COM-72-10419
Pnlychlorinated Biphenyls
and the Environment
Interdepartmental Task Force on PCBs
Washington D.C.
May 1972
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
ITF-PCB-72-1
4, Title and Subtitle
PCBS AND THE ENVIRONMENT
3. Recipient's Accession No.
COM-72-10lil9
5- Report Dace
20 Mar. 72
6.
7, Author(s)
8- Performing Organization Rept.
No.
9. Performing Organization Name and Address
Interdepartmental Task Force On PCBs
10. Projeci/Task/Work Unit No.
11. Contract/Grant No.
12. Sponsoring Organization Name and Address
Departments of Agriculture, Commerce, Health, Education, and
Welfare, and Interior; and Environmental Protection Agency;
plus other participating agencies.
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
16. Abstracts
This report is the product of a six month review of the chemicals known as PCBs--
polychlorinated biphenyls--by five Federal agencies, with participation by other
agencies. The Interdepartmental Task Force on PCBs had as its goal the coordination
of the scientific efforts of the Government aimed at understanding PCBs and the
strengthening of the Government's ability to protect the public from actual or
potential hazards associated with them. The task force made nine findings, con-
clusions, and recommendations, primarily pointing out that PCBs should be restricted
to essential or nonreplaceable uses which would minimize the likelihood of human
exposure or leakage to the environment. Supplementing the 20-page report are eight
appendices detailing current knowledge about various aspects of PCBs, including
their use and replaceability; occurrence, transfer, and cycling in the environment;
occurrence and sources in food; and PCBs effects on man and animals.
17. Key Words and Document Analysis. 17o. Descriptors
•fcPollution,
•^-Chlorine aromatic compounds,
•«-Biphenyl/chlor o,
Environmental surveys,
Insulating oil,
Economic factors,
17b. Identifiers/Open-Ended Terms
Government policies,
Toxicology,
Public Health.
17c. COSAT1 Field/Group -, ,g f™
18. Availability Statement
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21- No. of Pages
192
22. Price
PC $6.00
FORM NTIS-a9 IHEV. 3-72)
TJSCOMM-DC 14032.P72
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Table of Contents
Page
PREFACE 1
FINDINGS, CONCLUSIONS, AND RECOMMENDATIONS 2
I. PRODUCTION, DISTRIBUTION, AND USE OF PCBs $
II. CHEMICAL AND PHYSICAL PROPERTIES AND
IMPURITIES 10
III. BENEFITS, UTILITY, AND ESSENTIALITY 11
IV. OCCURRENCE, TRANSFER, AND CYCLING IN THE
ENVIRONMENT Ill
V.A. BIOLOGICAL EFFECTS ON MAN (METABOLISM, TOXICOLOGY,
AND RESULTS OF HUMAN EXPOSURES) 17
V. B. BIOLOGICAL EFFECTS ON ANIMALS OTHER THAN MAN 18
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Table of Contents: Appendices
Contents and Authors 21
A. Chemical and Physical Properties of PCBs , 22
B. Use and Rep lace ability of PCBs hi
C. The Need for Continued Use of PCBs as Electrical
Insulating Liquids 75
D. Occurrence, Transfer, and Cycling of PCBs in the
Envir onment 93
E. Occurrence and Sources of PCBs in Food 107
F. Human Directed Aspects of PCBs 122
G. Biological Data on PCBs in Animals Other Than
Man 158
H. Regulatory Action on PCBs 173
11
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Table of Contents (Continued)
Figures
Page
Chapter I
1. U. S. Domestic Sales of PCBs by Grade 8
2. U. S. Domestic Sales of PCBs by Category 9
Appendix A
1_6. Chromatograms of various representative
PCBs, according to Armour 31-36
Appendix F
1. Storage of PCB-Derived Material in Tissues _._
and Plasma
2. Excretion of PCB and PCB-Derived Material -.,..
in Feces and Urine
Tables
Chapter I
1. PCB Manufacturing and Sales
Data From Monsanto Industrial Chemicals Co.
1957 Through 1971 6
Chapter III
1. Underwriters' Laboratories Flammability ,»
Ratings
ill
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Tables
(continued) Page
APPENDIX A
1. General Physical Properties of the Aroclor
Clorinated Compounds 26
2. Relative Retentions, Mass Spectrometric
Data on PCB Fractionated Sample 30
APPENDIX B
1. Typical Properties of Liquids k5-k6
2. Physical and Other Properties of Lubricating
Oils , Engine Oils , and Hydraulic Fluids ............ hl-50
3. High-Temperature Lubricant Specifications
14. Some Properties of Pumping Fluids
5. Decomposition Temperature Ranges of Several
Chemical Classes ................................... 60
6. Approximate Maximum Compatibility, phr, of
Plasticizers With Various Resins ................... °1
7. General Properties of Some Aroclor s (PCB) .......... 6 3
APPENDIX C
1. Composition of Different Liquid Chlorinated
Biphenyls .......................................... 77
2. Underwriters' Laboratories Flammability Ratings ?6
3. Alternate Insulating Fluids ........................ 80
IV
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Tables
(continued) Page
APPENDIX D
1. PCB Manufacturing and Sales
Data From Monsanto Industrial Chemicals Co.
1957 Through 1971 85-86
2. Concentration of PCBs in Municipal Sewage
Treatment Plant Outfalls 88
3. PCB Concentrations in Industrial Effluents ........ 89
h. Total Estimated Contribution of PCBs to the
Aquatic Environment ............................... 90
5. Concentration of PCBs in Sewage Sludges ........... 91
6. A Sampling of Measured Occurrences of PCBs
in the Environment . ............................... 93-98
7. Accumulation of PCBs by Various Aquatic
Or ganisms .........................................
APPENDIX E
1. Positive Analyses of Random Food Samples .......... HI
2. Positive Follow-Up Investigate onal Samples ........ H2
3. Summary of PCB Findings in FDA Total Diet
Sample s ........................................... 117
h. Objective Samples - CY 1971 For PCBs .............. 120
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Tables
(continued) Page
APPENDIX F
1. Subjective Symptoms Complained by Yusho
Patients .............................................. 126
2. Oral Toxicity of Chlorinated Biphenyls ................ 12?
3 . Dermal Toxicity of Chlorinated Biphenyls .............. 128
h . Vapor Exposure Toxicity of Chlorinated
Biphenyls ............................................. 129
5 . Toxicity of Aroclors .................................. 131
6 . Pathologic Changes Induced by PCBs ................... 132-133
7. Residues in Tissues of Rats Orally Dosed With
Aroclor 125b (500 mg/kg) .............................. 13k
8. Storage of Aroclors (in PPM) 2ij-Hours After Oral
Ingestion by Stomach Tube ............................. 138
9. Distribution of PCB-Derived Material Following
98- Day Exposure to a Dietary Level of 1000 PPM
Aroclor 12$k .......................................... 139
10. Distribution of PCB Levels in Adipose of General
Population as Shown in Analysis of Human
Monitoring Survey Samples Since April IS, 1971 ........
11. Experiments to Date Not Included in the Manuscript
"Polychlorina ted Biphenyls: Distribution and
Storage in Body Fluids and Tissues of Sherman Rats"-
A. Curley, V. W. Burse, M. E. Grim, R. W. Jennings
and R. E. Linder
12. Some Biological and Toxicological Effects in the
PCBs .................................................. 153
13. Possible Future Studies Involving PCBs, Their
Individual Isomers and Contaminants ......... . .........
vi
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Tables
(continued) Page
APPENDIX H
1. FDA Proposed Temporary Tolerances for PCB
Residues 178
Vll
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PREFACE
On September 1, 1971, representatives of several agencies of the
Federal Government established an interdepartmental task force to co-
ordinate the scientific efforts of the Government aimed at understanding
the family of chemical compounds known as polychlorinated biphenyls (PCBs),
and to strengthen the Government's ability to protect the public from actual
or potential hazards from PCBs. On September 5 it was announced that the
task force would "coordinate a government-wide investigation into PCB con-
tamination of food and other products". On September 13 the task force,
made up of qualified specialists from a range of disciplines, held the first
of a series of meetings. Appropriate spokesmen on various problems assoc-
iated with PCBs were assigned to prepare a series of background papers,
drawing on the resources of their own and other agencies.
The task force included operating units of five Executive Branch depart-
ments: Department of Agriculture; Department of Commerce (Assistant Secretary
for Science and Technology and National Oceanic and Atmospheric Administration);
Environmental Protection Agency; Department of Health, Education, and Welfare
(Food and Drug Administration and National Institute of Environmental Health
Sciences of the National Institutes of Health); and Department of the Interior
(Bureau of Sport Fisheries and l&ldlife).
The report which follows represents the results of the task force's re-
view and reflects the position of the operating agencies of the Federal
Government which have major responsibilities concerning such chemicals as
PCBs in food and in the environment. The task force had the advantage of
some additional sources of information and review on PCBs. For example, dur-
ing the course of the study, the National Institute of Environmental Health
Sciences sponsored an international scientific meeting on PCBs on December
20-21, 1971, at the Quail Roost Conference Center, Rougemont, North Carolina.
One hundred persons — from Government, universities, industry, and the press--
attended. The proceedings of this conference soon will be published by the
Institute. The task force also met from time to time with a group of scienti-
fic advisors from outside the Federal Government, which was already at work
prior to September 1971 examining a number of hazardous trace substances, one
of which was PCBs.
The individuals who served on the task force included: Dr. John E.
Spaulding and Dr. Harry W. Hays (Department of Agriculture), Dr. Robert W.
Cairns and Dr. William Aron (Department of Commerce), Dr. John Buckley
(Environmental Protection Agency), Dr. Lawrence Fishbein, John R. Vfessel,
and Dr. Albert Kolbye (Department of Health, Education, and Welfare), Dr.
Lucille Stickel (Department of the Interior), Dr. Edward J. Burger, Jr.
(Office of Science and Technology), and Dr. Terry Davies (Council on Environ-
mental Quality). Many others participated in some of the meetings and lent
assistance in a variety of ways including authorship of background papers
published as appendices in this report. The task force is grateful for this
assistance.
The task force will continue to assess new information that comes to
its attention.
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FINDINGS, CONCLUSIONS, AND RECOMMENDATIONS
Polychlorinated biphenyls (PCBs) have been used in the United States
and elsewhere over the past UO years, for many industrial and consumer
applications. During the past three years evidence has accumulated to
indicate that PCBs are widely dispersed throughout the environment and
that they can have adverse ecological and toxicological effects.
The principal uses for PCB fluids are in the electrical industry.
PCBs have superior cooling, insulating, and dielectric properties and
hence are widely used in various electrical devices. Transformers and
capacitors filled with PCBs can be used in inside locations where fail-
ures of oil-insulated equipment would present a potential danger to life
and property. Because PCBs are relatively nonflammable, apparatus con-
taining them is essentially free from the fire and explosion hazards
associated with oil-insulated and oil-cooled electric devices. Stability
at high temperatures is another major factor in the attractiveness of
these compounds. The principal advantage of PCBs over substitutes is the
relative freedom from flairanability in some applications that previously had
been plagued by serious fires. PCBs also give electrical equipment the
critical advantages of reliabilityx..long life, and compactness. PCB
impregnated capacitors, for example, are markedly more reliable and long-
lived, and 1/6 the size, 1/5 the weight, and 1/h the cost of comparable
oil impregnated capacitors. Small capacitors with PCBs have a use-life
expectancy of 10 to l£ years, and large capacitors 20 to 25 years. PCBs
in transformers are replaced only every 25 to 30 years.
PCBs have been discovered to have a widespread distribution in the
environment, and some environmental occurrences have been associated
with adverse effects on certain forms of animal life. Beginning in 1971,
the Monsanto Company, the sole U.S. producer, has reported taking volun-
tary actions to reduce the volume of PCB production and to limit its
distribution to industries concerned with the manufacture of electrical
apparatus. Similar restrictions have been put into effect by statute in
Sweden and voluntarily in Great Britain.
A large use of PCBs had been in carbonless duplicating paper. This
use has been discontinued. The Food and Drug Administration and the food
industry have increased their surveillance to assure that PCBs are not
used in food plants, products, or packaging.
The task force has reviewed all of the available scientific informa-
tion on various aspects of the PCB problem. It has found much data that
it regards as inadequate and many questions that remain unanswered. But
on the basis of available information, the task force concurs on the
following findings, conclusions, and recommendations:
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1. PCBs should be restricted to essential or non-replaceable uses
which involve minimal direct human exposure since they can have adverse
effects on human health. There currently are no toxicological or ecologi-
cal data available to indicate that the levels of PCBs currently known to
be in the environment constitute a threat to human health, but additional
experiments are underway to evaluate the impact of low level, long-term
exposure to PCBs.
2. PCBs have been used so widely over such a long period that they
are ubiquitous. Even a total cessation of manufacturing and use of PCBs
would not result in the rapid disappearance of the material, and ultimate
disappearance from the environment will take many years. The elimination
of non-essential uses and prohibition of discharges from essential uses
will result in gradual elimination from the environment.
3. PCBs were first identified as potential food contaminants in 1966.
Three principal sources or routes of contamination of food have been identi-
fied. General environmental contamination has resulted in PCB residues in
some fresh water fish. Prohibition of PCB discharges into water will result
in the reduction of such residues. Another route occurs from the presence
in food packaging materials of PCB residues, some of which migrate into
packaged food. The FDA has proposed regulations for food packaging materials
and foods to deal with this problem. The third route involves accidental
contamination of food from leakage or spillage of PCBs into feed or directly
into food. The dietary intake of PCBs is of low order and does not present
an imminent health hazard. To date, all of the high levels of PCBs encountered
in human or animal foods have been associated with accidents, for which Govern-
ment agencies have exercised necessary regulation and control to minimize the
distribution of contaminated foods.
[4. The sole domestic producer of PCBs, Government agencies, and key
user industries are taking appropriate steps to cut off further introduction
of PCBs into the food supply and to reduce the current levels of PCBs as food
and environmental contaminants. The Food and Drug Administration (FDA) has
acted, under the authority of the Food, Drug, and Cosmetic Act, to preclude
the accidental PCB contamination of food. It has also proposed a prohibition
on the use in food packaging materials of pulp from reclaimed and salvaged
fibers that contain poisonous or deleterious substances that may migrate into
the food if the contamination by such substances is deliberate or avoidable.
It has proposed temporary tolerances for unavoidable PCB residues in food
packaging materials and in certain foods. The Department of Agriculture has
acted under the Wholesome Poultry Act and other statutes to prevent accidentally
contaminated foods from reaching the market.
The major gap in the regulatory system to deal with PCBs is the absence
of any broad Federal authority to restrict use or distribution of the chemical,
to control imports, and to collect certain types of information. The task
force believes that such authority is needed. This authority would be provided
by the Toxic Substances Control Act proposed by the Administration and now
pending before Congress.
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5- Housekeeping is particularly important in the manufacture, use,
and disposal of PCBs. Under a program of limitation on the sale of PCBs,
the electrical industry will continue to be the principal user of PCBs;
it, as well as industries now holding inventories of PCBs, have a special
responsibility for monitoring and controlling their wastes. In this con-
nection, the Environmental Protection Agency will restrict industrial
liquid discharges of PCBs from PCB users. To keep levels in fish as low
as possible, and in any case below FDA's interim action level of 5 parts
per million, concentrations in rivers or lakes from all sources should
not exceed 0.01 parts per billion.
6. The use of PCBs should not be banned entirely. Their continued
use for transformers and capacitors in the near future is considered
necessary because of the significantly increased risk of fire and explos-
ion and the disruption of electrical service which would result from a
ban on PCB use. Also, continued use of PCBs in transformers and capaci-
tors presents a minimal risk of environmental contamination. The Monsanto
Company, the sole domestic producer, has reported voluntarily eliminating
its distribution of PCBs to all except manufacturers of electrical trans-
formers and capacitors.
Pending passage of the Toxic Substances Control Act, the Federal
Government does not have the legal authority to impose restrictions
corresponding to the actions reported by Monsanto. Although some Federal
enforcement authority is available, the Federal Government does not have
the authority to control PCBs at their source.
7. Most capacitors presumably have been disposed of in landfills.
PCB containing material buried in soil is not expected to migrate but
should remain in place. In the past, many fluids containing PCBs have
been disposed of in sewers. More appropriate means of disposal such as
high-temperature (at least 970°C) incineration must be used instead.
8. PCBs are manufactured in countries other than the United States.
Importation of PCBs as a chemical or as a component in products remains
legally possible because the Toxic Substances Control Act has not yet
become law. Electrical products imported from abroad may contain PCBs.
The task force looks to international agreements to bring about some
multi-national understanding on the sale and use of PCBs globally. Im-
portation of PCBs for uses other than those singled out in the present
pattern of voluntary limitations should be avoided by users.
As an additional measure, the United States has asked the Organization
for Economic Cooperation and Development (OECD) through its Environment Com-
mittee to make a special review of member states' national policies concern-
ing PCBs and also to identify products moving in international trade which
contain PCBs. OECD, whose membership includes all major Western industriali-
zed states plus Japan and Australia, has been giving priority attention to
the problem of PCBs over the past year.
9. More scientific information about PCBs is needed, and several
Coverrment agencies are seeking it through research. The task force
recognizes that the scientific basis of much of our knowledge must be
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strengthened through research. The total exposure of a human being to a
given substance from all sources--air, water, and food—must be considered,
and interactions of PCBs and other substances within and outside the body
must be evaluated. Similar consideration must be given to the other body-
organisms .
Current scientific knowledge gained from laboratory animal experiments
is often inadequate to allow reliable interpretation of the data in terms
of possible effects on man. The scientific basis for interpreting such
tests must be improved.
The situation regarding PCBs is not significantly different from the
problem of other toxic susbstances which cause concern when they come into
contact with man, his foodj and his environment. Continuing vigilance on
the part of Government agencies, industry, universities, and many other
agencies both within and outside the Government will be necessary to achieve
an effective system for assessing and controlling the hazards of toxic sub-
stances, including PCBs.
The task force, by reviewing research needs and the present Federal
research effort, has helped to insure that these efforts of the agencies
are well planned and coordinated. Certain Government laboratories as well
as a number of non-Government scientists recently have embarked on additional
research on PCBs, and the results will be communicated to the scientific
public completely and promptly through normal channels such as meetings and
journals.
I. PRODUCTION, DISTRIBUTION, AND USE OF PCBS
Polychlorinated biphenyls (PCBs) were first manufactured commercially
in 1929. By virtue of their unusual chemical and physical properties, they
achieved widespread use in a variety of applications. PCBs are now manu-
factured in Great Britain, France, Germany, the USSR, Japan, Spain, Italy,
and Czechoslovakia, as well as in the United States.
In the United States, PCBs have been manufactured by a single producer,
the Monsanto Company, and marketed under the tradename "Aroclor". Table 1
gives a breakdown, by category of use and by type of PCB, of the total U. S.
production, domestic sales, and U. S. export sales from 1957 to the present.
Figure 1 and Figure 2 summarize these data for the years 1963 through 1971.
Both production and domestic sales of PCBs roughly doubled between
I960 and 1970. If one assumes a constant rate of growth of domestic sales
since 1930, the cumulative sales in North America by 1970 would be of the
order of 500,000 tons, (l) Corresponding data on production and use of
PCBs outside the United States are not available. Current estimates suggest
that total TJ. S. production represents roughly one-half of the total world
production.
As can be seen in Table 1, the majority of the PCB material produced
in the U. S. was marketed domestically. Between 1963 and 1971, the pro-
portion of the production which was exported averaged 13 percent. In 1971,
the Monsanto Company reportedly undertook a variety of voluntary restrictions
on the distribution of PCBs to various categories of industries. Both
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TABLE 1
PCB MANUFACTURING AND SALES
DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO.
1957 THROUGH 1971
(Thousands of Pounds)
TOTAL PRODUCTION
(For Domestic Sales
DOMESTIC SALES
1957
32299
1958
26061
1959
31310
DOMESTIC SALES BY CATEGORY
Heat Transfer
Hydraulics/Lubricants
Misc. Industrial
Transformer
Capacitor
Plasticizer Applications^2'
Petroleum Additives
Total
1612
7014
12955
17028
32299
151*9
755
5719
11*099
3939
26061
2685
1569
59814
161499
1*573
31310
2523
1559
7921
16967
621,14
U110
21114
6281
15935
9098
157
3915
1681
798U
15382
89214
3BOH3
DOMESTIC SALES BY PCB GRADE
Aroclor 1221
Aroclor 1232
Aroclor 121,2
Aroclor 121*8
Aroclor 12514
Aroclor 1260
Aroclor 1262
Arcolor 1268
Total
23
196
18222
1779
1*1*61
7587
31
-
32299
16
113
101*1*14
2559
6691
5982
18 li
72
26061
25^
2140
13598
6751*
6619
359
102
31310
103
155
18196
2827
6088
7330
326
189
35211*
91*
19827
1*023
6291*
65UO
361
158
37538
HO
2065U
31*63
6325
6595
1432
210
380143
NOTE: (l) Production amounts prior to I960 are not available.
(2) Amounts for plasticizer applications prior to 1958 are not available.
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TABLE 1 (cont.)
1963
1961*
U.S. PRODUCTION
DOMESTIC SALES (LBS.)
U.S. EXPORT SALES
1*1*731* 50833
38132 1*1*869
361*7 1*096
1965 1966 1967 1968 1969 1970 1971
601,80 6581*9 75309 82851* 76387 85051, 1,01,71
51796 59078 621,66 65116 67191* 73061 37635
1*231* 6852 8121* 11231 10621, 13651 9876
Prospect
1972
25-30 m
25-30 m
U.S. DOMESTIC SALES BY
CATEGORY
Heat Transfer
Hydraulics/Lubricants
Misc. Industrial
Transformer
Capacitor
Plasticizer Applications
Petroleum Additives
582 929
391*5 1*371*
1528 1692
7290 7997
15606 1951*0
9181 10337
1237
1*616
181*1
8657
2371*9
11696
1766
1*258
1779
8910
28881*
131*81
2262
1*61*3
11,26
11071
29703
13361
2529
5765
1283
11585
29550
11*1*01*
3050 3958 31*80
8039 71*03 161^3
1079 1627 578
12105 13828 11528
25022 26708 17305
I6ii60 19537 3102
25-30 m
25-30 m
U.S. DOMESTIC SALES
BY PCS GRADE
Aroclor 1221
Aroclor 1232
Aroclor 12ij2
Aroclor
Aroclor
Aroclor 1260
Aroclor 1262
Aroclor 1268
361
13
18510
5013
5911
7626
1*11*
596
13
23571
5238
6280
8535
190
369
7
31533
5565
7737
5831
558
196
528
16
39557
5015
7035
5875
768
25
1*3055
1*701*
6696
61,17
81*0
287
136
90
8891
5252
720
280
507
273
1,51*01
5650
9822
712
300
11*76 1600
260 211
1*8588 21000
1*073 261
121*21 5800
1*890 1750
1023
330 -
300
300
ItOOO
6000
600
-------
75,000
00
_Q
CO
CO
LU
_l
-------
00
_Q
00
o
CO
LU
_J
o
75,000
65,000
55,000
45,000
?5,000
25,000
15,000
5,000
Total
—— Misc. Industrial
-L
I9H7
YEAR
FIGURE2, US DOMESTIC SALES OF PC3s
U3T6pOPy (fhe uppermost curve represents the total sales.)
From Nisbet, I.C.T., and Sarofim, A.F. (I)
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production and sales figures for 1971 were roughly half of those for 1970,
when these volumes were at their peak (Table 1 and Figures 1 and 2). Pro-
jections for 1972 indicate an even lower volume.
Prior to 1971, about i»0 percent of the PCB material in the United
States was used in applications where containment was difficult and losses
into the environment were probable. These uses included plasticizers, hy-
draulic fluids and lubricants, surface coatings, inks, adhesives, pesticide
extenders, and microencapsulation of dyes for carbonless duplicating paper.
The remaining 60 percent of domestic sales was used mainly in electrical
applications (transformers and capacitors). In 1971* this fraction is ex-
pected to have reached approximately 90 percent of the total use, only about
half of the total use in 1970.
In terms of the grade or family of PCB manufactured, the lower chlori-
nated species have generally made up the majority of the products produced.
From the figures in Table 1 it can be seen that Aroclor 12li2 and grades with
lower percentages of chlorination characteristically composed one half or
more of the total production between 1963 and 1970.
The largest categories of use of PCBs have been in capacitors and
transformers and in certain "plasticizer" applications including carbonless
duplicating paper. A large percentage of the production of Aroclor 12b2
went into these three categories of products. (2) The major uses for PCBs
prior to 1970 (in the order of importance as a reflection of the volume of
material used) were:
Capacitors
Plasticizer applications
Transformer fluids
Hydraulic fluids and lubricants
Heat transfer fluids
II. CHEMICAL AND PHYSICAL PROPERTIES AND IMPURITIES
Chemical and Physical Properties of PCBs
Theoretically, there are 210 possible PCB compounds, but only about
100 are likely to occur in commercial products. The degree of chlorination
determines the chemical and physical properties of the Aroclors; the first
two digits of the numbered Aroclor represent the molecular type, the last
two digits the average weight percent of chlorine. Their physical state
thus varies from colorless, oily liquids to more viscous and increasingly
darker liquids to, in the higher series, yellow and then black resins.
The PCBs are not readily biodegradable. They resist breakdown by water,
acids, and alkalis and have boiling points ranging from 278 to h75°C.
Analytical Techniques
Whereas in the past it was difficult to identify PCBs in the presence
of other organochlorine compounds such as DDT and DDE, they can now be
separated from interfering compounds and identified and measured by means
of thin layer and gas liquid chromatography at levels less than 1 part
10
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per million in food and at significantly lower levels in air and water.
Confirmation of their presence and molecular structure is possible by mass
spectrometry. Various chromatographic columns and GLC detectors have been
most useful in the analyses. Increased precision of residue detection in
biological materials has also been made possible through the choice of
chlorine specific detectors such as the microcoulometric detectors.
Contaminants and Impurities
The starting materials used in synthesis of PCBs determine to a large
degree the type of impurity or contaminant in the commercial product. The
contaminant variation,, of course, renders some divergence in the LD 50
values or other toxicologic response of the PCBs. Fractionated samples of
some PCBs of foreign manufacture have shown them to contain as contaminants
the tetra- and pentachlorodibenzofurans, the hexa- and heptachloronaphtha-
lenes. Further work is needed to ascertain whether additional impurities or
contaminants are present in the various U. S. and foreign PCB products. Also,
variance in biological response to the various PCB products should be corre-
lated with analytical data obtained on the actual or likely presence of con-
taminants .
III. BENEFITS, UTILITY, AND ESSENTIALITY
fhe task force reviewed the several categories of uses GO which PCBs
had been put in the past to determine what was known of their utility and to
ascertain if alternate or substitute materials were available or whether any
of the present applications were essential.
The four major types of applications examined were:
1. Dielectric fluids for capacitors and transformers.
2. Industrial fluids for hydraulic, gas turbine, and
vacuum pump uses.
3. Heat transfer fluids.
ij. Plasticizers and miscellaneous uses.
This review of utility was undertaken by the National Bureau of Standards.
The review was materially aided by information from the National Industrial
Pollution Control Council and from certain professional Independent testing
and evaluation associations.
A major value of the PCB liquids is that those with four or more substi-
tuted chlorines per molecule are nonflammable as are their decomposition pro-
ducts, both vapors and arc-formed gaseous products. Thus they can be used as
fluids at temperatures up to ?00°F without the danger of explosions and fire.
The major disadvantage of the PCBs is their toxicity and environmental contami-
nation. The other comparable class of non-flammable fluids is the fluoro-
carbons, which typically have a lower vapor pressure and lower boiling point
than the chlorinated compounds.
11
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Electrical Uses
PCBs are used in fluids (known as askarels) for electrically insulating
and cooling transformers when the transformers are used in or near buildings.
Being virtually free of fire and explosion hazards, PCBs can be used where
failures of oil-insulated transformers would present a potential danger to
life and property. PCBs also are superior to oils in reliability, in making
small equipment possible, and in assuring long life and reliability to equip-
ment. Table 1 shows the flammability ratings of two PCBs compared to five
other common materials.
Table 1
Underwriters' Laboratories Flammability Ratings
Fluid Flammability Rating
Ether 100
Gasoline 90-100
Ethyl Alcohol 60-70
Kerosene (100 P.P.) 30-hO
Mineral Oil 10-20
Aroclor 12^2 and MCS 1016 2-3
PCBs are used in transformers wherever fire protection is particularly
important--for about 5 percent of all transformers.
Most of these transformers are located inside public, commercial, or
industrial buildings—or on the roof tops of, or in close proximity to, such
buildings—and require no special enclosures other than those necessary to
prevent accidental hazardous mechanical or electrical contact of persons with
the equipment.
The amount of Aroclor used in various types of transformers ranges from
hO to £00 gallons (£l6 to 6,1^0 pounds) with an average of about 235 gallons
(3,032 pounds). Daring 1968, the last complete "normal" year for the electri-
cal industry, the total amount of PCBs used in new transformers or as replace-
ment fluid was approximately 1.3 million gallons (Q.h thousand tons).
The only present alternatives to Aroclor-insulated transformers are
mineral oil-insulated transformers or dry-type transformers (either those
open to the atmosphere or those that are gas-filled and sealed). Mineral
oils are the preferred fluids when fire does not create a hazard. Dry
transformers also can be used when space is available to install them.
Fluorocarbon liquids require a special transformer design.
PCBs are used in more than 90 percent of the electric utility (large
power) type and smaller industrial type capacitors made today. They are
needed for safety, reliability, and long life, and to achieve sizes compati-
ble with equipment and installation requirements.
12
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Almost 80 million PCB-impregnated capacitors are manufactured annually,
most of them for first-time use. The principal types are high voltage power
capacitors used primarily for power factor correction in the distribution of
electric power; low voltage power capacitors installed in industrial plants
at the load (typically large motors); ballast capacitors to improve the
efficiency of lighting systems; and small industrial capacitors for power
factor improvement in such equipment as air conditioning units, pumps, fans,
etc.
Capacitors used in lighting and air conditioning applications contain
0.0005 to 0.09 gallons of PCB per unit. Ihe largest power capacitors contain
about 6.7 gallons of askarel. The National Electrical Code requires that any
installation of capacitors in which any single unit contains more than 3
gallons of combustible liquid shall be in a vault like that required for
transformers. During 1968, the last complete "normal" year for the electri-
cal industry, the amount of PCBs used in capacitors was approximately lU.ii
thousand tons.
Possible alternatives to PCB-impregnated capacitors are capacitors im-
pregnated with mineral oil or certain other liquids. Flammable fluids in
capacitors used in buildings are not allowed by insurance companies and
building codes.
If codes did allow flammable materials in this use, replacement of PCBs
in capacitors and transformers would require considerable time and money for
re-engineering, manufacture, and application of substitute equipment, and
lack of availability of PCBs for this equipment would cause a major and
lengthy disruption in the nation's electrical system.
Industrial Applications^
PCBs have been useful in hydraulic systems where leakage onto hot metal
surfaces could cause fire, but substitute fluids are available. Gas turbines
require lubrication at high temperatures. PCBs can be used but tend to be
corrosive. Phosphate ester lubricants seem better in this respect. Chemical
stability is more ijnportant than non-flammability for high temperature lubri-
cants. PCB fluids are useful in diffusion booster pumps, but non-flammability
is not especially important for diffusion pump liquids, and alternative liquids
are available.
Heat Transfer Materials
Flammable heat transfer fluids present a fire hazard if they leak into a
furnace or onto hot surfaces. The use of PCBs prevents this danger. In some
cases water is a suitable substitute at moderately high temperatures, and other
satisfactory heat transfer fluids are commercially available and in use.
Plasticizers
The PCBs are good plasticizers for use with adhesives, textiles, surface
coatings, sealants, and copy paper. In some cases the PCBs act as fire re-
tardants. There are no unique properties of PCBs for plasticizer uses, and
equally effective alternatives are generally available (e.g., phosphate esters
are often used as fire retardants).
13
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IV. OCCURRENCE, TRANSFER, AND CYCLING IN THE ENVIRONMENT
Given the diversity of uses of PCBs and their chemical characteristics
(greater stability in the higher chlorine species), it is not surprising
that the residues are widespread. While satisfactory quantitative estimates
of the contribution of various pathways into the environment are not possible
with existing data, there are enough data to be certain that PCBs do reach
the environment at least from the following sources:
-- Open burning or incomplete incineration (at usual temperatures)
of solid wastes, municipal and industrial. Incineration at
2000°F or above for two seconds will destroy PCBs, but poorly
operated incinerators or open burning may result in PCBs being
released to the atmosphere unchanged.
Vaporization from paints, coatings, plastics, etc. (Nisbet and
Sarofim, 1) estimate that as much as 20 percent may be vaporized.
— Municipal and some industrial sewers (PCBs present in treated
as well as untreated wastes).
Accidental spills or improper wastes disposal practices.
— Formerly, direct application to the environment as ingredients
of pesticides or as carriers for pesticides (such uses of PCBs
are now prohibited).
— Dumping of sewage sludge, municipal and industrial solid waste,
and dredge spoil at sea.
-- Sewage sludges disposed of on land.
-- Migration from surface coatings (paints, etc.) and packaging
materials into foods and feeds.
Probably the largest amounts of PCBs circulating in the environment
reach it through industrial and municipal discharges to inland and coastal
waters.
The recommendation by the task force that "more scientific information
about PC3s is needed" is illustrated by the sparsity of knowledge about PCBs
in the environment. Only general statements can be made about how PCBs reach
the environment, how they reach target organisms, and how much is present.
Nisbet and Sarofim (l) estimate that the total loss of PCBs into the U. S.
environment over the last hO years would approach 30,000 tons to the atmosphere,
60,000 tons to water and 300,000 tons to dumps. Of this total, remaining resi-
dues might be 20,000 tons from the air (which would be distributed on land or
water), 30,000 tons in water, and perhaps 250,000 tons in dumps.
-------
Thousands of environmental and biological samples have been analyzed
for the presence of PCBs. One or more of the PCB compounds have been de-
tected in all environmental media, and in many organisms.
Water
The water environment is probably the principal sink and transport
mechanism for PCBs. Calculations based on measured occurrences in municipal
and industrial outfalls, in the receiving waters, and in the downstream
reaches of the waterways demonstrate transport through the aquatic system.
Measured residues in fishes from various environments suggest accumulations
at the downstream ends of the drainageways.
There are few data on removal, disappearance, and sequestering of the
substances in soils or bottom sediments of rivers, lakes, estuaries, or the
ocean.
Organisms Other Than Man
PCBs being, like many of the organochlorine insecticides, fat soluble,
are stored in the lipids of animals. Also like the chlorinated hydrocarbon
insecticides, they resist metabolic changes, and tend to be concentrated at
succeedingly higher levels in animals higher in the food chain. The higher
chlorine PCBs are the most stable.
Occurrence and Sources of PCBs in Food
The identification of PCBs as a potential food contaminant was first
reported in 1966. Subsequent investigations, including the development of
analytical procedures for PCBs in foods and their incorporation in Federal
programs for monitoring the nation's food and feed supply for pesticide
residues and other chemical contaminants, established several sources from
which foods may become contaminated with PCBs.
Environmental Contamination of Food
PCB residues in fresh water fish appear to be widespread geographically
as a result of the environmental contamination of lakes and streams. Depending
upon the location of sampling and the species of fish, PCB levels generally
range from 1 to 10 parts per million. Foods of animal origin, such as meat,
poultry, eggs, and milk contain, in some instances, low background levels of
PCBs that may be attributable to environmental contamination.
Industrial Accidents
The widespread industrial uses of PCBs have resulted in a number of
identified isolated accidents involving the direct contamination of animal
feeds, which, in turn, caused human food to become contaminated.
— Poultry and eggs became contaminated as a result of the leakage
of PCB heat transfer fluid during the pasteurization of fish
meal (poultry feed component).
15
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-- PCS residues in milk have resulted from the use of PCB in certain
coatings on the inside walls of silos, which,, in turn, contaminated
the dairy feed silage.
-- The use of spent PCB transformer fluid as a herbicide spray vehicle
allegedly contaminated dairy cattle grazing areas thereby causing
residues in milk.
The grinding of bakery products along with their PCB-containing
wrappers for use as poultry feed is suspected to have caused
contamination of fowl.
These incidents, as well as others during the past several years, represent
localized sources of contamination. Federal, State, and industry actions pre-
vented most of the contaminated foods from being marketed.
Food Packaging
A significant percentage of food paper packaging materials contains PCBs
and has resulted in the migration of low levels to the packaged food. This
source of food contamination was identified in 1971. The origin of PCBs in
packaging materials is not fully understood. Recycled waste paper containing
PCB carbonless "carbon" papes. is the prime source of PCB in paperboard pro-
duct. Virgin paper products, however, have also been shown to contain PCB
residues, probably as a result of the paper manufacturing processes. Data on
current production of food packaging materials indicate that the levels are
decreasing and are controllable so that the potential for PCB contamination of
packaged foods can be minimized.
Dietary Intake
National monitoring data, and in particular FDA's total diet studies,
indicate that the human dietary intake of PCBs is of a low order. For
example: the dietary intake expressed as mg/kg body weight/day, and based
on food consumption approximately twice as high as the normal diet, was less
than 0.0001 in FY 1971 and 0.0001 in the first-half of FY 1972. As a point
of reference, from 1965 to 1970 dietary intake of DDT was 0.0007 mg/kg body
weight/day. Other investigations further disclose that except for unavoid-
able background levels in certain foods, the PCB contamination of food can
be significantly reduced or eliminated through appropriate controls.
Man and the Ecosystem
In air and water away from immediate sources of waste discharge, levels
of PCBs are low -- a few micrograms per cubic meter (parts per trillion; ppt)
in air and less than a. part per billion (ppb) in fresh water; soil or bottom
sedijnents contain a few parts per billion, up to several hundred parts per
million (ppm) near some industrial outfalls; from tenths of a ppm to tens of
ppm in fish and up to hundreds of ppm in some fish and birds near the top of
the food chain. To illustrate these relationships, 1/8 of an inch is about
16
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one trillio'nth of the distance to the moon; and a part per million is about
5 steps on a walk from Washington to San Francisco.
Man, who is at the top of a food chain, may also have PCB residues in
his body fat. Analyses of tissue residues from 688 persons from three States
showed two-thirds to have detectable residues, but only one-third contained
residues of 1 part per million or more.
PCBs have been shown to accumulate in fish and aquatic invertebrates to
levels of 75,000 times that present in the water, and to be accumulated from
concentrations as low as 0.06 parts per billion (the lowest concentration for
which experimental data are available). Thus, to keep levels in fish as low
as possible, and in any case from reaching the 5 parts per million established
by FDA as an interim action level for safety as food, concentrations in water
should be less than 0.07 part oer billion, or to allow some safety factor, 0.01
ppb. This level in water should be sufficiently low that fish and shellfish
are not themselves adversely affected.
Existing data suggest that the principal route of PCBs through the environ-
ment is from waste streams into receiving waters, downstream movement in the
waterways in the water and on sediments, accumulation from the water by aquatic
organisms, and transfer to birds and mammals (including man) through residues
in fish that are eaten.
Another route to man is through migration of residues to foods from PCB
containing packaging materials. A third route to man may have been absorption
through the skin from handling carbonless carbon paper. These exposures are
being rapidly diminished since PCBs are no longer used in carbonless carbon
paper. Presumably most of the PCB residues in paper made from waste paper
also came from used carbonless carbon paper, which is no longer used in making
food packaging material.
V.A. BIOLOGICAL EFFECTS ON MAN (METABOLISM, TOXICOLOGY, AND RESULTS OF
HUMAN EXPOSURES)
Human beings occasionally have been exposed to high levels of PCBs. Some
exposure has been the result of occupational experience or of accidental con-
centrations in food as in the accidental contamination of rice oil in Japan
("Yusho" episode). As far as can be determined, the rrraber of exposed persons
in these cases has been limited. Another source of contamination and exposure
(although at a lower level) has been fish containing PCBs.
Samples of human fat have been examined to a limited extent for the pre-
sence of PCBs. As a result of this limited sampling, it has been concluded
that some persons carry a body burden of PCB in their fat tissue. In contrast
to the ubiquity and levels of DDT and its metabolite, DDE, in humans in this
country, the current levels of PCBs do not appear to be as uniform in distri-
bution. At the levels in which they are found, PCBs do not appear to present
an imminent hazard.
17
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The acute toxicity of commercial PCBs in experimental animals appears
to be low. In the case of the human exposure with the Yusho episode, the
average dose to that exposed population -was calculated as 2 gm. From this
incident, it was estimated that the minimum dose necessary to produce posi-
tive clinical effects was 0.5 gm.
With a sufficiently high dose it is possible to distinguish a number
of toxic actions of PCBs and their contaminants in mammals. Alterations
in the functioning of the liver have been observed in a number of species,
and these are attributed to PCBs. It is likely that other conditions, such
as chloracne (severe skin eruptions), liver damage, and hydropericardium
(accumulation of fluid in the sac which surrounds the heart) may be caused
by a contaminant, chlorinated dibenzofuran.
The limited mammalian chronic studies of the Monsanto Company indicate
no evidence for carcinogenicity. The possibilities of embryotoxicity and
mutagenicity, however, are poorly studied and, hence, are ill-defined.
Because of the possibility of human exposure to PCBs, the task force
recommends the following additional studies:
1. Toxicological evaluation of a select number of representative,
purified PCB isomers as well as purified trace contaminants such as the
chlorinated dibenzofurans.
2. Definitive mammalian elaboration of the kinetics, absorption, dis-
tribution, metabolism, and excretion of the technical PCBs as well as a num-
ber of key isomers and the chlorinated dibenzofurans.
3- Elaboration of the subcellular and intracellular actions of the
technical PCBs as well as a number of representative isomers and chlorinated
dibenzofurans.
h- More definitive epidemiological studies of the PCBs with both more
representative population sampling and standardization on the basis of lipid
content of the' tissues.
V.B. BIOLOGICAL EFFECTS ON ANIMALS OTHER THAW MAN
The significance of PCBs to wild animals depends primarily upon the sub-
lethal physiological effects of these substances rather than upon their lethal
toxicity. They have accumulated in all portions of the natural environmental
complex in a manner predictable from their high solubility in fat and their
resistance to degradation.
