception for use in existing electrical
transformers where jsage should be strictly con-
trolled. But after hearing this afternoon's statement
about possible substitutes that have been used in
other countries, I'm riot too sure I even agree to my
exception any more.
Efforts should be made to achieve an interna-
tional agreement to the same goals. If legislation is
necessary to achieve such a ban, then we should all
get together to get it. passed.
Number two, we must establish a national
system to provide for safe disposal of PCB's already
•used in electrical equipment. We were shocked to
hear of the hundreds of millions of capacitors that
are in use and we can just envision that over the
344
-------
next 30 to 50 years these elements are going to be
disposed of without any control whatsoever, and
eventually they are going to leak into our environ-
ment.
Number three, the Toxic Substances Control
Act must be passed. We must avoid future problems
of this type with other chemicals. I admit our indus-
try has not worked hard enough to get this bill
passed. We did support it as it went through the
various stages of the Congress, but we did not really
get behind it and scream loud enough. I can assure
you we will do this from th's point on.
Number four, we believe the present Food and
Drug tolerance of 5 ppm in fish should be retained
pending further research on the toxic effects on
humans of RGB's. We believe that any reduction in
tolerance should be selective, based on the role and
the specific effect of the food in the diet.
Five, compensation, in all justice, must be made
to commercial fishermen whose livelihood is de-
stroyed by prohibition of sale of the species of fish
in which the presence of PCS exceeds the Food and
Drug tolerance. One element of our society must
not pay for the mistake of the entire society.
And sixth, Congress should investigate the Envi-
ronmental Protection Agency to determine why
effluent standards for PCB's have not yet been
established despite the clear mandate of the Water
Quality Act to do so. If EPA doesn't have the fund-
ing, we have to get it. If the deadlines were unrea-
sonable as set by Congress in 1972, then Congress
should know they were unreasonable. Nonetheless,
our industry would have expected results from this
act at this time. Thank you.
PCB BODY BURDENS DENY FULL USE OF
THE GREAT LAKES FISHERY RESOURCE
Carlos M. Fetterolf, Jr.*
The 1954 Convention on Great Lakes Fisheries
between the United States of America and Canada led to
establishment of the international Great Lakes Fishery
Commission in 1956. The Commission has two major
thrusts, control of the sea lamprey and determination of
research and management strategies to provide sustained
productivity in the convention area of any stock of fish
which is of common concern to the parties. The Com-
mission works cooperatively with the Canadian and U.S.
Federal agencies and the provincial and State govern-
ments of Ontario and eight Great Lakes States to
improve and perpetuate Great Lakes fishery resources.
The statement below is not Commission-approved.
It is an expression of my personal opinions as the Com-
mission's executive secretary.
The U.S. Food and Drug Administration guideline
of 5 /ug/g (ppm) in edible tissue of fish has been
exceeded in numerous species in lakes Michigan, Huron,
Erie, and Ontario, and in their connecting waters.
Several important sport and commercial species are
included with those that exceed the guideline. This situa-
tion casts a pall over the social and economic aspects of
Great Lakes fisheries. It creates a very real problem for
commerica! fishermen, processors, and retailers; a
*Executfve Secretary, Great Lakes Fishery Commission,
Ann Arbor, Michigan.
shadow of doubt in the minds of every consumer and
sport fisherman; an added question for the fishery man-
ager; a symbol of defeat for the water pollution control
agencies; and a mark for every environmental manage-
ment critic to flaunt as an example of the failure of the
"system." It denies full use of the Great Lakes fishery
resource.
I hope none of you have the feeling that if residues
in Great Lakes fish diminish to below 5 Mg/g that all is
well. A few years ago commercial mink ranchers fed
their animals Great Lakes fish until they noticed a dis-
turbing phenomenon, reproduction was falling off alarm-
ingly. This led to studies of the effects of PCB's in ranch
mink. Ringer et al. (ref. 1) demonstrated that 2 /Jg/g
PCB's in fish flesh prevented survival of newborn ani-
mals, and Platonow and Karstad (ref. 2) demonstrated
that reproduction was eliminated in mink fed a beef diet
containing 0.64 /^g/g Aroclor 1254, a PCB compound. If
regulatory agencies consider fish as animal feed a use to
be protected, application of a modest 0.2 safety factor
provides a tissue level of 0.1 /ug/g PCB in whole fish.
There aren't many adult fish in the Great Lakes system
that can meet that objective at this time.
The presence of PCB's in Great Lakes fish continues
to deny full use of the fishery resource. The Great Lakes
Fishery Commission is not a regulatory agency. We must
345
-------
depend on legislative action to pass the laws and enforce-
ment agencies to furnish the muscle which will provide
an aquatic environment that will produce usable fishery
products. It appears to me that some foot dragging has
been going on. How do we get response from a regula-
tory agency? Dr. Nisbet expressed disappointment that
so few people were aware of his $8 publication and con-
cluded that to have impact one must release large
amounts of reprints into the environment. I don't think
that's the answer.
How about development of data and publication by
the regulatory agency itself? You heard Charlie Walker
state that PCB's in fish were added in 1970 to the Na-
tional Pesticide Residue Monitoring Program partici-
pated in by EPA. Data showing PCB body burdens as
high as 213 /ug/g in the Hudson River and 133 /zg/g in
the Ohio River were available 5 years ago. FDA guide-
lines of 5/Kj/g were the same then as they are now.
How about the regulatory agency funding a study to
recommend allowable levels of contaminants? EPA
funded such a study by the National Academy of Sci-
ences/Engineering in 1971 and the first draft was deliv-
ered on schedule to EPA's Washington office in Decem-
ber 1971. The recommendation for PCB's in that draft
of Water Quality Criteria 1972 (ref. 3) read similarly to
that in the published document:
"Aquatic life should be protected where the maxi-
mum concentration of total PCB in unfiltered
water does not exceed 0.002 /ug/l at any time or
place, and the residues in the general body tissues
of any aquatic organism do not exceed 0.5//g/g."
The National Academy report concluded that water
quality levels alone were insufficient to predict what
body burdens could result and therefore combined a
body burden recommendation. If the body burden
exceeded the recommendation, then obviously the water
concentration was too high and should be further re-
stricted.
In the four years since EPA received that recom-
mendation from the National Academy of Sciences,
sufficient data have been developed so that the recom-
mendation of the Water Quality Objectives Subcom-
mittee to the International Joint Commission made in
June 1975 (ref. 4) could read:
The concentration of total polychlorinated bi-
phenyls in fish tissues (whole fish, calculated on a
wet weight basis), should not exceed 0.1 micro-
grams per gram for the protection of fish consum-
ing birds and animals.
NOTE: The Subcommittee expresses concern that
a water concentration objective for this ubiqui-
tous contaminant is unavailable. Based upon poor-
ly defined bioconcentration factors it may be con-
cluded that PCB's in water should not exceed
0.001 micrograms per litre (1 ppt). However, this
level may not be adequate to provide protection to
certain predators, and could presently not be
enforced because of insufficiently sensitive quanti-
fication limits.
This was a reduction to 0.1 /ug/g body burden in whole
fish from the NAS recommendation of 0.5 //g/g and a
reduction in water level concentration from the 0.002
/ug/| of the Blue Book to stating that 0.001 M9/I may be
inadequate.
I am pleased that EPA is currently releasing for re-
view their proposed Quality Criteria for Water. Remem-
ber yesterday Tom Kopp showed us the recommenda-
tion for PCB's, "0.001 M9/I for freshwater and marine
aquatic life and for consumers thereof." Wastes go into
systems, different systems have different capacities of
response to PCB.'s. Is a blanket nationwide water level
fair to industry, the environment, and the people? Will
this water concentration alone do the job?
Apparently there is no accompanying body burden
recommendation. This is disturbing to me. I didn't know
EPA was so confident that bioaccumulation from 0.001
won't be a problem. Remember I told you that 0.64
Aroclor 1254 in the diet of ranch mink eliminated
reproduction? A modest safety factor of 0.2 provided a
recommended residue in fish of 0.1 p.g/g used to feed
mink. You heard several speakers mention bioconcentra-
tion factors greater than 100,000, some as high as
270,000. Two hundred thousand multiplied by a water
concentration of 0.001 /ug/l yields a body burden of 0.2
Mg/g, double the recommended residue if you're in the
business of selling fish to mink ranchers.
I don't believe the concentration of PCB in the
waters of Lake Superior is known accurately enough
that it appears in the refereed literature. It is generally
believed to be 0.001 p'g/l, the concentration recom-
mended in EPA's proposed Quality Criteria for Water.
An analytical chemist o1 EPA's National Water Quality
Laboratory at Duluth on the shores of Lake Superior
estimates the PCB concentration in Lake Superior water
at 0.0004 jug/I, 0.4 parts per trillion. The total PCB body
burden of whole Lake Superior adult ciscoes is 5 /ug/g
and greater. Depending on which water concentration
one chooses, we have a bioconcentration factor of at
least 500,000 times. I don't believe the proposed EPA
water concentration is going to do the job necessary so
that Great Lakes fishery resources can be fully used.
Canada shares the Great Lakes with us. The November
17, 1975, announcemenl by its Department of Health
and Welfare, lowering its PCB regulatory level to 2 jug/g
346
-------
in edible tissue is going to further restrict the full use of
Great Lakes fishery resources.
You heard Dr. Munson say this morning that 99
percent of the PCB content in upper Chesapeake Bay
water is associated with suspended sediment. Obviously
it's going to affect analytical results if you measure
water concentrations unfiltered, settled, or filtered. I
was surprised EPA's proposed recommendation for PCB
did not include a mention of whether suspended mate-
rials should be included in the analysis. By the way, are
PCB's adsorbed to suspended materials biologically
important? If not, perhaps the water should be filtered
before analysis. Do regulatory agencies know the an-
swers to questions so critical to our environment and
economic welfare?
There are several avenues of problem solution open
to EPA. There are tough choices, and fortunately it is
not my responsibility to make a recommendation. All I
ask is that something be done, and that what is done will
permit full use of the Great Lakes fishery resource.
REFERENCES
1. R. K. Ringer, R. J. Aulerich,-and M. Zabik, "Effect
of Dietary Polychlorinated Biphenyls on Growth and
Reproduction of Mink," Amer. Chem. Soc. National
Meeting Preprints of Papers, Vol. 12 (1972), pp.
149-154.
2. N. S. Platonow and L. H. Karstad, "Dietary Effects
of Polychlorinated Biphenyls on Mink," Can. J.
Comp. Med., Vol. 37 (1973), pp. 391-400.
3. Water Quality Criteria 1972, National Academy of
Sciences, National Academy of Engineering, U.S.
Environmental Protection Agency Ecological
Research Series, EPA-R3-73-C33, Superintendent of
Documents, Washington, D.C., pp. 595.
4. Great Lakes Water Quality Board, third annual re-
port to the International Joint Commission, 1975,
IJC Regional Office, Windsor, Canada.
DR. WILBUR P. MCNULTY (Oregon Regional Primate
Research Center, Beaverton, Oregon): I will sum-
marize briefly a series of experiments on the toxic-
ity of polychlorinated biphenyls (PCB's) in rhesus
monkeys. Three preliminary conclusions can be
drawn from the results.
First, PCB's produce a unique and reproducible
constellation of pathologic changes in monkeys over
a wide range of doses. These changes are different
from those reported for other laboratory animals.
Furthermore, 2,3,7,8-tetrachlorodibenzo-p-dioxin
(TCDD) causes exactly the same constellation.
Second, rhesus monkeys are lethally poisoned
by very low levels of intake of PCB's in the diet,
roughly 100 times less than the levels which cause
serious illness in rats.
Third, some individual PCB components are
quite toxic for monkeys and some are not. Contami-
nating chlorodibenzodioxins or -furans probably
cannot account for the toxicity of commercial
Aroclor 1242 in monkeys.
Figure 1 shows extensive downgrowth of mu-
cous glands into the submucosa of the stomach of a
monkey which died after 8 months consumption of
regular monkey chow to which Aroclor 1242 was
added at 3 ppm. The development of this gastric
lesion was studied by monthly biopsies in monkeys
fed Aroclor 1242 at 3 to 10 ppm, and the results
will be discussed by my colleague Dr. Bell.
An early clinical sign of PCB poisoning in
rhesus monkeys is thickening and reddening of the
eyelids. The Meibomian (sebaceous) glands were
completely converted to squamous cysts (figure 2).
Sebaceous glands associated with hair follicles in the
face and and scalp similarly underwent squamous
metaplasia, with atrophy of the gland or, occasion-
ally, cyst formation (figure 3).
The thymus became markedly atrophic (figure
4); the thymocytic cortex disappeared entirely, and
the corpuscles formed small cysts.
Exactly the same pattern of changes was found
in monkeys accidentally poisoned with what subse-
quent chromatographic analysis of the tissues
showed was probably Aroclor 1260, presumably
used in construction materials in the pens. And
finally, the same pattern followed experimental
poisoning with TCDD—in only 12 days at an intake
of 20 ppb in the diet.
The spectrum was the same at exposure of from
3 to 800 ppm of Aroclor 1242, though of course
347
-------
Figure 1a. Normal gastric mucosa of young
male rhesus monkey. H&E, 30x.
Figure 1 b. Gastric mucosa of young male
rhesus monkey fed diet containing 3 ppm
Aroclor 1242 for 8 months. Extensive
mucous epithelial invasion of submucosa.
H&E,30x.
Figure 2a. Normal eyelid of young male
rhesus monkey. Transverse section, con-
junctival surface below. H&E, 30x.
it
Figure 2b. Eyelid of young male rhesus
monkey fed diet containing 3 ppm
Aroclor 1242 for 8 months. Squamous
metaplasia and cystic dilation of Meibo-
mian glands. H&E, 30x.
348
-------
Figure 3a. Normal vibrissae or sinus hairs
in lip of young male rhesus monkey. A
garland of sebaceous glands encircles the
hair follicle at the upper end of the blood
sinus. H&E,30x.
Figure 3b. Sinus hair of lip of young male
rhesus monkey fed diet containing 3 ppm
Aroclor 1242 for 8 months. Garland of
sebaceous glands is absent. H&E, 30x.
Figure 4a. Normal thymus of young male
rhesus monkey. H&E, 30x.
Figure 4b. Thymus of young male rhesus
monkey fed diet containing 3 ppm Aro-
clor 1242 for 8 months. Severe atrophy
and cyst formation in corpuscles. H&E,
30x.
349
-------
illness and death came sooner at higher doses. A
dietary level of 3 ppm corresponds to an intake of
150 /Jg/kg/day, or about 40 times the level that Dr.
Nisbet calculated might be the intake of a fisherman
or a nursing baby today.
At least with respect to the effects on seba-
ceous glands, the disease in monkeys resembles that
reported in the victims of Yusho, an accidental
poisoning of Japanese people.
I have tested three pure PCB compounds at 10
ppm; this is a reference level which, in the case of
Aroclor 1242, causes barely discernible histologic
changes in 30 days, slight clinical illness in 45 days,
and outspoken disease in 60 days.
At this level, 2,4,4'-trichlorobiphenyl and
2,4,5,2',5'-pentachlorobiphenyl, both major compo-
nents of Aroclor 1242, caused no clinical or histo-
logical changes in rhesus monkeys experimentally
fed for 80 days. On the other hand, 3,4,3',4'-tetra-
chlorobiphenyl, which is not significantly present in
Aroclor 1242 killed a monkey and caused the usual
pathologic changes in 34 days. This finding invites
the speculation that the metabolites of some RGB's
may be the actual toxins. For example, 2,3,7,8-tet-
rachlorodibenzofuran (TCDF), which is known to
be quite toxic for laboratory rodents but has yet to
be tested in monkeys, could conceivably be formed
from the 3,4,3',4'-tetrachloro-biphenyl by hydro-
xylation and condensation. But this lot of tetrachlo-
robiphenyl has yet to be analyzed for possible
preexisting contaminants.
However, it is not likely that contaminating
dioxins or furans can account for the toxicity of
commercial RGB's. Pilot experiments have indicated
that TCDD is about 10,000 times as toxic as Aro-
clor 1242 on a per gram basis. TCDF can be
expected to be somewhat less active. Since our
analysis of Aroclor 1242 has shown contamination
to be not more than 1 ppm, there is not enough
dioxin or furan present to account for the effects of
the Aroclor.
ULTRASTRUCTURAL FEATURES OF GASTRIC MUCOSA
AND SEBACEOUS GLANDS AFTER INGESTION
OF AROCLOR 1242 BY RHESUS MONKEYS
Mary Bell, Ph.D.
The effects of RGB's on the stomach, skin, and liver
of rhesus monkeys have previously been described by
Allen and his associates (refs. 1-5) and some of these
effects by McNulty (ref. 6). Of these organs, the liver has
been the only one on which any electron microscopic
observations have been made. In the liver, PCB adminis-
tration results in a proliferation of the smooth endo-
plasmic reticulum and, in some cases, the accumulation
of fat droplets within the hepatocyte. Because the cyto-
logical features of these organs are extremely diverse, it
is important to document the effects of RGB's of all of
them.
McNulty (ref. 6} has described a series of rhesus
monkeys that were fed either 3,10, 30, or 100 parts per
million (ppm) Aroclor 1242 until they became mori-
bund. The stomach and lip of each animal were serially
biopsied at monthly intervals beginning 2 weeks after
first ingestion of these compounds. The tissues were
'Assistant Professor of Environmental Health, University of
Cincinnati, Department of Environmental Health, Kettering Lab-
oratory, 3223 Eden Avenue, Cincinnati, Ohio 45267.
processed according to routine procedures for light and
electron microscopic observation. This report describes
the effects of ingestion of Aroclor 1242 on the cellular
components of the stomach and of the sebaceous glands
associated with the large tactile, facial hairs, vibrissae, of
these animals.
Figures 1 and 2 demonstrate the changes seen with
the light microscope in the gastric epithelium of an
animal fed 100 ppm Aroclor 1242. After 2 weeks inges-
tion, the stomach was still essentially normal (figure 1).
The mucus-secreting surface and the gastric glands that
contain parietal cells (hydrochloric acid secretors) and
zymogenic cells (enzyme secretors) showed no patho-
logic changes. After ingestion of 100 ppm PCB's for 2
months, however, the mucus-secreting surface had
become hyperplastic (figure 2); the parietal and zymo-
genic cells of the gastric glands had totally disappeared
and had been replaced by mucus-secreting cells. These
effects, though demonstrable at varying times after onset
of PCB administration, were identical in all animals at
any of the dose levels used. Figures 3 and 4 show the
350
-------
Figure 1. A light micrograph of the gastric
mucosa of a rhesus monkey fed 100 ppm
Aroclor 1242 for 2 weeks. The mucus-
secreting surface mucosa and the gastric
glands containing parietal and zymogenic
cells are of essentially normal appearance
(x140).
Figure 2. An oblique section of gastric mucosa
from a rhesus monkey fed 100 ppm Aroclor
1242 for 2 1/2 months. Most of the gastric
glands have been replaced by mucus-secret-
ing cells (x140).
effects after 5-1/2 months on the stomach of an animal
fed 3 ppm Aroclor 1242. At this time, most of the gas-
tric glands had been replaced by mucus-secreting epithe-
lium.
At the electron microscope level, the first PCB-
related changes were seen in the parietal cells of the
gastric glands, and some of these changes were observed
at the higher dosage levels shortly after the onset of PCB
ingestion. These cells normally have a distinctive cyto-
logy, which includes intracellular canaliculi through
which the hydrochloric acid is secreted, many small
cytoplasmic vesicles, and large numbers of mitochondria.
After PCB ingestion, the intracellular canaliculi became
somewhat distended, the cytoplasmic vesicles became
less discrete and tended to break down, and small dense
bodies, presumably containing hydrolytic enzymes,
accumulated (figure 5).
In the bases of the gastric glands, mucus-secreting
cells were interspersed among zymogenic cells after
ingestion of PCB's. Zymogenic cells normally contain
extensive concentrations of granular endoplasmic reticu-
lum located basally in the cells; this reticulum is respon-
sible for the production of enzymes. After PCB inges-
tion, however, mucus-secreting cells with typically little
endoplasmic reticulum began to appear adjacent to the
zymogen-secreting cells (figure 6). In some cells still
recognizable as zymogenic, the endoplasmic reticulum
was dilated and the cells contained large autophagic
vacuoles (figure 7). The latter usually occur in cells that
are undergoing degradation.
Figures 8 and 9 show the changes seen at the light
microscope level in the sebaceous glands associated with
the tactile hairs of the face after PCB ingestion. Nor-
mally, lipid production by the sebaceous glands begins
close to the peripheral portions of the glandular alveoli
and continues to the more central portions where the
351
-------
,
ra^'Mfci^^. •-•"''
Figure 3. Gastric mucosa ot a rhesus monKey
fed 3 ppm Aroclor 1242 for 5 1/2 months.
Most of the gastric glands have been replaced
by mucus-secreting cells. The effects are
similar to those shown in figure 2 (x140).
Figure 4. A higher magnification of a portion
of figure 3. The gastric glands are almost
completely composed of mucus-secreting
cells. Only one gland (at the left center
of the field) contains zymogenic cells
(x560).
lipid is secreted onto the hairs. After ingestion of Aro-
clor 1242, lipid synthesis and accumulation became
increasingly limited to the central zones of the alveoli;
ultimately, only small buds of cells no longer secreting
lipid droplets were found adjacent to the hair follicles in
the sites normally occupied by sebaceous glands. These
effects were identical in all animals fed PCB's, but they
occurred most rapidly at 100 ppm, least rapidly at 3
ppm Aroclor 1242.
As observed at the electron microscope level,
sebaceous cells normally contain large Golgi zones that
are the site of synthesis of the lipid droplets and many
profiles of agranular endoplasmic reticulum, which are
considered to participate actively in the production of
lipid (figure 10). After PCB ingestion, these membranes
acquired a softened appearance during stages when they
were still prominent. Many small electron-opaque
bodies, probably indicative of the presence of hydrolytic
enzymes, also occurred in these cells after PCB ingestion.
When no lipid droplets were detectable after PCB inges-
tion (f^ 2-y2 months al 100 ppm, -v 4-Y2 months at 3
ppm), filaments usually associated with epidermal-type
cells (from which sebaceous glands are embryologically
derived) often increased in abundance in the sebaceous
cells, they continued to contain a few profiles of granu-
lar endoplasmic reticulum, but smooth membranes could
no longer be detected (figure 11). Ultimately, the seba-
ceous cells no longer even resembled the epidermal cell
type, and they no longer appeared capable of producing
lipid.
These studies do not enable us to determine wheth-
er cells can change their direction of differentiation
under the influence of PCB's or whether they merely
differentiate in the only direction available to them
when PCB's are present. They do tell us, however, that
cells, depending on their location and function in the
body, respond in very different ways to PCB's.
352
-------
Figure 5. An electron micrograph of a parietal cell from the stomach
of a rhesus monkey fed 30 ppm Aroclor ^ 242 for 2 weeks Many
small permuclear cytoplasmic vesicles (v) are disrupted and a portion
of an mtracellular carialiculus is distended (arrow) (x6300).
353
-------
Figure 6. An electron micrograph of a portion of a gastric gland from
a rhesus monkey fed 10 ppm Aroclor 1242 for 4 1/:> months. Mucus-
secreting cells (M) have become interspersed with zymogenic cells
(Z) in this location (x3400).
354
-------
Figure 7. Portions of two zymogenic cells containing large autophagic
vacuoles (av) and dilated granular endoplasmic reticulum (er). The
animal from which the tissue was biopsied had been fed 3 ppm Aro-
clor 1242 for 5 1/2 months (x 13,150).
355
-------
Figure 8. An oblique section through a tactile
hair with associated sebaceous glands. Though
the glands are small, cell differentiation, evi-
denced by sebum droplets, is still occurring
close to the periphery of the alveoli (arrows).
This tissue was taken from an animal fed 3
ppm Aroclor 1242 for 3 1/2 months (x140).
:^f^ll^w "$$
Figure 9. A light micrograph of a comparable
site as that shown in figure 7 but after 3
ppm Aroclor 1242 for 4 Vz months. No
sebum droplets or differentiating cells are
visible in the sites (arrows) normally oc-
cupied by the sebaceous glands (x140).
356
-------
Figure 10. An electron micrograph of cells with essentially normal
features in a sebaceous gland associated with a large tactile hair.
The animal from which the tissue was biopsied had been fed 30
ppm Aroclor 1242 for 2 months. Although these cells are close
to the periphery of an alveolus, they are producing abundant lipid
droplets (Id) (x5600).
357
-------
»•'«"••
r—-r.^
: 1
; »*'
•*u
Figure 11. An electron micrograph of cells from a site similar to
that shown in figure 10, but from an animal fed 3 ppm Aroclor
1242 for A 1/2 months. The cells contain no lipid droplets, and
their cytoplasm appears largely amorphous (x7200).
ACKNOWLEDGMENT
All of the specimens and much of the data for this
study were collected at the Oregon Regional Primate
Research Center. Work was supported in part by Grants
AM08445 and RR00163 of the National Institutes of
Health and ES-00159-10 of the National Institute of
Environmental Health Sciences.
REFERENCES
1. D. H. Norback and J. R. Allen, "Pathobiological
Responses of Primates to Polychlorinated Biphenyl
Compounds," this conference.
2. D. H. Norback and J. R. Allen, "Chlorinated Aro-
matic Hydrocarbon Induced Modifications of the
Hepatic Endoplasmic Reticulum: Concentric Mem-
brane Arrays," Environ. Health Perspec., Vol. 1
(1972), p. 137.
3. L. J. Abrahamson and J. R. Allen, "The Biological
Response of Infant Nonhuman Primates to a Poly-
chlorinated Biphenyl," Environ. Health Perspec.,
Vol. 4 (1973), p. 81.
4. J. R. Allen and D. H. Norback, "Polychlorinated
Biphenyl and Triphenyl Induced Gastric Mucosal
Hyperplasia in Primates," Science, Vol. 179 (1973),
p. 498.
5. J. R. Allen, L. A. Carstens, and D. A. Barsotti,
"Residual Effects of Short-Term, Low-Level Expo-
sure of Nonhuman Primates to Polychlorinated Bi-
phenyls," Toxicol. App. Pharmacol., Vol. 30
(1974), p. 440.
6. W. P. McNulty, Jr., this volume.
358
-------
THE VIEW OF THE PAPER INDUSTRY ON
THE OCCURRENCE OF PCB'S IN THE
ENVIRONMENT AND THE NEED FOR REGULATION
Paul E. Trout*
My name is Paul E. Trout. I am Director of Environ-
mental Control for Container Corporation of America
and am presenting the following comments on behalf of
my company and the American Paper Institute.
The American Paper Institute is a national organiza-
tion composed of manufacturers of pulp paper, and
paperboard. Members utilize both virgin and recycled
fiber in the manufacture of paper products. In 1973, the
American paper industry and its wastepaper suppliers
recycled nearly 15 million tons of wastepaper (ref. 1) an
all time high. In the same year, approximately 41 per-
cent of the fiber used by Container Corporation of
America's 13 paperboard mills was derived from waste-
paper.
This recycling of wastepaper unwittingly plunged
my company and similar recyclers into the morass of the
PCB problem in late 1970.
I. THE PAPER INDUSTRY DOES NOT USE OR IN-
TRODUCE PCB'S INTO THE ENVIRONMENT
BUT RATHER RECIRCULATES PCB'S AL-
READY PRESENT, WHICH ARE UNAVOIDABLY
INCLUDED IN ITS MANUFACTURING INPUT
PCB's are not a part of the paper manufacturing
process. Consequently the paper industry does not add
new PCB's to the environment. PCB's are, however,
unavoidably included in certain inputs into the paper
manufacturing process. In particular, the water supply
used in paper making contains PCB's.,from other unre-
lated sources. The paper manufacturing process is not
designed to remove PCB's and consequently effluents do
contain low levels of this chemical which have entered
the mills in the intake waters.
The other PCB input to the paper manufacturing
process is the raw material used by recycling mills as a
fiber source. Until early 1971, NCR paper (carbonless
copy paper) used Aroclor 1242 enclosed in micro-
capsules coated on the paper. Thus business forms made
with carbonless copy paper have been a component of
office waste paper, a portion of which is recycled in the
papermaking process. Inevitably the PCB's present in the
office waste have been introduced into the paper
recycling process.
Again, no new PCB's are added to the environment
'Director of Environmental Control, Container Corporation
of America, Carol Stream, Illinois.
by paper mills but, rather, existing PCB's are simply
recirculated. If the paper mills could not recylce the
office waste containing PCB-bearing paper, the paper
would just as surely enter the environment either
through leaching in landfills or volatilization in incinera-
tors which are unable to destroy the PCB's. In either of
those events, municipal solid waste systems would have a
very substantial new burden added to their normal
operating loads and the important national recycling
would be significantly injured. Moreover, the PCB
present in the old NCR paper still occasionally finding
its way into the waste stream is Aroclor 1242, the one
not accumulating in the environment. It is this PCB that
is found both in the paper products and in the effluent
of paper mills.
Since 1971, when the use of PCB in the manufac-
ture of carbonless carbon paper was halted, PCB levels in
recycled-fiber paperboard used for food packaging have
continued to decline. The industry monitoring program
showed that, in the third quarter of 1975, 99.63 percent
of such paperboard had a PCB content less than 10 ppm
and 91.3 percent had a PCB content less than 2.5 ppm.
These results have been achieved through the most
careful selection of the wastepaper used in the recycling
process with rejection of all types of wastepaper sus-
pected to contain PCB's.
II. THE PCB RECIRCULATED BY THE PAPER
INDUSTRY, AROCLOR 1242, IS NOT FOUND
TO ACCUMULATE IN ANIMALS, MAN, OR IN
THE ENVIRONMENT
The PCB occasionally detected in paper products
and in the effluent of paper manufacturing plants is
Aroclor 1242. For the years 1960 through 1971,
Aroclor 1242 represented from 48.15 to 68.9 percent of
the total domestic PCB production, reaching this maxi-
mum percentage in 1967 and 1968 and decreasing there-
after. Accordingly, it would necessarily be the PCB most
widespread in the environment if all PCB's were all
equally degradeable In fact, however, Aroclor 1242 is
neither found in the tissues of man or animal nor in the
aquatic environment generally. This indicates that the
lower chlorinated PCB's such as Aroclor 1242 are either
metabolized, decomposed in aqueous environments, or
degraded by photolysis. If accumulation of PCB in aqua-
tic environments, and thereby in the food chain and
359
-------
man, is perceived to be a potential threat to" human
health, it is a threat unrelated to Aroclor 1242. Any PCB
regulation based on environmental needs must accomo-
date this fact.
III. THE CURRENT LEVELS OF DIETARY INTAKE
IS MANY ORDERS OF MAGNITUDE LOWER
THAN THE ALLOWABLE DAILY INTAKE AS
FOUND BY THE FOOD AND DRUG ADMINI-
STRATION
Evaluation of The need for regulatory controls of
the source and distribution of PCB's must begin with the
threat PCB's pose to the health of man or other parts of
the living environment. In the case of PCB's, the possible
threat to human health is through the food supply.
Accordingly, that evaluation should start with the levels
of dietary intake of PCB's with reference to the levels
posing a threat to man.
As a distinguished committee of the National
Academy of Sciences, National Research Council stated,
"For every chemical there is some finite level sometimes
called the 'safe' level, at or below which it can be present
in food without prejudicing safety (ref. 2)." Conversely,
as three other NAS committees have recently noted,
"There is no substance which under certain circum-
stances, could not be dangerous and unsafe (ref. 3)."
The possible need for regulatory controls of PCB's there-
fore must be assessed in terms not of the conceivable
danger posed by some amount of a substance but rather
in terms of the available margin of safety between con-
ceivably harmful dosages arid actual consumption.
According to the Food and Drug Administration's
Director of the Office of Science, Dr. Albert C. Kolbye,
Jr., the allowable daily intake of PCB's in the adult
human diet is 200 jug/g/day. This conclusion is based
upon Dr. Kolbye's analysis of available animal toxicity
studies including the recent investigations of Dr. Kim-
brough as well as upon analysis of human toxicity data
arising from the "Yusho" incident in Japan involving
massive intoxication by PCB's.
The Food and Drug Administration's "Total Diet
Studies" demonstrate that PCB average dietary intake
levels have never been remotely near this 200
^g/adOlt/day figure. On March 18, 1972, FDA stated in
a Federal Register notice that its tolal diet studies indi-
cated an average daily intake of 7/jug/day/adult or 4.7
ppb in the total diet. This is 3.5 percent of the amount
Dr. Kolbye concluded was plainly safe. Those data re-
flected the period of August 1969 through March 1972
when PCB exposure must have been at its peak since the
steps taken by Monsanto Company in early 1971 to
confine the sale of PCB's to closed systems had not yet
had time to be reflected in the data base.
Fifteen months later, on July 6, 1973, FDA an-
nounced that the quantitatively measurable residue of
PCB's were equivalent to an average dietary intake of 4.2
/xg/day/adult. This corresponds to a dietary intake of 2.8
ppb or about 2 percent of the level Dr. Kolbye identified
as safe. According to FDA's total diet studies for fiscal
year 1973, the dietary intake of PCB's was 1 jug/day/-
adult or .67 ppb. This is less than 1/2 percent of the st 'e
amount calculated by Dr. Kolbye. According to thjse
studies for the period of October 1972 to January 1975,
the average dietary intake was .178 jug/day/adult or .118
ppb (118 ppt), or below 1/10 of 1 percent of Kolbye's
safe level. An examination of the total dietary intake as
shown by FDA's total diet studies from January 1,
1974, through June 1975 shows PCB intake has been
zero: that is, not a single quantifiable residue of PCB has
been detected in the total diet study which would allow
any quantitative estimate whatsoever.*
In short, dietary intake of PCB has been declining
rapidly since approximately the time Monsanto imple-
mented its voluntary controls on the distribution of
PCB's to its customers. Even during the maximum expo-
sure period, the average dietary intake was nowhere near
what the Food and Drug Administration states to be an
allowable daily intake. At the present time, there is an
even vaster gulf—many orders of magnitude—between
the allowable daily intake and the amount of PCB posing
any conceivable hazard to man.
IV. ANY ADDITIONAL CONTROLS MUST ACHIEVE
MAXIMUM ENVIRONMENTAL COST-EFFEC-
TIVENESS
The paper recycling industry has been a participant
in the PCB drama through circumstance, not by choice,
and our industry is not alone in this. We thus appreciate
the need for procedures to prevent similar happenings in
the future as well as to correct remaining PCB problems.
Our industry approves the principle of restricting
the use of hazardous substances. We do not, however,
support far-reaching regulation of the nature of Senate
Bill S776. Such legislation simply would amount to the
"Biological and Analytical Chemist's Relief Act of
1975" and would, in addition, open a new Pandora's
box of legal mischief. We believe duplication of existing
legislation should be avoided and that deficiencies in
existing legislation be corrected by specific amendment
in order to maximize environmental benefit at minimum
cost to the public.
*lt is also significant that for FY 1975 the total diet studies
did not detect a single trace of Aroclor 1242, the PCB associated
with the recycled paper manufacturing process.
360
-------
We particularly urge States now considering new
regulations to combat the PCB problem to develop ra-
tional rather than simplistic solutions. Destruction of the
wastepaper recycling industry will benefit neither the
public health nor the public purse.
We commend the Environmental Protection Agency
for establishing a task group to investigate PCB imports.
We urge that they continue to track down specific uses
of these materials in the United States and publish this
information so that further unknowing use of PCB's can
be avoided.
We urge EPA to publicize abroad the self-regulatory
action taken by Monsanto Co. to minimize further PCB
contamination of the environment. Hopefully, such
enlightened action may spread worldwide.
And, finally, we urge the Environmental Protection
Agency to implement a program whereby PCB-contain-
ing wastepapers issuing from Federal agencies are dis-
posed of by incineration at a temperature sufficient to
destroy PCB. If Aroclor 1242 is an environmental
hazard, this procedure would prevent the' reservoir of
this material now residing in the files of the world's
greatest recordkeeper from contaminating the environ-
ment.
All of these control actions can be initiated immedi-
ately, without need for additional legislation and with
immediate positive results.
To conclude, 1 would like to summarize these
points:
I. The paper industry does not use or introduce PCB's
into the environment but rather recirculates PCB's
already present which are unavoidably included in
its manufacturing input.
II. The PCB recirculated by the paper industry, Aroclor
1242, is not found to accumulate in animals, man,
or in the environment.
III. The current levels of dietary intake is many orders
of magnitude lower than the allowable daily intake
as found by the Food and Drug Administration,
IV. Any additional controls must achieve maximum
environmental cost-effectiveness.
REFERENCES
1. F. L. Smith, Jr., "Wastepaper Recycling: Review of
Recent Market Demand and Supply/' Pulp and
Paper, September 1975, p. 148.
2. "Guidelines for Estimating Toxicoiogically Insignifi-
cant Levels of Chemicals in Food," Food Protection
Committee, Food and Nutrition Board, National
Academy of Sciences, National Research Council,
Washington, D.C., p. 1.
3; "Principles for Evaluating Chemicals in the Environ-
ment," a joint report of three NAS cornrr>ittees:
Committee for the Working Conference on Princi-
ples of Protocols for Evaluating Chemicals in the
Environment; Environmental Study Board, NAS,
National Academy of Engineering; and Committee
on Toxicology, National Research Council, Washing-
ton, D.C., p. 83.
MR. BERNARD A. KERNS (Westinghouse Electric
Corporation, Pittsburgh, Pennsylvania): I very
much appreciate the opportunity to make these
comments at this conference. It is the hope of
Westinghouse that this conference will bring to-
gether all of the scientific and technical information
that 4s available to identify the positive aspects of
the current mixtures that are being used by the elec-
trical industry.
The Westinghouse Transformer Divisions and
the Westinghouse Distribution Apparatus Division
are users of a substantial quantity of polychlori-
nated biphenyls in the production of transformers
and capacitors. At this point I should point out that
Westinghouse uses a term inerteen for the mixtures
of PCB's it uses as a dielectric, and that the generic
term used in the electrical industry is askarel. These
terms are really not interchangeable with the term
PCB's. While there are 209 isorners of PCB's; the
electrical industry uses only several mixtures of PCB
isomers as dielectric.
Of these, Westinghouse utilizes primarily only
two askarels, Aroclor 1242 for transformers and
Aroclor 1016 for capacitors as inerteen. Since the
early 1970's, when scientific studies indicated that
PCB mixtures presented some hazard in the arr. iron-
ment, Westinghouse has expended considerable
money and effort to reduce the amount that inight
escape into the environment.
Measures that have been employed are. The
sealing of drains in manufacturing areas where iner-
teen is used; utilizing specially designed incineration
facilities for the destruction of scrap inerteen and
special scientific landfills for the disposal of iner-
teen-contami rated materials; instructing operation
personnel am' our customers regarding the need for
361
-------
care and that special waste disposal is required; and
reducing the number of pounds of inerteen per
KVA in transformers and capacitors. Most of these
measures were implemented prior to the enactment
of the Federal Water Pollution Control Act amend-
ments of 1972. It is significant to note that France
has just enacted regulations on the use of PCB's
which require actions that have been taken by West-
inghouse since 1972.
Westinghouse recognized that these measures
could not prevent the total elimination of inerteen
escaping into the environment. Therefore, concur-
rent with the above measures, we have conducted
extensive evaluation programs designed to utilize
those mixtures of PCB's having low persistence and
high biodegradibility in the environment.
By February 1968, Westinghouse determined
that a mixture of PCB's sold by Monsanto as Aro-
clor 1242 would be satisfactory as inerteen for
transformers. Aroclor 1242 contains about 91 per-
cent of the lower isomers, containing four chlorines
or less that more readily biodegrade in the environ-
ment.
This material has been used by Westinghouse
since that time, with the understanding that over 90
percent of the small amount that did enter into the
environment would have relatively low persistence.
Monsanto subsequently developed a new material
from Aroclor 1242 which contains more of the
lower chlorinated isomers and marketed this mate-
rial as Aroclor 1016. By the first quarter of 1972,
this material was introduced by Westinghouse into
the manufacture of all capacitors.
This material contains 99 percent of the lower
biodegradible isomers, four chlorines or less, so that
less than 1 percent of this material that might
escape into the environment might be more resistant
to biodegradation. The industry, Monsanto, our
own research, scientific literature, and most of the
papers presented at this conference have indicated
that the lower chlorinated mixtures of polychlori-
nated biphenyls are more biodegradible and do not
present the same long-term toxic environmental
problems as those which contain the higher chlori-
nated isomers.
It is interesting to note, in this regard, that EPA
researchers have found a significant difference be-
tween the effects of Aroclor 1242 and Aroclor 1016
on rats, confirming our position. But they published
this information in Great Britain and did not make
the information available during the toxic hearings
of 1974. We believe the U.S. scientific community
should determine the benefits and the environ-
mental impact of the two or three askarels used by
the electrical industry on a scientific basis and not
let the desire to see a toxic substance bill passed
stampede us into a selection of an alternate fluid
which is more potentially dangerous to man and to
his environment. Thank you.
STATEMENT RELATING TO POLYCHLOR1NATED BIPHENYLS
ON BEHALF OF THE WISCONSIN PAPER COUNCIL
James S. Haney*
7"/7e Paper and Paper Recycling Industries in Wisconsin
I appear today on behalf of the Wisconsin Paper
Council, the trade association for the pulp and paper
industry within Wisconsin. I am chairman of the Wiscon-
sin Paper Council's Government Relations Committee.
There are 49 pulp and paper mills in Wisconsin
employing 46,000 people who produce in excess of 5
million tons of pulp and paper products annually.
Wisconsin manufactures more than 1 I percent of the
'Public Affairs Director, Bergstroin Paper Company,
Neenah, Wisconsin.
total production of pulp and paper products in the
United States and is the number one paper-producing
State in the country.
Not only do we lead the nation \r\papermaking, but
we are also the number one State in paper recycling. At
least 19 Wisconsin paper firms recycle fibers to some
extent and several firms make a specialty of it. A fifth of
Wisconsin's annual paper production, about 780,000
tons, is made from recycled, post-consumer wastes.
Some Wisconsin papermakers, like my own company,
have been producing recycled paper and paperboard
since the turn of the century.
362
-------
What Has The Wisconsin Paper Industry Done For The
Environment?
Manufacturing any product is not a clean, tidy
process. Generally, it is noisy, usually it is dirty, and
often it involves work with large machinery. It normally
takes skilled labor, of which Wisconsin is fortunate to
have an ample and sufficient supply. The point being,
however, that in the manufacturing process certain
natural resources are consumed and related byproducts
are discharged or emitted as a part of the process itself.
Recognizing this impact on the environment upon
which our industry depends, the Wisconsin paper indus-
try had expended approximately $126 million on water
pollution abatement equipment prior to 1975. It is esti-
mated by the industry that within the next 5 years an
additional $153 million, at a minimum, will be expended
for a total investment of approximately $280 million for
water pollution abatement equipment alone, not one
cent of which is attributable to new production equip-
ment.
As to air pollution, prior to 1975, the Wisconsin
paper industry had invested approximately $34 million
in air pollution abatement equipment and anticipates
that between 1975 and 1980 it will invest minimally an
additional sum in excess of $60 million. In rough figures,
therefore, the paper industry in Wisconsin alone will
have spent approximately $375 million by 1980 for air
and water pollution abatement equipment—approxi-
mately $8,200 per employee-on what is very environ-
mentally necessary, but absolutely unproductive, equip-
ment.
77?e Issue of Polychlorinaied Biphenyls
In light of previous comments at this conference, I
think I need spend little time in identifying polychlo-
rinated biphenyls (PCB's) or their historical uses. One of
the many varied uses of PCB's prior to 1971 had been in
carbonless copy paper, which has accumulated in the
files of many businesses and numerous governmental
agencies. From time to time, some of this paper is dis-
carded and becomes part of the solid waste chain.
At this time I wish to make one point very clear.
Wastepaper collectors and recyclers do not manufacture
PCB's nor do they use them in their manufacturing
process. To the extent that recyclable wastepaper does
contain traces of PCB's, this contaminant is introduced
into the industrial system and becomes part of the in-
dustrial waste discharge of recycling facilities. The only
other known PCB's on a paper mill's premises might be
PCB-containing transformers or capacitors.
The Wisconsin Paper Council is vitally concerned
that overly restrictive regulations of PCB's, both in fin-
ished paper or paperboard products or in effluent dis-
charges, could destroy the Nation's recycling efforts. We
strongly urge that those who are drafting regulations
concerning PCB's more fully analyze the impact of such
regulations on recycling industries.
You must understand, for example, that a very
small portion of the total amount of PCB's manufac-
tured domestically by Monsanto Company were used for
carbonless paper, which is the chief assumed source by
which wastepaper contains the PCB contaminant.
Aroclor 1242, by weight containing relatively lower
amounts of chlorine than other domestically produced
and sold PCB's, was used in the production of carbonless
paper. Between 1958 and 1971, at which time the use of
PCB's in the manufacture of carbonless paper was
ceased, approximately 48 percent of Monsanto's PCB
production was of Aroclor 1242. However, of its entire
domestically sold production during those years, only
about 22 percent was used for "plasticizer applications."