PCBs can be lethally toxic to some fish and aquatic invertebrates when
concentrations in the water are parts per billion or less. They are metabo-
lized and excreted very slowly by these organisms.
18
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They are only moderately toxic to birds and mammals; lethal levels
are similar to those of DDE. PCBs may have contributed to direct mortality
of some adult birds in the field, but not to an extent to affect populations.
In sublethal exposure, PCBs are physiologically active and induce
enzyme activity. Direct effects on reproduction have been shown for chickens,
but not for ducks, quail, or doves. Some studies tentatively suggest the
possibility of subtle behavioral effects and of interactions with disease
organisms or other environmental chemicals.
Full evaluation of actual or potential effects in the environment is
hampered by the complex nature of the mixtures that compose PCBs, and by
the inclusion of contaminants in these mixtures. As experimental studies
have been conducted with the unaltered products, as sold, the results may
not properly reflect the effects of the components as they exist in the
environment.
Although fully conclusive data are not available, the evidence for toxic
and physiological effects indicates that the PCBs must be viewed as potential
problems at present environmental levels.
19
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FOOTNOTES
1. Nisbet, I.C.T., and A.F. Sarofim, "Rates and Routes of Transport of PCBs
in the Environment". Paper delivered at International Scientific Meeting on
PCBs sponsored by the National Institute of Environmental Health Sciences,
and held at the Quail Roost Conference Center, Rougemont, North Carolina,
December 20-21, 1971. (Environmental Health in Perspective (in press) 1972.)
2. Data supplied by the Monsanto Company.
20
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APPENDICES
Page
Contents and Authors
Ao Chemical and Physical Properties of PCBs 22
H. F. Kraybill
Food & Drug Administration
Department of Health, Education, and Welfare
Bo Use and Replaceability of PCBs hi
Martin G. Broadhurst
National Bureau of Standards
Department of Commerce
C. The Need for Continued Use of PCBs as Electrical
Insulating Liquids 75
Electrical and Nuclear Sub-Council
National Industrial Pollution Control Council
Department of Commerce
D. Occurrence, Transfer, and Cycling of PCBs in the
Environment 83
John L. Buckley
Environmental Protection Agency (with assistance
of Edward Grenning, EPA)
EC Occurrence and Sources of PCBs in Food 107
John E. Spaulding
Department of Agriculture
John R. Wessel
Food & Drug Administration
Department of Health, Education, and Welfare
F. Human Directed Aspects of PCBs 122
Lawrence Fishbein
National Institute of Environmental Health Sciences
Department of Health, Education, and Welfare
G. Biological Data on PCBs in Anijnals Other Than Man 158
Lucaile F. Stickel
Bureau of Sport Fisheries and Wildlife
Department of the Interior
H. Regulatory Action on PCBs 173
Terry' Davies
Council on Environmental Quality
Executive Office of the President
21
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APPENDIX A
Chemical and Physical Properties of PCBs
Table of Contents
Page
I. Chemical and Physical Characteristics 23
II. Problems in Analytical Chemistry -
Comparison of Methods 27
II.1 Separation 2?
II.2 Quantitation 29
III. Contaminants, Impurities, or Other Chemical
Moieties in PCBs 37
Tables
1 - General Physical Properties of the Aroclor
Chlorinated Compounds 26
2 - Relative Retentions, Mass Spectrometric Data
on PCB Fractionated Sample 37
Figures
1-6. Chromatograins of various representative PCBs,
according to Armour 31-36
22
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APPENDIX A
Chemical and Physical Properties of PCBs
I. Chemical and Physical Characteristics
The PCBs (trade name Aroclors in the United States, unknown in Soviet
Union, Phenoclor in France, Colphen in Germany, and Kanachlor in Japan) are
manufactured in the United States primarily by Monsanto Chemical Company.
There are also suppliers in Europe and Japan. Because of their unique chemi-
cal and physical properties the PCBs have been widely used in paints, electri-
cal transformers, condensers, non-inflammable oils, adhesives, plasticizers,
heat transfer systems, hydraulic fluids,, caulking materials, printing inks,
and many other uses where the nonflammability and heat resistance properties
are useful. Monsanto Chemical Company, reacting to the concern about extensive
environmental contamination by the Aroclors, have recommended discontinuance
and curtailed uses in equipment or products which inadvertently lead to con-
tamination of the environment (food products, potable water supplies, and as
an air pollutant). Presumably the history of the polychlorinated biphenyls
started in 1930 when an industrial use of non-flammable oils was introduced
for electrical transformers, condensers, and paint. It was probably not un-
til the mid-sixties that an awareness of the environmental contamination
came about with the realization that after LiO years use of the Aroclors,
there was as extensive a problem of contamination as with the organochlorine
pesticide DDT. Swedish scientists drew attention to the fact that PCB has
been found in fish and birds in their surveillance in 1966, and soon this
alerted investigators in other countries to the problem. Surveillance of
total diets by FDA failed to report any PCB in fruits and vegetables.
Perhaps the accumulation of PCBs in environmental substrates or living
organisms can be associated with the particular chemical and physical proper-
ties of these series of synthetic chlorinated aromatic compounds. For example,
the nonenvironmental degradability or biodegradability accounts for it as a
residue in many media and for its persistence. Like DDT, closely related
structurally, -it will enter the organism, be stored in the depot fat, and thus
be transferred through the food chain at increasing concentrations. The basic
structure of PCBs is shown below where x represents any number of possible
positions for chlorination leading to about 210 possible combinations, of
which 102 are probable. (Widmark, l), who made this calculation in developing
criteria for these limitations, noted that the criteria were based on com-
pounds containing five to eight chlorine atoms per molecule and the number of
chlorine atoms per ring differing by not more than one.
The Aroclors may consist of chlorinated bipher&rlSj chlorinated terphenyls,
or a mixture of these compounds. Invariably, although a specific numbered
Aroclor may represent a molecular type and degree of chlorination or weight
percent of chlorine, the product is a mixture of compounds in a series such as
1200, 2^00, kkOO, and £ljOO. The first two digits represent the molecular type,
23
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and the last two digits give the weight percent of chlorine. For example:
1200 - chlorinated bipheynls
2500 - blend of chlorinated biphenyls and
chlorinated triphenyls (75:25)
IjljOO - b?_end of chlorinated biphenyls and
chlorinated triphenyls (60:ljO)
5hOO - chlorinated triphenyls
Thus Aroclor 12142 would be a chlorinated biphenyl containing h2 percent
chlorine. These biphenyls produced by Monsanto range from 21 to 68 percent
chlorine. To refer back to the existence of many possible isomers, it is
of interest that Aroclor 1260 would show the presence of 11 isomers; five
containing six chlorine atoms, five containing seven chlorine atons, and one
containing eight chlorine atoms (2). Bagley, et al, (3) studying Aroclor
125h, observed 18 distinct compounds. However, as previously stated,the num-
ber of compounds present or identified by mass spsctrographic studies is much
less than theoretically deduced.
The polychlorinated biphenyls which are chemically inert were described
in the literature back in 1881 by Schmidt and Shultz (ti) but achieved by Swann
Company in 1930 and fully developed for industrial use in that year. During
the IjO-year era, 1930-1970, it was discovered that Aroclors could be used to
extend the effectiveness or lethality of organochlorine Insecticides such as
chlordane, aldrin, and dieldrin in pesticidal formulations, thus enhancing
the possibilities for proliferation into the environment (£). Additionally,
there were indications that PCB had a synergistic effect on lindane (6).
The Aroclors, as previously stated, are chemically inert, making them
ideally suited for certain industrial uses. They are not hydrolyzed by
water and resist alkalis, acid, and corrosive0chemicals. Since they are not
volatile, their boiling points range from 278 C for Aroclor 1221 to l)£l°C
for Aroclor 1268. They are stable to long heating and can be distilled at
ordinary pressure without any carbonization or decomposition. As might be
expected, since they are insoluble in aqueous media, they are quite soluble
in hydrocarbon solvents. It is believed that PCBs are more stable than DOT
and metabolites and, accordingly, resistant to biodegradability or biological
decomposition. The proximity of the aromatic rings probably accounts for
the lack of degradation of transformation as with DDT, which has an ethane
linkage intervening the aromatic nuclie.
PCBs and formulations thereof have a wide range in viscosity and physi-
cal state, from colorless mobile-like oily characteristics tn yellow-green
clear mobile oil, to light yellow viscous oil, to light yellow soft sticky
resin, to white powder, to light yellow clear brittle resin, to yellow trans-
parent sticky resin, to clear yellow-amber brittle resin, to a black opaque
brittle resin. Other properties such as low solubility in water and high
dielectric constants make them versatile for industrial uses. Mary/" of these
-------
PCB preparations have strong adhesive properties, and it is this use in
bonding of paper and cardboard in certain packages for food, plus reuse
of printing paper in manufacture of grayboard, that has led to a few
problems of contamination of certain food products. A rather complete
compilation of these properties is listed in the attached table from a
report by Monsanto Company.
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Table 3
GET'ERAL PHYSICAL PROPERTIES OF THE
AROCLOR CHLORINATED COMPOUNDS
Aroclor 1232
Aroclor 1221 Practically
tor" Colorless colorless
mbile oil mobile oil
Color 50 Max. 50 Max.
(APHA) (APHA)
Acidity - Maxinun (ngm. KOH per Gri.) 0.011, O.Oll,
Averace Coefficient, of Expansion cc/cc/SC O.O0071 000073
q5°-LO°C) (25°-IOO°C)
Typical Density 1.182-1.192 1.270-1.280
Specific Gravity (25°/15.S°C) (?5°/15.5°C)
Pour.ds per gallon - 25 C (77 F) 9.85 10.55
Distillation Range - A SIM D-20 (Hod.)
c°-r- °C 275°-320° 290°-325°
Evaporation Loss - % - ASTH D-6 Mod.
163°C 5 hrs. .
100 C ...6 hrs. 1.0 to 1.5 1.0 to 1.5
Flash Point - Cleveland Open Cup °C ]1,1°-150° 152°-151i°
F 286 -302 305 -310
Fire Point - Cleveland Open Cup °c 176° 238°
°F 31.9° 1,60°
Pour Point - ASTH D-97 °C Crystals at -35-5°
l°c
F Crystals at -32°
3u°F
Softening Point - ASTM E-28 °C
Refractive Index - D-line - 20c'c 1.617-1.618 1.620-1.622
Aroclor 12lj2
Practically
colorless
mobile oil
Aroclor 12WJ
Colorless to
light yellow-
green, clear,
mobile oil
Aroclor 125U
Light yellow
viscous oil
Aroclor 1260
Light yellow
soft sticky
resin
50 Max.
(APHA)
50 Max.
(APHA)
50 Max.
(APHA)
50 Mai.
(APHA)
0.01L
0.00068
(25°- 65°C)
0.00070
(25°-65°C)
0.00066
(25°-65°C)
0.00067
(20°-100°C)
1.381-1.392
(25°/15.5°O
11.50
l.WS-l.UlS
(65°/15.5°O
12.OL
1.WS-1.50S
(65°/l5.S°C)
12.82
1.555-1.566
(90°/15.5°c)
13.50
325°-366°
3W-375"
365°-390°
385 -WO"
3.0 to 3.6
0.0 to O.h
3.0 to u.O
0.0 to 0.3
1.1 to 1.3
0.0 to 0.2
3u8 -356
193°-196°
379°-381i°
0.5 to 0.8
0.0 to 0.1
Hone
Kone*
-19°
2°
-7°
19.u°
10°
50°
1.627-1.629
1.630-1.631
1.639-1.6ul
31°
88°
1.61,7-1.61,9
Viscooity - Saybolt Universal 210°F (98.9°C) 30-31
Sec. (ASTH - D-88)
130°F (51,.li0C) 35-57
100°F (37.3°C) 38-1,1
31-32
39- bl
uu-51
3u-35
1,9-56
82-92
36-37
73-80
185-21,0
Lli-1,8
260-31,0
1800-2500
72-78
3200-1,500
*N01,1 indicates- "i:o fire point up to boiling
tenperature
398C->
Oral LD5o-rats (approx.) - ng/kg
Skir MLD - rabbits - ng/kg
adnir.is tared
-------
Aroclor 1262
Light yellow
sticky clear
resin
50 Max.
(APHA)
O.Olli
O.OO06L
(25°-65°O
1.572-1.583
(90°/15.5°C)
13.72
395°-L25°
0.5 to 0.6
0.0 to 0.1
Hone
!!one
350-38°
99°
-
1.6501-1.6517
86-100
600-850
(160°F or 71°C)
11,300»»
Aroclor 1268
White to
off-white
powder
1.5 Max.
l.TA (raolten)
0.05
0.00067
(20°-100°C)
l.BOIi-1.811
(250/2500
15-09
W5°-L50°
0.1 to 0.2
0.0 to 0.06
(lone
None
-
150°to 170°
(hold pt.)
(hold pt. )
-
10,900»
Aroclor LL65
Light-yellow,
clear, brittle
resin
2 Max.
NPA (molten)
0.05
".00061
(25°-65°C)
1.070
(25A/25°c)
13.91
230°-320°
at h msi. HK.
0.2 to 0.3
0.0 to 0.02
None
None
-
' 60°to 66°
lUO°to 151°
1.661i-1.667
90-150
(260°F or 130°C)
16,000**
2000"
•O160**
Aroclor 51jlj2
Yellow Trans-
parent sticky
resin
2 Max.
NPA (molten)
0.05
O.O0123
(25°-99°C)
1.1)70
(256/25°C)
215°-300°
at h nun. He .
0.2
0.01
2ti7°
Ii77°
>350°
^662°
&
Ii6°to 52°
H5°to 126°
-
300- LOO
10,600«
Aroclor 5L60
Clear , Yellow-
to-amber ,
brittle resin
2 Max.
NPA (molten)
0.05
0.00179
(25^/25°0
13-91
280°- 335°
at 5 mm. Hg.
0.03
1.5 to 1.7
(at 260°-5 hrs.)
None
None
-
98° to 105.5°
208° to 222°
1.660-1.665
-
19,200*
Aroclor 2565
Black, opaque
brittle resin
l.li
0.00066
(25C-65°C)
(25d/25°0
Ib.Uli
-
0.2 to 0.3
Hone
Hone
-
66°to 72°
lli9°to 162°
-
-
^3160
26a
-------
II . Problems in Analytical Chemistry - Comparison of Methods
II. 1 Separation
One of the primary and early problems in the identification of the
polychlorinated biphenyls (PCBs) was that of possible interference in the
GLC determination of or ganochlorine pesticides, where the PCB occurred along
with the pesticide residue. During 1969 and 1970, various investigators
worked on methods for separating PCB from pesticides (7-lh). An excellent
treatment of the subject of PCB as a contaminant in the environment, as '
related to its detection in the presence of other compounds, is covered by
Jensen
Jensen (15)., in his review, has shown that some of the earlier studies
of DDT and DDE in human fat by GLC must have been inordinately high. He
first identified some GLC peaks in wildlife in 196h-66 that were not recon-
cilable but later identified chromatograph peaks from human fat that were
not attributable to DDT or metabolites of DDT, which were more nearly com-
parable to peaks ascribed to PCB. The possibility that these peaks could be
attributed to naturally occurring constituents in fish eaten by man was dis-
carded when it was suggested that these same peaks could come from environ-
mental pollutants.
To further establish the then uncertain composition of the chemicals
causing the false DDT peaks, Jensen (l5) separated out one of the chemicals
by GLC and subjected this fraction to mass spectrometry. The mass spectro-
metry data showed compounds with molecular weights of 32k, 3%8 , 392, and k26.
The molecular weight differences or differences of 3k mass units suggested one
less chlorine atom per position on a carbon atom. In essence, through calcula-
tion, he deduced that these unknown chemicals could only be polychlorinated
hydrocarbons, in this case having 5> 6, 7, and 8 chlorine atoms in the molecule.
He verified his conclusion by introducing a synthetic or known PCB into the mass
spectrometer. He also found that PCB standard chromatogram matched those with
the same retention times as observed in various samples he analyzed, i. e.,
eagles, fish, or other wildlife.
It is interesting to point out that failure to recognize such inter-
ferences "led to spurious results and data and obviously led to the over-
estimation of DDT in our environment, in man, in wildlife, and aquatic
organisms. Jensen (l£) referred to PCB as a new pollutant, but, as stated
earlier, PCB was with us in the environment since 1930 and thus it would be
an old pollutant only recently correctly identified by appropriate analytical
chemistry.
In earlier work in the identification of some or ganochlorine pesticides
such as p,p'-DDT; o,p-TDE (ODD), lindane, dieldrin, aldrin, heptachlor, and
lindane, some unidentified spots and peaks in TLC and GLC interfered with the
detection of these pesticidal chemicals. Jensen (15>) in his work extracted
the compounds from biological samples and, by appropriate cleanup of some con-
taminants, identified the pesticides and PCBs by thin layer and gas liquid
chroma tography followed by mass spectrometry. In 19614, Jensen used TLC to
separate the fat soluble chlorinated hydrocarbons frqm the rest of the sample.
27
-------
For pesticide analysis, the common detector is the electron capture
detector. For sensitivity, one can determine levels at the picogram range.
However, this detector, not specific for chlorine, also gives an answer for
oxygen containing compounds. Although the response here is much lower, this
can be counter balanced if the level of oxygen containing impurity is some-
what higher. This system has certain inherent disadvantages in that two
different compounds can have the same retention time and thus be detected
as one compound or the recorded peak does not need to contain chlorine since,
as indicated above, the detector is not that specific (15). However, by using
different columns with variant properties, one can inject a sample into the
instrument and thus secure a good separation.
To further demonstrate whether a compound which is responsible for a
certain peak contains chlorine, one can concentrate the sample and analyze
by a less sensitive chlorine specific detector such as the microcoloumetric
detector. This, therefore, enhances the specificity in this residue analysis.
When Jensen (15) analyzed human fat for DDT by use of two columns, he
was able to separate from human fat the two "DDT" peaks into four peaks. Two
of these peaks were similar to those for o,p and p,p'-DDT, but two of the peaks
were unidentified. As indicated earlier, he thought these peaks were due to
naturally occurring components, which would be found in the fish consumed, such
as pike. He was able to rule out this premise by treating the sample with
alcoholic KOH and H2SOlj which would chemically alter DDT but not the more stable
or inert polychlorinated biphenyl. Jensen simultaneously noted that samples of
pike from a certain region, containing the then unidentified component, were
correlated or associated with an area of extreme pollution. Similarly, eagles
that fed on pike showed this unidentified component in their tissue. The com-
pound in the eagles had the same retention time as the pike, thus confirming
that this was a problem of biological magnification rather than the mere occur-
rence of a natural biochemical entity.
Another speculation was that metabolites of DDT could explain the appear-
ance of unidentified peaks. Interestingly enough, these same peaks were found
in an eagle sample collected in I9h3 (prior to use of DDT in Sweden), thus im-
plying that the DDT metabolites were not the potential unknowns. In addition,
mercurials were considered, but the occurrence in water, fish and pheasants did
not correlate or show a consistent pattern.
A method for the separation of polychlorinated biphenyls from DDT and its
analogs has been developed by Armour and Burke of FDA (l6). Identification by
means of a combination of high resolution gas chromatography and mass spectro-
metry has been carried out by three independent laboratories in Sweden (17),
Holland (2) and the United States (3) in addition to those named above.
There is a need to measure PCBs at extremely low levels of the order of
1 part in 10 or less. Accordingly, the method must be both specific and
highly sensitive. Hence gas chromatography, using electron capture detection,
has been extensively used with occasional identification and structure con-
firmation by gas chromatography mass spectrometry. This involves such steps
as (a) sample preparation, (b) extraction of PCBs, (c) removal of interferences,
(d) concentration, and (e) final gas chromatography and measurement.
28
-------
Some biological samples require more extensive pretreatment than for
water or effluents from industrial plants. The measurement of PCB concen-
tration of effluents is a simple procedure involving chromatogram of sample
and then chromatograms of standard samples developed from known PCBs. For
more accurate analysis s calibration graphs can be developed from known speci-
fic peaks in the standard samples (15).
In the following charts (Figures 1-6) some chromatograms of the various
representative chlorobiphenyl Aroclors are presented according to Armour (18).
Some additional points might be made relevant to separation and quantita-
tion of PCBs. First of all, in separation, the methods used prior to quanti-
tation of residues in samples containing PCBs and chlorinated hydrocarbons
fall essentially into two categories: (a) those which necessitate destruction
or alteration of one or more of the compounds and (b) those which do not.
Peakall and Lincer (19) have described in detail the procedures used for
separation.
p Briefly, the first group requires nitration (HNO ij ^I^SCj,) treatment at
0' C for 5> minutes, which destroys or alters many of the organochlorine pesti-
cides; thus PCB is left unaffected along with lindane and BHC. Some workers
such as Armour and Burke (l) reported that complex chromatograms resulted
after nitration, which could not be related to the unreacted DDT-PCB mixture.
Thus, nitration was not pursued as a practical means of separating DDT and
PCB for further analyses.
Saponification with alcoholic NaOH or KOH will dehydrochlorinate some
pesticides such as Perthane, Toxaphene, ODD and DDT to their respective ole-
finic compounds (20) .
Perhaps the more desirable technique allows for special separation of
many chlorinated hydrocarbon pesticides from PCB. This involves using various
columns and solvents. Another procedure is to use a series of differing
polarity columns in the gas chromatograph at the time of determination (2l).
II. 2 Quantitation
Koeman, et al (2) measured residues in Japanese quail by using one of
the peaks in a phenachlor DP6 mixture as standard. Risebrough (22) quanta -
tated relative levels of PCBs by assuming that each PCB compound produced
the same peak height with the electron capture detector as the same amount
of weight by p,p'-DDE. After adding the heights of the individual peaks,
the total was multiplied by a factor derived from measurements of standard
solutions with EC and MC detectors. Jensen and co-workers (23) reported
concentrations of PCB as the sum of all PCB components and based the esti-
mation on several detection systems such as mass spectrometry and EC and MC
detectors. In spite of all these techniques, these investigators consider
the method approximate and correct only within a factor of 2.
There are other modifications of techniques, but with all the quantita-
tion methodology available, relative estimates of concentrations of PCB are
-29
-------
GAS CHROMA TOGRAPHIC CONDITIONS
Figures 1-6
Columns: (l) 10$ DC-200 on Chromosorb W HP
Detector
(2) 15£ QF-lAO* DC-200 on Chromosorb W HP
6 ft x Iffnm. id.
200°C
120 ml N2/min.
electron capture (tritium)
200°C
one nanogram heptachlor epoxide causes one half
scale recorder deflection
30
-------
Figure 1.
Aroclor 1221
10% DC-200
VjJ
A 5
Aldrin
10
pp'DDT
-------
Figure 2.
A. Aroclor 1242
10% DC-200
) ' 5 11 ' '
Aldrin
10 15 A 20
pp'DDT
I 1
23
B. Aroclor 1248
1070 DC-200
Aldrin
25
TIME(MINUTES)
-------
Figure 3.
A. Aroclor 1254
10% DC-200
^B
3
• «. V - •*» *
— — 'VMW
5A 10 15
Aldrin
\_/ V^-'X *
A 20 25
pp'DDT
'X . •
30 95 40 45 50
B. Aroclor 1260
10% DC-200
i i i i i I i i i i i i i i i i i i i i i i
0 SA 10 15 A 20
Aldrin pp'DDT
25 30 35 40 45 50 55
C. Aroclor 1262
10% DC-200
i i i i i i i i i i i i i i i i i i i i i i i
SA 10 15 A 20
Aldrin pp'UDT
1)111111
30 35
40
45
50
TIME(MINUTES)
55
-------
Figure 4.
Aroclor 1221
15% QF-1/10% DC-200
10
Aldrin
A
pp'DDT
-------
Figure 5.
A. Aroclor 1242
15% QF-1/1070 DC-200
I I I I I . I I ' ' I ' ' '
o As 10 iis 20
Aldrin pp'DDT
25
30
B. Aroclor 1248
15& QF-1/1CU DC-200
Aldrin
pp'DDT15
TIME
-------
Figure 6.
A. Aroclor 1254
15% QF-l/KH DC-200
D
AS
Aldrin
IO A 15
pp ' DDT
•*»
20
i i i i
25
III!
30
11(11 1
35
40
B. Aroclor 1260
15% QF-1/107. DC-200
AS 10
Aldrin
I I I I I I I I I
A 15 20
pp'DDT
•m
25
II I I I I I I I I I I I I I I I | I
3O 35 40 45 SO
C. Aroclor 1262
15% QF-1/10% DC-200
«••••*-*'*• " •«,-••-A-••',!,"",'•' "'Vo'
Aldrin pp-ucrr TIME(MINUTES)
36
-------
only approximate. At such time, when one is able to synthesize the
individual PCB components commonly found in the environment and identify
them in terms of individual peaks, then the estimation remains, as stated,
a relative concentration.
However, for most biological assessment work, the correct order of
magnitude and accurate relative amounts of PCB provide the requisite in-
formation for tnis purpose.
Ill. Contaminants, Impurities, or Other Chemical Moieties in PCBs
In the analysis of the polychlorinated biphenyls, one encounters a
problem similar to that of the polychlorophenols ana 2,lj,5-T in that certain
contaminants or impurities prevail. These impurities arise from the basic
starting materials or compounds used in the synthesis and also from the pro-
cessing conditions used in the chlorination procedures. In this respect,
the series of compounds identified through GLC and mass spectrometry are
somewhat similar in nature to the spectrum of dioxins found in working with
chlorinated phenols, hexachlorophene, 2,b,5-T and related synthetic organic
chemicals.
It has been noted in the bioassay of various Aroclors for toxicity,
usually testing on chickens, that there was a variance in toxicity of cer-
tain PCB preparations. Since the occurrence of lesions resembled those of
chick edema in birds fed PCB, this prompted a comparative study between
three compounds, Phenoclor DP6, Clophen A60, and Aroclor 1260 by Vos et al
in 1970 (2h). In this study, the specific PCBs were fractionated, analyzed,
and bioassayed using the chick embryo assay.
These studies revealed the presence of certa.in polar compounds which
are present as impurities in the various PCBs and thus explain the variance
in toxicity of certain commercial PCB preparations. In Table 2 some of the
retentions and mass spectrometric data of some of the peaks identifying the
presence of some dibenzofurans, chlorinated napthalenes, and associated
chlorinated biphenyls are indicated, proving the presence of impurities.
Table 2
Relative Retentions, Mass Spectrometric Data on PCB Fractionated Sample
Peak No. Relative Mass Nos. and Identity of Compound
Retention No. of Cl atoms
per mol
1 l.hO 30lt (h Cl) Tetrachlorodibenzofuran
2 1.^8 332(6Cl) Hexachloronapthalene
3 1.7i4 358 (6 Cl) Hexachlorobiphenyl
392 (7 Cl) Heptachlorobiphenyl
k 2.lj2 338 (5 Cl) Pentachlorodibenzofuran
392 (7 Cl) Heptachlorobiphenyl
5 3.1jB 366 (7 Cl) Heptachloronapthalens
37
-------
Thus far, the dibensofurans, the chlorinated napthalonss and chlori-
nated dipehnyls appear to be the major contaminants or impurities detected
in'various PCB samples. It is not unlikely that other chemical moieties
will be characterized as further identification work proceeds. These con-
taminants arise, as p.-eviously indicated, by method of manufacture and the
procedure for distillation of PCB, in which NaOH can be used. Through this
NaOH treatment at elevated temperatures, sequentially polychlorohydroxy-
biphenyls are produced ana then, through loss of hydrochloric acid, the
dibenzofuran derivatives result (25).
The chloL-inated napthalenes are far less toxic than the chlorinated
dibeniv>furan« (26). Thus, one might expect, witti bhs varying ratios of
impurities with variant toxicities in different PCB samples assayed for
biological effects and toxlcity, thah the end result will depend on such
factors in examining various commercial PCB preparations.
38
-------
FOOTNOTES
1. Widmark, G. 1968 - OECD Report - Sweden.
2. Koeman, J. J., Ten Noeverde Brauv, M. C. and de Vos, R. H. (1969)
Nature 221 1126-28.
3. Bagley, G. E., Reichel, W. I. and Cromartie E. (1970) J. Assoc. Office,
Analytical Chemistry 53, 251-261.
U. Schmidt, H. and Schultz, G. (l88l). Ann Chem. 207, 338-3UU-
£. Sullivan, W. N. and Hornstein, I. (1953) J. ECon. Entomol h6, 158-159-
6. Tsao Ching Hsi, Sullivan, ¥. M. and Hornstein, I (1953) J- Econ.
Entomol Ij6, 882-881.
7. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918, July 1, 1969,
Armour, J. and Burke, J.
8. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918A, July 23, 1969,
Armour, J. and Burke, J.
9. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918B, Sept. 30, 1969,
Davenport, J. E.
10. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918C, Oct. 13, 1969,
Armour, J. and Burke, J.
11. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918D, Jan. 1U, 1970,
Armour, J. and Burke, J.
12. Laboratory Information Bulletin, FDA FSCS/ACFC No. 918E, Mar. 11, 1970,
Armour, J. and Burke, J.
13. Laboratory Information Bulletin, FDA FSCS/ACFC 1157, June 17, 1970,
Westfall, J. E. and Fehringer, N. V.
1U. Armour, J. and Burke, J. JAOAC 53, 761-768 (1970).
15. Jensen S. (1970) PCB Conference, Nat'l. Swedish Environment Protection
Board, Research Secretariat, Dec. 1970, Solna, Sweden.
16. Armour, J. and Burke, J. (1970), IAOAC, July Edition.
17. Widmark, G. (1967), JAOAC 50, 1069-
18. Armour, J. (1970) FDA Laboratory Information Bulletin No. 918F
FSCS/ACFC, pp. 1-17-
39
-------
19. Peakall, D. B. and Lincer, J. L. (1970) Bio Science 20, No. 17,
pp. 958-96k.
20. Archer, T. E. and Crosby, D. (1966), Bull Environ Contain Toxicol 1,
70-75-
21. Simmons, J. H. and Tatton, J. (1967) J. Chromatogr. 2_7, 253-255-
22. Risebrough, R. W.' (1969), Chemical Fallout, G. C. Berg and M. W. Miller (Ed.).
23. Jensen, S., Johnels, G. A., Olsson, J. and Otterlind, G. (1969),
Nature 22k, 250.
2k. Vos, J. G., Koeman, J. J.3 Van der MaAs,. H. L., Ten Noeverde Brauw, M. C.,
and DeVos, R. H. (1970), Fd. Cosmet. Toxicol £, 625-633.
-------
APPENDIX B
Use and Replaceability of PCBs
Table of Contents
Page
I. Dielectric Fluids 1^3
A. Capacitors h3
1. Advantages and Disadvantages of PCS
in Capacitors.
2. Replaceability of P3B in Capacitors.
3. Extent of Capacitor Use.
B. Transformers 51
1. Advantages and Disadvantages of PCS
in Transformers.
2. Replaseability of PCS Transformers.
3. Extent of Transformer Use.
II. Industrial Fluids For Hydraulic, Gas Turbine,
and Vacuum Pump Uses. 53
A. Hydraulic
B. Gas Turbines
C. Vacuum Pump Applications
III. Heat Transfer Applications 58
A. Advantages and Disadvantages of PCBs as Heat
Transfer Fluids.
B. Replaceability of PCBs as Heat Transfer Fluids.
IV. Plasticizer and Miscellaneous Uses. 59
A. Adhesives
B. Textile Coatings
C. Surface Coatings
D. Sealan ts
E. Printing
F. Fire Retardant ana Flame-Proofing Compositions.
G. Miscellaneous Applications.
ki
-------
APPENDIX B
Use and Replaceability of PCBs
Table of Contents (Continued)
Page
V . Summary ............................................ 66
Tables
1 . Typical Properties of Liquids
2. Physical and Other Properties of Lubricating
Oils, Engine Oils, and Hydraulic Fluids ............... Ii7-5>0
3. High-Temperature Lubricant Specifications ............. $6
£4. Some Properties of Pumping Fluids ........... . ......... 57
5. Decomposition Temperature Ranges of Several
Chemical Classes . . .......................... . ......... 60
6. Approximate Maximum Compatibility, phr, of
Plasticizers With Various Resins ..................... . 61
7. General Properties of Some Aroclors (PCB) ............. 63
-------
APPENDIX B
Use and Replaceability of PCBs
I. DIELECTRIC FLUIDS
Dielectric (electrically insulating) liquids are important to the
electrical industry for filling agents or impregnants in transformers,
capacitors, and other devices. Besides their electrical functions, the
liquids may also be used for cooling and arc quenching functions. De-
tailed discussions of dielectric fluid applications are available (l-M.
A. CAPACITORS
Generally, industrially important capacitors use liquid impregnated
cellulose paper as a dielectric. The required properties of the liquid
are:
1. Non-flammability (important for preventing fires, particularly
in indoor use).
2. Dielectric constant matching that of paper. A good match reduces
electric field inhomogeneities, increases dielectric strength and lifetime,
and allows decrease in capacitor size.
3. Low dissipation factor (reduces energy loss and destructive heat-
ing in a capacitor).
LI. High dielectric strength (prevents breakdown and allows decrease
in capacitor size).
5. High chemical stability (increases capacitor lifetijne and stabili-
zes its performance).
6. Low vapor pressure (increases physical stability).
7. Inert decomposition products in an electric arc (prevents explosion
or corrosion following breakdown).
8. Low toxicity of the material and its decomposition products.
9. Low cost.
1. Advantages and Disadvantages of PCS in Capacitors
The PCB capacitor liquids, commonly called askarels, are mixtures of
chlorinated biphenyls and chlorinated benzenes. Several standard mixtures
are specified by ASTM (5). The askarel capacitor liquids and their de-
composition products are non-flammable. Thus their use in capacitors
greatly reduces fire and explosion hazards. This characteristic permits
economies where safety codes require fireproof enclosures for capacitors
containing flammable liquids.
The dielectric constant or the askarels is high compared to other
common dielectric liquids. Doubling the dielectric constant of the dielec-
tric allows a reduction by half in the area of the capacitor electrodes,
and a significant saving in the cost of construction and installation.
The dielectric constant of askarels closely matches that of the capacitor
paper.
U3
-------
The askarels are adequate with regard to dissipation factor and
dielectric strength and have good chemical stability and low vapor pres-
sure. The breakdown products, in particular HC1, have the advantage of
being non-flammable, but are highly corrosive. This dictates the use of
special corrosion resistant materials inside the capacitors.
The major disadvantage of the askarels is their suspected toxLcity.
In ordinary capacitor usage the askarels are used in closed systems to pre-
vent contamination from moisture. This practice also prevents the askarels
from reaching the environment. However, when electrical failure occurs,
sealed capacitors can leak and are ordinarily discarded.
2. Replaceability of PCB in Capacitors
Capacitors can be made dry or with gas dielectrics. Dry capacitors
have inferior electrical strength to liquid-fined capacitors and, for
comparable performance, mus't be made larger.
The major disadvantage of alternative capacitor liquids is their
flammability. When comparing flash point data, as in Table 1, askarel flash
points comparable to those of other capacitor liquids are sometimes listed.
ASTM states that these are not true flash points but are pseudo-flash points
which differ noticeably from the flash obtained on combustible materials,
and such a flash point is not indicative of a fire hazard (£). The require-
ment of non-flammability for most capacitor uses is critical, and capacitors
with flammable liquids are forbidden in many cases by the National Electrical
Code (6). In other cases replacement of askarel capacitors with flammable
capacitors requires use of fireproof installations (6).
The fluorocarbons are one group of non-flammable liquids which are used
for some dielectric applications (l). The ones listed in Table 2 have low
dielectric constants and could not directly replace askarels without increas-
ing capacitor size. The fluorocarbons have low toxicity but the decomposi-
tion products may be toxic (l). They are generally more volatile than aska-
rels and are considerably more expensive. The fluorocarbons are a possible
replacement for PCB liquids for capacitor use, but no fluorocarbon liquid
is known to be available and acceptable for this purpose.
Besides the problem of flammability, possible PCB replacement liquids
generally lack either a sufficiently high dielectric constant to keep capaci-
tor size down or a sufficiently high dielectric strength. For example (see
Table l) the silicones have the disadvantage of a low dielectric constant
whereas the organic esters often have poor dielectric strength. Some sili-
cones deteriorate rapidly under electric arcing (7).
The acceptance of a PCB substitute is a complex process involving not
only users but also various regulatory groups. In most of the electrical
industry, regulation is non-governmental, and the primary regulatory influ-
ence comes from Underwriters Laboratories, who test products and decide on
their suitability (8). In addition, control over electrical materials is
-------
TABLE 1
TYPICAL PROPERTIES OF LIQUIDS
Viscosity, SUS. 25'C
37.8'C
99-lOtrC
Viscosity, cs. 25'C
' • 37.8°C
930-
0.001"
763'
60'
10
196.1"
0'
-26.1'
0.928"
0.00030™
0.072°
>30'
0.001"
Heavy
cable
oil
2365'
101°
21
Z43.3"
0'
—17.8'
0.926"
0.00030"
0.072"
>30'
0.001''
Pipe
cable
liquid
1,200'
: 63*
154»
0.01'
-•34'
0.862"
0.00078
>35"
2.14"
0.0005"
>lxl014>"
D . .
Paper
imprcgnant
8,000'
176"
160"
0.01 '
-23'
0.370"
0.00076
0.062'
>35"
2.16"
0.0005"
>1X10""
Capac-
itor
liquid
300,000'
2,200'
2521"
0.01'
1.7'
0.905"
0.062'
>35"
2.22"
0.0005"
>lxlO'"-
40-42
30-31
4.6
146.1'
0.0)0 max
1.1
1.18
0.00071
0.067
275.0
>35
4.5
- 0.001
>5xlO"
44-51
31-32
6.9
153.3'
0.010 max
-35.5
1.26
0.00073
0.063
290.0
>35
5.7
0.001
>5xl0lf
A 1 1
82-92
31-35
17.2
2.5
182.2'
0.010 max
1.38
0.00063
0.058
325.0
>35
5.8
0.001
>5xlO"
ie5-i!40
36-37 :.;
45.3
3.2"
192.8'
0.010 max
1.45
0.00070
0.057
340.0
>35
5.6
0.001
>SxlO"
1300-2500
46.4
• 0.14
Tilone
O.C1C max
10.0
1.54
. 0.00066'
0.054
365.0
35
5.0 •
0.001
>5x30"
-------
(C.F.).N
Viscosity, SUS, 25°C
37.8'C
99-100'C
Viscosity, cs, 25"C 2.59
37.8°C 1.80
99-100'C 0.48
Flashpoint, opsn cup, °C
Acidity, mgm KOH/qm
Pour point, "C —50.0
Specific gravity, 15.6'C 1.89
.25'C 1.88
Coef. of cxpan., cc/cc/'C . .0012
Thermal conduc..
(gm-cal/sec!(cnr)(°C/cm)
(BTU/hrMft'X'FXft) . 0.049
Boiling point at 760 mm, °C 177.8
Volatility, weight loss
Dislec. strength, kv/.l" (0.254cm) 35 min
Dielectric constant, 60 Hz 1.90
10° Hz 1.89
10" Hz* 1.90
Dissipation- factor, 60 Hz <0.0005"
10° Hz <0.0005
10* Hz <0.0005
Volume resistivity, -olirr.-cm 3x10''
'FICFCF.OJ.CHFCF.
' CF,
a ASTM 0446
b ASTM 092
C ASTM 097
d ASTM 01250
e AJTM D677. Suability of 0877 for
high viscosity oils such as cable oils and
polybi'tcnes listed in table has not been
drtcrminsd.
•f ASTM D924
g ASTM 0974
h VVe-qht loss on a 15 gm sample In a 50
rn. Lc.'ikrr at 150* for 24 hrs.
i ASTV Wi61
j ASTM 1169
k Weight loss after 48 hrs. at 200°C
TYPICAL
-Fluofocarbons •• —
«n~J/n = 5 C.F..O
-/35
. 0182- 10.5
—,'2.7 0.64
— /0.88 0.30
-154/-84 —100.0 . —90
1.57/1.82 1.79
1.54/1.79 1.77 0.940.
.00084/.00036 .0016 0.00095
0.00034
0.070/0.049' 0.081
40.8/224.2 '102.2
31%'
28/50 35 min ' 35*
3.02/2.45 1.86 2.7" .
3.02/2.4S 1.84
1.87 2.7"
<0.00006 <0.0005" .00015""
<0.00006 <0.0005
<0.0005 .00001"
-/>4xlO" 6x10" IxlO"1
\1
1 100eF- 1-
m O'C
n -8'C
0 ASTM 0287
p ASTM.D257
q 23°C
r 80°C
s 100'C
1 Hi unknown
u 100 Hz
v ASTM D149
w 10'Hz
x ASTM D150no
y • Askarels have true flash point.
PROPERTIES OF LIQUIDS— continued
Silicon:* : Organic Esters
Dielectric Glyceryl Butyl Butyl Butyl
Grade Tri- Stearate Sebacate Naphth-
. Castor acetoxy- enate
Oil Stearate
360 720 180 48 46
137.9
100 200 500
80 160. 400 7 6
29 58 148 98
>30 >315 >325 291 167.8 175.0
-55 —52.7 -50.0 —23 4.4 21.7 — 10;0
0.970 0.971 0.973 0.959 . 0.995
.00097. 0.00097 0.00097 0.00066 0.00066
C.00037
0.086 0.087 0088 0.103 0.103
1%° <2%*
35 35 .35
3.74" '3.57" - 3.3 4.4 .3.1
2.75 2.75 2.75
2.75 2.75 2.75
0.06° 0.0097' 0.01 0.01 0.016
<0.0001 <0.0001 <0.0001
0.00005 0.00013 0.00015 0.0013
>lxlC'" >lxlO" >lx!0" 3x10"™ 6.3x10"* 5x10" 1X10"
~
Tetra Ethylene Silicate
Hydro- Glyco! Ester
furfuryl Base
Oleate Fljid
61
10 12.2
3.95
203.9 116 187.8
0.15 max
^17.8 <-£9J
• I
1.1154 0.887
0.00062 .000863
-00063 .000327
0.080
196-206 >371.1
27' .
4.3
2.65
41 2.65
0.019
0 0336
0.00039 C.0f42
<1XJO" 9x10'" .