Plasticizer applications include not only use for carbon-
less paper, but also for adhesives, textile and other sur-
face coatings, inks, investment casting wax, and sealants.
Therefore, we know that something considerably less
than 10 percent of Monsanto's total PCB production
between 1958 and 1971 was used in the manufacture of
carbonless paper, all of it being of the Aroclor 1242
variety.
Aroclor 1242 has significantly different structural
constituent characteristics, whereby its stability and
persistence are less and its degradeability appears to be
significantly higher than its comparatively more highly
chlorinated Aroclor relatives. At least 1,500 reports in
scientific literature have been written relating to PCB's
and, whereas most of these deal with only the question
of reporting the presence of PCB's in the environment,
invariably these reports describe and relate to Aroclor
1254 and 1260, the more highly chlorinated PCB's
produced by Monsanto. In fact, a Monsanto spokesman
has indicated that it was his opinion that "if we could
just turn the clock back" and have produced only
Aroclors 1221, 1232, 1242, and no others, we probably
wouldn't be holding hearings today. We are told that the
principal Aroclors being found in Wisconsin fish are
Aroclor 1254 (Mississippi River) and Aroclor 1248
(lower Green Bay). Predominantly it is Aroclor 1254
that is found in the environment. In terms of degrada-
tion and degradeability, there is a definite difference
between Aroclors 1242 and 1254.
On the issue of bioconcentration, the EPA has
stated that Aroclor 1242 bioaccumulates on the order of
8 times less than the more highly chlorinated Aroclors.
On the issue of removal from effluent, the EPA has
predicted that we can look forward to significant reduc-
tions in discharge concentrations as the program and
363
-------
projected treatment systems required by the NPDES
program become effectively operational.
All of the above can be restated concisely as fol-
lows. Only a small portion of total PCB's domestically
produced were utilized for purposes of manufacturing
carbonless paper and, as to those particular Aroclors,
they are relatively less stable and persistent, appear to be
more degradeable, and are less susceptible to accumula-
tion in fish than are their related, more highly chlori-
nated Aroclors. As a result, the impact of the waste
paper recycling industry on the issue of PCB's must be
put into a more proper and positive perspective.
Concluding Remarks
I think the time has come for us to recognize that
we all know less than we would like to know about
PCB's. Because of their persistence and because of
uncertainties about their impact, the new production of
this substance has all but been eliminated and is now
used • ->f only very specific purposes. An inventory must
be n de of where PCB's are coming from; the type of
Arociors that are being discharged, emitted, and land-
filled; the best methods of decreasing these discharges,
emissions, and landfilling; and to put some proper per-
spective on the existence of this substance in our envi-
ronment. We know of no current practical method by
which to separate out of the wastepaper mass that por-
tion of paper that contains PCB's—particularly since
PCB'i have been recycled into paper products other than
carbonless paper. PCB's cannot be legislated out of the
recycled paper system. The whole concept of recycling
wastepaper is at stake in considering the promulgation of
regulations particularly at a time when, as a national
industry, the pulp and paper industry is expanding its
papermaking capacity at a faster rate than it is expand-
ing its ability to produce pulp. It simply must be a na-
tional priority to encourage recycling.
The Wisconsin Paper Council recognizes that there is
a potential problem with the introduction of PCB's into
the environment. We strongly support strict controls on
the manufacture, distribution, and use of PCB's and we
favor a national ban on the importation of PCB's. But
the paper industry has not created this problem, it does
not use PCB's in its processes, and it finds itself caught
in the middle of this controversy merely because of its
recycling efforts, which would be halted by the adoption
of overly restrictive regulations.
For example, proposed regulations in Wisconsin
place an incredible burden on our industry, requiring
removal of PCB's to levels 1,000 times smaller than the
Food & Drug Administration's temporary tolerances as
applied to food.
Our industry has a history of cooperation with gov-
ernment agencies to reduce PCB levels in our finished
products. We will continue to cooperate with the Food
& Drug Administration, with the EPA, and with our own
DNR to find solutions to the PCB problem in effluent.
We concurred with Mr. Schweitzer when he testified in
Wisconsin that "it is important to clarify the portion of
the PCB contamination problem which can be attributed
to specific discharges and the practical feasibility of
reducing the discharges." We hope that his Department
recognizes that there is a difference in terms of environ-
mental acceptance of various forms of PCB's and that
this should be taken into account when dealing with any
proposed regulations.
But we continue to appeal to you for reason. Let us
admit together that we do not know enough, at least at
this point, to promulgate reasonable regulations and
that ill-conceived rules could mean economic cata-
strophe for a significant portion of Wisconsin's paper
industry. The commitment of this industry is to Wiscon-
sin and to its environmentally pure future. It has invest-
ed and will invest over $300 million prior to 1980 to
accomplish that goal. We only hope that realistic, reason-
able, feasible, and responsible regulations will be pro-
posed by the EPA which will bolster its reputation as a
defender of the environment while at the same time not
place it in a position of ridicule because it has suggested
regulations so badly researched that they are either
unenforceable or that they destroy recycling—one of the
this country's most environmentally considerate indus-
tries.
CHAIRMAN TIMM: Now for another change of pace,
David Kotelchuck, followed by Lee Botts.
DR. DAVID KOTELCHUCK (United Electrical Workers
Union, New York, New York): At present, several
States are proposing new PCB standards while EPA
is actively considering such a standard. New stand-
ards for PCB's are clearly in process. I would like to
discuss a matter that is of great importance to elec-
trical workers, the people first affected by PCB's in
the environment and the people whose lives are
most immediately affected by the changes in the
standards, both in terms of the health and jobs.
364
-------
We want to point out that attempts to regulate
PCB's use State by State leaves workers in existing
plants subject to job loss through plants moving.
United Electrical Workers represents over 1,000
workers at GE Capacitor plants at Fort Edwards and
Hudson Falls, New York. Presently a New York
State law is being considered phasing out PCB by
next year. If the New York State laws pass in the
absence of a Federal standard, then workers in New
York and other States with stringent standards face
possible plant moves and subsequent job loss.
Local GE plant officials have already publicly
threatened to move if proposed New York State
standards pass. We recognize the need for change in
PCB standards to protect the health of workers and
the general public. But we insist that this must be
done by promulgating a Federal standard so as not
to subject workers to this threat and not prejudice
their job security relative to workers in other States.
It is incumbent upon EPA to set a new Federal
standard. We want to point out that this is also the
most effective way to regulate PCB in the environ-
ment.
One further point. We commend scientists who
have examined health and environmental hazards of
PCB. But a report of the results in medical and
scientific literature does not end the scientist's
responsibility in our opinion. We believe that
scientists also have a responsibility to inform elec-
trical workers, those most directly affected by any
PCB health hazard, of their results. In the past
several years neither workers at the Fort Edward
and Hudson Falls plants nor their national Union
were informed by scientists or government officials
of their findings or proposals. One cannot claim to
be helping mankind by researching PCB hazards and
regulating its use while ignoring precisely those
individuals most intimately affected by PCB.
We request that as new scientific studies are
conducted the authors please inform us of their
results. Our address: Research Department, United
Electrical Workers, 11 East 51st Street, New York,
New York 10022. Thank you.
BETTER LATE THAN NEVER: THE CASE FOR TREATING
PCB'S AS TOXIC SUBSTANCES NOW
Lee Botts*
My name is Lee Botts, and I represent the Lake
Michigan Federation, a coalition of citizen groups and
individuals with members in Wisconsin, Illinois,
Michigan, and Indiana. Our affilitates include organiza-
tions of conservationists, of sports fishermen, of orga-
nized labor, of school children, and of people who could
be classified under many other labels but share. a
common concern for protection of Lake Michigan from
manmade pollution. Today I am here to express the
dismay of our organization over the failure of the Gov-
ernment of the United States to protect the lake and
those of us who depend on it for drinking water, for
food, and for the quality of our lives in the future
against contamination by polychlorinated biphenyls
(PCB's).
The fact that such contimaination exists is not
news. Attention was called to PCB's as a potential dan-
ger in a Lake Michigan Enforcement Conference in
1971. We worked for and celebrated the passage of the
*Executive Director, Lake Michigan Federation, Chicago,
Illinois.
Water Pollution Control Act amendments in 1972. We
have asked for and waited for regulatory action on toxic
substances that would include PCB's as provided for
under Section 307. In the past year we have become
increasingly alarmed over the failure of EPA to make use
of its powers under Section 504.
Under this section, the administrator may bring suit
on behalf of the United States to stop pollution that
threatens either the public health or the means of liveli-
hood of people. PCB's do both, and yet what has EPA
done?
EPA ACTIONS TO DATE
Since 1972, EPA officials have been assuring them-
selves, if not the rest of us, that, in the words of John
Buckley, chairman of this conference, "The PCB prob-
lem is fairly well in hand." This statement was attributed
to him in a Science magazine discussion of PCB's in
October, 1972 (page 388, Vol. 178). Just how EPA
reached this conclusion is a mystery, since it was not
365
-------
confirmed by the monitoring efforts being made by
agencies here in Region V, including the National Water
Quality Laboratory in Duluth and the Great Lakes
Fishery Laboratory in Ann Arbor.
When confronted with the rising levels of PCB's
found by monitoring in the Great Lakes, Washington
EPA officials dismissed the problem as a regional one.
Now this is a fairly large region, and it might have
seemed reasonable to investigate whether PCB's were
present in other waterways when their existence in the
largest fresh water system in the world was so wide-
spread. But evidently the thought was that if you do not
look for a problem, you will not have to deal with it.
Unfortunately, the problem was not only present else-
where; research confirmed that it was growing worse.
NATURE OF THE PCB PROBLEMS
!n various research efforts, the nature of the prob-
lem was becoming clear. First, there is the fact that
PCB's have high concentration factors, considerably
higher than those of the chlorinated hydrocarbon pesti-
cides. Evidence suggests that PCB's may not be as solu-
ble in water, but there is no doubt now that biomagnif i-
cation of PCB's in the food chain is very great.
Second, a number of the 190 different PCB com-
pounds degrade very slowly. The U.S. Department of
Agriculture found in experiments reported in a 1972
conference that the isomers in the intermediate range of
chlorine content were more toxic to chickens than those
with either very small or very high chlorine content.
Third, it was learned that, like DDT and other pesti-
cides, PCB's are stored in fatty tissues of animals and
man, ready to be released with metabolism of the fat.
One 1974 report on this phenomenon in the Bulletin of
Environmental Control and Technology found that
normal persons seem to have small blood level concen-
trations of both DDT and PCB's even if they have higher
levels in stored fat. But nine persons with cancer were
found to have extremely high levels of both the
degraded form of DDT and PCB's in their blood, suggest-
ing that the toxic chemicals had been released into the
bloodstream during an illness that causes weight loss
through fat metabolism. The authors of this report
speculate that this mechanism may offer a much more
serious long-term threat to health than was previously
realized, since it would affect people already sick, or
growing old, or even those trying to improve their health
by dieting to lose weight.
The point is that for several years many investi-
gators have been trying to find out not only whether
PCB's are toxic but how they cause trouble. That is,
many investigators outside EPA were studying the prob-
lem.
WHAT EPA HAS NOT DONE
In this connection, let us consider what EPA has not
done that might have reasonably been expected of the
agency that has the charge of protecting the environ-
ment and public health in general but has the power to
regulate specific toxic substances.
The major action to determine sources of PCB's was
to request information from industries that might have
occasion to discharge wastes containing PCB's into
waterways, that is, to be point sources of PCB's. Since
Section 308 applies only to owners and operators of
such sources, this inquiry was not adequate to disclose
all the industrial users of PCB's nor means of distribu-
tion from manufacturers through middlemen to actual
users. Strictly speaking, an industry that did not dis-
charge PCB's directly would not have to provide infor-
mation under Section 308 letters about whether it made
and sold products containing the chemicals that might
ultimately reach the environment by other means.
Conceivably, EPA might have been trying to find
out for itself just how the PCB's were being scattered so
widely. But EPA did not, for example, investigate
whether PCB's are finding their way into rivers and lakes
from sanitary landfills. Nor did it obtain information
about possible atmospheric transfer, even though the
fact that other substances are carried into bodies of
water like Lake Michigan by rainfall is stimulating atten-
tion to this mechanism.
Having failed to take advantage of PL 92-500, it
might have been supposed that EPA would turn to other
means of regulation. Again, not so. PCB's are not regu-
lated under the Safe Drinking Water Act, either.
CONCLUSION
I spoke in the beginning of the failure of the Federal
Government to deal adequately with the PCB problem,
but in truth some agencies have already taken some
initiative. The Food and Drug Administration is amend-
ing its food packaging regulations to prevent contamina-
tion by plastic wrappings. The Department of Defense
and the General Service Administration have indicated
willingness to restrict purchase and use of items contain-
ing or using PCB's.
Some States have acted, at least to protect the
public even though such actions can do little to prevent
continuing environmental contamination. Wisconsin and
Michigan have issued warnings to the public about eating
366
-------
fish caught in Lake Michigan more than once a week.
This warning, of course, is cold comfort indeed to the
fishermen, whether for sport or for a living. Present at
this meeting are representatives of both groups who will
speak to their own interests in this matter.
In calling for decisive regulatory action by the Envi-
ronmental Protection Agency now, I would like to
submit to you several petitions signed by individual
members of one of the member organizations of the
Lake Michigan Federation, the National Council of
Jewish Women. This is tangible evidence of their con-
cern, but I can assert with confidence that it is shared
not only by other members of the Lake Michigan
Federation but almost everyone who understands the
nature of this problem. EPA must understand that its
leadership is needed to deal with this national problem
now.
A FAILURE OF GOVERNMENT
Richard R. Knabel*
Representing:
The Hudson River Fisherman's Association
The Hudson River Sloop Restoration
The Federated Conservationists of Westchester County
The Hudson River Fisherman's Association, the
Sloop Restoration, and the Federated Conservationists
of Westchester County together represent the major ele-
ments of the environmental movement in the Hudson
Valley. They have collectively helped to define many of
the environmental safeguards, such as they are, that have
come into being since public awareness of ecological
problems came into its own during the past 10 or 12
years.
My comments today, on behalf of these groups, are
intended to raise the "decibel level," as Administrator
Train commented yesterday, but not intended to criti-
cize the efforts of this conference or its participants.
What we in the Hudson Valley have experienced over the
past 3 months, and all that I have heard since arriving in
Chicago, indicates that the decibel level has not yet
reached the pain threshold in government offices. We are
astonished -at the delays. We cannot understand why it
has taken so long for the PCB menace to surface, and we
are horrified that so little action seems to be contem-
plated. We wonder what would have happened if the
expose begun by Commissioner of Environmental Con-
servation, Ogden Reid, in New York State had not
occurred.
As many of you may know, this conference owes its
genesis, in part, to the almost unbelievable revelations in
the Hudson Valley last August. On August 8, 1975,
Commissioner Reid dropped a bombshell on the public
*Director, Hudson River Fishermen's Association, York-
town Heights, New York.
by warning them not to eat striped bass from both the
Hudson River and Lake Ontario because data given him
by the EPA indicated levels of PCB's exceeding 5 ppm
were found in the fish taken from both waterbodies. He
identified the culprit in the case of the Hudson Riveras
primarily the two General Electric facilities at Fort
Edward and Hudson Falls, New York, whose massive
capacitor plants there were dumping an average of 30 Ib.
per day of PCB. The river is apparently contaminated
for a distance exceeding 100 miles, and the entire fishery
is in question.
As one might imagine, the reaction to this stunning
announcement was one of shock, frustration, disgust,
dismay and confusion. The reasonably successful clean-
up of sewage and industrial waste in the Hudson Valley,
while far from complete, was making visible progress.
The water was not only cleaner to the eye, but the
increased variety of fish returning to the river in num-
bers not seen by commercial fishermen for over 20 years
inspired confidence and pride. Since 1972, the Sloop
Restoration had been sponsoring an annual shad sail in
which thousands of people had participated by eating
freshly caught shad. Eating fish from a cleaner Hudson
was a natural outgrowth of the cleaner water we all
thought existed. Imagine the concern, and fright of all
these people on the morning of August 8th.
When the shock wore off somewhat, many of us
asked; was this a new discovery? Was this just another
layer of contamination that no one had looked for
before? Did new analytical techniques, or a fortuitous
367
-------
investigation produce this damaging information? To our
horror, consternation, and anger, what we found, in New
York State anyway, was an Environmental Watergate
that knows no parallel. The confusion rapidly changed
to an angry feeling of betrayal.
As early as February 17, 1971, we discovered, ef-
forts were made by Mr. Robert Boyle of Sports Illus-
trated, and perhaps others, to alert New York State envi-
ronmental officials, notably Mr. Carl Parker, chief of the
Bureau of Fisheries, to the presence of dangerously high
PCB levels in striped bass eggs, and levels approaching
the cutoff of 5.0 ppm in fish tissue. Mr. Boyle describes
the response he got as "derisive." Not only was no ac-
tion taken by State officials, but considerable evidence
exists that active efforts to suppress any information
about PCB contamination persisted within the depart-
ment for several years. All of this despite reports of the
problem written by Boyle in both Sports Illustrated and
Audubon Magazine in 1970.
In June, 1971, the New York State Department of
Health certified that the water quality of the discharge
from the two enormous General Electric plants met its
criteria. In spite of the fact that 5.7 million Ib of PCB's
are used at these plants each year, no mention of PCB's
was made by the health department.
In July and through September 1972 (11/2 years
after Boyle first signaled trouble), New York State
undertook PCB analyses in the mid-Hudson area and dis-
covered concentrations exceeding FDA limits of 5.0
ppm in fish. This information never saw the light of day.
The then Commissioner, Henry Diamond, recently dis-
claimed any knowledge of the study or its damaging
results. His successor, James Biggane, also denies knowl-
edge, and the new Commissioner claims he found out
from Federal sources, not from within his own depart-
ment. Reid said in a New York Times story, by Richard
Savero, "There has been a failure of government here...,"
referring to the suppression of information within his
newly aquired department. That was a masterful exam-
ple of understatement.
Subsequent further investigation revealed that
between 1970 and 1975, 99 analyses of Hudson River
fish were conducted by State officials, and in 52 cases
the PCB levels were greater than the maximum allowable
level of 5.0 ppm. A largemouth bass caught at the mouth
of Esopus Creek, about 80 miles north of New York
City, in 1970, but not analyzed until 1972, contained
53.8 ppm, or more than 10 times the maximum allow-
able limit. Subsequently, levels were detected in several
species that ranged to over 100 ppm, with levels gener-
ally decreasing as distance from the GE discharges
increased.
On September 8, 1975, GE was ordered by the
State to stop dumping its average of 30 Ib per day by
September 30, 1976, and to immediately curtail its dis-
charges to 2 Ib per day iss of September 30, 1975. Reid
required GE to post a $2 million performance bond to
back up his order. GE's response was to contest the
order, as it did the provisions of its NPDES permit,
which also required a major curtailment of PCB dis-
charges, and to claim that it had already voluntarily
reduced the discharge levels to under 2 Ib per day. How-
ever, in the course of hearings, going on at this moment
in Albany, it has been revealed that in the 24-hour
period between October 17 and 18, 1975, 75 Ib of PCB's
were dumped a1 the Fort Edward Plant, by virtue of
"heavy rain during sewer line repair." On September
13-14, 1975, a horrendous 116 Ibs of PCB's were
dumped by the Hudson Falls plant with no reason
stated. Both pieces of data came from GE's own written
responses to questions raised by State environmental
lawyers. Based upon data the EPA has presented at this
meeting, both ot these occurances represent major spills.
I wonder if the EPA is aware of them, and what they
will do about them.
In any case, it is clear that GE has not curtailed its
discharges, and it seems probable that this random and
massive dosing of the Hudson will continue to poison
and jeopardize the health, safety, and welfare of
residents not only in the valley, but all along the north-
eastern seaboard, where commercial fishermen catch fish
born and raised in the Hudson Estuary.
While the record of State officials is both shamefui
and scandalous, the EPA has not acted with openness, or
alacrity either. I should say that Region M's behavior has
left much to be desired in this matter. Without providing
the full details, which I will gladly do for anyone
desiring them, our investigations of the Region II office's
actions indicate that it too had knowledge of the sever-
ity and extent ot the PCB problem in the Hudson long
before it forwarded the data to Albany or made it public
themselves.
An internal EPA memo dated May 31, 1974, reveals
a request from Sandrai Kunsberg, attorney in the Water
Enforcement Branch, to Dr. Richard Spears, Chief of
Surveillance and Analysis Division, to conduct sampling
at the GE plant', and in the Hudson River, to "Deter-
mine whether or not there exists a health hazard within
the meaning of Sectioi 504 of the Water Pollution
Control Act." This request was occasioned by testimony
at the May 1974 EPA hearings on toxic substances
standards where GE revealed the extent of its PCB dis-
charges into the Hudson River.
The EPA lab report on this investigation, dated
October 1974, concluded "that the biotic component of
the river ecology are heavily contaminated with PCB's,
368
-------
grazing populations as well as carnivorous piscine popu-
lations," and notes that certain areas around Fort
Edward and Hudson Falls "are fished primarily by the
youngsters of Fort Edward. Ingestion of these fish by
the populus would certainly lead to contamination of
specific tissues in their bodies...." There was no health
alert. No news release. There was nothing.
Almost 1 year went by before this information
finally reached the new environmental commissioner of
New York. The question again is why? We must ask,
how can so-called public servants walk around with the
knowledge that commercial and sports fishermen up and
down the North Atlantic as well as on the Hudson were
catching Hudson River striped bass, shad, small mouth
bass, and eels for human consumption, knowing full well
that the likelihood of their contamination was great,
that the fish posed a health hazard, and that their oaths
of office required action. That this situation could per-
sist for literally years is unforgiveable. A failure of gov-
ernment? No. Indictable criminal offenses more suited
to investigation by a grand jury than discussion at a
conference such as this one.
As far as action to end the problem nationwide is
concerned, we decry the procrastination, fear, or what-
ever, that seems to underlie the apparent lack of direc-
tion and assertiveness thus far displayed. There still
appears to be a question about what comes first, the
national health or the business interests of the electrical
and other industries that rely upon PCB's for their
profits.
We fail to see how a proposed standard of 1 part per
trillion ambient in the Nation's waterways will solve the
problem. Is it low enough? Can it be enforced? How was
it arrived at? Can we live with PCB's at all? What will
happen, or rather what should happen to the more than
100 million Ib of PCB still available to be degraded or
released into the environment? How will we deal with
this problem?
It is equally alarming to note that the FDA has not
stated here one syllable about any proposed change in
the permissible PCB levels in food or fish. We wonder
why fish have highest permissible PCB level in the first
place. The suggestion that PCB levels are decreasing in all
foods except fish seems to contradict the ubiquitous
nature of PCB's, and creates a false sense of security.
Our Canadian neighbors have announced a new lower
standard of 2.0 ppm in food, and Commissioner Ogden
Reid has taken the position, to his credit again, that a
standard of 1.0 ppm seems to be desirable. When will the
FDA take some action?
Getting back to the Hudson Valley, which we hope
is riot the average situation around the country, the
fledgling Hudson River fishery, thanks to GE, is dead for
all intents and purposes. Commercial fishermen who had
hoped to go back to fishing full time have scrapped their
plans. Even if their catches were not contaminated, fish
markets won't buy them or pay such low prices that no
profit is possible. The public is now convinced that
Hudson fish are tainted, and will continue to think so
for many years regardless of cleanup requirements or
measurable improvements that may or may not take
place. The implications for the North Atlantic fishery
have yet to be explored or defined, but the potential
economic impact of the August 8th revelation, an envi-
ronmental Pearl Harbour, for fishermen everywhere is
devastating. Confidence in government and in the
Hudson's recovery is at a new low.
In conclusion, the time to act is now. Administrator
Train said yesterday that he hopes this will be his last
PCB conference. Well, we also hope that no more confer-
ences on PCB's will be necessary. How much data does it
take before action can be justified? Must we suffer an
outbreak of Yusho disease before the problem assumes
real proportions? We must have more than conferences.
And we expect more than talk.
Thank you for your attention, and for this opportu-
nity to speak.
MS. EILEEN JOHNSTON (Concerned citizen): Thank
you, Chris. Well, I would like to thank the U.S.
Environmental Protection Agency for putting on
this stimulating meeting. I felt privileged to be in
the room with so many fantastic research members
and I was a little encouraged and discouraged. I
happen to live in the Lake Michigan basin. I was
wondering, too, where are all the concerned citi-
zens. I really saw very few people from Illinois that
I felt should have been here if they were concerned
about PCB's.
I also want to congratulate the State of Wiscon-
sin for the hearings that they have held, and I'll be
very anxious to see what comes from those, and also
to congratulate the State of Michigan for the fine
presentation that John Hesse made. I will be inter-
ested to follow House Bill 5619 in Michigan.
My own great concern for PCB's in the environ-
369
-------
merit is due to my own Illinois Environmental Pro-
tection Agency. Last February the agency was asked
to host the February meeting for the Governor's
five-State Interdisciplinary Council on Pesticides.
Jim Frank, a very capable young man from EPA,
put on an all-day meeting on PCB's. I was the only
citizen at this meeting and it was so stimulating that
I started out to do what an individual citizen can
do. I talked to a few citizen groups that I am associ-
ated with and we decided to put on a meeting to
hHp warn the Lake Michigan fishermen about this
and we held the meeting in March or April.
I urged more citizen groups to do this sort of
thing—to take positive action. Citizens need more
education. I hope that USEPA and everybody else
concerned with PCB's will really listen to Carlos
FetterhoJf, who really socked it to people tonight.
Getting back to Illinois, I've talked to 225 citi-
zens quite recently and explained to them the perils
of PCB's and they signed petitions for me to take to
the Illinois Pollution Control Board to ask it to hold
informational hearings on PCB's, to get them in-
formed, and to get our own Illinois EPA and inter-
ested citizens to be better informed. They decided
to wait until after these meetings to decide whether
to hold hearings.
Another thing I heard today that the research-
ers mentioned is that we ought to get together and
get some standardized analytical methods. Remem-
ber when we were concerned about DDT? I attend-
ed a 2-day seminar out on Pershing Road at EPA
headquarters. Everybody was analyzing whole fish,
half fish, and it seems to me from what I heard that
they really should get together and develop uniform
procedures.
I think it was a great conference but I really
want to know what EPA is going to do. What are
you guys going to do? I have great faith in the U.S.
Environmental Protection Agency. I know so many
people in Region V—but what are you going to do?
Are you going to Congress? Are you going to take
action? Are you going to answer the questions
tonight, Chris? Thank you.
Session continued on next page.
370
-------
MR. RAY OLTMANNS (Illinois Wildlife Federation, letter (figure 1) that is going to go to Mr. Train; it is
Blue Island, Illinois): I am a delegate from the from Frank Goetschel, our president. Thank you.
Illinois Wildlife Federation. I am going to read a
IlLIMOI^xMM^
\AxAxL/*-/\_xvAIr^-X
FEDERATION^)
13005 S. WESTERN AVE. BLUE ISLAND. ILLINOIS 60406
r. O. IOX 116 PHONE 312-368-3995
November 18, 1975
Mr. Russell B. Train
Administrator
U. S. Environmental Protection Agency
Washington, D. C. 20460
Dear Mr. Train:
The Illinois Wildlife Federation concurs with the need for
immediate and strict regulations of production, distribution and
use of the industrial chemicals called polychlorinated biphenyls (PCB).
Failure of the Environmental Protection Agency to have restricted
these chemicals as toxic substances under the Federal Water Pollution
Control Act of 1972 cannot be excused. Their widespread distribution in
the environment and the threat they pose to public health has been fully
documented and are well known to your agency. Yet to date EPA has
contented itself with requests for voluntary action by industry even
while PCB's have continued to accumulate in ever higher levels in all
water wastes, and while research evidence has continued to confirm their
toxicity.
A
The chance to take preventive action was missed when EPA delayed
and delayed its regulations of PCBs as a toxic substance. We feel action
is now mandatory to ban the use of PCBs.
Sincerely yours.
Frank Goetschel
President
FG:sa
cc: Ace Extrom, Exec. Sec.
NATIOMAL WILDLIFE FFDERAT1ON AK-IUATe
PUBLISHERS OF
ILLIHOI
Figure 1. Letter.
371
-------
MR. BURNETT BAUER (State Senator from South
Bend, Indiana): First of all, I want to congratulate
the EPA for holding a meeting at which it can't
really win. I've heard in this meeting that they've
done too much and then I've heard them damned
for doing too little. And they don't have to do that;
we in politics every election have to stand up and
take it, but they really don't have to. But they did
call this meeting and I think it's been very beneficial
and the fact that we've had discussions is a real step
toward solving what all of us recognize is a real
problem.
Now the reason I want to talk here is because I
want to make one suggestion for those who want
the government to take some action. That was sug-
gested a number of times. It'll also maybe warn
those who don't want the government to do a darn
thing. What I'm suggesting is this, that you not wait
for the Federal Government to start action on PCB's
but you start it in the States. I know that's contrary
to most of the procedure and most of the thoughts
that people have, particularly those in State Govern-
ment. But the historical fact is most of the social
changes in our country started in States first. The
women's sufferage movement was not suddenly
brought on by the Federal Government; the States
first started allowing women to vote. We know that
most of the environmental actions were started in a
locality and in the State.
It's just a fact that once the Federal Govern-
ment sees States acting that this indicates to them
seriousness, and then they go in and invest the time
and money that they have. Now there are several
reasons why we want the States to do this. First of
all, most of the legislatures are citizen legislatures.
In one sense, we're not as vulnerable to lobbyists.
Most of us are serving there because we want to
better our State. We want to give our children a
better place in which to live, and we are doing what
we think primarily would be best in the long run.
Second, we are closer to specific problems and
when we put a solution in there, it is probably a lot
closer to a genuine solution. It's much harder for
people in Washington to try to legislate something
that applies over the 50 States. If you start with
your actions at home-and God bless these women
out here who have these groups, they'll bring you
specific instances you'll start legislating laws that
will work. I'll give you just .one instance and then
I'll sit down.
In Indiana we have pollution of a lot of our fine
lakes and we heard it was because of phosphates.
Indiana passed the first statewide ban against phos-
phates in detergents. I'm the grandfather of that bill
because it was my son, who just happened to be in
the House, who got it passed. He had more energy
than I did. The real fact was that I was out for 2
years and the lobbyists went out of the State. They
didn't think the bill would be brought up. By the
time they found out, the Governor had already
signed it. So there's something in passing the work
onto the next generation.
We have found as a result of that ban that our
State's lakes are clearing up fantastically. That law
works. New York now has it. We hope other States
of the Great Lakes will adopt it. One reason I'm
here is I have met with groups that are around the
Great Lakes and the Great Lakes are in danger of
many things. And I just want to urge you people
who are in favor of having something done to go
home and start working on your State legislatures. I
know I'll get some letters from some of those guys
saying, "why don't you shut up, Bauer, we've got
enough work to do." But do that if you really are
genuine in your interest of getting some action
toward cleaning up our environment, and in passing
on to the next generation an atmosphere and envi-
ronment that can make us happy, and can make us
really enjoy the greatest country in the world.
I want to congratulate again EPA and every one
of you who came here from industry. I've learned a
heck of a lot here, and I think that all those who
participated in this meeting are really leaders and
genuine pioneers in this country. I salute you.
372
-------
MR. BARRY SCHADE (Minnesota Pollution Control
Agency, Roseville, Minnesota): The Minnesota Pol-
lution Control Agency is a member of a task force
made up of 11 agencies which represent the various
interests of two States and the Federal Government.
This task force was formed to investigate the
PCS pollution problem in the upper Mississippi
River and its tributaries. In response to preliminary
information provided by this task force and by vari-
ous other studies, the Minnesota Pol.lution Control
Agency board passed a resolution related to PCB's
on June 24th, 1975. This resolution, which supports
a Federal ban on the sale and use of PCB's, is sub-
mitted as figure 1.
CERTIFICATE OF MINNESOTA POLLUTION CONTROL AGENCY'S
AUTHORIZING RESOLUTION
I, Peter L. Gove, do hereby certify that I am Executive
Director of the Minnesota Pollution Control Agency, and that the
attached is a true, complete ami correct copy of a resolution
adopted at a meeting of the Board of 'the Minnesota Pollution
Control Agency duly and properly called and held on the 24th
day of June, 1975, that a quorun was present at said meeting,
that those present unanimously voted for the resolution and
that said resolution is set forth in the minutes of said meeting
and has not been rescinded or modified.
IN WITNESS WHEREOF, I have hereunto subscribed my name
this 25th day of June, 1975:
Peter
Executive Director
-Subscribed and sworn to before
me this 25th day of June, 1975:
MARY E. WYATT
••*>•* 1 WTMY fOBUC - KINHESOTA
DAKOTA COUNTY
/Notary Public*/
Figure 1. Resolution of Minnesota
Pollution Control Board.
373
-------
STATE OF MINNESOTA
MINNESOTA POLLUTION CONTROL AGENCY
June 24, 1975
RESOLUTION
WHEREAS, the Agency is charged with the administration and enforcement of all laws
relating to the pollution of any waters of the state as given in Minnesota
statutes of 1971, Chapter 115.03, and;
WHEREAS, no sewage, industrial waste or other wastes shall be- discharged into any
of the interstate or intrastate waters classified as fisheries and recre-
ation so as to cause any material change in any other substances or
characteristics which may impair the quality of interstate or intrastate
waters or the aquatic biota in any manner render them unsuitable or ob-
jectionable for fishing, fish culture or recreational uses as per Minne-
sota Pollution Control Agency regulations WPC 14 and 15, (1973 Supplement),
and;
WHEREAS, significant concentrations of persistent organic compounds known as
poly chlorinated biphenyls (PCBs) have been identified within the
Mississippi River near the border areas of Minnesota-Wisconsin known as
Lake Pepin, and;
WHEREAS, the United States Food and Drug Administration has enforced the "Action
Limit" of five (5) parts per million total PCBs on several shipments of
commercially caught rough fish from the Lake Pepin area resulting in
voluntary disposal of the fish by the industry, and;
WHEREAS, as a result of the above, commercial fishing operations have temporarily
been ceased in the Lake Pepin area, and;
Figure 1. Resolution of Minnesota
Pollution Control Board (con.).
374
-------
WHEREAS, on May 27, 1975 Dr. Warren K. Lawson, Minnesota Commissioner of Health
advised the public to limit consumption to no more than one meal per
week of fish taken from the Mississippi River from the Minneapolis-St.
Paul metropolitan area and lower Lake Pepin, and;
WHEREAS, a major study completed by Dr. J.R. Allen of the University of Wisconsin
(1974) indicated short-term toxicity to a low-level exposure to PCBs in
nonhuman primates, and this study and others suggests that there exists
a significant potential for harmful effects to humans, and;
WHEREAS, and as a result of the above actions significant environmental effects
on the aquatic life and economics of commercial and sports fisheries
as well as tourism have occurred, and;
WHEREAS, the Great Lakes Environmental Contaminant Survey (GLECS) conducted yearly
by Michigan's Departments of Natural Resources and Agriculture, the U.S.
Food and Drug Administration - Detroit Region, and the Great Lakes
Fishery Laboratory has determined that Lake Superior lake trout collected
near Isle Royale are showing a pattern of elevated PCB residues similar
to Lake Michigan.
NOW THEREFORE BE IT RESOLVED, that the Minnesota Pollution Control Agency Board
hereby supports a Federal ban on the sale and use of PCBs.
Figure 1. Resolution of Minnesota
Pollution Control Board (con.).
375
-------
MR. RICHARD T. FERRY (Bio-International, Inc.,
Woods Hole, Massachusetts): Bio-International,
Inc., is principally located in Ft. Lauderdale,
Florida, and holds four U.S. patents covering its
processes for the microbial degradation of petro-
leum and petroleum byproducts. Bio-International
holds one United States patent for a microbial
degradation facility; that is, a mechanical facility
comprising an interconnected initial and final de-
gradation system, each containing an inlet and out-
let and a conveying means together with aeration or
stirring devices and a drainage means.
This patent was issued only 3 months ago, on
August 11, 1975. Of particular interest to the group
here today is a patent held by the company relating
to the microbial degradation of polychlorinated
biphenyls that was issued on December 18, 1973
(see figure 1).
Bio-International is currently engaged in the
optimization of its processes at three leading univer-
sities in the Southeast. The purpose of this ongoing
work is to further increase the efficiency of the inte-
grated system and to broaden the scope of field
applications.
In the process, a significant amount of scientific
and technical data is being electronically stored for
quick retrieval when circumstances demand. This
information is also being synthesized in order to
prepare an affirmative response to the revised
Annex Ten of the National Contingency Plan rela-
tive to the introduction of microbial additives to the
environment.
Additionally, Bio-International maintains a
staff of internationally recognized scientific authori-
ties whose main thrust is in the area of environ-
mental consulting. The company is now analyzing
the effluent of major industries who recognize their
own obligation to solve their own effluent prob-
lems, particularly where PCB contamination is
involved. Upon the completion of these analyses, it
is envisioned that the company's integrated proc-
esses will be brought to bear on the problem efflu-
ents.
I would be remiss if I did not note in closing
that our ongoing studies relative to the problems of
PCB's in the environment would be much more dif-
ficult were it not for -the cooperation of Mr.
Papageorge and his colleagues at Monsanto as well as
other representatives of government and industry,
particularly the fishing and marine-related indus-
tries. For those of you who may be interested in the
biodegradation approach to environmental prob-
lems, you're invited to contact me here or by letter
and we'll be happy to provide you with more specif-
ic data. Thank you very much.
Figure 1 on following'page.
376
-------
UNITED STATES PATENT
3,899,376
August 12, 1975
MICROBIAL DEGRADATION FACILITY
ABSTRACT
A facility for the microbial- degradation of petroleum and oil wastes, as contained
in, e.g., industrial effluent discharge materials, comprising an interconnected initial
and final degradation system, each of which contains at least one tank means, associates
inlet and outlet means, conveying means, aeration or stirring means and drainage means.
The effluent to be degraded is introduced into the initial degradation system together
with the microorganisms imployed "and nutrients therefore, and degradation proceeds with
aeration or stirring with the formation of a protein-containing cell mass. The sub-
stantially degraded effluent is conveyed to the final degradation systcn where addi-
tional microorganisms are added to obtain the final degradation or polishing. The
resulting effluent, after filtering, is clean and clear and may be discharged safely
into the environment.
UNITED STATES PATENT
3,779,866
Dec. 18, 1975
MICROBIAL DEGRADATION OF POLYCHLORIMATED BIP11ENYLS
ABSTRACT
A process for the microbial degradation of polychlorinated biphenyls (PCBs) which
comprises treating the PCBs with certain non-pathogenic, hydrocarbon-utilizing strains
of Cladosporium cladosporiodes, Candida lipolytica, Nocardia globerula, Nocardia rubra
and/or Saccharomyces cerevisiae until the PCBs have been substantially degraded. The
process is applicable degrading PCBs as they may be present as pollutants or contami-
nants in water, in industrial effluents, in various land areas such as industrial sites
and the like or in varied laboratory or commercial installations. The process may also
be used to clean up and degrade mixtures of PCBs and various hydrocarbon oils or petro-
chemicals whenever their presence constitutes a deleterious pollution.
Figure 1. Abstract of patent relating to the microbial
degradation of polychlorinated biphenyls.
MAJOR GORDON GOFF (U.S. Army Materiel Com-
mand, Alexandria, Virginia): The following descrip-
tion of the spill of 265 gallons of PCB's into the
Duwamish Waterway in Seattle is presented here as
an ongoing practical problem that we're facing in
the recovery and disposal of contaminated bottom
sediments from a busy waterway in this industrial
area.
The spill itself occurred on September 13,
1974, when a large electrical transformer fully
sheath-crated for open-deck shipment to Alaska was
being sling-loaded aboard a barge. As the slung crate
was about 2 feet off the dock the bottom members
gave way, the transformer fell to the dock, and the
outboard cooling fins struck the bull rail, rupturing
them and leaking approximately 265 gallons of PCB
material in the transformer onto the dock and into
the waterway.
At that point in time, because of a lack of
awareness of the people on the scene as to exactly
what was in the transformer and the lack of labeling
or warning on the crating itself, the normal oil spill
procedures used at that dock were instituted. Within
2 or 3 days, however, the possibility that PCB's
were implicated in the spill appeared. Subsequent
investigations bore out the fact that the spill was
indeed PCB's. EPA and the State of Washington
Department of Ecology instituted an emergency
cleanup procedure. Handheld dredges manned by
divers recovered the visible pools of PCB's which
were lying on the bottom of the waterway.
A filtration unit was then moved into the area
377
-------
and the recovered material was run through this fil-
tration unit and the sludge that resulted was drum-
med and was subsequently disposed of by a com-
mercial contractor.
In this emergency operation, approximately 80
gallons of visible pools of PCB's were recovered. The
remaining PCB's are now in the bottom sediments
and subsequent sampling has established an area of
relatively high RGB contamination in the area of the
spill.
To cover the proposed procedures for the re-
covery of this I'd like to ask Mr. Jack Thompson,
who is a fisheries biologist with the Seattle District
Corps of Engineers, to cover the details of it.
MR. JOHN S. THOMPSON (Seattle District, U.S. Army
Corps of Engineers, Seattle, Washington): The pre-
vious speaker described events leading up to the
accidental loss of PCB's into the Duwamish Water-
way, Seattle, Washington, and partial removal of the
PCB's by EPA and Washington Department of
Ecology. There remains about 185 gallons of
Aroclor 1242 in the immediate area where the spill
occurred. About 2 months ago the Corps was re-
quested by the Department of Defense to remove
the contaminated sediments. This decision is sup-
ported by EPA and the State of Washington.
The Duwamish Waterway is a dredged channel
in the Duwamish River. It is dredged a distance of 5
miles from salt water with one-half of the channel
dredged to 30 feet below mean lower low water
(MLLW). The spill occurred at about river mile 2,
where the dredged channel is 30 feet below mean
lower low water.
Background levels of PCB's in bottom sedi-
ments run from 0.16 ppm to about 2.5 ppm. Levels
of PCB's in the area of spill range from about 5.4
ppm up to 390 ppm in the sediments. We propose
to remove the contaminated sediments, which will
require dredging up to 40,000 cubic yards.
We plan to use a dredge called Pneuma pump,
which is manufactured in Italy and represented in
the United States by a Chicago firm. This type of
dredge has never been used in Puget Sound country
and it is a little experimental for us. The advantage
of this particular dredge is that small amounts of
water are used for the pipeline dredging; in other
wofds, about 60 percent of the material that will
enter the pipeline is sediments and about 40 percent
water. Also, this dredge is excellent for controlling
turbidity and has excellent control of dredging
depth.
We plan on including predredging and post-
dredging monitoring- sampling, which will be per-
formed by EPA. There will be sampling during the
actual dredging. We have looked at a number of
disposal sites and methods and we have selected
one. All of the areas have one thing in common and
that is that no one wants the stuff.
The proposed disposal method is as follows: (1)
We will pump, using the pneumadredge, into a
watertight 4,000-yd3 barge; (2) When full,,the barge
will be hauled 2 miles upstream to the disposal area;
(3) The pneumadredge will then be placed into the
barge and sediments will then be pumped into a
disposal area.
The disposal area will be prepared beforehand
and will be roughly 300 feet from the waterway. In
the Seattle area, we have a tide drain from about
plus 12 feet down to about minus 2 feet below
MLLW. The disposal area bottom will be at 0 feet
MLLW elevation. Consequently, this material will be
placed in the water table. The disposal area will be
filled to about the plus 14 foot level. The disposal
area will be covered with 2-3 feet of clean dredged
materials after dredging is completed and material
has solidified. All effluents leaving the disposal area
will be run through a sand filter to remove sus-
pended sediments.
The cost of this operation will be between
$300,000 and $500,000. This is about $2,500 per
gallon of PCB's removed. This case study has been
presented to you to show one removal operation
and illustrate the problems involved in removal and
disposal of hazardous materials. Thank you.
378
-------
CHLORINATION OF WATERS FOR DISINFECTION-A STUDY OF THE
PRODUCTION OF UNDESIRABLE CHLORINATED PRODUCTS
Richard Johnsen, Ph.D.*
The current emphasis on environmental preservation
and human health is resulting in an increased use of
chlorine for disinfection and waste treatment. Few ef-
forts, if any, are being made by those proposing such
procedures to determine the possible adverse impact of
increased usage.
The use of chlorine for water treatment falls into
two categories: protection of public health, and indus-
trial use for antifouling and for waste treatment. In the
United States, chlorination of municiple water supplies
and wastewater treatment plant effluents is the most
common procedure for disinfection. Most biologists who
have maintained aquatic animals in laboratories are
aware of the toxicity of chlorinated tap water. Brungs
(ref. 1) thoroughly reviewed the current knowledge of
the effects of residual chlorine on aquatic life. However,
this paper is not concerned directly, per se, with chlorine
toxicity but rather its reaction with other constituents
of waste waters to produce unwanted chlorinated prod-
ucts. The utility of chlorine in water treatment is at-
tributable to its toxicological characteristics and its
oxidative capacity. Chlorine is employed to destroy
pathogenic and nuisance bacteria and other microorgan-
isms, to modify the chemical constituents of the water
being treated (e.g., reduction of tastes and odors), or
both.
In Fort Collins, as well as in most other Colorado
cities, chlorination is used not only for disinfection of
community water supplies, but also in the disinfection
of effluent waters from the two sewage treatment plants.
This latter water is released, usually directly, into the
Cache La Poudre River, which is part of the South Platte
River system.
There are two sewage treatment plants in Fort Col-
lins, with the most recent one (onstream in 1969) cur-
rently undergoing a large expansion. The newer plant
currently "handles about 5.5 million gallons per day of
waste waters with a near tripling in capacity nearing
completion. Terminal chlorination at this plant site is
carried out on the effluent stream from the clarifying
tanks and just before the effluent enters the chlorination
holding basin from which the water is released to the
river.
* Associate Professor, Pesticide Research Laboratory,
Department of Zoology and Entomology, Colorado State Uni-
versity, Fort Collins, Colorado 80523.
The question that arises is whether this terminal
chlorination treatment, with a desired disinfection as its
goal, can give rise to undesired chlorinated products.
Recently considerable concern was voiced in the na-
tional wire services over the findings by regulatory
agencies of certain chlorinated compounds in the drink-
ing waters of numerous communities (e.g.. New Orleans)
which are potentially dangerous to human health. Most
of those cited to date include chlorinated alkanes (meth-
anes and ethanes, etc.) and chlorinated phenols. The
sources of these compounds were not ascertained but
were being attributed to industrial effluents.
The high reactivity of chlorine with many organic
compounds may provide another answer. Since sewage
effluent waters from one community become the
eventual drinking waters of communities downriver, it is
of considerable importance that it be known that a disin-
fection process at one point does not contribute to the
pollution burden at a second point. Another concern is
the effect on aquatic fauna of such chlorinated com-
pounds as may be formed by chlorination of waste
waters. Although tremendous amounts of data are avail-
able on many chlorinated compounds having deleterious
environmental effects (e.g., the insecticide DDT and the
herbicide 2,4,5-T), very little is known about chlorinated
compounds that may emanate from chlorinated sewage
effluent waters.
Review of the Literature
A recent release of preliminary results of an Envi-
ronmental Protection Agency (EPA) survey of U.S.
drinking waters suggest that chemical contamination is a
national problem (ref. 2). The report states that all 79
cities surveyed contained some amount of chloroform,
ranging from 0.1 part per billion (ppb) to 311 ppb. This
and other chemicals found were reported to be partially
due to chlorination of drinking waters, Delfino (ref. 3),
in response to earlier related reports, doubted the forma-
tion, of chloroform in the chlorine disinfection process
but called for more research in this area. Schwartz (ref.
4), in response to Delfino, cites the relative ease in which
one may expect to find chlorinated compounds after
chlorination considering all the possible organic com-
pounds found just in sewage effluents. Laubusch (ref. 5)
stated that when chlorine is added to water, a mixture of
hypochlorous (NOCI) and hydrochloric (HCI) acids is
formed and that this reaction is complete in a few
seconds. He points out that under some conditions,
379
-------
chlor-addition or chlor-substitution products may be
formed, but gives no further data. Gaffney (ref. 6), in a
letter in Science, found polychlorinated biphenyls
(RGB's) in a sewage treatment plant's trickling filter bed.
These RGB's were the result of a high biphenyl influx
from a textile mill coupled with waste water prechlorina-
tion.
Our interests in this area were rekindled with the
paper by Carlson et al. (ref. 7). They reported that not
only were 10 organic compounds, ranging from phenol
to benzene, chlorinated but also that biphenyl, used as a
fungicide, was chlorinated under various conditions to
varying extents. This latter compound was of particular
interest since we have been working with RGB's for
several /ears as an industrial pollutant. Glaze et al. (ref.
8) found a number of chlorinated compounds by gas
chromatography (GC) after extracting waste-water efflu-
ents containing from 10 to 100 ppm chlorine. Only
chloroform was identified although it was evident from
their chromatograms that higher molecular weight chlo-
rinated compounds also were involved. Although levels
of chlorine can be quite variable in effluent waters,
depending on the chlorine metering devices and operator
control, there are known to be some treatment plants
that discharge effluents containing as high as 15 ppm
total chlorine residual (ref. 9, p. 456).
The literature is replete with references to RGB's in
aquatic animals, such as fish, crayfish, snails, shellfish,
etc., in fish-eating birds, predatory birds, and other
vertebrates, and the question that now arises is whether
some of these RGB's are industrial pollutants or those
produced by chlorination of waste waters.
Background Experience
We have studied and monitored RGB Concentrations
in digested sewage sludge, fish, and effluent waters for
several years. We have shown that PCB levels have stabil-
ized in sewage sludge at about 4-6 ppm, that they are in
the effluent discharges from the sewage plants, and that
they are concentrating in the fish in the Poudre River at
levels often exceeding 5 ppm (refs. 10,11). Although we
have tried, we have been unsuccessful in determining the
source of RGB's into the sewage treatment plants. In
addition, the gas chromatograms of extracts from efflu-
ent waters and fish tissues are not the same as those
from digested sludge. If this is not due to some meta-
bolic process, it may possibly be due to chlorination of
the effluent water. This we would like to determine.
The fact that RGB's have been reported in effluents
from paper mills which use biphenyl in slime control and
chlorine in bleaching processes, gives credence to the
preliminary work we report below and that already
cited.
Preliminary Work
Recently we have conducted some preliminary work
using biphenyl in water (5 ppm) to which was added
chlorinated water to give chlorine concentrations of 8,
83, and 830 ppm. Under ambient conditions and after
aging for 24 hours and 1 week, the samples were
analyzed, along with suitable controls, by gas chromato-
graphy. The chromatograms shown in figure 1 indicate
at least 8 peaks attributed to RGB's. If the individual
chromatograms of A and C were superimposed over B,
one would see striking overlaps although relative peak
heights of most of the peaks aren't comparable. The
standard (B) is Aroclor 1221, an industrial formulation
containing 21 percent chlorine by weight. This is just
one of eight formulations. It is evident that the higher
level of chlorine resulted in higher chlorine substitution
levels, as indicated by the longer retention times. The
above data have not yet been quantitated nor have PCB
isomer assignments been made to the various peaks.
However, we have on hand over 50 pure PCB standards
ranging from several monochloro to decachloro bi-
phenyls which will be used for identification. Present
work has indicated that biphenyl is chlorinated readily
under conditions similar to those in the local sewage
treatment plants. Other work done has involved use of
sodium and calcium hypochlorite as chlorine sources.
Discussion of these preliminary studies need not be
included here since chlorine gas is used locally and we
will confine our work to this source initially.
Work Plan
Since we have on hand a very sizable supply of chlo-
rinated PCB isomers, i1 is our intent to study the chlorin-
ation process initially in the laboratory using biphenyl
and later Aroclor 1221, to determine the parameters
necessary for chlorination. Some of these parameters
would be pH, concentration of reactants, reaction time
and lastly, chlorine source. Since Fort Collins and most
other communities use chlorine gas, and since that is
what we have used primarily in the preliminary work, we
will continue using this form. After this work has been
completed, we plan on using effluent waters obtained
from the sewage treatment plant and conduct time-
course studies to determine extent of chlorination with
time. Chlorine concentration would be the next factor
studied. Probably of utmost concern is the unequivocal
identification of the products formed. The fact that we
have many of the potential products is extremely bene-
ficial. The water samples will be routinely extracted with
hexane and analyzed by GC using our Micotek MT-220
equipped with four columns and dual Ni 63 electron-
capture detectors. An infrared spectrophotometer
(Perkin-Elmer 337) is on hand for determination of
380
-------
^
J <-
i -
\~
Figure 1. Gas chromatograms of extract of biphenyl reacted with CI2
water (83 ppm CD for 1 day (A), 830 ppm Cl for 1 day (C) and com-
parison to Aroclor 1221 (B).
381
-------
B
-J
Figure 2. Gas chromatograms of extract of biphenyl reacted with CI2 -water
(83 ppm CD for 1 week (A) and comparison with Aroclor 1221 (B).
382
-------
/\
E
Figure 3. Gas chromatograms of extract of biphenyl reacted with CI2 -water
(830 ppm Cl) for 1 week (A) and comparison to Aroclor 1232 (B).
383
-------
infrared spectra of products isolated by thin-layer
chromatography. Confirmation of identities is planned
using a mass spectrometer coupled with a GC.
Figure 2 illustrates the similarity of the extract (A)
(the reaction of 83 ppm CI2 water with 5 ppm biphenyl
incubated 1 week) with that of Aroclor 1221 but not in
the same proportions. Using a light table, the peaks are
superimposable on one another. This is true also of
figure 3, where the chromatograms show the results of
830 ppm Cl and 5 ppm biphenyl incubated for 1 week in
comparison to Aroclor 1232. It is evident that increasing
chlorine dosages result in greater degrees of chlorination.
The chromatograms in both figure 2 and figure 3 were
very similar also after 1 day in incubation with the
exception that the later eluting peaks are more pro-
nounced. In figure 3 as in 2 above, all the peaks in the
extract are in the Aroclor 1232. It was surprising to us
that biphenyl was so readily chlorinated in light of its
assumed unreactivity.
Further work is planned along these lines using
shorter reaction time spans (hours), utilization of thio-
sulfate to terminate the reaction, use of CCI4 or CHCI3
instead of hexane as extracting solvent, and use of glass-
distilled water (rather than from Barnstead still) distilled
over basic KMnO4. We have used reagent-grade CI2 gas
and have not noticed any problem with bromine as an
impurity. We would like to get access to a MS to check
our peaks for chlorine content. We have checked the pH
of the saturated CI2-water and found it to be 2.4 and
after bubbling air through it, via a fritted disc, to be
2.45. So apparently the HOCI and HCI formed by the
reaction of CI2 gas with water is quite stable. Some early
peaks showing up in our blanks, especially the CI2 -water
blanks, are due possibly to the chlorination of hexane.
This is the main reason we want to terminate the chlo-
rination reaction with thiosulfate prior to extraction.
REFERENCES
1. W. A. Brungs, "Effects of Residual Chlorine on
Aquatic Life," J. Water Pollut, Contr. Fed., Vol. 45
(1973), pp. 2180-93.
2. Anonymous, "Water Contaminated Throughout
U.S.," Chem. Eng. News, April 28, 1975, pp. 18-19.
3. J. J. Delfino, "Drinking Water Study," Chem. Eng.
News, December 23, 1974.
4. H. Schwartz, "Chlorine in Water," Chem. Eng.
News, January 20, 1975, p. 5.
5. E. J. Laubusch, "Water Chlorination," J. S. Sconce,
ed., Chlorine, Its Manufacture, Properties and Uses,
Reinhold, New York, (1962), pp. 457-84.
6. P. E. Gaffney, "PCB's: Another Source," Science,
Vol. 183 (1974), pp. 367-8.
7. R. M. Carlson, R. E. Carlson, H. L. Kopperman, and
R. Caple, "Facile Incorporation of Chlorine Into
Aromatic Systems During Aqueous Chlorination
Processes," Envir. Sci. Techno/., Vol. 9 (1975), pp.
674-5.
8. W. H. Glaze, J. E. Henderson, IV, J. E. Bell, and V.
A. Wheeler; "Analysis of Organic Materials in Waste-
water Effluents After Chlorination," J. Chro-
matogr., Vol. II (1973), pp. 580-4.
9. G. C. White, "Handbook of Chlorination," Van
Nostrand Reinhold Company, New York, (1972), p.
744.
10. R. E, Johnsen, "Polychlorinated Biphenyls: An
Industrial Pollutant," Environmental Chemicals-
Human and Animal Health, Proc., Fort Collins,
Colorado. August 7-11, 1972, Environmental Pro-
tection Agency, 1973, pp. 213-20.
11. R. E. Johnsen, and L. Y. Munsell. "PCB's Their
Origin and Fate in A River Ecosystem." Environ-
mental Chemicals- Human and Animal Health, Pro-
ceedings Fort Collins, Colorado, 3rd Annual Confer-
ence, July 15-19, 1974, Environmental Protection
Agency, 1975, pp. 273-92.
HERBERT GILNER (Tivian Laboratories, Providence,
Rhode Island): I would like to address myself brief-
ly to the methods used to gather information about
polychlorinated biphenyls as environmental con-
taminants. I do not argue with the need, only with
the methods.
It has been claimed both in the press and at this
conference that of the 84 firms to whom letters
were sent in August concerning the use of PCB's,
only one has refused to respond. That company has
been named in the press. That company is Tivian.
However, to our knowledge, there is at least one
other company which has also refused.
There are two distinct principles involved in
this refusal. The first is that Tivian Laboratories
does not use PCB's. On hearing this, the Environ-
mental Protection Agency demanded information
concerning Tivian's use of polychlorinated ter-
phenyls, a series of compounds qualitatively differ-
ent from PCB's. There has been, to our knowledge,
384
-------
no evidence that the PCT's accumulate in human
tissues. Moreover, we state and have stated in the
past that Tivian Laboratories do not pollute the
environment.
Furthermore, and this gets us to the second
principle, Tivian feels that the information demand-
ed is proprietary and that EPA, having been set up
by executive order, has no constitutional or statu-
tory right to demand such information or to make
threats concerning penalties for noncompliance. The
company I represent feels that the harassing activi-
ties of the EPA, including trial by the press, are
totally illegal.
EPA has sought to vilify the name of Tivian by
passing its name to the press, claiming that Tivian
has contaminated the environment with PCB's,
which our company does not use.
Tivian Laboratories has filed a $20 million dam-
age suit against EPA for this release of false informa-
tion to the public. Tivian has further requested the
U.S. Marshall's Office in Providence, Rhode Island,
to issue a warrant for the arrest of EPA personnel
for the violation of Constitutional laws and con-
gressional statutes in its dealings with Tivian.
It is ironic that the company most responsible
for the manufacture and distribution of PCB's in
this country continues to do so, but a small
company which does not handle PCB's is harassed.
At our request, the EPA supplied us with a list
of companies to whom questionnaires were sent.
However, the names of certain firms, as we heard
again yesterday, were excized from the list. Is it not
strange that the name of one company is pejora-
tively released to the press while the identity of
others is concealed? Why?
Is it not capricious that under our unelected
administration in Washington, these names as well as
those of the companies dealing with the Arabs and
cooperating with the Arab boycott of Israel are kept
secret? The objectives of EPA are without a doubt
useful, necessary, and worthy, and we still support
them, but we will not submit to an agency which is
so blatantly being used as a tool of an unethical
policy.
Figure 1, literature handed out by Tivian
Laboratories, is on the following pages.
385
-------
I I VI AW UktORHTOBIJS IXC
' •••"•••-"- IMMEDIATE
^4 ^ RELEASE
November 18,1975
PROVIDENCE_.Ca
-------
(2)
refused by Tivian. When Tivien requested the exact contents of these letters
and their nature, they wero not given s. definite answer as to their content.
After Tivian had refused thiso letters, a letter was servad upon Tivi&n by
a U.S. Marshall, which contained a very lengthy questionaire form.
Melechinsky charges the EPA with several Constitutional violations in
sending out the form particularly Amendment Xln of the U.S. Constitution,
which states "Neither slavery nor involuntary servitude..,..shall exist within
the United States..." Any involuntary response to the subject letter would
constitute involuntary servitude.
Melechinsky further maintains that it is becoming a disgusting practice
for many states and federal agencies to harrass businessmen with lengthy forms.
He asksi 1. Do not such forma add to a tax bill which is already fantastica-
lly high? 2. Who pays companies for the time and effort required for
filling them out? 3. If such funds are available, isn't that * further
unwarranted expenditure of tax monies? ^, How can governments justify
adding another nuisance load to the many which various governmental
agencies are already seeking to impose on businesses? 5. Isn't this an inv-
asion of privacy? 6. What Constitutional authority is there for such forms?
The claim against EPA has been filed by Tivian*s Vice-President of Legal
Affairs, Paul Wallins.
Marvin Antelman the President of the Corporation, has stated that ha
believes that the Agency harrassed him because of his constant criticism, in
his capacity as an officer of the National Leadership Conference for The
Security of Israel of Kissinger and Ford for their hard line against the
State of lorael and Commerce Secretary's Mortton's support of the Arab Bo-
ycott. Antelman stated that the Company will attempt in its litigation to
document this. In a terse reply to Michael Deland Antelman stated "This most
recent incident smacks very much like that of a medieval antisemitic libel
Figure 1. (con.).
387
-------
(1)
such as*the Jews poisoned the walls."
Antelman fui-thor has stated that he views EPA extremism as following
in tho spirit of Karl Marx who wrote "A W^rjd VH thout Jews", and Marx equated
Jews with capitalism and urged their destruction. Acusing EPA of adopting^
a raidieval scenario in which tho capitalist replaces the Jewi Antelman stated
"This is one Jew who does not pollute the walls and who refuses to be intifai-
ti
dated by &n en ti-send tic EPA blood libeljand, accused. EPA of attempting to
dishonor responsible businessmen and to portray then before the public as poll-
uters.
Furthermore, Antelman stated it would be a good idea for Congress to
investigate intensively the backgrounds of some EPA people, as he has found
that there are members of the EPA today who have had past left wing associa-
tions with radical militant anti-business groups such as the Black Panthers
and S.D.S. as well as strong Coofisunistic leanings or who hava worked for
various foundations whose main programs and goals appear to bo the
destruction of American business and the substitution of a Socialist
or Communist state here in the U.S. and who fund radical organizations.
Antelman feels that while it is true that there ar« irresponsible
individuals who have polluted tho environment and, that measures should be
taken to improve the environment, the EPA smacks of too much harrassment and
too much hysteria and has substituted realistic objactives with impossible
and technologically unfeasible goals. Above all, if ther are polluters that
must be dealt with they should not be denied their Constitutional rights in our
society. Instead. EPA intimidation has resulted in vast destruction of the
industrial capacity of the United States and has weakened our economy.
Melechinsky in his reply to Marshall Wyatt accused EPA of practicing a vicious
form of extortion characteristic of a totalitarian government.
Figure 1. (con.).
388
-------
ournal. li^-riiy c^p'
BY ROBERT FREDERIKSEN
*w»tt« Rrtef
PROVIDENCE - Tivian La-
boralories. Inc . 330 Silver Sp-
ring SI , was identified yester-
day as (he only firm in the
nation that his ignored govern-
ment requests (or data on
highly toxic PCBs —
polychlorinaled bipheny is.
As a result, (he Envl-
ronmcnlal Protection Agency
has formally ordered officers of
the firm, said to be a "mapr
PCB user," to supply the data.
or face penalties of up to
$25.000 a day, a year in jail, or
both
Marvin S. Antelman of New-
Ion, Mass , president of the
iix-year-old chemical manufac-
turing firm, said it docs n it use
PCBs in its business of making
plating solutions for the jewelry
uid electronics industries.
He confirmed that two cer-
tified EPA data request letters
were ignored because of
rompany policy against ac-
:epring certified, or registered,
tilers on grounds that this
might be interpreted legally as
conscr.'ing. or complying, with
the cc-"tents.
An'.'lman also ronfirmed that
a IIS marshal had served tne
forma! EPA order, but said, "H
was not properly served he-
cause it was not placed in my
hands, as is required I read It
and will respond, however."
He accused EPA and the
federal Occupational Safety and
Health Administration o?
"harrsssing and bugging" him
because of his past criticicm of
them and of President Ford and
Secretary of State Henry
Kissirjer for their'hird treat;-
men! of Israel.
The state Health Department,
which was notified by EPA, but
has fjten no action in the case,
said lH.e firm appears to be on a
cily rarutary-storm sewer that
overflows into the MoshaSoUck
River afttr heavy ra;ns.
Antclman said, however, that
only domestic wiste from two
toilets and two sinks goes into
the sewer. Laboratory wastes
arc hauled away "We don't use
any FCBs. We don't put any in
the sfwer," he said.
Bljke Biles, of EPA's Wash-
inglcn office, said Tivian La-
boratories, was one of 84 firms,
including eight in New England.
that were sent letlers in August,
requesting PCB use and disposal
data for use in developing
controls because" of growing
concern over effects on public
health.
Tivian was the only one of,
the 84 firms that Ignored the
letters, itf several follovvup
phonr o.lls by EPA's Wash-
ington ar,d Boston oMifts before
the !orin.i! order wts iisued, be
saw!
The rrms' names were taken
frc-m customer lists of the
Konwrno Chemical Co., the
nation's largest PCB manufac-
turer. U S. Customs and EPA
hazardous materials -data. Biles
said
PCBs are rMorinated hydro-
carbons resembling DDT, which
EPA banned in 1972, the same
year it limited PCB use to c'.oswl
electrical systems to reduce wa-
ttr and lish contar.iination. ac-
cording to a recent news release
by John A. S. McGlennco, EPA
regional director in Boston.
Health effects associated with
PCBs include eye discharge,
acne, ulcers of the uterus, ab-
normal skin pigmentation and
reproductive failures. New
York recently urged the public
not to eat striped bass and
certain other fish from the
Hudson River and Lake Ontirio
because o! dangerously high
PCB levels, McGlennon noted,
Because some striped bass
spawned in the Hudson River
migrate to New England wa-
ters, extensive tests have been
started to determine PCB levels
in food (ish here, he said.' • r
"Fina! results of the testing
will not be available for a few-
months, but preliminary data
indicate that PCB levels are
writ below the live parts per
million tolerance level es-
tablished in 1972 by the US.
Food and Drug Administration,"
McGlcnnon said.
"There is no need for New
Englanders to stop eating
stnp«d bass or any other fish
because of possible PCB
contamination." he said, but
added that it Is crucial to
continue existing controls and
may be necessary to extend
them as a result of current
studies ar.d tests.
Figure 1. (con.).
389
-------
975
Novecber
ied envelope Ko. 155215, containing a letter from the United
n Agency to Tivian Laboratories, Inc., dated October 16, 1975
led PCLYCKLORLNATED BIFHENIL (PCB) COMPOUNDS OR MIXTURES.
rH
0) -P
x; +J
n 03
.q 5"
co cd
cu .C
•p to
Oj H
-P .g
"O
O ..
+' £3
•H P!
d t-<
r-
O
CT>
Orf
O
•tJ
d
d
rH
M U
ffM
•H
rH T)
•rj O
fy^ ^f\
rH •>
03 CU
(-1 0
1) (4
CJ t3
fK4 -rt
|>
IT» 0
O rH
^
+i
£4
CD
O
|
-P
u d
O) CD
•p
O CO
rH 0
a o
d XI
00
f^ CD
d bo
o a
rH O,
li
f, ^
CO
O R
-P
rrt _
our phone conversation of 10-27-75, the E.P.A. letter has no
e United States Constitution.
XI
M -P
U
P rH
> 0
+3
r) -H
0 T3
r— f
CO c)
"authority" contained in the unconstitutional Water Pollu-
ly illegal Clean Air Act and in demanding that certain
provided" within certain time limits, the Environmental
g a vicious form of extortion, characteristic of a totali-
•P rH
d 03
(D -3
-P O'
CO CD
.H
^S ®
d
o -a
0)
Ql
+3
o o
-P ~<
txO f~~t
d o
•H H
rH -P
rH d
a o
> ca
•H -P
rH O
n. h
«
-p
t^
a)
|
> •'< fi
03
O
•H
O
10
0)
•p
"S
•p
•H
pi
CD
5
Vl
o
d
o
•H
•P
^
•P
•rl
-P
OJ
j^
0
o
C!)
X!
f the people to be secure in their persons, houses, papers,
ble searches and seizures, shall not be violated, "
er constitute an attempted search of Tivian Laboratories,
O
0
0)
n
0)
•a
a]
-P
H
1
Vi
0
C9
J
•ri
0)
•a
CS
•t
.
o
d
390
-------
? U
-P O -H
I > 3 o
i > 2
>
&ZHBO
S
S0 1
a)
3 hp ^
w a 41
01 -H P
•H ,a -P
T) 01
a,
* S.-S
CIO
03 P
OJ Cl
U
•p o
M
•s
•p.
>- M
4» 03
X> bD
4)
4) -P
M M
Q. O
T» &
•H
• O
4)
•H
o tn
(0 4)
h n
01
•rH -P 41 G 3
rH C «M • O
ui co M 01 >^ o
Xi >1 41 I-l G O
• « M
4)
Tj O
S °
O M O
•p a +1
a-3 «
n *r4
41
U
b £ S3
KJ -P O
« 5)5 5
01
•p > -p
XJ 03 «
U)rH 4]
•H H
Si
3
ra g
• x! X!
o
bo o
4> •
O 4> ^ r.
rH O rH
^-t A XI M - •
O O -P £3 10 <|J
4> -H 4)' 4> •
•» O. 3 r-l -rl Oi
C U M •
O O 41 O U
•H X! 01 4) -P
•P *J (0 ^ 0) 4)
3 IB -! O
e° *i«^
01 ra G
(D •••HO)
.1 > P
O S>
3
«ii
" 4^
_g « o
•H G
1^
+J
i oJ
• tH O
«W n G
I rH 4)
3 . . j 0) O O
3 B -r( X! O
a &, H +> -
. J +J
ft'
C x; •
o +-> o
2 °r9
a) Q!
a
... O
O G
T< -P >>
U T) CO X> to
x! >-i e
c-< ^i O T) -H
E O X> 0) 03
3-P a, 4>
-P "H Q) -P
t-« H -P
a
•>
><)
M
o
O
> p,
o o
U,"
o
B «-. -rH • w
•j; P -P _ CW ^J
• C -H x! * O
vr\ o M p M G
ta
«
M XI
O -P
-P
v(
m
0] 4)
13 -H
<» . _
to t> O O d
G 3 x; ID
O -P +3
O O -P 3 +»
5 O 03 O
41 a « -<
^ BJ « »<
•P t) 4) O rH
O
>»-P *H OJ f4
x? a o .x 4>
m oo
bo g o
a xi o
o-§8
01
M -rl
0> J4
lla
Q) 0> 4) rH
•P XI X! C rH
iH -P +1 O O
G -HO,
61 0} 3 ^
o J3 x; -P 41
5-P T» +J
^> -P to
W -H 01 ^C
•P 10 01 O rH
o> a o a
T3 a 4> I-l
01
P 01 fl XI "O
03 -H 3 +^ 4)
&OX1 _, PS
T* 0)
w5
/—I V
4) q
•a s M
o
G
-a o
O -H O 01
o M ? q
M CX O O
4) -P O -H
3 ID OJ G 01
ox;
a.*3
o
XI
o
•H 01
O
+3 O
0]
•H -a
CD O
•p j tu a,
M
G 4> tlO
.s£.g
J-!
t-l
0)
r4 O
-P t< • J-l
•a a -P
a o
O -H
tJ
« 0) ^i 3 I
a> 01 -P a
£3 o G -ri o
--^ 1-1 O P T>
Cl fl)
>* ^-)
OJ 0)
l&
0)
M
O
o
U
4)
3 S
•H «
4)
^
0] 01
ll
rH 01
O 4)
Is
>
cd
4> •
X! O
+3 s ^
-p
•» 4)
M .. 01
M 01
P r?
^5
T) rH
-------
o I
*/l i
iii
| ;
C£
O
2
_}
y 2
PJ j»
H >
F
*• *^-^
f"
j*
>•
S *
* ° 0
a - M
z . - ..
i » J. o
t • N frt
* S < 0
tc " _ O
> o 2
Ms w
10 (t •
31 *
^L £Q
A r-
JM
>' 4)
!-X"*v rH
fA -P
1 I -rl
V J *•
under color of law, statute, or ordinance, regulation, or cus-
y inhabitants of env state to the deprivation of any rights,
secured or protected by the Constitution or Laws of the United
ed no more than $1000 or imprisoned one year or both."
to
V
o
0)
•
00
a m a
10 1) -rl
•H Vl
m -p
•P -^ D
o g jo
•*~? H rH
n gj r— i
3 -rl Ci
W Jd
M W
>> 0
3 10 •
-P
n -H oj
O to -P
•P AW
or nore persons conspire to injure, oppress, threoten or intimi-
rec exercise or enjoyment of any right or privilege secured to
r laws of the United States they shall be fined no more
not more than ten years or both."
ce, inconvenience and additional expense which a conscientious
Vt
§ 0
+J ^q
+3
CO
a
- o
O P,
n n
r-l CU
••"Jj M
hief Executive for Federal Affairs, I em assuming responsibility
to the letter of the Qivironoental Protection Agency.
o
•a
- a
m o
co a.
•H 01
to a>
O to
+>
a>
•H T)
H
01 o
•<
5
^
j^
r-<
01
O
•H
>
•a
o
0)
43
(0
P)
•j;
+» C n
3] Ct)
r-i « -H
a> cu .ri
o a -P
•r-l F< 3
0 T-,
01
liO ^ tj
m a
n +> 09
ti -.
-.< q
M O
•r-l
O -P
n o
ID
« n -p
3 (-1 O
(C ^> M
,-t CM P.
3
01
•rt
4)
a
o
o
S
o
t—
•8
+»
Bl ~.
a •
*
CO
IP rH
TJ O
•H 2
> O
0 ^1
pt Jj
+>
fi -H
O 4-^
3%
3 o
+J o
•H q
-p 3
en
a a
O CO
o
kfcj
CD O
J*3 *^
H O
•H
4) +*
n
« n.
•P CD
\\
h
a -P
S 0
_*J 0)
r-l a
r-l bO
0 3
a)
r-t •
O
JC r-i
^3
A
n n
•H *D
a M
o o
•rt -P «
-P a) M
3 i-i a>
•P O -P
•H ^S +J
•P -3 rH
n
o ri •
o ca <<
T4 «
CO I> PL(
j>4 *H *
H t-i W
C
o
E5
LL
392
-------
& r
® u
n a
H (D
a .a
* V'-* ~* — s
=> "3 -xT^K
R S " '^sJY |\
** M ^Or \ H 1
s § . - y \V
•* • 2 3^j?8
«jg i rc4t§1
^ S ^S
fr£S 5 33 -^
iSs !,J^
"* ° a 5 7? -^ S
00 5 '/^3-S
IP 4lif
{I! V-J5""
fljS-3
C +> 43
m Q
1-1
M +»
rt a tj
u
»/>
UJ
S
O
<
u
0
<
s
<
E
^
&.'V.
^>\
c*\'
STRtCT
Oa9O4
18
8-J
j K « -
!«?
ff i ~
' U u -
< 5*0
O a
g
-H
+>
O
a
V
,•»!
5
•o
1
X!
10
o
JH
4
n
s
n
i-H
s
i-t
n
>,
M C
01
3?g
-1
&5
!?
0 V)
•35
"•8
OT -H
3-S
r cement
db
•
4»
^
03
^
a.
ff
o
O
0)
3
a
TA
o
+>
"8
VI
u
o
I-t
ft.
a
o
«
If
o
6
+j
Is
.. 5)
O J5
ii
£?^
§-
3V
m
9
S
CN
Environmental Protection
John F. Kennedy Federal
Boston, Massachusetts 02
H
Q>
H
rH
S
O
!
^
S
*4
5
M
O
+>
S
-u
3
ba
§
5
O
ffl
Acting Assistant Adminis'
U. S. fiavironaental Proti
VasMngtoc, D. C. 20^.60
C
O
O
O5
393
-------
THE NEED FOR COST-BENEFIT ANALYSIS IN TOXIC
SUBSTANCE USAGE
A. Eatock*
INTRODUCTION
Yesterday, mercury had the limelight; today, it is
PCB's; tomorrow—what? We face a recurrent problem in
dealing with toxic substances in the national-social
context. Thus, this paper discusses the overall problem
of toxic substances rather than just PCB's.
The purpose of this paper is threefold:
a. to show the absolute necessity of cost-benefit
analysis in achieving an equitable balance be-
tween private and social costs and benefits;
b. to illustrate the need in cost-benefit analysis
for researchers to be specific in delineating the
chain of consequences together with the risks
involved in toxic substances; and
c. to illustrate the elements of a simplified cost-
benefit analysis based on PCB's.
Conceptually, cost-benefit analysis is quite simple in
that one places a value on the costs of an action or
program and a value on the benefits resulting therefrom.
If the dollar benefits exceed the dollar cost, then one
proceeds with the action or program. However, simple
ideas do tend to get complicated in practice and
cost-benefit analysis is no exception. One complication,
which will be ignored hereafter, is what interest rate to
use in finding the present value of future benefits such
that they can be compared to the costs. Another
complication is how to value intangibles (such as good
health and aesthetics) that do not have an established
price from being traded on the open market. There is no
easy, or even commonly accepted, method for valuing
the unintended effects of toxic substances resulting in
social costs. This results in considerable conflict due to
the judgmental valuing in estimating social costs and,
frequently, the ignoring of the whole issue of
intangibles.
MAGNITUDE OF THE PCB PROBLEM
To illustrate one aspect of the magnitude of the
PCB problem and to lay the groundwork for a
cost-benefit analysis, a hypothetical case on the
accumulated PCB loading to the Lower Great Lakes
from U.S. sources is worked out. There are three
categories of inputs as follows:
"Social Sciences Division, Inland Waters Directorate-
Ontario Region, Burlington, Ontario, Canada L7R 4A6.
1. Uncontrolled Imports:
a. Estimate (ref. 1) of uncontrolled imports of
PCB's as part of other products in 1972 =
375,000 Ib.
b. 1971 U.S. population in the Lower Great
Lakes Basin (ref. 2) 13 X 106 & 6.3 percent of
total population.
c. Lower Great Lakes water volume converted to
weight = 4,575 X 1012 Ib.
Assumptions:
a. The PCB distribution is similar to the
population distribution (ref. 2).
b. The continuing How of import products results
in a continuing equivalent amount going into
the environment.
c. Thirty percent of PCB's are of the persistent
(nonbiodegradable) types (ref. 4).
Then, 375,000 Ib of uncontrolled imports result in
an equivalent lake water PCB load of 1.5 ppt. Please
note the word "equivalent;" in actual fact, the lake
water has a very much lower level since PCB's tend to
accumulate in the biota and sediment.
2. Existing Pool:
It is reported (ref. 3) that the U.S. consumption was
approximately 1 billion Ib of PCB's during the 40-year
period from 1930 to 1970. The majority of this PCB
consumption must now be in the environment, primarily
in garbage dumps and sediment. If 0.1 percent of this
pool is released annually from the various sources, then
the equivalent lake load is 4 ppt PCB's in the water.
3. Continuing Use:
The third category is continuing authorized use for
transformers and power factor capacitors, which con-
stitute a consumption of more than 50 X 106 Ib/yr (ref.
4). An assumption of a 0.1 percent leakage rate to the
environment results in an equivalent lake load of 0.2 ppt
in the water.
This is the U.S. loading on the Lower Great Lakes,
to which the Canadian contribution must be added.
Keeping in mind that these figures are based on
unsupported assumptions, it is still interesting to
compare them with the proposed water quality target of
1 ppt. It does indicate that, since PCB's are so persistent,
the problem will have to be lived with for a long time.
How far to go in rectifying the problem is where
394
-------
A COST-BENEFIT FORMAT
Benefits
The chief benefit of RGB's is their nonflammability
in the liquid phase. This has resulted in only PCB-cooled
transformers and power factor capacitors being allowed
in the upper floors of tall buildings. On similar safety
grounds, it is the only fluid permissible for use in
electrostatic precipitators that keep the particulate
pollution from going up the stack of most industries. No
estimates for the value of these benefits, and others
which are not considered, are readily available, but they
must be substantial or the OECD (ref. 8) group would
not have recommended continuing these uses. While not
ignoring the necessity of confirming these benefits, the
cost-benefit analysis may be simplified to the tradeoffs
between direct costs of controlled usage and the cost of
damage to the natural and human environment.
At this point, the three sources of contamination
can be incorporated in the cost-benefit analysis, as
shown in table 1. These figures give some indication of
the most cost-effective tradeoffs between various control
methods and damages to the natural and human
environment.
COST OF CONTROLLING USAGE
The cost of controlling the authorized usages of
PCB's consists of the direct and indirect costs (table 2).
The direct costs include containment devices to avoid
leakages and losses; the handling of contaminated
containers, cloths, etc.; the decontamination of equip-
ment; the incineration of contaminated cleaning
solvents, clothes, etc.; and the cost of monitoring and
policing these activities to minimize leakages to the
environment.
Indirect costs could include the monitoring and
policing required to reduce unauthorized imports of
PCB's as part of other products, and sewage incineration
to reduce the environmental levels of PCB's. This latter
indirect cost is of considerable interest since high-
temperature incineration appears to be the only practical
method of destroying PCB's, and sewage sludge incinera-
tion has the potential to break the continuing cycle of
PCB through the environment. In Ontario, approxi-
mately 40 percent of the sewage sludge is incinerated,
principally by the larger centers that are the main
sources of PCB's. Unfortunately, temperatures well in
excess of 860° C are required to destroy PCB's and the
normal incinerator operation is just at or below this
temperature. Further, since considerable energy is
required to burn the wet sludge, optimization of sewage
plant operations dictates operating at even lower
operating temperatures as the cost of fuel increases.
Obviously, there is a need to optimize sewage plant
incinerator operations with the destruction of PCB's
included in the criteria. The higher cost of fuel can
possibly be alleviated by exhaust gas heat recovery to
dry the incoming sludge, which apparently is not
common practice at present.
SOCIAL COSTS
Social costs, including damage to the environment,
as shown in table 3, are again split into direct and in-
direct costs. The direct costs include loss of commercial
fishing and loss of recreational industry business due to
the contamination by PCB's of the larger predatory fish
which are at the top of the bioaccumulation chain (ref.
5). Another direct cost is the loss of foodstuffs due to
contamination during production and packaging. Should
PCB's continue to be dispersed to the environment from
sewage incineration stacks, and sewage sludge utilized as
fertilizer, there is a good possibility that the level of
PCB's in milk, presently as high as 0.1 ppm near indus-
trial centers in southern Ontario, will continue to rise
and result in value lost when the milk is not fit for
consumption. The occasional poisoning of industrial
workers working with PCB's, or the poisoning of individ-
uals in the general population due to accidental spills,
gives rise to costs from lost work time and medical atten-
tion.
Indirect costs (table 4) include such things as
fish-eating birds that have all but disappeared from the
lower lakes; these include osprey, bald eagle, cormorant,
bittern, herons, and loons (ref. 6). The herring gulls
would also disappear except for the influx from the East
Coast and the Upper Great Lakes (refs. 6,7). There are
two aspects related to the loss of these birds. One is that,
if the predator fish population declines, the alewife
population will increase, and if the gull population
declines, who is going to clean up, and at what cost, the
mess resulting from massive alewife dieoffs such as we
had a few years ago. This is what can happen if the
balance of nature is disturbed. However, the main
interest at the moment is the social cost aspect. How
does one cost the aesthetic value of the bird population?
This problem is typical of the multitude of social costs
that must be considered, and there is no easy answer or
agreement on methods.
EXAMPLE OF SOCIAL COST ANALYSIS
One approach taken to illustrate the problem is as
follows. According to the Federation of Ontario
Naturalists, there are approximately 750 bird watchers
395
-------
Table 1. Functional organizational model
Due Due Due
existing continuing uncontrolled
Benefits pool usage imports
Transformer and power factor
capacitators safety
Reduction in property loss
Reduction in loss of life
Reduction in mdeical costs
Reduction in employment loss
Reduction in pollution
(electrostatic precipitators)
Reduction in cost of controlling
pollution
Table 2. Costs of controlling the authorized usages of PCB's
Risk (cost) Risk (cost) Risk (cost)
due due due
existing continuing uncontrolled
pool usage imports
Cost of controlling usage
Direct costs
Containment
Contaminated
articles disposal
Decontamination
Incineration
Monitoring and
policing
Indirect costs
Monitoring and
policing (imports)
Sewage sludge
incineration
396
-------
Table 3. Social costs of RGB's
Risk (cost)
due
existing
pool
Risk (cost)
due
continuing
usage
Risk (cost)
due
uncontrolled
imports
Cost of controlling usage
Social costs (environ-
mental damage costs)
Direct costs
Commercial
fisheries
Recreation
industry
Contaminated
food
Worker lost
time
Worker medical
costs
Nonrecycling
of paper
in Ontario who report on migratory birds and spend
approximately 500 hours a year observing; there are
another 15,000 bird watchers who pay $12.00 per year
to belong to the organization, and it may be arbitrarily
assumed that they spend 10 days a year watching birds,
for a total of 60 hr/yr. Assuming this is an exponential
function tailing off to the 8 millionth person in Ontario,
who never looks at birds, it can be calculated that
125,000 hours are spent in bird watching. Again being
arbitrary, it could be assumed that 10 percent of the
pleasure in bird watching for Ontario residents is lost
with the loss of the previously mentioned birds. The loss
is then 12,500 hours of enjoyment, and there is still the
problem of putting a value on it. In the past, economists
have attempted to value recreation on the basis of travel
costs, money spent on equipment, the leisure hours
tradeoff against employment income, and many other
methods. The potential loss of employment income
probably sets the upper limit, while the casual observer,
at no cost, sets the lower limit. At this stage, no attempt
to put a value on leisure hours will be made.
The point to be made here is that the researchers
have to provide risk data on the consequences of varying
levels of toxic substances in the environment. Without
the probabilities of resultant consequences being
specified, no cost-benefit analysis can be performed a~d
resource allocation cannot be optimized. Note that the
incremental increases in social costs in the Legal Usage
columns and the Uncontrolled Imports columns in the
figures can be balanced against the same columns in the
Cost of Controlling Usage subsection. Alternatively, the
cost and effectiveness of sewage sludge incineration may
result in a considerable reduction in the Social (Risk)
Costs such that other Controlling Usage Costs may be
reduced. The combinations and permutations are
manifold, but operational research methods are available
to find the optimum least-cost arrangement.
STRUCTURE OF TOXIC SUBSTANCE RESEARCH
In conclusion, it will be indicated how cost-benefit
analysis relates to the overall scheme of things, along
with a few comments about the organizational structure.
The following (figure 1) shows a conical structure with
the research disciplines at the base, leading up through
Economic and Social Cost and Social Goals Policy to
Legislation and Regulation at the apex.
It may be observed that, at present, the research
397
-------
Table 4. Indirect costs of RGB's
Risk (cost)
due
existing
pool
Risk (cost) Risk (cost)
due due
continuing uncontrolled
usage imports
Cost of controlling usage
Social costs (environ-
mental damage costs)
Indirect costs
Aesthetics - loss
of osprey, bald
eagle, cormorant,
bittern, heron,
loon
Recreational
fishing
Recreational
hunting
Cleanup of
alewife dieoff
Human - loss
of physical
well-being
(including
abortions)
Loss of mental
well-being
Loss of social
well-being
tends to be fragmented and uncoordinated. The trans-
portation model (second level in the cone), which shows
how a particular toxic substance cycles through the
natural, biological, and economic environment, tends to
tie together all the various disciplines. The next level,
economic and social cost assessments, should also pro-
vide a unifying force among these disciplines, as well as
linking the research with the social goals.
Further, the ultimate unifying research objective
may be stated as:
To determine the tolerable level of specific toxic
substances in the environment with a holistic
approach that balances the direct and indirect,
private and social costs and benefits relevant to the
use, or nonuse of the substance.
Clearly, to meet this objective, some form of cen-
tralized body is needed in each country to integrate and
coordinate toxic substance research among the -various
agencies and disciplines involved. These bodies would
specify and insure the planning, implementation, and
control strategy for achieving the research objective,
including:
a. the organization and allocation of research
projects and subobjectives among the various
agencies;
b. the identification and effective communica-
tion of available information and data;
c. the periodic communication of the overall
strategy and progress in meeting objectives;
and
398
-------
o
'•M
CO
N
'c
CO
O5
O
§
•M
U
c
a.
E
cu
U
c
03
•M
(/)
.a
V)
O
'x
o
3
a>
399
-------
d. the formulation of recommendations based on
the research findings, and their communica-
tion to policy and decisionmakers.
Clearly, to meet this objective, some form of
centralized body is needed in each country to integrate
and coordinate toxic substance research among the
various agencies and disciplines involved. These bodies
would specify and insure the planning, implementation,
and control strategy for achieving the research objective,
including: (a) the organization and allocation of research
projects and subobjectives among the various agencies;
(b) the identification and effective communication of
available information and data; (c) the periodic
communication of the overall strategy and progress in
meeting objectives; and (d) the formulation of
recommendations based on the research findings, and
their communication to policy and decisionmakers.
All the elements for the lead agencies, the Depart-
ment of Environment and the Environmental Protection
Agency, appear to be present, such that they could grasp
the authority and carry out the above objectives. It is
suggested, as a first step, that each of these lead agencies
appoint a Toxic Substances Research Coordination Com-
mittee. Both these national committees should be
endowed with the power, through interdepartmental
agreements, to carry out their objectives effectively. If
we can proceed in this direction and if everyone pro-
motes these objectives, an effective solution to the toxic
substances problem will be realized.