-------
Table 2
Physical and Other Properties of Lubricating Oils, Engine Oils, and Hydraulic Fluids
. — : : ' ~~ s"
Vlscosltv. cs C
Fluid.
MIL-2190
Harmony 44 (Culf)
MI.0-5731
Hl.0-7277
MLO-60-294
Mjbll DTE-103
M1L-H-6083B
M1L-II-5606A
MIL-0-5606(Bs»o Unlvii J-O)
Chemical Clasa or Compound
Mineral Oil
ti II
" " - NaphthenU
n H ii
" " - Parafflnlc.
deep devaxed
Mineral Oil
II 1*
100'F
32.2
87.6
14
124
--
210°F (W
Mineral Oils
5.8
9.8
3.15
8.74 to 10.2
--
jeclflc
ravlty
itcr-1)
0.86
0.88
0.88
0.92
--
Point
zlll
385
390
255
195
Point
--
430
•-
_ —
225
/Vutolgnltloi\i'r Decomposition
Temperature Temperature
"F *F
665(5)
630(5)
464(50)
700(27)
702, 6_LS(50)
470(50)
437(4)
437(2)
640(28)
725(30)
/~620(30)
"_
.•.
--
Clycola and Water Glycola
Kthyltne Clycol
Propylene Glycol
Sthylene Clycol + 501 Water
Hough to -Safe 271
ii .1 520
n H A">n
O iU
Nyvnc 20(Kjt>tl)
Irua 902. (Shell)
Ucon SOMB-260
Ucon 50IU3-230-X
Ucon LB-60
Ucon LB-400-X
Houfchto-Safe 1010
" " 1055
" " 1115
" " 1120
" 1130
Clycol
i«
Vlater-Clycol
M II
WaterrClycol and addltlvea
Water-Oil Emulsion
PolyalVylene Clycol
it n
ii ii
•
Trlaryl Phosphate Eater
n «> **
n ii it
n ii n
n i> "
8.7
19.6
2.2
43.2
43.2
41
97.4
56
10.7
18.2
13.0
32.2
49.8
62.8
~16(150'P)
25.1(130*!')
29.8(150'F)
51
mm
Phoaphate Eaters
3.9
8.0
4.1
5.0
6.0
1.045
1.075
1.055
. 1.07
0.93
m m
..
1.20
1.145
1.165
1.15
1.145
240
230
--
455
500
310
505
505
-.
435
490
235
--
500
600
.325
__
670
680
680
690
680
856(38)
835(38)
903(38)
767(5)
--
750(51)
709(51)
7<.3(3fl)
743(20)
653(38)
752(20)
>1200(5l)
10'JO, 830(50)
>1200(51)
1020(5)
>1200(51)
-•
" "
--
--
--
::
•-
--
"
-------
Table2 (Cent)
Viscosity, cs (
Fluid
Chemical Class or Compound
100"F
210°" (I
Specific
Gravity
«'ater-l)
Flash
Point
*F
Fire
Point
°F
Autolgnltloti^
Tempera ture
»f
Decomposition
Temperature
°P
Phosphate Esters (Cent)
MlL-H-19457(Type 1)
Tricresyl Phosphate
Trloctyl Phosphate
Trihexyl Phosphate
Pydraul AC
Pydraul P-9
Cellulube 220 (Shell S.P.R.)
Pydraul 150 (Moneanto)
SUydrol
Plexol 201
Plexol 244
C- Plexol 273
00 Plexol 79
KIL-L-7803 (0-60-13, Esso 4040)
NlL-L-7308 (H-1026)
M1L-L-9236B (0-60-7, TP-653B)
MIL-L-9236 (0-60-27)
Mll-L-9236 (0-60-23)
MIL-L-9236' (0-61-17)
M1L-L-9236B
HLO- 54-581 (Texaco. TL-2456)
TP 65J3 (!ley. Newport)
P/0 (Esso 4275)
KLO-60-50
Trlmcthyolpropane Trl-
pclargonate
m.o-54-^oac
MLO-56-230
MLO-56-578
Trlaryl Phosphate Ester
n ii H
Trlalkyl Phosphate Ester
it it n
Phosphate Ester-Chlorinate*
Hydrocarbon
n ii
Phosphate Ester
ti n
M n
Dl-2-hexyl Sebacate
Dl-lsooctyl Adlpate
Dl-tsodecyl Adlpate
Polyester
Sebncate-adlpnte Dlester
Dl-2-ethylhexyl Sebacate
Trlinethylol Propane Ester
ii n n
11 II M
II II It
II II II
Dlester
Trlmethylol Propane Eater
Polyester
Trlmetliylbl Propane Enter
n n ti
Tetra Dodecyl Sllane
Dlphenyl dt-n-dodecyl Sllane
Octadecyl trloctyl Sllane
--
38.3
• -
--
88.8
50,9
43.4
30.5
--
Xono-
12.7
9.64
14.5
1,250
12.1
12.58
15.1
14.8
15.99
15.78
16
--
--
--
--
--
34.58
37.2
27.5
-.
4.48
--
--
5.0
5.9
4.9
7.9
--
and Dibasic Acid
3.31
2.77
3.56
108
3.1
3.3
3.4
3.45
3.62
3.59
3.2
--
8.04
--
--
Sllanea
6.37
6.2
5.76
-.
1.17
0.926
--
1.36
1.285
1.145
1.125
--
Esters
0.912
0.926
0.920
1.023
--
--
--
--
..
--
0.97
--
•vO.97
0.951
--
--
..
-.
--
..
470
405
--
450
430
455
380
360
420
400
425
5'.0
437
-.
430
435
470
490
425
435
--
510
--
--
555
530
520
..
..
--
745
675
665
470
470
450
445
460
620
460
.-
475
485
525
535
510
475
--
--
-.
--
625
580
590
1040(19)
1110(12)
545(13)
549(12)
1148(5)
1100(51)
1033(5)
971(51)
>1300(51)
._
712(12)
..
728. 486(7)
755(50)
73fl, 491(7)
..
..
-.
>800(51)
734(2)
703, 507(50)
711, 500(50)
--
.-
775(17)
690(17)
790(17)
m —
680(48')
^350(23)
..
__
m „
,.
..
--
_ m
. .
. .
..
490(26)
575(15)
-650(74)
..
..
*-650(24)
..
.-
..
7&fl(30)
606(26)
658(15)
>600(15)
--
-------
Table 2
VD
Fluid
MLO-56-582
MLO-5f.-6U>
KLO-56-611
MLO-57-9
Tetra ( Z-ethylhexyl)Slllcate
Orall B.F.I
Oronite 8200
Orunl t e 8S 1 5
MLO-54-645
MLO-S4-560 (Monsanto OS-45)
MLO-54-856 (Holllngshead ,
72073C)
Versilube F-50
Vcrsllube F-44
Uow Corning 190
Dou Corning 600
Dou Corning 500
Duu Corning 550
Dou Corning 700
Dou Corning 710
MLO- 59 -SO
Chemical Class or Compound •
Octadecyl trldecyl SUane
Dodecyl trldecyl SI lane
Dldodecyl dloctyl Sllane
Tetra undecyl Silane
Ethyl hexyl Silicate
(2-ethylhexyl) Silicate
Silicate Ester
It II
857. Oronite & 15% Plexol
Silicate Ester
n n
Slllcone
Polymethyl Slloxane
Polymethyl Slloxane
Polyethyl Slloxane
Slllccne
Poly (methyl, phenyl) Slloxane
Methyl Phenyl Slllcone
50Z Methyl Phenyl Slllcone
(DC 250) plus 501 TKP Adlpat*
Tetracoproate
Viscosity,
100°F
ca
210°F
Sllanes
33.9
26.4
23.1
29.26
Silicates
— —
31.75
24.3
..
--
--
52
55
22.6
10.9
44.9
65 to 87
2.8
220
61.8
6.8
5.6
5.0
6.11
and
m _
11.14
8.11
—
--
--
16
17
13.5
Hatogenated Slllconea
MLO- 53-666 (CE 81406)
MLO- 59-287 600(5l)
>600(5l)
760(20)
583(15)
625(30)
516(15)
630(30)
-------
Table 2 (Cone)
Fluid
OS-124 (Monsanto, SP4E)
MCS-293 (Monsanto)
MLO-59-692 (Monsanto)
mn-4P4E
pp-4P3£
mnini-5P4E
5P4E
PPPP-6P5E
Specific
Viscosity, cs Cravltv
Chemical Class or Compound
5 Ring Polyphenyl Ether
Aromatic Ether
Bis (phenoxyphenoxy) Benzene
Bls(m-phcnoxyphenyl) Ether
Bls(p-phenoxyphcnyl) Ether
m-Bls(m-phcnoxyphenoxy) Benzene
Bls(phenoxyphenoxy) Benzene
81s [j>-(p-phenoxvphenoxy)phenyl]
Ether
100°? 210°F (Water-1)
363
25.
--
60.
2.
332
380
4.
Aromatic
13.
2 '4.
-
9 5.
83(300*F) 1.
12.
13.
20(400'F) 1.
Ethers
1 1.20
13 1.19
.
98
51(400*F)
7
4
55(600*F)
Flash
Point
•F
550
428
465
516
540
560
635
Fire
Point
660
518
535
660
660
Autolgnltlon^' Decomposition
Temperature Temperature
1112(50)
914(50)
1095(17)
1040(17)
1050(17)
1130, 1030(7)
1030(17)
>3 30(30)
~675
943(30)
-'835(17)
~335(15)
fi70( 17)
870(26)
773(15)
Phosphonltrt lea
MLO-63-24
MLO-63-25
Hexaphenyltrlphosphonltrllc
Phenoxy base Trlphosphonltrlle
--
•-
-
-
-
-
...
--
--
--
910(30)
905(30)
Urd oil
Linseed oil
Lube oil, cylinder
" , light machtn*
. " " , spindle
Het.haden oil
Mineral seal oil
Olive oil
Palm oil
Hne oil
Rapeseed oil
Rosin oil
Soybean oil
Tung oil
Turkey-red oil
S.A.E. No. 10 lube oil
S.A.E. No. 60 lube oil
Tucramerlc Octylfluoroamyl
Fhosphoni.trI late
Mlgcellaneoua Oils
<1
0.93
<[
<1
0.927
--
0.91
0.92
0.86
0.915
0.98-1.1
0.925
0.94
.-
..
--
395
435
318
169
435
170
437
421
172
325
266
540
552
476
340
480
535
535
370
200
255
175
5SO
380
620
900(19)
833(47)
820(47)
783(47)
828(47)
826(47)
650(47)
836(47)
648(47)
833(47)
855(47)
833(47)
720(20).
770(20)
Viscosity, gpeclflc gravity, flash point, «nd fire
T/Autolgnltlon and decomposition temperature data from references cited In parentheses.
point data mainly from vendor's literature.
2/ Ignition evidenced by visible flame except for underlined values where sudden pressure rise was used. Bureau of Hlnes data (Refs 2 4, 5 7
•nd 50) were obtained using reaction vessels >200 cc. Values listed for other references were determined In reaction veaaels <125 cc.
-------
exercized through companies which insure against fire, utilities which
supply electrical power, and building codes.
3. Extent of Capacitor Use
Almost all industrial capacitors contain PCBs . In 1968 95> percent
of the U. S. production of capacitor liquids (2.U6 million gallons) were
PCBs (9). Two important types of capacitors are phase correction capaci-
tors on power lines and ballast capacitors for fluorescent lighting. Non-
ballast industrial capacitors produced in 196? had a value of $112 million
(10), and fluorescent lamp ballast capacitors produced that year numbered
21.7 million units with a value of $15-5 million (10) . In 1970 there were
50.9 million ballast units produced with a value of $163 million (ll).
These ballast units are in extensive use inside buildings where non-
flammability is important.
Phase correction capacitors are necessary on power circuits to correct
for the inductive loading of much electrical power equipment. The amount of
phase correction capacitance is ordinarily specified in kilovolt amperes of
reactive current or kvars. Most power capacitors are rated at from 1/2 to
25 kvars so that the number of capacitors is very roughly the kvar value
divided by 10 (12). As examples of the extent of power capacitor use, TVA
has 2-1/Ij million kvars (13), and a power company serving suburban New Jer-
sey has 3-6 million kvars on their power lines with 1/2 million kvars on
order (lb). The value of these capacitors is roughly $5> per kvar (llj).
More than 20 million kvars of power capacitors were produced in 1970 (16) .
The procurement lag for these capacitors is 1-1/2 to 3 years, and esti-
mates for redesigning new systems range from 3 to 10 years, according to
power company representatives to ASTM Committee D-27 (ll4,l5). Extensive
re-designing is anticipated if distribution capacitors were required to use
presently available non-PCB liquids. Askarel capacitors have been developed
to the point that failures are considered negligible (13,
Several private sources reported extensive efforts to find replacements
for PCB capacitor fluids, but none reported having a good substitute.
B. TRANSFORMERS
Most power transformers contain a liquid to electrically insulate and
remove heat from the core and windings. The properties required of these
liquids are:
1. Non-flammability (required for indoor use and desirable in remote
location use) .
2. High dielectric strength (prevents breakdown and allows transformer
size reduction) .
3. Low viscosity (promotes convective heat transfer).
h. High chemical stability (allows higher temperature operation and
reduces degradation of the transformer).
-------
5. Compatibility with other materials
6. Inert decomposition products (reduces fire danger and damage to
other materials following breakdown).
7. Low toxicity of the liquid and its decomposition products.
8. Low cost.
1. Advantages and Disadvantages of PCB in Transformers
The PCB transformer liquids, commonly called askarels, are mixtures of
chlorinated biphenyls and chlorinated benzenes. Several standard mixtures for
transformers (differing from the capacitor askarels) are specified by ASTM (17)<
These liquids are used to overcome the fire and explosion hazards present with
transformer oils. For most power transformer applications where occasional
explosions and fires do not endanger life and property, mineral oils are still
preferred. However, for distribution transformers which are located near
congested areas and in buildings, askarel and dry-type transformers are re-
quired by electrical codes (6). Other advantages of the askarels include: 1.
their superior chemical stability, which eliminates the sludge formation com-
mon in mineral oils, 2. a high dielectric strength, which reduces electrical
failures, and 3. suitable viscosity.
The disadvantage of the transformer askarels include: 1. a poorer resist-
ance to iinpulse voltages and production of highly corrosive HC1 during arcing,
2. a tendency to damage common insulating solids inside the transformer, 3«
probable toxicity, and ij. higher cost (about $1.80 per gallon compared to $.25
per gallon for mineral oil (l53 18).
2. Replaceability of PCB in Transformers
Askarel transformers cost about 1.3 times as much as oil transformers,
and dry types cost about 1.5 times as much as oil transformers. Thus most
users prefer to use the oil type where possible. This preference for oil
transformers accounts for the fact that 96 percent of transformer liquids
in use in 1968 were mineral oil (9). However, fire underwriters will not
accept the use of oils, silicones, and other flammable liquids for indoor
transformers. Dry-type transformers can be used indoors, but are generally
larger in size, require more copper and iron, and are somewhat more expensive,
as shown above. Dry-type transformers could possibly replace askarel trans-
formers in many cases.
No currently available liquid which will replace askarels in existing
transformers is known. Possibly, non-flammable fluorocarbons could be de-
veloped as a suitable fluid3 similar in important properties to the askarels.
Fluorocarbons are currently in use as convective and evaporative dielectric
coolants. One main disadvantage of the fluorocarbons is their high volatility
and high cost (about hO tijnes the cost of oil and 6 times the cost of askarels
(18) ).
3. Extent of Transformer Use
In 1967, 1.7 million liquid-immersed distribution transformers of £00
kva and smaller, valued at $350 million, were produced (10). These include
askarel-filled transformers placed under streets to serve 1 - h city build-
ings. These transformers can fail and cause fire damage if filled with a
52
-------
flammable liquid. An annual report on such failures is compiled by the
Edison Electric Institute (19)•
II. INDUSTRIAL FLUIDS FOR HYDRAULIC, GAS TURBINE, AND VACUUM PUMP USES
A. HYDRAULIC
Hydraulic fluids are liquids used as force transmitters (20, 21).
The characteristics of a good hydraulic fluid are (20):
1. High lubricity (lowers heating and increases lifetime of moving
components).
2. Stability (increases lifetime of use).
3. Appropriate viscosity and high viscosity index (2h).
h. Low pour point (necessary for material to flow at low temperatures
(25).
5. Compatibility (prevents interactions with other components, for
example, rubber seals).
6. Good heat transfer (reduces local heating and large temperature
gradients).
7. High bulk-modulus (important for extreme pressure applications).
8. Low volatility (necessary to prevent malfunctioning due to "vapor
lock").
9. Low foaming.
10. Low thermal expansion. Aside from the implication of a more con-
stant volume over a wide temperature range, a low thermal expansion implies
a high viscosity index and the constancy of certain other properties with
respect to temperature.
11. Good demulsibility.
12. Inhibitor (necessary to prevent oxidation of metals or rusting).
13- Good fire resistance (very important in high temperature environments).
iLi. Low density (desirable in transportation, particularly airborne,
applications).
15. Good dielectric properties (reduces arcing or short circuiting should
the fluids come in direct contact with electrical components).
16. Non-toxicity (reduces the danger to human beings from rupture of
hydraulic equipment or improper disposal and to maintenance personnel during
transfer of these fluids).
Since most commercial hydraulic fluid mixtures are proprietary, it is
difficult to obtain information with respect to their composition. The results
from inquiries with respect to PCB content have been somewhat contradictory.
No definite knowledge is available that PCBs are present in commercial hydrau-
lic fluids. Since composition specifications of these fluids are usually not
available to the public, PCB content should be established by chemical analysis.
PCBs are useful in hydraulic fluids as lubricating additives in extreme
pressure applications (26) and as pour point depressants. Although it is true
that the pour point of oils may be lowered by extensive dewaxing, the use of
additives is much cheaper. There are other inexpensive additives which are
often used for these applications and which appear to be adequate. For
-------
example, TCP (tricresyl phosphate) is chemically stable as an additive in
lubricants, and, although quite toxic, it is more biodegradable than the
PCBs.
An important requirement for many applications of hydraulic fluids is
good heat and fire resistance (2?). Table 2 (28) gives the ignition charac-
teristics for a. large number of lubricants; however, in view of the propriety
stated earlier, there is no detailed specification of the compositions of those
fluids which are given the brand names. PCBs have excellent fire resistance
characteristics. The flash and fire points given in the literature for the
pentachlorobiphenyls are attributed to the burning of residual contaminants
(29). At very high temperatures, however, PCBs with higher chlorine content
may emit phosgene (a very toxic gas) in the presence of oxygen. (No evidence
is available that high chlorine content PCBs are being used here).
Aircraft hydraulic fluids are an example of an application where excellent
heat and fire resistance are necessary in view of moderately high operating
temperatures and frequent accidents involving ruptured hydraulic components in
the proximity of hot metallic surfaces. Also the fiberglas acoustic blankets
in the jet engines become soaked with leaking hydraulic fluid within as little
as one year of use (30)' Fire resistance in phosphate ester type hydraulic
fluids has been related to PCB content (3l). Phosphate ester hydraulic fluids
have been used extensively for commercial aircraft (32). According to one
manufacturer, no PCBs are currently being incorporated in these fluids. PCBs
have been assumed to be useful as "snuffers" in that they tend to extinguish
a fire supported by other constituents.
The market value of used phosphate ester type hydraulic fluids is suf-
ficiently high that they are being recycled (33). The recycled products are
said to satisfy the same specifications as the uncycled fluids.
Considerable research is being done in connection with fire resistant
hydraulic fluids for military aircraft. Some of the hydraulic fluids being
tested do not contain PCB additives, but do contain TCP. It is possible
that under appropriate processing, PCBs may be replaced by TCP and perhaps
certain other additives to obtain satisfactory lubrication.
In naval applications current research includes development of water
based hydraulic fluids (3h), which would not contain PCBs. The boiling points
of these fluids are too low to permit their use in aircraft.
It is possible that PCBs are also used in phosphate ester and other
halogenated hydraulic fluids for industrial applications at high temperatures.
The requirements here are sijnilar to, but not as stringent as, those for air-
craft hydraulic systems.
B. GAS TURBINES
The characteristics of a good gas turbine lubricant are similar to those
of hydraulic fluids except for the additional requirement of lubricity at high
rates of shear (35). Particular emphasis is placed on heat resistance, high
-------
viscosity index, low pour point, and oxidation and foaming resistance.
Sample U. S. and U. K. military specifications are given in Table 3 (36).
Usually, dibasic acid esters containing appropriate additives meet the
above requirements. In the case of the turboprops, the same lubricant is
usually used for both the turbine and prop-drive gear.
PCBs would seem to be useful as additives in gas turbine lubricants,
but there is no evidence that PCBs are currently used for this purpose.
Research along these lines has been done, and there is some indication
that some PCBs have on occasion been added to gas turbine lubricants.
The objection to PCBs and other chlorinated hydrocarbons is that they
tend to be corrosive at the high temperatures reached in gas turbines.
This corrosion is accelerated by decomposition of the PCBs and the forma-
tion of hydrochloric acid at high temperatures. The corrosiveness of PCBs
is a major deterrent against their use in these lubricants. TCP also has
the desirable property of reacting with metallic surfaces at high tempera-
tures to form a protective coating.
Jet engines are run for approximately 18,000 hours (37) between over-
hauls. The lubricants are not usually changed during this period; however,
the appropriate "oil level" is maintained at frequent intervals. Immediately
before engine overhaul the lubricant is drained and discarded. Unlike the
situation with respect to hydraulic fluids used in commercial aircraft, there
appears to be no general recycling facility for gas turbine lubricants (37).
As a result of their increase in acidity and viscosity during use, recycling
of gas turbine fluids would demand expensive redistillation and reblending.
C. VACUUM PUMP APPLICATIONS (22, 23)
Both mechanical and diffusion pump applications require fluids of one
highly fractionated component. Accordingly, additives generally are not used.
However, PCBs are used in pure form as a diffusion pump oil in commercial
applications.
The characteristics (38) of a good diffusion pump fluid are:
1. Relatively high vapor pressure at operating temperatures.
2. Low vapor pressure at room and lower temperatures. (The vapor pres-
sure imposes a lower limit on the ultimate vacuum).
3. Heat resistance (prevents cracking or molecular degradation at
operating temperatures).
h. Narrow vapor pressure range and freedom from contaminants such as
absorbed gases and liquids with higher vapor pressures. (This requirement
often implies the necessity of a narrow fraction).
5. Oxidation resistance (important because air may enter a diffusion
pump during operation either accidentally or through slow leakage).
6. Nonhydroscopic (absorbed water increases pump maintenance and may
contaminate the vacuum system).
7. Compatibility (must be compatible with pump and vacuum system
components).
8. Stability in the presence of the vapor being pumped.
Some of the pertinent properties of many diffusion pump fluids are given
in Table h (39). The stability, oxidation resistance, appropriate vapor pres-
sures, and, in particular, the relatively low cost of PCBs make them a desirable
choice for many industrial applications. Although the ultimate vacuum using
-------
Table 3
High-Temperature Lubricant Specifications
Viscosity, ca at r,r>0°F
400 °F
210°F
100°F
-30°K
-40°F
Viscosity stability test temp
Vis change in 3 hr
Vis after 3 hr, cs
Vis after 72 hr, cs
Vis nt -40°F after 12 hr
Shear stability at 212°F
Pour point, ° F
Flash point, °F
Spontaneous ignition temp, °F
Vapor pressure at 500° F, mm Hg
Evaporation loss test temp
% Loss 6-1/2 hr at 29.9" Hg
% Loss 0-1/2 hr at 5.5" Hg
Specific heal, UTU/lb/°F at 100°F
Specific heat, B.TU/lb/°F at 500°F
Rubber swell, 72 hr
Rubber swell, 168 hr
Foaming sequence 1-2-3, max vol
'•'earning collapse time, max, min
Gear scuff at 165°F % reference
Clear scuff at test temp, % reference
Gear fatigue, hr to failure
M!!,-L-9236
1.0 min
Report
-65°F
6% max
21,000 mnx
24,000 max
—75 max
425 min
750 min
400°F
15 max
12-25% at 400°F
100-25-100 ml
5-3-5
56 min (8 sides)
Report (400°F)
Report (400°F)
MIL-L-27502
1.0 min
Report
Report
13,000 max
-30 °F
6% max
13,000 max
17,000 max
- 40 max
500 min
Report
5.0 max
500 °F
10 max
Report
0.35 min
0.45 min
12-25% at 500°F
100-25-100 ml
5-3-5
100 min (8 sides)
Report (500° F)
Report (500° F)
DKRD 2497
2.0 min
8.5 max
13,000 max
-65°F
Report
± 2% KV/210°F
500 min
752 min
392 °F
Report
15-25% at 15S°F
100-25-100 ml
5-3-5
100 min (392°F)
(Ref. oil at 230°F)
-------
Table 4
Some Properties of Pumping Fluids
VJT.
Fluid
Apiczon A
Apiczon B
A'piczoa BW
Apiczon C
Apiczoa G
Apiczon I7\V
Convoil 10
Convoil 20
Di-«-butyl plithalatc
Di-2-cthyl hcxyl plithalatc
Di-2-cthyl hcxyl scbacate
Di-nonyl phthalatc
Tri-crcsyl phosphate
Tri-xylcnyl phosphate
Glyccrol
Mixed clilorinatcd
diphcnyls
Mixed chlorinated
diphcnyls
Siliconc D.C. or M.S.702
Siliconc D.C. 703
Silicor.c D.C. or M.S. 704
Siliconc D.C. or M.S. 705
Convalcx 10 or V.R.T. fluid
Mercury
Proprietary
names
As under 'fluid'
"
"
"
"
" "
" "
Octoil
Octoil-S
Narcoil-20
Viacoil-20
Narcoil-40
Viacoil-40
Aroclor 1248
Convaclor 8
Clophcn A-40
Aroclor 1254
Edwards Booster fluid A
Narcoil-10
Viacoil-10
Convnclor-12
Clophcn A-50
As under 'fluid'
,.
E
—
Chemical nature
Paraflinic hydrocarbons
" |?
" ••
11 "
" >f
»» u
» '•
C H'fCOOC I1')
c H*(COOC'H \
CsH^COOCsHl,),
C6H<(COOC1,H10)3
(CH C H ) PO
[(CI-I )°C'H 1 P*O
(CH:OH)C;CH(OH)
Approx. CiaHcClt
Approx. CiaHsQj
\Mctliyl polysilo.x.incs
Tctraphcnyl fctrar.iethyl trisiioxan
Tcntaplicnyl trimcthyl :risiloxane
Mixed 5-rins polyphcnyl ethers
Hg
Specific
'titular gravity
,viy/if (room temp.)
-!6S
472
574
445
ISO
JOW
1 SO
4JV
400
273
391
427
419
36S
414
92
292
326
530
570
546
447
200-6
0-872
0-873
0-880
0-873
0-91
0-86
1-044
0-983
0-912
0-973
1-17
1-14
1-26
1-45
1-54
1-071
1-089
1-066
1-095
1-198
13-6
Flash
point
(open °Q
218
235
265
232
191
218
159
196
209
215
240
243
193
none
194
227
216
243
288
—
Viscosity
(centistokcs)
at 20'C
69
100
295
86
147
120
19
75
24
105
1GO
1180
400
~6000
38
40
47
170
(25°Q
2500
(25"Q
1-15
/f/i/iro.v.
pour point
(or freezing
point) °C
-12
-12
-9-5
-12
-23
-8-9
-71
-52
-56
-7
10
-40
-36
-38
-15
4-5
-38-9
dpprox.
boi'lii'!!
point fit
1 torr °C
190
220
225
255
210
165
150
195
102
204
215
215
'219
2
-------
PCBs is limited by their relatively high vapor pressure at Low temperatures,
their use at high boiler pressures makes possible operation with poor force
vacuums. Hence they are useful as booster pump fluids. In this respect the
vapor pressure-temperature properties are closely matched by amyl phthalate.
Except for certain applications where alternative liquids may be incom-
patible with the vapors being pumped, the advantage of using PCBs diffusion
pump oils appears to be mostly an economic one. Other fluids may often be
preferable through considerable more costly. TCP is used as a commercial
diffusion pump fluid and is also inexpensive. Its vapor pressure (L9) is
lower than that of the PCBs making it less desirable in booster pumps, but
in many applications TCP may be a suitable replacement. PCB diffusion pump
oils can be decomposed after usa by incineration. This service is available
mainly for disposal of Askarel transformer fluids containg PCBs.
III. HEAT TRANSFER APPLICATIONS
Heat transfer fluids are used to absorb thermal energy from a source and
by cooling or changing phase, deliver heat to a place of utilization. The re-
verse process, using a fluid as a coolant, requires similar fluid properties.
Summaries of heat transfer fluids and applications are available (hi, 12).
The properties required of heat transfer fluids are (Ijl) as follows:
1. Suitable density and expansion coefficient.
2. High heat capacity or heat content (increases amount of heat trans-
ferred during cooling or phase change).
3. High heat conductivity (increases heat transfer).
h. Low viscosity (necessary for fluid flow through system).
5. Physical stability (will not have unpredictable phase or property
changes).
6. Chemical stability (will not degrade, oxidize, etc.).
7. Radiolytic stability (will not suffer damage from radiation if
present).
8. Low cost.
9. Low surface tension (reduces fluid flow and heat transfer between
fluid and surroundings).
10. Low corrosion (reduces damage to metal parts of the system).
11. Low flammability (reduces fire and explosion danger).
12. Low toxicity.
Electrical properties, refractive index, appearance and odor may be
considered for some applications.
A. ADVANTAGES AND DISADVANTAGES OF PCBs AS HEAT TRANSFER FLUIDS
The main advantage of the PCBs as heah transfer fluids :-.3 their fire
resistance. This property if of primary importance where there is a possi-
bility that fire from high temperature leakage could endanger life and pro-
perty. The other advantages of PCBs are low pour points and viscosities and
good thermal stability up to 600°F. PCBs are relatively inert and have ex-
cellent electrical properties, which makes them valuable for cooling trans-
formers. The cost ±3 relatively low. Disadvantages of PCBs include possible
58
-------
toxicity, a tendency to decompose to form highly corrosive HC1, a lower
decomposition temperature than some alternate liquids (U3) and relatively
poor radiation resistance (UU).
B. REPLACEABILITY OF PCBs AS HEAT TRANSFER FLUIDS
Increased risk from fire and explosion is a major disadvantage with
most PCB replacement fluids. Other non-flammable fluids are: 1. fluoro-
carbons, which have low toxicity, high thermal stability, and in spite of
high cost are used as convective or evaporative coolants (l), 20 water,
which is quite corrosive, has a high temperature limit of 31h°C and requires
extremely expensive high pressure systems for its use above the atmospheric
boiling temperatures and 3. molten salts and metals which, because of their
resistance to radiation damage, are useful in reactor applications.
Several liquids are more stable at high temperatures than the PCBs0
Table 0 (Ij2) shows the decomposition point range of liquids in a variety of
chemical classes0 Few of these liquids are non-flammable, however, as can
be seen from Table 2» The phosphate esters, silanes, and aromatic ethers
have high fire points (around 600°F), but they are flammable and it is not
clear how high the fire point must be for a fluid to be safe in a high tem-
perature system, especially in the event of leakage into a furnace0 The
details of specific heat transfer applications are necessary to evaluate the
suitability of PCB replacement fluids.
IV. PLASTICIZER AND MISCELLANEOUS USES +
A plasticizer is a material incorporated in a plastic to increase its
workability and flexibility (h5,U6). The addition of a plasticizer may
lower the melt viscosity and flow temperature (increasing the ease with
which the plastic can be made to flow),or lower the elastic modulus (making
the plastic softer) (U6). Plasticizers are generally non-volatile liquids
or low-melting solids. A major requirement of a plasticizer is that it have
high compatibility*- (.mixes will to form a homogenous composition with useful
properties) (Ij2) with the material being plasticized. Figures are given in
Table 6 for the compatibility of some common plasticizers with some common
synthetic thermosetting or thermoplastic resins (h5)« Other properties which
are important when considering plasticizers are specific gravity, refractive
index, color, odor, moisture sensitivity, vapor pressure (volatility),
boiling range, stability (to light and heat) toxicity and cost (h7). Of
course, the properties of the final plasticized material are of prime importance.
Certain plasticizers provide formulations with specific properties such as:
1. phthalate esters - general purpose.
2. adipates and ozelates - low temperature flexibility.
3- highly aromatic esters - fast processing, strain and extraction
resistance.
U. epoxies - heat stabilization during processing.
$. phosphate esters and PCBs - fire retardant materials.
+ The information in this section about specific uses was obtained from Chemical
Abstracts (1928-1969) and patent claims. The Task Force has no knowledge whether
or not specific applications are in current production or use.
# Note that the term "compatibility", used here, has a meaning very different
from its use earlier in this appendix. In the earlier case, compatibility meant
that two materials could coexist without either being affected by the other.
The present meaning is quite the opposite.
59
-------
Table 5 U2)
Decomposition
Point
Range (°F) Chemical Class
Over 800 Unsubstituted Polyaromatic compounds
Unsubstituted Polyphenyl ethers
Unsubstituted Aromatic amines
Unsubstituted Aryl silicates
Unsubstituted Aryl silanes
Unsubstituted Aryl borates
700-800 Lower alkylaromatic ethers
Aromatic phosphates
Aromatic sulfones
Aromatic ketones
Silicones
Halo-substituted aromatic ethers
Halo-substituted polvphenvls (including PCB's)
600-700 Alkyl borates
Alkyl silicates
Higher alkylaromatic ethers
Highly refined mineral oils
Fluorinated esters
Neopentylpolyol esters
500-600 Sebacate esters
Methyl aryl esters
Aliphatic tertiary amides
60
-------
Table 6. Approximate Maximum Compatibility, phr+, of Plasticizers with Various Resins
I'hlliulyl
Adip:ik-:
l'o!ycst'¥is
Kp- Snlfon-
oxides amides MiseellMieui
poly(viny! chloride)
polvfvinvl :ti--et;itc)
poly(vin;,-|idcnu iliim-id':)
polystyrene
ctliylceilulo.se
cellulose tiitraiu
cellulose ncet. ite
cellulose ucL-Ute l.iutyrate
clilurinMcd rubber
lngli slyrcM:e-bi:t:»diein: copolynu1"
pro'.ein-ljn.v.'d pieties
shellac
acrylie. re-?ins
polynntidc.-;
polyesters
cpo.\y resin*
phenolic mins
nlkyd resin.-;
niul:iiniiiu fornnldeliyde. remind
polynrctlian
nitrile and neoprene. mbbor
0 Trademark Monsanto Co.
* Trademark Union Ciirbidc Corp.
' Trademark Holnn and Haas Co.
— •
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100
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vlhexvl I
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-------
PCBs are attractive as plasticizers because of their high compatability
factor. They have been made with a wide range of properties, as shown in
Table 7 (JaS). The PGBs are permanently thermoplastic, chemically stable, non-
oxidizing, non-corrosive, have excellent solvating powers, and are fire re-
sistant (Ij8, h9)« They are not normally attacked by acids, alkalines, or
water. They are insoluble in water, glycerol, and glycols, and are soluble
(at the lower chlorine contents) in organic solvents (Ij8).
The main disadvantages of PCBs are their possible toxicity, and relatively
high cost.
A. ADHESIVES
An adhesive is a substance capable of holding materials together by sur-
face attachment (51, 52). The major types of plasticized resin adhesives are
emulsion, hot-melt, delayed tack, solution, pressure-sensitive and adhesive
primers and coatings. Almost every thermoplastic resin is used individually
or in resin blends as a hot melt adhesive. This necessitates a wide range of
plasticizers. Of special value are the solid plasticizers. They plasticize
the resin while hot and while the bond is being formed, but solidify at lower
temperatures to overcome the problem of excessive softness (53). Among those
solid plasticizers used are: o,p-toluenesulfonamide, N-cyclohexyl-p-tolunesul-
fonamide, triphenyl phosphate, and diphenyl phthalates. The more resinous
chlorinated polyphenyls would also be included in this category. Hot melt
adhesive compositions based on phenolic resins are used in brake linings,
clutch faces, and grinding wheels. Reactive plasticizers, such as the toluene-
sulfonamides, are employed because they improve the flow properties by reducing
the viscosity of the phenolic resins (5M- They help the resin wet the fillers
and abrasives. Chlorinated polyphenyls and aryl phosphates (non-reactive
plasticizers) also improve flow properties of phenolic resins prior to curing
as well as imparting some flame proofing characteristics to the composition.
PCBs have also been used in laminating adhesive formulations involving poly-
urethanes and polycarbonates (55-57) to prepare safety and acoustical glasses.
The laminates have improved strength and resistance to delamination over a
broad temperature range, and improved sound-absorption and energy dissipation
properties.
Polyarylene sulfides, treated with chlorinated biphenyls, are employed to
laminate ceramics and metals (58, 59). An ethylene-propylene copolymer blended
with PCB has been used in a hot melt adhesive having improved toughness and re-
sistance to oxidative and thermal degradation. It has excellent adhesion to
polyethylene films (60). Similar adhesives, used to bond polyethylene to itself
or other plastics, were prepared from styrene, alpha-methylstyrene or methyl-
methacrylate (6l) Washable wall coverings and upholstering materials, made
from films of polyvinyl chloride, are claimed to be improved by the addition of
PCB to the adhesive formulation (62). PCBs can also be applied in the pre-
paration of polyvinyl alcohol adhesive compositions which are used to manufac-
ture envelopes (63), in self-adhering films (610, and in preparation of coatings
of pressure-rupturable capsules for adhesive tape (65).
B. TEXTILE COATINGS
A textile coating for ironing board covers can be formed from a mixture of
chlorinated biphenyl, cellulose acetobutyrate, and aluminum metal particles (66).
PCBs also can be used as a de-lustering agent for rayons (67, 68). Poly- alpha-
olefins, (i. e., polypropylene) films, when coated with a mixture of PCBs, UV
62
-------
Table 7. General Properties of Some Aroclors (PCB)
Os
VjJ
Material
Aroclor 1221'
Aroclor 1232
Aroclor 1242
Aroclor 1243
Aroclor 1254
Aroolor 1200
Arodor 5202
Aroclor 126S
Arocl-ir 1270
Aroclor 4465
Aroclor 5442
Aroclor 5400
Aroclor 25G5
Form and color
colorless, mobile oil
almost colorless,
mobile oil
almost colorless,
mobile oil
yellow-jjrccn tinted,
mobile nil
light yellow, vL«:ou9
oil
light yellow, soft,
aticky, rosin
light yellow, sticky,
clear resin
white to oil-white
powder
while crystalline
powder
transparent, yellow,
brittle resin
yellow, transparent,
aticky resin
clear, yol'.uw-toam-
ber, brittle resin
it *
hlai'k, <>i,;u;ue,
brittle resin
Specific
gravity
1.1S2-1.192
(25/15. 5°C)
1.270-1.2SO
(25/1 5. 5°C)
1.381-1.392
(25/15. 5°C)
1. 405-1. 415
(Go/15. 5°C)
1.4 1)5-1. 505
(05/15. 5°C)
1.555-1.500
(90/15. 5°C)
1.5 72-1.. '.S3
(90/1 5. 5°C)
1.S04-I.SH
(25/25cC)
1.9 14-1. OHO
(25/25°C)
1.070
(25/25'C)
1.470
(25/25°C)
1 . 070
(25/25-C)
1.734
(25/25'C)
Diatillation
°C (corr)
275-320
290-325
32.5-306
340-375
305-390
3S5-120
305-425
435-150
450-100
230-320
(4 mm H-)
215-300
(4 mm IT;;)
2SO-335
(5 mm Us)
Fl.-iah
point,6
°c
141-150
152-151
170-1SO
193-195
none
none
none
none
none
none
247
none
none
Fire
point,*
°C
170
238
none
none
none
none
none
none
none
none
>350
none
none
Pour
point, d
°C
crystals at
1'C
-35.5
-19
-7
10
31
35-3P
46
Softening
point,'
°C n?
1.017-1.01$
1.C20-1.622
1.627-1.C29
1.630-1. 031
1 .630-1 .041
1. 647-1. C4!>
1. 0501-1. C517
L50-170"
249-300*
GO-GO l.GC4-l.C(57
40-52
9S-105.5 1. 660-1. C05
60-72
Viscosity/ sec
:-;7.S°C. ' 93.9'C
:^-]i 30-31
44-51 31-';2
82-92 34-o5
lS'>-2-!0 30-37
1800-2500 44-4S
72-7S
SO- 100
OO-loO
(130°C)
300-400
" ASTM D-20 (modili.id). " C
' ASTM 1>2S. ' Sayboll Univeraal, ASTM U-SS.
* Hold poLot on solidification.
cup. e Cleveland open cup: none indicates no fire point up to boiling temperature. A.STM D-'.C
' Last twci digits indicate approximate chlorine content, ie, Aroclor 1221 contain? abo'it 21?^ eh!!-'-::1.-.1
-------
light absorbers, and antioxidants show increased stabilization to oxidative
degradation on exposure to sunlight and weathering (69, 70). Polyamide
(nylon- type) yarns were found to be flame proofed when treated with PG3 (7l).
Chlorinated biphenyls can also be used as ingredients in some sealing formula-
tions employed to waterproof canvas ([48).
C. SURFACE COATINGS
In paints and varnishes, the hard resinous PCBs impart increased hard-
ness to .films, and the softer resins give flexibility (h8). The role of
these materials is similar to the oil, except that they do not oxidize and
lose flexibility on aging. In nitrocellulose lacquers, PCBs either alone or
in combination with other plasticizers and resins impart increased weather-
ability, luster, adhesion, and decreased burning rates (hQ, 72).
Some comparison studies have been made recently on the effects of various
plasticizers upon the overall properties of paints and varnishes made from
acrylic latexes (73). Films plasticized with tricresyl phosphate (TCP) had
better stability, tensile strength, and adhesion than .did film plasticized
with dibutyl phthalate or PCB (73). For varnishes prepared from polyvinyl
chloride formulations, and plasticizsd with either di -butyl phthalate or PCB,
the films plasticized with PCB had better overall properties with or without
pigments (Ti02>
PCB and other plasticizers can be used in combination with poly (organo-
siloxanes) to prepare film casting solutions. These polymeric films could be
employed in electrical coatings, insulating tapes, and protective lacquers
(75-77).