REFERENCES
1. Statement by G. E. Schweitzer, Director, Office of
Toxic Substances, Environmental Protection
Agency, during hearings on RGB's by Wisconsin
Department of Natural Resources, August 29, 1975.
2. Population Estimates for the Great Lakes Basins and
Their Major Tributaries. Social Science Series No. 1,
Inland Waters Directorate, Canada Centre for Inland
Waters, 1973.
3. Kevin P. Shea, "PCB," Environment. Vol. 15, No. 9
(November 1973).
4. I. C. T. Nisbet and A. F. Sarofim, "Rates and
Routes of Transport of PCB's in the Environment,"
Environmental Health Perspectives, Experimental
Issue No. 1 (April 1972).
5. Great Lakes Water Duality, Third Annual Report to
the International Joint Commission, Great Lakes
Water Quality Board, July 1975, p. 641.
6. Glen Agnew, Federation of Ontario Naturalists,
Toronto, personal communication, November 1975.
7. D. P. Peakall, "PCB's and Their Environmental
Effects," CRC Critical Reviews in Environmental
Controls, Vol. 5, No. 4 (September 1975).
8. OECD Council Takes Major Decision with Regard to
the Control of Certain Toxic Chemicals, Organiza-
tion of Economic Cooperation and Development,
Press/A(73)3, Paris, February 14, 1973.
CHAIRMAN TIMM: I have just a few comments on
what kind of comes through to me, about three
things really. Hopefully it came through to you on
the various types of presentations we've had. Ob-
viously we are dealing with a very real problem that
impacts the livelihood of people in this country,
other countries, etc. Another big thing to come
through was that the technical people and the sci-
entific people have got to improve our communica-
tion of the scientific facts that we know to the
people that are affected. I think this is probably the
biggest frustration on the part of the average citi-
zen—he just doesn't understand what we're doing or
what we find out or maybe does not know what it
means. But I think we've got to continue to try.
Finally, no matter what action is taken, it will
have an adverse effect on some people, which of
course is an impact on the environment. I think like
the Senator says, EPA is in a "no win" situation as
far as everybody is concerned. But I think we've
learned some things tonight and gained some com-
ments good and bad that are going to help us to go
forward. Carlos wants to have some additional com-
ments and then we'll open to the floor.
MR. CARLOS FETTEROLF: I am very disturbed by
an item in the statement of the man from the Hud-
son Valley representing the Sloop Restoration
Society. He told us that Ogden Reid, Commissioner
of the New York State Department of Environ-
mental Conservation, applauded the Canada Depart-
ment of Health and Welfare for establishing its fish
400
-------
PCB regulation at 2 ppm and that Reid felt the
number should be 1 ppm.
I am also disturbed by the Indiana Senator
urging that we all go home and pound on our legis-
lators for action on PCB's.
There may not be one immediately correct
solution to the PCB problem, but there is a best
solution. The best solution is one which recognizes
all phases of the problem; weighs the advantages,
disadvantages, and costs; evaluates the impacts on
the environment, the industry, and the people. I
don't think Ogden Reid can do that off the top of
his head, nor do I think a State legislature can do it
without great thought and the wisest technical
guidance. I'm worried. I don't want to see a panic
situation. I hope USFDA does not panic. Once regu-
lators deviate from scientifically defensible environ-
mental actions, everyone loses. We waste resources,
we trade one problem for another, and we create
unnecessary costs and limitations on important seg-
ments of society. EPA must take some action.
Hopefully, it will be scientifically defensible and not
emotionally or politically motivated.
MR. JOHN CHASTAM (Lake Erie Cleanup Committee,
Toledo, Ohio): I represent the Lake Erie Clean Up
Committee, Michigan United Conservation Clubs,
and the Associated Yacht Clubs of Toledo, Ohio. I
wasn't going to get up to make any statement what-
soever, but after what I've heard here tonight. I feel
very much like Carlos.
Several years ago, you remember taconite was a
big issue after the mercury scare. Everybody was
under the impression that everything was all settled
and all of a sudden we had taconite. We got asbestos
and that worried me.
I contacted as many of the Governors and as
many of the State officials as I possibly could
around the Great Lakes for the simple reason that
you people out there as well as me own a part of
our Great Lakes. Industry doesn't own them, indivi-
duals don't own them, they're a collective thing that
we all have to enjoy. I just want you people to
know that the fight is ours. Industry should realize
what its doing to the very people they need for
help, the people that they employ.
GENERAL CHAIRMAN BUCKLEY: I want to say
about three words and they really are that I deeply
appreciate your being here. Obviously I can't agree
with each comment because there have been some
mutually exclusive ones, but 1 certainly found it
informative and really appreciate this. And the
other thing I have is a personal observation. I think
you're an enormously courteous audience and
you've sat, you've listened to views that were entire-
ly different from your own. I really enjoyed it, and
thanks again.
MR. TIMM: Good night. I got roasted literally as well as
physically.
401
-------
COMMUNICATIONS
TO THE CONFERENCE
403
-------
SOME ADDITIONAL COMMENTS WITH RESPECT-
TO AMBIENT AIR SAMPLING FOR PCB'S
Gordon H. Thomas*
The ORF, under contract to the Air Resources
Branch of the Ontario Ministry of the Environment, has
conducted ambient air sampling for RGB's.
The ambient air was sampled for gaseous
constituents by metering the air through impingers
containing ethylene glycol. In addition, sampling of the
ambient air for suspended particulates was performed
concurrently with the impinger sampling. For this
purpose, a Hi-Vol suspended particulate sampler using a
'Senior Research Scientist, Ontario Research Foundation,
Sheridan Park, Mississauga, Ontario, Canada, L5K 1B3.
glass fiber filter was employed.
Standard analytical procedures for the extraction,
cleanup, and separation of PCB's from interfering com-
ponents were followed. Final extracts were analyzed by
gas chromatography using electron capture detection.
Confirmation of the presence of PCB's in some of the
extracts was obtained with the aid of gas chromato-
igraphy-mass spectrometry.
PCB's were detected in both gaseous and particulate
sample extracts. Levels found were as follows:
Gaseous - 0.9 - 2.6 ng/m3
Particulate - 0.14 - 0.61 ng/m3
JACK TAYLOR: Gedcor Corporation markets a solvent
swellable polymer manufactured by Dow Chemi-
cal Company that possesses the unique ability to
absorb or imbibe a broad range of hydrocarbons,
including chlorinated ones such as askarels. The
polymer, sold under the name "Dow Imbiber
Bead," draws the hydrocarbon fluid into it's mole-
cular structure, thereby capturing and containing
the hazardous substance. The sealoff attribute of
the bead allows valves to be manufactured that will
allow water to pass and prevent free hydrocarbon
escape into the environment.
MS. DORCAS THOMPSON (private citizen): I would
like to speak on citizen involvement awareness and
communication. It is not enough to have hearings
on toxic substances, pollution problems, energy
problems, transportation. Ordinary citizens feel
they have much to do. They will not get interested
in any problems they should be concerned about,
because they are not at all aware of the problems. If
a problem such as PCB's is identified, EPA must
issue "educational" public releases before hearings
regularly to inform people of this threat to our
health. Of registered attendees at the conference
there are few Chicago suburban citizens-all
attendees connected with companies or agencies
such as EPA. Not one suburban environmentalist or
health person is registered. Several citizens such as
L. W. Van Audobon are present.
If dangers are identified, we need to be edu-
cated by "decree;" signs must be posted on all
areas of known PCB traces or presence—such as in
air, parks, streets, buildings, beaches, water, mar-
kets, and fish and other foods. (We need to treat
this similarly to the warning signs on cigarettes.)
The knowledge of the presence of PCB's in breast
milk must also be imparted to hospitals and new
mothers—if all of these warnings were posted with
addresses of persons to write, people would be con-
cerned and would know their opinions and concerns
are important. I disagree with Dr. Muir's concern
over industry—he is compromising by his "philo-
sophical" remarks. As we see Dow, Corning, and
Shell have a new product (we are not so entrenched
that we must consider economic factors of comp-
anies). Relocate company personnel, reeducate per-
sonnel to new job, retread personnel, computerize
information, and compare notes industry to indus-
try. After all, none of our businesses were in busi-
ness 100 years ago (in the same States they are in
today) so let us gear for change and not allow any
industries dangerous ecologically or environ-
mentally.
405
-------
LETTER TO CONFERENCE ON POLYCHLORINATED BIPHENYLS
Susan E. Caswell
Friends of the Earth, Madison, Wisconsin
November 19,1975
I am sending this statement to the Environmental Protection Agency technical conference on polychlorinated
biphenyls for the 200 members of the Madison, Wisconsin, branch of Friends of the Earth. We are deeply concerned
about the growing PCB contamination of rivers and lakes in the Midwest and throughout the country. We are
particularly disturbed by the apparent high levels of these chemicals in fish and fowl taken from Lake Michigan and
from the Upper Mississippi River.
Both of these great bodies of water have been major sources for recreational and commercial fishing in the
Midwest and provide the municipal water supplies for many communities. It seems to us that irreparable harm has
already been done to the sport and commercial fishing industries which utilize these water resources and that a very
real threat exists to the health of persons ingesting PCB contaminated fish and fowl or drinking from PCB contam-
inated waters.
We feel that scientific studies have proven the toxicity of PCBs to a wide variety of wildlife including primates
even at levels below the standards set by the Federal Drug Administration. That they are also toxic to man has been
shown by the tragic Japanese experience.
The fact that polychlorinated biphenyls are virtually indestructible by ordinary chemical or microbial processes
means that they will persist in the environment for all time, and since their uses in industry are so diverse and
widespread, the possibility for environmental contamination seems to us to be even more serious in the long run
than the analogous situation with DDT. Indeed, there is evidence that PCBs are already ubiquitous in the environ-
ment—having been detected in the sewage of all major cities, in snow melts, in organisms from the Atlantic Ocean, as
well as in fish and sediments of many lakes and rivers.
Therefore, we feel that the time to take effective action on this grave pollution problem is long past due. We
favor an outright Congressional ban on production and use of PCB's, but in the meantime, we call on the Environ-
mental Protection Agency to develop a comprehensive monitoring program for identifying sources of PCB pollution
of Lake Michigan and the Upper Mississippi River as well as other lakes and rivers and immediately begin to exercise
its authority under the Water Pollution Control Act of 1972 to regulate or eliminate PCB discharges. Thank you.
/s/ Susan E. Caswell
Friends of the Earth
Madison, Wisconsin
406
-------
LETTER TO THE ADMINISTRATOR OF
THE ENVIRONMENTAL PROTECTION AGENCY
Mrs. Meredith C. Tucker
September 8,1975
Russell Train, Administrator
U.S. Environmental Protection Agency
Waterside Mall
Washington, D.C.
Dear Mr. Train:
We are most concerned with the lack of action the EPA is taking with regard to PCB pollution in Lake Michigan
and other waterways. The seriousness of PCB pollution has been well known since 1972, yet nothing has been done
to control the release of PCB's into the environment.
It seems clear that Monsanto Company is not going to voluntarily withdraw the chemical from the market; nor
are imports of PCB's going to cease through informing industrial users about chemical concentrations in our water.
Much stronger enforcement measures are needed.
Banning the use of PCB's clearly seems to be the only real solution to the problem. Since substitute chemicals
are available for all uses of poly chlorinated biphenyls, banning PCB's should present no real hardship.
As a first step toward eliminating PCB's from Lake Michigan and other water sources, we advocate participation
in the National Conference on PCB's. Industrial users should be alerted to the dangers of PCB's and to alternative
chemicals they could use. In addition, the public should be aware of the dangers the chemical poses in use or
through human consumption of fish and water.
We urge you to take strong and immediate action to eliminate the environmental pollution of PCB's. Thank you
for your attention to this matter.
Sincerely,
/s/ Meredith C. Tucker (Mrs.)
Pesticide Control Committee
Chicagoland Chapter
Friends of the Earth
498 N. Inverway Road
Inverness, Palatine
Illinois 60067
Senator Percy
Senator Stevenson
Lake Mich. Fed.
407
-------
LETTER TO LAKE MICHIGAN FEDERATION
Chairperson, Pesticide Committee
Knob & Valley Audobon Society of Southern Indiana
November 17,1975
Lake Michigan Federation
5 3 W.Jackson
Chicago, Illinois 60604
Dear Sirs,
By unanimous decision the Knob & Valley Audobon Society of Southern Indiana voted to advocate the ban of
PCB's or the severe restriction of their use. This recommendation is based on several factors:
1. The permanent nature of PCB'S. They are not biodegradable and are stable to heat making them very
difficult to be destroyed.
2. The high levels of PCB's already found in fish in the Hudson River, Lake Michigan, and other bodies of
water.
3. The toxic nature of PCB's to human life.
If possible please have our position presented at the EPA conference in Chicago.
Sincerely,
/s/ Chairperson, Pesticide Committee
Box 237
Lanesville, Indiana 47136
LETTER TO THE ENVIRONMENTAL PROTECTION AGENCY, REGION V
Douglas V. Whitesides, Jr.
November 16,1975
U.S. - EPA, Region V
Chicago, Illinois
Re: PCB Problem Conference
November 19-20-21,1975, Chicago, Illinois
Gentlemen:
Due to the buildup of PCB's (polychlorinated biphenyls) in the environment and the serious problems caused by
this material, I believe that its manufacture and use should be completely banned immediately.
Surely the world will be a much better place without this extremely environmentally degrading substance.
Thank you,
/s/ Douglas V. Whitesides
Rt. 1, Box 296
Lanesville, Indiana 47136
408
-------
21 November 1975
Session VII:
APPROACHES TO CONTROL
John L. Buckley, Ph.D.
Session Chairman
409
-------
INTRODUCTORY REMARKS
John L. Buckley, Ph.D.
I would like to call to order the final morning of our
conference here and I would like to tell you also that I
have won an additional brass ring. I will be chairman of
the session this morning, not because I planned it that
way, but because Dr. Jim Brydon, who had agreed to
serve in this capacity and did his best to get here, could
not make it. He left Ottawa late yesterday afternoon,
having appeared before the Treasury Board in the morn-
ing and the Senate in the afternoon, and he made it as
far as Toronto, where apparently there were electrical
difficulties and so Jim will about this time be turning
around to go back to Ottawa instead of coming here.
I would like to explain to you what I have in mind
in the way we are going to try and operate. It is not all
that difficult or complex. It rather follows the statement
in the program. We will have a series of speakers, each of
whom has prepared remarks and that will be followed by
discussion among the speakers and in response to com-
ments or questions from the floor.
411
-------
A REVIEW OF FEDERAL AND STATE GOVERNMENT
ROLES IN CONTROLLING IMPACTS OF RGB's
ON THE ENVIRONMENT
A. Karim Ahmed, Ph.D.*
Abstract
Polychlorinated biphenyls (PCB's) have found ex-
tensive application in a large number of industrial prod-
ucts since they were first commercially used in the
1930's. Presently their use in the United States appears
to be principally restricted to closed electrical systems,
such as capacitors and transformers, though several tens
of millions of pounds are used each year as an insulating
fluid in these products. Numerous studies now clearly
indicate the contamination of PCB's in the environment.
Residues of PCB's are detected in many different aquatic
and animal species. They are found in high concentra-
tions in river bottoms, and in samples of commercial and
sport fish collected from the Great Lakes region and in
several rivers in the East Coast. They are found in
amounts greater than the Food and Drug Administra-
tion's tolerance limit of 5 ppm.
The roles of the Federal and State governments in
controlling the manufacture and use of PCB's are ex-
amined. It is concluded that, in most cases, little or no
regulatory activities have been initiated by government
agencies in recent years to address the problem, in spite
of the heightened concern over the potential threat of
PCB's on the environment and to public health. Only in
the past few months have several Midwestern States
bordering the Great Lakes and the State of New York
taken measures to control the discharge of PCB's from
known sources.
To cope with the problem, several recommendations
have been urged, which include: the complete phaseout
of the manufacture and use of PCB's, a ban on their
import and export, the development of a consumption
inventory, an accelerated program of monitoring and
surveillance, a moratorium on river bottom dredging,
promulgation of the PCB toxic effluent standard, a sig-
nificant lowering of present FDA tolerance limit on
PCB's, and Congressional passage of the Toxic Sub-
stances Control Act
INTRODUCTION
Polychlorinated biphenyls (PCB's) were first intro-
duced into commercial use over 45 years ago, and for a
*Staff Scientist, Natural Resources Defense Council, New
York, New York.
long time they were considered to be relatively nontoxic
substances. Their potential threat to the environment
was not recognized until 1966, when the Swedish scien-
tist, S. Jensen, observed the presence of PCB's in fish
and wildlife samples while analyzing for chlorinated
hydrocarbon pesticide residues (refs. 1,2). Since that
initial discovery, PCB's have been detected in numerous
aquatic and animal species, and have been noted in high
concentrations in industrial waste discharges, river bot-
tom sediments, food packaging materials, and in food
products, such as poultry, fish, and dairy products.
A large variety of industrial applications have been
found for PCB's, since they are endowed with a number
of desirable chemical and physical properties. They are
chemically stable, nonflammable, and essentially non-
soluble in water. They also possess a high dielectric con-
stant and are relatively viscous materials with a low vola-
.tility. Thus, they are used as heat-exchange fluids and as
a dielectric medium in electrical capacitors and trans-
formers. They have been used as hydraulic and lubricat-
ing fluids, and are used in gas turbines and vacuum
pumps. In the past, they were extensively used as plasti-
cizers in plastic products, as coatings in textile products,
and in paints and varnishes. They were also used as sea-
lants, as extenders in pesticides, and as an ingredient in
caulking compounds, adhesives, printing inks, and car-
bonless duplicating paper (refs. 3,4,5).
In 1971, over 106 million pounds of PCB's were
produced in the industrial countries of the world, with a
third or nearly 40 million pounds being manufactured in
the United States (ref. 4). During the late 1950's and
into the 1960's, U.S. domestic sales of PCB's increased
nearly threefold, reaching a peak of approximately 72
million pounds in 1970 (ref. 5). Prior to 1970, about 60
percent of U.S. domestic sales was for closed electrical
systems, such as capacitors and transformers. Another
25 percent was used as plasticizers and in the production
of carbonless duplicating paper (ref. 5). Since Septem-
ber, 1970, when Monsanto Company, the sole manufac-
turer of PCB's in the United States, restricted its sale of
PCB's to closed electrical systems, the U.S. consumption
has been reduced considerably. It is important to note,
however, that these reductions occurred mainly with the
use of PCB's as plasticizers, and as hydraulic and lubri-
cating fluids and other miscellaneous uses. The bulk of
PCB's, as mentioned above, had been used in electrical
systems, and it is still being used almost exclusively by
412
-------
manufacturers of large power and small ballast capaci-
tors, and electrical transformers, as the preferred dielec-
tric fluid.
ENVIRONMENTAL CONTAMINATION OF RGB's
Residues of RGB's in environmental samples have
now been reported in numerous studies conducted dur-
ing the past 10 years. They have been analyzed in wild-
life and fish samples in Holland, Germany, and in the
Baltic Sea (refs. 6,7). Off the coast of Scotland, RGB
residues were found in several marine species, the con-
tamination presumably having arisen from sewage wastes
being dumped into the open sea {ref. 8).
Unlike the almost ubiquitous presence of chlorinat-
ed hydrocarbon pesticides in the environment, PCB res-
idues are generally found in areas associated with high
industrial and urban activity. Little or no detectable
amounts of RGB's were found in wildlife sampled in re-
mote, nonpopulated areas, such as the Gulf of California
and Cape Crozier, Antarctica (ref. 9). Similarly, rivers
and lakes without known industrial discharges are gener-
ally found to be uncontaminated with RGB's, such as has
been shown for several watersheds and small lakes in the
upper Midwest and in Canada (refs. 10,11). On the other
hand, RGB's in increased amounts are detected in the
Eastern and Western coastal regions in highly urbanized
areas, such as the Chesapeake Bay, San Fransisco Bay,
and the Puget Sound, or in regions where industrial dis-
charges are known to occur, such as Escambia Bay,
Florida, and the Hudson River (refs. 9,12,13,14).
Studies on plankton species in the marine environ-
ment have shown them to contain detectable amounts of
RGB's. Zooplankton sampled off the Eastern continental
shelf area were observed to contain PCB levels ranging
between 0.07 and 3 ppm (ref. 15). Plankton species col-
lected in the Gulf of Mexico and the Gulf of St.
Lawrence have been found to contain PCB residues as
high as 1 ppm and 3 ppm, respectively (refs. 16,17).
Tuna caught off the Atlantic seaboard are shown to
contain PCB's with levels of 0.36 to 1.5 ppm (ref. 18).
Considerably high concentrations of PCB's are noted in
several predatory birds, with values from 30 to 900 ppm
in the livers of heron, 65 ppm (wet weight) in peregrine
falcons, 190 ppm (whole body weight) in white-tailed
eagles, to 93-470 ppm (wet weight) in the livers of cor-
morants (ref. 8, 9, 19, 20). Similarly, a number of
studies have shown relatively high levels of PCB's in the
eggs of wild birds, ranging from 1 to 44 ppm (refs. 18,
19,21).
An important impact of PCB's on the environment
has been contamination of sport and commercial fish-
eries in the Great Lakes region. Levels of PCB's in lake
trout and coho salmon from Lake Michigan show an
alarmingly increasing trend since 1972, in the average
range of 10 to 25 ppm, well above the present Food and
Drug Administration's maximum allowable concentra-
tion of 5 ppm for fish and shellfish (see figure 1) (ref.
22). On the other hand, DDT levels for the same species
of fish show a decreasing trend since 1970, when DDT
consumption in the United States was curtailed (figure
1). It is rather discouraging to note that even with the
restriction of domestic sales of PCB's to closed electrical
systems since the early 1970's there has been no corre-
sponding decrease in PCB levels in commercially impor-
tant fish species.
Fish samples collected by the Wisconsin Department
of Natural Resources last year showed extensive con-
tamination of several species of fish in Lake Michigan
(ref. 23). These include chinook salmon, coho salmon,
brown trout, tiger trout, lake trout, whitefish and carp.
Generally, the residue levels ranged well above 5 ppm,
with lake trout (up to 43.8 ppm) and carp (up to 51.6
ppm) showing the highest concentration values. In the
Upper Fox River fish sampled at one station earlier this
year by the Department showed high concentration of
PCB's in white suckers (32.7 ppm), carp (21.4 to 45.8
ppm, average 35.9 ppm) and northern pike (average 15.4
ppm). Samples analyzed by the Department in 1973
showed similar residues of PCB's in a number of fish
species in several reaches of the Mississippi River. These
data are summarized in table 1.
An interagency Task-Force on PCB's, formed of
Federal and several State agencies of Minnesota and
Wisconsin, sampled fish in the Mississippi River during
the early summer of this year and found similar levels of
PCB's in several fish species: carp (up to 33 ppm),
walleye (up to 9.8 ppm), white bass (up to 4.3 ppm).
Generally, PCB values were found at higher levels in
samples collected south of the Minneapolis-St. Paul
metropolitan area (ref. 24). More surprising is the detec-
tion of PCB residues in lake trout sampled last year in
Lake Superior by the Great Lakes Environmental Con-
taminants Survey (GLECS), which showed residue levels
ranging between 0.5 and 12.7 ppm in the Siscowet (fat)
variety of trout. The lean trout variety had lower PCB
residues, though the larger size fish often had residue
levels close to or above 5 ppm (ref. 25).
The Division of Fish and Game of the Common-
wealth of Massachusetts has in the past occassionally
sampled PCB levels in fish in several rivers and streams in
the State (ref. 26) and high levels have been detected in
several species. White sucker samples collected in 1971
m the Housatonic River showed mean PCB levels of
15.10 and 69.30 ppm at two sampling stations near the
General Electric plant in Pittsfield, Massachusetts, which
413
-------
tn
sl
O- I
o
Z 5
\
(Hdd) 33d
CM
4-^
CD
_c
C
CD
CT
O
CD
_*
CO
UJ <
>
UJ
UJ
cc
V)
T3
0}
Q
Q
T3
C
CO
CO
O
O.
414
-------
Table 1. PCB's residue in fish species in
Mississippi River, 1973 (ref. 23)
Species
Walleye
Largemouth bass
Northern redhorse
Carp
Station
Lake Pepin
Prescott
Wabasha
Trempealeau
Lake Pepin
Trempealeau
La Crosse
Lake Pepin
Prescott
Lake Pepin
Prescott
Wabasha
La Crosse
PCB(ppm)
11.9
7.21
3.84
3.16
1.65
1.74
1.49
3.45
1.01
5.49
0.57
4.31
1.95
- 31.4
- 1-1.1
- 9.00
- 6.34
- 10.5
- 5.92
- 4.24
- 8.53
- 16.2
- 11.2
- 20.44
- 10.5
- 4.05
PCB average
21.9
9.04
5.85
4.98
4.90
2.94
2.62
5.94
5.71
7.69
8.36
7.83
2.94
manufactures electrical transformers. Though it was de-
termined by the State agency that the contamination of
the fish was due to discharge of PCB's from the General
Electric plant, there has been no further monitoring of
the Housatonic River since 1971, and there is no indica-
tion whether abatement procedures used by the plant
were effective. From the data collected by the agency, it
is also clear that in 1972 there was extensive contamina-
tion of a large variety of fish species in nearly all the
rivers that were sampled in the State, with mean PCB
residue levels ranging between 1.11 and 197.0 ppm (see
table 2).
To date, the most contaminated fish sampled in this
country are found in the upper reaches of the Hudson
River, near and below two General Electric capacitor
plants in the Fort Edward-Hudson Falls area. Earlier
sampling by the Federal EPA last year had shown yellow
perch and shiner minnows to contain average PCB resi-
dues of 17 and 78 ppm, respectively, with one rock bass
sample containing 350 ppm (ref. 27). It appears that the
two General Electric plants had been discharging approx-
imately 30 pounds of PCB's per day into the river,
though in recent months there appears to have been a
reduction of daily discharges to less than 10 pounds. The
most recent fish samples collected by the New York
State Department of Environmental Conservation con-
firm the earlier findings. The composite PCB averages of
fish caught near the plant show typical values well above
20 ppm, with one American eel sample yielding residue
values of 403.4 ppm of Aroclor 1016/1242 (ref. 28).
These findings are partially summarized in table 3.
At the same time, the New York State Department
of Environmental Conservation sampling of fish species
of recreational and commercial importance in the lower
Hudson also shows high residues of PCB (ref. 28). Strip-
ed bass caught near the Albany area showed total PCB
residue values ranging between 11.08 and 89.76 pprn.
PCB residues in fish caught in the lower reaches of the
river have higher concentrations of Aroclor 1254, indi-
cating long-range transport of the previously used higher
chlorinated mixture of PCB discharged by industrial
activities in the past. Striped bass sampled near the West
Point and Tappan Zee area of the Hudson River (50
miles north of New York City and several hundred miles
south of the Fort Edward-Hudson Falls area) show total
PCB residues ranging between 1.16 and 7.54 ppm. Sim-
ilarly, a sample of American shad in the Poughkeepsie
area showed PCB residue levels of 9.0 ppm.
Of equal concern is the accumulation of PCB in
sediments of the river bottoms. PCB's, like most chlori-
nated hydrocarbons, are highly insoluble in water and
tend to settle on river sediment quite readily, being ad-
sorbed on silt and fine particles in river bottoms (ref.
12).
Data collected by the United States Geological Sur-
vey (USGS) on the Hudson River during the years
1973-74 show the presence of PCB's in the water and in
the bottom sediments of the river (ref. 29). Values rang-
ing between 0.3 and 3.0 ppb PCB have been reported in
water samples collected at several stations on the
Hudson River. These include locations near Poughkeeps-
ie, Waterford, Chelsea, and Rhinebeck.
415
-------
Table 2. Mean PCB concentration (ppm, dry weight) in fish collected
in Massachusetts rivers and streams (ref. 26)
Stream and
station
Town
No. and species
Aroclor
(ppm)
Rank
1972 1971
Millers
Deerfield
Merrimack #1
Connecticut
Merrimack #2
Chicopee
Westfield
Blackstone
Little
Ware
Athol
Deerfield
Tyngsboro
Northampton
Haverhill
Ludlow
Westfield
Mi 11vilie
Westfield
Thorndike
Aroclor 1248
1 White sucker 197.0
5 Fallfish 23.8
5 Pumpkinseed 19.1
5 Fallfish 17.7
3 Alewives 13.3
1 Eel
1 Banded killifish
5 Pumpkinseed 13.3
5 Pumpkinseed 11,9
5 White sucker 10,1
5 Golden shiner 9.41
5 Pumpkinseed 3.,32
1
2
3
4
5
6
7
8
9
10
a
5
6
4
2
3
1
7
Blackstone
Mi 11vilie
Aroclor 1260
5 White sucker
21.3
Aroclor 1254
Charles #2
Concord
Taunton
Quaboag
Cambridge
Concord
Taunton
Palmer
5 Pumpkinseed
5 Bluegill
5 Bluegill
5 Redbreast sunfish
8.3
5.96
3.13
1.11
1
2
3
4
1
2
3
-
No fish could be collected in previous years
On the other hand, PCB concentrations analyzed
from the bottom sediments of the river showed consider-
ably higher values characteristic of the insoluble nature
of RGB's. The USGS data are summarized in table 4.
More recently, the U.S. EPA conducted water and
sediment analysis for PCB's in the vicinity of Fort
Edward, near the GE plant. Water samples collected
immediately south of the GE outfalls had PCB values of
2.2 to 3.1 ppb. The sediments contained 540,000 to
2,980,000 ppb (540 to 2,980 ppm) PCB, with 6,600 ppb
being detected several miles downstream of the discharge
pipes (ref. 27).
These very high concentrations of PCB's in the sedi-
ments of the Hudson River for which dredging is
proposed are particularly troubling in light of the fact
that the highest concentrations are likely to exist in the
deep navigation channel. PCB is associated more with
finer grain particles than with particles of larger mean
grain-size diameters. This was clearly observed in exten-
sive studies carried out in a study conducted by the
State of Maryland Department of Natural Resources in
conjunction with Westinghouse Electric Company in the
Chester River (ref. 12). The study concluded as follows:
Laboratory and field studies by other work-
ers as well as the present study have indicated
that the relatively water-insoluble chlorinated
hydrocarbons readily adsorb to the surfaces of
suspended clay minerals, and, in turbid waters,
are found mainly attached to the suspended
416
-------
Table 3. Composite PCB residue in fish species sampled near the Fort
Edward-Hudson Falls area of the Hudson River (ref. 28)
Species
Station
PCB, ppm (Aroclor 1242/1016)
Rock bass
Walleye
Yellow perch
White sucker
Brown bullhead
Largemouth bass
Smallmouth bass
Fort Edward
Fort Edward
5 miles below
Fort Edward
5 miles below
Fort Edward
5 miles below
Still water
Waterford
5 miles below
Stillwater
Waterford
GE
GE
GE
GE
27.35
104.21, 81.12
157.27
61.10,236.4,
84.13, 35.5,
82.9, 8.8
51.39, 29.7,
10.3, 154.3
20.3, 36.0
73.24, 85.30
24.85, 14.31,
27.0, 36.0
, 9.88 •
128.3
88
36.03, 78.0, 57.5
8'. 99
Table 4. RGB's concentration in Hudson River
sediments, USGS (ref. 29)
Date
Station
PCB in sediments (ppb)
7/74
9/74
7/74
9/74
7/74
9/74
8/75
7/74
Chelsea
Chelsea
Poughkeepsie
Poughkeepsie
Waterford
Waterford
Roger's Island,
south of Glen Falls
Winebrook Hills
3,200
1,800
11,000
3,600
13,000
640
18,000
0.1
particulate matter. In the Chester River Study,
the inverse correlation between mean grain-size
diameter of the sediments and chlorinated hydro-
carbons content [including PCB] suggest that a
major route of transport of these compounds in-
to the Chester River is attached to the suspended
sediments that sweep into the lower river from
Chesapeake Bay. The sediments are distributed in
the bed of the Chester River in accordance to
their grain size and the local current velocity
regimes. The fine-grain materials (silts and clays)
are thrown into suspension in the shallow, shore-
line areas by wind-driven and tidal currents.
These materials tend to collect in the deeper
channels of the river, and, as is suggested by the
core data, the fine-grain sediment areas in the
deeper channels and submerged terraces probably
represent the major "sinks" for chlorinated
hydrocarbons in the Chester River. (Emphasis
added.)
The above observation of the transport and adsorp-
tion properties of several chlorinated hydrocarbons,
including RGB's, has been further confirmed by a recent-
ly completed study in the Upper Chesapeake Bay area
(ref. 30). Thus, it has been abundantly demonstrated
417
-------
that not only are PCB's adsorbed on fine-grain particu-
lates, but they are also found in highest concentrations
in the deeper channels of the river, where the channels
act as "sinks" for the insoluble hydrocarbons. Thus, the
very areas where dredging operations are being proposed
are the most contaminated,
TOXICITY OF PCB's-A BRIEF APPRAISAL
Effects on Aquatic Species
PCB's, as a class of compounds, are extremely per-
sistent and nonbiodegradable substances, and tend to
bioaccumulate in the aquatic environment by factors of
a few thousand-to several hundred-thousand-fold. PCB's
(Aroclor 1254) have been shown to concentrate over
20,000 times the water levels in Crustacea, 10,000-to
50,000-fold in certain estuarine fish species, to as much
as 200,000-fold with fathead minnows (Aroclor 1242
and 1254) (ref. 31).
The most serious effect of PCB's on aquatic species
is their ability to interfere in reproductive process and
hatchability of fish eggs. It appears that the thresholds
for whole salmon egg mortality is about 0.5 ppb (ref.
32). Similarly, the production and hatchability of fat-
head minnow eggs was adversely affected by 0.9 ppb of
Aroclor 1254 (ref. 33). Pinfish and spot were unable to
survive at 5 ppb of Aroclor 1254 (ref. 34) and many
aquatic invertebrates were clearly affected at concentra-
tion ranges of 1 to 10 ppb PCB, including blue crabs,
pink shrimp, and oyster (ref. 14). Studies by Hansen and
his colleagues at EPA's Gulf Breeze Environmental
Research Laboratory have indicated comparable mortal-
ity to several aquatic species exposed to Aroclor 1016
(ref. 35). These findings show that acute 96-hour LC50's
(or ECso's) for oyster, brown shrimp, and grass shrimp
were 10.2 ppb, 10.5 ppb and 12.5 ppb, respectively. It
thus appears that the substitution of the lower chlori-
nated homolog mixture, Aroclor 1016 (chlorine content,
41%), does not diminish the impact of PCB's on the
aquatic environment. Based on the high lethality of
PCB's to marine and freshwater aquatic species, the
National Academy of Sciences-National Academy of
Engineering Committee made the following recom-
mendation:
Aquatic life should be protected where the
maximum concentration of total PCB in unfilter-
ed water does not exceed 0.002 microgram per
liter [0.002 ppb] at any time or place, and the
residues in the general body tissues of any aqua-
tic organism do not exceed 0,5 microgram per
gram [0.5 ppm] (ref. 31).
Effects on Humans and Animals
The toxicity of PCB to humans has been clearly
demonstrated. IP 1968 a severe form of skin disease was
diagnosed in Japanese families that consumed rice oil
contaminated with Kanachlor400 (PCB with 48 percent
chlorine content) (refs. 36,37). A total of 1,057 poison-
ing cases have been recorded to date in Japan (ref. 38).
The disease is characterized by swelling of the upper
eyelids, visual impairment, acne-like formations, and
heightened pigmentation of the skin (ref. 36). Patients
with this disease also exhibited neurological disorders
and showed signs of hearing loss. Several babies born of
women patients had many of the symptoms of the dis-
ease, which indicated a placental transport of PCB, and
most fetuses were boirn smaller than the national aver-
age. Another disturbing feature of this disease was the
observation that most patients recovered very slowly,
which suggested that PCB was retained in the human
body over a very long period (ref. 38).
It should be noted here that human contamination
with PCB's is not isolated. PCB's have been detected in
human adipose tissue in such widespread occurrence that
over 40 percent of the U.S. population contains 1 part
per million (ppm) or more (ref. 39).
A number of studies have conclusively shown the
effect of PCB's on the reproduction of several animal
species. At 100 ppm in the diet of experimental rats,
PCB (Aroclor 1242 and 1254) caused a reduction in the
number of offspring that were born (ref. 36). Similarly,
in another study, dietary levels of as little as 20 ppm of
Aroclor 1254 caused a decreased number of litters to be
born to female rats (ref. 36). In a reproduction study
carried out with minks, dietary levels of less than 1 ppm
of PCB's caused a marked depression on the ability of
minks to reproduce (ref. 40).
The effects of PCB on the reproduction of pheas-
ants and chickens have also been demonstrated. Aroclor
1254 has a noticeable effect on both the production and
hatchability of pheasant eggs (ref. 41). With chickens,
dietary levels of as little as 10 ppm of Aroclor 1242 and
100 ppm of Aroclor 1254 caused thinning of eggshells,
reduced egg production, and reduced hatchability (ref.
42). In this context, it is important to note that homo-
logs of PCB with lower chlorine content may have a
greater effect on reproduction than biphenyls with high-
er chlorine content. In a recent review article on the
toxicology of PCB, Dr. Renate Kimbrough of the Center
for Disease Control in Atlanta, Georgia, stated:
The results obtained from the reproduction
studies in birds particularly seem to indicate that
418
-------
the lower chlorinated biphenyls affect reproduc-
tion more than the higher chlorinated biphenyls,
and it is very important to determine whether
the lower chlorinated biphenyls that have been
suggested as replacements for presently employ-
ed chlorinated biphenyls have an effect on repro-
duction (ref. 36).
In an extensive series of studies carried out by Dr.
James Allen and his colleagues at the University of
Wisconsin Medical School, PCB's fed in the diet of rhe-
sus monkeys caused significant effects that mimicked
both the symptoms of known human toxicity and repro-
duction failures in experimental animals. When female
rhesus monkeys were given 25 ppm of Aroclor 1248 for
a period of 2 months, severe symptoms of facial swelling
and skin eruptions were manifested (ref. 43). At lower
dietary levels of 5 ppm and 2.5 ppm (Aroclor 1248),
similar clinical symptoms were observed after a few
months, and more significantly, these low levels of PCB
caused marked effect on reproduction. After three
matings with male monkeys, only 12.5 percent of the 5
ppm PCB dietary group and 37.5 percent of the 2.5 ppm
group were pregnant as compared to 90 percent pregnan-
cies with a comparable control group (ref. 44). At the
same time, fetuses that were born were significantly
smaller in size and continued to ingest high PCB levels
from the nursed milk of their mothers (ref. 45). These
effects at low PCB levels are particularly important to
note, since the present Food and Drug Administration
tolerance limit for PCB residue in fish and shellfish is 5
ppm (ref. 46), and were based on an assumption of a
higher no-effect level.
Of serious concern is a recent study conducted by a
group of research investigators at the Center for Disease
Control, Atlanta, Georgia, the U.S. Environmental Pro-
tection Agency, the National Cancer Institute, and the
Johns Hopkins University School of Medicine (ref. 47).
They observed that when Sherman strain female rats
were fed 100 ppm of PCB (Aroclor 1260) for about 21
months, 26 of 184 of the experimental animals exam-
ined had malignant liver tumors (hepatocellular carcin-
oma), whereas only 1 of 173 control animals had the
same disease. At the same time, 146 of the experimental
and none of the control animals had tumorous lesions
(neoplastic nodules) in the liver.
Other toxic effects of PCB that have been reported
in the scientific literature include: (1) increase in the
biological activity of certain hydroxylating enzymes in
the liver and increased activity in the rat; (2) induction
of liver porphyria in several animal species; (3) interfer-
ence with the immune defense mechanisms of rabbits;
(4) neurological disorders in rats; (5) increased PCB resi-
due in fatty tissues, serum, and milk; and (6) teratogenic
effect in the chick embryo (refs. 48, 49).
IMPACT ON RECREATIONAL AND
COMMERCIAL FISHERIES
One of the most illustrative examples of the impacts
of PCB contamination on the environment is an exami-
nation of its effect on sport and commercial fisheries on
the Hudson River. The Hudson River is a productive
breeding ground for fish, not only for resident species
such as white perch, but also for migratory oceanic
species like striped bass, shad, and herring. The short-
nose sturgeon, which has been classified as an endanger-
ed species, is also an inhabitant of the Hudson River (ref.
50).
Striped bass are the most economically important of
the fish that spawn in the Hudson since the species sup-
ports a major recreational and commercial fishery. For
that reason, too, it is a species of particular concern
because of the high levels of public consumption of Hud-
son River striped bass and the economic dependence of
commercial fishermen on the species.
The weight in 1970 of the striped bass commercial
catch in the New England Region plus New York State
(including the Hudson River) was 2,780,000 pounds
(ref. 51). The weight in 1970 of the striped bass sport
catch in the North Atlantic (which includes New York
State) was 45,844,000 pounds (ref. 52). Hudson-
spawned striped bass are a major component of the
Atlantic stock. Though estimates have varied, there is no
doubt that the contribution is substantial. The staff of
the Nuclear Regulatory Commission (ref. 53) has taken
the position that:
1. The Hudson River stock is the major source of
striped bass caught in the Hudson River, the western half
of Long Island Sound, and the New York Bight (Barn-
egat Inlet, N.J., to Moriches Inlet, N.Y.). In this "Inner
Zone" of influence the NRC staff estimates that more
than 50 percent of the sports and commercial landings
are made up of Hudson-spawned striped bass and uses a
figure of 90 percent for its own estimates (ref. 53).
2. In the "Outer Zone" of influence, extending
from Maine to Cape May County, N.J, (less the Inner
Zone), Hudson-spawned striped bass constitute some-
where between 10 and 50 percent of the sports and
commercial fishery.
The average annual commercial catch of striped bass
for the years 1961-1969 in the Inner Zone was 268,200
pounds (ref. 53). Using the NRC's 90 percent figure.
419
-------
241,400 pounds represent the average annual commer-
cial catch in the Inner Zone attributable to Hudson
River striped bass. The average annual commercial catch
in the Outer Zone is 1,969,000 (ref. 53), 50 percent of
which is 984,500 pounds. The annual total for commer-
cial catch of Hudson River striped bass is therefore esti-
mated to be about 1,200,000 pounds.
In 1970, a pound of striped bass would bring a com-
mercial fisherman $.26/lb on the average. The retail
price would be, at a minimum, three times that amount.
Striped bass is now selling at $1/lb in New York. Using
this retail value of $1/lb, the value of commercial catch
of Hudson River striped bass appears to be in the range
of $1.2 million per year.
In 1970, the striped bass sports catch exceeded the
commercial catch in the North Atlantic (which includes
New York State) by a f£Ctor of 16.5 (ref. 53). Assuming
an annual commercial catch of 1,200,000 pounds of
Hudson River striped bass, one can extrapolate to a
sports catch of 21,200,000 pounds. This amount repre-
sents a little less than 50 percent of the 45,844,000
1970 sports catch of striped bass in the North Atlantic
and, therefore, is, if anything, an underestimation of the
Hudson River sports catch. In sum, something on the
order of 22,000,000 pounds of Hudson River striped
bass are probably consumed each year, if we combine
these commercial and sports catch figures. Moreover, the
problem is even more serious than the above information
would indicate. The striped bass is a migratory fish with
stock from various sources (e.g., the Chesapeake,
Delaware, and Hudson) intermingling. Since there is no
way to distinguish origin of a striped bass, the entire
North Atlantic stock may be contaminated.
An indication of the' magnitude of the total Great
Lakes fishery problem from PCB contamination can best
be seen by evaluating the value of sport and commercial
fisheries for the State of Michigan. The sport fisheries in
the Great Lakes are comprised of coho and Chinook
salmon, steelhead, brown and lake trout. This fishery is
known collectively as the salmon fishery. This is the
fishery most substantially effected by PCB contamina-
tion.
Value of sport fishery in Michigan is determined by
multiplying the number of angler days by $15 per day.
In the Great Lakes contiguous with the State of Michi-
gan in 1974, there were 3.1 million angler days devoted
to the anadromous and Great Lakes fishery. The total
value of this sports fishery is estimated at $46.5 million.
Another determination is a total value of the fishery to
resident and nonresident fishermen. Michigan has deter-
mined this to be $24 to $30 million—a somewhat lesser
figure but still quite substantial. The value of the total
Great Lakes sport fishery would be substantially larger
when data from other States are included (ref. 54).
The commercial fishery in the Great Lakes has been
on recent decline due to overfishing, so the value is sub-
stantially less than the sport fishery. In 1974, the num-
ber of pounds caught totalled 14,524,079, with an
estimated value of $3,814,840.
The commercial species most affected by PCB con-
tamination has been observed to be chubs. These fish are
caught commercially in Lake Michigan and Lake Supe-
rior. Their 1974 catch and value are recorded in table 5.