Plastic vessels, i. e. bottles, manufactured from polyethylene, polyvinyl
chloride, polyvinylidene chloride or similar resins coated with an epoxy
lacquer (which contains PCB) make the vessels pliant, impervious, and resistant
to aromas, acids, and alkalis (73).
Paints at atomic energy installations are needed for (a) contaminated areas,
(b) tolerance to high energy radiation, and (c) to meet clean condition standards,
Paints for (a) should be glossy and smooth and should not transmit contaminants.
For this purpose, the vinyl polymers are preferred over epoxy lacquers. The
best plasticizers for use in this area are claimed to be the PCBs (79). The
extent, if any, of their use in this application is unknown.
The PCBs are usually compatible with epoxy resins, and they give good final
hardness and impact resistance equal to the unmodified resin (80) . They also
aid in the acceptance by the resin of larger amounts of fillers. Epoxy resins
in combination with PCB can be used as protective coatings for metals, i.e.,
encapsulating electrical capacitors (8l), for ferrite magnet cores (82) (ussd
in computers), for corrosion resistant resistors (83), for pigmented metal
coatings (Qh, 85) for winter camouflage coatings (86), and for pipes and blocks
(87).
6U
-------
D. SEALANTS
Sealing and caxilking compositions include a wide range of compounds
which can be used to seal joints or voids against water and water vapor,
air and other gases, dust, sound, vermin, heat and cold (88). Specialized
applications require resistance to certain chemicals or atmospheric environ-
ments. PCBs can be used as,.plasticizers in the formulation of putties from
copolymers or ethylene-vinyl acetate or styrene (89). The products are non-
hardening, and resistant to moisture and frost and show good weatherability
A non-sticky, non-hardening putty was also prepared from polysulfide mix-
tures which employs PCB as the plasticizer. This putty gave good bonding
to building materials and had good extrudability and shape retention (90).
Elastic pavement or concrete sealing compositions, used for traffic markings,
were prepared from coal-tar-polysulfide mixtures which are plasticized with
PCB (91). A sealant, effective for concrete and asphalt applications, can be
formulated from a mixture of polysulfide, chlorinated rubber, and polyiso-
cyanate, and plasticized with PCB (92).
E. PRINTING
Chlorinated biphenyls have been employed as part of the formulations
used to prepare pressure-sensitive record (93, 9h) and colored copying papers
(95, 96, 102, 103). They have been used to coat papers used in thermographic
duplicating processes (97-101) as well as in xerographic transfer processes
(lOh, 105). Solvent-free printing on polyolefin plastics can be accomplished
by heating a mixture of low molecular weight material, chlorinated biphenyl or
terpene resin, and suitable pigments and dyes. Diarable prints can be made on
the surface of the polyolefin at the time of their thermoplastic shaping (106),
Printing plates, hard enough for high quality letterpress printing, and suf-
ficiently flexible for use as flexographic plates, can be prepared from com-
positions containing a liquid resin such as epoxy, polyester, urethan, acrylic
or vinyl with an excess of caring agent and PCB as the plasticizer (10?). The
extent, if any, of current uses of PCBs in printing application is unknown.
F. FIRE RETARDANT AND FLAME-PROOFING COMPOSITIONS
When PCBs are used as plasticizers, they impart a certain degree of non-
flammability to the objects as described previously. However, for increased
effectiveness in flame retardant applications, the PCBs can be admixed with
various metal oxides. Some flame retardant compositions based upon these
mixtures are: polyolefin yarns (108); organopolysiloxane sealants (109)j
thermoplastic poly (hydroxylethers) (110); fireproof panels made from starch
which can be used for doors, floors, ceilings, and partitions (ill); poly-
amides (112); and in fireproof fiberboards (113). Rigid polyurethane foams
(lll4-ll6) and hardboard compositions (117), when treated only with PCBs do
not show any significant increase in flame retardance.
G. MISCELLANEOUS APPLICATIONS
The wide range of chemical and physical properties exhibited by the PCBs
(see Tables 6 and 7) make them desirable for an assortment of miscellaneous
uses. Some of the more interesting and non-conventional uses are as follows:
-------
1. Catalyst carrier for polymerization of olefins(ll8).
2. Conversion of water-permeable soil to a non-permeable state.
Soil is made non-permeable by applying to the soil a composition con-
sisting of an ethoxylene-based resin, polyamide, camphor, and PCB as
plasticizer. The composition has a density greater than water, and it
hardens under water. It can be applied to river banks, where it flows
down the bank, and after hardening, prevents penetration of water
(soil erosion-retai-dant) (119).
3. Combined insecticide and bactericide formulations. The com-
position contains aldrin or dieldrin, naphthalene hydrocarbons, malathion,
methoxychlor, lindane, chlordane, tsrpineol, and chlorinated biphenyl as
active agents (120).
ii. Inhibitors of microbial growth in enamel clay formulations (121).
5. Plastic sound ins^Lkting materials for railway cars (122).
6. Plastic (PVC) decorative articles which give the impression of
internal scintillation (123).
7. Increasing the density of carbon plates by impregnation with
PCB (12U).
8. Graphite electrodes with low thermal expansion coefficients and
high bending strengths (125>).
9. Increasing the coke yield from coal pitch. The coke is very hard,
dark, and brilliant (126).
10. As a metal quencher or tempering agent for steel, alloys, and glass
(127, 128).
11. As an aid to fusion cutting of stacked metallic plates without ad-
herence. The cutting is done with an electric arc or oxy-gas torch (129).
We find no evidence that PCBs are indispensable to a particular plasti-
cizer or miscellaneous application. In most of thf3 formulations and composi-
tions cited, there were usually alternative plasticizers included in the
citation (see Table 6) which did not appear to be detrimental to the applica-
tion,
V. SUMARY
The major value of the PCB liquids is that those with four or more sub-
stituted chlorines per molecule are non-flammable as are their decomposition
products. Thus they can be used as fluids at temperatures up to 70CrF without
the danger of explosions and fire. The major disadvantage of the PCBs is t'neir
possible toxicity danger. The other comparable class of non-flammable fluids
are the fluorocarbons which typically have a lower vapor pressure and lower
boiling point than the chlorinated compounds.
PCBs are used in fluids (known as askarels) for electrically insulating
and cooling transformers when the transformers are used in or near buildings.
Mineral oils ar-^ the preferred .fluids when fire does not create a hazard.
Dry transformers can also be used but are larger and more expensive. Fluoro-
carbon liquids require a special transformer design. Fluorescent light bal-
last capacitors and phase correction capacitors utilize the high dielectric
constant of the PCBs to effect significant reduction in capacitor size and
cost. Few suitable fluids have a comparably high dielectric constant.
Flammable fluids are not allowed by insurance companies and building codes
in capacitors used in buildings. Replacement of PCBs in capacitors and
66
-------
transformers would require considerable time and money for reengineering,
manufacture, and application of substitute equipment.
PCBs are useful in hydraulic systems where leakage onto hot metal sur-
faces could cause a dangerous fire. Hydraulic fluids can also be made with
phosphate esters which are toxic and which will burn at'high temperatures.
Replacement of PCBs in some hydraulic systems could increase loss of life
due to fire. Gas turbines require lubrication at high temperatures. PCBs
can be used but tend to be corrosive. Phosphate ester lubricants seem
better in this respect. Chemical stability is more important for high
temperature lubricants than is non-flammability. PCB fluids are useful in
diffusion booster pumps to produce moderately high vacuums with relatively
poor fore vacuums. Non-flammability is not especially important for diffus-
ion pump liquids, and with a few possible exceptions alternative liquids are
available.
Flammable heat transfer fluids present a fire hazard if they leak into
a furnace or onto hot surfaces. The use of PCBs can prevent this danger.
In some cases water is a suitable substitute at moderately high temperatures.
Other heat transfer fluids are commercially available and in use. Replace-
ment of PCBs is satisfactory in some, but may be dangerous in other heat
transfer uses.
The PCBs are good plasticizers for use with adhesives, textiles, surface
coatings, sealants, and copy paper. In some cases the PCBs act as fire retar-
dants. There are no particularly unique properties of PCBs for plasticizer
uses, and equally effective alternatives are generally available (e.g. phos-
phate esters are often used as fire retardants). The extent of current use,
if any, in such applications has not been determined.
67
-------
FOOTNOTES
1. Directory/Encyclopedia Issue, Insulation/Circuits, Vol. 17, No. 7,
June/July (1971), p 17.
2. Encyclopedia of Chemical Technology, 2nd Edition (196U).
3. Dielectric Materials and Applications, A. R. von Hippel, ed.
Technology Press of MIT and John Wiley and Sons, Inc. N. Y. (195M,
pp 156, 189, 211, 221.
Iu Insulating Materials for Design and Engineering Practice, F. M. Clark,
John Wiley and Sons (1962).
5. Astm D2233-70 Standard Specification for Chlorinated Aromatic Hydro-
carbons (Askarels) for Capacitors, American Society for Testing and
Materials, Phil. Pa.
6. National Electrical Code Handbook 10th Ed., 1957 McGraw-Hill.
7. Insulating Materials for Design and Engineering Practice, F. M. Clark,
John Wiley and Sons, p 2^6, (1962).
8. Chemical and Engineering News, October 18, 1971, p 16.
9. National Industrial Pollution Control Council Report on the Use and
Disposal of Electrical Insulating Liquids, U. S. Government Printing Office,
Washington, D. C., June, 1971.
10. 1967 Census of Manufactureres, Commerce Publication MC67 (2)-36A,
Electrical Measurement and Distribution Equipment.
11. Fluorescent Lamp Ballasts, Summary for 1970 Commerce Publication
Series MQ-36C(70)-5, September (1971).
12. Dielectric Materials and Applications, A. R. von Hippel, ed. Technology
Press of MIT and John Wiley and Sons, Inc., N. Y. (19510 p 197.
13. Private communication. L. E. Smith, Special Engineer Transmission
Maintenance and Test Branch, Tennessee Valley Authority, Chattanooga, Tenn.
lh. Private communication. Herbert C. Erdman, Public Service Electric and
Gas Co., Maplewood, N. J.
15. Private communication. Earl Morrison, Chief Chemist. Los Angeles
Department of Power and Water, Los Angeles, California.
16. Private communication. Anthony J. Nesti, National Electrical Manu-
factureres Assoc., 155 E. hhth St., N. Y. N. Y. 10017.
17. ASTM D2283-71 Standard Specification for Chlorinated Aromatic Hydro-
carbons (Askarels) for Transformers, American Society for Testing and
Materials, Philadelphia, Pa.
68
-------
18. Private communication. E. L. Raab, Manager, Insulation Systems
Section, Power Distribution Div., General Electric Co., Pittsfield, Mass.
19. Report on Power Transformer Troubles, 1969* Edison Electric Institute
Publication No. 71-20, (1971).
20. "Introduction to Hydraulic Fluids", R. E. Hatton, Rheinhold Publishing
Co. (1962).
210 "Synthetic Lubricants", R. C. Grander son and A. W. Hart, Rheinhold
Publishing Co. (1962).
22. W. Espe, Materials of High Vacuum Technology, Vol. 3, Pergamon Press,
(1968).
23. "High Vacuum Pumping Equipment", B. D. Power, Rheinhold Publishing Co.
(1966).
2h. Viscosity index. A high V. I. means a low viscosity-temperature
coefficient.
25. The pour point is related to the lowest temperature a liquid can be
poured from a container. ASTM D 97-66 Standard Method of Test for Pour
Point, American Society for Testing and Materials, Phila., Pa.
260 Boundary lubricant additives cling to metal surfaces facilitating good
lubrication at high pressures. See ref. 21, pp llj-21.
27. "Fire Resistance of Hydraulic Fluids" ASTM Special Technical Publication
No. Ij06 (1966).
28. "Review of Ignition and Flammability Properties of Lubricants", J. M.
Kuchta and R. J. Kato, Bureau of Mines Technical Report AFAPL-TR-67-126 (1968).
29. ASTM D901-70 Standard Methods of Testing Askarels. Sees. 18, 19.
30. National Bureau of Standards Report of Tests No. TG 10210-2158: FR 3695.
31» See for example: Ref. 21, p 133.
32. Reference 21, Chapter k.
33. Phosphate ester type hydraulic fluids are being recycled by: Eppi Pre-
cision Products, 227 Burlington Ave., Clarendon Hill, HI.
3h. See for example: A. M. Dobry, E. A. Glass, and A. Zletz, "Improved
Non-flammable Hydraulic Fluid", Bureau of Ships Report H6j-lh (1967).
35. Ref. 21, Chapter 5.
36. Ref. 21, P 235.
37. Private communication, R. K. Crothers Maintenance Division, Federal
Aviation Administration,,
69
-------
38. Ref. 22, Chapter 18.
39. Ref. 23, p 66.
hO. Ref. 22, pp 352-353.
hi. W. J. Danziger, "Heat Transfer Media Other Than Water", Encyclopedia
of Chemical Technology, 2nd Ed., Vol. 10, pp 8ii6-86l (1965).
Ii2. Paul L. Geiringer, Heat Transfer Media, Rheinhold Publishing Co., N. Y.
(1962).
Ii3. Ralph L. LeMar, "Thermal Stability of High Temperature Fluids and Fluid
Intermixtures" U. S. Army Weapons Command Technical Report DA#lC02hl401A108
(1967).
hh. L. Mandelcorn and R. L. Miller, "Radiation Resistance of Capacitors -
Dry and Impregnated" paper # E-9, Conference on Electrical Insulation and
Dielectric Phenomena NAS-NRC (1971).
h5. Jt R. Darby and J. K. Sears, "Plasticizers", Encyclo. Poly. Sci. and
Tech., 10, 275 (1969).
U6. ASTM D 883-69a Standard Nomenclature Relating to Plastics, Amer. Soc.
For Testing and Materials, Phila., Pa.
hi* Gene Wilde and David Press, "Plasticizers", Modern Plastics Encyclo.,
U5, h28 (1968).
Ii8. H. J. Hubbard, "Chlorinated Biphenyls and Derivatives", Encyclo0 of
Chem. Tech., 5, 291 (196U).
h9* R. H. Mosher, "The Technology of Coated and Processed Papers", Remsden
Press Division, N. Y. p 368 (1952).
50. Ref. h9, p 2hO.
51. ASTM D 907-70 Standard Definitions of Terms Relating to Adhesives, Amer,
Soc. for Testing and Materials, Phila. Pa.
52. Irving Skeist "Adhesive Compositions" Encyclo. Poly. Sci. and Tech.,
Vol. 1, Interscience Publishers, N. Y. p U82 (196M.
53. Ref. U9, p 286.
5h. ibid, p 292
55o V. E. Hamilton and J. M. Roseland, S. African. 67 Oh,865 (McDonald
Douglas Corp.) (1968).
56. ibid, Fr. 1,519,535, (1968).
57. Brit. Patent l,lU8,Oh7 (Douglas Aircraft Co.) (1969).
70
-------
58. Harry Smith, U. S. Patent 3,395,132, (Dow Chemical Co.) (l968)0
59. David A. Frey, U. S. Patent 3,380,951 (Dow Chemical Co.) (1968).
60. T. P. Flanagan, U. S. Patent 3,220,966 (National Starch and Chemical
Co.) (1965).
61. R. P. Cox, J. L. Wagner, and R. J. Sere, U. S. Patent 3,117,000 (E. I.
Dupont de Nemours) (1969).
62 o P. Ruckstuhl, Ger. (East) Patent 1*0,92? (1965).
63. P. Prumier and J. Duthu, Fr. Patent 1,182,172 (1967).
6lt. P. Ruckstuhl, Ger. (East) Patent 37,967 (1965).
65. H. J. ELchel, U. S. Patent 2,988,Ij6l (National Cash Register Co.) (I96l).
66. H. G. J. Velthoven and H. J. Wienjes, Neth. Patent 109,025 (1961).
67. Erail Kline, U. S. Patent 2,077,699 (E. I. DuPont de Nemours) (1937).
68. ibid, U. S. Patent 2,077,700.
69. G. Listner, U. S. Patent 3,k58,li71 (Johnson and Johnson Co.) (1969).
70. ibid, U. S. Patent 3,277,0^6 (1966).
71. Brit. Patent 1,133,050 (E. I. DuPont de Nemours) (1968).
72. R. J. Jenkins and R. N. Foster, Ind. Eng. Chem. 23, 1362-1365 (1931).
73. N. V. Maiorova, M. I. Karyakina, V. A. Kargin, Z. Ya. Berestneva, L. P.
Malysheva, Lakokrasoch. Mater. 1Kb Primen, 3, 17-19 (1969). (Cf. C.A. 71,
62325j 1969).
7k. S. V. Yakubouich, N. Ya. Gicbkova, V. A. Zubchuk, and P. V. Kozlov Lako-
krasoch. Mater. IKh Primen h, h6 (1966). (C.A. 6_5, l8820f, 1966).
75. D. P. Spalding, Fr. Patent 1,353,506 (Compagnie Francaise Thomson-
Houston) (19614).
76. Brit. Patent 1,020,053 (General Electric Co.) (1966).
77. D. P. Spalding, U. S. Patent 3,288,7143 (General Electric Co.) (1966).
78. E. Kamp and Karl Jahn, U. S. Patent 3,393,087 (Monsanto Co.) (1968).
79. H. Wells (Atomic Energy Res. Establishment, Harwell, England) J. Oil
Color Chemists Assoc. 1$, (l) 28 (1965).
80. Ref. h9, p 293.
81. Francis J. Whilby, Brit. Patent 1,138,976 (Standard Telephone and Cables,
Ltd) January 1966.
71
-------
82. Robert S. Haines and Thomas J. Walsh, U. S. Patent 3,279,9^5 (IBM Corp)
October 1966.
83. Theo A. Tielens and Jan Kunnen, U. S. Patent 3,109,75h (North American
Phillips Co.) November 1963.
8h. Fritz F. Freitay, Herman H. Malter, and Lothar Kluth, U. S. S. R. Patent
157,031, September 1963.
85. Margarete K. Heimholtz and Waltraud H. E. Helmholtz, Ger. Patent 1,156,922,,
November 1963.
86. Fr. Patent l,358,68Ij (Kommanditbolaget Svenske Fargindustri Lundin and
Co.) April 196ti.
87. Irvin J. Steltz, Ger. Patent 1,279,262, October 1968
88. Charles T. Rairdon, "Sealants" Encyclo. Poly. Sci. and Tech., Vol. 12_,
p hi8 (1970) Interscience Publishers, N. Y.
89. Societe Civille Fiorillo, Fr. Patent 1,1402,991, June 1965.
90. Thiokol Chem. Corp. Neth. Patent Appl. 6,606,3U9, November 1966.
91. J. M. Pachuta, Fr. Patent l,566,Ul3 (Thiokol Chem. Corp.) May 1969.
92. Edward G. Millen, Fr. Patent 1,521,788 (Thiokol Chem. Corp.) May 1969.
93. Barret K. Green and Robert W. Sandburg, U. S. Patent 2,5l|8,3614-5
(National Cash Register Co.) (1951).
9ho ibid, U, S. Patent 2,5^8,366 (l95l).
95. S. Kimura, T. Kobayashi, S. Ishige, Fr. Patent, l,5It5,5U5 (Hodogaya
Chem. Co., Ltd.) November 1968,
96. A. Corredor Garcia, Span. Patent 3^5,298,November 1968.
97. Brit Patent l,OU7,5l2 (Minnesota Mining and Mfg. Co.) November 1966.
98. Richard Owen, U. S. Patent 3,315,598 (3M Co.) April 1967.
99. Buck Stricklin, U. S. Patent 3,360,367 (3M Co.) December 1967.
100. Martin Hepher, Brit. Patent 986,053 (Kodak, Ltd.) March 1965.
101. A. G. Gulko, U. S0 Patent 3,hOl4,99h, October 1968
102. S. Ancar, Brit. Patent 1,025,757, April 1966.
103. R. Oda, H. Fuju, H. Moriga, and S. Dotani, U. S. Patent 3,389,007,
June 1968.
10l4. Brit. Patent 1,1^9,265 (Xerox Corp.) April 1969.
72
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105. B. B. Jacknow, J. H. Moriconi, and F. M. Palermiti, S. African Patent
6,803,560 (Rank Xerox, Ltd.) January 1969.
106. Hans J. Lena, Ger. Patent 1,199,290 (Hoechst Fabweke) August 1965.
107. Daniel L. Goffredo, U. S. Patent 3,269,308, August 1966.
108. Brit. Patent 1,126,1(78 (Johnson and Johnson Co.) September 1968.
109. Charles A. Berridge, U. S. Patent 3,l5*4,5l5 (General Electric Co.)
October I961j.
110. R. H. Snedeker, U. S. Patent 3,^05,199 (Union Carbide Co.) October 1968.
111. D. Lurie, Fr. Patent 1,529,506, June 1968.
112. W. F. Busse, U. S. Patent 3,1*18,26? (E. I. DuPont de Nemours) December
1968.
113. R. G. Quinn, U. S. Patent 2,030,653 (international Paper Co.) February
1936.
lilt. H. Picchota, Kunstoff-Rundschau, 12. (I), 191 (1965).
115. Paul E. Burgess, Jr., Carlos J. Hilado, and William R. Proops, Space Mil.
Appl. Cell. Plast. Syst. Annu. Conf. Cell. Plast. Div., Soc. Plast. Ind., 12th,
1967, 3-C-1-3-C-10.
116. Carlos J. Hilado. Paul E. Burgess, Jr., and William R, Proops, J. Cell.
Plast. h (2), 67 (1968).
117. T. Hirata, H. Abe, and Y. Fukui, Ringyo Shakenjo Kenkyu Hokoku, 1967,
No. 200 155. Cf C. A. 70 12779u (1969).
118. H. W. Coover, Jr., and N. H. Shearer, Belg. Patent 652,653 (Eastman
Kodak Co.) December 196ti.
119. Hans Schumann, Ger. Patent 1,298,L£& (Deutsche Solvay-Werke) June 1969.
120. Rene Michael, Fr. Patent 1,532,115, July 1968.
121. H. T. Keinp, Jr.. T. L. Statler, and E. E. Muellar, Mitt. Ver. Daut.
Emailfachleute lij_ (5), 1|$ (1966).
122. Rolf Bremer, Eberhard Rheinhold, and Hermann Fiebig, Ger. (East)
Patent 66,712, May 1969.
123. Belg. Patent 696,820 (Establishment Marechal) October 1967.
1214. Brit. Patent 1,159,220 (Sigri Elektrograpit) December 1967.
125. R. B. Trask, and Mark J. Smith, Fr. Patent 1,520,177 (Air Reduction
Co.) April 1968.
73
-------
126. Fr. Patent 1,299,63/4, July 1962.
127. Neth. Patent Appl. 6,lai,l69 (Monsanto C0.) March 1965,
128. ibid, 6,hOI,h7h (Monsanto Co.) August 19614.
129. K0 Sato, U. S. Patent 3,^68,726, September 1969„
7U
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APPENDIX C
The Need For Continued Use of PCBs As Electrical Insulating Liquids
Table of Contents
Page
I. How are PCBs Used by the Electrical Industry? 76
II. The Need for PCBs in Transformers 76
A. ' Mineral oil-insulated transformers
B. Dry-type transformers
III. The Need for PCBs in Capacitors 79
A. Mineral Oil
1. Size
2. Reliability and life
3. Safety
B. Other Liquids
1. Castor Oil
2. Dibutyl sebacate
3. Silicone Fluids
IV« Environmental Protection o"!
Table s
1. Composition of Different Liquid Chlorinated Biphenyls 76'
2. Underwriters' Laboratories Flammability Ratings 77
3o Alternate Insulating Fluids 80
-------
APPENDIX C
The Need For Continued Use of PCBs As Electrical Insulating Liquids
I. HOW ARE PGBs USED BY THE ELECTRICAL INDUSTRY? (l)
The principal use of PCB fluid in the electrical industry is in trans-
formers and capacitors (both large and small) as an insulator and coolant.
Transformers are devices for converting electrical
power from one voltage and current level to another,
and the conducting parts of these devices must be
separated from each other by a suitable insulating
medium.
Capacitors are devices for storing electrical energy
through the physical separation of charged metal
surfaces by an insulating medium.
Because of the nonflammability (Table 1) of Aroclors (the trade name
of Monsanto), their vapors, and their arc-formed gaseous products, trans-
formers filled with PCBs are relatively free of fire and explosion hazards
and may be used in locations where failures of oil-insulated transformers
would present a potential danger to life and property. In addition to im-
proving the safety aspect of capacitors, Aroclors also have the advantages
of reliability, long life, and small size.
Table 1
Underwriters' Laboratories Flammability Ratings
Fluid Flammability Rating
Ether 100
Gasoline 90-100
Ethyl Alcohol 60-70
Kerosene (100° P.P.) 30-hO
Mineral Oil 10-20
Aroclor I2h2 and MCS 1016 2-3
II. THE NEED FOR PCBs IN TRANSFORMERS
PCBs are used in transformers wherever fire protection is particularly
important -- for about 5 percent of all transformers.
Most of these transformers are located inside public, commercial, or
industrial buildings; on the roof tops of such buildings or in close proxi-
mity to such buildings, and require no special enclosures other than nec-
essary to prevent accidental hazardous mechanical or electrical contact of
persons with the equipment. See Table 2 for some liquid chlorinated biphenyls,
76
-------
TABLE 2
Composition of Different Liquid Chlorinated Bipheryls
- given as % -
Chlorine
Biphenyl
Mono-chlorobiphenyl
Di-chlorobiphenyl
Tri-chlorobiphenyl
Tetra-chlorobiphenyl
Penta-chlorobiphenyl
Hexa- chlor obipheny 1
1221 1232
21 32
1)4.8
56.5
26.9 ^55
1.12
.06
MCS 101*3
32
.01
22.2
7l.li
3-3
1212
w
.02
.72
15.6
51.5
22.5
6.7*
MCS 1016 121]8
l< 2 i.8
.02
.93
19. h
6h,5
15.0 ~>55
.16*
12514 1260
5h 60
60
70
•«-Includes higher than penta-chlorinated isomers,
-------
The amount of Aroclor used in various types of transformers ranges
from hO to 500 gallons (5l6 to 6,U50 Ibs.) with an average of about
235 gallons (3,032 Ibs.). During 1968, the last complete "normal"
year for the electrical industry, the total amount of PCBs used in trans-
formers was approximately 1.3 million gallons (8.1» thousand tons).
The only present alternatives to Aroclor-insulated transformers are
mineral oil-insulated transformers or dry-type transformers (either those
open to the atmosphere or those that are gas-filled and sealed).
A. MINERAL OIL-INSULATED TRANSFORMERS
1. If one disregards safety considerations, there are no technical
reasons why mineral oil-insulated transformers could not be directly sub-
stituted for PCB insulated transformers. The size of the unit would be
unchanged; the weight and cost would be less.
2. But one cannot disregard safety considerations, which are often
embodied in legal codes. Obviating the safety hazards involves serious
economic and space constraints, that would occur either by the use of
protective vaults, or use of insulated buses (with the transformer located
outdoors). Either solution, if space is available, could cost $5,000—
$50,000 per transformer.
B. DRY-TYPE TRANSFORMERS
In most locations, dry-type transformers (either those open to the
atmosphere or those that are gas-filled and sealed) could not be directly
substituted for PCB-insulated transformers. There are several restrictions
to such a direct substitution:
1. The reliability of dry-type transformers is less than that of
comparably rated liquid-insulated transformers. An Edison Electric Insti-
tute survey of failures in network transformer banks showed a 7 percent
per year failure rate for dry-type units compared to 0.2 percent for liquid-
insulated units.
2. Furthermore, liquid-insulated transformers have a much greater
overload capability. Many liquid-insulated units can sustain a 100 per-
cent overload for 8 hours and a 200 percent overload for 2 hours. These
transformers are able to maintain continuity of electrical service during
periods of temporary malfunction of related equipment.
3. Some dry-type transformers are larger by 10 to 30 percent than
comparably rated liquid-insulated units, and most are expensive.
k. Dry-type transformers are noisier by 5-10 db than are liquid-
insulated transformers.
5. Open dry-type transformers, which are cheaper than sealed dry-
type transformers, cannot be used in certain corrosive or hazardous
atmospheres, e.g., on furnaces or on electrostatic precipitators near
hot stacks.
Clearly there is no substitute for PCB-filled transformers where
fire protection is required.
78
-------
III. THE NEED FOR PCBs IN CAPACITORS
PCBs are used in more than 90 percent of the electric utility
(large power) type and smaller industrial type capacitors made today.
They are needed for safety, reliability and long life, and to achieve
sizes compatible with equipment and installation requirements.
The principal types of PCS-impregnated capacitors and their
applications are high voltage power capacitors used primarily for power
factor correction in the distribution of electric power; low voltage
power capacitors installed in industrial plants at the load (typically
large motors); ballast capacitors to improve the efficiency of lighting
systems; and small industrial capacitors for power factor improvement
in such equipment as air conditioning units, pumps, fans, etc. Almost
80 million such capacitors are manufactured annually, most of them for
first-time use.
Capacitors used in lighting and air conditioning applications
contain 0.005 to 0.09 gallons of PCS per unit. The largest power
capacitors contain about 6.7 gallons of askarel. The most popular size
contains about 3.1 gallons. The National Electrical Code requires that
any installation of capacitors in which any single unit contains more
than 3 gallons of combustible liquid shall be in a vault like that re-
quired for transformers. During 1968, the last complete "normal"
year for the electrical industry, the total amount of PCBs used in capacitors
was approximately Ik.h thousand tons.
Possible alternatives to PCB-impregnated capacitors are capacitors
impregnated with mineral oil, or certain other liquids.
A. MINERAL OIL
1. Size
The single most important property of a liquid to be used
in a capacitor is its dielectric constant (the ratio of its ability to
store electrostatic energy relative to air). The dielectric constant of
the capacitor-grade PCB (Aroclor 121*2) is 5.85 while that of mineral oil
is 2.25. (See Table 3) Reverting to an oil-paper dielectric system would
increase the average capacitor.volumn(size) by approximately 600 percent
the weight by 500 percent,and the cost by approximately UOO percent. At
the present levels of demand for capacitor KVAR, there would be a shortage
of electrical grade paper and a shortage of capacitor factory facilities
further tending to increase the cost to the utility, and ultimately to the
consumer.
2. Reliability and Life
POBs are thermally and oxi_datiyely more stable than mineral
oils, and discharges, which can occur in capacitors, are less likely to
generate gases from askarels than from mineral oils. The chemical
stability of PCBs in the presence of capacitor tissue and plastic films and
the favorable stress distributions between solid and liquid have made it
possible to design low-cost capacitors with a life expectancy of more than
10 years life in lighting applications and more than 20 years in electric
utility applications. In each application the first-year failure rates
are less than 0.2 percent. This level of life and reliability had not
been achieved prior to the introduction of PCBs.
79
-------
oo
o
Table 3
Alternate Insulating Fluids
Some Significant Properties of Certain Candidate Insulating
Fluids to Replace Aroclor 12[|2
Fluid
Aroclor
Aroclor MCS 1016
Aroclor MCS
Mineral Oil
Dielectric Constant,
e'r, at 25° C
5-85
5.85
5-7
2.25
Cleveland Open Cup
Flash Point -°C -
1914
191
160
U5
Flammability
Fire Point
333
319
2lh
150
Density
1.38
1.36
1.28
.9
Cost,
# lb
18
18
18
3
-------
3. Safety
The relative non-flammability of PCBs significantly reduces
the fire hazard that might otherwise accompany those failures that result
in rupture of the case»
B. OTHER LIQUIDS
1. Castor Oil. The dielectric constant of castor oil is h-5, and
this material is useful as an impregnant in B.C. energy storage capacitors.
However, A.C. capacitors filled with this liquid have relatively short
lives and are not very stable under A.C. discharges and in the presence
of water derivable from the cellulosic paper.
2. Dibutyl sebacate. This ester is especially useful in high
frequency parallel plate capacitors because of its low, flat loss charac-
teristics over a broad frequency range. In this type of construction the
liquid is the sole dielectric material. When used in conjunction with
paper,this ester is also unstable.
3. Silicone Fluids. These materials have a dielectric constant of
2.7 and would generally be subject to the same disadvantages as mineral
oil.
In the interest of achieving a higher degree of environmental
compatibility the capacitor industry switched during 1971 from Aroclor
12l;2 to Aroclor MCS 1016, from which the higher-chlorinated persistent
fractions have been substantially removed.
IV0 ENVIRONMENTAL PROTECTION
The advantages to the public in terms of safe, reliable, and efficient
electrical equipment made possible by the use of PCBs have been documented
in the body of, and especially Appendix B to, this report. It is also
clear that there are no present or prospective substitutes for these
materials, and that the functions they perform are essential. Thus the
continuing need for PCBs in closed electrical system applications is con-
clusive. The electrical industry well understands, however, that continued
use of these materials requires unusual protective measures. These
measures were the subject of recommendations made by a previous NIPCC Sub-
Council report (The Use and Disposal of Electrical Insulating Liquids,
June 1971) and are judged to be well on their way toward implementation:
witness the introduction of the new capacitor dielectric, the provision
of facilities for the incineration of liquid and solid wastes,_and the
instructions to operating personnel and users regarding the need for care
in waste disposal, an activity now being further formalized and strengthened
by ANSI's committee C1070 The annual residual leakage to the environment
from the continued use in transformers and capacitors has been estimated
between one part in a thousand and one in ten thousand of the existing
environmental PCB burden.
1. The above paper was prepared by the Electric and Nuclear Sub-Council,
National Industrial Pollution Control Council: Chairman, D. C. Burnham,
Westinghouse Electric Corporation; Vice Chairman, Fred J.Borch, Chairman
and Chief Executive Officer, General Electric Company; Members: A. P.
Fontaine, President and Chairman, The Bendix Corporation; Raymond H. Giesecke,
81
-------
President and Chief Executive Officer, McGraw-Edison Company; C. Lester
Hogan, President and Chief Executive Officer, Fairchild Camera and Instru-
ment Corporation; Robert w. Sarnoff, Chairman of the Board and President,
RCA Corporation.
82
-------
APPENDIX D
Occurrence, Transfer, and Cycling
of PCBs in the Environment
Table of Contents
Page
I. Occurrence in the Environment 92
II. Behavior in the Environment 99
A. Air
B. Water and Sediment
III. Exposure and Biological Accumulation 99
IV. Discussion 102
V. Research Needs and Opportunities 103
Tables
1. PCB Manufacturing and Sales
Data From Monsanto Industrial Chemicals Co. 85-86
2. Concentration of PCBs in Municipal Sewage
Treatment Plant Outfalls 88
3. PCB Concentrations in Industrial Effluents 89
14. Total Estimated Contribution of PCBs to the
Aquatic Environment 90
5. Concentration of PCBs in Sewage Sludges 91
6. A Sampling of Measured Occurrences of PCBs in the
Environment 93-98
7. Accumulation of PCBs by Various Aquatic Organisms
83
-------
APPENDIX D
Occurrence, Transfer, and Cycling of PCBs in the Environment
PCBs have been in use for more than four decades, not only in the
United States but throughout the developed world. They were not recognized
as environmental contaminants until (Jensen , l) in Sweden identified a series
of unknown peaks on gas chromatograms of pesticide analyses as these sub-
stances. These first identifications were in fish and bird tissues; examina-
tion of other samples soon revealed that PCBs were widespread in biological
materials. Existing data suggest that although the greatest concentrations of
residues are found in the vicinity of industrial and municipal areas in the
Northern Hemisphere, residues exist in areas remote from civilization and in
both the Northern and Southern Hemispheres.
Data on sales of PCBs are available only for the United States from 1957-
1971, with sales reaching a high of 36,000 tons in 1970, Table 1. Sales doubled
1960-1970; assuming the same growth rate from 1930 to 1970, about 500,000 tons
have been sold in the United States. Data from outside the United States are
few. It is estimated that Japan manufactured 13,000 tons per year (2). PCBs
are also produced in West Germany, the United Kingdom, Spain, France, Italy,
Russia, and possibly new producers in Brazil, Argentina, India, and East Ger-
many. Assuming that the United States used half of the world total, world pro-
duction would have been about one million tons--approximately hall" the estimated
total production of DDT. Monsanto's 1971 sales dropped to half the 1970 level,
and 1972 sales are expected to be 12 - 15,000 tons. Prior to 1971, when Monsanto
(the sole U.S. manufacturer) curtailed sales to non-closed system uses, about
hO percent was used in plasticizers, hydraulic fluids and lubricants, surface
coatings, inks, pesticide extenders, and micro-encapsulation of dyes for carbon-
less duplication paper—uses that potentially result in environmental contamina-
tion .
If the same percentages held worldwide, i|0,000 tons might have been used
in ways that could easily reach the environment; accidents and careless disposal
practices would have increased this amount considerably, perhaps to 50,000 tons
or more.
(Nisbet and Sarofim, 3)provided rough estimates of the losses of PCBs to
the North American environment in 1970: 1500 to 2000 tons to the atmosphere
(mostly Aroclor 125k to 1260 from plastics and 12^2 from burning dumps); UOOO
to 5000 tons to fresh and coastal waters (Aroclor 12li2-1260); 22,000 tons into
dumps and landfills (mostly Aroclor 12l|2). Other losses were judged to be small,
but often locally significant. The total loss to the North American environment
from 1930 to 1970 was estimated to be:
Atmosphere - 30,000 tons
Water - fresh and coastal - 60,000 tons
Dumps and landfills - 300,000 tons
The total of 390,000 tons is within a factor of two of the estimate above
of 500,000 tons that might have reached the world environment. They further
8U
-------
oo
TABLE 1
PCB MANUFACTURING AND SALES
DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO.
1957 THROUGH 1971
(Thousands of Pounds)
TOTAL PRODUCTION
(For Domestic Sales )^'
DOMESTIC SALES
DOMESTIC SALES BY CATEGORY
Heat Transfer
Hydraulics/Lubricants
Misc. Industrial
Transformer
Capacitor . .
Plasticizer Applications^'
Petroleum Additives
Total
DOMESTIC SALES BY PJB GRADE
Aroclor 1221
Aroclor 1232
Aroclor I2h2
Aroclor 12^8
Aroclor 125h
Aroclor '1260
Aroclor 1262
Arcolor 1268
Total
NOTE: (l) Production amounts prior
(2) Amounts for plasticizer
1957
32299
1612
12955
17028
-
32299
23
196
18222
1779
141461
7587
31
-
32299
to I960 are
applications
1958
26061
_
15149
755
5719
114099
3939
-
26061
16
113
lOhhh
2559
6691
5982
I8h
72
26061
not available .
prior to 1958
1959
31310
__
2685
1569
598h
161499
14573
-
31310
25h
2UO
13598
3381
675U
6619
359
102
31310
are not
I960
37919
3521h
_
2523
1559
7921
16967
6211
-
3521H
103
155
18196
2827
6088
7330
326
189
3*U
available .
1961
36515
37538
-
huo
21U
6281
15935
9098
—
375307
914
211
19827
14023
629h
65140
361
158
37538
1962
38353
380h3
157
3915
1681
798h
15382
89214
~
38013
IliO
22lt
2065U
3^63
6325
6595
132
210
380143
-------
TABLE 1 (cont.)
U.S. PRODUCTION
DOMESTIC SALES (LBS.)
U.S. EXPORT SALES
1963
1*1*731*
38132
361,7
1961*
50833
1*1,869
1*096
1965
601,80
51796
1*2314
1966
658h9
59078
6852
1967 1968
75309
621,66
8121,
82851*
65116
11231
1969 1970 1971
76387 85051* 101,71
6719)4 73061 37635
10621, 13651 9876
Prospect
1972
25-30 m
25-30 m
CD
ON
U.S. DOMESTIC SALES BY
CATEGORY
Heat Transfer
Hydraulics/Lubricants
Misc. Industria]
Transformer
Capacitor
Plasticizer Applications
Petroleum Additives
U.S. DOMESTIC SALES
BY PCD GRADE
582
391,5
1528
7290
15606
9181
929
1*371*
1692
7997
1951*0
10337
1237
1*616
181,1
8657
2371*9
11696
1766
1*258
1779
8910
2888)4
2262
1*61*3
11*26
11071
29703
13361
2529 3050 3958 31*80
5765 8039 71,03 161,3
1283 1079 1627 578
11585 12105 13«28 11528
29550 25022 26708 17305
11,1*01, 161*60 19537 3102
11*39
25-30 m
25-30 m
Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
1221
1232
121*2
121,8
1251*
1260
1262
1268
361
13
18510
5013
5911
7626
1*11*
281,
596
13
23571
5238
6280
8535
1*1,6
190
369
7
31533
5565
7737
5831
558
196
528
16
39557
5015
7035
5875
768
281*
1*1*2
25
1*3055
1*701*
6696
61*17
81*0
287
136
90
1*1,853
1*891*
8891
5252
720
280
507 11,76 1600
273 260 211
1*51*01 1*8588 21000
5650 1,073 261
9822 121,21 5800
1*C 90 1750
1023
330 -
712
300
300
300
1*000
6000
600
-------
estimated that one-third of the PCBs released to the air and one-half of
those released to water have now been degraded. The PCBs in dumps probably
have undergone less degradation.
Given the diversity of uses of PCBs and their chemical stability
(greater stability in the higher chlorine species), it is not surprising
that residues are now widespread. While satisfying quantitative estimates
of the contribution of various pathways into the environment are not possible
with existing data, there are enough data to be certain that they do reach
the environment at least from the following sources:
— Open burning or incomplete incineration (at usual temperatures) 0
of solid wastes, municipal and industrial. Incineration at 2000 F
or above for two seconds will destroy PCBs, but poorly operated
incinerators or open burning may result in PCBs being released to
the atmosphere unchanged.
-- Vaporization from paints, coatings, plastics, etc. (Nisbet and
Sarofim, 3) estimate that as much as 20 percent may be vaporized.
-- Municipal and some industrial sewers (present in treated as well
as untreated wastes). Tables 2 and 3-
-- Accidental spills or improper waste disposal practices.
-- Formerly, direct application to the environment as ingredients
of pesticides or as carriers for pesticides (such uses are now
prohibited).
-- Dumping of sewage sludge, municipal and industrial solid waste,
and dredge spoil at sea.
— Sewage sludges disposed of on land.
-- Migration from surface coatings (paints, etc.) and packaging
materials into foods and feeds.
Probably the largest amounts of PCBs circulating in the environment
reach it through industrial and municipal discharges to inland and coastal
waters. Tables 2, 3j and h present data on such discharges. Based on Table
LI, we can estimate 6,000 tons per year may reach these environments.
In addition, PCB residues occur in sludge from municipal sewage systems.
Table 5> presents results of analyses from several such sludges. Sewage sludge
is disposed of by incineration, landfill, spreading on the land, and dumping
at sea. Four million tons per year reach the Atlantic Ocean and Gulf of Mexico,
which would include only 10 or so tons of PCBs (Li)- Analysis of the waste water
from the effluent scrubbers of three sludge incinerators showed no detectable
residues of PCBs (level of sensitivity 0.1 part per billion), suggesting that
most PCBs had been destroyed by incinera-tion. The total amount of PCBs con-
tained in the sludges would not be more than /•yo tons per year.
87
-------
TABLE 2 - CONCENTRATION OF PC'.IS IN MUNICIPAL SEWAGE TREATMENT PLANT OUTFALLS
Aroclor Flow per Est. PCB
c
Collection Site
Ohio -
Miami River
Dayton
Hamilton
Middleton
Wisconsin -
Milwaukee River
West Bend
Fredonia
Saukville
Graf ton
California
East Bay
(San Francisco)
San Francisco
Terminal Island
Orange County
Hyperion
White Point
Richmond
San Diego
:ollection Compound >Jg/l Day Mgd Discharged Source
Date Detected (ppb) I/ per day (Ibs.) of Data
1-19-71 1254 17 48 6.2 EPA
°800 Unpb>
to Data
1-20-71
0800
1-19-71 1248 10 8 0.6
0000
to
1-19-71
2400
1-19-71 ND* . _ ii
0800
to
1-20-71
0800
3-26-70 1254 0.25 1.4 0.002 Veith &
Lee
1254 0.12 0.1 0.002 "
1260 0.13 0.1 0.002 "
" 1254 0.04 0.8 0.002 "
12-70 1254 3.1-3.8 155 4.2 Schmidt,
et al, '71
" 1254 3.8-5.8 31.5 1.2 "
" 1254 5.8-12.8 9.3 0.7
1254 0.21-0.64 130 0.4 "
1254 0.16-0.37 340 0.7 "
1254 76 350 213
ND*
ND*
Oxnard
*ND - Not Detected
ND*
_!/ mgd = million gallons per day = (8,000,000 Ibs./day)
88
-------
TABLE 3. PCB CONCENTRATIONS IN INDUSTRIAL EFFLUENTS
Location
Saukville, Wise.
Ohio- Great
Miami River
Florida- Escambia
Kind of
Industry
Chemical Plant
Paper Coating Co.
Paper Treatment
Appliance
n
Chemical Plant
Date
3/70
1/71
1/71
1/71
1/71
4/69-10/69
Aroclor Concentration
Compound in Effluent
Detected (ppt>)
1242
1242 & 1248
1242
1254
1254
1254
2.50
27
430, 470*
5
18
2.5-275
Source of Data
Vieth and Lee , 1970
EPA data- Analytical
Quality Control Lab
ti
n
it
Duke, et al., 1970
-•Samples from treatment lagoon
-------
TABLE 4
TOTAL ESTIMATED CONTRIBUTION OF PCBS TO THE AQUATIC ENVIRONMENT
Municipal Outfalls
Assume: 150,000,000 sewered population x
130 gallons sewage per person per day x
8 pounds per gallon of sewage =
Approximately 160 billion Ibs./day.
With concentration of 0.1 ppb in sewage, 16 Ibs./day;
With concentration of 10 ppb in sewage, 1600 Ibs./day.
[Note that only the White Point outfall and Dayton
(largely serving industrial communities) exceed the
10 ppb concentration]
Annual contribution would not exceed 300 tons from
this source, even if the average concentration in
municipal sources was 10 ppb.
Industrial and Other Sources
Basis for Estimate;
Concentrations in the Great Miami River of 5.8 ppb
and flow rate of 728 cfs yield estimated daily
carriage to the Ohio River of '~95 Ibs. per day.
Contribution from the sewage treatment plants at
Dayton (6.2 Ibs./day) and Hamilton (0.64 Ibs./day)
account for 6.8 Ibs. (-^7% of the amount present in
the river).
In the Milwaukee River, the estimated discharge of
PCBs to Lake Michigan, based on a concentration in the
water of 0.15 ppb (Veith and Lee, 1970) and flow rate
of 500 cubic feet per second, is~0.5 Ib. per day.
Contributions from the sewage treatment plants at
West Bend, Fredonia, Saukville, and Grafton, total
0.002 Ibs./day, (about 0.4% of the amount present).
Extrapolation;
The Great Miami River drains a heavily industrialized
area and represents something near the upper limit of
PCBs to be expected in municipal discharges. The
Milwaukee River is less industrialized. If one assumes
that municipal sources contribute on the average not
more than 5% of the total, the annual contribution from
other sources would be on the order of 300 x 20 =
6,000 tons per year.
90
-------
TABLE 5. CONCENTRATION OF PCBS IN SEWAGE SLUDGES
Collection Site
Date
Aroclor
Detected
Concentration
(ppb)
Sludge
per day
tons/day
Est. PCB
Content
Day (Ibs.)
Sourc
Cali forr.ia
Hyperion (Los Angeles) 12/70
Barstow 7/21/71
1254
1254
85 (78.5-92.1) 20,00^
1400 1.4
Schmidt, ct. al. , (13)
EPA Unpublished datr.
Ohio
Dayton (Miami River)
Little Miami (Cincinnati)
Mill Creelc (Cincinnati)
Lebanon (Turtle Creek)
Shayler Run
1254
1254
1254
1254
1254
105,000
32,000
12,700
2,500
3,200
47.9
20.2
83.3
1.0
-
10.1
1.3
2.2
.005
-
EPA Unpublished data
Virginia
Lorton
1254
1,200
Indiana
Indianapolis
1254
3,SOO
126.1
1.03
_!_/ This number is based on outfall discharge and represents a relatively dilute sludge. The estimated PCB
content in Ibs./day is che important figure here.
Assumptions: Each million gallons of sewage contains about 1 ton of sludge. The daily output of sludge, then
is 150,000,000 sewered population x 130 gal. sewage per day = 19,500,000,000 gallons ner day and 19,500
tons of sludge per day.
At 10 ppm of PCBs (highest level found), the daily output would be 19,500 tons x 2000 Ibs. = 39 million Ibs.
x 10 ppm = 390 Ibs. per day, at 1 ppm, 39 Ibs./day. These-would be respectively 70 and 7 tons/year.
-------
By far the largest quantities of PCBs must end up in dumps and landfills.
As noted above, open burning will doubtless release some PCBs to the atmosphere.
Little is known about concentrations in landfills, degradation, leaching or
vaporization. Much of the material here will be in sealed containers, and will
be sequestered or only slowly released to the environment. Analyses of stagnant
water close to a Swedish landfill were below the level of detection of h parts
per billion, suggesting little leaching from such sources (5).
PCBs are known to have reached the environment or man's food supply in a
variety of other ways, no one of which is important as a source of environmental
contamination, but each of which may have serious consequences locally. Spent
transformer oil containing PCBs, used as an herbicide carrier, contaminated dairy
cattle grazing area and resulted in residues in milk. Silo paints containing
several percent of PCBs are thought to have migrated into silage, and in turn
resulted in residues in milk (6). A leak in a heating element used in pasteuri-
zing fish meal resulted in contamination of poultry feed which, in turn, resulted
in reduced hatchability of eggs in some chicken flocks, and residues in excess
of the FDA interim action level in some eggs and meat (6). In Japan, rice oil
contaminated from leakages during heat treatment resulted in poisoning of hun-
dreds of people and the only known disease attributable to PCBs. Residues in
packaging materials have contaminated the foods they contained; presumably, most
of the residues came from recycled paper which had included "carbonless" carbon
paper with relatively high PCB levels. Virgin paper products have also been
shown to contain PCBs, and their source of contamination is not well defined at
this time. There are other cases of food contamination in which the source of
the contaminant has not been identified.
From the sediment measurements, we can crudely estimate the burden in sedi-
ments underlying inland waters in the continental United States. There are about
58,000 square miles of such sediments. Assuming sediment has a specific gravity
of 2.5; residues are in the top 3 inches; the weight of 3 inches of sediment is
^£^x 62.14 (wt. of a cubic foot of water) x 1)3,560 sq. feet/acre=/»»l,600,000 Ibs./
acre, or^Jl billion Ibs. per square mile (1.6 million x 6^0). At 10 parts per
billion, the PCB burden would be 58,000 sq. miles x 10 Ib./sq. mile = 580,000 Ibs.
At 100 parts per billion, the PCB burden would be 5,800,000 Ibs. -- 290 to 2900
tons. The higher estimate is less than 1/10 the amount Nisbet and Sarofim (3)
estimate may be present in freshwater and coastal sediments.
I. OCCURRENCE IN THE ENVIRONMENT
Thousands of samples from various parts of the environment have been
analyzed for PCBs. Table 6 presents selected data on occurrence in air, water,
sediments, and various living organisms.
In air and water away from immediate sources of waste discharge, levels
are low—a few nanograms per cubic meter (parts per trillion, ppt) in air and
marine waters, and less than a part per billion (ppb) in fresh water; soil or
bottom sediments contain a few parts per billion, up to several hundred parts
per million (ppm) near some industrial outfalls; from tenths of a parts per
nillion to tens of parts per million in fish and up to hundreds of parts per
92
-------
TABLE 6. A SAMPLING OF MEASURED OCCURRENCES OF PCBS IN THE ENVIRONMENT
Aroclor
No.
Location Samples
Air
Precipitation United
Kingdom
Florida
Sweden
Suspended Par- 4 U. S.
ticulate cities
Water
Great Miami 19
River, Ohio
Ohio River 2
Big Suamico
River, Wise.
Pestigo River,
Wise.
Oconto River
Wise.
Milwaukee 10
River
Date
1968
1971
1970
1968-1970
11/70
11/70
-
11/70
4/71
Summer '71
11/70
4/71
Summer '71
1970
Compound
Detected
N.S.
N.S.
N.S.
N.S.
1242
1254
II
II
1254
II
II
1242
1260
Concentration
(ppb) Source of Data Remarks
Detected but Tarrant and
not quantified Tatton, 1968
Below level of USGS- Unpbl.
quantification
Present in snow Smithsonian Inst.
CFSLP- 1970
~ 27-230 ppm on EPA- Unpbl. Quantification
suspended solids questionable
ND to 15.8 EPA- Unpbl. 3 samples above
- = 5.7 Dayton below
level of detec-
tion. Mean of
16 samples 5.7
ND "
<0.01 Veith, 1972
0.31 "
0.38
<0.01
0.45 "
0.16
<0.01
0.03-2.07, x 0.29 Veith and Lee,
0.02-0.13, x 0.08 1970
-------
TABLE 6 (Continued)
Water (continued)
Sediments
A roc lor
No. Compound
Location _ Samples Date _ Detected
Concentration
(ppb)
Source of Data Remarks
Green Bay,
Wise.
Lake Michigan
South Florida
Escambia River
& Bay, Fla.
Irish Sea
11 lakes in
Pennsylvania
1254
Summer 1970
6-7/71 N.S.
Fall '69 1254
10/69
1971
N.S.
N.S.
0.04-0.07
0.013
<0.01-0.02
ND to <• 0.1
<0.01
<10-50
Veith, 1972
Veith,
Personal
Communication
USGS, Unpbl.
Duke, et. al.
1970
Holdgate, 1970
USGS, Unpbl.
x of 12 samples
h mi. off 12
river mouths.
Data con-
sidered good
to within
+ 50%
7 locations in
S.E. Florida
4 locations in
West Central Fla.
6 locations in
S. Florida
Escambia Bay,
Florida
1971
1971
8/69
8/69
8/69
N.S.
N.S.
N.S.
1254
1254
1254
10-3200 "
< 10-20 "
10-1500
max. of 486,000 Duke, et al.,
1970
1700 "
<300 "
Near indus-
trial outfall
6 mi. from
outfall
-------
TABLE 6 (Continued)
MD
VA
Biota
Marine Plankton
Zooplankton
Invertebrates
Mussels
ii
ii
Oysters
it
it
Blue Crab
Crabs
H
Shrimp
Norway Lobster
Location
No.
Samples
North Atlantic
Irish Sea
Irish Sea
Baltic Sea
Stockholm
Archipelago
Escambia Bay,
Fla.
ii
n
Florida
Georgia
S. C.
Florida
S. C.
Escambia Bay,
Fla.
n
Irish Sea
7
Date
1971
10/69
(about 200) 10/69
AO
15
18
2
2
8
12
3
10
33
1965-1968
f I
1971
1970
1969
196 A- 197.0
1967-1970
1965-1969
2-3/70
1969
1969
1969
Aroclor
Compound
Detected
N.S.
N.S.
N.S.
N.S.
125A
11
11
11
tt
N.S.
125A
125A
Concentration
(ppb) Source of Data Remarks
x 200 Harvey in Nesbit
& Sarofim, 1972
10-30 Holdgate in Nesbit
& Sarofim, 1972
50-500 "
A300 (1900-8600) Jenson, et al., '69
5200 (3AOO-7000)
650 (100-1AOO) EPA- Gulf Breeze,
Unpbl.
SAO (710-970) "
1050 (1000-1100) "
1400-2700 "
2000
Present but not "
quantified
n n
4100 Duke, et al., '70
1000-7000 "
1500-2500
10-100 Holdgate 1970 in
Nesbit & Sarofim,
1972
-------
TABLE 6 (Continued)
Biota (continued)
Fish
Marine (species
not stated)
Herring
10 species
Estuarine
Menhaden
Location
Aroclor
No. Compound
Samples Date Detected
Concentration
(ppb)
Source of Data
Remarks
North
Atlantic
Baltic Sea 18
Stockholm 4
Archipelago
Irish Sea 154
Bay of Fundy
Gulf of Me.
Florida
1971
N.S.
100
Harvey j^n Nisbet
& Sarofim, 1972
1965-1968
1969
1971 1254-1260
6800 (500-2300) Jensen, et al., '69
5100 (3300-8500) "
8/70
10/69
1254
1254
10-2000
70-1540
6700
7300
Zitko, et al., 1972
EPA- Gulf Breeze
Lab., Unpubl.
Freshwater
Nationwide fish-pesticide monitoring
1969. At least some fish at 47 of 50 sampling stations contained more than 100 ppb of PCBs (the
lower limit of detection). Levels ranged from <100 to 14,800 ppb. Henderson, et al., 1971.
1970. Only 1 fish of 40 sampled contained less than 1000 ppb. The highest 20 fish averaged
36,000 ppb, ranging from 9600 to 213,000 ppb. Fish from the Ohio River and the Hudson River
contained the highest residues— 4 fish from the Ohio averaged 80,000 ppb; one fish from the
Hudson River contained 213,000 ppb. Other waters in the top half included the Yazoo River,
Allegheny River, Delaware River, Cape Fear River, Mississippi River, Missouri River, and
Lake Ontario. (Stalling and Mayer, 1972)
-------
TABLE 6 (Continued)
Aroclor
No. Compound
Location .Samples Date Detected
Biota (continued)
Birds - Land
Starlings Continental 124 11-12/70 N.S.
U. S.
Woodcock N.S. - Noth- Fall 1971 N.S.
ern U. S.
Bald Eagle 25 states 69 1966-68 N.S.
Birds - Water
Guillemot Eggs Baltic Sea 9 5/68
White-tailed. Stockholm 4 3/65-6/66
Eagle Archipelago
Heron " U 4/67
Double-crested Bay of Fundy 1971? 1254
Comorant (eggs)
Abdominal fat " 1254
Herring Gull Bay of Fundy " 1254
Concentration
(pob)
x 660 (50-24,300)
4000-9000
Not quantified
250,000
14,000,000,
8,400,000-
17,000,000
9,400,000
17,200
52,000
75,000
Source of Data Remarks
Bureau of Sport
Fisheries &
Uildl., Unpubl.
ii
ii
Jensen, et al. .
1970 (22)
ti
Jensen, et al. ,
1969 (19)
Zitko, et al. .
1972 (20)
1 1
11
Fat
-------
vfl
CD
TABLE 6 (Continued)
Aroclor
No. Compound
Location Samples DaLe Detected
Concentration
(ppb)
Source of Data Remarks
Bicta (continued)
Mammals - Sea
Gray Seal Baltic Sea 2 9-11/68 N.S.
Gray Seal Stockholm 3 5/68 N.S.
Archipelago
Man
Plasma South Carolina 723 1968 1254-1260
Milk Sweden 22
California
Germany
Fat Germany
-Un.ited States 235
229
188
36
30,000
30,000
43% of samples
up to 29
x 40
x 60
x 100
5700
N.D.
<1000
1000-2000
>2000
Jensen, et al . ,
1969 (19)
tt
Finklea , ct ali ,
1971 (23)
Westo'o, et al., 1970 (2lt)
Riscbrough & Brodine, 1969(25)
Acker and Schulte, 1971 (26)
11
Yobs, 1972 (27)
— Unknown
N.S. Not specified
N.D. Not detected
-------
million in some fish and birds near the top of the food chain (l/8 of an
inch is about one trillionth of the distance to the moon; and a part per
million is about 5 steps on a walk from Washington to San Francisco). Man,
who is also at the top of a food chain, carries residues ranging up to 2
parts per million or occasionally more.
II. BEHAVIOR. IN THE ENVIRONMENT
A. Air - The relative importance of the atmosphere as a transport mechanism
is not known. While PCBs have been identified in air, the residence time,
transformations, and movement from air to land or water surfaces through fall-
out or rainout, or return to the atmosphere are virtually unknown. There are
at least two observations that suggest substantial aerial transport; data on
residues in fish in Lake Minto in a remote part of northern Quebec (7), and
residues in woodcock which feed almost exclusively on earthworms, which in
turn pick up residues from the soil. Only by invoking aerial transport can we
account for residues in arctic lakes or in more or leas wilderness areas of the
North where woodcock summer. Nisbet and Sarofim (3) suggest airborne PCBs will
have been adsorbed on particles and have a relatively short residence time--
thus most will have been redeposited on the U. S. continent, but some will have
reached the oceans.
B. Water and Sediment - The water environment is probably the principal sink
and transport mechanism for PCBs. Calculations based on measured occurrences
in municipal and industrial outfalls, in the receiving waters, and the down-
stream reaches of the waterways demonstrate transport through the aquatic sys-
tem. Measured residues in fishes from various environments suggest accumulations
at the downstream ends of the drainageways.
There are few data on removal, disappearance, and sequestering of the sub-
stances in soils or bottom sediments of rivers, lakes, estuaries, or the ocean.
Table 6 includes some data that indicate presence in bottom sediments, and sug-
gest that sediments may be a major reservoir of PCB residues. Work by Nimmo
and his colleagues at Gulf Breeze (8) has shown that at least pink shrimp and
fiddler crabs are able to take up PCB residues from this source. Fiddler crabs
and pink shrimp exposed to clean flowing sea water in aquaria containing sandy
silt with initial residues of 6l parts per million (dry weight basis) of Aroclor
125h accumulated an average of 80 ^ 25 parts per million in the whole crab and
2liO parts per million (one pooled sample) in the hepatopancreas of the shrimp.
Accumulation was much less, 17 i 9 parts per million and 6.1 parts per million,
respectively, with silt initially containing 30 parts per million. Some accumu-
lation took place 3.2 _+ 0.9 parts per million (in crabs) and 1.1 parts per mil-
lion (shrimp hepatopancreas) from silt initially containing 2.5 parts per mil-
lion. The same investigators have shown transfer of residues from sediments to
overlying water. Effluent water from the aquarium with 61 parts per million
Aroclor in sandy silt contained 3-5 parts per billion; from the aquarium with
30.0 parts per million in silt, effluent water contained 0.5 parts per billion.
III. EXPOSURE AND BIOLOGICAL ACCUMULATION
Experimental work on biological accumulation by individual species of
vertebrates and invertebrates has been conducted by a number of laboratories
in the United States and elsewhere. Table 7 presents selected data that demon-
strate accumulation factors of up to 75,000 in whole organisms, and in the
99
-------
TABLE 7. ACCUMULATION OF PCBS BY VARIOUS AQUATIC ORGANISMS
Species
Catfish
Envi ronmcntal
Aroclor Exp. Concentration Residue
CoiTOOimc Time (ppb) (ppb)
1248
1254
BluegJll 1248
1254
Fiddler Crab 1254
60
60
60
60
30
Pink Shrimp 1254 30
13.3
4.1
4.9
6.8
3.5
0.5
3.5
0.5
953,000
312,000
312,000
87,000
80,000
17,000
240,000
6,100
Concentration
Factor Sou re a
72,000
76,000
63,700
12,800
22,900
34,000
69,000
12,000
Stalling and
Mayer, '72(7)
100
-------
hepatopancreas of pink shrimp. The data reported in the preceding section
demonstrate that pink shrimp are able to accumulate PCB residues from environ-
mental levels as low as 0.5 parts per billion; and Table 7 shows accumulation
by fish from levels as low as 1 part per billion.
Evidence from environmental samples (Table 6) suggests uptake of PCB
residues from exceedingly low environmental concentrations. Thus the plankton
samples from the North Atlantic contain something like 200 parts per billion,
yet PCB levels in marine waters are believed to be exceedingly low--certainly
less than 0.01 parts per billion.
PCBs, like many of the organic insecticides, are fat soluble, and are
stored in the lipids of animals. Like the insecticides, they resist metabolic
changes, and tend to be concentrated (at least to some extent) at succeedingly
higher levels as they pass through various steps in the food chain.
The data presented in Table 6 suggest that there are two components of
movement through the biota. One is the familiar pattern of food chain accumu-
lations. The other involves direct uptake from the environment by various
trophic levels; e.g., soil to earthworms; water to phytoplankton, zooplankton,
larger invertebrates, and fish. The fish and plankton data from the North
Atlantic reported by Nisbet and Sarofim (3) are consistent with the hypothesis,
in that plankton residue levels are higher than fish levels, suggesting direct
accumulation rather than food chain transfers. So, too, is the evidence from
feeding studies reported by Stalling and Mayer (9) that suggest accumulations
of no more than a factor of 2 over dietary intake levels in fish. It seems
reasonable that food chain transfers are the principal route of accumulation
in warm blooded vertebrates, and possibly in the highest levels of carnivorous
fish. Conversely, direct environmental uptake is probably the most important
for aquatic invertebrates and fish.
That humans are exposed to PCBs is evident from the data in Table 6.
There are a number of possible routes: air, water, food. Fish and shellfish
through uptake from water would be expected to provide the principal continuing
source in the diet. Sampling of fish to keep those containing more than the
FDA interim action level from the market is carried out by FDA and the various
States where fish are known to have substantial PCB contamination. Other foods
have been found to contain PCB residues, but these residues are for the most
part traceable to accidents; e.g., residues in eggs and poultry whose diet in-
cluded fishmeal contaminated by leakage of PCBs from processing equipment
(Monsanto reports they no longer sell PCBs for'this purpose); residues in milk
traceable to silage stored in silos painted with PCB-containing paints; residues
in dry food packaged in PCB-contaminated packaging materials. Aside from the
occurrences traceable to incidents such as the above, residues have been found
in only 179 of 1^,000 food samples by FDA during November 1969-June 1971 (200 of
the h79 were followups on samples found to contain PCBs). In the FDA diet studies
during FY 70 and 71, only 22 of 720 composite samples contained PCB residues.
It is clear that only a small fraction of the U. S. food supply contains detect-
able levels of PCBs.
101
-------
Other routes by which man may be exposed, or may have been exposed,
include breathing of PCB-containing house dust and dermal uptake from carbon-
less copy paper or PCB-containing inks. One sample of house dust from Michigan
was reported to contain 200 parts per million of PCBs (10). Carbonless "carbon"
paper was reported to contain 2-6 percent of PCB Kanechlor 300 (ll); experiments
with this paper demonstrated that PCBs rubbed off when handled, and that even
after washing the hands, approximately two-thirds of the PCBs still remained on
the skin. Dermal uptake through intact skin has been demonstrated in the rabbit,
guinea pig, and rat, and presumably would occur in man.
IV. DISCUSSION
PCBs occur widely in the environment. It seems reasonable that by far the
largest amount is present in dumps and landfills where it is thought to be more
or less sequestered from the rest of the environment.
It is clear from environmental samples that smaller but significant amounts
are present in the terrestrial and aquatic environments. Much smaller total
amounts are present in the biota, but levels in some organisms in some places
are sufficiently high to cause undesirable biological effects. The residues
present in soils and bottom sediments are potentially available for transfer to
the biota, directly or through movement to water and uptake by aquatic organisms.
A relatively small amount of PCBs is required to contaminate a large part
of the biota (for example, 10 tons would be sufficient to contaminate the en-
tire U.S. population to a level of 1 part per million). Organisms can accumu-
late residues from remarkably low environmental concentrations. PCBs have been
shown to accumulate in fish and aquatic invertebrates to levels of 75,000 times
that present in the water (up to 200,000 times in selected tissues), and to be
accumulated from concentrations as low as 0.06 parts per billion. Thus, to pre-
vent levels in fish from reaching the 5 parts per million established by FDA as
the interijn action level for fish as human food, concentrations in water would
have to be less than 0.0? parts per billion, or, to allow some safety factor,
0.01 parts per billion. This level should be sufficiently low that fish and
shell fish would not be adversely affected.
Monsanto has taken a number of voluntary steps to reduce the amounts of
PCBs reaching the environment—both through restricting sales for such uses
and by providing a disposal service for its customers. (During the first year
after this service was announced, more than £00,000 pounds accumulated awaiting
disposal in the 10,000,000 pounds-per-year incinerator being constructed (3).
Despite these steps, substantial amounts of PCBs are still reaching the environ-
ment. They are present in detectable levels in virtually all municipal sewage
effluents. Effluents from many industrial plants such as paper mills, appliance
manufacturers, electrical equipment manufacturers, and chemical industries, in-
cluded higher levels than municipal sewage. As the restrictions continue, a
decrease in residues should occur through gradual exhaustion of existing stocks
and uses.
Mien the restrictions become fully effective, the principal source to the
aquatic environment can be expected to be that part of the electric equipment
manufacturing industry and the electric utility industry that require these
valuable materials because of their fire resistance and dielectric properties.
102
-------
The effluents from such installations should be regulated and closely moni-
tored to assure that no more than 0.01 parts per billion results in the re-
ceiving water. (So, too, should the manufacturing and disposal facilities
of Monsanto.) Good housekeeping should permit this level to be achieved.
An educational campaign aimed at users to assure proper disposal will also
be necessary--so long as the materials are referred to as transformer oils,
cutting oils, hydraulic oils or fluids, etc., care in disposal will be hard
to assure. After all, oils in moderate quantities aren't regarded as trouble-
some substances.
V. RESEARCH NEEDS AND OPPORTUNITIES
1. Data provided by Kuratsune and Masuda(ll) suggest that PCB-contain-
ing carbonless copy paper may have been an important source of PCB residues
in man. An epidemiological study, involving a group of regular users of such
copy paper (airline ticket salesmen; clerical workers; etc.), would shed much
light on this question.
2. The detection of high levels of PCBs in house dust by Price (10)
suggests that inhalation may be an important source of PCB levels in man. Both
the question of occurrence in dust and of respiratory uptake from such dust
should be explored.
3. Residues of PCBs have not been determined in soils, though by infer-
ence they must be present. A set of samples from the program of pesticides
monitoring in soils should be analyzed for PCBs; the set should be drawn with
care to illuminate distribution patterns in, near, and remote from industrial
areas.
h. Data on pesticides in air are unsatisfactory. A few samples, in-
cluding both vapor and particulates, should be collected from industrial areas
and analyzed. If the methodology proves satisfactory, a small-scale survey
should be undertaken to determine the importance of the atmosphere as a trans-
port mechanism.
5>. The presumption that PCBs do not move to ground water should be
tested. The volume of water in this reservoir, coupled with its relatively
long residence time, suggests that even very low levels of contamination may
be significant.
6. Dumps and landfills are thought to be the principal reservoir of PCBs,
but there are virtually no data on behavior of PCBs in these locations. Small-
scale sampling should be undertaken to determine the concentrations brought to
dumps, the fate of PCBs from open burning, and into leachate and gases from
sanitary landfills. Degradation in place should also be investigated.
7. The presumption that submerged sediments contain a large amount of
PCBs should be examined. Such questions as vertical distribution, degradation,
movement, transfer of water, should be explored as well as the current distri-
bution of residues beneath inland and inshore marine waters.
8. The reported finding of PCB residues on the order of 0.2 parts per
million in marine plankton of the mid-North Atlantic requires elaboration.
103
-------
PCB content of plankton from equal volumes of water in inshore and mid-
ocean waters, as well as sampling of the surface film in both areas, would
be informative.
9. Carbon filter samples going back to the mid-1960's are available
from some fresh water locations. If a satisfactory analytical method can
be worked out, samples from a few locations with continuous records should
be analyzed to provide some data on trends that might be useful for correla-
tion with manufacturing data. Fish samples should be considered for the
same purpose.
lOli
-------
FOOTNOTES
1. Jensen, Soren. 1966. Report of a new chemical hazard. New Scientist,
32:612.
2. Isono, N. 1970. Jishu Koza, 1 (l):60, 1 (l4):58 (in Japanese).
3. Nisbet, Ian and Adel Sarofim. 1972. Rates and routes of transport of
PCBs in the Environment. Environmental Health in Perspective. 1, (in press).
14. C.E.Q. (Council on Environmental Quality). 1970. Ocean dumping: A
national policy. Washington, D. C.
5- Lidgett, R. A. and H. A. Vodden. 1970. PCB — the environmental problem
pp 88-96 in PCB Conference, Wenner-Gren Center, September 29, 1970. Stockholm:
National Swedish Environment Protection Board.
6. Acker, L. and E. Schulte. 1971. Vorkommen von chlorieten biphenylen und
hexachlorobenzol neben chlorierten insektiziden in human milch and menschlichen
fettgewebe. Naturwiss, 57:197.
7. Risebrough, Robert W., and Brock de Lappe. 1972. Accumulation of poly-
chlorinated biphenyls in ecosystems. Environmental Health in Perspective. 1,
(in press).
8. Nimmo, D. R., P. D. Wilson, R. R. Blakman, and A. J. Wilson. 1971.
Polychlorinated biphenyl absorbed from sediments by fiddler crabs and pink
shrimp. Nature, 231:50-52.
9. Stalling, David and Foster L. Mayer, Jr. 1972. Toxicities of PCBs to
fish and environmental residues in fish. Environmental Health in Perspective.
1, (in press).
10. Price, Harold A. 1972. Occurrence of polychlorinated biphenyls in humans.
Environmental Health in Perspective. 1, (in press).
11. Kuratsune, Masanori and Yoshito Masuda. 1972. Polychlorinated biphenyls
in non-carbon copying papers. Environmental Health in Perspective. 1, (in press),
12. Veith, G. D. and G. F. Lee. 1970. A review of chlorinated biphenyl con-
tamination in natural waters. Water Research, Jj: 265-269.
13. Schmidt, T. T., R. W. Risebrough, and F. Gress. 1971. Input of poly-
chlorinated biphenyls into California coastal waters from urban sewage outfalls.
Bull. Envir. Contain. & Toxicol., 6(3) :235-2li3.
Ih. Duke, T. W., J. I. Lowe, and A. J. lAfllson, Jr. 1970. A polychlorinated
biphenyl (Aroclor 125M in the water, sediment, and biota of Escambia Bay,
Florida. Bull. Environ. Contamin. Toxicol., 5:171-180.
15. Tarrant, K. R. and J. O'G. Tatton. 1968. Organochlorine pesticides in
rainwater in the British Isles. Nature, 219:725-727.
105
-------
16. Smithsonian Institution, Center for Short-Lived Phenomena. 1970.
S. W. Sweden snow pollution. Event 19-70, Item 8?6.
17. Veith, G. D. 1972. Chlorobiphenyls (PCBs) in Wisconsin natural
waters. Environmental Health in Perspective. 1., (in press).
18. Holdgate, M. W. (ed.). 1970. The seabird wreck of 1969 in the
Irish Sea. Unpublished report (with supplement), Natural Enviroranent
Research Council. Referred to In Nisbet and Sarofim, 1972.
19- Jensen, S., A. G. Johnels, S. Olsson, and G. Otterlind. 1969-
DDT and PGB in marine animals from Swedish waters. Nature, 22t:2[i7-250.
20. Zitko, V., 0. Hutzinger, and P. M. K. Choi. 1972. Contamination of
the Bay of Fundy - Gulf of Maine area with polychlorinated biphenyls, poly-
chlorinated terphenyls, chlorinated dibenzodioxins, and dibensofurans.
Environmental Health in Perspective. 1, (in press).
21. Henderson, C., A. Inglis, and W. L. Johnson. 1971. Organochlorine
insecticide residues in fish. Fall 1969 National Pesticide Monitoring
Program. Pesticide Monitoring Journal, 5(l):l-ll.
22. Jensen, S., A. G. Johnels, T. Odsjo, M. Olsson,, and G. Otterlind.
1970. PCS - occurrence in Swedish wildlife. Presented at PCB Conference,
Wenner-Gren Center, Stockholm. Sept.
23. Finklea, John F., Lamar E. Priester, John P. Creason, Thomas Hauser,
and Tom Hinners, 1971. Polychlorinated biphenyl residues in human plasma
expose a major urban pollution problem. Read before the American Public
Health Association, Minneapolis, Minnesota. Oct.
n ii
2I|. Westoo, G. and K. Noren. 1970. Levels of organochlorine pesticides
and polychlorinated biphenyls in fish caught in Swedish water areas or kept
for sale in Sweden, 1967-1970. Var Foda, 22:93-1146.
2£. flisebrough, R. and V. Brodine. 1969- More letters in the wind.
Environment., 12:16-27.
26. Acker, L. and E. Schulte. 1971. Vorkommen von chlorieten biphenylen
und hexachlorobenzol neben chlorierten insektiziden in human milch und
menschlichen fettgewebe. Naturwiss, 57:U97.
27. Yobs, Anne R. 1972. Levels of polychlorinated biphenyls in adipose
tissue of the general population of the nation. Environmental Health in
Perspective. 1, (in press).
106
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APPENDIX E
Occurrence And Sources Of PCBs In Food
Table of Contents
Page
I. FDA Pesticide Surveillance Program 108
II. FDA Total Diet Studies 109
HI. USDA Sampling Programs 109
IV. Other Regulatory Programs 109
V. Sources of Contamination 110
VI. Results of Surveillance Sampling Programs HO
VTI. Industrial Accidents 113
A. Poultry
B. Meat By-Products
C. Milk
VIII. Paper Food Packaging
IX. Special Surveys
Tables
1. Positive Analyses of Random Food Samples
2. Positive Follow-Up Investigational Samples
3. Summary of PCB Findings in FDA Total Diet Samples
h. Objective Samples - CY 1971 for PCBs 120
107
-------
APPENDIX S
Occurrence and Sources of PCBs in Food
Residues of polychlorinated biphenyls (PCBs) as potential food con-
taminants were first identified by(Jensen, l) in fish from various Swedish
waters. Other early interests in the occurrence of PCB residues in foods
were directed to PCB interferences in the determination of organochlorine
pesticide residues, particularly DDT and its analogs. (Widmarck, 2).
In 196? the Food and Drug Administration initiated a methods
development project to determine the analytical behavior of PCBs and to
devise a means of separating PCBs from chlorinated pesticides in the regula-
tory analysis of food. Experiments demonstrated that PCBs are recovered
and detected by the FDA methodology routinely employed for multiple residues
of organochlorine pesticides at a sensitivity of detection approximately one-
tenth that for p,p'DDT. For example: using FDA's standardized procedures
the limit of detectability for p,p'DDT in butterfat is about 0.15 parts per
million, while for PCBs it is about 1.5 parts per million. Further investi-
gation led to a procedure,(Armour and Burke , 3) that separates PCBs from
organochlorine pesticides after initial sample extraction and cleanup, and
permitting separate determinations of the groups of chemicals. This procedure
is designed for use with the FDA multiple pesticide residue procedure as the
basic analytical method. The analytical method, along with the PCB-separation
step, has application to a wide variety of food and animal feed commodities
and many types of environmental substrates.
In July 1969, FDA field laboratories were provided with the analytical
instructions for separating and determining PCB residues in foods. Since all
objective food samples collected under FDA's pesticide surveillance programs
are examined for chlorinated pesticide residues, the advances in analytical
methodology facilitated analysis for PCBs in food. The food surveillance pro-
grams formally incorporated examination of all samples for PCBs and reporting
of results in November 1969. The United States Department of Agriculture in-
corporated similar procedures in its sampling programs for meat and poultry in
January 1971.
The objective sampling programs represent the basic Federal activity for
monitorine the Nation's food and feed supply for pesticide residues (Duggan and
Cook, h). T^6 main components of these programs are as follows:
I. FDA PESTICIDE SURVEILLANCE PROGBAM
This program is designed to gather information on the extent of pesticide
(including PCBs) contamination of foods and feeds on a geographical basis
through the use of a statistical sampling plan. Samples are collected at
shipping points to facilitate compliance action when illegal residues or
potential residue problems are encountered. FDA field offices select commodi-
ties grown or processed within their areas. Sampling is based on possible
residue problems, volume of production, and other related factors.
Commodities may include fresh fruits and vegetables, dairy products, shell
eggs., grains, fish, animal feeds, and processed foods. The limits of detect-
ability as applied to objective samples is about 0.3 - 0.5 parts per million
PCBs in non-fatty foods and about 1.5 parts per million PCBs in the fat for
fatty foods.
108
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II. FDA TOTAL DIET STUDIES
The total diet program is designed to determine the levels of pesticides,
PCBs, and trace heavy metals in the dietary intake on a geographical and
seasonal basis. Market basket samples, representing the two-week diet
of a 15-20 year old male — which is approximately twice that of the normal
diet — are collected at retail stores, bimonthly, in five regions of the
United States. Food items are cooked or prepared for table-ready use by
dieticians and. are divided into 12 food class composites, such as dairy
products; meat, fish and poultry; and leafy vegetables. Each composite
is analyzed for a variety of chemical contaminants, including PCBs. The
limit of detectability as applied to total diet composites is approximately
0.05 parts per million PCBs. When abnormally high residues are detected
in any composite., follow-up analysis is made of the individual food com-
modities of the composite to determine which food is contributing the ex-
cessive residues and. to determine whether compliance action is warranted.
III. USDA SAMPLING PROGRAMS
The Consumer and Marketing Service, USDA, has primary responsibility
for sampling and. analyzing meats, poultry, and broken egg products for
pesticide, environmental (PCB), and other chemical or biological con-
taminants. The USDA program involves all federally inspected slaughtering
plants (about 1,200) and egg breaking establishments (about lUO). The
instructions for sampling request that the agricultural producer of
the animal, bird, or eggs, be named so that the State of origin will
be known. This facilitates follow-up if a violative sample is found
and identifies those samples which originate from the same farm. Inspectors
are instructed to collect objective samples from different agricultural
producers. The time of sampling and the plant location are determined
on a random basis, by computer, for this program.
IV. OTHER REGULATORY PROGRAMS
In addition to these routine sampling activities, FDA and. USDA learn
6f PCB contamination of foods in other ways. As part of their enforcement
responsibilities, they conduct in-plant establishment inspections; con-
duct special investigations and surveys to determine the cause and extent
of specific PCB problems; and maintain close contact with State officials
and industry who also monitor the occurrence of chemical contaminants in
food.
When required, there is also a selective phase to these sampling
programs and investigations. Selective sampling is used to determine the
extent of violations when a violative sample is encountered or a report
of possible harmful residues is received by the responsible agency. An
increased number of samples is taken in the suspected area to determine
109
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the extent of the problem, and the degree of regulatory control required
to safeguard the wholesomeness of the food supply and to correct the
problem. The selective program has been used to control specific PCB
incidents.
V. SOURCES OF CONTAMINATION
Because of their widespread industrial applications, their chemical
stability and persistence, and their ubiquitous presence in the ecosystem,
it is not unexpected that PCB residues have been detected in a variety of
food commodities. Several sources of contamination have been identified.
These can be generally divided into three categories:
1. Environmental contamination - background levels of PCBs in fish
from contaminated lakes and streams.
2o Industrial accidents - isolated incidents involving direct
leakage and spillage or contact of PCB fluids and other PCB containing
materials on animal feeds, feed ingredients or food.
3. Food packaging materials - PCB migration to foods packaged, in
PCB contaminated paper products. Identification of these categories is
not intended to imply that all positive PCB findings in food and other
materials have been successfully traced to any one of the three sources.
Samples have been reported where the cause of the PCB residue was not
clearly defined,"and. one could only speculate as to the source of the
residue.
Since examination for PCB residues was incorporated into the routine
sampling programs of FDA and USDA, thousands of objective samples have
been analyzed. Additionally, numerous investigative surveys and selective
samplings have been conducted to respond to specific "accidents" and other
problems associated with PCBs in food.
VI. RESULTS OF SURVEILLANCE SAMPLING PROGRAMS
Since November 1969, FDA has analyzed for PCB residues all raw agri-
cultural commodities and other food classes sampled under its pesticide
surveillance program. More than 15>,000 sample examinations had been
completed as of June 1971. A total of 279 of the objective samples was
reported to contain PCBs (Table l). An additional 200 food samples,
collected as follow-up samples of suspected lots because previous analyses
indicated a potential problem, were also found to contain PCB residues
(Table 2).
PCBs were encountered most frequently in fish, with 317 of the total
positive samples (U79). The levels in fish reported in Tables 1 and 2
indicate that most residues are between 1 and 10 parts per million.