As the above table indicates, chubs represent
approximately 32 percent and 54 percent of the com-
mercial fishery, respectively, in these two lakes. Any
significant decrease in the availability of chub popula-
tion to the commercial fishery will have a negative
impact on the fish-related economy of the region. It is
possible that a decreased chub population would elimi-
nate commercial fishery from the Great Lakes altogeth-
er.
FEDERAL AND STATE GOVERNMENT ROLES
Since the early 70's, when it was increasingly realiz-
ed that widespread contamination of PCB's had occurred
in this country, a number of events highlight the role
that the Federal and State governments have taken, or
have failed to take, in addressing this problem. A Federal
Interdepartmental Task Force was convened in 1972,
which concluded that because of the highly persistent
nature of PCB's and their bioaccumulation in the food
chain, they posed a serious threat to human health. They
recommend restricting the use of PCB's to closed
electrical systems, such as electrical transformers and
capacitors (ref. 56), However, as mentioned before,
Monsanto Company had begun restricting its domestic
sales for such exclusive purposes since the fall of 1970,
and it is not clear what the Task Force's recommenda-
tions issued in May, 1972, had to do with the voluntary
move made earlier by the company as has been suggested
in recent remarks by an official of a Federal agency (ref.
57).
In July, 1973, the Federal Food and Drug Adminis-
tration established tolerance limitation in a variety of
food products as follows (table 6):
Toxicity data oblained during the past year that
show severe reproductive failure in low concentrations
of PCB in primates (5 and 2.5 ppm), and the recent
demonstration of carcinogenicity with Sherman strain
rats (refs. 44,47), clearly indicate the need to substanti-
ally revise the present FDA tolerance limitations of
PCB's in foods. This in turn will have the effect of com-
pletely changing the definition of "unacceptable" levels
of PCB's in fish and poultry, to be at times almost all
420
-------
Table 5. 1974 commercial fish catch and value in
Lakes Michigan and Superior (ref. 55)
Lake Michigan
Lake Superior
Chubs
Catch (Ibs)
1,154,067
1,011,234
Value ($)
780,793
464,499
Total Fish
Catch (Ibs)
10,924,961
1,5.29,736
Value ($)
2,496,208
826,592
Table 6. FDA tolerances for PCB in food and
food packaging (ppm) (ref. 46)
Product
Milka
Dairy product
Poultry ,
Fish and shellfish
Eggs
Infant and junior food
Complete and finished
animal feed
Animal feed components
Paper food-packaging
material
Tolerance level
2.5
2.5
5.0
5.0
0.5
0.2
0.2
2.0
10.0
(ppm)
On fat basis.
^Edible portion.
inclusive of many species that inhabit the polluted lakes,
streams, or feedlots, in this country.
In spite of the deficiencies of the present tolerance
standards, the FDA has in recent months taken seizure
action against several fish shipments earmarked for com-
mercial markets in Lake Michigan, since they exceeded
the present 5 ppm guideline (ref. 61). Similarly, the
FDA seized a shipment of carp this summer in Lake
Pepin on the Mississippi River (ref. 58). In view of a
recent legal decision that clearly allows the FDA to
define pesticide residues in foods as an indirect food
additive, the FDA is expected to enforce its guidelines
more forcefully in the future. FDA officials in the Great
Lakes region have warned that chubs, coho salmon, and
lake trout may be disallowed in interstate commerce,
since they continue to contain high residue levels of
PCB's (ref. 61). It is apparent that with a more thorough
monitoring and surveillance program, nearly all species
of fish in the Great Lakes region and in several rivers in
the East coast area will be essentially unavailable for
human consumption for many years to come.
One of the great ironies of the oresent situation is
that over 3 years ago the Federal Water Pollution Con-
trol Act (FWPCA) directed the Federal Government,
specifically the Environmental Protection Agency (EPA)
to take swift action to reduce the discharge of PCB's and
other toxic water pollutants to safe levels. The fact that
today there is no meaningful national program to regu-
late PCB discharges is a result of the Federal Govern-
ment's disappointing failure to carry out the FWPCA as
Congress wrote it or, for that matter, to take any other
strong regulatory action.
421
-------
The Congressional authors of the FWPCA believed
that the "hazards posed by toxic substances" made their
effective regulation "especially urgent" (ref. 59). Ac-
cordingly, they established in the act a "national policy
that the discharge of toxic pollutants in toxic amounts
be prohibited" (ref. 60) and added to the act a far-reach-
ing special provision, Section 307(a), to insure that this
goal was fully implemented. If Section 307 (a)'s manda-
tory deadlines had been met, toxic pollutant effluent
standards covering PCB's and other toxic pollutants
would have been promulgated by EPA roughly 2 years
ago and complied with by dischargers about 1 year ago.
Yet, to date EPA has failed to promulgate a single stand-
ard under this provision.
State officials have also expressed dismay over the
EPA's failure to promulgate toxic substances effluent
standards. John Hesse of the Michigan Department of
Natural Resources in recent comments at a regional con-
vention, stated:
I want to mention that the delay in this
standard [effluent standard for PCB] has weak-
ened the states attack on industrial sources and is
long over-due, (ref. 61)
It is instructive to review the events leading to the
current situation. Section 307(a) of the act requires EPA
to first develop a list of toxic water pollutants. For the
substances on this list EPA must subsequently develop
and enforce strict effluent standards, standards which
must protect the users of the waters with an "ample
margin of safety" (ref. 60) EPA began inauspiciously by
failing to meet FWPCA's January 12, 1973, deadline for
publication of the list of toxic pollutants. When 4
months later the list had still not been published, the
Natural Resources Defense Council brought suit chal-
lenging EPA's default. That suit ended on June 19,
1973, when the U.S. District Court ordered EPA to
publish the list "on or before August 31, 1973" (ref.
62). The list published by EPA as a result of this court
directive, though inadequate in many respects, did in-
clude PCB's along with eight other pollutants.
Section 307(a) also requires that prior to promulgat-
ing final standards for substances it has listed, EPA must
first propose such standards for public comment and
then hold a formal hearing on them. Standards for the
nine substances, PCB's included, were in fact proposed
by EPA on December 27, 1973. The required hearing
began a month loter and continued through May, 1974.
Under Section 307(a) EPA is mandated to promulgate
final standards not later than 6 months after publication
of proposed standards, or "immediately" if EPA chooses
to modify the proposed standards as a result of the hear-
ings (ref. 60) Yet, despite this requirement, 2 years have
elapsed without the promulgation by EPA of a single
standard under Section 307(a)
This failure to develop final standards is being chal-
lenged in a law suit brought in the District of Columbia
(ref. 63). The NRDC and the Environmental Defense
Fund (EOF), plaintiffs in the suit, are claiming that the
EPA's omission is contrary to FWPCA's requirements
and are seeking a ruling establishing court-ordered dead-
lines for final EPA action on toxic pollutant effluent
standards. In affidavits filed in this law suit, EPA has
stated that the record of the original hearing "could not
justify or support the promulgation of either the origin-
ally proposed standards or any specific modification
thereof" (ref. 64), In support of this conclusion, EPA
claims that the evidence at the hearing was inadequate to
permit the agency to determine "what level of each of
the toxic pollutants would provide an ample margin of
safety as required by Section 307(a) of the Act." EPA
also states that it was unable at the hearings "to either
assess or respond to" industry evidence "tending to
show" that the proposed standards would have substan-
tial economic repercussions on the regulated industries
(ref 64), Accordingly, EPA now intends to repropose,
i.e., to propose new toxic pollutant effluent standards,
and to begin the hearing process again. The agency states
that under its new schedule it "expects" to propose new
standards for PCB's in late February, 1976 (ref. 65).
EPA has also informed the parties to the ,aw suit that
these new PCB standards, unlike the original standards,
will be limited to dischargers who manufacture PCB's or
use PCB's in castings, electrical transformers and capaci-
tors.
Behind this record of delay lies a series of complex
problems which deserve to be examined in a far more
comprehensive manner than we can undertake here. Our
own judgment, based on our work in this area over the
past 3 years, is that several underlying factors are princi-
pally responsible for this failure of Federal regulation.
We offer them for further examination and discussion.
First, EPA has not had during this period a strong
institutional commitment to doing something about the
problem of toxic water pollutants. Partly this is a reflec-
tion of the historic concerns of the sanitary engineering
profession, concerns which still dominate much of EPA's
thinking, and partly it results from the failure of EPA
leadership to assign priority attention to this problem
during the formative period of the agency's programs.
Even as Congress was developing the act, EPA informed
the House Public Works Committee that "we do not
endorse the provisions of Section 307 relating to toxic
substances" (ref. 66). Subsequently, the resources EPA
allocated to the toxic pollutant problem were miniscule
422
-------
in comparison with the need, and this pattern continued
despite the fact that it was repeatedly criticized. As late
as March, 1975, EPA's priorities in the water pollution
area completely neglected control of toxic pollutants. In
a discussion of priorities for fiscal year 1976, EPA failed
to mention toxic pollutants in a table listing the agency's
first, second, and even third priorities for the coming
year (ref. 67).
A second factor has been the very large and well
financed efforts by the dischargers of toxic pollutants to
oppose development of standards under Section 307(a).
Approximately 35 major corporations and industry
groups challenged EPA's proposed standards in the for-
mal hearing that was held in early 1974. The talents of
many of the country's best paid lawyers and scientists
were at the disposal of the PCB, mercury, and cyanide
dischargers, and it seems almost certain that far more
resources were spent picking apart EPA's proposed
standards than EPA had used in developing them.
One theme developed by the dischargers at these
hearings was the potential economic impact of meeting
the proposed standards. Evidence was introduced at the
hearings to show that the technology to meet some of
the standards was not available or that where it was
available it could only be installed at substantial ex-
pense. It was also contended that the proposal would
force segments of major industries to shut down. EPA,
though it has never rigorously investigated these claims,
has nevertheless acted on them to the point that concern
over economic dislocations has become a major inhibit-
ing factor within the agency, overshadowing any concern
with public health and environmental quality. Environ-
mental organizations have urged EPA, unsuccessfully,
not to delay standards development on these grounds,
pointing out the self-interest in such claims of hardship
and also EPA's obligation to implement the act as Con-
gress wrote it. If a discharger believes that a variance
from a Section 307(a) standard is justified in light of
economic hardship, that plea, environmental groups have
urged, should first be addressed to Congress, since Sec-
tion 307(a) does not now contain a variance provision.
But the absence of such a variance provision should not
be used to justify inaction, or inadequate action, by
EPA.
Because of recent publicity in the media of PCB-
contamination in the Great Lakes region and the Hudson
River, it is encouraging to note that several States have
taken administrative and legislative initiatives to control
the discharge of PCB's into lakes and rivers. Earlier this
year, the Michigan Natural Resources Commission
endorsed the recommendation of the Lake Michigan
Toxic Substances Committee, calling for a ban on PCB
imports and use in the United States and for a rapid
replacement of PCB's in electrical capacitors and trans-
formers (ref. 61). At the same time, a bill has been intro-
duced in the State Legislature to place strict control on
the use and sale of PCB's in the State (ref. 61).
!n Wisconsin, the Division of Health of the State
Department of Natural Resources has issued warnings on
consumption of large size lake trout and salmon from
Lake Michigan and the upper Mississippi River. The
Department also held a hearing in August of this year,
with a view \o developing a strategy to control the sale
and distribution of PCB's within the State (ref. 61). In
Minnesota, an Interagency Ta^K Force was established,
principally to widen the monitoring of PCB's in fish in
several rivers and streams in the State {ref, 24).
In terms of administrative remedies, the strongest
action was taken this year in New York State, after it
was discovered that two G E plants on the Hudson
River appeared to be the major dischargers of PCB's in
upper regions of the river. The New York State Depart-
ment of Environmental Conservation on September 23,
1975, issued an abatement order requiring the G E
plants to achieve zero discharge of PCB's by September
30, 1976. Administrative hearings begun on October 6,
1975, are expected to continue for several weeks (ref.
69). At the same time, Commissioner Ogden Reid of the
department publicly cautioned consumers against eating
striped bass from the Hudson River and salmon caught
in Lake Ontario 'ref. 70).
On the international front, the Organization for
Economic Cooperation and Development (OECD) a few
years ago recommended to its member countries, which
includes the United States, West Germany, France,
United Kingdom, Japan, Italy, and Spain, involved in the
production of PCB's, to restrict the commercial use of
PCB's to closed systems (ref. 71). Only Japan has taken
further strict measures to completely eliminate the use
of PCB's in all commercial application, including capaci-
tors and transformers. It also prohibits the import and
export of the compound, and since September, 1972,
there has been a virtual elimination of almost all applica-
tions of PCB's in the country {ref. 57).
CONCLUSION AND RECOMMENDATIONS
On August 29 of this year, NRDC and the Hudson
River Fisherman's Association requested the Adminis-
trator of EPA to take immediate and decisive action to
curtail the discharge of PCB'3 into the Hudson River,
pursuant to § 504 of the^ Federal Water Pollution Con-
trol Act (FWPCA) (ref. 72). Under § 504, the EPA is
given authority to seek whatever emergency relief is
needed to seek abatement with pollution sources pre-
senting "an imminent and substantial enciangerment to
423
-------
the health of persons or to the welfare of persons'." To
date, we have received no indication that the EPA is
prepared to take emergency action against PCB dischar-
gers, and with respect to the G E plants on the Hudson
River, it has postponed its permit hearings pending the
present State of New York proceedings against the
company.
At the same time, we are very concerned about the
proposal by the U.S. Army Corp of Engineers to under-
take extensive maintenance dredging in shipping chan-
nels in the Hudson River. We have called upon the Corp
of Engineers to hold public hearings before the agency
prepares its final environmental impact statement, since
in the earlier draft statement the agency had failed to
recognize the problem of PCB contamination of sedi-
ments in river bottoms (ref. 73).
On behalf of three New York environmental and
conservation organizations, we have intervened in the
administrative proceedings now being conducted by the
New York State Department of Environmental Conser-
vation against the two G E plants in the Fort Edward-
Hudson Falls region of the Hudson River. We are in
general agreement with the State's abatement order of
achieving zero discharge of PCB's by September next
year.
Finally, we are at present, along with the Environ-
mental Defense Fund, planning to petition the Federal
Food and Drug Administration to lower the current PCB
tolerance limits on foods and food products in the
United States. This is, as mentioned previously, based on
recent long-term data that show considerably lower
"effect" levels of PCB's on experimental animals.
We recommend the following courses of action that
should be taken by Federal and State agencies to address
the problem of PCB's contamination of the environ-
ment:
1. A complete phase-out of the manufacture, sale,
use and distribution of PCB's in this country, including
its use in closed electrical systems;
2. A ban on the import and export of PCB's to
and from the United States;
3. Development of a PCB use and consumption
inventory, to pinpoint all point and nonpoint discharge
of PCB's to the environment;
4. An accelerated program of monitoring and sur-
veillance of PCB's in fish, wildlife, and foods by State
and Federal agencies;
5. A moratorium on all dredging of river bottoms,
until a complete study is conducted to examine the
resuspension of PCB's in river water from such activities;
6. Promulgation by the EPA of the toxic sub-
stances effluent standard with respect to PCB's, such
that water quality standard? in receiving streams be no
more than 0.001 ppb;
7. A significant lowering of present FDA tolerance
limitation of PCB's in foods to reflect present knowledge
of its long term chronic toxicity; and
8. A swift passage of the Toxic Substances Con-
trol Act, which is still pending in Congress, to provide
additional authority to Federal agencies to cope with the
manufacture and use of loxic substances.
ACKNOWLEDGEMENT
The author is grateful to Sarah Chasis, Esq., J.
Gustave Speth, Esq., Frances Beinecke, and Eileen
Richmond for their assistance in the preparation of this
report.
REFERENCES
1. S. Jensen, "A New Chemical Hazard," New Scien-
tist, Vol. 32 {1966), p. 612.
2. G. Widmark, "Possible Interference by Chlorinated
Biphenyls," J. Assoc. Offic. Anal. Chem., Vol. 50
' (1967), p. 1069.
3. M. G. Broadhurst, "Use and Replaceability of Poly-
chlorinated Biphenyls," Environ. Health Perspec-
tives, No. 1 (1972), p. 81.
4. 'Polychlorinated Biphenyls. Their Use and Con-
trol," published by the Environment Directorate,
Organization for Economic Cooperation and Devel-
opment (OECD), Paris, November 1973.
5. "Polychlorinated Biphenyls — Environmental Im-
pact," A review by the Panel on Hazardous Trace
Substances (Chairman: Norton Nelson), Environ-
mental Research, Vol. 5 (1972), p. 249.
6. J. H. Koeman, M. C. TenNoever DeBrauw, and R.
H. DeVos, "Chlorinated Biphenyls in Fish, Mussels
and Birds from the River Rhine and the Netherlands
Coastal Area," Nature, Vol. 22! (1969), p. 1126.
7. S. Jensen, A. G. Johnels, M. Olsson and G. Otter-
lind, "DDT and PCB in Marine Animals from
Swedish Waters," Nature, Vol. 224 (1969), p. 247.
8. A. V. Holden, "Source of Polychlorinated Biphenyl
Contamination in the Marine Environment," Na-
ture, Vol. 228 (1970), p. 1220.
9. R. W. Risebrough, P. Rieche, D. B. Peakall, S. G,
Herman and M. N. Kirven, "Polychlorinated Bi-
phenyls in the Global Ecosystem," Nature, Vol. 220
(1968), p. 464.
10. V. Zitko, "Polychlorinated Biphenyls and Organ-
ochlorine Pesticides in Some Freshwater and Marine
424
-------
Fishes," Bull. Environ. Contam. Toxicol., Vol. 6
(1970), p. 464.
11. G. D. Veith, "Recent Fluctuation of Chlorobi-
phenyls (RGBs) in the Green Bay Wisconsin Re-
gion," Environ. Health Perspectives, No. 1 (1972),
p.51.
12. "Chester River Study," published by Maryland
Department of Natural Resources and Westinghouse
Electric Co., Annapolis, Maryland, November 1972.
13. D. L. Stalling and F. L. Mayer, "Toxicities of PCBs
to Fish and Environmental Residues," Environ.
Health Perspectives, No. 1 (1972), p. 159.
14. T. W. Duke, J. I. Lowe, and A. J. Wilson, Jr., "A
Polychlorinated Biphenyl (Aroclor 1254) in the
Water, Sediment and Biota of Escambia Bay, Flor-
ida," Bull. Environ. Contam. Toxicol., Vol. 5
(1970), p. 171.
15. R. W. Risebrough, V. Vreeland, G. R. Harvey, H. P.
Miklas and G. M. Carmignani, "PCB residues in
Atlantic Zooplankton," Bull. Environ. Contam.
Toxicol., Vol. 8 (1972), p. 345.
16. C. S. Giam, M. K. Hong, A. R. Hanks, W. M. Sackett
and R. L. Richardson, "Chlorinated Hydrocarbons
in Plankton From the Gulf of Mexico and Northern
Caribbean," Bull. Environ. Contam. Toxicol., Vol. 9
(1973), p. 376.
17. D. M. Ware and R. F. Addison, "PCB Residues in
Plankton From the Gulf of St. Lawrence," Nature,
Vol. 246 (1973), p. 519.
18. V. Zitko and P. M. K. Choi, "PCB and Other Indus-
trial Halogenated Hydrocarbons in the Environ-
ment," Fish. Res. Board Canada, Technical Report,
Vol. 272 (1971), p. 1.
19. I. Prestt, D. J. Jeffries, and N. W. Moore, "Polychlo-
rinated Biphenyls in Wild Birds in Britain and Their
Avian Toxicity," Environ. Poll., Vol. 1 (1970), p. 3.
20. J. H. Koeman, "PCB in mammals and birds in the
Netherlands," PCB Conference II (S Lundstrom,
ed.) National Swedish Envrionmental Protection
Board publication 4E, Stockholm, 1972, p. 35.
21. Y. A. Greichus, A. Greichus, and R. J. Emerick,
"Insecticides, Polychlorinated Biphenyls and Mer-
cury in Wild Cormorants, Pelicans, Their Eggs, Food
and Environment," Bull. Environ. Contam. Toxi-
co/.,Vol. 9 (1973), p. 321.
22. J, L. Hesse, "Contaminants in Great Lakes Fish,"
staff report, Michigan Department of Natural
Resources, June 1975.
23. P, Degurse and V. Outer, "Chlorinated Hydrocarbon
Residues in Fish From Major Waters of Wisconsin,"
published by Bureau of Fish and Wildlife Manage-
ment, Wisconsin Department of Natural Resources,
Report No. 79, Madison, Wise., July 1975.
24. "Preliminary Report on the Polychlorinated Bi-
phenyls in Mississippi River and Lake Pepin," by the
Interagency Task Force on PCB's, obtained from
Minnesota Pollution Control Agency, St. Paul, Aug.
1975.
25. J. L. Hesse, "PCB Situation in Great Lakes Fish,"
report to the Michigan Water Resources Commis-
sion, April 17, 1975.
26. P. J. Palermo, "Progress Report, Massachusetts
Pesticide Monitoring Program, April 1972 to March
31, 1973," Division of Fisheries and Game, Com-
monwealth of Massachusetts, Boston, Mass., 1973.
27. R. J. Nadeau and R. Davis, "Investigation of Poly-
chlorinated Biphenyls in the Hudson River: Hudson
Falls-Fort Edward Area," EPA Region II Report,
circa, October, 1974.
28. "Monitoring of PCB's in Fish Taken From the Hud-
son River," published Bureau of Environmental
Protection, Division of Fish & Wildlife, New York
Department of Environmental Conservation, Al-
bany, N.Y., October 1975.
29. John Turk, United States Geological Survey, Al-
bany, N.Y., (private communication).
30. Thomas Munson, Westinghouse Ocean Research
Lab., Annapolis, Maryland (private communica-
tion). Also from preliminary draft of the Upper
Chesapeake Bay study.
31. "Water Quality Criteria," a report of the Committee
on Water Quality Criteria Environmental Studies
Board, National Academy of Sciences, National
Academy of Engineering, Washington, D.C., 1972.
32. S, Jensen, N. Johannson, and M. Olsson, "PCB -
Indications of Effects on Salmon," PCB conference
sponsored by Swedish Salmon Research Institute,
Stockholm, September 29,1970.
33. National Water Quality Lab., Quarterly Research
Report, Duluth, Minnesota, June, 1971.
34. D. J. Hanscn, P. R. Parrish, J. I. Lowe, A. J. Wilson,
Jrs., and P. D. Wilson, "Chronic Toxicity, Uptake,
and Retention of a Polychlorinated Biphenyl (Aro-
clor 1254) in two Estuarine Fishes," Bull. Environ.
Contam. Toxicol., Vol. 6 (1970), p. 113.
35. D. J. Hansen, P. R. Parrish, and J. Forester, "Aro-
clor 1016: Toxicity to and Uptake by Estuarine
Animals," Environ. Research, Vol. 7 (1974), p. 363.
36. R. D. Kimbrough, "The Toxicity of Polchlorinated
Polycyclic compounds and Related Chemicals",
CRC Critical Reviews in Toxicology, January 1974,
p. 445.
37. M. Kuratsune Y. Morikawa, T. Hirohata, M. Nishi-
zumi, S. Kohchi, T. Yoshimara, et al., "An Epidemi-
o logical Studv on 'Yusho' or Chlorobiphenyls
Poisoning", hnkuoks Acta Med., Vol. 60 (1939), p.
513.
38. M, Kuratsunp T, Yoshimura, J. Matsuzaka, and A.
425
-------
Yarnaguchi, "Epidemiologica! Study of Yusho, a
Poisoning Caused by Ingestion of Rice Oil Contami-
nated With a Commercial Brand of Polychlorinated
Biphenyls", Environ. Health Perspectives, No. 1
(1972), p. 119.
39. H. A. Price and R. L. Welch, "Occurence of PCB's in
Humans", Environ. Health Perspectives, No. 1
(April 1972).
40. N. S. Platonow and L. H. Karstad, "Dietary Effects
of Polychlorinated Biphenyls on Mink," Canadian J.
Comp. Med., Vol 37 (1973), p. 391,
41, R. B. Dahlgren, R, L. Linder, and C. W. Carlson,
"Polychlorinated Biphenyls: Their Effects on
Penned Pheasants", Environ. Health Perspectives,
No. 1 (1972), p. 402.
42, M. L. Keplinger, 0. E. Fancher and J. C. Calandra,
"Toxicologic Studies With Polychlorinated Bi-
phenyls", Toxicology & Applied Pharmacology Vol.
19 (1971), p. 402.
43. J. R. Allen, L. A, Carsteris, and D. A. Barsotti,
"Residual Effects of Short-Terrn, Low-Level Expo-
sure of IMonhuman Primates to Polychlorinated Bi-
phenyls," Toxicol. & Appl. Pharmacol., Vol. 30
(1974), p. 440.
44. J. R. Allen, "Response of the Nonhuman Primate to
Polychiorinated Bipheny! Exposure," Federation
Proceedings, Vol. 34 (1975), p. 1675.
45. J. R. Allen, University of Wisconsin Medical School,
Regional Primate Research Center, Madison, Wis-
consin (private communication).
46. Federal Register, Vol. 38, No. 129 (July 6, 1973),
p. 18096.
47. R. D. Kimbrough, R. A. Squire, R. E. Linder, j. D.
Strandberg, R. J. Montali, and V. W. Burse, "Induc-
tion of Liver Tumors in Sherman Strain Female
Rats by Polychloiinated Biphenyl Aroclor 1260,"
preprint of study obtained from R. D. Kimbrough,
Center for Disease Control, Atlanta, Georgia.
48. "Polycbloiinaied Biphenyls and the Environment,"
Interdepaitmentai Task Force on PCB's, Washing-
ton, n.c., May 1972.
49. J. R. Allen an :• 0. H. Norback, "Polychlorinated
Biphenyl and Terphenyl-lnduced Gastric Mucosal
Hyperplasia in Primates," Science, Vol, 179 (1973),
p. 498.
50. U. S. Department of the Interior, "Endangered
Species of the United States," Bureau of Sport Fish-
eries & Wildlife, U.S. Fish & Wildlife Service, 1970.
51. "Fisheries Statistics of the United States," National
Marine Fishen.": Service publication, 1971.
52. D. G. Deuei, "1Q70 Salt-Water / ngling Survey," U.
S. Department of Commeice NOAA, National
Marine Fisheries Service, Curre-* Hshery Statistics
No, 6200, 1973
53. Final Environmental Statement (FES), Operation of
Indian Point Nuclear Generating Station Unit No. 3,
Consolidated Edison Company of New York, Inc.,
February 1975.
54. "Michigan Great Lakes Trout and Salmon Fishery,
1969-1972"' Fisheries Management Report No. 5,
Michigan Department of Natural Resources, June,
1973.
55. J. L. Hesse and N. Fogle, Michigan Department of
Natural Resources, Fisheries Divison (private com-
munication),
56. "Polychlorinated Biphenyls and The Environment",
Interdepartmental Task Force on PCB's, Washing-
ton, D.C., May, 1972.
57. G. E. Schweitzer, Director, Office of Toxic Sub-
stances, Environmental Protection Agency, in state-
ments made at a Hearing on PCB's held by the Wis-
consin Department of Natural Resources, Madison,
Wisconsin, August 29, 1975.
58. "Mondale, HHH center PCB Fray", Minneapolis
Tribune, August 26, 1975, p. 1-B.
59. Senate Report No. 92-414, 92nd Congress, 1st Ses-
sion, (1971), p. 61.
60. Title 33, United States Code, R1251 (a) [FWPCA
R101 (a) (3); R307 (a) (4) ].
61. J. L. Hesse, Michigan Department of Natural Re-
sources, Lansing, Mich. "Summary of Regulatory
Efforts of The Greet Lakes Region Toward The
Environmental Control of PCB's (Polychlorinated
Biphenyls)", speech presented to the Governor's
Great Lakes Regional Interdisciplinary Pesticide
Council, Chicago, Illinois, September 18, 1975.
62. Natural Resources Defense Council v. Fri, D.D.C.
Civil Action No. 849-73, Decree and Stipulation
(June 19,1973).
63. Environmental Defense Fund and Natural Resource
Defense Council v. Train, D.D.C. Civil Action No.
75-0172.
64. R. V. Zener, affidavit filed August 12, 1975 in EOF
and NRDC v. Train, (reference 63).
65, K. M. Mackenthun, affidavit filed August 12, 1975,
in EOF and NRDC v. Train, (reference 63).
66. "A Legislative History of the Water Pollution Con-
trol Act Amendment's of 1972", Senate Committee
on Public Works, Serial No. 93-1, 93rd Congress,
1st. Session (1973), p. 1199.
67. BNA Environment Reporter, Current Develop-
ments, Vol. 5 (March 28, 1975), p. 1893.
68. Lake Michigan Toxic Substances Committee, EPA,
et al., a statement of concern relating to PCB's,
draft, 1975.
69. New York State Department of Environmental Con-
servation, Complaint (File No. 2833) issued against
General Electric Co. Sept. 23, 1975.
426
-------
70. "State Says Some Striped Bass and Salmon Pose a EPA, From NRDC and Hudson River Fisherman's
Toxic Peril," New York Times, August 8, 1975, p. Association, August 29, 1975.
1. 73. Comments of NRDC, Hudson River Fisherman's
71. Decision of the Council, Organization for Economic Association, and Hudson River Sloop Restoration, a
Cooperation and Development, on Protection of the proposal for maintenance dredging of The Hudson
Environment by Control of Polychlorinated Bi- River by The U. S. Army Engineer District, New
phenyls, adopted by Council on February 13, 1973. York, October 22, 1975.
72. Letter to Russell E. Train, Adminstration, U. S.
427
-------
FDA REGULATION OF PCB's IN FOOD
John R. Wessel*
Abstract
Investigations by the Food and Drug Administration
(FDA) during the period of 1969-1971 disclosed that
PCB's had become a significant contaminant of the
Nation's food supply. Spillage or leakage of PCB's from
manufacturing equipment or contact with PCB-contain-
ing materials were identified as routes of direct contami-
nation of food and animal feed. The presence of PCB's
in the environment was causing the indirect, unavoidable
contamination of certain types of food, particularly
those of animal origin. In March 1972, the Food and
Drug Administration formally proposed regulations to
limit bureau exposure to PCB's from these sources of
PCB's in the diet (the scientific and legal basis for these
regulations, which were finalized in July 1973, are de-
scribed). Presently, the problem of PCB contamination
of foods, except for certain freshwater fish, has substan-
tially diminished. Because of new scientific information
on the potential hazards of PCB's on the public health
and the continuing presence of high levels of PCB's in
certain freshwater fish, the Food and Drug Administra-
tion has initiated a review of its temporary tolerance of
5 ppm in fish.
In 1969, the Food and Drug Administration identi-
fied the presence of PCB residues in milk from several
dairy farms in West Virginia. Eventually, the source of
contamination was traced to spent PCB transformer
fluid that was used as a vehicle for a herbicide. The
herbicide-PCB mixture was sprayed along powerline
rights-of-way causing dairy cattle grazing,areas to be-
come contaminated. West Virginia officials were advised
that FDA would initiate regulatory action against ship-
ments of milk containing 5 ppm or more PCB's on a fat
basis. As a result, the involved dairy farms were placed
under State embargo until it was demonstrated that milk
from these farms contained acceptable levels of the con-
taminant.
I mention this incident for several reasons. First, it
represented the first documented incident in which an
industrial use of PCB's directly contaminated food, in
this case animal feed, which subsequently caused resi-
dues in milk. Second, it represented the first U.S. regula-
tory action taken because of PCB contamination of
"Scientific Coordinator, Office of the Associate Commis-
sioner for Compliance, Food and Drug Administration, Rock-
ville, Maryland.
food. Third, aside from historical interests, it represent-
ed a preview and start of what was to become a complex
and serious problem.
Within the next 2 years, seven other major incidents
of PCB contamination of food had occurred in the
United States. Not only did these so-called "industrial
accidents" present a threat to human health, they also
resulted in severe economic losses to the milk, egg,
poultry, and feed-producing industries. Since the details
on these accidents have been reported (ref. 1), I will not
describe the circumstances surrounding each. Suffice it
to say that by late 1971, it was quite apparent that
spillage or leakage of PCB's from manufacturing equip-
ment or contact with PCB-containing materials could,
and did, directly contaminate food and feed.
During the same period, FDA and other regulatory
agencies began to routinely test foods for the presence
of PCB residues. It soon became evident that because of
their widespread, uncontrolled industrial uses, PCB's had
also become persistent and ubiquitous contaminants in
the environment, causing the unavoidable, indirect con-
tamination of certain types of foods.
Although scientific information on their hazards
was limited in 1971, there was sufficient data for FDA
to conclude that the presence of PCB's in food posed a
potentially serious public health problem and that regu-
latory controls were necessary.
Accordingly, FDA developed and published a notice
of proposed rulemaking in March 1972 (ref. 2) to limit
human exposure to PCB's by dealing with the direct and
indirect sources of PCB's in the diet. On July 6, 1973, a
final order on the proposed regulations was issued in the
Federal Register (ref. 3).
The final regulations included two main provisions:
First, it banned the industrial uses of PCB's in estab-
lishments manufacturing, handling, or storing human
food, animal feeds, and paper food-packaging materials.
This was done to preclude the direct, accidental contam-
ination of these articles. The ban did not apply to the
use of PCB-containing electrical transformers and capaci-
tors.
The Federal Food, Drug, and Cosmetic Act pro-
vided the statutory authority for invoking these restric-
tions as part of FDA regulations on Current Good Manu-
facturing Practices. This preventive approach means that
the industrial uses of PCB's in firms subject to FDA
jurisdiction would be considered a violation of the law
without first having to demonstrate that products from
these firms were being contaminated.
428
-------
The second provision of the FDA regulations was
the establishment of temporary tolerance for unavoid-
able, indirect PCB contamination of milk and other
dairy products, eggs, poultry, baby foods, animal feed
and feed ingredients, and fish; also, since 1973, FDA has
had in effect an action level for RGB's in paper food-
packaging materials (table 1).
Table 1. FDA temporary
tolerances for RGB's
Commodity
Temporary
tolerance
(ppm)
Milk
Dairy products
Poultry
Eggs
Finished animal
feeds
Animal feed
components
Fish
Infant and
junior foods
Paper food-
packaging
material
2.5 (fat basis)
2.5 (fat basis)
5.0 (fat basis)
0.5
0.2
2.0
5.0 (edible
portion)
0.2
10.Oa
Action level
Prior to the 1972 issuance of the proposed PCB
regulations, FDA used guidelines or informal action
levels to control the marketing of foods and feeds with
excessive PCB residues.
The authority to establish the tolerances for PCB's
in these consumer products is found in section 406 of
the Federal Food, Drug, and Cosmetic Act. This section
provides that where the addition of a poisonous or dele-
terious substance to food cannot be avoided, regulations
shall be promulgated to set limits on the quantity of the
substance permitted. Section 406 contains three criteria
for the setting of these limits: (1) the extent to which a
limit is necessary for protection of public health, (2) the
extent to which the substance cannot be avoided, and
(3) the other ways in which the consumer may be af-
fected by the same or other poisonous or deleterious
substances.
In dealing with the problem of unavoidable PCB
contamination of foods,- FDA's principal objective was
to minimize human exposure from dietary sources of
PCB's. At the same time, the agency sought to avoid
serious disruption of the Nation's food distribution
system so as not to deprive the consumer of a significant
portion of his food supply. As a result, it was considered
necessary to establish separate and different limits for
each type of food shown to contain unavoidable resi-
dues. Only in this way would overall dietary levels be
kept at a minimum and would the public be assured that
PCB's, if present in these foods, are generally within safe
limits.
Thus, the selection of appropriate tolerance levels
for PCB's in the different foods represented a "bal-
ancing" between potential harm to the consumer and
economic impact. This balancing principle, which is
mandated by section 406 of the statute, necessitated the
use of subjective judgment regarding available informa-
tion on the toxicity of PCB's and on the occurrence of
PCB's in the food supply. In other words, while they
took into account established, acceptable daily intakes,
the tolerance levels were not based solely on ADI's, nor
can they be explained strictly in terms of ADI's.
Data from FDA total diet studies and surveillance
programs for 1969-1972 were also important considera-
tions. These data showed that PCB residues in food were
sporadic and that by eating a well-balanced diet, there
was only a remote possibility of systematic exposures to
PCB's at or above the ADI's over an extended period of
time. As a result, FDA concluded that the tolerance
levels would provide an adequate margin of safety for
the public, provided dietary exposure to PCB's remained
sporadic and, in time, would diminish. This approach
also allowed FDA to set the tolerance levels high enough
to minimize the economic impact that would result from
the food and feed industries' compliance with the toler-
ances.
Since issuance of the FDA regulations, the agency
has not encountered the types of "PCB-accidents" in-
volving food or feed that had occurred prior to 1972.
Current surveillance data form FDA, the U.S. Depart-
ment of Agriculture, and others show that with the ex-
ception of freshwater fish, the presence of PCB's in
those commodities subject to tolerances continue to be
random and sporadic, but with an overall substantial
decline in their frequency and levels.
This decrease is precisely what FDA intended when
429
-------
it promulgated the PCB regulations and, as I just men-
tioned, served as one of the basic premises for the tem-
porary tolerances.
FDA attributes the present situation to several fac-
tors:
1. Voluntary restrictions instituted by industry with
respect to the industrial uses of RGB's. This has
resulted in less potential for PCB contamination of
the environment and subsequent transfer to food.
2. Regulatory actions initiated by FDA, USDA, and
State agencies when excessive levels of RGB's in
food were encountered. This has had a salutary
effect on industry practices.
3. Efforts of the food and feed industries to conform
to Current Good Manufacturing Practices and to
market only those products that comply with the
tolerances.
I wish to emphasize, however, that the present situ-
ation does not mean that FDA considers RGB's to be no
longer a problem. Since occasional shipments of food
exceeding tolerance have been encountered during the
past 2 years, there is st!|- a need to monitor foods for
PCB residues and to have regulations governing the
presence of RGB's in the food supply. Furthermore, and
certainly of a more serious nature, is the continued prob-
lem of RGB's in fish as a result of continued industrial
discharges of the chemical into lakes and rivers. Needless
to say, reports of PCB levels in freshwater fish from
certain waters at 5 to 10 times higher than the FDA
tolerance of 5 ppm are reasons for concern, particularly
since there is little, if any, scientific disagreement that
the regular and consistent consumption of fish at these
levels may pose a potentially serious threat to the con-
sumer.
Because of this concern, FDA recently began evalu-
ating the adequacy of its current tolerance for RGB's in
fish. This evaluation includes a review of all recently
reported studies on the toxicity of RGB's, as well as a
review of available data on the current PCB levels in fish
and the economic impact that would result from a low-
ering of the 5 ppm tolerance.
-If the decision is made to lower the tolerance, a
proposed amendment to the existing regulation will be
published in the Federal Register along with a detailed
explanation of the basis for the proposal. Through this
rulemaking procedure, public comment will be solicited
and fully considered by FDA before final action is taken
and implemented.
Obviously, a lowering of the tolerance by FDA will
not in itself solve the many problems of pollution of the
environment with PCB's. Nor will it guarantee that fish
available for consumption will comply with the toler-
ance since only fish involved in interstate commerce are
subject to FDA's jurisdiction. Thus, FDA enforcement
of a lower tolerance will not necessarily result in addi-
tional protection for each and every consumer. Further-
more, even if warnings and advisories are issued by FDA
and State officials, there is no assurance that sports fish-
ermen and, perhaps others, would abide by these warn-
ings.
The same may also be said for foods other than fish
since, as long as the chemical is being used in a manner
that causes its introduction into the environment, the
potential for the indirect contamination of the food sup-
ply surely exists.
For these reasons, the Food and Drug Administra-
tion urges and will support the Environmental Protec-
tion Agency and State agencies in the initiation of con-
trols aimed at the industrial uses and particularly the
disposal of PCB's in order to curtail and eliminate
further pollution of the environment and the contamin-
ation of foods with PCB's.
REFERENCES
1. Polychlorinated Biphenyls and the Environment, In-
terdepartmental Task Force on PCB's, Washington,
D.C., May 1972.
2. Commissioner of Food and Drugs, "Proposed Rule-
making on Polychlorinated Biphenyls," Federal
Register, Vol. 37, No. 54 (March 18, 1972), pp.
5705-5707.
3. Commissioner of Food and Drugs, "Polychlorinated
Biphenyls — Contamination of Animal Feeds,
Foods, and Food Packaging Materials," Federal
Register, Vol. 38, No. 129 (July 6, 1973), pp.
18096-18103.
430
-------
PROGRAMS AND AUTHORITIES OF
THE ENVIRONMENTAL PROTECTION AGENCY
Walter C. Barber*
Abstract
The Environmental Protection Agency operates
under many constraints. Its research and regulatory
functions are influenced by Congress, court action, and
public opinion. The time and energy required to produce
even a simple regulatory action is substantial. And what
appears to be a large EPA staff is actually small when the
number of toxic substances and contaminant point
sources to be controlled are considered. When creating
regulations, EPA must attempt to make them reasonable
and enforceable; the regulations then must of necessity
be limited.
EPA's role with respect to the Federal Water Pollu-
tion Control Act and the Clean Air Act is herein ex-
plained. Recommendations are made that could improve
the Federal/State Point Source Regulatory Program:
public awareness could be increased among people who
use PCB's as to their handling and disposal; there is
potential for joint industry/government voluntary label-
ling and disposal control for PCB's; EPA could focus
attention on electric utilities, the major user of PCB's;
and finally, local water quality management programs
funded under the Federal Pollution Control Act could
be redirected so that they give PCB control greater em-
phasis.
The purpose of my talk is not to tell you again what
either EPA has or has not done to. control PCB's or to
tell you what we are going to do. Quite frankly, I do not
know what we are going to do beyond what you have
heard explained in terms of increased monitoring, re-
search, establishing a 307(a) toxic effluent limitation,
and establishing permit limitations for known dis-
chargers of PCB's.
Rather, what I thought I would do today is briefly
to review EPA's programs and authorities. I will try to
give you a feel for the context of our decisionmaking
and the limitations on it so that the non-EPA people
here have a better feel for what they can rely on the
Federal Government to do in the future and what things
they probably ought to think about doing at the State or
even, perhaps more importantly, at the local level.
Perhaps the overriding concern is that Federal regu-
lation in the environment (or anywhere else) requires a
"Director, Standards and Regulations Evaluation Division,
Office of Planning and Evaluation, Environmental Protection
Agency, Washington, D.C.
clear understanding of the consequences of regulatory
action. The law requires it, the public expects it, and we
are making every effort to do it. As a result, the regula-
tory process is not as responsive and rapid as we might
like it to be Dr. Ahmed made some pointed comments
about EPA progress in regulating under the Federal
Water Pollution Control Act. These comments were fac-
tually correct, but i think there are probably some rea-
sons for these things happening, generic reasons associ-
ated with Federal regulation that we should keep in
mind. I do not know that there is a way, even if all the
people in the Environmental Protection Agency were
replaced, to change substantially the approach to envi-
ronmental reguli ;on at the Federal level.
It is imporU for non-Federal people to remember
that the Federal Government is no more than a collec-
tion of people. The people who are going to regulate
PCB's are in this room or have been in this room over
this 3-day period. So when we say that EPA or the Fed-
eral Government should do something, in essence we are
saying that the people sitting here, who know no more
or less about PCB's than you do, should do something.
The Environmental Protection Agency is not a very
large o.ganization when you think about the scope of
the problems that Congress has asked it to deal with.
EPA is asked to regulate tens of thousands of station-
ary-point sources of air and water pollution, tens of
thousands of pesticides that are being used in the envi-
ronment, and tens and even hundreds of thousands of
drinking water supplies. We have programs on radiation
noise, solid waste, and toxic substances. In addition, we
have what is considered to be the largest Federal Public
Works program in our Municipal Construction Grants
effort. We also have a substantial research and develop-
ment program. There is no army of people to implement
these programs. There are fewer than 10,000 people in
the Agency with only a couple of hundred in the
Regional Office here. When they are divided among the
various programs and the number of sources to be con-
trolled, and the time and energy that goes into taking
even some of the most simplistic regulatory enforcement
steps is considered, it seems unlikely that EPA will be
able to revolutionize regulation or enforcement in the
area of PCB's.
Mr. Train has made it clear that he is going to
accord a high priority to PCB control, and hopefully, we
are going to do substantially better than we have. How-
ever, we do not have hundreds of Federal bureaucrats to
431
-------
locate and control all the sources of the RGB's that are
going into municipal sewers, being dumped on the
ground, and running off into streams and rivers. It is
important to remember that our resource allocations fre-
quently are driven by things that we cannot control. We
come under tremendous pressures from the public, the
courts, and from the Congress to do or take action in
various areas. A year ago, municipal construction grants
received a great deal of attention—we were not spending
the construction grants money fast enough or building
enough municipal treatment works. With regard to regu-
lations, our friends at NRDC have served a very valuable
public service by encouraging us to overcome our
bureaucratic inertia and to move faster in some areas.