The Department of the Interior and others have gathered extensive amounts
of data on PCB residues in fish, and it appears that the occurrence of
PCB residues in fresh water fish is widespread geographically. Residue
levels are related to location (highest in waters near industrial and
metropolitan centers) and the species of fish (high or low fat, and
feeding habits). In order to control the interstate shipment of fish
containing excessive residues of PCBs, FDA (February 1970) established
110
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Examining
Die crlct
Los Angeles
Minneapolis
New Orleans
New York
San Francisco
Seattle
Kansas City
Atlanta
Baltimore
Boston
Buffalo
Chicago
Cincinnati
Denver
Detroit
Dallas
Total
Positive
TABLE 1
Fish
Fish By Product
23(0.1-2.60).62 5(0.2-5.0)2.10
2(.12-35.29)17.70
23(T-1.70)0.4d
3(0.21-4.78)2.49
1(0.40).40
19<0.60-13.30)3.41
1(0.53).S3*
'" ru;nivK A;./.LYSJ-:S M KANJO
N.-n'.-mbrr 1T69 through Jim • 1971
(15,000 Samples Analyzed --all prior to
Erit Coast Torrolr.e.l Fish Meal Incident)
Number Positive Samples (Range-ppm) Avcr»oe ppra
Cheese4
1(6.08)6.08
l9(T-13.00)3.26d
55(0.04-4.70)1.77
49(0.25-15.5)2.96
196
1(T).00
Shell Eggs
6(0. 15-0.30). 19 1(0. 03). 03
Potato
By Product
Oysters Mi8c
1(0.50).50
1(T) 2(0.94-0.97).96
22(7-12.58)2.69 5
-------
PUSmVK FliL'.CM-UP WVKSTICAT10NAL SAMPLES
collected h •rau.se oC £u.-;pected PCB Residues
November J.y.jJ through June 1971
Number Positive SarapL:3 (Range-ppm) Average.ppm
Examining
District
Los Angeles
Minneapolis
New Orleans
New York
San Frsnclaco
Seattle
Kansas Clfy
Atlanta
Baltimore
Boston
Buffalo
Chicago
Cincinnati
Denver
Detroit
Dallas
Total
Positive
Fish
Fish • By Product Cheese8
31(0.1-6.0)1.54 63 (.03-l.0).10c
58
-------
an interim action level of $ parts per million in the edible portion of
the fish.
The surveillance data for milk and manufactured dairy products also
show . this class of food to have a relatively significant incidence of
positive findings. For the most part, the PCS sources were traceable
to localized "industrial accidents" which are described elsewhere in
this report and were not always present as environmental contaminants.
The occurrence of PCBs in milk does not appear to be widespread nationally.
Although no PCBs were found in fresh fruits or vegetables, residues
were reported in potato by-products used for animal feed. The source of
contamination in this case has not been established.
The FDA total diet studies for Fiscal Years 1970, 1971, and 1972
(first-half only) included PCB analysis for 75 market baskets representing
900 composite samples. These analyses showed 5U composite samples to
contain PCB residues ranging from a trace to 0.36 parts per million
(Table 3). Twenty-six of the positive samples were present in the meat,
fish, and poultry composite, and nineteen in the grain and cereal composite.
Findings in other food class composites were at less than 0.05 parts per
million, with no consistent pattern of PCB occurrence. These studies
indicate the dietarv intake of PCBs is of a low order. Expressed as
ms/ke body weight/day, the PCB level for FY 70 was less than 0.0001
and 0.0001 in FY 71 and FY 72.
The objective phase of the USDA sampling program for meat and
poultry during 1971 detected PCBs in l61j of the U,175 samples analysed.
There were 25 samples positive in the 2,hOU samples collected from cattle,
swine, calves, and sheep with a range in the positive results from .1 parts
per million to 3.0 parts per million. The poultry samples reflected the
contaminated feed supply in the Southeastern United States and in the 1,80k
samples analysed, there were lUO positive with an analytical range of 1
parts per million to over 15 parts per million. The three poultry classes,
young chickens, fowl, and turkeys, all had between 7-9 percent samples
positive for PCBs with a range of 1 parts per million. Only two samples
were over guidelines established by FDA.
VH. INDUSTRIAL ACCIDENTS
The following isolated incidents of avoidable PCB contamination of
food led to the actions described to remove the contaminated food from
the market.
A. POULTRY
1. New York State Incident. The Campbell Soup Company, Camden,
New Jersey, noted in December 1970 surveillance data excessive PCB
residues in chickens prown in New York State. T*16 s"tate of New York
placed a quarantine on the three counties involved and pretesting of
all fowl was mandatory before slaughter.
Analysis indicated PCBs in poultry fat varying from a non-
detectable level to 26o8 parts per million. FDA advised the State of
New York and USDA on February 1, 1971, that FDA would not object to the
113
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distribution of poultry containing less than 5 parts per million. This
level was applicable to the edible tissue on a whole tissue basis or
to the separate fat removed during slaughter or processing and intended
for use as a food or feed ingredient.
The regulatory control action extended from December 1970 until
August 1971, when all samples submitted for testing prior to slaughter
were found to be below the 5 parts per million guideline. To support
this control activity and determine disposition of the fowl scheduled
for slaughter the following samples were analyzed for PCBs: 1,5>66 dozen
eggs, 198 feed, and 5,790 chicken samples. Most of the analytical
work was done in the New York State chemical laboratory. On the results
of these samples, ll|0,U5>0 chickens were killed on the farm and buried,
75>,7UO chickens were passed for restricted slaughter, and ^095000 chickens
were released for normal slaughter.
The alleged source of the PCBs in this incident is believed by
State officials to be plastic bakery wrappers. Bakery goods were used
as a feed ingredient for the poultry and the plastic wrappers which may
have contained high PCB levels were ground with the bakery goods.
2. East Coast Terminal Incident (FDA Actions). The Monsanto
Chemical Company informed FDA in July 1971 that large amounts of fish meal
might have been contaminated with Aroclor 12U2 leaking from a heating system
during pasteurization of fish meal at East Coast Terminal, Wilmington,
North Carolina. Aroclor 12U2 was used as the heat exchange fluid. FDA
inspection revealed PCB contamination of processed fish meal on hand at
the firm. Investigation indicated the leak began in April 1971 and continued
through July.
The fish meal on the premises was embargoed and the firm initiated
a voluntary recall of fish meal processed since April 1971. An estimated
12,000 tons were distributed. Over 2,000 tons were recalled. Individual
fish meal samples examined contained from lU to 30 parts per million PCB.
FDA also initiated follow-up sampling of fish feeds, catfish
from fish farms, and eggs when the contaminated fish meal was implicated.
USDA was informed when investigation indicated eggs were being distributed
to commercial egg breakers. As of September 1971, 22k samples of eggs had
been analyzed with 71 containing residues in excess of 0.$ parts per million.
FDA seized 3 lots of eggs. The samples representing these lots
contained from 0.7 to 1.9 parts per million PCB.
FDA seized 5 shipments of fish feeds that were manufactured from
contaminated fish meal. These seizures were in the States of Louisiana,
Georgia, and Mississippi, and were on feeds that contained from 0.6 to
U-5 parts per million PCB. In addition, a shipment of the contaminated
fish meal from East Coast Terminal that had not been recalled was seized.
The analysis of this seized product showed levels in excess of 3!?0 parts
per million PCB. Catfish sampled from commercial fish farms contained less
than 3.0 parts per million PCB.
-------
3. East Coast Terminal Incident CUSDA Actions). The Meat and Poultry
Inspection Program,, USDA, was notified by Holly Farms, Wilkesboro, Worth
Carolina (July 1971) that poor hatchability had alerted them to a problem
in their poultry operation. The cause was PCBs in the poultry ration. The
contaminated feed ingredient was the fish meal from one supplier in North
Carolina. The USDA objective surveillance program had recent reports of
PCBs in poultry fat from the southeastern United States
The Food and Drug Administration informed USDA of the confirmed
PCS contamination problem on July 19, 1971. The 5 parts per million guide-
line for poultry was reaffirmed.
The list of primary consignees, received from FDA, showed the
contaminated fish meal had been distributed throughout 10 southeastern
States.
USDA required all poultry coming to market from this area to be
either pretested or tested after slaughter before marketing. This program
is continuing with owner's certification now being accepted since the source
and feed distribution channels have been identified.
The Poultry Division examined 900 lots of broken eggs, and 12337?0 Ibs,
of product were removed from the market. The Meat and Poultry Inspection
Program has examined samples from over 5,11k flocks of broilers, fowl, and
turkeys during this time. One producer had to destroy over 88,000 broilers.
The present trend in PCB levels is downward, and the contamination
is subsiding. Therefore, an effort is being made by, USDA to test all re-
maining flocks that were exposed to the contaminated feed so that the pre-
testing requirement can be discontinued. Any chicken or turkey flocks
identified as having violative levels of PCBs by this final testing program
will remain under surveillance until disposed of by slaughter.
h. Minnesota Incident. USDA notified FDA in August 1971 that USDA
and Swift and Company had found excessive PCB levels in turkeys.
Investigation indicated that the PCB residues found in the turkeys
were caused by the feed. In addition, it appeared that the fat used as an
ingredient of the turkey feed was the source of the PCB. The suspect fat
used by the feed mill was received from a processor in Minnesota. It was
found that the fat being manufactured at that time contained negligible
levels of PCB. The source of the PCB levels found in the turkeys was not
established.
USDA surveyed turkey flocks for PCBs in the immediate geographic
area, which included parts of Minnesota, North Dakota, and South Dakota.
There were lUO flocks tested, and no residues of PCBs were found above 2
parts per million (fat basis) except in the original grower's flocks,
where PCBs were present at levels up to 20 parts per million (fat basis).
This one grower has been required to pretest all flocks prior
to slaughtero Today the PCB level (fat basis) is approximately 1 part per
115
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million. Approximately 1 million turkeys approaching market weight were
withheld from market until residue levels were reduced to less than 5
parts per million.
5. Oklahoma Incident. On August 20, 1971, USDA informed FDA of
excessive PCS findings in chickens in Mississippi during routine sampling.
Investigation revealed that the birds came from a grower in Oklahoma and
the feed from a mill also in Oklahoma. FDA analysis of eggs and feeds
from these firms showed no PCBs.
6. California Incident. USDA examined turkeys after slaughter in
warehouse storage in California. PCBs were found in the amount of l.Ul to
28.0 parts per million in the fat tissue. There were 100,000 pounds of
turkeys detained until testing was completed. The turkeys had originated
from flocks raised in four counties in California. The source of the
PCBs could not be determined.
B. MEAT BY-PRODUCTS
National By-Products, Inc., Mason City, Illinois Incident - On
July 28, 1971, FDA inspection of this firm revealed that PCBs were used in
heat treatment equipment. Sampling showed the pasteurized meat meal to
contain PCBs. The firm initiated recall of the contaminated product.
C. MILK
1. West Virginia Incident. In July 1969, FDA's Baltimore District
found PCBs in milk samples collected in the routine food surveillance
program. Baltimore District investigated possible routes of contamination,
and by February 1970, the investigation pointed to spent transformer fluid
used 3.3 a vehicle for herbicide sprayed along power right-of-ways in the
Martinsburg, West Virginia area. Through this route, PCBs contaminated dairy
cattle grazing areas. The dairy farms involved were taken off production by
State officials.
2. Ohio Incident. In April 1970, the State of Ohio notified FDA's
Cincinnati District of unidentifiable residues in milk. FDA identified
the residues as PCBs and advised the State of a guideline of 0.2 parts
per million (whole milk). The State of Ohio and FDA investigated the
problem and determined that the dairy farms were using a PCB-containing
sealant in silos that migrated to the silage. The State of Ohio banned
milk from some producers and destroyed an undetermined amount of milk.
3. Florida-Georgia Incidents. The States of Florida and Georgia
reported findings of PCBs in milk to FDA's Atlanta District in August 1970.
A PCB-containing sealant in silos was found to be the source of contamination
in this incident. FDA found approximately 11 percent PCB in the silo
coating.
VTIIoPAPER FOOD PACKAGING
FDA first learned of the PCB food packaging problem in July 1971. The
total diet market basket samples showed low level PCB residue in a grain
and cereal composite (Table 3). The PCB was traced to the Shredded Wheat
116
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TABLE 3 - SUMMARY OF PCB FINDINGS IN FDA TOTAL DIET SAMPLES
FY 1970
30 Market
Baskets
360 Composites
I
II
III
IV
V
VI
Food Class Composites
Dairy Products
Meat, Fish, Poultry
Grain and Cereal Products
Potatoes
Leafy Vegetables
Legume Vegetables
Positive
1
3
-*
-
-
-
Range
(PPM)
T a
0.02-0.03
-
-
-
-
FY 1971
30 Market
360 Compos
Positive
-
14
A
-
-
-
Baskets
ites
Range
(PPM)
-
T-0.15
T-0.36
-
-
-
1/2 FY
15 Market
1972
Baskets •
180 Composites
Positive
1
9
15
1
-
-
Range
(PPM)
T
T-0.08
T-0.10
T
-
-
VII Root Vegetables
VIII Garden Fruits
IX Fruits
X Oils, Fats & Shortening
XI Sugar & Adjuncts
XII Beverages
0.08
T
T
TOTALS
a. Trace (generally less than 0.05
b- None detected
18
31
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packaging material was identified as the source of PCB in the food. The
manufacturer of the packaging material used about 95 percent recycled paper
to manufacture paperboard containers. FDA analysis of different types of
the firm's paperboard showed PCB levels ranging from about 2 to h33 parts
per million. Various types of packaged food products, some of which used
this firm's paperboard, were also analyzed as part of FDA's investigation.
Nine samples of the 28 packaged foods examined contained PCBs in the food
portion.
As a result of this limited investigation, FDA initiated a nationwide
survey in September 1971, to determine the extent of the PCB food packaging
problem. The survey included analysis for PCBs in all paper packaging
components and the packaged food portions of 15 different representative
food categories. This survey was completed in late December 1971. A
detailed statistical analysis of the results of the survey is currently
being compiled. Sixty-seven percent of the packaging portion of the
samples contained PCB residues as high as 338 parts per million; 19 percent
of the food portions of the samples contained PCB residues, with an average
PCB concentration of 0.1 parts per million. The maximum PCB level found
in food was 5 parts per million.
The FDA survey, as well as other studies by the paper and food industries,
show a significant correlation between the presence of PCB residues in the
food component and the packaging component. The mechanism of PCB migration
from the packaging to the food probably occurs through both the vapor phase
and abrasion or physical contact. The level of PCB contamination is
dependent upon many factors — levels of PCBs in the packaging materials,
type of food, length and conditions of storage, and others. The extent of
migration of PCB from paperboard packaging to the food contents is being
investigated (Trout, 5)- There is also significant correlation between
the presence of PCB residues in packaging and the presence of recycled paper
components in the packaging. The occurrence of PCBs in recycled paper materials
is attributed primarily to the recycling of the so-called "carbonless11 carbon
paper (contains 3-5 percent PCB -- use of PCBs for this purpose has been
discontinued) and to a lesser degree, the use of certain printing inks. PCB
residues also were found in some packaging components that appeared to be
composed entirely of virgin paper material. This source of PCBs probably
occurs in the packaging manufacturing processes.
Industry has taken steps to reduce the levels of PCBs in food packaging
materials by avoiding the recycling of carbonless carbon paper. Although
it is not know if this practice has been instituted industry wide, data
provided by the Grocery Manufacturers of America, Inc., does reflect a
change. For example: recycled board manufactured during the period June 1970 -
January 1972 shows that only 18 percent of the samples contained less than
5 parts per million PCB; the same type of recycled board manufactured from
November 1971 through January 1972 shows that 95 percent of the samples to
be below 5 parts per million PCB.
IXo SPECIAL SURVEYS
FDA is currently conducting a national survey to determine the extent
and levels to which complete animal feeds are contaminated with PCBs.
118
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The survey covers feeds for cattle, sheep, swine, chickens, turkeys, and
other miscellaneous animals. The survey results available to date show
that less than £ percent of the complete animal feeds sampled contain
PCBs. Levels range from non-detectable (less than 0.1 parts per million)
to a maximum level of 0.6 parts per million PCB.
Another investigation survey was recently initiated by FDA to survey
the milk supply on a State by State basis to determine the extent of PCB
contamination of milk intended for bottling and manufacturing use. Results
from this survey are not available at this time.
The results of tissue sample studies of several domestic animals and
poultry are shown in Table lj.
119
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TABLE
OBJECTIVE SAMPLES - CY 1971
for PCB's
SUMMARY
PPM - fat Basis
ANIMAL AND POULTRY TISSUE CY 1971
Class
Animals
Poultry
N.D. .01-
2379 1
1664 4
.1 .11-. 50
9
25
.51-1.5 1.51-3.0
11 4
53 23
PCB RESIDUES IN ANIMAL AND
Animal
or
Poultry
Cattle
Calves
Swine
Sheep
Young
Chickens
Mature
Chickens
Turkeys
Ducks
Number of
S amp 1 e s
Analyzed
722
66
1436
180
1637
69
88
10
TISSUES
Number of
Samples wi
A Residue
9
4
7
5
127
5
8
0
3.01-5.0 5.01-7
4 5
POULTRY
.01 7.01-15 Over 15
15 11
COLLECTED IN OBJECTIVE PHASE
DURING CY 1971
Percent of
th Samples with
A Residue
1.2
6.1
0.5
2.8
7.8
7.2
9.0
0.0
Number of
Samples Exceed-
ing Guidelines
0
0
0
0
2
0
0
0
Percent of
Samples Exceed-
ing Guidelines
0.0
0.0
0.0
0.0
0.1
0.0
0.0
0.0
4208
165
3.9
0.04
120
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FOOTNOTES
1. Jensen, S. (1966). New Scientist 32, 612.
2. Widmark, G. (1967). J. AOAC 50, 1069.
3. Armour, J. A. and Burke, J. A. (1970). J. AOAC £3_, 762-768.
h. Duggan, R. E. and Cook, H. R. (1971). Pesticide Monitoring
Journal 5., 37-k3-
5. Trout, P. E. (1971). Grocery Manufacturers of America "PCB Workshop",
November 17, 1971.
121
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APPENDIX F
Human Directed Aspects of PCBs
Table of Contents
Page
I. Introduction 12k
II. Toxicological Aspects
A. Human Episodes
B. Animal Toxicity
C. Contaminants in Polychlorinated Biphenyls
III. Epidemiological Aspects
IV. Studies in Progress
V. Summary and Conclusions 152
Tables
1. Subjective Symptoms Complained by Yusho Patients 126
2. Oral Toxicity of Chlorinated Biphenyls 12?
3. Dermal Toxicity of Chlorinated Biphenyls 128
h. Vapor Exposure Toxicity of Chlorinated Biphenyls 129
5. Toxicity of Aroclors 131
6. Pathologic Changes Induced by PCBs 132-133
7. Residues in Tissues of Rats Orally Dosed with Aroclor 1251) 13h
8. Storage of Aroclors (in PPM) 2l-Hours After Oral
Injestion by Stomach Tube 138
9. Distribution of PCB-Derived Material Following
98-Day Exposure to a Dietary Level of 1000 PPM
Aroclor 125k 139
10. Distribution of PCB Levels in Adipose of General
population as Shown in Analysis of Human Monitoring
Survey Samples Since April 15, 1971 Ilj5
122
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Tables Page
11. Experiments to Date not Included in the Manuscript,
"Polychlorinated Biphenyls: Distribution and Storage
in Body Fluids and Tissues of Sherman Rats" - A.
Cur ley, V. W. Burse, M. E. Grim. 1-?u
12. Some Biological and Toxicological Effects in the PCBs 153
13. Possible Future Studies Involving PCBs, Their Individual
Isomers and Contaminants
List of Figures
1. Storage of PCB-Derived Material in Tissues and Plasma ll»0
2. Excretion of PCB and PCB-Derived Material in Feces and Urine
-------
APPENDIX F
Human Directed Aspects of PCBs
I. INTRODUCTION
The salient aspects dealing with the chemistry and toxicology of the
polychlorinated biphenyls have been summarized previously in a number of
Status Reports of the FDA (Kolbye, 1; Burke and Fitzhugh, 2; Cook, 3).
Additional literature reviews have stressed the chemical and biological
aspects of the PCBs (Peakall and Lincer, h; National Swedish Environment
Protection Board, 5; Reynolds, 6; Zitko and Choi, 7; and Fishbein, 8).
The major objectives of this report are to review the current status
of the toxicologic (acute and chronic), carcinogenic, teratogenic, mutagenic,
metabolic, biological, and epidemiological aspects of the PCBs that are of
greatest relevance to man and, based on the above, to cite areas of suggested
future research that will more definitively relate to the human aspects of
the PCBs.
II. TOXICOLOGICAL ASPECTS
A. HUMAN EPISODES
Compared to the chlorinated hydrocarbon pesticides, definitive aspects of
acute, sub-acute and chronic toxicity still remain rather poorly known. Chlor-
acnegen effects were reported as early as 1936, following industrial exposure
to the PCBs,(Schwartz, 9, 10, 11; Jones and Alden, 12; Meigs, et al., 13).
Occupational chloracne, however, has not been a problem with recent usage of
the PCBs. Approximately 10 cases of fatal intoxication involving persons who
handled or were exposed to chlorinated biphenyls or naphthalenes in their
occupations have been described (Flinn and Jarvik, llj; Greenburg, et al., 15;
and Drinker, et al., 16). In all cases histological examination revealed
liver fatty degeneration, necroses and cirrhosis. It is important to note
that chlorinated naphthalene (as well as chlorinated dibenzofurans) have been
recently identified in two commercial polychlorinated biphenyl samples (Pheno-
clor DP 6 and Clophen A60), (Vos, et al., 17).
Human intoxication with the heat exchanger Kanachlor hOO, a Japanese manu-
factured PCB with 148 percent chlorine and containing as its main components, 2,lj,
3', li1-, 2,5,3', Ij'-:, 2,3,14,14'- and 3,^,3' ,b'-tetrachlorobiphenyl, and 2,3,li,3',
l4'-pentachlorobiphenyl,(Saeki, et al., 18), was reported in Western Japan in 1968.
More than 600 people were eventually affected following the consumption of
contaminated rice oil containing levels estimated to range from 2,000 to 3,000
parts per million PCBs (average of about 2,000 parts per million). These levels
were derived from the known organic chlorine content of the rice oil related to
the known organic chlorine content of Kanachlor IjOO. Exposure levels to the oil
were calculated to approximate 15,000 milligrams per day. The lowest reported
figures allow an estimate of a minimal positive effect level at 3 milligrams PCB
per day over several months. However, the average doses associated with signifi-
cant disease in the "Yusho" incident were much higher and were in the range of
30 milligrams/day. (Kolbye, l).
1214
-------
The clinical aspects associated with "Yusho" included: chloracne, blindness,
systemic gastrointestinal symptoms with jaundice, edema and abdominal pain.
Chloracne is very persistent with some patients showing evidence of it after
three years. Table 1 lists the subjective symptoms of 89 male and 100 female
Yusho patients .
New-born infants born from poisoned mothers had skin discoloration due to
the presence of PCB via placental passage. (The dark skin discoloration re-
gressed after a period of 2-5 months). Gingival hyperplasia with pigmentation
was seen in several cases. Decreased birth weights were also noted but no
evidence could be obtained in regard to the possible retardation in physical
and mental activities of the babies (Yamaguchi, et al., 19). The skin of still-
born infants showed hyperkeratosis and atrophy of the epidermis and cystic dila-
tion of the hair follicles. Residues of PCB have been found in fetal tissue
(Kojima et al., 20 ; Inagami et al., 21).
The components of Kaneclor IjOO with longer retention times have been detected
in sputa and fatty tissues of patients (Kojima, 22). Serum triglyceride levels
were higher than 300 mg/ml in 60 out of 396 subjects investigated before the end
of 1969 (Uzawa et al., 23, 21). Among the incidence of hyper glyceridemia
(triglyceride>300 mg/ml) of the six decade groups (age 0-9, 10-19, 20-29, 30-39,
Ii0-h9, 50-), that of the first decade group was the highest while that of the
third decade was the lowest. The mechanism of the hyper glyceridemia was suggested
to be possibly due to an observed decrease in post-heparin lipolytic activity and
impaired plasma triglyceride removal (Uzawa et al., 2l). Cholesterol and phos-
pholipid concentrations were increased while lecithincholesterol acyl transferase
activity was decreased. In female patients plasma lipoprotein lipase activity was
decreased (Uzawa et al., 2h; Nagai et al., 25). Nearly ijO percent of the examined
patients exhibited an elevated excretion of steroids with the 17-ketosteroids
(androsterone, etiocholanolone and dehydroepiandrosterone) found to increase in
males and to decrease in females (Nagai et al., 25).
Examination of autopsy tissues of two Yusho fatalities revealed the presence
of chlorobiphenyls in all of examined organs, especially mesenterial fatty tissues,
skin and bone marrow (Kikuchi, et al., 26). Kojima, et al.,(20) found PCBs with
longer retention times (probably pentachloro- and 'higher chlorinated biphenyls ) in
autopsy tissues and it was assumed that their presence might have been responsible
for the observed long duration of the intoxication symptoms.
B. ANIMAL TOXICITY
Early studies of acute oral, dermal and vapor exposure of the polychlori-
nated biphenyls have involved in many cases mixtures or compounds of undefined
specifications and hence have been difficult to interpret unambiguously. Tables
2-h describe the oral, dermal and vapor exposure toxicity involving a number of
chlorinated biphenyls and the results would suggest that the toxicity of these
compounds is proportional to their degree of chlorination. These investigations
have primarily focused on liver damage. The toxicity of 11 Aroclors in terms of
oral LD^o (rats) and skin MLD (rabbits) is summarized in Table 5-
a. Sublethal and acute effects; Analogously with the chlorinated hydro-
carbon pesticides, the most important effects are long-range sublethal effects.
The pathologic changes in various organs are summarized in Table 6 illustrating
some interesting differences between mammals and birds. For example, the most
125
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TABLE 1.
SUBJECTIVE SYMPTOMS COMPLAINED BY YUSHO PATIENTS3'b.
Symptom
Male
Female
Dark brown pigmentation of nails
Distinction of hair follicles
Increased sweating at palms
Acnelike skin eruptions
Red plaques on limbs
Itching
Pigmentation of skin
Swelling of 1 imbs
Stiffened sole and palm
Pigmented mucous membrane
Increased eye discharge
Hyperaemia of conjunctiva
Transient visual disturbance
Jaundice
Swelling of upper eyelids
Feel inrf of weakness
Numbness in limbs
Fever
Hearing difficulties
Spasm of 1 imbs
Headache
Vomiting
Diarrhea
83.1
64.0
50.6
87.6
20.2
42.7
75.3
20.2
24.7
56.2
88.8
70.8
56.2
11.2
71.9
58.4
32.6
16.9
18.0
7.9
30.3
23.6
19.1
75.0
56.0
55.0
82.0
16.0
52.0
72.0
41 .0
29.0
47.0
83.0
71.0
55.0
11.0
74.0
52.0
39.0
19.0
19.0
8.0
39.0
28.0
17.0
aEighty-nine male and 100 female patients diagnosed before October 31, 1968
were examined.
bFrom a report of "Yusho, A Poisoning Caused by Rice Oil Contaminated with
Chlorobiphenyls", Kuratsune, M., Yoshimura, T., Matsuzaka, J. and Yamaguchi,
A, Fukuoka Acta Med., 6£[6] (1969) 513.
126
-------
TABLE 2.
ORAL TOXICITY OF CHLORINATED BIPHENYLS,
Chi
%
42
42
65
orine
atoms
3
3
7
Animal
Guinea Pig
Rat
Rat
Dose
69 mg/animal
2 doses
1 week apart
139 mg/animal
25 daily doses
50 mg/animal
every second
day
Effect
Death in 11-29 days.
Liver damage.
(Miller, 1944) (53)
All animals
survived. Liver
damages. (Miller, 1944) i
(53) !
j 50% dead within
35 days.
Severe liver
i damages.
! (Bennett, ej aj, 1938). (5h)'
-------
TABLE 3.
DERMAL TOXICITY OF CHLORINATED BIPHENYLS,
CO
Chli
%
42
42
42
Drine
atoms
3
3
3
Animal
Guinea pig
Rat
Rabbit
Dose
34.5 mg/daily
over 11 days
34.5 mg/daily
over 25 days
86 mg/day with
2-day intervals
for 7 appl i-
cations and 172
mg/day with 2-day
intervals for 8
appl ications
Effect
All animals died
within 21 days.
Liver damage.
Miller, 1944) (53)
All survived.
Minor 1 iver changes.
Skin affected.
(Miller, 1944) (53)
All died between
17 and 98 days.
Liver damages more
pronounced than in rat
or guinea pig.
(Miller, 1944) (53)
-------
TABLE 4
VAPOR EXPOSURE TOXICITY OF CHLORINATED BIPHENYLS.
Chlo
%
42
42
54.3
54.3
65
rine
atoms
3
3
5
5
7
Concent
mg/m3
8.6
6.83
5.4
1.5
0.57
0.93
ration
ppm
830
660
410
115
Daily exposure
time (hours)
7
7
7
7
16
8
Exposure
number
17
84
83
150
Exposure
period
(Days)
24
122
121
213
37-134
42-143
Symptoms
No effect on cats,
rabbits, rats and mice.
Poor growth in guinea
pigs. (Treon, 1956) (55)
No effects on animals
as above, Treon, 1956)(^
Liver cell injury.
Increased liver
weight in the rat.
(Treon, 1956) (55)
Histologies! changes
in the liver in the
rat. (Treon, 1956) (55)
Advancing liver
damage.
(Bennett, et al., 1938).
(tt)
-------
striking findings in mammals are alterations to the liver, whereas fluid
in the pericardial sac, kidney damage and reduced spleen are found in
birds.
The FDA has conducted a subacute feeding study (lasting up to 90
days) in rats with dosage levels of 25, 75} 150, 300 and 500 parts per
million of Aroclors 125L and 1260 and including sacrifices at 5, 15, 30,
60 and 90 days (Burke and Fitzhugh, 2). Liver weight to body weight
ratios increased at all levels. Dose-related increases were also found
in liver aniline hydroxylase and nitroreductase activity at all levels
with the magnitude of the increases approximately the same at all time
levels for both Aroclors. Aroclors 1251 and 1260, in contrast to many
chlorinated hydrocarbon pesticides, did not stimulate liver aliesterase
activity.
(Nishizumij 2?) studied the effects on mouse and monkey liver of
chlorinated biphenyls (h8 percent chlorine, equivalent to three to four
atoms of chlorine per molecule, with a trace (0.01 percent) naphthalenes..
Groups of 30 female mice were given a dosage level of 0.2 ml rice bran
oil containing 1600 parts per million or 0.5 percent PCB in olive oil by
stomach tube each day for h to 26 weeks resulting in marked liver en-
largement. (Light microscopy revealed only slight liver changes, but
electron microscopy disclosed marked alterations in the liver cells.)
A similar study with eight monkeys (5 cynomolgus and 3 squirrel) given
chlorinated biphenyls in dosage levels of l.h to 16 mg/day in their diet
for hO to ii8 days showed both liver cell enlargement and fatty degenera-
tion. The major abnormality reported for the administration of chlori-
nated biphenyls to mice and monkeys was an increase in the smooth endo-
plasmic reticulum in the liver cells.
The metabolism and distribution of Aroclor 1251) in normal and carbon
tetrachloride-treated Wistar strain rats have been studied by (Grant, et
al., 28). Residues of Aroclor 125h (following oral administration of a
500 mg per ml corn oil solution of Aroclor at 500 mg/kg) were found in all
tissues analyzed with fat and blood having the greatest and least concentra-
tion, respectively (Table 7).
Aroclor 12%k was found to potentiate the toxicity of carbon tetra-
chloride in a manner similar to that reported for DDT (McLean and McLean,
1966; Cawthorne, et al., 1970). The studies (Grant, et al., 28) suggest.
that the liver is the main site of Aroclor 125ii metabolism since rats with
carbon tetrachloride damaged livers were unable to metabolize this mixture
of chlorinated biphenyls as rapidly as rats with normal livers. Aroclor
125b significantly increased the size of the liver and also the percent
lipid in the liver. The same study revealed that the components of Aro-
clor 125h with the shorter GLC retention times, presumably with the lowest
chlorine content (Bagley, et al., 29), were metabolized to a greater de-
gree than those with the longer retention times. This effect is in agree-
ment with the studies of Phenochlor D?6 fed to Japanese quail (Koeman, et
al., 30).
Yoshimura and co-workers, (31) studied the effects of a single 2.0 mg/
mouse dose of polychlorinated biphenyls of the KC-hOO type. The concentra-
tion of PCB in the skin one day after ingestion was twice as high as that
in the liver. Although tetrachlorobiphenyls were almost completely elimi-
nated from the tissues in 3-b weeks, small amounts of penta- and hexachloro-
biphenyls were still detectable after 9-10 weeks.
130
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TABLE 5.
TOXICITY OF AROCLORS*.
Aroclors
1221 1232 1242 1248 1260 1262 1268 4465 5442 5460 2565
Oral LD50 tug/Kg 3980a 4470a 8650a 11,000a 10,000b 11 ,300b 10,900b 16,000b 10,600b 19,200C 6,310C
(rats)
Skin MLD mg/Kg >2000a >1260a >794a >794a >1260b >1260b >2000b >1260b >7940C >2000C
(rabbits)
<3169a <2000a <1269a >1269a <2000b <3160b >2500C <3160b <2000b <3160
aUndiluted.
Administered as 50% solution in corn oil.
cAdministered as 33.3% solution in corn oil.
FDA Status Report on the Chemistry and Toxicology of Polychlorinated Biphenyls (PCB) or Aroclors as of June 1, 1970.
-------
TABLE 6.
PATHOLOGIC CHANGES INDUCED BY PCBs.
Treatment
Single oral dose
of 69 mg (42% Cl)
Animal
Guinea Pig
Rat
Rabbit
Liver Kidney
Small droplets Essentially
through lobules, normal
slight to moderate
central atrophy,
focal necrosis noted
in a few animals
Pericardium & Other
Peritoneum Observable Changes
No noteworthy Adrenals, spleen, &
changes pancreas showed no
noteworthy changes.
References
Miller, 1944
(53)
300 mg daily for Rat
6 days (65% Cl)
50 mg daily for Rat
up to 6 months
(65% Cl)
25,50 & 100 ppm Rat
in diet for 15
days (21-68°* Cl
Aroclors)
100 ppm in diet Chicken
200 ppm in diet
400 ppm in diet
800 ppm in diet
(Aroclor 1242)
Cells swollen, hyal-
ine granules present,
most died within few
days.
Enlarged (33% weight
increase), large
number of hyaline globules
in cytoplasm. Several
died during experiment.
Increase in weight, effect
increasing with increasing
chlorine content, Aroclor
1232-10%, 1242-12%, 1254-
14%, 1268-24% at 50 ppm.
No effect
No effect
Enlarged & Mottled
Damaged
Damaged
Slight
Hydropericardiurn
Hydropericardium
Hydroperlcardiurn,
hydroperitoneum,
Enlarged
Bennett,
et aU 1938
(5k)
Bennett, e_t
al... 1948
(5M
Street, et al
1969
(56)
McCune, et.
al_., 1962
(57)
-------
TABLE 6. (Cont'd.)
PATHOLOGIC CHANGES INDUCED BY PCBs.
Treatment
200 & 400 ppm
in diet for 3
weeks (42%,
Aroclor
Various doses
(54% Cl,
Aroclor)
M
UJ
VjO
Animal Liver Kidney
Chicken No changes noted Paleness at 200
ppm, extensive
hemorrhage, and
enlargment at
400 ppm
Bengalese No weight changes Weight was 32.4%
Finch of brain weight
for controls and
53.5% for those
dying from PCB
poisoning.
Pericardium & Other References
Peritoneum Observable Changes
Increased fluid Paleness of pancreas, Flick, et
in pericardia! enlargment of adrenal al., 1965
sac at the high- and small apleen at (58)
er concentration. low concentrations.
At higher concentrations
pale cream-colored pan-
creas, adrenals hemorrhagic.
Slight weight Presst, et.
increase, a few al . , 1970
showed liquid (59)
in pericardia!
sac.
400 ppm in diet
for 60 days
(60% Cla)
Chicken Centrolobular
necrosis (compd.
1 & 2). Liver
weight increased
from 2.76 g/!00g
to 4.31g/100g
(compd. 3). Fatty
degeneration.
Tubular dilata-
tion, compd. 1 &
2). Rare with
compd. 3.
Hydropericardium Increased porphyria, Vos and
common with
compds. 1 & 2.
Rare with compd.
3.
spleen small with
reduction of red
pulp and atrophy of
white pulp (compd.
1 & 2). Spleen de-
creased from 0.14g/
lOOg to 0.136g/100g.
(compd. 3).
Koeman, 1970
Phenoclor DP 6 (cpmpd. 1). Clophen A60 (compd. 2) and Aroclor 1260 (compd. 3) were used. Differential effects noted
under compd. numbers. All chickens died on compd. 1 and 2 within 60 days; only 15% mortality on compd. 3.
-------
TABLE 7.
RESIDUES IN TISSUES OF RATS ORALLY DOSED WITH AROCLOR 1254 (500 mg/kgf.
Residue found (ppm, wet tissue)
Group 1 234
Blood 1.96a+0.23b 0.42+0.07 3.85+0.46 0.25C
Testes 19.22 .+. 0.59 4.30 ± 0.44 33.18+1.35 5.62
Heart 24.16 ± 2.84 5.83 ± 0.53 62.40 + 4.37 6.17
Spleen 29.17+3.44 5.82+1.17 36.60+4.39 -
Kidney 31.14+2.09 11.20+1.76 57.38+3.91 11.08
Brain 39.98 ± 5.91 4.01 ± 0.31 41.91 + 3.30 5.96
Liver 115.66 ± 10.55 18.85+1.65 796.47 ±64.96 18.79
Liverd 1868.14 ± 166.63 — 6137.64 ± 556.06 —
Fat 996.16 ± 98.58 672.66 ± 155.12 900.46 ± 106.16 1149.05
aMean of five values.
^Standard error of the mean.
cSingle value.
on a fat basis.
Grant, D. L., Phillips, W. E. J. and Villeneuve, D. C., Bull. Env. Contam.
Toxicol., 6 (1971) 102.
131*
-------
Street and co-workers (32) studied the effects of diets of 50 parts per
million to 100 parts per million of 10 Aroclors ranging in chlorine content
and 21 percent to 68 percent fed to rats for 15 days. Their effect on sleep-
ing time induced by hexobarbital, in vitro rates of aniline hydroxylation and
demethylation of p-nitroanisole, and the rate of excretion were all found to
be increased with increasing chlorine content. Aroclor 1221 (50 parts per
million) reduced hexobarbital sleeping time by 11 percent, whereas for Aroclor
12lj8 and 1268 the figures were 35 percent and hQ percent, respectively. Liver
weights were also found to increase with increasing chlorine content of the
Aroclors. The storage of dieldrin was decreased in relationship to the chlorine
content. For example, with Aroclors containing 60 percent chlorine^ or more,
the storage in adipose tissue was reduced to the levels found in untreated con-
trol animals. The induction of PCBs of hepatic microsomal hydroxylating enzymes
has been demonstrated in the American kestrel (Peakall and Lincer, I), and
pigeons (Risebrough, et al., 33).
Fujita, et al. (66) studied the enhancement of the liver drug-metabolizing
enzyme system in the rat by several individual chlorinated biphenyls . The most
potent inducer was 2,3', h,hl , 5-pentachlorobiphenyl and the effect induced with a
single dose of 3,3' jl^l'-tetrachlorobiphenyl was found to persist for 6 weeks.
Villeneuve, et al. (3h) studied the effects of PCB administration on micro-
somal enzyme activity in pregnant rabbits. The no-effect level of Aroclor 12f?k
for enzyme induction in the pregnant rabbit is between 1.0 and 10 mg/kg body
weight when administered for 28 days during gestation. Aroclor 1221 did not in-
duce any enzyme activity in the dose, fetus or placenta, so its no-effect level
must be considered higher than that for Aroclor 1251i. Placental transfer was shown
to occur for both Aroclor 125U and 1221 but does not cause any changes in the bio-
chemical or physiological parameters measured, e.g., total amount of Vitamin A
stored per liver, protein levels, aniline hydroxylase enzyme activity, serum
cholesterol, no effect in reproductive processes. The drug-metabolizing enzymes
aniline hydroxylase and aminopyrine-n-demethylase were both induced by 10 mg/kg
Aroclor
Ito and co-workers (35) found that the administration of PCBs to rabbits in-
creases the total lipid, triglyceride, and cholesterol content of liver and de-
creases the total liver phospholipid content. (The concentration of serum tri-
glycerides was abnormally increased).
Kimbrough (36) described some aspects of the toxicity of Aroclor 125^ and
1260 in Sherman strain rats. The acute oral ~LD%Q for Aroclors 1251) and 1260 in
adult rats was greater than h and 10 grams/kg, respectively. The salient features
of the subacute feeding and reproduction study in both male and female rats can be
summarized as follows :
1. Feeding 500 parts per million of Aroclor 1251) and 1260, respectively, to
both male and female rats over a period of about 2liO days resulted in less weight
gain as well as lowered hematocrit.
2. Some male rats fed Aroclor 125h at a dietary level of 100 parts per million
(approximately 5 mg/kg per day) developed porphyria. Porphyria was also found in
female rats fed Aroclor 125^ at the 20 parts per million level and in both male
and female rats fed 100 parts per million Aroclor 1260.
135
-------
3. Liver changes found with both Aroclor 12|?Li and 1260 include accumulation
of fat, inclusions within the liver cells and so-called margination (also found
with chlorinated hydrocarbons).
Li. Male rats fed Aroclor 1260 at a dietary level of 100 pai-ts per million
on up had larger and heavier livers. In the females the liver weights were not
significantly increased at any of the dietary levels that were tested.
5. Adenofibrosis was found in: (a) 1/10 males and 6/10 females at the
dosage level of 100 parts per million Aroclor 12%h in the diet for about 8 months;
(b) in 1/10 female rats at 100 parts per million Aroclor 1260 in the diet for about
8 months; and (c) in several male rats at 1000 parts per million Aroclor 1260 in
the diet for 8 months (none at 500 parts per million). The adenofibrosis consisted
of fibrosis in the livers concomitant with a proliferation of cells which is con-
sidered by some to represent proliferated bile ducts.
6. Two bladder cancers in rats fed 100 parts per million of Aroclor 1260
were also found and the significance of this finding has not been fully assessed
at this time .
7. A definite effect on reproduction was produced by feeding 100 parts per
million of Aroclor 125L|. The first breeding was performed after 76 days on the
treated diets and resulted in less offspring. The offspring at weaning were
smaller and the survival was decreased compared to control animals. An increase
in the liver weight in the ^a generation of the weanlings at a dietary level of
20 parts per million Aroclor 12^h was also found.
8. A dosage of Aroclor 1260 equivalent to 100 mg/Kg/day during the 7th and
days of pregnancy reduced the survival and number of young.
Curley and co-workers (37, 38) studied the distribution and storage of PCBs
in body fluids and tissues of Sherman rats following: (a) a single oral dose;
(b) repeated dietary intake: and (c) after discontinuance. The salient findings
of this study could be summarized as follows:
(l) Following acute or chronic administration of Aroclor 125lt or 1260,
residue amounts can be detected in all body tissues, fluids and excrement.
(2) Pronounced changes in the gas chromatograms or mass spectroscopic total
ion current traces between the Aroclor standards and components observed in the
fat and urine suggest possible metabolism or differential absorption.
(3) Rats given single oral doses of Aroclor 125^4 at 1600 mg/Kg or of Aroclor
1260 at 3200 mg/Kg had essentially the same levels of residue in their tissues after
2h hours (although individual variation was high).
(li) At the same dosage level rats store more PCBs than DDT.
(5) No significant differences were apparent in the storage of PCBs by male
or female rats when fed the same dietary levels with PCBs stored primarily in
adipose tissues .
136
-------
(6) Toxicity of the Aroclors apparently increases with decrease in chlorine
content suggesting the enhanced reactivity and/or less stability of some isomeric
chlorobiphenyl in the mixture.
(7) Rats fed Aroclor 125h at 100 parts per million for 58 days and untreated
food for 71 days showed gradually increasing residues during dosage while the ex-
cretion trend was quite erratic.
(8) Aroclor 125h administered at a dietary dosage of 1000 parts per million
for 98 days resulted in deaths of 9 of 10 male rats and 8 of 10 females with deaths
commencing on the 35th day. Although the survivors appeared normal, there was no
weight gain after 77-8Li days.
Table 8 illustrates the storage of Aroclors 125b and 1260 in plasma and tis-
sues after oral ingestion by stomach tube at levels of 1600 mg/Kg and 3200 mg/Kg,
respectively. Table 9 depicts the distribution of PCB-derived material following
98-day exposure to a dietary level of 1000 parts per million of Aroclor 125k.
Figure 1 shows the storage (mean cone, vs. time) of PCB-derived material in
tissues and plasma. Figure 2 shows the excretion of PCB and PCB (mean cone. vs.
time) derived material in feces and urine.
The distribution of PCB in rats dosed with PCBs has been studied with the
aid of X-ray fluorescence analysis. PCB residues were found mainly in the skin,
and to a lesser degree in muscles, intestines, livers, pancreas and lungs, and
the GLC patterns of PCB varied from tissue-to-tissue (Sekita et al., 39).
The intestinal absorption in the rat of a number of isomeric chlorobiphenyls
has been studied by Albro and Fishbein•(hO). PCBs having from one to six chlorine
atoms per molecule were very well absorbed and/or metabolized when the compounds
were fed in a single dose between 5 and 100 mg/Kg body weight. No significant
difference in excretion rates (e.g., retentions) were observed over the molecular
weight range 116.5 to 289, suggesting that diffusion may not be rate-lijniting for
the uptake of these compounds. (When similar tests were performed using aliphatic
hydrocarbons, a clear relationship between percentage excreted in the feces and
molecular weight was observed). Less than 10 percent of the amount fed were ex-
creted in the feces (over a It-day period) indicating a high degree of absorption
and/or metabolism of these compounds.
b. Long-term studies: The chronic PCB studies of Monsanto with Aroclors
1212, 125h, and 1260, e.g., two-year albino rat and beagle dog, three-year rat
reproduction as well as the twenty-five week chicken, have been completed and a
copy of the results sent to the FDA. As of this writing, the full report has not
been evaluated. However, Dr. Elmer Wheeler of Monsanto has verbally touched on
the highlights of these studies supplementing information previously reported in
the FDA Status Reports of the PCBs of June, 1970, and December, 1970, as well as
reported by Keplinger and co-workers (hi) and discussed with the Interdepartmental
PCB-Task Force at a meeting in Washington on September 15, 1971. These results
can be briefly summarized as follows:
137
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TABLE 8.
STORAGE OF AROCLORS (IN PPM) 24-HOURS AFTER ORAL INGESTIOM BY STOMACH TUBE,
Aroclor 1254
(dosage level - 1600 mg/kg)
Aroclor 1260
(dosage level - 3200 nig/kg)
00
Plasma
Mean
SE
Brain
Mean
SE
Fat
Mean
SE
Liver
Mean
SE
Kidney
Mean
SE
Lung
Mean
SE
Muscle
Mean
SE
24.03
8.08
138.00
± 36.41
1146.9
± 574.5
141.20
47.80
274.03
30.47
65.91
29.48
80.29
67.58
15.79
0.99
145.17
23.50
930.0
± 426.6
236.1
116.3
328.5
114.9
105.17
21.13
37.00
22.37
-------
TABLE 9.
DISTRIBUTION OF PCB-DERIVED MATERIAL FOLLOWING 98-DAY EXPOSURE TO A DIETARY LEVEL OF 1000 PPM AROCLOR 1254.
•-o
Plasma
Mean
SE
Fat
Mean
SE
Muscle
Mean
SE
Lung
Mean
SE
Brain
Mean
SE
Kidney
Mean
SE
Liver
Mean
SE
Males (ppm)
17
± 6
11278
± 5742
155
± 117
78
± 23
111
± 14
56
± 9
155
± 30
Females (ppm)
18
5
8431
579
753
721
52
20
94
Zl
54
24
210
13
Males ys_. Females
p >0.50
p >0.50
p >0.20
p >0.50
p >0.50
p >0.50
p >0.20
-------
Figure 1. Storage of PCB-Derived Material in Tissues and Plasma.
O Fat
% Liver
Q Kidney
Q Muscle
£ Brain ~
A Plasma
10
30
30
TIME
-------
Figure 2. Excretion of PCB and RGB-Derived Material in Feces and Urine,
100
D
Q_
^ g
C-J
SI
o
SO.
s.
v.
.M
.'•>N
,'M
.-M
.9)
O
30
D Feces
O Urine
to
TIME (f)AYS)
-------
(l) Aroclor 12Li2 is the least toxic of the Aroclors tested in two-year
rat and dog studies. Aroclor I2k2 was negative at 1, 10 and 100 parts per
million levels.
(2) Rats fed compounds 125k or 1260 had increased liver weights at 100
parts per million, but not at 1 or 10 parts per million with no other effects
having been observed.
(3) Dogs fed 100 parts per million of 125k or 1260 did not gain weight as
well as the controls. Animals were sacrificed at 336 and 12 months and revealed
no abnormal tissue histology.
(ii) In the rat reproduction study, there was decreased survival of pups
at 100 parts per million of 12k2 or 125k, and decreased mating indices with
12li2 at 100 parts per million were also observed. No adverse effects were
found at any of the three levels of 1260 or at 1 or 10 parts per million levels
of Aroclors 12k2 and 125k.
In regard to the 25-week chicken study, there were no effects found follow-
ing feeding with Aroclor 1260 at 1, 10 and 100 parts per million levels. There
was anorexia, loss of body weight, decreased thickness of egg shells, and poor
hatchability of eggs from chickens fed 10 or 100 parts per million of 12142 or
100 parts per million of 125k. There were no effects observed for Aroclor 125k
at the 1 and 10 parts per million levels. Oral feeding studies with Aroclor
12k2 were repeated at the 2, k and 8 parts per million level and decreased hatch-
ability was observed at 8 parts per million.
A rat teratology study of Monsanto following FDA protocol in which 35-65
mg/Kg of PCB is administered has produced no effect.
In regard to the mutagenesis study of Monsanto (Dominant Lethal Test), two
dose levels of Aroclors 12k2, 125k and 1260 are being used, e.g., 500 and 1000
mg/Kg. As of the fourth week since mating, no adverse effects have been found.
It is of interest for comparison to recite the reproduction studies of
the Atlanta Laboratories of the FDA (FDA Status Report, December, 1970). Wean-
ling male and female rats were fed diets containing Aroclor 125k at dosage levels
of 0, 100 or 500 parts per million for 6? days and then pair-mated. The rats
fed 100 parts per million were comparable with the controls in numbers of litters
and pups per litter. However, 76.8 percent of the pups in the 100 parts per
million group survived to weaning compared with 95-5 percent of the controls.
The mean body weight of the 100 parts per million group at weaning was 31.h gm
and that of the controls was 39.2 gm. Only two of ten females fed 500 parts
per million of Aroclor 125k had litters (l and 7 pups, respectively), and these
pups died within 3 days after birth. In a similar study with Aroclor 1260 no
difference in reproduction was found between the controls and the 100 parts per
million group.
C. CONTAMINANTS IN POLYGHLORINATED BIPHEMLS
(Vos and Koeman, Ii2) reported a significant difference in toxicity between
three commercial PCB preparations (Clophen A60, Phenoclor DP6 and Aroclor 1260),
despite the marked resemblance of the gas chromatograms and the mass spectra
1U2
-------
(Koeman et al., 30). One hundred precent mortality, centrolobular liver.
necrosis and abdominal edema were found only in chicks fed the samples of Clophen
A60 and Phenoclor DP6. Hydropericardium was recorded in nearly all chicks fed
these PCBs and only rarely seen in chicks fed with Aroclor 1260. Porphoryia was
found as a general PCB effect in chicks as well as in Japanese quail and rats
(Vos and Koeman, l\2 ).
A subsequent study by Vos and co-workers (17) revealed the presence of
tetra- and pentachlorodibenzofuran as well as hexachloronaphthalene in Phenoclor
DP6 and Clophen A60, but not in the Aroclor 1260 sample. Since hydroperi-
cardium occurred occasionally in chicks fed Aroclor (Flick, et al.^3). Vos
and co-workers (17) felt that this could possibly be indicative of small quanti-
ties of a toxic factor in this preparation.
Dermal toxicity studies in rabbits of technical PCB samples which contain
an average of 60 percent chlorine (Phenoclor DP6, Clophen A60 and Aroclor 1260)
as well as fractions containing tetra- and pentachlorodibenzofuran have been
recently described by Vos and Beems (Iili). PCB-induced skin lesions were hyper-
plasia and hyperkeratosis of the epidermal and follicular epithelium following
application of 118 mg of the three PCBs (5 times per week for 38 days) in the
back skin of adult female New Zealand rabbits. Histopathology of the liver in-
cluded centrolobular degeneration, centrolobular liver cell atrophy, focal necor-
sis and cytoplasmic hyalin degeneration. PCB-induced kidney lesions were hydropic
degeneration of the convoluted tubules and tubular dilatation with the presence
of casts. Definitive hyperplasia and hyperkeratosis of the follicular epithelium
of the ear skin were seen after the topical application of fractions of Phenoclor
and Clophen (eluted from chromatographic columns with 25 percent diethyl ether in
hexane) while the fraction from Aroclor caused a minimal hyperplasia and hyper-
keratosis of the follicular epithelium. Other effects elicited by the dermal
application of the PCBs included thymus atrophy and lymphopenia as well as ele-
vated excretion of fecal coproporphyria and protoporphyria.
From the response of the back skin and the liver of the rabbit to the three
PCB mixtures, and from the response of the ear to the 25> percent diethyl ether-
hexane fractions, it was concluded that there were definite quantitative differen-
ces in toxicity, at least between the samples that were used in the above study
(Vos and Beems, Uk), and the prior studies (Vos et al., 17). The extent to which
these samples are representative of the normal commercial output has not been
established and emphasizes the difficulty in the evaluation of toxicity data of
PCBs in which the samples may differ in the amount and nature of toxic impurities.
Vos and Beems (lib) also raised the possibility that since PCB is a porphyro-
genic chemical, it is possible that the skin lesions in man due to PCB may be due
to a combination of chloracne and acquired porphyria cutanea tarda.
It is important to additionally stress the toxic nature of the polychloro-
dibenzofurans. For example, tri- and tetrachlorodibenzofuran in a single oral
dose of 0.5 -1.0 ing/Kg caused severe and often lethal liver necrosis in rabbits
(Bauer et al., W). The related compound 2,3,7,8-tetrachlorodibenzo-p-dioxin
-------
(which has been identified as a contaminant in 2,lj,5-trichlorophenol and 2,1|,5-T)
caused a lethal liver necrosis in the rabbit after a single oral dose of 0.0$ -
0.1 nig/Kg, and when applied to the ear again in a dose 10 times lower than that
found to be effective in the case of chlorinated dibenzofuran, resulted in chlor-
acne. Vos and co-workers (hh) calculated a maximum dose/egg of 0.2 ug penta-
chlorodibenzofuran (obtained from Clophen A60) that caused 100 percent embryonic
mortality when injected into the air cell of chicken eggs. (The analogous effect
was obtained with 0.05 ug hexachlorodibenzo-p-dioxin.) (Higginbotham et al., 60).
The relationship between the toxic nature of PCB and the chick edema factor l,2,3j
7,8,9-hexachlorodibenzo-p-dioxin has been described by Flick and co-workers (58).
III. EPIDEMIOLOGICAL ASPECTS
Finklea and co-workers (U6) compared both polychlorinated biphenyl and chlori-
nated hydrocarbon pesticide residues in 723 plasma samples collected from healthy
volunteers (not occupationally exposed to pesticides) who resided in Charleston
County, South Carolina. PCB residues were found in h3 percent of the samples
ranging up to 29 parts per billion. ODD and dieldrin residues were found in 8k
and 63 percent of the people, respectively, and p,p'-DDT and DDE residues were
almost universal. PCB residues were intermediate in concentration (e.g., less than
half those of p,p'-DDT and DDE but six or seven times those of o,p'-DDT, DDD and
dieldrin). Maximum levels of PCB, p,p'-DDT and DDE were similar, exceeding such
values for the other tested residues. The prevalence of PCB residues varied remark-
ably over race-residence groupings, being greatest in urban residents and rural
whites. PCB residues were rare (U.I percent) in rural blacks. Rural blacks had
atv arithmetic mean of 0.3 parts per billion, urban blacks, 1.9 parts per billion,
urban whites 2.3 parts per billion and rural whites 3-1 parts per billion, respec-
tively. Urban exposure to the PCBs was suggested to be via polluted air and con-
taminated water. (PCBs in suspended particulates have already been found).
Aspects of the determination of PCBs in the adipose of the general population
of the U.S.A. to date have been summarized by Dr. Yobs in a preliminary report in
the Human Monitoring Survey (originally established by the-Pesticides Program of
the DHEW, now Division of Pesticide Community Studies, EPA).
Table 10 depicts the preliminary summary of distribution of PCB levels in
adipose tissue of general population (as analyzed by three laboratories) in the
analysis of Human Monitoring Survey samples since April 15, 1971- A total of
688 samples were analyzed of which 235 (3h-2 percent) werje negative for PCBs
and 153 (65.8 percent) were positive for measurable amount of PCBs by TLC; of
these 229 (33-3 percent) contained trace to<1.0 parts per million and 188 (27-3
percent) contained^ 2.0 parts per million PCBs. The Aroclor formulation most
frequently encountered is 125U with Aroclor 1260 also well represented in human
tissues (Enos, h7). (Aliquots of all samples in which measurable amounts of PCBs
were found will be analyzed by mass spectroscopy at the Perrine Primate Laboratory
for future confirmation). The correlation of PCB information in this study with
age, sex, geographic distribution or diagnoses has not yet been completed.
These samples were collected in late 1968 and 1969 and the sties of the
positive samples were located in the following states: Michigan, New York,
Minnesota, California, Massachusetts, Georgia, Kentucky, Illinois, North Carolina,
South Dakota, Ohio, Louisiana, Delaware and Arkansas.
ilh
-------
TABLE 10.
DISTRIBUTION OF PCB LEVELS IN ADIPOSE OF GENERAL POPULATION AS SHOWN IN ANALYSIS
OF HUMAN MONITORING SURVEY SAMPLES SINCE APRIL 15, 1971.
(parts per million, wet tissue basis)
Michigan Florida Colorado Total
No. % flo. % No. % No. %
Samples Analyzed
PCB Levels
Negative
Trace — <1 .0 ppm
1 .0 - 2.0 ppm
>2.0 ppm
144 100 274 100 270 100 688 100
12 8.3 181 66.0* 42 15.6 235 34.2
64 44.4 44 16.0* 121 44.8 229 33.3
55 38.2 40 14.6 93 34.4 188 27.3
13 9.0 9 3.3 14 5.2 36 5.2
*
Actual decimal reading .05.
11*5
-------
Dr. G. J. Love (6l) of EPA has reported that 72 sets of specimens (blood, urine,
and hair) collected from 36 workers occupationally exposed to burning automobiles
or refuse dumps and from an equal number of controls are to be collected and
analyzed for PCB levels.
It is of interest to note the analysis of PCB in human adipose tissue. Biros
and co-workers (148) examined two human adipose tissue samples by combined GLC-mass
spectrometry and found substantial quantities of PCBs ranging from pentachloro-
biphenyl to decachlorobiphenyl and including at least Ih isomers and chlorine homo-
logs. The samples were estimated to contain 200 parts per million and 600 parts
per million total PCB., respectively, as determined by electron-capture gas chroma-
tography.
IV. STUDIES IN PROGRESS
Curley and co-workers (37) have described results in a study with Aroclor
125L to determine placental transfer, rates of excretion in milk and consequent
tissue distribution and storage levels in fetuses and weanling rats following
oral dosage to the mother daily on the 7th through the 15th day of gestation at
10 mg/Kg, respectively, by stomach tube. Table 11 lists the experimental protocol
for the above studies. This is summarized as follows:
Fetus Analysis: Samples were taken by Caesarian section on the 20th day of preg-
nancy. The mean .-concentrations of Aroclor are given for the respective dosages as
parts per million.
Controls 10 mg/Kg 50 mg/Kg
Mother 1 0 1.1,2 2.lj2
Mother 2 0 i.2ij 2.90
Mother 3 0 i.ii, 2.93
10 mg/Kg
Wt. at onset (gms) Age (days)
Mother 1 2%L\ QQ
Mother 2 265 90
Mother 3 258 90
50 mg/Kg
Mother 1 2lj2 90
Mother 2 2hh 90
Mother 3 26l 90
-------
Tissue Analysis: Samples were taken from 21-day-old male and female
weanling rats. The concentrations in the tissues for three animals are
given in ppm.
Controls
10 mg/Kq
Males
Liver <0.05
Females
<0.05
Hean X
S.E, ±
Controls
Males
Brain <0.08
Kidney <0.04
Females
<0.08
Mean X
S.E. ±
<0.04
Males
4.06
3.28
2.70
3.35
0.39
10
Males
1.96
2.28
2.24
2.16
0.10
1.52
2.42
1.14
1.69
0.38
Females
2.85
8.28
4.11
5.08
1.64
mg/Kg
Females
1.94
2.72
1.24
1.97
0.43
1.54
2.19
2.32
2.02
0.24
50 mq/Kq
Males
17.36
25.56
11.80
18.24
4.00
50
Males
10.16
5.44
7.47
7.69
1.37
7.53
6.73
6.70
6.99
0.27
Females
21.63
12.02
15.99
16.55
2.79
riq/Kq
Females
10.48
3.89
6.75
7.04
1.91
2.41
2.25
4.10
2.92
0.59
Mean X
S.E. ±
Milk Analysis: Milk samples were taken from suckling rats 11 days after
the last dose to the mother. Concentrations are given in ppm.
Controls
Range
Mean
S.E.
Ar 7-70-G4
0
0
10 mq/Kq
16.48 - 24.90
20.60
±1.59
50 mg/Kq
45.80 - 100.29
66.35
±8.36
-------
Kidney
Brain
Liver
M
F
M
F
M
F
7.38
5.44
7.53
7.76
12.80
16.13
The results of a study with Ar 1260 show consequent tissue distribution
and storage levels in weanling rats following oral dosage to the mother
daily on the 7th through 15th day of gestation at 50 mg/Kg by stomach
tube and is summarized as follows:
Note: One female and one male taken from each of 3 litters for analysis.
Tissue Sex Mean (3 animals) ±S.E.
2.56
1.41
1.04
2.54
1.72
6.75
Weights of Mothers 284, 264, and 288 gm.
Mean weight of Mothers 278 gm.
Additional residue studies completed include the following:
Experiment No. Tissue Mean ppm (4 animals) +S.E.
72.4
1.16
.95
.104
.68
.311
When compared to males at the same dosage level for an equal amount of
time, Student's t-test shows significant difference in brain and liver
storage. When these data are compared to data from male rats on the same
dosage for an equal amount of time, the Student's t-test shows significant
differences for brain and liver storage.
Ar-7-70-B12
Fat
Liver
Ki dney
Muscle
Brain
Plasma
778
9.9
5.1
1.22
6.96
1.6
-------
Experiment No. Tissue Mean ppm (3 animals) ±S.E.
Ar-7-70-B12 Fat 1022 127
Liver 14.6 0.69
Kidney 2.8 0.21
Muscle 1.2 0.11
Brain 9.3 0.57
Plasma 2.1 0.43
When these data are compared with 8 mo. study test for significant
difference shows p < 0.05 for liver only.
Experiment No. Tissue Mean ppm (3 animals) ±S.E.
Ar-7-70-B12 Fat 820 216
Liver 22.5 2.51
Kidney 4.7 .24
Muscle 2.9 .96
Brain 11.2 1.71
Plasma 3.0 0.78
When these data are compared with 10 mo. study t-test for significances
show p < 0.05 for liver and kidney.
Experiment No. Tissue Mean ppm (4 animals) ±S.E.
Ar-7-70-B10 Fat 274 48
Liver 2.2 .10
Muscle .32 .06
Kidney .60 .05
Brain 2.6 .50
Plasma .42 .06
1U9
-------
H
vn
O
TABLE 11.
EXPERIMENTS TO DATE NOT INCLUDED IN THE MANUSCRIPT, "POLYCHLORINATED BIPHENYLS: DISTRIBUTION AND
STORAGE IN BODY FLUIDS AND TISSUES OF SHERMAN RATS" - A. CURLEY, V. W. BURSE, M. E. GRIM, R. W.
JENNINGS AND R. E. LINDER. (37)
Experiment No.
Ar 7-70-B12
Ar-7-70-B12
Ar-7-70-B12
Ar-7-70-B10
Ar-8-71-B
Ar 7-70-G4
No. of Rats Sex Onset
4 (analyzed) F
3 (analyzed) F
3 (analyzed) F
4 (analyzed) F
Age at
of Experiment
30
30
30
30
(days) Wt. (Cms
224*
224*
224*
240*
) Dosage/Route
100 ppm in Diet
for 247 days
*8.1 mg/kg/day
100 ppm in Diet
for 300 days
*8.1 mg/kg/day
100 ppm in Diet
for 366 days
*8.1 mg/kg/day
20 ppm in Diet
for 280 days
*1 .6 mg/kg/day
A study to determine placental transfer, excretion in milk and consequent tissue
storage in weanling rats of Aroclor 1254 when the compound is given to the mother
rat during organogenesis.
The effect of Aroclor 1260 upon
given during organogenesis.
reproduction i
n female rats when the compound is
Average weight of group and average rate of food consumption for group.
-------
Mink reproductive studies are being carried out by Ringer, Johnson and
Hoopingarner (U9) of Michigan State University involving the initial feeding
salmon containing 15 parts per million PCB or 10 parts per million each of
Aroclor 12lj2, 125h and 1260 was fatal to mink which appear to be extremely
sensitive to PCB. Reproductive failure in ranch mink fed Coho salmon and
other Great Lakes Fish (possibly containing PCB) have been reported by Aulerich,
et al. (62).
Courtney and Chernoff (65) of the Perrine Primate Laboratory are studying
the teratogenicity of PCBs. No effects have been observed in rats (CD-I strain)
given a variety of Aroclors at a level of 200 mg/Kg. Mixtures of PCBs and DDT
have been found negative as well in the above strain of rats. Studies involving
individual isomeric chlorobiphenyls as well as commercial PCB mixtures in in-bred
strains of the rat will also be undertaken.
Wilson and Sharp (63) of the National Institute of Environmental Health
Sciences are studying aspects of the interaction of beef brain (Na++K+) ATPase
with the polychlorinated biphenyls. Enzyme activity was inhibited by $0 per
cent in the presence of Aroclor 1221 or Aroclor 125h at PCB concentrations in the
range of 8-12 parts per million at 37. Under similar conditions 2.5xlO-3>N
( 9 parts per million) DDT also inhibits the beef brain enzyme by about 50
percent. The PCB- and the DDT-sensitivity of the (Na++K+) ATPase are similar
whether the enzyme is obtained from beef brain or from fish (blue gill) brain.
On a parts per million basis a commercial preparation of 3-chlorobiphenyl is
about as inhibitory as Aroclor 1221, whereas biphenyl, k-chlorobiphenyl and
2, h-dichlorobiphenyl were less inhibitory. The technique for exposure of the
(Na++K+)ATPase to the Aroclor preparations was found to influence the degree
of the enzyme inhibitory response. Beef brain (Na++K+)ATPase responsiveness to
commercial PCBs has been demonstrated to simulate several aspects of enzyme
responsiveness to DDT.
Young (50) of the Virginia Polytechic Institute is studying PCB levels
(in feces and urine samples) of pre-adolescent girls fed diets typical of low
income families. PCB levels in paper bags, marking tags, turkey fat, heavy
fowls, eggs and poultry feeds are also being assessed and have been found in all
but two samples with concentrations ranging from 0.063 parts per million to lj.56
parts per million.
The possibility of the PCBs exhibiting immunosuppressive effects is being
further studied by,Vos (5l)- The leucopenia, the reduced number of germinal
centers in the spleens and lymph nodes, the atrophy of the cortex of the thymus
(Vos and Beems, Uh), and the atrophy of the white pulp and lymphoid foci found
in the spleens of chicks fed PCB (Vos and Koeman, Ij2) are believed by Vos to be
strong indications for an immunosuppressive effect. It -was further suggested
that the extent to which these observations are due to stress (release of gluco
corticoids) would have to be elaborated.
Flamm and Clive NIEHS (52) are studying the mutagencity of a spectrum
of Aroclors as well as individual isomers of polychlorinated biphenyls in L5178-Y
mouse lymphoma cells heterozygous at the thymidine kinase locus (TK+/~)3-
151
-------
Spalding NIEHS,(6L) is elaborating the effect of Aroclors 1221,
, 12^1, 1260 and 1268 as well as a number of isomeric poly-chlorinated
biphenyls on mouse lymphoma and DDT-resistant mouse lymphoma cells.
V. SUMMARY AND CONCLUSIONS
Despite the nearly four decades of PCB use in a broad spectrum of
applications, the increasing awareness of its environmental aspects as
well as an increasing number of recent mammalian toxicological investiga-
tions, aspects of definitive acute, sub-acute and chronic toxicity still
remain poorly known as regards man. The chemical and physical properties,
e.g., the stability,, complexity and heterogeneity of the material per se,
the difficulty of separation and analysis as well as the non- or ill-defined
nature of the material actually used or reported in many studies, have all
certainly contributed in making the evaluation of toxicity and biological
data difficult. Table 12 summarizes some biological and toxicological
effects of the PCBs.
The above review of the current status of the toxicologic and biologic
aspects of the PCBs suggests a number of future studies that hopefully
should yield additional information to enable a more definitive evaluation
of the risks involved in exposure to chlorinated biphenyls. A number of
possible future studies are outlined in Table 13-
152
-------
TABLE 12.
SOME BIOLOGICAL AND TOXICOLOGICAL EFFECTS IN THE RGB'S.
1. Acute oral LD^Q in mammals varies from approximately 2-10 gtn/kg.
(Apparent increase in mammalian toxicity with decrease in chlorine
content).
2. Generally, enzyme induction increases with increase in chlorination
of PCB's.
3. Induction of hepatic hydroxylating microsomal enzymes and increased
estrogenic activity in the rat.
4. Enlargement of the liver and vacuolar or fatty degeneration of liver
cells in rats, guinea pigs and monkeys,
5. Production of hydropericardial edema in chickens and Japanese quail.
6. Teratogenic effect in chick embryo.
7. Adverse reproductive effects in rats at levels of ca. 100 ppm in diet.
8. Possible adverse reproductive effects in mink.
9. Possible implications in aberrations in calcium metabolism and reproduction
in rinq doves.
10. Effects on hatchability in chickens, Japanese quail.
11. Skin, liver and kidney lesions in rabbits following dermal exposure.
12. Possible immunosuppressive effects in rabbits.
13. Chemical porphyrogenic effects in many species.
14. Chloracnegenic and hepatotoxic effects in man.
15. Hyperqlyceridemic effects in man.
16. Human miscarriages, still births and transplacental transmission in abnormal
pigmentation from "rice-oil disease" ("Yusho").
17. PCB residues in human adipose tissue, serum and milk.
18. Hepatoxic, chloracnegenic and porphyrogenic effects of chlorinated
dibenzofuran contaminants in several species.
19. Chloracnegenic effects of chlorinated naphthalene contaminants in man.
153
-------
TABLE 13.
POSSIBLE FUTURE STUDIES INVOLVING PCB'S, THEIR INDIVIDUAL ISOMERS AND
CONTAMINANTS.
1. Definitive studies on the mammalian distribution of the Aroclors, a
number of key common individual isomers and their metabolites and/or
degradation products in different tissues, the metabolic rate, retention
times or turnover and excretion rates.
2. Elaboration of the relative toxicity of a number of the various purified
isomers of PCB.
3. Elaboration of the effects of Aroclors and isomeric PCB's in mammalian
reproduction studies are required because of the apparent anomalous
relationship found in the pattern of chronic studies.
4. Elaboration of the teratogenicity of Aroclors and isomeric PCB's in
several mammalian species at a range of dose levels.
5. Mutagenic studies involving the Aroclors and isomeric PCB's in test
systems other than the Dominant Lethal (e.g., host mediated assay).
6. Elaboration of short-term toxicity effects on liver microsomal enzymes,
study the influence of dilantin and hexobarbital and possible synergism
and/or potentiation.
7. Study of the interaction of PCB's with other chemicals and drugs.
8. Study of the toxicity of the Aroclors and their individual isomers
for different cell systems.
9. Elaboration of mammalian tissue distribution, metabolic rate and retention
times of chlorinated dibenzofurans.
10. Liver function studies as well as cytogenic studies on workers in
a) PCB production, b) application, e.g., packing of transformers,
capacitors, c) waste disposal, and d) fishmeal processing plants.
11. Elaboration of aspects of hyperlipemia. Does it occur with low
exposures and could it aggravate arteriosclerosis? Does it
affect the pancreas, etc.?
12. Study of induced porphyria and clinical consequences.
-------
FOOTNOTES
1. Kolbye, A.C., Jr., Current Status of Toxicological Effects of PCBs (FDA),
Sept. 1 (1971); Sept. 29 (1971).
2. Burke, J. and Fitzhugh, 0. G., Suppl. No. 1 Status Kept, on the Chemistry
and Toxicology of PCBs (FDA), Dec., 1970.
3. Cook, J. W., Status Rept. on the Chemistry and Toxicology of PCBs (FDA),
June, 1970.
[4. Peakall, D. B. and Lincer, J. L., BioScience 20 (1970) 958.
5. National Swedish Environment Protection Board, PCB Conference,
Stockholm, Dec. (1970).
6. Reynolds, L. M., Residue Revs. 3k (171) 27.
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157-A
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APPENDIX G
Biological Data On PCBs In Animals Other Than Man
Table of Contents
Page
I. Toxicity 159
A. Birds
B. Insects
C. Fish and Aquatic Invertebrates
II. Physiology 162
A. Metabolism and Kinetics
B. Reproduction
III. Summary 166
IV. Conclusions 167
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APPENDIX G
Biological Data On PCBs In Animals Other Than Man
Polychlorinated biphenyls have become ubiquitous in the world ecosystem
in quantities similar to those of DDE. Their presence has caused concern and
stimulated research to evaluate their role in the biosphere.
The significance of PCBs to wild animals depends upon both their lethal
toxicity and their sublethal physiological effects. These are the subjects of
the present paper. Coordinate knowledge of level of exposure, as shown by
frequency and levels of occurrence of PCBs in the environment, is essential to
complete the understanding. These are summarized elsewhere in this report.
I. TOXICITY
Outright mortality of wild animals can affect populations, particularly
those of long-lived species. Measurements of direct toxicity are therefore
important first steps in evaluation of a chemical. Other laboratory studies
also are needed for proper interpretation of field observations. These in-
clude studies to diagnose cause of death by behavior of poisoned animals,
tissue changes, and concentrations of chemical in critical tissues.
A. BIRDS
The toxicities of different PCBs to pheasants (Phasianus colchicus ),
mallards (Anas platyrhynchos), bobwhite quail (Colinus virginianus), and
coturnix quail (Coturnix coturnix) were compared with the toxicities of DDT,
dieldrin, and other insecticides (Heath, et al ., l). Tests of six PCB mix-
tures, containing 32 to 62 percent chlorine, showed that the toxicity in-
creased with the percentage of chlorine. In general, toxicities were similar
to those of DDE. There were some differences in sensitivity of the species.
Bobwhite were most sensitive, followed in turn by pheasants, mallards, and
coturnix quail. Bobwhite were 3-h times as sensitive as coturnix. Special
tests with coturnix quail showed that the toxic effects of DDE and Aroclor
12514 were additive but not synergistic.
In other studies, Aroclor 123>b was approximately as toxic as DDE to
four species of blackbirds: grackles (Quiscalus quiscula), cowbirds
(Molothrus ater), starlings (Sturnus vulgaris), and redwings (Agelaius
phoeniceus) (Dustman, et al., 2]. Redwings were somewhat more susceptible
to DDE than to PCBs. Signs of poisoning were sluggishness with slight tre-
mors of moderate amplitude, much as with chemicals of the DDT group. Inter-
nally, livers frequently had hemorrhagic streaks or spots, and the gastro-
intestinal tract commonly contained blackish fluid, but these signs were not
sufficiently consistent for distinctive diagnosis.
Aroclor 125b was approximately 1/13 as toxic as DDT to Bengalese finches
(Lonchura striata) (Prestt, et al., 3). Tremoring and other signs were simi-
lar to those observed among blackbirds; the finches had enlarged kidneys and
some had hydropericardium.
159
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Chicks kept in batteries recently painted with an epoxy-resin paint,
(McCune et al., h). died as a result of Aroclor 12h2 in the paint. Others
fed this compound developed hydr©pericardium and enlarged livers and kidneys.
Egg injection studies showed that Aroclor 12^2 had a relatively high
toxicity (McLaughlin, et al., 5) •
Aroclor 121)8 fed to 10-day-old chicks depressed growth rates at dietary
levels of 50, 100, and l£0 parts per million (Rehfeld et al., 6). Only 2-1
of 10 chicks survived each of the three higher dosages. Growth rates were
reduced at 20, 30, and hO parts per million in a second experiment; mortality
was 16 of 30 birds at $0 parts per million dosage, h of 20 at hO parts per
million, and 1 of 30 at 30 parts per million to 5 weeks of age. Birds fed
diets containing more than 20 parts per million developed general edema;those
fed diets containing hO and 50 parts per million developed noticeably smaller
combs and wattles than normal. Liver weight increased as a percentage of body
weight, primarily as a reflection of lower body weights.
Mortality was high among White Leghorn cockerels fed a dietary dosage of
500 parts per million of Aroclor 125h from the day of hatching; the birds died
between the third and tenth week of feeding (Platonow and Funnell,- 7). At
250 parts per million birds did not die until the thirteenth week. At this
dosage, weight gain was poor, livers increased in weight relative to body
weight, combs and wattles were abnormally small, and testes were small. The
effect on combs appeared before the effect on the testes.
Polychlorinated biphenyls supplied by three different manufacturers gave
strikingly different results in toxicity tests with domestic chickens, although
all formulations contained 60 percent chlorine (Vos and Koeman, 8). The PCBs
were Phenoclor DP6, manufactured in France; Clophen A60, manufactured in Germany;
and Aroclor 1260, manufactured in the United States. Twenty-four birds fed hOO
parts per million of Phenoclor DP6 all died within 60 days; all had liver necrosis
and 18 had hydropericardium. Twenty-two of 2h birds fed Clophen at the same dosage
also died with liver necrosis and 20 with hydropericardium. However, none of
the birds fed Aroclor died; none had liver necrosis, and only three had hydro-
pericardium. Chickens fed all formulations developed atrophy of the spleen and
excess quantities of porphyrins. These different effects of the three brand-
named products were later largely explained by the identification of chlorinated
dibenzofuran and chlorinated naphthalene as contaminants in Phenoclor and Clophen
(Vos et alo 9).
In a further study with coturnix quail, porphyria again resulted from dosage
with Aroclor 1260 that was carefully tested to insure the absence of measurable
amounts of contaminants (Vos et al., 10). Males given a daily_dqse of' 50 mg/kg
of PCBs (the lowest dosage tested) developed porphyria, as did "females given 100
mg/kg, although those given 10 mg/kg or less did not. The porphyria was closely
associated with an increase of mitochondrial ALA synthetase.
160
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1. Residues in Birds Killed by PCBs. Chickens killed by PCB dosage in
the studies of(Vos and Koeman, 8) generally contained from 120 to 1420 parts
per million in the brains, but the overall range was from IjO to 700 parts per
million. Residues in livers were 120 to 2,900 parts per million.
Coturnix quail poisoned by PCBs (Phenoclor DP6) contained residues
of 3b2-1710 (av. ll£8) parts per million in the brain and 1079-8350 (av. 3280)
parts per million in the liver (Koeman, ll)., Bangales finches killed by PCBs
had residues of 70 to 697 parts per million in the livers; those sacrificed at
the end of the experiment contained 3 to 63k parts per million (Prestt,et al.,
8). Residues in brains were somewhat lower; the proportional amount in the
brain in comparison with the amount in the liver averaged higher in the birds
that died than in those that were sacrificed.
A bald eagle found sick in the field contained high residues of both
DDE and PCBs in its brain, suggesting that PCBs may have contributed to its
death. Residues of DDE in the brain were 385 parts per million, which is with-
in the lethal range for DDE (Stickel et al., 12). However, the brain also con-
tained 230 parts per million of PCBs, 6 parts per million of DDD, 2.2 parts per
million of dieldrin, and O.It parts per million of heptachlor epoxide.
B. INSECTS
The toxicity of PCBs to insects also is related to the chlorine content,
but in the reverse order to the result with birds. PCBs with lower amounts of
chlorine were more toxic to flies than PCBs with higher chlorine content, and
the toxicity of mixtures with more than 148 percent chlorine was very low
(Lichtenstein et al.;, ll). Toxicity of dieldrin and DDT was enhanced beyond
an additive effect by the addition of the lower chlorinated PCBs.
Topical applications of Aroclor 125h to a grasshopper (Clorthippus brunneus)
produced delayed mortality that occurred at the time of molt (Moriarty, lh).
C. FISH AND AQUATIC INVERTEBRATES
Shrimp (Panaeus duorarum) are sensitive to low concentrations of PCBs
(Duke,et al., 15). All individuals died as a result of a [(8-hour exposure to
flowing seawater containing 100 parts per billion of Aroclor 12514; 80 percent
died in 2li hours. These shrimp accumulated 3-9 parts per million in their tis-
sues. Shrimp exposed to 10 parts per billion did not die, but accumulated 1.3
parts per million of PCBs in their tissues.
Seventy-two percent of the juvenile shrimp died from a 20-day exposure to
5 parts per billion of Aroclor 12514 and the tissues accumulated 16 parts per
million. Crabs (Callinectes^ sapidus) were less sensitive, but accumulated an
average of 23 parts per million in a h-week exposure at 5 parts per billion and
still contained 22 parts per million after a week in clean water and 11 parts per
million after [| weeks in clean water .
The small crustacean,(Gammarus oceanicus) had a lethal threshold in 30-day
tests between 0.001 and 0.01 parts per billion in colloidal solution and between
161
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0.01 and 0.1 parts per billion in emulsions of Aroclor 1251 solubilized in
Corexit 766k (a commercial nonionic surfactant preparation) in seawater
(Wildish^ 16). Gammarus that died had severely necrosed branchiae, and
some animals exposed to as little as 0.001 parts per billion developed a
less extensive sublethal necrosis. Moulting or freshly moulted animals were
particularly vulnerable.
Shell growth of oysters stopped completely in a 96-hour exposure to
100 parts per billion of PCBs . Shell growth was reduced by 10 percent in
exposure to 10 parts per billion and the oysters accumulated 33 parts per
million of PCBs in their tissues (Duke, et al., 15).
Pinfish (Lagodon rhomboides ) survived exposure to 10 or 100 parts per
billion of Aroclor 125k for Ii8 hours, but those exposed to 100 parts per
billion accumulated 17 parts per million (Duke, et al. ,
In further studies at the same laboratory, pinfish and spot (Leiostomus
xanthurus ) died when exposed for Ih-hS days to 5 parts per billion of Aroclor
125li, but spot appeared unaffected by exposure to 1 part per billion for periods
up to 56 days (Hansen, et al., 17). Onset of death in both species exposed to
5 parts per billion was delayed. Pinfish developed fungus-like lesions on the
body, with some hemorrhaging. Spot usually ceased feeding, became emaciated,
and developed ragged fins and lesions. Some fish that survived exposure to 5
parts per billion Aroclor 125k became diseased and died even though they were
placed in flowing water free from PCBs.
Rainbow trout (Salmo gairdneri) are very sensitive to the terphenyls
(Guthrie and Acres, 18 Y. Fifty percent of the fish exposed to Santowax CM*
+ 30 percent high boilers at concentrations of 10 parts per billion or greater
died in L>8 hours or less under normal oxygen conditions. With reduced oxygen,
50 percent died in less than 2 hours even at a concentration of 2 parts per
billion (the lowest tested). The fish became hyperactive in less than 1/2
hour in water containing 25 parts per billion or more. Within 1 to 5 hours,
gills reddened, swimming slowed, and balance and avoidance reactions were
altered. Less than 5 percent of the fish recovered after showing these signs.
HB-liO# was less toxic, and less than 25 percent of the fish died within h8
hours .