But in fact our efforts to accelerate the regulatory proc-
ess have often resulted in the courts remanding our
decisions, doubling the work, with little or no environ-
mental benefit.
The Federal Water Pollution Control Act, for those
of you who have not had an opportunity to read it, is
extremely long and complex and has a number of pro-
visions that would bear on the PCS pollution problem.
They overlap, I won't say that they conflict, but they
have the potential to conflict in some cases. The act is
very demanding in terms of the things which the Federal
Government must consider in the process of developing
its regulations. When we do not consider them, the
courts require us to go back and do so.
We are caught somewhat in the middle. I see the
legislative history and the nature of environmental laws,
Federal Water and Pollution Control Act, and Clean Air
Act as essentially having established the purpose of
Federal involvement to be a reinforcement for State pro-
grams, with the State having the basic responsibility. The
Federal role is to establish national standards, provide
some financial and technical assistance, and to act where
a State government is unable or unwilling to enforce the
regulations.
Because of the way the acts are written, there are
some things that EPA can do well. There are other things
that the State and local governments can do much
better, and there are still other things that the public can
do. The strength of the environmental program is clearly
with the public, and then with the State and local
governments and must flow up rather than down.
Regulation, either for the control of toxic sub-
stances, of which PCB's are an example, or for the con-
trol of biochemical oxygen demand, will not be mean-
ingful and will not have any real impact on the environ-
ment unless reasonable limitations are applied. I do not
know what these reasonable limitations are for
PCB's—they may be zero. The reasonableness of a regula-
tion is determined by technology, economics, and en-
forceability. Based on what I have heard over the past
21/2 days, there are serious questions as to the enforce-
ability of regulatory actions which go beyond the 20
principal users.
EPA's legislative authorities and its principal areas
of effectiveness focus on major point sources and dis-
charges. With PCB's we do not have very many major
point source discharges. Although at .least some of those
point sources seem to be creating problems, it is not
clear to me, based on some of the numbers that were
presented, particularly for the Los Angeles area, that
controlling point sources is going to solve even a major
part of this problem.
We will regulate these point sources, and hopefully
we will be able to enforce those regulations so that the
contribution from the major point sources will be dimin-
ished, if not eliminated. Based on quantities of PCB's in
existence in the environment, we can say that those that
have been produced over the last 30 years have not de-
graded those that have been imported. It seems some-
what questionable to me, if not unlikely, that that con-
trol of major point sources of PCB's is going to solve the
fishery problem in the Great Lakes.
Let me take about 2 minutes to run through the
Federal Water Pollution Control Act and the Clean Air
Act, just to tell you where we are with regard to control-
ling PCB's. Under the Federal Water Pollution Control
Act, the Federal government can establish water quality
criteria, which we have done. This was done before the
current act was passed. We have proposed revisions, and
those final revisions have been printed and are creeping
their way through the bureaucracy and toward the
Federal Register. I expect that they will be published in
final form in the next several months. This is a fairly
substantial document and includes what we recommend
in terms of ambient water quality, which is adequate to
protect biological populations. The States in turn have
to set the standards based in part on these criteria and in
part on their own judgments of the local conditions.
Establishment of the standards does not solve any
problems because it does not eliminate any discharges.
Other sections of the act are designed to reduce dis-
charges to achieve the standards. Section 304 provides
for us to establish technology-based limitations and ef-
fluent guidelines upon which we base our industrial per-
mits. Section 307, the toxic substance part, has turned
out, at least in our minds, to be a very difficult section
of the act to implement. Perhaps it will not be as diffi-
cult to implement for PCB's as it is for some of the other
toxic substances and we are moving forward on it, al-
though belatedly.
Section 307(b) calls for pretreatment and is signifi-
cant because a substantial portion of the PCB's reaching
432
-------
our waterways are discharged from municipal treatment
works and not from direct discharges on the part of
industry. The pretreatment standards are going to pre-
sent enforcement problems because it is difficult for
municipalities and essentially impossible for the Federal
Government to trace down every discharger of toxic pol-
lutants to municipal sewer systems. We do not know
whether the discharger is throwing pollutants down a
manhole under the cover of darkness, whether he is dis-
charging regularly through drainage in a building, or
whether the pollutants are run off through combined
sewers from a nonpoint source.
Section 311, the hazardous substances section of
the act, is designed to protect from spills of hazardous
substances. We have had some spills of RGB's, however,
it seems clear to me that, unless someone has been
hiding a lot of spills, the quantities of RGB's that are in
the Great Lakes are several orders of magnitude larger
than anything you could attribute to spills into the
water. Spills on the land could be another question.
However, once again, a few hundred Federal bureaucrats
are not going to be able to chase a million capacitors or
transformers and find out whether someone is releasing
RGB's on the ground.
The section 402 permit program provides for efflu-
ent limitations for direct discharges to navigable waters.
In addition, we have the emergency power provisions of
section 504, which were alluded to by Dr. Ahmed, Quite
frankly, I do not know what the criteria are for employ-
ing the emergency powers or what Mr. Train proposes to
do in response to the petition.
The Clean Air Act might become a significant part
of the effort to control RGB's if the numbers for the Los
Angeles basin are accurate and representative. With this
act, we are in a more difficult position in my opinion
than we are with the Federal Water Pollution Control
Act. The Clean Air Act is based on ambient standards, as
opposed to technology-based effluent or emission limita-
tions. It is unlikely that we could establish, monitor, and
enforce an ambient standard for RGB's unless, by some
fortuitous happening, most of the RGB's emitted into
the air are coming from a few discreet point sources.
We can establish new source performance standards
for air emissions, which are in fact technology standards,
but I do not believe that new air emission sources are
going to be the key to the RGB problem.
The hazardous air pollutant section in 112 of the
Clean Air Act provides for emission limitations which
are adequate to protect the public health with an ade-
quate margin of safety. I have seen nothing in the infor-
mation presented that alluded to the health effects of
airborne RGB's. It seems to be more a question of the
airborne RGB's washing into the rivers. I think that we
would have a difficult time employing section 112.
I would like to run through what I personally think
might be attractive supplements to the Federal/State
Point Source Regulatory program. Based on what I have
heard over the last few days, I believe that a substantial-
ly increased level of public awareness is necessary among
the people who use RGB's. Working principally with
labor and the management of industries using RGB's, we
must try to improve the level of awareness about proper
handling and disposal.
I see potential for a joint industry/government
voluntary labeling.and disposal control program, which
would be substantially more restrictive than what we
have now. Given the magnitude of the problem, it would
appear that both the industry and the affected labor
unions might be sympathetic in trying something along
those lines to avoid the problems caused by unknowl-
edgeable dumping of RGB's.
It seems to me that we have a major resource in our
electric utilities, who apparently use the predominant
share of RGB's in closed electrical systems. Electric utili-
ties are fairly sensitive to public concern, and I would
think that the electric utilities as a group or perhaps even
individually might be sympathetic to mounting a signifi-
cant labeling and waste-handling campaign, which they
would subject to some public scrutiny.
Lastly, we are spending substantial sums of money
on funding local water quality management agencies un-
der section 208 of the Federal Pollution Control Act. It
seems to me that, with what is likely to be millions of
dollars available in the Great Lakes basin for water
quality management, the people who live here might be
well served by having the 208 agency work on the PCS
problem in addition to BOD reduction, waste load allo-
cations, and sediment laws. If in fact the RGB's remain
the dominant concern in the Great Lakes basin, then
maybe the 208 agency could help track down the
apparent myriad of small discharge sources, to educate
dischargers, and to help put controls on them.
433
-------
U.S. FEDERAL AGENCY ROLES AND ACTIONS:
THE DEPARTMENT OF THE INTERIOR
Nathaniel P. Reed*
Abstract
The Department of the Interior warns that its assess-
ment of the impact of polychlorinated biphenyls upon
national fish and wildlife resources, as determined by the
National Pesticide Monitoring Program, reveals environ-
mental hazards. The evaluation of data from the moni-
toring program has demonstrated a serious detrimental
impact by PCB's upon national fish and wildlife re-
sources and restoration programs. The Department of
the Interior recommends immediate toxic substances
legislation for control of domestic and imported sources
of toxic substances.
During the past 2 days numerous reports have been
given describing the uses and sources of PCB's, their
occurrence in various components of the environment,
and their real or potential threats to the health of our
natural resources. The documentation of the widespread
contamination of our environment by this group of com-
pounds demands that we elevate our recognition of
PCB's from a local concern to a national and global level:
We must immediately respond to the dangers posed by
PCB's; they represent an ubiquitous degenerative influ-
ence on our national health and well-being.
The reasons for this concern are simply stated: Our
food and water supplies are contaminated; our health is
threatened; and we are faced with "environmental
stress" about which we know comparatively little!
The PCS problem is a national problem that the
U.S. Fish and Wildlife Service has identified in both re-
search studies and in the National Pestjcide Monitoring
Program. As earlier papers pointed out, PCB residues
were found in all of the fish samples from 100 stations
located in major river systems throughout the United
States, and in almost all the bird samples taken since
1970.
I am deeply shocked by the pervasiveness of PCB's;
they are literally everywhere. And I am very troubled by
the exceedingly high levels found in fish from all our
drainage systems; and I do not mean just the Hudson
and the entire Great Lakes' system, but the Merrimac
and Connecticut Rivers of the Atlantic Coast, the
Mississippi, Missouri, and Ohio Rivers of the Midwest,
the Columbia River system in the Northwest, the Sacra-
mento in the West, Rio Grande River and other Gulf
Coast streams, and even the Yukon in Alaska!
•Assistant Secretary for Fish, Wildlife, and Parks, De-
partment of the Interior, Washington, D.C.
Fish are not alone in absorbing sizeable quantities of
PCB's. The birds we are monitoring are equally suscep-
tible. Waterfowl carry the highest residues in the Atlan-
tic flyway, followed in descending order by the
Mississippi, Pacific, and Central flyways. Further, all
starlings collected since 1970 contain PCB residues.
It is one thing to trot out all these scientific facts
and figures identifying quantitative residues in various
terrestrial and aquatic organisms; it is quite another to
assess the broad impact of PCB's upon our environment
and natural resources. What are the effects of pesticides,
heavy metals, and hazardous substances such as PCB's
and what do they mean to our fish and wildlife habitat?
Cleansed of all the details, the facts, simply stated,
are that we are in trouble. My department has spent
millions of dollars, and is programming millions more in
these times of fiscal austerity, on programs aimed at
reinvigorating our wildlife resources, and protecting and
restoring numerous threatened and endangered species.
The omnipresence of PCB residues in our environ-
ment looms as a very dark cloud casting an ominous
shadow upon all of our fish and wildlife resource pro-
grams which depend on environmental quality and
healthy habitats. In particular, PCB's pose an immediate
threat to our efforts to preserve and protect threatened
and endangered species. Under present conditions PCB's
may very well pull the rug out from beneath us by des-
troying marginal species in spite of our best efforts for
preservation.
Consider the Atlantic salmon, a species we are striv-
ing to reintroduce into our northeastern rivers. Atlantic
salmon egg mortality has been associated with a thres-
hold concentration of about 0.5 ppm of PCB. Our
scientists tell me that this threshold concentration in the
eggs would be equivalent to residual PCB levels in whole
fish of 2.5 to 5.0 ppm, comparable to unhealthy levels
found in many species throughout the United States.
I cannot justify a salmon restoration program in any
northeastern river system where the fish will be subject-
ed to PCB residues. Other recent tests show that rainbow
trout eggs containing as little as 2.7 ppm of the PCB,
identified as Aroclor 1242, and 90 ppb of DDT complex
caused 75 percent mortality—and about 60 to 70 per-
cent of the surviving fry were deformed.
Another test demonstrated that fish bioaccumulated
more than 40,000 times the concentration of PCB in the
water. I think the fish are telling us something. They are
stating unequivocally that our rivers and streams are
sick. We should not need a clarion call to realize that our
434
-------
rivers and lakes—the very lifelines of our environ-
ment-are in mortal danger.
I am aware that it took many years of research be-
fore we could identify the effects of DDT, dieldrin, and
other organochlorine pesticides in birds and mammals.
We know that the reproductive success of bald eagles has
been greatly reduced in Maine and along the shores of
Lake Michigan where high residues of DDE, dieldrin and
PCB are present in eagle eggs.
Similarly, the once abundant osprey population of
Long Island Sound has suffered a near total decline as a
result of chemical toxicants. Although our extensive
work on PCB-fed ducks revealed little reproductive loss
or eggshell thinning at environmental levels of PCB, I
hope we don't have to repeatedly demonstrate the dif-
ferences in susceptibility among wildlife species before
we establish the imminence of a hazard requiring drastic
national action. Remember that while we found quail
and pheasant resistent to DDE thinning of eggshells,
mallard and black ducks, american kestrels, screech owls,
and brown pelicans were all highly susceptible. It pains
me to remind you that the ban on DDT was not imposed
until long after its threat to wildlife was proved, and
action was taken only when studies showed the potential
hazard to human health.
I suggest that we cease to quibble over scientific
niceties and respond to the ailing resources around us. In
this day and age, we should not need to be told that if
the health of our natural resources is impaired, then
human health is next around the corner en route to the
sick bay.
We are meeting on the shore of one of a series of
lakes that represents the world's greatest single fresh-
water resource; appropriately, they are called the Great
Lakes. But how do we measure their greatness? Their
immense area and volume are sufficient to characterize
them as "great." They can also be considered "great"
because of their esthetic and recreational value. Perhaps
we could even classify them as "great" based on the
amount of municipal and industrial waste they hold.
The list of attributes for these lakes is long and
varied but regardless of the criteria used, the conclusion
remains the same-the lakes and everything contained
therein truly constitute a "great" resource.
The lakes' fisheries are particularly important both
as utilizable and renewable resources and as indicators of
the health of our Great Lakes. I am convinced that fish
and wildlife are the true barometers of the quality of our
environment. In my capacity as the steward of fish and
wildlife for the Department of the Interior, and as a
commissioner on the Great Lakes Fishery Commission, I
have an overwhelming concern for the protection and
management of Great Lakes Fishery resources.
During this century, the fisheries of the Great Lakes
have suffered from heavy fishing, relentless predation by
the parasitic sea lamprey, the influx of other nonnative
species like the alewife, and the diminished quality of
habitat as a result of waste disposal, uncontrolled shore-
line development, and numerous other water polluting
activities.
In recent years, however, we have taken significant
steps at great financial cost to stop the decline of Great
Lakes fisheries and to restore them to their former pro-
ductivity. As a first step in this restoration, we under-
took the control of the parasitic sea lamprey. Our co-
operative efforts with the States, Provinces, and the
Canadian Government achieved success in all the Great
Lakes except Lake Ontario, where intensive control
programs are now underway.
After 17 years and 33 million dollars, the sea
lamprey, with a continued sustained control effort, no
longer represents a major threat to the fisheries of the
upper Great Lakes. The dissolution of the lamprey
threat has allowed a successful State and Federal re-
stocking program involving more than 150 million lake
trout, splake, coho salmon, Chinook salmon, atlantic
salmon, and kokanee. Additional millions of rainbow,
brook, and brown trout have also been stocked.
These stocked salmonids have fed heavily on the
plentiful alewife and have rapidly grown to trophy size.
The resulting sport fishery of these salmonids, when
combined with the existing sport fisheries on other
species, currently contributes approximately 350 million
dollars annually to the Great Lakes States and the Pro-
vince of Ontario.
All our efforts are for naught if these fish cannot be
harvested—and we now face this stark possibility. A sig-
nificant portion of these fish contain PCB residues in
excess of the current 5.0 ppm action level established by
FDA. As a result, warnings have been issued about the
consumption of large lake trout and salmon from Lake
Michigan. To varying degrees a similar PCB problem
exists in Lakes Superior, Huron, and Ontario.
Although contamination by PCB's is particularly
evident in salmonids, the problem is also present in com-
mercial species such as carp, chubs, smelt, and alewives.
Carp from Lake Michigan have already encountered mar-
ketability problems because of PCB's, and chubs appear
to be at or just below the 5.0 ppm action level.
But if the current level were lowered to I or 2 ppm,
then virtually all species would be restricted and essenti-
ally the entire Great LakeV fishery would be curtailed.
The current guidelines of 5.0 ppm has already tabled any
serious consideration of commercially utilizing the sal-
monid populations in the near future. PCB's present a
major problem in the future maintenance and growth of
435
-------
commerical fisheries. These fisheries today have a
dock-side value of about $19 million annually and a
total economic contribution to the United States and
Canada of possibly $95 million annually when process-
ing, shipping, and retailing are included.
We must now consider the expenditure of millions
of dollars for controlling sea lamprey and stocking sal-
monids in the Great Lakes in the light of continued
contamination of the fish stocks with unacceptable
levels of RGB's. There are overriding reasons in favor of
continuing our program. These include aspects of
biology, economics, and ecology. The lake trout restora-
tion program exemplifies these considerations. More
than 17 years were required to restore lake trout to its
present abundance in Lakes Superior and Michigan. If
we stop our current programs, it is almost certain that
the sea lamprey would reestablish itself and the salmonid
populations and the fisheries dependent upon them
would collapse, thus wiping out the past Federal invest-
ment of many years and millions of dollars and a Great
Lakes economy worth several hundred million dollars.
Although we know considerably more now than we did
17 years ago about lamprey control and salmonid stock-
ing programs, it would still require at least 10 years to
recontrol the lamprey and rebuild the lake trout stocks.
Why so long? The reason is a simple biological
one—it takes 7 years for a lake trout to mature to an
adult, spawning fish. There are few overnight solutions
to natural resource restoration projects. Obviously, the
quickest and most economical solution to the problem is
to eliminate RGB's from the environment. With RGB's in
the lakes, the entire program of restoring self-sustaining
stocks of lake trout in the Great Lakes, or in fact all
salmonids, is in serious jeopardy. And yet if we cannot
eat these fish, I cannot justify spending millions of
dollars contributed by the American taxpayer.
We cannot wish this problem away. Nothing short
of immediate drastic action will enable us to raise any-
thing better than lakes full of eunuchized fish. With the
present preponderance of RGB's, the lifespan of the
Great Lakes fishery will be limited to a single generation.
The Great Lakes are a virtual "sink" for RGB's! It takes
more than 50 years for water to turn over in Lake Mich-
igan; there is no fast flushing action by mighty rivers or
ocean energies to mitigate the lakes' absorbance of toxi-
cants. Moreover, with more than one-third of the United
States population and an even greater proportion of the
Canadian population living near the lake shores, tons
upon tons of PCB-infested materials are daily deposited
into the Great Lakes receptacle. Transformer fluids, plas-
tic bottles, hydraulic fluids, carbonless paper, ink, and
other RGB-loaded wastes all find their way into the
lakes, where the percentages of RGB's amalgamate mal-
ignantly. As soon as the food chain absorbs these wastes,
the poison is off and running.
The tiny invertebrate fingernail clam'has demon-
strated an inordinate capacity to concentrate poisonous
RGB residues and pesticides and heavy metals, which
may ultimately spell the extinction of one of America's
favorite waterfowl, the canvasback, which feeds vora-
ciously on the clam. The clam was once common in the
Detroit River and Lake Si. Glair, habitats that used to
attract major flights of canvasbacks.
The dieoff of fingernail clams on the Illinois River
in 1956 spelled the end! of that favorite spot for the
canvasback. The canvasback represents a valuable water-
fowl resource struggling against many odds as a declining
species, but I foresee little succor for a population which
winters and breeds in areas heavily infested with RGB's.
No dollar values can be assigned to endangered
species, and even our society of technological whizzes
cannot rejuvenate a species when its sole environmental
niche is so totally contaminated with toxicants. The
complete disappearance of Atlantic salmon from Lake
Ontario during the early part of this century and blue
pike from Lake Erie in the early 1960's have served as
classic examples of man's impact on Great Lakes fishes
and their environment. Currently we appear to be losing
certain species, such as cisco and chubs, that are native
inhabitants of the deepwater portions of Lakes Superior,
Michigan, and Huron. Even restoration of self-sustaining
populations of lake trout is in doubt in Lake Michigan
because of an apparent lack of natural reproduction in
the lake.
Possible reasons for these species' decline are num-
erous and complex. Although we have yet to pinpoint
the interaction of dynamic ingredients, our scientists are
certain that toxic substances such as RGB's are playing
an important role. The potential effects of RGB residues
in excess of 20 ppm in adult, spawning lake trout cannot
be ignored.
I think I have gone far enough in detailing the prob-
lems that we face with this contaminant in the protec-
tion and management of Great Lakes fishery resources.
The potential impact oi RGB's on the future manage-
ment of the lakes' multimillion dollar sport and com-
mercial fisheries is tremendous, especially if the FDA
lowers its guidelines, or if average RGB concentrations in
fish increase.
Past attempts to control point sources of RGB's into
the environment have failed to bring about any measur-
able reduction in the contamination of Great Lakes
fishes. DDT levels in Lake Michigan fishes and mercury
levels in Lake St. Glair fishes, however, have declined
from between 50 and 87 percent in the past 4 to 5 years
as a result of controls on their use. Why haven't RGB
436
-------
levels responded similarly? Do they behave so differently
from DDT and mercury in the environment that we can-
not reasonably expect to have observed some decline by
this time? We will never know unless the flow of RGB's
to the environment is stopped. I remind you that it was
commonly thought that decades might elapse before
DDT and mercury would decline to satisfactory levels in
the great Lakes. It appears highly probable that the pri-
mary cause for the failure of PCB's to decline in Lake
Michigan fish is that their sources have not been cur-
tailed to any significant degree.
To sum up, the insidious character of PCB's is now
self-evident and presents a very serious problem to all of
us. These pollutants affect the very core of State and
Federal fisheries restoration programs throughout the
United States. Here in the Great Lakes, PCB's have the
potential of severely damaging multimillion dollar sport
and commercial fishing industries. We urgently need an
effective program of control capable of rapidly eliminat-
ing the release of PCB's into the Great Lakes and our
other national watersheds. Because of my deep concern
with the problem, I support the recommendation of the
Lake Michigan Toxic Substances Committee for a "na-
tional ban on all domestic and imported PCB's destined
for use other than in transformers and capacitors, and
[recommend] that the critical or essential use of PCB's
in transformers and capacitors be immediately and criti-
cally reviewed in light of current potential replacement
products."
There must be at the same time an immediate and
intensive evaluation of proposed replacement products
to determine their suitability for industrial use and the
hazards associated with their potential loss to the envi-
ronment. For the immediate range, our goat must be the •
elimination of all sources of PCB's in the environment
within 3 years; for the long haul, however, we must
vigorously pursue legislation that will preclude new
"PCB's" from being discharged into the environment.
I have addressed you on my professional concerns as
they apply to fish and wildlife. Now let me speak to you
as a citizen. I have demonstrated that the Fish and Wild-
life Service's pesticide monitoring program acts as a bell-
wether for measuring the future environmental impacts
of toxic substances upon mankind. I reiterate that one-
third of the population of the United States lives within
the drainage area of the Great Lakes. The domestic
water supplies for many millions of people are drawn
from these Great Lakes—the same lakes whose fish pop-
ulations are so contaminated with chemical toxicants
that they are unfit for human consumption even under
the present, outdated FDA regulations.
We are all aware that EPA is considering the estab-
lishment of PCB limits for water quality in the vicinity
of 1 ppt (trillion), which is truly startling when we real-
ize some of the lakes may already exceed 10 ppts right
now. The passage of an effective toxic substances act
and the complete control of PCB importation are imper-
ative to the health of the American people. A piecemeal
approach to toxic substances control would only delay
and hamper our efforts to stringently regulate the occur-
rence of poisons in our environment.
Philosophically, we must consider man's role in his
environment. Thoreau urged that we "probe the earth to
see where our main roots run." The health of our fish
and wildlife acts as a pulse indicator for human health.
As this conference has shown, all medical and environ-
mental gauges indicate this pulse to be unsteady and
irregular. The irony of our position today is that our left
hand is spending millions of dollars and thousands of
man-years to establish a crucial resource while our right
hand renders each new growth of this resource malig-
nant. Our new resource will not only self-destruct but
will place the human population in mortal danger.
As a final thought, let me stress that we should
consider all alternatives. Since drastic action is needed,
we should not be afraid to step back from industrial
efficiency if we can step forward to environmental
health.
Quite frankly, I am thoroughly disgusted by the
gnashing of teeth, wailing, and rubbing of hands. To the
agencies which have the enforcement responsibilities, a
word on behalf of the bewildered but concerned Ameri-
can people-GET ON WITH IT!
437
-------
U.S. FEDERAL AGENCY ROLES AND ACTIONS:
NATIONAL INSTITUTE OF OCCUPATIONAL SAFETY AND HEALTH
Richard A. Rhoden, Ph.D.*
Abstract
NIOSH activities regarding PCB'shave included: (1)
the issuance of a background information document on
PCB's for the occupational health community; (2) the
decision to develop recommended workplace standards
to be forwarded to the Department of Labor; and (3)
plans for conducting retrospective mortality studies of
workplaces where PCB's are processed. NIOSH is
equipped to perform onsite retrospective mortality
studies of workplaces, but as yet no facilities handling
PCB's have requested an analysis.
To date NIOSH activity in regard to PCB's has
consisted of three undertakings. On the 3rd of this
month, our Office of Occupational Health Surveillance
and Biometrics issued a PCB background information
document. Its purpose was to inform the occupational
health community of current knowledge concerning
industrial uses and the toxicity of PCB's. I have a few
copies of that document with me and others may be
obtained by writing to our Rockville, Maryland, offices.
(I might add right here that NIOSH would welcome any
technical input from members of the audience with
regard to case studies, hygiene surveys, workplace levels,
and so forth.)
In a second action of NIOSH, it has been decided
that criteria for our recommended workplace standards
will be developed and forwarded to the Department of
Labor Occupational Safety and Health Administration
with formal development efforts to commence in March
of next year. This will be an in-house effort, in contrast
to the case with many of our criteria development
efforts. It is anticipated that the final finished document
will be transmitted to OSHA in late 1976 or early 1977.
The Center for Disease Control has kindly made Dr.
Kimbrough available to aid us in this effort.
At present, U.S. workplace standards for PCB's
consist of environmental limits, time-weighted averages
of .5 mg/m3 for Aroclor 1254 and 1 mg/m3 for Aroclor
1242, with skin notations. NIOSH is acutely aware of its
responsibility to insure that its recommended workplace
practices will not result in increased contamination of
the general environment.
'Senior Research Reviewer (Pharmacologist), Office of
Research and Standards Development, National Institute of
Occupational Safety and Health, Washington, D.C.
The NIOSH division of field studies and clinical
investigations will conduct a retrospective mortality
study of an as yet unselected workplace where PCB's are
processed or handled. A cross sectional medical surveil-
lance of current workers at that facility is a possibility.
Such surveillance would be conducted by the medical
investigations branch of that division.
To our knowledge, no such studies have yet been
undertaken. A complete industrial hygiene survey will
also be conducted at the selected facility, including
personal air sampling, and checks of breathing zones of
workers, housekeeping, and other work practice
monitoring. The environmental investigations branch
will conduct the personal hygiene survey.
The mortality study to which I referred will be
conducted by the biometry branch. Mr. David Brown, an
epidemiologist with that branch, is here and is ready and
willing to discuss the protocol with interested people.
The mortality study will consist of first, cohort selec-
tion—that is, determination that the selected facility has
existed for at least 25 to 30 years so that sufficient time
has elapsed for cancer induction and so forth. Next is
cohort size determination; the cohort must be large
enough to insure detection of low-incidence events. And
there will be a personnel record evaluation; the person-
nel records must be comprehensive enough to permit
followup and determination of employee work history.
Once a facility is selected for study, personnel
records will be microlilmed and encoded into a data
bank. The followup to determine the vital status of the
cohort is then undertaken. That is, cause of death and so
forth and the findings are analyzed using modified life
tables in order to determine any excess mortalities and
the specifics thereof.
Attempts are then made to correlate the mortality
experience with workplace exposure levels, as ascer-
tained from work history data. Section 20A7B of the
Occupational Safety and Health Act of 1970 authorizes
the Department of Health, Education, and Welfare to
make inspections and question employers and employees
as provided in section 8 of the act in order to carry out
its functions and responsibilities.
The field investigations are conducted hopefully in
the spirit of government, management, and labor cooper-
ation. Section 20A6 of the Occupational Safety and
Health Act of 1970 charges the Department of Health,
Education, and Welfare with the responsibility for
evaluating the potential toxicity of the materials used or
438
-------
found in the workplace. That is upon receipt of written been received to date from any facility that can be
request by employers and employee representatives. identified as a PCB facility. I have a few health hazard
NIOSH is the agency which provides these onsite evaluation forms with me and I also have a few NIOSH
toxicity determinations. I found upon checking with the mailing list forms and with that I'll close. Thank you.
responsible NIOSH division that no such requests have
439
-------
PROPOSED CANADIAN REGULATORY
MEASURES FOR PCB'S
Maurice F. Millson, Ph.D.*
Abstract
A systematic approach to the development of regu-
lations intended to reduce environmental levels of PCB's
involves three aspects: the nature of the problem, the
ways of reducing the severity of the problem, and the
recognition of those ways in formulating the regulations.
Six regulatory packages are outlined. The Canadian legis-
lative base on which to impose these packages is indi-
cated, along with preparatory steps underway in antici-
pation of the coming into force of the Environmental
Contaminants Act.
The contrast between the purposes for which DDT
and PCB's have been used leads to the conclusion that
presently measured PCB residue levels in the environ-
ment should not be expected to decrease, in response to
Monsanto's imposed decrease in usage, at a rate compar-
able to that at which DDT residues have decreased.
The title given in the program is a bit optimistic. It
sounds as if we made up our minds to pass information
out, whereas in fact we are here to gather evidence in
order to decide exactly what regulations we need. I shall
deal only with an approach to regulations intended to
affect the situation in the open environment, not regula-
tions of food or other direct threats to humans. In this
presentation I plan to follow a systematic objective
approach to development of regulations, and it involves
three aspects: the nature of the problem, the ways of
reducing the severity of the problem, and how to recog-
nize those ways in formulating practical regulations.
From the regulatory point of view, the -nature of the
problem is that there are dangers posed to living things
by the presence of PCB's in their environment and levels
do not seem to be decreasing. The dangers are a combi-
nation of the inherent toxicity of various PCB's and the
exposure of susceptible species to those PCB's. Since we
cannot change the toxicity of the types of PCB's, we can
reduce the severity of the problem only by reducing the
exposure.
Exposure incurred by PCB's in the environment is a
little different from normal exposure. I think Dr.
Kimbrough touched on this. For humans, one talks of
exposure in terms of intake, whereas in the environment
we normally talk in terms of the residues of PCB's in an
organism or in a sediment. And it is those residues that
* Environmental Assessment Coordinator, Environmental
Contaminants Control Branch, Ottawa, Canada.
we need to reduce as far as the environment itself is
concerned. As a consequence, that would affect the
intake of humans. We can reduce the residue levels by
restricting the permitted range of uses of PCB's, by re-
stricting losses of PCB's into the environment from any
permitted uses, or by restricting the proportion of per-
sistent homologs in the PCB's that get into the environ-
ment.
This brings us to the third aspect: how to recognize,
it in the formulation of alternate regulations, the three
ways of reducing the residue levels. I have put together
six alternative regulatory packages of increasing severity
with regard to those three ways.
The first package prohibits all uses other than in
transformers and capacitors, and couples that with con-
trols on disposal of industrial sizes of capacitors and
transformers, the PCEI's in them, and manufacturing
wastes in making them.
The second package prohibits all uses other than
transformers and capacitors. It puts a restriction on the
higher chlorinated PCB's, meaning more than four chlo-
rines, in capacitors and puts controls on disposal of
industrial material.
The third package prohibits all uses other than
transformers and capacitors. It restricts higher chlori-
nated PCB's in any capacitors, with an additional restric-
tion on the medium chlorinated PCB's (more than three
chlorines) in small capacitors because of their disposal.
There are controls on disposal of industrial materials,
recognizing that small capacitors are inherently unregu-
latable as far as disposal is concerned.
The fourth package prohibits all uses other than
transformers and large capacitors, with a restriction on
the higher chlorinated PCB's (more than four chlorines)
in the capacitors, and has the disposal controls. This
package would remove PCB's from small disposable
capacitors.
The fifth package prohibits all uses other than for
transformers and capacitors, and places a restriction on
any PCB's with more than four chlorines. That would
wipe out Aroclor 1254. It would probably not entirely
wipe out the use in transformers; I think Westinghouse
has always used a brand of 1242 for certain trans-
formers.
The sixth package is total prohibition of PCB's. To
any of those six there could be slight modifications. We
might have to permit the use of PCB's in research; if
we're going to allow them at all then we should allow
440
-------
their use in research, otherwise we'll never know
any more about them.
We could permit their use as a chemical inter-
mediate. Somebody may have reason to use 4,4'-dichlo-
robiphenyl for conversion to something else. And with
sufficient restrictions on the conversion efficiencies and
the disposal of waste, it might be possible to allow them
to do that. We could add an fxtra restriction on the
concentration of the chlorinated dibenzofuran in any
fluid in which it appears to be a problem or in any fluid
in which it's possible to remove it or prevent it from
being there in the first place.
We are currently involved in examining the evidence
on which to decide what package of regulations should
be recommended to those who make the final decision.
How we could legally impose the chosen set? We have
the traditional fields of pollution control: waste water,
air pollution, solid waste disposal, and just as in the
United States, in Canada there is much legislation. We
have 10 provinces, all with different laws and regula-
tions. We have the Federal Government. Between them
they could cover the whole range if everyone used its
authority to pass, impose, and enforce the laws that are
available.
It is generally recognized, as you already heard from
EPA's point of view, that those sort of laws are not
adequate for the proper control of RGB's. That does not
mean they are not useful in conjunction with other legis-
lation on products.
Canada almost has a law on products—the proposed
Environmental Contaminants Act. It is Bill C25 at the
moment and whenever a civil servant speaks of a bill he
has to be careful to say he means the proposed act,
because if one talks of the act, the legislature gets rather
upset that you are taking it for granted. The reason that
Jim Brydon is not here today is that yesterday he had to
appear at a Senate committee hearing, and my under-
standing from phoning back this morning is that the
committee passed the bill. Now whether it passed it with
one amendment I am not sure. It passed the bill, which
means it will go to third reading in the Senate next
Tuesday, and then al! it requires is the signature of, or
Royal Assent from, the Governor General or whoever is
acting for him. At that point it is on the statutes books
but not-in force, it comes into force on a date to be
fixed by proclamation. When that will be I do not know.
Various people are pressing for an early proclamation;
certain others feel you need time to get organized before
you proclaim the act, otherwise you can get into serious
problems with handling paper.
In addition to that possibility of controlling prod-
ucts, the provinces have constitutional power, if they
care to use it, to pass laws to control in detail all indus-
trial activities within their boundaries. They can tell
industry it must do this and it may not do that. They
can control them in detail. They recognize that the regu-
lation of products is better done at the national level in
order to avoid fragmenting the markets and ending up
with 10 different classes of laws. The Contaminants Act
implicitly recognizes provincial power and requires the
Federal Government to consult the provincial govern-
ments before putting in any regulations, in fact, before
publishing the proposed regulations. The consultation is
to determine whether any particular province prefers to
deal with the problem itself. I do not imagine that any
province would want that option for RGB's, or else they
would have handled it already.
How to apply the new act when it becomes available
to the six packages? It cORtains an information gathering
power, which gives us the right to demand all kinds of
information if there is reason to believe a significant
danger exists. Those involved with a nominated sub-
stance must identify themselves, and on request must
identify what their involvement is.
The act contains three powers of prohibition.
Because of the nature of its constitution base, it may
only prohibit. It may not regulate in a management
sense merely because we feel it better that way.
The activities that can be prohibited are those liable
to injure health or the environment. With respect to
something such as RGB's, this could involve prohibition
of willful release into the environment and prohibition
of import, manufacture, processing, sale, or use for pre-
scribed uses. Another prohibition is that on incorpora-
tion of a substance into a product beyond a certain
specified concentration or proportion.
I should point out the possible strange regulations
on proportions of chlorine in RGB's. If we wish to regu-
late them, it would not be by naming allowable propor-
tions of specified substances by product, but by naming
classes of substances and prohibiting them for certain
uses. We can name substances or classes of substances
with some limitation on the type of class. These classifi-
cations are nowhere near as broad as some of those in
the draft U.S. toxic substances bills.
If we combine the three powers of prohibition in
the new act with the conventional pollution control
powers of the federal and provincial governments, you
can see that we could put in any of those six packages
on RGB's. In regard to what we actually intend to do,
there is no secret that the earliest regulation that would
be put forward would be very simply a restriction to no
RGB use other than for transformers and capacitors, with
the possible exception of research and maybe chemical
intermediates.
In effect that would initially confirm Monsanto's
441
-------
1971 curtailment of sales. And it would not disrupt the
market for electrical uses at the moment. It would dis-
rupt whatever other markets there are that we do not
have a handle on. We know some people are using RGB's.
We don't know where they got them from. We have
suspicions about who might be using them. Our informa-
tion gathering power could be used, when in force, to
find out who is using them. To go beyond the curtail-
ment to transformers and capacitors, I cannot tell you
what we shall do because we have not made up our
minds. We would have to consult other government
agencies or the Federal agencies. We would certainly
have to discuss the action with electrical equipment
manufacturers as to timing if or when we go beyond that
one step.
To go to regulations on composition of fluids by
prohibiting higher chlorinated PCB's, and certain chlo-
rinated dibenzofurans, we would have to be able to
specify analytical procedures. The procedure would have
to be developed and would have to stand up to interna-
tional comparisons; you do not do that overnight.
People do not agree, for good scientific reasons, particu-
larly on the chlorinated dibenzofurans as to exactly
what are you measuring when you go through different
procedures.
We have put together a good deal of information on
the situation in Canada because we would have to be
prepared to state the basis for a regulation. By we I
mean a task force from the National Health & Welfare
and Environment Departments, and the environment,
health, and agriculture ministries of the province of
Ontario. (Ontario controls the whole northern shore of
the Great Lakes other than Michigan.) Several members
of the task force are at this meeting; when we get back
we shall debate our impressions of the data reported
here, the opinions reported here, what we already know.
We were not all of the same opinion the last time we met
as to exactly what the evidence justified. We came here
with open minds, but I doubt whether we shall reas-
semble all with one opinion. We shall be better in-
formed, maybe a bit wiser, and a bit more scared about
difficulties.
I cannot describe the Contaminants Act to you in a
few minutes. It does require publication of any proposed
restriction after it's been discussed with the provinces
and before it comes into force. It provides for the crea-
tion of a board of review if a notice of objection is
lodged. For this reason we would have to be prepared to
submit to a board the evidence on which we claim to
have become satisfied that the substance constitutes a
significant danger to health or the environment. That is
the basis of the act—the Governor-in-Council, meaning
the Federal cabinet, has to be satisfied that a significant
danger exists. This means that we would have to con-
vince other departments whose interests are in promot-
ing economic development and so on, that the danger is
enough that the Federal Government as a whole should
become involved. That would prevent arbitrary and
capricious decisions.
We have come here partly to find evidence on the
more perplexing points, in particular, the degree of per-
sistence in the environment of the different PCB's. When
they appear, one does not know for sure whether it is
because they just came into that location or because
they are persistent, or even which ones do persist.
On a personal level, everyone is worried that the
Monsanto restrictions of 1973, '71, and '72 have not
caused a significant decrease of levels of PCB's; that is,
there has been no significant decrease in the levels of the
persistent PCB's-1254,1260.
I do not expect to see the persistent PCB's decrease
in the 1970's in the biological accumulators, the fish and
birds, and in sediments, which are nonbiological accumu-
lators. If you look back to DDT, use dropped off from
about 1963 around the Great Lakes and more or less
ceased about 1968, '69, and '70. Five years later, after
argument, people accepted the fact that DDT and DDE
were, decreasing.
All the DDT ever manufactured was intended to be
spread into the environment within 1 to 2 years of its
manufacture. Five years after stopping its production
and use, a decrease in the environmental level has been
shown. Almost all the PCB's ever made were intended to
be kept somewhere because they were long-life products,
and so they have not yet reached the open environment,
let alone begun to show decreasing levels. One member
of our task force, as a matter of fact, happens to analyze
from time to time his invoices, and the carbonless copy
paper invoice is still in use. It has not been manufactured
for 3 years. So not only has it not yet appeared to go
out of company files into the disposal system; it is not
yet even in the company files—it is in the stock of un-
used paper.
What I do expect to decrease, if only we had the
evidence, are the so-called less persistent PCB's—the
1242's or call them what you will. No one seems to have
evidence or data on 1242 types in biota or sediments
going back 5 years. Most people do not have any evi-
dence f.or it at all, because either it is not there or they
have not looked or the system cannot pick it up. There
is some hope that one group in the Wildlife Service may
be able to go back to some of its samples and determine
the trichloro, tetrachloro levels over the last 3 years, and
certainly over the next 3 years it can obtain samples and
follow the trend if it exists. If that one does not decrease
by 1980 or before, we have a bigger problem than any-
body thinks.
442
-------
RGB's IN FOODS: A LOOK AT FEDERAL
GOVERNMENT RESPONSIBILITIES
Joseph Highland, Ph.D.*
Abstract
Our growing concern over the continued contamina-
tion of food supplies by poly chlorinated biphenyls
(PCB's) reflects an ever increasing knowledge of the ex-
treme health hazards posed by these compounds. PCB's
are both subacutely and chronically toxic, and have
recently been shown to cause severe chronic effects at
dietary intakes as low as 2.5ppm in nonhuman primates
(refs. 1-4). To date, a no-effect level for PCB's in non-
human primates has not been established.
Federal sampling and surveillance programs have
continually demonstrated the presence of PCB's in our
food supply. Not only have the existing temporary toler-
ances for PCB's established by the FDA been insufficient
to protect the public health, but recent evidence also
indicates they must now be considered both obsolete
and inappropriate. A new regulatory posture is needed
which takes into account recent evidence of chronic
effects caused by low level dietary intakes of PCB's and,
more importantly, new evidence (ref. 5) substantiating
the carcinogen/city of these compounds.
Such a regulator/ approach is mandated by the
FDA's responsibilities under the Food, Drug, and Cos-
metic Act. It must involve the establishment of a zero
tolerance level for PCB's in food to be achieved by
means of a phased reduction to zero (using appropriately
set temporary tolerances} determined by the levels of
PCB's presently found in the environment. Such tempo-
rary tolerances must be sufficient to minimize the risks
to public health and must be based on a level of risk
which has been assessed using appropriate statistical
models to account for the potential carcinogenic risk
posed by any given residue level.
Appropriate regulatory action is long overdue. PCB
contamination of food clearly poses a potential health
hazard. The longer action is delayed, the longer society
will involuntarily be required to endure such health
hazards.
THE NEED TO REGULATE
The need to regulate the levels of PCB's in the food
supply is brought about by our knowledge of the health
hazards posed by the ingestion of these compounds.
Are PCB's Toxic?
PCB's are considered to have a low acute toxictty
(ref. 6). In adult rats, the oral LDSo ranges from 4-10 g
per kg body weight. In weaning rats, an oral LD5 0 for
Aroclorf 1254 of 1,295 mg per kg body weight and
1,315 mg per kg for Aroclor 1269 have been reported
(ref. 7). However, a low acute toxicity does not mean
the absence of health hazards. On the contrary, PCB's
are subacutely and chronically toxic at relatively low
dose levels (ref. 8).
The chemical nature of PCB's in part may help
explain why they are subacutely and chronically toxic
rather than being acutely toxic. They have a low solubili-
ty in water but are highly soluble in fat (ref. 9). There-
fore, they tend to accumulate and concentrate in the
body's fat stores rather than being rapidly metabolized
and excreted. It appears that the metabolism and excre-
tion of PCB's, especially of those Aroclors with high
chlorine content, are even slower than for some of the
most persistent pesticides, such as dieldrin and DDT (ref.
6). Thus, after ingestion, PCB's persist in the body for
long periods of time and thereby may elicit chronic
effects.
- Bioaccumulation of PCB's in Tissue
From both animal and human data we know that
PCB's accumulate in adipose tissue. Animals continuous-
ly fed PCB's show a steady buildup of these compounds
in their tissues; to date, no known upper limit for PCB
storage has been found. Steady-state levels of dietary
PCB's were reported for certain but not all tissues in rats
fed 100 ppm Aroclors 1248, 1254, and 1262 for approx-
imately 10 months (ref. 8). Once these levels were
reached, they appeared to remain relatively stable for a
long while even after dietary exposure to PCB's ceased.
Rats fed PCB's for 58 days showed levels in their adipose
tissue 5 times greater than their daily dietary intake (ref.
10). When the dietary exposure was for 240 days rather
than 58 days, levels of 10 times dietary intake were
noted. If PCB feeding was curtailed after 58 days and
the levels in tissue measured after 71 days on a PCB-free
diet, adipose tissue still showed 80 percent of the highest
*Director of the Toxic Chemicals Program, Environmental
Defense Fund, Washington, D.C.
tThe term Aroclor is Monsanto's trade name for the PCB's
it produces. Monsanto is the sole U.S. producer of PCB's. The
last two digits of the four-digit number indicate the percent
chlorination of the product (e.g., Aroclor 1260 contains 60%
chlorination). Other trade names for PCB's manufactured
outside the United States include: Kanaclor (Japan), and
Clophen, Flenclor, Phenoclor, and Sorol (Europe).
443
-------
level previously measured while the levels in the brain
showed no decrease but remained relatively constant.
As noted above, significant levels of PCB's have
been found in the adipose tissues of humans as well. It is
estimated that levels of 1 ppm PCB or more exist in 30
to 45 percent of the general U.S. population (refs.
11,12). In a few cases, levels as high as 200 and 600 ppm
have been reported. Moreover, as the PCB's continue to
be consumed, the composition of the residues stored in
the body no longer directly reflect what has been in-
gested (refs. 10,13-15). This is due to differences in the
body's retention of various PCB homologs. The more
highly chlorinated homologs, which tend to be more
chronically toxic, are retained longer. Therefore, the
toxicity of the PCB's stored in tissues may actually in-
crease and the mobiiization and metabolism of a given
amount of stored PCB can produce a more severe toxic
effect than the ingestion of an equivalent amount (by
weight) of a commercially produced PCB mixture.
Toxicity of PCB Metabolites
It is not only the direct toxic effects of PCB's with
which we must be concerned, but also the effects of
their metabolites as well. Many times metabolites are
more toxic than the parent compound. In fact, in the
case of the PCB metabolite 5-hydroxy-2,4,3',4'-tetra-
chlorobiphenyl, this has been shown to be the case (ref.
8).
The nature of PCB metabolites not only warns us of
possible increased toxicological risks, but also of the
types of toxicological responses that may be expected.
The metabolism of PCB's by monkeys (primates tike
man) occurs by way of the formation of an epoxide
intermediate (ref. 16). Aromatic hydrocarbons such as
PCB's, metabolized via this intermediate, often produce
cancer, birth defects, mutation, and cell death in experi-
mental animals (ref. 17).
The Toxicity of PCB's in Humans
In response to PCB poisoning several adverse effects
have also been observed in man. In 1968 over 1,000
Japanese experienced PCB poisoning after consuming
rice oil contaminated with Kanechlor 400 (refs. 18,19).
In addition to causing headaches, swelling of eyelids,
temporary loss of vision, and many other symptoms,
PCB's stored in the adipose tissue of pregnant women
were passed through the placental wall and into their
fetuses. As a result, 9 of the 10 live-born babies had
unusually greyish, darkened skin, and most were born
underweight. The importance of these observations can-
not be underestimated, especially in light of very recent
findings reported by Allen and coworkers on the effects
of low-level exposure of nonhuman primates to PCB's
(refs. 1-4). The effects seen in these monkey studies are
similar in appearance and persistence to the symptoms
of the human poisoning already discussed. Moreover,
these symptoms were documented at levels of dietary
intake of as low as 2.5 ppm. To date, a no-effect level for
PCB's in monkeys has not been established.
Carcinogen/city of PCB's
Although carcinogenicity in primates in response to
the dietary intake of PCB's has not yet been observed, it
has been reported for both mice and rats"(refs. 5,8). The
World Health Organization has reported that Kanechlor
500 and Aroclor 1254 are carcinogenic in mice and in-
duce both benign and malignant liver cell tumors follow-
ing oral ingestion. Most recently, a team of research in-
vestigators from the Center for Disease Control, Atlanta,
Georgia, the U.S. Environmental Protection Agency, the
National Cancer Institute and Johns Hopkins University
School of Medicine reported that 26 of 184 experimen-
tal animals (rats) fed 100 ppm of Aroclor 1260 for
approximately 21 months developed hepatocellular
carcinomas. Only 1 out of 173 control animals devel-
oped this lesion in the same period of time. Moreover,
146 of the experimental animals but none of the con-
trols had tumorous lesions (neoplastic nodules) of the
liver.
Appropriate regulatory action with regard to the
presence of PCB's in food must take into account the
following factors among others: the bioconcentration of
these compounds in human tissues; the selective nature
of this process which can lead to more severe toxic
effects than those expected from the ingestion of the
original PCB mixtures; the toxicity of the PCB metabo-
lites; the severe chronic effects observed in nonhuman
primates from dietary ingestion of low levels of PCB's;
and the demonstrated carcinogenicity of PCB's in two
animal species.
PCB's IN FOOD
The first evidence that food supplies had become
contaminated with PCB's was reported in 1966, when fish
from various Swedish waters were shown to contain
PCB's (ref. 20). Since then, PCB's have been identified as
contaminants in food supplies around the world. They
have been found in pike taken from a lake in Finland,
mollusks and marine fish from Scottish waters, a wide
variety of fish caught in the St. John River system, wild-
life in California, and in trout and salmon taken from
Lake Michigan (refs. 8,21). More recent findings indicate
that contamination by PCB's continues to be wide-
spread. Within the last few months, striped bass caught
in the Hudson River have been found to contain as much
as 90 ppm PCB's, while pike caught in the Baltic Sea
were shown to contain 0.31 ppm PCB in their muscle
444
-------
and up to 190 ppm in their ovaries (refs. 22,23). More-
over, plankton from the Baltic Sea, upon which many
fish feed, contained levels of 25 ppm PCB in their fat
(ref. 24).
Federal Sampling and Surveillance Programs for Chemi-
cal Residues in Food
The Federal government currently conducts three
separate programs in which the contamination of foods
by PCB's is measured. These programs include: the FDA
Pesticide Surveillance Program, the FDA Total Diet Pro-
gram, and the USDA Surveillance Program.
The FDA Pesticide Surveillance Program, which
began in 1968, was developed to gather information on
the levels of pesticides (including PCB's) in foods and
animal feeds based on a statistical sampling program
designed to cover specific geographical regions of the
United States. The program is intended to assure the
safety of the human food supply by screening and
removing shipments of foods containing PCB's or pesti-
cides in excess of established tolerances. Commodities
covered under this testing program include dairy prod-
ucts, eggs, fish, animal feeds, fruits, vegetables, and
processed foods.
In the FDA Total Diet Program, the levels of pesti-
cides, PCB's, and trace heavy metals in the diet are meas-
ured. Bimonthly, a diet approximating that which would
be consumed in a 2-week period by a hypothetical 15- to
20-year-old male is collected at retail stores in five
regions around the United States. The foods are cooked
or prepared in the appropriate manner and then divided
into 12 basic food composite classes. These include
meat, fish, poultry, leafy vegetables, etc. Each composite
is then analyzed for contaminants.
The USDA Surveillance Program consists of periodic
sampling and analysis of meats and poultry from chemi-
cal contaminants including PCB's. Samples are taken
from federally inspected slaughterhouses.
The Levels of PCB's Found in Food
A summary of the findings, with respect to PCB's,
of the survey and surveillance programs described above
are listed in tables 1 through 3. It represents a compila-
tion of data gathered from Federal sources (refs.
8,20,25).
Although the data are incomplete, it is clear that
PCB's continue to contaminate our food. Results of the
pesticide surveillance program appear to indicate an in-
crease in the extent of contamination, while those of the
USDA surveillance program indicate a decrease. This
apparent conflict may be explained by the fact that dif-
ferent foods are sampled in these programs and it is
quite possible that contamination of some foods has de-
creased while increasing for others.
The apparent decrease in the levels of PCB's report-
ed in the FDA total diet survey between FY 73 and the
first half of FY 74 must be viewed with caution. During
the first half of FY 74, the average PCB levels for milk
and other dairy products, for eggs and egg products, and
for animal feed ingredients were equal to or greater than
those reported for FY 73. Then why the apparent de-
crease? In large part this reflects an apparent decrease in
the numbers of fish that were found to be contaminated
with PCB's. In FY 73, 62.2 percent of the fish samples
examined contained PCB's in the range of trace amounts
to 123 ppm. In the first half of FY 74 only 35.3 percent
of the samples checked were contaminated and the levels
found ranged from trace amounts to 9.70 ppm. How-
ever, the fish data reported for FY 73 included mostly
freshwater fish, where the contamination with PCB's has
been shown to be the greatest, while during the first half
of FY 74 the FDA samples consisted mainly of marine
fish. Since the samples are not comparable, the apparent
decrease observed is more probably a reflection of the
difference between PCB contamination of freshwater
and marine fish than an indication of a decline in PCB's
in fish generally.
In addition to these observations, numerous specific
incidents of PCB contamination of food have been re-
ported by the FDA and USDA. A summary of these has
been compiled by Wessel (ref. 20). A few examples fol-
low. In 1970, the Campbell Soup Company detected
high levels of PCB's (26.8 ppm on a fat basis) in chickens
grown in New York State. As a result, 140,450 chickens
were destroyed. In July of 1971 Monsanto Chemical
Company'informed the Food and Drug Administration
that large amounts of fish meal might have been contam-
inated with PCB's during pasteurization from a leak in
the heating system at their East Coast Terminal in
Wilmington, North Carolina. An investigation by the
FDA revealed that the leak had begun in April of 1971
and had continued through July 1971. Contamination of
the fish meal was verified, and as a result, over 123,000
pounds of egg products and 88,000 chickens were de-
stroyed. That same year, the FDA was notified that high
levels of PCB's (20 ppm) had been found in Swift and
Company turkeys. As a result, approximately 1 million
birds were kept from market. These incidents and the
results of the Federal surveillance programs demonstrate
that the contamination of food by PCB's is not a new
phenomenon. It is a continuing problem, which has
resulted in part from the continued indiscriminate dis-
charge of PCB's into the environment, and one which
445
-------
Table 1. FDA total diet survey
Number of composite
Year food samples Percent contaminated
68-71 900 6%
FY 73 360 6%
FY 74 360 4%
"Levels of
contamination
trace--0.36 ppm
trace--6.0 ppm
trace--0.05 ppm
Table 2. FDA pesticide surveillance program
Year Number of samples Percent contaminated
68-71 15,000 3.2%
FY 73 7,882 4.0%
FY 74 1,723 5.4%
Levels of
contamination
"detectable"
(fish, speci-
fically: 1-10 ppm)
"detectable"
"detectable"
Table 3. USDA surveillance program
Year Number of samples Percent contaminated
71 4,175 4%
FY 73
(poultry only) 1,037 2.6%
FY 74
(poultry only) 574 <1%
Levels of
contamination
trace--15 ppm
trace--4 ppm
1 ;25 ppm
446
-------
must be eliminated because of the severe health hazards
posed by these compounds.
THE ESTABLISHMENT OF TOLERANCES
Existing Tolerances
In partial recognition of the health hazards posed by
PCB's, the FDA proposed the following temporary toler-
ances (in ppm) for the levels of PCB's which would be
permitted to contaminate food:
1. Milk (fat basis) 2.5
2. Dairy products (fat basis) 2.5
3. Poultry (fat basis) 5.0
4. Eggs 0.5
5. Complete and finished animal feeds 0.2
6. Animal feed components 2.0
7. Fish and shellfish (edible portion) 5.0
8. Infant and junior food 0.2
9. Paper food-packaging material 10.0
The FDA contends that these tolerances are sufficient to
protect the public health. However, careful considera-
tion of the available evidence indicates clearly that this
conclusion is unwarranted and unsupported by the facts.
The Toxicological Basis for Calculation of The "Accept-
able Dietary Intake" of PCB's
The FDA has calculated what is termed an "accept-
able daily dietary intake" for PCB's. Even if the validity
of such a concept is assumed, the basis for establishing
such a level must be evaluated in order to determine
whether the temporary tolerances that have been pro-
mulgated sufficiently limit PCB intake. In this connec-
tion the FDA's final environmental impact statement for
rulemakingon PCB's (ref. 26) indicated that both animal
and human toxicological data were used to establish an
allowable dietary intake.
According to data avilable at that time, long-term
animal studies showed no-effect levels in dogs and rats of
10 ppm for Aroclors 1242, 1254, and 1260. Employing
the standard 100-to-1 safety factor, a no-effect level for
man based on data derived from dogs was calculated to
be 2.5 Aig/kg body weight/day. From the data on rats, a
3 jug per kg body weight figure was obtained. Therefore,
the allowable level of PCB ingestion in man was figured
to be 0.175 mg per day for a 70-kg individual. However,
according to Dr. H. Blumenthal, Acting Director, Divi-
sion of Toxicology, Bureau of Foods, FDA (ref. 8), in
the time since these calculations were made, there have
been two important observations concerning PCB's
which alter our understanding. These observations make
the allowable daily intake previously calculated obsolete.
First, the recent studies cited earlier in this paper
dealing with experiments on nonhuman primates were
reported, indicating that the rat and dog are relatively
insensitive to many of the toxic effects of PCB's. As
stated previously, a no-effect level for PCB's has not yet
been determined for monkeys. Second, recent work by
Allen (ref. 1) indicates that the use of gross observations
of toxicity are not reliable in the study of PCB's. Allen
observed that routine toxicological evaluations of rats
fed 100 ppm Aroclor 1248 for 1 year revealed no abnor-
malities in growth, mortality, and hematology. However,
more sophisticated tests showed that these rates had
drastically altered fat and cholesterol metabolism as well
as changes in liver size and structure. Therefore, even if
one were willing to accept an allowable human daily
dose for PCB's calculated from animal toxicological
data, one would have to question seriously the basis for
the FDA's 1972 calculations.
The human toxicological data used to determine the
allowable daily dose came from the accident at Yusho
described earlier in this paper. The reasoning put forth
by the FDA (ref. 26) was as follows:
Since 2,000 mg was reported to be the average
total dose causing an effect in the Japanese, it
is possible that 200 mg total dosage PCBs
(applying a safety factor of 10 to 1 as above)
may be tolerated over a much more protracted
period of time without overt adverse effect if
daily exposure is held to minimal levels. This
would permit ingestion of 4 M9 per kg body
weight per day in a 70-kg man. Since the low-
est total dose producing an effect in man in
the Japanese incident was 500 mg, a similar
analysis leads to an allowable protracted inges-
tion of 1 //g per kg body weight per day as
derived from a 70-kg man.
On the basis of these data, the FDA arrived at an allow-
able dose of PCB's (for a 70-kg man) of between 70-280
/ig/day, although the significance of these calculations is
very questionable. Particularly suspect are the estimates
that had to be made of actual doses received by
the Japanese, as well as the arbitrary assumption that a
safety factor of 10-to-1 is sufficient to determine a safe
level of intake for a "protracted period of time." In
addition, the calculations fail to consider the potential
long-term effects caused by stored PCB residues. Recent
evidence from controlled feeding experiments of non-
human primates which demonstrated severe chronic
effects from low-level intakes of PCB's raises the ques-
tion of whether similar effects might also be seen in man
under the appropriate conditions.
The "Acceptable Daily Dietary Intake" Can Readily Be
Exceeded
The FDA's acceptable daily PCB intake of 75-210
jug/day for a 70-kg man seems questionable at best. As
447
-------
Dr. J. Wessel, Scientific Coordinator, FDA, has pointed
out (ref. 20), "it is quite clear that the acceptable daily
PCB intake of 75-210 Aig/day could easily be exceeded
by an adult consuming some of the heavily contamin-
ated foods in his diet." Table 4 below, taken directly
from the testimony of Dr. Wessel (ref. 20), illustrates
this point clearly.
As Dr. Wessel concludes, "Even when PCBs are pres-
ent at the tolerance level, it would be possible for an
adult, with normal dietary habits, to exceed 175^9 of
PCB per day." Adults with "normal dietary habits" are
not the only people unprotected. Perhaps at even greater
risk are those large groups within the population, such as
sport fisherman or people on special diets, who consume
above-average quantities of PCB-contaminated foods, or
nursing babies who ingest PCB's in their mothers' con-
taminated milk and who, for biochemical reasons, have a
very limited capacity to metabolize foreign chemicals
such as PCB's. Dr. A. Kolbye, Jr., Associate Director for
Science, Bureau of Foods, FDA (ref. 27), and Dr. H.
Blumenthal, Acting Director, Division of Toxicology,
Bureau of Foods, FDA (ref. 8), are clearly correct when
they say respectively: "Infants or young children could
also readily exceed the tolerable daily exposure," and
"Thus, the best evidence indicates that children would
be more susceptible to the poisoning caused by un-
metabolized PCBs, since they have not developed effec-
tive ways of eliminating them from the body."
The Need for Reevaluation of PCB Tolerances Is Ap-
parent
The FDA's temporary tolerances for PCB's in food
are both inadequate and inappropriate. They fail to pro-
tect the populace even if one accepts the concept of an
acceptable daily dose, because the dose calculated in
1972 is now obsolete in light of more recent findings.
More importantly, however, the appropriateness of any
"acceptable daily dose" fot PCB's is highly questionable
Packaged
food
Table 4. Relative contribution to acceptable daily intake (175
/zg/g by foods subject to PCB temporary tolerances)
Type of
food
Milk
Cheese
Poultry
Eggs
Fish
Serving
of food
800 ml
(3.5 cups)
100 g
(3.5 oz)
200 g
(7 oz)
100 g
(2 eggs)
200 g
(7 oz)
Equivalent
Temporary amount PCB
tolerance (ppm) in food
2.5 (fat basis) 80 yg
0.1 (whole product)
2.5 (fat basis) 60 yg
0.6 (whole basis,
assuming 25% fat)
5.0 (fat basis) 100 yg
0.5 (whole basis,
assuming 10% fat)
0.5 50 yg
5.0 1000 yg
Relative
contribution
to ADI
46%
35%
58%
29%
580%
100-200 g 10 ppm
(3.5-7.0 oz) (packaging)
10-60 ygc
6-35%
Based on 1971 FDA Survey that 10 ppm PCB in packaging can result in
migration of 0.1-0.6 ppm PCB to packaged food.
448
-------
in light of the evidence demonstrating in experimental
animals the carcinogenicity of these compounds. Since
there is, at the present time, no scientific evidence that
any level of intake of a carcinogen is safe, the entire
concept of an acceptable daily dose for a carcinogen
such as PCB is self-contradictory and scientifically un-
supportable. A new regulatory posture is therefore
needed.
A PROPOSAL FOR APPROPRIATE
REGULATION
Responsibility Under the Law
The FDA's responsibility and obligation to protect
the public health against hazardous substances in the
food supply were established by Congress in the Food,
Drug, and Cosmetic Act. Section 409 of the act em-
bodies in the Delaney Amendment the explicit Congres-
sional policy to prohibit all carcinogenic additives in
food. Since "food additive" has recently been judicially
interpreted to include any substance whose use can
reasonably be expected to result, directly or indirectly,
in its becoming a component of food,* the policy under-
lying the Delaney Clause is applicable to PCB's in food.
In addition. Section 406 of the act authorizes the estab-
lishment of tolerances for poisonous and deleterious sub-
stances in food. An appropriate regulatory policy with
respect to the contamination of food by PCB's must
therefore take cognizance of these expressions of legis-
lative intent.
A Regulatory Approach Consistent With the Health
Hazards Involved
Consistent with the foregoing expressions of Con-
gressional policy and with the evidence that PCB's are
both ubiquitous in the food supply and carcinogenic in
laboratory animals, the FDA should and indeed must
establish a zero tolerance for the levels of PCB's permit-
ted in food. New FDA regulations pertaining to PCB's
must start with the premise that elimination of PCB's
from the food supply is the ultimate goal. This does not
mean that all food supplies currently contaminated with
PCB's must be immediately condemned and confiscated.
Such an effort would be impracticable and irresponsible.
It does mean, however, that within a reasonable period
of time, PCB contamination of food supplies will no
longer be tolerated. In the interim, a temporary toler-
ance, sufficient to minimize the risks to public health,
must be established, and then progressively reduced to
zero. Such a regulatory posture would also require the
EPA to carry out, in a reasonable and appropriate man-
ner, its responsibilities with respect to environmental
•United States v. Ewing Bros. Co., 502 F.2d 715 (7th Cir.
1974).
contamination by PCB's and to stop the indiscriminate
discharge of PCB's into the environment.
The method used to establish temporary tolerances
for PCB's is very important. PCB's have been shown to
be carcinogenic in two species of laboratory animals. In
light of this evidence, it is clear that the routinely
applied 100-to-1 safety factor for toxic substances is
completely inappropriate. The FDA has already indi-
cated (ref. 27) its intention to adopt the Mantel-Bryan
method (refs. 28,29) of statistical analysis to establish
the required sensitivity of the testing method in cases
where carcinogenic additives or drjags are intentionally
added to animal feed or administered directly to ani-
mals. The FDA has adopted this position in an attempt
to satisfy the intent of Congress as expressed in the
Delaney Amendment. Temporary tolerances for PCB's,
established using the Mantel-Bryan or other (ref. 30) ap-
propriate statistical procedure, would be consistent with
this policy. Any values so obtained could not be con-
sidered a "safe" level since neither the Mantel-Bryan pro-
cedure nor any similar statistical method is intended to
be used to establish "safe" levels of exposure to environ-
mental carcinogens in food. On the contrary, they are
used to relate the dose of a carcinogen ingested to the
probability of the induction of cancer.
The establishment of temporary tolerances must be
viewed in light of the potential carcinogenic hazards
posed by PCB's. The rapid reduction to zero of such
-tolerances is the only reasonable and responsible action
that can be taken. Appropriate regulatory action is long
overdue. Any additional delay in reducing dietary levels
of PCB's can only result in increased exposure of the
population to potentially disastrous health risks which
neither they nor their elected representatives have under-
taken to assume.
REFERENCES
1. J. R. Allen, "Response of the Nonhuman Primate to
Polychlorinated Biphenyl Exposure," Federation
Proceedings, Vol. 34 (1975), p. 1675.
2. J. R. Allen, L. A. Carstens, and D. A. Barsotti,
"Residual Effects of Short-Term, Low-Level Ex-
posure of Nonhuman Primates to Polychlorinated
Biphenyls," Toxicology and Applied Pharmacology,
Vol. 30 (1974), p. 440.
3. D. A. Barsotti and J. R. Allen, "Effects of Poly-
chlorinated Biphenyls on Reproduction in the
Primate," Federation Proceedings, Vol. 34 (1975),
p. 338.
4. D. A. Barsotti, R. J. Marlar, and J. R. Allen, "Re-
productive Dysfunctions in Rhesus Monkeys Ex-
posed to Low Levels of Polychlorinated Biphenyls
449
-------
(Aroclor 1248)," Food and Cosmetics Toxicology,
in press.
5. R. D. Kimbrough, R. A. Squire, R. E. Under, J. D.
Strandberg, R. J. Montali, and V. W. Burse, "Induc-
tion of Liver Tumors in Sherman Strain Female
Rats By Polychlorinated Biphenyl Aroclor 1260,"
in press.
6. R. D. Kimbrough, "The Toxicity of Polychlorinated
Polycyclic Compounds and Related Chemicals,"
CRC Critical Reviews in Toxicology (January
1974), p. 445.
7. R. E. Linder, T. B. Gaines, and R. D. Kimbrough,
"The Effect of Polychlorinated Biphenyls on Rat
Reproduction," Food and Cosmetic Technology,
Vol. 12 (1974), p. 63.
8. H. Blumenthal, Testimony on PCBs in Paper Food
Packaging Materials, available from the hearing
clerk's office, FDA, Washington, D.C. (Docket No.
75N-0013).
9. J. R. Allen, D. H. Norback, and I. C. Hsu, "Tissue
Modifications in Monkeys as Related to Absorption,
Distribution and Excretion of Polychlorinated Bi-
phenyls," Arch. Environ. Contam. Toxicol., Vol. 2
(1974), p. 86.
10. A. Curley, V. W. Burse, M. E. Grim, R. W. Jennings,
and R. E. Linder, "Polychlorinated Biphenyls: Dis-
tribution and Storage in Body Fluids of Sherman
Rats," Environmental Research, Vol. 4 (1971), p.
481.
11. H. A. Price and R. L. Welch, "Occurrence of Poly-
chlorinated Biphenyls in Humans," Environmental
Health Perspectives, Vol. 1 (1972), p. 73.
12. A. R. Yobs, "Levels of Polychlorinated Biphenyls in
Adipose Tissue of the General Population of the
Nation," Environmental Health Perspectives, Vol. 1
(1972), p. 79.
13. B. Bush, C. F. Tumasonis, and F. D. Baker, "Toxici-
ty and Persistence of PCB Homologs and Isomers in
Avian Systems," Arch. Environ. Contam. Toxicol.,
Vol. 2(1974), p. 195.
14. G. Bagley and E. Cromartie, "Elimination Pattern of
Aroclor 1254 Components in the Bobwhite," J.
Chromatography, Vol. 75 (1973), p. 219.
15. D. L. Grant, W. E. J. Phillips, and D. C. Villeneuve,
"Metabolism of a Polychlorinated Biphenyl
(Aroclor 1254) Mixture in the Rat," Bulletin Envi-
ron. Cont. Toxicol., Vol. 6 (1971), p. 102.
16. A. M. Gardner, J. T. Chen, J. A. G. Roach, and E. P.
Ragelis, "Polychlorinated Biphenyls: Hydroxylated
Urinary Metabolites of 2,5,2',5' - Tetrachlorobi-
phenyl Identified in Rabbits," Biochem. Biophys.
Res. Commun., Vol. 55 (1974), p. 1377.
17. D. M. Jerina and J. W. Daily, "Arene Oxides: A
New Aspect of Drug Metabolism," Science, Vol.
185 (1974), p. 573.
18. M. Kuratsune, T. Yoshimura, J. Matsuzaka, and A.
Yamaguchi, "Epidemiologic Study on Yusho, a
Poisoning Caused by Ingestion of Rice Oil Con-
taminated with a Commercial Brand of Poly-
chlorinated Biphenyls," Environmental Health
Perspectives, Vol. 1 (1972), p. 119.
19. M. Kuratsune, "An Abstract of Results of Laborato-
ry Examinations of Patients with Yusho and of
Animal Experiments," Environmental Health Per-
spectives, Vol. 1 (1972), p. 129.
20. J^ R. Wessel, Testimony on PCBs In Paper Food
Packaging Materials, available from the hearing
clerk's office, FDA, Washington, D.C. (Docket No.
75N-0013).
21. G. Veith, "Baseline Concentrations of Polychlorin
ated Biphenyl and DDT in Lake Michigan Fish,
1971," Pesticide Monitoring Journal, Vol. 9 (1975),
p. 21.
22. R. Hanley, "PCB in Fish Stirs New State Study,"
The New York Times, September 16, 1975.
23. R. R. Linko, J. Kaitaranta, P. Rantamaki, and I.
Eronen, "Occurrence of DDT and PCB Compounds
in Baltic Herring and Pike from the Turku Archipel-
ago," Environmental Pollut, Vol. 7 (1974), p. 193.
24. R. R. Linko, P. Rantamaki, and K. Urpo, "PCB
Residues in Plankton and Sediment in the South-
western Coast of Finland," Bull, of Environmental
Contam. Toxicol., Vol. 12 (1974), p. 733.
25. P. E, Corneliussen, Testimony on PCBs In Paper
Food Packaging Materials, available from the hear-
ing clerk's office, FDA, Washington, D.C. (Docket
No.75N-0013).
26. "Supplement To The Final Environmental Impact
Statement Rule Making on Polychlorinated Bi-
phenyls," FDA (1973), p. 7.
27. A. C. Kolbye, Jr., Testimony on PCB In Paper Food
Packaging Materials, available from the hearing
clerk's office, FDA, Washington, D.C. (Docket No.
75N-0013).
28. N. Mantel and W. R. Bryan, "'Safety'Testing of
Carcinogenic Agents," Journal of the National
Cancer Institute, Vol. 27 (1961), p. 455.
29. N. Mantel and M. A. Schneiderman, "Estimating
'Safe' Levels, a Hazardous Undertaking," Cancer Re-
search, Vol. 35 (1975), p. 1379.
30. D. G. Hoel, D. W. Gaylor, R. L. Kirschstein, U.
Saffiotti, and M. A. Schneiderman, "Estimation of
Risks of Irreversible Delayed Toxicity," Journal of
Toxicology and Environmental Health, Vol. 1
(1975), p. 133.
450
-------
CONCERNS AND RECOMMENDATIONS OF THE NATIONAL
MARINE FISHERIES SERVICE REGARDING APPROACHES TO CONTROL
THE POLYCHLORINATED BIPHENYLS PROBLEM
Thomas J. Billy*
Abstract
AREAS OF CONCERN
The views of the National Marine Fisheries Service
concerning what can and should be done to (1) prevent
PCB's from further polluting the environment, (2) pro-
tect consumers and limit human exposure, and (3) avoid
unnecessary adverse publicity having a severe economic
impact upon the fishing industry are described. Specific
environmental, consumer,and fishing industry concerns
are discussed and recommendations made in light of
these concerns.
INTRODUCTION
On the occasion of this conference, the National
Marine Fisheries Service (NMFS) would like to express
its views concerning what can or should be done to (1)
reduce the amounts of PCB's reaching the environment,
(2) limit human exposure, and (3) avoid unnecessary
adverse publicity.
In earlier sessions, we have heard presentations on:
1. Health effects and human exposure, including the
available toxicological information.
2. The uses, sources, and identification of PCB's,
3. Discussion on the environmental fate and occur-
rence, including the ecological effects of exposure.
4. The availability and economics of substitutes.
5. The impact that the PCB pollution problem has
already had on people and their livelihoods.
During this session of the conference, presentations
have been made on what can be done to reduce the
amounts of PCB's reaching the environment and to limit
human exposure. Federal and State roles and responsi-
bilities have been described and the recent Canadian
regulatory measures have been presented.
With this information and data base and with the
approaches and responsibilities for control outlined in
this session, I would like to express our concerns and
recommendations, as the Federal Agency with the pri-
mary responsibility for the management and utilization
of our Nation's marine fishery resources.
*Chief, Fishery Products Inspection and Safety Division,
National Marine Fisheries Service, National Oceanic and Atmos-
pheric Administration, Department of Commerce, Washington,
D.C.
Our concerns can be put into the following three
categories:
1. Aquatic environment,
2. Consumers of fishery products, and
3. Fishing/seafood industry.
Let us take a brief look at each of these areas.
1. Environmental Concerns
Effective, comprehensive controls to prevent the
pollution of the environment from the manufacture,
sale, use, and disposal of PCB's in the United States have
not been implemented to date, resulting in the continu-
ing contamination of the ecosystem and the consequent
occurrence of PCB residues in a number of fish species
and other foods.
2. Consumer Concerns
We believe responsible regulatory action has been
taken already to deal with the public health issue, and
we fully support the current 5.0 ppm temporary toler-
ance for PCB's in fishery products. However, our con-
cern is that certain information being presented at this
conference and other pressures could result in precipi-
tous further regulatory actions that are not based upon
the full and complete information necessary to justify
such actions.
No change in the present tolerance should be con-
templated until full and proper consideration has been
given to:
a. New, conclusive toxicological information.
b. The role of the specific species in the diet.
c. Probable further decreases in PCB levels over an
extended period of time.
d. Direct economic impact to the fishing industry
as well as the overall economic impact.
e. Alternative government and industry ap-
proaches for assuring consumer protection.
Finally, there is concern that some of us in this
room may fail to recognize our responsibility to insure
that information reaching the public be completely fac-
tual, not speculative, and that it be presented fairly so as
to prevent unnecessary confusion on the part of con-
sumers and the resultant severe economic impact on the
fishing industry.
3. Seafood Industry Concerns
There is a lack of recognition by some that an indus-
try depends upon the natural resources which we are
451
-------
discussing, and we have imposed a serious problem on
them that is not of their making. The seafood industry is
concerned about the safety of their products and has
been and continues to be willing to take responsible ac-
tions to protect public health.
However, NMFS is concerned that the lessons from
the past in over-regulating or implementing unnecessary
regulatory actions will not be heeded.
RECOMMENDATIONS
In light of these concerns as well as the available
information, the National Marine Fisheries Service
recommends the following:
1. That Federal and State governments take immediate
steps to implement effective controls to prevent the pol-
lution of the environment by RGB's under the many
authorities available to them. These controls should con-
sider the manufacture, sale, use, and disposal of RGB's
and other similar hazardous substances.
2. That current tolerance for RGB's in seafood should
be maintained unless new and complete information
warrants consideration of specific actions to selectively
deal with specific problems.
3. That release of unnecessary or irresponsible adverse
publicity or other actions that will have a direct impact
on all seafood sales should be avoided.
In summary, let us not once again lay ourselves
open to the criticism of having only single purpose goals.
Let us evaluate all risks, costs, and benefits and then
take further regulatory actions, based on the greatest net
good to society.
452
-------
THE ROLE OF THE COAST GUARD
IN PCB POLLUTION CONTROL
Lt. Cmdr. J. A. MacDonald*
Abstract
In order for the Coast Guard to act in protecting the
environment, the substance to be controlled must be
designated as a harmful or a hazardous polluting sub-
stance by EPA. To this date, PCB's have not been offici-
ally established as such. Public awareness is also crucial
in helping the Coast Guard fulfill its role—handlers must
learn that PCB's are hazardous and treat them according-
ly, and those who detect spills should report them
promptly.
The Coast Guard's role in protecting the environ-
ment from PCB pollution is defined in Section 311 of
the Federal Water Pollution Control Act of 1972 as
amended. That role is to prevent transportation-related
spills of oil and hazardous polluting substances from
entering the navigable waters of the United States or the
contiguous zone, and to enforce the provisions estab-
lished in Section 311.
In order for the Coast Guard to initiate actions to
respond to this role, PCB's must be designated by the
Environmental Protection Agency as a harmful or
hazardous polluting substance, and a determination
made as to the amount that is hazardous. After this is
determined, the Coast Guard will address the problem in
three basic ways: detection of spills, prevention of
spills, and enforcement of statutory sanctions for such
spills.
Increased public awareness will help to reduce and
mitigate the effects of PCB spills. As soon as the public
*Chief, Pollution Prevention and Enforcement Branch, U.S.
Coast Guard.
is aware that PCB's are hazardous, and that special pre-
cautions should be taken in their jiandling and transpor-
tation, the number of spills involving PCB's will certainly
decline.
Detection is exceedingly difficult because PCB's are
a relatively colorless liquid. Oil, on the other hand, is
more easily detected although even certain oils present
problems for us from time to time. It may be possible
that some form of tagging, such as the utilization of
dyes, would assist in the detection of PCB spills.
Prevention also ties-back into public awareness. If
the stevedore handling a transformer containing PCB's
on a pier in Seattle had been aware that the transformer
contained a hazardous polluting substance, he might
have been more cautious while handling that trans-
former, and the resultant spill might have been averted.
Enforcement is predicated upon an illegal spill
being detected and reported to the proper authorities.
We must ascertain that a spill took place, establish its
cause, and identify the responsible party so that penalty
assessments and statutory sanctions can be invoked.
To reduce and mitigate the effects of a spill after it
has taken place, we would deal with it in a manner some-
what analagous to the manner in which we deal with oil
spills. Response teams capable of dealing with spills of
any number of hazardous substances of various mag-
nitudes would assist in the containment and cleanup.
Unfortunately, with PCB's these actions are made very
difficult by the physical properties of the liquid.
There are some hard questions that need answering
immediately. The Coast Guard, EPA, and other agencies
will address them as soon as practicable. I would re-
emphasize, however, the fact that our future actions in
regard to PCB's are predicated upon its establishment as
a hazardous polluting substance.
453
-------
CONSIDERATIONS BY THE DEPARTMENT OF TRANSPORTATION
Alfred W. Grella*
Abstract
The Department of Transportation (DOT) has nine
categories for hazardous materials. Packages containing
these substances are to be labeled by category and han-
dled accordingly. PCB's are not presently classified as
conventional toxic materials and are therefore not regu-
lated under DOT criteria. The department is now consid-
ering whether to develop a generic category of "hazard-
ous wastes" and/or similar categories for environmental-
ly hazardous materials, which would possibly include
materials such as PCB's.
I have just a few remarks which would point out
some of the thinking in DOT, some of the concerns we
have, and some reasons why we do not have any regula-
tory criteria at the present time for transportation
requirements for PCB's. It is important at the outset to
point out that the current standards and philosophies in
regulating hazardous materials in transportation are
based on considerations of preventing acute hazards
caused by release of hazardous materials from their
packaging. This philosophy is common to Doth the inter-
national and the domestic transportation requirements.
Another way of saying this is that ws do not regu-
late materials from a standpoint of the long-term effects
from chronic hazards. In transportation hazardous mate-
rials are grouped or categorized into approximately nine
classifications. The hazardous material may either be
listed by name and classification or under a generic head-
ing by classification.
The regulations, for the most part, provide test
criteria for persons to test a material to determine its
classification, if the material is not already listed. If it is
regulated under these criteria, then packaging, marking,
and labeling requirements are prescribed, and sometimes
carrier stowage requirements are indicated.
For -these purposes, the "conventional" poison
classification criteria relate to the effects of animal tests
against oral, inhalation, and skin-absorbtion criteria. It is
clear that the PCB's that we are aware of are not present-
"Chief, Technology Division, Office of Hazardous Materials
Operations, Materials Transportation Bureau, Department of
Transportation, Washington, D.C.
ly regulated as "conventional" toxic materials. There-
fore, they are not regulated in transportation under our
present DOT criteria.
Previously there has never been a statutory defini-
tion of "hazardous materials." Recent legislation, as
recent as January of this year, resulted in the Transpor-
tation Safety Act of 1974, Public Law 93-633. In sec-
tion 103, paragraph 2, "hazardous material" is defined
as "a substance or material in a quantity and form which
may pose an unreasonable risk to health and safety for
property when transported in commerce."
Therefore, it appears, for the first time, that we may
have some sort of a basis to look at criteria other than
the acute hazard, if such action appears appropriate.
And the same consideration is coming up more and more
when we talk about the generic term, "hazardous
wastes." Many hazardous wastes may already be regu-
lated now as hazardous materials. There are also many
types of hazardous waste that may not be quite toxic
enough or quite corrosive enough or quite flammable
enough to be regulated. But they still may be objection-
able with respect to release to the environment.
The other area is carcinogenic materials in general,
which do not meet the conventional toxicity criteria.
So in these three areas—PCB's, hazardous wastes,
and carcinogenic materials, we are starting to take a long
look at whether there is, a need for some degree of regu-
lation in transportation. The question would then arise:
What should that degree of regulation be? Certainly,
packaging requirements might have to be addressed and,
certainly, considerations for labeling. This will give you
some idea of the things we are thinking about. We have
not formed any actual, concrete plans. We are following
very closely what the other agencies are doing and are
maintaining as close contact as possible with those
agencies.
The UN Group of Experts on Dangerous Goods,
which is the international body that develops regulations
for the transport of hazardous materials, has been
debating the subject of PCB's and environmental pollut-
ants for several years and has not been able to come to
agreement as to whether they should undertake to regu-
late environmental hazards at all or whether this should
be left to the environmental groups.
454
-------
OBSERVATIONS ON AND SUMMARY OF SESSION VII
Albert Kolbye, M.D., M.P.H., J.D.*
It has been a very interesting meeting and we have
heard a lot of interesting data, opinions, and some
rhetoric. I would like to make a few quick points that I
think we should all keep in mind, because personally I
feel once again we in FDA are the straight men in a bad
joke. We are asked to mediate decisions that involve
many parameters, not the least of which concerns
human safety very directly.
We are asked to interpret data and to come up with
limits on human exposure over time. We have previously
dealt with environmental contaminants. We have a few
that we unfortunately have experience with that are
biologically persistent and for which experimental data
show that there are varying degrees of carcinogenic
potential, at least in animals.
1 should like to talk about a guideline for a moment,
because a guideline or a tolerance or however you wish
to think of it represents a level in a particular food. What
is really important in the long run is what the exposure
dose is that humans receive and how they receive it.
The major point that 1 am trying to make is that we
feel the average consumer is fairly well protected against
the hazards of PCB's. But if one eats food with a high
percentage of contaminating residues, and if one eats
that particular food commodity frequently, one's ex-
posure dose quite obviously goes up. As far as I can see,
the people who in this country bear the greatest poten-
tial risk are selected sport fishermen, "sport fisher
people," who, if they are catching and retaining and
consuming with a high degree of frequency certain'
species of fish from certain geographic locations, have
higher exposures than do the rest of us in this country.
One of the decisions we have to make is what incre-
mental degree of protection will be afforded to the pub-
lic by a decremental change in our guidelines. But please
'Associate Director for Sciences, Bureau of Foods, Food
and Drug Administration, Washington, D.C.
remember once again that a guideline itself represents a
judgment concerning dietary intake, which also repre-
sents a judgment about the frequency of food consump-
tion. And it is a little difficult sometimes to draw a
bright line in a gray zone and I believe you can expect
reasonable people to differ somewhat in their opinions
about where that bright line should be drawn.
I would like to say one other thing about a guide-
line, because it would appear from time to time here and
there that there has been some confusion about the
meaning of a guideline with reference to cooperative
action by various governmental sectors regarding the en-
vironment. An FDA guideline involving an environ-
mental contaminant in food is not, and I repeat, is not
equivalent to permitting pollution. It does not give
license to pollute. Some people seem to have thought in
the back of their minds that as long as fish did not
exceed such and such a level of PCB's, a certain amount
of PCB's entering the aquatic environment was per-
missible. That thinking is now obsolete.
The ecological criteria as far as I can see, with re-
spect to wildlife, are some of the most sensitive indi-
cators with respect to substances like PCB's, and I think,
as was mentioned earlier, we should take note of such
data in terms of our overall cooperative efforts to pro-
tect the environment.
I think health and environmental education should
be undertaken for the public (and in particular for cer-
tain people who are concerned with disposal of solid
waste) as to what containers are likely to contain PCB's
and the proper identification and disposal of transformer
fluid, etc.
I would also like to make one note. Let us not
unduly focus on the polychlorinated biphenyls. There
are other environmentally persistent compounds of con-
cern, and a recent episode has led us to fully appreciate
that the polybrominated biphenyls are also of concern.
Thank you very much.
455
-------
21 November 1975
Session VIII:
SUMMARY SESSION
John L. Buckley, Ph.D.
Session Chairman
457
-------
SUMMARY OF SESSION I
DR. J. G. VOS (Rijks Instituut voor de Volksgezond-
heid, Bilthoven, The Netherlands): Recent findings
on the biological action of PCB's, such as carcino-
genicity in rodents and the disturbed reproduction
in monkeys, greatly increase our concern of PCB's
as a health hazard.
In summarizing the papers presented in the
session on health effects, one is confronted already
in Dr. Kuratsune's paper with the problem of PCB's
and chlorinated dibenzofuran impurities. In the
"Yusho" disease, one is struck by the persistence of
symptoms present in patients, although there is a
shift in the pattern, a decrease over the years in the
skin lesions but a persistence of hypersecretion of
Meibomian glands. In "Yusho" patients, increased
urinary excretion of 17-ketosteriods was noted, as
was an increase in serum triglyceride levels. Changes
in the menstrual cycle were observed in a high per-
centage of female patients. Mean blood levels in
"Yusho" patients were 7 ppb. This level conflicts
with the high PCB concentrations in blood of work-
ers who are occupationally exposed yet who, for the
most part, show no indication of adverse effects.
A possible explanation for this difference was
the relatively high concentration (5,000 ppm on
PCB basis) of chlorinated dibenzofurans (including
2,3,7,8-TCDF) in rice oil. Apparently furans were
formed in the PCB during its use as a heat exchang-
er, since the level of chlorinated dibenzofuran in
Kanechlor KC-400 was approximately 17 ppm. Of
particular significance was the relatively high con-
centration of chlorinated dibenzofurans versus
PCB's in the liver of some patients who died, when
compared with adipose tissue values. Further studies
are required to solve the dilemma of the importance
of furans in the etiology of "Yusho" disease; and in
a wider context, to get information on possible
changes in composition or concentrations of chlo-
rinated dibenzofuran and other contaminants in
used PCB's and on their fate in the environment.
During the 1971 PCB conference, there was
some concern on a bladder tumor that was found in
a rat by Dr. Kimbrough. Now we know that this
tumor apparently developed spontaneously. But as
we heard from Dr. Kimbrough, in recent studies cer-
tain PCB mixtures induce tumors in rats and mice.
A spectrum of lesions are induced in livers of rats
fed 100 ppm Aroclor 1260 for 21 months: hyper-
plastic or neoplastic nodules in 80 percent of the
treated animals and in none of the controls, and
hepatocellular carcinomas in 14 percent of the ex-
perimental animals and in one out of 173 controls.
Metastases were not observed. However, hepato-
cellular carcinomas were not found in the chronic
study in rats, as reported by Dr. Calandra. A possi-
ble explanation can be the small number of animals
used in this study. Evidently, this question has to be
solved. Hyperplastic nodules were seen in 25 to 50
percent of rats fed 100 ppm Aroclor 1242, 1254, or
1260. These three mixtures did not appear to be
mutagenic or teratogenic. No-effect levels based on
2-year studies in rats and dogs and reproduction
studies in rats were 10 ppm.