II. PHYSIOLOGY
The effects of PCBs on reproduction and other physiological processes of
wild animals are apt ultimately to have the most serious impact on the popula-
tions. Yet these effects are the most difficult to evaluate. Pertinent data
are summarized here, with the exception of data for laboratory mammals, which
are included in other sections of this report.
A. METABOLISM AND KINETICS
In Swedish waters, lower organisms such as mussels and fish contained a
greater preponderance of PCBs with lower chlorination than did birds, which
suggested that the compounds with fewer chlorines were metabolized or excreted
* Monsanto Chemical Company trade name. Santowax is a mixture of ortho-, meta-,
and para- terphenyls. HB-ljO is a mixture of hydroterphenyls and terphenyls. High
boilers are tar-like decomposition products produced as a result of the exposure
of terphenyls to a high radiation field.
162
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faster than those with more chlorines, so that the latter were subject to
greater increase in the food chain (Jensen, et al. , 19).
In two simple food chains, fish to eagles (Haliaeetus albicilla) and
fish and mussels (Mytilus edulis) to seals (Phoca vitulina and Pusa hispida),
concentrations increased hundreds to thousands of times from prey to predator
(Jensen, et al.^ 19). Fish contained hundredths to tenths of parts per million;
fresh mussels contained hundredths of parts per million; seal blubber contained
5-21 parts per million; and the muscle of the white-tailed eagle contained 150-
2liO parts per million.
In Great Britain, birds that feed on birds or mammals contained the highest
concentrations of PCBs, those that have a mixed diet contained the next highest,
and those that feed on insects had the lowest (Prestt, et al., 3). The fish-
eating herons from the southeast of England contained higher residues of PCBs
than birds of any other area.
Many species of California birds contained hundredths to tenths of parts
per million of PCBs; peregrines (Falco peregrinus) contained greater amounts,
one as high as 98 parts per million in muscle (Risebrough, et al,, 20), while
fish in the same area contained only thousandths of parts per million.
Residues of PCBs in the industrially polluted Escambia Bay increased in
the expected order. Water contained a maximum of 275 parts per billion, and
sediment a maximum of 1)86 parts per million. Oysters (Crassostrea virginica)
contained 2-3 parts per million, shrimp (Penaeus duorarum) 1.5- 2. IT parts per
million, blue crabs (Callinectes sapidus) 1-7 parts per million, and pinfish
6-12 parts per million (Duke, et al.,
Subsequent samplings from three stations in the Bay showed little change
in concentrations of PCBs in sediments even after 9 months (Nimmo, et al., 21).
Experiments were then undertaken that showed that shrimps (Penaeus duorarum)
and fiddler crabs (Uca minax) could accumulate Aroclor 125h from the sediments.
Relationships between concentration of PCBs in sediment and concentration in
crabs and -shrimps were variable. The maximum accumulation was from sandy silt
containing 6l parts per million (dry weight) of Aroclor 1251; fiddler crabs
accumulated 80 parts per million (wet weight) in their bodies; shrimp accumula-
ted 2l»0 parts per million (wet weight) in the hepatopancreas . Some PCBs
were present in the water and a portion of the accumulation could have been
from that source. The ratio of individual PCB isomers maintained integrity in
the sediments and tissues of test animals throughout the investigation, indica-
ting no pronounced metabolic changes of the PCBs .
Spot (Leiostomus xanthurus ) exposed to 1 part per billion of Aroclor 125b
for 56 days attained maximum concentrations in lh-28 days, although absolute
amounts continued to increase as the fish grew (Hansen, et al.. 1?). Maximum
concentration in whole spot was 37,000 times that in the test water. These
results were very similar to those for DDT reported earlier from the same
laboratory. The PCBs were lost slowly from the tissues of spot after they were
placed in clean flowing water. After 8*4 days of flushing, the concentration had
dropped 73 percent and the absolute amount had dropped 61 percent. Isomers of
Aroclor 1251, with the exception of one peak, maintained their integrity in spot.
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Marine diatoms (Cylindrotheca closterium) exposed to Aroclor I_2k2 at
0.01 and 0.1 part per million in culture flasks absorbed the chemical to a
concentration of h-7 and 109.2 parts per million, b70 and 1,100 times the
concentrations in the surrounding medium (Keil, et al.^'22). The higher
concentration (0.1 part per million) sharply inhibited growth as indicated
by harvest weights and cell counts and reduced RNA synthesis and the chlorophyll
index but had no effect on DNA levels. No such effects were produced by the
0.01 part per million concentration. Some early eluting PCB materials not com-
mon to the known mixture of Aroclor 12I|2 were isolated from the diatoms, suggest-
ing possible metabolism of the Aroclor.
A species of salt-water diatom (Thalassiosira pseudonana) grew at a signi-
ficantly reduced rate when exposed to Aroclor 125k at concentrations of 25j 50,
and 100 parts per billion in the culture medium (Mosser, et al., 23). Survival
was reduced by exposure to 50 and 100 parts per billion. A second species
(Skeletonema costaturn) was more sensitive and grew somewhat more poorly when
exposed to 10 parts per billion. Both species were more sensitive to PCBs than
to an equivalent amount of DDT. By contrast, a marine green alga and two species
of freshwater algae were not inhibited by these or higher concentrations of PCBs.
The small crustacean,(Gammarus pceanicua )tappeared to absorb Aroclor 125h
across the general integument (Wildish and Zitko.? 2^). Uptake was not altered
by removal of branchiae epi-flora and by removal of epi-fauna, or by the stage
of intermoult. Rate of uptake was greater at higher concentrations and declined
after a few hours. Dead Gammarus absorbed significantly smaller amounts of PCBs
from the seawater than did the living animals.
PCBs inhibited ATPases in bluegills (Lepomis macrochirus). Aroclor 125h was
the most effective inhibitor, followed by Aroclor 1221 (Yap, et al., 25). Aroclor
1268 and 5^60 showed less pronounced effects. Tissues (brain, kidney, liver, and
muscle) also differed; muscle ATPase showed the greatest sensitivity, with a
response similar to that observed for DDT.
In the Netherlands, the PCBs of lower chlorination were more common in fish
(Leuciscus rutilus) than in sea birds, and it was concluded that compounds with
fewer chlorines probably were metabolized or excreted relatively rapidly (Koeman,
et al., 26). This hypothesis was confirmed in an experiment with Japanese quail;
the gas chromatographic pattern of PCBs in the quail tissues was considerably
altered from that of the fed material, and many of the peaks representing lower
chlorinated compounds disappeared. There was a similar difference in pattern
of the PCB compounds present in the egg of a mallard duck and the pattern of the
Aroclor 1251 that the duck had eaten (Heath, lj.
PCBs increased the breakdown of estradiol in domestic pigeons (Risebrough,
et al.} 20) and kestrels (Falco sparverious) (Lincer and Peakal]., 27). demon-
strating their capability to induce microsomal enzyme activity. The PCBs were
given by injection (pigeons) or ingestion (kestrels) of relatively high dosages;
the birds were sacrificed and in vitro laboratory studies were made of the homog-
enized livers.
I6h
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Mallard ducklings demonstrated the possibility of interacting effects
between PCBs and disease organisms (Friend and Trainer, 28). Thirty- five
to hh percent of the 10-day-old ducklings exposed for 10 days to a dietary
dosage of 25, 50, or 100 parts per million of Aroclor 125>li died upon sub-
sequent exposure to duck hepatitis virus in contrast to only lli percent of
the birds exposed only to the virus.
Swedish robins (Erithacus rubecula) given 5 micrograms of Clophen A50,
for 11-13 days showed a greater migratory restlessness than controls (Ulfstrand
and So"dergren, 29).
Pheasant hens absorbed 9h percent of the Aroclor 125k given as a single
capsule dose, a very efficient entry of this chemical into the system (Dahlgren,
et al.} 30). Residues in muscle declined 82 percent in 28 days after dosage.
Residue were excreted in both eggs and f eces .
Residues in the milk of cattle inadvertently exposed to PCBs declined at
the rate of 1.3 percent per day when uncontaminated feed was restored (Fries,
et al., 31). The rate of loss of DDE residues was identical. PCBs in milk fat
decreased from 12.6 parts per million to 5-8 parts per million in about 3 weeks
and to 2.1 parts per million in about h months.
A cow given 10 mg/kg of Aroclor 125h in a single dose released an average
of 3'9 parts per million into the whole milk during the next h days' milking.
A dosage of 100 mg/kg produced 36 parts per million in the milk of another cow
(Platonow, et al., 32). The gas chromatographic pattern of the Aroclors in
the milk was very similar to that of the fed compound.
B. REPRODUCTION
Pheasants given a capsule dose of 50 mg of Aroclor 1251) weekly for 17
weeks produced fewer eggs than controls , and a higher percentage of chicks
pipped the shell but did not hatch (Dahlgren and Linder, 33). Chicks that
hatched weighed less and survived more poorly than controls. Eggshell thick-
ness was not affected. In behavioral tests of the offspring on a visual cliff,
more of the chicks from the dosed parents made the undesirable choice of jumping
to the deep side, or made no choice, in the 5-minute test period. None of these
effects occurred among the groups whose female parents were dosed with 12.5 mg.
Mallards fed a dietary dosage of 25 parts per million of PCBs from about
11 weeks before their first breeding season and through their second year laid
eggs with shells of normal thickness (Heath, et al,, 1). The number of eggs
laid, hatchability, and survival of young did not differ significantly from the
untreated controls. In another test, mallard ducks fed 10 or 500 parts per
million of Aroclor 125h in the diet for about 5 weeks laid eggs with normally
thick shells. Bobwhite quail fed diets containing 50 parts per million of PCBs,
or 30 parts per million of DDE, or a combination of 25 parts per million of
PCBs plus 15 parts per million of DDE for about 11 weeks before their first
breeding season reproduced as well as controls.
Ring doves (Streptopelia risoria) fed 10 parts per million of Aroclor
for 6 months laid eggs no lighter than those laid by control birds. (Peakall,
3i4). Fourteen birds fed 10 parts per million of PCBs before and after dosage
and nine birds injected intraperitoneally with 160 mg/kg 1-b days before egg
laying confirmed the lack of effect of PCBs on shell weight.
165
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Chickens fed Aroclor 12^2 at 10 parts per million or 100 parts per million
and Aroclor 1251 at 100 parts per million laid fewer eggs, hatched fewer chicks,
and laid eggs with thinner shells than controls in tests made for the Monsanto
Chemical Company by the Industrial Bio-Test Laboratories. Those fed Aroclor
12lj2 at 1 part per million, Aroclor 12£lj at 1 part per million or 10 parts per
million, or Aroclor 1260 at 1 part per million, 10 parts per million, or 100
parts per million did not differ significantly from controls.
The studies with chickens and with ducks differed in dosage levels and in
the type of PCBs employed, so that the differences cannot necessarily be ascribed
to the difference in species. Further tests with ducks and with other species
are needed in order to understand the potential for PCBs to affect reproduction
of wild birds.
In recent studies at the Patuxent Wildlife Research Center, a statistical
evaluation of the role that different chemicals may play in thinning the shells
of brown pelicans in the field has shown that DDE residues correlate much better
with shell thinning than do residues of dieldrin or PCBs (Blus, et al.., 35;
Anderson, et al. } 36) reported similar results from studies of shell thinning
and residue content of the eggs of cormorants and white pelicans.
Reproductive failure occurred among ranch mink that were fed fish from the
Great Lakes and the Miramichi (Gilbert, 37 ; Aulerich, et al., 38). . Such
effects could not be produced experimentally by dosages of DDT or its metabolites
in levels far in excess of those present in the fish (Aulerich, et a.1., 38).
This led to the belief that other contaminants must be responsible, and tests
have been initiated with PCBs as a possible candidate.
III. SUMMARY
Polychlorinated biphenyls have become ubiquitous in the world ecosystem
in quantities similar to those of DDE.
Experimental studies have shown that PCBs have a toxicity to mallards,
pheasants, bobwhite quail, coturnix quail, red-winged blackbirds, starlings,
cowbirds, and grackles that is of the same order as the toxicity of DDE to
these species. Overt signs of poisoning also are similar to those caused by
compounds of the DDT group. Toxic effects of DDE and Aroclor 1251j to coturnix
chicks were additive, but not synergistic.
PCBs containing higher percentages of chlorine are more toxic to birds
than those containing lower percentages. PCBs of foreign manufacture contained
contaminants to an extent that greatly increased their toxicity.
Residues of PCBs in the brains of birds killed by these compounds measure
in the hundreds of parts per million. PCBs may have contributed to mortality of
some birds in the field.
Toxicity to insects of PCBs of different degrees of chlorination is the
reverse of the pattern in birds: the lower chlorinations are more toxic to
insects. PCBs enhanced the toxicity of dieldrin and DDT to insects.
166
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Shrimp are very sensitive to PCBs and most will die as a result of
20-day exposure to a concentration of 5> parts per billion. PCBs also inhibit
shell growth of oysters. Crabs are less sensitive; all accumulate residues
to many times the concentrations in the water, and a test with crabs showed
that they lost the residues very slowly.
Growth of certain species of marine diatoms was experimentally inhibited
by PCBs, but algae were not affected.
The small marine crustacean, Gammarus , is sensitive to PCBs in concentra-
tions of thousandths to tenths of a part per billion.
Exposure to 5 parts per billion of Aroclor 125^ caused mortality of two
species of fish in Ilj-l45> days. Onset of death was delayed and was accompanied
by fungus-like lesions.
Rainbow trout were quickly killed by polychlorinated terphenyls at 10
parts per billion under normal oxygen conditions and at 2 parts per billion
with reduced oxygen.
Metabolic changes of PCBs have been suggested by environmental observa-
tions of different isomeric patterns in animals of different trophic levels.
Quantitative differences also are pronounced, with magnifications of hundreds
to thousands of times.
Laboratory studies have shown no metabolic changes of PCBs by crabs and
shrimps, minimal changes by fish, and pronounced changes by birds.
PCBs induce microsomal enzyme activity in birds. Exposure to PCBs in-
creased the susceptibility of mallard ducklings to duck hepatitis virus.
Offspring of pheasants whose parents received high dosages of PCBs made
poor choices in visual cliff tests. Egg production and hatching after pipping
also were affected. Migratory restlessness was increased in English robins ex-
posed to PCBs .
Long-term studies of the reproductive effects of Aroclor 12^h on mallards
and bobwhite quail and of Aroclor 125k plus DDE on quail showed no significant
differences from controls. In studies of chickens, however, egg production and
hatchability were impaired by high doses of Aroclor 125>li and by low doses of
Aroclor I2k2.
Statistical evaluations of the role that different chemicals may play in
thinning eggshells of brown pelicans showed that DDE residues correlate better
with shell thinning than do residues of dieldrin or PCBs, confirming observa-
tions with cormorants and white pelicans.
IV. CONCLUSIONS
PCBs are man-made biologically active substances that are dispersed
throughout the environment and stored in the tissues of animals. They are
lethally toxic to fish and aquatic invertebrates in concentrations measured
-------
in parts per billion or less. They are metabolized and excreted very slowly
by these organisms.
They are only moderately toxic to birds and mammals and the lethal levels
are similar to those of DDE. In sublethal exposure, they are physiologically
active and induce enzyme activity. Effects on reproduction have been shown
for chickens but not for ducks, quail, or doves, and for rabbits only at high
dosages.
Full evaluation of their actual or potential effects in the environment
is hampered by the complex nature of the mixtures that compose them, and by
the inclusion of contaminants in these mixtures. Experimental studies have
been conducted with the unaltered products, as sold, and the results may not
properly reflect the effects of the components as they exist in the environ-
ment.
The evidence available, however, indicates that PCBs must be viewed as
potential problems. The difficulties of attaining a proper evaluation in any
reasonable length of time suggest that the least costly course would be to
take all measures possible to prevent their escape into the environment.
168
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FOOTNOTES
1. Heath, R. G., J. W. Spann, J. F. Kreitzer, and C. Vance.
1970. Effects of polychlorinated biphenyls on birds. Presented
at and to be published in proceedings of l$th International
Ornithological Congress. The Hague, 1970.
2. Dustman, E. H., L. F. Stickel, L. J. Blus, W. L. Reichel, and S. N.
Wiemeyer.
1971. The occurrence and significance of polychlorinated biphenyls
in the environment. Transactions of the 36th North American
Wildlife and Natural Resources Conference: 118-131.
3- Prestt, Ian, D. J. Jefferies, and N. W. Moore.
1970. Polychlorinated biphenyls in wild birds in Britain and
their avian toxicity. Environmental Pollution 1:3-26.
h- McCune, E. L., J. E. Savage, and B. L. O'Dell.
1962. Hydropericardium and ascites in chicks fed a chlorinated
hydrocarbon. Poultry Science 141:295-299.
5- Mclaughlin, Joseph, Jr., Jean-Pierre Marliac, M. Jacqueline Verrett,
Mary K. Mutchler, and 0. Garth Fitzhugh.
1963. The injection of chemicals into the yolk sac of fertile
eggs prior to incubation as a toxicity test. Toxicology
and Applied Pharmacology 5:760-771.
6. Rehfeld, Betty_M., R. L. Bradley, Jr., and M. L. Sunde.
1971. Toxicity studies on polychlorinated biphenyls in the chick.
Poultry Science 50(ii): 1090-1096.
7. Platono-w, N. S., and H. S. Funnell.
1971. Anti-androgenic-like effect of polychlorinated biphenyls
in cockerels. Veterinary Record 88(lj) :109-110.
8. Vos, J. G.j and J. H. Koeman.
1970. Comparative toxicologic study with polychlorinated
biphenyls in chickens with special reference to porphyria,
edema formation, liver necrosis, and tissue residues.
Toxicology and Applied Pharmacology 17:656-668.
9- Vos, J. G., J. H. Koemarij H. L. van der Maas, M. C. ten Noever de Brauw,
and R. H. de Vos.
1970. Identification and taxicological evaluation of chlorinated
dibenzofuran and chlorinated naphthalene in two commercial
polychlorinated biphenyls. Food and Cosmetic Toxicoloev
8:625-633-
169
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10. Vos, J. G., J. J. T. W. A. Strik, Catberina W. M. van Holsteyn, and
J. H. Fennings.
1971. Polychlorinated biphenyls as inducers of hepatic porpbyria
in Japanese quail, with special reference to 8 -aminole-
vulinic acid synthetase activity, fluorescence, and residues
in the liver. Toxicology and Applied Pharmacology 20(2)232-2ljO.
11. Koeman, Jan Hein.
1971. The occurrence and toxicological implications of some
chlorinated hydrocarbons in the Dutch coastal area in the
period from 1965 to 1970. Doctoral Dissertation, University
of Utrecht. 139 p.
12. Stickel, William H., Lucille F. Stickel, and Francis B. Coon.
1970. DDE and ODD residues correlated with mortality of experi-
mental birds, pp. 287-29U in "Pesticides Symposia,"
edited by W. B. Deichmann, Halos & Associates, Miami.
13- Lichtenstein, E. P., K. R. Schulz, T. W. Fuhremann, and T. T. Liang.
1969. Biological interaction between plasticizers and insecticides.
Journal of economic Entomology 62:761-765-
lh- Moriarty, F.
1969. The effects of polychlorobiphenyls on Chorttiippus brunneus
(SaltatoriarAcrididae). Entomologia Exp. and Appl. 12:206-210.
15- Duke, T. W., J. I. Lowe, and A. J. Wilson, Jr.
1970. A ploychlorinated biphenyl (Aroclor 125U) in the water,
sediment, and biota of Escambia Bay, Florida. Bulletin of
Environmental Contamination and Toxicology 5=171-180.
16. Wildish, D. J.
1970. The toxicity of polychlorinated biphenyls (PCS) in sea water
to Gammarus oceanicus. Bulletin of Environmental Contamina-
tion and Toxicology 5(3):202-20h.
17- Hansen, D. J., P. R. Parrish, J. I. Lowe, A. J. Wilson, Jr., and
P. D. Wilson.
1971. Chronic toxicity, uptake, and retention of Aroclor 125U in
tido estuarine fishes. Bulletin of Environmental Contamination
and Toxicology 6(2}: 113-119-
18. Guthrie, J. E., and 0. E. Acres.
1970. Toxicity to fish of two organic reactor coolants. Bulletin
of Environmental Contamination and Toxicology 5(2) :lii5-l5l.
19- Jensen, S., A. G. Johnels, M. Olsson, and G. Otterlind.
1969. DDT and PCB in marine animals from Swedish waters. Nature
22^:2^7-250.
20. Risebrough, R. W;., P. Reiche, D. B. Peakall, S. G, Herman, and
M. N. Kirven.
1968. Polychlorinated biphenyls in the global ecosystem. Nature
220:1098-1102.
170
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21. Nimmo, D. R. , P. D. Wilson, R. R. Blackman, and A. J. Wilson, Jr.
1971. Polychlorinated biphenyl absorbed from sediments by fiddler
crabs and pink shrimp. Nature 231:50-52.
22. Keil, Julian E., Lamar E. Priester, and Samuel H. Sandifer.
1971. Polychlorinated biphenyl (Aroclor 12U2): effects of uptake
on growth, nucleic acids, and chlorophyll of a marine diatom.
Bulletin of Environmental Contamination and Toxicology
6(2):156-159.
23. Mosser, Jerry L., Nicholas S. Fisher, Tzu-Chiu Teng, and Charles F.
Wurster.
1972. Polychlorinated biphenyls: toxicity to certain phytoplankters.
Science 175(1018):191-192.
2h. Wildish, D. J., and V. Zitko.
1971. Uptake of polychlorinated biphenyls from sea water by
Gammarus oceanicus. Marine Biology 9(3)-213-218.
25. Yap, H. H., D. Desaiah, L. K. Cutkomp, and R. B. Koch.
1971. The sensitivity of fish ATPases to polychlorinated biphenyls.
Nature (In press).
26. Koeman, J. H., M. C. ten Noever de Brauw, and R. H. de Vos.
1969. Chlorinated biphenyls in fish, mussels and birds from the
River Rhine and the Netherlands coastal area. Nature 221:
1126-1128.
27. Lincer, Jeffrey L., and David B. Peakall.
1970. Metabolic effects of polychlorinated biphenyls in the
American kestrel. Nature 228 :783-781j.
28. Friend, Milton, and Daniel 0. Trainer.
1970. Polychlorinated biphenyl: interaction with duck hepatitis
virus. Science 170:13lU-13l6.
29. Ulfstrand, S., and A. Sodergren.
1971. Effect of PCB on nocturnal activity in caged robins,
Erithacus rubecula L. Nature 231:^67-1(68.
30. Dahlgren, Robert B., Yvonne A. Greichus, and Raymond L. lander.
1971. Storage and excretion of polychlorinated biphenyls in
the pheasant. Journal of Wildlife Management 35(U):823-828.
31. Fries, G. F., G. S. Marrow, Jr., and C. H. Gordon.
1971. Similarity in behavior of DDE and polychlorinated biphenyl
(Aroclor 125ii) residues in an environmentally contaminated
herd of dairy cows. U. S. Department of Agriculture,
Agricultural Research Service Paper 130.Presented at the
Annual Meeting of the American Dairy Science Association,
East Lansing, Michigan, June 1971.
171
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32. Platonow, N. S., H. S. Funnell, D. H. Bullock, D. R. Arnott, P. W.
Saschenbrecker , and D. G. Grieve.
1971- Fate of polychlorinated biphenyls in dairy products
processed from the milk of exposed cows. Journal of
Dairy Science 5U(9) :1305-1308 .
33- Dahlgren, Robert B., and Raymond L. Linder.
1971. Effects polychlorinated biphenyls on pheasant repro-
duction, behavior, and survival. Journal of Wildlife"
Management 35(2) : 315-319.
3h- Peakall, David B.
1971- Effect of polychlorinated biphenyls (PCBs) on the egg-
shells of ring doves. Bulletin of Environmental Con-
tamination and Toxicology 6(2) : 100- 101.
35- Blus, Lawrence J., Robert G. Heath, Charles D. Gish, Andre A. Belisle,
and Richard M. Erouty.
1971- Eggshell thinning in the bro-wn pelican: implication of DDE.
BioScience 2l(2l/) :1213-12l5.
36. Anderson, Daniel W. , Joseph J. Hickey, Robert W. Risebrough, Donald F.
Hughes, and Robert E. Christensen.
1969. Significance of chlorinated hydrocarbon residues to
breeding pelicans and cormorants. Canadian Field-
Naturalist 83:91-112.
37- Gilbert, Frederick F.
1969. Toxicity to fish of two organic reactor coolants.
Bulletin of Environmental Contamination and Toxicology
38. Aulerich, R. J., R. K. Riger, H. L. Seagran, and W. G. Youatt.
1971. Effects of feeding coho salmon and other Great Lakes
fish on mink reproduction. Canadian Journal of Zoology
1*9(5) :
172
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APPENDIX H
Regulatory Action on PCBs
Table of Contents
Page
I. Existing Regulatory Authority 17lj
A. Federal Insecticide, Fungicide, and Rodenticide Act
B. Federal Water Pollution Control Act
C. The Refuse Act of 1899 (33 U.S.C. U07)
D. The Clean Air Act (U2 U.S.C0 l8$7 et seq)
E. The Egg, Meat, and Poultry Acts
F. The Occupational, etc...
Cr. Act to Regulate Transportation of Explosives and
Other Dangerous Articles (18 U.S.C. 831-83$)
II. Standards, Tolerances, or Guidelines Established 177
III. Application of Regulatory Authorities 179
IV. Future Actions and Needs 180
Tables
1. FDA Proposed Temporary Tolerances for PCB Residues 178
173
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APPENDIX H
Regulatory Actions on PCBs
I. EXISTING REGULATORY AUTHORITY
At least ten Federal laws are potentially relevant for the regulation
of PCBs. However, not all of them have actually been utilized to deal with
the PCB problem. Federal Food, Drug, and Cosmetic Act (21 U.S.C. 301 et.seq.)
Section i*02 of the Federal Food, Drug, and Cosmetic Act (FDC Act) de-
fines an "adulterated food" as a food which (among other criteria):
1. Contains any poisonous or deleterious substance which may render
it injurious to health; or
2. Contains any food additive unless the use of the additive con-
forms to exemptions or regulations issued by the Food and Drug Administration
(FDA). FDA has applied both of these criteria to PCBs, depending upon
the circumstances under which the PCB entered the food.
The FDC Act prohibits the introduction of adulterated food in interstate
commerce; prohibits the adulteration of food while moving in interstate
commerce; and prohibits the receipt of an adulterated food in interstate
commerce and subsequent delivery of it for sale or otherwise when the
initial recipient is aware that the food is adulterated. The Act also
authorizes FDA to seize any adulterated food products -which have entered
interstate commerce or which become adulterated while held for sale after
receipt in interstate commerce.
The FDA enforces the FDC Act by various means including inspections of
food establishments (other than meat, poultry, and egg breaking plants)
to determine whether the provisions of the Act are being violated. These
inspections include the collection and analysis of food samples. Some
of the samples are of a routine surveillance nature to determine the
presence of adulterants such as pesticides which exceed tolerance levels
and other contaminants such as mercury, lead, cadmium, harmful bacteria,
natural poisons, etc. However, the actual number of routine surveillance
samples taken is small, and effective enforcement relies heavily on informa-
tion on the known or suspected existence of specific instances of food
adulteration.
A. FEDERAL INSECTICIDE, FUNGICIDE, AND RODENTICIDE ACT (7 U.S.C. 135-135k)
Under the Federal Insecticide, Fungicide, and Rodenticide Act
all pesticides (referred to in the act as "economic poisons")
1714
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shipped in interstate commerce must be registered with the EPA. EPA
can refuse to register a product if it will cause injury to man or the
environment if used according to the label. The registration of a pro--
duct can be suspended or cancelled if it is found to no longer meet the
criteria for registration.
On October 29, 1970, the Pesticides Regulation Division (then in
the Department of Agriculture; now in EPA) issued a notice (PR Notice
70-25) to all pesticide manufacturers, formulators, and distributors.
The notice stated that, "Formulators and manufacturers of economic poisons
containing polychlorinated biphenyls and polychlorinated terphenyls
should change their formulations to eliminate such chemicals either as
active or inactive ingredients. It is believed that a period of six
months is a reasonable period of time within which to affect such formula
changes." Assuming that the notice has been complied with, there should
be no pesticides which currently contain PCBs.
B. FEDERAL WATER POLLUTION CONTROL ACT (33 U.S.C. h66 et.seq.)
The Federal Water Pollution Control Act (FWPC Act) authorizes the
Administrator of EPA to enforce State water quality standards established
by the States and approved by the Federal Government if the State is not
adequately enforcing the standards. No States have established water
quality standards relating specifically to PCBs. Thus the water quality
standards part of the FWPC Act is not a useful tool for dealing with the
PCB problem.
Section 12 of the FWPC Act applies primarily to accidential discharges
of hazardous polluting substances. It requires the immediate reporting
to EPA or the Coast Guard of any discharge of a hazardous substance from
a vessel or an onshore or off-shore facility. The discharger is responsible
for making the report and for clean-up, but EPA is authorized to remove or
arrange for the removal of the hazardous substance if the discharger is
unable or unwilling to do so. PCBs are being designated as hazardous sub-
stances under section 12, and the authority contained in the section could
be used if an accidental spill of PCBs into water should occur.
C. THE REFUSE ACT OF 1899 (33 U.S.C. U07)
Another legal authority for controlling water pollution is section 13
of the 1899 Refuse Act which forbids discharge of any wastes (other than
municipal wastes) into navigable waters without a permit, issued by the
Army Corps of Engineers, which can lijnit the discharge of substances into
water. EPA and the Justice Department are prepared to use the Refuse Act
to prevent PCB discharges.
D. THE CLEAN AIR ACT (U2 U.S.C. 185? et. seq.)
The general authorities contained in the Clean Air Act are not, for the
most part, applicable to PCBs because PCBs are not generally .emitted into
the air in the normal operations of a municipal or industrial facility.
PCBs may become air contaminants through the burning of refuse, but such
emissions usually could be controlled only by preventing the substance
from initially getting into the refuse.
175
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Section 112 of the Clean Air Act authorises the establishment of
national emission standards for hazardous air pollutants. However, it
is unlikely that section 112 would be invoked to deal with PCBs for the
same reasons that the other Clean Air Act authorities are generally not
applicable.
E. THE EGG, MEAT, AND POULTRY ACTS
The Consumer and Marketing Service of the U.S. Department of Agriculture
(USDA) administers three acts relevant to the PCS problem: The Egg Pro-
ducts Inspection Act (P0L. 91-597); the Wholesome Poultry Products Act
(P.L. 90-U92); and the Wholesome Meat Act (P.L. 90-201).
These authorities apply to meat, egg, or poultry products from the time
they reach the processing plant until they are purchased by the consumer.
Once they leave the plant, they also fall under the legal authority of the
FDC Act as do all foods. USDA routinely checks meat, poultry, and egg
processing plants, but relies primarily on local jurisdictions for inspection
at retail outlets.
The egg, meat, and poultry acts essentially define a product as adulterated
if it contains any substance in an amount i^hich is judged deleterious to
health. USDA. follows guidelines established by FDA under the FDC Act for
determining what amounts of a particular substance are deleterious. USDA
can seize adulterated products or prevent them from being distributed.
F. THE OCCUPATIONAL SAFETY & HEALTH ACT (29 U.S.C. 65l-6?8)
Chemical hazards in the workplace are regulated under the Occupational
Safety and Health Act. The Secretary of Labor, in cooperation with the
Secretary of Health, Education, and Welfare^ is authorized to set and
enforce occupational safety and health standards applicable to businesses
affecting interstate commerce.
No specific standard has been set for occupational exposure to PCBs.
However, the Department of Labor has set exposure limits for comparable
substances, and it could enforce limits on PCBs by applying limits set
for compounds such as chlorodiphenyl. The standard for chlorodiphenyl
is Img per cubic meter - 8 hour average exposure.
G0 ACT TO REGULATE TRANSPORTATION OF EXPLOSIVES AND OTHER DANGEROUS
ARTICLES (18 U.S.C. 831-835)
The Department of Transportation (DOT) regulates the transport of
hazardous substances under the Act to Regulate Transportation of Explosives
and Other Dangerous Articles. The Act authorises DOT to promulgate regula-
tions for the safe transportation of such materials.
DOT has issued tentative test protocols for classifying substances
according to their acute toxicity, but these have not yet gone into effect.
Responsibility for insuring that standards are complied with rests initially
with the manufacturer or shipper.
176
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II. STANDARDS, TOLERANCES, OR GUIDELINES ESTABLISHED
The most important limits which have been established for PCBs have
been those established by FDA to deal with particular instances of food
or feed contamination.
Standards or, more accurately, tolerances for products such as for
PGBs may be established under Section U06 or Section h09 of the Food,
Drug, and Cosmetic Act, which require a finding that the substance is
required in the production of the food or cannot be avoided by good
manufacturing practices or a showing of safety and a need for use. No
permanent tolerances for PCBs have been established, since all the safety
data necessary and the need for use to support such tolerances are not
available at this time. In the absence of tolerances, the Food and Drug
Administration, in order to respond to accidental contamination, has set
interim guidelines for levels of PCB in some foods at which it will take
action under the Food, Drug, and Cosmetic Act. It is now proposing to
establish temporary tolerances for permitting unavoidable PCBs in several
categories of food.
FDA has taken action to remove from the market shell eggs containing
more than 0.05 parts per million PCBs and feeds containing more than
0.5 parts per million PCB where the PCBs present appears to be from
accidental contamination of feed. The U.S. Department of Agriculture has
also t.j.ken action to remove poultry from the market containing 5.0 parts
per million PCBG where such contamination was the result of accidental
contamination of feed, fed to poultry. The action level of 5 parts per
million (whole tissue basis) was established in 1971 by FDA. This level
reduced to "7 parts per million on a fat basi:3 in 1972.
Trie Food and Drug Admnistration has taken no action against any
obher products for PCB contamination but has infor-ued the States and
others that it would consider action on ;-,ii.lk :if PCBs exceed 0.2 parbs
per million (whole basis) and on fish if PCB:> exceeds 5 parts per million.
Some States have takcr.i .action to remove milk from the market b-.iat .-.ontained
insre than 0.2 parts pur million PCBs.
The temporary tolerances recently proposed by FDA are listed in Table 1.
The guidelines and the temporary tolerances taken into account avail-
able toxicological data, the estimated amount and type of intake of PCB
from food, and also the sensitivity of the methods used for detecting PCB.
Thus more PCB is allowed in poultry than in eggs because children are fed
egg yolk, and children are not considered to have as efficient detoxication
mechanism for handling PCBs as adults. It should be noted that these limits
were established to deal with particular incidents, and thus may be changed
as new knowledge develops or as circumstances change.
Some food has been discovered to be contaminated because of migration
from food packaging materials containing PCBs. Thus FDA also has proposed
that a temporary tolerance of 5 parts per million in paper packaging
177
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Table 1
FDA Proposed Temporary Tolerances for PCD Residues
Food Tolerance
Milk
Dairy Products
Poultry
Eggs
Complete animal feeds
Animal feed components
(including fish meal)
Fish
Infant and junior food
Food-packaging materials
2.5 ppm (fat basis)
2.5 ppm (fat basis)
5 ppm (fat basis)
0.5 ppm
0.5 ppm
5 ppm
5 ppm
0.1 ppm
5 ppm
(edible portion)
178
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materials be established permitting unavoidable PCB residues in such
materials for a period of one year. This will provide an opportunity for
the orderly elimination of PCB-containing raw materials used in the
manufacture of food packaging materials.
EPA recently has proposed regulations which would prohibit all
intentional discharges of PCB into the water, and would limit PCB levels
in the water to .01 parts per billion. These regulations probably would
be enforced through use of the Refuse Act.
III. APPLICATION OF REGULATORY AUTHORITIES
Within the past two years there have been several incidents involving
PCB contamination. These include the following:
In September 1969 FDA detected PCBs in West Virginia milk. The source
of PCBs was suspected to be the use of spent transformer fluid as a solvent
for herbicide spray. Grade A milk shippers involved were taken off production
by the State.
In April 1970 FDA identified the presence of PCB residues in milk
sampled by the Ohio State Department of Agriculture. The Department removed
a large quantity of milk from the market. The chemical was traced to a
material used as a sealant in the silos where dairy feed was stored.
Similar occurrences of PCB contamination of dairy herds have been reported
in several Southeastern States.
Since June 1971, the Meat and Poultry Inspection Program (MPIP) and
the Poultry Division, Consumer and Marketing Service, USDA, have been survey-
ing specifically for PCBs. Prior to that time, the MPIP's ongoing survey of
chlorinated hydrocarbons should have detected any PCBs present in animal or
poultry fat at a level of 1 parts per million or above. None was detected
in the fat of poultry, swine, cattle, or sheep prior to December 1970. Since
that time, there have been five separate incidents of contamination of poultry
with PCBs. Each appears to be a single-source, one-time occurrence. The
Poultry Division's egg sampling program in the Southeastern U.S. and in
Minnesota has not detected levels of PCBs which are significant—most
values falling below the sensitivity of the method.
Contamination of hens slaughtered on December 2, 1970, led to placing
all laying hens in Orange, Sullivan, and Ulster Counties, New York, under
quarantine through August 30, 1971, requiring pretesting for PCBs prior to
slaughter. Levels up to 26.8 parts per million PCBs were found in the fat.
Approximately 137,100 hens were condemned and buried on the farms. Flocks
containing less than 5 parts per million PCBs were sold in commercial
channels, frequently at drastically reduced prices. Eggs from contaminated
flocks were destroyed. The source of contamination was feed containing
returned bakery product wrappings.
Frozen turkeys produced on farms from Modesto, Fresno, Stockton, and
Santa Rosa, California, were found to contain up to 28 parts per million of
of PCBs in the fat. The source of contamination is unknown. All turkeys
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from these sources (approximately 100,000 Ibs.) were detained until
testing -was completed (Feb.-May 1971). Muscle meat was salvaged and
used in turkey rolls. Fat and skin containing over 5 parts per million
PCBs went to nonfood uses.
Contamination of anchovy fish meal with PCBs from a leaky heat ex-
changer was discovered by -the Monsanto Company in July 1971 in Wilmington,
N.C. One immediate and noticeable result was poor hatchability of eggs
from the poultry fed the PCB contaminated diet. Accordingly, USDA
required that all poultry coming to market from_ these States be tested
before marketing. During the first 2 weeks of testing, £Ul samples were
analyzed, representing over 2.5 million birds. Of these, 2.It percent
were retained until disposition could be made. The 88,000 chickens which
had been fed the fish meal were destroyed by the owner of the chickens.
FDA seized 753000 eggs, 5 shipments of commercial fish feed, and 1 ship-
ment of fish meal which had been contaminated, and USDA barred from market
more than 30,000 pounds of processed frozen eggs. In addition, the processing
firm recalled over 16,000 tons of the PCB-contaminated fish meal.
In September 1971, turkeys from one grower on eight farms in Detroit
Lakes, Minnesota, were found to contain up to 20 parts per million PCBs
(fat basis). One hundred forty flocks in the immediate area, including
parts of Minnesota, North Dakota, and South Dakota, were tested , but no
levels above 2 parts per million were found. Approximately 1 million
turkeys were withheld from market by the single grower until residue levels
were acceptable. The source of the PCBs has not been determined, but
feedgrade fat contaminated with PCBs from a heat exchanger is suspected.
Also in September, the State of Michigan stopped its annual program
of distribution of Cohoe Slamon from Lake Michigan, because the fish
contained high residues of PCB and DDT.
In February 1972 chickens in Maine were discovered to contain PCB
contamination of up to 172 parts per million in their fat. These con-
taminated chickens had been given feed from a plant in Thorndike, Maine,
but officials have been unable to locate the exact source of the PCBs.
More than a million chickens have been destroyed.
Many of these incidents have evoked criticism of the Federal Government
for failure to detect the problem sooner or for failure to act more stringently.
It must be recognized that insofar as detection of problems relies on in-
spection of food products being shipped to market, it is impossible to
inspect even a small fraction of the foods being shipped. Factory inspection
can detect some problems, but even this approach is severely limited by
available resources. The prime reliance must be on controlling the use of
the offending substance.
IV. FUTURE ACTIONS AND NEEDS
Enough data are available to indicate that PCBs are pervasive in the
environment. The basic regulatory challenge is thus twofold: to minimize
human exposure to PCBs already present in the environment and to prevent
more PCBs from entering the environment.
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Based on available monitoring data and reports, one route of human
exposure to PCBs currently in the environment is through food. The PCB
contribution made by other routes of exposure has not been sufficiently
measured.
The FDA has issued a proposal which will prohibit the use of PCBs
in and around food processing plants and will establish limitations on
the use of salvaged paper containing industrial chemicals for food packag-
ing. These proposed actions should prevent occurrences such as the WiLning-
ton incident and the problem of PCBs in food packaging materials. However,
there will still be problems, as evidenced by the Coho Salmon contamination,
the mysterious Minnesota turkeys, and the discovery of high levels of
PCBs in cardboard food containers. The solution to these problems seems to
lie in a better understanding of the path which PCBs follow through the
environment and on full use of existing regulatory authorities. Even with
better understanding we can probably expect future isolated incidents of
PCB contamination.
Existing regulatory authority is generally inadequate to prevent more
PCBs from entering the environment. The Monsanto Company has reported volun-
tarily limiting the distribution of PCBs to "closed systems" but this limit
has no force of law behind it. The government has no power to restrict
imports of PCBs by foreign manufacturers, and if it disagreed with Monsanto1s
judgment on allowable uses it could not impose more stringent limitations
on Monsanto-or on any other potential manufacturer.
This regulatory gap would be filled by the Admin: -uration's proposed
Toxic Substances Control Act. The proposed Act, sent Congress in
February 1971, would authorize the Administrator of ER ^ restrict or
prohibit the use or distribution of a chemical substance if such restriction
were necessary to protect health and the environment, and it would also
authorize him to issue standards for tests to be performed and for results
to be achieved from such tests for various classes and uses of new substances.
Thus, in addition to providing the regulatory authority needed to deal with
the PCB problem, it would also establish a system for preventing new chemicals
from becoming similar problems. Action by the Congress to approve the Toxic
Substances Control Act is the most important step which can be taken to
deal with PCBs and sijnilar problems.
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