As reported by Dr. Allen, adult monkeys and in
particular the females are very sensitive to PCB's.
When Rhesus monkeys were fed 2.5 or 5 ppm Aro-
clor 1248—that is, approximately 0.1 or 0.2 mg/kg
body weight/day—skin lesions consisting of acne of
face and neck, edema, and hair loss developed in
some females already after 2 months. All females
exhibited these changes after 6 months, but males
were more resistant. Disturbances in reproduction
were present in females and not in males. Menstrual
cycles were irregular within 4 months. The concep-
tion rate in the 5-ppm group was decreased. Because
of resorptions and abortions, the birth rate was re-
duced and the infants born were small. Fifty per-
cent of them died before weaning, showing typical
lesions. These effects on reproduction may be due
to an estrogen/progesterone imbalance. Female
rhesus monkeys on a PCB diet had increased urinary
levels of ketosteriods.
By comparing the reports of Drs. Kuratsune
and Allen, one is struck by the similarity of lesions
present in "Yusho" patients and those produced ex-
perimentally in the monkey, with the exception o-f
the effect on serum triglycerides. Both species seem
also to be equally sensitive in a quantitative way.
Dr. Matthews studied the effect of chlorination
on tissue distribution and excretion of PCB isomers
in rats. Each of the PCB's studied was removed
rapidly from blood to liver and muscle. Redistribu-
tion to skin and adipose tissue increased with in-
creasing chlorine concentration, whereas elimination
via urine or feces was highest with the low chlorina-
ted isomers. After 6 weeks, 85 percent of the
2,4,5,2',4',5'-isomer was still present in adipose
tissue and skin, while the residue of
2,4,5,2',5'-isomer was only 5 percent. Significant
excretion occurs only after metabolism to polar
compounds. The necessary factor could be the pre-
sence of two adjacent unsubstituted carbon atoms
459
-------
that facilitate the formation of arene oxide inter-
mediates, as was also reported by Dr. Allen in his
study with the 2,5,2'5'-isomers in the monkey.
Dr. Ecobichon reported on the influence of
position and degree of chlorination of chloro-
biphenyl isomers on the hepatic function in the rat.
Substitution at the 4 and 4' positions, irrespective
of chlorination at other positions, enhanced the
activities of endoplasmic reticulum bound enzymes
0- demethylase and aniline hydroxylase. This is
probably due to their higher persistence. For en-
zymes less discretely localized in the liver cell, such
as carboxylesterase and sulfobromophthalein
-glutathion conjugating enzyme, the position of
chlorine atoms appears of less importance. Purified
unsubstituted biphenyl did produce enzyme induc-
tion, though enhanced effects were noted when one
or more chlorine atoms were present.
As can be concluded from the report of Dr.
Biocca, biological effects of symmetrical hexachlo-
robifenyl isomers differ not only quantitatively but
also qualitatively. Such comparative studies are
necessary for the ultimate goal—that is, the under-
standing of the biological effects produced by com-
plex mixtures that endanger human health, mixtures
that are different from those formulated commer-
cially. Of the three isomers tested in mice, 3,4,5,3',
4',5'-HCB was most toxic, followed by 2,4,6,2',4',6
'-HCB and 2,4,5,2',4',5'-HCB, respectively. Liver
weights were increased by all three isomers. Severe
thymus atrophy and a decrease in a- and 7-globulins
were produced only by 3,4,5,3',4',5'-HCB. In a
study in chickens, these isomers along with 2,3,4,2
',3',4'-HCB and 2,3,6,2',3',6'-HCB were given at 400
ppm in the diet for 3 weeks. Again, 3,4,5,3',4'
,5'-HCB was most toxic and was lethal even at 3
ppm. Chickens exhibited pronounced edema, thy-
mic involution, and marked liver pathology. How-
ever, chickens that were fed 100 ppm died earlier
and had only mild-liver pathology. The 2,4,6,2',4'
,6'-HCB was less toxic (no deaths at 400 ppm) but
caused marked liver pathology and highest liver
weight increase. The toxicological effects of
3,4,5,3',4',5'-HCB differ qualitatively from the
other HCB isomers studied, and resemble the lesions
produced by 2,3,7,8-TCDF.
Dr. McKinney reported on metabolism studies
of HCB isomers in the chicken using low resolution
mass spectrometry. When metabolites were detect-
ed, the three basic reactions were isomerization,
reductive dechlorination, and oxidation with and
without chlorine loss. Siginificant metabolites were
not detected in excreta of chickens fed 2,3,4,2',3',
4'-, 3,4,5,3',4',5'-, or 2,3,6,2',3',6'-HCB. Metahydr-
oxylation followed by parahydroxylation of the
same ring are favored processes for 2,4,5,2',4',
5'-HCB. Further oxidation could give quinone. The
presence of a metabolite with a trihydroxypenta-
chlorobiphenyl structure indicated that dechlorina-
tion can be concomitant with hydroxylation. A di-
benzofuran metabolite was not detected.
In the case of 2,4,6,2',4',6'-HCB, several re-
action types occurred: dechlorination, isomeri-
zation, and dibenzofuran formation. This isomer
had lowest effect on body weight, did not give a
high liver residue, but produced most severe liver
pathology despite the dibenzofuran formation. In
contrast, 3,4,5,3',4',5"-HCB accumulated most in
liver and fat, was most toxic with "furan"-type ef-
fects, but metabolites were not detected in the ex-
creta. However, one has to consider in the case of
2,4,6,2',4',6'-HCB and possibly 3,4,5,3',4',5'-HCB
the possibility of covalently bound metabolites that
may be of toxicological significance. A good corre-
lation, which may have predictive value, was ob-
served between the retention indices from gas chro-
matography with the adipose tissue concentration.
An exception was the 2,4,6,2',4',6'-isomer, which
had the smallest retention index but relatively high
tissue accumulation. The strong ortho effect could
be responsible for this discrepancy.
Dr. Moore reported on the first toxicity studies
with 2,3,7,8-TCDF. Marked thymus atrophy and
the presence of edema are seen in chickens dosed
daily with 1 jug/kg. Only mild liver pathology was
present at the 5-^g dose level, which produced 100
percent mortality. The LDSO in guinea pigs after a
single oral dose was approximately 7 /ug/kg body
weight. In chicken and guinea pigs, 2,3,7,8-TCDF is
lethal at dose levels that are less than one order of
magnitude higher than that of 2,3,7,8-TCDD and
share a number of biological effects. Mice and rats
are more resistant to TCDF. A single subcutaneous
dose of 6,000 fig/kg dicl not reduce body weight but
gave thymus atrophy and mild liver toxicity in mice.
No effect was noted in rats intubated with 1,000
/zg/kg body weight. Clearly, more research is needed
with different chlorinated dibenzofurans isomers in
order to assess their health hazards.
460
-------
SUMMARY OF SESSION II
MR. DAVID GARRETT (Environmental Protection
Agency, Washington, D.C.): In Session II, Dr.
James Mieure, who is research group leader, Mon-
santo Industrial Chemicals of St. Louis, spoke of
PCB's, their properties and mixtures, and presented
physical and chemical properties of commercial Aro-
clor products.
Dr. Stephen Safe, Associate and Professor, De-
partment of Chemistry, University of Guelph,
Ontario, presented an overview of analytical identif-
ication and spectroscopic properties. Key among the
points stressed were that sophisticated methods and
equipment are available for identification and quan-
tification of PCB's at extremely low levels.
Dr. Robert Durfee, Vice President of Versar,
Inc., presented topical information on the manufac-
ture and uses of Aroclors in the United States and
also gave a vivid description of the use of Aroclors
in the manufacture of closed electrical systems-in
particular, capacitors and transformer products. In
addition he presented an overview of PCB's uses in
investment casting waxes and the casting process it-
self was reviewed.
Thomas E. Kopp of the Office of Toxic Sub-
stances in the Environmental Protection Agency re-
viewed past, present, and possible future regulatory
activities of EPA concerning PCB's in the water
environment. He discussed proposed voluntary stan-
dards being prepared by NEMA, ANSI concerning
labeling and safeguards for handling askarels and
askarel-containing equipment.
Then, Mr. Stanton Kleinert, who is Chief of
Surveillance for the Wisconsin Department of Natu-
ral Resources, discussed sources of PCB's in the
State of Wisconsin, emphasizing the probable role of
intermedia transfer from air to water and describing
some possible sources of contamination for food
and water.
And lastly in this section, Mr. John Hesse,
Supervisor of the Toxic Material Unit, Department
of Natural Resources in Michigan, described uses of
PCB's and losses to the environment of Michigan.
Mr. Hesse also emphasized PCB losses to air and the
probably significant transfer of these PCB's into the
water medium. Data was presented on PCB concen-
trations in municipal treatment effluents and
sludges, which undoubtedly contributes to the con-
tinuous cycling in the environment of these persist-
ent pollutants.
Some of the salient points generally brought
forth in the meeting either presented or implied
were that PCB losses to air could be an important
contributor to the problems we encounter in water.
Disposal of PCB's waste to municipal sewage treat-
ment does not necessarily curtail the cycling and
environmental damage from PCB's. And undoubted-
ly there should be a greater sense of accountability
among users of PCB's and a closer control of inven-
tory.
Additionally, there is presently no corrective
U.S. authority which could regulate importation of
PCB's and PCB-containing products, nor other seri-
ous environmental contaminants which are not pes-
ticides, drugs, and the like.
And lastly, judging from estimates of PCB's
already contaminating the environment and its in-
habitants, the task of cleanup is monumental, even
if we had proven technology with which to accom-
plish this task. Thank you.
SUMMARY OF SESSION III
DR. IAN C. T. NISBET: Eleven major points came out
in the course of our session on transport and accu-
mulation of PCB's in the environment.
1. We know almost nothing about chlorinated di-
benzofurans, except that they are present in Aroclor
1242 and 1254, and we learned during Session I
that they are formed in use and they are formed by
metabolism. We know nothing whatsoever about
their subsequent behavior in the environment.
2. PCB's themselves remain universally distributed
in the environment. Although some releases have
been curtailed, otheY releases continue. These in-
clude releases from manufacturing, leaks from sup-
posedly closed systems, scrapping of PCB's manu-
factured before 1971 and of materials containing
them, and use in nonclosed systems of material that
461
-------
is either imported or diverted from other uses.
3. Surprisingly large quantities of PCB's which
match Aroclor 1254 or 1260 are still being found in
air and ;n dry fallout and precipitation. It is difficult
to account for these quantities in terms of known
past uses, and accordingly we may have to look for
a significant current source of air emissions. Perhaps
this may be air emissions from transformers, or dis-
posal of scrap materials from them.
4. There is circumstantial evidence that PCB's that
are now trapped in large quantities in sediments in
lakes, rivers, and estuaries will remain available for
resuspension and will continue to move slowly
downstream. We do not have any precise infor-
mation about their persistence or about the time it
will take them to move downstream into the sea,
but we believe that it is to be measured in years, if
not decades.
5. Although PCB levels have decreased consider-
ably in some components of the environment such
as terrestrial birds or the mussels collected off
California, as yet there is no clear indication of a
consistent decline in PCB residues in fish. We should
not expect a rapid decline, because of the long re-
tention time of PCB's in the environment and in
human tissue.
6. In addition, many items containing PCB's have
service lives of 10 to 20 years before they are dis-
carded, so that we are still experiencing releases of
materials manufactured before 1971.
7. Because of time lags in response we may not
yet have reached peak levels in some compartments
in the environment. I am thinking here particularly
of estuaries, where levels of PCB's may continue to
increase as sediments are transported downstream.
8. Most human exposure to PCB's in the diet is via
fish, although there is some human exposure via
other routes, such as milk, meat, and b'y inhalation
in the air. The information from the FDA total diet
program suggested that the dietary exposure of an
average adult in the United States is of the order of
10 micrograms per day. However, an average for
PCB's has little meaning because of the very wide
variations in individual consumption of fish and
enormous variations in the contamination levels.
9. Individuals who have a dietary preference for
freshwater fish will take in much more than the
average-in some cases at least a hundred times as
much as the average. Breast-fed infants appear to
have extremely high dietary intakes of PCB's, aver-
aging about 50 times higher than that of their
mothers on a milligram per kilogram basis. The
breast-fed infant appears to be one of Dr. Kolbye's
special consumers who is imprudent enough to eat
the same diet every day.
10. Monitoring of PCB residues in human fat in the
United States and Canada shows that the median
PCB concentration is of the order of 1 ppm. Again
there are enormous variations, at least a hundred-
fold variation between the highest level recorded
and lowest level detectable.
11. Finally, although tetrachlorobiphenyls are more
easily degraded in the environment than penta-
chloro- or higher chlorinated compounds, the tetra-
chlorobiphenyls are nevertheless accumulated and
retained by fish. Accordingly there are significant
human intakes of tetrachlorobiphenyls, even though
they are not retained in significant quantities in
human tissues. Therefore, release of either Aroclor
1016 or 1242 into aquatic systems will lead to some
human exposure to tetrachlorobiphenyls.
SUMMARY OF SESSION (V
DR. DONALD I. MOUNT (Environmental Protection
Agency, Duluth, Minnesota): Among and between
the birds, mammals, and aquatic organisms there are
marked differences in sensitivity to PCB's. Even so,
these differences are not large when compared to
species differences found for other pollutants. Like-
wise, there are differences in the toxicity of various
Aroclors and isomers of PCB's that are real but not
large.
While increasing chlorine content increases tox-
icity in warm-blooded animals, increasing chlorine
content decreases toxicity of PCB's to aquatic ani-
mals. This observation is exceedingly important in
determining the future actions to be taken on
PCB's. Increased chlorine content seems to increase
biological half-life and bioconcentration in all ani-
mal groups, but the evidence is not entirely clear cut
on this point.
To generalize, we can say that in most cases
acute lethal toxicity in birds and mammals occurs
462
-------
from 10 to 100 ppm in the food, while more sensi-
tive species may suffer death from 1 to 10 ppm in
the food, Concentrations of about 5 ppm in bird
eggs produced death. And concentrations of RGB's
from .5 to 5 ppm in food produced reproductive or
growth effects. For aquatic animals, water concen-
trations of 10 to 100 micrograms per liter are acute-
ly lethal. Concentrations of 1 to 10 micrograms per
liter produced chronic reproductive or growth ef-
fects and water concentrations of 1 to 10 nano-
grams per liter (ppt) produced residues of biological
or public health significance.
Direct uptake from water into aquatic orga-
nisms is very significant and appears to produce con-
centration factors on the order of one hundred
thousand or more times. Water uptake supplement-
ed by food intake results in concentration factors of
five hundred thousand or more times.
The metabolic pathways, biological half-life,
and selected isomer concentrations appear to be dif-
ferent, especially between cold-blooded and warm-
blooded animals and for various mixtures and iso-
mers of RGB's. Enzyme systems of poikilotherms
are vastly different among the various groups and
are also different from the enzyme systems of the
homeotherms.
Measurable harmful effects of RGB's in the envi-
ronment on organisms are not abundantly docu-
mented, and for the most part the effects that have
been found are limited to subtle ones except for
specific instances such as in mink and certain bird
populations. Based upon laboratory toxicity data
and contamination levels found in the environment,
one would predict only subtle effects to occur. This
is not to say they are not significant.
The greatest concern continues to be residues as
they affect the organisms carrying that residue—
especially in the eggs and sex products-and as they
effect the higher consumers. Apparently water con-
centrations will have to be kept in the range of .1 to
.5 nanograms per liter if unacceptable residues are
to be avoided. And the evidence to date is uncon-
vincing that 1016 is an acceptable substitute as far
as aquatic organisms are concerned.
SUMMARY OFSESSION V
DR. NICHOLAS A. ASHFORD (Massachusetts Institute
of Technology, Cambridge, Massachusetts): While
the effects of RGB's and their possible control are
being pursued it is quite necessary and natural that
development of substitutes and their economic and
health implications also be examined. In what fol-
lows, my purpose is to summarize the conference
section dealing with economics and substitutes for
RGB's. I shall present the summary in an order dif-
ferent from that in which the participants appeared,
so as to follow a logical sequence most meaningful
to the substitute issue. Duncan McArthur from the
Foster Snell operation presented an analysis of the
RGB case which was part of a larger study (called
"the Snell Report") of the probable effects of a
Toxic Substance Control Act. In the RGB analysis,
they addressed the direct and secondary impact of a
complete banning of RGB's in the absence of tech-
nological breakthroughs and new substitutes. They
postulated this prohibition would be effected over a
period of 76 months, 38 months of which would be
consumed with hearings and the promulgation of
standards, with 38 months remaining for the tech-
nological response to eliminate the use of RGB's.
The analysis focused on transformer and capacitor
manufacturing having a volume capacity of 45
million pounds in 1973. On this basis, they calculate
a one-time cost to society of $13.7 million, $8.8
million of which would affect the secondary users.
Thereafter, an annual cost of $110 million per year
was anticipated, of which $16.5 million fell upon
primary users and $93.3 million on the secondary.
There was no detailed examination of the health
and economic benefits to be derived from a banning
of RGB's.
Dr. Dale Hattis from MIT's Center for Policy
Alternatives reported on an examination of both
economic and environmental health changes that
may have occurred as a result of the past partial
withdrawal of the product from commerce by Mon-
santo. One of the factors covered was the increase in
fire insurance premiums, estimated as possibly in
the tens of millions of dollars and which presumably
represented the increased risk as viewed by the in-
surance industry. It is important to note that the
methodology was restricted by the availability of
information on the nature of substitutes. This
points out the complication of trade secrecy and
463
-------
proprietary information, which, while presumably
legitimate for other reasons, does complicate the
assessment of costs and benefits.
Two surprises appeared in the study. One had
to do with the use of PCB's in paint systems. It was
noted that a major group of substitutes evolved
which were more economical than the PCB's which
they replaced. This evidences a common inertial re-
sistance to technological change even when it could
be anticipated to be more beneficial (in a strictly
economic sense) than technology already in use. A
secondary benefit which should result from the de-
creased use of PCB's is a reduction in the threat to
sport fishing. A calculation of recreational value
could be very large even compared with the alterna-
tive recreational activities which occur as second
best choices on the part of sport fishermen. The
enormous size of the valuation inferred for sport
fishing makes it easily the largest of the defined
costs of unrestricted PCB disposal.
A third participant, Richard Rollins, spoke for
the Electronic Industries Association, which is con-
cerned for the manufacturers and users of capaci-
tors. He cited the issues of flammability and reliabil-
ity, and he urged the development of less toxic sub-
stitutes. This latter remark was consistent with one
very clear message embodied in remarks by the
group, namely that his industry was much more
concerned with the environmental consequences
than cost increases in the product. He stated that
there are no commercially available substitutes in
AC capacitors, including the substitutes presented at
this meeting, which are acceptable for safety and
reliability. One interesting point made was that
since the components of capacitor-grade PCB (Aro-
clor 1016) are not what are found in the environ-
ment, protection of the environment might not
profitably be served by attacking the issue of capaci-
tor use and disposal. It appeared to him that PCB
contamination must be coming primarily from some
other industrial source.
Dr. E. J. Inchalik for Exxon Chemical reported
on capacitor substitutes based on diisononylphthal-
ates with a flashpoint of 430° Fahrenheit and which
are essentially already developed, but not yet fully
proved and tested for health and environmental
effects.
The Prodelec operation from France presented
an approach which is an incremental modification
of previous technology. For transformer use, they
recommend keeping trichlorobiphenyl in mixtures
with chlorobenzene. Both compounds of course,
being chlorinated, have problems in that regard.
Secondly, for capacitors they propose a mixture of
dichlorobiphenyls and their alkylated derivatives, a
commercial mixture of which is called chloralky-
lene. These products are now being examined by an
institute in Bonn for environmental behavior and he
indicates that tests already show there is more
biodegradation and lower toxicity for these com-
pounds than for their PCB counterparts.
Mr. David Wood from Monsanto Company
described two new products, MCS-1238 and
MCS-1588, for capacitor usage. He warns that nei-
ther is fire resistant although they have much better
environmental characteristics. Their degradation is
more rapid and their accumulation potential in the
environment is considerably reduced. Occupational
and environmental health considerations indicate a
better product with lower acute toxicity. He also
announced that they do have candidates with inter-
mediate fire resistance between PCB's and mineral
oil, but did not elaborate on this further.
Dr. Dean Branson from Dow Chemical Com-
pany announced a substitute for use in power capa-
citors. This compound is called XFS-4169L and is a
butylated monochlorodiphenyl oxide. Once again
we find that a substitute is like the original, a chlo-
rinated compound. Its properties are worth noting
however. Dielectric losses are lower or slightly lower
than for capacitor-grade PCB, while the discharge
inception voltage is significantly higher. The size or
volume per unit of high-voltage power factor correc-
tion, called kVAR, is about that of the PCB coun-
terpart, which means that no redesign is necessary
for capacitors. There is little fire and explosion risk
indicated by comparing the flashpoints and fire-
points of PCB and XFS. The flashpoint for PCB is
166° centigrade, for XFS 174°. The firepoint for
PCB is greater than 316° centigrade, while XFS is
199°. This substitute is reported to be more reliable
and is anticipated to have a reasonable long-term
price. The increased expense is estimated to be less
than $20 for a 200 kVAR unit. The capacity in the
first quarter of 1976 should be in the range of 1
million pounds per year, and a multimillion pound
per year volume capability is estimated by the end
of 1976. This substitute is more biodegradable by a
factor of 45 and the bioconcentration is 30 times
less. There is little toxic activity in acute and in
90-day tests, although longer-term tests need to be
carried out. The accumulation in fat is 22 times less.
The toxicity in fish is on the order of 20 times less
than for PCB's.
464
-------
carried out. The accumulation in fat is 22 times less.
The toxicity in fish is on the order of 20 times less
than for RGB's.
Perhaps the most exciting substitute for use in
transformers was announced by Dow-Corning (rep-
resented by Richard Montgomery). He indicated
that the global silicone industry had been looking
for a replacement for the transformer fluid RGB's
for 5 years, and the technology was now developed
for the new fluid. It was to be commercially avail-
able in 1976 and had no known environmental
problems. Commercial production was available to
handle the global market. In the United States there
has been field-testing for 4 years and the product is
now ready to be used. The product is called Q2-10
90 dielectric fluid, and is a dimethyl silicone which
has been used in the military, in Japan, and in a
small experiment in Midland, Michigan. He pointed
out that this was not very dissimilar to "di-gel,"
which is used of course for human consumption. It
is less flammable than many RGB's with low heat of
combustion, high flashpoints and firepoints, and the
product is self-extinguishing in case of ignition by
violent transformer breakdown. Insurance compan-
ies have OK'd the substance for use indoors. The
cost is higher than RGB's but "not outrageous," giv-
ing rise to an estimated cost increase of about 6
percent in the transformer equipment. Of course,
the fluid itself is more expensive, with a higher per-
centage increase in cost. RGB transformers now in
service can be retrofitted and he believes that the
economics are favorable enough to stimulate compe-
tition. It is worthy to note that unlike the trade
industries representing the capacitor users presented
at the conference, there was no transformer user or
producer represented. It would be interesting to see
what General Electric's viewpoint would be on the
potential use for this transformer fluid substitute
since they have the capability to manufacture sili-
cone fluids. Their absence at the meeting might
leave one with an unwarranted optimism for the use
of these fluids in transformers. One further reflec-
tion is that we are badly in need of a frank assess-
ment of flammability risk requirements since the
substitute products vary in their flammability over
the great range between mineral oil and RGB's. It is
not clear what tradeoffs should be made between
the fire risks and the safety risks in the industrial
setting and the possible damage to humans from
substitute products which might get into the envi-
ronment. It is also not clear that PCB's flammability
characteristics should remain the benchmark for
compliance although the insurance industries may
see this differently.
SUMMARY OF SESSION VI
MR. CHRISTOPHER M. TIMM (Environmental Protec-
tion Agency, Region V, Chicago, Illinois): From a
very broad mixture of topics and points of views
that we were listening to last night, I believe the
following four points should be emphasized.
First, on top of all the human health and wild-
life effects that have been documented and thor-
oughly discussed, PCB's are having a definite and
drastic effect on the livelihood and future of the
freshwater fishery and fishermen. This is a very real
problem to the people in various parts of the conti-
nent and they see no improvement in the near
future.
Second, a ban on PCB's and better control of
other toxic substances to protect our natural re-
sources is long overdue. However, the actions of the
regulatory agencies such as EPA and FDA must be
based on scientific fact in the overall impact on the
nation.
Third, universally there is a belief that the
governmental bodies and agencies for whatever
reason are far, far too slow in solving environmental
problems like PCB's. This is a frustration to every-
body.
And finally, there is a need to find some way to
compensate the people like fishermen whose liveli-
hood is impacted by environmental pollution which
is PCB's. They do not cause the problem, they can-
not control the problem, and they often cannot find
anyone to blame or even talk to about it. But they
suffer the consequences of decades of incomplete
evaluations and testing of new compounds. Thank
you.
465
-------
SUMMARY OF SESSION VII
MR. CHARLES N. GREGG, JR. (Environmental Protec-
tion Agency, Washington, D.C.): Because most of
you have heard the discussion this morning, I will
try not to repeat it, but to provide some insights
and perhaps some of the highlights. I will not try to
give equal time to the various speakers.
First, there is an obvious distinction between
physical and technical methods of control, which
have been discussed in other sessions, and the regu-
latory and voluntary actions for achieving those
controls that were discussed by this morning's pan-
el.
Second, there is a distinction between the di-
rect control of human exposures as, for instance,
through limitations on PCB's in fish that can be sold
for human consumption, and limitations on use or
limitations on emissions into the environment,
which in the long run contribute to diminished ex-
posure. In our present situation, as you were told by
the speakers this morning, there are a vast number
of Federal agencies with roles. Our Government and
the Canadian Government both contribute to solu-
tions of the Great Lakes problem. We have a lot of
State Governments with roles to play. One of the
major problems will be sorting out roles, and finding
adequate cooperation in performing those roles,
among the several agencies and units concerned.
A further complication is that both in Canada
and here we not only have a number of regulatory
authorities now, but in each case we are looking for
additional authority which it is anticipated will per-
mit much more finely applied solutions. And at the
same time that we plan for the future, we do not
know for certain what authority we wjll have availa-
ble for use.
One observation I made was that there seemed
to be very little real optimism. If we applied all our
available resources and used all of our authorities as
best we could, .we could solve in any short time
frame the most pressing problem, which appears to
be the high levels in fish in a number of places
where they are caught and consumed in substantial
quantity. This lack of optimism did not, neverthe-
less, suggest to the speakers that we should not take
action. Everybody seemed to agree that it was ap-
propriate to move ahead as best one could with the
full range of authorities and voluntary programs
available.
Also, there was considerable emphasis on non-
regulatory action, and increasing communication
with people who have the opportunity to affect the
flow of PCB's first from industrial situations into
the environment and thereafter within the environ-
ment to locations where they can lead to higher
human and environmental exposures. In my view, a
voluntary program seems to present a very great op-
portunity for improvement, perhaps much greater
than a strictly regulatory program in the light of
some of the difficulties experienced in using our
current authorities.
Relatively less, it seemed to me, was said by
this morning's speakers about just how to control
PCB's, particularly how to control, through regula-
tion, those PCB's which are currently in industrial
use or elsewhere in products but not yet released
generally to the environment. There was some refer-
ence to controls over disposal, but to my best recol-
lection, there was no indication that we had any
directly applicable authorities with respect to dis-
posal.
Let me touch on a couple of this morning's
highlights. Dr. Ahmecl of the MRDC asserted that
the government had failed to carry out its responsi-
bilities adequately, particularly under Section
307(a) of the Federal Water Pollution Control Act.
He felt that we had a schedule on which we should
have produced regulations a couple of years ago,
with compliance a year ago, and he criticized EPA's
lack of attention and priority to toxics in our Water
Pollution Control program. He made several recom-
mendations: a phaseout of the manufacture and use
of PCB's, a ban on exports and imports, develop-
ment of an inventory of point sources, additional
monitoring in fish and elsewhere, a moratorium on
river bottom dredging until we have better indica-
tions of the trouble we stir up, effluent standards
that would allow us to arrive at 1 ppt in water,
lower FDA tolerance levels, and the passage of the
Toxic Substances Control Act.
Mr. Wessel of the Food and Drug Administra-
tion referred to its action in 1972 and 1973 to set
tolerance levels, indicating that various concerns had
to be balanced in setting levels under Section 406 of
the Food, Drug, and Cosmetic Act. He indicated
that FDA was examining the current tolerance level
in fish and considering whether or not to lower it.
He said that there would be adequate opportunity
for public comment on any proposal that was made.
But he felt that this would not solve the PCB prob-
lem and it would not necessarily prevent consump-
tion of fish with high levels of PCB's by private
fisherman.
466
-------
Dr. Kolbye of FDA added a discussion of some
of the problems in setting tolerance levels, and
something else I thought was significant: that steps
are particularly needed to identify where PCB's are
located so we can look to their proper disposal, and
education to this end is needed. He did feel that the
average consumer is fairly well protected against
PCB's by the current tolerance level, but acknowl-
edged that there would be higher exposures in some
cases and that this was not a concern to pass over
lightly.
Mr. Barber of the Environmental Protection
Agency, after talking about some of our authorities
and programs we have undertaken so far, gave con-
siderable attention to some of the realities involved
in EPA decisionmaking: the complexity and impli-
cations of taking various regulatory courses, and the
fact that there are limited resources in EPA, particu-
larly people, to handle a wide array of regulatory
responsibilities. He pointed out the importance of
the State role, and indicated that the Federal Gov-
ernment's role can best be viewed as one way of
encouraging the State to find ways to perform a
great deal of the regulatory and enforcement activi-
ty. He felt that regulation must represent some sort
of consensus and be enforceable in order to be pro-
ductive. He felt that a number of PCB problems
were difficult to control because of the numbers of
nonpoint sources.
He urged that we try tor more awareness among
the people who use PCB's, particularly the utilities,
and suggested voluntary labeling and use of the
planning process under Section 208 of the Federal
Water Pollution Control Act.
Secretary Reed described both the environmen-
tal problem caused by PCB pollution and the result-
ing fisheries resource problem. High investment in
restoring the Great Lakes fishery and future invest-
ment in this and other fisheries would be hard to
justify unless we can control the PCB situation. He
suggested particularly that since we find great reduc-
tions in DDT and mercury as a result of regulation,
it would certainly be worth a try to see if we can
reduce PCB levels in the water and in fish by taking
all of the regulatory steps we now can. He endorsed
the Toxic Substances Contro4 Act, and suggested we
cut off the importation of PCB's.
Dr. Rhoden outlined the plans of NIOSH.
Mr. Billy of the Marine Fisheries Service indi-
cated their environmental, consumer, and public
information concerns. They recommend not lower-
ing the FDA level until there has been a sound at-
tempt to understand the course to be followed, and
the avoidance of unproductive and unnecessary ad-
verse publicity.
Mr. Grella of DOT briefly described their incipi-
ent program to apply DOT authorities to PCB's,
though not much has yet been done.
The Coast Guard has a number of functions
under the Federal Water Pollution Control Act in
the event of, spills, but the Coast Guard representa-
tive told us that until we in EPA have designated
PCB's as a hazardous substance, the Coast Guard is
unable to go forward to use its authorities. He urged
public awareness of the needs for good handling and
precautions in transportation.
Dr. Millson of the Canadian Government urged
a systematic approach, and outlined six regulatory
control packages that Canada was considering. He
emphasized that Canada does not have a use control
act yet, but that such authority together with their
other authorities would permit them over some peri-
od of time to do a great deal about controlling
PCB's.
Since Dr. Highland spoke last, and I have
exhausted my time, with apologies to him I hope
you remember what he said.
467
-------
CONFERENCE HIGHLIGHTS
Richard A. Carpenter*
A summary of this complex and comprehensive con-
ference may be more useful if the information is orga-
nized in the format shown in the accompanying figure
(figure 1). The presentations have dealt with three gen-
eral topics:
A. The occurrence of PCB's in the environment-
sources, rates, routes, and sinks;
B. The toxicity of PCB's—inadvertent human
exposure, laboratory animal experiments, wild-
life, fish, and ecosystems;
C. The uses and benefits of PCB's to industrial
society and the possibilities of control.
to:
In each topic, information can be characterized as
1. What is known and generally agreed upon with
a reasonable degree of confidence.
2. Remaining uncertainties and the reasons why a
lack of understanding continues. Science is
probabilistic in nature and this concept of
uncertainty must be recognized when technical
information is used in deciding issues of public
policy.
3. Finally, the conference discussions have sug-
gested some courses of action which are pru-
A.
Occurrence in the
Environment
B.
Toxicology
C.
Uses, Benefits
and Control
1.
What is known
2.
Remaining
Uncertainties
3.
Prudent Actions
Figure 1. Organization of information about polychlorinated biphenyls.
"Executive Director, Commission on Natural Resources,
National Research Council, Washington, D.C.
468
-------
dent, i.e., could and should be set in motion.
These include setting priorities for obtaining
more information and reducing uncertainties
through additional research and monitoring.
The conference was not designed to produce con-
sensus judgments or to make recommendations. Thus,
the following summary must be viewed as the responsi-
bility of the author alone.
A-1. What is known about the occurrence of PCB's in
the environment
We have learned what should have been apparent
from the start—that any persistent, mobile, and foreign
or exotic compound is going to be detected everywhere
in the environment. In addition to current production
and uses, which may result in leaks, a nonpoint source
situation exists in that about 400 million pounds of
PCB's are already discarded in the environment and sub-
stantial amounts are apparently recirculating in sludge,
sediments, in air and dust, and in contaminated orga-
nisms.
There are about 300 million pounds in industrial
service and this material will be difficult to contain com-
pletely as it moves toward disposal. The sediments in
lakes, rivers, and estuaries provide a very large reservoir
of PCB's for contacting aquatic organisms. The material
in dumps (three-fourths of the total discarded) appears
to stay there for the most part. Current processing losses
are important and can be decreased.
Eventual removal is to sediments in the deep ocean
and we need to know more about the fate of this mate-
rial in the marine environment.
It is too early to see the effects of the 1972 volun-
tary action to limit uses to nondispersive applications,
but certainly it was a justified decision and a move in the
right direction.
There will be occasional catastrophic spills which
can cause substantial damage to fisheries in the future.
These will be localized impacts, and will be costly to
clean up.
Incineration is an effective method of destroying
PCB's if the temperature is high enough (i.e., about
2,700° F).
Analytical procedures now give confidence that we
can measure PCB's qualitatively and quantitatively down
to a few parts per trillion.
A-2. Uncertainties about PCB's in the environment
There is a real question as to whether the PCB con-
tent of the waters of the Great Lakes (particularly Lake
Michigan) can be lowered by any degre, of tightening-up
of the current use situation, because of the recirculating
contamination that is already there. There is the ques-
tion as to the role of air transport and the recirculation
of material that is deposited in rain or in dust back into
the air so that it is continually redistributed around the
world. The composition change of PCB's in the environ-
ment with aging is not well understood; there are ques-
tions as to their chlorine content changing and regarding
formation of diobenzofurans.
We need a mass balance and a model for transport
and removal in order to estimate the time that will be
required for these materials to eventually move to an
ultimate sink in the deep ocean sediments.
A question has been raised as to the possible conver-
sion of these materials into higher chlorinated com-
pounds during sewage chlorination.
We need to know more about the presence of the
materials in whole water; i.e., are we measuring material
on suspended sediments, in very small organisms, in
micelles, or actually dissolved in water? We need to
know about the biological activity of these various forms
of occurrence of PCB's in water.
A-3. Prudent actions
What can we do based on this information and
uncertainty? We can separate, to some extent, the prob-
lem of what is already in the environment from the con-
trol of material that has not yet been released. Even if all
manufacture and use were stopped immediately, envi-
ronmental contamination would remain for some time
to come. The PCB problem should be considered in the
context of other halogenated hydrocarbons in the envi-
ronment and it should not be separated from investiga-
tion and control of the residues of pesticides and other
halogenated materials. Work should begin on a more
systematic monitoring system and on the use of indica-
tor organisms, such as the suggested "mussel watch," on
a worldwide basis.
We can use some ingenuity in devising means of
cleaning up contaminated water. This problem is of a
magnitude that allows one to think about filtration or
adsorption concepts for waters that are somewhat con-
fined.
Ingenuity may suggest ways to make contaminated
fish suitable for use in animal feeds or human consump-
tion. Perhaps segregation of certain organs or particular
methods of cooking would serve this purpose, or some
other way of decontaminating these valuable animals
might be found.
B-1. What is known about toxicity
The Yusho incident proved the toxicity of used heat
transfer fluid to humans at a concentration in cooking
oil of about 1,000 ppm of PCB's. But interpretation of
this incident is confounded by dibenzofuran contamina-
469
-------
tion of the PCB fluid. Industrial hygiene experience is
somewhat reassuring as to toxicity to humans except
that the occasional symptoms and illnesses cannot be
related to known exposure doses in most instances. The
good housekeeping practiced by some large users and the
American manufacturer will probably be better than
that of the variety of secondary users. No human deaths
have been caused directly, but reports of serious illness
and persistent skin problems continue.
Exposure of the general public can be controlled by
avoiding food (mainly fish) contaminated with PCB's.
Exposure from environmental contamination or direct
-introduction into humans is unlikely. Averages for die-
tary intake can be misleading since some persons may
eat large quantities of fish.
Laboratory animals show effects when fed diets
containing contamination levels found in fish. Fish are
affected at the range of PCB levels found near industrial
outfalls into ambient waters, and the occurrence of fin
rot in fish near these "hot spots" is a direct confirmation
of laboratory tests as to the effects on fish.
Ecosystem simplification (fewer species and lower
populations) has been found in laboratory experiments
to occur at concentrations similar to those in hot spots
in natural ambient waters and could be expected to be
found at sludge disposal sites. It is hard to find evidence
of damage to terrestrial ecosystems. Biomagnification,
i.e., the ratio of the PCB content in aquatic organisms to
that of the water in which they live, can be as high as
several hundred thousand.
B-2. Uncertainties as to toxicity
There is confusion over the interpretation by patho-
logists of organ damage. It would be helpful if the highly
technical problems of ascertaining carcinogenicity could
be worked out by those scientists involved apart from
the complexity and emotionalism of a specific issue such
as the PCB problem. The effect of dibenzofurans, which
may be present as impurities or as metabolites, is still in
question.
There is a great variation as to the response of dif-
ferent species in laboratory animal tests. The range of
sensitivity is large. More needs to be known as to wheth-
er the reproductive problem is the most important ef-
fect. Fat metabolism is not well understood and since a
great proportion of the human population is carrying
around a few ppm of this material, we need to know
more about it.
Wildlife toxicity data is poor and we need to know
which wildlife species may react as do chickens and
mink.
The relationship of toxicity to chlorine content of
the PCB's is uncertain. Is the ability to metabolize these
compounds (which varies with the chlorine content)
desirable or not? The possibility of dioxin as a degrada-
tion product has been raised. We need to know about
the equilibrium distribution of these materials between
fish and water. Is it possible that depuration can be a
help? Are PCB's further accumulated up the food chain
after the biomagnification from water to the first orga-
nism?
B-3. Prudent actions based on toxicity knowledge
Certainly more experimental work in animals and
careful replication of reported tests are necessary. Prior-
ity should be given to chronic tests in various species,
detection of behavior change in animals, and laboratory
work at true environmental levels, rather than to greatly
increased levels of dose. Obviously it is of great impor-
tance to determine unequivically whether the PCB mate-
rials are carcinogenic.
We need to coordinate this work with experiments
and observations on other halogenated hydrocarbons,
particularly the chlorinated hydrocarbons, and to look
at combined effects on organisms, communities, and
ecosystems.
NIOSH should extract the maximum from industrial
hygiene data because these human exposures do not
necessitate the inferences from animal tests to human
toxicology.
The widespread occurrence of PCB's in the environ-
ment constitutes an inadvertent experiment on human
populations and the biosphere. A concerted effort at
monitoring and analysis is indicated in order to gain the
most useful knowledge for further decisions concerning
toxic substances at low levels in the environment.
C-1. What is known about uses, benefits, and control
problems
We know that about 700 million pounds of PCB's
have been manufactured, but the current annual produc-
tion volume is down to 40 million pounds from an 80
million pound level in 1970. About one quarter of pres-
ent production is going into small capacitors that are
scattered very widely throughout our industrial society.
The fire retardant benefits of PCB's are real and
important. An abrupt change in the availability of PCB's
would be disrupting, but that is unlikely in any event.
The estimate of 76 months to reach an end to manufac-
ture if the Toxic Substances Act existed today suggests
that industry will have a substantial transition period.
Forty-five years of use has imbedded PCB's in U.S.
industrial practice and it will be costly to replace these
unique materials. Alternative dielectric fluids are on the
way, but will not be suitable as replacements in existing
transformers.
470
-------
C-2. Remaining uncertainties
The decision by Japan apparently to move further
to eliminate these compounds is a real challenge in the
public mind to the regulatory policy of the United
States. If that Nation can do without RGB's, why cannot
we?
Is a total ban worldwide necessary in order to re-
duce and eliminate contamination to the North Ameri-
can environment? An inventory of PCB's in existence is
required and this must be international. We need to
know more about the changes in PCB's in use, i.e.,
dibenzofuran formation. How nondispersive are "clos-
ed" electric systems?
We need to reconcile the differences in human food
tolerance limits as established by the United States (5
ppm) and Canada (2 ppm) and in alternative proposals
from various protagonists on all sides of that question.
Cost/benefit analysis will not be very helpful in the
PCB contamination problem because of the great num-
ber of subjective judgments and different value systems
involved in arriving at a balance. In any event, the margi-
nal costs and the marginal benefits are what must be
determined.
We need to know how to remove PCB's from waste-
water, i.e., what would be best practicable technology
economically achievable in order to get to an effluent
standard, and whether that should be 5 ppb, or zero, or
what level. We need to know whether 1 ppt is a reason-
able ambient water standard in view of the large bio-
magnification factor.
C-3. Prudent actions
EPA has a responsibility to determine priorities and
it needs to review the PCB issue in terms of the total set
of pollution problems and the agency's resources. EPA
should proceed with effluent standard possibilities in
Section 307 of the Water Quality Act (PL 92-500),
although such action may end up in court tests. The
Endangered Species Act may be a means of cooperative
action by other Federal agencies.
Voluntary housekeeping by industry can be in-
creased to a substantial extent, but this requires special
attention to the weakest firms, always a problem with
voluntary cooperation.
Payment of compensation to fishermen may require
an act of Congress similar to the experience with hepta-
chlor in milk some years ago.
It is my personal opinion that the inadvertent and
unavoidable addition of PCB materials to foods could be
covered by the Delaney Clause if they are found to be
carcinogenic in appropriate animal tests.
This conference has addressed a real problem and
was not just a demonstration of the prowess of analyti-
cal chemistry. However, as with any environmental man-
agement issue, the PCB problem must be put in perspec-
tive.
PCB's will be in the environment for a long time.
Fisheries resources in some of the Great Lakes and rivers
have been lost. We can protect against any imminent
hazard to human health. Ecosystems are resilient but
local damage has occurred. Further leaks from the
industrial system must be prevented. Internalizing costs
will lead the market to produce replacements for PCB's.
Human health is most important but environmental
quality is a reflection of the ecosystem that we all share.
In this case there may be a coincidence, in that if we
protect human health adequately, we will have protected
the environment.
All elements of society are in this together and
recriminations are not very helpful. Scientists and engi-
neers can generate and deliver information for rational
enforcement decisions, searching for equity as the inevit-
able tradeoffs are made. Verified technical facts and
their implications must be communicated efficiently to
the public through education and information programs.
Most importantly, we must use our ingenuity in solving,
little parts of the problem when they are all that can be
solved as well as in working on an ultimate solution for
the problem as a whole.
471
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/6-75-004
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
National Conference on Polychlorinated Biphenyls
(November 19-21, 1975, Chicago, Illinois)
5. REPORT DATE
March 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Franklin A. Ayer (Compiler)
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Center for Technology Applications
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina
10. PROGRAM ELEMENT NO.
27709
11. CONTRACT/GRANT NO.
68-01-2928
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
Environmental Protection Agency
Washington, B.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Proceedings Nov.
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer - Thomas Kopp
16. ABSTRACT
The objectives of the conference where to bring together the latest data and
best available expertise to help clarify the problems associated with the
manufacture, use and disposal of PCBs ... help assess the effectiveness of steps
taken to reduce the problems associated with PCBs ... provide a platform for
interested parties to present previous neglected data concerning PCBs ... help
clarify the feasibility and complications of steps to reduce the problems
associated with PCBs.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Polychlorinated Biphenyls (PCBs)
PCB Health Effects
PCB Human Exposure
PCB Uses, Sources, Identification
PCB Environmental Fate
PCB Occurrence
PCB Ecological Effects & Exposure
PCR F^nnnrnjps ana Substitutes
3. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (9-73)
-------
------- |